25th International Meeting on Organic Geochemistry IMOG 2011

<strong>25th</strong> <strong>International</strong> <strong>Meeting</strong>
on Organic Geochemistry
IMOG 2011
18 - 23 September
Interlaken, Switzerland
Book of abstracts
www.imog2011.com

The 25 th <strong>International</strong> <strong>Meeting</strong> on
Organic Geochemistry
Interlaken, Switzerland
18 th – 23 rd September 2011
Book of Abstracts
IMOG 2011 Secretary, Rapiergroup, 113-119 High Street, Hampton Hill,
Middlesex, TW12 1NJ, UK
email: IMOGsecretary@rapiergroup.com

Dear Conference Delegates,
Preface
The Book of Abstracts represents the work that will be presented at the 25 th <strong>International</strong> <strong>Meeting</strong> on
Organic Geochemistry, held in Interlaken, Switzerland from 18 th – 23 rd September 2011. The conference is
organised under the auspices of the European Association of Organic Geochemists. A total of 586
abstracts were submitted for consideration by the Scientific Committee, of which all were accepted. Some
abstracts were withdrawn during the process of preparation of the abstract volume, leaving 580 papers to
be presented at the conference.
The Scientific Committee selected 85 abstracts to be presented orally in either plenary or parallel sessions.
In this volume, abstracts of the oral presentation are numbered from 1 – 85 with the prefix ―O‖. The
remaining 495 abstracts were accepted as poster presentations and grouped in themed sessions. The
posters will be split, with half on view for Monday and Tuesday and the remaining half on view for
Wednesday and Thursday. Each themes session will be ―open‖ on a specific day, when the presenting
author will be available for discussion. During this specific day the author should be in attendance during
the poster session. Abstracts of posters are numbered from 001 to 516 with the prefix ―P‖. Posters P001 to
P126 are open for discussion with the presenting author on Monday; P128 to P251 on Tuesday; P254 to
P377 on Wednesday and P380 to P516 on Thursday.
We hope that you will find this Book of Abstracts informative and wish you a successful and enjoyable
conference.
ORGANISING COMMITTEE
Volker Dieckmann - Shell, The Netherlands (Conference Chairman)
Erik Tegelaar - Shell, The Netherlands (Chairman Scientific Programme)
Pim van Bergen – Shell, Scotland
Stefano Bernasconi, ETH Zurich, Switzerland
Michael Schmidt, University of Zurich, Switzerland
Carsten Schubert, EAWAG, Switzerland
SCIENTIFIC COMMITTEE
Erik Tegelaar - Shell, The Netherlands (Chairman)
Jan de Leeuw – Royal NIOZ and Utrecht University, The Netherlands
Sylvie Derenne - CNRS Paris, France
Tim Eglinton - ETH Zurich, Switzerland
Francois Gelin - Total, France
Vincent Grossi - University of Lyon, France
Raymond Michels - CNRS Nancy, France
Richard Patience - Chevron, U.S.A.
Ann Pearson - Harvard University, U.S.A.
Alex Sessions - CalTech, U.S.A.
Tom Wagner - Newcastle University, U.K.
Heinz Wilkes - GFZ Potsdam, Germany
2

Oral Programme
Poster Programme
Oral Presentations
Contents
Monday 19 th September O-01 – O-18
Tuesday 20 th September O-19 – O-37
Wednesday 21 st September O-38 – O-54
Thursday 22 nd September O-55 – O-73
Friday 23 rd September O-74 – O-82
Poster Presentations
Monday 19 th September P-001 – P-126
Analytical developments P-001 – P-031
Kerogen and coal P-033 – P-056
Petroleum biomarkers 1 P-058 – P-076
Petroleum case studies 1 P-078 – P-112
Petroleum source rocks 1 P-114 – P-126
Tuesday 20 th September P-128 – P-251
Archeology P-128 – P-136
Environment and pollution 1 P-138 – P-154
Microbial geochemistry/lipidomics/genomics 1 P-156 – P-185
Proxies and paleoreconstructions 1 P-187 – P-221
Soil and peat and terrestrial OM 1 P-224 – P-251
Wednesday 21 st September P-254 – P-377
Gas geochemistry P-254 – P-266
Petroleum biomarkers 2 P-268 – P-284
Petroleum case studies 2 P-285 – P-318
Petroleum source rocks 2 P-319 – P-332
Reservoir/production P-335 – P-352
Sulfur chemistry P-354 – P-362
Unconventionals P-364 – P-377
Thursday 22 nd September P-380 – P-516
Environment and pollution 2 P-380 – P-399
Isotope geochemistry P-401 – P-420
Microbial geochemistry/lipidomics/genomics 2 P-423 – P-451
Proxies and paleoreconstructions 2 P-453 – P-489
Soil and peat and terrestrial OM 2 P-491 – P-516
Author Index
3

Monday 19 th September 2011 - Morning
Theater-Saal
08.30 – 09.30 Opening Ceremony
Plenary 1
Chair: Erik Tegelaar
09.30 – 09.55 O-01 Extractive and structural phenolic compounds in a Neolithic leather from the
Swiss Alps
Jorge E. Spangenberg, Albert Hafner
09.55 – 10.20 O-02 Melting history of West Antarctic ice sheet since the last glacial
maximum revealed by compound-specific radiocarbon dating
Nao Ohkouchi, Hisami Suga, Yoshito Chikaraishi, Yusuke Yokoyama, Takahiro
Yamazaki, Yosuke Miyairi, Hiroyuki Matsuzaki, John Anderson, John Southon,
Timothy Eglinton
10.20 – 10.45 O-03 Diamonds in the rough: identification of individual naphthenic acids in
petroleum and oil sands process water
Steven Rowland, Charles West, Alan Scarlett, David Jones, Richard Frank
10.45 – 11.10 Coffee break
Plenary 2
Chair: James Maxwell
11.10 – 11.35 O-04 Insights about the marine nitrogen cycle from nitrogen isotopes of
sedimentary porphyrins
Meytal B. Higgins, Ann Pearson
11.35 – 12.00 O-05 Highly condensed, sulfur-rich hydrocarbon detected in oils altered by
thermochemical sulfate reduction: precursors to TSR-solid bitumen
Clifford Walters, Kuangnan Qian, Chunpingq Wu, Anthony Mennito, Zhibin Wei
12.00 – 12.25 O-06 Eocene out-of-India dispersal of Asian dipterocarps
Suryendu Dutta, Suryakant Tripathi, Monalisa Mallick, Runcie Mathew, Paul
Greenwood, Mulagalapalli Rao, Roger Summons
12.25 – 13.40 Lunch
13.00 – 14:30 Short Course (In Ball-Saal)
Advances in geochemical proxies for methane cycling in the past
Thomas Wagner, Richard Pancost and Helen Talbot
13.40 – 15.05 Poster Session 1 (In Kongress-Saal)
Chair: Matthias Keym
Analytical developments, Kerogen & coal, Petroleum biomarkers 1,
Petroleum case studies 1, Petroleum source rocks 1 (P001- P126)
4

Monday 19 th September 2011 - Afternoon
Theater-Saal
Paleobiomarkers
Chair: Richard Pancost
15.05 – 15.30 O-07 The syngeneity of Precambrian sterane biomarkers
Amber Jarrett, Jochen Brocks
15.30 – 15.55 O-08 An integrated lipid biomarker and chemostratigraphic record of
biospheric evolution through the late Ordovician mass extinction event
Megan Rohrssen, Gordon Love
15.55 – 16.20 O-09 A high resolution compound specific carbon isotope study of the PETM in
Northern Spain
Hayley Manners, Stephen Grimes, Paul Sutton, Laura Domingo, Richard Pancost,
Melanie Leng, Kyle Taylor, Richard Twitchett, Malcolm Hart, Nieves Lopez-Martinez
16.20 – 16.45 Coffee break
IPL degradation and preservation
Kai Uwe Hinrichs
16.45 – 17.10 O-13 Degradation of intact polar lipids in sandy sediments: insights from a
laboratory experiment
Jörn Logemann, Jutta Graue, Jürgen Köster, Bert Engelen, Heribert Cypionka,
Jürgen Rullkötter
17.10 – 17.35 O-14 Exploring the diversity of archaeal ether lipids in marine sediments
Xiaolei Liu, Julius Lipp, Jeffrey Simpson, Roger Summons, Kai-Uwe Hinrichs
17.35 – 18.00 O-15 Differential degradation of intact polar lipid GDGTs upon oxidation of a
turbidite sediment
Sabine K. Lengger, Mariska Kraaij, Marianne Baas, Ellen C. Hopmans,
Jaap S. Sinninghe Damsté, Stefan Schouten
18.05 – 19.00 Treibs Award
5

Monday 19 th September 2011 - Afternoon
Ball-Saal
Sulfur chemistry
Chair: Daniel Dessort
15.05 – 15.30 O-10 Sulfur species as facilitators for water splitting to react with organic
matter under medium temperatures
Ward Said-Ahmad, Alon Amrani, Zeev Aizenshtat
15.30 – 15.55 O-11 Sulfur rich petroleum systems: TSR and thermal cracking in basin and
reservoir field studies, simulation experiments and model calibration
Olaf G. Podlaha, Henning Peters, Erdem Idiz, Volker Dieckmann
15.55 – 16.20 O-12 Sulfur isotope systematic of individual organic compounds during
thermochemical sulfate reduction
Alon Amrani, Andrei Deev, Alex Sessions, Yongchun Tang, Jess Adkins, Ronald Hill,
Michael Moldowan, Zhibin Wei
16.20 – 16.45 Coffee break
Petroleum system case studies
Chair: Shuichang Zhang
16.45 – 17.10 O-16 Improved genetic characterization of Brazilian oils using combined
molecular (biomarkers) and isotope geochemistry
Jarbas Vicente Poley Guzzo, Eugenio Santos Neto, Alexandre de Andrade Ferreira
17.10 – 17.35 O-17 Composition analysis of individual petroleum inclusions: Preliminary
application in the reservoir-filling history of the Tahe oil field, Tarim Basin, NW
China
Weijun Shi, Maowen Li, Binbin Xi, Jin Xu, Zhirong Zhang, Jianzhong Qin, Hong Jiang
17.35 – 18.00 O-18 Petroleum system analysis South East Abu Dhabi
Peter Nederlof, Özkan Huvaz, Andy Bell, Ahmed Khouri, Abdelfatah El
6

Tuesday 20 th September 2011 – Morning
Theater-Saal
09.00 – 09.05 Opening Remarks
Plenary 3
Chair: Alexei Milkov
09.05 – 09.30 O-19 The borolithochromes: boron-containing organic pigments from a
Jurassic red alga
Klaus Wolkenstein, Jürgen H. Gross, Heinz Falk
09.30 – 09.55 O-20 Organic aerosol transport and deposition over the southern ocean
Susanne Fietz, Alfredo Martínez-Garcia, Bastian Hambach, Sze Ling Ho, Frank
Lamy, Walter Geibert, Antoni Rosell-Melé
09.55 – 10.20 O-21 Study of the stable isotopic composition of severely biodegraded oils as
petroleum system correlation parameters
Norka Marcano, Steve Larter, Bernhard Mayer
10.20 – 10.45 O-22 New insights into the sources and application of biohopanoid molecular
proxies in diverse settings
Helen Talbot
10.45 – 11.10 Coffee break
Plenary 4
Chair: Simon Brassell
11.10 – 11.35 O-23 Novel applications of trace metals and Molybdenum isotopes in
petroleum fluid studies
Sander van den Boorn, Riccardo Avanzinelli, Pim van Bergen, Tim Elliott, Corey
Archer, Andrew Bishop, Volker Dieckmann
11.35 – 12.00 O-24 A biological source for the orphan branched tetraethers ubiquitously
occurring in soil and coastal marine and lake sediments
Jaap Sinninghe Damste, Irene Rijpstra, Johan Weijers, Ellen Hopmans, Baerbel
Foesel, Joerg Overmann, Svetlana Dedysh
12.00 – 12.25 O-25 The chemical structure of insoluble organic matter in carbonaceous
meteorites
Sylvie Derenne, François Robert
12.25 – 13.40 Lunch
13.00 – 14:30 Short Course (In Ball-Saal)
Shale gas
Brian Horsfield and Ger van Graas
13.40 – 15.05 Poster Session 2 (In Kongress-Saal)
Chair: Matthias Keym
Archeology, Environment and Pollution 1, Microbial Geochemistry/
Lipidomics/Genomics 1, Proxies & Paleoreconstructions 1, Soil & Peat & Terrestrial
OM 1 (P128 – P251)
7

Tuesday 20 th September 2011 – Afternoon
Theater-Saal
New approaches to microbial biogeochemistry
Chair: Josef Werne
15.05 – 15.30 O-26 A radiotracer experiment for investigating the degradation kinetics of
intact polar lipids in sediments
Sitan Xie, Julius Sebastian Lipp, Gunter Wegener, Timothy G. Ferdelman, Kai-Uwe
Hinrichs
15.30 – 15.55 O-27 Coenzyme factor 430: abundance and isotopic compositions for tracing a
key molecule of methanogenesis and reverse-methanogenesis
Yoshinori Takano, Hiroyuki Imachi, Nana O. Ogawa, Yoshito Chikaraishi, Nao
Ohkouchi
15.55 – 16.20 O-28 Nitrogen isotopic signatures of amino acids in microbes: culture
experiments and applications to marine sediments
Yasuhiko Yamaguchi, Yoshinori Takano, Yoshito Chikaraishi, Nanako Ogawa,
Hiroyuki Imachi, Hisami Suga, Yusuke Yokoyama, Naohiko Ohkouchi
16.20 – 16.45 Coffee break
Leaf wax hydrogen isotopes
Chair: Heinz Wilkes
16.45 – 17.10 O-32 The role of light intensity in controlling the δD and δ13C values
of organic compounds in leaf waxes: should we worry about it?
Nikolai Pedentchouk, Kirill Peskov, Tracy Lawson, Yvette Eley
17.10 – 17.35 O-33 Empirical relationship between leaf wax n-Alkane δD and altitude in the
Wuyi, Shennongjia and Tianshan Mountains, China: implications for
Paleoaltimetry
Pan Luo, Ping'an Peng, Gerd Gleixner, Zhuo Zheng, Zhonghe Pang,
17.35 – 18.00 O-34 Hydrogen isotopic composition of long chain n-alkanes from a marine
sediment core transect off Africa: implications for the tropical African rainbelt
James Collins, Enno Schefuß, Stefan Mulitza, Matthias Prange, Gerold Wefer
8

Tuesday 20 th September 2011 - Afternoon
Ball-Saal
Soil and peat
Chair: Rienk Smittenberg
15.05 – 15.30 O-29 Influence of temperature on methane cycling and methanotroph-related
biomarkers in peat moss
Julia van Winden, Gert-Jan Reichart, Helen Talbot, Niall McNamara, Albert Benthien,
Jaap Sinninghe Damsté
15.30 – 15.55 O-30 First detection of triterpenyl acetates in soils: sources and potential as
new palaeoenvironmental biomarkers
Marlène Lavrieux, Jérémy Jacob, Claude Le Milbeau, Jean-Robert Disnar,
Renata Zocatelli, Jean-Gabriel Bréheret, Kazuo Masuda
15.55 – 16.20 O-31 The fate of collembola derived organic matter in soil
Ian Bull, Andrew Rawlins, Philip Ineson, Richard Evershed
16.20 – 16.45 Coffee break
Petroleum biomarkers
Chair: Ken Peters
16.45 – 17.10 O-35 Biomarker evidence for the Late Neoproterozoic deep-water
oxygenation
Chunjiang Wang, Maoyan Zhu
17.10 – 17.35 O-36 Highest resolution for oil dating (≤ 10 Ma): implications for the
paleocene-eocene thermal maximum from stable isotope data
Christiane Eiserbeck, Kliti Grice, Joseph Curiale
17.35 – 18.00 O-37 The seco-oleananes: identification, origin, application and distributions
in late cretaceous/tertiary deltaic petroleum systems
Olukayode Samuel, Hans Peter Nytoft, Geir Kildahl-Andersen, Jon Eigill Johansen
9

Wednesday 21 st September 2011 – Morning
Theater-Saal
09.00 – 09.05 Opening Remarks
Plenary 5
Chair: Stefano Bernasconi
09.05 – 09.30 O-38 Microbial communities associated to deep subsurface coal layers: a
review of the DEBITS project
Kai Mangelsdorf, Clemens Glombitza, Andrea Vieth, Tiem Vu Thi Anh, Jens
Kallmeyer, Klaus Zink, Richard Sykes, R. John Parkes, John Fry, Brian Horsfield
09.30 – 09.55 O-39 The fate of terrestrial organic matter in the Yangtze River - East China
sea system and its implications for the use of terrestrial organic proxies
Chun Zhu, Thomas Wagner, Helen Talbot, Johan Weijers, Richard Pancost
09.55 – 10.20 O-40 The importance of geochemical analysis in shale gas plays: beyond just
the organic components
Harry Dembicki, Jonathan Madren
10.20 – 10.45 O-41 Multi technique approach resolves soft-tissue preservation in 50 million
year old reptile skin
Bart van Dongen, Phill Manning, Nick Edwards, Holly Barden, Peter Larson,
Uwe Bergmann, William Sellers, Roy Wogelius
10.45 – 11.10 Coffee break
Plenary 6
Chair: John Volkman
11.10 – 11.35 O-42 Charge history and petroleum geochemistry of dual phase accumulations
on the Norwegian continental shelf using comparative analysis of the liquid
and vapour phase
Linda Schulz, Michael Erdman, Olaf Thießen
11.35 – 12.00 O-43 Molecular study of organic residues in an exceptional collection of
potteries from Deir el-Médineh (XVIIIth dynasty, Egypt)
Claire Bastien, Armelle Charrié-Duhaut, Geneviève Pierrat-Bonnefois, Jacques
Connan, Claude Le Milbeau, Jorge Spangenberg
12.00 – 12.25 O-44 Bacterial formation of (di)ether lipids: a state of the art
Vincent Grossi, Agnès Hirschler-Réa, Philippe Schaeffer, Cristiana Cravo-Laureau
12.25 – 13.40 Lunch
13.00 – 14:30 Short Course (In Ball-Saal)
Using ToF-SIMS to study biomarkers
Volker Thiel and Sandra Siljeström
13.40 – 15.05 Poster Session 3 (In Kongress-Saal)
Chair: Henning Peters
Gas Geochemistry, Petroleum Biomarkers 2, Petroleum Case Studies 2, Petroleum Source
Rocks 2, Reservoir/Production, Sulfur Chemistry, Unconventionals (P256 – P379)
10

Wednesday 21 st September 2011 – Afternoon
Theater-Saal
Analytical developments
Chair: Tim Eglinton
15.05 – 15.30 O-45 Advancing trace-level analysis of marker compounds in ice cores to
generate records of South American fire activity
Matthew Makou, Lonnie Thompson, Timothy Eglinton, Daniel Montluçon
15.30 – 15.55 O-46 Development of a novel tool for paleoclimate research based on
compound-specific δ18O analyses of (hemi-)cellulose-derived
monosaccharides
Michael Zech, Bruno Glaser, Dieter Juchelka, Karsten Kalbitz, Christoph Mayr,
Mario Tuthorn, Roland Werner
15.55 – 16.20 O-47 Current developments and challenges in compound-specific radiocarbon
analysis
Rienk Smittenberg, Merle Gierga, Axel Birkholz, Irka Hajdas, Lukas Wacker,
Michael Schmidt, Stefano Bernasconi
16.20 – 16.45 Coffee break
Novel isotopes in proxies
Chair: Stefan Schouten
16.45 – 17.10 O-51 Role of biosynthesis leading to the saw-toothed profile in δ13C and δ2H
of n-alkanes and systematic isotopic differences between n-, iso- & anteisoalkanes
in leaf waxes of land plants
Youping Zhou, Kliti Grice, Hilary Stuart Williams, Graham Farquhar, Charles Hocart
17.10 – 17.35 O-52 Nitrogen isotopes of amino acids: first results in sediments and gorgonian
corals of a new tool to reconstruct organic nitrogen source and cycling from
paleoarchives
Matthew McCarthy, Owen Sherwood, Fabian Batista, Moritz Lehmann, Christina
Ravelo, Carsten Schubert
11

Wednesday 21 st September 2011 – Afternoon
Ball-Saal
Hydrocarbon generation and expulsion
Chair: Raymond Michels
15.05 – 15.30 O-48 Evolution of petroleum composition during generation and expulsion - a
case study on the Bakken formation
Philipp Kuhn, Brian Horsfield, Rolando di Primio
15.30 – 15.55 O-49 Determination of effective source rocks for quaternary biogenic gas
generation in the eastern Caidam Basin, NW China
Shuichang Zhang, Maowen Li, Yanhua Shuai, Jenny Wong, Junito Reyes, Sneh
Achal
15.55 – 16.20 O-50 Beyond orgas- BP's new predictive model for biogenic and thermogenic
gas expulsion from source rocks
Mark Osborne, Tony Barwise
16.20 – 16.45 Coffee break
Kerogen and coal
Chair: Richard Sykes
16.45 – 17.10 O-53 Biomarkers and stable isotopes of euxinia and their role in fossil
preservation
Ines Melendez, Kliti Grice, Kate Trinajstic, Katherine Thompson, Mojgan Ladjaverdi,
Arndt Schimmelmann, Paul Greenwood
17.10 – 17.35 O-54 Biomarker and petrographic evidence for the origin and maturity of
perhydrous arctic coal and associated bitumen
Chris Marshall, David Large, Colin Snape, Julius Babatunde, Will Meredith, Clement
Uguna, Baruch Spiro, Alv Orheim
19.00 – 20.00 Conference Drinks Reception, Casino Kursaal
20.15 - late Conference Dinner, Konzerthalle, Casino Kursaal
12

Thursday 22 nd September 2011 - Morning
Theater-Saal
09.00 – 09.05 Opening Remarks
Plenary 7
Chair: Chris Cornford
09.05 – 09.30 O-55 The organic geochemistry of carbon management
Steve Larter, Thomas Oldenburg, Haiping Huang, Ian Gates, Barry Bennett, Norka
Marcano
09.30 – 09.55 O-56 The two largest soil organic matter pools in Arctic permafrost show
different degradation potentials upon coastal expulsion
Örjan Gustafsson, Jorien Vonk, Emma Karlsson, Laura Sanchez-Garcia, Bart van
Dongen, Igor Semiletov, Oleg Dudarev, Alex Charkin, Tim Eglinton, August
Andersson
09.55 – 10.20 O-57 Exploring mass extinction events (Triassic/Jurassic and
Permian/Triassic): association with global warming events
Kliti Grice, Birgit Nabbefeld, Richard Twitchett, Lindsay Hays, Kenneth Williford,
Alex Holman, Roger Summons, Jennifer McElwain, Michael Böttcher
10.20 – 10.45 O-58 Enhanced biomarker detection in microbial mats using ToF-SIMS
Tim Leefmann, Christine Heim, Alexander Kaever, Peter Meinicke, Jukka Lausmaa,
Peter Sjövall, Volker Thiel
10.45 – 11.10 Coffee break
Plenary 8
Chair: Tanja Barth
11.10 – 11.35 O-59 Black shale formation by microbial mats, lacking sterane-producing
eukaryotes in the late mesoproterozoic Taoudeni Basin (1.1 Ga; Mauritania)
Martin Blumenberg, Joachim Reitner, Sascha Doering, Walter Riegel, Linda C. Kah,
Geoffrey J. Gilleaudeau, Volker Thiel
11.35 – 12.00 O-60 Assessing subsurface microbial carbon assimilation by lipid 13CDIC-DH2O
stable isotope probing
Gunter Wegener, Marlene Bausch, Nguyen Manh Thang, Matthias Kellermann,
Xavier Pietro, Kai-Uwe Hinrichs, Antje Boetius
12.00 – 12.25 O-61 The significant impact of weathering on spilled Gulf of Mexico MC252 oil
chemistry and its fingerprinting of samples collected from the sea surface and
shore between May and September 2010
Changrui Gong, Alexei Milkov, David Grass, Michael Sullivan, Tomieka Searcy, Leon
Dzou, Pierre-Andre Depret
12.25 – 13.40 Lunch
13.00 – 14:30 Short Course (In Ball-Saal)
Flow assurance
John Ratulowski
13

13.40 – 15.05 Poster Session 4 (In Kongress-Saal)
Chair: Henning Peters
Environment and Pollution 2, Isotope geochemistry, Microbial
Geochemistry/Lipidomics/Genomics 2, Proxies & Paleoreconstructions 2,
Soil & Peat & Terrestrial OM 2 (P381 – P516)
Thursday 22 nd September 2011 - Afternoon
Theater-Saal
Paleotemperature proxies
Chair: Nao Ohkouchi
15.05 – 15.30 O-62 A reappraisal of long-chain diol proxies
Stefan Schouten, Sebastiaan Rampen, Veronica Willmott, Jung-Hyun Kim, Eleonora
Uliana, Enno Schefuß, Jaap Sinninghe Damsté
15.30 – 15.55 O-63 Simultaneous shifts in temperature in Central Europe and Greenland
during the last deglaciation
Cornelia I. Blaga, Gert-Jan Reichart, Andre F. Lotter, Flavio S. Anselmetti,
Jaap S. Sinninghe Damsté
15.55 – 16.20 O-64 Simplification and recalibration of the MBT/CBT paleothermometer
based on branched tetraether lipids in globally distributed soils
Francien Peterse, Jaap van der Meer, Johan Weijers, Noah Fierer, Robert Jackson,
Jung-Hyun Kim, Stefan Schouten, Jaap Sinninghe Damsté
16.20 – 16.45 Coffee break
Water column microbial biogeochemistry
Chair: Stuart Wakeham
16.45 – 17.10 O-68 Latitudinal distribution of archaeal H-lipids
Carme Huguet, Susanne Fietz, Antoni Rosell-Melé
17.10 – 17.35 O-69 Role of photooxidative processes in senescent phytoplankton cells and
attached bacteria in the preservation of organic matter
Morgan Petit, Richard Sempere, Stuart G. Wakeham, John K. Volkman, Frédéric
Vaultier, Jean-François Rontani
17.35 – 18.00 O-70 Deciphering the physiological significance of hopanoids in the marine
geologic record
James Saenz, Roger Summons, Timothy Eglinton, Stuart Wakeham, John Waterbury
14

Thursday 22 nd September 2011 - Afternoon
Ball-Saal
Environment and pollution
Chair: Jan Schwarzbauer
15.05 – 15.30 O-65 Fluxes and isotope composition of selected halocarbons from sea grass
meadows
Enno Bahlmann, Ingo Weinberg, Richard Seifert, Walter Michaelis
15.30 – 15.55 O-66 Investigation of metagenomic clone library in biosurfactant synthesis and
hydrocarbon biodegradation processes
Suzan Vasconcellos, Bruna Dellagnezze, Valéria Oliveira, Philip Hendry, Carol
Nichols, Eugenio Santos Neto, Herbert Volk
15.55 – 16.20 O-67 Biogeochemical impact of CO2 exposure on reservoir rocks and the
indigenous microbial community
Ann-Kathrin Scherf, Maren Wandrey, Kornelia Zemke, Andrea Vieth-Hillebrand,
Ketzin group
16.20 – 16.45 Coffee break
Hydrocarbon production
Chair: Daniel Stoddard
16.45 – 17.10 O-71 Aquathermolysis: pressure effect on gas production and oil composition
Violaine Lamoureux-Var, Françoise Behar
17.10 – 17.35 O-72 Compositional kinetic model for thermal evolution of extra heavy oils
and tar sands
Luc Fusetti, Yongchun Tang, Françoise Behar, Tuong-Van Ledoan, Paul-Marie
Marquaire, Roda Bounaceur, François Gelin
17.35 – 18.00 O-73 Designing tight-shale production strategies using diamondoid
nanotechnology
Jeremy Dahl, Shaun Moldowan, J. Michael Moldowan
15

Friday 23 rd September 2011 – Morning
Theater-Saal
09.00 – 09.05 Opening Remarks
AOM Lipids
Chair: Daniel Birgel
09.05 – 09.30 O-74 Tracing 13 C-labeled inorganic carbon into intact polar lipids of
thermophilic anaerobic methanotrophs provides new insights into pathways of
archaeal lipid biosynthesis
Matthias Y. Kellermann, Gunter Wegener, Yu-Shih Lin, Marcos Y. Yoshinaga,
Thomas Holler, Marcus Elvert, Kai-Uwe Hinrichs
09.30 – 09.55 O-75 Methane derived carbonates as an indicator of the bottom water anoxia:
Nile deep sea fan, the Eastern Mediterranean
Alina Stadnitskaia, Volker Liebetrau, Jaap Sinninghe Damsté
09.55 – 10.20 O-76 Carbon fluxes in phylogenetically distinct AOM performing microbial
consortia
Sebastian Bertram, Martin Blumenberg, Richard Seifert, Martin Krüger, Walter
Michaelis
10.20 – 10.45 Coffee break
GDGT sources
Chair: Johan Weijers
10.45 – 11.10 O-80 Denitrifying bacteria as potential sources of isoalkane-GDGT
Cornelia Mueller-Niggemann, Andrea Bannert, Michael Schloter, Kai Mangelsdorf,
Lorenz Schwark
11.10 – 11.35 O-81 Hydrogen isotopic compositions of archaeal tetraethers
Masanori Kaneko, Hiroshi Naraoka
11.35 – 12.00 O-82 Tetraether lipid profiles in cultures and sediments: novel structures and
geochemical significance
Christopher Knappy, Hugh Morgan, Brendan Keely
12.00 – 13.00 Closing Ceremony
16

Friday 23 rd September 2011 – Morning
Ball-Saal
09.00 – 09.05 Opening Remarks
Fluid property predictions
Chair: Gary Muscio
09.05 – 09.30 O-77 Fluid API gravity prediction in basin modelling
Rolando di Primio, Eric Lehne, Philipp Kuhn, Friedemann Baur, Brian Horsfield
09.30 – 09.55 O-78 Fluid property prediction from advanced mud gas (AMG) systems:
opportunities and pitfalls
Daniel McKinney, Edward Clarke, E. Esra Inan
09.55 – 10.20 O-79 Metre-scale fluid property variation within an oil field revealed by Mud
Gas Isotope Logging (MGIL)
Andrew Murray, Daniel Dawson, Stephen Larter
10.20 – 10.45 Coffee break
Shale gas
Chair: Martin Fowler
10.45 – 11.10 O-83 Evolution of "shale gases" in fractured reservoirs in the foothills of the
Western Canada sedimentary basin
Barbara Tilley, Karlis Muehlenbachs
11.10 – 11.35 O-84 Prediction of gas volume and dryness in shale gas systems: kinetic
modeling of kerogen and retained hydrocarbons thermal cracking in barnett
and posidonia shales
Françoise Behar, Daniel Jarvie
11.35 – 12.00 O-85 Mechanistic study of shale gas generation and gas isotope fractionations
Yongchun Tang, Daniel Xia
17

Poster Sessions (in Kongress-Saal)
Poster Session 1 - Monday 19 th September 2011
13.40 – 15.05
Analytical developments
P-001 Maturity assessment based on dibenzothiophenes distribution analyzed by
comprehensive two-dimensional gas chromatography with time of flight mass
spectrometry in oils from Colombia
Raphael S. F. Silva, Hélen G. M. Aguiar, Mario D. Rangel, Débora A. Azevedo,
Francisco R. Aquino neto
P-002 Structure and function of asphaltenes: a geochemical and ultrasound study
Geoff Abbott, Malcolm Povey
P-003 Factors controlling extractability of polycyclic aromatic hydrocarbons from
sedimentary organic matter using non-ionic surfactant
Akinsehinwa Akinlua, Torsten Schmidt
P-004 Preliminary study of acid degradation of lignin using microwave energy
Béatrice Allard, Sylvie Derenne
P-005 A Monte Carlo application for introducing source variability in source
apportionment calculations
August Andersson, Rebecca Sheesley, Jorien Vonk, Örjan Gustafsson
P-006 Chemical and geochemical characterization of heavily biodegraded oils from
colombia by comprehensive two-dimensional gas chromatography coupled to
time-of-flight mass spectrometry (GCXGC-TOFMS)
Renata Filgueiras, Ricardo Pereira, Raphael Salles, Leonardo Mogollón, Débora
A. Azevedo
P-007 High resolution measurement of tarmat in cores using laser pyrolysis
Daniel Dessort, Philippe Lapointe, Dominique Duclerc, Robert Le-Van-Loi
P-008 High resolution measurement of petroleum potential of oil shales using laser
pyrolysis on cores
Daniel Dessort, Pierre Allix, Jean-Michel Krafft, Dominique Duclerc, Robert Le-
Van-Loi
P-009 A new method for the combined detection of different faecal biomarker classes
and their binding types in soils using GC/MS
Michaela Dippold, Jago Birk, Guido Wiesenberg, Bruno Glaser
P-010 Acidic fraction analyses of Brazilian oils using petroleomics
Célio Fernando Figueiredo Angolini, Eugenio Vaz dos Santos Neto, Anita
Jocelyne Marsaioli
P-011 Rapid geochemical typing using infrared spectroscopy
Andrew Bishop, Amy Kelly, Patrick Killough
P-012 Heteroatom-containing compounds in maltenes and asphaltenes separated from
a sequence of Fort McMurray crude oils detected by negative-ion ESI FT-ICR
MS
Yinhua Pan, Yuhong Liao
18

P-013 Study on non GC amenable fractions in biodegraded oils of the Liaohe Basin by
negative-ion ESI FT-ICR MS and PY-GC
Yuhong Liao, Quan Shi
P-014 Evaluation of hydropyrolysis as a method for the quantification of black carbon
via the testing of standard reference materials
Will Meredith, Emma Tilston, Philippa Ascough, David Large, Colin Snape,
Michael Bird
P-015 Can comprehensive analysis of degraded oil indicate the conditions under which
biodegradation occurred in an oil reservoir?
Thomas Oldenburg, Steve Larter, Melisa Brown, Ben Hsieh, Ian Head, Martin
Jones, Caroline Aitkins, Niel Gray
P-016 Iron isotopic compositions of crude oils – development of a new extraction
method and first results
Christian Ostertag-Henning, Ulia Hammer, Friedhelm von Blanckenburg
P-017 Brazilian Miocene amber from Acre Basin (Solimões Formation): comprehensive
two-dimensional gas chromatography coupled with time-of-flight mass
spectrometry applied on its paleobotanical source
Ricardo Pereira, Ismar de Souza Carvalho, Antonio Carlos Sequeira Fernandes,
Karen Adami Rodrigues, Raphael Salles Ferreira Silva, Renata Filgueiras
Soares, Rosane Aguiar da Silva San Gil, Débora de Almeida Azevedo
P-018 Evaluation of accelerated solvent extraction (ASE) for pigment extraction from
lake and marine sediments
Neungrutai Saesaengseerung, Brendan Keely
P-019 Influence of extraction temperature on the chemical composition of soil lipids
Csanád Sajgó, József Fekete, Tünde Nyilas, Magdolna Hetényi
P-020 Improvement of HPLC-protocols for intact polar lipid analysis
Jan Schröder, Julius Lipp, Lars Wörmer, Kai-Uwe Hinrichs
P-021 A new solid electrolyte reactor for CF-IRMS analysis of hydrogen of organic
gases and compounds
Eric Galimov, Vyacheslav Sevastyanov, Nataliya Babulevich, Alexander
Arzhannikov
P-022 Open-system hydrous pyrolysis of source rock with continuous recovery
Martin Stockhausen, Lorenz Schwark
P-023 Petroleum fluid and source rock database: best practices
Gunardi Sulistyo, Andrew Pepper, David Schmidt, Steven Crews
P-024 The phenolic characterisation of peat profiles along a vegetation succession
using 13C-labelled tetramethylammonium hydroxide (13C-TMAH)
thermochemolysis
Eleanor Swain, Geoffrey Abbott
P-025 Construction of an organic geochemical database for marine surface sediments
Timothy Eglinton, Maria Luisa Tavagna, David Griffith, William Martin
19

P-026 Comparison of comprehensive two-dimensional gas chromatography/time-offlight
mass spectrometry and gas chromatography-mass spectrometry for
calculating the geochemical parameter
Huitong Wang, Na Weng, Shuichang Zhang
P-027 Separation of biomarkers for their compound specific isotope analysis
Huitong Wang, Shuichang Zhang, Caiyun Wei
P-028 Characterisation of lignin degradation products from dissolved organic matter: a
comparison of different extraction and analysis techniques
Jonathan Williams, Jennifer Dungait, Roland Bol, Geoffrey Abbott
P-029 Mass spectrometric analysis of intact polar lipids: pros and cons of Q-ToF, Ion
Trap and Single Quadrupole detection
Lars Wörmer, Julius Lipp, Jan Schröder, Kai-Uwe Hinrichs
P-030 Trace analysis of methylated substrates in marine sediment
Guangchao Zhuang, Yu-Shih Lin, Eoghan Reeves, Kai-Uwe Hinrichs
P-031 New techniques for understanding and mapping high-maturity petroleum
systems: examples from the San Joaquin Basin, San Juan Basin, and US Gulf
Coast
David Zinniker, J. Michael Moldowan, Jeremy Dahl, Peter Denisevich
Poster Session 1 - Monday 19 th September 2011
13.40 – 15.05
Kerogen and coal
P-033 An evaluation of petroleum source potential of fresh water versus marineinfluenced
coals from Malaysian Tertiary basins
Wan Hasiah Abdullah, Peter Abolins
P-034 Chemical structure of kerogen before and after hydrous pyrolysis
Nadezhda Burdelnaya, Dmitry Bushnev, Maxim Mokeev, Alexsander Gribanov
P-035 Contrasting macromolecular organic matter composition in surface sediments off
the Eurasian Arctic Rivers
Ayca Dogrul Selver, Christopher Varden, Igor Semiletov, Örjan Gustafsson,
Steve Boult, Bart E. van Dongen
P-036 Geochemical characteristics of organic matter preserved in silicified wood of
variable age
Monika Fabiańska
P-037 Evolution of depositional environment and biological origin of kerogen in Lower
Miocene Cypris shale in the Eger Graben, Czech Republic
Juraj Francu, Ivana Sýkorová, Bohdan Kříbek, Karel Martínek, Petr Rojík, Achim
Bechtel, Daniela Mácová
P-038 Organic geochemistry of coals and carbonaceous shales from the Palaeocene
Los Cuervos Formation in San Pedro del Río (Táchira State, Venezuela)
Marcos Escobar, Manuel Martinez, José R. Gallego, Gonzalo Marquez Azucena
Lara-Gonzalo
20

P-039 Organic carbon content and character of Holocene–Eocene sediments recovered
during IODP Expedition 317, Canterbury Basin, New Zealand
Simon George, Julius Lipp, George Claypool, Toshihiro Yoshimura, Expedition
317 Shipboard Scientific Party Integrated Ocean Drilling Program
P-040 Evolution of organic matter in lignite-containing sediments under different
environmental conditions: analytical pyrolysis (Py-GC/MS) proxy
José A. González-Pérez, Abad Chabbi, Cornelia Rumpel, José Mª de la Rosa,
Francisco J. González-Vila
P-041 Organic geochemistry of entrapped bitumen within kerogen/mineral matrix of an
Australian Late Paleoproterozoic lead-zinc-silver deposit
Alexander Holman, Kliti Grice, Caroline Jaraula, Arndt Schimmelmann
P-042 Search for chemotaxonomic indicator by analyses of resistant macromolecules in
plant fossils from the Cretaceous Futaba Group, Japan
Kei Ikeda, Ken Sawada, Hideto Nakamura, Masamichi Takahashi
P-043 Petrological and organic geochemical characteristics of the No. 11 coal in
Antaibao mine, China
Kankun Jin, Yanheng Li, Xiaoli Deng, Shenjun Qin
P-044 Geochemical characteristics of organic matter in the Kupferschiefer strata in the
Fore-Sudetic Monocline, SW Poland
Paweł Kosakowski, Adam Kowalski
P-045 Occurrence and geochemical characteristics of fatty acids bound with clay
minerals in muddy hydrocarbon source rocks, Bohai Bay Basin, Eastern China
Longfei Lu, Tenger Borzijin, Tianzhu Lei, Jingong Cai, Jie Wang
P-046 Characterization of the source rock of Jurassic (Tithonian) in Southeastern
Mexico applying the organic facies
Jose Antonio Perez Ortiz, Luis Lopez Lopez, Esaul Gutierrez Mejia, Luis Manuel
Medrano Morales
P-047 Characterization of lignites from the Drmno field, Kostolac Basin, Serbia, based
on biomarker composition
Dragana Ţivotić, Ksenija Stojanović, Aleksandra Šajnović, Olga Cvetković, Hans
Peter Nytoft, Georg Scheeder
P-048 Relationship of lithium enrichment with macerals and organic compounds of Coal
Seam 6 from the Guanbanwusu Coal Mine, Inner Mongolia
Yuzhuang Sun, Yanheng Li, Shiming Liu, Cunliang Zhao, Kankun Jin
P-049 Organic matter of Lower Permian sediments from Subpolar Urals
Olga Valyaeva, Olga Protsko
P-050 Information provided by the Organic Matter contained in cherts of the Ras-Draâ
phosphate deposit (Tunisia) on their depositional environment
Aïda Ben Hassen, Jean Trichet, Jean-Robert Disnar, Habib Belayouni
P-051 Kerogen sulphur, hydrogen and carbon isotope variation across the Permian-
Triassic boundary in the South China
Chunfang Cai, Lei Xiang, Kaikai Li, Lei Jiang
21

P-052 Incorporation of Archaeal and Bacterial Lipids into Geomacromolecules:
Implications for Organic Matter Preservation
Lidia Chaves Torres, Katie L. H. Lim, Paul S. Monaghan, Richard P. Evershed,
Richard D. Pancost
P-053 Sulfur-bound compounds in free and bound lipids of recent sediment of
continental type
Tatyana Cheshkova, Tatyana Sagachenko
P-054 Hyper-accumulations of monosulfidic sediments in the Peel-Harvey Inlet,
Western Australia
Robert S Lockhart, Paul Greenwood, Richard Bush, Kliti Grice
P-055 Organic matter preservation in Cariaco Basin, a pyrolytic study
Melesio Quijada, Armelle Riboulleau, Pierre Faure, Olivia Bertrand
P-056 Detection of microbial biomass in subseafloor sediments by Pyrolysis-GC/MS
Rong Zhu, Gerard J.M. Versteegh, Kai-Uwe Hinrichs
Poster Session 1 - Monday 19 th September 2011
13.40 – 15.05
Petroleum biomarkers 1
P-058 Characterization of aromatic steroids in marine and lacustrine crude oils by
Comprehensive two-dimensional gas chromatography time-of-flight mass
spectrometry (GCxGC-TOFMS)
Cristiane Rossi Oliveira, Hélen Gomes Maria Aquiar, Débora Almeida Azevedo,
Eugênio Santos Neto, Francisco Aquino Neto
P-059 Update and Review of Recent Advances in Age-Related Biomarkers
Silvana Barbanti, J. Michael Moldowan
P-060 Biomarkers parameters used to assessment of petroleum biodegradation under
laboratory conditions
Georgiana Feitosa da Cruz, Eugênio Vaz dos Santos Neto
P-061 Geochemical characterization of biomarkers released from asphaltenes of
bitumen and expelled oil generated by hydrous pyrolysis
Noelia Franco Rondon, Milton Cézar da Silva, Luis Guilherme Costa dos Santos,
Tais Freitas da Silva, João Graciano Mendonça Filho
P-062 A diagenetic origin for the moretane anomaly at the Permian Triassic Boundary
Katherine French, Changqun Cao, Gordon Love, Roger Summons
P-063 Origin of crude oil with high concentration of dibenzothiophene in Tarim Basin
Zhu Guangyou, Zhang Shuichang, Jiang Naihuang, Su Jin, Cui Jie, Gu Lijing
P-064 Biodegradation of aromatic hydrocarbons at basin and laboratory scales
Frank Haeseler, Françoise Behar, Denis Blanchet, Marion Courtiade
P-065 Molecular maturation of Bitumen-1 versus Bitumen-2: a case study from the
Oligocene Enspel Formation
Christian J. Illing, Christian Hallmann, Roger E. Summons, Harald Strauss
22

P-066 Synthesis of hopanoid hydrocarbons from zeorin and identification of a new
series of rearranged hopanes
Geir Kildahl-Andersen, Hans Peter Nytoft, Jon Eigill Johansen
P-067 C21-C23 steroidal tricyclic terpanes from bitumen of Olenek field (East Siberia)
Vladimir Kashirtsev
P-068 Aromatic hydrocarbons in the Barents-Kara shelf
Anna Kursheva, Ivan Litvinenko, Vera Petrova
P-069 The age and palaeoenvironmental conditions spanning the Permian/Triassic
boundary in the northern onshore Perth Basin by using biomarker distributions
and stable isotopes (C,H)
Mojgan Ladjavardi, Kliti Grice, Chris Boreham, Dianne Edwards, Ian Metcalfe,
Roger Summons
P-070 Characterisation of biodegraded Australian oils via catalytic hydropyrolysis
Robert S Lockhart, Minh Tam Le, Kliti Grice, Will Meredith
P-071 Structural characterization of 1,6-dimethyl-5-isopentyltetralin from Cretaceous
conifer fossil resins and coals: a novel diterpene biomarker
Cesar Menor-Salvan, Marta Ruiz-Bermejo, Bernd R.T. Simoneit
P-072 High molecular alkanes С40+ in West Siberian oils
Marina Mozhayskaya, Galina Pevneva, Julia Golovko, Anatoly Golovko
P-074 Discussion on appliance of 25-norhopanoids compounds
Chunhua Ni
P-075 Bicadinanes extend to C39 in oils from Southeast Asia
Hans Peter Nytoft, Geir Kildahl-Andersen, Jon Eigill Johansen, Håkon Midtaune,
Herbert Volk
P-076 Lanostanes as the new biomarkers from organic matter of Cambrian black shales
in the Siberian platform
Tatyana Parfenova
Poster Session 1 - Monday 19 th September 2011
13.40 – 15.05
Petroleum case studies 1
P-078 The record of the early Aptian global oceanic event OAE1a in Goraa- Hammam
Biadha Basin (Northwestern Tunisia)
Soumaya Abbassi, Habib Belayouni, Moncef Saidi
P-079 Geochemistry of ―just generated‖ oils from Uzon volcano caldera(Kamchatka) in
comparison with oldest pre-Cambrian oils
Enver Ablya, Irina Slivko
P-080 Petroleum potential of Miocene heterolithic successions within the Sarawak
Basin, Malaysia: multiple role as source, carrier, and reservoir rocks
Peter Abolins, Wan Hasiah Abdullah, Meor Hakif Amir Hassan, Mohammed Hail
Hakimi
23

P-081 Geochemical evidence for two sources of oils in the Papuan Basin, Papua New
Guinea
Manzur Ahmed, Herbert Volk, David Holland, Tony Allan
P-082 Geochemical assessment of oil migration in the Upper Shuaiba of the Lekhwair
High in NW of Block 6, Oman
Mohammed Al Ghammari, Paul Taylor, Gordon Coy
P-083 Thermal maturity assessment of potential source rocks and reservoired
condensates in Kish Gas Field, Persian Gulf Basin
Bahram Alizadeh, Seyed Hossein Hosseini, Mehdi Khaleghi
P-084 The oil fraction composition of nonisothermic aquathermolysis products of sulfurrich
native asphaltite in the 200−575 °C temperature range
Vladimir Antipenko
P-085 Flash pyrolysis-gas chromatography-mass spectrometry of sulfur-rich native
asphaltite, its asphaltenes, resins and oils
Vladimir Antipenko, Vasilyi Melenevskiy
P-086 Migration tracers reveal long-range migration in the Summan exploration area
Khaled Arouri, S K Panda, S A Satti, Y Yang
P-087 Petroleum geochemistry of the Stord Basin, Norwegian North Sea
Mark Bastow
P-088 Crude oil in the Alpine Foreland Basin of Austria: a known petroleum system
revisited
Achim Bechtel, Reinhard Gratzer, Reinhard F. Sachsenhofer, Hans-Gert Linzer,
Doris Reischenbacher, Hans-Martin Schulz
P-089 Addressing thermogenic and biogenic gas emissions during the formation of the
oil sands deposits of the Western Canada Basin
Luiyin Berbesi, Rolando di Primio, Zahie Anka, Brian Horsfield, Heinz Wilkes
P-090 Hydrocarbon potential of the western Barents Sea – evaluation of sedimentary
rocks of Spitsbergen
Ulrich Berner, Bernhard Cramer, Karsten Piepjohn, Pjotr Sobolev
P-091 Investigation of oil stability under geological conditions using kinetics of C8
hydrocarbons cracking derived from MSSV pyrolysis
Regina Binotto, Rosane Fontes, Henrique Penteado, Denise Bohrer
P-092 Geochemistry of heterocyclic components from organic matter and oils of West
Siberia
Lyubov Borisova
P-093 Organic geochemistry, petroleum systems, history of oil and gas generation and
accumulation in northern part of West Siberian basin
Alexey Kontorovich, Lev Burshtein, Sergey Ershov, Valery Kazanenkov, Natalia
Kim, Vladimir Kontorovich, Vasiliy Melenevsky, Pavel Safronov, Alexander
Fomin, Elena Fursenko, Georgiy Shemin
24

P-094 Hybrid petroleum migration and accumulation systems in the central Junggar
Basin, northwest China
Zhijun Jin, Jian Cao, Xulong Wang, Wenxuan Hu, Suping Yao
P-095 Natural Petroleum Fractionation – what do we really mean?
Chris Cornford
P-096 Analysis on hydrocarbon accumulation and key controlling factors of oil & gas
accumulation in the Qaidam Basin, NW China
Shihu Fang, Mengjun Zhao, Shuichang Zhang, Dade Ma, Yongshu Zhang, Yan
Chen
P-097 Geochemistry of low-boiling С5-С8 hydrocarbons from Middle Ob‘ oils (West
Siberia)
Elena Fursenko
P-098 Differential entrapment of charged oil - new insights on McMurray formation oil
trapping mechanisms
Milovan Fustic, Barry Bennett, Haiping Huang, Thomas Oldenburg, Stephen
Hubbard, Steve Larter
P-099 Oxygen-containing compounds in crude oils of south-eastern part of West Siberia
Eugenia Strelnikova, Ivan Goncharov, Olga Serebrennikova
P-100 Diversity of source, biomarkers composition and maturity of crude oils in
Zechstein Main Dolomite deposits, NW Poland
Cezary Grelowski, Franciszek Czechowski
P-101 Formation of giant deep-buried old heavy oil reservoirs below 7000m in Tarim
Basin, China
Zhu Guangyou, Zhang Shuichang, Su Jin, Gu Lijing, Wang Yu, Zhang Bin
P-102 Origin of solid bitumen of Guizhong 1 in the Guizhong Depression, SW China:
evidence from carbon isotopes and biomarkers
Xunyun He, Genshun Yao, Xianghua Xiong, Chunfang Cai, Anjiang Shen,
Xiaosu He
P-103 Geochemical characteristics of crude oils from the Murzuq Basin, Libya
Tarek Hodari, Paul Philp
P-104 Effect of PDC-bit platelets on geochemical data quality and hydrocarbon-systems
evaluation
Daniel Jones, Cara Davis, Holger Justwan, Lloyd Wenger
P-105 Challenges on the origin of oil/condensate and presence of bitumen and oil
seeps in the Tanzania coastal basins
Meshack Kagya
P-106 Organic geochemistry of naphthides of the Anabar-Khatanga saddle
Natalya Kim, Vladimir Kashirtsev, Oksana Dzuba
P-107 Caldera of the Uzon volcano as a natural laboratory of the modern oil formation
Alexey Kontorovich, Svetlana Bortnikova, Gennadii Karpov, Vladimir Kashirtsev,
Elena Kostyreva, Alexander Fomin
25

P-108 Organic geochemistry and Mesozoic petroleum systems of the Yenisey-
Khatanga regional trough
Alexei Kontorovich, Natalya Kim, Sergei Yershov, Elena Kostyreva, Vasiliy
Melenevskiy, Aleksandr Fomin
P-109 A saga on organic geochemistry - 50 years of IMOG
Keith Kvenvolden
P-110 Geochemical characteristics of the mixed marine oils in the Tazhong Uplift of
Tarim Basin, NW China
Yankuan Tian, Chupeng Yang, Zewen Liao, Haizu Zhang
P-111 An integrated inorganic and organic geochemical study to evaluate the origin/age
of crude oils
Ercin Maslen, Kliti Grice, Tamara Pilgrim, John Watling, Dianne S Edwards
P-112 Hydrocarbon systems of the Russian Arctic continental shelf in view oil and gas
presence forecast
Eric Galimov, Alla Nemchenko-Rovenskaya, Vyacheslav Sevastyanov, Tatyana
Nemchenko
Poster Session 1 - Monday 19 th September 2011
13.40 – 15.05
Petroleum source rocks 1
P-114 Hydrocarbon generation potential, source rocks and oils of the Upper Jurassic–
Middle Cretaceous formations in the southern part of the Mesopotamian Basin
(Zubair Subzone), Southern Iraq
Qusay Abeed, Jan Schwarzbauer, Ralf Littke
P-115 The carbon isotopic composition of Upper Jurassic oil shales Russian plate
organic matter and its formation conditions
Dmitry Bushnev, Nadezhda Burdelnaya, Irina Smoleva
P-116 Marine transgressional event during the Early Cretaceous in southeastern China:
organic petrological and biomarker evidences
Jian Cao, Xiaomin Xie, Wenxuan Hu, Guang Hu, Yuqiao Gao, Chunhua Shi
P-117 Lithology, organic geochemistry, paleo-geography, oil bearing capacity and
petroleum-generating potential of the Bazhenovo Formation
Alexey Kontorovich, Valentina Danilova, Albina Zamiraylova, Yuriy Zanin, Elena
Kostireva, Vasiliy Melenevskiy, Valeriy Moskvin, Vika Eder
P-118 The cracking kinetics of two oil samples from Sichuan Basin, China
Liangliang Wu, Ansong Geng, Yuhong Liao, Yunxin Fang
P-119 Generation potential of Togur Formation rocks in the south-east of Western
Siberia (Russia)
Ivan Goncharov, Nikolay Oblasov, Vadim Samoylenko, Svetlana Fadeeva
P-120 The generation potential of the Bazhenov Formation and its stratigraphic
analogues in the east of Western Siberia
Ivan Goncharov, Vadim Samoylenko, Nikolay Oblasov, Svetlana Fadeeva,
Vladimir Krinin, Vladimir Volkov
26

P-121 Source rock characteristics of Cretaceous organic-rich black shales offshore
southwestern Africa
Alexander Hartwig, Rolando di Primio
P-122 Organic geochemical characterizations of organic-rich rocks of Beydili (Ankara,
Turkey)
Derya Koca, Ali Sarı
P-123 Organic matter characteristics of Bazhenov Formation in the central part of the
West-Siberian basin based on biomarker parameters and pyrolysis
Enver Ablya, Elena Kononchenko
P-124 Compositional features of organic matter in Jurassic and Lower Cretaceous
deposits located in the east of West Siberia
Natalya A. Krasnoyarova, Olga V. Serebrennikova
P-125 Organic geochemical and petrographic characterization of fluvial-lacustrine
source rocks and implications for hydrocarbon source correlation in Cenozoic rift
basins, NE China
Maowen Li, Xue Wang, Shuzhi Wang, Julito Reyes, Sneh Achal, Zihui Feng, Wei
Fang
P-126 The value of generation hydrocarbon and its application on the evaluation of
source rock: taking Liaodong Bay, China as an example
Shuifu Li, Shouzhi Hu, Jiaren Ye, Dongmei Zhang, Jun Ma
Poster Session 2 - Tuesday 20 th September 2011
13.40 – 15.05
Archeology
P-128 Investigation of fish pond management through pigment biomarkers in the
archaeological record
Angela Ballantyne, Brendan Keely
P-129 Characterisation of antique organic adhesives by GC-MS
Armelle Charrié-Duhaut, Jacques Connan, Pierre-Jean Texier, Thomas Hauck,
Jean-Marie Le Tensorer, Céline Leprovost, Mickaël Landolt
P-130 Bituminous mixtures of Hakemi Use (SE Turkey) form the Hassuna/Samarra
period (6100-5950 BC): origin of bitumen
Orhan Kavak, Jacques Connan, Halil Tekin, Kendra Imbus, John Zumberge
P-131 Interred with their bones: biomarkers in archaeological burials
Kimberley Green, Matthew Pickering, Don Brothwell, Brendan Keely
P-132 Combined d13C - dD analysis of pentacyclic triterpenes and their derivatives
Jérémy Jacob, Claude LeMilbeau, Nicolas Bossard, Jean-Robert Disnar, Yves
Billaud
27

P-133 Can we estimate catchment-scale biomass production from sedimentary
biomarkers? An attempt with miliacin in Late Bronze Age levels from Lake le
Bourget (French Alps)
Jérémy Jacob, Emmanuel Chapron, Yves Billaud, Grégoire Ledoux, Patrick
Lajeunesse, Jean-Robert Disnar, Guillaume St-Onge, Claude LeMilbeau, Nicolas
Bossard, Fabien Arnaud
P-134 Biomarkers preserved in cave sediments and their use as indicators of
environmental change in Trang An, Vietnam
Natalie F. Ludgate, Thomas A. Griffiths, Alison J. Blyth, William D. Gosling, Iain
Gilmour
P-135 Composition of aliphatic hydrocarbons in prehistoric rice paddy soils in China
Cornelia Mueller-Niggemann, Jin Zhang, Zhi-Hong Cao, Lorenz Schwark
P-136 Analysis of insoluble organic residues in graves by sequential thermal
desorption/pyrolysis-gas chromatography-mass spectrometry
Matthew Pickering, Kimberley Green, Don Brothwell, Brendan Keely
Poster Session 2 - Tuesday 20 th September 2011
13.40 – 15.05
Environment and pollution 1
P-138 Monitoring organic pollutants (PAHs, PCBs, OCPs) in German forest soils
Bernhard Aichner, Petra Lehnik-Habrink, Sebastian Hein, Bernd Bussian,
Wolfram Bremser, Irene Nehls
P-139 Role and nature of organic matter in the mobilisation of arsenic in shallow
reducing aquifers
Wafa. M. Al Lawati, Jiin-Shuh Jean, Ming-Kuo Lee, Thomas. R. Kulp, Michael
Berg, Elisabeth Eiche, Athanasios Rizoulis, Jon Lloyd, David Polya, Bart. E. van
Dongen
P-140 Effects of natural and artificial oxidation on dissolved organic matter: example of
Boom Clay
Pascale Blanchart, Pierre Faure, Raymond Michels, Christophe Bruggeman,
Mieke De Craen
P-141 Biosurfactants – a green alternative to synthetic surfactants
Gunhild Bødtker, Ina Hvidtsen, Tanja Barth
P-142 Geochemical parameters assessment in sediments of Lake Coari (Amazon)
Tatiana Santos da Cunha, Francisco Fernando Lamego Simões Filho, Celso
Marcelo Franklin Lapal, Maria de Lourdes Moreira, Luis Landau, Celeste Yara
dos Santos Ciqueira
P-143 Phenolic compounds in water leachates of Miocene lignites from the Konin
Brown Coal Basin (Poland)
Monika Fabiańska, Urszula Skręt
P-144 Organic compounds of geochemical origin in domestic furnaces coal ash (Upper
Silesia, Poland)
Monika Fabiańska, Danuta Smołka-Danielowska
28

P-145 Current level of the organic pollution in the Bílina river sediments (Czech
Republic)
Eva Francu, Milan Geršl, Kateřina Zelenková
P-146 Alteration of aromatic hydrocarbons from the oil pollutions by aerobic
biodegradation
Elena Fursenko, Vladimir Kashirtsev, Lyubov Altunina, Varvara Ovsyannikova,
Ludmila Svarovskaya
P-147 The d13C composition of individual n-alkanes in sediments from Brazilian
estuarine systems by GC/C/IRMS
Otávio Luiz Gusso Maioli, Cristiane Rossi Oliveira, Marco Aurélio Dal Sasso, Luiz
Augusto do Santos Madureira, Francisco Radler Aquino Neto, Débora Almeida
de Azevedo
P-148 Seasonal contamination in Lake Van (Turkey)
Carme Huguet, Susanne Fietz, Mona Stockhecke, Núria Moraleda, Antoni
Rosell-Melé
P-149 Targeted chemical and physical charachterisation of a biosurfactant produced by
the novel Actinobacterium
Ina Hvidsten, Gunhild Bødtker, Tanja Barth
P-150 Polycyclic aromatic hydrocarbons in surface sediments of the Jade Bay, North
Sea, Germany
Angelika Klugkist, Barbara M. Scholz-Böttcher, Jürgen Rullkötter
P-151 Cu(II) complexation with humic acid and humic-like ligands studied by Schubert‘s
method
Ivana Kostic, Tatjana Andjelkovic, Ruzica Nikolic, Milovan Purenovic, Aleksandar
Bojic, Darko Andjelkovic, Jelena Mitrovic
P-152 Stability of Cu(II) and Pb(II) salycilate complexes determined by modified
Schubert's method
Ivana Kostic, Tatjana Andjelkovic, Ruzica Nikolic, Milovan Purenovic, Aleksandar
Bojic, Darko Andjelkovic, Miljana Radovic
P-153 Differentiation of indoor and subsurface VOCs sources in residential air by CSIA
for vapor intrusion management
Paul Philp, Tomasz Kuder, Thomas McHugh, Kyle Gorder, Erik Dettenmaier
P-154 Adaptation of TO-17 thermal desorption protocol for CSIA of volatiles in air
Paul Philp, Tomasz Kuder, Thomas McHugh
Poster Session 2 – Tuesday 20 th September 2011
13.40 – 15.05
Microbial geochemistry/lipidomics/genomics 1
P-156 A detailed study of the intact polar lipids in Dutch coastal waters and microbial
mats using multistage liquid chromatography mass spectrometry
Nicole Bale, Ellen Hopmans, Laura Villanueva, Stefan Schouten, Jaap Sinninghe
Damste
29

P-157 Can laterally advected intermediate nepheloid layers affect the efficiency of the
biological pump? – a biomarker study of sub-surface alterations of marine snow
aggregates off Cape Blanc, NW Africa
Andreas Basse, Gesine Mollenhauer, Gerd Fischer, Morten Iversen, Gerard
Versteegh, Gökay Karakas
P-158 Unusual distribution of long-chain heterocyst glycolipids in an Icelandic hot spring
Thorsten Bauersachs, Marcel Van der Meer, Stefan Schouten, Jaap Sinninghe
Damsté
P-159 Archaeal and bacterial tetraether lipids in a oligotrophic and a eutrophic Swiss
lake: Insights into their sources and GDGT-based proxies
Achim Bechtel, Rienk H. Smittenberg, Stefano M. Bernasconi, Carsten J.
Schubert
P-160 Biomarker signatures of methane-oxidizing archaea and aerobic bacteria in seep
carbonates reveal changing redox conditions at cold seeps from Alaminos
Canyon, northern Gulf of Mexico
Daniel Birgel, Dong Feng, Harry H. Roberts, Jörn Peckmann
P-161 Biosignatures of microbial methane turnover in the water column and sediments
of the central Baltic Sea (Gotland Deep)
Martin Blumenberg, Christine Berndmeyer, Oliver Schmale, Volker Thiel
P-162 Lipid biomarkers and bulk biogenic components in sinking particles from the SW
Black Sea
Ioanna Bouloubassi, Alexandra Gogou, Anna Sanchez-Vidal, Spyros Stavrakakis
P-163 Fluxes and distributions of core and intact tetraether membrane lipids in the
water column of Lake Challa, East Africa
Laura Buckles, Johan Weijers, Gert-Jan Reichart, Dirk Verschuren, Jaap
Sinninghe Damsté
P-164 Chemotaxonomic composition and carbon fixation of the microbial community in
a shallow hydrothermal vent off Milos, Greece
Miriam Sollich, Marcos Yoshinaga, Roy Price, Kai-Uwe Hinrichs, Solveig Bühring
P-165 Characterisation of organic acids in geological samples
Jacqueline Mireya Calzada Mendoza, Andrea Vieth-Hillebrand, Heinz Wilkes
P-166 The role of two submarine canyons in the transport and accumulation of organic
matter in the south-eastern Brazilian continental margin
Renato Carreira, Lívia Cordeiro, Dulce Oliveira
P-167 Microbial deposits from Shark Bay and their geologic significance - a
multidisciplinary re-visit
Tobias Ertefai, Ricardo Jahnert, Grzegorz Skrzypek, John Dodson, Kliti Grice,
Lindsay Collins
P-168 Correlation of Crenarchaea and phytoplankton biomarkers indicate metabolic
dependence
Susanne Fietz, Carme Huguet, Alfredo Martinez-Garcia, Gemma Rueda, Vicky
Peck, Marina Escala, Antoni Rosell-Melé
30

P-169 Lipid biomarkers in ooids from different locations and ages provide evidence for
a common bacterial flora
Aimee Gillespie, Laurence Bird, Sara Pruss, Alex Sessions, Mark Roberts, Roger
Summons
P-170 Microbial activity and abundance in sediments Lake Van (Turkey), first results
from ICDP Project PALEOVAN
Clemens Glombitza, Jens Kallemyer
P-171 Lipid biomarkers and phylogenetic analysis indicating the variability of
methanogenic communities within terrestrial Late Pleistocene and Holocene
permafrost deposits in the central Lena River delta, Siberia
Juliane Griess, Kai Mangelsdorf, Dirk Wagner
P-172 Microbially mediated carbonate formation from gypsum and oil
Vincent Grossi, Marion Baudrand, Rich Pancost, Christophe Lécuyer, Marie-
Magdeleine Blanc-valleron, Mahmoud Aref, Jean-Marie Rouchy, Giovanni Aloisi
P-173 Oxidation and physical protection of organic matter by mineral matrix : their
influence on the diagenesis of hopanoids
Yann Hautevelle, Apolline Lefort, Pierre Faure, Raymond Michels
P-174 Distinct microbial inventories in terrestrial mud volcanoes of Northern Italy
controlled by the source and composition of emitted fluids
Christina Heller, Martin Blumenberg, Christoph Wrede, Michael Hoppert, Marco
Taviani, Joachim Reitner
P-175 Molecular and isotopic biosignatures in altered and unaltered hydrother-mal
precipitates of the southern Mid-Atlantic Ridge
Sascha Herrlich, Martin Blumenberg, Walter Michaelis, Anne Dreier, Richard
Seifert
P-176 Microbial consortium mediating carbon cycle in a subsurface and oliogotrophic
karst cave in China
Yang Huan, Xie Shucheng
P-177 Rhizoliths in loess: evidence for the heterotrophic lifestyle of branched GDGTproducing
bacteria
Arnaud Huguet, Guido L.B. Wiesenberg, Martina Gocke, Céline Fosse, Sylvie
Derenne
P-178 Diversity of microbial communities associated with low-temperature hydrothermal
venting at the ultra-slow spreading Arctic Mid-Ocean Ridge
Andrea Jaeschke, Gretchen L. Früh-Green, Stefano M. Bernasconi, Ida H.
Steen, Ingunn H. Thorseth, Rolf B. Pedersen
P-179 Tetraether membrane lipid distributions in lacustrine sediments: a study of 28
lakes in the Yangtze floodplain (SE China)
Li Jingjing, Yang Huan, Qin Yangmin, Huang Junhua, Xie Shucheng
P-180 Inhibition of anaerobic oil degradation by low molecular weight hydrocarbons
Angela Sherry, Russell Grant, Carolyn Aitken, Martin Jones, Neil Gray, Ian Head
P-181 Bacterial wax esters in fluvial sediments from the Danube River (Rep of Serbia)
Jürgen Köster, Vesna Micić, Michael A. Kruge, Thilo Hofmann
31

P-182 The influence of hydrogen on organic matter cycling at the lost city hydrothermal
field
Susan Lang, Gretchen Früh-Green, Stefano Bernasconi, Marvin Lilley
P-183 Characterization of dissolved organic matter in the hydrothermally altered
sediment of the Guaymas Basin, Gulf of California
Yu-Shih Lin, Boris Koch, Matthias Witt, Kai-Uwe Hinrichs
P-184 Have they lost their heads? Differential detection of archaeal IPLs and GDGTs
Sara A. Lincoln, Edward F. DeLong, Roger E. Summons
P-185 Biogeochemistry of sediments at ultra-deep burial depth recovered during IODP
Expedition 317, Canterbury Basin, New Zealand
Julius Lipp, Simon C. George, George E. Claypool, Toshihiro Yoshimura, Kai-
Uwe Hinrichs, IODP Expedition 317 Shipboard Scientific Party
Poster Session 2 - Tuesday 20 th September 2011
13.40 – 15.05
Proxies and paleoreconstructions 1
P-187 Paleohydrological changes on the n-alkane biomarker compositions of a
Holocene peat sequence in the Eastern European Russian Arctic
Rina Andersson, Philip Meyers, Peter Kuhry, Magnus Mörth, Yngve Zebühr,
Patrick Crill
P-188 Impact of degradation on the lipid biomarkers of a Holocene peat sequence in
the Eastern European Russian Arctic
Rina Andersson, Philip Meyers
P-189 Paleoenvironmental variations recorded by marine algal and terrestrial plant
biomarkers in black shales deposited during the mid-Cretaceous Oceanic Anoxic
Event 1b in the Vocontian Basin, SE France
Takuto Ando, Ken Sawada, Kazuki Okano, Hiroshi Nishi, Reishi Takashima
P-190 Large scale cooling in Tertiary Central Europe as inferred by the MBT/CBT
paleothermometer
Thorsten Bauersachs, Stefan Schouten, Lorenz Schwark
P-191 Highly branched isoprenoid alkenes as proxies for variable sea ice conditions in
the Southern Ocean
Steven Rowland, Guillaume Masse, Xavier Crosta, Simon Belt, Ian Snape, David
Thomas
P-192 Climate variability in the Lake Victoria region (East Africa) since the Late
Pleistocene as shown by molecular biomarkers
Melissa Berke, Josef Werne, Thomas Johnson, Kliti Grice, Stefan Schouten,
Jaap Sinninghe Damsté
P-193 A new global calibration for GDGTs preserved in stalagmites
Alison Blyth, Stefan Schouten
P-194 Palaeotemperatures and Palaeoenvironmental Changes during OAE 1a at
Shatsky Rise
Simon Brassell
32

P-195 Molecular fossils and the late rise of eukaryotes and oxygenic photosynthesis
Jochen J. Brocks
P-196 The holocene ecosystem of Lake Van, Eastern Turkey
Ozlem Bulkam, Heinz Wilkes, Naci Orbay, M.Namık Cagatay, M.Namık Yalcin
P-197 Sediment trap and core top study of organic (UK‘37 and TEX86) and inorganic
(d18O, Mg/Ca) sea surface temperature proxies in the Mozambique Channel
Isla Castañeda, Ulrike Fallet, Geert-Jan Brummer, Jaap Sinninghe Damsté,
Stefan Schouten
P-198 Reconstruction of sea surface temperature in the eastern Indian Ocean during
the last 22000 years
Wenwen Chen, Gesine Mollenhauer, Mahyar Mohtadi, Torsten Bickert
P-199 Detection of environmental changes in the Minho River Estuary (NW Iberian
Peninsula): a multi proxy approach
Jose María De la Rosa, Francisco J. Gonzalez-Vila, Heike Knicker, José Antonio
González-Pérez, Francisco Fatela, Eduardo Leorri, Reide Corbett, Antonio M.
Soares, Fátima Araújo
P-200 Palaeoenvironmental change reflected by carbon isotopes and palynology in the
early Silurian of the Tanezzuft Formation, Libya
Mohamed Elkelani, Gert Jan Reichart, Jaap Sinninghe Damsté, Zwier Smeenk,
Wolfram Kurschner, Henk Brinkhuis, Peter Nederlof
P-201 Carbon and hydrogen isotope biomarker records of methane release and
hydroclimatic variability from a thermokarst lake in the Alaskan Arctic
Marcus Elvert, Matthew J. Wooller, Kevin Becker, Benjamin Gaglioti, Kai-Uwe
Hinrichs, John W. Pohlman
P-202 Terrestrial higher plant biomarkers in hyperpicnite-like sedimentary sequence in
the Miocene Kawabata Formation, central Hokkaido, Japan: evidence for direct
transport of terrigenous matter by flood?
Satoshi Furota, Ken Sawada
P-203 Biogeochemical processes in Holocene-Pleistocene sediments at

P-207 Biomarkers along a holocene sedimentary sequence from the Guadiana river
estuarine area (Portugal/Spain border)
Francisco J. González-Vila, Kathrin Schütrumpf, José A. González-Pérez,
Tomasz Boski, José Mª de la Rosa, Heike Knicker, Dominik Faust
P-208 Alkenone producers during late Oligocene-early Miocene revisited
Julien Plancq, Vincent Grossi, Jorijntje Henderiks, Laurent Simon, Emanuela
Mattioli
P-209 A comparison of methane emission and oxidation histories on the Amazon and
Congo fans over the last 200 kyr
Luke Handley, Helen Talbot, Kate Osborne, Thomas Wagner (Newcastle upon
Tyne, United Kingdom)
P-210 The preservation of vascular plant biomolecules in a 155 million years old
sedimentary deposit: case of the Flogidarry Shale Member (Isle of Skye,
Scotland)
Apolline Lefort, Yann Hautevelle, Bernard Lathuillière, Vincent Huault
P-211 Paleocene-Eocene Thermal Maximum impacts on terrestrial environments.
Insights from the organic matter evolution in the Vasterival section (Dieppe-
Hampshire Basin, France)
Sylvain Garel, Johann Schnyder, Jérémy Jacob, Mohammed Boussafir, Christian
Dupuis, Jean-Yves Storme, Johan Yans, Alina Iakovleva, Emile Roche, Claude
LeMilbeau, Florence Quesnel
P-212 Constraining stable carbon and hydrogen isotope excursions of fire events from
controlled burning experiments and applications to the Triassic-Jurassic
extinction event
Caroline Jaraula, Kliti Grice, Christiane Vitzthum von Eckstadt, David Kelly,
Stephen Clayton, Luis Felipe Opazo, Richard Twitchett
P-213 Biomarker proxies indicate silicic acid transport from the Southern Ocean to
southeastern Australia during interglacials
Raquel Lopes dos Santos, Daniel Wilkins, Patrick De Deckker, Stefan Schouten
P-214 Crenarchaeotal tetraether index of TEX86 as an indicator of subsurface
temperatures in the South China Sea
Guodong Jia, Jie Zhang, Jianfang Chen
P-215 Distributions of long-chain diols in surface sediments from the North Pacific:
possible revised diatom biomarker paleothermometry
Madoka Kobayashi, Ken Sawada, Osamu Seki
P-216 A Pleistocene-Holocene transgressive sediment sequence in the southern North
Sea coast area seen from a biomarker perspective
Jürgen Köster, Fenja Müntinga, Jürgen Rullkötter
P-217 The Vinylguaiacol/Indole or VGI ("Veggie") ratio: assessing relative contributions
of terrestrial and aquatic organic matter to sediments
Michael Kruge, Kevin Olsen, Jaroslaw Slusarczyk, Elaine Gomez
P-218 Rainfall variability over NW Africa during the last glacial-interglacial cycle: a δD
record of the last 120 ka
Rony R. Kuechler, Lydie Dupont, Britta Beckmann, Enno Schefuß
34

P-219 The age and palaeoenvironmental conditions spanning the Permian/Triassic
boundary in the northern onshore Perth Basin by using biomarker distributions
and stable isotopes (C, H)
Mojgan Ladjavardi, Kliti Grice, Chris Boreham, Dianne Edwards, Ian Metcalfe,
Roger Summons
P-220 A multiproxy high-resolution approach for the reconstruction of sea surface
temperatures of the last 500 years at the southern Italian shelf
Arne Leider, Anna-Lena Grauel, Kai-Uwe Hinrichs, Stefano M. Bernasconi,
Gerard J.M. Versteegh
P-221 Differences in distribution of core lipids amongst intact polar tetraether lipids and
its implications for the TEX86 paleothermometer
Sabine K. Lengger, Ellen C. Hopmans, Angela Pitcher, Gert-Jan Reichart, Jaap
S. Sinninghe Damsté, Stefan Schouten
Poster Session 2 – Tuesday 20 th September 2011
13.40 – 15.05
Soil and peat and terrestrial OM 1
P-224 Diagenetic transformation of 2,3-dioxygenated triterpenoids from higher plants in
buried wood and sediments
Philippe Schaeffer, Claude Le Milbeau, Pierre Adam
P-225 The change of land plant derived n-alkane characteristics in ocean margin
sediments in relation to the distance from the continent
Tanja Badewien, Jürgen Rullkötter
P-226 Seasonal variations and characters of terrestrial particulate organic matter in
exterior rivers in Southeast China: inferred from bulk properties and lignin
phenols
Hongyan Bao, Ying Wu
P-227 Terrestrial organic matter in the sediments of the German Bight – estimate of
relative proportions using the BIT index in comparison to other proxies
Anna Böll, Barbara Scholz-Böttcher, Jörn Logemann, Jürgen Rullkötter
P-228 Soil organic matter in drylands: insights into selective degradation?
Arnoud Boom, Andrew S Carr, Zoë Roberts, Alex Cumming, Brian M Chase,
Michael E Meadows, Matthew Britton
P-229 Geochemical peculiarities of composition and structure of heterocyclic
components in bitumen extracts of organic matter of lacustrine recent sediments
Lyubov Borisova, Anatoliy Fomichev
P-230 Characterization and dating of soil humic material in holocene progradational
sequence, N. Santa Catarina Littoral, Brasil
Tomasz Boski, Heike Heike Knicker, Francisco Javier Gonzalez Villa, Trinidad
Trinidad Verdejo, José António González-Pérez, Rodolfo Angulo, Maria Cristina
Souza
P-231 Bacteriohopanepolyol content of pasture soils in NE England
Martin Cooke, Helen Talbot
35

P-232 Some experimental results on the influence of clay minerals on fossil organic
matter transformation in soil and sediments
Coralie Biache, Thierry Ghislain, Raymond Michels, Pierre Faure
P-233 Branched GDGTs in the Yenisei river catchment; the trans-Siberian CBT/MBT
signature of river and lake particulate matter
Cindy De Jonge, Alina Stadnitskaia, Georgy Charkashov, Andrei Fedotov,
Alexander Vasiliev, Jaap S. Sinninghe Damsté
P-234 Constraining the sources of dissolved and particulate organic carbon to the Arctic
Ocean using full-depth dual carbon isotope profiles of DIC, DOC, and POC
David Griffith, Ann McNichol, Li Xu, Timothy Eglinton, Fiona McLaughlin, Robie
Macdonald, Kristina Brown
P-235 Simulation of organic matter maturation in thermal waters by model experiments
József Fekete, Csanád Sajgó, Áron Kramarics, Zsuzsanna Eke, Zoltán Kárpáti
P-236 Distribution and fate of lignin in dissolved organic matter in world‘s large river
systems
Xiaojuan Feng, Valier Galy, Jorien E. Vonk, Britta Voss, Ying Wu, Bernhard
Peucker-Ehrenbrink, R. Max Holmes, Daniel B. Montlucon, Timothy I. Eglinton
P-237 Nature of C29 sterols in the high-molecular weight dissolved organic matter
(HMW-DOM) from a freshwater lake
Kazuo Fukushima, Koji Takahashi, Yasuko Yoshiyama, Yoshito Chikaraishi
P-238 Rhizoliths at the Nussloch loess profile (SW Germany) – assessment of source
vegetation using stable isotopes and n-alkane molecular proxies
Martina Gocke, Guido Wiesenberg
P-239 Differentiation of organic matter in soil, loess and rhizoliths at the Nussloch
sedimentary sequence via n-alkane molecular proxies
Martina Gocke, Guido Wiesenberg
P-240 Evidence for transport mechanisms of soil derived branched GDGTs
Hendrik Grotheer, Sabine Kasten, Gesine Mollenhauer
P-242 Changes of Rock-Eval HI, OI, and C-isotope ratios during decay of soil organic
matter in a temperate climate environment (Villiers, Switzerland)
Olivier Hasinger, Jorge E. Spangenberg, Eric P. Verrecchia
P-243 Organic matter composition and degradation in Siberian permafrost soils
Silke Höfle, Pascal Boeckx, Dries Roobroeck, Gesine Mollenhauer, Janet
Rethemeyer
P-244 Identification and distribution of intact branched tetraether lipids in peat and soils
Francien Peterse, Ellen Hopmans, Stefan Schouten, Anchelique Mets, Irene
Rijpstra, Jaap Sinninghe Damsté
P-245 Effects of in situ artificially increased temperature on the distribution of branched
GDGTs in a French peatbog
Arnaud Huguet, Céline Fosse, Fatima Laggoun-Défarge, Sylvie Derenne
36

P-246 Carbon isotopes and lipid biomarker investigation of sources, transport and
degradation of terrestrial organic matter in the SE Laptev Sea
Emma Karlsson, Alexander Charkin, Oleg Dudarev, Igor Semiletov, Jorien Vonk,
Laura Sanchéz-García, August Andersson, Örjan Gustafsson
P-247 Carbon capture by soil chemoautotrophs
Kris Hart, Brian Moran, Chris Allen, André Simpson, Brian Kelleher
P-248 Comparison of soil organic matter tracers (branched GDGTs and soil-specific
BHPs): a study of the NW Mediterranean shelf-slope region
Jung-Hyun Kim, Helen M. Talbot, Roselyne Buscail, Thomas Wagner, Jaap S.
Sinninghe Damsté
P-249 Habitat adaptation by compositional changes of cuticular needle waxes for the
Norway spruce (observation platform Eifel National Parc)
Gina Kuippers, Ulrich Mann, Jan Schwarzbauer
P-250 Biomarker distribution along a pedosequence recording a transition from pasture
to conifer forest (Massif Central, France)
Marlène Lavrieux, Jean-Gabriel Bréheret, Jean-Robert Disnar, Jérémy Jacob,
Claude Le Milbeau, Renata Zocatelli
P-251 Long-term, low temperature simulation of early diagenetic alterations of organic
matter from conifers: Terpenoids in the aromatic hydrocarbon fraction
Shenjun Qin, Yuzhuang Sun, Yuegang Tang, kankun Jin
Poster Session 3 – Wednesday 21 st September 2011
13.40 – 15.05
Gas geochemistry
P-254 The formation conditions of shallow gas and controlling factors of its reservoirs in
the Songliao Basin, NE China
Zihui Feng, Xue Wang, Qiuli Huo, Shibo Wang
P-255 Gas source classification in Paleozoic marine strata, China
Wenhui Liu
P-256 Late stage gas generation in source rocks and gas shales
Nicolaj Mahlstedt, Brian Horsfield
P-257 The components and carbon isotopic compositions of inorganic hydrocarbon
gases with different carbon origins synthesized in gold tube closed-system
Jingkui Mi, Shuichang Zhang, Kun He
P-258 Worldwide distribution and significance of secondary microbial methane formed
during petroleum biodegradation in conventional reservoirs
Alexei Milkov
P-259 Stable carbon isotopes of coal-derived alkane gases in China
Jinxing Dai, Yunyan Ni, Xiaoqi Wu, Shipeng Huang, Fengrong Liao
P-260 Geochemical characteristics of biogenic gases in China
Yunyan Ni, Jinxing Dai, Caineng Zou
37

P-261 Natural gas generation, migration and accumulation in the Jonah Field area,
Green River Basin, Wyoming: implications from chemical and isotopic
compositions of gaseous compounds in the Cretaceous Lance and Mesaverde
formations
Qilin Xiao, Paul Philp, Nicholas Harris, Jon Allen
P-262 Minsterry of the organic matter component during biogenic gas formation: based
on the quaternary of Qaidam basin
Yanhua Shuai, Shuichang Zhang, Pingan Peng, Hong Lu
P-264 Natural gas geochemistry of the southern offshore Brazilian Basins
Eugenio V Santos Neto, Jose R Cerqueira, Alain Prinzhofer
P-265 Analysis of dissolved gases from drilling mud samples for geochemical and
isotope mud gas logging
Philipp Weniger, Stefan Schlömer, Bernhard M. Krooss
P-266 Geochemical and isotopic characterization of coal-related gas from the SE Upper
Silesian Basin, Czech Republic
Philipp Weniger, Juraj Francu, Frantisek Buzek, Petr Hemza, Bernhard M.
Krooss
Poster Session 3 – Wednesday 21 st September 2011
13.40 – 15.05
Petroleum biomarkers 2
P-268 Hydrocarbon molecular markers in the upper Cenozoic sediments of the Arctic
megabasin: distribution, genesis & sources
Vera Petrova
P-269 Distribution of alkylbenzenes in oils from deposits of different geological ages
Galina Pevneva, Anatoly Golovko
P-270 Aromatic hydrocarbons in oils occurring in Lake Baikal
Galina Pevneva, Natalya Voronetskaya, Anatoly Golovko, Vladimir Kashirtsev
P-271 Terrestrial-derived biomarkers from Carboniferous coal deposits at Dunbar (East
Lothian, Scotland): palaeobotanical and palaeoenvironmental significance
Maria-Fernanda Romero-Sarmiento, Armelle Riboulleau, Marco Vecoli, Gerard
J.-M. Versteegh
P-272 Distribution of regular acyclic isoprenoidal alkanes in crude oils of SE Hungary
Csanád Sajgó, József Fekete, Balázs Badics
P-273 Preservation of β-carotane in sediments from the Lopare basin, Bosnia and
Herzegovina
Aleksandra Šajnović, Nenad Grba, Ksenija Stojanović, Branimir Jovančićević,
Biljana Dojčinović
P-274 Pr/Ph ratio in the Bazhenov formation rock samples (Western Siberia)
Ivan Goncharov, Vadim Samoylenko, Nikolay Oblasov, Vladimir Volkov
P-275 Aromatic hydrocarbons in oils from Cambrian and Precambrian deposits (East
Siberia, Russia)
Alexandra Akhmedova, Olga Serebrennikova, Olga Shiganova
38

P-276 Effects of biomarker biodegradation on tar sands of the Pirambóia Formation,
Paraná Basin, Brazil
Eliane Soares de Souza, Georgiana Feitosa da Cruz, Hélio Severiano Ribeiro
P-277 Statistical analysis of diamondoid and biomarker from Brazilian Basin oil samples
Marcia Springer, Debora Azevedo, Bruno Caldas, Luiz Landau
P-278 Short-chain steranes and isophopanes in Miocene source rocks from
hyperthermal basin (Banat Depression, S.E. Pannonian Basin, Serbia)
Ksenija Stojanović, Sanja Mrkić, Aleksandar Kostić, Hans Peter Nytoft,
Aleksandra Šajnović
P-279 Characterization of biomarkers occluded inside oil and coal asphaltenes
Ksenija Stojanović, Nikola Vuković, Vladimira Hrepić, Aleksandra Šajnović,
Dragana Ţivotić, Branimir Jovančićević
P-280 Biomarker hydrocarbons in schungites (Lower Proterozoic, Karelia)
Aleksey Kontorovich, Irina Timoshina, Tatyana Parfenova, Ananoliy Postnikov
P-281 The significance of novel A-norsteranes and perylene in Devonian reefs and
crude oils
Svenja Tulipani, Kliti Grice, Paul Greenwood, Robert Lockhart, Muhammad Asif,
Kenneth Williford, Arndt Schimmelmann
P-282 Land plant markers in Gippsland Basin oils, Australia
Herbert Volk, Manzur Ahmed, Se Gong, Chris Boreham, Peter Tingate, Dianne
Edwards
P-283 Correlation between composition of naphthenoarenes and their saturated
analogues in oils from different geological age deposits
Natalya Voronetskaya, Galina Pevneva, Anatoly Golovko
P-284 Nitrogen compounds in organic matter of rocks from upper Jurassic deposits of
Western Siberia
Svetlana Yanovskaya, Tatyana Sagachenko, Heinz Wilkes
Poster Session 3 – Wednesday 21 st September 2011
13.40 – 15.05
Petroleum case studies 2
P-285
Understanding Fluid Inclusion Stratigraphy (FIS) Data
Daniel Stoddart, Paul Farrimond
P-286 Comparison of natural gases in Middle Cambrian reservoir with hydrous pyrolysis
gases from Lower Palaeozoic source rocks from the Polish, Lithuanian and
Estonian parts of Baltic Basin
Maciej Kotarba, Michael Lewan
P-287 The Hydrocarbon Occurrence and Play-forming Genetic Relationships of the
Deep Palaeocene in Jiyang Depression, East China
Linye Zhang, Qing Liu, Xingyou Xu, Xiangxing Kong, Shouchun Zhang, Ru
Wang, Youshu Bao, Rifang Zhu, Zheng Li
39

P-288 Re/Os fractionation during generation and evolution of hydrocarbons
Fatima Mahdaoui, Laurie Reisberg, Raymond Michels, Yann Hautevelle, Yannick
Poirier, Jean-Pierre Houzay
P-289 Correlation of crude oils reservoired in the Polish Carpathian oilfields (the
Silesian and Skole Units)
Irena Matyasik, Wojciech Bielen, Marek Janiga, Leszek Jankowski
P-290 On the problem of preservation of hydrocarbons (HC) and organic matter (OM) at
high pressures (HP) and temperatures (HT) (experimental data)
Vasily Melenevskiy, Yury Palyanov, Alexander Sokol, Vladislav Maly
P-291 Geochemical parameters for unraveling mixtures. Examples from the South
Atlantic continental margins and the giant north-central West Siberian gas fields
John Moldowan, David Zinniker, Zhaoqian Liu, Alla Rovenskaya-Nemchenko,
Jeremy Dahl, Tatyana Nemchenko
P-292 A geochemical assessment of subsalt tar zones in the Gulf of Mexico
Erica Morais
P-293 Hydrocarbon biomarkers in the bottom sediments of the hydrothermal fields
Ashadze-1 and 2 (MAR, 13°N)
Inna Morgunova, Vera Petrova, Ivan Litvinenko, Georgiy Cherkashev
P-294 Petroleum generation and expulsion zones in Maturín subbasin: evaluation of
paleoenvironmental and lithologic variations of cretaceous source rocks
responsible for oil charges accumulated in Carabobo Area, Orinoco Oil Belt-
Eastern Venezuelan Basin
Wendy Murillo, Carolina Olivares (Los Teques, Venezuela
P-295 Using diamondoids to unravel alteration processes
Gary Muscio
P-296 Geochemical record of ancient sediments from the Potwar Basin Pakistan,
inferred by biomarker and stable isotopic signatures
Shahid Nadeem, Kliti Grice, Fazeelat Tahira
P-297 Significance of aromatic biomarkers to characterize the petroleum of the
Southern Indus Basin, Pakistan
Shagufta Nasir, Kliti Grice, Tahira Fazeelat
P-298 Petroleum generation in siliceous deposits of Sakhalin Island (Russia)
Nikolay Oblasov, Ivan Goncharov, Vadim Samoylenko, Svetlana Fadeeva
P-299 Drilling conditions making wells unsuitable for fluid inclusion studies
Sverre Ekrene Ohm, Helen Haneferd
P-300 The alteration of oil during formation of the low-temperature MVT Zn-Pb sulfide
ore deposit at Tres Marias, Chihuahua, Mexico
Christian Ostertag-Henning, Frank Melcher, Bernhardt Saini-Eidukat
P-301 Biomarker distributions and δ13C values of individual n-alkanes of source rocks,
crude oils and oil components from reservoir rocks of Tarim Basin, China
Changchun Pan, Shuang Yu, Jinji Wang, Xiaodong Jin, Lanlan Jiang, Dayong
Liu, Xiuxiang Lü, Jianzhong Qin, Yixiong Qian, Yong Ding, Honghan chen
40

P-302 Carbonaceous rocks of the Neoproterozoic (Vendian) Khatyspyt Formation as a
possible source of oils in the northeastern Siberian Platform
Tatyana Parfenova, Vladimir Kashirtsev, Lubov Borisova, Elena Ivanova, Boris
Kochnev, Konstantin Nagovitsyn, Vasily Melenevsky
P-303 Evaluation of petroleum systems in the area Carúpano Basin, offshore
Venezuela, through basin modeling 3D
Adriana Pérez, Irenio Berrios
P-304 Decision-tree chemometrics of biomarker and isotope data identifies multiple
petroleum systems in the San Joaquin Basin, California
Kenneth Peters, L. Scott Ramos, Leslie Magoon, Paul Lillis, John Zumberge
P-305 Geochemical Indices of Hydrocarbon Systems of Early Generation
Svetlana Punanova, Tatyana Vinogradova
P-306 Evaluation of surface geochemistry and data mining in Brazilian sedimentary
basins
Jean R. Heckmann, Débora A. Azevedo, Luiz Landau
P-307 Basin Modelling of the Hammerfest Basin and Loppa High (Southwestern
Barents Sea); investigating the leakage of hydrocarbons in a glacially influenced
marine environment
Enmanuel Rodrigues, Rolando di Primio, Zahie Anka, Daniel Stoddart, Brian
Horsfield
P-308 Evidence of hydrocarbon generation through decarboxylation reactions:
qualitative and quantitative analyses by FTICR-MS
Elodie Salmon, Françoise Behar, Patrick G. Hatcher
P-309 Comparative characteristics of molecular composition of basement oils in various
regions
Yury Savinykh, Vu Van Hai
P-310 Implications of source rock and oil geochemistry to the understanding of the
petroleum systems of the Northern Red Sea
Jennifer Scott, John Guthrie, Steve Crews, Graeme Gordon, Niall McCormack,
Dean Griffin, Laura Lawton, Andy Pepper
P-311 High water pressure induced combination reactions: a new mechanistic route for
post-oil bitumen formation in deep petroleum basins
Clement Uguna, Will Meredith, Colin Snape, Andrew Carr, Gareth Harriman
P-312 Molecular stable carbon isotopic Composition of Light Hydrocarbons as a method
to decipher hydrocarbon generation, accumulation and secondary alteration in
superimposed petroliferous basin: a case study from Tarim basin, NW China
Yongge Sun, Qilin Xiao, Aizhu Jiang, Chupeng Yang
P-313 Calibration of absolute maturity for terrestrial-sourced oils and gas condensates
using PLS regression
Richard Sykes, Klaus-Gerhard Zink
41

P-314 Chemometric analysis of oil-oil and oil-source rock correlations in New Zealand
basins
Richard Sykes, Klaus-Gerhard Zink
P-315 Organic geochemistry of lower proterozoic of Kodar-Udokan trough (Aldan
shield)
Irina Timoshina, Elena Fursenko
P-316 The occurrence of crude oil in the coal-bearing strata of Hulin Basin and its
hydrocarbon potential analysis, north-eastern China
Xue wang, Bo Chi, Wei Fang, Huasen Zeng, Zhongliang Dong, Xiaochang
Zhang
P-317 Laboratory simulation of vertical hydrocarbon microseepage from the reservior to
the surface using a 3-D model
Guojian Wang, Tongjing Cheng, Ming Fan, Li Lu
P-318 Kinetic study of primary cracking gases from a marine kerogen by stepwise open
system and its implications
Yunpeng Wang, Hongjun Wang, Changyi Zhao, Jinzhong Liu, Jialan Lu
Poster Session 3- Wednesday 21 st September 2011
13.40 – 15.05
Petroleum source rocks 2
P-319 Study on C1-C3 gas generation behavior of kerogen by closed-system thermal
simulation and Py-GC
Yuhong Liao, Xunyong Zhu, Ansong Geng, Yinhua Pan
P-320 Geochemical evaluation of sources rocks from Ain Regada Region, Northern
Algeria
Aziez Mebarka
P-321 Hydrocarbon potential of Maikopian source rocks within Black Sea petroleum
basin
Dmitry Nadezhkin
P-322 Сarbonaceous rocks of the Lower and Middle Cambrian Inican Formation in the
southeastern Siberian platform
Igor Korovnikov, Tatyana Parfenova, Victorya Eder
P-323 Paleoenvironment signnificance of geochemical characteristics of the
carboniferous source rocks in eastern part of the Junggar Basin
Wen Qi, Jianguo Pan, Peng Wang, Kunjun Tan
P-324 Occurrence of organic matter effect hydrocarbon generation and expulsion in
South China
Jianzhong Qin, Baojian Shen, Xiaodong Fu
P-325 Origin of abnormal sonic response in the shale interval of northern songliao
basin, China
Huo Qiuli, Zeng Huasen, Fu Li, Ren Zhigao, Fan Qinghua, Zhang Xiaochang
42

P-326 Source rock investigations on Palaeozoic and Mesozoic sediments of the Central
Congo Basin, Democratic Republic of Congo
Ralf Littke, Victoria Sachse, Damien Delvaux, Jan Schwarzbauer
P-327 Organic geochemistry and organic petrology of Lower Jurassic source rocks from
Aït Moussa, Middle Atlas, Morocco
Victoria Sachse, Detlev Leythaeuser, Jan Schwarzbauer, Ralf Littke
P-328 Alteration of macromolecular composition of palynomorphs as an effect of
thermal maturation
Nadia al Sandouk, Christoph Hartkopf-Fröder, Stephan Kaufhold, Jan
Schwarzbauer
P-329 Characterising the depositional environments of the massive lacustrine source
rocks of Nenjiang Formation in Songliao Basin, China
Zhiguang Song, Qin Yin, Sibo Wang
P-330 Hydrous pyrolysis experiments: new insights about generation, saturation and
petroleum expulsion through organic petrographic evidences.
Igor Souza, Carla Araujo, Taissa Menezes, Luiz Felipe Coutinho, Eugênio
Santos Neto, Regina Binotto, André Spigolon, Giovani Cioccari, Michael Lewan,
Noélia Rondon, João Mendonça Filho, Rosane Alves Fontes
P-331 Organic-geochemical characteristics of sediments from the Lopare basin, Bosnia
and Herzegovina
Nenad Grba, Aleksandra Šajnović, Ksenija Stojanović, Branimir Jovančićević
P-332 Source rock characterization and depositional environment of The Middle
Miocene Hirka Formation (Beypazari-Ankara/Turkiye)
Berna Yavuz Pehlivanli, Ali Sari, Şukru Koc
Poster Session 3 – Wednesday 21 st September 2011
13.40 – 15.05
Reservoir/production
P-335 Geochemistry of aqua-bitumoids from deposits in the West Siberian sedimentary
basin
Valentina Danilova, Alexey Kontorovich
P-336 Mechanistic model of the thermal evolution of n- and iso-alkanes (C1-C32) in oils
Valérie Burkle-Vitzthum, Roda Bounaceur, Paul-Marie Marquaire, François
Montel, Luc Fusetti
P-337 Application of electrospray ionization fourier transform ion cyclotron resonance
mass spectrometry on formation mechanism of high acidity oils
Cheng Dingsheng, Dou Lirong, Shi Quan, Hou Dujie
P-338 Examples of the relationship between reservoir character and hydrocarbon
signatures measured at the surface
Paul Harrington, Alan Silliman
P-339 Geochemical characterization of asphaltenes and maltenes in organic solid
deposits
Eric Lehne, Kentaro Indo, Fenglou Zou, Jose Zacharia, Kamran Akbarzadeh,
John Ratulowski
43

P-340 Atypical fluids in offshore shallow buried reservoirs
Denis Levaché, Christine Lafaurie, Yannick Poirier, Gérard Ségalini
P-341 Simulation studies on the adsorption/occlusion phenomena inside the
macromolecular structures of asphaltenes
Jing Zhao, Zewen Liao, Patrice Creux, Anna Chrostowka, Alain Graciaa
P-342 Chemometric analysis of crude oil composition and fluid properties
Andreas Linge Tomren, Tanja Barth, Kjetil Folgerø, Johan Carlson
P-343 Effective diffusivities of CO2 and associated noble gases in impermeable shale
caprocks of an EOR-CO2 field
Caroline Magnier, Alain Prinzhofer, Eric Flauraud, Sophie Giannesini
P-344 Can mud gas tell us a bigger story?
Daniel McKinney, Heidi Albrecht
P-345 Oil Fingerprinting associated with Well Temperature Profiles as an Alternative
Production Logging Tool
Alain Noyau, Dominique Andre, Jan Mersmann, Francois Dabat
P-346 Diamondoids, a tool in the geochemical studies to identify compartmentalized
reservoirs
Adriana Pérez, Ingrid Alfonzo, Federico Galarraga, Carmen Rodríguez, Ricardo
Harner, Ysmarline Rincones (Los Teques, Venezuela
P-347 Strategies for the assessment of fluid mixing in petroleum systems
Stefanie Pötz, Andrea Vieth-Hillebrand, Heinz Wilkes
P-348 Distribution of tetraprotic (―ARN‖) acids in different oilfield deposits determined
using high temperature gas chromatography and liquid chromatographyelectrospray
ionisation mass spectrometry
Paul Sutton, Steven Rowland, Ben Smith
P-349 Fluid pressure evolution and gas preservation of the Puguang Gasfield, Sichuan
Basin, China
Xiao Xianming, Liu Dehan, Tian Hui
P-350 Geochemical comparison of oil samples and core extracts from Yanchang
Formation in Ordos Basin, China
Weiwei Yang, Guangdi Liu
P-351 The releasing of covalently-bound biomarkers via hydropyrolysis for the bitumensource
correlation of Majiang paleo-reservoir
Fang Yunxin, Geng Ansong, Liao Yuhong, Wu Liangliang
P-352 Experimental simulation of gravity/density segregation by centrifugation
Fenglou Zou, Kentaro Indo, Eric Lehne
44

Poster Session 3 – Wednesday 21 st September 2011
13.40 – 15.05
Sulfur chemistry
P-354 Sulfur isotope fractionation during thermochemical sulfate reduction as reflected
by individual organic compounds
Alon Amrani, Andrei Deev, Alex Sessions, Yongchun Tang, Jess Adkins
P-355 H2S formation and enrichment mechanisms in Puguang gas field of the Sichuan
Basin, China
Tenger Borzijin, Wenhui Liu, Bo Gao, Zhongning Zhang
P-356 Controls on the kinetics of thermochemical sulfate reduction
Geoffrey Ellis, Tongwei Zhang, Qisheng Ma, Alon Amrani, Yongchun Tang
P-357 Mechanisms of Thermochemical Sulphate Reduction: Insights from redox
buffered laboratory experiments
Svenja Germerott, Christian Ostertag-Henning, Harald Behrens
P-358 Sulfur compounds in liquid products of the thermolysis of heavy oil asphaltenes
Andrei Grinko, Anatoly Golovko, Raisa Min, Tatyana Sagachenko
P-359 A laboratory study of H2S production from the thermal reactions of magnesium
sulfate and sulfur with a hydrocarbon reactant: implications for thermochemical
sulfate reduction
Hong Lu, Paul Greenwood, Tengshui Chen, Jinzhong Liu, Ping'an Peng
P-360 High pressure pyrolysis of hydrocarbons in the presence of H2S. Significance to
the composition of oils in reservoirs
Van Phuc Nguyen, Raymond Michels, Paul-Marie Marquaire, Valérie Burklé-
Vitzthum
P-361 H2S risking toolset – thermochemical sulphate reduction field study and
analytical efforts: sequential diagnostics for Fluid-fluid-rock interactions
Henning Peters, Olaf G. Podlaha, Erdem Idiz, Chad Glemser, Lavern Stasiuk,
Volker Dieckmann
P-362 The reaction of elemental sulfur with organic compounds: formation of
benzothiophenes and dibenzothiophenes
Zhibin Wei, Scott Northrop, Heather Rehmer, Steve MacFarland, Glenn Otten,
Clifford Walters, Paul Mankiewicz, Marlene Madincea
Poster Session 3 – Wednesday 21 st September 2011
13.40 – 15.05
Unconventionals
P-364 Shines bright for Jurassic exploration targets: case study of shale oil
characteristics
Rita Andriany, Awatif Al-Khamiss, Hussain Taqi, Abdulaziz Al-Fares
P-365 Geochemical evaluation of the origin and migration of gases present in natural
gas hydrates – an example from the Norwegian continental shelf
Tanja Barth, Espen N. Vaular, Irene Roalkvam, Ida H. Steen
45

P-366 Organic geochemical characterization and distribution of unconventional
hydrocarbon plays of the Lower Cretaceous of NW Germany
Ulrich Berner, Matthias Heldt
P-367 Geochemical controls on shale microstructural evolution
Nicholas Drenzek, John Valenza, Flora Marques, Hendrik Grotheer, Michael
Herron
P-368 Comparison of the geochemical and microstructural co-evolution of two shale
lithotypes through artificial maturation
Hendrik Grotheer, Nicholas Drenzek, John Valenza, Michael Herron, Sean Sylva,
Jeffrey Seewald, Roger Slatt
P-369 Evolution of pores in organic-rich shales during thermal maturation
Tian Hua, Zhang Shuichang, Liu Shaobo, Chen Jianping
P-370 Organic geochemistry of the Colorado Group shale sequence stratigraphic
framework of the Western Canada Sedimentary Basin: implications for shale gas
fairway identification
Haiping Huang, Per Pedersen, Ron Spencer, Andy Aplin, Dallin Laycock,
Samantha Taylor, Steve Larter
P-371 Preliminary investigations into gas-in-place and fraccability of shales from the
Sichuan Basin, China
Jingqiang Tan, Dorothee Hippler, Jinchuan Zhang, Ger van Graas, Nicolaj
Mahlstedt, Georg Dresen, Brian Horsfield
P-372 Transformation of organic matter of sedimentary rocks in model experiment with
the flow of supercritical CO2-fluid
Sara Lifshits, Olga Chalaya
P-373 Geochemistry of coalbed methane and co-production water of Fuxin basin,
Northeast China
Shaobo Liu, Yan Song, Xiaokang Gao
P-374 Bulk geochemical characterisation of the source rocks for shale gas in Poland
Irena Matyasik, Wojciech Bieleń, Tomasz Słoczyński
P-375 Integration of basin modeling and geochemistry to describe dual sourcing of
granite wash reservoirs, Anadarko Basin, USA
Tony McClain, Harris Cander, Jonathan Evenick
P-376 Organic geochemical variability of gas shales: Woodford Shale, Southeastern
Oklahoma, USA, a case study
Andrea Miceli Romero, R. Paul Philp
P-377 Oil shales occurring in Mongolia
Vadim Saveliev, Namkhainorov Jargalsaikhan, Galina Pevneva, Anatoly Golovko
P-378 East Texas-North Louisiana USA unconventional shale gas resource systems
Daniel Jarvie , Francoise Behar, Yongchun Tang, Rolando di Primio, Brian
Horsfield, Wilhelm Dominik
46

Poster Session 4 – Thursday 22 nd September 2011
13.40 – 15.05
Environment and pollution 2
P-380 Distribution, fate and formation of non-extractable residues of a nonylphenol
isomer in soil derived organo-clay complexes and first evidence for a
stereoselective incorporation process
Jan Schwarzbauer, Patrick Riefer, Timm Klausmeyer, Andreas Schaeffer,
Burkhardt Schmidt
P-381 Permissible concentration of petroleum contaminants as determined from
studying the adaptive reaction of plants in a model experiment with permafrost
soil of yakutia
Sara Lifshits, Olga Chalaya, Yulia Glaznetsova, Iraida Zueva
P-382 Polycyclic aromatic hydrocarbons in bottom sediments of the Laptev and the
East Siberian seas
Ivan Litvinenko, Vera Petrova, Galina Batova, Anna Kursheva
P-383 Accumulation and degradation of plastic pollutants and diisopropyl-naphthalenes
during composting of organic household waste
Cesar Menor-Salvan
P-384 Fingerprinting of oil sheens, slicks, and tarballs collected in response to the MC
252 oil spill
Alexei Milkov, Changrui Gong, David Grass, Mike Sullivan, Tomieka Searcy,
Leon Dzou, Pierre-Andre Depret
P-385 Source determination and depth translocation of PAH in Chinese paddy and nonpaddy
soils
Cornelia Mueller-Niggemann, Philipp Roth, Eva Lehndorff, Lorenz Schwark
P-386 Remediation of hydrocarbon contaminated soils by modified Fenton oxidation in
the presence of magnetite
Usman Muhammad, Faure Pierre, Hanna Khalil, Ruby Christian
P-387 The use of phospholipid fatty acid analysis and isotopic techniques to track the
fate of organic contaminants in environmental systems.
Brian Murphy, Chris Allen, Leonid Kulakov, Anna Kulakov, Michael Larkin, Brian
Kelleher
P-388 ESR spectroscopic study of humic acid-like materials obtained by the
autoxidation of caffeic and chlorogenic acid
Ruţica Nikolić, Tatjana Anđelković, Goran Nikolić
P-389 Biogeochemical process studies on oil sand tailings used for land reclamation
Mareike Noah, Andrea Vieth-Hillebrand, Beate Schneider, Bernd Uwe Schneider,
Heinz Wilkes
P-390 A three-year survey of fluorescent dissolved organic matter in the Arcachon Bay
(South Western France)
Edith Parlanti, Marie-Ange Cordier, Fabienne Ibalot
P-391 Environmental forensics-recent applications of C, H and Cl isotopes in the
determination of sources of groundwater contaminants
Paul Philp, Tomasz Kuder
47

P-392 Environmental forensic study of a complexly contaminated soil at a former
chemical plant
José Luis R. Gallego, Michael A. Kruge, Iván Lores, Azucena Lara, Carlos Sierra
(33600 - Mieres
P-393 Geochemical characterization of oil spills samples and oil samples from wells
adjacent areas in order to determine the origin by oil-oil correlation, two case
studies, Monagas, Venezuela
Ysmarline Rincones, Carmen Rodriguez, Jennifer Arenas (Los Teques/Miranda,
Venezuela
P-394 Polycyclic aromatic hydrocarbons in the Pichavaram Mangrove-Estuarine
sediments, South-Eastern India
Rajesh Ranjan, Joyanto Routh, AL Ramanathan, J Val Klump
P-395 Source characterization using molecular distribution and stable carbon isotopic
composition of n-alkanes in sediment cores from Mundaú-Manguaba estuarinelagoon
system, Brazil
Thaís Silva, Silvia Lopes, Débora Azevedo
P-396 Brominated flame retardants in German Wadden Sea sediments
Thorsten Stiehl, George Sawal, Barbara Scholz-Böttcher, Melanie Beck, Jürgen
Rullkötter, Peter Lepom
P-397 Impact of different operating modes on the indigenous microbial ecosystems in
energy storage systems in the North German Basin: Compositional changes and
membrane phospholipid adaptation
Alexandra Vetter, Kai Mangelsdorf, Stephanie Lerm, Mashal Alawi, Andrea Seibt,
Markus Wolfgramm, Hilke Würdemann, Andrea Vieth-Hillebrand
P-398 Stable carbon isotope fractionation of dissolved BTEX during progressive
volatilization
Yongqiang Xiong, Yun Li, Qianyong Liang, Chenchen Fang, Jingru Zhang
P-399 Resolving sources and preservation mechanism of ahthropogenic and natural
organic matter in sediment of Beijing-Hangzhou Great Canal, China with usage
of Hydropyrolysis (HyPy)
Xiaoyu Zhang, William Meredity, Colin Snape, Yongge Sun, Xin Chen, Yang Xu
Poster Session 4 – Thursday 22 nd September 2011
13.40 – 15.05
Isotope geochemistry
P-401 Hydrogen isotope ratios of leaf wax lipids illustrate temporal and spatial
variations in the hydrologic cycle – results from two calibration studies off NW
Africa
Britta Beckmann, Eva Niedermeyer, Alex Sessions, Enno Schefuss
P-402 New insights into soil organic carbon build-up from compound-specific
radiocarbon analysis
Axel Birkholz, Rienk Smittenberg, Irka Hajdas, Lukas Wacker, Jostein Bakke,
Stefano M. Bernasconi
48

P-403 Spatial variability of compound-specific dD at the field scale: a case study from
miliacin in broomcorn millet (Panicum miliaceum)
Nicolas Bossard, Jérémy Jacob, Claude LeMilbeau, Rachel Boscardin, Elisabeth
Lallier-Vergès
P-404 Amino sugars as biomarkers for transformation of organic nitrogen compounds in
two Swiss lakes
Dörte Carstens, Krista E. Köllner, Gijs Nobbe, Helmut Bürgmann, Bernhard
Wehrli, Carsten J. Schubert
P-405 A novel tool for food web study: compound-specific stable nitrogen isotope
analysis of amino acids
Yoshito Chikaraishi, Nanako Ogawa, Naohiko Ohkouchi
P-406 Biogeochemistry of lake Soppensee (Switzerland) using a biomarker and a
compound-specific isotope approach
Merle Gierga, Rienk Smittenberg, Irka Hajdas, Lukas Wacker, Stefano
Bernasconi
P-407 Compound specific hydrogen isotopes as indicator of core metabolisms of
benthic microorganisms in the Wadden Sea
Sandra Heinzelmann, Laura Villanueva, Stefan Schouten, Jaap Sinninghe
Damsté, Marcel van der Meer
P-408 Sea surface salinity reconstructions of the Agulhas current based on alkenone
hydrogen isotope ratios
Sebastian Kasper, Marcel T.J. van der Meer, Geert-Jan Brummer, Isla S.
Castañeda, Rainer Zahn, Jaap S. Sinninghe Damsté, Stefan Schouten
P-409 Confining the role of biotic and/or abiotic factors influencing the 14C isotopic
composition of chlorophyll a isolated from algal cultures grown under different
seawater DIC Δ14C concentrations
Stephanie Kusch, Albert Benthien, Björn Rost, Gesine Mollenhauer
P-410 Carbon cycling in lacustrine food webs
J. Marieke Lammers, Carsten J. Schubert, Jack J. Middelburg, Jaap S.
Sinninghe Damsté, Gert-Jan Reichart
P-411 Intramolecular radiocarbon dating on archaeal intact polar lipids
Chun Zhu, Gesine Mollenhauer, Julius Lipp, Yu-shih Lin, Kai-Uwe Hinrichs
P-412 Radiocarbon distributions in Lake Superior, the world‘s largest freshwater lake
(by area)
Prosper Zigah, Elizabeth Minor, Josef Werne
P-413 D/H ratios of plant waxes as recorder of past rainfall intensities – insights to the
Indonesian paleomonsoon
Eva M. Niedermeyer, Alex L. Sessions, Mahyar Mohtadi
P-414 European lake sediment calibration of long chain n-alkane δD values
Gert-Jan Reichart, Cornelia Blaga, Jaap S. Sinninghe Damste
P-415 Stable carbon isotope compositions of lignin phenols and cutin acids among C3,
C4 and CAM plants
Kazuhiko Sonoda, Masashiro Takahashi, Shuichi Yamamoto
49

P-416 Developing analytical protocols for the measurement of 13C and 15N of crucial
organisms within the food web of the Dutch Wadden Sea
Elisabeth Svensson, Tjisse van der Heide, Sander Holthuijsen, Stefan Schouten,
Henk W. van der Veer, Jack J. Middelburg, Jaap Sinninghe Damste
P-417 Contributions of δD analyses of plant-derived fatty acid methyl esters in ravine
deposits to understanding palaeoenvironmental changes during the rise and fall
of kingdoms in northern Ethiopia
Valery Terwilliger, Zewdu Eshetu, Marcelo Alexandre, Yongsong Huang, Marilyn
Fogel
P-418 Extreme intra- and intermolecular carbon isotopic disparity in individual archaeal
intact polar lipids from methane seep sediments
Marcos Yukio Yoshinaga, Marcus Elvert, Yu-Shih Lin, Kai-Uwe Hinrichs
P-419 Effect of leaf litter degradation and seasonality on D/H isotope ratios of n-alkane
biomarkers
Michael Zech, Nikolai Pedentchouk, Björn Buggle, Katharina Leiber, Karsten
Kalbitz, Slobodan Markovic, Bruno Glaser
P-420 δ 2 H differences among lipids synthesised via the ACT (acetogenic), MVA
(mevalonic) and DXP (1-deoxy-D-xylulose 5-phosphate) pathways in higher plant
leaves: possible evidence for intracellular water (H+) isotopic heterogeneity
Youping Zhou, Kliti Grice, Hilary Stuart-Williams, Graham Farquhar, Charles
Hocart
Poster Session 4 – Thursday 22 nd September 2011
13.40 – 15.05
Microbial geochemistry/lipidomics/genomics 2
P-423 Effects of long-term climatic manipulations on microbial communities in European
shrublands
Sharon Mason, Chiara Cerli, Andrew Smith, Albert Tietema
P-424 Intact polar lipid and genetic signatures of archaea in estuarine sediments
Travis B. Meador, Cassandre Lazar, Marcos Y. Yoshinaga, Andreas Teske, Kai-
Uwe Hinrichs
P-425 Insights into the microbial communities of modern stromatolites (Highborne Cay,
Bahamas) from bacterial and eukaryotic lipids
Sabine Mehay, Joan Bernhard, Anna McIntyre-Wressnig, Virginia Edgcomb,
Roger Summons
P-426 Bacterial versus archaeal activity in episodically flooded soils – a combined
lipidomics/genomics approach
Cornelia Mueller-Niggemann, Andrea Bannert, Michael Schloter, Kai
Mangelsdorf, Lorenz Schwark
P-427 Quantitative reconstructions of methanogenic and methanotrophic archaeal
communities in Lake Rotsee, Switzerland, using biomarker concentrations and
their carbon isotopic compositions
Sebastian Naeher, Rienk Smittenberg, Carsten Schubert
P-428 Study of microbial activity associated to SW-Barents sea pockmarks
Julia Nickel, Kai Mangelsdorf, Jens Kallmeyer, Rolando di Primio,Daniel Stoddart
50

P-429 Microbial diversity and organic matter cycling of methane-related seabed
seepage structures in Irish waters
Shane O' Reilly, Michal Szpak, Xavier Monteys, Christopher Allen, Brian Kelleher
P-430 New bacteriochlorophyll degradation products from a coastal salt pond
Raymonde Baltenweck-Guyot, Ruben Ocampo-Torres
P-431 Carbohydrate dynamics in Cariaco Basin pore water and sediments
Melesio Quijada, Armelle Riboulleau, Yann Guerardel
P-432 Thermally stable anammox biomarker lipids produced during hydrous pyrolysis
Darci Rush, Andrea Jaeschke, Stefan Schouten, Jaap Sinninghe Damsté
P-433 Environmental occurrence of oxic degradation products of anammox ladderane
lipids
Darci Rush, Andrea Jaeschke, Ellen Hopmans, Stuart Wakeham, Stefan
Schouten, Jaap Sinninghe Damsté
P-434 Impact of a high CO2 partial pressure on the methanogenic pathway in a hightemperature
petroleum reservoir
Daisuke Mayumi, Susumu Sakata, Haruo Maeda, Yoshihiro Miyagawa, Masayuki
Ikarashi
P-435 Impact of lake water pH on the distribution of branched tetraether membrane
lipids: further indication for an aquatic source
Petra Schoon, Anna de Kluijver, Jack Middelburg, John Downing, Jaap
Sinninghe Damsté, Stefan Schouten
P-436 Methane oxidation in the water column of Lago di Cadagno (Switzerland)
Carsten J. Schubert, Andreas Krupke, Mathias Kirf, Daniela Franzke, Marcel
M.M. Kuypers
P-437 Microbial community shifts at temperature and geochemical gradients at sulfurrich
shallow hydrothermal vents offshore Panarea Island, Sicily
Florence Schubotz, Chia-I Huang, Gunter Wegener, Jan P. Amend, Roy Price,
Thomas Holler, Anke Meyerdierks, Rudolf Amann, Roger E. Summons, Kai-Uwe
Hinrichs
P-438 Lipid biomarkers of archaeal and sulphate reducing bacterial aggregates in gas
hydrate-bearing deep sea sediment
Yong-Cheon Ahn, Jang-Jun Bahk, Jung-Hyun Lee, Kyung-Hoon Shin
P-439 Origin of alkane hydrocarbons in the hydrothermal deposits of the Mid-Atlantic
Ridge and East Pacific Rise
Natalia Shulga, Valerij Peresypkin
P-440 Estimation of endospore numbers in marine sediment samples by quantification
of dipicolinic acid
Marieke Sieverding, Bert Engelen, Henrik Sass, Barbara Scholz-Böttcher,
Heribert Cypionka, Jürgen Rullkötter
P-441 Investigating relationships between OM and diatom frustules and their
implications in the export of organic carbon in the ocean
Maxime Suroy, Brivaëla Moriceau, Madeleine Goutx
51

P-442 Deep-sea benthic archaea recycle relic membrane lipids: insight from ―in situ
13C-incubation experiment‖ and its lipidomics
Yoshinori Takano, Yoshito Chikaraishi, Nana O. Ogawa, Hidetaka Nomaki, Yuki
Morono, Fumio Inagaki, Kai-Uwe Hinrichs, Nao Ohkouchi
P-443 Hopanoids in silica sinters: identification of an unusual pathway in hopanoid
diagenesis with implications for the sedimentary biomarker record
Robert Gibson, Gurpreet Kaur, Bruce Mountain, Richard Pancost, Helen Talbot
P-444 Isolating and cultivating environmentally relevant micro-organisms as reference
point for linking phylogeny to activity in situ based on biomarker lipids
Marcel van der Meer, Christian Klatt, Jason Wood, Donald Bryant, Mary Bateson,
Laurens Lammerts, Stefan Schouten, Jaap Sinninghe Damste, Michael Madigan,
David Ward
P-445 The influence of geological and geochemical processes on microbial
biogeography at hydrothermal vents on the Mid-Atlantic Ridge: evidence from
the distribution of intact polar lipids
Robert Gibson, Marcel van der Meer, Ellen Hopmans, Anna-Louise Reysenbach,
Stefan Schouten, Jaap Sinninghe Damsté
P-446 Distribution of ammonia-oxidizing archaea and anammox bacteria in the arabian
sea OMZ using a combined approach based on intact polar lipids and
abundance/expression of specific genes
Laura Villanueva, Angela Pitcher, Ellen Hopmans, Stefan Schouten, Jaap
Sinninghe Damsté
P-447 The vertical niche of Thaumarchaota in Lake Malawi; implications for the TEX86
temperature signal in the sediment
Martijn Woltering, Josef Werne, Melissa Berke, Ellen Hopmans, Jaap Sinninghe
Damsté, Stefan Schouten
P-448 Genetic and metabolic characterization of methanogen microbial communities in
the Antrim gas shale formation
Cornelia Wuchter, Erin Banning, Nick Drenzek, Marco Coolen
P-449 Glycerol dialkyl glycerol tetraethers and the TEX86 index in sinking particles in
the western North Pacific
Masanobu Yamamoto, Yuichiro Tanaka, Akifumi Shimamoto
P-450 Proxies based on archaeal and bacterial GDGTs in surface sediments of the
Yangtze River Estuary, China: implications for marine organic biogeochemistry
Peng Yao, Brendan Keely, Zhigang Yu, Hongzhen Yin, Meixun Zhao
P-451 Methane fluxes modulating the molecular and carbon isotopic composition of
microbial lipids in gas hydrate bearing sediments from the northern Cascadia
margin
Marcos Yukio Yoshinaga, John W. Pohlman, Tobias Goldhammer, Nadine
Broda, Michael Riedel, Marcus Elvert, Kai-Uwe Hinrichs
52

Poster Session 4 – Thursday 22 nd September 2011
13.40 – 15.05
Proxies and paleoreconstructions 2
P-453 Experimental paleochemotaxonomy of conifers: the Araucariaceae family
Yueming Lu, Yann Hautevelle, Raymond Michels
P-454 Tracing of palaeofloristic changes in the Paris basin (France) during Jurassic:
contribution of the retene/cadalene ratio
Yueming Lu, Yann Hautevelle, Raymond Michels
P-455 Long term cooling and punctuated climate events recorded in Late Aptian to
Early Albian sediments from the eastern subtropical Atlantic (Mazagan Plateau,
DSDP Site 545)
Alison McAnena, Thomas Wagner, Helen M. Talbot, Jens Herrle, Joerg Pross,
Janet Rethemeyer, Peter Hofmann
P-456 Post-glacial paleoclimatic changes in northeastern Brazil inferred from depthsensitive
depositional records of organic matter in sediments of Lagoa do Caçó
Abdelfettah Sifeddine, Philip Meyers, Renato Campello Cordeiro, Ana Luiza
Spadano Albuquerque, Marcello Bernardes, Marie-Pierre Ledru, Bruno Turcq,
Jorge Joao Abrao
P-457 Molecular and isotopic evidence for differences in organic matter delivery and
preservation in two mid-Pleistocene light-dark color cycles in sediments beneath
the Benguela Current Upwelling System
Philip Meyers, Ioanna Bouloubassi, Richard Pancost
P-458 220 ka palaeoenvironmental reconstruction of the Fuentillejo maar-lake record
(Central Spain) using biomarker analysis
Laura Moreno, José E. Ortiz, Trinidad Torres, Juana Vegas, Blanca Ruiz-Zapata,
Ángel García-Cortés, Luis Galán, Alfredo Pérez-González
P-459 Long-term variations of palaeovegetation recorded by angiosperm and
gymnosperm biomarkers in the Late Cretaceous sequence of Kotanbetsu,
Hokkaido, Japan
Hideto Nakamura, Ken Sawada, Reishi Takashima
P-460 Geochemical and historical study of a 700 year old pond, Lansquenet -Lorraine,
France- A multidisciplinary approach
Olivia Bertrand, Laurence Mansuy-Huault, Emmanuelle Montargès-Pelletier,
Benoît Losson, Jacqueline Argant, Raymond Michels, Pierre Faure, Emmanuel
Garnier, Charles Kraemer
P-461 Miocene to Pliocene environmental changes recorded in South-West African
continental margin sediments
Florian Rommerskirchen, Lydie Dupont, Gesine Mollenhauer, Enno Schefuß
P-462 Branched tetraether lipid derived air temperature and soil pH in lake sediments
from Zeekoevlei, South Africa
Supriyo Das, James Bendle, Joyanto Routh
P-463 Holocene paleoclimatic variations recorded by biomarkers in sediment cores
from the Dabusu Lake, northeastern China
Ken Sawada, Makiko Ono, Yuroyuki Kitagawa, Hu Ke
53

P-464 Effects of within-catchment provenance on terrestrial climate parameters in
marine sediments off large rivers
Enno Schefuß, Gesine Mollenhauer, Holger Kuhlmann, Matthias Prange, Jürgen
Pätzold
P-465 Hydrological and biogeochemical variations in the hypersaline Lake Tswaing
(South Africa) during the last 84 ka BP
Frauke Schmidt, Hedi Oberhänsli, Heinz Wilkes
P-466 Can molecular markers for pyrogenic carbon help to reconstruct wildfire
temperatures?
Maximilian P.W. Schneider, William C. Hockaday, Caroline A. Masiello, Michael
W.I. Schmidt
P-467 Molecular hydrogen isotope systematics in Eocene lake sediments: Hydrogen
isotope exchange and estimate of paleo lake water hydrogen isotope
composition
Nils Andersen, Stefano M. Bernasconi, Robert M. K. Carlson, Martin Schoell
P-468 Carbon isotopic composition of Thaumarchaeotal ether-bound biphytanes during
the early Eocene carbon isotope excursions
Petra Schoon, Appy Sluijs, Henk Brinkhuis, Claus Heilmann-Clausen, Bo Pagh
Schultz, Jaap Sinninghe Damsté, Stefan Schouten
P-469 Impact of anaerobic methane oxidizing archaea on TEX86-L paleotemperature
records from Antarctica
Stefan Schouten, Veronica Willmott, Eugene Domack, Rieneke Gieles, Jaap
Sinninghe Damste
P-470 Organic-geochemical proxies for tsunami-events in sediment cores of the
Thermaikos Gulf
Frederike Wittkopp, Klaus Reicherter, Jan Schwarzbauer
P-471 Integrating biomarker and microfossil records across the Cretaceous-Paleogene
mass extinction event
Julio Sepulveda, Laia Alegret, Emily Wooton, Changqun Cao, Roger Summons
P-472 Variability of Sea Surface Temperature in the Eastern Equatorial Pacific Ocean
during Last Glacial Cycles
Hasrizal Shaari, Masanobu Yamamoto, Tomohisa Irino
P-473 Application of TEX86-paleothermometry in the Baltic Sea: Validation and
temperature reconstruction of the past 1000 years
Jaap Sinninghe Damsté, Karoline Kabel, Florian Adolphi, Marianne Baas,
Matthias Moros
P-474 Paleosalinity significance of the occurrence and distribution of MTTCs in the
Nenjiang Formation of Upper Cretaceous in Songliao Basin, China
Li Wang, Zhiguang Song, Qin Yin, Jiangtao Guo
P-475 Stable isotopes (C, S) and hydrocarbon biomarkers in Neoproterozoic sediments
of the Sierras Bayas Group, Argentina
Mariluz Bagnoud-Velasquez, Jorge E. Spangenberg
54

P-476 Geochemical appraisal of palaeovegetation and climate oscillation in the Late
Miocene of Western Bulgaria
Maya Stefanova, Dimiter Ivanov
P-478 The first findings of 12- and 13-monomethylalkanes in dispersed organic matter
of Upper Proterozoic and Cambrian of Siberian platform
Aleksey Kontorovich, Vladimir Kashirtsev, Konstantin Nagovitsin, Pyotr Sobolev,
Valentina Sukhoruchko, Irina Timoshina
P-479 Assessment of the 1,14 diol SST proxy based on sediment trap samples from the
NW African upwelling area
Eleonora Uliana, Gerard Versteegh, Gesine Mollenhauer, Enno Schefuss
P-480 The 3 P's* and the Albian oceanic anoxic event (OAE) 1b (*palaeoclimate,
palaeoenvironment & palaeooceanography)
Isabel Urbat
P-481 A biomarker reconstruction of Holocene changes in rainfall and runoff from
Charlotte Harbor (Florida)
Els E. van Soelen, Gregg R. Brooks, Rebekka Larson, Jaap S. Sinninghe
Damsté, Gert-Jan Reichart
P-482 Meter-scale oxygen gradients and selective organic matter degradation:
implications for proxy interpretation
Kara Bogus, Karin Zonneveld, David Fischer, Sabine Kasten, Gerard Versteegh
P-483 Selective aerobic and anaerobic degradation of lipids and palynomorphs in the
Eastern Mediterranean since the onset of sapropel S1 deposition
Gerard J.M. Versteegh, Karin A.F. Zonneveld, Gert J. de Lange
P-484 Coupling of Miocene-Pliocene (7-5 Ma) African climate, surface ocean
temperature and marine organic carbon burial: high-resolution, multi-proxy
records from the eastern equatorial Atlantic (ODP 959)
Thomas Wagner, Olubunmi Eniola, Erin McClymont
P-485 Complications in the interpretation of molecular paleotemperature
reconstructions using isoprenoid and branched tetraethers: lessons to be
learned
Josef Werne, Beth Bernhardt, Martijn Woltering, Melissa Berke, R. Douglas
Ricketts, Margarita Caballero, Ellen Hopmans, Stefan Schouten, Jaap Sinninghe
Damsté
P-486 New molecular marker and spectroscopic tools for reconstructing wildfire history
Daniel B. Wiedemeier, Simon G. Haberle, Evelyn S. Krull, Michael W.I. Schmidt
P-487 Late Quaternary environmental change of Yellow River Basin: an organic
geochemical record in Bohai Sea (North China)
Yunping Xu, Wenbing Tan, Dongyan Sun
P-488 Paleoenvironmental changes from organic matter composition in the California
margin sediments (ODP Leg 167, Hole1017E) during the last 45kyrs
Shuichi Yamamoto, Chieko Dairiki, Ryoshi Ishiwatari
P-489 Branched GDGTs as biomarkers for temperature reconstructions from paleosols.
Three case studies and potential complications
Roland Zech, Li Gao, Rafael Tarozo, Yongsong Huang
55

Poster Session 4 – Thursday 22 nd September 2011
13.40 – 15.05
Soil and peat and terrestrial OM 2
P-491 Methoxy-serratenes as discriminant biomarkers for soils developed under conifer
forests
Claude Le Milbeau, Marlène Lavrieux, Jérémy Jacob, Renata Zocatelli, Jean-
Robert Disnar
P-492 Investigating the microbial populations controlling the production and oxidation of
methane in water-saturated mineral soils
Katie Lim, Peter Maxfield, Edward Hornibrook, Richard Pancost, Richard
Evershed
P-493 Vegetation and soil organic matter input offshore southeastern Australia based
on organic proxies
Raquel Lopes dos Santos, Daniel Wilkins, Patrick De Deckker, Stefan Schouten
P-495 Testing branched GDGT-derived proxy parameters in the Arctic Ocean
Gesine Mollenhauer, Konstanze Schipper, Kirsten Fahl, Rüdigel Stein
P-497 Decomposition of wheat straw buried in a grassland soil: the fungi involved and
the products obtained
Rachel Muito-Kabuyah, Clare Robinson, Bart van Dongen
P-498 Molecular and isotope characterization of soil lipids along a savannah
(C4)/eucalyptus (C3) chronosequence (Pointe-Noire, Congo)
Thanh Thuy Nguyen Tu, Mercedes Mendez-Millan, Céline Egasse, Sylvie
Derenne, Bernd Zeller, Delphine Derrien, Jeremy Jacob, Christine Hatté
P-499 The relationship between peatland hydrology, biogeochemistry and biomarker
assemblages
Rich Pancost, Richard Evershed, Edward Hornibrook, Erin McClymont, Elizabeth
Bingham, Lidia Chaves, Katie Lim, Frank Chambers
P-500 Geochemical characterization of the impact of landuse change on soil and
riverine organic matter dynamics in a pristine tropical rainforest, Guyana
Ryan Pereira, Robert Spencer, Peter Hernes, Rachael Dyda, Isabella Bovolo,
Geoff Parkin, Thomas Wagner
P-501 Land use and climatic effects on hydrogen isotope compositions of long-chain nalkanes
and distribution of tetraether lipids in soils
Janet Rethemeyer, Michael Lappé, Stefan Schouten, Pascal Boeckx, Enno
Schefuß
P-502 Soil organic matter characteristics in the permafrost terrain, European Russian
Arctic: lability, storage, and impact of thawing
Joyanto Routh, Gustaf Hugelius, Timothy Filley, Patrick Crill, Peter Kuhry
P-503 Geochemical characterization of a meadow soil
Tünde Nyilas, Magdolna Hetényi, Nóra Czirbus, Anita Gál, Csanád Sajgó
P-504 Hydrocarbons occurring in peats of different types and origins (Southern Taiga of
Western Siberia, Russia)
Olga Serebrennikova, Yulia Preis, Elena Gulaya
56

P-505 Organic carbon composition and routing in alpine headwaters: the importance of
storms
Jo Smith, Niels Hovius, Albert Galy, Jens Turowski
P-506 Preservation of Particulate Organic Carbon from an active mountain belt in
shallow marine sediments
Robert Sparkes, Niels Hovius, Albert Galy, Vasant Kumar
P-507 Dynamics of soil organic matter and mineral nitrogen in soil: investigation into a
complex relationship
Priscillia Sémaoune, Joëlle Templier, Mathieu Sébilo, Christelle Anquetil, Sylvie
Derenne
P-508 Deltaic sediments as recorders of permafrost carbon dynamics within Arctic
drainage basins: a case study from the Mackenzie River
Jorien Vonk, Xiaojuan Feng, Angela Dickens, Zainab Hussain, Bokyung Kim,
Liviu Giosan, Sam Zipper, Daniel Montluçon, Timothy Eglinton
P-509 Exploiting isotopic, organic, and inorganic geochemical tracers of terrestrial
matter in suspended particles of the Fraser River, British Columbia
Britta M. Voss, Bernhard Peucker-Ehrenbrink, Timothy I. Eglinton, Valier Galy,
Daniel B. Montluçon, Ekaterina Bulygina, R. Max Holmes, Gregory Fiske, Li Xu,
Sharon L. Gillies, Steven Marsh, Alida Janmaat, Bryce Downey, Jenna Fanslau,
Helena Fraser, Garrett Macklam-Harron
P-510 Testing the potential of bacterial branched tetraether lipids as temperature proxy
in peat and immature coal deposits
Johan Weijers, Philipp Steinmann, Ellen Hopmans, Stefan Schouten, Jaap
Sinninghe Damsté
P-511 The effect of soil moisture on biosynthesis of lipids in plants and their
incorporation and preservation in soils
Guido Wiesenberg, Bidisha Majumder, Martina Gocke, Jennifer Dungait, Liz
Dixon, Roland Bol
P-512 The effect of fire intensity on alkane composition of plant organic matter and soils
affected by fire
Guido Wiesenberg, Andreas Nestler, Stefanie Birkner, Ulrich Hambach
P-513 Anaerobic oxidation of plant-derived 3-phenylpropanoids by the denitrifying
bacterium ―Aromatoleum aromaticum‖ EbN1
Heinz Wilkes, Kathleen Trautwein, Ralf Rabus
P-514 Molecular characterization of terrestrial, permafrost-derived organic matter along
a soil-river-ocean transect (Lena Delta, NE Siberia)
Maria Winterfeld, Miguel Goni, Gesine Mollenhauer
P-515 Variability of terrestrially-derived particulate organic carbon in the lower Yangtze
River (Changjiang): A monsoon dominated water system
Ying Wu, Hao Yu, Jing Zhang, ZhuoYi Zhu
P-516 Distributions of branched tetraethers in soils and suspended particulate matter in
the Amazon basin: implications for the MBT/CBT palaeothermometer
Claudia Zell, Jung-Hyun Kim, Marie-Paule Bonnet, Gwenaël Abril, Jean-Michel
Mortillaro, Rodrigo Sobrinho, Jaap Sinninghe Damsté
57

Monday Oral Presentations
58

O-01
Extractive and structural phenolic compounds in a Neolithic
leather from the Swiss Alps
Jorge E. Spangenberg 1 , Albert Hafner 2
1 Institute of Mineralogy and Geochemistry, University of Lausanne, Lausanne, Switzerland, 2 Archaeological
Service of the Canton Bern, Bern, Switzerland (corresponding author:Jorge.Spangenberg@unil.ch)
Archaeological finds of leather are rare. If preserved,
the leather has naturally been re-tanned at the
particular burial environment, such as an anoxic
acidic environment in peat bogs, saline environments
in salt mines, or polyphenol-rich mediums in wooden,
oakcoffins [1]. None of these archaeological finds can
be used to identify the prehistoric tanning methods.
Leather clothing of the iceman Ötzi from the
Hauslabjoch (3350-3300 cal BC) has, for the first
time, provided the possibility to determine such
methods without any secondary influence; but the
artifacts were swabbed with phenol soon after their
discovery, making such investigations impossible [2].
A late Neolithic leather legging (2914-2652 cal BC),
well-preserved in situ, frozen in ice and snow, under
anaerobic conditions, was recovered from the
Schnidejoch ice-patch (2750 m amsl) in the western
Swiss Alps. This material provides an unequalled
opportunity to study the methods used in curing skins.
An important amount of n-alkanoic acids, waxy nalkanes,
n-alkan-1-ols and phytosterols (β-sitosterol,
sitostanol), and a biomarker of conifers (nonacosan-
10-ol) in the lipids extracted from the legging leather
(made from the skin of a domestic goat) indicate that
the Neolithic people were active in a subalpine,
coniferous forest [3].
In this study, a lipid-free aliquot of Schnidejoch leather
was subjected to a methanol/water extraction to
obtain the extractible phenolic compounds (fraction
A). The solid residue (mostly collagen) was acid
hydrolysed with methanol/HCl 6M to obtain the
structural phenols (fraction B), forming strong
complexes with macromolecules of collagen proteins.
The GC-MS traces of the TMS derivates of both
fractions show that the most abundant compounds
were n-alkanoic acids (C9-18) and short chain α, ω
alkandioic acids (C4-8) as residual lipids from animal
skin (Fig. 1). The presence of lignin monomers, such
as polyphenols and phenols containing keto and
carboxyl units is a diagnostic biomarker of vascular
plant tannins. These results provide direct evidence
for the use of aqueous extracts of higher plant
material, including oak bark for tanning leather in the
Alpine domain, 3d millennium BC.
Fig. 1. GC-MS TIC of the TMS derivates of fractions A and B
of Schnidejoch leather (see text).
References
[1] Groenman-van Waateringe, W. Kilian, M., Van
Londen, M. (1999) Antiquity 73, 884-890.
[2] Rollo, F. et al. (2000) American Journal of Physical
Anthropology 111, 211-219.
[3] Spangenberg, J.E. et al. (2010) Journal of
Archaeological Science 37, 1851-1865.
59

O-02
Melting history of West Antarctic Ice Sheet since the last glacial
maximum revealed by compound-specific radiocarbon dating
Nao Ohkouchi 1 , Hisami Suga 1 , Yoshito Chikaraishi 1 , Yusuke Yokoyama 2 , Takahiro
Yamazaki 2 , Yosuke Miyairi 2 , Hiroyuki Matsuzaki 2 , John Anderson 3 , John Southon 4 ,
Timothy Eglinton 5
1 JAMSTEC, Yokosuka, Japan, 2 University of Tokyo, Kashiwa, Japan, 3 Rice University, Houston, United
States of America, 4 University of California, Irvine, Irvine, United States of America, 5 ETH, Zurich,
Switzerland (corresponding author:nohkouchi@jamstec.go.jp)
The stability of the marine-based West Antarctic
Ice Sheet (WAIS) is the subject of major scientific and
societal concern because of its potential susceptibility
to collapse as a consequence of global warming, with
resulting consequences for global sea level. On the
Antarctic margin, paleoclimatologic investigations of
the sediment record have been hindered seriously by
a paucity of calcareous fossils, which yield precise
chronology through their radiocarbon content. Recent
developments in molecular-level radiocarbon dating of
sediments provide tools for overcoming the problem
(Ohkouchi et al., 2003; Ohkouchi and Eglinton, 2008).
In this presentation, we report recent applications
of this method to the Ross Sea sediment cores. Fatty
acid ages from 7 sediment cores recovered in the
wide area of the Ross Sea (Fig. 1) indicated
substantially younger chronologies relative to bulk-
TOC based chronologies. Together with
atmospherically derived
10 Be concentration, we
estimated the precise timing when edge of Ross Ice
Shelf crossed over these core sites. It suggested that
the Ross Sea section of WAIS substantially retreated
during the Holocene. During the mid-Holocene, it
could have been located about 200-400 km north to
the modern shelf edge (Fig. 1).
Furthermore, hydrogen isotopic record of certain
marine biomarkers in a core from the NW Ross Sea is
punctuated by intervals of extremely D-depletions (�D
values as low as to -570‰) around 6.8, 5.7, 4.1, 2.5,
and 1.5 ka. We attribute these abrupt isotopic
excursions to freshwater discharge events,
suggesting the WAIS has experienced several
intermittent, rapid melting episodes during the
Holocene.
Our record suggested that the WAIS melting
episodes occurred after sea-level had returned to
within 4 m of the modern-day level, implying that the
WAIS at most supplied an equivalent to ~1.5 × 10 6
km 3 of water during the last 7 kyr. If these D-depletion
events were of the same magnitude, each event
would have produced up to ~3 × 10 5 km 3 of
meltwater, which is three orders of magnitude larger
than the contemporary annual meltwater flux from the
WAIS. Therefore, future sea-level rise associated with
the attrition of the WAIS could be rapid rather than
gradual given the intermittent, rather than continuous,
nature of prior melting events.
Ross Sea
WAIS
Fig. 1. Core sites (red dots) and estimated position of
WAIS edge in the Ross Sea (a blue broken line)
during the mid- Holocene (~5000 years ago).
References
Ohkouchi N, Eglinton TI, Hayes JM (2003)
Radiocarbon, 45, 17-24.
Ohkouchi N, Eglinton TI (2008) Quaternary
Geochronology, 3, 235-243.
60

O-03
Diamonds in the rough: identification of individual naphthenic
acids in petroleum and oil sands process water
Steven Rowland 1 , Charles West 1 , Alan Scarlett 1 , David Jones 1 , Richard Frank 2
1 Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth, PL4 8AA, UK,
Plymouth, United Kingdom, 2 Aquatic Ecosystems Protection Research Division / Water Science &
Technology Directorate, Environment Canada, 867 Lakesh, Burlington, Canada
Expansion of the oils sands industry of Canada has
seen a concomitant increase in the amount of process
water produced and stored in large lagoons.
Concerns have been raised, particularly about the
toxic complex mixtures of water–soluble naphthenic
acids (NA) in the process water, yet to date no
individual NA have been identified, despite numerous
attempts. Similarly, NA are also an integral part of
many biodegraded or partially biodegraded petroleum
systems.
The complexity of NA mixtures has prevented their
resolution and identification for over a century, except
in a minority of cases.
Here we describe the chromatographic resolution and
mass spectral identification of individual NA from
petroleum and in oil sands process waters. The
presence of tricyclic and pentacyclic diamondoid
acids, never before even considered as NA, revealed
the unprecedented biodegraded nature of some of the
samples. The identifications are supported by
analysis of numerous synthetic diamondoid acids and
should now be followed by quantitative studies and be
used to direct toxicity assays of relevant NA.
The novel two-dimensional comprehensive gas
chromatography-mass spectrometry method
described will also be important for helping to better
focus reclamation/remediation strategies for NA, as
well as in facilitating the identification of the sources
of NA in contaminated surface waters, offshore
produced waters and biodegraded petroleums.
61

O-04
Insights about the marine nitrogen cycle from nitrogen isotopes
of sedimentary porphyrins
Meytal B. Higgins 1,2 , Ann Pearson 1
1 Harvard University, Cambridge, United States of America, 2 Princeton University, Princeton, United States of
America (corresponding author:pearson@eps.harvard.edu)
Episodes of deposition of organic-rich sediments
in the mid-Cretaceous known as Oceanic Anoxic
Events (OAEs) are attributed to high productivity
resulting from increases in nutrient supply, or to
enhanced organic matter preservation resulting from
decreases in the ventilation of deep waters.
Sediments from the largest of these events, the
Cenomanian-Turonian Oceanic Anoxic Event (OAE2)
are characterized by low � 15 N values not seen in
modern marine settings. It has remained a challenge
to describe a nitrogen cycle that could achieve such
isotopic depletion. Here we use � 15 N values of
porphyrins to propose a conceptual model for the
nitrogen cycle in anoxic oceans.
The offset between � 15 N values of sedimentary N
and coeval porphyrins is known as �por. Differences in
the 15 N offset between chlorophyll and biomass in
cyanobacteria and eukaryotes results in systematic
differences in �por that depend on the taxonomic
source of organic matter in sediments. Using the
respective endmember values for �por, we show that
eukaryotes contributed the quantitative majority of
export production throughout OAE2 (Fig. 1). The
relative export of cyanobacteria increased during the
OAE event but on average did not contribute more
than ~20% of the export flux of nitrogen.
Such data require that any explanation for the
OAE nitrogen cycle and its isotopic values also be
consistent with a eukaryote-dominated ecosystem.
Our results agree with models suggesting that OAEs
were supported by upwelling of nutrient-rich waters,
which in anoxic basins primarily would have contained
reduced N species (i.e., NH4 + ). We propose that new
production primarily was driven by direct NH4 +
assimilation supplemented by diazotrophy, while
chemocline denitrification and anammox quantitatively
consumed downwelling NO3 - and NO2 - . We present a
simple isotope balance model using known kinetic
isotope effects, which shows that the NH4 + reservoir
can be depleted in 15 N when NH4 + assimilation
exceeds nitrification.
In this model, only a small fraction of net
production may be fueled by cyanobacterial N
fixation. Concurrent with this interpretation, N fixation
alone cannot generate biomass with � 15 N values as
depleted as are seen in many Mesozoic OAE
sections. Instead, our data suggest only a modest
increase in cyanobacterial production. A small deficit
in fixed N during OAEs is not surprising, as anoxia
promotes denitrification. What may be surprising is
that the deficit was not larger. We suggest that
counter-intuitively, rates of denitrification may
decrease under conditions of extreme basin-wide
anoxia. Denitrification and anammox both depend on
sufficient availability of NO3 - and NO2 - . Because these
oxidized N species are produced aerobically, extreme
oxygen limitation in the water column may decrease
their rate of formation, leaving a greater fraction of
remineralized organic nitrogen to enter the photic
zone as NH4 + . This in turn would limit the need for
compensating N-fixation. Evidence for photic-zone
sulfide oxidation during OAEs shows that NO3 - indeed
was completely absent beneath the photic zone, at
least episodically (1, 2). We suggest that this negative
feedback on the N cycle limits both the extent of
denitrification and the expansion of cyanobacteria.
(1) Kuypers MMM et al. (2002) Paleoceanogr. 17, 13PP. (2)
Pancost RD et al. (2004) J. Geol. Soc. 161, 353-364.
62

O-05
Highly condensed, sulfur-rich hydrocarbon detected in oils
altered by thermochemical sulfate reduction: Precursors to TSRsolid
bitumen
Clifford Walters 1 , Kuangnan Qian 1 , Chunpingq Wu 1 , Anthony Mennito 1 , Zhibin Wei 2
1 ExxonMobil Research & Engineering, Annadale, NJ, United States of America, 2 ExxonMobil Exploration
Company, Houston, TX, United States of America (corresponding
author:clifford.c.walters@exxonmobil.com)
Thermochemical sulfate reduction (TSR) involves a
complex series of free radical and redox reactions
that occurs in hot (>120°C) carbonate reservoirs
whereby petroleum is oxidized by sulfate forming
primarily H2S, CO2, and an insoluble, highly sulfurenriched
and largely polynuclear aromatic organic
solid. The process negatively impacts the quality and
quantity of the petroleum reserves. Using ultrahigh
resolution mass spectrometry, we show that the TSRorganic
solid is formed via condensation and
sulfurization reactions that take place within the
petroleum fluid.
A suite of Smackover Fm. oils from several subbasins
along the northern rim of the Gulf of Mexico was
analyzed using APPI- (atmospheric pressure
photoionization) and NESI- (negative ion electrospray
ionization) ion cyclotron resonance Fourier transformmass
spectrometry (ICRFT-MS). The absence or
extent of TSR alteration had been assessed by prior
isotopic and molecular analyses. The selected oils
thus represent fluids that were exposed to a range of
thermal maturity (from early oil generation through the
oil window into gas generation and oil cracking) with
and without the influence of TSR alteration.
The composition of oils unaltered by TSR changes in
a manner consistent with thermal processes. With
increasing thermal stress, the distributions of aromatic
hydrocarbons (HC) and heteroatomic species
containing one and two sulfur atoms (1S and 2S,
respectively) shift toward species with smaller
polynuclear aromatic cores and lower degrees of
alkylation. In contrast, TSR-altered oils contain
relatively high concentrations of species with highly
condensed, polynuclear aromatic cores that are
enriched in sulfur. The strongest enrichments are
seen in condensates that have experienced the
greatest degree of TSR alteration. These fluids are
produced from reservoirs with high concentrations of
H2S and they possess relatively high concentrations
of sulfur-containing diamondoids and light
hydrocarbons with very heavy δ 13 C values –
characteristics known to indicate the degree of TSR-
alteration. The degree of alkylation is lower in the
TSR-altered oils than non-TSR altered oils of
equivalent maturity suggesting that TSR also
promotes the oxidative removal of alkyl sidechains.
These sulphur-enriched species are termed ―protosolid
bitumen‖ as they are marginally soluble in the
TSR-altered oils and could easily precipitate with
slight chemical alteration or changes in reservoir
conditions.
The presence of these species prove that sulfurenriched-solid
bitumen may arise from the TSR
process and do not require the prior occurrence of
asphaltenes in the unaltered oil.
H/C
HC 1S 2S HC 1S 2S 3S
2.02
1.75
1.5
H/C
1.25
1.01
.75
Unaltered
37.3° API
0 mol% H 2 S
Brantley-Jackson Chitsey
Min
0.5.5
0 .05 .1
.15
0
.05 .1 .15
0 0.5 1.0 0 0.5 1.0 Min
* Only HC,1S,2S,3S Shown.
S/C
S/C S/C
TSR-altered
51.3° API
16 mol% H 2 S
Max
Max
ccwalte - 10-Jan-2011 11:55
APPI-ICR-FTMS comparing the relative distribution of
aromatic hydrocarbons (HC) and sulfur-containing
(1S, 2S, & 3S) species in unaltered and TSR-altered
oil from the Mexia-Talco trend (Tx). The TSR-altered
oil is enriched in highly condensed HC and contains
highly condensed 1S, 2S and 3S species that are not
present in the unaltered oil.
63

O-06
Eocene out-of-India dispersal of Asian dipterocarps
Suryendu Dutta 1 , Suryakant Tripathi 2 , Monalisa Mallick 1 , Runcie Mathew 1 , Paul
Greenwood 3 , Mulagalapalli Rao 2 , Roger Summons 4
1 Indian Institute of Technology Bombay, Mumbai, India, 2 Birbal Sahni Institute of Palaeobotany, Lucknow,
India, 3 The University of Western Australia, Perth, Australia, 4 Massachusetts Institute of Technology,
Cambridge, United States of America (corresponding author:s.dutta@iitb.ac.in)
Dipterocarpaceae comprise large trees that dominate
the canopy of lowland equatorial forests. They
typically contribute to 30% of the total basal area of
typical lowland evergreen forests in southeast Asia
and play a dominant role in Asian rain forest ecology.
Two opposing hypotheses have been proposed to
explain the origin of the Asian dipterocarps. Some
hypothesize that the family originated in Southeast
Asia, most probably from West Malaysia in the late
Mesozoic (Lakhanpal, 1970) and migrated into India
during the late Cenozoic Era. The occurrence of
bicadinanes diagnosic of Dipterocarpaceae resins in
late Cenozoic fluvio-deltaic oils from across SE Asia
(Dutta et al., 2009) represented a further connection
with this age. Others suggest that Dipterocarpaceae
have a Gondwanan origin and reached Asia by rafting
on the Indian plate (Ducousso et al., 2004).
The earliest dipterocarp fossils recorded in SE Asia
come from Oligocene (34-23 Ma) sediments of
Borneo (Muller, 1981). Here, we report an occurrence
of Asian dipterocarps from approximately 53 Ma
sediments from western India based on fossil resin
chemistry and palynological data. Early Eocene
lignites, carbonaceceous shales and resins were
collected from the Cambay, Kutch and Rajasthan
basins of Western India. Cadalene based C15 bicyclic
sesquiterpenoids and their dimer bicadinanes were
consistently identified as the major pyrolysis products
(Figure 1) from all Early Eocene resins identifying
them as angiosperm Dipterocarpaceae-sourced
dammar (Class II) resins (Dutta et al., 2009). We have
also recovered angiosperm pollen grains which show
close affinity with modern pollen of Dipterocarpus
indicus.
An important implication of the present finding is that
Asian dipterocarps must have originated in
Gondwana and dispersed out-of-India into Asia once
the land connection between Indian and Asian plate
was well established during the middle Eocene (49-41
Ma). Moreover, the present study supports the
hypothesis which suggests that many angiosperms
did not originate in the SE Asian region, but dispersed
into the area from western Gondwanaland.
References
Ducousso, M., Bena, G., Bourgeois, C., Buyck, B.,
Eyssartier, G., Vincelette, M., Rabevohitra, R.,
Randrihasipara, L., Dreyfus, B., Prin, Y., 2004.
The last common ancestor of Sarcolaenaceae
and Asian dipterocarp trees was ectomycorrhizal
before the India-Madagascar separation, about
88 million years ago. Molecular Ecology 13, 231-
236.
Dutta, S., Mallick, M., Bertram, N., Greenwood, P.F.,
Mathews, R.P., 2009. Terpenoid composition
and class of Tertiary resins from India.
<strong>International</strong> Journal of Coal Geology 80, 44–50.
Lakhanpal, R.N., 1970. Tertiary floras of India and
their bearing on the historical geology of the
region. Taxon 19, 675-694.
Muller, J., 1981. Fossil pollen records of extant
angiosperms. Botanical Review 47, 1-142.
64

O-07
The syngeneity of Precambrian sterane biomarkers
Amber Jarrett, Jochen Brocks
Research School of Earth Sciences, Australian National University, Canberra, Australia (corresponding
author:amber.jarrett@anu.edu.au)
Precambrian oceans and the organisms inhabiting
them were fundamentally different than today. In
modern oxygenated oceans algae such as diatoms,
dinoflagellates and coccolithophorids are the
dominant primary producers. Precambrian oceans
were hypothesised to be primarily anoxic and/or
sulfidic with eukaryotic organisms constrained to the
upper mixed zone in the water column [1]. Primary
productivity was controlled by single-celled organisms
such as cyanobacteria and various groups of primitive
algae, possibly Rhodophyta and Chlorophyta (red and
green algae respectively). The Proterozoic body fossil
record is patchy. From the late Mesoproterozoic to
early Neoproterozoic (~1,200 - 850 Ma) simple
microfossils of eukaryotes are present in low
abundance but begin to significantly diversify from the
middle of the Neoproterozoic (ca. 700Ma) to the
beginning of the Phanerozoic (542 Ma) [2].
Organic geochemistry has become a common
method for filling the gaps in this body fossil record.
The extraction and identification of molecular fossils
have been used to make far reaching assumptions on
the ecology and evolution on early life, such as the
first appearance of eukaryotes [3]. The most common
biomarkers for eukaryotic organisms are the steranes
cholestane (C27), ergostane (C28) and stigmastane
(C29). Previous studies have shown that the relative
concentration of sterane homologues changes
systematically through the Phanerozoic, with a
generalized increase in C28/C29 coinciding with the
shift in primary producers in the ocean [4]. However, it
is unusual that published sterane ratios from older
sequences (~1,700 - 635 Ma) are usually
indistinguishable to the Phanerozoic, despite the fact
that eukaryotic microfossils from this interval appear
to me primordial algal groups, not secondary and
tertiary endosymbiotic algae of Phanerozoic oceans.
In this study we completed a detailed re-assessment
of 50 Proterozoic sediments from the Amadeus and
Officer Basins of Australia over key intervals such as
the ‗Snowball Earth‘ events, the Acraman Impact,
through the Ediacaran to the Precambrian-Cambrian
boundary. Our methodology consisted of removing
exterior surfaces from a sample which could
potentially be exposed to anthropogenic
contaminants. We compared the exterior and interior
fractions, systematically investigating the permeability
of rock samples to hydrocarbon infiltration by
identifying polyethylene by-products such as BAQCs
and cyclopentanes [5].
The results of our study are surprising. We found 85%
of our samples only contain steranes of
anthropogenic origin. However, 15% had a clean
interior and yielded indigenous Precambrian steranes.
The indigenous sterane ratios appear to be more
compatible with the body fossil record. Our data
suggest that eukaryotes in the Mesoproterozoic were
not significant. This is then followed by the
appearance of red algae (predominance of C27) in the
early Neoproterozoic, and then green algae
(predominance of C29) in the late Neoproterozoic,
broadly consistent with the body fossil record.
References:
[1] Falkowski & Knoll, 2007, Academic Press
[2] Butterfield 2000, Paleobiology, 26(3), 386-404
[3] Brocks et al. 1999, Science, 285(5430), 1033-1036
[4] Schwark & Empt 2006, Paleoceanography
paleoclimatology, paleoecology 240, 225-236
[5] Brocks et al. 2008, Geochim. Cosmochim. Acta
72, 871-888
65

O-08
An integrated lipid biomarker and chemostratigraphic record of
biospheric evolution through the late ordovician mass extinction
event
Megan Rohrssen, Gordon Love
University of California, Riverside, Riverside, California, United States of America (corresponding
author:mrohr001@ucr.edu)
The Late Ordovician (~450-440 Ma)
witnessed the two-phased mass extinction of an
estimated 84% of all marine animal species, one of
the largest extinctions in the Phanerozoic eon [1].
Unlike other mass extinctions, marine fossil
communities after the Ordovician-Silurian (O-S)
boundary appear very similar to those that preceded
it. Bolide impact and gamma-ray bursts have both
been proposed as extinction triggers, but these
mechanisms lack robust supporting evidence for the
end Ordovician [e.g. 2]. There is strong evidence,
however, for major Southern hemisphere
glaciation/deglaciation episodes, with accompanying
water column temperature and chemistry change, sea
level fluctuations and positive carbon and oxygen
isotope excursions [3-4], putatively coincident with the
recorded faunal extinction.
Anticosti Island, Quebec, Canada, provides
an exceptional opportunity to assemble nearly
continuous chemostratigraphic records of the Late
Ordovician in a shallow, paleotropical mixed
carbonate / siliciclastic setting. In this study we have
used lipid biomarkers from bitumen and kerogens
from sedimentary rocks exposed in outcrop and drill
core to gain insight into the taxonomy of the major
marine primary producers, water column depositional
conditions and overall microbial community structure
during the Hirnantian Isotopes of Carbon Excursion
(HICE) and mass extinction.
Lipid biomarkers from Anticosti outcrops
have low thermal maturities consistent with the burial
history of the island and lack signs of younger
petroleum-derived hydrocarbons (e.g. zero oleanane
from angiosperms, HBIs from diatoms). In addition,
Anticosti biomarkers have low C28/C29 sterane ratios
(

O-09
A high resolution compound specific carbon isotope study of
the PETM in Northern Spain
Hayley Manners 1 , Stephen Grimes 1 , Paul Sutton 1 , Laura Domingo 2,3 , Richard Pancost 4 ,
Melanie Leng 5 , Kyle Taylor 4 , Richard Twitchett 1 , Malcolm Hart 1 , Nieves Lopez-Martinez 3
1 University of Plymouth, Plymouth, United Kingdom, 2 University of California Santa Cruz, Santa Cruz, United
States of America, 3 Universidad Complutense de Madrid, Madrid, Spain, 4 University of Bristol, Bristol, United
Kingdom, 5 NERC Isotope Geosciences Laboratory, Nottingham, United Kingdom (corresponding
author:hayley.manners@plymouth.ac.uk)
The Paleocene/Eocene Thermal Maximum (PETM)
occurred approximately 55 Ma, lasting for 100 – 200
Kyr, initiating a period of global warming, biotic
extinction, migration and turnover, and fundamental
changes in the carbon and hydrological cycles 1.
Marine and terrestrial sediments record the event,
however discrepancy between the carbon isotope
excursion (CIE) measured in the two realms has been
observed (δ 13 C marine 2.5 - 4‰, δ 13 C terrestrial 6 -
8‰) 2,3,4 . Two hypotheses have recently been
proposed for this discrepancy – the ―marine
modification‖ and the ―plant community change‖
hypothesis 5 . The plant community change hypothesis
states that the magnitude of the CIE is greater in the
terrestrial realm owing to major changes in floral
composition during the PETM, from mixed
angiosperm (flowering plants)/gymnosperm (conifers)
flora to a predominantly angiosperm flora 5,6 .
To date, evidence for the plant community change
hypothesis has been observed in North America 5 and
the Arctic 6 . Presented here are preliminary results
from eight sections in Northern Spain spanning the
Paleocene/Eocene boundary. Sections from (East to
West) Claret, Tendrui, Esplugafreda, and Berganuy
represent the terrestrial realm; La Cinglera and
Campo a shallow marine setting, and Zumaia and
Ermua a deep marine environment.
High resolution section sampling enabled the onset of
the CIE at all sections to be assessed in more detail
than previously reported. Total organic carbon (TOC)
δ 13 C along this transect illustrate that the CIE
associated with the PETM varies in magnitude
between ca. 2 and 5‰; however there appears to be
no correlation between magnitude and depositional
environment. Preliminary results from compound
specific carbon isotope analysis of higher molecular
weight n-alkanes at Claret follow a similar trend to
TOC δ 13 C data at this site (see Fig.1). However, the
results suggest that the bulk δ 13 C records a lower
magnitude excursion than the n-alkane data where
excursions of up to 8‰ are being found. This
apparent enhancement in the magnitude of CIE is
particularly significant when results for average chain
length (ACL) are considered, as thus far, no change
in ACL has been recorded for the Claret section. This
could suggest that there is no appreciable
reconfiguration of terrestrial higher plant biota
coincident with the PETM at the Claret site, which
would indicate that the plant community change is not
responsible for overestimation of the CIE in the
terrestrial realm.
Fig. 1 Bulk and n-alkane � 13 C data
References
1. Bowen, G. J. et al. 2006. EOS Trans. AGU, 87,
(17) 165 - 169.
2. Bains, S. et al. 1999. Science, 285, (5428) 724-
727.
3. Bowen, G. J. et al. 2001. University of Michigan
Papers on Paleontology, 33, 73 - 88.
4. Schmitz, B. and Pujalte, V. 2003. Geology. 689-
692.
5. Smith, F. A. et al. 2007. Earth and Planetary
Science Letters, 262, (1-2) 50-65.
6. Schouten, S. et al. 2007. Earth and Planetary
Science Letters, 258, (3-4) 581 – 592.
67

O-10
Sulfur species as facilitators for water splitting to react with
organic matter under medium temperatures
Ward Said-Ahmad 1 , Alon Amrani 2 , Zeev Aizenshtat 1
1 The Hebrew University of Jerusalem, Institute of Chemistry and Casali Institute, 2 Jerusalem, Israel, Institute
of Earth Sciences, The Hebrew University of Jerusalem, 91904 israel (corresponding author:
zeev@vms.huji.ac.il)
It has been suggested that water can act as hydrogen
and oxygen donor during thermal maturation of
sedimentary organic matter (OM).
The major hurdle to explain the water chemical
activity during the catagenetic stages or under
laboratory hydrous pyrolysis conditions is finding the
path lowering the very high activation energy required
for its splitting.
Homolytic cleavage of neat water without catalysis
require steam at >1200 0 C or ��
form H . and OH . radicals. Such high levels of energy
are not possible at natural depositional environments.
It is known that metals and sulfur (S) species can
catalyze the splitting of water even under mild
temperatures. Experiments performed under very
basic conditions (1 Molar NaOH) with elemental S
show that disproportionation occur at temperatures of
100-200ºC to the following species: S -2 ; Sn -2 ; SO3 -2 ;
S2O3 -2 and SO4 -2 (Lin et al., 2004).
In the present study we attempt to understand the role
of S species in the activation of water toward organic
matter in natural environments. We performed a set of
experiments to examined the effect of pH (from 4
to13), temperature (20-250°C), and the water-organic
interface by using emulsifiers.
The experiments between several S species (H2S ,
HS - ,Sx 2- , SO4 -2 ) and water performed with and
without the presence of organic model compounds.
In all the experiments we examined the organic and
inorganic products distribution and their δ 34 S values.
Our results show that elemental S in water
disproportionate above 120°C at pH 8-8.5 without the
presence of organic matter. As the pH and
temperature elevated this reaction is faster. In the
presence of organic compounds the disproportionate
of elemental S is significantly faster even at relatively
low pH and low temperature (80°C). This reaction
yields a variety of organosulfur compounds as well as
oxidized compounds (non-S) such as ketones (Fig.1).
The sulfurized and oxidized organic compounds seem
to form in parallel if no ammonia is present.
There is 5-13‰ fractionation between elemental S
and H2S which decrease as a function of temperature.
Organosulfur compounds and polysufides exhibit
smaller fractionation relative to elemental S of 0-3‰.
The sign of this fractionation is changing with the
temperature and organic substrate and the chemical
environment (such as the presence of emulsifiers).
This fractionation sign differences helps us to
determine formation pathway of certain products
(Amrani et al., 2008).
In summary, this study indicates that elemental S
catalyzes the splitting of water even at relatively low
temperatures. The hydroxyl radical which is form
(HO . ) react with both organic compounds and sulphur
species to produce oxidized compounds such as
ketones and oxosulfur (SnOx, x,n=1-4) as well as
radical sulphur species. S species such as thyil
radical (HS . ) reacts with organic compounds to form
organosulfur compounds.
Figure 1.
Conversion(%)
100
90
80
70
60
50
40
30
20
10
0
H2O +SReagent
130 o C
0 50 100 150 200 250 300 350 400
Time (h)
Hongfei Lin, Zhixia Li, Kazuyuki Tohji, Noriyoshi Tsuchiya and Nakamichi, 2004.
Proceeding of the Yamasaki 14th <strong>International</strong> Conference on the Properties of
Water and Steam in Kyoto , 356-368.
Amrani, A., Ma,Q., Said Ahmad, W. Aizenshtat, Z. and Tang, Y. 2008. Sulfur
isotope fractionation during incorporation of sulfur nucleophiles into organic
compounds. Chemical Communication. 11, 1356 – 1358.
HS
H2O H2S(aq) pH=8.5
Na2Sx(aq) pH=13
S8 pH=8.5
Na2Sx(aq) pH=8.5
(NH4)2Sx(aq) pH=8.5
S
S
S
S
O
S
S
S
S
S
68

O-11
Sulfur Rich Petroleum Systems: TSR and thermal cracking in
basin and reservoir field studies, simulation experiments and
model calibration
Olaf G. Podlaha, Henning Peters, Erdem Idiz, Volker Dieckmann
Shell Global Solutions <strong>International</strong> B.V., Rijswijk, Netherlands (corresponding
author:olaf.podlaha@shell.com)
Charge modelling and fluid property prediction in
petroleum system analysis relies on the integration of
field observations, appropriate simulation experiments
and risk reduction using up-to-date in-house modeling
tools. In complex systems such as Sulfur and its
inorganic and organic species in a petroleum system,
this approach allows us to accurately assess of a set
of key questions:
- How to model naturally observed Sulfur phases‘
variability as a result of (a) thermal cracking of
OM and (b) TSR processes ?
- How to model laboratory simulation experiments?
- How to use simulation experimental results for
generic process modeling?
- Which constraints from field studies will always
be needed to crosscheck models?
- Will modeling go beyond main fluid properties‘
prediction and allow for reconstruction of OM S
exchange reactions?
- Where is the boundary between a basin modeling
approach versus enhanced reservoir modeling
within the rock and brine framework?
In this study, a series of stacked Upper Devonian to
Mississippian sour gas reservoirs situated in the
Rocky Mountains Foothills of Alberta, Canada, serve
as natural labs. The Western Canadian Sedimentary
Basin (WCSB) is one of the most studied hydrocarbon
provinces in the world. Production from these
reservoir units is mainly dry gas and different forms
sulfur, with H2S contents ranging from 5% to almost
90% were studied. As a supplement, a Middle to
Upper Devonian condensate-sour gas reservoir (with
more than 35% H2S) in the Plains of Alberta was
investigated.
The field data studies [1] were supported
- Petrography (microscopy) of limestone and
dolostone in the petroleum reservoirs units
- Geochemical characterization of solid bitumen
using elemental analysis and X-ray absorption
spectroscopy (XANES)
- Carbon, oxygen and sulfur isotope analyses of
various phases
- Fluid inclusion studies using classic
microthermometry analysis and Raman
spectrometry for semiquantitative gas typing.
The results of this field study [1] were supplemented
by simulation experiments performing closed goldtube
pyrolysis to study the kinetics of both S-rich and
S-free OM thermal cracking in source rocks as well as
S-rich and S-free oil for a comparison of normal oil-togas-cracking
(OTGC) versus TSR controlled OTGC.
For OM thermal cracking it will be demonstrated that
the activation energies described in the literature for
hydreous and open pyrolysis experiments [2], [3]
differ from those obtained for gold tube pyrolysis,
though the general trend to lower activations energies
with increasing sulfur yield of the organic matter still
holds.
For TSR the role of catalysts such as Mg as well as
the importance of presence of different sulfur species
types for the onset and degree of TSR induced
hydrocarbon alteration as described in the literature
[4] will be shown in experiment and model results.
The simulation experiments furthermore suggest that
for higher maturities sulfur back-reaction at enhanced
TSR levels into aromatic hydrocarbon fraction allow
for the distinction of reactive and pyro-bitumen
forming hydrocarbon species.
As an outlook the importance of these results for the
modeling and prediction of fluid properties in S rich
petroleum systems will be demonstrated.
References
[1] Peters et al. (2011), this abstract volume
[2] Lewan and Ruble (2002), Org. Geochem., 33,
1457-1475
[3] Baskin and Peters (1992), AAPG Bull., 76, 1-13.
[4] Zhang et al. (2007), Org. Geochem., 38, 897-910
69

O-12
Sulfur isotope systematic of individual organic compounds
during thermochemical sulfate reduction
Alon Amrani 1 , Andrei Deev 2 , Alex Sessions 3 , Yongchun Tang 2 , Jess Adkins 3 , Ronald
Hill 4 , Michael Moldowan 5 , Zhibin Wei 6
1 The Hebrew University of Jerusalem, Jerusalem, Israel, 2 PEER Institute, Covina, United States of America,
3 California Institute of Technology, Pasadena, United States of America, 4 Marathon Oil Company, Houston,
United States of America, 5 Stanford University, Palo Alto, United States of America, 6 Exxon Mobile, Houston,
United States of America (corresponding author:aamrani@gsi.gov.il)
Thermochemical sulfate reduction (TSR) coupled
with oxidation of hydrocarbons occurs in hot
carbonate petroleum reservoirs (>100°C) and in
hydrothermal environments. It is one of the most
important organic-inorganic interactions and is well
documented by many geologic observations from
around the world.
Sulfur isotopes are useful for detecting the
occurrence of TSR, because the � 34 S value of H2S
approaches that of the CaSO4 being reduced.
Organosulfur compounds and pyrobitumen resulting
from back-reactions with TSR-derived H2S have been
proposed to have δ 34 S values close to parent sulfates,
though this has not been directly tested.
We have measured a suit of Upper Jurassic oil and
condensate samples generated from the Smackover
Fm. source rock in the Gulf of Mexico. We employed
a new technique capable of measuring precise δ 34 S
values in individual compounds by GC-MC-ICPMS
(Amrani et al., 2009).
S-isotopic differences of up to ~50‰ were
observed between individual organosulfur compounds
in these Smackover oils (Fig. 1). There is a clear
distinction between oils that experienced TSR and
those that did not. Oils that did not are relatively 34 S
depleted and have small δ 34 S variations between
individual compounds. Oils that did experience TSR
have significant S-isotopic differences between
benzothiophenes (BTs) and dibenzothiophenes
(DBTs). BTs are 34 S enriched, close to the δ 34 S
values of sulfate from evaporites in the Smackover
Fm. The δ 34 S values of DBTs are spread across a
wider range and are always more negative. These
differences represent different degrees of TSR
alteration of these oils.
We further conducted a series of gold-tube
hydrous pyrolysis experiments with three
representative oils and isotopically distinct CaSO4 to
determine the factors controlling δ 34 S values of
individual organic S compounds at different stages of
TSR. Our experiments show that isotopic alteration
does readily occur under TSR conditions and can
significantly effect the δ 34 S values of individual
compounds. Our results also show that BTs are
sensitive tracers for TSR as they formed readily under
TSR conditions, with δ 34 S values that are similar to
that of H2S derived from CaSO4. In contrast, DBTs
show relatively small δ 34 S changes, preserving their
original δ 34 S values longer because of their greater
thermal stability and slow rate of formation. These
observations support the notion that DBTs can
preserve the original (non TSR altered) δ 34 S signals
of the oils through low to moderate TSR alteration.
The use of these two groups of tracers in
combination allow us to detect TSR alteration of oils
from the very early stages up to highly altered oils, all
without measuring H2S or sulfate isotopes. The
approach should find numerous uses in exploration,
as well as for understanding the basic reaction
mechanisms and kinetics of secondary sulfur
incorporation into oils.
References
Amrani, A., Sessions A.L., Adkins J. 2009.
Compound-specific δ 34 S analysis of volatile organics
by coupled GC/ICPMS. Analytical Chemistry 81,
9027-9034
70

O-13
Degradation of intact polar lipids in sandy sediments: Insights
from a laboratory experiment
Jörn Logemann, Jutta Graue, Jürgen Köster, Bert Engelen, Heribert Cypionka, Jürgen
Rullkötter
University of Oldenburg, Oldenburg, Germany (corresponding author:j.logemann@icbm.de)
Intact polar lipids (IPLs) occur in the cytoplasm
membranes of all living organisms and are therefore
commonly used as biomarkers for living biomass
[1-5]. Also, IPLs are employed as chemotaxonomic
markers to distinguish living bacterial from living
archaeal cells [1, 6]. The analytical distinction of
microorganisms is possible due to the unique feature
of Archaea synthesizing IPLs containing ether-bound
isopreniod core lipid structures. In contrast, bacterial
and eukaryal cytoplasma membranes contain mainly
intact polar lipids with unbranched ester-bound
straight-chain fatty acid core lipids.
One fundamental assumption underlies these
applications: Intact polar lipids are considered to
degrade rapidly after cell death [7]. The lack of a
broad study on the degradation of intact polar lipids,
which encloses lipids with phosphoester and
glycosidically bound head groups and moieties that
occur in Bacteria and Archaea made it necessary to
revisit the degradation of IPLs to ensure the
robustness of this proxy.
The turnover of IPLs was investigated in a laboratory
experiment with anoxic sandy sediments from the
North Sea. As IPL sources intact cells of two
organisms that do not naturally occur in North Sea
sediments were chosen: (i) Saccharomyces
cerevisiae as the source of ester-bound acyl lipids
that also occur in bacteria, and (ii) the hypersaline
archaeon Haloferax volcanii as the source of etherbound
isoprenoid lipids. The degradation of these two
types of IPLs was monitored and concurrent changes
in the microbial community in the course of the
experiment were tracked. Pore water and 16S rRNAbased
DGGE analysis helped to gain background
information on processes occurring during the
experiment. The results of the degradation
experiment were tested with two controls: The first
control (named: ―abiotic control‖) was designed to
assess if any processes occur which lead to a
degradation of the added intact polar lipids but are not
mediated by microorganisms. The second control
(named: ―untreated control‖) was used to check the
influence of the addition of inactive biomass on the
microbial community without any further substrate
addition. Although a notable amount of IPL source
material was added, the obtained data showed only a
minor influence on microbial metabolism and
community profile.
Peak area ratio relative to day 0
2.0
1.5
1.0
0.5
Ester
Ether
0.0
0 20 40 60
Time [d]
80 100
Figure 1: Sum of ester- and ether-bound IPLs in the
degradation experiment and the abiotic control given in peak
area ratios relative to day 0. Closed symbols: degradation
experiment; open symbols: abiotic control. For creation of
plots for the abiotic control the same IPLs were chosen as
for the plots of the degradation experiment.
The results show relatively fast degradation of esterbound
IPLs and no significant degradation of archaeal
ether-bound IPLs. Thus, this differential degradation
of IPLs may lead to bias in the sedimentary record
and perhaps to an overestimation of active archaeal
communities.
[1] Biddle et al. (2006) PNAS 103, 3846-3851.
[2] Ertefai et al. (2008) Org. Geochem 39, 1572-1588.
[3] Rossel et al. (2008) Org. Geochem 39, 992-999.
[4] Sturt et al. (2004) RCM 18, 617-628.
[5] Zink et al.(2003) Org. Geochem. 34, 755-769.
[6] Lipp et al. (2008) Nature 454, 991-994.
[7] Harvey et al. (1986), GCA 50, 795-804.
71

O-14
Exploring the diversity of archaeal ether lipids in marine
sediments
Xiaolei Liu 1 , Julius Lipp 1 , Jeffrey Simpson 3 , Roger Summons 2 , Kai-Uwe Hinrichs 1
1 MARUM, University of Bremen, Bremen, Germany, 2 Department of Earth, Atmospheric and Planetary
Sciences, Massachusetts Institute of Technology, Cambridge, United States of America, 3 Department of
Chemistry, Massachusetts Institute of Technology, Cambridge, United States of America (corresponding
author:xliu@uni-bremen.de)
Archaeal lipids, such as glycerol diethers and
tetraethers, are common in marine sediments, and
their structural diversity is high [1]. The main
compounds studied to date include derivatives of
glycerol dibiphytanyl glycerol tetraethers (GDGTs)
and archaeol. We have now detected and/or identified
several novel groups of related ether lipid compounds
that expand the currently known pool of archaeal
ether lipid derivatives.
Most studies in the past decade have adopted the
protocol by Hopmans et al. [2] or slight modifications
thereof for the detection of archaeal core lipids. By
modifying the polarity gradient of the mobile phase
and expanding the scanned mass range, numerous
exotic archaeal lipids were revealed. Most of their
structural assignments are still based on interpretation
of mass spectra and therefore remain tentative but
selected compounds were also characterized by NMR
analysis.
Among the groups of novel lipids are glycerol dibiphytanol
diethers (GDDs); these lipids coexist with
their corresponding GDGTs in a wide range of
sediments and archaeal cultures., An example is
provided in Fig. 1, illustrating the structure of GDGT-0
and its GDD derivative. Given similar ring distributions
in a set of globally distributed marine sediments (Fig.
1), the biological source of GDDs and GDGTs is
probably identical. Multiple lines of circumstantial
evidence argue against their artificial formation during
sample preparation. The presence of GDDs may be
relevant to biosynthesis of archaeal lipids as well as
to the fate and degradation of GDGTs in marine
sediments, including the recently postulated recycling
of these compounds by benthic archaea [3]. We will
discuss the distribution and significance of this and
other novel groups of GDGT derivatives.
Fig. 1 Plot of 12 marine sediments showing the
relative abundance of GDGT-0 and GDD-0 in their
respective molecular series together with the
structures of both molecules.
References
[1] Schouten, S., Hopmans, E.C., Pancost, R.D.,
Sinninghe Damsté, J.S. (2000) Proc. Natl. Acad.
Sci. USA 97, 14421-14426.
[2] Hopmans, E.C., et al. (2000) Rap. Comm. Mass
Spectrom.14, 585-589.
[3] Takano, Y., et al. (2010) Nature Geosci. 3, 858-
861.
72

O-15
Differential degradation of intact polar lipid GDGTs upon
oxidation of a turbidite sediment
Sabine K. Lengger 1 , Mariska Kraaij 1,3 , Marianne Baas 1 , Ellen C. Hopmans 1 , Jaap S.
Sinninghe Damsté 1,2 , Stefan Schouten 1,2
1 NIOZ Royal Netherlands Institute for Sea Research, 't Horntje, Netherlands, 2 Utrecht University, Utrecht,
Netherlands, 3 University of Applied Sciences Utrecht, Utrecht, Netherlands (corresponding
author:sabine.lengger@nioz.nl)
Lipid biomarkers are widely used in ecology for
studying the diversity and activity of communities.
Archaeal membranes contain glycerol diphytanyl
diether- and glycerol dibiphytanyl glycerol tetraetherlipids
(GDGT) as core lipids (CL) with a variety of
headgroups (intact polar GDGTs; IPL-GDGTs),
including sugars (glyco-GDGTs) and phosphates
(phospho-GDGTs). IPL-GDGTs are being used as
biomarkers for live Archaea as they are thought to
degrade quickly after cell lysis [1]. Theoretical
modeling, however, suggests that glyco-GDGTs might
be preserved over geological timescales and may not
represent living Archaea [2].
Here, we tried to determine the preservation potential
of glyco- and phospho-GDGTs and their applicability
as biomarkers for live archaeal communities. To this
end, we compared lipid concentrations and
composition of the organic-rich sections with the
oxidized ones of the f-turbidite from the Madeira
Abyssal Plain (MAP). This turbidite is a layer of
sediment which was transported by a turbidity current
from its anoxic depositional environment on the
continental slope to the abyssal plain. As the organic
matter was completely mixed during transport, it is
homogenous while, due to the exposure to oxygen in
the bottom waters, it was gradually oxidized by a
downwards moving oxidation front. This makes it ideal
for studying the impact of oxygen on the degradation
of biomarkers [e.g. 3]. We determined CL- and total
IPL-GDGT concentrations by HPLC/APCI-MS and the
abundance of individual crenarchaeol-based IPLs by
HPLC/ESI-MS 2 . Total CL- and IPL-GDGT
concentrations were two orders of magnitude lower in
the oxidized part of the turbidite compared to the
unoxidized part. No phospho-crenarchaeol was
detected in either the oxidized or unoxidized part of
the turbidite, suggesting that phospho-crenarchaeol, if
present before, was degraded very fast. However, in
the unoxidized part, at least three different types of
glyco-GDGTs (monohexose, dihexose and an
unknown hexose+ 180 Da) were detected (Fig. 1). In
the oxidized section, concentrations of the glyco-
GDGTs with the dihexose- and the unknown
Depth [cm]
headgroup had decreased by three orders of
magnitude. In contrast, GDGTs with a monohexose
headgroup seemed to be more persistent and only
decreased by 2 orders of magnitude, similar to CL-
GDGTs. This suggests that this IPL is relatively better
preserved, a degradation product of the other lipids or
that it was biologically produced in the sediment after
oxidation, though no other indications for in situproduction
were found. Our results suggest that
degradation rates among IPL-GDGTs vary strongly, in
decreasing order: phospho-GDGTs >> dihexose-
GDGTs > monohexose GDGTs. IPL-GDGTs can
hence, depending on the type of headgroup, remain
in sediments longer than expected, especially when
deposited in low-oxygen environments, and are only
strongly degraded upon long-term exposure to
oxygen.
140
160
180
200
220
240
1
10 1 10 2 10 3 10 4 10 5 10 6 10 7
Rel. Abundance
D i h e x o s e
U n k n o w n ( m / z 1 8 0 ) M o n o h e x o s e
Figure 1. Relative
abundances for IPLcrenarchaeol
species unknown
(hexose + 180 Da),
dihexose and
monohexose, in the
unoxidized (below,
grey) and oxidized
(above, white)
sections of the
turbidite.
References:
[1] 260 Biddle J. et al. (2006) Proc Natl Acad Sci USA
103, 3846-3851.
[2] Schouten S. et al. (2008) Appl Env Microbiol 74,
2433-2440.
[3] Huguet C. et al. (2008) Geochim. Cosmochim.
Acta 72, 6061-6068.
73

O-16
Improved genetic characterization of Brazilian oils using
combined molecular (biomarkers) and isotope geochemistry
Jarbas Vicente Poley Guzzo, Eugenio Santos Neto, Alexandre de Andrade Ferreira
PETROBRAS, Rio de Janeiro, Brazil (corresponding author:guzzo@petrobras.com.br)
An extensive application of isotope geochemistry
combined with the traditional molecular (biomarkers)
approach over a large set of oils, gases and bitumens
enabled a detailed geochemical characterization of
Brazilian petroleum systems and, at the same time, a
rigorous evaluation of the potential and limitations of
both methods.
Carbon isotope profiles of n-alkanes show remarkably
consistent patterns between n-C13 and n-C33,
distinguishing the three main oil families known in
Brazil according to the depositional environment of
source-rocks (lacustrine, marine-evaporitic and open
marine). Lacustrine oils show a typical negative
sloping curve with a subtle sloping up trend between
n-C27 and n-C33 (asymmetric ―U‖ shape), and a large
amplitude of isotopic values (generally higher than
3‰, Fig. 1). Marine-evaporitic oils show a typical
symmetric ―U‖ shape curve between n-C13 and n-
C33, with n-C22 showing the most negative value, a
medium amplitude of isotopic values (generally about
3‰) and in general the heaviest isotopic profile of nalkanes
within the studied dataset. Open marine oils
show an overall ―flat‖ pattern, with small isotopic
variations from the main trend.
Besides its genetic discrimination efficiency, carbon
isotopic profiles of n-alkanes have also been used to:
� demonstrate oil mixing when hardly detected
or evaluated by biomarkers
� solve questions on possible migrationcontamination
of oils
� directly correlate oils and source-rocks
� identify the origin of high maturity oils with
severely degraded biomarker distribution
� describe sub-types of lacustrine and marine
oils
Several features described in this study were already
noted elsewhere, e.g. the trend toward isotopically
lighter values with increasing n-alkane chain length
(negative slope) of lacustrine oils and bitumens, the
flat character of n-alkane isotopic profile of open
marine oils, and the ubiquitous isotopic enrichment
with increasing thermal maturity (e.g. Murray et al.
1994, Pedentchouk 2004, Samuel et al. 2009).
A number of elements and processes of petroleum
systems identified and described using the biomarker
approach have their characterization reinforced using
isotopes. Even subtle compositional heterogeneities
hardly detected by biomarkers may generate
conspicuous features among isotopic profiles as, for
example, the remarkably depleted hydrogen isotope
profiles of early mature oils, and the late or early
petroleum charges detected by the isotopic
composition of gases.
In a more restricted set of oil samples, the carbon
isotopic composition of individual biomarkers
improved the genetic discrimination due to the large
differences between isotopic composition of specific
biomarkers (tricyclic and pentacyclic terpanes) among
oils of different origins.
The combined biomarker/isotope approach produced
a large empirical database that supported and refined
the interpretation of specific geological features and
processes like secondary migration, source-rock
facies succession, reservoir filling history and
complex petroleum systems.
� 13 C
-24
-26
-28
-30
-32
-34
-36
lacustrine marine-evaporitic open marine
3.4 ‰
nC22
4.7 ‰
nC27
1.2‰
13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33
n -alkane carbon number
Figure 1: Patterns of � 13 C profiles of individual n-alkanes of
the main Brazilian oil families. Notice some diagnostic
features of each oil family, e.g., amplitude of � 13 C values and
the isotopically lightest n-alkane.
References
Murray A. P., Summons R. E., Boreham C. J., Dowling L. M. 1994.. Org.
Geochem. 22(3-5): 521-542
Pedentchouk, Nikolai 2004. Lacustrine paleoenvironments from stable isotopes
of hydrogen and carbon in lipids. Ph.D. Dissertation, Pennsylvania State
University, State College, Pennsylvania, USA.
Samuel O. J., Cornford C., Jones M., Olabisi A. A., Akande S. O. 2009. Org.
Geochem. 40(4): 461-483
74

O-17
Composition analysis of individual petroleum inclusions:
Preliminary application in the reservoir-filling history of theTahe
oil field, Tarim Basin, NW China
Weijun Shi 1,2 , Maowen Li 1,2 , Binbin Xi 1,2 , Jin Xu 1,2 , Zhirong Zhang 1,2 , Jianzhong Qin 1,2 ,
Hong Jiang 1,2
1 Sinopec Research Institute of Petroleum Exploration and Production, Beijing, China, 2 Wuxi Institute of
Petroleum Geology, Sinopec Research Institute of Petroleum Exploration and Production, Wuxi, China
(corresponding author:shiwj0082@yahoo.com.cn)
Individual hydrocarbon fluid inclusions can be
extracted and verified under microscopic observation,
different types of inclusions formed at different
diagenetic stages can be then analyzed with a variety
of techniques. This report presents the results of our
recent project that uses an online gas
chromatography-mass spectrometer (GC/MS) to
study the chemical compositions of hydrocarbons in
individual petroleum inclusions in carbonate
reservoirs. Because of the small volume and the low
concentration of hydrocarbons in individual inclusions,
this work represents a significant technical
breakthrough in the petroleum system study of the
Tarim Basin, NW China..
Tahe oil field is situated in southwest of Arkekule
Uplift, Tarim Basin. Crude oils are produced
dominantly from the Ordovician carbonate reservoirs,
overlain by Triassic-Lower Jurassic strata. Upper
Carboniferous-Devonian and Upper-Middle Jurassic
strata are absent in the study area. Ordovician
carbonate core samples were collected from eastern
Tahe oil field and analyzed for petroleum inclusions.
Petroleum inclusions are extremely abundant in these
samples, occurring mainly in calcite and quartz
cements and calcite vein in carbonate rock matrix.
Coeval aqueous and petroleum inclusions are readily
identified and distinguished under the microscope by
their fluorescence properties, occurrences and
homogenization temperatures. Two types of
petroleum inclusions are identified. The first and
dominant type displays blue fluorescence, and the
homogenization temperatures of the associated
aqueous inclusions vary from 74 to 92 ooC. The
second type of petroleum inclusions display yellow
fluoresce, iand variable homogenization temperatures
from 58℃ to 113℃ .
Laser ablation supports the GCMS analysis of small
samples (< 100 mm). It affords ultra-high sensitivity
and an ability to separately analyse in situ
microscopically discrete morphological entities. The
new laser ablation GCMS facilities equipped with
identical GC inlets have been recently established at
the Wuxi Institute of Petroleum Geology, where the
instrument uses a pulsed 193 nm excimer laser
targeting the analyses of oil bearing inclusions.
Excimer laser is the most suitable tool to open the
fluid inclusions hosted in quartz or calcite and the high
performance inlet ensures excellent products transfer
.
Results of our on-line GCMS analysis for individual
inclusions indicate that C4-C30 hydrocarbons are
present, and two types of petroleum inclusions bear
distinctly different chemical compositions. The blue
fluorescence inclusions have higher proportions of
saturated hydrocarbons and gaseous hydrocarbons,
but lower proportions of aromatic hydrocarbons than
the yellow fluorescencing inclusions.. Normal alkanes
in the blue fluorescencing inclusions show a unimodal
distribution, with the maximum at n-C17, and
those in the yellow fluorescencing inclusions have
dual modal distribution, maximized at n-C15 and C25.
In general, the yellow fluorescencing inclusions
contain much more water soluble aromatic
hydrocarbons than those in the blue ones, as
indicated by the ratio of 1,7-dimethylnaphthalene/n-
C14 alkane. TBecause the GC retention time of both
compounds are similar, their ratio is unlikely to be
affected by sample handling processes. Five samples
were analyzed, and the results show that 1,7-
DMN/nC14 ratios in the yellow fluorescencing
inclusions are around 3.37, while those in the blue
fluorescencing ones are only 0.46. It is reasonable to
infer that the composition and the formation time are
different for these two types of inclusions.
On the basis of homogenization temperatures and
fluorescence, in particular the composition,it can be
delineated that there were two main stages of the
petroleum-filling in the Tahe oil field. Compared with
the blue fluorescence petroleum inclusions, the yellow
ones have a lower maturity level, which may be
caused by an early hydrocarbon charge.
75

O-18
Petroleum system analysis South East Abu Dhabi
Peter Nederlof 1 , Özkan Huvaz 1 , Andy Bell 1 , Ahmed Khouri 2 , Abdelfatah El Agrab 2 ,
Raphael Rosell 2 , Artur Stankiewicz 3
1 Shell <strong>International</strong> E&P, Rijswijk, Netherlands, 2 ADCO, Abu Dhabi, United Arab Emirates, 3 Shell Abu Dhabi,
Abu Dhabi, United Arab Emirates (corresponding author:p.nederlof@shell.com)
The Abu Dhabi Company for Onshore Oil Operations
(ADCO) is exploring for oil in a contract area in South
East Abu Dhabi. In order to better understand the
regional charge variations and to identify the best oil
prospects, a large scale petroleum system analysis
was carried out.
The petroleum system analysis was carried out
according to Shell‘s standards for Integrated Charge
Evaluation (ICE). This comprises (1) a source rock
evaluation, (2) a regional oil typing exercise and (3) a
3-D basin modelling study. The results from the oil
analyses indicated that the petroleum systems in
South East Abu Dhabi are different from the main
petroleum system in Central Arabia, as illustrated by
the compound specific isotope analysis of a suite of
Abu Dhabi oils (Figure below).
-24.0
-25.0
-26.0
-27.0
-28.0
-29.0
-30.0
-31.0
-32.0
C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28
The absence of the ‗regular‘ Hanifa hydrocarbon
family is supported by the results from the source rock
screening, which revealed that the Hanifa has little to
no source potential in the immediate area. However,
several source rock intervals were identified in the
Cretaceous Thamama Group, in agreement with an
earlier study by Taher (1997).
The regional oil typing suggests that the oils in South
East Abu Dhabi are generated in a separate kitchen
area to the north and migrated up-dip in a southerly
direction. The source rock maturation and
hydrocarbon migration history was then modelled in
3-D Results from this study were used to rank the
prospect portfolio and optimize the drilling sequence.
76

Tuesday Oral Presentations
77

O-19
The borolithochromes: boron-containing organic pigments from
a Jurassic red alga
Klaus Wolkenstein 1 , Jürgen H. Gross 2 , Heinz Falk 3
1 Staatliches Museum für Naturkunde Stuttgart, Rosenstein 1, 70191 Stuttgart, Germany, 2 Institute of
Organic Chemistry, University of Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany,
3 Institute of Organic Chemistry, Johannes Kepler University Linz, Altenbergerstraße 69, 4040 Linz, Austria
(corresponding author:klaus.wolkenstein@smns-bw.de)
The distinct pink colouration of specimens of the fossil
calcareous red alga Solenopora jurassica from the
Jurassic of Great Britain and France (Fig. 1) is well
known since the early 20th century [1]. Due to the
conspicuous colour of the fossils the former
occurrence has even been termed ―Beetroot Stone‖.
Previous reports suggested that the pigments may be
porphyrins [1] or polycyclic quinone pigments
(fringelites) [2]. However, detailed chemical analysis
of the pigments using high-performance liquid
chromatography–diode array detection–electrospray
ionization–mass spectrometry (HPLC-DAD-ESI-MS),
Fourier transform ion cyclotron resonance mass
spectrometry (FT-ICR-MS) and
11 B NMR
spectroscopy has now led to the discovery of a novel
class of complicated boron-containing organic
pigments, the borolithochromes [3].
The highly unusual pigments consist of several series
of homologues and their isomers, the main
compounds with the molecular formulae C50H36O12B,
C51H38O12B and C52H40O12B. Solvolysis and
hydrogen/deuterium exchange experiments monitored
by HPLC-DAD-ESI-MS revealed that the pigments
constitute a unique group of spiroborates (boric acid
esters) with two phenolic moieties as boron ligands
(Fig. 1). Astonishingly, the fossil pigments still show
distinct chiroptical properties, indicating that at least
the subchromophores (ligands) are of biological
origin.
The borolithochromes are exceptional due to the
occurrence of the element boron, which is rarely
found in natural products. The fossil compounds
represent the first boron-containing organic pigments
from a natural source at all. Moreover, the
borolithochromes are the first fossil boron-containing
organic compounds and the first specific pigments
from a fossil red alga. However, no analogy with
present-day red algal pigments or other known
biomolecules from any living organism was found.
The presence of the borolithochromes in Solenopora
specimens of different stratigraphic and geographic
origin suggests a widespread occurrence of the
pigments. Because the classification of fossil
calcareous red algae is partly controversial, due to
morphological similarities with other groups of
organisms such as chaetetid sponges, the specific
borolithochromes or their possible diagenetic products
in the fossil record may be of chemotaxonomic
importance.
Fig. 1. Specimen of Solenopora jurassica with preservation
of fossil boron-containing organic pigments
(borolithochromes) and chemical structure of the main single
isomeric borolithochrome (C50H36O12B).
References
[1] Harland, T.L., Torrens, H.S. (1982) Palaeontology 25,
905-912.
[2] Falk, H., Mayr, E., Richter, A.E. (1994) Mikrochim. Acta
117, 1-5.
[3] Wolkenstein, K., Gross, J.H., Falk, H. (2010) Proc. Natl.
Acad. Sci. USA 107, 19374-19378.
78

O-20
Organic aerosol transport and deposition over the Southern
Ocean
Susanne Fietz 1 , Alfredo Martínez-Garcia 2 , Bastian Hambach 1 , Sze Ling Ho 3 , Frank
Lamy 3 , Walter Geibert 4,5 , Antoni Rosell-Melé 1,6
1 Institut de Ciència i Tecnologia Ambientals (ICTA), Universitat Autònoma de Barcelona (UAB), Barcelona,
Spain, 2 ETH Zürich, Zürich, Switzerland, 3 Alfred Wegener Institute, Bremerhaven, Germany, 4 School of
Geosciences, University of Edinburgh, Edinburgh, United Kingdom, 5 Dunstaffnage Marine Laboratory,
Scottish Association for Marine Science, Oban, United Kingdom, 6 Institució Catalana de Recerca i Estudis
Avançats (ICREA), Barcelona, Spain (corresponding author:susanne.fietz@uab.cat)
The Southern Ocean plays a critical role in the
regulation of Earth‘s climate and atmospheric CO2
concentrations. The westerly winds drive the world‘s
largest current system, the Antarctic Circumpolar
Current, which connects the Atlantic, Pacific, and
Indian Oceans, and control the upwelling of CO2-rich
deep ocean waters to the surface. In addition, the
westerly winds are also responsible for the transport
of iron-rich terrestrial material into the Southern
Ocean, a process that can largely affect ocean
biogeochemical cycles. Indeed, windblown iron can
stimulate biological productivity in the Subantarctic
region, potentially affecting atmospheric CO2 uptake
through time.
In order to evaluate biomarker proxies to trace dust
inputs and the westerlies we have investigated the
importance and pathways of transport and deposition
of lithogenic material and associated biomarkers. We
focussed in the distribution of n-alkanes (derived from
plant waxes) and branched GDGTs (derived from soil
bacteria) in samples from the Atlantic and Pacific
sectors of the Southern Ocean (Fig. 1). Samples
investigated comprised air filters, particulate material
in surface and deep ocean waters, and surface
sediments. The n-alkane and GDGT export fluxes
towards the sea bottom were compared to proxies of
in-situ marine production (e.g., chlorins, alkenones,
and crenarchaeol).
Figure 1. Sample locations (black dots: aerosol filters,
surface water, deep water, and/or surface sediment;
red circle: ODP Site 1090, cf. Fig.2)
A further aim was to investigate the potential of nalkanes
and branched GDGTs as paleoclimatic
proxies of dust deposition over the Southern Ocean.
For that purpose, we also report a paleoceanographic
reconstruction from ODP site 1090 (see Fig. 1 for
location and Fig. 2 for record). We show that in this
record both biomarkers indicate an increase in dust
deposition during the glacial periods (Fig. 2) that is
closely linked to an increase in marine phytoplankton
(Fig. 2) and Archaea productivity.
Figure 2. Reconstructed SST (based on alkenone
unsaturation index UK37´), dust deposition (inferred
from branched GDGT and n-alkane concentrations),
and in-situ phytoplankton production (inferred from
chlorophyll transformation products, i.e. chlorins, and
alkenones) for the last 500 ky in the Subantarctic
Atlantic (ODP Site 1090)
79

O-21
Study of the stable isotopic composition of severely
biodegraded oils as petroleum system correlation parameters
Norka Marcano, Steve Larter, Bernhard Mayer
University of Calgary, Calgary, Canada (corresponding author:nimarcan@ucalgary.ca)
Oil-source rock or oil-oil correlation is one of the most
challenging steps in the analysis of complex
petroleum systems. It is generally based on molecular
fingerprints (biomarkers) and whole oil or oil fraction
carbon isotopic composition. When biomarkers are
unaltered by post expulsion processes, they can
constitute a powerful tool for correlation but effects on
biomarker concentrations in mixed oil charge
scenarios and even destruction of biomarkers at
severe biodegradation levels, may drastically affect
the viability of the approach. Biodegradation is one of
the most dominant post accumulation processes in
petroleum reservoirs 1,2 . One of the largest
accumulations of heavily to severely biodegraded oil
are the Alberta oil sands, where biodegradation is by
far the most important process responsible for
variations in the composition and oil properties 3 .
In this study, continuous petroleum columns from the
Alberta oil sands containing progressively
biodegraded oil (from level 5PM to 8PM) are studied
using molecular and isotopic analyses, with the
purpose of evaluating the effect of biodegradation in
the C, N, S and H isotopic compositions of bulk oil
and fractions of different polarities to assess the
viability of these proxies as oil correlation parameters.
The results show that even though the total
hydrocarbon fraction is highly depleted by
biodegradation to different degrees, this process does
not cause observable systematic carbon isotope
changes in either the bulk bitumen or in fractions of
different polarities in single oil columns. � 15 N values in
bulk bitumen also do not show any trend with
biodegradation, as may have been expected from the
observed destruction of carbazoles studied in the
polar fractions of the oils, which change both
concentration and distribution with biodegradation
levels. Organic sulphur compounds in the aromatic
hydrocarbon fraction are also progressively removed
down the oil columns, yet � 34 S values of bulk oil
remain essentially constant. Locally however, lower
� 34 S values suggest secondary incorporation of 32 Senriched
sulfur.
Variations in � 15 N and � 34 S measured on the aromatic
hydrocarbons, resins and asphaltene fractions, in oil
columns with increasing biodegradation levels toward
the bottom, suggest observed nitrogen and sulfur
isotopic compositions of oil fractions, unlike whole oil,
may be affected by the biodegradation process.
Finally, it is observed that S and N isotopic
compositions of bulk bitumen and heavy oils from the
main studied pools in the basin differ consistently
displaying what appears to be a regional trend (Fig.1).
The lack of significant changes of the bulk isotopic
composition of progressively biodegraded oils in
single oil columns, suggests that the observed
regional isotopic variations are source charge related.
We conclude that S and N isotopic compositions can
be used in biodegraded oils as stable source rock
proxy signatures.
� 34 S V-CDT (‰)
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
Peace River
Buffalo Head Hills
Alberta border
Athabasca
Lloydminster
0.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0
� 15 N N2 (‰)
Cold Lake
Fig. 1. Variations of � 34 S vs. � 15 N in oil sands bitumens and
heavy oils of the Alberta Basin.
References
[1] Roadifer, R.E., Exploration for Heavy Crude Oil and
Natural Bitumen 1987, 25, 3-23
[2] Head, I.M., Jones, D.M., Larter, S.R., Nature 2003,
426, 344-352
[3] Larter, S., Adams, J., Gates, I.D., Bennett, B., Huang,
H., Journal of Canadian Petroleum Technology 2008,
47, 52-61
80

O-22
New insights into the sources and application of biohopanoid
molecular proxies in diverse settings
Helen Talbot
School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, United Kingdom
(corresponding author:h.m.talbot@ncl.ac.uk)
Microbially-mediated processes at the Earth‘s
surface and in the subsurface are fundamental
controls on the global carbon and climate cycle. One
way to trace these processes in the geological record
is to through the application of bacteriohopanepolyols
(BHPs) 1 , membrane lipids biosynthesised by many,
but not all bacteria. These complex molecules
consisting of a stable pentacyclic hydrocarbon
skeleton with an extended, highly functionalised side
chain containing at least 4 functional groups, are
widely recognised as being significant components in
soils and sediments, both terrestrial and marine.
Some BHPs have a diverse range of biological
source organisms 1 whilst others have more restricted
origins making them highly diagnostic markers. New
correlations to environment are emerging as BHP
inventories are obtained from an ever broader range
of settings. For example, recent studies have
covered locations from the Arctic 2 to the Tropics 3 and
from geothermal cyanobacterial mats and silica
sinters to peat bogs and anoxic lakes (Table 1).
As expected, tetrafunctionalised BHPs (with
functional groups at C32,33,34 and 35) are common
in all settings but are typically the least diagnostic
with the widest range of sources; however, other
groups have emerged with potential as tracers for
specific processes.
The prevalence of adenosylhopane (and related
structures) in soils combined with their (near) total
absence in marine samples far removed from any
significant terrestrial source, has prompted the
proposal that the relative contribution of this group of
compounds to the sedimentary BHP pool may be a
useful proxy for soil organic matter input. As a
foundation to this potential application, we have
surveyed the BHP composition of over 600 soil
samples from around the world and the comparison
of these terrestrial BHP fingerprints to those from a
range of aquatic sediments of different ages reveals
significant differences.
More recently it has been observed that
unsaturated BHPs, which are only present in trace
amounts (if at all) in most settings including soils, are
highly abundant in surface peat layers and may
reflect the activity of nitrogen-fixing bacteria.
In geothermal settings with significant
cyanobacterial biomass, a suite of novel C-2
methylated and non-methylated structures are
common at diverse locations from North America,
Chile and New Zealand. 4 However, BHPs methylated
at the C-3 position are rarely observed in any setting
in stark contrast with observations of 3methylhopanes
in older systems.
Finally, recent data have highlighted the
significance and potential of aminoBHPs (and
aminobacteriohopanepentol in particular) as tracers
for aerobic methane oxidation in both terrestrial and
marine systems with these compounds observed in
samples up to 55Ma.
Table 1. Characteristic environmental BHP
compositions
Sample type BHP groups a
No. BHPs b
Soil T> A >> P and H 18-22
Peat (oxic) UT � T >> A, P and H > P and H > A 20-22
Lakes (small) T � P � H >> A 10-12
Lakes (large) T, A >> P and H 8-10
Rivers T, A >> P and H 10-15
Estuary T, A, H > P 8-12
Deep Sea Fan T, H>> A, P and An 8-12
Open Marine T, An 0-4
Silica Sinters T > P 10-15
Mats T, MT, P, MP 6-8
a
Key: A = adenosylhopane and related structures; An
= 32,35-anhydrobacteriohopanetetrol; M= methylated;
T, P and H = tetra-, penta- and hexafunctionalised
BHPs respectively; U = unsaturated (� 6 and/or 11 )
b
Number of BHPs observed; indicated values are
typical but not exclusive
References
[1] Talbot H.M. & Farrimond P., 2007. Organic
Geochemistry 38, 1212-1225.
[2] Rethemeyer, J. et al. 2010. Organic Geochemistry
41, 1130-1145.
[3] Handley, L., et al., 2010. Organic Geochemistry
41, 910-914.
81

O-23
Novel applications of trace metals and Molybdenum isotopes in
petroleum fluid studies
Sander van den Boorn 1 , Riccardo Avanzinelli 2,4 , Pim van Bergen 3 , Tim Elliott 2 , Corey
Archer 2 , Andrew Bishop 1 , Volker Dieckmann 1
1 Shell Projects and Technology, Rijswijk, Netherlands, 2 University of Bristol, Bristol, United Kingdom, 3 Shell
Upstream <strong>International</strong>, Aberdeen, United Kingdom, 4 Università degli Studi di Firenze, Firenze, Italy
(corresponding author:sander.van-den-boorn@shell.com)
The application of metals data in petroleum geochemistry
has been traditionally restricted to nickel (Ni) and vanadium
(V). Crude oils contain many other metal species, which are
routinely characterized in refining because of their role as
catalyst poisons. However, the geochemical significance of
metals other than Ni or V has not been well described, in
part due to historical limitations on their accurate
quantification. These metals have the potential to provide
additional valuable insights in to the origins of petroleum and
changes taking place during migration and accumulation.
Furthermore, recent developments in MC-ICP-MS have
opened up the field of non-traditional stable metal isotopes
(e.g. Mo) that may have applications in petroleum fluid
studies given their susceptibility to exhibit diagnostic
fractionation patterns (e.g. Anbar and Rouxel, 2007).
In this study analytical techniques to measure a large
number of trace metal concentrations and Mo isotope ratios
(reported as δ 98 Mo) in oils were developed. The extraction
procedure involves ashing crude oils in pressurized quartz
vessels in a High Pressure Asher (HPA) which results in the
quantitative removal of the organic matrix. Trace element
analyses were performed using ICP-MS with good precision
(

O-24
A biological source for the orphan branched tetraethers
ubiquitously occurring in soil and coastal marine and lake
sediments
Jaap Sinninghe Damste 1,2 , Irene Rijpstra 1 , Johan Weijers 2 , Ellen Hopmans 1 , Baerbel
Foesel 3 , Joerg Overmann 3 , Svetlana Dedysh 4
1 NIOZ Netherlands Institute for Sea Research, Department of Marine Organic Biogeochemistry, Den Burg,
Netherlands, 2 Utrecht University, Department of Earth Sciences, Geochemistry,, Utrecht, Netherlands,
3 Leibniz-Institut DSMZ - Deutsche Sammlung von Mikroorganismen und Zellkulturen, Braunschweig,
Germany, 4 S.N. Winogradsky Institute of Microbiology, Russian Academy of Sciences, Moscow, Russian
Federation (corresponding author:jaap.damste@nioz.nl)
Global climate change is a topic of major interest as it
has a large impact on human societies. Detailed
reconstruction of past climates, especially temperature,
is, therefore, of considerable importance.
Several organic proxies are available to reconstruct
absolute sea surface temperatures. Continental
temperature reconstructions, however, are hampered
by a lack of quantitative temperature proxies and,
consequently, are often qualitative rather than
quantitative. Recently, we discovered a new
quantitative continental temperature proxy, the
MBT/CBT index, which is based on the distribution of
branched glycerol dialkyl glycerol tetraethers (GDGT;
e.g. 1) membrane lipids of bacteria residing in soil and
peat [1]. Their composition is a function of annual
mean air temperature and pH. These lipids are
transported by rivers to the ocean and deposited in
marine sediments. Determination of the MBT/CBT
index in sediment cores from river fans can, thus,
potentially be used to reconstruct continental, river
basin-integrated, temperatures from a marine record
in front of large river outflows. For a full understanding
and validation of this proxy, the microbial origin of
branched GDGTs needs to be elucidated. In a study
of a Swedish peat, molecular ecological data pointed
to the potential of Acidobacteria, a highly diverse
phylum of the Bacteria, to biosynthesize branched
GDGTs but examined cultures did not reveal the
presence of branched GDGTs. In this study, we
systematically investigated 17 different, available and
newly isolated, cultured strains representing 13
different species of subdivisions 1 and 3 of the
Acidobacteria.
The distribution of membrane lipids were examined by
hydrolysis and GC/MS and by HPLC/MS of intact
polar lipids (IPLs). Upon both acid and base
hydrolysis of total cell material the uncommon
membrane-spanning lipid, 13,16-dimethyl octacosanedioic
acid (iso diabolic acid, 2), was released
from all studied acidobacteria in substantial amounts
(22-43% of all fatty acids). This lipid has previously
only been encountered in thermophilic Thermoanaerobacter
species but bears a structural
resemblance to the alkyl chains of bacterial glycerol
dialkyl glycerol tetraethers (GDGT) that occur
ubiquitously in peat and soil. As reported previously,
most species also contained iso C15 and C16:1ω7C as
major fatty acids but the presence of iso diabolic acid
was unnoticed in previous studies, most probably
because the complex lipid that contained this moiety
was not extractable from the cells and iso diabolic
acid only be released by hydrolysis. Direct analysis of
intact polar lipids in the Bligh Dyer extract of three
Acidobacterial strains did indeed not reveal the
presence of membrane spanning lipids. In two of the
17 strains ether-bound iso diabolic acid was detected
after a hydrolysis of the cells, including one branched
GDGT (1), containing iso diabolic acid-derived alkyl
chains. Although this represents an important step in
the identification of the biological source of the orphan
branched GDGTs, their distribution in soils is more
complex and the presence of additional (Acido)bacteria
have to explain the presence of the full
complement of branched GDGTs in soil and coastal
marine and lake sediments.
References
[1] Weijers, J.W.H., Schouten S., van den Donker
J.C., Hopmans E.C., Sinninghe Damsté J.S., 2007.
Geochim. Cosmochim. Acta 71, 703-713.
[2] Weijers J.W.H., Panoto E., van Bleijswijk J.,
Schouten S., Rijpstra W.I.C., Balk M., Stams A.J.M.,
Sinninghe Damsté J.S. 2009. Geomicrobiol. J. 26,
402-414.
OH
O
O
HOOC
1
2
O
O
COOH
OH
83

O-25
The chemical structure of insoluble organic matter in
carbonaceous meteorites
Sylvie Derenne 1 , François Robert 2
1 BioEMCo CNRS / UPMC, Paris, France, 2 LMCM CNRS / MNHN, Paris, France (corresponding
author:sylvie.derenne@upmc.fr)
Carbonaceous meteorites are the most primitive
objects of the solar system. They exhibit significant
carbon contents and most of this carbon occurs as
insoluble organic matter (IOM), which might be the
first OM available on early Earth for life. Moreover,
this OM may contain specific extraterrestrial
signatures and should provide information on solar
system history. It is therefore of special interest to
decipher the chemical structure of this IOM. Through
the use of numerous complementary analytical tools,
key information was obtained on this structure at a
molecular level and a model of structure was built up.
IOM was isolated from the Murchison meteorite using
successive extractions and acid treatments (HCl, HF).
Its chemical structure was investigated through a
combination of various spectroscopic methods
(Fourier transform infra-red, solid-state 13 C and 15 N
NMR, electron paramagnetic resonance (EPR), X-ray
absorption near-edge spectroscopy), chemical (RuO4
oxidation) and thermal (pyrolysis) degradations and
high resolution transmission electron microscopy.
Taken together, these techniques provided a wealth
of qualitative and quantitative information. The IOM is
therefore based on a network of relatively small
polyaromatic units (comprising 10-15 benzene rings in
average), cross-linked by short, highly branched
aliphatic chains that may include ester and ether
functions. Nitrogen was shown to mainly occur as
heterocycles whereas sulphur is distributed (3/1)
between thiophene rings and aliphatic sulphides.
A statistical model is proposed for this molecular
structure, fitting with 11 parameters derived from the
aforementioned analyses.
EPR revealed an heterogeneous distribution of free
organic radicals and presence of diradicals, which can
be both considered as an extraterrestrial signature.
Moreover, these carbonaceous meteorites are known
to be highly enriched in deuterium but the precise
location and origin of this deuterium was still to
determine. D/H ratio was determined in individual
compounds released through RuO4 oxidation and
pyrolysis. These two techniques allow studying both
the aromatic units and the aliphatic linkages.
Deuterium distribution within these compounds
revealed no significant difference between aromatic
and aliphatic moieties but led to consider deuterium
location in the macromolecule and to distinguish three
types of H, namely aromatic, benzylic and aliphatic.
These types of H exhibit different deuterium
enrichment and the latter is related to the C-H bond
strength. Based on this relationship, we propose that
the IOM formed in a D-poor environment and was
then transported and further enriched through
exchange in a D-rich medium.
Very recently, nanoSIMS analyses revealed a high
spatial heterogeneity for deuterium in IOM and
pointed to the occurrence of hot-spots of D. Following
the same reasoning, such hot spots should
correspond to molecules with very weak C-H bonds.
Based on their abundance and heterogeneous
distribution, we proposed the organic free radicals to
be the hosts of these D enrichments. This was further
confirmed using pulsed EPR.
These results are difficult to reconcile with the usual
interpretation according to which high D/H ratios
represent survivals of interstellar grains. More likely,
the deuterium-enrichment process took place after the
formation of organic grains characterized by low D/H
ratios, through an isotopic exchange-reaction with Drich
gaseous molecules, such as H2D + or HD2 +. This
exchange reaction most likely took place in the diffuse
outer regions of the protoplanetary disk around the
young Sun..
84

O-26
A radiotracer experiment for investigating the degradation
kinetics of intact polar lipids in sediments
Sitan Xie 1 , Julius Sebastian Lipp 1 , Gunter Wegener 2 , Timothy G. Ferdelman 2 , Kai-Uwe
Hinrichs 1
1 Marum Center for Marine Environmental Sciences, University of Bremen, Organic Geochemistry Group,
Bremen, Germany, 2 Max Planck Institute for Marine Microbiology, Bremen, Germany (corresponding
author:sitan.xie@uni-bremen.de)
Intact polar lipids (IPLs) constitute the cellular
membrane of every organism. As a consequence,
their analysis may provide an unselective view on
microorganisms present in an environmental sample.
Due to the nature of the bond between the headgroup
and the glycerol backbone, IPLs are assumed to be
unstable after cellular decay and are therefore used
as biomarkers for living microbial cells [1,2,3]. To act
as a proxy for live cells, the half life of extracellular
IPLs needs to be lower than the presumed cell
population turnover which is estimated to be on the
order of thousands of years [4]. Conversely, if the half
life is much higher, the fossil component could
potentially mask in situ IPL production [5,6]. A few
previous studies have investigated the degradation
kinetics of IPLs in shallow sediments. These studies
suggested that headgroups of bacterial phospholipids
degrade rapidly after cell lysis [1,2], whereas
glycosidic ether lipids, which are dominantly produced
by archaea, may be preserved longer [2]. However,
stability of IPLs has not been studied systematically
under conditions relevant to low-activity subsurface
sediments and the degradation kinetics of IPLs still
remains unclear. Therefore a better understanding of
IPL degradation is essential for the interpretation of
lipid signals in natural environments.
In this study, the degradation kinetics of IPLs has
been evaluated by a radiotracer incubation
experiment. Phosphatidylethanolamine diacylglycerol
(PE-DAG) and 1Gly-archaeol (1Gly-AR) were used as
model compounds representative for typical bacterial
and archaeal membrane lipids, respectively. The
carbons in the headgroups of IPLs were labeled by
14 C. Radio labeled IPLs were added to anaerobic
slurries of sediment from the Wadden Sea surface
and Cascadia Margin subsurface (138.21 mbsf)
sediments. The slurries were incubated at 4°C and
20°C to study the effect of temperature on the
degradation of IPLs. Independent of the chemical fate
of the polar headgroup after its hydrolysis from the
glycerol backbone, the 14 C enters the aqueous or gas
phase while the intact lipid is insoluble and remains in
the solid phase. Reaction progress is monitored by
quantifying the increase of radioactivity in the
aqueous solution and in the gas phase with a
scintillation counting technique.
The initial results of
14 C labeled PE-DAG
experiment (Fig.1) showed that about 48% of PE-
DAG was degraded after fourteen days of incubation
at 20°C. The degradation rate of PE-DAG and 1Gly-
AR is currently being examined by long-term
incubation. We will discuss the results in the context
of current applications of IPLs as proxies for live cells.
Fig.1. Initial degradation of 14 C labeled PE-DAG in Cascadia
Margin sediment slurry incubated at 20°C. A: negative killed
control experiment showing that no abiotic degradation takes
place. B: strong lipid degradation in the alive sediment.
References
[1] White, D.C., Davis, W.M., Nickels, J.S., King, J.D., Bobbie, R.J. (1979)
Oecologia 40, 51-62.
[2] Harvey, H.R., Fallon, R.D., Patton, S. (1986) Geochim. Cosmochim. Acta
50, 795-804.
[3] Lipp, J.S., Morono, Y., Inagaki, F., Hinrichs, K.U. (2008) Nature 454, 991-
994.
[4] Biddle, J.F., Lipp, J.S., Lever, M.A., Lloyd, K.G., Sørensen, K.B.,
Anderson, R., Fredricks, H.F., Elvert, M., Kelly, T.J., Schrag, D.P., Sogin,
M.L., Brechley, J.E., Teske, A., House, C.H., Hinrichs, K.U. (2006) Proc.
Natl. Acad. Sci. USA 103, 3846-3851.
[5] Lipp, J.S. and Hinrichs, K.U. (2009) Geochim. Cosmochim. Acta 73,
6816-6833.
[6] Schouten, S., Middelburg, J.J., Hopmans, E.C., Damsté J.S.S. (2010)
Geochim Cosmochim. Acta 74, 3806-3814.
85

O-27
Coenzyme factor 430: abundance and isotopic compositions for
tracing a key molecule of methanogenesis and reversemethanogenesis
Yoshinori Takano, Hiroyuki Imachi, Nana O. Ogawa, Yoshito Chikaraishi, Nao Ohkouchi
Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Yokosuka, Japan
(corresponding author:takano@jamstec.go.jp)
Introduction
Coenzyme Factor 430 (F430) is the prosthetic group
of methyl-coenzyme M reductase (MCR) and the key
enzyme in biological methane-forming step in
methanogenic archaea and methane-oxidizing step in
methanotrophic archaea [1-3]. The structure of F430
has been established based on spectroscopic studies
of isolated coenzyme and its partial synthetic
derivatives. The coenzyme is a yellow non-fluorescent
nickel hydroporphyrin having unique pentacarboxyl
structure (Figure 1: the reduced Ni(I) is active state for
the enzyme). We have recently established a method
to identify and quantify F430 in microbial slurry with its
compound-specific carbon and nitrogen isotopic
compositions for the applications of methane
biogeochemistry and global carbon cycle.
Experimental
We extracted yellowish F430 fraction (Fig.1) from
archaeal culture samples (methanogen assemblages,
e.g., Methanobacterium, Methanosarcina, and ANME
assemblages in sludge environments). Then, we
isolated F430 from the fraction by two steps column
chromatography (QAE Sephadex A25 and XAD (PAD
I) resin: [4]) and further purified by reversed-phase
high performance liquid chromatography/electrospray
ionization mass spectrometry (HPLC/ESI-MS: Agilent
1100) on the gradient program. The base-line
resolution of F430 was validated by photo diode array
detector (DAD), total ion chromatogram (TIC) and
selected ion monitoring (SIM). The carbon and
nitrogen isotopic compositions of the purified F430
and bulk cell were determined by an isotope ratio
mass spectrometer (IRMS; ThermoFinnigan Delta
plus XP) coupled with a Flash elemental analyzer
(EA; ThermoFinnigan EA1112) via a Conflo III
interface. We also conducted 16S rRNA gene-based
clone analysis for the archaeal culture samples.
Results and Discussion
Figure 1 shows 3-D chromatogram of the isolated
F430, whose purity is high enough for compoundspecific
isotope analysis. F430 is about 10‰ depleted
in 13 C relative to bulk microbial slurry on average. This
13 C depletion in F430 suggests that the methanogen
13
are substantially C-depleted relative to other
microbes. We estimated F430 abundance of 600-900
nmol/dry-cell gram in the methanogen. Although we
are still in a preliminary stage, we suggest that the
present method is useful for estimating activities of
methanogenesis and reverse-methanogenesis in the
sub-seafloor environment. Furthermore, carbon and
nitrogen isotopes of F430 will provide information on
the processes mediated by methanogens and
anaerobic methanotrophs.
References
[1]Thauer, R. (1998) Biochemistry of
methanogenesis. Microbiology, 144, 2377-
2406.
[2]Kruger, M. et al. (2003) A conspicuous nickel
protein in microbial mats that oxidize methane
anaerobically. Nature, 426, 878-881.
[3]Scheller, S. et al. (2010) The key nickel enzyme of
methanogenesis catalyses the anaerobic
oxidation of methane. Nature, 465, 606-608.
[4]Mayr, S. et al. (2008) Structure of an F430 variant
from archaea associated with anaerobic
oxidation of methane. J. Amer Chem Soc, 130,
10758-10767.
Figure 1 Online RP-HPLC/ESI-MS separation of the
nickel porphinoid, coenzyme F430 (C42H51N6NiO13),
from methanogen.
86

O-28
Nitrogen isotopic signatures of amino acids in microbes: culture
experiments and applications to marine sediments
Yasuhiko Yamaguchi 1,2 , Yoshinori Takano 2 , Yoshito Chikaraishi 2 , Nanako Ogawa 2 ,
Hiroyuki Imachi 2 , Hisami Suga 2 , Yusuke Yokoyama 1,2 , Naohiko Ohkouchi 2
1 Atmosphere and Ocean Research Institute (AORI), The University of Tokyo, Kashiwa, Japan, 2 Institute of
Biogeosciences, Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Yokosuka, Japan
(corresponding author:y-t-yamaguchi@aori.u-tokyo.ac.jp)
The microbial roles in biogeochemical cycles
remain largely unknown, mainly because of the lack
of tools to explore in situ metabolic activities of
microbes. The nitrogen isotopic composition (δ 15 N) of
individual amino acids, especially for glutamic acid
(Glu) and phenylalanine (Phe), had been
demonstrated as a promising tool for estimating the
food sources of organisms in the grazing food web
[e.g. Ref.1-5]. Applicability of this amino-acids method
to microbes or detritus food web, however, remains
uncertain, because the method has been constructed
based on the analytical results of aquatic
photoautotrophs, terrestrial higher plants, and
animals, but not chemotrophic microbes. In this study,
the δ 15 N of amino acids were investigated in 5
cultured microbes namely a fungus (Saccaromyces
cerevisiae), a bacterium (Escherichia coli) and
archaea (Sulfolobus tokodaii, Halobacterium
salinarum, and Methanothermobacter
thermautotrophicus) with controlling their nitrogen
sources.
When the microbes synthesized amino acids de
novo, the relative δ 15 N values of their amino acids
(e.g., δ 15 NGlu – δ 15 NPhe = +3.1±1.0‰, n=3) were
similar to aquatic photoautotrophs (+3.4±0.9‰, n=25;
Ref.1-5), whereas the case of the microbes
assimilated amino acids from diets, they showed 15 Nenrichment
on the amino acids (e.g., Δ 15 NGlu =
+8.2±0.8‰ and Δ 15 NPhe = +0.1 ±0.2‰, n=4) close to
that of animals (+8.0±1.1‰ and +0.4±0.4‰,
respectively, n=11; Ref.1,4,5) [Fig.1]. The results
suggest that the nitrogen-isotope fractionation
processes of amino acids are likely common among
various organisms covering the 3 domains [Fig.2] and
among various environmental conditions such as
growth temperature, pH, or salinity. Therefore, δ 15 N of
amino acids would potentially be a powerful tool to
clarify in situ microbial metabolism (amino-acids
synthesis or decomposition) and their biogeochemical
roles. In the presentation, we also show its
applications to marine sediments in various settings.
Fig.1. Conceptual diagrams of δ 15 N variation of glutamic
acids (Glu) and phenylalanine (Phe) in algae and animals
(A) [Ref.1-5], and in microbes (B) [this study]. Mean values
in each organism group are shown for relative δ 15 N values
and 15 N-enrichment factors.
Fig.2. Relative δ 15 N values and 15 N-enrichment factors of Glu
and Phe in the 3 domain including microbes, algae, and
animals. [Ref.1-5 and this study]
References
[1] McClelland, J.W. & Montoya, J.P. (2002) Ecology 83,
2173-2180.
[2] McClelland, J.W. et al. (2003) Deep-Sea. Res. I 50, 849-
861
[3] McCarthy, M.D. et al. (2007) Geochim. Cosmochim. Acta
71, 4727-2744.
[4] Chikaraishi, Y. et al. (2007) Mar. Ecol. Prog. Ser. 342, 85-
90.
[5] Chikaraishi, Y. et al. (2009) Limnol. Oceanogr.: Meth 7,
740-750.
87

O-29
Influence of temperature on methane cycling and methanotrophrelated
biomarkers in peat moss
Julia van Winden 1 , Gert-Jan Reichart 1 , Helen Talbot 2 , Niall McNamara 3 , Albert Benthien 4 ,
Jaap Sinninghe Damsté 1,5
1 Utrecht University, Utrecht, Netherlands, 2 Newcastle University, Newcastle, United Kingdom, 3 CEH,
Lancaster, United Kingdom, 4 AWI, Bremerhaven, Germany, 5 NIOZ, Texel, Netherlands (corresponding
author:j.vanwinden@geo.uu.nl)
Peat bogs are the largest terrestrial carbon sink and
an important source for atmospheric methane.
Methane emissions from peat bogs are, however,
reduced by symbiotic methane oxidizing bacteria
(methanotrophs), which live in association with peat
moss (Sphagnum). Future climate change projections
indicate that mid to high latitudes, especially Western
Siberia, with the largest peat bog occurrence globally,
may become increasingly wetter and warmer.
According to reaction kinetics, increasing
temperatures will enhance both biological methane
production as well as methane oxidation. It is,
however, impossible to a priori predict which process
will outcompete the other.
To unravel the effect of temperature on both methane
production and oxidation, intact peat cores containing
actively growing Sphagnum were incubated at 5, 10,
15, 20 and 25 ºC. Even though methane consumption
increased with increasing temperature, methanotrophs
were not able to compensate for the increased
methane production by methanogens. Moreover, the
efficiency of the Sphagnum-methanotroph consortium
as a filter for methane escape strongly decreased with
increasing temperature (Fig. 1).
Fig. 1. Methane retention [%] versus temperature
How temperature-related changes have affected
methane cycling in peat bogs in the past can be
studied by examining ancient peat cores. To resolve
the effect of temperature and methane cycling on
potential methanotroph proxies, Sphagnum mosses
grown during this mesocosm study were analyzed for
intact bacteriohopanepolyols (BHPs) and compound
specific carbon isotopes of hopanoids.
Aminobacteriohopanepentol (aminopentol) is a
marker for type I methanotrophs, while
aminobacteriohopanetetrol (aminotetrol) is produced
by type II methanotrophs, and to a lesser extent by
type I methanotrophs. These methanotroph BHPs
increased slightly with increasing temperature, with
especially high concentrations at 25 ºC. However, due
to the limited duration of the experiment it was, not
possible to show a direct relationship with methane
cycling. Aminotetrol was significantly more abundant
than aminopentol, particularly at higher temperatures,
indicating that type II methanotrophs more easily
adapt to changing environmental conditions
compared to type I methanotrophs.
Diploptene is a bacterial marker which is produced by,
but not exclusive to, methanotrophs. Compoundspecific
δ 13 C values of diploptene demonstrated a
strong decrease with increasing temperature, with
values of -33,9‰ at 5 ºC and -40,7‰ at 25 ºC. This
relationship is best explained by enhanced methane
cycling at higher temperatures, caused by increased
methanotroph abundance and/or enhanced isotopic
fractionation as a result of increased methane
availability.
Our study shows that extent of methane retention by
symbiotic methanotrophs in peat bogs decreases with
increasing temperature. Furthermore, a combination
of BHPs and δ 13 C values of diploptene, or its
diagenetic products, potentially provide powerful tools
to assess methanotrophic community structures and
methanotrophic activity, also in past environments.
88

O-30
First detection of triterpenyl acetates in soils: sources and
potential as new palaeoenvironmental biomarkers
Marlène Lavrieux 1,2 , Jérémy Jacob 1 , Claude Le Milbeau 1 , Jean-Robert Disnar 1 , Renata
Zocatelli 1 , Jean-Gabriel Bréheret 2 , Kazuo Masuda 3
1 Institut des Sciences de la Terre d’Orléans (ISTO), Université d’Orléans, CNRS/INSU, Université de Tours,
UMR 6113, Orléans, France, 2 Institut des Sciences de la Terre d’Orléans (ISTO), Université de Tours,
CNRS/INSU, Université d’Orléans, UMR 6113, Tours, France, 3 Laboratory of Phytochemistry, Showa
Pharmaceutical University, Machida, Tōkyō, Japan (corresponding author:marlene.lavrieux@etu.univtours.fr)
Understanding past reactions of ecosystems under
natural and anthropic constraints is of crucial
importance to anticipate the consequences of the
current global changes. Unraveling natural and
anthropic impacts on environments requires the
reconstruction of ancient land-uses. As a part of a
larger project aiming at developing new molecular
biomarkers in soils that could be specific of their
overlying vegetation, we have analyzed the neutral
lipid content of soils developed under distinct types of
plants. Soils were sampled around Lake Aydat, in
Central France, which catchment is covered with
pastures/meadows, forests and moors. The
ketone/ester lipid fraction from soils under pastures or
meadows contains a series of 14 pentacyclic
triterpenyl acetates with a large structural diversity
(Fig. 1).
This discovery motivated an extensive
phytochemical literature survey (240 references) that
showed restricted potential sources of triterpenyl
acetates. �-amyrin, taraxeryl, glutinyl, �-amyrin, and
multiflorenyl acetates are found in very distinct taxa
and are thus poorly informative. Conversely, lupeyl,
bauerenyl, isobauerenyl, taraxasteryl and �taraxasteryl
acetates appear more specific since they
are majoritary reported in Asteraceae. Pichierenyl,
isopichierenyl and gammacerenyl acetates seem to
be the more specific ones since they are produced by
a single known species, Picris hieracioides L.
(hawkweed oxtongue, Asteraceae).
Then, we investigated the possible local plants that
could have produced the triterpenyl acetates found in
the soils of Lake Aydat catchment. 97 Asteraceae
species are reported in the area [1], 8 being known as
triterpenyl acetate producers. Combined together,
these 8 species can explain the diversity of
compounds observed in soils, except for glutinyl and
swertenyl acetates. These two compounds could
either result from the diagenesis of other compounds
or could be produced by a yet unknown biological
source. To our knowledge, our work constitutes the
first report on acetates of bauerane and taraxastane
types in geosystems. Our compilation of data also
brings original insights into chemotaxonomical
relationships with Asteraceae.
Asteraceae are particularly adapted to anthropized
environments and rubble [1], but are more generally
defined as meadows and pasture species (semi-open
to open habitats), appreciating colonizing disrupted
environments and able to conquer arable lands lied
fallow [2], [3]. Considering the restricted ecological
requirements of this family and the ability of
pentacyclic triterpenes to survive in geosystems,
these new higher plant specific biomarkers could be
of direct relevance for the characterization of semiopen
to open habitats resulting from anthropic
disturbances.
Ac
O
Ac
O
Ac
O
Ac
O
Ac
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Ac
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Ac
O
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O
1 2 3 4 5 6
7 8 9 10 11 12 13
14
45 46 47 48 49 50 51 52
Retention time (min)
Fig. 1. GC-MS Total Ion Chromatogram (TIC) showing the distribution of
triterpenyl acetates (with the corresponding structures) in the ketone/ester
fraction from the lipid extract of a grassland soil from the Lake Aydat catchment).
1: Taraxeryl acetate (Taraxer-14-en-3�-yl acetate); 2: �-Amyrin acetate (Olean-
12-en-3�-yl acetate); 3: �-Amyrin acetate (Olean-13(18)-en-3�-yl acetate); 4:
Isobauerenyl acetate (Bauer-8-en-3�-yl acetate); 5: Glutinyl acetate (Glutin-5-en-
3�-yl acetate); 6: Lupeyl acetate (Lup-20(29)-en-3�-yl acetate); 7: Multiflorenyl
acetate (Multiflor-7-en3�-yl acetate); 8: Bauerenyl acetate (Bauer-7-en-3�-yl
acetate); 9: �-Taraxasteryl acetate (Taraxast-20-en-3�-yl acetate); 10:
Taraxasteryl acetate (Taraxast-20(30)-en-3�-yl acetate); 11: Isopichierenyl
acetate (Pichier-8-en-3�-yl acetate) – tentative identification; 12 Pichierenyl
acetate (Pichier-9(11)-en-3�-yl acetate); 13: Gammacerenyl acetate (Gammacer-
16-en-3�-yl acetate); 14: Swertenyl acetate (Pichier-7-en-3�-yl acetate).
References
[1] Antonetti, P., Brugel, E., Kessler, F., Barbe, J.P., Tort, M.,
2006. Atlas de la Flore d‘Auvergne. Conservatoire botanique
national du Massif Central, 981 pp.
[2] Cronquist A., Vascular Flora of the Southeastern United
States. Volume 1: Asteraceae. 1980, 276 p.
[3] Bouby, L., Billaud, Y., 2005. Identifying prehistoric
collected wild plants: a case study from Late Bronze Age
settlements in the French Alps (Grésine, Bourget Lake,
Savoie). Economic Botany 59, 3, 255-267.
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89

O-31
The fate of collembola derived organic matter in soil
Ian Bull 1 , Andrew Rawlins 1 , Philip Ineson 2 , Richard Evershed 1
1 University of Bristol, Bristol, United Kingdom, 2 University of York, York, United Kingdom
Soil collembola play an important role in the initial
degradation and physical structuring of organic matter
entering the soil environment, especially in soils that
are in the early succession stages (Rusek, 1975).
However, the consequences of digestion for organic
matter are poorly understood at the molecular level.
Most soils contain millions of collembola faecal pellets
per square metre and it is thought these are beneficial
in releasing nutrients to plant roots as the faecal
material is decomposed by microbes (Hopkin, 1992).
Despite its importance, very little is known about the
fate of collembola derived organic matter, i.e.
collembola faeces, in the soil.
Organic matter processed by collembola (and the
faecal pellets produced), in a series of time-course
laboratory studies, was assessed and compared
using a range of analytical techniques. 13 C-labelled
substrates were used to examine the differences in
the decomposition processes taking place and to
determine the microbial community responsible for
organic matter decomposition in soil microcosms.
The biochemical composition of collembola diets
and the corresponding faeces were determined and
revealed that labile components of the diet such as
triacylglycerols, sterols, carbohydrates and short
chain/unsaturated fatty acids were readily assimilated
by collembolan, most likely satisfying their nutritional
requirements. More recalcitrant components of the
fresh organic matter such as wax esters, n-alkanes
and long chain fatty acids were still degraded by
collembola, albeit more slowly than labile
components. Lignin exhibited a marked resistance to
degradation by passage through the collembolan gut,
although guaiacyl pyrolysis products appeared to be
least affected as they became more dominant in the
collembola faeces. These results agree with those of
a previous analogous study of the pill millipede
(Rawlins et al., 2006). Changes in the composition
and abundance of biopolymers in soil microcosms
were investigated using pyrolysis gas
chromatography mass spectrometry. An increase in
abundance of guaiacyl components with carbonyl
functional groups was observed in amended soil after
incubation, indicating that lignin present after
incubation was at a more advanced state of
degradation. The concentration of carbohydrates was
much lower after incubation, with all soils containing
roughly the same concentration. The microbial
community involved in the decomposition of organic
matter was investigated by combining phospholipid
fatty acid (PLFA) analysis with compound-specific
stable carbon isotope analysis. The microbial biomass
found in all incubated soils was of a similar size and
was dominated by Gram-negative bacteria, indicated
by the occurrence of a predomiant C18:1�7 PLFA in
most soils after incubation. An increase in
concentration and � 13 C value of 10methylhexadecanoic
acid in some of the amended
soils reflects the important role played by
actinomycetes in lignin degradation, indicating that
lignin transformations and/or wholesale degradation
occurred within the timescale (80 days) of the
experiment.
References
Hopkin, S. P. (1992) Colembola. In : R. LAL (Ed.)
Encyclopaedia of Soil Science. Marcel Dekker, New
York, pp. 207-210.
Rawlins, A. J., Bull, I. D., Poirier, N., Ineson, P. and
Evershed, R. P. (2006) The biochemical
transformation of oak (Quercus robur) leaf litter
consumed by the pill millipede (Glomeris
marginata). Soil Biology and Biochemistry38, 1063-
1076.
Rusek, J. (1975) Die bodenbildend Funktion von
Collembolen und Acarina. Pedobiologia 15, 299-
308.
90

O-32
The role of light intensity in controlling the �D and � 13 C values of
organic compounds in leaf waxes: Should we worry about it?
Nikolai Pedentchouk 1 , Kirill Peskov 2 , Tracy Lawson 3 , Yvette Eley 1
1 The University of East Anglia, Norwich, United Kingdom, 2 Institute for Systems Biology SPb, Moscow,
Russian Federation, 3 The University of Essex, Colchester, United Kingdom (corresponding
author:n.pedentchouk@uea.ac.uk)
Several recent studies have suggested that a
simultaneous analysis of � 13 C and �D of n-alkyl
biomarkers in leaf waxes may help identify the type of
vegetation contributing to the sedimentary record. The
rationale behind this approach is that in C3 plants the
� 13 C and �D are linked because of their dependence
on water use efficiency (WUE) [1]. Here we show that
the assumption about this link might not necessarily
be correct, because during biosynthesis �D of lipids
could also be influenced by other factors that are
decoupled from those controlling the � 13 C values.
We measured � 13 C and �D of leaf wax n-alkanes
from 4 lines of Arabidopsis thaliana grown indoors.
The plants were subjected to 3 light treatments, while
the rest of parameters (duration of illumination,
temperature, relative humidity, and water) were kept
constant. In addition, we measured leaf water �D,
transpiration, CO2 conductance, net photosynthesis,
as well as chlorophyll concentration and fluorescence.
The isotope and gas flux data were then used to
develop a kinetic model to estimate �D of NADPH.
As expected, the plants differed in their
physiological response to various light treatments.
WUE was considerably greater in high (HL) than in
middle (ML) and in low (LL) lights. We found that � 13 C
of n-C31 alkane are consistent with the differences in
WUE among the plants at 3 light levels. However, our
data also showed that �D of n-C31 in HL are more
negative than in ML and LL, which, unlike � 13 C in ML
and LL, almost totally overlap (Fig.1). Furthermore,
the pattern among �D of n-C31 at 3 light levels is
different from that shown by the transpiration data.
Our kinetic model, which includes the effects of
light sensitive enzyme-driven processes, allowed us
to estimate��D of NADPH at 3 light levels. We found
that the pattern among �D of NADPH is similar to nalkane
�D and dissimilar to transpiration.
The results of this work suggest that light intensity
is an important environmental parameter that
significantly influences both � 13 C and �D of leaf
waxes. However, �D is decoupled from � 13 C because
of the different biochemical mechanisms affecting D/H
and 13 C/ 12 C fractionations during photosynthesis.
Fig. 1. �D values of n-C31 alkane (measured) and NADPH
(modelled), and transpiration measured for 4 different lines
of Arabidopsis thaliana at 3 light levels. D/H fractionation
between H2O and NADPH equal to � = 0.40 [2] was used
during model simulations for calculating the resultant �D of
NADPH at each of 3 light levels.
References
[1] Hou, J. et al. (2007) Org. Geochem. 38, 1251-1255.
[2] Luo, Y.-H. et al. (1991) Plant Cell Physiol. 32, 897-900.
91

O-33
Empirical relationship between leafwWax n-alkane δD and
altitude in the Wuyi, Shennongjia and Tianshan Mountains,
China: implications for paleoaltimetry
Pan Luo 1 , Ping'an Peng 2 , Gerd Gleixner 3 , Zhuo Zheng 4 , Zhonghe Pang 1 , Zhongli Ding 1
1 Key Laboratory of Cenozoic Geology and Environment, Institute of Geology and Geophysics, Chinese
Academy of Sciences, Beijing, China, 2 Guangzhou Institute of Geochemistry, Chinese Academy of Sciences,
Guangzhou, China, 3 Max Planck Institute for Biogeochemistry, Jena, Germany, 4 Department of Earth
Sciences, Sun Yat-sen University, Guangzhou, China (corresponding author:pinganp@gig.ac.cn)
Estimating past elevation not only provides evidence
for vertical movements of the Earth‘s lithosphere, but
also increases our understanding of interactions
between tectonics, relief and climate in geological
history. Development of biomarker hydrogen isotopebased
paleoaltimetry techniques that can be applied
to a wide range of sample types is therefore of
continuing importance. Here we present leaf waxderived
n-alkane δD (δDwax) values along three soil
altitudinal transects, at different latitudes, in the Wuyi,
Shennongjia and Tianshan Mountains in China, to
investigate δDwax gradients and the apparent
fractionation between leaf wax and precipitation (εwaxp).
We find that soil δDwax values track altitudinal
variations of precipitation δD along the three transects
that span variable environment conditions and vertical
vegetation spectra (Fig.1) . An empirical δDwaxaltitude
relation is therefore established in which the
average δDwax lapse rate of -2.27±0.38‰/100 m is
suitable for predicting relative paleoelevation change
(relative uplift). The application of this empirical
gradient is restricted to phases in the mountain uplift
stage when the atmospheric circulation had not
distinctly changed and to when the climate was not
arid. An empirical δDwax-latitude-altitude formula is
also calculated: δDwax = 3.483LAT - 0.0227ALT -
261.5, which gives the preliminary spatial distribution
pattern of δDwax in modern China.
Mean value of εwax-p in the extreme humid Wuyi
Mountains is quite negative (-154‰), compared to the
humid Shennongjia (-129‰) and the arid (but with
abundant summer precipitation) Tianshan Mountains
(-130‰), which suggests aridity or water availability in
the growing season is the primary factor controlling
soil/sediment εwax-p. Along the Tianshan transects,
values of εwax-p are speculated to be constant with
altitude; while along the Wuyi and Shennongjia
transects, εwax-p are also constant at the low-mid
altitudes, but become slightly more negative at high
altitudes which could be attributed to overestimates of
precipitation δD or the vegetation shift to grass/conifer.
Additionally, a reversal of altitude effect in the vertical
variation of δDwax was found in the alpine zone of the
Tianshan Mountains, which might be caused by
atmospheric circulation change with altitude. This
implies that the paleo-circulation pattern and its
changes should also be evaluated when stable
isotope-based paleoaltimetry is applied.
Fig.1. Variations of δD values of n-alkanes derived
from soils along altitudinal transects
92

O-34
Hydrogen isotopic composition of long chain n-alkanes from a
marine sediment core transect off Africa: implications for the
tropical African rainbelt
James Collins, Enno Schefuß, Stefan Mulitza, Matthias Prange, Gerold Wefer
MARUM, Bremen, Germany (corresponding author:jcollins@marum.de)
The tropical African rainbelt, which oscillates on a
seasonal basis, forms an important component of the
climate system. However, millennial-timescale
changes in the distribution of rainfall are poorly
constrained, owing to the relative scarcity or poor
quality of terrestrial proxy data from this vast
continent.
Isotopic analyses of terrestrial lipid biomarkers are
proving to be useful tools for palaeoclimate
reconstructions. In particular, the hydrogen isotopic
composition of long-chain n-alkanes from marine
sediment cores has been used to infer changes in the
hydrological cycle (Schefuß et al, 2005, Niedermeyer
et al, 2010). More negative δD values are interpreted
to reflect more rainfall (‗amount effect‘) and/or
reduced evapotranspiration from plant leaves or soils.
However, the exact processes that are recorded by
hydrogen isotopic composition of sedimentary nalkanes
are not yet well constrained. For example,
precipitation δD may also be affected by changes in
moisture source area or extent of continental
recycling whilst any evapotranspirational enrichment
processes in the plant may be modulated by
vegetation type or photosynthetic pathway.
We have analysed the hydrogen isotopic composition
of n-alkanes from 9 marine sediment cores off
western Africa, covering the full range of the tropical
rainbelt. Samples were taken from the Last Glacial
Maximum (LGM; 19-23ka), Heinrich Stadial 1 (HS1;
16-19ka) and the mid-Holocene (6-8ka) and
compared to the late Holocene (last 2000yrs).
For the late Holocene (present day) timeslice, δD
values of the C29, C31 and C33 n-alkanes are more
negative in the regions at the Northern and Southern
rims of the rainbelt (-160 ‰) and are less negative in
the equatorial regions (-150 ‰). Although
instrumental data are sparse, this seems to reflect the
spatial pattern in the δD of precipitation, where most
negative values are found in areas experiencing a
brief but intense rainy season. However, the late
Holocene pattern in the n-alkanes may also be due to
the dominance of C4 vegetation in peripheral regions
and the dominance of C3 vegetation in the equatorial
regions.
For the LGM, HS1 and mid-Holocene, however, the
spatial pattern of δD values compared to the late
Holocene do not reflect the spatial pattern of
vegetation type as suggested by δ 13 C values from
these timeslices (Collins et al, 2011). As such, we
can rule out a dominant effect of vegetation type on
δD values. Instead, during the mid-Holocene, δD
values are more negative (by ~10 ‰) than the late
Holocene for all cores of the transect. We interpret
this to represent an increase in rainfall intensity
across the full range of the rainbelt and, in
combination with increased wet season length
(Collins et al, 2011), reflects increased rainfall
amount.
LGM and HS1 δD values are broadly similar to each
other for all cores. When compared to the late
Holocene, the six northernmost cores for the LGM
and HS1 display similar or slightly less negative δD
values, suggesting similar or reduced intensity relative
to the late Holocene. However, the three
southernmost cores of the transect display more
negative δD values (~5 ‰) relative to the late
Holocene. This may reflect a brief but intense wet
season, as characterises the modern day peripheral
regions. Alternatively, however, this may also reflect
a more distal moisture source. Overall, our results
show that when used together, δ 13 C and δD may
have potential for disseminating both the wet season
length and intensity.
Collins et al, 2011, Nature Geoscience 4, 42-45.
Schefuß et al, 2005, Nature 437, 1003-1006.
Niedermeyer et al, 2010, Quaternary Science
Reviews 29, 2996-3005.
93

O-35
Biomarker evidence for the Late Neoproterozoic deep-water
oxygenation
Chunjiang Wang 1 , Maoyan Zhu 2
1 Laboratory of Geochemistry and Environmental Sciences, China University of Petroleum, Beijing, China,
2 Nanjing Institute of Geology and Palaeontology, Chinese Academy of Sciences, Nanjing, China
(corresponding author:wchj333@126.com)
An important increase in atmospheric oxygen appears
to have taken place during the late Neoproterozoic
period [1, 2] . This increase may have stimulated the
evolution of macroscopic multicellular animals [1, 3] and
may have led to oxygenation of the deep ocean [4] .
Carbon, oxygen and sulfur isotopic data are widely
discussed for understanding the nature and timing of
Neoproterozoic oxidation, while the molecular
geochemical studies are limited, with an exception of
that abundant sedimentary 24-isopropylcholestanes
detected in the Huqf Supergroup (South Oman) may
indicate the presence of Metazoa (demosponges)
even before the end of the Marinoan glaciation (
635Myr ago) [5] . Here we present the results of a highresolution
molecular geochemical research on the
Doushantuo Formation at the Jiulongwan Section,
South China, which may have provided new evidence
for the stepwise oxygenation of the deep ocean. The
homologue of methylated steranes is mainly
composed of 3-me-steranes, 4-me-steranes and
dinosteranes. This sterane composition pattern
indicates that high diversity of alga appeared after
Marinoan glaciation and persisted over most of the
Ediacaran period (635~551 Myr) in the South China
Sea, and contributed greatly to the increased
atmospheric and marine oxygen. However, the 24iso-propylcholestanes
and 24-n-propylcholestanes
are of extremely low concentration or generally under
detection limit by GC-MS-MS method. In contrast with
the enrichment of 24-isopropylcholestanes in the Huqf
Supergroup, the absence of 24-iso-propylcholestanes
in the Doushantuo Formation may indicate that the
distribution or evolution of demosponges were
different worldwide. Hopanoids predominantly occur
in aerobic bacteria, such as methanothrophs,
heterotrophs, and cyanobacteria. Thus, the relative
abundance of hopanes in sediments is directly related
to relative contribution of the aerobic bacteria. We
have found two episodes of hopane enrichment
during the Ediacaran period, which just coincide with
the two major C-isotopic negative excursions of
carbonates. The covariation of hopane abundance
and C-isotopic negative excursion is suggested as a
robust evidence for the deep-water oxygenation.
YSJ-Ds-2B-4
414.4 > 98.1
1.13e5
414.4 > 217.2
2.35e5
414.4 > 231.2
1.81e6
3-m-
4-m-
Dinost.
400.4 > 217.2
3.54e6
Fig. 1. MRM GC-MS ion chromatograms of C29–C30
steranes in the typical argillaceous dolostone from the
Doushantuo Formation, South China.
References
[1] Fike D A, Grotzinger J P, Pratt L M, Summons R E (2006) Nature
444, 744–747
[2] Canfield D E, Poulton S W, Narbonne G M (2007) Science 315,
92–95.
[3] McFadden K A, et al. (2008), Proc. Natl. Acad. Sci. USA 105,
3197–3202.
[4] Rothman D H, Hayes J M, Summons R E. (2003) Proc. Natl.
Acad. Sci. USA 100, 8124–8129.
[5] Love G D, et al. (2009) Nature 457, 718–721.
94

O-36
Highest resolution for oil dating (≤ 10 Ma): implications for the
paleocene-eocene thermal maximum from stable isotope data
Christiane Eiserbeck 1 , Kliti Grice 1 , Joseph Curiale 2
1 Curtin University, Perth, Australia, 2 Chevron Energy Technology Company, Houston, United States of
America (corresponding author:christiane.eiserbeck@gmail.com)
The Tertiary was dominated by global warming
periods with the Paleocene-Eocene Thermal
Maximum (PETM) being the most dramatic global
warming event in Earth‘s history. The sudden
warming of about 5°C caused the release of massive
amounts of isotopically light methane from the melting
gas hydrates [1].
The Tertiary was also the period of the rise and
diversification of the angiosperms towards becoming
the dominant land plants.
Both characteristics of the Tertiary have great
potential to be significant age signals for samples
deposited during that period.
Biomarkers like oleanoids, lupanoids and ursanoids
have been attributed to angiosperms and shown to
become more prominent from the Late Cretaceous
onwards. Their abundance in geological samples
increased significantly with decreasing age [2].
We examined the molecular and compound specific
isotope composition (� 13 C and �D) of biomarkers in a
number of Tertiary deltaic crude oils and source rocks
from different localities (mainly from the Arctic).
We established several angiosperm-gymnosperm
indices (AGI) all including an exhaustive number of
oleanoids, ursanoids and lupanoids (saturated, ring-
A-degraded, tri- and tetraaromatic, di-and triaromatic
ring-A-degraded).
All AGI‘s increase with decreasing age which is in
perfect agreement with the increasing predominance
of angiosperm fossil pollen records over gymnosperm
pollen records. This AGI correlation with age taken
from sediment samples of known age could very
successfully be applied to date age-unknown oils with
detectable angiosperm input with a resolution of 5-10
Ma.
� 13 C and �D of pristane (Pr) and phytane (Ph)
revealed an increase of ��D of Ph to Pr (�DPh – �DPr)
with decreasing age (Fig. 1). �DPh values were
depleted by -15 ‰ compared to �DPr supporting the
release of isotopically light freshwater from the
melting of gas hydrates as well as the ice caps at high
latitudes.
Fig. 1. ��D of Ph to Pr with age.
Complementary correlations with age could also be
established from chemometric analyses of an
extensive molecular (including GCxGC-TOF data)
and isotopic data set completing a suite of age
relationships for Tertiary crude oils and source rocks.
References
[1] Pancost, R.D., et al., Nature, 2007. 449(7160): p.
332.
[2] Moldowan, J.M., et al., Science, 1994. 265(5173):
p. 768-771.
95

O-37
The seco-oleananes: identification, origin, application and
distributions in late cretaceous/tertiary deltaic petroleum
systems
Olukayode Samuel 1 , Hans Peter Nytoft 2 , Geir Kildahl-Andersen 3 , Jon Eigill Johansen 3
1 Mobil Producing Nigeria (an ExxonMobil subsidiary), Lagos, Nigeria, 2 Geological Survey of Denmark and
Greenland (GEUS), Øster Voldgade 10, DK-1350, Copenhagen K, Denmark, 3 CHIRON AS, Stiklestadvn. 1,
NO-7041, Trondheim, Norway (corresponding author:olukayode.j.samuel@exxonmobil.com)
The recognition of certain molecular compounds that
represent specific processes and products in time and
space over varying biological and chemical conditions
in the geosphere and their successful linkage to their
natural products in the biosphere has permitted the
use of compounds like oleanane, lupane,
gammacerane and bicadinanes in characterising
sedimentary organic matter and petroleum. Four
previously unreported seco-oleananes identified as
A1, A2, B1, B2 and a compound ―C‖ previously
identified as seco-hopane (Schmitter et al., 1982,
Fig.1) all occurring in Late Cretaceous/Tertiary Deltaic
oils of Assam, Beaufort-Mackenzie, Gulf of Mexico,
Niger Delta and Kutei basins are hereby reported.
The ―A‖ and ―B‖ series elute as isomeric doublets (Fig.
1). All the seco-oleananes contain the base peak m/z
123 ion and significant m/z 109 and m/z 137 ions in
their mass spectra. Compound C (seco-hopane) was
found to be present in both non-deltaic (North Sea)
and deltaic oil samples irrespective of the basin,
organic matter source and the source rock age.
Only seco-oleanane B2 was successfully synthesized
under laboratory condition of isomerisation and
hydrogenation of oleanenes mixture from pure lup-
20(29)-ene prepared from birch-bark. The
observations suggest that the natural B2 in the oil was
probably formed under conditions of isomerisation
and hydrogenation of acid catalysed ring-C opened
product of oleanenes derived from angiosperm higher
plant precursors. Such Ring C opening mechanism
can occur at super acidic sites on clay minerals. NMR
data confirm that A2 and B2 are isomeric 8, 14 secooleananes
(i.e. oleanane with an opened C-ring).
NMR also supports structures for B2 and A2 in which
both CH3-26 and CH3-27 have inverted configurations
compared to their suggested oleananoid precursors,
and thus isomerised to thermodynamically more
stable products.
The presence and abundance of A1, A2, B1, B2 show
a correspondence with the oleananes in an oil (Fig. 2),
thus suggesting a similar terrigenous angiosperm
higher plants precursor. K-index (K-index =
(A1+A2+B1+B2)/C) co-varies with oleanane index,
thus permitting K-index‘s usage in discriminating
organofacies among oils in the same basin (Fig. 2).
Fig. 1. M/z 414-123 GC-MS-MS transition showing the
distribution of the seco-oleananes A1, A2, B1, B2 and secohopane
―C‖ in end-member oils of the Niger Delta Basin.
K-Index
14
12
10
8
6
4
2
0
A1
A2
A1 A2
A1
A2
B1
B1
B1
B2
B2
B2
Assam
Beaufort-Mackenzie
Gulf of Mexico
Kutei
Niger Delta
C
C
C
C
NDO02 (Shallow water Terrigenous)
OL index = 0.57
NDO30 (shallow water mixed facie)
OL index = 0.41
NDO23 (Deepwater marine)
OL index = 0.25
North Sea (marine)
OL index = 0.00
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Oleanane Index
Fig. 2. Plot of oleanane and K-indices for some Tertiary
deltaic oils.
REFERENCE:
Schmitter et al., 1982. Occurrence of novel tetracyclic
geochemical markers: 8,14-seco-hopanes in a
Nigerian crude oil. GCA 46, 2345-2350
96

Wednesday Oral Presentations
97

O-38
Microbial communities associated to deep subsurface coal
layers: A review of the DEBITS project
Kai Mangelsdorf 1 , Clemens Glombitza 1,2 , Andrea Vieth 1 , Tiem Vu Thi Anh 1 , Jens
Kallmeyer 2 , Klaus Zink 3 , Richard Sykes 3 , R. John Parkes 4 , John Fry 4 , Brian Horsfield 1
1 Helmholtz Centre Potsdam GFZ German Research Centre for Geosciences, 14473 Potsdam, Germany,
2 University of Potsdam, 14476 Golm, Germany, 3 GNS Science, Lower Hutt 5040, New Zealand, 4 School of
Earth, Ocean and Planetary Sciences, Cardiff University, Cardiff CF10 3YE, United Kingdom
(corresponding author:K.Mangelsdorf@gfz-potsdam.de)
The DEBITS (Deep Biosphere in Terrestrial System)
project was a joint study between geologists,
biogeochemists and microbiologists from New Zealand
(NZ), Germany and the UK and was dedicated to the
investigation of deep microbial communities associated
to lignite and coal layers in terrestrial environments.
Within the project a 148 m deep well was drilled in the
Waikato coal area on the North Island of NZ, penetrating
several lignite/coal layers intercalated between sand, silt
and clay lithologies. Additionally, a coal series covering a
maturity range from 0.28 to 0.8% vitrinite reflectance (R0,
diagenesis to beginning of main catagenesis) was
collected from several mines and outcrops on the North
and South Island of NZ.
Microbiological investigations reveal a high molecular
prokaryotic diversity, with some groups of bacteria and
archaea similar to the marine deep biosphere. While
there are partly similar bacteria above and below the
unconformity, archaeal populations are different.
Microbial communities and activity changed with
lithology. Substantial numbers of viable heterotrophs and
lignite-degrading bacteria were present throughout the
whole DEBITS core.
Phospholipids, being molecular indicators for living
bacteria, were detected in sedimentary succession
associated to lignite and coal layers indicating that
substrates are released from the organic carbon rich
lignite and coal layers to sustain a microbial ecosystem in
adjacent clay and mainly silt and sand layers. In selected
transects petrological investigations show an enhanced
permeability in the sand layers.
Water extraction of the lignites and coals shows that the
organic carbon rich lithologies contain substantial
amounts of small organic acids such as formiate, acetate
and oxalate being important substrates for microbial
metabolism. Thus, pore water of the coal layers provide
sufficient substrates to feed associated microbial
populations.
To investigate the potential of these coals to provide
appropriate substrate for deep microbial life, the amount
of kerogen bound low molecular weight organic acids
(LMWOA) were determined in a series of NZ coals of
different thermal maturity. Kerogen-bound formate,
acetate and oxalate were detected in all samples.
However, their abundance decreases with increasing
maturity of the coals suggesting that the main release of
these compounds is related to the diagenetic and early
catagenetic phases, a range where temperature
conditions are still compatible with microbial life. The
release of these substrates might be controlled by abiotic
(equilibrium reactions with the pore water) and biotic
processes. First assessment of the feedstock pool
indicates that the NZ coals exhibit the potential to sustain
associated deep terrestrial microbial life over geological
time spans.
At greater depth, when geothermally driven processes
become more and more important, an additional
substrate pool becomes available for deep microbial
ecosystems. For NZ coals the onset of the main phase of
geothermal hydrocarbon generation was determined at
0.55 to 0.6% R0 (main catagenesis) at temperatures
being presumably above the limit of deep subsurface life.
However, it was shown that already at lower maturity (0.4
% R0) the thermal generation of hydrocarbons slowly
begins. Thus, during early catagenesis geothermally
released hydrocarbons form another possible feedstock
for deep microbial life. Indications for this are provided by
NZ coals from the early catagenetic stage. The C16 and
C18 fatty acids, being also main constituents of bacterial
cell membranes, initially decrease with ongoing
maturation, but during the early catagenesis they
significantly increase before decreasing again at higher
maturity.
The interdisciplinary approach in the DEBITS project
allowed a deep insight into the type, abundance and
distribution of terrestrial microbial ecosystems associated
to lignite and coal layers. Furthermore, it broadened our
understanding on feedstock supply and optimal life
habitats for deeply buried microorganisms.
98

