CSI2013_Program_and_Abstract_Book

XXXVIII CSI 2013 

Table of Content 

TABLE OF CONTENT 

Table of Content ................................................................................................................. 1 

Welcome! .............................................................................................................................. 2 

Organising and Scientific Committee ...................................................................... 3 

International Advisory Board ....................................................................................... 4 

Continuation Committee ................................................................................................ 4 

General Information ......................................................................................................... 5 

Social Programme ............................................................................................................. 8 

Scientific Programme ................................................................................................... 10 

Liability ................................................................................................................................ 10 

Sponsors and Exhibitors .............................................................................................. 11 

Correspondence after the conference ................................................................. 12 

Schedule of Events ......................................................................................................... 13 

Daily Programme ............................................................................................................ 15 

Poster Presentations ..................................................................................................... 25 

Plenary Lecture Abstracts .......................................................................................... 30 

Lecture Abstracts ........................................................................................................... 67 

Address list ...................................................................................................................... 241 

-1 -


Welcome Letter 

WELCOME! 

On behalf of the Norwegian Chemical Society, University of Tromsø and the Organising 

Committee it is an honour and pleasure to welcome you to Tromsø and the Colloquium 

Spectroscopicum Internationale XXXVIII in Tromsø, Norway, June 17 – 20, 2013. This 

conference provides both an international and a regional forum by which researchers and 

users have the opportunity to share their knowledge and exchange ideas. 

We know that the natural beauty of the area will captivate you, but we also hope that the 

conference excursions, social events and farewell dinner may complement the scientific 

endeavours. 

Yngvar Thomassen Jon Øyvind Odland Walter Lund 

-2 -


Committees 

ORGANISING AND SCIENTIFIC COMMITTEE 

ORGANISERS 

The Colloquium Spectroscopicum Internationale XXXVIII is organised by the Norwegian 

Chemical Society and the University of Tromso and in collaboration with International Union 

of Pure and Applied Chemistry. 

YNGVAR THOMASSEN 

(Chairman) 

National Institute of Occupational Health and 

Norwegian University of Life Sciences, Ås, Norway 

WALTER LUND 

(Vice-Chairman) 

University of Oslo, Norway 

ELIN GJENGEDAL 

Norwegian University of Life Sciences Ås, Norway 

IVAR MARTINSEN 

GE Healthcare, Oslo, Norway 

ARNE ÅSHEIM 

(Exhibition Coordinator) 

Molab AS, avd. Porsgrunn, Norway 

SVERRE OMANG 

(Treasurer) 

Oslo, Norway 

ODDVAR RØYSETH 

NIVA, Norwegian Institute of Water Research, Oslo, Norway 

GEORG BECHER 

Norwegian Institute of Public Health, Oslo 

BALÁZS BERLINGER 

(Secretary) 

National Institute of Occupational Health, Oslo 

JON ØYVIND ODLAND 

University of Tromsø 

ANNE REGINE LAGER 

University Hospital, Tromso, Norway 

-3 -


Committees 

INTERNATIONAL ADVISORY BOARD 

Freddy Adams 

Michael Bolshov 

Maria Luisa de Carvalho 

Albert Gilmutdinov 

Detlef Günther 

Klaus Heumann 

Gary Hieftje 

Alexander A. Kamnev 

Ryszard Lobinski 

Robert McCrindle 

Alfredo Sanz Medel 

János Mink 

Harpal Minhas 

Lars-Otto Reiersen 

Bernhard Welz 

Gyula Záray 

Belgium 

Russia 

Portugal 

Russia 

Switzerland 

Germany 

USA 

Russia 

France 

South-Africa 

Spain 

Hungary 

UK 

Norway 

Brazil 

Hungary 

CONTINUATION COMMITTEE 

Bernhard Welz 

Marco Aurélio Zezzi Arruda 

Yngvar Thomassen 

Balázs Berlinger 

Maria Luisa de Carvalho 

Joaquim dos Santos 

Department of Chemistry, UFSC, Brazil 

Institute of Chemistry, UNICAMP, Brazil 

National Institute of Occupational Health, Norway 

National Institute of Occupational Health, Norway 

Atomic Physics Center, University of Lisbon, Portugal 

Department of Physics, University of Coimbra, Portugal 

-4 -


General Information 

GENERAL INFORMATION 

Conference Desk 

Participants are requested to register as soon as possible upon arrival, preferably at Radisson 

Blu Hotel. 

The conference desk will operate as follows: 

Sunday, June 16 

16:00 - 20:00 Lobby of Radisson Blu Hotel 

Monday, June 17 

07:00 - 08:30 Lobby of Radisson Blu Hotel 

Monday, June 17 

13:00 - 18:00 Faculty of Health Sciences, First floor HE-building 

Tuesday, June 18 


Wednesday, June 19 


Thursday, June 20 


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Conference Venue 

All oral sessions will be held in the various auditoriums of University of Tromsø: 

The morning plenary sessions will be held in Auditorium 1, Teorifagbygget, House 1. 

The afternoon sessions will be held in the Auditoriums at the Faculty of Health Sciences, 

First floor HE-Building, Lysgården. 

"Lysgården" 

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Bus transportation from Tromsø City to University Campus 

Conference buses will leave from outside the main entrance of Radisson Blu Hotel every 

morning from Monday, June 17, including Thursday, June 20, at 08:00 and 08:30. 

Please consult the conference program for the bus return schedule. 

The public bus connection between the centre of the city and the university campus is quite 

good. Bus no. 20/21 leaves from Fr. Langes gate (F1) in the centre of the city, and from the 

university just below building 23 on the campus map. This trip takes approximately 10 minutes. 

The bus leaves every 15 mins from the centre of the city on weekdays. You can also take bus no. 

34 – but this route takes you on a longer journey round the southern parts of the island (nice, if 

you are not in a hurry). 

-7 -


Social Programme 

SOCIAL PROGRAMME 

Monday, June 17, 19:00-24:00, the CSI-Club 

Sponsored by Agilents Technologies and Matriks AS 

and 

Tuesday, June 18, 19:00-24:00, the CSI-Club 

The Ølhallen pub in Tromsø opened in1928 in the cellar of Macks Bryggeri, the most northerly 

brewery in the world. Here, in a world of what appears to be eternal candle-lit night, perched on 

wooden stools, every Tom, Dick and Harry in Tromsø takes his beer.This is no cool, trendy bar – 

Ølhallen is an original, in a class of its own. 

As a CSI-participant you go to Ølhallen to drink beer, Mack beer. Mack’s entire selection is 

available, on draught, in bottles, or both. Regular Gullmack Pilsner, the heavier Håkon beer, the 

dark, malty Bayer beer and all the new kinds of beer are offered, but Ølhallen’s regulars swear by 

Blanding: two parts dark Bayer and one part light Pilsner. 

Each CSI-participant is granted minimum two 0.5 L drafts free of charge! Cheaper beer is not 

available in town! 

A selection of Peppes famous pizzas will also be served free of charge. 

Ølhallen is at the southern end of Tromsø’s main street, Storgata 4, and is easy to find. 

-8 -


Social Programme 

Wednesday, June 19, 19:45: Conference Dinner at the Fram Centre 

Sponsors: Agilents Technologies and Matriks AS 

After an introduction to the scientific activities at the FRAM CENTRE a seafood buffet dinner will be 

served. Non-alcoholic and alcoholic beverages are included. 

NOK 500 (not included in the registration fee) 

The Fram Centre is based in Tromsø, and consists of about 500 scientists from 20 institutions 

involved in interdisciplinary research in the fields of natural science, technology and social 

sciences. FRAM contributes to maintaining Norway’s prominent status in the management of 

environment and natural resources in the North. 

-9 -


Scientific Programme 

SCIENTIFIC PROGRAMME 

Oral Presentations 

Invited plenary lectures and submitted oral contributions will be 30 and 20 minutes in length, 

respectively (including discussion). 

Video projectors and computers will be provided in all lecture rooms. 

Posters 

The posters should be mounted Monday June 17, in the poster area located at the Faculty of 

Health Sciences, First floor HE-Building, Lysgården. Materials for poster mounting are available 

either from the Conference Desk or in the poster mounting area. 

All posters will be exhibited throughout the whole conference. 

Language 

The working language of the conference is English. 

LIABILITY 

The Organising Committee declines any responsibility whatsoever for injuries or damages to 

persons or their property during the Conference. 

-10 -


Sponsors and Exhibitors 

SPONSORS AND EXHIBITORS 

The exhibition of scientific instrumentation, literature and consumables is located next to the 

auditoriums of Faculty of Health Sciences, First floor HE-Building, Lysgården. 

The following companies have registered for display and demonstration: 

AGILENT 

ANALYTIK JENA 

BRUKER 

MILESTONE SRL 

SHIMADZU 

THERMO SCIENTIFIC 

KAISER OPTICAL SYSTEMS 

PERKIN ELMER 

PANALYTICAL 

CPI INTERNATIONAL 

GAMMADATA 

MAGRITEK GMBH 

POSTNOVA 

-11 -

CORRESPONDENCE AFTER THE CONFERENCE 

-12 -


Schedule of Events 

SCHEDULE OF EVENTS 

June 16-20, 2013 

Time 

Sunday, 

June 16 Monday, June 17 Tuesday, June 18 

09:00 

Opening Ceremony 

09:15 

Plenary Lecture 

Aud. 1, Teorifagbygget, House 1 

09:30 

PL7-PL9 

09:45 


10:00 

10:15 

Inaugural Lecture 

PL1 

10:30 

Coffee Break,10:30-11:00 

10:45 

Coffee Break, 10:45-11:15 

11:00 

11:15 

11:30 


11:45 

PL10-PL12 


12:00 

PL2-PL4 

12:15 

12:30 

12:45 

13:00 

Lunch, Lysgården 

12:30-13:30 

13:15 

13:30 

Lunch, Lysgården, 

13:00-14:00 

13:45 

14:00 

Lecture Lecture Lecture 

Plenary Lecture PL5-PL6, 

14:15 

L25-L29 L30-L34 L35-L38 

Store Auditorium, Lysgården 

14:30 

Store Aud Aud. 3 Aud. 4 

14:45 


15:00 

L1-L4, L9-L12 L18-L21 

15:15 

Aud. 3 Store Aud. 4 Coffee Break, 15:20-15:40 

15:30 

Aud. 

15:45 

16:00 

Coffee Break, 16:00-16:20 

CSI award 

16:15 

Store Auditorium 

16:30 


16:45 

L5-L8 L13-L17 L22-L24 

17:00 

Aud. 3 Store Aud. 4 

NKS award, Store Auditorium 

17:15 

Aud. 

17:30 

17:45 

18:00 

18:15 

Registration 

Radisson 

Blu Hotel Bus Departures, 18:15 

Award Reception 

Lysgården 

Bus Departures, 18:15 

18:30 

18:45 

19:00 

19:15 

19:30 

19:45 

20:00 

The CSI-Club 

Ølhallen 

The CSI-Club 

Ølhallen 

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Schedule of Events 

Lecture 

L39-L44 

Aud. 3 

Wednesday, June 19 Thursday, June 20 Time 

09:00 

09:15 

09:30 



09:45 

PL13-PL16 

PL21-PL24 

10:00 



10:15 

10:30 

10:45 

Coffee Break, 11:00-11:20 Coffee Break 11:00-11:20 11:00 

Plenary Lecture PL17-PL19 

11:20-12:50 

Lunch, 

Lysgården, 12:50-13:50 

Plenary Lecture PL20 

Store Aud., 13:50-14:20 

Lecture 

L45-L50 

Store 

Aud. 

Lecture 

L51-L56 

Aud. 4 

Poster Discussions 

16:20 (16:50) -18:30 

Lecture 

L56-L63 

Aud. 2 


11:20-12:20 

Lunch, 

Lysgården, 12:20-13:20 


13:20-14:20 

Lecture 

L64-L67 

Store Aud. 

Lecture 

L68-L70 

Aud. 3 

11:15 

11:30 

11:45 

12:00 

12:15 

12:30 

12:45 

13:00 

13:15 

13:30 

13:45 

14:00 

14:15 

14:30 

14:45 

15:00 

15:15 

15:30 

15:45 

Closing Ceremony 

16:00 

15:45 

16:15 

Bus Departures, 16:30 16:30 

16:45 

17:00 

17:15 

17:30 

17:45 

18:00 

18:15 

Bus Departures, 18:30 18:30 

18:45 

19:00 

19:15 

19:30 

Conference Dinner, Fram Centre, 19:45 

19:45 

20:00 

-14 -


Daily Programme 

DAILY PROGRAMME 

Monday, June 17, 2013 

Time Abs. 

09:00 Opening Ceremony 

Auditorium 1, Teorifagbygget, House 1 

Chairman: Yngvar Thomassen 

09:45 PL1 Inaugural Lecture 

Hubble Space Telescope and Its Discoveries 

Richard E. Griffiths, Carnegie Mellon University, Pittsburgh, USA/NASA HQ 

10:45 Coffee Break 

Climate Change and Spectroscopy 



11:15 PL2 Climate Change and Mitigation: Carbon Capture – A Bridge Into a Low Carbon Economy 

Claus Jørgen Nielsen, University of Oslo, Norway 

12:00 PL3 Molecular - Level Analysis and Photochemical Aging of Atmospheric Organics in Ambient Particles 

and Aqueous Droplets 

Sergey A. Nizkorodov, University of California, USA 

12:30 PL4 Characterization of Atmospheric Aerosol Particles by Electron Microscopy 

Stephan Weinbruch, Technical University Darmstadt, Germany 

13:00 Lunch 

Faculty of Health Sciences, Lysgården. 

Store Auditorium – Lysgården 

14:00 PL5 Basic Research for Chemical Absorption of Carbon Dioxide Using NMR Spectroscopy 

Cristina Perinu, Telemark University College, Porsgrunn, Norway 

14:20 PL6 Molecular Analysis of the Organic and Elemental Carbon Fractions (EC/OC) of Ambient Particulate 

Matter by Coupling of a Thermal Carbon Analyzer to Photo-Ionization Mass Spectrometry 

Ralf Zimmermann, University of Rostock, Germany 

Time Abs. 

I. MATERIAL CHARACTERISATION 

Auditorium 3 – Lysgården 

Chairman: Irina Snigireva 

14:40 L1 X-Ray Refractive Optics: Present Status and New Developments 

Anatoly Snigirev, European Synchrotron Radiation Facility, France 

15:00 L2 Characterisation of Nanoparticles With Synchrotron X-Ray Standing Wave Fluorescence 

Roland Hergenröder, Leibniz-Institut für Analytische Wissenschaften, Dortmund, Germany 

15:20 L3 NEXAFS Spectroscopic Studies of Anodized Ti-6Al-4V Alloy With the Aide of First Principles 

Calculations 

Toshihiro Okajima, Kyushu Synchrotron Light Research Center, Japan 

15:40 L4 Microscale Mineral Analysis of Clay Rock Thin Sections After Sorption Experiment Using SRXRF 

Szabina Török, HAS Energy Research Institute, Budapest, Hungary 


16:20 L5 Synthesis and Characterization of Metal Nanoclusters: A New Generation of Luminescent Labels 

Laura Trapiella-Alfonso, University of Oviedo, Spain 

16:40 L6 Advanced Inspection Technologies in Extreme Scenarios: Standoff LIBS and Underwater LIBS 

Javier J. Laserna, University of Málaga, Spain 

17:00 L7 The UMS: A New Tool for Multi-Angle UV-VIS-NIR Photometric Spectroscopy 

Jan Wuelfken, Agilent Technologies,Waldbronn, Germany 

17:20 L8 57Fe-Mössbauer Study of Electrically Conductive Lithium Iron Vanadate Glass 

Shiro Kubuki, Tokyo Metropolitan University, Japan 

17:40 

18:10 Bus Departures 

-15 -



Monday, June 17, 2013 

Time Abs. 

II. PLASMA SPECTROCHEMISTRY 


Chairman: Maria Montes-Bayón 

14:40 L9 Breakthrough in Sensivity for Quadrupole ICP-MS 

Meike Hamester, Bruker Daltonics, Germany 

15:00 L10 Determination of Rare Earth Elements in Extracts from Oil Refinary Spent Catalyst by ICP-MS with 

a Reaction Cell 

Jessee Severo Azevedo Silva, Universidade Federal de Santa Catarina, Brazil 

15:20 L11 Some Procedures of Reducing Matrix Effects in ICP-MS Analysis of Biological Samples 

Konstantin Ossipov, Lomonosov Moscow State University, Russia 

15:40 L12 Development of an Analytical Method for Cd, Co, Cr, Cu, Ni and Pb Determination in Cosmetic 

Samples 

Edenir Rodrigues Pereira-Filho, Federal University of São Carlos, Brazil 


16:20 L13 The New 8800 ICP-QQQ: Handling the Most Difficult Samples With Ease 

Uwe Noetzel, Agilent Technologies, Germany 

16:40 L14 A Comparison of Conventional (Off-Line) and On-Line Isotope Dilution ICP-MS for the 

Determination of Total Selenium in Human Serum 

Petru Jitaru, Institut Polytechnique LaSalle Beauvais, Beauvais cedex, France 

17:00 L15 From 2D Towards 3D Elemental Imaging by Laser Ablation ICP-MS - A Study of Archaeological 

Glass 

Vid S. Šelih, National Institute of Chemistry, Ljubljana, Slovenia 

17:20 L16 Direct Solid Quantitative Analysis of Battery Components Using LA-ICP-MS and Development of 

Custom Made Solid Standard Materials Analysis of Battery Materials 

Björn Hoffmann, University of Münster, Germany 

17:40 L17 Direct Elemental Analysis of Nanodiamonds With ICP-OES 

Dmitry S. Volkov, Lomonosov Moscow State University, Russia 


Time Abs. 

III. THEORETICAL, STRUCTURAL AND MODELLING STUDIES 


Chairman: Arne Bengtson 

14:40 L18 Experimental Spectroscopic and Quantum Chemical Studies of the Reactivity of Alkylresorcinols in 

Redox Processes 

Alexander A. Kamnev, Institute of Biochemistry and Physiology of Plants and Microorganisms, Saratov, 

Russia 

15:00 L19 Vibrational Spectral Analysis of the Isotopic Species of Hydrogen Sulphide, Hydrogen Selenide and 

Water Using the U(4) Algebraic Model 

Nirmal Kumar Sarkar, Karimganj College, India 

15:20 L20 Theoretical Investigation of the CW Absorption, Resonance Raman and REMPI Spectroscopy of the 

S1 and S2 States of cis-1,3,5-Hexatriene and trans-1,3,5-Hexatriene 

Clemens Woywod, University of Tromsø, Norway 

15:40 L21 Basis Set Extrapolation for High Resolution Spectroscopy 

Kiran Sankar Maiti, University of Gothenburg, Sweden 


16:20 L22 Exploring Structure and Ultrafast Dynamics of Protein and Peptide Using Two Color 2D IR 

Spectroscopy 

Susmita Roy, University of Gothenburg, Sweden 

16:40 L23 Fat Determination of Intact Food Samples with Time-Domain Nuclear Magnetic Resonance 

Spectroscopy and Chemometrics 

Fabiola Manhas Verbi Pereira, Embrapa Instrumentation, São Carlos, Brazil 

17:00 L24 Diode Laser Absorption Spectrometry as a Tool for Contactless Diagnostic of a Hot Zone 

Michael A. Bolshov, Institute for Spectroscopy RAS, Moscow, Russia 


-16 -



Time 

Abs. 

Tuesday, June 18, 2013 

Pristine Environments and Spectroscopy 


Chairman: Klaus Heumann 

09:00 PL7 Arctic – From Cold War to Arctic Melt Down: 20 Years of Arctic Monitoring and Assessment of 

Pollutants and Climate Change by AMAP 

Lars Otto Reiersen, Artic Monitoring and Assessment Programme, Oslo, Norway 

09:30 PL8 Spectroscopy under Ice 

Carlo Barbante, University of Venice, Italy 

10:00 PL9 Bioluminescent Ecological Assay. Features and Scope of Applications 

Nadezhda Kudryasheva, Siberian Federal University, Krasnoyarsk, Russia 


11:00 PL10 FTIR Spectroscopy in Microbial Ecology: ‘Shedding IR Light’ on Cellular Metabolic Responses to 

Environmental Factors 

Alexander A. Kamnev, Institute of Biochemistry and Physiology of Plants and Microorganisms, Saratov, 

Russia 

11:30 PL11 Atmospheric Deposition of Trace Elements on the Local and Regional Scale Studied by ICP-MS 

Analysis of Moss Samples 

Eiliv Steinnes, Norwegian University of Science and Technology, Trondheim, Norway 

12:00 PL12 Mass Spectrometry Made Easy: The Quest for Simplicity in Forensic, Food, Pharmaceutical, 

Environmental, Medical and Biochemical Analysis 

Marcos Eberlin, Universidade Estadual de Campinas, Brazil 

12:30 Lunch 


Time Abs 

IV. MASS SPECTROMTRY 


Chairman: Georg Becher 

13:30 L25 Liquid Chromatography Mass-Spectrometry as a Tool for Detection of Chemicals Connected with 

Chemical Warfare Agents in Environmental and Bio Samples 

Igor A. Rodin, Moscow State University, Russia 

14:00 L26 Collision-Induced Dissociation of Hydroxylated Polycyclic Aromatic Hydrocarbons in an Ion Trap 

Tandem Mass Spectrometer 

Xue Li, ETH Zürich, Switzerland 

14:20 L27 Electrospray Ionization Mass Spectrometry Assisted by Inductively Coupled Plasma Mass 

Spectrometry as a Tool to Study the Se/S Substitution in Methionine and Cysteine in Se-Enriched 

Yeast 

Katarzyna Bierła, CNRS/UPPA, Laboratoire de Chimie Analytique Bio-inorganique et Environnement 

(LCABIE), Pau, France 

14:40 L28 Identification of Original Sources of Vermilion in Antiquity Using Sulfur Isotope Ratio Analysis 

Takeshi Minami, Kinki University, Osaka, Japan 

15:00 L29 Study of Interactions Between Reactive Gas Species and Microorganisms by Nano-Resolution Mass 

Spectrometry Imaging 

Jean-Nicolas Audinot, Centre de Recherche Public Gabriel Lippmann, Belvaux, Luxembourg 


15:40 

CSI AWARD 


Introduced by Yngvar Thomassen and Gary Hieftje 

16:40 NORWEGIAN CHEMICAL SOCIETY-DIVISION OF ANALYTICAL CHEMISTRY HONORARY AWARD 


Introduced by Elin F. Gjengedal and Freddy Adams 

17:15 




-17 -



Tuesday, June 18, 2013 

Time Abs. 

V. ATOMIC ABSORPTION SPECTROMTRY 


Chairman: Robert McCrindle 

13:30 L30 Solid Sampling Techniques for the Direct Elemental or Isotopic Analysis of Dried Matrix Spots 

Martín Resano, University of Zaragoza, Spain 

14:00 L31 Low Resolution Continuum Source Electrothermal Atomic Absorption Spectrometry: Clarification of 

Analytical Potential 

Dmitri Katskov, Tshwane University of Technology, Pretoria, South Africa 

14:20 L32 Trace Determination of Metals by In-Atomizer Hydride Trapping AAS: Method Development, 

Validation and Analytical Applications 

Jan Kratzer, Institute of Analytical Chemistry of the ASCR, Brno, Czech Republic 

14:40 L33 Optimization Study on Determination of Inorganic Arsenic Species in Hot Chilli Pepper and Tomato 

Varieties by Using Microwave Assisted Digestion Followed by Flow Injection-Hydride Generation 

Atomic Absorption Spectrometry 

Saksit Chanthai, Khon Kaen University, Thailand. 

15:00 L34 Preconcentration of Mercury from Natural Waters by Amalgamation of Hg 2+ on Copper Powder and 

Hg 0 on Gold Nanoparticles. 

Nikolay Panichev, Tshwane University of Technology, Pretoria, South Africa 


Time Abs. 

VI. GLOW DISCHARGE 


Chairman: Volker Hoffmann 

13:30 L35 Sampling of Liquids in Atomic Emission Spectrometry Using a Helium Atmospheric Pressure Glow 

Discharge 

José A.C. Broekaert, University of Hamburg, Germany 

14:00 L36 GD TOFMS with Pulsed Combined Hollow Cathode for Direct Analysis of Dielectric Samples 

Alexander Ganeev, St. Petersburg State University, Russia 

14:20 L37 Selective Excitation in Analytical Glow Discharges – Its Relevance in GD-OES Analysis 

Edward B. M. Steers, London Metropolitan University, UK 

14:40 L38 Molecular Emission in GD-OES Revisited – Strategies for Background Correction 

Arne Bengtson, Swerea KIMAB, Kista, Sweden 


15:40 

CSI AWARD 


Introduced by Yngvar Thomassen and Gary Hieftje 

16:40 NORWEGIAN CHEMICAL SOCIETY-DIVISION OF ANALYTICAL CHEMISTRY HONORARY AWARD 


Introduced by Elin F. Gjengedal and Freddy Adams 

17:15 




-18 -



Time 

Abs. 

Wednesday, June 19, 2013 

Human Health and Spectroscopy 


Chairman: Alexander Kamnev 

09:00 PL13 Confocal Spectral Imaging Technique in the Development of Photo- and Neutronsensitizers for 

Anticancer Therapy 

Alexey V. Feofanov, Lomonosov Moscow State University, Russia 

09:30 PL14 New Developments in Disease Recognition by Infrared and Raman Spectroscopy and Microscopy: 

Present Status and Future Promises 

János Mink, Institute of Molecular Pharmacology, Research Centre for Natural Sciences, Budapest, 

Hungary 

10:00 PL15 Metabolic Fingerprinting via Mass Spectrometric Analysis of Exhaled Breath 

Renato Zenobi, ETH Zürich, Switzerland 

10:30 PL16 Accurate Measurement of Iron Metabolism Biomarkers: New Tools and Remaining Challenges 

Maria Montes-Bayón, University of Oviedo, Spain 


11:20 PL17 SALDI Mass-Spectrometry: Principles and Application for Drug Analysis 

Alexander Grechnikov, Vernadsky Institute of Geochemistry and Analytical Chemistry of RAS, Moscow, 

Russia 

11:50 PL18 SIMS and the Single Cell 

Vic Norris, University of Rouen, France 

12:20 PL19 High Resolution MALDI Imaging: Reliable Molecular Information at Cellular Resolution 

Andreas Römpp, University of Giessen, Germany 

12:50 Lunch 

Faculty of Health Sciences, Lysgården 

Time Abs. 

Progress in Mass Spectrometry 


Chairman: Carlo Barbante 

13:50 PL20 New Approaches, Plasmas, and Instrumentation for Atomic Spectrometry 

Steven J. Ray, Indiana University, Bloomington, USA 

-19 -




Time Abs. 

VII. ENVIRONMENTAL APPLICATIONS I 


Chairman: Janos Mink 

14:20 L39 Chemical Characterization of Dekati ® Low Pressure Impactor (DLPI) Wall Deposits 

Thibaut Durand, Institut National de Recherche et de Sécurité, Vandoeuvre-lès-Nancy, France 

14:40 L40 Chemical Characterization and Oxidative Potential of PM2.5 Collected in Office Buildings in Greece 

and The Netherlands: A Cooperative Study 

Tamás Szigeti, Eötvös Loránd University, Budapest, Hungary 

15:00 L41 FTIR (DRIFT) Spectroscopic Analysis of Accumulation and Structural Features of Poly-3- 

Hydroxybutyrate in Cells of Azospirillum Brasilense: Effects of Copper(II) 

Anna V. Tugarova, Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and 

Microorganisms, RAS, Saratov, Russia 

15:20 L42 A New Hybrid Fluorometer-Spectrophotometer for Water Quality Analysis of Oil, Chromophoric 

Dissolved Organic Matter, Chlorophyll and -NHX 

Adam M. Gilmore, HORIBA Instruments Inc., Edison, USA 

15:40 L43 Occurrence of Polychlorinated Biphenyls (PCBs) and Polybrominated Diphenylethers (PBDEs) in 

Different Fish Species from Ilha Grande Bay, Southeastern Brazil. 

Isabel Moreira, Pontifícia Universidade Católica do Rio de Janeiro, Brazil 

16:00 L44 Application of Multi-Reflection, High Resolution Time-of-Flight-Mass Spectrometry as Detector for 

One- and Two-Dimensional Gas Chromatography: Characterization of Complex Mixtures 

Ralf Zimmermann, University of Rostock, Germany 

16:20 Poster Discussions 


19:45 Conference Dinner 

Time Abs. 

VIII. IMAGING AND MODELLING 


Chairman: José Broekaert 

14:20 L45 New Imaging Capabilities Using LA-ICP-TOF Mass Spectrometry 

Detlef Günther, ETH Zürich, Switzerland 

14:40 L46 Further Developments of an Energy- and Position-Sensitive XRF Imaging System Based on a 

THCOBRA Detector 

Analusia L.M. Silva, University of Aveiro, Portugal 

15:00 L47 Pharmaceutical Images Harvesting and Comparison 

Tomáš Pekárek, Zenitva, k.s., Prague, Czech Republic 

15:20 L48 Novel Multispectral Imaging Approaches For Recovering of Degraded Archaeological Wall 

Paintings 

Vincenzo Palleschi, CNR Area della Ricerca del CNR, Pisa, Italy 

15:40 L49 LA-ICPMS Imaging And Nuclear Forensics: Pu Isotope Ratios In Sediments From Mayak PA, Russia 

Simone Cagno, Norwegian University of Life Sciences, Ås, Norway 

16:00 L50 Physicochemical Investigation of The Wall Paintings of Petros Paulos Church, Ethiopia 

Kidane Fanta Gebremariam, Norwegian University of Science and Technology, Trondheim, Norway 

16:20 Poster Discussion 



-20 -




Time Abs. 

IX. HUMAN HEALTH 


Chairman: Elin Gjengedal 

14:20 L51 Comparison Between SR-XRF and ICP-AES 

Jun Kawai, Kyoto University, Japan 

14:40 L52 Analysis of Bones for Forensic Studies 

Vincenzo Palleschi, CNR Area della Ricerca del CNR, Pisa, Italy 

15:00 L53 Printable Surface Enhanced Raman Scattering Strips with In-Situ Growth of Gold Nanoparticles 

Wei Ju, Liao, National Yang-Ming University, Taiwan 

15:20 L54 Speciation and Cobalt Toxicity on Human Lung Cells: An Interdisciplinary Study 

Carole Bresson, Laboratoire de Développement Analytique Nucléaire, Isotopique et Elémentaire, Gifsur-Yvette, 

France. 

15:40 L55 Fast and Non-Destructive Quantification of Dapivirine in Hiv Preventive Intravaginal Rings by 

Raman Spectroscopy 

Lotte B. Lyndgaard, University of Copenhagen, Denmark 

16:00 L56 Titanium Measurement in Biofluids by ICP-OES (Simultaneous Inductively Coupled Plasma Optical 

Emission) and He-CC KED Quadrupole ICP-MS 

János Fucskó, NMS Labs, Willow Grove, USA 




Time 

Abs. 

X. ENVIRONMENTAL APPLICATIONS II 


Chairman: Eiliv Steinnes 

14:20 L57 Distribution and Source of Metals in Contaminated Sediments from Rivers in Coal Fields 

Rob McCrindle, Tshwane University of Technology, Pretoria, South Africa 

14:40 L58 Interpretation of the Plastic Life Cycle Using FTIR-ATR and ICP-OES Spectrometry 

Albert van Oyen, CARAT GmbH, Bocholt, Germany 

15:00 L59 Advanced Techniques for Environmental Analysis Using ICP-MS 

Shona McSheehy Ducos, Thermo Scientific, Bremen, Germany 

15:20 L60 Quantitative Analysis of Heavy Elements and Semi-Quantitative Evaluation of Heavy Mineral 

Compositions of Stream Sediments in Japan for Construction of a Forensic Soil Database Using 

Synchrotron Radiation X-Ray Analyses 

Izumi Nakai, Tokyo University of Science, Japan 

15:40 L61 Effect of Metal Stress on Pigments in Copper-Hyperaccumulating Lichens 

Hiromitsu Nakajima, Yokohama National University, Japan 

16:00 L62 High Sensitivity and Extended Scan Speed for Dedicated Isotope Ratio Determinations 

René Chemnitzer, Bruker Daltonics, Bremen, Germany 

16:20 L63 Determination of Heavy Metals at Ultralow Concentration Levels in Pristine Polar Snow and Ice 

Claude F. Boutron, University Joseph Fourier of Grenoble, France 




-21 -



Thursday, June 20, 2013 

Time Abs. 

Material Characterisation and Spectroscopy 


Chairman: Maria Luisa de Carvalho 

09:00 PL21 Pulsed Glow Discharge Time of Flight Mass Spectrometry: A Powerful and Versatile Tool for 

Elemental and Molecular Depth Profile Analysis 

Rosario Pereiro, University of Oviedo, Spain 

09:30 PL22 Coherent High Energy X-Ray Microscopy: A New Tool to Study Mesoscopic Materials 

Irina Snigireva, European Synchrotron Radiation Facility, Grenoble, France 

10:00 PL23 Analysis of Topical Biomedical and Technological Samples by Photothermal and Photoacoustic 

Spectroscopies Using Signal-Enhancement Techniques and Selective Reactions 

Mikhail A. Proskurnin, Lomonosov Moscow State University, Russia 

10:30 PL24 Progress and Demands in Analytical Glow Discharges 

Volker Hoffmann, Institute for Complex Materials, IFW Dresden, Germany 


11:20 PL25 Development and Characterization of Materials for Advanced Power Plants 

Hubertus Nickel, Research Centre Jülich/University of Technology Aachen, Germany 

11:50 PL26 Application of Synchrotron Microprobe Techniques to Speciation of Plutonium in Argillaceous Rocks 

Tobias Reich, Johannes Gutenberg-Universität Mainz, Germany 

12:20 Lunch 

Faculty of Health Sciences, Lysgården 

Progress in Analytical Spectrometry 


Chairman: Martín Resano 

13:20 PL27 An Analytical Technique on Its Way to Adulthood: Current Status and Future Perspectives of Mass 

Spectrometry Imaging 

Andreas Römpp, University of Giessen, Germany 

13:50 PL28 “Think Big! – Optimization of a Spectrometry Lab on the Industrial Scale 

Heiko Egenolf, BASF SE, Competence Center Analytics, Ludwigshafen, Germany 

XI. ENERGY STORAGE CHARACTERISATION 


Chairman: Michael Bolshov 

14:20 L64 Characterization of Decomposition Products in Energy Storage Materials by Chromatographic 

Methods 

Sascha Nowak, University of Münster, Germany 

14:40 L65 Lock-In Thermography – A Novel In-Situ Measurment Methode to Support Surface Spectroscopy for 

Lithium-Ion Cells 

Mathias Reichert, University of Münster, Germany 

15:00 L66 Characterization of the Decomposition Products of a Utilized Battery Electrolyte from a 

Commercial Available Hybrid Vehicle with Purposeful Analytical Methods 

Martin Grützke, University of Münster, Germany 

15:20 L67 Analysis of the Manganese Dissolution and Deposition in LiMn2O4/Li4Ti5O12 Based Lithium Ion 

Batteries 

Markus Börner, University of Münster, Germany 

15:45 Closing Ceremony 



-22 -



Thursday, June 20, 2013 

Time Abs. 

XII. SPECIATION ANALYSIS 



14:20 L67B UV-Photochemical Volatile Species Generation Employed as a Derivatization Technique Between 

HPLC Separation and AAS Detection within Speciation Analysis of Mercury(II), Methylmercury(I), 

Ethylmercury(I) and Phenylmercury(I) 

Vaclav Cerveny, Charles University in Prague, Czech Republic 

14:40 L68 Chemical Vapor Generation for Trace Analysis - Recent Developments 

Alessandro D’Ulivo, Institute of Chemistry of Organometallic Compounds, U.O.S. of Pisa, Italy 

15:00 L69 Influence of Selenium Species in Aquaculture Feeds on the Selenium Status of Farmed Rainbow 

Trout Fry 

Simon Godin, Université de Pau et des Pays de l’Adour, France 

15:45 Closing Ceremony 



-23 -

-24 -


Poster Presentations 

POSTER PRESENTATIONS 

Abstract 

P1 DETERMINATION OF TRACE SULFUR IN BIODIESEL AND DIESEL STANDARD REFERENCE 

MATERIALS BY ISOTOPE DILUTION SECTOR FIELD INDUCTIVELY COUPLED PLASMA MASS 

SPECTROMETRY 

Renata S. Amais, Stephen E. Long, Joaquim A. Nóbrega and Steven J. Christopher 

P2 DETERMINATION OF CHROMIUM SPECIES IN THE WORKPLACE AIR 

M. Stanisławska, B. Janasik; R. Brodzka; W. Wąsowicz 

P3 A NEW APPROACH FOR THE DETERMINATION OF ARSENIC IN THE WORKPLACE AIR. THE 

POSSIBILITY OF USING LA-ICP-MS TECHNIQUE. 

R. Brodzka, B. Janasik, M. Stanisławska, M. Trzcinka-Ochocka, W. Wąsowicz 

P4 DETERMINATION OF MERCURY SPECIES IN FISH USING HPLC-ICP/MS 

Syr-Song Chen, Che-Lun Hsu, Wei-Min Fu, Cheng-Ming, Chu, Su-Hsiang Tseng, Ya-Min Kao, Lih- 

Ching Chiueh and Yang-Chih Shih 

P5 DEVELOPMENT OF A QUANTUM DOT-BASED IMMUNOASSAY FOR SCREENING OF 

TETRACYCLINES IN BOVINE MUSCLE 

Jenifer García-Fernández, Laura Trapiella-Alfonso, José M. Costa, Rosario Pereiro, Alfredo Sanz- 

Medel 

P6 ICP-MS-BASED ISOTOPIC MEASUREMENTS OF ATMOSPHERIC LEAD IN POLAR REGIONS 

Marco Grotti, Andrea Bazzano 1 and Mery Malandrino 

P7 SIGNS OF SPATIAL HETEROGENEITIES WITHIN XLPE CABLE INSULATION PROBED BY 

SOLID STATE 1 H-NMR 

Jobby Paul, Eddy W. Hansen, Sissel Jørgensen, Bjørnar Arstad and Aud Bouzga 

P8 DELTA ( 13 C) DETERMINATION ON BIOFUELS AND BIOPLASTIC APPLYING CAVITY RING- 

DOWN SPECTROSCOPY 

Gisele Birman Tonietto, Jose M. Godoy, Julianna M. Martins , Walquiria R. S. Ribeiro, Mara A. Silva 

P9 THE STRUCTURAL AND MAGNETO-RESONANCE PROPERTIES OF THE POR-INP 

Suchikova Y. 

P10 57FE-MÖSSBAUER, XANES AND HR-TEM STUDIES OF ELECTRICALLY CONDUCTIVE BAO- 

FE 2O 3-V 2O 5 GLASES 

Satoru Yoshioka, Shiro Kubuki, Hitomi Masuda, Kazuhiko Akiyama, Kazuhiro Hara and Testuaki 

Nishida 

P11 MEASUREMENT OF ELEMENTAL CONTENTS IN HEMOLYMPH, MALPIGHIAN 

TUBULES, GUT AND URINE OF RHODNIUS PROLIXUS INVESTIGATED BY SR-TXRF 

Andrea Mantuano, Arissa Pickler, Regina C. Barroso, Liebert P. Nogueira, Carla L. Mota, André P. de 

Almeida, Delson Braz, Simone C. Cardoso, Marcelo S. Gonzalez, Eloi S. Garcia and Patricia 

Azambuja 

P12 CHARACTERIZATION OF SILVER NANOPARTICLES BY PAGE-LA-ICP-MS 

Maria S. Jimenez, Maria T. Gomez, Carmen Diez, Lluis Arola, M.Josepa Salvadó, Cinta Bladé, Juan R. 

Castillo 

P13 MERCURY LEVELS IN A POLLUTED RIVER ECOSYSTEM IN EAST BOHEMIA: FROM LONG- 

TERM MONITORING OF TOTAL CONTENT TO SPECIATION ANALYSIS 

Miroslav Soukup, Inga Petry-Podgórska, Stanislav Lusk, Lukáš Vetešník, Jan Zíka, Vlasta Korunová 

and Jan Kratzer 

-25 -




P15 ICP-MS METHODOLOGY FOR BLOOD TRACE ELEMENTS COMPOSITION ANALYSIS FOR 

PATIENTS WITH DIFFERENT STAGES OF TUMOR 

O.V. Kovalenko, I.V. Boltina, E.O. Pisarev, G. A.Liubchenko, L.S. Kyolodna, N.Ya. Gridina , I.V. 

Kalinitchenko 

P16 THE ISAS- X-RAY FLUORESCENCE BEAM LINE AT DELTA: POSSIBILITIES AND 

APPLICATIONS 

Roland Hergenröder, Alex von Bohlen and Martin Brücher 

P17 CHEMICAL SPECIATION OF INORGANIC BERYLLIUM FOR WORKING AREAS PARTICULATE 

MATTER SAMPLES: SEQUENTIAL EXTRACTION PROCEDURE DEVELOPMENT AND 

APPLICATION 

Thibaut Durand and Davy Rousset 

P18 SELECTIVE AND NON-SELECTIVE EXCITATION/IONIZATION PROCESSES IN AR/HE MIXED 

PLASMAS 

Sohail Mushtaq, Edward B. M. Steers, Juliet C. Pickering and Karol Putyera 

P19 THE MICROWAVE PHOTOCHEMICAL REACTOR FOR THE ON-LINE OXIDATIVE 

DECOMPOSITION OF P-HYDROXYMERCURYBENZOATE (PHMB)-TAGGED PROTEINS AND 

THEIR DETERMINATION BY LC-COLD VAPOUR GENERATION ATOMIC FLUORESCENCE 

DETECTION. 

Beatrice Campanella, Jose González Rivera, Carlo Ferrari, Massimo Onor, Emanuela Pitzalis, 

Alessandro D’Ulivo and Emilia Bramanti 

P20 STUDY OF THE INTERACTION OF CHLORINATED AND SULFOCHLORINATED PARAFFINS 

WITH GELATIN B AND SKIN POWDER. A MODEL FOR FATTENING IN THE LEATHER 

TANNING PROCESS 

Valentina Della Porta, Susanna Monti, Massimo Onor, Alessandro D’Ulivo, Emanuela Pitzalis, Alice 

D’Allara and Emilia Bramanti 

P21 OPTIMIZATION OF ANALYTICAL TESTS FOR THE CHARACTERIZATION AND VALIDATION 

OF MERCURY-SORBENT MATRICES 

Massimo Onor, Emanuela Pitzalis, Alessandro D’Ulivo, Valentina Della Porta, Marco Carlo 

Mascherpa and Emilia Bramanti 

P22 IMPROVEMENTS IN THE DETERMINATION OF SULFIDE, CYANIDE AND THIOCYANATE BY 

CHEMICAL VAPOR GENERATION COUPLED WITH HS-GC-MS 

Massimo Onor, Sara Ammazzini, Enea Pagliano, Emanuela Pitzalis, Emilia Bramanti and Alessandro 

D’Ulivo 

P23 DEVELOPMENT AND EVALUATION OF DESOLVATION SYSTEM FOR DROPLET DIRECT 

INJECTION NEBULIZER 

Yuki Kaburaki, Tomokazu Kozuma, Akito Nomura, Takahiro Iwai, Hidekazu Miyahara, Akitoshi 

Okino 

P24 STUDY OF THE EXCITATION PROCESSES INVOLVING OXYGEN AS AN ADDED GAS IN A 

NEON ANALYTICAL GLOW DISCHARGE PLASMA 

Sohail Mushtaq, Edward B. M. Steers and Juliet C. Pickering 

P25 INVESTIGATIONS ON THE USE OF AMMONIA AS A REACTION GAS TO OVERCOME 

INTERFERENCES IN RARE EARTH ELEMENTS BY ICP-MS 

Jessee Severo Azevedo Silva, Tatiane de Andrade Maranhão, Daniel L. Galindo Borges, Vera Lucia 

A. Frescura and Adilson José Curtius 

P26 STUDY OF TETRACYCLINE FRAGMENTATION WITH LC-MS 

Martin Šala, Drago Kočar, Tadeja Lukežič, Gregor Kosec and Hrvoje Petkovič 

-26 -




P27 METHOD DEVELOPMENT FOR THE ANALYSIS OF ORGANOPHOSPHORUS COMPOUNDS IN 

LIPF 6-BASED ELECTROLYTES 

Vadim Kraft, Martin Grützke, Martin Winter and Sascha Nowak 

P28 IN-SITU MÖSSBAUER SPECTROSCOPY AS A NON-DESTRUCTIVE TOOL TO ANALYZE 

LITHIUM-ION BATTERY AGING 

Sascha Weber, Thorsten Langer, Falko Schappacher, Rainer Pöttgen and Martin Winter 

P29 COMPARISON OF VARIOUS SPECTROSCOPIC IMAGING TECHNIQUES FOR 

INVESTIGATION OF HG AND SE METABOLISM IN PLANT TISSUES 

Marta Debeljak, Johannes Teun van Elteren 1 , Katarina Vogel-Mikuš, Alessandra Gianoncelli, David 

Jezeršek 

P30 SIZE CHARACTERISATION OF METALS IN TUNNEL WASH WATER AS A FUNCTION OF 

TIME AND DETERGENT 

Jon-Henning Aasum, Elin Gjengedal and Sondre Meland 

P31 DIRECT DETERMINATION OF BROMINE IN PLASTIC MATERIALS BY MEANS OF SOLID 

SAMPLING HIGH-RESOLUTION CONTINUUM SOURCE GRAPHITE FURNACE MOLECULAR 

ABSORPTION SPECTROMETRY 

María R. Flórez, E. García-Ruiz, Martín Resano 

P32 CHANGES IN CHEMICAL COMPOSITION OF URBAN PM 2.5 BETWEEN 2010 AND 2013 IN 

HUNGARY 

Tamás Szigeti, Mihály Óvári, Franco Lucarelli, Gyula Záray, Victor G. Mihucz 

P33 DETERMINATION OF FLUORINE USING HIGH RESOLUTION CONTINUUM SOURCE 

MOLECULAR ABSORPTION SPECTROMETRY (HR-CS MAS) 

René Nowka and Heike Gleisner 

P34 DETERMINATION OF TRACE ELEMENTS IN BLACK AND WHITE PEPPERS BY XRF 

SPECTROMETER EQUIPPED WITH POLARIZATION OPTICS AND ITS DEVELOPMENT TO 

IDENTIFICATION OF THEIR PRODUCTION AREA 

Akiko Hokura, Megumi Shibasawa and Noriko Kuze 

P35 DETERMINATION OF SELENIUM USING CHEMICAL AND PHOTOCHEMICAL VOLATILE 

COUMPOUNDS GENERATION COUPLED WITH ATOMIC ABSORPTION SPECTROMETRY 

Marcela Rybinova, Vaclav Cerveny and Petr Rychlovsky 

P36 EFFECT OF ZINC IN HISTORICAL IRON BASED INK CONTAINING DOCUMENTS: A MULTI- 

SPECTROSCOPIC APPROACH 

Marta Manso, Ana Mafalda Cardeira, Tânia Rosado, Mara Silva, Agnès Le Gac, Sofia Pessanha, 

Mauro Guerra, Stéphane Longelin, Ana Teresa Caldeira, António Candeias and Maria Luísa 

Carvalho 

P37 EVALUATION OF CALCIUM AND PHOSPHORUS IN TOOTH ENAMEL EXPOSED TO 

BLEACHING GEL 

Godinho J., Pessanha S., Silveira J, Mata A., Carvalho M.L. 

P38 ASSESSMENT OF ESSENTIAL ELEMENTS AND HEAVY METALS CONTENT ON MYTILUS 

GALLOPROVINCIALIS FROM RIVER TAGUS ESTUARY 

I. Santos, M. Diniz, M. L. Carvalho, J. P. Santos 

P39 CHARACTERIZATION OF CALCIUM SULPHATE AND GLUE SIZING UNDER CALCIUM 

CARBONATE GROUND LAYERS IN FLEMISH AND LUSO-FLEMISH PAINTINGS - ANALISYS 

BY SEM-EDS AND µXRD 

Vanessa Antunes, Maria José Oliveira, Helena Vargas , António Candeias , Maria Luísa Carvalho, 

Ana Isabel Seruya, João Coroado, Luís Dias, José Mirão, Vitor Serrão 

-27 -




P40 TRACE ELEMENT ENRICHMENT OF LIVING NOURISHMENT AQUATIC ORGANISMS AND 

DETERMINATION OF THEIR UPTAKE BY ATOMIC ABSORPTION SPECTROMETRY 

Milán Fehér, Edina Baranyai, Edina Simon, István Szűcs, Péter Bársony, József Posta, László Stündl 

P41 APPLICATION OF NON-MEMBRANE ELECTROLYTIC CELL FOR ELECTROCHEMICAL 

VOLATILE SPECIES GENERATION OF TRANSITION METALS 

Jakub Hraníček, Andrea Kobrlová, Václav Červený, Tomáš Vacek, Tomáš Matoušek and Petr 

Rychlovský 

P42 ASSESSMENT OF NUTRIENTS OF ESCAMOLES ANT EGGS LIMOTEPUM APICULATUM M BY 

SPECTROSCOPY METHODS 

Virginia Melo, Tomas Quirino, Concepción Calvo, Karina Sánchez and Horacio Sandoval 

P43 SPECTROSCOPIC STUDY OF THE AGEING PROCESSES IN TANNIN DYED TEXTILES 

S. Legnaioli, G.H. Cavalcanti G. Lorenzetti, V. Palleschi, E. Grifoni, I. Degano, M. P. Colombini, E. 

Ribechini 

P44 SPECTROSCOPIC STUDIES OF XII-XIV CENTURY ITALIAN GOLD COINS BY X-RAY 

FLUORESCENCE 

M. Baldassarri, G.H. Cavalcanti, M. Ferretti, A. Gorghinian, E. Grifoni, S. Legnaioli, G. Lorenzetti, L. 

Marras, E. Violano and V. Palleschi 

P45 SPECTROSCOPIC STUDIES ON ETRUSCAN ARCHAEOLOGICAL FINDINGS 

G. Sorrentino, S. Giuntoli, M. Lezzerini, S. Legnaioli, G. Lorenzetti, G.H. Cavalcanti and V.Palleschi 

P46 DETERMINATION OF METALS IN THE FOOD CHAIN USING THE HIGH SPEED SELF 

REVERSAL METHOD FOR BACKGROUND COMPENSATION 

Oppermann, Uwe and van Oyen, Albert 

P47 LO-RAY-LIGH ® DIFFRACTION GRATINGS IN UV-VIS SPECTROSCOPY 

U. Oppermann, M. Egelkraut-Holtus, and T. Fujiwara 

P48 PLASTC WASTE IN THE ENVIRONMENT – A NEW CHALLENGE IN SPECTROSCOPY 

Oppermann, Uwe and van Oyen, Albert 

P49 XRF DETERMINATION OF SILICON IN ALUMINA 

Michele Cowley and Johann Fischer 

P50 XRF DETERMINATION OF SULPHUR IN IRON OXIDE 

Michele Cowley , Johann Fischer and Willemien van Schalkwyk 

P51 ELEMENTAL MAPPING OF MOROCCAN ENAMELED TERRACOTTA TILE WORKS (ZELLIJ) 

BASED ON X-RAY MICRO-ANALYSES 

R. Bendaoud, A. Guilherme, A. Zegzouti, M. Elaatmani, J. Coroado, A. Le Gac,4, S. Pessanha, M. 

Manso, M. L. Carvalho and I. Queralt 

P52 DETERMINATION OF METALS IN LARVAE USING ICP-OES 

Blanca Paz,.Ciro Márquez, Olga Cabrera; Lydia Romero, Carlos Enrique Díaz 

P53 CHALLENGING SPATIAL RESOLUTION LIMITS OF LASER ABLATION INDUCTIVELY 

COUPLED PLASMA MASS SPECTROMETRY (LA-ICP-MS) IN ELEMENTAL DISTRIBUTION 

MAPPING APPLICATIONS EMPLOYING ACTIVE 2-VOLUME CELL TECHNOLOGY 

Dhinesh Asogan, Damon Green, John Roy, Stephen Shuttleworth, Bill Spence and Peter Winship 

P54 LOW VOLUME SAMPLE INJECTION FOR TRACE ELEMENT ANALYSIS EMPLOYING 

INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY (ICP-MS) 

David Clarke, Bill Spence and Peter Winship 

P55 APPLICATION OF LEAD ISOTOPE RATIO MEASUREMENTS FOR THE ORIGIN ASSESSMENT 

OF MARINE POLLUTION 

Emilia Vassileva and Anna Maria Orani 

-28 -




P56 APPLICATION OF HIGH RESOLUTION SECTOR FIELD ICP- MS FOR DETERMINATION OF 

LOW LEVEL PLUTONIUM IN MARINE SAMPLES 

Emilia Vassileva, Eunmi Han and Isabel Levy 

P57 FTIR EMISSION SPECTROSCOPIC STUDY OF 

ALUMINA-SILICATE BASED BLACK POWDER WITH PECULIAR PROPERTIES 

J. Mink, J. Mihály, Cs. Németh 

P58 NEW IMAGING CAPABILITIES USING LA-ICPTOF MASS SPECTROMETRY 

H.A.O. Wang, C. Giesen, D. Grolimund, B. Bodenmiller, D. Günther 

P59 TRACE ELEMENT DISTRIBUTION OF EXTRACELLULAR PROTEINS DETERMINED IN HUMAN 

SERUM BY MP-AES AND GFAAS 

Edina Baranyai, Csilla Noémi Tóth, Mihály Braun, Tünde Tarr, István Csípő, Margit Zeher, József 

Posta 

P60 THE ANALYSIS OF DDTS AND CHLORDANES AND THEIR METABOLITES BY GAS 

CHROMATOGRAPHY TANDEM MASS SPECTROMETRY: COMPARING ATMOSPHERIC 

PRESSURE IONISATION WITH ELECTRON IMPACT AND CHEMICAL IONISATION 

Sandra Huber, Nicholas A. Warner, Therese Haugdahl Nøst, Ole-Martin Fuskevåg and Jan Brox 

P61 PALM-TOP EPMA USING PYROELECTRIC ELECTRON BEAM FOR 100 MICROMETER BEAM SIZE 

Jun Kawai, Akira Imanishi, Susumu Imashuku 

-29 -


Plenary Lecture Abstracts 

PLENARY LECTURE ABSTRACTS 

(PL1) 

HUBBLE SPACE TELESCOPE AND ITS DISCOVERIES 

Richard E. Griffiths, 

Carnegie Mellon University, Pittsburgh, USA/NASA HQ 

-30 -



(PL2) 

CLIMATE CHANGE MITIGATION. 

CARBON CAPTURE – A BRIDGE INTO A LOW CARBON ECONOMY 

Claus Jørgen Nielsen, 

Department of Chemistry, University of Oslo 

Climate is often defined as “average weather” and described in terms of the mean and variability of 

observed temperature, precipitation and wind over a period of time. The most fundamental climate 

descriptor is probably the Earth annual average surface temperature. This temperature is controlled 

by the solar energy input and the surface reflectivity of the Earth. Climate is constantly changing due 

to dynamic interactions between atmosphere, land surface, snow, ice, oceans, rivers, lakes, biota, 

and due to changes in external factors (forcings) including natural phenomena such as volcanic 

eruptions and solar variations, as well as human-induced changes in atmospheric composition. The 

radiation balance of the Earth will change as a result of changes in the incoming solar radiation, 

changes in the fraction of solar radiation that is reflected, and changes in greenhouse gas (GHG) 

concentrations. 

The increasing emissions of GHGs from human activities have led to a marked increase in 

atmospheric concentrations of the long-lived GHG gases CO 2 , CH 4 , N 2 O, SF 6 , perfluorocarbons 

(PFCs), hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons 

(HCFCs) and halons, and the human-induced radiative forcing of the Earth’s climate is largely due 

to the atmospheric increases in these. 

Global energy use is projected to continue to grow. With no substantial change in policies, the 

energy sources to run the global economy will essentially remain unchanged – the majority of our 

energy supply will be based on fossil fuels, with consequent implications for GHG emissions. 

Carbon Capture and Storage (CCS) is seen as one way to mitigate climate change, and one of the 

more mature post combustion CO 2 capture technologies is based on amine absorbents. Given the 

scale of implementation of post-combustion CCS, it is likely that there will be relatively small but 

still significant discharges of amines to the atmosphere during operation. Quantitative knowledge 

about the atmospheric fate of amines including their partitioning to particles and droplets and their 

contribution to the formation of new particles, is therefore important to an environmental impact 

assessment of amine-based CO 2 capture. 

The CO 2 Technology Centre Mongstad (TCM) is the world’s largest facility for testing and 

improving CO 2 capture. The knowledge gained will prepare the ground for CO 2 capture initiatives to 

combat climate change. TCM is a joint venture between the Norwegian state, Statoil, Shell and 

Sasol. It is located at the West coast of Norway, north of the city Bergen. The main ambitions of 

TCM are: (1) to test, verify and demonstrate CO 2 capture technology owned and marketed by 

vendors; (2) to reduce cost, technical, environmental and financial risks; (3) to encourage the 

development of the market for carbon capture technology, and (4) to stimulate international 

development. The centre was officially opened on May 7 th 2012, and consists of two CO 2 capture 

demonstration plants and a utility system. One plant is an amine plant designed by Aker Clean 

Carbon, and the other is a chilled ammonia plant designed by Alstom. 

-31 -



(PL3) 

MOLECULAR-LEVEL ANALYSIS AND PHOTOCHEMICAL AGING OF 

ATMOSPHERIC ORGANICS IN AMBIENT PARTICLES AND AQUEOUS DROPLETS 

Sergey A. Nizkorodov 

Department of Chemistry, University of California, Irvine, CA 92697-2025, USA 

Organic aerosols make up a significant fraction of the atmospheric particulate matter. They affect air 

quality, visibility, and regional and global climate. What makes the representation of organic 

aerosols in climate and air pollution models especially challenging is their dynamic nature – they 

continuously change their chemical composition and physical properties as a result of various 

“aging” processes. This presentation will discuss the effects of particle-phase photochemical and 

dark reactions on the molecular level chemical composition of biogenic organic aerosols. This 

question will be addressed with a combination of novel methods of high resolution mass 

spectrometry and photochemistry. 

-32 -



(PL4) 

CHARACTERIZATION OF ATMOSPHERIC AEROSOL PARTICLES BY ELECTRON 

MICROSCOPY 

Stephan Weinbruch, Martin Ebert, Konrad Kandler, and Nathalie Benker 

Institute of Applied Geosciences, Technical University Darmstadt, Darmstadt, Germany 

Characterization of atmospheric aerosol particles is of special importance in a number of fields in 

environmental science including: 

climate research (e.g., optical properties of aerosols, cloud formation), 

ecology (e.g., input of organic and inorganic pollutants into ecosystems), 

public health (e.g., adverse health effects of aerosol particles), 

cultural heritage preservation (e.g., degradation of monument surfaces). 

In these applications, characterization of individual particles by electron microscopy (scanning and 

transmission electron microscopy) and related spectroscopic techniques (X-ray microanalysis, 

electron energy loss spectroscopy) complements or even replaces bulk chemical techniques. 

Information obtained by electron microscopy includes size, shape, morphology, nanostructure, 

fractal geometry, chemical composition (elemental composition and in selected cases oxidation 

state), phase composition, and mixing state of particles. In addition, environmental scanning and 

transmission electron microscopy can be used to study thermal, hygroscopic and ice-forming 

properties of individual particles in situ. Application of electron microscopy is especially suited for 

small sample amounts (e.g., airborne sampling with high time resolution), nanoparticles (where it 

may difficult to obtain an appropriate mass for bulk analysis), and for investigation of processes that 

are scaled with the particle number or particle surface (e.g., heterogeneous ice nucleation, systemic 

effects after inhalation of ultrafine particles). 

In the present contribution, an overview of the capability of electron microscopy in particle 

characterization is given first. In the second part, examples of recent applications from our research 

group in the context of climate research are given. These examples include the role of aerosol 

particles in heterogeneous ice nucleation and source apportionment of soot. 