O-39
The fate of terrestrial organic matter in the Yangtze river- East
China sea system and its implications for the use of terrestrial
organic proxies
Chun Zhu 1 , Thomas Wagner 2 , Helen Talbot 2 , Johan Weijers 1,3 , Richard Pancost 1
1 Organic Geochemistry Unit, Bristol Biogeochemistry Research Centre, School of Chemistry, University of
Bristol, Bristol, United Kingdom, 2 School of Civil Engineering and Geosciences, Newcastle University,
Newcastle, United Kingdom, 3 Utrecht University, department of Earth Sciences – Geochemistry, Utrecht,
Netherlands (corresponding author:czhu@uni-bremen.de)
Burial of organic carbon (OC) in marine
sediments represents the 2 nd largest sink of
atmospheric CO2 over geological time scales.
Although continental shelves receive massive OC
inputs, their role in OC accumulation vs. degradation
is still under debate. The Yangtze River-dominated
East China Sea (YR-ECS; Fig. 1) is characterized by
massive terrestrial inputs (the YR is the world‘s 4 th
largest river in terms of sediment discharge) onto a
well-ventilated, shallow (500 km)
continental shelf, distinct from most narrow shelves in
the world. We examine the unique role of the ECS on
the fate of terrestrial organic matter (TOM) and its
implications for the use of terrestrial biomarkers.
Highly degraded soil OM and organic pollutants
dominate the YR sediments. Such OM is degraded
effectively in the estuary, particularly in the turbidity
maximum zone, where an enhanced bacterial activity,
including the bloom of methane oxidizing bacteria, is
also recorded by higher concentrations and structural
diversity of bacteriohopanepolyols (BHPs). Although
TOM has been extensively degraded in the watershed
and estuary, degradation of TOM clearly continues
along the coast and across the shelf, which is driven
by constant coastal currents and intermittent bottom
currents. Due to strong winnowing, few riverdischarged
sediments are accumulated on the open
shelf whereas relict sands deposited during the low
sea level stands occur widely on the seafloor. Those
sands contain a persistent amount of relict OC (ca.
0.1%), which appears to be δ 13 C-depleted (ca. -24‰)
but terrestrial biomarker-absent. Relict OC on the
sandy open ECS shelf accounts for ~170% of the
particulate OC annually discharged by the YR. Given
the globally wide occurrence of relict sands, a
persistent amount of relict OC may complicate the
modern TOM budget on continental shelves.
The behaviour of novel soil bacterial biomarkers
including BHPs and GDGTs (glycerol dialkyl glycerol
tetraethers) in the YR-ECS system was examined.
BHP distribution from the watershed to the shelf edge
indicates a fundamental difference in hopanoidproducing
communities between soils (source) and
sediments (sink). The Rsoil index, based on the ratio of
soil-marker BHPs vs. bacteriohopanetetraol, is
proposed as a new approach to track soil OM
distribution in marine sediments. This index displays a
strong correlation (R 2 =0.75) with the BIT index and
moderate correlations with land plant biomarkerderived
proxies in this setting. Branched GDGT-based
proxies for soil pH and air temperature do not reflect
the actual catchment environmental conditions due to
their extensive degradation in the estuary and in-situ
production on the well-ventilated ECS.
Finally, the fidelity of a range of proxies for TOM
input is examined. All proxies showed similar land-sea
trends; however, two factors impact their applicability
significantly: 1) the distinct reactivity, with a
decreasing degradability order: soil-marker BHPs > αamyrin
> β-amyrin > taraxerol > lignin > HMW nalkanols
> HMW n-alkanes, and similarly, the Rsoil
changing faster than the BIT which changes faster
than δ 13 Corg; 2) the strong regional variations in
marine biomarker distributions, which complicate the
normalization of terrestrial signals. We thus suggest
using a multi-proxy approach, considering the nature
of biomarkers and the depositional settings, when
reconstructing OC supply on continental shelves.
Fig.1. Sampling sites of surface sediment (0-5 cm) in
the YR-ECS system
99

O-40
The importance of geochemical analysis in shale gas plays:
beyond just the organic components
Harry Dembicki, Jonathan Madren
Anadarko Petroleum Corporation, Houston, United States of America (corresponding
author:harry.dembicki@anadarko.com)
Shale gas plays are often viewed simply as
black shales that are sufficiently rich in organic
matter, at a high enough maturity, and within
economic depths for horizontal drilling that can be
induced to produce gas by artificially fracturing the
shale. However, experience with these
unconventional petroleum systems has shown that
although they have some commonality, more often
they are defined by unique sets of characteristics that
contribute to their successful development.
The Floyd shale in the Black Warrior Basin
has long been considered a potential shale gas play.
It is a known source rock in the basin, responsible for
conventional oil and gas production from
Mississippian age deltaic sands. It is also the
stratigraphic equivalent of successful shale gas plays
in the Barnett Shale in the Fort Worth Basin and the
Fayetteville Shale in the Arkoma Basin. Within the
Black Warrior Basin, there are areas where the Floyd
shale has an adequate thickness (up to 200 ft), has a
high enough organic matter content (2.0-7.0 % TOC),
and has reached a high enough thermal maturity
(vitrinite reflectance >1.30 % Ro) to pass the initial
screening for a shale gas opportunity. But tests of the
interval with both vertical and horizontal wells have
yet to produce gas volumes approaching commercial
quantities.
In order to determine what is limiting the
deliverability of gas from the Floyd Shale, the
characteristics of these sediments were compared to
more successful shale gas plays including the Eagle
Ford Shale (Cretaceous, Maverick Basin), Haynesville
Shale (Jurassic, East Texas Basin), and the Marcellus
Shale (Devonian, Appalachian Basin). The results
shows the Floyd compares favorably with respect to
kerogen type, organic matter content, thermal
maturity, and bulk mineralogy with at least one or
more of these plays. In addition, analysis of core and
cuttings samples indicates the Floyd Shale is charged
with gas and monitoring of the well completion
process indicated that fractures were opened during
reservoir stimulation. So why did the Floyd shale fail
to produce?
Detailed analysis of the mineralogy and
related rock properties of the sediments points toward
the reservoir characteristics of the shale as the cause.
Although bulk mineralogy compares favorably with
other shale plays, an examination of the clay species
present in the Floyd shale suggests potential water
sensitivity issues could have resulted in collapse of
fractures and embedment of proppant. This is a
reminder that shale is not just the source but also the
reservoir, and it demonstrates the importance of
integrating all data, including rock properties, and not
just geochemistry when evaluating source rocks as
potential shale gas plays.
100

O-41
Multi technique approach resolves soft-tissue preservation in 50
million year old reptile skin
Bart van Dongen 1,2 , Phill Manning 1,2,6 , Nick Edwards 1,2 , Holly Barden 1,2 , Peter Larson 3 ,
Uwe Bergmann 4 , William Sellers 5 , Roy Wogelius 1,2
1 University of Manchester, School of Earth, Atmospheric, and Environmental Sciences, Manchester, United
Kingdom, 2 University of Manchester, Williamson Research Centre for Molecular Environmental Science,
Manchester, United Kingdom, 3 Black Hills Institute of Geological Research, Inc., Hill City, United States of
America, 4 SLAC National Accelerator Laboratory, Linac Coherent Light Source, Menlo Park, United States
of America, 5 University of Manchester, Faculty of Life Sciences, Manchester, United Kingdom, 6 University of
Pennsylvania, Department of Earth and Environmental Sciences, Philadelphia, United States of America
(corresponding author:Bart.vandongen@manchester.ac.uk)
Recent palaeontological research suggests that
soft-tissue may be preserved during fossilization. A
recent study of a well-preserved Upper Cretaceous
dinosaur (specimen MRF-03) unequivocally showed
differences between the organic compounds present
within the fossilized skin envelope and the enclosing
sedimentary matrix [1], suggesting preservation of
residue from endogenous organic compounds, e.g. β
keratin, within soft tissue. Unfortunately, mapping of
the β keratin products in the skin was not possible
due to the friable nature of the available samples.
However, it suggested that using a combination of
modern analytical techniques, including infra-red
mapping of organic functional groups, and more
suitable specimens may provide new constraints on
interpreting fossil preservation without requiring
destructive sampling. Therefore, a well-preserved
fossilized reptile skin (Squamata: Reptilia tent; Fig.
1A) from the Green River Formation (Utah, USA; ~50
million year old) was analysed using FTIR mapping,
Py-GC/MS and Synchrotron Rapid Scanning X-Ray
Fluorescence (SRS-XRF).
FTIR mapping of organic functional units (Fig. 1D)
show a spatial distribution of endogenous organic
components, e.g amide and sulfur compounds,
comparable to the structure of extant tissue indicating
that these are most likely derived from the original β
keratin present in the skin. This is further confirmed
by absence of the intense amide or thiol absorption
bands in fossil leaf and other non-skin derived organic
matter from the same geological formation.
Maps/spectra from the fossil are also directly
comparable to extant reptile skin. Py-GC/MS analyses
yielded diagnostic n-alkane/alkene patterns with
comparable distributions for fossil plant material and
the sedimentary matrix, suggesting that the later
contains leaf derived organics. In contrast, the
distribution pattern of the fossil skin is completely
different, suggesting that there is minimal transfer of
organics from the matrix to the skin, confirming that
the compounds mapped by FTIR are original to the
skin. Furthermore, the Py-GC/MS results also
confirmed that the organic signal identified is most
likely not of aerobic microbial origin. Elemental
mapping using SRS-XRF further showed that the
presence of both organic sulfur (Fig. 1B) and trace
metals are almost exclusively observed in the skin,
with the later probably due to chelation by melanin.
Their distribution patterns correlate well with the
functional groups mapped by FTIR.
Taken together, all the analyses performed in this
study strongly suggest that the fossilized reptile skin
is not a simple impression, mineralized replacement,
or an amorphous organic carbon film, but contains a
partial remnant of the living organism‘s original
organics, in this case derived from proteinaceous
skin. In addition, it shows that valuable information
can be obtained from rare specimens where
destructive sampling is not possible.
Fig.1. (A) photograph, (B) organic sulfur distribution
map, (C) reflected light map and (D) FTIR absorption
map at 1653cm -1 [box in Fig. 1A] of fossilised skin.
References
[1] Manning, P.L. et al. Proc Royal Soc. B 276, 3429
3437 (2009)
101

O-42
Charge history and petroleum geochemistry of dual phase
accumulations on the Norwegian Continental Shelf using
comparative analysis of the liquid and vapour phase
Linda Schulz 1 , Michael Erdman 2 , Olaf Thießen 3
1 Statoil ASA, Exploration, Drammensveien 264, 0246 OSLO, Norway, 2 Statoil ASA, Exploration,
Sandsliveien 90, 5020 BERGEN, Norway, 3 Statoil ASA, Exploration, Grenseveien 21, 4035 STAVANGER,
Norway (corresponding author:lksc@statoil.com)
Understanding charge history of dual phase
accumulations may be challenging due to multiple source
contributions and phase separations. Identical gas data
of the oil associated gas and the non-associated gas
could indicate a single source rock whereas additional
data from the gasoline and biomarkers fraction results in
a different picture pointing towards multiple sources. The
main objective of this study has been to investigate
commonly applied geochemical parameters from all
hydrocarbon fractions in dual phase accumulations.
Additional PVT data and pyrolysis data from the main
sources have been considered to improve the
understanding of the charge history. Case studies from
the Norwegian Continental Shelf are used.
The first case shows a reservoir accumulation where the
petroleum most likely has been generated by a marine
source at peak to late-oil maturity. The gas isotope
profiles of oil associated gas and the gas-condensate are
identical (Fig.1, case 1). The maturity of the gasoline
fraction in the gas-condensate phase is slightly higher
than in the oil phase. The dual phase state appears best
explained by phase separation due to reduced pressure
and temperature conditions which is supported by
saturation pressures close to reservoir pressures. The
gas mass fraction of the discovery is about 0.44, while
pyrolysis experiments of marine source rock samples
indicate gas mass fractions of around 0.15 to 0.22 with
only minor increase at high maturity. Volumetric
recombination of both phases in PVTsim shows that the
charge fluid has a high GOR and possibly was an
undersaturated gas/ condensate. The high gas mass
fraction could be explained by liquid loss on the migration
pathway. Additional gas contributed from secondary
cracking is excluded from biomarker versus diamondoid
concentrations. Another explanation for the high gas
fraction could be that oil has been migrated up-flanks
whereas the gas has been efficiently trapped.
The second case shows accumulations in two reservoirs
which are separated by a pressure barrier at present day.
The oil associated gas in the lower reservoir shows a
very low gas mass fractions of about 0.07. The upper
reservoir contains a gas condensate with a gas mass
fraction of about 0.92. However, even volumetric
recombination of both phases will not increase the oil/gas
mass fraction above about 0.08 for the whole
accumulation. Thus, significant gas loss best explains the
observed ratios. At the same time the oil associated gas
and the gas-condensate do show similar isotope profiles
(Fig. 1, case 2). Moreover, gasoline and C15+ range
hydrocarbons indicate that the oil has been generated by
a source rock dominated by terrigenous organic matter,
while the gas-condensate has a marine origin. In spite of
partial loss of gas fraction, complex mixing and alteration
processes the gas isotope profiles appear similar in both
reservoirs. This observation appears to be ubiquitous,
pointing to homogenization of compositional differences
for gas being very fast in geologic time, also across
phase boundaries.
The conclusion is that lack of differences in isotopic
composition between the oil associated and nonassociated
gases not necessarily indicates that gas cap
and oil leg have the same origin. Consideration of all
petroleum fractions in both phases, ideally combined with
mass balance and PVT data, allows for a proper
interpretation of the charge history of dual phase
accumulations. This can contribute to a realistic
evaluation of the prospectivity of the areas adjacent to
discoveries.
� 13 C (‰) PDB
-30
-40
-50
Single-phase system
OIL (for comparison only)
Two-phase systems
1 - GAS_COND (GOR: 1900)
1 - OIL (GOR: 246)
2 - GAS_COND (GOR: 12585)
2 - OIL (GOR: 92)
Methane Ethane Propane i-Butane n-Butane
Fig.1. Compound specific carbon isotope profiles of oil-associated and free
gases/gas-condensates of two-phase systems. The grey shaded area represents
the carbon isotopic range of the gas generation index (GGI) according to Clayton
(1991).
102

O-43
Molecular study of organic residues in an exceptional collection
of potteries from Deir el-Médineh (XVIIIth dynasty, Egypt)
Claire Bastien 1 , Armelle Charrié-Duhaut 1 , Geneviève Pierrat-Bonnefois 2 , Jacques
Connan 1 , Claude Le Milbeau 3 , Jorge Spangenberg 4
1 Laboratoire de Biogéochimie Moléculaire (UMR 7177 CNRS et Université de Strasbourg), Strasbourg,
France, 2 Département des Antiquités Egyptiennes (Musée du Louvre), Paris, France, 3 Institut des Sciences
de la Terre d'Orléans (Université d'Orléans - INSU-CNRS), Orléans, France, 4 Institute of Mineralogy and
Geochemistry, Lausanne, Switzerland (corresponding author:acharrie@unistra.fr)
Within this study of molecular archaeology,
an exceptional set of Egyptian organic remains stored
in containers from Deir el-Médineh (XVIII th dynasty),
and put at disposal by the Department of Egyptian
Antiquities of the Louvre Museum has been analyzed.
These containers, still full (Figure 1), were found in a
necropolis located on the east side of the Valley of the
Kings. This necropolis, excavated by Bernard Bruyère
in 1933, was occupied by a population, who seemed
to have a particular socio-cultural profile (Pierrat-
Bonnefois, 2002). The identification of the complex
organic mixtures, present inside the containers via the
biomarkers analysis, may help to have some
information about this population, and to understand
their funeral rites.
Figure 1: Photographs of two containers (E14013 and
E16446).
The molecular and isotopic study of a
diversified sampling of these organic residues, based
on chromatographic techniques and mass
spectrometry (GC-MS, LC-MS and GC-C-irmMS),
was carried out. Half of the analyzed samples
contained about 40% of triglycerides which are
indicators of a lipid base (animal fat or vegetable oil).
Hydrolysis and oxidation products of triacylglycerols
are detected (diacylglycerols, monoacylglycerols, free
fatty acids, δ-lactones, γ-lactones, α,ω-dicarboxylic
acids, and dihydroxylated fatty acids). These results
and the analysis of stable carbon isotopes of the
methyl esters favoured plants over animals as the
lipid source (Romanus, 2008). The presence of odd
numbered n-alkanes, phytosterols and co-elutions of
wax esters, has highlighted the complex mixtures with
cuticular waxes of flowers or leaves (Ribechini, 2008).
The absence of diagnostic terpenic structures
excludes the use of natural resins. The others
samples are characterized by the presence of
degradation products of fatty material, but the
triglycerides are not detected, which could indicate
different preparation methods.
This investigation was completed by the study of fresh
plant oils and of oils submitted to thermal degradation
in order to determine their molecular fingerprint and
the alteration products.
These archaeological substances seem to
belong to the same family: ointments or cosmetics.
They were used by the population of the necropolis
but are they in relation with their profession or just
offerings for the eternity travel and their afterlife?
Pierrat-Bonnefois, G. (2002). Cimetière est du village
ou cimetière à l‘est de Deir el-Médineh?, Deir el-
Médineh et la Vallée des Rois, colloque, Musée du
Louvre, Edition Khéops-Musée du Louvre
Ribechini, E., Modugno, F., Colombini, M.P.,
Evershed, R.P. (2008). Gas chromatographic and
mass spectrometric investigations of organic residues
from Roman glass unguentaria. Journal of
Chromatography A, 1183, 158-169.
Romanus, K., Van Neer, W., Marinova, E., Verbeke,
K., Luypaerts A., Accardo, S., Hermans, I., Jacobs,
P., De Vos, D., Waelkens, M. (2008). Brassicaceae
seed oil identified as illuminant in Nilotic shells from a
first millenium AD Coptic church in Bawit, Egypt. Anal
Bioanal Chem, 390, 783-793.
103

O-44
Bacterial formation of (di)ether lipids: a state of the art
Vincent Grossi 1 , Agnès Hirschler-Réa 2 , Philippe Schaeffer 3 , Cristiana Cravo-Laureau 4
1 CNRS - Université de Lyon, Villeurbanne, France, 2 IRD, Universités de Provence et de la Méditerranée,
Marseille, France, 3 CNRS - Université de Strasbourg, Strasbourg, France, 4 Université de Pau et des Pays
de l’Adour, Pau, France (corresponding author:vincent.grossi@univ-lyon1.fr)
The actual knowledge of the biosynthesis of
glycerol ether lipids by Bacteria will be reviewed and
expanded with recent results showing for the first time
the production of dialkyl glycerol diethers (DGDs) by a
mesophilic (hydrocarbon-degrading) marine sulfatereducing
bacterium (SRB).
One of the distinguishing features between Archaea
and Bacteria is the chemical composition of their
cellular membranes. Bacteria generally synthesise
phospholipids (non-isoprenoid alkyl chains esterified
to glycerol) whereas archaeal membrane lipids are
composed of isoprenoid di- and tetraethers of glycerol
(isoprenoid DGDs and GDGTs, respectively). These
different chemical structures have implication in term
of ecology and evolution, and are frequently used to
distinguish between Bacteria and Archaea in
(paleo)environmental studies. Non-isoprenoid DGDs
and GDGTs constitute an exception to these chemical
distinctions as they exhibit an intriguing combination
of structural characteristics of Bacteria and Archaea.
Non-isoprenoid DGDs are relatively uncommon in
bacteria but have been reported in some
(hyper)thermophilic bacteria, planctomycetes and
myxobacteria [1]. However, these biomarkers are
omnipresent in different non-thermophilic soils and
aquatic sediments [especially those where anaerobic
oxidation of methane (AOM) occurs], where they are
supposed to originate from anaerobic bacteria
involved in sulfur and/or methane cycles and in
carbonate precipitation [2]. To date, this biological
origin is not demonstrated and the physiological role
of DGDs remains unknown.
The lipid composition of a newly isolated
hydrocarbon-degrading marine SRB, able to grow
between 20°C and 40°C, is dominated by nonisoprenoid
mono- and di-ethers of glycerol. The
chemical composition of ether lipids appears strongly
dependent on that of the growth substrate. Ethers
formed during growth on mid-chain n-alkenes (C14-
C16) have alkyl chains in the same carbon range,
whereas growth on shorter substrates (pyruvate,
octanoate, etc.) generally yields a more complex
mixture of DGDs. Interestingly, the fatty acid
composition of the strain resembles that of the ether
alkyl chains, suggesting a biosynthetic link between
both classes of compounds. Cultures performed with
synthetic (per)deuterated n-alkenes support these
links by unambiguously demonstrating the direct
incorporation of degradation intermediates [i.e.
corresponding labelled alcohols and (branched-) fatty
acids] into glycerol monoether/monoester and diether
lipids (Fig. 1).
R
R CH2OH
glycerol
diethers
sn-Glycerol-3-P
R COOH
+
ether/
ester
H
HO O
P
10-Me branching
10
�-oxidation
HO
R COOH
R COOH
Fig. 1. Formation of glycerol (di)ethers during the anaerobic
oxidation of n-alkenes by a newly isolated mesophilic SRB.
Besides describing the first production of diether
lipids in a mesophilic and heterotrophic anaerobic
bacterium, our work further extends the metabolic
pathways of unsaturated hydrocarbons in anaerobic
environments. The major geochemical and
biochemical implications of these findings and the
comparison of this strain with SRB involved in AOM
and/or carbonate precipitation will be discussed.
References
[1] Weijers, J.W., Schouten, S., Hopmans, E.C.,
Geenevasen, J.A., David, O.R., Coleman, J.M., et al. (2006)
Environmental Microbiology 8, 648-657.
[2] Bradley, A.S., Fredricks, H., Hinrichs K.-U.,
Summons, R.E. (2009) Organic Geochemistry 40, 1169-
1178.
104

O-45
Advancing trace-level analysis of marker compounds in ice
cores to generate records of South American fire activity
Matthew Makou 1 , Lonnie Thompson 1 , Timothy Eglinton 2 , Daniel Montluçon 2
1 Byrd Polar Research Center, Ohio State University, Columbus, OH, United States of America, 2 ETH Zurich,
Zurich, Switzerland (corresponding author:makou.1@osu.edu)
Stir bar sorptive extraction, which provides a
means of quickly and quantitatively recovering semivolatile
lipids from aqueous samples, was applied in
conjunction with coupled thermal desorption and gas
chromatography/time-of-flight mass spectrometry to
measure trace-level marker compounds preserved in
an ice core. We generated multi-molecular records
from the Quelccaya Ice Cap in Peru, which is situated
along the eastern flank of the Andes and thus is well
positioned for deposition of higher plant-derived
compounds originating from both the Amazon Basin
and higher elevations. Our analytical approach proved
effective in recovering several different types of
compounds from small volumes of melted ice (10-30
ml), resulting in century-scale fire and vegetation
records at better-than-annual resolution. For example,
we successfully recovered and analyzed diterpenoids,
fatty acids, and alkyl amides with mean
concentrations as low as 10 pg/ml. Diterpenoids such
as dehydroabietin and a variant of phenanthrenone
represent the biomarkers of greatest utility due to their
inferred specificity for conifer burning. Abrupt changes
in compound abundance are superimposed on
decadal variability (see figure) and are not strictly
associated with high-altitude temperature and aridity
changes inferred from inorganic ice core climate
proxies. This suggests that our approach provides
new lines of climate evidence indicative of tropical
carbon cycling. Inputs of organic carbon to the Andes
likely reflect a combination of sources from
anthropogenic burning and natural fires related to
aridity, and include both high and low elevation
vegetation. We are presently applying these
techniques to older ice to develop records of tropical
burning related to late Holocene climate variability
and Amazon Basin societal change.
Fig. 1. Records of selected marker compounds
preserved in the Quelccaya ice core. Elevated relative
concentrations suggest enhanced deposition of firederived
aerosols. Disparities between records likely
arise from the vegetation source specificity of each
compound.
105

O-46
Development of a novel tool for paleoclimate research based on
compound-specific δ18O analyses of (hemi-)cellulose-derived
monosaccharides
Michael Zech 1,2 , Bruno Glaser 2 , Dieter Juchelka 3 , Karsten Kalbitz 4 , Christoph Mayr 5 ,
Mario Tuthorn 1 , Roland Werner 6
1 Chair of Geomorphology and Soil Physics Department, University of Bayreuth, Bayreuth, Germany,
2 Department of Terrestrial Biogeochemistry, Martin-Luther University Halle-Wittenberg, Halle, Germany,
3 Thermo Fisher Scientific, Bremen, Germany, 4 Institute for Biodiversity and Ecosystem Dynamics, University
of Amsterdam, Amsterdam, Netherlands, 5 Institute of Geography, Friedrich-Alexander University Erlangen-
Nürnberg, Erlangen, Germany, 6 Institute of Plant, Animal and Agroecosystem Sciences, ETH Zurich, Zurich,
Switzerland (corresponding author:michael_zech@gmx.de)
For about 10 years, technical improvements allow the
coupling of gas chromatographs with isotope ratio
mass spectrometers via online pyrolysis reactors
(GC-Py-IRMS). While compound-specific �D analyses
e.g. of plant-derived n-alkanes for palaeoclimate
studies were readily adopted by the scientific
communities, there are only a few studies having
applied compound-specific �18O analyses, so far. We
see large potential for this method especially in
palaeoclimate research, because it is well known that
not only �D, but also �18O of precipitation and of
certain chemical compounds of plants (e.g. cellulose)
depend on climate parameters.
In order to overcome extraction, purification and
hygroscopicity problems of so far applied cellulose
methods based on TC/EA �18O analyses, we
developed a method for compound-specific �18O
analyses of plant-derived monosaccharides like
arabinose, fucose, xylose and rhamnose using GC-
Py-IRMS (Zech, M. and Glaser, B., 2009. Compoundspecific
�18O analyses of neutral sugars in soils using
gas chromatography–pyrolysis–isotope ratio mass
spectrometry: problems, possible solutions and a first
application. Rapid Communications in Mass
Spectrometry 23, 3522-3532).
� We propose to co-analyse n-alkanes
(hydrocarbons without oxygen atoms in the
molecules) in order to guarantee the absence of
oxygen contamination during measurements.
� The quantitative conversion of the analytes into
carbon monoxide (CO, m/z = 28) can be checked
by detecting also the mass m/z = 44 (carbon
dioxide, CO2).
� Theoretical considerations and experimental
results demonstrate that oxygen exchange
reactions do neither occur to (hemi-)cellulose
monosaccharides in natural archives nor during
our analytical workup.
� Results from an experimental field study suggest
the absence of oxygen fractionation of (hemi-)
cellulose monosaccharides during litter
decomposition.
� The sensitivity and comparability of the novel
proxy with conventional bulk �18O cellulose
methods is confirmed by results from a climate
chamber experiment.
� A first application is provided for Late Glacial and
Holocene high mountain lake sediment cores
from Helambu Himal, Nepal. Accordingly, �18O
variations of hemicellulose sugars record the
variability of the Asian Monsoon.
� More recent methodological improvements allow
the reductive elimination of the oxygen atoms in
C1-position and the �18O-analysis of glucose.
We conclude that in the near future the novel and
here presented method may become a valuable tool
in palaeoclimate research. It can be applied to a wide
range of different climate archives such as tree-rings,
peat bogs, lacustrine sediments and loess-palaeosol
sequences, and has potential in authenticity
evaluation of food and beverage, too.
106

O-47
Current developments and challenges in compound-specific
radiocarbon analysis
Rienk Smittenberg 1,2,3 , Merle Gierga 1 , Axel Birkholz 1 , Irka Hajdas 4 , Lukas Wacker 4 ,
Michael Schmidt 2 , Stefano Bernasconi 1,2
1 ETH Zurich, Geology, Zurich, Switzerland, 2 University of Zurich, Geography, Zurich, Switzerland,
3 Stockholm University, Geology, Stockholm, Sweden, 4 ETH Zurich, Ion Beam Physics, Zurich, Switzerland
(corresponding author: rienk.smittenberg@geo.su.se)
Besides its use as a dating tool for carbonaceous
materials, radiocarbon ( 14 C) analysis is also a
powerful tool for studies pertaining the carbon cycle,
from the global [1] to the local [2] scale, as well as
other biogeochemical processes. The 5730 yr half-life
of naturally-produced 14 C can provide insights into the
operation of the C cycle over longer time scales, while
C derived from fossil fuel burning ( 14 C-dead), as well
as the 14 C-spike introduced by atmospheric bomb
tests of the mid-20th century, are useful tracers for
the examination of C-cycling over shorter time scales.
Within this framework it is of great interest to look at
different fractions of the carbon pool, down to the
molecular scale, in order to also gain source-specific
insights.
The general introduction of Accelerator Mass
Spectrometry (AMS) in the early 1990s made it
possible to decrease sample size, which triggered the
introduction of compound-specific 14 C analysis in the
1990s [3]. Until recently, 50 microgram C was
regarded as a small sample, but recent improvements
in the design of AMS systems, ion sources and
sample introduction into the AMS, e.g. directly as CO2
gas instead of the traditional graphite, have lowered
the measurable amount of C to less than 5
micrograms [4-6].
Quality control and standard normalization is
traditionally performed by measuring reference
materials (' 14 C-dead' coal and ' 14 C modern' oxalic
acid) after combustion and graphitization. This basic
normalization will always need to be performed.
However, for very small samples significant offsets
from real values can be observed. These are summed
effects of sample preparation: 1) Insufficient
purification/isolation from the matrix, for instance in
the case of individual compounds. 2) Contaminations
added during the purification procedure, sample
handling, and combustion to CO2. 3) Transfer of CO2
to the ion source and subsequent continuous flow
ionization. The accuracy of small-sample radiocarbon
values can only be evaluated with a rigorous
assessment of the parts of this summed factor (see
also e.g. [7]), which may be different for different
types of sample. Hence there is a need for 14 C
standards that are the same as, or as similar as
possible to, the analytes of interest (e.g. a specific
lipid compound, protein, or batch of aerosols) in order
to evaluate and validate the preparation procedures.
We will present a general overview of small-scale
radiocarbon analysis as it is at present conducted at
the ETH Zürich. More specifically, we present a
comparison study between the purification of longchain
fatty acids by the traditionally used preparative
gas chromatography, with a method based on liquid
chromatography, as well as results from lake
sediment samples. Secondly we present a procedure
to isolate branched glycerol dialkyl glycerol
tetraethers, and 14 C results. Finally we present a new
HPLC-based method for the purification of benzene
carboxylic acids (BPCAs), which are molecular
markers for fire-derived black carbon, obtained by
nitric acid digestion of sediments, soils or other
matrices [8]. All these compounds are, once purified,
analyzed on the MIni CArbon Dating System
(MICADAS) equipped with a gas source [5,6].
Extensive testing of this system using a number of
standards indicates that routine compound-specific
radiocarbon analysis is possible on the 10 �g C level.
References:
[1] Galy, V., 2008. Science 322, 943; [2] Trumbore
S., 2009. Annu.Rev.Earth Pl.Sc. 37; [3] Eglinton, T.
I., 1996. Anal. Chem. 68, 904; [4] Bronk Ramsey, C.
1997, Nucl. Instr. Meth. Phys. Res. B 123, 539; [5]
Ruff, M., 2007. Radiocarbon 49, 307; [6] Ruff, M.,
2010. Nucl. Instr. Meth. Phys. Res. B268, 790; [7]
Shah, S. R., 2007. Radiocarbon 49, 82; [8] Schneider,
M.P.W., 2011, Org. Geochem.,42, 275.
107

O-48
Evolution of petroleum composition during generation and
expulsion - a case study on the Bakken Formation
Philipp Kuhn, Brian Horsfield, Rolando di Primio
GFZ German Research Centre for Geosciences, Potsdam, Germany (corresponding author:kuhn@gfzpotsdam.de)
The Devonian-Mississippian Bakken Formation of the
Williston Basin in central North America is generally
seen as a prime example of a self contained
petroleum system. It consists of the productive
reservoir member encased within the two source
rocks of the upper and lower Bakken Formation. A
distinguishing stratigraphic property of the Bakken
petroleum system is the immediate juxtaposition of
source and reservoir. This, coupled with negligible
influence of biodegradation, secondary cracking and
mixing from external sources make the Bakken
Formation a natural laboratory for studying expulsion
and retention phenomena, and their effects on
petroleum composition.
Based on a core sample set of more than 250
samples of all members of the Bakken and adjacent
formations from 22 wells, covering a natural maturity
range from 0.35 to 1.1% Ro as well as 27 produced
oil samples, the generation behaviour, the mass and
composition of the retained, expelled and produced
bitumen/petroleum was analyzed.
As a first step the transformation of the kerogen and
the evolution of the properties of the generated
hydrocarbon throughout the entire oil window were
characterized by Pyrolysis gas chromatography,
Rock-Eval pyrolysis (RE) and TOC measurements.
Further, the mass and composition of the retained
bitumen and its changes with maturity were
monitored: based on the S1 of RE and the bulk yield
of Thermovaporization gas chromatography a
maturity independent, low variability of the retained
bitumen per mass unit TOC was documented, which
remains below 8% of the original generation potential.
Thus, the Bakken source intervals are excellent
expellers, in agreement with earlier mass balancing
results [1+2] .
The extracted bitumen was further separated into four
fractions namely asphaltene (ASP) by precipitation,
and the aliphatic (SAT), aromatic (ARO), and hetero
compound (NSO) fractions (together comprising the
maltenes) using medium pressure liquid
chromatography [3] .
With increasing maturity the NSO yield falls from 60%
of the maltenes to about 30%. The SAT fraction
displays the exact opposite trend, with values
increasing from 20% of the maltene yield at the lowest
maturity to beyond 50% in the well exhibiting the
highest maturity. The ARO yield of the maltenes
varies between 15 and 30% without a significant trend
throughout the examined maturity range. The
asphaltene concentration reached a maximum of 30%
at a maturity of 433°C Tmax then dropping to 3% of the
retained bitumen at the highest maturity.
In contrast to the retained composition, extracted
material from the reservoir member did not display
any maturity related trends. In all sample extracts the
SAT fraction yield was dominant with ~60%, followed
by the ARO and NSO (10–30% each) and a low
percentage of ASP fraction (

O-49
Determination of effective source rocks for Quaternary biogenic
gas generation in the eastern Caidam Basin, NW China
Maowen Li 1 , Shuichang Zhang 2 , Yanhua Shuai 2 , Jenny Wong 3 , Julito Reyes 3 , Sneh
Achal 3
1 Sinopec Research Institute of Petroleum Exploration and Production, Beijing, China, 2 PetroChina Research
Institute of Petroleum Exploration and Development, Beijing, China, 3 Geological Survey of Canada, Calgary,
Canada (corresponding author:limw@pepris.com)
The Quaternary clastic sediments collected from the
eastern Qaidam Basin, NW China have been
investigated for their molecular geochemistry, stable
carbon and hydrogen isotopes, and organic and
inorganic petrology, where geochemical data of gas
samples from a number of large gas accumulations
clearly demonstrate a biogenic origin, likely formed by
anaerobic microbial breakdown of sedimentary
organic matter. The gases are dominated by
methane, with minor C2+ hydrocarbons, N2 and CO2
(all below 1%). The �13C values of methane in these
gases range from -68.51‰ to-65.00‰, typical of
biogenic gas. The��D values of methane in these
gases, ranging from-227.55‰ to -221.94‰, are much
higher than those generated from acetate
fermentation, indicating a probable origin from carbon
dioxide reduction. Quaternary strata in the study area
are characterized by inland evaporitic lacustrine
sediments, with generally low organic content (on
average only 0.3% TOC) and locally organic-rich
carbonaceous layers (up to 40% TOC). The organic
input is predominately from terrigenic herbaceous and
low shrubbery plants, relatively rich in cellulose,
hemicellulose, and carbohydrates such as starch, fat
and pectin. The average geothermal gradient in this
area is 25 oC/km, and the maximum temperature for
Quaternary sediments up to 2000 m in depth is still
below 70 oC or 0.5 %Ro. Against conventional
thinking, many previous studies on biogenic gas
generation suggest that the Quaternary deposit with a
low TOC content be the effective source rocks for the
bioigenic gases. The organic-rich carbonaceous
layers were deliberately excluded in the earlier rounds
of gas resource assessment, because mass balance
calculations in the literature claims that high TOC
content is not necessary for commercial biogenic gas
generation and a 10% conversion of sediments
containing greater than 0.2% TOC can potentially
generate a substantial amount of free gas phase.
Results of our petrographic study indicate that sulfate
occurs widely in the Quaternary sediments in eastern
Caidam Basin. Organic matter in almost all of the
organic-lean Quaternary samples (with less than 1%
TOC) are either inertinite or highly mineralized
organic detritus, co-occurring with sulfate and ferrous
oxide minerals. The trace amounts of organic extracts
in these samples also reveal strong molecular
evidence for oxidative degradation of sedimentary
organic matter. For example, the C29 sterane
transformation ratios are abnormally high, displaying
values normally expected in ―conventional peak oil
window‖. The data are clearly incompatible with the
low thermal maturity levels of the host sediments. As
factors such as contaminations from migrated
hydrocarbons, from drilling fluids, or laboratory
handling can be readily ruled out, the abnormal data
most likely indicate that these organic-lean sediments
were deposited and are still in aerobic environments
in spite of significant sedimentary burial! This is in
contrast with the organic-rich carbonaceous layers,
where molecular analysis of organic extracts indicates
highly anoxic depositional environments.
Petrographically, large amount of well-preserved plant
material co-occurs with pyrite, a reliable indicator for
anaerobic environment and sulfate-reducing bacteria.
The latter are common in anaerobic environments
where they aid in the degradation of organic
materials. The results indicate that only these organicrich
layers have been capable of providing the
competing methanogens with sufficiently available
substrates in subsequent diagenesis and biogenic
gas generation. When the sediments are buried to
some depth and reach the optimal temperatures for
methanogens to thrive, the dilution of water salinity by
groundwater infiltration would greatly facilitate the
flourish of the methanogens in shallow sediments and
hence the generation of large quantities of biogenic
methane.
109

O-50
Beyond Orgas- BP’s new predictive model for biogenic and
thermogenic gas expulsion from source rocks
Mark Osborne, Tony Barwise
BP Exploration Operating Co Ltd, Sunbury-on-Thames, United Kingdom (corresponding
author:Mark.Osborne@uk.bp.com)
BP‘s ‗Orgas‘ kinetic scheme, was created in the
1980‘s-early 1990‘s to predict the oil and gas volume
expelled from different source rock
organofacies[1,2,3]. The global kinetic model
assigned kinetic parameters based on gross
depositional environment and stratigraphic age-
useful in areas of low geochemical knowledge
including frontier exploration. The published scheme
has been implemented in most commercially available
basin modelling tools, becoming widely used
throughout the petroleum industry to the present day.
While Orgas is still considered to be technically
robust and pragmatic, BP has recently made
improvements to the scheme to provide enhanced
pre-drill predictions of the volume, composition and
physical properties of expelled petroleum fluids. This
information is important for understanding the likely
quality, value and volume of petroleum fluid that may
be present in a basin or prospect, for both
conventional or unconventional play types (e.g. shale
gas, coal bed methane, biogenic).
With regards to modelling of gas expulsion, the
modifications to our proprietary scheme fall into three
main categories:
1) Modelling of both biogenic (bacterial) and
thermogenic gas generation and expulsion. Our work
suggests biogenic gas is generated from typical
source rocks, as well as leaner sediments. Biogenic
and thermogenic gas should not be modelled
separately- they are part of the continuum of fluid
types that are generated during burial of most source
rocks (Fig 1).
2) A revised model for gas adsorption and retention.
Both adsorption of gas on kerogen and retention in
porosity are important factors controlling whether gas
remains trapped in a source rock or is expelled from
it. The old Orgas scheme considered only adsorption.
The new model is critical for the correct evaluation of
shale gas plays.
3) Prediction of the isotopic composition of the
expelled gases. As biogenic and then thermogenic
gas is generated and becomes mixed in the source,
the expelled gas isotopic composition systematically
evolves in a predictable manner. This model is
consistent with global observations from isotube data
collected from exploration wells.
Collectively these three modifications produce more
realistic assessments of gas expelled from (and
retained within) source rocks
Fig. 1. An example of biogenic and thermogenic
expulsion rates and their variance with source rock
thermal stress
References
[1] Pepper AS and Corvi PJ. Simple Kinetic Models of
Petroleum Formation: Oil and Gas Generation from
Kerogen. Marine and Petroleum Geology 12 (1995):
291-319.
[2] Pepper AS and Corvi PJ. Simple Kinetic Models of
Petroleum Formation: Modelling an Open System.
Marine and Petroleum Geology 12 (1995): 417-452.
[3] Pepper AS and Dodd TA. Simple Kinetic Models of
Petroleum Formation Part II: oil-gas cracking. Marine
and Petroleum Geology 12 (1995): 321-340.
110

O-51
Role of biosynthesis leading to the saw-toothed profile in δ13C
and δ2H of n-alkanes and systematic isotopic differences
between n-, iso- & anteiso-alkanes in leaf waxes of land plants
Youping Zhou 1,2 , Kliti Grice 1 , Hilary Stuart_Williams 2 , Graham Farquhar 2 , Charles
Hocart 2
1 Curtin University, Perth, Australia, 2 Australian National University, Canberra, Australia (corresponding
author:y.zhou@curtin.edu.au)
The n-fatty acids containing an even number of
carbons (ECN-n-FAs) in higher plants are synthesised
by repetitive addition of a 2 carbon unit from malonyl-
CoA (synthesised from acetyl CoA which is in turn
derived from pyruvate). The n-alkanes containing an
odd number of carbons (OCN-n-alkanes) are
generally formed by the decarboxylation of ECN-n-
FAs, but it is unknown how the less abundant evencarbon-numbered
alkanes (ECN-n-alkanes) are
biosynthesised in higher plants [1,3,4] .
We have observed a distinctive compositional pattern
of incorporation of stable carbon ( 13 C) and hydrogen
( 2 H) isotopes in co-existing ECN- and OCN-n-alkanes
in leaves of higher plants, such that the OCN nalkanes
are more enriched in 13 C but more depleted
in 2 H than the ECN-n-alkanes [2,7] .
� 13 COCN-n-alkanes>� 13 CECN-n-alkanes
� 2 HOCN-n-alkanes

O-52
Nitrogen isotopes of amino acids: first results in sediments and
gorgonian corals of a new tool to reconstruct organic nitrogen
source and cycling from paleoarchives
Matthew McCarthy 1 , Owen Sherwood 2 , Fabian Batista 1 , Moritz Lehmann 3 , Christina
Ravelo 1 , Carsten Schubert 4
1 University of California, Santa Cruz, Santa Cruz, CA, United States of America, 2 Memorial University of
Newfoundland, Memorial University of Newfoundland, Canada, 3 Universität Basil, Basil, Switzerland, 4 Swiss
Federal Institute of Aquatic Science and Technology, Kastanienbaum, Switzerland (corresponding
author:mccarthy@pmc.ucsc.edu)
Most paleoceanographic studies of the N cycle
use the bulk � 15 N values (� 15 Nbulk) in sediments or
other paleoarchives as a proxy for � 15 N of surface
water nitrate, which assumes that � 15 Nbulk represents
integrated exported organic nitrogen. However,
� 15 Nbulk can be impacted by multiple factors, including
the addition of microbial biomass, trophic transfers,
and microbial reworking during degradation and early
diagenesis, all potentially varying based on local and
regional oceanic and depositional environments.
Here we describe first results in the development
of a fundamentally new approach toward
understanding � 15 N records, as well as nitrogen
source and transformation in organic matter paleoreservoirs:
compound-specific isotopic analyses of
amino acids (δ 15 N-AA). We hypothesize that aspects
of δ 15 N-AA patterns can be combined to deconvolute
the effects of trophic transfer, heterotrophic microbial
reworking, and autotrophic versus heterotrophic
sources on δ 15 N values, and potentially reconstruct
the average δ 15 N of exported primary production. We
present an overview of first δ 15 N-AA results for two
paleoarchives, ocean sediments and deep-sea
gorgonian corals.
The � 15 N-AA measurements in gorgonian corals
off the Nova Scotia shelf represents the first
application of this approach in a paleoarchive, and
demonstrates the potential to clarify previously
ambiguous bulk � 15 N records. In this region multiple
archives indicate a decline in � 15 Nbulk of exported
production over approximately the past century.
However, the � 15 Nbulk record inherently reflects both
source nitrate � 15 N, and also δ 15 N change due to
zooplankton trophic transfers. Therefore, at least two
different interpretations of existing � 15 Nbulk data are
possible: 1) a small shift in average trophic structure
(possibly driven by ecosystem shifts or climate
change), or 2) a shift in nitrate δ 15 N values,
associated with a shift in local current regimes. The
� 15 N-AA derived parameters ΣV and �Tr allowed us
for the first time to decouple these two factors. The
low degree of bacterial degradation indicated by the
ΣV parameter gives strong confidence in the integrity
of the δ 15 N-AA record in the coral protein skeleton.
The constant trophic structure indicated by the �Tr
parameter over the centennial record then indicates
that bulk δ 15 N trends likely are tied to physical shifts
in local current regimes (with their associated nitrate
� 15 N offsets), with timing suggestive of recent climate
change linkage.
We also recently completed the first sedimentary
� 15 N-AA measurements, from surface sediments in
the suboxic Santa Barbara Basin (SBB). We
analysed fluff layer and shallow intervals, to focus on
the transition from surface sources to sediments, in
the context of overlying plankton and sinking POM
samples
The basic � 15 N-AA patterns, as well as the
diagnostic Phe � 15 N values, appear preserved
essentially unchanged from plankton, through POM,
and into accumulating sediments. This indicates that
despite perhaps two orders of magnitude attenuation
in ON flux (expected from primary production to
surface sediment burial), the sedimentary � 15 N-AA
patterns show little change in individual isotopic
values, attributable to bacterial resynthesis. Certainly
bacterial degradation has been occurring, but the
molecular level data (and ΣV values) suggest that
preserved proteinaceous material in these samples is
composed of AA isotopically similar to their original
planktonic sources. The data ultimately suggests that
microbially resynthesis of AA (the process which
would alter � 15 N-AA patterns) has been minor. We
hypothesize finding similar preservation of � 15 N-AA
patterns with deeper burial.
Together, these first data from two paleoarchives
suggests that δ 15 N-AA can represent a powerful new
set of tools for understanding δ 15 Nbulk records of
organic matter in diverse paleoarchives.
112

O-53
Biomarkers and stable isotopes of euxinia and their role in fossil
preservation
Ines Melendez 1 , Kliti Grice 1 , Kate Trinajstic 1 , Katherine Thompson 1 , Mojgan Ladjaverdi 1 ,
Arndt Schimmelmann 2 , Paul Greenwood 3
1 WA Organic and Isotope Geochemistry Centre, Department of Chemistry, Curtin University of Technology,
Perth, Australia, 2 Indiana University, Dept. of Geological Sciences, Bloomington, United States of America,
3 University of Western Australia, Perth, Australia (corresponding author:ines.melendez@curtin.edu.au)
The Gogo Formation, located in the Canning Basin,
north-western Western Australia, shows remarkable
preservation of a Late Devonian (380 MYA) reef
fauna. The exceptional preservation, including original
bone and mineralized soft tissues, has resulted from a
combination of rapid burial and cementation within a
relatively tectonically stable environment. Soft-tissues,
including muscle bundles, nerve cells, and umbilical
structures, have been identified and described in the
vertebrate fauna (1, 2, 3). Through improved sampling
and preparation techniques extensive areas of soft
tissue have now been recovered from the Gogo
Formation. However, the exact mode of preservation
is yet to be determined.
To determine the palaeoenvironmental conditions that
resulted in the exceptional preservation of the ―Gogo‖
Formation an invertebrate fossil, containing soft
tissue, and the carbonate nodule were investigated
for the presence of biomarkers.
The nodule was divided in two with only one half used
for the experiments described below. The fossil was
extracted and separated into different fractions.
Dominant n-alkanes ranging from C15 to C32
(maximizing at n-C18 and n-C25) were identified. Their
� 13 C (-34 ‰ to -40 ‰) and �D values considering Denrichment
produced by thermal maturity (-230 ‰ to
270 ‰) are consistent with a source from
chemotrophic sulfate reducing bacteria (4, 5, 6). In
addition, the fossilised matrix was dominated by
cholestane (with a � 13 C value of -30.5 ‰) �bearing the
22R isomer (biological stereoisomer, reflecting an
immature signal) and high relative amounts of
phytane (� 13 C value of -34 ‰) probably derived from
sterols and chlorophyll of phytoplankton, respectively
in the upper water column on which the crustacean
used for its diet (7).
The desulfurised polar fraction (using Raney Nickel)
yielded a similar distribution of biomarkers to those
found in the free bitumen fraction. This observation is
remarkable for a sample 380 million years old. This
data supports rapid burial and preservation through
sulfurisation during the early stages of diagenesis.
Consistent with this hypothesis is the presence of
abundant Chlorobi biomarkers present in both the free
bitumen and sulfurised polar fraction. Markers of
Chlorobi, like isorenieratane and derivatives
therefrom, globally identified across Permian/Triassic
mass extinction boundary, have also been identified
here also supporting photic zone euxinic conditions
(H2S and light) in the water column (8, 9).These
results also support a recent study (10) which has
demonstrated that the Gogo Formation, Western
Australia, and the equivalent aged - Duvernay
Formation, western Canada (and their associated
oils) were deposited under highly euxinic conditions
based on the presence of biomarkers associated with
Chlorobi.
In marked contrast to the immaturity reflected by the
sterane distributions, the Ts/Tm ratio (0.62) of the
sample supports late thermal maturity. In order to
investigate the variations in maturity reflected by
these different biomarkers the second bitumen (after
isolation of kerogen) through heavy mineral
separation has been performed and compared with
the other fractions from the free bitumen (cf. work
carried out by 11).
(1) K. Trinajstic et al., Biology Letters 3(2),197-200 (2007)
(2) J. A. Long et al., Nature 453:650–652 (2008)
(3) J. A. Long and K. Trinajstic, Annual Reviews of Earth and
Planetary Sciences 38, 255- 270 (2010)
(4) K. Londry and D. Des Marais. Appl. Environ. Microbiol.
69:2942–2949 (2003)
(5) K. Londry et al., Appl. Environ. Microbiol. 70:745–751 (2004)
(6) X. Zhang et al., PNAS 106(31):12580-12586 (2009)
(7) K. Grice et al., Paleoceanography 13, 686-693 (1998)
(8) K, Grice et al., (2005) Science 307, 706-709.
(9) B. Nabbefeld et al., Earth and Planetary Science Letters 291,
84–96 (2010a)
(10) E. Maslen et al., Organic Geochemistry 49, 1–17 (2009)
(11) B. Nabbefeld et al., Organic Geochemistry 41, 78–87 (2010b)
113

O-54
Biomarker and petrographic evidence for the origin and maturity
of perhydrous arctic coal and associated bitumen
Chris Marshall 1 , David Large 1 , Colin Snape 1 , Julius Babatunde 1 , Will Meredith 1 , Clement
Uguna 1 , Baruch Spiro 2 , Alv Orheim 3
1 University of Nottingham, Nottingham, United Kingdom, 2 Natural History Museum, London, United Kingdom,
3 GeoArktis As, Stavanger, Norway (corresponding author:colin.snape@nottingham.ac.uk)
Oil prone perhydrous coals are economically
important as oil source rocks and as targets for coal
liquefaction. Abundant perhydrous (>5.6% H dmmf
basis) coal deposits are preserved within the high
latitude, middle Palaeocene, Todalen Member of the
Central Tertiary Basin, Svalbard. Previous work
regarding the extent and characteristics of high
latitude perhydrous coals is limited. These coals
provide a significant opportunity to understand the
processes which controlled hydrogen rich coal
production during this period of unprecedented global
warmth.
This paper provides the initial findings from three
samples from the Svea and Longyear seams.
Hydropyrolysis-GCMS and coal maceral analysis
were used to determine the origin of the perhydrous
coal and associated bitumen in the Longyear and
Svea seams. Biomarker analysis was used to provide
insight into the depositional environments required to
form high latitude hydrogen rich coals at a time of
global warmth.
The principal findings of this study are;
� The Svalbard coals contain significant
amounts of fluorescent vitrinite and
detrovitrinite with low liptinite content (3-6%).
This implies perhydrous vitrinites are a
significant role in the oil potential of these
coals
� Comparison of hopane, sterane, n-alkane
and tricyclic diterpanes maturity and
biomarker ratios for the asphaltene and
kerogen phases indicates a terrestrial source
for the bitumen with no evidence of inmigration
from marine shales found deeper
within the basin. The Pr/nC17 ratio of the
maltene (free phase) is higher than that of
the bound asphaltene phase (4.5 vs. 0.1 in
the Longyear seam) which is likely to be
evidence of expulsion
� Unusually the Svalbard coals (figure 1)
contain extremely high concentrations of
hopanes (72,000ng/g C). These are
attributed to rapid biodegradation rates
caused by the unique climatic position of
Svalbard in the Palaeocene and preservation
by organo-sulphur compound formation.
The presence of 3-methylhopanes indicates
that significant methanotrophic bacterial
communities were present during coal
formation.
� It is proposed that seasonal control,
alongside coastal pH regulation and higher
temperatures/productivity of the early
Palaeocene, could allow optimal growth of
bacterial communities. This would provide all
the conditions required for preservation of
hydrogen rich, functionalised molecules
including bacterial hopanes. Organo-sulphur
molecule formation during early diagenesis
would explain the subsequent oil-rich,
vitrinite dominated nature of these coals.
� The extent of methantrophic communities
within the Svalbard coals may provide
evidence for increased terrestrial methane
cycling in the Paleocene Arctic much earlier
than previously reported at lower latitudes
((Pancost et al., 2007).
Figure 1 –TIC Chromatogram of the extracted free aliphatic
phase from the Longyear coal.
References
Pancost, R.D., Steart, D.S., Handley, L., Collinson, M.E.,
Hooker, J.J., Scott, A.C., Grassineau, N.V., Glasspool, I.J.,
2007. Increased terrestrial methane cycling at the
Palaeocene-Eocene thermal maximum. Nature 449, 332-+.
114

Thursday Oral Presentations
115

O-55
The organic geochemistry of carbon management
Steve Larter, Thomas Oldenburg, Haiping Huang, Ian Gates, Barry Bennett, Norka
Marcano
PRG, University of Calgary, Calgary, Canada (corresponding author:slarter@ucalgary.ca)
We review current and future organic geochemical
applications to managing carbon emissions
associated with fossil fuel recovery and use. While
low carbon fuel alternatives are urgently needed, the
slow deployment of new energy generation
technologies means fossils fuels will be burnt for
decades. Decarbonising fossil fuel usage has a major
geochemical component with geochemical
applications in the areas of:-
1. Carbon efficient recovery and processing of
fossil fuels such as oil, gas and coal (CERP).
2. Industrial carbon dioxide capture and
storage in subsurface reservoirs (CCS).
3. Geoengineering for removal of carbon
dioxide from the atmosphere via air capture
or accelerated rock weathering (GCDR).
Organic geochemical applications are of several
types. In the CERP area there are many traditional
applications relating to assessment of resource type
and fossil fuel recovery. Thus petroleum systems
studies are used to improve energy recovery and
emissions efficiency. The many established
geochemical methodologies are not discussed here.
Recovery of unconventional oil and gas is an
increasing component of energy production and the
organic geochemistry of heavy oil and shalegas is
intimately involved with its efficient recovery.
Assessment of oil biodegradation and fluid properties
vertically and laterally in reservoirs is a direct input
into well placement and operational decision making
and we describe case histories showing how organic
geochemistry is used as a direct input into reservoir
engineering practices. A key factor is the conversion
of geochemical measurements and concepts to inputs
relevant to reservoir engineering protocols. The
commercial application of organic geochemistry to
real time production problems has required invention
of several new methods of sample extraction and
these are described. A potential game changing area
in CERP is the gasification, in situ of heavy oil or
coals. Methane has half the CO2 emissions of coal for
the same amount of energy generation. While thermal
gasification of coal is well developed and microbial
conversion of oil to methane has been researched for
energy recovery, the commercial conversion of coal to
methane microbiologically is still in its infancy with
rudimentary understanding of the processes involves.
Even the details of which compounds are being
degraded remains poorly described. We examine
progress and the need for new analytical
methodologies such as FTMS, looking theoretically at
organic geochemical and mass transport bottle necks
to large scale in situ microbial gasification of coal at
rates sufficient to replace coal mining and burning.
In the CCS storage area, inorganic geochemical
applications related to the CO2-bicarbonate-carbonate
system are self evident. Organic geochemical
applications are less obvious, but organic
geochemists may have great interests in economic
production and biogeochemical fates of some of the
alternative insoluble carbon storage vectors such as
whewellite (calcium oxalate) or DOM analogs, or in
biogeochemical routes to enhanced aqueous CO2
dissolution rates which have been proposed. We
review new organic geochemical focii in the carbon
storage area.
It is likely humankind will not get its act together in
time and that emergency carbon dioxide reduction
procedures may be needed mid century. Such
processes are termed geoengineering and if done
geochemically, can be at the safer end of that
technology domain. While organic geochemistry is
unlikely to be important in large scale air capture of
CO2, it may be crucially important in understanding
how to biologically accelerate carbon dioxide-mineral
reactions as a means of large scale atmospheric CO2
removal. Thus the biogeochemistry of mineral
carbonation reactions is a potential growth area for
organic geochemists.
116

O-56
The two largest soil organic matter pools in Arctic permafrost
show different degradation potentials upon coastal expulsion
Örjan Gustafsson 1 , Jorien Vonk 1,5 , Emma Karlsson 1 , Laura Sanchez-Garcia 1 , Bart van
Dongen 1,2 , Igor Semiletov 3,4 , Oleg Dudarev 4 , Alex Charkin 4 , Tim Eglinton 5 , August
Andersson 1
1 Stockholm University, Stockholm, Sweden, 2 University of Manchester, Manchester, United Kingdom, 3 IARC,
University of Alaska, Fairbanks, United States of America, 4 Russian Academy of Sciences, Vladivostok,
Russian Federation, 5 ETH, Zürich, Switzerland (corresponding author:orjan.gustafsson@itm.su.se)
About half of global soil organic carbon (OC) resides
in the top three meters of circum-Arctic permafrost.
Climate warming, particularly amplified over the
Arctic, may lead to permafrost thawing and the
potential for degradation of its organic matter to
greenhouse gases, a positive feedback to climate
warming. However, our mechanistic understanding of
the fate of Arctic soil OC in a warming climate is poor.
The shelf seas around the Eurasian Arctic, the world‘s
largest continental shelf, provide an integrating
window on the sources and fate of terrestrial organic
matter (terrOM) exported from its vast drainage
basins. Our investigations are applying lipid biomarker
and 13C+14C analysis of the exported terrOM in both
particulate organic carbon (POC) in surface water and
sedimentary organic carbon (SOC) collected from the
underlying surface sediments to deduce (a) the
relative contribution of various soil OC pools and (b)
the propensity of the different terrestrial OC pools to
degrade in the marine recipient.
Clear gradients in both molecular and isotopic signals
of source contributions and the extent of degradation
were observed both between surface water POC and
surface sediment SOC as well as over distance away
from the coast in three targeted systems; the SE
Laptev Sea, the central East Siberian Sea and the
northernmost sub-Arctic Baltic Sea. Depleted d13C-
OC and high HMW/LMW n-alkane ratios in both SOC
and POC signaled that terrOM was dominating over
marine/planktonic sources in all three systems.
Despite shallow water columns (10-50 m) in the
Laptev and East Siberian Seas, there was a large
isotopic shift in D14C between SOC and POC of +300
to +450 per mil. At the same time, the ratio of HMW
n-alkanoic acids to HMW n-alkanes was much greater
in the SOC than in the POC. Taken together, this
suggests that the terrOM in the surface sediment was
substantially older yet less degraded than in the
surface waters. This degradation trend is contrary to
what is normally observed.
Numerical modeling that allowed accounting for the
uncertainty in end-member composition, was applied
to 13C and 14C in both POC and SOC to deduce the
relative contribution of – marine OC, soil OC from the
annual thaw layer and OC from Yedoma/mineral soil.
This three end-member dual-carbon-isotopic mixing
model suggests quite different scenarios for the POC
vs the SOC. Surface soil is dominating (63±10%) in
surface water POC of SE Laptev Sea. In contrast, the
Yedoma/mineral soil OC is accounting for 60±9% of
the surface sediment OC in the SE Laptev Sea and
55±12% in the central East Siberian Sea.
We hypothesize, that Yedoma-OC, associated with
heavy mineral-rich matter is ballasted and quickly
settles out. This mineral association is also likely to
explain the greater resistance to degradation of this
terrOM component in the marine environment due to
physical protection against microbial enzymes. In
contrast, more humic-like (amorphous and buoyant)
terrOM from surface soil and recent vegetation
represents the younger, more bioavailable and thus
degraded terrOM component of the surface waters.
To address whether intrinsic chemical resistance or
physical protection is the dominant factor in this large
difference in degradation potential between the
surface soil vs mineral soil components from these
high latitudes, compound-specific radiocarbon
analysis (CSRA) was applied. CSRA of identical
HMW n-alkanes and HMW n-alkanoic acids were
performed along an offshore transect from the mouth
of the Kalix River to the central Bothnian Bay in
northernmost Baltic Sea. The CSRA was performed
both in SOC and here, for the first time, also in
seawater POC. The CSRA revealed a remarkable
fractionation for structurally identical vascular plant
markers (�400 ‰). This corresponds to an ―aging‖ of
�6000 years in a system where the hydraulic and
settling transport times are on the order of months – a
few years. The data suggest that identical lipid
biomarkers of different reservoir ages and different
physical protections exhibit different propensity to
degradation. Hence, these two soil OC components
also represent different propensity to contribute to a
positive feedback to Arctic climate warming.
117

O-57
Exploring mass extinction events (Triassic/Jurassic and
Permian/Triassic): Association with global warming events
Kliti Grice 1 , Birgit Nabbefeld 1 , Richard Twitchett 2 , Lindsay Hays 3 , Kenneth Williford 1 , Alex
Holman 1 , Roger Summons 3 , Jennifer McElwain 4 , Michael Böttcher 5
1 Curtin University, Perth, Australia, 2 Plymouth University, Plymouth, United Kingdom, 3 Massachusetts
Institute of Technology, Cambridge, United States of America, 4 University College Dublin, Dublin, Ireland,
5 Leibniz Institute for Baltic Sea Research, Warnemünde, Germany (corresponding
author:K.Grice@curtin.edu.au)
The Late Permian mass extinction event was the
most profound extinctions of the entire Phanerozoic.
Biomarker evidence for photic zone euxinic (PZE)
conditions within Permian/Triassic (P/Tr) setions,
where concentrations of sulfide, are sufficient to
support anoxygenic photosynthesis, come from
components derived from pigments of Chlorobi (Grice
et al., 2005; Hays et al., 2007; Nabbefeld et al., 2010).
Evidence for such conditions occurs at 6 localities
globally. Perturbations in the marine sulfur cycle and
thus the redox-state of the ancient seas are also
reflected in � 34 S of pyrite (e.g. from China, Italy, Iran,
Western Australia, East Greenland, Western Canada
and Spitsbergen) supporting widespread euxinic
conditions in both Palaeotethys and Panthalassa
oceans (e.g. Grice et al., 2005; Hays et al., 2007).
The aromatic biomarkers, dibenzothiophene,
dibenzofuran and biphenyl have been detected in
high abundances in samples prior to the marine
ecosystem collapse in East Greenland, Spitsbergen,
South China and Western Canada (e.g. Nabbefeld et
al., 2010). We have proposed that lignin derived from
land plants, present during the Late Permian is their
likely source. We provide sedimentological data,
biomarker abundances and compound specific
isotopic data (� 13 C and �D) along with bulk isotopes
(� 34 Spyrite, � 13 Ccarbonate, � 13 Corg) for several Late
Permian sections. At two localities sedimentological
and geochemical data supports a marine
transgression and collapse of the marine ecosystem
occurring in the Late Permian (Nabbefeld et al.,
2010). δ 13 C data of algal and land-plant derived
biomarkers, δ 13 C carbonate & organic matter support
synchronous changes in δ 13 C of marine and
atmospheric CO2, attributed to a 13 C-depleted source
( 13 C depleted methane and/or CO2 derived from
degradation of organic matter due to the marine
ecosystem collapse- Nabbefeld et al., 2010).
Evidence for waxing and waning of PZE throughout
the Late Permian is provided by Chlorobi derived
biomarkers and � 34 S pyrite implying multiple phases
of H2S outgassing and potentially several prolonged
pulses of extinction at several global localities. We
suggest that high levels of CO2 and H2S were the
drivers of the extinction. The Triassic/Jurassic (Tr/J)
extinction is regarded as being the fourth most acute
extinction event of the Phanerozoic in terms of
ecological impact. A number of mechanisms have
been proposed to account for the mass extinction,
including the release of CO2 associated with
emplacement of the Central Atlantic Magmatic
Province (CAMP). A negative carbon isotope
excursion has been detected in many sections, also
supporting a perturbation in the global carbon cycle. It
is clear that major and abrupt ecological change
including 80% extinction among terrestrial plant
species coincides with increased atmospheric CO2
concentration (CO2atm, based on stomatal analysis of
fossil Ginkoales leaves) and a negative excursion in
� 13 C of fossil wood from a Tr/J section at Astartekløft,
East Greenland. We have evidence for carbon cycle
perturbation, extreme heat stress and fire in the form
of molecular and compound specific stable isotopic
compositions of biomarkers from the boundary
section. Decreasing � 13 C and increasing �D of
terrestrial plant wax lipids together with increases in
combustion ascribed polycyclic aromatic
hydrocarbons, charcoal and gymnosperm resin
derivatives co-occur with ecosystem decline (Williford
et al., 2011).
References
Grice K, Cao C, Love GD, Bottcher ME, Twitchett R,
Grosjean E, Summons R, Turgeon S, Dunning W,
Jin Y 2005. Photic Zone Euxinia During the
Permian-Triassic Superanoxic Event. Science 307,
706-709.
Nabbefeld B, Grice K, Twitchett RJ, Summons RE,
Hays L, Böttcher ME, Muhammad A 2010. An
integrated biomarker, isotopic and
palaeoenvironmental study through the Late
Permian event at Lusitaniadalen, Spitsbergen. Earth
and Planetary Science Letters 291, 84-96.
Williford KH, Grice K, Holman A, McElwain JC.
Molecular and stable isotopic signatures of extreme
heat stress at the Triassic/Jurassic Boundary Nature
Geoscience Submitted Jan 2011.
118

O-58
Enhanced biomarker detection in microbial mats using ToF-
SIMS
Tim Leefmann 1 , Christine Heim 1 , Alexander Kaever 2 , Peter Meinicke 2 , Jukka Lausmaa 3 ,
Peter Sjövall 3 , Volker Thiel 1
1 Geobiology Group, Geoscience Centre, Georg-August-University of Göttingen, Göttingen, Germany,
2 Department of Bioinformatics, Institute of Microbiology and Genetics, Georg-August-University Göttingen,
Göttingen, Germany, 3 Department of Chemistry and Materials Technology, SP Technical Research Institute
of Sweden, Borås, Sweden (corresponding author:Tim.Leefmann@geo.uni-goettingen.de)
During the last years, Time-of-Flight Secondary Ion
Mass Spectrometry (ToF-SIMS) has increasingly
attracted the interest of organic geochemists by
offering a new way of studying biomarkers at the
microscopic level, and without extraction, thus largely
maintaining the physical integrity of the sample. Major
drawbacks, however, of ToF-SIMS as a new organic
geochemical technique are (i) a lack of reference
spectra, as electron impact mass spectra are not
necessarily similar to SIMS spectra [1], and (ii)
insufficient knowledge on the influence of matrix
effects on the SIMS spectra.
In this study these problems are addressed by the
analyses of seven standard substances that represent
commonly targeted compound classes in biomarker
studies (chlorophyll a, β,β-carotene, ergosta-5,7,22trien-3β-ol,
5α-cholestane, 5α-cholesta-3-one, L-αphosphatidylcholine,1,2-di-O-hexadecyl-sn-glycero-3phosphoethanolamine).
These compounds were
analysed on silicon wafers, on agarose films, on an
embedding agent for cryosections, and on slices of
marble, thus simulating the molecular environments of
typical matrices present in biomarker analyses by
ToF-SIMS. An auto-peak-search routine was used to
generate peak lists from the mass spectra.
Compound specific peaks were extracted from these
peak lists by Wilcoxon rank-sum test and translated
into compound-specific, matrix-independent mass
spectra. Using these reference spectra it was possible
to identify the target biomarkers in extracts from
cyanobacterial mats and, in a second step, image
their lateral distribution in corresponding microbial mat
cryosections with ToF-SIMS. Summing of all peaks
assigned to a specific compound led to a strong
signal enhancement, e.g. the signal intensity of β,βcarotene
in both, extract and mat cryosections,
increased by ~2 orders of magnitude compared to the
molecular ion peak. Similar amplification factors were
found for chlorophyll a in the same samples.
These results underpin the careful interpretation and
statistical evaluation of reference spectra as essential
prerequisites for the successful use of ToF-SIMS in
the analysis of trace amounts of biomarkers in
complex environmental samples.
References:
[1] Spool, A.M., Interpretation of static secondary ion
spectra. Surface and Interface Analysis, 2004. 36(3):
p. 264-274.
119

O-59
Black shale formation by microbial mats, lacking steraneproducing
eukaryotes in the Late Mesoproterozoic Taoudeni
Basin (1.1 Ga; Mauritania)
Martin Blumenberg 1 , Joachim Reitner 1 , Sascha Doering 2 , Walter Riegel 1 , Linda C. Kah 3 ,
Geoffrey J. Gilleaudeau 3 , Volker Thiel 1
1 Geoscience Center, Geobiology Group, Georg-August-University Göttingen, Göttingen, Germany,
2 Wintershall Holding GmbH, Kassel, Germany, 3 Department of Earth & Planetary Sciences, University of
Tennessee, Knoxville, United States of America (corresponding author:martin.blumenberg@geo.unigoettingen.de)
The composition of organisms thriving in Proterozoic
oceans is still controversial. Recently the early
emergence of 4-desmethyl sterane-producing modern
algae, dated back to at least 2.7 Ga [1], was seriously
questioned [2]. Likewise, the idea of algae as
important primary producers in earlier Proterozoic
Oceans was rejected [3], but the number of settings
studied so far is still limited.
Here we examine organic molecular components
within 1.1 Ga [4] black shale from Mauritania. By 1.1
Ga, algal components are well established [5], but
their ecosystem contribution is unknown. Within Late
Mesoproterozoic strata of the Taoudeni Basin
(Mauritania), various black shales were deposited in
the Touirist Formation. These shales partially contain
more than 20% organic carbon and show a very low
maturity. Hydrocarbon biomarkers in these black
shales were analysed for palaeoenvironmental
reconstruction. Microfacies and biomarkers support
stratigraphic interpretation of a shallow marine (likely
within wave base), high productivity-, low oxygen
setting with benthic mats as key-players in the
accumulation of organic matter. High TOC/S-ratios
and the occurrence of rearranged hopanes suggest
that euxinic conditions were not prevalent in these
environments, but do not preclude deeper-water
euxinia. The lack of steranes indicates that modern,
eukaryotic algae were of minor importance or even
absent, consistent with data from older
Mesoproterozoic settings [3]. However, palynological
survey of black shales from the Touirist Formation
revealed the presence, although in low abundance, of
simple acritarchs. Inputs of highly aromatic
biopolymers typical of those Mesoproterozoic
arcritarchs or exopolymeric substances may account
for unusually high aromaticity of biomarker extracts.
High amounts of hopanes and mid-chain branched
alkanes suggest that the benthic mats were strongly
influenced by cyanobacteria. Furthermore, the
presence of 2,3,6-trimethyl arylisoprenoids points at
contributions of organic matter from anoxygenic
phototrophic bacteria.
However, low concentrations of these compounds
and stable carbon isotope signatures of biomarkers
argue against major photic zone anoxia in these
depositional settings. More likely is the role of
anoxygenic phototrophs as part of the benthic
microbial mat communities, or the presence of other,
yet unknown, bacterial sources for arylisoprenoids.
Hopanes are very abundant in the samples from the
Touirist Formation. Since hopanes are common in
nitrogen fixing (cyano)bacteria, nitrogen-limited
conditions may have prevailed in the Taoudeni basin
at 1.1 Ga.
Our results support ideas of widespread nitrogen
deficiency that emerged in Mesoproterozoic oceans
resulting from enhanced denitrification rates in anoxic
deep waters [6]. Cyano- and other phototrophic
bacteria, as well as simple acritarchs were able to
cope with N-limited conditions, as well as associated
limitation of bioavailable trace metals, much better
than modern algae with their higher demands of
bioavailable nitrogen and essential trace metals [7].
[1] Brocks J.J., Logan, G.A., Buick, R., Summons, R.E. (1999)
Science 285, 1033-1036
[2] Rasmussen B., Fletcher, I.R., Brocks, J.J., Kilburn, M.R. (2008)
Nature 455, 1101-1104.
[3] Brocks, J. (2009) Geochim. Cosmochim. Acta 73, A161
[4] Rooney, A.D., Selby, D., Houzay, J.-P., Renne, P.R. (2010) Earth
Planet. Sci. Lett. 289, 486-496.
[5] Javaux, W.J., Knoll, A.H., Walter, M.R. (2004) Geobiology 2, 121-
132.
[6] Zerkle, A.L., House, C.H., Cox, R.P., Canfield, D.E. (2006)
Geobiology 4, 285-297.
[7] Anbar, A.D, Knoll, A.H. (2002) Science 297, 1137-1142.
120

O-60
Assessing subsurface microbial carbon assimilation by lipid
13CDIC-DH2O stable isotope probing
Gunter Wegener 1,2 , Marlene Bausch 1,2 , Nguyen Manh Thang 1 , Matthias Kellermann 2 ,
Xavier Pietro 2 , Kai-Uwe Hinrichs 2 , Antje Boetius 1,3
1 Max Planck Institute for Marine Microbiology, Bremen, Germany, 2 MARUM, University Bremen, Bremen,
Germany, 3 Alfred Wegener Institute for Polar and Marine Research, Bremerhaven, Germany
(corresponding author:gwegener@mpi-bremen.de)
Microbial metabolism predominates
remineralization of organic matter in marine
sediments. The catabolic reactions during carbon
mineralization in sediments are fairly well understood
and quantified, whereas in vivo anabolic activity of the
microbiota, including the extent of (lipid) biomass
formation and the biomass carbon sources of the
different organisms, are poorly constrained.
To characterize microbial membrane lipid
production we developed a combined 13 CDIC-DH2O
stable isotope probing (SIP) approach and tested it on
cultures of Desulfosarcina variables, grown on
heterotrophic and autotrophic substrates. At both
conditions hydrogen isotopic compositions of formed
lipids were almost in equilibrium with the deuterium
labelled water, indicating that D2O assimilation can be
used to integrate total lipid production. The dominant
pathway (hetero- or autotrophy) is displayed in
different 13 CDIC / DH2O assimilation ratios.
We applied our method to natural sediments from
a Swedish fjord (Himmersfjarden, Baltic Sea).
Sediments were incubated with 13 CDIC and DH2O
labelled brackish medium for 21 days. Total lipids
were extracted using Bligh and Dyer protocol. TLEs
were saponified or cleaved with boron tribromide to
yield total bacterial fatty acids and archaeal
isoprenoids, respectively. Deuterium and carbon
isotopic compositions of bacterial lipids were heavily
altered compared to the start conditions, especially in
terminally branched and unsaturated fatty acids,
whereas isotopic changes in archaeal biphytanes
were low. In control experiments (incubation of killed
sediments with 13 CDIC and DH2O amended medium),
no significant changes were detected in carbon or
hydrogen isotopic compositions.
Lipid formation rates, determined from changes
of deuterium isotopic compositions, labelling strength
and lipid concentrations, show that more than ¾ of
anaerobic microbial membrane lipid formation in a
72 cm core appears in its uppermost 5 cm (Fig 1). By
comparing 13 CDIC and DH2O derived lipid assimilation
rates we conclude that most lipids are produced by
heterotrophs (Fig 1). Only for some lipids (e.g. C16:1ω5)
autotrophic origin is dominant. Comparison of
sediment age and DH2O-SIP derived lipid turnover
times indicates that bacterial fatty acids were most
likely formed within the sediment. Turnover times of
archaeal biphytanes are several times higher than the
sediment ages. Hence we assume mainly
allochthonous origin (from the water column) of these
compounds.
Due to the high sensitivity of deuterium labelling
and the absence of artificial energy source additions,
we propose our method as tool to assess microbial
assimilatory activity in deep subsurface habitats.
Fig. 1. Left: Concentrations of bacterial lipids in
different horizons (bars) and their averaged weight
balanced carbon isotopic composition (black dots)
before incubation with 13 C-DIC and D2O-amended
medium. Right: Bacterial lipid formation in the
different horizons based on D2O-labeling (black bars)
and 13 C-DIC labelling (grey bars) and the ratio of the
lipid formation proxies (white circles).
121

O-61
The significant impact of weathering on spilled gulf of Mexico
mc252 oil chemistry and its fingerprinting of samples collected
from the sea surface and shore between May and September
2010
Changrui Gong 1 , Alexei Milkov 2 , David Grass 1 , Michael Sullivan 1 , Tomieka Searcy 1 ,
Leon Dzou 3 , Pierre-Andre Depret 1
1 BP America, Houston, United States of America, 2 BP Russia, Moscow, Russian Federation, 3 BP Asia
Pacific, Jakarta, Indonesia (corresponding author:changrui.gong@bp.com)
The spilled Gulf of Mexico MC252 reservoir fluid (oil with
dissolved gas) underwent tremendous changes to its
physical and chemical properties through multiple
processes, including, but not limited to, evaporation,
dissolution, dispersion, photooxidation, emulsification,
biodegradation and sedimentation, as it moved along a path
from the reservoir to the wellhead, then to the water column,
to the sea surface, and in some cases, to the shoreline.
As part of Gulf spill response effort, over 1500 samples of
source oil, sea surface slicks, emulsions, and tarballs were
collected (beginning from early May) for geochemical
fingerprinting (GC, MPLC, Isotope, GCMS, CSIR), and were
interpreted as ―PROBABLY‖, ―MAY BE‖, or ―NOT‖ related to
MC252 oil [1]. Five hundred and thirteen source oil, oil,
emulsion, and tarball samples ―PROBABLY‖ derived from
the MC252 spill available as of Jan 18 th were studied to
understand the relative importance of weathering processes,
and their impact on the oil budget at the surface and to
examine the effect of weathering on geochemical
parameters of MC252 oil.
In the first part of its path, from reservoir at 18,000 feet
deep to the sea surface, MC252 fluid lost up to 40% of its
weight (mostly gas range and soluble aromatic components).
Phase separation and dissolution in water were the main
processes responsible for this mass loss. These processes
substantially removed compounds smaller than C7. A
subsea hydrocarbon plume formed by suspended small oil
droplets was identified by multiple scientific survey ships [2]
from the MC252 spill. Respiration by methanotrophs and
other indigenous oil-degrading psychrophilic bacteria has
quickly removed dissolved hydrocarbon gas components [3,
4] and higher molecular weight hydrocarbons [5].
Oil droplets that survived the trip from well head to surface
appeared as surface slicks and emulsions. In the second
part of its path, from sea surface to landfall, evaporation,
and, less importantly, dispersion and dissolution, caused
further depletion totaling up to ~63% of the oil weight
affecting compounds up to C21. In the tar samples analyzed
from the spill significant biodegradation had affected a few
samples at the time of the sample analyses, but will play a
larger role in hydrocarbon‘s ultimate fate in the environment.
Weathering has a much bigger effect on aromatic
components than on saturate components due to the higher
solubility of aromatics in water and their susceptibility to
photooxidation. The impact of weathering on major aromatic
compound groups decreases from biphenyls to
naphthalenes, to dibenzothiophenes, and to phenanthrenes
(Fig. 1). Higher molecular weight compounds, especially
saturate biomarkers, were more resistant to these
weathering processes. Natural weathering seems to shift
isotopes of aromatic and asphaltene fractions to slightly
more enriched in 13C, and isotopes of resins to more
negative values (Fig. 2). The depletion of resin isotopes with
weathering might be due to continued conversion of
isotopically lighter saturate and aromatic fractions to resin
fraction during photooxidation [6] and, to a lesser extent,
biodegradation. In addition some commonly used
geochemical indicator ratios, such as MPI and C23tri/C30H,
are affected by the weathering processes.
Total naphthalenes/total dibenzothiophenes
100
10
1
0.1
Source oil Weathered oils
0.01
0.01 0.1 1 10 100
nC17/nC35
Figure 1. A decreasing ratio of total naphthalenes to total
dibenzothiophenes with increasing weathering as indicated by
decreasing nC17/nC35 ratios (nC35 conservative during weathering)
delta C13 of resin fraction
-25.8
-26
-26.2
-26.4
-26.6
-26.8
-27
-27.2
-27.4
Source oil Weathered oils
-27.6
0.01 0.1 1 10 100
nC17/nC35
Figure 2. A depletion in C13 for resin fraction isotope values with increasing
weathering
References
[1] Milkov et al. (2011) IMOG abstract volume
[2] Camilli et al. (2010) ScienceExpress. 19 Aug 2010
[3] Valentine et al. (2010) ScienceExpress. 16 Sept 2010
[4] Kessler et al. (2011) ScienceExpress. 6 Jan 2011
[5] Hazen et al. (2010) ScienceExpress. 26 Aug 2010
Dutta T.K. and S. Harayama, (2000) Environ. Sci. Technol. 34, 1500-1505
122

O-62
A reappraisal of long-chain diol proxies
Sebastiaan Rampen 1 , Veronica Willmott 1 , Jung-Hyun Kim 1 , Eleonora Uliana 2 , Enno
Schefuß 2 , Jaap Sinninghe Damsté 1 , Stefan Schouten 1
1 NIOZ Netherlands Institute for Sea Research, Den Burg, Netherlands, 2 Marum Center for Marine
Environmental Sciences, University of Bremen, Bremen, Germany (corresponding
author:sebastiaan.rampen@nioz.nl)
Since their first identification in the early 1980s, longchain
1,13-, 1,14- and 1,15-diols have been reported
widespread as often abundant biomarkers in
Quaternary marine sediments. Long-chain 1,13- and
1,15-diols were identified in eustigmatophyte algae
but their distribution differed from those in sediments,
making the role of these algae as a major source of
long-chain diols in marine environments questionable
[1]. Long-chain 1,14-diols were reported in the diatom
genus Proboscia and it was suggested that these
algae could be a major source for these specific longchain
diol isomers in upwelling areas [2]. This resulted
in the introduction of a long-chain 1,14-diol proxy as a
marker for upwelling intensity [3], and a study of the
relationship between temperature and the long-chain
1,14-diol chain-length in Proboscia diatoms
suggested the potential application as a
palaeotemperature proxy [4].
In this study, we performed an extensive global
marine surface sediment study on long-chain diols to
test various long-chain diol proxies. A total of 179
marine surface sediments, collected from worldwide
locations, were analyzed for long-chain diols. 82% of
these sediments contained quantifiable long-chain
1,14-diols although unsaturated long-chain 1,14-diols
were only detected in 60% of the sediments.
Quantifiable amounts of long-chain 1,13- and/or 1,15diols
were present in 76% of the marine surface
sediments In 73% of the sediments both 1,14-diols
and 1,13- and/or 1,15-diols were present at
quantifiable concentrations.
The results show that the use of the 1,14-upwelling
proxy is limited on a global scale and that there is no
clear relation between temperature and 1,14-diol
chain-length in surface sediments, possibly due to
input of different algal species. However, analysis of
the dataset did result in a novel proxy, the Diol Isomer
IndeX (DIX), based on distributions of long-chain
1,13- and 1,15-diols, and this index shows a
significant relationship with sea surface temperatures
(r 2 = 0.97, p < 0.001, Fig. 1). The new index was
tested on a core from the Congo fan, covering the last
43 kyr, and, like the U K‘ 37, the DIX recorded known
climate events such as the Younger Dryas and the
Last Glacial Maximum. Thus, the DIX may potentially
be used as a proxy for palaeo-SST complementary to
other organic SST proxies such as the U K‘ 37 and the
TEX86.
DIX DIX
1.0
0.5
y = 0.03x + 0.01
r2 y = 0.03x + 0.01
r = 0.97 2 = 0.97
-5 0 5 10 15 20 25 30
Annual mean SST, 0 m (°C)
Fig. 1. DIX values vs. Annual mean SST.
References
[1] Volkman J.K. et al. 1992. Org. Geochem. 18, 131-
138.
[2] Sinninghe Damsté .S.J. et al. 2003. Geochim.
Cosmochim. Acta 67, 1339-1348.
[3] Rampen S.W. et al. 2008. Earth Planet. Sci. .Lett.
276, 207-213.
[4] Rampen S.W. et al. 2009. Org. Geochem. 40,
1124-1131.
123

O-63
Simultaneous shifts in temperature in Central Europe and
Greenland during the last deglaciation
Cornelia I. Blaga 1 , Gert-Jan Reichart 1 , Andre F. Lotter 1 , Flavio S. Anselmetti 2 , Jaap S.
Sinninghe Damsté 3
1 Utrecht University, Utrecht, Netherlands, 2 Eawag, Dübendorf, Switzerland, 3 NIOZ, Den Burg, Netherlands
(corresponding author:blaga@geo.uu.nl)
The transition from the cold Last Glacial to the
warmer early Holocene is well documented in glacier
ice and marine sediments. Also from the continental
realm a large number of high-resolution records exist,
however, independent quantitative continental proxies
are scarce but important for our full understanding of
the climate system. Palaeoclimatic studies focusing
on the last deglaciation showed unstable climatic
conditions in Central Europe, based on correlations of
isotope records, pollen, cladoceran and chironomids
from lakes in Germany and Switzerland with the
Greenland isotope records.
Here we present the first decadal-resolution record of
the dynamic continental temperature changes in
Central Europe during the last deglaciation (~14,600
to 10,600 cal. yr BP) based on the organic
geochemical palaeothermometer TEX86. We analyzed
changes in isoprenoid and branched GDGTs in 200
contiguous samples encompassing the Glacial-
Interglacial transition as well as the Late Glacial
Interstadial in a core from Lake Lucerne
(Vierwaldstättersee). To determine where and when
glycerol dialkyl glycerol tetraether (GDGT) membrane
lipids are produced, we collected descending particles
using two sediment traps with a monthly resolution
from January 2008 to late March 2009. Suspended
particulate matter (SPM) was monthly filtered from the
water column at three different depths. Fluxes of
GDGTs and their concentrations in the water column
vary according to a seasonal pattern, showing a
similar trend in the SPM and sediment traps. Fluxes
and concentrations of isoprenoid GDGTs increase
with depth, maximum values being observed in the
deeper part of the water column, indicating production
of isoprenoid GDGTs by Thaumarchaeota in the deep
(~50 m), aphotic zone of Lake Lucerne. The fluxweighted
average of TEX86 is consistent with a
deeper water origin.
Our sedimentary record shows a remarkable
resemblance with the Greenland stable oxygen
isotope record on the centennial timescale. The
TEX86-inferred lake temperature record reveals the
typical oscillations during the Late Glacial Interstadial,
followed by an abrupt cooling of 1.2°C at the onset of
Younger Dryas and a rapid warming of 4-5°C at the
Younger Dryas/Holocene transition within less than
200 years. BIT values vary between 0.2 and 0.5 with
relatively high values in the middle part of the record.
Thus, the BIT record clearly reflects changes in
landscape openness and soil erosion in the
hydrological catchment. Our data imply that the
regional temperature changes in continental Europe
were dominated by large-scale reorganizations in the
northern hemispheric climate system.
Fig. 1 Comparison of the high resolution BIT, TEX86
and TEX86-inferred temperature record from
sediments of Lake Lucerne with the δ 18 O values from
the NGRIP record. Thick black line represents the
three-point moving average.
124

O-64
Simplification and recalibration of the MBT/CBT
paleothermometer based on branched tetraether lipids in
globally distributed soils
Francien Peterse 1 , Jaap van der Meer 1 , Johan Weijers 2 , Noah Fierer 3 , Robert Jackson 4 ,
Jung-Hyun Kim 1 , Stefan Schouten 1 , Jaap Sinninghe Damsté 1
1 Royal NIOZ Netherlands Institute for Sea Research, Texel, Netherlands, 2 Department of Earth Sciences,
Utrecht University, Utrecht, Netherlands, 3 Department of Ecology and Evolutionary Biology, University of
Colorado, Boulder, United States of America, 4 Department of Biology, Duke University, Durham, United
States of America (corresponding author:francien.peterse@nioz.nl)
The recently developed MBT/CBT proxy for the
reconstruction of continental air temperature and past
soil pH is based on the distribution of branched
glycerol dialkyl glycerol tetraether (GDGT) membrane
lipids in soils. An empirical study of soils from over 90
locations worldwide, showed that the relative
distributions of branched GDGTs correlate well with
mean annual air temperature (MAAT) and soil pH [1].
To quantify these changes, the Methylation of
Branched Tetraether (MBT) and the Cyclisation of
Branched Tetraether (CBT) indices were developed.
Combination of the indices resulted in the MBT/CBT
proxy, which has subsequently been used to
reconstruct climatic changes in several areas of
different geological age [2-5].
In this study, we extended the initial soil calibration
data set, now including 175 globally distributed
surface soils (Fig.), and reassessed the relation of the
different branched GDGTs with MAAT and soil pH.
Statistical analyses showed that only five of the nine
branched GDGTs are needed to describe the
relations with the environmental parameters.
Subsequently, we statistically correlated all possible
indices based on these five GDGTs, which lead to the
new MBT‘ and CBT‘ indices, and transfer functions to
estimate MAAT and soil pH. MAAT can now be
estimated with an accuracy of 4.8˚C (original
error=5.2˚C), solely using the MBT‘ index (r 2 =0.62).
The relation with pH is described by the CBT‘ index
(r 2 =0.74) with an accuracy of 0.7 pH unit (originally
0.8).
We tested these new indices on previously published
MBT/CBT-derived records. The records represent
large temperature shifts of different geological eras;
atmospheric warming of tropical Africa [2] and
southeast Asia [3] over the last deglaciation, the onset
of long-term cooling near the Eocene-Oligocene (E-O)
boundary [4], and the period of extreme warmth
during the Paleocene-Eocene thermal maximum
(PETM) at the Arctic [5].
For all tested records, the newly derived temperature
records follow the same warming and cooling trends
as those based on the original MBT/CBT proxy,
indicating that the MBT‘ index reflects changes in
temperature as expected. Regarding the absolute
values of reconstructed MAAT, the Eocene-Oligocene
boundary record remained practically unchanged.
However, the new temperature estimates for the other
records, i.e. deglacial tropical Africa and southeast
Asia, and the Arctic PETM are all substantially lower,
varying between 4-5˚C in Africa to 4-11˚C in Asia,
than the original MBT/CBT-derived temperatures.
The pH record for the Congo River basin [2],
representing the hydrologic changes in this region,
was again reconstructed, now using the CBT‘ index.
The obtained pH record follows the exact same trends
as the original CBT-derived record, but absolute
values are offset by 0.2 pH unit. However, this is well
within the error of both the CBT and the CBT‘ index.
The MBT‘ and CBT‘ indices thus result in MAAT and
pH estimates within the expected range, and can now
be calculated based on only five branched GDGTs.
The widespread occurrence and generally high
abundance of the selected branched GDGTs should
make quantification more straight forward and hence
improve the accuracy of the proxy.
Fig. Extended global soil calibration set. Soil locations
included in the original calibration are indicated in
black, and locations of the additional soils in red.
References:
[1] Weijers et al., 2007, GCA 71, 703-713
[2] Weijers et al., 2007, Science 315, 1701-1704
[3] Peterse et al., 2011, EPSL 301, 256-264
[4] Schouten et al., 2008, Geology 36, 147-150
125

O-65
Fluxes and isotope composition of selected halocarbons from
sea grass meadows
Enno Bahlmann, Ingo Weinberg, Richard Seifert, Walter Michaelis
Institute for Biogeochemistry and Marine Chemistry, University of Hamburg, Hamburg, Germany
(corresponding author: enno.bahlmann@zmaw.de)
Coastal areas are considered to be a significant
source of reactive trace gases to the atmosphere. In
the past, emissions of halocarbons and the underlying
mechanisms have been studied for macroalgae [1, 2],
plankton [3], and saltmarsh plants [4, 5]. In contrast,
data about trace gas emissions from sea grass
meadows are hardly available. Sea grass beds
covering about 10% of the coastal oceans are
amongst the most productive marine ecosystems [6]
and might represent an additional significant source of
halocarbons to the atmosphere.
We conducted flux chamber measurements on a sea
grass meadow in List/Sylt, Northern Germany to study
halocarbon fluxes. The isotopic compositions of the
emitted halocarbons were determined to elucidate the
underlying biogeochemical processes.
The stable carbon isotope ratios of chloromethane
and iodomethane ranged from δ 13 C of -46‰ to -58‰
and from -52‰ to –68‰, respectively. On average,
both compounds were depleted in 13 C by 40– 60‰ as
compared to the bulk biomass of sea grass. This
large isotopic shift relative to the plant material is in
the same range as previously reported for
chloromethane formed by higher plants and ascribed
to a methyltransferase catalysed reaction [7]. In
contrast, the carbon isotope compositions of
bromoform, iodoethane, iodopropane, and
vinylchloride were not more than 10‰ depleted in 13 C,
relative to the bulk sea grass biomass. This small
isotopic shift points towards a different building
mechanism, presumably the haloperoxidase pathway
(Fig. 1). The emitted bromomethane showed
intermediate carbon isotope ratios (δ 13 C -28‰ to -
41‰) as compared to the other compounds.
Measurements over adjacent bare sediments
revealed up to 45% of the newly formed
bromomethane to become readily degraded on the
sediment surface with this degradation being
associated with a fractionation factor of 45‰.
Although we cannot rule out that the production of
bromomethane is at least partly catalyzed by a
haloperoxidase reaction, we rather presume the shift
in 13 C of bromomethane to result from its immediate
degradation in the surface sediments.
δ 13 δ C [‰] 13C [‰]
-70
-60
-50
-40
-30
-20
-10
Methyltransferase
Methyltransferase
Degradation Degradation Degradation ? ? ?
Haloperoxidase
Haloperoxidase
seagrass CH CH3Cl 3Cl CH CH3Br 3Br CH CH3I 3I CHBr 3 C C2H 2H5I 5I C C3H 3H7I 7I C C2H 2H3Cl 3Cl
Fig. 1. δ 13 C values of emitted halocarbons and presumed
building mechanism from sea grass biomass
References
[1] Carpenter, L.; Malin, G.; Liss, P.; Küpper, F. 2000. Global
Biogeochemical, 14, 1191-1204.
[2] Laturnus, F.; Giese, B.; Wiencke, C.; Adams, F. 2000.
Fresenius Journal of Analytical Chemistry, 368, 297-302.
[3] Class, T.; Ballschmiter, K. 1998. Journal of Atmospheric
Chemistry, 6, 35-46.
[4] Bill, M.; Rhew, R.; Weiss, R.; Goldstein, A. 2002.
Geophysical Research Letter, 29, 2-5.
[5] Manley, S.; Wang, N.; Walser, M.; RJ. 2006. Global
Biogeochemical Cycles, 20, 1-13.
[6] Yamamuro, M.et al. 2002. Recent Advances in Marine
Science and Technology, 1-6.
[7] Harper et al. 2003. Chemosphere, 52, 433-436
126

O-66
Investigation of metagenomic clone library in biosurfactant
synthesis and hydrocarbon biodegradation processes
Suzan Vasconcellos 1 , Bruna Dellagnezze 2 , Isabel Natália Sierra Garcia 2 , Valéria
Oliveira 2 , Philip Hendry 4 , Carol Nichols 5 , Eugenio Santos Neto 3 , Herbert Volk 4
1 Federal University of São Paulo - UNIFESP, São Paulo, Brazil, 2 Campinas University - UNICAMP,
Campinas, Brazil, 3 PETROBRAS R & D Center, Rio de Janeiro, Brazil, 4 CSIRO, Sydney, Australia, 5 CSIRO,
Hobart, Australia (corresponding author:supantaroto@yahoo.com.br)
Many studies of physiologically diverse bacterial
communities, present in petroleum reservoirs have
been reported. These include thermophilic and
methanogenic archaea, hydrocarbon-oxiding bacteria,
sulfate reducing bacteria, manganese and iron
reducing bacteria and many fermenting
microorganisms. These metabolically different
microorganisms can be responsible for petroleum
biodegradation, which decreases the economic value
and increases loss and difficulties in oil exploration
and refining. In this context, through projects linked to
Petrobras, a metagenomic library of 31,000 clones
was constructed from the microbiota present in a
Brazilian petroleum reservoir, located at Potiguar
Basin (Mossoró, RN) (Vasconcellos et al., 2010).
From this metagenomic library, biocatalytic and
biosynthetic investigations are being developed and
8,000 clones were screened to assess their ability to
biodegrade and emulsify hydrocarbon. From these,
10 clones were selected as candidates in a more
detailed investigation. The present study sought to
evaluate these clones for their ability to (1)
biodegrade different hydrocarbons and (2) to produce
exopolymers (EPS) with emulsifying activity.
The selected clones were pre-cultured, individually
or in a consortium (300 mL LB media, 37 o C, shaking
at 150 rpm for 24 h), according to methods described
by Vasconcellos et al (2010). The culture assays were
developed by combining the following ingredients: 10
mL microbial suspension (OD ≥ 1.0, absorbance at
600 nm); 100 mL Bushnell Haas mineral medium; 50
µL chloramphenicol (12.5 µg/mL); 200 µL vitamin
solution. In addition, 1 mL or 0.1 g of hydrocarbon:
hexadecane, naphthalene or 0.33 mL of each of three
hydrocarbon, n-alkanes mix (dodecane, tetradecane
and hexadecane) was added. The assays were run in
triplicate. After 10 days of incubation (37 o C), the EPS
from the cultures assays were extracted. according
methods described by Klock et al. (2007). It was
observed that the mixture of n-alkanes resulted in a
better performance of the clones, with respect to EPS
yields (>1 g EPS/ g cells). The partial structural
elucidation of the extracted EPS was determined
through colorimetric analysis for total carbohydrate,
protein and uronic acid content. The results
demonstrated that the EPS fractions were composed
mainly of proteins. The ability of the extracted EPS to
emulsify hydrophobic compounds was evaluated
using hexane and hexadecane (Fleck et al., 2000).
The results were compared to Triton 100 as positive
control. EPS solutions from 4 clones showed
emulsification higher than for Triton X (65 to 80%).
GC-MS analyses were performed to evaluate the
potential of the clones to biodegrade the
hydrocarbons, added as carbon sources. The
obtained results experiments demonstrated that 1
clone could be considered as a potential hydrocarbon
biodegrader. It was able to degrade, to some extent
(43 to 99%), all of the evaluated substrates during the
10 day experiment. Results of this study
demonstrated that the clones that gave the highest
EPS yields and emulsification indexes were not the
same as those that showed the highest hydrocarbon
biodegradation indexes. By combining clones that
presented the highest biodegradation index for each
substrate of interest, it may be possible to achieve
effective biodegradation when aiming their application
towards a bioremediation processes. If the application
of these clones in MEOR is a desired goal, a
combination of clones that produced high amounts of
EPS with others that demonstrated optimum
emulsification indexes would be a good environmental
friendly solution.
References
[1] Fleck, L.C., Bicca, F.C., Ayub, M.A.Z. (2000) Biotech.
Lett. 22: 285-289.
[2] Klock, J-H, Wieland, A., Seifert, R., Michaelis, W.
(2007). Mar. Biol. 152:1077-1085.
[3] Vasconcellos, S.P., Figueiredo Angolini, C.F., Sierra
García, I.N., Dellagnezze, B.M., Silva, C.C., Marsaioli,
A.J., Santos Neto, E.V., Oliveira, V.M. (2010) Org.
Geochem. 41:675-681.
127

O-67
Biogeochemical impact of CO2 exposure on reservoir rocks and
the indigenous microbial community
Ann-Kathrin Scherf, Maren Wandrey, Kornelia Zemke, Andrea Vieth-Hillebrand, Ketzin
group
German Research Centre for Geosciences - GFZ, Potsdam, Germany (corresponding author:scherf@gfzpotsdam.de)
In recent years the widespread occurrence of
microorganisms was demonstrated in the subsurface.
Low molecular weight organic acids (LMWOA) form a
potential feedstock for indigenous microbial
community and represent also intermediate products
of bacterial metabolism.
As a part of the ongoing efforts to understand the
intra-reservoir processes and potential of using deep
saline aquifers for long term storage of CO2 in Ketzin
(Northeast German Basin) CO2 is injected into a
Triassic saline aquifer at a depth between 630 and
710 m below surface since June 2008. Within the two
projects CO2SINK and CO2MAN the injection and
propagation of the CO2 is monitored and the
geochemical, geophysical and microbiological effects
are analysed in situ as well as in laboratory
experiments. Among those this long-term experiment
was set up in September of 2007 to study changes in
biogeochemical and microbiological processes and
petrophysical properties of the rocks.
Fresh, pristine reservoir rock samples from the Ketzin
site have been incubated with artificial high salinity
brine and CO2 in high pressure at 5.5 MPa and 40°C.
Generally, rock and fluid samples were analysed with
respect to geochemistry, microbial community, as well
as mineralogical and petrophysical characteristics
[1,2,3]. The focus of the research presented here, is
the amount of LMWOA in the fluid phase and its
change over time. After 15, 21, 24 and 40 months of
CO2 exposure, fluid samples were analysed using ion
chromatography to obtain information on the
alteration of the concentrations of low molecular
weight organic acids.
In the cause of the experiment formate and acetate
concentrations showed first only slight, but later on
partly exponential increase. This may reflect an
increased production of organic acids by microbial
activity, as the change of reservoir (here,
experimental) conditions due to the injection and
storage of CO2 in geological formations may induce
changes in the indigenous microbial community and
thus, the overall microbial activity. But also
mobilisation of organic molecules from mineral
phases during CO2 exposure may take place as
(supercritical) CO2 is an excellent solvent for certain
organic molecules.
To unravel changes in the microbial community and
thus, metabolic activity pristine rock samples as well
as selected incubated core pieces have been
analysed for the composition of the inhibiting
microbial community using molecular biological
methods. Here it has been shown, that the
composition of the microbial community in the
reservoir sandstone mainly consists of
chemoheterotrophic bacteria [1]. So far, only minor
changes of the microbial community composition
were observed. However, evaluating the results
regarding the timescale of the shifts in LMWOA
concentrations in the brine makes an adaptation of
the microorganisms to the modified conditions more
likely then a ―late‖ mobilisation event due to the
presence of CO2. This is supported by the results of
another set of laboratory experiments where the
mobilisation of LMWOA through the exclusive
exposure to (supercritical) CO2 has been
demonstrated [4]. In these experiments strongest
mobilisation effects were observed in the first few
hours.
Summarised we conclude that the increased
concentration of the LMWOAs formate and acetate
has its main origin in increased microbial activity and
not in mobilisation / solution effects through the
presence of brine and CO2. These results may be
extended by the comparison of PLFA profiles of fresh
and CO2-treated twin samples and furthermore,
LC-ir-MS analyses of LMWOA.
References
[1] Wandrey, M. et al., 2011. Energy Procedia 4,
3644-3650.
[2] Zemke, K. et al., 2010. <strong>International</strong> Journal on
Greenhouse Gas Control 4, 990-999.
[3] Fischer, S. et al, 2010. Chemie der Erde 70, 155-
164.
[4] Scherf, A.-K. et al., 2011. Energy Procedia 4,
4524-4531.
128

O-68
Latitudinal distribution of archaeal H-lipids
Carme Huguet 1 , Susanne Fietz 1 , Antoni Rosell-Melé 1,2
1 aInstitut de Ciència i Tecnlogia Ambientals, Universitat Autònoma de Barcelona, Cerdanyola, Spain,
2 cInstitució Catalana de Recerca i Estudis Avançats (ICREA), Barcelona, Spain (corresponding
author:carme.huguet@uab.es)
The unique composition of Archaea‘s membrane
lipids allows them to maintain integrity and exchange
capabilities in moderate and extreme conditions 1 .
They adapt to a wide range of temperatures by
changing the number of rings in their glycerol dialkyl
glycerol tetraether (GDGT) membrane lipids, which is
used to estimate past water surface temperature via
the TEX86 index 2 . Here we report that mesophile
Archaea also synthesize an additional set of core
membrane lipids with a covalent bond between the
two chains (H- GDGTs) which were previously
thought to be restricted mainly to extremophiles 3 . We
propose that these lipids help mesophile Archaea to
adapt to cold conditions, maintaining their membrane
exchange capabilities. However, this contradicts
previous hypothesis that suggested H-GDGTs to be
an adaptation to withstand high temperatures. We
observe that H- GDGTs are widespread and
abundant in mesophilic marine and lacustrine
environments, and that surprisingly they increase in
abundance towards higher and colder latitudes (Fig.
1). The lowest H-GDGT abundances (0-23%) were
found between 0-45 ºN and 0-30 ºS strongly
increasing to 35-95% at 60-87ºN and 60-70ºS (Fig.
a b
1a). Moreover the contribution of H-GDGTs increases
as temperature decreases with values ranging from 0
at 25 ºC to 95% below 0 ºC. In fact the relative H-
GDGT abundance is significantly correlated with
temperature (R²= 0.64 p

Bacteria number ml-1 Bacteria number ml-1 1.2 E+07
1.0 E+07
8.0 E+06
6.0 E+06
4.0 E+06
2.0 E+06
O-69
Role of photooxidative processes in senescent phytoplankton
cells and attached bacteria in the preservation of organic matter
Morgan Petit 1 , Richard Sempere 1 , Stuart G. Wakeham 2 , John K. Volkman 3 , Frédéric
Vaultier 1 , Jean-François Rontani 1
1 Laboratoire de Microbiologie Géochimie et Ecologie Marines (LMGEM -UMR 6117), Marseille, France,
2 Skidaway Institute of Oceanography, Savannah, United States of America, 3 CSIRO Marine and
Atmospheric Research, Hobart, Australia (corresponding author:jean-francois.rontani@univmed.fr)
Visible-light-induced photosensitization processes are
intense during the senescence of phytoplankton cells.
These processes mainly involve singlet oxygen ( 1 O2)
and act on most of the unsaturated lipid components
(including sterols, unsaturated fatty acids and the
chlorophyll phytyl side-chain) of these organisms. The
effects of photooxidation, however, may go beyond
the algal cellular lipids that are initially affected. If the
photochemical production of
1 O2 exceeds the
quenching capacity of the photoprotective system,
this excited form of oxygen can migrate outside the
chloroplasts and induce degradation of components
of attached heterotrophic bacteria [1]. Cellular
damage resulting from the transfer of high amounts of
1
O2 to heterotrophic bacteria may be significant due
to the lack of efficient photoprotective and antioxidant
systems in these microorganisms. This transfer may
thus affect the preservation of algal material in the
marine environment.
In order to check this hypothesis, non-axenic cells of
Emiliania huxleyi were grown under consecutive
irradiance regimes: light and dark, dark and light and
dark.
Dark incubation
Return
to light
0
0
0 2 4 6 8 10 12 14 16 18 20
Sampling day
7.0
6.0
5.0
4.0
3.0
2.0
1.0
Fig1. Evolution of bacterial number (diamonds) and of
the amounts of vaccenic acid oxidation products
(open boxes) during the experiment
Bacterial counts showed a strong increase during the
incubation under darkness and a significant decrease
Vaccenic oxidation products (ng ml-1 Vaccenic oxidation products (ng ml ) -1 )
after return to light (Fig. 1). The simultaneous
increase in the amount of oxidation products resulting
from the attack by singlet oxygen on vaccenic acid (a
typical bacterial fatty acid) and decrease in bacterial
numbers observed after the return to light (Fig. 1) fits
nicely with this hypothesis.
In order to better understand unexpected abundances
of labile OM at depth in the Equatorial Pacific we reinvestigated
lipids in suspended and sinking
particulate organic matter (POM) samples that had
been analyzed previously [2]. Biodegradation was
more intense in sinking POM than suspended POM.
We could attribute this difference to an efficient
transfer of singlet oxygen from suspended and
senescent phytoplankton cells to associated bacteria
and subsequent inhibition of heterotrophic
degradation [3]. On the other hand, we speculate that
an abundance of charged mineral surfaces, such as
siliceous diatom frustules or carbonaceous coccoliths
in sinking particles, may reduce the lifetime of 1 O2
and allow for enhanced bacterial growth and
biodegradation in sinking particles compared to
suspended particles [3]. It thus seems that there is a
direct link between the photooxidation state of lipids of
senescent phytoplanktonic cells in suspended
particles and their recalcitrance towards biotic
degradation. These results could explain some
previous observations showing that in northeast
Pacific Ocean sinking particles contain a more active
bacterial community than suspended particles [4].
[1] Rontani J.-F., M. Koblizek, B. Beker, P. Bonin, and
Z. Kolber. 2003. Lipids 38: 1085-1092.
[2] Wakeham S.G., J.I. Hedges, C. Lee, M.L.
Peterson, and P.J. Hernes. 1997. Deep-Sea Res. II
44: 2131-2162.
[3] Rontani J.-F., N. Zabeti, S.G. Wakeham. 2010
Limnol. Oceanogr. 56: 333-346.
[4] Karl, D. M., and G. A. Knauer. 1984. Deep-Sea
Res. 31: 221-243.
130

O-70
Deciphering the physiological significance of hopanoids in the
marine geologic record
James Saenz 1,2 , Roger Summons 1 , Timothy Eglinton 2 , Stuart Wakeham 3,4 , John
Waterbury 2
1 Massachusetts Institute of Technology, Cambridge, MA, United States of America, 2 Woods Hole
Oceanographic Institution, Woods Hole, MA, United States of America, 3 Skidaway Institute of Oceanography,
Savannah, GA, United States of America, 4 University of Washington School of Oceanography, Seattle, WA,
United States of America (corresponding author:jsaenz@whoi.edu)
Lipids have a legacy in the geologic record
extending back to the Archaean. Since the
phylogenetic diversity of life is reflected in the
structural diversity of biomolecules, lipid biomarkers
that are shown to be diagnostic of certain organisms
that carry out specific biochemical processes or that
are demonstrated to have unique physiological roles
can be used to trace the biogeochemical influence of
bacteria in modern and ancient environments.
Hopanoids have been broadly applied in the marine
sedimentary record as taxonomic markers for certain
groups of bacteria and their associated
biogeochemical processes. However, our ability to
rigorously interpret the significance of hopanoids in
the geologic record has been greatly limited by a
dearth of knowledge surrounding the sources of
hopanoids in marine environments. Despite the
ubiquity of hopanoids in modern and ancient marine
sediments, their provenance in the modern oceans is
unknown. In this study, we present a survey of
bacteriohopanepolyols (BHPs) in a diverse selection
of marine and proximal marine environments, and in
marine cyanobacterial cultures and enrichment
cultures. Our work establishes the presence and
ubiquity of hopanoids in the oceans, and provides
fresh insight on the environmental sources and
biogeochemical significance of hopanoids in marine
sediments.
In the marine realm, we observe pronounced
heterogeneity in the spatial and temporal distribution
of BHPs, indicating the potential for the application of
hopanoids as biomarkers for biological processes in
the upper ocean and as tracers for organic matter
input to sediments. In particular, BHPs appear to be
relatively abundant and structurally diverse in low
oxygen and oligotrophic environments and in
particulate organic matter (OM) transported by rivers
from terrestrial environments. Given the rich structural
diversity of BHPs in terrigenous OM, interpretations of
the sedimentary record of hopanoids in coastal
marine settings must resolve inputs from marine
pelagic and terrestrial sources. Furthermore, BHPs
produced in suboxic and anoxic pelagic environments
likely represent an important input to the sedimentary
hopanoid inventory in upwelling environments and
anoxic marine basins. Our findings reveal that marine
suboxic and anoxic environments can be important
sources of hopanoids to the marine sedimentary
record.
There is evidence to suggest that hopanoids
may be diagnostic of cyanobacteria in the
environment, and therefore could serve as biomarkers
for cyanobacteria in past and present environments.
However, very little is known about the distribution or
physiological roles of hopanoids in marine
cyanobacteria. Our survey of a diverse range of
marine cyanobacterial cultures, and cyanobacterial
enrichment cultures indicates that hopanoid
production may be unique to, or at least widespread
among, the nitrogen-fixing cyanobacteria in marine
environments. We observe a very high structural
diversity of BHPs in the marine cyanobacterial
enrichment cultures, which stands in stark contrast to
the low structural diversity observed in pure cultures.
This demonstrates that there are diverse and
presently un-accounted for marine bacteria, possibly
cyanobacteria, that are capable of synthesizing a
diverse range of BHP structures in the marine
environment.
Interpreting the significance of hopanoids in
the sedimentary record relies on a presently
incomplete understanding of their phylogenetic
associations, biological functions, and spatial and
temporal disposition within the environment. From the
perspective of the marine geologic record, the
environmental distribution of BHPs is particularly
important since it provides constraints on the
provenance of hopanoids that are present in marine
sediments, which may in turn provide clues about the
biological source or function. We explore the current
state of knowledge of BHPs in modern environments,
and entertain the question: ―What can the vast
majority of hopanoids preserved in the sedimentary
record tell us about life in ancient environments?
131

O-71
Aquathermolysis: pressure effect on gas production and oil
composition
Violaine Lamoureux-Var, Françoise Behar
IFP Energies Nouvelles, Rueil-Malmaison, France (corresponding author:violaine.lamoureux-var@ifpen.fr)
Steam injection is one of the main thermal production
processes for enhancing oil recovery in petroleum
reservoirs. This process induces gas generation and
oil composition modification, resulting from
physicochemical transformations in the reservoir
called aquathermolysis. Until now, little attention has
been given to the possible influence of steam
pressure and/or water phase on gas generation and
oil composition. To address this issue,
aquathermolysis laboratory experiments were carried
out under various pressures, on an oil sand sample
with added distilled and free-oxygen water (1/1,(v/v)),
at 250°C/1 month in sealed gold tubes. The applied
external pressure was constant, in the range from 40
to 120 bar, enabling the water to be either in vapour
phase (40 bar), or in liquid phase (120 bar) or in a
coexisting liquid/vapour phase. At the end of the
experiments, the total gas was recovered and
quantified in absolute amounts. For some
experiments, mass balance on the liquid products
was done on the C14+ hydrocarbons, the resins and
asphaltenes.
Gas results show clearly that both CO2 and H2
absolute yields decrease between 40 and 60 bar and
then increase between 60 and 80 bar (Fig. 1).
Although H2S was difficult to quantify, the H2S/H2
molar yields ratio evolves clearly: it increases from 40
to 60 bar and then decreases from 60 bar to 80 bar
(Fig. 1).
The presence of hydrocarbon gases reveals some oil
cracking. The C1/ C2-C4 molar yields ratio appears to
decrease from 40 to 60 bar, indicating the production
of a wetter gas as pressure increases, and then
seems to remain constant. Moreover, it is observed
an increase of isomerisation for the butane
compounds below 60 bar, since the ratio iC4/n-C4
increases from 40 to 60 bar.
All these results suggest that the pressure has a
strong impact on the oil sand reactivity under
aquathermolysis experiments. So far, two factors may
be responsible to these observed data: either the
pressure and/or the water phase. In order to
distinguish the possible causes, complementary work
is in progress, in particular by running the same set of
experiments without water.
CO2 yield (µg CO2/g oil
sand)
H2S/H2 (mol/mol)
2000
1800
1600
1400
1200
1000
800
600
400
200
0
18
16
14
12
10
8
6
4
2
0
CO2
vapour
water water
phase
transition
liquid
water
30 35 40 45 50 55 60 65 70 75 80 85
Pressure (bar)
vapour
water
H2S / H2
water
phase
transition
30 35 40 45 50 55 60 65 70 75 80 85
Pressure (bar)
liquid
water
Aquathermolysis experiments conducted on an oil sand
sample, at 250°C, during 1 month, for different pressures
from 40 bar to 80 bar. Upper: CO2 absolute yield. Lower:
H2S/H2 absolute molar yields ratio.
Figure 1: Pressure effect on non-hydrocarbon gases
generation during aquathermolysis.
132

O-72
Compositional kinetic model for thermal evolution of extra heavy
oils and tar sands
François Gelin 1 , Luc Fusetti 1 , Yongchun Tang 2 , Françoise Behar 3 , Tuong-Van Ledoan 1 ,
Paul-Marie Marquaire 4 , Roda Bounaceur 4 ,
1 TOTAL, Pau, France, 2 PEERI, Los Angeles, United States of America, 3 IFP, Paris, France, 4 ENSIC, France,
France (corresponding author:luc.fusetti@total.com)
The production of extra heavy oils and tar sands
resources faces the challenge to mobilize
hydrocarbon fluids of extremely high viscosities due to
the extended alterations (e.g. biodegradation) these
resources have overcome through geological time.
When such unconventional hydrocarbons plays are
too deep to enable pit mining, flow assurance
becomes a serious issue and, in addition to the use of
high efficiency pumps, its improvements often passes
through the application of enhanced thermal recovery
techniques.
Among thermal EOR techniques:
(i) Steam Injection has become very popular to
decrease the viscosity of hydrocarbon fluids in place
by increasing the formation temperature with steam
In Situ Upgrading (IUP) via Subsurface Pyrolysis is
debated in order to pre-upgrade the oil in situ by
substantial heating of its environment, theoretically
inducing the production of higher quality oil.
(ii) Both steam injection and IUP processes imply
chemical modifications within the OIP which cannot
be correctly predicted without an accurate kinetic
model that would account for the compositional
changes related to a given thermal history.
The present study proposes the development of a
compositional kinetic model that has been optimized
in order to predict the compositional evolution of extra
heavy oils and bitumen when submitted to thermal
stress. The model is based on 11 lumped chemical
classes and chemical 22 equations. It also includes
32 stoichiometric coefficients and 30 activation
energies/frequency factors.
On a range of several hundred degrees centigrade, it
is able to predict the evolution of cumulated (Figure
1) and instantaneous yields for the whole range of
molecular weights i.e.:
� The decrease of aromatics and polar
compounds (heavy cuts),
� The generation of hydrocarbon gases and
acid gases,
� The generation and potential destruction of
light cuts,
� The generation of pyrobitumen.
Figure 1: Evolution of various reactivity lumps of
an heavy oil under isothermal stress
Such prediction, either under isothermal or nonisothermal
heating conditions, provides key
arguments in the discussion to determine the most
appropriate (temperature-time) conditions needed to:
� Enhance the generation of light cuts,
� Minimize the generation of pyrobitumen than
could seriously damage formation porosity
and permeability,
� Reduce acid gases generation to manage
HSE and corrosion issues.
In a near future, it is expected to couple such kinetic
model with a thermal propagation model and a
polyphasic thermodynamic model to improve reservoir
simulation of thermal EOR processes using various
well patterns.Please place the text of your abstract
here after you have composed it according to the
guidelines and the example contained in the
instructions. The text will automatically wrap into the
second column.
133

O-73
Designing tight-shale production strategies using diamondoid
nanotechnology
Jeremy Dahl, Shaun Moldowan, J. Michael Moldowan
Stanford University, Stanford, California, United States of America (corresponding
author:dahl@Stanford.edu)
Organic carbon content (TOC), hydrogen to carbon
ratio (H/C ratio) and thermal maturity all play an
important role in mapping out potentially productive
regions of tight shales (e.g. Barnett, Marcellus,
Eagleford, Fayetteville etc). TOC and H/C ratio can
be measured directly and accurately from cores and
cutting samples. Thermal maturity, on the other hand,
and in particular the extent of oil cracking (thermal
conversion of liquid to gas), can only be qualitatively
estimated based on indirect techniques such as
vitrinite reflectance, gas isotope data and Rock-Eval
pyrolysis. Furthermore, the lack or paucity of vitrinite
in some shales such as the Marcellus, makes
accurate thermal maturity assessment difficult. The
determination of diamondoid concentrations in tight
shale core and cutting samples provides the first
direct indication of natural oil cracking and also
provides the first means of calculating the percentage
of liquid within the shale which has been converted to
gas.
Diamondoids are hydrogen-terminated nanodiamonds
that are present in all source rock extracts and oils.
Like larger diamond, diamondoids have high thermal
stability that makes them ideal natural internal
standards for studying oil cracking. Diamondoid
results presented for Barnett cores and cuttings along
with samples from other tight shales show that where
there is no oil cracking (thermal conversion of liquid to
gas), there is no production. Where there is extensive
oil cracking, e.g. over 90% of the liquid has been
converted to gas (resulting in very high diamondoid
concentrations), there is only gas production with very
little associated liquid. It is where diamondoids
reveal intermediate amounts of cracking (10-90%)
that both gas and liquid are produced and where
adjacent oil fields occur.
Furthermore, because it is possible to calculate the
amount of cracking using diamondoid concentrations,
combined with TOC and H/C one can estimate the
increase in pore pressure due to the natural
conversion of oil to gas. Our results show that
intermediate amounts of natural oil cracking in the
Barnett results in pressures in excess of those used
to hydro-fracture the rock.
By making maps of tight shale TOCs, H/C ratios, and
diamondoid concentrations, it is possible to map out
regions where little or no production is possible,
regions where the shale will be productive but the
hydrocarbons produced will be gas with no or very
little liquid, and regions where both gas and liquid can
be produced and where adjacent oil fields may be
found. Other measurements of thermal maturity
including vitrinite reflectance, gas isotopes, and Rock-
Eval, all provide complimentary information to
diamondoid results and rather than choosing a single
analysis, it is best to run them all. However of these
methods, diamondoid analysis is the first and only
direct, quantitative measurement of liquid to gas
conversion, i.e. oil cracking, a process which appears
to be fundamental to designing optimal tight shale
productions strategies.
134

Friday Oral Presentations
135

O-74
Tracing 13C-labeled inorganic carbon into intact polar lipids of
thermophilic anaerobic methanotrophs provides new insights
into pathways of archaeal lipid biosynthesis
Matthias Y. Kellermann 1 , Gunter Wegener 1,2 , Yu-Shih Lin 1 , Marcos Y. Yoshinaga 1 ,
Thomas Holler 2 , Marcus Elvert 1 , Kai-Uwe Hinrichs 1
1 MARUM and Dept. of Geosciences, University of Bremen, 28359 Bremen, Germany, 2 Max Planck Institute
for Marine Microbiology, 28359 Bremen, Germany (corresponding author:m.kellermann@uni-bremen.de)
Stable isotope probing using 13 C-labeled substrates is
widely applied in microbial biogeochemistry to trace
the incorporation of carbon into cell components. The
anaerobic oxidation of methane (AOM) has been
investigated by labeling of lipids [1,2] . However,
previous studies have combined the free and intact
lipid pools, thereby potentially mixing signals from
dead and living microbial biomass. Here we
conducted an in vitro stable isotope probing
experiment with a novel enrichment of thermophilic
ANME-1 archaea in order to identify substrate
specificities and patterns of lipid biosynthesis in
uncultured microorganisms.
A thermophilic active AOM community dominated by
ANME-1 consortia was enriched from hydrothermally
influenced Guaymas Basin sediments [3] . Sediment
aliquots were incubated with 13 C labeled bicarbonate
under a CH4 headspace. After extraction, we
separated individual intact polar lipids (IPLs) into
several fractions with normal- and reverse-phase
preparative HPLC. Selected archaeal IPLs were then
subjected to intramolecular isotopic analysis of their
isoprenoid chains (phytane and biphytane), sugar
headgroups [4] and the glycerol backbone [5] by GCirMS.
Pronounced differences in 13 C uptake were observed
among IPLs (e.g., 2Gly-AR and 2Gly-GDGT; Fig.1)
and within IPL components (i.e., sugars, glycerol and
isoprenoid chains; Fig.1). Weak 13 C incorporation of
2Gly-GDGT compared to other IPLs is likely due to
the succession of biosynthetic steps, with synthesis of
phosphatidylglycerol (PG)-GDGT preceding formation
of glycosidic GDGTs [6] . The stronger 13 C incorporation
of 2Gly- and PG-GDGT-PG suggests these
compounds are precursors of Gly-GDGTs.
The strong inter- and intramolecular variations in 13 C
uptake of IPLs open a new avenue for studying
membrane lipid biosynthesis of uncultured archaea
and identifying compounds diagnostic of various
stages of growth and activity. Time series incubations
of 24 day duration, different 13 C labeled substrates
and a comparison between bacterial and archaeal
IPLs will provide additional insights into the complex
biogeochemical processes involved in AOM.
Fig. 1. Differences in 13 C uptake of selected IPLs (e.g. PG-
AR, 2Gly-AR, 2Gly- and PG-GDGT-PG and 2Gly-GDGT),
including the hexose headgroups and glycerol are illustrated.
References
[1] Wegener et al. (2008) Envir. Microbiol. 10: 2287-2298.
[2] Blumenberg et al. (2005) Appl. Environ. Microbiol. 71: 4345-4351.
[3] Holler et al. (in review, ISME J.).
[4] Lin et al. (2010) Rapid Commun. Mass Spectrom. 24: 2817–2826.
[5] Lin et al. (unpublished protocol).
[6] Nemoto et al. (2003) Extremophiles 7: 235-243.
136

O-75
Methane derived carbonates as an indicator of the bottom water
anoxia: Nile Deep Sea Fan, the Eastern Mediterranean
Alina Stadnitskaia 1 , Volker Liebetrau 2 , Jaap Sinninghe Damsté 1
1 Royal Netherlands Institute for Sea Research, 't Horntje, Netherlands, 2 Leibniz-Institut für
Meereswissenschaften, IFM-GEOMAR, Kiel, Germany (corresponding author:alina@nioz.nl)
The precipitation of carbonate in methane saturated
environments is a common phenomenon that is
caused by the increase of alkalinity due to the
microbial process of anaerobic oxidation of methane
(AOM) accomplished by a consortium of sulfate
reducing bacteria and methanotrophic archaea
(Boetius et al., 2000). Since the formation of such
carbonates is irrespective to climate changes and to
the depth of the carbonate compensation, they
represent unique archives of the time and duration of
methane seepage, adjacent sedimentary/water
column environments and associated bionetwork.
The Nile Deep Sea Fan basin is known for the
widespread occurrence of seabed methane/fluid
seepage linked to mud volcanoes and pock marks.
Massive accumulations of methane-derived carbonate
pavements and up to one meter buildups were often
encountered in the vicinity or even within mud volcano
structures. Here we analyzed at high resolution the
differences in stable carbon and oxygen isotope
compositions and lipid biomarker composition,
accompanied with U/Th dating of the topmost part of
a ~1 m-high carbonate edifice sited at the margin of
the Amon mud volcano. The uppermost part of the
edifice has been dated at ~7.8 - 9.1 kyr B.P. This is
synchronous with the increase of fresh-water fluxes in
the Eastern Mediterranean resulting in density
stratification of the water column (~ 10.5 - 5.0 14 C kyr
B.P.), with the formation of S1 sapropel (~9.7 – 5.7
14 C kyr B.P.; De Lange et al., 2008), and with the
Holocene warm climatic optimum (Rohling and
Hilgen, 1991). Significant changes of � 13 CCaCO3
values, from -32 to -9‰ (VPDB), indicate swings in
methane flux, which affected rates of AOM and the
consequent production of 13 C-depleted HCO3 - . Lipid
biomarkers revealed the presence of methanotrophic
archaea of the ANME-2 group due to the dominance
of sn-2-hydroxyarchaeol over archaeol and the low
abundance of tetraether lipids (Blumenberg et al.,
2004). Ecologically these archaea are associated with
elevated methane fluxes. Lipid biomarkers indicative
of aerobic microorganisms were not detected.
The precipitation of AOM-related carbonates is limited
to oxygen-free conditions since both AOM-performing
microorganisms are so far known as obligate
anaerobes. It is clear that the formation of carbonate
build-ups above the seafloor is only possible in an
anoxic water column. De Lange et al. (2008) reported
that the whole Eastern Mediterranean Basin has been
predominantly oxygen-free below ~ 1.8 km during 4
kyr of S1 sapropel formation. The Amon mud volcano
is located at the water depth of ~ 1100 m. Our results
thus potentially indicate that during the accretion of
the studied carbonate build-up the oxycline was most
likely shallower. The U/Th age determinations were
only performed for the uppermost part of the
structure, i.e. for the latest phase of the edifice
development. Bayon et al. (2007) reported continuous
carbonate precipitation over the last ~5000 years for a
5.5 cm thick crust in this area. The timing of the buildup
formation is consistent with the period when
bottom waters of the Eastern Mediterranean were
anoxic. Most likely such carbonate edifices in the Nile
Deep Sea Fan basin are fossil analogue of the
currently existed microbial carbonate reefs in the
Black Sea fuelled by AOM (Michaelis et al., 2002).
References:
Bayon et al., 2009. Chem. Geol. 260: 47–56.
Blumenberg et al., 2004. PNAS 101: 11111–11116.
Boetius et al., 2000. Nature 407:577-579.
De Lange et al., 2008. Nature Geosci. 1: 606-610.
Michaelis et al., 2002. Science 297: 1013-1015.
Rohling & Hilgen, 1991. Geol. Mijnbouw 70: 253-264.
137

O-76
Carbon fluxes in phylogenetically distinct AOM performing
microbial consortia
Sebastian Bertram 1 , Martin Blumenberg 2 , Richard Seifert 1 , Martin Krüger 3 , Walter
Michaelis 1
1 Institute of Biogeochemistry and Marine Chemistry, University of Hamburg, Hamburg, Germany,
2 Geobiology Group, Geoscience Centre (GZG), University of Göttingen, Göttingen, Germany, 3 Section
Geomicrobiology, Federal Institute for Geosciences and Natural Resources, Hannover, Germany
(corresponding author:walter.michaelis@zmaw.de)
The anaerobic oxidation of methane (AOM) coupled
to sulphate-reduction is an important process in
marine settings. However, it is still not completely
understood, and is considered as a reverse process
of methanogenesis. An unknown electron shuttle
transfers the energy between syntrophic anaerobic
methane-oxidising archaea (ANME) and sulphatereducing
bacteria (SRB). Moreover, while
metagenomic investigations by several groups
demonstrate a high microbial diversity in AOMsettings,
the physiological capabilities of such
involved organisms are widely unknown.
One promising approach to get information on
metabolic capabilities of microbial systems is
compound specific stable isotope probing with carbon
isotopically labelled substrates, since none of the
involved organisms has been isolated in pure culture
so far.
Previous in-vitro studies with labelled methane and
bicarbonate revealed uptake into archaeal and
bacterial lipids and indicate autotrophic growth of SRB
[1, 2].
We extended our previous incubation experiments,
among others, with isotopically labelled acetate and
methanol to investigate further heterotrophic
capabilities within two different AOM communities.
These mat samples are dominated by ANME-1 or
ANME-2, respectively. They emerged under similar,
anoxic environmental conditions from the Black Sea
(Krüger et al., 2008). Our results showed an
unexpected high 13 C-uptake into archaeal lipids with
labelled methanol as substrate. Assimilation rates of
methanol-derived carbon were especially high for
sn2-hydroxyarchaeol. In contrast to experiments with
other substrates, a significant
13 C-uptake from
methanol into archaeal lipids also occurred in the
absence of methane. This suggests a strong
adaptation of involved archaea to methylotrophic
substrates. We also observed high rates of
autotrophic and heterotrophic methanogenesis. By
analysing the isotopic enrichments of methane, we
found individual impacts of different (isotopically
labelled) substrates on methanogenesis. We detected
specific lipid biomarkers for methylotrophic bacteria in
these consortia and elevated assimilation rates with
methanol indicate a homoacetogenic metabolism of
involved source organisms. Our work further suggests
chemoorganotrophic and AOM independent
autotrophic metabolic life styles of associated
bacteria. These new data reveal much higher
physiological capabilities of AOM-communities than
previously shown. Especially the so far unknown
methylotrophic physiology of anaerobic
methanotrophs or other archaea present in recent and
ancient sediments is of great importance and subject
of forthcoming studies.
References:
[1] Blumenberg M., Seifert R., Nauhaus K., Pape T.,
and Michaelis W. (2005) AEM 71:4345-4351.
[2] Wegener, G., Niemann H., Elvert M., Hinrichs K.-
U., and Boetius A. (2008) EMI 10:2287–2298.
[3] Krüger, M., Blumenberg M., Kasten K., Wieland A.,
Layla K., Klock J.-H., Michaelis W., and Seifert R.
(2008) EMI 10:1934-1947.
138

O-77
Fluid API gravity prediction in basin modelling
Rolando di Primio 1 , Eric Lehne 1 , Philipp Kuhn 1 , Friedemann Baur 2 , Brian Horsfield 1
1 GFZ German Research Centre for Geosciences, Potsdam, Germany, 2 RWTH Aachen, Aachen, Germany
(corresponding author:dipri@gfz-potsdam.de)
Kinetic models of petroleum generation are the
standard tool for the prediction of hydrocarbon
distribution and properties using basin modelling.
Such models are based on laboratory analysis of
hydrocarbon generation and extrapolation of the
reactions characterised to geologic heating rates. Our
compositional kinetic approach is termed
PhaseKinetics (di Primio, R., Horsfield, B. (2006)
AAPG Bull. 90, 1031-1058), and is based on a
combination of bulk kinetics and closed system
pyrolysis experiments to describe the compositional
evolution of generated fluids as a function of
increasing maturity. Due to the compositional
resolution used, which is based on that of PVT data
formats, the prediction of petroleum phase properties
is possible.
The prediction of phase properties of evolving
fluids, while successful with respect to GOR,
saturation pressures and phase state, lacked an API
gravity predictive capacity. Here we present results
from the GFZ project Predicting Petroleum Quality in
which this topic was addressed.
API gravity of petroleum fluids is generally assumed
to increase with increasing fluid maturity. Accordingly
trends of increasing fluid maturity, e.g. based on
biomarker parameters or physical properties such as
GOR, are expected to correlate to API gravity. Such
trends have been reported in the literature, however
they are only obvious in large data sets which include
a large variety of primary and secondary fluids. When
we exclude altered fluids from such trends, e.g. the
biodegraded fluids as well as the gas condensates
which usually contain gas generated by secondary
cracking processes, a correlation between API gravity
and maturity is very difficult to ascertain. For oilwindow
mature oils we generally observe only a very
vague correlation of API gravity and maturity, or none
at all. However, in genetically related fluids a range of
API gravities is common, usually showing a Gaussian
distribution.
Based on an extensive oil dataset, including fluids
generated by source rocks from distinctly different
depositional environments, we have been able to
identify characteristic API gravity ranges for
respective source rock types. By linking source rock
petroleum type organofacies and kerogen type, as
determined by open system PyGC, to generated fluid
API ranges we developed an approach for the
prediction of initial fluid API gravity using the
PhaseKinetic approach.
Our natural datasets indicated that typical
Paraffinic-Naphthenic-Aromatic (PNA) petroleums
show API gravity ranges between 32° and 46°,
centering around 39°API; Paraffinic-High-Wax (P-HW)
petroleums range from 35° to 50° and with a
maximum at 43°API, light oils range from 35 to 46 and
maximise at 42°API and sulphur-rich oils (PNA S-rich)
have the broadest API gravity range from 19 to 42
with a weak maximum at 29°API. Each of the
petroleum types described can be linked to a specific
source rock depositional environment using PyGC
analysis of the source rock.
Our PhaseKinetic approach uses a 14 compound
model of the generated petroleum which includes the
physical properties of each individual compound in
order to be able to calculate the phase behaviour of
the generated fluids. While the physical properties of
the compounds in original models were constant for
any fluid type, we have now generated liquid
compound physical property descriptions for four
different fluid types: PNA, PNA S-rich, P-HW and light
oils and gas condensates. In addition to the
characterisation of the primary fluid properties
generated by the respective source rocks during
maturation, the changes during maturation and
cracking were also characterised and included in the
model using compound specific secondary cracking
descriptions. This new approach was tested on a
variety of petroleum system models including a North
Sea area and the Williston Basin with excellent
results.
139

O-78
Fluid property prediction from advanced mud gas (AMG)
systems: opportunities and pitfalls
Daniel McKinney 1 , Edward Clarke 2 , E. Esra Inan 1
1 Shell <strong>International</strong> E&P, Inc., Houston, United States of America, 2 Shell <strong>International</strong> E&P B.V., Rijswijk,
Netherlands (corresponding author:daniel.mckinney@shell.com)
Fluid property prediction from mud gas logging has
been a staple of the oil industry for decades (e.g.,
Kandel 1 and references within). However, meaningful
interpretation of these data was long plagued by
inconsistent datasets resulting from poor mud gas
extraction. Recently, a step change was made in the
extraction efficiency of light hydrocarbons in mud
systems with the advent of semi-permeable
membrane technology and heated extractors. These
technologies led to more accurate assessment of the
reservoir fluid composition in, mainly, the C1-C5
range 2 . With these developments, has the ability to
accurately predict fluid properties and phase
behaviour from mud gas data improved?
In this study, insights from petroleum system analysis
and PVT are combined for accurate fluid property
prediction from AMG logging as well as outline
potential pitfalls for misinterpretation of mud gas data.
Petroleum system analysis is a key input because
both oil/source correlation as well as in-reservoir
transformation affect reservoir fluid composition, and,
thus the ability to accurately predict fluid properties
from mud gas data. For instance, oils sourced from
terrigenous material will have significantly different
composition for a given fluid GOR and in situ density
as compared to marine oils with similar properties.
Where local calibration exists, accurate assessment
of fluid properties can be ascertained. For example,
GOR can be easily estimated for an exploration well
in a setting where it has been demonstrated that there
is strong correlation with gas wetness (Wh) (Fig. 1).
Limitations to predictive capabilities can be found,
typically, in mixed petroleum systems or transformed
oil columns. For instance, mixing of dry biogenic gas
with low mature oil can be problematic for AMG
interpretation. Figure 2 shows an example where
there is a strong correlation in a given basin between
the Wh and reservoir fluid in situ density. However,
several outliers exist which have significantly higher in
situ density than what would be predicted from the
Wh value. Upon further inspection, it was understood
that these outliers are due to dilution of a low mature
oil with significant quantities of biogenic gas; a result
not appreciated until methane carbon isotopic data
had been integrated with the results.
In conclusion, great strides have been made to
improve the data quality issues that have hampered
mud gas interpretations in the past. Integration of
these data with basin modelling and petroleum
system analysis can greatly improve predictive
capabilities.
Fig. 1. Fluid property correlation (data in blue) and accurate
prediction (red star) of fluid properties from mud gas data.
Fig. 2. Fluid property correlation to in situ density and
outliers that have been diluted with biogenic gas.
References
[1] Kandel, D., Quagliaroli R., Segalini G., and
Barraud B. (2001) SPE 75307.
[2] McKinney D.E., Flannery M., Elshahawi, H.,
Stankiewicz A., Clarke E., Breviere J. and Sharma S. (2007)
SPE 109861.
140

O-79
Metre-Scale fluid property variation within an oil field revealed
by Mud Gas Isotope Logging (MGIL)
Andrew Murray 1 , Daniel Dawson 1 , Stephen Larter 2,3
1 Woodside Energy Ltd, Perth, Australia, 2 University of Calgary, Calgary, Canada, 3 Gushor Inc., Calgary,
Canada (corresponding author:andrew.murray@woodside.com.au)
The Vincent Field, on the North West Shelf of
Australia, is an oil and gas accumulation containing ~
300 mmbbls of biodegraded, heavy oil in an 18m thick
column under a dry gas cap. Development of the field
was challenging due to the oil rim being thin and the
oil of high viscosity.
Oil samples from the discovery and appraisal wells
indicated variable solution GOR and in-situ oil
viscosity but it was unclear how much of this
variability was due to structural/stratigraphic
compartmentalisation as opposed to incomplete fluid
mixing. The high porosity and permeability of the
reservoir sands together with lack of significant fault
offsets argued against compartmentalisation.
Geochemical studies of oil, free gas, solution gas and
mud gas collected while drilling were used to
determine the reasons for the fluid property variation
and allow prediction of fluid properties away from well
control. Biodegradation introduces complexity into the
assessment for two reasons: Firstly, it erases much of
the classical oil fingerprinting information which would
normally be used to assess connectivity. Secondly,
biodegradation, secondary gas generation and a
multi-phase charge history creates non-equilibrium
conditions not easily modelled by standard PVT
simulators.
Oil in the Vincent field is nearly uniformly biodegraded
everywhere. However, solution GOR varies widely on
a metre scale, causing variability in the in-situ
viscosity. The molecular and isotope composition of
the gas suggests that it is almost entirely of
secondary biogenic origin, i.e. formed during the
methanogenic biodegradation of oil. This gas appears
to have been emplaced after or during formation of
the oil leg and is still in the process of mixing into the
oil. The low differential buoyancy pressure of the
fluids means even minor discontinuities in the
reservoir matrix - unrecognisable on seismic or
petrophysical logs - can prevent fluid homogenisation,
even over geological time frames.
Because the main source of gas in the Vincent Field
is microbial methanogenesis there is a correlation
between the carbon stable isotope signature of
methane and solution GOR. This allowed mapping of
GOR and viscosity at high spatial resolution, using the
methane isotope signature as a proxy. Over 500 mud
gas samples were collected while drilling the vertical
appraisal and horizontal producer wells. The degree
of heterogeneity revealed by these measurements
was far greater than anticipated from geological
considerations and prompted re-evaluation of
production forecasts. Mud gas samples were also
taken during drilling of a horizontal well into a
downthrown fault block adjacent to the main field.
This allowed a GOR and oil viscosity estimate to be
made for this part of the field despite no oil samples
having been recovered to surface.
141

O-80
Denitrifying bacteria as potential sources of isoalkane-GDGT
Cornelia Mueller-Niggemann 1 , Andrea Bannert 2 , Michael Schloter 2 , Kai Mangelsdorf 3 ,
Lorenz Schwark 1
1 Institute of Geosciences, Christian-Albrechts-University of Kiel, 24118 Kiel, Germany, 2 Department for
Terrestrial Ecogenetics, Helmholtz Centre München, 85764 Neuherberg, Germany, 3 GFZ Potsdam German
Research Centre for Geosciences, 14473 Potsdam, Germany (corresponding author:cmn@gpi.uni-kiel.de)
Glyceroldialkylglycerol tetraethers (GDGT) have been
identified as specific membrane lipids in archaea, where
the alkyl chains are isoprenoidal and bacteria, where the
alkyl chains are composed of isoalkanes. GDGT are
biosynthesized in adaption to ambient temperatures
whereby microbes maintain the fluidity of their plasma
membranes by introducing cyclopentyl rings and methyl
groups into the alkyl chains. The distribution of GDGT is
therefore a well used biomarker in paleobiology.
Calibration of paleo-temperature proxies based on GDGT
distribution is hampered by a lack of archaeal isolates to
be grown at different temperature and a presently
unknown origin of bacteria biosynthesising isoalkane
GDGT.
Acidobacteria have been proposed as likely biological
sources for GDGT extracted from a peat bog [1] but the
examination of different culturable acidobacterial strains
revealed an absence of isoalkane-GDGT. The origin of
this abundant class of soil lipids thus still remains
enigmatic.
Rice paddy soils from the Zhejiang province of China are
rich in isoalkane-GDGT and their origin is of major
concern regarding microbial processes in this specific
environment. In order to unravel the potential origin and
ecological function of GDGT-synthesizing bacteria we
have combined bacterial lipidomics with genomics. Lipids
analyzed for bacterial sources were core-GDGT and
phospholipid fatty acids (PLFA), the latter allowing for
bacterial group fingerprinting. Genomics were conducted
by DNA extraction and quantification of genes encoding
for enzymes that are particularly important in nitrogen
cycling in paddy fields. Ammonia oxidation was assessed
by determination of bacterial amoA genes, whereas
denitrification was assessed by bacterial nirK and nirS
(nitrite reductase) as well as bacterial nosZ (nitrous oxide
reductase) gene copy numbers.
We observed a strong correlation between total soil
nitrogen and branched GDGT (Fig.1). Whereas no
correlation was found between branched isoalkane
GDGT and amoA gene copy numbers, excellent
correlation was found for nirK gene copy numbers and
the abundance of branched bacterial GDGT (Fig.1),
arguing for an origin of branched isoalkane GDGT from
members of the nitrite reducing bacteria. Correlation with
nosZ is negative (Fig.1), indicating that bacteria carrying
out this step in denitrification are not major producers of
branched GDGT. The PLFA profiles of the paddy soils
showed high abundances of C19 fatty acids with a
cyclopropyl moiety (Fig.1), correlating positively with high
numbers of nirK gene copies. As the C19 cyclopropyl fatty
acid is known to occur in Gram-negative anaerobic
bacteria and its abundance has been shown to correlate
with N2O fluxes in soil [2] the PLFA patterns corroborate
an activity of nitrite reducing bacteria in the investigated
paddy soils.
Most bacteria, which are able to denitrify, use nitrate as
alternative electron acceptor when oxygen is missing in
soil. Therefore, it might be speculated that branched
isoalkane GDGTs are metabolized by this functional
group as a response of oxygen concentrations in soil.
Fig.1. Correlation of GDGT with soil nitrogen, nirK and nosZ gene
copies and cyclopropyl C19 PLFA
[1] Weijers et al. (2009) Geomicrobiol J. 26, 402-414
[2] Balser and Firestone (2005) Biogeochem. 73, 395-415
142

O-81
Hydrogen isotopic compositions of archaeal tetraethers
Masanori Kaneko 1 , Hiroshi Naraoka 2
1 University of Nevada-Reno, Reno, United States of America, 2 Kyushu University, Fukuoka, Japan
(corresponding author: m_kaneko@jamstec.go.jp)
During the past decade, compound-specific
hydrogen isotope (δD) analysis has been conducted
on eukaryotic and bacterial lipid biomarkers, which
provides us information about paleoclimate,
paleosalinity, and metabolic pathways (Pagani et al.,
2006; Zhang et al., 2009). However, the hydrogen
isotopic composition of archaeal membrane lipids has
not been explored because of analytical difficulty.
Recently we have developed δD analysis of
archaeal tetraether lipid in which biphytane iodide
produced by HI treatment of the tetraether lipid is
quantitatively hydrogenated with H2 bubble on a
catalyst PtO2. Using the developed method, we will
present the δD values of archaeal membrane lipids in
sediment cores (Sites U1327 and U1328) collected
from the northern Cascadia margin accretionary prism
during IODP Expedition 311.
Lipids were extracted using organic solvents, and
tetraether lipids were separated using silica gel
column chromatography. The tetraether lipids were
reacted with HI at 110°C for 3h to cleave ether bonds.
Resulted biphytane iodides were recovered with
hexane and were subsequently hydrogenated as
descrived above. δ 13 C and δD analyses of BPs were
performed by GC/IRMS. δD value of incorporated
hydrogen to BPs was determined by hydrogenation of
δD–known iodeoctadecane, which allowed to correct
δD value of BPs.
In the sediment cores, BPs with the valuable
number of cycloalkane ring (BP[0] to BP[3], [n] is the
ring number) were existed as components of
tetraether lipids. BP[3] contained a cyclohexane ring,
suggesting a marine crenarchaeotic origin. From an
aspect of δ 13 C values of BPs (Fig. 1), archaeal
sources in this study were divided into two groups,
crenarchaeotic origin (BP[3], BP[0] and BP[2] with
−19.9±1.8‰) and other (BP[1] with −16.1 to −48.8‰).
The BPs derived from Crenarchaeota are a little
enriched in 13 C relative to bulk organic carbon
(−23.7‰), which indicates the Crenarchaeota are
heterotroph. On the other hand, the 13 C-depletion of
BP[1] suggests an additional mixing of archaeal
source (e.g. methaogen).
δD variation of BPs ranges from −324 to −181‰
with a unique δD distribution pattern: δDBP[0]< δDBP[2]<
δDBP[3]< δDBP[1]. This distribution pattern is consistent
with a relationship between δD value and the ring
number of BPs in Sulfolobus culture (Kaneko et al, in
press), except for BP[1]. This observation also
suggests the two archaeal sources. Considered large
hydrogen isotope fractionation during lipid synthesis
by heterotrophic archaea (−213 to −161‰, Kaneko et
al., in press), it is possible that BP[3], BP[2], and
BP[0] is derived from heterotrophic Crenarchaeota.
On the other hand, contribution of methanogen
accounts for D-enrichment of BP[1] because more
than 60% of hydrogen of BP synthesized by
methanogen can be same to that of methane (−180‰,
Pohlman et al., 2010). Thus, δD value of BPs should
reflect archaeal metabolic pathways.
Fig. 1. Carbon and hydrogen isotopic composition
of biphytanes from this study.
REFERENCES
Kaneko et al, Organic Geochemistry in press.
Pohlman et al. (2009) Earth Planet. Sci. Lett. 287,
504–512.
Pagani et al. (2006) Nature 442, 671–675.
Zhang et al. (2009) Proc. Natl. Acad. Sci. U.S.A.
106,12580–12586.
143

O-82
Tetraether lipid profiles in cultures and sediments: novel
structures and geochemical significance
Christopher Knappy 1 , Hugh Morgan 2 , Brendan Keely 1
1 University of York, York, United Kingdom, 2 University of Waikato, Hamilton, New Zealand (corresponding
author:brendan.keely@york.ac.uk)
Since the recognition of the presence and
significance of mesophilic archaea throughout the
oceans, numerous studies have included the
measurement of their glycerol dialkyl glycerol
tetraether (GDGT) lipid cores and related structures
to enable reconstruction of features of the
palaeoenvironment (e.g. Schouten et al., 2008).
Such studies have utilised proxies based on GDGT
lipid cores to reveal sea surface water temperature,
atmospheric air temperature and terrestrial input to
marine and lacustrine environments. The
determination of the tetraether lipid core relative
abundances that are crucial to these proxy
measurements has relied on the measurement of
chromatographic peak areas obtained duing
atmospheric pressure chemical ionisation liquid
chromatography mass spectrometric (APCI LC-MS)
analysis of sediment extracts.
The application of tandem mass spectrometry
during APCI-LC/MS represents a straightforward
means to distinguish structurally distinct families of
tetraether lipid cores in which variation exists in the
number of alkyl chains. Thus, the corresponding
trialkyl (GTGT) and monoalkyl (GMGT) structures
can readily be distinguished from each other and
from the GDGT lipids from their product ion spectra
(Knappy et al., 2009).
An additional benefit of the application of tandem
mass spectrometry is demonstrated by this study.
APCI LC-MS/MS analysis reveals a level of
complexity in the tetraether lipid core distributions
that has not previously been recognised. The
distributions in cultures that have been well
described (e.g. Sulfolobus acidocaldarius) are
shown to contain a series of minor components in
which additional methyl groups appear at various
positions within the structures. The differing
positions of attachment suggest differences in the
biological roles and functions of the different
structural types. Extracts of hyperthermophiles
containing both GDGT and GMGT lipids show a
dominance of the latter and reveal changes in the
lipid core distributions with change in the
temperature at which the cultures are grown,
implying functional significance in the lipid
membrane structure.
The high levels of the GMGT lipid cores in a
Crenarchaeote indicates, contrary to the previous
suggestion that these structures may represent
kingdom-specific biomarkers for the Euryarchaeota
(Schouten et al., 2008), that GMGT lipids are more
widespread throughout the Archaea. The
recognition of the wide structural diversity that
exists among tetraether lipids of organisms grown
in culture indicates that considerably more effort is
required to understand the functional and
distributional significance of the lipids and to
optimise the use of their distributions of the lipid
cores in palaeoenvironmental assessment.
The analysis of sediment extracts by APCI LC-
MS/MS shows the distributions of the tetraether
lipid cores to be highly complex and to contain a
large number of novel and remarkable structures
that challenge our understanding of the routes by
which tetraether lipid cores are formed.
Knappy C.S., Chong J.P.J., Keely B.J. (2009).
Journal of the American Society of Mass
Spectrometry. 20, 51-59.
Schouten S, Baas M, Hopmans EC, Damsté JSS
(2008). Organic Geochemistry, 39, 1033-1038
144

O-83
Evolution of ―shale gases‖ in fractured reservoirs in the foothills
of the Western Canada sedimentary basin
Barbara Tilley, Karlis Muehlenbachs
University of Alberta, Edmonton, Canada (corresponding author:btilley@ualberta.ca)
We have reported that isotopically reversed gases
predominate in Permian and Triassic fractured, mixed
clastic-carbonate reservoirs in the Western Canada
Foothills. We suggest that this resource is actually
mature shale gas in disguise (Tilley et al., AAPG
Bulletin, 2011, in press). Simultaneous cooking of
kerogen, oil and gas in closed system shales yielded
gas with light � 13 C ethane and heavy � 13 C methane.
This very mature gas was released from the shales
and trapped in fractured folds of brittle clasticcarbonate
rocks during deformation and thrust faulting
of the Laramide Orogeny, creating prolific gas pools.
Whereas conventional gas reservoirs worldwide, that
show no isotope reversal, have captured gas released
from shales during burial, shale gas is a resource
retained in place as the gas evolves from the
simultaneous destruction of kerogen, oil and gas.
The presence of reversed gases in the fractured
reservoirs in the WCSB Foothills is due to the unique
combination of (a) high maturity of the shale source
rocks, (b) tight, non-permeable rocks surrounding the
source shale (c) intense tectonic disturbance after the
source rocks reached advanced stages of maturation,
ie. after oil and gas cracking had been initiated, and
(d) deformation of the shale source rocks to both
squeeze out the gas into surrounding newly fractured,
brittle rock as well as to provide a seal.
Foothills gas reservoirs are highly compartmentalized
as reflected in the large variation of isotope ratios
from closely spaced wells (Fig. 1). Gases can be
grouped according to putative differences in the
timing of gas release from the shale and the degree of
openness or closeness of the system and whether or
not the entire gas package was preserved.
Gp 1: - Mature gas released from shale during the
tectonic disturbance.
Gp 2: - Shale gas with a greater contribution from oil
cracking than Gp 1. (The most prolific gas producing
wells).
Gp 3: - Conventional gas reservoirs. Early gas
released during burial after only kerogen maturation.
Gp 4: - Gas from oil cracking. Over mature methane
from kerogen has been mostly lost. (Poor producers)
Gp 5: - Loss of some of the Gp 1 shale gas package.
(Wells may have a water leg.)
Questions to be asked are: Can one generalize from
the Foothills‘ reservoirs to mature shale gas
worldwide? Are the isotope reversals or ―rollovers‖
that are frequently seen in productive shale gas plays
the result of closed system, simultaneous kerogen
and oil cracking? The shale gases in the Foothills
fractured reservoirs and in the Horn River Basin are
very dry compared to shale gases reported from the
U.S.A. How and why does the magnitude of the
isotope effect in gases varying with an order of
magnitude difference in gas wetness? We suggest
that prolific reserves of gas in high maturity shales
around the world have formed analogously to Groups
1 and 2 gases in the Foothills. It would seem that in
the very dry gas systems, the magnitude of the
isotopic reversal is much larger than in the wet
systems, perhaps reflecting a greater degree of oil
cracking.
Fig.1. � 13 C methane versus � 13 C ethane cross plot of WCSB Foothills gases.
Gas groups 1 to 5 are described in the text. Symbol shapes indicate location:
crosses:-Sukunka, BC; triangles –Narraway, Alberta; squares - Minnow, Alberta.
Green symbols - Permian, blue and purple - Triassic; grey -Devonian.
145

O-84
Prediction of gas volume and dryness in shale gas systems:
kinetic modeling of kerogen and retained hydrocarbons thermal
cracking in Barnett And Posidonia shales
Françoise Behar 1 , Daniel Jarvie 2
1 IFP Energies Nouvelles, Rueil-Malmaison, France, 2 Worldwide Geochemistry Company, Humble, United
States of America (corresponding author:francoise.behar@ifpenergiesnouvelles.fr)
The aim of the present study is to predict the volumes
of the different sources of gas generated during
kerogen cracking in the Ro range 0.5 to 3.0 and to
add the contribution of generated gas from secondary
cracking of retained hydrocarbon compounds in
source rocks after the main phase of primary
expulsion. For that purpose, two immature kerogens
from the Barnett Shale (US) and from the Posidonia
Shale (Germany) were selected. First they were
artificially matured by closed system pyrolysis in the
temperature range 250-350°C and with durations
between 1 to 216h. Then, for late gas generation,
kerogens already matured at 375°C/24h, were heated
between 400 and 600°C.
The following kinetic schema was optimised (Behar et
al., 2008a) :
Kerogen = non HC gas + HC1 + Asp. + kerogen 2
Asphaltenes = non HC gas + HC1 + Resins + prechar
Resins = HC1 + prechar
HC1 = HC2 + prechar
The optimised kinetic parameters show that the
asphaltenes are as unstable as the kerogen from
which they originate. Their maximum yields are 64 –
65% for the two samples, with those of the resins
being respectively 19 and 28% for the Barnett and
Posidonia. The associated gas generated with oil
does not exceed 5% and is mainly wet. The maximum
yield of late gas is respectively 6% and 4% for the
Barnett and Posidonia kerogens. It is almost pure
methane since the ethane yield does not exceed
0.4% and neither propane and butane are produced.
For the two shale gas kerogens, a full compositional
kinetic model (Behar et al., 2008b) was used to
predict both the mass balance and chemical
composition of the retained compounds after the main
phase of oil generation and expulsion. Then, from this
mass balance, it was possible to predict the gas
volume and dryness during further thermal maturation
for Ro range between 1.0 and 2.7 %Ro. Results are
shown on Fig. 1 for the Barnett shale. In the Ro range
between 1 and 1.5%, the gas dryness rapidly
increases from 65 to 80% with a maximum yield of
4%. Then, an additional contribution of 3% of dry gas
leads to a final gas dryness at almost 90% These
results are in excellent agreement with observed data.
dryness dryness (%) (%)
yield yield (%) (%)
6.0
4.5
3.0
1.5
Gas generation
0.0
1.0 1.5 2.0 2.5
100
90
80
70
60
Ro (%)
Gas dryness
50
1.0 1.5 2.0 2.5
Ro (%)
wet gas
dry gas
Fig. 1: Prediction of gas volume and dryness under
geological conditions in the Ro range from 1 to 3%.
References :
Behar, F., Lorant, F., Lewan, M.D., 2008a.
Elaboration of a new compositional kinetic schema for
oil cracking. Organic Geochemistry 39, 764-782.
Behar, F., Lorant, F., Mazeas, L., 2008b. Elaboration
of a new compositional kinetic schema for oil
cracking. Organic Geochemistry 39, 764-782.
146

O-85
Mechanistic study of shale gas generation and gas isotope
fractionations
Yongchun Tang, Daniel Xia
PEER Institute, Covina, United States of America (corresponding author:tang@peeri.org)
Recently abundant production and geochemical data
of shale gas accumulated during the extensive
exploration and development in the U.S provide
geochemists with a close look at the details of shale
gas generation. In particular, the systematic
measurements show a surprising patterns of carbon
isotope composition (� 13 C) of C2H6 and C3H8, which
becomes more negative at deeper depth (known as
―rollover‖). [1] Similar phenomenon was also found in
the conventional gas reservoir in the Ordos Basin,
China. In addition, the hydrogen isotope of CH4 (�D1)
from the Appalachian Basin of USA also shows a
reversal trend with depth. [2] This abnormal
phenomenon may relate to some special processes of
natural gas generation under geological condition.
In order to explain the isotope reversal phenomenon,
different mechanisms have been proposed.
Fractionation caused by adsorption/desorption is
unlikely the reason, since one would not expect to see
large reversal of � 13 C2 (>10 per mil) due to small
differences of any adsorption/desorption energies of
13 C labeled and unlabeled C2H6. Diffusion might
cause strong fractionation during shale gas
production; however the effect would be stronger for
CH4 than C2H6 (due to the larger isotope effect on
molecule mass of methane).
Gas mixed from dominant amount of late gas (dry gas
generated from high mature kerogen) and minor
amount of secondary gas, with volume ratio around
99% : 1%, may fit well to the ―rollover‖ trend of � 13 C2
against wetness and the normal trend of � 13 C1; but
the �D1 values become more negative with increasing
maturity and depth remains unknown. Since �D of
water in shale formation (-50 to -80 per mil) is much
more positive than organic matter, the reversal of �D1
is unlikely due to isotope exchange. The overall of �D1
values can only be explained by the contribution of
hydrogen from oil or condensate. Since the oil or
condensate cracking will generate more wet gases
and it is impossible to explain the rollover of hydrogen
isotope by oil cracking.
One of our considerations is hydrocarbon reforming
reaction with water to form CO2 and H2 under shale
gas geological condition. To address this issue, we
performed sealed gold tube pyrolysis of model
compounds under conditions with and without water.
The model compounds included in this study are
isooctane, benzene, toluene and 1-methylnaphtalene
(1-MN). Significant amount of CO2 and H2 were
generated at vitrinite reflectance equivalent of 2%.
Based on the model compound study, the relative
rates of the hydrocarbons water reforming reactions
are: branched alkane > alkyl polyaromatics > alkly
benzene > benzene.
Hydrocarbon reforming reaction with water is very
important toward the mechanism of shale gas
generation. CO2 generated from this reaction may
have dissolved certain minerals and increased the
porosity and permeability. Based on the observation
of geothermal fluid methane formation, the reforming
product of CO2 and H2 may generate relative dry
methane with ethane and propane isotopically lighter
than methane, [3] and decrease water saturation.
References
[1] Zumberge, J. E., Ferworn, K. A., Curtis, J. B.
(2009) Gas character anomalies found in highly productive
shale gas wells. Geochim. Cosmochim. Acta 73, A1539.
[2] Burruss, R. C., Laughrey, C. D. (2010), Carbon
and hydrogen isotopic reversals in deep basin gas: Evidence
for limits to the stability of hydrocarbons. Org. Geochem. 41,
1285-1296.
[3] Sherwood Lollar, B., Westgate, T. D., Ward, J. A.,
Slater, G. F., Lacrampe-Couloume, G. (2002), Abiogenic
formation of alkanes in the Earth's crust as a minor source
for global hydrocarbon reservoirs, Nature, 416, 522-524.
147

Monday Poster Presentations
148

P-001
Maturity assessment based on dibenzothiophenes distribution
analyzed by comprehensive two-dimensional gas
chromatography with time of flight mass spectrometry in oils
from Colombia
Raphael S. F. Silva 1 , Hélen G. M. Aguiar 2 , Mario D. Rangel 2 , Débora A. Azevedo 1 ,
Francisco R. Aquino neto 1
1 LAGOA-LADETEC, Departamento de Química Orgânica, Instituto de Química, Universidade Federal do
Rio de Janeiro, Rio de Janeiro, Brazil, 2 Petrobras/Cenpes/PDEXP/GEO, Rio de Janeiro, Brazil
(corresponding author:debora@iq.ufrj.br)
Dibenzothiophenes (DBTs) are aromatic sulphur
compounds used to maturity assessment [1]. In this
work the maturity level of ten oil samples from
Colombia was evaluated by comprehensive twodimensional
gas chromatography with time of flight
mass spectrometry (GC×GC-TOFMS). Several
studies using GCxGC have been published in the
literature [2].
The oil samples are from Upper Magdalena Valley
Basin, Colombia. The aromatic fraction of all oil
samples were analysed in a GCxGC-TOFMS System
Pegasus 4D. The column set used was a DB-5MS (30
m) as first dimension and a BPX-50 (1.3 m) as
second dimension.
The DBTs distribution of one sample is shown in
Fig.1a. Three ratios (4-/1-MDBT, 4,6-/1,4-DMDBT
and 2,4-/1,4-DMDBT) have been calculated by
GC×GC-TOFMS. The values for 4-/1-MDBT ratio
ranged from 1.16 to 2.40. The values for ratio 4,6-
/1,4-DMDBT ranged from 0.29 to 1.22. The values for
2,4-/1,4-DMDBT ratio ranged from 0.20 to 0.83.
Classical maturity biomarker parameters were
calculated for oils. Ts/(Ts+Tm) ranged from 0.40 to
0.51, C29ααα S/(S+R) from 0.47 to 0.57, C29
ββ/(αα+ββ) from 0.42 to 0.52 and TA/(TA+MA)
ranged from 0.36 to 0.51. These parameters did not
vary significantly for the samples, which show similar
levels of thermal evolution for the oils.
However, the maturity assessment based on DBT
ratios has a greater range, which allows a better
evaluation of thermal evolution. In Fig.1b is presented
a plot of the RMDBT 4/1 versus RDMDBT 4.6/1.4
ratios. The oils A, C and J were considered the most
mature, while oil H was the less mature. DBT ratios
allowed a better grouping of oils with similar maturity
level as oils E and F.
The aromatic compounds are more resistant to
biodegradation than saturated one which makes them
useful for maturity assessment. The BPX-50 column
used as second dimension provides better resolution
DBTs furnishing the peak area without coelutions.
(a)
(b)
Fig.1. (a) 3D view of the two-dimensional chromatogram of DBTs analysis for one Colombian oil
sample: dibenzothiophene (DBT), methyl-dibenzothiophenes (MDBTs), dimethyldibenzothiophenes
(DMDBTs), trimethyl-dibenzothiophenes (TMDBTs) and tetramethyldibenzothiophenes
(TeMDBTs). (b) Plot of two DBTs ratios for the oils analyzed.
References
[1] Chakhmakhchev, A. et al. (1997). Org. Geochem. 26, 483-490.
[2] Aguiar, A. et al. (2010). Fuel, 89, 2760-2768.
149

P-002
Structure and function of asphaltenes: a geochemical and
ultrasound study
Geoff Abbott 1 , Malcolm Povey 2
1 Newcastle University, Newcastle upon Tyne, United Kingdom, 2 Leeds University, Leeds, United Kingdom
(corresponding author:geoff.abbott@ncl.ac.uk)
Asphaltenes are well known to be the most important
components causing blockages in oil pipelines and
fouling in refineries which lead to enormous costs
They are also responsible for the formation of tar
mats in petroleum reservoirs, which can impede crude
oil recovery (Wilhelms and Larter, 1994). Despite the
amount of effort that has been expended on studying
these nanoparticles there is still a great deal of debate
surrounding a number of their fundamental properties.
For instance there is the question of whether the
solution behaviour of associating molecules better
explain the features of asphaltene-containing
systems, where the high viscosity of bitumen and
asphaltenic mixtures is related to their proximity to the
glass transition (Sirota, 2005), or is the colloidal
model the more useful one in establishing structural
features of asphaltene aggregates including their
shape and size? In this presentation we integrate
petroleum geochemistry with ultrasonic spectrometry
and microscopy to gain new insights into the
aggregation properties of asphaltenes.
Our working hypothesis is that the asphaltenes, under
certain conditions of solvent, ionic strength and type
of ion, form vesicles and that the swelling of the
vesicles by solvent increases the volume occupied by
asphaltene particles. A glass transition may then
occur due to excluded volume effects amongst the
particles (e.g. Tanaka, 2000). These differences in
asphaltene properties are supported by the
ultrasound spectrometry of these three sample types.
When we diluted fresh North Sea oil with 50%
toluene, we observed that the oil, when swilled
around the walls of the glass container had a grainy
appearance. In the spectrometer sample cell, as the
sample levels went up and down it left rivulets of oil
streaming down the walls (see inset to Fig. 1). This
indicates phase instability. The attenuation spectrum
contained breaks and departures from the normal
power law dependence (see ▲in Fig. 1). Where the
curves depart from power law dependence, this
indicates that the samples change DURING a single
frequency sweep. The fresh crude oil therefore shows
clear signs of a changing size of the scattering
entities. In contrast, the toluene diluted biodegraded
oils and bitumen (including the isolated asphaltenes)
behave exactly like the toluene in which they are
suspended, indicating that in this case no measurable
excess scattering was occurring. These results
demonstrate the potential that lies in bringing together
the normally disparate disciplines of organic
geochemistry and ultrasonic spectroscopy in order to
improve our fundamental understanding of the
asphaltene fraction.
REFERENCES
1. Wilhelms, A. and Larter, S.R. (1994) Marine
and Petroleum Geology 11, 418-441.
2. Sirota, E.B. 2005 Energy and Fuels 19, 1290
– 1296.
3. Tanaka, H. (2000) Journal of Physics:
Condensed Matter 12, R207–R264
Figure 1. Ultrasound attenuation plotted as a function
of frequency for a range of North sea crude oils,
source rock bitumen and isolated asphaltenes.
Attenuation (dB/in)
1000
100
10
1
0.1
y = 0.0189x 1.9999
0.01
1 10 100 1000
Frequency (MHz)
Toluene Attenuation (dB/Inch)
R 2 = 1
Fresh oil maltenes Attenuation (dB/Inch)
Fresh oil Attenuation (dB/Inch)
Biodegraded oil asphaltenes Attenuation (dB/Inch)
Diluted crude 1 Attenuation (dB/Inch)
diluted crude 2 Attenuation (dB/Inch)
diluted crude 3 stirred 1190 Attenuation (dB/Inch)
diluted crude 4 stirred 300 Attenuation (dB/Inch)
Kimmeridge asphaltenes Attenuation (dB/Inch)
Kimmeridge bitumen Attenuation (dB/Inch)
Power (Toluene Attenuation (dB/Inch) )
150

P-003
Factors controlling extractability of polycyclic aromatic
hydrocarbons from sedimentary organic matter using non-ionic
surfactant
Akinsehinwa Akinlua 1 , Torsten Schmidt 2
1 Obafemi Awolowo University, Ile-Ife, Nigeria, 2 University of Duisburg-Essen, Essen, Germany
(corresponding author:geochemresearch@yahoo.com; aakinlua@oauife.edu.ng)
The extraction of polycyclic aromatic hydrocarbons
(PAHs) from sedimentary organic matter by non-ionic
surfactants with the assistance of microwave was
investigated and the conditions for maximum yield
were determined. The results showed that the
extraction temperatures and kinetic rates have
significant effects on extraction yields of the PAHs.
The optimum temperature for microwave-assisted
non-ionic surfactant extraction of PAHs from
sedimentary organic matter was 120 o C. The optimum
extraction time for most of PAHs was at 40 minutes
while a few had it at 30 minutes. The results also
show that microwave-assisted non-ionic surfactant
extraction is a good and efficient green analytical
preparatory technique for leaching PAHs from
sedimentary organic matter.
151

P-004
Preliminary study of acid degradation of lignin using microwave
energy
Béatrice Allard, Sylvie Derenne
BIOEMCO CNRS/UPMC, Paris, France (corresponding author:beatrice.allard@upmc.fr)
Lignin is a heterogeneous and highly cross-linked
macromolecule particularly resistant to
biodegradation. This complex macromolecule is
composed of methoxylated phenol units linked by
ether and carbon bonds. It has long been known that
arylglycerol-�-O-aryl ether linkages are the most
abundant linkages in lignin. Acid-catalyzed
degradation generally cleaved these ether bonds
providing structural information on ether-linked units
in lignin.
Microwave irradiation has been successfully applied
in organic chemistry with reported more rapid
reactions, higher yields and improved product purities.
Microwaves are high frequency electromagnetic
waves which are strongly absorbed by polar
molecules. Absorption results in rapid and intensive
dielectric heating. Microwave systems using closed
vessels can operate at high temperature and pressure
and the temperature of solvent can be raised above
its theoretical boiling point.
In this preliminary study we explored the influence of
microwave irradiation on acid degradation of lignin.
Two types of lignin, namely hydrolytic (LHE) and
organosolv (LOS), were submitted to HCl 1N
degradation under microwave irradiation. The
investigated parameters were, the power of the
microwave source (100 and 300 W) and the nature of
the solvent (dioxane and 2-propanol). Due to their low
and high microwave absorbing capacities,
respectively, these solvents exhibit different efficiency
in the conversion of electromagnetic energy into heat
energy. Lignin monomeric and dimeric products
released under these conditions were analysed using
GC-MS.
The relative proportions of cinnamyl, guaiacyl and
syringyl units in the monomeric fraction depends on
the origin of the lignin. The composition of this fraction
does not appear to depend on the solvent and on the
delivered power. Acid degradation of LHE in dioxane
resulted in very low amounts of dimers whatever the
power used. On the other hand, an increase in the
relative proportions of dimers is observed when 2propanol
is used. These dimers consist mainly of
stilbene- and pinoresinol-related structures.
In contrast, acid degradation of LOS yielded high
amounts of dimers, even in dioxane. This indicates
the high level of ether linkages in this lignin. Stilbene-
and pinoreresinol-like substructures largely dominate
the dimer fraction.
This degradation technique could be a valuable
method for the analysis of lignin in complex sample
matrix such as soils and sediments.
GC-MS total ion chromatograms of products
recovered following acid degradation of LHE and LOS
in dioxane and 2-propanol.
152

P-005
A Monte Carlo application for introducing source variability in
source apportionment calculations
August Andersson 1 , Rebecca Sheesley 1,2 , Jorien Vonk 1,3 , Örjan Gustafsson 1
1 Stockholm University, Stockholm, Sweden, 2 Baylor University, Waco, United States of America, 3 ETH,
Zurich, Switzerland (corresponding author:august.andersson@itm.su.se)
End-member mixing analysis (EMMA) using e.g.
molecular and isotopic markers are commonly used to
decipher the relative contributions from different
sources to a mixed environmental sample. By setting
up a set of linear equations with N+1 sources and N
source markers, the relative source contributions may
be solved analytically. A major drawback of that
standard approach is that the natural variability of the
source markers (the end-members) is not taken into
account. Here a Monte Carlo approach for accounting
of the end-member variability in source calculations is
presented.
This methodology is exemplified by two applications:
1. Apportioning relative contributions to organic
carbon (OC) in Arctic Ocean surface sediments from
marine, riverine and erosion sources using 13C and
14C isotope [1]. Interestingly, the erosion component
was found to be around 50%, irrespective of the
distance of the sampling site to the Kolyma river
mouth, Figure 1.
2. Apportioning relative contributions to carbonaceous
aerosols in southern Asia from biomass combustion,
liquid petroleum combustion and coal combustion
using various polyaromatic hydrocarbon (PAH)
signals as molecular source markers [2]. This study
shows that the fossil fuel contribution is roughly
equally split between petroleum- and coal combustion
sources.
Taken together, these results points to the general
conclusion that source variability influences both the
calculated relative contributions from different sources
and the precision by which it may be calculated. This
conclusion is reinforced by analysis of synthetic data
sets, designed to span the main source configurations
possible.
Figure 1 Relative contributions (with error bars) of
riverine, erosion and marine contributions to OC in
surface sediments along the Kolyma paleoriver.
References
[1] Vonk, J. et al. (2010) Biogeosciences, 7, 3153-
3166
[2] Sheesley, R. et al. (2011) Atmospheric
Environment, Accepted for publication.
153

P-006
Chemical and geochemical characterization of heavily
biodegraded oils from Colombia by comprehensive twodimensional
gas chromatography coupled to time-of-flight mass
spectrometry (GCXGC-TOFMS)
Renata Filgueiras 1 , Ricardo Pereira 1 , Raphael Salles 1 , Leonardo Mogollón 2 , Débora
Azevedo 1
1 Universaidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil, 2 Ecopetrol, Piedecuesta, Colombia
(corresponding author:renata_filgueiras@yahoo.com.br)
Biodegradation of crude oil in subsurface petroleum
reservoirs is an important alteration process with
major economic consequences. Geochemical
parameters using biomarkers are important to
characterization of oil-oil and oil-rock source
correlations. 1 In this way, the correct identification of
biomarkers is important to knowledge concerning
origin and migration of oil, even in biodegraded
samples. Comprehensive two-dimensional gas
chromatography coupled with time-of-flight mass
spectrometry (GC×GC-TOFMS) is an appropriate
technique for the elucidation of molecular composition
of complex petrochemical samples, such as
biodegraded oils. 2 This work provides the first study
concerning biomarker geochemical characterization of
heavily biodegraded oils from Colombia by GCxGC-
TOFMS, aiming the separation, identification and
quantification of biomarkers to determine geochemical
ratios.
Saturated fractions of four heavily biodegraded oil
samples from Colombia, named oils #1, #4, #5 and
#6, were analyzed on a GCxGC-TOFMS Leco
Pegasus 4D. The column set used was a HP-5MS (30
m) as first dimension and a BPX-50 (1.5 m) as
second dimension. The compounds were tentatively
identified by the use of ChromaTOF 4.0 Software.
The geochemical parameters calculated for all
samples are given in table 1. The samples have
distinct characteristics mainly concerning
biodegradation, which can influence parameters
related to thermal evolution and origin. Tri and
tetracyclic terpanes, esteranes, hopanes,
bisnorhopanes (BNH), trisnorhopanes (TNH), 25norhopanes
(C26-C34), norgammacerane,
secohopanes and n-alkanes were detected in
samples #4, #5 and #6. The detection of these
compounds is characteristic of a mixture of nonbiodegraded
and biodegraded oils. On the other
hand, the same compounds were identified in the
sample #2, except n-alkanes, esteranes and
homohopanes (C31-C35), characterizing heavily
biodegraded oil. This distinction is based on the
increasing 25-norhopane/C30-hopane ratios
(25NH/H30), which have high values between 1.36
and 6.04 (Table 1).
Table 1. Some geochemical correlations showing
source parameters of samples.
Parameter Oil 2 Oil 4 Oil 5 Oil 6
25NH/H30 6.04 2.14 2.38 1.36
Hop/St nd 0.9 0.99 1.08
H30/C27 ααα nd 1.55 0.97 1.87
C27 (%)
C28 (%)
C29 (%)
nd
nd
nd
49.0
34.4
16.6
41.8
27.7
30.5
42.6
33.7
23.6
Tr23/H30 7.77 8.66 3.89 5.91
Te24/H30 nd 0.80 0.64 0.53
Tr25/Tr26 0,64 0.74 1.05 1.74
H35/H34 nd 1.39 1.49 1.57
nd = not detected.
Hopane/Sterane ratios between 0.97 and 1.87 are
indicative of marine organic matter deposition with
contribution of algae and plankton. The predominance
of C27 steranes indicates major contribution of marine
phytoplankton. 5
For all samples the low concentration of tricyclic
terpanes C19 and C20, when compared to C23, is
also indicative of marine oils. The detection of
tetracyclic poliprenoids, C30 sterane, 28,30-BNH and
25,28,30-TNH are indicative of oils samples probably
derived of anoxic marine depositional environment. 2
The higher sensibility and chromatographic
resolution allowed a better characterization of oil
fractions. In addition, geochemical parameters were
calculated, demonstrating the applicability of GCxGC-
TOFMS in biomarker ratios. So, the use of GCxGC-
TOFMS in geochemical analysis can easily support oil
exploration.
References
[1] Peters, K.E. et al. (2005). The Biomarker Guide,
2 nd Edition, Cambridge University Press: New
York, 1155 pp.
[2] Aguiar et al. (2011).Energy & Fuels, in press.
154

P-007
High resolution measurement of tarmat in cores using laser
pyrolysis
Daniel Dessort, Philippe Lapointe, Dominique Duclerc, Robert Le-Van-Loi
Total S.A., Pau, France (corresponding author:daniel.dessort@total.com)
Tarmat is a dark brown to black, thick, semisolid to
viscous mixture of heavy hydrocarbons enriched in
asphaltenes that occurs naturally in reservoirs.
Tarmat cannot be produced and is a nuisance
because it impacts on OIP assessment, on reservoir
quality (porosity, permeability, wettability...), on
development plans when tarmat forms permeability
barrier and on the response of electric logs.
Thus the Prediction and the Modeling of the vertical
and horizontal distribution of Tar mats require high
resolution & quantitative analysis.
Conventional core- or log-based methods for solid
bitumen analysis are not always satisfactory (poor
resolution and/or not reliable data).
The LIPS (Laser Induced Pyrolysis System) is a new
instrument developed by TOTAL. It performs the
automatic acquisition of quantitative and high
resolution (centimetric or sub-centimetric) logs of
organic carbon on cores (Tar mats, source rocks, oil
shales, gas shales).
The LIPS consists in:
1. One mobile bench carrying the core,
2. One power laser providing a continuous infra-red
laser beam through an optical fiber,
3. One 3D movable head which guides the laser
beam and collects the material expelled from the
core during the laser shoot,
4. One or more detectors which can be used for
analyzing the material pyrolyzed and expelled
from the core during the laser shoot (mass
spectrometer, PID, FID, sulphur detector…)
5. An acquisition and data processing system.
Typically one data point can be acquired every
minute.
The LIPS data are calibrated using the Rock- Eval in
reservoir mode allowing the quantitative analysis of
solid bitumen (sum of S2b peak + refractory organic
carbon). Thus, the results can be expressed as %
bitumen in whole rock or in porosity, when the
porosity is known.
155

P-008
High resolution measurement of petroleum potential of oil
shales using laser pyrolysis on cores
Daniel Dessort, Pierre Allix, Jean-Michel Krafft, Dominique Duclerc, Robert Le-Van-Loi
Total S.A., Pau, France (corresponding author:daniel.dessort@total.com)
Conventional core- or log-based methods for TOC
and petroleum potential measurement are not always
satisfactory. For oil shale these parameters are
important:
� For calculating the yield of petroleum which
can be produced from oil shale pyrolysis,
� For extrapolating, modeling and mapping the
remaining petroleum potential of oil shale
deeper in the basin (oil shales may have
deeper gas shale potential).
The LIPS (Laser Induced Pyrolysis System) is a new
instrument developed by TOTAL. It performs the
automatic acquisition of quantitative and high
resolution (centimetric or sub-centimetric) logs of
organic carbon on cores (Tar mats, source rocks, oil
shales, gas shales).
The LIPS consists in:
1. One mobile bench carrying the core,
2. One power laser providing a continuous infra-red
laser beam through an optical fiber,
3. One 3D movable head which guides the laser
beam and collects the material expelled from the
core during the laser shoot,
4. One or more detectors can be used for analyzing
the material pyrolyzed and expelled from the core
during the laser shoot (mass spectrometer, PID,
FID, sulphur detector…)
5. An acquisition and data processing system.
Typically one data point can be acquired every
minute.
The LIPS data are calibrated using the Rock- Eval or
Fisher assays. Thus, the results can be expressed as
log of Total Organic Carbon or Petroleum Potential.
The figure below shows an example of high resolution
log of petroleum potential obtained on a single well of
Jordan oil shale. Blue dots are Rock-Eval controls
every 50 cm.
Lithology TH U Color
Hydrocarbon
Yield % w/w
10 20 30
• Rock-Eval
Control
156

P-009
A new method for the combined detection of different faecal
biomarker classes and their binding types in soils using GC/MS
Michaela Dippold 1,2 , Jago Birk 1,3 , Guido Wiesenberg 2 , Bruno Glaser 3
1 Soil Physics Section, BAYCEER, University of Bayreuth, Bayreuth, Germany, 2 Department of
Agroecosystem Research, BAYCEER, University of Bayreuth, Bayreuth, Germany, 3 Soil Biogeochemistry,
Institute of Agricultural and Nutritional Science, Martin-Luther-University Halle-Wittenberg, Bayreuth,
Germany (corresponding author:midipp@gmx.de)
The detection of faeces in lacustrine, marine and
terrestrial ecosystems has already been established
based on quantification of several derivatives of the
∆ 5 -steroles, namely the stanoles, the stanones and
the bile acids. However, up to now, the combined
detection of these substance classes in soil was not
reliably possible so far. A joint quantification of these
substances would have the advantage to assess
robust and specific information about the faecal input
into soils. Thus, the objective of this work was the
development of a GC-MS-method for these faecal
biomarkers in soils, which accounts for the
methodological difficulties due to the high organic
matter contents of many Anthrosols and for the
different binding types of these biomarker classes.
For this purpose, a joint method was developed
based on existing methods for single biomarker
classes. After the weak alkaline saponification of the
total lipid extract separation of the neutral (∆ 5 -sterols,
stanoles and stanones) and the acidic lipid fraction
(bile acids) was performed by means of a sequential
liquid-liquid-extraction. The neutral fraction was
directly purified by deactivated silica whereas the
acidic lipids first had to be methylated before purifying
their methyl esters using activated silica. Finally both
fractions were derivatized by silylation. Evaluation of
this method was performed by standard addition to
lipid extracts from three Anthrosol-reference-profilepairs
with different soil properties and history: one
sandy and one clayey Amazonian Anthrosol under
pre-Columbian settlements, one loamy German
Anthrosol next to a Celtic settlement and reference
soils close to each Anthrosol. To get further
information about the content of faecal biomarkers in
differently bound lipid fractions saponified lipid
extracts were compared with not-saponified extracts
and direct saponification of soil samples.
The method evaluation by standard addition revealed
no significant differences between the recoveries of
the single substances and the applied first internal
standard. The precision and the high recoveries
(> 84%) of this method confirm its applicability in soils.
The different saponification treatments show that at
least 20% of the neutral biomarker classes were
bound to the soil matrix. For bile acids, which were
bound to about 50% to the soil matrix, this could be
explained by ester bondings via their carboxyl groups.
However, for less polar alcohol substance classes
(∆ 5 -steroles and stanoles) there are two potential
mechanisms for their stabilization. These include
covalent bonding of the hydroxyl group and a close
association of these hydrophobic molecules to the
organic substance of the soil, which could not be
distinguished by this method. The high content of
stanones in the bound lipid fraction can be attributed
to a very efficient association of this hydrophobic
substance class with the macromolecular network of
the organic substance. These stabilization processes
prevent the extraction of bound or encapsulated
molecules. Thus, a direct saponification of the soil is
necessary to make a high amount of faecal
biomarkers accessible for extraction.
The determination of the faecal biomarker fingerprint
in the Anthrosol-reference pairs revealed that input of
omnivorous faeces was only present in the
Amazonian Anthrosols but not in the reference
profiles. By means of bile acid fingerprint, these inputs
were identified as human faeces. The profiles
sampled in Germany showed a combined influence of
herbivorous and omnivorous faeces in both profiles,
which could be attributed to cattle, human, pig and
chicken.
Thus, this method copes with the often stipulated
multiproxy-approach for the quantification of faecal
biomarkers of different substance classes. The
additional consideration of the bound lipid pool in soil
enables the detection of a wide range of lipids
differing in age and origin in soil. Due to polygenetic
sources and the high recalcitrance of faecal
biomarkers, this is decisive for a correct and
comprehensive interpretation of ancient deposition of
faeces. Therefore this method is especially suitable
for the application in geoarcheological investigations
of Anthrosols.
157

P-010
Acidic fraction analyses of Brazilian oils using petroleomics
Célio Fernando Figueiredo Angolini 1 , Eugenio Vaz dos Santos Neto 2 , Anita Jocelyne
Marsaioli 1
1 Chemistry Institute, University of Campinas - UNICAMP, Campinas, Brazil, 2 PETROBRAS R&D Center,
Cidade Universitária, Brazil (corresponding author:anita@iqm.unicamp.br)
Introduction
Recent advances in mass spectrometry allow a more
precise and rapid characterization of petroleum
constituents for the determination of the elemental
composition of heteroatoms containing species (N, S
and O). These components are important in studies
focusing solid deposition, floculation, catalyst
deactivation, refinary corrosion problems and storage
instability. This methodology has been named
petroleomics [ 1], however petroleomics parameters
have not been correlated to the organic geochemical
parameters yet. Considering this premise, we used
samples of naturally biodegraded petroleum which
were previously characterized in order to correlate the
O2 class compositional variation to the biodegradation
process.
Material and Methods
Representative samples of lacustrine oils with P&M
biodegradation levels from 1 to 7 [2] from the Campos
Basin were used in the study. Biodegradation
intensity increases in the following order: P1, P5, P3,
P2 and P4 samples. Acidic fraction of petroleum
samples were obtained by KOH modified silica gel
column chromatography (200 g of silica + 40g of
KOH), eluted with ether (neutral fraction) and
diethylether:formic acid 20% (acidic fraction). These
were typically dissolved at 0.5 mg mL -1 in toluene:
methanol (1:1 vol:vol) with 0.5 % of NH4OH for ESI
analysis by a ESI GC/MS LTQ XL Orbitrap (Thermo
Scientific).
Results and Discussion
The bulk distribution of some classes of compounds
in the acidic fractions of the oil samples are depicted
in Figure 1. Typically biodegradation occur by
depletion of the less complex, hydrogen-rich
compounds first shifting the maximum of the O2 class
to lower levels of DBE (P1 to P5). Analyzing the
carboxylic acid ratios, Table 1, of compounds with
DBE 4 (tricyclic terpanoic acids)/DBE 3, DBE 6
(hopanoic acids)/ DBE 3 and DBE 8 (naphthalenic
acids)/ DBE 3 (bicyclic acids, more abundant) it can
be observed a general increasing trend of these ratios
with the growing intensity of biodegradation. These
bulk parameters are consistent with the classical
rational that bicyclic terpanoic acids DBE 3 are more
abundant and usually present in a wide range of
biodegraded samples.
DBE
DBE
20
10
0
0 10 20 30 40 50 60 70
20
10
0.000
12.50
25.00
37.50
50.00
62.50
75.00
87.50
100.0
0.000
12.50
25.00
37.50
50.00
62.50
75.00
87.50
100.0
Carbon number
P1 - O 2
0
0 10 20 30 40 50 60 70
Carbon number
DBE
20
10
0.000
12.50
25.00
37.50
50.00
62.50
75.00
87.50
100.0
P3 - O 2
DBE
DBE
0
0 10 20 30 40 50 60 70
Figure 1 – Plots of DBE versus carbon number for O2 class
species from the negative-ion ESI LTQ XL Orbitrap of acid
fraction, using Origin® 8.
Table 1 – Ratios of compound class in oil samples.
DBE P1 P5 P3 P2 P4
4/3 0.97 0.99 0.82 0.7 0.92
6/3 0.63 0.50 0.49 0.39 0.57
8/3 0.44 0.38 0.28 0.21 0.31
Conclusion
Results confirm that the bulk analysis of the acidic
components can be readily assessed in crude oils or
in acidic fractions by petroleomics, providing a rapid
characterization of crude oils regarding their
biodegradation levels. Caution should be taken when
applied this approach for oils with P&M
biodegradation levels higher than 6.
References
[1] Marshall, A.G., Rodgers, R.P. (2008) PNAS, 105,
18090-18095.
[2] Peters & Moldowan (1993).The Biomarker Guide.
Acknowledgment
20
10
0.000
12.50
25.00
37.50
50.00
62.50
75.00
87.50
100.0
0
0 10 20 30 40 50 60 70
20
10
Carbon number
0.000
12.50
25.00
37.50
50.00
62.50
75.00
87.50
100.0
Carbon number
P5 - O 2
P2 - O 2
0
0 10 20 30 40 50 60 70
Carbon number
P4 - O 2
158

P-011
Rapid geochemical typing using infrared spectroscopy
Andrew Bishop, Amy Kelly, Patrick Killough
Shell Projects & Technology, Houston, United States of America (corresponding
author:andrew.bishop@shell.com)
Prior to the advent of capillary gas
chromatography, infrared spectroscopy was
commonly used to provide typing information on oil
samples. However, the complexity of sample
preparation and data interpretation, plus the lack of
the type of detailed information available with capillary
GC, led to the abandonment of this method of
analysis. Improvements in this technology mean that
the instrumentation available today is vastly superior
and offers advantages of speed, ease of use and
portability which behove a revisit of infrared
spectroscopy for applications in geochemistry.
Several studies have documented geochemical
applications of Near-infrared (NIR) Spectroscopy, e.g.
Bement et al. 1996, Mullins et al. 2006, Leach et al.
2008. Mid-infrared (MIR) spectroscopy has received
less attention, thought it offers the advantage over
NIR in that functional group information is discernible,
and this may provide geochemical typing information.
Permanyer et al. (2005) describe the use of MIR for
oil-oil correlation in a group of fields in the Ebro delta,
offshore Spain. They conclude that MIR spectral
characteristics can be used for the assessment of
maturity, in-reservoir mixing and
compartmentalization. Abbas et al. (2006) showed
that oils from several different petroleum systems can
be successfully discriminated using MIR.
The objective of this investigation has been to
assess the suitability of MIR for the geochemical
interpretation of oil and condensate samples.
Approximately 350 oils have been analysed by this
method. The samples represent a range of source
ages, types, levels of maturity and extent of
biodegradation.
The analysis was performed on a Nicolet 6700
Response
1.8
1.6
1.5
1.4
Response
1.2
1.0 1.0
0.5
0.8
0.6
0.4
0.2
0.0
0.0
3650
CH3
CH3, CH2
CH3, CH2
Full Data-2
3037.383057 2073.134521 1108.885864
3150
2650
Variable
2150
1650
1150
Wavenumber cm -1
CH3, CH2
CH3
Aromatic
Figure 1. Example crude oil mid-range infrared
spectrum, with key bands identified.
C=O
S=O
650
Figure 2. Relationship of an example IR parameter
with Pristane/Phytane, illustrating response of IR
spectra to specific geochemical signatures.
FTIR spectrophotometer, with a trough plate ATR
interface. This enables the analysis of a dead oil
sample in about 5 minutes, with virtually no sample
preparation. The data has been interpreted using
peak heights, ratios and chemometrics on specific
spectral windows.
The results show that infrared spectra can be used
to rapidly assess the source type, maturity and level
of biodegradation of an oil sample. This method does
not offer the specificity of contemporary molecular
analysis, but it does offer a means to rapidly screen
large sample sets and identify unusual outlier
compositions. This method can also be used to
generate data fast in locations where sample export
restrictions and lack of local infrastructure, may
preclude timely analysis using standard petroleum
geochemistry procedures.
References
Abbas et al. (2006) Applied Spectroscopy 60, 304-
314.
Bement et al. (1996) Organic Geochemistry 24, 1173-
1178.
Leach et al. (2008) Organic Geochemistry 39, 910-
914.
Mullins et al. (2006) Energy and Fuels 20, 2448-2456.
Permanyer et al. (2005) Fuel 84, 159-168.
159

P-012
Heteroatom-containing compounds in maltenes and asphaltenes
separated from a sequence of fort mcmurray crude oils detected
by negative-ion ESI FT-ICR MS
Yinhua Pan, Yuhong Liao
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China (corresponding
author:liaoyh@gig.ac.cn)
The application of Fourier transform ion cyclotron
resonance mass spectrometry (FT-ICR MS), which
has ultra-high available broadband mass resolution,
mass resolving power and mass accuracy, makes it
possible to identify thousands of heteroatomcontaining
compounds in crude oils at molecular level
with higher resolution. In this research, electrospray
ionization ESI FT-ICR-MS was used to study a
sequence of 5 crude oils from one oil column of Fort
McMurray (FM) of Canada, which are of different
depth (280.75-310.00m). Separated maltenes and
asphaltenes were analyzed by ESI FT-ICR MS,
respectively (Fig. 1).
Fig. 1. Negative-ion ESI FT-ICR mass spectrum of
maltenes and asphaltenes separated from one FM
crude oil.
The results show that maltenes fraction in these crude
oils contains N1, N1O1, N1O2, N1S1, O1, O1S1, O2,
O2S1, O3, O3S1, O4, O4S1 and S1 heteroatom classes,
and 15-48 carbon atoms with double-bond equivalent
(DBE) values of 1-19 (Fig. 2). Asphaltenes fraction
contains more heteroatom classes of N1, N2, N1O1,
N1O2, N1O3, N1S1, O1, O1S1, O1S2, O2, O2S1, O2S2, O3,
O3S1, O3S2, O4, O4S1, O4S2, O5, O5S1, O5S2 and O6
with highly sulfur-containing compounds and DBE of
0-23 (Fig. 3). Heteroatom-containing compounds in
asphaltenes show a longer broadband up to 1000
(m/z) than in maltenes. The distribution patterns of N1
and O2 classes as the major species in maltenes and
asphaltenes. Specially, asphaltenes contain acidic
classes rich in OxSy (x:2-5; y:0-2) compounds. Sulfur
species are of both non-polar (thiophene-like) and
polar (sulfoxide) classes. Sulfur species are usually
the most abundant of the heteroatom-containing
species and are broadly distributed across the carbon
number range of petroleum fractions. Surfurcontaining
compounds make higher proportion in
asphaltenes than in maltenes. There is no obvious
trend in compositional variation with depth among FM
crude oils in maltenes while there is obvious trend in
asphaltenes. In asphaltenes, species containing the
same number of oxygen atoms obey the same trend.
For example, O2, O2S1 and O2S2 keep a raising trend.
While the trends of both O2Sx and O4Sx (x:0-2)
classes of the FM crude oils are different. It may be
due to the differences in biodegradation.
Fig. 2. Relative abundance of heteroatom class
species in maltenes.
Fig. 3. Relative abundance of heteroatom class
species in asphaltenes.
160

P-013
Study on non GC amenable fractions in biodegraded oils of the
Liaohe Basin by negative-ion ESI FT-ICR MS and PY-GC
Yuhong Liao 1 , Quan Shi 2
1 Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China, 2 China
University of Petroleum, Beijing, Beijing, China (corresponding author:liaoyh@gig.ac.cn)
In our research, 7 biodegraded oils extracted from
reservoir cores of two columns of the Liaohe Basin,
NE China, were studied. These tar sand extracts are
of known identical source and similar maturity,
representing a natural sequence of increasing degree
of biodegradation. These bitumens are termed with
the degrees of biodegradation on Peters and
Moldowan scale (abbreviated as PM level). Kim et al.
(2005) showed that biodegradation alters both the
core nuclei and alkyl side chain distributions in neutral
nitrogen and oxygen polar compounds using ESI FT-
ICR-MS. The methods of elemental composition,
δ13C, δ15N, together with ESI FT ICR-MS and Py-
GC, were used to study the influence of
biodegradation on heavy fractions in crude oils of the
Liaohe Basin.
In our research, ESI FT-ICR MS suggested that
relative abundance of O2 species in asphaltene
fraction are no less than in maltene fraction though
asphaltenes were re-precipitated repeatedly,
sonicated and washed by n-alkane repeatedly,
indicating that organic acids may be linked to
functionalities of asphaltene structure by such as Hbonding.
In maltenes fraction, N1 species are
dominated by carbazoles, benzocarbazoles and
dibenzocarbazoles. N1 species decrease much with
biodegradation. NO species decrease significantly
with biodegradation, especially in the range of PM
level 2-4 (Es3 column). In asphaltene fraction, N1
species are dominated by dibenzocarbazoles and N1
compounds with even higher aromaticity. The
distribution of N1 species at various biodegradation
levels is very similar. NO species in asphaltenes show
higher aromaticity than maltenes. NO species also
decrease with biodegradation, but the distribution is
very similar. The more condensed and multiheteroatomic
nitrogen-containing species will likely be
in the asphaltene fraction, and the least condensed
nitrogen species are likely in the resin fraction. N1
and NO species with higher aromaticity and less alkyl
side chains show higher polarity and are likely
precipitated by n-hexane as a part of asphaltene
fraction. The progressive consumption of susceptible
nitrogen species may continually change δ15N values
in biodegradation. Conversely, the δ15N values of the
asphaltenes are fairly constant at PM levels > 3,
suggesting that once the most susceptible nitrogen
species are removed, the remaining species are
relatively stable.
Py-GC can provide structural information of alkyl
side chains of asphaltenes by crack them into small
ones. In the range of PM level 5-8, TOC-normalized
intensity of n-alkanes plus n-alkenes of identical
carbon number produced by quantitative pyrolysis
(PY-GC) of asphaltenes decrease with biodegradation
(Fig. 1), especially at PM level 8. It suggested that
alkyl side chains of asphaltenes are progressively
shortened during biodegradation.
TOC TOC normalized normalized Intensity Intensity
1200
900
600
300
Es 1
0
6 8 10 12 14 16 18 20 22 24 26
Carbon number
L-5 L-6 L-7 L-8
Fig. 1 TOC normalized intensity of n-alkanes plus nalkenes
with identical carbon numbers
Reference:
Rubinstein, I., Spyckerelle, C., Strausz, O.P., 1979.
Pyrolysis of asphaltenes: a source of geochemical
information. Geochimica et Cosmochimica Acta 43, 1-6.
Connan, J., 1984. Biodegradation of crude oils in
reservoirs. In: Brooks, J., Welte, D.H. (Eds.), Advances
in Petroleum Geochemistry I. Academic Press, London,
UK, pp.298–335.
Kim, S., Stanford, L.A., Rodgers, R.P., Marshall, A.G.,
Walters, C.C., Qian, K., Wenger, L.M., Mankiewicz, P.,
2005. Microbial alteration of the acidic and neutral polar
NSO compounds revealed by Fourier transform ion
cyclotron resonance mass spectrometry. Organic
Geochemistry 36, 1117-1134.
161

P-014
Evaluation of hydropyrolysis as a method for the quantification
of black carbon via the testing of standard reference materials
Will Meredith 1 , Emma Tilston 2 , Philippa Ascough 2 , David Large 1 , Colin Snape 1 , Michael
Bird 3
1 Universtiy of Nottingham, Nottingham, United Kingdom, 2 SUERC, East Kilbride, United Kingdom, 3 James
Cook University, Cairns, Australia (corresponding author:william.meredith@nottingham.ac.uk)
Black carbon (BC) is the aromatic, recalcitrant product
of incomplete combustion of biomass and fossil fuels.
An accurate and reproducible method for BC
quantification is desirable if we are to assess its
occurrence and stability in a range of environments.
Currently a variety of thermal, chemical and optical
methods are used which inevitably give a wide range
of results, as demonstrated by Hammes et al (2007)
in the BC inter-comparison study [1].
A new approach is hydropyrolysis (hypy), in which
pyrolysis assisted by high hydrogen pressure (15
MPa) facilitates reductive removal of labile organic
matter. The high hydrogen pressure and slow heating
rate employed, together with the presence of a Mo
based catalyst prevent generation of secondary char.
Here, we present results evaluating the potential of
hypy for the isolation and quantification of BC from
the 12 reference materials used in the BC intercomparison
study, comprising 3 laboratory-produced
BC-rich materials, 5 BC-containing environmental
matrices and 4 non-BC containing potentially
interfering materials [1].
By increasing the maximum hypy temperature in 25°C
increments from 450°C to 595°C (Fig. 1), it is possible
to identify conditions under which lignocellulosic and
other labile organic carbon material (e.g. humic acids,
lipids, proteins etc) are fully removed (by 550°C), but
at which degradation via hydrogasification of the BC
component has not yet commenced (over 575°C).
This plateau in the carbon content of the hypy
residues (as measured by elemental analysis)
between 550 and 575°C is apparent in the soil and
sediment samples, suggesting that hypy reproducibly
isolates a carbonaceous fraction of consistent relative
stability in samples from different environments.
The resulting BC contents (as determined at 550°C)
for all 12 samples fall within the range reported in the
BC inter-comparison study [1], with BC also
distinguished successfully from the potentially
interfering materials. Hypy is also able to differentiate
―low BC‖ biochars from ―high BC‖ n-hexane soot.
Additionally, the results are highly reproducible, with
BC determinations from triplicate analyses typically
within ±1%.
Fig. 1. BC (%) as proportion of organic carbon (OC)
as measured for the environmental matrices.
Within BC-containing environmental matrices hypy is
able to discriminate between those with high fossil
fuel derived BC contents, dominated by soot (e.g. the
marine sediment and urban aerosol from
industrialised environments), and those with lower BC
contents derived from vegetation burning (e.g.
agricultural soils).
It appears that hypy can reduce labile organic matter
to volatile products in a controlled manner, and so
isolate rapidly and reproducibly the most resistant BC
fraction from carbonaceous samples, independent of
the environmental matrices in which it is found. This
makes it an attractive new approach for quantification
of BC across a wide range of sample types.
[1] Hammes, K., et al. (2007) Global Biogeochemical
Cycles 21, GB3016, doi: 10.1029/2006GB002914.
162

P-015
Can comprehensive analysis of degraded oil indicate the
conditions under which biodegradation occurred in an oil
reservoir?
Thomas Oldenburg 1 , Steve Larter 1,2 , Melisa Brown 1 , Ben Hsieh 1 , Ian Head 2 , Martin
Jones 2 , Caroline Aitkins 2 , Neil Gray 2
1 University of Calgary, Calgary, Canada, 2 Newcastle University, Newcastle upon Tyne, United Kingdom
(corresponding author:toldenbu@ucalgary.ca)
Most of the world petroleum reserves are
biodegraded with the largest oil reserves being found
on the flanks of foreland basins in Canada and
Venezuela. A significant fraction of the conventional
oil reserves are also biodegraded and major future oil
discoveries are likely to be mainly biodegraded, too
as they are expected in deep-water areas with low
thermal gradients and shallow exploration targets.
These petroleum reservoirs are cooler than 80ºC and
therefore ideal environments for microbial
degradation. As it became accepted only recently that
biodegradation of petroleum in reservoirs proceeds
anaerobically little is known about the processes and
the controlling factors involved in subsurface
hydrocarbon and non-hydrocarbon degradation.
A laboratory microcosm study of anaerobic
petroleum degradation under sulphate-reducing and
methanogenic conditions was undertaken over a
period of two years. The microbial communities and
hydrocarbon distribution patterns were analysed
parallel to the detailed analysis of the distribution of
polar compounds using an ultra-high resolution 12T
Fourier Transform Ion Cyclotron Resonance Mass
Spectrometer (FTICRMS). The whole degraded oil
samples were analysed for acidic components (using
electrospray ionisation (ESI) in negative mode), basic
compounds (ESI positive mode) as well as for low
A
original 302 days metha. 686 days metha.
polar and highly aromatic components such as
sulphur and aromatic hydrocarbon compounds using
Atmospheric Pressure Photoionisation (APPI)
techniques.
The forming or destruction of some polar compound
classes indicates the conditions under which oil
B
biodegradation occurs. Whereas many hydroxy and
carboxylic acid compounds are formed (Fig 1A-C) the
occurrence of e.g. some NOx classes are related to
biodegradation mechanism. This novel knowledge
received from laboratory experiments will be used to
predict the biodegradation history of natural
biodegraded oil reservoirs.
C
163

P-016
Iron isotopic compositions of crude oils – development of a new
extraction method and first results
Christian Ostertag-Henning 1 , Ulia Hammer 1 , Friedhelm von Blanckenburg 2
1 Bundesanstalt fur Geowissenschaften und Rohstoffe, Hannover, Germany, 2 Deutsches
Geoforschungszentrum GFZ, Potsdam, Germany (corresponding author:Christian.Ostertag-
Henning@bgr.de)
Metals in oils may contain valuable information about
the redox conditions during the deposition and early
diagenesis of the source rocks (e.g. [1]). But generally
only data of a limited number of metals - mainly V
and Ni - are used for the interpretation and for
correlation purposes. As [2] stated for a series of oils
from the German Molasse basin, ―in contrast to the
contents of S, V, Co, Ni and Se, those of Cr, Fe, Zn,
Br and I show strong oscillations within the different
oil fields.‖ – even if these oil fields belong to the same
oil family. This invokes the importance of in-reservoir
alteration of oils on the content of some metals. For
Kuparuk oil field on the North Slope of Alaska, [3]
noted a close covariance of strong biodegradation of
the oils with the occurrence of glauconite and hence
Fe III -rich intervals in the reservoir. They argue for an
anaerobic biodegradation mainly by ferric-iron
reducing bacteria.
To unravel potential information of the iron isotopic
composition about the extent of biotic and abiotic
processes involving the reduction of iron and
concomitant oxidation of hydrocarbons a method for
the determination of the iron isotopic composition of
crude oils and asphaltenes was established. The acid
digestion of samples cleaned of traces of formation
water and inorganic particles was performed in
microwave reaction vessels, the purification of the
resulting dissolved iron was ensured by ion-exchange
chromatography and coprecipitation (cf. [4]). The
complete extraction of iron from the hydrocarbon
phase or the asphaltenes was verified using standard
NIST 1084a. The concentrations of iron and other
metals have been measured by ICP-OES, the isotopic
composition of iron by MC-ICP-MS.
The iron isotopic composition of different oils
analyzed encompasses a very large range of values
up to +0.8 permil � 56 / 54 – a remarkable high value (cf.
[5]). One likely explanation for the strong enrichment
in 56 Fe is the dissimilatory iron reduction by bacteria in
the reservoir. Additional information on processes
during secondary migration might be revealed if
analysis of related oilfield waters are available – as [6]
have discussed.
Fig. 1: Range of iron isotopic compositions of sediments and
diverse biological materials – and the investigated crude oil
samples.
References
[1] Lewan, M. (84) Geochim. Cosmochim. Acta 48: 2231-8.
[2] Ellrich, J.; Hirner, A. & Stärk, H. (85) Chem.Geol. 48:313-
23.
[3] Holba, A.; Wright, L.; Levinson, R.; Huizinga, B. &
Scheihing, M. (04) In: Cubitt et al. (ed.): Understanding
Petroleum Reservoirs: Towards an integrated reservoir
engineering and geochemical approach. Geol. Soc. Spec.
Publ. London, 237: 53-88.
[4] Guelke, M. & von Blanckenburg, F. (07) Envir. Sci. and
Technol. 41: 1896-1901.
[5] Dauphas, N. & Rouxel, O. (06) Mass Spectrom. Rev. 25:
515-50.
[6] Busigny, V. & Dauphas, N. (07) EPSL 254:272-87.
164

P-017
Brazilian Miocene amber from Acre Basin (Solimões Formation):
comprehensive two-dimensional gas chromatography coupled
with time-of-flight mass spectrometry applied on its
paleobotanical source
Ricardo Pereira 1 , Ismar de Souza Carvalho 1 , Antonio Carlos Sequeira Fernandes 1 ,
Karen Adami Rodrigues 2 , Raphael Salles Ferreira Silva 1 , Renata Filgueiras Soares 1 ,
Rosane Aguiar da Silva San Gil 1 , Débora de Almeida Azevedo 1
1 Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil, 2 Universidade Federal de Pelotas, Pelotas,
Brazil (corresponding author:ricardo.geologia@uol.com.br)
Amber is a fossil resin mainly constituted of organic
polymers originated through complex maturation
processes [1]. Despites the occurrence of important
amber deposits around the world, registers of this
material in Brazil are rare being known in Lower
Cretaceous sediments from Amazonas, Araripe and
Recôncavo basins. All Brazilian samples analyzed
until this moment were linked to conifer families
mainly Araucariaceae, Podocarpaceae or
Cheirolepidiaceae [2,3]. Comprehensive twodimensional
gas chromatography coupled with timeof-flight
mass spectrometry (GC×GC-TOFMS) could
be particularly useful for investigating the composition
of complex mixtures, such as amber extracts. The aim
of this study was to carry out an individual
identification of terpenes in extracts from amber
samples collected in fluvial sediments of Miocene age
localized in Solimões Formation (Acre Basin, Brazil)
by GCxGC-TOFMS. The data obtained were used to
assess the paleobotanical source of the amber.
Three amber samples, named SOL-01, SOL-02
and SOL-03, were extracted (CH2Cl2:CH3OH, 1:1,
V:V) and analysed in a GCxGC-TOFMS System
Pegasus 4D (Leco). The column set used was a DB-
5MS (30 m) as first dimension and a BPX-50 (1.3 m)
as second dimension.
The total ion chromatogram (TIC) for the SOL-03
sample is showed in the Figure 1. TIC acquired are
analogous for the three samples, indicating that the
amber samples are probably derived from the same
or similar botanical source. The chromatograms
revealed three distinct regions, associated to
monoterpenoids, hydrocarbonic sesquiterpenoids and
decalines, and polar sesquiterpenoids and
diterpenoids. Several compounds of aromadendrane,
humulane, germacrane caryophyllane, bisabolane,
labdane, abietane and kaurane skeletons were
present. These compounds were tentatively identified
by the use of ChromaTOF 2.32 Software, Nist Mass
Spectral Database and elution order.
The molecular composition pointed to Fabaceae
(Leguminosae) family. This angiosperm group have
resins based on sesquiterpenes that most often occur
as hydrocarbons as well as diterpenes of labdane
class [1], both identified in the analyzed samples.
Moreover, Fabaceae fossilized leaves were found in
the same stratigraphic level of the amber samples. In
this way, the family indicated by the molecular
composition of ambers finds support in the fossil
record of the Solimões Formation. So, this work
allowed expanding the knowledge about Brazilian
fossil resins and its botanical source, including
angiosperms as amber producers and using GCxGC-
TOFMS to elucidate amber chemical composition.
Fig. 1. Total ion chromatogram for SOL-03 sample extract,
showing some compounds identified: (1) Camphene, (2)
Cymene, (3) Fenchol, (4) Borneol, (5) Aromadendrene, (6)
Methyloctahydronaphthalenone, (7) Germacrene, (8)
Humulene, (9) Bisabolene, (10) Kaur-16-ene, (11) Abieta-
8,11,13-trien-18-ol, (12) Kauren-13-ol.
References
[1] Langenheim, J.H. (2003). Plant Resins:
Chemistry,Evolution, Ecology, and Ethnobotany, 1 st
Edition, Timber Press: Portland, 586 pp.
[2] Pereira, R., Carvalho, I.S., Simoneit, B.R.T., Azevedo,
D.A. (2009). Org. Geochem. 40, 863-875.
[3] Pereira, R., San gil, R.A.S., Carvalho, I.S., Fernandes,
A.C., Azevedo, D.A. (2011). J. Braz. Chem. Soc. 22,
92-97.
165

P-018
Evaluation of accelerated solvent extraction (ASE) for pigment
extraction from lake and marine sediments
Neungrutai Saesaengseerung, Brendan Keely
University of York, York, United Kingdom (corresponding author:ns540@york.ac.uk)
Chlorophylls and their derivatives are widely
occurring biomarkers for the primary producer
communities in lake and marine sediments. Their
abundances and distributions have been related to
the intensity of palae-production at the time of the
deposition 1 and to changes in relative sea level 2 and
ice cover 3 . Generally, analysis of these compounds in
sediments involves solvent extraction followed by
identification using liquid chromatography coupled
with photodiode array detection and mass
spectrometry.
Sonic extraction is the conventional method for
recovery of these sensitive pigments from lake and
marine sediments 2,3,4 . Although the method gives high
yields of extract, it is time consuming and is not
readily amenable to automation, a limitation to the use
of pigments in profiling at high sampling rates.
Accelerated solvent extraction (ASE) enhances
extraction efficiency by using elevated temperature
and pressure with liquid solvents to reduce extraction
times and solvent consumption 5 . It is becoming widely
utilisted in geochemistry for extraction from ancient
sediments because of the potential for automation.
Although the method offers potential advantages, its
suitability for extraction of the highly sensitive chlorin
pigments has not been tested.
To evaluate the applicability of ASE for chlorin
extraction from lake and marine environments,
sediments from several distinct locations were
extracted by sonic extraction and ASE over series of
temperatures (RT to 175�C). Pigments extracts were
analysed by LC/MS n and components identified on the
basis of their HPLC retention times and their online
UV/Vis and multistage tandem mass spectra. Total
yields of pigments and the formation of structural
alteration products are considered to evaluate the
potential use of ASE in pigment analysis.
Pigment quantification indicates that the total
yields of pigments from ASE and from sonic
extraction do not different significantly for ASE
temperatures around 80�C. At high temperatures
alteration of the pigment structure occurs during ASE
extraction; for example, demetallation of chlorophyll a,
forming phaeophytin a, and decarbomethoxylation at
C13 2 -phaeophytin a forming to pyrophaeophytin a
(Figure 1)
O
N N
N
Mg
N
O O
OMe
OPhytyl
demetallation
- Mg
O
NH N
N
HN
O O
OMe
OPhytyl
decarbomethoxylation
-COOMe
O
NH N
N
HN
OPhytyl
Chlorophyll a Phaeophytin a Pyrophaeophytin a
Figure1: Alteration of pigments in Lake Reid sediment
extraction by the ASE 150�C.
In addition to chlorophylls and their derivatives,
representing oxygenic primary producers, bacterio-
chlorophylls and their derivatives, representing
anoxygenic photoautrophs, have been examined in
the ASE suitability study for sediment extraction.
At the optimised ASE conditions, extraction time
and solvent consumption are reduced, leading to
increases in efficiency. Furthermore, the high
throughput and ability to automate the extraction
enables the profiling of sediment cores at higher
sampling resolutions within reasonable timescales.
References
1. Harris, P.G., et al., (1996), Nature, 383(6595), 63.
2. Squier, A.H., et al., (2002), Organic Geochemistry,
33(12), 1655.
3. Squier, A.H., et al., (2004), Organic Geochemistry,
35(2), 203.
4. Airs, R.L., et al., (2001), Journal of Chromatography A,
917(1-2), 167.
5. Richter, B.E., et al., (1996), Analytical Chemistry,
68(6), 1033.
O
166

P-019
Influence of extraction temperature on the chemical composition
of soil lipids
Csanád Sajgó 1 , József Fekete 1 , Tünde Nyilas 2 , Magdolna Hetényi 2
1 Institute for Geochemical Research, Hungarian Academy of Sciences, Budapest, Hungary, 2 University of
Szeged, Szeged, Hungary (corresponding author:sajgo@geochem.hu)
The composition of soil lipids was compared in five
samples at three sites having different soil characters
from Hungary. The aim of this work is to study the
lipid fractions of the organic matter occurring in
different soil environment and the effect of extraction
temperature on lipid composition. Chernozem (A, AB
and B horizons), red clayey rendzina (A horizon),
typical meadow soil (A horizon) soils were chosen for
this study. For the extraction of lipids from soils
traditional solvents were used: i) n-hexane (Ha) ii)
chloroform/methanol (3/1, v/v; CMa), both shaken
rigorously (3*20 hours) at room temperature and iii)
chloroform (Cb), iiii) benzene/acetone/methanol
(70/15/15, v/v; BAMb), both extracted for 40 hours at
elevated temperature in Soxhlet apparatus (a:
ambient, b: boiling). The carbon-normalized averaged
lipid content varied: 0.22, 0.69, 0.34 and 1.48 mg/g in
different extracts, respectively. The proportion of
aliphatic hydrocarbons relative to aromatic ones and
the proportion of �CH to �NSO (resins) show
characteristic variation (0.9, 1.12, 0.75 and 0.34, 0.25,
0.11) in CMa, Cb, BAMb lipids, respectively.
GC examinations of the non-aromatic hydrocarbon
fractions from lipids at ambient temperature extraction
revealed mainly even-numbered n-alk-1-enes ranging
from n-C14:1 to n-C28:1, maximizing at n-C18:1, n-C20:1
and n-C22:1, n-C24:1, n-C26:1, with moderate
contribution of n-alkanes (n-C14–n-C26). Similar
distributions are rare [1, 2]. The ―boiling extracts‖
show reverse picture. Five n-alkane and alk-1-ene
ratios demonstrate the very considerable difference
between compositions of extraction yields of soils
gained at room temperature and boiling temperature
of solvents [(o+n)C22-/(o+n)C23+, �o/�n, �odd/�even,
Paq, �o+�n (Paq = (nC23 + nC25)/(nC23 + nC25 + nC29 +
nC31); o = n-alk-1-enes, n= n-alkanes)] in Fig 1.
Similar differences are also reflected in the stable
isotopic composition. The small (~0.5‰), but regular
variance of δ13C, and the large (~20‰) variance of
δD in the resin fractions show that the compositions of
the OM obtained with different solvents and
temperatures are different, as well as the proportions
of the exchangeable H.
Our observation of temperature effect on composition
of lipids is scientific novelty.
Fig. 1 n-alkane and alk-1-ene ratios in hexane
a(mbient) and benzene/acetone/methanol b(oiling)
extracts
This work was funded by the Hungarian Scientific
Research Fund (OTKA) through grant K81181.
References
[1] Hetényi, M., Nyilas, T., Sajgó, Cs. 2010. Organic
geochemical evidence of late Pleistocene–Holocene
environmental changes in the Lake Balaton region
(Hungary). Organic Geochemistry, 41, 915-923
[2] Ekpo, B. O., Oyo-Ita, O. E., Wehner, H., 2005.
Even-n-alkane/alkene predominances in surface
sediments from the Calabar River, SE Niger Delta,
Nigeria. Naturwissenschaften 92, 341–346.
167

P-020
Improvement of HPLC-protocols for intact polar lipid analysis
Jan Schröder, Julius Lipp, Lars Wörmer, Kai-Uwe Hinrichs
MARUM Center for Marine Environmental Sciences, University of Bremen, Organic Geochemistry Group, D-
28359 Bremen, Germany (corresponding author:jschroeder@marum.de)
Intact polar lipids (IPL) are the building blocks of
microbial membranes and have been successfully
applied as biomarkers in a variety of environmental
samples. Due to their taxonomic specificity and
property to select for live biomass, IPLs offer a
detailed view of abundance and composition of
microbial communities [1,2].
The analysis of IPLs relies on traditional protocols
for solvent extraction and chromatographic separation
by high-performance liquid chromatography coupled
to mass spectrometry (HPLC-MS) [1,3]. However, the
underlying analytical procedures have remained
virtually unchanged for several years and recent
technological advancements have not yet been
implemented. Only recently, Huguet et al. compared
different extraction methods for quantitative analysis
of IPLs and showed significant differences in
extraction yields also differing between the different
IPL classes [4].
Most environmental samples comprise a very
complex mixture of organic compounds and pose a
challenge to separation and identification. Typical
analytical problems are low IPL concentrations
combined with a high background of sample matrix.
These issues can be overcome by efficient extract
clean-up and sample pre-concentration followed by
improved HPLC-MS methods.
The established chromatographical protocol uses a
column with diol packing material and normal-phase
eluents for chromatographical separation according to
the polarity of the polar head group [1]. We have
tested columns with different packing materials for
their potential for IPL analysis. Additionally, we
evaluated the effect of eluent system, buffer
concentration and composition, and injection volume
on the chromatographic resolution and selectivity. In a
first step, we implemented an analytical protocol on a
reversed phase column where IPLs are separated by
polarity of their apolar core lipid, i.e. side chain length.
Besides type and purity of the reversed-phase
packing material, the buffer concentration was found
to have a dramatic effect on peak shape and peak
tailing (Fig. 1).
We will present a comprehensive overview of
current analytical problems and show results of newly
developed extract clean-up protocols and further
optimization of existing extraction methods of samples
covering a variety of environmental settings.
Additionally, we will compare different HPLC methods
and highlight their specific advantages and
disadvantages for IPL separation and mass
spectrometric characterization.
Fig. 1 Mass chromatograms of an IPL standard mixture
analysed by reversed phase HPLC-MS using (A) an
unoptimized method adapted from the established normal
phase method, and (B) an improved separation with a
modified buffer system. Peaks: (1) C16phosphoethanolamine-DAG,
(2) C16-phosphocholine-DAG,
(3) C16-phosphocholine-DEG, (4) C16-plasmalogenphosphocholine-DAG,
(5) phosphocholine-archaeol, (6) C21phosphocholine
DAG.
References
[1] Sturt, H.F. et al. (2004) Rapid Commun. Mass
Spectrom. 18, 617-628.
[2] Biddle, J. F. et al. (2006) Proc. Natl. Acad. Sci. USA
103, 3846-3851.
[3] Rütters, H. et al. (2002) J. Microbiol.: Meth. 28, 149-
160.
[4] Huguet, C. et al. (2010) Limnol. Oceanogr.: Methods 8,
127-145.
168

P-021
A new solid electrolyte reactor for CF-IRMS analysis of hydrogen
of organic gases and compounds
Eric Galimov 1 , Vyacheslav Sevastyanov 1 , Nataliya Babulevich 2 , Alexander Arzhannikov 1
1 Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow, Russian Federation, 2 NRC
Kurchatov Institute, Moscow, Russian Federation (corresponding author:vsev@geokhi.ru)
In the past few years, an increase in interest in
oxygen-conducting solid electrolyte has been
observed. The present study is devoted to
development of the high-temperature solid electrolyte
reactor (SER) based on yttria-stabilized zirconia for
water decomposition. Earlier we set up a similar
device for oxidation of organic compounds. The
reduction SER proposed was installed into a system
consisting of HP 6890 capillary chromatograph, a
standard oxidation reactor followed by SER and the
Delta Plus XP isotope ratio mass spectrometer. A
solid electrolyte possesses the oxygen ions related
conductivity at high temperatures (800-1000 o C). This
reactor is made of tubular, thin-walled zirconia
ceramics with inner diameter of 1 mm and of 10 cm
total length. To produce electrodes, both inner and
outer surfaces of this tube were coated by platinum
paste and then annealed in the air. The solidelectrolyte
reactor was connected in three-electrode
circuit. Three-electrode system involved the Elins PS8
Potentiostat. The inner electrode of the reactor served
as the working electrode. Reference electrode was on
the outer side.
After hydrocarbon gases are separated by a GC
column, they are converted into simple gases. The
H2O formed in the oxidation process is decomposed
on the triple-phase interface of the solid electrolyte
reactor. The optimal mode of the solid-electrolyte
reactor operation is the mode that achieving the
complete reduction of water. Oxygen was turned into
ions which under electrical voltage (1.2V) were moved
through solid electrolyte wall outward. The flow of a
He carrier gas swept hydrogen to a Delta Plus XP
isotope ratio mass spectrometer (Thermo Fisher
Scientific). During several seconds compounds
passed through the SER.
A gas mixture in argon (14.8 vol % N2, 6.1 vol % CO2,
9.5 vol % CH4, 6.8 vol % C2H4, 5.6 vol % C3H8, 3.0 vol
% n-C4H10, 7.0 vol % i-C4H10) as well as some other
gases were used for studying. Typically 200 μL gas
mixture (20:1) was injected to HP 6890 GC with
PoraPlot Q column (25 m X 0.32 mm). A GC flow rate
of 1.5 mL/min was used.
We measured δD values of reference natural gas
NIST NGS3 (δD=-176.3 ‰; -175.6 ‰) and obtained
results of δD= -177.2±1.1‰ close to the calibrated
δD values. For the hydrocarbon gas mixture, the
following results were obtained: δD(CH4)= -195.6±1.2
‰, δD(C2H4)=-104.2±1.1 ‰, δD(C3H8)=-110.2±2.7 ‰,
δD(iso-C4H10)=-199.1±0.5 ‰,
δD(n-C4H10)= -173.4±2.3 ‰.
Solid-electrolyte reactors do not require any additional
equipment and extra disposal materials as well. Thus,
the application of a solid-electrolyte in the reduction
reactor design allows to essentially simplify the device
design for δD measurements of hydrocarbons and to
improve its reliability.
169

P-022
Open-system hydrous pyrolysis of source rock with continuous
recovery
Martin Stockhausen, Lorenz Schwark
Christian-Albrechts-University - Institute for Geosciences, Kiel, Germany (corresponding
author:mst@gpi.uni-kiel.de)
In order to understand the generation of petroleum
fluids from kerogen under increasing thermal stress,
laboratory pyrolysis procedures have been applied for
several decades. Pyrolysis techniques vary
substantially and can be generally separated into
open versus closed and dry versus hydrous pyrolysis.
Hydrous pyrolysis has been found to mimic natural
processes more closely leading preferentially to
formation of oil-like products, whereas dry pyrolysis
often leads to production of less soluble bitumen not
comparable to free oil. The application of closed
pyrolysis suffers from the formation of primary
generation products, which are subject to subsequent
secondary reactions in the closed system. These
reactions can either break down primary products or
lead to neo-formation from primary compounds by
condensation or recombination reactions.
The combination of hydrous pyrolysis with open
conditions has not been realized routinely. It has thus
been the aim of this study to perform open hydrous
pyrolysis by connecting a continuous recovery system
to a hydrous pyrolysis vessel in order to directly
capture the generated oil/water emulsions and gases.
The water content in the reaction vessel was
maintained stable by adding appropriate amounts of
water via a pump. It is expected that the continuous
recovery of the generated fluids diminishes the effect
of secondary alteration reactions.
Results from the open hydrous pyrolysis experiments
are compared with closed hydrous pyrolysis
experiments applying the same autoclave assembly
(600 ml capacity) for larger sample volumes (50 – 100
g of source rock). In addition smaller volume closed
vessel hydrous pyrolysis using 30 ml reaction tubes
and 500 to 1000 mg of source rock at several
temperatures were conducted for comparison. In the
temperature regime up to 300-320°C differences in
generation yield are small for hydrous and anhydrous
pyrolysis. At temperatures in excess of 300-320°C an
increase in pyrolysis yields under hydrous conditions
occurs. We have thus conducted experiments up to
360°C for hydrous as well as anhydrous pyrolysis
employing small and large volume reactors to
estimate the differences in pyrolyzate formation under
these conditions.
Open system dry pyrolysis was conducted as
reference using Rock Eval techniques. The samples
utilized in the different experiments are chemically
homogenous and derived from a single plate (200 cm
x 100 cm x 5 cm) of Toarcian source rock from the
Dotternhausen quarry in SW-Germany. The thermal
maturity of the sample was 0.4 % Rr, the TOC value
of the starting material was 10.31% TOC, the HI value
was 656 [mgHC/gTOC] and the PI value
corresponded to 0.06.
The data obtained from closed hydrous and
anhydrous pyrolysis, using small and large volume
reactors and those obtained from large volume
continuous open hydrous pyrolysis will be discussed.
This will include mass balances between gases, free
floating oil in the water phase, free oil collected from
the reactor wall and the residual bitumen and also the
analysis of the hydrocarbon compositions.
Fig 1: Schematic setup for an open hydrous pyrolysis
unit with continuous pyrolyzate recovery.
170

P-023
Petroleum fluid and source rock database: best practices
Gunardi Sulistyo, Andrew Pepper, David Schmidt, Steven Crews
Hess Corporation, Houston/Texas, United States of America (corresponding author:gsulistyo@hess.com)
Petroleum geochemists are often faced with the
daunting tasks of searching and compiling fluid and
source rock data whenever they work in the field of
geochemistry in either the exploration and/or
production areas. Having a good, reliable, fit-forpurpose
database is critical for geochemists, in order
to be able to work efficiently and effectively.
Several important factors have to be considered when
initiating the building of a database to successfully
accommodate and manage the current and future
needs: database format, content, structure, reporting,
interpretation and access.
Choosing the appropriate database format is the first
decision to be made. It is also preferable that the
database format be one that is easy to use, requiring
minimal maintenance, but also can be subsequently
migrated to a more robust system with minimal work.
The next decision concerns the type of data to be
included in the database. A comprehensive database
that contains a wide spectrum of geoscience
disciplines other than geochemistry is not
recommended. On the other hand, a database that
contains only geochemical data will be of limited use.
PVT data are the most useful non-geochemistry data
that need to be linked together with the geochemistry
data. Also, it can be useful to have a vehicle for
attaching relevant files from other disciplines such as
basin models, well log files, photomicrographs and
reports at the site or sample level.
It is common for some analysis to be performed by
multiple vendors that use various methods. In addition
to this, fluid samples are affected by drilling mud
contamination at various contamination levels and are
run multiple times. All of these issues can cause
potential confusion to the database users if they are
not properly managed. A well thought-out database
structure is of considerable help in minimizing or
eliminating these potential problems. Using a specific
nomenclature for samples will provide the linkage
between PVT and geochemical data.
For maximum efficiency, it is preferable to have some
built-in interpretive tools and a reporting system that
do not involve maintenance from another type of
database. Using data normalization is necessary for
calculating commonly used parameters that may
come calculated differently from different data
sources. For interpretation purposes, we recommend
using the index such as A/(A+B) in fraction, rather
than using the ratio of A/B or percentages. Entering
some information about the purpose of the analysis
will help in the data retrieval process.
A good database should be easily accessible via a
website, so that the users can access the most up-todate
data in real time.
171

P-024
The phenolic characterisation of peat profiles along a vegetation
succession using 13C-labelled tetramethylammonium hydroxide
(13C-TMAH) thermochemolysis
Eleanor Swain, Geoffrey Abbott
Newcastle University, Newcastle upon Tyne, United Kingdom (corresponding author:geoff.abbott@ncl.ac.uk)
Northern peatlands cover an area of around 350 x10 6
ha, and store approximately one-third of global soil
carbon (C) 1 . Peatland vegetation varies in response to
external drivers including climate induced
disturbance, due to differences in tissue biochemistry
and changes in litter reactivity. These factors are
poorly understood, but critical to understanding soil
organic matter turnover in peatlands and its response
to a changing climate. This study aims to provide a
detailed and comprehensive SOM characterisation of
a peatland using thermally assisted hydrolysis and
methylation (THM) in the presence of 13 C-TMAH.
Peat profiles were sampled from Wark Forest, an
afforested moorland site in northeast England. The
site includes two soil profiles in an undisturbed open
bog and four profiles in a bog margin. The bog margin
comprised two pits amongst Sitka spruce but not
situated underneath the canopy, and two pits located
directly under the canopy of Sitka spruce.
Figure 1: Depth profile showing changes in total lignin
products (Λ) (x10 -2 mg/100mg OC). SE = 4.
The addition of 13 C-TMAH allows the distinction
between intact lignin, degraded lignin and non-lignin
phenols to be made 2 .
This site was selected due to the absence of any
recent human influence on the peat, to allow us to
explore the effect of direct lignin and tannin inputs on
the geochemical and carbon contents of the peat
down the profile.
A high Sphagnum input is observed in the surface
litter of the peat beneath the Sitka Spruce, indicating
a current vegetation cover of Sphagnum. The
Sphagnum and lignin inputs (Figs.1 & 2 respectively)
are very low in the deeper organic horizons,
suggesting an increased SOM turnover.
The phenolic composition of the SOM of the surface
litter reflects the vegetation input at all three sites.
However, these molecular characteristics are lost with
increasing depth. The open bog site with no
Sphagnum at the surface had a significantly higher
carbon storage compared to the bog margin sites
(409 and 290 t C/ha respectively). This suggests that
Sphagnum moss may not incorporate more carbon
than any other plant genus as previously thought 3 .
Figure 2: Depth profile showing changes in total
Sphagnum products (mg/100mg OC). SE = 2.
[1] Gorham, E. (1991) Ecological Applications 1(2)
182-195; [2] Filley, T., Minard, R., and Hatcher, P.
(1999) Organic Geochemistry 30(7) 607-621; [3]
Clymo, R., and Hayward, P.(1982) in Bryophyte
Ecology 229-289.
172

P-025
Construction of an organic geochemical database for marine
surface sediments
Timothy Eglinton 1,2 , Maria Luisa Tavagna 1 , David Griffith 2 , William Martin 2
1 ETH Zurich, Zurich, Switzerland, 2 Woods Hole Oceanographic Institution, Woods Hole, United States of
America (corresponding author:timothy.eglinton@erdw.ethz.ch)
Information on organic geochemical properties of
sedimentary organic matter is rapidly expanding, both
in terms of the density and diversity of data. This
stems from increasingly streamlined analytical
methods, expanding analytical windows, and the
growing ability to determine multiple properties of
specific organic compounds. Both structural and
isotopic characteristics of sedimentary organic matter
can now be obtained at high spatial, temporal and
molecular resolution. While there have been
numerous detailed organic geochemical studies of
sediments from specific locations and depositional
settings, there has been less effort invested in
bringing this information together to explore
compositional characteristics of sedimentary organic
carbon over a range of spatial scales and within a
broader biogeochemical and sedimentological
context.
We are constructing a database containing bulk and
molecular-level geochemical information on organic
matter within marine surface sediments. The
database is biased towards continental margin
environments because of their disproportionately
large role in organic carbon burial. The database
includes information on bulk organic matter content,
elemental and isotopic composition, as well as
biomarker abundance, distribution and isotopic
composition. This information is placed in
geographic, depositional and biogeochemical context
in order to facilitate geospatial data analysis and
explore overarching controls on sedimentary organic
matter abundance and composition.
We will provide examples of the types of information
that are emerging from the database and will solicit
feedback on how the database can be improved and
expanded.
Figure 1. Example map showing current data
coverage for bulk organic carbon 14 C in surface
marine sediments.
173

P-026
Comparison of comprehensive two-dimensional gas
chromatography/time-of-flight mass spectrometry and gas
chromatography-mass spectrometry for calculating the
geochemical parameter
Huitong Wang 1,2,3 , Na Weng 1,2 , Shuichang Zhang 1,2,3
1 Petroleum Geology Research and Laboratory Center, Institute of Petroleum Exploration & Development,
PetroChina, Beijing, China, 2 Key Laboratory of Petroleum Geochemistry of PetroChina, Beijing, China,
3 State key laboratory of enhanced oil recovery, RIPED, PetroChina, Beijing, China (corresponding
author:wanght@petrochina.com.cn)
In this paper, comprehensive two-dimensional gas
chromatography / time-of-flight mass spectrometry
and gas chromatography-mass spectrometry are
applied respectively to analyze saturated and
aromatic hydrocarbons of crude oil, moreover,
differences of some common oil and gas geochemical
parameters are compared.
Comparison of parameter results obtained from
different instruments shows that, among calculated 20
common oil and gas geochemical parameters, most
of them (17 parameters) have a deviation within 5%,
which indicates that comprehensive two-dimensional
gas chromatography / time-of-flight mass
spectrometry is equivalent to traditional gas
chromatography-mass spectrometry analysis in
respect of calculation of oil and gas geochemical
parameters.
However, for gammacerane/αβ-hopane, 2-ethylnaphthalene/1-ethyl-naphthalene
(ENR), (2,6dimethyl-naphthalene
+ 2,7- dimethylnaphthalene)/1,5-
dimethyl-naphthalene (DNR), the
results from two instruments deviate significantly. This
is because during traditional gas chromatographymass
spectrometry inspection, because of the
limitation of the peak capacity and separating power
for chromatographic column, compounds will form
codistilled peak, or disturbed by other substances,
quantitative results are influenced.
Comprehensive two-dimensional gas chromatography
/ time-of-flight mass spectrometry prevails over
traditional gas chromatography-mass spectrometry in
terms of removing ―codistilled peak‖ effectively.
The former may generate relatively real baseline,
more accurate quantitation of compounds and
accordingly more objective oil and gas geochemical
parameters.
Comprehensive two-dimensional gas chromatography
/ time-of-flight mass spectrometry is one of effective
tools for oil and gas geochemical study.
174

P-027
Separation of biomarkers for their compound specific isotope
analysis
Huitong Wang 1,2,3 , Shuichang Zhang 1,2,3 , Caiyun Wei 1,2
1 Petroleum Geology Research and Laboratory Center, Institute of Petroleum Exploration & Development,
PetroChina, Beijing, China, 2 Key Laboratory of Petroleum Geochemistry of PetroChina, Beijing, China,
3 State key laboratory of enhanced oil recovery, RIPED, PetroChina, Beijing, China (corresponding
author:wanght@petrochina.com.cn)
The study of compounds specific isotope analysis of
biomarkers can effectively solve the difficulties that
regular geochemical experiments cannot conquer,
such as oil-source correlation, the hydrocarbon
resource rocks assessment and etc. Compound
specific isotope analysis(CSIA) is a useful method in
geochemistry, it can be used for reconstruction of
paleoenvironment (Summons and Powell, 1987) and
oil-oil and oil-source rock correlation(Guthrie et al.,
1996). To carry out CSIA accurately, analysis of the
entire peak without co-elution of other compounds is
required, and during preparative separation of organic
compounds without isotopic fractionation of individual
compounds is also necessary (Bidigare et al.,1991).
Molecular sieves are shape-selective separation
materials which have no fractionation effect during
separation of organic compounds (M.Schoell et al.,
1992, Kening et al., 2000, Moldowan and Dahl, 2004).
It becomes one of the development directions for
petroleum geology experimental technique. Based on
large quantities of experiments, the paper describes
absorption and remain behaviors of 9 kinds of
Chinese molecular sieves, establish compounds
specific isotope analysis of biomarker method, and
applies this method to determinate the source rocks
of ancient hydrocarbon and classify the crude oil in
the southern depression of the Juggar Basin.
REFERENCES
[1] Summons,R.E. and Powell,T.G. Identification of
aryl isoprenoids in a source rock and crude
oils:biological markers for the green sulphur bacteria.
Geochimica et Cosmochimica Acta, 51, 557-566,1987
[2] Guthrie,J.M.,Trindade,L.A.F.,Eckardt,C.B.and
Takaki,T Molecular and carbon isotopic analysis of
specific biological markers:evidence for distinguishing
between marine and lacustrine depositional
environments in sedimentary basins of Brazil.
Presented at the Annual <strong>Meeting</strong> of the American
Association of Petroleum Geologists,1996,San
Diego,CA.
[3] Kenig , F. , Popp,B.N. and Summons,R.E.
Preparative HPLC with ultrastable-Y zeolite for
compound-specific carbon isotopic analyses. Organic
Geochem.,2000,31,1087-1094.
[4] Moldowan J.M.and Dahl J., presented at the
Abstract of AAAPG meeting, 2004, Beijing, China
[5] M.Schoell, M.A. Mccaffrey, F. J. Fago, and J. M.
Moldowan, Carbon isotopic compositions of 28,30bisnorhopanes
and other biological markers in a
Monterey crude oil. Geochimica et Cosmochimica
Acta, 56, 1391-1399, 1992
175

P-028
Characterisation of lignin degradation products from dissolved
organic matter: a comparison of different extraction and
analysis techniques
Jonathan Williams 1,2 , Jennifer Dungait 2 , Roland Bol 2 , Geoffrey Abbott 1
1 Newcastle University, Newcastle upon Tyne, United Kingdom, 2 Rothamsted Research North Wyke,
Okehampton, United Kingdom (corresponding author:jonathan.williams@ncl.ac.uk)
Lignin can degrade rapidly in soils. Recent research
has shown that white-rot fungi, such as Pleurotus
ostreatus, can oxidise lignin within a timescale of 7 to
63 days 1,2 and lignin decomposition is monomer
specific 3 . This has highly significant implications for
determining the mechanisms for C sequestration in
soils. Lignin degrades into phenolic compounds which
are water-soluble and, therefore, prone to be
transported through the soil-water continuum.
Guaiacyl and syringyl lignin monomer units have been
detected in fresh, estuarine and marine waters 4 , and
in deep ocean dissolved organic matter (DOM) 5,6
allowing these compounds to be used as geochemical
biomarkers of plant inputs in diverse systems.
After it is degraded at source, the initial forms in which
lignin enters watercourses are not yet known. In order
to characterise and quantify degraded lignin products
entering the soluble phase in soils, it is first necessary
to determine the best approach to extract and analyse
them. Therefore, the aims of this work were to:
(1) determine the best method for the extraction of
lignin-derived compounds from freshwater (draining
from grassland) in terms of recovery and timeefficiency,
i.e. C18 solid phase extraction (SPE) or
freeze-drying.
(2) compare analytical methods, i.e. on-line py-GC-
MS in the presence of TMAH versus on-line py-GC-
MS versus GC-MS of trimethylsilyl (TMS) derivatives.
The results showed that freeze-drying recovered
considerably more DOM than SPE in terms of mass
(Figure 1). However, C18 silica-based SPE recovered
a greater proportion of identifiable lignin- and
carbohydrate-derived compounds than freeze drying
Gas chromatography-mass spectrometric (GC-MS)
analyses of TMS derivatives of samples extracted by
SPE from freshwater identified: benzoic acid, 4-
[(trimethylsilyl)oxy]-,TMS ester; benzoic acid, 3methoxy-4-[(trimethylsilyl)oxy-],
TMS ester; and 3,4bis[(trimethylsilyl)oxy]-,
TMS ester. Abundant
carbohydrate-derived compounds were also
identified: α-D-Ribofuranoside, methyl 2,3,5-tris-O-
(TMS)-; α-1-Mannopyranoside, methyl 6-deoxy-2,3,4tris-O-(TMS)-;
and β-L-Arabinopyranose, 1,2,3,4tetrakis-O-(TMS)-;
and also lipids including C16:0 and
C18:0 fatty acids. C23 to C32 n-alkanes were the most
abundant compounds from the same samples
extracted using freeze-drying.
Figure 1. Yields of DOM recovered by solid phase
extraction (SPE) and freeze-drying (FD) in relation to
TOC from a range of natural freshwaters, showing
standard error bars.
References
[1] Robertson, S., Mason, S., Hack, E., Abbott, G.D.
(2008) Org. Geochem. 39: 945-951; [2] Vane, C. H.,
Martin, S. C., Snape, C. E., Abbott, G. D. (2001). J.
Agric. Food Chem. 49: 2709-2716; [3] Dungait, J.A.J.,
Stear, N.A., van Dongen, B. E., Bol, R., Evershed,
R.P., (2008). Rapid Commun. Mass Sp. 22: 1631-
1639; [4] Louchouarn, P., S. Opsahl, et al. (2000).
Anal. Chem. 72(13): 2780-2787; [5] Opsahl, S. and R.
Benner (1997). Nature 386(6624): 480-482; [6]
Opsahl, S. and R. Benner (1999). Limnol. and
Oceanogr. 44(8): 2017-2023.
176

P-029
Mass spectrometric analysis of intact polar lipids: pros and cons
of Q-ToF, Ion Trap and Single Quadrupole detection
Lars Wörmer, Julius Lipp, Jan Schröder, Kai-Uwe Hinrichs
Org. Geochemistry Group, MARUM Center for Marine Environmental Sciences & Dept. of Geosciences,
University of Bremen, Bremen, Germany (corresponding author:lwoermer@marum.de)
Intact polar lipids (IPLs) have gained importance as
biomarkers, as demonstrated for example by the
inferred high quantity of archaeal biomass in
subseafloor sediments [1]. Thanks to soft ionization
techniques such as electrospray ionization, mass
spectrometry is a suitable method for the detection of
these lipids and is being successfully employed
widely. But to keep advancing the understanding of
the significance of these biomarkers, analytical
improvement is due. Goals to be fulfilled deal, among
others, with chemical characterization of novel lipids,
the accurate quantification of lipid concentration and
the reduction of detection limits in complex matrices.
In the current work we present the optimization of IPL
detection on a Bruker maXis Q-ToF and compare the
obtained results with analyses performed on a
Thermo Finnigan LCQ Deca XP Plus Ion Trap and an
Agilent Technologies 6130 Quadrupole.
Concerning proper identification of unknown lipids, Q-
ToF mass spectrometry shows the advantage of high
mass accuracy. Mass-to-charge (m/z) ratios showed
an error below 5 ppm, which is orders of magnitude
more accurate than the tested Ion Trap and Single
Quadrupole equipment. This is an important
advantage, as chemical composition may often be
directly inferred from the observed m/z ratio if proper
mass calibration is performed. Additionally, in the
case of archaeal GDGT lipids, fragmentation patterns
obtained from Ion Trap and Q-ToF differ clearly. The
latter one not only showed the loss of polar
headgroups, but also allowed the detection of single
biphytane chains, an observation which may be useful
for structural elucidation.
Concerning the quantification of lipids, calibration
curves were performed for eight compounds in a
range from 0.5 to 25 ng injected lipids (e.g. Figure 1).
Overall good linearity was observed for Q-ToF and
Single Quadrupole, but Ion Trap showed evident
signs of curve saturation at the higher concentrations.
Considering all eight compounds, flattening of the
response always began at the same intensity,
independently from actual analyte concentration.
Therefore, and because saturation is mainly observed
at the Ion Trap, we tentatively explain this
phenomenon with issues related to space-charge
effects. Dimer formation, which was observed in all
three systems, also appears to play an important role.
The strong linearity observed is important as it
confirms the robustness of relative abundances to be
measured in environmental samples.
The matrix effect due to the complexity of non-defined
compounds becomes evident when pure IPLs are
added to sediment extracts. Responses and signal-tonoise
ratios in these samples may be more than 10fold
decreased in comparison with pure compounds.
This decrease is system- and compound specific, and
best results were obtained with the Single
Quadrupole, where use of SIM mode provides great
additional sensitivity. Independent of this loss of
sensitivity, linearity appears to be largely maintained.
Still, matrix effects have to be dealt with in order to
guarantee optimal IPL detection. Therefore, further
methodological development is needed concerning
extract clean-up prior to MS detection. Our
presentation will highlight the advantages and
disadvantages of individual MS detection techniques
and provide recommendations for maximizing
performance when analyzing IPLs in highly complex
matrices.
100
80
60
40
20
0
0 5 10 15 20 25
0 5 10 15 20 25
0 5 10 15 20 25
Figure 1: Calibration data for C21-PC (black circle), PEarchaeol
(white circle) and C16-PME (gray triangle)
measured at (from left to right) Ion Trap, Q-ToF and Single
Quadrupole. Data for each system are normalized to largest
peak
References
[1.]Lipp et al. 2009. Nature. 454: 991-994
177

P-030
Trace analysis of methylated substrates in marine sediment
Guangchao Zhuang, Yu-Shih Lin, Eoghan Reeves, Kai-Uwe Hinrichs
MARUM, Center for Marine Environmental Sciences, University of Bremen, Organic Geochemistry Group,
D-28334 Bremen, Germany (corresponding author:gzhuang@marum.de)
Methane in marine sediment has received great
attention because of its role as greenhouse gas and
as major constituent in gas hydrate and its
significance in driving the benthic carbon cycle in
many seep environments. Among all the biological
pathways leading to methane production in marine
sediment, methyltrophic methanogenesis via noncompetitive
substrates, such as methylated sulfides,
methylamines, and methanol, is the least understood
one. The existing knowledge of methylated substrates
and their precursors (summarized in Fig.1) mostly
came from studies of hypersaline environments and
freshwater sediments [1]. Activity studies
demonstrated that degradation of volatile methylated
compounds could account for the substantial fraction
of methanogenesis in some anoxic sulfate-rich
sediments [2].
Fig.1. Summary of source and sink of methylated substrates
for methanogenesis in marine sediments. Solid lines indicate
direct process, and dashed lines represent a series of
sedimentary, chemical, biological processes. Involved
conversion pathways have been proposed through
incubation experiments, but further evidence is needed for
in-situ sediments.
There has been sporadic evidence suggesting that
methylotrophic methanogenesis could contribute to
biogenic methane in subseafloor sediment.
Microbiological studies showed that the potential
methanogenic rates from methylated substrates were
high enough to be detected in subseafloor sediment
samples, and known methylotrophs, members of
Methanosarcinales, have been detected in hydratebearing
sediments drilled by IODP [3]. Yet, the
significance of this process under in situ conditions
remains unclear. A main reason for the uncertainty
comes from the lack of concentration data of these
compounds in subseafloor sediment. The only
published data, to our knowledge, came from the
carbonate sediments of the Great Australian Bight [4]
where the biogenic carbonates are suggested to
contain a protein matrix that is embedded in the
mineral structure and releases amino acids during
diagenesis. The relatively high concentrations of
glycine (up to 1 mmol/kg) and hence elevated levels
mol/kg) could
explain the substantial amounts of methane in the
sulfate-reducing zone. Nevertheless, this case may
not apply to the majority of clastic sediments at
continental margins. Constraining the sources and
fluxes of methylated low-molecular-weight organic
compounds in subseafloor sediments is of great
importance for our understanding carbon flow and
methane biogeochemistry in subseafloor sediments.
We are currently establishing analytical protocols
suitable for the quantitative and isotopic analysis of
methlyated sulfides, methylamines, and methanol. We
are adapting and improving two existing preconcentration
methods, i.e., solid-phase microextraction
and purge-and-trap techniques, for
quantification of these compounds in diverse
sediment samples. Once the analytical barrier is
overcome, we envision extensive application of the
method, such as down-core survey of marine
sediment and further adaptation of the method for
isotope ratio analysis. Our paper will discuss the
success and challenges of the molecular-isotopic
analysis of these trace constituents.
Reference:
1. Lomans, B. P., et al. (2002). Cell. Mol. Life Sci.,
59, 575-588.
2. Oremland, R. S. and Polcin, S. (1982). Appl.
Environ. Microbiol., 44, 1270-1276.
3. Yoshioka, H., et al. (2010). Geobiology, 8, 223-
233.
4. Mitterer, R. M., et al. (2001). Geophys. Res. Lett.,
28(20), 3931-3934.
178

P-031
New techniques for understanding and mapping high-maturity
petroleum systems. Examples from the San Joaquin Basin, San
Juan Basin, and US Gulf Coast
David Zinniker, J. Michael Moldowan, Jeremy Dahl, Peter Denisevich
Stanford University, Stanford, United States of America (corresponding
author:dzinniker@stanfordalumni.org)
While high-maturity petroleum systems play an
increasingly important role in exploration, the
geochemical tools available for their characterization
remain limited. Traditional organic geochemical
analyses focusing on easily-cracked components like
biomarkers are blind to high-maturity contributions
and other analyses (i.e. light hydrocarbon analysis
and diamondoid abundance) hint at their presence but
do not narrow down the geological source, thermal
maturity, or expulsion, migration, or degradation
processes important in its history.
Our work focuses on new analytical techniques for
quantifying and isotopically characterizing a range of
persistent compounds that can survive the extreme
processes involved in the formation of high-maturity
hydrocarbons. Compounds studied include simple
and higher diamondoids, volatile hydrocarbons,
persistent aromatic compounds, and ―high-stability
biomarkers‖ formed from traditional biomarkers by
rearrangement or cracking.
These techniques are showing promise for
fingerprinting the sources of high-maturity liquids and
thermogenic gas – and for identifying and mapping
the contribution of high-maturity liquids to conduits,
reservoirs, and seeps. The work also points toward
important signatures that may help us decipher
evaporative fractionation, cracking, expulsion and
retention in tight source rocks, migration, and catalytic
degradation.
Novel aspects of this research include the routine
extenstion of quantitative diamondoid analysis to
higher diamondoids with four to seven cages, the
extension of diamondoid carbon isotope analysis to
trimantanes and tetramantanes, isotopic
measurement of diverse mono-, di-, tri-, and tetra-
aromatic hydrocarbons, and isotopic measurement of
low ppm / high ppb concentrations of ―high-stability
biomarkers‖.
Model systems with vertically stacked source rocks
were explored to test the utility of these new
techniques. These include Tertiary and Mesozoic
systems in the San Joaquin Basin, Paleozoic and
Mesozoic systems in the San Juan Basin, and
Mesozoic systems along the United States Gulf
Coast.
These new techniques show potential for identifying,
mapping, and understanding high-maturity petroleum
systems. Their utility extends to many petroleum
mixtures because high-maturity contributions will be
the dominant source of ultra-stable compounds
across a broad range of dilutions.
Diamondoid Carbon IsotopeValue,‰
Diamondoid Relative Abundance
-16
-20
-23
-27
10
1
0.1
0.01
0.001
0.0001
0.00001
Adamantane
Smackover
Tuscaloosa
1 2 3 4 5 6 7 8 9 10 11 12
Compound #, adamantane and alkyladamantanes
Diamantane
Triamantane
Tuscaloosa
Smackover
Tetramantane 1
Tetramantane 2
Tetramantane 3
Pentamantane 2
Figure 1. CSIA-D and extended diamondoid profiles
easily distinguish Smackover- and Tuscaloosasourced
petroleum samples from the US Gulf Coast.
The set includes uncracked, cracked, and TSRaltered
samples.
179

P-033
An evaluation of petroleum source potential of fresh water
versus marine-influenced coals from Malaysian Tertiary basins
Wan Hasiah Abdullah 1 , Peter Abolins 2
1 University of Malaya, Kuala Lumpur, Malaysia, 2 PETRONAS Carigali Sdn Bhd, Kuala Lumpur, Malaysia
(corresponding author:wanhasia@um.edu.my)
An integrated evaluation was performed on 5 coal
samples from Malaysian Tertiary basins to assess
their oil-generating potential. These coals were either
deposited in a fresh water terrestrial setting or in a
marine-influenced paralic setting, two of the latter
being mangrove coals. Methods of assessment
include optical, physicochemical (FTIR and NMR) and
pyrolysis techniques (Rock-Eval and Py-GC).
The TOC of the analysed samples ranges from about
42-72 %wt, whilst the HI ranges from 101 to 560
mgHC/gTOC. All samples are either immature or
early mature for oil generation as suggested by the
vitrinite reflectance in the range of 0.42%-0.60%. This
low thermal maturity is supported by Tmax values of
404-431 0 C and strong yellow fluorescing liptinitic
macerals. All of the coals analysed are dominated by
vitrinite. Inertinite content are generally low (< 10% by
volume) and liptinite content varies from
approximately 10-40%. A rather poor correlation was
observed between liptinitic content and the HI values.
The aliphatic to aromatic ratios were obtained based
on NMR and FTIR fingerprints and show a reasonably
good correlation with C8/xylene ratio based on Py-GC
pyrograms.
This study indicates that marine-influenced mangrove
coals possess good oil-generating potential based on
high HI values (513-560 mgHC/gTOC) and supported
by the presence of n-alkene/alkane doublets.
Exsudatinite, bituminite and suberinite are common
liptinitic macerals of these mangrove coals and are
considered as the most oil-prone macerals within
Malaysian Tertiary basins. One of the mangrove coal
samples contains very high amounts of vitrinite
(approximately 90% by volume) thus suggesting the
oil-prone nature is also attributable to the vitrinitic
constituents.
Oil-prone mangrove coal dominated by vitrinite and
exsudatinite from a Tertiary basin of Malaysia; under
reflected ‗white‘ light and blue light excitation (field
width = 0.25 mm).
180

P-034
Chemical structure of kerogen before and after hydrous
pyrolysis
Nadezhda Burdelnaya 1 , Dmitry Bushnev 1 , Maxim Mokeev 2 , Alexsander Gribanov 2
1 Insitute of Geology of Komi SC of RAS, Syktyvkar, Russian Federation, 2 Institute of Macromolecular
Compounds of RAS, Saint-Petersburg, Russian Federation (corresponding
author:burdelnaya@geo.komisc.ru)
The natural organic matter (OM) maturation is a
long process inaccessible to direct observation. In
laboratory conditions at stage-by-stage growth of
temperature it is possible to simulate the process of
artificial OM maturation and to track changes in the
structure of kerogen.
To carry out the hydrous pyrolysis experiments we
chose samples of different type of kerogen (I, II, II-S
and III). The samples were Estonian kukersite (type I);
the Upper Jurassic oil shales from the Sysolsky shale
area (type II and II-S); Oxford and Domanik
carbonaceous shales (type II); coal of the Nechensky
deposit (type III). Pieces of rocks (by 25 g) were put in
autoclave, and 20 ml of distilled water was added.
The thermolysis was performed by 24 h at
temperature 300 о С. The bitumen was extracted by
chloroform, then kerogen was isolated from the rock.
The of bitumen content, Corg, elemental composition
of kerogen were determined before and after hydrous
pyrolysis. NMR high resolution spectra was received
at spectrometer BRUKER AVANCE II-500 (frequency
at 13 С – 125.77 MHz).
All types of kerogen lost hydrogen and oxygen that
is expressed in decrease in H/C and O/C ratios.
Kerogen types II and II-S are characterized by
sharper decrease of Corg and loss of aliphatic
structures (H/C sharply drops). The maximum yield of
bitumen was received in the Volga shales with high
content of sulfur organic structures in kerogen
(kerogen type II-S).
According to solid state 13 С NMR spectroscopy
significant changes in kerogen structure after the
experiment were observed in Jurassic samples (type
II and II-S). The most intensive signal in 13 С NMR
spectrum of all samples is in area 10 - 45 ppm, which
corresponds to absorption of carbon of methyl,
methylene groups, and also tertiary and quaternary
atom of carbon. The highest concentration of aliphatic
carbon is related to kerogen of kukersite with
prevalence of methylene carbon of n-alkyl chain. After
heat treatment the structure of aliphatic chains does
not change practically. Considering spectra of
kerogen type II С-6/9, М-1/2, D-1/30 it is possible to
testify the results in favor of the relation of spectral
pattern of their aliphatic and aromatic structural units.
After autoclaving significant changes in transformation
of chemical structure of kerogen in these samples are
observed, but these changes proceed in one
direction, and it is connected to the increasing
concentration of aromatic nuclea in geopolymer. It is
expressed in increasing signal intensity in band 100 -
160 ppm, a special signal at 127 ppm, corresponding
to chemical shift of protonated carbon in aromatic
rings. The Caliph/Carom ratio in the specified samples -
М-1/2, С-6/9, D-1/30 and V-1/5 tends to one. In the
spectrum of coal kerogen before heat treatment three
intensive signals in band from 100 to 160 ppm are
determined, which are characteristic for carbon in
aromatic structures. After hydrous pyrolysis of rocks
the signal sharply increases at 127 ppm, which
intensity is more than 50% from intensity of other
signals. Probably, there is a rearrangement of mono-,
bycyclic systems into a more compact condensed
polyaromatic structure, which is simultaneously
accompanied by aromatization of acyclic and cyclic
methylene chains and loss of methyl groups.
Nevertheless, the Caliph/Carom ratio, which is less than
one after hydrous thermolysis, changes insignificantly.
Strong changes in the ratio of aliphatic and aromatic
groups were determined in kerogen of type II-S. If the
considered ratio before heat treatment was 3.9, then
after aqueous thermolysis we observed sharp loss of
aliphatic units and aromatization of chemical structure
of kerogen.
The available data confirms non-uniform thermal
influence on structural change of the organic matter
characterized by various types of kerogen. Direct
studying of kerogen structure by solid state 13 С NMR
spectroscopy showed that aqueous thermolysis at
300 о С equally influences on the change of chemical
structure of OM types II and II-S. These changes are
not as noticeable for types I and III due to features of
their chemical structure of kerogen.
181

P-035
Contrasting macromolecular organic matter composition in
surface sediments off the Eurasian Arctic Rivers
Ayca Dogrul Selver 1,2 , Christopher Varden 1,2 , Igor Semiletov 3,4 , Örjan Gustafsson 5,6 ,
Steve Boult 1,2 , Bart E. van Dongen 1,2
1 School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Manchester, M13
9PL, United Kingdom, 2 Williamson Research Centre for Molecular Environmental Science, University of
Manchester, Manchester,M13 9PL, United Kingdom, 3 <strong>International</strong> Arctic Research Center, University of
Alaska, P.O. Box 757340, Fairbanks, AK, 99775, United States of America, 4 Pacific Oceanological Institute,
Far-East Branch of Russian Academy of Science, Vladivostok 690041, Russian Federation, 5 Department of
Applied Environmental Science (ITM), Stockholm University,SE-10691, Stockholm, Sweden, 6 Bert Bolin
Center for Climate Research,SE-10691, Stockholm, Sweden (corresponding
author:ayca.dogrulselver@postgrad.manchester.ac.uk)
Recent climate observations indicate that the largest
effect of global warming is to be expected in the
Arctic, containing half of the global soil carbon [3], yet
this is currently one of the most understudied regions
of the globe. Warming could cause an increase in
active layer depth, enlarging of taliks, and general
reduction of the total volume of permafrost. Recent
studies, suggest that this might also change the input
fluxes, the radiocarbon age and the composition of
the terrestrial organic carbon (terrOC) remobilized to
the Eurasian Arctic Shelf [1]. However, little is known
about changes in the macromolecular terrOC
component.
To improve our understanding of climate warming on
the remobilization of the macromolecular terrOC
sediment samples from five Great Russian Arctic
River estuaries (GRARs) [1] were analysed by py-GC-
MS. In addition, obtaining information on the fate of
the remobilized terrOC is also of major importance.
Therefore sediments from a transect off the Kalix
River (northern Sweden) were also analyzed. This
transect is used because of the geochemical similarity
between the Kalix river and the western GRARs Ob
and Yenisey [2].
Analyses indicate that all pyrolysates were dominated
by four main classes of compounds; furfurals, alkylbenzenes,
nitriles and phenols (Fig. 1). The results
indicate substantial differences of the relative
contributions to the macromolecular terrOC between
the west (Ob, Yenisey & Kalix) and the east (Lena,
Indigirka, and Kolyma) (Fig. 1B). Furfurals
(Polysaccharide moieties) are relatively more
abundant in the western region pyrolysates (19% to
33%) than in the eastern region (4 to18%). In contrast
an opposite trend for the phenols (probably primarily
protein derived) can be observed (30 to 34% in the
west and 37 to 44% in the east). Considering
discontinuous or island permafrost coverage in the
western region and a continuous permafrost coverage
in the drainage basins of the eastern rivers, these
results could indicate a difference in the type of
material released due to the presence/absence of
permafrost.
Analyses of the Kalix River transect indicate a relative
increase in furfurals (from 23% to 36%) but a relative
decrease in phenols (from 41 to 30%) off the river
(Fig. 1A). These results support the idea that the
phenols predominantly originate from relatively labile
terrOC sources (e.g. proteins) and are preferentially
degraded along the transect.
Taken together, this study suggests resolvable
differences between the macromolecular terrOC
composition across the west-east set of five GRARs
as well as in the Kalix River transect. These
differences may assist in predicting how the
composition and the biogeochemical fate of the
macromolecular terrOC may change if the climate in
the eastern Russian-Arctic region becomes more like
that in the western part.
Fig. 1. Percent total index of terrOC composition in A)
Kalix River Transect Sediments and B) GRAR estuary
sediments.
References
[1] van Dongen, B.E. et al. Global Biogeochem.
Cycles 22, GB1011 (2008).
[2] Vonk, J.E. et al. Mar. Chem. 112, 1-10 (2008).[3]
Tarnocai, C. et al Global Biogeochem. Cycles 23,
GB2223 (2009).
182