In the atmosphere, homogeneous ice nucleation is only observed at temperatures below -39 °C. At 

higher temperatures, ice nucleation requires the presence of aerosol particles which act as ice nuclei 

(IN). Minerals dust (especially clay minerals) and biological particles are efficient IN. In addition, 

lead compounds present as heterogeneous inclusions (often with diameters of a few nanometer only) 

seem to enhance the ice forming capability of aerosol particles substantially. Environmental 

scanning electron microscopy was used to determine the ice nucleation behavior different minerals 

in laboratory experiments (Zimmermann et al., 2007, 2008). In addition, scanning and transmission 

electron microscopy are used for identification of IN nuclei in various field experiments (Cziczo et 

al. 2009; Ebert et al., 2011). 

Soot (black carbon) is a strongly absorbing aerosol component. Therefore, soot deposited on snow 

will strongly reduce the albedo of the snow, and may also lead to increased melting. On a global 

scale, biomass burning, coal burning and traffic are the major sources of soot. Based on 

nanostructure, minor element contents and the presence of heterogeneous inclusions it is attempted 

to develop a fingerprint for the different soot sources. 

-33 -



References: 

Cziczo D., Stetzer O., Worringen A., Ebert M., Weinbruch S., Kamphus M., Gallavardin S.J., Curtius J., 

Borrmann S., Froyd K.D., Mertens S., Möhler O., and Lohmann U. (2009): Inadvertent climate modification 

due to anthropogenic lead., Nature Geoscience 2, 333-336. 

Ebert M., Worringen A., Benker N., Mertes S., Weingartner E., and Weinbruch S. (2011): Chemical 

composition and mixing-state of ice residuals sampled within mixed phase clouds., Atmospheric Chemistry 

and Physics, 11, 2805-2816. 

Zimmermann F., Ebert M., Worringen A., Schütz L., and Weinbruch S. (2007): Environmental scanning 

electron microscopy (ESEM) as a new technique to determine the ice nucleation capability of individual 

atmospheric aerosol particles., Atmos. Environ. 41, 8219-8227. 

Zimmermann F., Weinbruch S., Schütz L., Hofmann H., Ebert M., Kandler K., and Worringen A. (2008): Ice 

nucleation properties of the most abundant mineral dust phases., J. Geophys. Res. 113, D23204, doi: 

10.1029/2008JD010655. 

-34 -



(PL5) 

BASIC RESEARCH FOR CHEMICAL ABSORPTION OF CARBON DIOXIDE USING 

NMR SPECTROSCOPY 

Cristina Perinu, 1 Bjørnar Arstad, 2 Aud M. Bouzga, 2 Klaus J. Jens 1 

1 Faculty of Technology, Telemark University College, Kjølnes ring 56, 3901 Porsgrunn, Norway 

2 SINTEF Materials and Chemistry, Forskningsveien 1, 0314 Oslo, Norway 

e-mail: cristina.perinu@hit.no 

Nowadays, there is strong concern with the anthropogenic CO 2 (carbon dioxide) emission activities, mainly 

the combustion of fossil fuels and chemical transformation, which is driving the global warming. Several 

options for the reduction of CO 2 emissions have been proposed. Among them, post-combustion capture 

(PCC) technology based on the chemical absorption of CO 2 in aqueous amines is considered the most feasible 

and robust technology to be applied in short-term on a larger scale. The process of chemical absorption in 

PCC involves the reaction of CO 2 with an amine solvent to form an intermediate compound which, with the 

application of heat, will be regenerated to give the original solvent and a CO 2 stream (that will be transported 

for storage). However, the main drawbacks still limiting the application on an industrial scale are represented 

by the high energy demand for CO 2 release and amine regeneration, the corrosivity of the amine solution and 

the tendency of degradation. In order to develop novel absorbents and improve the efficiency of PCC 

technology, an accurate understanding of the fundamental chemical processes (such as equilibriums, kinetics 

and thermodynamics) involved in the capture and release of CO 2 in aqueous amine solvents is of paramount 

importance. Reliable estimates of the liquid phase composition (identification and quantification, called 

speciation) are a prerequisite both to perform chemical investigations and develop theoretical models for 

kinetic and thermodynamic studies. In the present context, speciation is rather involved since several parallel 

reactions that give rise to a large number of species occur. For primary (RNH 2 ) and secondary amines, the 

following main equilibrium reactions are considered to take place in the liquid phase: 

2 RNH 2 + CO 2(aq) RNHCOO - + 

+ RNH 3 (1) 

RNHCOO - - 

+ H 2 O RNH 2 + HCO 3 (2) 

- 

HCO 3 + H 2 O CO 2- 3 + H 3 O + (3) 

RNH + 3 + H 2 O RNH 2 + H 3 O + (4) 

Within the analytical techniques used to chemically investigate these multi-equilibrium systems, Nuclear 

Magnetic Resonance (NMR) is considered to be the most valuable and successful tool because direct 

qualitative and quantitative information about all the species formed during the absorption and desorption of 

CO 2 can be gathered (including unknown compounds, degradation and/or secondary products). By speciation, 

relationships between amine structures can be unveiled, hypothesis on reaction mechanisms may be proposed 

and other information on factors influencing reactions may be obtained. 

In the present work, a NMR investigation on a series of aqueous primary alkalonamines as absorbents for 

CO 2 capture is carried out in order to understand the influence of the amine chemical structure on the 

absorption of CO 2 . By proper optimization of NMR parameters, extensive quantitative 13 C NMR experiments 

to determine the concentrations of all the species at the equilibrium and consequentially the carbamate 

hydrolysis constant (2) are performed. These data will be used for the establishment of the linear free-energy 

relationships between the different amines. Moreover, further NMR experiments are also acquired to support 

the quantitative results in revealing relationship between amine structures and deriving hypothesis on reaction 

mechanisms. 

In the context of the present contribution, the methods used to carry out quantitative NMR experiments and 

the main results showing the influence of structural change on the activities of amines in CO 2 capture will be 

presented. Moreover, some considerations on the important contribution that NMR can give in the 

investigation of chemical equilibriums to improve amine characteristics and rationalize the development of 

high performance CO 2 absorbents will be discussed. 

-35 -



(PL6) 

MOLECULAR ANALYSIS OF THE ORGANIC AND ELEMENTAL CARBON 

FRACTIONS (EC/OC) OF AMBIENT PARTICULATE MATTER BY COUPLING OF A 

THERMAL CARBON ANALYZER TO PHOTO-IONIZATION MASS SPECTROMETRY 

J.Grabowski a , T.Streibel a , J.Chow b , L.-W. Chen b , M.Sklorz a , J. Passig a H. Czech a , O. Sippula a and 

R.Zimmermann a 

Joint Mass Spectrometry Centre of University of Rostock, Chair of Analytical Chemistry, 

Rostock/Germany and Helmholtz Zentrum München,CMA, Neuherberg/Germany (O.S. on leave 

from University of Eastern Finland), Contact: ralf.zimmermann@uni-rostock.de 

DRI-Desert Research Institute, Reno, NV, USA 

Carbonaceous material in airborne particulate matter (PM) is of increasing interest due its adverse 

health effects and its potential influence on the climate. Its analytical ascertainment on a molecular 

level is still challenging. Hence, analysis of carbonaceous fractions for many studies is often solely 

carried out by determining sum parameters such as the overall content of organic carbon (OC) and 

elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC). The used 

thermal analyzing procedure, however, allows to get additional interesting information: By defining 

different thermal OC fractions (i.e. temperature steps in the thermal analyzer) also information on 

the refractory properties of the carbonaceous material is obtained. In this context it is particularly 

interesting to investigate the release and formation behaviors of the evolved molecular species 

responsible for the different OC and EC fractions. Thus after initial promising results of a pre-study 

[1] in the current work a thermal EC/OC carbon analyzer (Model DRI 2000) and a homebuilt photoionization 

time-of-flight mass spectrometer (PI-TOFMS) were hyphenated [2] to investigate 

individual organic compounds in particular from the different OC fractions The carbon analyzer 

enables the stepwise heating of quartz filter samples loaded with PM and provides the sum values of 

the carbon release (Used temperature steps: “Improve protocol” [2]: OC1 - 120 °C, OC2 - 250°C, 

OC3 - 450°C OC4 - 550°C). With the on-line coupled PI-TOFMS now in addition the organic 

compounds which are released during the thermal profile are detectable in real time. This is possible 

by the soft photo ionization methods (SPI - single photon ionization and REMPI - resonanceenhanced 

multi photon ionization) which are suppressing fragmentation upon ionization. The two 

instruments were coupled by a newly developed interface and characterized with standard 

substances. The final thermal EC/OC-analyzer-PI-TOFMS hyphenated instrument then was applied 

to several types of PM filter samples, such as ambient aerosol, gasoline/diesel emissions and wood 

combustion emission. Ambient filter samples e.g. showed a strong impact of organic wood 

combustion markers. This was revealed by comparison to the thermal release signatures of pure 

cellulose, lignin and wood combustion PM with samples of ambient air PM. At higher temperatures 

(450 °C) often a shift to smaller molecules is visible in the mass spectra. This is due to the thermal 

decomposition of larger oligomeric or polymeric molecular structures comparable to lignocelluloses 

and similar oxygenated humic-like substances. PM from vehicle exhaust (gasoline and diesel with 

10% biodiesel) was analyzed. Gasoline PM exhibited large polycyclic aromatic hydrocarbons, 

whereas diesel PM showed a much higher total organic content in the REMPI measurements. The 

detected pattern (SPI) revealed a strong influence of the biodiesel content on the nature of the 

organic PM material. Finally the added value of this specialized thermal analysis technology for the 

field of environmental research is discussed. 

The health effects of organic fractions in anthropogenic aerosols are currently further investigated in 

the framework of the Helmholtz Virtual Institute of Complex Molecular Systems-Aerosols and Healt 

in Environmental Health, HICE (www.hice-vi.eu). 

References: [1] T. Streibel et al., (2006). Anal. Chem. 78, 5354-5361; [2] J. Grabowsky et al. (2011). Anal Bioanal 

Chem 401, 3153–3164 

-36 -



(PL7) 

ARCTIC – FROM COLD WAR TO ARCTIC MELT DOWN 

20 YEARS OF ARCTIC MONITORING AND ASSESSMENT OF POLLUTANTS AND 

CLIMATE CHANGE BY AMAP 

Lars Otto Reiersen, 

Artic Monitoring and Assessment Programme, Oslo, Norway 

Introduction 

AMAP was initiated in 1991 by Ministers from the eight Arctic countries (Canada, Denmark, 

Finland, Iceland, Norway, Russia, Sweden and USA) that today is the Arctic Council. AMAP was 

tasked to monitor and assess the pollution of the Arctic, including effects on ecosystems and 

humans. In 1993, AMAP was asked to include assessments of climate change - including UV/ozone 

and its effects on Arctic ecosystems and humans. 

Since 1993 AMAP has delivered more than 30 scientific and technical assessments. During the first 

ten years the main focus was on contaminants like persistent organic pollutants (POPs), heavy 

metals (especially mercury, lead and cadmium), radionuclides, acidification (especially forest death 

around smelters) and petroleum hydrocarbons. During the following ten years the climate change got 

increasing priority, and today it is the combined effects of climate, pollutants and other stressors that 

have the main focus. Over all the years, the effects due to pollution and climate change on humans, 

especially the Arctic indigenous peoples has been a priority area in relation to their food security and 

life style and to provide advice to health workers. 

Materials and methods 

AMAP has developed strict Guidelines for the work to be done, both for the monitoring part, the 

assessment and data handling. AMAP recommend methodologies accepted by international 

scientific communities and other international organization to achieve comparable data. There are 

special requirements for QA/QC programmes and reporting to Thematic Data Centers. The 

Guidelines are updated when new components are added or new methods accepted. All of these 

Guidelines are available from AMAP web site www.amap.no . 

Results 

The assessments have documented that a range of contaminants: POPs, mercury, radionuclides and 

acidifying components have been and still are transported into the Arctic area and deposited in the 

environment. Some of these contaminants accumulate in food chains, and some also bio-magnify in 

species that feed high in the food chain, including humans. POPs accumulate mainly in the marine 

food web and are bound to lipids (fat), with potential to affect high trophic level predators such as 

polar bears and killer whales, but also indigenous human populations that consume marine mammals 

as part of their traditional diet. The same goes for mercury which also accumulates in fish and 

marine mammals, whereas for radionuclides, the terrestrial food chain is most affected and 

indigenous people living on reindeer meat are the most exposed groups. 

Effects due to the exposure to POPs and methyl mercury have been documented in Arctic animals 

(e.g. polar bear and glaoucous gulls) and humans. This paradoxical situation –- where Arctic people 

that hardly used and had little benefit from products containing these harmful contaminants, are 

among the most highly exposed groups to these contaminants anywhere on the planet - has resulted 

in the so-called “the Arctic dilemma”. The marine food chain is rich in fat, which provides energy as 

well as essential vitamins for humans. POPs accumulate in the blubber and mercury in the meat of 

Arctic marine organisms - two main components of a diet that can be a key to survival under the 

harsh conditions that exist in the Arctic. 

The last eight years have been among the warmest years ever recorded in the Arctic since 1880. The 

-37 -



melting of the Greenland ice sheet and Arctic mountain glaciers and ice caps have increased over the 

last decades, the permafrost is thawing and the sea ice has been thinner and the extent of the summer 

sea ice reduced since satellite observations started in the 70-ties. Combined effects with Short Lived 

Climate Forces (black carbon, ozone, etc.) and feedback mechanisms (reduced albedo and increased 

heat adsorption) have been documented in the latest reports. Climate models predict temperature 

increases that may have a dramatic effect on the ice and snow conditions in large parts of the Arctic 

on time scales as short as a few decades. The melting of multiyear land ice and thawing of 

permafrost is remobilizing contaminants that has been deposited. AMAP has also reported an 

interesting link between climate change and the transport of contaminant and precipitation over the 

Arctic – combined effects. In May this year AMAP delivered the first assessment on Arctic Ocean 

Acidification (AOA). 

The climate change is affecting the Northern areas and it is creating challenges and opportunities. 

Challenges for the local people to continue the traditional life style, e.g. when sea ice is no longer 

close to the coast bring seals to the hunters, and then change in snow and permafrost are affecting 

terrestrial ecosystems and thereby herding, hunting and food storage. Opportunities are for increased 

sea transport, mining and oil and gas exploration and exploitation, tourism, etc. 

The results from AMAP have played a significant role in the establishment of international protocols 

and conventions to handle pollution, e.g. the Århus protocol and the Stockholm convention. AMAP 

has established a close cooperation with UNEP Chemicals to achieve a better control for global 

emission of mercury and a new global agreement to reduce emission of mercury will be signed this 

autumn – the Minamata agreement. 

AMAP is at present implementing a scientific project assessing the combined effects of climate 

change and contaminants on human health – the ArcRisk project to be presented in January 2014. 

AMAP together with international organizations has put priority on analysing the combined effects 

of several stressors or drivers on Arctic ecosystems, the human health and the societies. We intend to 

perform a significant work on the effects and adaptation to the Arctic Change issue the next five 

years. 

All AMAP assessment reports are available from the AMAP web site www.amap.no . 

-38 -



(PL8) 

SPECTROSCOPY UNDER ICE 

Carlo Barbante 

- Institute for the Dynamics of Environmental Processes –CNR ,University of Venice, Italy 

- Department of Environmental Sciences, Informatics and Statistics, University of Venice, Italy 

- Centro Linceo interdisciplinare B. Segre, Accademia Nazionale dei Lincei, Rome, Italy 

Polar ice caps are among the best archives of atmospheric composition of the past. Analysing the 

snow layers continuously deposited during centuries and millennia, it is possible to reconstruct the 

chemical composition of the atmosphere of our planet. Many chemical species are entrapped in 

gaseous or particulate phases into the snow and ice and thanks to sophisticated analytical techniques 

we are able to quantify their fluxes on the Earth’s surface. In addition, ice caps sometime conceal 

enormous undisclosed subglacial lakes, buried under hundreds meters of ice, which have preserved 

fossil liquid water for millions of years. 

The analysis of these matrices, the purest water on the Earth’s surface, poses a real challenge to 

analytical chemists that have to develop ultrasensitive analytical methods and stringent protocols to 

avoid sample contamination. 

In this talk I will review the recent developments in the speciation analyses of these ultra-clean 

matrices. In particular I’ll present a novel method coupling a high-performance liquid 

chromatography with ion chromatography and inductively coupled plasma mass spectrometry, 

which allows the determination of iodine (I) and bromine (Br) species (IO 3 − , I − , Br − , BrO 3 − ). Iodine 

and bromine species participate in key atmospheric reactions including the formation of cloud 

condensation nuclei and ozone depletion. Additional examples on the state of the art in this field of 

research will also include the iron speciation analysis using Collision Reaction Cell-Inductively 

Coupled Plasma-Mass Spectrometry (CRC-ICP-MS) that we have recently applied to Antarctic ice 

samples. This has shown the importance of moving a step forward from the traditional elemental 

analyses in snow and ice cores, applying the elemental speciation approach to these extremely 

diluted chemical matrices. 

-39 -



(PL9) 

BIOLUMINESCENT ECOLOGICAL ASSAY. FEATURES AND SCOPE OF 

APPLICATIONS 

Nadezhda Kudryasheva 1,2 

1 Institute of Biophysics SB RAS, Akademgorodok, 50/50, Krasnoyarsk, 660036, Russia 

2 Siberian Federal University, Svobodniy Pr., 79, Krasnoyarsk, 660041, Russia 

e-mail: n_qdr@yahoo.com 

Luminous marine bacteria can emit green light as a result of enzymatic chemiluminescent (i.e. 

bioluminescent) reactions involved in metabolic processes. Bacterial bioluminescent spectra are 

wide and asymmetric, their maxima are around 490-500 nm. The spectral shape is stable, but 

luminescent intensity is highly sensitive to toxic compounds. This is why bacterial bioluminescent 

assays have been widely used to monitor environmental toxicity for more than forty years, and now 

they are conventional and important biotechnological applications of the bioluminescence 

phenomenon. The tested parameter here is the luminescent intensity that can be easily measured 

instrumentally. The advantages of bioluminescent assays are high sensitivity, simplicity and rapidity 

of measurements (1–3 min), and availability of simple devices to register toxicity. Bioluminescent 

assay systems can be based on biological objects of different levels of organization – bacteria-based 

or enzyme-based bioassays, providing for a study of the effects of toxic compounds on cells or 

enzymes, respectively. 

Bioluminescent assays are classified as biological assays. Interrelations between biological and 

chemical assays have been intensively discussed till now. 

As a matter of fact, the main feature of all bioassays is an integral response that accounts for nonadditivity 

of the effects of numerous environmental pollutants and natural components. It implies 

that the toxic effect of a sum of compounds can be higher or lower than the sum of the effects of 

these compounds taken separately. Chemical analyses per se do not evaluate hazard to living 

organisms; they take no account of non-additivity of the effects and differences in the sensitivity of 

various organisms. Additionally, in should always be implied that chemical assays were initially 

calibrated using a standard biological test system under standard environmental conditions. 

It is supposed that only a combination of chemical and biological methods can provide complete 

information on the ecological state of a medium. This combination should involve bioassays of 

different sensitivity to toxic compounds. Analyses of complex results of biological and chemical 

assays require understanding the mechanisms of toxic effects in organisms. 

It is known that toxic effects of exogenous compounds are determined by physicochemical 

characteristics of the compounds in aqueous solutions; the effects can be classified as physical, 

chemical and/or biochemical ones in the bioluminescent assay systems. 

Basing on a broad investigation of effects of model toxic exogenous compounds on bioluminescent 

assay systems, classification of the effects on the bioluminescent enzyme reaction is suggested. Five 

mechanisms are discussed (Fig.1): (1) change in electron-excited states’ population and energy 

transfer, (2) change in the efficiency of the S-T conversion in the presence of an external heavy 

atom, (3) change in the rates of coupled reactions, (4) interactions with enzymes and variation of the 

enzymatic activity, (5) nonspecific effects of electron acceptors. 

-40 -



Chemical reaction 

S 2 

* 

T 2 

* 

Effects of exogenous compounds: 

1. electron-excited states population 

2. S-T conversion 

3. coupled reactions 

4. enzymes 

5. electron density distribution (all stages 

of the bioluminescent process) 

S 1 

* 

hv 

T 1 

S 0 

Bioluminescent emitter 

Fig.1. Classification of effects of exogenous compounds at different stages of bioluminescent 

process. 

Effects of different groups of exogenous compounds were discussed according to the classification 

suggested. Energy transfer processes (mechanism 1) contribute to the bioluminescent intensity 

change in the presence of exogenous compounds with the energy of electron-excited states lower 

than that of the bioluminescent emitter. Fluorescent exogenous compounds of this kind can provoke 

changes in bioluminescent spectra. Iodine- and bromine-substituted exogenous compounds change 

the efficiency of the S-T conversion (mechanism 2), but the contribution of this mechanism is much 

lower than that of mechanism (4). Organic and inorganic oxidizers (quinones, metals with variable 

oxidation numbers, etc.) produce specific changes in bioluminescence kinetics: a bioluminescent 

induction period appears; its value depends on concentration and redox potential of the oxidizers. A 

competition of the oxidizers with FMN for NADH in the reaction of NADH:FMN-oxidoreductase is 

responsible for these changes (mechanism 3). Such specific kinetic changes make a bioluminescent 

enzymatic assay specific to oxidizers: oxidative toxicity of solutions can be evaluated using the 

bioluminescent induction period, while general toxicity – using the maximal luminescent intensity. 

Interactions with enzymes (mechanism 4) is a prevalent mechanism for most exogenous compounds; 

its efficiency depends on the hydrophobicity of organic exogenous compounds, atomic weight of 

haloid substituents, or electron-accepting properties of metal ions. Interactions of exogenous 

compounds with enzymes studied using time-resolved fluorescent techniques are discussed. 

Mechanism 5 is specific for solutions of polar exogenous compounds, e.g., metal salts. 

Bioluminescent assays were found to be sensitive to alpha- and beta-radionuclides. The role of 

peroxides (mechanism 3) and electron transfer (mechanism 5) in bioluminescence activation and 

inhibition in radionuclide’ solutions are under discussion. 

Acknowledgements: The work was supported by Grant from the RFBR (N 13-04-01305) and the 

Programme ‘Molecular & Cellular Biology’ of the Russian Academy of Sciences. 

-41 -



(PL10) 

FTIR SPECTROSCOPY IN MICROBIAL ECOLOGY: ‘SHEDDING IR LIGHT’ ON 

CELLULAR METABOLIC RESPONSES TO ENVIRONMENTAL FACTORS 

Alexander A. Kamnev, 

Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and 

Microorganisms, Russian Academy of Sciences, 410049 Saratov, Russia 

e-mail: aakamnev@ibppm.sgu.ru; a.a.kamnev@mail.ru 

Infrared (IR) spectroscopy, from its early decades up to now, has been used as a routine technique 

for structural analysis in materials science. The main advantage of this type of vibrational 

spectroscopy techniques representing, on the other hand, its complicacy is that virtually all major 

chemical functional groups of the sample under study contribute to the resulting spectrum. The latter 

includes not only bands featuring all possible vibration modes ‘visible’ in the IR, but also reflects all 

possible non-covalent interactions between functional groups in a sample which affect bonding 

energies and, therefore, vibrational frequencies. Moreover, IR spectroscopy is, in my opinion, one of 

the most ‘provocative’ spectroscopic techniques. While in most others a wrong methodology or 

sample preparation would result in obtaining a clearly poor or no spectrum, a ‘rich’ IR spectrum 

could almost always be recorded. However, in order for the IR spectrum to represent the real ‘state 

of the matter’, both the sample preparation and the methodology used for recording a spectrum 

should be absolutely adequate and ‘compatible’ with each other. Finally (last but not at all least!), 

the most creative and often complicated part is the interpretation of the spectrum thus obtained, 

which may appear to be quite a challenging task. 

All the aforementioned features of IR spectroscopy are even more important in modern Fourier 

transform IR (FTIR) spectroscopy featured by significantly improved instrumental capabilities, 

greatly enhanced sensitivity and signal-to-noise ratio. Its applications in biological fields, commonly 

characterised by extremely sophisticated and highly heterogeneous samples (from 

biomacromolecules to cells and tissues), yet steadily grow. For instance, while the first IR 

spectroscopic studies of microbiological objects appeared already in the middle of the XX century, 

the real development of efficient bioanalytical applications in microbiology started after the 1980s 

with FTIR spectrometers becoming more available. 

In our laboratory, for over a decade we have been conducting collaborative research on microbial 

cellular metabolic responses to various environmental factors using FTIR spectroscopy as the main 

analytical tool [1–4] or in combination with other techniques [5–7]. In this talk, representative 

examples will be given illustrating the fascinating possibilities of FTIR spectroscopy in microbial 

ecology related to analysing fine structural and quantitative modifications of major cellular 

components which reflect microbial adaptation to unfavourable conditions. These include 

modifications of cellular proteins with a redistribution of their secondary structure components as a 

response to stress factors or molecular signals; biosynthesis and intracellular accumulation of 

biopolyesters, fine changes in their structure and degree of crystallinity as a microbial adaptation 

strategy to nutritional and other stresses. 

The FTIR methodology used in these studies included the diffuse reflectance (DRIFT) mode. This 

method allows the microbiological samples under study, usually dry biomass, to be analysed without 

using highly polar matrices such as KBr and thus to avoid uncontrollable and often quantitatively 

unpredictable shifts of vibrational bands of some polar functional groups, especially those involved 

-42 -



in H-bonding. This is most important for analysing intracellular proteinaceous components, the 

secondary structure of which is formed by various types of H-bonds between polypeptide chains. 

However, for microbial intracellular polyester granules, both conventional strong H-bonding 

(involving water molecules remaining within the granules as a result of polycondensation) and weak 

C–H...O bonds play a significant role. 

Our studies mostly involved bacteria of the genus Azospirillum [1–6] which are capable of 

establishing effective associative symbioses with higher plants and therefore belong to the diverse 

family of plant-growth-promoting rhizobacteria (PGPR). This feature, together with their high 

adaptability and resistance to stresses, is of significant importance for agricultural biotechnology, 

including PGPR-assisted phytoremediation of contaminated soils. Thus, these bacteria have been 

attracting the steadily increasing attention of researchers already for over three decades. Another 

advantage of these microorganisms is that some of their ubiquitous species, e.g. A. brasilense, 

comprise different strains which occupy different ecological niches in the rhizosphere of host plants. 

Such strains may be used as model microorganisms exhibiting different ecological behaviour under 

similar stress conditions owing to their different adaptation strategies. 

The author’s research related to FTIR spectroscopy in microbiology has been supported in part 

within the recent years by grants from NATO (Projects LST.NR.CLG.981092 and ESP.NR.NRCLG 

982857), from The Siberian Health International LLC (Novosibirsk, Russia; Call for Projects, 2012) 

as well as under the Agreement on Scientific Collaboration between the Russian and Hungarian 

Academies of Sciences for 2011–2013 (Project # 28). 

1. Kamnev A.A., Sadovnikova J.N., Tarantilis P.A., Polissiou M.G., Antonyuk L.P. Microb. Ecol., 

2008, 56: 615-624. 

2. Kamnev A.A. Spectroscopy Int. J., 2008, 22: 83-95. 

3. Tugarova A.V., Kamnev A.A., Tarantilis P.A., Polissiou M.G. Eur. Biophys. J., 2011, 40 (Suppl. 

1): S240. 

4. Kamnev A.A., Tugarova A.V., Tarantilis P.A., Gardiner P.H.E., Polissiou M.G. Appl. Soil Ecol., 

2012, 61: 213-216. 

5. Kamnev A.A., Tugarova A.V., Antonyuk L.P., Tarantilis P.A., Kulikov L.A., Perfiliev Yu.D., 

Polissiou M.G., Gardiner P.H.E. Anal. Chim. Acta, 2006, 573-574, 445-452. 

6. Kamnev A.A., Tugarova A.V., Kovács K., Kuzmann E., Biró B., Tarantilis P.A., Homonnay Z. 

Anal. Bioanal. Chem., 2013, 405: 1921-1927. 

7. Kamnev A.A., Tugarova A.V., Selivanova M.A., Tarantilis P.A., Polissiou M.G., Kudryasheva 

N.S. Spectrochim. Acta Part A: Mol. Biomol. Spectrosc., 2013, 100: 171-175. 

-43 -



(PL11) 

ATMOSPHERIC DEPOSITION OF TRACE ELEMENTS ON THE LOCAL AND 

REGIONAL SCALE STUDIED BY ICPMS ANALYSIS OF MOSS SAMPLES 

Eiliv Steinnes 1 , Hilde Thelle Uggerud 2 , Torunn Berg 1 and Katrine Aspmo Pfaffhuber 2 

1 

Department of Chemistry, Norwegian University of Science and Technology, NO-7491 

Trondheim, Norway 

2 Norwegian Institute for Air Research, NO-2027 Kjeller, Norway 

e-mail: eiliv.steinnes@chem.ntnu.no 

Naturally growing moss is a useful substrate for large-scale studies of atmospheric deposition of 

trace elements. Starting in 1977 the temporal trends of trace element deposition has been studied 

every five years in Norway using this approach. Since 1990 ICPMS has been the analytical 

technique of choice for this purpose, and in the most recent survey in 2010 the geographical trends 

were reported for as much as 53 elements in Hylocomium splendens moss samples from 464 sites 

situated all over the country. Since 2000 results from these campaigns are reported to the joint 

European deposition survey employing moss biomonitoring. Extensive contamination by a number 

of metals in the south of Norway from trans-boundary pollution has been substantially reduced over 

time. 

Starting in 2000 the moss sampling technique was also used for mapping metal deposition patterns 

around 15 major industrial point sources, including aluminium and ferroalloy smelters, cement mills, 

and copper-nickel smelters. The most severe contamination was observed in the vicinity of two 

Russian smelters situated close to the Norwegian border. Appreciable deposition of some metals was 

also observed locally around metal industries at Mo i Rana and Odda. 

Results from such multi-element studies of moss samples do not necessarily represent contribution 

from air pollution only. Previous studies by the authors comparing concentrations in moss with 

atmospheric deposition rates from precipitation sampling over a corresponding time period showed 

significant positive correlations for trace elements such as V, As, Cu, Zn, Mo, Cd, Sb, Tl, Pb, and 

Bi. For some elements the content in moss is affected by uptake from the growth substrate, as in the 

case of K, Ca, Mn, Rb, Cs, Ba, and partly Cu and Zn. Another source is local windblown soil dust, 

such as for Ti, Fe, REE, Th, and U. Finally contribution from the marine environment is important 

for the supply of some elements to the moss, such as B, Na, Mg, and Sr. Principal component factor 

analysis is a convenient tool for distinguishing contributions of elements from different pollution 

sources and separating natural and anthropogenic contributions to the element distribution in moss 

samples. 

-44 -



(PL12) 

MASS SPECTROMETRY MADE EASY: THE QUEST FOR SIMPLICITY IN FORENSIC, 

FOOD, PHARMACEUTICAL, ENVIRONMENTAL, MEDICAL AND BIOCHEMICAL 

ANALYSIS 

Marcos N. Eberlin 

Universidade Estadual de Campinas, Brazil 

Mass spectrometry is generally viewed as a highly complex and demanding technique, full of 

difficulties and apprehensions, particularly for the non expert. Ease and simplicity are therefore 

infrequently used descriptors of MS but a series of revolutionary developments are turning a 

complex technique into a model of simplicity making MS easier than ever. Focusing on spray-based 

ambient desorption/ionization techniques, I will illustrate using applications in forensic, food, 

pharmaceutical, environmental, medical and biochemical analysis, that previously unthinkable goals 

for MS, that is: 

a) to bring it to the real world open atmosphere environment; 

b) to perform fast, selective and highly sensitive chemical and biochemical MS analysis with ease 

while 

c) avoiding pre-separation and sample work-up for samples at their natural environment 

And therefore, at the end, that the task of making MS accessible at wherever MS is needed and by 

whoever needs it – has become fully feasible. 

The applications that will be highlighted will illustrate that, without compromising the unique 

combination of high speed, selectivity, sensitivity and separation competences, simplicity has 

become a new MS attribute – a 5th “S” in the unique 5S set of MS trademark features. 

Immediate MS can now also be performed by non-specialists with ease and simplicity using no preseparation 

and sample work-up protocols. We can now offer mass spectrometry to the “masses” – 

wherever it is needed and to whoever needs it. 

-45 -



(PL13) 

CONFOCAL SPECTRAL IMAGING TECHNIQUE IN THE DEVELOPMENT OF PHOTO- 

AND NEUTRONSENSITIZERS FOR ANTICANCER THERAPY 

Alexey V. Feofanov 1,2 , Anastasija V. Efremenko 1,2 , Anastasija A. Ignatova 1,2 , George V. Sharonov 1 

and M.V. Astapova 1 

1 Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences, ul. 

Miklukho-Maklaya 16/10, 117997 Moscow, Russia 

2 Biological Faculty, Lomonosov Moscow State University, Vorobyevi Gori 1, Moscow, 119992, 

Russia 

e-mail: avfeofanov@yandex.ru 

Photosensitizers and neutronsensitizers are compounds that are non-toxic themselves for cells, but 

able to accumulate in cancer cells and kill them in the course of irradiation with photons and 

neutrons, respectively. Photosensitizers are essential component of photodynamic therapy (PDT). 

Photoinduced cell death occurs because of generation of reactive oxygen species by a 

photosensitizer. Boron-bearing neutronsensitizers are used for boron neutron capture therapy 

(BNCT). Neutronsensitizer that contains nonradioactive 10 B isotopes interacts with thermal 

neutrons, and excited boron nuclei break into high energy α and 7 Li particles, which destroy cells. 

Efficiency and selectivity of cancer treatment depends critically on enhanced accumulation of such 

sensitizers in cancer cells as compared to normal cells. Development of new improved photo- and 

neutronsensitizers is an actual pharmaceutical task. 

photons 

3 O 2 

H 

H 3 C 

NH 

N 

H 

H 3 CO 2 C 

H 3 CO 2 C 

neutrons 

N 

HN 

HN 

linker 

O 

Reactive oxygen species 

other than 1 O 2 

fluorescen 

1 O 2 

Photodynamic therapy 

10 В 

α 

7 Li 

γ 

Boron neutron capture 

680 700 720 740 760 780 

, nm 

680 700 720 740 760 780 

, nm 

Photosensitizers are fluorophores that absorb light and fluoresce in red and far region (650-850 nm). 

Therefore, fluorescence microscopy can provide useful data about accumulation and distribution of 

photosensitizers in cells and tissues, can greatly help in a structural optimization of new 

photosensitizers. 

Since many porphyrin-based photosensitizers were found to accumulate in malignant cells, an idea 

appeared to conjugate boron nanoparticles with porphyrin derivatives for improved boron delivery in 

cancer cells. And again, fluorescence microscopy can assist in the development of such fluorescent 

nanoconjugates-neutronsensitizers. 

Microenvironment and molecular interactions of fluorophores affect quantum yield, maximum and 

shape of fluorescence spectra. Therefore, spectral characteristics of fluorescent sensitizers should be 

-46 -



known in biological environment in order to use correctly fluorescence techniques in the studies of 

sensitizer cellular uptake, localization, pharmacodynamics and pharmacokinetics. A powerful tool 

being able to resolve this problem is a confocal spectral imaging (CSI) technique. 

The CSI technique measures a two-dimensional set of spectra with a three-dimensional spatial 

resolution from a tissue section or an intact living cell treated with a sensitizer. After, a 

decomposition procedure is applied: each original spectrum is decomposed into a sum of the 

reference spectra with appropriate coefficients. The reference spectra come from detailed in vitro 

study of spectral changes induced by environmental factors and molecular interactions of fluorescent 

sensitizer. The decomposition coefficients are used to create spectral images describing subcellular 

(tissue) quantitative distribution of the sensitizer. 

The CSI technique is utilized by us in order to: 

analyze and compare ability of sensitizers to penetrate in cancer cells; 

identify and map molecular interactions of sensitizers in cells; 

quantify accumulation, localization and retention of sensitizers in cells and tissues; 

reveal chemical modifications of sensitizers in cellular environment; 

analyze photostability of sensitizers. 

The CSI technique helps us to perform a multiparametric selection of leading sensitizers, opens a 

way to their structure-functional optimization. Features of the CSI technique are illustrated with our 

data obtained in the course of development and studies of advanced sensitizers for photodynamic 

and boron neutron-capture anticancer therapies. 

-47 -



(PL14) 

NEW DEVELOPMENTS IN DISEASE RECOGNITION BY INFRARED AND RAMAN 

SPECTROSCOPY AND MICROSCOPY: PRESENT STATUS AND FUTURE PROMISSES 

János Mink 1,2 , Veronika Gombás 2 , Judith Mihály 1 , Csaba Németh 1 and László Hajba 2 

1 Institute of Molecular Pharmacology, Research Centre for Natural Sciences, Hungarian Academy 

of Sciences, H-1525 Budapest, Hungary. 

2 

Research Institute of Chemical and Process Engineering, Faculty of Information 

Technology, University of Pannonia, H-8201 Veszprém, Hungary. 

e-mail: jmink@chemres.hu 

The fast development of infrared and Raman spectroscopic instrumentation during the past decades 

has made possible their application to complex problems of biology and medicine. With the 

availability of ultraviolet and near infrared laser excitation to replace the traditional visible lasers, 

the problem of background fluorescence of biological Raman samples can be avoided. The new 

methods of spectral manipulation and decoding the enormous informational content of vibrational 

spectra is aided by the availability of high-power computer workstations and advanced algorithms 

for data processing. The progress has been especially manifested in the field of cancer diagnostic. In 

this paper we try to summarise the progress achieved over the past ten years in applying vibrational 

spectroscopy to problems of medical diagnostic including our novel achievements. 

It was recently discovered in our laboratory that the infrared spectra of human skin (measured on 

forearm) and hair fibre showed definite correlations with the general physiological condition of the 

human organism. Especially strong spectral deviations were observed in case of cancerous patients 

even in very early stage of the illness. More than 3000 patients have been examined and based on 

our spectral library and developed special spectral data processing it can be suggested as a good 

screening methodology adequate for mass measurements. Both the developing process of the certain 

illness and the process of recovery can be clearly monitored. Future perspectives and limitations will 

be discussed. 

Beside the “screening“capabilities of the general health condition unique illness specific infrared 

signals have been observed by skin measurement of diabetic patients. Due to the great interest in 

dermatology and in cosmetic industry, reflective FTIR spectroscopic studies of human skin have 

been widely published ([1-3] and references therein). Accordingly to our best knowledge there are 

no publications about detection of diabetes based on mid-infrared spectra of human skin but great 

number of papers report about human blood measurements. 

Infrared spectra were compared for 39 patients suffering from diabetes and 59 healthy persons by 

principal component analysis (PCA). The chemometric analysis results in separation of healthy and 

diabetic patient’s spectra, i.e. the spectral features of healthy and diabetic patients resulted in plot of 

scores that fall in two sets within their respective group. The ‘infrared diagnosis’ results were 

compared with the genuine medical diagnosis, and among the 39 patients’ skin samples no one was 

misclassified. In some cases diabetes was detected in very early stage. Consequently FTIR detection 

can be used for prevention, early diagnosis and monitoring the status of diabetes as well. 

1. Ch. Xiao, D.J. Moore, C.R. Flach, R. Mendelsohn, Vibrational Spectroscopy, 38, 151-158, 2005. 

2. R. Mendelsohn, C. R. Flach and D. J. Moore, Biochimica et Biophysica Acta (BBA) - 

Biomembranes, 1758, 923-933, 2006. 

3. A. N. Crowson, Modern Pathology 19, S155–S163, 20064. G. Hosafci, O. Klein, G. Oremek, W. 

Mantele, Anal. Bioanal. Chem., 387, 1815-1822, 2006. 

-48 -



(PL15) 

METABOLIC FINGERPRINTING VIA MASS SPECTROMETRIC ANALYSIS OF 

EXHALED BREATH 

Renato Zenobi, Pablo Martinez-Lozano Sinues, Lukas Bregy, Xue Li, and Jingjing He 

Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093 Zurich, Switzerland. 

e-mail: zenobi@org.chem.ethz.ch 

Ambient ionization mass spectrometry offers attractive new perspectives for real-time, on-line 

metabolic fingerprinting of the exhaled breath of patients as well as healthy individuals. Ion 

formation at ambient pressure avoids problems with limited detection sensitivity and scope arising 

from introducing breath into a low pressure environment for ionization. We are using a nanoESIbased 

secondary electrospray ionization (SESI) as well as a dielectric barrier discharge (DBD) 

plasma ionization [1] maintained in an active sampling capillary to achieve efficient ambient 

ionization of compounds in exhaled breath. ppb … ppt limits of detection can be achieved, and 

compounds with molecular weights up to 400 Da are observed. 

With this technology, several interesting questions about metabolic signatures in the body can be 

addressed: Is there a core pattern for individual phenotypes visible in mass spectrometric 

“breathprints” [2]? Can diurnal changes be monitored via exhaled breath [3]? Can diseases be 

diagnosed via exhaled breath, and if yes, which ones? Can proper drug use (or drug abuse) be 

detected via analysis of the chemical composition of exhaled breath? These studies have obvious 

ramification for using exhaled breath as a non-invasive alternative to the analysis of blood or urine 

in medical diagnosis, doping control, forensics, and other areas. 

Figure: photograph 

of the DBD source 

mounted on the inlet 

of a Synapt G2S 

instrument. 

Capillary 

containing 

DBD 

Breath 

inlet 

References: 

[1] M.M. Nudnova, L. Zhu, and R. Zenobi, Active Capillary Plasma Source for Ambient Mass 

Spectrometry, Rapid Commun. Mass Spectrom. 26, 1447-1452 (2012). 

[2] P. Martinez-Lozano Sinues, M. Kohler, and R. Zenobi, Human Breath Analysis May Support the 

Existence of Individual Metabolic Phenotypes. PLoS ONE 8(4): e59909. 

doi:10.1371/journal.pone.0059909 (2013). 

[3] P. Martinez-Lozano Sinues, M. Kohler, and R. Zenobi, Monitoring Diurnal Changes in Exhaled 

Human Breath, Anal. Chem. 85, 369-373 (2013). 

-49 -



(PL16) 

ACCURATE MEASUREMENT OF IRON METABOLISM BIOMARKERS: NEW TOOLS 

AND REMAINING CHALLENGES 

Maria Montes-Bayón, Tobias Konz, Alfredo Sanz-Medel. 

Department of Physical and Analytical Chemistry. Faculty of Chemistry. University of Oviedo. 

Iron balance is tightly regulated in our organism and such regulation occurs exclusively at the site of 

absorption, as there is no physiological process to excrete the iron excess. The majority of iron 

absorption occurs via enterocytes in the proximal small intestine and is then transported to other 

sites within the body by transferrin, the main Fe transporter in human serum. Ferroportin is a newly 

identified iron efflux pump that mediates the export of iron from the enterocyte into the blood stream 

for transferrin binding. While much remains to be discovered regarding the control of iron balance, 

hepcidin, a recently discovered 25 amino acid protein, is believed to be critical to this process. 

Hepcidin serves as a negative regulator, and when elevated, results in reduced intestinal iron 

absorption and macrophage iron release [1]. 

Tranferrin carries Fe to, among others, the liver where the metal is stored in Ferritin. Ferritin makes 

iron available for critical cellular processes while protecting lipids, DNA, and proteins from the 

potentially toxic effects of iron. Alterations in ferritin are seen commonly in clinical practice, often 

reflecting perturbations in iron homeostasis or metabolism. Therefore, for a better understanding of 

the iron metabolism disorders the development of analytical strategies that permit the specific 

monitoring of new biomarkers with high accuracy and precision in mandatory. In this work we will 

illustrate the new tools for characterization of hepcidin based on mass spectrometric (MS) and 

immunochemical assays. In addition, the quantitative determination of ferritin in human serum as 

well as its Fe binding characteristics will be introduced as potential specific biomarkers of iron 

metabolic diseases. 

[1] Kroot JJC, Tjalsma H, Fleming RE, Swinkels DW (2011) Clin Chem 57:1650-166 

-50 -



(PL17) 

SALDI MASS-SPECTROMETRY: PRINCIPLES AND APPLICATION FOR DRUG 

ANALYSIS 

Alexander Grechnikov 

Vernadsky Institute of Geochemistry and Analytical Chemistry of RAS, Kosygin str., 19, 119991 

Moscow, Russia 

e-mail: grechnikov@geokhi.ru 

The development of laser-assisted mass spectrometric techniques has resulted in new opportunities, 

approaches, and methods. Surface-Assisted Laser Desorption-Ionization (SALDI) is an excellent 

example, which holds great promise for analytical applications. In SALDI the gas-phase ions are 

formed from molecules deposited on a particular surface substrate that is irradiated with a pulsed 

laser. This process does not require the entrainment action of an added matrix compound for 

desorption and ionization. 

This lecture consists of three parts. In the first part the main factors determining the analytical 

performance of SALDI are reviewed and analyzed. These factors are the following: 

- electronic structure of SALDI active materials; 

- laser irradiation parameters; 

- surface chemistry of SALDI active substrates; 

- basicity of analyte. 

The results and experiences from rather extensive SALDI experiments are reported. A very strong 

dependence of SALDI ion generation on the electronic, physical, and chemical properties of the 

substrates are demonstrated. The sensitivity of silicon based SALDI for about 50 compounds with 

varying proton affinity ranging from 800 to 1000 kJ/mol was determined, and it was found that the 

ion signal showed an exponential dependence on compound proton affinity. Based on experimental 

results and quantum chemical calculations, a model for SALDI ion generation from silicon surfaces 

is proposed. 

The details about the current state of SALDI instrumentation will be discussed in the second part of 

the lecture. Main concepts of SALDI realization in a comparatively simple, affordable, and highly 

efficient instrument are reviewed. The traditional approach for SALDI analysis is the use of a 

standard MALDI ion source. Two novel strategies for the construction and application of SALDI 

instruments are presented. The first strategy is based on a combined gas chromatography (GC) – 

SALDI time-of-flight mass-spectrometry. The second one includes novel methods of surface 

activation and sample deposition with the rotating ball inlet. It is shown that SALDI has excellent 

potential both for powerful liquid chromatography-SALDI MS and gas-phase SALDI MS analysis. 

The SALDI technique is applicable to a broad range of analytical problems and areas, including 

ambient air analysis, organic mass spectrometry and biochemical analysis. The third part of the 

lecture is focused mainly on drug analysis. Various examples including the rapid screening of 

pharmaceutical products without any sample pretreatment, GC-SALDI mass spectrometry of 

amphetamine-like drugs, protein analysis and the determination of metal-organic complexes are 

presented. It is shown that with simple preparation steps, biological samples can be analyzed using 

the SALDI technique with the detection limits at a subfemtomole level. 

This work was partially supported by the Program for basic researches of the Presidium of RAS №9. 

-51 -



(PL18) 

SIMS AND THE SINGLE CELL 

Vic Norris 1 Ghislain Gangwe Nana 2 , Armelle Cabin 2 , Jean-Nicolas Audinot 3 , David Gibouin 2 , 

Rabah Boukherroub 4 , and Camille Ripoll 2 

1 Theoretical Biology Unit, University of Rouen, 76821, Rouen, France 

2 Equipe Assemblages Moléculaires: Modélisation et Imagerie SIMS, Laboratoire MERCI EA 3829, 

University of Rouen, 76821, Rouen, France 

3 

Institut de Recherche Interdisciplinaire (IRI, USR-3078) and Institut d’Electronique, de 

Microélectronique et de Nanotechnologie (IEMN, CNRS-8520), Cité Scientifique, Avenue 

PoincaréB.P. 60069, 59652 Villeneuve d’Ascq, France 

4 

Département Science et Analyse des Matériaux, Centre de Recherche Public Gabriel Lippmann, 

4422 Belvaux, Luxembourg 

e-mail: Victor.Norris@univ-rouen.fr 

Secondary Ion Mass Spectrometry (SIMS) is particularly suited for addressing a number of 

fundamental problems in biology. One of these problems is how cells reconcile the conflicting 

strategies required to grow in favourable conditions and to survive in harsh conditions. Using the 

model bacteria, Bacillus subtilis and Escherichia coli, we find evidence that a partial solution to this 

problem occurs at the level of the population. Cells were labelled with 13 C-glucose and 15 N- 

ammonium chloride as sources of carbon and nitrogen for times ranging from a tenth of a generation 

to three generations; this was followed by the use of a NanoSIMS 50 to locate the incorporated 

isotopes and to obtain isotope ratios. This dynamic SIMS analysis revealed a remarkable metabolic 

heterogeneity consistent with (1) some cells growing rapidly to profit from the availability of 

nutrients and (2) other cells growing slowly in readiness for an environmental challenge. These 

results complement other results revealing population heterogeneity obtained using fluorescence 

microscopy to localise RNA and proteins, as in the case of the toponome, and using optical 

microscopy and nanodevices to study growth rates, as in the case of the suspended microchannel 

resonator. 

Where does this heterogeneity come from? This question is related to the more general problem of 

how cells manage to generate coherent, reproducible behaviours (i.e., phenotypes) at all; the root of 

the problem here is that even bacterial cells can produce tens of thousands of types of molecules and 

macromolecules and therefore appear to be able to generate hyperastronomical numbers of 

combinations of these products; the result ought to be a phenotype space so vast that coherent 

phenotypes rarely recur. 

A partial solution to this problem of phenotype space may involve the extended assemblies of 

molecules and macromolecules, known as hyperstructures, which have been proposed to constitute a 

level of intracellular organisation between the lower level of the gene or protein and the higher level 

of the cell itself. This solution would help with the phenotype problem by attributing behaviour to 

the action of a much smaller number of combinations of scores of hyperstructures. Again, using 15 N- 

labelling and detection on the 50 nm scale by dynamic SIMS, we find evidence in a population of E. 

coli growing in steady state that hyperstructures exist in different metabolic states within the same 

cells. We argue that this is consistent not only with the hypothesis that hyperstructures limit 

phenotype space but also with the hypothesis that hyperstructures control the bacterial cell cycle. 

The cell cycle in bacteria consists essentially of three events: the initiation of replication of the 

chromosome, the segregation of the chromosomes, and division of the cell. Although the cell cycle 

-52 -



has been intensively studied, surprisingly, the nature of the fundamental control of the cell cycle 

remains unknown. One possibility is that this control is based on the dynamics of hyperstructures 

and, further, that the cell cycle itself serves to generate the heterogeneous population needed to 

ensure growth in heaven and survival in hell. By combining the isotope labelling of DNA, the 

combing of this DNA on silicon surfaces, caesium flooding and analysis by SIMS, we have 

developed a technique that may allow, on the scale of 150 base pairs, the quantification of DNA 

replication in individual chromosomes and the localisation of the molecules and macromolecules 

that bind to the origin of replication and to other regions on the DNA. This techique should therefore 

facilitate the testing of hypotheses for the control of the initiation of DNA replication. 

-53 -



(PL19) 

(HIGH RESOLUTION) 2 MALDI IMAGING: RELIABLE MOLECULAR INFORMATION 

AT CELLULAR RESOLUTION 

Andreas Römpp and Bernhard Spengler 

Institute of Inorganic and Analytical Chemistry, Justus Liebig University, Schubertstrasse 60, D- 

35392 Giessen, Germany 

e-mail: Andreas.Roempp@anorg.chemie.uni-giessen.de 

Mass spectrometry imaging is a versatile and powerful analytical technique. Our work is focused on further 

increasing the biologically relevant information that can be obtained by mass spectrometry imaging. Here we 

present a number of improvements in instrumentation, sample preparation, measurement parameters and data 

processing. The discussion will be based on phospholipids in mammalian samples, but the method was also 

successfully used for other applications including insect and plant specimen. 

MS imaging experiments were performed with a high resolution atmospheric-pressure imaging source 

[Römpp et al., 2010] attached to ‘LTQ Orbitrap’, ‘Exactive Orbitrap’ or ‘Q Exactive’ mass spectrometers 

(Thermo Scientific GmbH, Bremen). Pixel size was between 2 and 10 µm. Mass accuracy was better than 2 

ppm (root mean square) under imaging conditions. Tentative identification based on accurate mass was 

confirmed by on-tissue MS/MS experiments. 

A dedicated sample preparation protocol was established for the analysis of cell cultures. Phospholipids and 

smaller metabolites such as nucleic acids and cholesterol were imaged in single cells. A full metabolic profile 

was obtained from a single 7 µm pixel. Phospholipids were investigated in detail in mouse brain and human 

tumor samples. Proteins were analyzed after on-tissue tryptic digestion at 25 μm pixel size. MS image 

analysis for all these experiments showed excellent agreement with histological staining evaluation. In 

addition it provided highly specific molecular information. In many cases signals with very similar mass 

(∆m/z



(PL20) 

NEW APPROACHES, PLASMAS, AND INSTRUMENTATION FOR ATOMIC 

SPECTROMETRY 

Steven J. Ray 1 , Alex Graham 1 , Elise Dennis 1 , Christie Enke 2 , Andrew Schwartz 1 , Charles Barinaga 3 , 

Anthony Carado 3 , David Koppenaal 3 , and Gary M. Hieftje 1 . 

1 Department of Chemistry, Indiana University, Bloomington, IN 47405 

2 Department of Chemistry, University of New Mexico, Albuquerque, NM 87131 

3 Pacific Northwest National Laboratory, Richland, WA, 99352 

e-mail: sjray@indiana.edu 

It is a truth universally acknowledged that the introduction of any new and successful 

analytical technique will not only address some current need of chemical measurement science, but 

will also cause a new and even more challenging set of chemical questions to be formulated. In 

many instances, these new chemical questions will require novel analytical approaches to be 

developed to address them, thus closing one of the catalytic loops that drives science forward. In 

this presentation, several new analytical instrumentation approaches under developed to speak to 

pressing needs in atomic spectroscopy will be examined. 

The first example examined will be a new type of mass analyser known as the distance-offlight 

mass spectrometer (DOFMS). The concept behind DOFMS is best explained by comparison 

with traditional time-of-flight mass spectrometry (TOFMS). Time-of-flight mass analyzers measure 

the m/z of an ion by imparting the same energy to all ions and then measuring the time required for 

each m/z to traverse a known distance and arrive at a single detector. In contrast, DOFMS measures 

the m/z of an ion by measuring the distance each ion travels during a set time period. More 

specifically, ions accelerated to a constant momentum separate in space according to their various 

m/z-dependent velocities, with ions of lower m/z traveling longer distances than ions of greater m/z. 

At a specific instant after acceleration, all m/z will achieve a sharp spatial focus and can then be 

directed onto the surface of a position-sensitive ion detector where their m/z is determined based 

upon location. 

The DOFMS 

strategy offers a number of 

significant benefits. Like 

TOFMS, DOFMS is 

architecturally simple, rapid, 

and has an unlimited m/z 

range. However, DOFMS is 

able to employ new solidstate 

array ion detectors to 

great advantage, providing 

greater detection efficiency 

and dynamic range than 

typical TOFMS, and 

obviating the need for fast 

electronics and timing 

circuits. As important, the 

DOFMS strategy permits 

new experiments to be 

performed not possible with 

Figure 1: The Distance of Flight mass spectrometer 

typical TOFMS. The theory 

-55 -



of operation and experimental advantages of DOFMS will be discussed, and the analytical 

performance of this new type of mass spectrometer will be described 

In a second discussion, a novel alternative to the conventional plasma excitation sources commonly 

used for atomic emission spectroscopy will be examined. The solution-cathode glow discharge 

(SCGD) is a novel direct-current atmospheric pressure glow discharge source sustained in the 

ambient atmosphere under ambient conditions. The simple approach obviates the need for complex 

electronics and expensive plasma gases, and makes the SCGD particularly attractive for use in 

remote or low-cost instrumentation. Illustrated in Figure 2, the SCGD is an atmospheric pressure 

glow discharge that is sustained in the open atmosphere between an anode pin and a sample solution, 

which acts as the discharge cathode. Because the plasma lies directly atop the liquid surface, the 

plasma itself is responsible for sampling analyte from the solution. This same plasma then 

subsequently desolvates and atomizes the analyte and excites the constituent atoms to be observed 

by atomic emission spectroscopy. 

The SCGD offers a number of significant advantages over 

conventional plasma emission techniques in AES. Introduction of 

the analyte solution into the plasma occurs by a unique and direct 

sputtering mechanism, which obviates the need for a sample 

nebulization step. This direct solution sampling promises high 

efficiency and rapid response, and because the liquid surface of the 

flowing solution cathode is self-renewing, memory effects are 

reduced. Moreover, and unlike many conventional commercialized 

plasma sources, the SCGD operates in the open atmosphere, 

employs a very simple experimental setup, requires no compressed 

gases, and consumes only 70W of power. Thus, it is well suited for 

portable instrumentation, and its simple construction and glow 

Figure 2: A Photograph of 

the SCGD During the 

Analysis of a Tl solution. 

discharge structure make it amenable to miniaturization. 

Experimental construction, spectroscopic characteristics, and 

analytical figures of merit of this SCGD-AES instrument will be 

presented. 

-56 -



(PL21) 

PULSED GLOW DISCHARGE TIME OF FLIGHT MASS SPECTROMETRY: A 

POWERFUL AND VERSATILE TOOL FOR ELEMENTAL AND MOLECULAR DEPTH 

PROFILE ANALYSIS 

Rosario Pereiro 1 , Beatriz Fernández 1 , Nerea Bordel 2 and Alfredo Sanz-Medel 1 

1 Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo. C/ 

Julian Claveria, 8. 33006 Oviedo. Spain. 

2 Department of Physics, University of Oviedo, c/ Gonzalo Gutiérrez Quirós. 33600 Mieres. Spain. 

e-mail: mrpereiro@uniovi.es 

The coupling of radiofrequency pulsed glow discharges (RF-PGDs) to time of flight mass 

spectrometry (TOFMS) provides an amazing amount of data because the TOFMS time-gated 

detection permits to collect complete mass spectra produced by different ionization mechanisms 

within each single glow discharge pulse cycle. This emerging technique makes possible to obtain 

multielemental depth-profiles with high depth resolution and good sensitivity, isotope ratio 

measurements, as well as the simultaneous production of elemental, structural and molecular 

information. As a result, the use of RF-PGD-TOFMS allows the analytical characterization of a high 

variety of samples. Moreover, the analytical capabilities of the RF-PGD-TOFMS for some 

applications can be considered as really unique. 

Considering the promising analytical performance brought about by RF-PGD-TOFMS, further 

research is still welcomed to achieve the best performance of this direct solid analysis tool. In this 

context, and having in mind that the development of an optimum GD design is crucial, the 

evaluation of different GD sources will be presented. Also, the analytical potential of RF-PGD- 

TOFMS will be shown through an overview of recent applications including: 

glasses coated with films a few nanometers thick, 

photovoltaic materials including thin film solar cells based on amorphous silicon, and quantitative 

depth profiling of ultra low energy implants, 

nanostructured materials, such as metallic nanowires, grown by template-assisted electrochemical 

deposition procedures in self-ordered nanoporous alumina, 

polymeric samples, e.g. screening of polymer-based coatings containing brominated flame retardants 

and analysis of conductive polymeric coatings. 

It is expected that in the next years the routine use of RF-PGD-TOFMS will become commonplace. 

The traditional application field of GD spectrometry is elemental direct solid analysis. Here, RF- 

PGD-TOFMS is expected to become a common tool for the characterization of innovative materials 

allowing for the fast quantitative multielemental (major, minor and trace elements) and isotopic 

depth-profile analysis of thin films and dopants distribution, and to investigate the presence of 

surface contaminants. Also, the capabilities of RF-PGD-TOFMS to provide molecular information 

directly from the solid-state call for further research to better define its application niche in those 

important fields. 

-57 -



(PL22) 

COHERENT HIGH ENERGY X-RAY MICROSCOPY: A NEW TOOL TO STUDY 

MESOSCOPIC MATERIALS 

Irina Snigireva and Anatoly Snigirev 

European Synchrotron radiation Facility (ESRF), 38043 Grenoble France 

e-mail: irina@esrf.fr 

In this talk we present a novel X-ray microscopy technique to study mesoscopically structured 

materials, employing compound refractive lenses. The obvious advantage of using lens methodology 

is the possibility to retrieve high resolution diffraction pattern and real-space images in the same 

experimental setup [1-3]. Methodologically the proposed approach is similar to the studies of 

crystals by high resolution transmission electron microscopy. 