P-036
Geochemical characteristics of organic matter preserved in
silicified wood of variable age
Monika Fabiańska
University of Silesia, Sosnowiec, Poland (corresponding author:monika.fabianska@us.edu.pl)
Ancient wood can be preserved when silica
dissolved in ground waters infiltrate its cellular voids
and crystallise in them. Since this occurs when wood
structure is relatively intact, wood fossils preserve the
original pattern of tissues, both in its macro-forms and
its microscopic structure [1]. Organic substances are
entrapped by layers of precipitating silica and
preserved, despite unfavourable conditions or their
relative low resistance. Due to its high hardness,
silicified wood is very durable, and can survive
weathering and reworking, unlike the most of fossils.
Chemical investigations of such well-preserved fossil
remains has enabled recognition of their main
constituents - macromolecular and bituminous organic
matter (e.g. [2]).
The aim was (i) to characterise organic matter
found in silicified wood; and (ii) to identify its biological
source. Analyses included solvent extraction and gas
chromatography-mass spectrometry. Cellular
structure preservation was examined by reflected light
microscopy under white and UV light.
Samples show well preserved xylem cellular
structure, with rare deformation of cell walls. Better
preserved are interiors of larger fragments. The cell
lumina are filled with monocrystaline quartz, much
lighter in colour than the cell-wall filling. The darker
outline of the cell walls most probably indicates
organic material preserved between layers of
crystallised silica. Strong fluorescence of cell walls
and weak fluorescence of cell lumina suggests that
cell walls are the main site of organic matter
occurrence in silicified wood. This agrees with the
supposed order of wood tissue decay with the living
cell content destroyed as the first.
Silicified wood shows low extract yields in the
range of 0.001-0.065% (wt.), particularly in fragments
transported by water or glacier and re-deposited in
the Quaternary beds. Age influence seems to be of
the lower importance here.
Several groups of compounds were found in the
wood extracts. The range of n-alkanes correspond to
the range of terrestrial plants fatty acids and alkanols
and their distributions show slight odd-over-even
carbon number predominance (CPI = 1.1-1.6).
Diterpanes related to wood resin included 16�(H)phyllocladane
(Podocarpaceae family), ent-beyerane
and abietane. Hopanes show low concentration, what
may indicate low bacterial degradation of preserved
wood tissue, i.e. cell walls. It seems that bacterial
influence was limited to the organic cell content. Next
this part of xylem was replaced by silica with only low
amount of organic matter (low or no fluorescence in
UV light) leaving intact or almost intact cell walls.
Steranes distributions are of terrestrial type, i.e.
dominated by stigmastanes (C29 sterane) while the
distribution of triaromatic steroids contains higher
amounts of C28 steroids deriving from their C29
sterane precursors. Polycadinene derivatives found in
only one sample, probably of angiosperm wood (oak),
comprised two calamenene isomers, curcumene, and
cadalene.
Fatty acids esters with even-carbon-number
aliphatic alcohols such as esters of lauric) (C12),
myristic (C14), palmitic (C16), stearic ( (C18) and
behenic (C22) acids were found. Esters with oddcarbon
number aliphatic alcohols occurred in lower
concentration. Water washing did not affected these
compounds since their biological function is to protect
tissues against water. As a result even the samples
which organic matter was highly altered in transport
show wide distributions of these compounds.
Identified compound groups predominantly come
from wood tissue, mostly cell walls which seem to be
main source of organic material in silicified wood.
Some features of organic remains are different that
these found in organic material dispersed in
sediments and coals of various maturity, e.g. low
content or absence of pentacyclic triterpanes and
preservation of intact ester waxes. It may be assumed
that rapid enclosing of cell walls material by siliica
organic matter together with less stable compounds
and prevent its water washing or bacterial
degradation.
[1] Manchester R. (1996) Petrified woods in Florida,
Papers in Florida Paleontology No. 8,
[2] Ewbank G., Edwards D. and Abbott G.D. (1996)
Chemical characterisation of Lower Devonian
vascular plants. Org. Geochem. 25, 461-473.
183

P-037
Evolution of depositional environment and biological origin of
kerogen in Lower Miocene Cypris shale in the Eger Graben,
Czech Republic
Juraj Francu 1 , Ivana Sýkorová 2 , Bohdan Kříbek 6 , Karel Martínek 3 , Petr Rojík 5 , Achim
Bechtel 4 , Daniela Mácová 1
1 Czech Geological Survey, Brno, Czech Republic, 2 Institute of Rock Structure and Mechanics, CAS, Praha,
Czech Republic, 3 Charles University, Praha, Czech Republic, 4 Chair of Petroleum Geology,
Montanuniversität, Leoben, Austria, 5 Sokolovska uhelna a.s., Sokolov, Czech Republic, 6 Czech Geological
Survey, Praha, Czech Republic (corresponding author:juraj.francu@geology.cz)
Organic matter in a 75 m cored profile was
investigated in Lower Miocene lacustrine offshore
clays of the Cypris Formation. The purpose was to
identify organic proxies related to the environmental
changes induced by subsidence, lake level
fluctuation, climatic perturbation and bioproductivity.
The Sokolov Basin was situated in a failed rift of the
Eger Graben in the NW Czech Republic. A 30 m thick
brown coal seam produced in an open pit mine was
deposited during the Eggenburgian. It was typical by
periodical occurrence of sporinite rich layers and was
conformably overlain by up to 130 – 180 m thick
monotonous offshore lacustrine succession, the
Cypris shale of Eggenburgian to Karpatian age. At
present, the basin covers ca 20 km2 but the original
area was probably larger. Nearshore facies are rarely
preserved.
Depth (m)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
0 1 2
Pri/Phy
0 1 2
Pri/n-C 17
oxic
dysoxic
0 1 2 3 4 0 1 2
n-C19 /n-C31 n-C23/n-C31 Fig. 1. Isoprenoid and n-alkane ratios in the
Eggenburgian to Karpatian profile.
Based on the sedimentology, bulk rock data, and
biomarkers the profile provides a geochemical archive
of 19 to 17 Ma bp with several partial intervals related
to principal phases of basin evolution. The lower part
of the profile is characteristic by abrupt flooding of
older fluvial to overbank alluvial coal-bearing
sediments manifested by shale deposition. Kerogen
consists of redeposited humic matter with partly
decomposed plant tissues mixed with macrophytes
and minor algae. Pristane/phytane ratio suggests that
the water column became very soon dysoxic.
Increased n-C23/n-C31 indicates growth of aquatic
plants - macrophytes, their contribution diminished
with time. Sudden drop in lake level resulted in a thin
coal seam with high TOC and low hydrogen index
(HI). The algal bloom occurred in the middle and
upper part of the basin fill during the stagnant water
phase and resulted in HI as high as 900 mg/g TOC.
Additional two oxic events occurred in the later lake
evolution indicated by TOC and HI drop, increase in
Pri/Phy, Pri/n-C17 and lower algal molecular
signature. The final phase of lake evolution is marked
by occurrence of carbonate layer followed by
oscialting bioproductivity and organic matter
preservation.
184

P-038
Organic geochemistry of coals and carbonaceous shales from
the palaeocene Los Cuervos formation in San Pedro Del Río
(Táchira State, Venezuela)
Marcos Escobar 1 , Manuel Martinez 2 , José R. Gallego 3 , Gonzalo Marquez 4 , Azucena
Lara-Gonzalo 3
1 University of Zulia & CARBOZULIA, Maracaibo, Venezuela (Bolivarian Republic of), 2 Central University,
Caracas, Venezuela (Bolivarian Republic of), 3 University of Oviedo, Mieres, Spain, 4 University of Huelva,
Palos de la Fra., Spain (corresponding author:escomar24@gmail.com)
Several authors [1] have previously postulated good-
to moderate-quality continental source rocks in the
Palaeocene Los Cuervos Formation (Venezuela).
This possibility makes it feasible to undertake an
organic geochemical and petrographical investigation
of the carbonaceous shales and coals in a geological
section of this formation opposite San Pedro del Río
village (Táchira State). It should be noted that the
heterogeneous character of sedimentary depositional
environments of continental facies, a common
occurrence in a fluviodeltaic system such as the one
that gave rise to the aforementioned unit [1], involves
the need to perform a detailed evaluation of the study
section since possible transgressive or regressive
pulses may alter the quality of the source rocks
throughout any given stratigraphic column.
Twelve samples, six of carbonaceous shales and the
rest of coals, were collected and analysed. These
samples (TLC-1 to TLC-12) were numbered from the
bottom of the stratigraphic column of the Los Cuervos
Formation in San Pedro del Río. The following
analyses were performed: shales (COT and Rock-
Eval pyrolysis), coals (vitrinite reflectance, organic
petrographic and Rock-Eval pyrolysis), and bitumens
(SARA method and gas chromatography coupled to
mass spectrometry for the saturate fraction: acyclic
isoprenoids, n-alkanes, steranes, and terpanes).
Results clearly indicate that vitrinite reflectance, Rock-
Eval, %22S, %20S, and COT values are
characteristic of moderate to good source rocks that
have reached an early oil window maturation level
(�0.6) [2]. Likewise, the n-alkane distribution patterns,
pristane to phytane ratios (>3), presence of 18�(H)oleanane
and predominance of ���C29 steranes over
C27 homologues suggest a type III kerogen [2].
The increase in the total sulfur content in these coals
from bottom (�0.8%) to top (�1.4%) of the sequence
suggests the existence of a transgressive pulse [3],
whose maximum corresponds with the TLC-10 and
TLC-11 samples, within a regressive event, typical of
the rest of the Los Cuervos Fm. There is also an
evolution towards a fluvial depositional environment
that characterizes the overlying formation: El Mirador.
The predominant maceral group in these coals,
except TLA-6, is the vitrinite type (80%). The upward
increase in desmocollinite and corpocollinite
concentrations, as well as of exinites, may be
attributed to a change in the dominant vegetation in
the swamp or peatbog, from woody plants at the base
to mangroves or ferns, with slight gymnosperm input
and a marine influence at the top of the sequence [4].
The facies diagram based on the tissue preservation
index (TPI) and gelification index (GI) [5] (Figure 1)
denotes that the study section represents a
progressive transition between a limnotelmatic facies
in the lower part of the Los Cuervos Fm., associated
with a meandering fluvial channel system, and a
limnic facies in the central and upper part deposited
in a barrier-protected swamp in a low coastal area.
Fig. 1. TPI vs GI diagram for the study coals.
References
[1] Boesi, T., et al. (1988). Stratigraphic study of the
Northandean Flank. In: Memoirs of III Bolivarian Symposium
on Petroleum Exploration of the Subandean Basin, 613-637.
[2] Hunt, M. (1996). Petroleum Geochemistry and Geology,
2nd Edition. Freeman, New York.
[3] Caruccio, F.T., et al. (1977). Paleoenvironment of Coal and
its Relation to Drainage Quality. US EPA Agency, Cincinnaty.
[4] Teichmüller, M. (1989). Int. J. Coal Geol., 12, 1-87.
185

P-039
Organic carbon content and character of Holocene–Eocene
sediments recovered during IODP Expedition 317, Canterbury
Basin, New Zealand
Simon George 1 , Julius Lipp 2 , George Claypool 3 , Toshihiro Yoshimura 4 , Expedition 317
Shipboard Scientific Party, Integrated Ocean Drilling Program 5
1 Macquarie University, Sydney, Australia, 2 University of Bremen, Bremen, Germany, 3 Lakewood, Colorado,
United States of America, 4 The University of Tokyo, Chiba, Japan, 5 Texas A&M University, College Station,
United States of America (corresponding author:Simon.George@mq.edu.au)
Integrated Ocean Drilling Program (IODP)
Expedition 317 aimed to derive an understanding of
the relative importance of global sea level changes
versus local tectonic and sedimentary processes in
controlling continental margin sedimentary cycles [1].
Four shelf-upper slope sites were cored in the
Canterbury Basin on the eastern margin of the South
Island of New Zealand in water depths of 85-344 m.
Eocene to recent sedimentary sequences, influenced
by a high rate of sediment supply from the uplifting
Southern Alps, were cored in a transect of three sites
on the continental shelf (landward to basinward, Sites
U1351, U1353, U1354) and one site on the
continental slope (U1352). More than 530 core
samples were analysed on-board ship by elemental
analysis, coulometer for carbonate content and
pyrolysis (source rock analyser). This dataset
provides an unparalleled opportunity to understand
organic matter content, character, preservation and
the influence of increasing thermal maturity in a
terrestrially-influenced basin.
Organic carbon content was generally low (1% TOC.
Analyses of sediment samples at Site U1352 also
distinguished the clay-rich lithostratigraphic Unit I from
the carbonate-dominated Unit II. The organic matter is
mainly terrestrial plant in origin, based on the majority
of hydrogen indices

P-040
Evolution of organic matter in lignite-containing sediments
under different environmental conditions. Analytical pyrolysis
(Py-GC/MS) proxy
José A. González-Pérez 1 , Abad Chabbi 2 , Cornelia Rumpel 3 , José Mª de la Rosa 4 ,
Francisco J. González-Vila 1
1 IRNAS-CSIC, Seville, Spain, 2 INRA-UEFE, Lusignan, France, 3 INRA-BIOEMCO, Thivernal-Grignon, France,
4 ITN, Sacavém, Portugal (corresponding author:jag@irnase.csic.es)
Mine soils and sediments in Lusatian open-cast lignite
mining district (Germany) contain a mixture of lignite
and recent organic matter. Organic matter (OM)
characterization and its transformation in mine soils
and sediments is essential to understand ecosystem
functioning in this region. For this study analytical
pyrolysis (Py-GC/MS) was used as a geochemical
proxy to complement previous studies done at a
rehabilitated site for soil development 45 years ago
and directed to monitor the different C sources (lignite
or plant derived) in soils and sediments and its degree
of degradation in contrasting environments (Chabbi et
al., 2006, 2007).
Representative vegetation and organic carbon (OC)
rich soil/sediment fraction (humus fraction separated
by flotation) from lake sediments were sampled at two
depths (0-5 and 5-10 cm) in three plots along a
transect covering: an 1) upland forest soil, 2) partially
submerged sediment at the land–water interface and
3) constantly submerged sediment.
The analysis of plant (lipds, isoprenoids,
methoxyphenols & carbohydrates) and possible lignite
(alkyl-napththalenes, alkyl-benzenes & PAHs)
biomarkers released after pyrolysis (500 ºC) supports
previous findings in the area using different proxies.
The conditions in the submerged sediment favors OM
protection and the accumulation of decomposing plant
material, whereas a more intense OM degradation
process seems to be occurring in the land–water
interface area that is characterized by fluctuating
water levels. In addition, the presence of organic
sulfur compounds (OSC); a well resolved series of
alkyl-thiophenes (6 to 24 C) with marked dominance
of even C number molecules, indicate the possible
occurrence of particular mechanisms of C
preservation in this extreme anoxic S rich
environment i.e. via sulfur ―quenching‖ with plant
derived lipids during early diagenesis (Sinninghe-
Damsté et al. 1989; Sinninghe-Damsté & de Leeuw,
1990) in the submerged sediments of rehabilited
lakes.
References:
Chabbi A., Rumpel C., Kögel-Knabner I. (2007) Org.
Geochem. 38: 835–844;
Chabbi A., Rumpel C., Grootes P.M., Mariotti A. Hüttl
R.F. (2006) Org. Geochem. 37: 740–753
Sinninghe-Damsté J.S.; de Leeuw J.W. (1990) Org.
Geochem. 16: 1077–1101
Sinninghe Damsté J.S., Rijpstra W.I.C., Kock-van
Dalen A.C., de Leeuw J.W., Schenck P.A. (1989)
Geochim. Cosmochim. Acta: 53, 1343–1355.
187

P-041
Organic geochemistry of entrapped bitumen within
kerogen/mineral matrix of an Australian Late Paleoproterozoic
lead-zinc-silver deposit
Alexander Holman 1 , Kliti Grice 1 , Caroline Jaraula 1 , Arndt Schimmelmann 2
1 Western Australia Organic and Isotope Geochemistry Centre, Department of Chemistry, Curtin University,
Perth, Australia, 2 Department of Geological Sciences, Indiana University, Bloomington, United States of
America (corresponding author:alexander.holman@student.curtin.edu.au)
Hydrothermal fluid transport essential in forming
the Late Paleoproterozoic McArthur River or "Here's
Your Chance" Pb/Zn/Ag ores in the Northern Territory
of Australia is also reflected in low δD and δ 13 C
values of n-alkanes and a decrease of polyaromatic
hydrocarbon content with diminishing hydrothermal
alteration. Estimates of maturity based on organic
molecular proxies calculated from abundances of
freely extractable hydrocarbons (Bitumen I) in this
ore, however, may not be reliable due to recent
hydrothermal alteration and transport processes.
Maturity proxies are calculated with abundances of
isomers of methylphenanthrene, phenanthrene,
steroids and triterpenoids. There is strong evidence
for differing thermal stabilities of these compounds
with increasing clay content, such that a more pristine
record of maturity is preserved in hydrocarbons
occluded in the kerogen/mineral matrix (Bitumen II)
(Nabbefeld et al., 2010). To test this hypothesis, we
have investigated the biomarker distributions and
stable carbon and hydrogen isotope ratios of Bitumen
II and compared these with those reported in Bitumen
I (Williford et. al. 2011). Bitumen II has been obtained
after initial extraction of Bitumen I by Williford et al.
(2011) through extensive demineralistion with HCl
and HF/H3BO3 (as shown by Nabbefeld et al. 2010
and references therein) to isolate organic components
entrapped within the kerogen/mineral matrix. The
differing mineral structures within the matrix have
been investigated with microscopy techniques.
References
Nabbefeld B, Grice K, Schimmelmann A, Summons
R, Troitzsch U, Twitchett RJ (2010). A comparison
of thermal maturity parameters between freely
extracted (Bitumen I) and a second extract
(Bitumen II) from within the kerogen matrix of
Permian and Triassic sedimentary rocks. Org.
Geochem. 41, 78-87.
Williford KH, Grice K, Logan G, Chen J, Huston D
(2011). The molecular and isotopic effects of
hydrothermal alteration of organic matter in the
Paleoproterozoic McArthur River Pb/Zn/Ag ore
deposit. Earth Planet. Sci. Lett. 301, 382-392
188

P-042
Search for chemotaxonomic indicator by analyses of resistant
macromolecules in plant fossils from the Cretaceous Futaba
Group, Japan
Kei Ikeda 1 , Ken Sawada 1 , Hideto Nakamura 1 , Masamichi Takahashi 2
1 Faculty of Science, Hokkaido University, Hokkaido, Japan, 2 Faculty of Science, Niigata University, Niigata,
Japan (corresponding author:ikedakei@mail.sci.hokudai.ac.jp)
Resistant macromolecules as cutin and suberin
constituting living plants are stable and have
resistance to microbial degradation and diagenesis.
The composition of molecular unit (monomer)
constituting resistant macromolecules are various
according to taxonomy. If variability of the
composition remained in plant fossils which had
undergone diagenesis, the composition can be
chemotaxonomic indicator, and it is useful for
classification. On the other hand, if the composition of
molecular unit constituting resistant macromolecules
changed according to environmrnt and diagenesis, it
can be indicator of paleoenvironment and mechanism
of diagenesis. However, it is unknown that what factor
affects the preservation of composition of molecular
unit. In this study, we analyzed resistant macromolecule
of a wide variety of plant fossils collected
from the same Cretaceous coal bed and investigated
variability of composition of their molecular units.
We analyzed mesofossils of angiosperms and
gymnosperms collected from Ashizawa Formation,
Futaba Group, Kamikitaba, northeastern Japan. For
example, fruit fossils of Hironoia fusiformis and
Archaefagacea futabensis, flower fossils of Esgueiria
futabensis, leaf fossils of Juniperus, a stem fossil of
Ephedra and some fossils of fruits, seeds and woods
which are uncertain about taxonomy. Extraction and
saponification were performed as reported previously
[1]. Briefly, powder samples of above fossils were
solvent-extracted under room temperature and 110°C
to be removed free compounds completely. The
residues were hydrolyzed by KOH / methanol under
room temperature and 110°C. GC-MS are used for
identification and quantification of compounds.
As main molecular units released from resistant
macromolecule of all samples, n-alkanoic acids (fatty
acids; C10-C28) and n-alkanols (C10-C28) were
detected. Distributions of carbon number of fatty acids
were clearly different according to a part of samples.
In woody fossils, the ratios of C14 /C16 released fatty
acids are low, while the ratio of C18 /C16 released fatty
acids are high. On the other hands, the C14 /C16 ratios
of released fatty acids are high and the C18 /C16 ratios
are low in non-woody organs such as cuticles (e.g.
flowers, fruits and leaves). These results indicate that
the woody and non-woody fossils reflect the
composition of suberin and cutin, respectively. As
Figure 1, the relationships between these ratios can
be distinguish non-woody fossils such as flower, fruit
and leaf from wood fossils. From these results, we
suggest that such diagram can be useful to identify
the kinds and parts of broken fossils. Also, by the
relationship between C20 /C18 ratios and C20 /C16
ratios of n-alkanols released from resistant
macromolecule, woody fossils can be separated from
flower, fruit and leaf fossils roughly. The high ratio of
n-C20alkanol may reflect the composition of suberin.
C18/C16
140
120
100
80
60
40
20
0
ester-bond FA
y = 1.78x + 29.78
0 10 20 30 40
C14/C16
angio-fruit
gymno-leaf
gymno-stem
gymno-seed
wood
系列6
線形 (系列6)
Fig. 1 Relationship between the ratios of C18 / C16 and
C14 / C16 fatty acids released from resistant macromolecules
in plant fossils. Line represents the
boundary between datasets of woody and non-woody
fossils based on the linear discriminant function.
Reference
[1] Sawada, K., Arai, T. and Tsukagoshi, M. (2008)
Organic Geochemistry 39, 919-923.
189

P-043
Petrological and organic geochemical characteristics of the No.
11 coal in Antaibao mine, China
Kankun Jin, Yanheng Li, Xiaoli Deng, Shenjun Qin
Hebei University of Engineering, Handan, China (corresponding author:wsaluo@163.com)
Twenty one bench samples were collected from
the No. 11 coal in the Pingshuo Coalfield. The
samples were analysed by petrological and organic
geochemical methods.
The Antaibao mine in the Pingshuo Coalfield is
located in the Shanxi province, Northern China. The
coal-bearing sequences in the Pingshuo Coalfield
include Benxi Formation and Taiyuan Formation (both
Pennsylvanian) and Shanxi Formation (Lower
Permian) [1]. The No.11 coal is in the Taiyuan
Formation and has a total thickness of 3-5m. The
thickness of the coal seam of the sampling location is
4.25 m.
Random vitrinite reflectance (Rr) was measured
by using a Leitz MPV3 reflected light microscope
fitted with a halogen lamp (oil 32/0.65, 548 nm, 3×3
�m, EMI9592 S-11; glass standard Leitz, Ro=0.889%).
The average value is 0.65% Rr. The results indicate
that the vitrinite content of the Late Carboniferous
coals from Antaibao mine varies from 17.48 to
90.91%, and the average value is 55.30%. According
to the GI-TPI diagram, the swamps of the No. 11 coal
are main lowstand systems tract and wet forest
swamps.
For organic geochemical analyses, samples were
Soxhlet-extracted for 48 h using chloroform as solvent.
Extract yields were determined gravimetrically after
removal of the solvent. The extract yields vary from
1.26 to 7.34 mg/g. The extracts were separated into
three fractions by column chromatography over prewashed
silica gel (70-230 mesh, 50×1 cm). The gas
chromatographic (GC) analyses were carried out on a
HP-5890 gas chromatograph fitted with a silica
capillary column (25m×0.2mm i.d.) coated with SE-54.
Gas chromatography-mass spectrometry (GC/MS)
analyses were performed on a Finnigan-Mat SSQ70
GC-MS. A fused silica capillary column (25m×0.25mm
i.d.) coated with SE-54 was used.
The saturated hydrocarbons occur from C11 to
C25, and the main peaks are observed before C24. The
result indicates that the predominant plant sources in
the swamps are lower aquatic organisms [2,3].
Sixty five aromatic compounds of the samples
were identified by GC/MS analysis. The data show
that they are preferentially composed of alkylated
naphthalenes and phenanthrenes. Abundant sulfur
containing polycyclic aromatic compounds were also
observed. These compounds are related to the
marine environments during swamp and peat
formation stages [4].
References
[1] Liu, D. M., Yang, Q., Tang, D. Z. (2001) Int. J.
Coal Geol. 46, 51-64.
[2] Ren, Y. J., Yang J. N., Qiu L. W., Liu K. Y.
(2010) Geol. J. China Univ. 16, 63-72.
[3] Yao, S. P., Hu, W. X., Xue, C. Y., (2004) Acta
Sedimentol. Sin. 22,519-524.
[4] Sun, Y. Z., Li, Y. H., Zhao C.L., Lin M. Y.,
Wang J. X. Qin S. J. (2010) Energ. Explor. & Exploit.
28, 97-104.
190

P-044
Geochemical characteristics of organic matter in the
Kupferschiefer strata in the Fore-Sudetic Monocline, SW Poland
Paweł Kosakowski, Adam Kowalski
AGH-University of Science and Technology, Krakow, Poland (corresponding author:kosak@agh.edu.pl)
The Polish Permian Basin (PPB) is part of the great
Permian sedimentary basin in Europe extending from
England through Holland, Germany, Denmark, Poland
up to Lithuania and western Belarus. The SW part of
this basin forms the Fore-Sudetic Monocline.
The Kupferschiefer strata are less than one metre
thick and consist of rich organic laminated black
mudstones, marls and carbonates, deposited in
anoxic or suboxic shallow shelf conditions. The
Kupferschiefer shales were deposited following a
rapid marine transgression over an area that had
been subject to a very long period of arid to semi-arid
conditions. A characteristic feature is the presence of
large amounts ore of metals. The ores in such regions
contain sulfides of Cu, Pb, and Zn and may be
enriched in a variety of other elements.
Pyrolysis assay was done with a Delsi Model II
Rock-Eval® instrument. The saturated and aromatics
hydrocarbons extracted and separated from bitumens
separately underwent gas chromatography analysis
on Agilent Technologies type 7890A apparatus,
coupled with mass spectrometer typ 5975C Network.
As an internal standard β-Cholan and o-Terphenyl
were used for saturated fraction and aromatics
fraction, respectively. The analysis of metals was
made by ICP-MS method on samples treated with
HClO4-HNO3-HCl-HF at 200°C with a Perkin Elmer
SCIEX ELAN 6000 spectrometer at ACTLABS
Laboratories Ltd., Canada.
The organic carbon (TOC) contents in the
Kupferschiefer marine bituminous shales of Upper
Permian (Zechstein) age vary from 0.01 up to 16 wt.%
[1]. As pointed out by Bechtel and Puttmann [2] the
organic carbon content generally decreases from the
bottom to the top of the Kupferschiefer profiles. Data
from Rock-Eval pyrolysis and biomarkers analyses
show the presence of sapropelic Type-II kerogen at a
maturity level corresponding to the initial stage of lowtemperature
thermogenic processes. The interesting
information can be found in the distribution of aliphatic
hydrocarbons. The even-carbon unsaturated
hydrocarbons (Fig. 1 - black triangles) are very
intense in the samples. Their maximum intensity can
be observed for 20-22 carbon atom. The presence of
such compounds can be indicative of relatively low
maturity level of the organic matter. However, the
analyses of the studied aromatic fraction revealed that
its maturity level was 0.6 - 0.7 %Ro. This can prove
that organic matter disposed in the Kupferschiefer
shale could initiate transformation of kerogen to liquid
hydrocarbons. As a result of this process, the part of
fatty acids in esters coming from Eubacteria and
Eukarya was reduced to unsaturated hydrocarbons.
Intensity
Intensity Intensity
C C
15
16
Nor
C 17
C 18
Ph
Pr
C19 C 20
C21
10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00
C 22
Stęszew-9/2950,4m
C 25
C24
C23 Retention time (min.)
C27 C29 C26 C28 C30
C 31C32
C 33C34
Kaleje-2/3095,6m
Antonin-17/1740,6m
Fig. 1. The distribution of the n-alkanes and
izoprenoids (m/z 71)
The research was undertaken as research project
of Polish Ministry of Science and High Education Nos
18.18.140.624 and 18.18.140.881. This study was
financed from the scientific fund of 2010-2012.
References
[1] Sawłowicz, Z, Gize, A. P., Rospondek, M., 2000.
Kluwer Academic Publ. Dordrecht, 220-242
[2] Bechtel and Puttmann 1997. Palaeogeogr.,
Palaeoclimatol., Palaeoecol., 136, 331-358.
191

P-045
Occurrence and geochemical characteristics of fatty acids
bound with clay minerals in muddy hydrocarbon source rocks,
Bohai Bay Basin, Eastern China
Longfei Lu 1,2 , Tenger Borzijin 1,2 , Tianzhu Lei 3 , Jingong Cai 4 , Jie Wang 1,2
1 Sinopec Research Institute of Petroleum Exploration and Production, Wuxi, China, 2 Wuxi Institute of
Petroleum Geology, Sinopec Research Institute of Petroleum Exploration and Production, Wuxi, China,
3 Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou,, Lanzhou, China, 4 Tongji
University, Shanghai, China (corresponding author:llf779712@163.com)
Sorptive protection of clay minerals is thought to play
an important role in stabilizing organic matter in
hydrocarbon source rocks and marine sediments. In
order to explore adsorption sites of organic matter
binding to clay minerals and their influences on
organic matter stability, we focus on occurrence mode
of fatty acids in clay minerals and their degradation.
Clay minerals from two lacustrine hydrocarbon source
rocks (TOC, 6.8% and 9.1%; Ro, 0.5% and 0.7%), the
third member of Shahejie Formation, Tertiary, eastern
China, were subjected to sequential treatments
including soxhlet extraction, base hydrolysis and acid
hydrolysis, and three acids moieties were obtained. Xray
diffraction (XRD) and Gas Chromatography-Mass
Spectrometer (GC-MS) were employed to
characterize clay minerals and fatty acids,
respectively.
XRD results show that the d001 diffraction peak of
smectite of clay minerals is 1.434nm and 1. 416nm.
After chloroform extracted, the d001 peak is 1.434nm
and 1.416nm, after base hydrolysis is 1.315nm nm
and 1.331nm, and after acid hydrolysis are 1.273nm
and 1.227nm, respectively. It indicates that sorption
sites of fatty acids binding to clay minerals are of
great difference, ie three occurrences of fatty acids
sorption to clay minerals: free acids extracted by
soxhlet extraction occur in micropores of clay
minerals, ―OH - ‖ labile acids obtained by base
hydrolysis adsorb to stacking edges and/or outside
surface of clay minerals, and ―H + ‖ labile acids
obtained by acid hydrolysis intercalate interlayer of
smectite.
GC-MS analysis shows that fatty acids are enriched in
clay minerals, and fatty acids of the various fractions
are different in quatity, composition and distribution.
With respect to the degradation level of the acid
moieties, the following order was obtained: ―OH - ‖
labile acids > free acids > ―H + ‖ labile acids as
indicated by (i) Percentage composition of
unsaturated fatty acids, more susceptible to alteration,
is the highest in ―H + ‖ labile acids, followed by free
acids and ―OH - ‖ labile acids, (ii) Percentage of
branched acids of ―OH - ‖ labile acids > free acids >
―H + ‖ labile acids, (iii) i+a15:0/n15:0 and i17:0/n17:0
ratio of ―OH - ‖ labile acids (>1) > free acids > ―H + ‖
labile acids and (iv) CPIA of ―OH - ‖ labile acids < ―H + ‖
labile acids < free acids.
―OH - ‖ labile acids and ―H + ‖ labile acids were
transformed from adsorption of free acids by clay
minerals, which experience a higher degradation than
free acids since deposition and in low evolution stage.
With evolution increase, free acids experience an
intense degradation while ―OH - ‖ and ―H + ‖ labile acids
experience a limited degradation for clay minerals
adsorption protection, resulting degradation level of
bound acids near or even less than free acids. Since
our samples are in a low thermal maturity stage,
degradation level of ―H + ‖ labile acids has been less
than free acids. Moreover, ―OH - ‖ labile acids occur in
stacking edges of clay minerals, part of which are not
protected well by clay minerals, leading to its
degradation level a bit higher. In addition, part of free
acids encapsulated in clay matrixes (aggregation
pores) were also obtained by soxhlet extraction,
which reduces the general degradation level of free
acids.
Our results show that the ―OH - ‖ labile acids
experienced a substantial level of degradation, the
free acids appeared a limited degradation, and the
―H + ‖ labile acids was subjected a low level of
degradation and was preserved effectively. It is
because interlayer, stacking edges and aggregation
micropores of clay minerals can influence accessibility
of substrate to bacterial and rates of penetration of
dissolved oxygen in different level. The stability of
sedimentary organic matter is influenced by the type
of adsorption sites of clay minerals, which would
result in different degradation rate and preservation
during diagenesis and hydrocarbon generation
process.
192

P-046
Characterization of the source rock of Jurassic (Tithonian) in
Southeastern Mexico applying the organic facies
Jose Antonio Perez Ortiz 1 , Luis Lopez Lopez 1 , Esaul Gutierrez Mejia 1 , Luis Manuel
Medrano Morales 2
1 Instituto Mexicano del Petroleo, Pachuca, Mexico, 2 Petroleos Mexicanos, Cd. del Carmen, Mexico
(corresponding author:jortiz@imp.mx)
We performed optical-geochemical study of 10 wells
located in the Southeastern Mexico Basins in order to
make a correlation of organic facies.
The wells studied they are located in the marine
region, the call Sonda of Campeche, where the
carbonated rocks, they are rich in organic matter
laminated of algal-sapropelic and ligneous type.
In Sonda of Campeche, in which to the Upper
Jurassic it corresponds, we can mention that are
rocks of Tithonian age, which are represented by
calcareous argillaceous limestones and shales; with
an irregular distribution rocks of Kimmeridgian age,
composed by fine terrigenous horizons and micritic
carbonates. Finally we can indicate rocks of Oxfordian
age, where some associate fine terrigenous horizons
with evaporítes
Optical and geochemical characterization studies
were made in order to know whether these are source
or reservoir facies.
We studied 250 samples of core and 25 oil samples
from these 10 wells. Geochemical studies were
applied to these samples:
- Gas Chromatography
- Saturated biomarkers
- Diamondoids
- Pyrolysis
- Compositional kinetic
- Carbon isotopy
While optical analysis the samples were made:
- Transmitted Light
- Fluorescent Light
- Reflected Light
- Confocal Study
The analysis of reflected light allowed to know the
range of maturity of organic matter and studies with
confocal microscopy were performed to correlate the
oils with organic facies.
Thanks to the findings and conclusions of this study,
largely eliminated the geological and economic risk,
as recommended and prevented the drilling of new
wells in areas of low maturity of organic matter.
In addition, this study allowed to know and
characterization of oils in relation to the organic facies
and characterize mixtures of oils
193

P-047
Characterization of lignites from the Drmno field, Kostolac Basin,
Serbia, based on biomarker composition
Dragana Ņivotiš 1 , Ksenija Stojanoviš 2 , Aleksandra Ńajnoviš 3 , Olga Cvetkoviš 3 , Hans
Peter Nytoft 4 , Georg Scheeder 5
1 University of Belgrade, Faculty of Mining and Geology, 1100 Belgrade, Serbia, 2 University of Belgrade,
Faculty of Chemistry, 11000 Belgrade, Serbia, 3 Center of Chemistry, IChTM, 11000 Belgrade, Serbia,
4 Geological Survey of Denmark and Greenland, DK-1350 Copenhagen, Denmark, 5 Federal Institute for
Geosciences and Natural Resources, 30655 Hannover, Germany (corresponding
author:xenasyu@yahoo.com)
The Kostolac lignite basin of Upper Miocene age is
located about 90 km east of Belgrade. It is divided
into three coal fields: Drmno in the eastern, Širikovac
in the central, and Smederevsko Podunavlje in the
western part of the basin. Coal from the Drmno field is
typical humic coal with huminite concentrations
between 50.8 and 90.3 vol.%, liptinite less than 6
vol.% and inertinite between 1.5 and 21.6 vol.%.
Saturated and aromatic hydrocarbons were analyzed
by GC-MS. The relative proportions of hydrocarbons
in the SOM are low (< 11 %), consistent with the low
maturity of the organic matter. The n-alkane patterns
of the coal samples are dominated by long-chain nalkanes
(C27-C33) with a marked odd over even
predominance (CPI 3.1-5.6), indicating a significant
contribution of epicuticular waxes. The
pristane/phytane (Pr/Ph) ratio varies in range 0.24 to
1.74. Based on the maceral composition, it could be
concluded that Pr and Ph most probably originated
from chlorophyll in land plant-dominated organic
matter. Therefore, the values of Pr/Ph could imply
anaerobic to slightly oxic conditions during
sedimentation, consistent with maceral composition.
In all samples, aromatic sesquiterpenes are observed
in low quantities. Cadalene predominates over
cuparene, calamenene and 5,6,7,8-tetrahydrocadalene.
Diterpenoids are main constituents of
saturated and aromatic fractions of investigated coals.
16�(H)-phyllocladane and pimarane are dominant by
far in the saturated fractions, whereas norpimarane,
kaurane and beyerane are present in minor amounts.
The aromatic diterpenoids consist of norabietatetraenes,
norabieta-trienes, dehydroabietane,
bisnorsimonellite simonellite, retene, sempervirane,
totarane, bisnordehydroabietane, hibaene, ferruginol,
with 18-norabieta-triene, dehydroabietane, simonellite
and retene predominating. Due to the fact that in all
samples totarane was identified, the precursor of
which is totarol [1], it was assumed that ferruginol, 18norferruginol
and 12-hydroxysimonellite may be
subjected to the same diagenetic transformations as
totarol, specially in anoxic conditions, forming
dehydroabietane, 18-norabieta-triene and simonellite,
which are dominant compounds in aromatic fraction
(Fig. 1). Almost all of the samples contain nonhopanoid
triterpenoids in very low amounts,
consisting of de-A-ring degraded triterpenoids (des-Aolean-enes,
des-A-urs-enes, des-A-lupane,
tetramethyl-octahydro-chrysenes and trimethyltetrahydro-chrysenes).
Strong domination of
diterpenoids over triterpenoids implies that the coalforming
plants were mostly gymnosperms (conifers).
A high amount of 16α(H)-phyllocladane and presence
of pimarane, ferruginol, totarane, hibaene, and
cuparene indicates that the coal forming plants
belonged to the conifer families Taxodiaceae,
Podocarpaceae, Cupressaceae, Araucariaceae and
Phyllocladaceae [1,2].
The hopanoid patterns are characterized by the
occurrence of C2713,18-hop-ene, 17α,21β(H)- and
17β,21β(H)- hopanes from C27 to C32 with the C28
being absent. Domination of ββ-isomers in range C27 -
C30 over αβ-hopanes confirms an immature stage of
the organic matter. Steroid biomarkers in Drmno
samples consist of C29 Δ 2 -, Δ 4 - and Δ 5 -sterenes. Low
steroids/hopanoids ratio (0.07-0.22) indicates a more
bacteria-influenced facies and argues the role of
bacteria in degradation of plant tissue.
Fig. 1. Proposed diagenetic pathways for the
degradation of ferruginol.
References
[1] Otto et al., 1997. Org. Geochem. 26, 105-115.
[2] Otto, A., Wilde, V., 2001. Bot. Rev. 67, 141-238.
194

P-048
Relationship of lithium enrichment with macerals and organic
compounds of Coal Seam 6 from the Guanbanwusu Coal Mine,
Inner Mongolia
Yuzhuang Sun, Yanheng Li, Shiming Liu, Cunliang Zhao, Kankun Jin
Hebei University of Engineering, Handan, China (corresponding author:sun_yz@hotmail.com)
The thace elements in coals have been studied
by many coal geologists since long time [1, 2]. Both
useful and harmful elements have been reported by
many authors [2]. Lithium is the associated valuable
element in coal and is also a kind of very important
energy metals. Lithium has been named as ―new
energy metal‖ and ―metal to promote the world
advance‖. One gram lithium may release 3400 kWh
energy. Nuclear fusion energy is higher stage of
energy use after fission type reactor. A lithium reactor
to generate 10 billion kWh energy needs lithium only
10 tons [3](Metal, 2006).
The concentrations of lithium in coals have been
studied by some geologists [4]. US National
Committee for Geochemistry (1980) reported that the
average content of lithium in coas of the world is 15.6
mg/kg; Finkelman [4] reported that the average lithium
content in USA is 16 mg/kg. More statistic data about
lithium contents in coals were given by Sun et al. [5].
All data indicate that the lithium contents vary in
different coalfields. Except in China, average lithium
conntents in coals are lower than 20 mg/kg in all other
countries. Neither important progresses on the oreforming
theories of Li in coal were made nor coal
associated lithium ore deposits were discovered.
The Guanbanwusu Coal Mine is located at the
southern Inner Mongolia. The mine district is 1.94-km
long (N-S) and 1.82-km wide (W-E), with a total area
of 3.5 km2. Geologically, it belongs to the Junger
Coalfield. The coal-bearing sequences in the
Guanbanwusu Coal Mine include Benxi Formation
and Taiyuan Formation (both Pennsylvanian) and
Shanxi Formation (Lower Permian) with a total
thickness of 90–210 m. Coal reserves of the
Guanbanwusu Coal Mine amount to 92.4 Mt.
36 coal samples from Coal Seam 6 were taken
from the Guanbanwusu Coal Mine, Junger Coalfield,
Inner Mongolia, and the samples were analysed by
microscope, ICP-MS, GC and GC-MS analyses. The
results indicate that the lithium contents have reached
0.2829%. This content is higher than the Geology and
Ore Deposit Standard Specifications for Rare Metal
Mineral Exploration (>0.2%) of the People‘s Republic
of China (DZ/T 0203-2002). According to this
standard, lithium content has reached an associated
deposit in this mine.
The results of maceral analyses indicate that the
enrichment of lithium have positive relationship with
inertinite contents. The samples with high lithium
contents have also inertinite contents.
The results of GC and GC-MS analyses indicate
that the enrichment of lithium have positive
relationship with some aromatic compounds,
especially, with polycyclic aromatic sulfur compounds
and polycyclic aromatic oxygen compounds
References
[1] Dai, S. F., Ren, D. Y., Tang, Y. G., Yue, M. and Hao, L. M.
(2005) <strong>International</strong> Journal of Coal Geology 61, 119-137.
[2] Swaine, D. J. (1990) Trace Elements in Coals. Butterworth,
London, pp. 278.
[3] Metal (2006) Non-ferrous Metallurgy in China 2, 54-56 (in
Chinese).
[4] Finkelman, R. B. (1993) Organic Geochemistry. New York,
Plenum Press, pp. 593-607.
[5] Sun Yuzhuang, Li Yanhen, Zhao Cunliang, Lin Mingyue,
Wang Jinxi and Qin Shenjun (2010) Energy Exploration &
Exploitation 28(2), 97-104.
195

P-049
Organic matter of Lower Permian sediments from Subpolar
Urals
Olga Valyaeva, Olga Protsko
Institute of Geology of Komi Science Center of RAS, Syktyvkar, Russian Federation (corresponding
author:valyaeva@geo.komisc.ru)
The object of researches is the Lower Permian
sediments on the outcrops of the river of Kozhym of
Subpolar Urals.
In the studied section the kungurian sediments are
represented by kosyinskaya formation. This is organic
matter (OM) of IV type located in clay sediments of
alluvial fan. The quantity of organic matter, measured
by value of organic carboneum (Сorg) in samples, is
low, changes from 0.56 (sample 5/9/1, siltstone) to
0.91% (sample 5/7, clay siltstone). The sample 5/11 is
marked by the high value of bituminous index - 1,15%
that is characteristic for epigenetic bitumen. Initial OM
has a mixed character and contains components of
inertinite, vitrinite and transitive varieties, which is also
testified by the distribution of n-alkanes and
isoprenoids. The distribution peaks in medium
molecular region fall on С16, С20 that is characteristic
for bioproducers of zoo- and algal material. In the
high-molecular area distribution peaks fall on n-С27,
С29 that is characteristic for terrigenous material.
Among isoprenoids it was possible to determine iso-
С15, С16, С18, С19 and С20. The prevalence of prystane
(Pr/Ph˃1) is considered as indication of humic ОM,
which accumulation occurred in oxidative conditions.
Chernorechenskaya formation
The content of organic carbon varies in the
sediments of Chernorechenskaya formation from 0.11
to 1.47 %. The increased Corg contents were observed
in clay aleurite varieties, and minimum ones - in the
sandy varieties. The general constant level of Corg
contents in aleurite-argillite rocks of verkhneartinsky
sediments testifies to similar to kosyinskaya
sedimentation conditions.
Inclusions of scattered organic matter (SOM) of
inertinite group occur as separate slurry scraps with
cellular structure and uniform mass filling every
possible voids and fractures. Also dendrite-like
accumulations, filled by inertinite OM, were found.
Vitrinite inclusions are represented by gelified
lumpy mass, and liptynite – by deformed remains of
sporingite shells and cutinite scraps.
Often the studied samples revealed development
of ore minerals on the surface of organic inclusions,
forming a kind of joints of organic and or material.
The analysis of samples by the gas-liquid
chromatography revealed that ОM has a mixed
character displayed in bimodal distribution of nalkanes.
However, they differ by quantitative
contribution of humic and sapropelic components that
is displayed in various distribution of n-alkanes in
medium- and high molecular areas. Thus, samples
24/2 24/5 are characterized by the high content of
С11-С18 - to 31.24% and low relative concentrations of
high molecular normal alkanes (С25-С35 from 18.87 to
22.24%). In such bitumoids the distribution peak falls
on n-C16 and n-C20, the prevalence of even alkanes is
determined, which is more noticeable for n- С16
(2*С16/(С15+С17) to 1.84, 2*С20/(С19+С21) – до 1.2).
According to some researchers the prevalence of
even medium molecular n-alkanes is characteristic for
hydrocarbons of bacteria, in particular, n-C16 is a sign
of heterotrophic microorganisms. In high molecular
area the distribution peaks fall on n-C27 and n-C29.
For samples 24/12 and 24/13 the share of medium
molecular alkanes is lower (С11-С18 - 15.63-18.10%),
high molecular compounds dominate (С25-С35 from
31.32 to 32.85%). The predominance of odd nalkanes
of composition С17, С19, С27 and С29 is
observed. The 2*С17/(С16+С19) index fluctuates from
1.06 to 1.19. The prevalence of n-C17 alkane testifies
to the participation of algal ОM (phytoplankton) in the
initial biomass.
All bitumoids among isoprenoids are marked by
increased concentration of phytane (Pr/Ph - 0.51-
0.99) and Ph/C18 index; it can testify to the
regenerative conditions of sedimentation.
According to data in literature the sedimentation
conditions of the given formation are characterized as
delta front.
Thus, on the basis of the conducted researches it
is possible to make a conclusion that initial ОM of
Lower Permian sediments of the river of Kozhym has
a mixed character. The pyrolitic data showed very low
generation potential and hydrogen index of the
rocks.The bacteria-algal component has insignificant
character. Organic matter is at stage of catagenesis
МК1-МК2. The material is oxygenated. The rocks
possess a very low oil-gas generation potential and
are mainly gas source.
196

P-050
Information provided by the Organic Matter contained in cherts
of the Ras-Draâ phosphate deposit (Tunisia) on their
depositional environment
Aïda Ben Hassen 1 , Jean Trichet 2 , Jean-Robert Disnar 2 , Habib Belayouni 3
1 Centre de Recherche et des Technologies de l'Energie, Technopôle Borj Cédria, Hammam-Lif, Tunisia,
2 Institut des Sciences de la Terre d'Orléans, Orléans, France, 3 Faculté des Sciences de Tunis, El Manar,
Tunisia
In the Paleocene-Early Eocene Ras-Draâ (Tunisia)
phosphate outcrop formation a laminated (siliceous)
chert level is interbedded between two phosphatic
strata (CVI and CVII phosphorites; P2O5 > 18%). The
study of the organic matter (OM) associated to the
chert aims at bringing some light on the nature and
the geochemical properties of this OM and then to
draw some conclusions on the genesis of these
sediments.
The main results of this study can be summarized
as follows:
1. The Total Organic Carbon (TOC) content, given
by Rock-Eval pyrolysis, is about 1.6%.
2. The geochemical characterization of the OM
contained in cherts, by Rock-Eval (RE) pyrolysis
concludes to: (i) a high aliphatic character (Hydrogen
Index IH value ~ 499 mg d‘HC/g TOC) and thus to a
marine planktonic origin of the OM (Type II), (ii) a low
degree of OM maturity (Rock Eval Tmax = 429 °C)
and (iii) to the presence of little oxidized organic
components due to the lower Oxygen Index IO (about
50 mg de CO2/g TOC).
3. The chemical extraction of the humic substances
(HS) associated to the cherty sediments (following the
<strong>International</strong> Humic Substances Society protocol)
evidences significant amounts of extractable humic
compounds (~20% TOC) and higher proportions of
non extractible residue or "humin" (~ 80% TOC). Such
significant amounts of HS were reported by Kahouach
(1989) (up to 27% TOC) in chert interlayers from
tunisian phosphatic series. However, higher HS
proportions were found by Bein et Amit (1982), in
cherts associated to Negev phosphorites (more than
40% of OM are in humic form). According to Kolodony
(1969), such results suppose that the cherts formation
is due to the silicification of phosphatic materials that
were probably rich in HS. In our study, RE parameters
– markedly high HI and distinctly low OI values –
respectively suggest the autochthonous origin of this
OM and, the absence of oxidative destruction of the
initial organic material during chert formation.
4. The main geochemical and spectroscopic
features of the humic acids (HA) extracted from the
cherts are the following ones: (i) atomic O/C and H/C
ratio values of 0.27 and 1.53% signify that these
humic compounds originated from marine aliphatic
OM; (ii) FTIR analysis of cherts-extracted HA show
that these organic compounds are rich in aliphatic
structures that is typical for an algae derived material.
5. The occurrence of fossil molecules in chert lipidic
extract (C22 predominance in n-alkane distributions,
presence of steroids and benzohopanoids) confirms
the autochthonous marine origin and the low degree
of maturity of the OM. With regards to chert age, the
abundance of HS implies their good preservation in a
reducing depositional environment (Belayouni et
Trichet, 1983).
Finally, the study of the OM associated to the
cherts interbedded within P-rich levels brings clear
evidence that these sediments were deposited in a
reducing marine environment marine and that they
only experienced limited diagenesis (that led them to
the humic stage).
References
[1] Bein, A., Amit, O., 1982. Depositionnal
environments of the Senonian chert phosphorites and
oil shales sequence in Israel as deduced from their
organic matter composition. Sedimentology 29, 81-90.
[2] Belayouni, H. and Trichet, J. [1983] Preliminary
data on the origin and diagenesis of the organic
matter in the phosphate basin of Gafsa (Tunisia).
Advances in Organic Geochemistry 1981, 328-335.
[3] Ben Hassen, A. [2007] Données nouvelles sur la
matière organique associée aux séries du bassin
phosphaté du sud-tunisien (Gisement de Ras-Draâ)
et sur la phosphatogenèse. Thèse de Doctorat,
Université d‘Orléans. France.
[4] Kahouach, H., 1986. Abondance, nature et
composition de la matière organique contenue dans
les sédiments de la série phosphatée du gisement de
Ras-Draâ (Nefta-Tozeur). Application à la valorisation
des minerais phosphatés. Rapport de DEA. Université
de Tunis. Tunisie.
[5] Kolodony, Y. 1969. Petrology of siliceous rocks in
the Mishtah Formation (Negev, Israel). J. Sedim.
Petrol. 39, 166-175.
197

P-051
Kerogen sulphur, hydrogen and carbon isotope variation across
the Permian-Triassic boundary in the South China
Chunfang Cai, Lei Xiang, Kaikai Li, Lei Jiang
Key Lab of Petroleum Resource, Institute of Geology and Geophysics, Chinese Academy of Sciences,
Beijing, China (corresponding author:cai_cf@mail.iggcas.ac.cn)
The biogeochemical cycle of organic and inorganic
carbon and pyrite and sulphate sulphur across the
Permian-Triassic boundary (PTB) has been widely
studied to determine the cause of mass extinction and
environment change in the PTB. However, organically
bound sulphur and hydrogen in kerogen have been
seldom characterised. Kerogen δ 34 S and δD values
are measured to reflect the change cross-checked
δ 13 CKerogen values from four sections nearby the PTB.
Broadly parallel changes of Kerogen δ 34 S, δD and
δ 34 C values occur across the PTB for the all four
sections (Fig.1)
In the Meishan section (Changxing, Zhejiang)
deposited in an upper slope environment, δ 34 Skerogen
values range from -20.5 to -8.3‰ (n=7) below PTB
with the heaviest δ 34 Skerogen and δ 34 Spyrite values and
the lightest δ 13 Ckerogen measured in the bed 22 and
bed 24, where abundant aryl isoprenoids were
detected (at the bottom of bed 24, mass extinction
occurred). δDkerogen values show dramatic change with
the lightest value (-174‰) above the PTB at bed 28.
Shangsi and Guangzi sections, NW Sichuan were
deposited in a deeper lower slope environment. In
Shangsi and Guangzi section, δ 34 Skerogen values range
from -42.3 to -10.6‰ (n=11) and δ 34 Spyrite from -35.9
to -5.0‰ below the PTB with the heaviest δ 34 Skerogen
and δ 34 Spyrite values measured from the uppermost
Changxing Fm (P3ch). Much heavier δ 34 Skerogen value
of -12.6‰ was measured from the below Longtan Fm
(P3l). In Guangzi section, Changxing Fm δ 34 Skerogen
values are -30.5‰ and -27.1‰, and δ 34 Spyrite from -
32.6‰ and -34.5‰. Longtan Fm δ 34 Skerogen values
show a wide range from -32.2‰ to -13.1‰ (averaged
-24.2‰, n=9), and δ 34 Spyrite from -37.2‰ to -22.5‰
(averaged -30.5‰, n=5). Abundant aryl isoprenoids
were detected nearby the PTB in the both section.
In Wanyuan section, NE Sichuan, much heavier
δ 34 Skerogen values (+5.5‰ and -1.7‰) were detected
from the uppermost Changxing Fm (P3ch) (Cai et al.,
2010) and similar values from -6.6 to +4.1‰ in the
below Longtan Fm (P3l) (averaged -0.5‰). No aryl
isoprenoids were detected from the Longtan Fm.
From the above, there exists large variation in δ 34 S
values of kerogen and pyrite with geographical
location: the heaviest values in NE Sichuan and the
lightest values in NW Sichuan and Meishan section
ranging in between. A shallower environment for the
Meishan during the deposition than the NW sections
may indicate water depth may have controlled the
δ 34 S values. This is likely due to euxinic and stratified
water column and recycling of H2S by green and
purple sulphur bacteria to greater degree in deeper
water. Decades of reefs found in the NE Sichuan
suggest a shallow water and oxygen is not too limited
before the end of Permian in this area.
Interestingly, those samples with abundant aryl
isoprenoids show the heaviest δ 34 Skerogen and δ 34 Spyrite
values in the all three sections. Possible reasons
among others include 1) much lower sulphate
concentration of seawater during the period; 2)
bacterial sulphate reduction in the sediments not in
water columns, i.e., in a relatively closed system with
a limited supply of sulphate (Cai et al., 2009).
A significant negative shift in δDkerogen value above
PTB is associated with high Pr/Ph ratio, indicating an
influx of more freshwater carrying organic matter as a
result of terrestrial ecological collapse into the ocean.
P d
Strata T f
1
3
P l
3
Shangsi
Kerogen
δ C
13
δ S
-40 -10
34
-28 -25
Py OS
Strata
T f
1
P d
3
P w
3
Guanzi
δ S
34 Kerogen
δ C
13
-34 -16 -29 -26
Py OS
Strata
T f
1
P d
3
P l
Wanyuan
3
Kerogen
δ C
-27 -3 -28 -22
13
S δ34
Py OS
Beds
Formation
Strata
T f
1
P d
3
P l
3
YinKeng
Changxing
Meishan
Kerogen
δ S
δD
-165 -125
34 Kerogen
δ C
-22 -2
13
-29 -25
31
29- 30
28
Py OS
27
26
25
24
23
22
21
20
18-19 17
15-16 12-13 10-11 8-9 7
2-6 1
Py—Pyrite
OS—Organically bound sulfur
Fig. 1. Variation of kerogen � 34 S,� 13 C and �D and
pyrite � 34 S values across the PTB from four sections
from NW and NE Sichuan and Changxing, Zhejiang.
Acknowledgement
This work is financially supported by NSFC 40839906.
References
[1] Cai, C.F. (2009) Organic Geochemistry 40, 755-
768.
[2] Cai, C.F. (2010) Organic Geochemistry 41, 871-
878.
198

0 - 69.99
0 - 69.99
P-052
Incorporation of archaeal and bacterial lipids into
geomacromolecules: implications for organic matter
preservation
Lidia Chaves Torres, Katie L. H. Lim, Paul S. Monaghan, Richard P. Evershed, Richard
D. Pancost
Organic Geochemistry Unit, University of Bristol, Bristol, United Kingdom (corresponding
author:chylc@bristol.ac.uk)
The incorporation of organic matter into
geomacromolecules during diagenesis contributes to
their formation and composition. These
geomacromolecules are generally resistant to
degradation, and thus, their formation is a crucial
aspect of understanding the bioavailability of organic
carbon in the geosphere, the carbon cycle and its role
in climate regulation, and the formation of source
rocks. However, the mechanisms by which
geomacromolecules are formed, including the
incorporation of lipids, remains poorly understood.
Sulfurisation processes have been shown to be
important in S-rich marine contexts, but in other
settings, oxidative cross linking appears to be
extensive (e.g. Versteegh et al., 2004 [1]).
In order to better understand geomacromolecule
formation, we are examining the nature and timing of
the incorporation pathways of archaeal and bacterial
lipids, as they have diagnostic structures that act as
robust tracers among the different organic matter
fractions. Furthermore, the wide range of different
functionalities of these compounds allow us to
examine which chemical moieties might be most
prone to cross-linking reactions. Thus, the purpose of
the research is analyzing the fate of structurally
diagnostic archaeal and bacterial membrane lipids
through the comparison of free biomarkers (free;
those that are extractable with organic solvents,
including core lipids and intact polar lipids) with their
structural equivalents released from
geomacromolecular fractions via sequential chemical
degradation (incorporated).
In the first instance we have focused on a core with
significant methanogenic activity, whose redox
gradient across the water table enables the
exploration of both aerobic and anaerobic conditions.
In such a terrestrial setting sulfur does not play a
predominant role, and instead oxidative
polymerization may be the key pathway responsible
for the geomacromolecule formation. We have started
by characterizing the free archaeal and bacterial
membrane lipids, archaeol and branched fatty acids,
respectively, and their occurrence as either core
lipids, phospholipids or glycolipids. Selected sections
Relative Abundance
of the core were analyzed and the results show that
archaeol concentrations increased with depth,
especially below the water table, whereas bacterial
phospholipid fatty acid concentrations decreased.
These observations collectively show a shift in the
population towards a relatively smaller bacterial
community and larger archaeal community.
Ongoing work is now focussed on the incorporation
of these different compounds into the non-extractable
fraction. Initially, we have hydrolysed the peat residue
under basic and then acidic conditions releasing
bacterial and archaeal biomarkers. Given the age of
the core (

P-053
Sulfur-bound compounds in free and bound lipids of recent
sediment of continental type
Tatyana Cheshkova, Tatyana Sagachenko
Institute of Petroleum Chemistry SB RAS, Tomsk, Russian Federation (corresponding
author:chtv12@mail.ru)
In this work SC of polar fractions of free and bond
(hydrolyzed) lipids from the sediment of continental
type (Lake Tukhloye, West Siberia) have been
studied.
By literature data sulfur in OM structures of
recent sediment occurs as sulfide and/or polysulfide
bridges mainly in intermolecular bonds. Reductive
desulfurization on Ni-Raney is widely used to
characterize such sulfur-bond structures followed by
isolation and analysis of the products obtained [3]. We
carried out comparative analysis of the individual
composition of the saturated hydrocarbons (HC)
isolated by a method of liquid-adsorption
chromatography from non-polar compounds (fraction
A) and desulfurization product of polar compounds of
the lipids under study (fraction B). By the data of gasliquid
chromatography and chromatography-massspectrometry
bond-free (А) and sulfur-bond (B)
saturated HC in free and hydrolyzed lipids are
presented by normal (m/z 57) and isoprenoid (m/z
113) alkanes, steranic (m/z 217) and terpanic (m/z
191) structures.
In both lipid forms sulfur-bond alkanes differ from
bond-free ones by a lower portion of n-alkanes and a
higher portion of isoprenoids. Relative content of
phitane increases in the composition of sulfur-bond
isoprenoid and one observes the appearance of
phitene and 5-octadecen (С18:1). The determined
character of the distribution of acyclic HC proves an
earlier conclusion that sulfurization of isoprenoids
proceeds more active as compared with n-alkanes [3].
Besides the indicated compounds we determined 4methylheptadecan
in fraction B of the hydrolyzed
lipids. Its appearance can testify that SC of the bond
lipids contain alkyltiacyclane structures, which under
desulfurization conditions are destructed to form the
identified HC.
Chromatography-mass-spectrometry analysis of
fractions A and B of the both lipid forms demonstrated
that HC С27–С29 of configurations ���20R,S and
�ββ20R,S. are included into the composition of
steranes. Higher concentration of �ββ20R,S –
steranes is typical for the compounds of fraction A.
Fraction A of the hydrolyzed lipids has a lower portion
of low-molecular homologues. Fraction A of the
hydrolyzed lipids has a lower content of pregnane
(С21) and contains no 20-methylpregnan С22. Sulfurbond
HC (fraction B) of the both lipid forms were
determined to have the same composition of regular
steranes С27–С29, among which ���20R,S – steranes
predominate. The absence of low-molecular
homologues of С21,22 composition is a special feature
of fractions B in sterane HC. The data obtained
testify that high-molecular steranes of ���configuration
are the first to enter sulfurization
process.
HC of terpane series in fractions A of the both
lipid forms are presented by tricyclic (cheilanthanes),
tetracyclic and 17�21β(С29, С30, С31 S,R) pentacyclic
(hopanes) structures. Fraction A of the hydrolyzed
lipids contain no hopanes of biological form
17β(Н),21β(Н) of С29, С31 S,R composition and
moretane – 17β21�С30. Hopanes 17�21β(С32, С33
S,R) appear in the composition pentacyclic
hydrocarbons, while monosaturated 17�21βС30hop-
17-21-en disappears. Fraction B of the both lipid
forms contain the same types of terpane HC:
17β21�С27, 17β21βС29, 17�21βС30 and 17β21β(С31
С32 S,R). For free lipids their content in fraction B is
higher as compared with fraction A. The concentration
of pentacyclic structures increases mainly due to
homologues of biological form 17β(Н),21β(Н).
Fraction B of the hydrolyzed lipids contain no
cheilanthanes С20H36, C22H40 and C25H46, tetracyclic
terpanes, pentacyclic HC 17�21βС27, 17β21�С30,
17β21βС30 and 17�21βС31 S,R, and monosaturated
17�21βhop-28-30-enС29. Sulfur-bound HC of the
hydrolyzed lipids differ from HC of fraction A by the
appearance of homologues of biological form
17β21β(С31,С32S,R). Biological β-hopanes are
characterized by thermodynamic instability
determining their participation in the processes of
sulfurization of lipid substances.
200

P-054
Hyper-accumulations of monosulfidic sediments in the Peel-
Harvey Inlet, Western Australia
Robert S Lockhart 1 , Paul Greenwood 1,2 , Richard Bush 3 , Kliti Grice 1
1 WA Organic and Isotope Geochemistry Centre, Curtin University, Bentley, WA, Australia, 2 John de Laeter
Mass Spectrometry Centre, University of Western Australia, Crawley, WA, Australia, 3 Southern Cross
GeoScience, Southern Cross University, Lismore, NSW, Australia (corresponding
author:R.Lockhart@curtin.edu.au)
Recently discovered hyper-accumulations of reactive
iron monosulfides, in association with high
concentrations of organo-sulfur compounds (OSC),
within the eutrophic environment of the Peel-Harvey
estuary in Western Australia, are the subject of
current scientific interest (Sullivan et al., 2006).
Linked to major algal bloom episodes, the deposits
manifest themselves as a viscous monosulfidic black
ooze (MBO) which, in addition to physically choking
this busy water-way, pose a series of potential
environmental hazards including rapid deoxygenation
and acidification of surface waters and release of
potentially toxic metals (Bush et al., 2004a; Ward et
al., 2010). While much published research focuses
on the role of inorganic sulfur geochemistry in such
environmental systems (Burton et al., 2006; Bush et
al., 2004b; Rickard & Luther, 2006), reactions
involving organo-sulfur compounds, which are also
likely to play a key role in biomineralisation pathways,
remain poorly understood.
In response, a range of analytical techniques were
employed to characterise the dynamic organic
geochemistry of these deposits, via detailed
examination of a series of cored sections recovered
from several key accumulations within the estuary.
Analysis of extractable lipid hydrocarbon fractions has
been complimented by chemical degradation
techniques for polar and/or refractory material which,
along with catalytic Hydropyrolysis (Hypy), allow the
selective cleavage of specific structural bonds (e.g. C-
S, S-S, C-N or C-O) within residual macromolecular
material, in order that the products are more
amenable for GC-MS and CSIA analysis. This
approach has provided the first fundamental
knowledge regarding the primary sources of
sedimentary organic carbon involved in the formation
of MBO in eutrophic estuaries. Furthermore, this
study is unique in that it examines the interaction
between organic and inorganic sulfur compounds in a
natural anoxic environment.
Investigation of extract and hydropyrolysate fractions
confirms a dominantly algal and higher plant derived
source of organic matter. Meanwhile, a range of
unique hydrocarbons have been released following
Raney nickel desulfurisation of the polar fraction,
extracted from the sediments. This indicates that
reactions between reduced sulfur-species played an
important role during the incorporation of organic
matter within the early stages of diagenesis in this
contemporary, highly sulfidic and toxic, environment.
In addition, phospholipid fatty acid analysis (PLFA)
has revealed information regarding microbial
community (aerobic and anerobic) structure within the
sediments.
References
Burton, E. D., Bush, R. T., and Sullivan, L. A., (2006)
Chemosphere, 64:1421-1428.
Bush, R. T., Fyfe, D., and Sullivan, L. A., (2004a)
Australian Journal of Soil Research, 42:609-616.
Bush, R. T., Sullivan, L. A., Fyfe, D., and Johnston,
S., (2004b) Australian Journal of Soil Research,
42:603-607.
Rickard, D. and Luther, G. W., III, (2006) Reviews in
Mineralogy and Geochemistry, 61:421-504.
Sullivan, L. A., Bush, R. T., and Burton, E. D., (2006)
Report produced for the Department of Environment,
Western Australia
Ward, N. J., Bush, R. T., Burton, E. D., Appleyard, S.,
Wong, S., Sullivan, L. A., and Cheeseman, P. J.,
(2010) Marine Pollution Bulletin, 60:2130-2136
201

P-055
Organic matter preservation in Cariaco Basin, a pyrolytic study
Melesio Quijada 1 , Armelle Riboulleau 1 , Pierre Faure 2 , Olivia Bertrand 2
1 FRE 3298 CNRS Géosystèmes, UFR des Sciences de la Terre, Université de Lille 1, Villeneuve d'Ascq,
France, 2 UMR 7566 G2R, Université Henri Poincaré, Vandeuvre-les-Nancy, France (corresponding
author:ma.quijada-hermoso@gmail.com)
The Cariaco Basin is an east-west trending pull-apart
basin (Schubert 1982), located on the continental
shelf of the northern coast of Venezuela. The limited
exchange with open ocean and the high oxygen
demand from organic matter (OM) decomposition,
makes that its water column is anoxic below
approximately 275 m. (Thunell et al., 2000). Cariaco
Basin is the second largest euxinic basin on Earth
and has been widely used for studying
biogeochemical processes.
OM preservation pathway in the sediments of the
Cariaco Basin has previously been studied with a
6000 years focus (Aycard et al. 2003). This study
revealed the presence of melanoidin moieties in
kerogens, pointing to an important role of the
degradation-recondensation pathway. Sulfurization
appeared as a minor process, though from its high
content of inorganic sulfur in the water column and
sediment, Cariaco Basin presents favorable
conditions for sulfurization of OM.
Classical treatment for kerogen isolation may induce
artifactual formation of melanoidin-like moieties
leading to inaccurate interpretation of preservation
processes (Allard et al. 1997, Quijada et al. 2009).
To overcome this problem, we analyzed by flash
pyrolysis 13 kerogen samples isolated using a
sequential hydrolysis method avoiding artifacts
formation (Riboulleau et al. 2005; Quijada et al.
2009). The studied kerogens ranged in age from 0.4
to 135 ky, allowing to survey relatively long-term
diagenetic evolutions.
The total ion current (TIC) of flash pyrolysates
showed a complex mixture dominated by n-alkanes,
n-alkenes, alkylbenzenes and alkylthiophenes.
Alkylpyrroles and branched alkanes are also present
in relatively high abundance. Phenols, furans,
alkylindanes and alkylbenzothiophenes are minor
constituents of these pyrolysates.
A large number of C0- to C4-alkylbenzenes was
identified. Their abundance increases with depth
suggesting several contributors (algae and
cyanobacteria lipids, bacterial isoprenoids) and
progressive condensation of the organic matrix with
time. Alkylthiophenes are the second (in abundance)
most important compounds found in the TIC trace of
all samples. Two different groups of alkylthiophenes
were identified: (i) C1- to C5- alkylthiophenes,
suggesting sugars sulfurization (Sinninghe Damsté et
al. 1998; Kok et al. 2000; van Dongen et al. 2003); (ii)
isoprenoid thiophenes dominated by 3-methyl-2-
(3,7,11-trimethyldodecyl)-thiophene, described as an
early stage diagenetic product coming from the
incorporation of sulfur into chlorophyll-derived phytol
or archaebacterial phytenes and their diagenetic
products (Brassell et al. 1986; Sinninghe Damsté et
al. 1998). These two groups of thiophenes present a
global increase with depth, suggesting progressive
incorporation of their precursors to the
macromolecular organic matrix through sulfurization.
The relative abundance of pyrolitic yields
(alkylbenzenes, alkylthiophenes, alkylpyrrols) of
kerogens isolated by sequential hydrolyses are
significantly different to those of kerogens isolated by
the classical treatment, and characterized by a higher
alkylthiophene abundance. This observation confirms
that artifactual formation of melanoidin during kerogen
isolation during the previous study lead to wrong
interpretation of OM preservation process in the
Cariaco Basin.
In addition, while Aycard et al. (2003) showed a
substantial increase of sulfur incorporation with time
(6 ky), we here evidence that incorporation of
inorganic sulfur into organic matter continues with
depth, suggesting that natural sulfurization is not
restricted to early diagenesis but also operates on a
longer period of time (130 ky).
References:
- Aycard et al. (2003). Org. Geochem. 34, pp. 701-
718
- Brassell et al. (1986). Nature. 320, pp.160-162.
- Eglinton et al. (1994). Org. Geochem. 22, pp. 781-
799.
- Kok et al. (2000) Geochim. Cosmochim. Acta. 64,
pp. 2689-2699.
- Schubert (1982). Mar. Geol. 47, pp. 345–360.
- Sinninghe Damsté et al. (1998) Earth Planet. Sci.
Lett.164, pp. 7-13.
- Thunell et al. (2000). Limnol. Oceanogr. 45, pp. 300-
308
- van Dongen et al. (2003). Org. Geochem. 34, pp.
1129-1144.
202

P-056
Detection of microbial biomass in subseafloor sediments by
pyrolysis-GC/MS
Rong Zhu, Gerard J.M. Versteegh, Kai-Uwe Hinrichs
MARUM - Center for Marine Environmental Sciences, University of Bremen, Organic Geochemistry Group,
D-28334 Bremen, Germany (corresponding author:rongzhu@uni-bremen.de)
Pyrolysis-GC/MS is an excellent approach to
rapidly generate low-molecular fingerprints from
organic macromolecules. It has been successfully
applied to characterize microorganisms and
differentiate between them [e.g., 1, 2]. These previous
studies on microbes principally used ratios of
diagnostic fragments and multivariate analyses (e.g.,
principal components analysis) to differentiate
between the taxa [e.g., 3, 4]. Considering this, we
want to explore if we can use pyrolysis-GC/MS as a
method to rapidly screen for the presence of labile
macromolecules associated with living microbes in
the deep biosphere.
To adapt this method to the analysis of
sedimentary matrices, we first pyrolyzed cells of
different archaeal and bacterial lineages (Fig.1 A, B)
as well as reference substances and model
compounds to obtain a fingerprint for living microbial
biomass. Pyrolysis products derived from proteins,
carbohydrates and nucleic acids generally dominated
the pyrolysates. Although the relative distributions of
these compounds varied between the strains, no
specific archaeal or bacterial fingerprint could be
identified so far. By pyrolyzing surface sediments from
the Peru Margin (Fig.1 C) we tested to what extent
the fingerprint of microbial biomass could be
recovered from the benthic ecosystem. As expected
some nitrogen-bearing fragments derived from
proteins, amino sugars and nucleic acids occur both
in microbial cultures and surface sediments (Fig. 1).
Although in the surface sediments, proteins, amino
sugars and nucleic acids may also be derived from
fresh organic matter from the overlying water column,
such contribution is not expected to play a role in
more deeply buried sediment. Momentarily we are
testing to what extent we can follow our target
compounds down into the deep biosphere.
Furthermore, we are generating a calibration curve as
basis for estimating sedimentary microbe
concentrations from pyrolysates. Preliminary analyses
show that at around 100 m below the sea floor signals
can be still detected. We will further explore the
occurrence of living microbial biomass in deeply
buried sediments. We also intend to apply this
approach for off-line isotope ratio mass spectrometry
(IRMS) to track the carbon substrates and nutrient
cycling of subsurface microbial communities.
Fig.1. Characteristic partial pyrolysis-GC/MS
chromatograms of Acetobacterium woodii (A),
Methanosarcina barkeri (B), and a surface sediment
from the Peru Margin (C). (1: nitrile derivatives; 2:
pyridine and derivatives; 3: acetic acid; 4: pyrrole and
derivatives; 5: furan derivatives; 6: acetamide; 7:
phenol and derivatives; 8: indole)
References
[1] Irwin, W.J. (1979b) J. Anal. Appl. Pyrolysis. 1, 89-
122.
[2] Snyder, A.P. et al. (2004) Anal. Chem. 76, 6492-
6499
[3] Goodacre, R. and Kell, D.B. (1996) Curr. Opin.
Biotechnol. 7, 20-28.
[4] Barshick, S.A., Wolf D.A. and Vass A.A. (1999)
Anal. Chem. 71, 633-641.
203

P-058
Characterization of aromatic steroids in marine and lacustrine
crude oils by Comprehensive two-dimensional gas
chromatography time-of-flight mass spectrometry (GCxGC-
TOFMS)
Cristiane Rossi Oliveira 1 , Hélen Gomes Maria Aquiar 2 , Débora Almeida Azevedo 1 ,
Eugênio Santos Neto 2 , Francisco Aquino Neto 1
1 Universidade Federal do Rio de Janeiro, Rio de Janeiro/RJ, Brazil, 2 Petrobras-CENPES, Rio de Janeiro/RJ,
Brazil (corresponding author:rossi.cristiane@yahoo.com.br)
Aromatic steroids from sedimentary organic matter
provide valuable information to assess organic matter
input [1], thermal maturity [2] and correlation of crude
oils [3]. The identification of these compounds is
typically achieved by a series of chemical and
chromatographic separations. The GCxGC technique
proved to be a powerful tool in solving co-elution
problems, commonly observed in GC oil analysis
[4,5]. The aim of this work is to favor the identification
and quantification of aromatic steroids as well as to
improve their application in geochemical studies, due
to difficulties in identifying this class of compounds.
Six Brazilian crude oil samples (three marine and
three lacustrine) were fractionated by liquid
chromatography with silica gel and the aromatic
hydrocarbons were analyzed by GCxGC-TOFMS.
GCxGC separations were performed using a quad-jet
dual-stage N2 modulator and non-polar to polar
column set. The GCxGC-TOFMS system used was a
Pegasus 4D (Leco, St. Joseph, MI, USA).
Analyzing the extracted ion chromatogram (m/z
231+253) of the oil samples (Figure1); it is possible to
see that the amount of monoaromatic steroids with
27, 28 and 29 and triaromatic steroids with 26, 27 and
28 carbon atoms decreases in lacustrine samples
when compared to marine samples.
It is known that with the increase in the degree of
thermal maturity the conversion of long-chain
aromatic steroids homologues (structures 2 and 4)
into short-chain homologues (structures 1 and 3)
increases as the lateral side chains are broken. The
short-chain triaromatic steroid/(short-chain triaromatic
steroid + long-chain triaromatic steroid) ratio values
vary from 0.06 to 0.21 for marine samples and from
0.31 to 0.77 for lacustrine samples, suggesting that
the lacustrine samples have a higher level of thermal
maturity than the marine samples. However, maturity
parameters based on 20S/(20S+20R) and
αββ/(αββ+ααα) sterane (St), TeT24/H30 and Tr/H
ratios showed values varying from 0.13 to 0.45, 0.44
to 0.51, 0.06 to 0.12 and 0.15 to 0.30, respectively,
and are typical values for mid-oil window thermal
maturity. The differences in the distribution of longchain
and short-chain aromatic steroids may reflect
the different origin of these oils and this aspect is
being further evaluated.
References
[1] Requejo, A.G., Sassen, R.; McDonald, T., Denoux, G., Kennicutt,
M.C., Brooks, J.M. (1996) Org. Geochem. 24, 1017-1033.
[2] Zhanjun, Z., Yongjian, J., Zhe, C. (2009) Pet. Explor. Dev. 36, 790-
796.
[3] Hostettler, F.D., Rosenbauer, R.J., Kvenvolden, K.A. (1999) Org.
Geochem. 30, 873-879.
[4] Aguiar, A., Silva Junior, A.I., Azevedo D.A., Aquino Neto F. R.
(2010) Fuel 89, 2760-2768.
[5] Aguiar, A., Aguiar, H., Azevedo, D.A., Aquino Neto, F.R. (2011)
Energy & Fuels, in press
Fig.1. Aromatic biomarker series (m/z 231+253) extracted ion chromatogram obtained by GCxGC-TOFMS from
representative marine and lacustrine crude oil samples.
204

P-059
Update and review of recent advances in age-related biomarkers
Silvana Barbanti 1 , J. Michael Moldowan 2
1 Integrated Petroleum Expertise Company, Rio de Janeiro, Brazil, 2 Geological & Environmental Sciences,
School of Earth Sciences, Stanford University, Stanford, United States of America (corresponding
author:silvana.barbanti@ipexco.com.br)
Petroleum exploration geologists and basin modelers
have often faced the challenge of defining the age of
petroleum that has not been rigorously correlated to a
source rock. Biomarkers have been applied with
success in many cases due to the high taxonspecificity
of some of these compounds. For example,
24-norcholestanes are more prominent in some oil
samples from Jurassic, Cretaceous, and Tertiary
source rocks than oil from older source rocks, which
is consistent with a possible origination from diatoms
[1]. Triaromatic 24-norcholesteroids are abundant
from Jurassic to Cretaceous and to Tertiary exhibiting
a similar trend to the nordiacholestanes, but also
show more sensitivity in the Jurassic than their
saturate analogs [2]. 24-iso-Propylcholestanes are
particularly abundant in some Ediacaran and
Ordovician oil and extracts [3, 4, 5]. The C28/C29
sterane ratios increase in the Cretaceous or at the
transition between the Jurassic and Cretaceous for
marine oil samples [6, 7]. Marine oils derived from
older than Silurian source rocks show particularly low
non-zero values for C30 sterane and C30 diasterane
indexes indicating that these ratios can be useful for
distinguishing marine oil samples from Silurian and
older [8]. Recent work has demonstrated non-zero
values for these indices in lacustrine oil, albeit orders
of magnitude less than for marine oil of similar age
(Zinniker, personal communication).
The combined application of some biomarkers is an
even more powerful tool for defining the geological
age of oil samples. Triaromatic 4,23,24trimethylcholesteroids
(TA-dinosteroids) and 23,24dimethylcholesteroids
(TA-DMC) are useful
parameters to distinguish oil samples as being
derived either from the Paleozoic or from the
Mesozoic through Tertiary [9, 10]. The combined
application of oleanane and bicadinane indices can
signal Mesozoic and Tertiary ages from the
contributions of terrestrial plants. From the standpoint
of algal taxa, biomarkers most likely based on
different diatoms including the C25-highly branched
isoprenoid (C25-HBI) and the saturate and aromatic
24-norcholestanes are also active in the Mesozoic to
Tertiary time period, while the as yet not fully
understood tricyclic terpanes (however, probably
algal) carve out the Jurassic. Therefore, based on
many taxon specific biomarkers the Triassic, Jurassic,
Cretaceous and Tertiary Periods and the Paleozoic
Era can often be differentiated.
References
[1] Holba, A.G., et al. (1988) Application of 24norcholestanes
for constraining source age of petroleum.
Organic Geochemistry 29, 1269-1283.
[2] Barbanti et al. (2009) New triaromatic steroids with
taxon and age-specificity [abs.], in Proceedings of 24 th Int.
<strong>Meeting</strong> on Organic Geochemistry, Bremen, Germany.
[3] McCaffrey, M.A., et al. (1994) Paleoenvironmental
implications of novel C30 steranes in Precambrian to
Cenozoic age petroleum and bitumen. Geochimica et
Cosmochimica Acta 58, 529-532.
[4] Love, G.D., et al. (2009) Fossil steroids record the
appearance of Demospongiae during the Cryogenian period.
Nature 457, 718-721.
[5] Peters, K.E., Walters, C.C., Moldowan, J.M.
(2005) The Biomarker Guide, 2nd Edition. Cambridge
University Press, Cambridge.
[6] Grantham P.J., Wakefield L.L. (1988) Variations in
the sterane carbon number distributions of marine source
rock derived oils through geological time. Org. Geochem. 12,
61-73.
[7] Moldowan, J.M., Barbanti, S.M., Trindade, L.A.
(2002) A new look at one of the first age-related biomarker
parameters, the C28/C29 sterane ratio [abs.], in Proceedings
of 8 th Latin American Congress on Organic Geochemistry,
Cartagena, Colombia.
[8] Barbanti, S.M. and Moldowan, J.M. (2005)
Relationship between petroleum biomarker composition,
depositional environment and age of the source rock
(revisited) [abs.], in Proceedings. of 22 nd Int. <strong>Meeting</strong> on
Organic Geochemistry, Seville, Spain.
[9] Moldowan, J.M., et al. (1996) Geology 24, 159-
162.
[10] Barbanti S.M., et al. (1999) Analysis and
occurrence of novel triaromatic 23,24-dimethylcholestanes in
geological time [abs.], in Proceedings. of 19 th Int. <strong>Meeting</strong> on
Organic Geochemistry, Istanbul, Turkey, p. 159-160.
205

P-060
Biomarkers parameters used to assessment of petroleum
biodegradation under laboratory conditions
Georgiana Feitosa da Cruz 1 , Eugênio Vaz dos Santos Neto 2
1 North Fluminense State University/Petroleum Engineering and Exploration Laboratory (UENF/LENEP),
Macaé, Brazil, 2 Leopoldo Américo Miguez de Mello Center for Research and Development (CENPES), Rio
de Janeiro, Brazil (corresponding author:geofec@gmail.com)
Biodegradation geochemical parameters based on
the sequential removal of biomarkers are commonly
applied to indicate the preference metabolic of
degradation of the aerobic and anaerobic
microorganisms 1 . The reliable biomarker
interpretation about these information are usually
based on multiple biomarker parameters which should
be resistant to secondary processes, such as
biodegradation 2 . In this sense, the aim of this study
was to investigate the biomarker parameters that are
influenced by biodegradation process under
laboratory conditions. For this we use the following
ratios: Carbon Preference Index (CPI), pristane/nC17
and phytane/nC18, pristane/phytane (Pr/Ph), C28 and
C29 tricyclic terpanes (22R + 22S) to C35 17�(H),
21�(H)-homohopane (22R + 22S) (C28TT/C35Ho and
C29TT/C35Ho ), C35 17�,21�(H)-homohopane (22R +
22S) to C30 17�,21�(H)-hopane (C35Ho/C30H), C27
18�(H)-22,29,30-trisnorneohopane (Ts) to C27
17�(H)-22,29,30-trisnorhopane (Tm) (Ts/Tm), C35 to
C31-C35 homohopane (22R + 22S) (Homohopane
Index, HI), C27, C28,C29 ��� (20R + 22S) and ���
(20R + 22S) steranes to C29-C33 17�(H)-hopanes
(20R + 22S) (sterane/hopane) and C30-C34 25norhopanes
to C31-C35 hopanes ( 25-NH ratio).
The samples were collected from the Pampo field in
the southern part of the Campos Basin. They were
generated from the Lagoa Feia Formation source rock
in differ temperature and depth, allowing a variable
level of oil degradation (oil A, 82 ºC; 2405–2588 m
and oil B, 71 ºC; 1988–2222 m).
The results showed that in aerobic conditions
occurred progressive removal of even carbon
numbered n-alkanes, increase of ratio Pr/nC17
Ph/nC18 and decrease in the ratio Pr/Ph. It is
commonly accepted that odd number n-alkane
preference is associated with low oil thermal maturity,
however these experimental data reveal that the
alkane carbon number predominance can change
with the type of biodegradation and should be
interpreted with caution. In addition, there was an
increase of ratios C28 and C29TT/C35Ho, (Fig. 1),
sterane/hopane, 25-NH, revealing a preferential
depletion of R C35 hopane in relation to tricyclic
terpane, of hopane in relation to sterane and
enrichment of 25-NH.
Fig. 1. Plot of C28TT/C35Ho ratio during biodegradation
process.
The homohopane index decrease showing that C35
is more biodegradable than C31-C34 homohopanes.
Unlike what occurred under aerobic conditions,
anaerobic consortium showed greater susceptibility to
biodegradation of odd numbered n-alkanes, decrease
of ratios C28 and C29TT/C35Ho, sterane/hopane, 25-
NH and increased of homohopane index. The
geochemical parameters calculated from mixed
consortium revealed that there was joint action
between aerobic and anaerobic consortia, as
expected.
A comparative biodegradation of terpanes,
hopanes, 25-norhopanes and steranes under aerobic
and anerobic conditions indicated that some of the
controversial biomarker parameters can be easily
explained by taking into consideration the microbiota
and oxygen content.
Acknowledgment
Unicamp, Capes, Finep, Petrobrás and Profa Dra Anita J.
Marsaioli.
[1] da Cruz, G. F., Santos Neto, E. V. & Marsaioli, A. J.
(2008) Organic Geochemistry 39, 1204-1209.
[2] Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The
Biomarker Guide, second ed. Cambridge University Press,
Cambridge, UK.
206

P-062
A diagenetic origin for the moretane anomaly at the Permian
Triassic Boundary
Katherine French 1 , Nicholas Tosca 1 ,Changqun Cao 3 , Gordon Love 2 , Roger Summons 1
1 Massachusetts Institute of Technology, Cambridge, MA, United States of America, 2 University of California
Riverside, Riverside, CA, United States of America, 3 Nanjing Institute of Geology and Palaeontology,
Nanjing, China (corresponding author:klfrench@mit.edu)
The Permian-Triassic Boundary (PTB;
~252.2 Ma) marks the greatest loss of biodiversity in
Earth‘s history with an estimated 95% of species
becoming extinct (1). Many mechanisms have been
proposed as triggers for this mass extinction event
and these are still a matter of considerable debate.
Despite the persisting ambiguity of how the event was
initiated, it has become increasingly evident that both
the marine and terrestrial ecosystems deteriorated
rapidly (2-4). Geochemical techniques have helped to
elucidate the nature of the PTB transition but have
simultaneously opened new questions that require
explanation.
Anomalous C30 moretane (17β(H), 21α(H)hopane)
abundances at the PTB have been reported.
The moretane/hopane ratio is widely used as a
thermal maturity indicator, but like other geochemical
parameters, organic matter sources and depositional
environment can modulate the measured
moretane/hopane ratios of lipid extracts (5). Previous
workers have eliminated thermal maturity as the
underlying cause of the observed C30 moretane
excursions at Meishan. Alternatively, they have
proposed that the C30 moretane/hopane excursion at
the PTB signals either enhanced terrigenous input to
a marginal marine ecosystem, increased marine
acidification, or lithological effects (6-8). Improved
understanding of the moretane record stands to
further constrain our knowledge of the PTB.
For this purpose, we present the
moretane/hopane record of extended desmethyl
homohopanes and methylated hopanes from the
Meishan section in South China. The samples are
from a drill core that spans the lead-up and recovery
intervals and are expected to have minimum surficial
weathering alteration. The desmethyl homohopane
(C31-C34) and 2α- and 3β-methylated hopanes echo
the same moretane/hopane stratigraphic trend
previously observed for C30 hopanes (6). These new
results require a mechanism that can account for the
parallel excursions in the desmethyl and methylated
hopane records. Our results do not preclude the
possibility that enhanced terrigenous organic input
was characteristic of events at the PTB, but this
mechanism does not account for the observed
moretane anomalies in the Meishan section.
Carbonate measurements and clay analysis implicate
lithology as the key factor for generating the
moretane/hopane excursions at the PTB.
Furthermore, our results indicate that caution must be
used when interpreting moretane/hopane data.
References
1. D. Raup, Science 206, 217 (1979).
2. G. Retallack, Science 267, 77 (1995).
3. R. Twitchett, C. Looy, R. Morante, H.
Visscher, P. Wignall, Geology 29, 351
(2001).
4. P. Michaelsen, Palaeogeography,
Palaeoclimatology, Palaeoecology 179, 173
(2002).
5. K. E. Peters, C. C. Walters, J. M. Moldowan,
(Cambridge University Press, Cambridge,
UK ; New York, ed. 2nd, 2005).
6. C. Cao et al., Earth and Planetary Science
Letters 281, 188 (2009).
7. C. Wang, Organic Geochemistry 38, 52
(2007).
8. S. Xie et al., Geology 35, 1083 (2007).
207

P-063
Origin of crude oil with high concentration of dibenzothiophene
in Tarim Basin
Zhu Guangyou, Zhang Shuichang, Jiang Naihuang, Su Jin, Cui Jie, Gu Lijing
Research Institute of Petroleum Exploration and Development, PetroChina, Beijing, China (corresponding
author:zhuguangyou@petrochina.com.cn)
Dibenzothiophene series is one of the most important
compositions in crude oil, which generated under
multiple geological and geochemical processes. The
relationships between dibenzothiophene series and
other biomarker (C29 αα sterane 20R, C28 triaromatic
sterane 20R) , Combining with the research of TSR,
biodegradation, geological ages, and oil source in
Paleozoic oils in Tazhong area, indicate that there are
three factors for high concentration of
dibenzothiophene series. First, both oil source rocks,
no matter middle-upper Ordovician or lower
Ordovician-Cambrian, are marine carbonate
sediments which could produce abundant organic
sulfur compounds including dibenzothiophene series.
Second, biodegradation can result in the enrichment
of organic sulfur compounds. In addition, sulfate
reducing bacteria is able to transfer hydrocarbons and
S in SO4 2- in oil-bearing formation water into organic
sulfur compound. It might be a main path to produce
dibenzothiophene series. Third, sulfur compounds
might form by TSR reaction because S of SO4 2- in oilbearing
formation water could be also transfered to
H2S and organic sulfur compounds under high
temperature, which might result in increase of
dibenzothiophene series in crude oil.
208

P-064
Biodegradation of Aromatic Hydrocarbons at Basin and
Laboratory Scales
Frank Haeseler, Françoise Behar, Denis Blanchet, Marion Courtiade
IFP New Energy, Rueil Malmaison, France (corresponding author:frank.haeseler@ifpen.fr)
Oil biodegradation at Basin scale has been shown by
Haeseler et al. 2010 to be a compositional process for
which different classes of hydrocarbons are degraded
in parallel. These concepts are implemented in the
BioClass 0D model which describes the compositional
changes and determines the hydrocarbon losses. In
this model the classes are subdivided according to
chemical criteria (saturated and aromatic, light and
heavy) and they are characterised by specific relative
kinetics. The susceptibility to biodegradation (Kbio
factors) has been found very similar for two very
different Basins: Potiguar and Williston.
The aim of the present study is to quantify the
hydrocarbon loss in the aromatic fraction. For that
purpose we used a quantitative GC2D technique
described by Vendeuvre et al. (2005) in which
aromatics are characterized in both number of
aromatic rings and length of site chain. Consequently
it is possible to quantify the loss of HC as a function of
aromatic rings and carbon number of the alkyl chain.
The Figure 1 illustrates the separation and
identification potential of this method for the
phenanthrene / alkyl-phenanthrene region of the 2D-
GC chromatogram. This procedure was applied to a
natural series of reservoir biodegraded oil and to an
oil that has been exposed under aerobic and
anaerobic conditions to specifically adapted
hydrocarbon degrading microflora. So far a
comparison can be done between basin and aerobic
condition.
C 1 -Phe
0,170%
Phe
0,066%
C 1 -Phe
0,375%
(-3,3%)
Phe
0,166%
(-8,6%)
C 3 -Phe
0,189%
C 2 -Phe
0,211%
C 3 -Phe
0,0572%
(-3,0%)
C 2 -Phe
0,603%
(-2,7%)
Figure 1: Zoom in a GCxGC chromatogram of an oil before
biodegradation.
Figure 2a shows that the C1-monoaromatic (e.g.
toluene) behaves in a very similar way under lab and
basin conditions. The sum of the C6-monoaromatic
hydrocarbons present a linear trend in the aerobic lab
scale oil whereas its biodegradation seems to start
and to become very efficient at later times in basins
(Fig. 2b). The C15-monoaromatic hydrocarbon class
shows another behaviour: linear loss for the aerobic
process, no biodegradation in basins (Fig. 2c). C2naphtenodiaromatics
are recalcitrant in lab conditions
and become strongly biodegraded in severely
biodegraded oils at basin scale (Fig. 2d).
Residual mass in one Ton [kg] aerobic
Residual mass in one Ton [kg]
20
18
15
13
10
8
5
3
Aerobic
a
Basin
0,40
0,30
5
4
b
0
0,00
0 10 20 30 40 50 60 70 80 90
2,5
2,0
1,5
1,0
0,5
Biodegradation loss, oil [%]
0,0
0 10 20 30 40 50 60 70 80 90
c
Biodegradation loss, oil [%]
Aerobic
Basin
0,50
0,20
0,10
Residual mass in one Ton [kg] Basin
Residual mass in one Ton [kg]
Residual mass in one Ton [kg]
6
3
2
1
0
0 10 20 30 40 50 60 70 80 90
2,0
1,8
1,5
1,3
1,0
0,8
Biodegradation loss, oil [%]
Aerobic
Basin
0,5
0 10 20 30 40 50 60 70 80 90
Biodegradation loss, oil [%]
Figure 2: Residual mass of C1- (a), C6- (b) and C15-(c)
monoaromatic and C2- (d) napthenoaromatic hydrocarbons.
This work shows that aromatic hydrocarbons with
different number of carbon atoms (7, 12, 19 and 25)
can behave very differently according to their
chemical structure (ring numbers and chain length)
and to the biological process they have been
subjected to.
Insight in their structure with GCxGC contributes to a
far better understanding of the biodegradation and
may contribute in the future to determine the process
(aerobic or anaerobic).
Furthermore, GCxGC analyses also provide similar
data for saturated hydrocarbons and particularly
napthenes. These data of course also contribute to a
better understanding of the hydrocarbon
biodegradation and will be presented during the
conference.
References
Haeseler et al, 2010, Organic Geochemistry, 41, 1156–1170.
Vendoeuvre et al., 2005, Journal of Chromatography. 1090,
116-25.
Aerobic
Basin
d
209

P-065
Molecular maturation of Bitumen-1 versus Bitumen-2: a case
study from the Oligocene Enspel Formation
Christian J. Illing 1 , Christian Hallmann 2 , Roger E. Summons 2 , Harald Strauss 1
1 Westfälische Wilhelms-Universität Münster, Münster, Germany, 2 Massachussetts Institute of Technology,
Cambridge, United States of America (corresponding author:c.illing@uni-muenster.de)
Sedimentary biomarkers can be utilized as a major
source of information on past organismic diversity and
environmental conditions. The bitumen that contains
these molecules is released from macromolecular
kerogen during thermal maturation and is typically
extracted from powdered sediments. Already in 1970
it was recognized that typically-extracted bitumen
does not constitute 100 % of the extractable organic
matter, and that a second bitumen, extracted after
digestion of the mineral matrix with mineralic acids, is
frequently characterized by a differing chemical
signature (Smith et al., 1970). This concept was
revived recently by Sherman et al. (2007) and
Hallmann (unpublished), who suggested that the
mineral-occluded portion of the bitumen (bitumen-2) is
significantly less endangered by contamination issues
than the free bitumen. Little is however known on the
origin and nature of this bitumen-2. Does it represent
a subset of bitumen, adsorbed to clay minerals; is it
unexpelled bitumen that is still tightly associated with
the kerogen? And why do chemical signatures
between bitumen-1 and bitumen-2 differ? Is this due
to contamination of bitumen-1 or do molecular
parameters evolve differently in these two organic
matter pools?
To answer some of these questions, we focused on a
natural maturity sequence. This project examined a
series of lacustrine sediments from the Oligocene
Enspel Formation (Germany) to increase our
understanding of the information contained in mineraloccluded
bitumen (bitumen 2). Enspel is a maar-like
lake whose sediments were covered by a lava flow.
This induced a thermal maturation sequence
decreasing from the top of the succession
(overmature) to very immature sediments a few
meters below the lava flow. The environmental
conditions and the geochemistry of those sediments
are well known (e.g. Lueninger & Schwark, 2002).
We analyzed 6 shale samples that span a
stratigraphic interval of 1.2m from the base of the lava
flow. Besides their interest for studies short-lived
thermal stress in respect to conservation of typical
biomarker ratios (Peters et al. 2005) these samples
permit comparisons of how the molecular signature of
bitumen-2 changes in comparison to that of bitumen-1
over the same stratigraphic interval.
The analytical approach generally followed a protocol
set up for biomarker analysis in Precambrian
sedimentary rocks (Hallmann et al. 2011), despite the
fact that the samples used here originated from
outcrop. The samples were first rinsed with organic
solvents to remove surface contaminants and
subsequently powdered, extracted with
dichloromethane/methanol (93:7). The first extraction
step used an ultrasonication method (100 mL solvent,
2x 15 min. at 50°C) that was repeated 6 times. To
ensure a maximal extract yield and a minimum
amount of remaining free bitumen, the samples were
subsequently extracted 13 times by ‗accelerated
solvent extraction (Dionex ASE 200). Subsequent to
this exhaustive extraction, samples were treated with
hydrochloric and hydrofluoric acid in Teflon bottles to
remove the majority of the inorganic mineral matrix.
Remaining heavy minerals, sulfides and neofluorides
were not removed to minimize alteration of the
organic matter. After the digestion, the kerogen
concentrate was extracted three times by
ultrasonication with hexane to obtain the mineraoccluded
bitumen (bitumen-2). Bitumen-1 was
fractionated in to saturated hydrocarbon, aromatic
hydrocarbon and polar fractions. Individual
compounds were analyzed by SIM and MRM
methods.
This data set shows interesting trends with regard to
the question on the differences between the two
bitumen fractions. Those results help to improve our
understanding of biomarker information contained in
bitumen II.
References:
Hallmann, et al. (2011) In: Topics in Geobiology 36
Lüniger & Schwark (2002) Sed. Geol
Peters et al. (2005) The Biomarker Guide
Smith et al. (1970) GCA
210

P-066
Synthesis of hopanoid hydrocarbons from zeorin and
identification of a new series of rearranged hopanes
Geir Kildahl-Andersen 1 , Hans Peter Nytoft 2 , Jon Eigill Johansen 1
1 Chiron AS, Trondheim, Norway, 2 Geological Survey of Denmark and Greenland, GEUS, Copenhagen,
Denmark (corresponding author:jon.johansen@chiron.no)
Dehydration by perchloric acid treatment of zeorin
(6�-hopane-6,22-diol) provided the two rearranged
hopanoid dienes 1 and 2, identified by way of NMR, in
addition to hopa-5,17(21)-diene (3) and zeorinin (6�hop-17(21)-en-6-ol).
Catalytic hydrogenation of a
mixture of 2 and 3 in presence of perchloric and
acetic acid, gave several new products. In addition to
the partly hydrogenated hopene 4, three saturated
hopanoid products were isolated. Proton and carbon-
13 chemical shifts of compounds 5 and 6 were fully
assigned, whereas the third saturated compound was
isolated in too small quantities for complete structural
assignment. Compounds 4 and 6 are both structurally
related to and therefore also probably formed from
diene 2, while 5 is likely to be formed from diene 3
during hydrogenation. Compound 5 has a similar
structure as 17�(H)-hopane (��30), except for an
unusual 5�(H) configuration.
NMR data of 6 suggested a main conformer in which
the A and B rings, and possibly also the C and D
rings, have reversed conformations compared to
regular hopanes. Moreover, a characteristic fragment
in the mass spectrum at m/z 327 was present, Fig. 1,
formed by fragmentation of the A ring. A homologous
series of compounds (containing 27, 29, 30, 31, 32
and 33 carbon atoms, respectively) with similar
fragmentation patterns was identified in small
quantities in sample oils with high contents of
rearranged hopanes. By way of GC-MS-MS, the C30
homolog was shown to have identical retention time,
mass spectrum, and daughter ion spectrum as the
rearranged synthetic compound 6.
Fig. 1. Mass spectrum of compound 6 obtained from
GC-MS analysis.
211

P-067
C21-C23 steroidal tricyclic terpanes from bitumen of Olenek field
(East Siberia)
Vladimir Kashirtsev
Trofimuk Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation
(corresponding author:KashircevVA@ipgg.nsc.ru)
Jiang Zhusheng et al. [1], V.Kashirtsev [2] identified
(by GCMS, m/z 219) unusual biomarkers associated
with biodegraded oils and natural bitumen. In the first
case, researchers studied the oils of Kelamayi oilfield
(China) interpreted the structures of the C28 and C29
as de-A-steroidal tricyclic hydrocarbons. In the
another case author considered close or similar
hydrocarbons C27,C28 and C29 from Olenek bitumen
field like structures 8-14 sekosteranes. S.Norden,
J.Christoffers and J.Rullkotter had attempted a
synthesis 5-methyl-19-nor -4,5-seco-sterane [3].
Tricyclic compounds having common structural
features with the aforementioned secosteranes, they
have been found along with regular pregnanes (Fig.
1). The mass spectra of these compounds are
characterized by molecular ions at m/z 290, 304 and
318, with a base peak m/z 219, indicating that they
originate from C21, C22 and C23 tricyclanes. Features
of the fragmentation under electron impact (m/z 95
instead m/z 97; mz/ 262 instead m/z 263,264 and m/z
219) indicate that the rings A, B and D are not broken
by C-C bonds.
The Permian bitumen from Olenek field underwent
the strongest biological oxidation (rank 8 by Peters et
al. [4]) they virtually lack normal and branched
alkanes. The concentrations of terpanes are much
higher than those acyclic hydrocarbons.
Chromatograms scanned by ions m/z 123, 177, and
191 show that regular hopanes are almost completely
transformed to a homologous series of 25norhopanes,
with a predominance of 25-noradiantane
C28 [5]. Normally demethylated hopanes represent
biomarkers of intensely biodegraded oils (rank 8).
Among the identified terpanes, a homologus series of
secohopanes (C-ring opened i.e. hopanes with a
broken chain between carbon atoms 8 and 14) is of
special interest. These variations suggest that the
microbial biodegradation of terpanes proceeds along
to different pathway: oxidation of the alkyl side chain
and alteration cyclic core.
On the other hand, 8-14-secohopanes and steroidal
tricyclic terpanes can be primary compounds
synthesized in minor quantities by prokaryotes during
the OM transformation. They appear to be the most
resistant to biodegradation, and their significant
"residual" amounts are due to the bacterial utilization
of labile hydrocarbons in the pool.
Fig 1. Mass-chromatogram of saturated HC from
the natural bitumens of Olenek field (by m/z 217,218
and m/z 219). Lower part is mass-spectrum for the
peak H (C23H42).
References
[1] Jiang Zhusheng, Fowler M.G., Lewis C.A. and
Philp R.P. (1990) Organic Geochemistry, 15, .35-46.
[2] Kashirtsev V.A. (2009) The 24-th IMOG Abstracts,
529.
[3] .Norden S, Christoffers J. and Rullkӧtter J (2009).
The 24-th IMOG Abstracts, 526.
[4] Peters K.E., Walters C.C., Moldowan M.(2005)
The biomarker guide. Cambridge UP, vol.1,2,1155.
212

P-068
Aromatic hydrocarbons in the barents-kara shelf
Anna Kursheva 1 , Ivan Litvinenko 2 , Vera Petrova 3
1 Anna Kursheva, Saint-Peterburg, Russian Federation, 2 Ivan Litvinenko, Saint-Peterburg, Russian
Federation, 3 Vera Petrova, Saint-Peterburg, Russian Federation (corresponding
author:A.Kursheva@mail.ru)
Information about the content and distribution of
hydrocarbons (HC), including aromatic (AHC) in the
components of the geological environment of aquatic
ecosystems allows predicting of oil and gas presence
and simultaneously creates a basis for further
geoecological monitoring. However, be aware that
hydrocarbons are widely distributed in the lithosphere
and form a stable geochemical background due to the
specifics of the initial organic matter (OM), the terms
of the accumulation and transformation. Application in
the multi-geological survey of on-board study by
fluorescence spectrometry allowed not only identifying
the background geochemical parameters, lithologicalfacial
features of sedimentation, but also abnormal
zones of endogenous and exogenous genesis [1].
This study based on measurements of sea water
and sediments samples (> 500 geological stations)
from the Barents-Kara shelf during the expeditions
carried out by VNIIOkeangeologia in 2000-2007.
Analysis of data on the distribution and
composition of aromatic HC in sediments of Western
Arctic Shelf showed that the low content (Xave = 4.3
mg/g) is typical for sandy sediments, with a
predominance of bi- and tri-aromatic compounds
(�max270-310 nm). It corresponds with a low sorption
capacity of coarse-grained sediments and a lack of
organic-mineral complexes containing the source of
destruction of initial OM in them.
In clay sediments (Xave = 13.0 mg/g) is
dominated by tetra- and penta-aromatic structures,
typical components of OM lipid fractions on postsedimentological
and early-diagenetic stage of
transformation. In doing so, change of the spectral
characteristics of sediments in the stratigraphic
section fully reflects the processes of diagenetic
transformation of OM, including aromatization and
formation of several compounds, such as perylene (�
max 435 nm).
The presence in the sediments of highly maturated
(post-diagenetic) organic matter, forming a special
(petrogenic) type of spectrum (� max 370-380 nm),
which is fundamentally different from the appropriate
spectrum typical for modern marine sediments.
This type of spectrum, combined with
abnormally high content of aromatic HC (Xave =
349.1 mg/g), is characteristic for the Svalbard
offshore area, erosion and redeposition of coal rocks
which play a significant role in the sedimentation [3].
A similar composition of aromatic HC was recorded in
the sediments on the shelf of the Kolguev Island, in oil
producing region, where exogenous anomaly is,
apparently, the case of technogenic factors [2].
The influence of endogenous processes (seeping
migration of HC) can also lead to a distortion of the
background spectrum because of formation of the
intense stripe in the short-wave range (� max 240-260
nm). Thus, in the Prirazlomnoye oil field area
(Pechora Sea) abnormal distribution of aromatic HC
observed in the sediments and in the water column
where the aromatic HC content in the bottom waters
exceeds the background value of two orders of
magnitude. Endogenous nature of anomalies is
confirmed by seismic profiling data, which showed the
presence of gas saturation and gas fluid.
A significant role of aromatic compounds in
fluid makes the dubious assumption about the
diagenetic and/or gas hydrate nature of emanation,
the most typical components of which are to be
methane and its homologues. On the contrary, the
fluid relation with productive horizons of hydrocarbon
deposits to be consistent, because the high content of
benzole homologues in the produced water is a direct
hydrochemical measure of oil and gas presence.
References
[1] Galishev M. (2004) Integrated research
methodology of oil products dispersed in the
environment in emergency situations. St.
Petersburg.: St. Petersburg Institute of the State
Fire Service EMERCOM of Russia, 157. [in
Russian]
[2] Hovland M., Judd A.G. (1998) Seabed
Pockmarks and Seepages. Graham & Trotman,
175.
[3] Petrova V., et al. (2000) Correlation diagnostics
of HC anomalies in bottom sediments of the
arctic shelf. Geochemistry 3, 311-308. [in
Russian]
213

P-069
The age and palaeoenvironmental conditions spanning the
Permian/Triassic boundary in the northern onshore Perth Basin
by using biomarker distributions and stable isotopes (C, H)
Mojgan Ladjavardi 1 , Kliti Grice 1 , Chris Boreham 2 , Dianne Edwards 2 , Ian Metcalfe 3 , Roger
Summons 4
1 WA Organic and Isotope geochemistry centre, Department of Chemistry, Curtin University of Technology,
Perth, WA, Australia, 2 Geoscience Australia, GPO BOX 378, Canberra, Australia, 3 Schools of environmental
and Rural science, University of New England, NSW, Australia, 4 Massachussetts Institue of Technology,
Earth and Planetary Sciences, Cambridge, United States of America
The Perth Basin petroleum system has been
intermittently explored for the last few decades,
resulting in the production of gas and oil from several
onshore fields (e.g. Summons et al., 1995). The
effective source rock for petroleum in the Perth Basin
is the marine Kockatea Shale, with the hydrogenrichest
interval being the Sapropelic Unit of the Hovea
Member (Thomas et al., 2004). The Perth Basin in
southwest Western Australia (WA) is a deep, north to
south trending basin, extending over 1,000 km from
Geraldton to the north of Perth. The Perth Basin
sediments comprise of rocks of Permian−Early
Cretaceous in age. The current perception is that the
area is gas prone and has been challenged with the
recent discovery of the near-shore Cliff Head oil field.
The Dongara gas field in the onshore Perth Basin
contains more than half the oil and gas reserves. The
Perth Basin sediments used in this study are from the
Senecio-1 core which is located approximately 15.5
km from the north of Dongara. Stable carbon and
hydrogen isotopic composition of biomarkers
measured by compound specific isotopic analysis
(CSIA) has been shown to be an effective tool for
establishing biogeochemical changes across the
Permian/Triassic boundary (e.g. Nabbefeld et al.,
2010). In the present study bulk geochemical,
biomarker and CSIA of biomarkers are used to
restrain the age and palaeoenvironmental conditions
spanning the Permian/Triassic in the northern
onshore Perth Basin and to compare these results
with the Hovea-3 drill core ‗type-section‘ (Grice et al.,
2005a). For this purpose 31 samples from the
Senecio-1 cored including Permian/Triassic interval at
1 m spacing were selected. The ages of the samples
have been determined by conodont biostratigraphy.
Rock-Eval & TOC analyses have been performed to
identify the type and maturity of organic matter and to
evaluate the petroleum potential of these samples.
The samples were analysed following the
methodology of Grice et al. (2005b). Each sample
was ground to a fine powder and extracted using an
Accelerated solvent extractor. The extracts were
separated into 6 fractions by liquid chromatography.
Saturate and aromatic hydrocarbon fractions were
characterised by GC-MS. The saturated hydrocarbon
fractions were separated from branched and cyclic
hydrocarbons by treating with 5A molecular sieves
and CSIA of biomarkers was performed for these
fractions. Bulk stable isotopic compositions were
measured on the kerogens isolated from the extracted
powders. The data is consistent with Hovea-3 for both
Rock-Eval and kerogen type. � 13 C of the bulk organic
matter is consistent with the Permian interval of the
core being mainly land plant derived, whereas the
Triassic interval is mainly phytoplanktonic, the change
in stable isotopes is not as abrupt as shown in Hovea-
3.
References
Grice, K., Cao C., Love G.D., Bottcher M.E., Twitchett R.,
Grosiean E., Summons R., Turgeon S., Dunning W. J., Jin
Y., 2005a. Photoc Zone Euxinia during the Permian-Triassic
Superanoxic Event. Science 307,706-709.
Grice, K., Summons, R.E., Grosjean, E., Twitchett, R.J.,
Dunning, W., E., Wang, S.X., Boettcher, M.E., 2005b.
Depositional conditions of the northern onshore Perth Basin
(Basal Triassic). Australian Petroleum Production and
Exploration Association Journal 45, 263-273.
Nabbefeld, B., Grice, K., Twitchett, R.J., Summons, R.E.,
Hays, L., Boettcher, M.E., Asif, M., 2010. An integrated
biomarker, isotopic and palaeoenvironmental study through
the late Permian event at Lusitaniadalen, Spitsbergen. Earth
and Planetary Science Letters 291, 84-96.
Summons R.E., Boreham, C.J., Foster, C.B., Murray, A.P.,
Gorter, J.D., 1995. Chemostratigraphy and the composition
of oils in the Perth Basin, Western Australia. Australian
Petroleum Exploration Association Journal 35, 613-632.
Thomas, B.M., Willink, R.J., Grice, K., Twitchett, R.J.,
Purcell, R.R., Archbold, N.W., George, A.D., Tye, S.,
Alexander, R., Foster, C.B., Barber, C.J., 2004. Unique
marine Permian-Triassic boundary section from Western
Australia. Australian Journal of Earth Sciences 51(3), 423-
430.
214

P-070
Characterisation of biodegraded Australian oils via catalytic
hydropyrolysis
Robert S Lockhart 1 , Minh Tam Le 2 , Kliti Grice 1 , Will Meredith 3
1 WA Organic and Isotope Geochemistry Centre, Curtin University, Bentley, WA, Australia, 2 Clermont
Université, Ensemble Scientifique des Cézeaux, Aubière Cedex, France, 3 Nottingham Fuel and Energy
Centre, University of Nottingham, Nottingham, United Kingdom (corresponding
author:R.Lockhart@curtin.edu.au)
Asphaltene fractions isolated from a series of
biodegraded crude oils, reservoired in Australian
sedimentary basins (Gippsland and Carnarvon
Basins), have been subjected to catalytic
Hydropyrolysis (Hypy) in order to investigate the
characterisation potential of the ―bound‖ hydrocarbon
product. Hypy is pyrolysis assisted by high hydrogen
pressure (~150 Bar) and a dispersed sulfidic Mo
catalyst. Developed as a rapid characterisation
technique, Hypy possesses proven ability to release
high yields (>65%) of covalently-bound biomarkers
from petroleum source rocks and high volatile coals,
with overall conversions of organic matter >85%
(Love et al., 1995; Love et al., 1996). Owing to a
unique hydrogen gas sweep mechanism,
Hydropyrolysates benefit from superior carbon
skeletal preservation where compared with more
conventional pyrolysis methods (Lockhart et al., 2008;
Love et al., 1996; Murray et al., 1998).
Results support the findings of previous workers, who
have consistently demonstrated the ability of Hypy to
maximise yield of the significant pool of highly
informative biomarkers covalently-bound within the
complex macromolecular structures of a range of
solvent insoluble organic fractions (Bowden et al.,
2006; Russell et al., 2004; Sonibare et al., 2009). The
crude oils examined range in severity of
biodegradation, from non-biodegraded oils to those
lacking straight-chain, branched and cyclic alkanes,
while the most strongly altered samples display
depletion of polycyclic aromatic compounds and large
unresolved complex mixtures (Grice et al., 2000).
Figure 1, illustrates a typical example, where Hypy
has generated a ―bound‖ oil from the isolated
asphaltene, which is believed to be representative of
the original parent source rock. Findings further
illustrate the potential application of Hypy as a
powerful correlation technique, in conjunction with
compound specific isotope analyses.
Relative response
(b) Asphaltene “Bound”
nC17
UCM
nC18
nC26
(a) “Free” crude oil
nC30
nC35
Relative retention time
Figure 1. Total Ion Chromatograms (TIC) showing (a)
the saturate fraction of a biodegraded Australian
crude oil (Gippsland Basin) and (b) corresponding
results obtained following Hypy of the asphaltene
fraction. UCM = unresolved complex mixture.
References
Bowden, S. A. et al., (2006) Org. Geochem., 37:369-
383.
Grice, K. et al., (2000) Org. Geochem., 31:67-73.
Lockhart, R. S. et al., (2008) Org. Geochem., 39:
1119-1124.
Love, G. D. et al., (1995) Org. Geochem., 23:981-986.
Love, G. D. et al., (1996) Energy & Fuels, 10:149-157.
Murray, I. P. et al., (1998) Org. Geochem., 29:1487-
1505.
Russell, C. A. et al., (2004) Org. Geochem., 35:1441-
1459.
Sonibare, O. O., et al., (2009) J. Anal. Appl. Pyrolysis,
86, 135-140.
215

P-071
Structural characterization of 1,6-dimethyl-5-isopentyltetralin
from Cretaceous conifer fossil resins and coals: a novel
diterpene biomarker
Cesar Menor-Salvan 1 , Marta Ruiz-Bermejo 1 , Bernd R.T. Simoneit 2
1 Centro de Astrobiologia (INTA), Torrejon de Ardoz, Spain, 2 Department of Chemistry, Oregon State
University, Corvallis, United States of America (corresponding author:menorsc@cab.inta-csic.es)
Recently, the gas chromatographic-mass
spectrometry (GC-MS) study of the individual
components of Cretaceous ambers (fossil resins)
shown the presence of a previously unidentified
compound with a molecular peak at m/z 230 (Pereira
et al. 2009; Menor-Salvan et al. 2010). This
compound, one of the main components of the
extractable fraction of amber, is also common in the
associated sediments, plant fossils and coals of the
amber deposit.
These authors suggested a 2,5,6-trimethyl-1butyltetralin
structure for the molecule, interpretation
based largely in the fragmentation pattern observed in
mass spectrum. In order to confirm this structure, we
carried out the isolation and purification of the
molecule from amber of the Cretaceous deposits
located at Basque-Cantabrian Basin (Cantabria,
Spain). For purification, the crude amber extract was
fractionated by sequential elution in silica gel column
followed by semi-preparative high performance liquid
chromatography of the fraction containing the target
compound and purity testing using GC-MS.
The pure compound, a colorless oil, was then
characterized by nuclear magnetic resonance (NMR).
Using the NMR and fragmentation data, we could
infer a 1,6-dimethyl-5-isopentyltetralin structure (Fig.
1) for the unknown compound, discarding the
structure previously suggested in the literature.
Fig. 1: Structure of 1,6-dimethyl-5-isopentyltetralin,
isolated from Cretaceous amber.
The biochemical precursors of this molecule are not
identified, but taking into account the structures
identified in the amber extracts and the preservation
of original biomolecules, the origin of the 1,6-dimethyl-
5-isopentyltetralin could be the oxidative degradation
of diterpenoids of the labdane class, as communic or
agathic acids. The association with conifer fossil
resins and the possible diterpene precursor suggest a
coniferous botanical origin. Therefore, the presence of
1,6-dimethyl-5-isopentyltetralin in the sedimentary
record could be indicative of conifer resin contribution
to the organic matter.
Spectroscopic characterization:
1 H NMR (CDCl3, 400 MHz) δ 6.97 (s, 1H), 6.96 (s,
1H), 2.89 (m, 1H), 2.70 (m, 2H), 2.55 (m, 2H), 2.27 (s,
3H), 1.88 (m, 2H), 1.67 (m, 1H), 1.34 (m, 2H), 1.27 (d,
J=7.02 Hz, 3H), 0.97 (d, J=6.25 Hz, 6H)
13 C NMR (CDCl3, 100 MHz) δ 140.3, 139.7, 134.8,
133.3, 127.8, 126.0, 38.2, 33.1, 31.1, 29.2, 27.4, 26.8,
23.6, 22.7, 20.8, 19.8.
EI-MS m/z (%) 230 (M + , 25), 215 (M-CH3, 14), 173
(29), 159 (100), 143 (13), 128 (12), 115 (7).
References:
Pereira, R., de Souza Carvalho, I., Simoneit, B.R.T.,
de Almeida Azevedo, D., 2009. Molecular
composition and chemosystematic aspects of
Cretaceous amber from the Amazonas, Araripe and
Recôncavo basins, Brasil. Organic Geochemistry 40,
863-875.
Menor-Salvan, C., Najarro, M., Velasco, F., Rosales,
I., Tornos, F., Simoneit, B.R.T., 2010. Terpenoids in
extracts of Lower Cretaceous ambers from the
Basque-Cantabrian basin (El Soplao, Cantabria,
Spain): Paleochemotaxonomic aspects. Organic
Geochemistry 41, 1089-1103.
216

P-072
High molecular alkanes С40+ in West Siberian oils
Marina Mozhayskaya 1 , Galina Pevneva 1 , Julia Golovko 2 , Anatoly Golovko 1
1 Institute of Petroleum Chemistry SB RAS, Tomsk, Russian Federation, 2 University of Houston, Houston,
United States of America (corresponding author:mozhayskaya@ipc.tsc.ru)
Organic geochemistry is concerned with the
study of biomarkers containing carbon atoms in a
molecule ranging from С1 to С40. They are widely
spread in geosphere and are analyzed by gas-liquid
chromatography and chromatography-mass
spectrometry. The development of instrumental
methods for the analyses enables us to study
composition and distribution of high molecular
alkanes C40+ in oils.
The oils occurring in Cretaceous, Jurassic and
Paleozoic deposits of West Siberian oil-and-gas
bearing province were the objects of the investigation.
High-molecular alkanes were extracted using a
modified Burger method.
In the oils from Cretaceous deposits a content of
waxes varies from 2.8 to 11.3 % mass and that of nalkanes
in the same factions varies from 10 to 40 %.
In major oils a homologous series of n-alkanes in wax
fractions is composed by the compounds with a
number of carbon atoms up to С44-50 and maximum
falls on n-alkanes С23-С26.
In the oils from Jurassic deposits the content of
waxes increases up to 2.9-16.8 % as compared with
Cretaceous deposits. The oil from Gorstovoye oil field
contains an abnormally high amount of waxes – 47.4
%. A content of n-alkanes can reach 40 % mass in all
wax fractions occurring in Jurassic oils as well as in
analogues fractions of Cretaceous oils. Compounds
with a number of carbon atoms in a molecule up to
С65 compose a homologous series of n-alkanes in a
wax fraction, whereas in the waxes of oils from
Cretaceous deposits it does not exceed 51 carbon
atoms in a molecule.
MMD of n-alkanes in major oils from Jurassic
deposits is unimodal. The concentration of С23-С26
compounds is maximal. There are samples among
Jurassic deposits in which maximum of n-alkanes
distribution is shifted to a high-molecular region (С39-
С41).
As opposed to Cretaceous and Jurassic oils a
higher content of waxes was determined in Paleozoic
oils (14.6-26.5 % mass). n-Alkanes are the main
components of this fraction as in the waxes of oils
occurring in the deposits of other geological ages.
Compounds containing up to 58 carbon atoms in a
molecule compose a homologous series of n-alkanes
in waxes of major Paleozoic oils.
Besides n-alkanes the oils occurring in the
deposits of all geological ages contain homologous
series of 2- and 3-methylsubstituted alkanes and
alkylcyclopentanes. Their content is smaller as
compared with that of n-alkanes and varies ranging
from trace amounts to 0.82 % mass for methylalkanes
and up to 0.34 % mass for alkylcyclopentanes.
Along with other biomarkers the data on
distribution of n-alkanes, methyl-substituted and
alkylcyclopentanes occurring in wax fractions can be
used as additional information about the conditions of
the initial OM sedimentation. The authors of
publications [1, 2,] proposed to use a ratio of even
and odd (parameter CPI) of n-alkanes, methylalkanes
(CPI 2,3 ) and alkylcyclopentanes (CPI a ) to estimate a
type of the initial OM and sedimentation conditions.
CPI 2,3 and CPI a values for the major oils under study
vary from 1.2 to 1.3, that corresponds to a marine
environment of sedimentation. The oil from
Verkhnesalatskoye oil field is an exception to the rule:
its CPI a is equal to 0.7 and it probably indicates
evolution of oil in salt lacustrine environment [2].
Thus, the analysis of wax fraction demonstrated
that a homologous series of n-alkanes and
concentration of waxes in oil increases with the
increases in the age of the enclosing sediments. The
study of these hydrocarbons enables us to obtain new
information about compositional features and
distribution of high molecular n-alkanes, which can be
used to determine sedimentation conditions.
References
1. Philp R.P., Mansuy L. // Energy & Fuels – 1997 -
№4 - p. 749-760.
2. Hong Z., Guanghui H., Cuishan Z., Peirong Z.,
Yongxin Y. // Org. Geochem. – 2003 - v. 34, № 7, p.
1037-1046
217

P-074
Discussion on appliance of 25-norhopanoids compounds in
organic geochemical research
Chunhua Ni 1,2
1 Sinopec Research Institute of Petroleum Exploration and Production, Beijing, China, 2 Wuxi Institute of
Petroleum Geology, Sinopec Research Institute of Petroleum Exploration and Production, Wuxi, China
(corresponding author:nichunhua.syky@sinopec.com)
Abundant of crude oil which suffers from different
biodegradation degrees occurs widely in the world. At
present, the biodegradation degrees of crude oil are
mainly under qualitative identification based on some
biomarkers detected in the crude oil which stand for
different antibiodegradation abilities.
19 oil samples collected from the primary oil and gas
structures of Bohai Bay Basin, North China have been
investigated for their physical properties, molecular
geochemistry and carbon stable isotope. According to
the comparison of geochemical parameters, 4 oil
samples from the same oil and gas structure show the
similar characteristics which prove they have the
same genetic type, although there are some
differences in their physical properties. The theory
research indicates that there is a relative positive
relationship between the abundance or concentration
of 25-norhopnoids and the biodegradation degree of
crude oil. Therefore, the two ratios which are C29nor(25-norhopane)/C30-17
α -hopane ratio and C28nor(25-norhopane)/C29-17
α -norhopane ratio
respectively are applied to semi-quantitatively
evaluate the biodegradation degree of the four crude
oil. They distribute obviously in the different areas
from the figure which reveals there are four
biodegradation degrees. The results of our study
coincide well with the conventional knowledge, the
higher the biodegradation degree of crude oil is, the
heavier its density is, that is to say, the oil sample with
the highest biodegradation degree has the heaviest
density. In addition, the crude oil with lower burial
depth is more likely to suffer from biodegradation, so
the No. 4 oil sample whose burial depth is only 1131.6
meters encounters the highest biodegradation degree
among them.
In contrast with foreign petroliferous basins, Chinese
basins are famous for their more complex evolution
history of tectonic movements and most of them have
two or more phases of hydrocarbon generation,
migration and accumulation.
Geochemical characteristics of the crude oil from Well
B1 with underproductive oil flows in Southern North
China Basin are studied and they show the crude oil
is characterized by higher abundance of C16
homodrimane, C23 tricyclic terpanes, pentacyclic
terpanes, C31 homohopane and C27 sterane. Oilsource
correlation shows it is from the source rock of
the Lower Cretaceous, which belongs to an
indigenously generating and accumulating oil
reservoir. According to the biodegradation sequences
of different biomarkers, normal alkanes are prior to be
destroyed by the bacteria and 25-norhopanoids series
usually appear when the crude oil undergoes severe
biodegradation. Interestingly, normal alkanes and 25norhopanoids
series coexist in the oil sample from
Well B1. How to explain this strange phenomenon?
With the rapid development of numerical simulation
technology, more and more professional software are
used to complete the inversion of the evolution history
of the petroliferous basins, including thermal history,
hydrocarbon generating history and hydrocarbon
charging history. Correspondence with the analysis of
burial-thermal evolution history, there were at least
two phrases of hydrocarbon charging of the crude oil
from Lower Cretaceous of Well B1, the first charging
phrase was the Early Cretaceous when it was
dominated by low-matured oil with 0.50% Ro and
suffered from biodegradation, the second charging
phrase was from late Tertiary to Quaternary
predominant with high-matured oil with 0.70-1.30%
Ro. So the crude oil from Well B1 in Southern North
China Basin is the mixture of the two-phase charging.
It has been noticed that different biomarkers have
their specific prerequisite and they should be
comprehensively analyzed in combination with other
research methods to promote their effectiveness. 25norhopanoids
compounds is no exception.
218

P-075
Bicadinanes extend to C39 in oils from Southeast Asia
Hans Peter Nytoft 1 , Geir Kildahl-Andersen 2 , Jon Eigill Johansen 3 , Håkon Midtaune 3 ,
Herbert Volk 4
1 Geological Survey of Denmark and Greenland (GEUS), Copenhagen, Denmark, 2 Department of Chemistry,
University of Oslo, Oslo, Norway, 3 Chiron AS, Trondheim, Norway, 4 CSIRO Petroleum, North Ryde,
Australia (corresponding author:hpn@geus.dk)
Bicadinanes are pentacyclic C30H52 hydrocarbons
derived from thermal breakdown products of
polycadinene, a polymer present in dammar resins
(van Aarssen 1992a,b). Bicadinanes are abundant in
Tertiary oils from Southeast Asia but low
concentrations can be found in Tertiary oils from other
parts of the world (Nytoft et al., 2010). Oils with
bicadinanes also contain C31 bicadinanes.
Bicadinanes up to C35 have been noted (van Aarssen,
personal communication). In this study we show that
bicadinanes extend to C39 but not any further. A
biodegraded Malaysian oil had a particularly high
content of bicadinanes. Analysis in MRM mode using
the m/z 412 → 369 and 426 → 383 transitions etc.
showed one dominating isomer in all cases (Fig. 1).
The C38 and C39 compounds appeared as partly
resolved doublets. Clean EI mass spectra and MS-
MS daughter spectra were obtained of the whole
series from HPLC purified fractions. EI and M+ .
daughter spectra of all major compounds indicated a
trans-trans-trans-bicadinane structure like bicadinane
T. Most of the late eluting bicadinanes had similar
spectra and could have structures similar to the C30
bicadinanes T1 and R, whereas the major early
eluting bicadinanes (e.g. 33W) appear to have a ciscis-trans
structure like bicadinane W. Compounds
having EI mass spectra with an intense m/z 411
fragment but almost no molecular ion were also
observed from C33 and up. The MS-MS daughter
spectrum of such a C33 compound (33*) is shown in
Fig. 2. Its response using the m/z 454 → 411
transition is lower than that of isomeric C33
bicadinanes. These mass spectral features suggest
the loss of a C3 side-chain from a quaternary carbon
atom. The structure of the higher bicadinanes may be
a bicadinane moiety and a partly degraded cadinane
moiety linked by one carbon-carbon bond. The
relative abundance of the major C30-C39 bicadinanes
(―T-series‖) in the Malaysian oil was 100; 20; 1.0; 2.5;
0.5; 0.5; 0.1; 0.04; 0.4; 0.08 respectively. Oils from
Assam, India and the Kutei Basin, Indonesia showed
similar distributions of C30-C39 bicadinanes.
W
T
T1 R
33W
33T
33*
3.6
454 411
42 44 46 48
Retention time (min)
Fig. 1. C30 and C33 bicadinanes in a Malaysian oil
33W
151
233
383411
343
439
454
100 200 300 400 500
W
191
301
273
33*
397
341
369
412
100 200 300 400 500
315 355
33T
151
205
259
315
355
100
412 369
411
439
454
100 200 300 400 500
T
411
151
454
100 200 300 400 500
205
313
273
369
397
412
100 200 300 400 500
Fig. 2. MS-MS daughter spectra of C30 and C33
bicadinanes in a Malaysian oil
References
[1] Van Aarssen et al., 1992a. Organic Geochemistry
18, 805-812.
[2] Van Aarssen et al., 1992b. Geochimica et
Cosmochimica Acta 56, 1231-1246.
[3] Nytoft et al., 2010. Organic Geochemistry 41,
1104-1118
219

P-076
Lanostanes as the new biomarkers from organic matter of
Cambrian black shales in the Siberian platform
Tatyana Parfenova
Trofimuk Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation
(corresponding author:parfenovatm@ipgg.nsc.ru)
Lanosteroids are tetracyclic triterpenoids
containing, unlike steroids, additional methyl
substituents at the C4 and C14 atoms of the A- and Ccycles.
Only a few identifications of lanosteroids in the
Cenozoic organic matter (OM) are known [1, 2, 7, 9].
This study deals with the collection of limestones of
the Lower Cambrian Sinskaya (Sinyaya) Formation.
The samples of OM-enriched rocks were obtained
from a section of the Sinyaya River at the northern
slope of the Aldan anteclise [8]. It is known that the
rocks of the Sinskaya Formation are considered as a
potential oil-producing rocks [4, 5, 8, etc.]. In m/z 217
chromatograms, С27–С30 steranes were identified.
The analysis has shown that their contents vary from
25 to 37% for С27, from 8 to 13% for С28, from 49 to
62% for С29, and from 1 to 4% for С30 for total of
steranes. During the studies of diasteranes, two
peaks of unknown compounds were found in the
m/z 259 chromatograms of 22 samples. The spectra
of these compounds are identical and coincide with
the С30 lanostane spectrum. The latter compound was
identified by the molecular mass М equal to 414, М –
15 = 399, and a high intensity of the ions (259, 190,
231, and 274) [2, etc.]. The lanostanes have not yet
identifies in Proterozoic and Phanerozoic oils and
scattered OM of Eastern Siberia [4, 6, etc.]. The
complementary studies of OM from the Kuonamka
formation (a facial analogue of the Sinskaya
sediments [5]) showed the absence of lanostanes.
The lithological, paleontological, and geochemical
studies showed that the OM of carbonaceous rocks of
the Sinskaya Formation was accumulated in the
marine basin with an excess of hydrogen sulfide in
carbonate sediments and, probably, in near-bottom
waters [3, 5, 8, etc.]. It was found that the lanostanecontaining
dolomite claystones were formed in a lake
of increased water salinity [2]. The studies of oils in
Wubei province revealed the lanostane sulfides [9].
The authors think that these oils have been derived
from Paleocene evaporite sediments. The evaporites
were accumulated under reductive conditions of
saline lakes. The lanostanes of Pietralunga (Italy)
were extracted from the lipids of Miocene marine
limestones [1]. The OM was preserved owing to the
rapid transformation of oxidizing conditions into
reducing ones.
Conclusions. 1. This report describes the first
occurrence of lanostanes in the Cambrian OM. 2.
Lanostane compounds could be markers for
carbonate or carbonate-containing rocks of lacustrine
or marine basins and for reducing conditions in
diagenesis. 3. The identification of these biological
markers in naphthides of the northern slope of the
Aldan anteclise should be a strong evidence of
realization of generative potential of oil-producing
rocks in the Sinskaya Formation.
This study was supported by the Russian Foundation for
Basic Research ( no. 10-05-00705, 11-05-0034), by the
Leading Scientific Schools Grant of the President of the
Russian Federation (grant no. NSh-6244.2010.5).
References
[1] Birgel D., Peckmann J., Org. Geochem. 39, 1659-
1667 (2008).
[2] Chen J.H., Philp R.P., Fu J.M., et al., Geochim.
Cosmochim. Acta 53, 2775-2779 (1989).
[3] Ivantsov A.Yu., Zhuravlev A.Yu., et al.,
Palaeogeogrh., Palaeoclimat., Palaeoecol 220, 69-88
(2005).
[4] Kashirtsev V.A., ―Organic Geochemistry of
Naphthides of the East Siberian Platform― (Yakutsk, 2003)
[in Russian].
[5] Kontorovich A.E. ―Geochemical Methods of
Quantitative Forecasting for Oil-and-Gas content‖, in
Proceedings of the Siberian Research Institute of Geology,
Geophysics and Mineral Resources, V. 229 (Moscow, 1976)
[in Russian].
[6] Kontorovich A.E., et al., Dokl. Earth Sciences 403,
754-759 (2005).
[7] Murae T., Naora M., Hosokawa K., et al.,
Geochim. Cosmochim. Acta 54, 3253-3257 (1990).
[8] Parfenova T.M., Pushkarev M.S., Ivanova E.N.,
Dokl. Earth Sciences 430,129-133 (2010).
[9] Peng. Ping‘an, A. Morales-Izquierdo, Jiamo Fu et
al., Org. Geochem. 28, 125–134 (1998).
220

P-078
The record of the early Aptian global oceanic event OAE1a in
Goraa-Hammam Biadha Basin (Northwestern Tunisia)
Soumaya Abbassi 1,2 , Habib Belayouni 2 , Moncef Saidi 3
1 Macquarie University, Sydney, Australia, 2 Faculty of Sciences of Tunis, Tunis, Tunisia, 3 Entrprise
Tunisienne des Activites Petrolieres, Tunis, Tunisia (corresponding
author:soumaya.abbassi@students.mq.edu.au)
the organic geochemical study, based on both Rock-
Eval and total lipidic extracts data, of two outcropping
sections across the Goraa-Hammam Biadha Basin
have led to point out the following results and
conclusions: (1) the Barremian-Aptian series are
made up of pelagic successsion which is
characterized by cyclically arranged marls and
argillaceous/massive limestones with the occurrence
of some thin black shale horizons; (2) the most
organically rich materials appear to be associated
with massive limestones and with black shale levels;
(3)The Barremian-Aptian series exhibit significant
thickness variation along a NW-SE axis. The highest
thickness (up to 90 meters) is reached towards the
Triassic massif of Arkou-Fedj El Hdoum, while to the
NW, close to the Triassic Massif of Thibar, series are
only 30 meters thick; (4) along a NW-SE axis
addressed across the investigated basin, the Total
Organic Carbon (TOC) average amounts decrease
from 2.5% to 1.72%, a TOC amount as high as 5.8%
has been registered only at the north western part of
the study basin; (5) the total pyrolitic yields (S1+S2)
are also found to decrease from 8.27 mg HC/ g rock
in the NW to 1.69 mg HC/ g rock in the SE, thus
confirming that the Barremian-Aptian series have
good potential oil and gas prone source rocks (HI
indices values for immature levels are up to 435 mg
HC/ g TOC ), with a singular and uncommon
petroleum potential differentiationalong a NW-SE
axis; (6) in term of thermal maturity evolution
(deduced from the Tmax measured values), the late
Barremian-Aptian organic matter displays a variable
and an increased rank of thermal maturity towards the
same direction of the thickening trend (Immature to
early mature source rock: 438°C to the NW and over
mature source rock: Tmax: 495°C to the SE). The
occurrence of these sediments reflects restricted
conditions leading to the accumulation of nutrients
and mainly to the development of anoxia. Accordingly,
such anoxic environment within the basin can be
explained by the existence of physical barrier which
prohibited the changes with the open sea. In addition,
The Goraa-Hammam Biadha basin effectively acted
as a half-graben structure tilted to the south-east
(Fig.1) which had been initiated under a general
extensional regime. Within such a half-graben basin,
the present day Triassic massifs of Thibar to the NW
and Fedj El Hdoum to the SE, acted as active
extensional NE-SW trending faults through which the
rising up of Triassic sediments has induced the
initiation of uplifted structures, and the formation of a
semi-enclosed basin, favourable to the accumulation
and preservation of high amounts of organic matter
associated to typical syn-rift deposits.
Fig1. Lateral correlation between the two studied sections along
a NW-SE axis.
REFERENCES
Langford F. F., and Blanc-Valleron M. M. (1990) Interpreting rock-Eval pyrolysis
data using graphs pyrolyzable hydrocarbons vs.total organic carbon. Am Assoc
Pet Geol Bull 74, 799-804.
221

P-079
Geochemistry of ―just generated‖ oils from Uzon volcano
caldera(Kamchatka) in comparison with oldest pre-Cambrian
oils
Enver Ablya, Irina Slivko
Moscow State University, Moscow, Russian Federation (corresponding author:eablya@yandex.ru)
Uzon volcanic caldera is the largest geothermal
field located in the eastern part of Kamchatka,
Russia. Some hot springs and lakes are notable,
because some are highly acidic and are location
of the occurrence of specific algae and
extremophile. But it is also amazing place of the
generation and occurrence of ―youngest‖ oils. This
oils appear as stains on solutions surface and
quickly evanesce, some oils saturates sediments
around geothermal fields. We studied different oil
samples collected periodically at the same place –
near highly acidic and hot lake. Oils have different
phase from diesel type to very waxy . Oils have
different HC distribution - some as marine type with
prevalence of normal alkanes and Pr/Ph ratio
around 1, and some with prevalence of iso-alkanes
with unusual Pr/Ph ratios less then 0.5-0.3.
Surprisingly that some oils have unusual HC‘s as-
12-and13-methylalkanes. The distribution of
terpanes are characterised by different
concentrations of tri- and tetracyclic - some oils with
low but some – with sharp high value of the C19/C23
ratios; all oils with predominance of the C30hopane
over the C29-norhopane. In some oils
prevalence of C 32 and C 35 homo-hopanes
Saturate and aromatic fractions of Uzon oils are
characterized by polar �13C values from –27‰ to
–34‰. Based on biomarker parameters (steranes,
Ts/Tm, 4-MDBT/1 MDBT, the thermal maturity of
Uzon oils is assessed as low or non-mature ( Fig.
1-2, GC-MS -m/z 217). Oils have relatively low
concentrations of C26 tri and C27 monoaromatic HC
and abundant dibenzotiophen. Distribution of
steranes are also unusual with a significant
predominance of C29 , less C28 and very low C27
steranes (Fig 1-2) . Very interesting that Uzon oils
not content trace elements excluding a hundred
ppm content of As among studied tens usual oils.
We discovered that some Proterozoic (PR) sourced
oils in East Siberia have geochemical fingerprints
similar to those found in some Uzon oils. These PR
oils are characterised by a dominance of C29
steranes ( fig.3), and the occurrence of 12- and 13methylalkanes.
PR oils are characterized by �13C
values around – 33 ‰. . It must be note that some
oldest pre-Cambrian oils from East Siberia and
Paleozoic oils from West Siberia also shows
considerable content of As.
So it believes that this Uzon oils ―just‖
generated by high plant fossils, algae with ―help‖ of
bacteria in boiling toxic geothermal solutions.
Extremophiles are believed to have been some of
the earliest lifeforms on earth, since such early
organisms would have to be adapted to harsh
conditions, for example, Picrophilus torridus, an
extreme archaean acidophile, thrives at pH of
essentially zero, equivalent to a 1.2 molar
concentration of sulfuric acid. Some of ―oldest‖ oils
generated in same conditions ?
Fig.1
Fig.2
Fig.3
222

P-080
Petroleum potential of Miocene heterolithic successions within
the Sarawak Basin, Malaysia: multiple role as source, carrier,
and reservoir rocks
Peter Abolins 1 , Wan Hasiah Abdullah 2 , Meor Hakif Amir Hassan 2 , Mohammed Hail
Hakimi 2
1 PETRONAS Carigali Sdn Bhd, Kuala Lumpur, Malaysia, 2 University of Malaya, Kuala Lumpur, Malaysia
(corresponding author:petera@petronas.com.my)
The petroleum-producing Balingian Province is
situated in northwest Borneo and is a sub basin of the
greater Sarawak Basin, Malaysia. The province,
straddling both onshore and offshore, consists of a
thick clastic succession ranging in age from
Oligocene to plio-pleistocene. Oil production is limited
to the offshore areas but stratigraphic equivalents of
the offshore producing sections are exposed onshore.
The field observations and laboratory analyses of
these onshore successions carried out in this study
suggest an almost self contained petroleum system
within these thick heterolithic clastic sections.
The onshore section is dominated by the Oligocene-
Miocene Nyalau Formation. Within the Nyalau
Formation fine-grained lithofacies occur in close
association with heterolithic facies of interlayered
muddy/sandy sediments within a tidally-influenced
succession of delta plain deposits. Oil-prone coaly
constituents are common, particularly in
carbonaceous shales or carbargillites. Terrigenous
organic matter is observed to be not only restricted to
the coaly and shaley sediments but is also widely
distributed in coarser grained sediments including the
sands and silts of the heterolithic facies.
Petrographic and organic geochemical characteristics
denote good petroleum source potential within these
heterogenous facies association as suggested by
reasonably high HI in the range of about 250-
550mgHC/gTOC (in support of the predominance of
type II & III kerogen), rich in extractable organic
matter and Py-GC pyrograms that are dominated by
n-alkene/alkane doublets.
Onshore field studies show the heterolithic facies that
developed within the lower coastal plain setting to be
laterally extensive within the Sarawak Basin. Such
sequences thicken up in the offshore where they
provide an additional source bearing section in
addition to the already proven thin (

P-081
Geochemical evidence for two sources of oils in the Papuan
Basin, Papua New Guinea
Manzur Ahmed 1 , Herbert Volk 1 , David Holland 2 , Tony Allan 1
1 CSIRO Earth Science and Resource Engineering, North Ryde, Australia, 2 InterOil, Cairns, Australia
(corresponding author:manzur.ahmed@csiro.au)
Two major groups of hydrocarbons, Family A and
Family B, can be distinguished by detailed organic
geochemical assessment of 34 oils/condensates,
inclusion oils and solid bitumens from the Eastern
Papuan Basin (EPB) and the Western Papuan Basin
(WPB) (Fig. 1). Both groups of oils/condensates could
be further divided into two subgroups based on minor
variations in source facies. Family A2 samples in the
EPB were generated at peak to late oil-window
maturities from a clay-rich marine source rock
containing predominantly terrestrial higher plant
derived organic matter deposited in suboxic to anoxic
environments. Biomarker signatures are related to the
crude oils from the WPB Fold Belt region, and similar
to those oils (Family A1), this family was probably
generated from the Late Jurassic Imburu Formation.
Family B samples were also generated at peak to late
oil-window maturities, but from a clay-poor, possibly
calcareous marine source rock, richer in prokaryotic
organic matter, and deposited in suboxic to anoxic
environments. This is indicated by higher abundances
of C29 �� hopane,�C35 homohopanes and
2��methylhopanes. Oleanane±lupane and the
distributions of nordiacholestanes and norcholestanes
suggest that the Family B oils/condensates were
derived from Cretaceous or younger source rock(s).
Hydrocarbons in the Elk-Antelope gas-condensate
field, a significant recent discovery in the EPB, cluster
in Family B. The molecular and isotopic signatures of
thermogenic gases in this field show very little
variation and are also consistent with marine source
rocks. The presence of two major groups of
oils/condensates in the EPB is consistent with the two
families of solid bitumens and an inclusion oil from the
Aure Scarp area (George et al., 2007), and different
types of oils and inclusion oils in the WPB region
(George et al., 1997).
Although the exact origin of Family B hydrocarbons is
unclear, source rock intervals may be hosted in
Cretaceous or Palaeogene strata, e.g. in the
Cretaceous Ieru or Chim Formations. New total
organic carbon and Rock Eval pyrolysis data indicate
that the Late Jurassic / Early Cretaceous Tubu and
Maril Shales in the Papuan Gulf region are also
potential source rocks.
Figure 1. Dendrogram of hierarchical cluster analysis of 13
source-specific biomarker parameters showing genetic
groups of oil/condensates in the Papuan Basin. Data for
solid bitumens; Puri-1 and Bwata-1 oils/condensates are
1.0
P'nyang-2X 1922 m FI oil
Iagifu-7X 2615 m FI oil
Iagifu-7X 2564 m FI oil
Triceratops-1-1805 m oil show
Triceratops-1-1844 m oil show
CN405 Family B solid bitumen
ELK-2 oil show
CN360 Family B solid bitumen
Moose-2 513 m oil show
0.8 0.6 0.4 0.2 0.0
Elk-1 oil/condensate
CN540 Family B solid bitumen
CN409 Family B solid bitumen
Yawiyo seep sample-1
Family B1
CN457 Family B solid bitumen
Bwata-1 oil/condensate
North Ox seep
Moose-2 753 m oil show
Moose-2 634 m oil show
Family B
Antelope-1 DST-11 oil/condensate
Antelope-1 DST-12 oil/condensate
Antelope-1 DST-14 oil/condensate
Antelope-1 DST-13 oil/condensate
from George et al. (2007), and Western Fold Belt
oils/inclusion oils are from George et al. (1997). Sample
names in black for the Eastern and in red for the Western
Papuan Basin.
References
Elk-4 oil-condensate
Antelope-1 1747 oil/condensate
Antelope-1 D-8 oil/condensate
Iagifu-7X DST-1 crude oil
Iagifu-7X DST-3 crude oil
Iagifu-7x DST-5 crude oil
Iagifu-7X DST-2 crude oil
Pangia seep
CN415 Family A solid bitumen
CN383 Family A solid bitumen
Puri-1 oil/condensate
CN381 Family A solid bitumen
Similarity value
Family A1
Family B2
Family A
Family A2
[1] George, S.C., Krieger, F.W.,Eadington, P.J., Quezada,
R.A., Greenwood, P.F., Eisenberg, L.I., Hamilton, P.J. and
Wilson, M.A., 1997. Geochemical comparison of oil–bearing
fluid inclusions trapped in quartz grains and live oil from the
Toro Sandstone, Papua New Guinea. Organic Geochemistry
26, 155-173.
[2] George, S.C., Volk, H., Ahmed, M., Pickel, W., and Allan,
T., 2007. Biomarker evidence for two sources for solid
bitumens in the Subu wells: implications for the petroleum
prospectivity of the East Papuan Basin. Organic
Geochemistry, 38, 609-642.
224

P-082
Geochemical assessment of oil migration in the Upper Shuaiba
of the Lekhwair High in NW of Block 6, Oman
Mohammed Al Ghammari 1 , Paul Taylor 2 , Gordon Coy 1
1 Petroleum Development of Oman, Muscat, Oman, 2 Shell, Houston, United States of America
(corresponding author:Mohd.MRK.Ghammari@pdo.co.om)
The Upper Shuaiba oil play in the Northwestern
corner of Block 6 (PDO concession) has been central
to PDO‘s exploration strategy for a number of years.
With the expansion of the play away from the
sweetspot of the Lekhwair high an improved
understanding of hydrocarbon migration into the area
was required for improved prospect risking and
ranking.
The majority of oil discoveries in the North western
part of block 6 (PDO concession) occur on or around
the Lekhwair High, where two major oil families have
been identified. They are the Precambrian-Cambrian
Huqf and Jurassic Tuwaiq oil families. The Tuwaiq oil
is believed to have migrated laterally from Tuwaiq
source rocks in the western UAE, whereas the deeper
Huqf charge is thought to come from the Fahud Basin
by migrating up and along N-S trending regional faults
and through extensional fractures on the foreland
bulge. It is believed that after vertical migration of the
Huqf charge it migrated laterally below regional Nahr
Umr seal into Upper Shuaiba reservoirs making them
a very attractive exploration target.
The two oil families form a SE/E-NW/W mixing trend
where the pure Tuwaiq oils are restricted to the
Northwestern and western part of the Lekhwair High,
whereas pure Huqf oils occur to the SE and East of
the high. Gas compositions in the area show mixing
characteristic of a Huqf gas with an isotopically
heavier gas charge.
Well results to the southeast of the Lekhwhair high,
on a proposed Huqf migration path were variable.
Well A successfully tested oil in the uppermost part of
Upper Shuaiba, whereas adjacent wells, which were
also believed to be on the Huqf migration pathway
were dry. In order to explain these dry holes, a charge
shadow model for the Huqf was proposed.
The aim of this study was to help understand the well
results by delineating the Huqf migration pathway in
the area to the southeast of the Lekhwair High, and
proves or disproves a Huqf charge shadow in this
area. The study consists of three parts:
•Oil-oil correlation and understanding of the
distribution of oil types in Lekhwair High
•Fluid inclusions analysis in the dry holes.
•Crusher CSIA analysis of microshows identified
It is found that Well A correlates well with Huqf typical
oil and fits the SE-NW trend of Huqf-Tuwaiq
distribution. The microshows found towards the upper
most part of Upper Shuaiba of Well A and two of the
dry well, Well B and Well C which are located
southwest to Well A correlates well with the gases
found in the area which are a mixture of Huqf and the
isotopically heavier gas charge. This finding is
supported by the presence of oil fluid inclusion and
the carbon isotopes of C1-C8 carbon isotopes (CSIA).
CSIA analysis indicates a gradation from mixed Huqf
and the isotopically heavier charge in the C1-C4
range to predominating Huqf in the C5-C8 range.
This mixing of Huqf and heavier charge elements is
not observed in microshows from the Shuaiba in Well
D, a dryhole in the southernmost part of the area,
which only show the isotopically heavier gas charge.
This suggests that this area did not receive Huqf
charge. This study proposed a wider area for
exploration in the southeastern area of Lekhwair High,
but also proved that the southernmost area (around
well D) of Lekhwair High lacks the typical Huqf
charge.
d13C
-20
-25
-30
-35
-40
-45
Crusher_C1
Crusher_C2
Crusher_C3
Crusher_nC4
Crusher_nC5
C7_NC4
C7_NC5
C7_NC6
C7_NC7
C7_NC8
NC9
NC10
NC11
NC12
NC13
NC14
NC15
NC16
NC17
NC18
NC19
NC20
NC21
NC22
NC23
NC24
NC25
NC26
NC27
NC28
NC29
NC30
Well D
Gradation to Lighter carbon isotopes
(in Well B & Well C microshows)
Well A
Well A (1509-1511)
Well A (1517-1521)
Well A (1545-1560)
Naga-1(1422-1434)
Well B (1446-1458)
Well B (1474-1486)
Well C 1462.7
Well C 1471.6
Well C 1488.23
Well C 1466.72
Well C 1464.65
Well C 1481.06
Well C 1469.02
Well D (1546.6)
Well D (1544.94)
Well D (1544.94)
Well D (1545.64)
Well A
225

P-083
Thermal maturity assessment of potential source rocks and
reservoired condensates in kish gas field, Persian Gulf Basin
Bahram Alizadeh 1 , Seyed Hossein Hosseini 1 , Mehdi Khaleghi 2
1 Department of Geology, Faculty of Earth Sciences, S. Chamran University of Ahvaz, Ahvaz, Iran, Islamic
Republic of, 2 National IranianOil Company, Tehran, Iran, Islamic Republic of (corresponding
author:alizadeh@scu.ac.ir)
Persian Gulf is the location of phenomenal
hydrocarbon reserves and is an area of the world
where the oil industry is engaged in intense
hydrocarbon exploration and production. Kish gas
field is a giant gas field which was discovered in 2006
and holds 59 Tcf of gas in place of which 45 Tcf is
recoverable. The field also holds 946 Million barrels of
condensate of which 331 million barrels are
recoverable.
Thermal maturity of Kish gas field has been studied
using preliminary and complementary analyses such
as Rock Eval Pyrolysis, Vitrinite Reflectance (VRo)
and maturity related biomarkers. For this a total of 31
well cutting samples from potential source rocks (e.g.
Pabdeh, Gadvan, Surmeh, Dashtak, Dalan and
Faraghun Formations) and 2 condensate oils from
Dehram Group Reservoirs (Permian - Triassic) in Kish
gas field were selected.
The amounts of Tmax parameter for potential source
rocks ranges between 429 - 443 °C, and increased by
depth gradually from Pabdeh (Tertiary) to Faraghun
Formation (Permian). Based on Tmax parameter,
Faraghun unit is the only Formation that enters the oil
window (Tmax > 435 °C). Conclusions on thermal
maturity based on Tmax was supported by other
geochemical measurements such as VRo, and
biomarkers (Peters et al., 2005).
For vitrinite reflectance five polished samples with
highest TOC have been prepared from potential
source rocks. Measured VRo values are 0.48, 0.5,
0.65, 0.68 and 0.7% for Pabdeh, Kazhdomi, Gadvan,
Surmeh and Faraghun Formations respectively.
The C32–homohopane results were used to calculate
the 22S/((22S+22R) ratio rising from 0 to 0.6 during
maturation. This ratio for Pabdeh and Gadvan
Formations (0.37 and 0.52) indicate that both the
units are immature. These results for other potential
source rocks, as well as two condensate oils from the
Dalan Formation range between 0.59 - 0.62 and
suggest that the condensate oils have been
generated at the peak of oil window and even beyond
the zone of petroleum generation. The
moretanes/hopanes ratio for studied samples
indicates that Pabdeh Formation has the highest
value of the ratio (0.24) and for other potential source
rocks as well as condensate samples this ratio ranges
between 0.08 – 0.14. These values determine the
lowest maturity for Pabdeh Formation and also
suggest that in other samples the VRo should be
greater than 0.6 (Catagenesis Stage). There is a
systematic increase in the relative abundance of Ts
and a decrease in C27 17β-trisnorhopane compared
with Tm with depth (0.2 – 0.6). As it is predictable,
among the studied samples condensate oils have the
highest values of this ratio. Diasteranes/(Dia +
Regular) C27 steranes versus Ts/(Ts+Tm). The Plot
clearly indicates increasing maturity with depth in
studied samples (Fig. 1). Ts/hopanes ratio, C29 Ts/(C29
hopane + C29 Ts) ratio as well as metylphenanthrenes
index (MPI-I) to MPI-II all authenticate that maturity of
potential source rocks in Kish gas field increase with
depth while the source for condensates must be at
gas window and deeper than studied source rocks.
Fig.1: Plot of Ts/(Ts+Tm) vs. C27 Dia /(Dia+Reg)
Steranes demonstrating the increase in maturity of
source rocks with depth.
Reference:
Peters, K. E., Walters, C. C., Moldowan, J. M. (2005).
The Biomarker Guide: Biomarkers in Petroleum
System and Earth History. Vol.2. Second Edition.
Cambridge University Press.United Kingdom.
226

P-084
The oil fraction composition of nonisothermic aquathermolysis
products of sulfur-rich native asphaltite in the 200−575°C
temperature range
Vladimir Antipenko
Institute of Petroleum Chemistry SB RAS, 4, Akademicheskiy Avenue, Tomsk, Russian Federation
(corresponding author:avr@ipc.tsc.ru)
Using a GC/MS method normal and isoprenoid
alkanes, steranes and pregnanes, hopanes and
cheilanthanes, mono-, bi-, tri- and tetracyclic aromatic
hydrocarbons, as well as bi-, tri and tetracyclic sulfurcontaining
aromatic compounds were identified in oil
fractions of the products of sulfur-rich native asphaltite
aquathermolysis carried out in a flow reactor at a
pressure of 15 MPa. The fractions were obtained at
the temperatures ranging from 200 to 575 °C. The
presence of alkenes (α-olefins) was typical only for
the products formed at temperature of 400−575 °С.
Aliphatic compounds were found to predominate
(50.34−89.90 %) in the oil fractions of
aquathermolysis products in the whole temperature
interval. The content of tetracyclic aromatic
hydrocarbons (0.08−0.94 % - total fluoranthene,
pyrene, chrysene and benzo[a]anthracene) and that
of tetracyclic sulfur-containing aromatic compounds
(0.05−0.87 % - total acenaphtho[1,2-c]thiophene and
three benzo[b]naphthothiophene isomers) were the
lowest.
Relative content of the compounds of different
types in oil fractions of the products obtained at
different temperatures varied in a polyextreme
manner. The highest total content of alkanes and αolefins
was observed at 575 °С (89.90 %). However
even at this temperature resin-asphaltene substances
generate a complete set of the compounds included
in the composition of oil fractions of the initial
asphaltite. Therefore excluding α-olefins these
compounds occur in resins and asphaltenes as
structural fragments.
The appearance of anthracene and 2methylanthracene
at high concentrations in the
products of aquathermolysis at 400−575 °С testifies
the presence of these compounds in resin and
asphaltene molecules as structural fragments.
Dihydroanthracene fragments of asphaltene and resin
molecules, which can undergo dehydrogenation
under the experiment conditions, can also be a
source of anthracene structures.
Phenylalkanes predominate among
monoalkylbenzenes in the oil fractions of the initial
asphaltite and in those of aquathermolysis products
obtained at the temperatures ranging from 200 to 450
°С, while at 475 °С and a higher temperature nalkylbenzenes
were found to predominate. It testifies
the presence of the latter in the molecules of resins
and asphaltenes as structural fragments.
For naphthalenes, phenanthrenes,
benzothiophenes and dibenzothiophenes a ratio of
high-molecular homologues to low-molecular ones
gradually increases to a certain limit and then it
noticeably decreases. The lowest values of these
ratios in dibenzothiophenes and phenanthrenes are
typical to the products obtained at the temperature
range of 475−575 °С. In case of benzothiophenes a
portion of high-molecular homologues (С5−С15)
noticeably decreases, while that of low-molecular
homologues (С2−С4) increases. It is conditioned by
the increased role of processes of alkyl chain
cracking.
In oil fractions of the initial asphaltite high- and
low-molecular steranes (steranes and pregnanes,
respectively) occur in comparable concentrations. At
increase in the temperature of products sampling a
portion of high-molecular homologues evidently
decreases and at 575 °С steranes are mainly
presented by low-molecular homologues – pregnanes
of С21 and С22 compositions.
A character of triterpane compositional changes
consists in a sharp increase of the relative content of
hopanes of С27 composition and in a noticeable
decrease of the relative content of homohopanes in
high-temperature products. It is important to notice
predominant generation of Tm isomer among hopanes
of C27 composition indicating a lower thermal maturity
of the ―bound‖ forms of hopanes as compared with
hopanes occurring in the oil fractions of the initial
asphaltite.
227

P-085
Flash pyrolysis-gas chromatography-mass spectrometry of
sulfur-rich native asphaltite, its asphaltenes, resins and oils
Vladimir Antipenko 1 , Vasilyi Melenevskiy 2
1 Institute of Petroleum Chemistry SB RAS, 4, Akademicheskiy Avenue, Tomsk, Russian Federation,
2 Trofimuk Institute of Oil and Gas Geology and Geophysics SB RAS, 3, Prosp. Acad. Koptuga, Novosibirsk,
Russian Federation (corresponding author:avr@ipc.tsc.ru)
Asphaltite recovered from Ivanovskoye oil field,
Orenburg region, and the products obtained
(asphaltenes, benzene and ethanol-benzene resins,
oil fractions) were characterized combining
successive flash-pyrolysis at the temperatures of 400
and 650 °С and ―on line‖ GC/MS analysis of the
yielded volatile products. It was determined that
compositions of the volatile products at 400 °С were
mainly determined by evaporation process, while
signs of thermodestruction of the products under
study were also observed.
The volatile products of high-temperature (650 °С)
flash pyrolysis of all the components of sulfur-rich
natural asphaltite contain the same set of compounds
(normal and isoprenoid alkanes, alkenes,
cyclohexanes, cheilanthanes and hopanes, hopenes
C27 and C30, pregnanes and steranes, mono-, bi-, tri-
and tetrasubstituted alkylbenzenes, (С1−С4)naphthalenes,
(С0−С4)-phenanthrenes, anthracene
and 2-methylanthracene, (С0−С4)-dibenzothiophenes
and (С1−С20)-benzothiophenes). It proves the
presence of major enumerated compounds in the
compositions of oil fractions and resin-asphaltene-
substances (RAS) of the natural asphaltite under
study as structural fragments.
By relative contents in the volatile products of a
high-temperature flash-pyrolysis the identified
compounds are ranged in the following series:
1) In case of oil fractions – (alkanes+alkenes),
alkylbenzenes, benzothiophenes, (hopanes +
hopenes), dibenzothiophenes, cyclohexanes,
naphthalenes, steranes and phenanthrenes;
2) In case of benzene resins –
(alkanes+alkenes), alkylbenzenes, benzothiophenes,
dibenzothiophenes, (cyclohexanes and
naphthalenes), (hopanes+hopenes), steranes and
phenanthrenes;
3) In case of ethanol-benzene resins –
(alkanes+alkenes), alkylbenzenes, benzothiophenes,
dibenzothiophenes, (cyclohexanes and
naphthalenes), (hopanes+hopenes), phenanthrenes
and steranes;
4) In case of asphalnetes – (alkanes+alkenes),
alkylbenzenes, benzothiophenes, dibenzothiophenes,
(cyclohexanes and naphthalenes), (hopanes+
hopenes), phenanthrenes and steranes.
For RAS these series are nearly identical
indicating genetic unity of resins and asphaltenes.
Total alkanes and alkenes are the most widespread
types of the compounds for all the initial samples in
the volatile products of the high-temperature flash
pyrolysis. Their total content varies from 80.4 to 86.5
%. Alkylbenzenes (8.7−12.6 %) are the second
compounds by their representation. Then one ranges
benzothiophenes (1.9−3.1 %) and dibenzothiophenes
(0.7−1.5 %) in accordance with the decrease in
relative contents
The calculations carried out taking into account the
yields of the volatile products of pyrolysis and coke
from the studied asphaltite components determined
using ―Rock Eval‖ device, demonstrate that paraffin
chains (24.0−56.7 %) and non-identified cock-forming
fragments (34.5−70.2 %) are the most widespread
structural fragments both in oil fractions and in RAS of
the asphaltite under study. Benzene (3.7−6.1 %)and
benzothiophene (0.9−1.3 %) cycles are presented in
the lesser degree.
Thus, combined low- and high-temperature ―on line‖
flash-pyrolysis is effective means aimed to obtain
information of the presence, forms of occurrence and
relative contents of different structural fragments in
RAS and oil fractions of the natural asphaltite.
The results obtained are meaningful to understand
the ways of catagenetic transformation of organic
matter in sedimentary rocks in order to predict
compositions of distillate fractions in the products of
thermal cracking of heavy oil residues and natural
bitumens as well as to extend our knowledge about
compositions of petroleum RAS and related natural
objects.
228

P-086
Migration tracers reveal long-range migration in the summan
exploration area
Khaled Arouri 1 , S K Panda 2 , S A Satti 3 , Y Yang 1
1 EXPEC Advanced Research Center, Saudi Aramco, Dhahran, Saudi Arabia, 2 Research and Development
Center, Saudi Aramco, Dhahran, Saudi Arabia, 3 Area Exploration Department, Saudi Aramco, Dhahran,
Saudi Arabia (corresponding author:khaled.arouri@aramco.com)
Exploration around the Summan Platform, north of
Saudi Arabia, is progressively extending west and
south. The shift of exploration effort away from the
kitchen, which lies to the north of the Summan
Platform, has increased the risk of charge access to
the prospects further away to the south and west. A
migration study — based on the geochemical
characteristics of oils — can mitigate this risk and
help better understand the migration extent from the
Late Jurassic kitchen.
Benzocarbazoles
(benzo[a]carbazole/benzo[c]carbazole; BC) have
been suggested as odometers for oil migration (Larter
et al., 1996). The systematic BC behavior — for Late
Jurassic Arab-A oils from oilfields in the Summan
area — suggests that these accumulations are
charged via long-range migration, rather than multiple
sourcing from different local kitchens. The BC ratio
systematically decreases southwards from Field A to
Field E (Fig. 1), apparently as a response to the
increase in migration distance from a kitchen to the
north. While Field E is believed to be the most distal
oil belonging to this petroleum system, any traps
(whether structural or stratigraphic) — along this
north-south trending long-range migration pathway —
are high-graded, especially those closer to the entry
point north of Field A.
The reduction in BC ratio with increasing migration
distance is accompanied by a decrease in oil maturity,
with early-generated, lower-maturity oil (Field E) being
the most-fractionated, shallowest and furthest away
from the source kitchen. This reduction in ratio is also
associated with a clear API gravity gradient across
the basin, together with a gentle compositional
(molecular and isotopic) gradient, indicative of
increasing contribution by more mature oil with depth
toward the north (Field A).
Long-range migration has probably been facilitated by
a displacement (fill-and-spill) mechanism through
intermediary fields along the migration route.
Interestingly, the southward migration effect
manifested at a regional scale is also evident at a field
scale, where the north of each field contains its last
charge, whereas the south contains its migration
front. Vertical and lateral compositional grading in
some Summan fields is likely due to poor mixing of
several viscous charges from a common carbonate
source. This observation highlights the importance of
interpreting the compositional grading of reservoirs
within the larger context of regional migration and
regional compositional grading.
Reference Cited
Larter, S.R., Bowler, B., Li, M., Chen, M., Brincat, D.,
Bennett, B., Noke, K., Donohoe, P., Simmons, D.,
Kohnen, M., Allan, J., Telnaes, N., Horstad, I., 1996.
Benzocarbazoles as molecular indicators of
secondary oil migration distance. Nature 383, 593–
597.
Depth (ft) below sea level
S.L
-2000
-4000
-6000
-8000
-10,000
-12,000
-14,000
S N
E
15
0.28
a c
most-fractionated
= most-migrated
D
23
0.59
a c
C
26
0.63
a c
~ 200 km
B
32
0.89
decreasing API
decreasing oil maturity
lighter � 13 C updip
similar source signature (carbonate)
a c
decreasing BC ratio
A
33
0.97
a c
least-fractionated
= least-migrated
API
Kitchen
BC ratio
Figure 1. Oilfield compositional gradients as a
function of distance from the kitchen, including:
benzocarbazole (BC) ratio, API gravity, isotope ratios
and maturity versus depth below sea level. The
benzo[a]carbazole (labeled a) is preferentially
removed relative to benzo[c]carbazole (labeled c).
229

P-087
Petroleum geochemistry of the Stord Basin, Norwegian North
Sea
Mark Bastow
Applied Petroleum Technology AS, Kjeller, Norway (corresponding author:mb@aptec.no)
The Stord Basin centred on Quadrants 26/27 and
31/32 in the Norwegian North Sea remains virtually
unexplored, due largely to the shallow depth of burial
of the Jurassic section and consequent concerns
regarding maturation levels for petroleum generation.
For wells drilled around the margins of the basin,
available data and results of new geochemical
analyses have been combined in order to identify
potential source rocks and the challenges for working
petroleum systems within the basin.
The Draupne Formation is generally organically rich
with good oil source potential and around the margins
of the Stord Basin is generally early mature to
marginally middle mature for oil generation and
immature for significant gas generation. Well 26/4-1
demonstrates extension of this source rock interval
into the Stord Basin, where the Draupne Formation
may attain marginal middle maturity for oil generation
but with low transformation ratio and consequently
with significant risk for expulsion of economic
hydrocarbon volumes. Atypical oils from the
Norwegian North Sea have been suggested to be
derived from locally developed carbonate facies of the
Draupne Formation. These may generate oil at lower
maturation level compared to typical siliclastic source
rock facies and may be important for the prospectivity
of areas, including the Stord Basin, that have
undergone limited subsidence and burial.
The Heather Formation is interpreted to have mainly
gas source potential but is known to have localized oil
source potential on the Horda Platform and the
development of similar source facies within the Stord
Basin cannot be discounted.
The Drake Formation generally has fair to good gas
source potential. Within thick Drake Formation
sections wireline logs indicate thin intervals with
possible oil source potential that can be correlated
between wells. In study wells around the margins of
the Stord Basin, the Drake Formation is generally
early to marginally middle mature for oil generation
and immature for significant gas generation. Within
the Stord Basin the Drake Formation is likely to attain
middle maturity for oil generation.
Coals within the Ness/Sleipner Formations and thin
coals within the Statfjord Formation are unlikely to
attain maturity for significant gas generation within the
Stord Basin.
Uplift and erosion of the eastern margin of the Stord
Basin is indicated, in the south by well 17/3-1 and in
the north mainly by wells 31/6-3 and 32/4-1.
Estimated thicknesses of section missing estimated
are about 1000m. The timing of uplift and erosion is
late, post-dating deposition of the Hordaland Group
and pre-Quaternary Nordland Group and followed by
deposition of sediments of Quaternary age.
Well 26/4-1 reported weak oil shows in the Hugin and
Statfjord Formations. Core samples from the Hugin
Formation indicate no significant oil stain and very
weak, possibly diesel contamination of the core. To
date, discoveries and significant shows of
thermogenic hydrocarbons on the Utsira High (well
25/6-1) and on the Horda Platform (Troll Field) are
related to migration from source rocks outside the
Stord Basin. Discovery well 17/3-1 tested gas of
biogenic origin in the Sandnes Formation.
3D modelling of seismic depth maps would enable
maturity mapping of potential source rock intervals,
indicate possibilities for both expulsion and migration
within the Stord Basin, and also model temperatures
for evaluation of both degradation risk in shallow
prospective reservoir intervals and phase separation
due to uplift and erosion.
230

P-088
Crude oil in the Alpine Foreland Basin of Austria: a known
petroleum system revisited
Achim Bechtel 1 , Reinhard Gratzer 1 , Reinhard F. Sachsenhofer 1 , Hans-Gert Linzer 2 ,
Doris Reischenbacher 1 , Hans-Martin Schulz 3
1 Montanuniversitaet, Leoben, Austria, 2 Rohoel-Aufsuchungs AG, Vienna, Austria, 3 GFZ German Research
Centre for Geosciences, Potsdam, Germany (corresponding author:Achim.Bechtel@mu-leoben.at)
The Alpine Foreland Basin is a minor oil and
moderate gas province in central Europe. The
majority of the fields is located in southeastern
Germany and Austria. In the Austrian part of the
Alpine Foreland Basin, oil and minor thermal gas are
thought to be predominantly sourced from lower
Oligocene horizons (i.e. the Schöneck, Dynow, and
Eggerding formations). The source rocks are
immature where the oil fields are located and enters
the oil window at ca. 4 km depth beneath the Alpine
nappes indicating long-distance lateral migration.
Most important reservoirs are Upper Cretaceous and
Eocene basal sandstones.
Stable carbon isotope and biomarker ratios of oils
from different reservoirs indicate compositional trends
in W-E direction which reflect differences in source,
depositional environment (facies), and maturity of
potential source rocks (Fig. 1). Thermal maturity
parameters from oils of different fields are only in the
western part consistent with northward displacement
of immature oils by subsequently generated oils. In
the eastern part of the basin different migration
pathways must be assumed (Fig. 1c). The trend in
S/(S+R) isomerisation of ��� C29 steranes versus the
��� (20R)/��� (20R) C29 steranes ratio from oil
samples can be explained by differences in thermal
maturation without invovling long-distance migration.
The results argues for hydrocarbon migration through
highly permeable carrier beds or open faults rather
than relatively short migration distances from the
source. The lateral distance of oil fields to the position
of mature source rocks beneath the Alpine nappes in
the south suggests migration distances between less
than 20 km and more than 50 km.
Biomarker compositions of the oils suggest Oligocene
shaly to marly succcesions (i.e. Schoeneck, Dynow,
and Eggerding formations) as potential source rocks,
taking into account their immature character. Best
matches are obtained between the oils and units a/b
(marly shale) and c (black shale) of the ―normal‖
Schöneck Formation, as well as with the so-called
―Oberhofen facies‖. Results from open system
pyrolysis-gas chromtography of potential source rocks
indicate sligthly higher sulfur content of the resulting
pyrolysate from unit b. The enhanced dibenzo–
thiophene/phenanthrene ratios of oils from the
western part of the basin would be consistent with a
higher contribution of unit b to hydrocarbon expulsion
in this area. Differences in the relative contribution of
sedimentary units to oil generation are inherited from
thickness variations of respective units in the
overthrusted sediments. The observed trend toward
lighter � 13 C values of hydrocarbon fractions from oil
fields in a W-E direction are consistent with lower
� 13 C values of organic matter in unit c.
231

P-089
Addressing thermogenic and biogenic gas emissions during
the formation of the oil sands deposits of the Western Canada
Basin
Luiyin Berbesi, Rolando di Primio, Zahie Anka, Brian Horsfield, Heinz Wilkes
GFZ German Research Centre for Geosciences, Potsdam, Germany (corresponding author:berbesi@gfzpotsdam.de)
The thermal maturation of organic matter in
sedimentary basins implies, in general lines, the
generation, migration, and accumulation of
hydrocarbons, and in many cases, its subsequent
alteration in reservoir. During the different stages of
this process, a portion of the generated hydrocarbons
escapes from the sedimentary basin and may enter
the hydro- and atmosphere, with methane (CH4) being
one of the main expelled gases.
The strong greenhouse gas potential of methane is
well known [1] , and it could suggest the existence of a
link between gaseous hydrocarbon leakage and
climate history. In this context, an evaluation of the
amount of methane released during the evolution of
sedimentary basins worldwide as well as the timing of
these processes is required.
A very good target for this approach is the Western
Canada Basin, given its immense quantities of heavy
oil deposits, estimated over 250 x10 9 m 3 [2] . The
geological setting is that of a foreland basin, where
the generation and accumulation of oil was followed
by uplift during the Laramide orogeny and subsequent
biodegradation of original oil.
In this project, the hydrocarbon generation and
accumulation, as well as thermogenic gas emission
were assessed using a 3D basin model that covers
most of Alberta and Saskatchewan, and a part of the
Rocky Mountains in British Columbia, Canada. The
stratigraphic sequences were reproduced by 22
isopach maps covering middle Devonian to Tertiary
strata. The lithologies correspond to those described
in the Atlas of the Western Canada Sedimentary
Basin [3] . The kinetic parameters applied to source
rocks were based on the relationship between the
organic sulfur content of kerogen and the kinetic
parameters determined by hydrous pyrolysis [4] . We
used a constant heat flow map containing values
between 45 mW/m 2 and 70 mW/m 2 for the study
area [3] . The magnitude of the Laramide erosion
ranges from 180 to 2400 meters [5] . A hybrid
calculation method combining Darcy flow and flowpath
(ray tracing) techniques was used for
hydrocarbon migration simulation. The model
suggests that a peak of gas leakage at the upper
boundary of the model occurred between 80 to 60
Ma, concordant with the major phase of generation
and migration. The amount of thermogenic gas
released during this period of time was approximated
to be in the order of 10 16 to 10 17 grams.
Additionally, the amount of generated, and possibly
released secondary biogenic methane was addressed
by estimating the rate of petroleum degradation and
the magnitude of petroleum loss. We calculated the
amount of generated biogenic methane following a
model [6] that assumes hexadecane (C16H34) as a
representative compound for the saturated
compounds. Based on this methodology, the total
amount of generated methane during 60 million years
of biodegradation is in the order of 10 17 g , of which
50 % would probably have been generated during the
first 20 million years after the main charge phase.
Our estimates for combined thermogenic and
biogenic methane emitted during the evolution of the
Western Canada Basin, amount to 8 x 10 17 g. The
estimated amount of secondary methane, generated
during the first million years of biodegradation,
corresponds to around 50 times the total present-day
annual flux of methane into the atmosphere.
However, the possible influence of the estimated
leaked gas on past climate evolution will depend not
only on the rate at which this methane leaks from the
basin, but also on the rate of its further oxidation.
These processes remain to be constrained.
References
[1] United Nations Framework Convention on Climate Change
(UNFCCC) 1995.
[2] National Energy Board Canada, 2000,NEB Report, p.5.
[3] Mossop, G., and I. Shetson, eds., 1994, Geological atlas of the
Western Canada sedimentary basin.
[4] Higley, D., Lewan, D., Roberts, N., and Mitchell, H., 2009, AAPG
Bulletin, v. 93, no 2, p. 203-230.
[5] Nurkowski, J.,1984, AAPG Bulletin, v. 68, no 3, p. 285-295.
[6] Zengler, K., Richnow, H., Rosselló, Mo., Michaelis, W, and F.
Widdel, 1999, Nature, v. 401, 266-269.
232

P-090
Hydrocarbon potential of the western Barents Sea – Evaluation
of sedimentary rocks of Spitsbergen
Ulrich Berner 1 , Bernhard Cramer 1 , Karsten Piepjohn 1 , Pjotr Sobolev 2
1 Federal Institute for Geosciences and Natural Resources, Hannover, Germany, 2 Karpinsky Russian
Geology Research Institute, VSEGEI, St. Petersburg, Russian Federation (corresponding
author:ulrich.berner@bgr.de)
Seventy-five potential source rocks from Upper
Permian to Lower Tertiary of Spitsbergen have been
sampled during a joint project of BGR (Hannover,
Germany) and VSEGEI (St. Petersburg, Russia). The
sample sites are associated with the Central Basin of
Spitsbergen, and are located along the coastline of
Isfjorden and the southern Advendalen.
Organic geochemical investigations have been
performed; the latter include pyrolysis methods,
molecular as well as stable isotope analyses of
organic matter and sediment extracts. The
investigations aim at a better understanding of
Spitsbergen sediments as indicators of hydrocarbon
source rocks within the western Barents Sea region.
Within the marine Upper Permian Kap Starostin, and
the Lower Triassic Vikinghøgda Fms. consists of clay
stones and marls, whereas the Botneheia Fm. is
dominated by marls. The organic matter in both
formations consists of mixtures of aquatic and
terrestrial precursors as seen from pyrolysis and
biomarker data. The quality of the organic matter of
the Botneheia Fm., which has been deposited under
anoxic to dysoxic conditions is very good, as it
contains a higher contribution from hydrogen-rich
aquatic precursors. The upper section of the Lower
Triassic (Tschermakfjellet Fm.) is influenced by
terrestrial organic matter, which is also true for the
Middle Triassic De Geerdalen Fm. and the Upper
Triassic Knorringfjellet Fm.
The Middle Jurassic Agardhfjellet Fm. contains locally
variable mixtures of terrestrial and aquatic organic
matter. The depositional environment was likely dys-
to anoxic as seen from the elemental and biomarker
data. The sediment samples of the Upper Jurassic
Rurigfjellet Fm. are however dominated by terrestrial
organic matter.
The sediments of the Lower Cretaceous Helvetiafjellet
and Carolinefjellet Fms contain abundant land plant
material, which is also true for the Palaeocene
Firkanten Fm.
Likely oil source rocks of the western Barents Sea
region as indicated by data from Spitsbergen are
Early Triassic Vikinghøgda and Botneheia Fms as
well as the Jurassic Agardhfjellet Fm. All other
organic rich sediments are rather gas than oil prone.
A general trend from marine (partly anoxic and
dysoxic) depositional conditions during Upper
Permian and Triassic times to terrestrial palustrine
deposits during Palaeocene is observed (Fig. 1).
The thermal maturity of the investigated samples
reaches peak-oil generation in the Lower Triassic and
is only slightly lower in the Jurassic sediments. The
samples of the Lower Cretaceous Helvetiafjellet Fm.
touch the onset of the oil window at the sites along
the Isfjorden but samples from Carolinefjellet Fm. and
the Palaeocene Firkanten Fm. reveal a higher
maturity due to the structural position of the sample
sites south of Advendalen. The thermal regime in the
larger area is likely very heterogeneous due to the
presence of igneous intrusions which have been
described at different site on Spitsbergen and are
likely to occur also in the larger western Barents Sea
region.
Figure 1: The terrestrial-aquatic ratio (TAR) derived
from light aliphatic compounds indicates a shift from
marine depositional systems to terrestrial/pluvial
environments during Cretaceous and Palaeogene
times.
233

P-091
Investigation of oil stability under geological conditions using
kinetics of C8 hydrocarbons cracking derived from MSSV
pyrolysis
Regina Binotto 1 , Rosane Fontes 1 , Henrique Penteado 1 , Denise Bohrer 2
1 Petrobras Research Center, Rio de Janeiro, Brazil, 2 Federal University of Santa Maria, Santa Maria, Brazil
(corresponding author:binotto@petrobras.com.br)
One of the most fundamental problems in
petroleum systems modeling for deep offshore
prospects is to determine the spatial (depth) and
temperature limits of oil occurrence [1]. Reservoirs
that were originally filled with oil might be subjected to
further burial, and liquid petroleum may be cracked to
gas. Oil-to-gas cracking is governed by a large
number of chemical reactions that are not known in
detail, but are recognized as being irreversible firstorder
reactions following the Arrhenius law.
Oil-to-gas cracking kinetics applied to petroleum
systems modeling were derived from cracking
experiments using different pyrolysis techniques [2].
Whole oils, light fractions or individual compounds
have been submitted to artificial cracking using
different methods, thus making a comparison of their
relative kinetic behavior not straightforward.
The objective of this study was to improve the
understanding of oil-to-gas cracking and the extreme
geological conditions for oil preservation by deriving
kinetics through experimental cracking of compounds
present in the light fraction of petroleum. A
methodology was developed using MSSV (microscale
sealed vessel) coupled with gas
chromatography with flame ionization detector
(MSSV-GC-FID) to assess the thermal degradation of
C8 pure hydrocarbons that occur among the lightest
and most stable compounds in natural oils.
The selected compounds are representative of
each class of light hydrocarbons: a normal-chain
alkane (n-octane), a branched alkane (2,3,4trimethylpentane),
a cyclic alkane (ethylcyclohexane),
and an aromatic (o-xylene).
By performing the same analytical protocol in these
pyrolysis experiments, kinetic parameters were
obtained (Ea, activation energy, and the frequency
factor A) for the thermal degradation of the four
selected C8 compounds. This approach allows a
direct comparison of the derived kinetics, since
differences due to various analytical setups were
avoided. MSSV Pyrolysis experiments were carried
out in an anhydrous closed system under isothermal
conditions from 0 to 7 hours (470-530°C). The global
rate constants were determined based on the reactant
conversions obtained at various temperatures. For all
temperatures, bulk decomposition of the studied
substances obeys first-order kinetics and the resulting
apparent activation energy (Ea, kcal/mol) and the
corresponding frequency factor (A, s -1 ) derived from
the Arrhenius diagram are: n-octane (57; 5.62x10 12 ),
2,3,4-trimethylpentane (54; 6.71x10 11 ),
ethylcyclohexane (49; 1.76x10 10 ) and o-xylene (40;
3.96x10 6 ).
These kinetic parameters were used to
extrapolate the behavior of compounds at low
temperatures over geologic time. First, the
extrapolation of laboratory cracking rate constants
showed that the Arrhenius plots cross at 200-300°C
(Fig. 1). This means that o-xylene, which is more
stable than the other compounds at higher
temperatures, becomes the most labile below 200-
300°C. This reverse behavior, i.e. the lower stability of
aromatics under geological conditions, explains why
oils found in deep reservoirs are more depleted in
aromatics and consequently enriched in n-alkanes [3].
ln k (s -1 )
0
-10
-20
-30
-40
Lab
Conditions
(470-530°C)
~300°C
~200°C
n-octane ethylcyclohexane
2,3,4-trim ethylpentane o-xilene
-50
0,6 0,7 0,8 0,9 1 1,1 1,2 1,3 1,4
1/RT (kcal/mol)
Natural
Conditions
(120-200°C)
Fig. 1. Comparison of the Arrhenius diagram obtained for noctane,
2,3,4-trimethylpentane, ethylcyclohexane and oxylene
degradation.
Geological simulations using the acquired
kinetics and a constant heating rate of 1°C/ million
years indicated that the temperature ―windows‖ of
compound cracking (between 10% and 90%
conversion) are: n-octane 171-202°C, 2,3,4trimethylpentane
163-195°C, ethylcyclohexane 144-
177°C, and o-xylene 126-164°C.
References
[1] Welte, et al., Springer-Verlag, 1997.
[2] Waples, D.W., Org. Geochemistry, 31, 553-575, 2000.
[3] Behar et al., Energy & Fuels, 13, 471-481, 1999.
234

P-092
Geochemistry of heterocyclic components from organic matter
and oils of West Siberia
Lyubov Borisova
Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation (corresponding
author:BorisovaLS@ipgg.nsc.ru)
Multiyear studies conducted by the author [1-3] in
IPGG SB RAS (Novosibirsk) have shown that the
parameters of asphaltenes and resins, along with
hydrocarbon indices, allow the effective solution of
fundamental problems of the theory of formation and
transformation of oil in the Earth‘s sedimentary cover.
In order to study in detail these complex highmolecular
compounds of oils and dispersed organic
matter (DOM), a single complex of physicochemical
methods has been devised (elemental, isotopic, x-ray
diffraction analyses, spectrometry in the visible and IR
regions, NMR, EPR, electron microscopy, and Rock-
Eval pyrolysis).
The composition and structure of resins and
asphaltenes of DOM of variable genetic nature from
petrographically pure rocks, like hydrocarbon (HC)
components of bitumen extracts, are essentially
different, depending on assigning to aquagene
(marine) or terragene (continental) type. Up and down
the section of the Volgian stage, a gradual
carbonization of heteroatomic components occurs,
carbon content increases, and hydrogen and sulfur
content decreases. At the same time, the
hydrocarbon potential value declines, and vanadylporphyrin
complexes almost completely disappear.
These differences in the composition and structure of
heteroatomic components of OM from Lower
Cretaceous and Lower-Middle Jurassic deposits
suggest that terragene components have been
contributed to the OM of these deposits.
Geochemical structural features of resins and
asphaltenes of DOM are substantially defined by
catagenesis processes. In mesocatagenesis, the
composition of asphaltenes undergoes directed
changes, similar to those revealed by A.E.
Kontorovich [4] for debitumenized OM of
corresponding genetic nature: carbonization of
heterocyclic components is accompanied by the
decrease in hydrogen and heteroatoms, and the
growth of the degree of aromaticity of their molecules.
No unidirectional relationship between the resin
composition of various genetic types of OM and the
level of OM thermal maturity during mesocatagenesis
is marked. Only the redistribution of resins occurs: the
content of benzene resins increases and that of
alcohol-benzene ones decreases. At the same time,
benzene resins are carbonized, and alcohol-benzene
ones become more aliphatic and oxidized. During
apocatagenesis, the carbonization process of
asphaltenes changes, on the one hand, into their
polymerization and transition into insoluble forms, and
on the other hand, into aliphatization and partial
transition of their lighter form into resins, and the latter
into aromatic HC. Thus, during catagenesis of DOM
not only kerogen, but also asphaltenes and resins are
destructed and newly form [1, 5].
Investigation of asphaltenes and resins of West
Siberian oils of variable age has revealed the genetic
features of their structure and variation under the
impact of biodegradation and categenesis.
Genetic relations have been established in the
series: asphaltenes, resins of DOM – asphaltenes,
resins of oils. They are most clearly defined in the
content of sulfur, oxygen, vanadyl-porphyrins, and
isotope carbon composition.
Asphaltenes are of complex significance in the
geochemical history of oil, being a source of new HC,
on the one hand, and the inhibitor, impeding the oil
transformation processes both in catagenesis and
hypergenesis zone, on the other.
References
[1] Borisova, L.S. (2004) Russian Geology and
Geophysics 45, N 7, 884-894.
[2] Borisova, L.S. (2009) Geologiya nefti i gaza, (in
Russian), N 1, 76-80.
[3] Borisova, L.S., Kontorovich, A.E. (2008) Dokl. RAN
420, N 3, 1-3.
[4] Kontorovich, A.E. (2004) Sketches of theory of
naphthide genesis (in Russian), SB RAS, Novosibirsk
[5] Kontorovich, A.E., et al. (1988) Sovetskaya
geologiya (in Russian), N 7, 26-35.
235

P-093
Organic geochemistry, petroleum systems, history of oil and gas
generation and accumulation in northern part of West Siberian
basin
Alexey Kontorovich, Lev Burshtein, Sergey Ershov, Valery Kazanenkov, Natalya Kim,
Vladimir Kontorovich, Vasiliy Melenevsky, Pavel Safronov, Alexander Fomin, Elena
Fursenko, Georgiy Shemin
Trofimuk Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation
(corresponding author:burshteinlm@ipgg.nsc.ru)
The present study is considered regional in scope,
aiming to refine on the conceptualization of
hydrocarbon accumulation processes in the area of
northern, the deepest part of West Siberian basin
including the Kara Sea off-shore area.
The main processes of hydrocarbon generation in the
basin took place in Later Cretaceous and Cenozoic.
Three distinctly different stages have become
apparent over its geological history, each of them
being equally important for the evolution of oil and gas
generation and accumulation in the north of the West
Siberian basin; however, the nature of processes
occurred during those stages proved crucially distinct.
The separation of the stages was driven by global
geodynamic and climatic changes.
During the Palaeogene time, which is comprised in
the first stage, likewise in Mesozoic, the West
Siberian geocyneclise continued downwarping. There
accumulated thick strata of Paleocene, Eocene and
Oligocene sediments, with the temperature of rocks
in the Jurassic and Cretaceous complex continuing to
grow, and the processes of katagenetic
transformations of organic matter occurring actively,
accompanied by the intense generation of liquid and
gaseous hydrocarbons.
The second stage began late in Late Oligocene and
continued throughout all the Neogene. At this stage,
in close connection with the history of the Arctic
Ocean evolution, proceeded the uplift of the northern
portion of the geosyneclise and the intense erosion of
the previously accumulated sediments. The
temperatures rising during the uplift ceased to
increase in the sedimentary cover. As a result, the
generation of hydrocarbons either slowed, or ceased.
The third stage began in Late Pliocene and comprised
the entire Pleistocene. It is associated with the drastic
cooling of climate in the northern hemisphere,
followed by the permafrost and thick ice sheets build
up, which radically changed the thermodynamic
conditions of the sedimentary cover and also had a
significant impact on the formation of hydrocarbon
accumulations.
Geological model of the study area, reflecting its
modern state, contains a set of regional structural
maps for Jurassic, Cretaceous, and Cenozoic
reference horizons, actual thicknesses maps for some
separate stratigraphical complexes with established
lithological varieties, as well present-day
temperatures and heat-flow maps; thickness maps for
rocks eroded in Cenomanian –Cenozoic, and glacier
and permafrost thickness maps. The model includes a
series of paleo-geographic maps for various time
intervals.
The work defines the main source-rock complexes
and the type of OM predominant in them, as well as
its modern and initial concentrations. Some special
geochemical studies done resulted in building
schematic maps for katagenetic transformation of
OM and Corg content, complemented by geochemical
characteristics of OM of oil-and-gas –source rocks,
and oils, gases and condensates derived from them.
In addition, the evaluation of kerogenes‘ kinetic
parameters was carried out for basic types of oil and
gas source-rocks. Assessed were both the dynamics
and scales of hydrocarbons generation therewith, and
the phase composition of the products generated.
Analyzed the relations of timing of seals formation
(lithification), timing of traps formation and the phases
of HC generation by various types of source-beds. A
special attention was called to early katagenetic
hydrocarbons generation.
In the study to follow the mentioned geological and
geochemical modeling, there were built variouslyscaled
4D (3D+T) models of oil and gas generation,
migration and accumulation simulations both for all
the study area and with the focus on some local
zones within its borders.
236

P-094
Marine transgressional event during the Early Cretaceous in
southeastern China: organic petrological and biomarker
evidences
Zhijun Jin 1 , Jian Cao 2 , Xulong Wang 3 , Wenxuan Hu 2 , Suping Yao 2
1 Exploration and Production Research Institute, SINOPEC, Beijing, China, 2 Department of Earth Sciences,
Nanjing, China, 3 PetroChina Xinjiang Oilfield Company, Karamay, China (corresponding
author:jcao@nju.edu.cn)
The Early Cretaceous in southeastern China has
been widely believed to feature a volcanic eruption
intercalated with non-marine deposition, with the
exception of some marine records (paleontological in
particular) along the roughly NE-SW trending
coastline due to marine transgression. Furthermore,
the transgression has been suggested to be held up
by the famous NE-SW trending Zhenghe-Dapu fault,
which is roughly parallel to the coastline. However,
the fault may not activate during the Early Cretaceous
and has started to activate since the Late Cretaceous
according to some tectonic studies. Thus, whether the
transgression has records in the area west to the fault
is an important scientific issue, implying for the activity
of the fault and the intensity of marine transgression.
In this study, dark mudstones samples were
collected from sites west to the Zhenghe-Dapu fault,
including mudstones from the Bantou Formation (K1b)
in Fujian province, Shouchang (K1s) and Guantou
formations (K1g) in Zhejiang province. They were
conducted by an integrated paleontological and
biomarker study. The paleontological
microobservation showed that typical marine fossils
such as red and brown alga are present besides
higher plants. Biomarker features also indicate marine
signatures, such as detection of gammacerane with
the ratio of gammacerane to C30 hopane ranging from
0.11 to 0.18, detection of C30 diahopane,

P-095
Natural petroleum fractionation – what do we really mean?
Chris Cornford
IGI Ltd, Bideford, United Kingdom (corresponding author:chris@igiltd.com)
Fractionation is defined as the separation of a mixture
into some or all of its component parts. Petroleum can
be considered a mixture in terms of molecular types
(homologues), carbon number (‗size‘ of molecule) &
stable isotopic composition (typically carbon +
deuterium). Petroleum fractionates at a number of
points during the life of a petroleum system: during
generation from kerogen in the source rock, during
expulsion from the source, migration and phase
separation on the way to a primary trap, during
remigration from trap to trap (stacked reservoirs or
Gussau displacement), and finally to survival within
the reservoir to the present day (various alteration
processes). At low temperatures biochemical
(bacterial) processes can also lead to isotopic
fractionation. The re-mixing of fractionates (e.g.
thermogenic with biogenic methane or fresh with
biodegraded oil) is also an additional complication.
Processes leading to fractionation at the bulk,
molecular and isotopic levels are listed in Table 1.
Table 1: A summary of processes potentially
leading to compositional or isotopic fractionation.
Term used Process
Pressure (buoyancy)
Effect (proven
or predicted)
Migrational
fractionation
gradient leading to
fluid flux of a single
phase through low
permeability/high
tortuosity porosity or
fractures
Strong light
molecular and
isotope
fractionation 2
Adsorption
geochromatography
Migrating petroleum
molecules partition
between fluid phase
and solid kerogen &
minerals
Strongest for
migration
through coals;
gas isotopic
fractionation?
Phase
separation 1
P-T control - starts at
bubble or dew point
boundary and
continues
progressively with
up-dip migration
Strong bulk,
medium
molecular but
little isotopic
fractionation 2
Diffusion 1
From high to low
concentrations so
requires gradient
Transient
compositional
effects, esp. for
Water
washing
Requires active flux
of external fluid
gases 4
Strong
compositional
Gas
washing/
stripping 1
Biodegradation
Biogenic
gas
Gravity
segregation
(water +/- dissolved
solids i.e. ‗salinity‘)
Requires active flux
of external fluid (gas,
typically methane but
could be CO2, N2)
Preferential bacterial
attack on � 13 C3
(residue) and isotopic
fractionation of CH4
and CO2 products
(fractionate)
Biochemical
fractionation of CH4
(a bacterial metabolic
waste product) with
respect to substrate
(proto-kerogen)
‗Heavy‘ molecules
separate to base of
accumulation or
reservoir
but minor
isotopic
fractionation 3
Strong
compositional
but little
isotopic
fractionation 5
Bulk &
molecular
changes +
isotopic
fractionation of
gas & CO2
Isotopic
fractionation
only since
product is pure
methane 6
Mostly bulk
and molecular
fractionation;
can be seen for
gases
1 a confusion of these processes is commonly termed
‗evaporative fractionation‘; fractionation it is but
evaporation it is not! 2 common to most oils; 3 examples
from foredeep basins; 4 examples from top and base
seal of deltaic sands; 5 stacked reservoir sands; 6 can
be mistaken for products of diffusional fractionation
The presentation reviews the geochemical literature,
quantifies these processes using simple physical
chemistry, and shows that the results of the
calculations agree with composition and isotope
gradients observed in exploration and production
wells.
238

P-096
Analysis on hydrocarbon accumulation and key controlling
factors of oil & gas accumulation in the Qaidam Basin, NW
China
Shihu Fang 1,2 , Mengjun Zhao 1,2 , Shuichang Zhang 2 , Dade Ma 3 , Yongshu Zhang 3 , Yan
Chen 3
1 Key Laboratory of Basin Structure and Petroleum Accumulation, CNPC, Beijing, China, 2 Research Institute
of Petroleum Exploration and Development, Petrochina, Beijing, China, 3 Qinghai Oilfield Company,
Petrochina, Dunhuang, China (corresponding author:shfang@petrochina.com.cn)
The three tectonic events and uplift around the
Qaidam basin and peripheral areas were mostly
related to the tectonisms during the middle-late
Himalayan Period, due to the distant influence of the
India-Tibet collision. The hydrocarbon generation,
migration and accumulation in Qaidam basin were
controlled by these tectonisms, as showed in the
influences of tectonic events on evolution of source
rock, formation of trap and reservoir-cap rock play,
fault system, and stages of hydrocarbon charging. All
the controlling factors led to differential distribution of
oil and gas in the Qaidam badin.
As study proved, there developed two-type of
accumulation models in the western Qaidam basin,
formed by the combination between the two stages of
hydrocarbon accumulation in this area. One is the
accumulation during the last stage of N2 1 or combined
with that during N2 3 -Q in the south part of western
Qaidam, and the other is that accumulating during
N2 3 -Q in the north part of western Qaidam. The twotype
of accumulation models can be subdivided into
four types. The structural formation during the late
Himalayan Period and its relationship with critical
period of accumulation led to differences in
hydrocarbon accumulation and related key controlling
factors. The differential response of late tectonic
events, major source rock evolution and fault system
are the three key factors that led to the obvious
differences of reservoir forming characteristics and
models between the north part and south part of the
western Qaidam. The role of fault in hydrocarbon
accumulation is analyzed according to the coupling
relationship between fault active periods and
hydrocarbon accumulation periods. Oil and gas
reservoir-controlling mode of faults is subdivided into
4 types: early accumulation-late preservation type,
early accumulation-late adjustment type, late
accumulation type and late dissipation type. The first
three types are main goals of oil and gas exploration
in western Qaidam basin, and deep reservoirs are still
the main target layers of exploration.
The unique strike slip-compressional tectonic settings
in northern Qaidam were formed due to intensively
strike slip and related compression in the late
Himalayan Period. The strike slip-compressional
tectonic system mainly composed of three types of
structures: broken strike slip -compressional structure
before mountain, broken strike-slip structure and
adjusted strike slip structure. Two stages of
hydrocarbon accumulation during the Himalayan
period and its combination with accumulation
conditions and structural formation determined the
continuing palaeo-structures since early Himalayan
period can be advantageous area for oil and gas
exploration in the northern Qaidam. But the
hydrocarbon distribution became complex due to the
adjustment and destruction of strike-slip tectonism.
The control of strike slip-compressional tectonic
system on hydrocarbon accumulation and distribution
and its combination with palaeo-structure, source rock
evolution and generation of oil and gas imply palaeostructure
flanks toward depression can be
advantageous exploration areas for hydrocarbon
enriched.
Key words: Qaidam basin, strike-slip compressional
tectonic system, hydrocarbon accumulation model,
differential accumulation, key controlling factor.
239

P-097
Geochemistry of low-boiling С5-С8 hydrocarbons from Middle
Ob’ oils (West Siberia)
Elena Fursenko
Trofimuk Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation
(corresponding author:fursenkoea@ipgg.nsc.ru)
The object of this study is C5-8 hydrocarbons (HC) in
oils from the Mesozoic deposits (K1 - 47 samples, J3 -
20 samples, J2 - 12 samples) in the Middle Ob‘ region
of West Siberia. Additionally, it was used another data
on physical and chemical composition (density; sulfur
and paraffins contents; structural and group
composition; V and Ni content; δ 13 С of saturated and
aromatic fractions), geochemical parameters by the
composition of n-alkanes C10 +, acyclic isoprenoids,
high polycyclic hydrocarbon biomarkers (steranes,
terpanes).
The comparative analysis of the C5-8 HCs distribution
in the studied oils points to the aquagene genesis of
the organic matter they were, mainly, formed of /3/. By
a bigger half, the group composition of C5-8 HCs in
these oils is represented by alkanes, light arenes
concentrations are low, the values of cyclopentanes/
cyclohexanes ratios are high (> 0,7), as well as those
of ethylbenzene/ xylenes (> 0,3), and n-heptane/
methylcyclohexane (> 0,9); the values of m-xylene/ oxylene
ratios are low (< 2,0). Genetic parameters in
the context of high-molecular saturated hydrocarbons
composition (low values of n-C27/ n-C17 - < 0,4,
pristane/ phitane - < 1,5, C29 steranes/ C27 steranes
2,0), and light isotopic composition
(δ 13 C < -30,0 ‰) altogether attest to the genotype of
the studied oils being aquagene /1, 3, 5, 6/.
These oils are most likely to have derived from
organic matter (OM) of the Bazhenovo Fm /2, 4/.The
differences observed in the studied oils, can be
explained by differences in biogeochemical facies of
the Bazhenov Sea (the oxidation-reducing conditions
of diagenesis, hydrodynamics and salt regime of the
sea basin, and possibly, the biota). On the other
hand, the vertical migration of oil components from
source-rock stratum J1-2 with mixed composition of
OM (aquagenous - terragenous, terragenous-
aquagenous) can not be excluded /2, 4/.
Several samples from the examined samples from
J2 deposits differ significantly both in terms of C5-8
hydrocarbons composition (cyclopentanes/
cyclohexanes < 0,4); ethylbenzene/ xylenes < 0,1;
m-xylene/ o-xylene > 2,0) and by the high-molecular
hydrocarbon biomarkers composition (pristane/
phytane > 3,0; C29 steranes/ C27 steranes > 1,0,
elevated concentrations of tricyclanes C19-20, etc.).
Such characteristics of hydrocarbon composition are
indicative of their genesis being predominantly
terragenous /1, 3, 5, 6/. The source of these oils could
have been the OM accumulated in shallow-water
marine and lacustrine facies in the Lower-Middle
Jurassic time /2, 4/.
In general, the studied oils are mature. Similar
maturity of hydrocarbon fluids caused the insignificant
scattering of katagenesis coefficients in the
composition of light HСs. Furthermore, the ratio of
even и odd n-alkanes (CPI) in most samples is ≈1. The
data on the steranes‘ and terpanes composition also
prove the studied oils to have been formed in the ―oilwindow‖
zone /1, 3, 5, 6/.
Some single samples from the studied oils showed
low value of some ratios (С5-8 alkanes/ С5-8 cyclanes,
n-heptane/ methylcyclohexane, n-alkanes/ isoalkanes),
and high coefficient Kiso = (Pr+Ph)/ (n-C17+n-C18).
N-alkanes С10+ are not identifiable in these oils. They
are confined to the Lower Cretaceous shallow-depth
deposits with low formation temperature (≤ 70-75 0 С).
The distributions in the steranes and terpanes
compositions, likewise in oils diagnosed as aquagenous.
Therefore, these oils can be considered biodegraded to
a moderate degree /3/.
References
[1] Hunt, J.M., (1982). Petroleum geochemistry and
geology. (in Russian) Moscow: Mir, p. 703
[2] Kontorovich, A.E., et al. (1975). Geology of oil and
gas of West Siberia: Moscow, Nauka, 679p
[3] Peters, K.E. The biomarker guide/ 2 nd ed./
K.E. Peters, C.C. Walters, J.M. Moldovan/ USA, New
York: Cambridge University Press, 2007. – P. 1155
[4] Petroleum-bearing basins and areas in Siberia.
Edition 2. West Siberian basin/ Edited by
А.E. Kontorovich. Novosibirsk: UIGGM SB RAS,
1994. p. 200
[5] Petrov A.A. (1984) Hydrocarbons of crude oil.
Moscow: Nauka, p.243
[6] Tissot, B. P. and Welte, D.H., (1981). Petroleum
Formation and Occurrence. (in Russian) Moskow: Mir,
p. 502
240

P-098
Differential entrapment of charged oil - new insights on
McMurray formation oil trapping mechanisms
Milovan Fustic 1,2 , Barry Bennett 2 , Haiping Huang 2 , Thomas Oldenburg 2 , Stephen
Hubbard 2 , Steve Larter 2
1 Nexen Inc., Calgary, Canada, 2 University of Calgary, Calgary, Canada
The Lower Cretaceous McMurray Formation is the
primary host of the Athabasca oil sands deposit, one
of the largest petroleum deposits in the word.
Regional studies shows that bitumen saturated
reservoir sands are encountered within the central
and western part of the basin, while the eastern part
of the basin has never been charged by petroleum.
The lateral contact between petroleum and water
saturated reservoir sands is characterized by rapid
changes in bitumen saturation even between closely
spaced wells and different petroleum entrapment
schemes have been employed to explain the trapping
mechanism of this vast resource, but they still remain
a matter of great debate.
In this work integration of a reservoir charging and an
inter-compartmental reservoir charging and spillingmixing
petroleum geochemical model combined with
the detailed knowledge of reservoir architecture
allows us to look at petroleum ―fill and spill‖ among
lateral reservoir compartments separated by mud
filled channel sections as part of the trapping
mechanism. Classical molecular maturity parameters
measured by gas chromatography - mass
spectrometry of bitumen from neighboring reservoir
compartments show notable changes confirming that
compartments at the eastern edge of the Athabasca
oil sands are sometimes filled by separate petroleum
charges.
Implications for reservoir development are immense,
including using the principles and geochemical
gradients as a tool for defining the presence and the
extent of individual compartments as an aid to well
placements. The results also suggest oil charge was
very limited locally and individual compartments may
not have seen the multiple charges evident in the oil
sands to the west. The concepts presented should be
applicable to other meandering fluvial belt reservoirs
worldwide and suggests a necessity to revise existing
stratigraphic trap schemes by including stratigraphic
trap compartmentalization as one of the trapping
mechanisms.
241

P-099
Oxygen-containing compounds in crude oils of south-eastern
part of West Siberia
Eugenia Strelnikova 1 , Ivan Goncharov 2 , Olga Serebrennikova 1
1 Institute of Petroleum Chemistry SB RAS, Tomsk, Russian Federation, 2 TomskNIPIneft, Tomsk, Russian
Federation (corresponding author:seb@ipc.tsc.ru)
Crude oils contain about 1% of oxygen in form of
various oxygen-containing compounds (OC) which
are mainly distributed among high-molecular
petroleum components - resins and asphaltenes. At
present time numerous works prove the sulfur nature
in crude oils. Abundantly clear that petroleum nitrogen
is inherited from proteins, lipid compounds (pigments)
and complex fats (phospholipids) of primary
organisms. However there is no uniform point of view
about an oxygen origin in oils.
More than 50 tests of crude oils a southeast part of
Western Siberia of deposits in a range from the Lower
Cretaceous to a Paleozoic are analyzed. The content
of sulfur (S), nitrogen (N), oxygen (O), carbonyl
groups of ketones (CO), carboxyl groups of acids
(COOH) and hydroxyl groups of phenol (OH) was
defined.
It is known that the structure and quantity of formed
hydrocarbon fluids are influenced very strongly by
depth of oxidation of organic matter (OM) in initial
processes of depositions. Anoxic conditions promote
preservation of unstable and active moieties
containing O, S and N, inherited from live ОM which
give rise to oils heteroatom compounds eventually
(fig. 1). It is not so important that there is a negative
correlation between the content of various classes OС
and Pr/Ph as that there is a close interrelation
between oxygen and nitrogen compounds. It means
that their quantity in oil is supervised by the same
group of factors. As petroleum nitrogen is inherited
from connections of the albuminous nature of live
organisms hence petroleum oxygen also is relic, i.e.
inherited from a biomass, and has not been
introduced in petroparent ОM as a result of its
oxidation at stage of sedimentation. Negative
correlation between OC and Pr/Ph specifies that
biomass transformation at a stage of its deposition
proceeds with loss of basic oxygen functional groups
and the oxygen as a whole. Products of oxidation
formed thus aren't involved in structure OM, dropping
out on a bottom, and mineralized to water and
carbonic gas.
Thus, the high content of oxygen is characteristic for
oils, whose initial ОM wasn't exposed to deep aerobic
oxidation at a stage of sedimentation. Often these oils
Content, %
2.00
1.00
Marine Oils
Terrestrial Oils
0.00
0.0 2.0 4.0 6.0 8.0
Pr/Ph
O
CO
S
COOH
Fig.1. Relationships between Pr/Ph ratio and S, N, O and
OC content of the samples of oils from the south-eastern
part of West Siberia
are the heaviest and resinous that gives the grounds
to some authors to name them «oxidized, unripe, oils
of early generation» etc.
Now deposits of all investigated oils are on different
depths and at different temperatures (70-115 °С) that
also could affect quantity and structure of OC. The
Isoprenoid parameter (Ki) and dibenzothiophene ratio
(4МDBT/1МDBТ) are the convenient parameters
characterizing degree of thermal influence on ОM and
oils. It is remarkable that factors of correlation of
these parameters with content OC and others
heteroatoms have appeared not significant. This
result once again specifies that in a range of
temperatures in oil reservoir 70-115°С processes of
thermal transformations don't make essential impact
on the general properties of oil (density, viscosity,
quantities resins and asphaltenes and their structure).
Possibly, here the leading role belongs to processes
of primary and secondary migration (migration
distance, mineralogical and granulometric
composition of rock on a way migration).
OH
N
242

P-100
Diversity of source, biomarkers composition and maturity of
crude oils in Zechstein Main Dolomite deposits, NW Poland
Cezary Grelowski 1 , Franciszek Czechowski 2
1 Polskie Gornictwo Naftowe i Gazownictwo SA, Oddzial w Zielonej Gorze, Pila, Poland, 2 Faculty of Earth
Science and Environmental Management, University of Wroclaw, Wroclaw, Poland (corresponding
author:cezary.grelowski@zgora.pgnig.pl)
Zechstein Main Dolomite (Ca2) deposits are the
most perspective oil-bearing horizon in NW Poland.
Over earlier years till the end of 2010, more than 70
crude oil accumulations have been discovered mainly
in traps of structural type, which occur in evaporitic
system carbonate rocks, the most frequently within
platforms (Stassfurt cyclothem). In Poland the largest
oil accumulations are Barnowko-Mostno-Buszewo
(BMB) and Lubiatow-Miedzychod-Grotow located in
Wielkopolska petroleum province (Gorzow Block and
southern part of Szczecin Trough).
The onset of petroleum generation from the Ca2
source rocks occurred from the Late Triassic through
the Tertiary period. Liquid hydrocarbon (HC) shows
and accumulations represent variable molecular
composition and maturity. However, there is no clear
and continuous horizontal trends in the gradient of
selected geochemical parameters. In larger scale
variability is more perceptible than in smaller regions.
In this work oils from 70 wells deriving from Western
Pomerania, Gorzow Block and Fore-Sudetic
Monocline regions were analyzed. Their geochemical
characteristics on biomarkers composition were
achieved from GC-MS analyses of aliphatic and
aromatic fractions. The data allowed to group oils of
common source.
Oils occurring in western part of the Western
Pomerania (Blotno-1, Kamien Pomorski-5, -25,
Wapnica-1, -2K, Rekowo-1, Wysoka Kamienska-1, -7
wells) were sourced from type II kerogen deposited
under reducing conditions in carbonate matrix. It is
indicated by CPI values of n-alkylcyclohexanes above
unity (from 1.16 to 1.38) and elevated relative
concentration of C21 homologue in n-alkylbenzenes,
occurrance of phytanylbenzene and phytanyltoluene
as well as gammacerane, predominance of C35
homologues of extended hopanes. Clay minerals
presence within carbonate matrix is reflected by
abundant diasteranes. Biomarker maturity indices are
in the range of initial stage of oil window and oil peak
generation (0.55 – 0.8% Rr). Wells from the central
part of this region (Petrykozy-7, Daszewo R-1K, -14
and Sidlowo-1) comprise oils of similar origin, which
direction of maturity increase is towards east (Rr of
0.55, 0.80, 1.0 – 1.1% and MDR within 2.46 – 4.38
range, accordingly). Bimodal distribution of n-alkanes
and n-alkylbenzenes is observed in Sidlowo-1 oil. A
high MPI1 value (1.35) of this oil is interpreted as due
to the HC inflow from the Zechstein surface
underlying strata. Crude oils of eastern part of region
(Brzozowka-1a, Drzonowo-1, Wilcze IG-1 wells)
derive from type II kerogen deposited in marine
environment under highly reducing conditions (nalkanes
CPI of 0.97 – 0.99, elevated concentration of
C35 extended hopanes, etc.). Oils maturities are in the
range of peak HC generation and transition oil
window through. They positively correlate with
respective maturity indices of the source kerogens.
Oils from the Gorzow Block are distinct by
increased maturity and molecular composition of
biomarkers. The maturity level evaluated from
distribution of alkylaromatic HCs is within Rr range of
1.0 – 1.3%. They are lacking steranes as well as
hopanes due to their aromatisation. Based on
correlations of Pr/n-C17 (0.44 – 0.62) and Ph/n-C18
(0.68 – 1.11) ratios the oils derive from type II
kerogen of marine carbonate environment. Liquid
HCs are epigenetic and their migration was driven by
geothermal gradient. Namely, for oils of Zielin-2, -3K,
Marwice-1, Rozansko-1, -4 and Namyslin-1 wells
(partly generated from type III kerogen) the
decreasing maturity trend proceeds from north to
south of the region (Rr from >1.3 to 0.8%).
Oils in Ca2 deposits of the Fore-Sudetic Monocline
contain benzohopanes, which is in accordance with
HCs low maturity (0.55 – 0.75% Rr). Oils originate
from type II kerogen of marine environment (Gorzyca-
2, -3, Chartow-6, Jeniniec-1, Kosarzyn-2, -8 and
Cychry-2 wells). In the eastern part of this region oils
exhibit higher maturity level.
References
Czechowski F. et al. (1998) Geol. Rev. 46, 171-177.
Kosakowski P. et al. (2003) Geol. Rev. 51, 663-672.
243

P-101
Formation of giant deep-buried old heavy oil reservoirs below
7000m in Tarim Basin,China
Zhu Guangyou, Zhang Shuichang, Su Jin, Gu Lijing, Wang Yu, Zhang Bin
Research Institute of Petroleum Exploration and Development, PetroChina, Beijing, China (corresponding
author:zhuguangyou@petrochina.com.cn)
Giant heavy oil pools were discovered in deep buried
Ordovician carbonate reservoirs (6500~7000m) in
Tabei area of Tarim basin, China. Ground oil density
ranged from 0.92 g/cm 3 to1.05 g/cm 3 (20℃), viscosity
from 20 to 9142 mPa.s, solidifying point from -16℃ to
-30℃, paraffin content from 2 to 14%,sulfur content
from 0.5 to 3.2%, resin and bitumen from 7 to
20%,average initial gas/oil ratio was 50m 3 /m 3 . All
were non-saturated reservoir. The daily oil production
of heavy oil wells ranged from several tens to several
hundreds m 3 , gas production rate was lower and
averaged at several thousands m 3 . Exploitation were
carried out by adding light oil to heavy oil reservoir.
Analysis of biomarkers indicated that deep heavy oil
major originated from middle-upper Ordovician source
rocks in south depression. High concentration of C25norhopane
showed in mass chromatogram m/z=177
and chromatography of crude oil had obvious bulging
baseline both implied oil had been severely
biodegraded.
Fluid inclusions data obtained from Ordovician
carbonate reservoirs showed hydrocarbon charged
during late Permian. Homogenization temperatures of
fluid inclusions from well H601-4 Ordovician sparite
reservoir(6654m) were concentrated in 83~89℃, fit
the thermal history curve(Fig 1) at late Permian.
Tabei area experienced long time deep bury and
subsidence from Triassic and Ordovician paleohydrocarbon
reservoirs were well preserved.
Densification of Ordovician oil was happened during
late Permian, degradation happened after charging.
Tabei heavy oil reservoir was an old hydrocarbon
system which accumulated before 250Ma and
degraded and experienced long time deep burial.
In conclusion, Deep reservoir of Tabei area in Tarim
basin had large distribution of heavy oil resources,
which formed before 250Ma and was a old deep
heavy oil reservoir. The low geothermal gradient and
quick deep burial since 5Ma were both important
conditions for the preservation of deep heavy oil
reservoir.
Fig 1 Burial history curve of well H601-4 and
distribution diagram of homogenization temperatures
of fluid inclusions
Fig 2 Marine hydrocarbon accumulation in the
northern Tarim Basin evolution profile (N-S direction)
Notes: ①before the sedimentation of upper
Ordovician, sedimentary strata was exposed and
formed karst reservoirs; ② before the sedimentation of
Devonian, strata uplifted, Silurian denuded, enhanced
formation of the karst reservoirs; ③late Hercynian(late
Permian),oil originated from middle-upper Ordovician
source rocks charged from north to south along the
Ordovician karst reservoirs, formed hydrocarbon
pools; ④ before the sedimentation of Triassic,
tectonic uplifted and hydrocarbon in Ordovician
reservoirs biodegraded and formed heavy oil; ⑤since
the sedimentation of Mesozoic, Ordovician reservoirs
experienced sustain quick burial and the paleoreservoir
was well preserved
244

P-102
Origin of Solid bitumen of guizhong 1 in the guizhong
depression, SW China: evidence from carbon isotopes and
biomarkers
Xunyun He 1,2,3 , Genshun Yao 1 , Xianghua Xiong 1 , Chunfang Cai 2 , Anjiang Shen 1 , Xiaosu
He 1
1 Hangzhou Research Institute of Geology, PetroChina, Hangzhou, China, 2 Institute of Geology and
Geophysics, Chinese Academy of Sciences, Beijing, China, 3 Graduate University of Chinese Academy of
Sciences, Beijing, China (corresponding author:hexy_hz@petrochina.com.cn)
The Guizhong Depression is located in the centre
of Guangxi Province, China. It is a large marine
sedimentary unit with an area of 4.6×10 4 km 2 and a
gross thickness of more than 8,000m from the
Devonian to Carboniferous. A total of 47 wells were
drilled to date (December, 2010) in the area, only 7 of
which have the depths of more than 1000m. The
deepest well, the Guizhong 1, was drilled in 2007 to a
depth of 5151.86m and completed in the Lower
Devonian Nagaoling Formation (D1n). Lots of solid
bitumen have been found in the well and filled in
porosities and fractures of limestone and dolomite
from four intervals with a total thickness of 709m. This
is an exciting finding which probably indicates that it
has good oil and gas exploration prospect in the
Guizhong Depression.
In order to elucidate the origin of the solid
bitumen, twenty six solid bitumen samples from the
Devonian in the Guizhong 1, and twenty one potential
source rock samples from the Lower-Middle
Devonian(D1-2) of the Guizhong Depression and the
Lower Cambrian Niutitang Formation (Є1n) of the
adjacent Qiannan Depression were analyzed for
δ 13 C(PDB) values and biomarkers.
The results show that firstly the solid bitumen
samples have bulk δ 13 C values from -27.4‰ to -
23.0‰, average-25.8‰(n=26), and the individual
normal alkanes (nC15-nC29) δ 13 C values from -31.0%
to -28.2%. The values are well-correlated with bulk
δ 13 C values from -27.4‰ to -24.8‰, average -26.4‰
(n=13) and the individual normal alkanes (nC15-nC29)
δ 13 C values from -32.3‰ to -28.9‰ of the Lower-
Middle Devonian source rocks, respectively. While the
Niutitang Formation source rocks (Є1n) have bulk
δ 13 C values from -35.8‰ to -30.8‰, average -
34.0‰(n=8), which dramatically distinguish from that
of the bitumens and the Lower-Middle Devonian
source rocks(Fig.1). Importantly, the bitumens and the
Lower-Middle Devonian source rocks show similar
distribution pattern of the individual normal alkanes
(nC15-nC29) δ 13 C values. Secondly, they are both
relatively rich in tricyclic terpanes and C30 hopane,
and poor in gammacerane, while the Niutitang
Formation source rocks are relatively rich in
gammacerane and C30 hopane, and poor in tricyclic
terpanes(Fig.2). Finally the bitumens and the Lower-
Middle Devonian source rocks have no triaromatic
steroids, while the Niutitang Formation source rocks
are relatively rich in them.
In summary, it can be concluded that solid
bitumen of Guizhong 1 must have been derived from
the Lower-Middle Devonian source rocks based on
carbon isotopes and biomarkers distribution.
Moreover, the δ 34 S values of the solid bitumen
and potential source rock samples are analyzing for
further supporting proof.
-36.0 -34.0 -32.0 -30.0 -28.0 -26.0 -24.0 -22.0
δ 13 C value(‰,PDB)
1 2 3
Fig.1 Correlation of bulk δ 13 C values between
bitumens and potential source rocks.1. bitumens(D1-3)
of Guizhong 1; 2.source rocks (D1-2) in Guizhong
Depression;
Depression
3. source rocks (Є1n)in Qiannan
M/Z191
GZ-26,D 3 ,bitumen
GZ-68,D 2 ,mudstone
YTZ9-T 1 ,Є 1 n,mudstone
C30h
Fig.2 Correlation of terpane fingerprint of the bitumen
and the potential source rocks
G
245

P-103
Geochemical characteristics of crude oils from the Murzuq
Basin, Libya
Tarek Hodari, Paul Philp
School of Geology and Geophysics, University of Oklahoma, Norman, United States of America
(corresponding author:pphilp@ou.edu)
The study area is situated within the Murzuq Basin
of Southwest Libya. Murzuq Basin is an intra-cratonic
sag basin situated on the North African Saharan
Platform (Aziz ,2000; Echikh and Sola, 2000; Fello et
al., 2006). The Palaeozoic sediments within the basin,
comprised of Cambrian, Ordovician, Silurian,
Devonian and Carboniferous rocks, are
unconformably overlain by up to 1500m of Mesozoic
continental deposits and Cainozoic sequences. The
maximum depth to Precambrian basement reaches
up to 3500m in the central part of the basin. The lower
Silurian Tanezzuft Formation (hot shale) and Middle-
Late Devonian Awaynat Wanin Formation shale are
thought to be the main source rocks along with other
local source rocks. These have been recognized
within Palaeozoic sequences, and have contributed to
charging of the Palaeozoic and Mesozoic reservoirs in
the Murzuq Basin. Only one effective petroleum
system (Tanezzuft-Mamuniyat) has been found in the
Murzuq Basin to date, although others may remain to
be discovered.
Twenty crude oil samples from the Murzuq Basin
(NC-115 Concession) were used for this study.
Complete removal of asphaltenes from oils was
assured by using n-pentane, and the maltenes were
subsequently fractionated into saturate hydrocarbons,
aromatic hydrocarbons, and polar compounds using
high-performance liquid chromatography (HPLC).
Analytical techniques such as gas chromatography
(GC) and gas chromatography-mass spectrometry
(GCMS) were used to characterize the saturate
fractions. The distributions of n-alkanes, isoprenoids,
terpanes, and steranes were used to determine
organic matter (OM) composition, depositional
environment conditions, and extent of biodegradation.
Results reveal that the elevated values of
nC17/nC25 ratios in the n-alkane profiles suggest a
high input of marine-derived OM if not resulting from
maturity. However, values of Pr/nC17 vs. Ph/nC18
indicate that the crude oils were sourced from a
source rock of mixed marine/terrigenous OM inputs.
The predominance of C29 steranes, with relatively low
concentrations of C27 and C28 steranes, in all of the
oils may suggest higher inputs of terrestrial OM with
some contribution from marine OM and lacustrine
algae. The higher Pr/Ph ratios in all oils suggest that
these sediments were deposited in mixed oxic to suboxic
(high Eh) conditions as indicated by the high
concentrations of C30-diahopane, and high ratios of
diasterane/sterane in most of samples. The presence
of pregnane and homopregnane in all oil samples
suggest that these oils have been sourced from
sediments deposited under hypersaline conditions.
Based on the distributions of n-alkanes in all of
crude oils (ranging from C11 to C32), it appears that
these oils are non-biodegraded. Oil to oil correlations
permit the establishment of one genetic family that
has been divided into three subfamilies based on the
differences in the absolute concentration of
biomarkers, biomarker distribution pattern of steranes
(m/z 217) and triterpanes (m/z 191). These oils are
generally characterized by early to intermediate levels
of thermal maturity as indicated by the ratios of
ββ/(ββ+αα) and 20S/(20S+20R) as well as
22S/(22S+22R), and sourced mainly from source
rocks of mixed marine/terrestrial organic matters with
higher inputs from terrestrial origin (Philp, 1985; Philp
et al., 1992).
Selected References
Aziz, A. (2000) Stratigraphy and hydrocarbon
potential of the lower Palaeozoic succession of
licence NC 115, Murzuq Basin, S.W. Libya.
Symposium on Geological Exploration in Murzuq
Basin (Eds. M.A. Sola and D. Worsley), Elsevier,
Amsterdam, p. 349-368.
Echikh, K., and Sola, M.A. (2000) Geology and
hydrocarbon occurrences in the Murzuq Basin, S.W.
Libya. Symposium on Geological Exploration in
Murzuq Basin (eds. M.A. Sola and D. Worsley),
Elsevier, Amsterdam, p. 175-222.
Fello, N., Lüning, S., Ńtorch, P., Redfern, J. (2006).
Identification of early Llandovery (Silurian) anoxic
palaeo-depressions at the western margin of the
Murzuq Basin (southwest Libya), based on gammaray
spectrometry in surface exposures. GeoArabia 11
(3), p. 101-118.
Philp, R.P. (1985) Fossil Fuel Biomarkers. Elsevier
Science Publishers B.V. New York, p. 294.
Philp, R.P., Chen, J.H., Fu, J.M. and Sheng, G.Y.
(1992) A geochemical investigation of crude oils and
source rocks from Biyang Basin, China. Org.
Geochem. Vol. 18, No. 6, p. 933-945.
246

P-104
Effect of PDC-bit platelets on geochemical data quality and
hydrocarbon-systems evaluation
Daniel Jones, Cara Davis, Holger Justwan, Lloyd Wenger
ExxonMobil Upstream Research Company, Houston, United States of America
Over the past two decades, technological advances in
polycrystalline diamond compact (PDC) bits have led
to increased drilling efficiency and prolonged bit life.
As a result, PDC bits are now more widely used than
traditional roller-cone bits. PDC-bits, however, alter
rock textures potentially impacting geochemical data
quality and hydrocarbon-systems evaluation in
frontier-exploration areas.
The formation of PDC-bit platelets is one component
of a spectrum of drill-bit generated artifacts, ranging
from slight textural alteration to extensive drill-bit
metamorphism (DBM) where partial melting and
quenching result in glassy cuttings (Wenger et al.
2009). Even when DBM is not severe, drill cuttings
generated by PDC-bits have an unnatural ‗platelet‘
texture (Figure 1) that suggests the rock has been
compromised. Previously, little was known about the
structure and composition of PDC-bit platelets, and
whether platelet formation itself alters geochemical
parameters in the absence of severe DBM.
As cuttings are a primary source of geologic and
geochemical information, it is critical to understand
the effect of PDC-bit platelets on geochemical data
quality and if parameter correction is possible. The
effect on data quality was evaluated by comparison of
data gathered from analysis of platelets and cores
from the same depth using a sample set from several
wells representing a range of lithologies and drilling
conditions. Platelets were observed to form in finegrained
sediments, including shales, siltstones,
evaporates, and limestones. However, within this
sample set SEM and XRD analyses of shale platelets
show that the ‗plates‘ are composed of putatively
unaltered sediments that retain their original
elemental composition and mineralogy. All platelets
are contaminated to varying degrees by drilling mud
solids that partially fill the areas between the plates
and this contamination offsets elemental and organiccarbon
analyses between core and cuttings. TOC
values from platelets are systematically shifted with
respect to cores, suggesting addition of drilling mud
solids. Rock-Eval measurements are also affected by
organic additives in the mud, and the impact on
Hydrogen Index (HI) and Oxygen Index (OI) values is
significant enough that it could change source-rock
quality interpretations.
Results suggest that, with sufficient information on
elemental and organic composition of mud solids, it is
possible to ―correct‖ affected TOC and Rock-Eval
measurements if platelets have not experienced
severe DBM. Corrections have been developed to
add/subtract from TOC and Rock-Eval parameters
based on analyses of drilling muds for individual
wells. These findings provide support for when
geochemical analyses of PDC-bit platelets may
provide useful information versus when they are too
altered to yield meaningful data.
Figure 1. a) Picture of a PDC-bit platelet showing the
characteristic structure generated by the shearing
action of the drill-bit b) Secondary electron SEM
image of a PDC bit platelet showing contamination
with mud solids (predominantly barite) in-between
plates.
References:
Wenger, L.M., Pottorf, R.J., Macleod, G., Otten, G.,
Dreyfus, S., Justwan, H., Sekula-Wood, E. 2009. Drillbit
metamorphism: Recognition and impact on show
evaluation. SPE paper 125218 presented at the 2009
SPE Annual Technical Conference and Exhibition,
New Orleans, LA, 4-7 Oct.
247

P-105
Challenges on the origin of oil/condensate and presence of
bitumen and oil seeps in the Tanzania Coastal Basins
Meshack Kagya
Tanzania Petroleum Development Corporation, Dar es Salaam, United Republic of Tanzania
(corresponding author:mkagya@tpdc-tz.com)
Oil or condensates have been encountered in Songo
Songo and Mnazi Bay gas fields. In Songo Songo, the
oil/condensate are produced from the Albian and
Neocomian sandstone. Physically, they are colourless
to brown in colour with gravity ranging from 33 to 47˚
API. Isoprenoid to n-alkane ratios envisage a
transitional to peat-coal depositional environment of
parent organic matter. However, the carbon isotopic
signature (� 13 C12) of saturated and aromatic
hydrocarbon fractions, and other parameters correlate
to a restricted marine source. Diasterane/regular
sterane ratios (0.92) infer a highly mature source
origin (>1%Ro), whereas regular sterane ratios have
values around 0.52 and 0.6 suggesting a thermal
maturity of >0.7%Ro. A maturity value of ~0.8%Ro
was deduced from naphthalenes and phenanthrenes
ratios. Source rock of predominant terrestrial organic
matter is indicated in Songo Songo by lignitic
sediments encountered in Tertiary formations. On
pyrolysis they gave good hydrocarbon yield (13.8 to
71.5 kg/tonne), likely to source oil plotting in the peatcoal
zone of the isoprenoid/n-alkane cross plots.
However the Tertiary section in this region is quite
immature to generate neither oil nor gas. Therefore
the source of such oil is possibly being generated
from deeper shelf off Songo Songo Island.
Nevertheless another source could be restricted
marine source observed in Mandawa Basin west of
Songo Songo. In Mnazi Bay the Tertiary formations
produce oils/condensate with API gravity ranging from
18˚ to 32˚. Such gravities are apparently indicative of
heavy crude, contrary .to their physical appearance
and volatility They are maturity range between 0.67
and 0.77% Rc. Oleanane compounds are apparently
present indicating the input of Tertiary organic matter.
The source rock data from the Tertiary interval is
shown to be immature to generate the observed oil.
Several oil seeps and bitumen occur along the coast.
The bitumen occurs as bituminous sands and tar balls
along the shore line. The Gas Chromatograms of
extracts from some of bitumen and oil seeps have
light end hydrocarbon signature, thus an indication of
being active seeps. The origin for these seeps
remains debatable.
248

P-106
Organic geochemistry of naphthides of the Anabar-Khatanga
saddle
Natalya Kim, Vladimir Kashirtsev, Oksana Dzuba
Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation (corresponding
author:KimNS@ipgg.nsc.ru)
In the Anabar-Khatanga saddle, several small oil
fields are known and numerous bitumen shows have
been revealed in heterochronous deposits of natural
outcrops of the Nordvik Peninsula. The first
suggestions regarding the genesis of these
naphthides have been stated by one of the authors as
early as 2003 [1], based on the detailed molecular
analysis of oil from Permian deposits of well Yuzhno-
Tigyanskaya-102R. The present work is the
continuation of naphthide investigation in this area.
Using gas-liquid chromatography and gas
chromatography-mass spectrometry methods, oil from
well Nordvik-42 (T2) and natural bitumens from the
outcrops of Cape Yuryung-Tumus of the Nordvik
Peninsula (J1-2) have been analyzed.
The chromatograms of naphthides of the Nordvik
Peninsula show a ―naphthene hump‖ that suggests
biodegradation processes. In oils and some bitumen
extracts, where normal alkanes have still preserved,
the peak falls on n-C17 hydrocarbons. The Pr/Ph ratio
values are equal to 0.70-1.00. С30 squalane is present
in significant concentrations.
С27-С29 sterane hydrocarbons are dominated by С29
ethylcholestanes (45-47 %), and the value of
diasteranes to regular steranes ratio is not high, 0.13-
0.19.
Terpane hydrocarbons contain the highest
concentrations of hopanes, among which С29
adiantanes are predominant. С35 homohopanes
dominate over С34 homohopanes. Naphthides are
characterized by higher concentrations of
gammacerane. 28,30-bisnorhopane have been
identified, the appearance of which usually is related
to the existence of specific bacteria at the early
stages of OM transformation [2]. Besides, a series of
25-norhopanes (m/z 191, 384, 177, 355) have been
identified, which form due to microbial oxidation of
regular hopanes [2]. 3�-methylhopane, synthesized
by specific methanotrophic bacteria, has been found
in all of the studied naphthides. Tricyclic
hydrocarbons are dominated by С23-С24
cheilanthanes. Significant concentrations of С24
tetracyclic terpane are marked.
The values of isotopic carbon composition are equal
to -28.2 ‰ in Nordvik oil, and in the bitumens of Cape
Yurung-Tumus, the values vary from -29.6 to -29.2 ‰.
In these naphthides, the content of sulfur is 1.2-2.4 %.
The geochemical parameters indicate a single
genetic nature of the studied naphthides as well as
Yuzhno-Tigyanskaya oil, examined earlier [1].
Thus, the initial OM of naphthides of the Anabar-
Khatanga saddle has formed under the conditions of
highly saline Proterozoic-Lower Paleozoic marine
basin. According to geologic information, in the
considered region, salt strata are associated with
Devonian deposits [3] that require their further
investigation to establish naphthide – oil source rock
relationships.
References
[1] Kashirtsev V.A. Organic geochemistry of naphthides in
the east of the Siberian Platform. Yakutsk: SB RAS, YaD,
2003. – 160 p.
[2] Peters K.E., Walters С.C., Moldowan J.M. The
biomarker guide. 2 nd ed. – Cambridge University Press, New
York , 2005. – V. 2. – 1155 p.
[3] Kalinko M.K. Geologic history and petroleum potential of
the Khatanga depression // Proceedings of NIIGA, v. 104, L.,
Gostoptekhizdat, 1959, 353 p.
249

P-107
Caldera of the Uzon volcano as a natural laboratory of the
modern oil formation
Alexey Kontorovich 1 , Svetlana Bortnikova 1 , Gennadii Karpov 2 , Vladimir Kashirtsev 1 ,
Elena Kostyreva 1 , Alexander Fomin 1
1 Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation, 2 Institute of
Volcanology and Seismology FEB RAS, Petropavlovsk-Kamchatsky, Russian Federation
The advocates of abiogenic origin of oil
frequently give examples of naphthide occurrence in
the craters of modern volcanoes. Authors selected
and examined oil shows from the caldera of the Uzon
volcano (Kamchatka). The hydrocarbon type content
of oil shows is dominated by hydrocarbons (HC) (90-
93%). The concentration of saturated hydrocarbons
by weight in them is two times as much as that of
aromatic ones. The concentration of heterocyclic
compounds is 7-10%. Few asphaltenes are present in
the examined samples (< 0,3%). The composition of
saturated and aromatic hydrocarbons of oil shows in
the Uzon volcano caldera shows that they have been
derived from lipids of land plant remains brought into
sediments (the ratio of sterane concentrations
С29/С27>2,5, tricyclane index 2(С19+С20)/ΣСi (i = 23,
24, 25, 26)>1,5, relatively high concentration of
triaromatic steroids), aquabionts, inhabitants of
caldera sediments and bottom waters (the ratio n-
С27/n-С17

P-108
Organic geochemistry and Mesozoic petroleum systems of the
Yenisey-Khatanga regional trough
Alexei Kontorovich, Natalya Kim, Sergei Yershov, Elena Kostyreva, Vasiliy Melenevskiy,
Aleksandr Fomin
Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation
(corresponding author: KimNS@ipgg.nsc.ru)
Recently, the northeastern part of West Siberia
attracts attention of a large number of investigators in
connection with the discovery of the Vankor group of
gas-oil fields with giant reserves. In order to reveal oiland-
gas source rocks in the Mesozoic section of this
area, the core from wells of the western part of the
Yenisey-Khatanga regional trough has been
examined: organic carbon content in rocks and
isotopic carbon composition of insoluble organic
matter have been determined, Rock-Eval pyrolysis
has been made, and vitrinite reflectance R 0
vt has
been identified by the coal-petrographic method. The
results of investigation of biomarker hydrocarbons in
bitumen extracts and oils of Mesozoic deposits of this
region were presented at the IMOG -2009 [1].
The organic carbon contents in Cretaceous rocks
(192 samples) are lower than those of Jurassic rocks,
and the TOC values for 70% of Early Cretaceous
samples are lower than the Clarkes. The organic
carbon content in Jurassic deposits varies from 0.5 to
10.2 % of rock, averaging 1.7 % for 206 samples.
The Vym, Malyshevka and Sig Formations are highly
enriched in organic carbon (average values of
TOCг >2.3 % of rock). For the stratigrapic analogs of
the Bazhenovo Formation, Yanovstan and Golchikha
Formations, the TOC values average 1.6 and 2.0 % of
rock, respectively.
Isotopic carbon composition was studied in 120
samples. Bitumen extracts, having aquagene nature
of lipids, are characterized by higher values of δ 13 С (-
26.6…-30.9 ‰) as compared to typically marine OM
of bitumen extracts of the Bazhenovo Formation (-
28.9…-32.0 ‰).
Data on vitrinite reflectance resulting from the
examination of 139 samples have shown that the
most favorable for liquid hydrocarbon generation are
deposits with the level of OM maturity corresponding
to grades MC1 1 –MC2 (R 0 vt=0.60-1.15 %) – the
Malyshevka, Yanovstan, Golchikha, Nizhnyaya Kheta
and Shuratov Formations. Judging from coalpetrographic
data, Jurassic deposits up to depths of
about 4.0 km have not yet passed out of the main
zone of oil generation and could be of interest for oil
pool exploration.
Pyrolytic data (387 samples) correspond to the
results of petrographic analysis of OM. The
established relationships between hydrogen index HI
and Тmax suggest that Mesozoic deposits occur mostly
in the main zone of oil generation and are
represented both by OM of type II (aquagene marine,
samples from the Malyshevka, Yanovstan, Golchikha,
Nizhnyaya Kheta, Shuratov and Sukhodudinka
Formations, HI to 380 mg HC/g TOC), and OM of type
III (terragene).
Thus, based on a set of geochemical parameters, it
has been established that the Yanovstan (J3–K1) and
Golchikha (J2–K1) Formations, and, to a lesser extent,
the Malyshevka Formation (J2) include the widely
distributed levels where OM of rocks is aquagene
(type II), and organic carbon concentrations and the
level of OM maturity in these rocks make it possible to
consider them as oil source rocks.
Lower Cretaceous bitumen extracts (Nizhnyaya
Kheta, Shuratov Formations) with aquagene nature of
OM are confined to thin regional deep-water members
of clays. Organic carbon concentrations in samples
from these members account for 0.5-2.3 % (averaging
1.6 %) of rock. For the rocks from the Nizhnyaya
Kheta and Shuratov Formations, analyzed by the
coal-petrographic method, the OM maturity suggests
that 78% of all samples have reached the main zone
of oil generation. Therefore, Lower Cretaceous rocks
of the Nizhnyaya Kheta and Shuratov Formations
could generate liquid hydrocarbons, but not in so
significant amounts as the above-indicated Jurassic
deposits. The other examined deposits contain
organic matter related to higher land plants and are
assigned to gas-generating ones.
References
[1] Kontorovich, A., Kostyreva, E., Kim, N. (2009)
IMOG 2009, Abstract Book, 252
251

P-109
A saga on organic geochemistry—50 Years of IMOG
Keith Kvenvolden
Emeritus, U.S. Geological Survey, Menlo Park, California, United States of America (corresponding
author:kkvenvolden@usgs.gov)
In the march of history through time, events are often
noted on decadal or semi-decadal intervals; the
history of organic geochemistry is no exception. For
example, in 2010 the Organic Geochemistry Division
(OGD) of The Geochemical Society (GS)
acknowledged its 50 th year by posting a summary of
the event in Elements (v. 6, p. 338), the journal of GS.
In this same year, the Gordon Research Conferences
(GRC) celebrated 40 years of conferences devoted
specifically to organic geochemistry by inviting
conferees from the first of these meeting in 1970 to
participate in the 2010 conference. Twelve conferees
from the 1970 meeting were able to attend. All twenty
Gordon Research Conferences on organic
geochemistry have taken place at Holderness School
in New Hampshire (USA) every other year since
1970; this series was preceded by related
conferences in 1963 and 1968.
Now, the year 2011 marks the 50 th anniversary of
the <strong>International</strong> <strong>Meeting</strong>s on Organic Geochemistry
(IMOG) with the advent of the 25 th IMOG in
Switzerland. Beginning in 1962, IMOG has convened
every other year except for a three-year hiatus
between 1968 and 1971; this adjustment was made
so that IMOG and the GRC on organic geochemistry
would occur in alternate years. IMOG has convened
in eleven different countries: four times in France and
the UK; three times each in The Netherlands,
Germany, and Spain; twice each in Italy and Norway;
and once each in the USSR, Turkey, Poland, and
Switzerland. The flags of the IMOG host nations from
1962 to 2011 make a colourful statement that attests
to the vibrancy of the organization. The proceedings
of IMOG, consisting of compilations of papers
assembled as ―Advances in Organic Geochemistry‖
have presented an up-to-date view of the scientific
content of each IMOG. The year 2011 also marks the
28 th anniversary of the European Association of
Organic Geochemists (EAOG), which is now
responsible for the organization of each IMOG, and
the official journal of EAOG is Organic Geochemistry,
now in its 33 rd year of publication.
These temporal events acknowledge activities that
formally document the saga of organic geochemistry,
which began at least 80 years ago and is now a wellrecognized
global, interdisciplinary geoscience.
252

P-110
Geochemical characteristics of the mixed marine oils in the
Tazhong Uplift of Tarim Basin, NW China
Yankuan Tian 1 , Chupeng Yang 2 , Zewen Liao 1 , Haizu Zhang 3
1 State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of
Sciences, Guangzhou, China, 2 Guangzhou Marine Geological Survey, Ministry of Land and Resources,
Guangzhou, China, 3 Institute of Petroleum Exploration and Development, Tarim Oilfield Company, Korla,
China (corresponding author:liaozw@gig.ac.cn)
Tazhong oil reservoirs are located in the central
Tarim Basin, NW China, which have been charged
mainly by two sets of marine source rocks, namely
the Cambrian-Lower Ordovician (∈-O1) and the
Middle-Upper Ordovician (O2+3). Due to the complex
post-depositional alterations such as the multiple
hydrocarbon generation, migration and accumulation
episodes, most oils in this area existed as the mixed
oils. The contribution proportions from each source
rocks are significant for petroleum exploration and the
evaluation of hydrocarbon resource in this area.
1. Geochemical studies
Geochemical study of three oils from different
subunits and strata were performed, exemplified by
the oils of Tz104, Tz122 and Tz4-7-38.
The terpane distributions of crude oils were
characterized by higher concentrations of tricyclic
terpanes, C29 norhopane/C30 hopane > 1, reflecting
the last charge from the Middle-Upper Ordovician
(O2+3) source rocks. Adsorbed compounds inside
asphaltenes had similar terpane distribution patterns.
However, terpanes occluded inside asphaltenes,
which represented the origin oils directly derived from
kerogens (Liao et al., 2006), suggested contributions
from the Cambrian-Lower Ordovician (∈-O1) source
rocks. Likely, the sterane distributions implied the
mixed oils deriveded from both source rocks.
2. Quantifying the contribution proportions
In Tarim Basin, the oils sourced from ∈-O1 are
more enriched in 13 C than those from O2+3. Oil Tz62
with δ 13 C -28.606‰ sourced from ∈-O1 and YM2 with
δ 13 C -33.462‰ from O2+3 were widely accepted as
two end member oils (Li et al., 2010). The bulk stable
carbon isotope values of mixed oils are restricted by
the following formula:
δ 13 Cmixed = δ 13 C∈ -O1 * f+δ 13 CO2+3 * (1-f),
where δ 13 Cmixed , δ 13 C∈ -O1 and δ 13 CO2+3 stand for the
bulk stable carbon isotopes of the mixed oils, Tz62
and YM2 oils, f stands for the contribution proportions
from the ∈-O1 source rocks to the mixed oils.
According to the formula, the relative contribution
proportions for 108 oils collected from different
subunits in the Tazhong area were quantified and
discussed. The results (Fig.1) indicated that on the
whole the O2+3 source rocks contributed more to most
oil reservoirs in this area. However, the relative
contribution of both source rocks varied a lot, without
evident regularity for the different oil reservoirs in
different subunits of the Tazhong area.
Fig. 1. Diagram of the compositions of the mixed oils
from different subunits in the Tazhong area, Tarim
Basin.
References
Li, S., Pang, X., Jin, Z., Yang, H., Xiao, Z., Gu, Q.,
Zhang, B., 2010. Organic Geochemistry 41, 531-
553.
Liao, Z., Graciaa, A., Chrostowska, A., Creux, P.,
Geng, A., 2006. Organic Geochemistry 37, 291-
303.
253

P-111
An integrated inorganic and organic geochemical study to
evaluate the origin/age of crude oils
Ercin Maslen 1,2 , Kliti Grice 1 , Tamara Pilgrim 3 , John Watling 4 , Dianne S Edwards 5
1 WA Organic and Isotope Geochemistry Centre, Applied Chemistry, Curtin University of Technology GPO
Box U1987, Perth, WA, Perth, Australia, 2 TOTAL E&P QATAR Total Research Center, P.O. Box 9803, Doha,
Qatar, 3 TSW Analytical Pty Ltd, PO Box 240 Como, WA, 6952, Perth, Australia, 4 Centre for Forensic
Science, University of Western Australia, WA, 6009, Perth, Australia, 5 Geoscience Australia GPO Box 378
Canberra, ACT, 2601, Canberra, Australia (corresponding author:ercin.maslen@total.com)
Selected trace elements (e.g. V, Mo, Fe and Zn) in
oils have been previously used for oil-oil and oilsource
rock correlations [1, 2]. Trace element
contents may predict crude oil origin, maturity,
migration pathways and establish sources of heavily
biodegraded petroleum samples. A novel rapid,
reliable and accurate method of determination of
major and trace element contents of crude oils has
been developed based on Laser Ablation Inductively
Coupled Plasma-Mass Spectrometry (LA-ICP-MS) [3].
For the first time this method has been applied to a
series of petroleum samples for analysis of Fe, Mg,
Zn, Cu, Cr, Ni, Co, V, As, Mo and Se at trace levels,
with little or no sample pre-treatment.
Bulk stable carbon isotopic analyses of saturate and
aromatic fractions of crude oil have been previously
used to differentiate marine from non-marine sources,
however, Australian crude oils do not appear to follow
this trend [4]. Carrying out δ13C/δD of individual
hydrocarbons (of known origin- non-marine and
marine) in a systematic manner may provide a better
understanding on the origins of crude oils in
Australian petroleum systems. Oils analysed include a
series from Australian and Western Canadian basins
of different geological age (e.g. Jurassic, Cretaceous,
Ordovician, and Devonian). The application of linear
discriminant analysis of the stable carbon and
hydrogen isotope ratios and trace element
concentrations has allowed the classification of crude
oils to their geographical (or basinal) sources and
age. The use of complimentary inorganic and organic
isotope techniques for the petroleum samples may
provide a new highly discriminant tool for petroleum
exploration.
[1] Barwise, A.J.G. (1990) Energy Fuel 4, 647-52. [2]
Odermatt, J. and Curiale, J.A. (1991) Chemical
Geology 91, 99-113. [3] Pilgrim, T., et al. (2009)
submitted to Journal of Analytical Atomic
Spectrometry.[4] Edwards, D.S., et al. (2007) IMOG
2007 Abstract Book 827-828.
254

P-112
Hydrocarbon systems of the Russian Arctic continental shelf in
view oil and gas presence forecast
Eric Galimov, Alla Nemchenko-Rovenskaya, Vyacheslav Sevastyanov, Tatyana
Nemchenko
Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow, Russian Federation
(corresponding author:vsev@geokhi.ru)
Russia is blessed with the largest area in the world
and major part of this area in the Arctic zone. There
on the Arctic shelf the abundant resources of
hydrocarbons are concentrated that makes this area
one of the most important sources of hydrocarbons in
the XXI century. Fundamental geochemical research
– carbon isotopic analysis, gas-phase
chromatography, chomato-mass–spectrometry,
microelement analysis and tests Rock-Eval pyrolysis
has made it possible to evaluate the oil and gas
potential of Arctic from viewpoint of its genetics.
Based on the comparative analysis of
hydrocarbons of Arctic it made conclude that the
hydrocarbon potential of Arctic (Barents sea, from
Svalbard)
Archipelago Fran Josev Land is significal.
Considerable volumes of the sedimentary mantie
concentrated in negative structures suggest geat
hydrocarbon generating potential of the province
while vast positive structures adjacent to these
generation sources and reginal collectors (reservoirs)
and seals contained to these generation sources
and regional collectors and seals contained in the
section prove great accumulation capacities within the
boundaries of the entire province. These factors give
reason to view it as one of the most promising
petroleum provinces of Russia.
The Arctic shelf -a new highly prospective region on
the XXI century. The Russian Arctic shelf with total
area of more than 6 million square kilometers. The
unique oil and gas fields Prirazlomnoe oil field,
Shtokmanovskoe gas-condensate, Russanovskoe
and Leningradskoe gas field are comparable with
Yamal giant gas fields. The Kara Sea water area is
the largest by hydrocarbon resources volume and
density. Analysis of the Arctic hydrocarbons
geochemistry on the basis hydrocarbons and rocks
analytical investigations: carbon isotopic composition,
gas chromatography, V and Ni content,
chromatography –mass spectrometry, biomarkers,
generation potential according to Rock-Eval data of oil
and gas fields allowed to work out the complex of
geological and geochemical criteria for scientific
grounds of oil and gas content prospect and
elaboration of future exploration trends on Russian
Arctic shelf.
So further increase of hydrocarbon resources in the
West –Siberian petroleum province is connected with
the development of its Arctic shelf with potential
resources estimated at 15-20 trillion m3. According
prognostic estimation of reserves aquatorial part of
the West Siberian is the largest on size and density
of resources (60 trl.m3 of gas). Rusanovskoe and
Leningradskoe fields – reserves 9trl.m3-stand in on
line with the giant gas fields of Jamal peninsular. The
unique and largest gas fields of the Northern West
Siberia .As well as the first discoveries in the Kara
Sea, are restricted to the coal-bearing Aptian-Albian
Cenomanian complex.
255

P-114
Hydrocarbon generation potential, source rocks and oils of the
Upper Jurassic–Middle Cretaceous formations in the southern
part of the Mesopotamian Basin (Zubair Subzone), southern Iraq
Qusay Abeed, Jan Schwarzbauer, Ralf Littke
University of Aachen, Aachen, Germany (corresponding author:littke@lek.rwth-aachen.de)
The Cretaceous sequences of Iraq host around 80 % of
Iraq's proven oil reserves with more than 70 % of its
probable unproven reserves. In particular, the Cretaceous
sediments of the Mesopotamian Basin host one of the
richest petroleum systems in the world. Nevertheless, these
sequences have been poorly studied so far and only a
limited number of these studies have been published. Each
major sequence contains well-recognized stacked carbonate
and sandstone reservoirs. These are overlain by multiple
tight carbonate and shale seals. The main emphasis of this
presentation is on the Upper Jurassic-Middle Cretaceous
source rocks and crude oils in southern Iraq. On all source
rocks inorganic and organic carbon as well as sulphur
content, Rock-Eval data, vitrinite reflectance, maceral
assemblages were determined. In addition, solvent extracts
from source rocks were analysed by GC-FID and GC-MS
methods in order to characterize the depositional
environment and perform oil-source correlations. Cretaceous
source rocks are at moderate levels of maturity, whereas
Jurassic source rocks (Sulaiy Formation) are clearly beyond
peak oil generation (Figure 1). In addition, some clues on the
paleoenvironment during deposition were reached.
Figure 1. Maturity of the source rocks
31 crude oil samples representing different producing and
non-producing oil fields of southern Iraq were analyzed by
using different bulk properties and molecular geochemical
information to determine their maturity and biomarker
characteristics, as well as to obtain information on their
respective source rocks and possible migration pathways.
Results showed that all the studied oils have high sulphur
content and the specific gravities range from 0.83 to 0.94.
API gravities are in the range of light-heavy oil (19-40° API)
(Figure 2). The average Pr/Ph ratio for the studied oils is
0.79, the average CPI (carbon preference index) is 0.81, and
short chain n- alkanes predominate over long chain nalkanes
(nC17/nC27 ranges between 7 and 15). In
summary, these three parameters indicate that the studied
oils are mature and have been generated from marine
carbonate source rocks. The whole oil chromatograms (GC-
MS) are similar to each other suggesting that either these
oils were generated from the same source or from very
similar source rocks. No biodegradation of n-alkanes has
been observed in the studied samples. However, the
observed heaviness of some oils may be due to water
washing in the study area and/or because of the early
generation from kerogen type II-S.
Figure 2. Crude oils API and sulphur content diagram
Various triterpane and sterane biomarkers were evaluated to
identify the source rocks and indicate that the possible
source of these oils is the Jurassic-Cretaceous carbonate
successions. Several seismic sections reveal possible
migration pathways of the oils.
256

P-115
The carbon isotopic composition of Upper Jurassic oil shales
Russian plate organic matter and its formation conditions
Dmitry Bushnev, Nadezhda Burdelnaya, Irina Smoleva
Institute of Geology of Komi SC of RAS, Syktyvkar, Russian Federation (corresponding
author:boushnev@geo.komisc.ru)
The rock samples with a wide range of Сorg content
were selected to study the carbon isotopic
composition of Middle Volgian kerogen of Russian
plate. The collection represents rocks from outcrops
Vazh-yu, Koigorodok, Ib, Sinegorye, Ayyuva, Kashpir
and Gorodishche. Totally 31 kerogen samples,
isolated from oil shales and clays, were studied. The
� 13 C values of kerogen were measured using mass
spectrometer Delta V Advantage (Thermo), linked to
element analyzer Flash EA. The � 13 C values of
kerogen vary from -22.2 to -28.3‰. The organic
matter of the studied deposition was characterized by
our previous works (Bushnev and Burdelnaya, 2008),
the model of chemical composition for ―average‖
kerogen was suggested (Burdelnaya and Bushnev,
2010).
The analysis of the data we received testifies the
kerogen carbon enrichment by 13 C isotope with the
growth of the Сorg content in rocks. The same trend
was observed for Kimmeridge Clay Formation (KCF)
where � 13 C depends by Corg content of decarbonated
rock. Previously published data (Van Kaam-Peters et
al., 1998), related to isotope composition of organic
carbon of KCF rocks, were interpreted as the
evidence of preservation of isotopically heavy
carbohydrate of organic matter due to their early
diagenetic sulfurisation.
The part of dots on the plot of � 13 C vs. Сorg ―jumps‖
toward relatively lighter kerogen carbon. These dots
correspond to the samples from outcrops of Ayyuva
and Vazh-yu. We believe that such heterogeneity of
the sample can testify to the presence of certain
source of isotopically light OM affecting the total
isotope composition of kerogen of the given samples.
The other part of the collection is related to outcrops
Kashpir, Gorodishche, Koygorodok, Sinegorye, Ib,
where accurate correlation between Сorg content
decarbonated residue of the rocks and � 13 Ckerogen was
observed. The comparison of the published data (Van
Kaam-Peters et al., 1998) on � 13 CTOC for KCF and our
data testifies to their coincidence both in the sense of
variation trend, and absolute values (Figure). It is
possible to consider that this coincidence is not
casual, and testifies to the generality of processes of
organic matter accumulation on the vast territory of
Upper Jurassic sedimentation basins.
� 13 C of kerogen
-20
-21
-22
-23
-24
-25
-26
-27
R² = 0,55
our data
KCF by Van Kaam-Peters et al., 1998
-28
0 20 40 60 80
Corg of decarbonated residue of rock, %
Figure. � 13 C of kerogen vs. Corg content of
decarbonated rock. Our data is related to Kashpir,
Gorodishche, Koygorodok, Sinegorye and Ib samples.
The isotope composition of kerogen carbon and
such index as 2,5-DMT/(2-ET+2,3-DMT+2,4-DMT)
ratio, assessed by the composition of pyrolysis
products of kerogen, are perfectly correlated for our
collection of Middle Volga oil shales, as well as for
KCF, that additionally testifies to the wide
development of early diagenetic sulfurisation of
carbohydrates.
References
Bushnev D.A., Burdel‘naya N.S. // Geochemistry
<strong>International</strong>, 2008. Vol. 46, No. 10, pp. 971 – 984.
Burdel‘naya N.S and Bushev D.A. // Geochemistry
<strong>International</strong>, 2010. Vol. 48. No. 5. Pp. 492 – 504.
Van Kaam-Peters H.M.E., Schouten S., Köster J.,
Sinninghe Damsté J.S. // Geochim. Cosmochim. Acta,
1998. Vol. 62. Pp. 3259–3284.
257

P-116
Marine transgressional event during the Early Cretaceous in
southeastern China: organic petrological and biomarker
evidences
Jian Cao 1 , Xiaomin Xie 2 , Wenxuan Hu 1 , Guang Hu 1 , Yuqiao Gao 1 , Chunhua Shi 1
1 Department of Earth Sciences, Nanjing University, Nanjing, China, 2 Wuxi Research Institute of Petroleum
Geology, SINOPEC, Wuxi, China (corresponding author:jcao@nju.edu.cn)
The Early Cretaceous in southeastern China has
been widely believed to feature a volcanic eruption
intercalated with non-marine deposition, with the
exception of some marine records (paleontological in
particular) along the roughly NE-SW trending
coastline due to marine transgression. Furthermore,
the transgression has been suggested to be held up
by the famous NE-SW trending Zhenghe-Dapu fault,
which is roughly parallel to the coastline. However,
the fault may not activate during the Early Cretaceous
and has started to activate since the Late Cretaceous
according to some tectonic studies. Thus, whether the
transgression has records in the area west to the fault
is an important scientific issue, implying for the activity
of the fault and the intensity of marine transgression.
In this study, dark mudstones samples were
collected from sites west to the Zhenghe-Dapu fault,
including mudstones from the Bantou Formation (K1b)
in Fujian province, Shouchang (K1s) and Guantou
formations (K1g) in Zhejiang province. They were
conducted by an integrated paleontological and
biomarker study. The paleontological
microobservation showed that typical marine fossils
such as red and brown alga are present besides
higher plants. Biomarker features also indicate marine
signatures, such as detection of gammacerane with
the ratio of gammacerane to C30 hopane ranging from
0.11 to 0.18, detection of C30 diahopane,

P-117
Lithology, organic geochemistry, paleo-geography, oil bearing
capacity and petroleum-generating potential of the Bazhenovo
Formation in West Siberia
Alexey Kontorovich, Valentina Danilova, Albina Zamiraylova, Yuriy Zanin, Elena
Kostyreva, Vasiliy Melenevskiy, Valeriy Moskvin, Vika Eder
Trofimuk Institute of Petroleum Geolodgy and Geophysics SB RAS, Novosibirsk, Russian Federation
(corresponding author:DanilovaVP@ipgg.nsc.ru)
In the course of a detailed study of lithology
and organic geochemistry of the Bazhenov Formation
there was obtained new factual material at IPGG
RAS, which allows to improve and develop existing
ideas about the conditions of origination of the
Bazhenov Formation, and assumptions on its
petroleum potential.
There present two main types of rocks in its
section. First, with low content of clay minerals -
carbon-clayey-carbonate-siliceous and siliceous
rocks, characterized by abnormally high (10-25% and
more) concentrations of TOC and authigenic biogenic
silica. N.B. Vassoevich called these rocks
‗bazhenovites‘. The second type is of high clayey
content - mudstone and siliceous mudstone
containing 5-7, rarely up to 10% TOC. Both the
amount of bazhenovites in the section and the
concentration of TOC in them increase from the
periphery to the central, deepest part of the basin.
Bazhenovites and mudstones differ in terms
of indications of salinity, oxidation-reduction (redox)
sedimentation conditions, and in volumes of eolian silt
inclusions, as well as textural characteristics.
Bazhenovites and mudstones also differ in
the specific features of OM. Residual oil and gas
generating potential of the OM of bazhenovites
amount to 350-450 mgHC / g TOC, averaging at 236
mgHC / g TOC in mudstones - 122 mgHC / g TOC.
OM characterized by such diversity in volume and
composition when entering the main zone of oil
generation (oil window) prove to have been the
source of various bitumens. In mudstones their
content varies from 0.06 to 0.77%, making on the
average 0.26%. The bazhenovites are uniquely
enriched in bitumoids (chloroform extractable
bitumens) (their content account for 0.33 – 2.73%,
averaging at 1.30%). By their physico-chemical
parameters and biomarker characteristics, the
bitumoids of the types of rocks under consideration
are not identical, although they all belong to the
marine genotype.
Bitumoids (chloroform extractable bitumens)
of mudstones, compared with those of bazhenovites,
are characterized by low (0.5-1%) sulfur content, by
the dominance of saturated structures in the mass of
hydrocarbons, and by increased ratios n- С 27/ C17 (>
2) and Pr / Ph (> 1). Ethylcholestanes slightly
predominate among steranes. Concentrations of C21,
C23 and C29 appear to be leading in the mass of
tricyclanes. Tetracyclanes are represented, mainly, by
tetracycline C24.
Bitumoids, chloroform extractable bitumens,
of the bazhenovites are known to be richer in sulfur
(3-5 %) and vanadyl porphyrins (2-3 %). Given that
the ratios of n-С27/С17 are not high (from 0.1 to 0.4) и
Pr/Ph (< 1), the CPI approximates 1. Steranes С27,
С28, С29 are present in approximately equal
concentrations Tricyclanes predominate among
terpanes, cheilanthanes С23-С25 concentrations
prevailing in their mass. The tricyclane index value is
2(С19+С20)/(С23-26), on average