The microscope operates under a coherent illumination where a diffraction pattern of the specimen is 

formed in the back focal plane of the condenser and an inverted two-dimensional image of the object 

is formed by objective lens in the image plane [4]. The diffraction mode is used to investigate the 

crystal structure over the macroscopic distances and to orient the crystals parallel to the low index 

direction to perform high resolution imaging on the local scale. The structural image formation relies 

on phase contrast since it is made by interference of several diffracted beams. 

The microscope was realized at the MOTB ID06 beamline using X-rays from 10 to 30 keV. It 

consists of the condenser, the objective lens and two X-ray CCD cameras – large area detector for 

diffraction and high resolution CCD for imaging. Condenser and objective assemblies were 

comprised of Beryllium parabolic refractive lenses. Switching from the diffraction mode to the 

imaging was achieved by placing the objective lens into the beam, and the chosen detector (Fig. 1). 

The tunable objective lens provides a magnification between 10 and 30. At maximum magnification 

a resolution of 100 nm was achieved. The microscope was applied for structural characterization of 

mesoscopic materials such as natural and synthetic opals, metal inverted photonic crystals. As an 

example figure 2 shows X-ray enlarged image of Ni inverted photonic crystal recorded at different 

crystal orientations. 

The proposed approach provides the ultimate tool for the efficient studies of real structure of 

mesoscopic materials. Short acquisition times with modern area detectors allow the method to be 

extended to time-resolved studies and combined 3-D real/reciprocal space mapping. As immediate 

practical application of the microscope is the in-situ characterization of the real crystal structure 

during photonic crystal growth. 

References 

1. A. Snigirev, V. Kohn, I. Snigireva, B. Lengeler, Nature (1996), 384, 49-51. 

2. V. Kohn, I. Snigireva, A. Snigirev, Opt. Comm. (2003), 216, 247-260. 

3. M. Drakopoulos, A. Snigirev, I. Snigireva, J. Schilling, Appl. Phys. Lett. (2005), 86, 014102. 

4. A. Bosak, I. Snigireva, K. Napolskii, A. Snigirev, Adv. Mater., (2010), 22, 3256-3259. 

-58 -



(PL23) 

ANALYSIS OF TOPICAL BIOMEDICAL AND TECHNOLOGICAL SAMPLES 

BY PHOTOTHERMAL AND PHOTOACOUSTIC SPECTROSCOPIES 

USING SIGNAL-ENHANCEMENT TECHNIQUES AND SELECTIVE REACTIONS 

Mikhail A. Proskurnin, Ivan V. Mikheev, Kristina V. Lobko, Dmitry S. Volkov, 

Ivan M. Pelivanov 

Lomonosov Moscow State University, 119991, Leninskie gori, MSU, Moscow, Russia 

e-mail: proskurnin@gmail.com 

We will survey the main trends in photothermal and photoacoustic spectroscopies related, directly or 

indirectly, to analytical chemistry and applied chemical analysis of biomedical and technological 

samples. Since the 1980s, these methods had been used in various analytical applications including 

highly sensitive photometric optical measurements and versatile detection schemes. Recently, much 

attention is paid to the microfluidic applications (µ-TAS) of these methods, which begin to play a 

key role in analytical chemistry [1]. Still, their potentialities in analytical chemistry and 

(bio)chemical analysis are even wider. The advantages (see the figure) and drawbacks of 

photothermal spectroscopy will be considered. Particular attention will be given to the coupling of 

photothermal spectroscopy to other analytical techniques and advances over conventional methods. 

Measurement of biomedical samples and disperse systems and the prospects for the practical 

analysis will be discussed. 

Drawbacks of 

spectrophotometry 

Shifting to 

photothermal methods 

is expedient... 

Photothermal 

procedure classes 

New features of 

photothermal techniques 

Features of 

photothermal 

spectroscopy 

Sensitivity of 

spectrophotometry is 

relatively low 

Spectrophotometry 

provides the 

information on the 

sample transmittance, 

not absorption 

If no sensitive 

procedure for this 

substance exists 

If the thermal response 

of electromagnetic 

radiation should be 

known 

If direct measurements 

of light absorption are 

required 

If high sensitivity is 

dictated by low 

contents of the test 

substance in the 

sample 

Development of novel 

procedures for lowly 

absorbing substances 

Studies of diffusion, 

thermal diffusion and 

related processes 

Simultaneous 

determination of light 

absorption and 

photochemical or 

radiative (fluorescence) 

processes 

High-precision low 

molar and linear 

absorptivities 

Remaking of existing 

photometric 

procedures with due 

account for trace level 

of the analyte and 

matrix effects 

Variability of solvent 

composition for enhancing 

the sensitivity 

Time-resolved and steadystate 

signal dependences 

bear complementary 

information on the sample 

Excitation power density can 

be adjusted depending on 

the study aim (microcopy, 

photochemical or biological 

samples) 

Power can be adjusted for 

enhancing the sensitivity 

Signal depends on 

photothermal 

properties of the 

sample 

Signal obeys the 

Bouguer-Lambert- 

Beers’ law 

The sensitivity of optical 

detection of 

photothermal effects 

than transmittance 

measurements in 

spectrophotometry 

A power-based method 

Spectrophotometry 

Photothermal spectroscopy 

Figure. Advances of photothermal spectroscopy over conventional absorption methods. 

-59 -



As photothermal and photoacoustic spectroscopies are ‘not just highly sensitive photometry’, their 

field of application for heterogeneous materials (solid or liquid), including dynamically appearing 

and changing heterogeneities, develops rapidly. The examples will include the formation of 

nanoparticles, crystalline and amorphous residues and protein-lipid complexes. Photothermics shows 

wide potentialities both for the determining the absorption-band parameters of proteins and for 

detecting laser-induced photochemical reactions; high precision of the measurements of absorption 

spectra is observed both in solutions and in cellular structures. 

The application of photothermal spectroscopy for the quantification, size estimation of heme 

proteins and carbon nanomaterials (nanodiamonds, fullerenes) will be discussed. The examples of 

multi-wavelength photothermal and photoacoustic imaging and determination of carbon 

nanomaterials and heme proteins (including and photochemical processes and in vivo analysis) will 

be discussed. We will discuss multiwavelength photothermal analysis (including flow applications) 

in blood and cytometry with multiple dyes in vivo and in real-time mode. 

Some examples of new relevant analytical applications based on well-known and novel selective 

photometric reactions will be given, especially those of optical chemical sensors [2]. Novel sensible 

materials — specially designed polymer matrices or surface-enhanced glasses/films with grafted or 

absorbed photometric reagents — can be used in the form of transparent chips, films, or resins. 

These materials serve as transducers in novel gas/aerosol/solute optical sensors and in microfluidics 

and state-of-the-art separation/preconcentration analytical methods. Photothermal spectroscopy is 

used for a considerable increase in the sensitivity of photometric measurements of such materials. 

The examples that will be given include trace metal determination, classical and enzyme kinetic 

indicator systems for phenolic compounds, immunoassays, and nanoparticle-assisted sensible 

materials. Moreover, lasers can be used for photoinduced synthesis of nanoparticles in polymer 

matrices with simultaneous online photothermal control. 

Finally, some schematics under discussion involve differential and wide-beam schemes and those 

combining several photothermal methods (with laser and non-laser excitation sources), fluorescence, 

scattering, photoacoustics, etc., relevant for analytical practice (aerosol analysis, table-top analytical 

instruments, etc.) will be discussed. The possibilities of photoacoustic spectroscopy for the chemical 

analysis of highly concentrated samples as ‘scattering-proof’ high-accuracy technique for the 

determination and estimation of physicochemical parameters will be discussed and exemplified. 

Acknowledgements. This work is supported by the RFBR, grants nos. 12-03-00653-а and 12-03- 

31569-mol_a and the MST of Russian Federation, contract no. 16.740.11.0471. 

References 

[1] S.E. Bialkowski “Photothermal spectroscopy methods for chemical analysis”. New York: 

(1996). 

[2] R. Narayanaswamy and O. S. Wolfbeis, Eds., “Optical Sensors. Industrial, Environmental 

and Diagnostic Applications” Berlin, Heidelberg, New York (2004) 

-60 -



(PL24) 

PROGRESS AND DEMANDS IN ANALYTICAL GLOW DISCHARGES 

Volker Hoffmann 

IFW Dresden, Institute for Complex Materials, P.O. Box 270116, D-01171 Dresden, Germany 

e-mail: V.Hoffmann@IFW-Dresden.de 

Glow Discharge Optical Emission Spectrometry (GD-OES) is one of the most frequently applied 

techniques for the direct analysis of solid materials, including the main components and the 

impurities. The dynamic range (µg/g 100%), high sample throughput (≈ 5 min/sample), good 

depth resolution (z/z ≈ 5%) over the range from several nm to > 100 µm depth and the multielement 

capability (including the light elements) make this method unique among the other 

techniques for elemental analysis and has led to the introduction of this method for quality control in 

many industrial laboratories. 

Since the introduction of radio-frequency (rf) discharges the analysis of non-conductors became 

possible. In combination with the feature to analyze extremely thin layers in the nm range, new 

demands for the glow discharge sources and power supplies exist. Sources for small and non-flat 

samples are needed and sputter craters with diameters up to 0.3 mm are possible nowadays. The 

investigation of the electrical characteristics, sputtering rates and crater shapes helps to find 

similarities and differences e.g. with the well-tried 4 mm sources (see Fig. 1). 

Rel. Intensity 

5,0 

4,5 

4,0 

Al 

Rel. Intensity 

5,0 

4,5 

4,0 

Al 

3,5 

3,0 

3,5 

3,0 

Ni 

2,5 

Ni 

2,5 

2,0 

1,5 

1,0 

P 

Ar 

Ar 

2,0 

1,5 

1,0 

P 

Ar 

Ni 

Ar 

P 

0,5 

Ni 

Al 

P 

0 

0 10 20 30 40 50 60 70 80 90 100 

Time [s] 

0,5 

Al 

0 

0 5 10 15 20 25 30 35 40 

Time [s] 

Figure 1: DC-GD-OES intensity-time profile of a hard drive at 1000 V, 3 hPa 

left: 4 mm, 56 mA, right: 0.3 mm, 0.25 mA 

For the analysis of non-conductors many investigations about rf-discharges and the corresponding 

equipment were going on, because the discharge should be stable in milliseconds. After the 

application of matched rf-generators also free running generators are now commercially applied. 

More recently IFW and Ingenieurbüro Birus have developed a frequency controlled system. Its 

advantage for special applications will be shown. 

More and more pulsed dc- and rf-discharges are applied in GD-OES and -MS. On the one hand, 

pulsed discharges reduce the thermal stress of the sample. On the other hand, this type of discharge 

offers a lot of additional possibilities - e.g. to optimize the crater shape or to get molecular and 

elemental information in glow discharge mass spectrometry (GD-MS). Up to now only pulsed dcdischarges 

are commercially available in GD-MS and rf at all is offered by just one GD-MS 

-61 -



producer. Applications of pulsed rf-GD-OES in the field of solar cell development will be shown. 

The measurement of the electrical discharge parameters proved to be very essential for the 

optimization of the equipment and for the evaluation of the analytical results. As an example in Fig. 

2 the influence of the duty cycle on the discharge conditions is shown for pulsed rf at constant 

voltage and pressure. 

Figure 2: Ionic part of the I-U characteristics of an rf-discharge at 3.4 MHz at different pressures and 

duty cycles (50 µs constant pulse length, cycle during the last µs). 

Those people, who deal with electron microscopy, know that existing sample preparation methods 

such as polishing, chemical etching, and ion beam etching are laborious and time consuming. 

Sputtering in the glow discharge has a great number of attractive features and thus lends itself to a 

fast and simple sample preparation. The low energy of the sputtering ions and atoms together with 

the high erosion rate make glow discharges useful for the preparation of samples, which are 

afterwards analyzed by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy 

(TEM), Electron BackScatter Diffraction (EBSD) etc. This part of the presentation is dedicated to 

possibly new applications of the glow discharge sputtering. A new source for the preparation of 

TEM-samples will be presented. 

-62 -



(PL25) 

DEVELOPMENT AND CHARACTERIZATION OF MATERIALS 

FOR ADVANCED POWER PLANTS 

Hubertus Nickel 

Research Centre Jülich and University of Technology Aachen, Germany 

The development of modern combined cycle power plants with high thermal efficiency requires 

constructional materials of high strength and improved resistance against aggressive service 

atmospheres. After giving an introduction into the actual situation of energy resources world wide 

the talk concerns questions of material research for combined steam and gas turbine cycle power 

plants. 

1) An increase of thermal efficiency of fossil fuel fired steam power plants can be achieved by 

increasing steam temperature and pressure. This requirement has provided the incentive for the 

development of 9 wt.-% chromium steels towards improved creep rupture strength as well as 

oxidation resistance in combustion gases. During the last decades such steels have been developed 

for power plant construction. 

Results of experiments using 18O isotopes and simulated combustion gases will be discussed with 

respect to oxidation mechanism of 9 wt.-% Cr steels. Also the investigation to improve these 9 wt.- 

% Cr steels and the use of Ni-based alloys like Inconel 617 for applying higher steam temperature 

and pressure will be shown. 

2) The increase of efficiency of large land-based stationary gas turbines for electric power 

generation requires increased gas inlet temperature. Gas temperature higher than 1300 °C can only 

be handled using air-cooled structures to keep the metal temperature below 1000°C. Only columnar 

grained directionally solidified (DS) or single crystal (SC) superalloys possess required creep 

strength and thermo-mechanical fatigue resistance. Superalloys like IN 792 DS or CMSX-4 SC with 

excellent mechanical properties have been developed. 

But the increase of component surface temperatures leads to an enhanced oxidation attack in 

stationary gas turbines of thermal barrier coating consisting usually of ZrO2+8-wt.-%Y2O3 on top 

of a MCrAlY (with M=Ni and/or Co) bond coat. Air plasma spraying (APS) and electron beam 

physical vapour deposition (EB-PVD) are discussed with respect to new coating materials and 

improved corrosion resistance. 

One of our research was directed to the improvement of the high temperature properties of MCrAlY 

alloys by addition of minor alloying elements to clarify the effect of yttrium, silicon and titanium 

additions on corrosion resistance. 

The corrosion mechanisms as well as the microstructure stability of the high temperature materials 

and the protective coatings were studied by combining the results of kinetic studies with extensive 

analytical investigations using techniques like SNMS, SIMS, SEM, TEM, Rutherford backscattering 

(RBS), Laser Raman Spectroscopy (LRS) as well as X-ray diffraction. 

-63 -



(PL26) 

APPLICATION OF SYNCHROTRON MICROPROBE TECHNIQUES TO SPECIATION 

OF PLUTONIUM IN ARGILLACEOUS ROCKS 

Tobias Reich 1 , Ugras Kaplan 1 , Samer Amayri 1 , Jakob Drebert 1 and Daniel Grolimund 2 

1 Institute of Nuclear Chemistry, Johannes Gutenberg-Universität Mainz, 55099 Mainz, Germany 

2 Swiss Light Source, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland 

e-mail: tobias.reich@uni-mainz.de 

In several European countries, e.g., France, Germany and Switzerland, argillaceous rocks are 

considered as a potential host rock for the construction of nuclear waste repositories. Detailed 

information on the interaction between the clay and plutonium, which is a major contributor to the 

radiotoxicity of spent nuclear fuel after storage times of more than 1,000 years, is required for the 

safety assessment of future nuclear waste repositories. 

The interaction between redox-sensitive plutonium and natural clay has been investigated in batch 

and diffusion experiments and by X-ray techniques. Opalinus Clay (OPA, Mont Terri Rock 

Laboratory, Switzerland), which was used as a reference for natural clay, consists of different clay 

minerals (66%), quartz (14%), calcite (13%), iron(II) minerals (4%) and traces of other minerals and 

organics. Due to this mineralogical heterogeneity, a combination of different synchrotron based 

techniques with micrometer resolution was used to study the sorption and diffusion of Pu(V) and 

Pu(VI), which have a high solubility at near neutral pH conditions. Different thin sections of OPA 

were contacted with 20 µM Pu(V) or Pu(VI) solutions at pH 7.6 under aerobic conditions for several 

days. In the diffusion experiment, plutonium was allowed to diffuse from a reservoir with 20 µM 

Pu(V) into an intact OPA bore core during one month before it was removed from the diffusion cell. 

The thin sections and small pieces of the bore core were investigated at the microXAS beamline at 

the Swiss Light Source using monochromatic synchrotron radiation with a beam size of typically 

3 1.5 µm 2 . 

Micro-X-ray fluorescence (µ-XRF) mappings of both sorption and diffusion samples showed 

heterogeneous distributions of plutonium and other heavy elements (Ca, Mn, Fe, Sr) contained in 

OPA. Regions with high concentrations of plutonium, which frequently occurred in close vicinity to 

areas enriched in iron, were investigated by Pu L III -edge micro-X-ray absorption near-edge structure 

(µ-XANES) spectroscopy. By comparing these XANES spectra to those of reference spectra of 

plutonium in different oxidation states, it was shown that the highly soluble Pu(V) and Pu(VI) 

species were reduced to the less soluble tetravalent oxidation state in all investigated samples. In 

some areas also Pu(III) was identified, although Pu(IV) remained the dominating oxidation state. To 

obtain further information about the minerals present in areas enriched in plutonium, micro-X-ray 

diffraction (µ-XRD) was applied. In addition to the clay mineral illite, siderite (FeCO 3 ) could be 

identified near plutonium spots by µ-XRD in several thin section samples, indicating that this Fe(II) 

mineral acts as a reducing agent and causes the immobilization of plutonium in OPA. The examples 

given in this presentation illustrate that µ-XRF, µ-XANES, and µ-XRD are a powerful combination 

of techniques for studying the speciation and migration behaviour of actinides and other heavy toxic 

metals in heterogeneous natural systems like argillaceous rocks with high spatial resolution. 

-64 -



(PL27) 

AN ANALYTICAL TECHNIQUE ON ITS WAY TO ADULTHOOD: CURRENT STATUS 

AND FUTURE PERSPECTIVES OF MASS SPECTROMETRY IMAGING 

Andreas Römpp 

Institute of Inorganic and Analytical Chemistry, Justus Liebig University, Schubertstrasse 60, 

D-35392 Giessen, Germany 

e-mail: Andreas.Roempp@anorg.chemie.uni-giessen.de 

Mass spectrometry imaging (MS imaging) is the method of scanning a sample of interest and 

generating an image of the intensity distribution of a specific analyte ion. A full mass spectrum is 

generated for each position sequentially. In contrast to most histochemical techniques, mass 

spectrometry imaging can differentiate (amino acid) modifications and does not require labelling of 

compounds. 

Matrix-assisted laser desorption/ionization (MALDI) and secondary ion mass spectrometry (SIMS) 

are the most widely used ionization techniques for mass spectrometry imaging, but a number of 

alternative techniques have been developed in recent years. In particular, atmospheric pressure 

ionization techniques such as desorption electrospray (DESI), low-temperature plasma (LTP) and 

laserspray are increasingly operated in imaging mode. Each of these techniques has specific 

analytical capabilities that are highly complementary. 

While SIMS has been routinely used in material science for many years, the situation is much more 

challenging for MS imaging of biological (tissue) samples. Mass spectrometry imaging has seen 

impressive instrumental and methodological progress in the last decade. The number of groups who 

are working on this topic is constantly increasing. However, the field is very diverse and results are 

often highly dependent on the experience of the operator. In order to become a (more) routinely used 

method, the MS imaging workflow needs to be more robust and user-friendly. An activity that 

targets these issues is the EU-funded COST action (European Cooperation in Science and 

Technology) „Mass Spectrometry Imaging: New Tools for Healthcare Research” (BM1104). This 

network, which includes more than 30 MS imaging groups, aims to establish MS imaging as a 

routine method in clinical research. This includes setting up best practice examples for sample 

preparation and measurement protocols as well as by providing reference sample material for quality 

control. 

Mass spectrometry imaging produces large and complex data sets, and thus efficient strategies for 

processing and analyzing data are essential. A common data format for the flexible exchange and 

processing of mass spectrometry imaging data was developed: imzML (www.imzml.org). Data sets 

from more than 10 different MS imaging platforms (including MALDI, SIMS, DESI and LA-ICP) 

have been converted into imzML so far. A growing number of software tools support imzML 

(including commercial and open-source software packages). This allows for choosing from a variety 

of options to display and process MS imaging data. Users are no longer limited to proprietary 

software, but are able to use the processing software best suited for a specific question or 

application. A common data format is not a mere technical detail, but has significant impact on 

practical work: fully searchable mass spectrometry imaging data can be shared with collaborators in 

biological or clinical labs without being restricted to proprietary vendor software. 

Additional aspects of MS imaging that will be discussed include quantitation, on-tissue digest of 

proteins, compound identification and ‘round-robin’ experiments. 

-65 -



(PL28) 

“THINK BIG! – OPTIMIZATION OF A SPECTROMETRY LAB ON THE INDUSTRIAL 

SCALE 

Heiko Egenolf 

BASF SE, Competence Center Analytics, GMC/E - M320, 67056 Ludwigshafen, Germany 

e-mail: heiko.egenolf@basf.com 

BASF is the world’s leading chemical company: The Chemical Company. Its portfolio ranges from 

chemicals, plastics, performance products and crop protection products to oil and gas. We combine 

economic success with environmental protection and social responsibility. Through science and 

innovation, we enable our customers in nearly every industry to meet the current and future needs of 

society. Our products and solutions contribute to conserving resources, ensuring nutrition and 

improving quality of life. We have summed up this contribution in our corporate purpose: We create 

chemistry for a sustainable future. BASF had sales of €72.1 billion in 2012 and more than 110,000 

employees as of the end of the year. Further information on BASF is available on the Internet at 

www.basf.com. 

With the Competence Center Analytics, BASF operates a central unit with 350 employees that are 

solving all analytical problems of research, development, and production. Three factors determine 

the excellence of an analytical service provider; quality, speed and analysis costs. Short turnover 

times in compliance with the requisite quality standards at reasonable prices are key factors 

determining long-term success in the analytical market. 

The high amount of analysis samples processed at the Competence Center Analytics – approx. 

250,000 per year – requires efficient organization of the structures and workflows in the laboratories. 

Using the example of the atomic spectrometry lab, some insights will be given into the method 

portfolio covering “routine” tasks as well as customized solutions for special analytical problems. In 

addition, the optimization of an industrial analysis lab is explained. One key feature has been the 

development and construction of several robotic analysis systems for sample preparation and 

measurement. The modes of operation for automated sample preparation of both organic and 

inorganic samples are demonstrated, and the benefits of the robotic systems are explained. 

-66 -


Lecture Abstracts 

LECTURE ABSTRACTS 

(L1) 

X-RAY REFRACTIVE OPTICS: PRESENT STATUS AND NEW DEVELOPMENTS 

Anatoly Snigirev 

European Synchrotron Radiation Facility (ESRF), 38043 Grenoble, France 

e-mail: snigirev@esrf.fr 

Soon after the first experimental demonstration of X-ray focusing by refractive lenses at the ESRF in 

1996, it became immediately clear that the refraction-based methods traditionally used in the visible 

light regime can be successfully applied for X-rays. The use of X-ray refractive optics has rapidly 

expanded and they are now in common use on various beamlines at 15 synchrotrons in 10 countries. 

Firstly, this dramatic progress was driven by the unprecedented properties of X-ray beams delivered 

by third generation synchrotron sources such as very low emittance coupled with high brilliance. 

Secondly, refractive optics offers number of advantages over the existing optics taking into account 

applicability, tunability and diversity in terms of energy range, focal distance and focal spot. 

The talk will give a short overview of ongoing and future activities on the development of refractive 

optics at the ESRF. Over the past, most of our developments were driven by the demands of the 

Upgrade Program. The significant progress has been made in extending the diapason of applications 

of the refractive lenses in terms of energy range and tunability. The applicability of Be lenses has 

been extended to softer X-rays - down to ~2 keV opening new opportunities for spectroscopy and 

diffraction applications. On the nano-beam front we have taken steps to improve the performance of 

the planar Si lenses. The resolution below 100 nm has been demonstrated at 30-50 keV. 

Finally we will shortly present the latest developments of new techniques based on refractive optics: 

A coherent diffraction microscopy for mesoscopic materials, photonic and colloidal crystals. 

A new concept of a dark-field diffraction microscopy for 3D stress mapping of single grains. 

An in-line multi-lens interferometry for nano-scale measurements and coherence diagnostics. 

-67 -



(L2) 

CHARACTERISATION OF NANOPARTICLES WITH SYNCHROTRON X-RAY 

STANDING WAVE FLUORESCENCE 

Roland Hergenröder and Martin Brücher 

Leibniz-Institut für Analytische Wissenschaften-ISAS, Interface Processes, Bunsen-Kichhoff 

Str.11, 44139 Dortmund, Germany 

e-mail: roland.hergenroeder@isas.de 

Since the development of total reflection X-ray fluorescence (TXRF) spectroscopy in 1971, 

measurements basing on the generation of a Standing Waves interference pattern produced by total 

X-ray reflection (XSW) have found a wide range of applications. The main advantage of this 

powerful technique is the extremely low detection limit of the analyte, made possible by a greatly 

reduced spectral background compared to conventional X-ray fluorescence analysis. Furthermore, 

the absence of any matrix effects makes TXRF suited for exact quantitative analyses. 

If the TXRF set-up is equipped with a high resolution goniometer and if a coherent X-ray radiation 

source like a synchrotron can be applied, then the method can be extended to provide high resolution 

in-depth profiles of elemental distributions of surfaces. The sub-nanometre wavelength domain of 

X-ray provides a spatial resolution on molecular scale. Main advantages of this technique are low 

detection limit and sub-nanometer resolution, enabling space-resolved measurements on molecular 

scale. [1-3] 

In X-ray standing wave (XSW) experiments need a beam of coherent and monochromatic X-rays, 

hitting a flat surface under grazing incidence that is totally reflected. In the overlap of incoming and 

reflected beam, an interference pattern of alternating minima (nodes) and maxima (antinodes), the 

X-ray Standing Waves field, is generated. (see Figure 1) 

Figure 1 Angular and vertical distribution of intensity in a 15 keV X-ray Standing 

Waves field generated inside a poymer layer on a reflecting substrate. At c polymer 

0.07°, the incoming X-rays are refracted into the layer and interfere after reflection at 

the layer/substrate interface. (b) The scheme visualizes the refraction and reflection of 

-68 -



Atoms or ions within the interference volume are excited to fluorescence depending on the local 

intensity I(α,z) of the XSW field. The position of the fluorescence maxima depends on the incident 

angle α, so by recording fluorescence spectra with a stepwise variation of α between the single 

measurements, the distribution of elements above the reflecting surface is scanned vertically. The 

XSW method has successfully been applied to the investigation of particles, layered structures, 

electric double layers, adsorbates and biofilms. 

Here, the versatility of this method is demonstrated by examples from 

Determination of element-specific nanoparticle size distributions. 

Metallic nanoparticles produced by laser ablation under varying liquid conditions are dried on a 

silicon wafer. The median size of such particle is known to be under 20 nm und therefore difficult to 

determine. XSW enables a direct measurement of the vertical mass distribution on the surface which 

then can be fitted to different assumed distribution of spheres. As a result a best-fit size distribution 

function is provided. No not verifiable ad-hoc assumption about the distribution is necessary. 

Because fluorescence is element specific the additional advantage to measure elementally mixed 

particle distribution is provided. 

Measurements of elemental distribution at the solid/ liquid are presented. 

Measuring the distribution of elements contained in a liquid contacting directly a solid surface is 

another interesting application. Numerous natural and technological processes are taking place on 

surface. Bulk concentration of a liquid gives only limited information of the relevant concentration 

of compounds in proximity to the surface. Electrostatic interaction may considerably modify the 

concentration (e.g. electric double layer, stern layer) and an in-situ measurement of the distribution 

above the surface is of great interest. Measurement of hydrophobic/ hydrophilic and chemically 

(“soft”) surface is presented. 

A.von Bohlen, M. Krämer, C. Sternemann, M. Paulus, Spectrochim. Acta, Part B 2009. 

P. Wobrauschek, H. Aiginger, Analytical Chemistry 1989, 47, 852. 

M. J. Bedzyk, D. H. Bilderback, G. M. Bommarito, M. Caffrey, J. S. Schildkraut, Science 1988, 241, 

1788. 

-69 -



(L3) 

NEXAFS SPECTROSCOPIC STUDIES OF ANODIZED Ti-6Al-4V ALLOY WITH THE 

AIDE OF FIRST PRINCIPLES CALCULATIONS 

Toshihiro Okajima 1,2 , Yoshiteru Mizukoshi 3 and Naoya Masahashi 3 

1 Kyushu Synchrotron Light Research Center, 8-7 Yayoigaoka, Tosu, Saga, 741-0005, Japan 

2 Research Center for Synchrotron Light Applications, Kyushu University, 6-1 Kasugakohen, 

Kasuga, Fukuoka 816-8505, Japan 

3 Kansai Center for Industrial Materials Research, Institute for Materials Research, Tohoku 

University, 1-2 Gakuen-cho, Naka-ku, Sakai, Osaka, Japan 

e-mail: okajima@saga-ls.jp 

Introduction 

Titanium dioxide (TiO 2 ) is a well-known photocatalyst. Many efforts including doping ions to TiO 2 

have been paid for the improvement in the visible light response of the photocatalytic activities. 

More recently, Mizukoshi et. al. reported that the visible light response was improved in the 

anodized Ti-6Al-4V (hereafter described as Ti64) alloy [1], which is one of the commonly used Ti 

alloys due to its balanced workability and strength. The anodization can lead TiO 2 containing V, but 

the details of V are not elucidated. In the present study, we investigated the local structures of V ion 

in the anodized Ti64 alloy by a combination of NEXAFS spectroscopy and first-principles DFT 

calculations. 