P-118
The cracking kinetics of two oil samples from Sichuan Basin,
China
Liangliang Wu, Ansong Geng, Yuhong Liao, Yunxin Fang
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China (corresponding
author:asgeng@gzb.ac.cn)
It has been widely accepted that Oil cracking gas is
one of the main sources of natural gas in the Sichuan
Basin, China. Actually, thermal decomposition of oil
lead to the generation of gaseous hydrocarbons and
pyrobitumen at high maturity. The thermal
decomposition can be kinetically described by
chemical kinetic equation (Ungerer et al.,1987; Wang
et al. 2004). Sealed gold tube pyrolysis is an effective
research means for kinetic study of oil cracking in
closed system (Hill et al.,2004). Two oil samples with
different maturity from the Sichuan basin, China were
selected to perform the thermal simulation experiment
and the cracking kinetic parameters were calculated.
W-oil sample was slight biodegraded, while C-oil is a
transparent condensate oil with little heavy fraction.
The total yields of hydrocarbon gases generated
from the C-oil and the W-oil are similar (Fig. 1). For Coil
at the rate of 2℃/h, when the yield of C2-5 reached
its maximum value (250ml/g.oil) at 470℃, the yield of
C1 is 290ml/g.oil, whereas the maximum yield of C1
is 730mg/g.oil at 600℃.The results indicated that C2-
5 gradually increases with the rising thermal stress at
the early stage of oil-cracking, liquid hydrocarbons
crack accompanying the generation of C2-5 gases. At
the late stage of oil-cracking, decomposition of C2-5
becomes dominated process which may significantly
contribute to the increase of methane and
pyrobitumen. C1 is the stable end gaseous product at
high maturation stage.
Fig. 1 The yields of the two oil samples for C1, C2,
C3 and C2-5 respectively.
Figure 2 illustrates the activation energy
distribution and frequency factor for kinetic models
derived from the selected oil samples. A single
frequency factor (A) of 1.0E+14s -1 was assumed for
all different parallel reactions to make the data
comparable. The average value of activation energy
of C1 is 65.40 Kcal/mol for C-oil and 65.84 Kcal/mol
for W-oil. The average values of activation energy of
C2-5 for C-oil and for W-oil are 59.37 Kcal/mol and
59.56 Kcal/mol, respectively. Obviously, the average
activation energy of C1 is higher than that of C2-5.
The distribution of activation energies of W-oil is wider
than that of C-oil, which could be attributed to the
difference in maturity between the two oils. Oil at
lower thermal stress usually has more heavy
constituents than that at higher thermal stress. It is
obvious that the maturity of W-oil is lower than that of
C-oil which is mainly composed of saturated
hydrocarbon with smaller molecular weight and of
lower density. The total H/C atomic ratio of the oils
rich in heavy constituents usually is lower than that of
condensate oil. Hydrogen content should be factor
controlling the ultimate volume of C1 generated.
Condensate oil is rich in saturated hydrocarbon and
total H/C ratio of bulk oil should be higher. Therefore,
C-oil has narrower distribution of activation energies
and higher yield in C1 than W-oil.
Fig. 2 The activation energy distribution(Ea)and the
frequency factor (A) calculated for the two oil samples.
References
Ungerer, P., Pelet, R., 1987. Nature 327,52-54
Wang, Y. P., Geng, A. S., Liu, D. Y., Xiong, Y. Q.,
Shen, J. G., 2004. Acta Sedmentologica Sinica 22
Suppl., 106-110
Hill, R. H., Tang, Y. C., Kaplan, I. R., 2003. Organic
Geochemistry 34, 1651-1672
260

P-119
Generation potential of Togur Formation rocks in the south-east
of Western Siberia (Russia)
Ivan Goncharov, Nikolay Oblasov, Vadim Samoylenko, Svetlana Fadeeva
TomskNIPIneft, Tomsk, Russian Federation (corresponding author:goncharoviv@nipineft.tomsk.ru)
Togur Formation is considered to be the major source
rock among Lower Jurassic depositions of Western
Siberia. Its formation was the result of early Toarcian
transgression, while sedimentation developed under
conditions when large lakes periodically
communicated with open seas [1]. This resulted in the
unstable formation distribution continuity in area, as
well as, unstable rock composition and properties,
which in its turn, created significant difficulty in
studying this formation.
102 Togur Formation rock samples from 12 well
areas in East of Khanty-Mansiysk autonomy and
Tomsk region were studied (Fig. 1).
The most low-content Togur Formation rock organic
matter was discovered in the wells of Archinskaya,
Elleyskaya, Kolpashevskaya, Stolbovaya,
Urmanskaya and Voskresenskaya fields. The organic
carbon content in these rocks was not more than
1.0% (in separate samples up to 2-3%). Organic
matter in these rocks have a low generation potential
(HI ranges from 13 to 178 mg HC/g TOC, and even
higher).
Togur Formation rocks with a rich TOC content was
discovered in Duklinskaya, Prikoltogorskaya and
Sutiginskaya areas. Organic carbon content in most
investigated rock samples changes from 0.3 to 5.2%,
however, there were samples with a rather high
content (TOC 7.9-20.6%). Nevertheless, organic
matter in these rocks is not of high quality and HI is
usually not more than 300-320 mg HC/g TOC.
The most significant results were obtained in
investigated rock samples from Kulginskaya, Yuzhno-
Tabaganskaya and Lar‘igolkuskaya areas. In these
areas the Togur Formation rocks contain organic
matter with high generation potential. The average HI
is 400-500 mg HC/g TOC, where maximum value is
about 600 mg HC/g TOC. The rocks in Kulginskaya
and Yuzhno-Tabaganskaya areas (in south-western
Tomsk oblast) have rather low carbon content (TOC
0.6-4.9%). Togur Formation rock samples with rather
rich organic matter content were found in wells of
Lar‘igolkusk field (TOC 0.3-17.6%), located in East
Khata-Mansisk autonomy. Togur Formation rocks,
rich in TOC (2.7-19.7%), were earlier discovered in
wells of Vatinskaya, Severo-Orekhovskaya and
Sugmutskaya fields, Khanty-Mansiysk and Jamalo-
Nenechk autonomies, [2], though highly mature
(Tmax=445-466 o C, HI=101-164 mg HC/g TOC).
Different sedimentation conditions of the Togur
Formation significantly affected the extract
hydrocarbon composition of these rocks. Pr/Ph ratio
ranges from 1.0 to 5.0, while Sterane C29/C27 ratio–
from 1.0 to 3.0, which in its turn, reflects the wide
variation of sedimentation oxidation-reduction
environment and bioproducer composition. However,
it can be stated that the oil generation of Togur
Formation played a significant role in the formation of
Verkhekolik-Eganskaya and Suslikovskaya fields in
Eats of Khanty-Mansiysk autonomy. The oil biomarker
composition in these fields is about the same as that
of the rock extract composition in the Togur
Formation, located near Lar‘igolkuskaya area.
Fig.1. Characteristic feature of the generation
potential of Togur Formation.
References
[1] Shurygin B.N. et al. Stratigraphy of oil and
gas basins of Siberia. Jurassic System. Novosibirsk:
Publ. House SB RAS, Department ―GEO‖, 2000.
480p.
[2] Lopatin N.V., et al. (1997) Oil source ,
discovered in crust weathering and mantle of
Paleozoic base in Sredne Pre-Ob areas \\ Geology,
geophysics and oil field development. 7, 7-22p.
261

P-120
The generation potential of the Bazhenov Formation and its
stratigraphic analogues in the east of Western Siberia
Ivan Goncharov 1 , Vadim Samoylenko 1 , Nikolay Oblasov 1 , Svetlana Fadeeva 1 , Vladimir
Krinin 2 , Vladimir Volkov 3
1 JSC «TomskNIPIneft», Tomsk, Russian Federation, 2 CJSC «Vankorneft», Krasnoyarsk, Russian
Federation, 3 SE «SAC RNM named after V.I. Shpilman», Tyumen, Russian Federation (corresponding
author:GoncharovIV@nipineft.tomsk.ru)
Bazhenov formation, the major hydrocarbon source in
Western Siberia, is part of the same regional horizon,
which, in its turn, is located within the top lower
Volgian and bottom lower Berriasian. In the east of
Western Siberia, the investigated area, Bazhenov
horizon includes bituminous Bazhenov formation
rocks (south-east) and partially rocks of Mariyanov
(east) and Yanovstan (north-east) formations.
Bazhenov formation thickness ranges from 5 to 40 m,
while Yanovstan formation thickness is up to 600 m.
More than 3300 Bazhenov formation rock samples
(cores and cuttings) from the east area of Western
Siberia were analyzed. Rock-Eval 6 results showed
that the rocks of Bazhenov, Mariyanov and Yanovstan
formations have S2 value of more than
20 mg HC/g rock, which indicate that these rocks are
of excellent generation potential. Rock organic matter
(OM) in the investigated area has different
catagenesis. Tmax value ranges from 423 to 448 °С
and 4MDBT/MDBT value ranges from 0.4 to 10.0.
Average hydrogen index value (HI) for Bazhenov
formation and its stratigraphic analogues in east of
Western Siberia changes from 225 to
710 mg HC/g TOC. Thus, in single areas, the quality
of OM even exceeds that of kerogen-type II, the HIo
value of which is 627 mg HC/g TOC.
Rock-Eval 6 determines only the residual generation
rock potential; however, it is necessary to know the
initial potential in order to evaluate the volume of
hydrocarbon generation. There were zones of low OM
maturity in each of the above-mentioned investigated
formations. The whole complex of molecular and
Rock-Eval parameters shows the low OM catagenesis
of these rocks, which, in its turn, allows evaluating
HIo. If the HIo value for rock OM of Bazhenov
formation in the south-east of Western Siberia is 600-
710, then for Mariyanov formation rock OM – 500-
600, and for Yanovstan formation rock OM – 400-500
(Fig.). HIo decrease in Bazhenov-Mariyanov-
Yanovstan formation series is accompanied by TOC
decline. If the average TOC content in Bazhenov
formation rocks is not less than 6.0%, then the TOC
content in Yanovstan formation rocks is rarely more
than 5.0%.
It is noteworthy to mention that for rock OM of
Bazhenov, Mariyanov and Yanovstan formations the
sterane ratio 29/27 St has sufficiently close and low
values (Fig.). This fact shows that marine OM
dominates throughout the Bazhenov horizon.
Probably, OM quality (HIo) was mainly determined by
the character of aerobiotic and anaerobic
transformations of initial biomass during
sedimentogenesis and early daigenesis, which is
verified by the pristane/phytane (Pr/Ph) ratio (Fig.).
262

P-121
Source rock characteristics of Cretaceous organic-rich black
shales offshore south-western Africa
Alexander Hartwig, Rolando di Primio
GFZ Helmholtz Centre Potsdam German Research Centre for Geosciences, Potsdam, Germany
(corresponding author:dipri@gfz-potsdam.de)
The source rock potential of Cretaceous organic-rich
whole rock samples from deep sea drilling project
(DSDP) wells offshore south-western Africa was
investigated using bulk and quantitative pyrolysis
techniques. The sample material was taken from
organic-rich intervals of Aptian-, Albian-, and
Turonian-aged core samples from DSDP sight 364
offshore Angola, DSDP well 530A north of the Walvis
Ridge offshore Namibia, and DSDP well 361 offshore
South Africa. The analytical program included TOC,
Rock Eval, bulk pyrolysis GC, bulk kinetics and microscale
sealed vessel pyrolysis (MSSV) experiments.
The results were used to determine differences in the
source rock petroleum type organofacies, petroleum
composition, GOR, and PVT behavior of
hydrocarbons generated from Aptian, Albian, and
Turonian black shales for petroleum system modeling
purposes.
The Aptian organic-rich shales investigated are very
similar throughout the eastern South Atlantic. The
highest source rock potential was identified in
sapropelitic shales in DSDP well 364, containing very
homogenous Type II and organic sulfur-rich Type IIS
kerogen (Fig. 1). Bulk kinetic experiments on these
samples indicate that organic sulfur contents
influence kerogen transformation rates, Type IIS
kerogen being the least stable. TOC contents of up to
31% and HI‘s of 663 mg HC/g TOC were measured.
Average values in all wells are generally in the range
of 6.9 % TOC and an HI of 477 mg HC/g TOC in
black shale intervals with a potential to generate P-N-
A low wax to paraffinic high wax oils, whereas Type III
kerogen with similar TOC values and an average HI
of 53 mg HC/g TOC in intercalated silty sandstones of
DSDP well 361 shows a potential for gas/condensate
generation.
The Albian is a very good mixed Type II/III kerogen
source rock in DSDP well 361. Higher contents of
marine organic matter occur north of the Walvis Ridge
in DSDP wells 364 and 530A. The latter also
containing Type IIS kerogen. The total organic carbon
content can be as high as 37% with HI‘s of 526 mg
HC/g TOC offshore Angola. Average TOC values
reach 5.9% with average HI‘s of 327 mg HC/g TOC.
The kerogen has a potential to generate intermediate
to aromatic P-N-A low wax oils.
South of the Walvis Ridge, the Turonian contains
predominantly a Type III. North of the Walvis Ridge,
the Turonian black shales contain Type II kerogen
with an average TOC of 8.6% and HI of 523 mg HC/g
TOC. These source rocks have the potential to
generate paraffinic and P-N-A high wax oils. The
assessment of the phase properties of the potentially
generated fluids is currently ongoing.
Our results demonstrate the excellent source rock
potential of early Cretaceous organic-rich black
shales, especially of the Aptian-aged source rock, that
has been recognized in a number of the South
Atlantic offshore basins. Further, they emphasize the
effects of changes in ocean water circulation related
to the South Atlantic opening and its influence on
organic matter preservation in Cretaceous-aged
organic-rich sediments along the southwest African
margin.
Fig. 1: Kerogen type according to pyrolysis-GC.
263

P-122
Organic geochemical characterizations of organic-rich rocks of
Beydili (Ankara, Turkey)
Derya Koca, Ali Sarı
Ankara University, Faculty of Engineering, Department of Geological Engineering, Ankara, Turkey
(corresponding author:derya.koca@gmail.com)
The investigated area which is located between
Sarıcakaya (Eskişehir) and Nallıhan (Ankara)
occurres in the valley of Sakarya river that flows from
east to west. The investigated area consists of
Paleozoic, Mesozoic and Cenozoic sedimentary and
volcanic units. Samples investigated in this work are
composed from Paleocene-Eocene organic-rich black
shales of Çamalan Formation. This work is aimed at
investigating the organic geochemistry characteristic
and determining the source rock potential of Beydili
organic-rich black shales.
For achieve the goal, several organic geochemical
analysis were applied to 26 black shale samples
collected from the investigated area. Organic carbon
values of samples range between 1.35 – 11.2 % wt.
(with an average of 5.78) however they show goodexcellent
source rock potential.
Organic material types of samples were
determined by pyrolysis (Rock-Eval-6) and organic
petrographic analysis. Obtained datas show that they
have amorphous and algal organic material type. The
average of Hydrogen Index (HI) values are 670 mg
HC/g Corg, 2 samples show Type II kerogen, while 24
samples are Type I kerogen. Furthermore average of
Tmax of samples are 441°C, therefore samples
indicate immature-early mature stage. Maturation was
determined also with Production Index (OI) and Spor
Color Index (SCI) parameters. PI and SCI values
indicate immature stage, respectively between 0,1 and
0.21 and 3.0-4.0.
According to S1 (0.08 – 0.97 mg HC/g Rock) and
S2 (4.96 – 81.59 mg HC/g Rock) hydrocarbon values,
samples show that range from weak to excellent oil
potential. Pr/Ph values obtained by Gas
Chromatography analysis (GC) show that BD15,
BD27 and BD56 samples are > 1.0 that which indicate
oxic depositional environment and terrestrial organic
material; for the BD3 and BD34 samples Pr/Ph values
are < 1.0 which indicate anoxic depositional
environment and marine organic material.
264

P-123
Organic matter characteristics of Bazhenov Formation in the
central part of the West-Siberian basin based on biomarker
parameters and pyrolysis
Enver Ablya, Elena Kononchenko
Moscow State University, Moscow, Russian Federation (corresponding author:lena.konon@mail.ru)
Bazhenov Formation (BF) (J3) is just 20m thickness
but it is believed a main source rock in the West-
Siberian basin. It is heterogeneous on the area. There
is a central part in its structure which is characterized
by high content of organic matter. It is considered that
in the central part of the basin BF is presented mainly
by bazhenovites which have TOC reaching to 25%
(on the average more than 7-10 %).
In this work it is shown that the structure of BF
organic matter (OM) is more difficult than it was
represented earlier. As an object of research there
were samples from BF at close area of the central
part. Studying of conditions of accumulation and
transformation of OM was a research objective.
Macroscopic description of core, pyrolysis by Rock-
Eval and GC-MS have been carry out. It has been
established (fig.) presence of two extremely different
types of organic matter (including degree of maturity).
The first type (1) is characterized by low Pr/Ph,
abnormal high content of C27 steranes in comparison
with С29, also high ratio t23/t24 (tricyclic terpanes)
that indicates enough deep-water conditions of
sedimentation. It is possible to interpret high
Dibenzotiofene/Phenantrene index as a sign of low
Eh. Together with the pyrolysis data (high HI) this
type of organic matter can be carried to the typically
marine. The second type (2) of organic matter has
opposite characteristics and also higher concentration
of gammacerane that speaks about conditions of the
high salinity. This type can be named terrigenous.
Different degree of maturity of two types is very
interesting. For the first type maturity is relatively high
according to the Ts/Tm and �� sterane ratios, for the
second type (terrigenous) it is much lower (very low
Ts/Tm and �� sterane ratios, the presence of
moretanes). However, according to Rock-Eval data
(Tmax), which always gives the average rate, maturity
is near. Thus, we have two types of organic matter
with different degrees of transformation, and possibly
generated different hydrocarbons, but, nevertheless,
passed virtually the same thermal history.
Terrigenous type formed apparently under intensive
influence of adjacent continent that early thought is
not typical for the central part of the basin. In the
neighbouring areas zones of distribution of abnormal
BF have been identified (thickness up to 100 m, with
Mass chromatogram m/z 191
seams of sandstones).
Them
genesis is
associated with
descent of
turbidites flows
from the continent.
In the
study area
normal BF is
distributed. However,
descent of
turbidites in
adjacent areas
can affect the
formation of it.
265

P-124
Compositional features of organic matter in Jurassic and Lower
Cretaceous deposits located in the east of West Siberia
Natalya A. Krasnoyarova, Olga V. Serebrennikova
Institute of Petroleum Chemistry Siberian Branch of the Russian Academy of Sciences, Tomsk, Russian
Federation (corresponding author:natalex@ipc.tsc.ru)
Compositions of bitumens occurring in Lower
Cretaceous and Jurassic deposits and in crude oil
from a conjunction zone of ancient East-Siberian and
later West-Siberian consolidated crustal blocks of
Earth‘s crust have been analyzed.
The analyzed collection of 140 samples
included cores from Jurassic - Lower Cretaceous
section of four parametrical oil wells: Vostok 1, Vostok
3, Vezdekhodnaya 4 and Yuzhno-Pyzhinskaya 1, as
well as oil of Yuzhno-Pyzhinskaya 1 area.
The concentration of bitumens recovered from
Yuzhno-Pyzhinskaja-1 well is not high in siltstones
occurring in Lower Cretaceous deposit (0.05 %) and it
increases up to 0.20 % in mudstones occurring in
Middle Jurassic deposit. Considerable fluctuations of
bitumens content from 1.1 up to 0.08 % were
observed in Lower Jurassic section.
OM of Cretaceous siltstones is characterized
by the predominance of С23-С27 n-alkanes and the
presence of perylene, vanadyl (VO-P) and nickel (Ni-
P) porphyrin complexes. This organic material was
deposited under reducing conditions (ratio of pristane
(Pr) to phytane (Ph) equals 1.1). A high value of СPI –
an oddness coefficient (1.9) and estimated reflective
capacity of vitrinite (Rc) indicate low thermal
transformation of OM in this section area.
The СPI value decreases in OM of Upper
Jurassic deposit and estimated reflective capacity of
vitrinite is 0.6. OM is lower matured according to the
ratio of isoprenoid to normal alkanes: Pr/n-С17 and
Ph/n-С18, the value of isomers С31 to hopane
homologues S/(S+R) – a homohopane index (0.50)
also indicates low thermal transformation. The
maximum of n-alkanes distribution is shifted in a lowmolecular
area and the ratio of pristane to phytane is
1.9.
The concentration of perylene sharply
decreases and the contents of Ni-P and VO-P
increase in Upper Jurassic mudstones as compared
with Cretaceous ones. A specific set of alkylbenzenes
was registered in organic substance. Along with nalkylbenzenes
isomers of alkylbenzene С17 with С11
alkyl substituent branched on �-atom of the alkyl
chain (i-C11) occur in OM.
The higher Pr/Ph values (> 2) were observed
in OM nearly across the whole section of Lower
Jurassic deposit. The OM of Lower Jurassic deposit is
mature and capable to generate hydrocarbon fluids
according to the ratio of isoprenoid alkanes to normal
ones. The values of the homohopane index (0.54-
0.70) and Rc (0.75-0.80) testify the same.
Comparison of oil composition and that of
dispersed OM of even-aged subjacent rocks indicates
their genetic commonality. The oil and bitumen of
rocks from the depth of 2987.4 meters well correlate
with each other not only by alkanes structure, but also
by the content of separate groups of aromatic
hydrocarbons and heteroatomic compounds; by the
hopanes structure the oil is similar to bitumen
occurring in rocks from depth of 2990.1 meters.
The vanadyl complexes of porphyrins are
absent in bitumens across the whole investigated
section of Vostok 1 oil well. Thermal transformation of
OM is low: Rc – 0.51-0.62 and CPI-1 – 1.4-3.4. The
relative content of isoprenoid and normal alkanes and
homohopane index (0.40) also testify low maturity of
OM. The bitumen molecular composition indicates
dominating contribution of land and coastal water
plants to structure of the initial OM, shallowness of
sedimentation pool and frequent replacement of
oxidation-reduction conditions. The presence of
alkylbenzenes with a substituent branched on �-atom
of the alkyl chain was registered in organic substance
of Upper Jurassic deposits.
In the section of Vostok 3 oil well the OM of
Lower Cretaceous and Upper and Middle Jurassic
deposits is characterized by low maturity. The
sediments of Lower Jurassic deposit can be
considered as the source sediments by OM
composition data. They were formed in the marine
environment and phytoplankton mainly served as OM
source, Rc was equal to 0.72-0.73. The presence of
significant amount of alkylbenzols with substituent
branched on �-atom of the alkyl chain was observed
in Upper Jurassic deposits.
In the presence of VO-P and Ni-P in overlying
rocks, and for underlying ones – only Ni-P, the
predominance of dibenzothiophenes over
dibenzofurans was determined in one of the Lower
Jurassic interlayers of Vostok 3 and Vezdehodnaja-4
oil wells as opposed to over- and underlying
interlayers. It can serve as a marker to correlate the
sections of these oil wells.
266

P-125
Organic geochemical and petrographic characterization of
fluvial-lacustrine source rocks and implications for hydrocarbon
source correlation in Cenozoic rift basins, NE China
Maowen Li 1 , Xue Wang 2 , Shuzhi Wang 2 , Julito Reyes 3 , Sneh Achal 3 , Zihui Feng 2 , Wei
Fang 2
1 Sinopec Research Institute of Petroleum Exploration and Production, Beijing, China, 2 PetroChina Daqing
Oilfield Company, Daqing, China, 3 Geological Survey of Canada, Calgary, Canada (corresponding
author:limw@pepris.com)
Bulk and molecular organic geochemical analyses of
source rock and oil samples from the Fangzheng,
Tangyan and Hulin rift basins, NE China indicate the
presence of fluvial and lacustrine-sourced petroleum
systems in this frontier exploration region. Samples of
potential source rocks include the Eocene-Oligocene
coal, oil shale and lacustrine mudstone litholohgies
and represent a variety of depositional environments.
Rock-Eval and total organic carbon data from these
samples reflect generally high quality source rocks,
including both oil- and gas-prone kerogen types, in
the early to peak stages of hydrocarbon generation.
Petroleum source rocks in the study area generally
belong to the fluvial-lacustrine facies association,
characterized by freshwater lacustrine mudstones and
oil shales interbedded with fluvial-deltaic deposits
including coal. Shoreline progradation dominated
basin fill, resulting in the stacking of indistinctly
expressed sedimentary cycles. Transported terrestrial
organic matter contributes to mixed type I-III kerogens
that generate waxy oil. Based on whole-rock organic
petrographic observations, we propose a three-fold
organic facies classification in the study area: (1) oil
shales and laminated mudstones containing oil-prone,
type I kerogens, mainly in the form of Prasinophyte,
filamentous and coccoidal algal mats; (2) silty
shales containing mixed vitrinite, sporinite and
Prasinophyte and filamentous alginite macerals;
and (3) coals and carbonaceous shales that are
enriched in vitrinite, with trace to variable
sporinite, suberinite, cutinite, and resinite.
Results of open-system pyrolysis experiments
reveal hydrocarbon generation kinetics typical of
type I, I-III and III kerogens respectively. Thus,
hydrocarbon generation from type III source
rocks begins at about 0.6%Ro, with almost 75-
80% of liquid hydrocarbon potential having been
realized at ~0.8 %Ro. In contrast, hydrocarbon
generation from type I source will not begin prior
to 0.7 %Ro, with only 20-25% of liquid
hydrocarbon potential realized at 0.8 %Ro.
Bulk geochemical and biomarker data indicate that
organic rich fluvial-lacustrine facies in the Eocene
Xinancun Formation is the most likely source rocks in
these Cenozoic rift basins. Oils and source rocks from
the Tangyan Trough demonstrate geochemical
characteristics consistent with lacustrine
environments and indicate strong evidence for algal
input into fresh to brackish-water source facies
including elevated relative concentrations of C28
steranes. Despite similarities between oils from the
Fangzheng and Hulin troughs, biomarker parameters
suggest higher algal input in facies sourcing
Fangzheng oils compared to Hulin oils. Based on
sterane isomerisation ratios and diamondoid
concentrations in the oil, the thermal maturity levels of
discovered oils tend to increase from Hulin,
Fangzheng to Tangyan trough, consistent with the
change in the dominant source kerogen types.
The hydrocarbon gases in these rift basins occur
either as biogenic gas pools, or as thermogenic gases
associated with the oil pools. The thermogenic gases
are interpreted to have been generated from the
Eocene-Oligocene fluvial-lacustrine source rocks, with
mixed type I and type III sources, and the biogenic
gases are more likely derived from the coarser parts
of the source beds that have a predominance of
terrigenous plant organic matter and are more likely to
experience freshwater infiltration .
Fluvial-lacustrine sediments in these rift basins
generally contain vertically stacked cycles, and are
laterally discontinuous with strong facies contrasts.
Thus, it is not easy to define a single oil window in a
given basin, but it is common to observe large
fluctuations in the properties of reservoired
hydrocarbon fluids, both vertically and laterally.
267

P-126
The value of generation hydrocarbon and its application on the
evaluation of source rock: taking Liaodong Bay, China as an
example
Shuifu Li, Shouzhi Hu, Jiaren Ye, Dongmei Zhang, Jun Ma
The Faculty of Earth Resources, China University of Geosciences, Wuhan, China (corresponding
author:lishf@cug.edu.cn)
The evaluation of hydrocarbon source rock is one of
the key works in the oil and gas exploration. In order
to evaluate hydrocarbon source rock more
impersonally and effectively, we carried on the
research of the evaluation of hydrocarbon source
rocks in the area of Liaodong Bay, China.
Along the analysis of the common parameters which
is very popular in the present hydrocarbon source
rock evaluation and the factors that can affect the
evaluation of hydrocarbon source rocks, we suggest a
new index——value of hydrocarbon of generation
(VGH), which is a characteristic function of organic
abundance, type and maturity, to evaluate the
hydrocarbon source rock. Based on the data achieved
from the study area, the VGH index can be calculated:
VGHPY=(S1+S2)/10×S2/S3×(Tmax-435).
According to the value of VGH, we suggest five
different grades of the capability to generate
hydrocarbons for the hydrocarbon source rocks in
Liaodong Bay. Using this new index, we evaluate the
capability to generate hydrocarbons for the
hydrocarbon source rocks in each group in Liaodong
Bay. Moreover, the comparison between the new
method and the common method has been made
(Figure 1), and the results are in good agreement.In
addition, we evaluate the capability to generate
hydrocarbons for the hydrocarbon source rocks in the
individual source rock sample in Liaodong Bay. Also,
the correlations between the new and old have been
made.
In conclusion, not only does the new evaluation
method provide the results by the common
evaluation, it can make the evaluation of hydrocarbon
source rock more reasonable and intuitive as well.
References
[1] JIN Zhijun, WANG Qingchen. Recent developments in
study of the typical superimposed basins and petroleum
accumulation in China: Exemplified by the Tarim Basin [J].
SCIENCE CHINA Earth Sciences (Science in China Series
D), 2004, 47 (S2): 1- 15.
[2] TENGER, LIU Wenhui, XU Yongchang, et al.
Comprehensive geochemical identification of highly evolved
marine carbonate rocks as hydrocarbon-source rocks as
exemplified by the Ordos Basin [J]. SCIENCE CHINA Earth
Sciences (Science in China Series D), 2006, 49 (4): 384-
396.
2
1.5
1
0.5
0
10
5
0
30
20
10
0
TOC ( %)
1.31
D2L
(7)
S1+S2(mg/g)
2.86
D2L
(7)
VGHPY
0.62
D2L
(7)
1.59
D3
(12)
5.75
D3
(12)
9.72
D3
(12)
1.80
Sh1-2
(23)
8.79
Sh1-2
(23)
20.97
Sh1-2
(23)
1.23
Sh3M
(15)
4.60
Sh3M
(15)
18.61
Sh3M
(15)
1.01
Sh3L
(34)
2.95
Sh3L
(34)
20.70
Sh3L
(34)
Frequency ( %)
0.3
0.2
0.1
0
1600
1200
800
400
0
80
60
40
20
0
EOM (%)
0.08
D2L
(19)
HC(10 -6 )
324.71
D2L
(19)
72.53
general
contribution
0.13
D3
(71)
556.44
D3
(71)
58.24
0.29
Sh1-2
(11)
1428.14
Sh1-2
(11)
great
contribution
47.25
0.11
Sh3M
(3)
922.25
Sh3M
(3)
significant
contribution
VGHPY
0.15
Sh3L
(9)
749.06
Sh3L
(9)
6.59
large
contribution
>1 >5 >10 >50
268

Tuesday Poster Presentations
269

P-128
Investigation of fish pond management through pigment
biomarkers in the archaeological record
Angela Ballantyne, Brendan Keely
University of York, York, United Kingdom (corresponding author:brendan.keely@york.ac.uk)
Chlorophyll a is the light capturing pigment present in
all plants, algae and cyanobacteria. During the
senescence of primary producers in oxygenated, well
illuminated aquatic systems, the majority chlorophyll a
produced is destroyed by photooxidation within 3
days. 1 By contrast, sedimented chlorophyll
derivatives have a much slower rate of degradation.
Anoxic conditions, present in some aquatic systems
further act to preserve photosynthetic pigments due to
the absence of oxygen. 2
The presence of certain pigment derivatives can be
indicative of the main groups of primary producers
within an aquatic system. For example,
phaeophorbides and sterol chlorin esters are widely
viewed as transformation products associated with
zooplankton grazing the primary producer
community. 3
Stratification of an aquatic system results from poor
mixing of the water body, creating oxygen depleted
bottom waters that underlay oxygenated upper
waters. This effect can be amplified by high
productivity. The growth of anoxygenic primary
producers is facilitated by stratification, as expansion
of oxygenic communities is restricted.
Bacteriochlorophylls are the light capturing pigments
in anoxygenic primary producers.
The aim of this work was to investigate if the
photosynthetic pigments preserved in sediments
could be utilised as biomarkers for the management
of farmed fish in times past.
Sediment cores and auger samples were collected
from dried areas in three archaeological sites:
1. Beningbrough Hall, York, a sediment core from a
fishpond and auger samples from two points in a
canal.
2. Cawood Castle, Cawood, a sediment core from a
fishpond and an auger sample from a moat.
3. Hall Garth, Bolton, sediment cores from a
suspected fishpond and a moat.
HPLC analysis with online UV/vis detection of
organic extracts from Beningbrough Hall and Hall
Garth fishpond sediments revealed only two
components present in very low abundance,
phaeophytin a and pyrophaeophytin a. The results
suggest the use of both sites has been
misinterpreted. The farming of fish can be expected
to cause high productivity and, consequently, create
greater abundances of pigments than found in these
sediments. The analysis of fishpond sediment from
Cawood Castle revealed both chlorophyll and
bacteriochlorophyll derivatives. The presence of
pigments originating from oxygenic and anoxygenic
organisms suggests very high productivity in the pond
caused by fish-farming activities. Archaeological
researchers investigating the site have found fish
bones, thus supporting the hypothesis drawn from
HPLC analysis.
The canal samples from Beningbrough Hall are
more likely to have originated from an aquatic system.
Several chlorophyll derivatives have been identified
but almost no bacteriochlorophyll derivatives,
suggesting the canal was not eutrophic. HPLC
analysis of moat samples from Cawood Castle and
Hall Garth revealed bacteriophaeophytin a,
phaeophytin a and pyrophaeophytin a as the most
abundant compounds in both samples. Thus, it can
be inferred that both moats (Cawood and Hall Garth)
were managed, productive aquatic systems that held
populations of fish.
References
1.Carpenter S. R., M. M. Elser, J. J. Elser (1986)
Limnology and Oceanography 31: 112 – 124. 2.
2.Hurley J. P., D. E. Armstrong (1990) Limnology and
Oceanography 35: 384 – 398.
3. Harradine P. J., P. G. Harris, R. N. Head, R. P.
Harris, J. R. Maxwell (1996) Geochimica Et
Cosmochimica Acta 60: 2265 – 2270.
270

P-129
Characterisation of antique organic adhesives by GC-MS
Armelle Charrié-Duhaut 1 , Jacques Connan 1 , Pierre-Jean Texier 2 , Thomas Hauck 3 , Jean-
Marie Le Tensorer 3 , Céline Leprovost 4 , Mickaël Landolt 5
1 Laboratoire de Biogéochimie Moléculaire, Institut de Chimie de Strasbourg, UMR 7177, CNRS et Université
de Strasbourg, Strasbourg, France, 2 UMR 5199 - PACEA, CNRS et Université de Bordeaux1, Talence,
France, 3 Department of Prehistory, IPNA, University of Basel, Basel, Switzerland, 4 PAIR Pole d'Archéologie
Interdépartemental Rhénan, Sélestat, France, 5 PAIR Pole d'Archéologie Interdépartemental Rhénan UMR
7044, Sélestat, France (corresponding author:acharrie@unistra.fr)
The history of organic adhesives began
probably during the Middle Paleolithic and continued
until the development of synthetic substances.
Although organic glues are very sensitive towards
alteration, they may be preserved in various
archaeological contexts. These materials are the
witnesses of activities from past societies, of their
know-how and of available natural substances. They
can be characteristic of a population, an area or a
period. This paper presents the molecular and
isotopic study of three examples of glues illustrating
the high diversity of adhesives.
As in bio-organic geochemistry,
chromatographic techniques in tandem with mass
spectrometry and isotopic data (δ 13 C) supply a large
range of molecular tools to establish composition and
origin of archaeological organic materials and to
follow the molecular transformations induced by
alteration processes (biodegradation, abiotic
oxidation, evaporation,…). Each antique sample was
compared to its present-day reference: tar sands of
the Bichri desert, fresh Podocarpus bark, birch bark
tar freshly made.
a
b
Figure 1: Photographs of a) a Mousterian tool from
Hummal (Syria), b) a semi-cortical flake from
Diepkloof rock shelter (South Africa), c) a sickle from
Entzheim (France).
The first example corresponds to a
Mousterian tool (50000 BP at least) from the Hummal
Palaeolithic site in Syria. It presents a black macroresidue
on the underside, which has impregnated the
underlying sediment, leaving a clear imprint (Fig.1a).
Bitumen from the Bichri desert was clearly identified
by the distributions of hopanes and steranes, and
isotopic data. The Bichri massif was already identified
in 1996 as the source of bitumen stuck on Mousterian
c
tools excavated at Umm el Tlel (Syria, 70000 BP [1]).
Molecular differences among Hummal residue and
Bichri references are due to variations in degree of
alteration.
The second residue (Fig.1b) corresponds to
a fine deposit coating the cortical back of a semicortical
flake collected at Diepkloof Rock Shelter
(Western Cape, South Africa) from the upper part of
the Howiesons Poort complex (65000-55000 BC)
[2,3,4]. The GC-MS total ion current traces consist
mainly in linear and diterpenoid structures belonging
to the series of totarol and ferruginol. These
distributions are characteristic of Podocarpaceae
conifers. The degree of alteration of the
archaeological resin was studied by comparison with
fresh extract from South African Podocarpus. In
addition, Podocarpus wood remains were identified by
C. Cartwright among the charcoals from this site [5].
The last samples correspond to black matter
surrounding a lithic artefact, clearly drawing a sickle
(Entzheim, France). The sickle (Fig.1c) was found
near a skeleton in a necropolis dated from
Grossgartach period (4900-4700 BC).The results
show that birch bark tar, a triterpenoid adhesive made
by distillation of white birch bark, was used as glue.
This glue was already used during the Middle
Paleolithic period [6].
These works attest to the ability of our
ancestors, whatever the period considered, to use
surrounding natural products for practical use.
[1] Boëda et al. (2008) Antiquity 82, 853-861.
[2] Rigaud et al. (2006) C. R. Palevol. 5, 839-849.
[3] Texier et al. (2010) Proceedings of the National
Academy of Sciences 107, 6180-6185.
[4] Tribolo et al. (2008) J. Archaeol. Sci. 36, 730-739.
[5] Cartwright (2008) Interim report on DRS.
[6] Koller et al. (2001) European Journal of
Archaeology 4, 385-397.
271

P-130
Bituminous mixtures of Hakemi Use (SE Turkey) from the
Hassuna/Samarra Period (6100-5950 BC): origin of bitumen
Orhan Kavak 1 , Jacques Connan 2 , Halil Tekin 3 , Kendra Imbus 4 , John Zumberge 4
1 Dicle University, Muhendislik Faculty, 21280-Diyarbakir, Turkey, 2 Strasbourg University-Laboratoire de
Biogéochimie Moléculaire, 67087-Strasbourg, France, 3 Beytepe, Department of Archaeology, Faculty of
Letters, 06532-Ankara, Turkey, 4 GeoMark Research Ltd, TX-77095-Houston, United States of America
(corresponding author:connan.jacques@orange.fr)
Hakemi Use is one of the archaeological sites to be
flooded by the Illisu Dam which will be built on the
Upper Tigris River. Salvage excavations were
conducted by one of us [1] since 2001. Hakemi Use
belongs to the Pottery Neolithic Period and reflects
the Mesopotamian Hassuna/Samarra culture and is
an important reference point for the Neolithic of the
Upper Tigris region.
Potsherds with bitumen patches, inside or outside,
were selected for analyses using the techniques of
petroleum geochemistry and were compared to
archaeological bitumen of Kavuşan Höyük (2200 BC-
1300 AD) in the vicinity and to oil seeps in the area.
The geochemical analysis of 8 samples show
classical carbon isotopic and biomarker
characteristics of bitumen elsewhere in many
archaeological sites of the Near East and the Arabian
Gulf. A plot of geochemical parameters (Fig.1) for
archaeological samples of Kavuşan Höyük, Hakemi
Use, and oil seeps from the area reveals diagnostic
features. Bitumens from Hakemi Use are generally
more biodegraded than those from Kavuşan Höyük
with respect to the steranes (altered order:
C27

P-131
Interred with their bones: biomarkers in archaeological burials
Kimberley Green, Matthew Pickering, Don Brothwell, Brendan Keely
University of York, York, United Kingdom (corresponding author:kas516@york.ac.uk)
Archaeological investigation of graves has for a
long time been a crucial means to glimpse into past
cultures. Studies of graves have revealed vital
archaeological information indicating that in the
past, as today, great cultural importance was
placed on death and the ritual of burial. Well
preserved graves can provide evidence of clothing
and grave objects that have shown ritual
significance. Excavations of these graves usually
consist of grave detection, excavation and removal
of human remains and recognisable objects.
It is apparent that the information is being
recovered from graves during archaeological
excavation is not maximised. Even in graves that
are not especially well preserved there exists the
potential to obtain vital information from the soil
through microscopic features and organic residues
preserved within. By means of micromorphological
and trace organic analysis there is the potential to
reveal information on body decay; pre-burial
treatment; drug treatment and evidence of
morbidity.
The InterArChive team combines both
archaeological and chemical backgrounds to build
analytical methods and sampling techniques in
order to develop a process that archaeologists can
use to maximise the evidence obtained from the
graves and therefore improve the interpretations of
the grave.
This part of the project focuses on detailed analysis
of the extractable organic matter from 20 sampling
points within each grave to determine the extent of
variation surrounding the skeletal remains and to
determine if sampling from fewer points would be
sufficient to provide a similar level of information. In
addition, samples have been recovered fro
materials and objects, such as burial pots and
clothing, present in some of the graves.
Fig 1: 17 Sampling points from around the body
Dried and sieved (

P-132
Combined � 13 C - �D analysis of pentacyclic triterpenes and their
derivatives
Jérémy Jacob 1 , Claude LeMilbeau 1 , Nicolas Bossard 1 , Jean-Robert Disnar 1 , Yves
Billaud 2
1 Institut des Sciences de la Terre d’Orléans (ISTO), Université d’Orléans, CNRS/INSU UMR 6113, Orléans,
France, 2 Ministère de la Culture, DRASSM, Marseille, France (corresponding author:jeremy.jacob@univorleans.fr)
Compound-specific carbon and hydrogen analyses
have been proposed to quantify environmental
variables because they afford a remarkable constrain
on the biological source through the selection of
specific biomarkers. Upon these biomarkers, higher
plant pentacyclic triterpenes are reputed
chemotaxonomical markers and can, in favourable
cases, be related to a restricted number of taxa. Once
they integrate geological systems, these compounds
can undergo several structural modifications that
potentially affect their original �D and � 13 C. Previous
work showed that the aromatisation of pentacyclic
triterpenes has little effect on the � 13 C (Freeman et
al., 1994). Reversely, there is presently no estimate
on the impacts of pentacyclic triterpene diagenesis on
�D.
Here we report on the �D and � 13 C of pentacyclic
triterpenes and their diagenetic derivatives recovered
from Bronze Age settlement layers preserved in subaqueous
conditions (3 m depth) at the Châtillon
station of Lake le Bourget (Chindrieux, France). This
site was selected because preserved organic matter
is constituted by restricted sources of C4 plant
material (Panicum miliaceum and Setaria italica) that
produce original compounds such as �- and �amyrins,
miliacin, germanicol and glutinol (Tulloch,
1982).
Lipids were extracted and separated into neutrals and
acidic compounds. The neutral compounds were
further separated into aliphatics, aromatics, ethers
and ketones before identification and quantitation by
GC-MS and �D/� 13 C determination by GC-irMS.
Pentacyclic triterpenes and their diagenetic
derivatives are the dominant compounds in the lipid
extract. The aliphatic fraction comprises a set of des-
A-triterpenes with various structures. Aromatic
derivatives of intact or ring A-degraded pentacyclic
triterpenes are found in the aromatic fraction. Miliacin
was found at high concentrations in the ether fraction.
The ketone fraction contains several triterpenoids
ketones such as friedelin, taraxerone, lupanone,
lupenone, and isomultiflorenone. The variability in
triterpene imprints probably reflects variable sources
of organic material in archaeological levels and
differential
medium.
physico-chemical conditions in the
�D (‰ VSMOW)
-120
-140
-160
-180
-200
-220
-240
-260
-280
-35 -33 -31 -29
�13C (‰VPDB)
-27 -25 -23 -21
9
8
15
11
5
6
14
13 12
1
2 3 4
Figure 1: �D and � 13 C of pentacyclic triterpenes and their diagenetic derivatives
extracted from archaeological layers. 1: des-A-olean-13(18)-ene; 2: des-A-olean-
12-ene; 3: des-A-olean-18-ene; 4: des-A-urs-12-ene; 5: des-A-lupane; 6: 24,25dinorolean-1,3,5(10)-triene;
7: 24,25-dinorolean1,3,5(10),12-tetraene; 8:
24,25,26,27-tetranorolean(ursan)-1,3,5(10),6,8,11,13-heptaene; 9: 24,25,26,27tetranorlupan-1,3,5(10),6,8,11,13-heptaene;
10: miliacin; 11: taraxerone; 12:
isomultiflorenone; 13: lupenone; 14: lupanone; 15: friedelin.
Miliacin � 13 C is in agreement with its C4 origin.
Taraxerone and friedelin are characterized by low
� 13 C that attest to a quasi-exclusive C3 origin.
Lupanone, lupenone and isomultiflorenone could
originate from mixed sources.
Miliacin is enriched in deuterium when compared to
other pentacyclic triterpenes of C3 origin (-140 and -
180 ‰, respectively). Des-A-triterpenes 1, 2, 3, 4, 5
and aromatic des-A-triterpenes 9 and 8 are depleted
in D by ca. 30 ‰ when compared to pentacyclic
triterpenes of C3 origin. Pentacyclic aromatic
derivatives 6 and 7 are the most D-depleted
compounds found in our extracts.
These results indicate the diagenesis of pentacyclic
triterpenes can lead to �D shifts as large as 100 ‰.
The analysis of triterpene alcohols and minor
diagenetic derivatives in the same sample is expected
to give additional information on genetic relationships
between original compounds and their diagenetic
derivatives and to provide more quantitative data on
the isotopic effects associated with these
transformations.
Freeman, K.H., Boreham, C.J., Summons, R.E. and Hayes, J.M. (1994). The
effect of aromatization on the isotopic compositions of hydrocarbons during early
diagenesis. Organic Geochemistry 21, 1037-1049.
Tulloch, A.P., 1982. Epicuticular waxes of Panicum miliaceum, Panicum texanum
and Setaria italica. Phytochemistry 21, 2251-2255.
7
10
274

P-133
Can we estimate catchment-scale biomass production from
sedimentary biomarkers? An attempt with miliacin in Late
Bronze Age levels from Lake le Bourget (French Alps)
Jérémy Jacob 1 , Emmanuel Chapron 1 , Yves Billaud 5 , Grégoire Ledoux 2 , Patrick
Lajeunesse 2 , Jean-Robert Disnar 1 , Guillaume St-Onge 3 , Claude LeMilbeau 1 , Nicolas
Bossard 1 , Fabien Arnaud 4
1 Institut des Sciences de la Terre d'Orléans, ISTO, Université d'Orléans, UMR 6113 du CNRS/INSU,
Orléans, France, 2 Centre d'Etude Nordique (CEN) Université de Laval, Québec, Laval, Canada, 3 ISMER,
Université du Québec à Rimouski, Rimouski, Canada, 4 EDYTEM, UMR 5204 CNRS/Université de Savoie,
Le Bourget du Lac, France, 5 Ministère de la Culture, DRASSM, Marseille, France (corresponding
author:jeremy.jacob@univ-orleans.fr)
The evaluation of demography for proto- and
prehistoric times is still complex due to the rareness
of human remains. Here we propose an original
approach based on the combination of geophysical
and organic geochemical techniques applied to the
Late Bronze Age sedimentary infill of Lake le Bourget
(French Alps). Deep sediments were recently mapped
by multibeam bathymetry and their volume estimated
by sub-bottom seismic profiling calibrated
(acoustically and chronologically) on piston cores
(Chapron et al. 2005; 2007). Sub-bottom profiling
combined to a subaquatic archaeological survey
allowed us to precisely identify the extension of Late
Bronze Age palafittic stations in shallow waters and to
determine the volume of the associated organic rich
deposits.
The concentration of miliacin, a molecular biomarker
of cultivated millet that is preserved in sediments
(Jacob et al., 2008), was determined in Late Bronze
Age levels both in deep sediments (on piston cores)
and in organic levels developed under palafittic
stations (short gravity cores). Miliacin concentrations
were very similar (ca. 300 ng/g) in two piston cores
drilled 4 km apart, revealing the homogeneity of
concentrations over the basin. Miliacin concentrations
are ten to hundred times higher in shallow organic
deposits. By combining concentrations of miliacin, the
volumes of deep and shallow sediments, and
considering sediment density, we estimated the total
amount of miliacin deposited at this time. The analysis
of ancient millet cultivars showed that miliacin is
essentially concentrated in seeds and allowed us to
convert the total amount of miliacin into total weight of
millet seeds produced in the catchment, assuming
that miliacin was entirely transported to the sediment
and was not affected by early diagenesis.
Future work will focus on the carbon isotopic analysis
of human and animal remains in order to determine
the amount of millet in their respective diet (millet
being the only C4 plant at that time). The comparison
of our results with demography data estimated from
habitat density will allow identifying possible
methodological biases in our approach.
Figure 1: Isopack map of the Holocene lacustrine drape identified in
Lake Le Bourget by high-resolution seismic reflection profiling (ms
TWT are milliseconds two-way-travel times). Using P waves velocity
measurements on two long piston cores (LDB01 & LDB04) with a
Geotek multisensor core logger (mean values of 1.5 km/s, cf Chapron
et al., 2005), the thickness of Late Bronze Age sediments can be
determined.
References
Chapron E., Arnaud F., Noel H., Revel M., Desmet M., Perdereau L.
2005. Rhone River flood deposits in Lake Le Bourget: a Proxy for
Holocene environmental changes in the NW Alps. Boreas, 34, 404-
416.
Chapron E., Arnaud F., Marguet A., Billaud Y., Perdereau L., Magny
M. 2007. Evolution des paléoenvironnements alpins durant l‘age du
Bronze : apports des archives sédimentaires littorales et profondes
du lac du Bourget (Savoie, France). Editions du Comité des travaux
historiques et scientifiques (CTHS). Documents préhistoriques n°21,
45-55.
Jacob, J., Disnar, J.R., Arnaud, F., Chapron, E., Debret, M., Lallier-
Vergès, E., Desmet, M., Revel-Rolland, M. 2008. Millet cultivation
history in the French Alps as evidenced by a sedimentary molecule.
Journal of Archaeological Science 35, 814-820.
275

P-134
Biomarkers preserved in cave sediments and their use as
indicators of environmental change in Trang An, Vietnam
Natalie F. Ludgate 1 , Thomas A. Griffiths 2 , Alison J. Blyth 1 , William D. Gosling 1 , Iain
Gilmour 1
1 The Open University, Milton Keynes, United Kingdom, 2 University College London, London, United
Kingdom (corresponding author:n.f.ludgate@open.ac.uk)
The aim of the Trang An archeological project is to
understand hunter-gatherer mobility at the end of the
last glacial maximum (LGM) [1]. Research into
terrestrial flora since the LGM is of key importance in
understanding hominid movement and cultural
development. Floral reconstructions can then be
integrated with cultural and dietary information
deduced from archaeological finds [1]. Clastic cave
sediments may thus provide an important terrestrial
record. Here we propose a novel technique using
biological markers found in clastic cave sediments.
The focus of this study is the use of lipids, including nalkanes,
and n-fatty acids, derived from higher plants
and molluscs from cave sediments in Vietnam.
Previous studies have shown that lipid biomarkers are
a valuable palaeoenvironmental resource in soils,
sediments and chemically precipitated speleothems
[e.g. 2,3,4]. Caves can provide an ideal environment
for lipid biomarker preservation. Within caves,
sediments are accumulated by aeolian or fluvial
deposition, with relatively little further digenesis or
post-depositional alteration. Lipid biomarkers from
local flora will therefore be transported into caves and
preserved.
Two caves in Vietnam (Ninh Bình province); Hang
Boi, and Hang Trong have been chosen as study
sites. Bulk sediment samples were taken from
stratigraphic layers within each archeological trench:
where strata were not determinable samples were
taken in 10 cm spits. Hang Boi is an open cave
situated at 78 m a.s.l. charcoal radiocarbon dates
indicate c.20 cm of sediment was deposited between
c. 12,400 and 12,100. The second site, Hang Trong,
is situated 142 m a.s.l. formed with openings on each
sides of a karst tower, allows detailed investigation of
airborne deposition. Radiocarbon dates, from
charcoal, indicate the immediate sub-surface
sediment is recent whilst at approximately 1.5 m from
the surface it dates to 18,500 yrs. b.p. The sites are
dominated by anthropogenic shell middens
interspersed with aeolian sediments and bed-rock
break down. For each stratum, freeze dried subsamples,
were Soxhlet extracted with 93:7
CH2Cl2/CH3OH. After evaporation of the excess
solvent, the samples were derivitised with boron
triflouride methanol in addition to BSTFA + TMCS.
Sample analysis is completed on a GC-MS; Agilent
Technology gas chromatograph coupled with a 5973
mass spectrometer. Separation was performed on a
J&W Scientific HP-5MS capillary column the He
carrier gas at a constant flow rate of 1.1 ml min -1 . The
GC oven temperature was held for 2 min at 50°C and
ramped to 300°C at 5°C min -1 and then held for 9 min.
A wide range of lipids in the extracted fraction
including: alkanes, alcohols, fatty acids, sterols, and
triterpenoids. The content of total extractable organic
matter in the sediment ranges from 110-880 µg/g of
dry sediment. Normal alkane homologues in the
extracts range from C26 to C34 with an average
maxima at C31. There is distinct odd-over-even carbon
predominance, indicating a vegetational source.
Normal fatty acids and alkanol range from C24 to C34
with average maxima at C30 and a strong even-overodd
carbon predominance.
This is first comprehensive investigation of lipid
biomarkers from plants preserved in clastic cave
sediments. The study will reconstruct the local
vegetational history using both palynological and lipid
biomarker analyses. The lipid biomarker time series
can then be compared with the palynological record to
determine the effectiveness of the method, providing
key insights into the local palaeoenvironmental
conditions and ecological impact on hominids. The
lipid analysis technique developed during this project
will support established methods and provide
information from sites where existing techniques are
unsuitable.
[1] Rabett, R., et al., (2010). Quaternary <strong>International</strong>, Article in Press
[2] Blyth, A.J., et al., (2007). Quaternary Research, 68(3), 314-324.
[3] Bull, I.D. et al (2000). Organic Chemistry, 31, 389-408.
[4] Meyers, P.A. et al., (2003). Organic Chemistry, 34, 261-289.
276

P-135
Composition of aliphatic hydrocarbons in prehistoric rice paddy
soils in China
Cornelia Mueller-Niggemann 1 , Jin Zhang 2 , Zhi-Hong Cao 3 , Lorenz Schwark 1
1 Institute of Geosciences, Christian-Albrechts-University of Kiel, 24118 Kiel, Germany, 2 School of Environ.
Science and Technology, Zhejiang A & F University, Lin`an 311300, China, 3 Institute of Soil Science,
Chinese Academy of Sciences, Nanjing 210008, China (corresponding author:cmn@gpi.uni-kiel.de)
Cultivation of rice in China dates back as far as 8000
years as documented by archaeological harboring
rice field management tools and carbonized grains of
cultivated rice species. At the Chuodun site north of
Hangzhou Bay major relics of the Neolithic Majiabang
culture, including ancient paddy rice fields have been
excavated. At this site two prehistoric rice paddy
horizons are overlain by a recent rice paddy soil. The
base of the older prehistoric paddy was dated to
6280a b.p., that of the younger to 3300a b.p. [1].
From here, recent and ancient paddy soils, rice plants
and in-field rice combustion residues have been
analyzed for their lipid content. The results show, that
recent and ancient paddy soils retrieve substantial
input of n-alkyl lipids not only from pristine plant
waxes but in significant amounts from combustion
residues.
Combustion in heaps of wet rice straw in the field
leads to commonly observed PAH but also to a suite
of n-alkanes and n-alkenes. The extract of rice straw
ash containing residual charred plant fragments is
shown in Figure 1. Three suites of acyclic aliphatic
hydrocarbons can be differentiated. Firstly, a series of
n-alkenes ranging from nC15 to nC28 and maximizing
at nC22 reveals a CPI value of 1.0. Secondly, an
envelope of n-alkanes from nC15 to nC35 and
maximizing at nC26 exhibits a CPI value around 1.0.
Only a few primordial wax alkanes with a chain length
of 29, 31 or 33 extend from this envelope.
The even numbered n-alkanes contributing to this
envelope are assumed to derive from direct
dehydration and hydrogenation of even numbered nalcohol
precursors. Formation of n-alkane distribution
with CPI values around 1 has been previously
described [2] for artificial combustion of maize and rye
straw at temperatures between 300 to 500°C. At
temperatures of 300°C sterenes, formed via sterol
dehydration, dominated and n-alkenes with even
carbon number predominance were present in minor
concentrations. At 400°C the aliphatics consisted
almost exclusively of n-alkanes with a CPI of 1.0. By
comparison we infer an average temperature ranging
between 300 and 400°C for the in-field combustion of
rice straw. The n-alkyl lipid signature determined from
the analysis of rice ash is thus taken as an input
indicator for rice cultivation into recent and fossil soils.
The recent paddy soil analyzed from the Chuodun site
revealed an n-alkane distribution similar to that of the
rice straw ash. In soils of the Chuodun archaeological
site and in a variety of rice paddy soils from China,
Java and Sumatera, n-alkenes have not been
detected, arguing for a rapid conversion into their
corresponding saturated analogues.
Fig.1. Distribution and source allocation of
alkanes/alkenes in rice field combustion residues.
Contamination of paddy soils with fossil hydrocarbons
has been observed in other paddy sites but was
accompanied by traces of steranes and hopanes. As
no such triterpane contaminants were detected in the
recent and ancient soils from the Chuodun site, the nalkanes
with even carbon distribution are indicative of
rice ash input and thus of rice cultivation. The 3300
year old paddy contained minor amounts of ashderived
alkanes, preferentially at the base. In the
6620 year old paddy horizon (80 cm thick) all samples
show a prominent ash pattern. Soil lipid analysis
identified rice paddy cultivation and fire management
practices for fertilization in the Neolithic Majiabang
cultural sites in East China.
[1] Cao et al. (2006) Naturwissenschaften 93,232-236
[2] Wiesenberg et al. (2009) Organic Geochemistry
40, 167-174.
277

P-136
Analysis of insoluble organic residues in graves by sequential
thermal desorption/pyrolysis-gas chromatography-mass
spectrometry
Matthew Pickering, Kimberley Green, Don Brothwell, Brendan Keely
University of York, York, United Kingdom (corresponding author:brendan.keely@york.ac.uk)
The archaeological investigation of human burials
provides valuable insights into past populations. The
approaches employed focus mainly on the recording,
examination and interpretation of the visible human
remains, grave goods, burial structures and soil
features. While grave soil in direct contact with the
body is sometimes examined for physical traces such
as seeds, pollen and parasite eggs, it has rarely been
examined in detail and is often discarded.
The InterArChive project has adopted a combination
of approaches: organic geochemistry and soil
micromorphology; to characterise organic matter in
grave soils in order to reveal signatures of body
decay, mortuary practices, clothing, diet and morbidity
and to evaluate soil compositions and types that lead
to enhanced preservation of the organic signatures.
The work presented here focuses on one aspect of
the organic analysis: the use of sequential thermal
desorption-gas chromatography (TD-GC-MS) and
pyrolysis-gas chromatography-mass spectrometry
(Py-GC-MS) to characterise the constituents of
solvent insoluble organic residues associated with
human burials.
Burials spanning a wide range of ages, geographical
locations and soil types have been sampled at
specific locations around the skeletal remains and
from any associated artefacts (e.g. burial pots, coffin
stains). In addition, visible fragments of hair, coffin
wood, textiles, leather and paper have been collected.
Control samples of the grave fill and from outside the
grave enable the organic geochemical background to
be established. Duplicate samples of undisturbed soil
have been collected from key positions around the
skeletal remains for micromorphological analysis.
Elemental analysis (C/H/N/S/O and total organic
carbon content) provided a broad indication of the
nature and quality of the organic matter present and
has been used to identify soils containing sufficient
organic matter concentrations for pyrolysis. Analyses
of the solvent insoluble organic residues by TD- and
Py-GC-MS have been compared with those from
modern reference materials, revealing information
regarding the identity, composition and preservation
state of these materials from their chemical
signatures. The pyrograms from partially preserved
coffin woods recovered from sites in Scotland and
Belgium (e.g. Fig. 1) show marked similarities in the
profiles of lignin-derived guaiacyl subunits, these
more closely matching the signatures of modern pine
than of oak, and exhibit preferential breakdown of the
cellulose component of the wood. The project aims to
evaluate the potential for the detection of such
remains in grave soils in which visible remains are
absent.
A fundamental goal of the InterArChive project is to
provide sampling recommendations that can be used
to inform future archaeological excavations of human
burials in order to maximise the amount of information
retrieved. In addition, the methodologies and data are
relevant in the context of the forensic examination of
more recent burials.
Fig. 1. Partial Py-GC pyrogram (610°C) of a sample of
coffin wood collected from a grave in Belgium.
278

P-138
Monitoring organic pollutants (PAHs, PCBs, OCPs) in German
forest soils
Bernhard Aichner 1 , Petra Lehnik-Habrink 1 , Sebastian Hein 1 , Bernd Bussian 2 , Wolfram
Bremser 3 , Irene Nehls 1
1 BAM Federal Institute for Materials Research and Testing, Division 1.2, Berlin, Germany, 2 Federal
Environment Agency of Germany, Division II 2.7, Dessau-Roßlau, Germany, 3 BAM Federal Institute for
Materials Research and Testing, Division 1.4, Berlin, Germany (corresponding
author:bernhard.aichner@bam.de)
Polycyclic aromatic hydrocarbons (PAHs),
polychlorinated biphenyls (PCBs) and organochlorine
pesticides (OCPs) are three classes of persistent organic
pollutants (POPs) which are ubiquitous in the
environment. To gain a better understanding of the
ecological cycling of POPs through the environment,
reliable monitoring data are indispensible. The
<strong>International</strong> Cooperative Program on Assessment and
Monitoring of Air Pollutants Effects on Forests (ICP
Forests) was launched in 1985. This program connects
several national monitoring projects of different EU
member states in order to monitor effects of
anthropogenic and natural stress factors on the condition
and development of forest ecosystems. In 2005, the
federal states of Germany approved a concept to monitor
POPs within the framework of ICP Forests. This program
was launched and financed by the Federal Environment
Agency of Germany (UBA) and the method for
simultaneous screening of PAHs, PCBs and OCPs was
developed at the BAM Federal Institute for Materials
Research and Testing.
The focus was set on 16 priority PAHs of the US
Environmental Protection Agency, six principal PCBs
(IUPAC No´s 28, 52, 101, 138, 153, 180) and on major
OCPs: dichlorodiphenyltrichloroethane (DDT) and five of
its metabolites, aldrin, dieldrin, hexachlorobenzene
(HCB) and hexachlorocyclo-hexanes (α-, β- and γ-HCH).
Samples were derived from 448 spots distributed in a 16
km x 16 km raster over Germany. Sampling plots are
located in forests only. On each location, the O-horizon
(humic horizon) and the mineral top soil in the depths 0-5
cm and 5-10 cm were sampled.
At most sampling sites pollutant concentrations gradually
decrease with depth. Only few spots showed highest
concentrations in the upper mineral soil. The sum
concentration of 16 PAHs in the O-horizon range from
110 to ca. 13,000 µg / kg d.w. (median: ca. 1,500 µg / kg
d.w.). Relatively high concentrations are associated with
open cast mining of brown coal in the eastern part of
Germany, with mountainous regions and with
industrialized and urban areas. The PAH pattern is
mostly dominated by benzo(b)flouranthene, flouranthene
and chrysene. About 5% of the samples (all of them
derived from the eastern part of Germany) had enhanced
relative abundances of phenanthrene which is probably
induced by the vicinity to strip mining sites.
The concentration of ∑6 PCBs range from 1 to 96 µg / kg
d.w. (median: 13 µg / g d.w.) in the O-horizon. All
samples show similar PCB patterns with highlychlorinated
congeners as dominating compounds
(153>138>180), while lower chlorinated congeners occur
in traces only. Generally, there is a trend towards higher
concentrations in the western and north-western part of
Germany compared to the east and south-east. Peak
concentrations occur close to industrialized urban areas
such as the Ruhr Metropolitan Region.
In the O-horizon, the sum concentration of DDT and
metabolites range from

P-139
Role and nature of organic matter in the mobilisation of arsenic
in shallow reducing aquifers
Wafa. M. Al Lawati 1 , Jiin-Shuh Jean 2 , Ming-Kuo Lee 3 , Thomas. R. Kulp 4 , Michael Berg 5 ,
Elisabeth Eiche 6 , Athanasios Rizoulis 1 , Jon Lloyd 1 , David Polya 1 , Bart. E. van Dongen 1
1 School of Earth, Atmospheric and Environmental Sciences, The University of Manchester, Manchester,
United Kingdom, 2 Department of Earth Sciences, National Cheng Kung University, Tainan, Taiwan (Province
of China), 3 Department of Geology and Geography, Auburn University, Auburn, United States of America,
4 U.S. Geological Survey, Water Resources Division, Menlo Park, United States of America, 5 Eawag, Swiss
Federal Institute of Aquatic Science and Technology, Dubendorf, Switzerland, 6 Institute of Mineralogy and
Geochemistry, Universitat Karlsruhe, Karlsruhe, Germany (corresponding
author:Wafa.AlLawati@postgrad.manchester.ac.uk)
Over a hundred million people across the globe are
chronically exposed to high concentrations (>10 ppb)
of the geogenic poison, As, in shallow reducing
groundwaters utilised as drinking water. The detailed
mechanisms by which As is mobilized into the waters
of these aquifers is still a matter of debate. However,
it is generally believed that microbes play a key role
through the reductive dissolution of As-bearing Fe(III)
hydrated oxides and/or the reduction of sorbed As(V).
Electron donors such as organic matter (OM) are
required to drive this process, yet As release rates are
often poorly correlated to total OM – this may in part
reflect the varying bioavailabilities of different types of
OM [1,2], the importance of other electron donors or
the confounding influence of other, notably
mineralogical or microbiological, processes. The role
and nature of OM in As mobilisation therefore remains
rather unambiguous, perhaps in part due to the
limited number of studies to date. An improvement in
understanding of this link is required to better inform
theories of long-term anthropogenically driven secular
increases in groundwater As in these aquifers [3].
In this project, we further investigate the correlation
between As release from aquifers and the OM
present. To date, all aquifer sediments analysed,
including new sediments from well known As hotspots
in Vietnam, West Bengal and Taiwan, revealed inputs
from comparable multiple sources including
contributions from naturally occurring petroleum
seeping into the shallow aquifer sediments from
deeper thermally mature source rocks. However,
comparison between core-sites with contrasting As
concentrations (e.g. < 10 ppb and up to 600 ppb) in
the groundwater indicated no noticeable differences in
biomarker distribution patterns, suggesting that As
mobilisation is not associated with a specific organic
source at these sites.
Microcosm experiments were used to determine the
correlation between different sources of OM and As
mobilisation. No correlation between any OM source
and the amounts of As(III) released could be
observed (Fig.1). This suggests that As mobilisation
might not be exclusively associated with a specific
type of OM but could be different from site to site.
Further more, microcosms using OM-lean aquifer
sediments (TOC < 0.02%) showed that As can even
be mobilised in the absence of substantial amounts of
bioavailable organics [4] suggesting that other
electron donors need to be considered as well.
Combined, these studies show that the precise
mechanism of As mobilisation in a variety of
sediments is still unknown but at best, a complex
interplay between microbiology, mineralogy and
geochemistry at the nano-scale should be expected.
Fig.1. Correlations between (a)TOC, HMW (b)nalkanes,
(c)n-alkanoic acids and (d)n-alkanols and the
% As(III) released in microcosm experiments using
sediments from a Taiwanese As hot spot aquifer.
References:
[1] Rowland, H.A.L. et al. J. Environ. Qual. 38, 1598-
1607 (2009)
[2] van Dongen, B.E. et al. Appl. Geochem. 23, 3047-
3058 (2008)
[3] Polya, D.A. and Charlet, L. Nature Geosc. 2, 383-
384 (2009)
[4] Hery, M. et al. Geobiol. 8, 155-168 (2010)
280

P-140
Effects of natural and artificial oxidation on dissolved organic
matter: example of Boom Clay
Pascale Blanchart 1 , Pierre Faure 1 , Raymond Michels 1 , Christophe Bruggeman 2 , Mieke
De Craen 2
1 UMR7566 G2R, CNRS, Nancy Université, Vandoeuvres-lès-Nancy, France, 2 SCK-CEN, Mol, Belgium
(corresponding author:Pascale.blanchart@g2r.uhp-nancy.fr)
The Boom Clay (Belgium) is studied as a
reference host rock for methodological studies on
the geological disposal of high-level and longlived
radioactive waste. The drilling of galleries in
the Boom Clay at Mol lead to perturbations of the
initial physical and chemical conditions. Since
organic matter is present in this argillaceous
formation, it is important to know its response to
these new conditions.
The Boom Clay pore water (20% in mass of
rock) contains significant quantities of Dissolved
Organic Carbon (DOC) with a mean concentration
of 115+/-15 mg/L, determined on the basis of
piezometer water as well as rock squeezing and
leaching experiments. Yet, in piezometers, the
DOC may show considerable and irregular
variations through time, with values ranging
between 80 and 425 mg/L [1]. The origin and biophysico-chemical
controls of such variations are
yet unknown. In this presentation the influence of
oxidation on the aforementioned observations is
studied.
Three categories of samples were studied:
1) Fresh as well as air-oxidized Boom Clay
samples were collected in the
Underground Research Facility (URF) of
SCK•CEN (Mol, Belgium); they represent
a natural series of oxidation
2) A fresh Boom Clay sample was
submitted to air oxidation (artificial
series). In these experiments, powdered
clay was heated at 80°C under air flow
during 1, 3, 6, 9, 12, 18 months,
3) Four water samples were collected from
different horizons in the Boom Clay by
means of piezometers located in the
Underground Research Facility during
January 2010.
The Dissolved Organic Matter (DOM) of natural
and artificial oxidation series was extracted by
soxhlets and leaching experiments using pure
water.
Different analyses were conducted and their
results will be presented in detail: DOC
measurements give a quantitative evolution of
DOM with the oxidation process, while PyGC, 3D-
Fluorescence, FTIR, GPC and APPI-QTOF were
used to characterize the DOM.
The evolution of DOM as a function of oxidation
could be evidenced in the natural and the artificial
oxidation series. The composition of the DOM
samples collected from the piezometer waters
was homogeneous.
All the results allow to describe the different
stages of organic matter oxidation in relationship
to the formation of dissolved organic matter:
kerogen decomposition, formation of free organic
matter, clay catalysis, neoformation of water
solubles. Geochemical tracer parameters of the
alteration process could be identified. These can
be used to assess the alteration state of samples
in the Boom Clay and to infer if air oxidation has
an influence on the composition of the formation
water.
This study thus brings a sound background to
the understanding of the reactivity and mass
balances implied in the oxidation of fossil organic
matter from clay. This may be of broader interest
to issues like continental erosion in relationship to
fossil carbon input into the surface carbon cycle.
[1] De Craen M., Wang L., Van Geet, M. & Moors H. (2004)
The geochemistry of Boom Clay pore water at the
Mol site, status 2004. SCK•CEN Scientific Report.
BLG 990.
281

P-141
Biosurfactants – a green alternative to synthetic surfactants
Gunhild Bødtker 1 , Ina Hvidsten 2 , Tanja Barth 2
1 Uni CIPR, Uni Research, UoB, Bergen, Norway, 2 Petroleum and Colloid Chemistry Research Group,
Department of Chemistry, UoB, Bergen, Norway (corresponding author:gunhild.bodtker@uni.no)
Surfactants are amphiphilic compounds that have a
wide range of application in commercial production of
food, cosmetics and pharmaceuticals in addition to
applications in agriculture and petroleum industry.
The steady demand for new specialty surfactants
have lead to an increased interest in biologically
produced surfactants, termed biosurfactants. In
addition to being generally nontoxic, biosurfactants
tend to be more effective (low critical micelle
concentration, CMC) and stable than synthetic
biosurfactants. They are also biodegradable and
environmentally friendly, thus fitting the definition of
currently sought-after ―green chemicals‖. The
properties of biosurfactants have high commercial
value, as are reflected in the recent years increase in
research interest [2].
Biosurfactants may be produced by animals, plants
and microorganisms, but are most often associated
with bacteria growing on water-immiscible oily
substrates such as high-molecular-weight
hydrocarbons. Biosurfactant production is initiated as
a response to the presence of specific substrates
(e.g. hydrocarbons) and requires multi-component
enzymes for its synthesis. They may be cell-bound or
excreted into the surrounding environment.
Biosurfactants are a diverse group of biomolecules
varying in composition from low molecular-weight
glycolipids and lipopeptides to high-molecular-weight
lipopolysaccharides, proteins and lipoproteins (figure
1). The amphiphilic composition of biosurfactants,
which orients these molecules towards both
hydrophilic and hydrophobic phases, gives
tensioactive properties that reduce surface and
interfacial tensions. Extracellular biosurfactants have
emulsifying properties that form oil-in-water emulsions
that leaves the oil accessible for uptake and
degradation by bacteria. Cell-bound biosurfactants on
the other hand, enables bacteria to be situated at the
oil/water interface. Subsequent exponential growth at
the interface leads to a corresponding exponential
reduction of the interfacial tension (IFT). Growthdependent
reduction in oil/water IFT is believed to be
one of the key mechanisms in microbial enhanced oil
recovery (MEOR).
We are in the process of isolating and characterizing
biosurfactants produced by oil-degrading bacteria
isolated from petroleum environments with regard to
their molecular structure and physiochemical
properties. Present research is focusing on the very
efficient biosurfactants produced by a new
Actinobacterium. This oil field bacterium is able to
reduce oil/water IFT by close to ~10 4 while growing at
an n-dodekan/water interface at ~20 o C [1].
Characterization of cold-loving oil-degrading bacteria
from geoactive sites in the arctic region show high
potential for long-chained n-alkane degradation,
which suggests production of cold adapted
biosurfactants. Our overall aim is to assess
biosurfactants as candidates for development of
green chemicals for the oil industry. The major
challenges related to the commercial use of
biosurfactants are the high-cost production compared
to synthetic surfactants, and their biodegradability that
may lead to loss of efficiency during application.
Fig. 1 Structures of biosurfactants [2]
References
1.Kowalewski E, Rueslåtten I, Gilje E, Sunde
E, Bødtker G, Lillebø BLP, Torsvik T, Stensen JÅ,
Bjørkvik B, and Strand KA (2005) Interpretation of
microbial oil recovery from laboratory experiments.
13th European Symposium on Improved Oil
Recovery, Budapest, Hungary 25-27 April
2.Soberón-Chávez G Biosurfactants: From Genes to
Applications (2011) Springer-Verlag Berlin,
Heidelberg
282

P-142
Geochemical parameters assessment in sediments of Lake
Coari (Amazon)
Tatiana Santos da Cunha 1 , Francisco Fernando Lamego Simões Filho 1 , Celso Marcelo
Franklin Lapal 2 , Maria de Lourdes Moreira 1 , Luis Landau 3 , Celeste Yara dos Santos
Ciqueira 3
1 Instituto de Engenharia Nuclear - Comissão Nacional de Energia Nuclear, Rua Hélio de Almeida, 75,Zip
Code 21941-906, Rio de Janeiro, Brazil, 2 Instituto Nacional de C&T de Reatores Nucleares Inovadores, Rio
de Janeiro, Brazil, 3 Centro de Tecnologia - Bloco I sala 214, Av. Athios da Silveira Ramos, 149, Rio de
Janeiro, Brazil (corresponding author:tatianadantasrj@yahoo.com.br)
This study aims to understand Lake Coari function
through the geochemical analysis of sediments,
assessing the contaminants input into the lake and
also their behavior in case of environmental accident
in the region.
To achieve this proposal, we collected samples an
surface sediments located downstream (Tesol 1) and
upstream (Tesol 2) of Petrobras Terminal; a core at
the entrance of Lake Coari and another in front of the
Coari city.
The objective was to compare the concentrations of
metals, organic matter with possible factors
controlling the deposition process in these different
points. The deposition of 210 Pb was also evaluated in
order to correlate the geochemical parameters with
their respective sources.
The sediment profile at the entrance of Lake Coari
(P4) showed higher values of TOC (0.72%) and C/N
(27.4%), whereas in the sediment profile P5, situated
into the lake Coari, the TOC values (0 44%) and C/N
(18.3%) were lower. It suggested higher affinity of P4
with the material carried by the Solimões river.
The predominance of odd n-alkanes of higher
molecular weight and higher intensities for n-C29 in
surface samples of the P4 sediment profile and Tesol
corroborate the terrestrial debris as the main source
of those materials. Records of perylene in some of
those samples reinforce this origin.
Highest concentrations of metals with anthropogenic
origin corresponded to excess
210 Pb, ie, the
sediments brings the latest sign of anthropogenic
disturbance within the lake Coari. Thus, the effects of
the material transported by the Solimões river
reaches the entrance of the lake while the sediments
within the lake portray a system without the influence
of the main river. At this site the sediment deposition
reflects the input of material from the kale‘s drainage
basin and lake primary productivity.
The analysis also confirmed the absence of
petrogenic material in the region, proving that it was
not yet impacted by oil activities.
Figure 1: Study area
References:
[1] Aquino Neto, F.R.; Nunes, D.S.S. Cromatografia -
Princípios básicos e técnicas afins. Rio de Janeiro,
Editora Interciência Ltda., 2003.
[2] Baird, C. 1999. Environmental Chemistry. 2a Ed.,
New York: W. H. Freeman, 557p.
[3] Barrocas, P.S.R. 1998. Estudos da concentração
de metais pesados nos igarapés Matrinxã, Acará,
Bolívia, Tarumã (Manaus-AM). Dissertação de
Mestrado em Ciências Ambientais. Centro de
Ciências Ambientais. Universidade Federal do
Amazonas.
[4] Bouloubassi, I. 1990. Aspects de la biogéochimie
des hydrocarbures non aramatiques dans La colonne
d‘eau et lês sediments du milieu côtier: cas du delta
du Rhône, Thése de Doctorat, Université Paris 6,
France, p. 344.
[5] Bouloubassi, I.; Saliot, A., 1993. Dissolved,
particulate and seidimentary naturally derived
polycyclic aromatic hydrocarbons in a coastal
environment: geochemical significance. Marine
Chemistry, 42, 127-143.
283

P-143
Phenolic compounds in water leachates of Miocene lignites from
the Konin Brown Coal Basin (Poland)
Monika Fabiańska, Urszula Skręt
University of Silesia, Sosnowiec, Poland (corresponding author:monika.fabianska@us.edu.pl)
High degree of functionality of Miocene lignites
likely renders them susceptible to leaching of organic
matter by water [1]. As Finkelman et al. [2] indicates
such solutions of organic compounds should be
considered the reason of considerable health and
environmental hazard. The first aim of the project
was to determine whether low-weight organic
compounds could be transported outside of the mine
outcrops and/or lignite beds in water solutions and to
what extent. The second one was to identify and
characterize distributions of soluble compounds and
to explore their possible application as a fingerprint
indicating lignite source in future research on
groundwater and soil contamination in the nearby
area.
To this end, ten samples of Miocene lignites were
selected from a set of 65 previously investigated
samples from the Konin Brown Coal Basin (Poland) of
variable litotype and petrography. The highest
dichloromethane (DCM) extract yields and gas
chromatography-mass spectrometry data were used
as a guide. Petrologic analyses were carried out in
reflected, white light. Analytical procedures used in
microscopic studies followed ICCP standards. Waterwashing
processes were simulated by stirring 50 g of
powdered lignites with distilled water (200 ml, 3x30
min). Collected water extracts were filtered and
dissolved organic compounds isolated by solid phase
extraction on BAKERBOND Speediscs PolarPlus
(C18) (procedure as applied for drinking water).
Separated organic phases were analysed by GC-MS
on a HP-5 column, 60 m, id = 0.20 mm (EI mode at
70eV, full scan mode). Compounds were identified by
their spectra, and by comparison with standards
analysed previously and with literature data [3].
While the DCM extraction yields of lignites lie in the
range 0.9-20.2% (wt.), the water-extraction yields fall
in the range 0.001-0.048% (wt.).Extractability of
water-washed lignites was in the range of 0.2-6.0%
(wt.), i.e. much lower than that of non-washed lignites.
The main components of the leachtes are aliphatic
phenol derivatives related to lignins being the main
component of the lignite macromolecule, particularly
in macerals of huminite group. These macerals occur
in ca 59.2-87.5% in the lignites investigated. Phenols
form ca 70-95% of organic phases leached from
lignites. The type of phenols shows unambiguous
relationship to the parent lignite and its biological
origin, i.e. a leachate of deciduous wood-derived
xylithe contained compounds of syringic molecular
structure such as 2,6-dimethoxybenzoquinone and
syringic aldehyde. That phenolic unit is commonly
found in lignin of deciduous trees. More common
were phenolic compounds being guaiacol derivatives
such as ethyl homovanilone, vanilline, homovanilic
acid, and apocynine which indicate conifers input.
Leachate minor components were aliphatic ketones
and aldehydes, aliphatic alcohols and esters of fatty
acids. Aromatic hydrocarbons occur in a limited range
and comprised phenanthrene, fluorene and pyrene
among unsubstituted compounds. In a few leachates
also methyl- and dimethylnaphthalenes were found.
In a view of other environmental investigations the
concentration of water-soluble phenol derivatives and
lighter aromatic compounds in leachates mean a
significant hazard to health and environment [2].
These compounds could be transferred to
groundwater from large open cast mines of lignites
exploited in several large brown coal basins in Poland
and Germany.
References
[1] Stefanova M., Oros D.R., Otto A.. Simoneit B.R.T.
2002, Polar aromatic biomarkers in the Miocene
Maritza-East lignite, Bulgaria, Org. Geochem., 33,
1079-1091.
[2] Finkelman R.B., Orem W.H., Castranova V., Tatu
C.A, Belkin H.E., Zheng B., Lerch H. E., Maharaj
S.V., Bates A.L. 2002. Health impacts of coal and
coal use: possible solutions. <strong>International</strong> Journal
of Coal Geology 50, 425– 443.
[3] The Wiley/NBS Registry of Mass Spectral Data,
Wiley, New York (2000).
284

P-144
Organic compounds of geochemical origin in domestic furnaces
coal ash (Upper Silesia, Poland)
Monika Fabiańska, Danuta Smołka-Danielowska
University of Silesia, Sosnowiec, Poland (corresponding author:monika.fabianska@us.edu.pl)
Coal combustion generates a great amount of ash
exceeding 550 . 10 6 tonnes/year worldwide. While in
power plants most of ash is collected in cyclones, in
domestic combustion finer fractions of ash are emitted
to the air or dumped out without any control. Due to
its adsorbing properties coal ash can contain organic
compounds deriving from parent coal or formed in
burning. Since domestic coal combustion is the most
hazardous to the environment it is important to find
what biomarker distributions are characteristic for this
emission source. In future, these results may help to
distinguish the domestic combustion input to organic
pollution and to the general background of organic
compounds present in the urban air. The research
aim was: (i) to establish what organic compounds are
present in coal ash from domestic furnaces, (ii) to find
their source, and (iii) to assess changes in biomarker
distribution caused by combustion.
Coal ash was sampled in two domestic furnaces
using Upper Silesia coals (Poland) for central heating,
located in the Orzesze and Piekary Śląskie towns.
Analyses comprised ash ultrasonic extraction and gas
chromatography–mass spectrometry (GC–MS) of the
total extracts.
Ash extract yields were in the range 0.002-0.032
% (wt.). Aliphatic hydrocarbons dominate in extracts
chemical composition, particularly n-alkanes. Lightweight
compounds were not common, with the
Orzesze domestic coal ash more often containing
them than the Piekary Śląskie ash extracts. All coal
ash extracts show a monomodal distribution of nalkanes
in the range from n-C13 to n-C35 without oddover-even
carbon number atom predominance
(CPI~1.0). Long-chain n-alkanes predominate over
lighter compounds. Values of pristane/phytane ratio
are > 1.00 in the Orzesze ash extracts while the
Piekary Śląskie extracts show more various
distributions, with these compounds absent in many
samples. Pentacyclic triterpanes are present in the
range from 18α(H)-22,29,30-trisnorneohopane (Ts) to
trishomohopanes (C33). The distribution is mature in
almost all Orzesze extracts, however, in some cases
it is thermally degraded. Only a few Piekary ash
extracts contained pentacyclic triterpanes. Steranes
occur in few samples and in very low concentrations.
This feature is inherited from the source Upper Silesia
coals in which steranes are often absent or present in
low amounts. Stigmastanes dominate whenever
steranes are present in extracts. Polycyclic aromatic
hydrocarbons comprised compounds with 2-5
aromatic rings unsubstituted and substituted with C1-
C4 alkyl groups, with naphthalene occurring in low
amounts or absent, and phenanthrene showing the
highest concentrations. Also polar compounds were
found mainly phenol and its derivatives (4methylphenol,
4-propylophenol, 3,4- and 3,5dimethylphenol).
These compounds probably come
from thermal destruction of vitrinite macromolecule or
conifer wood applied together with coal since phenolic
units are considered to be of lignin origin [1].
Due to relatively low combustion temperatures in
domestic furnaces (270 o C) and incomplete
combustion many biomarkers from the parent coal
survived the process. Their distributions are
unchanged or only slightly changed by heat and show
features of the source fuel, i.e. bituminous coal of the
Upper Silesia Coal Basin [2]. Such compounds as
steranes, or pentacyclic terpanes obviously come
from unburnt particles of coal. Compounds
considered to be formed in combustion are minor
components of ash extracts. Two series of samples
differ due to slightly higher temperature of the Piekary
Śląskie furnace and better oxygenation of its coal
combustion zone.
[1] Hatcher P.G., Faulon J-L., Wenzel K.A., Cody
G.D. 1992. A structural model for lignin-derived
vitrinite from high-volatile bituminous coal
(coalified wood), Energy & Fuels, 6, 813-820.
[2] Kotarba M.J., Clayton J.L. 2003. A stable carbon
isotope and biological marker study of Polish
bituminous coals and carbonaceous shales.
<strong>International</strong> Journal of Coal Geology, 55, 73-94.
285

P-145
Current level of the organic pollution in the Bílina river
sediments (Czech Republic)
Eva Francu, Milan Gerńl, Kateřina Zelenková
Czech Geological Survey, Brno, Czech Republic (corresponding author:eva.francu@geology.cz)
The occurrence and distribution of selected
persistent organic pollutants in sediments of
the Bilina River (a tributary of the Elbe River,
Czech Republic and Germany) was
investigated in order to receive current level
of pollution. The area along the Bilina River is
the highest polluted area in the Czech
Republic with extreme risks. During the past
100 years, the region is loaded by the
opencast brown coal mining and coal
processing, petroleum refineries, and
chemical plants. As by-product waste
deposits were accumulated as additional
potential source of secondary contamination.
The Bilina River itself has limited natural part
and most of the river is artificial hydrological
system comprising complex water pipeline
network. In this study the level of the DDT,
PCB, PAH, and compounds indicating oil
contamination was investigated. Samples of
river sediments were taken at 33 sampling
sites on an 82 km longitudinal section of the
Bilina River. Two river sediment samples
from Elbe River before and after Bilina
confluence were collected.
Contamination in the river sediments coming from
petrogenic sources is indicated by an elevated level of
total extractable hydrocarbons (up to 7917 mg/g) and
is supported by high amount of saturated steranes
and hopanes. These sediments have also specific
pattern of selected polyaromatic hydrocarbons (PAH)
(Fig.1). All examined river sediments have very high
amount of the sum of PAHs ranging from 1149 μg/kg
in the sources of the river area to 226307 μg/kg in the
central part. Using the classification diagram designed
by [1] we define three different possible PAH sources.
First petroleum group represent area close to the
refinery; second group includes sources of the river
where the petroleum signatures are present even in
the area is in front of the refinery. That can be
explained by the atmospheric transport of the light
PAH from refinery. The last pyrogenic group
represents samples from natural part of the river and
samples collected under coal waste. The extreme
concentration of the DDT 53 594 μg/kg in the area
together with the presence of p,p'-DDT indicates
current source. This work has been supported by The
Ministry of the Environment of the Czech Republic,
Project MZP-OOHPP-87/08/GP.
IP/(IP+Bghi)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
Petroleum
Petroleum
Combustion
rs close to
petroleum refinery
Grass/Wood/Coal
Combustion
rs from natural part
or under coal waste
rs from quelle part
0.3 0.4 0.5 0.6 0.7 0.8
Fl/(Fl+Py)
Figure 1. Bílina river sediments (rs) in the PAH cross
plot of IP/IP+Bghi vs. Fl/Fl+Py ratios (fields designed
by [1])
References
[1] Yunker, M.B., Macdonald, R.W., Vingarzan, R.,
Mitchell H., Goyette, D., Sylvestre, S., 2002. PAHs in
the Fraser River basin: a critical appraisal of PAH
ratios as indicators of PAH. Organic Geochemistry 33,
489-515.
286
Grass/Wood/Coal
Combustion
Petroleum
Combustion

esponce
P-146
Alteration of aromatic hydrocarbons from the oil pollutions by
aerobic biodegradation
Elena Fursenko 1 , Vladimir Kashirtsev 1 , Lyubov Altunina 2 , Varvara Ovsyannikova 2 ,
Ludmila Svarovskaya 2
1 Trofimuk Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation,
2 Institute of Petroleum Chemistry SB RAS, Tomsk, Russian Federation (corresponding
author:fursenkoea@ipgg.nsc.ru)
At present, in organic geochemistry quite a
considerable interest has been invited by works
addressing compositional changes in oil components
under their biodegradation. Such type of works are
important both when evaluating the biodegradation
intensity of oil pollution and in determining the degree
of natural oil and bitumens microbial oxidation.
This paper offers a comparative analysis for
distribution of aromatic hydrocarbons (HC), identified
by GCMS method in naphthene-aromatic fractions of
chloroform extracts (Echl), obtained prior to and after
modeling the aerobic biodegradation processes in
petroleum drilling mud by aboriginal microflora (two
experiments). Under biodestruction, the mass of
petroleum mud has decreased by 20-30%, on
average, per month. According to the data on the
composition of saturated fraction of Echl, the
biodestruction of petroleum sludge varies from slight
to moderate degree /1, 2/: in the biodegraded
samples the concentration of n-alkanes has
decreased (down to their total disappearance), with
acyclic isoprenanes (mainly, pristine & phytane)
content going higher, in the meantime;
concentration‘s ratios of steranes to terpanes have
not changed.
In chromatograms for total ion current (TIC) in the
biodegraded samples, unlike in the initial ones, there
was observed the escalation of the peaks intensity,
characterizing methylphenanthrenes and
dimethylphenanthrenes (fig. 1).
1 2
initial sample biodegradated sample
retention time (min)
1 2
retention time (min)
Figure 1. Total ion current (TIC) in the naphthenearomatic
fraction of the studied samples
(1 - methylphenanthrenes,
2 - dimethylphenanthrenes)
Alkylbenzenes (fig. 2), methylalkylbenzenes (m/z
105, 106) and dimethylalkylbenzenes (m/z 119, 120),
responce
observed in the initial samples, have disappeared in
the biodegraded samples.
initial sample biodegradated sample
m/z 92
m/z 91
retention time (min)
m/z 92
m/z 91
retention time (min)
Figure 2. The mass chromatograms
for alkylbenzenes
Alkylnaphthalenes (m/z 128) have been hardly
identifiable in the composition of naphthalenes in the
biodegraded samples; whereas the concentrations of
dimethylnaphthalenes (m/z 142, 156) and
trimethylnaphthalenes (m/z 170) have considerably
diminished.
Thus, the comparative analysis performed for the
data on the composition of aromatic HCs in both initial
and biodegraded products has shown that already at
initial stages of biodegradation, alkylbenzenes and,
partly, alkylnaphthalenes undergo a complete
reduction. Whereas dimethylnaphthalenes
trimethylnaphthalenes have been affected by
biodegradation to a lesser extent. At earlier stages of
biodegradation the phenanthrenes and more
condensed structures are known not to be subjected
to alteration. So, apart from the data on the
composition of saturated fractions of oils and
bitumens, it is advisable to use the ratios of aromatic
HCs by their composition for evaluation of the
intensity of their microbial oxidation. We can
recommend to use some specific HC-biomarkers (e.g.
retene) as markers for detection of sources of oil
pollution.
This work was supported by the Interdisciplinary
Integration Project of SB RAS № 31.
References
[1] Kashirtsev, V.A. Organic geochemistry of
naphthides in Siberian Platform. – Yakutsk,
Izdatelstvo SB RAS, YaF, 2003. – p. 160.
[2] Peters, K.E. The biomarker guide/ 2 nd ed./ K.E.
Peters, C.C. Walters, J.M. Moldovan. – USA, New
York: Cambridge University Press, 2007. – P. 1155
287

P-147
The d13C composition of individual n-alkanes in sediments from
Brazilian estuarine systems by GC/C/IRMS
Otávio Luiz Gusso Maioli 1 , Cristiane Rossi Oliveira 1,2 , Marco Aurélio Dal Sasso 1 , Luiz
Augusto do Santos Madureira 2 , Francisco Radler Aquino Neto 1 , Débora Almeida de
Azevedo 1
1 Federal University of Rio de Janeiro, Rio de Janeiro, Brazil, 2 Federal University of Santa Catarina,
Florianópolis, Brazil (corresponding author:otaviomaioli@iq.ufrj.br)
The carbon isotopic signature can be used to better
distinguish among sources because n-alkanes have
non-unique chain length signatures [1]. The 12 C/ 13 C
(δ 13 C) isotope ratio in natural materials varies slightly
as a result of isotopic fractionation during physical,
chemical and biological processes and can be used
as diagnostic tool of key environmental processes [2].
The δ 13 C composition of n-alkanes (from C16 to C34)
were measured in surface sediments from Babitonga
Bay (BAB), Imbituba (IMB) and Itajaí-Açu River (ITA)
(three estuarine systems from Santa Catarina State,
Southern Brazil), Manguaba Lagoon region (MAN)
(an estuarine lagunar system of Alagoas State,
Northeastern Brazil) and Paraíba do Sul River (PSR)
and its estuary (PSE) (an estuarine deltaic system of
Rio de Janeiro State, Southeastern Brazil). These five
estuarine systems are impacted by different activities
such as harbor, urbanization, industrialization and
sugar cane plantation. The aim of this study was to
evaluate the impact of the anthropogenic activities in
these estuarine systems and to determine the origins
of the organic matter. The n-alkanes were analyzed
by gas chromatography-combustion-isotope ratio
mass spectrometry (GC/C/IRMS) and quantification
was performed on a GC-FID.
The levels of n-alkanes ranged from 0.34 to 18.14
�g kg -1 , being relatively low compared to other studies
in the world, such as, Azerbaijan, near oil fields (0.1 to
17.0 mg kg -1 ) [3]. The Carbon Preference Index (CPI)
calculated in the C23-C34 range indicates that nalkanes
are mainly inherited from cuticular waxes of
higher plants. The � 13 C compositions of n-alkanes
ranged from -41.8 to -18.3 ‰, showing different
sources for the studied estuarine systems. Principal
Component Analyses (PCA) suggest a petrogenic
source, which was justified by differences between
δ 13 C of odd and even carbon number, as seen in the
example of Fig. 1A. The enrichment of � 13 C values for
C27, C29, C31 and C33 (Fig. 1B) indicates contribution
of C4 plant (sugar cane residues) in PSR-1 and PSR-
2, both located close to an ethanol plant.
Influence of C3 plant (probably characterized by
dense Ombrophile forest) was observed in ITA by
decrease of 13 C (about 10‰ compared to PSR � 13 C
values of C27, C29 and C31).
δ13C (‰ VPDB)
δ13C (‰ VPDB)
-18
-24
-30
-36
-42
-18
-24
-30
-36
-42
nC16
nC17
nC16
nC17
nC18
nC19
nC18
nC19
nC20
nC21
nC20
nC21
nC22
nC23
nC22
nC23
nC24
nC25
n-alkane
nC24
nC25
n-alkane
nC26
nC27
nC26
nC27
nC28
nC29
nC28
nC29
nC30
nC31
nC30
nC31
nC32
nC33
nC32
nC33
PSE-1
PSE-2
PSE-3
PSE-4
nC34
PSR-1
PSR-2
Fig.1. Profiles of the n-alkane isotopic composition (� 13 C) in
surface sediments of the Paraíba do Sul, one of the studied
Brazilian estuarine systems. A) estuary; B) river.
The assessment of δ 13 C of n-alkanes in sediments
from five Brazilian estuarine systems played a role
about the understanding of impacts from harbor
activities, industrialization, urbanization and sugar
cane plantation.
References
[1] Sikes, E. L., Uhle, M. E., Nodder, S. D., Howard, M. E.
(2009). Mar. Chem. 113, 149-163.
[2] Meyers, P.A. (2003). Org. Geochem. 34, 261-289.
[3] Tolosa, I., Mora, S., Sheikholeslami, M. R., Villeneuve,
J. P., Bartocci,J., Cattini, C. (2004). Mar. Poll. Bull. 48,
44-60.
A
B
nC34
288

P-148
Seasonal Contamination in Lake Van (Turkey)
Carme Huguet 1 , Susanne Fietz 1 , Mona Stockhecke 2 , Núria Moraleda 1 , Antoni Rosell-
Melé 1,3
1 Institut de Ciència i Tecnlogia Ambientals, Universitat Autònoma de Barcelona, Cerdanyola, Spain, 2 Eawag,
Swiss Federal Institute of Aquatic Science and Technology, Department of Surface Water Research and
Management, Dubendorf, Switzerland, 3 cInstitució Catalana de Recerca i Estudis Avançats (ICREA),
Barcelona, Spain (corresponding author:carme.huguet@uab.es)
Lake Van in Eastern Anatolia (Turkey) is the world‘s
largest soda lake (3570 Km 2 ) 1 . It is located in a
heavily populated area and receives over 1 million m 3
of domestic wastewater a year 2 . Moreover oil
contamination was detected in sediments but its origin
could not be determined 2 . This study aimed to assess
contamination seasonality and sources. This was
achieved by measuring biomarkers in monthly
sediment traps
Biomarkers such as hopanes, steranes and n-alkanes
provide information on anthropogenic contamination,
especially from petrogenic sources 3 , while branched
tetraethers abundance and the BIT index indicate
natural terrestrial input 4 . Natural terrestrial input was
found to be mainly related to increased precipitation
and snowmelt in autumn and spring (Fig. 1). While
almost all n-alkanes in summer 2006 and at least half
in summer 2007 are derived from natural sources, in
winter we observe a marked increase in
anthropogenic contamination related n-alkanes (Fig.
1). This winter peak has a carbon preference index
(CPI) below 1 (Fig. 1) indication of a kerogen rich
source and petrogenic contamination. This is
supported by higher hopane and sterane maturity
indices during the winter months. Contrastingly the
summer peaks show a relatively high CPI and lower
maturity values indicating a different source of
contamination.
We postulate that the winter peak is due to the winter
fossil fuel contribution from domestic heating, while
the summer increase is caused by touristic activity.
References
[1] Kempe, S. et al. 1991 Nature 349, 605-608.
[2] Öğün E. et al. 2005. Fres.Envir. Bull. 14, 1031-
1035.
[3]Hostettler, F. D. et al. 1999. Mar. Chem. 64, 115-
127.
[4] Hopmans, E.C. et al., 2004. Earth and Planet, Sci.
Let. 224, 107-116.
Figure 1. Terrestrial input (August 2007 to July
2007; 38º38‘N 42º46‘E). a) branched GDGT
abundance (orange) and BIT index (grey line), b) nalkane
abundance divided into algal (green),
terrestrial plants (brown) and anthropogenic
contamination (yellow), carbon preference index CPI
(black line), c) Temperature (solid line), wind speed
(dashed line) and precipitation (histogram).
289

P-149
Targeted chemical and physical characterisation of a biosurfactant
produced by the novel Actinobacterium
Ina Hvidsten 1 , Gunhild Bødtker 2 , Tanja Barth 1
1 Petroleum and Colloid Chemistry Research Group, Depatment of Chemistry, University of Bergen, Bergen,
Norway, 2 Uni CIPR, Uni Research AS, Bergen, Norway (corresponding author:ina.hvidsten@kj.uib.no)
The research findings of the last two decades have
already proved that chemical compounds of biological
origin can be both valuable for industrial applications
and environmentally friendly [1]. Identification of such
compounds produced by prokaryotic microorganisms,
referred to as metabolites, is one the major tasks of
metabolomics, see Table 1 for the summary of
approaches and techniques.
Major metabolomic approaches
(applicable also for extracellular metabolites)
Metabolic Semi-quantitative, pre-defined metabolite type.
profiling Analytical Techniques (AT): TLC, FT-IR.
Targeted Quantitative, structure analysis, extensive sample
analysis preparation.AT: HPLC-UV/ELCD, LC/GC-MS,NMR.
Metabolic High throughput, global analysis pattern recognition
fingerprinting for sample classification. AT: FT-IR, NMR.
Metabolic Analysis of chemical/biochemical alterations
footprinting produced by an organism on its environment.
Table 1: Summary of metabolomics approaches and techniques,
those used in this project are highlighted. Modified after [2].
These structurally diversified compounds are seconddary
metabolites of wide range molecular mass
produced by microorganisms either in the late log
phase and/or as a response to different stresses
imposed on the cell, though carbon source (cs) is the
major regulative factor [3]. BSs exhibit interesting
properties in respect to MEOR [4, 5] due to their
amphiphilic nature.
Our project addresses the characterisation as specified
in Table 1 of surface active compounds. These
bio-surfactants (BSs) are produced by a novel Grampositive
mesophilic aerobic chemo-organotrophic
prokaryote, phylum Actinobacteria, family Corynebacteriaceae.
Experimental:
Samples: Pure culture incubations were set up with
a). different carbon sources (sugar; n-dodecane n-
C12) in 2L round flasks and b). different volumes in 2L
and 10L flasks, added n-C12 as the only cs. The
cultures were incubated at optimal temperature 30 o C
w/t agitation and harvested at the early stationary
phase - after 4 weeks. Two types of samples were
obtained: 1. aqueous medium 2. bacterial cell
biomass.
Pre-treatment and –separation: centrifugation
(7000rpm, 25 min.); sample-type 1: quenching of
enzymatic activity; sample-type 2: lyophilisation.
Preliminary screening: oil-spreading test;
determination of cell-surface charge. Fractionation
and purification for sample-type 2: Soxhlet extraction:
a crude extract; Solid Phase Extraction (SPE):
fractionation of the crude extract; purity check by
normal phase/NP- and reverse phase/RP-TLC; FT-IR.
Surface-active fractions: Reverse Phase High
Pressure Liquid Chromatography (RP-HPLC); LC-
ESI/MS. Structure identification by NMR was
attempted.
Results and Discussion:
The results show that production of BS in this microorganism
is regulated by the carbon source, and that
it is coupled to utilisation of certain water-immiscible
substrates (here, a straight chain alkane). A large
area of water-to-carbon-source interface is vital for
high BS-yield. Further, both sample pre-separation
and oil-spreading tests indicate that the BS is both
strongly cell-associated and partially released into the
aqueous medium by the end of the log phase. Cellsurface
charge tests, along with oil-spreading tests,
indicate production of a potent anionic BS. The SPE
polar fractions that exhibited highest activity in oilspreading
test were analysed further by FT-IR: which
identified presence of aliphatic (Cn), ether (C-O-C),
carbonyl (C=O) and amine moieties, TLC indicated
peptide moieties. Further characterisation indicates
production of lipopeptide-type BSs. Method
reproducibility is challenged by matrix interferences
due to the complexity of samples. Therefore, we also
present a flowchart of the reliable and detailed
analysis protocol and suggestions for calibration
methods for complex biological samples in targeted
metabolomics analysis.
References:
[1] Banat et al. (2010) Appl. Microbiol. Biotechnol. 87,
427-444.
[2] Shulaev, V. (2006) Brief. Bioinf. 7:2, 128-139.
[3] Ruiz et al. (2010) C.Rev.Microbiol. 36:2,146-167.
[4] Bødtker et al. (2009)Ant. van Leeuw.96,459-469.
[5] Kowalewski et al. (2005) 13 th Europ. Sym. on IOR.
Acknowledgments: 1. Statoil, Norway; 2. Terje
Lygre, UoB, Norway.
290

P-150
Polycyclic aromatic hydrocarbons in surface sediments of the
Jade Bay, North Sea, Germany
Angelika Klugkist, Barbara M. Scholz-Böttcher, Jürgen Rullkötter
Institute of Chemistry and Biology of the Marine Environment (ICBM), Carl von Ossietzky University of
Oldenburg, P.O. Box 2503, D-26111 Oldenburg, Germany (corresponding author:angelika.klugkist@unioldenburg.de)
The Jade Bay, with an areal extension of 190 km 2 , is
a tidal flat embayment in the eastern part of Lower
Saxony west of the Weser and Elbe estuaries. In
contrast to the nearby estuaries, the Jade Bay has no
significant fluviatile inflow. Besides some small
streams there is only a temporary freshwater
discharge through tidal gates [1]. Hence, most of the
allochthonous organic matter and pollutants enter this
system via aeolian deposition and the tidal currents.
As part of an interdisciplinary scientific monitoring
program investigating the present environmental
status of the Jade Bay in terms of nutrients, heavy
metals and organic pollutants, the distribution of the
16 EPA polycyclic aromatic hydrocarbons (PAHs) in
surface sediments are presented here. More than 105
sediment samples from a sampling grid covering the
whole Jade Bay were analysed by ultrahigh
performance liquid chromatography (UPLC) with
fluorimetric detection.
The PAHs are not homogeneously spread over the
sampling area. On a dry sediment basis low amounts
of the 16 EPA PAHs were found in the eastern and
central Jade Bay, whereas PAH loadings were higher
in the southern, western and northern part of the
study area. The PAH contents, ranging from less than
50 µg/kg dw to more than 500 µg/kg dw in the area of
the Nassau harbour, Wilhelmshaven, are below
legally permitted values [2]. High proportions of
naphthalene, phenanthrene and fluoranthene relative
to total PAHs point to domestic fuel and industrial
combustion processes as main emission sources.
The TOC content of the Jade Bay samples is closely
associated with the grain size fraction

P-151
Cu(II) complexation with humic acid and humic-like ligands
studied by Schubert’s method
Ivana Kostic 1 , Tatjana Andjelkovic 1 , Ruzica Nikolic 1 , Milovan Purenovic 1 , Aleksandar
Bojic 1 , Darko Andjelkovic 2 , Jelena Mitrovic 1
1 University of Nis, Faculty of Sciences and Mathematics, Nis, Serbia, 2 Water Works Association "Naissus",
Nis, Serbia (corresponding author:ivana.kostic83@gmail.com)
Humic substances are colloidal, heterogeneous,
polydisperse macromolecules. They are the major
organic constituents of soil, water sediments, being
main representatives of complex environmental
chemical systems. Due to the presence of hydroxyl,
phenyl and carboxyl-reactive groups, coordination
compounds of HA with metals are formed. This is
extremely important in affecting the retention and
mobility of metal contaminants in soil and water. In an
effort to understand and quantify humic-metal
interactions some ligand models (such as citric,
salicylic, benzoic and phthalic acids) have been used
in the study of complexation properties of humics. In
this paper, salicylic and benzoic acids are used as
humic-model ligands. [1]
Schubert‘s ion-exchange method for determing
conditional stability constants involves measuring the
distribution coefficients of a metal ion between a
cation-exchange resin and solution phase, in both the
presence and absence of the complexing agent. [2, 3]
Metal solutions were prepared by dissolving an
appropriate quantity of Cu(NO3)2 in HNO3. All the
metal solutions were adjusted to pH 4.0 by 0.1M HCl
and 0.1M NaOH with ionic strenght is set by NaCl to
value 0.01. The concentration of stock solutions of
humic (HA), benzoic (BA) and salicylic acid (SA) were
5, 7.5 and 10 moldm -3 . The concentration of stock
solutions of all three acids were 5, 7.5 and 10 meq/l
with ionic strenght of 0.01. The cation-exchange resin
used was Dowex 50WX8 (100-200 mesh), Na-form,
analytical grade from Fluka. Copper was determined
by atomic absorption spectrophotometry with a Varian
Aanalyst 300 with an air-acetylene flame.
The logarithm of the stability constant of the
complex (log βmn) was evaluated from the following
relationship:
� D0
�
log��
� 1 � log K � n log
D
��
� �
�L� where D0 is distribution constant of the Cu 2+ in
absence of ligand; D is distribution constant of Cu 2+ in
the presence of ligand; log βmn is stability constant of
Cu(II)complex; n is number of moles of ligand which
combine with one mole of Cu(II); [L] is concentration
of ligand in mole per litre.
Do was determined from the expression:
0
0
(100 0 ) resin
m α
α �V
D �
� �
where α0 is percent of total metal bound to
exchange resin (Dowex AG 50W-X8); 100-α0 is
percent of total metal remaining in solution; V is
volume of solution; mresin is weight of exchange resin.
D is measured in the same manner as D0 in presence
of different ligand concentrations. Metal-ligand ratios
were obtained from slopes of curves log (D0/D)-1 vs.
log CL for Cu-benzoate and Cu-humate complexes
according to Schubert‘s method, and log MC vs. log
CL for Cu-salicylate complexes according to modified
Schubert‘s method. The obtained results are shown in
Table.
Table. Stability constants of Cu(II)-complexes and
metal : ligand ratio at pH 4.0,
under constant ionic strenght of 0.01 and at 25˚C.
BA SA HA
M:L 1:1 2:3 1:1
log K 1.65 10.34 2.36
The Schubert‘s ion-exchange method is applicable
to determination of conditional stability constants of
mononuclear complexes such as Cu-benzoate and
Cu-humate. Salicylic acid forms polynuclear
complexes with Cu(II). Formation of polynuclear
salicylate complexes disables the application of
classical Schubert‘s method. Value of log βmn and
stoichiometry of Cu-salicylate was determinated by
modified Schubert‘s method.
The obtained log K values show the following
sequence: SA > HA > BA. Thus, the most stable
complex is formed between Cu 2+ and SA, due to Cu 2+
ions form polynuclear complexes with salicylic acid.
References
[1] E. Tipping, Cation binding by humic
substances, Cambridge University Press, Cambridge,
2002.
[2] H. Baker, F. Khalili, Annals of Environmental
Science, 2003, 497, 235-248.
[3] Schnitzer M. and Skinner S.I.M. (1966) Soil
Science, 6, 361-363.
292

P-152
Stability of Cu(II) and Pb(II) salycilate complexes determined by
modified Schubert's method
Ivana Kostic 1 , Tatjana Andjelkovic 1 , Ruzica Nikolic 1 , Milovan Purenovic 1 , Aleksandar
Bojic 1 , Darko Andjelkovic 2 , Miljana Radovic 1
1 University of Nis, Faculty of Sciences and Mathematics, Nis, Serbia, 2 Water Works Association "Naissus",
Nis, Serbia (corresponding author:ivana.kostic83@gmail.com)
Understanding environmental behavior of some
heavy metals, such as Cu(II) and Pb(II) in systems
containing natural organic matter (NOM) requires
knowledge of metal-NOM complexes. Salicylic acid is
a commonly used model for NOM and has an
aromatic nucleus and phenolic and carboxylic
functional groups. [1]
One approach for determining an average stability
constant for a metal-ligand system is to use the wellknown
Schubert equation that can be used effectively
to determine binding constants for metal/ligand
complexes under environmentally relevant
concentrations of metal ions. [2]
The complexation of salicylic acid with two heavy
metal ions Cu(II) and Pb(II) was investigated at pH
4.0, under constant ionic strength of 0.1 and at
temperature 25°C. This investigation was done by
using modified Schubert‘s ion-exchange method. [3]
Stock solutions (1000 mg/l) of Pb(II) and Cu(II) were
prepared by dissolving an appropriate quantity of
these metal nitrate powder in 0.1M HCl. All the metal
solutions were adjusted to pH 4.0 by 0.1M HCl/0.1M
NaOH and ionic strenght was set by NaCl to value
0.01. The cation-exchange resin Dowex 50WX8 (100-
200 mesh), Na-form, analytical grade from Fluka was
used. Metal ions were determined by atomic
absorption spectrophotometry with a Varian Aanalyst
300 with an air-acetylene flame.
The linear range for copper was obtained from
isotherm curve to estimate the Do in order to choose
the appropriate concentrations for metal ion and
ligand to avoid the effect of metal loading. Clasical
Schubert‘s method is applicable for determing stability
constants logβmn of mononuclear complexes and is
shown by following equation:
Possible problems with the Schubert‘s method
occur when complex, MmLn, is not mononuclear (m ≠
1). The following equation presents equation of
modified Schubert‘s method and was used to
eliminate this source of errors and presents the
modified method of data treatment and analysis:
It is expected that salicylic acid form polynuclear
complexes due to the presence of two functional
groups, thus modified Schubert‘s method was
applied.
Metal-ligand ratios were obtained from slopes of
curves log MC vs. log CL according to modified
Schubert‘s method. The slopes of these plots give the
composition of these complexes and values of n near
1.5 indicate that stoichiometries of complexes are 2:3.
Table. Stability constant, log βmn, and metal-ligand
ratio for complexes Cu(II)-salicylate and Pb(II)salicylate,
at pH 4.0 and ionic strength of I = 0.01, by
modified Schubert‘s method
Pb
(ppm)
M:L logβmn
5 2:3 10.90
10 2:3 10.60
15 2:3 10.44
Cu
(ppm)
M:L logβmn
5 2:3 10.54
10 2:3 10.22
15 2:3 10.10
The modified Schubert‘s ion-exchange method
applied for conditional stability constants
determination of Cu-salicylic polynuclear complex
gave comparable results to the reference data. Obtain
results indicate that Pb(II) and Cu(II) form polynuclear
complexes with salicylic acid with metal : ligand ratio
2:3. Pb(II)-salicylate complex show higher stability
constant than Cu(II)-salicylate. It was found that log
βmn decreases with increase of metal concentration.
Reference
[1] E. Tipping, Cation binding by humic
substances, Cambridge University Press, Cambridge,
2002.
[2] Schnitzer M. and Skinner S.I.M. (1966) Soil
Science, 6, 361-363.
[3] H. Baker, F. Khalili, Annals of Environmental
Science, 2007, 1, 35-44.
293

P-153
Differentiation of indoor and subsurface VOCs sources in
residential air by CSIA for vapor intrusion management
Tomasz Kuder 1 , Thomas McHugh 2 , Kyle Gorder 3 , Erik Dettenmaier 3 , Paul Philp 1
1 University of Oklahoma, Norman, United States of America, 2 GSI Environmental Inc., Houston, United
States of America, 3 Hill AFB Environmental Restoration Branch, Hill AFB, United States of America
(corresponding author:tkuder@ou.edu)
At corrective action sites with potential vapor intrusion
(VI) concerns, the presence of indoor sources of
volatile organic compounds (VOCs) complicates the
exposure pathway investigation. Indoor sources of
VOCs in residences are ubiquitous and the
background indoor air concentrations of VOCs can
increase or decrease over time based on changes in
the use of these VOCs in consumer products [1].
Because of this, the detection of a target VOCs in a
potentially affected building at a concentration above
the regulatory screening level does not necessarily
indicate a VI impact. Unfortunately, the current
methods for identification of indoor sources are
expensive and have limited effectiveness. A novel
alternative approach presented herein relies on
determination of stable isotope ratios of the target
VOCs present in the air and/or soil gas ( 13 C/ 12 C,
37 Cl/ 35 Cl for PCE and TCE; 13 C/ 12 C and 2 H/ 1 H in the
case of benzene) by compound-specific isotope
analysis (CSIA). The isotope ratios can be used to
differentiate between VOCs sourced from subsurface
(the true vapor intrusion) and those sourced from
miscellaneous household products. The premise for
such discrimination is that the isotope compositions of
a given chemical compound manufactured at different
facilities and/or at different times tend to vary,
reflecting the isotope ratios inherited from the
manufacturing precursors and processes. Moreover,
subsurface biodegradation of VOCs sources often
results with an enrichment of the heavier isotope
species in the remaining residue, while no such
enrichments are feasible for household product VOCs
[2]. The similarity/dissimilarity of the isotope ratios
between VOCs in indoor air, in soil gas and in
household products (if identified on site) permits
identification of those sources with best match to the
indoor air VOCs isotope composition.
Samples of TCE and/or PCE were collected and
analyzed by CSIA, to determine C and Cl isotope
ratios of the target compounds in residential indoor
air, soil gas and in the ground water in the proximity of
a chlorinated solvent plume at Hill AFB (Utah, USA).
At one of the residences, a household product
containing PCE was found and it was possible to
provide a specimen of that product for direct
comparison with the isotope ratios of indoor air PCE.
The residences were selected for the study based on
previous work – sites with and without likely VI impact
were chosen to allow independent validation of the
CSIA results.
Key challenge of applying CSIA to indoor VOCs is the
low concentration of the analytes. In the present
study, an application of thermal desorption sorbent
tubes was proven to be successful and isotope ratios
could be determined for TCE and PCE at low ug/m 3
concentrations. The results of the survey of the four
residences demonstrated that the isotope ratios of
VOCs present in indoor air may be similar to those of
the same VOCs in soil gas or in household products.
In the former case, VI scenario is suggested; in the
latter case, domestic product impact is suggested.
Combined carbon and chlorine data were more
informative than single isotope data, permitting 2Dcorrelation
of the sources and indoor air samples. In
one residence, the isotope ratios of TCE were clearly
indicative of extensive degradation of the compound.
In such case, even if soil gas samples are not
available, the TCE can be inferred to originate from
the subsurface, as degradation of household product
VOCs is not feasible. The conclusions from CSIA
matched the conclusions from traditional assessment
of VI impact, with a benefit of simplified
implementation.
References
[1] Hers, I., Zapf-Gilje, R. Li, L. Atwater J. (2001) J.
Air & Waste Management Association 51, 1318-1331.
[2] Meckenstock, R.U., Morasch, B., Griebler, C.,
Richnow, H.H. (2004) J. Contam. Hydrology 75, 215-255.
294

P-154
Adaptation of TO-17 thermal desorption protocol for CSIA of
volatiles in air
Tomasz Kuder 1 , Paul Philp 1 , Thomas McHugh 2
1 University of Oklahoma, Norman, United States of America, 2 GSI Environmental Inc., Houston, United
States of America (corresponding author:tkuder@ou.edu)
Identification of sources of volatile organic
compounds (VOCs) in vapor intrusion studies is often
complicated, due to the potential of the same VOCs to
be introduced from various household chemicals [1].
Compound-specific isotope analysis (CSIA) permits
determination of isotope ratios of those target
compounds and thus makes it possible to directly
compare the isotope ratios of, e.g., trichloroethylene
(TCE) present in indoor air, soil gas and various
household products to determine whether the soil gas
is a feasible source of the VOCs present in indoor air.
CSIA requires relatively large mass of the analyte
(tens to hundreds on nanograms), often (in particular
for indoor air samples) requiring preconcentration of
VOCs from large air volumes (>100L). Use of sorbent
tubes similar to those utilized in USEPA TO-17
method allows such preconcentration to be conducted
on site. Precise and accurate determination of isotope
ratios of VOCs after preconcentration on sorbent
tubes requires that one of the following criteria is met:
1) the process does not introduce isotope
fractionation; 2) if isotope fractionation does occur, its
magnitude has to be predictable. Isotope fractionation
would results from a difference in recovery of VOC
molecules with variable isotope substitution. Ideally, a
TO-17 sampling process with 100% mass recovery
would assure that no isotope fractionation is present.
The main objective of the present study was to
investigate the performance of the selected types of
sorbents as applied to sampling of a large volume of
air, i.e., under conditions that are conducive to isotope
fractionation.
The sorbent tubes have been spiked with standard
solutions of TCE and PCE and then flushed with air
volumes equal to the expected sampling volumes for
indoor air. Additional parameters, such as humidity
and occurrence of other VOCs were manipulated to
simulate the conditions of actual sampling. Some of
the tubes were analyzed immediately, while other
tubes were refrigerated and analyzed at later date to
simulate the effects of sample storage. The spiked
tubes were subjected to CSIA and the isotope ratios
obtained for TCE and PCE were compared to the
ratios determined independently. The magnitudes of
isotope fractionation, if any, were recorded and
interpreted in terms of the sampling and analytical
conditions.
Most of work to date centered on a combination of
Tenax GR and Carboxen 569 (Supelco). The carbon
isotope ratios of TCE were adversely affected by the
sampling volume, resulting with artifactual enrichment
of 13 C in the recovered TCE. The significance of other
sampling process parameters was limited. Unlike
TCE, PCE showed very limited fractionation caused
by the sorption-desorption process. While the
fractionation of TCE was predictably tied to the
sampling volume and could be corrected in data
calibration, the presence of such fractionation
increases the analytical uncertainty for the determined
isotope ratios. The observed effects can be
rationalized by the properties of Tenax GR and
Carboxen 569 – specifically, the fractionation of TCE
may be attributed to strong retention of TCE on the
Carboxen 569 bed (i.e., the recovery of TCE was

P-156
A detailed study of the intact polar lipids in Dutch coastal waters
and microbial mats using multistage liquid chromatography
mass spectrometry
Nicole Bale, Ellen Hopmans, Laura Villanueva, Stefan Schouten, Jaap Sinninghe
Damste
Royal Netherlands Institute for Sea Research, Texel, Netherlands (corresponding
author:nicole.bale@nioz.nl)
Nitrogen is a key nutrient in marine waters and can be
a limiting factor for primary production. The marine
nitrogen cycle involves many complex and
interrelated process driven by microbial activity. As
part of the NICYCLE project (The nitrogen cycle and
changes in the carrying capacity of coastal waters) we
have been analysing Intact Polar Lipids (IPLs) in
order to examine the abundance, distribution and
activity of microorganisms involved in marine nitrogen
cycling, specifically in coastal environments. A
principle focus of this study was to examine the
spatial and temporal variability of the nitrogen cycling
microorganisms and we have, with this aim, collected
samples from three different time series in the Dutch
Coastal environment, both from the North Sea and
Wadden Sea.
For the first time series we collected North Sea water,
from a fixed station in the Marsdiep Tidal inlet, every
two weeks for 1.5 years. Secondly we collected
microbial mats from the beaches of a Wadden Sea/
North Sea barrier island bimonthly for a year. The
third time series is made up of four seasonally-distinct
research cruises in one year, carried out along a 235
km transect from the barrier islands into the North
Sea. On these cruises we have collected particulate
matter in the water column as well as sediment.
We have used two analytical approaches in the study
of the microbial IPLs. We worked firstly with a
‗lipidomic‘-style method using liquid chromatography-
multistage mass spectrometry (LC-MS/MS),
whereby we looked at the ‗fingerprint‘ of IPLs in each
sample and examined how this changes, spatially and
temporally between seasons and geographical
settings. The second approach will concentrate on
changes in specific ‗target‘ IPLs which are indicative
of nitrogen-cycling microorganisms, e.g. the IPLs of
crenarchaeol (for ammonia-oxidizing
Thaumarchaeota), heterocyst glycolipids (for nitrogenfixing
cyanobacteria) and ladderanes (for anaerobic
ammonia-oxidizing anammox bacteria). This will be
done using specific LC-MS/MS essays such as
selective reaction monitoring (SRM).
Using the first approach we have identified a range of
IPLs in the samples examined, including
phospholipids such as phosphatidylglycerols (PGs),
phosphatidylethanolamines (PEs) and
phosphatidylcholines (PCs) as well as phosphorousfree
IPLs such as the nitrogen-containing betaine
lipids, the sulphur-containing sulfoquinovosyl
diacylglycerols (SQDGs) and galacto lipids (Fig. 1).
The presence, abundance and range of these IPLs
vary between the sampling sites (spatially) as well as
during the time series (temporally).
Using the second, SRM-based approach we can
monitor whether there are observable changes in our
target lipids over annual timescales. The data will be
compared with those obtained using molecular
ecological techniques on complimentary samples.
Our results will shed light on the utility of IPLs as
markers for general microbial community
composition as well as the presence and abundance
of microbes involved in the marine nitrogen cycle.
Figure 1. A Base peak LC/MS
chromatogram of a Bligh Dyer
Extract from a microbial mat
sample collected from
Schiermonnikoog, a North
Sea/Wadden Sea barrier
island, in February 2010.
296

P-157
Can laterally advected intermediate nepheloid layers affect the
efficiency of the biological pump? – a biomarker study of subsurface
alterations of marine snow aggregates off Cape Blanc,
NW Africa
Andreas Basse 1,2 , Gesine Mollenhauer 1,2 , Gerd Fischer 2 , Morten Iversen 2 , Gerard
Versteegh 2 , Gökay Karakas 1
1 Alfred-Wegener-Institute for Polar and Marine Research (AWI), Bremerhaven, Germany, 2 Universiti of
Bremen, Bremen, Germany (corresponding author:abasse@marum.de)
Marine particulate organic matter (POM) is an
important part of the global carbon cycle, since its
production in the surface waters and subsequent
export to the deep ocean and sediments causes a net
removal of CO2 from the atmosphere. This process is
called the ‗Biological Pump‘ (Volk & Hoffert 1985).
The NW-African upwelling system is the second most
productive of the four eastern-boundary upwelling
systems and is characterized by high export of POM.
Previous studies have shown that the transport of
POM to the deep sea is not only controlled by the
vertical flux, but also by lateral advection from the
shelf area. Field observations and models show
intermediate and near-bottom nepheloid layers (NLs).
(Karrakas et al. 2006, Fischer et al. 2007). It has been
shown that biological alterations are controlling POM
export from the surface ocean (Iversen et al. 2010),
and an equally important alteration of the POM may
occur as it sinks through the NLs by scavenging of
laterally advected particles.
We analyzed samples collected with in-situ pumps,
core top sediment samples, and surface water
filtrations along an EW-transect off Cape Blank.
We found the lipid composition of the POM to change
significantly with water depth. This suggests that
degradation processes at all depths alter the POM as
it sinks, and/or that the NLs contain distinct lipids
which are scavenged by the POM aggregates during
their vertical flux through the NLs.
We measured UK‘37, TEX86 and bulk radiocarbon age.
The UK‘37 showed no significant changes throughout
the water column, indicating that the UK‘37-Index is
not affected by lateral transport and alteration. The
TEX86, however, showed significant increases
correlating with the nepheloid layers. This implies that
the material in the NLs has either 1) a different source
of POM compared to the water layers above and
below the NLs, or 2) that the POM in the NLs
undergoes different alteration processes than the rest
of the POM in the water column. The age
determinations via 14 C indicated that the NLs
contained a mixture of fresh and very old material
compared to the water layer above and below. to the
old material was probably laterally advected from the
shelf area (Karakas et al. 2006), while the fresh
material likely derived from surface produced POM
aggregates. Hence, we have a complex system
where biological and physical processes influence the
efficiency of the biological pump at different depths
through the water column.
References
Fischer, G., Karakas, G., Blaas, M. Ratmeyer, V.,
Nowald, N., Schlitzer, R., Helmke, P., Davenport, R.,
Donner, B., Neuer, S. and Wefer, G. (2007). Mineral
ballast and particle settling rates in the coastal
upwelling system off NW Africa and the South
Atlantic. Int. J. Earth Sci., doi 10.1007/s00531-007-
0234-7.
Karakas, G., Nowald, N., Blaas, M., Marchesiello, M.,
Frickenhaus, S. and Schlitzer, R. (2006). High
resolution modelling of sediment erosion and particle
transport across the NW African shelf. Journal of
Geophysical Research, 111, C06025,
doi:10.1029/2005JC003296, 2006.
Iversen, M. H., Nowald, N., Ploug, H., Jackson, G. A.,
and Fischer, G.: High resolution profiles of vertical
particulate organic matter export off Cape Blanc,
Mauritania: Degradation processes and ballasting
effects, Deep-Sea Res. I, doi:
10.1016/j.dsr.2010.1003.1007, 2010.
Volk, T., Hoffert, M.I., 1985. Ocean carbon pumps:
analysis of relative strengths and efficiencies in
ocean-driven atmospheric CO2 changes. In:
Sundquist, E., Broecker, W.S. (Eds.), The Carbon
Cycle and
Atmospheric CO2: Natural Variations Archean to
Present.AGU, Washington, DC, pp. 99–110.
297

P-158
Unusual distribution of long-chain heterocyst glycolipids in an
Icelandic hot spring
Thorsten Bauersachs, Marcel Van der Meer, Stefan Schouten, Jaap Sinninghe Damsté
Royal Netherlands Institute for Sea Research, Texel, Netherlands (corresponding author:thb@gpi.unikiel.de)
Heterocyst glycolipids (HGs) represent novel
biological markers for diazotrophic (N2-fixing)
heterocystous cyanobacteria. These components
surround the heterocysts - specialized cells dedicated
to the fixation of N2 - and act as an effective gas
diffusion barrier that prevents O2 diffusion into the cell
[1]. HGs have recently been used to trace for
diazotrophic heterocystous cyanobacteria in modern
and ancient environments, including coastal microbial
mats as well as lacustrine and marine sediments [2].
The HGs detected in this environments solely
consisted of C26 and C28 diols, triols as well as their
corresponding ketone varieties.
Here, we report on the intact polar lipid (IPL)
composition of a microbial mat growing in a sulfidic
Icelandic hot spring, which was dominated by green
non-sulfur bacteria closely related to Chloroflexus
aurantiacus and the heterocystous filamentous
cyanobacterium Mastigocladus sp. The IPL
composition of the microbial mat was characterized
by the dominance of the glycolipids MGDG, SQDG,
DGDG and the phospholipid PG, which are common
in photosynthetic organisms. In addition, a suite of
components with retention times similar to those
previously reported for heterocyst glycolipids was
present. Based on the mass spectral characteristics,
we identified these components as C30 and C32 HG
triols.
In order to identify the source of these unusual longchain
HGs, we grew a physiologically related strain of
Mastigocladus sp. under nitrogen-depleted conditions
and environmental parameters similar to those
encountered in the Icelandic hot spring. The analysis
of its intact polar lipid content indeed revealed the
presence of the C32 HG triol and thus established
Mastigocladus sp. as the probable source of this longchain
HG (Fig. 1). Surprisingly, no C30 HG triol was
detected in our isolate. The HG composition between
different species and strains of the same genus,
however, might vary and Mastigocladus sp. is thus
the most likely source of both long-chain HG triols in
the hot spring microbial mat.
Heterocystous cyanobacteria have previously been
suggested to vary their HG composition with
temperature in order to compensate for increased O2
fluxes into the heterocyst under elevated ambient
temperatures [3]. Our results suggest that
thermophilic heterocystous cyanobacteria are indeed
characterized by a HG composition that is distinctly
different from what is observed in other moderate and
tropical environments and that the increased chainlength
might be an adaptation to the increased
temperatures in hot springs. In addition, C30 and C32
HG triols have not yet been reported from
cyanobacteria other than Stigonematales suggesting
a possible chemotaxonomic value for the long-chain
heterocyst glycolipids.
Fig. 1. Base peak chromatogram of the total lipid extract of
the heterocystous cyanobacterium Mastigocladus sp.
References
[1] Nichols and Wood (1968) Nature, 217, 767-769
[2] Bauersachs et al. (2010) PNAS, 107, 19190-19194
[3] Staal et al. (2007) Nature, 425, 504-507
298

P-159
Archaeal and bacterial tetraether lipids in an oligotrophic and a
eutrophic Swiss lake: Insights into their sources and GDGTbased
proxies
Achim Bechtel 1 , Rienk H. Smittenberg 2 , Stefano M. Bernasconi 2 , Carsten J. Schubert 3
1 Montanuniversitaet, Leoben, Austria, 2 ETH, Zürich, Switzerland, 3 EAWAG, Kastanienbaum, Switzerland
(corresponding author:Achim.Bechtel@mu-leoben.at)
Distributions of isoprenoid (isoGDGT) and branched
glycerol dialkyl glycerol tetraethers (brGDGT) were
measured in the water column and sediments of the
eutrophic Lake Lugano and the oligotrophic Lake
Brienz, Switzerland. Both lakes, including the anoxic
bottom water of Lake Lugano, are characterised by
GDGT distributions typical for group I Crenarchaeota
with GDGT-0/crenarchaeol ratios of around 1
(Sinninghe Damsté et al., 2002). Comparison of the
present and past trophic levels of both lakes with
POM and sedimentary isoGDGT concentrations
suggest that GDGT concentrations in lacustrine
sediments might be used to detect periods of
euthrophication.
TEX86 index values reflect the lake surface
temperatures (LST) reasonably when applying the
lake-specific calibration of Powers et al (2010). TEX86
–derived temperatures in the deeper parts of the
water column of both lakes suggest mixing of
exported and in situ produced GDGTs or the
presence of older isoprenoidal GDGTs, reflecting
different temperature regimes. Reconstructed mean
LST from Lake Brienz sediments matched the
instrumental record until soil-derived OM input
increased in the second half of the 20 th century,
evidenced by increased BIT indices. In Lake Lugano,
the TEX86-based temperatures exhibit a -4°C offset.
This is at the edge of the calibration error, but can
also be interpreted as a springtime temperature
record, or an annual record that is influenced by
GDGT production in deeper and colder water.
BIT index values in Lake Brienz sediments (~0.4)
were significantly higher than water column values
(~0.1), most probably because terrestrial run-off
events were not captured during the water
sampling. In Lake Brienz the brGDGTs appear to
be genuinely soil-derived, but, based on their
distribution through the water column and the
calculated MBT/CBT proxy, the brGDGTs in Lake
Lugano appear to be at least partially produced in
situ.
Overall, the data presented in this paper appear to
validate the new TEX86 calibration for lacustrine
sediments, but also show that this can only be done
after careful examination of the sources of archaeal
GDGTs. This is even truer for the sources (i.e. soil
versus lacustrine) of the brGDGTs, and the use of
the MBT and CBT proxies.
References:
Sinninghe Damsté, J.S., Hopmans, E.C., Schouten,
S., van Duin, A.C. & Geenevasen, J.A.J. (2002):
Crenarchaeol: the characteristic core glycerol
dibiphytanyl glycerol tetraether membrane lipid of
cosmopolitan pelagic Crenarchaeota. Journal of
Lipid Research 43, 1641-1651.
Powers L.A., Werne J. P., Vanderwoude A. J.,
Sinninghe Damsté J. S., Hopmans E. C. &
Schouten S. (2010): Applicability and calibration of
the TEX86 paleothermometer in lakes. Organic
Geochemistry 41, 404-413.
299

P-160
Biomarker signatures of methane-oxidizing archaea and aerobic
bacteria in seep carbonates reveal changing redox conditions at
cold seeps from Alaminos Canyon, northern Gulf of Mexico
Daniel Birgel 1 , Dong Feng 2,3 , Harry H. Roberts 3 , Jörn Peckmann 1
1 Department of Geodynamics and Sedimentology, Center for Earth Sciences, University of Vienna,, 1090
Vienna, Austria, 2 CAS Key Laboratory of Marginal Sea Geology, Guangzhou Institute of Geochemistry,
Chinese Academy of Sciences, Guangzhou 510640, China, 3 Coastal Studies Institute, Department of
Oceanography and Coastal Sciences, Louisiana State University, Baton Rouge, LA 70803, United States of
America (corresponding author:daniel.birgel@univie.ac.at)
The anaerobic oxidation of methane (AOM) often
leads to the formation of authigenic carbonates at
methane seeps in anoxic sediments. Recently,
however, it was shown that redox conditions
prevailing during seep carbonate precipitation may
vary to some degree. We analysed several authigenic
carbonate samples from Alaminos Canyon lease
block 645 of the northern Gulf of Mexico. The
carbonates have been characterized by means of
inorganic and organic geochemistry. Samples were
collected from deposits of various seafloor
morphologies, including extensive pavements,
mounds, and fractured carbonate slabs surrounded
by dense bivalve shells and vestimentiferan tubeworm
colonies. All carbonates studied are composed almost
entirely of aragonite. Based on the obtained � 18 O
values of aragonite (+2.6 to +5.8‰ V-PDB),
precipitation occurred in slight disequilibrium with the
surrounding pore fluids. The δ 13 C values of aragonite
fall between –33.9 and –20.4‰ V-PDB and agree
with carbonate derived from various sources, but
especially from oxidation of thermogenic methane and
crude oil. Abundant 13 C-depleted molecular fossils,
including the isoprenoids sn-2-hydroxyarchaeol and
archaeol with δ 13 C values as low as �118‰, and
various fatty acids with δ 13 C values as low as �97‰
reveal that methane was oxidised in an anaerobic
process by the well-known AOM consortium.
Moreover, the observed inventories of molecular
fossils in the authigenic carbonates mirror those of
known consortia of anaerobic methane oxidizing
archaea (ANME) and sulphate-reducing bacteria,
namely the ANME-2/Desulfosarcina/Desulfococcus
(DSS) and ANME-3/Desulfobulbus (DBB) consortia.
In contrast, the same carbonates exhibit shalenormalized
rare earth elements patterns that all
display real negative Ce anomalies (Ce/Ce* < 0.78),
suggesting that precipitation proceeded at least
partially under oxic conditions. The episodic
occurrence of oxic conditions is confirmed by the
presence of molecular fossils of aerobic
methanotrophic bacteria, including 4�-
methylcholesta-8(14),24-dien-3�-ol, and two
abundant bacteriohopanepolyols (BHPs), aminotetrol
and aminotriol. The δ 13 C values of the sterol and
cleaved BHPs, as well as other hopanoids, are more
or less uniform (as low as –58‰). The molecular
fossils of aerobic methanotrophic bacteria are
consequently less 13 C-depleted than those of the
prokaryotes performing anaerobic oxidation of
methane. This compound-specific isotope pattern is in
accord with culture experiments on aerobic
methanotrophs. We further compared our findings
with other modern and some ancient seep sites,
where aerobic methanotrophy was recognised.
Overall, our results suggest that redox conditions at
cold seeps are variable. This variability most likely
reflects changes in seepage flux. The combination of
an inorganic and an organic geochemical approach
used here is promising to better assess the variability
and diversity of past fluid and gas expulsion at seeps.
300

P-161
Biosignatures of microbial methane turnover in the water
column and sediments of the central Baltic Sea (Gotland Deep)
Martin Blumenberg 1 , Christine Berndmeyer 1 , Oliver Schmale 2 , Volker Thiel 1
1 Geoscience Center, Geobiology Group, Georg-August-University Göttingen, Göttingen, Germany, 2 Leibniz
Institute for Baltic Sea Research Warnemünde, Rostock, Germany (corresponding
author:martin.blumenberg@geo.uni-goettingen.de)
Methane (CH4) is an important atmospheric trace gas,
influencing the climate with a global warming potential
25 times higher than that of CO2. Marine and limnic
sediments are considerable sources of methane
originating from thermogenic deep sources or from
microbial methanogenesis [1]. However, in sediments
and overlying water bodies, most methane is oxidized
by phylogenetically and metabolically versatile
prokaryotes [2]. In marine environments, the sulfatedependent
anaerobic oxidation of methane (AOM) is
of particularly high relevance because it eliminates
the vast majority of methane before reaching
overlying oxygenated waters or the atmosphere.
However, other anaerobic pathways of methane
turnover, potentially prevailing in freshwater,
terrestrial and brackish environments were recently
described [3,4].
In the Baltic Sea geochemical and seismoacoustic
studies of the seabed reveal large areas with high
concentrations of dissolved methane and free gas
occurring within an organic-rich postglacial sediment
layer of the Littorina facies [5]. Moreover, surface
waters of the Baltic Sea are considerably methaneoversaturated
with respect to the atmospheric
equilibrium [5]. In this regard of particular interest are
the deep basins in the central Baltic (Gotland-Deep
and Landsort-Deep). Here the strong permanent
density stratification leads to large vertical redox
gradients in the water column, which are perturbed by
saline inflows from the North Sea. Although dissolved
methane is highly abundant in the deep anoxic water
body of these basins (up to 1090nM) [5], little is
known about the methane turnover in this
environment.
Here we present preliminary biomarker data on the
distribution of lipids specific for methanotrophic
prokaryotes in the water column of the central Baltic
Sea (Gotland Deep). These molecules include
specific bacteriohopanepolyols (BHPs; i.e., 35aminobacteriohopanetetrol)
that show a maximum
abundance in the particulate organic matter sampled
at the oxic/anoxic transition zone of the water column
at about 120 m water depth. Consequently, the
occurrence of aerobic methane consumption is
indicated, a process which is also recorded in the
underlying sediments. In anoxic deeper waters
(sample from 135 m water depth), these BHPs were
absent, but specific biomarkers for sulphate reducing
bacteria (ai15/ai15-dialkyl glycerol diether; hexadec-
11-enoic acid) and archaea (archaeol) were found.
The majority of the source organisms, however,
appears to be not involved in the consumption of
methane since compound specific δ 13 C-analyses
revealed no significant 13 C-depletions (-28 to -33‰
vs. VPDB), as it would be expected for AOM
performing organisms. Assessing the importance of
sulphate-dependent and -independent AOM in the
Baltic Sea clearly requires further studies. However,
our data indicate the existence of a ‗microbial filter‘ of
most likely aerobic methanotrophs at the oxic/anoxic
boundary of the central Baltic Sea water column that
considerably reduces the amounts of sedimentary
methane before entering the atmosphere.
[1] Reeburgh, W.S. (1976) Earth and Planetary
Science Letters 28, 337-344.
[2] Knittel, K., Boetius A. (2009) Annual Review of
Microbiology 63, 311-334.
[3] Ettwig, K.F., et al. (2010) Nature 464, 543-548.
[4] Raghoebarsing, A.A., et al. (2006) Nature 440,
918-921
[5] Schmale, O., et al. (2010) Geophysical Research
Letters 37, L12604.
301

P-162
Lipid biomarkers and bulk biogenic components in sinking
particles from the SW Black Sea
Ioanna Bouloubassi 1 , Alexandra Gogou 2 , Anna Sanchez-Vidal 3 , Spyros Stavrakakis 2
1 LOCEAN, IPSL, CNRS/UPMC/IRD, Paris, France, 2 HCMR, Institute of Oceanography, Anavyssos, Greece,
3 GRC Geociencies Marines, Universitat de Barcelona, Barcelona, Spain (corresponding
author:ioanna.bouloubassi@upmc.fr)
Sinking particles were obtained with an instrumented
array moored in the SW Black Sea (2000 m water
depth) over a period of 12 months (Oct. 2007-
Oct.2008), equipped with two sediment traps (at
1000m and 1965m) with a sampling period of 15
days. The settling material was investigated in terms
of total mass flux, major biogenic components
(organic carbon, carbonates, opal) and lipid
biomarkers.
The mean annual mass fluxes were 109 and 86 mg
m -2 d -1 , at 1000m and 1965m, respectively. The
composition of particulate matter was similar at both
depths, characterized by high organic carbon
contents, reaching 11%. Overall, the biogenic
components were dominant, accounting for ca. 54%.
Mass fluxes showed strong temporal variations over
the experimental period with three major maxima in
early summer and fall/winter. Organic carbon fluxes
averaged 11 and 9 mg/m 2 /d in mid- and deep waters
and they generally followed the temporal pattern of
total mass fluxes. Carbonates showed a major peak
in late spring/summer reaching 178 mg/m 2 /d, while
high opal fluxes were recorded mainly in winter, with
secondary peaks in late spring/summer and fall.
Source-specific lipid biomarkers allowed assessing
the composition and variability of settling material in
detail. Terrestrial biomarkers (long chain n-alkanes)
were minor components, with high values reflecting
the periods of enhanced discharges of the Danube
River that control the pattern of lithogenic fluxes.
Marine biomarkers, deriving from primary producers,
were fairly predominant. High amounts and fluxes of
alkenones were observed, consistent with the high
coccolithophorid production in the Black Sea. The
temporal patterns delineate a major bloom in late
spring/summer that clearly controls the carbonate flux
variability. The concentrations and fluxes of diatombiomarkers
(C28 sterols, HBI) depict the temporal
patterns of downward organic carbon fluxes,
suggesting that diatom production exerts a main
control on carbon export. Moreover, diatom
biomarkers portray the temporal variability of opal
fluxes. Biomarkers tracing mainly dinoflagellates (e.g.
dinosterol) also show important temporal variation.
Besides, biomarkers derived mainly from zooplankton
show elevated concentrations and fluxes and their
temporal patterns indicate their links with enhanced
organic carbon export.
Comparisons between the mid-depth and deep traps
show that the transfer is rapid and that carbon
recycling is not very important, leading to enhanced
carbon sequestration in this marine site.
Overall, the lipid biomarker data set sheds light on the
origin of organic carbon in settling particles in the SW
Black Sea and, coupled to bulk parameters, enables
assessing the primary controls on the downward
biogenic fluxes.
302

P-163
Fluxes and distributions of core and intact tetraether membrane
lipids in the water column of Lake Challa, East Africa
Laura Buckles 1 , Johan Weijers 1 , Gert-Jan Reichart 1 , Dirk Verschuren 2 , Jaap Sinninghe
Damsté 1,3
1 Utrecht University, Utrecht, Netherlands, 2 Ghent University, Ghent, Belgium, 3 NIOZ Royal Netherlands
Institute for Sea Research, ’t Horntje, Texel, Netherlands (corresponding author:l.buckles@geo.uu.nl)
The methylation index of branched tetraethers/
cyclisation ratio of branched tetraethers (MBT/CBT)
palaeotemperature proxy measures the distribution of
branched glycerol dialkyl glycerol tetraether bacterial
membrane lipids (brGDGTs) to generate a
quantitative mean annual air temperature (MAAT)
estimate [1]. This proxy has been applied mostly to
marine sediment records that contain a large
proportion of terrestrial organic matter, for example
near river outflows. The prospective use of the
MBT/CBT in lake sediment archives would vastly
extend the proxy‘s area of application; however, some
recent studies have discovered a mismatch between
the distributions of these brGDGTs in catchment area
soils versus those found in lake sediments. These
suggest that brGDGTs may be produced in-situ in
lakes, with obvious implications for MBT/CBT
application [2,3]. In order to investigate the potential
and limitations of the MBT/CBT proxy in lakes, it is
necessary to look at modern fluxes of GDGTs in lake
systems to resolve the exact sources and distributions
of these compounds.
The bacterial source of brGDGTs remains unknown,
making it difficult to use microbiological techniques to
trace their sources within the lake and its catchment
area. Using a novel separation method, GDGTs can
be split into intact polar tetraether membrane lipids
(IPLs) and core tetraether membrane lipids (CLs) [4].
IPLs are commonly believed to degrade rapidly upon
cell lysis when the labile polar head group is
hydrolysed, thereby converting the ‗living‘ IPLs to the
more stable ‗fossil‘ CLs [5]. This makes it possible to
use IPLs as a tracer for living, GDGT-synthesising
bacteria.
This study concentrates on Lake Challa, a
permanently stratified crater lake in equatorial East
Africa. Thirty-three contiguous monthly sediment trap
samples (December ‗07 to August ‗10) from 35
metres depth, as well as lake surface sediments and
catchment soils, were analysed for both brGDGT IPLs
and CLs. Increased fluxes of CL and IPL brGDGTs in
the water column do not correspond to precipitation
events, while brGDGT distributions in sediment trap
material differ from those of the surrounding soils
(Fig.), arguing against these soils as the dominant
source. The African lake calibration of the MBT/CBT
proxy was applied to each monthly collection of the
sediment trap material [3], yielding estimated MAATs
that show a strong seasonal signal. This signal is
offset by 5-6 months against measured mean monthly
air temperatures. The amplitude of variation in
estimated MAAT over the season is also much larger
than the measured temperature range. Not only do
brGDGT distributions differ between catchment soils,
sedimenting matter and surface sediments (Fig.), but
catchment soils are also characterised by a much
lower proportion of IPLs (compared to CLs) than
either sedimenting matter or sediments. This sum of
evidence shows significant in-situ production of
brGDGTs occurring in the water column of Lake
Challa.
Figure: Plot of MBT vs. degree of cyclisation of
brGDGT CLs in and around Lake Challa.
This includes lake surface sediments (0-1cm
depth), catchment soils and sediment traps.
[1] Weijers et al. (2007) Geochim. Cosmochim.
Acta, 71, 703-713.
[2] Sinninghe Damsté et al. (2009) Geochim.
Cosmochim. Acta, 73, 4232-4249.
[3] Tierney et al. (2010) Geochim. Cosmochim.
Acta, 74, 4902-4918.
[4] Pitcher et al. (2009), Org. Geochem., 40, 12-19.
[5] Lipp et al. (2008) Nature, 454, 991-994.
303

P-164
Chemotaxonomic composition and carbon fixation of the
microbial community in a shallow hydrothermal vent off Milos,
Greece
Miriam Sollich, Marcos Yoshinaga, Roy Price, Kai-Uwe Hinrichs, Solveig Bühring
MARUM, University of Bremen, Bremen, Germany (corresponding author:solveig.buehring@uni-bremen.de)
Submarine hydrothermal venting at shallow depths
(

P-165
Characterisation of organic acids in geological samples
Jacqueline Mireya Calzada Mendoza, Andrea Vieth-Hillebrand, Heinz Wilkes
Deutsches GeoForschungsZentrum, Potsdam, Germany (corresponding author:mireya@gfz-potsdam.de)
It was long thought that life on Earth is restricted to
the surface and the upper few meters of sediment.
The relatively recent discovery of deep microbial life
brought up an important topic in geobiological
research: the question what the potential carbon and
energy sources sustaining microbial ecosystems in
geological habitats are and how they are generated
[1-3].
Most organic carbon-rich deposits are formed in
sedimentary environments, where the organic matter
suffers biochemical and geochemical processes
which control its preservation and degradation. It is
still not well known, however, which fractions of the
organic matter are available for utilization by
heterotrophic microorganisms. Several studies have
been performed to show that organic carbon rich
lithologies like lignites, coals and kerogen could act as
potential ―feeder‖ lithologies for the deep biosphere
[4-6], leading to the conclusion that abiotically driven
degradation reactions of the buried organic matter
may provide substrates for microbial activity in deep
sediments. It has been proposed that carbonaceous
sediments can supply low molecular weight organic
acids (LMWOA) to the deep biosphere [7], however,
rates and quantities of these processes have not
been elucidated until now.
LMWOA play an important role in biogeochemical
processes as products or reactants of various types of
reactions. They may be formed abiotically through
thermal breakdown of organic matter or by microbial
metabolism of organic components of higher
complexity. It is known since long that many LMWOA
can be utilized by numerous types of microorganisms
as carbon and/or energy sources. Thus their
metabolism by microorganisms plays an active role in
carbon cycling in the geosphere. LMWOA may also
be used as basic building blocks in biosynthesis of
complex lipids with functions as structural
components, in energy storage, and in signalling [8].
This contribution presents the analytical strategy and
first results about the qualitative and quantitative
assessment of the natural variability of LMWOA in
the C2 – C10 range in different organic-rich sediment
and rock samples, e.g. samples representing early
diagenesis, a maturity sequence of coals and a series
of reservoir rocks from biodegraded oil reservoirs. We
applied gas chromatography–mass spectrometry
(GC-MS) using a polar column for the identification
and quantification of underivatized organic acids and
gas chromatography-isotope ratio mass spectrometry
(GC-IRMS) to determine the carbon and hydrogen
isotopic composition of individual LMWOA. The
obtained data will be interpreted in the framework of
comprehensive characterization of the bulk dissolved
organic carbon (DOC) and its different fractions. This
includes also the quantification of inorganic anions
and LMWOA with less than 5 carbon atoms (e.g.
acetate, formate) by ion chromatography (IC) and the
characterization of dissolved organic matter by size
exclusion chromatography (liquid chromatographyorganic
matter detection LC-OCD).
References
[1] Kerr, R. A. (1997). Science 276, 703-704.
[2] Parkes, R. J., Cragg, B. A. and Wellsbury, P. (2000).
Hydrogeology Journal 8, 11-28.
[3] Whitman, W. B., Coleman, D. C. and Wiebe, W. J.
(1998). Proceedings of the National Academy of Sciences of
the United States of America 95, 6578-6583.
[4] Horsfield, B., Schenk, H. J., Zink, K., Ondrak, R.,
Dieckmann, V., Kallmeyer, J., Mangelsdorf, K., di Primio, R.,
Wilkes, H., Parkes, R. J., Fry, J. and Cragg, B. (2006). Earth
and Planetary Science Letters 246, 55-69.
[5] Krumholz, L. R., McKinley, J. P., Ulrich, G. A. and Suflita,
J. M. (1997). Nature 386, 64-66.
[6] L'Haridon, S., Reysenbacht, A. L., Glenat, P., Prieur, D.
and Jeanthon, C. (1995). Nature 377, 223-224.
[7] Vieth, A., Mangelsdorf, K., Sykes, R. and Horsfield, B.
(2008). Organic Geochemistry 39, 985-991.
[8] Timmis, K. N., López-Lara, I. M. and Geiger, O. (2010). In
"Handbook of Hydrocarbon and Lipid Microbiology", pp. 385-
393. Springer Berlin Heidelberg.
305

P-166
The role of two submarine canyons in the transport and
accumulation of organic matter in the south-eastern Brazilian
continental margin
Renato Carreira 1,2 , Lívia Cordeiro 2 , Dulce Oliveira 2
1 Department of Chemistry, Pontifical Catholic University, Rio de Janeiro, Brazil, 2 School of Oceanography,
Rio de Janeiro State University, Rio de Janeiro, Brazil (corresponding author:rscarreira@gmail.com)
The geochemistry of organic matter in recent
sediments from the South-Eastern Brazilian
Continental Margin (SEBCM; 20-29°S, 39-48°W) has
been considered in detail only in the last 5-10 years.
Studies using isotopic and sedimentological
information [p.ex, 1] as well as lipid biomarker
distributions [2, 3] suggest that organic matter (OM)
accumulating in these sediments is mainly derived
from autochthonous production, which is enhanced by
the occurrence of coastal and shelf-break upwelling
events of the cold and nutrient-rich South Atlantic
Central Water (SACW) [4]. On the other hand, the
presence of only small to medium estuaries in this
region results in low input of continental sources of
OM.
Under the ―Habitats Project – Campos Basin
Environmental Heterogeneity by CENPES
/PETROBRAS‖ we used lipid biomarkers (fatty acids,
n-alcohols and sterols) to evaluate the origin and
bioavailable fraction of organic matter in superficial
sediments from two canyons and two adjacent
transects in the slope (400 to 1300 m water-depths) of
the Campos Basin, in the SEBCM. Assignment of
lipids to distinct sources of organic matter,
considering all the data in two samplings (winter/2008
and summer/2009), revealed preferential
accumulation in the canyons (compared to adjacent
transects) of organic matter derived from primary and
secondary production in the water column. Our results
support the hypothesis that these topographical
features are responsible for the accumulation and
transport of labile organic matter to deeper portions of
the continental margin.
Figure 1. Results from two samplings (median=bar,
25 th and 75 th percentis=box and min/max=whisker)
for the grouping of lipids according to distinct sources
of organic matter: (i) terrestrial: sum of long-chain
(>C23) fatty acids and n-alcohols; (ii) zoo/fauna:
cholesterol, 18:1 fatty acid; (iii) primary production:
C27, C28, C30 sterols and C18,C20 polyunsaturated fatty
acids; (iv) bacterial: iso and anteiso-C15/C17 and 10methyl-C16
fatty acids. CANG = Grussaí canyon
CANAC = Almirante Câmara canyon.
References:
1. Mahiques, M.M., et al., Anais da Academia
Brasileira de Ciências, 2005. 77(3): p. 535-548.
2. Yoshinaga, M.Y., P.Y.G. Sumida, and S.G.
Wakeham, Organic Geochemistry, 2008. 39(10):
p. 1385-1399.
3. Carreira, R.S., et al., Organic Geochemistry, 2010.
41: p. 879-884.
4. Valentin, J.L., D.L. André, and S.A. Jacob,
Continental Shelf Research, 1987. 7(1): p. 77-88.
306

P-167
Microbial deposits from Shark Bay and their geologic
significance - a multidisciplinary re-visit
Tobias Ertefai 1,2 , Ricardo Jahnert 3 , Grzegorz Skrzypek 4 , John Dodson 2 , Kliti Grice 1 ,
Lindsay Collins 3
1 WA Organic & Isotope Geochemistry Centre, Curtin Univsersity, Perth, Australia, 2 Insitute for
Environmental Research, ANSTO, Sydney, Australia, 3 Department of Applied Geology, Curtin University,
Perth, Australia, 4 West Australian Biogeochemistry Centre, University of Western Australia, Perth, Australia
(corresponding author:t.ertefai@curtin.edu.au)
Accumulations of modern microbial mats resemble
carbonate systems of the Neoproterozoic to Mesozoic
from which significant commercial oil and gas
reservoirs have been identified (e.g. Oman, Brazil).
Cyanobacterial mats and living stromatolites
represent life forms similar to those preserved in
rocks of some 3.5 billion years in age. At Shark Bay
(Western Australia), a variety of distinct
cyanobacterial mat morphotypes grow within distinct
zones of the intertidal plain, while the reasons for this
striking succession are not resolved. Mat
morphologies are likely linked to the interplay of
different microbial consortia and their metabolic
pathways that influence mat geochemistry and
lithification via the ―alkalinity engine‖ and extracellular
polymeric substances as potential nucleation sites for
carbonates [1].
The geological significance of modern photosynthetic
mats inspired us to investigate these features within a
multidisciplinary approach combining
sedimentological, organic and inorganic geochemical
and molecular techniques. Using LC-MS techniques,
we observe profiles of intact polar lipids (IPLs) that
are typical of photosynthetic microbial mats [2]. The
complex microbial community is represented by 9 IPL
classes including phospho- and glycolipids, N- and Scontaining
IPLs. Systematic differences in the
abundance of betaine lipids vs. ornithine lipids
suggest a different contribution of S-cycling bacteria
to the microbial community within smoothly layered
mats as opposed to other morphotypes. The analysis
of phospholipid fatty acids (PLFAs) is in good
accordance with the profiles of IPL acyl side chains
(range: C14:0 to C19:1 fatty acids) and allow the
discrimination of different biochemical pathways, as
isotopic signatures of the PLFAs range from -11.3 to
-29.6 ‰ vs. VPDB. δ 13 C values of C17-n-alkanes
attributed to cyanobacteria support differences
between mat types (range: -18.6 to -31.2 ‰),
whereas discrete mat morphotypes (e.g. smooth
mats) reflect isotopic similarities across the
embayments (-18.6 to -23.5 ‰). Isotopic values of
bulk organic matter (-10.6 to -30.0 ‰, Fig. 1) and
dissolved organic carbon in the porewater of the mats
(-9 to -19 ‰) are consistent with rising salinity levels
between the embayments (40,000-80,000). Dissolved
inorganic carbon isotope values are relatively
depleted (-1.4 to -12.9 ‰) compared to δ 13 C values of
carbonates (update: 2.2 to 4.4 ‰).
Fig. 1: δ 13 C of bulk organic matter (OM) liberated from
intertidal microbial mats (tufted, pustular, smooth, colloform)
at four locations (Hutchinson and Nilemah are within
Hamelin Pool, Rocky and Garden Point outside of it, Shark
Bay, Western Australia).
References
[1] Dupraz, C., Reid, P., Braissant, O., Decho, A.,
Norman, S., Visscher, P. (2009) Earth. Sci. Rev. 96, 141-
162.
[2] Hoelzl, G., Doermann, P. (2007) Prog. Lip. Res.
46, 225–243.
307

P-168
Correlation of crenarchaea and phytoplankton biomarkers
indicate metabolic dependence
Susanne Fietz 1 , Carme Huguet 1 , Alfredo Martinez-Garcia 3 , Gemma Rueda 1 , Vicky Peck 4 ,
Marina Escala 1 , Antoni Rosell-Melé 1,2
1 Institut de Ciència i Tecnlogia Ambientals (ICTA), Universitat Autònoma de Barcelona (UAB), Barcelona,
Spain, 2 Institució Catalana de Recerca i Estudis Avançats (ICREA), Barcelona, Spain, 3 ETH Zürich, Zürich,
Switzerland, 4 British Antarctic Survey, Cmbridge, United Kingdom (corresponding
author:susanne.fietz@uab.cat)
Archaea are ubiquitously distributed and usually
constitute a large part (up to 30%) of the
picoplankton. However, their metabolic pathway
(chemoautotrophic, mixotrophic or heterotrophic) is
still discussed, and it remains debatable whether
phytoplankton derived organic matter is an important
energy or carbon source for Archaea. For bacteria, in
contrast, the dependence on phytoplankton and
consequent co-variation with phytoplankton has long
been established. To seek new evidence on the
existence of a coupling between phytoplankton and
Thaumarchaea 2 , we investigated the occurrence of
specific biomarkers of these organisms in
sedimentary archives, which encompass larger timespans
than snap-shot water column samples. We
used chlorins, chlorophyll transformation products
indicative of phytoplankton production 3 and
crenachaeol, a marker for Thaumarchaea
abundance 4 . Sedimentary records of freshwater (Lake
Baikal, Russia) and marine settings (Arctic Ocean,
Atlantic Ocean and Southern Ocean) covering glacial
and interglacial time spans were studied.
Despite the wide range of environmental conditions of
these records, we observed a pervasive tight (rs>0.75)
and statistically significant coupling between both
biomarkers at all investigated sites (example for Lake
Baikal in Fig.1A). The slopes of the regression line
between the two compounds (Fig. 1B) indicated
differential Crenarchaeal response strengths to
phytoplankton productivity between the studied
systems. Various factors such as degradation,
transport mechanisms or a common environmental
trigger may in part account for the tight correlation,
but these mechanisms cannot fully explain our
observations. Our findings instead indicate that
Thaumarchaea are dependent on resources released
by phytoplankton, such as organic carbon or
ammonium.
1 Könneke, M. et al. 2005. Nature 437: 543-546
2 Brochier-Armanet, C. et al. 2008. Nat Rev Microbiol
6: 245–252.
3
Sinninghe Damsté, J.S. et al. 2002. J. Lipid Res.
43:1641–1651.
4
Harris ,P.G. et al. 1996. Nature 383: 63–65.
Figure 1. Examples of the correlation of chlorins
(chlorophyll transformation products) and crenarchaeol A)
chlorins and crenarchaeol concentrations per gram dry
matter in Lake Baikal during the Last Interglacial
(approximate MIS5e) and transitional periods; B)
Correlation between chlorins and crenarchaeol
concentrations in Lake Baikal and the subantarctic
Southern Ocean (ODP site 1090); the log-log fits were
significant at 1%CI level with R²=0.90 in Lake Baikal and
R²=0.78 in the Southern Ocean.
308

P-169
Lipid biomarkers in ooids from different locations and ages
provide evidence for a common bacterial flora
Aimee Gillespie 1 , Laurence Bird 2 , Sara Pruss 3 , Alex Sessions 4 , Mark Roberts 5 , Roger
Summons 1
1 Massachusetts Institute of Technology, Cambridge, MA, United States of America, 2 Pennsylvania State
University, University Park, PA, United States of America, 3 Smith College, Northampton, MA, United States
of America, 4 California Institute of Technology, Pasadena, CA, United States of America, 5 Woods Hole
Oceanographic Institution, Woods Hole, MA, United States of America (corresponding
author:aimeeg@mit.edu)
Ooids are an important but enigmatic part of
the sedimentary carbonate system. They form in low
latitude, agitated, shallow water environments that are
supersaturated with respect to calcium carbonate. At
present,ooids are actively precipitating in only a few
places, notably the tropical Atlantic and Indian
Oceans. However oolitic limestones have been found
in many sedimentary sections throughout Earth
history. Ooids are useful as stratigraphic markers and
as indicators of paleoenvironment; they are also a key
component of the carbonate that is being trapped and
bound in modern and ancient stromatolites.
Despite their importance in the carbonate
system and usefulness in stratigraphic reconstruction,
the ooid formation process is not well understood. A
particularly contentious aspect is the role of
microorganisms in carbonate precipitation,
cementation (in the case of oolites), and
remineralization. Early research on the topic
suggested that organic matter, and perhaps biofilms,
plays a key role in the concentric layering that
characterizes ooids.
Modern and Holocene ooid samples,
collected from outcrops and beaches in the Bahamas
and in Shark Bay in Western Australia, were
examined for their contents of lipid biomarkers.
Modern samples from Cat and Andros islands in the
Bahamas and from Carbla Beach in Hamelin Pool,
Western Australia, showed abundant and surprisingly
similar distributions of hydrocarbons, fatty acids, and
alcohols. A large fraction of these lipids were bound
into the carbonate matrix and only released on acid
dissolution, which suggests that these lipids were
being incorporated continuously during ooid grow.
This is further evidenced by older 14 C ages of the
carbonate-bound lipids.
The distributions of hydrocarbons, and their
varied � 13 C values, were consistent with mixed inputs
from cyanobacteria (C17-C19; � 13 C = -15 to -24
‰VPDB) together with small and variable amounts of
vascular plant leaf wax (C27-C35; � 13 C = -25 to -32
‰VPDB). The fatty acids (FA) comprised a complex
mixture of C12-C18 normal and branched short chain
isomers with the predominant straight-chained
components attributable to bacteria and/or
cyanobacteria.
Branched FA isomers, especially 10-MeC16
and 10-MeC18, together with the prevalence of
elemental sulfur in the extracts, indicate an origin from
sulfate reducing bacteria. The iso- and anteiso- FA
were quite variable in their 13 C contents suggesting
that they come from organisms with diverse
physiologies. Hydrogen isotopic compositions
provide further insights into this issue, with branched
fatty acids having relative D-enrichments
characteristic of heterotrophic bacteria.
The most enigmatic lipid assemblage is a
homologous series of long-chain (C24-C32) FA with
pronounced even carbon number preference.
Typically such long-chain FA are thought to come
from land plant leaf wax but their relative 13 C
enrichments (C24-C32; � 13 C = -18 to -22 ‰VPDB),
indicate a microbial origin in this case.
The distributions of lipids isolated from
Holocene oolites from the Rice Bay Formation of Cat
Island, Bahamas were very similar to the beach ooids
described above and, in total, these biomarker data
lead us to hypothesize that ooid formation in tropical
marine environments is mediated by a defined
microbial community.
References:
Duguid et al.,80 (3): 236. Journal of Sedimentary
Research (2010).
Taylor and Parkes 129 (11): 3303. Journal of General
Microbiology (1983).
Zhang et al., 106: 12580. Proceedings of the National
Academy of Science (2009).
309

P-170
Microbial activity and abundance in sediments Lake Van
(Turkey), first results from ICDP Project PALEOVAN
Clemens Glombitza, Jens Kallmeyer
University of Potsdam, Potsdam, Germany (corresponding author:clemens.glombitza@geo.uni-potsdam.de)
Studies during the past two decades have
demonstrated the importance of microbial life in the
deep subsurface. So far, most studies focused on life
in the subseafloor, only few dealt with terrestrial
environments. With the exception of some very few
and solitary projects, lacustrine sediments received
almost no attention.
In summer 2010 the ICDP drilling operation at Lake
Van (Eastern Anatolia, Turkey) recovered long
sediment cores at two sites (Northern Basin and Ahlat
Ridge). At both sites, sample material was obtained
from undisturbed core catchers and selected whole
round cores, ranging in depth from the sediment
surface down to 140 mblf (meters below lake floor).
Coring was mainly carried out by hydraulic piston
coring, providing largely uncontaminated samples, as
seen by the porewater composition in the sample.
However, certain intervals with thick layers of volcanic
ash required extended core barrel and rotary coring,
the obtained cores were at least partially infiltrated by
drilling fluid. Additionally, short gravity cores of 75 cm
length were retrieved at both sites, providing the
undisturbed sediment-water interface, which is too
liquid to be recovered by hydraulic coring.
Radiotracer experiments for the quantification of
sulfate reduction, anerobic oxidation of methane and
methanogenesis were initiated on site, using the
mobile Geomicrobiology Laboratory BugLab, owned
by GFZ Potsdam. Porewater was squeezed and split
between the different working groups. Samples for
cell enumeration and anion porewater analysis were
preserved for analysis at the University of Potsdam.
Although the distance between the two sites is only
approx. 7 km, they exhibit significant differences,
both in porewater geochemistry and in microbial
abundance and activity.
The results of the cell enumeration are strikingly
different to marine sediments. Whether these trends
are the result of sedimentological changes or lateral
fluid flow remains unclear at the moment, as a full
sedimentological description of the cores is still
lacking. Cell abundance appears to be slightly higher
at the Northern Basin site, at which sulfate reduction
rates measured by radiotracer are also generally
higher than at Ahlat Ridge. Despite the higher sulfate
reduction rates at the Norther Basin site, sulfate
penetrates down to 40 mblf, about twice as deep than
at Ahlat Ridge. This is most probably caused by the
lateral influx of a saline brine between 20 and 40 mblf.
The significant biogeochemical differences between
both sites indicate that lacustrine sediments are very
sensitive to changes in sedimentary and organic
matter input. Studies of the deep subsurface of lake
sediments are still in their infancy but due to strong
biogeographical gradients they may offer a unique
chance to study the effects of even small geological
changes on deep subsurface life.
310

P-171
Lipid biomarkers and phylogenetic analysis indicating the
variability of methanogenic communities within terrestrial Late
Pleistocene and Holocene permafrost deposits in the central
Lena River delta, Siberia
Juliane Griess 1,2 , Kai Mangelsdorf 1 , Dirk Wagner 2
1 GFZ German Research Centre for Geosciences, Potsdam, Germany, 2 Alfred Wegener Institute for Polar
and Marine Research, Potsdam, Germany (corresponding author:juliane.griess@awi.de)
Permafrost environments of the Northern
hemisphere are suspected to be strongly affected by
the currently observed and predicted global
temperature rise (IPCC, 2007). Given that about one
third of global soil stored carbon is preserved in high
Arctic environments, a degradation of permafrost due
to potential future increases of atmospheric and soil
temperatures might lead to an increased
bioavailability of recent as well as ancient carbon.
Thus, an intensified microbial turnover of these
particular carbon pools, driven by substrate
availability and temperature, might cause the release
of large amounts of greenhouse gases such as
methane.
To predict the risk for future climate and
estimate the global atmospheric carbon budget, it is
important to understand the microbial driven methane
dynamics of the Siberian Arctic and their response to
climate changes in the past. Therefore, a combination
of quantitative and qualitative analyses of recent and
fossil methanogenic communities were performed to
reveal variations in permafrost deposits of the
Siberian Arctic.
The Lena River Delta, northeast Siberia, is the
largest delta within the circum arctic land masses with
approximately 29000 km². Drilling of a 23 m
permafrost core was conducted on Kurungnakh
Island, Central Lena Delta (N 72°20, E 126°17) in
2002. Kurungnakh Island is located in the zone of
continuous permafrost and composed of late
Quaternary sediments. The permafrost sequence is
characterized by Late Holocene deposits of sandy
layers, covered by a huge, second formation called
'Ice complex' (IC), with inclusions of large peat blocks
with less decomposed organic material. Furthermore,
Holocene layers of about 2-3 m thickness on top of
the IC are containing ice-wedges of 3-5m width.
The recovered permafrost sequence is
characterized by strong vertical variations of the total
organic carbon (TOC) and in-situ methane content.
The TOC content varies from 2 to 14%, whereas the
methane concentrations range from 2 to 1600 ppm in
certain layers.
Generally, in-situ methane contents reflect the
TOC profile with depth. In this context the questions
are: Is this methane produced by recently active
methanogenic communities in permanently frozen soil
or was the methane produced and trapped during
times of sediment deposition and permafrost
progression and, thus, originate from fossil
communities?
Lipid biomarkers and amplifiable DNA were
successfully recovered throughout the whole
Kurungnakh permafrost sequence with an age of up
to 42 ka. Analysis on the abundance and distribution
of branched and isoprenoidal glycerol dialkyl glycerol
tetraether (GDGT) core lipids (being indicators for
bacteria and archaea, respectively) revealed
variations within the vertical profile following the
trends outlined by the TOC and methane contents.
At 17 m soil depth an interesting interval is
indicated by a pronounced occurrence of archaeal
GDGTs. Additionally, a variety of intact phospholipid
esters indicate the presence of a viable microbial
community at this depth. Furthermore, the respective
interval is characterized by comparably low
abundance of methane, but high amounts of archaeol
and a high diversity of methanogenic archaea, as
shown by genetic fingerprints obtained from
denaturising gradient gel electrophoresis (DGGE).
This suggests the possibility of recent
methanogenesis in permanently frozen ground,
whereas methane might have diffused through the
soil and been trapped in overlaying TOC-rich layers.
Phylogenetic analysis on the basis of clone
libraries of the respective methanogenic communities
show changes in composition and dominance of the
different genera with depth. This observation is
discussed as an adaption of microorganisms to
substrate quality and quantity of soil organic matter or
sedimentation conditions during times of sediment
deposition.
311

P-172
Microbially mediated carbonate formation from gypsum and oil
Vincent Grossi 1 , Marion Baudrand 1 , Rich Pancost 2 , Christophe Lécuyer 1 , Marie-
Magdeleine Blanc-valleron 3 , Mahmoud Aref 4 , Jean-Marie Rouchy 3 , Giovanni Aloisi 1,5
1 CNRS - Université de Lyon, Villeurbanne, France, 2 University of Bristol, Bristol, United Kingdom, 3 CNRS -
Muséum National d'Histoire Naturelle, Paris, France, 4 Cairo University, Giza, Egypt, 5 CNRS - Université
Pierre et Marie Curie, Paris, France (corresponding author:vincent.grossi@univ-lyon1.fr)
Large amounts of evaporitic gypsum are present
in sedimentary basins worldwide, which may come
into contact with organic matter(OM)-rich sediments.
If the temperature is below 80°C, microbial
communities which include sulfate-reducing bacteria
(SRB) may develop, dissolving gypsum and
promoting carbonate and sulfur precipitation:
OM + CaSO4, 2H2O � S0 + CaCO3 + H2O
In order to study this biogeochemical process in
hydrocarbon-rich environments, we investigated
sulfur-bearing carbonate samples from Egypt which
are in close stratigraphical contact with Miocene
evaporitic gypsum deposits and with petroleum
seepage.
Mineralogical and petrographical observations
indicate the presence of carbonate pseudomorphs
after gypsum crystals which are often associated with
euhedral elementary sulfur. The studied carbonates
are composed of calcite and/or dolomite. A new semiautomatic
analytical method was developed to
differentiate between carbon and oxygen stable
isotopic compositions of each carbonate pool in these
natural mixtures of calcite and dolomite [1]. All
carbonates are depleted in 13 C (-24.5‰ < δ 13 C (vs
PDB) < -2.8‰) but only calcite bears a clear OM
isotopic signature (-15‰ < δ 13 C < -25‰) similar to
that of oil associated to it. This suggets that: 1) calcite
was precipitated from a 13 C-depleted fluid produced
by a bacterial activity and, 2) (part of) the carbon
incorporated in calcite comes from petroleum
hydrocarbons.
GC-MS analysis of the lipids present in the
carbonates show the presence of more or less
biodegraded petroleum hydrocarbons. The most
degraded sample also contains specific bacterial (e.g.
macrocyclic non-isoprenoid dialkyl glycerol diethers,
DGDs) and archaeal (e.g. archaeol) lipids indicating
the presence of a mixed microbial community
characteristic of this specific ecosystem [2; Fig. 1].
The compound specific stable carbon isotopic
composition (δ 13 C) of petroleum hydrocarbons ranges
from -24 to -28‰. The isotopic compositions of
bacterial DGDs are slightly depleted (-28 to -30‰)
compared to hydrocarbons whereas the isotopic
signature of archaeol is slightly enriched (~ -23‰).
Fig. 1. Chromatograms of biodegraded oil and polar
microbial lipids present in diagenetic carbonates from Egypt.
The data allow proposing a model for the formation
of diagenetic carbonates by SRB using petroleum
hydrocarbons as carbon source and gypsum sulfate as
terminal electron acceptor. The heavier carbon isotopic
composition of carbonates compared to bacterial lipids
suggests however that an additional, isotopically
heavier, carbon source has been incorporated into
carbonates.
References
[1] Baudrand, M., Aloisi, G., Lécuyer, C., Martineau, F., et al.
(2011) Appl. Geochem., in press.
[2] Baudrand, M., Grossi, V., Pancost R., Aloisi, G. (2010)
Org. Geochem. 41, 1341-1344.
312

P-173
Oxidation and physical protection of organic matter by mineral
matrix : their influence on the diagenesis of hopanoids
Yann Hautevelle, Apolline Lefort, Pierre Faure, Raymond Michels
UMR7566 G2R, CNRS, Nancy Université, Vandoeuvre-lès-Nancy, France (corresponding
author:yann.hautevelle@g2r.uhp-nancy.fr)
Hopanoids are among the most abundant
organic compounds in the geosphere. Their
distribution is classically studied in organic
geochemistry for assessing the thermal history of
sedimentary series. Indeed, it is now well known that
hopanoids are biosynthesized under a
thermodynamic unstable biological conformation.
Furthermore, thermal immature sedimentary rocks are
typically characterized by the presence of hopenes.
During thermal stress, hopenes are hydrogenized into
hopanes, the 22S isomer appears for each
homohopanes and the biological conformation is
transformed into the more stable geological
conformation.
However, some of our work suggests that the
classical interpretation of hopane distributions, based
on the influence of heating, should be moderated due
to the fact that other stresses, like oxidation, have a
similar incidence on the diagenesis of hopanoids.
Indeed, experiments show that oxidation of the
thermally immature Callovian-Oxfordian claystones
from the east of the Paris basin also induces a
progressive decrease of hopenes, the apparition of
22S isomers as well as the transformation of
biological conformation into the geological.
We also studied these Callovian-Oxfordian
claystones as well as their Oxfordian surrounding
limestones. The claystones are characterized by a
clearly immature distribution of hopanoids
(abundance of hopenes, hopanes in the biological
conformation and the large predominance of the 22R
epimers over the 22S). Surprisingly, a more mature
distribution was found in the limestones (lower
abundance of hopenes, the presence of higher
proportion of hopanes in the geological conformation
and the significant presence of 22S epimers). In this
case, thermicity cannot be invoked to explain this
discrepancy because the Oxfordian limestones lie
above the claystones and their temperature has not
exceeded 50°C since deposition. So, another
explanation must be advanced to account for this
difference. As oxidation seems to have a similar effect
than thermicity on hopanoid distributions, we can
expect that the ―mature‖ distribution characterizing the
limestones can be related to a more intense post-
depositional oxidation. At the opposite, the hopane
distribution indicates that the organic matter of the
claystones was not oxidized although the deposit
conditions were also oxic. This can be explained by a
protective matrix effect of clay minerals.
In the Cretaceous siltites of Marcoule, we show that
hopanoids also underwent oxidation but only in
specific layers associated to bioturbation. In this case,
oxidation seems to be favored by the disturbation of
the embedding sediment which lowers the protective
matrix effect.
More recently, we focused our investigation
on the carbonate Oxfordian-Kimmeridgian platform at
Gudmont-Villiers (Eastern Paris basin). These
limestones were deposited in a lagoon & shallow
marine environments. They present an alternation of
carbonate mudstone and grainstone beds. These
deposits underwent a similar and very low thermicity
after their deposition since they are located above the
Callovo-Oxfordian claystones. In this case, carbonate
mudstone beds also present a typically ―immature‖
distribution of hopanes while the grainstones show a
more ―mature‖ distribution. Once again, thermicity
cannot be at the origin of this discrepancy. However,
mudstones are associated to a settling hydrodynamic
regime and are rather impermeable, while grainstones
are related to more agitated conditions and typically
porous at deposition time. In mudstones organic
matter is much more protected from oxidation than in
grainstones.
This work clearly shows that care must be
taken when interpreting the distribution of hopanoids
in terms of thermicity. Yet, differences in hopanes
distributions as a function of facies may be combined
with other biomarkers to infer diagenetic/
palaeoenvironmental conditions during deposition.
313

P-174
Distinct microbial inventories in terrestrial mud volcanoes of
Northern Italy controlled by the source and composition of
emitted fluids
Christina Heller 1 , Martin Blumenberg 1 , Christoph Wrede 2 , Michael Hoppert 2 , Marco
Taviani 3 , Joachim Reitner 1
1 Geoscience Centre, University of Goettingen, Goettingen, Germany, 2 Institute of Microbiology and Genetics,
University of Goettingen, Goettingen, Germany, 3 ISMAR-CNR, Bologna, Italy (corresponding
author:cheller1@gwdg.de)
Mud volcanoes are geological structures that occur in
terrestrial and marine environments worldwide and
are caused by various geological processes e.g.
tectonic accretion and faulting. In Italy such fluid
venting structures occur along the external
compressional margin of the Apennine chain, where
the mud volcanoes are distributed along two belts [1].
The natural Salse di Nirano (near Modena) is one of
the largest mud volcano areas in Italy, emitting gas
with approximately 99 % methane and only minor
amounts of higher hydrocarbons. The fluids seeping
out in Nirano pass through geological formations from
the Jurassic to the lower Pleistocene [2]. In doing so,
the mud is getting enriched in various electron
acceptors (e.g. SO4 2- , NO2 - /NO3 - , O2), potentially
fueling microbial aerobic and anaerobic oxidation of
hydrocarbons, in particular methane [3,4,5]. A
second, smaller and geologically distinct mud volcano
area is situated in Puianello (near Modena). In
Puianello methane concentrations in the gases are
lower ~48 % and, in contrast to Nirano, the fluids do
not cross Messinian formations, thus, ions like sulfate
are relatively lower in concentration.
Our biomarker and molecular microbiological (16S
rDNA) data show that microbial communities in the
different mud volcanoes are distinct. We found signals
of various eukaryotes, bacteria and archaea at both
sites. In Nirano, however, specific bacterial dialkyl
glycerol diethers (DAGE; in particular ai15/ai15- and
16/16-DAGE) were found which are putatively
sourced by sulfate-reducing bacteria (SRB) [6,7,8].
The presence of archaea is evidenced by archaeol
and hydroxyarchaeol and isotopic analyses of SRBderived
bacterial DAGE as well as hydroxyarchaeol
demonstrated 13 C-depletions with δ 13 C values low as -
54‰, suggesting an involvement of the source
organisms in the sulfate-dependent anaerobic
turnover of methane. By contrast, typical SRBbiomarkers
were absent in sulfate-poor mud
volcanoes in Puianello. But, various 13 C-depleted
hopanoids e.g. 17β(H)21β(H)-bishomohopanol
17β(H)21β(H)-bishomohopanoic acid and 3Me-
17β(H)21β(H)-bishomohopanol were highly abundant.
Since the latter are typical biomarkers for aerobic
methanotrophs, those bacteria appear to be keyplayers
in this environment.
Our data demonstrate a high microbial and metabolic
diversity in terrestrial mud volcanoes in Italy, which is
most likely controlled by different geological settings
and thus mud compositions.
[1] Minissale, A., Magro, G., Martinelli, G., Vaselli, O.,
Tassi G.F. (2000). Tectonophysics 319, 199-222.
[2] Bonini, M. (2008). Geology 136, 131-134.
[3] Nauhaus, K., Albrecht, M., Marcus Elvert, Boetius,
A., Widdel F. (2007). Environ. Microbiol. 9, 187–196.
[4] Wrede, C. Brady, S., Dreier, A., Rockstroh, S.,
Kokoschka, S., Heinzelmann, S.M., Heller, C, Reitner,
J., Taviani, M., Daniel, R., Hoppert, M. (2011). Sed.
Geol. (in revision).
[5] Alain, K., Holler, T., Musat, F., Elvert, M., Treude,
T., and Krüger, M. (2006). Environ. Microbiol. 8, 574-
590.
[6] Pancost, R.D., Bouloubassi, I., Aloisi, G.,
Sinninghe Damsté, J.S., Party, T.M. S. (2001a). Org.
Geochem. 32, 695-707.
[7] Pancost, R.D., Hopmans, E. C., Sinninghe
Damsté, J. S., Party, T.M.S. (2001b). Geochim.
Cosmochim Acta 65, 1611-1627.
[8] Blumenberg, M., Seifert, R., Reitner, J., Pape, T.,
and Michaelis, W. (2004). Proc. Nat. Acad. Sci. 101,
30, 11111-11116.
314

P-175
Molecular and isotopic biosignatures in altered and unaltered
hydrothermal precipitates of the southern Mid-Atlantic Ridge
Sascha Herrlich 1 , Martin Blumenberg 2 , Walter Michaelis 1 , Anne Dreier 3 , Richard Seifert 1
1 Institute of Biogeochemistry and Marine Chemistry, University of Hamburg, Hamburg, Germany,
2 Department of Geobiology, Geoscience Centre (GZG), Georg-August-University of Göttingen, Göttingen,
Germany, 3 Department General Microbiology, Institute of Microbiology and Genetics, Georg-August-
University of Göttingen, Göttingen, Germany (corresponding author:richard.seifert@zmaw.de)
Deep sea hydrothermal systems are outstanding
geobiological habitats. Steep redox gradients
between hydrothermal fluids and sea water offer an
excellent basis for chemoautotrophic microorganisms
and massive metal sulphide precipitates provide a
long-lasting energy source for Fe/S-oxidizers.
Recent studies on autochthonous microbial
communities of unaltered hydrothermal precipitates
using chemical structures and stable isotope ratios of
organic compounds revealed specific biomarkers and
indicated an extraordinary phylogenetic and metabolic
diversity. [1,2]. However, similar studies on microbial
communities invading hydrothermal deposits after the
active state are almost missing.
In this study we compare molecular biosignatures
enclosed in an almost unaltered fresh metal sulphide
precipitated by an active black smoker emitting
extraordinarily hot fluids with those of a subrecent
altered chimney having been exposed to seawater for
an extended time period.
Samples were obtained in 2009 by a remotely
operated vehicle (ROV Kiel 6000) from 3000m water
depth during R/V Meteor cruise M78/2 between 5°
und 9°S at the Mid-Atlantic Ridge.
The observed differences in distribution and isotopic
composition of biomarkers between the active and the
altered black smoker mirrors the change from the
microbial community inhabiting the active
hydrothermal system to a secondary community
dominant during early diagenetic alteration of the
precipitates.
For the active smoker sample, high concentrations of
fatty acids strongly enriched in 13 C (� 13 C-values of
about -10 ‰) point to chemolithoautotrophic,
hydrogen-oxidizing bacteria using the rTCA-cycle for
carbon fixation (e.g., Hydrogenobacter, Aquifex [3].
By contrast, the altered black smoker contains high
concentrations of 13 C-depleted iso-, anteiso-, and mid
chain-branched penta- and heptadecanoic fatty acids.
Some of these compounds might originate from
sulphur-oxidizing bacteria fixing carbon via the Calvin
cycle as reported for relatives of Thiobacillus,
Acidithiobacillus [3].
Both samples contain a huge variety of bacterial and
archaeal Dialkyl Glycerol Diethers (DAGE). The wide
range of � 13 C-values of the DAGE in both samples
points to consortia of bacteria and archaea using
different carbon fixation pathways.
13 C-depleted
hydroxyarchaeol (� 13 C of -70‰) indicates
methanotrophic archaea (ANME-2) in the altered
sample.
Interestingly there was a regular C25 isoprenoid
analyzed after ether cleavage suggested to originate
from C25,25 or C20,25 archaeol. The latter is described
from halophilic archaea, while the former was
reported from the aerobic, hyperthermophilic
crenarchaeon Aeropyrum pernix, isolated from a
solfataric vent [4].
For the altered black smoker sample, high amounts of
acyclic, monocyclic and bicyclic biphytanes were
released by cleavage of ether bonds from archaeal
Glycerol Dialkyl Glycerol Tetraethers (GDGT). Among
clear signals from methanogens, the prevalence of
monocyclic and bicyclic biphytanes indicated
contributions from mesophilic to moderately
thermophilic, Fe-oxidizing archaeon Ferroplasma
acidophilum [5] and/or from the thermoacidophilic
sulphur oxidizing archaeon.
Preliminary lipid data of selected, yet unstudied
extremophilic isolates, accompanying our work on
hydrothermal sulfides, indicate that e.g. the nitratereducing
thermophilic Caldithrix abyssi is an important
member of the microbial community in the altered
sulfide.
References
[1] Blumenberg M, Seifert R, Petersen S, Michaelis
W. 2007. Geobiology 5:435-450.
[2] Bradley AS, Hayes JM, Summons RE. 2009.
Geochim Cosmochim Acta 73:102-118.
[3] Naraoka H., Uehara T., Hanada S., Kakegawa T.
2009. Org. Geochem., 41, 398-403.
[4] Sako Y., et al. 1996. J. System. Bacteriol., 46,
1070–1077
[5] Golyshina O. V., Timmis K. N. 2005. Environ
Microbiol., 7, 1277–1288.
315

P-176
Microbial consortium mediating carbon cycle in a subsurface
and oliogotrophic karst cave in China
Yang Huan, Xie Shucheng
Key laboratory of Biogeology and Environmental Geology of Ministry of Education, China University of
Geosciences, Wuhan, Wuhan, China (corresponding author:yanghuansailing@163.com)
The karst topography is widely distributed in
southwestern China and exerts significant influence
on people‘s lives in this region. The stone
desertification in karstified areas has become a
serious problem in agriculture because crops are not
able to grow on the barren lands. In addition,
stalagmites in karst caves are extraordinarily good
archives of paleoenvironmental reconstruction due to
their precise and high-resolution chronology, and little
diagenesis influence.
The inorganic carbon kinetics in soil-dripwaterstalagmite
system has been well documented to
delineate the paleoenvironmental information of δ 13 C
values for stalagmites [1]. However, most carbon
kenetic models in karst environment are restricted to
thermodynamic processes, whether the biological,
especially microbial activities may influence carbon
cycle is poorly understood. The karst cave can be
considered as an oligotrophic and aphotic ‘extreme’
environment as nutrients can not be readily
transported to caves through subterranean water
drainage system and light are usually unavailable.
The phototrophs, e.g. cyanobacteria can not survive
and thus provide no dissolved organic matter to the
heterotrophic bacteria in the cave. Although cavederived
stalagmites have attracted numerous
attentions, little is known about the microbial
community structure and their function in
biogeochemical cycles in this subsurface habitat.
We collected stalagmites, dripwater, cave
sediments, the surface sediments of growing
stalagmites and weathered surface of collapsed
parent rock inside the Heshang cave in central China
to explore the microbial community structure and their
putative function in carbon cycle in karst cave. The
microbial lipids were extracted repeatedly with
dichloromethane/methanol (9:1, v/v) in an ultrasonic
apparatus. The archaeal and bacterial tetraether
membrane lipids, glycerol dialkyl glycerol tetraethers
(GDGTs) were analyzed by high performance liquid
chromatogram and mass spectrometer while fatty
acid, alcohols, sterols and hopanoids were analyzed
by gas chromatography and mass spectrometer.
Previous work has demonstrated that the majority of
archaeal isoprenoid and bacterial branched GDGTs in
stalagmites were probably both in situ produced on
the surface of stalagmites [2]. A newly-recovered
surface sample of a growing stalagmite shows also
significant predominance of crenarchaeotal GDGTs
over bacterial GDGTs and very high diversity of
bacterial lipids including branched fatty acids,
branched fatty alcohols, monoalkyl glycerol ethers
(MAGEs), diethers, hopanols and hopanoic acids
with little contribution from plant lipids in overlying
soils. Most crenarchaeota and MAGEs-producing
bacteria are believed to be chemoautotrophic
microbes and they may uptake bicarbonate as the
sole carbon source for biosynthesis. Therefore the
chemoautotrophs living on the surface of stalagmites
may influence the carbon dynamic fractionation during
the stalagmite formation.
Phylogenetic analysis reveals that marine group
1.1a and 1.1b crenarchaeota, two groups of
ammonia-oxidizers, dominate in the Heshang cave
sediments. The high abundance of crenarchaeol and
low abundance of branched GDGTs were present in
most cave sediments and all stalagmites samples,
which were flushed continuously or discontinuously by
bicarbonate-saturated dripwater. In contrast,
sediments distant from dripwater site show much
higher branched GDGTs than archaeal GDGTs,
indicating that crenarchaeota may uptake bicarbonate
and play a vital important part in carbon and nitrogen
cycle in karst cave. The microbial lipids from the
sediments in the drainage system show apparently
higher abundance than that away from drainage
system, implying that dripwater carry bicarbonate and
other nutrients, thus may fuel the microbial growth in
sediments. Therefore the dripwater may function as
the key energy source for microbes living in the karst
cave environment.
References
[1] Dreybrodt, W. and Scholz, D. (2011) Geochim.
Cosmochim. Acta 75, 734-752.
[2] Yang, H., Ding, W., Zhang, C.L., et al., (2011) Org.
Geochem. 42:108–115.
316

P-177
Rhizoliths in loess: evidence for the heterotrophic lifestyle of
branched GDGT-producing bacteria
Arnaud Huguet 1 , Guido L.B. Wiesenberg 2 , Martina Gocke 2 , Céline Fosse 3 , Sylvie
Derenne 1
1 BioEMCo, CNRS/UPMC UMR 7618, Paris, France, 2 Department of Agroecosystem Research, BayCEER,
University of Bayreuth, Bayreuth, Germany, 3 Chimie ParisTech (ENSCP), Laboratoire de Spectrométrie de
Masse, Paris, France (corresponding author:arnaud.huguet@upmc.fr)
Over the last years, an increasing number of
studies have focused on glycerol dialkyl glycerol
tetraethers (GDGTs), which are complex lipids of high
molecular weight (>1000 Da) present in membranes
of archaea and some bacteria. Isoprenoid GDGTs
with acyclic or ring containing dibiphytanyl chains are
known to be synthesized by archaea. In soil, another
type of GDGTs, which can be distinguished from
tetraethers of archaeal origin by way of the branched
nature of the alkyl chain, was discovered recently.
Branched GDGTs were subsequently detected in a
large variety of environments (peats and soils, hot
springs, lacustrine and marine sediments) and are
synthesized by still unknown bacteria. The relative
distribution of branched GDGTs can be related mainly
to mean annual air temperature (MAAT) and soil pH.
The cyclisation ratio of branched tetraethers (CBT),
quantifying the relative abundance of cyclopentyl
rings of branched GDGTs, correlates rather well with
soil pH, whereas the methylation index of branched
tetraethers (MBT), expressing the degree of
methylation of branched GDGTs, depends on MAAT
and, to a lesser extent, on soil pH. The MBT and CBT
can be used as proxies for paleotemperatures and
paleo soil pH. The aim of the present work was to
examine the distribution and abundance of GDGTs in
rhizoliths (calcified roots) and surrounding loess
collected from a loess-palaeosol sequence in
Nussloch (SW Germany). For two rhizoliths from a
depth between 2.2 m and 2.6 m below present
surface, loess transects were sampled from the
former root towards root-free loess at distances of 0-
2.5 cm and 2.5-5 cm (rhizoloess samples). Two
reference loess samples without visible root remains
were taken at a distance of 50-70 cm from the
rhizoliths.
Branched GDGTs were much more abundant in the
rhizoliths than in the rhizoloess and almost absent in
reference loess samples. The very high abundance of
branched GDGTs in the rhizoliths suggests that
branched GDGT source organisms feed on root
remains. In larger distances to root surfaces, nutrient
and energy supply decreases, likely leading to the
lower abundance of branched GDGT source
microorganisms observed in the rhizoloess and
reference loess compared to the rhizoliths. Branched
GDGT distribution patterns were different for
individual sample types. The MBT was lower in the
rhizoliths (0.23-0.26) than in the rhizoloess (0.37-
0.47) and loess samples (0.39-0.41). Branched
GDGTs in the rhizoliths and loess might have been
produced during different time intervals, since
radiocarbon dating of one rhizolith revealed its
Holocene age (3150 years b.p.), in contrast to late
Pleistocene age of surrounding loess (17-20 ka). In
rhizoliths, branched GDGTs were very likely
generated during and/or after plant death (i.e. about
3000 years ago), whereas in loess they were probably
formed after sedimentation and/or during earlier
pedogenesis of the modern soil. Consequently, the
age of branched GDGTs in the rhizoliths and
reference loess may differ, which could explain the
differences in GDGT composition between the former
roots and the loess.
MAAT and pH were reconstructed using the MBT
and CBT indices. Consistent results were obtained for
each sample type (rhizolith, rhizoloess, loess). Thus,
MAAT estimates derived from the two rhizoliths (2.9–
3.7 °C) were lower than those derived from rhizoloess
(9.1–14.6 °C) and loess (10.1–10.8 °C) samples. At
the time of the formation of rhizoliths, temperature
might have been like present MAAT (10 °C), implying
that MBT/CBT-derived MAAT estimates for the
rhizoliths (ca. 3 °C) are likely lower than the ―real‖
MAAT value. In contrast, MAAT estimates based on
branched GDGT distribution in the loess seem too
high (ca. 10 °C). Indeed, loess was deposited during
cold periods, with assumed temperatures close to
zero. The reasons for the deviation between real and
reconstructed MAAT values remain unclear,
suggesting that caution should be exercised when
applying and interpreting temperature estimates
derived from bacterial GDGTs in loess-paleosol
sequences, considered as important terrestrial
archives for studying Quaternary climate. In contrast
to temperature, CBT-derived pH values were in the
same range (7.7–8.1) for the three sample types and
are consistent with the actual pH of reference loess
(8.1). To the best of our knowledge, this is the first
time that the heterotrophic lifestyle of branched
GDGT-producing bacteria is evidenced solely based
on GDGT abundance.
317

P-178
Diversity of microbial communities associated with lowtemperature
hydrothermal venting at the ultra-slow spreading
Arctic Mid-Ocean Ridge
Andrea Jaeschke 1 , Gretchen L. Früh-Green 1 , Stefano M. Bernasconi 1 , Ida H. Steen 2 ,
Ingunn H. Thorseth 2 , Rolf B. Pedersen 2
1 ETH Zürich, Zürich, Switzerland, 2 University of Bergen, Bergen, Norway (corresponding
author:andrea.jaeschke@erdw.ethz.ch)
A low-temperature hydrothermal field hosting
numerous barite chimneys is located at the flank of a
large sulphide mound of the Loki‘s Castle black
smoker vent field at about 73°N on the Arctic Mid-
Ocean Ridge (AMOR) [1]. The dense field of small
(

P-179
Tetraether membrane lipid distributions in lacustrine sediments:
a study of 28 lakes in the Yangtze floodplain (SE China)
Li Jingjing, Yang Huan, Qin Yangmin, Huang Junhua, Xie Shucheng
China University of Geosciences, Wuhan, China (corresponding author:ljjvalerie@gmail.com)
Recently, several climate and environmental proxies
based on glycerol dialkyl glycerol tetraethers
(GDGTs) from Archaea and Bacteria have been
developed and applied in diverse environments
(Powers et al., 2004; Weijers et al., 2006). However,
there are many unknown questions about the source
and mechanism of GDGTs. Do the chemical and
physical property (i.e. TP, TN, DO, COD, the
concertration of Mg 2+ , Cl - , Ca 2+ , SO4 2- , etc.) of lake
sediments influence the GDGTs the distribution? In
this study, we studied the distribution of GDGTs in the
surface sediment of 28 lakes in the Yangtze floodplain
(SE China). A comparison has been made to testify
the chemical and physical property and GDGTs
distribution of lake sediments. It suggests the
chemical and physical property do affect the
distribution of GDGTs, while lakes with exceptional
chemical and physical property are consistent with the
abnormal GDGTs distribution. Compared to bacterialderived
branched GDGTs, the isoprenoid GDGTs
derived from archaea were less affected. The results
indicate the property of lake sediments may influence
the habitats of bacteria and archaea, which may lead
to the distinct distribution of GDGTs from different
lakes. Further studies will determine which property
would affect the bacteria and archaea activity.
References
Powers, L.A., Werne, J.P., Johnson, T.C., Hopmans,
E.C., Damste, J.S.S., Schouten, S., 2004.
Crenarchaeotal membrane lipids in lake sediments: A
new paleotemperature proxy for continental
paleoclimate reconstruction? Geology 32, 613-616.
Weijers, J.W.H., Schouten, S., Spaargaren, O.C.,
Sinninghe Damst? Jaap, S., 2006. Occurrence and
distribution of tetraether membrane lipids in soils:
Implications for the use of the TEX86 proxy and the
BIT index. Organic Geochemistry 37, 1680-1693.
319

P-180
Inhibition of anaerobic oil degradation by low molecular weight
hydrocarbons
Angela Sherry, Russell Grant, Carolyn Aitken, Martin Jones, Neil Gray, Ian Head
Newcastle University, Newcastle upon Tyne, United Kingdom
Long lag phases of several months before
hydrocarbon degradation becomes measurable in
laboratory experiments under anaerobic,
methanogenic conditions, have been noted previously
(e.g. Townsend et al., 2003; Jones et al., 2008).
Some reports of a lag phase in methane production
after the addition of hydrocarbons to methanogenic
enrichment cultures suggest that light end n-alkanes
(

P-181
Bacterial wax esters in fluvial sediments from the Danube River
(Republic of Serbia)
Jürgen Köster 1 , Vesna Miciš 2 , Michael A. Kruge 3 , Thilo Hofmann 2
1 Institute of Chemistry and Biology of the Marine Environment, Carl von Ossietzky University, Oldenburg,
Germany, 2 Department of Environmental Geosciences, University of Vienna, Vienna, Austria, 3 Department
of Earth and Environmental Studies, Montclair State University, Montclair (NJ), United States of America
(corresponding author:juergen.koester@icbm.de)
Extracts of fluvial sediments from the Serbian part of
the Danube River contain wax esters with an unusual,
complex distribution. The carbon number range from
C28 to C36 and the high proportion of iso- and anteisomethyl-branched
constituents strongly point to a
bacterial origin.
Carbon number distributions of the wax esters show
two distinct patterns: First, wax esters with even
numbers are dominated by compounds with two
straight chains that dominate over combinations with
methyl branched moieties (n-/n-: 63 %, n-/br-: 23 %,
br-/br-: 14 %); second, in case of odd carbon
numbers: combinations with straight and methylbranched
isomers prevail (n-/n-: 27 %, n-/br-: 64 %,
br-/br-: 9 %). Each peak comprises several (up to 6)
isomers that arise from different combinations of
chain lengths.
Overall, the fatty acid pool involved in wax ester
formation contains mainly C16 and C15 fatty acids (30
% and 27 %, respectively) followed by C14 (10%), C17
(9 %) and C18 (5 %) compounds.
In addition to the saturated wax esters,
monounsaturated ones occur. They are dominated by
n-/n- C32 and C34 compounds with minor contributions
of n-/i- and n-/ai isomers with odd carbon numbers:
Wax esters with a phytyl chain were found in
combination with n-alkyl chains from C14 to C18 (with
dominance of n-C16). Also phytyl phytanoate is
present.
The elution order and retention times agree well with
calculated relative retention indices for methylated
compounds and values reported for long-chain wax
esters (Moldowan et al. 2002, J. Chrom. A 952).
The highest wax ester content was found in a sample
characterized by particularly abundant phytadienes
and n-C17 alkane indicating a high primary productivity
(Miciš et al. 2011, Sci. Tot. Env. 409). Literature
reports on similar wax ester distributions are sparse
(e.g. Cranwell 1984, Org. Geochem. 6) and the exact
origin of these compounds is not known yet. The
distributions of isomers suggest that the wax esters
are preferentially synthesized from indigenous
compounds typical for bacterial cell wall constituents,
rather than from external, assimilated compounds.
TIC
m/z 452 (C 30)
m/z 466 (C 31)
4
*
12
3
5
m/z 480 (C 32)
6
m/z 494 (C 33)
58 60 62 64 66 68 70 72 74 76 78
Retention time (min)
Partial total ion chromatogram of a wax ester fraction
and selected chromatograms of molecular ions of wax
esters. Asterix: n-C30 and n-C32 monounsaturated
wax esters, P: C34 and C36 wax esters with phytyl
chains, Pp: phytyl phytanoate; elution order of isomer
mixtures (1-6): i-/i-, i-/ai-, ai-/ai-, n-/i-, n-/ai-, n-/n-.
P
*
P
Pp
321

P-182
The influence of hydrogen on organic matter cycling at the lost
city hydrothermal field
Susan Lang 1 , Gretchen Früh-Green 1 , Stefano Bernasconi 1 , Marvin Lilley 2
1 ETH Zürich, Zürich, Switzerland, 2 University of Washington, Seattle, United States of America
(corresponding author:susanqlang@gmail.com)
Fluids from the Lost City Hydrothermal Field are rich
in hydrogen and methane, with high pHs (9 – 11), as
a result of serpentinization reactions at moderate
temperatures of approximately 120-200°C [1].
Carbonate chimneys in the middle of the field vent
fluids that are warmer (up to 91�C) and have higher
hydrogen concentrations (up to 14 mmol/kg) than
those on the periphery of the field (as low as 47�C,
1.3 mmol/kg) [2]. The decreases of hydrogen
concentrations have been attributed to sulfate
reduction. To gain insight into organic matter cycling
under these different chemical conditions, the organic
matter incorporated into high-hydrogen chimneys was
compared to that in low-hydrogen and extinct
chimneys that were no longer venting fluids. Chimney
samples were decarbonated and the residual was
analyzed for total organic carbon, total organic
nitrogen, stable isotopic composition ( 13 C, 15 N), and
radiocarbon content (Δ 14 C).
Residuals from actively venting chimneys had C/N
ratios similar to that of fresh microbial biomass, and
low � 15 N values that could be attributed to either
nitrogen fixation or assimilation of seawater nitrate.
No significant variations between chimneys hosting
low- or high- hydrogen fluids were found in C/N or
� 15 N values. Residuals from extinct structures had, on
average, higher C/N ratios and higher � 15 N values
than those of actively venting structures. While it may
not be the sole processes, these trends are consistent
with diagenesis.
In general, chimneys hosting high hydrogen fluids
were extremely low in total biomass. That biomass
was significantly more enriched in 13 C than typical
marine organic matter, as has been observed in other
studies [1,3]. Comparatively, chimneys hosting low
hydrogen fluids had higher biomass and were more
depleted in 13 C. Initial results also indicate differences
in the radiocarbon content of the biomass between
high- and low- hydrogen chimneys, suggesting there
is variability in the amount of mantle carbon
incorporated into microbial cellular components.
Further radiocarbon analyses are underway and will
help to constrain the processes that result in these
distinct signatures.
References:
[1] Kelley et al., (2005) Science 307:1428-1434.
[2] Proskurowski et al., (2006) Chemical Geology
229(4) 331-343.
[3] Bradley et al., (2009) Geochim. Cosmochim. Acta
73(1): 102-118
322

P-183
Characterization of dissolved organic matter in the
hydrothermally altered sediment of the Guaymas Basin, Gulf of
California
Yu-Shih Lin 1 , Boris Koch 2 , Matthias Witt 3 , Kai-Uwe Hinrichs 1
1 MARUM, University of Bremen, Bremen, Germany, 2 Alfred Wegener Institute for Polar and Marine
Research, Bremerhaven, Germany, 3 Bruker Daltonik GmbH, Bremen, Germany (corresponding
author:yushih@uni-bremen.de)
Guaymas Basin, located in the central part of the
Gulf of California, is part of a rift zone that links the
East Pacific Rise in the south with the San Andreas
Fault leading north. Covered with thick layers of
sediment, the basin is of special biogeochemical
interest because of the hydrothermal activities
inferred from high heat flow values [1]. Sediments are
typically heated to >100°C within the upper 50 cm,
providing excellent material for investigating thermal
alteration of sedimentary organic matter (OM) and the
accompanying heat-adapted microbial communities.
Petroleum, normally generated at great depths at
geological time scales, has been observed in shallow
sediments [2]. Pore waters in the upper 50 cm of
sediment are usually rich in sulfate, providing
sufficient oxidizing power for OM remineralization [3].
Although microbiological data showed the extensive
presence of thermophiles [e.g., 4], microbial activities
in deeper sediments, where the in-situ temperature
should favor these organisms, are relatively low.
When labile organic substrates were added to deeper
sediments, microbial activities could be enhanced [5].
This suggests the role of OM quality as a limiting
factor of thermophilic life in the sediments.
In this study, we seek to improve the understanding
of OM composition of Guaymas Basin sediments by
molecular characterization of dissolved organic matter
(DOM) in pore waters. Samples were retrieved by DV
Alvin at Station 4568 during RV Atlantis ATT15-56
(2009). The temperature was 102°C at 35 cmbsf.
Concentrations of dissolved organic carbon (DOC)
were >80 µM and have a maximum of 330 µM at
16 cmbsf (Table 1). DOM was concentrated by solidphase
extraction and analyzed using Fourier
transform ion cyclotron resonance mass
spectrometry.
Our preliminary results showed notable differences
between the upper three samples (Table 1). While the
(H/C)wa ratios change only slightly, the (O/C)wa ratios
decrease significantly with depth. In all the three
samples, there is only a small fraction of formulas
(

P-184
Have they lost their heads? Differential detection of archaeal
IPLs and GDGTs
Sara A. Lincoln, Edward F. DeLong, Roger E. Summons
Massachusetts Institute of Technology, Cambridge, MA, United States of America (corresponding
author:slincoln@mit.edu)
The use of intact polar lipids (IPLs) as tools for
obtaining ecological and taxonomic information has
burgeoned in the past decade. Notably, they have
been used as markers for living biomass in the
environment. This application is based on the
assumption that hydrolysis of labile polar head
groups, such as the cleavage of hexose from an
archaeal tetraether IPL yielding a glycerol dialkyl
glycerol tetraether (GDGT) core lipid, occurs shortly
after cell death. Consequently, the presence of intact
archaeal IPLs in environmental samples can be
viewed as evidence of an active archaeal community.
As part of an effort to understand the ecology of
modern marine archaea and the distribution of their
fossil lipids in the geologic record we have analyzed
archaeal IPLs and GDGTs in suspended marine
particulate matter from five sites. We report the
striking, apparent absence of archaeal IPLs in our
sample set, even in those samples in which abundant
GDGTs have been detected. This absence is
surprising for several reasons: living archaea are
nearly ubiquitous in the world‘s oceans; large volumes
(600-1500L) of seawater were filtered; bacterial IPLs
were detected in the same samples, indicating proper
sample handling and extraction; and synoptic
microbiological studies have shown high archaeal cell
counts and activity at a number of depths/sites.
Following established protocols, IPLs were analyzed
by high performance liquid chromatography mass
spectrometry (HPLC-MS) using electrospray
ionization (ESI), while GDGTs were analyzed using
atmospheric pressure chemical ionization (APCI). We
conclude that the limits of detection (LOD) for IPLs
and GDGTs analyzed using these two analytical
techniques differ significantly.
To determine the extent to which established IPL
analysis may underestimate active archaeal
communities several HPLC-MS experiments were
conducted. A laboratory stock seawater extract, a
commercially available intact GDGT mixture and acid
hydrolyzed aliquots of both were analyzed at a range
of concentrations in order to determine limits of
detection and to compare response factors. We also
compare LODs obtained using quadrupole-time-offlight,
single quadrupole and ion trap instruments.
Our results suggest that caution is warranted when
drawing conclusions about active archaeal
communities from IPL analysis, particularly in lowbiomass
environments such as the oligotrophic open
ocean.
324

P-185
Biogeochemistry of sediments at ultra-deep burial depth
recovered during IODP Expedition 317, Canterbury Basin, New
Zealand
Julius Lipp 1 , Simon C. George 2 , George E. Claypool 3 , Toshihiro Yoshimura 4 , Kai-Uwe
Hinrichs 1 , IODP Expedition 317 Shipboard Scientific Party 5
1 MARUM Center for Marine Environmental Sciences & Department of Geosciences, University of Bremen,
28359 Bremen, Germany, Germany, 2 Department of Earth and Planetary Sciences, Macquarie University,
Sydney, NSW 2109, Australia, 3 8910 W 2nd Ave, Lakewood, Lakewood, CO 80226, United States of
America, 4 Atmosphere and Ocean Research Institute & Graduate School of Frontier Science, The University
of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8563, Japan, 5 Integrated Ocean Drilling Program (IODP),
Texas A&M University, 1000 Discovery Drive, College Station, TX 77845-95, United States of America
(corresponding author:jlipp@uni-bremen.de)
Integrated Ocean Drilling Program (IODP)
Expedition 317 aimed to derive an understanding of
the relative importance of global sea level changes
versus local tectonic and sedimentary processes in
controlling continental margin sedimentary cycles [1].
Four shelf-upper slope sites were cored in the
Canterbury Basin on the eastern margin of the South
Island of New Zealand in water depths of 85-344 m.
Eocene to recent sedimentary sequences, influenced
by a high rate of sediment supply from the uplifting
Southern Alps, were cored in a transect of three sites
on the continental shelf (landward to basinward, Sites
U1351, U1353, U1354) and one site on the
continental slope (U1352).
Cores at all four sites were routinely sampled for
traces of residual dissolved gas, both as a
hydrocarbon safety procedure and as a sensitive
technique to determine the status of the microbial and
thermal degradation of organic matter. In combination
with pore water samples, this approach led to detailed
profiles covering the biogeochemical zones of sulfate
reduction, anaerobic oxidation of methane (AOM),
and methanogenesis at all sites.
Site U1352 is the deepest IODP site which was
systematically sampled for molecular biological and
chemical analyses and covers a complete section
from modern slope terrigenous sediment to Eocene
limestone reaching into the early oil-generating
window. Preliminary analysis of hydrocarbon gases
shows signs of microbial activity and the influence of
depth and temperature (Fig. 1). The methane to
ethane ratio (C1/C2) decreases three orders of
magnitude to the bottom of the hole at 1920 m as
δ 13 C values gradually increase, which is in
accordance with an increase of thermogenic methane
with depth. At an apparent unconformity near 1400 m,
C1/C2 ratios drop to minimum values of 7, while δ 13 C
values of methane increase from ~-70‰ to ~-50‰,
suggesting an abrupt, substantial increase in the
proportion of thermogenic gas below this depth.
The combination of concentration and isotopic
data of carbon substrates and intermediates with
analysis of lipid biomarkers has proven to be a
powerful tool to assess microbial activity and carbon
flow in sedimentary ecosystems [2,3]. We will discuss
the depth profiles of headspace gas, dissolved
inorganic carbon, and volatile fatty acids in concert
with selected samples analysed for intact polar lipids
as proxy for live biomass and provide insight into the
biogeochemistry of terrestrially influenced sediments,
including samples from burial depths around 1900 m.
Figure 1: Plots of headspace methane and ethane
concentrations (A), C1/C2 ratios (B) and δ 13 C values (C) vs.
depth of sediment samples from IODP Site U1352.
References
[1] Fulthorpe CS, Hoyanagi K, Blum P, and the Expedition
317 Scientists, 2011. Proc. IODP, 317: Tokyo
(Integrated Ocean Drilling Program Management
<strong>International</strong>, Inc.). doi:10.2204/iodp.proc.317.2011.
[2] Biddle JF, Lipp JS, et al., 2006. Proc. Natl. Acad. Sci.
USA. doi:10.1073/pnas.0600035103.
[3] Heuer VB, et al., 2009. Geochim. Cosmochim. Acta,
doi:10.1016/j.gca.2009.03.001.
325

P-187
Paleohydrological changes on the n-alkane biomarker
compositions of a Holocene peat sequence in the Eastern
European Russian Arctic
Rina Andersson 1 , Philip Meyers 2 , Peter Kuhry 1 , Magnus Mörth 1 , Yngve Zebühr 1 , Patrick
Crill 1
1 Stockholm University, Stockholm, Sweden, 2 University of Michigan, Michigan, United States of America
(corresponding author:rina.garcia@geo.su.se)
Combined analysis of n-alkane biomarkers and plant
macrofossil residues of a peat plateau deposit in the
Northeast European Russian Arctic were carried out
to assess the effects of past hydrology on the
molecular compositions. The peat profile accumulated
over approximately 9 kyr and records a succession of
vegetation changes where the onset of permafrost in
the late Holocene marked a transition from a wet fen
to a relatively dry peat bog. The results show that the
contribution of the n-C31 homologue from the rootlet
layers of Betula -rich in fine and dark roots- to the nalkane
compositions is important and has to be taken
into consideration in paleoreconstruction studies
based in n-alkane analyses. Other results show that
the proxies commonly used in the reconstruction of
past water table Paq and n-C23/n-C29 can lead to
wrong interpretations in the assessment of past
moisture at depths where Betula and Sphagnum
fuscum are present in the profile. Both plants that can
thrive in drier conditions are abundant in the n-C23
and n-C25 homologues giving therefore high values for
the Paq and n-C23/n-C29 proxies with a consequent
false interpretation of the water table. In this profile,
the C23/(C27+C31) n-alkane ratio provides a better
description of past moisture and seems to correct for
the presence of Betula and S. fuscum. Also the ACL
proxy records changes in moisture giving the highest
values for this proxy at depths where vascular plants
dominated under drier conditions. In general the
results indicate that in this complex peat system,
there is a good agreement between the
hydrologically-sensitive paleoenvironmental proxies:
the n-alkane biomarkers and the plant macrofossil
assemblage.
326

P-188
Impact of degradation on the lipid biomarkers of a Holocene
peat sequence in the Eastern European Russian Arctic
Rina Andersson 1 , Philip Meyers 2
1 Stockholm University, Stockholm, Sweden, 2 University of Michigan, Michigan, United States of America
(corresponding author:rina.garcia@geo.su.se)
To help characterize the organic matter content of a
core taken from a peat plateau deposit in the
Northeast European Russian Arctic, the
concentrations and carbon preference indices (CPI) of
the n-alkanols, n-alkanoic acids and n-alkanes were
measured. This peat profile is a complex system that
experienced a transition from a wet fen to a relatively
dry bog during the onset of permafrost in the late
Holocene (~2500 yr BP). In the profile, the n-alkanoic
acids are the most abundant lipids and their
concentration is higher in the fen peat area, especially
immediately before the transition to the bog peat
before permafrost aggradation. The CPI values of the
n-alkanes are higher in the non-humified peat bog
area and diminish with increasing depth, which is
consistent with progressively greater degradation.
However, the CPI values for the n-alkanols and nalkanoic
acids display a complex trend that increases
with depth in the humified peat area. This apparent
contradiction in degradation as indicated by the CPI
patterns of the n-alkane and the other lipid fractions
may indicate that n-alkanoic acids and n-alkanols are
secondary products of the microbial impact on other
plant leaf waxes (Zhou et al., 2010). Decomposition of
wax esters that release free fatty acids and free
alcohols can also occur during sedimentation
(Simoneit and Mazurek, 2007) or release of fatty
acids and alkanols can be the result of the hydrolysis
of the wax esters in the acidic conditions of the mire
(Ficken et al., 1998). An increase with depth in the
relative amounts of stanols – considered to be the
products of microbial alteration of their corresponding
stenols - is revealed by an increase in the
stanol/sterol ratio and suggests the progressive
alteration of the original sterol inputs in the zone of
the peat deposit that was previously a wet fen.
References
Ficken, K., Barber, K., and Eglington, G., 1998, Lipid
biomarker, δ 13 C and plant macrofossil
stratigraphy of a Scottish montane peat bog
over the last two millennia.: Organic
Geochemistry, v. 28, p. 217-237
Simoneit, B.R.T., and Mazurek, M.A., 2007, Organic
Matter of the Troposphere--II.: Natural
Background of biogenic lipid matter in
aerosols over the rural western United
States: Atmospheric Environment, v. 41, p.
4-24.
Zhou, W., Zheng, Y., Meyers, P.A., Jull, A.J.T., and
Xie, S., 2010, Postglacial climate-change
record in biomarker lipid compositions of the
Hani peat sequence, Northeastern China:
Earth and Planetary Science Letters, v. 294,
p. 37-46.
327

P-189
Paleoenvironmental variations recorded by marine algal and
terrestrial plant biomarkers in black shales deposited during the
mid-Cretaceous Oceanic Anoxic Event 1b in the Vocontian Basin,
SE France
Takuto Ando 1 , Ken Sawada 1 , Kazuki Okano 1 , Hiroshi Nishi 2 , Reishi Takashima 2
1 Faculty of Science, Hokkaido University, Sapporo, Japan, 2 Tohoku University Museum, Sendai, Japan
(corresponding author:tact@mail.sci.hokudai.ac.jp)
Black shales were occasionally discovered in the
mid-Cretaceous formations, and depositions of these
sediments are closely associated with the expansion
of oxygen-poor water in the ocean, called the oceanic
anoxic events (OAEs). In this study, the biomarker
analyses of the black shales corresponding to the
OAE1b (the Jacob, Kilian, Paquier, and Leeenhardt
levels) from the Vocontian Basin of SE France are
curried out in order to reconstruct the changes of
environmental systems and marine ecosystems, and
to elucidate the mechanism for expansion of anoxic
waters during this OAE.
Black shales and adjacent sediments were
collected from the outcrops and cores in SE France.
The Kilian and Paquier are composed of laminated
black shales, several faintly laminated layers, and
adjacent marls. The sediment samples were crushed
to fine powder. Lipids were ultrasonically extracted
from the powder samples as reported previously [1].
These fractions were analysed by gas
chromatography / mass spectrometer (GC/MS).
In the OAE1b samples, the terrestrial higher plant
biomarkers such as the retene and the dibenzofuran
are abundantly identified. The concentrations of these
biomarkers are relatively low in the Jacob level, but
high in the middle part of the Paquier level. Moreover,
the concentrations of marine algal biomarkers such as
steranes and dinosteranes are high in the Kilian and
Paquier levels, while these are low in the Jacob and
Leenhardt levels. These trends are similar to those of
terrestrial biomarker concentrations, which indicate
that the nutrient was transported from land to ocean.
During the Jacob and Leenhardt levels, terrestrial
input presumably decreased in the ocean. Therefore,
the structure of clear lamination and prominent
variation of carbon isotope ratios are not recognized
in the Jacob and Leenhardt levels.
In the Kilian and Paquier levels, the archaeal
biomarkers such as 2,6,15,19- tetramethylicosane
(TMI) and 2,6,10,15,19-pentamethylicosane (PMI) are
detected [1], but are not detected in the Jacob and
Leenhardt levels. Carbon isotope ratios of TMI and
PMI range -35 to -20‰, suggesting that these
biomarkers are originated from methanogenic
archaea. Thus, these expansions of methanogenic
archaea during the Kilian and Paquier levels were
possibly related to the intensification of anoxic
condition. As mentioned above, the deposition of
black shales are strongly related to terrestrial input. In
addition, variations of dinoflagellate and
cyanobacteria productions were recorded by aromatic
dinosteroids and hopanoids, respectively. The
productions of these marine primary producers
tended to increase with increasing terrestrial input in
the Paquier level.
The same mechanisms are observed in modern
tropical ocean areas such as the Bismarck Sea
(Papuwa New Guinea), where is characterized by
strong stratification and supply of a large amount of
terrigenous materials by riverine flow system of the
Sepik River, and productivity of marine phytoplankton
is high in the stratified surface water, resulting in
deposition of sediment rich in organic matter [2]. In
this study, it is suggested that the Bismarck Sea is
typical ocean model for the paleo-Tethys Sea during
OAE1b, called ‗Bismarck Sea-type OAE‘.
References
[1] Okano, K., Sawada, K., Takashima, R., Nishi, H.,
Okada, H. (2008) Org. Geochem. 39, 1088-1091.
[2] Burns, K.A., Brunskill, G., Brinkman, D., Zagorskis,
I. (2008) Continent. Shelf. Res. 28, 283-301.
328

P-190
Large scale cooling in Tertiary Central Europe as inferred by the
MBT/CBT paleothermometer
Thorsten Bauersachs 1 , Stefan Schouten 2 , Lorenz Schwark 1
1 Christian-Albrechts-University, Kiel, Germany, 2 Royal Netherlands Institute for Sea Research, Texel,
Netherlands (corresponding author:thb@gpi.uni-kiel.de)
Earth‘s climate experienced dramatic changes
throughout the last 65 Ma. Starting at the
Paleocene/Eocene thermal maximum, the global
climate underwent a gradual cooling that eventually
resulted in the glaciations in the Neogene [1]. Most
reconstructions of climate variability are derived from
the marine realm using global deep sea oxygen
isotope curves or molecular paleotemperature proxies
[1]. In contrast, only little information on the changes
of the continental climate is available, which is mainly
due to a lack of continuous high resolution records
and suitable quantitative temperature proxies.
The methylation index of branched tetraethers
(MBT) is a novel temperature proxy based on
temperature-driven changes in the membrane-lipid
composition of presumably anaerobic soil bacteria [2].
These changes correlate well with mean annual air
temperature (MAAT) and the MBT proxy has thus
been used to reconstruct paleotemperature records in
terrestrial as well as coastal marine sediments [3].
In this study, we employed the MBT Index on a
number of lacustrine deposits ranging in age from the
Early Eocene to the Late Oligocene in order to
reconstruct climate evolution of the Central European
continent. The Messel oil shale (Germany)
accumulated in a small crater lake during the Eocene
climate optimum and thus allows reconstructing
temperature development in a so-called green house
world. Methylation of the branched glycerol dialkyl
glycerol tetraethers (GDGTs) suggests that the MAAT
at time of oil shale formation ranged from 20-32 °C
over an estimated time period of ca. 1 Ma. This is in
good agreement with temperature estimates based on
paleontological observations suggesting a
paratropical climate in Eocene Central Europe with an
average air temperature of ca. 25-30 °C [4].
In contrast, to the green house period of the Early
Eocene, the climate of the Oligocene was significantly
cooler reflected by low MAAT of 8-15 °C in the
lacustrine deposit of Lake Enspel (Westerwald,
Germany). These MBT-derived air temperatures are
similar to those previously reconstructed using floral
elements of the Enspel deposit [5].
Our results indicate that the paleotemperature
trends of the Central European continent, based on
the distribution of branched GDGTs in Tertiary
lacustrine deposits, resemble those previously
obtained from marine records and that the MBT proxy
might be a valuable tool for reconstructing terrestrial
paleoclimate records.
Fig. 1. Mean annual air temperature (MAAT) reconstructed
from the distribution of branched GDGTs in (a) the Eocene
Messel oil shale and (b) the Oligocene Lake Enspel deposit.
References
[1] Zachos et al. (2001) Science 292, 686-693
[2] Weijers et al. (2007) Geoch Cosmoch Ac 71, 701-703
[3] Donders et al. (2007) EPSL 281, 215-225
[4] Wilde (1989) Cour. Forsch. Senk 115, 1-213
[5] Herrmann (2007) PhD Thesis, Tübingen University
329

P-191
Highly branched isoprenoid alkenes as proxies for variable sea
ice conditions in the Southern Ocean
Steven Rowland 1 , Guillaume Masse 2 , Xavier Crosta 3 , Simon Belt 1 , Ian Snape 4 , David
Thomas 5
1 Biogeochemistry Research Centre, University of Plymouth, Drake Circus, Plymouth, Devon, PL4 8AA,
Plymouth, United Kingdom, 2 LOCEAN, UMR7159 CNRS/UPMC/IRD/MNHN, Université Pierre et Marie
Curie, 4 Place Jussieu, 75252 Paris, Paris, France, 3 Environnement et Paléoenvironnement Océaniques,
UMR5805, Université Bordeaux 1, Avenue des Facultés, 33405 Talence, Bordeaux, France, 4 Australian
Antarctic Division, Channel Highway, Kingston Tasmania 7050, Hobart, Australia, 5 of Ocean Sciences,
Bangor University, Menai Bridge, Anglesey, LL59 5AB, Bangor, United Kingdom
We show that the concentrations of a highly branched
isoprenoid (HBI) diene determined in over 200
sediment samples from the Arctic co-vary with those
of an HBI monoene (IP25) shown previously to be a
sedimentary sea-ice proxy for the Arctic. The same
diene, but not monoene IP25, is now reported herein in
nine sea ice samples collected from various locations
around Antarctica. The diene has been reported
previously in Antarctic sea-ice diatoms and the 13 C
isotopic compositions of the diene determined in two
Antarctic sea-ice samples herein were also consistent
with an origin from sea-ice diatoms (δ 13 C -5.7 to -8.5
‰). In contrast, HBIs found in two Antarctic
phytoplankton samples examined herein did not
include the diene but comprised a number of tri- to
pentaenes. In sediment samples collected near Adélie
Land, East Antarctica, both the diene and the tri-to
pentaenes often co-occurred.
13 C isotopic
compositions of the tri- to pentaenes in three
sediment samples ranged from -35 to -42 ‰ whereas
that of the diene in a sediment sample was -18 ‰.
We suggest that the presence of this isotopically 13 C
enriched HBI diene in Antarctic sediments might be a
useful proxy indicator for contributions of organic
matter derived from sea ice diatoms. A ratio of the
concentrations of, for instance, diene/trienes might
reflect the relative contributions of sea-ice to
phytoplanktonic inputs of organic matter to Antarctic
sediments and, although it is acknowledged that
diagenetic effects on these di-and polyenes might be
more important than for IP25, recent studies of
Antarctic sediment cores support this suggestion.
330

P-192
Climate variability in the Lake Victoria region (East Africa) since
the Late Pleistocene as shown by molecular biomarkers
Melissa Berke 1 , Josef Werne 2 , Thomas Johnson 1 , Kliti Grice 3 , Stefan Schouten 4 , Jaap
Sinninghe Damsté 4
1 Large Lakes Observatory & Department of Geological Sciences, University of Minnesota Duluth, Duluth,
United States of America, 2 Large Lakes Observatory & Department of Chemistry and Biochemistry,
University of Minnesota Duluth, Duluth, United States of America, 3 Department of Chemistry, Curtin
University, Perth, Australia, 4 Royal NIOZ, Department of Marine Organic Biogeochemistry, Den Burg,
Netherlands (corresponding author:berk0135@umn.edu)
Recent organic geochemical advances have
facilitated the comparison between continental
temperature change, hydrologic variability, and
terrestrial vegetation response. TEX86, a proxy based
on the lipids of aquatic Crenarchaeota that show a
positive correlation with growth temperature, was
used to reconstruct surface water temperatures from
Lake Victoria, East Africa during the latest
Pleistocene-Holocene. Hydrologic conditions were
then interpreted using compound specific δD of fatty
acids from sediments and compared to hydrologic
implications from paleoecological data, specifically
pollen and diatom assemblages found in the lake
(Kendall, 1969; Stager et al., 2003). Compound
specific δ 13 C data from terrestrial leaf wax biomarkers
(n-alkanes) was then evaluated in order to determine
how the patterns of rainfall and aridity in this region
have affected the terrestrial vegetation in the
watershed. Initial comparisons of climatic changes
seen in temperature, vegetation, and hydrologic
records appear to show some periods of consistency
between warm/wet intervals and cool/dry intervals,
which is expected for this region, but far less often
shown. This is one of the first studies from a tropical
East African lake to compare all three of these
biomarkers (TEX86, δD, and δ 13 C) in order to
reconstruct a complete regional-scale picture of
climate variability since the Late Pleistocene.
Lake Victoria temperatures show a steady
warming beginning 16 cal ka, with a pause around the
Younger Dryas, dominated by arid conditions and
strong savannah grassland development during this
interval. There is continued warming to a sustained
thermal maximum for this portion of the record at
~10.5-8.5 ka, which generally coincides with the
Northern Hemisphere summer insolation maximum.
This thermal maximum occurs during the most humid
interval of this record (~9.5-8.3 ka), shown by an
increase of humid forest pollen and high diatom
abundance (due to increased water column mixing
and nutrient runoff). Temperatures abruptly cool
~1.5ºC in

P-193
A new global calibration for GDGTs preserved in stalagmites
Alison Blyth 1 , Stefan Schouten 2
1 The Open University, Milton Keynes, United Kingdom, 2 NIOZ, Den Burg, Netherlands (corresponding
author:a.blyth@open.ac.uk)
Recovering reliable temperature records is central to
palaeoclimatic research, informing our understanding
of the past and our models of the future. Organic
geochemistry has provided a number of
palaeotemperature proxies including TEX86, UK‘37,
and the MBT/CBT index. However, despite good
calibrations of the latter in soils, to date these have
primarily been of use in the aquatic realm, due to the
better preservation conditions provided by the
sedimentary environment.
Here we expand the range of palaeoenvironmental
records to which organic temperature proxies can be
applied, and present global calibration data for
bacterial glycerol dialkyl glycerol tetraethers
preserved in stalagmites. Stalagmites are chemically
precipitated cave deposits which grow incrementally
where drip-waters enter a cave. As they are formed
from waters transported from the overlying soil, they
contain a wide range of environmental proxies
including stable isotope records linked to rainfall and
climate, and organic matter derived from the overlying
vegetation. Due to the nature of their calcite matrix,
stalagmites are also easy to date accurately and
precisely via U-Th dating. The development of a well
calibrated palaeothermometer in this context is
therefore of considerable importance, as, by
combining the temperature record with the other
available proxies, it will be possible to create an
integrated record of changes in temperature, rainfall,
and the associated environmental response.
Glycerol dialkyl glycerol tetraethers (GDGTs) are
microbial membrane lipids, which vary in structure
with temperature and pH [1]. Bacterially derived
GDGTs have been used to measure terrestrial
organic matter input to aquatic deposits via the BIT
index [2], and developed into a temperature related
index (MBT/CBT) in soils and near-shore marine
sediment, based upon the degree of branching and
cyclicisation of the carbon skeleton [3].
Our previous analysis of speleothem samples has
shown that GDGTs are recoverable from stalagmites,
but that the relationship with temperature is not
simple. Therefore a stalagmite specific calibration is
required. Here we present the first attempt at a global
stalagmite based calibration for bacterial GDGTs.
Thirty-eight modern or known age calcite samples
from twenty one different cave sites around the world
were cleaned and decalcified with HCl, and lipids
extracted into dichloromethane via liquid-liquid
extraction. Each extract was then prepared and
analysed via HPLC-MS following Weijers et al. [3].
The results show low but usable levels of GDGTs in
all but one sample. Peak size measurements were
made for all recognised compounds associated with
BIT and MBT/CBT.
Using MBT/CBT, significant correlation is seen
between calculated MAT and known air temperature;
following the methodology used by Weijers et al. [3]
this has a 2-D correlation of r2 = 0.68, indicating a
genuine temperature signal is present. However, the
results have a large degree of scatter, predominantly
representing an under-estimation of temperature. We
hypothesise that this is due to the potential mixture of
sources for the signal (cave bacteria, aquifer bacteria,
soil bacteria, and compounds from the degraded
organic matter pool). One of the most striking
aspects of the results is that the BIT index for the
samples is generally very low (23 samples have a BIT

P-194
Palaeotemperatures and palaeoenvironmental changes during
OAE 1a at Shatsky Rise
Simon Brassell
Indiana University, Bloomington, United States of America (corresponding author:simon@indiana.edu)
Validation of the temperature dependence in the
natural distributions of select molecular components,
such as alkenones [1] and glycerol dialkyl glycerol
tetraethers (GDGTs; [2]), has proven the potential and
utility of biomarkers as palaeotemperature proxies
and demonstrated that such measures can contribute
to the description of ancient climate change. In
addition, stratigraphic variations in the abundances or
compositions of other geochemical properties, both
molecular and elemental, can provide evidence of
biological responses to temperature fluctuations and
trends and their relationship to palaeoenvironmental
conditions, notably the levels of oxygenation (oxic,
dysoxic, anoxic, euxinic) of the depositional setting.
The potential influence on biomarker abundances
of changes in ocean temperatures accompanying
stratification and anoxicity is illustrated by the
observed higher concentrations of isorenieratane and
chlorobactane in sediments corresponding to the
Cenomanian-Turonian oceanic anoxic event (OAE2)
during warmer episodes [3]. It is therefore pertinent to
examine whether similar phenomena are features of
other OAE [4]. The presence of two cooler intervals
based on TEX86 measurements [5] within the organicrich
sediment sequence from Shatsky Rise (ODP Site
1207) that corresponds to OAE1a (early Aptian; [6])
affords the opportunity for such assessment.
The major variations in biomarkers and other
geochemical proxies observed through this OAE1a
interval include: (i) decreasing concentrations of 2methylhopanes
derived from cyanobacteria [7,8] with
increasing temperature (Fig. 1), (ii) a correspondence
of the lycopane index [9] with Mo concentrations [10],
which both reflect anoxic conditions that appear more
prevalent during warmer intervals, and (iii) fluctuations
in V concentrations that reflect temperature trends,
and correspond closely with organic C contents,
except where Corg >30%. These results suggest that
changes in ocean temperatures during OAE exert an
influence on surface ocean conditions that govern
seasonal productivity and stratification, but remain
independent from the primary controls on anoxia.
References
[1] Brassell et al., Nature, 320, 129-133 (1986)
OAE1a
ODP Site 1207
Shatsky Rise
Fig. 1: Plot of values for methylhopane index [7]
versus TEX86 temperatures
[2] Schouten et al., Earth Planetary Sci. Letts., 204,
265-274 (2002)
[3] van Bentum et al., Palaeogeog., Palaeoclimatol.,
Palaeoecol., 280, 489-498 (2009)
[4] Jenkyns, Geochem., Geophys., Geosystems, 11
10.1029/2009GC002788 (2010)
[5] Dumitrescu et al., Geology, 34, 833-836 (2006)
[6] Dumitrescu & Brassell, Palaeogeog., Palaeoclimatol.,
Palaeoecol., 235, 168-191 (2006)
[7] Summons et al., Nature, 400, 554-557 (1999)
[8] Dumitrescu & Brassell, Org. Geochem., 36,
1002-1022 (2005)
[9] Sinninghe Damsté et al., Earth Planetary Sci.
Letts., 209, 215-226 (2003)
[10] Lyons et al., Ann. Rev. Earth Planetary Sci., 37,
507-534 (2009)
333

P-195
Molecular fossils and the late rise of eukaryotes and oxygenic
photosynthesis
Jochen J. Brocks
Research School of Earth Sciences, The Australian National University, Canberra, Australia (corresponding
author:Jochen.Brocks@anu.edu.au)
In 1999, a study reported the discovery of molecular
fossils in 2.7 to 2.5 Ga old, mildly-metamorphosed
shales from the Pilbara Craton in Western Australia 1 .
Based on apparently typical Precambrian composition
and high thermal maturity, the biomarkers were
characterized as ‗probably syngenetic‘ with the
Archean host rocks 2 . The findings led to far reaching
conclusions about the Archean biosphere. 2�methylhopanes
were interpreted as evidence for the
existence of cyanobacteria more than 300 million
years before the atmosphere became widely
oxygenated 1,3 , and the presence of steranes
suggested that ancestral eukaryotes existed 2.7 Ga
ago, 800 million years before the first eukaryotic body
fossils appear in the geological record 1 . However,
here we present evidence that the biomarkers entered
the Archean rocks at a much later point in time.
In a recent study, Rasmussen et al. 4 detected
microscopic spherules of thermally solidified bitumen
in the Archean shales and compared their carbon
isotopic composition with liquid bitumen and kerogen
in the same rocks. The indigenous pyrobitumens had
approximately the same carbon isotopic composition
as co-occurring kerogens, but were depleted in 13 C by
10 to 20‰ relative to extractable alkanes. The
isotopic discrepancy between solidified and liquid
bitumens indicates that the extractable phase entered
the rock after peak-metamorphism 2.2 Ga ago.
If the hydrocarbons were indeed later additions, then
they should have left a distinct spatial distribution in
the Archean rocks. In the simplest case, recent
contaminants should be entirely surficial, while
syngenetic hydrocarbons should be homogeneously
distributed throughout the rock. However, liquid
contaminants might also diffuse into fissures and pore
space creating distinct concentration gradients 5 .
Similarly, an indigenous oil is not necessarily
homogeneously distributed in its host rock.
Hydrocarbons might be driven to rock surfaces by
pressure release when the core is recovered from
great depths after drilling, leading to an accumulation
on rock surfaces. To study these phenomena in the
Archean rocks, we determined the spatial distribution
of biomarkers in drill core material. Rock samples
were cut into millimeter thick slices, and the molecular
content of each slice was quantified. In the drill core,
saturated and aromatic hydrocarbons of low
molecular weight had gradually increasing
concentrations from the surfaces to the center of the
rock while the abundance of higher molecular weight
hydrocarbons, including steranes and hopanes,
steeply decreased with distance from the outer
surfaces.
We propose two mechanisms that may have caused
the inhomogeneous distribution: diffusion of
petroleum-based contaminants into the rock
(‗contamination model‘) and leaching of indigenous
hydrocarbons out of the host shales driven by
pressure release after drilling (‗condensate-escape
model‘). To test these models, we compared the
hydrocarbon distribution in the Archean shales with
artificially contaminated rocks, and with younger
mudstones where leaching of ‗live-oil‘ had been
observed after drilling. Although the condensateescape
model is consistent with some of the observed
patterns in the Archean shales, the observed relative
migration depth of different hydrocarbon classes is
only consistent with chromatographic effects caused
by diffusion of contaminants from the surfaces of the
rock towards the centre. The results confirm that the
biomarkers are not of Archean age and entered the
samples during and after drilling.
[1] Brocks, J. J., Logan, G. A., Buick, R. &
Summons, R. E. (1999) Science 285, 1033-1036.
[2] Brocks, J. J., Buick, R., Logan, G. A. &
Summons, R. E. (2003) Geochim. Cosmochim. Acta
67, 4289-4319.
[3] Summons, R. E., Jahnke, L. L., Hope, J. M.
& Logan, G. A. (1999) Nature 400, 554-557 (1999).
[4] Rasmussen, B., Fletcher, I. R., Brocks, J. J.
& Kilburn, M. R. (2008) Nature 455, 1101 - 1104.
[5] Brocks, J. J., Grosjean, E. & Logan, G. A.
(2008) Geochim. Cosmochim. Acta 72, 871-888.
334

P-196
The holocene ecosystem of Lake Van, Eastern Turkey
Ozlem Bulkam 1 , Heinz Wilkes 2 , Naci Orbay 3 , M.Namık Cagatay 4 , M.Namık Yalcin 1
1 Istanbul University, Engineering Faculty, Geological Engineering Department, Avcılar/Istanbul, Turkey,
2 Helmholtz Centre, GeoForschungsZentrum-Potsdam, Section 4.3 Organic Geochemistry,
Telegrafenberg/Potsdam, Germany, 3 Istanbul University, Engineering Faculty, Geophysical Engineering
Department, Avcılar/Istanbul, Turkey, 4 Istanbul Technical University, Engineering Faculty, Geological
Engineering Department, Maslak/Istanbul, Turkey (corresponding author:bulkan@istanbul.edu.tr)
The ecosystem of Lake Van (LV) deserves special
attention as the largest soda lake of the Earth (area:
3522 km 2 , maximum water depth: 451 m; water
volume: 576 km 3 ) which exhibits an extremely high
alkalinity level (152 meq L -1 ) (Kempe, 1991; Thiel,
1997). The lake deposits are characterized by a very
distinct varving due to seasonal sedimentation
variability and the lack of bioturbation. Therefore, its
sedimentary record keeps highly sensitive paleoenvironmental
and ecological information for Eastern
Anatolia.
In order to contribute to the general knowledge on this
unique ecosystem, a multidisciplinary approach,
combining the bulk/molecular organic and inorganic
geochemical methods, was applied to LV sediments.
Two cores were studied: P01 from the eastern (4,5m;
corresponding to 10500 a BP) and P07 from western
part (5m; 9200 a BP) of the lake. A total of 65
samples were selected for basic organic geochemical
analysis (LECO and Rock-Eval) and the detailed
geochemical methods were applied to 19 of the
samples. Elemental composition of the sediments
were determined using XRF-scanner at 0.5 cm
resolution along each core.
Main organic geochemical characteristics of the EP
(eastern part) and WP (western part) of the lake are
somewhat different (Figure 1). EP sediments contain
relatively high amounts of TOC (0.69% - 5.03%) and
algal to terrestrial organic matter (OM) (HI: 62-818
mgHC/gTOC; C/N: 7-11). WP sediments contain
relatively lower TOC (0,9 to 2.8%) dominated by
terrestrial to mixed type of OM (HI: 78-330
mgHC/gTOC; C/N: 8-10). Additionally, the isotopic
compositions of the EP sediments fluctuate in a wider
range (δ 13 C: -22,9‰ to -25,5‰; δ 15 N: 3‰-12‰) than
of the WP (δ 13 C: -22,8 to -23,9‰; δ 15 N: 2‰-5‰). This
is probably a result of differences in intensity of
terrestrial OM flux and/or primary production between
the WP and EP of LV.
Lake sediments were also investigated in terms of
their n-alkane distributions. Recent EP sediments (0-
118 cm) are characterized by a n-alkane distribution,
which has its maximum at n-C17, typical for aquatic
producers (Meyers, 1997). Below 118 cm level the
main source are probably terrestrial plants, indicated
by the dominance of the C29 and C31 n-alkanes
(Meyers, 1997), except at 236 cm. Different from the
EP, terrestrial plant input was probably higher during
the entire depositional period for the WP sediments,
indicated by the general dominance of the C29 and/or
C31 n-alkanes. These conclusions are also supported
by HI values.
Figure 1. Variations of amount, type and isotopic
composition of the OM in the LV sediments.
The major and trace element profiles from XRF core
scanner analysis was partly used as proxies for water
chemistry (salinity, redox) and nutrient supply
mechanisms. The results suggest that periodical
changes in the LV ecosystem occurred over the last
10 500 a.
REFERENCES
Kempe S., Kazmirczak J., Landmann G., Konuk T.,
Reimer A., and Lipp A. 1991, Largest known
microbialites discovered in Lake Van, Turkey. Nature
349,605-608.
Meyers, P.A., 1997, Organic geochemical proxies of
paleoceanographic, paleolimnologic and paleoclimatic
processes. Organic Geochemistry 27, 213-250.
Thiel, V., Jenisch, A., Landman, G., Reimer, A.,
Michaelis, W., 1997, Unusual distributions of longchain
alkenones and tetrahymanol from the highly
alkaline Lake Van, Turkey. Geochimica et
Cosmochimica Acta, 61, 10, 2053-2064.
335

P-197
Sediment trap and core top study of organic (UK’37 and TEX86)
and inorganic � 18 O, Mg/Ca) sea surface temperature proxies in
the Mozambique Channel
Isla Castañeda, Ulrike Fallet, Geert-Jan Brummer, Jaap Sinninghe Damsté, Stefan
Schouten
NIOZ Royal Netherlands Institute for Sea Research, Den Burg, Netherlands (corresponding
author:isla.castaneda@nioz.nl)
Proxies for reconstructing past sea surface
temperatures (SST) are critical for paleoceanographic
and paleoclimatic studies; however, several factors
can influence their reliability. Here, we examine
organic (U K‘ 37 and TEX86) and inorganic (� 18 O and
Mg/Ca) SST proxies from a deep moored sediment
trap and surface sediments in the Mozambique
Channel (SW Indian Ocean). To evaluate
environmental factors influencing each proxy, we
compare this data to satellite-derived SST and to insitu
measurements of a number of physical properties
including salinity, current velocity and direction,
oxygen and nutrient concentrations.
A time series of sinking particles was collected at 21
day intervals from Nov. 2003 to April 2009 from a
deep sediment trap (2250 m depth; 250 m above the
seafloor) in the mid-Mozambique Channel. While the
Mg/Ca of surface dwelling foraminifer G. ruber
captured the seasonal variability in SST, the organic
proxies did not (Fig. 1). However, flux weighted mean
SSTs of all proxies (28.1 °C for Mg/Ca, 28.1 °C for
U K‘ 37 and 27.9 °C for TEX86) are in close agreement
with mean annual SST (27.6 °C). Times-series
analysis of all geochemical parameters examined
revealed a dominant peak at four to six cycles per
year, which is attributed to the passage of anticyclonic
meso-scale eddies (―Agulhas rings‖) through
the Mozambique Channel. The lack of seasonality in
the organic SST proxies is hypothesized to result from
eddy transport of organic carbon; however, this
material must be derived from a nearby location
because the reconstructed SSTs are in good
agreement with measured SST.
Radionuclide ( 14 C, 210 Pb, 234 Th) analysis of an E-W
transect of surface sediments extending across the
Mozambique Channel revealed that core top
sediments contain a mixture of pre-aged material and
fresh sediment. 14 C AMS ages of foraminiferal calcite
and TOC in surface sediments yielded ages of
977±35 yr BP and 887±30 yr BP, respectively, while
the 210 Pb profile displays a diffusive mixing pattern
and the 234 Th profile displays high activity in the
surface sediments (

P-198
Reconstruction of sea surface temperature in the eastern Indian
Ocean during the last 22000 years
Wenwen Chen 1 , Gesine Mollenhauer 2,3 , Mahyar Mohtadi 3 , Torsten Bickert 3
1 Department of Geosciences, University of Bremen, Bremen, Germany, 2 Alfred-Wegener Institute for Polar
and Marine Research, Bremerhaven, Germany, 3 Center for Marine Environmental Sciences, University of
Bremen, Bremen, Germany (corresponding author:wenwen.chen@uni-bremen.de)
The tropics play a crucial role in modulating regional
and global climate owing to their large heat and
moisture storage capacity. The tropical Indian Ocean
forms the major part of the largest warm pool on
Earth, and its interaction with the atmosphere triggers
important climate variations on both regional and
global scales. To date, numerous palaeoclimatic
studies have focused on the tropical Pacific zonal sea
surface temperature (SST) gradient-related shifts in
convection, extending an El Niño-Southern Oscillation
(ENSO) framework to interpret millennial-scale
climate variability. However, little is known about the
past SST changes of the tropical Indian Ocean.
We picked a sediment core (GeoB10053-7) and a
sediment trap (Jam2) from the Indonesian continental
margin off Java. We performed measurements of
U K‘ 37 ratio of long-chain unsaturated ketones and
TEX86 (tetraether index of GDGTs with 86 carbon
atoms) temperature proxies on the collected particles
and on the glacial to Holocene sediments,
respectively.
Results from the sediment trap show that the
alkenone flux was declining from March to May, and
rapidly increasing from May to November 2002,
similar to the TOC. The GDGT flux shows the same
pattern, but the amount of GDGT is lower than
alkenone flux from August to November. The average
SST from December 2001 to April 2002 using TEX86
is 26.8°C, slightly warmer than the SST from U K‘ 37
(25.7°C). In contrast, the average SST from April
2002 to November 2002 derived from TEX86 is
25.9°C, slightly cooler than the SSTs using U K‘ 37
(26.6°C). Trap studies show that most of the flux to
the sediments occurs during the SE monsoon season,
when dry air from Australia induces coastal upwelling
in the study area.
The age model of core GeoB10053-7 for the last
22,000 years is based on AMS 14 C dates. The TEX86
and U K‗ 37 show core top SSTs of 26.1°C and 27.1°C,
respectively (0-3 cm depth representing the last 300
years). Considering the calculation error of 0.1°C and
1.1°C , these results are in line with present-day
annual mean SST of 26°C. Holocene average SST
using TEX86 is 26.3°C, slightly warmer than the SST
derived from U K‗ 37 (25.4°C). Glacial average SST
based on TEX86 is 23.5°C, slightly cooler than the
SST based on U K‗ 37 is 23.9°C. There is a discrepancy
between the two lipid-based SST-reconstructions
mainly between 17,000 and 22,000 years BP. Both
proxies are generally assumed to represent annual
mean SSTs. Currently discussed hypotheses suggest
different seasonality and/or depth habitat of the
precursor organisms as explanations for the
discrepancy between the records. Our trap data,
however, do not provide evidence for different
seasonality for the modern situation. Stronger
upwelling during the glacial might have caused a
different ecological pattern.
Fig.1 Data from sediment trap JAM2. a) Calibrated SST
reconstructions: TEX86 SST (sky blue line), U k‘‗ 37 SST(violet
line); b) Satellite-derived monthly averaged SST(black line);
c) TOC flux relative to the total flux; d) alkenones and
branched GDGTs flux (ng/m2/day)
Fig.2 Data from core GeoB10053-7. Triangles denote
AMS 14C dating points. Calibrated SST
reconstructions: TEX86 SST (sky blue line), U k‗ 37 SST(
violet line)
337

P-199
Detection of environmental changes in the Minho River Estuary
(NW Iberian Peninsula): A multi proxy approach
Jose María De la Rosa 1 , Francisco J. Gonzalez-Vila 2 , Heike Knicker 2 , José Antonio
González-Pérez 2 , Francisco Fatela 3 , Eduardo Leorri 4 , Reide Corbett 4 , Antonio M.
Soares 1 , Fátima Araújo 1
1 Instituto Tecnológico e Nuclear, Estrada Nacional 10, 2685-953., Sacavém, Portugal, 2 Instituto de
Recursos Naturales y Agrobiología de Sevilla-CSIC, Avda. Reina Mercedes, 10, 41012, Seville, Spain,
3 Centro e Departamento de Geologia, Faculdade de Ciências, Universidade de Lisboa, Campo Grande,
1749-016, Lisbon, Portugal, 4 East Carolina University, East Fifth Street, NC 27858-4353,, Greenville, United
States of America (corresponding author:jmrosa@itn.pt)
Biogeochemical processes and environmental
conditions that lead to the preservation of organic
matter (OM) in coastal and marine sediments has
been the subject of a wealth of studies in the last
decades (Hedges et al., 1999). It is estimated that
more than 80% of the total organic carbon preserved
in marine sediments is buried in deposits along the
continental margins in "terrigenous-deltaic" regions
near river mouths. In such semi-enclosed scenarios,
significant environmental changes, such as climatic
warming, flooding caused by an increase in the
riverine water discharge or alteration of the sea level
may be reflected in the characteristics of organic
carbon supplied to and buried in their sediments.
In this sense, the study of the biomarker
assemblages, which are specific and sensitive to
trace compounds biogenic sources (Goñi et al.,
1998), has become a valid tool to interpret the
changes that occurred within those ecosystems and
to explore the possibility of short-term environmental
changes and geochemical processes.
This communication presents geochemical data of a
tidal marsh sediment core (1m depth) taken at the
Minho estuary (NW Iberian Peninsula). Five replicates
were collected with a Van der Horst manual sampler,
to be used in the different analysis. The core chosen
for the biomarker approach was stored in glass
cylinders, sliced into samples of 2 cm of thickness
and kept frozen (-20ºC) to avoid OM degradation.
Free lipids were sohxlet-extracted with a solution
containing dichloromethane-methanol (3:1) for 16 h
and total extracts were saponified with 0.5 mol L -1
KOH in methanol for 8 h under reflux. In order to
remove elemental sulphur, copper curls were added.
The analysis of lipid biomarkers was carried out by
gas chromatography-mass spectrometry (GC-MS)
according to Gonzalez Vila et al., (2003).
Sample resolution was 1 cm for 210 Pb and 137 Cs
analysis, which are used to determine the
accumulation rates. In addition sediments were
characterized by elemental analysis (C, TOC, H, N,
S), whereas isotopic analysis (δ 13 C, δ 15 N) is being
developed.
Preliminary results can be summarized as follows:
The Minho estuary presented very low sedimentation
rates, recording the last 100 years in the top 4-6 cm,
the limiting factor was the sampling resolution (1 cm
samples). Geochronological data estimated by 210 Pb
and 137 Cs suggested a sedimentation rate of about
0.6 mm yr -1 .
Concerning the chromatographic data, several
downcore fluctuations were observed in the patterns
of the most abundant alkyl series (n-alkanes and nfatty
acids), as well as in several biomarker ratios
such as C31 /C17 or C31/C19. In general, our findings
are indicative of the existence of a complex input of
organic matter (OM) to the estuarine area studied,
mainly of terrestrial origin. In addition, significant
changes were observed in the elemental analysis
(TOC decreased from 14% (10-12cm) to 2% (92 cm);
C/N ratio ranged from 17 (10cm) to 10 (92 cm).
Temporal variations could be attributed to terrigenous
contributions from Minho River sediment load,
although different degradation rate of individual
biomarkers as well as that of OM from different origins
should not be neglected when interpreting biomarker
assemblages in these geodynamically active
environments. Prior confirm those findings further
data such as the stable isotopic analysis and
radiocarbon dating are being carried out.
References:
Hedges, J.I., Keil, R.G., 1999. Marine Chemistry 65,
55-65.
González-Vila, F.J, Polvillo, O., Boski, T., Moura, D.,
de Andres, J.R., 2003. Organic Geochemistry 34.
1601-1613.
Goñi, M.A., Ruttenberg,K.C., Eglintong, T.I.,1998.
Geochimica et Cosmochimica Acta 62, 3055-3075.
Keywords: biomarkers patterns, sedimentary organic
matter; Minho tidal marsh
338

P-200
Palaeoenvironmental change reflected by carbon isotopes and
palynology in the early Silurian of the Tanezzuft Formation,
Libya
Mohamed Elkelani 1 , Gert Jan Reichart 1 , Jaap Sinninghe Damsté 1,3 , Zwier Smeenk 2 ,
Wolfram Kurschner 2 , Henk Brinkhuis 2,4 , Peter Nederlof 1,5
1 Utrecht Universities, Faculty of Geosciences, Department of Earth Sciences-Organic Geochemistry.,
Utrecht, Netherlands, 2 Utrecht Universities, Institute of Environmental Biology, Faculty of Science,
Laboratory of Palaeobotany and Palynology, Utrecht, Netherlands, 3 NIOZ Royal Netherlands institute for
sea Research., Texel, Netherlands, 4 Utrecht Universities, Institute of Environmental Biology, Biomarine
Sciences, Laboratory of Palaeobotany and Palynology., Utrecht, Netherlands, 5 Shell Exploration &
Production., Rijswijk, Netherlands (corresponding author:m.elkelani@geo.uu.nl)
The glaciations at the end of the Ordovician attracted
interest not only because of the associated major
extinction event, but also because they resulted in
widespread graptolitic black shales deposition.
Deposition of this organic-rich (‗hot‘) shale unit in the
North African/ Arabian region was restricted to the
earliest Silurian Rhuddanian stage and is currently the
source of almost all Palaeozoic oils in North Africa
and the Middle East. Two cores covering the early
Silurian Tanezzuft Formation from the Ghadames and
Murzuq Basins in western Libya were studied for the
palynological composition and carbon isotopic
composition of the bulk organic matter (δ 13 Corg).
Informal acritarch assemblage biozones were
identified based on the known ranges of key marker
taxa and on overall palynomorph assemblages
calibrated with high-resolution graptolite stratigraphy.
Unfortunately data on graptolites are scarce in Libya.
The palynomorph assemblages from the Tanezzuft
Formation appear to be largely influenced by periodic
environmental changes recorded from early to late
Llandovery. The marine acritarchs flora is
accompanied by common non-marine miospores and
cryptospores suggesting a proximal position and
significant admixing of land-derived material into the
marine setting. Some similarities are evident between
this Rhuddanian assemblage and those of Saudi
Arabia and British acritarch. This high-resolution
biostratigraphy for the same records across the early
Silurian (Llandoverian) allows comparison the δ 13 Corg
signatures between basins with events recorded from
elsewhere, such as Argiles Principales Formation
(Tunisia), Cornwallis Island (Canadaian Arctic), and
Dob‘s Linn (Scotland). The δ 13 Corg record from the
deeper-water successions on Cornwallis Island, and
Dob‘s Linn shows evidence of a significant positive
δ 13 Corg excursion in the upper Aeronian and weak
positive shifts in the mid-Rhuddanian and uppermost
Rhuddanian and the global environmental effect of
the early Rhuddanian and late Aeronian glaciations.
The base of the Tanezzfut Formation is marked by a
conspicuous high gamma ray intensity interval with a
high total organic content (TOC wt%), which can be
traced along the North African Gondwana margin.
This formation represents a progressive,
transgression, first drowning the deepest parts of the
palaeodepressions, but at a later stage also extending
to the basins palaeohighs. The δ 13 Corg record shows a
significant positive excursion during the onset of the
hot shale (Rhuddanian) deposition in the Ghadames
Basin with a rapid onset and gradually recovery. The
δ 13 Corg record from the Murzuq Basin, in contrast,
shows no clear isotope excursion. Since the hot shale
in Murzuq Basin is also much thinner than that of
Ghadames, the lack of a carbon isotope excursion at
the Murzuq Basin suggests a shift in the black shale
deposition from the central part of the basin to the
margin. Comparison of the biomarker signatures
between the two basins suggests a much more
intense biodegradation in Murzuq Basin compared to
Ghadames Basin.
The lowermost Tanezzuft Formation (hot shale) is
characterized by low abundances of acritarchs
assemblages and some prasinphytes occur in time of
high stable isotope values and dominated by what
was probably originally well preserved AOM, which is
typical of laminated black shales with (Type II) oil
prone kerogen deposited in distal stratified shelf sea
basin with dysoxic-anoxic depositional conditions.
339

P-201
Carbon and hydrogen isotope biomarker records of methane
release and hydroclimatic variability from a thermokarst lake in
the Alaskan Arctic
Marcus Elvert 1 , Matthew J. Wooller 2 , Kevin Becker 1 , Benjamin Gaglioti 2 , Kai-Uwe
Hinrichs 1 , John W. Pohlman 3
1 Department of Geosciences & MARUM Center for Environmental Sciences, University of Bremen, Bremen,
Germany, 2 Water and Environmental Research Center, University of Alaska Fairbanks, Fairbanks, United
States of America, 3 U.S. Geological Survey, Woods Hole Coastal & Marine Science Center, Woods Hole,
United States of America (corresponding author:melvert@uni-bremen.de)
Permafrost thaw during recent arctic warming has
stimulated the expansion of some thermokarst lakes
and, in the process, mobilized vast quantities of labile,
Pleistocene-aged soil organic matter. Presently,
methane produced during anaerobic degradation of
this organic matter accounts for 10-50% of the
methane emitted from northern wetlands [1]. With at
least 500 Gt (10 15 g) of carbon stored in permafrost
soils [2], continued warming of the Arctic has the
potential to provoke a positive feedback response
leading to greater emissions of greenhouse gases
from high-latitude wetlands.
To determine if thermokarst lake environments in
the Alaskan Arctic have previously responded in such
a way, we reconstructed the methane flux and
regional climate from preserved lipid biomarkers and
fossil chironomids in a radiocarbon-dated lake
sediment core representing the last ~12 kyr. In the
time period before 10 kyr BP, temperature estimates
based on cyclisation and methylation indexes of soilderived
branched glycerol dialkyl glycerol tetraether
(GDGT) membrane lipids [3] corresponded with the
Holocene Thermal Maximum (HTM) of North Alaska
[4] and recorded annual mean air temperatures (MAT)
around 2.6 o C warmer than the rest of the Holocene
(Fig. 1). For the HTM interval, hop-17(21)-ene, a
hopanoid biomarker for bacteria including aerobic
methanotrophs [5], was most abundant and 13 Cdepleted
down to -56‰, suggesting intense methane
turnover and flux during the HTM.
Stable hydrogen isotopes of terrestrial-derived C23
and C27 n-alkanes were used to constrain the regional
hydroclimatic conditions during the record. Within the
HTM zone, �D values of n-C27 are around 12‰ more
negative relative to recent times indicating deuteriumdepleted
lake and meteoric water sources that very
likely result from addition of glacial melt-water. By
contrast, the D-enrichment in n-C23 by ~20‰ is
generally observed in terrestrial plants [6]. Above the
HTM zone, �D profiles invert with more negative �D
values found for n-C23 suggesting substantial
contributions of submerged mosses or aquatic plants
[7] which is additionally supported by a shift to lower
values in average chain length (n-C21 to n-C31). The
overall constant �D profiles for the past 10 kyr BP
indicate an isotopically uniform water source and are
consistent with a relatively steady and cool climate.
Our results document the presence of strong
environmental change and abundant aerobic
methanotrophs during the HTM, an event that could
serve as a harbinger for how the Arctic may respond
to additional global warming.
Fig. 1. Biomarker downcore profiles from Lake Qualluuraq
on the Alaskan North Slope: a) �D values of n-C23 and n-C27,
b) concentration and � 13 C values of hop-17(21)-ene, and c)
reconstructed MAT based on soil-derived branched GDGTs.
References
[1] Walter, K.M. et al. (2006) Nature 443: 71-75.
[2] Zimov, S.A. et al. (2006) Science 312: 1612-1613.
[3] Weijers, J.W.H. et al. (2007) Geochim Cosmochim Acta
71: 703-713.
[4] Kaufman, D.S. et al. (2004) Quat Sci Rev 23: 529-560.
[5] Birgel, D. and Peckmann, J. (2008) Org Geochem 39:
1659-1667.
[6] Sachse, D. et al. (2006) Org Geochem 37: 469-483.
[7] Mügler, I. et al. (2008) Org Geochem 39: 711-729.
340

P-202
Terrestrial higher plant biomarkers in hyperpicnite-like
sedimentary sequence in the Miocene Kawabata Formation,
central Hokkaido, Japan: Evidence for direct transport of
terrigenous matter by flood?
Satoshi Furota, Ken Sawada
Faculty of Science, Hokkaido University, Sapporo, Japan (corresponding
author:furota@mail.sci.hokudai.ac.jp)
Turbidity current is a main system for transport and
redeposition of organic matter from coastal to deepsea
provinces. The turbidite sediment provides us
multiple information for both marine and terrestrial
environments because it contains the autochthonous
matter derived from marine organisms and
terrigenous matter transported from land areas. It was
reported that biomarker compositions were quite
different between turbiditic and pelagic mudstone
layers in the Miocene turbiditic sequences of outcrops
in Hokkaido [1]. Studies on the turbiditic sequences
suggested that organic geochemical characteristics
were strongly controlled by types and phases of
transport, redeposition and postdepositional
diagenesis of turbidites. It, recently, has been known
that heavily sediment-laden effluent of flooding rivers
can form peculiar turbidity current, referred to as
hyperpycnal flow, in marine environment. The
hyperpycnal flow is thought to be direct transport
system of terrigenous matter from land to ocean. In
the present study, we focus terrigenous biomarker
compositions in the hyperpycnite-like sedimentary
sequence. Furthermore, we discuss the
biogeochemical interaction between land and ocean
such as higher marine primary production attributed to
efficient transport of terrigenous matter by flood
system.
We discovered a peculiar turbiditic sequence with
about 50 cm thick in an outcrop of the Miocene
Kawabata Formation in Yubari, central Hokkaido. The
Kawabata Formation is characterized by turbidite
facies that consist of alternations of conglomerate,
sand, and mudstones, and is thick sediments filled
with the Ishikari Trough during the Middle- Late
Miocene. This sequence consists of homogenous
mudstone, coarsening-upward sandstone, sandstone
intercalated thin layers of plant fragments, sandstone
randomly contained plant fragments, fining-upward
sandstone, sandstone with horizontal lamination, and
homogenous mudstone, which is resemble to that in
hyperpycnite sequence. The sediment samples were
crushed to fine powder. Carbonate-free samples were
analyzed for total organic carbon content (TOC; %) by
a J-Science Micro Corder. Lipids were ultrasonically
extracted from the powder samples as reported
previously [1]. These fractions were analysed by gas
chromatography / mass spectrometer (GC/MS).
TOC content was found to increase remarkably
from sandstone layers with plant fragments to
horizontal lamination layer, which is concordant with
hyperpycnite [2]. Organic geochemical characteristics
for biomarker were followings, 1) concentrations of
coniferous biomarker such as phyllocladane were
remarkably higher in homogenous mudstone below
the sandstones and coarsening-upward sandstone, 2)
concentrations of degraded oleanenes originated from
angiosperm were higher in sandstone layers with
plant fragments, and 3) maturity levels were
significantly lower in sandstone layers with plant
fragments. From these results, we conclude that this
sedimentary sequence was hyperpycnite that had
been formed by flooding river. Furthermore, we found
that concentrations of marine algal biomarkers such
as steranes and highly branched isoprenoid (HBI)
alkanes remarkably increased with increasing those
of terrigenous biomarkers in homogenous mudstones
above the sandstones. This fact suggests that marine
primary production was activated by efficient transport
of terrigenous materials by flood system in the Ishikari
Trough during Late Miocene. These results are
important for understanding material cycling and
biogeochemical processes with geological time scale.
References [1] Okano, K., Sawada, K. (2008)
Geochem. J. 42, 151-162. [2] Yoshida, M., Yoshiuchi,
Y., Hoyanagi, K. (2009) Island Arc 18, 320-332.
341

P-203
Biogeochemical processes in Holocene-Pleistocene sediments
at

P-204
Are poriferan biomarkers preserved in the geological record? A
study on sponge fossils and sponge-rich sediments of various
ages
Juliane Germer, Martin Blumenberg, Joachim Reitner, Volker Thiel
Georg-August-University, Göttingen, Germany (corresponding author:jgermer@gwdg.de)
Sponges are considered to be the most ancient
metazoans. 14 fossilized sponges and sediments
containing abundant sponge remains were extracted
to test the preservation potential of four classes of
sponge-derived lipid biomarkers in the bitumen
fractions of geological samples (mid-chain branched
fatty acids, demospongic acids, sterols and
brominated secondary metabolites). Modern sponges
and sponge-microbial carbonate crusts were used as
reference materials.
The recent samples contain large amounts of midchain
branched fatty acids (MBFA) characterized by a
remarkable variety of structural isomers in the C16 to
C26 range. Specific, yet unknown sponge-associated
bacteria are suggested to be the producers of shortchain
MBFA (C16 – C19) which are subsequently
elongated by the sponge cells to long-chain MBFA [1].
Monomethylated mid-chain branched alkanes,
potential diagenetic derivatives of MBFA, occurred in
small amounts in some of the ancient samples
studied. These compounds showed, as well as the
MBFA, a great variety of structural isomers in the C16
– C20 range. Comparisons with the hydrocarbon
compositions of ancient carbonates and the fatty acid
and desulphurized hydrocarbon patterns of a recent
demosponge suggested that MBFA represent
plausible biological precursors of mid-chain branched
alkanes found in the ancient materials. However,
interpretations should be drawn with caution, since
other non-sponge sources may also account for midchain
branched alkanes in ancient sediments.
Long-chain demospongic acids (Δ 5,9 unsaturated,
≥C24) are widespread in members of the sponge
classes Demospongiae and Hexactinellida. However,
no plausible geological derivatives could be
recognized in ancient sponge-derived sediments,
suggesting that these compounds do not provide
suitable biomarkers for the contribution of spongederived
organic matter in the bitumen fractions of
ancient sediments.
Using MS/MS, the samples were carefully examined
for 24-isopropycholesterol and its geological
counterpart, 24-isopropylcholestane (24-ipc), whose
presence in ancient sediments and oils has been
proposed to record the first occurrence of metazoans
in the geological biomarker record [2][3]. However, no
24-ipc was detected in the ancient sponge-derived
samples.
Brominated organic compounds, potentially derived
from secondary metabolites, were observed as trace
compounds in the majority of the ancient samples
studied. These structures, however could not be
unambiguously assigned to biogenetic sources, but
may also be due to anthropogenic contamination,
which argues against an application of brominated
secondary compounds as sponge-derived
biomarkers.
Additionally, two methane-seep derived carbonates
containing ample sponge fossils were investigated for
their potential to preserve poriferan biomarkers under
conditions of early and rapid lithification. It was found
that signals from the microbial anaerobic oxidation of
methane were preserved remarkably well in these
seep carbonates, but again, no distinctive sponge
biomarkers were detected.
Summarizing, this study did not reveal a preservation
of sponge-cell derived biomarkers in the bitumen
fractions of ancient samples.
1. Pape, T., Lipidbiomarker
schwammassoziierter Bakterien und
Archaeen, in Institute of Biogeochemistry
and Marine Chemistry. 2003, University of
Hamburg: Hamburg. p. 164.
2. McCaffrey, M.A., et al., Paleoenvironmental
implications of novel C30 steranes in
Precambrian to Cenozoic age petroleum and
bitumen. Geochimica et Cosmochimica Acta,
1994. 58: p. 529-532.
3. Love, G.D., et al., Fossil steroids record the
appearance of Demospongiae during the
Cryogenian period. Nature, 2009. 457(7230):
p. 718-721.
343

P-205
Lipid biomarker analysis of faeces from modern and ancient
herbivores
Fiona Gill 1 , Richard Pancost 2 , Richard Dewhurst 3 , Emma McGeough 3 , Padraig O'Kiely 3 ,
Ian Bull 2
1 University of Leeds, Leeds, United Kingdom, 2 University of Bristol, Bristol, United Kingdom, 3 Animal &
Grassland Research and Innovation Centre,, Dunsany, Ireland (corresponding author:F.Gill@leeds.ac.uk)
Coprolites (fossilised faeces) are an underutilised
source of palaeoecological information. The
potential for lipid biomarkers preserved in coprolites to
reveal unique details of the diet, digestive processes
and digestive tract microbiota of extinct animals has
already been demonstrated [1]. However, in order to
fully exploit the benefits of this new approach it is
necessary to investigate further the controls on faecal
biomarkers in modern animals and on preservation of
lipids in coprolites.
Previous studies [2] found the methanogen
biomarker archaeol to be present in the faeces of
foregut-fermenting herbivores, but not hindgut
fermenters, suggesting that archaeol found in
coprolites therefore could be interpreted as evidence
that the producer was a foregut fermenter. More
recent research [3] has shown a correlation between
the concentration of archaeol in the faeces of modern
cattle and their methane emissions (Fig. 1). Archaeol
has also been detected in a 2500 year old ovi-caprid
dung pellet, raising the possibility that this method
may be used to estimate methane emissions from
ancient fauna. This could be used to test recent
suggestions of a causal link between megaherbivore
extinctions and global cooling in the Pleistocene [4].
However, a recent survey of over 20
coprolites from Cretaceous to Pleistocene in age has
shown that the preservation of lipids in herbivore
coprolites is highly variable and is related to factors
including age, mode of preservation and diagenetic
history of the material. Ancient faeces preserved by
desiccation have been found to contain
concentrations of lipids order of magnitude higher
than those recovered from lithified coprolites. This
suggests that further research efforts should focus on
desiccated coprolites or exceptionally well preserved
lithfied coprolites with high organic carbon content.
References
[1] Gill et al. (2009) Quaternary Research 72, 284-288
[2] Gill et al. (2010) Organic Geochemistry 41, 467-
472
Methane g -1 kg DMI
Archaeol μg -1 g dry weight faeces
individual animals
Silage diet
Concentate
diet
individual animals
Figure 1 Methane emissions and faecal archaeol
concentration in cattle (DMI = dry matter intake)
[3] Gill et al. Animal Feed Science and Technology, in
press
[4] Smith et al. (2010) Nature Geoscience 3 374-375
O
O
OH
344

P-206
Biomarker proxy-reconstructions of climatic and productivity
patterns in the NE Mediterranean Sea during the Holocene
Alexandra Gogou 1 , Ioanna Bouloubassi 2 , Georgios Katsouras 1 , Vasilios Lykousis 1
1 Hellenic Centre for Marine Research, Institute of Oceanography, 19013, Anavyssos, Greece, 2 LOCEAN,
CNRS UMR 7159, Université P. Et M. Curie, Paris, France (corresponding author:agogou@ath.hcmr.gr)
Early Holocene sediment records collected in the
Eastern Mediterranean Sea (EMS) bear witnesses for
the formation of the most recent sapropel S1, closely
associated with distinct minima in the orbital
precession cycle and the insolation-driven monsoon
maxima. The different scenarios of S1 deposition
involve changes in marine productivity, organic matter
preservation and circulation changes and are still
under debate ([1], [2], [3]).
Herewith, we present a high-resolution study of
organic geochemistry proxies in three gravity cores
collected from the EMS, namely the cores SL152 and
NS-14 collected from the Aegean Sea (north and
southeast, respectively), and core HCM2/22 collected
from the open EMS. Our goal is to investigate the
patterns of organic matter accumulation and
preservation and reconstruct paleo-SSTs based on
alkenone unsaturation index Uk´37 during the last
20,000 yrs with focus on the deposition of sapropel
S1 along a north-south transect in the EMS.
Depending on the water column depth, the sediment
accumulation rates and the proximity to freshwater
and water formation sources, S1 deposited in our
records between ~9.8 to 6.4 kyr BP. During the
Holocene climatic optimum, SSTs increase gradually
more than 4°C and reaches values as high as 21.2°C,
22.5°C and 23°C (in cores 152SL, NS-14 and
HCM2/22 respectively). Our records also show a
pronounced centennial-scale cooling that culminates
from ~8.2 to 7.6 kyrs BP, coeval to the N. Atlantic
cooling event ([4]), causing an interruption in the
deposition of S1 in all sites. SST fluctuations are
detected between 4.9 and 4.1 kyr BP in core NS-14,
with a sharp positive shift to 24.9°C indicating the
presence of a warm period in the mid Holocene ([8]).
The higher accumulation rates of TOC and all marine
biomarkers within the sapropelic layer S1a and less
pronounced within S1b in the Aegean Sea compared
to the open EMS site. Organic carbon stable isotopes
values span a narrow range. The different types of
δCorg excursions associated with stronger fluvial
delivery (terrestrial inputs) in the north Aegean Sea
whereas the other two sites received most marine
organic matter. The distributions of land plant
biomarkers are indicative of variable terrigenous
organic matter supply and the concomitant transport
of nutrients to surface waters. Furthermore,
distribution patterns and characteristic ratios of
marine biomarkers exhibit differences in the
paleoproductivity trends and ventilation changes over
the last 20 kyr. Lighter values of δ Ν within S1 and
Mid Holocene Humid (MHH) phases reflect a
significant contribution of N-fixing organisms to the Ncycle
related probably to higher demand for nitrogen
(denitrification/ P regeneration) due to the established
dysoxia in the water column/sediment interface.
References
1 - Emeis, K.-C., U. Struck, H.-M. Schulz, S.
Bernasconi, T. Sakamoto, and F. Martinez-Ruiz,
2000. Palaeogeography, Palaeoclimatology,
Palaeoecology, 158, 259-280.
2 - Casford, J.S.L., Rohling, E.J., Abu-Zied, R.H.,
Fontanier, C., Jorissen, F.J., Leng, M.J., Schmiedl,
G., Thomson, J., 2003. Palaeogeography,
Palaeoclimatology, Palaeoecology, 190, 103-119.
3 - De Lange, G.J., J. Thomson, A. Reitz, C.P. Slomp,
M. Speranza Principato, E. Erba, and C. Corselli,
2008. Nature Geoscience, 1 (9), 606-610.
4 - Rohling, E. J., Pälike, H., 2005. Nature 434, 975–
979.
345

P-207
Biomarkers along a holocene sedimentary sequence from the
Guadiana River Estuarine Area (Portugal/Spain Border)
Francisco J. González-Vila 1 , Kathrin Schütrumpf 3 , José A. González-Pérez 1 , Tomasz
Boski 2 , José Mª de la Rosa 4 , Heike Knicker 1 , Dominik Faust 3
1 IRNAS-CSIC, Seville, Spain, 2 CIMA-Universidade do Algarve, Faro, Portugal, 3 Technische Universität
Dresden, Dresden, Germany, 4 ITN, Sacavém, Portugal (corresponding author:fjgon@irnase.csic.es)
A wide range of recent sediments, such as algal mats
and aquatic or sapropelic sediments, has been used
as model systems for studying the formation of
ancient sediments and the fate of organic materials
after its deposition, in particular the early diagenesis
of lipids, which is not until now a well-defined process
in terms of time scale and end products (Killops and
Killops, 1993 and references therein).
Estuarine zones, due to the fast accumulation of fine
sediments, appear to be a suitable area for the study
of the accumulation and post-depositional
transformation of organic matter. In such a semienclosed
environment the period of climatic warming
and sea level rise (which occurred since the last
glacial maximum) can be properly characterized in
terms of organic carbon transfer and burial in
coastal/marine sediments.
This communication is a part of a wider study of
diagenetic processes in the area of Guadiana River
Estuary (Spain/Portugal border) where its submerged
delta is representative of natural changes occurred
during the transition from Late Pleistocene
Weichselian Pleniglacial to the present Holocene
Interglacial period. In this communication the vertical
distribution of terrestrial and phytoplankton biomarker
compounds in a sediment core (65 m depth) going
down to the Pleistocene surface is studied by gas
chromatography-mass spectrometry (GC-MS).
Sediment samples were taken at different depth each
0.5 m from a drilling cored borehole (65 m deep) in
the area of Ayamonte (Spain) down to the Pleistocene
surface. Samples were immediately frozen to prevent
microbial growth, and freeze-dried before analysis.
Lipids were solvent extracted using a
dichloromethane-methanol (2:1) mixture during 24
hours. Total extracts were concentrated at reduced
pressure, derivatized with trimethylsylildiazomethane
and subjected to GC-MS analysis. Further details on
the extraction and fractionation protocol, and the
conditions for separation and identification of
individual components were published elsewhere
(Gonzalez-Vila et al., 2003).
The main conclusions drawn can be summarized as
follows:
a) There is a close similarity between the
biomarker distributions along the core. The most
relevant parameters of source and maturity, such as
the ratios pristane/phytane, pristane/C17 and
phytane/C18 do not change significantly.
b) Terrestrial plants and plankton are the
prevalent biogenic sources for the aliphatic
hydrocarbons and fatty acids detected in the
estuarine sediment. Their distributions also reflect the
low maturity level of this sedimentary organic matter.
The lack of typical unresolved mixtures of branched
and cyclic aliphatic hydrocarbons indicates no
contamination by petroleum residues or urban runoff.
c) It is noteworthy the detection of a series of
resinic acids, typical biomarkers of conifer vegetation.
The observed changes in the hydrocarbon
assemblage within the Holocene are discussed in
terms of possible variations in the planktonic and
terrigenous supply, which could be mainly attributed
to the evolution of the circulation pattern in the
estuary and to the alteration in vegetation cover within
the Guadiana drainage basin.
Gonzalez-Vila et al. (2003). Org. Geochem. 34: 1601-
1613.
Killops, S.D. and Killops, V.J. (1993): An introduction
to Organic Geochemistry. Longman Scientific &
Technical, Harlow.
346

P-208
Alkenone producers during late Oligocene-early Miocene
revisited
Julien Plancq 1 , Vincent Grossi 1 , Jorijntje Henderiks 2 , Laurent Simon 1 , Emanuela Mattioli 1
1 CNRS - Université de Lyon, Villeurbanne, France, 2 Uppsala University, Uppsala, Sweden (corresponding
author:vincent.grossi@univ-lyon1.fr)
Since the nineties, alkenones have been widely
used as proxies for (paleo)oceanographic
reconstructions. In modern oceans, these long-chain
lipids are specifically produced by a few species of
coccolithophores, namely Emiliania huxleyi and
Gephyrocapsa oceanica. It is commonly assumed
that the most probable Cenozoic alkenone producers
are to be found within the family Noelaerhabdacaea,
notably the genera Reticulofenestra and
Dictyococcites (grouped as reticulofenestrids). To
date, the contribution of reticulofenestrids species to
alkenone production has never been clearly
demonstrated and has received little attention.
This study investigates ancient alkenone
producers at Deep Sea Drilling Project Site 516
during the late Oligocene-early Miocene. Studies by
Pagani et al. [1, 2] and Henderiks and Pagani [3]
showed the simultaneous presence of nannofossils
and alkenones at this site, but neither alkenone
concentrations nor absolute abundances of coccoliths
were determined.
A comparison between nannofossil speciesspecific
absolute abundances and alkenone content
in the same sedimentary samples shows, for the first
time, that the species Cyclicargolithus floridanus was
a major alkenone producer at the studied site. This
interpretation is supported by statistical analyses
(linear regressions) which show that only absolute
and relative abundances of the genus Cyclicargolithus
produce a significant and positive correlation with the
total alkenone content. However, Cyclicargolithus
abundances explain 40 % of the total variance of
alkenone concentration, suggesting that other taxa
also contributed to the alkenone production at DSDP
Site 516. Among the reticulofenestrids, the
contribution by the large Dictyococcites seems
relatively significant, whereas that of Reticulofenestra
appears questionable. This study thus suggests that,
contrary to common assumptions, Reticulofenestra
was not the most important alkenone producer
throughout the studied time interval.
On the other hand, the distribution of the different
alkenone isomers (MeC37:2, EtC38:2, and MeC38:2)
remains unchanged across the sedimentary interval
considered, which may imply that there was no
species-specific bias in alkenone molecular ratios
within the Noelaerhabdaceae Family during the late
Oligocene-early Miocene.
Our results challenge the use of alkenone-based
proxies in sediments pre-dating the first occurrence of
modern producers and underscore the importance to
carefully evaluate the likely alkenone producers in
(paleo)oceanographic studies. The implications of our
findings, especially concerning the reconstruction of
ancient partial pressure of CO2 (pCO2), will be
discussed.
References
[1] Pagani, M., Freeman K.H., Arthur M.A. (2000a),
Geochimica et Cosmochimica Acta, 64, 37-49.
[2] Pagani, M., Arthur M.A., Freeman K.H. (2000b),
Paleoceanography, 15, 486-496.
[3] Henderiks, J., Pagani M. (2007), Paleoceanography, 22,
PA3202.
347

P-209
A comparison of methane emission and oxidation histories on
the Amazon and Congo fans over the last 200 kyr
Luke Handley, Helen Talbot, Kate Osborne, Thomas Wagner
Newcastle University, Newcastle upon Tyne, United Kingdom (corresponding
author:luke.handley@gmail.com)
The Congo and Amazon fans are important
regions of methane (CH4) storage and seepage, with
gas hydrates abounding in the shallow subsurface
alongside more deeply-buried thermogenic methane
reservoirs linked with hydrocarbon source rocks.
However, past changes in CH4 emission and
oxidation at these localities remain unconstrained
primarily due to the lack of adequate geochemical
tracers for such processes.
Bacteriohopanepolyols (BHPs) are lipid
membrane constituents and occur with a wide range
of structural and functional variability in many
bacteria. AminoBHPs are produced by methaneoxidising
bacteria and 35-aminobacteriohopane-
30,31,32,33,34-pentol (aminopentol) is highly specific
to Type I aerobic methane oxidising bacteria. Here,
we present new BHP data from the Amazon fan (ODP
Site 942) and compare aminopentol and other paleorecords
to similar data from the Congo fan (ODP Site
1075) to investigate how aerobic methane oxidation,
and inferred emission, varied over the last 200 kyr on
opposite sides of the tropical Atlantic.
BHP concentrations and diversity in the Amazon
are generally greater than in the Congo, with a
number of uncommon compounds such as a
methanotroph-derived unsaturated aminopentol,
bacteriohopanehexol and others occurring throughout
the core. Indeed, the BHP assemblage from the
Amazon fan is to date by far the most complex BHP
signature reported from marine sediments. This may
be due to the unique setting in a region characterised
by a large terrigenous input and high primary
productivity, leading to a diverse array of precursor
bacteria.
These new biomarker records from the Amazon
fan also reveal dramatic variability in aminopentol,
and other aminoBHP, concentrations over the last
200 kyr. We have previously reported that in the
Congo core, changes in aminopentol concentration,
and hence fluctuations in the intensity of aerobic
methane oxidation (AMO) and inferred CH4 emission,
follow a distinct pattern that appears to correlate with
late Quaternary glacial-interglacial climate cycles, with
generally higher emissions during interglacials, and
we hypothesised that our record reflects orbitallydriven
shifts in the gas hydrate stability zone within
the shallow subsurface. In the Amazon, although
concentrations do vary within each climate mode,
aminoBHP concentrations are also generally higher
during interglacials, with a particularly strong increase
in AMO intensity during marine isotope stages (MIS) 5
and 3, suggesting a possible link between Quaternary
climate and methane emission on the Amazon fan, as
is the case in the Congo. However, on the Congo Fan
MIS 3 is the only interglacial period over the last ca.
900 kyr that is not characterised by a notable increase
in sedimentary aminopentol concentrations. This
could reflect local differences in the susceptibility of
the respective methane reservoirs to climate
variability. Also, aminopentol concentrations are much
higher in the Amazon core, with maximum values
more than double those reported from the Congo,
suggesting that AMO intensity and methane emission
into the water column was generally greater off the
Amazon.
To summarise, although there are some
differences between the BHP paleo-records from the
Congo and the Amazon fan over the last 200 kyr,
there appears to be a link between aerobic methane
oxidation (and inferred emissions) and Quaternary
climate variability at both sites of the tropical Atlantic,
with greater emissions during interglacials. This work
continues to highlight the biomarker potential of BHPs
and in particular aminopentol as a sedimentary tracer
for the aerobic oxidation of methane.
348

P-210
The preservation of vascular plant biomolecules in a 155 million
years old sedimentary deposit. Case of the Flogidarry Shale
Member (Isle of Skye, Scotland)
Apolline Lefort, Yann Hautevelle, Bernard Lathuillière, Vincent Huault
UMR7566 G2R, CNRS, Nancy Université, Vandoeuvre-lès-Nancy, France (corresponding
author:yann.hautevelle@g2r.uhp-nancy.fr)
The Oxfordian/Kimmeridgian Flodigarry
Shale Member (Isle of Skye, Scotland) represents a
continuous succession of silty claystones and nodular
limestones. This outcrop may be a potential stratotype
(GSSP) for the Oxfordian/Kimmeridgian boundary.
So, many studies were conducted on these deposits,
covering the fields of lithology, biostratigraphy (using
both micro and macrofossils), sedimentology, isotopic
geochemistry and magnetostratigraphy (Wierzbowski
et al., 2006). Although these shales are particularly
rich in organic carbon, available data about their
organic molecular composition are very scarce. We
sampled all beds of the argillaceous succession in
order to conduct molecular analyses of the soluble
organic matter. Originally, the main objective was to
trace and document any evolution of the molecular
signature in these shales which could be related to
the Oxfordian/Kimmeridgian boundary.
The molecular compounds preserved in
these deposits shows that the organic component of
the Flogidarry Shale Member is a mixture of both
marine (algae, plankton, bacteria) and terrestrial
(vascular plants) organic matter. Excepted for one
single bed, the terrestrial contribution is clearly
important. This can be linked to the palaeogeography
of Scotland during the Oxfordian/Kimmeridgian
transition. Indeed, the Flogidarry area was located in
a narrow sea channel between the Hebrides and the
Irish massif. In regard to this palaeogeographic
background, it is not surprising to record a substantial
terrestrial molecular biomarkers supply to this
sedimentary succession.
No significant evolution of the molecular
signature is recognizable from one layer to another,
especially at the Oxfordian/Kimmeridgian boundary.
From a molecular point of view, the
exceptional preservation of the organic matter
remains the most interesting characteristic of these
sedimentary rocks deposited 155 million years ago.
Indeed, the Flogidarry Shale Member is characterised
by the abundance of diasterenes, hopenes, the large
predominance of ββ-hopanes over the αβ-hopanes as
well as the absence of the R epimers for
homohopanes. This distribution demonstrates the
thermal immaturity of the Flogidarry Shale Member.
Most interesting are the still functionalised
biomolecules (meaning molecules having escaped
diagenetic transformations since biosynthesis) like
cadinol, ferruginol and podocarpatrienol. This clearly
proves the excellent preservation of this sedimentary
organic matter deposited some 155 million years ago.
The preservation of such bioterpenoids in
sedimentary rocks as old as Jurassic is clearly
uncommon. Their recognition in deposits older than
50 million years are very scarce because they are
metastable and thus rapidly degraded during the first
steps of diagenesis. In fact, to our knowledge, there is
only one report of biomolecules preserved in
sedimentary deposits older than Kimmeridgian, dated
from Callovian (Marynovski & Zaton, 2010). Thus, this
makes the Flogidarry Shale Member the second
oldest sedimentary deposit to contain well-preserved
bioterpenoids and emphasizes the exceptional
preservation conditions associated to this outcrop.
These well-preserved biomolecules suggest
a palaeovegetation largely composed of pinophytes
on the nearest emerged lands. After the plant
biomarkers distribution, these landmasses were
probably covered by pinophytes forests especially
composed on Cupressaceae, Taxodiaceae or
Cheirolepidiaceae. This observation is moreover in
accordance with palynological studies (Riding &
Thomas, 1997).
Marynowski & Zaton (2010). Applied Geochemistry
25, 933-946.
Wierzbowski et al. (2006). Jurassica, Volumen IV, 17-
33.
Riding & Thomas (1997). Scottish Journal of Geology
33, 59-74.
349

P-211
Paleocene-Eocene Thermal Maximum impacts on terrestrial
environments. Insights from the organic matter evolution in the
Vasterival section (Dieppe-Hampshire Basin, France)
Sylvain Garel 1 , Johann Schnyder 1 , Jérémy Jacob 2 , Mohammed Boussafir 2 , Christian
Dupuis 3 , Jean-Yves Storme 4 , Johan Yans, Alina Iakovleva 5 , Emile Roche 6 , Claude
LeMilbeau 2 , Florence Quesnel 7
1 ISTeP, Université P. & M. Curie, UMR 7193 du CNRS, Paris, France, 2 Institut des Sciences de la Terre
d'Orléans, ISTO, Université d'Orléans, UMR 6113 du CNRS/INSU, Orléans, France, 3 Service de Géologie
Fondamentale et Appliquée, Université de Mons, Mons, Belgium, 4 FUNDP, Département de Géologie,
Université de Namur, Namur, Belgium, 5 Geological Institute, Russian Academy of Sciences, Moscow,
Russian Federation, 6 Laboratoire de Paléontologie Végétale, Université de Liège, Liège, Belgium,
7 GEO/G2R, BRGM, Orléans, France (corresponding author:jeremy.jacob@univ-orleans.fr)
The Paleocene-Eocene Thermal Maximum (PETM,
55.8 Ma [1]) is regarded as one of the most rapid
global warming of the Cenozoic era, with temperature
increase of 4-8°C in about 10-20 ka [2]. Thus, it is
often proposed as a potential analogue of future
climatic conditions expected in the IPCC screenplays.
The PETM is recorded in both marine and continental
deposits by an abrupt negative Carbon Isotope
Excursion (CIE) associated with other sedimentary
and biological anomalies. The consequences of the
PETM on terrestrial environments are less
documented than in marine ones. This limits our
regional- and global-scale understanding of the
impact of such a climate change on continents and
the associated response of ecosystems.
This study focuses on the Vasterival section (Seine-
Maritime, Upper Normandy) located in the southern
part of the Dieppe-Hampshire Basin, in which the
PETM is attested by a negative δ 13 Corg shift in the
organic matter (OM), and confirmed by the
stratigraphic record in this locality belonging to the
Cap d‘Ailly composite section [3]. The 2 m thick
section, which presents a notably well preserved OM,
is mainly constituted by terrestrial sediments from
lacustrine to coastal swamp environments, and in
which OM-poor clays are followed by OM-rich clays,
centimetric lignite beds and clays with roots
evidences. The uppermost part of the section is
constituted by 50 cm thick lagoonal clay with shell
debris that records the Apectodinium acme.
Global organic geochemical, palynofacies and
isotopic analyses were performed on thirty samples.
The total organic carbon of this section is ranging
from 0.5 % for OM-poor-clays to 45 % for lignite levels.
Hydrogen Index (from 6 to 210 mg HC/g TOC),
Oxygen Index (from 80 to 630 mgCO2/g TOC) and
Tmax values (from 410 to 430°C) show that the OM is
of Type III (terrestrial higher plants), and immature.
These results are reinforced by palynofacies
observations that show a large amount of lignocellulosic
phytoclasts in most of the samples. In the
uppermost shale the presence of many Apectodinium
species would suggest the continuity of the PETM in
marine deposits. Thus, the continental deposits would
represent a time interval that includes the uppermost
Paleocene and the basal part of the PETM.
Lipid biomarkers extracted from twenty five samples
were quantified and their hydrogen and carbon
isotopic composition were determined by GC-irMS.
Important changes in palynofacies, biomarker
assemblages and compound-specific isotopic data
are coincident with the CIE onset interval. This is
consistent with an important environmental
modification in the Vasterival area during the Early
Eocene that could be linked to the PETM climatic
change.
References
[1] Aubry, M. P., Ouda, K., Dupuis, C ., Berggren, W.
A., Van Couvering, J A., and the Members of the
Working Group on the Paleocene/Eocene Boundary,
2007. The Global Standard Stratotype-section and
Point (GSSP) for the base of the Eocene Series in the
Dababiya section (Egypt). Episodes 30 (4): 271-286.
[2] Zachos, J. C., Pagany, N., Sloan, L., Thomas, E.,
Billups, K., 2001. Trends, rythms, and aberrations in
global climate 65 Ma to Present. Science 292: 686–
693.
[3] Dupuis, C., Steurbaut, E., De Coninck, J. and
Riveline, J., 1998. The Western Argiles à Lignites
facies. In: M. Thiry and C. Dupuis (Eds.), The
Paleocene/Eocene boundary in Paris basin: the
Sparnacian deposits. Field trip guide. ENSMP Mém.
Sc. De la Terre, 34, 60-71.
350

P-212
Constraining stable carbon and hydrogen isotope excursions of
fire events from controlled burning experiments and
applications to the Triassic-Jurassic extinction event
Caroline Jaraula 1 , Kliti Grice 1 , Christiane Vitzthum von Eckstadt 1 , David Kelly 2 , Stephen
Clayton 1 , Luis Felipe Opazo 3 , Richard Twitchett 3
1 Curtin University, Bentley, Western Australia, Australia, 2 Curtin University, Margaret River, Western
Australia, Australia, 3 University of Plymouth, Plymouth, United Kingdom (corresponding
author:C.Jaraula@curtin.edu.au)
Controlled burning experiments were conducted
separately on Australian C3 eucalyptus trees (Marri,
Karri, Jarrah), conifer, wild oats &C4 spinifex &
kangaroo grasses to constrain isotopic shifts for
plants due to burning. Unburnt biomass, resulting
ashes & emitted volatile organic compounds (VOCs)
were analysed for changes in biomarker distributions
& their stable C & H isotopic compositions. The
biomass primarily contain odd/over/even
predominance of long chain n-alkanes (n-C27 to n-C33)
& their δ 13 C are consistent to those reported for C3 (-
22 to -42‰) & C4 (-9 to -29‰) plants (e.g. Rieley et
al., 1991). VOCs trapped on a TenaxTA resin were
thermally desorbed for compound-specific isotope
analyses & yield heavier δ 13 C (Table 1; Vitzthum von
Eckstaedt et al., 2010 submitted) than ash or
biomass. In the ash, the predominant n-alkanes are
shorter (n-C20 to n-C23) & useful in tracking fire
history. Experiments are underway to ascertain
Table 1. Compound-specific C isotope of VOCs
compound C3 plants δ 13 C (‰) C4 plants δ 13 C (‰)
Max Min Max Min
Benzene -26.3 -30.4 -14.7 -17.8
Toluene -26.3 -29.4 -14.0 -18.1
Ethylbenzene -26.3 -26.3
m-xylene -25.2 -26.8
Styrene -25.4 -29.0 -13.2 -16.4
Naphthalene -24.6 -26.5 -17.4 -18.3
Bulk (‰) -24.6 -30.4 -13.2 -18.3
whether these alkanes are from burnt wood or leaves.
On the average, δ 13 Cn-alkanes in C3 plant ash are 4‰
enriched compared to the unburnt biomass, whereas
C4 plant ash are depleted by 6.39‰. It is likely that
burning releases 13 C-depleted hydrocarbons occluded
in phytoliths, which are more prominent in C4
grasses, causing the overall depletion of δ 13 Cn-alkanes
in C4 ash consistent with previous studies (e.g. Krull
et al., 2003). These n-alkanes attributed to biomass
burning is investigated across several localities
bearing the Triassic/Jurassic boundary deposits (Tr/J)
as combustion biomarkers & fossil charcoal have
been reported in abundance. H & O indices from rockeval
pyrolysis of Tr/J classify St. Audries Bay, Engl&
as most immature, with the highest TOC typical of
Type II deposits compared with those from Lyme
Regis & Larne, Northern Ireland. Each locality is
characterised according to their change in terrestrial
plant biomarkers (i.e. waxes), marine-derived
biomarkers & HMW PAHs across Tr/J. Compoundspecific
δ 13 C & δD are tracked before, during & after
the extinction event (Grice et al., 2010 this volume;
Williford et al., 2010), compared with marine
carbonates, & their isotopic excursions hypothesized
to be influenced by massive fire events associated
with the extinction event.
References
Grice K, Nabbefeld B, Twitchett R, Summons RE,
Hays L, Williford K, McElwain J, Holman A, Böttcher
M 2011. Exploring mass extinction events
(Triassic/Jurassic & Permian/Triassic): Association
with global warming events. IMOG these
proceedings.
Krull E, Skjemstad JO, Graetz D, Grice K, Dunning W,
Cook G, Parr JF 2003. 13 C-depleted charcoal from
C4 grasses & the role of occluded carbon in
phytoliths. Org Geochem 34, 1337-1352.
Rieley G, Collier RJ, Jones DM, Eglinton G 1991. The
biogeochemistry of Ellsmere Lake, UK-I Source
correlation of leaf wax inputs to the sedimentary
lipid record. Org Geochem 17, 901-912.
Williford KH, Grice K, Holman A, McElwain JC.
Molecular & Stable Isotopic Signatures of Extreme
Heat Stress at the Triassic/Jurassic Boundary
Nature Geoscience Submitted Jan 2011.
Vitzthum von Eckstaedt C, Grice K, Ioppolo-Armanios
M, Chidlow G. δD & δ13C analyses of
atmospheric volatile organic compounds by
thermal desorption gas chromatography
isotope ratio mass spectrometry. Journ of
Chrom A. Submitted Jan 2011.
351

P-213
Biomarker proxies indicate silicic acid transport from the
Southern Ocean to southeastern Australia during interglacials
Raquel Lopes dos Santos 1 , Daniel Wilkins 2 , Patrick De Deckker 2 , Stefan Schouten 1
1 Royal Netherlands Institute for Sea Research (NIOZ), Texel, Netherlands, 2 The Australian National
University (ANU), Canberra, Australia (corresponding author:raquel.santos@nioz.nl)
The Southern Ocean (SO) has been
identified as having a major role in regulating
productivity at lower latitudes due to the formation of
different water masses that transport nutrients to
other oceans. For instance, silicic acid is thought to
be an important nutrient leaked from the SO during
glacials via intermediate waters and stimulate
phytoplankton production at mid to lower latitudes.
Additionally, planktonic foraminiferal carbon isotope
minima during deglaciations have been observed in
numerous cores from the southern hemisphere (SH)
mid-lower latitudes and has been suggested as an
isotopical signal of upwelled deep SO waters.
Here we compared planktonic � 13 C of
Globigerina bulloides with organic proxy records for
Proboscia diatom (1,14-diol index) and haptophyte
algae abundances (alkenones) from a core in the
Murray Canyons region of South East Australia (SEA)
to estimate the influence of deep SO waters in the
productivity of SEA. The Diol index is based on the
ration of 1,14 diols, lipids produced by Proboscia
diatoms and 1,15 diols, lipids related to unidentified
algae, possibly Eustigmatophytes. For haptophyte
abundances, we measured alkenones distribution,
lipid specific for this group of algae.
Our result shows that although SO waters
were upwelled during deglaciations, as revealed by
foraminifera isotopic minima, this did not result in
increased productivity. Instead, Proboscia diatoms
proliferated after the � 13 C minima during interglacials
and MIS 3, likely because silicic acid was leaked to
this area only after a SO decrease in diatom
production. Furthermore, haptophyte algae only
proliferated when Proboscia diatom productivity
decreased suggesting that silicic acid concentration
was insufficient for the needs of Proboscia.
Thus, our study suggests a wider
distribution of silicic acid leakage during glacialinterglacial
cycles likely controlled by the intensity of
water masses transporting this nutrient.
Fig. 1 Comparison of geochemical records of core
MD03-2607 from southeastern Australia with the opal
flux record of a core in the SO. A) U K‘ 37 sea surface
temperature, B) planktonic � 13 C of Globigerina
bulloides, C) Diol index, D) alkenones concentration
and E) Opal flux record from SO. Blue shaded area
indicate periods of depleted planktonic � 13 C
suggesting input of deep SO waters in the Murray
Canyons region.
� 13 C G.bull.
MD03-2607
Alkenones 37:2+37:3
[ng/g sed.]
OPAL flux TN057-13
[g cm -2 kyr -1 ]
1.5
1.0
0.5
0.0
-0.5
-1.0
-1.5
-2.0
80
60
40
20
0
7
6
5
4
3
2
1
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
Age [kyrs]
A
B
C
D
E
22
20
18
16
14
12
10
8
0.6
0.4
0.2
0.0
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
Diol index
MD03-2607
OPAL flux TN057-14
[g cm -2 kyr -1 ]
352
U K'
37 SST
[ 0 C]

P-214
Crenarchaeotal tetraether index of TEX86 as an indicator of
subsurface temperatures in the South China Sea
Guodong Jia 1 , Jie Zhang 1 , Jianfang Chen 2
1 Guangzhou Institute of Geochemistry, Guangzhou, China, 2 Second Institute of Oceanography, Hangzhou,
China (corresponding author:jiagd@gig.ac.cn)
Global core-top calibrations of the organic
paleothermometer, TEX86, have been performed
extensively. However, few data from the global
dataset were from the pacific, and some studies have
suggested the importance of local calibrations due to
the spatiality and seasonality of marine crenarchaeota
production. Here, we examined and calibrated the
TEX86 index in 32 surface sediments in the South
China Sea (SCS), a tropical marginal sea in the
western Pacific. Another widely used
paleothermometer, U37 K′ , having been calibrated
previously to reflect 0-30 m sea surface temperature
(SST) in the SCS, was also examined. TEX86 and
U37 K′ indices were correlated with averaged
temperatures of various depth levels and seasons.
Our results revealed a contrast that U37 K′ correlated
significantly with spring, autumn and winter SSTs,
whereas TEX86 showed strong correlations with
summer and autumn subsurface temperatures
(sSST). However, the strong signals of annual mean
temperatures in both the indices indicated that
seasonality in coccolith and marine crenarchaeota
growth seemed unlikely to bias them towards a
certain seasonal temperatures. The best curve fittings
of the TEX86 measurements were obtained for the
annual mean 30-125 m water column temperatures,
providing a linear equation of sSSTannual =
38.73*TEX86–5.04. Due to their indexing temperatures
of different water column intervals, the difference
between U37 K′ - and TEX86-derived temperatures
(ΔTAlkenone-GDGT) was hypothesized as a novel proxy
for upper ocean vertical thermal gradient in the SCS.
This hypothesis was confirmed by a strong correlation
between ΔTAlkenone-GDGT and the depth of thermocline
defined as the 18°C isothermal depth (Fig. 1).
Fig. 1 Correlation of the difference between U37 k′ - and
TEX86-derived temperatures (ΔTAlkenone-GDGT) with the
depth of thermocline (DOT) defined as the 18°C
isothermal depth.
353

P-215
Distributions of long-chain diols in surface sediments from the
North Pacific: possible revised diatom biomarker
paleothermometry
Madoka Kobayashi 1 , Ken Sawada 1 , Osamu Seki 2
1 Fuculty of Science, Hokkaido University, Sapporo, Japan, 2 Institute of Low Temperature Sciences,
Hokkaido University, Sapporo, Japan (corresponding author:kmadoka@mail.sci.hokudai.ac.jp)
Biomarker thermometers such as alkenone
unsaturation index (U K 37 and U K‘ 37) have been often
used for reconstructing paleo-sea surface
temperatures since 1980s. The alkenones are well
known to be derived from Haptophycean algae, which
are ubiquitous species in shallow to open ocean
areas at low to high latitude, and therefore, their
thermometers are powerful proxies in the almost over
the world oceans. However, it has been pointed out
that there were limitations for alkenone proxies;
physiological effect, deflection of temperature records
during the season of high production, variability of
source species, and so on.
More recently, several researchers [1] suggest new
algal biomarker thermometer, the ratios of 28 carbon
numbers (C28) and C30 1,14-diols in marine
sediments. These compounds are likely to be derived
from specific diatom Proboscia.
In this study, we examine the applicability of such
diatom biomarker thermometer from thirty six surface
sediments around the Pacific Ocean. Three
sediments were collected by multiple corer, while
thirty three sediments are a part of ODP cores.
Annual mean SST range is 5°C to 29°C. Freeze dried
sediment samples were extracted and extracts were
fractionated by silica gel chromatography before
analyses using GC/MS.
The diol thermometer is proposed as the ratio of
monounsaturated and saturated C28 to monounsaturated
and saturated C30 1,14-diols, called
Proboscia diol index (PDI), by the analyses of the
Proboscia cultures and the sediments in the Atlantic
and Southern Oceans [1, 2].
The C28 and C30 1,14-diols could be detected in
most of sediment samples in this study (Fig.1). We
compared some kinds of the 1,14-diols ratios and
annual mean SST. It was clear that the PDI were not
correlated with annual mean SST in the Pacific
sediments. In addition, the PDI were not correlated
with U K‘ 37 in the most of samples. On the other hand,
the unsaturation ratios of C28 1,14-diols and C30 1,14diols,
which were newly defined as UD28 and UD30,
respectively, were well correlated with annual mean
temperature and U K‘ 37. These UD28 and UD30 indices
can be revised paleothemometer by using diatom
biomarkers for PDI. These results might be attributed
to the differences of source species (and/or genetic
variations) producing the long-chain 1,14-diol in the
North Pacific from those in the Atlantic and Southern
Oceans as reported by literature [1, 2].
Fig.1 Partial mass fragmentograms of C28 (m/z 299)
and C30 (m/z 327) 1,14-diols in a surface sediment
from the northwestern Pacific off northern Japan.
References
[1] Rampen, S.W., Schouten, S., Schefus, E.,
Sinninghe Damste, J.S. (2009) Organic
Geochemistry 40, 1124-1131.
[2] Willmott, V., Rampen, S.W., Domack, E., Canals,
Sinninghe Damste, J.S. Schouten, S.(2010)
Antarctic Science 22(1), 3-10.
354

P-216
A Pleistocene-Holocene transgressive sediment sequence in the
southern North Sea coast area seen from a biomarker
perspective
Depth (m)
0
2
4
6
8
10
12
14
16
18
Grain size
Jürgen Köster, Fenja Müntinga, Jürgen Rullkötter
ICBM, Carl von Ossietzky University of Oldenburg, Oldenburg, Germany (corresponding
author:juergen.koester@icbm.de)
Biomarker investigations of a 20-m sediment core
from the coast of the southern North Sea reveal
differences in the marine and terrestrial sources of
organic matter between Pleistocene sediments,
Holocene channel fill deposits and modern intertidal
sediments.
A sediment core taken in the back-barrier area of the
C 20:1 HBI
[µg/g TOC]
Mud Sand Sh/X 0 2 4 6 8 10 12
C 37 Alkenones
[µg/g TOC]
0 5 10 15 20 25
Temperature
[°C]
8 10 12 14 16
ACL 23-31
26 27 28
20
Fig. 1: Lithological core log (green: mud, yellow: sand, orange: shells and gravel), depths profiles of selected
biomarkers and temperatures calculated from C37 alkenone distributions (ACL: average chain length index).
island of Spiekeroog (Germany) comprises a
transgressive sequence of Pleistocene sands at the
bottom, ca. 9 m of mud-rich sediments (filling up the
Pleistocene paleo-relief in the course of the Holocene
transgression), and 3.5 m of modern tidal-flat sands
on top.
Biomarkers in the channel sediments are
characterized by compounds of marine origin like C37
and C38 alkenones derived from Haptophyte algae
and monounsaturated C20 highly branched
isoprenoids (HBI; five isomers) originating from
diatoms. Perylene and a series of aromatized
triterpenoids (Freemann et al. 1994) occur almost
exclusively in the channel sediments and are possibly
related to microbial activity (Beck et al. 2011)
Different sources and transport processes for
terrestrial organic matter are indicated by the
abundances of pentacyclic triterpenoids. Further, the
distribution patterns of n-alkanes show differences in
the Holocene and Pleistocene sediments. This
indicates distinct units within the stratigraphically
poorly defined Pleistocene sands.
Elevated alkenone-derived temperature data in the
channel deposits are consistent with the channel
filling during times of relatively warm climatic
conditions (Atlantic period, ca. 7500-5000 a BC) and
of rapid sea-level rise.
References:
Beck et al. (2011) Biogeosciences 8, 55-68
Freemann et al. (1994) Org. Geochem. 21, 1037-49
355

P-217
The Vinylguaiacol/Indole or VGI ("Veggie") Ratio: Assessing
Relative Contributions of Terrestrial and Aquatic Organic Matter
to Sediments
Michael Kruge, Kevin Olsen, Jaroslaw Slusarczyk, Elaine Gomez
Montclair State University, Montclair (NJ), United States of America (corresponding
author:krugem@mail.montclair.edu)
In studies of the organic matter (OM) fraction of
marine, estuarine, fluvial, or lacustrine sediments, one
of the most fundamental distinctions to be made is
that between terrestrial and aquatic OM. To
supplement the parameters commonly used for this
purpose (e.g., C/N and stable isotope ratios), we
proposed the Vinylguaiacol/Indole or VGI ("Veggie")
ratio, defined as [vinylguaiacol / (indole +
vinylguaiacol)] using data produced by analytical
pyrolysis-gas chromatography/mass spectrometry of
dried, homogenized sediment samples [1]. The ratio
employs the peak areas of these two compounds on
the mass chromatograms of their molecular ions (m/z
150 and 117, respectively). Major pyrolysis products
of terrestrial plant lignin include a variety of
methoxyphenols, notably 4-vinylguaiacol. In contrast,
aquatic algae and bacteria characteristically produce
distinctive organonitrogen compounds upon pyrolysis,
particularly indole, derived from the amino acid
tryptophan. The end member VGI ratio value of 1.00
is nearly obtained for reference land plant matter,
such as maple wood (Fig. 1d). The end member
value of 0.00 is obtained for cultured microbes,
including Escherichia coli (Fig. 1a). Vinylguaiacol and
indole are commonly detected in Recent sediment
pyrolysates. We hypothesized that their relative
quantities therein should be proportional to the
contributions of land plant and aquatic OM,
respectively [1]. While soil microbes in terrestrial OM
would lead to a diminution of VGI values, stable
isotope and C/N ratios would likely be similarly
perturbed.
Systematic variations in VGI ratio values are
observed among estuarine sediments from southern
New York and New England (USA). Samples taken
from Spartina peat marshes at the mouths of major
rivers entering Long Island Sound have high (> 0.8)
VGI ratio values. Jamaica Bay (New York), behind an
Atlantic barrier island and with marsh islands and
multiple urbanized tidal creeks, displays a very wide
VGI range (Fig. 1b,c), affected by proximity to stands
of marsh vegetation, bathymetry, and sediment grain
size. Sediments from New Haven (Connecticut)
harbour show a diminution in VGI values from 0.66 at
the mouth of a river in the innermost harbour to 0.08
at the harbour entrance over a distance of only 4 km,
as terrestrial influences wane moving towards open
water. In Long Island Sound, deep water sediments
show a strong predominance of aquatic OM (VGI
about 0.05), while nearshore sediments collected
close to the mouths of rivers have a greater terrestrial
OM component (VGI of 0.15 to 0.23). The results
demonstrate a precipitous decrease in the relative
amounts of unaltered land plant OM in the offshore
direction, but also that a minor fraction persists in
deeper water environments.
Figure 1. Partial summed m/z 117 + 150 mass
chromatograms of pyroysates of sediment samples
and reference biological materials. I: indole; VG:
vinylguaiacol. VGI ratio values are given for each.
[1] Micic et al., 2010, Org. Geochem. 41:971-974.
356

P-218
Rainfall variability over NW Africa during the last glacialinterglacial
cycle: a δD record of the last 120 ka
Rony R. Kuechler, Lydie Dupont, Britta Beckmann, Enno Schefuß
MARUM - Center for Marine Environmental Sciences, University of Bremen, Bremen, Germany
(corresponding author:kuechler@uni-bremen.de)
Palaeoenvironmental studies of NW African climate
and vegetation changes during the Pleistocene
suggest periodical alternations of humid and arid
conditions [3]. For the last 120 ka, three distinct wet
intervals, i.e., the Holocene African Humid Period, a
period within Marine Isotope Stage (MIS) 3 and the
early MIS 5, were inferred to have experienced much
wetter conditions than the present [1; 2]. It has been
proposed that these humid periods reflect favourable
conditions for mammalian and hominid migrations out
of Africa [1]. Moreover, it has been shown that these
humid events were coupled to maximum summer
insolation in the northern low-latitudes causing strong
monsoonal rainfall with additional influence of highlatitude
climate variability [3]. In particular, the Atlantic
meridional overturning circulation and the associated
heat transport appear to be of main importance for
controlling vegetation distributions [1].
The purpose of this study is to decipher rainfall
variability over NW Africa during the last glacialinterglacial
cycle (last 120 ka). Previous studies [e.g.,
1] infer humidity changes from vegetation type
changes and dust fluxes, but so far, continental
palaeo-hydrologic conditions have not been assessed
directly. Therefore, a molecular isotopic approach will
be applied by using hydrogen, as well as stable
carbon isotope analyses on terrestrial plant waxes.
These compounds will be extracted from deep-sea
sediments, cored off Mauritania at ODP Site 659. This
site is located below the tracks of the African Easterly
Jet and the Northeast Trade Winds to record
environmental shifts of the Sahara/Sahel transition.
The hydrogen isotopic changes of land-derived nalkanes
will be used as a proxy for past rainfall
variability, as applied successfully by Niedermeyer et
al. (2010) for the last 44 ka. Additionally, the δ 13 C
signature of the same compounds will be analysed to
reconstruct variations in vegetation composition
(C3/C4 plants), whereas the accumulation rates of
these compounds will provide information on density
of the vegetation cover and aeolian transport strength.
Furthermore, sea-surface temperatures (SST) will be
estimated by using the U k‘ 37 Index of alkenones to
correlate continental climate with SST. These results
will be compared with palynological data and with
both δ 13 C of benthic foraminifers and dust fluxes
covering this time-interval. The δ 13 C of benthic
foraminifers will be used to assess deep-ocean
circulation changes. In this way, we tend to a better
understanding of the NW African hydrological cycle
during the last glacial-interglacial cycle, its relation to
SST and Atlantic circulation changes, as well as to
identify potential feedbacks between hydrology,
vegetation changes and dust export.
References
[1] Castañeda, I.C., Mulitza, S., Schefuß, E., Lopes
dos Santos, R.A., Sinninghe Damsté, J.S. & Schouten, S.
(2009): Wet phases in the Sahara/Sahel region and human
migration patterns in North Africa.- PNAS 106(48), 20159-
20163.
[2] Niedermeyer, E.M., Schefuß, E., Sessions, A.L.,
Mulitza, S., Mollenhauer, G., Schulz, M. & Wefer, G. (2010):
Orbital- and millenial-scale changes in the hydrologic cycle
and vegetation in the western African Sahel: insights from
individual plant wax δD and δ 13 C.- Quat. Sci. Rev. 29, 2996-
3005.
[3] Tjallingii, R., Claussen, M., Stuut, J.-B.W.,
Fohlmeister, J., Jahn, A., Bickert, T., Lamy, F. & Röhl, U.
(2008): Coherent high- and low-latitude control of the
northwest African hydrological balance. Nat. Geosci. 1, 670-
675.
357

P-219
The age and palaeoenvironmental conditions spanning the
Permian/Triassic boundary in the northern onshore Perth Basin
by using biomarker distributions and stable isotopes (C, H)
Mojgan Ladjavardi 1 , Kliti Grice 1 , Chris Boreham 2 , Dianne Edwards 2 , Ian Metcalfe 3 , Roger
Summons 4
1 WA Organic and isotopic Geochemistry centre,Curtin university of technology, Perth, WA, Australia,
2 Geoscience Australia, Canberra, Australia, 3 Schools of Environmental and Rural Science,University of New
England, NSW, Australia, 4 Massachussetts Institue of Technology, Earth and Planetary Sciences,
Cambridge, United States of America (corresponding author:M.Ladjavardi@curtin.edu.au)
The Perth Basin petroleum system has been
intermittently explored for the last few decades,
resulting in the production of gas and oil from several
onshore fields (e.g. Summons et al., 1995). The
effective source rock for petroleum in the Perth Basin
is the marine Kockatea Shale, with the hydrogenrichest
interval being the Sapropelic Unit of the Hovea
Member (Thomas et al., 2004). The Perth Basin in
southwest Western Australia (WA) is a deep, north to
south trending basin, extending over 1,000 km from
Geraldton to the north of Perth. The Perth Basin
sediments comprise of rocks of Permian−Early
Cretaceous in age. The current perception is that the
area is gas prone and has been challenged with the
recent discovery of the near-shore Cliff Head oil field.
The Dongara gas field in the onshore Perth Basin
contains more than half the oil and gas reserves. The
Perth Basin sediments used in this study are from the
Senecio-1 core which is located approximately 15.5
km from the north of Dongara. Stable carbon and
hydrogen isotopic composition of biomarkers
measured by compound specific isotopic analysis
(CSIA) has been shown to be an effective tool for
establishing biogeochemical changes in the early
Triassic (e.g. Nabbefeld et al., 2010). In the present
study bulk geochemical, biomarker and CSIA of
biomarkers are used to restrain the age and
palaeoenvironmental conditions spanning the Triassic
in the northern onshore Perth Basin and to compare
these results with the Hovea-3 drill core ‗type-section‘
(Grice et al., 2005a). For this purpose 31 samples
from the Senecio-1 cored at 1 m spacing were
selected. The ages of the samples have been
determined by conodont biostratigraphy. Rock-Eval &
TOC analyses have been performed to identify the
type and maturity of organic matter and to evaluate
the petroleum potential of these samples. The
samples were analysed following the methodology of
Grice et al. (2005b). Each sample was ground to a
fine powder and extracted using an Accelerated
solvent extractor. The extracts were separated into 6
fractions by liquid chromatography. Saturate and
aromatic hydrocarbon fractions were characterised by
GC-MS. The saturated hydrocarbon fractions were
separated from branched and cyclic hydrocarbons by
treating with 5A molecular sieves and CSIA of
biomarkers was performed for these fractions. Bulk
stable isotopic compositions were measured on the
kerogens isolated from the extracted powders. The
data is consistent with Hovea-3 for both Rock-Eval
and kerogen type. � 13 C of the bulk organic matter is
consistent with land plant derived material and
phytoplanktonic, the change in stable isotopes is not
as abrupt as shown in Hovea-3.
References
Grice, K., Cao C., Love G.D., Bottcher M.E., Twitchett R.,
Grosiean E., Summons R., Turgeon S., Dunning W. J., Jin
Y., 2005a. Photoc Zone Euxinia during the Permian-Triassic
Superanoxic Event. Science 307,706-709.
Grice, K., Summons, R.E., Grosjean, E., Twitchett, R.J.,
Dunning, W., E., Wang, S.X., Boettcher, M.E., 2005b.
Depositional conditions of the northern onshore Perth Basin
(Basal Triassic). Australian Petroleum Production and
Exploration Association Journal 45, 263-273.
Nabbefeld, B., Grice, K., Twitchett, R.J., Summons, R.E.,
Hays, L., Boettcher, M.E., Asif, M., 2010. An integrated
biomarker, isotopic and palaeoenvironmental study through
the late Permian event at Lusitaniadalen, Spitsbergen. Earth
and Planetary Science Letters 291, 84-96.
Summons R.E., Boreham, C.J., Foster, C.B., Murray, A.P.,
Gorter, J.D., 1995. Chemostratigraphy and the composition
of oils in the Perth Basin, Western Australia. Australian
Petroleum Exploration Association Journal 35, 613-632.
Thomas, B.M., Willink, R.J., Grice, K., Twitchett, R.J.,
Purcell, R.R., Archbold, N.W., George, A.D., Tye, S.,
Alexander, R., Foster, C.B., Barber, C.J., 2004. Unique
marine Permian-Triassic boundary section from Western
Australia. Australian Journal of Earth Sciences 51(3), 423-
430.
358

P-220
A multiproxy high-resolution approach for the reconstruction of
sea surface temperatures of the last 500 years at the southern
Italian shelf
Arne Leider 1 , Anna-Lena Grauel 2 , Kai-Uwe Hinrichs 1 , Stefano M. Bernasconi 2 , Gerard
J.M. Versteegh 1
1 Org. Geochemistry Group, MARUM Center for Marine Environmental Sci. & Department of Geosciences,
University of Bremen, Bremen, Germany, 2 Geological Institute, ETH Zürich, Zürich, Switzerland
(corresponding author:arneleider@uni-bremen.de)
The southern Italian shelf harbors excellent sites for
high-resolution paleoenvironmental reconstructions [1
and references therein]. Furthermore, Italy provides a
unique archive of instrumental and historical records
of climate and environment in the Mediterranean.
Previous core-top calibrations along the southern
Italian shelf showed clear discrepancies between sea
surface temperature (SST) proxies based on the U K‘ 37
and TEX86 indices as well as � 18 O of the planktic
foraminifer G. ruber (white) (Fig. 1A-D). The
alkenone-based SSTs reflect maxima in haptophyte
production during colder seasons. The TEX86-derived
temperatures increase with distance from shore, so
that at least offshore TEX86-derived SSTs reflect
summer temperatures in the stratified and oligotrophic
water column of the Ionian Sea [2]. � 18 O based
temperatures of G. ruber (white) also reflect a
summer signal but variations seem to be influenced
offshore by changes in water depth habitat and
salinity of Ionian Sea waters [3].
In this study we have extended the previous
temperature proxy comparison [2] to a time series
using a core from the southern Italian shelf covering
the last 500 years with a 3-year sample resolution
(39.76°N, 17.89°E, 173 m water depth).
The SST proxy signals show a high variability during
the last 500 years with amplitudes of up to 3°C that
could not be explained by variations in regional
instrumental temperature records alone. The
alkenone-based temperatures (14.6-19.4°C; Fig. 1E)
are up to 5°C lower compared to TEX86 temperatures
(18.0-22.0°C). However, both proxies show covariations
with maxima at 1500 AD, 1800 AD and a
decrease in SST during the last century which
contrasts with the global temperature trend [e.g., 4]. In
general, � 18 O based temperatures (15.9-21.9°C)
agree with TEX86 SST estimates, but show periods
with opposing trends. We speculate that these reflect
variations in the balance between near-coastal and
more saline Ionian Sea waters from the Eastern
Mediterranean partly affecting the � 18 O composition
and carrying a high TEX86 temperature signal.
References
[1] Versteegh, G.J.M., de Leeuw, J.W., Tarricco, C.,
Romero, A. (2007) Geochem. Geophys. Geosyst. 8,
doi:10.1029/2006GC001543.
[2] Leider, A., Hinrichs, K.-U., Mollenhauer, G., Versteegh,
G.J.M., (2010) Earth Planet. Sci. Lett. 300, 112-124.
[3] Grauel, A.L., Bernasconi, S.M., (2010) Mar.
Micropaleontology 77, 175-186.
[4] IPCC (2007) WG1, Cambridge Univ. Press, New York.
Fig. 1. Distribution of sea surface temperatures (A-D) based on annual mean satellite data and the temperature proxies
U K‘ 37, TEX86 and � 18 O of G. ruber (white) in surface sediments at the southern Italian shelf [adapted from 2, 3]. E) Depth
profile of alkenone-based SSTs in core GeoB 10709-4, black curve indicates 3-point running mean.
359

P-221
Differences in distribution of core lipids amongst intact polar
tetraether lipids and its implications for the TEX86
paleothermometer
Sabine K. Lengger 1 , Ellen C. Hopmans 1 , Angela Pitcher 1 , Gert-Jan Reichart 2 , Jaap S.
Sinninghe Damsté 1,2 , Stefan Schouten 1,2
1 NIOZ Royal Netherlands Institute for Sea Research, 't Horntje, Netherlands, 2 Utrecht University, Utrecht,
Netherlands (corresponding author:sabine.lengger@nioz.nl)
The TEX86 is an increasingly used paleotemperature
proxy and relies on the fact that temperature affects
the number of cyclopentane moieties in
thaumarchaeal membrane lipids (glycerol dibiphytanyl
glycerol tetraether lipids, GDGTs). In living Archaea,
these lipids are present as intact polar lipids (IPLs)
with sugar- and/or phosphate-containing groups
attached to the core lipids (CL). IPL-GDGTs are often
seen as diagnostic for living Archaea. It has been
shown that IPL-derived GDGTs often have TEX86values
higher than those of CL-GDGTs (e.g. Peru
Margin [1]), suggesting that the distribution of in situ
produced GDGTs differs from that of fossil GDGTs.
In this study, we examined the underlying causes for
observed differences between TEX86-values of CL
and IPL-GDGTs. We isolated IPL-GDGTs, from
Arabian Sea sediments from different water depths
and bottom water oxygen concentrations, according
to head groups, by preparative HPLC. Monohexose-,
dihexose- and hexose, phosphohexose-GDGTs were
subjected to hydrolysis. Ring distributions and TEX86
of the resulting IPL-derived GDGTs were measured
by HPLC/APCI-MS. We observed large differences in
GDGT-composition amongst head groups: the CLs
GDGT-2 and -3 (numbers indicate the number of
cyclopentane moieties) are predominantly associated
with glycolipids, while CL GDGT-1 is associated
predominantly with a phosphoglycolipid. This
observation is in agreement with results from the
thaumarchaeotal culture Nitrosopumilus maritimus,
where acid hydrolysis of the dihexose-GDGTs did not
yield GDGT-1, contrary to the phosphohexose-
GDGTs [2].
We also investigated IPL-GDGTs of recently enriched
Thaumarchaeota and found strikingly similar results to
those of N. maritimus, i.e. GDGT-0, -1 and
crenarchaeol predominantly occurring as CL of a
hexose-phosphohexose GDGT-IPL, and GDGT-2, -3
and -4 as CLs of dihexose GDGT-IPLs. As a
consequence, the TEX86 shows a relation with the
relative amount of dihexose GDGT-IPLs, i.e.
increasing TEX86 with increasing amount of dihexose-
IPLs. Analysis of suspended particulate matter from
the Arabian Sea also showed a strong relation
between TEX86 values and the relative amount of
dihexose GDGT-IPLs.
Our results thus show that TEX86-values generated by
GDGTs derived from glycolipids are substantially
higher than those generated from the phospholipidderived
GDTGs. Consequently, the substantial
differences in preservation potential between
phosphoglycolipids and glycolipids [3], and perhaps
even within the class of glycolipids, will lead to
changes in TEX86 of IPL-GDGTs with progressing
degradation. Therefore, differences in TEX86 between
IPL-derived and CL-GDGTs do not necessarily
indicate differences in origin (e.g. synthesis
temperature or thaumarchaeal community).
Furthermore, the non-random distribution we find
implies the existence of mechanisms for linking
specific GDGTs to specific headgroups. A systematic
distribution of GDGTs amongst headgroups, in
conjunction with the dissimilar degradation rates of
the latter, is complicating TEX86 calibration with water
column SPM and rendering in-situ calibration with
culture-material difficult. In contrast, IPLs are already
mainly degraded to CL-GDGTs in core-top sediments
and therefore core-top calibrations are likely to be
more reliable.
References: [1] Lipp J. S., Hinrichs K. U. (2009)
Geochim Cosmochim Acta 73, 6816-6833.
[2] Schouten S., Hopmans E. C., Baas M., Boumann
H., Standfest S., Könneke M., Stahl D. A., Sinninghe
Damsté J. S. (2008) Appl Env Microbiol 74, 2433-
2440.
[3] Schouten S., Middelburg J. J., Hopmans E. C.,
Sinninghe Damsté J. S. (2010) Geochim Cosmochim
Acta 74, 3806-3814.
360

P-224
Diagenetic transformation of 2,3-dioxygenated triterpenoids
from higher plants in buried wood and sediments
Philippe Schaeffer 1 , Claude Le Milbeau 2 , Pierre Adam 1
1 Laboratoire de Biogéochimie Moléculaire - UMR7177 / Université de Strasbourg - CNRS, Strasbourg,
France, 2 Institut des Sciences de la Terre d'Orléans / Université d'Orléans, Orléans, France (corresponding
author:padam@unistra.fr)
Following the recent identification of novel aromatic
oleanane-related triterpenoids bearing an oxygenated
functionality at C-2 in buried oak wood (1, 2, 3a, 4a;
Fig. 1), a novel diagenetic transformation pathway of
2,3-dioxygenated triterpenoids widely distributed in
higher plants has been proposed [1] and involves
aromatization from ring D to ring A (as opposed to the
―classical― pathway starting from ring A; e.g. [2]).
These aromatic triterpenoids were indeed postulated
to derive from functionalized precursors such as 5a
and 6a occurring in oak as glycosides (e.g. [3]) We
report here the identification by mass spectrometry
(GC-(HR)MS) and NMR of some of the postulated
diagenetic intermediates (7a/b-14) in a series of
buried wood samples collected from riverine and
freshwater lake sediments.
GC-MS investigation of the solvent extracts of wood
samples shows that straight-chain lipids have almost
completely disappeared upon diagenetic alteration,
whereas C-2- and C-2,C-3- oxygenated triterpenoids
appear to be predominant along with steroids. In
particular, the structural assignment of the alcohols 7a
and 8a relies on NMR investigations and chemical
correlation with the ketones 3a and 4a. The
monoaromatic diols 9a and 10a, key intermediates in
the pathway leading from the biological triterpenes
(e.g. 5a and 6a) to C-2 oxygenated triterpenoids
presented in Fig. 1, could be recognized based on
mass spectrometry studies. In addition to these
triterpenoids belonging to the oleanane series, oak
wood samples proved to contain also ursane
analogues in varying amounts. Furthermore, the
identification of ring E demethylated analogues (3b,
4b, 7b-10b) in one wood sample suggests the
occurrence of functionalized molecule precursors
bearing, for instance, a carboxyl group at C-20 (e.g.
5b and 6b) from which the demethylated analogues
might derive by decarboxylation.
The variety of structural modifications (e.g. loss of
methyl groups, ursane vs. oleanane skeletons,
presence of aromatic rings) observed on the reported
C-2- and C-2,C-3- oxygenated triterpenes reflects the
structural variety of their parent molecules, and might
thus be interpreted in terms of biological source(s).
These triterpenoids might therefore be used as
specific chemotaxonomic markers for higher plant
species synthesizing C-2,C-3-oxygenated
triterpenoids.
Fig. 1: Diagenetic pathway leading from C-2,C-3- dioxygenated triterpenoid
precusors to C-2 oxygenated sedimentary triterpenoids. All the compounds
presented (except 5a/b and 6a/b) were detected in buried wood samples.
References
[1] C. Le Milbeau, P. Schaeffer, J. Connan, P. Albrecht, P. Adam
(2010) Org. Lett. 12, 1504-1507.
[2] G.A. Wolf, J.M. Trendel, P. Albrecht (1989) Tetrahedron 45, 6721-
6728.
[3] G. Arramon, C. Saucier, D. Colombani, Y. Glories (2002)
Phytochem. Anal. 13, 305-310.
361

P-225
The change of land plant derived n-alkane characteristics in
ocean margin sediments in relation to the distance from the
continent
Tanja Badewien, Jürgen Rullkötter
Institute of Chemistry and Biology of the Marine Environment (ICBM), Carl von Ossietzky University of
Oldenburg, P.O. Box 2503, D-26111 Oldenburg, Germany
(corresponding author: t.badewien@icbm.de)
The ocean is an important sink for terrigenous organic
matter transported off shore by wind and rivers. The
composition of the land plant derived organic material
varies due to changing environmental conditions on
the continent. Thus, marine sediments preserve a
record of continental vegetation and climate for
instance by the incorporation of land plant derived
biomarkers (e.g. n-alkanes). But it was postulated that
the biomarker characteristics may vary as a function
of the distance to the continent [1]. This possibly
obscuring effect on continental climate assessment
from sediment analyses is in the focus of this study.
The seven surface sediment samples investigated
were recovered off southwest Africa (approximately
26°S) from water depths between 100 and 4700 m
during RV Meteor cruise M76/1. The chain lengths
and isotopic compositions of long chain n-alkanes
were analyzed. In the course of the transect the
average chain length (ACL) of the odd carbon
numbered n-C27 to n-C33 alkanes is fairly uniform for
water depths from 100 to 3000 m but decreases
toward greater depths (Fig. 1). With ACL27-33
endmember data for C3 and C4 plants [2, 3] the
contribution by C4 plants was estimated. The results
indicate that the abundance of C4 plants decreases
from an exclusive C4 signal to 77% with increasing
water depth. These results are substantiated by
decreasing δ 13 C values of the n-alkanes.
The samples are located off a C4 plant dominated
area on the adjacent continent (Fig. 1). From the
continent the plant material is transported into the
ocean by roughly latitudinal winds during austral
winter. However, not only short-range but also longrange
eolian contributions have to be taken into
account. A higher proportion of C3 material at greater
water depths may be caused by a higher significance
of long-range transport from the hinterland with higher
C3 plant abundance. Thus, the differences in the
observed contributions by C4 plants are possibly due
to different catchment areas.
Fig. 1: Simplified present-day land cover map of
southwest Africa (based on [4]) with sampling
locations (rectangles), ACL27-33 of n-alkanes and the
calculated contribution by C4 plants to the sediment.
Arrows indicate generalised wind directions according
to [5].
However, the main statement that the plant material in
the sediments is derived from a C4 dominated area
remains valid whatever sample is considered.
References
[1] Rommerskirchen et al., 2003, Geochem. Geophys.
Geosyst. 4, 1101.
[2] Vogts et al., 2009, Org. Geochem. 40, 1037-1054.
[3] Rommerskirchen et al., 2006, Org. Geochem. 37,
1303-1332.
[4] Mayaux et al., 2004, J. Biogeogr. 31, 861-877.
[5] Dupont, L.M., Wyputta, U., 2003, Quatern. Sci.
Rev. 22, 157-174.
362

P-226
Seasonal variations and characters of terrestrial particulate
organic matter in exterior rivers in Southeast China: inferred
from bulk properties and lignin phenols
Hongyan Bao, Ying Wu
State Key Laboratory of Estuarine and Coastal research, Shanghai, China (corresponding
author:baohy.ecnu@gmail.com)
Exterior rivers can significantly influence the
biogeochemical processes of the coastal area. East
China Sea accepts suspended sediment derived from
Yangtze River and Zhejiang Mountainous Rivers.
Though the sediment load of Zhejiang small rivers is
only 6% of the Yangtze river, but since the southeast
China is under the impact of subtropical monsoon,
water discharge during extreme events could be more
than 40 times of averaged water discharge,
sometimes 1000 times (Li et al., 2009; Yu, 2009),
those small rivers might transport significant
suspended particles during extreme event (Hilton,
2008). Previous studies regarding the terrestrial
organic carbon buried in East China Sea mainly
focused on Yangtze river (Zhu et al., 2008), studies
concerning those small mountainous rivers are
seldom. Here we present a study focuses on the
characters and seasonal variations of terrestrial
organic matter in Zhejiang mountainous river, and
compare to Yangtze river, find out the potential role of
these rivers in transporting terrestrial organic carbon.
Suspended particles of 7 rivers were sampled in
rainy season and dry season, respectively. The
elevation of these 7 rivers ranged from 500m to
1200m, with a drainage basin area varied from
1500km 2 to 55600km 2 . Bulk properties (POC% and
δ 13 C) and lignin phenols were analysed. POC%
showed higher variation in the rainy season than in
dry season, averaged at 2.0±1.6% and 1.0± 0.2% in
rainy season and dry season, respectively. Lignin
phenol concentrations (Σ8) ranged from 0.7 to
3.9mg/10g dw in the rainy season and 0.5 to
3.6mg/10g dw in the dry season. S/V and C/V ratio
suggested that terrestrial OM mainly came from the
mixture of angiosperm nonwoody and woody tissues,
in some rivers, e.g. Qiantang river, a significant
proportion was derived from woody tissues. The bulk
properties and lignin phenols signals of Qiantang river
are significantly different to that of other mountainous
rivers. This might caused by its relatively larger
drainage basin area (55600km 2 ) and lower
elevation/length ratio, so we exclude this river from
statistics analysis.
Statistics analysis indicated that though bulk
properties showed no differences between rainy
season and dry season, lignin phenol concentration
(Σ8) and degradation parameter ((Ad/Al)v) showed
significant differences between two seasons.
Generally, compared to dry season, in rainy season,
the particles contains more fresh terrestrial OM
(higher Σ8 and lower (Ad/Al)v ratio), which suggest
that during flood season, more fresh plant debris or
newly formed soils were rushed out from the drainage
basin. Compare to Yangtze river, in the rainy season,
bulk properties of these small rivers were close to that
of Yangtze river, but with a higher (Ad/Al)v ratio,
which inferred that during rainy season, small
mountainous river contains more soil derived OM than
Yangtze river; in the dry season, bulk properties and
lignin phenols all showed significant differences to
that of Yangtze river, with lower POC% and lower
terrestrial OM. The differences in chemical properties
between Yangtze river and Zhejiang river sediments
in different seasons may provide a way to quantify the
source of sedimentary organic carbon preserved in
the coastal region.
References
Li, B. G., Wang, C. H., Zhou, H. Q., Wu, X. Y.
and Yang, H., 2009. Adjustment mechanism on the
erosion and accretion of riverbed in the Jiaojiang
Estuary in Zhejiang Province, China. Acta
Oceanologica Sinica, 31, 89-100. (in Chinese)
Hilton, R. G., Galy, A., Hovius, N., Chen, M. C.,
Horng, M. J., and Chen, H.,2008. Tropical-cyclonedriven
erosion of the terrestrial biosphere from
mountains. Nature geoscience, 1, 759-762.
Yu, T., 2009. Overview of rivers into the sea in
Zhejiang Province and suggestions on the
management of the river-sea region and river-sea
delimitation. Journal of marine science ,27, 17-22. (in
Chinese)
Zhu, C., Xue, B., Pan, J. M., Zhang, H. S.,
Wagner, T. and Pancost, R. D., 2008. The dispersal
of sedimentary terrestrial organic matter in the East
China Sea (ECS) as revealed by biomarkers and
hydro-chemical characteristics. Organic chemistry, 39,
952-957.
363

P-227
Terrestrial organic matter in the sediments of the German Bight
– estimate of relative proportions using the BIT index in
comparison to other proxies
Anna Böll, Barbara Scholz-Böttcher, Jörn Logemann, Jürgen Rullkötter
Institut of Chemistry and Biology of the Marine Environment (ICBM), Oldenburg, Germany
The Branched and Isoprenoid Tetraether Index (BIT
index) is a recently developed proxy for estimating the
fluvial transport of soil-derived terrestrial organic
matter into marine sediments. The BIT index is based
on the relative abundance of terrestrially derived
tetraether lipids versus crenarchaeol of marine origin.
In this study, the distribution and sources of terrestrial
organic matter in the surface sediments of the
southeastern part of the North Sea (German Bight)
was investigated. The BIT index (analysed by
HPLC/MS adapted from [1,2]) was compared to wellestablished
proxies such as C/N ratios, stable carbon
isotopes ratios and n-alkane distribution patterns in
order to investigate the applicability of the BIT index in
the German Bight.
To assess the amount of terrestrial organic matter in
the sediments of the German Bight two binary mixing
models and a three end member mixing model were
applied [3]. The binary mixing models were based on
δ 13 C content and BIT index, respectively, and for the
three end-member mixing model δ 13 C values, BIT
index and C/N ratio were used (e.g. see Figure 1).
BIT values ranged from 0.29 to 0.89. The bulk proxies
applied, δ 13 C value and C/N ratio, ranged from -25‰
to -18.15‰, and from 1.71 to 6.91, respectively. Only
a weak correlation was found between BIT index and
other proxies. Overall, all proxies indicate a decrease
of terrestrial organic matter in the surface sediments
with increasing distance from the coast.
In contrast to open marine areas (3%-43%), the
sediments from the Jade Bay and the Elbe river
mouth contain high proportions of terrestrial organic
matter (32% to 77% and 55% to 66%, respectively).
Furthermore, it is shown that the terrestrial organic
matter is mainly derived from soil.
Although the BIT index and the other proxies show a
similar trend, BIT index values indicate higher
fractions of terrestrial organic matter in the surface
sediments than δ 13 C values.
Thus, the BIT index should only be used as a
qualitative proxy for the relative amount of terrestrial
organic matter in the German Bight.
Terrestrial OC [%]
100
90
80
70
60
50
40
30
20
10
0
South of Helgoland
Binary mixing model (BIT index)
Binary mixing model (� 13 C)
Three end-member mixing model
North of
Helgoland
99-101 99-102 99-103 99-104 10697 10685 10689 10691 10693 10695
Sample
40'
20'
54 o N
40'
20'
40'
North of
Helgoland
Helgoland
South of
Helgoland
8 o E
20' 40'
Figure 1: Estimate of the proportions of terrestrial
organic matter in the sediments of the German Bight
based on two end-member mixing models and on a
three end-member mixing model (based on δ 13 C
values, BIT index and C/N ratio).
References
[1] Hopmans, E.C., Schouten, S., Pancost, R.D., van
der Meer, M.T.J., Sinninghe Damsté, J.S., 2000.
Rapid Commun. Mass Spectrom. 14, 585-589.
[2] Hopmans, E.C., Weijers, J.W.H., Schefuß, E.,
Herfort, L., Sinninghe Damsté, J.S., Schouten, S.,
2004. Earth Planet. Sci. Lett. 224, 107-116.
[3] Weijers, J.W.H., Schouten, S., Schefuß, E.,
Schneider, R.R., Sinninghe Damsté. J.S., 2009.
Geochim. Cosmochim. Acta 73, 119-132.
9 o E
364

P-228
Soil organic matter in drylands: insights into selective
degradation?
Arnoud Boom 1 , Andrew S Carr 1 , Zoë Roberts 1 , Alex Cumming 1 , Brian M Chase 2 , Michael
E Meadows 3 , Matthew Britton 3
1 University of Leicester, Leicester, United Kingdom, 2 CNRS, Institut des Sciences de l’Evolution de
Montpellier, UMR 5554 Université Montpellier 2, France, 3 University of Cape Town, Capetown, South Africa
(corresponding author:ab269@le.ac.uk)
Warm conditions and strongly oxidising conditions in
semi-arid environments typically promote the rapid
turnover of the SOM pool in such regions. The theory
of selective degradation implies that the most labile
OM fractions are rapidly mineralised, resulting in the
preferential preservation of more recalcitrant OM (de
Leeuw et al 2006). The concept of recalcitrant OM in
soils is currently debated (Marschner et al. 2008). A
source of recalcitrant soil OM is potentially the
resistant leaf cuticles of succulent plants (cutan;
Boom et al., 2005). Cutan, an aliphatic biopolymer,
which is resistant to acid hydrolysis and base
saponification should produce soils characterised by
highly aliphatic OM. Despite debate concerning the
presence of cutan in samples of geological antiquity
(Gupta et al. 2007), we have isolated cutan in a
variety of dryland succulent plants from southern
Africa. The confirmation of this potential cutan source
in this semi-arid setting allows further study of cutan
existence/persistence in the wider geosphere.
Here, we examine the OM composition of
contemporary soils and sediments in the Succulent
Karoo of southern Africa. A programme of field
sampling provided plants and soils across a number
of major climatic and ecological transitions in this
region. SOM and plant cuticles were then
characterised by pyrolysis-GC/MS and FTIR
analyses.
Typical Succulent Karoo SOM comprises a diverse
array of plant-derived aliphatic and aromatic pyrolysis
products. These soils were taken from plots
containing plant genera containing cutan. There is
however a consistent occurrence of an aliphatic signal
extending beyond n-C30. This is the dominant signal in
a number of lipid-extracted soil residues (R1). Further
isolation of the most resistant organic fraction by
means of acid hydrolysis and saponification (R3)
reveals the persistence and enhancement of this
aliphatic signal in a number of samples. The wider
implications of these findings for SOM
turnover/preservation in dryland environments will be
discussed.
A) Isolated cutan pyrolysate from the succulent plant
Aloë jacksonii; B) Typical R1 pyrolysate from Karoo
soils, displaying a prominent aliphatic signal.
References:
Boom A. et al (2005) Cutan, a common aliphatic
biopolymer in cuticles of drought-adapted plants.
Organic Geochemistry, 36(4), 595-601.
de Leeuw, J.W. et al (2006) Biomacromolecules of
algae and plants and their fossil analogues. Plant
Ecology 182, 209-233.
Gupta, N.S., et al (2007) Experimental evidence for
the formation of geomacromolecules from plant leaf
lipids. Organic Geochemistry, 38(1), 28-36.
Marschner, B. et al (2008) How relevant is
recalcitrance for the stabilization of organic matter in
soils? J Plant Nutrition Soil Sci 171, 91-110.
365

P-229
Geochemical peculiarities of composition and structure of
heterocyclic components in bitumen extracts of organic matter
of lacustrine recent sediments
Lyubov Borisova 1 , Anatoliy Fomichev 2
1 Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation, 2 Siberian
Research Institute of Geology, Geophysics and Mineral Resources, Novosibirsk, Russian Federation
(corresponding author:BorisovaLS@ipgg.nsc.ru)
Investigations of the composition and structure of
asphaltene components (AC) in the recent sediments
are not numerous [1, 2 and oth.]. This work is aimed
at revealing the peculiarities of the composition and
structure of AC in organic matter (OM) at the stage of
their initiation during diagenesis.
The subjects of inquiry are asphaltenes and
asphaltogene acids of OM from peats in the fields of
the Novosibirsk and Tomsk regions and sapropels
from the lakes of the Kulunda salt zone (West
Siberia). Lacustrine sediments are composed of siltsand,
sand-silt muds and sapropels. Extraction of
bitumen extracts of bottom sediments and AC was
performed according to the procedure developed by
V.P. Danilova [3 and oth.]. The composition and
structure of AC were examined by a complex of
physicochemical methods: elemental and x-ray
diffraction analyses, IR-, NMR-spectrometry, EPR,
and electron microscopy.
Based on data of elemental analysis, AC of
peats, as compared to AC of bottom sediments are
enriched in carbon, are depleted in hydrogen and
heteroatoms, and they have lower values of atomic
ratios H/C (1.7 – 1.9 against 1.8-2.0 for bottom
sediments). Asphaltogene acids relative to
asphaltenes for all samples are notable for the high
content of heteroelements and lower content of
hydrogen.
Based on the results of IR-, and NMRspectroscopy,
the structure of AC from OM of
diagenetic stage is characterized by a low degree of
aromaticity (averaging 0.2) as compared to AC from
OM of fossil sediments (0.5 – 0.8) [4 and oth.], high
carbon content in the long paraffin chains and
oxygen-containing groups. Aromatic structures are
represented by benzene. AC are almost identical and
by their structure resemble aliphatic esters and, to a
lesser extent, aromatic esters (of phthalate type).
EPR of AC from recent lacustrine sediments
indicates a low concentration of paramagnetic centers
(PMC) (10 15 pmc/g against 10 18 pmc/g for AC of OM
at the early stages of catagenesis [4]). A hyperfine
structure has been identified, which, judging from a
number of lines, is characteristic of copper linked with
4 atoms of nitrogen. A spectrum of tetravalent
vanadium (V +4 ) in AC of recent lacustrine sediments
has not been identified [4]. Spectroscopy results in
the visible region confirm the presence of copper
porphyrins and the absence of VO-porphyrins in AC
of recent lacustrine sediments. Previously, chlorines
have been identified in them by M.M. Gubina [5].
Based on x-ray diffraction data, AC of recent
lacustrine sediments show no crystal-like structure
(there are no clearly defined ordered hexagonal
structures), and they are composed of amorphous
mass. This is confirmed by electron microscopy: a
fibriform-lumpy structure is observed, representing the
onset of asphaltene initiation in diagenesis, while AC
of fossil sediments show a graphite-like structure.
Thus, during diagenesis, not asphaltenes proper
are produced, but only their precursors,
protoasphaltenes, less condensed compounds with
looser structure and higher content of
heteroelements. The chemical and supramolecular
structures of protoasphaltenes are predetermined by
the composition of the initial lipid-lipoid fraction of
living matter and are controlled by the geochemical
environment of accumulation in diagenesis.
References
[1] Galimov E..M., Kodina L.A. Investigation of organic
matter and gases in sedimentary strata of the World Ocean
bottom. – M.: Nauka. - 1982. - 288 p.
[2] Chernova, T.G., et al. (1974) Geokhimiya, N 8, 24-29.
[3] Kontorovich, A.E. (2004) Sketches of theory of naphthide
genesis (in Russian), SB RAS, Novosibirsk
[4] Borisova, L.S. (2004) Russian Geology and Geophysics
45, N 7, 884-894.
[5] Gubina, M.M. (1999) Organic geochemistry of oilgenerating
rocks of West Siberia (in Russian), IPG SB RAS,
Novosibirsk, 144-146.
366

P-230
Characterization and dating of soil humic material in holocene
progradational sequence, n. Santa Catarina Littoral, Brasil
Tomasz Boski 1 , Heike Heike Knicker 2 , Francisco Javier Gonzalez Villa 2 , Trinidad
Trinidad Verdejo 2 , José António González-Pérez 2 , Rodolfo Angulo 3 , Maria Cristina
Souza 3
1 CIMA, Universidade do Algarve, Faro, Portugal, 2 IRNAS-CSIC, Seville, Spain, 3 LECOST-Universidade
Federal do Paraná, Curitiba, Brazil (corresponding author:tboski@ualg.pt)
Piçarras (a vernacular term for podzols) occur along
the South Eastern costal zone of Brazil between Rio
Grande do Sul and Rio de Janeiro States. Piçarras
are formed as a result of cemenentation of the soil B
horizon formed on mostly sandy littoral barrier
sediments covered by the lush Atlantic forest. The
cementing material is composed by the mixture of
sesquioxides (2-4%) and humic material exhibiting the
elemental C content between 1 and 3%, calculated
per dry weight of the sediment. It is assumed that the
colonization of the accreted littoral bodies by
vegetation occurred rapidly and contributed to the
accumulation of humic material.
Our study was carried out along a 3 km trench
profile, perpendicular to the shore line in Volta Velha
which is a private biological reserve area situated in
the municipal district of Itapoá, in the northeast of
Santa Catarina State, and is part of the area
considered as the Atlantic Forest Biosphere Reserve.
The investigated trench profile is also roughly
perpendicular to the front of prograding Holocene
barriers composed of fine to medium sand weekly
cemented by humic material and sesquioxides
produced by the weathering of heavy minerals. 14
samples were collected from the studied transect and
submitted to inorganic, and organic elemental
analyses, lipid extract GC-MS determination based on
flash pyrolisis and 13 C nuclear magnetic resonance
(NMR) characterisation of organic matter, which was
further dated by 14C AMS method .
Most of the intensity in the solid-state 13 C NMR
spectrum of the both VV1 and VV2 analysed samples
sample is detected in the chemical shift region of alkyl
C between 45 and 0 ppm. This regions is most
tentatively assigned to methylene groups i.e. in fatty
or amino acids but also in paraffinic structures.
Comparable high intensity is seen in the chemical
shift region of Carboxyl/carbonyl C, which is also
assignable to amide C. A smaller signal at 205 ppm
can be attributed to aldehyde or ketone C.
Considering the low ratio between the intensity of in
the carboxyl/carbonyl C region and the alkyl C region,
a high contribution of long chain alkyl structures is
unlikely. A further strong signal can be seen at 130
ppm, assignable to unsubstituted aromatic C. The
signal between 140 and 160 ppm derives from O/Naryl
C as it occurs in phenolic structures for example
of lignin or tannins. The signal at 55 ppm is only
visible as a shoulder and may derive from NH-C of
peptide structures but is also attributable to methoxyl
groups i.e. in lignin side chains.
The signal at 75 ppm in the chemical shift region
of O-alkyl C (110 to 60 ppm) originates most likely
from carbohydrates. The low relative contribution of
this signal indicates a high humification degree of the
sample VV1. Comparing the samples VV1 and VV2
we observed a clear time dependent decrease in the
carbohydrate content , most probably reflecting the
time of exposure of organic matter to bacterial
respiration.
Three AMS 14C datings of the B horizon material
taken at 80 cm depth, at the inland margin of the
accreted area ca 2.6 km, 1.4 km and 0.5 km from
shore gave the ages of 6.890-6.670 (VV1), 2.690-
2.340 (VV2) and 1300 – 1170 (VV7) Cal BP. The
starting point of the sequence corresponds to the
period antecedent to the mid-Holococene highstand
which occurred between 5800 - 5000 Cal BP. The first
period of costal accretion embracing the time span
between the points VV1 and VV2 corresponds to a
slower (0.28 m/yr) progradation. Indeed the
deceleration of the sea level rise provided only limited
space for accommodation of sand bodies. During the
second more recent period marked by the samples
VV2 and VV7 the accretion is much faster (0.64 m/yr)
the because the lowering of the RSL permitted the
formation of the broad prograding barriers. The
presented results after further confirmation and
refinements in sampling technique open new
perspectives for the development of a new
geochronological tool based on dating of fast
accumulates soil organic matter.
367

P-231
Bacteriohopanepolyol content of pasture soils in NE England
Martin Cooke, Helen Talbot
Newcastle University, Newcastle Upon Tyne, United Kingdom (corresponding author:M.P.Cooke@ncl.ac.uk)
Bacteriohopanpolyols (BHPs) are a group of
membrane lipids synthesized by a wide range of
prokaryotes with a high degree of structural specificity
relative to bacterial source. BHPs are pentacyclic
triterpenoids with a 5-carbon side chain which can
contain 4, 5 or 6 functional groups (Tetra-, Penta- and
Hexa-functionalisation), predominantly hydroxyls,
amine or composite groups such as amino sugars. In
addition to the functional groups BHPs can be
methylated at either C-2, C-3 or C-12 and unsaturated
at C-6 or C-11.
Recent investigations into the BHP content
of soils have shown a high number of BHP structures
(e.g. Cooke et al., 2008). This observation opens up
the possibility that variations in BHP content of soils
may be used as proxies for a variety of bacterially
driven processes in soils.
The Palace Leas experimental pasture plots
(Cockle Park Farm, Northumbria), consist of 14 plots
that have received consistent fertilizer treatments
since 1896. The plots studied here have received: no
fertilizer, manure, potassium, nitrogen or phosphorous
fertilizer only. In this study we investigated the semiquantitative
BHP concentration (indicated as [BHP])
of pasture soils in Northern England. BHPs were
extracted from freeze dried soils and analysed by
HPLC-MS n (Cooke et al., 2008).
Investigation into the [BHP] of the plots
during 2006 and 2007 identified 38 different BHPs
with the distribution being dominated by 5 compounds
(Fig.1):, bacteriohopanetetrol (m/z 655), aminotriol
(m/z 714), adenosylhopane (m/z 746),
adenosylhopane type-1 (m/z 761) and
bacteriohopanetetrol cyclitol ether (m/z 1002 ce).
Principle component analysis identified a
separation based upon their BHP profile indicating
that the different fertilizer treatments had influenced
the BHP producing bacterial population of the plots.
An apparent annual cycle to the BHP concentration
with peaks during the summer and autumn months
and significant reduction in BHP concentration during
the winter was observed at all depths (Fig. 2).
Analysis of the variation in [BHPs] during this
time indicated that there was a rise in the
concentrations of most BHPs during this time implying
a rise in total BHP producing bacterial population or
an increase in BHP production by the existing
bacterial population.
These observations suggest that analysis of
the [BHP] in soils could reflect active BHP-producing
populations and therefore provide insight into current
population dynamics and environmental factors.
µg BHP/gTOC
350
300
250
200
150
100
50
0
655
2Me 669
712
714
2Me 728
Palace Leas Plot 2 May 2006
3Me 728
772
830
844
746
760
m/z
761
775
0-5 cm 5-10 cm 10-15 cm
1002 ce
1002 glu
2Me 1016
3Me 1016
1060
2Me 1060
3Me 1060
1086
1118
2Me 1132
Fig. 1. Plot 2, May 2006 [BHP]. Manure treatment.
BHPs are identified by the m/z value of the acetylated
form with amine containing BHPs being [M+H] and
other forms being [M+H-CH3COOH] (Talbot et al.,
2003).
µg BHP/gTOC
2500
2000
1500
1000
500
0
Jan 06, 0-5 cm
May 06, 0-5 cm
Oct 06, 0-5 cm
Jan 07, 0-5 cm
Palace Leas Plot 2, Total [BHP]
Jan 06, 5-10
cm
Fig. 2 Annual variation in [BHP], Plot 2 May 2006.
May 06, 5-10
cm
Cooke, M.P., Talbot, H.M., Farrimond, P., 2008.
Organic Geochemistry 39, 1347-1358.
Talbot, H.M., Squier, A.H., Keely, B.J., Farrimond, P.,
2003. Rapid Communications in Mass Spectrometry
17, 728-737.
Oct 06, 5-10
cm
Jan 07, 5-10cm
Jan 06, 10-15
cm
May 06, 10-15
cm
Oct 06, 10-15
cm
Jan 07, 10-15
cm
368

P-232
Some experimental results on the influence of clay minerals on
fossil organic matter transformation in soil and sediments
Coralie Biache, Thierry Chislain, Raymond Michels, Pierre Faure
UMR7566 G2R, CNRS, Nancy Université, Vandoeuvre-lès-Nancy, France (corresponding
author:Pierre.Faure@g2r.uhp-nancy.fr)
Because of their toxicity, the fate of Polycyclic
Aromatic Hydrocarbons (PAHs) is of uppermost
interest to agro- and hydrosystems investigations.
Polluted soils and sediments are the major source of
long term diffusion of PAHs in the environment.
Although artificial remediation solutions exist (thermal
desorption for instance) or are of current intense
research, their applications may often be problematic
in regards to the huge amount of polluted material to
be treated and their elevated cost. Hence, natural
recovery is often the only remaining perspective.
Therefore, it is important to understand the fate and
reactivity of PAHs during the evolution through space
and time of these complex systems.
Polluted soils and sediments are likely to be in
contact with air, where oxidative chemistry is active.
Thus, chemical air oxidation may be a major factor
influencing PAHs in soils and sediments.
In this perspective, we studied the artificial air
oxidation of coal tar, polluted soil and model
compounds. Air oxidation was conducted at 100°C in
sealed glass reactors periodically aerated after CO2
measurements.. Oxidation of a coal tar (essentially
composed by PAHs) reveals, after 6 months, a
decrease in the PAH concentration (~ 50% of 16 PAH
including in the US/EPA list). This decrease can not
be explained only by mineralization processes (CO2
production represents only 0,5% of initial COT).
Molecular investigations reveal the increase in the
oxygenated PAH concentration and mass balance
suggests the formation of a solid organic constituent.
The same experiments, carried out on a real soil
from an ancient coking plant site, reveal similar
results (decrease in PAH concentration, O-PAH
productions, weak mineralization and organic extract
decrease). However, the intensity of these
parameters is higher (especially PAH degradation and
CO2 generation). This more intense evolution in the
case of the soil can be explained by the occurrence of
reactive mineral phases absent in the coal-tar.
The air oxidation of the model compound
fluoranthene, a dominant PAH in coal tar, allowed to
investigate the major reactive pathways. Fluoranthene
was oxidized alone and in presence of different
mineral matrices representative of soils (quartz sand,
calcite, clay). The experiments show that very little
CO2 is formed. Instead, series of higher molecular
weight compounds could be evidenced by HLPC-
SEC—QTOF mass spectrometry. Indeed,
fluoranthene units follow an oxidative mineral
catalyzed polymerization process leading to the
formation of a carbonaceous residue. This result was
not expected, as in literature high activation energies
(and thus high pyrolysis temperature) are usually
considered in the oxidation process of PAHs.
We thus propose that the air oxidation catalyzed
by minerals may be a novel pathway to the
immobilization of PAHs in the subsurface.
369

P-233
Branched GDGTs in the Yenisei river catchment; the trans-
Siberian CBT/MBT signature of river and lake particulate matter
Cindy De Jonge 1 , Alina Stadnitskaia 1 , Georgy Charkashov 2 , Andrei Fedotov 3 , Alexander
Vasiliev 4 , Jaap S. Sinninghe Damsté 1
1 Department of Marine Organic Biogeochemistry, Royal Netherlands Institute for Sea Research (Royal
NIOZ), Texel, Netherlands, 2 All-Russian Research Institute for Geology and Mineral Resources of the World
Ocean (VNIIOkeangeologia), Ministry of Nat, St.Petersburg, Russian Federation, 3 Limnological Institute,
Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russian Federation, 4 Earth Cryosphere
Institute Siberian Branch of Russian Academy of Science, Tumen, Russian Federation (corresponding
author:cindy.de.jonge@nioz.nl)
Continental temperature reconstructions are
hampered by a lack of quantitative temperature
proxies. Weijers et al. (2007) described proxies that
allow to estimate both palaeo-soil-pH as palaeocontinental-temperature
based on branched GDGT
membrane lipid distributions [the methylation index of
branched tetraethers (MBT) and the cyclisation ratio
of branched GDGTs (CBT)]. These soil-derived lipids
can be recovered from ocean sediments, providing an
opportunity to reconstruct long-term climate changes.
In order to test the applicability of these new proxies,
they need to be further tested in geographically
contrasting settings, as for instance the Arctic region.
Therefore, we performed a detailed study on the
sources of soil GDGTs, mode of their transport, and
re-deposition in the Yenisei river – Kara Sea system
(Fig. 1). The Yenisei starts in the Asian Tuva and
flows through the Central Siberian Plateau into the
Arctic Ocean through the Kara Sea, covering different
climatic zones and biomes (tundra, taiga/boreal
forest). We determined BIT (Branched and Isoprenoid
Tetraether) and MBT/CBT indices in suspended
particulate matter (SPM) of the Yenisei river and their
geographical variation.
At 36 sites, 20 to 100L of water was sampled and
filtered to collect the SPM. Not only the Yenisei river
and its main tributaries were sampled, but also a
number of lakes in the Yenisei catchment. The BITindex,
describing the relative abundance of branched
GDGTs over aquatically produced crenarchaeol, of
the river SPM ranges between 0.18 and 1.00 (mean is
0.87), with values

P-234
Constraining the sources of dissolved and particulate organic
carbon to the Arctic Ocean using full-depth dual carbon isotope
profiles of DIC, DOC, and POC
David Griffith 1 , Ann McNichol 2 , Li Xu 2 , Timothy Eglinton 3 , Fiona McLaughlin 4 , Robie
Macdonald 4 , Kristina Brown 5
1 MIT/WHOI Joint Program in Oceanography, Woods Hole, MA, United States of America, 2 NOSAMS,
Woods Hole Oceanographic Institution, Woods Hole, MA, United States of America, 3 Dept. of Chemistry and
Marine Geochemistry, WHOI, Woods Hole, MA, United States of America, 4 Institute of Ocean Sciences,
Fisheries and Oceans Canada, Sidney, BC, Canada, 5 University of British Columbia, Vancouver, BC,
Canada (corresponding author:dgriffith@whoi.edu)
The ability to predict how the Arctic Ocean will
respond to a changing climate is hindered by our
limited understanding of the factors that control
organic carbon (OC) dynamics in this unique system.
Dual carbon isotope ( 13 C and 14 C) measurements are
a powerful tool for characterizing ocean water masses
and studying carbon cycling in a variety of marine
environments. As such, isotopic measurements
represent a great opportunity to improve our
understanding of the Arctic Ocean carbon cycle and
set a baseline for monitoring biogeochemical changes
that may occur in the coming decades. Yet there exist
only a few full-depth ocean profiles of coupled 13 C and
14 C measurements of dissolved and particulate OC
(DOC and POC), and none have been reported for
the Arctic Ocean. In this study we present full-depth,
dual isotope profiles of dissolved inorganic carbon
(DIC), DOC, and suspended POC at two sites in the
Canada Basin with different seasonal ice coverage
characteristics.
Our results are consistent with the dominant water
masses of the area, and point to the importance of
river discharge, sea-ice algae, OC sorption, lateral
particle transport, and the potential for
chemoautotrophic production. Although the two sites
have similar DI 13 C and DI 14 C profiles, the seasonally
ice-free site (CB4) has a depleted (older) 14 C
signature in the DOC, suspended POC, and sinking
POC pools compared to the perennially ice-covered
site (CB9). And unlike other ocean basins, suspended
POC in the Canada Basin is significantly younger
than sinking POC throughout the water column, which
raises questions as to the source of suspended POC
in the mesopelagic Arctic Ocean.
Figure 1. Profiles of � 14 C at a seasonally ice-free
station (CB4) in the Canada Basin.
371

P-235
Simulation of organic matter maturation in thermal waters by
model experiments
József Fekete 1 , Csanád Sajgó 1 , Áron Kramarics 2 , Zsuzsanna Eke 2 , Zoltán Kárpáti 1
1 Institute for Geochemical Research, Hungarian Academy of Sciences, Budapest, Hungary, 2 Eötvös Loránd
University, Joint Research and Training Laboratory on Separation Techniques, Budapest, Hungary
(corresponding author:feketej@geochem.hu)
Dissolved aromatic compounds in Hungarian thermal
waters were first reported and later described by
Kárpáti et al. [1, 2]. Among the identified compounds
were alkylbenzene, alkylthiophene, alkyl-indane and
heteroaromatic (pyrrole, furan) homologue series. The
appearance of dissolved organic compounds is bound
to a threshold temperature at ~70°C, and their
distribution is influenced by the water temperature.
Demethylation and aromatisation were observed with
increasing temperature. The origin of these
compounds is not known, precursor candidates are
lignites, humic substances, and bitumen.
Simulation experiments were carried out on different
materials: humic and fulvic acids (HA and FA); a HA
and FA mixture obtained from thermal water (HAFA),
bitumen obtained from lignite (BIT); a lignite sample
(C); and on organic matter precipitated on the filter of
an active geothermal well (P). The samples were
treated in a Parr reactor vessel in 3 g/L NaHCO3
distillated water for 24 or 72 hours on 220°C, 250°C,
300°C and 320°C under reductive conditions. Three
samples were treated under oxidative conditions too.
The compounds formed were identified by GC/MS. In
this paper we focus on volatile aromatic and
heteroaromatic compounds.
Under oxidative conditions the amount of benzene
increases and the amount of toluene and thiophene
decreases with increasing temperature. Other
alkylbenzenes are missing.
In the case of reductive sample treatment, with
increasing temperature the amounts of benzene,
toluene and thiophene increase in every sample. The
benzene/toluene ratio increases in FA, HAFA and P,
but decreases in HA, C and BIT (Fig. 1). Main
compounds are toluene and benzene. The amount of
thiophene increases, with the ratio of
thiophene/alkylbenzenes remaining constant up to
300°C, and decreasing at 320°C. C produces the
most thiophene.
The amount of heteroaromatics increases with
temperature, but the heteroaromatics/aromatics ratio
decreases. At higher temperatures the proportion of
heteroaromatic compounds containing N (pyrrole and
alkyl-pyrroles) decreases and S and O containing
ones (thiophene and furan homologues) become
dominant. The effects of duration and increasing
temperature are similar but not equal: demethylation
and aromatisation can be observed.
Fig. 1 Benzene and benzene/toluene distributions
This work was funded by the Hungarian Scientific
Research Fund (OTKA) through grant T 048829.
References
[1] Kárpáti, Z., Sajgó, Cs., Vető, I. Klopp, G. and
Horváth, I. 1995. Identification of various organics in
thermal waters in the Pannonian Basin. Preliminary
reports. Organic Geochemistry� Developments and
applications to energy, climate, environment and
human history. (eds. Grimalt J. O. and Dorronsoro
C.), A. I. G. O. A. Donostia-San Sebastian, 594-596.
[2] Kárpáti Z., Sajgó Cs., Vető I., Klopp G.,
Horváth I. 1999 Organic matter in thermal waters of
the Pannonian Basin - A preliminary report on
aromatic compounds. Organic Geochemistry 30(7):
701-712.
372

P-236
Distribution and Fate of Lignin in Dissolved Organic Matter in
World’s Large River Systems
Xiaojuan Feng 1,2 , Valier Galy 2 , Jorien E. Vonk 1 , Britta Voss 2 , Ying Wu 3 , Bernhard
Peucker-Ehrenbrink 2 , R. Max Holmes 4 , Daniel B. Montlucon 1,2 , Timothy I. Eglinton 1,2
1 Geological Institute, ETH, Zürich, Zurich, Switzerland, 2 Department of Marine Chemistry & Geochemistry,
Woods Hole Oceanographic Institution, Woods Hole, MA, United States of America, 3 State Key Laboratory
of Estuarine and Coastal Research, East China Normal University, Shanghai, China, 4 Woods Hole Research
Center, Woods Hole, MA, United States of America (corresponding author:xfeng@erdw.ethz.ch)
Dissolved organic matter (DOM) represents
one of the largest active organic carbon reservoirs in
the world and terrestrial organic carbon is a major
contributor to DOM in rivers, lakes and the coastal
ocean. As an important and ubiquitous component of
terrestrial organic matter, lignin is widely distributed in
riverine and oceanic DOM. However, we know very
little about the fate of lignin in riverine DOM — How
much does it contribute to the dissolved organic
carbon in rivers? What environmental parameters
control its supply to, and fate within the DOM? What
are the timescales involved in the transport of
dissolved lignin from land to rivers and the ocean?
Answers to these questions are crucial for
understanding the role of DOM within the global
carbon cycle. Here we investigate the distribution and
composition of lignin in the DOM from several major
river systems around the globe with contrasting
drainage basin properties, climate and hydrological
conditions (including Congo, Fraser, Ganges-
Brahmaputra, Kolyma, and Yangtze, etc.). Dissolved
lignin is collected from filtered river water onto C18
solid phase extraction cartridges and extracted using
CuO oxidation method. Lignin-derived phenols are
identified and quantified on gas
chromatography/mass spectrometry and normalized
to the dissolved organic carbon content of river water.
We compare the abundance, composition, and
degradation stage of dissolved lignin across these
different river systems to understand the
environmental variables that govern the transport and
transformation of lignin in aquatic systems. We also
compare lignin phenol composition in the riverine
DOM with that in the suspended particles collected
from the same river system to assess lignin
fractionation and degradation in the dissolved and
particulate phases during the land-river transport.
Furthermore, we collected large-volume samples of
riverine DOM and isolated lignin phenols by high
pressure liquid chromatography for compoundspecific
radiocarbon and stable carbon isotopic
analysis. The radiocarbon age of dissolved lignin
versus lignin in sedimentary particles provides
insights on the source and turnover time of terrestrial
organic matter within fluvial systems. Overall, this
project will provide new insights into the geochemical
cycling of terrestrial DOM in riverine environments.
373

P-237
Nature of C29 sterols in the high-molecular weight dissolved
organic matter (HMW-DOM) from a freshwater lake
Kazuo Fukushima 1 , Koji Takahashi 1 , Yasuko Yoshiyama 1 , Yoshito Chikaraishi 2
1 Shinshu University, Matsumoto, Japan, 2 JAMSTEC-IFREE, Yokosuka, Japan (corresponding
author:kfukush@shinshu-u.ac.jp)
In our previous works, HMW-DOM (High-Molecular
Weight Dissolved Organic matter) were quantitatively
separated from some freshwater and blackish water
lakes in Japan, by using a Tangential-flow
ultrafiltration apparatus (TFF) [1,2]. The gross
chemical nature of the HMW-DOM as revealed by
bulk carbon (� 13 C) and nitrogen (� 15 N) isotope
composition, and fatty acid composition in the HMW-
DOM suggested that organic matter produced in-situ
within the lake water primarily by phytoplankton and
bacteria may contribute much to the formation of
HMW-DOM.
On the contrary, 24-ethyl-cholesta-5,22-diene-3�-ol
(stigmasterol) predominated in the neutral lipid class
of HMW-DOM and its abundance decreased
considerably from summer to winter. Under these
circumstances, compound-specific carbon and
hydrogen isotope compositions were examined to
further discriminate the sources of sterols in the
HMW-DOM from a freshwater Lake Kizaki (water
depth 29m) water, Japan. Water samples (100L) were
collected in May-Dec 2007 from around 10-15m depth,
which corresponds to the lowest layer of the
thermocline developing in summer seasons.
The technique used for condensation and isolation
of solid powder HMW-DOM was TFF (Millipore Ltd.,
Pellicon Lab Cassette, 5 ft 2 ) followed by classic
stirring ultrafiltration (Toyo Ltd., 9 cm�), both equipped
with cellulose membrane filter of nominal molecular
cut-off of 1 kDa, and finally lyophilization. The solid
HMW-DOM was directly saponified by heating in
alkaline aqueous (5%) methanol (1M KOH).
Sterols/alcohol fraction was purified by column
chromatography and quantitated by GC and GC-MS.
Stable isotope ratios, � 13 C and �D of individual sterols,
were determined by GC-IRMS, Agilent 6890N
coupled to a Thermo Fischer Deltaplus XP
(Chikaraishi et al., 2005).
Stigmasterol comprises only less than 5% in the Lake
Kizaki particulate matter (PM) and surface sediment,
whereas in HMW-DOM, it amounted to 58-63% of the
total sterols (0.83-0.88 of 1.3-1.5 �g/L) in summer and
20% (0.11 of 0.55 �g/L) in winter. Such large
variation presumably indicates that both autochtonous
and allochthonous biota should participate in the
occurrence of stigmasterol in the lake water.
Meanwhile, abundance of another C29 sterol, 24-ethylcholest-5-en-3�-ol
(�-sitosterol) was almost constant
at 0.25 �g/L in all samples. It indicates that �sitosterol
may be solely derived from terrestrial plants,
irrespective to the biological production within the lake.
Evidences supporting the assumption were
obtained by stable carbon and hydrogen isotope
analyses. Both terrestrial �-sitosterol and algal
brassicasterol fell in the narrow ranges, respectively,
while stigmasterol showed a meaningful seasonal
variation (Fig.1).
Fig. 1. � 13 C-�D plots of stigmasterol in HMW-DOM and
sediment
References
1) Yoshiyama et al. (2003) Res. Org. Geochem. 18,
37-45 (in Japanese)
2) Takahashi et al.(2007) IMOG23, P92.
3) Chikaraishi et al. (2005) Limnol. Oceanogr. 50,
1763-1770.
374

P-238
Rhizoliths at the Nussloch loess profile (SW Germany) –
assessment of source vegetation using stable isotopes and nalkane
molecular proxies
Martina Gocke, Guido Wiesenberg
Department for Agroecosystem Research, University of Bayreuth, Bayreuth, Germany (corresponding
author:martina.gocke@uni-bayreuth.de)
Rhizoliths are a special type of pedogenic carbonates
which formed mainly under arid and semiarid climatic
conditions. They represent former roots that were
encrusted by secondary carbonate, often leading to
selective preservation of the former root tissue. Such
concretions have been described previously in
paleosols and various terrestrial sediments including
loess. In contrast to other types of pedogenic
carbonates, rhizoliths were formed during rather short
periods, i.e. during the life span of the root. Therefore,
they are used as sensitive paleoenvironmental
archives. It has been speculated that rhizoliths are
formed solely around tree roots, or even solely around
roots of coniferous trees. In modern soils, they were
observed to form under various wooden plants like
pine, peach or vine, but sometimes also under
herbaceous plants. However, source plants of
rhizolith formation are commonly unknown, because
the rhizoliths found in terrestrial sediments are not
connected to the aboveground plant parts any more.
Our aim was to assess the origin of rhizoliths, which
occur locally abundant at the late Pleistocene loesspaleosol
sequence at Nussloch, SW Germany. These
rhizoliths are considerably younger than the
surrounding sediment (� ≈ 12-14 ka, [1]). They
appear in a depth between 0.8 m and 8 m below
present soil surface, with diameters of up to ~ 5 cm
and length between some cm and 1.5 m. Within the
depth interval of highest rhizolith abundance (0.8-6.9
m), rhizoliths of different shape and size were
sampled. Small amounts of organic remains
preserved within the rhizoliths allowed stable C
isotopic (δ 13 C) and lipid analyses of organic matter
(OM).
As to be expected under humid temperate climatic
conditions of SW Germany, δ 13 C of rhizolith OM
indicated C3 plants as source vegetation for all
samples, with values between -24 and -25.5‰.
Alkane composition revealed predominance of long
chain (C25+) odd homologues, thus confirmed the
higher plant origin of rhizoliths. The carbon preference
index (CPI) of rhizolith OM was comparable to
modern root biomass, which is lower than
aboveground plant biomass due to the presence of
associated microbial biomass and missing
epicuticular waxes. The most abundant long chain
alkane in most rhizoliths was either C27 or C29,
suggesting tree or shrub source vegetation rather
than grass plants which are usually dominated by C31
long chain alkane [2]. On the other hand, variation of
the alkane composition between rhizoliths of different
depth concerning e.g. CPI and n-C27/n-C31 ratio (Fig.
1) indicate that rhizoliths at Nussloch derive from
various source plants.
However, these results do not exclude the possibility
of rhizolith formation taking place under smaller plants
like herbs. Therefore, further investigations on
rhizoliths, combined with comparison to modern
analogues, are under progress to further elucidate
source vegetation of rhizoliths in terrestrial sediments.
Fig. 1: n-C27/n-C31 ratio of rhizoliths from various
depth intervals.
References
[1] Gocke M., Pustovoytov K., Kühn P., Wiesenberg
G.L.B., Löscher M., Kuzyakov Y. 2011, Chemical
Geology.
[2] Schwark L., Zink K., Lechterbeck J. 2002,
Geology.
375

P-239
Differentiation of organic matter in soil, loess and rhizoliths at
the Nussloch sedimentary sequence via n-alkane molecular
proxies
Martina Gocke, Guido Wiesenberg
Department for Agroecosystem Research, University of Bayreuth, Bayreuth, Germany (corresponding
author:martina.gocke@uni-bayreuth.de)
Loess-paleosol sequences are important terrestrial
archives to study Quaternary climate, based on
proxies like pollen, stable carbon isotope composition
(δ 13 C) of organic matter (OM) and many others.
Commonly, loess OM is thought to represent the
signal of the vegetation prevailing during deposition,
i.e. mainly grass vegetation without large abundances
of trees or shrubs.
However, the presence of large calcified roots
(rhizoliths) in the loess profile of Nussloch (SW
Germany) gives an example, how loess-paleosol
sequences have been penetrated postsedimentary by
deep-rooting plants. These plants could have a
different size and shape compared to synsedimentary
grass vegetation and likely modified the initial loess
OM via release of root exudates and fine root hairs.
This can entail uncertainties for paleoenvironmental
studies based on loess OM. Therefore, identification
and source apportionment of OM of different origin in
loess is required to reduce related uncertainties.
However, this remains difficult due of low organic
carbon (Corg) contents in loess (usually < 0.5%). Lipid
molecular proxies, e.g. from n-alkanes and fatty acids,
enable the required source apportionment of OM in
recent and ancient soils and sediments [1].
The aim of this study was to identify different sources
of OM in the loess sequence of Nussloch, SW
Germany, and to demonstrate the relevance of
postsedimentary incorporation of root-derived OM for
an overprint of the original Corg signal in terrestrial
sediments. Therefore, pairs of rhizoliths and reference
loess without visible root remains were sampled from
the profile in depths between 0.8 and 6.9 m. For
comparison, the modern soil and recent vegetation,
consisting of grasses, herbaceous plants and robinia,
were sampled. Further, loess in direct vicinity to the
rhizoliths up to a distance of 5 cm (rhizoloess), was
sampled. The samples were compared for their
alkane composition, lipid and Corg contents.
Alkane composition with C31 as most abundant long
chain homologue revealed that both, loess and soil
organic matter (OM), were derived from grass
vegetation. While arable crops mainly contributed to
the recent soil OM, these were natural grasses for
loess. The recent vegetation did not contribute to OM
in rhizoliths and rhizoloess. Rhizoliths were formed
under tree and/or shrub vegetation more than 3000
years BP and reflect the natural former vegetation,
which likely was dominated by beech, oak, alder and
hazelnut. Low values for the carbon preference index
(CPI) in rhizoliths and rhizoloess revealed the
presence of former root tissue and associated
rhizomicrobial remains [2]. The overprint of loess
organic matter even distant to former roots cannot be
excluded as revealed by molecular proxies like
average chain length (ACL) or CPI. Therefore,
paleoenvironmental investigations of terrestrial
sediments based only on bulk carbon analyses should
be regarded with caution.
Besides further investigations on recent root biomass
and rhizoliths, rhizoloess must be investigated in
more detail to assess the postsedimentary
modification of loess OM near to the former roots and
to determine the extension of the former rhizosphere.
Fig. 1: CPI and ACL of rhizoliths, loess, soil and
modern vegetation at the Nussloch site.
References
[1] Harwood J.L., Russel N.J. 1984. Lipids in plants
and microbes. Allen & Unwin, London.
[2] Cranwell P.A. 1981. Organic Geochemistry.
376

P-240
Evidence for transport mechanisms of soil derived branched
GDGTs
Hendrik Grotheer 1 , Sabine Kasten 2 , Gesine Mollenhauer 1,2
1 Department of Geosciences, University of Bremen, Klagenfurter Str., 28359 Bremen, Germany, 2 Alfred-
Wegener-Institute for Polar and Marine Research, Am Handelshafen 12, 27570 Bremerhaven, Germany
(corresponding author:h.grotheer@freenet.de)
Input of terrigenous material to the oceans is an
important process in global element cycles, including
the carbon cycle. Therefore, many studies in the past
have used either organic or inorganic proxies to
quantify the terrigenous contribution and paleoclimatic
interpretations were made based on these proxy
records. Among the more recently introduced proxies
for export of soil-derived organic matter and the
reconstruction of environmental conditions on land
like mean air temperature and soil pH, respectively,
are the so-called BIT, MBT and CBT indices [1, 2] , using
abundance ratios of branched tetraether lipids
(GDGTs) believed to derive from unknown soildwelling
anaerobic bacteria. The habitat of these soilorganisms,
however, is not well constrained, nor is
the association of these lipids with mineral grains
exported to the ocean.
We therefore analysed abundance of these branched
GDGTs using HPLC-APCI-MS and measured
concentrations of the elements iron, titanium,
aluminium, and potassium, typically taken as
indicators for terrigenous material, by ICP-OES on
sediment core (GeoB3910-2). The core was
recovered 100 km north-east of the Brazilian coast at
4°14.7‘S and 36°20.7‘W in 2362 m water depth in the
deposition area of the Piranha River (Açu River). We
investigated a segment deposited between 10 and 20
ka B.P. containing records of climate response to the
Younger Dryas (YD) and the Heinrich Event 1 (H1)
cold events in NE Brazil.
Our results confirm previous data suggesting a
southward shift of the ITCZ during YD and H1 leading
to an increase in precipitation in NE Brazil [3] and
therefore to enhanced erosion of organic and
lithogenic material. The calculated pH-values also
support previous findings of a two-step vegetation
response to the enhanced precipitation [4] during H1.
Furthermore the combination of organic and inorganic
analyses allows a partial reconstruction of transport
pathways for GDGTs from anaerobic soil bacteria.
A clear correlation between branched GDGT
concentration and aluminium content suggests the
formation of insoluble organo-metal complexes [5] in
anaerobic and acidic podsol horizons. These
complexes are then leached out and transported
towards the river system. Additionally, the titanium
and iron content show a similar correlation to the
GDGT concentration implying that besides aluminium
the formation of organo-metal complexes with other
elements can serve as a transport host as well.
Figure 1: Correlation between terrigenous elements and
sum of branched GDGTs. Squares (H1) and diamonds
(YD) indicating periods with increased precipitation.
1. Hopmans, E.C., et al., Earth and Planetary Science
Letters, 2004. 224(1-2): p. 107-116.
2. Weijers, J.W.H., et al., Geochimica et Cosmochimica
Acta 2007. 71: p. 703-713.
3. Jaeschke, A., et al., Paleoceanography, 2007. 22(4): p.
PA4206.
4. Dupont, L.M., et al., Global Change Biology, 2009.
5. Bardy, M., et al., Geochimica et Cosmochimica Acta,
2007. 71(13).
377

P-242
Changes of Rock-Eval HI, OI, and C-isotope ratios during decay
of soil organic matter in a temperate climate environment
(Villiers, Switzerland)
Olivier Hasinger 1 , Jorge E. Spangenberg 2 , Eric P. Verrecchia 1
1 Institute of Geology and Paleontology, University of Lausanne, Lausanne, Switzerland, 2 Institute of
Mineralogy and Geochemistry, University of Lausanne, Lausanne, Switzerland (corresponding
author:olivier.hasinger@unil.ch)
Four hypotheses have been formulated to explain the
13 C enrichment in soil organic matter (SOM) with
increasing depth: (i) a change in the isotopic
composition of atmospheric carbon, (ii) a higher
contribution of microbial biomass in deeper soils, (iii)
kinetic fractionation during plant respiration, and (iv)
preferential decay of labile organic compounds [1, 2].
In this study, we explore the combined use of C
isotope ratios and Rock Eval HI and OI values to get
further insight into the increase of � 13 CSOM along soil
profiles. Data have been gathered in a 1.4 m deep
reference soil in Villiers (Switzerland, 47°04‘N, 6°59‘E,
769 m asl). Bulk soil samples were collected along
the soil profile at different depth. Three fractions were
separated from each sample, including (i) lignin
(alkaline CuO oxidation with a microwave digestion
system); (ii) humic substances (alkaline extraction);
(iii) labile sugars (hot water extraction).
The C isotopic composition of TOC varies
between -26.9 and -25‰ VPDB with depth (Fig. 1A).
The sugar is the isotopically heaviest fraction of SOM
whereas the lignin is the most 13 C depleted. Trends
toward higher � 13 C values with depth suggest
(bacterial) decomposition of the SOM fraction with
release of isotopically light moieties (e.g., CO2, short-
C-chain lipids). The OI values increase with depth
from ~183 to ~377, and the HI values decrease from
~186 to ~84. The opposite trends between the
� 13 CTOC and the OI and HI values suggest that
oxidation of SOM through (bacterial) oxidative
decarboxylation along the soil profile is most probably
the main process triggering the 13 C-enrichment (Fig.
1B).
In conclusion, the Rock-Eval HI, OI, and � 13 C
values of the soil organic fractions bring new insights
into the processes responsible for the 13 C enrichment
of TOC during soil formation. These results support
the hypothesis of a preferential decay of given organic
components in soils. Nevertheless, these results
cannot be generalized to other soils, as different
humification pathways may occur in soils with
different SOM composition.
A
B
Fig.1. A. Vertical distribution of the � 13 C values of TOC and
various extracted fraction of SOM B. � 13 CTOC vs Rock-Eval
OI and HI values.
References
[1] Boström et al. (2007), Oecologia 153, 89-98.
[2] Wynn et al. (2005), Geochimica et Cosmochimica Acta
69, 1961-1973.
378

P-243
Organic matter composition and degradation in Siberian
permafrost soils
Silke Höfle 1 , Pascal Boeckx 2 , Dries Roobroeck 2 , Gesine Mollenhauer 3 , Janet
Rethemeyer 1
1 Institute of Geology and Mineralogy, University of Cologne, Cologne, Germany, 2 Faculty of Bioscience
Engineering, Ghent University, Ghent, Belgium, 3 Alfred-Wegner Institute for Polar and Marine Research,
Bremerhaven, Germany (corresponding author:silke.hoefle@uni-koeln.de)
Enhanced microbial activity in thawing permafrost soil
is assumed to increase decomposition and carbon
emissions to the atmosphere [1]. Microorganisms are
the main drivers of the decomposition of soil organic
matter (SOM). It remains difficult to estimate changes
in organic carbon stocks for future warming scenarios
because of the heterogeneous mixture of organic
components and spatial variability in permafrost
landscapes. Thus, it is essential to better characterize
SOM composition and identify temperature sensitive
carbon pools which are preferentially degraded.
We analyzed depth intervals in the active layer
thawing during summer of two characteristic
cryogenic structures (rim and centre) of the polygonal
tundra in the Lena Delta, Siberian Arctic. SOM
composition was characterized by elemental and lipid
analysis including n-alkanes and n-fatty acid.
Microbial communities were studied by phospholipid
fatty acid (PLFA) analysis indicative of viable
microorganisms and the degradation of labile/'young'
and stable/'old' SOM will be identified by 14 C analysis
of individual PLFAs.
The very different SOM quality in the polygon rim and
centre profiles is reflected by bulk soil parameters and
lipid distributions. Total organic carbon (TOC)
contents decrease from 2.8 to 0.8 wt-% in the centre,
while an increase with depth (1.6 to 3.3 wt-%TOC) is
observed in the rim. The polygon centre consists of
peaty, mostly undecomposed plant material
dominated by terrestrial plant lipids with C22 and C24
fatty acid and C27 and C29 n-alkanes being the most
dominant compounds. High C/N ratios (35-51) and
CPI values for both lipid fractions are further
indicators for slow decomposition and low microbial
activities, respectively in the water saturated active
layer during the summer season. Likewise PLFA
concentration decline strongly with depth (Fig.1)
indicating that (aerobic) bacterial activities are mainly
taking place in the uppermost layer. Declining 14 C
contents of bulk SOM (113 to 95 pMC) are assumed
to reflect mainly the 14 C signature of plant and root
biomass.
The polygon rim contains organic rich mineral soil
with fewer recognizable plant remains. The stronger
decomposition of SOM is displayed by lower C/N
ratios (16-20) and CPI values for n-fatty acids and nalkanes
throughout the profile. Similar long-chain
plant lipids are observed as in the polygon centre.
The abundances of the n-alkanes decrease with
depth. However, long-chain fatty acid concentrations
show a considerable increase with depth and yield
higher concentrations near the permafrost table and
even in the uppermost frozen soil layer than in the
surface soil suggesting better preservation or in-situ
production of these compounds. Regarding the strong
decrease in 14 C concentration (90 to 68 pMC) parallel
to increasing TOC contents in the rim profile, we
assume that both factors may be important here. High
abundances of gram- and gram+ bacterial PLFAs
within the active layer give indication for a large
microbial community. 14 C data of individual PLFAs –
still in process – will indicate if production or
preservation is more important and if the 'old' SOM in
the permafrost is microbial metabolized.
Fig. 1: PLFA concentrations for gram+ (i14:0, i/a15:0, a16:0,
i/a17:0), gram- (16:1‘9c, 16:1‘11c, 18:1‘11c), fungal (18:1‘9c)
biomarkers and 14 C values of the polygon rim and centre
References:
[1] Khvorostanov D V et al., 2008, Tellus, 60B, 265-275
379

P-244
Identification and distribution of intact branched tetraether lipids
in peat and soils
Francien Peterse, Ellen Hopmans, Stefan Schouten, Anchelique Mets, Irene Rijpstra,
Jaap Sinninghe Damsté
NIOZ Royal Netherlands Institute for Sea Research, Den Hoorn (Texel), Netherlands
Branched glycerol dialkyl glycerol tetraether
(GDGT) lipids are membrane spanning tetraether
lipids that occur ubiquitously in soils and peats (1,2).
The branched GDGTs form the base of several
proxies, like the BIT index that is used to determine
the relative input of soil organic matter into marine
sediments (2), and the MBT/CBT proxy for the
reconstruction of continental air temperatures and
past soil pH (3).
Most studies so far focused on the
distribution of core lipids (CLs) only, however, by
analyzing just the core lipids, only the pool of fossil
material in a soil is covered. In order to differentiate
between branched GDGTs derived from living cells
and those from the fossil GDGT pool, also their intact
polar precursors need to be analyzed. Here we
directly analyzed, using HPLC/ESI-MS 2 , the
occurrence and distribution of intact polar lipid (IPL)
branched GDGTs throughout a depth profile of a
Swedish peat bog, and quantified CL en IPL-derived
branched GDGTs by HPLC/ APCI-MS for
comparison. Some soils were also analyzed.
In addition to two previously discovered
glycosidic IPL-branched GDGTs (4), we identified
IPL-branched GDGTs with a hexose-glucuronyl,
phospho-hexose, phospho-inositol, or hexosephosphoglycerol
headgroup. A Selected Reaction
Monitoring (SRM) assay was developed to monitor
changes in headgroup distribution with depth. The
abundance of all monitored IPL-branched GDGTs
increases below the water table (Figure). However,
individual IPL trends differ; especially the
phospholipids show a relatively much larger increase
with depth than glycosidic IPLs. The oxic part of the
peat bog contains much less IPL-branched GDGTs,
probably due to rapid oxic degradation of any material
produced at times of high water levels and anaerobic
conditions. It is also in this part that we observe a
higher relative abundance of glycolipids compared to
phospholipids. This observation is in agreement with
the more recalcitrant nature of glycolipids (5). Thus, it
seems that the best marker for in situ production of
branched GDGTs is the phospho-hexose branched
GDGT. Comparison of trends in phospho IPLbranched
GDGTs with changes in absolute amounts
of IPL-derived and CL branched GDGTs with depth
indicates that branched GDGTs are mainly produced
by anaerobic bacteria, possibly from a subdivision of
the phylum Acidobacteria, in the anoxic part of the
peat. Some of the IPL-branched GDGTs are also
present in soils, although their distributions differ from
that in the peat profile.
1. Sinninghe Damsté et al., 2000. Chem. Comm.
17, 1683-1684.
2. Hopmans et al., 2004. EPSL 224, 107-116.
3. Weijers et al., 2007. GCA 71, 703-713.
4. Liu et al., 2001. Org. Geochem. 41, 653-660.
5. Harvey et al., 1986. GCA 50, 795-804.
Depth profiles of the Saxnäs Mosse peat bog showing the IPL-branched GDGTs included in the SRM assay and the
concentrations of CL (blue), IPL-derived (open blue), and phospho-IPL derived (grey triangles) branched GDGTs. The
horizontal dotted lines indicate the level of the water table at the time of sampling (14 cm), and at its lowest point (25 cm ).
380

P-245
Effects of in situ artificially increased temperature on the
distribution of branched GDGTs in a French peatbog
Arnaud Huguet 1 , Céline Fosse 2 , Fatima Laggoun-Défarge 3 , Sylvie Derenne 1
1 BioEMCo, CNRS/UPMC UMR 7618, Paris, France, 2 Chimie ParisTech (ENSCP), Laboratoire de
Spectrométrie de Masse, Paris, France, 3 Université d’Orléans, CNRS/INSU, ISTO UMR 6113, Orléans,
France (corresponding author:arnaud.huguet@upmc.fr)
Glycerol dialkyl glycerol tetraethers (GDGTs) are
complex lipids of high molecular weight, present in
cell membranes of archaea and some bacteria.
Archaeal membranes are formed predominantly by
isoprenoid GDGTs with acyclic or ring-containing
biphytanyl chains. Another type of GDGTs with
branched instead of isoprenoid alkyl chains was
recently discovered in soils and was suggested to be
produced by anaerobic bacteria. The relative
distribution of branched GDGTs was shown to be
determined primarily by two environmental
parameters: mean annual air temperature (MAAT)
and soil pH. The degree of methylation, expressed in
the methylation index of branched tetraethers (MBT),
was shown to depend on MAAT and to a lesser extent
on soil pH, whereas the relative abundance of
cyclopentyl rings of branched GDGTs, expressed in
the cyclisation ratio of branched tetraethers (CBT),
was observed to correlate well with soil pH. The MBT
and CBT indices have recently been shown to be
useful tools for the reconstruction of past continental
temperatures. Nevertheless, the MBT and CBT have
been empirically established and the direct impact of
temperature on these two proxies has been rarely
evaluated.
The aim of this work was to study the effects of in
situ artificially increased temperature on the
abundance and distribution of branched GDGTs in a
Sphagnum-dominated peatland located in the Jura
Mountains (Frasne, France). In this peatland,
temperature was experimentally increased using a
warming system consisting of in situ open minigreenhouses
(Open-Top Chamber – OTC). 12
randomised plots have been chosen (6 controls and 6
OTCs). Two years after the installation of the warming
system, MAAT was observed to be 1.6°C higher in
the OTCs than in the control plots. 3 peat samples (5-
7, 7-12 and 12-17 cm depth) were collected from
each plot. GDGTs occur under two broad forms: core
lipids, presumed to be of fossil origin, and intact polar
lipids, derived from recently active microorganisms.
Both lipid pools were investigated in this study. Core
lipids were observed to represent between 75 and
85% of the total pool of branched GDGTs (i.e. core +
intact polar GDGTs), indicating that branched GDGTs
are predominantly of fossil origin in Frasne peatland.
In addition, the MBT was observed to be
systematically higher in the OTCs than in the controls
at all depths, implying that the average degree of
methylation of branched GDGTs decreased with
increasing temperature. This confirms the effect of
temperature on branched GDGT distribution
previously established in a large range of soils and
supports the empirical relationship between MBT and
MAAT. Last, the analysis of the MBT and CBT
revealed no significant differences in branched GDGT
distribution between the core and intact polar lipid
pools, suggesting that the fossil pool of branched
GDGTs has a very fast turnover (less than the 2 year
duration of the experiment) at the peat surface. To the
best of our knowledge, these results are the first
evidence of a direct influence of temperature on
branched GDGT distribution.
381

P-246
Carbon isotopes and lipid biomarker investigation of sources,
transport and degradation of terrestrial organic matter in the SE
Laptev Sea
Emma Karlsson 1 , Alexander Charkin 2 , Oleg Dudarev 2 , Igor Semiletov 2 , Jorien Vonk 1,3 ,
Laura Sanchéz-García 1 , August Andersson 1 , Örjan Gustafsson 1
1 Department of Applied Environmental Science (ITM) and the Bert Bolin Centre for Climate Research,
Stockholm University, Stockholm, Sweden, 2 Pacific Oceanological Institute, Russian Academy of Sciences,
Vladivostok, Russian Federation, 3 The Swiss Federal Institute of Technology (ETH), Department of Earth
Sciences, Zürich, Switzerland (corresponding author:emma.karlsson@itm.su.se)
The world‘s largest continental shelf, the East
Siberian Shelf Sea, receives a substantial input of
terrestrial organic matter (terrOM) from both its large
rivers and from erosion of its coastline. Degradation of
organic matter from thawing permafrost in the Arctic is
likely to increase, potentially creating a positive
feedback mechanism to climate warming. This study
focuses on the Buor-Khaya Bay (SE Laptev Sea), an
area with strong terrOM input from both coastal
erosion and the Lena river (abstract Fig.), traceable
over long distances in the East Siberian Shelf Seas.
To better understand the fate of the terrOM in these
coastal waters, molecular (acyl lipid biomarkers) and
isotopic tools (stable carbon and radiocarbon
isotopes) have been applied to both particulate
organic carbon (POC) in surface water and
sedimentary organic carbon (SOC) collected from the
underlying surface sediments.
Clear gradients in molecular and isotopic signals of
both extent of degradation and differences in source
contributions were observed. These gradients were
both seen between surface water POC and surface
sediment SOC as well as over the 100s km
investigation scale (about 20 stations). Depleted
d13C-OC and high HMW/LMW n-alkane ratios in both
SOC and POC signalled that terrOM was dominating
over marine/planktonic sources.
Despite a shallow water column (10-40 m), the
isotopic shift between SOC and POC varied
systematically from +2 to +5 per mil for d13C and
from +300 to +450 for D14C from the Lena prodelta to
the Buor-Khaya Cape. At the same time, the ratio of
HMW n-alkanoic acids to HMW n-alkanes, indicative
of degradation, was about 5 times greater in the SOC
than in the POC. The HMW n-alkane CPI was also
higher in SOC than in POC. Taken together, this
suggests that the terrOM was substantially older yet
less degraded in the surface sediment than in the
surface waters. This degradation trend is contrary to
what is normally observed [1] but consistent with what
was recently found for the central East Siberian shelf
Sea [2].
Numerical-modelling (Monte Carlo) was applied using
13C and 14C in both POC and SOC to deduce the
relative contribution of – marine OC, surface soil layer
OC and Yedoma/mineral soil OC. This three endmember
dual-carbon-isotopic mixing model suggests
quite different scenarios for the POC vs the SOC.
Surface soil is dominating (63±10%) the suspended
organic matter in the surface water of SE Laptev Sea.
In contrast, the Yedoma/mineral soil OC is accounting
for 60±9% of the surface sediment OC. We
hypothesize that Yedoma-OC, associated with
mineral-rich matter from coastal erosion is ballasted
and Yedoma quickly settles to the bottom. The
mineral association is also likely to explain the greater
resistance to degradation of this terrOM component.
In contrast, more humic-like terrOM from surface soil
and recent vegetation represents the younger but
more bioavailable and thus degraded terrOM
component buoyant in surface water. Hence, these
two terrOM components may represent different
propensities to contribute to a positive feedback to
climate warming by converting OC from coastal and
inland permafrost into CO2.
Fig.1. East Siberian Arctic Shelf, with the Buor-Khaya
Bay on insert. Sampled stations in blue.
References:
[1] Vonk et al. Marine Chemistry, 112(1-2): 1-10.
(2008).
[2] Vonk et al. Biogeosciences, 7(10): 3153-3166.
(2010)
382

P-247
Carbon capture by soil chemoautotrophs
Kris Hart 1 , Brian Moran 1 , Chris Allen 2 , André Simpson 3 , Brian Kelleher 1
1 Dublin City University, Dublin, Ireland, 2 Queens University Belfast, Belfast, Ireland, 3 University of Toronto,
Toronto, Canada (corresponding author:brian.kelleher@dcu.ie)
Soil Organic Matter (SOM) is the most complicated
biomaterial on Earth. It has been shown to contain
significantly more carbon than is currently present in
the atmosphere (approx twice as much) [1, 2]. It has
been recently reported that humic material in SOM is
a highly complex mixture of microbial and plant
biopolymers and not a distinct chemical fraction as
previously thought [2]. Furthermore, it has been
reported that the microbial biomass contribution to
SOM is not comprised of mainly humic materials and
that in fact the contribution to SOM by soil
microorganisms has been seriously underestimated
[3]. Therefore, the question arises if we underestimate
microbial biomass in soil do we also underestimate
carbon uptake by soil microbes? The presented
material herein is part of a project to develop a
methodology to combine ecological studies with
molecular characteristics using soil chemoautotrophic
bacteria in vivo and measurements of CO2 uptake
using a stable carbon isotope ( 13 C). Soil microcosms
were developed in an environmental incubation
chamber under short term incubations (≤24 hr).
Detection of the labelled biomass within the SOM
fraction was performed using GCMS-IRMS. IRMS
analysis revealed isotopic enrichment of lipids up to
91%, which can be directly affiliated to atmospheric
CO2 capture. High resolution infra-red detection of
internal CO2 concentrations indicate that maximum
uptakes rates of 1574 mg CO2/Ha/100 hr were
incorporated into biomass. Complimentary analysis
using 13 C solid state HR-MAS-NMR confirmed
enrichment had taken place leading to the detection
of complex biomaterial such as carbohydrates and
proteins. Preliminary identification of CO2 assimilating
microbes was performed using ultra-centrifugation
stable isotope probing (SIP) to separate the ‗heavy‘
labelled DNA fraction from the total DNA. The isolated
13 C-DNA was then cloned into E.coli using standard
molecular biological techniques and the identification
of Acidothiobacillus ferrooxidans and Thiobacillus
denitrificans was made by comparison to the BLAST
DNA sequence database.
383

P-248
Comparison of soil organic matter tracers (branched GDGTs and
soil-specific BHPs): A study of the NW Mediterranean shelfslope
region
Jung-Hyun Kim 1 , Helen M. Talbot 2 , Roselyne Buscail 3 , Thomas Wagner 2 , Jaap S.
Sinninghe Damsté 1
1 NIOZ, ‘t Horntje (Texel), Netherlands, 2 Newcastle University, Newcastle, United Kingdom, 3 CEFREM,
Perpignan, France (corresponding author:Jung-Hyun.Kim@nioz.nl)
The transport of terrestrial organic matter (OM) to
coastal sediments represents a significant flux in the
global carbon cycle. Although a large range of bulk
and molecular proxies for terrestrial OM is available,
quantification of the relative inputs of terrestrial OM to
marine sediments is still difficult due to large
variations in concentrations of compounds in various
higher plants and different degradation rates. The
incomplete understanding of the transfer of terrestrial
OM from land to the ocean is probably due to the lack
of diagnostic (geochemical) proxies especially for soil
OM, which accounts for two third of the total terrestrial
carbon budget.
Recently, several developments have led to
new insights into the recognition of soil OM in marine
environments. The Branched and Isoprenoid
Tetraether (BIT) index has been introduced as a
proxy to trace soil OM input from land to the marine
environments [1]. This index is based on the relative
abundance of branched glycerol dialkyl glycerol
tetraethers (GDGTs) versus a structurally related
isoprenoid GDGT ―crenarchaeol‖. More recently, four
bacteriohopanepolyols (BHPs, adenosylhopane
adenosylhopane-type 1, 2-methyl adenosylhopane,
and 2-methyl adenosylhopane-type 1), have been
suggested to be characteristic of soil microbial
communities [2] and potentially can also serve as
molecular markers for soil OM supply in river, lake,
and marine sediments [3,4].
In this study, we compared both soil OM
tracers in peats and soils collected in the Rhône and
Têt watersheds (Southern France) and surface
sediments of the Gulf of Lions (NW Mediterranean,
Figure 1). Branched GDGTs and soil-specific BHPs
occur ubiquitously in peats and soils. The comparison
of soil-specific BHP parameters with those of
branched GDGTs shows no clear relationship in the
watersheds. This suggests that these two groups of
soil-specific compounds are synthesized by different
microbial organisms living in different niches and/or
separate depths in the soil profile (oxic top versus
anoxic deep). Nevertheless, marine surface
sediments show that both branched GDGTs and soilspecific
BHPs decrease offshore, indicating the
delivery and preservation of these soil OM tracers in
marine environments.
Our initial results suggest that soil-specific
BHPs are transported from land to the sea via rivers
similar to branched GDGTs and thus soil-specific
BHPs may have potential to also serve as a tracer for
soil OM input from land to marine environments.
However, our study also shows that the current state
of knowledge does not allow for a simple direct
comparison of soil-specific BHP parameters with
branched GDGTs indicating that care must be taken
when comparing both soil OM proxies. More work is
required to extend our limited knowledge on the
production, occurrence and preservation of both
groups of biomarkers in various environmental
settings.
Latitude (N)
44.0
43.5
43.0
42.5
Têt River
42.0
2.5 3.0 3.5 4.0 4.5 5.0 5.5
Longitude (E)
Rhône River
Figure 1. Sampling locations in the Gulf of Lions
considered in this study.
References:
[1] Hopmans et al., 2004, Earth Planet. Sci. Lett., 224,
107-116.
[2] Cooke et al., 2008a, Org. Geochem., 39, 1347-
1358.
[3] Talbot et al., 2007, Org. Geochem., 38, 1212–
1225.
[4] Cooke et al., 2008b, Org. Geochem., 39, 965-971.
384

P-249
Habitat adaptation by compositional changes of cuticular needle
waxes for the Norway Spruce (Observation Platform Eifel
National Parc)
Gina Kuippers 1 , Ulrich Mann 2 , Jan Schwarzbauer 1
1 RWTH Aachen University, Lehrstuhl für Geologie, Geochemie und Lagerstätten des Erdöls und der Kohle,
Aachen, Germany,
2 Forschungszentrum Jülich, Institut für Bio- und Geowissenschaften, Jülich, Germany,
(corresponding author: ginakuippers@web.de)
The organic-geochemical composition of cuticular
needle waxes of the Norway spruce from the Eifel
National Parc was investigated by semi-quantitative
GC/MS analyses. Needles of different ages (recent
vs. older generations) and from different altitude (364
m vs. 603 m) were compared to each other.
Aliquot samples were subjected to a combined
polarity/affinity gas chromatographic separation into
functionalized monoaromatics, fatty acids, fatty acid
methyl esters, n-alkanes as well as terpenoids.
Relative concentrations of the dominant compound
groups of the needle waxes were represented by
monoterpenes, sesquiterpenes and fatty acids (Fig.
1). According to the age of the cuticular waxes, a
decrease of sesquiterpenes besides an increase of
monoterpenes was observed. By far the most
important representatives of the monoterpenes were
β-phellandrene and camphene, whereas the group of
sesquiterpenes was dominated by δ- and γcadinenes.
The concentration of fatty acids increased
with sea level. Palmitic acid was particularly prevalent
in the cuticulae of the spruces at high sea level, while
dehydroabietic acid and arachidic acid features were
more prominent at the lower sea level.
Although n-alkanes did not represent a dominant
fraction of the spruce cuticulae, their most prominent
chain length increased with sea level (Fig. 2). In total,
the chain length of the carbon atoms ranged from n-
C21 to n-C33 alkanes. Whereas at the lower site the n-
C27 alkane predominates, at the higher location the n-
C29-alkane clearly represents the dominating chain
length.
Based on the amount of samples, present results
can be regarded as a random inspection only.
Nevertheless, especially the compositional
differences of the cuticular waxes were surprisingly
high related to a relative low sea level difference of
239 m between the two sample sets. On the other
side, these results may indicate the high potential of
the Norway spruce for habitat adaptations during
climate changes.
Acknowledgement
This study was conducted as part of project TERENO.
Fig. 1: Relative amounts of compound groups for site
Wüstebach (samples 1a-c, 603 m) and site
Wilderness Trail (samples 2a-b, 364 m).
Fig. 2: Relative contents of n-alkanes. Numbers
marking the peak of each distribution.
385

P-250
Biomarker distribution along a pedosequence recording a
transition from pasture to conifer forest (Massif Central, France)
Marlène Lavrieux 1 , Jean-Gabriel Bréheret 2 , Jean-Robert Disnar 1 , Jérémy Jacob 1 , Claude
Le Milbeau 1 , Renata Zocatelli 1
1 Institut des Sciences de la Terre d’Orléans (ISTO), Université d’Orléans, CNRS/INSU, Université de Tours,
UMR 6113, Orléans, France, 2 Institut des Sciences de la Terre d’Orléans (ISTO), Université de Tours,
CNRS/INSU, Université d’Orléans, UMR 6113, Tours, France (corresponding
author:marlene.lavrieux@etu.univ-tours.fr)
Anticipating the consequences of future global
changes on natural systems requires the
understanding of the responses of past ecosystems
under climatic and anthropic constraints. As natural
archives, soils are particularly relevant since they
potentially preserve indications of their previous uses.
Such uses are known to have irreversible impacts on
soils, in terms of bulk chemical properties, soil
nutrients availability, soil structure and local
vegetation communities, at least at the historical scale
(e.g. [1]). However, little is known about the
persistence of lipid imprints through time in soils. The
aim of this study is to compare the lipid imprint of
three soils that suffered distinct land use histories in
order to evaluate the possibilities offered by lipids to
preserve information on past land uses.
Three soils were sampled in the catchment of Lake
Aydat (Central France) and then subsampled into 2
cm thick slices. Two of these soils remained under the
same overlying vegetation (pasture: S-p, and forest:
S-f) for the last 60 years. They constitute ―reference‖
soils. These soils are compared to a soil formerly
covered by a pasture/grassland 60 years ago and
now by a conifer forest (S-pf). Bulk organic matter
(OM) characterisation was performed by Rock-Eval
pyrolysis. Lipids were extracted by ASE using
DCM:MeOH and then separated into neutral, acidic
and polar compounds on aminopropyl bonded silica.
The neutral fraction was submitted to further
separation by flash chromatography using solvents of
increasing polarity. Lipid fractions were then identified
by gas chromatography-mass spectrometry.
Rock-Eval results suggest that, in the three soil
profiles, the time of turnover and OM stabilisation
increases with depth, with a global tendency toward
increasing oxidation with depth. Combined with the
absence of aromatic compounds, this indicates that
lipids were not strongly affected by alteration.
Degradation can thus not be invoked to explain
variations in molecular content between the three soil
profiles.
Several classes of compounds were tested as
potential tracers of former land uses: n-alkanes,
tricyclic diterpenes, wax esters, FAMEs, steroids and
triterpenes (e.g. [2], [3]). Although the most abundant
n-alkane homologue is clearly defined in reference
soils (n-C29 in S-f and n-C31 S-p), there is no shift
from n-C31 to n-C29 in S-pf. Tricyclic diterpenoids,
that are conifer markers, are present all along the S-f
profile and are totally absent in S-p. These
compounds are only present in the upper part of S-pf.
Methoxyserratenes follow tricyclic diterpenes,
although they also appear in low amount at the base
of S-pf. Reversely, triterpenyl acetates are detected in
S-p but are totally absent from S-f. Most of detected
triterpenyl acetates are present all along the S-pf
profile.
This study highlights the variable potential of soil
molecular biomarkers to record former land-uses, at
least on decadal scales. The most specific and
resistant families, such as pentacyclic triterpenes and
tricyclic diterpenes, provide the most useful
information but did not allow observing an obvious
vertical zoning of molecular imprints in S-pf. This
could result from mixing processes such as leaching,
bioturbation and root penetration that affected this
soil. Finally, criteria based on the presence/absence
of given compounds appear more powerful than
compound relative abundances.
References
[1] Hurtt, G.C., Frolking, S., Fearon, M.G., Moore, B.,
Shevliakova, E., Malyshev, S., Pacala, S.W., Houghton,
R.A., 2006. The underpinnings of land-use history: three
centuries of global gridded land-use transitions, woodharvest
activity, and resulting secondary lands. Global
Change Biology 12, 7, 1208-1229.
[2] Lavrieux, M., Jacob, J., Le Milbeau, C., Disnar,
J.R., Zocatelli, R., Bréheret, J.G., Masuda, K., 2011. First
detection of triterpenyl acetates in soils: sources and
potential as new palaeoenvironmental biomarkers. <strong>25th</strong>
<strong>International</strong> <strong>Meeting</strong> on Organic Geochemistry, Interlaken,
Switzerland.
[3] Le Milbeau, C., Lavrieux, M., Jacob, J., Zocatelli,
R., Disnar, J.R., 2011. Methoxyserratenes as discriminant
biomarkers for soils developed under conifer forests. <strong>25th</strong>
<strong>International</strong> <strong>Meeting</strong> on Organic Geochemistry, Interlaken,
Switzerland.
386

P-251
Long-term, low temperature simulation of early diagenetic
alterations of organic matter from conifers: Terpenoids in the
aromatic hydrocarbon fraction
Shenjun Qin 1,2 , Yuzhuang Sun 1 , Yuegang Tang 2 , Kankun Jin 1
1 Hebei University of Engineering, Handan, China, 2 China University of Mining and Technology, Beijing,
China (corresponding author:qin_s_j@hotmail.com)
Early diagenesis of terrestrial organic matter
from higher plants, in modern sediments, peat, lignite,
etc., is a focus of geological research. With the aim to
investigate early diagenetic alterations of organic
matter from conifers, a long-term (more than five
years) simulation experiment at low temperature
(80°C) has been carried out. The experimental results
about the formation of peat macerals and the
characteristics of aliphatic hydrocarbons have been
reported [1, 2]. In the present study, the coniferous
diagenetic products, mainly terpenoids, in the
aromatic hydrocarbon fraction were analysed.
Leaves, branches and barks from contemporary
Cedrus deodara (Pinaceae) and Platycladus orientalis
(Cupressaceae) were divided into several groups and
mixed with different inorganic materials to keep each
sample in a unique condition. All samples covered by
purified water in closed wide-mouthed bottles were
put into an oven, whose temperature was maintained
at 80°C. In the earlier and later stage of this
simulation experiment, i.e. when it has continued for
approximately one year and five years, a part of each
sample was taken out for the organic geochemical
analyses. GC and GC-MS analyses of the aromatics
from conifers were performed on a Hewlett-Packard
model 6890 GC and that coupled to a Hewlett-
Packard model 5973 quadrupole MSD.
The GC and GC-MS data of selected samples
show that the composition of the aromatic fraction is
more complex than that of the aliphatic one. They
consist of common polycyclic aromatic hydrocarbons
(PAHs), aromatic terpenoids and several unexpected
polar terpenoids (Fig.1). Otto et al. (1997) has also
detected high percentage of similar polar terpenoid
(ferruginol) in the aromatic fraction from conifers [3].
In contemporary samples (P & C) and simulated
samples (Ax-1) in the earlier simulation, no common
PAHs were detected. In the simulated samples (Ax-2)
in the latter simualtion, minor common PAHs were
tested. They may be produced by early diagenesis
but not by biosynthesis [4].
Abundance
100000
80000
60000
40000
20000
Abundance
0
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
50000
sesquiterpenoids
U1~U3
(MW286)
10 20 30 40 50 60 70 80
Y2
Y1
U1 U2
Y3
Time
0
32.00 34.00 36.00 38.00 40.00 42.00 44.00 46.00
Time-->
TIC
sesquiterpenoids
P
methyl dehydroabietate
dehydroabietate aldehydes
Y1~Y3 (MW 284) A11-1 diterpenoids
Abundance
Abundance
1600000
1400000
1200000
1000000
800000
600000
400000
200000
700000
600000
500000
400000
300000
200000
100000
0
0
sesquiterpenoids
U1~U3(MW286)
10 20 30 40 50 60 70 80
Time
~P+~DPB+diterpenoids
cadalene
TMN P
dehydroabietane
retene
10 20 30 40 50 60 70 80
Fig. 1. GC and GC-MS (TIC) traces of the aromatic fractions
In all coniferous samples, considerable aromatic
and polyunsaturated terpenoids were found. The
variations of their composition and relative abundance
during the simulation show the early diagenetic
pathways of terpenoids from their biogenic precursors.
Furthermore, several natural and evolutionary
polar terpenoids (Ux and Yx), which are seldom
reported in the geosphere, were detected and
identified tentatively. They possibly are isomers of
functionalized abietane-type diterpenoids, which may
give meaningful information about the resources of
coniferous biomarkers and the alternations of
diterpenoids in their early diagenesis.
References
[1] Qin, S. J., Sun, Y. Z., Tang, Y. G. (2010) Geochem. J. 44,
247-259.
[2] Sun, Y. Z., Qin, S. J., Zhao, C. L., Kalkreuth, W (2010) Energ.
Fuel 24, 1124-1128.
[3] Otto, A., Walther, H., Puttmann, W. (1997) Org. Geochem. 26,
105-115.
[4] Meyers, P.A., Ishiwatari, R. (1993) Org. Geochem. 20, 867-
900.
U5
Time
C
A 11 -2
387

Wednesday Poster Presentations
388

P-254
The Formation Conditions of Shallow Gas and Controlling
Factors of Its Reservoirs in the Songliao Basin, NE China
Zihui Feng, Xue Wang, Qiuli Huo, Shibo Wang
Exploration and Development Research Institute, PetroChina Daqing Oilfield Company, Da qing, China
(corresponding author:fengzihui@petrochina.com.cn)
The Songliao basin lies in the northeastern part of
China with a total area of 260 thousands square
kilometers. The Cretaceous sediments dominated in the
basin, with much thinner layers of Tertiary and
Quaternary strata. The biggest oilfield of China-the
Daqing oilfield was founded there. After many years of
exploration, especially the studies performed in recent
years, it is clear that not only abundant oil accumulated in
the Songliao Basin, considerable quantity of natural gas
was also discovered in the shallow layers of the
Cretaceous strata less than 1500m, including the
Heidimiao, Saertu and Putaohua oilbeds, where the
vitrinite reflectance (Ro) of the rock is lower than 0.6%.
The discovery of these shallow gas proved that the
shallow strata are also an important field for oil and gas
exploration, which will provide new basis for the
development of the already-matured oilfield.
The shallow gas of Songliao basin are mainly of
biogenic origins, including biogenic methane gas
originated from source rocks, biogas from the
degradation of crude oil and sub-biogas equivalent to
immature and low mature gas. The types of natural gas
in the Songliao Basin are similar with the results reported
from other basin by domestic and foreign scholars while
the formation and distribution of shallow gas in the
Songliao Basin do have their own features. At first, the
gas reservoir in the Songliao Basin formed relatively old
and mainly in the Cretaceous, though most biogas of
China distribute in the Tertiary and Quaternary stratum.
Secondly, the source rocks distributed widely and stably
with little lateral variation for they were deposited during
the period when large area of depression developed in
this basin, but the gas reservoirs are mainly dominated
by thin sandstones with a large lateral changes. Thirdly
the currently discovered shallow gas reservoirs have the
characteristics of high production, low abundance, small
scale and wide distributions. Obviously all of these
features are different from other large biogas reservoirs
discovered in the world. For example the biogas
reservoirs in middle and upper Miocene of Italy are
mainly of structural trap and the shallow natural gas
reservoirs of upper Devonian in Michagan basin are
closely related to fractures, while the biogas reservoirs in
Quaternary system of Qaidam Basin are characterized
by numerous thin layers, which are only slightly affected
by the tectonic activities and faults. Therefore, the further
geological and geochemical study to elucidate the
formation conditions of shallow gas and controlling
factors for their accumulation in the reservoirs of
Songliao Basin will not only accelerate the exploration of
shallow gas in the basin, but also improve our
understanding on the formation and distribution of
shallow gas reservoirs.
The shallow layers of Songliao Basin refer to the late
Cretaceous and Tertiary stratum buried less than 1500m.
At present, many gas reservoirs and evidences showing
the existence of gas which is of biogenic origin are
discovered in the Cretaceous stratum. The formation
conditions of shallow gas and controlling factors for its
accumulation in the reservoirs in the Songliao Basin are
studied in the paper with the combination of geological,
geochemical and biochemical methods. The result shows
that the higher pH in the strata of the basin plays
negligible roles on biogas formation. The type II kerogen
of hydrocarbon source rock has the highest producing
rate of biogenic gas, with a maximum of 997.25ml/gToc.
Secondly are the type III and I kerogen of hydrocarbon
source rock with producing rate of 615.95ml/gToc and
447.89ml/gToc, respectively. There are two peaks of the
biogas formation in the basin: one is 35°C and the other
is 60°C. The biogas formation of the type II kerogen is
chiefly at the first one. The immature to low mature
source rocks are widely distributed in the basin. The thick
Unit 1 of Qingshankou formation and Unit 1-2 of Nenjiang
formation with higher abundance and various types of
organic matter have shown the most important potential
for the biogas formation. The shallow gas reservoirs in
the Songliao Basin are mainly of lithologic and structurallithologic
type. The formation of the gas reservoirs are
chiefly controlled by the gas generating intensity of the
source rock, the distribution of sand body, and the
occurrences of faults. It is suggested by the work that
Songliao Basin are of high prospective potentials for the
exploration of shallow gas.
389

P-255
Gas source classification in Paleozoic marine strata, China
Wenhui Liu 1,2
1 Sinopec Research Institute of Petroleum Exploration and Production, Beijing, China, 2 Wuxi Institute of
Petroleum Geology, Sinopec Research Institute of Petroleum Exploration and Production, Wuxi, China
(corresponding author:whliu@pepris.com)
The Paleozoic marine sequences in China are
dominated by carbonate, with subordinate amounts of
clastic rocks. Due to their multiple tectonic history and
deep burial,these rocks has often experienced
multiple episodes of hydrocarbon generation,
expulsion, migration and accumulation. Where the
sedimentary basins are in continuous subsidence,
kerogens in the sediments would undergo continuous
thermal maturation to generate oil and then gas, and
are now in highly mature to over-mature stages with
respect to hydrocarbon generation. Where the
sediments underwent initial burial, then uplift and
subsequent deep burial, the originally thermally
matured kerogens would experience a second-period
(or late) hydrocarbon generation; dispersed
sedimentary organic matter and previously migrated
oils in the carrier beds or reservoirs would also be
subject to thermal cracking to form separate gas
phase,and the dominant hydrocarbon potential in
these situations would be derived from the secondary
cracking process of these paleo oil or bitumen
accumulations. Therefore, natural gases in a given
reservoir are potentially derived from thermal
maturation of kerogens in conventional petroleum
source rocks, thermal cracking of paleo oil
accumulation and / or dispersed bitumens in
sediments, or high temperature hydrogenation of
overmatured sedimentary organic matter. As a result,
it would be prudent and logical to include paleo oil
accumulation, bitumens, whether in concentrated or
dispersed form, in the gas source consideration, in
addition to the conventional hydrocarbon source rocks.
The latter may become the dominant sources for
gases derived in highly mature-over-mature
sedimentary strata.
Traditional scheme to classify hydrocarbon source
organic matter is largely based on the chemical
characteristics of insoluble organic matter, and the
latter were commonly classified into type I, II and III
kerogens. This classification scheme is very useful for
evaluating the biological sources of the sedimentary
organic matter, their thermal behaviors (oil or gas
prone), and general capabilities for oil or gas
generation, under early stages of thermal maturation
that involves only first-order chemical reactions.
However, this scheme is not sufficient to capture the
essence of the prevailing chemical reactions in the
deep subsurface that are responsible for natural gas
generation. To overcome the shortcomings of the
conventional scheme, an alternative classification is
proposed in Fig. 1, where the gas sourcing organic
matter is now subdivided into one of the three general
categories: organic matter that is (1) insoluble in
organic solvent, (2) soluble in organic solvent and (3)
released only after acid digestion of host sediments.
Sedimentary organic matter could occur naturally in
dispersed, concentrated or chemically covalent
bonded form. While the first two forms occur mostly in
traditional hydrocarbon source rocks, coal and oil
shales contain mainly concentrated form of organic
matter. Dispersed soluble organic matter within the
conventional source rocks or carrier beds/reservoirs
can act as the hydrocarbon source for secondary gas
generation. In particular, secondary cracking of paleo
oil accumulation has proven to be one of the most
important sources for many of the gas accumulations
discovered in the Paleozoic marine strata in southern
and western China. Solid bitumens, heavy oils, migrobitumens
and dispersed bitumens in oil source rocks
can be the source for subsequent thermal cracking, to
form light oil or condensate gas accumulations. As
dispersed bitumens in source rocksand carrier beds
are quantitatively very large, they are considered to
be another important source for gas generation.
Results of laboratory thermal simulation indicate that
kerogens in overmatured sedimentary rocks bear
relatively limited hydrocarbon potential, while
substantial amounts of the newly formed gas come
from thermal cracking of dispersed bitumens or preexisting
hydrocarbons. In addition, significant
proportions of polar organic material are incorporated
into rock matrix through organic acid-inorganic
mineral reactions, to form complex or organic salts,
particularly in carbonate rocks. The gas potential of
these organic salts may have been underestimated in
most of the previous studies. Therefore, the interreactions,
inter-conversion and temporal succession
of the different organic matter forms in the
sedimentary strata may be invoked as the primary
reason for the preservation of giant gas
accumulations in ultra-deep carbonate reservoirs
recently discovered in southern China.
390

P-256
Late stage gas generation in source rocks and gas shales
Nicolaj Mahlstedt, Brian Horsfield
Deutsches GeoForschungsZentrum GFZ, 14473 Potsdam, Germany (corresponding author:nick@gfzpotsdam.de)
Late dry gas generation can be expected for organic
matter with R0 > 2.0% and for geologic temperatures
well in excess of 200°C [1, 2]. This ―High Temperature
Methane‖ goes largely unnoticed when evaluation of
immature source rocks is based on routinely used
open-system pyrolysis screening-methods alone and
contributes, in addition to the cracking of unexpelled
oil, significantly to the accumulation of thermogenic
gas in low-porosity, low permeability gas shales as
well as in coal seams.
In this study we consider in detail to what extent late
stage gas generation is a function of depositional
environment and organic matter evolution using a
rapid, closed-system-pyrolysis-based screening
approach on a large world wide sample set (~100
samples) of immature source rocks as well as both
natural and artificially prepared maturity series. We
show that for almost any kind of organic matter the
late gas potential is not fixed at immature stages but
seems to increase up to ~40 mg/g TOC by the end of
catagenesis stage. Additional thermal stress during
metagenesis leads to decreasing potentials indicating
late gas generation.
The closed-system screening method basically
consists of heating crushed whole rock samples
(2°C/min) in micro-scale sealed vessels (MSSV) to 2
different end temperatures (560°C; 700°C) spanning
the range of late gas generation which occurs
subsequent to cumulative primary and secondary gas
formation. The possibility of discriminating between
source rocks with low, intermediate or high late gas
generative properties has been previously presented
[3] and can be applied to immature organic matter in
relation to its total hydrocarbon potential. High late
gas potentials are associated with heterogeneous
organic matter exhibiting a high aromaticity, mainly
terrestrial influenced type III to type II/III shales and
coals; low late gas potentials are associated with
homogeneous, paraffinic organic matter.
In the course of catagenesis late gas potentials
increase up to ~40 mg/g TOC for natural maturity
series samples (Westphalian Coals, Wealden Coals,
Barnett Shale) indicating that predicted late gas
amounts of immature equivalents are underestimates.
During natural maturation, chain shortening reactions
via β–scission related to hydrocarbon generation
might lead to a concomitant enrichment of methylaromatics
and hence late gas precursor structures
within the residual organic matter. This interpretation
is corroborated by the preparative pyrolysis of 2
immature coal samples (Åre Fm., R0 ~ 0.4%;
Westphalian Coal, R0 ~ 0.99%) under open- and
closed-system pyrolytic conditions. Starting at 250°C,
samples were heated to 400, 450, and 500°C using a
1°C/min heating rate. Despite differences in the stage
of artificially induced maturity, late gas potentials of
residues increase for both analytical set-ups. Thus,
second-order recombination reactions between firstformed
bitumen and residual organic matter seem
not, as previously assumed [1, 2], to be a prerequisite
for the generation of late gas but can be viewed as
being supportive for the retention of TOC enhancing
the amount of high temperature methane generated
from a given mature source rock unit during
metagenesis.
The decrease of late gas potentials during
metagenesis (R0 > 2.0%) demonstrates that dry gas
generation takes place under geologic conditions and
indirectly confirms previous [1, 2] and new (this study)
compositional MSSV-kinetic calculations.
References
[1] Erdmann and Horsfield (2006), Geochim. Cosmochim.
Acta 70, 3943-3956.
[2] Dieckmann et al. (2006), Mar. Pet. Geol. 23, 183-199.
[3] Mahlstedt and Horsfield (2009) Geochim. Cosmochim.
Acta 73, A817-A817
391

P-257
The components and carbon isotopic compositions of inorganic
hydrocarbon gases with different carbon origins synthesized in
gold tube closed-system
Jingkui Mi 1,2 , Shuichang Zhang 1,2 , Kun He 1,2
1 Research Institute of Petroleum Exploration and Development, PetroChina, Beijing, China, 2 State Key
Laboratory for Enhanced Oil Recovery, Beijing, China (corresponding author:jkmi@petrochina.com.cn)
This paper reports the components and carbon
isotope compositions effects of the abiotic
hydrocarbon gases produced by Fischer-Tropsch
synthesis under 50MPa pressure in gold tube closedsystem
in which the reactants are two kinds of CO2
with different δ 13 C values (δ 13 Cheavey-CO2=-0.5‰ 、
δ 13 Clight-CO2=-16.51‰) , a graphite(δ 13 Cgraphite=-
21.05‰) and hydrogen, with montmorillonite loading
the chloridate of iron and nickel as catalysts. The
components and carbon isotopic compositions of
synthetic alkane gases will produce great change with
the constant temperature time lasting at different
temperature. All the carbon isotope trends of synthetic
alkane gases (C1~C4) show from inverse trend, partial
reverse to normal trend with the constant temperature
time lasted from 2hr to 60hr at 400℃ in three groups
experiments in which the carbons of three different
origins are hydrogenated into inorganic hydrocarbon
gases, but the periods of the inverse trend of alkane
gases carbon isotopic holding are different. At 400℃,
the period of the inverse trend of carbon isotopic
gases holding is only 2hr when light CO2is
hydrogenated, the period of the inverse trend of
carbon isotopic gases lasting is less than 5hr if the
reactants are heavy CO2 and H2, and the period of the
inverse trend of carbon isotopic gases lasting could
maintain 20hr as the graphite is hydrogenated. The
fractionations of 24.24‰, 11.33‰, 5.02‰ and 4.22‰
among CH4, C2H6, C3H8 and C4H10 show in the
synthesis process with light CO2 and H2 as reactants,
the fractionations of 17.73‰, 5.57‰, 4.43‰ and
1.85‰ among CH4, C2H6, C3H8 and C4H10 show in the
synthesis process with heavy CO2 and H2 as
reactants, and, the fractionations of 8.22‰,
3.58‰, 3.83‰ and 4.81‰ among CH4, C2H6, C3H8
and C4H10 show in the synthesis process with
graphite and H2 as reactants, respectively. Generally,
all the maximum yield of total alkane gases occurs in
the stage the inverse trend turning to that partial
reverse of their carbon isotope in all three groups
experiment at 400℃. There is only a little ethane in
products besides methane with 2 hr constant
temperature at 700℃. With time of constant
temperature at 700℃ increasing, ethane disappear.
Moreover, the longer does constant temperature last,
the less of the amount of methane and the heavier of
carbon isotope of methane are. We suggest that the
reaction mechanisms of the carbon with different
origins affiliating inorganic gases synthesis are
different in the mantle or in meteorites. The
monatomic carbon is easier to take part in the
reaction to generate inorganic hydrocarbon gas
formation than that of gaseous carbon if the
hydrocarbon gases with inverse carbon trend of
C1~C4 are sure to be inorganic origin, and, the
gaseous carbon with enrichment 13 C is easier to enter
in to inorganic hydrocarbon gas than that with poor
13 C. The inorganic hydrocarbon gases does not yield
in the very deeper layers of the earth with high
temperature, but in a shallower layers of the earth
with relatively lower temperature in a short time,
because the heavy hydrocarbon gases would be
broken into methane with the temperature and the
time hold in a relatively high temperature increasing,
the reaction mechanism in different matter will turn
from dynamic reaction to thermal one. Methane could
also be broken into monatomic carbon and hydrogen
with temperature further increasing. This may be a
main reason that no commercial perfect inorganic
hydrocarbon gas pool is found at present.
392

P-258
Worldwide distribution and significance of secondary microbial
methane formed during petroleum biodegradation in
conventional reservoirs
Alexei Milkov
BP Russia, Moscow, Russian Federation (corresponding author:alexei.milkov@bp.com)
Around half of world‘s endowment of in-place oil and
bitumen experienced biodegradation, which is now
believed to be largely an anaerobic methanogenic
process. However, the distribution and scale of
methanogenic biodegradation in world‘s petroleum
accumulations and the significance of its terminal
product, secondary microbial methane, in global gas
endowment and carbon cycle are largely unknown.
Here, I present geological and geochemical criteria to
recognize secondary microbial methane in
conventional petroleum reservoirs. These include the
presence of biodegraded oil (as pools, legs or shows)
in the reservoir or down-dip, the relatively dry
(methane-dominated) gas containing methane with
δ 13 C values between -55‰ and -35‰ and, most
importantly, CO2 with δ 13 C >+2‰ (Fig. 1). Based on
these criteria, the presence of secondary microbial
methane is apparent in 22 basins, probable in 12
basins and possible in six basins worldwide (Fig. 2).
Reservoirs apparently containing secondary microbial
methane are mostly Cenozoic and clastic and occur
at depths 37–1834 m below surface/mudline and
temperatures 12–71 ºC. Using the current global
endowment of in-place oil and bitumen and
reasonable assumptions about conversion of oil into
methane during biodegradation, I estimated that
~65,500 tcf of secondary microbial methane could
have been generated in existing worldwide
accumulations of oil and bitumen through their
geological history. From 1461-2760 tcf in-place (845-
1644 tcf recoverable) of secondary microbial methane
may be accumulated as free and oil-dissolved gas in
petroleum reservoirs. I also updated the inventory of
primary microbial methane and estimated that the
global primary microbial gas endowment (free and oildissolved)
is from 676-797 tcf in-place (407-589 tcf
recoverable). Secondary microbial methane may
account for ~5–11% of the global conventional
recoverable gas endowment and appears more
abundant than primary microbial gas (~3-4% of the
global gas endowment). Most of the generated
secondary microbial methane probably is aerobically
and anaerobically oxidized to CO2 in the overburden
above petroleum reservoirs. However, some
secondary microbial methane may escape from
shallow reservoirs into the atmosphere and affect
present and past global climate.
Fig. 1. δ 13 C of methane vs δ 13 C of CO2 in gases
within global biodegradation zone with genetic fields
defined after [1] and the field of significant secondary
microbial gas defined in this study. Thick brown line
shows the pathway of secondary microbial gas
generation consistent with the model in [2].
Fig 2. Worldwide distribution of secondary microbial
methane.
[1] Whiticar, M.J., Chem. Geol., 161, 291–314.
[2] Jones, D.M. et al., Nature, 451, 176–180.
393

P-259
Stable carbon isotopes of coal-derived alkane gases in China
Jinxing Dai, Yunyan Ni, Xiaoqi Wu, Shipeng Huang, Fengrong Liao
Research Institute of Petroleum Exploration and Development, PetroChina, Beijing, China (corresponding
author:djx@petrochina.com.cn)
There were six main coal-forming periods in China
including Carbonaceous, Permian, Triassic, Jurassic,
Cretaceous and Tertiary, and each period had
corresponding coal measures. Hydrocarbons
generated from these coal measures were dominated
by gas, with subordinate amounts of oil. Coal-derived
gas played a key role in the Chinese natural gas
industry. To date, coal-derived gas accounted for over
65% of the total proved gas reserves and 65.6% of
the annual gas production in China. In the past 30
years, we collected 500 primary gas samples which
were sourced from the Carbonaceous coal measures
in the Junggar Basin, Permian coal measures in the
Ordos Basin (Figure 1), Triassic coal measures in the
Sichuan Basin, Jurrasic coal measures in the Tarim
Basin, Cretaceous coal measures in the Songliao
Basin and Tertiary coal measures in the Yingqiong
Basin. 1600 carbon isotopic data (� 13 C1-4) were
determined and main characteristics of these coalderived
gases were as follows:
1. Patience (2003) proposed that � 13 C of coal-derived
methane ranges from - 38‰ --22‰, however,
coal-derive methane in China has much wider
variance, -43‰--23‰. This is due to the multistages
of reservoir formation of coal-derived gases in
China. The Chinese coal-derived gases have � 13 C2 of
- 28‰ --15.7‰, � 13 C3 of - 43‰ --23‰, and
� 13 C4 of -43‰--23‰.
2. The Chinese coal-derived gases are characterized
by a normal carbon isotopic distribution pattern
whereby gases become more enriched in 13 C with
increasing molecular mass among the C1-C4 alkanes
(� 13 C1

P-260
Geochemical characteristics of biogenic gases in China
Yunyan Ni, Jinxing Dai, Caineng Zou
Research Institute of Petroleum Exploration and Development, PetroChina, Beijing, China (corresponding
author:niyy@petrochina.com.cn)
Alkane gases are formed largely by the digestion of
organic compounds by microorganisms (biogenic gas)
and the thermal decomposition of organic matter
(thermogenic gas). Bacterial process is a widespread
phenomenon in nature and over 20% of the world
natural gas accumulations are of biogenic origin. In
China biogenic gases account for 7% of the total
proved gas reserves. Recent discovery of the largest
terrestrial biogenic gas field with proved gas reserves
of 3000×10 8 m 3 in the Qaidam Basin has
demonstrated the huge resource potential. Due to its
wide distribution, shallow burial depth and low
exploiting cost, biogenic gases play more and more
important role in the gas explorations. Here we
demonstrate the main geochemical characteristics of
biogenic gases in China and their possible formation
mechanisms according to around 200 samples from
various biogenic gas fields, wells or gas seeps.
To date, biogenic gases are mainly distributed in the
strata of Quaternary, Paleogene, Neogene and
Cretaceous with shallow burial depth. The deepest
one is from south Qaidam basin, where burial depth
can be up to 1900 m. The shallowest one is from
Zhejiang, where biogenic gas reservoirs are only
several meters deep. Burial depth of most commercial
biogenic gas reservoirs ranges from 400 to 1800
meters.
Biogenic gases in China are dominated by methane,
with little amount of ethane and propane (normally
less than 1%). � 13 C1 values vary from -89‰~-
55‰ and �D1 values range from -287‰~-108‰.
Previous studies proposed that variations in �D in
biogenic methane are predominantly due to
environmental changes. A differentiation of ‗terrestrial‘
(�D1-190‰
or - 200‰) biogenic gases has been suggested
(Schoell, 1980; Shen et al., 1991). As shown in Figure
1, biogenic gases in China are mainly of terrestrial
origin and a result of bacterial carbonate reduction.
Samples from Yingqiong Basin and Jiangsu province
are relatively more enriched in D, which are closely
related to the marine environments or seawater
intrusion in these areas. Several samples from
Baoshan Basin show a mixture feature of bacterial
carbonate reduction and bacterial methy-type
fermentation. This might be related to its relatively
high geothermal temperature (7-8 ℃ ) which is
favorable for the bacterial methyl-type fermentation.
Fig. 1 Stable carbon and hydrogen isotopes of
biogenic gases in China
References:
[1] Schoell, M. The hydrogen and carbon isotopic
composition of methane from natural gases of various
origins. Geochimica et Cosmochimica Acta, 1980, 44,
649-661.
[2] Shen, P., Xu, Y.C., Wang, X.B., et al. Geochemical
characteristics of gas source rocks and natural gas
genesis. Gansu Science and Technology Press,
LanZhou, 1991.
395

P-261
Natural gas generation, migration and accumulation in the
Jonah Field area, Green River Basin, Wyoming: implications
from chemical and isotopic compositions of gaseous
compounds in the Cretaceous Lance and Mesaverde formations
Qilin Xiao 1 , Paul Philp 1 , Nicholas Harris 2 , Jon Allen 1
1 School of Geology and Geophysics, University of Oklahoma, Norman, United States of America,
2 Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, Canada (corresponding
author:pphilp@ou.edu)
Jonah Field is located in Sublette County, Green
River Basin, Wyoming. Five Cretaceous source rocks
developed in this region, deposited in nonmarine,
marginal-marine and marine environments,
respectively [1]. Natural gas is produced mainly from
the Cretaceous Lance Fm, and partly from the deeper
Cretaceous Mesaverde Fm. The occurrence of
multiple gas sources in different sedimentary
environments and complex tectonic movements make
it difficult to provide an unambiguous conclusion
surrounding gas generation, migration and
accumulation in this area. Combined with basin
modelling results, chemical and isotopic compositions
of gaseous compounds in gas samples from the
Lance and Mesaverde Fms were utilized to identify
and clarify the generation, migration and
accumulation of natural gas in the Jonah Field area.
Methane is the principle component in the samples
from the Lance and Mesaverde Fms, resulting in
C1/C2+C3, C1/C1-C5 and CO2/C1-C5 ratios in the range
of 3 – 10, 80 – 90%, and 0 – 10%, respectively; δ 13 C
values are mainly -45.0‰ to -35.0‰ for methane, -
30.0‰ to -24.0‰ for ethane, -28.0‰ to -24.0‰ for
propane, -26.0‰ to -24.0‰ for butanes and
pentanes, and -15.0‰ to -12.0‰ for CO2,
respectively; δD values range from -220‰ to -160‰
for methane, -180‰ to -150‰ for ethane and
propane. Molecular and stable carbon and hydrogen
isotopic compositions of individual gaseous
compounds in samples from the Cretaceous Lance
and Mesaverde Fms suggests thermogenic gas
associated with oil and condensate.
From the shallow Lance to deep Mesaverde Fms,
the gases become progressively wetter and
isotopically lighter. Ratios from Lance are normally
>85% for C1/C1-C5,

P-262
Minsterry of the organic matter component during biogenic gas
formation: based on the Quaternary of Qaidam Basin
Yanhua Shuai 1 , Shuichang Zhang 1 , Pingan Peng 2 , Hong Lu 2
1 Research Institute of Petroleum & Development of CNPC, Beijing, China, 2 Guangzhou Institute of
Geochemistry,CAS, Guangzhou, China (corresponding author:yhshuai@petrochina.com.cn)
At present, the formation mechanism of earlygeneration
biogenic gas is still mysterious because of
many processes unknown to us. According
conventional thinking, many previous studies on
biogenic gas generation suggest that reactive organic
matter (ROC) be the main and effective substance for
sustaining microbial thriving during biogenic gas
forming. And the ROC was inborn and well reserved
at the beginning of deposit and burial history because
of special geological conditions such as cool
circumstance and high burial rate. However, the
results of organic composition in the Quaternary
deposit in Sanhu depression of Qaidam basin, NW
China, tell us a different story.
Sanhu depression is representative of earlygeneration
biogenic gases area with a proved reserve
of 300 bil steres. Isotopic data of natural gases have
δ 13 CCH4 value ranging from -62‰ to -68.6‰ (VPDB)
and δDCH4 from -218‰ to -245.8‰. Most values of
δ 13 CC2H6 range from -42.4‰ to –44.5‰. Gases
contain 0~0.5% ethane, propane. These data suggest
that gases should be bacterial gases generated by
bacterial reduction of CO2. Almost all the previous
studies think a quick average deposition rate of 800
m/Ma and the frigid climate with an annual average
temperature of 2 O C during the whole Quaternary are
the keys in preserving reactive organic matter which
would be converted into biogenic gases by
methanogen after buried to some depth.
However, the total reactive organic carbon
ultrasonic extracted by acid solution at ambient
temperature (Ingalls et al., 2004) is relatively low,
ranging from 0.4mg/g.sediment to 1.1mg/g.sediment.
ROC is in good relationship with depths, and
decreases with the increasing depth from 100m to
2000 m. Similarly, simple type of reactive organic
matter, as protein and cellulose, were detected in very
low concentrations. The content of protein range from
4.2ug/g to 1570.2ug/g based on per gram of
sediment, and from 10ug/g to 1000ug/g based on per
gram organic carbon. The content of Cellulose is
much higher, ranging from 0.26mg/g.sediment to
7.7mg/g.sediment, and from 0.57mg/g.TOC to
21.2mg/g.TOC, respectively. All those data
demonstrate that reactive organic matter in the
Quaternary is too low to sustain methanogen to
produce such a large scale of biogenic gas.
As a supplement, quantity of subsequent thermal
―reactive organic matter‖ (ROC) was produced by
weak thermal degradation of organic matter. ―ROC‖
content extracted at 80 o C experiment condition was
dramatically higher than that at ambient temperature
of 20 o C. The increment for some samples was even
up to 200%. It demonstrates that secondary ―ROC‖ by
thermo degradation of organic materials, other than
inborn ROC, would be the major nutrient for the deep
biospheres in most geological basins.
As therogenic gases, rapid and sustained longterm
burial background should promote ―ROC‖
generation, and promote biogenic gas formation.
Reference:
Ingalls AE., et al. GCA 2004, 68(21):4363~4379
*Funded by NSFC (40306015,40873031)
397

P-264
Natural gas geochemistry of the southern offshore Brazilian
Basins
Eugenio V Santos Neto 1 , Jose R Cerqueira 1 , Alain Prinzhofer 2
1 Petrobras R&D Center, Rio de Janeiro, Brazil, 2 French Institute of Petroleum, Rueil-Malmaison, France
In the last decades the petroleum exploration in Brazil
has been developed mostly in offshore basins,
especially those located along its southern littoral.
More recently, drilling activities have targeted
prospects pertaining to increasingly deeper, under
thick salt layers and more complex geological
settings. Among many geological aspects that add
complexity to the prospects one is very conspicuous:
the unusual gas composition of many accumulations.
In order to better understand the origin and evolution
of the gas hydrocarbons and non-hydrocarbons was
collected a representative set of gas samples from
two southern Brazilian offshore basins for an
integrated geochemistry study. The samples were
analyzed by GC for the relative quantification of each
gas fraction and carbon isotopic ratios were
measured in hydrocarbons and CO2. That part of the
work was developed in the Gas Geochemistry
Laboratories of the PETROBRAS R&D Center. Noble
gas quantification and isotopes were analyzed in the
Geochemistry Branch of the French Petroleum
Institute.
Gas hydrocarbons have relatively low and
homogeneous values for C2/C3 versus C2/iC4 ratios
suggesting common sources and comparatively
moderate degree of thermal maturity and no evidence
of biodegradation [1]. The low thermal maturity and
the typical primary cracking (kerogen → oil + gas) are
corroborated by the pattern given by the plot � 13 C2-
� 13 C3 versus C2/C3 [2].
The most abundant non-hydrocarbon is CO2 that can
reach up to 80% in some accumulations. Values of
� 13 CCO2 are between -5‰ and -9‰ typical of mineral
origin. Ratios of R/Ra (R = 3 He/ 4 He of sample, Ra =
3 He/ 4 He of the air � 1.4x10 6 ) of helium within those
basins have shown variable but strong mantle
signature. The abundance of CO2 increases with the
strengthening of mantle signature (Fig. 1).
Micropyrolysis performed in samples of the same
stratigraphic interval has shown values of � 13 C for the
produced CO2 significantly different from those found
in natural CO2, e.g., carbonates: +3‰ < � 13 C < +9‰,
carbonates + kerogen � 13 C � -13‰, and kerogen
� 13 C � -20‰.
Carbon isotopic ratios of methane are within -41‰
and -35‰, and C2-C4 mostly in the range of -32‰ and
-29‰. The relatively small difference between � 13 C of
methane and components of the C2+ fraction suggests
a contribution of dry gas from deeper ―gas kitchens‖.
However, the unusual geologic framework of the
region, with extensive crustal thinning and mantle
exhumation [3], may influence somehow the
conventional petroleum system above.
CO2 CO2 (%) (%)
90
80
70
60
50
40
30
20
10
0
0 1 2 3 4 5 6
R/Ra
Fig. 1 – Abundance of CO2 versus R/Ra. Notice that
the values of the end-members for crust and mantle
are 0.01 and 8.00, respectively.
The hydrocarbon accumulations discovered in the
pre-salt in the southern offshore Brazilian basins have
a gas fraction generated mainly by thermal cracking,
with homogeneous low maturities in the C2+ fraction,
and no biodegradation. Isotopically heavy methane
may be sourced by deeper kitchens. High and
variable proportions of CO2, mainly derived from the
mantle, are associated with these fluids.
References
[1] Prinzhofer, A., Mello, M.R., Freitas, L.C.S. & Takaki, T.
(2000). AAPG Memoir 73, p. 107-119.
[2] Lorant, F., Prinzhofer, A., Behar, F., Huc, A.Y. (1998).
Chemical Geology, vol. 147, p. 249-264.
[3] Zalán, P.V., Severino, M.C., Oliveira, J.A.B., Magnavita,
L.P., Mohriak, W.U., Gontijo, R., Viana, A.R., Szatmari,
P. (2009) 2009 AAPG <strong>International</strong> Conference &
Exhibition, Rio de Janeiro, Abstracts.
398

P-265
Analysis of dissolved gases from drilling mud samples for
geochemical and isotope mud gas logging
Philipp Weniger 1 , Stefan Schlömer 2 , Bernhard M. Krooss 1
1 Institute of Geology and Geochemistry of Petroleum and Coal, RWTH Aachen University, Aachen,
Germany, 2 Federal Institute for Geosciences and Natural Resources (BGR), Hannover, Germany
(corresponding author:weniger@lek.rwth-aachen.de)
The chemical and isotopic composition of gas
dissolved in drilling mud provides information on the
penetrated rocks as well as the origin of fluids in
these rock formations. Mud gas isotopic analysis is
frequently applied during petroleum exploration.
Especially in shale gas exploration, the identification
of isotopic anomalies e.g. ethane ‗rollover‘ could
improve the identification of productive zones.
Commercial mud gas logging equipment extracts gas
mechanically from the drilling mud by a mud trap
(mud gas separator), which is then analyzed online or
transferred to sample vessels for analysis in a
laboratory. In many instances, mud gas logging is not
performed in order to reduce drilling costs.
The purpose of the present study was to investigate
the feasibility of gas extraction from drilling mud
samples without an installed mud gas separator.
Drilling mud samples were collected at the well-site at
regular depth intervals during coal bed methane
(CBM) and mine gas drilling operations. The
dissolved gas was extracted using helium as host
gas. The chemical and stable carbon isotopic
composition of the extracted gas was analyzed by gas
chromatography (GC), and isotope ratio mass
spectrometry (GC-IRMS). Carbon isotope analyses
on hydrocarbons (C1 – C4) and CO2 were
successfully performed at concentration levels down
to

P-266
Geochemical and isotopic characterization of coal-related gas
from the SE Upper Silesian Basin, Czech Republic
Philipp Weniger 1 , Juraj Francu 2 , Frantisek Buzek 3 , Petr Hemza 4 , Bernhard M. Krooss 1
1 Institute of Geology and Geochemistry of Petroleum and Coal, RWTH Aachen University, Aachen,
Germany, 2 Czech Geological Survey, Brno, Czech Republic, 3 Czech Geological Survey, Prague, Czech
Republic, 4 GreenGas, DPB a.s., Paskov, Czech Republic (corresponding author:weniger@lek.rwthaachen.de)
Based on their chemical and isotopic composition,
coal-related gases in the Upper Silesian Coal Basin
(USCB) are commonly classified as either
thermogenic or microbial (Kotarba 2001). In the
Ostrava-Karviná coal district in the NE of the Czech
Republic gas occurs in the coal seams of the Ostrava
formation below the nappes of the Carpathian
overthrust, in the coal seams of the Karviná
Formation and the overlying sediments of the
Miocene Foredeep. The subthrust reservoirs contain
predominantly thermogenic methane, whereas
microbial methane prevails below the Carpathian
Foredeep.
In the present study, coal-related gas from different
mines in the Ostrava-Karviná Coal District was
analyzed to evaluate the influence of sorption and
desorption processes on gas composition. For this
purpose, the chemical and stable carbon isotopic
composition of methane and carbon dioxide,
desorbed from coal samples, as well as from mine
face extraction/degassing was compared.
Additionally, gas contents and methane sorption
capacities of related bituminous coal samples have
been determined. Gas desorbed from the Karviná
coal contained mostly methane with δ 13 C values
between -44‰ and -71‰. Gas desorbed from
Ostrava coal had higher C2+ hydrocarbon
concentrations with δ 13 C of methane between -35‰
and -45‰. The geochemical composition of the mine
face gas differed only slightly from the corresponding
desorbed gas composition. However, somewhat
larger differences were apparent in their isotopic
compositions.
According to the classification scheme by Whiticar
(1999), both, the mine face gas and the gas desorbed
from the Karviná coal are attributed to methyl
fermentation, while δ 13 C values of CO2 in the
desorbed gas indicate partial microbial methane
oxidation. The chemical and isotopic composition of
gases from the Ostrava formation indicates a
thermogenic generation process.
During up to 40 days canister desorption, the isotopic
composition of the desorbed CH4 did not show any
consistent trend and fluctuated in a range of +/- 5‰. A
substantial enrichment in 13 C methane by up to 15‰
was observed in a few instances. These could be due
to contamination and need to be verified. Even such a
degree of fractionation, however, would not be
sufficient to significantly alter the original isotopic
signature. It is concluded that the observed variation
in chemical and isotopic composition during
desorption alone cannot explain the differences
between coal-related gases of the Karviná and
Ostrava formations.
C1/(C2+C3)
100000
10000
1000
100
Staric mine face
CSM mine face
CSM desorbed gas
10
1
Lazy desorbed gas
Staric desorbed gas
Polish USCB (Kotarba 2001)
-100 -90 -80 -70 -60 -50 -40 -30 -20
δ13C-CH4 (‰)
Fig.1. Genetic characterization of coal-related gas
from the Upper Silesian Coal Basin using the scheme
from Whiticar (1999)
References
Kotarba, M.J., (2001) Organic Geochemistry 32. 163-
180
Whiticar, M.J., (1999) Chemical Geology 191. 291-
314
400

P-268
Hydrocarbon molecular markers in the upper Cenozoic
sediments of the Arctic megabasin: distribution, genesis &
sources
Vera Petrova
Federal state enterprise ―Academician I.S. Gramberg All-Russia Research Institute for Geology and Mineral
Resources of, St.Petersburg, Russian Federation (corresponding author:petrovavi@mail.ru)
The investigation purpose and idea is to determine
the distribution patterns of hydrocarbon molecular
markers in the sediments of different geostructural
areas of the Eurasian Arctic megabasin in a context of
general geochemical ways of dispersed organic
matter (DOM) transformation and to identify their
indicator functions. This brief is based on the
materials of VNIIOkeangeologiya electronic database
(>2500 bottom stations), formed during long-term
(1980-2008) geological and geochemical studies of
the Russian sector of the Arctic Ocean water areas.
The scale of expeditionary work (regional,
subregional, local) and a wide range of used
analytical methods (bituminology, physical-chemistry,
gas chromatography-mass spectrometry) allowed to
characterize the Pleistocene-Holocene sedimentary
DOM and identify the main factors controlling the
geochemical background formation of the different
litho-facial zones of the region: from estuarine-deltaic
to abyssal. Analysis of hydrocarbon molecular
markers (123 bottom stations, >1000 samples) of the
Holocene-quaternary sediments from the Arctic
Ocean Eurasian sector has revealed their basic
compositional and lateral distribution patterns. The
geohopanes and geosteranes are almost absent in
river and estuarine sediments and only the
components characteristic for the earliest stages of
biogenic OM transformation (hopanols, hopenes,
sterols) have been recorded. Moreover, the chemical
taxones which often mark the specific types of higher
terrestrial plants - D-Friedoolean- 14-ene (gen.
polipodium) and Olean-12-ene (angiosperms) and
miss in the shelf and deep-sea sediments have been
identified.
Both bio- and geoisomers have been fixed in the
terpenoid composition of the offshore sediments.
However the geoisomers structure reflects the low
diagenetic level of DOM transformation. The share of
biological taxones in continental slope sediments is
naturally decreasing to the pelagic region and in the
abyssal zone they haven‘t been detected.
Cadalen and abietic acid transformation products
such as reten, tetrahydroreten, dihydroabietan have
been identified in the aromatic biomarkers
composition of the studied sediments.
On the sea-river transect a consistent increase of
abietan aromatization level, wich agrees with the
postsedimentary DOM transformation trend, have
been fixed.
Reconstruction of the late Cenozoic sedimentation
process was carried out using materials of the
sediment core columns and shallow (12 m) wells
complex study and included seismo-acoustic,
paleomagnetic, biostratigraphic, palynological and
organic-geochemical studies. The result revealed the
characteristic features of the lipid biomarker
composition of the Arctic shelf upper Pleistocene-
Holocene and Eopleistocene-Pliocene sediments.
Thus, the comparative study of the Arctic
megabasin multifacial sediments evaleates the
contribution of different sources (river run-off, turbidity
flows, ocean currents, subaqueous erosion and
redeposition of bedrocks) to the formation of loose
sedimentary cover. In particular, the leading part of
terrigenous material in the Late Cenozoic sediment
composition of the shelf and deep Arctic Basin
including the North Pole area has been shown during
the investigation. At the same time, a complex study
of organic-geochemical and geology-geophysical
parameters of bottom sediments made it possible to
surely identify and characterize the glacial/deglacial
and transgressive-regressive stages of the Late
Cenozoic sedimentation process.
401

P-269
Distribution of alkylbenzenes in oils from deposits of different
geological ages
Galina Pevneva, Anatoly Golovko
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russian
Federation (corresponding author:pevneva@ipc.tsc.ru)
The investigation of composition and distribution
of aromatic hydrocarbons in oils and organic matter of
rocks along with saturated hydrocarbons enables one
to obtain information about the source and
accumulation conditions of the initial organic matter
and its transformation in geological period.
We investigated the composition of alkyl
derivatives monocyclic aromatic hydrocarbons in
order to reveal regularities in their compositions and
distribution in Phanerozoic oils of different oil-and-gas
bearing basins. We have studied compositions of
alkylbenzenes in oils from Cainozoic (Sakhalin,
Pannonsky basin (Serbia), China, Vietnam, Saxony),
Cretaceous (West Siberia, Mongolia), Jurassic (West
Siberia, Baltic Republics) and Paleozoic (West
Siberia, Timano-Pechersky and Volgo-Ural oil-andgas
bearing basin) deposits occurring at the depths
from 200 to 4500 m.
Using chromatography-mass-spectrometry we
have identified the following homologous series of
alkylbenzenes containing a chain of normal structure:
n-alkylbenzenes (n-AB) (m/z 91); 1-methyl,2alkylbenzenes
(1,2-MAB); 1-methyl,3-alkylben-zenes
(1,3-MAB); 1-methyl,4-alkylbenzenes (1,4-MAB) (m/z
105); ethyl- or dimethylalkylbenzenes (m/z 119); as
well as 1-alkyl-2,3,6–thimethylbenzenes containing an
isoprenoid chain of irregular structure (m/z 133). They
were identified by characteristic ions.
Homologous series of alkylbenzenes are
composed by the compounds containing from 10 to
30 carbon atoms in a molecule. In major oils their
molecular-mass distribution has a unimodal character
with a maximum falling on low-molecular
alkylbenzenes of С14-С17 compositions. It should be
also noted that n-AB21 predominates over the content
of adjacent members in the homologous series and it
is the most pronounced in oils from Jurassic and
Paleozoic deposits. According to the opinion of
authors in such an abnormal content of n-AB21 is
probably connected with its relict character. Cortisalin
is considered as a probable precursor of n-AB21. It is
a natural polyene pigment having a bacterial origin,
though possible formation of n-AB21 from natural fat
acids and alcohols should not be excluded.
A homologous series of 1-alkyl-2,3,6–trimethyl
benzenes (i-AB) with an isoprenoid chain of irregular
structure was identified in Paleozoic oils in Timano-
Pecherskaya oil-and-gas bearing province, Ulyanovsk
Region, in Middle Jurassic oils in Nizhne-
Tabaganskoye oil field and in Paleozoic oils in
Gerasimovskoye and Severo-Kalinovskoye oil fields
of West Siberian oil-and-gas bearing basin, as well as
in some oils from Cainozoic deposits located on
Sakhalin island. Homologous of these compounds
contain from 13 to 23 carbon atoms in a molecule.
According to literature data i-AB are isorenieratene
derivatives. This carotinoid is included into the
composition of lipids of green sulfur bacteria which
inhabit waters contaminated by hydrogen sulfide. The
presence of such AB in the oils can testify to the
conditions of hydrogen sulfur contamination at the
stage of sedimentogenesis. Paleozoic oils occurring
in Usinskoye, Dzhyerskoye and Yaregskoye oil fields
of Timano-Pecherskaya oil-and-gas bearing province
contain mainly i-AB.
Among alkylbenzenes in the oils occurring in
deposits of all ages 1,2-MAB predominate over n-AB,
1,3-MAB, 1,4-MAB and ethylAB. The ratio of total
content of n-AB homologous to total content of MAB
varies from 0.3 for Cainozoic to 0.5 for Paleozoic oils.
In oils of Middle, Lower and Paleozoic deposits the
concentration of 1,4-MAB increases as compared with
the content of 1,3-MAB. Accumulation of 1,4-MAB,
which are the most thermodynamically stable isomers
among methyl-substituted alkyl benzenes, depends
on the increased transformation from Cainozoic to
Paleozoic oils.
Thus based on the results of the study on composition
and distribution of alkylbenzenes in the oils occurring
in deposits of different ages it was shown that
alkylbenzenes along with alkanes are carriers of
genetic information; differences in the distribution of
alkylbenzenes depend on the effect of catagenetic
factors which promote secondary isomerization
reactions.
402

P-270
Aromatic hydrocarbons in oils occurring in Lake Baikal
Galina Pevneva 1 , Natalya Voronetskaya 1 , Anatoly Golovko 1 , Vladimir Kashirtsev 2
1 Institute of Petroleum Chemistry SB RAS, Tomsk, Russian Federation, 2 Institute of Oil-and-Gas Geology
and Geophyisics SB RAS, Novosibirsk, Russian Federation (corresponding author:pevneva@ipc.tsc.ru)
Both geologists and biologists pay great attention
to the investigation of oil shows in Lake Baikal
because of fear of eco-catastrophe [1,2].
Physicochemical characteristics and
compositions of alkyl-aromatic hydrocarbons have
been investigated in an oil film gathered from Lake
Baikal surface and in natural oil show – bitumen taken
from the bottom of the lake at a depth of 869 m. The
samples were taken in 2008 during diving of a deepwater
station ―Mir‖. The samples were preliminary
dehydrated and purified from mechanical
contaminations.
The oil gathered from the surface greatly differ
from a bottom bitumen sample by lower values of
density (886 and 994 kg/m 3 , respectively), molecular
mass (352 a.u.m. and 584 a.u.m.) and pour point
(minus 11 о С and plus + 44 о С). The samples also
differ in element compositions. The oil sample
contains С=85.6 %; Н=13.4 %; N=0.48 % S=0.17 %
and O=0.4 %. The bitumen contains С – 87.5 %; Н –
9.9 %; N – 0.8%; S – 0.1 % and O – 1.8 %. In the oil
the content of hetero-elements is lower than in the
bitumen sample however the oil is more sulfurous.
The amount of resins in the bitumen is 17.3 % and
that of asphaltenes – 6.9 %. In the oil the content of
resins is 2.3 times and that of asphaltene – 5 times
lower as compared with the bitumen.
In both samples saturated hydrocarbons have
maximal concentrations, i.e. 55.2 and 58.0 %. Amount
of aromatic hydrocarbons in the bitumen is lowers as
compared with that in oil. Triaromatic hydrocarbons
predominate among arenes in both samples. In the oil
amount of mono- and biarenes is comparable (8.5
and 8.4 %, respectively). In the bitumen sample the
content of monoarenes is ~ twice lower than that of
biarenes (1.7 and 3.6 %, respectively).
Using chromatography-mass-spectroscopy we
analyzed compositions of alkyl-aromatic
hydrocarbons of benzene (m/z 91, 105, 119, 133),
naphthanene (m/z 128, 142, 156, 170, 184) and
phenanthrene (m/z 178, 192, 206, 220) series in the
both samples. In the oil among alkylbenzenes ortomethyl-substituted
isomers (1,2-MAB) predominate
over meta-isomers (1,3-MAB) and alkylbenzenes with
a chain of normal structure (n-AB) and para-methyl
isomers (1,4-MAB). There are no tetra-substituted
alkylbenzenes in this sample. Homologous series of
n-AB and methylalkylbenzenes consist of the
compounds with a number of carbon atoms ranging
from 12 to 27. Molecular-mass distribution of both n-
AB and MAB is unimodal with a maximum falling on
low-molecular alkylbenzenes С14-С16. In the elution
region of high-molecular alkylbenzenes containing 23-
27 carbon atoms in a molecule one observes a
―naphthenic hump‖ though peaks of alkylbenzenes
are clearly recorded in a chromatogram.
Among alkylnaphthalenes the concentration of
trimethylnaphthalenes is maximal. Such distribution is
typical to the oils occurring in Lower Jurassic deposits
of West Siberia and in Paleozoic deposits of major oiland-gas
bearing basins. Group composition of
alkylphenanthrenes in the oil from Lake Baikal is
similar to that of major oils. In the Baikal oil
dimethylphenanthrenes predominate over methyl- and
trimethylphenanthrenes.
In the bitumen sample alkyl-aromatic
hydrocarbons of benzene, naphthalene and
phenanthrene series were not determined. Probably
fractions of mono-, bi- and triarenes of this sample
mainly contain naphthenoaromatic compounds.
Thus it was shown that oil sample gathered from
the Baikal surface and that of natural oil show -
bitumen, taken from the bottom of the lake, differ in
oily, resin and asphaltene contents as well as in
hydrocarbon composition. In oil aromatic
hydrocarbons of benzene, naphthalene and
phenanthrene series are presented by alkylsubstituted
isomers, whereas in bitumen naphthenosubstituted
compounds predominate.
1. Khlystov O.M., Gorshkov A.G., et al. //Proc. of the
Russian Academy of Sciences. 2007. V.414. № 5.
P.656-659.
2.Kontorovich A.E., Kashirtsev V.A., et al. // Geologia
I Geofizika. 2007.V.48. № 12. P.1346-1356.
403

P-271
Terrestrial-derived biomarkers from Carboniferous coal deposits
at Dunbar (East Lothian, Scotland): Palaeobotanical and
palaeoenvironmental significance
Maria-Fernanda Romero-Sarmiento 1,2 , Armelle Riboulleau 2 , Marco Vecoli 2 , Fatima
Laggoun-Défarge 4 , Gerard J.-M. Versteegh 3
1 IFP Energies Nouvelles, Rueil-Malmaison cedex, France, 2 Université Lille 1 & CNRS FRE 3298, Villeneuve
d'Ascq cedex, France, 3 MARUM Universität Bremen, Bremen, Germany, 4 Université d'Orléans-INSU-
CNRS (corresponding author:maria-fernanda.romero-sarmiento@ifpen.fr)
Carboniferous (Viséan) coals from Dunbar, East
Lothian – Scotland contain well-preserved miospore
and megaspore assemblages suggesting a lycopoddominated
forest ecosystem with some ferns,
sphenopsids and pteridosperms [1-2].
The thermal immaturity of the organic matter and
the well defined microflora permit to assess the
palaeoenvironmental significance of lipid biomarkers
extracted from these coals. Rock-Eval and lipid
analyses indicate a fully terrestrial depositional
environment. Although a wide diversity of other lipid
biomarkers (alkanes, hopanoids, steroids) was
detected, we focus on the terrestrial-derived
biomarkers.
Combustion-derived PAHs pyrene, fluoranthene,
benzo[a]anthracene (Fig. 1) indicate the occurrence
of forest fires in the study areas during Early
Carboniferous times. Ionene and alkyldibenzofurans
derive from sporopollenins and lichen-biomass
respectively. Retene, cadalene, simonellite,
tetrahydroretene and kaurane are poorly specific and
can derive from a variety of early Palaeozoic land
plants.
Fig. 1. Total ion current (TIC) for selected sample.
Abietane, phyllocladane, ent-beyerane (Fig. 2) and
4β(H)-eudesmane as well as bisnorsimonellite,
diaromatic totarane, diaromatic sempervirane and 2methylretene,
however, as yet had only been reported
from conifers, which do not appear in the fossil record
until the Late Carboniferous [3]. Within the lower
Carboniferous forest ecosystem documented by the
spore content of these coals, arborescent lycopsids
are proposed as alternative sources for these
compounds.
Fig. 2. Partial m/z 109+123+193+233 fragmentogram
for selected sample.
References
[1] Spinner, E. Palaeontology 12
[2] Spinner, E., Clayton, G. Pollen & Spores XV.
[3] Scott, A. Nature 251.
404

P-272
Distribution of regular acyclic isoprenoidal alkanes in crude oils
of SE Hungary
Csanád Sajgó 1 , József Fekete 1 , Balázs Badics 2
1 Institute for Geochemical Research, Hungarian Academy of Sciences, Budapest, Hungary, 2 Statoil Global
Exploration, Stavanger, Norway (corresponding author:sajgo@geochem.hu)
The pristane to phytane ratio (pr/pr) is the most
important organic redox parameter to elucidate
depositional environment in organic geochemistry.
The value of the ratio increases with increasing
temperature or maturation. Nevertheless, the
temperature dependence and the reasons of the
variation are only known partly. The aim of this work
is to study the distribution of regular acyclic
isoprenoidal alkanes (iC13-iC20 range) in different oils
of the most important Hungarian oil region (e. g.
Algyő). This distribution has been only occasionally
studied [1, 2]. The interpretation of these markers is
rarely applied. The area studied (SE-Hungary)
includes two very deep subbasins of the Pannonian
Basin. These are filled with Neogene and Quaternary
marls, clays and sands up to the thickness of 7000
meters. The source rocks of the studied oils haven‘t
been proven yet, their origin is an opened question.
Over 40 oil samples have been chosen for this study
from relatively small and scattered reservoirs (depth
and temperature between 1 - 5 km, and 80 - 210°C,
respectively), trapping petroleum accumulations of
various age, origin, maturity parameters and migration
history. The oil geochemistry of the area (including
pr/ph and biomarkers) was studied [3, 4], but without
the isoprenoidal HCs in question.
The oils were sorted to 3 groups on the basis of the
distribution of 7 studied isoprenoidal HCs (in Fig 1.
typical representatives are shown). In the ―S‖ type oils
(~21) proportions of isoprenoidal HCs are similar. In
the ―D‖ types (~4) the amount of pr and ph is relatively
small, and the proportions of longer chain isoprenoids
steadily decrease. In ―I‖ oils (~16) the proportions of
given isoprenoids grow parallel with chain length. The
notations ―pr‖ and ―ph‖ denote pr or ph dominance,
respectively.
Pr vs. ph and pr/�(iC13-iC20) vs. ph/�(iC13-iC20) ratios
follow a linear trend in oils showing low (0.04-0.13)
ph/�(iC13-iC20) and high (0.12-0.28) iC13/�(iC13-iC20)
values (―low-ph‖). In these oils the pr/�(iC13-iC18) and
ph/�(iC13-iC18) ratios show a negative, parallel trend
with very close to each other, with the same slope of
tangent: 0.5. This suggests that in these oils both the
pr and the ph have produced the lighter/shorter
isoprenoid alkanes (iC13-iC18 range), in similar ratio
(cracked parallel). In the other oils (―high-ph‖)
characterized by higher (0.1-0.28) ph/�(iC13-iC20) and
low (0.05-0.12) iC13/�(iC13-iC20) values the
concentration of ph is increased (pr/ph ratio
decreased) without any trend which may refer to more
reductive depositional environment and less intensive
cracking compared to those of the other oils.
Correlation between ph and iC13-iC19 in low-ph and
between pr and iC13-iC18 in high-ph oils was
observed.
0,3
0,2
0,1
0
Üllés DK-2, "S" type
Algyő-502, "D" type
Forráskút-5, "I-pr" type
Ruzsa-6, "I-ph" type
iC13 norfar far iC16 norpr pr ph
Fig. 1 Distribution of regular acyclic isoprenoidal
alkanes in typical crude oils of the four groups
This work was funded by the Hungarian Scientific
Research Fund (OTKA) through grant K84086.
References
[1] Kissin, Y. V. 1993. Catagenesis of light acyclic
isoprenoids in petroleum. Organic Geochemistry 20.
1077-1090
[2] Illich, H. A. 1983. Pristane, Phytane, and Lower
Molecular Weight Isoprenoid Distributions in Oils
AAPG Bulletin 67. 385-393.
[3] Sajgó, Cs. 1984. Organic geochemistry of crude
oils from South-east Hungary. Organic Geochemistry
6, 569-578.
[4] Sajgó, Cs. 2000. Assessment of generation
temperatures of crude oils. Organic Geochemistry 31,
1301-1323.
405

P-273
Preservation of β-carotane in sediments from the Lopare basin,
Bosnia and Herzegovina
Aleksandra Ńajnoviš 1 , Nenad Grba 2 , Ksenija Stojanoviš 3 , Branimir Jovanţiševiš 3 , Biljana
Dojţinoviš 1
1 Center of Chemistry, IChTM, 11000 Belgrade, Serbia, 2 Faculty of Ecology and Environmental Sciences,
11000 Belgrade, Serbia, 3 University of Belgrade, Faculty of Chemistry, 11000 Belgrade, Serbia
(corresponding author:sajnovica@chem.bg.ac.rs)
β-Carotane and other diagenetic products of βcarotene
are specific indicators of anoxic lacustrine
environments. Preliminary organic geochemical
studies of sediments of Lopare basin show that they
contain a moderate amount of immature algal organic
matter (OM) deposited in reducing to anoxic
conditions with high salinity. The investigation was
performed on 27 sedimentary rocks with depth of 344
m. The majority of samples contain β-carotane in
relatively high quantities, and in some, it is the most
abundant compound in the total distribution of
hydrocarbons. Therefore, the Lopare basin is chosen
for study and determination the conditions, which are
favorable to β-carotane precursors and/or
preservation of its hydrocarbon skeleton. The relative
content of β-carotane was correlated with the specific
organic geochemical parameters and contents of
macro-, microelements and rare earth elements.
After the isolation of soluble organic matter using
column chromatography, saturated and aromatic
hydrocarbons were analyzed by gas chromatographymass
spectrometry (GC-MS). The content of macro-,
microelements and rare earth elements (a total of 47
elements) were determined by means of ICP-OES
spectrophotometer.
The relative content of β-carotane in the total
distribution of hydrocarbons is up to 25%. As the OM
is immature; C31(S)/C31(S+R)

P-274
Pr/Ph ratio in the Bazhenov formation rock samples (Western
Siberia)
Ivan Goncharov 1 , Vadim Samoylenko 1 , Nikolay Oblasov 1 , Vladimir Volkov 2
1 JSC «TomskNIPIneft», Tomsk, Russian Federation, 2 SE «SAC RNM named after V.I. Shpilman», Tyumen,
Russian Federation (corresponding author:GoncharovIV@nipineft.tomsk.ru)
Bazhenov formation, the major oil source in
Western Siberia, includes an area of about 1 mil.
km 2 . Rock lithology and organic matter (OM)
content and quality changes throughout the central
regions of Western Siberian to its periphery, which,
in its turn, affects the rock potential generation and
molecular composition of generated hydrocarbons.
Thus, in this case, an important factor is the
regional feature of molecular parameter changes,
defining the source rock organic material, as this
gives more reliable correlation of oils of this genetic
type.
One of the major features determining the rock
organic material quality is the oxidation-reduction
regime during sedimentogenesis and diagenesis.
The most frequently applied molecular parameter to
evaluate the oxidation-reduction conditions of
sedimentation is Pr/Ph ratio.
The zone of minimum parameter value Pr/Ph (0.6-
1.0) for Bazhenov formation rocks is confined to the
central part of the sedimentation basin [1]. Pr/Ph
ratio increases from central zones to the periphery.
However, this parameter value for Bazhenov
formation rocks is not more than 2.0 throughout the
area [2].
The regional behavior distortion of Pr/Ph changes
was firstly detected in the eastern part of Western
Siberia within Pyl-Karaminsk arch (east of Khanty-
Mansi Autonomous Okrug). This region pertains to
the marginal distribution boundary of Bazhenov
formation rocks, where eastward they are
substituted by less bituminous rocks of Mariyanov
formation. According to the regional behavior of
Pr/Ph ratio it should be 1.4-1.7. However, research
results of 40 sample-extracts from Bazhenov
formation cross-section, in 8 wells of Pyl-Karaminsk
arch area indicated that the average value of Pr/Ph
ratio is 0.81-1.20, while for some other samples the
Pr/Ph ratio is 0.63. At the same time, OM of
Bazhenov formation rocks is characteristic of rather
low maturity. Thus, the ratio S/(S+R) St29 for all
investigated samples ranges from 0.09 to 0.20.
It is obvious that the Pr/Ph ratio in this region could
not have such a low value. It is possible that such a
low maturity indicates the fact that rock OM has not
even generated the first hydrocarbon portions.
Therefore, free hydrocarbons in the rock pore
space are transformation products of initial OM
during diagenesis. As stated earlier, in several
cases of rather low maturity, Pr/Ph ratio parameter
could be significantly distorted [3].
Actually, the investigated regional behavior of Pr/Ph
ratio in adjoining areas indicated that this value
parameter increases with OM maturity growth (Fig.)
When the S/(S+R) St29 ratio is 0.25-0.30, then
Pr/Ph ratio in Bazhenov formation rocks reaches
the corresponding value of this region. It is obvious
that at this stage of maturity the amount of
generated hydrocarbons already significantly
exceeds the amount of free hydrocarbons, which
were initially in rock pore space.
Pr/Ph
2.0
1.6
1.2
0.8
Pyl-Karaminsk arch
adjoining areas
0.4
0.00 0.10 0.20 0.30 0.40 0.50 0.60
S/(S+R) St29
Fig. Relationship of Pr/Ph and S/(S+R) St29)
References[1] Goncharov I.V. Geochemistry of
oils in West Siberia. Moscow: Nedra, 1987, 181
p.;[2] Goncharov I.V. et al. Source rocks and oils in
eastern part of West Siberia / Oil industry, 2010,
№8, p.24-28; [3] Volkman J.K. and Maxwell J.R.,
1986. Acyclic isoprenoids as biological markers //
Biological Markers in the Sedimentary Record (R.B.
Johns, ed) / Elsever, New York, p. 1-42.
407

P-275
Aromatic hydrocarbons in oils from cambrian and precambrian
deposits (East Siberia, Russia)
Alexandra Akhmedova 1 , Olga Serebrennikova 2 , Olga Shiganova 1
1 Siberian Research Institute of Geology, Geophysics and Mineral Resources, Novosibirsk, Russian
Federation, 2 Institute of Petroleum Chemistry, SB RAS, Tomsk, Russian Federation (corresponding
author:ahmedova-sniiggims@yandex.ru)
Oil fields in the East Siberia are found within
Riphean, Vendian and Cambrian deposits. Typical
oils from three of the main East Siberian oil regions
(Nepa-Botuobinskaya - NB, Baikitskaya - B and
Katangskaya - K) were investigated in order to get
special characteristics of aromatic HC composition in
them. The investigated area covers the so called
―gold belt‖ of Lena-Tungusskaya basin.
Oils from 8 areas of Riphean-Vendian-
Cambrian deposits from test and exploration drill
boreholes were investigated. Total content of mono-,
bi- and tricyclic aromatic HC, which was detected by
GC-MS technique, relative to the concentration of nalkanes
fluctuates from 6% up to 34%; it is maximum
(15-34%) in oils from NB region but it is much lower in
oils from K (5-16%) and in oils from B (6-11%)
regions. Compounds of benzene, naphthalene (N),
fluorene (F) and phenanthrene (P) types are identified
in investigated oils. Monoaromatic HC are
predominating in the major part of oils; but the oil from
Sobinskaya area has 11% of condensed arenes only
and only three from oils are the exclusion of this rule;
Ns are predominating in these oils. Comparatively to
all the other aromatic HC, Fs are presented in much
lower concentrations (not more than 2%). The
concentration of Ps in the most part of oils is 18-23
relative %.
Monoarenes. Homological series of
alkylbenzenes with normal composition and with one
substituent radical (n-AB) are identified among
monoarenes; this substituent is usually a linear
aliphatic chain with 10-30 atoms of C (C10-C30). In oils
from NB region the maximum distribution is on C17
and C21, mostly on C21. In oils from B region the main
maximum is on C11-C13.
Also isomeric ortho-, meta- and para-
methylalkylbenzenes (MAB), dimethylalkylbenzenes
(DMAB) and trimethylalkylbenzenes (TMAB) were
identified. Phytanilbenzene (PhB, C26) with isoprenoid
aliphatic chain C20 and its methyl- and dimethyl-
substituted homologs were identified in all oils.
DMAB is predominating in the monoarenes
mixture in oils from Riphean deposits; their
concentration is increasing up along a stratigraphic
cross-section while the concentrations of TMAB are
going down and the concentrations of MAB and n-AB
are increasing.
Biarenes. Identified biarenes include N, F and
their alkyl-substituted homologs which have up to two
methylene groups (Fs) and up to four methylene
groups (Ns) in their side alkyl chains.
The content of appropriate Ns in oils from
Lower Cambrian strata is growing up while the
quantity of methylene groups in side substituents of
aromatic rings is increasing. Going down along
stratigraphic cross-section one can find similar
concentrations of compounds with two (DMN) and
three (TMN) atoms of C in oils from the top of
nonsegmented Vend-Cambrian Stratum (Usolskaya
Formation); N and methylnaphthalene (MN) have high
relative concentrations in these oils. TMN is the main
compound in more aged oils. The oils from K region
have the biggest concentrations of unsubstituted N.
Methylfluorenes (MF) are predominating in Fs
of Riphean oils from B region. Dimethyl-substituted
fluorenes (DMF) are predominating in oils from more
recent deposits.
Triarenes. P and its alkyl-substituted
homologs with 1-4 atoms of C were identified in
investigated oils. Phenanthrenes with two methylene
groups in the side chains (DMP) are predominating
among all homologs of phenanthrene in all
investigated oils. Their concentrations are between 26
and 44 relative %.
Analysis of the data showed that there is a
wide variety of alkyl-substituted benzenes, Ns,
fluorenes and Ps in ancient oils. The highest
concentrations of these compounds were found in oils
from NB region. Relative concentrations of special
types of arenes varies in different oils; but in the most
part of oils alkylbenzenes are the most representative
type of arenes.
408

P-276
Effects of biomarker biodegradation on tar sands of the
Pirambóia Formation, Paraná Basin, Brazil
Eliane Soares de Souza, Georgiana Feitosa da Cruz, Hélio Severiano Ribeiro
North Fluminense State University/Petroleum Engineering and Exploration Laboratory (UENF/LENEP),
Macaé, Brazil (corresponding author:eliane@lenep.uenf.br)
Major magmatic events are believed to have been
effective in the generation, migration and
accumulation of significant quantities of oil in Paraná
Basin 1 . The genesis of the tar sands accumulations
has been attributed to the Irati-Pirambóia petroleum
system 2 . The Irati Formation has an organic matterrich
rock mature due to the thermal effect of the Early
Cretaceous basic igneous intrusions, and hence offer
real prospects of large-scale oil generation 1 . The oil
migrated along the diabase dike / sedimentary rock
contact to form the reservoir rocks of eolian
sandstone of the Pirambóia Formation 2 .
The geology, organic facies, maturation and
migration on the organic matter-rich rock focused
primarily on the saturated hydrocarbon fractions (e.g.,
n-alkane distribution, isoprenoid/n-alkane ratios,
biomarker maturity parameters) have been discussed
by a number of authors 1,2,3 . However, biomarker
biodegradation studies of these samples have not
been addressed. In this sense, the aim of this work
was to examine to rank the extent of biodegradation
in tar sands of the Pirambóia Formation with particular
emphasis on determination of variations on hopane
(and homologues) biomarker distributions.
We studied 6 (S1 to S6) tar sands samples from
Pirambóia Formation (FB and GI). The samples were
pulverized extracted with dichloromethane in a
Soxhlet apparatus for 40 hours. The extract was
fractionated by liquid chromatography and analyzed
by GC-FID and GC-MS.
The Pirambóia tar sands evaluated were severely
biodegraded and of the n-alkanes, isoprenoid alkanes
and light aromatics compounds were removed by
waterwashing and/or biodegradation. During the
advanced stages of biodegradation, such as these tar
sands, hopanes and other pentacyclic triterpanes can
be altered, being converted either to 25-norhopane
homologues 4 or to other, as yet uncharacterized,
products.
In this work, the hopane distributions have been
altered to differing degrees with the homologues
above C30 decreasing in concentration prior to the
tricyclic and C24-tetracyclic terpanes. The high
resistance this compounds to biodegradation indicate
that they are well suited to serve as correlation
parameters in heavily altered samples. Da Cruz et al. 5
showed a preferential depletion of R C35 hopane in
relation to tricyclic terpane, under aerobic conditions.
Demethylation at the C25 position is observed for
most hopanes in severely biodegraded samples. The
Figure 1 showed relatioship between C35 hopane
index versus 25-norhopane ratio used to rank the
extent of biodegradation.
C35 Hopane Index
40
35
30
25
20
15
10
5
0
S5
S6
S2
S3
S1
0 5 10 15 20 25
25-Norhopnae Ratio
Tar sand FB
Tar sand GI
Fig. 1. Plot of C35 hopane index (100 x C35/C31-35) and the 25norhopane
ratio [(100 x C30-34 25-norhopanes (m/z 177) / �
C31-35 hopanes (m/z 191) + C30-34 25-norhopanes (m/z 177)].
In the most biodegraded samples (S1 and S5,
Fig.1) the hopanes index decrease showing That C35
is more biodegradable than C31-34 homohopanes. The
same effect was observed on 25-norhopane ratio
showing that in severely biodegraded oils the 25norhopanos
are also consumed during the process.
References
[1] Thomaz-Filho, A., Mizusaki, A. M. P., Antonioli, L. (2008)
Marine and Petroleum Geology 25, 143-151.
[2] Araújo, C. C. de, Yamamoto, J. K., Rostirolla, S. P.,
Madrucci, V., Tankard, A. (2005) Marine and Petroleum
Geology 22, 671-685.
[3] Araújo, L. M., Trigüis, J. A., Cerqueira, J. R., Freitas, L.
C. da S. (2000) in Mello, M. R. and Katz, B. J., Eds.,
Petroleum systems of South Atlantic margins: AAPG Memoir
73, 377-402.
[4] Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The
Biomarker Guide, second ed. Cambridge University Press,
Cambridge, UK.
[5] da Cruz, G. F., Santos Neto, E. V. & Marsaioli, A. J.
(2008) Organic Geochemistry 39, 1204-1209.
S4
409

P-277
Statistical analysis of diamondoid and biomarker from Brazilian
Basin oil samples
Marcia Springer, Debora Azevedo, Bruno Caldas, Luiz Landau
Federal University of Rio de Janeiro, Rio de Janeiro, Brazil (corresponding
author:marcia_springer@hotmail.com)
Biomarker distributions are widely used in assessing
oil maturity [1]. Many of the isomeric biomarker
maturity parameters reach equilibrium before the
main part of the oil window and, in some cases, show
inversion at high maturity levels. Consequently, these
ratios are not effective as indicators for highly mature
oils. Diamondoids have an unusually high thermal
stability and resistance to biodegradation compared to
other crude oil constituents. Using ratios of
diamondoids and biomarkers in combination provides
a more refined assessment of maturity and
depositional environment [2,3,4].
In the present study, sixteen samples of oils from
Sergipe/Alagoas sedimentary basins of Brazilian
continental margin were selected and studied on
diamondoids and biomarkers. The oil samples were
analyzed by gas chromatography coupled to mass
spectrometry and hierarchical group analysis (Cluster)
aiming to correlate biomarker and diamondoid
parameters. Cluster analysis is an exploratory data
analysis tool for solving classification problems.
Results indicate that the selected crude oils display a
high degree of thermal maturity, when plotting
biomarkers versus diamondoid concentrations (Fig.1)
(e.g. Stigamastane versus 3-+4- Methyldiamantane).
Four groups were well detected: the sample SES45
is highly mature and cracked oil; the samples SES14
and ALS27 are mature and medium cracked oils; the
sample CAP1 is low mature oil; and a fourth group
formed by mature but not cracked oils.
The hierarchical cluster analysis (Fig. 2) allows
recognizing groupings of oil samples according to
obtained in scores plot. Both stigmastane versus
methyldiamantane concentration graphic and
statistical analysis show similar results: the sample oil
CAP1 showed to be the less mature and the oils
ALS27 and SES14 are closer to another group –
sample SES45. The statistical analysis was a
powerful mean to the understanding, analysis and
visualization of the data.
STIGMASTANE STIGMASTANE ( ( ng ng / / mg mg ) )
300.0
250.0
200.0
150.0
100.0
CAP1
4SES12
7D14
SES83
50.0
ALS8
ALS3
4RB19 7CB28
SES14
ALS27
SES45
0.0
6PDM NAB6
20.0 40.0 60.0 80.0 100.0 120.0 140.0
3-+4-METHYLDIAMANTANE 3-+4- 3-+4-METHYLDIAMANTANE 3-+4-
( ng / mg )
Fig.1: Correlation between biomarker (stigmastane)
and diamondoids (methyldiamantanes) concentration
in oils.
Similarity Similarity % %
0
25
50
75
100
SES45 SES45 SES45 SES45
SES14 SES14 SES14 SES14
ALS27 ALS27 ALS27 ALS27
RR1 RR1 RR1 RR1
SES107 SES107 SES107 SES107
6PDM 6PDM 6PDM 6PDM
Fig.2: Dendrogram of hierarchical cluster analysis
calculated using Euclidean distance.
References
[1] Peters, K.E., Moldowan, J. M., 1993. The
Biomarker Guide. Interpreting Molecular Fossils in
Petroleum and Ancient sediments. Pentice-Hall. New
Jersey.
[2] Dahl, J.,et al. (1999). Nature 399, 54-56.
[3] Springer, M.V., Garcia, D.F., Gonçalves, F.T.T.,
Landau, L., Azevedo, D.A. (2010). Organic
Geochemistry, 41(9), 1013-1018.
[4] Azevedo et al. (2008) Fuel 87, 2122-2130.
ALS3 ALS3 ALS3 ALS3
7D14 7D14 7D14 7D14
SES83 SES83 SES83 SES83
7CB28 7CB28 7CB28 7CB28
RB19 RB19 RB19 RB19
NAB6 NAB6 NAB6 NAB6
4SES12 4SES12 4SES12 4SES12
ALS8 ALS8 ALS8 ALS8
CAP1 CAP1 CAP1 CAP1
410

P-278
Short-chain steranes and isophopanes in Miocene source rocks
from hyperthermal basin (Banat Depression, S.E. Pannonian
Basin, Serbia)
Ksenija Stojanoviš 1,2 , Sanja Mrkiš 2 , Aleksandar Kostiš 3 , Hans Peter Nytoft 4 , Aleksandra
Ńajnoviš 2
1 University of Belgrade, Faculty of Chemistry, 11000 Belgrade, Serbia, 2 Center of Chemistry, IChTM, 11000
Belgrade, Serbia, 3 University of Belgrade, Faculty of Mining and Geology, 11000 Belgrade, Serbia,
4 Geological Survey of Denmark and Greenland, DK-1350 Copenhagen, Denmark (corresponding
author:xenasyu@yahoo.com)
Short-chain (C21 and C22) steranes and isohopanes
were investigated in Miocene source rock samples
originated from Banat Depression, S.E. Panonian
Basin, Serbia. This area, like the entire basin, is
characterized by hyperthermicity (geothermal gradient
4.0-7.5 o C/100m) and by an exceptionally high heating
rate for Miocene sediments (9-21.9 o C/Ma). Organic
matter (OM) of the samples consists predominantly of
Type II kerogen. Oil window began at 110-120 o C and
vitrinite reflectance (Rc) ca. 0.53-0.58%, reached a
maximum at 145-150 o C and Rc ca. 0.72-0.75% and
ended at 170-175 o C and Rc ca. 0.89-0.93%, which
correspond, to relative depths between 1850 and
2100 m, 2600 and 2900 m, and ca. 3500 m,
respectively. Numerous biomarker parameters
indicated a mixed terrestrial-marine origin of the OM,
related to a lacustrine sub-oxic depositional setting.
After bitumen extraction and isolation of saturated,
aromatic and NSO fraction, saturated hydrocarbons
were analyzed using GC-MS-MS.
All the samples contained relatively high amount of
C21 and C22 steranes. [C21+C22(αα+ββ)steranes]/[ΣC27-C29(αα(R+S)+ββ(R+S))-steranes]
ratio, (C21+C22)/ΣC27-C29 showed statistically
significant correlation with present temperature,
production index (PI), Tmax and biomarker maturity
ratios. No statistically significant correlation between
the (C21+C22)/ΣC27-C29 and pristane/phytane (Pr/Ph)
as well as C35H(S)/C34H(S) homohopane ratio was
observed. In addition, the ratio did not correlate with
the source parameters, distribution of C27-C29 regular
steranes, oleanane index and C30 sterane index.
Therefore the ratio was used for an estimate the OM
maturity Samples, whose OM attained a maturity
corresponding to the late stage of oil generation
(present temperature and Tmax >153 o C and 447 o C,
respectively and originate from depths >3050 m) have
values of (C21+C22)/ΣC27-C29>0.25. The value of the
ratio for immature samples is 2), which are also
characterized by slightly higher temperatures are
close to the values of these parameters for
moderately mature samples the OM of which was
deposited in anoxic conditions (Pr/Ph

P-279
Characterization of biomarkers occluded inside oil and coal
asphaltenes
Ksenija Stojanoviš 1 , Nikola Vukoviš 2 , Vladimira Hrepiš 1 , Aleksandra Ńajnoviš 3 , Dragana
Ņivotiš 4 , Branimir Jovanţiševiš 1
1 University of Belgrade, Faculty of Chemistry, 11000 Belgrade, Serbia, 2 University of Belgrade, Innovation
Center of the Faculty of Chemistry, 11000 Belgrade, Serbia, 3 Center of Chemistry, IChTM, 11000 Belgrade,
Serbia, 4 University of Belgrade, Faculty of Mining and Geology, 11000 Belgrade, Serbia (corresponding
author:xenasyu@yahoo.com)
Maltenes occluded inside asphaltene structures are of
the great importance in organic-geochemical studies
of biodegraded crude oils [1, 2]. In this work, occluded
maltenes have been released from asphaltene
aggregates using three methods: a) mild pyrolysis of
asphaltenes at 250°C, during 4h in inert atmosphere
of nitrogen; b) mild oxidation of asphaltenes using
H2O2/CH3COOH reagent and c) mild oxidation of
asphaltenes using NaIO4/NaH2PO4 reagent [1].
Asphaltenes isolated from a non-biodegraded crude
oil of mixed terrestrial-marine origin and from bitumen
of a humic bituminous coal were used as substrates.
Maltenes from oil, from coal bitumen and those
released from asphaltenes were separated into
saturated, aromatic and NSO fractions. Saturated
hydrocarbons were analyzed using GC-MS.
Occluded maltenes yields, relative to initial mass of oil
or coal asphaltenes, were relatively low in all the
experiments (

P-280
Biomarker hydrocarbons in schungites (Lower Proterozoic,
Karelia)
Aleksey Kontorovich, Irina Timoshina, Tatyana Parfenova, Ananoliy Postnikov
Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation (corresponding
author:TimoshinaID@ipgg.nsc.ru)
In this study we examined organic matter (OM) of
shungites (2100-1950 Ma) from the Lower Proterozoic
Trans-Onega Formation in the section of
Zazhoginskaya-175 well within Onega synclinorium
(the Baltic shield). TOC concentrations in schungites
from the well account for 1.6-27.5%, with δ 13 С ranging
from ─39.7 to ─28.1 ‰, i.e. there was preserved
carbon isotopic composition featuring mature marine
polymer-lipid OM. The OM was metamorphosed to a
stage of graphite (the atomic ratio (H/C)at of kerogen
not exceeding 0.06-0.08), which is characterized by
low contents of chloroform-extractable bitumens
(0.007-0.021%). The main components of chloroformextractable
bitumen are known to be saturated
hydrocarbons (HC) (35.9-60.7%) and resins (27.5-
53.9%).
In acyclic hydrocarbons, the n-C27/n-C17 ratio of nalkanes
and Pr/Ph ratio of isoprenoids range within
0.0-0.1 and 0.5-1.1, respectively. C27 and C29 sterane
contents are shown to be close, (С29/С27 ratio
averages at 0.9-1.2), and the Dia/Reg ratio amounted
to 0.3-0.4. In hopanes, the Ts/Tm (trisnorhopanes)
and C35/C34 (homohopanes) ratios range within 0.9-
1.1 and 0.6-0.8, respectively. In some samples, the
tricyclane 2С19-20/С23-26 index rises to 1.8, it averages,
however, at

P-281
The significance of novel A-norsteranes and perylene in
Devonian reefs and crude oils
Svenja Tulipani 1 , Kliti Grice 1 , Paul Greenwood 1,2 , Robert Lockhart 1 , Muhammad Asif 3 ,
Kenneth Williford 1 , Arndt Schimmelmann 4
1 WA Organic and Isotope Geochemistry Centre, Applied Chemistry, Curtin University of Technology, Perth,
Australia, 2 University of Western Australia, Perth, Australia, 3 Chemistry Department, University of
Engineering and Technology, Lahore, Pakistan, 4 Department of Geological Sciences, Indiana University,
Bloomington, United States of America (corresponding author:s.tulipani@curtin.edu.au)
Distributions of unusual compounds including a series
of putative C19 A-norsteranes - potential novel sponge
biomarkers originating from stromatoporoids - have
been detected in Devonian sediments and crude oils
[Canning Basin, Western Australia and Western
Canada Sedimentary Basin (WCSB)]. A similar series
of low-molecular-weight A-norsteranes was also
generated from an extant sclerosponge by catalytic
hydropyrolysis (Hypy).
The samples from the Canning Basin are of Givetian
and Late Devonian age and were presumably
deposited in a shallow marine setting. The sediments
from the WCSB originate from the Frasnian Duverney
Formation which was mainly deposited in palaeowater
depths >100m. The dominant reef-building
organisms throughout the Devonian until the
Frasnian-Famennian mass extinction were
stromatoporoids. The oldest fossil remains of these
organisms date to the early Cambrian.
Stromataporoids were particularly abundant from the
Middle Ordovician to Late Devonian and from the
Jurassic to the Cretaceous [1]. It is now commonly
accepted that stromatoporoids are members of the
phylum porifera [1, 2]. Their closest living relatives are
presumably found amongst the sclerosponges since
both types of organisms show similar growth forms
and structural elements [1, 2]. Whereas various
studies have revealed a great diversity of sterol
structures within the class Demospongea [3], the
sterol compositions of sclerosponges have not been
robustly investigated. In this work we extracted a
sclerosponge collected from the Jamaican coast and
conducted Hypy on the residue. The pyrolysate was
further fractionated by silica gel column
chromatography. A series of C19 A-norsteranes was
tentatively identified in the Devonian stromatoporoidrich
sediments and crude oils as well as in the
aliphatic fraction of the pyrolysate of the extant
sclerosponge. We therefore propose that the putative
C19 A-norsteranes are novel biomarkers for
stromatoporoids and sclerosponges. This also
supports the theory of a close relationship between
extant sclerosponges and stromatoporoids. A
Precambrian oil from the South Oman Salt Basin [4]
was used as a reference to identify the putative Anorsteranes.
Furthermore, the polyaromatic hydrocarbon perylene
and aromatic compounds bearing the perylene
backbone - potential precursor fragments in the
sedimentary formation pathway to perylene - have
been detected in the Givetian sediments from the
Canning Basin. Perylene has been frequently
reported in Mesozoic and Cenozoic sediments, but it
has only occasionally been found in Paleozoic
samples [5]. Perylenequinone pigments present in a
variety of extant organisms including wood-degrading
fungi and crinoids have been suggested as potential
precursors on the basis of structural similarities [5, 6].
The sedimentary abundance of perylene has also
been linked with the activity of wood degrading fungi
[5]. Potential sources of perylene which might explain
its unusual appearance in these presumably marine
samples include perylenequinones in crionoids or
marine fungi. Furthermore, the perylene might
originate from terrestrial input and fungal lignin
degradation of early trees or from the organism
prototaxites, a giant terrestrial fungus abundant from
the Late Silurian until the Late Devonian.
In future studies we hope to examine the biomarker
composition – with special regard to the potential
novel sponge biomarkers - of additional samples from
the Canning Basin (Western Australia) to span the
Givetian-Frasnian boundary.
References
[1] Stearn, C.W., et al., Acta Palaeontologica
Polonica, 1999. 44(1): p. 1-70.
[2] Stearn, C.W., Lethaia, 1972. 5: p. 369-388.
[3] Bergquist, P.R., et al., Biochemical Systematics
and Ecology, 1991. 19(1): p. 17-24.
[4] Grosjean, E., et al., Organic Geochemistry, 2009.
40(1): p. 87-110.
[5] Grice, K., et al., Geochimica et Cosmochimica
Acta, 2009. 73(21): p. 6531-6543.
[6] Jiang, C., et al., Organic Geochemistry, 2000.
31(12): p. 1545.
414

P-282
Land plant markers in Gippsland Basin oils, Australia
Herbert Volk 1 , Manzur Ahmed 1 , Se Gong 1 , Chris Boreham 2 , Peter Tingate 3 , Dianne
Edwards 2
1 CSIRO, North Ryde, Australia, 2 Geoscience Australia, Canberra, Australia, 3 GeoScience Victoria,
Melbourne, Australia (corresponding author:Herbert.Volk@csiro.au)
The Gippsland Basin is one of Australia‘s most prolific
oil provinces and is dominated by oils with strong
terrestrial signatures. A previous study of over 60 oils
used multivariate statistical analyses of aliphatic
biomarkers and stable carbon isotope signatures to
define two main oil families, ‗GA‘ and ‗GB‘ [1]. The
larger and less variable oil family (GA) was further
distinguished into two sub-families, GA1 and GA2
oils, which occur in differnt parts of the basin. GB oils,
and to a lesser degree GA2 oils, have both mature
and immature biomarker features, possibly acquired
during petroleum migration. Some oils remained
unclassified or were classified as vagrant, but all other
oils were suggested to be derived from coals and
carbonaceous shales of the Latrobe Group. This
study investigated the distribution of land plant
markers in a subset of 23 oils representatiing all the
oil families for a more precise understanding on the
source characteristics and migration of petroleum in
the Gippsland Basin. The studied markers include di-,
tri- and tetracyclic diterpanes derived chiefly from
Southern Hemisphere gymnosperms, oleanane ±
lupane and their A-ring contracted counterparts
originating from angiosperm plants, bicadinanes that
are particularly abundant in Dipterocapacea
hardwood trees, and aromatic land plant markers
such as retene and cadalene.
Studies on Cretaceous and Palaeogene sediments of
the Taranaki Basin, [2] defined an age-specific
angiosperm/gynmosperm index (AGI), which when
applied to the Gippsland Basin oil samples analysed
in the present study suggests Late Cretaceous source
rocks, except for a West Seahorse oil which may be
derived from Palaeogene source rocks. The
Gippsland Basin oils are dominated by 16� (H)phyllocladane
and in some cases by 4�(H)-19norisopimarane,
except for an ―unassigned‖ Marlin 1
oil dominated by isopimarane. This oil also contains
the highest amount of A-ring contracted lupane,
indicating that angiosperm contributions are also
distinct (Figure 1). Bicadinanes, often interpreted as
angiosperm markers for Dipterocapacea, were
present in low amounts in all the oils studied. Their
abundance relative to C30 �� hopane falls within a
very narrow range for GA1 oils and is more variable
for other samples. The widespread occurrence of
bicadinanes is noteworthy, since Dipterocarpacea did
not evolve until the Oligocene, whereas the source
rocks for most of the oils are probably hosted in the
Cretaceous Latrobe Group. This observation confirms
that bicadinanes are not exclusive to oils containing
Dipterocarpaceae input. Aromatic land plant marker
input to unassigned Mulloway 1 and Marlin 1 oils is
much greater than for other oils, in particular it is
higher than for the West Seahorse 1 oil and the tightly
clustering oils from Family GA1.
dO
Figure 1. Ternary diagram of de-A-oleanane (dO), de-Alupane
(dL) and de-A-ursane (dU). Oil families after [1].
References
Marlin 1
dU
[1] Summons et al., (2002) The Oils of Eastern Australia,
Geoscience Australia GeoCat# 68754.
[2] Killops, S.D., Raine, J.I., Woolhouse, A.D. and Weston,
R.J., (1995) Chemostratigraphic evidence of higher-plant
evolution in the Taranaki Basin, New Zealand. Organic
Geochemistry 23, 429-445.
dL
GA1 GA2 GB GV Unassigned
415

P-283
Correlation between composition of naphthenoarenes and their
saturated analogues in oils from different geological age
deposits
Natalya Voronetskaya, Galina Pevneva, Anatoly Golovko
Institute of Petroleum Chemistry SB RAS, Tomsk, Russian Federation (corresponding
author:voronetskaya@ipc.tsc.ru)
Now hydrocarbons of hybrid structure containing
simultaneously aromatic and naphthenic cycles –
naphthenoarenes are the least studied class of oil
compounds. The structure of naphthenearene
molecules determined in oils is similar to that of
saturated cyclic compounds (cyclanes). The aim of
the present work was to study compositions and
distributions of naphthenoarenes and cyclanes in oils
of multihorizon fields. The oils recovered from
multihorizon oil fields Sirakovo (5 samples) and
Bradarac-Maljurevac (3 samples) (Serbia) occurring
in Cainozoic deposits, as well as oils from Usinskoye
oil field (5 samples), Paleozoic deposits (Russia) were
used as the objects of investigation.
The oils in Sirakovo oil field occur in the depths
ranging from 1400 to 1800 m and oils in Bradarac-
Maljurevac oil field - from 1800 to 2200 m. The depth
of occurrence of Paleozoic oils in Usinskoye oil field
ranges from 1190 to 1400 m.
Concentrates of saturated, mono-, bi- and
triaromatic hydrocarbons were isolated by a column
liquid-adsorption chromatography. The concentrates
of arenes were divided into fractions of alkyl- and
naphthenoarenes by extraction with methanol.
Carbamide dewaxing was used to separate cyclanes
from acyclic alkanes.
Compositions of cyclanes, naphthenobenzenes,
naphthenonaphthalenes and
naphthenophenanthrenes were determined by a
mass-spectrometry method via direct introduction of
the sample into an ionization chamber. The energy of
ionizing electrons was 12 eV.
Cyclanes contain from 1 to 5 saturated cycles in
a molecule. Naphthenoarenes are presented by the
compounds with a number of aromatic cycles from 1
(naphthenobenzenes) to 3
(naphthenophenanthrenes). Total number of cycles in
a molecule of naphthenoarenes does not exceed five.
The content of compounds with two cycles in a
molecule – mononaphthenobenzenes and their
saturated analogues bicyclanes – symbately
decreases with the depth of oil occurrence.
Tricyclic compounds are presented by
naphthenobenzenes, mononaphthenonaphthalenes
and their saturated analogues – tricyclanes. The
content of dinaphthenobenzenes decreases with the
depth of oil occurrence. The content of
naphthenonaphthalenes increases in oils from
Cainozoic deposits with the depth of occurrence and
decreases in Paleozoic oils. The concentration of
tricyclanes in oils from Cainozoic deposits decreases
with the depth of occurrence, while in Paleozoic oils it
increases.
Among tetracyclic compounds we have studied
distributions of trinaphthenobenzenes,
dinaphthenonaphthalenes,
mononaphthenophenanthrenes and their saturated
analogues – tetracyclanes. The content of
trinaphthenobenzenes decreases with the depth of oil
occurrence. The contents of
dinaphthenonaphthalenes and
mononaphthenophenanthrenes increase in Cainozoic
oils with the depth of occurrence and decrease in
Paleozoic oils. The content of tetracyclanes increases
in deeper occurring oils both from Cainozoic and
Paleozoic deposits.
Pentacyclic compounds are presented by
tetranaphthenobenzenes, trinaphthenonaphthalenes,
dinaphthenophenanthrenes and their saturated
analogues – pentacyclanes. The contents of both
naphthenoarenes and their saturated analogues –
pentacyclanes increase in Cainozoic and Paleozoic
oil with the depth of occurrence. One observes slope
opposition in the changes of
trinaphthenonaphthalenes and pentacyclanes
concentrations with the depth.
Based on the investigations it was shown that the
content of naphthenonaphthalenes and
naphthenophenanthrenes with total number of cycles
3-4 increases in Cainozoic oils with the depth of
occurrence, whereas in Paleozoic oils it decreases.
In spite of the age of deposits the content of
cyclanes (4-5 cycles) and naphthenoarenes with total
number of cycles in a molecule 5 increases with the
depth of occurrence, whereas the content of
naphthenobenzens with a number of cycles in a
molecule from 2 to 4 decreases.
416

P-284
Nitrogen compounds in organic matter of rocks from Upper
Jurassic deposits of Western Siberia
Svetlana Yanovskaya 1 , Tatyana Sagachenko 1 , Heinz Wilkes 2
1 Institute of Petroleum Chemistry SB RAS, Academichesky Avenue, 4, Tomsk, Russian Federation,
2 Deutsches GeoForschungsZentrum, Potsdam, Germany
Distribution and compositions of nitrogen
compounds (NC) in organic matter (OM) of rocks from
Upper Jurassic deposits of West Siberia
(Bazhenovskaya suite) have been studied.
Bitumens were extracted using a methanolchloroform
mixture (7 : 93). The studied samples
differed with respect to the conditions of the initial OM
deposition (Pr/Ph=0.92–2.46) and the level of thermal
maturity (lower, moderate and higher).
To isolate NC we used a 25 % solution of sulfuric
acid in a 80 % solution of acetic acid. Based on nonaqueous
potentiometric titration and IR spectroscopy
the extracted NC in OM of rocks represent a mixture
of strong and weak bases. Depositional conditions
and the degree of OM thermal maturity had practically
no effect on total NC yield, the ratio of strongly and
weakly basic components and quantitative
compositions of the extracted compounds.
To obtain detailed information about NC
compositions the concentrates were divided into
fractions of strong and weak bases using a liquidadsorption
chromatography method.
Based on mass spectrometric data strong bases
of all samples under study are represented by alkyl-
and naphtheno-derivatives of quinoline, benzo- and
dibenzoquinoline, azapyrene, benzothiazole, and
thiopheno- and benzothiophenoquinoline. Weak
bases are represented by alkyl- and naphthenoderivatives
of cyclic amides of pyridine type and their
hydrated analogues – lactames. Alkyl- and
naphtheno-substituted quinoline-, benzoquinoline-
and dibenzoquinolinecarboxylic acids occur among
the bases of both types. Weak bases predominate
among the identified compounds.
Using a gas chromatography-mass spectrometry
it was determined that in all OM samples
alkylquinolines are represented by С4–С7 homologues
(m/z 185–227), alkylbenzoquinolines by С1–С5
homologues (m/z 193–249) and
mononaphthenobenzoquinolines by the first member
of the series and by С1–С2 homologues (m/z 233–
261). Based on the fragmentation patterns and
comparison with the published data we identified 2-
and 8-ethyldimethyl-, 2,4-dimethyl-8-isopropyl-, 2ethyltrimethyl-,
ethyltetramethyl-, 2,3,4-trimethyl-8-
isopropyl- and 8-isopropyltetramethylquinolines within
the alkylquinolines.
Among the С1–С3-alkylbenzoquinolines we
detected structures containing methyl substituents
only. Identified were 2-methyl-, 2,4- and 2,3-dimethyl-
and 2,4,6-trimethylbenzo(h)quinolines. It follows from
the analysis of mass spectra representing С4benzoquinolines
that they are composed of both fully
methylated structures and structures containing an
ethyl substituent in the position remote from a
nitrogen atom. Structural details and positions of the
substituents for С5-benzoquinolines have not been
determined.
Alkyl substituted mononaphthenobenzoquinolines
probably contain methyl substituents only.
Besides, we found the presence of С3–С4azapyrenes
(m/z 245–259), С1–С2-dibenzoquinolines
(m/z 243–257), С2–С4-thiophenoquinolines (m/z 213–
241) and С2–С3-benzothiophenoquinolines (m/z 263–
277) as constituents of the strong bases. The
substituents in azapyrenes are represented by methyl
or ethyl groups, while they are methyl groups only in
dibenzoquinolines and thiophenoquinolines. The
structures of substituents for
alkylbenzothiophenoquinolines have not been
determined.
It was shown that an oxidizing depositional
environment of the OM and its thermal transformation
result in an increased portion of polycyclic and
alkylated structures as well as thermodynamically
stable isomers within the strong nitrogen bases.
Using the data of mass spectral libraries NIST 21
and 107 it was determined that weak nitrogen bases
in the OM may have the structure of 2-hydroxy-3methyl-
(m/z 159) and 2-hydroxy-3,4dimethylquinolines
(m/z 173), 9(10H)-acridinone
and/or 6-hydroxyphenanthridinine (m/z 195) and
methylacridinone, in which a methyl group is loctaed
at positions 1, 2, 4 and 10 (m/z 209).
417

P-285
Understanding Fluid Inclusion Stratigraphy (FIS) Data
Daniel Stoddart 1 , Paul Farrimond 2
1 Lundin Norway AS, Oslo, Norway, 2 Integrated Geochemical <strong>International</strong> (IGI) Ltd, Bideford, United
Kingdom (corresponding author:daniel.stoddart@lundin-norway.no)
Fluid Inclusion Stratigraphy (FIS) involves the
analysis by mass spectrometry of volatile components
present in rock samples, performed on each sampled
cuttings interval and core chips throughout a well.
We applied Principal Components Analysis (PCA)
to FIS data from wells in the Barents Sea with the aim
of better understanding the data and the interrelationships
between the different ions to define
source rock vs. hydrocarbon-bearing intervals, marine
vs. terrestrially deposited organic matter, and an oil
characterization scheme. An attempt has been made
to integrate well log, bulk and molecular geochemical
data with FIS data to refine interpretations.
FIS data were available for 23 wells in the Barents
Sea. 15 wells were selected for individual analysis by
PCA. Several PCA approaches were tested, using
different selections of FIS data (all ions, selected ions,
ratios & parameters) and different data pre-treatments
(normalisation and autoscaling [standardisation]);
optimal results were obtained using a suite of 166 ion
abundances (14 ions being excluded due to their
frequent absence or apparent unreliability) which
were normalised and autoscaled prior to PCA.
Example data from 7220/6-1 well, a commercially
dry hole with good oil shows and residual
hydrocarbons in carbonates. PC1 scores data are
coincident with a sharp increase in methane and
paraffin FIS responses in the carbonates. The PC1
loadings plot indicates that PC1 is dominated by
heavier hydrocarbon ions, thus producing a
―hydrocarbon log‖. A ratio of (as logs) 111+113 AMU
to 29 AMU gives a ―C8/C2 log‖ which interestingly
shows a more consistent oil signature throughout the
carbonates, but falling towards its base. This may
indicate that ratios (i.e. compositional information) are
more reliable than raw ion abundances, the latter
being influenced by too many other factors (e.g.
inclusion abundance).
High acetic acid concentrations are evident
directly below a zone of high methane and paraffin
values. Gas chromatograms from in/around the high
acetic acid zones show water washing/biodegradation
effects lending credence to the idea that this may
represent a paleo-OWC.
Source rocks and coaly intervals produce similar
FIS spectra to oil-bearing intervals, and respond
similarly in PCA. Hekkingen Fm. samples often show
a good relationship between PCA response and total
organic carbon content, suggesting that kerogen
content may control the FIS signal in these intervals.
Parameters including aromatic ions or methane (15
AMU) intensity are useful in distinguishing between
FIS responses from marine source rocks and coaly
intervals.
This study will show how FIS data can be more
fully explored.
418

P-286
Comparison of natural gases in Middle Cambrian reservoir with
hydrous pyrolysis gases from Lower Palaeozoic source rocks
from the Polish, Lithuanian and Estonian parts of Baltic Basin
Maciej Kotarba 1 , Michael Lewan 2
1 Faculty of Geology, Geophysics and Environmental Protection, AGH University of Science and Technology,
Krakow, Poland, 2 US Geological Survey, Denver, United States of America (corresponding
author:kotarba@agh.edu.pl)
The Baltic Basin is a large NE-SW trending
depression on the NW margin of the Precambrian
East European Craton. In the onshore and offshore
Polish Baltic Basin, seven small oil and five gascondensate
accumulations were discovered in the
years1970-1999. In Lithuania, the first oil discovery
was made in 1960 and oil exploitation was started in
1990. In Estonia, no oil and gas deposits have been
discovered to date, but considerable kukersite oil
shale resources occur. A few potential source rock
horizons are present in the Lower Palaeozoic
(Cambrian, Ordovician and Silurian) section. The
Upper Cambrian-Tremadocian strata contain the best
source-rocks with low-organic sulphur, oil-prone
Type-II kerogen and are considered the most likely
source of these offshore petroleum accumulations.
Kukersite contains lacustrine Type-I kerogen.
The objective of this study is to determine
the origin of the natural gases dissolved in oil and in
gas-condensate accumulations of Middle Cambrian
sandstone reservoir of the Polish and Lithuanian parts
of Baltic Basin. The study involves molecular and
stable-isotope characterization of natural gases and
gases generated from Upper Cambrian-Llandovery
source rocks by hydrous pyrolysis. Hydrous pyrolysis
experiments were conducted for 72 h at 330 °C and
355 °C on seven thermally immature samples
representing Upper Cambrian (1 sample),
Tremadocian (3 samples), Llandovery (2 samples)
shales and Upper Ordovician kukersite (1 sample)
from Poland and Estonia. Fifteen natural gas samples
were collected from Middle Cambrian sandstone
reservoir in the Polish Baltic basin and five samples
from Lithuanian Baltic basin. Molecular compositions
of the gases and stable carbon isotope analyses of
methane, ethane, propane, butanes, pentanes and
carbon dioxide, stable hydrogen isotope analyses of
methane and stable nitrogen isotope analyses of
gaseous nitrogen were analysed.
Results of the investigation indicate that
there exist distinct δ 13 C signatures but non-distinct
molecular compositions of gases generated by
hydrous pyrolysis of the representative Upper
Cambrian-Tremadocian complex. In particular, the
trend between δ 13 C of methane, ethane, propane,
butanes and pentanes and their reciprocal carbon
number is not always linear as prescribed by some
investigators. Instead, a ―dog-leg‖ trend may exist,
which makes prediction of the δ 13 C of the source rock
kerogen problematic. Experimentally determining this
trend and establishing how it changes during
petroleum generation provides a correlation
parameter that can help differentiate between end
members of thermogenic and microbial gas input in
natural gas accumulations. This approach cannot
account for the isotopic changes that may incur during
migration and in-reservoir alterations, but it does
provide an isotopic signature of the primary gas
generated from a source rock at pre-oil-cracking
thermal maturities.
Isotopic characterization of natural gases as
compared to hydrous pyrolysis gases revealed that
these natural gases were generated by microbial and
thermogenic processes from oil-prone Type-II
kerogen contained in Upper Cambrian-Tremadocian
source rock complex. Subsequently, the gases have
undergone migration and mixing of microbial and lowtemperature
thermogenic gases. The most significant
microbial component was found in the B-3 offshore oil
and gas field. The traps within the Middle Cambrian
reservoir had already formed in middle Ordovician
through early Silurian time, when migration of
microbial methane took place. The microbial methane
was generated from immature organic matter
contained in the Upper Cambrian-Tremadocian
source-rock complex. Oil and thermogenic gas
occurred later and charged the same traps containing
the microbial gas. Carbon dioxide and nitrogen gases
are considered to be thermogenic from the source
rocks with some possible contributions from the crust.
419

P-287
The hydrocarbon occurrence and play-forming genetic
relationships of the deep palaeocene in Jiyang Depression, East
China
Linye Zhang, Qing Liu, Xingyou Xu, Xiangxing Kong, Shouchun Zhang, Ru Wang,
Youshu Bao, Rifang Zhu, Zheng Li
Geological Scientific Research Institute, Shengli Oilfield Branch Company, SINOPEC, Dongying, 257015,
China, Dongying, China (corresponding author:liuq_1230@sina.com)
The Jiyang Depression lies in the southeastern
part of the Bohai Bai Basin (East China) as one of its
subsidiary tectonic units. Four sags (Dongying,
Huimin, Zhanhua and Chezhen) were developed in
the Jiyang Depression. Now the deep Palaeocene
(>3500m) of Jiyang Depression faces high exploration
risks for the low recognition. So sedimentary-organic
facies and its spatial distribution, hydrocarbon
generation, migration and accumulation of the deep
source rocks (including Member of E1-2k 2 and E2-3s 4 )
are studied in order to decipher the relationships
between hydrocarbon generation and accumulation,
and to propose the favorable exploration prospects.
According to the sedimentary structures,
palaeoontolgy associations and organic matter
occurrence analysis, the Paleocene lacustrine
hydrocarbon source rocks are divided into four types
of sedimentary organic facies, namely Anoxic facies,
Anaerobic facies, Dysaerobic facies and Aerobic
facies. Combinating with well logging, the
identification marker of each facies are summarized
and the deep source rocks are evaluated. The
sedimentary organic facies distribution shows great
distinguish for the upper E2-3s 4 from the east to the
west, with most of the anoxic and anaerobic facies
occurring in the Dongying and Zhanhua Sags, while
Dysaerobic facies and Aerobic facies dominating in
the Chezhen and Huimin Sags. And the source rocks
of E1-2k 2 are also dominated by aerobic and
dysaerobic facies. It suggests there is higher
exploration potential in the east than in the west for
the deep Palaeocene.
Based on the systematical analysis of the phase state
evolution of hydrocarbon products, the minerals
catagenesis and the mechanical properties changes
of the excellent source rocks of anoxic-anaerobic
facies in E2-3s 4 , the whole hydrocarbon expulsion
process can be divided into 3 stages, including free
water expulsion stage, hydrocarbon generation and
energy rising stage, and microfracture expulsion
stage (figure 1). The major hydrocarbon expulsion of
the deep Palaeocene source rocks occur during the
microfracture expulsion stage. During the
microfracture expulsion stage, 3 oil and gas migration
modes including vertical migration, lateral migration
and downward migration can occur in different
geology conditions. Oil and source correlation indicate
that the shallow and medium depth reserves sourced
from E2-3s 4 excellent hydrocarbon source rocks of
anoxic and anaerobic facies are mainly formed
through vertical migration, and there are still plenty of
reserves forming by lateral migration and downward
migration in the deep Palaeocene for the low proved
exploration efficiency. So there is still high exploration
potential in the deep Palaeocene of Jiyang
depression.
Figure1. the microscopic lithology characteristics
of different sedimentary organic facies in Jiyang
Depression
A, B: Anoxic facies; C, D, E: Anaerobic facies; F,
G: Dysaerobic facies; H: Aerobic facies
Contribution of the deep source rocks to the
proved reserves are comparison with the basin
resources of the deep source rocks. It shows that
there is still much resources provided by the source
rocks of E2-3s 4 . Combinating with the oil and gas
migration modes analysis above mentioned, it is
concluded there is still high exploration potential in the
deep Palaeocene, including every kinds of
conventional reservoirs and the source rocks
themselves in the deep Palaeocene, and the pre-
Paleogene buried hills.
REFERENCES
Wignall, P. B. (1993) J. Geol. Soc., 150, 193-196
Zhang Linye. (2008). Petroleum Geology &
Experiment, 30(6): 591-595 (in Chinese).
Liu Qing, Zhang Lin-ye, Shen Zhong-min, et al. (2004)
Acta Petrolei Sinica (in Chinese), 25(4): 42-45.
Linye Zhang, Qing Liu, Rifang Zhu, et al. (2009)
Organic Geochemistry, 40: 229-242
420