Experimental and computational procedures 

Anodization of Ti64 plate was carried out in an aqueous solution of acetic acid (2M) using a Pt mesh 

electrode as the cathode. The oxidation was conducted for 0.5 h. The anodized Ti64 was annealed at 

723 K for 5 h in air [1]. 

V and Ti K-edge NEXAFS spectra were measured at the beamline BL11 of Kyushu Synchrotron 

Light Research Center with convergent electron yield (CEY) mode for Ti64 plates before and after 

anodization and with transmission mode for reference samples. The theoretical V K-edge NEXAFS 

spectra were also obtained with GGA using full-potential augmented plane wave plus local orbitals 

(APW + lo) calculations [2]. The core-hole effects were fully taken into account in the present 

calculations. The theoretical spectral profiles were obtained by a product of the radial part of the 

transition matrix element and the corresponding projected partial density of state. Each of calculated 

spectrum was broadened by the Gaussian function of =1.0 eV full width at half maximum. 

Results and Discussions 

The measured Ti K-edge and V K-edge NEXAFS spectra of before and after anodized Ti64 plates 

are shown in Figures 1 and 2, respectively. The Ti K-edge spectra obtained from some reference 

samples are also shown in the Figure 1. The Figure 2 (c) shows the calculated V K-edge NEXAFS 

spectrum for V substitutional model. In the model, a Ti 4+ ion in the 2×2×1 surpercell of an anatase 

type TiO 2 unit cell were substituted by a V 5+ ion. The V ion is 4-fold coordinated with O ions in the 

alloy. 

In Figure 1, the spectral features of Ti64 alloy before and after anodization are drastically changed, 

and are similar to those of Ti metal and anatase type TiO 2 , respectively. These results show that Ti 

metals in Ti64 alloy are oxidized to anatase type TiO 2 by anodization. This result consistent with 

that obtained from XRD shown in previous paper [1]. The spectral features in V K-edge NEXAFS 

region shown in Figure 2 (a) and (b) also change between before and after the anodization. The V in 

Ti64 alloy before anodization exists in a metal from the spectral features. On the other hand, it is 

-70 -



thought that the V in Ti64 alloy after anodization is oxidized. However, the V ion is not simply 

oxidized state such as VO 2 , V 2 O 3 and V 2 O 5 from the comparisons of the spectral features previously 

reported for reference samples [3]. On the comparison of V K-edge region between the anodized 

Ti64 alloy and the calculation, the spectral features around 5490 to 5510 eV are similar between 

both spectra. However, the differences are seen clearly at pre-edge region around 5470 eV between 

both spectra. This result shows that the V substitutional model is not suitable to explain the local 

structures of V ions in the anodized Ti64 alloy. 

We will discuss the local structures of V ion in the anodized Ti64 alloy and also discuss the 

mechanism of improvement in the visible light response of the photocatalytic activities in the 

presentation. 

Acknowledgment 

This work was supported in part by Izumi Science and Technology Foundation. 

References 

[1] Y. Mizukoshi and N. Masahashi, Chem. Lett., 41, (2012), 544. 

[2] P. Blaha, et. al., WIEN2k, an augmented plane wave +local orbitals program for calculating 

crystal properties, Karlheinz, Achwarz, TechnicalUniversitat Wien, Austria, 2001. 

[3] J. Wong, F.W. Lytle, R.P. Messmer and D.H. Maylotte, Phys. Rev. B30, (1984), 5596. 

-71 -



(L4) 

MICROSCALE MINERAL ANALYSIS OF CLAY ROCK THIN SECTIONS AFTER 

SORPTION EXPERIMENT USING SRXRF 

János Osán 1 , Annamária Kéri 1 , Daniel Breitner 1 , Margit. Fábián 1 , Rainer Dähn 2 and 

Szabina. Török 1 

1 Environmental Physics, HAS Energy Research Institute, H-1121 Budapest, Hungary 

2 Laboratory for Waste Management , Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland 

e-mail: szabina.torok@energia.mta.hu 

Argillaceous rock of the Boda Claystone Formation (BCF) is considered in Hungary as suitable host 

rock formations for the deep geological disposal of radioactive waste. The most important chemical 

characteristics in this respect is their generally strong radionuclide retention property due to the 

high sorption capacity. Consequently, the physico-chemical parameters of this process have to be 

studied in great detail. Synchrotron based XRF and XRD have sufficient sensitivity to study these 

processes on the microscale without the need to use radioactive substances. The present study 

focuses on the interaction of escaped ions with the host-rock surrounding the planned high-level 

radioactive waste (HLW) repository. 

The aim of our study is to investigate the uptake mechanisms of key ions presents at high 

conectration in such wastes. For this reason, combined synchrotron-radiation micro-XRF mapping, 

micro-XRD measurements were performed on thin sections subjected to sorption experiments 

using 5 µm spatial resolution at the ANKA FLUO beamline (Karlsruhe, Germany). Inactive Cs(I), 

Ni(II ) and natural U(VI) were selected for the experiments chemically representing key 

radionuclides. 

The thin sections were prepared from geochemically characterized cores from drillings of BCF. Thin 

sections were prepared on 350-µm thick high-purity silicon wafers as acceptable backing for XRD. 

The average thicknesses of the sections are 30-60 µm. Samples were subjected to 72-hour sorption 

experiments with one ion of interest added, using synthetic porewater solution. 

The elemental micro-XRF maps taken usually on several thousand pixels indicate a correlation of 

Cs, Ni and with Fe- and K-rich regions suggesting that these elements are predominantly taken up 

by these phases. Micro-XRD can identy the mineral composition of the particular interesting pixel. 

However, XRD takes at least one order of magnitude longer counting time so it can be only 

performed on limited number of pixels. When multivariate mathematical statistics is used for the 

processing of elemental maps significant information can be obtained in most cases that can be 

related to the uptake of element by a particular mineral phase. 

Factor profiles obtained by positive matrix factorization show which elements of the rock-forming 

minerals are present together with the (sorbed) element (of interest), delivering information on the 

mineral phases responsible for the uptake. In addition, cluster analysis was found to be a useful tool 

for semi-quantitative calculation of the uptake capacity of regions dominated by different mineral 

phases. The presence of mineral phases was verified by micro-XRD. 

-72 -



(L5) 

SYNTHESIS AND CHARACTERIZATION OF METAL NANOCLUSTERS: A NEW 

GENERATION OF LUMINESCENT LABELS 

Laura Trapiella-Alfonso 1,2 , Mónica Fernández-Ujados 1 , Mario Menéndez-Miranda 1 , José M. Costa 1 , 

Rosario Pereiro 1 , M.A. Habeeb Muhammed 2,3 , Hedi Mattoussi 2 , Alfredo Sanz-Medel 1 . 

1 

Department of Physical and Analytical Chemistry, University of Oviedo, Avd. Julián Clavería 8, 

33006 Oviedo, Spain. 

2 

Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, 

Tallahassee, Florida 32306, United States. 

3 Present address: Department für Physik and CeNS, Ludwig-Maximilians-Universtität München, 

Amalienstr. 54, D-80799 München, Germany 

e-mail: trapiellalaura@uniovi.es 

The advance in nanomaterials research has brought about a new class of fluorescent nanoprobes 

known as metal nanoclusters (NCs). Being composed of several to tens of atoms NCs present 

distinct optical, electrical, and chemical properties as compared to other large-scale nanomaterials or 

bulk materials with the same chemical composition. NCs exhibit luminescence from ultraviolet to 

the near infra-red regions, large Stokes shifts, two-photon absorption, lack of intermittency, low 

photobleaching, electroluminescence and huge surface-to-volume ratio. Moreover, their tunable 

emission is size, core composition and environment dependent. All those features make them 

promising materials for developing a new generation of sensors, catalysts, optoelectronic devices or 

for biological applications. Thus, NCs can be treated as alternatives to quantum dots and organic 

dyes, being highly attractive for bio-imaging and bio-labeling applications due to their smaller size 

and because they do not present the stigma of potential toxicity often attributed to some luminescent 

quantum dots. As this is a new nanomaterial class, they also offer a great and challenging 

fundamental problem to understand cluster growth, stability, and functionality. 

In this communication we present a simple and efficient synthetic route approach for the preparation 

of Ag 1 and Cu nanoclusters in aqueous media. For both type of nanomaterials, the synthesis process 

is based on the direct reduction of the metal in the presence of thiotic acid (TA)-appended 

poly(ethylene glycol) (PEG) ligands, requiring to ensure slight different experimental conditions, 

depending on the nanocluster composition (Cu or Ag), such as different metal:ligand ratios, 

temperature and reaction times. The TA-PEG ligand acts as a strong metal affinity anchor onto the 

metal surface while promoting aqueous compatibility over a broad range of conditions (pH, ionic 

strength media, cell culture media) and reduce significantly the nonspecific interaction in biological 

systems. The above route also allows easy surface-functionalization of the NCs with reactive groups 

(e.g. carboxylic acid or amine). We will describe in detail the proposed synthetic route along with 

the structural, optical and spectroscopic characterization of these materials. 

Additionally, some insights about the mechanism involved in the growth of these nanomaterials 

could be provided (see Fig. 1). These studies were carried out by three different ways: (1) optical 

monitoring of the synthesis; (2) size focusing methodology; (3) asymmetrical flow field-flow 

fractionation technique (AF4) coupled to several detectors (UV-vis, Fluorimeter and ICP-MS). The 

results obtained are in agreement among them, confirming that the synthesis of the metal clusters 

was driven by the previous formation of the corresponding metal nanoparticle. 

Finally, photostability and long-term storage stability of the new synthesized fluorescent 

nanoclusters were investigated, in order to establish its manipulation and its possible applications. 

Different behaviours versus UV irradiation were observed depending on the core composition. 

-73 -



While AgNCs loss their optical properties after 30 min of UV irradiation, CuNCs seem to be highly 

photostable, retaining their optical properties after 24 hours of continuous UV exposition. Observed 

AgNCs optical properties degradation could be a result of three possible issues: (1) the liberation of 

free silver ions from the core that implies the total destruction of the NC; (2) the aggregation of the 

NCs catalized by UV light or (3) the formation of a higher-size nanostructure driven by a 

photoreaction. To try to elucidate which process is the responsible, we make use of the AF4 

technique, coupled to different molecular and elemental detectors, and the HR-TEM as confirmatory 

analysis. We can conclude that the most probable mechanism explaining the reduced photostability 

of AgNCs could be a fusion of nanoclusters, catalyzed by UV irradiation, resulting in larger-size 

non-fluorescent silver nanostructures. 

Figure 1. Proposed mechanism for the synthesis of metal nanocluster. 

So we can conclude that these new nanoprobes have a great promising applicability in different 

fields such as sensors, catalyst or labels for bioanalytical applications. 

1 M.A. Habeeb Muhammed, Fadi Aldeek, Goutam Palui, Laura Trapiella-Alfonso, Hedi Mattoussi, Growth of 

in-situ functionalized luminescent silver nanoclusters by direct reduction and size focusing, ACS Nano, 2012, 

6, 8950-8961 

-74 -



(L6) 

ADVANCED INSPECTION TECHNOLOGIES IN EXTREME SCENARIOS: STANDOFF 

LIBS AND UNDERWATER LIBS 

J.J. Laserna, J. Moros, F.J. Fortes, I. Gaona, S. Guirado and J. Serrano 

Department of Analytical Chemistry, University of Málaga, Málaga, Spain 

e-mail: Laserna@uma.es 

Development and application of advanced laser technologies for materials characterization offers 

quick-turn-around, cost-effective solutions to a variety of research and technical problems in diverse 

application areas, including process monitoring technologies, environment, cultural heritage, 

defence and security, and steel products and processes. Among the techniques available for field 

operation, laser-induced breakdown spectroscopy (LIBS) constitutes one of the most advanced 

solutions for real world problems. Standoff inspection of materials at distances up to 100 m based on 

LIBS will be presented. Also, systems for underwater analysis of materials at depth of up to 50 m in 

the ocean will be discussed. The underlying technology used in both approaches and a survey of its 

applications in the inspection of cultural heritage assets and in the detection of explosives and other 

threats will be presented. 

-75 -



(L7) 

THE UMS: A NEW TOOL FOR MULTI-ANGLE UV-VIS-NIR PHOTOMETRIC 

SPECTROSCOPY 

David L Death 1 , Robert J Francis 1 , Cameron Bricker 1 , Travis Burt 1 and Jan Wuelfken 2 

1 Agilent Technologies Australia, 679 Springvale Road, Mulgrave VIC 3170, Australia 

David.Death@agilent.com 

2 Agilent Technologies Sales & Service GmbH & Co. KG, Hewlett-Packard Straße 8, 38179 

Waldbronn, Germany 

jan.wuelfken@agilent.com 

Abstract: The UMS is a new, high performance, Cary UV-Vis-NIR spectrophotometer system 

which provides a wide range of functionality for the routine measurement of both reflectance and 

transmittance of specular and/or diffuse samples. 

1. Introduction 

The Universal Measurement Spectrophotometer (UMS) is a versatile new system designed for 

Multi-Angle Photometric Spectroscopy applications. Multi-angle Photometric Spectroscopy (MPS) 

measures the reflectance and/or transmittance of a sample across a range of angles from near 

normal 1 to oblique incidence. The UMS combines both reflection and transmission measurements 

from the same patch of a sample’s surface in a single automated platform for angles of incidence in 

the range 5°≤| i |≤85° 2 (I.E. angles on either side of beam normal noted as +/-). The UMS also 

functions as a goniometer providing further capability for diffuse reflectance measurements of nonspecular 

surfaces and diffuse transmittance measurements of translucent materials. The addition of 

an automated polarizer further enables accurate measurement at S, P or user specified polarization 

angles. 

2. Optical Characterization of thin films 

Reflection (R) and transmission (T) are the most fundamental measurements available for 

characterizing optical materials and coatings. Historically the characterization of optical materials 

and coatings for precision optics has been largely accomplished on the basis of normal and near 

normal incidence measurements due to the experimental simplicity of such an approach. This 

simplicity, however, is not without compromise. Normal incidence transmission measurements are 

typically conducted in the sample chamber of a spectrophotometer whilst near normal reflectance 

measurements require the use of a suitable reflectance accessory. A consequence of this approach is 

that there is never any guarantee that reflectance and transmission measurements are made from 

exactly the same patch on the sample due to sample repositioning during the significant changes in 

instrument configuration between R and T measurements. 

The Agilent Technologies Universal Measurement Spectrophotometer provides multi-angle 

measurement capability for both specular reflectance and direct transmittance measurements in a 

single fully automated unit without the need to reposition the sample. For example figure 2 shows 

sequential measurements made on the same patch of sample of 1 mm thick fused silica without 

repositioning of the sample. This simple measurement of the transmission and reflection from a 

1mm thick plate of fused silica was conducted at angles of incidence ranging from 0 to 82° in 

transmission and 6 to 82° in reflection in both S and P polarization. The physical size of the silica 

1 Near normal for reflectance, Normal incidence for transmittance. 

2 In Reflection. 0°≤| i |≤85° direct transmission. 

-76 -



sample limited the measurable range of angle of incidence to 82° without the incident beam falling 

off the sample surface. The measurements shown include contributions from both the front and 

internal rear surface reflections and transmissions. The individual points represent the measured 

values and the underlying solid lines indicate the total reflectance and total transmittance predicted 

by the Fresnel equations. 

Figure 1. Reflectance and transmittance of a 1mm thick silica sample plate as a function of angle of 

incidence. The solid lines are calculated from the Fresnel equations the symbols are values measured 

using the UMA. Measurement wavelength: 500nm; Physical size of the Silica sample limited AOI 

range to 0-82°. 

For materials and coatings routinely used in normal or near normal incidence applications it makes 

sense to analyze their performance at or near normal incidence. However the analysis of optical 

coatings routinely employed over a range of oblique angles requires a degree of extrapolation from 

data collected solely at near normal incidence. Further as the complexity of the coatings increase to 

include multiple stacks and/or absorbing layers the ambiguity introduced by this extrapolation 

becomes progressively worse [1]. Such analysis is typically used to fine tune coating parameters 

and/or reverse engineer coatings to enable a better understanding of those parameters and to improve 

production of desired performance [2]. The accurate characterization of the optical parameters of 

materials used in thin film production is thus a critical factor for improving thin film performance. 

Recent work has demonstrated the utility of increasing the range of data available for use in reverse 

engineering films to extract optical parameters. The inclusion of MPS data at angles greater than 

normal and near normal incidence lessens ambiguities in analysis providing better reverse 

engineering of complex thin films [2]. Additionally multi-angle photometric spectroscopic data has 

also provided insight into oscillations in the total losses in thin dielectric films [3]. 

This talk will further examine the utility of multi-angle photometric spectroscopy data provided by 

the UMS for the accurate characterization of a number of different sample types. 

3. Conclusion 

The measurement of spectral data across a wide range of angles of incidence (multi-angle 

photometric spectroscopy) provides for better characterization of the performance of materials and 

coatings employed for precision optics. These data can also assist in the validation of optical coating 

designs by reducing the uncertainties encountered in reverse engineering of coating parameters. The 

UMS is a new, high performance, Cary UV-Vis-NIR spectrophotometer which provides a wide 

range of functionality for the routine measurement of multi-angle photometric spectra for both 

reflectance and transmittance of specular and/or diffuse samples. It will prove to be a valuable tool 

for the characterization of optical materials, coatings and components in a wide range of industrial 

and laboratory applications. 

-77 -



(L8) 

57 FE-MÖSSBAUER STUDY OF ELECTRICALLY CONDUCTIVE LITHIUM IRON 

VANADATE GLASS 

Shiro Kubuki 1 , Koken Matsuda 1 , Kazuhiko Akiyama 1 and Testuaki Nishida 2 

1 Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan 

University, Minami-Osawa 1-1, Hachi-Oji, Tokyo 192-0397, JAPAN 

2 Department of Biological and Environmental Chemistry, Faculty of Humanity-Oriented Science 

and Engineering, Kinki University, Kayanomori 11-6, Iizuka, Fukuoka 820-8555, JAPAN 

e-mail: kubuki@tmu.ac.jp 

Vanadate glass has an electrical conductivity () of 10 -7 -10 -5 Scm -1 caused by small polaron hopping 

from V IV to V V . Nishida et al. firstly reported that a remarkable increase in took place from the 

order of 10 -8 to 10 -3 Scm -1 in K 2 O-Fe 2 O 3 -V 2 O 5 glasses after isothermal annealing at temperatures 

between glass transition temperature (T g ) and crystallization temperature (T c ) [1]. Kubuki et al. 

revealed that xLi 2 O•(20-x)BaO•10Fe 2 O 3 •70V 2 O 5 glass showed a larger increase in from the order 

of 10 -4 to 10 -1 S cm -1 after isothemal annealing [2]. Structural relaxation of these vanadate glasses, 

i.e., a decrease in the local distortion of Fe III O 4 and VO 4 tetrahedra constituting the glass network 

was successfully elucidated by 57 Fe-Mössbauer study [1-3]. Vanadate glass with higher will 

contribute to the development of cathode-active material for secondary battery of high performance. 

In order to reveal the relationship between and structural change of vanadate glass in more detail, 

characterization of 20Li 2 O•10Fe 2 O 3 •70V 2 O 5 glass (20LFV glass) was carried out by means of 57 Fe- 

Mössbauer spectroscopy and dc-probe method. 

In Fig. 1, of 20LFV glass is plotted against different annealing temperatures. When 20LFV was 

annealed for 100 min at 400, 410, 430 and 450 o C, increased from 2.4×10 -2 to 2.1×10 -2 , 5.8×10 -2 

and 1.0 ×10 -1 S cm -1 , respectively. On the other hand, a gradual decrease in was observed from 

3.4×10 -2 to 7.5×10 -2 , 2.0×10 -2 , 1.0×10 -2 and 1.2×10 -2 S cm -1 when it was annealed at 460, 470, 480, 

490 and 500 o C. These results indicate that change of in annealed 20LFV glass depends on the 

annealing temperature. 

Figure 1 Electrical conductivity () of 20Li 2 O•10Fe 2 O 3 •70V 2 O 5 glass annealed 

for 100 min at different temperatures. 

-78 -



Mössbauer spectra of 20LFV glass annealed at temperature for 100 min between 400 and 500 o C are 

shown in Fig. 2. One paramagnetic doublet due to distorted Fe III O 4 tetrahedra was observed with 

identical isomer shift () value of 0.39 mm s -1 and decreasing quadrupole splitting () from 0.67 to 

0.52 mm s -1 when the annealing temperature was changed from 400 to 450 o C (Fig. 2 a-d). On the 

other hand, three paramagnetic doublets with and of 0.40 and 0.25 mm s -1 , 0.38 and 0.60 mm s -1 , 

and 0.31 and 1.11 mm s -1 , respectively were observed when annealed for 100 min above 460 o C 

(Fig. 2 e-h). In these samples, absorption area of outer-most and inner-most peaks was increased 

(a) 

(e) 

(b) 

(f) 

(c) 

(g) 

(d) 

(h) 

with Figure an 2 increase 57 Fe-Mössbauer of annealing spectra temperature of 20Li 2 O•10Fe and became 2 O 3 •70V identical 2 O 5 glass to each annealed other, for which 100 min is ascribed at to 

the precipitation (a) 400, of semiconducting 

(b) 410, (c) 430, (d) 450, (e) 460, (f) 470, (g) 490 and (h) 500 o C. 

FeVO 4 [4, 5]. These results indicate that isothermal annealing of 20LFV glass at temperature higher 

than 460 o C results in the precipitation of FeVO 4. It is considered that isochronal annealing of 

20LFV glass at 400-450 o C causes an increase of due to the structural relaxation, as was confirmed 

from the decrease in (Fig. 2a-d), while it decreases owing to the precipitation of semiconducting 

FeVO 4 particles when annealed above 460 o C. 

References 

[1] T. Nishida, J. Kubota, Y. Maeda, F. Ichikawa and T. Aomine, J. Mater. Chem., 6 [12], 1889- 

1896 (1996). 

[2] S. Kubuki, Y. Tomota, R. Yoshimura, Z. Homonnay, K. Sinkó, E. Kuzmann and T. Nishida, 

Journal of Physics: Conference Ser., 217, 012026 (2010). 

[3] S. Kubuki, H. Sakka, K. Tsuge, Z. Homonnay, K. Sinkó, E. Kuzmann, H. Yasumitsu and T. 

Nishida, J. Ceram. Soc. Jpn., 115 [11], 776-779 (2007). 

[4] L. M. Levinson and B. M. Wanklyn, J. Solid State Chem., 3, 131-133 (1971). 

[5] V.D. Nithya and R. Kalai Selvan, Physica B, 406 (2011) 24–29. 

-79 -



(L9) 

BREAKTHROUGH IN SENSIVITY FOR QUADRUPOLE ICP-MS 

Meike Hamester 1, René Chemnitzer 1 and Søren Dalby 2 

1 Bruker Daltonics, Fahrenheitstrasse 4, 28359 Bremen, Germany 

2 Bruker Daltonics, Kallerupvej 39 d, 2640 Hedehusene, Denmark 

e-mail: meike.hamester@bdal.de 

Quadrupole ICP-MS became a robust analytical instrument to measure almost all elements of the 

periodic table and in almost any matrix. Sensitivity specifications increased with every new 

generation but high resolution magnetic sector field ICP-MS still exceeded sensitivities of 

quadrupole ICP-MS by far. However, the combination of a high efficient interface, an sophisticated 

ion optical system with a robust plasma could demonstrate for the first time ever that quadrupole 

ICP-MS (Bruker aurora Elite) can get clearly ahead of sensitivity specifications of magnetic sectorfield 

ICP-MS. More important: without compromising other parameter such as background, spectral 

interferences, or stability. 

The presentation will describe the technical layout of the high sensitivity ICP-MS (Bruker aurora 

Elite) and will elaborate for which applications such high sensitivity is beneficial (e.g. nanoparticles, 

laser ablation but also isotope ratio analysis. 

-80 -



(L10) 

DETERMINATION OF RARE EARTH ELEMENTS IN EXTRACTS FROM OIL 

REFINARY SPENT CATALYST BY ICP-MS WITH A REACTION CELL 

Jessee Severo Azevedo Silva 1 , Tatiane de Andrade Maranhão 2 , Fernando J. S. Oliveira 3 , Vera Lucia 

A. Frescura 1 

1 Universidade Federal de Santa Catarina, Florianópolis, SC, Brazil 

2 Universidade Federal do Rio Grande do Norte, Natal, RN, Brazil 

3 

Petróleo Brasileiro S.A, Gerência de Meio Ambiente, Rio de Janeiro, RJ, Brazil 

e-mail: jesseesevero@yahoo.com.br 

One primary process used in petroleum refining industry is the fluid catalytic cracking (FCC). Many 

catalysts are impregnated with rare earth elements (REE) in order to improve their cracking 

characteristics. With repetitive usage, the catalyst loses its activity and is rejected as a waste. Every 

year, hundreds of thousands of spent catalysts are produced and their applications and re-use are 

proposed, mostly as filler in cement. The use of FCC spent catalyst as a source of REE could be a 

very interesting application, considering the recovery and recycling concept. In order to evaluate the 

potential application of FCC spent catalyst as a REE source, studies were performed both to 

determine the concentration of REE in spent catalyst samples and the feasibility of their extraction. 

The FCC spent catalyst samples were digested in a microwave oven in a medium containing nitric 

and hydrochloric acids, hydrogen peroxide and HF. After the digestion procedure has been carried 

out, boric acid was added in excess and a second procedure, assisted by microwave irradiation, was 

carried out aiming at the dissolution of the REE complexes and to assure the complete elimination of 

fluoride ions. This treatment guaranteed the complete digestion of the samples and eliminated the 

risks of damage to the ICP-MS sample introduction system. Prior to the determination by ICP-MS, 

studies using a reaction cell with ammonia as the reaction gas were conducted. Four elements, Gd, 

Lu, Nd and Yb, required the use of ammonia to overcome polyatomic interferences. The optimized 

flow rates were 0.4 mL min -1 for Nd and Yb and 0.6 mL min -1 for Gd and Lu. The average 

concentration, in µg g -1 , for ten FCC spent catalyst samples are shown in Figure 1.All sixteen REE 

found in nature were present in the samples. The most significant element present in spent catalyst 

samples was lanthanum, with an average concentration of about 2.4% m/m. Other REE, as for 

instance Ce, Nd and Gd, were found in significantly high concentrations. 

Since FCC catalysts are impregnated with REE, it should be expected that obtaining REE from these 

samples will imply in a less expensive and easier process, when compared to their extraction from 

natural sources. In this sense, studies of extraction media, acid concentration, extraction time and 

temperature were carried out. After each study the analyte concentrations were measured by ICP-MS 

using the same method described before. The four media evaluated, HNO 3 , HCl, HNO 3 :HCl (1:3) 

and HNO 3 :HCl (3:1), at a temperature of 100 ºC for three hours, were very efficient in extracting the 

analytes, but nitric acid was the medium with the higher extraction potential as can be seen in Figure 

2. In this medium, the extraction percentage, compared with the concentration obtained for the 

digested sample, was higher than 80% for nine elements, including three elements for which the 

percentage was higher than 95% (La, Gd and Nd). 

-81 -



24000 

Average concentration, g g -1 

250 

200 

150 

100 

50 

Extraction percentage 

100 

80 

60 

40 

20 

La; Ce; Nd; Gd; 

Pr; Sm; Y; Others 

0 

La Ce Nd Gd Pr Sm Sc Y Others 

Figure 1. REE average concentrations, in µg g -1 , 

for ten FCC spent catalyst sample by ICP MS. 

0 

HNO 3 

HCl HNO 3 

:HCl 3:1 HNO 3 

:HCl 1:3 

Extraction media 

Figure 2. Extraction media evaluation using one 

FCC sample at a temperature of 100 ºC. 

Another study was carried out to evaluate if the extraction would be advantageous at lower 

concentration of HNO 3 . The same sample was submitted to extraction in nitric acid at concentrations 

of 1.4, 3.5, 7.0 and 10.5 mol L -1 for three hours at a temperature of 100 ºC. The results presented in 

Figure 3 show that even at low concentrations of HNO 3 a good recovery of REE from FCC spent 

catalyst sample can be achieved. 


100 La; Ce; Nd; Gd; 


80 

60 

40 

20 


60 

50 

40 

30 

20 

10 

La; Ce; Nd; Gd; 


0 

1.4 3.5 7.0 10.5 14.0 

HNO 3 

Concentration, mol L -1 

Figure 3. HNO 3 concentration study for REE 

extraction in a FCC sample at a temperature of 

100 ºC. 

0 

30 60 90 120 150 180 

Extraction time (at 30 0 C), min 

Figure 4. Study of REE extraction time using a 

FCC spent catalyst sample in a 1.4 mol L -1 HNO 3 

medium, at a temperature of 30 ºC. 

Two other studies were performed. Firstly, the extraction was carried out using the lower 

concentration of HNO 3 , 1.4 mol L -1 , at 100 ºC in intervals from 30 min to 180 min. The time was not 

an important factor in the extraction process, since no significant difference in the concentrations 

obtained within the studied time range was observed. Good recoveries were accomplished even 

after 30 min extraction. The second study was similar to the first, but at a temperature of 30 ºC. The 

results, shown in Figure 4, demonstrate that the temperature is a key factor in extracting REE from 

FCC spent catalyst samples. However, the previous conditions, which employ low acid 

concentration, low temperature and a short time result in significant extraction of the analytes, and it 

may appear as a more attractive approach, particularly considering that the process could be repeated 

one or two times to increase the extraction. Taking into account that hundreds of thousands of FCC 

spent catalyst are generated every year as waste, requiring investments in their treatment, the use of 

this material could be a very interesting and cheap a source of REE, especially La, and also be in 

agreement with the recycling concept. 