P-288
Re/Os fractionation during generation and evolution of
hydrocarbons
Fatima MahdaouI 1,2 , Laurie Reisberg 1 , Raymond Michels 2 , Yann Hautevelle 2 , Yannick
Poirier 3 , Jean-Pierre Houzay 3
1 Centre de Recherches Petrographiques et Geochimiques, Nancy Université, CNRS UPR2300,
Vandoeuvre-lès-Nancy, France, 2 UMR7566 G2R, CNRS, CREGU, Nancy Université, Vandoeuvre-lès-Nancy,
France, 3 TOTAL Centre Scientifique et Technique Jean-Féger, Pau, France (corresponding
author:fatima.mahdaoui@g2r.uhp-nancy.fr)
Rhenium (Re) and osmium (Os) are organophile
elements. For this reason, the Re-Os radiogenic
system is well adapted to the dating of organic-rich
rocks such as black shales. Recently, it has been
suggested that this system can also be used to date
the major events occurring during the evolution of
hydrocarbons (Selby and Creaser, 2005) [1]. In
particular, in their study of oil sand from western
Canada, these authors found a correlation between
187 Os/ 188 Os and 187 Re/ 188 Os, which they interpreted
as an isochron dating the time of oil migration.
In order to permit the effective use of the Re-Os
system to date hydrocarbon evolution, we need a
better understanding of the events that could
fractionate the Re/Os ratios of petroleum fluids. One
process that is particulary important in the evolution of
these fluids is the precipitation of asphaltenes. The
asphaltene fraction frequently concentrates most of
the metals contained in petroleum. For this reason,
we have undertaken an experimental study of the
effects of progressive asphaltene precipitation on Re
and Os contents and Re/Os ratio.
The experiments were performed on two oils. The first
is a conventional oil, containing about 6%
asphaltenes. Given the very chalcophile behavior of
rhenium and osmium, we also chose to work on a
sulfur rich oil. The asphaltenes used in the
precipitation experiments were pentane-insoluble
fractions of these oil samples.
The first phase of our study was aimed at developing
a method of sequential precipitation. For this, we used
techniques inspired by Nalwaya (1999) [2]. For the
fractionation procedure, we used a binary mixture of
dichloromethane (DCM) and n-pentane: the bulk
asphaltene fraction was dissolved in DCM. Increasing
quantities of pentane were then added, permitting the
precipitation of progressively less polar asphaltenes.
These various fractions revealed differences in
structure or composition when analyzed by gel
permeation chromatography and FTIR spectroscopy
The asphaltene fractions underwent a chemical
treatment to extract, separate and purify Os and Re.
Re and Os concentrations were determined by
isotope dilution. Os isotopic compositions were
determined by Negative Thermal Ionization Mass
Spectrometry (N-TIMS) using a Finnigan MAT262
instrument. Re isotopic compositions were
determined by Inductively Coupled Plasma Mass
Spectrometry (ICP-MS), using an Elan 6000.
We found similar Re and Os profiles as a function of
the asphaltene precipitation sequence for the two oils.
We also analyzed other metals such as vanadium and
nickel. Comparison with the Re-Os results suggested
that that these metals do not occupy the same sites
as rhenium and osmium. This observation provides
important constraints on the nature of the association
between Re, Os and organic matter.
Our results also suggest fractionation of the Re/Os
ratio after more than 50% of the asphaltenes are
precipitated. This mechanism could be responsible for
fractionation of Re and Os during the evolution of
hydrocarbon in petroleum systems. Consequences for
the use of the Re/Os geochronometer will be
discussed.
References
[1] Selby D. and Creaser R.A. (2005b). Direct
radiometric dating of hydrocarbon deposits using
rhenium-osmium isotopes. Sciences 308, 1293-1295.
[2] Nalwaya V., Tantayakom V., Puimsomboon P. and
Folger S. (1999). Studies on Asphaltenes through
Analysis of Polar Fractions. Ind. Eng. Chem. Res. 38,
964-972.
421

P-289
Correlation of crude oils reservoired in the Polish Carpathian
oilfields (the Silesian and Skole Units)
Irena Matyasik 1 , Wojciech Bielen 1 , Marek Janiga 1 , Leszek Jankowski 2
1 Oil and Gas Institute, Cracov, Poland, 2 Polish Geological Institute, Cracov, Poland (corresponding
author:matyasik@inig.pl)
This region is located in the eastern part of
the Polish Outer Carpathians; traditionally there are
distinguished three tectonic units: the Silesian Unit in
the south, the Weglowka Unit and the Skole Unit in
the north. Oil fields are stretched on both sides of the
Weglowka Unit zone or its prolongation (eastern
direction).
This oil fields are located within the tectonic
flower structure and the role of the master fault acts
the Weglowka ramp. Tectonically active zone of the
ramp is a place of hydrocarbons migration but also
may be an insulating zone.
Until now, there is no clear explanation of the
origin of crude oils accumulated in different tectonic
units of the Carpathian Flysch. [2] One of the source
rocks, which shows a positive correlation with the
most of crude oils in this region are Menilite Beds. As
part of the correlation works GC, GC/MS and
EA/IRMS analysis were performed. Studied crude oils
were collected from the eastern part of the Silesian
Unit (Grabownica Fold) and the folds of the Skole Unit
(Łodyna-Wańkowa Fold, Brzegi Dolne well).
The correlation was performed in order to
determine sedimentation environment, type of
sediment, thermal maturity and degree of degradation
of oils (by geochemical indicators). The results
indicated a distinction between crude oils of the
Silesian Unit and the Skole Unit. Parameters
differentiating those oils are: sulfur content, Pr/Ph
indicator, isotopic composition (δ 13 C) and the
presence of bisnorhopane and tricyclic terpanes.
Crude oils of Skole Unit have a low sulfur content
and crude oils of the Silesian Unit are classified as
unsulphur. Bisnorhopane is present only in crude oils
of the Skole Unit, however tricyclic terpanes were
present (in high concentrations) in crude oils of the
Silesian Unit. Bisnorhopane presence can be
explained in three ways: degradation of crude oil (not
always confirmed by other factors) or bacterial activity
in the destruction of organic matter during
sedimentation in a shallow reservoir or paleoleakage.
Crude oils of the Grabownica Fold have high Pr/Ph
indicator (>2). Geochemical indicators of crude oils of
the Skole Unit show various sedimentation conditions
(from unoxic through sub-oxic to oxic environment). In
addition, variation of the the Silesian Unit and the
Skole Unit crude oils was confirmed by carbon
isotopic composition.
All those parameters were correlated with
corresponding parameters obtained from the
analysis of outcrop samples representing Menilite
Beds. All outcrops samples of the Skole Unit showed
a low thermal maturity (proved by Tmax and
biomarkers distribution – steranes), which excludes
those Menilite Beds as a source rock of crude oils
accumulated in the Skole Unit folds. However genetic
signatures (for example presence of BNH, isotopic
composition) may suggest that deeper Menilite Beds
(in Brzegi Dolne or Paszowa wells) are source rocks.
[1] Crude oils of the Silesian Unit may have another
source rock.
References:
[1] Kuśmierek J., Subsurface structure and tectonic
style of the eastern Polish Carpathians on the basis of
integrated 2D interpretation of geological and
geophysical image.
[2] Więcław D., Kotarba M. J., Koltun Y., Identification
of kerogen type in the menilite shales of the Skole
and Silesian units of the Polish and Ukrainian
Carpathians.
422

P-290
On the problem of preservation of hydrocarbons (HC) and
organic matter (OM) at high pressures (HP) and temperatures
(HT) (experimental data)
Vasily Melenevskiy 1 , Yury Palyanov 2 , Alexander Sokol 2 , Vladislav Maly 3
1 Institute of Petroleum Geology and Geophysics, Siberian Branch of the Russian Academy Science (SB
RAS), Novosibirsk, Russian Federation, 2 Institute of Geology and Mineralogy SB RAS, Novosibirsk, Russian
Federation, 3 Institute of Hydrodynamics SB RAS, Novosibirsk, Russian Federation (corresponding
author:vmelenevsky@yandex.ru)
We studies the behavior of HC and coal in
the conditions of supercritical fluid at HP and HT,
which account for diamond stability conditions, and
that of dispersed OM and coal under shock-wave
loading. The reaction products were examined by
means of chemical, X-ray and pyrolytic (Rock – Eval)
methods. The analysis technique, and the experiment
procedures, and, partly, the findings of the studies
are described in the works [1 - 4].
Supercritical fluids Experiments were
carried out in a multi-anvil high-pressure apparatus of
the ‗‗split-sphere‖ type at temperature 1200 ’ 1420 о С
and pressure 5,2 ÷ 5,7 GPa [3, 4]; eicosane,
anthracene and bituminous coal (R o vt=0.94 %, HI=
225 mg HC/g Соrg) were used as the objects of the
study.
When heated in HT-HP conditions, the first
processes starting to proceed in coal is cracking,
followed by further decomposition of the hydrocarbon
products yielded and ending by the build-up of
metamorphized residuals. The data analysis showed
that the coal has metamorphically altered to pass to
the metaanthracitic stage of coalification (atomic ratio
(Н/С)at was shown to decrease against the initial
value of 0.84 to 0.24). X-ray diffraction data for the
residual solid OM after the experiment on HCs have
proven it to be represented by graphite. The
accuracy of establishing the HC decomposition
degree was defined with the analysis blank value in
the experiment. Under the HT-HP experiment
conditions, the decomposition degree value might not
exceed 0.999, according to our estimations.
However this estimation proved correct only
for HC with nCi>10. For the light HC additional
investigations are needed.
Shock wave experiment. To model the
impact processes going on when a meteorite hits the
surface of the Earth, we used explosion technique in
the geometrical version of cylindrical symmetry [1, 2].
Maximum (calculated) pressure within the front of a
detonation wave varied within the interval 2.0÷ 6.0
GPa. OM proved to have morphed into graphite
during the experiment; neither gaseous or heavy
hydrocarbon have been detected in the sample after
the experiment.
8 cm
Fig. This picture shows longitudinal section
of the container with the sample subjected to
explosion with intensity of 2.00 Gpa. The upper arrow
indicates the detonation wave direction.
In the left portion of the picture we can see a
cone-shaped darkened area, an indication of the
largest transformations, consisting in graphitization of
OM; whereas, the starting OM has hardly been
altered outside this area. Thus after the explosion
there was formed practically non-gradient boundary
between high and low maturity OM.
References
[1] Melenevsky V. N., et al. (2003) Geokhimia, №12,
p.1332-1336.
[2] Melenevsky V. N. et al. (2005) DAN, v. 405, p. 1-
3.
[3] Melenevsky V., Kontorovich. A. (2007) Problemy
TEC (In Russian), #1, p.18-21.
[4] Alexander G. Sokol et al. (2009) Geochim. et
Cosmochim. Acta, v. 73, p.5820–5834.
423

P-291
Geochemical parameters for unravelling mixtures. Examples
from the South Atlantic continental margins and the giant northcentral
West Siberian gas fields
John Moldowan 1,2 , David Zinniker 1 , Zhaoqian Liu 1 , Alla Rovenskaya-Nemchenko 3 ,
Jeremy Dahl 1 , Tatyana Nemchenko 4
1 Geological & Environmental Science, Stanford University, Stanford, United States of America, 2 Biomarker
Technology, Sebastopol, United States of America, 3 The Foundation for East-West Cooperation, Moscow,
Russian Federation, 4 Vernadsky Institute of Geochemistry and Analytical Chemistry (GEOKHI), Moscow,
Russian Federation (corresponding author:moldowan@yahoo.com)
The recognition, correlation and quantification of oil
mixtures remain challenging in many petroleum
system studies. Most prolifically productive basins or
regions have multiple source rocks generating at wide
ranges of maturity. Mixtures present themselves in
many forms, including any proportions of black oil,
light oil and condensate, which can be single-sourced
or co-sourced. Knowledge of all active sources and
the maturities of their generated hydrocarbons is the
critical starting point to develop correct basin models.
Selection of the best parameters to de-convolute oilsource
mixtures can best be determined from singly
sourced end-member oil and source rock samples.
The ideal parameters show very large differences in
magnitude between the candidate sources and are
independent of maturity difference. In parallel,
maturity differences can be taken into account and
also provide useful information about the mixtures.
In the absence of data from end-member samples
such parameters can be construed by inference
based on information about source rock depositional
environment and burial depth or history (maturity)
where different source types often have widely
contrasting characteristics.
In the south atlantic margins, we are faced with oil
mixtures that may include oil generated in the
lacustrine rift sections of Barremian-Aptian age,
transitional to marine post-rift sources of late Aptian
into the late Cretaceous and Tertiary marine-deltaic
oil from the latest Cretaceous through the Tertiary.
Parameter value ranges depend on the specific basin
in question and analysis of some end-member
samples from the area of interest can more precisely
define those values. However, we find that purely
lacustrine sourced oil samples from Angola show C29hopane
C-isotope ratios of < -35 ‰, near absence of
C30 (desmethyl) steranes (C30/C29 ≤ 0.01%), and
concentration ratio differences from other sources for
diamondoid pseudohomologues (e.g., adamantanes /
diamantanes).
Post-rift marine sources generally show C29-hopane
C-isotope ratios > -24‰, C30/C29 sterane ratios ~10%.
Younger marine-deltaic oil often shows geochemical
parameter values intermediate between the marine
and lacustrine end-members. TPP ratios and certain
plant biomarkers (diterpanes, oleanane, bicadinane
and their C-isotope ratios) differentiate those sources.
The source(s) of gas in the giant gas fields (e.g.,
Urengoi, Yamburg) of north central Western Siberia
has been a subject of studies that have reached
different conclusions. The possibilities include
thermogenic origins of various source ages and facies
versus biogenic. Our recent studies show that at
least some of the gas is thermogenic in origin. This is
indicated by elevated diamondoid concentrations in
light oil samples obtained from those fields. Further,
the C-isotope ratios of diamondoids correlate them to
end-member Early – Middle Jurassic Tyumensourced
oil (Figure 1). This correlation strongly infers
a Tyumen source for the gas, which is probably,
therefore, the major source. Some samples in the
basin also show mixtures of Late Jurassic Bashenov
oil with Tyumen condensate that can be unravelled by
compound specific isotope analysis of biomarkers
(CSIA-B) and diamondoids (CSIA-D).
� 13 C PDB (‰)
Urengoi & Yamburg
cracked -19 oil samples
-20
-21
-22
-23
-24
-25
-26
-27
-28
-29
-30
-31
-32
-33
-34
-35
-36
All cracked oil & Tyumen
end-members
(heavy isotope group)
Only non-cracked oil and
Bashenov end-members
(lighter isotopes group)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Diamondoids (adamantane & alkyladamantanes)
Figure 1. CSIA-D distinguishes Bashenov and Tyumen oil. In every
case the deep source correlates with the Tyumen
424

P-292
A geochemical assessment of subsalt tar zones in the Gulf of
Mexico
Erica Morais
Petrobras, Rio de Janeiro, Brazil (corresponding author:ericat@petrobras.com.br)
Gulf of Mexico (GOM) deep water showed to be one
of the most prolific oil production provinces in the
world. Information collected during drilling operations
revealed noteworthy unexpected challenges into
subsalt plays. Among the various challenges found
into subsalt plays is the occurrence of bitumen zones
(here bitumen will be called ―tar‖) that can be
investigated from the geochemical perspective.
Tar zones have been noticed by operating companies
in deep waters of GOM (1). The presence of tar zones
is not apparent on seismic, representing an
unpredictable event this way. Thus it is important
collect information from pre drilled wells and use it in
understanding their theoretical origin. This study is
addressed in helping our understanding regarding the
origin and occurrences of tar zones.
To help understand the controls regarding to tar
origin, detailed geochemical analyses were conducted
in two tar samples. Subsequently, the results were
compared to two oil samples previously collected at
wells from the same block and to immature extracts
adjacent to reservoir intervals.
The two ―tar" samples recovered during the drilling
were submitted to extraction using dichloromethane
as solvent. The extracts then underwent the following
sequence of geochemical analysis: Medium Pressure
Liquid Chromatography, Gas Chromatography, Total
Carbon Isotope Composition and Gas
Chromatography coupled to Mass Spectrometry
(GCMS).
The extraction using dichloromethane recovered
approximately 80% of NSO compounds, and 20% of
hydrocarbons, without solid residual (mineral matrix).
This confirms the idea proposed during the drilling by
which the tar would exist as separate levels either as
layers directly below the salt or filling fault planes. The
gas chromatogram from tar samples showed
contamination by drilling mud apart from light and
heavy n-paraffins. Biomarker GCMS analyses of the
saturated fractions showed a high degree of similarity
among the tar and oil samples (Fig. 1). The samples
display low Ts/Tm ratios and significant quantities of
homomoretanes (C31-C35), which are consistent with
lower maturity from the oils recovered at this portion
of GOM. The source rock of the tar and oil is
apparently the same, possible marine carbonates
from Oxfordian Smackover Formation. The relative
lack of biodegradation indicators may denote that the
tar formation was not associated to biological
processes. The biomarker profiles recovered from the
extracts of immature rocks adjacent to the reservoir
rocks do not show similarity to the tar, suggesting that
immature material was not remobilized to the
reservoir from nearby formations. Isotopic analyses
could not be applied due to high drilling fluid
contamination.
Ts Ts
Tm Tm
H29 H29
H30 H30
Tar sample 1
Tar sample 2
Fig. 1: Fragmentograms m/z 191 from the samples analyze.
Considering the above discussed, the origin of the tar
appears to be a combination of processes over
geologic time. Probably oil trapped into reservoir
layers suffered effects of pressure release during the
fault reactivation that occurred during the salt growth.
This pressure variation could have promoted the
precipitation of NSO compounds formed either at
reservoir forming layers or along the migration
pathways due to differences in permeability.
Although the main limitation of geochemical studies is
that samples are not always available, the application
of geochemical analysis together with a geological
and engineering approach help constrain the fluid
origin, reducing uncertainties associated to each
individual exploration or developing phase and
providing a most reliable assessment.
[1] Weatherl, M.H., 2007. SPE/IADC105619.
H29 H29 H29
Ts Ts Ts
Tm Tm Tm
H28 H28 H28
H30 H30 H30
Immature extract
Well #C
C31-35
Extended
Hopanes
Oil sample
Well #A
Oil sample
Well #B
425

P-293
Hydrocarbon biomarkers in the bottom sediments of the
hydrothermal fields Ashadze-1 and 2 (MAR, 13°N)
Inna Morgunova, Vera Petrova, Ivan Litvinenko, Georgiy Cherkashev
I.S. Gramberg All-Russia Research Institute for Geology and Mineral Resources of the World Ocean, Saint-
Petersburg, Russian Federation (corresponding author:inik@list.ru)
The rift hydrothermal circulation system is a
complex geostructural formation, which can be used
as a model of natural laboratory for detail geological,
geophysical, geochemical, biological and other
investigations. Enormous amounts of heat released
with the endogenous fluid into near-bottom layers and
their enrichment with a highly mineralized substance
during the fluid discharge stimulates the development
of unique chemosynthetic biocenoses. Specific
patterns of diagenetic transformation of organic
matter (OM) are influenced by a set of physical and
chemical factors.
Samples of sediments (9 stations, 31 sample) were
collected from two active hydrothermal fields
Ashadze-1 and Ashadze-2 (13 ° N, MAR) during the
joint 22 cruise of PMGE and VNIIOkeangeologiya onboard
of the R/V ―Professor Logachev ‖ in 2003. The
significant part of work was conducted during the
French-Russian expedition "Serpentine" on-board
«Pourquoi Pas» in 2007 [1, 2].
The sediments were collected using a box-corer,
TV-grab and drag and kept until the laboratory
investigations in sterile containers at -18 ° C. The
standard analytical procedure included the
determination of elementary (Corg, Norg, Ccarb)
composition of sediments and group and molecular
composition of the soluble part of the dispersed
organic matter (DOM) by methods of preparative
liquid chromatography and GC-MS using Agilent
Technologies GC System 6850/5973.
The comparative study has shown that lowcarbonate
muds and hydrothermal metalliferous
sediments collected directly from the hydrothermal
fields Ashadze-1 and 2 cardinally differ in their
geochemical characteristics from the background
samples: the organic carbon content is sufficiently low
Corg = 0.1 ÷ 0.6%, while hydrocarbons reach 234.4
µg/g of sediment in the surface layer, which is an
order of magnitude greater than the background
values (~ 26 µg/g of sediment). In the group
composition of DOM an increasing content of oil
fraction has been identified and it reaches maximum
values in the sediments of hydrothermal field
Ashadze-1. The presence of isoprenoids, hopenes
and ββ-biohopanes in the composition of DOM gives
the evidence of the fresh biogenic input to the
sediments and the values of maturity indices point to
the intensive OM alteration processes (OEP ~ 1,
sterane C29 20S/(20S +20 R) ≥ 0.5). Three intense
peaks of biphytanes in the high molecular weight
region (C37 ÷ C41) have been detected for both
hydrothermal zones. This similarity allows us to
assume the existence of common processes of DOM
alteration influenced by the hydrothermal
environmental conditions.
A surprisingly high degree of DOM maturity (OEP ~
1) in one of background station surface sediments
agrees with fixed nearby hydrophysical water
anomaly (T °, salinity and turbidity) [3], and indicates
the active thermal catalytic alteration of DOM.
Therefore, the result of two active hydrothermal
fields Ashadze-1 and 2 investigation suggests the
existence of common sources and mechanisms of
DOM generation for them. The similarity may be
connected both with the influence of biological
communities, distributed mainly in sites of
hydrothermal activity, and with specificity of OM
transformation under the whole set of physical and
chemical factors of hydrothermal environment.
References
[1] Beltenev V., Nescheretov A., Shilov V. (2003)
InterRidge News. V. 12. № 1. P. 13-14.
[2] Fouquet Y., G. Cherkashov, J.L. Charlou (2008)
InterRidge News. V. 17. P. 15-19.
[3] Kaminski D.V., Narkevski E.V., Sudarikov S.M.
(2007) Materials from 26 <strong>International</strong> Scientific
conference (school) of marine geology. V. 2. Moscow.
GEOS. 324 p.
426

P-294
Petroleum generation and expulsion zones in Maturín sub-basin:
Evaluation of paleoenvironmental and lithologic variations of
cretaceous source rocks responsible for oil charges
accumulated in Carabobo Area, Orinoco Oil Belt- Eastern
Venezuelan Basin
Wendy Murillo 1 , Carolina Olivares 2
1 PDVSA-Intevep, Los Teques, Venezuela, 2 PDVSA-Oriente, Puerto la Cruz, Venezuela
(Corresponding author:murillow@pdvsa.com)
The petroleum accumulations in Carabobo area
come from lateral migration to long distances from
the north and northwest and were generated from
Cretaceous source rocks in the north of Maturín
sub-basin. The objective of this contribution is to
investigate the oil migration and charging based on
integration of data from organic geochemistry and
1-D petroleum generation and expulsion basin
modeling in wells which penetrated the oversthrust
slab of the Pirital and Frontal Thrust and
rocks beneath them. This integrated approach
provides new insights about the accumulations of
heavy and extra-heavy oils in the Carabobo area
(Orinoco Oil Belt), Eastern Venezuelan Basin.
In the southern part of the Frontal Thrust,
petroleum is still being generated and expulsed
from one tectonic unit. Generation in this unit (here
referred to as tectonic unit 1) occurred from Late
Cretaceous to Recent, while the expulsion
occurred in several episodes during early
Paleocene, early Miocene and late Miocene. In
contrast, in the thrust zone generation and
expulsion occur from two or more tectonic units,
defined and separated by thrust-faults. Oil
generation from the source rocks in the tectonic
unit 2 occurred mainly from early Eocene and
expulsion from early Miocene. There are three
main zones of petroleum expulsion in Maturín subbasin,
which are defined as: zone of expulsion I
where the petroleum expulsion occurred from early
Eocene to early Miocene, although it could be as
old as early Paleocene. In the zone II the expulsion
occurred during the early Miocene-middle Miocene
times while in the zone III it occurred during the
late Miocene to Recent, mainly below the Frontal
thrust (southern part of the deformation zone).
The crude oils in Carabobo area were generated
and expulsed from the Guayuta Group during the
early and middle Miocene, before the
emplacement of the Frontal thrust. These rocks
have continued the petroleum generation in the
sub-thrust positions during the late Miocene-
Recent. Oils existing in the different members of
the Oficina Formation come from predominantly
marine organic matter and correlate with the
calcareous shale and limestone of the Guayuta
Group. There are mixing of unaltered oils with
highly altered residues of earlier generated oils
and oils that do not show evidences of alteration of
n-paraffins, regular steranes nor homohopanes.
In general, the oils in Carabobo area show high
norhopane/ hopanes >1 combinated with C35/C34
22 S-hopane ratio(1.0-2.5) which are characteristic
of crude oils generated from marine carbonate
rock deposited under anoxic conditions with
restricted water circulation1. Nevertheless, the
non-biodegraded oils in the east and southeastern
part of Carabobo area, which have similar maturity
level (early maturity stage to maximum generation
of petroleum at the moment of expulsion), were
generated from a marine source rock with a more
siliciclastic input based on higher diasterane/
sterane ratio and C29/C30 hopane

P-295
Using diamondoids to unravel alteration processes
Gary Muscio
Chevron, Houston, Texas, United States of America (corresponding author:Gary.Muscio@Chevron.com)
The controls on phase (oil vs. gas) and volumes of
hydrocarbons in petroleum systems is the cumulative
effect of source facies, source rock maturity and
alteration processes. In Tertiary Deltas, source rocks
and reservoirs are typically stratigraphically separated
by a thick sedimentary section. In such basins, postexpulsion
alteration processes can have a significant
effect on the composition of a hydrocarbon phase
migrating from the source kitchen to the trap, resulting
in complex, multi-stage charge histories. Alteration
processes can include phase segregation, mixing of
hydrocarbons derived from source rocks of different
facies and/or maturity, and biodegradation.
Understanding the extent and magnitude of alteration
processes can help predict distribution and quality of
petroleum in an exploration environment.
In addition to classifying source rock facies and
maturity [1, 2], diamondoids have been used to
evaluate alteration processes such as biodegradation
and temperature-induced cracking of liquid
hydrocarbons to gas [3, 4, 5]. Their thermal stability
results in a progressive increase in concentrations in
oils that have been submitted to high levels of thermal
stress during cracking.
A set of oils from a Tertiary deltaic basin was
submitted to a comprehensive geochemical analytical
program, including GC, GCMS and GCIRMS, in order
to characterize the samples for their source facies,
level of thermal maturity and alteration. The present
study focuses on using diamondoids to assess how
the process of oil-to-gas cracking and mixing may
have altered the composition of reservoired oils.
For the diamondoid analyses, samples were selected
that were largely unaffected by biodegradation, in
order to minimize any effects of biodegradation on
concentrations of relevant biomarker compounds. The
oils were derived from reservoirs from different
subregional structural trends in the same basin.
Despite subtle compositional variations, suitable
molecular and isotope data suggest that the oils are
derived from source rocks that were deposited in
similar depositional environments.
Results indicate that while concentrations of
methyldiamantanes are lower compared to published
data from similar depositional settings [6], oils from
different structural trends appear to be affected to
varying degrees by contributions from a highly
cracked, diamondoid-rich source, as reflected by
higher concentrations of diamondoids. Furthermore,
samples from the same well but from different depths
also exhibit varying levels of cracking.
Due to the low temperatures (ranging from 65 to 110
C based on MDT temperature data) and relatively
recent charge, it is unlikely that the oils analysed in
this study have been submitted to in-situ cracking
reactions. Rather, the variations in diamondoid
concentrations are believed to be related to
hydrocarbons migrating from deeper sections where
conditions are more conducive for cracking. Hence,
nature and quality of migration pathways and their
variability between different structural trends play a
significant role.
Additionally, mixing of low mature oil with oil that has
been submitted to cracking has also altered the
composition of selected samples.
References
[1] Schulz L.K., et al. (2001) Org. Geochem. 32, 365-
375.
[2] Chen, J.H, et al. (1996) Org. Geochem. 25, 179-
190.
[3] Grice K., et al. (2000) Org. Geochem. 31, 67-73.
[4] Dahl J.E., et al. (1999) Nature 399, 54-56.
[5] Wei et al. (2006) Org. Geochem. 37, 891-911.
[6] Springer, M.V. et al. (2010) Org. Geochem. 41,
1013-1018.
428

P-296
Geochemical record of ancient sediments from the Potwar Basin
Pakistan, inferred by biomarker and stable isotopic signatures
Shahid Nadeem 1,2 , Kliti Grice 1 , Fazeelat Tahira 2
1 WA-OIGC, Department of Applied Chemistry, Curtin University, Perth, Australia, 2 Department of Chemistry,
University of Engineering and Technology, Lahore, Pakistan (corresponding author:snk777@gmail.com)
Cambrian and Infra-Cambrian source potential has
been universally recognised. A major portion of the
petroleum systems in the Potwar Basin of Pakistan
comprises of Permian or Cambrian and infra-
Cambrian aged-oils. The source potential of early
Permian and Cambrian sequences has been
recognised in the Potwar Basin. The present study
deals with the organic geochemical characterisation
of Cambrian sequences from the Eastern Potwar
Basin. A total of 24 sediment samples from 150m
thick organic-rich Cambrian and ~200m early-Permian
shales comprising of 6 geological formations have
been selected at 10m depth of intervals. These
sequences contain types I/II Kerogens based on the
Rock Eval data. n-Alkane profiles of the bitumens of
the sediments show a variation in the algal to
terrestrial source inputs. Very low Pr/Ph ratios 0.1-0.7
are indicative of strong anoxic conditions in the
original depositional environment. High
hopane/sterane ratios are consistent with a high
bacterial input.
Pyrolysis mainly by MSSV and HyPy has been
performed on the source rock kerogens and the
asphaltenes of the related oils. Biomarkers and
carbon isotopic profiles of individual aromatic
hydrocarbons such as 1,6-DMN, 1,2,5-TMN, 1,MP,
1,9-DMP have been used and cross plots have been
constructed along with Pr/Ph and P/DBT to establish
source and age of organic matter. Thermal history
has been evaluated using hopanes, steranes, alkylnaphthalenes
and alkyl-phenanthrene isomerisation
ratios. An oil to source correlation has been made
based on CSIA approach.
References
Aamir, M., Siddiqui, M.M., 2006. Interpretation and
visualization of thrust sheets in a triangle zone in
eastern potwar, Pakistan. The Leading Edge January
2006, 24-37.
Kadri, I.B., 1995. Petroleum geology of Pakistan,
Ferozsons (Pvt.) Ltd. Lahore-Pakistan.
Wandrey, C.J., Law, B.E. Shah, H.A., 2004. Patala-
Nammal Composite Total Petroleum System, Kohat-
Potwar Geologic Province, Pakistan. U.S. Geological
Survey Bulletin 2208-B.
(http://pubs.usgs.gov/bul/b2208-b/)
Kliti Grice, Birgit Nabbefeld, Ercin Maslen., 2007.
Source and significance of selected polycyclic
aromatic hydrocarbons in sediments (Hovea-3 well,
Perth Basin, Western Australia) spanning the
Permian–Triassic boundary. Organic Geochemistry
38,11,1795-1803.
Ercin Maslen, Kliti Grice, P. Le Métayer, Daniel
Dawson, Diane Edwards, 2011, Stable carbon
isotopic compositions of individual aromatic
hydrocarbons as source and age indicators in oils
from Western Australian basins. Organic
Geochemistry, accepted.
Asif, M., Grice, K., Fazeelat, T., 2009. Assessment of
petroleum biodegradation using stable hydrogen
isotopes of individual saturated hydrocarbons and
polycyclic aromatic hydrocarbon distributions in oils
from the Upper Indus Basin, Pakistan. Organic
Geochemistry 40, 301-311.
van Aarssen, B.G.K., Bastow, T.P., Alexander, R.,
Kagi, R.I., 1999. Distributions of methylated
naphthalenes in crude oils: indicators of maturity,
biodegradation and mixing. Organic Geochemistry 30,
1213–1227.
Hughes, W.B., Holba, A.G., Dzou, L.I., 1995. The
ratio of dibenzothiophene to phenanthrene
andpristane to phytane as indicators of depositional
environmentand lithology of petroleum source rocks.
Geochimica et Cosmochimica Acta 59, 3581-3598.
Budzinski, H., Garrigues, P., Connan, J., Devillers, J.,
Domine, D., Radke, M., Oudin, J.L., 1995. Alkylated
phenanthrene distributions as maturity and origin
indicators in crude oils and rock extracts. Geochimica
et Cosmochimica Acta 59, 2043–2056.
Lyndon J. Berwick, Paul F. Greenwood, Will Meredith,
Colin E. Snape, Helen M. Talbot, 2010, Comparison
of microscale sealed vessel pyrolysis (MSSVpy) and
hydropyrolysis (Hypy) for the characterisation of
extant and sedimentary organic matter. J. Anal. Appl.
Pyrolysis 87, 108–116
429

P-297
Significance of aromatic biomarkers to characterize petroleum
of the Southern Indus Basin, Pakistan
Shagufta Nasir 1,2 , Kliti Grice 1 , Tahira Fazeelat 2
1 WA-OIGC, Department of Chemistry, Curtin University,, Perth, Western Australia., Australia, 2 University of
Engineering & Technology,, Lahore, Pakistan (corresponding author:shagufta.nasir@gmail.com)
A suite of 21 oils from different fields have been
analysed to investigate the depositional environment,
maturity sources and in reservoir mixing of the oils
from the Southern Indus Basin (Pakistan). The
dibezothiophene/phenanthrene and pristane/phytane
ratios divide the oils into two groups of depositional
settings. The first group of oils, with low
dibenzothiophene/phenantherene ratio (

P-298
Petroleum generation in siliceous deposits of Sakhalin Island
(Russia)
Nikolay Oblasov, Ivan Goncharov, Vadim Samoylenko, Svetlana Fadeeva
TomskNIPIneft, Tomsk, Russian Federation (corresponding author:oblasovnv@nipineft.tomsk.ru)
In the Far East of Russia, Sakhalin Island is the
center of hydrocarbon production, where there are
about 70 oil and gas fields within the territory itself, as
well as, in the offshore area. According to numerous
researches, the major source rocks in this region are
Neogene – paleogene siliceous deposits [1]. The
characteristic feature of Sakhalin siliceous rocks is
considered to be the rather early process origin of oil
and gas generation in comparison to the classical
scheme. It was supposed that the oil window zone is
within the limits of vitrinite reflectance changes from
0.4 to 0.8%, while oil formation begins at a depth of
1.5km or even deeper [1, 2, 3].
Rock-Eval and GC/MS research of siliceous rocks,
chloroform extracts of rocks and oils from wells drilled
in Sakhalin onshore and offshore areas was
conducted. According to the Rock-Eval results in the
sedimentary mantle cross-section, there are rocks
with high organic carbon content (up to 3.7%) and
high hydrogen index value (up to 571 mg HC/g TOC),
which correspond to kerogen type II. Most
investigated rocks with high generation potential are
related to Pilsk Formation depositions, which could be
the major source rock in Sakhalin. Besides the abovementioned
formation, high organic matter content can
be found in Matituksk, Majamrafsk, Vengerisk and
Kaskadian formation depositions. The territorial well
placement, containing siliceous rocks of rather high
generation potential, is in the north and north-east
Sakhalin offshore, where the major oil and gas
deposits have been discovered.
GC/MS research included 15 oil samples from 7 oil
fields in Sakhalin (Vostochnoe Ehkhabi, Zapadnoe
Sabo, Nel‘ma, Okruzhnoe, Pela-Lech, Shkhunnoe,
Udachnoe).All these oils are a single genetic group of
organic matter source, formed from marine
bioproducers with an insignificant amount of land
vegetation. Despite the biodegradation of most
studied oil samples, their biomarker composition
considerably matches the chloroform composition of
extracts from potential source rocks. Correlation of
some molecular parameter values of the thermal
maturity in rock and oil extracts (Fig. 1) showed that in
most investigated rock samples the organic matter
has not reached the thermal maturity level of existing
oils. The most near-maturity value for oils was
discovered in rock samples of Pilsk Formation, from
Vostochnyy Kaygan №2 well, the depth of which is
3.3-3.6km. The Rock-Eval value of Tmax parameter for
these samples ranges within 431-434 о С, which
proves that the rock organic matter is on set of oil
generation. It could be stated that the major oil
formation zone is located at a depth of more than
3.5km.
Fig.1. Relationship of molecular parameters of
thermal maturity for oil and extracts from silica rocks.
References
[1] Koblov E. G. et al (1997) Geology and
Development of oil and gas in Sakhalin and offshore.
Moscow: Nauchin Mir - 198 p.
[2] Bazhenova O.K. et al. (2000) Geology and
geochemistry of oil and gas, M,: MSU Publishing
House.- 384p..
[3] Punanova S. A. and Vinogradova T. L.
(2010) Geochemistry <strong>International</strong> 48, 1138-1147.
431

P-299
Drilling conditions making wells unsuitable for fluid inclusion
studies
Sverre Ekrene Ohm, Helen Haneferd
ConocoPhillips, Tananger, Norway (corresponding author:sverre.e.ohm@conocophillips.com)
A fluid inclusion study carried out on a well in the
Northern North Sea showed a remarkable correlation
between fluid inclusion stratigraphy responses and
depths of bit changes. Further investigation of the well
data suggested that extreme temperatures
occasionally had been generated at the bit-sediment
interface during drilling. Cracking of larger molecules
to an abundance of smaller ones and trapping of
these in inclusions formed by super-cooling of partly
melted sediment explain the correlation. Not all wells
are consequently suitable for fluid inclusion screening
analyses. Thus, before initiating fluid inclusion
studies, wells which have experienced intense heat
during drilling should be identified and avoided.
Figure
To the left various Fluid Inclusion Stratigraphy (FIS)
responses are shown through the well. The right part
of the figure shows a blow-up of that part of the well
which shows the most significant FIS responses. The
gamma ray (GR) and sonic velocity (DT) logs are also
displayed for this depth interval. The numbers 1 – 14
represent bit changes at associated depths and the
colour bar reflects the FIS interpretations. A close
correlation is noted between FIS responses and some
of the bit changes
432

P-300
The alteration of oil during formation of the low-temperature
MVT Zn-Pb sulfide ore deposit at Tres Marias, Chihuahua,
Mexico
Christian Ostertag-Henning 1 , Frank Melcher 1 , Bernhardt Saini-Eidukat 2
1 Bundesanstalt fuer Geowissenschaften und Rohstoffe, Hannover, Germany, 2 North Dakota State University,
Fargo, United States of America (corresponding author:Christian.Ostertag-Henning@bgr.de)
The ore body in the Tres Marias Mine in Mexico is
exceptionally rich in germanium and occurs in a
carbonate collapse breccia. It consists of two major
ore types reflecting the history of the ore deposit
formation: The primary Zn-Pb-sulfide ore deposit and
a secondary sulfide poor oxidized ore body with Zn
silicates, carbonates and other oxide minerals (Saini-
Eidukat et al., 09).
Within the primary sulfide ore body, there is an
intimate association of the type I Zn-sulfide crystals
with abundant bitumen (fig. 1). Common modes of
bitumen occurrence include vein fillings in the host
rock or sulfide ore, masses within vugs associated
with sulfides, as fluid and solid inclusions in
sphalerite, and as small stalagmites or seeps in the
mine stopes. At some places the texture of the Znsulfide
crystals seem to indicate the growth of the ore
into an oil-rich fluid.
The sulfur isotopic values of the Zn,Pb-sulfide
samples cluster between +4.8 to +8.3 ‰ and confirm
the invoked low-temperature Mississippi Valley type
origin for the primary ore deposit. For this type of
deposits a major source of the sulfide could be
provided by thermochemical sulfate reduction
concomitant with alteration of hydrocarbons in the
vicinity.
To elucidate the timing of the oil emplacement, its role
for the ore deposit formation – and perhaps the
importance for the unusual enrichment of some
elements as germanium, cadmium and arsenic -
bitumen from the primary ore body has been analyzed
with GC-FID, GC-MS, Py-GC-MS and EA-irmMS. The
samples investigated include bitumen extracted from
small closed vugs, bitumen from whole ore extraction,
aliphatic and aromatic fractions as well as separated
asphaltene fractions.
The microscopic investigations clearly indicate that
the bitumen was in place before the ore formation has
commenced. The bitumen content in the whole ore
samples ranges from 0.2 to 1.8%. The organic
geochemical analyses depict an increasing level of
alteration on the compound class and molecular level.
Clear indications of alteration of oil include the
increase of the percentage of the asphaltenes, an
increase in the aromatic/aliphatic ratio, the
progressive removal of n-alkanes and isoprenoids
(fig. 2), ring-opening of some terpenoids, progressive
incorporation of S into the bitumen as indicated by
pyrolysis products, and depletion of hydrogen in the
bitumen. It is interesting to note that most of the
observed bitumen alteration patterns could be caused
by both abiotic as well as biotic alteration of the oil –
which is further discussed in the contribution with its
implications for the ore formation/oxidation.
Fig. 1: Backscattered micrographs of minerals (Zn-sulfides:
dark/light grey) of the primary ore body with bitumen (black)
in vugs..
Fig. 2: Examples of observed changes during alteration of
bitumen.
References
[1] Saini-Eidukat, B.; Melcher, F.; Lodziak, J. Miner.
Deposita 44: 363-70.
433

P-301
Biomarker distributions and δ13C values of individual n-alkanes
of source rocks, crude oils and oil components from reservoir
rocks of Tarim Basin, China
Changchun Pan 1 , Shuang Yu 1 , Jinji Wang 1 , Xiaodong Jin 1 , Lanlan Jiang 1 , Dayong Liu 1 ,
Xiuxiang Lü 2 , Jianzhong Qin 3 , Yixiong Qian 4 , Yong Ding 4 , Honghan Chen 5
1 State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of
Sciences, Guangzhou, China, 2 Basin & Reservoir Research Center, China University of Petroleum, Beijing,
China, 3 Wuxi Institute of Petroleum Geology, Sinopec, Wuxi, China, 4 Research Institute of Exploration and
Development, Northwest Oil Company, Sinopec, Urumqi, China, 5 Department of Petroleum Geology, Faculty
of Earth Resources, China University of Geosciences, Wuhan, China (corresponding
author:cpan@gig.ac.cn)
Numerous studies have been performed in oil
source correlation in Tarim Basin, however, the
origins of the discovered oils in the cratonic region of
this basin remain unresolved [1-3]. In the present
study, 54 oils and 70 oil-containing sandstones and
carbonates from the boreholes in the Tazhong Uplift
and the Tahe Oilfield in the Tabei Uplift, along with 24
source rocks within the Cambrian-Ordovician strata
from the boreholes of this Basin were analyzed using
GC-MS and GC-IRMS. Based on the ratios of
gammacerane/C31 hopanes and C28/(C27+C28+C29)
steranes, 3 of the 15 oils from the Tazhong Uplift
correlate with Cambrian-Lower Ordovician source
rocks while the other oils from the Tazhong Uplift and
all the 39 oils from the Tahe Oilfield correlate with
Middle-Upper Ordovician source rocks (Fig. 1a).
These two ratios further demonstrate that most of the
free oils and nearly all the adsorbed and inclusion oils
of oil-containing reservoir rocks from the Tazhong
Uplift correlate with Cambrian-Lower Ordovician
source rocks (Fig. 1b) while the free and inclusion oils
of the oil-containing carbonates from the Tahe Oilfield
correlate mainly with Middle-Upper Ordovician source
rocks (Fig. 1c). This result suggests that the crude oils
in the Tazhong Uplift are partly derived from
Cambrian-Lower Ordovician source rocks while those
in the Tahe Oilfield are overwhelmingly derived from
Middle-Upper Ordovician source rocks.
The δ 13 C values of individual n-alkanes are
relatively high for both the Cambrian-Lower
Ordovician and Middle-Upper Ordovician source
rocks, ranging (-32)−(-29)‰ (Fig. 1d) while relatively
low for the crude oils both from the Tazhong Uplift
and the Tahe Oilfield, ranging (-36)−(-32)‰ and (-
35)−(-33)‰, respectively (Fig. 1e). In addition, these
values are higher in the inclusion oils than free oils for
the oil-containing carbonates from the Tahe Oilfield
(Fig. 1f), implying that the initial charging oils are
heavier than the current in carbon isotopic
compositions of n-alkanes for these reservoirs.
Fig. 1 Crossplot of the ratios of C28/(C27+C28+C29) steranes
versus gammacerane/C31 hopanes (a-c) and theδ 13 C values
of individual n-alkanes (d-f) for the extracts of source rocks,
crude oils and the free, adsorbed and inclusion oils in the
reservoir rocks. In (a), (d) and (e), S1: the Cambrian-Lower
Ordovician source rocks; S2: the Middle-Upper Ordovician
source rocks; O1: oils from the Tazhong Uplift; O2: oils from
the Tahe Oilfield in the Tabei Uplift.
References
[1] Zhang, S. et al. (2000) Org. Geochem. 31, 273-
286.
[2] Sun, Y. et al. (2003) Org. Geochem. 34, 629-634.
[3] Pan, C., Liu, D. (2009) Org. Geochem. 40, 387-
399.
434

P-302
Carbonaceous rocks of the Neoproterozoic (Vendian) Khatyspyt
Formation as a possible source of oils in the northeastern
Siberian Platform
Tatyana Parfenova, Vladimir Kashirtsev, Lubov Borisova, Elena Ivanova, Boris Kochnev,
Konstantin Nagovitsyn, Vasily Melenevsky
Trofimuk Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsc, Russian Federation
(corresponding author:parfenovatm@ipgg.nsc.ru)
Organic-rich carbonate rocks of the Khatyspyt
Formation of the Neoproterozoic (Vendian – 544-
550 Ma) in the western and northern slopes of the
Olenek uplift are considered as potential oil source
rocks in the northeastern Siberian Platform. The
organic carbon content (TOC) in the rocks is known to
vary from 0.04 to 14 % [1, 4-6, and oth]. Comparative
analysis of the molecular composition of saturated
hydrocarbons (HCs) of the Khatyspyt Formation has
allowed identification of the features similar to those of
bitumens occurring in Vendian-Cambrian deposits of the
Olenek uplift. The major of them include the absence
of 12- and 13-monomethylalkanes, anomalously high
contents of ethylcholestane in sterane HCs and
gammacerane in terpane HCs, and the presence of
29,30-bisnorhopane. The authors suggest that
bitumens of the Olenek uplift and bitumen extracts
from the examined carbonate deposits have been
generated from a single source, the Khatyspyt
Formation rocks [1-5, and oth.].
A collection of rocks (8 samples) of Khatyspyt
deposits of 245 m thick from the outcrops of the
Khorbusuonka R. has first been studied by pyrolysis
method. It has been established that the organic
matter content in 2 samples is below the limit of
satisfactory estimate of generative properties of rocks.
S1 in 6 samples vary from 0.01 to 0.50 mg HC/g rock.
S2 is within the range 0.08-16.00 mg HC/g TOC. Thus,
the generative potential (S1+S2) of rocks varies from
0,00 до 16.50 mg HC/g TOC. Hydrogen index (HI) in
OM of rocks varies from 56 to 382 mg HC/g TOC.
High values of HI indicate that OM is type II.
Generally, the low values (less than 150-200 mg HC/g
TOC) suggest that OM is of type III. Lower HI values
seem to be related to the hydrogen loss in oxidizing of
OM in diagenesis or hypergenesis. Tmax of rocks vary
within the range of 437-444 °С.
Kerogens were extracted from 3 samples. Two
samples contain 75.9 and 81.58 % carbon (C), 6.9
and 7.1 % hydrogen (H), 0.01 and 3.8 % sulfur (S),
2.4 and 1.2 % nitrogen (N), 14.8 and 6.30 % oxygen
(O), respectively. HI values in these samples amount
to 322 and 364 mg HC/g TOC. One sample shows an
anomalously low content of C in bitumens (71.4 %)
and H (4.7 %), and high content of O (21.8 %). Its HI
is 184 mg HC/g TOC. The lower HI values and the H
and C content in kerogen are likely to be resulted
from OM oxidation. For the first time, stable carbon
isotopes (δ 13 С) of kerogens (2 samples) have been
examined, δ 13 С is equal to –32.3 and –33.5 ‰. The
δ 13 С average value of bitumens is –33.0 ‰ in Vend-
Cambrian deposits of the Olenek uplift [1, and oth.].
Tmax of kerogens varies from 438 to 441 °С. They
confirm the estimates obtained from rock analysis,
and agree with the known values of molecular
coefficients of maturity [5].
Conclusion. The OM-depleted rocks have a low
generative potential according to [7]. Organic-rich
limestones are characterized by a moderate and high
generative potential. The results of rock and kerogen
pyrolysis, elemental composition of kerogens, and
molecular parameters suggest that Khatyspyt
deposits entered the oil window during their geologic
history. In some intervals of the section of the
Khatyspyt Formation, OM is oxidized. Similar values of
δ 13 С in the examined kerogens and bitumens of the
Olenek uplift have first allowed the confirmation of
genetical relation of bitumens and OM of the
Khatyspyt Formation at the atomic level. New results
show that the section of the Vendian Khatyspyt
sequence contains carbonaceous rocks, a source of
naphthides in the northeast of the Siberian Platform.
References
[1] Kashirtsev V.A., ―Organic Geochemistry of
Naphthides of the East Siberian Platform―. (Yakutsk, 2003)
[in Russian].
[2] Kashirtsev V.A., et al. Deposits of natural
bitumens in the northeastern Siberian Platform (Russian
Arctic sector) // Rus. Geol. and Geophys. 2010. No 1.
[3] Kontorovich A.E., et al. // DAN. 2005. V. 402. № 5.
[4] Kontorovich A.E., et al. // DAN. 1995. V. 345. № 1.
[5] Kontorovich A.E., et al. Organic geochemistry of
the Vendian Khatyspyt Formation (northeast of the Siberian
Platform) // The 24 th <strong>International</strong> meeting on organic
geochemistry. Bremen. Germany. 2009. P. 174.
[6] Natapov L.M. // Soviet Geology. 1962. № 11.
[7] Tissot B., Welte D. Petroleum formation and
occurrence. Moscow: Mir, 1981. 502 p.
435

P-303
Evaluation of petroleum systems in the area Carúpano Basin,
offshore Venezuela, through basin modeling 3D
Adriana Pérez, Irenio Berrios
PDVSA-Intevep, S.A., Los Teques, Venezuela (Bolivarian Republic of) (corresponding
author:perezacy@pdvsa.com)
Carúpano Basin is an oval depression covering some
30000 km 2 with a southwest-northeast orientation. It
has around 300 km long and extends from the
Margarita Platform to the Tobago Island. The
presence of hydrocarbons in this area had been
confirmed by the production data of the wells, which
have reported condensate and gaseous
hydrocarbons. The geochemical features of these
hydrocarbons, based in the molecular and isotopic
composition of some samples of gases, suggest the
presence of at least two petroleum systems,
thermogenic and biogenic systems. The aim of this
study was to identify and evaluate the thermogenics
petroleum systems in the area by 3D basin modeling,
in order to contribute to the reduction of uncertainty in
exploratory risk in the basin.
The methodology of this study was based on 1) the
construction of the 3D block 2) gridding, 3) allocation
of the properties of the elements of the petroleum
system and 4) backward and forward modeling. This
methodology permitted to get a 3D block with the
main characteristic of the Carúpano Basin.
Additionally, in this study was done a semiquantitative
evaluation of hydrocarbons thermogenic
generated in the Carúpano Basin, in order to get the
Generation – Acummulation Efficiency (GAE) of the
petroleum systems identified in the basin.
The results of simulations made suggest that of "all
potential source rocks" evaluated in the area, the
Eocene and Oligocene corresponding to principal
sequences that have generated, expelled and have
succeeded in generating accumulations in the
hydrocarbons in the area. Early Miocene sequence
has a level of maturity suitable for the generation but
it has not expelled hydrocarbons to generate
significant amounts of commercial accumulations.
Probably to the moment it began the expulsion, the
traps had not yet developed. At the time of early
Miocene just began the expulsion of hydrocarbons,
the main reservoir (Late Miocene) started its
sedimentation. This reflects the lack of
synchronization between the event generation,
migration and accumulation of hydrocarbons to come
from the lower Miocene sequence, so these
hydrocarbons could not be accumulated. However,
hydrocarbons come from the Eocene and Oligocene
sequences could be accumulated in the sandy facies
of the upper Miocene and lower Pliocene.
Additionally, the Eocene was able to achieve oil
accumulation in the upper sand interval of the same
sequence, in traps associated with anticlines. The
values of the GAE obtained for petroleum systems
described (Eoceno – Eoceno (?), GAE: 0,015 % and
Oligoceno –Mioceno Tardío (?), GAE: 4,12 x 10 -4 %)
are considerably lower and they can be classified as
inefficient.
An important aspect to be considered in the models of
generation, migration and entrapment of
hydrocarbons in this basin is associated with the
distribution of sedimentary facies and especially the
quality of reservoir sands, because information
available from the sedimentary view to define the
extent and thickness of these sequences is limited,
due to the large extension that exists between the
boreholes and the low number of cores and electric
logs. This aspect has affected the value of GAE and
limited the reach and resolution of the models
generated in this study, coupled with the lack of
geochemical data related to the characterization of
the fluids found in the area.
However, the results presented here suggest that this
area has a high potential for hydrocarbon exploration
in the area, not only in the intervals already drilled but
in deeper intervals like Eocene, which should be
studied more carefully, so as to assess in detail the
potential of them, which could increase opportunities
for exploration in the area.
436

P-304
Decision-tree chemometrics of biomarker and isotope data
identifies multiple petroleum systems in the San Joaquin Basin,
California
Kenneth Peters 1 , L. Scott Ramos 2 , Leslie Magoon 3 , Paul Lillis 4 , John Zumberge 5
1 Schlumberger and Stanford University, Mill Valley, United States of America, 2 Infometrix, Inc., Bothell,
United States of America, 3 USGS Emeritus and Stanford University, Menlo Park, United States of America,
4 USGS, Denver, United States of America, 5 GeoMark Research, Ltd., Houston, United States of America
(corresponding author:kpeters2@slb.com)
Chemometric analysis of 17 source-related biomarker
and stable carbon isotope ratios was conducted on
185 oil samples from the San Joaquin Basin. The
results identify three tribes and 14 families of oils (Fig.
1), which retain the imprint of the vertical and lateral
organofacies variations in their source rocks: (1)
Eocene Kreyenhagen and Tumey formations (four
families) (2) Miocene Monterey Formation (North
depocenter, eight families), and (3) Miocene Monterey
Formation (South depocenter, two families).
Fig. 1. Automated chemometric decision-tree can be
used to classify newly collected oil samples into one
of 14 San Joaquin Basin oil families.
Tribe 1 originated in one depocenter from basal
Kreyenhagen and overlying Tumey source-rock
organofacies. Families in Tribe 1 have more negative
isotope ratios and higher diasteranes than Tribes 2 or
3. Miocene Tribes 2 and 3 originated from Upper and
Lower Monterey source rock in two depocenters.
Tribe 2 originated from the Buttonwillow depocenter,
while Tribe 3 originated from the Tejon depocenter
north and south of the Bakersfield Arch, respectively
(Fig. 2). Unlike the other six oil families in Tribe 2
generated from the Upper Monterey Formation,
Families 22 and 231 originated mainly from the Lower
Monterey Formation and have low 25,28,30trisnorhopane
and 28,30-bisnorhopane ratios.
Fig. 2. The Bakersfield Arch plays a key role in the
distribution of Miocene oil families. Tribe 2 originates
from the North (Buttonwillow) depocenter, while Tribe
3 originates from the South (Tejon) depocenter.
Tribe 3 oils from south of the Arch have higher C19/C23
tricyclic terpane, oleanane/hopane, and %C29 sterane
ratios than Tribe 2 from north of the Arch. Therefore,
the Monterey source rocks for Tribe 3 were enriched
in higher plant input compared to Tribe 2. Based on
production intervals, Families 31 and 32 are from
Upper and Lower Monterey source rock, respectively.
Family 31 has lower C19/C23 tricyclic terpane,
oleanane/hopane, and diasterane ratios and higher
steranes/hopanes, indicating a more distal source
rock with less higher plant input than Family 32.
Both the Eocene and Miocene families show little
cross-stratigraphic migration due to internal seals
within the source rocks as evidenced in outcrops at
Chico Martinez Creek and elsewhere in the basin.
These results show the value of chemometrics
applied to large petroleum databases where all
samples are analyzed using the same procedures
and instrumentation.
437

P-305
Geochemical indices of hydrocarbon systems of early
generation
Svetlana Punanova, Tatyana Vinogradova
Institute of Oil and Gas Problems, Russian Academy of Sciences, Moscow, Russian Federation
(corresponding author:punanova@mail.ru)
This study analyzed and categorized geochemical
composition of early catagenetic hydrocarbon (HC)
accumulations of petroliferous basins of Russia,
Azerbaidzhan, Turkmenistan, Belorussia, Japan,
China, Australia, Indonesia, USA, Canada, Israel and
Guatemala. Oils from these basins were grouped by
lithofacial conditions of their source OM: marine (deep
and shallow water) and continental (lacustrine, coal-
bearing and subcoal alluvial-paludal) [1].
The following indices were used in the study: contents
of n-alkanes, isoprenoids, arenes, odd-even CPI,
biomarkers (steranes, hopanes, mono and tri-
aromatic steranes); ratios of some of the biomarker
indices and also trace elements (TE) and
metalloporphyrin complexes (MPC). We utilized
classification of chemical composition of oils [2]. The
presence of moretanes and low ratios of HC
biomarkers in fluids of all facies, such as 20S/20
(S+R) – by C29 (less than 55%); 22S/22 (S+R) – by
H31 (48% - 58%); 22S/22 (S+R) by M32 (~35%)
demonstrates early-generation stage of oil generation.
Compared to mature fluids, immature accumulations
of chemical types A-2, A a -1, A b -1 and A c -1 have
elevated values of P/n-C17 (up to 9.7) and Ph/n-C18
(up to 5.2).
Oils generated by OM of marine deep water facies
have low ratios of P/Ph (up to 1.7), prevalence of
steranes C27 (cholestanes) and wide range of
hopanes H27-H35. Oils of terrigenous-siliceous facies
have monomodal distribution of n-alkanes in C15-C19
domain, prevalence of P over Ph, tricyclanes over
tetracyclanes, trisnorhopane Tm over Ts, steranes
over hopanes, presence of oleanane and 28,30bisnorhopane.
Oils of terrigenous-carbonate and
carbonate facies have bimodal distribution of nalkanes,
prevalence of even n-alkanes in C22-C28
domain, Ph over P, tetracyclanes over tricyclanes,
trisnorhopane Ts over Tm, hopanes over steranes,
presence of gammacerane.
Oils generated by OM of shallow water facies have
equal contents of steranes C28 and C29, low quantities
of light steranes C21-C22, sterane C30 and oleanane,
as well as some hopanes H27-H33.
Oils of marine genesis have low contents of V+Ni (6.9
ppm), MPC (52 ppm) and V/Ni < 1 (0.6). However,
oils generated by OM of the Monterey Formation
(California) have higher concentrations of these
elements V+Ni (348 ppm), MPC (300 ppm) and V/Ni >
1. Oils of the Monterey Formation were generated in
strongly reducing conditions of diagenesis during the
longlasting and stable subsidence of the
sedimentation basin. The OM of the source rocks (an
analogue of the Domanik Formation in the Eastern
European Platform) shows a higher grade of
catagenesis.
Oils generated by OM of continental lacustrine facies
have the increased content of tricyclic HC C20-C29,
wide presence of light steranes C21-C22, steranes C30,
dinosteranes and gammacerane. Oils of lacustrine
salty facies are distinguished by prevalence of even
n-alkanes over odd n-alkanes, Ph over P, abundance
of alicyclic isoprenoids, and wide range of hopanes
H27-H35. Oils and condensates generated by OM of
continental coal-bearing and subcoal alluvial-paludal
facies have high concentrations of P, with P/Ph up to
13.8. Wide presence of bisnorlupanes and oleanane
is found in West Canada, while 25,30-bisnorhopane,
25,28,30-trisnorhopane and 25-norhopane are found
in West Siberia. Oils of these facies have significantly
lower contents of TE and MPC. Contents of Ni in
these oils is usually higher than V (V/Ni = 0.1-0.7).
Similar ratio is characteristic of MPC (Vp/Nip < 1).
Due to the prevalence of Ni over V these oils are
combined into a group of Ni-bearing oils.
The established specific indices of early-generation
oils and condensates are recommended to be used in
geochemical correlation of oils and in predicting of
both HC and TE compositions of oils generated by
OM of different lithofacial types.
References
[1] Vinogradova, T., Punanova, S. Hydrocarbon
Systems of Early Generation, Geokhimiya, No. 1,
103–108 (2009)
[2] Petrov, Al. Oils of the Early Generation
Stages, Geol. Nefti Gaza, No. 10, 50–53 (1988)
438

P-306
Evaluation of surface geochemistry and data mining in Brazilian
sedimentary basins
Jean R. Heckmann 1 , Débora A. Azevedo 2 , Luiz Landau 1
1 LAMCE/COPPE, Universidade Federal do Rio de Janeiro, Rio de Janeiro/RJ, Brazil, 2 Departamento de
Química Orgânica, Instituto de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro/RJ, Brazil
In recent years we have seen significant progress in
the advancement of geosciences. This have been
accomplished due to many aspects, such as, the
improvement in computer hardware, data integration,
quantification of uncertainties, effective use of
geochemistry data and reservoir properties, and the
consideration of unconventional statistical methods.
Thus, the use soft computing tools might be a keypoint
that will facilitate, in a substantial way, the
access to this dataset. Among other highlights, the
computational techniques to Data Mining (KDD -
Knowledge Discovery in Data Base) and / or simply
the discovery of robust data in a volume have an
implicit knowledge.
Stages of the Knowledge Discovery Database
technique (KDD), figure 1:
Data
Coords.
Grid
Clustering
Classifier
Geo-
Processing
Groups
Groups
Model
Groups
Mapping
Fig. 1: Knowledge Discovery Database
From the numerical analysis it is performed an
integrated evaluation of the geochemical parameters
that can provide a better understanding of the basin
formation.
The database corresponds to the data provided by
the BDEP/ANP (Banco de Dados de Exploração e
Produção/Agência Nacional do Petróleo) results
acquired from evaluations of the 500 piston cores of
the Santos basin: Fluorescence int, Emission max,
Excitation max (nm); Total alkanes, Total UCM (ppb);
Methane, Ethane, Propane, i-Butane, n-Butane and n-
Pentane (ppm).
One of the main tasks of data mining is the step of
grouping (clustering). This step identifies data sets
that have similar characteristics among themselves
and groups that have different characteristics.
In order to perform the cluster analysis it was used
software called Matlab (version 2007).
The assumption of the number of cluster database is
the first step in the process of clustering. Therefore,
the algorithm Fuzzy C-Means (FCM), were performed
to validate the Index (PBM).
PC2
PC1
Fig. 2: Pertinence functions FCM 2D
Fluorescence, emission, excitation and total alkanes
were the factors that had higher values of pertinence
for principal component 1 (PC1), while for component
2 (PC2) were the fluorescence, emission, excitation
and methane. Thus, the data mining resulted in well
resolved three main groups with the values of piston
cores with similar characteristics among themselves,
as highlighted in red, figure 2.
The authors would like to thank the Brazilian National
Petroleum Agency (ANP, PRH-02) for the financial
support.
References
[1] Jones, V. T., Burtell, S. G. Hydrocarbon Flux
Variations in Natural and Anthropogenic Seeps.:
.
Acessed: 28/01/2011.
[2] Aminzadeh, F., 2005. Journal of Petroleum
Science and Engineering 47, 5-14.
439

P-307
Basin modelling of the Hammerfest Basin and Loppa High
(Southwestern Barents Sea); investigating the leakage of
hydrocarbons in a glacially influenced marine environment
Enmanuel Rodrigues 1 , Rolando di Primio 1 , Zahie Anka 1 , Daniel Stoddart 2 , Brian
Horsfield 1
1 GeoForschungsZentrum, Potsdam, Germany, 2 Lundin Norway AS, Lysaker, Norway (corresponding
author:rodrig@gfz-potsdam.de)
The Barents Sea has a complex geologic history,
especially during the Cenozoic period, because at this
time the area was clearly influenced by tectonic,
paleoceanographic and paleoclimatic events 1,2 . These
events were determinant as they have caused the
redistribution and leakage of the hydrocarbons in the
system 3 . Present-day accumulations are underfilled
and are known to have leaked in the past; however
the timing and extent of the leakage are largely
unconstrained. This study aims to assess and
quantify the amount of hydrocarbons generated by
the main source rocks in the Barents Sea (focussed in
the Hammerfest Basin and the Loppa High), and
determine the proportion leaked to the hydro- or
atmosphere. The effects of glaciation and
deglaciation, and the formation of gas hydrates
together with their possible destabilization, which also
leads to the sequestration and release of gaseous
hydrocarbons, were included in this study. A
quantification of the amount of hydrocarbons leaving
the system was made for the Hammerfest Basin and
is currently carried out for the Loppa High.
The Hammerfest Basin (HB) model reproduces most
of the known oil and gas accumulations in the area
(Snøhvit, Albatross, Askeladden and Goliat fields),
mainly in the most important reservoir: the middle
Jurassic Stø Formation. The main source rocks for
our models are the Jurassic Hekkingen Formation
and the Triassic Snadd and Kobbe formations. The
phase state in the HB accumulations corresponds
mainly to gas with a thin oil leg, except for the Goliat
field, which is filled with oil and has a very thin gas
cap. According to the volumetrics, the present-day
accumulations in the Stø Fm. unit are around 314
Mton (314 x 10 9 kg) for the liquid phase and around
300 Mton (300 x 10 9 kg) for the vapour phase, with
about 213 Mton (213 x 10 9 kg) corresponding to CH4.
The model predicts a slight overpressure in the main
reservoir (Stø Fm.) during glacial loading. The cyclic
loading and unloading of the basin during glacial and
interglacial periods generated pressure fluctuations
(overpressure) which reached up to 5 MPa in
magnitude.
Our preliminary results allow to investigate how ice
loading and unloading affected the reservoir fill,
resulting in spill and leakage. Also the temporal
variability of gas hydrate stability conditions can be
inferred for the HB model, in the timespan between
1.00 Ma and 11,500 years. Investigation of sediment
surface temperature and depth during the glacial and
interglacial periods shows that during the glacial
periods the shallowest parts of the HB were well
within the gas hydrate stability zone, while during
interglacial periods conditions are generally outside
the stability boundary. Moreover, leakage from the
reservoir is predicted to occur preferentially at the
transition from glacial to interglacial times. Leaking
gas was likely sequestered in gas hydrates below the
decaying ice sheet and then released during the
following marine transgression. Modelled cumulative
lost or leaked volumes of CH4 from the reservoir are
in the range of 200 Mton (200 x 10 9 kg). These results
support the possible sequestration of CH4 in gas
hydrates during the glacial periods in the HB, their
likely destabilization during the interglacials, and the
possible leakage to the surface. Methane is known to
be a potent greenhouse gas and atmospheric
contents have been reported to increase since begin
of the last interglacial 4 . Accordingly, our results
contribute to the understanding of global-paleoclimatic
changes.
References
1. Dimakis, P., B.I. Braathen, J.I. Faleide, A. Elverhøi, and
S.T. Gudlaugsson, 1998, Cenozoic erosion and the
preglacial uplift of the Svalbard–Barents Sea region:
Tectonophysics, v. 300, p. 311-327.
2. Vorren, T.O., G. Richardsen, S.-M. Knutsen, and E.
Henriksen, 1991, Cenozoic erosion and sedimentation in the
western Barents Sea: Marine and Petroleum Geology, v. 8,
p. 317-340.
3. Ohm, S.E., D.A. Karlsen, and T.J.F. Austin, 2008,
Geochemically driven exploration models in uplifted areas:
Examples from the Norwegian Barents Sea: AAPG Bulletin,
v. 92(9), p. 1191-1223.
4. Maslin, M., M. Owen, S. Day, and D. Long, 2004, Linking
continental-slope failures and climate change: Testing the
clathrate gun hypothesis: Geology, v. 32, p. 53-56.
440

P-308
Evidence of hydrocarbon generation through decarboxylation
reactions: qualitative and quantitative analyses by FTICR-MS
Elodie Salmon 1 , Françoise Behar 2 , Patrick G. Hatcher 1
1 Old Dominion University, Department of Chemistry and Biochemistry, Norfolk, VA, United States of America,
2 IFP Energies Nouvelles, Rueil-Malmaison, France (corresponding author:esalmon@odu.edu)
The aim of the present study is to demonstrate that
decarboxylation reactions are the main processes
occurring during hydrocarbon generation from
kerogen. To ascertain this conclusion, a Type I
kerogen from the Green River formation was
pyrolyzed in a closed system at various T/t conditions.
The NSO compounds generated during the artificial
maturation were collected by successive n-pentane
and dichloromethane (DCM) extractions and analyzed
using electrospray ionization Fourier transform ion
cyclotron resonance mass spectrometry (ESI-FTICR-
MS) to identify dominant series of compounds.
A large variety of 75 homologous series is identified
across the entire m/z range of each mass spectrum
and represents at least 72% of the total peak area of
each spectrum. Several series of polar CHO, CHOS,
and CHON compounds between C12 and C50+ are
observed. During the artificial maturation, the
molecular weights of these C12 - C50+ compounds tend
to decrease with increase severity. The CHO
compounds that are dominant in each spectrum
represent, at low conversion (275°C/9h), 58% and
23% of the total peak area in the n-pentane and DCM
extracts, respectively. Within these CHO compounds,
more than half of are comprised in the 4 series,
CnH2nO2, CnH2n-2O2, CnH2n-2O4, CnH2n-10O2, which all
correspond to carboxylic acid compounds.
Similar to previous studies involving
extraction/derivatization approaches, we show that
the distribution of these carboxylic acid compounds
(Figure 1) detected by ESI-FTICR-MS is directly
correlated to the distribution of hydrocarbons using
the carbon preference index (CPI). This index is
commonly used to characterize oils and source rock
extracts and is defined as the predominance of odd or
even numbered hydrocarbons or carboxylic acids.
The correspondence of CPI between saturated
hydrocarbons (odd-dominated) and saturated
monoacids CnH2nO2 (even-dominated) is suggestive
of a genetic link that involves decarboxylation.
We have quantified the amount of carboxylic acids
that is converted to hydrocarbons using external
(calibration curves) and internal (by standard
additions) calibration of each extract and using
oxygenated model compounds (linear, alicyclic,
saturated, and unsaturated) containing acid and
alcohol groups. We show that almost the entire
amount of hydrocarbons generated during the artificial
maturation can be related to one of the carboxylic
acid compounds extracted from the kerogen. This
strongly suggest that decarboxylation of acid
compounds from kerogen is the main process for the
generation of hydrocarbons.
441

P-309
Comparative characteristics of molecular composition of
basement oils in various regions
Yury Savinykh 1 , Vu Van Hai 1
1 Institute of Petroleum Chemistry, Siberian Division of the Russian Academy of Sciences, Tomsk, Russian
Federation, 2 Nanional Research Tomsk Politechnic University, Tomsk, Russian Federation (corresponding
author:yu-sav2007@yandex.ru)
The present stage of development oil-gas
exploration geology is characterized by the greater
orientation on discovering non-traditional objects.
Such objects are natural reservoirs formed by
fractured crystal rocks. The major part of hydrocarbon
(HC) accumulations in such reservoirs is in buried
ledges of the basement represented by fractured
metasomatic igneous rock, quartzites, granites,
dolomites. The question of genesis of these oils
remains debatable till now. Among variety of
publications two ideas of HC genesis in fractured
basement can be emphasized:
-Oil-gas generating systems are located above the
basement or on slopes of ledges;
-Basement is considered as an independent oil-gas
generating object, in structure of which various types
oil-gas generating systems functioning under
influence of deep factors are developed, in form of
spontaneous, periodically shown deep ascending HC
streams.
Correlation of molecular structure of oils from
sediments and the crystal basement of Southern -
Tatar arch (STA) has shown both their syngenesis
and sharp distinction. And, in the latter case similarity
of molecular parameters of bitumen from
metamorphic rock of STA basement with the oil from
fractured basement of the White Tiger field (on the
shelf of Southern Vietnam) is marked. For fractured
reservoirs of Western Siberia two models of oil and
gas formation have been offered: additional, actually
Paleozoic not found out yet the source of
hydrocarbons and above laying sediments [1].
Correlation of oils from the basement and
sediments of Lower Oligocene of White Tiger field has
shown similarity of their molecular parameters,
however, a greater degree of maturity of basement
oil.
In this connection, it is interesting to compare the
molecular structure of oils from the basements of two
different regions of the planet. For the analysis, the oil
from fractured rock of Palaeozoic era of Western
Siberia (WS): Maloichskoe (WS-ML), Archinskoe
(WS-Ar), Urmanskoe (WS-Urm) oilfields, oil from
weathering crust: Ostaninskoe oilfield (WS-Ost) and
the oil from Basement fractured granitoids of White
Tiger oilfield (WT) have been chosen.
Oils of WS and WT oilfields have similar physical
and chemical properties. They are light, highly waxy,
low in sulphur, with low content of asphaltenes and
naphthenes. They have Pr/Phy index, which is typical
of reducing-low oxidizing conditions of sedimentation
(1,1-2,1).
Source of initial material.
As a whole, in С27-C28-С29 (m/z=217) steranes С27
(41-58 %) prevails as compared with C28 and С29
steranes (except for oil from WS-Ar). It indicates that
these oils were formed in open marine and delta
source zones.
In all oils Oleanane is present: a compound
generated by angiosperms. Oleanane Index is useful
to distinguish lacustrine-algal oils from terrigenous
fluvial-deltaic oils in South-East Asia. This biomarker
is present only in oils generated from Late Cretaceous
deposits or younger age. Its presence in Palaeozoic
oils of Western Siberia has no explanation.
Parameters of maturity.
The maturity of the investigated samples oils is
evaluated by the following basic geochemical
parameters: Ts / (Ts+Tm), MPI-1. White Tiger field
oils have a higher degree of maturity due to higher
temperature (140-150 O С) in a formation as compared
with Western Siberia oils (80-90 0С).
As a whole, comparison of a wide set of biomarkers
in the oils of WT and WS fractured reservoirs show a
uniform distribution pattern of steranes, hopanes, the
saturated and aromatic hydrocarbons. These
parameters are similar or identical: that can confirm
the idea of belonging of these oils to a common
genetic family. This is possible, when an additional
deep oil-generating source has the same mechanism
and generates oil of similar composition.
[1] Goncharov I.V., et al. (2003) Genetic types of oils
from Tomsk region [abs], In Proceeding of 15 th
Int.<strong>Meeting</strong> Oil and Gas Chemistry, Tomsk, Russia,
p.10.
442

P-310
Implications of source rock and oil geochemistry to the
understanding of the petroleum systems of the Northern Red
Sea
Jennifer Scott 1 , John Guthrie 2 , Steve Crews 2 , Graeme Gordon 1 , Niall McCormack 1 , Dean
Griffin 1 , Laura Lawton 1 , Andy Pepper 2
1 Hess, London, United Kingdom, 2 Hess Corporation, Houston, United States of America
The integration of data from onshore samples, basin
modelling, and oil and source rock geochemistry, has
resulted in a better understanding of the petroleum
systems of the Northern Red Sea (NRS), Egypt.
The primary source rock in the NRS is thought to be
the pre-rift Dakhla Formation. These Maastrichtian
marls and calcareous shales outcrop onshore on the
western rift shoulders of the NRS. They were
probably deposited as part of the southerly marine
transgression of the Neo-Tethys during the mid-late
Cretaceous. There is also a lesser contribution from
the syn-rift source rocks of the Miocene Rudeis
Formation. Onshore pre-rift samples were analysed to
quantify organic carbon content, hydrogen index, and
geochemical characteristics. From these results, it
appears that the Maastrichtian Dakhla Formation is a
rich oil-prone source rock, analogous and genetically
related to the prolific late Campanian - early
Maastrichtian Brown Limestone in the Gulf of Suez.
Saturate biomarkers from oil shows in offshore
cuttings from NRS were used to identify the relative
contributions from pre-rift and syn-rift source rocks.
Figure 1 shows that oils sourced from the pre-rift
Dakhla/Brown Limestone are characterised by low
oleanane and high C29 (hopane) indices, and
isotopically light δ13C values (depleted in 13C),
indicating a more carbonate-rich source rock.
Meanwhile syn-rift sourced oils have higher oleanane
and are isotopically heavier (enriched in 13C).
Offshore NRS oil shows can be typed to both syn-rift
and pre-rift source rocks, indicating that the Dakhla is
both present and mature in the offshore NRS.
By comparing the geochemical characteristics of the
pre-rift from the NRS to a large number of oil and
source rock samples from the Gulf of Suez, source
rock facies and thermal maturity variations within the
pre-rift can be identified. Regional thermal maturity
modelling calibrated to well temperature data and
biomarker thermal maturity parameters (Figure 2) of
reservoir oils has improved the evaluation of thermal
maturity variations. Biomarkers and carbon isotopes
have been used to distinguish facies variations within
the pre-rift, and a potential proximal-distal marine
facies trend within the Brown Limestone/Dakhla has
been identified. This work has allowed for a better
understanding of the environment of deposition of
these world-class source rocks.
Figure 1: Carbon isotope parameters of oils and
source rocks (SR) from the Gulf of Suez and Northern
Red Sea.
Figure 2: Sterane maturity parameters used to
assess the relative thermal maturity of oils and source
rocks from the Gulf of Suez and Northern Red Sea.
Thank you to Hess and Premier for permission to
publish this work.
443

P-311
High water pressure induced combination reactions: a new
mechanistic route for post-oil bitumen formation in deep
petroleum basins
Clement Uguna 1 , Will Meredith 1 , Colin Snape 1 , Andrew Carr 2 , Gareth Harriman 3
1 University of Nottingham, Nottingham, United Kingdom, 2 Advanced Geochemical Systems Ltd,
Loughborough, United Kingdom, 3 GHGeochem Ltd, Liverpool, United Kingdom (corresponding
author:colin.snape@nottingham.ac.uk)
Asphaltenic tars and bitumens are common in both
carbonate and clastic reservoirs, occurring either as
droplets, grain coats lining the reservoir pores, or
entire layers. The presence of tars and bitumens can
reduce field productivity, cause significant problems
during drilling operations, and in basins such as
deepwater Gulf of Mexico can also add significantly to
the cost. Currently the formation mechanisms for
bitumens and tars include gas deasphalting,
biodegradation, oil cracking, thermochemical sulphate
reduction and oil mixing. However, in the past
decade numerous wells in the Gulf of Mexico have
encountered significant amounts of anomalous high
asphaltene (~70%) tars, apparently generated from
low maturity carbonate sourced bitumens and oils
with much lower asphaltene (~5%) contents.
However, none of the current formation mechanisms
can account for these tars. This paper provides
evidence from bound biomarker profiles for a Gulf of
Mexico bitumen and high pressure water hydrous
pyrolysis experiments at pressures up to 1000 bar
that bitumen formation arises from high pressure
mediated exothermic combination reactions.
Our extensive investigations using hydropyrolysis
(hypy) to characterise oil and bitumen asphaltenes, in
relation to fingerprinting heavily biodegraded oils,
have established that the bound biomarkers are
considerably less mature than their free counterparts
(Sonibare et al., 2009). Figure 1 compares the
sterane profies for the free and bound phases in a
Gulf of Mexico tar with the same maturity being
displayed and diasteranes present in both fractions.
The only explanation for this trend is the free steranes
in the precursor oil being incorporared into the
bitumen by pressure-induced combination reactions.
It has been established that water retards oil cracking
and this trend can potentially be magnified by high
pressure. Indeed, our preliminary work indicated that
when oil cracking is conducted in pressurised liquid
water, significant retardation occurs at 500 bar
compared to normal hydrous conditions at much
lower steam pressures. The investigation has been
extended to 1000 bar and it has been found that the
disappearance of light hydrocarbons (

P-312
Molecular stable carbon isotopic composition of light
hydrocarbons as a method to decipher hydrocarbon generation,
accumulation and secondary alteration in superimposed
petroliferous basin: a case study from Tarim basin, NW China
Yongge Sun 1 , Qilin Xiao 2 , Aizhu Jiang 2 , Chupeng Yang 2
1 Department of Earth Science, Zhejiang University, Hangzhou 310027, China, 2 State key laboratory of
Organic geochemistry, Guangzhou Institute of geochemistry, CAS, Guangzhou 510640, China
(corresponding author:ygsun@zju.edu.cn)
Light hydrocarbons (LHs, C5-C10), as one of the most
abundant constituents in crude oil, have received
special consideration in petroleum geochemistry for
long history. Theoretically, LHs from kerogen are
directly degraded from macromolecular network and
will migrate out of the source rock via generation and
expulsion once hydrocarbon concentration reaches
up to the saturated threshold of rock, whereas
gasoline hydrocarbons from oil-cracking are formed
via C-C bond cleavage of high molecular weight
compounds, cyclization and aromatization, and
involved an isotopic kinetic fractionation, although
they will be destroyed under very high temperature.
Different pathways of LHs generation led us to
construct new parameters to characterize processes
involved in oil and gas generation, accumulation and
destruction, using molecular and isotopic
measurements.
Compared to the measurements on normal alkanes
and biomarkers in crude oils, individual LHs have
analytical constraints because many compounds in
this range have high vapor pressures and low boiling
points, and tend to be the gas phase at room
temperature. Although care can be taken to minimize
the evaporation losses during oil sample collection,
transportation, storage, and preparation, the success
application of molecular and individual δ 13 C values of
LHs requires a full evaluation induced by evaporation
under natural conditions, especially on the magnitude
and direction determination during the progressively
vaporized losses. Here, a vaporization experiment on
crude oil was conduced before applications. The
results showed that most of molecular parameters
associated with C7 hydrocarbons are influenced by
evaporation process except interpretive schemes
such as P2 versus N2/P3 and the invariant ratio
developed by Mango. It was also found that stable
carbon isotopic fractionation effects of LHs due to
vaporization were strongly compound classdependant,
and within the analytical error, δ 13 C
values of cycloalkanes remained similar to that of
fresh sample, and can be used with confidence for
petroleum geochemistry.
Taking the theoretical consideration and laboratoryverified
parameters, molecular stable carbon isotopic
Composition of LHs was used to decipher
hydrocarbon generation, accumulation and secondary
alteration in Tarim basin, NW China, a typical
superimposed petroliferous basin with multiple source
kitchens, multiple phase filling histories, and severely
secondary in-reservoir alterations. Crude oils from
Paleozoic petroleum system in Central Tarim Basin
were studied. Combined with the δ 13 C values of nalkanes
and biomarker assemblages, it was found
that, (1) oil reservoirs from the Central Uplift of
Tazhong experienced multiple periods of oil
generation, migration, accumulation and in-reservoir
cracking as indicated by maturity range of crude oil;
(2) oil and gas from reservoirs in the Slope-break Belt
of No.1 and the Structural Belt of Tazhong 10 were
mainly derived from deep buried in-reservoir oil
cracking as revealed by distributions of
monoaromatics and δ 13 C compositions of
methylcyclohexane (Fig.1).
Fig.1 The distribution of monoaromatics V.S. δ 13 C of
methylcyclohexane in crude oils from The Central
Uplift of Tazhong (▲), the Structural Belt of Tazhong
10 (□) and the Slope-break belt of No.1 (×) in the
central Tarim basin.
445

P-313
Calibration of absolute maturity for terrestrial-sourced oils and
gas condensates using PLS regression
Richard Sykes, Klaus-Gerhard Zink
GNS Science, Lower Hutt, New Zealand (corresponding author:r.sykes@gns.cri.nz)
The absolute thermal maturity of petroleum fluids can
be used to help constrain the depth and timing of
expulsion from source rocks and to clarify genetic
relationships. For example:
� Do suspected oil shows represent indigenous or
migrated oil?
� Are various oils from the same or sequential
charges?
� Did gas condensates form via phase separation
from oils or directly from source rocks at higher
maturity?
Absolute maturities are usually determined by
calibrating the fluids‘ molecular maturity parameters
against equivalent parameters for bitumens extracted
from source rocks of known maturity. Use of individual
parameters can be problematic if the selected
parameters reach equilibrium partway through the oil
window or are adversely affected by variation in
source organofacies. In this paper, we present and
apply a method for predicting absolute maturities of
terrestrial-sourced oils and gas condensates based
on Partial Least Squares (PLS) regression. The use
of factor-based regression allows multiple maturity
parameters to be used collectively, thus minimising
potential errors associated with individual parameters.
Initially, 28 molecular maturity parameters were
determined for 129 New Zealand coaly source rocks
with known Suggate coal rank [Rank(Sr)] and Tmax
values from throughout the oil window. Then, using
bivariate correlations, Principal Component Analysis
and PLS regression, two PLS regression models were
developed for prediction of Rank(Sr) and Tmax. The
first, optimised for Rank(Sr), uses a training set of 58
source rocks and 5 methylnaphthalene maturity
parameters; the second, optimised for Tmax, uses 52
source rocks, the same 5 methylnaphthalene
parameters and 3 methylphenanthrene parameters.
Internal cross-validation shows that the models
predict known Rank(Sr) and Tmax values with standard
errors of 0.40 rank units and 2.7°C, respectively,
which are comparable to those of measured values.
Application of the PLS models to a set of 132 New
Zealand terrestrial-sourced oils and gas condensates
predicts maturity values that are largely consistent
with Rank(Sr) and Tmax limits for the oil and gas
windows determined independently from source rock
pyrolysis studies (Fig. 1) [1, 2]. One notable exception
is the Galleon-1 condensate, which is thought to have
been generated via rapid, intrusion-related heating.
Tmax (°C)
475
470
465
460
455
450
445
440
435
430
onset oil expulsion for coals
near top of NZ Coal Band
Oils
Gas conds
Oil shows
onset oil expulsion for coals
near base of NZ Coal Band
Ga1
~Ro 0.90% ~Ro 1.15%
onset gas generation
end of oil window
~Ro 1.6%
11 12 13 14 15 16 17
Rank(S r)
Fig. 1. Calibrated Rank(Sr) and Tmax values for New
Zealand petroleum fluids. Ga1 = Galleon-1.
The gas condensates are overall more mature than
the oils, but with significant overlap in their maturity
ranges. Variations in maturity between petroleum
fluids within individual families and fields provide
useful insights relevant to understanding migration
pathways, charge histories and possible causes of
well failure.
[1] Sykes, R., Snowdon, L.R. (2002) Org.
Geochem. 33, 1441–1455.
[2] Sykes, R., Johansen, P.E. (2007)
Proceedings, 23rd IMOG, Torquay, P226-WE.
446

P-314
Chemometric analysis of oil-oil and oil-source rock correlations
in New Zealand basins
Richard Sykes, Klaus-Gerhard Zink
GNS Science, Lower Hutt, New Zealand (corresponding author:r.sykes@gns.cri.nz)
This paper presents a chemometric-based study of
oil-oil and oil-source rock correlations in Taranaki and
other New Zealand basins. Using Hierarchical Cluster
and Principal Component Analysis and a preferred set
of 14 source-related biomarker and carbon isotope
parameters, correlations are established between 134
oils and gas condensates and 95 source rocks of
known age and organofacies. The selected biomarker
parameters provide effective characterisation of the
angiosperm, gymnosperm, total higher plant, and
marine organic matter inputs to the respective source
rocks. Moreover, the parameters are not unduly
affected by source rock maturity, low–moderate
biodegradation (up to level 3–4) or petroleum phase
fractionation, and thus appear to provide generally
robust correlations of the oils and gas condensates.
The correlations herein refine and expand previous
identifications of oil families and provide improved
characterisation of source rocks. Five oil (and gas
condensate) tribes and 13 families are identified:
Tribe 1: Late Cretaceous, terrestrial source rocks
with high gymnosperm inputs:
� Family 11: Offshore Taranaki (Tui and Maui
fields, Taranui-1, Maui-4) and Grey Valley Basin
(Niagara-1)
� Family 12: Offshore Taranaki (Pukeko-1) and
Grey Valley Basin (Petroleum Creek-3 and
Kotuku, Mt Davy Mine and Spark & Party Mine
seeps)
� Family 13: Offshore Taranaki (Maari Field)
Tribe 2: Paleocene–Eocene, terrestrial source rocks,
intermediate gymnosperm and angiosperm inputs:
� Family 21: On- and offshore Taranaki, Manaia
Trend area (Kupe and Kapuni fields, Toru-1)
� Family 22: Onshore Taranaki Peninsula (Ngatoro
and Goldie fields)
Tribe 3: Eocene, terrestrial source rocks with high
angiosperm inputs:
� Family 31: Onshore Taranaki Peninsula,
southern Tarata Thrust area (Waihapa, Ngaere,
Cardiff, Stratford, Ahuroa, Cheal and Wingrove
fields, Huinga-1B, Rimu-B1, Kauri-A2 and -F1)
� Family 32: Onshore Taranaki Peninsula, northern
Tarata Thrust area (McKee, Tariki, Kahili and
Mangahewa (Zone B) fields)
� Family 33: On- and offshore northern Taranaki
Peninsula (Moturoa, Pohokura and Mangahewa
fields, Pukearuhe-1) and Waihapa-1A.
Tribe 4: Late Cretaceous–Eocene, marine and
coastal facies source rocks with relatively high marine
organic matter inputs:
� Family 41: Offshore northern Taranaki (Pluto-1)
� Family 42: Offshore northern Taranaki (Kora
Field)
� Family 43: Onshore northern and southern East
Coast Basin (Rotokautuku, Totangi, Waitangi,
Isolation Creek and Kaikoura seeps)
Tribe 5: Jurassic–mid Cretaceous?, terrestrial source
rocks characterised by relatively low total higher plant
input:
� Family 51: On- and offshore southern Taranaki
(Rimu and Kauri fields), offshore northern
Taranaki (Te Ranga-1)
� Family 52: On- and offshore southern Taranaki
(Kauri Field)
Oil families within the essentially terrestrial-sourced
tribes (1–3, 5) are distinguished primarily by variations
in the levels of synsedimentary marine influence,
anoxicity and/or angiosperm input within the coalbearing
sequences of the respective kitchen areas.
Within Taranaki Basin, the oil family groupings tend to
be geographically constrained and help to identify
source kitchens and migration pathways. The Kupe
and Kapuni fluids, for example, cannot be
distinguished by field, strongly suggesting derivation
from a common source kitchen.
447

P-315
Organic Geochemistry of Lower Proterozoic of Kodar-Udokan
trough (Aldan shield)
Irina Timoshina, Elena Fursenko
Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation (corresponding
author:TimoshinaID@ipgg.nsc.ru)
Within the bounds of the Kodar-Udokan trough in
the Aldan shield, the studied Lower Proterozoic (1.86
Ga) organic matter (OM) contains Сorg 0.03-0.05%
and chloroform-extractable bitumens 0.0009-
0.0015%. OM is overmature, judging from the
isotopically heavy carbon of the insoluble OM (δ 13 С
value −29.5…−27.0‰) and low concentrations of
chloroform-extractable bitumens, represented by
mainly resins (64.0-83.6%).
Saturated fraction of chloroform-extractable
bitumens (13.7-26.9%) was analyzed with a gas
chromatography / mass spectrometry method.
The peaks in normal alkanes pertain to nC18-20;
phytane is predominating (Pr/Ph

P-316
The occurrence of crude oil in the coal-bearing strata of Hulin
Basin and its hydrocarbon potential analysis, north-eastern
China
Xue Wang, Bo Chi, Wei Fang, Huasen Zeng, Zhongliang Dong, Xiaochang Zhang
Exploration and Development Research Institute, PetroChina Daqing Oilfield Company, Da qing, China
(corresponding author:xuewang@petrochina.com.cn)
Oil contribution from coal and coaly shale is still
controversial. Gippsland oilfield in Australia and
Mahakam oilfield in Indonesia are the earlier places to
find oil from coaly strata; and oil in Turpan basin that
is in western China is thought to have been generated
from lower Jurassic coal-bearing formations. In 2009,
Paleocene coal-bearing strata in Hulin Basin that is in
north-eastern China was first to produce oil. Multiple
geochemical indices were integrated by this study to
characterize the crude oil from Hulin Basin and to
estimate the hydrocarbon potential.
Hulin Basin with an area of 9150km 2 lies in
Heilongjiang province, north-eastern China and to the
east of Songliao Basin. Hulin Basin was over upon
Paleozoic metamorphic rock and Precambrian
crystalline basement. Hulin basin is widely covered by
Mesozoic-Cenozoic strata, including upper Jurassic
Peide formation, Paleogene Hulin formation, Neogene
Fujin and Daotai formations, and of which Hulin
formation spreads widely in the basin and is the main
exploration target. At the base of Hulin formation,
rocks are sandstones, siltstones, and grey-dark
mudstones with tens of coal interbeds which contain
plenty of plant fossils. In the mid of Hulin formation
are thick dark mudstones and in the top are
interbeded grey-green mudstones and argillaceous
siltstones with some coal beds. Hulin basin has
experienced early extension and then depression
expansion followed by contraction phase and the
distribution of Mesozoic-Cenozoic strata is controlled
by those extensional faults. Hulin Basin has been
explored since 1980s and well Hu-1 as the only oilproducing
well of all the six drilled wells was
completed early in 2009. Hulin formation in well Hu-1
produces 0.058 tons of oil daily and is considered to
be the breakpoint in its exploration history.
Crude oil in Hu-1 is black solid at atmospheric
temperature with density of 0.85g/cm 3 , wax content of
34.6%, viscosity of 44.4mPa.s, and molecular weight
of 330. As shown in figure 1, the crude oil of Hu-1 is
characterized by (1) high saturate content at 74%, (2)
high Pr (pristane) content with Pr/Ph ratio (pristane
vs. phytane) at 11.39 and Pr/nC17 at 4.6, (3) low
content of Gammacerane, (4) low content of tricyclic
terpanes with the presence of tetracyclic terpanes, (5)
prevailing content of C29 hopanes with low content of
Ts and high content of C29 steranes with abundant C29
diasteranes, (6) content of 1-methylphenanthrene is
twice that of other methylphenanthrenes, (7)
abundant retene, and (8) stable carbon isotope of
single compound in saturated hydrocarbons ranges -
27.6% ~ -30.14% and decreases with carbon number
while δ 13 C29 is the lightest. These geochemical
characteristics indicate that the source rock of crude
oil was deposited in fresh water and the crude oil is
characterized Prby
higher-plant input.
TIC
m/z191
m/z217
C 30 hopane
C 29 sterane
Fig.1 mass fragmentograms for oil sample
of Well Hu-1
The source rock of Hulin Basin is thought to be
Paleogene Hulin formation, which contains thick
mudstones and coal beds. Take well Hu-1 as
example, the thickness of mudstone is 729.7 meters
while that of coal is 184.8 meters. The source rock is
organic-rich with TOC (total organic carbon) of 68% of
samples higher than 2%. The kerogen type is
dominated by II2-III while hydrogen-rich macerals
mainly contain sporinite, cutinite, suberinite, and
resinite. The distribution of biomarker and componentspecific
stable carbon isotope is close to that of crude
oil. Based on the source rock distribution and thermal
history, the oil potential is assessed to be 0.84×10 8
tons and the gas is about 60 ×10 8 cubic meters.
The discovery of crude oil in Hulin Basin adds
another proof that coaly formation can generate liquid
petroleum. The area of Hulin Basin is small while the
449

P-317
Laboratory simulation of vertical hydrocarbon microseepage
from the reservior to the surface using a 3-D model
Guojian Wang 1,2 , Tongjing Cheng 1,2 , Ming Fan 1,2 , Li Lu 1,2
1 Sinopec Research Institute of Petroleum Exploration and Production, Beijing, China, 2 Wuxi Institute of
Petroleum Geology, Sinopec Research Institute of Petroleum Exploration and Production, Wuxi, China
(corresponding author:kingdomjian@126.com)
Surface Geochemistry Exploration (SGE) based on
hydrocarbon microseepage theory is still called
‗unconventional‘ and not widely accepted. One of the
primary impediments to acceptance of SGE methods
in the petroleum industry has been the lack of
experimental verification of the transport of gases
(microseepage) from an oil and/or gas reservoir to the
surface without significant dilution and dispersion.
Understanding of the processes and mechanisms of
hydrocarbon microseepage is thought to result in
acceptance of SGE and improving its applying effect.
it is necessary to conduct laboratory simulation of
vertical hydrocarbon microseepage.
Based on a conceptual model of hydrocarbon
microseepage, an experimental 3-D model was
constructed, which includes a point gas source, an
injecting water system, a temperature controlling
system, and a 3-D sampling sites. A cuboid which is a
mixture of cement, quartz sand, and water is used as
simulated caprock and its overlying strata. The cuboid
is 100 cm long, 100 cm wide and 120 cm high. The
soil profile on the top of model is 30 cm thick. Gas
composition of the point gas source used in the
experiments is composed of light hydrocarbons
according to the composition of the real wet gas in
one gas accumulation in a petroliferous basin in
China, which includes 89% methane, 4.4% ethane,
2.3% propane, 0.66% i-butane, 1.04% n-butane,
0.096% i-pentane, 0.104% n-pentane, 2.4% Nitrogen.
The 13 C value of methane is -33.68‰, typical of
thermogenic gas. Controlling temperature system at
the bottom of the model can simulate temperature
field. Injecting water system at the bottom of the
model can infiltrate through the cuboid and keep its
pores wet. The porosity and permeability of the
simulated caprock is in accordance with that of some
mudstone caprock of natural gas. The soil profile is
similar to Quaternary sediments.
The experiments were operated at a room
temperature of 25ºC. The bottom temperature of the
cuboid was held at 65ºC, similar to the temperature at
a depth of about 1330m. A stable temperature
gradient was formed from bottom to top in the
simulated rock cuboid after a week of temperature
control. The pressure of the point-gas source was
controlled at 0.2 MPa (~2 atmospheres). Water was
injected under 0.2 MPa pressure into the bottom of
simulated rock cuboid. The natural gas composition
was injected from the point source for a period of 102
days. Hydrocarbon concentrations at each sampling
site were then determined in order to explore the
dynamics of hydrocarbon microseepage.
Results of our experiment study indicate that on
the path of hydrocarbon microseepage, the
distribution of hydrocarbon concentration is fanshaped;
differential adsorption of alkanes by the
simulated caprock and its overlying strata results in
the occurrence of a chromatographic effect, which the
ratio C1/C2 increased gradually from base to top over
point gas source, but this is not the case for vertical
detecting lines far from the point gas source. Different
migrating patterns within simulated caprock are
shown by the ratio of i-butane to n-butane (iC4/nC4),
following diffusion and infiltration (buoyant)
mechanisms. An upwelling gas flow in the form of a
plume was found during hydrocarbon microseepage.
A notable question is that the 13 C value of methane in
the sampling site near point gas source became -
15.94‰. It may be indicated an aerobic environment
where 12 C is preferentially oxidized by aerobic
bacteria.
The dispersive halo of microseeping hydrocarbons in
the subsurface is adequately discribed with the 3-D
model used in this simulation experiment. The
features and pathways of hydrocarbon microseepage
with depth that connect the source with the surface,
and the possible formation process of anomalies in
SGE are revealed. ―Vapor infiltration along fracture
driven by pressure‖ has been proposed as the
possible main formation mechanism of surface
geochemical anomaly. Hydrocarbon micro-seep
always along the predominant pathways, such as
faults, fractures, micro-fractures. The concentration
location of active state hydrocarbon microseepage is
dominated by the predominant pathways.
450

P-318
Kinetic study of primary cracking gases from a marine kerogen
by stepwise open system and its implications
Yunpeng Wang 1 , Hongjun Wang 2 , Changyi Zhao 2 , Jinzhong Liu 1 , Jialan Lu 1
1 SKLOG, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China,
2 Research Institute of Petroleum Exploration and Development, PetroChina, Beijing, China (corresponding
author:wangyp@gig.ac.cn)
Marine hydrocarbon gases can be generated from
kerogen itselt as well as its product oil or liquid
hydrcargons. The former is primany cracking gases
generated from the cracking of kerogen, and the latter
is secondary gases generated from the caracking of
oil. The widely used simulation apparatus in
laboratory is pure closed or open system. In closed
system, gas yields in higher temperatures are often
the mixture of primary and secondary gases, while in
open system, the gas yileds measured are always an
instanuous one which is proved very low and hard to
be measured. In this study, we developed a stepwise
open system, which is composed of a pyrolysis cavity
and computer-cotrolled multi-traps in vacuum tanks.
Kerogen is heated to the pre-set temperatue and all
the gases generated in the temperature range from
beginning to this temperature point are collected in a
tank. Gas chemical composition and carbon isotopes
will be measured by a on-line GC and GC-IRMS
nennected to the tanks using a multi-way valve.
Because the heating caivty is connected to a vacuum
tank, the yields will expeled to the tank without
retaining. Due to the gases collected in each tank is a
cumulative gases from the room temperature to the
pre-set temperature point, the result is a cumulative
primary gases rather than a instanuous one. This
apparatus provides an ideal tool to study the primary
cracking gases.
The sample we used is a typical marine kerogen
extracted from a Protezoic shale from Zhangjiakou,
north of China, which have been studied in closed
system and the results have been reported before. It
can be compared with the reults of this study.
The generation process of gases look similar with
those in closed system, but the gas yields are quite
low. The maximum yiled of C1 is about one third of
that in closed system, and the maximum yiled of C2,
C3 and C4+C5 in this study are more lower than those
in closed system.
The kinetc parameters of gas generation were
calculated which are 50-72 kcal/mol of activation
energy with a frequency factor of 6.5х10 15 s -1 for C1,
44-61 kcal/mol of activation energy with a frequency
factor of 2.63х10 13 s -1 for C2, 38-49 kcal/mol of
activation energy with a frequency factor of 2.56х10 11
s -1 for C3, and 38-51 kcal/mol of activation energy
with a frequency factor of 6.5х10 15 s -1 for C4+C5,
respectively. In general, the values of activation
ennergy are relatively lower than those in closed
system, especially for the heavy gases of C2, C3 and
C4+5.
The kinetic parameters were used to extropolate our
resluts to geological condittions of 5 o C/My. It is clear
that C4+5 and C3 gases start their generation around
105 o C (0.4%Ro) and reach 90% conversion at around
150 o C (1.1%Ro), while C2 gases begin its generation
at 110 o C(0.5%Ro) and reach 90% conversion at
around 160 o C (1.5%Ro%). Although C1 gas begins its
generation at around 120 o C, it reaches its fast
generation process only after 150 o C, and reaches its
90% conversion at around 220 o C (2.5%Ro). The
complete conversion of C1 gas will reach 245 o C
(3.4%Ro). These results suggest that primary heavy
gases of C2-C5 start at very early maturities and
lower temperatures, while primary C1 gas is mainly
generated in later stages greater than 1.5%Ro, which
is similar to the secondary C1 gas in closed system.
In the diagram of ln(C1/C2)-ln(C2/C3), primary gases
are mainly plotted in the area of lower C2/C3 and
C1/C2. Comparing with the gases in closed system,
primary gases show less fractionation of defferent
molecular compostions. Less C2/C3 and C1/C2
suggest that the generation of primary gases is mainly
from the cracking of kerogen rather than the cracking
of oil. In the diagram of C2/C3-δ 13 C2-C3, the primary
gases are also show less fractionation of carbon
isotopes, while gases from closed system show both
greater compositional and isotopic fractionation. It
also suggests that gases from the closed system are
a mixture of primary and secondary ones.
Acknowledgments
China Giant S&T Programs (2011ZX05008-002-13),
China 973 program (2007CB209501) and NSFC
project (40872091) are thanked for the support.
451

P-319
The study of C1-C3 gas generation behavior of kerogen by
closed-system thermal simulation and Py-GC
Yuhong Liao, Xunyong Zhu, Ansong Geng, Yinhua Pan
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China (corresponding
author:liaoyh@gig.ac.cn)
In closed thermal simulation system, the C1 directly
generated by kerogen was mixed with C1 generated
by oil cracking. It is hard to eliminate the actual gas
generation behavior of kerogen. In this research,
kerogen was heated at two rates, 20ºC/h and 2 ºC /h
in a closed system from 350 ºC to 600 ºC. The
volume of C1, C2 and C3 was measured and weight
normalized. Conversions of C1, C2 and C3 were
calculated based on gas generated (conversion in
Fig. 1(a)). Then the reacted kerogens were
pyrolyzated by Py-GC at 800 ºC for 10s to study the
residual C1, C2 and C3 potential of kerogen. The real
conversion rates of C1, C2 and C3 of kerogen were
calculated based on residual rates of conversion
(conversion in Fig. 1(b)). The thermal maturities of
kerogen were calculated based on Easy Ro
(Sweeney et al., 2000). The conversions measured
were plotted against calculated Ro.
The Py-GC results indicated that more than 90% of
C1, C2 and C3 potentials of kerogen were
progressively consumed up before Ro% reach 1.3.
While weight-normalized volume of C1, C2 and C3
generated in closed system simulation suggest that
the generation of C1, C2 and C3 extends to much
higher maturity range. The generation of C1 doesn‘t
reach its end though Ro% reaches 3.0. So there
exists dramatically difference in gas generation
behavior between closed system and open system
thermal simulation. It is due to significant
hydrocarbon secondary cracking in closed system
thermal simulation. Kerogen first releases
hydrocarbons with higher molecule weight during
thermal maturation, then these hydrocarbons crack
into smaller ones step by step and the final products
are methane and pyrobitumen. Thus the generation of
methane can last very broad maturity range. In open
system thermal simulation, the alkyl side chains are
released from structure of kerogen as volatile
molecules and blown away, and there is no
secondary cracking of hydrocarbons during kerogen
thermal maturation. Most C1 can only be generated
by the primary cracking.
The experimental results also indicate that the
distribution of activation energy (E) based on closed
system pyrolysi are much higher than the distribution
of activation energy at identical frequency factor (A =
1.0E+14). The average activation energy of C1
generation is 62.53 kcal/mol in closed system
pyrolysis, while average activation energy of C1
generation is 52.75 kcal/mol. In open system
pyrolysis, average activation energy of C2 generation
is 52.33 kcal/mol, and average activation energy of
C3 generation is 49.78 kcal/mol. Average activation
energy of C3 is much lower than C1. It indicated that
C3 alkyl side chains are much easier to be broken
apart from kerogen structure. It is consistent with
common accepted rules of hydrocarbon generation.
Fig. 1 (a) Conversion of C1, C2 and C3 in closed system
simulation based on volume of gas generated; (b) Real
conversion of C1, C2 and C3 of kerogen based on residual
rate of conversion measured by Py-GC
452

P-320
Geochemical evaluation of sources rocks from Ain Regada
region, Northern Algeria
Aziez Mebarka
Sonatrach, Exploration Division, Boumerdes, Algeria (corresponding author:anissaz2001@yahoo.fr)
The present study focuses on the
geochemical evaluation as well as the molecular
organic geochemistry, especially biological marker
distributions of sources rocks in Ain Regada region,
northern Algeria.
The study area is situated in northern Algeria
and bounded to the east by the Tunisian border, to
the north by the high plains and to the south by the
Sahara platform. This area contains several gas and
oil shows.
This paper reports a study of a geochemical
evaluation involving 50 outcrop samples from
Coniacian, Paleocene, Cenomanian/Santonian and
Albian sediments.
From the bulk data of these outcrop samples,
there are some excellent Cenomanian/Coniacian,
Paleocene source rocks.
Based on biological marker distributions,
these source rocks appear to be of marine input and
depositional environment. They are constituted by a
combination of algal and amorphous material. Based
on maturity parameters, these outcrop rock samples
are mature and probably have generated already
liquid hydrocarbons in the area of study.
The whole variations recovered depend on
the nature and maturity of the source rocks and they
are the results of thermal and geodynamic activities
happened in northern Algeria.
Key-words: Northern Algeria, Cenomanian,
Coniacian, Paleocene, outcrops, biological markers,
source rocks,
453

P-321
Hydrocarbon potential of Maikopian source rocks within Black
Sea petroleum basin
Dmitry Nadezhkin
Moscow State University, Moscow, Russian Federation (corresponding author:dvnadezhkin@gmail.com)
Nowadays there is huge interest in the deep-sea
part of the Black Sea region. Multiple direct features
of petroleum potential in the area such as oil and gas
seepages, active mud volcanoes, gas hydrates have
been detected.
Samples were collected during several scientific
cruises in the Black Sea within Training Trough
Research program. Rock clasts derived from mud
breccia and oil from deep sea mud volcanoes were
analyzed. Additionally collection of Maikopian
(Oligocene – Lower Miocene) oil and rock samples
from onshore drilled wells and outcrops was chosen
for comparison (fig. 1).
Fig.1. Scheme of sampling for geochemical studies.
Age determination shows that most of
semilithified rock clasts are from upper part of
Maikopian formation.
The total organic carbon content (TOC) in rock
clasts based on Rock-Eval pyrolysis varies from 0.2 to
9.37%. The hydrocarbon potential (S1+S2) is 0.25-18
mg/g that belongs to a source rock with a moderate
and good oil/gas potential. Samples demonstrated
relatively low maturity based on pyrolysis data
(maximum temperature (Tmax) less than 429 o ) and
biomarker analysis. Nevertheless samples of oil were
found in seabed sediments.
Since Maikopian sediment thickness in the
Tuapse, Sorokin and East Black Sea depressions
around 5-6 km we expect existence of active oil
generation in the middle and lower parts of formation.
As a result the question arises about the
potential of these parts of Maikopian formation.
Samples from adjacent land were analyzed to
evaluate oil/gas potential due to the lack of
information and lack of drilling in the deep part of the
Black Sea. Some of them were collected within Sochi-
Adler depression which is a continuation of the
Tuapse Trough onshore [1].
TOC in these samples varies from 0.3 to 4.06%.
Petroleum potential (S1 + S2) ranges from 0.17 to
18.38 mg HC / g rock. Thus potential of middle and
lower parts of Maikopian formation varies from low to
very high. Also values of potential increased up to
18.38 mg HC / g rock in the lower part of Maikopian
sediments within the Sochi-Adler depression and
Abkhazia region.
Finally studies show that the upper part of
Maikopian formation has enough potential to generate
hydrocarbons but it is immature.
The onshore data convincingly prove presence
of high oil/gas potential in the lower and middle part of
the Maikopian formation.
Since Maikopian sediment thickness within
depressions is around 5-6 km we expect existence of
active oil generation in the middle and lower parts of
formation.
References
[1] Afanasenkov A.P., Nikishin A.M, Obukhov A.N.
East Black Sea Basin: geological structure and hydrocarbon
potential. Moscow, 2007.
454

P-322
Сarbonaceous rocks of the Lower and Middle Cambrian Inican
Formation in the southeastern Siberian platform
Igor Korovnikov, Tatyana Parfenova, Victorya Eder
Trofimuk Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation
(corresponding author:parfenovatm@ipgg.nsc.ru)
In the north and east of the Siberian Platform, the
organic-rich Cambrian Kuonamka complex
(Kuonamka, Sinskaya, Shumnaya and Sekten
Fomations), a potential oil-generating sequence, has
been established [3 and oth.]. The goal of
investigation is to specify the age and composition of
carbonaceous rocks and the conditions of their
formation in the Lena-Amga interfluve (southeast of
the Siberian Platform). A collection of samples from
well Khotochu-7 from the interval of 388-309 m has
been examined. It is known the Lena-Amga interfluve
borders on the Sinskaya Formation in the west and on
the Inikan Formation in the east. Paleontologic
observations show that carbonaceous rocks of well
Khotochu-7 contain trilobite imprints, characterizing
the older zones as compared to the reported for the
Sinskaya Formation. The rocks of the upper part of
the section, containing the fauna of the Tomagnostus
fissus zone and generally characterizing Inikan
carbonaceous deposits, are composed of light
limestones depleted in OM. The results of lithologic
and geochemical examination of rocks and OM
allowed separation of sample collection into two
groups [5]. The first group includes predominantly
low-carbonaceous and carbonaceous limestones
silicites of the lower part of the section (354-388 m)
with TOC from 0.2 to 7.5 % (in average 3.48 %). The
carbonate material mainly consists of calcite. Clays
generally account for less than 5 %. The βα/(αα+ββ)
ratio of cholestane, methylcholestane and
ethylcholestane is 0.09-0.19. The average content of
С23 tricyclane is higher than 30 % of total tricyclanes.
The concentration of С29 norhopane is higher than
that of С30 hopane. The average ratio
(steranes+pregnanes)/terpanes is 0.1 (!). Only in 4
samples from 13, homohopane content decreases in
the series С31>C32>C33>C34>C35, and С35/С34 is 0.8-
09. Usually, С35/С34 is higher than 1. The second
group includes low-carbonaceous rocks, generally of
mixed siliceous-dolomitic composition, less
commonly, silicites and limestones of the upper part
of the section (309-346 м). The average content of
TOC in them is 1.6 %, dolomite– 35-40 %, and clays
– 5-15 %. The βα/(αα+ββ) ratio of cholestane,
methylcholestane and ethylcholestane is 0.22-0.38.
The average content of С23 tricyclane is lower than
30 %. The С29/С30 ratio is less than 1. The average
ratio of (steranes+pregnanes)/terpanes is 0.4. The
С35/С34 ratio is less than 1.
Saturated HCs of two groups show common features:
generally, maximum concentrations of n-С16-n-С19
alkanes; absence of 12- and 13-monomethylalkanes;
high (more than 30 %) concentrations of tricyclanes;
tricyclane index 2*∑(С19-20)/∑(С23-26) is less than 1,
gammacerane content accounts for less than 1 %;
ethylcholestane is predominant (more than 40-50 %).
These features are characteristic of OM from the
Kuonamka Formation [1; 2; 4 and oth.].
Conclusion. Paleonthological, lithologic and
geochemical studies have shown that the section of
OM-enriched rocks from Lower and Middle Cambrian
deposits of the Lena-Amga interfluve is transitional
between the known sections of the Sinskaya and
Inikan Formations and has two-member structure.
Carbonaceous sediments accumulated in the marine
basin with normal water salinity. The rocks of the first
group formed under sharply reducing conditions and
the rocks of the second group – in normal reducing
ones. OM is likely to be derived mainly from algae
and bacteria. The difference in terpane and sterane
ratios indicates that the share of bacterial matter is
four times as much as in carbonaceous silicites and
carbonate rocks as compared to that of their overlying
low-carbonaceous rocks. It is likely that either the
contribution of prokaryotes into the composition of
microbiocenoses was higher, or the primary OM in
sediments of the lower part of the section was
essentially transformed by bacteria.
References
[1] Kashirtsev V.A. Organic geochemistry of
naphthides in the east of the Siberian Platform. Yakutsk:
Yakutsk Affiliate of SB RAS Publishing House, 2003, 159 p.
[2] Kontorovich A.E., et al. // DAN. 2005. V. 402. № 5.
[3] Kontorovich A.E., Savitsky V.Е. On
paleogeography of the Siberian Platform in the Early and
Middle Cambrian // Problems of lithology and
paleogeography of Siberia. SNIIGGiMS. Novosibirsk. 1970.
[4] Parfenova T.M., et al. // Rus. Geol. and Geophys.
2004. V. 45. № 7.
[5] Parfenova T.M., et al. // Geologiya nefti i gaza.
2009. № 1. P. 87-91.
455

P-323
Paleoenvironment significance of geochemical characteristics of
the carboniferous source rocks in eastern part of the Junggar
Basin
Wen Qi, Jianguo Pan, Peng Wang, Kunjun Tan
Research Institute of Petroleum Exploration and Development -Northwest,Petrochina China, Lanzhou,
China (corresponding author:morababy83@126.com)
Carboniferous source rocks of Junggar Basin include
dark shale, coal, tuff and sedimentary tuff.And the
tuffs, tuffites are products of volcanic events in the
area. This study learns the characteristics of organic
geochemistry and trace element by analysing
samples of logging core and outcrop rock. Then,
combined with fossils trait of the Carboniferous strata
to probe the relationship between the environment
and source rocks geochemistry characteristics in the
depositional Basin.
The organic matter of the research area is mainly type
Ⅲ and Ⅱ2. In general , the majority macera of the
upper and lower Carboniferous source rocks is
vitrinite (Upper Carboniferous is 33.2%;Lower
Carboniferous is 65.6%), followed by inertinite,which
shows that the matter influx is dominated terrestrial
higher plants. However , there are differences in
different secondary structural units. By the relative
content of macerals and steranes, the sendimentay
environment of Baijiahai salient and Beisantai salient
are fresh water lacustrine environment or river delta
sediments; Wucaiwan sag and Dajing present
characteristics of transitional facies. And also,
evidence from the Isoprenoid hydrocarbons reflects
that the depositional environment transits from
Oxidizing reduction environment to oxidation
cinditions ,indicating that Carboniferous strata of east
of the Junggar Basin is transitional facies.
For trace elements, the following four element ratios:
Sr/Ba , B/Ga , V/(V+Ni) andCa/(Ca+Fe),can
effectively reflect the Carboniferous
Paleoenvironment . Baijiahai saline and Baijiahai
salient are semi-reuction fresh water facies.
Wucaiwan Sag and Dajing area are reduced
tranzitional facies. Dinan salient are freshwater and
brackish water lacustrine facies deposits. Huoshen1
well are strong reducing offshore sediments.
Fossils evidence indicates that in the late Late
Carboniferous, eastern part of the Junggar Basin
have been in littoralregion condition.In some local
areas. gypsum has appeared lacustrine environment
during the quiet time of Carboniferous. The
emergence of bioclastic limestone indicates the sea
retreating.
In summary, we can see that in the Late
Carboniferous, it is mainly shallow sea transitional
facies in north and south of research area.The west is
wide lake sediments t.Middle part is the river and
shallow lake deposits.Which determine Distribution of
Carboniferous source rocks.
456

P-324
Occurrence of organic matter effect hydrocarbon generation and
expulsion in South China
Jianzhong Qin 1,2 , Baojian Shen 1,2 , Xiaodong Fu 1,2
1 Sinopec Research Institute of Petroleum Exploration and Production, Beijing, China, 2 Wuxi Institute of
Petroleum Geology, Sinopec Research Institute of Petroleum Exploration and Production, Wuxi, China
(corresponding author:qinjz@mail.wuxisuo.com)
Eight samples were collected from the hydrocarbon
reservoirs of the Sichuan Basin, which is located in
the Northwest of China. The samples are from
Paleozoic marine source rocks, including the Lower
Cambrian, Silirian, the Lower and the Upper Permian.
The geochemical characteristics of the samples with
high-over mature marine source rocks are as follows:
1) the TOC is mainly range of 3.93~14.95% and
kerogen Type belongs to II; 2) the minerals are
composition of quartz, calcite, dolomite and clay
minerals. An accurate assessment of oil generation
potential and expulsion efficiency of source rocks,
amongst other important features of a petroleum
All the source rock samples were simulated in the
same semi-closed generation–expulsion system. The
results of our simulated experiments shows petroleum
(oil and gas) generating were strongly dependent on
lithology in the same experiment condition. the marine
siliceous or carbonate rock has relatively higher
accelerating effect on hydrocarbon generation from
kerogen in comparison with marine mudstone and
shale during early stage, and siliceous or carbonate
rock easy generated heavy oil, clay rock generated
normal oil and gas, so siliceous or carbonate rock has
lowers the temperature of peaks of total oil
generation, and easily forms immature-low mature
heavy oil, and enlarging yields of total gas, CO2, H2,
total oil, oil carried by gas, residual oil, hydrocarbon
gas and total hydrocarbons with the temperature
increasing. This is because certain proportions of the
petroleum generated remains in the pore system of
the source rock, or adsorbed by kerogen and
minerals, there more oil was absorbed in clay rock
relative siliceous or carbonate rock. The results show
that minerals such as quartz, calcite has a positive
correlation with the quartz content but a negative
correlation with clay minerals content. And the marine
excellent source rock mainly consists of siliceous or
calcareous. It was mainly generated heavy oil in the
stage of early-middle maturation.
system, is essential. The purpose of this paper is � The marine siliceous or carbonate rock has the higher
using simulated experiments to distinguish oil expulsion efficiency than clay rock during the early-
occurrence of organic matter effecting hydrocarbon
middle maturation stage, but they have the same oil
generation and evaluate their oil expulsion efficiency.
expulsion efficiency which is about 60% in the late
Organic matters in these source rocks have three maturation stage. So in the early-middle stage organic
main occurrences by scanning electron microscope matter associated with siliceous or calcareous is more
and energy spectrum: 1) organic matter associated easy expulsive heavy oil, thus the clay rock hardly
with siliceous or calcareous matter. It is the main expulsive heavy oil. There distributed much bitumen
occurrence in the quality marine source rock in South
in the reservoir which came from the early generation
China; 2) organic matter associated with calcareous
matter. It is the main occurrence in some quality
of heavy oil in Sichuan basin, and the early expulsive
calcareous source rock in the Permian; 3) organic heavy oil would be cracked into gas with the buried
matter associated with clay, or coated by flaky clay depth. This cracking gas of heavy oil is the main
particles and associated with siliceous and calcareous source of gas pools in Sichuan basin.
biofacies.
Based on the experimental results and the discussion
above, it can be concluded that: Super thin siliceous
or calcareous layers rich in organic maters are easy
to expel early generated heavy oil, and thus a giant
heavy oil pool may be formed. On the contrast,
organic matters coated by flaky clay particles are hard
to expel early-generated heavy oil, and thus a light oil
pool may be formed. The natural gas of Sichuan
basin is come from heavy oil cracking.
457

P-325
Origin of abnormal sonic response in the shale interval of
Northern Songliao Basin, China
Huo Qiuli, Zeng Huasen, Fu Li, Ren Zhigao, Fan Qinghua, Zhang Xiaochang
Exploration and Development Research Institute, Daqing Oilfield Company Ltd., PetroChina, Daqing, China
(corresponding author:yjydh206@yahoo.com.cn)
The deviation of sonic transit time log from normal
trend in the shale interval has been widely interpreted
as overpressure since Magara (1978). The
prerequisite for the relationship between sonic transit
time and overpressure is that overpressure is induced
by undercompaction or disequilibrium. The origin of
overpressure is still in controversial, however. Aplin et
al.(1995) suggested that the relationship of porosity
vs. depth was influenced by lithology heterogeneity.
Another example is that overpressure can exist in the
shale interval of normal pressure (e.g. Teige et al.,
1999, Hao et al., 2007). It seems that overpressure
and the deviation of sonic transit time log from normal
trend are not necessary closely correlated. The
deviation of sonic transit time log from normal trend is
widespread in the shale interval of Qingshankou
formation at the basin scale, especially on the bottom
of Qingshankou 1st member (K2qn1) which is the
main source rock in the Songliao Basin. In most of
past studies (e.g. Wang, 1984, Chi et al., 2000, Xiang
et al., 2006), those deviations of sonic transit time are
considered to be induced by overpressure of shale
based on undercompaction or disequilibrium
mechanisms, and as the main force that migrated the
oil generated from K2qn1 downward to the underlying
Fuyang reservoirs. However, our recent studies
showed that the deviations of sonic transit time may
be more closely correlated to the organic carbon
content in the shale interval which has never been
noticed before. Profiles of sonic log and total organic
carbon content (TOC) of three representable wells
with different organic maturities, which excludes the
hydrocarbon generation origin of overpressure, show
that the sonic log nearly traces the TOC profile in
each well (see Fig. 1). It is accordingly believed that
the deviation of sonic log is induced by organic
content heterogeneity in the shale interval (i.e.
lithology heterogeneity). The sonic transit time of
shale in K2qn1 with different burial depths was then
plotted by depth in Fig. 2 to decrease the effect of
lithology heterogeneity. The result is obvious and the
sonic transit time decreases as the depth increases
without any deviation, which corroborated that the
sonic transit time deviation in the shale interval is
most likely the result of lithology heterogeneity
(organic content) instead of overpressure induced by
undercompaction or disequilibrium.
Fig. 1 Sonic transit time and TOC profiles by depth in the
Songliao Basin. TOC log were calculated using method
described by Passey et al.(1990) while calibrated by
measured data (solid circle). SK-I is a scientific drilling well
from ICDP project. Ro is the reflectance of vitrinite.
Depth(m)
0 60 120 180
0
Du 401
500
1000
1500
2000
2500
Jin 37
Gu 302
SonicTransit Time(us/ft)
Shengshen 2
Si 103
Shuang 11
Fig. 2 Sonic transit time (of shale) profile by depth in the
K2qn1. Short horizontal lines are the sonic transit time
ranges.
References
1.Aplin, A.C., Yang, Y., Hansen, S., 1995. Assessment of
[beta] the compression coefficient of mudstones and its
relationship with detailed lithology. Marine and Petroleum
Geology 12, 955-963.
2.Magara, K., 1978. Compaction and Fluid Migration.
Elsevier Science & Technology.
458

P-326
Source rock investigations on Palaeozoic and Mesozoic
sediments of the Central Congo Basin, Democratic Republic of
Congo
Ralf Littke 1 , Victoria Sachse 1 , Damien Delvaux 2 , Jan Schwarzbauer 1
1 RWTH Aachen University, Institute of Geology and Geochemistry of Petroleum and Coal, Aachen,
Germany, 2 Royal Museum for Central Africa, Tervuren, Belgium (corresponding author:sachse@lek.rwthaachen.de)
The Congo Basin is one of the largest intracratonic
sedimentary rift basins in the world, but still poorly
investigated with respect to petroleum potential. Up to
now, the investigations by Daly et al. (1) contain the
most comprehensive source information on the
Congo Basin, including the basin structure and its
post- Paleozoic history. In addition, Giresse (2)
compiled the Mesozoic-Cenozoic history of the Congo
Basin. The approach of this work is to document
various types of source rocks of the Congo Basin,
their quantity, quality and maturity of OM as well as
the depositional environment in relation to tectonic
evolution. For this purpose, in total 147 samples
stored in the rock collection of the Royal Museum for
Central Africa, Belgium, covering various stratigraphic
units of the Congo Basin were investigated, including
samples of two wells (Samba and Dekese).
Palaeozoic and Mesozoic outcrop and core samples
covering various stratigraphic intervals from the
central Congo Basin were analyzed for total organic
carbon (Corg), total inorganic carbon (Cinorg) and total
sulfur content (TS). Rock-Eval analysis and vitrinite
reflectance measurements were performed on the
basis of the Corg content. Non-aromatic hydrocarbons
were analyzed by way of gas chromatography-flame
ionization detection (GC-FID) and GC-mass
spectrometry (GC-MS).
Our data revealed two highly potential source rocks in
the Congo Basin: sediments of the Loia and
Stanleyville Formation. All of the Pre-Mesozoic
sediments contain only a small amount of OM.
Samples of the Alolo shales, which belong to the Lindi
Supergroup (late Neoproterozoic / early Paleaozoic)
are in general very poor in Corg and contain a high
amount of degraded organic matter. All samples of
this formation revealed a Type III/IV kerogen and
cannot be considered as a potential source rock.
Sediments from the Lukuga Formation (Permo-
Carboniferous) contain moderate contents of organic
carbon, representing hydrogen-poor Type III/IV
kerogen having at best a very minor gas generation
potential. Tmax values indicate early mature organic
matter, and a slight higher level of maturity is
indicated by vitrinite reflectance and PI values. The
kind of OM as well as the biological markers led to the
conclusion of a terrestrial dominated depositional
environment.
Organic geochemical investigations on Late Jurassic
(Stanleyville Formation) to Early Cretaceous (Loia
Formation) samples from the Samba well and outcrop
localities, in the north-eastern part of the Congo
Basin, revealed moderate to high contents of organic
carbon (up to 25 %). The kerogen is characterized by
very high hydrogen index (HI) values reflecting Type I
kerogen of excellent quality in the Stanleyville
Formation and Type I/II kerogen in the overlying Loia
Formation. All of the samples studied here are too
immature for petroleum generation. Based on
biomarker analysis/n-alkane distribution a lacustrine,
anoxic depositional environment can be assumed for
these units. Stanleyville and Loia Formation can be
regarded as excellent petroleum source rocks and
could be part of a petroleum system if sufficient burial
and maturation has occurred.
Finally, vitrinite reflectance data was used to calibrate
1D models for wells Dekese and Samba, which give
an overview about burial-, thermal-, and maturity
history of the area.
Figure 1 Bulk geochemical data of various samples of
the Congo Basin: Rock-Eval HI and OI values.
(1) GIRESSE, P., 2005. Mesozoic-Cenozoic history of the Congo
Basin, Journal of African Earth Science, 43, 301-305.
(2) DALY, M. C., LAWRENCE, S.R., DIEMU-TSHIBAND, K. and
MATOUANA, B.,1992. Tectonic evolution of the Cuvette Centrale,
Zaire, Journal of Geological Society, 149, 539 – 546.
459

P-327
Organic geochemistry and organic petrology of Lower Jurassic
source rocks from Aït Moussa, Middle Atlas, Morocco
Victoria Sachse, Detlev Leythaeuser, Jan Schwarzbauer, Ralf Littke
RWTH Aachen University, Institute of Geology and Geochemistry of Petroleum and Coal, Aachen, Germany
(corresponding author:sachse@lek.rwth-aachen.de)
Proven petroleum systems of Morocco occur chiefly in
the Essaouria, Prerif and Rharb Basins. Several
source rocks have been discussed, i.e. Silurian
(eastern Essaouira), Liassic (Prerif), Oxfordian
(western Essaouira), Cretaceous (Ain Hamra) and an
intra-Miocene biogenic source rock system in the
Rharb Basin. The origin of the Cap Juby oil shows in
the offshore Tarfaya basin as well as the oil shows
encountered in Guettata wells in the onshore of
Essaouira Basin are of uncertain origin, with a
Jurassic carbonate source (Toarcian) being currently
the favored interpretation. Due to well known Toarcian
source rock systems worldwide and a similar
depositional history of Toarcian and Pliensbachian
sediments, the main objective of the present study
was to improve the characterization of the petroleum
generation potential of a Pliensbachian source rock in
the Middle Atlas using detailed molecular
geochemical analysis as well as organic petrological
studies.
The locality Aϊt Moussa (Pliensbachian to earliest
Toarcian, Boulemane province, Middle Atlas) is the
only example of an effective petroleum source rock in
the Moroccan Atlas rift basins. To get more
information about its source rock potential, Corg/Ctotalmeasurements,
sulphur measurements (TS), Rock-
Eval pyrolysis, vitrinite reflectance measurements,
fluorescence microscopy and organic-geochemical
analyses were carried out to get basic information on
their thermal maturity, the potential to generate
hydrocarbons and their depositional environment.
Investigations revealed the presence of a type-I/II
kerogen (Fig. 1), which was deposited under marine
conditions with an input of predominantly algalderived
organic matter. The presence of woody
particles indicates a small input of terrestrial organic
matter. The organic-geochemical and biomarker
analyses indicate a deposition of the carbonate-rich
sediments under oxygen-depleted conditions (Fig. 2).
Rock-Eval data as well as biomarker evaluation
revealed that oil window maturity has been reached
but not the peak of oil generation. An initial stage of
petroleum generation and migration is indicated by
geochemical and microscopic evidence. Kinetic
parameters on petroleum generation characteristics
reveal that this kerogen decomposes within a narrow
temperature interval due to a quite homogenous
structure of the algal-derived organic matter. Finally,
the kinetic parameters and the vitrinite reflectance
were used to create a 1D model which gives an
overview about burial-, thermal-, and maturity history
of the area of Aït Moussa as well as timing and
generation potential of petroleum.
Figure 1 Bulk geochemical data of Pliensbachian
samples: Rock-Eval HI and OI values.
Figure 2 Pr/nC17 vs. Ph/nC18 for selected
Pliensbachian samples (Interpretation scheme
according to Shanmungam, 1985).
Shamungam, G., 1985. Significance of coniferous rain
forests and related organic matter in generating
commercial quantities of oil, Gippsland Basin,
Australia. AAPG Bull., 69 (8), 1241-1254.
460

P-328
Alteration of macromolecular composition of palynomorphs as
an effect of thermal maturation
Nadia al Sandouk 1 , Christoph Hartkopf-Fröder 3 , Stephan Kaufhold 2 , Jan Schwarzbauer 1
1 RWTH Aachen University, Aachen, Germany, 2 Federal Institute for Geosciences and Natural Resources,
Hannover, Germany, 3 Geological Survey of North Rhine Westphalia, Krefeld, Germany (corresponding
author:al_sandouk@lek.rwth-aachen.de)
To study thermal maturity of sediments
microscopic properties such as reflectance and color
of vitrinites and palynomophs are very important.
Because of their small size pure concentrates are
difficult to obtain and, hence, information on specific
chemical composition and structure is still very
limited. Therefore, alteration of the macromolecular
composition of palynomorphs during thermal
maturation is even nearly unexplored. Although many
pyrolytic studies are devoted to the composition of
modern and fossil sporopollenin the chemical
changes due to the maturation process have only
rarely been elucidated using pyrolysis methods.
The aim of this research was the comparison
of the analytical results get by different methods such
as µ-FTIR and Curie-Point-Pyrolysis. For this
suppose, sample material was taken from six
boreholes drilled at the southwestern rim of the Hils
Syncline (Lower Saxony Basin, NW-Germany). All
boreholes encounter the uppermost part of the
Pliensbachian, the complete Toarcian Posidonia
Shale and the lower part of the Aalenian. These
samples represent complete maturation series within
the oil window, meaning Vitrinite Reflectance from
0.48 % to 1.45 %. To release organic microfossils
from the sediment and for preparation of kerogen
concentrates several standard palynological
techniques have been followed using HCl and HF.
These acid treatments are believed not to influence
the chemical composition of palynomorphs [1].
Fig 1: µ-FTIR analysis of bisaccate pollen with
interpretation of the bands [2]
Bisaccate pollen, not separated from the
kerogen concentrates with different thermal
maturities, have been analyzed with µ-FTIR. As
Figure 1 shows, the contribution of methylene C-H
anti-symmetric stretch (γCH2-asym) as well as
methylene C-H symmetric stretch (γCH2-sym)
changes noticably, whereas the band representing
the C=C aromatic ring stretch remains roughly the
same. Also the bands describing the alcohol or alkylsubstituted
ethers C-O stretch (~1165-~1030 cm -1 ) or
the γC-H aromatic deformation (~970 - ~630 cm -1 )
show significant alterations.
These maturity-dependent changes are also
apparent in pyrograms, measured by Curie-Point-
Pyrolysis. Fig 2 shows a pyrogram from a bulk
kerogen sample with a thermal maturity of 0.48 % VR,
Fig.3 a sample with a maturity of 0,68 % VR.
Fig 2: Curie-Point-Pyrolysis of a bulk kerogen
concentrate, VR 0.48 %
Fig 3: Curie-Point-Pyrolysis of a bulk kerogen
concentrate, VR 0.68 %
This study clearly reveals systematic changes in
chemical structural properties of palynomorphs and
related kerogen concentrations with maturity.
References:
[1] van Bergen, P.F. 1999: Collection and storage of
fossil plant remains for organic geochemical analyses.
In Jones, T.P., Rowe N.P. (eds): Fossil Plants and
Spores:Modern Techniq2ues, 135-138. The
Geological Society, London
[2]Steemans, P., Lepot, K., Marshall C.P., Le Hérissé,
A., Javaus, e.J. 2010: FTIR characterization of the
chemical composition of Silurian miospores
(cryptospores and trilete spores) form Gotland,
Sweden. Review of Paleobotany and Palynology
461

P-329
Characterising the depositional environments of the massive
lacustrine source rocks of Nenjiang Formation in Songliao Basin,
China
Zhiguang Song, Qin Yin, Sibo Wang
State Key Laboratory of Organic Geochemistry, Guangzhou, China (corresponding author:zsong@gig.ac.cn)
Songliao Basin is the largest petroleum-containing
and producing basin in China. Two sets of massive
lacustrine source rocks were developed during the
Upper Cretaceous time. The major source rocks are
both in great thickness and massive distribution
associated with high abundance of organic matter and
higher hydrogen index (IH) which indicated type I and
II kerogen. The organic matter is characterized by the
high carbon numbered long-chain alkanes and longchain
alkyl naphthalenes. The organic matter were
mainly originated from the specific aquatic algae input,
while high plants input were very limited as there are
no distinguishing terrestrial biomarker identified. The
pristane/phytane ratio and the occurrence of
gammacerane and aryl isoprenoids suggest that
anoxic and salinity stratified water column were
prevailed during the sedimentation of petroleumprone
source rocks, while non-stratified water and
anoxic depositional environment were contributed to
the deposition of organic poor sediments.
Furthermore, the profile variation in the composition
and distribution of hydrocarbon including the carbon
isotopic composition suggest that there were short
period of rapid fluctuation in the climate related
environmental changes.
(This research are financially supported by the NSFC
fund of 40973033 and State ―973‖ Project
(2006CB701404)
462

P-330
Hydrous pyrolysis experiments: new insights about generation,
saturation and petroleum expulsion through organic
petrographic evidences
Igor Souza 1 , Carla Araujo 1 , Taissa Menezes 1 , Luiz Felipe Coutinho 1 , Eugênio Santos
Neto 1 , Regina Binotto 1 , André Spigolon 1 , Giovani Cioccari 1 , Rosane Alves Fontes 1 ,
Michael Lewan 2 , Noélia Rondon 3 , João Mendonça Filho 3
1 PETROBRAS/CENPES/GEOQ, Rio de Janeiro, Brazil, 2 U.S. Geological Survey, Denver, United States of
America, 3 Federal University of Rio de Janeiro, Rio de Janeiro, Brazil (corresponding
author:igorviegas@petrobras.com.br)
Hydrous pyrolysis experiments were conducted on
immature organic-rich rock of the Oligocene-Miocene
Tremembé Formation in the Taubaté Basin (Brazil) to
evaluate petroleum generation, saturation and
expulsion processes, mainly based on optical
analysis. For this propose, twenty two experiments
were carried out under isothermal conditions at ten
different temperatures (280° through 360°C) for nine
different durations between 18 and 144 h. Total
Organic Carbon (TOC), Rock-Eval pyrolysis, vitrinite
reflectance (%Ro), spectral fluorescence and visual
characterization, under reflected white light and
fluorescence mode, were carried out on recovered
and original rocks. TOC, source rock potential (S2)
and hydrogen index (HI) tend to decrease with the
increment of temperature and duration of the
experiments. These behaviors are normal and can be
attributed to oil generation process. Conversely,
residual free hydrocarbons (S1) increase to
intermediate conditions of maturation, decreasing
thereafter. This S1 feature is related to the generation
and some changes in the fabric of the rock that
reduces the oil retention capability and facilitates the
expulsion process. Palynofacies results demonstrated
a predominance of amorphous organic matter (AOM)
and low content of palynomorphs and phytoclasts,
which corroborates with interpreted kerogen type
based on hydrogen and oxygen indices (i.e., type I
kerogen). The palynomorphs are mainly represented
by fresh water algae (Botryococcus). The %Ro varies
from 0,32% to 0,74% and are not totally reliable
because of the low number of vitrinite particles
suitable for measurement and a high standard
deviation. The transformation rate (%TR) obtained
from S2 was chosen as a guide for thermal evolution
instead of %Ro. The spectral fluorescence data
obtained in telalginites (Botryococcus) are probably
affected by the presence of bitumen and the type of
organic matter available for measurements. It is worth
mentioning that the content of Botryococcus
decreases with increasing %TR, which can be
explained as a result of oil generation. The good
correlation between spectral fluorescence and vitrinite
reflectance of the samples recovered from the lowerthermal
maturity (%TR lower than 17%) experiments
indicates the absence of suppressed vitrinite.
However, the rocks recovered from the higher
thermal-maturity experiments (%TR higher than 66%)
contain suppressed vitrinite, which may be due to the
presence of bitumen [1]. Correlation between %TR
and %Ro suggested that the organic matter is
reactive, and in agreement with results from opensystem
global kinetics. Fluorescence color and
quantity of Botryococcus, quantity and types of
bitumen, fluorescence of matrix (AOM + mineral
matrix and bitumen), and vugs and fractures were
observed in all samples. The bitumen production
increases with %TR and two types of bitumen were
differentiated by fluorescence color. Bitumen with
yellow fluorescence is attributed to n-alkanes and
isoprenoids and was generated earlier than bitumen
with brown fluorescence. The visual analysis
suggested that the major volume of bitumen with
yellow fluorescence is derived from Botryococccus.
The bitumen with brown fluorescence is attributed to
high NSO-compound content derived from the AOM.
The impregnation by bitumen was observed with
increasing fluorescence of the matrix. The greatest
bitumen impregnation was indicated by the matrix
fluorescence color becoming yellow. This stage
happens when the %TR is around 41% to 45%, which
occurs when the S1 reaches its highest values. The
decrease of bitumen impregnation of the matrix and
consequential oil expulsion is marked by a reduction
in S1 values and fluorescence color. This
phenomenon occurs with the development of
fractures and vugs in the matrix. It is very interesting
to notice that the expulsion of products occurs at low
transformation rates. These results help us to better
understand the processes related to the oil
generation, saturation, primary migration, expulsion
and type of generated fluid. Each type of organic
matter has its own kinetics and starts to generate
bitumen and oil at different %TR having distinct
products. The comprehension of these processes can
help to improve petroleum system models.
463

P-331
Organic-geochemical characteristics of sediments from the
Lopare basin, Bosnia and Herzegovina
Nenad Grba 1 , Aleksandra Ńajnoviš 2 , Ksenija Stojanoviš 3 , Branimir Jovanţiševiš 3
1 Faculty of Ecology and Environmental Sciences, 11000 Belgrade, Serbia, 2 Center of Chemistry, IChTM,
11000 Belgrade, Serbia, 3 University of Belgrade, Faculty of Chemistry, 11000 Belgrade, Serbia
(corresponding author:sajnovica@chem.bg.ac.rs)
In this study the molecular composition and biomarker
distribution of sediments of Neogene age (Lopare
basin, Bosnia and Herzegovina) were investigated. A
total of 46 samples originated from two boreholes
POT-1 (depth of 193 m) and POT-3 (depth of 344 m).
The organic carbon content was determined by
elemental analysis after carbonate removal with dilute
HCl (1:3, v/v). The bitumen was extracted from
sediments using a soxhlet with an azeotropic mixture
of dichloromethane and methanol. The saturated and
aromatic fractions were isolated using column
chromatography. Saturated and aromatic
hydrocarbons were analyzed by gas chromatographymass
spectrometry (GC-MS).
The organic carbon content, Corg varies in
approximately similar ranges in the sediments of both
boreholes, with average values of 0.86 and 0.80%.
The relative proportions of hydrocarbons in the
bitumen are low (< 20%).
The distribution of saturated hydrocarbons is
dominated by phytane, β-carotane and regular C27-
C29αα(R)-steranes, indicating the low maturity of the
organic matter (OM). n-Alkane distribution of the
almost all the sediments is characterized by marked
dominance of lower homologues n-C17, n-C21 or n-
C22, typical of organic matter of algal.
Domination of phytane in the majority of samples and
values of pristane/phytane (Pr/Ph) ratio < 0.60; for a
great number of sediments are even below 0.20,
indicate reducing to anoxic conditions during
deposition of OM.
All the samples contain squalane. Values of
squalane/n-C26 alkane ratio are in average 2.89 and
3.14 in the boreholes POT-1 and POT-3, respectively
(in some sample are more than 8) indicating saline to
hypersaline depositional environment [1].
Distributions of polycyclic alkanes of sterane and
hopane types are characterized by the domination of
thermodynamically less stable isomers. Values of the
maturation parameters, C31(S)/(C31(S+R) < 0.40;
C29ααS/(ααS+ααR) < 0.30 indicate that the samples
contain OM with maturity, which corresponds to the
diagenetic phase. In the majority of the samples C28
sterane content accounts for approximately 30 % in
total distribution of C27-C29 regular sterane
homologues. This fact is consistent with literature
data for regular sterane distribution in hypersaline
environments [2].
β – Carotane, the relative percentage of which in the
total distribution of hydrocarbons is up to 25%, and
many other diagenetic derivates of β – carotene were
identified. These compounds are associated primarily
with anoxic, saline lacustrine, or highly restricted
marine settings, where organisms such as unicellular
algae Dunaliella, developed as the dominant biota [3].
Some of the samples contained diagenetic products
of isorenieratene, such as diaromatic carotenoids with
40 carbon atoms, C33 and C32 compounds and short -
chain compounds - aryl isoprenoids. The presence of
mentioned compounds indicates contribution of green
sulfur bacteria (Chlorobiaceae) to precursor OM
deposited in photic zone anoxia (PZA) [4].
Sediments from both boreholes POT-1 and POT-3 of
the Lopare basin contain immature algal organic
matter deposited under anoxic, saline to hypersaline
conditions. The biomarker patterns are in agreement
with geological history of the basin. Namely, during
Oligocene and Lower to Middle Miocene, Lopare
basin was the part of the same deposition basin which
included also Tuzla basin with salt formation, which is
exploited for decades.
References
[1] Grice, K. et al., 1998. Organic Geochemistry 28,
349-359.
[2] Yangming, Z., et al. 2005. Applied Geochemistry
20, 1875-1889.
[3] Peters, K.E., Walters, C.C., Moldowan, J.M., 2005.
The Biomarker Guide, Volume 2: Biomarkers and
Isotopes in Petroleum Exploration and Earth History.
Cambridge University Press, Cambridge, UK.
[4] Clifford, D. et al. 1998. Organic Geochemistry 29,
1253-1267.
464

P-332
Source rock characterization and depositional environment of
The Middle Miocene Hirka Formation (Beypazari-Ankara/Turkiye)
Berna Yavuz Pehlivanli 1 , Ali Sari 2 , Şukru Koc 2
1 Bozok University, Department of Geological Engineering, 66100, Atatürk Yolu, Yozgat, Turkey, 2 Ankara
University, Faculty of Engineering, Department of Geological Engineering, Ankaka, Turkey (corresponding
author:bernayavuz80@gmail.com)
Hırka Formation oil shales (~100 km NE of Ankara,
Turkiye) occured in Middle Miocene. Hırka Formation
become volcano-sedimentary stack that is generally
formed from claystone, oil shale, trona, mudstone,
intra-formation pebblestone, siltstone and pyroclastic
rocks. All this lithofacies developed to change
environment condition from consistently lake to playa
lake.
This formation has been studied by a combination of
organic geochemical methods (LECO/Rock-Eval) and
elemental analysis (ICP-MS) in order to assess the
hydrocarbon source potential of the abundant and
extensive shale intervals presents in the formation.
According to V / Cr, Ni / Co, V / (V + Ni) and V / Ni
ratios show that the organic matter of the source
rocks had been deposited in between oxic - disoxic
and anoxic conditions. Co/Ni and V/Ni ratios and
cross plots of the absolute values of V and Ni indicate
that these samples had significant terrestrial input.
Organic geochemical methods (LECO / Rock-Eval)
were used to determine oil- source rock potential of
oil-shales Total organic carbon (TOC) values (2.08
and 48.48 wt%) in oil shale samples indicates that it
has a very good-excellent source rock potential.
Furthermore the shales with hydrogen index (HI)
values (from 252 to 911; average 711) was found to
be generally excellent petroleum potential. Rock-Eval
(TOC,S1, S2, HI, OI and Tmax) and organic
petrography (amorphous/alga and inertinit) and
indicate that the shales are dominantly oil and gas
potential, containing Type 1 and II organic matter.
Thermal maturity, assessed from Tmax (Tmax value
between 381 and 447 °C), indicates that Middle
Miocene Hırka Formation range from diagenetic to
over mature with respect to oil generation and may
produce gas and oil.
465

P-335
Geochemistry of aqua-bitumoids from deposits in the West
Siberian sedimentary basin
Valentina Danilova, Alexey Kontorovich
Trofimuk Institute of Petroleum Geolodgy and Geophysics SB RAS, Novosibirsk, Russian Federation
(corresponding author:DanilovaVP@ipgg.nsc.ru)
A systematic study of aqua-bitumoids (AB)
(bitumoids -chloroform extractable bitumens) from
West Siberian sedimentary basin have been
conducted for several years in the Organic
Geochemistry laboratory, SB RAS IPGG, which
allowed us to developed a method for their extraction
and schematics for their study.
It‘s been established that the concentration
of bitumoids in reservoir waters varies widely - from 4
to 390 mg / l (litre), reaching in some waters 1-3 g / l
and more. Based on the geological setting of waters
localization, and the concentration and composition of
bitumoids there were defined two types of groups in
the West Siberian basin. The first group characterizes
regional background of primary and secondary
migrations of dispersed bitumoids. Whereas the
second one describes the anomalies associated with
dispersion of oil components from the reservoirs. For
both the generations of AB the analysis was given to
the changes in their content, as well as element,
group and hydrocarbon composition through the area
and in the context of the increasing age of
hydrogeological complexes [1].
Applying cluster analysis method, on the
base of a large set of biomarker parameters, each of
the AB groups was divided into three families, with
their biomarkers specific features and stratigraphic
confinement being established therewith [2].
In each water aggregate entity, aquabitumoids
from the first family by their biomarker
parameters are assigned to the continental type,
which is likely to have sourced from DOM with a
significant portion of terragenous constituent, and the
dissipated from reservoirs oil components,
genetically related to higher terrestrial vegetation.
The third family of AB from the both groups
based on biomarker characteristics was diagnosed as
marine. Thereby, this family in both AB groups I and II
is believed to have originated from DOM of marine
facies and scattered components of oil of marine type.
The second family of AB from both the
groups is closer to the marine family in the context of
biomarker parameters. Their source might have been
dispersed OM mixed with a small portion of
terragenous constituent and scattered components of
oil mixed from the reservoirs.Genetic relations
established at the molecular level between HC
DOM→ AB → oils showed that the source of AB in
the West Siberian basin including its northern areas at
present stage of its history, appeared to have been
not only DOM from the Lower-Middle Jurassic
horizons with different proportions of terragenous and
aquagenous constituents (the Tyumen and Togur
Fms and their analogues), but inherently aquagenous
OM of the Bazhenovo Fm and its analogs. With
regard to northern parts of the basin, there has been
not sufficient information, even enough to make
assumptions of this kind, which leaves the fact
obscure from the point of view of sedimentarymigration
theory of oil formation.
In the issue, the comprehensive studies of
AB have shown that the possibility of hydrocarbons
migration, including hydrocarbons-biomarkers, resins
and asphaltenes, together with waters in natural
systems appear to have been much greater than
anticipated by some researchers [3].
It is shown that the extent of bitumoids‘ comigration
with waters is enormous. Given the large
number of cycles of expelled water exchange in the
basin, even being significantly scattered, they could
have provided established at present oil and gas
resources.
By AB content and composition there have
been developed criteria for prognosis evaluation of
the poorly explored sedimentary basins.
This work was supported by RFBR (10-05-00705), the
Interdisciplinary Integration Project of SB RAS N 36.
References
[1] Kontorovich, A.E. Aquabitumoids // Gubkin‘s Scientific Inheritance
in Petroleum Geology of Siberia. Novosibirsk, Nauka, 1980, pp. 73-
85.
[2] Danilova, V.P. Geochemistry of Aquabitumoids // Geologia I
geofizika, 2004, v. 45, № 7, pp. 803-814.
[3] Uspenskii, V.A. Introduction to Petroleum Geochemistry.
Leningrad, Nedra, 1969, p. 307.
466

P-336
Mechanistic model of the thermal evolution of n- and iso-alkanes
(C1-C32) in oils
Valérie Burkle-Vitzthum 1 , Roda Bounaceur 1 , Paul-Marie Marquaire 1 , François Montel 2 ,
Luc Fusetti 2
1 Laboratory of Reactions and Process Engineering, Nancy, France, 2 TOTAL Exploration and Production,
Pau, France (corresponding author:valerie.vitzthum@ensic.inpl-nancy.fr)
The purpose of the present work is to construct a
model able to take into account the cracking of a
complete distribution of n-alkanes as well as of a
distribution of branched alkanes from C1 to C32. The
choice of the iso-alkane model compounds is done on
the basis of the observations of biological systems
and sedimentary organic matter. The model takes into
account 46 iso-alkanes and 32 n-alkanes; this mixture
is meant to represent the major part of the saturated
fraction of petroleum.
A rigorous lumping together procedure is applied to
build the mechanistic model that consists of 13 206
lumped free radical reactions (initiations,
decompositions via �-scission, H-transfers, additions,
terminations) using rate constants available from the
literature. With this model, the cracking global
activation energy of n-C15 as well as iso-C15 is close
to 69 kcal/mol in the range 200-350 °C.
The model is validated on the basis of several
literature experimental results concerning pure alkane
cracking. The conversion as well as the product
distribution are well simulated up to 50% conversion
(300-450 °C and 90-700 bar).
The model is compared also to the saturated fraction
obtained from pyrolysis of Elgin oil (North Sea, UK) at
372 °C up to 1000 h. In this oil, the polar compounds
are negligible and the saturated fraction particularly
abundant. Fig. 1 shows the experimental product
distribution of the Elgin saturated fraction after whole
oil isochoric pyrolysis (TOTAL, unpublished data).
The C1-C10 fraction was analyzed by GCMS and the
C11+ fraction by GPC. The simulated alkanes
distribution is in Fig. 2. Gas and C10+ are well
represented whereas some discrepancies are
observed for C6-C10, but they are essentially due to
cycloalkanes that are not included into the model but
not negligible for these C numbers. In order to
characterize the C10+ decrease, the Ci+1/Ci ratios are
calculated: the model fits the experimental values up
to 500 h.
% mole
% mole
10
1
0,1
0,01
0,001
0,0001
0 10 20 30 40 50
Carbon number
Initial
30 hours
100 hours
200 hours
500 hours
1000 hours
Fig. 1: Elgin oil pyrolysis: experimental distribution.
100
10
1
0,1
0,01
0,001
0,0001
0,00001
0 5 10 15 20 25 30 35
Carbon number
initial
30 hours
100 hours
200 hours
500 hours
1000 hours
Fig. 2: Elgin saturated fraction: simulated distribution.
This model should lead to new insights into
thermogenic gas generation and relative thermal
reactivity of n- and iso-alkanes at a geological scale.
One additional potential application of our model is
the theoretical reconstruction of the real distribution of
n-alkanes of the produced oil from its analytical
distribution of iso-alkanes. Indeed, as opposed to isoalkanes,
the distribution of n-alkanes obtained from
the analysis of the produced oil is biased due to
partial precipitation of the n-alkanes population in the
subsea tubing.
467

P-337
Application of electrospray ionization fourier transform ion
cyclotron resonance mass spectrometry on formation
mechanism of high acidity oils
Cheng Dingsheng 1 , Dou Lirong 2 , Shi Quan 3 , Hou Dujie 4
1 RIPED, Petrochina, CNPC, Beijing, China, 2 CNODC, Petrochina, CNPC, Beijing, China, 3 China University
of Petroleum, Beijing, China, 4 China University of Geosciences, Beijing, China (corresponding
author:chengdingsheng@petrochina.com.cn)
Although content of NSO-compounds in crude oils is
very low, they can seriously affect the processing
technology and product property of crude oils. The
composition of heteroatom compounds, especially the
heteroatom compounds with big molecular weight, is
the key and difficult aspect domain in petroleum
geochemistry for a long time. During the recent years,
great advancements have been achieved on the
composition analysis of heteroatom compounds of
heavy oils by the Electrospray Ionization (ESI)
coupled with Fourier Transform Ion Cyclotron
Resonance Mass Spectrometry (FT-ICR MS).
In order to study the genetic mechanism of high
acidity oils, the authors sampled 58 oil samples from
three rift basins (18 oil samples from Muglad Basin &
Melut Basin in Sudan, 40 samples from Bohai Bay
Basin in China) to compare the compositional
characteristics of crude oils in different basins by ESI
coupled with FT-ICR MS, and probed into the
formation mechanism of high acidity oils in different
rift basins.
Using ESI coupled with FT-ICR MS on 58 crude oils
with different total acid number (TAN), 7 heteroatom
types have been identified in these oil samples,
namely, N, NO, NO2, O1, O2, O3 and O4,
corresponding carbazole compounds, phenolic
compounds containing N, carboxylic acid containing
N, phenolic compounds, carboxylic acid compounds,
carboxylic acid with hydroxyl, dicarboxylic acid,
respectively. Relatively, N1- and O2- compounds
have abundant content in high acidity oils, which
occupied more than 80% in NSO-compounds.
Different types of heteroatom compounds are different
in the degree of ring condensation, for example, O2compounds
range in the degree of ring condensation
between 0 to -34 and N-compounds range between -9
to -27.
Further analysis indicated that the organic acids of
crude oil consist mainly of naphthenic acids with the
TANs increasing gradually with the increment of
biodegradation degree. The naphthenic acids of high
TAN oils consist mainly of mono-cyclic, bi-cyclic, tricyclic
naphthenic acids. With increasing of intensity of
biodegradation, the ratio of the content of naphthenic
acids to fatty acids and the content of multicyclic
naphthenic acids will be increased among the
naphthenic acids, especially the bi-cyclic, tri-cyclic
naphthenic acids. The degree of ring condensation of
carbazole will be increased during biodegradation,
and the relative molecular weight of benzocarbazole
and dibenzocarbazole have good relationship with the
intensity of biodegradation. The average molecular
weight of benzocarbazole and dibenzocarbazole will
be reduced with the increment of the intensity of
biodegradation, that is, the alkyl chain of
benzocarbazole and dibenzocarbazole will be shorter.
The authors conclude that FT-ICR MS is a powerful
analysis technology for petroleum geochemistry,
which can provide very wide applications in petroleum
and petroleum chemical industry. The only origin of
high TAN oils is biodegradation.
References
[1] Shi Q, Deng ZY, Zhang YH et al. 2008. Data
processing of crude components by negative ion
electrospray Fourier transform ion cyclotron resonance mass
spectrometry. Journal of Instrument Analysis, 27(1) (in
Chinese with English abstract)
[2] Shi Q, Zhou YC, Hou DJ et al. 2007. Analyses on
naphthenic acids of Liao He crude oils by negative ion
electrospray Fourier transform ion cyclotron resonance mass
spectrometry. Journal of Instrument Analysis, 26(1):317-320
(in Chinese with English abstract)
[3] Shi Q, Zhao SQ, Xu CM and Hou DJ. 2008. Fourier
transform ion cyclotron resonance mass spectrometry and
its application in petroleum analysis. Journal of Chinese
Mass Spectrometry Society, 29(6): 367-378 (in Chinese with
English abstract)
468

P-338
Examples of the relationship between reservoir character and
hydrocarbon signatures measured at the surface
Paul Harrington, Alan Silliman
W. L. Gore & Associates, Inc., Elkton, MD, United States of America (corresponding
author:asilliman@wlgore.com)
Adsorbent-based surface geochemical samplers are
used to detect a wide range of volatile organic
hydrocarbon compounds in soil. Many of these
compounds are of likely thermogenic origin, from
underlying petroleum reservoirs. Microbuoyancy
theory has been proposed as the mechanism for
vertical migration of organic compounds, through the
stratigraphic column to the surface. Heavy saturated
compounds as heavy as phytane (C20) are
detectable in minute amounts (10 -9 grams).
Geochemical samplers are used to collect surface
geochemical data from exploration areas, and also
from available regional petroleum production and dry
well sites (―control samples‖).
A relationship is noted between reservoir quality, as
measured by the net pay thickness – porosity product,
and strength of surface geochemical signature, as
measured by pattern and mass of hydrocarbon
compounds. A relationship is also noted between
strength of surface signature and current production
volume at numerous well sites. Reservoir pressure is
correlated positively with the strength of surface
geochemical signature.
Examples of the correlation between reservoir
character and surface hydrocarbon signature are
presented from geochemical surveys in the Anadarko
Basin of Oklahoma, Oriente Basin of Ecuador, the
Pietu Siupariai Field of Lithuania, the East Texas Salt
Basin, the Green River Basin of Wyoming, and the
Western Canadian Sedimentary Basin.
Practical applications of this relationship are shown by
results from the Banff B Pool reservoir, where a map
of geochemical signature over the reservoir matches
closely a map of (Øh) product for the Banff Formation.
Another example of the correlation between
production strength and geochemical signature
strength is provided by work over the Woodbine sand
trend in eastern Texas. Interpreted well log crosssections
through the Double A Wells gas field show
sand thickening with consequent increase in surface
geochemical signature quality.
In concept, the measurement of local surface
geochemical signal may be used to reveal bypass pay
sections in existing wells. For exploration regions and
proposed well locations, the strength of geochemical
signature would allow priority assignment and ranking
of sites and prospects. The application may also be
used to define sweet-spots in unconventional
hydrocarbon plays. When properly integrated with
other geological and geophysical information, this
surface geochemical technology can significantly
reduced exploration risk.
469

P-339
Geochemical characterization of asphaltenes and maltenes in
organic solid deposits
Eric Lehne, Kentaro Indo, Fenglou Zou, Jose Zacharia, Kamran Akbarzadeh, John
Ratulowski
Schlumberger DBR Technology Center, Edmonton, Alberta T6N 1M9, Canada (corresponding
author:elehne@slb.com)
Flow assurance is a critical concern in
ultradeepwater subsea developments because of the
long flow distances and the high-temperature, highpressure
regimes. Organic and inorganic deposits are
significant flow assurance issues. Well and pipeline
clogging can lead to economic losses and operational
delays. Asphaltenes are known to deposit in both the
petroleum recovery and topside refining processes.
The asphaltenes are normally in equilibrium under
reservoir conditions. During oil production this
equilibrium can be disrupted by a number of factors
including pressure reductions, introduction of miscible
gases and liquids, mixing with diluents and other oils,
and operations such as acid stimulation.
A high-pressure deposition cell was used in this
study to investigate two different oils from one
petroleum system that show different mass/extent of
deposited solids. Both oils are similar in thermal
maturity and are related to the same organofacies but
trace to different lithofacies sources. The crude oil
related to a carbonaceous lithofacies has much higher
amounts of deposited solids than the oil related to a
shaly facies. We compared the asphaltenes from the
parent oils and from the organic solid deposits using
different pyrolysis techniques, elemental analysis, and
UV-visible spectroscopy. Maltenes extracted from the
solid deposits were compared to the parent oils in
terms of bulk composition and biomarker
characteristics using gas chromatography time-offlight
mass spectrometry.
Oil asphaltenes from both parent crudes are very
similar in chemical structure, as indicated by the
analytical techniques. This supports same
organofacies for the oils. Previous studies have
suggested that asphaltenes extracted from organic
deposits are enriched in oxygenated species and
multiple heteroatom classes compared with their
crude oil counterpart [2]. The results of this study
showed that asphaltenes from the deposition cell
reflect only slightly higher aromatic character than
those extracted from the parent oils. This finding
suggests particles of lower molecular weight are
enriched in deposits, which increase slightly the
aromaticity and thermal stability (Fig. 1), and the
atomic O/C ratio of asphaltenes. However, no findings
based on chemical differences between asphaltenes
explained the differences in the deposits.
The occluded maltenes in deposits, however,
differed significantly from those in related parent oils
and between the carbonaceous and shale-sourced
oils. Generally, the abundance of GC-unresolved
complex molecules (UCM), isoprenoids, and cyclic
saturates is much higher in occluded maltenes than in
related parent oils. Occluded maltenes are more
abundant in the deposition cell deposit from the
carbonaceous oil. These maltenes also show a
greater number of biomarkers and aromatics than
those in the deposition cell deposit from the shalesourced
oil.
The results of this study suggest that extent of
asphaltene deposition in a high-pressure deposition
cell is not controlled by asphaltene properties. The
composition of the parent oil (e.g., maltenes) also
impacts the depositional characteristics.
Fig. 1 Activation energy distribution for n-C7 - asphaltenes
from a parent crude oil and for n-C7 - asphaltenes extracted
from related organic solid deposition control experiments.
References
[1] Akbarzadeh, K., Ratulowski, J., Lindvig, T., Davies, T.,
Huo, Z., Broze, G. (2009) SPE 124956-PP.
[2] Juyal, P., Yen, A.T., Rodgers, R.P., Allenson, S., Wang,
J., Creek, J. (2010) Energy Fuels 24, 2320–2326.
470

P-340
Atypical fluids in offshore shallow buried reservoirs
Denis Levaché, Christine Lafaurie, Yannick Poirier, Gérard Ségalini
TOTAL Exploration & Production, Pau, France (corresponding author:denis.levache@total.com)
In (deep)offshore exploration, shallow buried
reservoirs are usually avoided due to the strong risk
of biodegradation and consequently highly viscous
fluids. Indeed the maximum risk of biodegradation
being situated towards 40-50°C, reservoirs around
900-1000m of depth are the riskiest.
However recent discoveries of light fluids in reservoir
at shallow depths have triggered questions regarding
the charge and preservation of the HC in these
reservoirs.
Typically these fluids have an apparent low
biodegradation level and good physical properties (i.e.
low in-situ viscosities and API above 30°). Strikingly
the molecular distribution of the oil is very unusual as
seen in Figure 1. Almost no n-alkane is present after
n-C17/C18 where Pristane and Phytane dominate.
The geochemical study on liquids by GC and GC-MS,
detailed analysis of associated gases (composition
and isotope ratio measurement � 13 C and � 2 H) and
mud gas analyses allow to propose a complex filling
history of these reservoirs involving multiple steps:
� A first phase of filling by an early charge that
is quickly biodegraded in reservoirs
subjected to temperatures lower than 60°C.
Such fluids are usually encountered in the
shallow reservoirs of these formations.
� The second phase of filling by retrograde
condensation of a light fluid and also
possibly a stripping by methane. The
reservoirs cannot hold the gas phase thus
generated as shown by the isotopic analysis
of mud gases that indicates continuous gas
fluxes from deeper origin.
The remaining fluid consists of the retrograde
condensate overprinting the initial biodegraded
charge.
The use of the geochemical interpretation helps to
build the proper thermodynamic model that match the
behavior of these fluids in these reservoirs. The
model used here involves two source rocks that have
expelled at various stages of maturities. The predicted
expelled fluids placed at the reservoir conditions have
a behavior in good agreement with the observed fluid
composition.
Norm.
Finally 1400 the understanding of the presence of these
gas fluxes is the main driver to predict the HC fluid
quality and thus the success of a prospect in these
1200
shallow reservoirs.
1000
800
600
400
200
0
*FID1 A, (L:\POLE MOLECULAIRE\GC-ID\ANALYSES\CAMEROUN 2008\NJOM001B\165171ID.D - NOVEMBRE\BL081118.D)
nC6
nC5
nC7
nC8
nC9
nC10
nC11
nC12
nC13
nC14
nC15
0 25 50 75 100 125 150 175 200 225
nC16
Pr
nC17
nC18
Ph
N-alkanes depleted from nC18
Fig.1 C6+ fraction Gas Chromatography of a selected
atypical oil.
471
min

P-341
Simulation studies on the adsorption/occlusion phenomena
inside the macromolecular structures of asphaltenes
Jing Zhao 1,2 , Zewen Liao 1 , Patrice Creux 2 , Anna Chrostowska 3 , Alain Graciaa 2
1 State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of
Sciences, Guangzhou, China, 2 Laboratoire des Fluides Complexes, UMR 5150 TOTAL-CNRS-UPPA, Pau,
France, 3 Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux, UMR CNRS 5254,
UPPA, Pau, France (corresponding author:liaozw@gig.ac.cn)
Some microporous units were found inside the
macromolecular structures of asphaltenes, and some
other molecules can be occluded inside these
structural units. Mild oxidation treatment was applied
to release these occluded compounds and their
geochemical significance probed (Liao et al., 2006).
However, the adsorption/occlusion phenomena inside
asphaltenes are not commonly recognized by the
research colleagues and more efforts needed for
some further work in this field.
Then the asphaltenes, prepared from one low
matured crude oil from the Shengli Oilfield, North
China, was applied to simulate the occlusion
processes for the deuterated alkane n-C20D42 under
the conditions of high T, P. Three batches of
simulation experiments were performed under 240,
270 and 290 o C, respectively with the pressure at
20MPa inside the gold tubes for 72, 48 and 24 hours,
respectively. At the same time the control experiment
was carried out under ambient conditions. The
pyrolysates from the simulation experiments and the
mixtures from the control experiment were Soxhlet
extracted successively by n-hexane and acetone, and
then the occluded fractions were obtained according
to Zhao et al. (2010).
The experimental results indicate that
adsorption/occlusion extensively took place inside
asphaltenes. Fig.1 as exemplified from one simulation
experiment showed that the deuterated hydrocarbon
n-C20D42 was occluded inside the asphaltenes, while
n-C24D52 was used as the internal standard for
quantifying n-C20D42. Amounts of the occluded n-
C20D42 inside asphaltenes for different simulation
experimental compositions and the control experiment
were reported in Fig.2.
Adsorption/occlusion may occur through chemical
processes, e.g. polymerization or condensation of the
functional groups of the asphaltene molecules, and
then caves developed inside which some other
molecules are trapped. On the other hand,
adsorption/occlusion can take place through physical
processes possibly by the strong polar-polar
interactions such as H-bonding between asphaltene
molecules, and then inside the networks some other
compounds are trapped.
Fig.1. Chromatogram of the n-hexane eluents from
the oxidation products of pyrolysates from one
simulation experiment.
Fig.2. Histogram of the amounts of n-C20D42 (the
occluded fraction) from the pyrolysates from different
simulation experiments (based on the amount of initial
n-C20D42; CE for the result of control experiment).
References
Liao, Z., Geng, A., Graciaa, A., Creux, P.,
Chrostowska, A., Zhang, Y., 2006. Organic
Geochemistry 37, 291-303.
Zhao, J., Liao, Z., Zhang, L., Creux, P., Yang, C.,
Chrostowska, A., Zhang, H., Graciaa, A., 2010.
Applied Geochemistry 25, 1330-1338.
472

P-342
Chemometric analysis of crude oil composition and fluid
properties
Andreas Linge Tomren 1 , Tanja Barth 1 , Kjetil Folgerø 1,2 , Johan Carlson 1,3
1 University of Bergen, Bergen, Norway, 2 Christian Michelsen Research, Bergen, Norway, 3 Luleå University
of Technology, Luleå, Sweden (corresponding author:andreas.tomren@kj.uib.no)
Background: Multiphase flow meters provide online
monitoring of the flow rates of oil, water and gas in
pipelines for the oil industry. Multiphase meters can
help optimize the petroleum production, increasing
the oil recovery and lowering the investments and
operational costs [1][2]. Due to the complex composition
of petroleum, the accuracy of the multiphase
meters may still be enhanced, which can be done by
improved understanding of the relationship between
chemical variability and physical principles that
determine fluid properties and behaviour. Multivariate
analysis of different data types describing the
chemical composition of crude oils relative to their
electrical, physical, chemical and magnetic properties
have therefore been carried out. The aim of the
present work is to identify correlations between the
crude oil properties and composition, and to see if it is
possible to build quantitative calibration models
describing the influence of oil composition on the
measured signals used for online monitoring.
Results: Principal Component Analysis (PCA) [3]
performed on Infrared (IR) spectra of a set of crude
and model oils show that three groupings occur,
separating biodegraded oils, nonbiodegraded oils and
condensates. PCA performed on Gas Chromatography
(GC) data of the same set of crude and model
oils show similar groupings, indicating that it is
possible to separate the three types of oils.
Partial Least Squares [4] calibration models for
prediction of different properties based on GC and IR
have been built. Some models give good results, for
example for density, permittivity and the biodegradation
level. This indicates that the models can
predict some unknown properties of new oils based
on GC and IR data with reasonably good results.
Predicted (e_st)
2.80
2.60
Predicted vs Measured for e_st
2.40
2.20
29
4
10 3
12
1
7
5
6
2.00
8
2.00 2.20 2.40 2.60 2.80
Measured (e_st)
Figure 1: Plot of predicted vs measured value for
prediction of static permittivity based on GC data. Red
numbers indicate objects used to build the model,
blue numbers indicate objects that were used to
validate the predictive quality of the model. A
maximum of 5% error was obtained
More complex relationships have also been explored
with the aim of quality control of the multiphase meter
settings. At present, the signals used to quantify the
phases are calibrated at the initial startup of each
measuring unit, and changes in oil composition over
the production lifetime may require recalibration for
accurate measurement. Models that relate the
signals to oil composition based on widely available
chemical crude oil characterisation techniques are
being developed and tested for practical applications.
[1]: Thorn, R.; Johansen, G.A.; Hammer, E. A. Threephase
flow measurement in the offshore oil industry:
Is there a place for process tomography. In
1st World Conference on Industry Process Tomography,
Buxton, Greater Manchester, U.K., 1999.
[2]: Falcone, G.; Hewitt, G.F.; Alimonti, C.; Harrison,
B. Multiphase flow metering: Current trends and
future developments. J. Pet. Technol. 2002, 54, 77.
[3]: Wold, S.; Esbensen, K.; Geladi, P. Principal com
ponent analysis. Chemometrics and Intelligent Laboratory
Systems, 1987, 2, 37.
[4]: Hoskuldsson, A. A combined theory for PCA
and PLS. J. Chemometrics 1995. 9, 91.
11
473

P-343
Effective diffusivities of CO2 and associated noble gases in
impermeable shale caprocks of an EOR-CO2 field
Caroline Magnier 1 , Alain Prinzhofer 1 , Eric Flauraud 1 , Sophie Giannesini 1,2
1 IFP New Energy, Rueil Malmaison, France, 2 IPGP, Paris, France (corresponding
author:caroline.magnier@ifpen.fr)
Present research on CCS (Carbon Capture and
Storage) is concerned on mitigation options for the
increasing atmospheric CO2 concentrations. The
petroleum industry is studying different liabilities for
the injection of acid gases in geological structures,
deep saline aquifers or depleted petroleum reservoirs.
Some of the options are thought for permanent
storage if and when a good efficiency of seal rocks is
proven to acid gas mobility. In that respect, recent
experimental studies have been described that
estimate gas migration distances in overlying low
permeability cap rocks when CO2 gas, dissolved or
not, plumes upward in geological sediments by
diffusion or advection flow, through faults or leaking
wells.
If shales and limestones sediments are mostly
encountered as seals above hydrocarbon
accumulations and over CO2 potential storage
reservoirs, it is because shales are impermeable
natural barriers. This is one of the reasons why it is
important to assess their capacity to remain
impermeable to fluids, regardless of what is injected
in the underlying cavities.
Experiments on clays were conducted on different
rock sediments of an EOR-CO2 field to investigate
the transport by diffusion of CO2 and noble gases in
water saturated pore networks. Effective diffusivities
for each gases were obtained by a model and
compared as a function of the rock type.
pressure
gauge
pressure
gauge
CO 2 +
noble
gases
parent
other gas
daughter
sampling
zone
Rock sample
sampling
zone
sample
primary / secondary
vacuum
sample
primary / secondary
vacuum
Figure 1: The experimental setup for measuring effective
diffusivities of gases in saturated pores
The experimental setup consists of a stainless steel
reactor with separate gas reservoirs (parent/daughter)
with volumes of 175 cm 3 filled and put at near equal
pressures.
A gas is mobile with a same flow rate in a given rock
type regardless of the porosity while a gas production
is inversely proportional to the thickness of the
sample (Figure 2).A gas is mobile with a same flow
rate in a given rock type regardless of the porosity
while a gas production is inversely proportional to the
thickness of the sample (Figure 2).
The dissolved CO2 gas migrated differently in the
natural clays. The lowest CO2 retention was found in
caprocks 1 with a Dw/Deff ratio between 15-18 while
caprock 2 or caprocks 3 (B-45) have greater CO2
retention, with Dw/Deff ratios at 30 and 45 respectively.
Noble gases followed a decreasing mobility from
helium, neon, argon and krypton respectively,
krypton being very much more retained.
% CO2 PRODUCTION
20
15
10
5
0
Caprock 1 (B-419)
B-419 5 mm
B-419 10.2 mm
B- 419 12.6 mm
0 500 1000 1500 2000
TIME (HRS)
Figure 2: CO2 production vs. time in a shaly caprock sample
The effective diffusivity of helium was found to
be equal to the rocks tortuosity.
From such results, larger scale simulations of
gas flows of CO2 associated with inert tracers
with effective diffusion rates or ratios of diffusion
rates between gas compounds in a given rock
type are now considered in order to attempt to
quantify leakage amounts CO2 in aquifers.
% CO2 PRODUCTION
20
15
10
5
0
0 20 40 60 8
t Dw /L 2 (ADIMENSIONAL)
474
B-419 5 mm
B-419 10.2 mm
B- 419 12.6 mm

P-344
Can mud gas tell us a bigger story?
Daniel McKinney, Heidi Albrecht
Shell <strong>International</strong> E&P, Inc., Houston, United States of America (corresponding
author:daniel.mckinney@shell.com)
Traditionally, mud gas analysis has consisted of
qualitative mud gas extraction coupled to a slow, low
resolution GC-FID gas analyzer. These mud gas
logging techniques look at only a small portion of the
entire reservoir fluid, typically methane through
pentane, with only qualitative assessment of some
isomers of C6 in advanced systems (e.g., benzene, n-
C6, and cyclohexane). In contrast, open hole
samples permit the chemistry and petroleum system
analysis of the gasoline range hydrocarbons, mainly
isomers of C6 and C7, as well as full biomarker
studies. Past efforts have developed these methods
to yield fundamental understanding about an oil or
condensate's geochemical history such as
biodegradation, water washing, source rock origin,
thermal maturity, etc. (See Mango, 1997 and
references within). But what if you do not have an oil
sample? Can you get the same type of C6 or C7
isomer analysis from a mud gas sample?
In this study, we investigate the potential of C6 and
C7 isomer analysis from isotube® samples of
entrained mud gas collected from Geoservices' FLAIR
system (Breviere et al., 2007). The FLAIR system
was essential for this study as it assesses the
extraction efficiency of C1-C5 in the drilling mud. An
extraction efficiency coefficient (EEC) is calculated for
each unique well and drilling mud combination and
applied to each C6 and C7 isomer as a function of
boiling point. Figure 1 shows the C7 ternary ring
preference diagram for 3 separate prospects using 3
different mud systems: A) water based mud (WBM),
B) Saraline 185V OBM, and C) Accolade OBM. EEC
corrected isotube data, for the majority of the samples
analyzed, mimicked the standard C6/C7 analysis
approach, within reasonable expectation, when
compared to oil samples collected from the same
intervals. A few notable exceptions were documented
which were mainly tied to contamination from drilling
mud. For example, Saraline 185V base oil, is a broad
molecular weight aliphatic mixture, and it
contaminated the isotube sample (Isotube B in Figure
1) with additional n-heptane. Isotube samples
collected from WBM yielded the best match to the
reservoir fluid, and the isotube sample collected from
the Accolade drilling mud was only slightly impacted
by contamination; most likely from recycling issues.
Thus, this methodology allows the geochemist to
gather additional information, relative to the standard
mud gas and show analysis reports, to further
fingerprint reservoir hydrocarbons.
Figure 1. C7 ring preference comparison between FLAIR
isotube and oil obtained from the same reservoir interval: A =
WBM, B = Saraline 185V OBM, and C = Accolade OBM.
References
[1] Mango, F.D. (1997) The light hydrocarbons in
petroleum: a critical review. Org. Geochem. 26, 417-440.
[2] Breviere J., Lessi, J., Jaulneau, P. and Shell‘s
FEAST Team (2007) Abstract. 23 rd <strong>International</strong> <strong>Meeting</strong> on
Organic Geochemistry, Torquay, United Kingdom.
475

P-345
Oil Fingerprinting associated with Well Temperature Profiles as
an Alternative Production Logging Tool
Alain Noyau, Dominique Andre, Jan Mersmann, Francois Dabat
TOTAL Centre Scientifique & Technique, Pau, France (corresponding author:alain.noyau@total.com)
To monitor reservoir production when wells produce
multiple zones it is necessary to allocate the
production of each formation. The most commonly
used technique is the PLT (Production Logging Tool)
acquisition using various sensors such as spinner,
densimeter, pressure and temperature, the last one,
being rarely used or only for qualitative data until
recently.
However PLT interpretation is occasionally unreliable
or even unachieved.
Reservoir geochemistry based on statistical
processing on molecular fingerprints of oils or
condensates using Gas Chromatography (GC)
techniques has been successfully applied for decades
as a PLT alternative tool for production allocation.
Contamination-free DST reference samples with
clearly different signatures are usually needed for
production split calculations.
The goal of this paper is to demonstrate that
allocation can also be successfully done using a
combination of:
- Molecular fingerprinting of oils from downhole
samples containing OBM contaminants used as
references (end-members).
- A quantitative interpretation of PLT temperature
sensor tool string and pressure data.
In this particular case study a classical PLT was run.
However due to high formation temperature and
consequent electronic failure, spinner data acquisition
was not possible but a temperature data interpretation
was performed to estimate production influx at each
layer. In addition, geochemical analysis by fingerprints
of the oil samples taken at surface during the test and
downhole acquisitions was carried out. These
analyses validated the flow profiles per interval
resulting from the temperature log matching (see
illustration).
Excellent split concordance is obtained between
allocation by geochemistry (25-75%) and using
temperature flow profiles (24-74%) for the PLT2
sample. It provided confidence to calculate the
allocation of the PLT3 (18-82%) using only
geochemical fingerprinting in absence of a reliable
temperature data. Moreover cross flow was identified
for the PLT1 since there was discrepancy between
the geochemical and the temperature results.
In the past, when spinner failed, a new PLT run was
often performed leading to additional cost and lost
time of production.
Oil fingerprinting in tandem with well temperature
profiles can be two complementary operational tools
with strong impact in the deep offshore context for
reservoir monitoring purposes when traditional PLT
acquisition is challenging and costly.
476

P-346
Diamondoids, a tool in the geochemical studies to identify
compartmentalized reservoirs
Adriana Pérez 1 , Ingrid Alfonzo 1 , Federico Galarraga 2 , Carmen Rodríguez 1 , Ricardo
Harner 1 , Ysmarline Rincones 1
1 PDVSA-Intevep, S.A., Los Teques, Venezuela (Bolivarian Republic of), 2 Instituto de Ciencias de la Tierra.
Universidad Central de Venezuela, Caracas, Venezuela (Bolivarian Republic of) (corresponding
author:perezacy@pdvsa.com)
In this study were evaluated the distribution
specifically diamondoids group of adamantanes and
diamantanes, in condensate samples from two
producing fields (Santa Rosa and Pirital) in the area
of the Oriental Basin of Venezuela, in order to assess
geochemical parameters proposed based on the
abundance, distribution and relations of diamondoids
compounds to identify families and/or groups that
permit the inference reservoir communication.
These compounds were analyzed by CG-MS and
quantified by using certified standards (adamantane;
1-methyladamantane; 1,3-dimethyladamantane;
1,3,5-trimethyladamantane; 2-methyladamantane;
1,4-dimethyladamantane (cis); -1,4dimethyladamantane
(trans); 1,2-
dimethyladamantane; 1-ethyladamantane; 1-ethyl-3methyladamantane;
2-ethyladamantane, diamantane
and 1-methyldiamantane). The following ions were
monitored for diamondoids analysis: m/z 135, 136,
149, 163, 187 and 188.
In the Santa Rosa Field were evaluated the CW-1,
CW-2, CW-3 and CW-4 samples, which are come
from Interval B of San Juan Formation of Cretaceous
age (Maastrichtiense), Interval A of Vidoño Formation
of Cretaceous (Campanian) - Tertiary (Early Eocene)
age, and the sands of Oficina Formation of Early-
Middle Miocene age, interval K and I of Moreno
Member, respectively. In the Pirital Field, the samples
evaluated: CY-1, CY-2, CY-3 and CY-4,
corresponding from 4 wells producing from some
sandstones Naricual Formation of Late Oligocene
Early Miocene age, only the sample CY-2 was taken
from the sand KP corresponding to Cretaceous-
Paleocene (?) unit. The concentration of diamondoids
compounds in samples condensates were in a range
from 121.82 to 22563.63 ppm (mg/L), considering all
the compounds evaluated in two fields.
In the Santa Rosa Field, according to the previous
characterization of the samples, the condensed CW-1
and CW-2 are compositionally correlated, thus
suggesting that units have vertical communication.
For samples CW-3 and CW-4, they also reveal
vertical communication because the samples are
compositionally similar, but different to samples CW-1
and CW-2. In both cases, the abundance of
diamondoids compounds in terms of concentration
were similar (relatively similar orders of magnitude) in
addition to the parameters of maturity, level of
biodegradation and depositional environments as well
as type of organic matter were similar for each of the
families or groups of samples. These results support
the compartmentalization of these reservoirs.
In the Pirital field, samples CY-1 and CY-3 showed a
positive correlation in the parameters evaluated from
the concentration of diamondoids compounds
confirming the communication of fluids. It was
suggested to by other author through the analysis
conventional parameters. The CY-2 and CY-4
samples even previous studies suggest that they are
compositionally similar however, from the point of
view of diamondoids concentration there is differ
considerably by several orders of magnitude, so these
samples are not similar, and this which might suggest
that both reservoir (Cretaceous - Paleocene unit (?))
and sand 5 of Naricual Formation) are not connected.
Regarding the parameters evaluated as source,
maturity and alteration by biodegradation, only there
are differences in the EAI (Index Ethyl-Adamantane)
which assesses the relationship origin. It could
explain the high concentration of diamondoids in the
sample CY-4. It is possible that condensates might be
related to variation in organic facies of the source rock
presenting a mayor terrestrial input, which could
explain the high values obtained in the EAI. However,
it requires further study in determining the
concentration of diamondoids in the condensates
produced in that field, so to determine if the
characteristics of this sample are identify in other
condensates.
477

P-347
Strategies for the assessment of fluid mixing in petroleum
systems
Stefanie Pötz, Andrea Vieth-Hillebrand, Heinz Wilkes
GFZ German Research Centre for Geosciences, Potsdam, Germany (corresponding author:poetz@gfzpotsdam.de)
The issue of fluid mixing is of increasing importance
for the assessment of petroleum systems. It is now
regarded as one of the key controls on petroleum
composition, properties and quality, since essentially
all petroleums are mixtures with different components
charged from source rocks at different temperatures
[1].
Reservoired oils may derive from mixing of
petroleums expelled from similar organic facies
source rocks at different maturities, from mixing of
petroleums from two (or more) different source rocks,
from mixing of petroleums with different levels of
secondary alteration, in particular biodegradation, as
well as from any combination of the aforementioned
types. Mixing processes are mainly driven by
differences in fluid density and composition and
limited by reservoir compartmentalisation.
Additionally, migration contamination in the carrier
may be a further mechanism of petroleum mixing.
Mixing has crucial but so far widely overlooked effects
on geochemical tools conventionally used in
petroleum system evaluation such as oil-oil- and oilsource-correlation
or maturity assessment. With
regard to multiple-sourced petroleum reservoirs,
many studies focus on the identification of the
different sources based on biomarker and/or carbon
isotopic compositions of crude oils or core extracts.
Geochemical approaches to quantify the contribution
from each source rock depend on calculations using
relative peak ratios from gas chromatography or
absolute concentrations. Relative peak ratios are now
considered unreliable due to non-linear mixing
behaviour. For most of the applications described in
the literature, which are based on absolute
concentrations, end-member oils of each source rock
have to be available for geochemical treatment. This
is crucial because the availability of the correct endmember
oils is an extremely unlikely case in real
world petroleum exploration. The quantitative
determination of the contribution of mixing petroleums
to different component fractions of the resulting fluid is
even less well constrained. With this in mind improved
and reliable tools are required to assess the
relevance and effects of petroleum mixing during
petroleum system evaluation.
Inconsistencies in petroleum composition considering
different component fractions of the oil which may
have been contributed from different mixing
petroleums to a different extent are the main criterion
to identify mixed oils. An example is the determination
of different maturities for a single oil from parameters
based on light hydrocarbons, aromatic hydrocarbons
and biomarkers. In general, trace components are
less reliable for the assessment of mixing than main
components. Likewise, components varying in
concentration over several orders of magnitude are
less reliable than those varying over only one (or two)
order(s) of magnitude. The often used biomarker
approaches overestimate the proportion of the
contributing petroleum with the higher biomarker
concentrations. So far no generalisable procedures
are known that allow an unequivocal assessment of
mixing in natural petroleum fluids.
In this study mixing was investigated for crude oils of
3 different study areas (Offshore West Africa,
Offshore Norway, Western Desert in Egypt) with the
focus on quantitative compositional differences of
main and trace compounds and the carbon and
hydrogen stable isotopic composition of individual
components within the crude oils. In addition, artificial
mixing experiments have been done to evaluate linear
and nonlinear mixing behaviour and the influence of
differences in the absolute concentration of
compounds in the contributing oils on the ―endconcentration‖
in the mixed petroleum. This
contribution will discuss the implications for the
assessment of mixing processes and the use of
geochemical tools in petroleum exploration.
References
[1] Wilhelms A. and Larter, S., In: Cubitt, J.M.,
England, W.A., Larter, S.R. (Eds.), Understanding
Petroleum Reservoirs: Towards an Integrated
Reservoir Engineering and Geochemical Approach.
2004. Geological Society, London, pp. 27-35.
478

P-348
Distribution of tetraprotic (―ARN‖) acids in different oilfield
deposits determined using high temperature gas
chromatography and liquid chromatography-electrospray
ionisation mass spectrometry
Paul Sutton 1 , Steven Rowland 1 , Ben Smith 2
1 University of Plymouth, Plymouth, United Kingdom, 2 Oil Plus Limited, Newbury, United Kingdom
Regioisomeric mixtures of C80 tetraprotic (―ARN‖)
acids with 0 - 8 cyclopentyl rings are regarded as the
principal organic components in calcium naphthenate
deposits encountered in some oilfields [1,2] . These
compounds are H-shaped with an acid group at the
end of each ‗arm‘ (eg Fig 1) and have the generic
formula CnH(2n-6)-(2R)O8 (n = carbon number, R =
number of rings), range in molecular weight from
1243 – 1227 Da at 2 Da intervals for 0 – 8 rings,
respectively, have z-numbers from -6 to -22 at -2
intervals (for 0 – 8 ring, respectively) and double bond
equivalence of 4 - 12 DBE ( 0 – 8 ring, respectively).
To date, most of the research into this family of
tetraacids has been directed towards their
involvement in deposit formation [eg 3] . Besides interest
in the role of C80 tetraprotic acids in deposit formation
they are also of geochemical interest as they possibly
constitute a biomarker signal from parent oil
reservoirs.
H
O
O
H
O
O
O
O
Fig 1. Structure of C80 tetraprotic acid with 6 rings [1]
H
O
O
H
We have isolated the C80 tetraprotic acids from five
deposit samples, three from different North Sea
locations and two from different West African
locations. Isolated acids were converted to their
methyl esters and the relative distribution in different
deposits determined using high temperature gas
chromatography (HTGC) and identification using
liquid chromatography coupled with electrospray
ionization-mass spectrometry (LC-ESI/MS).
Typically all deposits contained C80 tetraprotic acids
as major constituents with 2 – 8 rings, however the
distribution by ring number varied between deposits.
The C80 tetraprotic acid with 6 rings dominated all
deposits (~45 – 50%; eg Fig 2) except one from the
North Sea which contained higher amounts of 7 and 8
ring compounds (36 and 37%, respectively; Fig 3).
Distributions of other homologs varied to a lesser
extent.
response (pA)
300
200
100
2R
3R
4R
5R
6R
0
35 36 37 38 39 40 41 42
7R
retention time (min)
Fig 2. HTGC chromatogram of C80 tetraprotic acid
methyl esters from a West African deposit
response (pA)
300
200
100
4R
5R
6R
8R
8R
7R
0
35 36 37 38 39 40 41 42
retention time (min)
Fig 3. HTGC chromatogram of C80 tetraprotic acid
methyl esters from a North Sea deposit
Identification of the original source of C80 tetraprotic
acids in oilfield deposits, whether from: novel extant
reservoir archaeal lipids, degradation products of
archaeal ether lipids, or produced by oil degrading
archaea as biosurfactants [4] , remains unresolved.
However, we have demonstrated the varied relative
distribution of C80 tetraprotic acids in different oilfield
deposits.
[1] Baugh et al. (2005) SPE93011
[2] Sutton et al. (2010) Rapid Commun. Mass
Spectrom. 24, 3195-3204
[3] Shepherd et al (2006) SPE 100517
[4] Lutnaes et al (2006) Org. Biomol. Chem. 4, 616-
620
479

P-349
Fluid pressure evolution and gas preservation of the Puguang
Gasfield, Sichuan Basin, China
Xiao Xianming, Liu Dehan, Tian Hui
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of
Sciences, Guangzhou, China (corresponding author:xmxiao@gig.ac.cn)
Previous studies have indicated that the natural gas
of Puguang Gasfield of the Sichuan Basin, China, is a
typical oil-cracking origin. However, there is no report
on the fluid pressure evolution and gas preservation
related to the oil cracking processes of this reservoir
during geological history. This study investigated the
fluid pressure variation and its influences on loss and
storage of hydrocarbons in the reservoir of the
Puguang Gasfield by means of PVTsim software
modeling based on the gas generation kinetics of oil
cracking and geothermal history of this area. The
result has shown that the fluid pressure was 25 – 50
MPa with a pressure coefficient less than 1.2 during
175 to 157 Ma in the reservoir where oil was not
cracked. The oil was significantly cracked from 157Ma,
which resulted in a fast increase of pressure in the
reservoir. At about 142 Ma, the pressure coefficient
reached 2.4 in the reservoir when about 80% oil was
cracked into gas. The seal rock was broken under this
pressure condition, the gas leaked out and the
reservoir pressure returned to the hydrostatic
pressure. It was supposed that the reservoir was resealed
after the gas leakage, and its pressure would
increase again with residual oil cracking and
subsequently the secondary cracking of C2-5
hydrocarbons. At 132 Ma, the pressure coefficient
reached 2.4, gas leaked out and the reservoir was resealed
again. It is estimated that about 23% and 33%
of petroleum in the reservoir was loosed during the
two times of break, respectively. In the interval of 132
- 96Ma for further burial of the gas reservoir, the
pressure was mainly affected by temperature increase
since the C2-5 gas was almost cracked during the
previous two stages. In the interval of 96Ma to the
present time, this area was uplifted to erode about
2800 m thick sediments, the pressure of the gas
reservoir, as affected by temperature decrease,
decreased to 56.9-61.0MPa, with a current pressure
coefficient of 1.1. It is estimated that about 46% of gas
resulted from oil cracking was preserved in the
reservoir to form the current gas pool. The
overpressure resulted from gas generation due to oil
cracking was validated by a discovery of high density
(0.34-0.35 g /cm 3 ) methane inclusions from reservoir
rocks. This type of inclusions has a trapping pressure
up to 150-160MPa, with a pressure coefficient of 2.0-
2.2. This present research provides a case study of
an oil-cracking origin gas pool and its fluid pressure
evolution, which is useful to gas exploration in areas
with similar geological and geochemical conditions in
China petroleum-bearing basins.
Keywords: Puguang Gasfield; oil-cracked gas; high
density methane inclusion
480

P-350
Geochemical comparison of oil samples and core extracts from
Yanchang Formation in Ordos Basin, China
Weiwei Yang, Guangdi Liu
State Key Laboratory of Petroleum Resource and Prospecting in China University of Petroleum, Beijing,
China (corresponding author:yangweiwei_850101@yahoo.com.cn)
Geochemical analysis of core extracts is often in
place of oil samples for oil-source correlation and
exploration when no tested or produced oil samples
are available. The geochemical characteristics of
solvent extraction from cores and tested or produced
oil are similar, but some differences have been
observed between them (Horstad et al., 1990; Larter
and Aplin, 1995; Stoddart et al., 1995; Baylis, 1998;
Jianhui Feng et al. 2003).
In order to identify the differences, a geochemical
study was carried out to compare the geochemical
parameters obtained from the analysis of tested oil
samples and reservoir cores extracts in the laboratory
using GC and GCMS. In Yanchang Formation of
Ordos Basin, eight tested oil samples and eleven
cored reservoir samples from the same horizons were
collected and analyzed from six wells. The results
show that the oil samples are more enriched in lighter
molecular weight components than that of the core
extracts, with the C21-/C22+ ratios ranging from 2.1 to
3.7 much higher than those of the core extracts
ranging from 0.9 to 1.3. This phenomenon is due to
evaporation during cores preserved in the core
storage for many years. Besides, remarkable
differences are observed between the distribution
patterns of terpanes for some of the oil samples and
their respective core extracts samples, from the same
intervals in the same wells, which demonstrates the
heterogeneity of tested intervals. Some source
indicators, e.g. relative contents of 17α (H)-C30
diahopanes (C30*) and tricyclic terpanes, suggest that
oils from extracted reservoir cores and produced oil
samples derive from different types of sources. Take
the Well Bai284 (Chang8 Member) for example, the
tested oil sample (1857-1862m) is lower C30* and
tricyclic terpanes contents relating to the oil shale,
whereas the solvent extraction from the core
(1857.9m) is higher C30* and tricyclic terpanes
contents relating to the black mudstone.
So examination of core extracts instead of tested or
produced oils may be misleading in oil-source
correlation, we should take these differences into
account in exploration.
References
[1] Baylis, S.A. (1998) Geochemical comparison
of core extracts and oil samples in reservoir. Organic
Geochemistry 29, 463-484
[2] Horstad, I., Larter, S. R., Dypvik, H., et al.
(1990) Degradation and maturity controls on oil field
petroleum column heterogeneity in the Gullfaks field,
Norwegian North Sea. Organic Geochemistry 16,
497-510.
[3] Jianhui, F., Yuming, T. Xiaoping, L. et al.
(2003) Geochemical comparison and implications of
oils, core extracts and oil-bearing fluid inclusions in
reservoirs of Dongpu Depression. Geochemica 32,
591-600
[4] Larter, S.R., Aplin, A.C. (1995) Reservoir
geochemistry: methods, applications and
opportunities. In the Geochemistry of Reservoir, eds.
Cubitt J.M., England, W.A., Geological Society
Special Publication 86, 5-32
[5] Stoddart, D.P., Hall, P.B., Larter, S.R., et al.
(1995) The reservoir geochemistry of the Eldfisk field,
Norwegian North Sea. In the Geochemistry of
Reservoir, eds. Cubitt J.M., England, W.A.,
Geological Society Special Publication 86, 257-279
481

P-351
The releasing of covalently-bound biomarkers via
hydropyrolysis for the bitumen-source correlation of Majiang
paleo-reservoir
Fang Yunxin, Geng Ansong, Liao Yuhong, Wu Liangliang
Guangzhou Institute of Geochemistry,Chinese Academy of Sciences, Guangzhou, China (corresponding
author:asgeng@gzb.ac.cn)
There are different viewpoints on the bitumensource
correlation of Majiang paleo-reservoir in the
Southern Guizhou Depression of China. Three
potential source rocks in this depression could be
inferred: the Lower-Cambrian marine mudstone,
Lower-Silurian shale and Lower-Permian mudstone.
Most of the potential source rocks and solid bitumens
are of high maturity. The low yields of extracts from
bitumens and source rocks in Majiang area can not
satisfy the detection limit of analytical instruments,
such as GC-MS and GC-IRMS. And the severe
thermal alterations obscure oil-source correlations by
routine biomarkers of extracts. Routine biomarkers in
EOM of source rocks and solid bitumen, such as
C27~C29-regular steranes and C31~C35 homohopanes,
may be altered during maturation. Due to all these
factors, it is difficult to use routine biomarkers of
extracts for the bitumen-souce correlation.
Catalytic hydropyrolsis refers to pyrolysis assisted
by high hydrogen pressure (15 MPa) and a dispersed
sulfided molybdenum catalyst, which permits covalent
bond cleavage at relatively low temperature (

P-352
Experimental simulation of gravity/density segregation by
centrifugation
Fenglou Zou, Kentaro Indo, Eric Lehne
DBR Technology Center, Schlumberger, Edmonton, Alberta, Canada (corresponding author:fzou@slb.com)
Compositional variations in reservoir fluids with depth
are common and have been observed in many
reservoirs throughout the world. This phenomenon is
not limited to thick reservoirs, but is also observed
over relatively short vertical columns. It also occurs in
reservoirs containing gas condensates or volatile oils,
as well as heavy oil reservoirs [1, 2].
Fluid gradients can originate from gravitational or
density segregation, thermal gradients, water
washing, biodegradation, fluid-rock interactions,
multiple charges to the reservoir, or leaky seals.
Compositional gradients can also occur in large oil
columns that are in apparent pressure
communication. Such pools are described as
segregated oil columns, showing characteristics of
changes in API gravity, gas-to-oil ratio (GOR),
composition or asphaltene content.
We present the results of experiments to simulate
gravitational segregation using a centrifuge technique
under reservoir pressure and temperature conditions
[3]. It is believed that asphaltene content strongly
determines the degree of segregation [4, 5]. We
compared compositional segregation characteristics
of two different oils: a black oil (oil #1) with 30 °API
and 5% asphaltene content, and a light oil (oil #2) with
40 °API and less than 0.5% asphaltenes. Oil #1 is
from marine shale source rock with Rc (calculated
vitrinite reflectance from methylphenanthrene index)
of 0.68, and #2 is a Tertiary oil from terrigenous shale
source rock with Rc of 0.83. Different cuts after
centrifugation, e.g. simulated reservoir depth, were
analyzed with UV-Vis spectroscopy, 2D GC-FID and
GC-FID and GC-MS.
GORs of the centrifuged cuts of both oil #1 and #2
do not show significant differences. However, the
analytical results from UV-Vis spectroscopy, 2D GC-
FID and GC-MS indicate that oil #2 exhibits vertical
compositional variation, while oil #1 lacks
segregation. The grading in oil #2 is obviously seen
from cut1 to cut7 (from top to bottom) that is at
equivalent field depth of 545 feet based on a
formula reported by Ratulowski et al. [3]. 2D GC-FID
as well as GC-MS analytical results indicate that the
main variation in oil #2 is in the abundance of
polycyclic aromatics, which complements the
analytical results from UV-Vis spectroscopy.
The study indicates that gravitational gradients are
not strictly related to asphaltene content and GOR,
but are also influenced by other oil properties, such
as thermal maturity and resin/aromatics ratios.
Figure 1. Compositional gradients in oil #2
observed by UV-Vis spectroscopy and 2D GC in
relation to simulated reservoir depth.
References
[1] Mullins, O.C., Betancourt, S.S., et al., 2007,
Proceedings - SPE <strong>International</strong> Symposium on
Oilfield Chemistry, 502-507.
[2] Fujisawa, G., Betancourt, S.S., et al., 2004,
Proceedings - SPE Annual Technical Conference and
Exhibition , 59-64.
[3] Ratulowski, J., Fues, A.N., Westrich, J.T., Sieler,
J.J., 2003, SPE 84777, 168-175.
[4] Indo, K., Ratulowski, J., Dindoruk, B., Gao, J., Zuo,
J., Mullins, O.C., 2009, Energy & Fuels 23, 4460-
4469.
[5] Hirschberg, A., 1988, SPE13171, 89-94.
483

P-354
Sulfur isotope fractionation during thermochemical sulfate
reduction as reflected by individual organic compounds
Alon Amrani 1 , Andrei Deev 2 , Alex Sessions 3 , Yongchun Tang 2 , Jess Adkins 3
1 The Hebrew University of Jerusalem, Jerusalem, Israel, 2 PEER Institute, Covina, United States of America,
3 California Institute of technology, Pasadena, United States of America
(corresponding author: alon.amrani@mail.huji.ac.il)
Thermochemical reduction of sulfate (TSR) to
sulfide and oxidation of organic matter involves
multiple reactions and redox changes. The
mechanism controlling this process is still enigmatic.
Attempts to study it were mainly focused on analysis
of inorganic sulfur reactants and products. However,
organic sulfur compounds have been shown to from
rapidly and affect significantly the rate of TSR (Amrani
et al., 2008). Their structural and isotopic analysis
may shed light on important and unexplored aspects
of the TSR mechanism.
In the present study, we performed a set of laboratory
simulation experiments to study how individual
organic compounds effected by TSR. The gold tubes
hydrous pyrolysis experiments performed at 360°C
with mineral buffer (silica gel and talc), n-C16 as an
organic model compound, and several inorganic
sulfur oxidizers, CaSO4, Na2SO4, Na2SO3 and S° with
distinct δ 34 S values. We applied a new technique
capable of measuring precise δ 34 S values in individual
compounds by GC-MC-ICPMS (Amrani et al., 2009).
We focused mainly on benzothiophenes (BT) and
dibenzothiophenes (DBT) as TSR tracers.
We observed large δ 34 S fractionation between DBT
and sulfates (Na2SO4 and CaSO4) of up to -21.6‰.
This fractionation was reduced rapidly with increase
of TSR reaction time, but never approached the initial
sulfate δ 34 S value. Hydrogen sulfide exhibits similar
fractionation as DBT at the earlier reaction time but
rapidly approach sulfate value. BT started with similar
fractionation as DBT but as the reaction proceeds it
has intermediates values between the DBT and H2S.
Experiments with 10 folds excess of sulfate have little
effect on the fractionation and the trend of reducing
fractionation with increasing TSR reaction time was
similar. The results for sodium and calcium sulfate
were close, suggesting that the dissolution of solid
CaSO4 was not a limiting factor. These results
suggest that other processes rather than the
concentration of sulfate, dominate the fractionation
during TSR. These processes may include isotopic
exchange between sulfate and it reduced forms that
mask the original kinetic isotope effect.
Experiments with elemental sulfur show small and
consistent δ 34 S fractionation between BT and initial S°
of -1 to -2.4 at all reaction times. This shows that the
δ 34 S recorded by the organosulfur compounds
reflecting the δ 34 S value of the TSR reduced sulfur
rather than isotope effect during their formation.
Therefore we can use organosulfur compounds as
markers for the δ 34 S of H2S derived from TSR.
The reaction with Na2SO3 yielded DBT and BT with
maximum fractionation of up to -9.6‰. As observed in
the experiments with sulfates, this fractionation
decreased rapidly with reaction time and BT changed
more rapidly than DBT. In this case H2S exhibit no
fractionation relative to Na2SO3 at all reaction times.
The fractionation during SO3 -2 reduction is surprisingly
large as the common assumption is that the most
significant fractionation occurs during the reduction of
SO4 -2 to SO3 -2 . The fractionation during SO3 -2
reduction could not be detected by H2S, because the
reaction is too rapid and mask the initial fractionation.
DBT can preserve the initial fractionation signal
because it stability and slow rate of formation. BT is
less stable and reflecting the cumulative δ 34 S values
during the course of reaction. These TSR markers
can therefore allow us to follow the initial steps of
TSR. Better understanding of these fractionations and
their kinetics will help us follow and understand more
closely TSR reaction mechanism.
References
Amrani, A., Sessions A.L., Adkins J. 2009.
Compound-specific δ 34 S analysis of volatile organics
by coupled GC/ICPMS. Analytical Chemistry 81,
9027-9034
Amrani, A., Zhang, T., Ma,Q., Ellis, G. S. ,Tang, Y.
2008. The role of labile sulfur compounds in
thermochemical sulfate reduction. Geochimica et
Cosmochimica Acta 72, 2960-2972.
484

P-355
H2S formation and enrichment mechanisms in Puguang gas
field of the Sichuan Basin, China
Tenger Borzijin 1,2 , Wenhui Liu 1,2 , Bo Gao 1 , Zhongning Zhang 3
1 Sinopec Research Institute of Petroleum Exploration and Production, Beijing, China, 2 Wuxi Institute of
Petroleum Geology, Sinopec Research Institute of Petroleum Exploration and Production, Wuxi, China,
3 Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou,, Lanzhou, China
(corresponding author:tenger@pepris,com)
The Upper Permian Changxing - Lower Traissic
Feixianguan formations (P2ch-T1f) is one of the most
important habitats for H2S-bearing gas pools in NE
Sichuan Basin, SW China. High H2S concentrations
(10-17%) in the Puguang gas field add great difficulty
for safe production, thus the mechanisms for H2S
formation and enrichment have therefore become an
important issue for our investigation. Thermochemical
Sulfate Reduction (TSR) involving hydrocarbon
cracking and S/Mg-enriched fluids is commonly
accepted mechanism for H2S formation in the studied
carbonate reservoirs. Sufficient reactants, enough
energy supply, adequate accumulation space and a
rigid reduction environment are the main controlling
factors for H2S formation and the enrichment in the
Puguang gas field.
Dissolution of sulfate can provide a rich source of
sulphur. Laboratory simulation experiments show that
significant amounts of H2S are formed under high
temperatures and in the presence of Mg2+, SO4 2solution
and hydrocarbons. The generation rate is
much higher than that for thermochemical reactions
between gypsum and organic matter, and thermal
degradation of sulfur-rich organic matter. This
indicates that TSR is the main mechanism for the
formation of large amounts of H2S under deep burial
and high temperature, and suggest Mg 2+ is a factor
deserving attention. The close correlation between
the sour gas fields and reservoir dolomitization in NE
Sichuan indicates that there is complex
interrelationship between abundant H2S, TSR, Mg 2+
and reservoir dolomitization. The ocurrence of solid
bitumens in sour gas reservoirs in the Puguang field
is a direct evidence for earlier oil migration and
accumulation, thus providing abundant hydrocarbon
source for later reactions with sulfate-rich
(magnesium) formation waters in the P2ch-T1f
reservoirs.
TSR occurs at high temperatures with an initial
reaction temperature of at least 120°C. The P2ch-T1f
reservoirs in the Puguang gas field were buried to a
depth of 4000 m or 120°C in the Middle Jurassic; by
the Late Cretaceous, the burial depth reached 7500 m
or over 150°C. Currently, it is buried to 4500-6000 m
or 120-130°C. Thus, the P2ch-T1f reservoir fluids were
over the activation energy range for TSR production
from the Middle Jurassic.
There are worldwide occurrences of large to extralarge
sour gas fields, such as the Puguang studied
here and Astrakhan gas field of the Near Caspian
Sea. The common feature of these examples is their
occurrence in dolomitized reef flat facies of palaeouplifts
or palaeo-slope settings, accompanied by large
amounts of solid bitumen. During diagenesis, early
dolomitization and organic acid corrosion lead to high
quality reservoir prior to peak hydrocarbon generation
in the source rocks, thus providing favorable storage
space for early accumulation of large amounts of
crude oil.
H2S, a strong reductant with high levels of chemical
activity can be easily consumed under many
conditions during its formation, migration and
accumulation. In order for H2S to migrate, accumulate
and reside with other gases, additional conditions
must be met beside the normal principles in migration,
accumulation and preservation of natural gas. Ironpoor
fluids, timely development of accumulation
space (specifically in carbonate rocks), in-situ or near
accumulation of hydrocarbons are all important
factors for H2S enrichment and preservation. As a
result, many highly sour gas fields discovered in the
world are found distributed in carbonate rock or
evaporitic sequences rather than in clastic rocks.
Therefore, long distance migration and accumulation
increases the chance of H2S consumption, while
reduction reactions and closed systems are the most
important guarantee for H2S enrichment and
preservation in NE Sichuan Basin.
485

P-356
Controls on the kinetics of thermochemical sulfate reduction
Geoffrey Ellis 1 , Tongwei Zhang 2 , Qisheng Ma 3 , Alon Amrani 4 , Yongchun Tang 3
1 U. S. Geological Survey, Denver, United States of America, 2 Bureau of Economic Geology, Austin, United
States of America, 3 Power, Environmental, Energy Research Institute, Covina, United States of America,
4 Geological Survey of Israel, Jerusalem, Israel (corresponding author:gsellis@usgs.gov)
Published estimates of the kinetic parameters
describing the rate of thermochemical sulfate
reduction (TSR) vary widely and are inconsistent with
geologic observations. Recent experimental and
theoretical evidence indicates that TSR in natural
environments probably involves a two-stage reaction
mechanism. The initial stage involves the reduction
of a reactive sulfate species to hydrogen sulfide (H2S)
in the absence of reduced sulfur. The second stage
involves a much more rapid catalyzed reaction once a
threshold partial pressure of H2S has been attained.
Extensive experimental evidence shows that aqueous
CaSO4 and free sulfate ions (SO4 2- ) are not readily
reduced by TSR. Aqueous geochemical modeling of
typical reservoir brines shows that the dominant
reactive sulfate species at common reservoir
temperatures (100-200°C) is aqueous MgSO4 contact
ion-pairs (CIP‘s). However, when aqueous solutions
containing Mg and SO4 are heated to temperatures
>200°C used in laboratory simulations, the
precipitation of magnesium hydroxide sulfate hydrate
precludes the formation of MgSO4 CIP‘s and bisulfate
(HSO4 - ) becomes the predominant sulfate species.
Ab initio quantum chemical calculations indicate that
the kinetic parameters for the uncatalyzed reduction
of HSO4 - and MgSO4 CIP‘s are equivalent (Ea~56
kcal mol -1 and Af~1.5e+13 sec -1 ). Moreover,
experimental simulations of the initial TSR reaction
involving HSO4 - and several different crude oils
provide a range of activation energies from 55.3 to
58.9 kcal mol -1 and frequency factors from 5e+16 to
1e+17 sec -1 . The variation in the kinetic parameters
observed for different oil types appears to be related
to the concentration of labile sulfur compounds in
whole crude oil. Once the threshold concentration of
H2S has been exceeded, the rate of TSR increases
significantly, and detailed experimental work shows
that the activation energy for the catalyzed reaction is
directly proportional to the concentration of H2S. This
relation can be expressed as:
Ea = -0.066(pH2S) + 58.01
where Ea is the activation energy in kcal mol -1 and
pH2S is the partial pressure of H2S in psi (see figure).
Recalculation of the kinetics of sulfate reduction using
two previously published datasets (Kiyosu, Chem
Geol., 30: 47-56; Goldhaber and Orr, in Geochemical
transformations of sedimentary sulfur, Vairavamurthy
and Schoonen, eds., p. 612), and taking into account
the effect of HSO4 - concentration, produces results
that generally agree with our observations. These
findings lay the foundation for a predictive model of
TSR in geologic environments; however, accurate
determination of the H2S-generation potential likely
requires some knowledge of the chemistry of
petroleum present, the local water chemistry, and the
thermal history of the reservoir.
486

P-357
Mechanisms of thermochemical sulphate reduction: Insights
from redox buffered laboratory experiments
Svenja Germerott 1 , Christian Ostertag-Henning 2 , Harald Behrens 1
1 Leibniz University Hannover, Institute for Mineralogy, Hannover, Germany, 2 Federal Institute for
Geosciences and Natural Resources, Hannover, Germany (corresponding
author:s.germerott@mineralogie.uni-hannover.de)
Cai et al. (2003) showed that high H2S concentrations
in the Wolonghe Field (Sichuan Basin, China) of up to
32% have been generated by thermochemical
sulphate reduction (TSR). This finding is just one
example that stresses the relevance of TSR for
petroleum reservoirs. TSR refers to the abiotic
reduction of sulphate by the oxidation of
hydrocarbons. The accumulation of the major reaction
products (H2S and CO2) reduces the quality of the
reservoir. In spite of its importance, the understanding
of the TSR process is not adequate and the
extrapolation of many experimental results to natural
systems is critical because key chemical variables,
e.g. the redox conditions, were not adjusted to
geologically reasonable values [2].
In this study experimental findings on TSR in a
controlled, redox buffered system are presented in
order to elucidate fundamental mechanisms of the
process and thus to improve the general
understanding of TSR.
The experimental approach involves the use of a
redox-mineral buffer, consisting of pyrite (FeS2),
pyrrhotite (FeS) and magnetite (Fe3O4), in order to
constrain the chemical environment during the
experiments with respect to H2 and H2S fugacities.
Na2SO4, dissolved in water, was used as sulphate
source and C8H18 as model hydrocarbon.
Furthermore, the influence of elemental sulphur on
the reaction mechanisms and progress was
investigated. Experiments were conducted in coldseal
pressure vessels using gold capsules as sample
containers. Temperature was adjusted to either 300
or 350 °C at a pressure of 350 bar. Duration of the
experiments ranged from 24 to 336 h. After the end of
the experiments the samples were analyzed by
different gas chromatographic techniques. In addition
to CO2, gaseous and highly volatile hydrocarbons, we
focused on the analysis of ketones and organosulphur
compounds.
Main findings of this study are:
1) We observed an increase of the CO2 yield
[Fig. 1] with an enhanced TSR reaction
which is in line with the reaction proposed by
Orr (1974). However, our results show that
the oxidation of carbon proceeds via one or
more intermediate steps, such as the
formation of ketones [Fig. 1].
2) Aromatisation and isomerisation are also
promoted with an increased TSR reaction.
The formation of aromatic compounds
reflects an oxidation of hydrocarbons. The
raised yield of branched hydrocarbons
correlates with an increase in the formation
of radicals that are suggested to play a
significant role for the TSR process.
3) Last but not least, consistent with previous
TSR studies, our results confirm the catalytic
influence of elemental sulphur and show that
organosulphur compounds facilitate the TSR
reaction.
Fig. 1: Abundance of CO2 (left) and selected
ketones (right) after experiments for 168 h.
Pyrolysis (PPM+H2O+C8H18), TSR (PPM+H2O+
C8H18+Na2SO4) and TSRcat. (PPM+H2O+
C8H18+Na2SO4+S) refer to the three different
educt combinations used for the experiments.
Error bars are 10%.
References
[1] Cai, C., Worden, R.H., Bottrell, S.H., Wang, L.,
Yang, W. (2003) Chemical Geology 202, 39-57.
[2] Seewald, J.S. (2001) GCA 65, 1641-1664.
[3] Orr, W.L. (1974) American Association of
Petroleum Geologists Bulletin 58, 2295-2318.
487

P-358
Sulfur compounds in liquid products of the thermolysis of heavy
oil asphaltenes
Andrei Grinko, Anatoly Golovko, Raisa Min, Tatyana Sagachenko
Institute of Petroleum Chemistry Russian Academy Sciences Siberian Branch, Tomsk, Russian Federation
(corresponding author:)
Investigation of the structure and properties of
asphaltenes is of great importance for understanding
of their formation and geochemistry, as well as to
develop new ways of processing heavy crude oil,
natural bitumen and oil residues. Knowledge about
the composition of asphaltene molecules, the nature
(type) of structural fragments containing heteroatoms
is of particular importance, since they determine
thermal stability and reactivity of the asphaltene
molecules.
The purpose of this study is to investigate sulfurcontaining
fragments in the structure of the
asphaltene molecules.
Organic sulfur compounds, yielded by
thermolysis of asphaltenes occurring in heavy highsulfur
oil recovered from Usinsk oil field (Russia),
have been investigated.
The asphaltenes, isolated by 40-fold excess of nhexane,
were separated into 4 fractions (A1, A2, A3
and A4) by fractional precipitation with
chloroform:hexane mixtures 30:70, 30:75, 30:120 and
30:150, respectively. Molecular weights and contents
of heteroatoms (S, N and O) decreased from A1 to A4
fractions.
Thermolyses of the initial asphaltenes and their
fractions were carried out in a steel reactor 12 cm 3
during 1 hour at the preset temperatures: 160, 200,
250, 300, 450 and 650 °C. Temperatures correspond
to the maximum rates of fractions decomposition
recorded by a derivatograph. Thermolysis products
were separated into hydrocarbons (oil fraction) and
resins using a column liquid-adsorption
chromatography on silica gel. Oil fractions were
analyzed by gas chromatography-mass spectrometry
quadrupole system GCMS-QP5050 Shimadzu.
In the oil fraction of the products of the initial
asphaltene thermolysis carried out at 450 °C we
identified (in order of content decrease) unsubstituted
and alkyl-substituted (C1-C4) dibenzothiophenes,
phenanthro[4.5-bcd]thiophene, benzo[b]naphthothiophenes,
benzo[b]thiopheno[2.3.4.5-d.e.f] phenanthrene,
dinaphtho[2.3-b:2‘.3‘-d]thiophene,
perilo[1.12]thiophene, benzothieno[3.2-b]benzothiophene,
benzo[1.2-b:3.4-b']bis-benzothiophene and
4-phenyldibenzothiophene.
In the oil fraction of the thermolysis products up
to 300 °C sulfur compounds occurred in trace
quantities. Oil fraction of the thermolysis carried out at
300 °C contained mainly dibenzothiophene and its
alkyl substituted homologues. At the increase in the
temperature of the initial asphaltene thermolysis up to
650 °C we identified phenanthro [4,5-bcd]thiophene,
benzo[b]naphtho[1,2-d]thiophene, benzo[b]naphtho
[2,1-d]thiophene, benzo[b]naphtho[2,3-d]thiophene,
triphenyleno[1,12-bcd]thiophene, dinaphtho[2,3b:2‘,3‘-d]thiophene,
perilo[1,12-bcd]thiophene, benzothieno[3,2-b]benzothiophene,benzo[1,2-b:3,4-b']bisbenzothiophene
and 4-phenyldibenzothiophene in the
oil fraction. Dibenzothiophene was the main
component.
Oil fractions of the products of A1, A2 and A4
asphaltene fractions thermolysis carried out at 175 °C
and those of A3 fraction thermolysis at 210 ° C are
mainly represented by dibenzothiophene and alkyl
dibenzothiophene and phenanthro[4.5-bcd]
thiophene. At 455 °C thermolysis of asphaltene
fractions mainly yields benzothiophene and benzo[b]
naphthothiophene. Dibenzothiophene is a major
component generated by thermolysis at 650 °C
though a greater number of organic sulfur
compounds: phenanthro[4.5-bcd]thiophene,
benzo[b]naphthothiophene, benzo[b]thiopheno-
[2.3.4.5-d.e.f]phenanthrene, dinaphtho[2.3-b:2‘.3‘d]thiopheno,
perilo[1.12]thiophene, benzothieno[3.2b]benzothiophene,benzo[1.2-b:3.4-b']bisbenzothiophene
and 4-phenyldibenzothiophene are also
generated. Benzothiophene and its alkyl-substituted
homologues are found in trace quantities in the oil
fractions of the thermolyses (450, 455 and 650 °) of
the initial asphaltenes and their fractions.
It should be noted that the Usinsk oil contains
mainly benzo-, dibenzo- and naphthobenzothiophene
compounds and their homologues.
Thus, we have identified sulfur compounds which
occur as fragments in the structure of oil asphaltene
molecules. The asphaltenes contain all compounds
occurring in crude oil as structural fragments.
488

P-359
A laboratory study of H2S production from the thermal reactions
of magnesium sulfate and sulfur with a hydrocarbon reactant:
implications for thermochemical sulfate reduction
Hong Lu 1 , Paul Greenwood 2,3 , Tengshui Chen 1 , Jinzhong Liu 1 , Ping'an Peng 1
1 State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, China Academy of
Sciences, Guangzhou, China, 2 WA Biogeochemistry and John De Laeter Mass Spectrometry Centres,
University of Western Australia, Crawley-6009, WA, Perth, Australia, 3 Western australia Organic Isotope
Geochemistry Centre, Curtin University GPO Box U1987, Bentley, WA 6845, Australia (corresponding
author:luhong@gig.ac.cn)
The reactions of pure n-C24 with MgSO4 elemental
sulfur were investigated by monitoring the yields,
stable carbon and hydrogen isotopic composition of
gaseous products from their separate gold–tube
pyrolysis treatment at a series of temperatures over
the range 220–600 ℃. Thermal cracking via pyrolysis
of just n-C24 were also conducted as a Control. H2S
from the thermochemical sulfate reduction (TSR) of
MgSO4 was initiated at 431 ℃, coincident with the
evolution of C2–C5 hydrocarbons. Whereas the yields
of H2S increased progressively with pyrolysis
temperature, the hydrocarbon yields decreased
sharply above 490 ℃ due to TSR consumption.
Ethane and propane were initially very 13 C depleted,
but became progressively heavier with pyrolysis
temperature and were more 13 C enriched than Control
values above 475 ℃.
TSR of MgSO4 also led to progressively higher
concentrations of 13 C depleted CO2 —due to
preferential reaction of 12 C–bonds and precipitation of
13 C rich MgCO3 —at pyrolysis temperatures above
430 ℃. Sulfur reacted with n-C24 to produce H2S at
the relatively low temperature of 250 ℃, implicating
S–hydrocarbon reactions at practical geological
conditions as a potentially important source of H2S
subsurface deposits. Sulfur produced only low
amounts of CO2 to 430 ℃, indicating abstraction of
the H source for H2S occurred in the absence of C–C
bond cleavage. Higher yields of 13 C depleted CO2—
sulfur also showing a reactive preference for 12 C
bonds—and low MW hydrocarbons were evident from
431 ℃, although a moderate reduction (i.e., not as
rapid as with MgSO4 -TSR) of hydrocarbon levels
above 492 ℃ was indicative of their TSR participation,
consistent also with the increased yields of H2S and
13 C depleted CO2 at high temperatures. The reaction
of low MW hydrocarbons with sulfur—added in the
Sulfur treatment and also produced by sulfate
oxidation in the MgSO4 treatment—may also account
for the elemental sulfur (S8, S7, S6 and S4) and
organic sulfur products detected in the solvent
extractable fraction of their pyrolysis residues.
Key words: TSR, H2S, MgSO4, elemental sulfur,
sulfur radical, catalytic hydrogen abstraction.
489

P-360
High pressure pyrolysis of hydrocarbons in the presence of H2S.
Significance to the composition of oils in reservoirs
Van Phuc Nguyen 1 , Raymond Michels 1 , Paul-Marie Marquaire 2 , Valérie Burklé-Vitzthum 2
1 UMR 7566 G2R, CNRS, Nancy Université, Vandoeuvre-lès-Nancy, France, 2 CNRS - Laboratoire Réactions
et Génie des Procédés, LRGP-UPR 3349 , Nancy Université, ENSIC, NANCY, France (corresponding
author:Van-Phuc.Nguyen@g2r.uhp-nancy.fr)
The understanding of the reactivity of sulfur species in
petroleum reservoirs is of prime interest to
geosciences. The origin of H2S in reservoirs can be
related to sulfur rich source rocks, to the
thermochemical reduction of sulfates, or to bacterial
sulfate reduction for instance. The H2S source may be
readily elucidated by isotope measurements of sulfur.
Yet, the understanding of the reactivity of H2S in the
presence of hydrocarbons is still of concern in many
aspects of petroleum interests, as to predict sulfur
species in high sulfur reservoirs, hydrocarbons
stability in deep-hot reservoirs, H2S yields forecast
during heavy oil recovery, or H2S sequestration during
acid gas injection.
In order to study the reactivity of H2S in the presence
of hydrocarbons, pyrolysis experiments were
conducted on whole oils and pure compounds using
gold cell pyrolysis conducted at 200°C

P-361
H2S risking toolset – thermochemical sulphate reduction field
study and analytical efforts: Sequential diagnostics for Fluidfluid-rock
interactions
Henning Peters 1 , Olaf G. Podlaha 1 , Erdem Idiz 1 , Chad Glemser 2 , Lavern Stasiuk 2 , Volker
Dieckmann 1
1 Shell Global Solutions <strong>International</strong> B. V., Rijswijk, Netherlands, 2 Shell Canada Energy, Calgary, Canada
(corresponding author:Henning.Peters@shell.com)
The distribution of non-hydrocarbon ―sour‖ gases
(H2S, CO2) in hydrocarbon reservoirs is controlled
mainly by thermochemical sulphate reduction (TSR)
and organic matter cracking of organic sulfur
compounds (OSC) in high temperature reservoirs
versus bacterial sulfate reduction (BSR) in lowtemperature
reservoirs.
In this study we focus on TSR, which is by far the
most important process in the subsurface for the
generation of significant levels of H2S. Over the past
years continuous progress has been made in the
understanding of chemical mechanisms, major
catalysts, temperature thresholds and kinetics for the
generation of H2S from TSR, [1], [2], [3], [4]. However,
the complexity of sulphur chemistry and water-rock
interaction limits our ability to extrapolate from
experimental data to field scale. On how that can be
translated into predicitive capabilities we refer to [5].
Consequently, understanding and risking H2S
formation in the subsurface begins with the use of
diagnostic tools 1) to approximate the H2S source, 2)
gather lateral and vertical subsurface variabilities, 3)
to relate the degree of H2S variability to chemical
process and subsurface conditions including the
interaction with fluids and rock matrix.
We present the main elements of a diagnostic
workflow that was developed and is in more detail
explained in [5] to first understand and then quantify
the subsurface distribution of H2S.
Throughout the TSR process the natural incorporation
of sulphur into bitumen (natural vulcanization) was
investigated to elucidate the evolution of H2S
formation in using sulphur compound class
distributions.
The field studies were supported by a sequence of
analytical efforts including:
- Petrography (microscopy) of limestone and
dolostone in the petroleum reservoirs units
- Geochemical characterization of solid bitumen
using elemental analysis and X-ray absorption
spectroscopy (XANES)
- Carbon, oxygen and sulfur isotope analyses of
various phases
- Fluid inclusion studies using classic
microthermometry analysis and Raman
spectrometry for semiquantitative gas typing.
The newly gathered workflow data compared with
production data reveal good correlation to support the
approach.
The workflow was developed on stacked Upper
Devonian to Mississippian sour gas reservoirs
situated in the Rocky Mountains Foothills of Alberta,,
Western Canadian Sedimentary Basin (WCSB),
Canada. Production from these reservoir units is
mainly dry gas and different forms of sulfur. H2S
contents ranging from 5% to almost 90% were
studied. Prolonged history in production data
combined with the close proximity of reservoir
intervals with different levels of H2S are excellent
natural laboratories to reveal the main drivers of its
distribution resulting from TSR.
[1] Zhang et al. (2007): Org. Geochem. 38, 897-910.
[2] Kelemen et al. (2010): GCA 74, 5305-5332.
[3] Ma et al. (2008): GCA 72, 4565-4576.
[4] Machel (2001): Sed. Geol. 140, 143-175.
[5] Podlaha et al. (2011): This abstract volume
491

P-362
The reaction of elemental sulfur with organic compounds:
formation of benzothiophenes and dibenzothiophenes
Zhibin Wei 1 , Scott Northrop 2 , Heather Rehmer 3 , Steve MacFarland 3 , Glenn Otten 4 ,
Clifford Walters 5 , Paul Mankiewicz 1 , Marlene Madincea 4
1 ExxonMobil Exploration Company, Houston, United States of America, 2 ExxonMobil Development
Company, Houston, United States of America, 3 ExxonMobil Production Company, Houston, United States of
America, 4 ExxonMobil Upstream Research Company, Houston, United States of America, 5 ExxonMobil
Research & Engineering Company, Houston, United States of America (corresponding
author:zhibin.wei@exxonmobil.com)
Dibenzothiophene (DBT) can be formed at low
temperatures from aromatic hydrocarbons upon
treatment with sulfur with the aid of catalyst (e.g.,
AlCl3). Many organic compounds can cyclize to form
thiophenes when heated with sulfur or H2S. Sulfur is
known to abstract hydrogen from organic compounds
at high temperatures to produce fragments that
ultimately give stable products by aromatization, ring
formation, or dimerization. However, it is unclear that
benzothiophenes (BTs) and DBTs can be formed
from smaller ring cyclics (e.g., cyclohexane),
aromatics (e.g., toluene) when heating with sulfur at
higher temperatures. To address this issue, heating
experiments were conducted on a variety of individual
reagents including cyclohexane, xylenes,
trimethylbenzenes, toluene, and cyclohexamylamine
in the presence of sulfur using sealed gold tubes to
investigate if BTs and DBTs can be generated. In
addition, these reagents were reacted as mixtures
with cyclohexylamine to determine if the yields of
these thiophenic compounds increase. The
experiments were conducted at different
temperatures and time scales to determine the
influece of these parameters on BT and DBT yields
and distributions.
Our results show that DBT is not observed when
cyclohexane is reacted with sulfur at 190 °C (Fig. 1).
However, DBT and 2,5-dimethylthiophene and are
generated in significant yields as the reaction
temperature is elevated to 250 °C and the yield of
DBT slightly increases with increasing reaction time.
Although cyclohexanethiol is readily formed at 190 °C,
it is very reactive and tends to disappear to form
benzenethiol at 250 °C as reaction proceeds.
Diphenyl sulfide and diphenyl disulfide are both
formed at higher temperature, but are nearly absent
at lower temperature. Sulfur can cause
dehydrogenation of organic compounds, cyclization,
and in some instances, reduction. Upon treatment
with elemental sulfur at 190 °C and 250 °C, xylenes
did not form DBTs. However, BTs are formed at both
heating temperatures. A fair quantity of 4,5-
dihydrobenzothiophene is produced from the reaction
of xylenes and sulfur at 250 °C for 1 day. As the
reaction proceeds, sulfur abstracts more hydrogen
from this compound, leading to the formation of BT.
Trimethylbenzene generated abundant alkylated BTs
but no DBTs upon treatment with sulfur.
Cyclohexylamine forms much more BTs and DBTs
than cyclohexane in the presence of sulfur. The
yields of the BTs and DBTs are improved by the
presence of cyclohexylamine and the reactions are
considerably accelerated due to the heterolytic
cleavage of the covalent S-S bond in the cyclic S8
molecule with the formation of polysulfide ions. These
ions undergo hemolytic cleavage with the formation of
free radicals which then serve as initiators of
dehydrogenation. The occurrence of dimeric products
(e.g., diphenyl sulfide) is consistent with radical
reactions. In addition, the yields of these thiophenic
compounds slightly increase with increasing reaction
time.
Relative abundance
A
B
C
SH
SH
S
S
S
SH
SH
S
SH
SH
HS
SH
HS
HS
20 40
Retention time (minute)
SH
Fig. 1. Total ion chromatograms of the reaction
products from cyclohexane and elemental sulfur at (A)
190°C for 7 days, (B) 250°C for 1 day and (C) 250°C
for 7 days
S
SH
SH
s s
s s
s s
s s
S SH
S S
S
SH S
S
S
S
S
S
S
492

P-364
Shines Bright for Jurassic exploration targets: case study of
shale oil characteristics
Rita Andriany, Awatif Al-Khamiss, Hussain Taqi, Abdulaziz Al-Fares
Kuwait Oil Company, Ahmadi, Kuwait
An integrated understanding of the shale oil
characters will be supplies a brightly light in the
darkness of an exploration target. The previous study
of the most reliable correlation parameters of
biomarker and carbon stable isotope (Rita and Awatif,
GEO 2010) proved that Najmah Shale oil Jurassic
age as effective source rocks. Crude oils trapped
between the Najmah effective source rock and
overburden rock Gotnia Formation having 95%
similarity. These correlation parameters can be as
effective tools to characterizing or correlating oilsource
of Jurassic age within regional area of Middle
East.
It believed that each period or each basin would be
distinct by abundance or disappearance of certain
biomarkers. Furthermore, each shale oil layer may
represent the unique characteristics in biomarker
abundances reflection of the chemical and physical
reactions during sedimentation and preservation of
organic matter through geological time. Due to the
accuracy and capability to maintain their carbon
skeleton like ―DNA‖ which produced by relatively
expensive analysis Gas Chromatograph Mass
Spectrometry (GCMS), thus can be utilized to answer
a big question in exploration of ―where ‖ the
accumulation or active pod kitchen were located.
Distribution of active pod from a numerous effective
oil shale layers may offer clues as delineation path
that enable to reduce the uncertainty level in
exploration target.
Shale oils of Jurassic age (Callovian to Oxfordian)
that preserved within Dibdibba basin in Kuwait
characterized by presence of terpanes (m/z 191)
includes pentacyclic, tetracyclic, and tricyclic terpanes
with variety of predominance ratios in each potential
layer of shale oil. Tricyclic terpane (t23), tetracyclic
terpane (T24), 28,30-Bisnorhopane, and
homohopanes (C31 to C35) are among of the
terpanes biomarker families that present relatively
abundance in the Jurassic shale oil. The presence of
these biomarkers indicates that source of organic
matter possible originated from algae or marine
microorganisms, which deposited in carbonate or
evaporate depositional environment.
Steranes (m/217) in Jurassic shale oil appear
relatively less abundant compared to terpanes. These
imply the steranes nearly reach the equilibrium level
or window of the disappearance. Nevertheless, the
diversity of steranes spikes C27, C28, and C29 within
each Jurassic shale oil layer indicates the organic
matter supplied from at least three main sources.
Due to the sensitivity of sterane isomerization ratios
(20S/20R) for moderate to high stage of maturities, it
seems more realistic to use this valuable ratio to
define the degree of maturity for Najmah shale oil in
study area. The active pod kitchen in North Kuwait
appears to be mature zone by having sterane
isomerization ratios ranges 0.49 – 0.55. This
additional evidence supports the previous study that
the effective shale oils in North Kuwait as most
important area to be developed.
Degrees of sterane isomerization ratios 20S/20R tend
to decreasing from northern part to southern part
within ranges 0.49 – 0.55 and 0.29 – 0.42
respectively. Despite having a lower range, but these
indices imply that potential shale oil in South East
Kuwait were reach the oil window. Maturity
investigation from biomarker arise good news and
brightly shines for South East Kuwait due to contained
the potential shale oil to charge the surrounded
reservoirs.
493

P-365
Geochemical evaluation of the origin and migration of gases
present in natural gas hydrates – an example from the
Norwegian continental shelf
Tanja Barth 1 , Espen N. Vaular 1 , Irene Roalkvam 2 , Ida H. Steen 2
1 Department of Chemistry, University of Bergen, Bergen, Norway, 2 Centre for Geobiology, University of
Bergen, Bergen, Norway (corresponding author:Tanja.Barth@kj.uib.no)
Introduction
Natural gas hydrates are found widely distributed in
deep sea sediments. Their occurrence is primarily
detected using seismic mapping, with only a limited
number of samples available for geochemical analysis
and interpretation. Thus, the origin of these large
volumes of methane rich gas is still open for investigation
and discussion. Although a thermochemical
source is often assumed, recent results point at
microbial processes in the sediments as providing a
major part of the gas (1, 2). Due to the simple
chemical structure of the hydrocarbon gases, the
tools for assessing their origin are limited to
compositional and isotopic characterisation. Thus the
basis for the source evaluation needs to include any
information available on the sedimentary environment
to support the conclusions. In this context, interdisciplinary
input from especially microbiological
characterisations of the hydrate bearing sediments
are of high value. The interpretation of the isotopic
compositions of the gases is a critical factor, and all
potentially significant types of fractionation processes
must be critically evaluated, including the potential for
isotopic fractionation during the physical-chemical
process of hydrate formation and dissolution.
Samples and analysis
Headspace from seabed samples, and hydrate gases
have been analysed as previously reported (2,3). The
microbial communities in the same sediments have
been mapped at the Centre of Geobiology at UiB. In
addition, laboratory experiments in a stirred, highpressure,
temperature controlled hydrate incubator
have been performed using both a natural gas mix
and pure methane. Both the hydrate gas and the
residual gas phase were analysed for their isotope
values to evaluate the possibility of isotopic
fractionation when hydrates were formed.
Results and discussion
Figure 1 illustrates schematically our initial interpretation
of the fluid flow that provides the gases incorporated
in the hydrates sampled at the seabed at the
G11 pockmark at Nyegga. The free gas system is
believed to include a contribution from the polygonal
faults in the deep sediment over the Helland Hansen
Arch (HHA). The migrating fluid from the expulsions
forms the chimney ending in the pockmark and feeds
the gas hydrate located in the pockmarks. It contains
primarily microbial methane, while a proportion of
microbial ethane, thermogenic ethane and traces of
higher homologues are also indicated. However, this
interpretation can be challenged, and alternative interpretations
where the thermogenic contribution is of
less importance can be proposed. These hypotheses
will be discussed and tested using extensive data,
including evaluation of the pore water geochemistry,
sediment microbiology and laboratory results.
Figure 1: Schematic drawing of fluid flow systems at
the G11 pockmark at Nyegga (from reference 2).
References
1. Pohlman et al (2009) Methane sources and production
in the northern Cascadia margin gas hydrate
system. Earth Planet Sci. Lett. 287 (2009) 504
2. Vaular et al. (2010) Geochemical characteristics of
the hydrate-bound gases from the Nyegga pockmark
field, Norwegian Sea. Org. Geochem. 41 (2010) 437
3.Vaular et al. (2011) Comparison of Vestnesa and
Nyegga Pockmark Fields using light hydrocarbon parameters
for geochemical profiling. Subm. Marine
Geol.
494

P-366
Organic geochemical characterization and distribution of
unconventional hydrocarbon plays of the Lower Cretaceous of
NW Germany
Ulrich Berner, Matthias Heldt
Federal Institute for Geosciences and Natural Resources, Hannover, Germany (corresponding
author:ulrich.berner@bgr.de)
Within the Lower Saxony Basin (LSB) of NW
Germany sediments of the Lower Cretaceous are
known to contain abundant organic material at
different stratigraphic levels. We present a
geochemical high-resolution study of sediments of the
German Wealden (Berriasian) and compare the data
to Barremian and Aptian organic-rich sediments.
A complete succession comprising 360 m of the
German Wealden (Berriasian) has been investigated
at a drill site located in the western part of the LSB,
representing typical basin sediments of the larger
area. Thermally immature Barremian and Aptian
sediments where obtained from three wells of the
eastern part of the LSB. Samples have been collected
at all drill sites at a minimum spacing of 1 m in order
to better describe facies changes. Organic
geochemical investigations including pyrolysis
methods as well as molecular and carbon isotope
analyzes have been performed on the collected
sediments.
Our data combined with additional geochemical
information show that the Berriasian sediments have
been deposited in a predominantly lacustrine
environment that however experienced marine
ingressions. The numerous facies changes within the
Wealden are likely related to climatically driven
precipitation changes, which have lead to lake level
variations. The observed depositional changes are
associated with variations of the organic facies.
During periods of high lake levels, the organic matter
of the clay stones and marls is hydrogen-rich and
likely derived from aquatic precursors. The associated
anoxic to dysoxic water conditions are obvious from
the stable carbon isotopic composition of the organic
carbon which is highly enriched in 12 C suggesting that
a microbial methane cycle had established during the
deposition of the sediments and the organic matter
experienced a significant contribution from the
microbial pool. Low lake levels were associated with
the deposition of hydrogen-depleted organic matter,
which either relate to land plant and/or highly oxidized
material.
Our data of the Barremian to Lower Aptian organicrich
Dark Shale Sequence shows that the sediments
contain variable amounts of terrestrial and aquatic
organic matter deposited in a marine environment.
The Lower Aptian Fish Shale is dominated by aquatic
organic matter, and both Barremian and Lower Aptian
sediments contain rather high concentrations of C28steranes
(Fig. 1), which could be related to observed
higher abundances of coccolithophores.
Figure 1: Relative abundances of C27 to C29 ��steranes
of Lower Cretaceous sediments of the Lower
Saxony Basin.
Although, basin sediments of the Wealden are highly
variable the anoxic to dysoxic facies types containing
type I kerogens are excellent sources for in-situ oil
and gas (at higher maturities). Favorable targets for
the extraction of unconventional hydrocarbons in the
NW German Basin would likely be sections of
Wealden 3 and 4.
The Barremian and Aptian organic-rich shales
exceeding partly 100 m of thickness contain type II
kerogens, and would generate oil and gas, if the
maturities were sufficiently high in the basin.
The Lower Saxony Basin is tectonically segmented
with highly variable heat flow regimes, which set the
boundary conditions for the mapped distribution of
unconventional Lower Cretaceous plays.
495

P-367
Geochemical controls on shale microstructural evolution
Nicholas Drenzek, John Valenza, Flora Marques, Hendrik Grotheer, Michael Herron
Schlumberger-Doll Research, Cambridge, MA, United States of America (corresponding
author:ndrenzek@slb.com)
The complex chemical and structural properties of
shale source rocks, primarily a reflection of the intimate
association of organic matter with mineral grains and
their combined maturation history, regulate the
physiochemical speciation and transport of petroleum
during generation, migration, and production stages. In
order to better understand the fundamental relationship
between these constituents and pore network
characteristics, we analyzed the variation in rock matrix
microstructural properties with organic and mineral
composition, distribution, and maturity in core samples
from the Barnett, Woodford, Caney, Haynesville,
Fayetteville, Marcellus, Mancos, Antrim, and Green
River formations in the continental United States.
Samples were petrographically described (including
vitrinite reflectance) by thin section optical microscopy,
and measured for total elemental (C,H,N,O,S) and total
organic carbon (TOC) content by combustion elemental
analysis (EA), mineral composition by Fourier
transform infrared (FTIR) spectroscopy, organic matter
composition by Rock-Eval pyrolysis, pyrolysis GC-MS,
and NMR spectroscopy, and matrix microstructure by
gas sorption and scanning electron microscopy (SEM).
Compositional and microstructural measurements were
then repeated following the sequential removal of
bitumen and kerogen via solvent extraction and
combustion, respectively.
Native state samples exhibit slit-like pore geometry with
pore widths ranging from 100 nm. Samples
in the oil and gas generation thermal windows contain
micropores (

P-368
Comparison of the geochemical and microstructural coevolution
of two shale lithotypes through artificial maturation
Hendrik Grotheer 1 , Nicholas Drenzek 1 , John Valenza 1 , Michael Herron 1 , Sean Sylva 2 ,
Jeffrey Seewald 2 , Roger Slatt 3
1 Schlumberger-Doll Research, Cambridge, MA, United States of America, 2 Woods Hole Oceanographic
Institution, Woods Hole, MA, United States of America, 3 University of Oklahoma, Norman, OK, United States
of America (corresponding author:ndrenzek@slb.com)
Driven by the recent expansion in unconventional gas
and oil shale resource development, renewed study of
source rock microstructure has underscored the
importance of organic matter maturity and distribution
in regulating fluid flow dynamics. Quantitative models
describing the catagenic co-evolution of shale organic
and mineral composition with matrix microstructure at
the micro- to nanometer scale remain ill-constrained,
however, hampering efforts to predict reservoir quality
in such complex and heterogeneous systems.
In order to more directly relate the effects of thermal
maturation to pore structure changes and
corresponding petroleum generation, migration, and
storage potential, hydrous pyrolysis experiments were
performed on calcareous- and organic rich core
horizons from the Barnett formation (Texas, USA)
using the sealed gold capsule technique. 1 We
monitored kerogen morphology by optical and SEM
microscopy, kerogen and petroleum composition by
elemental analysis, GC-MS, and pyrolysis GC-MS,
co-generated gas composition and isotopic signature
by headspace GC and GC-IRMS, mineralogy by FTIR
spectroscopy, and matrix microstructure by
conventional gas sorption techniques at three
different time points (2, 6, and 18 days) under
constant temperature (350°C) and hydrostatic
pressure (250 bar) conditions.
Hydrocarbon gas yields increased over time, with the
organic-rich interval generating approximately five
times more C1-C4 gases (500 µg/g) of wetter
composition (C1/C2+ ~0.4) after 18 days than the
calcareous interval (Figure 1). Large amounts of CO2
(~15,000 µg/g), likely the result of carbonate thermal
decomposition, were also generated after only 2 days
and remained nearly constant thereafter. Bitumen
extracts, while low in mass typical of many gas-stage
shales, displayed classic early ingrowth of a broad, low
CPI paraffin distribution followed by cracking to lighter
compounds.
Interestingly, specific surface areas of both native state
and pyrolyzed samples with and without their bitumen
extracted increased initially and declined at later stages
(Figure 1), possibly reflecting creation and subsequent
consolidation of kerogen-hosted, partially fluid-filled
micropores. Nanoscale SEM imagery of ion-polished
matrix surfaces reveal a fine pore network that is both
primarily confined to kerogen maceral structures and
more fully developed near organic-mineral interfaces.
Coupled with FTIR mineralogy, these findings likely
reflect the importance of catalysis reactions, moisture-
and heat-sensitive mineral transformations, and the
interplay of differential fluid and interfacial chemistries.
Reference
[1] Seewald et al., 2000. GCA 64 (9), 1577-1591.
Figure 1 – Specific surface areas (left axis) of untreated
(closed symbols) and bitumen-extracted (open symbols)
shale microstructure along with hydrocarbon gas generation
(right axis) as a function of artificial maturation (pyrolysis)
time.
497

P-369
Evolution of pores in organic-rich shales during thermal
maturation
Tian Hua, Zhang Shuichang, Liu Shaobo, Chen Jianping
Research Institute of Petroleum Exploration and Devolopment, Beijing, China (corresponding
author:sczhang@petrochina.com.cn)
1. Introduction
It is important to understand the evolution of pores in
organic matters during the process of thermal
maturation in order to quatitatively predict shale
porosity in shale gas exploration. This study aims to
document the changes of size, morphology, and
abundance of pores in an initial low maturity organicrich
shale during thermal maturation, so as to
evaluate the storage ability of shale at different
maturities.
2. Sample and method
In this study, an immature (Ro~0.6%) shale outcrop
sample from Fushun mine, Northeast China was
selected for pyrolysis. A set of mature samples were
also selected for comparison. The solid residual
samples of pyrolysis at different temperatures were
used to compare with the shale at different maturities.
The initial sample is relatively immature, with a
vitrinite reflectance value of 0.6%, TOC of 7.35%,
Hydrogen Index (HI) of 440. The mature outcrop
samples are with vitrinite reflectance values of 1.3%-
2.8%, TOC values of 5.0-11.2%, HI values of 440-
680.
An alloy reactor pyrolysis experimental setup (Figure
1) was set up to performpyrolysis experiments on the
immature shale under elevated pressure and heating
rate conditions(0.1-10MPa, 0-600 oC ,1oC/h). This
setup includes SKETCH the MAP use OF of ALLOY a back-pressure REACTOR valve, with
which the user PYROLYSIS can set a EXPERIMENTS
specific pressure value.
SHALE
OVEN
ALLOY
REACTOR
BACK-PRESSURE
VALVE
LIQUID
PRODUCT
GAS PRODUCT
Figure1. Alloy Reactor Pyrolysis Experimental Setup
3. Results and discussion
With the increase of thermal maturity, pore
abundance becomes higher. Pores in the lowthermal-maturity
samples are much fewer than that at
high maturity. Two SEM examples are presented here
(Figure 2). Sample B (right) have VRo values less
than 0.7%, which are at the low end of the
hydrocarbon generating window. There are little pores
in the organic matters; the surface of the organic
matters is relatively flat. Pore networks in sample B
contrast greatly with that in sample A (left) of highermaturity
(VRo values > 1.0%). The primary difference
is that grains of organic matter in these less mature
samples have few or no pore. Also, during thermal
maturation, the surface area of shale increase, the
percentage of micropores increase.
A
Figure 2. SEM images of organic matters in shale of
different maturities. A) shale with VRo values> 1.0%
showing well developed pores presented in the
organic matters. B) shale with VRo values< 0.7%
showing striped organic matters in the matrix with few
pores in the organic matters.
The percentage of micropores and mesopores
increase in SEM imagines, CO2 low pressure
isotherm analysis (D-R method), N2 low pressure
isotherm analysis (BET theory), and Hg porosimetry
analysis. Pore morphology changed much during
thermal maturation. Most pores in immature shale are
bubble like and isolated. By contrast, stripe, elliptical
and connected pores are much common in mature
shale.
During thermal maturation, Pores are formed as
kerogen is converted to hydrocarbons, resulting in the
formation of liquids and gases (Loucks et al, 2009).
Pore body and pore throat size distributions are
typically smaller ranging, well below the micro
porosity classification (

P-370
Organic geochemistry of the Colorado Group shale sequence
stratigraphic framework of the Western Canada Sedimentary
Basin: Implications for shale gas fairway identification
Haiping Huang 1 , Per Pedersen 1 , Ron Spencer 1 , Andy Aplin 2 , Dallin Laycock 1 , Samantha
Taylor 1 , Steve Larter 1
1 University of Calgary, Calgary, Canada, 2 University of Newcastle upon Tyne, Newcastle upon Tyne, United
Kingdom (corresponding author:huah@ucalgary.ca)
For a better understanding of shale gas fairways,
organic geochemistry is used in order to characterize
the origin and variability of the organic matter in a well
defined sequence stratigraphic package of thermally
immature Upper Cretaceous Colorado Group shale in
the Western Canada Sedimentary Basin. The distal
marine shales of the Colorado Group were studied in
a 200 m long continuous core.
This study involves the use of Rock-Eval data and
quantitative molecular analysis of aliphatic and
aromatic hydrocarbon fractions as stratigraphic
correlation markers. We observe a good correlation
between the organic data and sequence stratigraphic
structure with changes in geochemical signatures
reflecting the 3rd order depositional cycles. The
relative sea-level variations exerted the major control
on the composition of primary produced organic
matter and on its redox-controlled preservation as
indicated by TOC, HI, C27, C28 and C29-sterane
distributions, steranes versus hopanes ratio, and Cring
monoaromatic steroid hydrocarbons to cadalene
and retene ratios.
Bulk and molecular compositional changes delimitate
three depositional cycles with regressive units of the
Belle Fourche Formation, the Carlile Formation and
Medicine Hat Member of the Niobrara Formation and
transgressive units of the Second White Specks
Formation, Verger Member and First White Specks
Member of the Niobrara Formation. The shales in the
transgressive phase (outer shelf environment) was
largely marked by high TOC content (3-5%), high HI
values (>300 mgHC/g TOC), and biomarkers
indicative of high cyanobacterial input, and lower
bacterial productivity. Regressive phase (inner shelf
environment), with relative low TOC and HI, was
influenced by molecular markers of terrestrial organic
input present in the argillaceous detrital fraction,
probably transported by storm activity.
The organic geochemistry variations revealed
changes in sedimentary environment that had also
been detected by sedimentological methods. Trace
element profiles of Zr, Mo and U show the same three
cycles as facies tracking biomarker distributions.
Similarly, quartz content tends to be lower in
transgressive units and higher in regressive units,
while clay content shows the opposite variations.
A proper understanding of the organic geochemistry
improves our understanding of vertical facies
variations and provides important constraints on shale
gas exploration in terms of defining the best source
and reservoir shale geobodies. The definition of
correlative geochemical and sedimentary facies within
the shale dominated clastic wedge of the Colorado
Group could serve as an analogue for other similar
gas bearing shales.
499

P-371
Preliminary investigations into gas-in-place and fraccability
of shales from the Sichuan Basin, China
Jingqiang Tan 1 , Dorothee Hippler 2 , Jinchuan Zhang 3 , Ger van Graas 4 , Nicolaj Mahlstedt 1 ,
Georg Dresen 1 , Brian Horsfield 1
1 German Research Center for Geosciences, Potsdam, Germany, 2 Technical University of Berlin, Berlin,
Germany, 3 China University of Geosciences, Beijing, China, 4 Statoil, Oslo, Norway (corresponding
author:jqtan@gfz-potsdam.de)
In China, black shales deposited in marine and
terrestrial settings have a large distribution area of
over 3×10 6 km 2 [1]. The great thickness, high maturity
and high TOC of many shale formations may translate
into a huge gas potential. The total shale gas
resource is estimated at 100×10 12 m 3 , and the
recoverable reserves reported range from 21.5 to 45
×10 12 m 3 [1-2]. The most promising areas are located
in south China, especially in the Sichuan Basin and its
adjacent regions. In this study, we are investigating
the gas-in-place and fraccability of shales in the
Sichuan basin by combining regional geology with a
series of experiments on organic geochemistry and
geomechanics.
In the Sichuan Basin, black shales are prominent from
the upper Sinian to lower Cambrian, from the upper
Ordovician to lower Silurian and from the upper
Triassic to lower Jurassic systems [3]. In the lower
Cambrian (Qiongzusi Fm.) and lower Silurian
(Longmaxi Fm.), kerogens are dominantly of type I
and II with an average organic carbon content of
usually higher than 2%. Brittle minerals make up
between 37.1 and 80.8% of the total inorganic
fraction. Meanwhile, the microfissures and micropores
are developed well, total porosity can reach up to
8.10% (core sample) and 24.24% (outcrop sample)
for the Qiongzusi formation and 15.72% (core
sample) and 16.85 % (outcrop sample) for the
Longmaxi formation [4-5]. These two formations are
generally buried more than 4000 m and reach
maturities greater than 2% R0.
Our preliminary results on the lower Cambrian black
and siliceous shale outcrop samples from the
Guizhou, Hunan and Yunan provinces also suggest
high shale gas potentials. More than half of the
organic matter rich samples (up to 19.0% TOC) are in
mature (Tmax >435°) or over mature (Tmax >450°)
stages and elevated S1 values indicate high amounts
of gas-in-place (Figure 1).
References
Figure 1 PI-Tmax plot
1. Zhang Jinchuan, Jiang Shengling, Tang
Xuan, Zhang Peixian, Tang Ying, Jin Tieya.
Natur. Gas Ind. 2009, 29(12):109-114 (In
Chinese with English abstract).
2. Liu Honglin, Wang Hongyan, Liu Renhe,
Zhao Qun, Lin Yingji. Acta Geologica Sinica,
2010, 84(9): 1374-1379 (In Chinese with
English abstract).
3. Editorial Committee of ―Petroleum Geology
of China‖. Sichuan Oil & Gas Field.
Petroleum Industry Press, 1987, 28-80 (In
Chinese).
4. Dong Dazhong, Chen Keming, Wang Yuman,
Li Xinjing, Wang Shejiao, Huang Jinliang. Oil
& gas geology, 2010, 31(3): 288-300 (In
Chinese with English abstract).
5. Pu boling. China University of Petroleum
Master Degree Thesis, 2008, 50(In Chinese
with English abstract).
500

P-372
Transformation of organic matter of sedimentary rocks in model
experiment with the flow of supercritical CO2-fluid
Sara Lifshits, Olga Chalaya
Institute of Oil and Gas problems SD RAS, Yakutsk, Russian Federation (corresponding
author:s.h.lifshits@ipng.ysn.ru)
According to our model of oil generation the
sedimentary rocks with a dispersed organic matter
under the conditions of oil window can be regarded as
a natural ―mechanochemical reactor,‖ which is
triggered for oil production by the flow of plutonic
fluids in the supercritical (SC) state [1]. The SC fluid
evidently performs the function of not only a solvent,
but also a medium in which chemical reactions occur.
The fragments of kerogen molecules and bituminous
substances entrained by the SC fluid will experience
very strong deformation stresses because they are
comparable in size to the micropores and microcracks
of petroleum mother rocks (5–10 nm). This
mechanical energy will probably suffice for C–C bond
cleavage in high molecular substances; i.e., for
initiating mechanochemical reactions. We can thus
assume that solution and migration in a flow of SC
fluid are accompanied by mechanochemical
transformations of DOM and form the light-volatile
components of oil.
To check this oil formation model, we performed
experiments to study the possibility of hydrocarbons
transferred and transformed in a SC fluid medium.
The samples used for supercritical fluid extraction
(SCFE) included bituminous limestone and clay sand
soil. As a supercriticall medium, we chose CO2
because it is one of the main components of plutonic
fluids. Hot chloroform extraction of the samples was
performed simultaneously with SCFE.
The presence of relict hydrocarbons in the
supercritical extract and the distribution of the
individual hydrocarbons close to that in the starting
rock indicate that the supercritical fluid can dissolve,
transfer, and accumulate petroleum like organic
substances. The organic substance of the
sedimentary rock sample under study has already
been transformed in dia- and catagenesis. As a
consequence, the transformations that can occur in
the micropores and microcracks of sedimentary rocks
in the SCFE are less pronounced. To study all
possible transformations, we performed an
experiment on SCFE of a soil sample because soils
contain a geochemically immature organic substance.
The extract was dissolved in hexane and studied by
GC/MS. Figure 1 presents the mass fragmentograms
(m/z=57) of the hydrocarbons fractions of the
hydrocarbon fractions of the chloroform and
supercritical extracts of the clay sand samples. The
compositions of the hydrocarbon fractions of the
supercritical and chloroform extracts differ
substantially. The distribution of the individual
hydrocarbons in the SC extract became close to that
for oil contaminated soils. Thus, the ratio of the odd to
even normal alkanes in the supercritical extract was
1.5 versus 5.2 in the chloroform extract. The ratio of
relatively low molecular n-alkanes to high molecular
ones was twice higher (0.32%) than the ratio in the
chloroform extract (0.15%). The amount of isoalkanes
in the supercritical extract (43.0%) was almost eight
times larger than that in the chloroform extract (5.5%).
The maximum of n-alkanes shifted from the high
molecular region nC31 to the medium molecular one
nC25.
Fig. 1. Mass-fragmentograms (m/z = 57) of the alkane
hydrocarbons of the (a) chloroform and (b) supercritical
extracts of soil.
The data obtained suggest that the supercritical
extraction is accompanied by a possibly
mechanochemical transformation of the natural
organic substance. As a result, the composition,
structure, and distribution of individual hydrocarbons
of the supercritical extract change toward
geochemical maturity characteristic of petroleum
mother rocks [2]. The formation of oil hydrocarbons in
nature can thus result not only from the evolution
changes in the organic matter of sedimentary rocks in
dia- and catagenesis, which lasts for millions of years,
but also probably from fast mechanochemical
transformation in a flow of the supercritical fluid,
where the micropores and microcracks of petroleum
mother rocks play the role of nanomechanical
reactors. The proposed mechanism allows the time
scale of oil field formation to be revised from millions
to possibly hundreds of years.
501

P-373
Geochemistry of coalbed methane and co-production water of
Fuxin basin, Northeast China
Shaobo Liu, Yan Song, Xiaokang Gao
Research Institute of Petroleum Exploration and Development (RIPED), PetroChina, Beijing, China
(corresponding author:lsb@petrochina.com.cn)
Coalbed methane have been commercially produced
in Liujia block, Fuxin basin, Northeast China. Gas
composition, �D and � 3 C of coalbed methane;
chemical composition, �D and � 8 O of production
water were analyzed in this study.
TDS (total dissolved solids)of production water is
low (1601 to 2384 mg/l) and exclusively NaHCO3
type. �D (-85.3 to -78.9 per mil), � 8 O (-10.9 to -9.9
per mil), TDS of production water have a narrow
range.
The isotopic values of water from production wells,
mine, river plot below the global meteoric water line
(GMWL) on a line near but above the values of
present-day water. The results indicates that all the
water comes from meteoric water and has the similar
distillation.
�D (-258.8 to -230.41 per mil) and � 3 C (-52.7 to -44.7
per mil) of coalbed methane plot on the thermogenic
area of Whiticar‘s CD diagram (Fig.1). High C1/C2+
ratio (above 3000) and �DCH4-DH2O diagram show that
CO2-reduction secondary biogenic gas mixed with
thermogenic gas. � 3 C (-22.6 to -18.6 per mil) of
coalbed dioxide indicates that the mixing amount of
biogenic gas is low.
Three stages of coalbed methane accumulation is put
forward: (1) In early Cretaceous, the original low
mature (Ro=0.5 to 0.61%) thermogenic gas
accumulated in the Fuxin group coal; (2) The basin is
uplift and the sedimentary rock is eroded in late
Cretaceous; (3) Diabase intrudes the coal-bearing
strata in Tertiary and highly permeable contact zone
is developed. Thermogenic gas from the contact
metamorphic coal and deep strata, secondary
biogenic gas from meteoric water along the contact
zone, mixed with original low mature thermogenic
gas.
� 13 C-CH4(‰ vs.PDB)
-120
-100
-80
-60
-40
-20
Fuxin Powder River
II
IV
IV
0
-450 -400 -350 -300 -250 -200 -150 -100 -50 0
III
I
�D-CH4(‰ vs.SMOW)
Fig.1 Whiticar‘s CD diagram methane
showing compositional fields for gases of various
origins (Whiticar, 1999).
①-thermogenic gas;②-bacteria methyl type
fermentation gas;③-bacteria carbonate reduction
gas;④-mixed and transition gas. Data of Powder
River from Flores et al.(2008) are used for
comparison.
References
[1] Flores R M, Rice C A, Stricker G D, Warden A,
Ellis M S. Methanogenic pathways of coal-bed
gas in the Powder River Basin, United States:
The geologic factor [J]. <strong>International</strong> Journal of
Coal Geology, 2008,76: 52–75
[2] Whiticar M J. Carbon and hydrogen isotope
systematics of bacterial formation and oxidation
of methane [J]. Chemical Geology, 1999, 161:
291–314.
502

P-374
Bulk geochemical characterisation of the source rocks for shale
gas in Poland
Irena Matyasik, Wojciech Bieleń, Tomasz Słoczyński
Oil and Gas Institute, Cracov, Poland (corresponding author:matyasik@inig.pl)
This paper presents the general geochemical
characteristics of Silurian shale with the aim to
constrain its shale gas potential.
Detailed biomarker and light hydrocarbons
geochemistry confirms that the marine Silurian Shale
is the primary source rock for exploration shale gas in
Poland. Study of the area has been divided into four
parts: Baltic Basin, NE part of Poland (EEC), Lublin
Area and Carpathian Foredeep.
In the Baltic Basin source rocks richest in organic are
observed within Llandovery section. Organic matter of
the shale is characterized by II type of kerogen.
Average TOC contents of Silurian shale are very
different, and vary from less than 0,5 wt. % to 12
wt.%. In the Baltic Basin lateral changes of thermal
maturity correspond to changes of present day burial
[2]. Maturity increases to the west, as the burial does,
and there thermal maturity reaches the value above
3,5 %Ro at the depth 4300m.
In the NE part of Poland the Silurian Shale were not
buried to deep so they are relatively of low mature
(0,6 – 0,75%Ro) and could be considered as source
for both oil and gas generation due to high Hydrogen
Index (above 300 mg HC/g TOC).
Other shale – gas system in Poland is located in
Lublin area where Silurian has been recognized as
good source rocks with II type kerogen. Average
organic matter content is usually in range of 0,25
wt.% to 7,92wt.%. Thermal maturity increases
towards the southeast thus TOC would be expected
to show a general decrease in this direction as
hydrocarbons are generated and expelled (Fig.1).
Organically enriched Silurian Shale with lower thermal
maturity occurs in the last of investigated basins -
Foredeep Carpathian. Most of the samples have HI
values (at present day) between 350 and 500mg
HC/g TOC with S2 values up to 20,5mg HC/g of rock
indicating oil-prone source rock potential. Organic
maturity parameters and modelling indicate that this
formation is at the peak maturity for hydrocarbon
generation.
Remaining Hydrocarbon Potential [mg HC/g Rock]
0 2 4 6 8 10 12 14 16
60
55
Lublin Area
Carpathian Foredeep
Type II
Oil Prone
60
55
50
Baltic Basin
50
45
40
35
30
25
20
15
10
East European Craton
Mixed Type II/III
Oil/Gas Prone
Type II
Gas Prone
5
Dry Gas Prone
5
0
0
0 2 4 6 8
TOC [%]
10 12 14 16
Fig.1. Present-day kerogen type of Silurian Shale in
Poland
Taking into consideration the American expierence in
exploration and exploitation, the most favourable
condition for shale gas exploration in Poland can be
expected in Baltic Basin.
References:
[1] Hill, R. J., Jarvie D.M., Pollastro R.,M., Mitchel H.
and King J.D. 2007. Oil and gas geochemistry and
petroleum systems of the Fort Worth Basin. AAPG
Bull. , Vol. 91, No.4, pp.437- 444.
[2] Poprawa.P.,2010. Shale gas potential of the Lower
Paleozoic Complex in the Baltic Basin and Lublin-
Podlasie Basin (Poland). Geological Review, 58, 226-
249.
503
45
40
35
30
25
20
15
10

P-375
Integration of basin modeling and geochemistry to describe dual
sourcing of granite wash reservoirs, Anadarko Basin, USA
Tony McClain 1,2 , Harris Cander 3,4 , Jonathan Evenick 5,6
1 Texas A&M University, College Station, United States of America, 2 Brigham Young University, Provo,
United States of America, 3 University of Texas, Austin, United States of America, 4 SUNY, Stony Brook,
United States of America, 5 University of Tennessee, Knoxville, United States of America, 6 University of
Buffalo, Buffalo, United States of America (corresponding author:tony.mcclain@bp.com)
In the onshore of the United States, exploration and
development plays rich in liquid hydrocarbons are
rapidly taking the spotlight away from dry gas plays in
the present economic environment. The
Pennsylvanian (PENN) Granite Wash (GW) is one
such play in the Anadarko Basin of Oklahoma and
Texas, U.S.A. Reservoir lithologies are highly
variable, and were shed northward into the basin as
the Wichita Mountains to the south were eroded. The
range was stripped down to the Precambrian
basement before being buried by Permian carbonates
and Mesozoic clastics [1] . Reservoirs were deposited
as alluvial fans and fan-deltas into the sea
immediately adjacent to the mountain front [1] .
The most important source rock in the Anadarko
basin has long been understood to be the Woodford
(WDFD) shale (Devonian-Mississippian). Wang and
Philp [2] established geochemical evidence for
significant generative capacity of the oil-prone Viola
Group (Ordovician), as well as the gas-prone Springer
Formation and Morrow Group (lower PENN) which lie
immediately below the GW. Burruss and Hatch [3] also
discussed the source potential of middle PENN
shales equivalent to and inter-bedded with GW
reservoirs. They demonstrated geochemically that
many oils in the Anadarko basin are mixtures, having
been sourced from up to three different source
intervals.
Twenty gas samples from PENN and deeper
formations were acquired and analyzed for
composition and stable carbon isotopes. Figure 1
shows two different gases, as distinguished by stable
carbon isotopes data. Related to source rock kinetics
(curves on the graph), the two families are interpreted
to represent gases originating from the WDFD and
PENN shales. The WDFD gases were obtained from
GW and other Pennsylvanian reservoirs as well as
deep Arbuckle and Hunton reservoirs. Whole oil gas
chromatography data from GW reservoirs also reveal
at least two different sources, consistent with the
interpretation from the gas isotopes samples. Basin
modeling suggests that while much of the WDFD
charge moved laterally out of the basin via pre-WDFD
strata, some also migrated vertically, focused by local
structures near the mountain front. Thus, petroleum
in GW reservoirs can be explained by charging from
proximal PENN shales, from the deeper WDFD shale,
or a varying mixture of the two.
Fig. 1. Del C13 ethane vs. Del C13 methane crossplot.
References
[1] Sorenson, R.P., 2005, A dynamic model for the
Permian Panhandle and Hugoton fields, western Anadarko
basin, AAPG Bull., v. 89, No. 7, pp. 921-38.
[2] Wang, H.D., and Philp, R.P., 1997, Geochemical
Study of Potential Source Rocks and Crude Oils in the
Anadarko Basin, Oklahoma, AAPG Bull., v. 81, No. 2, pp.
249-75.
[3] Burruss, R.C., and Hatch, J.R., 1989,
Geochemistry of oils and hydrocarbon source rocks, greater
Anadarko basin: evidence for multiple sources of oils and
long-distance oil migration, Oklahoma Geological Survey
Circular 90, pp. 53-64.
504

P-376
Organic geochemical variability of gas shales: Woodford Shale,
Southeastern Oklahoma, USA, a case study
Andrea Miceli Romero, R. Paul Philp
The University of Oklahoma, Norman, United States of America (corresponding
author:andreamiceli@ou.edu)
It has been very common to consider shales
as uniform stratigraphic sequences in terms of
physical and chemical properties. However, a more
detailed analysis of these source/reservoir rocks can
provide greater insight about variations in the
depositional and environmental factors that influenced
source rock deposition. The Woodford Shale (Upper
Devonian-Lower Mississippian), once considered as a
source rock for both oil and natural gas in the United
States Southern Midcontinent, has recently evolved
as an important shale gas play due to its high
hydrocarbon potential [1-2]. The use of geochemistry
to characterize these unconventional reservoirs has
played a significant role in shale gas evaluation in
terms of helping to determine the type of organic
matter, thermal maturity, paleoenvironmental
conditions, and to be effective for establishing
sequence stratigraphic frameworks of these
source/reservoir rocks.
Woodford Shale samples obtained from a
cored outcrop in southeastern Oklahoma were
analyzed geochemically to determine vertical
variations of organic facies, thermal maturity and an
evaluation of the depositional environments. Samples
were characterized on the basis of total organic
carbon (TOC), Rock Eval pyrolysis, and measured
and calculated vitrinite reflectance (%Ro). Additionally,
crushed rock samples were extracted and extracts
were subjected to gas chromatography (GC) and gas
chromatography-mass spectrometry (GCMS) for
biomarker analyses.
The Woodford Shale was subdivided into
lower, middle and upper members based on the
integration of geochemical and geological data.
Moreover, the presence and extent of photic zone
anoxia was determined by the presence of aryl
isoprenoids. Aryl isoprenoids also helped to infer the
position of the chemocline during deposition of the
different members. The relative hydrocarbon potential
(RHP) parameter derived from Rock Eval data was of
use in determining transgressive and regressive
cycles within the Woodford Shale. TOC values ranged
from 5.01% to 14.81% indicating good source rock
potential. In the study area the Woodford Shale is
mature to marginally mature as indicated by vitrinite
reflectance values; therefore, it is unlikely that the
Woodford Shale has generated high quantities of
hydrocarbons in this area. Biomarker ratios based on
pristane, phytane, steranes, and hopanes show a mix
of marine and terrestrial organic matter with the
middle member showing the greatest marine input.
Integration and correlation of Pr/Ph ratios, aryl
isoprenoids ratios and relative hydrocarbon potential
(RHP) indicate that the lower Woodford was
deposited under dysoxic/suboxic conditions and
episodic periods of photic zone anoxia (PZA) during a
major transgressive-regressive-trangressive cycle; the
middle Woodford was deposited under anoxic
conditions and persistent PZA during a major
transgression (sea-level rise); and the upper
Woodford was deposited under dysoxic/suboxic
conditions and episodic PZA during a general
regression (HST with high sedimentation rate). These
interpretations are consistent with a sequence
stratigraphic framework already proposed for the
Woodford Shale in the study area. High salinity
conditions and water density stratification also
prevailed during deposition of this formation as
indicated by the presence of gammacerane. The
chemocline was located at shallower depths during
middle Woodford deposition and fluctuated within
different depths during deposition of lower and upper
members.
This work undoubtedly demonstrates the
significant lithological and chemical variability that
occurs within shales, a factor that needs to be taken
into account when exploring and producing from
these self-sourced reservoirs.
REFERENCES
[1] Cardott B. J. (2005) Ok. Geol. Surv. Circ. 110, 7-
18.
[2] Comer J. B. (2007) GSA <strong>Meeting</strong> – Abstracts with
programs, pp. 356.
505

P-377
Oil shales occurring in Mongolia
Vadim Saveliev 1 , Namkhainorov Jargalsaikhan 2 , Galina Pevneva 1 , Anatoly Golovko 1
1 Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russian
Federation, 2 Institute of Chemistry and Chemical Technology of the Mongolian Academy of Sciences, Ulan
Batar, Mongolia (corresponding author:savel@ipc.tsc.ru)
Geological resources of oil shales occurring in
Mongolia amount to about 788.0 million tons. Only
20 % of them are characterized in detail including
estimation and kinds of geological resources of the
natural caustobioliths. The oil shales occurring in
Mongolia can be considered as alternative
hydrocarbon raw material.
The present work is aimed to investigate
composition of organic matter in oil shales occurring
in Mongolia for possible production of liquid and
gaseous products.
Six samples of raw oil shales mined from Baliin
jis, Khuut bulag, Tukhurmiin nuur and Khugshin gol
fields have been investigated. Ash content of the
samples reaches 70-83 % mass. A mineral
constituent of oil shales is mainly presented by
carbonates, 15-52 %, and silicates, 18-66 %. The
yield of volatile products varies from 14.7 (a sample
from Tukhurmiin nuur field) to 26.6 % mass (Baliin
jis). The kerogens were separated by a method
described in work [1]. The content of kerogenes in
oil shales amounts to 4-15% mass and that of
chloroform bitumoids A – 0.2–1.0 % mass.
Table – Characteristics of kerogens in oil shales
Kerogen Н/С О/С S
Sample yield, %
mass
Baliin jis 4.2 2.3 0.2 1.9
Khuut bulag-1 8.0 1.8 0.1 0.4
Khuut bulag–2 15.3 2.2 0.1 1.3
Khuut bulag-3 11.1 1.5 0.1 0.6
Tukhurmiin nuur 13.1 2.3 0.2 2.1
Khugshin gol 15.2 2.0 0.1 1.9
By the values of atomic ratios of the basic
elements (С, Н and О) kerogenes refer to type I,
they were generated under similar conditions from
marine sediments enriched with algal lipids
accumulated in reducing environment [2].
The data of IR-analysis of structural features of
kerogens in oil shales proved shale belonging to
OM of I type. Considerable excess of aliphatic
fragments over aromatic structures in OM assumes
predominance of low-molecular hydrocarbon
components and a low yield of shale resin in the
products of the oil shale pyrolysis.
We used a thermal analysis to reveal specific
character of the compositions of organic and mineral
substances in oil shales. Diagrams of mass losses in
oil shales depending on the temperature are
presented in the Figure below.
The mass loss in shales occurs up to the
temperature range of 200-250 0 С caused by
exudation of moisture – hygroscopic and ―bound‖
water. Destruction of organic compounds bound by
heteroatomic elements is also possible. The mass
losses in oil shales in this temperature interval
amount to 1.5-4.8 %.
At temperature increase up to 500-550 0 С
thermal-oxidative conversions of OM proceed at
high rates. Relatively easy oxidation of oil shales
testifies predominance in OM structure of labile
components of mainly aliphatic nature, with which
oxygen reacts first as with the most energyweakened
sections of molecules [2]. The loss of
mass was maximal in this temperature interval and
amounted to 10-25 %.
Thermal-oxidative destruction of a mineral
constituent in oil-shales proceeds in the temperature
range of 600-900 0 С at negligible changes in the
rate of mass loss. For the samples mined from
Baliin jis and Tukhurmiin nuur one determined a
sharp increase in the rate of mass loss at 730-780
0 С, typical for decomposition of low-basic calciumsodium
hydrosilicates. [3]. The samples of oil shales
mined from Khuut bulag-1and Khuut bulag–3 fields
have the highest oil-generating potential.
Thus, a high content of hydrogen and rather
low contents of sulfur and nitrogen as well as
structural features of kerogen are the reasons to
suppose the production of high-quality and
ecologically pure ―synthetic‖ oil at complex
processing of oil-shales occurring in Mongolia.
Reference
1. B. P. Tissot, D. H. Welte. Oil generation and
distribution. M.: Mir. – 1981.-501 p.
2. Goftman M.V. Applied chemistry of solid fuel. M.:
1963., 235 P.
3. Sidorovich Ya.I. // Oil shale.1984. V. 1. №2. P. 171-
174.
506

P-378
East Texas-North Louisiana USA unconventional shale gas
resource systems
Daniel Jarvie 1 , Francoise Behar 2 , Yongchun Tang 4 , Rolando di Primio 3 , Brian Horsfield 3 ,
Wilhelm Dominik 1
1 Technische Universitat Berlin, Berlin, Germany, 2 Insitut Francais du Petrole, Rueil-Malmaison, France,
3 GFZ, Potsdam, Germany, 4 PEER Institute, Covina, United States of America (corresponding
author:danjarvie@wwgeochem.com)
Unconventional shale gas accounts for about
20% of the available gas resource in the USA with a
resource amounting to about 1000 tcf of gas-in-place
(GIP). There are over 50 shale resource plays active
in North America either for shale gas or shale oil. The
focus of this work is the shale gas systems present in
the East Texas-North Louisiana Salt Basin (ETNLSB)
consisting of gas with minor condensate from
Tithonianian Bossier and Kimmeridigian Haynesville
shales.
Petroleum system analysis of gas petroleum
systems is difficult when attempting to correlate to
high maturity gas source rocks. However, recovery of
gases and in some cases, condensates directly from
the source rock aids this assessment. In the case of
the principal source rocks in the ETNLSB, the
Tithonian Bossier and the Kimmeridgian Haynesville
shales are highly mature typically over 1.2%Roe.
Age-equivalent immature source rocks from the
deepwater Gulf of Mexico provide material for
evaluation of this resource by laboratory maturation
experiments optimized to field results.
The original source potential of the Tithonian
and Kimmeridigian systems can be subdivided into
multiple mappable organofacies based on hydrogen
indices (HI) and TOC. The Bossier Shale is
subdivided into three mappable organofacies with
variable hydrogen indices, whereas the Haynesville
Shale is divided into two mappable organofacies
based on TOC differences.
Not unexpectedly condensate analysis
shows oil cracking by loss of the labile
dimethylcyclopentanes consistent with MSSV oil
cracking experiments. Comparison of light
hydrocarbon data to diamondoid cracking parameters
shows good correlation. Interestingly, the C2 isotopic
rollover does not occur in certain parts of the basin
despite high thermal maturity (ca. 2.0%Ro), behaving
in a purely thermogenic realm following model
predictions (Jarvie et al., 2010) (Fig. 1). Other areas
of the basin at comparable thermal maturity show C2
carbon isotopic rollover with increasing gas dryness
Ethane Carbon Isotope (� 13 C 2)
0 5 10 15 20 25
-20
-25
-30
-35
-40
-45
-50
Thermogenic trend
Rollover
Gas Wetness (%C2+)
Shale 1
Shale 2
Haynesville
Figure 1. No rollover in high maturity ETNLSB gas.
(Figure 1) where C2 carbon isotopes become lighter at
high maturity (Ferworn et al., 2008). Tang and Xia
(2010) have observed a new reaction where water
can react with condensates to generate CO2 and
hydrogen. It is not clear under what condition the CO2
and hydrogen can generate methane, ethane and
propane with isotope reversal (like abiogenic gases
from geothermal fluid). Rollover and non-rollover
systems may be a function of Tithonian organofacies
differences.
Phase kinetics and gold tube pyrolysis on
age-equivalent immature Tithonian and Kimmeridgian
immature samples substantiated yields and
composition at various levels of maturation for these
source units. These results are applicable to
evaluation of petroleum generation in the ETNLSB as
well as the Deepwater Gulf of Mexico.
References
Jarvie, D., F. Behar, L. Mazeas, 2010,
Decomposition of organic matter and impact on shale
resource play assessments, AAPG New Orleans ACE
Ferworn, K., Zumberge, J., Reed, J. and
Brown, S., Gas Character Anomalies Found in Highly
Productive Shale Gas Wells, GeoMark Research
Technical Presentation, Houston, October 2008, 26 p.
Tang, Y. and X. Xia, 2010, Kinetics and
mechanism of shale gas formation: a quantitative
interpretation of gas isotope ―rollover‖ for shale gas
formation, AAPG Hedberg Research Conf., Austin,
Texas, December 5-10, 2010, abstract.
507

Thursday Poster Presentations
508

P-380
Distribution, fate and formation of non-extractable residues of a
nonylphenol isomer in soil derived organo-clay complexes and
first evidence for a stereoselective incorporation process
Jan Schwarzbauer, Patrick Riefer, Timm Klausmeyer, Andreas Schaeffer, Burkhardt
Schmidt
RWTH Aachen University, Aachen, Germany (corresponding author:schwarzbauer@lek.rwth-aachen.de)
Xenobiotics released to soil undergo complex processes
which lead to extractable but also non-extractable residues
(NER). The latter are characterized by interactions with
humic substances or mineral surfaces covering the range
from weak adsorptive to reversible or irreversible covalent
bonds. Generally,the formation of NER in soil have huge
implications in the fate of pollutants (e.g. bioavailability, plant
uptake, microbial degradation and toxicity).
Within soil, the clay fraction plays a major role in the
formation of non-extractable residues (NER) due to its
specific surface characteristics and the preferred association
of soil organic matter to the minerals.
4-Nonylphenols are of high environmental interest due to
their ubiquitous appearance and ability to disrupt the
endocrine system of higher organisms. Technical
nonylphenol is an isomer mixture used industrially to
produce nonlyphenol polyethoxylates (NPnEO) which act as
nonionic surfactants in many products. However, these
surfactants once released into the environment undergo
microbial degradation with release of nonylphenols as major
metabolites.
The aim of the presented study was to investigate the fate
and distribution of a specific NP isomer (353-NP) within soil
and soil derived organo-clay complexes. Therefore, 14 C- and
13 C-labeled 353-NP was added to soil samples and
incubated up to 180 days. Mineralization was measured and
soil samples were fractionated into sand, silt and clay. The
clay fraction was further separated in humic acids, fulvic
acids and humin. Lastly, the NER in the different humic
fractions were released by common organic-geochemical
approaches like alkaline hydrolyses, BBr3-treatment, RuO4oxidation
and TMAH-thermochemolysis.
After 180 days of incubation the predominate incorporation
sites of 353-NP were the organo-clay complexes (27% of
applied radioactivity), whereas only 22 % was mineralized.
The water extractable portion was low (9 % of applied 14 C)
and remained constant during the entire incubation period.
Separation of organo-clay complexes, after extraction with
solvents to release weakly incorporated, bioaccessible
portions, showed that non-extractable residues (NER) were
preferentially located in the humic acid fraction.
water solved
(15.11) 11.9%
CO 2 (1.62)
1.3%
loss (16.11)
12.7%
clay (55.32)
43.6%
sand (4.35)
3.4%
silt (34.45)
27.1%
Fig. 1: Distribution of NP radioactivity between individual soil
particle size fractions, water phase and CO2 as
mineralization indicator.
More detailed investigations by means of sequential
chemical degradation indicated a predominant incorporation
of non-extractable NP isomer residues via ester bonds as
released by alkaline hydrolysis. The amount of releasable
compounds decreased until day 180 indicating a change of
the incorporation behavior as a consequence of ageing
processes. BBr3-treatment, RuO4 oxidation and TMAHpyrolysis
released only low portions of non-extractable 14 C
giving evidence of minor influence of ether and C-C-linkages
in the incorporation processes.
Analysis of the diastereomeric composition of 353-NP in the
extractable and non-extractable fractions and comparison of
these ratios from biotic and abiotic experiments revealed
significant alterations. These systematic changes gave clear
evidence that the process of microbial assisted incorporation
of 353-NP into soil organic-clay complexes is a
stereoselective process. To our knowledge, this is the first
report on a stereoselective incorporation process of organic
substances forming non-extractable residues.
Fig. 2: Diastereomeric ratios of NP in soil derived organic-clay complexes. o =
extractable fraction,square = hydrolysable fraction from humic acids, triangle =
hydrolysable fraction from humins.
water solved
(434.26)
74.3%
509
loss (23.11)
3.9%
sand (15.49)
2.7% silt (43.01)
7.4%
clay (67.93)
11.6%
CO 2 (0.60)
0.1%

P-381
Permissible concentration of petroleum contaminants as
determined from studying the adaptive reaction of plants in a
model experiment with permafrost soil f yakutia
Sara Lifshits, Olga Chalaya, Yulia Glaznetsova, Iraida Zueva
Institute for Biological Problems of Cryolithozone, Siberian Department, Russian Academy of Sciences,
Yakutsk, Russian Federation (corresponding author:s.h.lifshits@ipng.ysn.ru)
The behavior of plants (Lepidium ruderale L. and
Artemisia vulgaris L.) was studied in a model
experiment with permafrost sod-and-grass soil of
Yakutia contaminated with petroleum. It has been
shown that of all the physiological characteristics of
plants, the most informative in studying the process of
adaptation to petroleum contamination is the survival
coefficient calculated as the ratio of the number of
survived plants to that of germinated seeds. Variation
of the coefficient with the amount of petroleum
introduced into soil is, for both plants, bimodal in
character, with a tendency for a decrease. One can
see two areas of maximum coefficient values in each
of the plots given below, which seem to reflect
different strategies in plant adaptation to the growing
intensity of the stress factor (Fig.1). Addition of
petroleum in quantities of 0.25% for Lepidium
ruderale L. and 0.32% for Artemisia vulgaris L.
resulted in a more intense accumulation of
contaminants in soil (Fig. 1). The proportion of
hydrocarbon fractions in the composition of
contamination and the distribution of individual
alkanes became close to those in reduced crude.
Fig. 1. Plots of the survival coefficient of plants and
the intensity of contaminants accumulation versus the
amount of petroleum added into soil.
Comparison of the results of experiments with and
without growing plants revealed a more profound
transformation of petroleum pollutants in the presence
of plants. The growing plants sped up the destruction
of petroleum hydrocarbons. As a result, the level of
contamination decreased by 60.2% (Artemisia
vulgaris L.) and 66.8% (Lepidium ruderale L.) as
compared with 31.5% observed in cases when
biodegradation of contaminants was only caused by
soil microflora. Studies on the regularities in the
distribution of individual hydrocarbons showed that
not only do the present plants increase the degree of
pollutants transformation but widen the range of
structural isomers of alkanes undergoing
biodegradation too (along with n-alkanes and 2- and
3-methyl alkanes, subjected to transformation were
12- and 13-methyl alkanes and isoprenoids). Thus,
the varying hydrocarbon composition of bitumoids
reflects a tendency toward restoration of the natural
geochemical background (Fig. 2).
Fig. 2. Mass-fragmentograms (m/z 57) of hydrocarbon
fractions in soil samples. Sample A: 0.16% petroleum,
without plants; C: 0.16% petroleum, with growing
Artemisia vulgaris L.; D: 0.16% petroleum, with
growing Lepidium ruderale L.; E: initial soil sample.
The results of studying the adaptive potential of plants
and the efficiency of contaminants transformation
permitted us to estimate the permissible concentration
of contaminants in soil as 1g/kg on average.
510

P-382
Polycyclic aromatic hydrocarbons in bottom sediments of the
Laptev and the East Siberian seas
Ivan Litvinenko, Vera Petrova, Galina Batova, Anna Kursheva
I.S.Gramberg VNIIOkeangeologia, Saint-Petersburg, Russian Federation (corresponding
author:ivanlitvinenko@mail.ru)
This study is devoted to the eastern seas of
Russia - The Laptev Sea and The East Siberian Sea.
This is due to several reasons. Firstly, the region is
still not as well studied as the Western Arctic.
Secondly as other high Arctic ecosystem has a low
tolerance to human impacts. And also because even
slight human impact in the region, we can say that the
real parameters of the different components of the
environment can be considered as background. And
that they can be used in future evaluation of changes
in the conditions of marine ecosystems. Bottom
sediments from the eastern part of Russian Arctic
were analysed to identify major sources and
pathways of polycyclic aromatic hydrocarbons
(PAHs).
Materials for the research were sediments
sampled at 97 stations from the bottom sediments of
the Eastern Arctic shelf during Russian and
international research-vessel expeditions carried out
in 1993-1995s. The bottom sediments were taken by
grabs and gravity corers with plastic liners. Samples
from the surface layer (0–5 cm) were placed into
sterile boxes and kept under a temperature of –18°C.
Natural organo-geochemical background of PAH
in the marine sediments is formed under the influence
of genetic and lithological–facial factors, while its
variations depend on conditions of sedimentation. In
the sediments of the eastern Arctic shelf, the total
PAH contents vary from 3 to 180 ng/g with the
average value not exceeding 40 ng/g, which is
substantially lower as compared with that previously
reported for the sediments of its western part [1, 3, 4].
The study of the spatial PAH distribution in the
sediments reveals the dominant role of the river
discharge. For example, the elevated PAH contents
are confined to delta zones of large rivers and are
traced along their paleovalleys up to deposition areas
of the sedimentary material near the continental
slope. Their composition is dominated by
phenanthrene and chrysene structures. The
distribution of perylene, which is indicator of a
terrestrial organic matter flux, confirms this. The
pyrogenic component in the PAH composition is
poorly pronounced (Fl/202 = 0.25) and is registered
mainly in the sediments of the Lena River delta area.
In conclusion, the PAH distribution in the
sediments sampled in Tiksi Bay should be mentioned.
The total PAH content in the sediments of the harbor
amounts to 3695 ng/g, which is two orders of
magnitude as high as the background values. The
dominant component is represented by pyrogenic
group 202, the content of which is as high as 1193
ng/g, which is characteristic of strongly polluted
technogenous sediments [2,3].
References
1. V. I. Petrova, ―Geochemistry of Organic Matter
in Estuarine–Shelf Sediments: Polycyclic Arenes in
the River–Sea Cross Section,‖ in Experience of
System Oceanological Studies in the Arctic (Nauchnyi
Mir, Moscow, 2001), pp. 235–243 [in Russian].
2. F. Ya. Rovinskii, T. A. Teplitskaya, and T. A.
Alekseeva, Background Monitoring of Polycyclic
Aromatic Hydrocarbons (Gidrometeoizdat, Leningrad,
1988) [in Russian].
3. S. Dahle, V. Savinov, V. Petrova, et al.,
―Polycyclic Aromatic Hydrocarbons (PAHs) in
Norwegian and Russian Arctic Marine Sediments:
Concentrations, Geographical Distribution, and
Sources,‖ Norwegian J. of Geology 86, 41–50 (2006).
4. M. B. Yunker, L. R. Snowdon, R. W.
Macdonald, et al.,―Polycyclic Aromatic Hydrocarbon
Composition and Potential Sources for Sediment
Samples from Beaufort and Barents Seas,‖ Environ.
Sci. Technology 30 (4), 310–1320 (1996).
511

P-383
Accumulation and degradation of plastic pollutants and
diisopropyl-naphthalenes during composting of organic
household waste
Cesar Menor-Salvan
Centro de Astrobiologia (INTA-CSIC), Torrejon de Ardoz, Spain (corresponding author:menorsc@cab.intacsic.es)
Composting of household and urban organic waste
received much attention by municipal authorities due
to its utility in the recycling and volume reduction of
waste. According with the waste management plan of
the Spanish Government (Plan Nacional Integrado de
Residuos 2007-2015, PNIR), in Spain, the 45-53% of
the solid urban waste are composed by food or
gardening residues and most of these waste is
processed in 65 composting plants that generated
720.000 tons of compost in 2006. This compost is
used mainly for agriculture and gardening. Following
this effort, the market of small units for homebrew
compost using household waste increased in parallel
with the ecological education of the public and now is
a widespread practice. In spite, little attention has
been received the molecular composition of compost
(Spaccini and Piccolo, 2007). Also, the non-beneficial
effects of application of compost on the soil quality or
incorporation of contaminants to farm products is still
not very well understood. In this sense, González-Vila
et al (1999) noted the increase of phthalate esters in
juice of tomatoes growth in compost-amended soils,
together with changes in the lipid composition,
suggesting a potential risk in the use of compost in
the food industry.
Following this line of evidence and the potential use of
composting units as a model of concentration and
early diagenesis of terpene biomarkers, the study of
the organic solvent extractable fraction of compost,
generated using household units, was carried out. For
this study, a small compost unit (1,5 m 3 ) situated in an
urban environment was filled exclusively with food
and gardening residues free of paper, plastic or noncompostable
debris during five years. Yearly, samples
of compost were extracted in
dichloromethane/methanol 3:1 and analyzed by gas
chromatography/mass spectrometry (GC-MS)
Results and conclusion
The main single components of the extractable
fraction of compost (mean 29.6% of total compost) is
constituted by plant lipids, n-alkanes and plastic
contaminants. The plastic contaminants found are
dominated by phthalate esters, followed by
2,4.ditertbutylphenol and bisphenol A. Other relevant
anthropogenic compounds found are the diisopropylnaphthalene
isomers (DIPNs). The DIPNs could be
accumulated in compost from the food residues, as
consequence of migration from cardboard or paper
packages (George et al. 2010; Sturaro et al., 1994).
DIPNs and phthalates are effectively degraded during
compost maturation: 15.4% of total extract after 1
year, 0.9 % after 5 years with only phthalates
remaining. On the contrary, bisphenol A show
resistance to degradation with accumulation on
compost (0.1% of total extract after 1 year, 0.59%
after 5 years).
Further study is necessary in order to understand the
fate of organic pollutants during composting and to
evaluate possible risks of the use of poorly maturated
composts in agriculture.
References
George, S.C., Volk, H., Romero-Sarmiento, M.F.,
Dutkiewicz, A., Mossman, D.J., 2010. Diisopropyl
naphthalenes: Environmental contaminants of
increasing importance for organic geochemistry
studies. Organic Geochemistry, 41, 901-904.
González-Vila, F.J., Almendros, G., Madrid, F., 1999.
Molecular alterations of organic fractions from urban
waste in the course of composting and their further
transformation in amended soil. The Science of Total
Environment, 236, 215-229.
Spaccini, R., Piccolo, A., 2007. Molecular
characterization of compost at increasing stages of
maturity. 1. Chemical fractionation and infrared
spectroscopy. Journal of Agricultural and Food
Chemistry, 55, 2293-2302.
Sturaro, G., Parvoli, G., Rella, R., Bardati, S., Doretti,
L., 1994. Food contamination by diisopropyl
naphthalenes from cardboard packages. <strong>International</strong>
Journal of Food Science & Technology, 29, 593-603.
512

P-384
Fingerprinting of oil sheens, slicks, and tarballs collected in
response to the MC 252 oil spill
Alexei Milkov 1 , Changrui Gong 2 , David Grass 2 , Mike Sullivan 2 , Tomieka Searcy 2 , Leon
Dzou 2 , Pierre-Andre Depret 2
1 BP Russia, Moscow, Russian Federation, 2 BP America, Houston, United States of America (corresponding
author:alexei.milkov@bp.com)
Petroleum leaked into the Gulf of Mexico (GoM) water
column as a result of Deepwater Horizon (DWH)
incident which occurred in Mississippi Canyon Block
252 (MC 252) on April 20th, 2010. 1553 samples of oil
sheens, slicks and tarballs were collected from the
sea surface and along the coastlines in Texas,
Louisiana, Mississippi, Alabama and Florida in
response to the incident from May 11th to November
21st, 2010. The samples were subjected to a
comprehensive geochemical analysis. At the time of
writing (January 18th, 2011), we analyzed and
interpreted 839 samples of oil sheens, slicks and
tarballs. The vast majority of the interpreted samples
(93%) were collected prior to August 15th, 2010.
Origin and source of collected oil sheens, slicks and
tarballs samples were determined based on a
geochemical fingerprinting workflow. First, ranges of
geochemical parameters in the source oils were
established. For the source oils we used three MDT
samples collected in the MC 252 well, nine samples
collected during oil production at the Enterprise and
Q4000, and 21 skimmed oils that were judged to be
sourced by MC 252 oil spill based on their physical
appearance, chemical fingerprint and geographic
location. The studied geochemical parameters include
ratios of alkanes and isoprenoids, δ 13 C of SARA
fractions, and weathering-resistant high molecular
weight biomarkers reflecting the depositional
environment as well as the maturity of source rocks.
The established ranges of parameters account for
variations in the source oils and accuracy of analytical
measurements. Second, geochemical parameters in
the studied weathered oil samples were compared to
those in the source oils. Finally, the weathering trend
was established based on the skimmed source oils
and samples of weathered oils and tarballs were
plotted to check the conformance to that trend.
Samples of oil sheens, slicks and tarballs were
interpreted to be probably from MC 252 if they had
the same geochemical fingerprints (accounting for
weathering) as MC 252 source oils. Among the
analyzed and interpreted 818 samples of unclear
origin, 466 samples are probably from MC 252. Such
samples occurred mostly within the areal extent of
sea surface oil and along coastlines of Louisiana,
Mississippi and Alabama where more oil emulsion
reached the shore. Based on a basic preliminary
statistical analysis of biomarkers in all samples, we
determined samples which have fingerprints not
identical but relatively similar to the known MC 252
source oils. Such samples may have originated from
yet unknown MC 252 source oils and were interpreted
as may be from MC 252. There are 47 such samples.
Samples that had geochemical fingerprints clearly
different from those in the source oils were interpreted
to be not from MC 252. There are 305 such samples,
and they were collected every week after the DWH
incident.
Our interpretation suggests that 305 samples of oil
slicks, sheens and tarballs of unclear origin, or 37% in
the studied dataset, did not match the DWH oil spill
fingerprint. The percentage of samples matching the
DWH fingerprint was higher for beaches near the
wellhead and lower for beaches further away. Some
of the samples were in a heavily weathered state,
indicating that they had been released months or
years before the DWH incident occurred. Some of the
samples had biomarkers that are not found in the
DWH fingerprint. Because this study did not include a
program to take representative samples of all oil
found in the DWH incident response, it does not
identify the percentage or volume of oil resulting from
the DWH incident, in comparison to other oil existing
in the GoM. There are many possible sources of
these non-MC 252 samples. Around 1,000,000
barrels of petroleum per year [1] or more may be
released into the GoM from natural seeps and some
of that oil ends up as tarballs along the Gulf shores.
Other sources include oil releases from pipelines and
wells in the Gulf Coast rich petroleum infrastructure
[2], spills from bypassing vessels through operational
discharges [3], cargo washing and direct spills [4].
[1] Kvenvolden, K.A., Cooper, C.K., GeoMar. Let., 23,
140–146.
[2] www.incidentnews.gov
[3] Oil in the Sea III, 2003.
[4] Dalton, T., Jin, D., Mar. Poll. Bull., 60, 1939-1945.
513

P-385
Source determination and depth translocation of PAH in Chinese
paddy and non-paddy soils
Cornelia Mueller-Niggemann 1 , Philipp Roth 2 , Eva Lehndorff 2 , Lorenz Schwark 1
1 Institute of Geosciences, Christian-Albrechts-University of Kiel, 24118 Kiel, Germany, 2 Institute of Crop
Science and Resource Conservation, Soil Science and Soil Ecology, University of Bonn, 53115 Bonn,
Germany (corresponding author:cmn@gpi.uni-kiel.de)
The incomplete combustion of organic residues leads
to the formation of polycyclic aromatic hydrocarbons
(PAH) and a macromolecular, highly condensed
complex residue termed black carbon (BC).
Widespread fertilization practices are burning of crop
residues in the field or adding ashes from domestic
burning to the field, which introduces large quantities
of condensed organic matter (OM) into soils.
We present results from a chronosequence study of
paddy and non-paddy soils with different and well
known starting dates of cultivation in the Zhejiang
province (Yangtze River delta) by land reclamation
through the building of protective dikes over the past
2000 years. The end member of natural sediments
subjected to land reclamation, a marine tidal mudflat
in the Yangtze delta, represent the substrate on which
the soil evolution started. In the study area a
traditional method of rice straw disposal is open field
burning, which leads to the incorporation of specific
PAH and BC into paddy soils.
As expected, the quantitatively dominant fraction of
the condensed, highly aromatic soil OM is
macromolecular BC with a range of 1.1 to 2.1 mg/g
dw in paddy topsoils (TS) and 0.7 to 1.1 mg/g dw in
non-paddy TS. Preferentially adsorbed to the BC or to
clay minerals are monomolecular PAH that occur in
trace amounts only. The sum of PAH detected in
paddy TS is higher than in non-paddy TS, with a
range from 247 to 978 ng/g dw in paddies and from
54 to 167 ng/g dw in non-paddies. Additionally, in
paddy TS an increasing trend with cultivation time
was observed.
The lowest BC (0.3-0.8 mg/g dw) and PAH (10-30
ng/g dw) concentrations were found in regular
subsoils, with no significant difference between paddy
and upland use. Extremely high concentrations of BC
were detected in dark buried horizons (at the 700 and
1000 year old site), which were either assumed to be
former A-horizons or sedimentary layers due to
inundations of soils by marine or limnic flooding.
The higher compositional variability of PAH, despite of
their low concentration, were used for differentiation
of combustion effects in substrates, topsoils and
subsoils (local combustion and soil erosion of the
hinterland).
Fig.1. Relative distribution of 5-ring PAH in substrate
end-members and soils.
The marine tidal flat substrate contains predominantly
OM of terrigenic origin, derived from soil and
sediment erosion in the catchment area of the
Yangtze River. This is shown by enrichment with
perylene and depletion in benzofluoranthenes and
benzopyrenes, also observed in other studies [1].
Regular subsoils show a PAH pattern identical to that
of the marine substrate, whereas TS and buried
horizons yield a distinctive rice ash derived PAH
pattern (Fig.1). Subsoils adjacent to the buried Ahorizons
reveal a PAH pattern similar to that of the
latter indicating postdepositional translocation of BC
and PAH from buried TS into over- and underlying
strata. A major proportion of the SOM in paddy rice
soils is derived from in-field rice straw combustion.
This management practice is expected to phase out
over the next decade due to environmental legislation.
A proposed diminished input of combustion residues
may lead to significant changes and yet unpredicted
consequences in stabilization of SOM in paddy soils.
[1] Liu et al. (2008) Environ. Pollution 154, 298-
305.
514

P-386
Remediation of hydrocarbon contaminated soils by modified
Fenton oxidation in the presence of magnetite
Usman Muhammad 1,2 , Faure Pierre 1 , Hanna Khalil 2 , Ruby Christian 2
1 UMR CNRS G2R Nancy Université, Vandoeuvre les Nancy, France, 2 UMR CNRS LCPME Nancy
Université, Villers les Nancy, France (corresponding author:pierre.faure@g2r.uhp-nancy.fr)
The intense use of fossil organic matter (petroleum
and coal) since 18 th century for industrial purposes
(petroleum extraction, refinery, steel industries, coking
plant etc.) has resulted in numerous contaminated
sites that cause environmental and health concerns.
Especially, polycyclic aromatic hydrocarbons (PAHs),
well known carcinogenic pollutants, are resistant to
environmental degradation and imply huge industrial
treatments (e.g. thermal desorption…). On the
contrary, petroleum hydrocarbons are easily
biodegradable by soil microorganisms or by biological
treatments. However, refractory fractions (especially
asphaltenes) remain difficult to eliminate and can
induce major perturbation of flora and fauna in the
environment.
In situ chemical oxidation (ISCO) especially Fenton
oxidation can be a potential remediation processes
susceptible to degrade these recalcitrant organic
compounds. Instead of applying traditional Fenton
oxidation (dissolved Fe II + H2O2, optimal pH 3-4),
modified Fenton oxidation was developed in this study
by using iron minerals which allows the oxidation at
circumneutral pH. Indeed, soil iron minerals
containing both Fe II -Fe III are more reactive but rare in
soil system than only Fe III minerals which are
abundant. Firstly endogenous soil Fe III minerals were
transformed into magnetite (Fe II Fe III 2O4), a more
reactive phase, so that it can be used as an iron
source to promote oxidation of pollutants.
Then the kinetic degradation of i) Fluorenone (model
pollutant of PAHs) ii) Organic extract from a PAHs
polluted soil from an industrial site, iii) n-Eicosane
(model pollutant of petroleum) iv) Organic extract from
a petroleum contaminated soil was investigated
through modified Fenton oxidation. All experiments
were conducted in batch reactors with magnetite rich
sand at circumneutral pH.
Almost 90% of fluorenone abatement was achieved
after 48 hours of reaction with H2O2 in the presence of
magnetite and no pollutant traces were detected after
one weak. Significant degradation (81%) of 16 PAHs
was found in case of PAHs polluted soil (Fig. 1).
Almost 90% and 85% of n-eicosane and petroleum
hydrocarbons respectively was degraded after one
week (Fig. 1). Also no by-products were observed
through GC-MS analysis for model compounds as
well as for organic extracts which indicates the
complete oxidative degradation of pollutants. In
parallel, the FTIR analysis shows no modification of
the molecular structure (especially oxygenated
functions) for all organic samples. Moreover, a nonselective
degradation was revealed for all
contaminants as no molecule was preferably
degraded.
Figure 1: Abatement of pollutants with the course of
time represented in terms of C/C0 where C0 is initial
pollutant concentration and C is the concentration at
specified time point.
Currently oxidation experiments are in process on real
soil. This study has important implications in the
remediation of polluted soils by using the reactivity of
soil endogenous iron which can be used as a feasible
source of iron catalyst to promote modified Fenton
oxidation. Moreover, this chemical treatment should
be carried out in situ avoiding soil excavation.
515

P-387
The use of phospholipid fatty acid analysis and isotopic
techniques to track the fate of organic contaminants in
environmental systems
Brian Murphy 1 , Chris Allen 2 , Leonid Kulakov 2 , Anna Kulakov 2 , Michael Larkin 2 , Brian
Kelleher 1
1 Dublin City University, Dublin, Ireland, 2 Queens University, Belfast, Ireland (corresponding
author:Brian.kelleher@dcu.ie)
This project focuses on analysis of soils and
sediments contaminated with petroleum compounds.
By using gas chromatograph mass spectroscopy
(GCMS) to identify and quantify 1)petroleum
pollutants 2)pospholipid fatty acids (PLFA‘s) then
combining the use of stable isotope studies, an
improved understanding of the fate of particular
organic compounds in complex microbial systems can
be gained. PLFA‘s are particularly useful as
biomarkers as they are contained solely in the cell
membrane as storage products. This is important as
the cell membrane rapidly degrades after cell death;
therefore PLFA‘s are good indicators of living
microbial biomass rather than non-living microbial
biomass [1] .
Total petroleum hydrocarbon (TPH) analysis
is an accepted benchmark used to evaluate the extent
of petroleum contamination in environmental
samples [2] . Sediment contaminated with petroleum
hydrocarbons was sourced from a petroleum
company (See Chromatogram 3). Volatile compounds
from another sample contaminated with heavy fuel oil
were extracted using solid phase micro extraction
(SPME). Lipid extraction: PLFA‘s are extracted and
isolated from soil using a modified Bligh Dyer
extraction and solid phase extraction (SPE)
respectively. The total lipid (TLE) extracts are then
transferred to SPE columns the PLFA‘s are isolated
and derivitised to fatty acid methyl esters
(FAME‘s).(See Chromatograms 1&2). Isotopic
analysis is performed using GCMS hyphenated to
isotope ratio mass spec (IRMS). Soils amended with
C 13 labelled tracers are extracted and enriched
PLFA‘s are identified using the C 12 /C 13 ratio.
Chromatogram 5 shows enriched PLFA‘s from soil
incubated with C 13 Vanillin.
GCMS Chromatogram 1: Total lipids extracted from park soil
GCMS Chromatogram 2: Isolated PLFA‘s after SPE
GCMS Chromatogram 3: TPH with Hrdrocarbons and known
oil spill biomarkers
GCMS Chromatogram 4: SPME results contaminated site
containing C11 to C16 Hydrocarbons and naphthalene.
IRMS Chromatogram 5: C13 enriched Fatty acids
Discussion: SPE allows the isolation of PLFA‘s so
they can be used as taxonomic discriminators for
microbial species [1] . Analysis of volatile and non
volatile petroleum contaminants gives an indication of
the level of soil pollution. Fluorene, anthracene,
phenanthrene and naphthalene are known markers
for oil spills this preliminary analysis helps in
identifying a suitable compound for C 13 labelled tracer
studies. Microbes which degrade the labelled marker
will incorporate C 13 into their PLFA‘s. By tracing all the
enriched PLFA‘s using IRMS and lipid fingerprinting,
the microbial species responsible for uptake of the
labelled compound can be identified.
References: [1] G.T.Hill et al. Applied Soil Ecology 15 (2000)
25-36. [2] Guibo Xie, Journal of Analytical Chemistry 71
(19199) 1899-1904
516

P-388
ESR spectroscopic study of humic acid-like materials obtained
by the autoxidation of caffeic and chlorogenic acid
Ruņica Nikoliš 1 , Tatjana AnŤelkoviš 1 , Goran Nikoliš 2
1 University of Niš, Faculty of Sciences, Department of Chemistry, Niš, Serbia, 2 University of Niš, Faculty of
Medicine, Department of Chemistry, Niš, Serbia (corresponding author:ruzicanf@yahoo.com)
Electron spin resonance (ESR) spectroscopy is
widely used technique for the investigation of both
natural humic acids and humic acid-like materials
obtained from various phenolic compounds [1,2].
Beside the characterization of organic radicals it is
also possible by using ESR to study interactions of
such samples with paramagnetic metal ions some of
which (eg. Fe 3+ , Cu 2+ , Mn 2+ ) are ubiquitous in natural
samples [3].
As far as organic radicals in humic acids and humic
acid-like materials are concerned the researchers
mainly reported ESR spectra consisting of one broad
symmetrical line with no hyperfine structure for both
solid samples and samples in solutions. These
organic radicals thus were characterized by the
linewidth of ESR signal and its g-value, and it was
possible to determine the free radical concentration in
solid samples. Only in few cases ESR spectra with
some hyperfine structure were obtained [1], but the
reason for that might be that modulation amplitudes
used for recording most of the ESR spectra reported
in the literature were to high (usually values between
0.1 and 0.2 mT were reported).
In this work we recorded ESR spectra of humic
acid-like materials obtained by the prolonged
autoxidation of 20 mM solutions of caffeic or
chlorogenic acid at pH 8.4 (Tris buffer) in the
presence of an excess of Mg ions. ESR
measurements were carried out in a quartz flat cell
using an X-band Bruker ESP-300 spectrometer by
employing microwave power of 2.0 mW and
modulation amplitude of 0.01 mT. The spectra
obtained immediately after starting the autoxidation
reaction displayed well resolved hyperfine structure
which enabled characterization of initially formed spinstabilized
ortho semiquinone radicals. After prolonged
autoxidation solutions became turbid and
corresponding ESR spectra lost some, but not all, of
its hyperfine structure. The ESR spectrum of system
based on caffeic acid is shown in Fig. 1. and its
appearance is very similar to the ESR spectrum of the
unfractionated Tsubame humic acid in solution [1].
For the chlorogenic acid system under the same
conditions we obtained similar ESR spectrum, but
with much more noise and less resolved hyperfine
structure. In some earlier experiments after prolonged
autoxidation of rutin under the same conditions we
obtained ESR spectra consisting of one
unsymmetrical line but without hyperfine structure [4].
Fig. 1. ESR spectrum of humic acid-like material
obtained by the 7 day autooxidation of caffeic acid in
the presence of Mg ions at pH 8.4 in aqueous
solution.
Our results suggest that ESR spectra of humic
acids and humic acid-like materials should be
recorded with the use of small enough values of
modulation amplitude in order to see whether some
hyperfine structure is present. This may help better
characterization of such samples.
References
[1] Watanabe, A., McPhail, D.B., Maie, N.,
Kawasaki, S., Anderson, H.A., Cheshire, M.V.
(2005) Org. Geochem. 36, 981-990.
[2] Giannakopoulos, E., Drosos, M., Deligiannakis,
Y. (2009) J. Coll. Int. Sci. 336, 59-66.
[3] Barriquello, M.F., da Costa Saab, S., Filho,
N.C.,Martin-Neto, L. (2010) J. Braz. Chem. Soc.
21, 2302-2307.
[4] Nikoliš, G.M., Nikoliš, R.S., Miliš, B.Lj.,
Ţanadanoviš-Brunet, J.M. (2000) Proceedings of
the 5th <strong>International</strong> Conference on Fundamental
and Applied Aspects of Physical Chemistry,
Belgrade, Yugoslavia, 123-125.
517

P-389
Biogeochemical process studies on oil sand tailings used for
land reclamation
Mareike Noah 1 , Andrea Vieth-Hillebrand 1 , Beate Schneider 2 , Bernd Uwe Schneider 1 ,
Heinz Wilkes 1
1 Helmholtz Centre Potsdam GFZ German Research Centre for Geosciences, Telegrafenberg, Potsdam,
14473, Germany, 2 University of Potsdam, Karl-Liebknecht-Strasse 24-25, Potsdam, 14476, Germany
(corresponding author:noah@gfz-potsdam.de)
The Athabasca region of northern Alberta, Canada, is
home to deposits of oil sands containing vast
amounts (~ 173 billion barrels) of heavily biodegraded
petroleum, known as bitumen.
Oil sands are recovered by surface mining or by in
situ steam injection. The extraction of bitumen from oil
sands by caustic hot water processing results in large
volumes of fluid tailings, which are stored in on-site
settling basins. There the tailings undergo a
compaction and dewatering process, producing a
slowly densifying suspension. The released water will
be recycled for extraction. The fine tailings will be
reclaimed as either dry or wet landscapes. [1]
Oil sands are the result of very intense anaerobic
biodegradation processes that occurred since
expulsion of oil from the source rock and have been
controlled by temperature and the presence of water
and nutrients. Also after oil sands extraction
anaerobic biodegradation will occur within the tailing
ponds leading to a release of greenhouse gases into
the atmosphere. Anaerobic biodegradation of
hydrocarbons to end products like methane and
carbon dioxide is possible by different groups of
microorganisms: denitrifying bacteria, sulfate-reducing
bacteria and methanogens. [2]
Open pit mining and the extraction of the bitumen
from the oil sands creates large and intense
disturbances of varying landscapes. The area
currently disturbed by mine operation covers about
530 km 2 and the area of tailing ponds surpasses
130 km 2 .
To produce 1 barrel of crude oil, 2 tons of oil sand and
2 – 3 tons of water (including recycled water) are
required. [3]
An issue of increasing importance is the land
remediation and reclamation of oil sand areas in
Canada and coal mining sites in Germany and the
reconstruction of these disturbed landscapes back to
working ecosystems similar to those existing prior to
disturbance.
For that reason the identification of oil sand-derived
organic compounds in the tailings, their environmental
behaviour and the resulting chances and limitations
are key topics for land reclamation. Furthermore the
biodegradation processes that occur in the tailings
and that could lead to a decrease in hazardous
organic compounds are important challenges, which
need to be investigated.
This presentation will give a detailed overview of our
compositional and quantitative characterisation of
organic matter in oil sand, coal and oil sand tailing
samples. The analytical characterisation is based on
the extraction of the soluble organic matter, its
subsequent separation into asphaltenes, aliphatics,
aromatics, neutral NSO (nitrogen, sulphur, oxygen)
compounds and fatty acids. The asphaltene fractions
are analysed using Pyrolysis-GC, all other fractions
are analysed by GC-MS. Furthermore, details of
biogeochemical processes will be elucidated by
establishing an inventory of phospholipids and
biomarkers as well as determining the carbon and
hydrogen stable isotopic composition of individual
organic compounds.
References
1. Leung, S.S.-C., MacKinnon, M.D., and Smith, R.E.H.,
Aquatic reclamation in the Athabasca, Canada, oil
sands: Naphthenate and salt effects on phytoplankton
communities. Environmental Toxicology and Chemistry,
2001. 20(7): p. 1532-1543.
2. Salloum, M.J., Dudas, M.J., and Fedorak, P.M.,
Microbial reduction of amended sulfate in anaerobic
mature fine tailings from oil sand. Waste Management &
Research, 2002. 20(2): p. 162-171.
3. Kelly, E.N., et al., Oil sands development contributes
polycyclic aromatic compounds to the Athabasca River
and its tributaries. Proceedings of the National Academy
of Sciences, 2009. 106(52): p. 22346-22351.
518

P-390
A three-year survey of fluorescent dissolved organic matter in
the Arcachon Bay (South Western France)
Edith Parlanti, Marie-Ange Cordier, Fabienne Ibalot
Université de Bordeaux, UMR 5805 CNRS, EPOC - LPTC, Talence, France (corresponding
author:e.parlanti@epoc.u-bordeaux1.fr)
Transitional and 0.8 coastal 0.8
0.8 0.8environments
represent Fig. 1: HIX and BIX variations for water samples
complex systems
0.8
submitted 0.8
0.8 0.8 to high tidal conditions, collected in Arcachon Bay sites in 2010.
intensive exchange 0.8
0.8
0.8 0.8
0.8
0.8 and 0.8 mixing 0.8 between fresh water
inputs and seawater. 0.8 The 0.8
0.8 0.8aim
of this work was to No marked seasonality was shown for the tributaries;
apply fluorescence 0.7
0.7
spectroscopy 0.7
0.7
0.8
0.7
for tracing dissolved on the other hand a specific FDOM from each
organic matter 0.7 0.7(DOM)
sources 0.7
0.7
and cycling in an tributary site was observed (Fig 2.)
economically 0.7
0.7
important 0.7
0.7
coastal
0.7
area: the Arcachon
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
Bay (French Atlantic 0.6 coast). 0.7 0.6This
site is well known for
BIX La Leyre
0.6
0.7 0.6
BIX La Leyre
0.6 0.7
BIX Banc d‘Arguin BIX Lanton
tourism and 0.6 0.6French
0.6
BIX
oyster production and is
Bélisaire
BIX Canal des étangs
0.6 0.6
BIX Grand Banc BIX Cirès
particularly sensitive 0.6 to 0.6 environmental degradation
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7 0.7
0.7
0.7
0.7
BIX Ile aux Oiseaux BIX Bourg
0.6 0.6
BIX Eyrac
BIX La Hume
and to anthropogenic 0.6 inputs 0.6 mainly due to urban,
BIX Le Tès
BIX Craste de Nezer
agricultural, tourism 0.5
0.6 0.5
BIX Betey
0.5
0.6 0.5
BIX Betey
and harbour activities.
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6 0.6
0.6
0.6
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
0.5
0.5 0.6
BIX Ponteils
0.6
0.5
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6 0.6
0.6
0.6
0.6
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX
0.5
0.5 0.6
BIX Ponteils
0.5 0.6
BIX Ponteils
0.5
0.5 0.5
A three-year survey
0.5 0.5
0.5 of fluorescent 0.5 dissolved organic
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
matter (FDOM) 0.5 0.5was
undertaken
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
on 15 stations of the
0.4 0.5 0.4
Arcachon Bay 0.4from
2008 0.4 0.5
0.4
0.4 0.5
until 2010. Surface water
samples were
0.4
0.4
collected 0 0.4 from 5 0
the Arcachon 105 1510 Bay (6 2015 2520 3025 3530
35
0.4
0.4
0.4
0.4
0.4 0.4
0.4
0.4
0.4 0.4
0.4 0.4
0 0.4 5
0 10 5
10
5 15 10
15
10 20 15
20
15 25 20
0.4
0.4
0.4
0.4
25
20 30 25
30
25 35 30 35
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4 0.4
0.4
0.4
0.4 0.4
0.4 0.4
0 0.4
0.4
35
30 35
stations) with 0.4a
step 0
5
0
of 0.4 sampling 5
0 10
of 10
5 15
3-4 months 15
10 20
HIX for 20
15
HIX
25
25
20 30
0 0 0 0 0 0 0 0 0 0 0 5 5 5 5 5 5 5 5 5 5 5 30
25 35
10 10 10 10 10 10 10 10 10 10 35
30 35
0.4 0 15 15 15 15 15 15 15 15 15 15 15 20 20 20 20 20 20 20 20 20 20 20 25 25 25 25 25 25 25 25 25 25 25 25 30 30 30 30 30 30 30 30 30 30 30 35
35
35
35
35
35
35 35
35
35
35
0.4
0 5 10 15 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 020 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 25 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 30 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 35 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 35
35
35
35
35
35
35
35
35
35 35
35
35
35
35
0 0.4
5
0 10
5
10
5 15
10
15
10 20
15
5 0 10 5 1510HIX 20
25
25
30
30
35
35
0.4 0
FDOM screening. On the other hand, the 9 HIX
2015 HIX2520
3025 3530
35
0 0.4
5 10 15 HIX 20
15
20
0.4
HIX25
20
25
30
25
30
35
30
35
0.4
0 5 10 15 35
0.4
0 5 10 15 HIX
20 25 30 35
0 0.4 0 5 10 15 20 25 30 35
5 0 10 5 15 10
5 0 10 5 1510main HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX 2015 HIX25
30 35
tributaries of the Bay
0
0.4
HIX
20 25 30 35
0 5
were
5 0 10
monthly sampled.
10 5 15 HIX
20 15 HIX2520
3025 3530
35
0 0.4
HIX 20 25 30 35
0.4 5 0 10 5 1510 15 10
HIX 2015 HIX
HIX 20 25 30 HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX
HIX 20 25 35
2520 30
3025 35
0 5 3530
35
0
10
0
5
15 HIX 2015 HIX25
30 35
0
0.4 0.40
HIX
5 0
5
10 5
10
15 10
15
5
10 HIX 20 15 HIX 20 25 30 35
10
15 HIX
HIX 20
25 2520 FIG. 2: 20
30 3025 HIX and 25
35 3530
35
0
0
5
5
10
10
15 HIX 20
25
25
30
30
35
35
0
0
5
5
10
10
15 BIX variations 30 - Arcachon 35 Bay and
EEM fluorescence spectra were recorded using
HIX 15
20
HIX 20
25
25
30
30
35
HIX 20 25 30 35
HIX HIXa
HIX
tributaries. HIX
Fluorolog FL3-22 SPEX – JOBIN YVON fluorometer. HIX
Spatial and temporal variations of DOM fluorescence
properties were observed. We observed seasonal
effects and different trends in composition as well as
in behaviour or production of FDOM.
Fluorescence indices were also calculated and
discussed (HIX -humification index, and BIX -
biological autochthonous input index). These two
indices showed spatial and seasonal variations of the
quality of FDOM from the Arcachon Bay as shown as
an example in Fig. 1 for samples collected in 2010.
BIX BIX
BIX BIX
BIX BIX
BIX BIX
BIX BIX
BIX BIX
0.8
0.8
0.8
0.8
0.8
0.8
0.7
0.7
0.7
0.7
0.7
0.7
0.6
0.6
0.6
0.6
0.6
0.6
0.5
0.5
0.5
0.5
0.5
0.5
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
SUMMER
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
BIX BIX BIX
JULY-
OCTOBER
MARCH
WINTER
JANUARY
15 20 25 30 35
15 20 25 30 35
BIX Banc d‘Arguin
BIX Bélisaire
BIX Grand Banc
BIX Ile aux Oiseaux
BIX Eyrac
BIX Le Tès
0.4
0.4
0.4
0.4
0.4
0.4
15 HIX 20 0 0 0 0 0 0 5 5 5 5 5 5 25 10 10 10 10 10 10 30 15 15 15 15 15 15 20 20 20 20 20 20 35 25 25 25 25 25 25 30 30 30 30 30 30 35
35
35
35
35
35
15 HIX 20 25 30 35
15
HIX
20 25 30 35
15 HIX
20 25 30 35
15 20 25 30 HIX
HIX
HIX
HIX
HIX
HIX 35
15 HIX
HIX 20 25 30 35
HIX
HIX
BIX
BIX
BIX
BIX
BIX
BIX
BIX BIX BIX BIX
BIX BIX BIX BIX BIX BIX
BIX BIX BIX BIX BIX BIX
BIX BIX BIX BIX BIX BIX
BIX BIX BIX BIX BIX BIX
BIX BIX BIX BIX BIX BIX
BIX BIX BIX BIX BIX BIX
BIX BIX BIX BIX BIX BIX
BIX BIX BIX BIX BIX BIX
BIX BIX BIX BIX
BIX BIX BIX BIX
BIX BIX BIX BIX
BIX BIX BIX BIX
BIX BIX BIX BIX
BIX BIX BIX BIX BIX BIX
The analysis of FDOM of waters from the Arcachon
Bay and from its main tributaries during a three-year
survey allowed to discriminate between various
sources of colloidal organic matter and showed the
spatial and temporal variability of the signatures of the
various sources.
519

P-391
Environmental forensics-recent applications of C, H and Cl
isotopes in the determination of sources of groundwater
contaminants
Paul Philp, Tomasz Kuder
School of Geology and Geophyscis, University of Oklahoma, Norman, United States of America
(corresponding author:pphilp@ou.edu)
Since the commercial availability of gas
chromatograph-isotope ratio mass spectrometer
systems, the number of environmental forensic
applications has increased exponentially. There are
many well documented EPA methods used in
environmental studies but these methods are of little
use in environmental forensic studies, where the
major goal is to find responsible parties rather than
simply obtaining concentration data. In general
environmental forensic studies utilize a tiered
approach, with gas chromatography (GC) providing
an initial indication of the contaminant type; gas
chromatography-mass spectrometry (GCMS)
identifying specific compounds and undertaking
correlation or discrimination studies. However in many
cases the results at this point may still be ambiguous
and not clearly pointing to any specific source(s) for
the contaminant. This is particularly true in the case of
contaminated ground water where there might be a
single component such as MTBE or PCE etc., where
GC and GCMS, whilst telling us it is one compound,
will certainly not differentiate sources of the
contaminant. Differentiation of more complex mixtures
such as crude oils, refined products, and PAHs may
also benefit from using stable isotopes as an
additional line of evidence in distinguishing potential
sources.
There are two major applications of stable
isotopes in environmental forensics, the first being a
tool to differentiate sources and the second to monitor
the onset and extent of natural attenuation. This
paper will provide examples from both of these areas.
First though it is important to mention that early
applications of stable isotopes only considered
utilization of carbon isotopes, but in recent years
utilization of H and, even more recently, Cl isotopes
has become more widespread. A number of isotope
specific challenges have become apparent along the
way to developing these as routine tools for these
applications. For example whilst H isotopes can be
readily determined in the case of hydrocarbons, in a
compound such as TCE (trichloroethylene) with only
one H and 3 Cl, this requires higher contaminant
concentrations for the H but at the same time may
provide valuable information as to whether the TCE
was an original synthetic product or formed from
degradation of PCE. Determination of Cl isotopes of
individual compounds is now becoming a routine tool
and can be obtained through the use of GCMS and
does not require GCIRMS.
The outcome is that it is now possible to use
2D or 3D stable isotope fingerprinting to study both
sources of contaminants as well as the onset of
natural attenuation. In this paper a number of case
histories will be described where stable isotopes, C, H
and Cl, have been used to discriminate sources of
MTBE, chlorinated solvents and hydrocarbons in the
environment. Whilst this approach may not provide
the silver bullet every attorney is looking for, it will
certainly provide additional evidence not available
from the traditional techniques of GC and GCMS.
Ranges of isotope values for non-degraded samples
of many of the common groundwater samples are
now well established and samples with isotope values
heavier than these values are typically considered to
have undergone natural attenuation. At the same time
it is important to point out certain misconceptions
about utilization of stable isotopes in environmental
forensic studies. As a result of a small number of
papers published several years ago, it is believed in
some areas that one can use isotope compositions of
groundwater contaminants to actually identify the
company that made the contaminant of interest. This
is totally incorrect and any investigation into the
manufacturing process involved in making these
compounds will quickly show the potential for isotopic
variations as a result of changing feedstocks and
other variables.
In brief stable isotopes are playing an
invaluable role in environmental forensic
investigations but a huge potential for additional
applications remains.
520

P-392
Environmental forensic study of a complexly contaminated soil
at a former chemical plant
José Luis R. Gallego 1 , Michael A. Kruge 2 , Iván Lores 1 , Azucena Lara 1 , Carlos Sierra 1
1 Environmental Biotechnology and Geochemistry Group, Campus de Mieres, University of Oviedo., 33600 -
Mieres (Asturias), Spain, 2 Department of Earth and Environmental Studies, Montclair State University,
Montclair, NJ 07043, United States of America (corresponding author:jgallego@uniovi.es)
A detailed environmental forensic study of a former
chemical plant (Asturias, Northern Spain) was
performed to establish a relationship of spills and
other pollution events to the present state of its soil
and surficial water. The investigation employed a
three step process: First, we acquired general data on
the hydrological, soil, and geological conditions of the
site. Then we completed a comprehensive search for
information about the industrial activities performed in
the abandoned plant. Finally, the application of
molecular techniques and a forensic interpretation
permitted a detailed view of the different contaminants
affecting the site and their linkage with the former
industrial activity. Identification of pollutants and
evaluation of weathering was performed by different
applications of GC-MS techniques [1], whereas a
detailed study on the origin of the predominant ones
(PAHs) was carried out using Pyrolysis-GC/MS [2].
The study site comprises about 2.5 ha and had been
completely cleared of buildings then abandoned
before this study started. A typical soil column in the
affected area has a highly polluted sandy surface
layer averaging about 50 cm thick with interbedded
pebble layers in which infiltrating water accumulated.
From 50 cm to 4 m deep there are compact, nonpermeable
carbonate and clay strata, which contain
most of the contamination in the top two meters. The
water table is below 5 m, in a more permeable
alluvium layer. An extensive compilation of historical
data (personal interviews, legal registers, etc.) yielded
a comprehensive list of processes and activities at the
plant likely to have produced contamination,
summarized as follows:
a) As the principal activity at the site during the 1970's
and 1980's, two separate units produced
naphthalene, phenol, and other compounds from coal
tar.
b) Another unit of production was dedicated to the
manufacture of resins. A considerable amount of
other chemical products (pesticides, solvents, etc.)
was stored, although probably not manufactured, in
the plant.
c) In the 1990‘s the plant was closed and then used
for years to store chemical waste, particularly
polychlorinated biphenyls, coolants and other
unspecified products.
As a main result of the forensic study we were able to
divide the area affected in several subareas. In all of
them, PAHs (mostly of combustion origin), and
specifically naphthalene, were the most abundant
contaminants in GC-MS determinations, while indene
was also remarkably abundant in soil pyrolyzates. We
also found areas for which hydrocarbon fingerprinting
indicated fuel spills (petrogenic origin, associated with
old heating systems). Additionally, evidence of animal
fats was detected and this was linked to the former
storage of ‗Tinol‘, a residue from steel plants,
composed of a mixture of animal fats, mineral
lubricants and chips (Fe oxides mainly). Many other
contaminants were detected and classified (Table 1).
The conclusions obtained were useful to select
strategies for site remediation.
Comp Possible sources Comments
PAHs
Coal tar processing
Fuel spills
Predominance of
parent PAHs
Aliphatics Fuel and diesel spills Slightly weathered
Phenols Coal tar processing Predominant in water
Phthalates Resins manufacture DEHP predominance
Chlorinated
Waste and solvent
storage
CAHs and PCBs in
low concentrations
Fats ‗Tinol‘ storage Oleic acid and others
Table 1: Main contaminants and sources found.
[1] Gallego, J.R. et al. (2010) Organic Geochemistry
41, 896-900.
[2] Kruge, M., Permanyer, A. (2004) Organic
Geochemistry 35, 1395-1408.
521

P-393
Geochemical characterization of oil spills samples and oil
samples from wells adjacent areas in order to determine the
origin by oil-oil correlation, two case studies, Monagas,
Venezuela
Ysmarline Rincones, Carmen Rodriguez, Jennifer Arenas
PDVSA, Intevep, Los Teques/Miranda, Venezuela (Bolivarian Republic of) (corresponding
author:rinconesyj@pdvsa.com)
The geochemical characterization is a specialty
widely used in the oil industry with multiple
applications that help in understanding the petroleum
system in the area. Below are two case studies in
which geochemical characterization was applied to
determine the source of oil spills in the area North of
Monagas in Venezuela.
Case 1: This study is about geochemical
characteristics of a oil sample A-1 from a spill in area
C and a oil sample B-1 from well B located in the area
C. The samples were analyzed by general and
special geochemical techniques to determine the
origin and maturity of these, as well as any possible
oil-oil correlation, to determine the source of the spill.
For the evaluation and characterization of the
samples collected, the following geochemical analysis
were carried out: SARA, GC on saturates fraction and
GC-MS of saturates and aromatic fraction.
The results showed clear differences between the
samples, indicating a negative oil-oil correlation
between oil samples A and B, which indicates that the
oil sample A does not come from wells in the area,
although samples are associated with a carbonate
rock deposited under anoxic conditions and a marine
origin, the differences were found in the maturity and
biodegradation.
Case 2: This study is about geochemical
characteristics of oil seepage samples E-1, E-2, E-3,
E-4, E-5, E-6, detected in the field D and a oil sample
F-1 from wells F located in the field D, in order to
conduct an evaluation to determine if these oil
samples correspond to a oil seepages or if spills
caused by abandoned wells in the area.
For the evaluation and characterization of the
samples collected were performed as for Case 1,
SARA, GC on saturates fraction and GC-MS of
saturates and aromatic fraction.
The results suggest that the oil seepage samples and
the well oil sample are positively correlated, indicating
that the abandoned wells are leaking oil, in addition,
the characterization determined that the samples are
associated with a carbonate rock deposited under
anoxic conditions, a marine origin and maturity is
between early and oil window. Besides the lack of
paraffins and isoprenoids and the presence of the
compound 25-Norhopane established that the
samples show a high degree of alteration (grade 8)
due to the effect of biodegradation and / or oxidation
of the compounds
522

P-394
Polycyclic aromatic hydrocarbons in the Pichavaram Mangrove-
Estuarine sediments, South-eastern, India
Rajesh Ranjan 1,2 , Joyanto Routh 3,4 , AL Ramanathan 1 , J Val Klump 5
1 School of Environmental Sciences, Jawaharlal Nehru University, New Delhi, India, 2 Centre for
Environmental Sciences, Central University of Bihar, Patna, India, 3 Department of Earth Sciences, IISER-
Kolkata, Mohanpur, Mohanpur, West Bengal, India, 4 Department of Natural Sciences and Technology, MTM,
Örebro University, 70182 Örebro,, Örebro, Sweden, 5 Great Lakes WATER Institute, University of Wisconsin-
Milwaukee, Milwaukee, United States of America (corresponding author:joyanto.routh@iiserkol.ac.in)
Polycyclic aromatic hydrocarbons (PAHs) have
received much attention due to their carcinogenic and
mutagenic potential and ubiquitous presence [1].
They enter the aquatic environment via industrial
discharge, petroleum spills, combustion of fossil fuels,
and non-point source inputs such as agricultural and
urban runoff and atmospheric deposition [2]. Because
of their poor solubility and hydrophobic nature, PAHs
entering the environment preferentially adsorb to
particulates and accumulate in sediments.
The primary objectives of this study are to
investigate the 1) different sources of PAHs and its
concentration in the Pichavaram mangrove-estuarine
sediments and, 2) historical variations in PAH
deposition related to human activities. 16 PAHs listed
as ―priority pollutants‖ by the USEPA were
investigated in five 210 Pb dated sediment cores. The
study area was divided into three zones – the Vellar
estuary, mangrove forests and Coleroon estuary on
the basis of vegetation, land-use pattern, and
anthropogenic influence. Organic matter (OM) was
extracted using an accelerated solvent extractor and
the extracts were analyzed on a GCMS.
TOC concentration in sediments ranged from
0.06 to 1.97 % of dry weight. The mean ΣPAH
concentrations in mangrove and estuarine sediments
were 0.18 (±0.09) and 0.14 (±0.09) μg/g, respectively.
The PAH distribution trends indicate higher PAH
concentrations in mangrove than estuarine
sediments, and is influenced by the TOC content and
grain-size. However the PAH concentrations in
Pichavaram are below those of other mangrove
sediments [3]. Diagnostic PAH ratios and congener
pairs (Fluor(Fluor/Pyr) vs. Anth/(Anth+Phen) and
Fluor(Fluor/Pyr) vs. BaA/(BaA+Chry) show that most
PAHs are derived from a mixture of petrogenic
(automobile exhaust, oil spills from fishing boats)
sources with limited inputs from pyrogenic processes
involving combustion of wood and lignite/coal.
The ΣPAH deposition flux shows that deposition of
high molecular weight (HMW) PAHs has increased in
mangrove surface sediments, and is associated with
increase in anthropogenic activity. The ΣPAH flux
roughly follows the low molecular weight (ΣLMW)
PAH trend in estuarine sediments, whereas in
mangrove sediments the ΣPAH flux roughly follows
the high molecular weight (ΣHMW) PAH trend (Fig.
1). The relatively high flux for ΣHMW PAHs in
mangrove sediments could be explained by two
reasons. First, OM in mangrove sediments is mainly
derived from higher terrestrial matter (mainly in situ
mangrove vegetation) or riverine material. During
sediment transport due to solubilization and
volatilization the LMW PAHs degrade easily [4].
Secondly, biodegradation depletes preferentially the
LMW PAHs over HMW PAHs [5]. In the organic-rich
mangrove sediments there is more burrowing and
turning over of sediments and microbial activity than
estuarine sediments, and perhaps therefore, the LMW
PAHs in these sediments are degraded preferably.
Fig.1. Down core variations of PAHs flux (μg/cm 2 /yr)
References
[1] Flowers, L. et al. (2002) Polycyclic Aromatic Comp. 22,
811–821.
[2] Macdonald, R.W. et al. (2005) Sci. Tot. Environ. 342, 5–
86.
[3] Domínguez, C et al. (2010) Arch. Environ. Contam.
Toxicol. 59, 49-61.
[4] Christensen, E.R., Arora, S. (2007) Water Research, 41,
168-176.
[5] Brito, E.M.S. et al. (2005) Química Nova 28, 941–946.
523

P-395
Source characterization using molecular distribution and stable
carbon isotopic composition of n-alkanes in sediment cores
from Mundaú-Manguaba estuarine-lagoon system, Brazil
Thaís Silva, Silvia Lopes, Débora Azevedo
Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil (corresponding author:thaisreis@iq.ufrj.br)
Ocean waters, marine organisms and sediments
contain hydrocarbons derived from many sources.
The wide variability in the hydrocarbon composition
from different sources makes the study of these
compounds a useful tool in geochemical
investigations [1]. The Mundaú-Manguaba estuarinelagoon
system (MMELS) constitutes one of the most
representative ecosystems of the State of Alagoas,
NE-Brazil. It has been subject to multiple
anthropogenic activities, mainly from urbanization,
sugarcane agriculture and chemical industries [2].
This study aims to provide temporal distributions of nalkanes,
together with their compound-specific � 13 C
values in core sediments from the MMELS, in order to
characterize the contribution and the sources of these
compounds over the past 40 years. The core samples
were collected at three sites: Manguaba Lagoon
(C03), Mundaú Lagoon (C07) and Mundaú River
(C08) in 2007. The cores were sectioned at 2 cm
intervals. About 4 g of each dry sediment was
extracted with dichloromethane:methanol 8:2. The
extracts were concentrated and fractionated using an
activated silica gel column. The analyses were carried
out by GC-FID and GC/C/IRMS.
The MMELS cores had a total organic carbon
(TOC) ranging from 1.88 to 3.35%. The C/N values
fluctuated between 9.6 and 13.2 for Manguaba and
Mundaú lagoon indicating mainly algal, bacterial and
non-vascular plant origins. For Mundaú River the
values ranged from 11.7 to 17.8 except for two
section of the top of the core that presented values
25.3 and 22.0. The n-alkanes ranged from C15 to C35,
with total aliphatic hydrocarbon (TAH) concentration
in the range 27.8–139.5 µg g -1 . The unresolved
complex mixture (UCM) was observed in all
sediments. The distribution of individual n-alkanes in
each core was different. For C03, the predominance
of C31 suggested terrestrial higher plant input. The
prominance of C18 in C07 suggested contribution of
marine algae and bacteria and the higher abundance
of C16, C18, C27 and C29 in C08 indicated mixture of
these sources. The terrigenous/aquatic ratio (TAR)
and carbon preference index (CPI) values showed
that the terrigenous input was predominant in
samples. The average chain lengths (ACL) do not
show significant variations (28.5 to 29.4), suggesting
stronger terrestrial influences [3].
The � 13 C values of individual n-alkanes (C16–33)
varied between -22.7‰ and -35.8‰. Individual nalkanes
carbon isotope values of Manguaba Lagoon
core (C03) are showed in Fig. 1. The � 13 C values for
the long-chain n-alkanes (C27, C29, C31 and C33) are
characteristic for n-alkanes biosynthesized by the C3
plants and coastal mangrove sources [3].
� 13 C (‰)
� 13 C (‰)
-20
-22
-24
-26
-28
-30
-32
-34
-36
-38
-20
-22
-24
-26
-28
-30
-32
-34
-36
-38
Carbon number
15 17 19 21 23 25 27 29 31 33
C03-1 C03-3 C03-5 C03-7 C03-9
15 17 19 21 23 25 27 29 31 33
C03-11 C03-13 C03-15 C03-17 C03-21
Fig.1. Individual n-alkanes carbon isotope values of
Manguaba Lagoon core (C03). The sections C03-1, C03-3,
C03-5, C03-7, C03-9, C03-11, C03-13, C03-15, C03-17 and
C03-21 correspond to the depths 1, 5, 9, 13, 17, 21, 25, 29,
33 and 41cm, respectively.
References
[1] Harada, N., Handa, N., Fukushi, M., Ishiwatari, R.
(1995) Org. Geochem. 23, 229-237.
[2] ANA/CELMM. (2006) Agência Nacional de Águas
Brazil.
[3] Sikes, E. L., Uhle, M. E., Nodder, S. D., Howard, M. E.
(2009) Mar. Chem. 113, 149-163.
[4] Silva, L. S. V., Piovano, E. L., Azevedo, D. A., Aquino
Neto, F. R. (2008) Org. Geochem. 39, 450-464.
524

P-396
Brominated flame retardants in German Wadden Sea sediments
Thorsten Stiehl 1 , George Sawal 2 , Barbara Scholz-Böttcher 1 , Melanie Beck 1 , Jürgen
Rullkötter 1 , Peter Lepom 2
1 Institute of Chemistry and Biology of the Marine Environment (ICBM), University of Oldenburg, P.O. Box
2503, Oldenburg, Germany, 2 Laboratory for Water Analysis, Federal Environment Agency, Bismarckplatz 1,
Berlin, Germany
To prevent or at least delay combustion of
commercial and consumer products brominated flame
retardants (BFR) are added to a variety of industry
goods such as electronics, plastics or textiles. BFRs
can be either of aromatic, aliphatic, or cycloaliphatic
structure and have different degrees of bromination.
Among the group of BFRs decabromodiphenyl ether
(BDE209) is one of the most commonly utilised
chemicals. As many of the BFRs are admixtures and
not chemically bound to the matrix, they can easily
enter the environment. Their unique physico-chemical
properties make them persistent and allow long-range
transport as well as bioaccumulation in different
environmental matrices and along food chains [1].
Penta- and octabromodiphenyl ethers are listed in the
amendments to the Stockholm Convention on
Persistent Organic Pollutants in 2010.
So far, data on BFR levels in sediments of the
German Bight are scarce, and none were available for
the Jade Bay, which forms part of the large tidal flat
system in North West Germany.
Twenty-three polybrominated diphenyl ethers
(PBDEs) and six novel BFRs were determined in
Wadden Sea surface sediments collected in the Inner
Jade Bay using a fully optimised and validated GC-
ECNI-MS method. Analyses of PBDEs,
pentabromotoluene (PBT), pentabromoethylbenzene
(PBEB), hexabromobenzene (HBB), brominated
biphenyls (BB153, BB209) and
1,2-bis(tribromophenoxy)ethane (BTBPE) were
performed as described previously 2 with some
modifications [2].
In the studied sediments, BDE209 prevailed. In
addition, low concentrations of BDE28, BDE47,
BDE49, BDE66, BDE99, BDE100, BDE183,
BDE196 and BDE197 were detected in all samples.
The levels of the remaining congeners were below the
limit of detection (LoD

P-397
Impact of different operating modes on the indigenous microbial
ecosystems in energy storage systems in the North German
Basin: Compositional changes and membrane phospholipid
adaptation
Alexandra Vetter 1 , Kai Mangelsdorf 1 , Stephanie Lerm 1 , Mashal Alawi 1 , Andrea Seibt 2 ,
Markus Wolfgramm 3 , Hilke Würdemann 1 , Andrea Vieth-Hillebrand 1
1 GFZ German Research Centre for Geosciences, Potsdam, Germany, 2 BWG Geochemische Beratung GbR,
Neubrandenburg, Germany, 3 Geothermie Neubrandenburg GmbH (GTN), Neubrandenburg, Germany
(corresponding author:vetter@gfz-potsdam.de)
The composition of microbial communities was
examined in three geothermal energy storages in the
North German Basin. These aquifer thermal energy
storages (ATES) differ in depth (20 to 1250 m), in fluid
chemistry (freshwater, brine), and functionality
(heat/cold storage). To investigate the microbial
ecosystems the bacterial membrane phospholipid
fatty acid (PLFA) composition and the fluid chemistry,
especially, of potential nutrient for the indigenous
microorganisms such as sulfate, nitrate, low
molecular weight organic acids and DOC as well as
its carbon isotopic composition was evaluated.
A solar assisted heat storage located in a quaternary
freshwater aquifer in 15 to 30 m depth was monitored
concerning its microbial composition with respect to
the seasonal changes of charge and discharge of
heat. The plant stores the surplus heat with
temperatures of 50°C from the solar energy
production during summertime (charge mode).
Therefore, water is pumped from the cold side with
temperatures of 8 to 20°C, loaded with heat in a heat
exchanger and re-injected into the warm well.
Discharge of heat is carried out in wintertime, when
heat demand increases for space heating and
domestic hot water preparation in multi-family houses.
In wintertime, the PLFA composition of the indigenous
microbial community, mainly 16:1, 16:0, 18:1, 18:0,
and branched fatty acids (FA) with 15 and 17 carbon
atoms, showed an adaptation of the cell membrane
during the discharge mode, when temperature
decreases from 50 to 13.7°C during time of heat
extraction. This is reflected by a shift of 13.4 %
towards more unsaturated fatty acids (FA) and of 10.8
% towards more FAs with shorter chain length.
Moreover, the anteiso/iso ratio was higher at cooler
temperatures indicating a membrane temperature
adaptation of these microorganisms.
World‘s deepest heat storage in the North German
Basin (1250 m depth) stores surplus heat from a gas
and steam cogeneration plant in summertime, which
is used in wintertime for district heating. The fluid is
NaCl dominated with high sulfate concentration (ca. 1
g/L) and the DOC can account for 18 mg C/L.
Temperature ranges on the warm side from 90 to
65°C and on the cold side from 50 to 45°C. PLFA
profiles are dominated by iso- and anteiso-15:0 on the
cold side, while on the warm side 16:0 is the major
compound. Moreover, the PLFA patterns indicate
different compositions of the microbial communities
on the warm and cold side.
In contrast to shallow and deep heat storages,
another system, located in 30 to 60 m depth, in the
North German Basin is used as a cold storage for air
conditioning of buildings in summertime (discharge
mode). In wintertime (charge mode) the freshwater
from the warm side is pumped up, cooled down by an
air cooler and subsequently re-injected into the cold
side. Temperature ranges on the warm side from 14
to 30°C and on the cold side from 6 to 10°C. Within a
four years monitoring, two clogging events occur
during the discharge phase and the injection rates on
the warm side was reduced. PLFA pattern clearly
reveals changes in the microbial community
composition during the clogging events. During these
events the 16:1�7 fatty acid and 18:1�7 significantly
increase compared to the normal operating mode.
These fatty acids are known to be main constituents
of the iron oxidizing bacterium Gallionella [1] and the
sulphur oxidizing bacterium Thiothrix [2]. Both
bacteria are known to be involved in clogging events.
Microbiological analysis confirmed the occurrence of
these species during the disturbance time in the
storage system and inorganic investigations reveal
iron scales in the plant.
The study shows clearly that microorganisms are
capable to adapt to specific conditions within short
times and can influence the working reliability of
geothermal energy storages.
[1] Sahl et al. (2008) Appl. Environ. Microbiol., 74(1),
143-152.
[2] Zhang et al. (2005) Appl. Environ. Microbiol.,
71(4), 2106-2112.
526

P-398
Stable carbon isotope fractionation of dissolved BTEX during
progressive volatilization
Yongqiang Xiong, Yun Li, Qianyong Liang, Chenchen Fang, Jingru Zhang
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of
Sciences, Guangzhou, China (corresponding author:xiongyq@gig.ac.cn)
Benzene, toluene, ethylbenzene, and xylenes
(BTEX) have attracted much attend because of their
significant hazard to human health and the
environment. In addition to biodegradation,
attenuation of BTEX contamination can be caused by
different processes, such as sorption, dispersion,
diffusion, and volatilization. Compound-specific stable
isotope analysis (CSIA) has been widely used to trace
the source of contaminants and monitor the
processes controlling their fate and transport in
subsurface environments. To accurately interpret
isotopic data of BTEX in the environment, the isotopic
effects of various subsurface processes should be
better understood, particularly in different environment
conditions. For example, in the saturated zone,
sorption and degradation are the primary processes
of contaminant attenuation. The equilibrium model is
probably appropriate for describing isotope
fractionation in the zone, because where the
movement of water and contaminants is slow enough
and contact times are long enough. In the unsaturated
zone, however, diffusion and volatilization are
important transport processes for VOCs. Thus, the
Rayleigh fractionation model is more compatible with
the open system.
An experiment of open, progressive volatilization
was conducted in order to investigate stable carbon
isotopic fractionation of dissolved BTEX in the
unsaturated zone. Headspace single-drop
microextraction (HS-SDME), coupled to gas
chromatography (GC) and gas chromatographyisotope
ratio mass spectrometry (GC-IRMS), was
employed to determine concentration and carbon
isotopic values of the residual BTEX in the aqueous
solutions by optimizing extraction conditions.
Fig. 1 demonstrates a good linear least-squares fit
between ln[(1000+δ 13 Cresidual) /(1000+δ 13 Cinitial)] and lnf
for each compound of BTEX, with R 2 being 0.9072,
0.9166, 0.8065, and 0.8064, respectively. This
suggests that the volatilization of dissolved BTEX
follows the Rayleigh distillation trend. Although the
isotope fractionation enrichment factors are small
(△ 13 Cvapor-liquid falling in the range of -0.2 ~ -0.1‰), a
significant shift of δ 13 C values (>0.5‰) are observed
when extensive volatilization of BTEX has taken place
(such as >75% for Benzene and > 95% for toluene,
ethylbenzene, and o-xylene, respectively). Therefore,
before the corresponding change points are reached,
� 13 C signature of BTEX can potentially be used to
trace their source and transport in the subsurface.
Moreover, it is also used to assess the remediation
implementation (such as soil vapor extraction) by
monitoring the stable isotope values vs. time.
Removal of most of the initial contaminants will result
in a remarkable shift of the isotopic composition of the
residual BTEX, which can provide useful information
on the efficacy of soil vapor extraction as a
remediation technique.
ln[(δ 13 Cr+1000)/(δ 13 Ci+1000)]
ln[(δ 13 Cr+1000)/(δ 13 Ci+1000)]
Fig. 1. Carbon isotope fractionation of BTEX, as ln[(1000+δ 13 Cr)
/(1000+δ 13 Ci)] vs. fraction of BTEX remaining, presented as lnf,
during progressive evaporation
0.0014
0.0012
0.001
0.0008
0.0006
0.0004
0.0002
0
α=0.9998
Benzene
y = -0.0002x + 0.0002
R 2 = 0.9072
-0.0002
-7.00 -5.00 -3.00 -1.00
lnf
1.00
0.0014
0.0012
0.001
0.0008
0.0006
0.0004
0.0002
0
Ethylbenzene
y = -0.0001x + 7E-05
R 2 = 0.8065
lnf
α=0.9999
0.0002
lnf
α=0.9999
-0.0002
-7.00 -5.00 -3.00 -1.00 1.00
0.0014
0.0012
0.001
0.0008
0.0006
0.0004
0.0002
0
0.001
0.0008
0.0006
0.0004
0
α=0.9998
y = -0.0001x + 4E-05
R 2 = 0.8064
Toluene
y = -0.0002x - 8E-05
R 2 = 0.9166
-0.0002
-7.00
0.0014
-5.00 -3.00
lnf
-1.00 1.00
o- Xylene
0.0012
-0.0002
-7.00 -5.00 -3.00 -1.00 1.00
527

P-399
Resolving sources and preservation mechanism of
ahthropogenic and natural organic matter in sediment of Beijing-
Hangzhou Great Canal, China with usage of Hydropyrolysis
(HyPy)
Xiaoyu Zhang, William Meredity, Colin Snape, Yongge Sun, Xin Chen, Yang Xu
Earth Science, Zhejiang University, Hangzhou, China (corresponding author:zhang_xiaoyu@zju.edu.cn)
Traditionally, most investigations of sources of
organic materials in sediments regarded the
extraction fraction exclusively. Actually, low molecular
weight organic compounds can be affected by
intermolecular interactions with geomacro-molecules,
preventing their extraction. The major quantities of
bound residues in sediments (soils) are thought to be
incorporated reversibly, implying the classification of
the phenomenon as a temporary sink for
contaminants on the one hand. On the other hand,
bound residues recover an additional contamination
potential, which is not concerned by conventional
analyzes, considering extractable compounds only.
HydroPyrolysis at high hydrogen pressures (>10 MPa)
in the presence of a dispersed sulphided molybdenum
catalyst has demonstrated the unique ability of
maximizing yields of aliphatic skeletons with
minimizing the structural rearrangement of
stereochemistry, releasing incorporated bound lower
molecular aromatic hydrocarbon through degrading
geo-macromolecules whilst keeping the low molecular
stable. Furthermore, Staged HydroPyrolysis has
confirmed that molecular biomarkers release at higher
temperatures through cleaving relatively strong bonds
are quantitatively more significant than those released
at lower temperatures for immature source rock. Thus,
HydroPyrolysis is considered to be an attractive route
to provide better insight into the preservation of
covalently-bound biomarker and useful especially for
assisting organic compounds source correlations.
In this study, comparisions of covalently-bound
aliphatic and aromatic hydrocarbon and aliphatic
biomarkers released via Single and Staged HyPy with
their solvent-extractable counterparts for the sediment
collected at Beidaqiao Bridge, Jing-Hang Great Canal,
Hangzhou, China have been carefully analyzed to
illustrate the main sources and preservation
mechanism of anthropogenic and natural organic
matter in this highly polluted river sediment.
The results from solvent-extractable aliphatic and
aromatic both strongly suggest that the organic
materials in the Canal sediment are the admixture of
sources from uncombusted fossil fuel residues and
land derived higher plant waxes inputs and also from
combustion/pyrolysis of fossil fuels, although the
evidence of combustion/pyrolysis of fossil fuels are
relatively weak.
The comparison of yields from Single and Staged
HyPy indicate that most n-alkanes (>80%) are
generated at stage ~350°C, with decreasing yield of
n-alkane under higher temperatures, only 5% of nalkanes
are genereated under 400~450°C. Both
Single HyPy and Staged HyPy at lower temperature
demonstrate the prevalence distribution of precursers
of fatty acid derived from land higher plants in this
case. The distribution pattern of n-alkanes at
400~450°C Staged HyPy suggest that small amount
of petroleum residue combined in the sediment.
Meanwhile the 20S/(S+R) ratio of C29 sterane
increases obviously with increasing temperature,
which indicate the capability of Staged HyPy to
release the biomarker species for tracing the source
of oil pollutant in environmental samples. On the
contrary, yields of PAHs increase with temperature
which need further research especially from evidence
of δ13C information to illustrate the possible sources
correlations of PAHs.
The research indicates that major quantity of
anthropogenic organic matter in the sediment are
extractable, while very few amount of them exist with
covalently bound. Further research need to carry out
especially for the PAHs in the sediments.
This work was financially supported by ZJNSF(No.
Y5100117), Education of Zhejiang Provence (No.
Y200907741) and The State Key Laboratory of
Organic Geochemistry, China (No. OGL-200810).
528

P-401
Hydrogen isotope ratios of leaf wax lipids illustrate temporal and
spatial variations in the hydrologic cycle – results from two
calibration studies off NW Africa
Britta Beckmann 1 , Eva Niedermeyer 2 , Alex Sessions 2 , Enno Schefuss 1
1 MARUM – Center for Marine Environmental Sciences - University of Bremen, Bremen, Germany,
2 California Institute of Technology - Division of Geological & Planetary Sciences, Pasadena, United States of
America (corresponding author:bbeckman@uni-bremen.de)
We worked on marine sediments deposited off NW
Africa to explore how continental (paleo)-hydrologic
conditions preserved in the hydrogen isotopic
composition (δD, in ‰ relative to VSMOW) of
terrestrial plant waxes are reflected in marine
sediments. In the first study, δD values of long-chain
n-alkanes extracted from surface sediments along a
transect paralleling the arid sub-Saharan to the moist
subhumid Sudanian climate zones on land were
compared to the isotopic composition of precipitation
over the continent. To address temporal variations on
short time-scales, we examined in a second study the
δD values in n-alkanes from a short sediment core
(GeoB9501-4) covering the past 100 years (Mulitza et
al., 2010) and compared them with instrumental data
before, during and after the Sahel drought.
n-alkane distributions and concentrations in surface
sediments indicate considerable contribution of
terrestrial organic matter at all sites. Values of the
carbon preference index (CPI, n-C25 to n-C33) vary
between 3.4 and 4.6. Distribution patterns of n-C29
and n-C31 alkanes illustrate the dominance of grasses
in the northern part of the investigated region. Shrubs
and trees appear to prevail in the southern part of the
study area as indicated by a dominance of n-C29
alkanes (e.g., Rommerskirchen et al., 2006; Vogts et
al., 2009), which is in accordance with the vegetation
distribution on the continent. δD values of the n-C31
alkanes vary between -125‰ and -150‰ in the
surface samples. In general, δD values are higher in
n-alkanes from the northern part of the study area (~
21°N) and decrease southward. Lowest δD values
were measured in samples from the southernmost
part of the study area around 13°N. The observed
spatial distribution of δD values from n-C31 alkanes
resembles the distribution of growing season
precipitation δD on the continent (Bowen et al., 2005)
which shows highest values along the coast between
21° and 28°N and lowest values between 9° and
14°N.
Information on short time-scales come from sediment
core GeoB9501-4 taken north of the Senegal rivermouth
and sampled in high temporal resolution (each
sample covering approx. 4 years). Here, δD values of
the n-C31 alkane (which was the most cleanly
separated compound of adequate abundance) reveal
temporal variations that can be linked to hydrologic
conditions over the western Sahel as captured by the
instrumental record. Among other features, the onset
and persistence of the Sahel drought in the late 1960s
to the mid 1990s can be traced in a positive 12‰ shift
of the δD signal. In a further step, this shift will be
related to instrumental data of continental runoff and
average precipitation amounts (annual and growing
season) in NW African sub-Saharan countries.
References
[1] Bowen, G.J. et al. (2005) Oecologia. 143, 337-
348.
[2] Mulitza, S. et al. (2010) Nature 466, 226-228.
[3] Rommerskirchen, F. et al. (2006) Org. Geochem.
37, 1303-1332.
[4] Vogts, A. et al. (2009) Org. Geochem. 40, 1037-
1054.
529

P-402
New insights into soil organic carbon build-up from compoundspecific
radiocarbon analysis
Axel Birkholz 1 , Rienk Smittenberg 1 , Irka Hajdas 2 , Lukas Wacker 2 , Jostein Bakke 3,4 ,
Stefano M. Bernasconi 1
1 ETH Zürich, Geological Institute, Zürich, Switzerland, 2 ETH Zürich, Laboratory of Ion Beam Physics, Zürich,
Switzerland, 3 Bjerknes Centre for Climate Research, Bergen, Norway, 4 University of Bergen, Department of
Geography, Bergen, Norway (corresponding author:axel.birkholz@erdw.ethz.ch)
With ~1500 Gt, Soil Organic Carbon (SOC) is the
second largest active carbon pool in the world, and
hence plays an important role in the global carbon
cycle. However, there are still many uncertainties
about the reactivity of the SOC in response to climatic
and environmental changes. In this respect,
especially the role of refractory SOC is important, as
this pool is ultimately responsible for long-term carbon
storage. It is, for instance, still uncertain how fast the
large amount of terrigenous carbon at higher latitudes
was accumulated after deglaciation, and if this buildup
is still ongoing or not [1]. To understand the longerterm
dynamics of this large carbon pool, one needs to
resort to sedimentary records, as experiments are not
possible at the time scales involved.
In order to gain more insight into SOC dynamics,
we expanded on the successful approach of
Smittenberg et al. [1] by analyzing the radiocarbon
content of soil-derived molecular compounds
preserved in a well-dated sedimentary record. When
compared to the depositional age of the sediment, the
age of the terrestrial lipids and organic carbon
fractions gives an average residence time of these
lipids and fractions in the SOC pool. Changes in the
age-differential between sediment and soil-derived
organic compounds over time give an estimate of
SOC build-up and evolution.
Since a large portion of terrigenous carbon is stored
at higher latitudes, we investigated the area of Lake
Lusvatnet, located on Andoya, Lofoten, Norway
(69°N), which was deglaciated shortly after the last
glacial maximum, unique for Scandinavia. In contrast
to the generally peat-dominated landscape the
catchment area of lake Lusvatnet is characterized by
relatively steep slopes and a relatively large amount
of mineral soil. In 2007 a ca. 5.5 m long lake sediment
core was taken. A preliminary age model suggests
that the core dates back to ca. 15 ka cal. BP. We
analyzed samples from twelve depth-horizons, each 4
cm thick, collected every 50 cm starting from the top
of the core, together with a higher resolution record
from the bottom of the core. Due to sediment
characteristic this part is thought to show the time of
deglaciation (14.6 to 11.6 ka cal. BP). In addition, a
short core was retrieved from the same location in
2008.
We present selected biomarker profiles especially
from the sediment deposited during the time of
deglaciation. In addition we present TOC contents,
� 13 C and � 15 N data for bulk samples. The data are
compared with other sedimentary, paleoenvironmental
and –climatic information available for
the region.
For radiocarbon analysis, compounds with an
unequivocal terrigenous source were isolated from
the total lipid extract, in order to separate them from
the aquatic – derived compounds. The isolated
compounds are branched glycerol dialkyl glycerol
tetraethers (brGDGTs), long chain n-alkanes and long
chain fatty acids (LCFAs). For the isolation and
purification of these compounds semi-preparative
High-Performance Liquid Chromatography - Mass
Spectrometry and preparative capillary Gas
Chromatography were used. Radiocarbon dating was
performed using an Accelerator Mass Spectrometer
interfaced with a gas source, allowing the analysis of
very small samples [2]. As expected, the isolated
compounds show a significant age difference to their
depositional age. We discuss the results in the
framework of SOC build-up and evolution.
References
[1] Smittenberg, R.H., Eglinton, T.I., Schouten, S., Damste,
J.S.S. (2006) Science 314, 1283-1286.
[2] M. Ruff, et al., Radiocarbon 49 (2007) 307.
530

P-403
Spatial variability of compound-specific �D at the field scale: A
case study from miliacin in broomcorn millet (Panicum
miliaceum)
Nicolas Bossard, Jérémy Jacob, Claude LeMilbeau, Rachel Boscardin,
Elisabeth Lallier-Vergès, Valery J. Terwilliger
Institut des Sciences de la Terre d’Orléans (ISTO), Université d’Orléans, UMR6113 du CNRS/INSU, Orléans,
France (corresponding author:jeremy.jacob@univ-orleans.fr)
The hydrogen isotopic composition (�D) of individual
compounds preserved in lake sediments has been
proposed as a proxy of the hydrological conditions
that prevailed at time of their synthesis. Numerous
parameters are susceptible of influencing this proxy,
the first of them being the �D of meteoritic waters.
Then, the combination of environmental (aridity, soil
properties…) and biological parameters modify the �D
of leaf water. Finally, the incorporation of hydrogen in
organic molecules during enzymatic reactions is
accompanied by isotopic fractionation. Lake
sediments accumulate organic matter produced at
catchment scale, thus produced by various organisms
developed on soils of potentially different properties.
The spatial variability of �D in plants at a catchment
scale is rarely taken into account [1], although it might
represent a serious source of uncertainty on the
paleoclimatic interpretation of sedimentary lipids �D.
In order to assess the confidence level in the �D of
sedimentary lipids, we have measured the �D of
miliacin (olean-18-en-3�ol ME), a biomarker specific
of broomcorn millet (Panicum miliaceum L.; [2]).
Miliacin was extracted from the seeds of millet plants
collected from 26 stands (3 replicates per stand)
randomly distributed in a field that shows a strong
heterogeneity in soil physico-chemical properties in
Mézières-lez-Cléry (Loiret, France; Figure 1). After
extraction and purification, miliacin was quantified and
its purity assessed by GC-MS. Miliacin was then coinjected
with a series of n-alkanes of known �D (Arndt
Schimmelmann, Indiana University) on a TraceGC
chromatograph coupled to a DeltaV Advantage irMS
through an Isolink interface and a Conflo IV system.
Precision for n-alkanes was around 3 ‰ and accuracy
of miliacin �D was better than 6 ‰. Miliacin �D values
range from -90 to -140 ‰ V-SMOW with an average
of -121.3+/-9.1 ‰ V-SMOW, i.e. close to values
reported for other pentacyclic triterpenes [3]. The
range of miliacin �D values (50 ‰) is unexpectedly
large and corresponds to radical environmental
changes (i.e. savannah to tropical forest) when
detected in sedimentary archives [4]. Standard
deviation average at single stand was 6.9 ‰ (from 2
to 16.5 ‰). High standard deviation is observed for
the smallest plants (developed on sandy soils) and for
plants collected in stands that exhibit the highest plant
density. Hence, in addition to soil properties, microcontrols
on humidity related, for example, to canopy
effects can significantly influence miliacin �D [5].
However, the Gaussian distribution (p>0.95) of
miliacin �D values indicates that they are governed by
a single dominant parameter.
Our study demonstrates that a significant variability of
compound-specific �D values is to be taken into
consideration at a catchment scale and shows, by
using a compound specific of a single plant, that �D
spatial variability cannot solely be imputed to different
plant types [1]. The propagation of this uncertainty
from spatially distributed biological sources towards
sedimentary archives through temporal storage in
soils remains to be estimated.
Figure 1: (a) Location of P. miliaceum field, heterogeneity of soil
properties on aerial picture (grey scale) and location of samples; (b)
Structure of miliacin (c) Distribution of miliacin �D values per plant.
References
[1] Hou, J., D'Andrea W., MacDonald D., Huang Y., 2007. Organic
Geochemistry 38, 977-984.
[2] Jacob, J., Disnar, J.R., Arnaud, F., Chapron, E., Debret, M.,
Lallier-Vergès, E., Desmet, M., Revel-Rolland, M. 2008. Journal of
Archaeological Science 35, 814-820.
[3] Sessions, A.L., 2006. Geochimica et Cosmochimica Acta 70,
2153–2162.
[4] Jacob, J., Huang, Y., Disnar, J.R., Sifeddine, Boussafir, M., A.,
Albuquerque, A.L.S., Turcq, B., 2007. Quaternary Science Reviews
26, 1004-1015.
[5] Farquhar, G., Cernusak, L., Barnes, B. 2007. Plant Physiology
143, 11-18.
531

P-404
Amino sugars as biomarkers for transformation of organic
nitrogen compounds in two Swiss lakes
Dörte Carstens, Krista E. Köllner, Gijs Nobbe, Helmut Bürgmann, Bernhard Wehrli,
Carsten J. Schubert
Swiss Federal Institute for Aquatic Science and Technology (Eawag), Surface Waters Research and
Management, Kastanienbaum, Switzerland (corresponding author:doerte.carstens@eawag.ch)
Studies on the fate of organic nitrogen
compounds in aquatic systems mostly concentrate on
marine environments. As amino sugars (AS) are
nitrogen and carbon containing molecules they are
important contributors to the nitrogen and carbon
cycle. Microorganisms mediate substantially
biogeochemical cycles as they represent both
contributors and degraders of organic matter. In order
to study the fate of organic nitrogen compounds and
the role of bacteria to organic matter transformation in
lacustrine systems Lake Brienz (oligotrophic,
holomictic) and Lake Zug (eutrophic, meromictic)
were chosen as study sites.
Water and particulate matter (> 0.7 μm) were
sampled in ten depths distributed over the entire
water columns in fall 2009. Plankton as source of
autochthonous material was collected in the
epilimnion. Additionally, sediment cores were
recovered. Concentrations of single AS in the
particulate fraction of the water samples, the plankton
and the first centimeters of the sediments were
measured by gas chromatography (GC). AS
concentrations of the unfiltered water samples were
determined by high performance liquid
chromatography. GlcN:GalN ratios were used to
identify the AS sources, as chitin-rich plankton has
GlcN:GalN ratios >14 and heterotrophic bacterial
communities ratios smaller than three [1]. Additionally
the Chlorin Index (CI) was applied as a pigment
based degradation parameter for organic matter
freshness. Concentrations of pheophytin and longchain
fatty acids in the sediments were measured by
GC. With the pheophytin and long-chain fatty acids
concentrations the input of terrestrial material to the
sediments was estimated.
The results showed decreasing carbon
normalized AS yields with increasing water depths
indicating enhanced degradation of AS compared to
the bulk organic matter in both lakes. Within the
sediments the AS yields were fluctuating with an
increasing trend for Lake Brienz and a decreasing
trend for Lake Zug with depth. The values of the CI
displayed degradation of particulate matter settling
towards the bottom of the lake and within the
sediments. The GlcN:GalN ratios showed a
replacement of the AS composition of the plankton by
the AS signature of heterotrophic microorganisms
along the water column. Even smaller values for the
ratio were found in the sediment samples indicating
ongoing degradation of the buried organic matter by
bacteria. Fluctuating AS yields within the sediments
could be explained by different fractions of
allochthonous material in the samples. Higher AS
yields were found in sediment layers with major input
of terrigenous organic matter. These findings indicate
that AS from autochthonous sources are more
degradable than those from allochthonous sources,
which are accumulating in the lake sediments.
Reference
[1] Benner, R. and Kaiser, K. (2003). Abundance of
amino sugars and peptidoglycan in marine particulate
and dissolved organic matter. Limnology and
Oceanography, 48(1):118–128.
532

P-405
A novel tool for food web study: compound-specific stable
nitrogen isotope analysis of amino acids
Yoshito Chikaraishi, Nanako Ogawa, Naohiko Ohkouchi
Japan Agency for Marine-Earth Science and Technology,, Yokosuka, Japan (corresponding
author:ychikaraishi@jamstec.go.jp)
Knowledge of the trophic position (TP) of organisms
in food webs allows understanding of biomass flow
and trophic linkages in complex networks of
ecosystems. Compound-specific stable isotope
analysis (CSIA) of amino acids is a new method with
that enables TP estimates of organisms in food webs
[Fig. 1; 1-4]. This approach is based on contrasting
isotopic fractionation during metabolic processes
between two common amino acids: glutamic acid
(Glu) shows significant 15 N-enrichment of +8.0‰
during reactions (transamination, deamination) that
cleaves the carbon-nitrogen bond, whereas
phenylalanine (Phe) shows little change in δ 15 N
values (by +0.4‰) during conversion to tyrosine that
neither forms nor cleaves the carbon-nitrogen bond
[3]. In the previous studies [3,4] we established based
a number of natural and laboratory grown organisms
a general equation for estimating the TP of organisms
by CSIA of amino acids:
TP = [(δ 15 NGlu – δ 15 NPhe + β)/7.6 ] + 1
where β represents the isotopic difference between
Glu and Phe in primary producers (–3.4‰ for aquatic
cyanobacteria and algae, +8.4‰ for terrestrial C3,
and –0.4‰ for terrestrial C4 plants). This method has
three key advantages.
1. The TP is estimated based on the δ 15 N of Glu and
Phe only from the target organism. Consequently,
unlike the bulk isotopic methods, it does not require
characterization of the δ 15 N values of primary
producers or baseline consumers.
2. A small uncertainty is expected. The fractional TP
standard deviation (1ζ) is only 0.12 and 0.20 units
for aquatic and terrestrial organisms, respectively.
3. A small sample size (nanomolar amount of N) is
required for CSIA of amino acids by GC/C/IRMS.
These advantages mean that CSIA overcomes a
number of concerns associated with the bulk isotope
analysis; consequently, it has been applied in
elucidating the TP of organisms in recent studies [5].
In the presentation, we review amino acid methods
and show its application to various natural organisms
in aquatic marine and freshwater as well as terrestrial
food webs.
Fig.1. The TP (a) is clearly proportionate to difference
in δ 15 N between Glu and Phe (b).
References
[1] McClelland & Montoya (2002) Ecology 83, 2173-
2180.
[2] Popp et al. (2007) In Stable isotopes as indicators
of ecological change. Academic Press. pp 173-190.
[3] Chikaraishi et al. (2009) Limnol. Oceanogr.: Meth
7, 740-750.
[4] Chikaraishi et al. (2010) In Earth, Life, and
Isotopes. Kyoto University press. pp. 37-51.
[5] Hannides et al. (2009) Limnol. Oceanogr. 54, 50-
61.
533

P-406
Biogeochemistry of lake Soppensee (Switzerland) using a
biomarker and a compound-specific isotope approach
Merle Gierga 1 , Rienk Smittenberg 1 , Irka Hajdas 2 , Lukas Wacker 2 , Stefano Bernasconi 1
1 ETH Zürich - Geological Institute, Zürich, Switzerland, 2 ETH Zürich - Laboratory of Ion Beam Physics,
Zürich, Switzerland (corresponding author:merle.gierga@erdw.ethz.ch)
We present the results of a biogeochemical study of
the sedimentary record of the Swiss lake Soppensee
covering the last 14,000 years BP. The small,
eutrophic, hard-water lake is situated on the central
Swiss Plateau (596 m a.s.l.). This is a very well dated
[1] and studied [e.g. 2,3] lake with undisturbed organic
carbon-rich and partially laminated sediments. The
master chronology of the record was established by
the use of a varve chronology and 14 C dating of
terrestrial macrofossils [1].
We show biomarker profiles, in combination with
compound-specific isotope analysis (δ 13 C and radiocarbon,
Δ 14 C), in order to gain insight in a number of
topics: a) The limnological and environmental history
of the lake; b) The potential of using specific
compounds for either radiocarbon dating of the
sediment core, or the extent to which terrestrial lipids
are pre-aged on land. The latter provides insight in
terrestrial carbon build-up through time; c) Early
diagenetic processes taking place in the lake environment.
The main lipid signature derives from higher
terrestrial plants. We have identified a suite of sterols,
long-chain alkyl lipids, and various pentacyclic
triterpenoid alcohols (PTAs). In the early Holocene,
just after deglaciation of the area, we found a range of
long-chain alkenones in some sediment layers that
are typically not found in fresh water environments,
but in cold, brackish systems [4,5].
We found a large number of specific degradation
products of the PTAs, like des-A triterpenoids and �2triterpenes,
together with partially unsaturated
carotenoids from photosynthetic sulfur bacteria, �2
and �3 sterenes, thiosterols and phytadienes. These
are all diagenetic products and provide evidence for
the processes of reductive dehydration, sulfurization
and the two-step process of sulfurization and
subsequent desulfurization described by Hebting
[6,7]. We also report the occurrence of 13�malabarica-14(27),17,21-triene,
which appears to be
a novel biomarker for anoxia, or even photic zone
euxinia.
Individual long-chain n-alkanes and fatty acids were
purified by preparative gas and liquid chromatography
for subsequent radiocarbon analysis. As in other
systems, they show an increasing age difference with
increasing age of deposition. This gives a measure for
residence time of these plant-derived compounds in
soils before entering the lake.
References
[1] Hajdas, I., Michczynski, A., Radiocarbon 52,
(2010), 1027-1040
[2] Lotter, A., J. Paleolimn. 25 (2001), 65-79
[3] Fischer, A., (1993), Diss. ETH Zürich No. 11924
[4] Toney, J. et al., GCA 74 (2010), 1563-1578
[5] Zink, K.G. et al., GCA 65 (2001), 253-265
[6] Hebting, Y. et al., Org. Lett. 5 (2003), 1571-1574
[7] Hebting, Y., et al., Science 312 (2006), 1627-1631
534

P-407
Compound specific hydrogen isotopes as indicator of core
metabolisms of benthic microorganisms in the Wadden Sea
Sandra Heinzelmann, Laura Villanueva, Stefan Schouten, Jaap Sinninghe Damsté,
Marcel van der Meer
NIOZ Netherlands Institute for Sea Research, Den Burg, Netherlands (corresponding
author:sandra.heinzelmann@nioz.nl)
The low elevation coastal zone is extremely
important since 10% of the human population lives
within 10 meters above the current sea level. In
addition, coastal areas form the habitat of a crucial
part of global biodiversity and play important roles in
global biogeochemical cycles. Climate changes of the
magnitude projected for the present century by the
Intergovernmental Panel on Climate Change would
impact the coastal zone in a number of ways, but
mainly by the projected global sea level rise. Microbial
communities in coastal environments are important in
this respect as they are at the bottom of the food
chain and thus often the first to deal with both natural
and human induced disturbances of the environment
and thereby form a natural buffer for the entire coastal
ecosystem. Microbial ecosystems also play an
important role in the intertidal areas of coastal zones
by sediment stabilization leading to sediment
accretion and even ―land‖ formation and thus form a
―natural‖ protection against potential sea level rises.
However, little is known about the fundamental role of
microbial communities in coastal zones and how this
might change under changing conditions. To
investigate their role, the main microbes in these
communities and especially the metabolisms
expressed in situ needs to be determined.
In this study, we examined microbial
communities present in different areas of the
Waddensea with a focus on the microbial mats on the
sandy beaches of the island Schiermonnikoog. These
microbial mats are ideal environments to study
different microbial metabolisms since they are formed
by photoautotrophic organisms producing organic
carbon used by heterotrophic organisms that deplete
the oxygen in the sediment. This enables sulphate
reducers to grow and produce sulphide, which in turn
is used by chemolithoautotrophic, photoautotrophic
and photoheterotrophic sulphide oxidizers.
We are also applying hydrogen isotopic
composition of lipid biomarkers as a new culture
independent tool for assessing the core metabolisms
of microorganisms as it has recently been shown that
there might be relatively large differences in hydrogen
isotopic composition of lipids produced by
microorganisms with different core metabolisms (1).
The results will be compared with those obtained by
stable isotope labelling of 16S rRNA and RNA
expression of specific genes for autotrophic and
heterotrophic microbes.
Figure 1: Indicated are those organisms that form
visible, well defined layers. Among the organisms that
are present, but do not produce visible layers are:
heterotrophs, Archaea and colorless sulfur bacteria
(chemolithoautotrophs).
1. X. Zhang, A. L. Gillespie, A. L. Sessions, Proc.
Natl. Acad. Sci. U. S. A 106, 12580 (2009).
535

P-408
Sea surface salinity reconstructions of the Agulhas current
based on alkenone hydrogen isotope ratios
Sebastian Kasper 1 , Marcel T.J. van der Meer 1 , Geert-Jan Brummer 2 , Isla S. Castañeda 1 ,
Rainer Zahn 3 , Jaap S. Sinninghe Damsté 1 , Stefan Schouten 1
1 Royal Netherlands Institute for Sea Research, Department of Marine Organic Biochemistry, 1790 AB Den
Burg (Texel), Netherlands, 2 Royal Netherlands Institute for Sea Research, Department of Marine Geology,
1790 AB Den Burg (Texel), Netherlands, 3 Universitat Autònoma de Barcelona, Institut de Ciència i
Tecnologia Ambientals, 08193 Bellaterra, Spain (corresponding author:sebastian.kasper@nioz.nl)
The South Equatorial Current transports
water masses with relatively high temperatures and
salinity across the Indian Ocean from Indonesia to
Africa. In front of Madagascar it branches into the
Northern Boundary Current and the East Madagascar
Current going south. Northwest of Madagascar the
Northern Boundary Current divides into the East
African Coastal Current and the Mozambique Current.
The latter is dominated by strong eddies which form
the Mozambique Channel. The Mozambique current
and the East Madagascar Current unite at 27°S to
form the Agulhas Current. At the southern tip of the
African shelf the Agulhas Current retroflects back into
the Indian Ocean whereby so called ‗Agulhas rings‘
spin off and release warmer and more saline water
into the South Atlantic Ocean. The magnitude of the
Agulhas leakage, therefore, has a strong impact on
the Atlantic Meridional Overturning Circulation and
hence the entire meridional heat flux. Thus, glacial –
interglacial fluctuations of the Agulhas leakage into
the Atlantic Ocean can affect global temperatures (1).
Reconstructions of the dynamics of the Agulhas
current based on geochemical proxies for sea surface
temperatures and salinity could help to understand
the link between the magnitude of the Agulhas current
and global temperatures.
Although there are a number of proxies
available for reconstructing sea surface temperatures,
few tools are available for salinity reconstructions. It
has been suggested that alkenone-derived hydrogen
isotope ratios are linearly related to salinity and
therefore could be used as a tool for sea surface
salinity reconstructions (2, 3). To investigate the
possibility of using deuterium isotopes of alkenones
as a proxy for salinity reconstructions of the Agulhas
current we are currently performing a core top study
from the Mozambique Channel and the Agulhas
current. In addition, we are generating long term
alkenone hydrogen isotope records of selected
sediment cores to examine temporal variations in
salinity in the Agulhas system with focus on the
transition from marine isotope stage (MIS) 6 to 5.
During MIS 6 the subtropical front is thought to have
moved northwards (4) weakening the exchange
between the Indian and Atlantic Ocean and a build-up
of warm saline water at the tip of South Africa. During
early MIS 5 the exchange is thought to increase again
resulting in a decrease in SST and salinity. This drop
in salinity is reflected in a decrease in Δδ 18 Osw in the
same core from the Agulhas corridor (Fig. 1) (4).
Initial results show that there is a decrease of
approximately 15 per mill in the alkenone hydrogen
isotope ratio from MIS 6 to 5 in agreement with the
suggested drop in salinity, suggesting that it can be a
useful tracer for salinity changes in the Agulhas
region.
1. C. S. M. Turney, R. T. Jones, Journal of
Quaternary Science 25, 839 (2010).
2. S. Schouten et al., Biogeosciences 3, 113
(2006).
3. M. T. J. van der Meer et al., Earth and
Planetary Science Letters 262, 594 (2007).
4. G. Martinez-Mendez et al., Paleoceanography
25, (2010).
536

P-409
Confining the role of biotic and/or abiotic factors influencing the
14C isotopic composition of chlorophyll a isolated from algal
cultures grown under different seawater DIC Δ14C
concentrations
Stephanie Kusch 1,2 , Albert Benthien 1 , Björn Rost 1 , Gesine Mollenhauer 1,2
1 Alfred Wegener Institute for Polar and Marine Research, Bremerhaven, Germany, 2 University of Bremen,
Bremen, Germany (corresponding author:Stephanie.Kusch@awi.de)
Tetrapyrrole molecules are found abundantly
throughout the geological record. Such molecules
unambiguously derive from chlorophyll a and can,
thus, directly be linked to photosynthesis. The
diagenetic alteration of chlorophyll a itself is generally
assumed to occur on rapid timescales on the order of
days to weeks as determined from laboratory studies
(e.g. Sun et al., 1993). However, in a study of Kusch
et al. (2010) chlorophyll a from NW Black Sea coretop
sediments was found to be much older than
expected based on such previously reported data.
Chlorophyll a Δ 14 C concentrations were translated
into absolute ages of roughly 50 years to up to 1300
years for anoxic and oxic sedimentary conditions,
respectively. The enhanced preservation was
attributed to result from protective mechanisms most
likely including mineral association, hypoxia and light
limitation. Nevertheless, a final identification of the
controlling preservation parameters could not be
achieved based on the isotopic analysis of the
investigated environmental samples.
In order to help in understanding the diagenetic fate of
chlorophyll a, we performed a culturing study to
confine the role of biotic and/or abiotic processes
altering the compound-specific
14 C isotopic
composition of chlorophyll a. Batch cultures of the
haptophyte Emiliania huxleyi and the diatom
Thalassiosira pseudonana were grown under different
seawater dissolved inorganic carbon (DIC) Δ 14 C
concentrations representing fossil (-1000‰), modern
(+30‰), and intermediate (ca. -520‰) values. To
stimulate algal growth and pigment production the
seawater was enriched in nutrients according to f/2
medium (Guillard & Ryther, 1962) and temperature
and photon flux intensity were set to 15°C and
100 µmol photons m –2 s –1 , respectively. Chlorophyll a
was isolated using a two-step reversed-phase HPLC-
DAD method. Additionally, alkenones and highly
branched isoprenoids (HBIs) were purified from the E.
huxleyi and T. pseudonana cultures, respectively,
using wet-chemical techniques or PCGC.
Here we show Δ 14 C concentration data of
chlorophyll a, alkenones, HBIs, and seawater DIC.
Our results, for the first time, allow a precise
determination of both the modern and fossil HPLC
processing blanks influencing the compound-specific
14 C results. Such precise determination of the blank C
14 C isotopic composition is a pre-requisite for a valid
assessment of biotic or other abiotic factors
influencing the chlorophyll a Δ 14 C concentrations. For
example, our data allow assessing potential
metabolically-driven alterations by comparison of the
chlorophyll a Δ 14 C with the respective alkenone or
HBI (for which the blank C isotopic composition is
known) and pre- and post-growth seawater DIC Δ 14 C
concentration data.
References
Guillard, R.R.L., Ryther, J.H. (1962): Studies of
marine planktonic diatoms: I. Cyclotella nana Hustedt,
and Detonula confervacea (cleve) gran. Canadian
Journal of Microbiology, 8, 229-239.
Kusch, S., Kashiyama, Y., Ogawa, N.O., Altabet, M.,
Butzin, M., Friedrich, J., Ohkouchi, N., Mollenhauer,
G. (2010): Implications for chloro- and pheopigment
synthesis and preservation from combined
compound-specific δ 13 C, δ 15 N, and Δ 14 C analysis,
Biogeosciences, 7, 4105-4118.
Sun, M., Lee, C., and Aller, R. C. (1993): Anoxic and
oxic degradation of 14 C labeled chloropigments and a
14 C labeled diatom in Long Island Sound sediments,
Limnology and Oceanography, 38, 1438-1451.
537

P-410
Carbon cycling in lacustrine food webs
J. Marieke Lammers 1 , Carsten J. Schubert 2 , Jack J. Middelburg 1 , Jaap S. Sinninghe
Damsté 1,3 , Gert-Jan Reichart 1
1 Universiteit Utrecht, Utrecht, Netherlands, 2 EAWAG, Kastanienbaum, Switzerland, 3 Netherlands Institute for
Sea Research, Den Burg, Netherlands (corresponding author:M.Lammers@geo.uu.nl)
Heterotrophs in freshwater systems rely on three
major sources of carbon/energy: (1) local primary
production, (2) terrestrial input from plants and soils
and (3) methanotrophic biomass (depending on either
locally produced or imported methane). The
availability of these three energy sources has major
consequences for food web functioning and structure,
and determine the carbon fluxes within the lake and
how much carbon is ultimately exported from the lake
to rivers or the atmosphere. Terrestrial
(allochthonous) organic carbon is traditionally
assumed to be aged and thus refractory, yet evidence
indicates that it may fuel parts of the food web [1, 2],
enhancing secondary production [1, 3]. So far, the
secondary producers involved and relative
contributions of in situ produced and allochthonous
organic matter to secondary productivity remains
poorly quantified.
Processing of terrestrial organic matter in lakes is
highly variable through the year [3], and possibly
depending on trophic level [1]. This research,
therefore, focuses on identifying main organic carbon
fluxes and elucidating food web functioning in
freshwater systems with variable trophic levels.
Energy flow at higher food web levels can be studied
using stable isotope analyses [4]. Two frequently
used approaches, sampling primary producers or bulk
particulate organic matter (POM), both have their
inherent problems. Putative primary consumers may
sometimes consume small heterotrophs and bulk
POM comprises not only primary producers but also
bacteria, small heterotrophs and detritus. Compound
specific isotope analysis (CSIA) of lipid biomarkers
allows including the microbial compartment of food
webs [5].
Two Swiss lakes are studied for food web
structure and carbon flows. Lake Lucerne is a prealpine,
oligotrophic lake with limited terrestrial input.
Rotsee, a small eutrophic lake just north of Lucerne,
has a major methane-based productivity. Samples for
characterizing DIC, DOC and POM were collected at
different water depths. Also, samples of soil
surrounding Lake Lucerne were collected. DIC, DOC
and POM concentrations and carbon isotopic
analyses of inflowing streams, lake water and
outflowing streams are used to deduce whether the
lakes are a net carbon source or sink. DOC is the
main coupling between autotrophs and heterotrophic
bacteria. It forms an important step in the food web
and is therefore analyzed for bulk isotopic
composition. POM is often used as a representative
of phytoplankton carbon and is therefore analyzed for
bulk carbon and nitrogen isotopic composition. To
differentiate between algal and bacterial classes,
POM is also analyzed for biomarker presence and
abundance and subsequently for CS-δ 13 C. As a first
order approximation, functional groups are assigned
using analyses of phospholipid-derived fatty acids
(PLFA). More specifically, other lipid biomarkers such
as free fatty acids, sterols and hopanoids are used to
identify and quantify algal and bacterial classes.
Samples of soil surrounding Lake Lucerne are
analyzed similarly to POM samples in order to obtain
isotopic signature and compositional information on
allochthonous material entering the lake.
References
[1] Cole et al. (2006) Ecology Letters 9: 558-568
[2] Cole et al. (2007) Ecosystems 10: 171-184
[3] Pace et al. (2004) Nature 427: 240-243
[4] Peterson and Fry (1987) Annu. Rev. Ecol. Syst.
18: 293-320
[5] Middelburg et al. (2000) Limnol. Ocean. 45: 1224-
1234
538

P-411
Intramolecular Radiocarbon Dating on Archaeal Intact Polar
Lipids
Chun Zhu 1 , Gesine Mollenhauer 2 , Julius Lipp 1 , Yu-shih Lin 1 , Kai-Uwe Hinrichs 1
1 Organic Geochemistry Group, Dept. of Geosciences and MARUM Center for Marine Environmental
Sciences, Bremen, Germany, 2 Alfred Wegener Institute for Polar and Marine Research, Bremerhaven,
Germany (corresponding author:czhu@uni-bremen.de)
Investigations on intact polar lipids (IPLs) and
their δ 13 C values have suggested that vast archaeal
communities characterized by a heterotrophic lifestyle
are prevalent in deep-sea subsurface sediments
(Biddle et al., 2006; Lipp et al., 2008). In situ 13 Ctracer
experiments in surface sediments further
suggested that benthic archaea are capable to build
their membranes partially by recycling fossil archaeal
membranes and detritus (Takano et al., 2010) to
minimize energy expenditures, supporting the
hypothesis that adaptations to chronic energy stress
are a unifying ecological principle of archaea
(Valentine, 2007).
Lipid recycling as proposed by Takano et al.
(2010) involves a mechanism in which the biphytanes
in GDGTs (glycerol dibiphytanyl glycerol tetraethers)
are sourced from a different carbon pool than the
glycerol and by inference, presumably also the polar
headgroups. Disparity of radiocarbon age between
these molecular moieties likely results and may
encode valuable information on metabolic traits of the
benthic archaeal communities and on the fate of
archaeal lipids in sediments. Intramolecular
radiocarbon dating on IPLs in subseafloor sediments
can provide direct evidence for mechanisms of in situ
archaeal lipid synthesis and substantiate the fidelity of
IPLs as molecular tracers for a living deep biosphere.
We therefore developed a new analytical
protocol for intramolecular Δ 14 C dating on specific
IPLs. Individual IPLs (i.e. diglycosyl-GDGTs and
H341-GDGTs) were isolated and purified from the
sediment matrix using orthogonal columns (Fig. 1a,b).
Headgroups and core-GDGTs are cleaved from IPLs.
Subsequently, an improved chromatography of core-
GDGTs with a separation of GDGT-4 (GDGT bearing
four pentacyclic rings) from crenarchaeol was
achieved for the first time through a reverse phase
(RP) HPLC (Fig. 1c). Finally, sample processing
blanks are systematically assessed and corrected.
Sediments were collected from the eastern
Mediterranean Sea, the Marmara Sea and the Black
Sea. These sites are characterized by high
sedimentation rates and pre-aged terrestrial OM and
well-dated sapropel deposition. Down-core analysis of
Δ 14 C ages on headgroups, caldarchaeol and
crenarchaeol cleaved from diglycosyl-GDGTs
and H341-GDGTs, respectively, as well as fossil core
GDGTs and dissolved inorganic carbon (DIC) in pore
water are currently undertaken. Those Δ 14 C values
will be compared to the established age models of the
cores. Finally, the metabolism of benthic archaea and
the fidelity of IPLs as living biomass tracers in deeply
buried sediments will be discussed.
Fig.1. Partial HPLC–ESI–MS density maps showing
the peaks of H341-GDGTs (a) and diglycosyl-GDGTs
(b) purified by orthogonal columns, and partial
reversed phase chromatogram of core-GDGTs
determined by HPLC-APCI-MS (c). (number 0-5 and
5‘ denote GDGT-0, GDGT-1, GDGT-2, GDGT-3,
GDGT-4, crenarchaeol and regioisomer of
crenarchaeol, respectively).
References
Biddle, J.F. et al., 2006. PNAS 103, 3846-3851.
Lipp, J.S. et al., 2008. Nature 454, 991-994.
Takano et al., 2010. Nature Geosciences 5, 316-323
Valentine 2007. Nature Reviews Microbiology 5, 316-
323.
539

P-412
Radiocarbon distributions in Lake Superior, the world’s largest
freshwater lake (by area)
Prosper Zigah 2 , Elizabeth Minor 1 , Josef Werne 1
1 Large Lakes Observatory and Dept of Chem and Biochem, University of Minnesota Duluth, Duluth, MN,
United States of America, 2 Water Resources Science and Large Lakes Observatory, University of Minnesota
Duluth, Duluth, MN, United States of America (corresponding author:eminor@d.umn.edu)
Lake Superior, as a deep (average depth 150 m;
maximum depth 406 m), oligotrophic large lake
dominated by planktonic processes, provides a
unique opportunity to understand biogeochemical
processes occurring at meso-to-synoptic scales, and
at basin-wide integrated level, something that is
logistically difficult to do in the world ocean. Lake
Superior‘s biogeochemistry appears similar to openocean
marine systems, with low water-column
nutrient levels, an ecosystem weighted toward
microbial processes, and low inputs of terrestrial
material due to a low watershed to surface area ratio.
The lake‘s mixing regime, however, is radically
different from that of the open ocean, with complete
water column overturn occurring in both spring and
fall and stable summer stratification. Thus Lake
Superior becomes a very interesting system for
studying interactions between the various pools within
the aquatic carbon cycle and seeing how the
biogeochemistry reacts when placed within very
different timescales of physical mixing processes.
Here, we report the ∆ 14 C, δ 13 C values and the
concentrations of dissolved inorganic carbon (DIC),
dissolved organic carbon (DOC), and particulate
organic carbon (POC) at multiple offshore sites during
mixed and stratified conditions in Lake Superior. DIC
in the lake was marked by homogeneity in
concentration and in ∆ 14 C and δ 13 C values across the
lake. DOC concentrations exhibited spatial
patchiness, ranging from 88-122 μM in the surface
water during stratification in August. While ∆ 14 C of
DOC did not exhibit considerable variation, the values
in the surface waters at the southern and northern
provinces of the lake were consistently, and uniquely,
low. ∆ 14 C of POC was consistently and significantly
depleted relative to DIC and DOC and was spatially
very heterogeneous (range, modern to 2840 BP yrs).
Its variable age appears to be the result of sediment
resuspension, which reaches even into surface
waters at certain sites and appears more prevalent in
the eastern lake and during the mixed water-column
period. Thus in this lake burial in the sediments does
not necessarily lead to sequestration; as lake
sediments are often resuspended back into regions of
higher reactivity, e.g., the water column and surface
sediment zones.
540

P-413
D/H ratios of plant waxes as recorder of past rainfall intensities –
Insights to the Indonesian paleomonsoon
Eva M. Niedermeyer 1 , Alex L. Sessions 1 , Mahyar Mohtadi 2
1 California Institute of Technology (Caltech), Pasadena, United States of America, 2 Marine Center for
Environmental Sciences (MARUM), Bremen, Germany (corresponding author:eniedermeyer@caltech.edu)
The Indo-Pacific-Warm-Pool is one of the key
evaporative sites for the global hydrologic cycle. Here,
ocean-surface water evaporates to enter the
Australasian monsoon system. Understanding its
variability and underlying driving forces is important
for both the local population as well as for the
development of adaptive strategies to global climate
change. Reconstructions of the terrestrial
paleomonsoon from e.g. Dongge cave [1] (China),
Borneo [2] and Flores [3] (both Indonesia) show that
there have been considerable variations in rainfall
intensities. However, the records exhibit equivocal
patterns, suggesting locally different behavior of the
monsoon and clearly demonstrating the further need
of paleomonsoon reconstructions from other locations
to better understand the complex atmospheric
circulation pattern.
We worked on marine sediment core SO189-144KL
retrieved from the Nias Basin off northwestern
Sumatra (Indonesia, Indian Ocean side) from 480 m
water depth. AMS radiocarbon dating suggests that
the core covers the past ~25,000 years. Sediments
consist of material from marine and terrestrial sources
with the latter being transported mainly by riverine
runoff. The position of the core (1°09,300 N;
98°03,960 E) is close to the equator and therefore
well suited to fill the data gap between northern- and
southern hemisphere palemonsoon reconstructions.
We used Deuterium/Hydrogen ratios (expressed as
δD in permil, relative to V-SMOW) of long chained nfatty
acids from terrestrial plant waxes as a proxy for
past rainfall variability on land. In the tropics, the
amount of precipitation produces a distinct isotopic
signature of rainwater which gets recorded in plant
organic matter such as n-hydrocarbons during
biosynthesis. Because carbon-hydrogen bonds are
stable to exchange and n-fatty acids are relatively
resistant and to degradation, the hydrogen isotopic
composition of our target compound is expected to be
well preserved in our sediment. Moreover, n-fatty
acids are not part of fossil organic carbon sources
such as n-alkanes in oil and therefore most likely
represent past rainfall isotopic composition of the
referred time period.
In order to verify δD of fatty acids as a proxy for
rainfall δD we compared the δD value of n-fatty acids
extracted from coretop sediments along a north-south
transect off west Sumatra to the isotopic composition
of precipitation from the GNIP database. Rainfall δD
in this area shows fairly good correlation with rainfall
amount. Analytical and modeled data show good
agreement supporting the applicability of fatty-acid δD
as a proxy for past rainfall intensities in the study
region.
Results from downcore analyses indicate that rainfall
intensities over west Sumatra varied considerably
during the past 25,000 years. However, in contrast to
the northern hemisphere paleomonsoon, average
Sumatran rainfall intensities during the last glacial
compare to Holocene rainfall. We furthermore identify
a dry period at the end of the last glacial as well as a
pronounced humid interval during the mid-Holocene.
Further radiocarbon dating will reveal a better time
constraint to these events and their relation to the
equivocal reconstructions from the neighboring sites
Borneo and Flores.
References
[1] Yuan, D., et al. (2004): Timing, duration, and
transitions of the last interglacial Asian monsoon. Science,
304, 575-578
[2] Partin, Judson W., Kim M. Cobb, Jess Adkins,
Brian Clark, Diego P. Fernandez (2007): Millennial-scale
trends in west Pacific warm pool hydrology since the Last
Glacial Maximum. Nature, 449, 452-455
[3] Griffiths, et al. (2009): Increasing Australian-
Indonesian monsoon rainfall linked to early Holocene sealevel
rise. Nature Geoscience, 2, 636-639
541

P-414
European lake sediment calibration of long chain n-alkane δD
values
Gert-Jan Reichart 1 , Cornelia Blaga 1 , Jaap S. Sinninghe Damste 1,2
1 Department of Earth Sciences - Geochemistry Faculty of Geosciences, Utrecht University, Utrecht,
Netherlands, 2 Department of Marine Organic Biogeochemistry, NIOZ Royal Netherlands Institute for Sea
Research, Den Burg, Netherlands (corresponding author:reichart@geo.uu.nl)
Lacustrine sediments provide high-resolution records
of past climatic and environmental change. The, often
laminated, sediments are rich in organics and hence
excellently suited for the application of biomarker
proxies. Compound specific stable hydrogen isotope
(δD) analyses can be used to reconstruct past
changes in the hydrological cycle and thus climate.
Especially long chain n-alkanes, which predominantly
originate from plant leaf-waxes, have the potential to
unravel changes in moisture supply and evaporation
in the lakes‘ catchment area. The application of
compound specific δD analyses in lake sediments,
however, critically depends on a robust calibration.
Different plant communities, changes in local
precipitation over evaporation and differences in
biomarker transport all potentially affect δD values in
n-alkanes and should, therefore, be included in such
a calibration.
In the present study we determined the compound
specific δD ratios of long-chain n-alkanes from
surface sediments of 20 lakes from Europe. The lakes
are situated along a north–south transect (from
Sweden to Italy) and encompass a large temperature
and moisture gradient, as well as contrasting local
settings, allowing for a robust test of the application of
δD values of sedimentary n-alkanes as paleoclimatic
and paleoenvironmental proxies.
δD ratios were measured on C25, C27, C29 and C31 nalkanes,
the most abundant n-alkanes present. From
some sediments also the C23 n-alkane was abundant
enough to allow δD analyses. We observed a large
latitudinal δD change of more than 50‰, which is in
line with the change observed in the precipitation as a
consequence of hydrological cycle. Even though
between individual n-alkanes a large offset was
observed, spanning from -108 to -209‰ for n- C25, -
130 to -209‰ for C27, -162 to -214‰ for C29, and from
-164 to -210‰ for C31, all n-alkanes show a close
correspondence to the analyzed lake water stable
isotopic values, which integrates the catchments area
hydrological cycle. This is in line with previous studies
that showed that the δD of plant leaf wax tracks the
decreasing trend of precipitation δD with increasing
latitude.
δD stable isotopic values of the most abundant nalkanes
in lacustrine sediment are strongly correlated
with the isotopic values of the lake water, collected at
the same time as the sediment samples (r 2 between
0.5 for C31 and 0.75 for C27). This implies that
although several complicating factors potentially offset
the δD values as proxy for the hydrological cycle, the
organic compounds integrate hydrological changes in
the lakes‘ catchment area similarly as the lake water
itself.
542

P-415
Stable carbon isotope compositions of lignin phenols and cutin
acids among C3, C4 and CAM plants
Kazuhiko Sonoda, Masashiro Takahashi, Shuichi Yamamoto
Faculty of Engineering, Soka University, Tokyo, Japan (corresponding author:e09d5702@soka.ac.jp)
Compound-specific stable isotope analysis (CSIA) by
gas chromatography/combustion/isotope ratio mass
spectrometry (GC/C/IRMS) yields the isotopic
composition of individual compounds in natural samples,
and has been employed as a powerful tool for tracing the
source and delivery of biomarkers in geographical
samples and for reconstructing the paleoenvironment
[1,2].
An analysis of the carbon isotopic compositions
(� 13 C, ‰) of lignin phenols and cutin acids enables a
quantitative assessment of the properties of plant matter
input into geochemical samples. We have achieved the
CSIA of lignin phenols and cutin acids based on off-line
degradation and derivatization by the TMAH
(tetramethylammonium hydroxide) method, semipurification
using high-performance liquid
chromatography (HPLC), and CSIA by GC/C/IRMS [3]. In
this study, we report the measurement of the carbon
isotope compositions of lignin phenols and cutin acids
among C3, C4 and CAM plants using the method.
Fifteen terrestrial plant leaves including two C3 herbs,
five C3 woody plants, five C4 plants and three CAM
plants were used in this study. These plants were
analyzed off-line using the TMAH thermochemolysis
method. Semi-purification, isotope analysis and correction
methods of � 13 C values for lignin phenols and cutin acids
used have been reported [3]. � 13 C values of bulk tissues
from these plants were determined by elemental
analysis/isotope ratio mass spectrometry (EA/IRMS),
GC/C/IRMS.
Table 1 shows � 13 C values of bulk tissue, lignin phenols
and cutin acids in C3, C4 and CAM plants. In all plants,
lignin phenols (Va, Sa, Vc) and cutin acids are depleted in
� 13 C values (3.5 to 15.7‰) relative to bulk tissue. In
addition, the magnitude of 13 C-depletion of lignin phenols
and cutin acids are distinctive depending on plant classes.
For example, C4 plant lignin phenols are less depleted in
Va (9.7‰), Sa (9.4‰) and Vc (4.0‰) relative to bulk
tissue, respectively, while C3 woody plant lignin phenols
are more depleted in Va (9.8‰), Sa (15.7‰) and Vc
(7.2‰). However, � 13 C values of Pc are rarely different
from bulk tissue in all plants. On the other hand, � 13 C
values of cutin acids from all plants are depleted in Cutin
A (up to 9.8‰) and Cutin C (up to 10.3‰) relative to bulk
tissue.
The above results are compatible with observations of
C3, C4 and CAM plants. Different 13 C-depletions among
lignin phenols and cutin acids were observed in all plants,
where the fractionation trends were consistent with
different isotopic fractionations among photosynthesis,
and different growing rates of perennial or yearly plants.
Table 1. Carbon isotopic composition (‰, av. ± s.d.)
of bulk tissue, lignin phenols and cutin acid from C3, C4
and CAM plants.
C3 herbaceous
plant (n=2)
C3 woody plant
(n=5)
C4 plant (n=5) CAM plant (n=3)
� 13 Cbulk -25.6 ± 0.2 -28.9 ± 1.1 -12.2 ± 0.7 -20.2 ± 4.8
Lignin phenols
Va -33.8 ± 0.2 -38.7 ± 1.5 -21.9 ± 3.1 -30.6 ± 2.3
Sa -37.0 ± 1.2 -44.5 ± 1.8 -21.6 ± 1.0 -33.8 ± 0.1
Pc -25.0 ± 0.4 -27.9 ± 1.7 -11.4 ± 0.9 -21.6 ± 3.8
Vc -29.1 ± 0.3 -36.1 ± 0.9 -16.2 ± 1.3 -27.0 ± 2.1
Cutin acids
Cutin A -37.4 ± 0.7 -38.7 ± 1.5 -23.2 ± 0.7 -31.8 ± 3.6
Cutin C -38.8 ± 0.9 -39.2 ± 1.9 -22.8 ± 0.7 -32.1 ± 3.2
Va: 4-hydroxy-3-methoxybenzoic acid, Sa: 4-hydroxy-3,5dimethoxybenzoic
acid, Pc: p-Coumaric acid, Vc: Ferulic
acid, Cutin A: 8,16-/9,16-/10,16-dihydroxy C16 acid, Cutin
C: 9,10,18-trihydroxy C18 acid
References
[1] Chikaraishi, Y. (2007) Res. Org. Geochem. 22, 1-18.
[2] Chikaraishi, Y. and Oba, Y. (2008) Res. Org.
Geochem. 23/24, 99-122
[3] Sonoda, K., et al. (2010) Res. Org. Geochem 26, 115-
122.
543

P-416
Developing analytical protocols for the measurement of 13C and
15N of crucial organisms within the food web of the Dutch
Wadden Sea
Elisabeth Svensson 1 , Tjisse van der Heide 2 , Sander Holthuijsen 1 , Stefan Schouten 1 ,
Henk W. van der Veer 1 , Jack J. Middelburg 3 , Jaap Sinninghe Damste 1
1 NIOZ Royal Netherlands Institute for Sea Research, 't Horntje, Netherlands, 2 University of Groningen,
Groningen, Netherlands, 3 Utrecht University, Utrecht, Netherlands (corresponding
author:elisabeth.svensson@nioz.nl)
Over the last decade, stable isotopes of carbon and
nitrogen have become widely used tools in ecological
studies. The source of organic carbon can be traced
using the ratio of 13 C to 12 C, (� 13 C), while trophic
levels can be distinguished using the ratio of 15 N to
14 N (� 15 N) (e.g. Fry, 1999). Although the analytical
techniques are the same for both biological and
abiotic samples, the wide range of sample matrixes of
different organisms and sediments requires that
different sample preparation procedures are required
for each sample type (e.g. Logan et al., 2008;
Schielke and Post, 2010; Smyntek et al., 2007). In
addition care needs to be taken during sample
preparation to minimize loss of carbon and nitrogen,
e.g. due to acidic treatment for removal of inorganic
carbon, as that will most likely have an effect on the
stable isotope data (e.g. Brodie et al., in press).
The Wadden Sea is the world‘s largest soft-bottom
intertidal ecosystem as it stretches from the
Netherlands to Denmark. It hosts unique species and
also serves as a fueling station for migratory birds and
in 2009 UNESCO named the Dutch-German Wadden
Sea as a World Heritage site because of its
―outstanding universal value‖. Due to the ecological
importance of the Wadden Sea, understanding the
structure of the food web of the Wadden Sea is
essential and also to determine if the source of the
organic carbon that makes up the base of that food
web is produced within the sea itself or transported
there from external sources such as the North Sea or
land.
To this end we are determining the bulk isotopic
carbon and nitrogen composition of a variety of
organisms from a large number of stations along a
grid over the Dutch Wadden Sea. Samples were
taken for sedimentary organic matter, phyto- and
zooplankton, sea weeds, worms, fish and shellfish.
We have elaborated a sample preparation scheme
that simplifies, while ensuring analytical accuracy, the
analysis of a large and diverse number of biological
and sediment samples from that area. Initial results
show that acidification within a tin cup can result in
small but significant shifts in 13 C as well as sometimes
15 N for tissue or biomass of a number of organisms.
References
Brodie, C.R. et al., in press. Evidence for bias in C
and N concentrations and δ 13 C composition of
terrestrial and aquatic organic materials due to
pre-analysis acid preparation methods. Chemical
Geology.
Fry, B., 1999. Using stable isotopes to monitor
watershed influences on aquatic trophodynamics.
Canadian Journal of Fisheries and Aquatic
Sciences, 56(11): 2167-2171.
Logan, J.M. et al., 2008. Lipid corrections in carbon
and nitrogen stable isotope analyses: comparison
of chemical extraction and modelling methods.
Journal of Animal Ecology, 77(4): 838-846.
Schielke, E.G. and Post, D.M., 2010. Size matters:
comparing stable isotope ratios of tissue plugs
and whole organisms. Limnology and
Oceanography: Methods, 8: 348-351.
Smyntek, P.M., Teece, M.A., Schulz, K.L. and
Thackeray, S.J., 2007. A standard protocol for
stable isotope analysis of zooplankton in aquatic
food web research using mass balance correction
models. Limnology and Oceanography, 52(5):
2135-2146.
544

P-417
Contributions of δD analyses of plant-derived fatty acid methyl
esters in ravine deposits to understanding palaeoenvironmental
changes during the rise and fall of kingdoms in northern
Ethiopia
Valery Terwilliger 1,2,3 , Zewdu Eshetu 4 , Marcelo Alexandre 5 , Yongsong Huang 6 , Marilyn
Fogel 7
1 Institut des Sciences de la Terre d’Orléans (ISTO), Université d’Orléans, UMR 6113 du CNRS/INSU,
Université d’Orléans, Orléans, France, 2 Le STUDIUM/CNRS, Orléans, France, 3 University of Kansas,
Lawrence, United States of America, 4 Ethiopian Institute of Agricultural Research, Forestry Research Center,
Addis Ababa, Ethiopia, 5 Universidade Federal de Sergipe, São Cristóvão, Brazil, 6 Brown University,
Providence, United States of America, 7 Carnegie Institution of Washington, D. C., Washington, D. C., United
States of America (corresponding author:valery.terwilliger@cnrs-orleans.fr)
Knowledge of relationships between past
environmental changes and the rise and fall of
civilizations is contributing to strategies to best
manage today‘s environmental changes. The Tigrean
Plateau of northern Ethiopia and Eritrea has excellent
potential for the study of relationships between
environmental change and the rise and fall of
sophisticated societies. Nonetheless, the
palaeoenvironments of the region have been scarcely
studied and the reasons for the fall of even its most
powerful polity, Aksum, are the least understood of
the world‘s major ancient empires.
We are developing the potential of the Tigrean
Plateau to test a hypothesis that there are
generalizable relationships between environmental
(climate and land clearance in this study) changes
and the trajectories of civilizations. We have been
using stable hydrogen isotopic analyses of specific
plant-derived lipids because of their powerful potential
to record palaeoprecipitation as well as developing a
suite of soil chemical, macro and micromophological,
rockeval, and more rapid stable isotopic proxies for
past environmental characteristics.
We sampled 3 sections in each of 3 ravines in the
hinterlands of the earliest known kingdom (D‘MT) and
of the Aksumite Empire. Chronologies were achieved
from radiocarbon dating of charcoal [1]. Samples
were too low in alkanes for reliable δD analyses but
good records were obtained for plant-derived (≥ C26)
fatty acid methyl esters (FAMEs). The most abundant
FAME was hexacosanoic acid (C26) [2].
δDFAME C26 values were lower before 5600 cal yr BP
than after and this may indicate a shift from wetter to
drier climate. δDFAME C26 values tended to increase
implying continued drying until 1200 cal yr BP albeit
with significant periodic exceptions. Two exceptions
were declines in δDFAME and implied increases in
precipitation that corresponded to the rises of both
D‘MT and Aksum (Fig. 1). If effects of changes in C3
and C4 plant composition on the δD values are
accounted for, these increases in rainfall were higher.
Other proxies suggest that land clearance
dynamics were not similar between or within sites
during the times of the two polities. In conclusion,
climate had a more generalizable relationship to polity
trajectory than land clearance.
Fig. 1. Changes in proxy measurements during the times of
D‘MT and Aksum at one site.
References
[1] Gebru T. et al. 2009. Palaeogeography,
Palaeoclimatology, and Palaeoecology 282: 67-80.
[2] Courat, M. 2010. Rapport Master de Sciences de la
terre et environnement. Université d‘Orléans.
545

P-418
Extreme intra- and intermolecular carbon isotopic disparity in
individual archaeal intact polar lipids from methane seep
sediments
Marcos Yukio Yoshinaga, Marcus Elvert, Yu-Shih Lin, Kai-Uwe Hinrichs
MARUM, University of Bremen, Bremen, Germany (corresponding author:marcosyukio@gmail.com)
Large carbon isotopic heterogeneity has been
observed in specific lipids and individual cells of
archaeal anaerobic methanotrophs (ANMEs) [1,2,3].
To examine this isotopic variability in detail, we
studied the carbon isotopic compositions of archaeal
intact polar lipids (IPLs) and sedimentary carbon
pools (TOC, lactate, acetate, methane, dissolved
inorganic carbon) in a push corer (0-14 cm) from a
methane seep off Pakistan. After preparative liquid
chromatography (LC) separation, individual IPLs were
subjected to ether cleavage and reduction, followed
by isotopic ratio analysis of the resulting phytane and
biphytanes derivatives as well as of sugar
headgroups that were obtained from glycosidic (Gly)
IPLs after hydrolytic cleavage [4]. This IPL-specific
isotopic analysis is expected to strongly reduce
effects related to mixing of lipid pools from different
sources and is more likely to resolve the true diversity
of carbon metabolisms within complex microbial
communities.
Isotopic offsets of up to 80‰ were observed
between core lipids and related hexoses within 2Glyglyceroldialkylglyceroltetraether
(2Gly-GDGT, Fig. 1),
one of the most common archaeal IPLs in marine
sediments. A large isotopic difference is as well
evident between biphytanes from 2Gly-GDGT and
other archaeal IPLs, i.e. glycerolphosphate (PG)-
GDGTs. The data can be divided in two clusters: (1)
higher 13 C-depletion than methane; (2) close to or
more positive than � 13 C-TOC. The latter values are
low compared to typical marine sediments, but
comparable to the � 13 C of lactate, suggesting partial
contribution of methane-related organic carbon via
fermentation. Because a considerable fraction of � 13 C
values from sugars and lipids fall into the range of
TOC and lactate, heterotrophy appears to be an
important archaeal metabolism, which is especially
observed in surface sediments and diminishes with
depth. Low �� 13 C values for acetate throughout the
sediment column exclude acetoclastic
methanogenesis as a relevant archaeal metabolism.
The lowest � 13 C values of IPL-derived compounds
result from methane and/or CO2 assimilation by
ANMEs [5]. We estimated the probable � 13 C signature
of CO2 uptake [cf. 6] (gray rectangle in Fig. 1), giving
a � 13 C range lower than IPL derivatives in surface
sediments and one being higher in deeper horizons.
Our results suggest that the diversity of archaeal
metabolic traits in seep sediments is diverse and
responsible for the extreme intra- and intermolecular
� 13 C disparity found in IPLs and prominent carbon
pools.
Figure 1. � 13 C values (‰) of archaeal IPLs derivatives and
carbon metabolites at the 2-3 cm horizon. Gray areas
represent the expected � 13 C range for lipids and biomass of
a methanogen assimilating CO2 [6]. Biphytanes with (0) to
(3) rings. Gal = galactose, Glc = glucose, Man = mannose.
References
[1] Hinrichs, K.-U. et al. (2000) Org Geochem 31: 1685-
1701.
[2] Orphan, V. et al. (2002) PNAS 99: 7663-7668.
[3] House et al. (2009) Environ Microbiol 11: 2207-2215.
[4] Lin, Y.-S. et al. (2010) Rapid Comm Mass Spec 24: 2817-
2826.
[5] Wegener et al. (2008) Environ Microbiol 10: 2287-2298.
[6] Alperin, M.J. and Hoehler, T.M. (2009) Am J Sci 309:
958-984.
546

P-419
Effect of leaf litter degradation and seasonality on D/H isotope
ratios of n-alkane biomarkers
Michael Zech 1,2 , Nikolai Pedentchouk 3 , Björn Buggle 1,2 , Katharina Leiber 1 , Karsten
Kalbitz 4 , Slobodan Markovic 5 , Bruno Glaser 2
1 Chair of Geomorphology and Department of Soil Physics, University of Bayreuth, Bayreuth, Germany,
2 Department of Terrestrial Biogeochemistry, Martin-Luther University Halle-Wittenberg, Halle, Germany,
3 School of Environmental Sciences, University of East Anglia, Norwich, United Kingdom, 4 Institute for
Biodiversity and Ecosystem Dynamics, University of Amsterdam, Amsterdam, Netherlands, 5 Chair of
Physical Geography, University of Novi Sad, Novi Sad, Serbia (corresponding
author:michael_zech@gmx.de)
During the last decade, compound-specific hydrogen
isotope analysis of plant leaf-wax and sedimentary nalkyl
lipids has become a promising tool for
paleohydrological reconstructions. However, with the
exception of several previous studies, there is a lack
of knowledge regarding possible effects of early
diagenesis on the �D values of n-alkanes. We
therefore investigated the n-alkane patterns and �D
values of long-chain n-alkanes from three different C3
higher plant species (Acer pseudoplatanus L., Fagus
sylvatica L. and Sorbus aucuparia L.) that have been
degraded in a field leaf litterbag experiment for 27
months.
We found that after an initial increase of the total longchain
n-alkane mass (up to ~50%), decomposition
took place with mean turnover times of 11.7 months.
Intermittently, the total mass of mid-chain n-alkanes
increased significantly during periods of highest mass
losses. Furthermore, initially high odd-over-even
predominance declined and long-chain n-alkane
ratios like n-C31/C27 and n-C31/C29 started to converge
to the value of 1. While bulk leaf litter became
systematically D-enriched especially during summer
seasons (by ~8‰ on average over 27 months), the
�D values of long-chain n-alkanes reveal no
systematic overall shifts, but seasonal variations of up
to 25‰ (Fagus, n-C27, average ~13‰).
These findings suggest that a microbial n-alkane pool
sensitive to seasonal variations of soil water �D
rapidly builds up. We propose a conceptual model
that accounts for the decomposition of plant-derived
n-alkanes and the build-up of microbial n-alkanes.
Model results are in good agreement with measured
n-alkane �D results. Since microbial ‗contamination‘ is
not necessarily discernible from n-alkane
concentration patterns alone, care may have to be
taken not to over-interpret �D values of sedimentary
n-alkanes. Furthermore, since leaf-water is generally
D-enriched compared to soil and lake waters, soil and
water microbial n-alkane pools may help explain why
soil and sediment n-alkanes are D-depleted
compared to leaves.
547

P-420
� 2 H differences among lipids synthesised via the ACT
(acetogenic), MVA (mevalonic) and DXP (1-deoxy-D-xylulose 5phosphate)
pathways in higher plant leaves: possible evidence
for intracellular water (H+) isotopic heterogeneity
Youping Zhou 1,2 , Kliti Grice 1 , Hilary Stuart-Williams 2 , Graham Farquhar 2 , Charles Hocart 2
1 Curtin University, Perth, Australia, 2 Australian National University, Canberra, Australia (corresponding
author:y.zhou@curtin.edu.au)
Carbon-bound hydrogen atoms in lipids from higher
plant leaves have three immediate sources: 1)
inherited from biosynthetic precursors, 2) water (H + ) in
which biosynthesis occurs and 3) bio-reductant
NAD(P)H [1,2,3,4,5] . Hydrogen isotopic ratios ( 2 H/ 1 H) of
lipids are determined by those of the sources modified
by isotopic fractionations during biosynthesis. Lipids
synthesised via the ACT pathway (e.g. n-alkanes), the
MVA (e.g. sterols) and the DXP pathway (e.g. phytol)
were isolated from leaves of C3 and C4 species
grown under controlled and field conditions.
Compound-specific isotopic analysis (CSIA) of these
lipid revealed that an inter-pathway hydrogen isotopic
enrichment order: � 2 HACT > � 2 HMVA > � 2 HDXP exists in
all species examined [1,3,5] . There is an isotopic
enrichment ordering between photosynthetic modes:
� 2 HC4 < � 2 HC3 (for ACT), � 2 HC4 > � 2 HC3 (for MVA and
DXP) [1,3,5] . Average inter-pathway differences for C4
plants are smaller than for C3 plants.
An investigation of the histories of the individual
hydrogen atoms in these lipid molecules, based on
available knowledge of their biosynthetic chemistry,
indicated that the observed inter-pathway order is a
result of intracellular NADPH variation and
intracellular water isotopic heterogeneity. NADPH and
water (H + ) in the chloroplast are isotopically more
depleted in 2 H than their respective cytosolic
counterparts. The inter-compartmental water and
NADPH isotopic differences are passed onto lipid
molecules synthesised in each cellular compartment
via enzyme-catalysed hydration or NAD(P)H
reduction of metabolic intermediates.
Compartmentalisation of initial photosynthetic CO2
fixation into the C4 mesophyll (M) cell and final CO2
fixation in the bundle sheath (BS) cell results in more
2 H-depleted pyruvate (in comparison to C3), the
precursor for lipids synthesised via the ACT pathway
in the chloroplast, due to the exchange of carbonbound
hydrogen in pyruvate with the less enriched
cellular water in the BS cell (relative to M cellular
water) during the malate-pyruvate shuttle.
Compartmentalisation in C4 plants also results in less
depleted NADPH in the M chloroplast (in comparison
to C3) for lipid synthesis via DXP pathway due to the
selective export of 2 H-depleted NADPH from the M
cell to the BS cell and a less depleted pyruvate in the
BS cytosol for lipid synthesis via MVA pathway due to
the suppression of photorespiration (Fig 1) [5] .
Mesophyll chloroplast
malate
malate
NADP +
NADPH
pyruvate
Bundle sheath cytosol
COO
O
-
H �
H �
H b
COO
OH
-
H �
H �
O - 2e + H OPi RuBP
GAP O
H C5 H
H C3C HO HO O
C4 H
C3 H
C2 H
H
C24 OH
C H
15
OPi H
OC
H C1 H
OPi HO
CO2 H
H
FBP
O
OH
C3C H C3C H G6P
C24 OH
C24 O
Starch
C15 H
H C15 H
OPi DHAP Maltose
OPi + + NADP + NADPH + H +
H
+ -
H2O H + HO
Calvin Cycle
+
+ -
H2O H + HO
H
lumen
sterol
O
HO
H
HO
HO
C15 H
C24 H
C3C OH
C3C H
C24 H
+
H + H +
H +
H +
H +
H +
H +
H + H +
H +
H +
H +
H +
H +
stroma
PS I
Cyt bf
Cyt bf
pyruvate
malate pyruvate
PS I
PGA
PGA
NADPH NADP +
DHAP Maltose
DHAP
COO
OPi -
H �
H �
O
COO
CO2 -
H �
H �
O - COO
O
OC
-
H �
H �
O - NADP
OC
+
COO
OH
NADPH
-
H �
H �
O - H
OC
COO
OPi
-
H ��b
H ��b
COO
O
ATP
AMP
-
H �
H �
H b
malate pyruvate
PGA OH H
O C3C C24 C15 OPi OH H H
PS I
PS II
H
Cyt bf
OAA
PEP
GAP OH H
OPi O C3C C24 C
H
15
H H H
TPI H
OH Cyt bf
C3C H
C24 O
PS II
C15 H
PS I
C18 Fatty acid
Mesophyll cytosol
+
H +
H +
H +
H +
H +
H +
H +
H +
H +
H +
H +
PGA
DHAP
Fig 1. Compartmentalisation of C4 photosynthesis into
mesophyll cell and bundle sheath cell.
[1] Chikaraishi et al. (2009) Phytochem 70, 569-573
[2] Schmidt et al. (2008) Phytochem Rev 2, 61-85
[3] Sessions et al. (1999) Org Geochem 30, 1193-1200
[4] Zhang et al. (2009) PNAS 106, 12580-12586
[5] Zhou et al. (2010) Phytochem 71, 388-403
stroma
lumen
2H 2 O 4H + + O 2 + 4e
Bundle sheath chloroplast
H 2 O H + + HO -
H
glycolysis TCA
C 15 H
OP i
H 2 O H + + HO -
2e + H + + NADP + NADPH + H +
glucose
548

P-423
Effects of long-term climatic manipulations on microbial
communities in European shrublands
Sharon Mason 1 , Chiara Cerli 1 , Andrew Smith 2 , Albert Tietema 1
1 University of Amsterdam, Amsterdam, Netherlands, 2 Centre for Ecology and Hydrology, Bangor, United
Kingdom (corresponding author:s.l.mason@uva.nl)
Soil microbial communities are key regulators of soil
organic matter (SOM) dynamics. Therefore, shifts in
microbial community composition in response to
environmental change may significantly affect key
ecosystem processes, such as nutrient cycling and
soil organic carbon (SOC) turnover. Previous studies
have shown significant, yet contrasting microbial
response to increased soil temperature and altered
precipitation patterns [1, 2 & 3], highlighting the need
for a greater understanding of how different
ecosystems respond to such changes.
Climate change effects on European shrublands have
been investigated for more than 10 years during the
EU-funded projects of CLIMOOR (1998-2000),
VULCAN (2001-2004) and INCREASE (2009-2012),
with continued measurements at many sites in the
intervening years. A network of 6 large scale field
experiments simulate realistic levels of climatic
change in 20 m 2 plots, that are superimposed across
a natural temperature and precipitation gradient (Fig.
1). Each site has 9 experimental plots; 3 x control, 3
x warming and 3 x drought. Warming treatment is
achieved by covering plots with a reflective curtain at
night to prevent heat loss (increases soil temperature
by 0.4-1.2 ºC), whilst drought treatment is simulated
by covering plots with a transparent cover for 1-2
months during the growing season (Fig. 2). How the
different sites respond to climatic manipulation is most
intriguing, with findings indicating that the effect of
warming might be seen across all sites, whilst the
effect of drought could be more significant in Northern
as opposed to the drier Southern European soils [4].
Significant effects on soil processes have been found
but a greater understanding of molecular level
response is still required. In this study we assess and
report changes in phospholipid fatty acid (PLFA)
profiles to determine how microbial communities are
affected by climatic manipulations imposed across
experimental sites. Soil samples were collected from
plots in The Netherlands, Denmark, Italy, Hungary
and Wales (UK) in November 2009 and analysed for
PLFA content and composition using a modification of
the method outlined in [5]. We hypothesised that
warming would increase fungal:bacterial ratios, whilst
drought would reduce fungal community composition.
An initial assessment of outside plot samples showed
variation between sites in both total active microbial
biomass and fungal:bacterial ratios due to natural
differences between ecosystems. Linking these
findings with further molecular geochemical
assessment and investigation of microbial activity will
in future be critical to our overall understanding of the
shrubland ecosystem response to climate change.
Fig. 1. Location of infrastructures, showing natural gradients
in temperature and precipitation (left).
Fig. 2. Climate manipulation techniques (right).
References
[1] Feng, X. J., Simpson, A. J., Wilson, K. P., Williams, D. D.
and Simpson, M. J. (2008) Nature Geosci. 1, 836-839.
[2] Frey, S.D., Drijber, R., Melillo, J. (2008) Soil Biol.
Biochem. 40, 2904-2907.
[3] Toberman, H., Freeman, C., Evans, C., Fenner, N. and
Artz, R. R. E. (2008) FEMS Microbiol. Ecol. 66, 426-436.
[4] Sowerby, A., Emmett, B., Beier, C., Tietema, A.,
Penuelas, J., Estiarte, M., van Meeteren, M.J.M., Hughes,
S., Freeman, C. (2006) Soil Biol. Biochem. 37, 1805-1813.
[5] Elvert, M., Boetius, A., Knittel, K., Jorgensen, B. B. (2003)
Geomicrobiol J. 20, 403-419.
549

P-424
Intact polar lipid and associated genetic signatures of archaea in
estuarine sediments
Travis B. Meador 1,2 , Cassandre Lazar 2,3 , Marcos Y. Yoshinaga 1,2 , Andreas Teske 3 , Kai-
Uwe Hinrichs 1,2
1 University of Bremen, Bremen, Germany, 2 MARUM Center for Environmental Sciences, Bremen, Germany,
3 University of North Carolina, Chapel Hill, Chapel Hill, United States of America (corresponding
author:travis.meador@uni-bremen.de)
Members of the Miscellaneous Crenarchaeotal Group
(MCG) appear to have a widespread global
distribution but their metabolic capabilities or
ecological relevance remain uncertain. [1,2] Some
studies have suggested that these crenarchaeota
may be involved in the anaerobic oxidation of
methane. [3,4,5] Recently, the archaeal community in
sediments of the White Oak River Estuary (NC, USA)
was shown to be primarily composed of MCG. [6] We
collected sediment cores from this estuary to further
explore the distribution of MCG by intact polar lipid
(IPL) and genetic signatures, as well as the
geochemical conditions that give rise to their success
in this environment. We targeted sediments with a
distinct sulfate-methane transition zone (SMTZ),
where there may exist a natural enrichment of MCGspecific
IPLs.
Reports of IPL distributions in the natural
environment are limited to a few studies, which have
shown that archaeal diether and tetraether lipids
comprise the bulk of IPLs in subsurface sediments. [7]
However, there was relatively little variability observed
in lipid headgroup distribution compared to the
diversity of microbial assemblages inferred from
analysis of nucleic acids. [8] The most ubiquitous IPL
reported in this study, diglycosyl glycerol dibiphytanyl
glycerol tetraether (2Gly-GDGT), accounted for more
than half of all IPLs from sediment horizons located
within the sulfate-methane transition zone of
sediments collected from the Peru Margin.
In the White Oak River Estuary, we observed a
subsurface sulfate maximum in all cores (up to
16 mM; 10-12 cm), with subsequent depletion
downcore to below detection limits at 30 cm. At this
depth, methane concentrations began to increase,
reaching a maximum at the deepest depth horizons
(~0.5 mM; 50 cm). Within this SMTZ, we detected
2Gly-GDGT in addition to several other archaeal IPLs
(Fig. 1). In particular, we observed relatively higher
abundances of tetraethers with a headgroup of mass
341 Da (H341-GDGT(1); m/z=1656.5 Da) and
phosphatidyl-N-methylethanolamine (PME-GDGT,
m/z =1427.3 Da). These IPLs increase in
concentration within the SMTZ and are likely products
of the active populations of Archaea that inhabit these
estuarine sediments. Further evaluation of the
archaeal communities associated with these IPL
signatures by clone libraries, and pyrosequencing, in
addition to intramolecular and isotopic composition
analysis of these archaeal IPLs will help to unveil the
metabolic activity associated with natural populations
of MCG.
Figure 1. Depth profiles of selected IPLs in estuarine
sediment. Phosphatidylcholine diacylglycerol (PC-DAG; ‚) is
included as reference for bacterial lipid contribution. Relative
abundances of each IPL are expressed as the response of
molecular ions generated during LC-ESI-MS, [9] normalized to
that of an internal extraction standard (C21-PC-DAG). The
grey box represents the depth of the SMTZ.
1. Parkes, R. J., et al. 2005. Nature 436: 390-394.
2. Teske, A. and K. B. Sørensen. 2008. ISME J. 2: 3-18.
3. Reed, D. W., et al. 2002. Appl Environ Microbiol 68(8):
3759-3770.
4. Biddle, J. F., et al. 2006. PNAS 103(10): 3846-3851.
5. Inagaki, F., et al. 2006. PNAS 103(8): 2815-2820.
6. Lloyd, K. 2009. Microbially-driven methane and sulfur
cycling in a Gulf of Mexico methane seep and the White
Oak River Estuary. PhD Thesis, U. North Carolina.
7. Lipp, J.S., et al. 2008. Nature 454: 991-994.
8. Lipp, J.S. and K. Hinrichs. 2009. Geochim Cosmochim Ac
73: 6816-6833.
9. Sturt, H.F., et al. 2004. Rapid Commun Mass Sp 18: 617-
628.
550

P-425
Insights into the microbial communities of modern stromatolites
(Highborne Cay, Bahamas) from bacterial and eukaryotic lipids
Sabine Mehay 1 , Joan Bernhard 2 , Anna McIntyre-Wressnig 2 , Virginia Edgcomb 2 , Roger
Summons 1
1 Earth, Atmospheric and Planetary Department, Massachusetts Institute of Technology, Cambridge, United
States of America, 2 Geology and Geophysics Department, Woods Hole Oceanographic Institution, Woods
Hole, United States of America (corresponding author:mehay_s@hotmail.com)
Stromatolites are the oldest visible form of
life on Earth. Widespread throughout the Proterozoic
Eon, these distinctively laminated microbial mats are
now relatively rare in contemporary environments. We
are investigating the biochemical processes involved
in stromatolite formation, and why their abundance
and variety drastically decreased at the end of the
Proterozoic, based on the study of modern analogs.
The role of cyanobacteria has been extensively
investigated since the first characterizations of
stromatolitic mats for evidence of particles
agglutination and carbonate precipitation and
cementation. However the microbial communities
involved are complex and this complexity may play a
significant role in various processes taking place
within the mat. The role of eukaryotic microorganisms
has been poorly appreciated in this respect. Algae,
but also non-photosynthetic protists could be
implicated in mat evolution and taphonomic
processes including the fabric modification of
laminated stromatolites into clotted thrombolites.
Here, we show lipid biomarker data from
various forms of microbialites collected in Highborne
Cay (Bahamas) in April 2009. This set of samples
includes intertidal and subtidal stromatolites,
thrombolites and ooids. Ooids, roughly spherical
sedimentary grains largely composed of aragonite,
are the major carbonate constituent of the Bahamian
stromatolites and thrombolites.
Steroids isolated from stromatolites show
that eukaryotes were present in every sample. We
also identified a diverse assemblage of
bacteriohopanepolyols (BHP) including BHT,
aminotriol, lactone, cyclitol ether and guanidine
substituted cyclitol ether. Methylated analogs for BHT,
aminotriol and lactone were also tentatively identified.
Thrombolite samples showed the same variety of
BHP as stromatolite samples. Ooid samples display
most of the same BHP found in stromatolites and
thrombolites although at lower abundance. We also
observed significant variations in the relative amounts
of hopanoids independently of the nature of the
samples.
The observation of similarly complex BHP
distributions in stromatolites, thrombolites and ooids
implies that similar bacterial taxa are present.
However differences in the relative abundance of
these BHPs indicate that the corresponding
physiological processes are variably active. We did
not find any hopanoid fingerprints that were specific to
stromatolites or thrombolites. Production of these
lipids, therefore, may be more related to biochemical
processes occurring in specific zones within the
microbial mat rather than to the laminated or clotted
nature of the mat.
Further work on the characterization of the
steroid distributions is in progress. Concurrently, we
are analyzing the lipids of cultured Allogromia
laticollaris, a foraminiferan closely related to some
previously identified in Bahamian stromatolites (JMB,
unpubl.), with the aim of identifying lipid biomarkers
specific to protists that are active with stromatolitic
and thrombolitic communities.
551

P-426
Bacterial versus archaeal activity in episodically flooded soils –
A combined lipidomics/genomics approach
Cornelia Mueller-Niggemann 1 , Andrea Bannert 2 , Michael Schloter 2 , Kai Mangelsdorf 3 ,
Lorenz Schwark 1
1 Institute of Geosciences, Christian-Albrechts-University of Kiel, 24118 Kiel, Germany, 2 Department for
Terrestrial Ecogenetics, Helmholtz Centre München, 85764 Neuherberg, Germany, 3 GFZ Potsdam German
Research Centre for Geosciences, 14473 Potsdam, Germany (corresponding author:cmn@gpi.uni-kiel.de)
Microbial processes in episodically dry and flooded
soils, e.g. in rice paddy fields, are highly variable due
to alternating changes in environmental conditions.
The characterization of such complex biogeochemical
systems affords combined approaches, for example
microbial lipid analysis coupled to molecular genetics.
Nitrogen cycling in alternately dry and flooded rice
paddy soils is exceptionally rapid due to intensive
fertilization and substantial nitrogen loss via leaching.
It is now well established that ammonium oxidation,
the first step in the nitrification is carried out by
archaea and, bacteria. The key enzyme for this
process, the ammonium mono-oxgenase is found in
bacteria (amoA AOB) and in archaea (amoA AOA). At
present it is still disputed whether archaeal or
bacterial ammonium oxidation dominates in soil. A
predominance of archaea from the mesophilic phylum
thaumarchaeota (previously crenarchaeota) [1] has
been documented in several dry upland soils using
genomic and lipidomic techniques [2]. The key lipids
for detection of archaeal contribution to soil organic
matter are the isoprenoidal glyceroldialkylglycerol
tetraethers (GDGT). These specific GDGT may
originate from Euryarchaeota preferentially
participating in methanogenic and methanotrophic
processes, whereas crenarchaeol is exclusively
biosynthesed by Thaumarchaea. In contrast, the
isoalkanoidal GDGT found in sediments are attributed
to bacterial sources, whereby the likely sources are
denitrifying bacteria (see Mueller-Niggemann et al.,
this meeting).
We have analyzed a series of soils utilized under
alternating flooded and dry regimes in a coastal
region of China. These soils developed on a marine
tidal wetland substrate and differ in the duration of
cultivation time from 50 to 2000 years. This allows to
study the adaption of soil microbial communities to
changes in the nitrogen cycling regime. Microbial
ecology based on genomics demonstrates equal
abundances of amoA AOA and amoA AOB gene
copies in the marine realm. In paddy soils a
dominance of amoA AOA over amoA AOB is
established very rapidly, followed by a continuous
increase of amoA AOA over 2000 years of paddy
management. GDGT analysis of marine sediment
gave a high value of crenarchaeol derived from
ubiquitous mesophilic crenarchaea. In the paddy soils
a decline in crenarchaeol compared to caldarchaeol
and its isomers was attributed to the presence of
methanogenic/-trophic Euryarchaeota.
Comparison of amoA AOA gene copies and
isoprenoidal GDGT abundances shows a covariance
(Fig.1) better than for crenarchaeol with amoA AOA.
This may indicate an origin of crenarchaeol from
different archaeal lineages in marine sediment versus
paddy soils.
Abundance of both, archaeal GDGT and amoA AOA
gene copies show higher ammonium oxidation in the
paddy field cultivated for 300 versus 2000 years.
Archaea seem to outcompete bacteria in ammonium
oxidation only under N depletion. This is verified by
the dominance of archaea in the N-poor 300 year
paddy, versus the N-rich 2000 year paddy.
Combined genomic and lipidomic analysis of paddy
soils and substrates indicates a dependence of
microbial N-cycling by archaea or bacteria on the
highly variable N-availability in these man-made
agricultural ecosystems.
Fig.1. Comparison of archaeal abundance based on
amoA AOA gene copies and GDGT lipids.
[1] Spang et al. 2010, Trends in Microbiol., 331-340
[2] Leininger et al. 2006, Nature, 806-809
552

P-427
Quantitative reconstructions of methanogenic and
methanotrophic archaeal communities in Lake Rotsee,
Switzerland, using biomarker concentrations and their carbon
isotopic compositions
Sebastian Naeher 1,2 , Rienk Smittenberg 3 , Carsten Schubert 1
1 Swiss Federal Institute of Aquatic Science and Technology (Eawag), Department of Surface Waters-
Research and Management, Kastanienbaum, Switzerland, 2 ETH Zurich, Department of Environmental
Sciences, Institute for Biogeochemistry and Pollution Dynamics, Zurich, Switzerland, 3 ETH Zurich,
Department of Earth Sciences, Climate Geology, Zurich, Switzerland (corresponding
author:sebastian.naeher@eawag.ch)
We quantitatively reconstructed methanogenic and
methanotrophic archaeal community changes from a
sediment core of the eutrophic Lake Rotsee in
Switzerland. This study is based on biomarker
concentrations in the sediment with a temporal
resolution of up to 3 years per sample, carbon
isotopes, combined with results from an earlier study
on vertical distributions of active methanogens in the
sediment of Lake Rotsee [1].
Lake Rotsee is a monomictic and stratified lake with
an anoxic hypolimnion most of the year. Because of
the shallow water column of Lake Rotsee (maximum
water depth 16m) and the stratification, relatively little
degradation of organic matter occurs. Methane
concentrations in the hypolimnion were up to 1mM in
fall 2007 [2].
Around 1920 not only the bioproductivity increased in
Lake Rotsee, but in coherence also the abundance of
methanogenic archaea, indicated by elevated
concentrations of caldarchaeol. In addition to
caldarchaeol also diplopterol and 17β(H),17β(H)homohopanoic
acid concentrations increased. We
relate this to the construction of a tunnel from Reuss
River which was constructed in 1922. The tunnel was
an unsuccessful attempt to increase the freshwater
input to recover the lake [3]. Zepp Falz et al. [1] could
show that on average 91% of the archaeal population
in Lake Rotsee is represented by the acetoclastic
Methanosaeta spp. alone. The methanogenic archaea
dominance is indicated by carbon isotopes
measurements from glycerol dialkyl glycerol
tetraethers (GDGTs) obtained by ether cleavage. Few
years later, higher concentrations of biomarkers
related to methanotrophic archaea could be
determined because of their highly depleted carbon
isotopic signal of diploptene, archaeol,
hydroxyarchaeol and 17β(H),17β(H)-homohopanoic
acid. In the 1970s Lake Rotsee reached another high
eutrophication state. During this time, stratification
seemed to become more stable and anoxic conditions
increased because of higher supply of organic
material into the sediment which triggered increased
abundances in methanogenic and methanotrophic
archaea.
Based on Zepp Falz et al. [1], microbial densities
could be calculated under certain assumptions
concerning biomarker degradation for the last 100
years.
References
[1] Zepp Falz K., Holliger C., Grosskopf R.,
Liesack W., Nozhevnikova A.N., Müller B., Wehrli B.,
Hahn D. (1999) Vertical distribution of methanogens
in the anoxic sediment of Rotsee (Switzerland). Appl
Environ Microbiol 65(6):2402–2408
[2] Schubert C.J., Lucas F.S., Durisch-Kaiser
E., Stierli R., Diem T., Scheidegger O., Vazquez F.,
Müller B. (2010) Oxidation and emission of methane
in a monomictic Lake (Rotsee, Switzerland). Aquat
Sci 72:455–466
[3] Kohler H-P, Ahring B, Albella C, Ingvorsen K,
Kewelsh H, Laczko E et al. (1984) Bacteriological
studies on the sulfur cycle in the anaerobic part of the
hypolimnion and in the surface sediments of Rotsee
in Switzerland. FEMS Microbiol Lett 21:279–286
553

P-428
Study of microbial activity associated to SW-Barents Sea
pockmarks
Julia Nickel 1,2 , Kai Mangelsdorf 1 , Jens Kallmeyer 2 , Rolando di Primio 1 , Daniel Stoddart 3
1 Helmholtz Centre Potsdam GFZ German Research Centre for Geosciences, Telegrafenberg, Potsdam,
14473, Germany, 2 University of Potsdam, Karl-Liebknecht-Strasse 24, House 27, Potsdam, 14476,
Germany, 3 Lundin Petroleum Norway, Strandveien 50D, Lysaker, 1366, Norway (corresponding
author:nickel@gfz-potsdam.de)
Widespread areas of the seabed in the southwestern
Barents Sea are characterized by pockmarks, which
are manifestations of hydrocarbon venting, as well as
plough marks from rafting icebergs. Pockmarks
received considerable interest as possible indicators
for deeper hydrocarbon reservoirs. Concomitantly,
submarine hydrocarbon seeps form habitats for
specific microbial communities. These microbial
ecosystems and their processes are in the focus of
the current study using biogeochemical and
microbiological approaches.
During a 10-day research cruise on the Norwegian
research vessel HU Sverdrup in November 2009,
funded by the Swedish oil company Lundin, 350
sediment cores of up to 2.5 m length were taken
inside and outside of the pockmark structures,
forming a local and regional grid. 35 cores were
selected for detailed studies and sampled in 10 depth
intervals. Except for direct turnover rate
measurements with radiotracers (sulfate reduction,
anaerobic oxidation of methane) samples were
preserved or frozen for later analysis in the home
laboratory. All other cores were only sampled for gas
measurements.
In marine sediments, dissimilatory sulfate reduction is
the quantitatively most important electron acceptor
process in the degradation of organic matter [1]. We
determined sulfate reduction rates by radiotracer
incubations with 35 SO4 2- , followed by separation of the
reduced inorganic sulfur compounds by the cold
chromium distillation as described by Kallmeyer et al.
[2]. Additionally, general geochemical parameter like
pore water sulfate concentration, TOC and the total
amount of methane (free, occluded and adsorbed
gas) were measured.
Sulfate reduction rates in the entire sampling area are
astonishingly low. This result is also supported by the
analysis of methane concentrations, showing only
marginal amounts of free and occluded gas and slight
concentrations of adsorbed gas. This indicates that
nowadays the pockmarks system is more or less
inactive.
Porewater sulfate profiles also show only a minimal
decrease with depth, indicating very little net sulfate
consumption.
These results reveal that the observed pockmarks are
not indicators for active leakage and are rather relicts
of paleo-seepage. Therefore, it is hypothesized that
their formation is most likely related to paleo-events of
decaying gas hydrates induced by the pressure
release from the melting ice shield during last
deglaciation (approx. 13 ka B.P.).
Microbial biomarkers are currently being analyzed
with depth to investigate the history of the pockmarks.
In this context data from pockmarks will be compared
to data from reference sites. This should lead to a
better understanding of the whole pockmark system.
The focus will be placed on specific biomarkers and
its carbon isotopic signature indicating fossil microbial
populations and its microbial processes in the past.
Initial results reveal the presence of glycerol dialkyl
glycerol tetraethers (GDGTs) indicating fossil
microbial populations.
Additional samples will be gathered in a second
cruise to the Barents Sea in February 2011. The aim
is to locate pockmarks showing visible indications for
active seepage, such as gas bubbles, carbonate
crusts or macrofauna like beggiatoa mats. For this
purpose a ROV (Remotely Operating Vehicle) will be
used. The obtained results will be compared with the
current data from the cores of inactive pockmarks
which where taken during the cruise in 2009.
References
[1] Jørgensen, B.B., (1982) Mineralization of organic matter
in the sea bed - the role of sulphate reduction. Nature,
296(5858), 643-645.
[2] Kallmeyer, J., Ferdelman, T.G., Weber, A., Fossing, H.,
Jørgensen, B.B., (2004) A cold chromium distillation
procedure for radiolabeled sulfide applied to sulfate
reduction measurements. Limnology and Oceanography-
Methods, 2, 171-180.
554

P-429
Microbial diversity and organic matter cycling of methanerelated
seabed seepage structures in Irish waters
Shane O' Reilly 1 , Michal Szpak 1 , Xavier Monteys 2 , Christopher Allen 3 , Brian Kelleher 1
1 Dublin City University, Dublin, Ireland, 2 Geological Survey of Ireland, Dublin, Ireland, 3 Queen's University
Belfast, Belfast, United Kingdom (corresponding author:brian.kelleher@dcu.ie)
Introduction: Seabed seepage structures –
pockmarks and methane-derived authigenic
carbonate (MDAC) mounds in Irish waters have been
investigated using � 13 C monitoring of lipid biomarkers,
denaturing gradient-gel electrophoresis (DGGE) and
phylogenetic analysis of bacterial and archaeal 16S
rRNA genes. In Irish waters, pockmarks have been
documented in the Malin Sea (Monteys et al, 2008),
the Porcupine Bank (Games, 2001) and in the W.
Irish Sea. In the Irish Sea at the Codling Fault Zone
(CFZ) gas seepage, and anaerobic oxidation of
methane) has facilitated the formation of c. 30 MDAC
mounds (Croker et al. 2005). Selected data from
pockmarks in the Malin Sea and Dunmanus Bay, and
MDACs in the Irish Sea are presented here.
Methods: SEM was performed using a Hitachi
S3400-N. Lipids were extracted by modified
Bligh/Dyer or ultrasonic-assisted extraction and nonextractable
lipids were obtained from base-/acid-
hydrolysis of residues. Desulphurized extracts were
fractionated, derivitized and analysed on an Agilent
6890N/5975C GC-MS coupled to an Isoprime 100
irMS. DNA was extracted and purified according to
Zhou et al (1996). 16S bacterial and archaeal rRNA
genes were PCR-amplified using universal primers
(63f/1387r and Arch-25f/Arch-907r). DGGE was
performed on nested GC-clamp PCR products (CBS
Scientific DGGE 2401). 16S rDNA clone libraries
were created using CloneJET PCR cloning kit
(Fermentas), clustering by restriction analysis, and
representative clones were sequenced, and analysed
using NCBI BLAST, ClustalW and MEGA4 software.
Results
Figure 1: MDAC SEM Images A. Quartz cemented by aragonite &
dolomite crystals. B. Aragonite crystals & framboidal pyrite.
Total
Br- Br-
PLFA SATFA MUFA PUFA SATFA UFA δC 13
MDAC 1.83 0.49 0.43 n.d. 0.67 n.d -27.6
Pockmark 13.84 3.44 2.35 0.74 6.07 0.17 -27.7
Table 1: MDAC and Dunmanus PLFA abundances (�g g -1 ) and
average � 13 C values. (SATFA- saturated FA, MUFA- monounsaturated FA, PUFApolyunsaturated
FA, Br-SATFA- branched saturated FA, Br-UFA- branched unsaturated FA)
Figure 2: Dendrogram comparing DGGE profiles in Dunmanus Bay
pockmark field (GC04, GC09, GC10) and control (GC14)
2mbsf 6mbsf
Species
Clones
%
Total
Clones
%
Total
Psychrobacter sp. 35 54 22 44
Sulfitobacter sp. 9 14 13 26
Alcanovirax borkumensis SK2 4 6 - -
Acinetobacter baumannii 3 5 - -
Geobacillus sp. 3 5 - -
Stenotrophomonas maltophilia 2 3 - -
Aromatoleum aromaticum 1 2 - -
Marinomonas sp. 1 2 - -
Pseudoalteromonas halo. 1 2 2 4
Thiobacillus thioparus - - 2 4
Variovorax paradoxus - - 1 2
Colwellia sp. - - 1 2
Uncultured α-proteobacterium - - 2 4
Table 2: Bacterial species vertical distribution in Malin pockmark
Discussion: PLFA and DGGE profiles indicate a
more diverse bacterial population in the Dunmanus
pockmarks, compared to the MDAC site and a lower
bacterial abundance in the MDAC (Table 1.). DGGE
profiles show a statistically heterogenous bacterial,
but homogenous archaeal community in the
Dunmanus pockmarks compared to the surrounding
environment and interestingly, the opposite within the
MDAC (Figure 2.). DGGE band sequencing indicate
dominant bacteria within the Dunmanus pockmark
field are Achromobacter and Stenotrophomonas sp.
16S rRNA bacterial phylogenetic analysis in the Malin
pockmark show dominant species belong to
Psychrobacter and Sulfitobacter sp., which decrease
and increase in abundance with depth, respectively.
Notably, minor species composition is also markedly
different (Table 2.).
References
1. Croker, P.F. et al. (2005) SEA6 Report 2. Games,
K.P. (2001) Geol. Soc. Of London 3. Monteys , X. et
al. (2008) OSP-01, 33rd Inter. Geol. Congr., Oslo 4.
Zhou, J. et al. (1996) Appl. Environ. Microbiol. 62:316-
322
555

P-430
New bacteriochlorophyll degradation products from a coastal
salt pond
Raymonde Baltenweck-Guyot, Ruben Ocampo-Torres
CNRS-UdS UMR7177, Strasbourg, France (corresponding author:ocampo@unistra.fr)
Photosynthetic sulphur bacteria inhabit the upper part
of the anoxic layer, located in the photic zone, of
some stratified water bodies (ponds, lakes and
estuarine habitats). The photosynthetic pigments
present in brown, green and red sulphur bacteria is a
complex group of bacteriochlorophylls c, d and e is
called Chlorobium chlorophylls. These pigments have
a commun number of structural features and present
some structural differences compared to other
chlorophylls and bacteriochlorophylls. They are
chlorins, they lack the 13 2 -carbomethoxy group, they
be -hydroxyethyl substituent at position C-3,
and probably the most important, at least for organic
geochemists, they may bear extended alkyl groups at
positions C-8, C-12 and for bacteriochlorophylls c and
e a methyl group at position C-20. These alkyl groups
are very resistant through diagenetic transformations
and are still present in some porphyrins isolated from
geological samples. Geological pigments bearing
such as alkyl groups at positions C-8, C-12 and C-20
are biological markers of photosynthetic sulphur
bacteria and are used for paleoenvironmental
reconstructions. Here we report the presence of
several novel bacteriopheophorbides series isolated
from a coastal salt pond sediment (Salt Pond, MA,
U.S.A.). Two pigments series (bacteriopheophorbides
and methylbacteriopheophorbides), isolated from this
sediment, present the same carbon framework than
bacteriopheophorbides c but bear an acetonyl group
at the C-7 position. These compounds are presents in
this sediment as free compounds as well as linked to
the macromolecular material via ester bridges. These
series were studied by RP-18 HPLC, UV-Vis, SM and
LC-MS (APPI mode) and the structure determination
of some of their members were obtained by 1 H NMR.
They point to be fossils of an unknown photosynthetic
bacteriochlorophyll series even if an origin from water
column or post sedimentary transformations can not
be excluded.
REFERENCES
Keely, B.J., Maxwell, J.R., 1993. The Mulhouse basin:
evidence from porphyrin distributions for water
column anoxia during deposition of marls. Organic
Geochemistry 20, 1217-1225.
Ocampo Torres, R., 1985. Porphyrines dans le
schiste de Messel : Etude structurale et signification
géochimique. Ph D. Thesis, Université Louis Pasteur
de Strasbourg.
Ocampo, R., Bauder, C., Callot, H.J., Albrecht, P.,
1992. Porphyrins from Messel oil shale (Eocene,
Germany): Structure elucidation, geochemical and
biological significance, and distribution as a function
of depth. Geochimica et Cosmochimica Acta 56, 745-
761.
Scheer, H., 1991. Chemistry of chlorophylls. In: Sheer,
H. (Ed.), The Chlorophylls, pp. 3-30. CRC Press.
Wilson, M.A., Hodgson, D.A., Keely, B.J., 2004.
Structural variations in derivatives of
bacteriochlorophylls of Chlorobiaceae: impact of
stratigraphic resolution on depth profiles as revealed
by methanolysis. Organic Geochemistry 35, 1299-
1307.
556

P-431
Carbohydrate dynamics in Cariaco Basin pore water and
sediments
Melesio Quijada 1 , Armelle Riboulleau 1 , Yann Guerardel 2
1 FRE 3298 CNRS Géosystèmes, UFR des Sciences de la Terre, Université de Lille 1, Villeneuve d'Ascq,
France, 2 UMR 8576 CNRS Laboratoire de Glycobiologie Structurale et Fonctionnelle, Université de Lille 1,
Villeneuve d'Ascq, France (corresponding author:ma.quijada-hermoso@gmail.com)
Carbohydrates are one of the major constituents of
the biomass, and account for a substantial amount of
the total organic carbon (TOC) in water and
sediments in marine environments.
It is often accepted that structural carbohydrates are
rapidly re-mineralized during early diagenesis and do
not make substantial contribution to total organic
carbon in ancient sediments and kerogens.
However some studies has shown that structural
carbohydrates may escape decomposition and
remineralization depending on different factors, such
as paleoproductivity, presence of oxygen in water and
sediments and sedimentation rate (Moers et al. 1994).
Even more, some studies report that once particulate
carbohydrates escape water column in non
oxygenated environments, they may be preserved
within the organic matrix (Cowie and Hedges, 1984).
In our study we investigated the neutral
carbohydrates (NCHO) variation in sediments from
Cariaco Basin, covering a period of time of 135ky.
For that, 15 sediment samples were obtained from
sediment cores 1002 D & E collected on the central
saddle of the Cariaco Basin during the ODP Leg 165.
The NCHO where determined quantitatively after (i)
water extraction to explore pore water carbohydrates
(PNCHO) and (ii) acid hydrolysis to investigate
structural and sediment-attached monomers
(HNCHO).
Monosaccharides were analyzed by GC-FID and
GC/MS after derivatization of aldoses to their
corresponding alditol acetates as described in Eder et
al. (2010).
Sequential hydrolysis (2N, 4N and 6N trifluoroacetic
acid) was used to avoid amino-acids and
carbohydrates glycosidic reaction to form melanoidins
(Quijada et al. 2008). Variations in acid concentration
during hydrolysis yielded different amounts of
individual monosaccharides for the same sample.
These differences are related with differences in
glycosidic bonds behavior during hydrolysis (Mopper,
1977).
The total content of carbohydrates ranged from 0,66
to 2,25 wt% of the TOC in PNCHO and from 5,3 to
11,36 wt% of the TOC in HNCHO. Hydrolysates were
dominated by hexoses in both fractions, and no
correlation with TOC was found.
Nine monosaccharides were identified in the 15
samples. Deoxysugars (fucose and rhamnose) are
apparently more susceptible to 2N TFA hydrolysis.
The contribution of deoxysugars to the TOC (focusing
on rhamnose) is considered to be indicative for the
presence of bacteria.
Hexoses (galactose, manose, glucose) yielded mostly
in the 4N hydrolysis. The large contribution of glucose
is related with the presence of storage
polysaccharides (cyanobacteria accumulate polyglucoses
in certain conditions. Lehmann and Wöber,
1976). Manose and galactose present a large
contribution to the total NCHO budget, corresponding
to structural sugars of microorganisms.
Xylose was more susceptible to 6N hydrolysis in all
samples suggesting to be a building block
carbohydrate, like previously reported for microbial
resistant sheath material (Klok et al. 1984).
We used the hexose to pentose ratio (Oades, 1984)
to investigate the origin of sugars and its variation
with depth. The (galactose + manose) / (arabinose +
xylose) ratio>2 indicated an algae and zooplankton
origin for NCHO during the all period studied.
The NCHO profile present individual variations with
depth depending on their individual reactivity and
resistance to degradation. Some sedimentary facies
are characterized by a rather increase in NCHO
content reflecting environmental control. Globally, the
NCHO content decrease with depth reflecting
heterotrophic degradation and/or preservation via
natural sulfurization (van Dongen et al. 2006).
References:
- Cowie and Hedges (1984). Geochim. Cosmochim.
Acta 48, pp. 2075-2087.
- Eder et al. (2010). Org. Geochem. 41, pp. 580-585.
- Lehmann and Wöber (1976) Arch. Microbiol. 111,
93-97
- Klok et al. (1984). Org. Geochem. 7, pp. 73-84.
- Mopper (1977). Mar. Chem. 5, pp. 585-603.
- Oades et al. (1984). Plant Soil 76, pp. 319–337.
- Quijada et al. (2009) 24 th IMOG. Poster.
- van Dongen et al. (2006) Org. Geochem. 37, pp.
1052-1073.
557

P-432
Thermally stable anammox biomarker lipids produced during
hydrous pyrolysis
Darci Rush 1 , Andrea Jaeschke 1,2 , Stefan Schouten 1 , Jaap Sinninghe Damsté 1
1 NIOZ Royal Netherlands Institute for Sea Research, Department of Marine Organic Biogeochemistry, Den
Hoorn, Netherlands, 2 ETH Zürich, Institute of Geochemistry and Petrology, Zurich, Switzerland
(corresponding author:darci.rush@nioz.nl)
The anaerobic oxidation of ammonium (anammox)
has been shown to account for a significant part of the
loss of fixed inorganic nitrogen from the world‘s
oceans [1]. Anammox is performed by a bacterial
group within the Planctomycetes. The cells of these
bacteria contain a specialized organelle-like
compartment, named the anammoxosome.
Ladderane lipids surround the anammoxosome,
protecting cell function from the diffusion of the toxic
intermediates of the anammox reaction. Ladderanes
are unique to anammox bacteria and their presence in
modern environmental settings is a biomarker of the
occurrence of anammox [2]. Other lipids found to be
common in anammox cultures include hopanoids,
9,14-dimethylpentadecanoic and 10-methylhexadecanoic
acids, and squalene [3]. Understanding the
role of anammox in different environments is crucial in
characterizing the nitrogen cycle. However, little is
known of the importance of anammox in past nitrogen
cycling, as ladderanes are thermally labile (due to
their cyclobutane structure [5]) and do not preserve
well as such in the sediment record.
In this study we investigated the potential production
of thermally stable lipids derived from ladderane
lipids. For this, anammox biomass was artificially
matured by hydrous pyrolysis for 72 hours at
temperatures between 120 and 365°C.
The anammox biomass residue was extracted after
the hydrous pyrolysis experiments. Analyses using
HPLC/APCI-MS/MS indicated that during thermal
maturation, ladderane lipids undergo similar structural
rearrangements as those observed during GC
analyses i.e., opening of a cyclobutane ring and
formation of a double bonded ladderane [5].
Fig. 1. Weight of oil generated during hydrous
pyrolysis experiment as a function of temperature.
Oil was
generated at hydrous pyrolysis temperatures between
220 to 365°C (Fig. 1) and analyzed for degradation
products.
GC-MS analyses of the aliphatic fractions of these oils
showed the presence of C29-C35 hopenes and
hopanes as well as other lipids that, to our
knowledge, have not previously been identified.
Some of the alkanes had a m/z fragment of 161, also
found in mass spectra of ladderane fatty acids,
indicating they may be products derived there from.
Furthermore, they were comprised of C16 to C19
homologs, in agreement with a decarboxylation of
C18-C20 ladderane fatty acids. The presence of these
lipids at hydrous pyrolysis temperatures above 260°C
indicate that they are thermally stable and may be
better suited as biomarkers for anammox activity in
mature sediments. Preliminary identification of these
components suggests that their carbon chain lengths
are in agreement with a structural rearrangement of
the C18-C20 ladderane fatty acids. We are currently
isolating the alkanes by preparative GC for rigorous
identification by NMR techniques.
[1] Hamersley, M.R., et al. (2007) Limnol. Oceanogr.
52, 923-933.
[2] Kuypers M.M.M. et al. (2003) Nature 422, 608-
611.
[3] Sinninghe Damsté, J.S., et al. (2005) FEBS
Journal 272, 4270-4283.
[4] Lewan, M.D. et al. (1979) Science 203,897-899.
[5] Jaeschke, A. et al. (2008) Org. Geochem. 39,
1735-1741.
Fig. 2. Oil generated at 260°C. (a) Total Ion Current
and (b) mass chromatogram of m/z 161 revealing the
unknown ladderane products .
558

P-433
Environmental occurrence of oxic degradation products of
anammox ladderane lipids
Darci Rush 1 , Andrea Jaeschke 1,2 , Ellen Hopmans 1 , Stuart Wakeham 3 , Stefan Schouten 1 ,
Jaap Sinninghe Damsté 1
1 NIOZ Royal Netherlands Institute for Sea Research, Department of Marine Organic Biogeochemistry, Den
Hoorn, Netherlands, 2 ETH Zürich, Institute of Geochemistry and Petrology, Zurich, Switzerland, 3 Skidaway
Institute of Oceanography, Savannah, United States of America (corresponding author:darci.rush@nioz.nl)
Anaerobic ammonium oxidation (anammox), a
bacterially mediated process in the marine nitrogen
cycle, has been shown to contribute substantially to
the loss of fixed inorganic nitrogen from the ocean
system [1]. Understanding the role of anammox in
different environments is crucial in characterizing the
nitrogen cycle. Ladderane lipid biomarkers are unique
to the bacteria performing anammox and their
presence in modern environmental settings is
indicative of the occurrence of anammox [2].
However, little is known of the importance of
anammox in past nitrogen cycling, as ladderanes are
thermally labile (due to their cyclobutane structure)
and do not preserve well as such in the sediment
record.
Recently, we found that under oxic conditions
ladderane lipids were degraded to short-chain
ladderane degradation products (Fig 1), which were
rigorously identified by 2D-NMR. The most
pronounced production of these short-chained lipids
during the degradation experiments was at 40 °C and
not at higher temperatures. This suggests that the
degradation of ladderane lipids was microbially
mediated, likely through a β-oxidation pathway, in
which the alkyl side chain of the cyclobutane rings is
shortened in a sequence of reactions that removes
two carbon atoms at a time.
Based on these results, we developed a method to
detect two new biomarkers (I-II; Fig. 1) for the oxic
degradation of ladderane lipids in order to trace their
occurrence in ancient sediments. These shortchained
ladderanes were found in sediments under
the major upwelling area off the coast of Peru even
deeper than the original ladderane biomarkers (42
mbsf), suggesting they might be better preserved.
In the Arabian Sea, the degradation biomarkers were
found to be present already in the oxygen minimum
zone of the water column, suggesting that oxidation of
ladderane lipids may already occur at very low
oxygen concentrations. However, they were not
detected in the euxinic water column of the Cariaco
basin suggesting inhibition of the degradation
pathway in the presence of sulfate. In the Arabian
Sea, these ladderane degradation products increased
in abundance relative to original ladderanes with
sediment depth, which indicates that short-chained
ladderanes might prove to be a more useful marker
for past anammox activity. Moreover, the presence of
short-chained ladderanes in past settings may be
indicative of anammox living under oxygen minimum
conditions rather than in euxinic water columns.
Fig. 1. Structures of ladderane lipids derived from
anammox enrichment cultures (1-4) and their
transformation products derived from microbial oxic
degradation (I-III). 1) C18-[5]-ladderane FA, 2) C20-
[5]-ladderane FA, 3) C18-[3]-ladderane FA, 4) C20-
[3]-ladderane FA, I) C14-[5]-ladderane FA, II) C14-[3]ladderane
FA, III) C16-[3]-ladderane FA.
[1] Hamersley, M.R., et al. (2007) Limnol. Oceanogr.
52, 923-933.
[2] Sinninghe Damsté, J.S., et al. (2002) Nature 419,
708-712.
[3] Dutta and Harayama. (2001) Appl. Environ.
Microbiol. 67, 1970-1974.
559

P-434
Impact of a high CO2 partial pressure on the methanogenic
pathway in a high-temperature petroleum reservoir
Daisuke Mayumi 1 , Susumu Sakata 1 , Haruo Maeda 2 , Yoshihiro Miyagawa 2 , Masayuki
Ikarashi 2
1 National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan, 2 INPEX
Corporation, Tokyo, Japan (corresponding author:su-sakata@aist.go.jp)
Injection of CO2 into deep subsurface petroleum
reservoirs has been planned and implemented
worldwide for the purpose of enhanced oil recovery
(EOR) and CO2 storage. Meanwhile, the development
of microbial EOR by stimulating the activity of in situ
microbes to produce methane has been suggested
[1]. Little is known, however, about the influence of a
high CO2 partial pressure on the activity of microbes
inhabiting the reservoirs. Here, we investigated the
influence of CO2 on in situ methanogenic microbes by
conducting high temperature and pressure
incubations mimicking the reservoir conditions.
Methanogenic pathways were determined by
combination of stable isotope (SI) tracer methods and
molecular biological analyses.
Produced water and crude oil samples were
collected at the wellhead in Yabase oil field, Japan.
The incubation experiments were conducted using
microcosms comprised of the produced water, crude
oil and traces of [2- 13 C]-acetate or [ 13 C]-bicarbonate.
The microcosms were pressurized with either N2 or
N2+CO2 (90:10) at 5 MPa and then incubated at 55°C,
simulating the reservoir conditions before and after
CO2 injection. Headspace gas and incubated water
samples were periodically measured for � 13 C values
of methane and DIC (dissolved inorganic carbon) with
GC-C-IRMS. Microbial communities of the incubated
water were analyzed by the methods of 16S rRNA
gene clone libraries and group-specific real-time PCR.
Details of the sampling and experiments are as in
Mayumi et al. [2].
In all the microcosms, methane production was
observed in response to the decrease of acetate
included in the produced water. The acetate
consumed was nearly equivalent to the methane
produced. The methane production rates in the
microcosms pressurized with N2+CO2 were
significantly higher than those pressurized with N2.
Among those pressurized with N2, an immediate and
distinct increase in � 13 C was observed for methane in
the bicarbonate-labelled microcosm, while a small
and gradual increase in � 13 C was observed for
methane in the acetate-labelled microcosm. Methane
was depleted in 13 C relative to DIC by a similar
magnitude in both microcosms. Microbial community
analyses of the incubated water showed bacterial
communities dominated by the genus
Thermacetogenium, known as a thermophilic
syntrophic acetate-oxidizing bacterium, and archaeal
communities dominated by thermophilic
hydrogenotrophic methanogens belonging to the
genus Methanothermobacter. These results
consistently indicate that acetate oxidation coupled
with hydrogenotrophic methanogenesis [3] was the
major pathway in the microcosms pressurized with N2.
Among those pressurized with N2+CO2, an
immediate and distinct increase in � 13 C was observed
for methane in the acetate-labelled microcosm, while
no appreciable increase in � 13 C was observed for
methane in the bicarbonate-labelled microcosm.
Microbial community analyses of the incubated water
showed archaeal communities dominated by
acetoclastic methanogens belonging to the genus
Methanosaeta. These results consistently indicate
that acetoclastic methanogenesis was the major
pathway in the microcosms pressurized with N2+CO2.
We therefore conclude that injection of CO2 into a
high-temperature petroleum reservoir for EOR and
CO2 storage will cause a drastic change in the in situ
methanogenic pathways.
References
[1] Jones, D.M., Head, I.M., Gray, N.D., Adams, J.J.,
Rowan, A.K., Aitken, C.M. et al. (2008) Nature 451,
176-180.
[2] Mayumi D., Mochimaru H., Yoshioka H., Sakata
S., et al., Environmental Microbiology (in press)
[3] Hattori, S. (2008) Microbes and Environments 23,
118-127.
560

P-435
Impact of lake water pH on the distribution of branched
tetraether membrane lipids: further indication for an aquatic
source
Petra Schoon 1 , Anna de Kluijver 2,3 , Jack Middelburg 2,3 , John Downing 4 , Jaap Sinninghe
Damsté 1 , Stefan Schouten 1
1 NIOZ Royal Netherlands Institute for Sea Research, Department of Marine Organic Biogeochemistry, 't
Horntje, Texel, Netherlands, 2 NIOO Netherlands Institute of Ecology, Department of Ecosystem Studies,
Yerseke, Netherlands, 3 Department of Earth Sciences - Geochemistry, Faculty of Geosciences, Utrecht
University, Utrecht, Netherlands, 4 Iowa State University, Department of Ecology, Evolution, and Organismal
Biology, Ames, Iowa, United States of America (corresponding author:petra.schoon@nioz.nl)
Recently, the distribution of branched glycerol dialkyl
glycerol tetraethers (GDGTs) in lake sediments have
gained increased interest for their potential use in
reconstructing paleoenvironmental conditions [e.g. 1,
2]. Branched GDGTs are membrane lipids produced
by yet unidentified bacteria that thrive in soils, peat
bogs and likely lake waters or sediments. Branched
GDGTs comprise methylated C28 alkyl chains, which
are ether-linked to a glycerol backbone at either side.
Additionally, some of these alkyl chains contain a
cyclopentyl moiety. Weijers et al. [3] found a
correlation between the relative degree of cyclization
of these branched tetraether lipids with soil pH (CBTindex)
for soils and peats. However, application of this
proxy in lake sediments may be complicated as the
sources of the branched GDGTs can be both
autochtonous and allochtonous [4].
Here we studied the distribution of branched GDGTs
in suspended particulate matter sampled from 23
lakes in Iowa and Minnesota (USA). These lakes
have been selected to encompass a wide range in pH
(6.1 to 9.8) and alkalinity (8 to 237 mg CaCO3/L).
Such a cross-system lake study will allow us to test
the CBT-index on variations in water column pH. The
sampled lakes in Minnesota have an overall lower pH
than the sampled lakes in Iowa (Fig. 1). We find that
branched GDGT concentrations are higher in the (low
pH) Minnesota lake suspended matter, compared to
those in Iowa. This is in agreement with observations
in soils where the amount of branched GDGTs is
higher with lower pH [5], thus suggesting that these
compounds are produced, at least partly, in situ in the
lake. Furthermore, our preliminary results show a
linear correlation between observed lake water pH
and the CBT-index, although lakes with a pH above
8.5 do not seem to fit this correlation. The same kind
of relationship has recently been found in a study of
Chinese lake surface sediments [6]. Our findings
suggest that the CBT proxy may potentially be used
to reconstruct the pH of ancient lakes [cf. 1], although
the application of the CBT-index on high pH lakes
should be performed with care.
Fig. 1. Range in pH and alkalinity of the analyzed lakes in
Iowa and Minnesota, USA.
References
[1] Tyler et al. (2010), J. Geophys. Res. 115, doi: 10.1029/
2009JG001109.
[2] Blaga et al. (2010), Org. Geochem. 41, pp. 1225-1234.
[3] Weijers et al. (2007), GCA 71, pp. 703-713.
[4] Tierney & Russell (2009), Org. Geochem. 40, pp. 1032-
1036.
[5] Peterse et al. (2010), Org. Geochem. 41, pp. 1171-
1175.
[6] Sun et al. (2011), J. Geophys. Res. 115, doi: 10.1029/
2010JG001365.
561

P-436
Methane oxidation in the water column of Lago di Cadagno
(Switzerland)
Carsten J. Schubert 1 , Andreas Krupke 2 , Mathias Kirf 1 , Daniela Franzke 2 , Marcel M.M.
Kuypers 2
1 Eawag, Swiss Federal Institute of Aquatic Science and Technology, Kastanienbaum, Switzerland, 2 MPI for
Marine Microbiology, Bremen, Germany (corresponding author:carsten.schubert@eawag.ch)
The methane cycle in the water column of Lago di
Cadagno was investigated. Lake Cadagno is a
meromictic lake located in the catchment area of a
dolomite vein rich in gypsum in the Piora valley in the
Southern Alps of Switzerland (46°33‘N, 8°43‘E). The
lake lies at 1923 m above sea level and has a
maximum water depth of 21 m in summer. It covers
an area of 26 ha with a volume of 2.4*10 6 m 3 and a
water temperature of 4-6°C below 13 m (Del Don et
al. 2001). The water column is characterized by a
high salinity monimolimnion and a permanent
chemocline moving during the year between a depth
of 9 and 14 m, separating the oxic epilimnion from the
anoxic, sulfidogenic hypolimnion. The lake bottom
below the redox transition zone is anoxic all the time
(Wagener et al., 1990). Due to the infiltration of
subaquatic spring water flowing through gypsum rich
dolomites, Lake Cadagno water contains relatively
high concentrations of sulfate (1.5 mmol l -1 ),
hydrogen-carbonate, calcium, magnesium, and
sulfide (1 mmol l -1 ) resulting from sulfate reduction in
the hypolimnion and sediments (Hanselmann &
Hutter, 1998; Del Don et al., 2001; Dahl et al., 2010).
We detected no oxygen below 10.8 m but high sulfide
(up to 280 �M) in the hypolimnion. Nitrate was not
available below 12.5 m, ammonium concentrations
increased to 40 �mol l -1 at 17.5 m depth (Halm et al.,
2009) and iron (II) was below 5 �mol l -1 in the bottom
water and not available in the uppermost sediments
(Hanselmann & Hutter, 1998).
High methane concentrations occur in the
hypolimnion (up to 48 �mol l -1 ) until methane
oxidation in the chemocline reduces methane
concentrations (300 nmol l -1 ). Methane oxidation is
indicated by an increase in carbon isotopic
composition from the hypolimnion (-76 ‰ VPDB) to
very heavy values (11 ‰ VPDB) in the chemocline.
Incubations at in-situ temperatures revealed methane
oxidation rates to be lowest in 9 m water depth (50
nmol l -1 h -1 ) under oxic conditions and highest in 13m
water depth (3300 nmol l -1 h -1 ) under anoxic
conditions. No common anaerobic methane oxidizers
(ANME group) were detected using FISH and also
AAA cells recently shown to occur in Lake Cadagno
sediments (Schubert et al. 2011) were missing.
Investigations using nano-SIMS measurements on
microbial cells from water samples incubated with 13 C
13
labeled methane showed highly C enriched
methanotroph type I cells at 10 m. Furthermore, we
will present the results from a combination of single
cell and lipid analysis.
References
Dahl, T.W., Anbar, A.D., Gordon, G.W., Rosing, M.T.,
Frei, R., and Canfield, D.E. (2010) The behavior of
molybdenum and its isotopes across the chemocline
and in the sediments of sulfidic Lake Cadagno,
Switzerland. Geochimica et Cosmochimica Acta 74:
144-163.
Del Don, C., Hanselmann, K. W., Peduzzi, R., and
Bachofen, R. (2001) The meromictic alpine Lake
Cadagno: Orographical and biogeochemical
description. Aquat Sci 63: 70-90.
Halm, H., Musat, N., Lam, P., Langlois, R., Musat, F.,
Peduzzi, S. et al. (2009) Co-occurrence of
denitrification and nitrogen fixation in a meromictic
lake, Lake Cadagno (Switzerland). Environmental
Microbiology 11: 1945-1958.
Hanselmann, K. and Hutter, R. (1998)
Geomicrobiological coupling of sulfur and iron cycling
in anoxic sediments of a meromictic lake: sulfate
reduction and sulfide sources and sinks in Lake
Cadagno. In Lake Cadagno: a meromictic Alpine lake.
Peduzzi, R., Bachofen, R., and Tonolla, M. (Eds),
Documenta Ist. Ital. Idrobiol., 63: 85-98.
562

P-437
Microbial community shifts at temperature and geochemical
gradients at sulfur-rich shallow hydrothermal vents offshore
Panarea Island, Sicily
Florence Schubotz 1,4 , Chia-I Huang 2 , Gunter Wegener 2 , Jan P. Amend 3 , Roy Price 3 ,
Thomas Holler 2 , Anke Meyerdierks 2 , Rudolf Amann 2 , Roger E. Summons 4 , Kai-Uwe
Hinrichs 1
1 Department of Geosciences and MARUM - Center for Marine Environmental Sciences, Bremen, Germany,
2 Max-Planck Institute for Marine Microbiology, Bremen, Germany, 3 Department of Earth, Atmospheric and
Planetary Sciences, Washington University, St. Louis, Germany, 4 Department of Earth, Atmospheric and
Planetary Sciences, Massachusetts Institute of Technology, Cambridge, United States of America
(corresponding author:schubotz@uni-bremen.de)
The active volcanic islands of the Eolian
Archipelago north of Sicily, Italy, have been used for
many decades as a natural laboratory for the study of
thermophilic Bacteria and Archaea [1]. Most recently,
the shallow marine hydrothermal vents off the coast of
Panarea Island have attracted attention due to a
submarine volcanic exhalative event in 2002. Some
sites (Blackpoint) are characterized by vigorous
venting with maximum temperatures of up to 135°C,
whereas other sites exhibit more diffusive venting with
temperatures ranging from 40 to 70°C (Hot Lake).
The hydrothermal fluids off Panarea Island are rich in
CO2 (up to 97 vol.%), and H2S (up to 2 Vol.%) [2], and
are slightly acidic (pH 5-6; Fig. 1a).
Investigations of the intact polar membrane lipid
(IPL) composition in sediments ranging from ca. 40-
90°C (Fig. 1a) showed a dominance of bacterial lipids
at lower temperatures (Hot Lake I) mainly comprised
of ornithine lipids and the phospholipids
phosphoethanolamine, phospho-(N)-methylethanolamine,
phosphocholine, phosphoglycerol and
diphosphoglycerol (Fig 1b). Betaine lipids and
glycolipids, which are likely derived from phototrophic
organisms in the surface sediments decrease with
increasing sediment depth. Notable is a shift to a
dominance of archaeal lipids with depth and/or
temperature at Hot Lake II and Blackpoint I. The
observed archaeal IPLs are diglycosidic glycerol
dibiphytanyl tetraethers (GDGT) with core lipids
comprised of 0 to 2 pentacyclic rings and a series of
H-shaped GDGTs. IPL investigations are
accompanied by a series of molecular biological
analyses such as fluorescence in situ hybridization
(FISH) and comparative 16S rRNA gene analyses.
FISH results are consistent with an increase of
Archaea relative to Bacteria with increasing sediment
depth. Epsilonproteobacteria, Bacteriodetes and
Deltaproteobacteria are identified as major bacterial
groups at lower temperatures while clones affiliated to
the crenarchaeotal Desulfurococcaceae and
Korarchaeota are found with increasing temperature
and sediment depth.
To investigate major pathways of carbon turnover
under anaerobic conditions in the sediments we have
conducted a 13 C and deuterium lipid-labelling study.
The results will be evaluated by head group specific
label uptake [2] in concert with gene-based analyses
to enable more detailed chemotaxonomic
assignments.
Fig. 1. a) Depth profiles of temperature, pH, and IPL
total concentration at sites Hot Lake and Blackpoint.
b) Composition of IPLs at two depth intervals of the
three investigated sites.
References
[1] Amend J.P. and Shock E.L. (2001) FEMS
Microbiol. Rev. 25, 175-243.
[2] Schubotz F., et al. (2011) Geochim. Cosmo-chim.
Acta. doi:10.1016/j.gca.2011.05.018
563

P-438
Lipid biomarkers of archaeal and sulphate reducing bacterial
aggregates in gas hydrate-bearing deep sea sediment
Yong-Cheon Ahn 1 , Jang-Jun Bahk 2 , Jung-Hyun Lee 3 , Kyung-Hoon Shin 1
1 Hanyang University, Ansan, Republic of Korea, 2 Korea Institute of Geoscience and Mineral Resources,
Daejeon, Republic of Korea, 3 Korea Ocean Research and Development Institute, Ansan, Republic of Korea,
4 Hanyang University, Ansan, Republic of Korea (corresponding author:shinkh@hanyang.ac.kr)
Gas hydrate has an importance as new
alternative energy in the future and it is necessary to
understand microorganism activity related to the
production and consumption of the gas hydrate and
methane biogeochemical cycle. In the present study,
origin of sedimentary organic matter related to the
production of gas hydrate in the gas hydrate-bearing
core sediment and non bearing core sediment were
determined using carbon and nitrogen stable isotope
ratio and C/N ratio. Bulk organic matter of all sediment
cores nearly seems to be marine algal origin,
considering carbon and nitrogen stable isotope ratio
and C/N ratio.
Also, lipid biomarkers concentrations of archaeal
and bacterial aggregates in the gas hydrate-bearing
sediment were measured in the gas hydrate-bearing
sediment. Some biomarkers (PMI and crocetane)
related to the AOM(Anaerobic Oxidation of Methane)
and sulfate reducing bacteria(i-C15:0 and a-C15:0)
were apparently detected at 100 ~ 150 cm depth in
the gas hydrate-bearing core sediment(St.12-2),
corresponding to metagenomic characterization of
sulfate-methane transition zone (SMTZ).
The current results provide useful information to
understand distribution of microorganism aggregate
related to the production and consumption of methane
in the gas hydrate-bearing deep sea sediment from
Ulleung-Basin, East Sea.
564

P-439
Origin of alkane hydrocarbons in the hydrothermal deposits of
the Mid-Atlantic Ridge and East Pacific Rise
Natalia Shulga 1 , Valerij Peresypkin 2
1 P.P. Shirshov Institute of Oceanology, Moscow, Russian Federation, 2 P.P. Shirshov Institute of Oceanology,
Moscow, Russian Federation (corresponding author:nash.ocean@gmail.com)
The purpose of this abstract is to present results of
initial investigation related to n-alkanes distribution in
various regions of the oceanic rift systems. Alkane
hydrocarbons are type of biomarkers show little or no
change in structure from their parent organic
molecules in living organisms, bacteria or plants.
They are chemically stable and, hence, retain primary
biological and geological information.
The samples for research were collected from
numerous expeditions by using deep manned
submersibles Mir-1 and Mir-2.
Molecular and group composition of n-alkanes were
analyzed in sulphide and carbonate deposits of
hydrothermal fields from the Mid-Atlantic Ridge and
East Pacific Rise, related to the process of
serpentinization of ultrabasic rocks in the oceanic
core (Rainbow, Lost City); basaltic volcanism (Broken
Spur, Lucky Strike, TAG, Snake Pit, 9°50‘N) and oilsaturated
ores from Guaymas Basin. All solvent
extracts from samples have been studied by gas
chromatography/ mass-spectrometry method.
Total n-alkanes concentrations in the samples are low
and vary widely from 0,01 to 1,82 µg/g of dry weight
of ore deposits, but this values incommensurable low
in comparison with concentrations of hydrothermal
sediments. These differences can be explained by
organic matter formation features of both in
hydrothermal deposits and sediments (pressure,
temperature, different mineralogical composition etc.).
It was shown a presence of n-alkanes C12-C35 in most
explored samples of hydrothermal deposits. The
major amount of n-alkanes from hydrothermal
deposits has a biologic origin (transformation of
chemoautotrophic organisms), except samples from
Guaymas Basin, where instant thermolytic generation
of hydrocarbons (so-called ‘‘hydrothermal petroleum‘‘)
has been observed [1].
The n-alkane distributions in the hydrothermal
formations from Rainbow, 9°50‘N East Pacific Rise
and Guaymas Basin has comparable concentrations
of even/odd homologies (CPI=0,90÷1) while the
values of C23-C35 range from 11,7 to 29,6 (% relat.).
This distribution can be interpreted as abiogenic
thermocatalitic oil, since it difficult to supply highmolecule
weight odd n-alkanes derived from
terrestrial plants to these sediment-free hydrothermal
systems of the ocean. Along with this, one may
assume that in the hydrothermal systems with no
sedimentary layer, oil hydrocarbons are also formed
owing to the Fisher-Tropsch type reactions [2].
Fig.1. Relative distribution of n-alkanes in the
samples from the A) Rainbow (4396-1), B) 9°50‘N
East Pacific Rise (4658-3), C) Guaymas Basin (4713-
3).
References
[1] Simoneit, B.R.T. Appl. Geochem., No. 6, 49-56
(1985).
[2] McCollom, T.M., Seewald, J.S. Chem. Rev.
107(2), 382-401 (2007).
565

P-440
Estimation of endospore numbers in marine sediment samples
by quantification of dipicolinic acid
Marieke Sieverding 1 , Bert Engelen 1 , Henrik Sass 2 , Barbara Scholz-Böttcher 1 , Heribert
Cypionka 1 , Jürgen Rullkötter 1
1 Institute of Chemistry and Biology of the Marine Environment (ICBM), Carl von Ossietzky University of
Oldenburg, P.O. Box 2503, D-26111 Oldenburg, Germany, 2 School of Earth, Ocean and Planetary Sciences,
Cardiff University, Cardiff CF10 3YE, United Kingdom (corresponding author:marieke.sieverding@unioldenburg.de)
For more than 20 years, the scientific drilling
community has studied microbial life in deeply buried
sediments [1,2]. During these studies, prokaryotes
were detected even at 1600 mbsf [3]. Extrapolation of
direct counts of microbial cells leads to the estimate
that one tenth to one third of the world‘s living
biomass may be stored in the marine sub-seafloor
biosphere [4]. Until today, it is unclear as to what
extent these prokaryotes are active, since
fluorescence dyes, like acridine orange or DAPI, do
not discriminate between metabolically active,
dormant or dead cells. These dyes even stain
endospores. In this study we show that in marine
sediments endospores contribute up to 19 % to the
total cell numbers at some tens of meters of depth.
Depth (m)
0,1
1
10
100
1000
3 4 5 6 7 8 9 10 11
Log 10 (spores g -1 sediment)
Fig 1: Depth distribution of endospores in tidal flat sediments
(black data points) and in sediments from ODP Leg 201
(green squares) in comparison with the depth distribution of
prokaryotes in the deep biosphere (red line) determined by
[5] (in log10[cells cm -3 sediment]; red dashed lines: 95 %
upper and lower prediction limits).
Dipicolinic acid (DPA), which is a major component of
endospores, was used to quantify endospores in up to
20 m long sediment cores collected from a tidal flat
area near Spiekeroog Island, NW Germany, as well
as in several sediment samples from ODP Leg 201.
DPA contents were determined fluorimetrically using
a highly sensitive post-column complexation HPLC
approach [6]. DPA contents ranged from 0.004 to
1.7 nmol DPA g -1 sediment dry weight, corresponding
to 1.6 × 10 4 to 7.7 × 10 6 spores g -1 sediment dry
weight (Fig. 1). For conversion of dipicolinic acid
contents into endospore numbers an average DPA
content of 2.24 × 10 -16 mol per endospore was
assumed. The endospore depth profiles of the tidal
flat sediments were non-linear, but reflected the
vertical changes in lithology. The highest endospore
numbers were found in muddy samples, while
significantly lower numbers were detected in sandy
Janssand
ODP-Proben
sediments. The contribution of endospore numbers to
total cell counts increased with sediment depth
reaching up to 10 % of total cell counts in the deepest
layer. In sediment samples from Leg 201 the
contribution of endospores to total cell numbers is
even higher, ranging from 3 to 19 %. The relative
increase of endospore contribution to total cell
numbers with sediment age is explained by the
longevity of endospores, whereas numbers of
vegetative cells are expected to decrease more
rapidly due to starvation (Fig. 1).
References
[1] Whelan et al., 1986. Initial Reports of the Deep
Sea Drilling Project 96, 6578-6583.
[2] Parkes et al., 1994. Nature 371, 410-413.
[3] Roussel et al., 2008. Science 320, 1046.
[4] Whitman et al., 1998. Proceedings of the
National Academy of Sciences of the USA 95,
6578-6583.
[5] Parkes et al., 2000. Hydrogeology Journal 8, 11-
28.
[6] Fichtel et al., 2007. Journal of Microbiological
Methods 70, 319-327.
566

P-441
Investigating relationships between OM and diatom frustules
and their implications in the export of organic carbon in the
ocean
Maxime Suroy 1 , Brivaëla Moriceau 2 , Madeleine Goutx 1
1 Laboratoire de Microbiologie, Géochimie et Ecologie Marines, Université de la Méditerranée, CNRS UMR
6117, Marseille, France, 2 Laboratoire des Sciences de l’Environnement Marin, CNRS, UMR 6539, Site du
technopôle Brest-Iroise, Plouzané, France (corresponding author:maxime.suroy@univmed.fr)
One of the major processes of the biological carbon
pump (BCP) is the colloquially known ―ballasting‖ that
involves the association of mineral ballast with sinking
particles. Those minerals increase the density of
particles and the settling velocity leading to a
temporary or permanent sequestration of carbon into
the deep ocean. Among those minerals, three have
important role in ballasting because of their
concentrations and their abundance. These minerals
are biogenic silica, calcium carbonate and lithogenic
silica. The weak relationships between organic carbon
and biogenic silica at 1800m depth have led many
authors to hypothesize a lowest carrying capacity for
the biogenic silica of frustules compared to the
calcium carbonate of coccoliths. To understand
relationships between phytoplanktonic organic matter
(OM) and silica, at first, we conducted a degradation
experiment of a Thalassiosira weissflogii culture.
During 21 days, we measured lipid classes, sugars,
biogenic (BSi) and dissolved silica (DSi), and) for
modelling relationships between OM and BSi under
two growth conditions. A model taking into account 2
phases of silica with different polymerization degrees
(M3) gave a better fit with the BSi dissolution and
could explain the shape of some sugars and lipids
degradation curves.
Fig1. BSi dissolution rate of a degradation experiment
of a diatom culture and 2 model curves with one
phase (M1) or two phase of BSi (M3).
In a second step, we developed a method to identify
lipids within frustules. Indeed, proteins and
carbohydrates have been extensively studied in
diatom frustules showing molecular bindings between
some molecular species and silica phases into the
frustule. Lipid content of frustules is far less
understood. (Kates and Volcani, 1968) [1]. More
recently, Tesson et al (2008) [2] using X-Ray
photoelectron spectroscopy and Soler et al (in review)
[3] using FTIR reported the presence of lipids within
the frustule. Though these methods use the same first
steps (a separation of the frustule and the protoplast
using differential centrifugation after a vigorous
sonication [1,4]), they cannot identify the OM at the
molecular level and especially lipids. The assessment
of OM quality embedded within the frustule requires
the dissolution of this frustule and, therefore,
denaturing conditions. Kröger et al (1997) [4] have
developed a method to isolate a new family of
proteins using hydrofluoric acid (HF) which dissolve
the frustule after isolation. We will present a
development of this method applied to lipid analysis
by GC/MS. and will discuss its ability to bring new
insight into the lipid content of the diatom frustule and
to decipher the role of the interactions between
organic carbon and biogenic silica in the BCP.
[1] M. Kates, B. E. Volcani, Zeitschrift
Pflanzenphysiol. 1968, 60, 19.
[2] B. Tesson, M. J. Genet, V. Fernandez, S. Degand,
P. G Rouxhet and V. Martin-Jézéquel. 2009.
ChemBioChem. 10: 2011–2024
[3] C. Soler, B. Moriceau, C. Amiel, M. Goutx, O.
Ragueneau, P. Claquin. In review.
[4] N. Kröger N. Kröger, G. Lehmann, R. Rachel, M.
Sumper. 1997. Eur.J. Biochem. 250, 99.
567

P-442
Deep-sea benthic archaea recycle relic membrane lipids: insight
from ―in situ 13C-incubation experiment‖ and its lipidomics
Yoshinori Takano 1 , Yoshito Chikaraishi 1 , Nana O. Ogawa 1 , Hidetaka Nomaki 1 , Yuki
Morono 2 , Fumio Inagaki 2 , Kai-Uwe Hinrichs 3 , Nao Ohkouchi 1
1 Japan Agency for Marine-Earth Science & Technology (JAMSTEC), Yokosuka, Japan, 2 Kochi Inst. Core
Research, JAMSTEC, Kochi, Japan, 3 MARUM & Dept. Geosciences, University of Bremen, Bremen,
Germany (corresponding author:takano@jamstec.go.jp)
Introduction
Deep-sea sediments harbour a vast and unusual
biosphere with as yet undetermined importance in the
global carbon cycle. Carbon isotopic signatures of
archaeal intact polar lipids from sediments dominated
by benthic archaeal communities indicate utilization of
sedimentary organic carbon [1]. Since most benthic
archaea are viable but non-culturable microbes and
difficult to study in the laboratory [2], we conducted in
situ 13 C-tracer experiments to determine the metabolic
activity, especially for deep-sea benthic archaea
focused on the biogeochemical processes of specific
membrane lipids.
Experimental
In situ 13 C-tracer experiments during 0-405 days were
performed with the incubation chamber [3] operated
by ROV Hyper-Dolphin and its mother research
vessel Natsushima at Sagami Bay, Japan (35˚00.7‘N,
139˚22.5‘E, depth 1,453 m). 13 C-labeled glucose
(99%, 13 C6H12O6: hereafter, G-n) or 13 C-Chlorella
(99%: ibid, C-n) were injected by the 5mL syringe
attached on the top. The incubation cores and a
reference core were recovered after 9 and 405 days
deployment. After in situ tracer experiments, archaeal
GDGTs (glycerol dialkyl glycerol tetraethers) were
extracted from the core samples and purified by
HPLC/APCI-MS combined with a fraction collector
(Agilent 1100) for compound-specific carbon isotopic
analyses of GDGTs. After ether-bond cleavage
treatment, the intramolecular carbon isotopic
compositions of each isoprenoid (biphytanes; BP[0],
BP[2], BP[3]) and their 2,3-sn-glycerols were also
directly measured by online GC/C/IRMS [4].
Results and Discussion
We found that the 13 C was peculiarly enriched into the
2,3-sn-glycerol backbone (< 2200‰ in G-405; <
3020‰ in C-9) of archaeal membranes during 405
days, while the isoprenoid chain of the membranes
remained unlabelled (i.e., natural abundance). 16S
rRNA and quantitative PCR (qPCR) analysis indicated
a community shift in the composition of the benthic
archaeal community and its abundance (10 5 -10 7
copies g-sed -1 ) during the course of the experiment,
whereas the relative abundances (%) of archaeal
GDGT compositions were almost constant during 405
days. On the basis of the differential uptake of 13 Ctracer,
we suggest that only the glycerol unit is
synthesized de novo, whereas the isoprenoid unit is
recycled from relic archaeal membranes and detritus,
because of the prevalence of these compounds in
marine sediments. We therefore suggest that benthic
archaea build their membranes by recycling
sedimentary relic membrane lipids in order to
minimize the energy expenditure for de novo lipid
synthesis.
References
[1] Biddle, J.F. et al. (2006) PNAS, 103, 3846-3851.
[2] Teske, A. & Sorensen, K.B. (2008) ISME Journal,
2, 3-18. [3] Nomaki, H. et al. (2006) Mar. Ecol. Prog
Ser., 310, 95-108. [4] Takano et al. (2010) Nature
Geosci., 3, 858-861.
Figure 1 Carbon isotopic compositions of
caldarchaeol, crenarchaeol and its intramolecular
moieties (2,3-sn-glycerol and biphytanes: ‰ PDB
scale) at core top section (0-1cm) by in situ 13 Cglucose
experiments during 405 days.
568

P-443
Hopanoids in silica sinters: identification of an unusual pathway
in hopanoid diagenesis with implications for the sedimentary
biomarker record
Robert Gibson 1,2 , Gurpreet Kaur 3 , Bruce Mountain 4 , Richard Pancost 3 , Helen Talbot 2
1 NIOZ Royal Netherlands Institute for Sea Research, 't Horntje, Netherlands, 2 Newcastle University,
Newcastle, United Kingdom, 3 Bristol University, Bristol, United Kingdom, 4 GNS Science, Taupo, New
Zealand (corresponding author:Robert.gibson@nioz.nl)
Geohopanoids, i.e. geohopanols, hopanes,
hopenes and hopanoic acids, are the molecular
fossils of bacteriohopanepolyols (BHPs) that are
produced by a diverse array of bacteria and are
widespread throughout modern and ancient
sedimentary depositions. Previously, we have shown
that BHPs are produced by bacteria that colonise
terrestrial geothermal vents and BHPs are well
preserved in silica sinters collected from the Taupo
Volcanic Zone, North Island, New Zealand (TVZ)[1].
In this study we have analysed the geohopanoid
composition of geothermal silica sinters from the TVZ
with a view to understanding mechanisms of
diagenesis affecting preserved BHPs and to assess
the potential of geohopanoids as biomarkers in
ancient geothermal siliceous deposits.
Throughout our investigations, a high proportion of
C31 �� hopanol relative to C32 or C30 �� hopanols was
observed. This is in stark contrast to studies of the
distribution of geohopanoids from other depositional
settings where C32 hopanol tends to predominate.
Previously, it has been suggested that the formation
of homohopanols is directly related to the degree of
functionalisation in precursor BHPs [2]. However, in
our study this is not the case as C31 �� hopanol,
which would be expected to derive from
pentafunctionalised BHPs, is the most abundant
geohopanol but pentafunctionalised BHPs do not
dominate the BHP distribution to the same extent,
(Figure 1).
Hopanoic acids dominate distributions in older
sinters and were found to closely-mirror BHP
distributions. However, hopanoic acids were less
prevalent in sinters deposited under acidic conditions.
This may reflect reduction of the acid functionality to a
terminal hydroxyl group leading to the observed
predominance of geohopanols in sinters from acidic
vents.
This investigation has highlighted a unique
mechanism of BHP diagenesis that is significantly
controlled by environmental setting and not, as
previously assumed, entirely based on biological
input. Furthermore, geohopanoids appear to be well
preserved in older sinters suggesting that hopanoids
may be useful biomarkers in ancient siliceous sinter
material.
1
0.8
0.6
0.4
0.2
0
1
0.8
0.6
0.4
0.2
0
‘Active’ C 31/(C31+C32) hopanol index
P/(T+P) BHP index
‘Non-active, older’
Figure 1. Relative distributions of bio- and
geohopanoids observed in active sinters (above) and
non-active sinters (below). Sample codes: CP -
Champagne Pool; LR - Loop Road; OP - Opaheke
Pool. C31/ C31+C32 hopanol index = ∑C31 ��+��+��
hopanol/(∑ C31 ��+��+�� hopanol + ∑ C32 ��+��+��
hopanol); P/(P+T) BHP index =[∑ pentafunctionalised
BHPs/(∑ tetrafunctionalised BHPs + ∑
pentafunctionalised BHPs)].
[1] Gibson R.A., Talbot, H.M., Kaur, G., Pancost,
R.D., Mountain, B.W., 2008. Organic geochemistry
39, 1020, 1023
[2] Farrimond, P., Head, I.M., Innes, H.E., 2000.
Geochimica et Cosmochimica Acta 64, 2985 – 2992.
569

P-444
Isolating and cultivating environmentally relevant microorganisms
as reference point for linking phylogeny to activity in
situ based on biomarker lipids
Marcel van der Meer 1 , Christian Klatt 2 , Jason Wood 2 , Donald Bryant 4 , Mary Bateson 2 ,
Laurens Lammerts 1 , Stefan Schouten 1 , Jaap Sinninghe Damste 1 , Michael Madigan 3 ,
David Ward 2
1 NIOZ Royal Netherlands Institute for Sea Research, Den Burg, Netherlands, 2 Montana State University,
Bozeman, United States of America, 3 Southern Illinois University, Carbondale, United States of America,
4 The Pennsylvania State University, University Park, United States of America (corresponding
author:Marcel.van.der.Meer@nioz.nl)
Biomarker lipids and their stable carbon
isotope ratios, both natural abundance and from
labelling studies, have been a useful tool in linking
activity to phylogeny in situ. However, the
interpretation of the sources of biomarker lipids in
natural environments is strongly relying on culturebased
information and cultivated isolates are often not
representative of the micro-organisms actual present
in the environment, according to molecular
microbiology studies.
For example, in the past we have made
inferences about the activity of green nonsulfur
bacteria present in hot spring microbial mats based
on the stable carbon isotope ratios of C30-C35 wax
esters found in hot spring microbial mats (1). Similar,
but not identical, wax ester distributions had been
reported for cultivated Chloroflexus spp. (2). However,
phylogenetic analysis of especially the microbial mats
in low sulfide systems indicated that Chloroflexus spp.
only form a very small fraction of the green nonsulfur
bacteria in situ (3). The closest cultivated relative of
the majority of the green nonsulfur bacteria in these
mats is Roseiflexus castenholzii (4), an organism that
produces completely different wax esters than those
found the Yellowstone hot spring microbial mats (5).
This raises the question how valid the inferences are
based on biomarker distributions of green nonsulfur
bacteria that are only a minor component of the
microbial mat.
In this study we were able to isolate and
cultivate Roseiflexus spp. strains from a microbial mat
of an alkaline siliceous hot spring in Yellowstone
National Park. These strains are genetically closely
related to predominant green nonsulfur bacteria found
in the mat, as judged by the high similarity of smallsubunit
rRNA, and genomic and metagenomic
sequences. Like R. castenholzii, the Yellowstone
isolates contain bacteriochlorophyll a, but not
bacteriochlorophyll c or chlorosomes, and grow
photoheterotrophically or chemoheterotrophically
under dark aerobic conditions. The genome of one
isolate, Roseiflexus sp. strain RS1 contains genes
necessary to support these metabolisms. This
genome also contains genes encoding the 3hydroxypropionate
pathway for CO2 fixation and a
hydrogenase, which might enable photoautotrophic
metabolism, even though neither isolate could be
grown photoautotrophically with H2 or H2S as a
possible electron donor. The isolates exhibit
temperature, pH, and sulfide preferences typical of
their habitat. Importantly, the wax esters produced by
these isolates, C30-C35 straight and iso-branched,
match much better with those found in the
Yellowstone mats than wax esters produced by R.
castenholzii or Chloroflexus isolates (see Fig.1).
Our study thus shows that there is a need for
environmentally relevant microbial isolates as
reference organisms for molecular and lipid
biomarkers studies in linking phylogeny to activity.
1. M. T. J. van der Meer, S. Schouten, J. W. de
Leeuw, D. M. Ward, Env. Microbiol. 2, 428 (2000).
2. J. Shiea, S. C. Brassell, D. M. Ward, Org.
Geochem. 17, 309 (1991).
3. U. Nübel, M. M. Bateson, V. Vandieken, M. Kühl,
D. M. Ward, Appl. Environ. Microbiol. 68, 4593
(2002).
4. S. Hanada, S. Takaichi, K. Matsuura, K. Nakamura,
Int. J. Syst. Evol. Microbiol. 52, 187 (2002).
5. M. T. J. van der Meer et al., Arch. Microbiol. 178,
229 (2002)
570

P-445
The influence of geological and geochemical processes on
microbial biogeography at hydrothermal vents on the Mid-
Atlantic Ridge: evidence from the distribution of intact polar
lipids
Robert Gibson 1 , Marcel van der Meer 1 , Ellen Hopmans 1 , Anna-Louise Reysenbach 2 ,
Stefan Schouten 1 , Jaap Sinninghe Damsté 1
1 NIOZ Royal Netherlands Institute for Sea Research, 't Horntje, Netherlands, 2 Department of Biology,
Portland State University, Portland, United States of America (corresponding author:Robert.gibson@nioz.nl)
Hyperthermophilic microbes are known to
occupy the deepest branches of the 16s rRNA gene
based universal tree of life. Thus, microbial
communities associated with modern deep-sea
hydrothermal vents likely closely resemble the life
which occupied the early Earth. However, the factors
that affect the distribution and diversity of microbial
communities in modern hydrothermal settings are not
well constrained. Important questions such as what
effect does fluid chemistry have on microbial
populations and who are the key players in each
particular setting have yet to be addressed. In an
attempt to answer some of these questions, we have
investigated the intact polar lipid (IPL) composition of
twelve vent deposits from two distinct hydrothermal
vent fields located on the Mid-Atlantic Ridge (MAR).
The two locations investigated are the ‗Rainbow‘
hydrothermal vent field (RHF), an ultra-mafic system
characterised by high-temperature vent fluids (up to
365 0 C), which contain large amounts of hydrogen,
methane and other reduced carbon compounds. The
second location is the ‗Lucky Strike‘ hydrothermal
vent field (LSHF), a basalt-hosted system where vent
fluids reach up to 300 0 C and contain relatively high
amounts of H2S but lower methane and much lower
hydrogen than RHF.
Analysis of vent material from both RHF and
LSHF showed large difference in the abundance of
lipids produced by Archaea and Bacteria (Figure 1). In
the RHF samples approximately 50% of the IPLs are
from Archaeal origin, while in LSHF this is usually less
than 10%. One other clear difference between the two
vent fields is that vent deposits from RHF contain a
predominance of IPLs with archaeol and macrocyclic
archaeol core lipids, which are absent in vent material
from the LSHF.
The results of the IPL analysis are in good
agreement with those of molecular analysis of the
same samples by 454 pyrosequencing of the
hypervariable V4 region of Archaeal rRNA genes.
Members of the Methanocaldococcaceae and
Methanococcaceae were identified as important
community members in RHF, but were absent in
LSHF (Flores et al., unpublished data). The presence
of Methanocaldococcaceae, Methanococcaceae and
macrocyclic archaeol IPLs in RHF and absence in
LSHF seems to be directly linked to the hydrogen
availability at both vent fields.
Bacterial IPLs containing PE, PG and PC
headgroups were also identified and likely derive from
members of the epsilonproteobacteria, which are
known to be prevalent in hydrothermal settings.
The general matching of IPL composition
with those of community diversity studies of RHF and
LSHF (Flores et al., unpublished data) suggest IPLs
are applicable as live markers in these environmental
settings and provide complimentary information to
studies of microbial communities.
RHF
LSHF
1
3
5
6
7
8
9
11
12
0 20 40
% composition
60 80 100
Archaeal IPLs Bacterial IPLs IPLs of unknown origin
Figure 1. IPL composition, based on total peak
response area, of MAR vent deposits as percentage
of total identifiable IPLs. Three samples (2, 4 and 10)
did not contain any identifiable IPLs.
571

P-446
Distribution of ammonia-oxidizing archaea and anammox
bacteria in the Arabian Sea OMZ using a combined approach
based on intact polar lipids and abundance/expression of
specific genes
Laura Villanueva, Angela Pitcher, Ellen Hopmans, Stefan Schouten, Jaap Sinninghe
Damsté
Royal Netherlands Institute for Sea Research, Den Burg, Texel, Netherlands (corresponding
author:laura.villanueva@nioz.nl)
Oxygen Minimum zones (OMZs) play a critical role in
the marine microbial community structuring and global
biochemical cycles [1]. Two microbial groups
inhabiting OMZs are receiving special attention
because of their role in the marine carbon and
nitrogen cycles: Anammox Bacteria and ammoniaoxidizing
Archaea (AOA, Thaumarchaeota). AOA
oxidize ammonia aerobically to nitrite by the ammonia
monooxygenase enzyme (amoA) and they play a
major role in oceanic nitrification due to their high
affinity for ammonia [2]. Anammox Bacteria display an
chemoautotrophic metabolism combining ammonia
and nitrite to form N2 (N-loss to the atmosphere) [3].
Both groups of microbes also produce specific
biomarker lipids, i.e. AOA produce crenarchaeol while
anammox Bacteria produce ladderane lipids. Previous
studies have suggested that AOA and nitrifiers can
provide nitrite for anammox Bacteria. However, little is
known about their distribution and interaction.
In this study, we investigated the distribution,
abundance and activity of AOA and anammox
Bacteria in the OMZ of the Arabian Sea. We applied a
combined approach based on quantification of both
intact polar lipids (IPLs) and DNA/RNA (functional)
genes. IPLs consist of the core membrane lipids still
covalently linked to polar head groups which are
relatively labile, and thus represent lipids synthesized
by living, or recently living cells. We used a newly
developed HPLC/MS 2 method to target AOA-specific
crenarchaeol IPLs as well as a previously published
method targeting C20-[3]-monoether ladderane lipid
with a phosphatidylcholine headgroup (PC-monoether
ladderane) specific for anammox Bacteria. Targeting
genes at the level of DNA (16S rDNA gene and
metabolic genes such as AOA amoA gene and
hydrazine oxidoreductase (hzo) anammox) provided
information on the abundance and metabolic activity
of these microbial groups. The results showed that
hexose-phosphohexose (HPH)-crenarchaeol showed
a substantial increase from the surface waters with a
maximum relative abundance at 170 m depth, which
was coincident with copy numbers and expression
(RNA) of thaumarchaeotal 16S rDNA and amoA
genes. On the contrary, lowest values of AOA genes
and IPLs were detected in the core of the OMZ (600–
750 m) where oxygen concentrations are minimal.
Anammox bacterial markers (PC-monoether
ladderane, 16S rRNA anammox and hzo gene) covaried
well throughout the water column and, in
contrast to AOA, maximum abundances were
observed in the core of the OMZ.
Our results thus show that specific phospholipids can
be excellent tracers of active anammox bacteria and
AOA. The occurrence of HPH-crenarchaeol in all AOA
samples screened to date, the labile nature of the
phosphate-ester bond, and the correlation with
nucleic acid-based profiles, render HPH-crenarchaeol
as the most fitting biomarker to track living AOA in
comparison with hexose-based IPLs. Furthermore,
our findings indicate that the distribution and activity
of anammox Bacteria is concentrated at the core of
the OMZ, which can be an indication of their
importance in removing nitrogen in anoxic waters.
Although AOA could theoretically provide substrates
for anammox and thus occupy similar niches, our
results indicate that this is not the case evidenced by
the large vertical segregation (>400 m) of their niches.
Ref: [1] Diaz & Rosenberg (2008) Science 321:926.
[2] Arrigo (2005) Nature 437:349. [3] Kuypers et al
(2003) Nature 422:608. [4] This work published :
Pitcher et al. (2011) ISME Journal
572

P-447
The vertical niche of Thaumarchaota in Lake Malawi;
implications for the TEX86 temperature signal in the sediment
Martijn Woltering 1 , Josef Werne 2 , Melissa Berke 1 , Ellen Hopmans 3 , Jaap Sinninghe
Damsté 3,4 , Stefan Schouten 3,4
1 University of Minnesota, Duluth, United States of America, 2 University of Minnesota Duluth, Duluth, United
States of America, 3 Royal Netherlands Institute for Sea Research, Texel, Netherlands, 4 Utrecht University,
Utrecht, Netherlands (corresponding author:wolte082@umn.edu)
Previous studies applied the TEX86 paleo temperature
proxy to sediment archives from Lake Malawi to
produce records of past temperature variability that
spanned the Holocene to middle Pleistocene time
periods (Powers et al., 2005 Science; Powers et al.,
p 3 in press ;Woltering et al., p 3 in press). Based on the
observation that core top sample yielded
temperatures in the range of annual mean lake
surface temperatures (LST) and that trends of TEX86
values down core appear to capture well documented
global climate events, these previous studies
interpreted TEX86 as reflecting annual mean surface
water temperature. However, there is no information
on the ecology of the Group 1 Crenarchaeota (now
named Thaumarchaeota) in the water column of Lake
Malawi to test the hypothesis that TEX86 values from
the sediments represent an annual mean LST. Here
we present data from a study of suspended
particulate matter (SPM) in the water column of the
north, central and south basins of Lake Malawi during
the austral summer (wet season) that investigated the
vertical niche of Thaumarchaeotal production. SPM
was extracted and analysed to produce vertical
profiles of core and specific intact Thaumarchaeotal
glycerol dialkyl glycerol tetraether (GDGT) membrane
lipid abundances. The intact crenarchaeol-hexosephosphohexose
lipid (HPH crenarchaeol) has low
abundances in the warm surface water layer and a
maximum in abundance at 50m depth, beneath the
chlorophyll maximum at the base of the thermocline,
and declining abundance with depth. Profiles of other
intact crenarchaeol lipids: crenarchaeol di-hexose,
crenarchaeol hexose and crenarchaeol hexose ‗180‘
differ from the profile of HPH crenarchaeol with
maxima at greater depths suggesting that these lipids
may be degradation products of HPH crenarchaeol
and crenarchaeol di-hexose and thus may not be
ideal markers for living Thaumarchaeota (cf.
Schouten et al., 2010).
TEX86 derived temperatures from SPM from the
epilimnion are significantly lower than the actual
surface water temperature. At 50m depth there is
good agreement between TEX86 temperature and the
in situ water temperature. Between 50-150m there is
a distinct trend (5-6 o C) of increasing TEX86
temperature with increasing depth, while between
depths of 150-300 TEX86 temperatures show a similar
decrease in TEX86 temperature to 300m, where
values were close to those observed at 50m depth.
This pattern of increase and subsequent decrease of
TEX86 temperatures may be caused by a potential
difference in degradation rate as well as in situ
production of different intact GDGTs in the water
column yielding different ratios of core GDGTs, thus
affecting the TEX86. Our observation that at the time
of sampling Thaumarchaeota predominantly live at
~50m water depth would mean that the TEX86 signal
produced does not capture the epilimnetic water
temperatures during this warmest part of the year,
and therefore the TEX86 signal in the sediments may
underestimate the temperature relative to the annual
mean LST. However, our sampling took place during
the austral summer which is characterized by a
shallow thermocline due to diminished wind activity
over the lake during this season. The dry season,
however, is characterized by windy conditions with
strong winds coming from the north, which can mix
surface waters down to 200m. The deepening of the
thermocline during the windy season likely results in
that isoprenoid GDGTs at this time are being
produced in the epilimnion and are therefore could
reflect surface water temperature. This would explain
why the TEX86 derived temperature from a core top
sediment from the study site yields temperatures that
are lower than the summer surface water
temperature, but higher that the hypolimnetic water
temperature. This may also explain why Powers et al.
(p 3 in press) observed that although absolute TEX86
derived temperatures from a shallow sediment core
from Lake Malawi agree well with instrumental
summer water temperatures, the TEX86 trend down
core corresponds more with the trend of the winter
surface water instrumental record.
An investigation of sinking particles over an annual
cycle for TEX86 in Lake Malawi may provide a more
definitive insight on actual temperature reflected by
the TEX86 proxy in the sediments of Lake Malawi.
573

P-448
Genetic and metabolic characterization of methanogen microbial
communities in the Antrim gas shale formation
Cornelia Wuchter 1 , Erin Banning 1 , Nick Drenzek 2 , Marco Coolen 1
1 Woods Hole Oceanogaphic Institution, Marine Chemistry and Geochemistry Department, Woods Hole, MA
02540, United States of America, 2 Schlumberger-Doll Research, Cambridge, MA 02139, United States of
America (corresponding author:c_wuchter@hotmail.com)
Geochemical evidence from the Antrim Shale
(Michigan, USA) indicates that a significant portion of
the economically relevant quantities of natural gas
currently in production has been generated by
microbial methanogenesis over the late Pleistocene
[1]. These biogenic gas deposits are located near the
basin margins where the shale source rock is laden
with organic matter of low thermal maturity and
infiltrated by fresh water flow through a relatively
permeable fracture network [1]. The goal of this study
was to further investigate methanogen community
structure, biogeochemical cycling, and environmental
sensitivity in an effort to enhance formation evaluation
and well completion design.
A 40 m long core was retrieved from the margin of the
Antrim basin and subsampled into sterile desorption
canisters at ten depth horizons corresponding to
distinct lithological and historical gas production units.
Aliquots were subsequently pulverized under an inert
atmosphere and used to initiate incubations with an
array of known methanogen or fermentative bacteria
substrates. Phylogenetic analyses of PCR amplified
core and incubation extracts were also performed by
denatured gradient gel electrophoresis.
Headspace gas analysis of the incubation bottles
revealed substantial methane generation rates at four
different depths that generally correspond to more
organic carbon rich core sections. Interestingly, direct
methane production was stimulated by a typical
methanogen substrate (acetate) at only one depth,
with the other three responding indirectly to the
addition of fermenting bacteria substrates (bitumen,
glucose and yeast extract). Bacterial and archeal 16S
rRNA genes recovered from the incubation bottles
and subsequently DNA fingerprinted revealed a
correspondingly diverse microbial population. Similar
findings have been reported for methanogenic
consortia from a variety of terrestrial and coastal
habitats that can only be isolated after enrichment in a
fermenting co-culture, implying that the hydrogenproducing
fermenting bacterium provides the
methanogenic substrate at low, environmentally
relevant levels [2]. Combined, these results suggest
that biogenic shale gas generation is likewise reliant
on low substrate fluxes provided by fermenting
bacteria. Further research is now underway to isolate
both fermenting bacteria and methanogenic archaea
from the shale formation and constrain the kinetics of
stimulated methane production from gas shale
communities.
References:
[1] Martini et al., 2003. AAPG 87 (8), 1355-1375.
[2] Sakai et al., 2007. AEM doi:10.1128/AEM.03008-
06, 4326-4331.
574

P-449
Glycerol dialkyl glycerol tetraethers and the TEX86 index in
sinking particles in the western North Pacific
Masanobu Yamamoto 1 , Yuichiro Tanaka 2 , Akifumi Shimamoto 3
1 Hokkaido University, Sapporo, Japan, 2 Geological Survey of Japan, AIST, Tsukuba, Japan, 3 the General
Environmental Technos, Osaka, Japan (corresponding author:myama@ees.hokudai.ac.jp)
Seasonal and depth variations in the flux of
glycerol dialkyl glycerol tetraethers (GDGTs) and the
TEX86 values in sinking particles were examined
using a 21-month time-series sediment trap
experiment at a mooring station WCT-2 (39°N, 147°E)
in the mid-latitude NW Pacific to understand the
delivery process of GDGTs produced in surface water
to the deeper water column. A study of the same trap
samples was conducted for alkenones and U K 37‘
(Yamamoto et al., 2007), and we tried to understand
the behavior of GDGTs by comparing with that of
alkenones. Lateral advection of particles is negligible
at the study site (Yamamoto et al., 2007).
Alkenone sinking flux and U K 37‘–based
temperature showed strong seasonal variability. The
variations at three different depths were synchronous.
Alkenone fluxes were higher from spring to fall than
they were from fall to spring. During periods of high
alkenone flux, the U K 37‘–based temperatures were
lower than the contemporary SSTs, suggesting
alkenone production in a well-developed thermocline
(shallower than 30m). During low alkenone flux
periods, the U K 37‘–based temperatures were nearly
constant and were higher than the contemporary
SSTs, suggesting that fresh and labile particles sank
from spring to fall, while old and stable particles sank
from fall to spring (Yamamoto et al., 2007).
Isoprenoid GDGT sinking flux showed strong
temporal variability at the shallow traps (~1300 m),
whilst the fluxes at the deeper traps (~2500–4800 m)
did not vary in harmony with that at the shallow trap.
In contrast to U K 37‘, TEX86 did not show seasonal
variability. The average value of TEX86 corresponds to
the sea surface temperature in cooler seasons. The
sinking flux of isoprenoid GDGTs decreased with
increasing depth. The half depth, the depth interval in
which sinking flux becomes half, of total isoprenoid
GDGTs is ~3100 m, which is higher than that of
alkenones (~1700 m). The sinking fluxes of isoprenoid
GDGTs showed a good correlation with those of
organic carbon. The TEX86 values in sinking particles
at all depths were nearly identical and correspond to
sea surface temperatures.
These results suggest that the GDGTs
produced in surface water are suspended and
homogenized over annual cycles in the uppermost
water column and delivered to the deeper water
column along with the bulk organic particles. TEX86
values are stable during vertical transportation. The
above delivery mechanism is consistent with that
proposed by Wuchter et al. (2005). We also suggest
that isoprenoid GDGTs are relatively stable
(Yamamoto and Polyak, 2009), in contrast to a
suggestion by previous studies on the stability of
GDGTs, and they are preserved in oxic surface water
in a certain period, at least more than one year.
References
Wuchter, C., Schouten, S., Wakeham, S.G., Sinninghe
Damsté, J.S., 2005. Temporal and spatial variation
in tetraether membrane lipids of marine
Crenarchaeota in particulate organic matter:
Implications for TEX86 paleothermometry.
Paleoceanography, 20, PA3013.
Yamamoto, M., Shimamoto, A., Fukuhara, T.,
Naraoka, H., Tanaka, Y., Nishimura, A., 2007.
Seasonal and depth variations in molecular and
isotopic alkenone composition of sinking particles
from the western North Pacific. Deep-Sea
Research Part I, 54, 1571-1592.
Yamamoto,M., Polyak, L., 2009. Changes in
terrestrial organic matter input to the Mendeleev
Ridge, western Arctic Ocean, during the Late
Quaternary. Global and Planetary Change, 68, 30–
37.
575

P-450
Proxies based on archaeal and bacterial GDGTs in surface
sediments of the Yangtze River Estuary, China: implications for
marine organic biogeochemistry
Peng Yao 1,2,3 , Brendan Keely 3 , Zhigang Yu 1,2 , Hongzhen Yin 1 , Meixun Zhao 1,2
1 Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, China, Qingdao, China,
2 Institute of Marine Organic Geochemistry, College of Chemistry and Chemical Engineering, Ocean
University of China, Qingdao, China, 3 Department of Chemistry, University of York, UK, York, United
Kingdom (corresponding author:yaopeng@ouc.edu.cn)
Glycerol dialkyl glycerol tetraethers (GDGTs) are
derived from archaeal and bacterial membrane lipids,
which occur ubiquitously in aquatic environments and
soils (Rueda et al., 2009). In recent years, proxies
based on GDGTs, such as TEX86, BIT, MBT/CBT
have been used successfully to reconstruct past sea
surface temperature (SST), continental mean annual
air temperature (MAT) and soil pH changes, and to
determine the relative inputs of fluvial soil organic
matter (OM) in marine environments [1] .
In China, similar studies are few, though the
importance of such studies has been recognized and
preliminary studies in lake sediments have been
conducted
[2] . The determinations of GDGTs in
China‘s estuaries and coastal environments, however,
have not been performed.
As the third largest river in the world (~6300 km in
length), the Yangtze River is of particular interest to
biogeochemists and organic geochemists because of
its high water runoff and sediment discharge. In
recent years, frequent harmful algal blooms and
increasing hypoxia area within the Yangtze River
Estuary (YRE) and its adjacent sea areas further
highlight the importance of studies in this estuary [3, 4] .
Therefore, comprehensive studies of marine organic
biogeochemistry in such an estuary are very
important and meaningful.
Here, we report GDGTs in surface sediments
collected from the upper YRE to the inner-shelf of the
East China Sea (ECS) in order to establish the
suitability of the use of the TEX86, BIT, MBT and CBT
proxies in this area. This is the first large scale test
case to validate the applicability of these novel
molecular proxies in China‘s seas and estuaries.
The high BIT values in upper estuary and river
mouth sediments, and further offshore, decrease
rapidly seaward, indicative of soil OM transport from
the upper estuarine regions.
Reconstructed SST values of samples from the
inner-shelf of the ECS, where marine OM dominates
relative to soil OM, compare well with multi-year
average SST obtained from historical records. By
contrast, the river mouth area, which has high BIT
values high sedimentary OM contents and high
deposition rate, is suitable for studies of historical
changes in river flow and soil OM contributions.
The distributions of branched GDGT-based MAT
and soil pH at the YRE are characterized by low
values at river mouth area, gradually increasing
seaward. The distribution differences of MAT and soil
pH could be caused by several factors, such as
differences in the deposition rates of sediments, in
situ production and selective degradation of GDGTs.
The high OM content and deposition rate of
sediments make the river mouth area a better place to
obtain a high resolution reconstructions of MAT and
soil pH for the Yangtze River drainage basin.
References
[1] Weijers et al., 2009. Geochimica et Cosmochimica Acta
73, 119–132.
[2] Yao et al., 2010. Advances in Earth Science 25, 474-483.
[3] Chen et al., 2007. Marine Environmental Research 64,
399–408.
[4] Li et al., 2010. Harmful Algae 9, 531–539.
576