-82 -



(L11) 

SOME PROCEDURES OF REDUCING MATRIX EFFECTS IN ICP-MS ANALYSIS OF 

BIOLOGICAL SAMPLES 

Konstantin Ossipov 1 , Irina F. Seregina 1 , Mikhail A. Bolshov 1, 2 

1 Chemistry Department, Lomonosov Moscow State University, 1-3 Leninskie Gory, 119991 

Moscow, Russia 

2 Institute for Spectroscopy, Russian Academy of Sciences, 142190 Moscow, Troitsk, Fizicheskaya 

5, Russia 

e-mail: ossipovk@yandex.ru 

Inductively coupled plasma – mass spectrometry (ICP-MS) has already established itself as a routine 

method for analysis of biological samples. ICP-MS is widely used in clinical laboratories on account 

of indisputable advantages: multielemental determination, high sensitivity, high throughput and 

possibility of small volume sample analysis. However, spectral interferences and matrix effects can 

significantly complicate the determination of elements in such samples as blood, plasma, urine and 

hair and affect the accuracy of the results. In spite of great number of investigations the new 

approaches to suppress or account for the interferences in bio-samples analysis are still actual. 

Two techniques of bio-samples pre-treatment are mostly used – 1) acid mineralization (in open or 

closed vessels or MW digestion), and 2) dilution by the mixture of reagents (Triton X-100-EDTAbutanol) 

for whole blood or 1% HNO 3 1:10 for urine and plasma. The second technique is evidently 

simpler and less time consuming and successfully applied for the analysis of urine, plasma, 

lyophilized blood. But there are number of biological samples, which cannot be diluted - hair, dried 

blood, etc. 

The goal of this work is the investigation of the factors affecting the accuracy of the analysis of such 

bio-samples by MW digestion-ICP-MS technique. 

First experiments showed the noticeable (up to 30-40%) decrease of the Cu and Zn concentrations 

measured in blood samples after mineralization as compared to simple dilution of the same samples. 

Internal standards (IS) with different first ionization potentials were used to overcome this effect. It 

was shown that application of IS Rh (7.46 eV) is preferable only for elements with approximately 

the same IP (Co, Cu, Mn, Pb, Cr, Al) under conditions of optimal sensitivity (RF power 1440 W and 

nebulizer gas flow rate 1.2 L min -1 ). The discrepancy for elements with high IP (As, Se, Zn, Cd) 

cannot be fully eliminated even using IS Be (9.32 eV), while for Co, Cu, Mn, Pb, Cr, Al a 40-50% 

increase in relative signals is observed. 

The main reason of remaining difference between mineralization and dilution techniques might be 

high acidity of the digested samples. It was estimated that the residual content of nitric acid in 

digested solutions is 10-15% (v/v) for blood and 10% (v/v) for urine samples while 1% HNO 3 

solutions are used for dilution. The variation of ICP and sample introduction parameters is known as 

the strategy to overcome the acidic effect. Contrary to the published recommendations the decrease 

of RF power to 900 W had no effect on the measured analytes concentrations. The nebulizer gas 

flow rate did affect the analytical signals. The maximal RF power of 1440 W and the nebulizer gas 

flow rate of (0.8 – 1.0) L min -1 were found as the optimal parameters. Combination of application of 

the optimal parameters and IS provides adequate accuracy of the determination for Al, Cr, Mn, Co, 

Cu, Zn, As, Se, Cd, Pb in blood and hair samples. The accuracy of the developed strategy was 

proved by the analysis of the standard reference samples of blood (Seronorm Trace Elements Whole 

Blood, Norway) and hair (GBW 07601, China). 

-83 -



(L12) 

DEVELOPTMENT OF AN ANALYTICAL METHOD FOR Cd, Co, Cr, Cu, Ni and Pb 

DETERMINATION IN COSMETIC SAMPLES 

Amanda dos Santos Augusto, Érica Ferreira Batista and Edenir Rodrigues Pereira-Filho 

Federal University of São Carlos, Chemistry Department, P.O. Box 676, Zip Code 13565-905 São 

Carlos – São Paulo State, Brazil 

e-mail: erpf@ufscar.br 

This study presents a method for metals determination in some cosmetic samples such as, blush and 

eye shadow products. Elements as Cd, Co, Cr, Cu, Ni and Pb were determined using a ICAP 6000 

series, Thermo Scientific ICP OES (Inductively Coupled Plasma Optical Emission Spectrometry) 

and the most favourable working conditions were identified using desirability function [1] combined 

with a fractional factorial design (2 9-5 = 16 experiments). An aqueous multi element standard 

solution containing 1 mg/L of each analyte was introduced in the equipment and two responses were 

observed: signal area and relative standard deviation (RSD) for each analyte in the 16 experiments. 

Nine variables were investigated and a total of 78 responses were recorded. Four variables presented 

significant contrasts (Integration time for low wavelengths, flow rate during the analyses, radio 

frequency power and flow rate of nebulisation gas). The most favourable condition was identified 

when the highest signal and the lowest RSD were observed. Table 1 shows the final conditions. 

Table 1: Experimental conditions obtained for Cd, Co, Cr, Cu, Ni and Pb determination in ICP OES. 

Variables Most favourable (nm) in Axial and Radial 

condition 

views 

Integration time for low (variable 1) 

and high (2) wavelengths 

5 s for both Cd: 228.802; 

Co: 228.616; 

Flow rate of sample introduction (3) 4.2 mL/min 

Cr: 357.869; 

Flow rate during the analyses (4) 2.1 mL/min 

Cu: 324.754; 

Time for stabilization pump (5) 25 s 

Ni: 341.476; 

Radio frequency power (6) 

1150 W 

Pb: 220.353. 

Flow rate of auxiliary gas (7) 0.25 L/min 

Flow rate of nebulisation gas (8) 0.65 L/min 

Flow rate of coolant gas (9) 16 L/min 

The sample preparation procedure was performed using a microwave oven system (Berghof, 

Speedwave) and the conditions were also studied using a full factorial design (2 4 = 16 experiments). 

Sixteen experiments were performed in order to see the effects of four variables: HNO 3 

concentration (2 or 7 mol/L), sample mass (150 or 250 mg), power and temperature microwave oven 

program. Two millilitres of H 2 O 2 was also added in each experiment, the microwave oven power 

and temperature did not present significant effects in the studied range and the following conditions 

were fixed: between 800 and 1400W for power and between 180 and 210 o C for temperature. Nitric 

acid concentration and sample mass presented significant effects and these variables were fixed at 2 

mol/L and 250 mg, respectively when residual carbon content (RCC), residual acidity and analytes 

recovery were observed. Residual carbon content was calculated after C determination using ICP 

OES ( = 193.091 nm) [2] at a linear range of 15 to 1000 mg/L (LOD = 5.0 mg/L in Axial and 

Radial views). The RCC observed for the best condition was 2.8 ± 0.4 % (m/v, n = 5) and the 

residual acidity ranged between 90 to 105%. Cobalt, Cr, Ni and Pb concentration were not observed 

-84 -



in any sample. Copper and Cd were detected in blush and eye shadow samples, respectively. Table 2 

shows the results obtained for the determinations of Cu and Cd. 

Table 2: Cu and Cd concentrations obtained for blush and eye shadow samples. 

Sample [Analyte] (mg/kg), n = 3 Recovery (%) LOQ (mg/kg) 

Blush Cu = 0.96 ± 0.01 (Axial) 114 (Conc. added = 6 0.2 

µg/L) 

Eye shadow Cd = 1.04 ± 0.06 (Axial) 

Cd = 1.15 ± 0.09 (Radial) 

87 (Axial) 

96 (Radial) 

(Conc. added = 20 µg/L) 

0.01 (Axial) and 0.1 

(Radial) 

References: 

[1] Derringer, G.; Suich, R.; J. Qual. Technol.; 1980 12, 214. 

[2] Gouveia, S. T.; Silva, F. V.; Costa, L. M.; Nogueira, A. R. A.; Nóbrega, J. A.; Anal. Chim. Acta; 

2001, 445, 269; 

Acknowledgments: 

The authors are grateful to Thermo Scientific for the instruments, Fapesp (12/10680-6 and 

12/01769-3) and CAPES for the financial support. 

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(L13) 

THE NEW 8800 ICP-QQQ: HANDLING THE MOST DIFFICULT SAMPLES WITH EASE 

Uwe Noetzel 1 and Ed McCurdy 2 

1 Agilent Technologies, Germany, 

2 Agilent Technologies, UK. 

e-mail: uwe_noetzel@agilent.com 

ICP-MS has been widely accepted for inorganic analysis in reason to its fast, sensitive and multielemental 

capacities. However, the plasma, solvent and sample matrix give rise to polyatomic 

interferences on many analytes, so modern quadrupole ICPMS instruments employ a 

collision/reaction cell (CRC) to reduce these interferences. Indeed collision mode (using He cell gas) 

is used successfully in ICP-QMS to remove polyatomic interferences in high matrix samples since 

many years. However He mode cannot provide effective removal of intense interferences on some 

key analytes such as P, S and Se, or enable ppt-level analysis in high-purity materials. For ultra-trace 

analysis with ICP-QMS, reaction mode (using a reactive cell gas) can be more efficient than He 

mode, but often gives erratic results due to unpredictable reaction processes and cell-formed product 

ions. The 8800 employs MS/MS to solve these problems, enabling reaction mode to be used to its 

full potential. 

The 8800 ICP-QQQ features an additional quadrupole mass analyser (Q1) in front of the ORS 3 cell 

and analyser quadrupole (Q2). This configuration is called MS/MS or tandem MS. 

Combining the proven capabilities of ICP-MS with the unique power of MS/MS, the 8800 ICP- 

QQQ is a new analytical tool that can handle even the most difficult samples and applications with 

ease. 

In the current presentation, few examples will be given to illustrate the increase of performances that 

can be expected from the new 8800 ICP-QQQ. 

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(L14) 

A COMPARISON OF CONVENTIONAL (OFF-LINE) AND ON-LINE ISOTOPE 

DILUTION ICP-MS FOR THE DETERMINATION OF TOTAL SELENIUM IN HUMAN 

SERUM 

Petru Jitaru 1,2 , Caroline Oster 2 , Guillaume Labarraque 2 , Maria Estela del Castillo, Sophie Vaslin- 

Reimann 2 and Paola Fisicaro 2 

1 

HydrISE, Institut Polytechnique LaSalle Beauvais, 19 rue Pierre Waguet, 60026 Beauvais cedex, 

France 

2 

Laboratoire National de Métrologie et d’Essais (LNE), Department of Biomedical and Inorganic 

Chemistry, 1 rue Gaston Boissier, 75024 Paris Cedex 15, France 

Selenium is one of the most widely investigated of all the trace element nutrients in the last decades, 

mainly due to its role in cancer prevention. It has been demonstrated that most biological functions 

attributed to Se are mediated by the selenoproteins. For biomedical applications, the serum 

selenoproteins, namely glutathione peroxidase (GPx) and selenoprotein P (SelP) as well as the Secontaining 

protein, selenoalbumin (SeAlb) are of main interest for the assessment of the Se status. 

Accurate determination of the selenoproteins is still challenging, especially because of the lack of 

standards commercially available as well as the difficulty of their preparation in-house. In these 

circumstances, the only method nowadays available for the quantification of selenoproteins is the 

on-line (post-column) isotope dilution (ON-IDMS) after their HPLC separation and further (on-line) 

detection by ICP-MS. Briefly, this technique relies on spiking the eluted species post column with 

an isotopically enriched material (‘spike’), which is generally an inorganic species of the analyte. It 

is worth to emphasize that ON-IDMS is not recognized as a primary method of chemical analysis, as 

it is the case of the conventional off-line IDMS (OFF-IDMS) where the analytes (the total element or 

specific chemical species) are mixed with the spikes prior to the ICP-MS (total element) or HPLC- 

ICP-MS (species-specific) measurements. Therefore, validation of ON-IDMS is required, especially 

when applied to bio-inorganic speciation analysis. Nevertheless, for such applications, the validation 

of ON-IDMS can be tentatively carried out only against a primary method such as OFF-IDMS 

applied for total element determination. 

This study presents a comparison between OFF-IDMS (primary method) and the ON-IDMS for the 

determination of total selenium in human serum. Firstly, the serum was analyzed OFF-ID-ICP-MS 

using two sample preparation procedures. In a first instance, the serum was digested by an acidic 

microwave treatment in order to destroy the proteins and hence obtain the (total) inorganic selenium. 

In parallel, the serum was diluted (1:25) with ultra-pure water before total selenium quantification 

by OFF-ID-ICP-MS. The latter approach, apart from being considerably more simple and rapid, 

provided also a 7 times signal enhancement hence leading to significant increase in the precision of 

the isotopic ratios measurements. Therefore, in view of comparison of OFF-IDMS and ON-IDMS 

methods, the whole serum was diluted with ultrapure water and analyzed further on. Each analysis 

step was repeated at least three times, and a complete uncertainty budget was evaluated for each 

analysis. 

The two methods developed in this study, namely OFF-IDMS and ON-IDMS were applied to the 

analysis of three commercially available serums with certified (BCR-637, IRMM, Geel, Belgium) or 

indicative (Seronorm Trace Elements-Level 1 and Level 2 serums, SERO AS, Billingstad, Norway) 

values for total selenium. Both methods provided results in good agreement with the certified and 

indicative values, respectively. In addition, the expanded uncertainty was calculated for the analysis 

of each serum both by OFF-IDMS and ON-IDMS with emphasis on the most predominant 

uncertainty sources in each case. 

This work comparing OFF- and ON-IDMS from a metrological perspective could be considered as a 

case study providing pro evidence for the use of ON-IDMS, either for speciation analysis of biomolecules 

or for the total element determination in biological fluids, due to its simplicity (no sample 

preparation required at all), versatility and accuracy. 

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(L15) 

FROM 2D TOWARDS 3D ELEMENTAL IMAGING BY LASER ABLATION ICP-MS - A 

STUDY OF ARCHAEOLOGICAL GLASS 

Vid S. Šelih 1 , Johannes T. van Elteren 1 , Martin Šala 1 , Andrei Izmer 2 , Frank Vanhaecke 2 , Emilio F. 

Orsega 3 , Serena Panighello 3 and Norman H. Tennent 4 

1 Analytical Chemistry Laboratory, National Institute of Chemistry, Hajdrihova 19, SI-1000 

Ljubljana, Slovenia, 

2 Department of Analytical Chemistry, Ghent University, Krijgslaan 281-S12, B-9000 Ghent, 

Belgium 

3 Department of Molecular Sciences and Nanosystems, University Ca'Foscari Venezia, Calle Larga 

S. Marta 2137, IT-30123 Venice, Italy 

4 

Faculty of Humanities, University of Amsterdam, Hobbemastraat 22, Amsterdam 1071 ZC 

The Netherlands 

e-mail: vid.selih@ki.si 

Archaeological glass has been a subject of many studies that try to reveal ancient glass 

manufacturing techniques, sources of materials used during production (sands, fluxes, colourizers, 

opacifiers, etc.) and provenance studies as well as studies that focus on mechanisms of degradation 

of glass artefacts during time. Various techniques of elemental analysis, such as e.g. SEM-EDS, 

EMPA, TEM, micro-XRF, SIMS, LA-ICP-MS have been used for such studies and they mainly 

focus on bulk or localized microanalysis of the sample. However useful the bulk or localized 

analyses are, even more information can be retrieved from surface (2D) and depth (3D) elemental 

distributions. Laser ablation ICP-MS is particularly suitable for such studies, as it is very versatile 

with a very large dynamic range, low detection limits and the potential for imaging on scales from 

hundreds of μm 2 to tens of mm 2 . 

We developed a two-dimensional LA-ICP-MS imaging procedure that succesfully extracts the 

sample's surface elemental features. For this purpose the laser beam is scanned across the surface of 

the sample along parallel lines and the data obtained are manipulated so that a “map” of the element 

distributions is obtained. Aided by sum-normalization calibration approaches 1 such element 

distributions can be converted to quantitative 2D elemental images. In this way maps for 54 

elements (oxides) in archaeological glass 2 were obtained (Figure 1). 

To further study processes such as weathering and degradation of surface layers of archaeological 

glass, 2D surface distributions are not enough and a novel three-dimensional LA-ICP-MS analysis 

approach was very developed recently 3 . This approach is a combination of rastering and depth 

profiling, and allows for direct 3D mapping of “hard” materials such as glass but it might also be 

used for similar (or even "soft") materials. 

The 3D mapping procedure (see Figure 2) features slow laser drilling on a virtual grid on the surface 

of the sample and ultrafast ICP-MS acquisition to resolve individual ablation pulses. Acquired data 

is then manipulated in such way that 3D quantitative elemental (volume) images are created. These 

can be visualized as 3D volume images or time-lapse movies. 

We successfully tested this approach to investigate mechanisms behind the degradation of a 

medieval, weathered glass artifact using colocalization analysis of selected cross-sectional 2D 

elemental images constructed in arbitrary planes of the acquired 3D volume images. 

-88 -



(L16) 

DIRECT SOLID QUANTITATIVE ANALYSIS OF BATTERY COMPONENTS USING LA- 

ICP-MS AND DEVELOPMENT OF CUSTOM MADE SOLID STANDARD MATERIALS 

ANALYSIS OF BATTERY MATERIALS 

Björn Hoffmann, Martin Winter, Sascha Nowak * 

* (sascha.nowak@uni-muenster.de) 

University of Münster, MEET Battery Research Centre, Corrensstraße 46, 48149 Germany 

Laser ablation is a method that allows direct sampling of solids. This is done by evaporating small 

spots of the sample with a high powered pulsed laser in an argon-helium-atmosphere. The aerosol is 

transported into an inductively coupled plasma and subsequently analyzed in a mass spectrometer. 

This approach retains spatial information, within certain limitations and can be used to record three 

dimensional concentration profiles. 

Lithium-ion batteries still experience a loss in performance over time. Although the technology is 

state of the art in portable consumer electronics, widespread application in automobiles requires 

improvement beyond the current capabilities. Understanding deterioration processes and 

mechanisms requires the examination of aged cells. As electrochemical cells do not age 

homogeneously and electrochemistry in general is heavily dependent on surface properties, bulk 

analysis is not suitable for investigating these phenomena. LA-ICP-MS promises to be a suitable 

tool to study these issues. 

Our initial studies show that battery materials are challenging samples that require thorough 

optimization of the ablation conditions. Due to analysis of the undiluted and undissolved solid 

sample, laser ablation offers detection limits comparable to liquid analysis with easier sample 

preparation and most importantly offers spatial information on analyte concentrations. 

-89 -



(L17) 

DIRECT ELEMENTAL ANALYSIS OF NANODIAMONDS WITH ICP-OES 

Dmitry S. Volkov, Mikhail A. Proskurnin, and Mikhail V. Korobov 

Lomonosov Moscow State University, Chemistry Department, 119991, 1-build. 3, Leninskie gori, 

MSU, Moscow, Russia 

e-mail: dmsvolkov@gmail.com 

Detonation nanodiamonds (DNDs) gain much attention for biomedical and clinical applications [1], 

and high-technology purposes [2-7] due to their unique properties. However, many DND properties, 

which are relevant for such uses (aggregate size, surface groups, optical and colloidal properties, 

etc.), depend on their production and purification technology. In particular, it is very important to 

know, reliably and precisely, the DND impurity composition — content of metals and nonmetal 

elements first — because some chemical elements may be hazardous even in trace quantities, 

especially if we deal with nanomaterials. In addition, they also change the DND properties, e.g. 

thermal and oxidative resistance [8, 9]. Thus, the replicability of DND technology is a topical 

problem in the industry [10]. 

The development of reliable chemical analytical control is the obvious first step to render traceable 

DND properties and to improve and advance the required technologies. This usually means sensitive 

and selective multielement analysis because the impurities in DNDs have various nature and 

quantity level — metal-oxide nanoparticles, carbides, silicon dioxide, insoluble salts as well as 

cations and anions adsorbed at DND surface [11-13]. They appear due to the interactions in the 

detonation reaction chamber (Fe and Cr) or from the explosion initiation (Cu, Pb, and Hg) [12], or 

adsorbed [14] on already formed DNDs from liquids (acids and water) used for their isolation from 

the detonation-chamber charge [13, 15]. To the best of our knowledge, the problem of quantitative 

multielement analysis of DNDs was not sufficiently investigated. 

In our opinion, analysis of NDs can be reliably solved using the state-of-the-art method of atomic 

spectroscopy — optical-emission analysis with inductively coupled plasma (ICP-OES). This method 

is de facto standard for various environmental, high-technology, clinical and pharmaceutical 

analysis. In this paper, we will discuss the analytical possibilities of ICP-OES for accurate and 

precise quantifications of various elements in DNDs. 

We developed a technique for quantitative multielement analysis of DND impurities by ICP-OES 

using a slurry nebulization technique. We found out that the most of analysed DNDs contain 

relatively high amounts of Fe, Na, Si; Cu, B, Ni, Al (>100 ppm), while Pb, Zn, K, Mn, B, Cr, Mg, 

Mo, Sn, W, Ba, Sb, Co, Sr are in low but significant amounts. Moreover, we measured generalised 

indicator property — the ash mass after combustion — and found that all incombustible impurities 

comprise 1–3% of the total DND mass. In commercially available «deeply purified» DND samples, 

we detected much lower impurities of Сu, Ni, Al and slightly lower amounts of Fe, while other 

elements were almost at the same average level as in not so thoroughly purified DND species. This 

means that the purification process is possible, but needs improvement. We have found that DNDs 

from different manufacturers contain very different impurities and even for a single product type, 

they change from lot to lot. This means that DND purity needs to be monitored, and additional 

purification might be made if necessary 

Acknowledgements. This work was supported by the RFBR, grants nos. 12-03-00653-а and 12-03- 

31569-mol_a and the MST of Russian Federation, contract no. 16.740.11.0471. 

-90 -



(L18) 

EXPERIMENTAL SPECTROSCOPIC AND QUANTUM CHEMICAL STUDIES OF THE 

REACTIVITY OF ALKYLRESORCINOLS IN REDOX PROCESSES 

Alexander A. Kamnev 1 , Roman L. Dykman 1 , Alexei G. Shchelochkov 1 , Krisztina Kovács 2 , Ernő 

Kuzmann 2 and Alexei N. Pankratov 3 

1 Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and 


2 Laboratory of Nuclear Chemistry, Institute of Chemistry, Eötvös Loránd University, P.O.Box 32, 

H-1512, Budapest, Hungary 

3 Division of Analytical Chemistry and Chemical Ecology, Institute of Chemistry, N.G. 

Chernyshevskii Saratov State University, 410012 Saratov, Russia 

e-mail: aakamnev@ibppm.sgu.ru; a.a.kamnev@mail.ru 

The physical chemistry and reactivity of extracellular signalling molecules, which are used by 

microbial consortia as a “chemical language”, is of importance for understanding and predicting 

abiotic impacts of the environmental conditions on microbial communication [1]. Any possible 

chemical transformations of such molecular signals (e.g., hydrolysis, complexation or oxidation 

reactions) would result in their exclusion from the signalling pathways, which is equivalent to a 

“message non-delivery”. 

In our earlier studies, it was shown using a variety of spectroscopic techniques that indolic 

phytohormones of the auxin series (e.g. indole-3-acetic acid synthesized by many soil bacteria and 

excreted into the environment), involved in plant-microbe interactions and signalling, can be 

gradually oxidised in moderately acidic media in the presence of iron(III) [2, 3]. 

In this work, chemical reactivity under similar conditions (simulating acidic soil environment) was 

studied for alkylresorcinols (ARs; 1,3-dihydroxybenzenes with alkyl substituents in positions 4 or 

5), chemical analogues of extracellular microbial autoinducers with adaptogenic functions [4, 5]. 

The kinetics of iron(III) reduction by ARs with different molecular structures and the ironcontaining 

products formed both in the solutions and in the dried solids were studied using freezequench 

57 Fe Mössbauer spectroscopy. Soluble products in the course of ARs oxidation were 

monitored using UV spectrophotometry [4, 5] and analysed using GC-MS and FTIR spectroscopy. 

The results obtained have shown that the AR redox-reaction rate strongly depends on the length and 

position of the alkyl substituent in the aromatic ring. Thus, at pH~3, 4-n-hexylresorcinol is much 

more rapidly (within minutes) oxidised than 5-methylresorcinol under similar conditions. The results 

of GC-MS and FTIR spectroscopic analyses of 4-n-hexylresorcinol oxidation products have shown 

that the first step of AR oxidation in the presence of iron(III) in weakly acidic aqueous media 

involves an additional hydroxylation of the benzene ring in the position C6. This abiotic oxidation 

pathway is similar to enzymatic oxidation of ARs reported in the literature. The observed chemical 

transformations show possible routes of mutual influence of Fe III in acidic soils and organic 

biomolecules of microbial origin, including extracellular molecular signals. These routes are of 

importance both for soil microbial ecology and for biogeochemistry of iron. 

In order to obtain theoretical evaluations of the ARs reactivities in redox processes, quantum 

chemical computations at the B3LYP/6-311++G(3d,3p) level were carried out to elucidate the steric 

and electronic structures of resorcinol as well as its 4-n-hexyl- and 5-methyl-substituted analogues. 

-91 -



The results have shown that 4-n-hexylresorcinol has the highest propensity for oxidation as 

compared with 5-methylresorcinol, while resorcinol has the lowest propensity. This trend is in line 

with our experimental data showing that 4-n-hexylresorcinol is much more rapidly oxidised at pH~3 

in the presence of iron(III) than 5-methylresorcinol, while non-alkylated resorcinol is not prone to 

oxidation under similar conditions (see [1] and references therein). Regioselectivity of the 

hydroxylation process in the positions C4 and/or C6 of the benzene ring for resorcinol and its 

alkylated analogues has been shown to correlate with the calculated spin density values at the atoms 

in the corresponding cation radicals. This implies a homolytic mechanism of the hydroxylation 

process. 

Acknowledgements. This work was supported in part by NATO Grant ESP.NR.NRCLG 982857 

and under the Agreement on Scientific Cooperation between the Russian and Hungarian Academies 

of Sciences for 2011–2013 (Project # 28). 

1. Kamnev A.A., Kovács K., Kuzmann E., Vértes A. (2009) J. Mol. Struct. 924, 131-137. 

2. Kovács K., Sharma V.K., Kamnev A.A., Kuzmann E., Homonnay Z., Vértes A. (2008) Struct. 

Chem. 19, 109-114. 

3. Kovács K., Kamnev A.A., Mink J., Nemeth Cs., Kuzmann E., Megyes T., Grosz T., 

Medzihradszky-Schweiger H., Vértes A. (2006) Struct. Chem. 17, 105-120. 

4. Kamnev A.A., Kovács K., Dykman R.L., Kuzmann E., Vértes A. (2010) Bull. Russ. Acad. Sci. 

Phys. 74, 394-398. 

5. Kamnev A.A., Dykman R.L., Kovács K., Kuzmann E. (2013) Bull. Russ. Acad. Sci. Phys. 77 (6), 

in press (DOI: 10.7868/S0367676513060161). 

-92 -



(L19) 

VIBRATIONAL SPECTRAL ANALYSIS OF THE ISOTOPIC SPECIES OF HYDROGEN 

SULPHIDE, HYDROGEN SELENIDE AND WATER USING THE U(4) ALGEBRAIC 

MODEL 

Nirmal Kumar Sarkar 

Department of Physics, Karimganj College, Karimganj – 788710, India 

Email : nksarkar49@gmail.com 

With the development of more powerful experimental techniques, molecular spectroscopy is now 

going through an exciting time of renewed interest. Tunable, stable and powerful lasers are now 

available to create highly excited levels with unprecedented resolution. Further more, new detection 

techniques are constantly being developed with sensitivities far exceeding the limits of detectors 

used just a few years back. To maintain resonance with the rapid development of sophisticated 

experimental approaches, theoretical physics has also been constantly tested to provide a collection 

of satisfactory models that can account for the experimental observations. It should be noted that 

molecular spectroscopy is undergoing a radical change not simply due to the development of more 

powerful experimental techniques. Also, one should realize that as a consequence of new (and quite 

often unexpected) experimental results, unprecedented efforts towards constructing alternative 

theoretical models have taken place in recent years. 

A comprehensive theoretical treatment for most aspects of molecular spectroscopy necessarily has to 

rely on a Hamiltonian formulation. The typical theoretical procedure used to study a given molecule 

consists of (i) separating the electronic and nuclear motions (assuming the Born-Oppenheimer 

approximation ) and (ii) solving the Schrödinger equation in the potential surface for the rovibrating 

nuclei. For large molecule (larger than a diatomic), the potential energy surface is a very complex 

function, composed of a discouragingly large number of coordinates. To this problem, a standard 

approach involves approximating the potential energy surface by convenient analytical functions. 

Various approaches have been used so far in the study of molecular spectra. Out of these, two 

important approaches are – ( i ) Dunham expansion[1] and ( ii ) potential approach[2]. A simple 

analysis of molecular rovibrational spectra is provided by the Dunham expansion. This is an 

expansion of the energy levels in terms of vibration-rotation quantum numbers. This expansion, 

however, does not contain any information about the wave functions of individual states. Thus, 

matrix elements of operators cannot be directly calculated. In the Dunham expansion, one needs a 

large number of parameters to account for a large polyatomic molecule. Further, these parameters 

have to be adjusted by a fitting procedure over a conveniently large experimental database, which is 

not always available. This is another serious drawback for this approach. Compared to the Dunham 

expansion, a better analysis is provided by the potential approach in the study of molecular spectra. 

Energy levels are obtained by solving the Schrödinger equation with an inter atomic potential. 

The potential is expanded in terms of inter atomic variables. The solution of the 

Schrödinger equation here provides wave functions from which matrix elements of various operators 

can be calculated. In this approach, all manipulations are either differentiations or integrations. 

Though the potential approach is better compared to the Dunham expansion, one should note that 

this approach also encounters difficulties as soon as we consider highly excited levels. Once more, a 

large number of parameters are needed here to achieve meaningful results for a large polyatomic 

molecule. 

Since the last part of the 20 th century, an algebraic approach[3-4] has been used in the study of 

molecular spectra. The algebraic approach attracted a wider scientific community in recent years for 

-93 -



the analysis and interpretation of experimental rovibrational spectra of small and medium-sized 

molecules. This approach is based on the idea of dynamical symmetry and is expressed through the 

language of Lie algebras. This approach can account for any specific mechanism relevant for the 

correct characterization of the molecular dynamics and spectroscopy. Applying algebraic techniques, 

in this approach, one obtains an effective Hamiltonian operator that conveniently describes the 

rovibrational degrees of freedom of the physical system. Unlike the more familiar differential 

operators of the potential approach, the Hamiltonian used in the algebraic approach is 

algebraic and so are all the operations in the method. The technical advantage of the 

algebraic approach is the comparative ease of algebraic operations. Equally important is the 

results, obtained by comparison with experiment. For this approach, another important 

advantage is that there are general forms of algebraic Hamiltonians and that entire classes of 

molecules can be described by a common Hamiltonian where only the ( typically, linear ) 

parameters are different for the different molecules. Furthermore, in algebraic approach, we can 

have a good accuracy in the study of vibrational spectra of a molecule, by using only a fewer 

parameters than in the traditional approaches. 