P-451
Methane fluxes modulating the molecular and carbon isotopic
composition of microbial lipids in gas hydrate bearing
sediments from the northern Cascadia margin
Marcos Yukio Yoshinaga 1 , John W. Pohlman 2 , Tobias Goldhammer 1 , Nadine Broda 1 ,
Michael Riedel 3 , Marcus Elvert 1 , Kai-Uwe Hinrichs 1
1 MARUM, University of Bremen, Bremen, Germany, 2 U.S. Geological Survey, Woods Hole Science Center,
Woods Hole, MA, United States of America, 3 Geological Survey of Canada, Sydney, BC, Canada
(corresponding author:marcosyukio@gmail.com)
A consortium of methane oxidizing archaea and
sulfate reducing bacteria critically regulates the flux of
methane between marine sediments and the oceans.
The process, known as the anaerobic oxidation of
methane (AOM), occurs within the sulfate-methane
transition (SMT)[1]. Under methane flux conditions
typical of most continental margins, AOM consumes
virtually all methane migrating to the seafloor.
However, at gas hydrate-bearing seeps and other
seep types (e.g., mud volcanoes[2]), the methane flux
often overwhelms the oxidative capacity of the AOM
consortium and passes into the water column. Seeps
presently emitting methane are analogs for largescale
methane releases that could be stimulated by
global warming. Understanding how the structure and
function of the AOM consortium responds to different
flux regimes at methane emitting seeps is crucial for
predicting how the marine methane cycle might be
affected by extreme environmental changes.
The objective of this study is to understand how
methane flux intensities and the sedimentary
microbial communities are spatially oriented around a
gas hydrate-bearing seep on the northern Cascadia
margin. We conducted detailed pore water
geochemical measurements in combination with
molecular and carbon isotopic analysis of intact polar
lipids (IPLs) in shallow subsurface sediments (ca. 5 m
depth).
The highest concentration and diversity of IPLs (a
proxy for the overall microbial diversity) occurred at
the SMT, with higher concentrations found in the
higher methane-flux core with the shallower SMT. In
general, the archaeal IPL concentration and diversity
was higher than the bacterial IPLs (Fig. 1). Bacterial
diether IPLs, likely derived from sulphate-reducing
bacteria, were found in high concentrations at the
SMT. The archaeal IPLs above and below the SMT
have mainly glycosyl (Gly) headgroups, while the
archaeal IPLs with phosphatidyl (Phos) headgroups
were concentrated near the SMT.
� 13 C values of archaeal and bacterial lipids were
more negative at the SMT than at the other horizons,
suggesting methane and/or CO2 assimilation [3].
Interestingly, in the SMT the � 13 C values of the
Phos-glyceroldialkylglyceroltetraethers (GDGTs) are
more negative than the Gly-GDGTs. This novel
intermolecular isotopic variation in archaeal lipids
suggests archaea with phosphatidyl headgroups are
more closely affiliated with AOM than those with
glycosyl headgroups, a conclusion supported by pore
water profiles that suggest uptake of phosphate at the
SMT.
Our results confirm that the methane flux into the
SMT is correlated with microbial biomass
accumulation. We also demonstrate that the flux
intensity influences the magnitude of isotopic lipid
fractionation, and that different microbial metabolisms
and communities may be differentiated by careful
analysis of the IPL structure.
Figure 1. Porewater profiles of methane, sulfate and
phosphate and selected IPLs groups concentrations at
Amnesiac Vent from the Northern Cascadia margin.
References
[1] Iversen, N. and Jorgensen,B.B. (1985) Limnol Oceanogr
30: 944-955.
[2] Niemann, H. et al. (2006) Nature 443: 854-858.
[3] Wegener, G. et al. (2008) Environ Microbiol 10: 2287-
2298.
577

P-453
Experimental palaeochemotaxonomy of conifers: the
Araucariaceae family
Yueming Lu, Yann Hautevelle, Raymond Michels
UMR7566 G2R, CNRS, Nancy Université, Vandoeuvre-lès-Nancy, France (corresponding
author:yueming.lu@g2r.uhp-nancy.fr)
Numerous studies of the molecular composition
of extant terrestrial plants pointed out the
chemotaxonomic value of a large assortment of
biological compounds. This means that these
biomolecules are synthesized by a restricted number
of taxa and can be used as specific biomarkers. Thus,
the distribution of vascular plant biomarkers
preserved in sedimentary material could serve as
proxy for terrestrial palaeoflora assessment.
Furthermore, as each flora is associated to more or
less precise climatic conditions, vascular plant
biomarkers may also serve as palaeoclimatic proxies.
However, our knowledge about
palaeochemotaxonomy of vascular plants is still
incomplete. Difficulties are related to 1) organic
diagenesis which may significantly modify the initial
molecular fingerprints; 2) the scarcity of well
preserved reference fossils; 3) the need to obtain a
collection of fossils covering all known species of
conifers. In order to help fill these gaps, we use an
experimental method based on artificial maturation of
extant plants by confined pyrolysis (Hautevelle et al.
2006). This technique allows to simulate conversion
of biomolecules into diagenetized compounds.
Within the 7 extant conifers families, we
investigated the palaeochemotaxonomy of
representatives of the Araucariaceae family. The aim
of this study are 1) to determine the
palaeochemotaxonomic signature common to all
Araucariaceae representatives, 2) to highlight the
molecular characteristics which should allow their
distinctions from other conifer families, 3) to evaluate
the inter- and intra-generic differences within the
Araucariaceae family.
12 species of Araucariaceae were selected.
They are well representative of the 3 extant genera:
Agathis (3 sp.), Araucaria (8 sp.) and Wollemia (1
sp.).
The result from GC-MS analysis shows that,
generally, the pyrolysates of Araucariaceae family are
characterized by a diversity of sesquiterpenoids and
diterpenoids. The sesquiterpanes are represented by
the cadalane group compounds (C15H18), bisabolane
isomers, and in some cases by farnesane. For the
aromatic sesquiterpenoids, the dominant compounds
are of the cadalene type (like calamenene, calamene
and cadalene), of the bisabolene type (like dihydro-arcurcumene)
and chamazulene. The distinction within
the different genera and species on the basis of the
sesquiterpenoids seems to be unlikely.
Concerning the aliphatic diterpenoids, all
families of Araucariaceae show a high abundance of
tetracyclic compounds, except those of Araucaria.
nemorosa and Agathis robusta. The tricyclic
compounds appear either alternatively to the
tetracyclic compounds, or sometimes co-exist (like
Araucaria bernieri, Araucaria bidwillii, Araucaria
laubenfelsii, Agathis australis). The bicyclic compound
like labdane is present in all species. Issues about the
significance of diterpenes are more complex because
of many unidentified compounds. Also tricyclic
compounds, like retene, 1,2,3,4-tetrahydroretene, 18-
and 19-norabieta-8,11,13-triene are common to all
species. Methyl-retene is also detected and shows a
relative lower abundance in some species.
Furthermore, the compounds having molecular mass
m/z 240 and 238 with a characteristic ion at m/z 169
and 168 respectively show a relative high abundance
in all species. No specific polar compounds could be
detected, except that of dehydroabietic acid.
The preliminary comparison of our results with
the occurrence of fossil Araucariaceae biomarkers are
in agreement with the few information described in the
literature: high abundance of tetracylic diterpanes and
lower abundance of tricyclic diterpanes. This feature
of Araucariaceae family could serve as a first criterion
to differentiate it from other conifer families.
Reference:
Hautevelle, Y., R. Michels, F. Lannuzel, F. Malartre,
and A. Trouiller (2006b), Confined pyrolysis of extant
land plants: A contribution to palaeochemotaxonomy,
Organic Geochemistry, 37(11), 1546-1561.
578

P-454
Tracing of palaeofloristic changes in the Paris basin (France)
during Jurassic: contribution of the retene/cadalene ratio
Yueming Lu, Yann Hautevelle, Raymond Michels
UMR7566 G2R, CNRS, Nancy Université Faculté des Sciences Boulevard des Aiguillettes BP 70239,
Vandoeuvre-lès-Nancy, France (corresponding author:yueming.lu@g2r.uhp-nancy.fr)
Vascular plants synthesize a large diversity
of low molecular weight compounds and more
particularly bioterpenoids. Many biochemical studies
on extant plants have pointed out that certain
bioterpenoids are specific and only occur in precise
taxa while others are generic and are widely
distributed in plant kingdom. Because these
bioterpenoids can be preserved within sediments,
their diagenetic counterparts (also called
geoterpenoids) are useful proxies of ancient
vegetation. Therefore, vascular plant biomarkers can
be used as a chemostratigraphic tool for tracing
palaeovegetation changes on hinterlands. Because
these changes are under climatic control, they can
also be used for tracing climatic evolutions through
geological times.
Among all these plant biomarkers, cadalene
and retene are certainly the most well-known.
Cadalene is a sesquiterpenoid considered as a
generic plant biomarker because it comes from the
diagenesis of cadinenes and cadinols. Indeed, these
biological compounds are synthesized by many plant
taxa. At the opposite, retene is a more specific
diterpenoid since it comes from the diagenesis of
biological abietanoids (abietic acid, ferruginol, etc.)
mainly produced by conifers.
This is why, the ratio retene/cadalene
(Re/Ca) can be used, in a first approach, to trace
paleofloristic changes through geological times (van
Aarssen et al., 2000). Then, a careful study of plant
biomarkers can allow to assess more precise
information on palaeofloras.
Hautevelle et al., (2006) pointed out a
significant increase of the Re/Ca ratio at the end of
the Lower Oxfordian in the eastern part of the Paris
basin. This evolution is also remarkably synchronous
with the progressive installation of the Oxfordian
carbonate platform. A careful study of the
diterpenoids associated to retene shows that their
distribution is very typical of those of fossil Pinaceae.
This increase in the Re/Ca ratio were thus interpreted
as an increase of the proportion of Pinaceae on the
London-Brabant massif at the end of the Lower
Oxfordian which can be linked to an increase of
aridity.
Then, this same approach was extended to
the study of the whole Jurassic of the Paris basin. For
this, we calculated the Re/Ca ratio for nearly 60
samples coming from the A901 core. It is located in
the Northern part of the Paris basin and the studied
sedimentary series are dated from Hettangian to
Middle Oxfordian. Calculated ratios show significant
evolutions through the Jurassic indicating
palaeofloristic and palaeoclimatic changes.
Furthermore, these evolutions seem to be correlated
to the 2 nd order alternations of carbonate platforms
and argillaceous deposits. Unfortunately, it is not
possible to determine more precisely these floristic
and climatic changes as it was the case for the Lower
Oxfordian.
More recently, we studied two another cores
(EST 432 & EST 433) drilled in the eastern part of the
Paris basin and allowing the study of the whole
Jurassic. More than 50 samples were studied in order
to calculate the Re/Ca ratio. The preliminary study
shows that we found the same evolutionary trend as
that obtained in the northern part of the Paris basin.
Furthermore, the evolution of the Re/Ca ratio
through Jurassic in the Paris basin appears to be
quite similar to that published by van Aarssen et al.
(2000) concerning the Jurassic of the Carnarvon
Basin (Australia). Such similarities in places very
remote lead us to believe that these evolutions are
linked to global palaeofloristic and palaeoclimatic
changes.
References:
Hautevelle, Y., R. Michels, F. Malartre, and A.
Trouiller (2006), Vascular plant biomarkers as proxies
for palaeoflora and palaeoclimatic changes at the
Dogger/Malm transition of the Paris Basin (France),
Organic Geochemistry, 37(5), 610-625.
van Aarssen, B. G. K., R. Alexander, and R. I. Kagi
(2000), Higher plant biomarkers reflect
palaeovegetation changes during Jurassic times,
Geochimica et Cosmochimica Acta, 64(8), 1417-
1424.
579

P-455
Long term cooling and punctuated climate events recorded in
Late Aptian to Early Albian sediments from the eastern
subtropical Atlantic (Mazagan Plateau, DSDP Site 545)
Alison McAnena 1 , Thomas Wagner 2 , Helen M. Talbot 2 , Jens Herrle 3 , Joerg Pross 3 , Janet
Rethemeyer 1 , Peter Hofmann 1
1 Department of Geology and Mineralogy, University of Cologne, 50674 Cologne, Germany, 2 School of Civil
Engineering and Geosciences, Newcastle University, Newcastle Upon Tyne, NE1 7RU, United Kingdom,
3 Institute of Geosciences, Goethe University Frankfurt, 60438 Frankfurt am Main, Germany (corresponding
author:amcanena@uni-koeln.de)
The Late Aptian-Early Albian reflects a period of
global transition towards the mid-Cretaceous
greenhouse, with heightened tectonic, volcanic and
hydrothermal activity, and an increase in organic
carbon burial in combination leading to a global
adjustment of climate conditions. In order to
document the response of the tropical North Atlantic
to this global climatic readjustment, we investigate the
sea surface temperature development over 5 million
years in the late Aptian expressed in marine
sediments from DSDP Site 545, Mazagan Plateau
(NW Africa).
Detailed new records of TEX86-derived sea surface
temperature (SST), organic carbon (TOC) and
carbonate content, grain size composition, δ 13 Ccarb
and δ 13 Corg confirm a >1.5 Ma cooling trend off NW
Africa that culminated in the Late Aptian ‗cold snap [1] ,
before the onset of OAE 1b. Superimposed on this
long term cooling trend three short term intervals are
identified where surface waters either markedly
cooled or warmed. Notably, these short-term SST
perturbations are stratigraphically linked to small
(

P-456
Post-glacial paleoclimatic changes in northeastern Brazil
inferred from depth-sensitive depositional records of organic
matter in sediments of Lagoa do Caçó
Abdelfettah Sifeddine 1,2 , Philip Meyers 3 , Renato Campello Cordeiro 2 , Ana Luiza
Spadano Albuquerque 2 , Marcello Bernardes 2 , Marie-Pierre Ledru 1 , Bruno Turcq 1 , Jorge
Joao Abrao 2
1 Institut de Recherche pour le Développement, France (IRD), LOCEAN, UMR 7159 CNRS-IRD-Univ. P. & M.
Curie-MNHN), Bondy, France, 2 Departamento de Geoquímica, Universidade Federal Fluminense, Niteroi,
Brazil, 3 Department of Geological Sciences, The University of Michigan, Ann Arbor, United States of
America (corresponding author:pameyers@umich.edu)
Elemental and isotopic compositions of organic matter
in surficial sediments from five transects across
Lagoa do Caçó (Brazil) have been analyzed to
identify the depth-related processes that affect the
production, preservation, and deposition of
sedimentary organic matter in this shallow tropical
lake. Each of four transverse transects begins at a
margin dominated by aquatic macrophytes
(Eleocharis), crosses the central deep part of the lake,
and finishes in the opposite macrophyte-dominated
margin. In each transect, TOC concentrations, C/N
ratios, and � 13 C values decrease between 0 to 4 m,
whereas � 15 N values increase. The parameters
remain stable in sediment from water depths from 4 m
to the center of the lake at 10 m. The depth-related
patterns reflect differences in both the delivery and
the deposition of organic matter in the lake. Organic
matter is abundantly produced in the marginal area by
emersed and submerged macrophyte vegetation that
diminishes with depth and disappears at 4 meters.
After the disappearance of macrophytes, organic
matter is principally produced at low rates by openlake
phytoplankton. Drawdown of dissolved oxygen is
high in the lake margins, but it is low in the
oligotrophic open waters of the lake. Preservation of
organic matter is consequently better in sediments of
the lake margins than in deep waters. The depthrelated
pattern of organic matter delivery and
deposition in the sediments of Lagoa do Caçó, in
which water levels are sensitive to groundwater
fluctuations, was combined with pollen data to
reconstruct changes in the post-glacial
paleohydrology of this lake system. A sediment core
from the lake margin and another from the center of
the lake record different histories of organic matter
accumulation that reflect changes in lake level over
the last 21 kyrs. At the end of the last glacial
maximum, a predominantly dry regional climate was
interrupted by short humid phases as reflected by a
succession of very thin layers of sand and organic
matter. The subsequent late glacial climate was
relatively wet and included two rapid lake-level
increases accompanied by forest expansion. The two
moist phases were separated by a phase where the
lake level remained stable and a cool climate
―Podocarpus‖ forest developed. These humid climate
periods differed significantly from the presently warm
tropical conditions. We conclude that post-glacial to
Holocene climate moisture has been controlled by
intensifications or positional shifts of the Intertropical
Convergence Zone that affected lake levels, which in
turn have left an imprint on the elemental and isotopic
compositions of sediment organic matter.
581

P-457
Molecular and isotopic evidence for differences in organic
matter delivery and preservation in two mid-Pleistocene lightdark
color cycles in sediments beneath the Benguela Current
Upwelling System
Philip Meyers 1 , Ioanna Bouloubassi 2 , Richard Pancost 3
1 Marine Geology and Geochemistry Program, Department of Geological Sciences, The University of
Michigan, Ann Arbor, United States of America, 2 L'OCEAN, UMR 7159 CNRS-IRD-UPMC-MNHN, IPSL,
Paris, France, 3 Organic Geochemistry Unit, School of Chemistry, University of Bristol, Bristol, United
Kingdom (corresponding author:pameyers@umich.edu)
The light-dark color cycles that are distinctive features
of late Neogene-Quaternary sediment beneath the
Benguela Current Upwelling System imply repetitive
alternations in organic matter delivery and
preservation. We employed molecular and isotopic
proxies for paleoproductivity and for depositional
conditions to investigate the processes involved in
creating these cycles. We selected two sediment
sequences from ODP Site 1084 that correspond to
0.7 and 1.1 Mya, the earlier one representing a world
in which glacial-interglacial cycles were paced by
eccentricity and the older one a world dominated by
obliquity. TOC concentrations vary from ca. 5% in
lighter sediments to ca.18% in darker sediments in
both sequences. Large Rock-Eval HI values indicate
that marine organic matter dominates the TOC in all
these sediments. Bulk organic δ 13 C values in the
darker sediments at 0.7 Mya are -21.5 ‰ and -19.5 ‰
at 1.1 Mya, implying that marine productivity was
greater in the older sequence. However, alkenonebased
sea-surface temperatures were lower at 0.7
Mya (15°C) than at 1.1 Mya (21°C) and bulk δ 15 N
values are also different. Both parameters suggest
that water-mass properties had changed in the 400 ky
between the deposition of the two light-dark cycles.
Biomarker molecular compositions in both sequences
reflect a range of marine organic matter sources.
Algal biomarkers are abundant and diverse,
represented by 4-desmethyl and 4-methylsterols
(diatoms), dinosteral (dinoflagellates), and alkenones
(haptophytes). These biomarkers have δ 13 C values
ranging from ca. -21 to -24 ‰, consistent with a
marine origin. A difference in the algal communities
that produced the organic matter in the two light-dark
sequences is recorded by an alkenone/sterol
concentration ratio in the 0.7 Mya cycle that is twice
that in the 1.1 Myr cycle. Stenol/stanol ratios are
consistently >1, and they are somewhat larger in the
younger sequence than the older one, indicating
relatively better preservation of the marine organic
matter in the younger light-dark cycle. Distributions of
long-chain n-alkanes with CPI values that generally
are between 6 and 9 record inputs of land-plant
waxes, likely by eolian delivery from Namibia. n-
Alkane δ 13 C values that range from -24 to -28 ‰
suggest a mixture of C3 and C4 sources. The δ 13 C
values of the C33 n-alkane are consistently 2-3 ‰
larger than those of the C31 n-alkane, confirming an
important contribution of this vascular plant biomarker
from C4 grasses. All of the long-chain n-alkanes
exhibit smaller δ 13 C values in the younger cycle than
in the older one, suggesting that a drier continental
climate accompanied the colder sea surface
temperatures recorded by the alkenones in the 0.7
Mya cycle. Other terrestrial biomarkers (e.g.
triterpenoid acids and alcohols) are present but in
very low abundances. Our molecular and isotopic
comparison of these two cycles evidently captures
some of the consequences of the progressive cooling
of global climate and the associated changes in
ocean-continent interactions.
582

P-458
220 ka palaeoenvironmental reconstruction of the Fuentillejo
maar-lake record (Central Spain) using biomarker analysis
Laura Moreno 1 , José E. Ortiz 1 , Trinidad Torres 1 , Juana Vegas 2 , Blanca Ruiz-Zapata 3 ,
Ángel García-Cortés 2 , Luis Galán 2 , Alfredo Pérez-González 4
1 Biomolecular Stratigraphy Laboratory. E.T.S.I. Minas, Universidad Politécnica Madrid. Ríos Rosas 21,
Madrid, Spain, 2 Instituto Geológico y Minero de España (IGME). Ríos Rosas 23, Madrid, Spain, 3 Dpto.
Geología. Facultad Ciencias. Campus Universitario. Universidad Alcalá, Alcalá de Henares, Spain, 4 Centro
Nacional de la Evolución Humana. Avda. de la Paz 28, Burgos, Spain (corresponding
author:laura.moreno@upm.es)
The sedimentary record of the volcanic lake-maar of
Fuentillejo (Central Spain) offers the opportunity to
determine palaeoenvironmental evolution during the
Middle and Upper Pleistocene of the Central-
Southern part of the Iberian Peninsula, a warmsteppe
zone with peculiar environmental
characteristics. The complete sedimentary record was
obtained from a continuous core (142.4 m long),
although here we addressed only the upper 88 m, in
which a total of 439 samples were taken at 20-cm
intervals. Biomarkers were extracted using an ASE-
200 and analyzed in a CG-MS (Agilent 6890/5973).
Several radiometric datings ( 14 C and U/Th) allowed us
to determine an age-depth function and the record
was calculated to cover a time span of 350 ka.
Here we present results on the n-alkane distribution,
although we also include other biomarkers such as nketones,
n-alkanoic acids, organic sulphur and
sterols.
We used a number of n-alkane indexes, such as the
predominant n-alkane chain, the aquatic macrophytes
proxy index (Paq), the carbon preference index (CPI),
and the relative percentage of high molecular weight
n-alkanes.
At the bottom of record we interpreted a mixed input
of terrestrial plants and algae in which a bimodal
distribution of C17 and high molecular weight nalkanes
was observed. C27 and C29 n-alkanes were
dominant from 76.80 to 71.80 m, thus indicating a
major input of terrestrial vegetation, while again a
mixed input was detected between 71.80 and 60 m.
However, there was a clear record of organic matter
of algal origin from 60 to 22.5 m. Low CPI values and
C29 n-alkane dominance were observed in the upper
25.5 m of the record, these linked to organic matter
derived from terrestrial plants.
Using the wide range of information obtained from the
n-alkane indexes, we perform a series of statistical
analyses (cluster and spectral analysis) to synthesize
geochemical data. We identified six biomarker
associations from the cluster analysis, these ranging
from group 1 (the wettest environmental conditions) to
6 (the driest phases). Thus, we constructed a
palaeoenvironmental index of the Fuentillejo record.
This index showed marked variations that can be
linked to distinct palaeoclimatic scenarios (more
humid vs. drier phases). The spectral analysis
showed palaeoenvironmental variations linked to 100,
41 and 26 ka periods (Milankovitch cycles).
Figure 1. Palaeoenvironmental index along the upper
88 m of Fuentillejo record.
583

P-459
Long-term variations of palaeovegetation recorded by
angiosperm and gymnosperm biomarkers in the Late
Cretaceous sequence of Kotanbetsu, Hokkaido, Japan
Hideto Nakamura 1 , Ken Sawada 1 , Reishi Takashima 2
1 Department of Natural History Sciences, Faculty of Science, Hokkaido University, Sapppro, Japan, 2 Tohoku
University Museum, Sendai, Japan (corresponding author:hideton@mail.sci.hokudai.ac.jp)
The Cretaceous is an interval of exceptional
interest for understanding the early evolution and
expansion of angiosperm. The reconstruction and
ecological interpretation of the Cretaceous flora,
however, are far from complete because of some
disadvantages of classical palaeobotanical and
palynological studies (e.g. Rare occurrence of
morphologically well-preserved fossils). Meanwhile,
terrestrial plant biomarkers preserved in ancient
sediments have been proposed as useful tool for
reconstruction of palaeovegetational and
palaeoclimatic conditions (e.g. [1, 2]). However, there
are few biomarker studies focused on reconstruction
of the early evolution of angiosperms [3, 4].
Palynological studies reports that angiosperm pollen
explosively advanced in diversity in the Late
Cretaceous sequences in Japan [5]. Thus, we
analyzed terrestrial plant biomarkers from sediments
of the Lower Cenomanian to the Lower Campanian of
the Yezo group, Hokkaido, Japan, in order to
reconstruct palaeovegetation and to examine the
applicability for its indicator.
Mudstones, sandy siltstone and sandstone
samples were collected from the middle-upper part of
the Yezo Group exposed along the Kotanbetsu River
and its tributary in northern Hokkaido, Japan. The
high-resolution litho-, bio-, and carbon-isotope
stratigraphy of studied section have been established
in [6], and the samples range from the latemost Albian
to the Early Campanian.
The maturity indices ������������� of
hopanes show gradual decrease toward the bottom of
the sequence (0.49–0.05), while 20S/(20S+20R) of
C29 steranes show low values (

P-460
Geochemical and historical study of a 700 year old pond,
Lansquenet -Lorraine, France - a multidisciplinary approach
Olivia Bertrand 1 , Laurence Mansuy-Huault 1 , Emmanuelle Montargès-Pelletier 2 , Benoît
Losson 3 , Jacqueline Argant 4 , Raymond Michels 1 , Pierre Faure 1 , Emmanuel Garnier 5 ,
Charles Kraemer 6
1 G2R, CNRS-Nancy University, 54506 Vandoeuvre-lès-Nancy, BP. 239, France, 2 LEM, CNRS-Nancy
University, 54501 Vandoeuvre-lès-Nancy, BP. 40, France, 3 CEGUM, UPV-Metz, 57006 Metz Cedex 1, BP.
30309, France, 4 LAMPEA, CNRS-Aix University, 13094 Aix-en-Provence, BP. 647, France, 5 LSCE, CEA-
CNRS Saclay, 91191 Gif-sur-Yvette Cedex, France, 6 HISCANT MA, Nancy University, Nancy 2, 54015
Nancy Cedex, BP. 3397, France (corresponding author:olivia.bertrand@g2r.uhp-nancy.fr)
The pond of Lansquenet, in the north eastern part of
France, was artificially created in the thirteenth
century, for fish farming/fish breeding. The analysis of
historical records provided information about the
evolution of land use in the vicinity of the pond and in
the upstream watershed, about the management of its
fishery resources and could evidence striking
meteorologic events (floods, draughts) over the last
centuries. Additionally, sedimentary deposits could be
sampled as core samples on a final depth of 2m35.
Such sediment cores were submitted to
sedimentological, palynological, mineralogical and
geochemical (organic and inorganic) analyses. The
organic matter content varies from 1 to 4% of total
organic carbon throughout the sedimentary record.
The combination of palynological data and organic
geochemistry allowed us to reconstruct the evolution
of vegetation around the pond. The deepest
sediments are characteristic of a swamp. A particular
level between 1 and 1.2 m, dated between 1040 and
1378 years AD retained our attention due to
accumulations of woody material. This portion of
sediments is characterized by an increase of
terrigenous inputs as shown by global and molecular
biomarkers (TOC, C/N, TARHC, C29/C27(ST), perylene)
(fig. 1) and by a relatively (more) oxic environment as
suggested by organic markers (Pr/(Pr+Ph),
Hopenes/Hopanes) as well as by the apparition of
gypsum (X-ray diffraction), strongly suggesting a low
water level period. Perylene, a marker of wooddegrading
fungi, appears as a good indicator of this
massive wood input. From the 1 m depth layers to the
upper layers, the organic inputs evolve toward an
increasing contribution of emerging macrophytes
indicating an eutrophication of the pond in the last
decades evidenced by the occurrence of genus
spirogyra, the high concentration of n-C17 and the
increase of the Paq = (C23+C25)/(C23+C25+C29+C31).
Whereas the PAH concentrations remain very low in
the deeper layers with a distribution assigned to
biomass combustion, the last five decades are
marked by an increase of PAH concentrations
originating from petroleum combustion. Traces of
coprostanol, a marker of human faeces and waste
waters, are also observed during the same period. A
second oxic event was recorded at a depth of
60 cm, associated with high organic matter
degradation evidenced by a decrease of TOC
associated to an increase of Pr/(Pr+Ph)). The
oxic events could be indicative of draining
occurring regularly in the management of such
a pond. While this sampling site was selected
for its rural context and its low human
pressure, anthropogenic impacts could
however be evidenced: changes in land use
and more recently pollutant inputs.
Figure 1: Variations in COT content (%), Paq
and in the concentration of fluoranthène and
perylene (ng/g) based on depth
585

P-461
Miocene to Pliocene environmental changes recorded in South-
West African continental margin sediments
Florian Rommerskirchen 1 , Lydie Dupont 1 , Gesine Mollenhauer 2 , Enno Schefuß 1
1 Marum - Center for Marine Environmental Sciences, University of Bremen, D-28334 Bremen, Germany,
2 Alfred Wegener Institute for Polar and Marine Research, D-27570 Bremerhaven, Germany (corresponding
author:rommerskirchen@uni-bremen.de)
The Miocene epoch is characterized by the
transition from relatively warm greenhouse conditions
to cooler, drier and less stable climates [1,2,3]. During
the late Miocene rapid cooling in mid- to highlatitudes,
surface ocean circulation and enhanced
deep water production were triggered by a permanent
establishment of Antarctic ice-sheets [1,3,4]. On
tropical and subtropical continents plants using the
CO2 concentrating C4 mechanism for photosynthesis
expanded nearly simultaneously at different places in
the world, while temperatures declined and global
CO2 levels exhibited no corresponding decrease [1,5].
Main aim of this study is thus to unravel the climatic
changes in South-West Africa from the Miocene to
Pliocene which led to the expansion of C4 plants in
that area.
We use organic geochemistry combined with
palynology on sediments of ODP Site 1085 to
evaluate the linkage of sea surface temperature
(SST) changes and continental vegetation. The site is
located in the Cape Basin at the south-west African
continental margin, within today‘s Benguela Upwelling
System (BUS). Sea surface and sub-surface
temperatures estimated by U K‘ 37 and TEX86 indicate a
cooling from above approximately 27 to 18°C over a
time period from 13.7 to 2.8 Ma. Differences in rate
and timing between these two temperature proxies
are related to differences in the habitat of the source
organisms, where U K‘ 37 represents surface and TEX86
subsurface temperatures [6]. Increased upwelling led
to lower SSTs and enhanced marine primary
production after 11 Ma. Synchronously, stronger
cooling in sub-surface waters by increased advection
of cold Antarctic intermediate waters is suggested by
TEX86 estimates. Concurrently, the abundance of
marine cysts and terrestrial pollen and spores
increased. The relative contribution of organic river
run-off from the nearby Orange River declined, as
indicated by the decrease in BIT-index from ~0.8 to

P-462
Branched tetraether lipid derived air temperature and soil pH in
lake sediments from Zeekoevlei, South Africa
Supriyo Das 1,2 , James Bendle 2 , Joyanto Routh 1,3
1 MTM, Örebro University, Örebro, Sweden, 2 Department of Geographical and Earth Sciences, Glasgow
University, Glasgow, United Kingdom, 3 Dept. of Earth Sciences, IISER-Kolkata, Mohanpur, India
(corresponding author:supriyo.das@oru.se)
Here, we apply branched glycerol dialkyl glycerol
tetraethers (br-GDGTs) based methylation index of
branched tetraethers/cyclisation ratio of branched
tetraethers (MBT/CBT) proxy to reconstruct decadal
scale changes in terrestrial temperature from an
urban shallow (mean depth < 5m) oxic lake sediment.
We estimate the mean air temperature (MAT) and
catchment soil pH from 1946 to 2004 in a sediment
core collected from Zeekoevlei, the largest freshwater
lake in South Africa, which is located 20 km south of
Cape Town. The lake falls in the sub-tropical
Mediterranean winter rainfall climate zone, and is a
warm-water lake. The annual lake surface
temperature ranges between 10.3°C and 28.5°C. We
compare the reconstructed br-GDGT derived MAT
(TMBT) with the historical air temperature data from
1946 to 2004, which is available in Global Historical
Climatology Network (GHCN-monthly) Version 2
database (www.ncdc.noaa.gov/oa/climate/ghcnmonthly/index.php).
The monthly temperature data
were recorded at the World Meteorological
Organization (WMO) station in a United States of
America Navy site in Cape Town. We have used a
yearly mean of the GHCN-monthly temperature
record in this abstract.
TMBT closely follows the mean annual GHCN-monthly
temperature record (TGHCN; Fig. 1). However, the TMBT
values are ~2ºC warmer than TGHCN. This indicates
that br-GDGT bacterial production is biased towards
the summer, and yields temperature estimates that
fall between summer (Austral summer) and TGHCN.
Our finding lies in line with similar findings in
Greenland 1 that suggests bias of br-GDGT derived
MBT/CBT proxy towards warmer temperature. This
finding may also indicate an in-situ production of br-
GDGTs 2,3,4 .
We infer the variation in TMBT (Fig. 1) in Zeekoevlei
with regard to El Niño events and post-apartheid rapid
urbanization. We also find a reflection of
socioeconomic changes in the lake‘s catchment in the
reconstructed soil pH. Our results provide an example
of the application of the MBT/CBT-MAT proxy to lake
sediments in catchment settings impacted by
agricultural and urban pollution.
Fig. 1 Variation in GHCN-monthly summer, winter and
yearly mean temperature (TGHCN), TMBT and CBT
derived catchment soil pH from 1946 to 2004. Bold
line in TGHCN represents smoothening of data in
CBT
Soil pH
±1 σ
9.5
8.5
1
GHCN-Monthly
Summer temperature
T MBT in Zeekoevlei
±1 ζ
T TGHCN GHCN
GHCN-Monthly
Winter temperature
SigmaPlot 8.02
References:
8
1946 1954 1962 1970 1978 1986 1994 2002
Year
1 Schouten, S. et al. Geology 36, 147-150
(2008).
2 Peterse, F. et al. Organic Geochemistry 40,
692-699 (2009).
3 Tierney, J. E. et al. in AGU 2010 Fall
<strong>Meeting</strong> (2010).
4 Buckles, L. K. et al. in AGU 2010 fall <strong>Meeting</strong>
(2010).
22
20
18
16
14
12
10
Air Air Temperature Temperature (ºC) (ºC)
587

P-463
Holocene paleoclimatic variations recorded by biomarkers in
sediment cores from the Dabusu Lake, northeastern China
Ken Sawada 1 , Makiko Ono 1 , Yuroyuki Kitagawa 2 , Hu Ke 3
1 Faculty of Science, Hokkaido University, Sapporo, Japan, 2 Nagoya University, Nagoya, Japan, 3 Jilin
University, Chanchun, China (corresponding author:sawadak@mail.sci.hokudai.ac.jp)
The Dabusu Lake (44°49‘N, 123°40‘E) is a
continental saline lake in the northeastern China. The
climate around this lake is affected by East Asian
monsoon. Biomarker found in such lacustrine
sediment can be useful as powerful proxy for
reconstructing paleoclimatic and paleoenvironmental
variations in intercontinental area. In this study, we
analyzed biomarkers such as long-chain n-alkanes
and alkenones to reconstruct paleotemperature and
lake water level, respectively. From these biomarker
records, we suggest the millennial-scale variations of
Holocene paleoclimate in northeastern China.
Two cores (DB-A and DB-B) were collected during
January, 2004 in the Dabusu Lake. The DB-A and
DB-B core sites are located near the shore, where
lake water is completely dried in winter at present,
and central area of the lake, respectively. Humic
substance was separated from the DB-B sediments
by HF and HCl acidification. Radiocarbon ( 14 C) ages
of the humin were determined by using AMS of the
Paleolabo Co. Japan. Extraction and separation of
lipids were performed as reported previously [1].
Long-chain n-alkanes and alkenones were analyzed
by GC and GC/ MS. Alkenone unsaturation indices
(U K 37 and U K‘ 37) and carbon preferential index (CPI) of
n-alkanes were individually calculated by using
conventional equations [2,3]. The n-alkane proxy for
submerged and floating aquatic macrophyte (Paq=
(C23+C25)/(C23+C25+C29 + C31)) [4] was also calculated.
The C37-C40 di- to tetra-unsaturated alkenones were
identified in all samples of DB-A and DB-B cores. The
U K 37 and U K‘ 37 values varied by depths in both DB-B
and DB-A cores, especially with some higher spikes
of U K‘ 37 values. Annual and summer temperatures
from the U K‘ 37 were calculated by using the equations
which previously established in lacustrine sediments
of Chinese lakes [5,6]. Annual and summer
temperatures of DB-A and DB-B cores were
estimated to be -0.46 to 6.29°C and -4.65 to 9.61°C,
respectively. The larger variability of paleotemperature
observed in DB-A may be caused by
local effects such as seasonality of alkenonesynthesizing
algal production. Interestingly, highest
spikes (6.29°C) of temperatures were found at 333-
335 cm depth in DB-B. Calendar ages converted from
AMS 14 C ages are 4230±27 yrBP in 100 cm depth and
5551±28 yrBP in 370 cm depth of DB-B. The age of
the layer of warmer spike (333-335 cm depth) is
estimated to be ca. 5350 yrBP by interpolation.
Previous pollen study suggested that the Holocene
Optimum was observed in north-central China region
during 7900-4450 yrBP [7], which includes the timing
of the warmer spikes in the Dabusu Lake.
The CPIs tended to increase, while Paq decreased
from bottom to top (over the past about 6500 years) of
DB-A and DB-B, especially DB-A. The trend of CPI
variation indicates increase of input of terrestrial
higher plant wax to lacustrine sediments. The Paq
trend indicates that aquatic plant community decline
within this lake. These findings suggest that the lake
water level was lower, resulting from change to arid
condition around the lake from bottom to top. These
aridity variations recorded by the n-alkane proxies
were concordant with those of alkenone-based
temperatures.
References
[1] Sawada, K., Handa, N., Shiraiwa, Y., Danbara, A.,
Montani, S. (1996) Org. Geochem. 24, 751-764.
[2] Prahl, F.G., Muehlhausen, L.A. and Zahnle, D.
(1988)Geochim. Cosmochim. Acta. 52, 2303-2310.
[3] Bray, E.E. and Evans, E.D. (1961) Geochim.
Cosmochim. Acta. 27, 1113-1127.
[4] Ficken, K.J., Li, B., Swain, D.L. and Eglinton, G.
(2000) Org. Geochem. 31, 745-749.
[5] Sun, Q., Chu, G., Li, S., Lu, C. and Zheng, M.
(2004) Chinese Sci. Bull. 49, 2082-2086.
[6] Chu, G., Sun, Q., Li, S., Zheng, M., Jia, X., Lu, C.,
Liu, J. and Liu, T. (2005) Geochim. Cosmochim.
Acta 69, 4985-5003.
[7] Xiao, J.L.J., Xu, Q., Nakamura, T., Yang, X., Liang,
W. and Inouchi, Y. (2004) Quat. Sci. Rev. 23,
1669-1679.
588

P-464
Effects of within-catchment provenance on terrestrial climate
parameters in marine sediments off large rivers
Enno Schefuß 1 , Gesine Mollenhauer 1,2 , Holger Kuhlmann 1 , Matthias Prange 1 , Jürgen
Pätzold 1
1 MARUM - Center for Marine Environmental Sciences and University of Bremen, Bremen, Germany, 2 Alfred
Wegener Institute for Polar and Marine Research, Bremerhaven, Germany (corresponding
author:schefuss@uni-bremen.de)
Reconstructions of terrestrial climate conditions are
often applied by using lipid biomarker proxies in
marine sediment cores off large rivers to assess
continental climate changes in the catchments (e.g.,
(Schefuß et al., 2005; Weijers et al., 2007). The
assumption to reconstruct catchment-integrated
climate changes is challenged by studies reporting
overprint of organic particulate material compositions
during fluvial transport (e.g., (Bouillon et al., 2009).
Here, we present a multi-proxy comparison of climatic
changes recorded in a sediment core taken offshore
the Zambezi River in southeast Africa. Compoundspecific
hydrogen isotope analyses of long-chain nalkanes
reveal profound changes in continental
hydrology. Depleted hydrogen isotope compositions
are found for time intervals corresponding to northern
high-latitude cold events such as the Younger Dryas
suggesting higher rainfall in the catchment. Parallel
depletions of soil pH estimates based on
compositional changes in terrestrial GDGTs (CBT
index) support this finding. Lower soil pH values are
caused by higher rainfall amounts due to the removal
of cations from surface soils (Johnson et al., 1998).
Additionally, synchronous increased sedimentary
terrigenous elemental and biomarker concentrations
as well as elevated relative contributions of terrestrial
GDGTs (high BIT index) suggest strong fluvial
discharge during these events. Taken together, these
proxies would indicate higher rainfall in the catchment
leading to lowered soil pH and increased contributions
of terrestrial elements, plant lipids and soil organic
matter to the marine sediments.
In contrast to these observations suggesting wetter
conditions, stable carbon isotope analyses of longchain
alkanes reveal higher contributions of C4 plants
during these times. Under present-day conditions, C4
plants (tropical grasses) prevail over C3 plants in
Africa when rainfall amounts are too low to permit C3
trees to grow or when the rainy season is too short.
For past climate conditions, also atmospheric CO2
levels and growing-season temperatures potentially
affect the relative abundance of C4 plants in the
vegetation cover. The elevated C4 plant contributions
during the discharge events would thus suggest drier
conditions, lower atmospheric CO2 concentrations or
higher temperatures. As atmospheric CO2 levels rose
during the Younger Dryas changing atmospheric CO2
concentrations are ruled out as potential driver of the
observed C3/C4 changes. Parallel to the increase in
C4 plant contribution, estimates of mean annual
temperatures based on terrestrial branched GDGT
compositions (MBT index) suggest slightly warmer
temperatures. The relatively small amplitude of the
reconstructed temperature changes, however, cannot
explain the observed strong C3/C4 plant changes.
Therefore, we infer that catchment-internal shifts of
the main rainfall area towards the headwaters of the
Zambezi River currently vegetated by C4 grasslands
and experiencing warmer temperatures caused the
observed coherent, but apparently contradicting
climate reconstructions.
When considered alone, the terrestrial proxy
parameters would lead to deviating climate
interpretations. However, when judging their
significance for each specific setting and interpreted
in conjunction, they may provide insights into withincatchment
provenance changes.
Bouillon, S. et al. (2009) Biogeosciences 6, 2475-
2493.
Johnson, D.W. et al. (1998) Water Air Soil Pollut. 105,
251-262.
Schefuß, E. et al. (2005) Nature 437, 1003-1006.
Weijers, J.W.H, et al. (2007) Science 315, 1701-1704.
589

P-465
Hydrological and biogeochemical variations in the hypersaline
Lake Tswaing (South Africa) during the last 84 ka BP
Frauke Schmidt, Hedi Oberhänsli, Heinz Wilkes
Helmholtz Centre Potsdam GFZ German Research Centre for Geosciences, Potsdam, Germany
(corresponding author:frauke.schmidt@uni-bremen.de)
Organic matter in lacustrine sediments of endorheic
lakes has generally a great potential of recording
changes in the regional climate and the environmental
conditions during deposition. Lake Tswaing is a small
impact crater lake in the NE of South Africa; its
sediments represent the longest continuous record of
environmental change on the southern African
subcontinent. The present regional climate is
characterized by an unbalanced hydrology with
elevated lake water evaporation resulting in a highly
alkaline, saline and anoxic lake body which is
primarily inhabited by cyanobacteria and bacteria. A
recent study investigated the modern carbon cycle in
Lake Tswaing via stable carbon isotope analyses of
total organic carbon (TOC) and lipid biomarkers [1].
Here, we analysed lipid biomarkers and their stable
carbon and hydrogen isotopic signatures in a 35 m
long sediment core for a comprehensive
understanding of the climatic influence on the lake
evolution and for insights into the adaption of the lake
biocoenosis to the extreme and changing
environmental conditions during the last 84 ka BP.
The hydrogen isotopic composition of higher plantderived
n-alkanes (δDwax) varied strongly between
−155 and −106‰ indicating highly variable
hydrological conditions which partly controlled TOC
content in the sediments. Periods with low TOC
contents corresponded to heavy δDwax values, i.e., dry
climate conditions which lowered the allochthonous
input and the productivity in the lake. On the other
hand, high amounts of fresh organic matter from land
plants and aquatic organisms were deposited under
humid climate conditions resulting in sedimentary
TOC contents of up to 9.8%. Low values of the higher
plant n-alkane index (HPA [2]) suggested that the
increased rainfall during these periods reduced the
vertical salinity gradient resulting in water column
mixing and oxygenation of the bottom water. The
biocoenosis in the lake consisted primarily of algae
and bacteria. It showed strong variations in the
abundance of the different organisms and a temporal
succession in response to the changing nutrient
conditions in the lake during specific intervals. For
example, dinoflagellates were most prominent in the
time before 66 ka BP followed by a period with higher
bacterial activity (Fig.1). δ 13 C of dinosterol varied
strongly and showed partly very heavy values of up to
−0.5‰ pointing to a strong limitation in dissolved CO2
during times of high aquatic productivity and/or high
lake alkalinity. The occurrence of 4,4-dimethylcholest-
8(14)-enol, a specific marker for methanotrophic
bacteria, and light δ 13 C values of bacteria-derived
moretene provided evidence for methanotrophic
activity in certain time intervals.
Fig. 1. TOC content, lipid biomarker concentrations
and their δ 13 C values in the time from 71 to 57 ka BP.
13 C-depleted values for 4,4-dimethylcholest-8(14)enol
and moretene indicate methanotrophic activity in
Lake Tswaing.
References:
[1] Kristen, I., Wilkes, H., Vieth, A., Zink, K.-G.,
Plessen, B., Thorpe, J., Partridge, T., Oberhänsli, H.,
2010. J. Paleolimnol. 44, 143 – 160.
[2] Poynter, J., Eglinton, G., 1990. Proc. ODP Sci.
Results 116, 155 – 161.
590

P-466
Can molecular markers for pyrogenic carbon help to reconstruct
wildfire temperatures?
Maximilian P.W. Schneider 1 , William C. Hockaday 2 , Caroline A. Masiello 2 , Michael W.I.
Schmidt 1
1 University of Zurich, Department of Geography, Zurich, Switzerland, 2 Rice University, Department of Earth
Science, Houston, United States of America (corresponding author:maximilian.schneider@geo.uzh.ch)
The maximum temperature experienced by charcoals
strongly influences relevant properties, such as
surface area (Brown et al., 2006), sorption capacity
(Chen et al., 2008) and degradability (Bruun et al.,
2008; Zimmerman, 2010). Yet information about the
temperature during formation of natural charcoals in
the environment is difficult to obtain.
Benzenepolycarboxylic acids (BPCA) are molecular
markers specific for pyrogenic carbon (PyC) and are
used to quantify PyC in soils, sediments and oceans
(Hammes et al., 2008; Dittmar & Paeng, 2009).
Additionally to quantitative information, the
concentration of one of the marker molecules, B6CA
(mellitic acid), provides information on the degree of
aromatic condensation in charcoals and probably,
also the intensity of the heat treatment during the
pyrolysis process (Schneider et al., 2010). We
calibrated this ―molecular thermometer‖ by using a
thermosequence of charcoals (200 to 1000°C),
produced under N2 atmosphere from two different
types of biomass (grass and wood) in a tube furnace
(Schneider et al., 2011).
So far it is not clear how other factors during
pyrolysis, such as availability of oxygen, moisture and
exposition time, influence the resulting molecular
marker pattern. Here we apply the molecular marker
method to a set of 10 charcoals produced during a
controlled burn experiment, which was conducted at
the US Forest Service Silas Little Experimental
Forest, located near New Lisbon, New Jersey. The
charred samples were derived from litter and bark of
pitch pine (Pinus rigida) and inkberry (Ilex glabra)
plants. Thermo-sensitive paints were used to keep
record of the upper temperature range that a sample
experienced during the fire event. Maximum
temperatures of 260 to 650°C were monitored, which
are typical temperatures for wildfires and which is well
within the calibrated temperature range of the
thermosequence charcoals. We compare the
estimated formation temperatures derived from
molecular marker patterns with those measured by
the thermo-sensitive paints. Our results show if the
―molecular thermometer‖ can be used to estimate the
formation temperature of natural charcoals.
References
Brown, R.A., Kercher, A.K., Nguyen, T.H., Nagle,
D.C., Ball, W.P., 2006. Production and
characterization of synthetic wood chars for use as
surrogates for natural sorbents. Organic
Geochemistry 37, 321-333.
Bruun, S., Jensen, E.S., Jensen, L.S., 2008. Microbial
mineralization and assimilation of black carbon:
Dependency on degree of thermal alteration. Organic
Geochemistry 39, 839-845.
Chen, B.L., Zhou, D.D., Zhu, L.Z., 2008. Transitional
adsorption and partition of nonpolar and polar
aromatic contaminants by biochars of pine needles
with different pyrolytic temperatures. Environmental
Science & Technology 42, 5137-5143.
Dittmar, T., Paeng, J., 2009. A heat-induced
molecular signature in marine dissolved organic
matter. Nature Geoscience 2, 175-179.
Hammes, K., Torn, M.S., Lapenas, A.G., Schmidt,
M.W.I., 2008. Centennial black carbon turnover
observed in a Russian steppe soil. Biogeosciences 5,
1339-1350.
Schneider, M.P.W., Hilf, M., Vogt, U.F., Schmidt,
M.W.I., 2010. The benzene polycarboxylic acid
(BPCA) pattern of wood pyrolyzed between 200 °C
and 1000 °C. Organic Geochemistry 41, 1082-1088.
Schneider, M.P.W., Smittenberg, R.H., Dittmar, T.,
Schmidt, M.W.I., 2011. Comparison of gas with liquid
chromatography for the determination of
benzenepolycarboxylic acids as molecular tracers of
black carbon. Organic Geochemistry (in press).
Zimmerman, A.R., 2010. Abiotic and microbial
oxidation of laboratory-produced black carbon
(biochar). Environmental Science & Technology 44,
1295-1301.
591

P-467
Molecular hydrogen isotope systematics in Eocene lake
sediments: Hydrogen isotope exchange and estimate of paleo
lake water hydrogen isotope composition
Nils Andersen 1,2 , Stefano M. Bernasconi 1 , Robert M. K. Carlson 3 , Martin Schoell 4
1 ETH Zurich, Geologisches Institut, Zurich, Switzerland, 2 University of Kiel, Radiocarbon Laboratory, Kiel,
Germany, 3 Chevron Research And Technology Co., Richmond, United States of America, 4 GasConsult
<strong>International</strong> Inc., Berkeley, United States of America (corresponding author:mschoell@gas-consult.com)
Hydrogen isotopic signatures in individual compounds
(n-alkanes, isoprenoids, steranes and carotenoids)
are reported for products of the Eocene Green River
shale and exhibit variations in �D between -135 and -
296‰ VSMOW. The �D values of n-alkanes and
isoprenoids are consistent with a primary biosynthetic
origin. However, formerly poly-unsaturated
carotenoids, perhydro-�-carotene and lexane, are
strongly depleted in deuterium, both in the immature
gilsonite and a more mature oil. This suggests that
during early diagenesis, the biological precursor
carotenoids become saturated with hydrogen from an
external, non-biological source with estimated �D
values of about –600‰. Using the primary
biosynthetic-derived D-concentrations of steranes, nalkanes
and isoprenoids and applying known �DH20
fractionations between water and organic compounds,
results in a narrow range of estimates of the Dconcentration
of lake water of 0-20 ‰. This
enrichment in deuterium is consistent with an arid
lake environment similar to today's desert lakes in
California and other parts of the world.
592

P-468
Carbon isotopic composition of Thaumarchaeotal ether-bound
biphytanes during the early Eocene carbon isotope excursions
Petra Schoon 1 , Appy Sluijs 2 , Henk Brinkhuis 2 , Claus Heilmann-Clausen 3 , Bo Pagh
Schultz 4 , Jaap Sinninghe Damsté 1 , Stefan Schouten 1
1 NIOZ Royal Netherlands Institute for Sea Research, Department of Organic Biogeochemistry, 't Horntje,
Texel, Netherlands, 2 Biomarine Sciences, Institute of Environmental Biology, Faculty of Science, Utrecht
University, Utrecht, Netherlands, 3 Aarhus Universitet, Geologisk Institut, Aarhus, Denmark, 4 Fur Museum,
Fur, Denmark (corresponding author:petra.schoon@nioz.nl)
Marine non-thermophilic archaea (recently
reclassified within the new phylum Thaumarchaeota
[1]) are important organisms among present day
marine microbes. Their membrane lipids, analyzed as
glycerol dialkyl glycerol tetraethers (GDGTs) by
means of HPLC, or as biphytane moieties after
laboratory ether-bond cleavage with HI/LIAlH4, are
ubiquitous, and are found in recent and ancient
sediments [2]. Crenarchaeol is thought to be a
specific GDGT for Thaumarchaeota and consists of
two biphytanes, one with two cyclopentyl moieties and
the other with an additional cyclohexyl moiety (c and
d; Fig. 1A). Stable carbon isotopic measurements of
these bihytanes have revealed a remarkably
consistent � 13 C value of ca. 20-22 ‰ [2]. As archaea
utilize dissolved bicarbonate as carbon source [3],
variations in � 13 C of the biphytanes may thus reflect
variations in � 13 C of DIC. Indeed, this can probably
explain the enrichment in biphytane 13 C content
during the Cretaceous anoxic event 1b [3]. However,
the controlling factors on the stable carbon isotopic
composition of crenarchaeol are not well known.
Here we report the results of � 13 C analyses of
biphytanes from crenarchaeol, and other GDGTs, in
sediments deposited during two Eocene
hyperthermals. The Paleocene-Eocene Thermal
Maximum (PETM; ~55 Ma) and Eocene Thermal
Maximum 2 (ETM2; ~53 Ma) are geological short
episodes of extreme global warming and
environmental change. Furthermore, both events are
characterized by a negative carbon isotope excursion
(CIE) of several ‰, induced by the injection of 13 Cdepleted
carbon in the ocean-atmosphere system.
However, among the various carbon reservoirs, such
as marine and terrestrial carbonates, the magnitude
of the CIEs vary, making it difficult to constrain the
actual CIE and thereby the amount of carbon that was
involved during these hyperthermals. Our � 13 C results
of sediments deposited in the Arctic Ocean showed
that at maximum of the CIE of ETM2, crenarchaeol
was ~2.5 ‰ more negative than prior to the event.
However, this � 13 C negative shift of the biphytanes
coincided with peak concentrations of derivatives of
the specific biomarker isorenieratene and during
cooler sea water temperatures inferred from TEX86.
This may imply that the Thaumarchaeota responded
to the arising euxinic conditions at this location by
migrating to below the chemocline. It is therefore not
certain whether this 2.5 ‰ truly reflects the CIE in
DIC. In addition, changing climate and oceanography
may have altered the � 13 C of DIC differently in this
relatively restricted basin than in the global ocean.
Currently we are analyzing the � 13 C composition of
GDGTs in sediments deposited during the PETM, at
three off-shore sections in Denmark. This may
provide the first continuous � 13 C DIC record across an
Eocene hyperthermal and may provide knowledge on
the CIE in the DIC pool during the PETM.
Fig. 1. Structure of acyclic and cyclic biphytanes (A) and
their distribution (B) in a sediment deposited during ETM2
with their corresponding � 13 C values.
References
[1] Spang et al. (2010), Trends Microbiol 18, pp. 331–340.
[2] Schouten et al. (1998), Org. Geochem. 29, pp. 1305-
1319.
[3] Kuypers et al. (2001), Science 293, pp. 92-94.
593

P-469
Impact of anaerobic methane oxidizing archaea on TEXL86
paleotemperature records from Antarctica
Stefan Schouten 1 , Veronica Willmott 1 , Eugene Domack 2 , Rieneke Gieles 1 , Jaap
Sinninghe Damste 1
1 Royal Netherlands Institute for Sea Research, Den Burg, Texel, Netherlands, 2 Hamilton College, Clinton,
NY, United States of America (corresponding author:stefan.schouten@nioz.nl)
The TEX86 (TetraEther indeX of lipids with 86 carbon
atoms), is an organic paleothermometer based on the
relative distribution of glycerol dibiphytanyl glycerol
tetraether lipids (GDGTs) biosynthesized by marine
Thaumarchaeota, one of the dominant prokaryotes of
today‘s oceans. Mesocosm studies show that this
ratio increases with increasing temperatures and core
top studies have shown that TEX86 correlates well
with annual mean sea surface temperatures.
Recently, a revised index, the TEX L 86, was proposed
to reconstruct temperatures in polar area‘s [1]. The
use of TEX L 86 in polar areas is potentially promising
because it can be measured in carbonate poor
sediments and is unlikely to be influenced by soil
input in this region.
Here we generated a TEX L 86 temperature
record in a Holocene, 20 m long sediment core from
the Western Antarctic Peninsula. The TEX L 86 derived
temperature (Fig. 1) of the upper section of the core,
between 0 and 6.5 mbsf, oscillates slightly between 0
and 2°C, consistent with the annual temperature
fluctuation of Antarctic Surface Water (AASW) in the
Western Antarctic Peninsula. However, below 6 m
core depth, the calculated temperatures increase to
values up to 25°C, which is entirely inconsistent with
the climate development in this geographical location
during the Holocene period. The data clearly show
that the proxy is not working in this section of the core
and is severely biased. Since the extreme high
TEX L 86 temperatures also cannot be caused by a bias
in seasonality or depth habitat of the
Thaumarchaeota, the likely cause must be an input of
GDGTs not derived from the pelagic water column.
An input of soil GDGTs can be excluded as the BIT
index, a proxy for the input of soil derived GDGTs,
were always

P-470
Organic-geochemical Proxys for Tsunami-Events in sediment
cores of the Thermaikos Gulf
Frederike Wittkopp, Klaus Reicherter, Jan Schwarzbauer
RWTH Aachen University, Aachen, Germany (corresponding author:schwarzbauer@lek.rwth-aachen.de)
Nowadays, researchers have access to a broad range
of indicators for palaeotsunamis, such as
stratigraphical and sedimentological, archaeological
and palaeontological methods. Although
palaeosalinity is used very often as a proxy, there is a
lack in use of geochemistry as an indicator for
palaeotsunamis. In particular, the usage of organic
geochemical proxies is limited to the values of loss on
ignition although there is a lot more potential.
Therefore, this study was initiated to test sediment
samples of proposed tsunami layers using organicgeochemical
parameter. The overall aim was to
identify organic-geochemical proxies to trace and to
quantify the effect of mixing marine and terrigenous
matter in sedimentary material by a tsunami event
A 4 m sediment core from a lagoon at Thermaikos
Gulf (Northern Greece) was taken in 2008. Distinct
layers have been selected for which a tsunami event
has been postulated (based on sedimentological
methods) as well as unaffected layers. These
samples have been subjected to extensive organicgeochemical
analyses. Beside the extractable low
molecular compounds also the molecular composition
of the non-extractable fraction as released either by
alkaline hydrolysis or pyrolysis has been investigated.
Beside the loss of ignition (LOI) a special focus was
laid on a preselected set of common biomarkers. In
detail the following compounds and corresponding
ratios have been analyzed:
� n-alkanes (extractable and non-extractable) -
LHCPI, TAR
� isoprenoids (extractable and nonextractable)
- pr/ph
� fatty acids (extractable and non-extractable)
� sterenes (extractable and non-extractable)-
C27,C28,C29 composition
� n-aldehydes
� aromatic functionalized substances and nalkanes
(pyrolysis products)
Generally, compound ratios were calculated to
differentiate marine and terrigenous contributions.
Example is the TAR ratio, which expresses the
contribution of higher n-alkanes as representatives of
higher land plant input and, consequently, represents
terrigenous matter.
The organic-geochemical analyses revealed on the
one hand differences between the biomarker
compositions of the extractable and non-extractable
fractions, but also points to different qualities of
individual substance classes or biomarker groups to
act as tsunamite-indicators. In particular, specific
variations in n-alkane and isoprenoid distributions
were detected, whereas e.g. for aldehydes and
FAMEs no clear correlation of pattern with tsunami
affected layers was observed.
However, using LHCPI, TAR and pr/ph ratio two
layers, for which tsunami related events have been
postulated, were clearly differentiated from other core
material as illustrated in Fig 1.
To our knowledge this is the first study testing a
comprehensive set of organic-geochemical
parameters as indicators for tsunamites.
a)
b)
Fig. 1: Selected biomarker ratios detected in the
extractable (a) and hydrolysable fraction (b) of
different core layers. Based on the relative proportion
it was able to differentiate layers that were either
affected or unaffected by tsunami related events.
595

P-471
Integrating biomarker and microfossil records across the
Cretaceous-Paleogene mass extinction event
Julio Sepulveda 1 , Laia Alegret 2 , Emily Wooton 1 , Changqun Cao 3 , Roger E. Summons 1
1 Massachusetts Institute of Technology, Cambridge, United States of America, 2 Universidad de Zaragoza,
Zaragoza, Spain, 3 Chinese Academy of Sciences, Nanjing, China (corresponding author:juliosep@mit.edu)
Currently, two hypothesized post-extinction models
(―Strangelove‖ and ―Living Ocean‖ [1,2]) for the status
of marine primary productivity and the global carbon
cycle following the Cretaceous-Paleogene (K-Pg)
mass extinction exist. However, these models have
been recently challenged by geochemical and
micropaleontological studies suggesting an early
resurgence in marine primary production and food
supply reaching the seafloor after the K-Pg [3,4].
Fundamentally, these results conflict with the
mechanisms proposed to elucidate carbon isotopic
anomalies preserved in deep-sea sediments. Here,
we present a comprehensive investigation of the postimpact
ecosystem recovery based on the study of
lipid biomarkers and bulk stable N- and C-isotopes in
combination with the assemblage of benthic
foraminifera. Eight remarkably expanded K-Pg
sections (clay layers) representative of different
bathymetric zones along a latitudinal gradient were
studied (Stevns Klint in Denmark, Loya and Bidart in
France, Agost and Caravaca in Spain, and El Kef and
Aïn Settara in Tunisia).
The Tunisian outcrops presented the lowest degree of
thermal maturity and appear as the most suitable for
organic geochemical work. Sections from Spain,
France and Denmark presented intermediate and
fluctuating levels of maturity, likely invoking mixtures
of organic matter of differing ages and thermal
histories through differential preservation of in-situ
organic matter. Only minor changes in eukaryotic
sources relative to bacteria were observed between
pre- and post-boundary sediments, as evidenced by
the relative contribution of steranes over hopanes
[S/S+H], except for a conspicuous and short-lived
algal decrease in the Danish section. Similarly, the
relative contribution of C28 and C29 steranes [C28/C29]
indicated insignificant changes in the ecological
dominance of their algal precursors throughout the
boundary layers. Peaks of dinosteranes were only
found in the clay layers of Tunisia, whereas they
remained unchanged or were absent in other
sections. A marked latitudinal trend in decreasing
prevalence of algal dominance (low [S/S+H]) and a
reduction in the C28/C29 ratio were observed towards
higher latitudes. A high contribution of hopanoid-
producing cyanobacteria (2-methylhopanoid index
>10%) is only observed in the aftermath of midlatitude
and upper-bathyal sections (Agost, Caravaca
and Bidart). The � 15 N record exhibits generally more
negative values before and immediately above the
boundary clay layer, whereas a gradual enrichment is
observed up section. The benthic foraminiferal
assemblage displays a reduction of infaunal species
relative to epifaunal groups following the boundary,
suggesting a reduction of food supply to the seafloor.
These results allow us to provide the following
insights regarding the post-impact environment:
a) Major changes in planktonic microfossils across the
K-Pg are not reflected in the biomarker record.
b) The lack of major variations in the relative
contribution of main phytoplanktonic groups and the
persistence of algal biomarkers throughout the
boundary suggest that primary production was only
slightly or briefly affected by the impact event.
c) A decreasing algal contribution towards high
latitudes, associated with major changes in algal
ecology, suggest a northward increase in
bacterioplankton dominance and possible mixotrophy.
d) The co-occurrence of epifaunal, shallow infaunal
and deep infaunal species, and the lack of significant
extinctions among benthic foraminifera, suggests a
relatively continuous nutrient supply to the seafloor in
the aftermath of the K-Pg, as also suggested by the
biomarker record.
References:
[1] Hsü et al., 1982. Science 216, 249–56; [2] D‘Hondt
et al., 1998. Science 282, 276–79; [3] Sepulveda et
al., 2009. Science 326, 129-132; [4] Alegret and
Thomas, 2009. Mar. Micropal. 73, 105-116.
596

P-472
Variability of Sea Surface Temperature in the Eastern Equatorial
Pacific Ocean during Last Glacial Cycles
Hasrizal Shaari, Masanobu Yamamoto, Tomohisa Irino
Hokkaido University, Sapporo Shi, Japan (corresponding author:hasrizals@ees.hokudai.ac.jp)
Various marine proxies has been used
intensively in the reconstruction of paleoclimate and
paleoceanography in the Eastern Equatorial Pacific
(EEP). In this study, we discussed the sea surface
temperatures (SSTs) produced by TEX86, U K‘ 37 and
Mg/Ca in Ocean Drilling Program (ODP) Leg 202
sites 1239, 1237 and the nearby core during the last
glacial cycles.
Multi-proxy data show a synchronous SST
variability in the glacial-interglacial cycles, and the
core-top segments were in agreement with the
modern EEP‘s SST (24.4–25.2 o C). The variation
patterns of the proxies were comparable to the global
stack of benthic δ 18 O records by Lisiecki and Raymo
(2005) and the regional δ 18 O records from
Globigerinoides ruber (G.ruber) by Lea et al. (2000),
and the CO2 concentration recorded in Dome Fuji
(Kawamura et al., 2007) they were delayed behind
the variation.
The amplitude of variation was larger in the
TEX86-derived SST record than those in U K‘ 37 and
Mg/Ca-derived SSTs. The average glacial-interglacial
amplitude contrast was ~5.2 o C in TEX86 and ~2.4 o C in
U K‘ 37 at site 1239,~2.4 o C in Mg/Ca at site TR163-19
and ~1.8 o C in U K‘ 37 at site 846.
The low value of TEX86-derived SST than the
U K‘ 37 and Mg/ca especially between MIS 2 and MIS 4
is yet remain puzzle, however there are two posibility
which could explain those condition; (1) the
production of isoprenoid GDGTs by crenarcheota
species within that period likely occured in the
subsurface water, instead of surface water; or (2) the
strengthening of upwelling systems which bring up the
cooler bottom water to the surface and decrease the
SST.
The result of TEX86 also indicated ~4.2 o C
latitudinal temperature gradiant between the EEP (site
1239) and Peruvian upwelling systems (site 1237)
and show the unifrom SST gradient during glacialinterglacial.
This suggests that the upwelling intensity
of the Peruvian Cold Tongue unchanged in glacialinterglacial
contrast.
References
Kawamura, K., F. Parrenin, L. Lisiecki, R. Uemura, F.
Vimeux, J.P. Severinghaus, M. A. Hutterli, T.
Nakazawa, S. Aoki, J. Jouzel, M. E. Raymo, K.
Matsumoto, H. Nakata, H. Motoyama, S. Fujita, K.
Goto-Azuma, Y. Fujii, and O. Watanabe. 2007.
Northern Hemisphere forcing of climatic cycles in
Antarctica over the past 360,000 years. Nature,
Vol. 448, pp. 912-916.
Kim, J.H., van der Meer, J Schouten, S., Helmke, P.,
Willmott, V., Sangiorgi, F., Koç, N.,
Hopmans, E. C,; Sinninghe Damsté, J.S.
2010.New indices and calibrations derived from
the distribution of crenarchaeal isoprenoid
tetraether lipids: Implications for past sea surface
temperature reconstructions. Geochimica et
Cosmochimica Acta 74.4639–4654
Lea D. W., Pak D. K., Spero H. J., 2000. Climate
impact of late Quaternary equatorial Pacific sea
surface temperature variations. Science
289(5485), 1719-1724
Lisiecki, L. E., Raymo, M. E., 2005. A Pliocene-
Pleistocene stack of 57 globally distributed benthic
δ 18 O records, Paleoceanography, 20, PA1003
Liu, Z., T.D. Herbert. 2004. High-latitude influence on
the eastern equatorial Pacific climate in the early
Pleistocene epoch. Nature, Vol. 427, No.6976, pp.
720 - 723
597

P-473
Application of TEX86-paleothermometry in the Baltic Sea:
Validation and temperature reconstruction of the past 1000
years
Jaap Sinninghe Damsté 1 , Karoline Kabel 2 , Florian Adolphi 2 , Marianne Baas 1 , Matthias
Moros 2
1 NIOZ Netherlands Institute for Sea Research, Department of Marine Organic Biogeochemistry, Den Burg,
Netherlands, 2 The Leibniz Institute for Baltic Sea Research, Department of Marine Geology, Warnemünde,
Germany (corresponding author:jaap.damste@nioz.nl)
The Baltic Sea is a brackish, enclosed shelf sea
located in the center of northern Europe. The
surrounding continent is densely populated. The
Baltic Sea is, therefore, strongly influenced by human
impact on the one hand and on the other hand the
health of its ecosystem is important for human welfare
in the Baltic region. Today eutrophication,
cyanobacterial blooms and anoxic bottom water
masses are major problems of the Baltic Sea
environment. To answer the question to which degree
these are caused by human activities sound data
about the functioning of the Baltic system and its
natural elasticity is needed. The BONUS project
INFLOW aims to deliver such data for the past 6000
years using sediment cores and evaluating the data
using a modeling approach. In this context the
reconstruction of surface water temperature, as a
driving factor for primary production, is of major
importance.
Due to the fact that the Baltic is a brackish sea,
common methods for marine temperature
reconstruction like δ 18 O of planktonic foraminifera and
U k‘ 37 of alkenones do not work because the specific
organisms are absent in this brackish setting. We
tested the use of the molecular temperature proxy
TEX86 since it has been successfully applied in both
marine and lacustrine settings [1-3]. The TEX86
temperature proxy is based on temperature-induced
changes in the distribution of membrane lipids of
thaumarchaeota which are found in high abundances
in the Baltic Sea.
To provide a local calibration for the Baltic Sea a set
of surface sediment from 23 locations as well as
sediment trap samples covering several seasonal
cycles and from different stations were analyzed and
compared with instrumental data. The trend in TEX86
values of surface sediments was in line with mean
annual (sub)surface water temperature and these
data were used to construct a local calibration for this
area. Sediment trap data indicate that TEX86-derived
temperatures are predominantly influence by summer
temperature. The local calibration was subsequently
applied on short cores covering the past 1000 years.
Our reconstructions indicate that for the Medieval
Warm Period temperatures were similar to present
day temperatures, whereas a temperature decrease
of 3-4°C can be observed during the Little Ice Age.
Our data indicate that TEX86-paleothermometry
provides useful reconstructions of past climate
development in the Baltic region.
References
[1] Schouten S., Hopmans E.C., Schefuss E. and
Sinninghe Damsté J.S., 2002. Earth Planet. Sci. Lett.
204, 265-274.
[2] Kim J.H, van der Meer J., Schouten S., Helmke P.,
Willmott V., Sangiorgi F., Koç N., Hopmans E.C.,
Sinninghe Damsté J.S., 2010. Geochim. Cosmochim.
Acta 74, 4639-4654.
[3] Powers L.P., Werne J.P., Vanderwoude A.J.,
Sinninghe Damsté J.S., Hopmans E.C. and Schouten
S., 2010. Org. Geochem. 41, 404-413.
Fig. 1. The Baltic Sea area with the locations of the
sites where surface sediments were sampled. Core
sampling and sediment trap deployment was in the
central basin of the Baltic.
598

P-474
Paleosalinity significance of the occurrence and distribution of
MTTCs in the Nenjiang Formation of Upper Cretaceous in
Songliao Basin, China
Li Wang 1,2 , Zhiguang Song 1 , Qin Yin 1,2 , Jiangtao Guo 1,2
1 Guangzhou Institute of Geochemistry, Chinese Academy of Sciences,, Guangzhou, China, 2 Graduate
School of Chinese Academy of Sciences, Beijing, China (corresponding author:zsong@gig.ac.cn)
A group of methylated-2methyltrimethyltridecylchromans
(MTTCs) is identified
in the core samples of Member 1 (K2n 1 ) and Member
2 (K2n 2 ) of Nenjiang Formation of Upper Cretaceous
from SK-l drilling borehole of Songliao Basin. This is
the first time that these compounds are reported from
the sediments older than Tertiary in China. Their
composition and distribution are mainly indicative of
the redox and salinity conditions of depositional
environments. Among these MTTCs, δ-MTTC is found
in relative abundant in enhanced salinity and reduced
environment, but absent in oxic and much less salinity
environment, while α-MTTC appears to be a nonsalinity
dependent compound and presents in all
environments. It is also found that α-MTTC/γ-MTTC
(α/γ) ratio has similar salinity indication as that of α/δ
ratio but is more widely applicable. The combination
of all related index and biomarkers suggest that the
massive lacustrine petroleum-prone source rocks
within K2n 1 member were likely developed under a
stratified water column environment with the reduced
and enhanced salinity of bottom water layer, which
was associated with a much less salinity top layer of
water(fresh to brackish). Finally, this study suggests
that the MTTC compounds were formed abiotically
from the precursors that originated from various
species of algae under a broad range of redox and
salinity depositional conditions.
Key words: MTTCs; depositional environment;
paleosalinity; Nenjiang formation; Songliao Basin
Acknowledge: This research was supported by
NSFC project of 40973033 and State ―973‖ Project
(2006CB701404)
599

P-475
Stable isotopes (C, S) and hydrocarbon biomarkers in
Neoproterozoic sediments of the Sierras Bayas Group,
Argentina
Mariluz Bagnoud-Velasquez, Jorge E. Spangenberg
Institute of Mineralogy and Geochemistry, University of Lausanne, Lausanne, Switzerland (corresponding
author:Jorge.Spangenberg@unil.ch)
The late Neoproterozoic or Ediacaran period, (635
to ~543 Ma) is a primordial time in the Earth history
corresponding to the beginning of animal life and the
most extreme ice ages on Earth. This contribution is
part of a long-standing project whose aim is to
reconstruct the palaeoenvironmental conditions for
Ediacaran, post-Gaskiers (last major Neoproterozoic
glaciation, ~580 Ma) shelf deposits in SW-Gondwana
and evaluate their changes according to the diversity
of organisms. To address the question of interactions
between increase of biodiversity and environmental
change a detailed elemental and isotopic geochemical
study of sedimentary rocks and associated
organic matter in conjunction with biomarker
investigations were performed on sedimentary
sequences from a large basin extended from the
Paraguay belt to the Rio de la Plata craton. The
studied Neoproterozoic to Cambrian sections include
the Corumbá Group (CG) in SW-Brazil, the Arroyo del
Soldado Group (ASG) in Uruguay and the Sierras
Bayas Group (SBG) in Argentina [1]. These
sedimentary successions have been investigated by
means of stable isotopes from carbonates (� 13 Ccar
and � 18 O), their associated organic carbon (� 13 Cker,
� 15 Nker), Rock-Eval and biomarker analyses, and
concentrations of major, trace and rare earth
elements (REE).
In all studied sections, the � 13 Ccarb excursions, the
strong enrichment of authigenic trace-elements, the
occurrence of longer chain n-alkanes, gammacerane
and low Pr/Ph and Ph/n-C18 ratios, combined with the
previous sedimentological and paleontological
observations indicate that the chemistry of the ocean
was strongly controlled by the oxygen availability;
waters being moderately oxic at the surface and
anoxic at depth for much of the Neoproterozoic. This
water column stratification was favourable to the
storage of large amounts of nutrients in the deep
ocean. During upwelling periods, the export of
nutrient-rich waters may have triggered an important
bioproductivity in surface waters. Drops in ∆ 13 Ccarb-ker
and positive � 13 Ccarb excursions record the increase in
primary productivity. Preservation of organic carbon
was ensured by reducing conditions at the bottom.
The ∆ 13 Ccarb-ker excursions could also reflect changes
in the primary biomass. Here we present new
geochemical data including sulfur isotope composition
of pyrite and structurally substituted carbonateassociated
sulfate (� 34 Spy and � 34 SCAS) from the
central region of the Tandilia orographic belt, Sierras
Bayas Group, Argentina.
The occurrence of 34 S enriched sulfides, with � 34 S
values (32.5‰) locally exceeding coeval � 34 SCAS
values (24.2 and 28.9‰) is viewed as a combined
product of globally low seawater sulfate, high rates of
bacterial sulfate reduction, and sulfate limitations
under a stratified water column inherited from
glaciations, particularly the lower water layer. The 34 Senriched
pyrites were plausibly derived from the
anoxic bottom waters while the relatively 34 S-depleted
CAS may have come from surface waters or be
produced in the redox chemocline by direct oxidation
of sulfides The sulfate concentration from a
weathering input should be higher in surface waters
than in the deep ocean and therefore, hardly
consumed due to its low abundance in the seawater.
Alternatively, direct oxidation of deep water sulfide
could also take place in the redox chemocline
producing 34 S-depleted sulfate. Diverse geochemical
proxies in the red limestones of Loma Negra
Formation are pointed to reducing conditions during
its deposition and/or early diagenesis (e.g., higher
concentrations of Fe, Mo, Zn and REE, the
occurrence of authigenic isotopically-enriched pyrite
and a molecular-inferred microbial ecosystem most
probably including green non-sulfur bacteria).
Reference
[1] Bagnoud, M. (2010) PhD thesis, University of
Lausanne, 200 pp.
600

P-476
Geochemical appraisal of palaeovegetation and climate
oscillation in the Late Miocene of Western Bulgaria
Maya Stefanova 1 , Dimiter Ivanov 2
1 Insitute of Organic Chemistry Bulgarian Academy of Sciences, Sofia, Bulgaria, 2 Institute of Biodiversity and
Ecosystems Research Bulgarian Academy of Sciences, Sofia, Bulgaria (corresponding
author:maia@orgchm.bas.bg)
The Neogene basins in Bulgaria are very important in
the system of sedimentary complexes on the Balkan
Peninsula. They contain valuable information on the
development of the flora during the Miocene. The
territory of the peninsula played a crucial role in the
evolution and migration of the Mediterranean flora
because of its specific geographical location between
the Tethyan and Paratethyan basins. Changes in the
vegetation, emergence of sclerophyll woody plants,
and dissemination of the herbaceous communities
reflect the regional palaeographic and climate
changes.
The aim was to relate palaeobotanical observations
with chemical data for Late Miocene sediments some
with lignitic-clayey units. In the study assumptions for
palaeovegetation changes and climate oscillations in
the late Miocene of Western Bulgaria based on pollen
and statistical analysis will be appreciate with
geochemical proxies.
Samples from Western Bulgaria, i.e. sediments of 5-
10 m and 20-26 m as well as coal-bearing material
were characterised by bulk and spectral methods.
GC/MS study of ―free‖ bitumens (20 ÷ 66 mg/gCorg)
revealed the presence of n-alkanes and terpenoids.
The n-alkanes, hopanes and C27 D-ring mono
aromatic hopane were present in the first fractions,
while alkan-2-ones, mid-chain ketones, polar di-and
triterpenoids were registered in the polar aromatics.
Extremely high quantities for keto triterpenoids and
products of their photochemical degradation were
determined, 50 ÷60 ug/gCorg in clay sediments and 30
ug/gCorg in coal-bearing sample.
Diterpenoids were determined only in clay sediment
sample of 20-26 m depth, up to 4.3 rel. % aromatic
hydrocarbons and 2.3 rel % polar diterpenoids.
Registered compounds were assigned to the abietane
and phyllocladane structural groups. 16�(H)-
Phyllocladane was identified in the neutral fraction,
while abietanes occurred as aromatic hydrocarbons
(dehydroabietane, simonellite, retene) and polar
derivatives like ferruginol, dehydroferruginol and 7oxo-dehydroabietane
in the aromatic/polar fraction.
Diterpenoids were observed only in sample
palaeobotanically characterized by dry and cool
climate. Friedelin, M + 426, in comparable quantities of
25 ug/gCorg was registered in all polar aromatic
fractions It is a common epicuticular wax component.
Taken alone high quantity of friedelin is not unusual in
Miocene sediments. Its high presence was registered
in Neogene lignites, Bulgaria and potential progenitor
Taxodium dubium. It is highly abundant in clay
sediments, fossil plants, oak covered soil, etc.
The novelty in this study is the extremely high
quantities of A-Norfriedel-8-en-10-one, M + 342, m/z
123 (100%), ~ 45 ug/gCorg in clay samples and in
comparable quantity with the parent friedelin, in coalbearing
sample, 27.3 ug/gCorg.
In fact A-Norfriedel-8-en-10-one could be regarded as
a product of loss of ring A in triterpenoids. First Corbet
et al. [1] described 3,4-seco-triterpenoids as major
products of photochemical/photomimetric alteration of
3-oxygenated triterpenoids. Later on reactivity of high
plant 3-oxy-triterpenoids to sunlight under real solar
exposure is investigated and assumed an analogy in
behaviour in sediments during diagenetic reworking of
parent triterpenoids [2-4]. In the set of species of the
series one more compound in high content appeared,
A-Norfriedel-dien-10-one, M + 340, with similar pattern
of mass fragmentation. Its retention time with
appearance just before A-Norfridel-8-en-10-one, gave
as ground to assume ―diene‖ structure.
The biomarker assemblage accompanied by bulk
chemical data indicated that for samples under
consideration gymnosperms were not an important
vegetation component in the palaeo mire. For organic
matter formation results accept highly reworked
angiosperm rich flora altered by climate oscillations
during the Late Miocene of Western Bulgaria.
References
[1] Corbet et al., 1980. JACS 102-3, 1171.
[2] Jaffé,R. et al., 2006. Chemosphere 64, 1870.
[3] Simoneit, B.R.T. et al., 2009. Ibid 74, 543.
[4] Bakar, N.A. et al., 2011. Ibid (submitted).
601

P-478
The first findings of 12- and 13-monomethylalkanes in dispersed
organic matter of Upper Proterozoic and Cambrian of Siberian
platform
Aleksey Kontorovich 1 , Vladimir Kashirtsev 1 , Konstantin Nagovitsin 1 , Pyotr Sobolev 2 ,
Valentina Sukhoruchko 2 , Irina Timoshina 1
1 Institute of Petroleum Geology and Geophysics SB RAS, Novosibirsk, Russian Federation, 2 Siberian
Research Institute of Geology, Geophysics, and Mineral Raw Materials, Novosibirsk, Russian Federation
(corresponding author:TimoshinaID@ipgg.nsc.ru)
Mid-chain branched monomethylalkanes, or 12-
and 13-monomethylalkanes (12- and 13-mma), were
first documented in relatively high concentrations (up
to 18%) in the Upper Proterozoic oils in Siberian
Platform (SP) by A.A. Petrov, O.A. Aref‘ev and others
[1-4 and others]. Later, hydrocarbons from this
homologous series were detected in the Precambrian
oils of Oman [5]. It became evident that this group of
biomarker hydrocarbons characterizes the
biochemistry of lipids of the specific Pre-Cambrian
biota (eukaryotes?) in some ecological niches. In the
Upper Proterozoic oils from SP and Oman [5, 6] apart
from the presence of 12- and 13-mma there were
observed steranes abnormally rich in ethylcholestane
(60-70% per the sum of steranes) [7].
12- and 13-mma were first detected by P.J.
Grantham and others [5] in the dispersed organic
matter of Upper Proterozoic source-rocks in Oman.
Later, O.K. Bazhenova and O.A. Aref‘ev identified
those hydrocarbons in some single samples of the
Upper Proterozoic from East European Platform [8];
however, hydrocarbons from this homologous series
have not been established in oils from this region.
Until present, 12- and 13-mma have not been
observed in dispersed organic matter of Upper
Proterozoic sedimentary rocks in SP [3, 9-11 and
others].
In 2010, first findings of these hydrocarbons were
made by the authors in mudstones of the Kumakha
Formation from the Lakhanda Group (Upper
Proterozoic) in the Maya depression in the southeast
of SP (7.3-9.0% per the sum of alkanes), as well as in
mudstone of the Kuonamka Formation (Lower
Cambrian) in the northeast of SP (18%), and in
Middle Cambrian marls and mudstones in
Nizhneimbakskaya-219 well (about 7%), located
within the Bakhta megasalient in the west of SP.
Thus, there have been discovered possible
sources for the specific Pre-Cambrian oils in the
Siberian Platform. For the first time, hydrocarbons
from 12 - and 13-mma homologous series have been
identified in the Cambrian organic-rich marine rocks.
The latter allows extending the stratigraphic range of
organisms known to have contained structures that
had given birth to mid-chain branched
monomethylalkanes, up to and including Cambrian.
This work was supported by RFBR (10-05-00705),
the Earth Sciences Department Program N 15, the SB
RAS Program (Project VII.59.2), the ESD-1
Programme (Project 2.8), the Interdisciplinary
Integration Project of SB RAS N 36.
References
[1] Aref‘ev, O.A., et al. (1980) Izvestiya AN SSSR,
Ser.geol. (in Russian), N 3, 135-140.
[2] Petrov, A.A. (1984) Hydrocarbons of oil (in
Russian), Moscow, Nauka, 263 p.
[3] Kontorovich, A.E., et al. (1999) Russian Geology
and Geophysics 40, N 11, 1647-1665.
[4] Kontorovich, A.E., et al. (2005) Petroleum
Frontiers 20, N 3, 11-26.
[5] Grantham, P.J., et al. (1988) Journal of Petroleum
Geology 11, 61-80.
[6] Grosjean, E., et al. (2009) Organic Geochemistry
40, 87-110.
[7] Kontorovich, А.E. (2004) Russian Geology and
Geophysics 45, N 7, 738-754.
[8] Bazhenova, O.K., Aref‘ev, O.A. (1998)
Geokhimiya, N 3, 286-294.
[9] Kashirtsev, V.A. (2003) Organic Geochemistry of
naphthides of the eastern Siberian Platform (in
Russian), Yakutskii Filial Izdatel‘stva SO RAN, 160 p.
[10] Parfenova, T.M., et al. (2004) Russian Geology
and Geophysics 45, N 7, 862-874.
[11] Timoshina, I.D. (2004) Russian Geology and
Geophysics 45, N 7, 852-861.
602

P-479
Assessment of the 1,14 diol SST proxy based on sediment trap
samples from the NW African upwelling area
Eleonora Uliana 1 , Gerard Versteegh 1 , Gesine Mollenhauer 1,2 , Enno Schefuss 1
1 MARUM, Bremen, Germany, 2 Alfred Wegener Institut, Bremerhaven, Germany (corresponding
author:euliana@marum.de)
The most commonly applied organic proxies for sea
surface temperature (SST) so far are the alkenonebased
U K 37 index and TEX86 based on glyceroldialkyl-glycerol-tetraethers
from marine
crenarchaeota. However, both proxies are not always
reflecting precisely the environmental signal recorded
in surface waters. In areas with input of upwelled,
nutrient-rich waters siliceous phytoplankton
suppresses coccolithophorid productivity by
competition as long as silica is available. Therefore,
U K 37-based SST estimates are often too high and
don‘t reflect the cooling during full upwelling
conditions. They record mean annual SSTs rather
than upwelling SSTs (Müller et al. 1998). In contrast
diatoms bloom especially in times of high nutrient
availability, making their biomarkers a potentially ideal
SST-proxy for paleo-reconstructions during upwelling
conditions. Recently, a new biomarker specific for
upwelling diatoms has been proposed. Rampen, et al.
(2009) have introduced a new index (1,14 diol chain
length index: 1,14DI) which combines long chain 1,14
diols obtained from diatom cultures of the genus
Proboscia and those from surface sediments from the
eastern South Atlantic. The new index has shown a
clear correlation between chain length and
temperature.
The presented study is based on measurements of a
series of sediment trap samples collected off Cape
Blanc in the upwelling area off Mauritania (NW
Africa). Sediment traps were analysed to investigate
the seasonal variations in diol index-based SST
estimates. Seasonal changes in both Proboscia sp.
frustules as well as long chain diols (1,14 C28 and C30)
have been recorded. Calculation of the 1,14 DI
following the method of Rampen et al. (2009) results
in two well defined groups of samples. The first group
(open dots in Fig. 1) coincides with the period of
stratification of the water column (non-upwelling
season) and has a 1,14DI value range between 0.25
and 0.35.The second group of samples with much
higher 1,14DI values (0.43 - 0.65, filled dots in Fig. 1)
corresponds to the upwelling season. While the DI
values of upwelling samples (filled dots) correspond
well with the core top SST calibration (filled triangles,
Rampen et al. (2009), the non-upwelling samples
C30/(C28+ C30) 1,14-diols
(open dots) reveal lower than expected 1,14DI values
resulting in too low SST estimates compared to actual
SSTs based on satellite measurements. These values
seem to fall more on the temperature calibration
derived for cultures of Proboscia sp. (open triangles,
Rampen et al.,2009) .
1
0.8
0.6
0.4
0.2
0
y = 0.028x - 0.023
R 2 = 0.52
0 10 20 30
Temperature [°C]
Fig. 1. Correlation of Diol Index values from sediment trap
samples from Cape Blanc (dots, filled: upwelling season, open:
non-upwelling season, our study) and core tops from the eastern
south Atlantic (filled triangles) plus cultures (open triangles) with
temperature. Core-tops, culture data and correlation from Rampen
et al. (2009).
Rampen, et al. 2009. Org. Geochem., 40, 1124-1131.
Mueller et al. 1998. Geochim. Cosmochim. Acta, 62,
1722–1757
Proxies to assess past sea surface temperature
(SST) variations are a powerful tool to infer past
changes in ocean circulation and upwelling.
603

P-480
The 3 P’s* and the Albian oceanic anoxic event (OAE) 1b
(*palaeoclimate, palaeoenvironment & palaeooceanography)
Isabel Urbat
Fugro Robertson Limited, Llandudno, North Wales, United Kingdom (corresponding
author:isabel.urbat@fugro-robertson.com)
The Cretaceous OAE 1b is one of the major
perturbations of the global carbon cycle. It is
documented in Albian black shale deposits from the
Atlantic regions as well as in regions of the Western
Tethys. In the here presented study, high-resolution
geochemical profiles from two palaeogeographically
distinct locations (Mazagan Plateau DSDP Site 545
and the Vocontian Basin) are established. The
Mazagan Plateau was located in the lower Albian
tropical climate belt offshore Morocco and the
Vocontian Basin was situated in the subtropical Albian
climate belt in the western Tethys region.
High-resolution geochemical profiles show, that the
perturbation of the carbon cycle occurred
synchronously in the oceanic- and atmospheric
carbon reservoirs. This is indicated by the stable
isotopic composition of biomarkers for terrestrial
higher plant waxes and marine algal lipids. OAE 1b is
associated with a pronounced negative shift in various
carbon isotope reservoirs. Negative shifts in the
carbon isotopes are also observed for the Toarcian
OAE and the early Aptian OAE 1a and are thought to
result from the catastrophic release of methane from
marine gas hydrates. Climate proxies indicate a shift
towards more humid climate conditions. The effects of
this major perturbation of the climate had also
consequences for the biota. At the Mazagan Plateau
the organic matter production increased even though
the upwelling weakened probably due to an increased
influx of nutrients from the adjacent African Continent.
The bioproduction of the Vocontian Basin shifted
towards bacterial dominated communities.
Discussing the trigger mechanisms leading to the
abrupt onset and termination of OAE 1b is another
important feature of this work. The magnitude of the
isotope excursion at the Mazagan Plateau remains
constant over several ten thousand years. By
contrast, a single methane blast would strongly affect
the atmospheric signal, but the concentration of light
carbon dioxide would than constantly exhaust. Hence,
the Mazagan record rather suggests a constant
supply of 13 C-depleted CO2 during the entire black
shale interval. Therefore, a combination of moderate
scale methane pulses supplemented by continuous
methane emission at elevated levels over a longer
time interval is indicated. The two pulses encompass
the total trigger period of OAE 1b, estimated to be
about 25 ka. The results calculated with a coupled
atmosphere–land–ocean–sediment model presented
for the Mazagan Plateau reveal similarities to the
Vocontian Basin record. Nevertheless, both climate
systems reacted differently due to the perturbation at
the onset of OAE 1b. These differences can be
explained by a shifting Inter Tropical Convergence
Zone (ITCZ). Modelled net flux rates, using an
Atmospheric General Circulation Model (AGCM),
highlight precipitation and evaporation rates for the
studied sections during the Cretaceous and highlight
strong regional differences dependent on
palaeolatitudes. A moderate ITCZ shift during OAE 1b
explains the beginning humid climate conditions
coupled to alleviative tradewinds at the Mazagan
Plateau and also the enhanced climate contrasts at
the Vocontian Basin with a general trend towards
higher aridity. In summary, the OAE 1b is recorded at
several distinctive settings reflecting specific climatic
and environmental conditions. These are still
identifiable due to characteristic C-isotope curves and
temperature proxies. Furthermore, the isochronous
widespread deposition and a comparison to literature
data indicate that OAE 1b was a global rather than a
supraregional event.
604

P-481
A biomarker reconstruction of Holocene changes in rainfall and
runoff from Charlotte Harbor (Florida)
Els E. van Soelen 1 , Gregg R. Brooks 2 , Rebekka Larson 2 , Jaap S. Sinninghe Damsté 3 ,
Gert-Jan Reichart 1
1 Utrecht University, Utrecht, Netherlands, 2 Eckerd College, St. Petersburg, Netherlands, 3 Royal Netherlands
Institute for Sea Research, Den Burg, United States of America (corresponding
author:e.vansoelen@geo.uu.nl)
Climate in Florida is characterized by a strong annual
hydrological cycle, with wet summers and dry winters.
Precipitation is regulated by, amongst others, annual
shifts in the position of the Intertropical Convergence
Zone (ITCZ). During the Northern Hemisphere
summer, the ITCZ moves North of the equator
thereby increasing transport of Caribbean and moist
air into the Gulf of Mexico. Currently, also the El Niño
Southern Oscillation (ENSO) affects precipitation in
Florida, especially by increasing the amount of winter
rainfall during an El Niño event. ENSO
reconstructions show a modern type periodicity
throughout the Late Holocene, but limited ENSO
activity during the mid Holocene [e.g. 1]. To study
long term changes in the hydrological cycle of Florida,
a paleoclimate reconstruction was made, of the past
~9000 years using sediments recovered from a
shallow marine setting in southwest Florida (Charlotte
Harbor).
Sediments from Charlotte Harbor allow for
the simultaneous reconstruction of both terrestrial and
marine environmental changes. Whole core XRF
scanning was used to reconstruct variations in quartz
and carbonate content, which was used to correlate
different sediment cores. Changes in runoff were
reconstructed by looking at fluxes of terrestrial
biomarkers, e.g. long chain n-alkanes, n-alcohols and
friedelan-3-one, which are all produced by higher
plants. Primary productivity was reconstructed based
on, amongst others, fluxes of dinosterol, (proxy for
dinoflagellates), C30 and C32 1,15 diols, (which likely
derive from eustigmatophytes) and C36 alkenones
(position of double bonds at ω15,20, unknown origin).
The BIT index (an index of Branched (terrestrial)
versus Isoprenoidal (marine) Tetraethers [2]), and
C/N ratios were used to estimate the relative input of
terrestrial versus marine organic matter.
The biomarker fluxes show maxima during
the mid Holocene and in the past century. High fluxes
of terrestrial biomarkers indicate an increase in runoff;
in a response to this, primary productivity increases
which results in higher fluxes of aquatic biomarkers.
Between 6000 and 5000 years BP there is a
maximum in runoff, likely due to enhanced rainfall in
this period. Reconstructions of runoff and precipitation
in the Gulf of Mexico and Caribbean also indicate
increased moist conditions during the mid Holocene
[3] and increased moisture transport into the Gulf of
Mexico between 6500 and 4500 years BP [4].
Warmer northern Hemisphere temperatures during
the mid Holocene and, as a consequence of this, a
more northward position of the ITCZ might have been
responsible for this, because this would enhance
easterly winds which are responsible for bringing
moist air to the Gulf of Mexico.
From 3500 years BP onwards, the terrestrial
input strongly decreases and organic proxies indicate
a change towards relatively more marine conditions.
This change coincides with an intensification of ENSO
activity. Pollen reconstructions in a wetland in
southwest Florida show a development from grass
vegetation during the mid Holocene to a Cypress
swamp forest in the late Holocene because of wetter
conditions (longer growing season) [5]. This
development in vegetation would increase the water
retaining capacity of the soils and prevent erosion,
which explains the observed decrease in terrestrial
biomarkers. Over the last century, runoff increased
again due to human activity, like deforestation and
wetland drainage.
[1] Moy et al., 2002. Nature 420, 162-165
[2] Hopmans et al., 2004. Earth Planet. Sci. Lett. 224,
107-116
[3] Montero-Serrano et al., 2010. Global Planet.
Change. 74, 132–143
[4] Poore et al., 2003. Paleoceanography, 18, 2, 1048
[5] Donders et al., 2005. PNAS 102(31), 10904-10908
605

P-482
Meter-scale oxygen gradients and selective organic matter
degradation: implications for proxy interpretation
Kara Bogus 1 , Karin Zonneveld 1,2 , David Fischer 2 , Sabine Kasten 3 , Gerard Versteegh 2
1 Universität Bremen, Bremen, Germany, 2 Marum — Center For Marine Environmental Sciences, Bremen,
Germany, 3 Alfred Wegener Institute for Polar and Marine Research, Bremerhaven, Germany
(corresponding author:ka_bo@uni-bremen.de)
Organic matter (OM) degradation processes
selectively preserve the more recalcitrant fractions in
sediments. For environmental reconstructions through
the application of OM-based proxies, this degradation
bias has to be accounted for. The oxidation state of
the sediments is an important variable influencing OM
degradation whereby low oxygen levels result in much
less degradation. This is demonstrated by the
elevated carbon contents in black shales, sediments
from oxygen minimum zones (OMZ) and anoxic
basins as well as at oxidation fronts like the Madeira
Abyssal Plain and Eastern Mediterranean sapropels.
Most studies investigating the impact of the oxidation
state on OM degradation do not involve samples with
identical initial OM composition since the samples
compared have been deposited at different locations
or differ in age. Others compare pre-aged material,
thus missing the early and most rapid degradation
process. This degree of uncertainty makes it difficult
to separate initial environmentally-induced changes
from those induced by selective aerobic degradation.
In order to constrain these problems and evaluate the
extent of early selective aerobic degradation on
proxies in surface sediments, we restricted sampling
distance to a meter-scale oxygen gradient associated
with a cold seep in the northeastern Arabian Sea.
Samples taken along a similar seep within the OMZ
and on a larger transect through the OMZ served as
controls. Here, we report on the impact of selective
oxic degradation at the sediment-water interface on
the relative lipid and palynomorph proxy composition.
Biomarker-based proxies used to represent sediment
alteration, including the diol/keto-ol (DOXI) ratio and
alcohol preservation index (API), are predicated on
selective degradation of the more labile components.
They indicated increased sediment alteration with
increasing oxygen concentrations at the sedimentwater
interface. Additionally, proxies used to
reconstruct productivity, such as Brigantedinium spp.
dinoflagellate cysts, phytol, cholesterol, and dinosterol
were highly labile in the oxygen-rich surface
sediments. However, the development of indices
based on the abovementioned biomarkers as well as
TEX86, and their degradation products exhibited a
more complex picture. It appears that for the
productivity proxies, factors additional to the oxygen
concentration, most likely sorptive protection of the
molecular proxies, to some extent protect these labile
components from early diagenesis. In contrast, the
seep environment and not the oxygen state of the
sediments influence the TEX86. Overall, the
differences between OM composition in relation to
oxygen availability on very small spatial scales clearly
demonstrate the importance of oxygen in the
degradation of OM. Therefore, care must be taken
when using these sensitive proxies for oceanographic
reconstructions in areas where changing redox
conditions at the sediment-water interface could be
expected.
606

P-483
Selective aerobic and anaerobic degradation of lipids and
palynomorphs in the Eastern Mediterranean since the onset of
sapropel S1 deposition
Gerard J.M. Versteegh 1 , Karin A.F. Zonneveld 1 , Gert J. de Lange 2
1 MARUM Bremen University, Bremen, Germany, 2 Faculty of Earth Sciences, Utrecht University, Utrecht,
Netherlands (corresponding author:versteegh@uni-bremen.de)
Selective degradation of organic matter (OM) in
sediments is important for reconstructing past
environments and understanding the carbon cycle.
We present changes between and within lipid classes
and kerogen types (as palynomorph groups) in
relation to the OM flux to the sea floor and oxidation
state of the sediments since the early Holocene for
Eastern Mediterranean site ABC26. This includes the
initially oxic but now anoxic presapropel, the still
unoxidised lower part of the organic rich S1 sapropel,
its postdepositionally oxidised and now organic-poor
upper part as well as the overlying postsapropelic
sediments, which have always been oxic. A general
~2.3 times increase in terrestrial and marine input
during sapropel formation is estimated on the basis of
the total organic carbon (TOC), pollen, spore,
dinoflagellate cyst, n-alkane, n-alkanol and n-alkanoic
acid concentration changes in the unoxidised part of
the sapropel (Fig. 1). The long-chain alkenones, 1,15
diols and keto-ols, loliolides and sterols indicate that
some plankton groups, notably dinoflagellates, may
have increased much more. Apart from the terrestrial
and surface water contributions to the sedimentary
OM, anomalous distributions and preservation of
some C23–C27 alkanes, alkanols and alkanoic acids
have been observed, which we consider as a
contribution by organisms living in situ.
Comparison of the unoxidised S1 sapropel with the
overlying oxidised sapropel and the organic matter
concentration profiles in the oxidised postsapropelic
sediments demonstrate strong and highly selective
aerobic degradation of lipids and palynomorphs.
There seems to be a fundamental difference in
degradation kinetics between lipids and pollen which
may be possibly related with the absence of sorptive
preservation as a protective mechanism for palynomorph
degradation. The n-alkanes, Impagidinium,
and Nematosphaeropsis are clearly more resistant
than TOC. The n-alkanols and n-carboxylic acids are
about equally resistant whereas the pollen, all other
dinoflagellate cysts and other lipids appear to degrade
considerably faster, which questions the practice of
normalising to TOC without taking diagenesis into
account. Selective degradation also modifies the
relative distributions within lipid classes, whereby the
longer-chain alkanes, alcohols and fatty acids
disappear faster than their shorter-chain equivalents.
Accordingly, interpretation of lipid and palynomorph
assemblages in terms of pre- or syndepositional
environmental change should be done carefully when
proper knowledge of the postdepositional
preservation history is absent. Two lipid-based
preservation proxies are tested the diol-keto-ol
oxidation index based on the 1,15C30 diol and keto
ols and the alcohol preservation index (API) whereby
the former seems to be the most promising.
Fig. 1 Concentration changes over the oxidation front
and within the visible sapropel. Each open circle
represents a lipid or palynomorph taxon. Closed
circles represent group averages OS, oxidised
sapropel; VS, visible sapropel.
607

P-484
Coupling of Miocene-Pliocene (7-5 Ma) African climate, surface
ocean temperature and marine organic carbon burial: highresolution,
multi-proxy records from the eastern equatorial
Atlantic (ODP 959)
Thomas Wagner, Olubunmi Eniola, Erin McClymont
Newcastle University, Newcastle upon Tyne, United Kingdom (corresponding
author:thomas.wagner@ncl.ac.uk)
The late Miocene to early Pliocene was a period of
major climate transition with events that impacted on
large-scale ocean and atmospheric circulation and
consequently global climate. Tectonic events such as
the Tibetan and Himalaya uplift and the closing of
ocean gateways are proposed to have caused a long
term cooling trend and a principal change in
vegetation in the low latitudes, including a general
shift from C3 vegetation to C4 vegetation in Africa
around 8-6 Ma 1 . Large-scale hydrological changes
are also recorded by carbon isotopic ratios in
carbonates and soil organic matter 2 .
With regard to the tropical Atlantic corridor the
establishment of modern type atmospheric and ocean
circulation at about 4.4-4.3 Ma 3 has been proposed.
Further studies on ODP 959 off tropical West Africa 4
showed that the late Miocene to early Pliocene
climate records were modulated by cyclic high
amplitude swings in TOC which were linked to the
evolution of African trade winds, continental upwelling
and eustatic sea level fluctuations. For these
sediments Norris 3 inferred cooling of surface waters
by 2-3°C (6.7-5.9 Ma) and proposed the onset of
modern type climate ocean dynamics ~4.4 Ma.
Here, we take these previous studies further and
present new complementary high-resolution (2.5 cm,
~2.5-5 kyr) records of sea-surface temperatures
(SSTs, alkenone derived U K 37‘), supply of terrestrial
organic matter (leaf wax lipids) and organic carbon
burial (TOC) for ODP Site 959. The complementary
new data provide, in combination with detailed
frequency analyses, new insights into the causal
relationships and trends between African climate,
marine response, and links with high latitude climate
forcing during the critical time interval 7-5 Ma. All
geochemical records show distinct high frequency
(millennial time scale) fluctuations that argue for a
highly dynamic and sensitive response of the tropical
Atlantic to African climate and orbital forcing. TOC is
low (in general

P-485
Complications in the interpretation of molecular
paleotemperature reconstructions using isoprenoid and
branched tetraethers: Lessons to be learned
Josef Werne 1 , Beth Bernhardt 1 , Martijn Woltering 1 , Melissa Berke 1 , R. Douglas Ricketts 1 ,
Margarita Caballero 2 , Ellen Hopmans 3 , Stefan Schouten 3 , Jaap Sinninghe Damsté 3,4
1 Large Lakes Observatory, University of Minnesota Duluth, Duluth, United States of America, 2 Institute of
Geophysics, Universidad Nacional Autonoma de Mexico, Mexico City, Mexico, 3 Dept. of Marine Organic
Biogeochemistry, Royal Netherlands Institute for Sea Research (NIOZ), Texel, Netherlands, 4 University of
Utrecht, Utrecht, Netherlands (corresponding author:jwerne@d.umn.edu)
Research efforts over the past decade have
highlighted the potential for new, microbial lipid based
proxies for temperature to be applied in lake
sediments. Schouten et al. (2002) proposed a new
molecular temperature proxy based on the distribution
of specific isoprenoid GDGT (glycerol dialkyl glycerol
tetraether) lipids derived from marine Group I
Crenarchaeota (now Thaumarchaeota) called the
TEX86. More recently, structurally similar branched
GDGT lipids have been identified widespread in soils
and peats. Based on analysis of globally distributed
soils, Weijers et al. (2007) proposed a pair of
molecular proxies, the ―MBT‖ (methylation index of
branched tetraethers) and ―CBT‖ (cyclization index of
branched tetraethers) that can be used in conjunction
to reconstruct the pH and temperature of the soil in
which the bacteria were living.
TheTEX86 and CBT/MBT have been applied in
several lacustrine and marine systems, often
producing robust paleotemperature records. For
example, the TEX86 record from Lake Malawi, in East
Africa, is currently the longest, most high-resolution
temperature record from the African continent
(Woltering et al., 2010), and the MBT/CBT record
from Valles Caldera in New Mexico, USA, provides
realistic temperatures spanning two full glacial/
interglacial cycles, and is one of the few records from
MIS-11 in North America (Fawcett et al., 2011).
Despite, the significant advances derived from these
and other paleotemperature records, not all records
result in the anticipated trends.
Here, we present data from a suite of systems in
which the temperature profiles reconstructed using
the TEX86 or MBT/CBT proxies are not consistent with
known environmental change or with other
temperature reconstructions made in the same
system. In some systems, the poor TEX86 and
MBT/CBT temperature records are due to inputs from
Euryarchaeota, either from soils (Lake Victoria, East
Africa and Lago Verde, Mexico) or from anaerobic
water masses (Cariaco Basin, Venezuela).
Euryarchaeotal contributions of GDGTs, cause a
breakdown between the TEX86 temperature (derived
from Thaumarchaeota) and the annual mean surface
water temperature that we seek to reconstruct. In
contrast, in Lake Superior the TEX86 in fact reflects
the temperature of the mid-water depth of
Thaumarchaeotal growth rather than surface
temperatures – thus it does in fact reflect the
temperature of the growth environment, it is simply
not the temperature that is sought after in most
paleoclimate studies. Similarly, in Issyk-Kul,
Kyrgystan, evidence suggests that the TEX86 is
influenced by depth of Thaumarchaeotal growth, the
unusual circulation patterns in this system, and
possibly by development of a freshwater cap over
brackish bottom waters during glacial melt.
Analysis of small lakes from the USA, including
Deming Lake, MN, Bath Pond, OH, and Lake Tulane,
FL, reveal other complexities. Generally, the
temperatures produced match instrumental
measurements within the error of the calibration, both
in core-top sediments and downcore. However, a
rapid downcore MBT/CBT temperature increase in
surface sediments (e.g. 7ºC in 7 years/5 cm in Bath
Pond) suggests that in situ growth of the source
bacteria and/or diagenesis altering the suite of
GDGTs may influence the MBT/CBT.
This study allows us to provide constraints on the
applicability of these temperature proxies and
indicates the types of environmental data that can be
derived from ―bad‖ GDGT-based temperature profiles.
Schouten et al. (2002) EPSL 204:265-274.
Weijers et al. (2007), GCA, 71:703-713.
Woltering et al. (2010) Palaeogeogr, Palaeoclim,
Palaeoecol. doi:10.1016/j.palaeo.2010.02.013
Fawcett et al. (2011) Nature. In press.
609

P-486
New molecular marker and spectroscopic tools for
reconstructing wildfire history
Daniel B. Wiedemeier 1 , Simon G. Haberle 2 , Evelyn S. Krull 3 , Michael W.I. Schmidt 1
1 Department of Geography, University of Zurich, Zurich, Switzerland, 2 Archaeology & Natural History,
Australian National University, Canberra, Australia, 3 CSIRO Land and Water, Glen Osmond, Australia
(corresponding author:daniel.wiedemeier@geo.uzh.ch)
Wildfire regimes have been changing during the late
Quaternary under the influence of changing climate
and vegetation, and by anthropogenic impact.
Wildfires are an important parameter in the biosphereclimate
system and affect the carbon cycling. Thus,
reconstructing their history helps to understand
palaeoenvironmental conditions and is essential to
project future biosphere-climate interactions and
associated carbon cycles.
Late Quaternary wildfire reconstruction has mainly
been based on dated lake sediment cores, where the
number of microscopically detected charcoal particles
has served as the raw data for assessing the past fire
frequency [1]. Quantifying (microscopically) visible
charcoal may reflect the relatively large and
structurally sound charcoal particles from forest fires.
However, this technique is at best semi-quantitative
and less likely to quantify submicroscopic charcoal
fractions [2], e.g. derived from grasses.
Therefore, we are developing a new methodology to
infer past wildfires from lacustrine sediments by using
molecular marker and spectroscopic tools. Such
geochemical methods could assess the whole size
range of charred fire residues in sedimentary records
and could yield additional information about the
burned vegetation when only microscopically invisible
fire residues are present. In particular, we are
adapting a geochemical marker method (benzene
polycarboxylic acids (BPCA) [3]) for this task.
In order to calibrate and validate the BPCA method
for sedimentological fire reconstruction, we used well-
characterized lake sediment cores from Australia.
They exhibit distinct wildfire histories (charcoal
counting method). We compared these data with the
results of the BPCA method. In addition, we examined
the cores with Mid InfraRed spectroscopy coupled
with Partial Least Square analysis (MIR-PLS), which
is another geochemical method that can detect
pyrogenic material independent of its particle size. We
used MIR-PLS as a screening method to locate
interesting sections of the cores and it provided an
additional dataset of fire residue contents, to which
the BPCA molecular marker analysis was compared.
By using the multi-proxy approach of the standard
(charcoal particle counting), molecular marker (BPCA)
and spectroscopic (MIR-PLS) method, reconstruction
of wildfire history is improved and allows a better
comparison between different ecosystems.
[1] Conedera, M. et al. (2009) Reconstructing past fire
regimes: methods, applications, and relevance to fire
management and conservation. Quatern. Sci. Rev.
[2] Skjemstad, J. et al. (1999) Soil organic carbon
dynamics under long-term sugarcane monoculture.
Austral. J. Soil Res.
[3] Schneider, M.P.W. et al. (2011) Comparison of
gas with liquid chromatography fort he determination
of benzenepolycarboxylic acids as molecular tracers
of black carbon. Org. Geochem.
610

P-487
Late Quaternary environmental change of Yellow River Basin: an
organic geochemical record in Bohai Sea (North China)
Yunping Xu 1,2 , Wenbing Tan 1 , Dongyan Sun 1
1 MOE Laboratory for Earth Surface Processes, College of Urban and Environmental Sciences, Beijing,
China, 2 Center for Ocean Studies at Peking University, Beijing, China (corresponding
author:yunpingxu@pku.edu.cn)
Bulk geochemical characterization (total organic
carbon, grain size distribution, carbon isotope
composition) and molecular biomarkers (lignin
phenols, straight chain aliphatic hydrocarbons,
glycerol dialkyl glycerol tetraethers) were analyzed for
a 21 m deep core from the Bohai Sea (north China),
spanning ca 21 ka BP. These paleo-proxies
presented remarkable differences between the late
glacial period and the Holocene, reflecting continental
and coastal environments, respectively. Two peat
layers were deposited during the period of ca 9000–
8460 yr BP. Thereafter the core site has been
consistently covered by seawater until recent
reclamation of land from sea. The occurrence of a
total organic carbon maximum from ca 6000–3800 yr
BP was attributed to delivery of organic carbon
enriched sediments via the Yellow River, consistent
with increased vegetation density and higher
development of soil under warm and humid mid-
Holocene climate conditions. The distributions of
lignin phenol compositions and C31/C29 n-alkanes
suggested the largest expansion of woody plants
between ca 5300 and 4000 yr BP, corresponding to
the extremely favorable climatic conditions. Since ca
3800 yr BP, an abrupt increase in the C31/C29 nalkane
ratio suggested higher abundance of grasses,
consistent with a drying climate trend after the mid-
Holocene. Since our coastal sediments close to the
Yellow River outflow contain a catchment-integrated
environmental signal of the river basin, molecular
proxies demonstrate that the variability of vegetation
distributions in the Holocene is a widespread
phenomenon in those areas adjacent to Yellow River
basin.
Reference:
Shi, Y., Kong, Z., Wang, S., Tang, L., Wang, F., Yao,
T., Zhao, X., Zhang, P., Shi, S., 1993. Mid-Holocene
climates and environments in China. Global &
Planetary Change 7, 219–234
611

P-488
Paleoenvironmental changes from organic matter composition
in the California margin sediments (ODP Leg 167, Hole1017E)
during the last 45kyrs
Shuichi Yamamoto 1 , Chieko Dairiki 1 , Ryoshi Ishiwatari 2
1 Soka University, Tokyo, Japan, 2 Tokyo Metropolitan University, Tokyo, Japan (corresponding
author:syama@soka.ac.jp)
Climate instability during the last glacial period
which correspond to Dansgaard-Oeshger (D-O)
events has already been recognized in the California
margin of the northeast Pacific from investigations of
18 O in foraminifera and sea surface temperature
(SST) by alkenone [1][2]. However, it is still important
to clarify how the marine and land ecosystems
responded to climate changes during the last glacial
period.
The sediment samples for our study were obtained
from ODP Hole 1017E located on the Santa Lucia
slope (34°32.10‘ N, 121°06.43‘ W). Eighty two organic
compounds such as fatty acids, alcohols, lignin
phenols, cutin acids and sterols in the sediment
during the last 45 kyrs were analyzed by
thermochemolysis with tetramethyl ammonium
hydroxide and GC-MS.
The vertical distribution of the total amount of
organic compounds identified is synchronized to total
organic carbon (Fig. 1 (a)) and SST (Fig. 1(g) as
shown in Fig. 1(b) with high concentration during the
periods of interglacial and interstadial warming during
the Holocene, Bølling/Allerød and D-O events. The
vertical profiles of proportions of marine derived (e.g.,
phytol, n-C14-C18 fatty acids, almost sterols), land
derived (e.g., lignin phenols, n-C28-C32 fatty acids,
cutin acids) and the other organic compounds show
that the percentages of marine origin and land origin
correspond well to the SST (Fig. 1(c) and (d)); the
proportion of marine origin is high (64.2 %) during
Holocene and low (49.4 %) during Younger Dryas to
marine isotope stage 3, while those of land origin is
low (15.8 %) and high (31.0 %), respectively. Results
from factor analysis to the vertical profiles of organic
compounds indicates that the first and second factor
loadings also correlate well to the SST (r 2 =0.724,
r 2 =0.736, Fig. 1(e) and (f)). Then, the results suggest
that contribution to sedimentary organic matter from
marine and land depend on temperature.
[1] Kennett et al. (2000) Proc. Ocean Drill. Program
Sci. Results, 167, 249.
[2] Seki et al. (2002) Geophysical Research Letters,
29, 1.
612

P-489
Branched GDGTs as biomarkers for temperature
reconstructions from paleosols. Three case studies and
potential complications
Roland Zech 1 , Li Gao 2 , Rafael Tarozo 2 , Yongsong Huang 2
1 Geological Institute, ETH Zurich, Zurich, Switzerland, 2 Geological Institute, Brown University, Providence,
United States of America (corresponding author:godotz@gmx.de)
Branched Glycerol Dialkyl Glycerol Tetraethers
(GDGTs) are membrane lipids derived from yet
unknown soil bacteria. Empirical studies have shown
that the composition of branched GDGTs in topsoils
varies in their degree of cyclisation and methylation,
which is expressed as CBT and MBT (i.e. cyclisation
and methylation index of branched tetraethers)
depending on soil pH and mean annual air
temperature [1]. Can we use MBT and CBT to
reconstruct past pH and temperatures from loesspaleosols-sequences?
First applications on the
Chinese Loess Plateau seem to be promising [2,3].
Here we present results from three case studies –
three well-studied loess-paleosol sequences, in which
we measured branched GDGTs in order to empirically
test the applicability of the newly discovered
biomarkers for paleoenvironmental reconstruction and
to possibly obtain quantitative records for regional
paleotemperatures [4]. The results show that
significant disagreements exist between
interpretations based on available stratigraphic,
pedological and geochemical data on the one hand,
and GDGT-derived reconstructions on the other hand.
The case study from the ~150 ka loess section
‗Crvenka‘ in Serbia, for example, shows an almost
monotonous increase in GDGT-derived temperatures
from the bottom of the profile to the top (Fig. 1).
Reconstructed temperatures for the loess V L1L1 are
thus much higher than one would expect from its
correlation with Marine Isotope Stage (MIS) 2, while
the paleosol V S1 shows the lowest reconstructed
temperatures of the whole record, which seems to be
at odds with its correlation with the last interglacial
(MIS 5).
Another case study, the ~6.5 m deep and ~80 ka
paleosol sequence ‗Maundi‘ from Mt Kilimanjaro
shows GDGT-derived temperatures that are
monotonously increasing with depth by more than
10°C. This contradicts the fact that most of the
sediments below the uppermost Holocene soils were
deposited during MIS 2 to 4, i.e. under presumably
cold, last glacial conditions.
Given that very little is known about the GDGTproducing
organisms so far, we speculate that there
might be several reasons that are currently
complicating the straight-forward interpretation of the
respective indices: (i) Some of the target peaks in the
HPLC chromatograms consist of multiple, yet
unidentified compounds. Further research is
necessary to improve compound separation,
identification and, accordingly, calibration. (ii) GDGT
patterns may not only depend on soil temperature and
pH. Other potential factors, such as redox conditions,
nutrient availability, seasonality, changes in the
bacterial communities etc, need to be tested. (iii)
GDGT-producing bacteria do not only live in the
topsoils, and a non-negligible subsurface production
of GDGTs could thus result in an overprint of ‗older‘
paleo-environmental signals at depth, a concern that
could be coined the ―growth depth effect‖. (iv) Eolian
transport might contribute non-negligibly to the
amounts of GDGTs in some loess-paleosols. This
might overprint the in-situ signal of the proxies.
Fig. 1. The loess-paleosol-sequence Crvenka, in Serbia,
and results of the GDGT measurements.
References
[1] Weijers, J.W.H. et al. (2007), Geochim. Cosmochim.
Acta, 71, 703–713.
[2] Peterse, F. et al. (2011), Earth Plan. Sci. Lett., 301, 256-
264.
[3] Gao, L. et al. (2011), Palaeo3, submitted.
[4] Zech, R., Gao, L., Tarozo, R. and Huang, Y. (2011), Org.
Geochem., submitted.
613

P-491
Methoxy-serratenes as discriminant biomarkers for soils
developed under conifer forests
Claude Le Milbeau, Marlène Lavrieux, Jérémy Jacob, Renata Zocatelli, Jean-Robert Disnar
Institut des Sciences de la Terre d'Orléns, ISTO, Université d'Orléans, UMR 6113 du CNRS/INSU, Orléans,
France (corresponding author:claude.le-milbeau@univ-orleans.fr)
The evolution of landscapes through time
constitutes a challenge for both archaeologists and
paleoenvironmentalists. For example, human
deforestation (for cultivation and building) strongly
affected the shape of continental surfaces with
supposed impacts on the global carbon cycle of which
the timing and extent remains controversial.
Molecular biomarkers detected in soils can
provide clue information on the past local vegetation,
and thus on past land uses. In addition, if these
biomarkers are transferred from soils to sedimentary
archives, they can be used to reconstruct the
evolution of ecosystems through time. Higher plant
pentacyclic triterpenes are commonly associated with
angiosperms and are increasingly used in
environmental reconstructions. Due to their wide
diversity of structures, functions and configurations,
they constitute valuable chemo-taxonomic targets,
considering that a restricted number of organisms are
able to synthesize specific structures. For example,
pentacyclic triterpene methyl ethers can be related to
Gramineae [1], [2] whereas triterpenyl acetates are
mainly produced by Asteraceae [3]. Both reflect the
development of open vegetation, either under the
influence of climate or due to human activities.
In order to search for such compounds, we have
analysed the lipid content of soils developed under
conifer forest (spruces and pines) in the catchment of
Lake Aydat (Massif Central, France). Lipids were
extracted by ASE with DCM:MeOH 9:1 and then
separated into classes by flash chromatography with
solvents of increasing polarity before being analysed
by GC-MS.
Apart from n-alkanes and diterpenoids, a series
of 11 original compounds were detected in the ketone
and alcohol fractions (Figure 1). These compounds
are unsaturated pentacyclic triterpenes with a
serratane structure, a methoxy group and various
additional oxygenated functions (methoxy, acetoxy,
ketone or alcohol). Their concentrations range from 1
to 20 µg/g of soil.
Serratane compounds are biosynthesized by
many plants such as pines, spruces, ferns and club
mosses. Reversely, serratane triterpenes bearing a
methoxy group have, up to now, only been reported in
Pinaceae.
Methoxy-serratenes constitute novel tracers of
conifers that are far more specific than classical
diterpenoids. In addition, considering their lower
volatility, they are likely to be preserved in lacustrine
archives, although their resistance to early diagenetic
processes remains to be documented. If resistant,
there are likely to provide crucial information on the
evolution of pine and spruce forests over decadal to
millennial timescales.
Figure 1: GC-MS Total Ion Chromatogram (TIC) of (a) the ketone fraction and
(b) the alcohol fraction from the lipid extract of a soil developed under a conifer
forest : 1: 3�-methoxyserrat-13-en-21-one; 2: 3�,21�-dimethoxyserrat-14-ene; 3:
21�-methoxyserrat-14-en-3-one; 4: 3�-methoxyserrat-14-en-21-one; 5: 21�methoxyserrat-14-en-3-one;
6: 3�-methoxyserrat-14-en-21-yle acetate; 7: 21�methoxyserrat-14-en-3�-ol;
9: 3�-methoxyserrat-14-en-21�-ol; 10: 3�methoxyserrat-14-en-21�-ol;
11: 21�-methoxyserrat-13-en-3,15-dione.
References:
[1] Jacob J., Disnar J.R., Boussafir M., Albuquerque A.L.S., Siffedine A., Turcq
B., 2005. Pentacyclic triterpene methyl ethers in recent lacustrine
sediments (Lagoa do Caço, Brazil). Organic Geochemistry, 36, 449-461.
[2] Zocatelli R., Jacob J., Turcq B., Boussafir M., Siffedine A., Bernades M.C.,
2010. Biomarker evidence for recent turf cultivation in Northeast Brazil
(Lagoa do Boqueirao, RN State). Organic Geochemistry, 41, 427-430.
[3] Lavrieux M., Jacob J., Le Milbeau C., Disnar J.R., Zocatelli R., Bréheret J.G.,
Masuda K., 2011. First detection of triterpenyl acetates in soils: sources
and potential as new palaeo-environmental biomarkers. 25 th IMOG.
Interlaken (Switzerland)
614

P-492
Investigating the microbial populations controlling the
production and oxidation of methane in water-saturated mineral
soils
Katie Lim 1 , Peter Maxfield 1 , Edward Hornibrook 2 , Richard Pancost 1 , Richard Evershed 1
1 Organic Geochemistry Unit, School of Chemistry, University of Bristol, Bristol, United Kingdom,
2 Department of Earth Sciences, University of Bristol, Bristol, United Kingdom (corresponding
author:k.lim@bristol.ac.uk)
There is significant concern regarding the projected
emissions of the prominent greenhouse gas methane
(CH4) from known sources, e.g. wetlands, and the
potential impact on future climate change. In contrast,
mineral soils are generally regarded as CH4 sinks,
due to the presence of high abundances of
methanotrophic populations able to consume ambient
levels of CH4. However, the flux of CH4 from certain
mineral soils is a delicate balance between the
simultaneous production and oxidation carried out by
methanogenic archaea and methanotrophic bacteria
they contain. For example, mineral soils experiencing
regular water saturation, although not always fully
anoxic, may host methanogenic communities and act
as CH4 sources (Teh et al., 2005). It has become a
concern that in such mineral soils, termed ‗transitional
soils‘, internal CH4 production may be significantly
underestimated, and that a ‗tipping-point‘ may occur
where marginal increases in water-content may
increase their capacity to act as a net CH4 source.
The aim of this research was to investigate CH4
cycling in transitional soils susceptible to frequent
seasonal water-logging using a combination of CH4
flux measurements, 13 C-stable isotope probing and
biomarker analyses. A major aim was to develop new
methods for monitoring C flow between methanogenic
and methanotrophic microbes. Methanotrophic activity
is based upon phospholipid fatty acid (PLFA) profiling
in combination with 13 C-stable isotopic probing (SIP;
Maxfield et al., 2006), confirming a dominance of
18:1�7 producing high affinity bacteria. In order to
assess methanogenic archaeal communities we
developed the use of archaeol, determined using gas
chromatography/mass spectrometry (GC/MS), as a
proxy for in situ methanogenesis. This holds particular
potential, as evidenced by the vertical distribution of
archaeol in both free, phospholipid- and glycolipidbound
forms, in mineral soils (see Fig. 1). These
results show for the first time in UK mineral soils an
increased population of methanogenic archaea at
depth due to the increase in anoxia induced by
increased water content. Significantly, >90% of the
total archaeol was present in ‗bound‘ glycolipid and
phospholipid forms, indicating an origin from the living
archaeal biomass. The link to methanogenesis was
confirmed through increased CH4 production rates.
We are now using these techniques to assess the
true ‗sink‘/‗source‘ capacity of mineral soils subjected
to frequent water saturation as basis for further
predicting trends in emissions related to greenhouse
gas driven climate change.
Depth / cm
0
2
4
6
8
10
12
14
Concentration / µg g -1 dry wt.
0.00 0.05 0.10 0.15
Free archaeol
Phospholipid bound archaeol
Glycolipid bound archaeol
Figure 1. Vertical distribution of free and bound
archaeol detected using GC/MS in a mineral soil.
References
[1] Maxfield, P. J., Hornibrook, E. R. C. and
Evershed, R. P., 2006. Applied and
Environmental Microbiology 72 (6), 3901-
3907.
[2] Teh, Y. A., Silver, W. L. and Conrad, M. E.,
2005. Global Change Biology 11 (8), 1283-
1297.
615

P-493
Vegetation and soil organic matter input offshore southeastern
Australia based on organic proxies
Raquel Lopes dos Santos 1 , Daniel Wilkins 2 , Patrick De Deckker 2 , Stefan Schouten 1
1 Royal Netherlands Institute for Sea Research (NIOZ), Texel, Netherlands, 2 The Australian National
University (ANU), Canberra, Australia (corresponding author:raquel.santos@nioz.nl)
The Murray-Darling Basin (MDB) is the
largest river basin of Australia. The river and its
tributaries drain 1/7 th of the Australian continent and
had changed its course and outflow intensively over
the last 600 kyrs. Yet, not much is known about
changes in the vegetation of the basin and its outflow
during the last 2 glacial-interglacial cycles.
Here, we evaluate soil organic matter input
from the Murray-Darling river system to offshore
southeastern Australia (SEA) for the last ~135 kyrs
measuring the Branched and Isoprenoid Tetraether
(BIT) index. This index is based on a ratio between
branched GDGTs produced by soil bacteria and
crenarchaeol, a compound mainly produced by
marine Achaea. Additionally, we evaluate the
vegetation input by analyzing concentrations and
isotopic compostion of long chain n-alkanes. Odd long
chain n-alkanes are mainly derived from terrestrial
plants and their isotopic composition depends on the
isotopic composition of the atmospheric CO2,
physiological responses to environmental changes
and plant-types. Thus, we measured the carbon
isotopic composition of the long chain n-alkanes to
reconstruct vegetation changes during the wet and
dry phases of Australia. Sea surface temperature
offshore SEA was estimated using U K‘ 37 index.
BIT index was always very low (

P-495
Testing branched GDGT-derived proxy parameters in the Arctic
Ocean
Gesine Mollenhauer 1,2 , Konstanze Schipper 2 , Kirsten Fahl 1 , Rüdigel Stein 1
1 Alfred-Wegener-Institute, Bremerhaven, Germany, 2 University of Bremen, Bremen, Germany
(corresponding author:gesine.mollenhauer@awi.de)
The Arctic land masses are covered by vast areas of
permafrost soils, in which high amounts of fossil
organic matter are freeze-locked accounting for up to
50% of the estimated global soil carbon pool
(Tarnocai et al., 2007). Climate warming is expected
to affect the Arctic region unproportionally strongly
resulting in mobilization and transport of this fossil
organic matter to the ocean, where it becomes bioavailable
and can be respired to the atmosphere.
Therefore, quantifying export of soil organic carbon
and characterizing the conditions in the source region
is of great interest.
Several organic-geochemical proxy parameters to
quantify terrigenous organic matter input to ocean
sediments have been used, including bulk
measurements like C/N ratios and � 13 C values as well
as more specific biomarker based proxies (e.g.,
abundance of leaf-wax derived lipids or sterols
specific for terrestrial plants). In the past decade, the
BIT index proxy based on soil-derived branched
GDGTs has been suggested to provide an estimate of
soil organic matter input (Hopmans et al., 2004).
Furthermore, two proxy indices based on abundance
ratios of the same compounds have been suggested
to provide estimates of soil-pH and mean air
temperature (MAT) in the source regions of the soilderived
particles (Weijers et al., 2007). These proxy
parameters have been successfully applied in
temperate and tropical regions.
We analyzed the GDGT-based indices BIT, MBT, and
CBT in core-top sediments collected along four
transects reaching from the mouths of the Russian
Arctic Rivers Ob, Yenisei, Olenek, and Lena, to the
open ocean. The BIT index values are compared with
existing and published bulk parameters and terrestrial
biomarker proxy data (Fahl & Stein, 2007). Generally,
a good agreement is observed between these
indicators for terrestrial organic matter contribution.
Using the MBT index to derive estimates of MAT in
the source-regions of the branched GDGTs yields
temperatures around the freezing point in samples
collected near the river mouths with high terrestrial
organic matter contribution, while values at the more
offshore positions are significantly higher, suggesting
that either the proxy parameter is not reliable when
BIT index values are lower than 0.5, or that
sedimentological conditions favor deposition of
material derived from more inland regions at the
offshore sites. TEX86 estimates for SST are
consistently too high for the Arctic Ocean, including
the offshore sites where BIT index values are low.
Our data show that branched GDGT-derived proxy
parameters hold strong potential for reconstructing
export of permafrost soil organic matter and, to some
extent, of environmental conditions prevailing in the
source regions.
BIT index
1
0.8
0.6
0.4
TOC (%)
4
3
2
1
0
0 200 400 600
Distance from mouth of Yenisei (km)
400
300
200
100
0
concentration (�g/g)
long-chain n-alkanes
�-sitosterol
Figure 1: Proxy data from of the core-top transect off
the Yenisei River. Note inverted scale for MAT
estimates.
Fahl & Stein, 2007. Geo-Marine Letters 27, 13-25.
Hopmans, E.C., et al., 2004. Earth and Planetary Science Letters 224,
107-116.
Tarnocai, C., et al., 2009. Global Biogeochem. Cycles 23, GB2023.
Weijers, J.W.H., et al., 2007. Geochimica et Cosmochimica Acta 71,
703.
-4
-2
0
2
4
6
8
MAT estimate (°C)
617

P-497
Decomposition of wheat straw buried in a grassland soil: the
fungi involved and the products obtained
Rachel Muito-Kabuyah 1 , Clare Robinson 1 , Bart van Dongen 2
1 University of Manchester, School of Earth, Atmospheric and Environmental Sciences, Manchester, United
Kingdom, 2 University of Manchester, Williamson Research Centre for Molecular Environmental Science,
Manchester, United Kingdom (corresponding author:rachel.muitokabuyah@postrgrad.manchester.ac.uk)
Decomposition of dead plant material in soils is a
process of equivalent importance to primary
production in ecosystem functioning, and is driven
partly by saprotrophic fungi. Basidiomycete fungi are
particularly important in lignin degradation [1] but their
contribution is still a matter of ongoing debate. The
aims of this project are, using a combination of
mycological and organic geochemical techniques, to
characterise the diversity of saprotrophic
basidiomycete, ascomycete and zygomycete mycelia
in a representative sandy grassland soil and to
determine their influence on the fate of soil organic
matter, particularly lignin and cellulose.
Bait bags of winter wheat straw (Triticum aestivum
var. Swatham) were buried at two defined depths and
several defined horizontal distances in the field at a
UK coastal grassland (Ainsdale National Nature
Reserve) in May 2005. These baits were retrieved
approximately 4 years later. Visual analyses of the
retrieved bags indicated substantial degradation of
the wheat straw buried (not shown). The fungi present
in the degraded straw were isolated using two types
of selective media: one medium to isolate the general
fungi and a second lignin-rich medium specifically to
isolate basidiomycete fungi. Fungal isolates obtained
showed, that at both soil depths, the fungal
community was dominated by the cellulose
decomposing fungi Trichoderma species and lignin
modifying fungi (Fig. 1a & b). Interestingly,
basidiomycetes were not observed. Pyrolysis GC-MS
analyses of both upper and lower layer samples
showed a substantial degradation of the wheat straw
confirming the earlier visual observations [2].
Acid/aldehyde (Ad/Al) ratios were used as a relative
decomposition state proxy for the syringyl lignin
monomer and describe the ratio of 3,4,5trimethoxybenzoic
acid, methyl ester (S6) to 3,4,5trimethoxybenzaldehyde
(S4) (Fig. 1c). Results
suggest that although no basidiomycetes could be
observed in the fungal frequency analyses,
basidiomycetes were present and must have played
an important role in straw decomposition as the
results infer that the fungi in the soil had induced
oxidative cleavage following degradation of lignin, in a
manner similar to numerous previous laboratory
studies with basidiomycetes [e.g. 3].
Future research will include a combination of
mycology and organic geochemistry to explore
hypotheses developed from the field experiment in a
mechanistic way.
12%
[Ad/Al]S
A
12%
C
10
5
0
0%
6%
70%
B
38%
8%
0%
15%
39%
0 2 4 6 8 10
Distance (m)
Cellulolytic
Lignin modifier
Weakly
cellulolytic
Not
cellulolytic/lign
inolytic
Unidentified
fungi
lower
upper
original straw
Fig.1a & b Fungal frequency of isolation and their
primary enzymatic capabilities from a lowert depth
isolated on media. Fig.1c. Acid/aldehyde ratio
([Ad/Al]S) in THM products from wheat straw. The
original straw, buried in 2005, had an [Ad/Al]S ratio in
the range of 0.6- 1.5 represented by the rectangle.
References:
[1]Kirk, T.K. & Farrell, R. L.
Annu Rev Microbiol 41, 465-505 (1987).
[2]Filley, T.R. et al. Org Geochem 30, 607-621
(1999).
[3] Vane, C. H. et al. J Anal Appl Pyrol 60: 69-78
(2001).
618

P-498
Molecular and isotope characterization of soil lipids along a
savannah (C4)/eucalyptus (C3) chronosequence (Pointe-Noire,
Congo)
Thanh Thuy Nguyen Tu 1 , Mercedes Mendez-Millan 3 , Céline Egasse 1 , Sylvie Derenne 2 ,
Bernd Zeller 4 , Delphine Derrien 4 , Jeremy Jacob 5 , Christine Hatté 3
1 CR2P Université Pierre & Marie Curie, Paris, France, 2 BioEMCo Université Pierre & Marie Curie, Paris,
France, 3 LSCE CNRS, Gif sur Yvette, France, 4 BEF INRA, Nancy, France, 5 UMR6113 CNRS, Orléans,
France (corresponding author:ttnguyen@snv.jussieu.fr)
The surfaces dedicated to forestry
plantations are rapidly increasing throughout the
world, especially in the tropics [1]. The impacts of
such a rapid afforestation on global carbon cycle and
on soil that constitutes one of its key compartment, is
therefore a critical issue [2]. Stable carbon isotope
characterization of C4/C3 chronosequences has
proven useful in assessing the dynamics of organic
carbon in soils [3]. Lipids are important contributors to
organic matter in soils since they can influence
aggregate stability, water retention and fertility.
Nevertheless, little is known on the effects of
afforestation on lipid composition and dynamics in
tropical soils. The eucalyptus plantation located in the
area of Pointe-Noire (Republic of Congo) is a prime
field to study the impact of afforestation on organic
carbon dynamics. Indeed, a eucalyptus forest (C3)
has been progressively planted on savannah (C4)
during the last 30 years [4]. Lipids were solventextracted
from the top soil (0-20 cm) of stands planted
for 7, 17, 30 years, and of a reference plot of the initial
savannah. They were also extracted from the main
savannah species and from eucalyptus.
Lipids accounted for 0.3 to 0.9 wt % of the
dried soils. Gas chromatography-mass spectrometry
analyses of soil lipids revealed a complex mixture
comprising more than 100 identified constituents,
belonging to diverse chemical families (e.g. fatty
lipids, triterpenes, sterols, glycerols). Most of these
molecules correspond to plant components,
emphasizing the importance of this source of organic
matter to soil lipids. Afforestation did not appear to
affect significantly bulk lipid yields. Most of the
identified components are present all along the
chronosequence. Nevertheless, quantification of the
main compounds revealed, for some of them,
significant trends related to the vegetation changes:
(i) decrease of savannah grasses markers (very long
chain fatty lipids, pentacyclic triterpene methyl
ethers), (ii) increase of eucalyptus contribution (long
chain fatty lipids) and (iii) increase of microbial marker
(cholesterol). Compound-specific � 13 C analyses were
performed (1) on odd carbon chain length n-alkanes
from 25 to 31 carbon atoms that are specific to higher
plants and common to both vegetations and (2) on
savannah grass markers. After 30 yrs of eucalyptus
crop, the � 13 C of soil C25 and C27 n-alkanes displayed
typical trend of a C4/C3 vegetation shift with a
depletion of 4.4 ‰ and 6.4 ‰. Surprisingly, the C29 nalkane
� 13 C is of -30.5 ‰ for all stands, pointing to
additional sources for this compound. The isotopic
signature of the C31 n-alkane showed no incorporation
from the eucalyptus plant, as for pentacyclic triterpene
methyl ethers. Compound-specific 14 C analyses are
under progress to precise the origin and the residence
time of the different markers in soil.
This work is part of the DynaMOS ANR project.
References
[1] FAO, State of the World's Forests, Food and
Agriculture Organization of the United Nations, Rome
(2003) 151 pp.
[2] Garcia-Quijano J.F., Deckmyn G., Moons E.,
Proost S., Ceulemans R. and Muys B. (2005). An
integrated decision support framework for the
prediction and evaluation of efficiency, environmental
impact and total social cost of domestic and
international forestry projects for greenhouse gas
mitigation: description and case studies. Forest Ecol.
Manage. 207 pp. 245–262.
[3] Cerri C., Feller Ch., Balesdent J., Victoria R. and
Plenecassagne A. (1985) Application du traçage
isotopique naturel en 13 C à l'étude de la dynamique
de la matière organique dans les sols. C.R. Acad.
Sci., Sér. D, 300 Sér. II 9, pp. 423–427.
[4] Bernhard-Reversat F. (1993) Dynamics of litter
and organic matte rat the soil-litter interface in fastgrowing
plantations on sandy ferralitic soils (Congo).
Acta Oecol. 14, pp.179-195.
619

P-499
The relationship between peatland hydrology, biogeochemistry
and biomarker assemblages
Rich Pancost 1 , Richard Evershed 1 , Edward Hornibrook 2 , Erin McClymont 1 , Elizabeth
Bingham 1 , Lidia Chaves 1 , Katie Lim 1 , Frank Chambers 3
1 Organic Geochemistry Unit, School of Chemistry, University of Bristol, Bristol, United Kingdom, 2 Bristol
Biogeochemistry Research Centre, School of Earth Sciences, University of Bristol, Bristol, United Kingdom,
3 Department of Natural & Social Sciences, University of Gloucester, Cheltenham, United Kingdom
(corresponding author:r.d.pancost@bristol.ac.uk)
Lipid biomarkers are now widely applied in the study
of peatlands, both in modern biogeochemical and
ancient palaeoclimate contexts. However, little work
has attempted to bring these two lines of inquiry
together and it remains unclear exactly how, or if at
all, biomarker distributions in peat reflect microbial
populations or biogeochemical processes at the time
of peat deposition. To address that, we have
determined archaeal (archaeol and hydroxyarchaeol)
and bacterial (hopanoid) concentrations as well as
stanol/sterol ratios in four Holocene ombrotrophic
peatlands, spanning a range of European climate
zones.
Neither ether lipid was present in the aerobic acrotelm
of the peat, consistent with an origin from anaerobic
archaea, presumably methanogens. At the depth of
the maximum seasonal water table, archaeol and
hydroxyarchaeol concentrations markedly increase at
all four sites, again consistent with an anaerobic
source, but the concentrations differed strongly
among sites, apparently reflecting a combination of
vegetation and temperature influences on
methanogenesis (Fig. 1). In particular, low ether lipid
concentrations in Finland probably reflect the lack of
vascular vegetation having well developed root
systems, together with low mean annual
temperatures. Similarly low concentrations of
archaeol and sn-2-hydroxyarchaeol in the German
bog most likely result from below freezing winter
temperatures and a short growing season. The
occurrence of hydroxyarchaeol is limited to a narrow
and shallow depth range, suggesting that it is poorly
preserved, but archaeol persists throughout the peat
cores. Decoupling of archaeol and the more labile
hydroxyarcheol concentrations below ca 50 cm
suggests that the former records fossil rather than
living biomass. If so, then downcore variations in
archaeol concentration likely reflect past changes in
peatland hydrology, biogeochemistry and rates of
methanogenesis.
Figure 1. Comparison of annual (open circle) and
minimum air temperatures (closed circle) with
maximum concentrations of archaeol observed in four
European peatlands (GB= Butterburn Flow, Great
Britain; IR = Ballyduff Bog, Ireland; DM = Bissendorfer
Moor, Germany; FI = Kontolanrahka Bog, Finland).
Stanol/sterol ratios exhibit remarkably similar trends.
Ratios are low in shallow acrotelm peat but then
increase dramatically at and just below the water
table. Moreover, in deeper horizons the ratios co-vary
with archaeol concentrations and reconstructed water
table levels, with low ratios and low archaeol
concentrations occurring during times when the water
table level was deep and more oxidising conditions
presumably prevailed. This indicates that the
transformation of plant sterols to their stanol
analogues is associated with reducing conditions, as
has been suggested for marine settings.
Combined, the records could provide new insights
into past changes in peat redox conditions. Caution is
required in interpretation due to the complex controls
on, especially, methanogen biomass, however, our
data suggest that a combination of biomarker and
other proxies could be used to identify times when
shallow water tables were associated with reducing
and methanogenic conditions.
620

P-500
Geochemical characterization of the impact of landuse change
on soil and riverine organic matter dynamics in a pristine
tropical rainforest, Guyana
Ryan Pereira 1 , Robert Spencer 3 , Peter Hernes 2 , Rachael Dyda 2 , Isabella Bovolo 4 , Geoff
Parkin 1 , Thomas Wagner 1 , Nikolai Pendentchouk 5
1 Newcastle University, Newcastle upon Tyne, United Kingdom, 2 University of California Davis, Davis, United
States of America, 3 Woods Hole Research Centre, Falmouth, United States of America, 4 Iwokrama
<strong>International</strong> Centre for Rain Forest Conservation and Development, Georgetown, Guyana, 5 University of
East Anglia, Norwich, United Kingdom (corresponding author:Ryan.Pereira@ncl.ac.uk)
The two greatest threats to terrestrial
ecosystems are land-use and climate change.
Tropical forest ecosystems store ~50% of the World‘s
living terrestrial carbon pool and �12% soil carbon
(SOM) pool. With respect to Amazonia, seasonal
variability can trigger an almost instantaneous and
large increase in the release of carbon from soils into
rivers when linked to transitional periods of extreme
precipitation. 1,2 Rivers reflect this intense cycling, with
the largest fluxes of water and carbon to the ocean
coming from tropical rivers such as the Amazon,
Congo, or Orinoco Rivers, exporting 26-28% of global
riverine dissolved organic carbon 3 (DOC).
Iwokrama <strong>International</strong> Centre for Rainforest
Conservation and Development (www.iwokrama.org)
is a 371,000 hectare reserve situated within the
largely pristine rainforest of the Guiana Shield.
Iwokrama is defined by the catchment of the Burro
Burro River, which flows into the Essequibo River,
(av.discharge ~5000m 3 /s; 4 ).However, no geochemical
information exists to gauge future changes.
A new geochemistry program established in
2010 examines the capacity of pristine tropical
rainforest and its soils to generate, store and recycle
carbon and water; and to address the issue of the
forests‘ response to natural climate variability and
land-use, thereby characterising the current state of
the forest and how it responds to external forcing.
Here we present geochemical data for soils
and river water collected from two small headwater
catchments during the peak dry and wet seasons of
2010. The data are used to provide a direct
comparison of two river catchments situated on
nutrient-poor bedrock with similar vegetation but with
pristine and perturbed land uses (sustainable timber
harvesting) to examine and quantify the differences in
terrestrial carbon cycling. Using lignin-phenol
biomarkers and stable isotope (δ 18 O, δD & δ 13 C)
analyses, we characterize the sources and
processing of dissolved organic matter (DOM).
Evaporation dynamics in rivers of both catchments
show seasonal transitions of δ 18 O isotopes (dry: -2.1
to -3.9‰, wet: -4.6 to -6.3‰) and increased humidity
in the wet season (δ 18 O vs δD slope

P-501
Land use and climatic effects on hydrogen isotope
compositions of long-chain n-alkanes and distribution of
tetraether lipids in soils
Janet Rethemeyer 1 , Michael Lappé 1 , Stefan Schouten 2 , Pascal Boeckx 3 , Enno Schefuß 4
1 Institute of Geology and Mineralogy, University of Cologne, Cologne, Germany, 2 NIOZ Royal Netherlands
Institute for Sea Research, Department of Marine Organic Biogeochemistry, Texel, Netherlands, 3 Faculty of
Bioscience Engineering, Ghent University, Ghent, Belgium, 4 Department of Geosciences, University of
Bremen, Bremen, Germany (corresponding author:janet.rethemeyer@uni-koeln.de)
Distributional and isotopic analyses of terrestrial lipid
biomarkers are powerful tools used for paleoenvironmental
reconstructions. These analyses are
commonly performed on marine or lacustrine
sediment records. The abundance as well as the
isotopic composition of the organic compounds from
terrestrial source organisms, however, may be
significantly altered until organic matter burial in
sediments. Intermediate storage in soil as well as
differences in the recorded signals between
ecosystems may be considerable factors affecting the
reliability of the lipid based proxies, which have not
yet been studied in any detail.
We investigated two terrestrial lipid based proxies in
modern soils under different land use and climatic
conditions: (a) the distribution of branched glycerol
dialkyl glycerol tetraethers (GDGTs) used as
indicators for past changes in continental air
temperature and soil pH [1], and (b) the hydrogen
isotopic composition of long-chain n-alkanes as an
indicator for hydrological changes. The study area is
the south-western Ethiopian highland where soil
samples have been taken along a topo-sequence
from 1770 to 2650 m altitude. Mean annual air
temperature and precipitation range from about 15 to
21 °C and 1500 to 2200 mm, respectively. At six
altitudes agricultural, forest and pasture soils (Nitisols)
were analysed.
Bulk soil properties including total organic C, total N
and pH indicate a more intense cultivation and more
pronounced soil degradation, respectively, of the sites
at lower altitude. Soil pH values of all cultivation
variants showed a decrease with altitude from about
pH 5.8 to 5.4, which was less pronounced in the
arable soils. We used the cyclisation ratio of branched
tetraethers (CBT) to estimate soil pH [1]. The results
however, differed strongly from the measured soil pH
values with no consistent trend. This is caused by the
relatively large uncertainty of the CBT index as well
as the low abundance of cyclopentane moeities of
branched GDGTs at low soil pH. We also tested the
methylation index of branched tetraethers (MBT),
used to reconstruct mean annual air temperatures.
The GDGT based data showed a linear increase with
altitude, which is most pronounce for the undisturbed
forest soils. The calculated mean annual air
temperatures however, overestimate the measured
temperature by about 3 to 4.5°C, which may reflect
that main GDGT production by soil bacteria occurs at
warmer periods, suggesting the need for a local
calibration.
The hydrogen isotope composition of long chain nalkanes
(n-C25 - n-C33) derived from higher plants leaf
waxes showed a strong scatter and no clear trend
with altitude. We thus examined the � 13 C composition
of the n-alkanes and found higher values for n-C31
and n-C33 reflecting a higher contribution of C-4 plant
material. C-4 plant have a higher water use efficiency
than C-3 plants and thus differ from C-3 plants in their
apparent hydrogen isotopic fractionation between
precipitation and lipids. After excluding these two
compounds, weighted average δD values for n-C27
and n-C29 alkanes showed a significant correlation
with altitude. The most prominent trend was observed
for the forest sites (R 2 = 0.87) most probably due to
the long term growth of C-3 vegetation while the
isotopic signal in the two other soils is biased by
cultivation. This altitude trend line can be translated
into a δD lapse rate (n-C27 and n-C29) of 17.9 ‰ per
1000 meters which agrees well with global
observations of altitudinal isotopic changes in rainfall.
These results indicate that land use can considerably
bias terrestrial lipid based proxies. The results
emphasize the need for source-area specific
calibrations of proxy parameters.
References
[1] Weijers, J.W.H. et al., 2007. Geochimica et
Cosmochimica Acta 71, 703–713.
622

P-502
Soil organic matter characteristics in the permafrost terrain,
European Russian Arctic: lability, storage, and impact of
thawing
Joyanto Routh 1,5 , Gustaf Hugelius 2 , Timothy Filley 3 , Patrick Crill 4 , Peter Kuhry 2
1 Department of Earth Sciences, IISER-Kolkata, Mohanpur, India, 2 Department of Physical Geography and
Quaternary Geology, Stockholm University, Stockholm, Sweden, 3 Department of Earth and Atmospheric
Sciences, Purdue University, West Lafayette, United States of America, 4 Department of Geological Sciences,
Stockholm University, Stockholm, Sweden, 5 MTM, Örebro University, Örebro, Sweden (corresponding
author:joyanto.routh@iiserkol.ac.in)
Soils in high latitude terrestrial ecosystems store huge
stocks of organic carbon because the low
temperature and anoxic conditions from water logging
reduce decomposition rates. Redistribution of these
huge reservoirs of surface carbon pools driven by
climate change poses a challenge. Particularly, the
soils in permafrost regions including peatlands are
most vulnerable to remobilization because of thawing
and change in hydrologic conditions (1). The net C
flux from these reserves however depends on the size
and lability of the soil organic matter (SOM) pools.
Here, we have characterized the SOM stored in soils
representative of major land cover and soil types in
the discontinuous permafrost terrain of European
Russian Arctic. We are using an array of chemical
analyses involving elemental ratios (C, N, and H),
stable isotopes (C and N), and specific biomarkers (nalkanes,
sterols, and lignin). The detailed
characterization of SOM is supposed to yield
information about: 1) the major components of SOM
and it sources, 2) chemically labile vs. refractory
fractions in SOM, and 3) OM preservation affected by
depth/age in the soil profile in relation to permafrost
conditions and/or changes in the active layer depth.
Samples were collected from the tundra near Seida in
the Usa Basin, west of the Ural Mountains. The mean
annual temperature and precipitation are –6.1°C and
538 mm, respectively. The landscape is underlain by
discontinuous permafrost (70-90%). The peat
plateaus are underlain by nearly continuous
permafrost, whereas permafrost-free sections are
found in uplands and along river/stream valleys.
Shrubs, lichens and mosses characterize the upland
tundra on mineral soils. Isolated stands of spruce and
downy birch can be found on permafrost -free ground.
Peat plateaus were sampled near thermally eroding
edges. Permafrost soils were cored using steel pipes
hammered into the frozen peat. Permafrost-free fens
were sampled using Russian corers. The samples
were sectioned and freeze-dried. Radiocarbon
analysis of bulk SOM samples was done at the
Poznan Radiocarbon Laboratory, Poland. Elemental
and stable isotope (C and N) analyses were done in
decarbonated samples. Lipids were extracted and the
samples were further cleaned/fractioned and
derivitized (2) for analyses of n-alkanes, alkanols, and
sterols. Lignin was analyzed using the CuO method
(3). The OM extracts were analyzed on a GCMS.
Basal peat ages range from 1500 (fens) to 9000 (peat
plateaus) cal years B.P. Organic matter deposited is
immature. The biomarkers indicate that higher plants
are the primary source of OM. The concentrations of
different biomarkers (e.g., n-alkanes sterols and
lignin) increase with depth before reaching the
mineral soil interface. The trend coincides with
increase in age and humification. The low
concentration of different biomarkers in upper
samples results from OM degradation in surface
exposed to thawing. The biomarker profiles vary
suggesting dominance of one or more higher plant
types in the peats or soils (e.g. Sphagnum vs.
Equisetum). There is little indication of SOM
degradation in the peats with depth. High
Acid/Aldehyde ratio in lignin, which suggests OM
degradation only occurs in surface sediments. In
contrast, the permafrost free non-peatland soils
indicate more decomposed material with increasing
depths. The more labile components such as sterols
and alkanols show greater variability in concentration
with depth than n-alkanes and lignin.
References:
1. Tarnocai, C., Canadell, J., Mazhitova, G., Schuur,
E.A.G., Kuhry, P., and Zimov, S. (2009) Global
Biogeochemical Cycles 23, GB2023.
2. Wakeham, S.G., Peterson, M.L., Hedges, J.I., Le,
C. (2002) Deep-Sea Research II 49, 2265–2301.
3. Filley, T.R., Freeman, K.H., Bianchi, T.S.,
Baskaran, M., Colarusso, L.A., and Hatcher, P.G.
(2001) Organic Geochemistry 32, 1153-1167.
623

P-503
Geochemical characterization of a meadow soil
Tünde Nyilas 1 , Magdolna Hetényi 1 , Nóra Czirbus 1 , Anita Gál 2 , Csanád Sajgó 3
1 University of Szeged, Department of Mineralogy, Geochemistry and Petrology, Szeged, Hungary, 2 Szent
István University, Department of Soil Science and Agrochemistry, Gödöllő, Hungary, 3 Institute for
Geochemical Research, Hungarian Academy of Sciences, Budapest, Hungary (corresponding
author:nyilas@gmail.com)
During the last decade the geochemical
investigation of soils has received increasing attention
owing to the significant role played by both their
mineral and organic composition in the processes of
pedogenesis, in the migration of contaminants and in
the global carbon cycle. Obtaining detailed
information about different soil-chemical processes
and determination of geochemical lines are based on
the organic and inorganic geochemistry of soils. The
soil organic matter has a great impact on the
weathering of rocks and pedogenetic processes. Not
only the amount and the bulk geochemical features of
the organic matter but also the proportion of carbon
pools with different thermal stability influence these
processes. Changes in hydrological conditions can
lead to the modification of soil-types.
The aim of this work was to investigate mineral and
organic geochemical characteristics of a typical
meadow soil according to the Hungarian Soil
Taxonomy [1]. Depth profile of elements, geochemical
characterization of the organic matter (lipid contents,
E4/E6 ratios of humic and fulvic acids) and soil
chemical data were determined, as well as the
mathematical deconvolutions of Rock-Eval pyrograms
were performed.
The soil profile was opened at Lake Csorba (North-
East Hungary) on a former floodplain of River Sajó,
currently under plowing. The pH is neutral-slightly
alkaline (7.75, 7.89), the parent material is loess with
sandy alluvial sediment. The main properties which
are characteristic of the whole profile are the result of
hydromorphic features including dark blackish-brown
colour, Fe- and Mn-concretions, gleyic colour pattern
and an abrupt change in organic matter content at
~80 cm. The organic matter content of the humus
containing horizons is 2.8-2.2 %, with high base
saturation (93-92 %) and high cation exchange
capacity (36-28 cmol/kg).
The humus content is lower than it could be
expected on the basis of the colour of the humus
containing horizons. This colour is due to the
presence of Fe(II)-humus complexes formed under
anaerob conditions. At ~80 cm organic matter content
decreased to a minimum value (0.3 %) accompanied
by the essentially increased amount of carbonate
concretions. Between ~80-120 cm three (carbonate,
gleyic and gravel) horizons can be distinguished.
Similar organic matter (2.8, 2.2 %) and the same lipid
(0.24 mg/g) contents were measured for the humus
containing horizons. The depth trend of the E4/E6 ratio
measured on fulvic and humic acids, together with
that of the proportion of humic substances and
resistant bio-macromolecules, reflected an intense
leaching. It is supported by the increasing values
(from -0.23 to 0.60) of I-index [2], which shows the
relative importance of biomass versus the humic
substances.
Combined interpretation of the organic geochemical
and inorganic soil chemical data revealed leaching.
Besides the A horizon of constant organic matter
content, the development of a thin transitional
accumulation zone with downward decreasing organic
matter content began. It suggested that features of
chernozem soils started to evolve.
As a consequence of the slight changes in the
organic and inorganic features, resulting from the
decreased water level, the studied meadow soil is
classified as a Calcic Chernozem (Taptogleyic)
according to the World Reference Base for Soil
Resources [3] with a mollic diagnostic horizon.
The project was supported by the Hungarian
Scientific Research Found (OTKA) through grant K
81181.
References
[1] Stefanovits, P., 1963. The soils of Hungary.
Akadémiai Kiadó. Budapest (in Hungarian)
[2] Sebag, D., Disnar, J.R., Guillet, B., Di Giovanni,
C., Verrecchia, E.P., Durand, A., 2006. Monitoring organic
matter dynamics in soil profiles by Rock–Eval pyrolysis: bulk
characterization and quantification of degradation. European
Journal of Soil Science 57, 344–355.
[3] FAO/ISRIC/ISSS, 2006. World Reference Base for
Soil Resources. World Soil Resources Reports. No. 103.
FAO. Rome.
624

P-504
Hydrocarbons occurring in peats of different types and origins
(Southern Taiga of Western Siberia, Russia)
Olga Serebrennikova 1 , Yulia Preis 2 , Elena Gulaya 1
1 Institute of Petroleum Chemistry SB RAS, Tomsk, Russian Federation, 2 Institute for Monitoring of Climatic
and Geological Systems SB RAS, Tomsk, Russian Federation (corresponding author:gulaya@ipc.tsc.ru)
The compositions of n-alkanes, arenes and
terpenoids of peats, formed in forested herbaceous
tussock sedge swamp – sogra, two pine dwarf shrubs
sphagnum bogs – ryams and in two oligotrophic
floating mires located in the southern taiga of Western
Siberia, have been investigated.
A comparative analysis of hydrocarbon compositions
in peats formed under various conditions
demonstrated specific features characteristic of
individual peat types, which reflect their origin. But in
all peats other than sapropel, alkylbenzenes
consisted of two equal forms. These were benzenes
with a normal alkyl substituent and benzenes with a
substituent branched at the atom of the alkyl chain;
the latter were predominant in the majority of peats
but absent in sapropel. These benzenes with a
branched chain occurred in peats as three groups of
C17-C19 isomers different in the length of the alkyl
chain, in which a pentyl, butyl, propyl, ethyl, or methyl
group was attached at the exposition. In the majority
of peats, C19 isomers were predominant; C18
isoalkylbenzenes dominated in low-mire peat at a
depth of 200 cm. Benzenes with unbranched
substituents were mainly C15-C24 homologs with a
maximum concentration of C21. In sapropel, nalkylbenzenes
were C15-C21 homologues, whereas
they were absent in floating mire fuscum peat at a
depth of 200 cm.
The sogra low-mire peats differed from the others by
the occurrence of perylene among hydrocarbons,
higher concentrations of retene and intermediate
products of abietic acid transformation (saturated and
monoaromatic tricyclic terpenoids) and by the
absence of oleanene derivatives. Down the sogra
deposit profile, going from woody grass peat to grass
peat, the concentrations of bituminous components
and all hydrocarbon groups excepting tetracyclic
arenes (the concentration of which dramatically
decreased) increased. The relative concentration of nalkanes
in the mixture of hydrocarbons decreased;
the fraction of C15, C17, C21 and C25 homologues in nalkanes
increased. The ratio of hopanoids, which are
characteristic of bacteria, to tricyclic terpenoids
(gymnosperms are the main source) increased by a
factor of >20 to indicate an increased contribution of
bacterial biomass to the organic matter of peat at the
bottom of the peat deposit profile. The fraction of
unsaturated structures increased among pentacyclic
terpenoids, diploptene in particular. This suggests a
low diagenetic conversion of the organic matter of
peat, and it is consistent with a low degree of
diploptene decomposition. Among aromatic
hydrocarbons the perylene concentration
considerably increased. The concentrations of retene
and cadalene dramatically increased to suggest an
increased contribution of coniferous trees to the
formation of peat at this period of time.
The concentrations of bituminous components and
hydrocarbons in ryam raised bog fuscum peats
increased, as compared to those in sogra peats. In
the top portion of the peat deposit profile, C29 and C31
homologues were the main components of n-alkanes;
unsaturated hopane and oleanane precursors
dominated in the mixture of pentacyclic terpenoids;
diploptene was predominant. Among pentacyclic
terpenoids, the concentration of diploptene sharply
decreased and concentration of friedoolean-14-en,
which are characteristic of flowering plants, as well as
concentrations of cadalene and retene increased.
The floating mire deposit consisted of peats with considerably
different concentrations of bituminous components
and individual hydrocarbon groups. The distinctive
features of peats from this area were an
anomalously high concentration of pentacyclic
terpenoids in redeposited transitional peat and the
predominance of 17 (H),21 (H)-homohopane (22R)
among these terpenoids over the entire deposit
profile. The concentration of 17 (H),21 (H)homohopane
(22R)varied from 24% (sapropel and
redeposited peat) to 38-48% (fuscum peat) of the total
pentacyclic terpenoids basis. This can be a
consequence of a specific set of terpenoids in peatforming
plants or deposition conditions. The
unsaturated hopane and oleanane precursors, which
occur in living organisms and predominate in ryam
peats, occurred in floating mire peats in inferior
amounts. This was likely due to a rapid transfer of
biomass to anaerobic conditions because of a high
level of mire water in this area and the hydrogenation
of double bonds in biomolecules. The floating mire
peats were also characterized by a minimum cadalene
and oleanane precursors content (as compared
625

P-505
Organic carbon composition and routing in alpine headwaters:
the importance of storms
Jo Smith 1 , Niels Hovius 1 , Albert Galy 1 , Jens Turowski 2
1 Department of Earth Sciences, University of Cambridge, Cambridge, United Kingdom, 2 Eidg.
Forschungsanstalt für Wald, Schnee und Landschaft, Birmensdorf, Switzerland (corresponding
author:jcs74@cam.ac.uk)
The erosion of continental biomass in the form of
particulate organic carbon (POC) is a poorly
constrained flux in the global carbon cycle. It has
received little attention in the past because its
potential for carbon dioxide drawdown was thought to
be insignificant in comparison to silicate weathering
and burial of marine organic matter. However, recent
studies suggest that storm-driven POC erosion is an
effective way of sequestering carbon in tectonically
and climatically extreme regimes.
In order to assess whether biomass erosion and
burial is a globally significant carbon sink, we need to
know how much POC is harvested from less intense
geomorphic settings. More insight is also needed into
the processes involved in mobilizing organic carbon in
catchment headwaters, including its sources and
pathways and how these change under different
hydrologic conditions.
To these ends, we have collected both weekly flowproportional
samples (over a period of two years) and
higher-frequency grab samples (during storms in July
2010) of riverine and runoff suspended sediment from
the Erlenbach, a small catchment in the Swiss
Prealps. We have obtained their C and N
concentrations and isotopic ratios using stable isotope
mass spectrometry.
Riverine suspended sediment contains a mixture of
POC derived from contemporary sources (soils and
vegetation) and fossil POC found in bedrock, which
are characterised by their N/C and δ 13 Corg. Only the
modern component will have a direct effect on
atmospheric CO2.
By determining the same chemical parameters on
soil, bedrock, channel material and vegetation
samples collected throughout the catchment, we
define a mixing line between endmember sources
dominated by modern and fossil carbon. We find that,
while POC as a percentage of suspended load
remains constant regardless of the suspended
sediment concentration, it contains a significantly
higher fraction of modern POC during storms than
under normal flow conditions. The effect is most
pronounced at higher suspended sediment
concentrations and during the rising limb of the
hydrograph.
The fact that rising limb samples are closer to the
modern endmember than storm samples overall
provides clues to the mechanisms by which POC is
harvested. We propose that, during the initial storm
phase, litter and topsoil are delivered to the channel
by runoff, but that as the water level and erosive
power of the stream increase, more of the fossil
carbon that forms the channel sides and bottom is
incorporated into the suspended load.
The fact that samples collected at high suspended
sediment concentrations are closer to the modern
endmember than storm samples overall is also
significant. Long-term records of discharge and
suspended sediment concentration from the
catchment show that they are related by a power law;
that is, the vast majority of sediment is transported by
just a few very large floods. Our results suggest that
these are optimal conditions for exporting modern
POC. If these relationships and processes are typical
of temparate montane forests globally, then the
erosion of continental biomass is a potentially
significant carbon sink
626

P-506
Preservation of particulate organic carbon from an active
mountain belt in shallow marine sediments
Robert Sparkes, Niels Hovius, Albert Galy, Vasant Kumar
University of Cambridge, Cambridge, United Kingdom (corresponding author:rbs26@cam.ac.uk)
Particulate Organic Carbon (POC) export from active
mountain belts can be a more effective sink of CO2
than silicate weathering. Foreland basin deposits in
these environments are supplied by large amounts of
sediment, containing a mixture of organic carbon
particles. Woody debris, litter and soil carbon
removed by landsliding from mountain slopes is
mixed with petrogenic carbon sourced from bedrock.
Both forms of carbon can be exported by hyperpycnal
discharge from the fluvial and shallow-marine system,
and have the potential to be stored on a geological
timescale in foreland basins. Storage of fresh POC
and subsequent forest re-growth leads to a sink of
carbon from the hydrosphere-biosphere-atmosphere,
while efficient transport and burial of petrogenic
carbon prevents oxidation of this material and limits
the effects of this possible carbon source.
Using coupled carbon and nitrogen isotope
measurements and Raman Spectroscopy, we have
investigated the Miocene export of POC from the Alps
into the Marnoso Arenacea Formation, exposed in the
present-day Apennines. The Marnoso Arenacea
Formation is a 3500 m thick turbidite sequence in
which individual beds can be correlated over large
areas. This has allowed vertical profiling through
representative turbidite deposits in several places
along their 100 km length. Both petrogenic graphite
and disordered carbonaceous material were found in
the turbidites. Permeability of the lower, sandy units of
turbidites has permitted oxidation of disordered
carbonaceous material. These units tend to have a
relatively low Total Organic Carbon (TOC) content of
around 0.05 % with POC only as graphite, as this is
much more stable than the disordered forms. Muddy
parts of the turbidites contain similar amounts of
graphite, but also preserve disordered material, with
TOC up to 0.8 %.
Combining published volumetric estimates for the
turbidite sequences with our carbon profiles, we
estimate that a turbidites in the Marnoso Arenacea,
with volume 7 km 3 , contains 46 Mt of carbon. This is
~50 % of the annual global CO2 consumption by
silicate weathering.
627

P-507
Dynamics of soil organic matter and mineral nitrogen in soil:
investigation into a complex relationship
Priscillia Sémaoune, Joëlle Templier, Mathieu Sébilo, Christelle Anquetil, Sylvie Derenne
BioEMCo, UMR 7618 CNRS/UPMC, 4 place Jussieu, 75252 Paris cedex 05, France (corresponding
author:priscillia.semaoune@upmc.fr)
Soil organic matter (SOM) comprises complex
macromolecular structures which play a major role in
soil as they produce inorganic nitrogen (NH 4 + , NO2 -
, NO 3 - ) by mineralization, and can also contribute to
mineral nitrogen stabilization. Furthermore, SOM is
related to dissolve organic matter (DOM), via
decomposition and humification processes. The
DOM fraction only represents a small proportion of
soil Corg, but it is the most reactive to the
environmental factors. However, in spite of its
importance, the relation SOM-DOM is still partly
unknown. As SOM is tightly related to the mineral
nitrogen in soil, the aim of the present study is to
investigate the relation between SOM chemical
structure (C & N) and inorganic (NH 4 + , NO3 - ) and
organic (COD, NOD) species present in soil solution.
This should allow improving the understanding of the
relationship between the dynamics of SOM/DOM
and of mineral nitrogen. Processes associated in
SOM turn-over are mediated by microbial organisms,
depending mainly on water and oxygen
environmental conditions which determine the
degree of anoxia and the possibility of migration for
molecule and organisms in soil. As a result, to test
the influence of water content on the dynamic of
organic matter, soil samples were collected along a
transect with a hydromorphic gradient and at
different depth in a grassland site in Quimper,
France (ORE AgrHys). Samples were also collected
during high flow and low flow period. SOM and DOM
were chemically characterized at a molecular level
using spectroscopic ( 13 C solid state NMR) and
pyrolytic methods. Isotopic biogeochemistry was
used to identify the origin of carbon and nitrogen
species present in the environment and to follow the
processes affecting their concentration. The global
isotopic values (δ 15 N and δ 13 C) of bulk soil, SOM
and DOM and inorganic nitrogen (NH 4 + , NO3 - ) were
measured. The soil δ 15 N varies between 3.6 ‰ and
7.8 ‰ and for all soil profiles we observed an
increase in δ 15 N values with depth and the
decrease in % N. On the same time the δ 15 N values
of nitrate increase with the depth. We observed no
significant tendency with the water content. The
processes susceptible to generate an increase of
δ 15 N in soil are gaseous loss denitrification and
volatilization. Indeed, this processes undergoing a
significant isotopic fractionation leading to 15 N
enrichment of the residual substrates. The deepest
zones are subject to a higher number of
volatilization/nitrification-denitrification cycles which
are enriched in 15 N the substrates (NH 4 + , NO3 - ). In
parallel, SOM and DOM compositions exhibit
differences. NMR spectra of SOM show a
predominance of C aliphatic whereas DOM is
dominated by carbohydrate signal. Pyrograms of
SOM show an important contribution of lignin derived
pyrolysis products and alkane/alkene doublets, in
agreement with NMR. Pyrolysis in the presence of
TMAH, which allows the detection of polar
compounds, reveals numerous fatty acids (C16-C30)
along with characteristic lignin derived acids. DOM
pyrograms are almost similar except a relative lower
contribution of lignin derived pyrolysis products. No
significant modification of structure for SOM or DOM
is observed either with depth or with the moisture
content.
628

P-508
Deltaic sediments as recorders of permafrost carbon dynamics
within Arctic drainage basins: a case study from the Mackenzie
River
Jorien Vonk 1 , Xiaojuan Feng 1 , Angela Dickens 3 , Zainab Hussain 3 , Bokyung Kim 3 , Liviu
Giosan 2 , Sam Zipper 2 , Daniel Montluçon 1 , Timothy Eglinton 1
1 ETH Zürich, Geological Institute, Zürich, Switzerland, 2 Woods Hole Oceanographic Institution, Geology and
Geophysics, Woods Hole, United States of America, 3 Mt. Holyoke College, South Hadley, United States of
America (corresponding author:jorien.vonk@erdw.ethz.ch)
Only a few mechanisms on earth have the
potential to release significant amounts of carbon into
the atmosphere, causing a positive feedback on
global warming. Thawing of carbon pools stored in
circum-arctic permafrost is one of these mechanisms.
Here, the large stocks of organic carbon (OC), ca.
50% of the global terrestrial belowground pool, are
susceptible to remobilization upon permafrost
degradation under intensifying climate warming.
Fluvial transport of aged soil carbon, released from
permafrost, is one possible fate of this OC. This
export has shown to predominantly take place in the
particulate form. The Mackenzie River in Arctic
Canada is the largest source of particulate OC (POC)
to the Arctic Ocean. Half of the Canadian permafrost
is within 2 degrees of thawing, and the southern limits
of sporadic permafrost in this region are already
retreating with on average 4.5 km per year,
suggesting an increased export of fluvial POC. There
is a strong need for long-term records of OC
dynamics to provide context for ongoing climateinduced
changes in the drainage basin.
Ice build-up and scouring in combination with
storms and waves makes Arctic estuaries problematic
regions to obtain sediment cores for long-term
studies. A large fraction of Mackenzie River
suspended sediments are efficiently trapped during
the spring flood in the wide mosaic of deltaic lakes
before arriving in the Beaufort Sea. These lakes have
a great potential to reconstruct past records of
sediment and POC discharge, tracing changes in
permafrost dynamics. ―Low-closure‖ lakes, which are
only connected to the main channel during spring
flood, host a valuable annual archive in their lake
sediments. We have sampled and dated sediment
cores from numerous lakes that show the potential to
reconstruct fluvial deposition over decadal to
millennial scales. For example, a short core from Lake
7, a low-closure lake in the middle-delta, shows
continuous, ~1 cm thick yearly laminations spanning
the last ~90 yrs. This high-resolution archive offers a
unique opportunity to reconstruct past fluvial OC
dynamics in great detail.
Bulk and molecular geochemical and
isotopic comparisons on spring flood suspended POC
and sediments of Lake 7 demonstrate that the lake
sediments are reliable recorders of fluvial OC
discharged to the delta. TOC:TN ratios and total lignin
concentrations of suspended sediments lie in a similar
range as delta lake sediments. Lignin phenol
analyses confirm that the lake sediments provide a
good representation of fluvial POC flux by showing
syringyl/vanillyl, cinnamyl/vanillyl and acid/aldehyde
ratios in the same range as suspended sediments in
the Mackenzie main channel.
Downcore bulk OC 14 C ages are between 11
and 12.5 ky, suggesting a significant contribution of
ancient OC from sedimentary rock erosion. Despite
this, a weak trend towards younger 14 C ages can be
seen in the last 25 years, suggesting a greater input
of aged, but relatively younger permafrost OC.
Increasing sedimentation rates since the 1970s, and
possibly even 1950s, support the notion of changing
fluvial discharge to the delta. However, more in-depth,
molecular-level measurements are required to confirm
this trend. To obtain an unbiased permafrost soil OC
signal, we are analyzing the abundance, distribution
and radiocarbon content of terrestrial biomarkers
(plant wax-derived n-alkanoic acids and lignin-derived
phenols) throughout the sediment core. These
vascular plant markers will be used to reconstruct the
composition and flux of POC in response to changing
permafrost dynamics in the Mackenzie River drainage
basin.
629

P-509
Exploiting isotopic, organic, and inorganic geochemical tracers
of terrestrial matter in suspended particles of the Fraser River,
British Columbia
Britta M. Voss 1,2 , Bernhard Peucker-Ehrenbrink 1 , Timothy I. Eglinton 1,3 , Valier Galy 1 ,
Daniel B. Montluçon 1,3 , Ekaterina Bulygina 4 , R. Max Holmes 4 , Gregory Fiske 4 , Li Xu 1 ,
Sharon L. Gillies 5 , Steven Marsh 5 , Alida Janmaat 5 , Bryce Downey 5 , Jenna Fanslau 5 ,
Helena Fraser 5 , Garrett Macklam-Harron 5
1 Woods Hole Oceanographic Institution, Woods Hole, United States of America, 2 Massachusetts Institute of
Technology, Cambridge, United States of America, 3 Eidgenössische Technische Hochschule, Zürich,
Switzerland, 4 Woods Hole Research Center, Woods Hole, United States of America, 5 University of the
Fraser Valley, Abbotsford, Canada (corresponding author:bvoss@whoi.edu)
Rivers are a critical component of the global
transfer of terrestrial organic matter from land to the
ocean. Suspended particulate matter incorporates
weathered eroded lithologic material and organic
matter of geologic and biologic origin. The
association of organic carbon with mineral particles is
a complex process not adequately understood over
space and time throughout river transit and is highly
variable from one drainage basin to the next. The
Fraser River in southwestern Canada provides a
valuable testing ground for detailed geochemical
characterization of particle sources and
transformations across a large, climatically and
geologically diverse river basin with no dams on its
main stem. Bulk stable and radioisotopic analyses of
organic carbon on particles, as well as of dissolved
organic and inorganic pools, offer insight to the
sources of different components of the carbon load
carried—and possibly transformed within—the Fraser
River. We add to this suite of measurements detailed
analyses of the particles themselves, including
mineral surface area and scanning electron
microscopy visualization. We also measure various
elemental and organic compound concentrations on
particles, such as lipid biomarkers, lignin phenols,
trace metals, and 187 Os/ 188 Os. Radiogenic Os isotope
signatures provide lithological age information on
timescales far exceeding that of radiocarbon. This
coupling of organic and inorganic characterization of
particles along a river course, along with quantitative
and qualitative spatial metrics of individual particles,
offers a unique, in-depth perspective on organic
carbon-mineral association and exchange between
dissolved, particulate, and sedimentary phases from
weathering source to coastal sink. In addition to
detailed basin-wide snapshots, our collaboration with
scientists at University of the Fraser Valley in
Abbotsford has initiated time series sampling, which
will allow us to characterize seasonal variability in
particle flux and composition. In the future, these
methods will be extended to other rivers with very
different particle concentration and size spectrum
regimes (ranging from the particle-rich Ganges-
Brahmaputra River system to the much less turbid
Congo River). Ultimately, this work on the Fraser
River will serve as a foundation for similar studies on
other river systems in order to better constrain global
fluxes and transformations of carbon and other
biogeochemically important elements to the world
ocean, and the response of these processes to the
effects of climate change and other human-induced
alterations.
Segregation of carbon pools in the Fraser River by
stable and radiogenic isotope signatures: particulate
(POC) and dissolved (DOC) organic carbon and
dissolved inorganic carbon (DIC). Atmospheric,
biologic, and geologic endmembers are plotted for
reference. Samples collected at various points along
the Fraser River main stem and at significant
tributaries in late summer 2009.
630

P-510
Testing the potential of bacterial branched tetraether lipids as
temperature proxy in peat and immature coal deposits
Johan Weijers 1,2 , Philipp Steinmann 3 , Ellen Hopmans 2 , Stefan Schouten 1,2 , Jaap
Sinninghe Damsté 1,2
1 Utrecht University, Utrecht, Netherlands, 2 NIOZ Royal Netherlands Institute for Sea Research, Den Burg -
Texel, Netherlands, 3 Université de Neuchâtel, Neuchâtel, Switzerland (corresponding
author:j.weijers@geo.uu.nl)
Branched glycerol dialkyl glycerol tetraether
(brGDGT) membrane lipids occur ubiquitously in peat
and soil and derive from as yet unknown bacteria. In
soils, the degree of methylation and cyclisation of
branched tetraethers (MBT index and CBT ratio,
respectively) have shown to relate to both soil pH and
annual mean air temperature (MAT). Using this
relation, past annual MATs can be reconstructed by
analysing brGDGTs in marine sediment records near
large river outflows. More recently, the potential of this
MBT/CBT proxy is also being explored in lakes.
Despite being more abundant in peat than soils,
however, the utility of the proxy has not yet been fully
explored in peat records. Present day peat records
generally extent back to the early Holocene, but if the
MBT/CBT proxy were shown to be applicable in peat
deposits, there is also potential to apply it to immature
coal deposits which could provide valuable snapshots
of continental climate back to the early Cenozoic.
To test the utility of the MBT/CBT proxy in peat,
brGDGTs have been analysed in the Etang de la
Gruère (EGr) peat bog from the Jura Mountains,
Switzerland, extending back ca. 13ka. Annual MAT
reconstructed for the top of the bog (i.e., at the water
table level) is with 13°C clearly higher than measured
annual MAT (5.5°C) and annual mean in situ
temperature of the bog (~8°C). Also in other peat
bogs reconstructed MAT seems slightly higher than
measured MAT although the magnitude differs [1,2].
Analysis of more peat bogs is needed to verify the
consistency of this offset.
Comparison of down-core MBT/CBT-derived
temperature with in situ measured pore water pH and
temperature of EGr bog indicates that the brGDGT
composition does not reflect present day in situ
conditions (Fig). Instead, the CBT-derived pH record
reflects a stratigraphic boundary between Carex and
Sphagnum dominated peat at 4 m depth that is not
present in the pore water profile, testifying to a ‗fossil‘
nature of the brGDGTs down the peat bog. Similarly,
reconstructed MAT also shows a pronounced shift at
this stratigraphic boundary that is too large to be
accounted for by natural climate change during the
Holocene. It is suggested that a change in wetness
and nutrient status accompanying the boundary had
an impact on the bacterial community composition,
including the brGDGT synthesising bacteria.
In addition to EGr bog, three immature coals from the
Argonne Premium Coal Series were analysed.
Branched GDGTs are clearly present in the Beulah
Zap lignite (Ro = 0.25%) but only just above detection
limit in the Wyodak Anderson coal (Ro = 0.32%),
which is of about the same age (Late Palaeocene)
and location (central U.S.A.). In the more mature
Illinois #6 coal (Ro = 0.46%), brGDGTs are completely
absent. Reconstructed annual MAT for the Beulah
Zap lignite is ca. 29°C, several degrees higher than
estimates based on leaf margin and oxygen isotope
analyses. It does testify, however, to the warm
continental conditions at the late Palaeocene of the
central U.S.A..
Although further validation is required, these results
do show potential for application of the MBT/CBT
temperature proxy in peat and lignite deposits.
Reconstructed (black) and measured (blue) pH and
temperature down the EGr peat core.
[1] Huguet et al. (2010) Org. Geochem. 41, 559-572.
[2] Liu et al. (2010) Org. Geochem. 41, 653-660.
631

P-511
The effect of soil moisture on biosynthesis of lipids in plants
and their incorporation and preservation in soils
Guido Wiesenberg 1 , Bidisha Majumder 1 , Martina Gocke 1 , Jennifer Dungait 2 , Liz Dixon 2 ,
Roland Bol 2
1 Department for Agroecosystem Research, University of Bayreuth, Bayreuth, Germany, 2 Rothamsted
Research, North Wyke, Okehampton, United Kingdom (corresponding author:guido.wiesenberg@unibayreuth.de)
Soil properties like e.g. pH, oxygen availability and C
storage are influenced by environmental factors such
as soil moisture. Especially water-logged and peaty
soils can be characterized by large amounts of
organic C and provide opportunity for improved
preservation of total organic matter. Especially for
comparatively recalcitrant compounds like alkanes
this is relevant at a molecular scale. However, long
term effects of different soil moisture on identical soils
are investigated seldom and therefore it remains
unknown, if even low differences in soil moisture (10-
30 %) might have an effect on C incorporation and
preservation in soils. Additionally, it remains still
unknown, if different C incorporation or preservation
mechanisms are relevant to increase especially
recalcitrant components in soil.
A long term field experiment on drained vs. undrained
grassland plots from the Rowden plots (North Wyke
Research, Okehampton, UK) provides the unique
opportunity for studying long term influences of
different soil moisture on biodiversity of plants and soil
C storage. After establishment of drainage the plant
community changed within several decades from
predominant species adopted to wet conditions like
Juncus effusus towards predominant grasses that are
more tolerant to lower soil moisture like Lolium
perenne. In the drained soil, Corg and extractable lipid
contents decreased throughout the soil profile by ~20
% due to lower soil moisture, which results in drought
conditions during summer time. However, it remains
unknown, if this change in drained vs. undrained plots
is related to a modified plant biomass input due to
changing plant community or an improved
degradation of organic matter in drained plots.
To investigate these effects in detail, we carried out
laboratory experiments, where identical plants (Lolium
perenne and Juncus effuses) are kept under
controlled conditions at two different soil moisture
levels, which were adjusted daily to 70% and 100% of
WHC, respectively. For Lolium the plant pots were
kept open, which led to drought conditions during later
stages of the experiment. For Juncus the plant pots
were closed except of a narrow opening, where
shoots could grow. Short and medium term responses
of plants and C incorporation in soil are followed by
combining lipid and Corg analyses with the 14 C pulse
labeling technique. The 14 C label is determined
several times after the labeling in plants and soils for
bulk Corg and at a molecular level (for total extractable
lipids, fatty acids and alkanes).
Higher soil moisture resulted in an improved growth of
biomass, which was 30-70% higher than under low
moisture, depending on sampling date. This was
almost identical for shoot and root biomass, and for
both investigated plant species. Epicuticular and
internal lipid contents and distribution patterns in
plants were almost identical for both moisture
variants, whereas previous studies demonstrated an
effect of moisture on the lipid content and composition
of plants.
The 14 C data revealed no effects of different soil
moisture on carbon utilization and biosynthesis for
Juncus plants. For Lolium an improved re-utilization of
C within plants under low moisture due to lower
stomatal conductance was observed. The
translocation of 14 C into soil was higher in the low
moisture variant. This argues for an improved
preservation of C in moist soils, whereas the
incorporation of C must not be improved.
Both, laboratory and field experiments provide
evidence that difference in biomass production, but
also different soil moisture levels regulate C
incorporation and storage in soil. Under comparatively
low moisture, C incorporation into soil can be
stimulated, whereas high moisture improves
preservation of C – even at a molecular level.
632

P-512
The effect of fire intensity on alkane composition of plant
organic matter and soils affected by fire
Guido Wiesenberg 1 , Andreas Nestler 1,2 , Stefanie Birkner 1 , Ulrich Hambach 2
1 Department for Agroecosystem Research, University of Bayreuth, Bayreuth, Germany, 2 Geomorphology
Department, University of Bayreuth, Bayreuth, Germany (corresponding author:guido.wiesenberg@unibayreuth.de)
Plant-derived biomass entering soil commonly leads
to a typical chemical composition of soil organic
matter (SOM), whereas alteration of biomass during
microbial and thermal degradation results in chemical
changes of plant-derived SOM. On a molecular level
plant-derived SOM is characterized by a
predominance of long-chain alkanes, fatty acids and
alcohols within the lipid fraction with a strong relative
predominance of odd or even carbon-numbered
homologues depending on the lipid fraction. E.g.
plant-derived alkanes as typical epiculticular wax
components and degradation products of
functionalized lipids are dominated by odd long-chain
alkanes. Contrastingly, a progressive increase in
short-chain even-numbered alkanes was found in
charred biomass with increasing temperature
associated by a decrease in chain-length and a
decrease in the predominance of odd n-alkanes [1].
Thermal degradation of plant biomass during a fire
results in a modification of lipid distribution patterns
that differs from microbial degradation. Not only the
composition, but also the total amount of lipidic
components changes. The aim of the current study
was to assess effects of temperature oxygen
availability and source biomass on amount and
composition of thermal degradation products.
Additionally, we compared results from laboratory
experiments with soil and archaeological samples of
well known burning history.
During charring at low temperatures (400°C) a decrease in abundance of the all lipidic
fractions occurs including aromatic hydrocarbons with
a stronger depletion in aliphatic than in aromatic
components. At higher temperatures (>350°C) even
carbon numbered monoalkenes increase in
abundance presumably due to degradation of ester
bound lipids containing side chains with 14-18
carbons. In general this is in agreement with NMR
spectra [2], indicating a higher aromaticity at higher
charring temperatures.
The effect of oxygen availability improved degradation
of alkanes, whereas under nitrogen atmosphere
degradation was limited and resulted in larger
amounts of alkanes, alkenes and PAHs.
All these observations indicate that incomplete
burning results in large amounts of complex organic
remains in soil, where with increasing temperature
burning gets more complete leaving less burning
residues. Recent investigations indicate a structural
re-arrangement of lipidic components in burned plant
biomass not only as a function of temperature,
duration of thermal degradation, and oxygen
availability, but also as a function of the initial plant
biomass composition.
Additionally, we compared burning residues from the
laboratory experiment, where thermal degradation
was carried out from 200-700°C, the Roman Furnace
Project at Velzeke (Belgium) with furnaces managed
at 550°C and 1070°C, respectively, recent burnt
agricultural residues derived from agricultural plots in
Russia, material from ancient anthropogenic pits as
well as fire places from different ancient settlements.
The alkane distribution patterns clearly correlated with
proposed temperatures. Therefore, alkanes and
alkenes as molecular marker might be useful to trace
not only fire in recent and ancient soils, but also the
burning conditions and potentially the initial biomass.
References
[1] Wiesenberg GLB, Lehndorff E, Schwark L 2009.
Org Geochem 40, 167.
[2] Baldock JA, Smernik RJ 2002. Org Geochem 33,
1093.
633

P-513
Anaerobic oxidation of plant-derived 3-phenylpropanoids by the
denitrifying bacterium ―Aromatoleum aromaticum‖ EbN1
Heinz Wilkes 1 , Kathleen Trautwein 2,3 , Ralf Rabus 2,3
1 Helmholtz Centre Potsdam GFZ German Research Centre for Geosciences, Potsdam, Germany, 2 Institute
of Chemistry and Biology of the Marine Environment (ICBM), University Oldenburg, Oldenburg, Germany,
3 Max Planck Institute for Marine Microbiology, Bremen, Germany (corresponding author:wilkes@gfzpotsdam.de)
Phenylalanine-derived 3-phenylpropanoids (e.g.
cinnamic acid, p-coumaric acid, ferulic acid, sinapinic
aicd) are widespread in nature. They represent the
building blocks of lignin, which is the second most
abundant terrestrial biopolymer after cellulose,
accounting for approx. 30% of the organic carbon in
the terrestrial biosphere [1]. As components of
secondary metabolites (anthocyanins, flavonoids or
phytoalexins) 3-phenylpropanoids play also an
important role in plant stress responses [2]. Release
of 3-phenylpropanoids into the environment arises
mainly from the biodegradation of plant material. In
accordance with the natural abundance, many
microorganisms are able to utilize 3phenylpropanoids.
Their metabolism has been
studied in a variety of bacteria, and different
degradation pathways have been proposed to be
employed by these bacteria.
Here we present results of studies on the metabolism
of 3-phenylpropanoids by the denitrifying bacterium
―Aromatoleum aromaticum‖ EbN1 under aerobic and
anaerobic conditions based on identification of
metabolites and differential protein profiling. Strain
EbN1 was originally isolated with ethylbenzene from
freshwater sediments and demonstrated to utilize a
large variety of aromatic compounds under anoxic
conditions [3]. This includes p-ethylphenol which is
oxidised via a degradation pathway reminiscent of
known anaerobic ethylbenzene degradation in the
same bacterium [4].
The present study revealed that strain EbN1 is
capable of utilizing cinnamyl alcohol, hydrocinnamic
acid, cinnamic acid, 3-(4-hydroxyphenyl)propanoic
acid, p-coumaric acid, m-coumaric acid, 3-(3,4dihydroxyphenyl)propanoic
acid and caffeic acid
under anoxic conditions. GC-MS analysis of
metabolites formed during growth with these
substrates provided evidence for their degradation via
a �-oxidation pathway as outlined for
hydrocinnamic/cinnamic acid in Figure 1. 3-Hydroxy-
3-phenylpropanoate was strongly prevailing upon
growth with hydrocinnamate and cinnamate while the
respective substrate as well as benzoate were
present in small relative amounts only. This could
indicate that the hydration of cinnamoyl-CoA takes
place at a high rate while one of the following steps
required to form benzoyl-CoA from 3-hydroxy-3phenylpropanoyl-CoA
might be rate limiting.
Experiments performed to test the potential of strain
EbN1 to co-metabolize 3-phenylpropanoids that do
not support growth indicated a high substrate
specificity of the involved enzymes. The capacity of
strain EbN1 for lignin monomer degradation is of
ecophysiological relevance, since it could potentially
contribute to the formation and fate of dissolved
organic matter in freshwater and soil environments.
HO
COO -
COSCoA
O
COSCoA COSCoA
COSCoA
COSCoA
+ Acetyl-CoA
Fig. 1. Simplified pathway of oxidation of
hydrocinnamic and cinnamic acid to benzoic acid in
strain EbN1.
References
[1] Boerjan, W., Ralph, J., Baucher, M., 2003. Annu Rev
Plant Biol 54, 519-546.
[2] Dixon, R.A., Paiva, N.L., 1995. The Plant Cell 7, 1085-
1097.
[3] Rabus, R., Widdel, F., 1995. Arch Microbiol 163, 96-103.
[4] Wöhlbrand, L., Wilkes, H., Halder, T., Rabus, R., 2008. J
Bacteriol 190, 5699-5709.
634

P-514
Molecular characterization of terrestrial, permafrost-derived
organic matter along a soil-river-ocean transect (Lena Delta, NE
Siberia)
Maria Winterfeld 1,2 , Miguel Goni 3 , Gesine Mollenhauer 1,2
1 Alfred Wegener Institute for Polar and Marine Research, 27570 Bremerhaven, Germany, 2 Department of
Geosciences, University of Bremen, Klagenfurther Str., 28359 Bremen, Germany, 3 College of Oceanic &
Atmospheric Sciences, Oregon State University, 104 Ocean Administration Building, COAS, Corvallis, OR
97331, United States of America (corresponding author:Maria.Winterfeld@awi.de)
About 50% of the global soil organic carbon (OC) is
stored in Arctic permafrost soils [1]. In response to
global climate warming vast amounts of this mainly
freeze-locked, old OC will likely be remobilized and
released during permafrost thawing. However, until
now the fate of organic matter released from
permafrost and its possible feedbacks for the global
carbon cycle are hardly understood. It is rather
unknown which proportions of the previously frozen
OC will be released into the atmosphere as carbon
dioxide or methane or remain fixed in soils and
tundra/taiga biomass. Likewise, it is unknown how
much of the OC will be exported in
particulate/dissolved state via fluvial runoff and
coastal erosion and become further degraded in the
riverine and oceanic water column.
In recent years, there have been few studies along
the East Siberian Shelf Seas qualitatively
investigating permafrost OC exported to the ocean on
a molecular level (e.g. [2]). These studies mainly
focused on the analysis of terrestrial lipids found in
sediments and particulate organic carbon (POC) from
the oceanic water column in order to investigate the
sources, transport processes and degradation of
terrigenous OC on the shelves. Nevertheless, in these
studies the original molecular composition of the
terrestrial OC source, the permafrost soils, was not
analysed although such characterization is essential
to study the fate of terrestrial OC in the Arctic.
In order to characterize the molecular composition of
permafrost soils as well as potential compositional
changes during transport from land to ocean, we
analyzed biomarkers from soil samples, suspended
particulate matter (SPM) and sediments from the
Lena Delta and adjacent Buor Khaya Bay, NE Siberia.
The soil samples were analyzed for their biomarker
composition including leaf wax & soil derived lipids,
and lignin phenols to identify those permafrost
compounds that should also be detectable in riverine
and shelf-derived surface water POC and sediments,
respectively. Here, we report the lignin phenol
composition of soil samples, POC, and sediments and
use the acid/aldehyde ratios ([Ad/Al]) of lignin phenols
in soils to determine the degree of oxidative lignin
degradation (e.g. [3]) before it is exported to the
ocean. Furthermore, we report syringyl/vanillyl (S/V)
and cinnamyl/vanillyl (C/V) ratios of soil, POC and
sediments in order to distinguish between different
vegetation types (i.e. angiosperm vs. gymnosperm
and woody vs. non-woody plants, e.g. [4]). This will
help distinguishing spatially different terrestrial OC
sources since the southern Lena River catchment is
mainly characterized by taiga forest whereas the Lena
Delta is characterized by tundra vegetation. With
these results, we provide new molecular data for
determining the current state of permafrost-derived
OC transferred from land to ocean in the Lena Delta
region.
References
[1] Tarnocai, C., Canadell, J.G., Schuur, E.A.G.,
Kuhry, P., Mazhitova, G. & Zimov, S. (2009). Soil
organic carbon pools in the northern circumpolar
permafrost region. Global Biogeochemical Cycles 20,
doi: 10.1029/2008GB003327.
[2] Vonk, J.E., Sánchez-García, L., Semiletov,
I., Dudarev, O., Eglinton, T., Andersson, A. &
Gustafsson, Ö. (2010). Molecular and radiocarbon
constraints on sources and degradation of terrestrial
organic carbon along the Kolyma paleoriver transect,
East Siberian Sea. Biogeosciences 7, 3153-3166.
[3] Goñi, M.A., Yunker, M.B., Macdonald, R.W.
& Eglinton, T.I. (2005). The supply and preservation
of ancient and modern components of organic carbon
in the Canadian Beaufort Shelf of the Arctic Ocean.
Marine Chemistry 93, 53-73.
[4] Hedges, J.I. & Ertel J.R. (1982). Lignin
geochemistry of a Late Quaternary sediment core
from Lake Washington. Geochimica et Cosmochimica
Acta 46, 1869-1877.
635

P-515
Variability of terrestrially-derived particulate organic carbon in
the lower Yangtze River (Changjiang): A monsoon dominated
water system
Ying Wu, Hao Yu, Jing Zhang, ZhuoYi Zhu
State Key Laboratory of Estuarine and Coastal Research, Shanghai, China (corresponding
author:wuying@sklec.ecnu.edu.cn)
As human impacts on the environment increase,
rivers and coastal systems are becoming more
vulnerable through enhanced fertilizer usage,
damming, deforestation and other land-use changes.
Additionally, phenomena associated with climate
change, such as the increase frequency of ENSO or
extreme climate events, have resulted in changes in
riverine runoff and sediment load. Both changes will
certainly impact the flux and composition of materials
from the rivers to the ocean.
Particulate organic matter from the lower reach of the
Yangtze River was collected monthly from 2003
through 2006. The samples were then examined
using elemental (%OC, C/N), carbon isotopic and
terrigenous biomarker analyses. The composition of
lignin phenols exhibited distinguishable seasonal
variation. The seasonal variation in various
parameters was found to be larger than the
interannual variability in the lower Yangtze River,
which is dominated by a monsoon climate.
Additionally, the mass-normalized lignin yields were
negatively correlated with the water discharge.
Furthermore, the S/V and C/V ratios of the samples
indicated that both woody and non-woody angiosperm
plant detritus were the primary sources of lignin
phenols. Moreover, the (Ad/Al)v ratios revealed that
most SPM samples were relatively fresh, although
more degradation was observed in 2006. A three-endmember
model was built with plant detritus, soils and
phytoplankton as three sources of organic matter in
SPM and the results showed that the soil was the
dominant contributor of organic matter to the SPM.
Although variability in the lignin composition of
particulate organic matter is related to the sources, it
can also be attributed to other factors. Climate
change could be a large driving force in alteration of
the flux of terrestrial-derived organic matter. A good
correlation between the Nino 3.4 Index and sediment
load & �8 was observed from 2003 to 2006,
especially when a 2 months lag was considered.
However, during 2006, the precipitation was also
impacted by global warming, which resulted in
extreme drought over the drainage basin. Moreover,
reservoir impoundment resulted in a longer retention
time for terrigenous organic matter. Additionally,
elevated Chl-a concentrations were observed as the
SPM decreased. These findings indicate that a
decrease in sediment load will not only result in
altered particulate organic matter concentrations, but
also in changes in the structure of organic material.
These changes will result in more fresh and labile
organic material being transported into coastal
systems, which will have an important impact on the
regional carbon cycle and marine ecosystem.
However, these findings are based on continuous
observations from one lower reach station. In the
future, data from more sampling stations located at
different distances from the Estuary should be
considered to gain a better understanding of the
biogeochemistry of terrestrial-derived organic matter
in the Yangtze River.
636

P-516
Distributions of branched tetraethers in soils and suspended
particulate matter in the Amazon basin: Implications for the
MBT/CBT palaeothermometer
Claudia Zell 1 , Jung-Hyun Kim 1 , Marie-Paule Bonnet 2 , Gwenaël Abril 3 , Jean-Michel
Mortillaro 4 , Rodrigo Sobrinho 5 , Jaap Sinninghe Damsté 1
1 NIOZ Royal Netherlands Institute for Sea Research, Den Hoorn, Netherlands, 2 Universite Toulouse,
Toulouse, France, 3 Laboratoire Environnements et Paléoenvironnements Océaniques, Talance, France,
4 CNRS, Paris, France, 5 Universidade Federal Fluminense, Niteroi, Brazil (corresponding
author:claudia.zell@nioz.nl)
Branched glycerol dialkyl glycerol tetraethers
(GDGTs) are membrane lipids of bacteria living
predominantly in soils. Their distribution reflects mean
annual air temperature (MAAT) and soil pH, which
was used to develop the Methylation index of
Branched Tetraethers (MBT) and Cyclization ratio of
Branched Tetraethers (CBT) [1]. By erosion of soil,
branched GDGTs are transported from the continent
to the ocean by rivers. Hence, branched GDGTs
found in marine sediments deposited close to the river
mouth may record an integrated climate signal of the
river drainage basin [2, 3]. In this study, we address
the processes that affect the distribution of branched
GDGTs in the Amazon basin before it enters the
ocean. We compared branched GDGT distributions in
Amazon soils and suspended particulate matter
(SPM) collected in the Amazon River, its tributaries,
and floodplain (varzea) lakes. For the conversion of
the MBT/CBT values into MAAT and soil pH, we
applied two different calibrations: the global soil
calibration [1] and a regional calibration [3]. For soils
from the Amazon low lands, instrumental data show a
mean annual air temperature of about 27ºC and a soil
pH of 4.8±0.1 was measured. The MBT/CBT-derived
average temperature of the soils using the regional
calibration is about 23.9ºC±1.0 (n=18), which is cooler
but less scattered in comparison to that calculated
with the global calibration (25.0ºC±3.0, n=18). Both
calibrations result in similar reconstructed soil pH of
4.6±1.4 (global) and 4.6±1.3 (regional) (n=18).
The SPM of the Amazon River shows MBT/CBTderived
MAAT of 25.7ºC±1.3 (n=4, global calibration)
or 22.6ºC±0.7 (n=4 regional calibration). MBT/CBTderived
MAAT obtained from SPM in tributaries
originating in the Andes (Madeira and Solimões) do
not show significantly lower MBT/CBT-derived MAAT
compared to other tributaries originating from the
Amazon low lands (Negro, Tapajos and Trombetas),
even though a lower temperature signal was expected
for the rivers originating in the Andes as soils at
higher altitude experience lower temperatures. The
CBT-derived pH signal in the Amazon River SPM is
relatively constant around 5.8±0.2 (n=4, global
calibration) or 5.4±0.2 (n=4, regional calibration). The
rivers Negro and Trombetas show a reconstructed pH
of about one pH unit lower. The pH measured in the
water column of the Amazon River and its tributaries
is 6.3±0.1 (n=5) except those of the Negro and
Trombetas river which have pH values of 4.9 and 5.3,
respectively. That the CBT-derived pH signal of
branched GDGTs from river SPM is higher than that
of most of the Amazon soil which has a pH of 4-5 may
suggest an influence of in-situ produced branched
GDGTs in the river water column. Our study implies
that the regional calibration needs to be further
developed for more precise MAAT predictions in the
Amazon basin. As MBT/ CBT-derived MAAT from
river SPM are not significantly lower than those of soil
we conclude that the MBT/CBT signals in the Amazon
River mostly reflect Amazon basin low land conditions
and thus no major influence of colder mountainous
Andes region although this has been suggested for
the Early Holocene [3].
Temperature o C
26
25
24
23
22
21
Soil
(n=18)
River Varzea
SPM
(n=8)
SPM
(n=7)
pH
6
5
4
3
Soil
(n=18)
River Varzea
SPM
(n=8)
SPM
(n=7)
Figure 1: Box plot of MBT/CBT-derived pH and
temperature, calculated with the regional formula [3].
[1] Weijers, J.W.H., et al. (2007), Geochim.
Cosmochim. Acta 71, 703–713.
[2] Weijers, J.H.W., et al. (2007), Science 315, 1701.
[3] Bendle, J.A., et al. (2010), Geochem. Geophys.
Geosyst. 11, Q12007.
637

Author Index
638

Abbassi Soumaya P-078
Abbott Geoffrey P-002, P-024, P-028
Abdullah Wan Hasiah P-033, P-080
Abeed Qusay P-114
Ablya Enver P-079, P-123
Abolins Peter P-033, P-080
Abrao Jorge Joao P-456
Abril Gwenaël P-516
Achal Sneh O-49, P-125
Adam Pierre P-224
Adami Rodrigues
Karen
P-017
Adkins Jess O-12, P-354
Adolphi Florian P-473
Aguiar Helen G. M. P-001
Aguiar da Silva San
Gil Rosane
P-017
Ahmed Manzur P-081, P-282
Ahn Yong-Cheon P-438
Aichner Bernhard P-138
Aitken Carolyn P-180
Aitkins Caroline P-015
Aizenshtat Zeev O-10
Akbarzadeh Kamran P-339
Akhmedova
Alexandra
P-275
Akinlua Akinsehinwa P-003
Al Ghammari
Mohammed
P-082
Al Lawati Wafa. M. P-139
al Sandouk Nadia P-328
Alawi Mashal P-397
Albrecht Heidi P-344
Alegret Laia P-471
Alexandre Marcelo P-417
Al-Fares Abdulaziz P-364
Alfonzo Ingrid P-346
Alizadeh Bahram P-083
Al-Khamiss Awatif P-364
Allan Tony P-081
Allard Béatrice P-004
Allen Chris P-247, P-387, P-429
Allen Jon P-261
Allix Pierre P-008
Almeida de Azevedo
Débora
Aloisi Giovanni P-172
Altunina Lyubov P-146
Alves Fontes Rosane P-330
Amann Rudolf P-437
Amend Jan P. P-437
Amir Hassan Meor
Hakif
P-006, P-017, P-058, P-147,
P-277, P-395
P-080
Amrani Alon O-10, O-12, P-354, P-356
AnŤelkoviš Tatjana P-388
Andersen Nils P-467
Anderson John O-02
Andersson August O-56, P-005, P-246
Andersson Rina P-187, P-188
Andjelkovic Darko P-151, P-152
Andjelkovic Tatjana P-151, P-152
Ando Takuto P-189
Andre Dominique P-345
Andriany Rita P-364
Angulo Rodolfo P-230
Anka Zahie P-089, P-307
Anquetil Christelle P-507

Anselmetti Flavio S. O-63
Ansong Geng P-351
Antipenko Vladimir P-084, P-085
Aplin Andy P-370
Aquino Neto
Francisco
Araujo Carla P-330
Araújo Fátima P-199
Archer Corey O-23
Aref Mahmoud P-172
Arenas Jennifer P-393
Argant Jacqueline P-460
Arnaud Fabien P-133
Arouri Khaled P-086
Arzhannikov
Alexander
P-001, P-058
P-021
Ascough Philippa P-014
Asif Muhammad P-281
Avanzinelli Riccardo O-23
Azevedo Débora A. P-001, P-306
Baas Marianne O-15, P-473
Babatunde Julius O-54
Babulevich Nataliya P-021
Badewien Tanja P-225
Badics Balázs P-272
Bagnoud-Velasquez
Mariluz
P-475
Bahk Jang-Jun P-438
Bahlmann Enno O-65
Bakke Jostein P-402
Bale Nicole P-156
Ballantyne Angela P-128
Baltenweck-Guyot
Raymonde
P-430
Bannert Andrea O-80, P-426
Banning Erin P-448
Bao Hongyan P-226
Bao Youshu P-287
Barbanti Silvana P-059
Barden Holly O-41
Barth Tanja P-141, P-149, P-342, P-365
Barwise Tony O-50
Basse Andreas P-157
Bastien Claire O-43
Bastow Mark P-087
Bateson Mary P-444
Batista Fabian O-52
Batova Galina P-382
Baudrand Marion P-172
Bauersachs Thorsten P-158, P-190
Baur Friedemann O-77
Bausch Marlene O-60
Bechtel Achim P-037, P-088, P-159
Beck Melanie P-396
Becker Kevin P-201
Beckmann Britta P-218, P-401
Behar Françoise O-71, O-72, O-84, P-064, P-
308
Behrens Harald P-357
Belayouni Habib P-050, P-078
Bell Andy O-18
Belt Simon P-191
Ben Hassen Aïda P-050
Bendle James P-462
640

Bennett Barry O-55, P-098
Benthien Albert O-29, P-409
Berbesi Luiyin P-089
Berg Michael P-139
Bergmann Uwe O-41
Berke Melissa P-192, P-447, P-485
Bernardes Marcello P-456
Bernasconi Stefano O-47, P-159, P-178, P-182,
P-220, P-402, P-406, P-467
Berndmeyer Christine P-161
Berner Ulrich P-090, P-366
Bernhard Joan P-425
Bernhardt Beth P-485
Berrios Irenio P-303
Bertram Sebastian O-76
Bertrand Olivia P-055, P-460
Biache Coralie P-232
Bickert Torsten P-198
Bieleń Wojciech P-289, P-374
Billaud Yves P-132, P-133
Bin Zhang P-101
Bingham Elizabeth P-499
Binotto Regina P-091, P-330
Bird Laurence P-169
Bird Michael P-014
Birgel Daniel P-160
Birk Jago P-009
Birkholz Axel O-47, P-402
Birkner Stefanie P-512
Bishop Andrew O-23, P-011
Blaga Cornelia O-63, P-414
Blanchart Pascale P-140
Blanchet Denis P-064
Blanc-valleron Marie-
Magdeleine
P-172
Blumenberg Martin O-59, O-76, P-161, P-174,
P-175, P-204
Blyth Alison P-134, P-193
Bødtker Gunhild P-141, P-149
Boeckx Pascal P-243, P-501
Boetius Antje O-60
Bogus Kara P-482
Bohrer Denise P-091
Bojic Aleksandar P-151, P-152
Bol Roland P-028, P-511
Böll Anna P-227
Bonnet Marie-Paule P-516
Boom Arnoud P-228
Boreham Chris P-069, P-219, P-282
Borisova Lyubov P-092, P-229, P-302
Bortnikova Svetlana P-107
Borzijin Tenger P-045, P-355
Boscardin Rachel P-403
Boski Tomasz P-207, P-230
Bossard Nicolas P-132, P-133, P-403
Böttcher Michael O-57
Bouloubassi Ioanna P-162, P-206, P-457
Boult Steve P-035
Bounaceur Roda O-72, P-336
Boussafir Mohammed P-211
Bovolo Isabella P-500
Brassell Simon P-194
Bréheret Jean-
Gabriel
O-30, P-250
Bremser Wolfram P-138
641

Brinkhuis Henk P-200, P-468
Britton Matthew P-228
Brocks Jochen O-07, P-195
Broda Nadine P-451
Brooks Gregg R. P-481
Brothwell Don P-131, P-136
Brown Kristina P-234
Brown Melisa P-015
Bruggeman
Christophe
P-140
Brummer Geert-Jan P-197, P-408
Bryant Donald P-444
Buckles Laura P-163
Buggle Björn P-419
Bühring Solveig P-164
Bulkam Ozlem P-196
Bull Ian O-31, P-205
Bulygina Ekaterina P-509
Burdelnaya
Nadezhda
Bürgmann Helmut P-404
Burklé-Vitzthum
Valérie
Burshtein Lev P-093
Buscail Roselyne P-248
Bush Richard P-054
P-034, P-115
P-336, P-360
Bushnev Dmitry P-034, P-115
Bussian Bernd P-138
Buzek Frantisek P-266
Caballero Margarita P-485
Cagatay M.Namık P-196
Cai Chunfang P-051, P-102
Cai Jingong P-045
Caldas Bruno P-277
Calzada Mendoza
Jacqueline Mireya
Campello Cordeiro
Renato
P-165
P-456
Cander Harris P-375
Cao Changqun P-062, P-471
Cao Jian P-094, P-116
Cao Zhi-Hong P-135
Carlos Sequeira
Fernandes Antonio
P-017
Carlson Johan P-342
Carlson Robert M. K. P-467
Carr Andrew P-311
Carr Andrew S P-228
Carreira Renato P-166
Carstens Dörte P-404
Castañeda Isla P-197
Castañeda Isla S. P-408
Cerli Chiara P-423
Cerqueira Jose R. P-264
Chabbi Abad P-040
Chalaya Olga P-372, P-381
Chambers Frank P-499
Chapron Emmanuel P-133
Charkashov Georgy P-233
Charkin Alexander O-56, P-246
Charrié-Duhaut
Armelle
Chase Brian M P-228
Chaves Lidia P-499
Chaves Torres Lidia P-052
O-43, P-129
Chen Honghan P-301
642

Chen Jianfang P-214
Chen Tengshui P-359
Chen Wenwen P-198
Chen Xin P-399
Chen Yan P-096
Cheng Tongjing P-317
Cherkashev Georgiy P-293
Cheshkova Tatyana P-053
Chi Bo P-316
Chikaraishi Yoshito O-02, O-27, O-28, P-237, P-
405, P-442
Christian Ruby P-386
Chrostowska Anna P-341
Cioccari Giovani P-330
Clarke Edward O-78
Claypool George P-039, P-185, P-203
Clayton Stephen P-212
Collins James O-34
Collins Lindsay P-167
Connan Jacques O-43, P-129, P-130
Cooke Martin P-231
Coolen Marco P-448
Corbett Reide P-199
Cordeiro Lívia P-166
Cordier Marie-Ange P-390
Cornford Chris P-095
Courtiade Marion P-064
Coutinho Luiz Felipe P-330
Coy Gordon P-082
Cramer Bernhard P-090
Cravo-Laureau
Cristiana
O-44
Creux Patrice P-341
Crews Steve P-310
Crews Steven P-023
Crill Patrick P-187, P-502
Crosta Xavier P-191
Cumming Alex P-228
Curiale Joseph O-36
Cvetkoviš Olga P-047
Cypionka Heribert O-13, P-440
Czechowski
Franciszek
P-100
Czirbus Nóra P-503
Dabat Francois P-345
Dahl Jeremy O-73, P-031, P-291
Dai Jinxing P-259, P-260
Dairiki Chieko P-488
Dal Sasso Marco
Aurélio
P-147
Danilova Valentina P-117, P-335
Das Supriyo P-462
Davis Cara P-104
Dawson Daniel O-79
de Andrade Ferreira
Alexandre
O-16
De Craen Mieke P-140
De Deckker Patrick P-213, P-493
De Jonge Cindy P-233
de Kluijver Anna P-435
de la Rosa José Mª P-040, P-207
De la Rosa Jose
María
P-199
de Lange Gert J. P-483
de Lourdes Moreira
Maria
P-142
643

de Souza Carvalho
Ismar
P-017
Dedysh Svetlana O-24
Deev Andrei O-12, P-354
Dehan Liu P-349
Dellagnezze Bruna O-66
DeLong Edward F. P-184
Delvaux Damien P-326
Dembicki Harry O-40
Deng Xiaoli P-043
Denisevich Peter P-031
Depret Pierre-Andre O-61, P-384
Derenne Sylvie O-25, P-004, P-177, P-245,
P-498, P-507
Derrien Delphine P-498
Dessort Daniel P-007, P-008
Dettenmaier Erik P-153
Dewhurst Richard P-205
di Primio Rolando O-48, O-77, P-089, P-121,
P-307, P-428
Dickens Angela P-508
Dieckmann Volker O-11, O-23, P-361
Ding Yong P-301
Ding Zhongli O-33
Dingsheng Cheng P-337
Dippold Michaela P-009
Disnar Jean-Robert O-30, P-050, P-132, P-133,
P-250, P-491
Dixon Liz P-511
do Santos Madureira
Luiz Augusto
P-147
Dodson John P-167
Doering Sascha O-59
Dogrul Selver Ayca P-035
Dojţinoviš Biljana P-273
Domack Eugene P-469
Domingo Laura O-09
Dong Zhongliang P-316
dos Santos Ciqueira
Celeste Yara
dos Santos Neto
Eugenio Vaz
P-142
P-010
Downey Bryce P-509
Downing John P-435
Dreier Anne P-175
Drenzek Nicholas P-367, P-368, P-448
Dresen Georg P-371
Duclerc Dominique P-007, P-008
Dudarev Oleg O-56, P-246
Dujie Hou P-337
Dungait Jennifer P-028, P-511
Dupont Lydie P-218, P-461
Dupuis Christian P-211
Dutta Suryendu O-06
Dyda Rachael P-500
Dzou Leon O-61, P-384
Dzuba Oksana P-106
Eder Victorya P-322
Eder Vika P-117
Edgcomb Virginia P-425
Edwards Dianne P-069, P-111, P-219, P-282
Edwards Nick O-41
Egasse Céline P-498
Eglinton Timothy O-02, O-45, O-56, O-70, P-
025, P-234, P-236, P-508,
P-509
Eiche Elisabeth P-139
644

Eiserbeck Christiane O-36
Eke Zsuzsanna P-235
El Agrab Abdelfatah O-18
Eley Yvette O-32
Elkelani Mohamed P-200
Elliott Tim O-23
Ellis Geoffrey P-356
Elvert Marcus O-74, P-201, P-418, P-451
Engelen Bert O-13, P-440
Eniola Olubunmi P-484
Erdman Michael O-42
Ershov Sergey P-093
Ertefai Tobias P-167
Escala Marina P-168
Escobar Marcos P-038
Eshetu Zewdu P-417
Evenick Jonathan P-375
Evershed Richard O-31, P-052, P-492, P-499
Fabiańska Monika P-036, P-143, P-144
Fadeeva Svetlana P-119, P-120, P-298
Fahl Kirsten P-495
Falk Heinz O-19
Fallet Ulrike P-197
Fan Ming P-317
Fang Chenchen P-398
Fang Shihu P-096
Fang Wei P-125, P-316
Fang Yunxin P-118
Fanslau Jenna P-509
Farquhar Graham O-51, P-420
Farrimond Paul P-285
Fatela Francisco P-199
Faure Pierre P-055, P-140, P-173, P-232,
P-460
Faust Dominik P-207
Fazeelat Tahira P-297
Fedotov Andrei P-233
Feitosa da Cruz
Georgiana
P-060, P-276
Fekete József P-019, P-235, P-272
Feng Dong P-160
Feng Xiaojuan P-236, P-508
Feng Zihui P-125, P-254
Ferdelman Timothy
G.
O-26
Fierer Noah O-64
Fietz Susanne O-20, O-68, P-148, P-168
Figueiredo Angolini
Célio Fernando
P-010
Filgueiras Renata P-006
Filgueiras Soares
Renata
P-017
Filley Timothy P-502
Fischer David P-482
Fischer Gerd P-157
Fiske Gregory P-509
Flauraud Eric P-343
Foesel Baerbel O-24
Fogel Marilyn P-417
Folgerø Kjetil P-342
Fomichev Anatoliy P-229
Fomin Alexander P-093, P-107, P-108
Fontes Rosane P-091
Fosse Céline P-177, P-245
Francu Eva P-145
645

Francu Juraj P-037, P-266
Frank Richard O-03
Franklin Lapal Celso
Marcelo
P-142
Franzke Daniela P-436
Fraser Helena P-509
French Katherine P-062
Früh-Green Gretchen P-178, P-182
Fry John O-38
Fu Xiaodong P-324
Fukushima Kazuo P-237
Furota Satoshi P-202
Fursenko Elena P-093, P-097, P-146, P-315
Fusetti Luc O-72, P-336
Fustic Milovan P-098
Gaglioti Benjamin P-201
Gál Anita P-503
Galán Luis P-458
Galarraga Federico P-346
Galimov Eric P-021, P-112
Gallego José R. P-038, P-392
Galy Albert P-505, P-506
Galy Valier P-236, P-509
Gao Bo P-355
Gao Li P-489
Gao Xiaokang P-373
Gao Yuqiao P-116
García-Cortés Ángel P-458
Garel Sylvain P-211
Garnier Emmanuel P-460
Gates Ian O-55
Geibert Walter O-20
Gelin François O-72
Geng Ansong P-118, P-319
George Simon P-039, P-185, P-203
Germer Juliane P-204
Germerott Svenja P-357
Gerńl Milan P-145
Ghislain Thierry P-232
Giannesini Sophie P-343
Gibson Robert P-443, P-445
Gieles Rieneke P-469
Gierga Merle O-47, P-406
Gill Fiona P-205
Gilleaudeau G . J. O-59
Gillespie Aimee P-169
Gillies Sharon L. P-509
Gilmour Iain P-134
Giosan Liviu P-508
Glaser Bruno O-46, P-009, P-419
Glaznetsova Yulia P-381
Gleixner Gerd O-33
Glemser Chad P-361
Glombitza Clemens O-38, P-170
Gocke Martina P-177, P-238, P-239, P-511
Gogou Alexandra P-162, P-206
Goldhammer Tobias P-451
Golovko Anatoly P-072, P-269, P-270, P-283,
P-358, P-377
Golovko Julia P-072
Gomes Maria Aquiar
Hélen
P-058
Gomez Elaine P-217
Goncharov Ivan P-099, P-119, P-120, P-274,
P-298
646

Gong Changrui O-61, P-384
Gong Se P-282
Goni Miguel P-514
Gonzalez Villa
Francisco Javier
González-Pérez José
António
González-Vila
Francisco J.
P-230
Gorder Kyle P-153
Gordon Graeme P-310
Gosling William D. P-134
Goutx Madeleine P-441
Graciaa Alain P-341
Grant Russell P-180
P-040, P-199, P-207, P-230
P-040, P-199, P-207
Grass David O-61, P-384
Gratzer Reinhard P-088
Graue Jutta O-13
Grauel Anna-Lena P-220
Gray Neil P-015, P-180
Grba Nenad P-273, P-331
Green Kimberley P-131, P-136
Greenwood Paul O-06, O-53, P-054, P-281,
P-359
Grelowski Cezary P-100
Gribanov Alexsander P-034
Grice Kliti O-36, O-51, O-53, O-57, P-
041, P-054, P-069, P-070,
P-111, P-167, P-192, P-212,
P-219, P-281, P-296, P-297,
P-420
Griess Juliane P-171
Griffin Dean P-310
Griffith David P-025, P-234
Griffiths Thomas A. P-134
Grimes Stephen O-09
Grinko Andrei P-358
Gross Jürgen H. O-19
Grossi Vincent O-44, P-172, P-208
Grotheer Hendrik P-240, P-367, P-368
Guangyou Zhu P-063, P-101
Guerardel Yann P-431
Gulaya Elena P-504
Guo Jiangtao P-474
Gusso Maioli Otávio
Luiz
P-147
Gustafsson Örjan O-56, P-005, P-035, P-246
Guthrie John P-310
Gutierrez Mejia Esaul P-046
Haberle Simon G. P-486
Haeseler Frank P-064
Hafner Albert O-01
Hai Vu Van P-309
Hajdas Irka O-47, P-402, P-406
Hakimi Mohammed
Hail
P-080
Hallmann Christian P-065
Hambach Bastian O-20
Hambach Ulrich P-512
Hammer Ulia P-016
Handley Luke P-209
Haneferd Helen P-299
Harner Ricardo P-346
Harriman Gareth P-311
Harrington Paul P-338
Harris Nicholas P-261
Hart Kris P-247
647

Hart Malcolm O-09
Hartkopf-Fröder
Christoph
P-328
Hartwig Alexander P-121
Hasinger Olivier P-242
Hatcher Patrick G. P-308
Hatté Christine P-498
Hauck Thomas P-129
Hautevelle Yann P-173, P-210, P-288, P-453,
P-454
Hays Lindsay O-57
He Kun P-257
He Xiaosu P-102
He Xunyun P-102
Head Ian P-015, P-180
Heckmann Jean R. P-306
Heike Knicker Heike P-230
Heilmann-Clausen
Claus
P-468
Heim Christine O-58
Hein Sebastian P-138
Heinzelmann Sandra P-407
Heldt Matthias P-366
Heller Christina P-174
Hemza Petr P-266
Henderiks Jorijntje P-208
Hendry Philip O-66
Hernes Peter P-500
Herrle Jens P-455
Herrlich Sascha P-175
Herron Michael P-367, P-368
Hetényi Magdolna P-019, P-503
Higgins Meytal B. O-04
Hill Ronald O-12
Hinrichs Kai-Uwe O-14, O-26, O-60, O-74, P-
020, P-029, P-030, P-056,
P-164, P-183, P-185, P-201,
P-220, P-411, P-418, P-424,
P-437, P-442, P-451
Hippler Dorothee P-371
Hirschler-Réa Agnès O-44
Ho Sze Ling O-20
Hocart Charles O-51, P-420
Hockaday William C. P-466
Hodari Tarek P-103
Höfle Silke P-243
Hofmann Peter P-455
Hofmann Thilo P-181
Holland David P-081
Holler Thomas O-74, P-437
Holman Alex O-57
Holman Alexander P-041
Holmes R. Max P-236, P-509
Holthuijsen Sander P-416
Hopmans Ellen O-15, O-24, P-156, P-221,
P-244, P-433, P-445, P-446,
P-447, P-485, P-510
Hoppert Michael P-174
Hornibrook Edward P-492, P-499
Horsfield Brian O-38, O-48, O-77, P-089, P-
256, P-307, P-371
Hosseini Seyed
Hossein
P-083
Houzay Jean-Pierre P-288
Hovius Niels P-505, P-506
Hrepiš Vladimira P-279
Hsieh Ben P-015
Hu Guang P-116
648

Hu Shouzhi P-126
Hu Wenxuan P-094, P-116
Hua Tian P-369
Huan Yang P-176, P-179
Huang Chia-I P-437
Huang Haiping O-55, P-098, P-370
Huang Shipeng P-259
Huang Yongsong P-417, P-489
Huasen Zeng P-325
Huault Vincent P-210
Hubbard Stephen P-098
Hugelius Gustaf P-502
Huguet Arnaud P-177, P-245
Huguet Carme O-68, P-148, P-168
Hui Tian P-349
Huo Qiuli P-254
Hussain Zainab P-508
Huvaz Özkan O-18
Hvidsten Ina P-141, P-149
Iakovleva Alina P-211
Ibalot Fabienne P-390
Idiz Erdem O-11, P-361
Ikarashi Masayuki P-434
Ikeda Kei P-042
Illing Christian J. P-065
Imachi Hiroyuki O-27, O-28
Imbus Kendra P-130
Inagaki Fumio P-442
Inan E. Esra O-78
Indo Kentaro P-339, P-352
Ineson Philip O-31
Integrated Ocean
Drilling Program
Expedition 317
Shipboard Scientific
Party
Irino Tomohisa P-472
Ishiwatari Ryoshi P-488
Ivanov Dimiter P-476
Ivanova Elena P-302
Iversen Morten P-157
Jackson Robert O-64
P-039, P-203
Jacob Jérémy O-30, P-132, P-133, P-211,
P-250, P-403, P-491, P-498
Jaeschke Andrea P-178, P-432, P-433
Jahnert Ricardo P-167
Janiga Marek P-289
Jankowski Leszek P-289
Janmaat Alida P-509
Jaraula Caroline P-041, P-212
Jargalsaikhan
Namkhainorov
P-377
Jarrett Amber O-07
Jarvie Daniel O-84, P-378
Jean Jiin-Shuh P-139
Jia Guodong P-214
Jiang Aizhu P-312
Jiang Hong O-17
Jiang Lanlan P-301
Jiang Lei P-051
Jianping Chen P-369
Jie Cui P-063
Jin Kankun P-043, P-048, P-251
Jin Su P-063, P-101
Jin Xiaodong P-301
649

Jin Zhijun P-094
Jingjing Li P-179
Jocelyne Marsaioli
Anita
P-010
Johansen Jon Eigill O-37, P-066, P-075
Johnson Thomas P-192
Jones Daniel P-104
Jones David O-03
Jones Martin P-015, P-180
Jovanţiševiš Branimir P-273, P-279, P-331
Juchelka Dieter O-46
Junhua Huang P-179
Justwan Holger P-104
Kabel Karoline P-473
Kaever Alexander O-58
Kagya Meshack P-105
Kah Linda C. O-59
Kalbitz Karsten O-46, P-419
Kallmeyer Jens O-38, P-170, P-428
Kaneko Masanori O-81
Karakas Gökay P-157
Karlsson Emma O-56, P-246
Kárpáti Zoltán P-235
Karpov Gennadii P-107
Kashirtsev Vladimir P-067, P-106, P-107, P-146,
P-270, P-302, P-478
Kasper Sebastian P-408
Kasten Sabine P-240, P-482
Katsouras Georgios P-206
Kaufhold Stephan P-328
Kaur Gurpreet P-443
Kavak Orhan P-130
Kazanenkov Valery P-093
Ke Hu P-463
Keely Brendan O-82, P-018, P-128, P-131,
P-136, P-450
Kelleher Brian P-247, P-387, P-429
Kellermann Matthias
Y.
P-60, O-74
Kelly Amy P-011
Kelly David P-212
Khaleghi Mehdi P-083
Khalil Hanna P-386
Khouri Ahmed O-18
Kildahl-Andersen
Geir
Killough Patrick P-011
Kim Bokyung P-508
O-37, P-066, P-075
Kim Jung-Hyun O-62, O-64, P-248, P-516
Kim Natalya P-093, P-106, P-108
Kirf Mathias P-436
Kitagawa Yuroyuki P-463
Klatt Christian P-444
Klausmeyer Timm P-380
Klugkist Angelika P-150
Knappy Christopher O-82
Knicker Heike P-199, P-207
Kobayashi Madoka P-215
Koc Şukru P-332
Koca Derya P-122
Koch Boris P-183
Kochnev Boris P-302
Köllner Krista E. P-404
Kong Xiangxing P-287
Kononchenko Elena P-123
650

Kontorovich Alexey P-093, P-107, P-108, P-117,
P-280, P-335, P-478
Kontorovich Vladimir P-093
Korovnikov Igor P-322
Kosakowski Paweł P-044
Köster Jürgen O-13, P-181, P-216
Kostiš Aleksandar P-278
Kostic Ivana P-151, P-152
Kostyreva Elena P-107, P-108, P-117
Kotarba Maciej P-286
Kowalski Adam P-044
Kraaij Mariska O-15
Kraemer Charles P-460
Krafft Jean-Michel P-008
Kramarics Áron P-235
Krasnoyarova
Natalya A.
P-124
Kříbek Bohdan P-037
Krinin Vladimir P-120
Krooss Bernhard M. P-265, P-266
Kruge Michael A. P-181, P-217, P-392
Krüger Martin O-76
Krull Evelyn S. P-486
Krupke Andreas P-436
Kuder Tomasz P-153, P-154, P-391
Kuechler Rony R. P-218
Kuhlmann Holger P-464
Kuhn Philipp O-48, O-77
Kuhry Peter P-187, P-502
Kuippers Gina P-249
Kulakov Anna P-387
Kulakov Leonid P-387
Kulp Thomas. R. P-139
Kumar Vasant P-506
Kurschner Wolfram P-200
Kursheva Anna P-068, P-382
Kusch Stephanie P-409
Kuypers Marcel M.M. P-436
Kvenvolden Keith P-109
Ladjavardi Mojgan O-53, P-069, P-219
Lafaurie Christine P-340
Laggoun-Défarge
Fatima
Lajeunesse Patrick P-133
Lallier-Vergès
Elisabeth
P-245, P-271
P-403
Lammers J. Marieke P-410
Lammerts Laurens P-444
Lamoureux-Var
Violaine
O-71
Lamy Frank O-20
Landau Luiz P-142, P-277, P-306
Landolt Mickaël P-129
Lang Susan P-182
Lapointe Philippe P-007
Lappé Michael P-501
Lara Azucena P-392
Lara-Gonzalo
Azucena
P-038
Large David O-54, P-014
Larkin Michael P-387
Larson Peter O-41
Larson Rebekka P-481
Larter Steve O-21, O-55, 0-79, P-015, P-
098, P-370
Lathuillière Bernard P-210
651

Lausmaa Jukka O-58
Lavrieux Marlène O-30, P-250, P-491
Lawson Tracy O-32
Lawton Laura P-310
Laycock Dallin P-370
Lazar Cassandre P-424
Le Milbeau Claude O-30, O-43, P-224, P-250,
P-491
Le Minh Tam P-070
Le Tensorer Jean-
Marie
P-129
Lécuyer Christophe P-172
Ledoan Tuong-Van O-72
Ledoux Grégoire P-133
Ledru Marie-Pierre P-456
Lee Jung-Hyun P-438
Lee Ming-Kuo P-139
Leefmann Tim O-58
Lefort Apolline P-173, P-210
Lehmann Moritz O-52
Lehndorff Eva P-385
Lehne Eric O-77, P-339, P-352
Lehnik-Habrink Petra P-138
Lei Tianzhu P-045
Leiber Katharina P-419
Leider Arne P-220
LeMilbeau Claude P-132, P-133, P-211, P-403
Leng Melanie O-09
Lengger Sabine K. O-15, P-221
Leorri Eduardo P-199
Lepom Peter P-396
Leprovost Céline P-129
Lerm Stephanie P-397
Levaché Denis P-340
Le-Van-Loi Robert P-007, P-008
Lewan Michael P-286, P-330
Leythaeuser Detlev P-327
Li Fu P-325
Li Kaikai P-051
Li Maowen O-17, O-49, P-125
Li Shuifu P-126
Li Yanheng P-043, P-048
Li Yun P-398
Li Zheng P-287
Liang Qianyong P-398
Liangliang Wu P-351
Liao Fengrong P-259
Liao Yuhong P-012, P-013, P-118, P-319
Liao Zewen P-110, P-341
Liebetrau Volker O-75
Lifshits Sara P-372, P-381
Lijing Gu P-063, P-101
Lilley Marvin P-182
Lillis Paul P-304
Lim Katie P-052, P-492, P-499
Lin Yu-Shih O-74, P-030, P-183, P-411,
P-418
Lincoln Sara A. P-184
Linge Tomren
Andreas
P-342
Linzer Hans-Gert P-088
Lipp Julius O-14, O-26, P-020, P-029,
P-039, P-185, P-203, P-411
Lirong Dou P-337
Littke Ralf P-114, P-326, P-327
652

Litvinenko Ivan P-068, P-293, P-382
Liu Dayong P-301
Liu Guangdi P-350
Liu Jinzhong P-318, P-359
Liu Qing P-287
Liu Shaobo P-373
Liu Shiming P-048
Liu Wenhui P-255, P-355
Liu Xiaolei O-14
Liu Zhaoqian P-291
Lloyd Jon P-139
Lockhart Robert S P-054, P-070, P-281
Logemann Jörn O-13, P-227
Lopes dos Santos
Raquel
Lopes Silvia P-395
Lopez Lopez Luis P-046
Lopez-Martinez
Nieves
P-213, P-493
O-09
Lores Iván P-392
Lossons Benoît P-460
Lotter Andre F. O-63
Love Gordon O-08, P-062
Lu Hong P-262, P-359
Lu Jialan P-318
Lu Li P-317
Lu Longfei P-045
Lü Xiuxiang P-301
Lu Yueming P-453, P-454
Ludgate Natalie F. P-134
Luo Pan O-33
Lykousis Vasilios P-206
Ma Dade P-096
Ma Jun P-126
Ma Qisheng P-356
Macdonald Robie P-234
MacFarland Steve P-362
Macklam-Harron
Garrett
P-509
Mácová Daniela P-037
Madigan Michael P-444
Madincea Marlene P-362
Madren Jonathan O-40
Maeda Haruo P-434
Magnier Caroline P-343
Magoon Leslie P-304
Mahdaoui Fatima P-288
Mahlstedt Nicolaj P-256, P-371
Majumder Bidisha P-511
Makou Matthew O-45
Mallick Monalisa O-06
Maly Vladislav P-290
Mangelsdorf Kai O-38, O-80, P-171, P-397,
P-426, P-428
Mankiewicz Paul P-362
Mann Ulrich P-249
Manners Hayley O-09
Manning Phill O-41
Mansuy-Huault
Laurence
P-460
Marcano Norka O-21, O-55
Markovic Slobodan P-419
Marquaire Paul-Marie O-72, P-336, P-360
Marques Flora P-367
Marquez Gonzalo P-038
653

Marsh Steven P-509
Marshall Chris O-54
Martin William P-025
Martínek Karel P-037
Martinez Manuel P-038
Martínez-Garcia
Alfredo
Masiello Caroline A. P-466
Maslen Ercin P-111
Mason Sharon P-423
Masse Guillaume P-191
Masuda Kazuo O-30
Mathew Runcie O-06
Matsuzaki Hiroyuki O-02
Mattioli Emanuela P-208
O-20, P-168
Matyasik Irena P-289, P-374
Maxfield Peter P-492
Mayer Bernhard O-21
Mayr Christoph O-46
Mayumi Daisuke P-434
McAnena Alison P-455
McCarthy Matthew O-52
McClain Tony P-375
McClymont Erin P-484, P-499
McCormack Niall P-310
McElwain Jennifer O-57
McGeough Emma P-205
McHugh Thomas P-153, P-154
McIntyre-Wressnig
Anna
P-425
McKinney Daniel O-78, P-344
McLaughlin Fiona P-234
McNamara Niall O-29
McNichol Ann P-234
Meador Travis B. P-424
Meadows Michael E P-228
Mebarka Aziez P-320
Medrano Morales
Luis Manuel
P-046
Mehay Sabine P-425
Meinicke Peter O-58
Melcher Frank P-300
Melendez Ines O-53
Melenevskiy Vasiliy P-085, P-093, P-108, P-117,
P-290, P-302
Mendez-Millan
Mercedes
P-498
Mendonça Filho João P-330
Menezes Taissa P-330
Mennito Anthony O-05
Menor-Salvan Cesar P-071, P-383
Meredith Will O-54, P-014, P-070, P-311
Meredity William P-399
Mersmann Jan P-345
Metcalfe Ian P-069, P-219
Mets Anchelique P-244
Meyerdierks Anke P-437
Meyers Philip P-187, P-188, P-456, P-457
Mi Jingkui P-257
Miceli Romero
Andrea
P-376
Michaelis Walter O-65, O-76, P-175
Michels Raymond P-140, P-173, P-232, P-288,
P-360, P-453, P-454, P-460
Miciš Vesna P-181
Middelburg Jack P-435
654

Middelburg Jack J. P-410, P-416
Midtaune Håkon P-075
Milkov Alexei O-61, P-258, P-384
Min Raisa P-358
Minor Elizabeth P-412
Mitrovic Jelena P-151
Miyagawa Yoshihiro P-434
Miyairi Yosuke O-02
Mogollón Leonardo P-006
Mohtadi Mahyar P-198, P-413
Mokeev Maxim P-034
Moldowan J. Michael O-73, P-031, P-059
Moldowan John P-291
Moldowan Michael O-12
Moldowan Shaun O-73
Mollenhauer Gesine P-157, P-198, P-240, P-243,
P-409, P-411, P-461, P-464,
P-479, P-495, P-514
Monaghan Paul S. P-052
Montargès-Pelletier
Emmanuelle
P-460
Montel François P-336
Monteys Xavier P-429
Montluçon Daniel O-45, P-236, P-508, P-509
Morais Erica P-292
Moraleda Núria P-148
Moran Brian P-247
Moreno Laura P-458
Morgan Hugh O-82
Morgunova Inna P-293
Moriceau Brivaëla P-441
Morono Yuki P-442
Moros Matthias P-473
Mörth Magnus P-187
Mortillaro Jean-
Michel
P-516
Moskvin Valeriy P-117
Mountain Bruce P-443
Mozhayskaya Marina P-072
Mrkiš Sanja P-278
Muehlenbachs Karlis O-83
Mueller-Niggemann
Cornelia
Muhammad Usman P-386
Muito-Kabuyah
Rachel
O-80, P-135, P-385, P-426
P-497
Mulitza Stefan O-34
Müntinga Fenja P-216
Murillo Wendy P-294
Murphy Brian P-387
Murray Andrew O-79
Muscio Gary P-295
Nabbefeld Birgit O-57
Nadeem Shahid P-296
Nadezhkin Dmitry P-321
Naeher Sebastian P-427
Nagovitsin Konstantin P-478
Nagovitsyn
Konstantin
P-302
Naihuang Jiang P-063
Nakamura Hideto P-042, P-459
Naraoka Hiroshi O-81
Nasir Shagufta P-297
Nederlof Peter O-18, P-200
Nehls Irene P-138
Nemchenko Tatyana P-112, P-291
655

Nemchenko-
Rovenskaya Alla
P-112
Nestler Andreas P-512
Nguyen Tu Thanh
Thuy
P-498
Nguyen Van Phuc P-360
Ni Chunhua P-074
Ni Yunyan P-259, P-260
Nichols Carol O-66
Nickel Julia P-428
Niedermeyer Eva M. P-401, P-413
Nikoliš Goran P-388
Nikoliš Ruņica P-151, P-152, P-388
Nishi Hiroshi P-189
Noah Mareike P-389
Nobbe Gijs P-404
Nomaki Hidetaka P-442
Northrop Scott P-362
Noyau Alain P-345
Nyilas Tünde P-019, P-503
Nytoft Hans Peter O-37, P-047, P-066, P-075,
P-278
O' Reilly Shane P-429
Oberhänsli Hedi P-465
Oblasov Nikolay P-119, P-120, P-274, P-298
Ocampo-Torres
Ruben
P-430
Ogawa Nanako O-27, O-28, P-405, P-442
Ohkouchi Nao O-02, O-27, O-28, P-405, P-
442
Ohm Sverre Ekrene P-299
Okano Kazuki P-189
O'Kiely Padraig P-205
Oldenburg Thomas O-55, P-015, P-098
Olivares Carolina P-294
Oliveira Dulce P-166
Oliveira Valéria O-66
Olsen Kevin P-217
Ono Makiko P-463
Opazo Luis Felipe P-212
Orbay Naci P-196
Orheim Alv O-54
Ortiz José E. P-458
Osborne Kate P-209
Osborne Mark O-50
Ostertag-Henning
Christian
Otten Glenn P-362
Overmann Joerg O-24
Ovsyannikova
Varvara
P-016, P-300, P-357
P-146
Palyanov Yury P-290
Pan Changchun P-301
Pan Jianguo P-323
Pan Yinhua P-012, P-319
Pancost Richard O-09, O-39, P-052, P-172,
P-205, P-443, P-457, P-492,
P-499
Panda S K P-086
Pang Zhonghe O-33
Parfenova Tatyana P-076, P-280, P-302, P-322
Parkes R. John O-38
Parkin Geoff P-500
Parlanti Edith P-390
Pätzold Jürgen P-464
Pearson Ann O-04
Peck Vicky P-168
656

Peckmann Jörn P-160
Pedentchouk Nikolai O-32, P-419
Pedersen Per P-370
Pedersen Rolf B. P-178
Pendentchuk Nikolai P-500
Peng Ping'an O-33, P-262, P-359
Penteado Henrique P-091
Pepper Andrew P-023, P-310
Pereira Ricardo P-006, P-017
Pereira Ryan P-500
Peresypkin Valerij P-439
Pérez Adriana P-303, P-346
Perez Ortiz Jose
Antonio
Pérez-González
Alfredo
P-046
P-458
Peskov Kirill O-32
Peters Henning O-11, P-361
Peters Kenneth P-304
Peterse Francien O-64, P-244
Petit Morgan O-69
Petrova Vera P-068, P-268, P-293, P-382
Peucker-Ehrenbrink
Bernhard
P-236, P-509
Pevneva Galina P-072, P-269, P-270, P-283,
P-377
Philp Paul P-103, P-153, P-154, P-261,
P-376, P-391
Pickering Matthew P-131, P-136
Piepjohn Karsten P-090
Pierrat-Bonnefois
Geneviève
O-43
Pierre Faure P-386
Pietro Xavier O-60
Pilgrim Tamara P-111
Pitcher Angela P-221, P-446
Plancq Julien P-208
Podlaha Olaf G. O-11, P-361
Pohlman John W. P-201, P-451
Poirier Yannick P-288, P-340
Polya David P-139
Postnikov Ananoliy P-280
Pötz Stefanie P-347
Povey Malcolm P-002
Prange Matthias O-34, P-464
Preis Yulia P-504
Price Roy P-164, P-437
Prinzhofer Alain P-264, P-343
Pross Joerg P-455
Protsko Olga P-049
Pruss Sara P-169
Punanova Svetlana P-305
Purenovic Milovan P-151, P-152
Qi Wen P-323
Qian Kuangnan O-05
Qian Yixiong P-301
Qin Jianzhong O-17, P-301, P-324
Qin Shenjun P-043, P-251
Qinghua Fan P-325
Qiuli Huo P-325
Quan Shi P-337
Quesnel Florence P-211
Quijada Melesio P-055, P-431
Rabus Ralf P-513
Radler Aquino Neto
Francisco
P-147
657

Radovic Miljana P-152
Ramanathan AL P-394
Ramos L. Scott P-304
Rampen Sebastiaan O-62
Rangel Mario D. P-001
Ranjan Rajesh P-394
Rao Mulagalapalli O-06
Ratulowski John P-339
Ravelo Christina O-52
Rawlins Andrew O-31
Reeves Eoghan P-030
Rehmer Heather P-362
Reichart Gert-Jan O-29, O-63, P-163, P-200,
P-221, P-410, P-414, P-481
Reicherter Klaus P-470
Reisberg Laurie P-288
Reischenbacher
Doris
P-088
Reitner Joachim O-59, P-174, P-204
Rethemeyer Janet P-243, P-455, P-501
Reyes Julito O-49, P-125
Reysenbach Anna-
Louise
P-445
Riboulleau Armelle P-055, P-271, P-431
Ricketts R. Douglas P-485
Riedel Michael P-451
Riefer Patrick P-380
Riegel Walter O-59
Rijpstra Irene O-24, P-244
Rincones Ysmarline P-346, P-393
Rizoulis Athanasios P-139
Roalkvam Irene P-365
Robert François O-25
Roberts Harry H. P-160
Roberts Mark P-169
Roberts Zoë P-228
Robinson Clare P-497
Roche Emile P-211
Rodrigues Enmanuel P-307
Rodríguez Carmen P-346, P-393
Rohrssen Megan O-08
Rojík Petr P-037
Romero-Sarmiento
Maria-Fernanda
Rommerskirchen
Florian
P-271
P-461
Rondon Noélia P-330
Rontani Jean-
François
O-69
Roobroeck Dries P-243
Rosell Raphael O-18
Rosell-Melé Antoni O-20, O-68, P-148, P-168
Rossi Oliveira
Cristiane
Rost Björn P-409
Roth Philipp P-385
Rouchy Jean-Marie P-172
P-058, P-147
Routh Joyanto P-394, P-462, P-502
Rovenskaya-
Nemchenko Alla
P-291
Rowland Steven O-03, P-191, P-348
Rueda Gemma P-168
Ruiz-Bermejo Marta P-071
Ruiz-Zapata Blanca P-458
Rullkötter Jürgen O-13, P-150, P-216, P-225,
P-227, P-396, P-440
Rumpel Cornelia P-040
658

Rush Darci P-432, P-433
Sachse Victoria P-326, P-327
Sachsenhofer
Reinhard F.
P-088
Saenz James O-70
Saesaengseerung
Neungrutai
P-018
Safronov Pavel P-093
Sagachenko Tatyana P-053, P-284, P-358
Said-Ahmad Ward O-10
Saidi Moncef P-078
Saini-Eidukat
Bernhardt
P-300
Sajgó Csanád P-019, P-235, P-272, P-503
Ńajnoviš Aleksandra P-047, P-273, P-278, P-279,
P-331
Sakata Susumu P-434
Salles Ferreira Silva
Raphael
P-017
Salles Raphael P-006
Salmon Elodie P-308
Samoylenko Vadim P-119, P-120, P-274, P-298
Samuel Olukayode O-37
Sanchéz-García
Laura
Sanchez-Vidal Anna P-162
Santos da Cunha
Tatiana
O-56, P-246
P-142
Santos Neto Eugênio O-16, O-66, P-058, P-264,
P-330
Sari Ali P-122, P-332
Sass Henrik P-440
Satti S A P-086
Saveliev Vadim P-377
Savinykh Yury P-309
Sawada Ken P-042, P-189, P-202, P-215,
P-459, P-463
Sawal George P-396
Scarlett Alan O-03
Schaeffer Andreas P-380
Schaeffer Philippe O-44, P-224
Scheeder Georg P-047
Schefuß Enno O-34, O-62, P-218, P-401,
P-461, P-464, P-479, P-501
Scherf Ann-Kathrin O-67
Schimmelmann Arndt O-53, P-041, P-281
Schipper Konstanze P-495
Schlömer Stefan P-265
Schloter Michael O-80, P-426
Schmale Oliver P-161
Schmidt Burkhardt P-380
Schmidt David P-023
Schmidt Frauke P-465
Schmidt Michael W.I. O-47, P-466, P-486
Schmidt Torsten P-003
Schneider Beate P-389
Schneider Bernd Uwe P-389
Schneider Maximilian
P.W.
P-466
Schnyder Johann P-211
Schoell Martin P-467
Scholz-Böttcher
Barbara
Schoon Petra P-435, P-468
P-150, P-227, P-396, P-440
Schouten Stefan O-15, O-62, O-64, P-156, P-
158, P-190, P-192, P-193,
P-197, P-213, P-221, P-244,
P-407, P-408, P-416, P-432,
P-433, P-435, P-444, P-445,
P-446, P-447, P-468, P-469,
P-485, P-493, P-501, P-510
659

Schröder Jan P-020, P-029
Schubert Carsten J. O-52, P-159, P-404, P-410,
P-427, P-436
Schubotz Florence P-437
Schultz Bo Pagh P-468
Schulz Hans-Martin P-088
Schulz Linda O-42
Schütrumpf Kathrin P-207
Schwark Lorenz O-80, P-022, P-135, P-190,
P-385, P-426
Schwarzbauer Jan P-114, P-249, P-326, P-327,
P-328, P-380, P-470
Scott Jennifer P-310
Searcy Tomieka O-61, P-384
Sébilo Mathieu P-507
Seewald Jeffrey P-368
Ségalini Gérard P-340
Seibt Andrea P-397
Seifert Richard O-65, O-76, P-175
Seki Osamu P-215
Sellers William O-41
Sémaoune Priscillia P-507
Semiletov Igor O-56, P-035, P-246
Sempere Richard O-69
Sepulveda Julio P-471
Serebrennikova Olga P-099, P-124, P-275, P-504
Sessions Alex O-12, P-169, P-354, P-401,
P-413
Sevastyanov
Vyacheslav
Severiano Ribeiro
Hélio
P-021, P-112
P-276
Shaari Hasrizal P-472
Shaobo Liu P-369
Sheesley Rebecca P-005
Shemin Georgiy P-093
Shen Anjiang P-102
Shen Baojian P-324
Sherry Angela P-180
Sherwood Owen O-52
Shi Chunhua P-116
Shi Quan P-013
Shi Weijun O-17
Shiganova Olga P-275
Shimamoto Akifumi P-449
Shin Kyung-Hoon P-438
Shipboard Scientific
Party IODP
Expedition 317
P-185
Shuai Yanhua O-49, P-262
Shucheng Xie P-176, P-179
Shuichang Zhang P-063, P-101, P-369
Shulga Natalia P-439
Sierra Carlos P-392
Sierra Garcia Isabel
Natália
O-66
Sieverding Marieke P-440
Sifeddine Abdelfettah P-456
Silliman Alan P-338
Silva Raphael S. F. P-001
Silva Thaís P-395
Simões Filho
Francisco Fernando
Lamego
P-142
Simon Laurent P-208
Simoneit Bernd R.T. P-071
Simpson André P-247
Simpson Jeffrey O-14
660

Sinninghe Damsté
Jaap
Sjövall Peter O-58
Skręt Urszula P-143
Skrzypek Grzegorz P-167
Slatt Roger P-368
Slivko Irina P-079
Słoczyński Tomasz P-374
Sluijs Appy P-468
Slusarczyk Jaroslaw P-217
Smeenk Zwier P-200
Smith Andrew P-423
Smith Ben P-348
Smith Jo P-505
O-15, O-24, O-29, O-62, O-
63, O-64, O-75, P-156, P-
158, P-163, P-192, P-197,
P-200, P-221, P-233, P-244,
P-248, P-407, P-408, P-410,
P-414, P-416, P-432, P-433,
P-435, P-444, P-445, P-446,
P-447, P-468, P-469, P-473,
P-481, P-485, P-510, P-516
Smittenberg Rienk O-47, P-159, P-402, P-406,
P-427
Smoleva Irina P-115
Smołka-Danielowska
Danuta
P-144
Snape Colin O-54, P-014, P-311, P-399
Snape Ian P-191
Soares Antonio M. P-199
Soares de Souza
Eliane
P-276
Sobolev Pyotr P-090, P-478
Sobrinho Rodrigo P-516
Sokol Alexander P-290
Sollich Miriam P-164
Song Yan P-373
Song Zhiguang P-329, P-474
Sonoda Kazuhiko P-415
Southon John O-02
Souza Igor P-330
Souza Maria Cristina P-230
Spadano
Albuquerque Ana
Luiza
Spangenberg Jorge
E.
P-456
Sparkes Robert P-506
Spencer Robert P-500
Spencer Ron P-370
Spigolon André P-330
Spiro Baruch O-54
Springer Marcia P-277
Stadnitskaia Alina O-75, P-233
Stankiewicz Artur O-18
Stasiuk Lavern P-361
Stavrakakis Spyros P-162
O-01, O-43, P-242, P-475
Steen Ida H. P-178, P-365
Stefanova Maya P-476
Stein Rüdigel P-495
Steinmann Philipp P-510
Stiehl Thorsten P-396
Stockhausen Martin P-022
Stockhecke Mona P-148
Stoddart Daniel P-285, P-307, P-428
Stojanoviš Ksenija P-047, P-273, P-278, P-279,
P-331
St-Onge Guillaume P-133
Storme Jean-Yves P-211
Strauss Harald P-065
661

Strelnikova Eugenia P-099
Stuart-Williams Hilary O-51, P-420
Suga Hisami O-02, O-28
Sukhoruchko
Valentina
P-478
Sulistyo Gunardi P-023
Sullivan Michael O-61, P-384
Summons Roger O-06, O-14, O-57, O-70, P-
062, P-065, P-069, P-169,
P-184, P-219, P-425, P-437,
P-471
Sun Dongyan P-487
Sun Yongge P-312, P-399
Sun Yuzhuang P-048, P-251
Suroy Maxime P-441
Sutton Paul O-09, P-348
Svarovskaya Ludmila P-146
Svensson Elisabeth P-416
Swain Eleanor P-024
Sykes Richard O-38, P-313, P-314
Sýkorová Ivana P-037
Sylva Sean P-368
Szpak Michal P-429
Tahira Fazeelat P-296
Takahashi Koji P-237
Takahashi Masamichi P-042
Takahashi Masashiro P-415
Takano Yoshinori O-27, O-28, P-442
Takashima Reishi P-189, P-459
Talbot Helen O-22, O-29, O-39, P-209, P-
231,P-248, P-443, P-455
Tan Jingqiang P-371
Tan Kunjun P-323
Tan Wenbing P-487
Tanaka Yuichiro P-449
Tang Yongchun O-12, O-72, O-85, P-354, P-
356
Tang Yuegang P-251
Taqi Hussain P-364
Tarozo Rafael P-489
Tavagna Maria Luisa P-025
Taviani Marco P-174
Taylor Kyle O-09
Taylor Paul P-082
Taylor Samantha P-370
Tekin Halil P-130
Templier Joëlle P-507
Terwilliger Valery P-403, P-417
Teske Andreas P-424
Texier Pierre-Jean P-129
Thang Nguyen Manh O-60
Thiel Volker O-58, O-59, P-161, P-204
Thießen Olaf O-42
Thomas David P-191
Thompson Katherine O-53
Thompson Lonnie O-45
Thorseth Ingunn H. P-178
Tian Yankuan P-110
Tietema Albert P-423
Tilley Barbara O-83
Tilston Emma P-014
Timoshina Irina P-280, P-315, P-478
Tingate Peter P-282
Torres Trinidad P-458
Tosca Nicholas P-062
Trautwein Kathleen P-513
662

Trichet Jean P-050
Trinajstic Kate O-53
Trinidad Verdejo
Trinidad
P-230
Tripathi Suryakant O-06
Tulipani Svenja P-281
Turcq Bruno P-456
Turowski Jens P-505
Tuthorn Mario O-46
Twitchett Richard O-09, O-57, P-212
Uguna Clement O-54, P-311
Uliana Eleonora O-62, P-479
Urbat Isabel P-480
Val Klump J P-394
Valenza John P-367, P-368
Valyaeva Olga P-049
van Bergen Pim O-23
van den Boorn
Sander
O-23
van der Heide Tjisse P-416
van der Meer Jaap O-64
van der Meer Marcel P-158, P-407, P-408, P-444,
P-445
van der Veer Henk
W.
P-416
van Dongen Bart O-41, O-56, P-035, P-139,
P-497
van Graas Ger P-371
van Soelen Els E. P-481
van Winden Julia O-29
Varden Christopher P-035
Vasconcellos Suzan O-66
Vasiliev Alexander P-233
Vaular Espen N. P-365
Vaultier Frédéric O-69
Vaz dos Santos Neto
Eugênio
P-060
Vecoli Marco P-271
Vegas Juana P-458
Verrecchia Eric P. P-242
Verschuren Dirk P-163
Versteegh Gerard P-056, P-157, P-220, P-271,
P-479, P-482, P-483
Vetter Alexandra P-397
Vicente Poley Guzzo
Jarbas
Vieth-Hillebrand
Andrea
O-16
O-38, O-67, P-165, P-347,
P-389, P-397
Villanueva Laura P-156, P-407, P-446
Vinogradova Tatyana P-305
Vitzthum von
Eckstadt Christiane
P-212
Volk Herbert O-66, P-075, P-081, P-282
Volkman John K. O-69
Volkov Vladimir P-120, P-274
von Blanckenburg
Friedhelm
P-016
Vonk Jorien O-56, P-005, P-236, P-246,
P-508
Voronetskaya
Natalya
P-270, P-283
Voss Britta P-236, P-509
Vu Thi Anh Tiem O-38
Vukoviš Nikola P-279
Wacker Lukas O-47, P-402, P-406
Wagner Dirk P-171
Wagner Thomas O-39, P-209, P-248, P-455,
P-484, P-500
Wakeham Stuart O-70, P-433
663

Wakeham Stuart G. O-69
Walters Clifford O-05, P-362
Wandrey Maren O-67
Wang Chunjiang O-35
Wang Guojian P-317
Wang Hongjun P-318
Wang Huitong P-026, P-027
Wang Jie P-045
Wang Jinji P-301
Wang Li P-474
Wang Peng P-323
Wang Ru P-287
Wang Shibo P-254
Wang Shuzhi P-125
Wang Sibo P-329
Wang Xue P-125, P-254, P-316
Wang Xulong P-094
Wang Yunpeng P-318
Ward David P-444
Waterbury John O-70
Watling John P-111
Wefer Gerold O-34
Wegener Gunter O-26, O-60, O-74, P-437
Wehrli Bernhard P-404
Wei Caiyun P-027
Wei Zhibin O-05, O-12, P-362
Weijers Johan O-24, O-39, O-64, P-163, P-
510
Weinberg Ingo O-65
Weng Na P-026
Wenger Lloyd P-104
Weniger Philipp P-265, P-266
Werne Josef P-192, P-412, P-447, P-485
Werner Roland O-46
West Charles O-03
Wiedemeier Daniel B. P-486
Wiesenberg Guido P-009, P-238, P-239, P-511,
P-512
Wiesenberg Guido
L.B.
P-177
Wilkes Heinz P-089, P-165, P-196, P-284,
P-347, P-389, P-465, P-513
Wilkins Daniel P-213, P-493
Williams Jonathan P-028
Williford Kenneth O-57, P-281
Willmott Veronica O-62, P-469
Winterfeld Maria P-514
Witt Matthias P-183
Wittkopp Frederike P-470
Wogelius Roy O-41
Wolfgramm Markus P-397
Wolkenstein Klaus O-19
Woltering Martijn P-447, P-485
Wong Jenny O-49
Wood Jason P-444
Wooller Matthew J. P-201
Wooton Emily P-471
Wörmer Lars P-020, P-029
Wrede Christoph P-174
Wu Chunpingq O-05
Wu Liangliang P-118
Wu Xiaoqi P-259
Wu Ying P-226, P-236, P-515
Wuchter Cornelia P-448
Würdemann Hilke P-397
664

Xi Binbin O-17
Xia Daniel O-85
Xiang Lei P-051
Xianming Xiao P-349
Xiao Qilin P-261, P-312
Xiaochang Zhang P-325
Xie Sitan O-26
Xie Xiaomin P-116
Xiong Xianghua P-102
Xiong Yongqiang P-398
Xu Jin O-17
Xu Li P-234, P-509
Xu Xingyou P-287
Xu Yang P-399
Xu Yunping P-487
Yalcin M.Namık P-196
Yamaguchi Yasuhiko O-28
Yamamoto
Masanobu
P-449, P-472
Yamamoto Shuichi P-415, P-488
Yamazaki Takahiro O-02
Yang Chupeng P-110, P-312
Yang Weiwei P-350
Yang Y P-086
Yangmin Qin P-179
Yanovskaya Svetlana P-284
Yans Johan P-211
Yao Genshun P-102
Yao Peng P-450
Yao Suping P-094
Yavuz Pehlivanli
Berna
P-332
Ye Jiaren P-126
Yershov Sergei P-108
Yin Hongzhen P-450
Yin Qin P-329, P-474
Yokoyama Yusuke O-02, O-28
Yoshimura Toshihiro P-039, P-185, P-203
Yoshinaga Marcos
Yukio
Yoshiyama Yasuko P-237
Yu Hao P-515
Yu Shuang P-301
Yu Wang P-101
Yu Zhigang P-450
Yuhong Liao P-351
Yunxin Fang P-351
Zacharia Jose P-339
Zahn Rainer P-408
Zamiraylova Albina P-117
Zanin Yuriy P-117
Zebühr Yngve P-187
Zech Michael O-46, P-419
Zech Roland P-489
Zelenková Kateřina P-145
Zell Claudia P-516
Zeller Bernd P-498
Zemke Kornelia O-67
Zeng Huasen P-316
Zhang Dongmei P-126
Zhang Haizu P-110
Zhang Jie P-214
Zhang Jin P-135
Zhang Jinchuan P-371
O-74, P-164, P-418, P-424,
P-451
665

Zhang Jing P-515
Zhang Jingru P-398
Zhang Linye P-287
Zhang Shouchun P-287
Zhang Shuichang O-49, P-026, P-027, P-096,
P-257, P-262
Zhang Tongwei P-356
Zhang Xiaochang P-316
Zhang Xiaoyu P-399
Zhang Yongshu P-096
Zhang Zhirong O-17
Zhang Zhongning P-355
Zhao Changyi P-318
Zhao Cunliang P-048
Zhao Jing P-341
Zhao Meixun P-450
Zhao Mengjun P-096
Zheng Zhuo O-33
Zhigao Ren P-325
Zhou Youping O-51, P-420
Zhu Chun O-39, P-411
Zhu Maoyan O-35
Zhu Rifang P-287
Zhu Rong P-056
Zhu Xunyong P-319
Zhu ZhuoYi P-515
Zhuang Guangchao P-030
Zigah Prosper P-412
Zink Klaus-Gerhard O-38, P-313, P-314
Zinniker David P-031, P-291
Zipper Sam P-508
Ņivotiš Dragana P-047, P-279
Zocatelli Renata O-30, P-250, P-491
Zonneveld Karin P-482, P-483
Zou Caineng P-260
Zou Fenglou P-339, P-352
Zueva Iraida P-381
Zumberge John P-130, P-304
666

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