Till today, the algebraic models have been applied successfully in the study of vibrational spectra of 

linear triatomic, linear tetratomic and some other small and medium-sized molecules[5-10]. A 

limited number of successful attempts[5,9-10] has been reported so far in the application of 

algebraic models to study the vibrational spectra of bent XY 2 and bent XYZ molecules. For 

algebraic models, a large sector of bent triatomic molecules has been remained unattended till today. 

In this study, a successful application of U(4) algebraic model has been reported in the vibrational 

spectral analysis of the isotopic species of hydrogen sulphide, hydrogen selenide and water. The 

inclusion of intermode couplings in algebraic models has been stated to give a deep insight into 

detailed spectroscopy of the molecules. With a detail spectral analysis, in this study it has been 

shown that the isotopic species of hydrogen sulphide, hydrogen selenide and water can be 

approximated very well using the U(4) algebraic model. 

References 

[1] J. L. Dunham, Phys. Rev. 1932, 41, 721-731. 

[2] G. Herzberg, Spectra of Diatomic Molecules, Van Nostrand, Toronto, (1950). 

[3] R. D. Levine and C. E. Wulfman, Chem.Phys.Lett. 1979, 60, 372-376. 

[4] F. Iachello, Chem. Phys. Lett. 1981, 78, 581-585. 

[5] F. Iachello, R. D. Levine, Algebraic Theory of Molecules, Oxford University Press, 

Oxford, 1995. 

[6] Nirmal Kumar Sarkar, Joydeep Choudhury and Ramendu Bhattacharjee, Mol. Phys. 

2006, 104, 3051-3055; Nirmal Kumar Sarkar, Joydeep Choudhury, Srinivasa Rao 

Karumuri and Ramendu Bhattacharjee, Mol.Phys. 2008, 106, 693-702. 

[7] Nirmal Kumar Sarkar, Joydeep Choudhury, Srinivasa Rao Karumuri and Ramendu 

Bhattacharjee, Eur. Phys. J. D. 2009, 53, 163-171. 

[8] Srinivasa Rao Karumuri, Nirmal Kumar Sarkar, Joydeep Choudhury and Ramendu 

Bhattacharjee, J. Mol. Spectrosc. 2009, 255, 183-188. 

[9] Nirmal Kumar Sarkar, Joydeep Choudhury, Srinivasa Rao Karumuri and Ramendu 

Bhattacharjee, Vib. Spectrosc. 2011, 56, 99-104. 

[10]Nirmal Kumar Sarkar, Joydeep Choudhury, Ramendu Bhattacharjee, Vib. Spectrosc., 

2012, 60, 63-67. 

-94 -



(L20) 

THEORETICAL INVESTIGATION OF THE CW ABSORPTION, RESONANCE RAMAN 

AND REMPI SPECTROSCOPY OF THE S 1 AND S 2 STATES OF CIS-1,3,5-HEXATRIENE 

AND TRANS-1,3,5-HEXATRIENE 

Clemens Woywod 1 

1 Centre for Theoretical and Computational Chemistry, 

Chemistry Department, University of Tromsø, N-9037 Tromsø 

The 2 1 A g and 1 1 B u states of trans-1, 3, 5-hexatriene (THT) are vibronically interacting to first order 

via modes of b u symmetry. Likewise, vibrations transforming according to the b 1 irreducible 

representation are linearly coupling the 2 1 A 1 and 1 1 B 1 states of cis-1, 3, 5-hexatriene (CHT). We 

have developed vibronic coupling Hamiltonians for a description of the photoinduced excited state 

dynamics of both isomers based on ab initio electronic structure information [1,3,5,6]. Solution of 

the vibronic Schr¨odinger equation for each system allows for the simulation of continuous wave 

ultraviolet photoabsorption and resonance Raman spectra [2, 4]. In addition, the observed resonance 

enhanced multiphoton ionization (REMPI) spectrum of the 2 1 A 1 state of CHT has been modeled. 

The results of the calculations provide evidence for strong S 1 –S 2 vibronic coupling in both 

molecules and an explanation for the elusiveness of the 2 1 A g state of THT to observation. 

[1] C. Woywod, W. C. Livingood and J. H. Frederick, J. Chem. Phys. 112, 613 (2000). 




[5] C. Woywod, J. A. Snyder and J. H. Frederick, J. Phys. Chem. A. 105, 2903 (2001). 

[6] C. Woywod, Chem. Phys. 311, 321 (2005). 

-95 -



(L21) 

BASIS SET EXTRAPOLATION FOR HIGH RESOLUTION SPECTROSCOPY 

Kiran Sankar Maiti 

Department of Chemistry and Molecularbiology, University of Gothenburg, PO Box 462, SE-40530 

Gothenburg, Sweden 

e-mail: kiran.maiti@gu.se 

Recent development on experimental method of coherent multi–dimensional infrared spectroscopy 

provides a powerful new tool to study structure and dynamics of proteins and other biomolecules 

with a temporal resolution down to the sub–picosecond regime. The observed multidimensional 

spectra contain structural and dynamical information in terms of diagonal and cross–peak shapes, 

locations, and intensities and their respective temporal evolution. Extensive theoretical modeling is 

required to invert this data to obtain insight into the molecular dynamics. 

The important spectral features are due to anharmonicities in the vibrational Hamiltonian and 

nonlinearities in the dipole operator of the molecule. The accuracy of the anharmonic spectra depend 

upon the accurate potential energy surface (PES) calculation through the internal degrees of 

freedom. The recent development of high level quantum chemical ab initio method reached to 

spectroscopic accuracy for small molecules. The highly accurate ab initio calculation requires the 

basis functions to be as large as possible. As the basis function increases, the computational expense 

grows much faster than the rate at which the accuracy is improved, which makes the method 

unaffordable for the highly accurate PES calculation. On the other hand, spectroscopic accuracy can 

not be achieved by the smaller basis sets. In such a situation extrapolation of the energy to the basis 

set limit may speed up the PES calculation if there is a general extrapolation scheme. 

It is well known that Hartree-Fock (HF) energy converges very quickly and essentially reaches the 

basis set limit with the small basis set. Therefore spectroscopic accuracy only depends upon the 

accurate calculation of the correlation energy, which is known to converge very slowly. Two point 

extrapolation of the correlation energy, proposed by Halkier et al. reached to the spectroscopic 

accuracy but this method suggests to extrapolate from two larger basis sets, which is not feasible for 

large molecules. Inclusion of fifth order term from Schwartz’s formula provides an efficient route to 

extrapolate the correlation energy from small basis sets and reduces the computational expenses by 

two to three order of magnitude to reach the basis set limit correlation energy. 

-96 -



(L22) 

EXPLORING STRUCTURE AND ULTRAFAST DYNAMICS OF PROTEIN AND PEPTIDE 

USING TWO COLOR 2DIR SPECTROSCOPY 

Susmita Roy and Kiran Sankar Maiti 

Department of Chemistry and Molecularbiology, University of Gothenburg, PO Box 462, SE-40530 

Gothenburg, Sweden 

e-mail: kiran.maiti@gu.se 

A significant technological development on laser science and spectroscopy is going on during last 

couple of decads. Specially generation and control over the femtosecond infrared pulse, permits to 

visualize the time-dependent structural changes of fundamental physical processes in complex 

material and biological system. One of these development is two-dimensional infrared (2DIR) 

vibrational echo spectroscopy which has essentially sufficient time resolution to observe the 

structure and dynamics of proteins and peptides. Mainly three sequence of ultrafast pulses with 

phase match conditions are employed experimentally. Depending upon the sequence and data 

collection, the technique varies and named differently, but the 2DIR spectra looks same. The 

structural information is typically present in terms of the position, strength, and shape of the offdiagonal 

cross-peaks in the 2D spectrum. These are directly related to the anharmonic vibrational 

structure of the molecule. 

-97 -



(L23) 

FAT DETERMINATION OF INTACT FOOD SAMPLES WITH TIME-DOMAIN 

NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY AND CHEMOMETRICS 

Fabiola Manhas Verbi Pereira and Luiz Alberto Colnago 

Embrapa Instrumentation, St Quinze de Novembro, 1452, 13561-260 São Carlos/São Paulo state, 

Brazil 

e-mail: fmverbi@uol.com.br 

The analytical technique time-domain nuclear magnetic resonance (TD-NMR) is a potential 

alternative to distinguish between fat and water molecules, mainly in food products. The high 

specificity of this technique for total fat or oil content is based on signal from protons, in our study 

hydrogen protons, that is recorded as relaxation decays. For instance, the decays acquired using the 

sequence of pulses Carr-Purcell-Meiboom-Gill (CPMG) comprise analytical information from oil 

and water of samples. The differences within signals are directly related to the fat/water composition 

and 1H transverse relaxation time (T2) is usually applied to differentiate both components, because 

this physical property depend on molecular mobility. The sequence known as Continuous Wave- 

Free Precession (CWFP) is able to measure longitudinal relaxation time (T1) and T2 in a single and 

fast experiment. The main objective of this study is to develop accurate models for prediction of the 

fat content in mayonnaise and beef cattle samples. This method was previously applied to measure 

moisture on frozen-thawing meat and to classify plums according to sugar content. The direct 

application is to help the consumers to better choice the food product according to their needing and 

diet. 

The tested mayonnaise samples were purchased at the local markets (São Carlos, São Paulo State, 

Brazil). Twenty one samples were from the same lot and, 10 remaining samples from another lot 

were used to test the prediction ability of the models. All samples were taken of three worldrenowned 

manufacturers. The number of samples varying in fat according to the label product was: 

3 of 10.0 g 100 g-1, 19 of 15.0-22.5 g 100 g-1 and 9 of 30.8-55.8 g 100 g-1. The volume of the packing 

was between 107 and 109 cm3, corresponding to net weight up 400 to 500 g. Sixty-one Bonsmara 

heifers were separated into five groups according to genetic (breeding composition) and feed system 

(grain and grass feed). After harvest and chilling, a portion of each left side strip loin (Longissimus 

dorsi muscle) was collected and vacuum packaged. The through-package signal acquisition of intact 

mayonnaises were recorded using NMR spectrometer (Spinlock Magnetic Resonance Solution, 

Cordoba, Argentina) with a permanent Halbach magnet of 0.23 T (9 MHz for 1H), 10 cm bore, 50 

cm of analytical magnet and 120 cm of pre-polarizer magnet. The applied sequence of pulses for 

CPMG was π/2 and π pulses of 9.2 and 18.08 µs, respectively; echo times τ = 200 µs and 2500 

echoes. After thawing, each raw beef sample was separated into three cylindrical slices using a 

cylinder cutter with a diameter of 2 cm. For beef cattle measurements, a benchtop SLK 100 TD- 

NMR spectrometer (Spinlock Magnetic Resonance Solution, Cordoba, Argentina) equipped with a 

0.23 T permanent magnet (9 MHz for 1H) and a 13 x 30 mm probe head was applied to collect 

CPMG and CWFP decay signals. The CPMG sequence was executed using π/2 and π pulses of 6.28 

and 12.56 µs, respectively, and echo times of τ = 300 µs with a total of 1500 echoes. The dead time 

was approximately 50 µs. The CWFP [6] sequence also used π/2 and π pulses of 6.28 and 10.6 µs, 

echo times of τ = 141.56 µs and 1501 echoes. The frequency offset was 5 KHz. Each signal for both 

sequences was the result of an average of four scans. The room temperature was held constant at 23 

°C for every measurement. Three replicates for each sample were carried out for the extraction of 

lipids using the Bligh and Dyer method. Firstly, 

the signals of TD-NMR CPMG were investigated using the principal component analysis (PCA). 

-98 -



The univariate model for fat prediction was performed using the transverse relaxation time (T2) 

values exponentially fitted to a function available on Origin 8.1 (OriginLab, Northampton, MA, 

USA). The chemometric technique partial least squares (PLS) was used to compute the multivariate 

model. PCA and PLS are available at Pirouette 4.0 rev. 2 software (Infometrix, Bothell, USA). 

The exploratory analysis of mayonnaise data using PCA shows the tendency of samples to spread 

along a first principal component (PC1) according to the fat range with 99.5% of total explained 

variance for the PC1 and PC2, as shown in Figure 1a. On right side of the plot of Figure 1a, the 

scores represent the samples with low values of total lipids (g 100 g-1) up 10.0 (dark circles) and on 

opposite side the scores with dark triangles symbols are the highest ones up 30.8 to 55.8 g 100 g-1. 

No outliers were observed in this data. The loadings plot related to independent variables was 

represented in Figure 1b. The best pre-processing applied to the signals was mean-centering. In this 

case, the auto-scaling of the independent variables (X matrix) was not adequate, because the spectral 

nature of data. The profiles of the signals represent more or less short decays according to fat content 

on samples under analysis. 

A very good linear fitting was verified between the reference values and those predicted by PLS 

with values of 0.93 and 0.97 for training and validation data sets. The total fat content of 10 

remaining samples was also successfully predicted by PLS with high linear correlation coefficient of 

0.93. For PLS model, the highest values of r prove better fat predictability than univariate model. 

The results from PLS model shown indicates a potential of TD-NMR for industrially applicable in 

food analysis considering the high linearity and, regarding the signals were obtained from entire 

content of packing of mayonnaise. Otherwise, the bulk material was used for lipids extraction. 

For beef cattle, the potential of these multivariate models was also confirmed by the low values for 

RMSEP, between 1.16 (CPMG) and 1.55 (CWFP). Thus, the multivariate models can help predict 

the studied properties by measuring of fat content using TD-NMR. The correlation coefficients (r) 

between the values of reference methods and those predicted by the PLS models for CPMG is very 

promising with r value of -0.91. Otherwise, CWFP signals have higher correlation for fat content (r 

= 0.99) than CPMG. 

The main advantage verified here is the no-invasive measurement of fat content performed for intact 

packing of food products. The high linear correlation coefficients between the reference values from 

Bligh and Byer lipids extraction and those predicted by PLS model evidences the accuracy of 

multivariate model against the univariate fitting with the discrete T2 values. 

-99 -



(L24) 

DIODE LASER ABSORPTION SPECTROMETRY AS A TOOL FOR CONTACTLESS 

DIAGNOSTIC OF A HOT ZONE 

M. A. Bolshov, Yu. A. Kuritsyn, V. V. Liger, and V. R. Mironenko 

Institute for Spectroscopy RAS, 5 Fizicheskaya str., 142190, Moscow, Troitsk, Russia 

mbolshov@mail.ru 

Temperature is the critical parameter of any combustion process. In particular, temperature of the 

combustion zone in mixing flows of oxidant and fuel characterize the efficiency of a jet and fuel 

consumption. Absorption spectrometry with tunable diode lasers (TDLAS) is a powerful tool for 

contactless measurements of gas concentration and temperature in hot zones. The technique is based 

on the registration of the experimental transient absorption spectra of water molecules and fitting of 

the experimental spectra by the simulated ones constructed using the spectroscopic data bases. 

Wavelength scale, frequency, temperature, pressure, base line and the concentration of water 

molecules were the parameters of the fitting. Specific technique of transient data processing and 

algorithm of fitting will be discussed. 

The advantages and limitations of the developed technique will be discussed in the talk with the 

emphasis on the problems of the experimental spectra fitting and different fitting algorithms. The 

efficiency of the developed technique was exemplified by the measurement of the temperature and 

water vapor concentration in the hot zone of plasma-assisted combustion in air-fuel supersonic flow. 

The combustion is ignited and sustained by the pulsed electric discharge in experimental 

aerodynamic tube, characterized by rather strong fluctuations, vibrations and different optical and 

electrical noises. The air flow parameters were: Mach = 2, total pressure 150-300 torr. Air was used 

as the oxidant, hydrogen or ethylene were used as the fuel. 

The mean temperature of the hot tail of the combustion zone varied within (800-1200)K for 

hydrogen and (700-1000)K for ethylene, the water concentration varied within 10-20 Torr interval. 

The high signal-to-noise ratio enabled to obtain the temporal profile of both parameters with the 

resolution of ~ 1 ms. Precision of the temperature evaluation was estimated to ~ 40 K. 

-100 -



(L25) 

LIQUID CHROMATOGRAPHY MASS-SPECTROMETRY AS A TOOL FOR DETECTION 

OF CHEMICALS CONNECTED WITH CHEMICAL WARFARE AGENTS IN THE 

ENVIRONMENTAL AND BIO SAMPLES 

Igor A. Rodin 

Chemistry Department Moscow State University 119991 Leninsky Gory 1-3 Moscow Russia 

e-mail: Rodin@analyt.chem.msu.ru 

The development, production, stockpiling and use of chemical weapons are prohibited under the 

Chemical Weapons Convention [1]. In cases of alleged use of chemical warfare (CW) agents, 

environmental samples may be collected and analyzed for agents and their degradation products 

presented as a supporting evidence of a CW attack. Biomedical samples, e.g. blood and urine, may 

be analyzed for biological markers of poisoning as evidence that individuals have been exposed to a 

CW agent. Biomedical sample analysis also has applications in exposure monitoring, e.g. in 

individuals engaged in demilitarization activities, and for the diagnosis of poisoning prior to the 

administration of medical countermeasures. Common technique for organic toxicants is a gas 

chromatography-mass spectrometry. 

In general, chemical warfare agents are rather volatile and easy to degrade. Once exposed to the 

environment chemical warfare readily degrade by rapid hydrolysis or oxidation to the corresponding 

degradation chemicals which never exist in nature. These chemicals are highly polar and unsuitable 

to direct separation by gas chromatography. Liquid chromatography is a good alternative to 

separation for low volatile and highly polar compounds, and mass-spectrometry detection provides 

excellent sensitivity and selectivity. 

Several novel analytical methods for chemicals connected with various types of chemical warfare 

agents detection (nerve agents and vesicants) were developed using liquid chromatography massspectrometry. 

Development, validation and using in OPCW Proficiency Tests of techniques for 

sulfur mustard metabolites detection [3], nerve agents metabolites detection (alkylmethylphosphonic 

acids and dyalkyltaurines) [4-5] and lewisite metabolites detection [6] will be reported. 

References 

Convention on the Prohibition of the Development. Production. Stockpiling and Use of Chemical 

Weapons and on their Destruction. Technical Secretariat for the Organization for the Prohibition of 

Chemical Weapons. The Hague. 1997. 

Rodin, I. A., Braun, A. V., Savelieva, E. I., Rybalchenko, I. V., Ananieva, I. A., & Shpigun, O. A. 

(2011). Rapid method for the detection of metabolite of sulfur mustard 1,1'-sulfonylbis[2-S-(Nacetylcysteinyl)ethane] 

in plasma and urine by liquid chromatography-negative electrospray-tandem 

mass spectrometry. Journal of Liquid Chromatography and Related Technologies, 34(16), 1676. 

Rodin, I. A., Braun, A. V., Anan'eva, I. A., Shpigun, O. A., Savel'eva, E. I., Rybal'chenko, I. V., 

(2011). Detection of nerve agent markers by liquid chromatography - mass spectrometry. Journal of 

Analytical Chemistry, 66(14), 1417. 

I. Rodin, A. Stavrianidi, R. Smirnov, A. Braun, O. Shpigun, I. Rybalchenko (2013) New Techniques 

for Nerve Agent Oxidation Products Determination in Environmental Water by HPLC-MS and CE 

with Direct UV Detection. Environmental Forensics, 2(14). In press. 

Rodin, I., Braun, A., Stavrianidi, A., Shpigun, O., & Rybalchenko, I. (2011). Lewisite metabolites 

detection in urine by liquid chromatography-tandem mass spectrometry. Journal of Chromatography 

B: Analytical Technologies in the Biomedical and Life Sciences, 879(32), 3788. 

(L26) 

-101 -



COLLISION-INDUCED DISSOCIATION OF HYDROXYLATED POLYCYCLIC 

AROMATIC HYDROCARBONS IN AN ION TRAP TANDEM MASS SPECTROMETER 

Xue Li 1,2 and Renato Zenobi 2 

1 Institute of Environmental Pollution and Health, Shanghai University, Shanghai 200444, PR China 

2 Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093 Zurich, Switzerland 

e-mail: xue.li@org.chem.ethz.ch 

Hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) are important biomarkers of 

carcinogenic PAHs and widely used for assessing health risks due to exposure to PAHs. Tandem 

mass spectrometry (MS/MS) based methods have advantages in both sensitivity and selectivity for 

the detection of OH-PAHs; however, MS/MS fragmentation efficiency still needs to improve due to 

the stable fused-ring aromatic structure of OH-PAHs. 

100 

6000 NCE = 60%@AQ = 0.45 

239 

Rel. Int. (%) 

50 

Intensity 

4000 

2000 

3-Hydroxybenzo[a]pyrene 

267 

267 

CO (28 Da) 

0 

180 200 220 240 260 

m/z 

0 

Instrument 

Default Value 

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 

AQ 

Fig.1. Relative intensity variation of 3-OHBaP fragment ion ([M–H–CO] – ) as a function of AQ 

In this study, eight OH-PAHs (with 2 to 5 rings) were selected as target compounds, including 1-/2- 

naphthol (1-/2-OHNap), 3-/4-/9-hydroxyphenanthrene (3-/4-/9-OHPhe), 1-hydroxypyrene (1- 

OHPyr), 6-hydroxychrysene (6-OHChr) and 3-hydroxybenzo[a]pyrene (3-OHBaP). Collisioninduced 

dissociation (CID) MS/MS analyses were performed using a LCQ Deca XP ion trap mass 

spectrometer (Thermo, San Jose, CA, US). The effects of CID parameters, such as the activation Q 

(AQ) and normalized collision energy (NCE) on fragmentation efficiency of all eight OH-PAHs 

were systematically investigated. 

By optimizing NCE and AQ in the CID experiments, the fragment ion [M–H–CO] – generated from 

the parent ion [M–H] – was monitored. Compared with previous results, 3-OHBaP was efficiently 

fragmented (Fig.1), and the MS/MS fragmentation efficiencies for 1-OHNap, 3-/4-/9-Phe and 6- 

OHChr were clearly improved, too. AQ was found to be the critical parameter for fragmenting OH- 

PAHs in the LCQ ion trap tandem mass spectrometer. A possible explanation is that as AQ is raised 

above a threshold value, parent ions of each OH-PAHs can be efficiently trapped even at increased 

NCE, and thus ion internal energy of the parent ion can be greatly increased, resulting in effective 

fragmentation (Fig. 1). 

(L27) 

-102 -



ELECTROSPRAY IONIZATION MASS SPECTROMETRY ASSISTED BY 

INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY AS A TOOL TO STUDY 

THE SE/S SUBSTITUTION IN METHIONINE AND CYSTEINE IN SE-ENRICHED YEAST 

Katarzyna Bierła, Juliusz Bianga, Laurent Ouerdane and Joanna Szpunar 

CNRS/UPPA, Laboratoire de Chimie Analytique Bio-inorganique et Environnement (LCABIE), 

UMR5254, Hélioparc, 2, av. Pr. Angot, 64053 Pau, France 

e-mail: katarzynabierla@wp.pl 

Selenium-enriched yeast produced by growing Saccharomyces cerevisiae in the presence of selenite 

is a popular food supplement and an established ingredient of Se-enriched feed premixes and 

finished feed product. The latest patents issued indicate possible emerging uses of the Se-yeast and 

its extracts for cultivating mammalian cell cultures and altering cell functions for therapeutic 

applications. The development of suitable methods for speciation analysis is necessary to understand 

the Se-involving biochemical processes during Se-rich yeast production, the optimization of the Seincorporation 

during the yeast growth and the characterization of the final products in terms of the 

selenium chemical forms present which is requested by regulatory agencies. 

Till now most of the methodological developments concerning analysis of Se-rich yeast have been 

focused on the quantitative determination of selenomethionine (SeMet) leading to several round 

robin exercises culminated at the issue of a certified reference material (SELM-1). The improvement 

of analytical methods allowed the SeMet content above a certain value to be accepted as an 

indispensable parameter of the quality control of marketed products. The other mainstream of 

analytical chemistry developments included the identification of the myriad of selenium metabolites 

allowing the quasi-complete characterisation of the water soluble part of the Se metabolome. 

Nevertheless, none of these approaches allowed to balance an account of selenium species. 

We developed a proteomics approach (based on 2D gel electrophoresis followed by capillary HPLC 

with ICP MS and electrospray Orbitrap MS/MS parallel detection) allowing an investigation of the 

replacement and the degree of the Se/S substitution in methionine and cysteine and quantification of 

Se-compounds in Se-rich yeast. Mass spectrometry enabled to demonstrate for the first time a 

considerable incorporation of selenocysteine (SeCys) in proteins of the yeast proteome despite the 

absence of the UGA codon. The SeMet/Met and SeCys/Cys ratios were determined in a large 

number of peptides (57 and 26, respectively) issued from the tryptic digestion of 19 Se-containing 

proteins located in the gel by laser ablation - ICP MS imaging. The average Se/S substitution in 

methionine was 42.9 ± 35.0 and was protein dependent with ratios ranging from 5 to 160 for 

individual peptides. The substitution of sulphur in cysteine (14.1 ± 4.8 %) in the cysteine - 

containing peptides was relatively similar (ratios from 9 to 23). Taking into account that the 

cysteine/methionine average ratio (2:1) in the yeast protein fraction, the study allowed the 

conclusion that 10-15% of selenium present in Se-enriched yeast is in the form of selenocysteine 

making up the mass balance of selenium species. 

-103 -



(L28) 

IDENTIFICATION OF ORIGINAL SOURCES OF VERMILION IN ANTIQUITY USING 

SULFUR ISOTOPE RATIO ANALYSIS 

Takeshi Minami 1 , Bálint Péterdi 2 , and Miguel Angel Cau 3 

1 School of Science & Engineering, Kinki University 3-4-1 Kowakae, Higashi-osaka, Osaka 577- 

8502 Japan 

2 Geological and Geophysical Collections, Geological and Geophysical Institute of Hungary, 

Stefánia út 14, Budapest 1143, Hungary 

3 Institució Catalana de Recerca i Estudis Avançats (ICREA)/director of Equip de Recerca 

Arqueològica i Arqueomètrica, Universitat de Barcelona (ERAAUB), Department de Prehistòria, 

Història Antiga i Arqueologia, Montalegre, 6-8, 08001 Barcelona, Spain 

e-mail: minamita@life.kindai.ac.jp 

Vermilion is a vivid red colour pigment used for decorating in ancient times worldwide. The 

chemical identification for vermilion is mercuric sulfide, and it was purified from cinnabar ore. A 

fine vermilion increases the vividness of the red colour. Cinnabar ores might have been collected 

from the outcrop of mines, and it is believed that a large amount of vermilion was necessary for 

decorating. Therefore, it is thought that there were not so many mines where a large amount of 

vermilion could have been collected in ancient times. 

We observed that the ratio of sulfur isotope of cinnabar ore varies according to the main mines of 

Europe. The samples were taken from the collections of the Geological and Geophysical Institute of 

Hungary. The ratio of sulfur isotope is measured by using Elemental Analyzer (Euro EA HEKAtech 

GmbH, Germany) and IsoPrism High Performance Stable Isotope Ratio MS (GV Instrument Ltd, 

Germany). As shown in Table 1, the sulfur isotope ratio of cinnabar ore from Almaden mine was 

very different from the value of other European mine ores. Then, we measured the ratio of sulfur 

isotope of vermilion used in Roman paintings collected from two Spanish Roman cities, Clunia 

(Burgos) and Baetulo (Badalona, Catalonia), in order to examine whether it was possible to 

determine the original source. 

The results of the analysis and the calculation of the ratio of sulfur isotope for the four samples 

collected from Clunia gave a value of +9.85 ± 0.94 ‰ and the ratio for the three samples from 

Badalona was +13.11 ± 2.67 ‰. From these results, 

vermilion used in Clunia could have been originally collected Table 1. Sulfur isotope ratio of cinnabar ores of 

from the Almaden mine. However, the value of vermilion European main mines 

used in Badalona is slightly higher than the value of the ore Mine Country mean SD (n) 

of the Almaden mine. The possibility of the use of ore from Almaden Spain +8.78 ± 1.20 (9) 

another mine ─but not the other mines shown in Table 1─ in 

Monteamiata Italy -0.97 ± 0.51 (2) 

order to produce the vermilion used in the paintings of 

Erzberg Austria +0.65 ± 3.47 (3) 

Badalona cannot be excluded. 

Idria Slovenia -1.33 ± 0.50 (6) 

In conclusion, the analysis of sulfur isotope ratio in vermilion 

Rudnany Slovakia -1.60 ± 0.16 (2) 

is an effective method to identify the original sources of 

δ 34 S(‰) 

vermilion used in ancient times. 

-104 -



(L29) 

STUDY OF INTERACTIONS BETWEEN REACTIVE GAZ SPECIES AND 

MICROORGANISMS BY NANO-RESOLUTION MASS SPECTROMETRY IMAGING 

Jean-Nicolas Audinot 1 , David Duday 1 , Franck Clément 2 , Elodie Lecoq 1 , Christian Penny 1 , Thierry 

Belmonte 3 , Kinga Kutasi 4 , Henry-Michel Cauchie 1 , Patrick Choquet 1 

1 Centre de Recherche Public Gabriel Lippmann – SAM & EVA, 41 rue du Brill, L-2422 Belvaux, 

Luxembourg 

2 Pau University UPPA – IPREM UMR 5254 – LCABIE, Plasmas & Applications, 2 Avenue du 

Président Angot, F-64000 Pau, France 

3 Nancy University – Institut Jean Lamour UMR CNRS 7198, Chemistry and Physics of Solids and 

Surfaces, CS 14234, F-54042 NANCY Cedex, France 

4 Research Institute for Solid State Physics and Optics - Hungarian Academy of Sciences, POB 49, 

H-1525 Budapest, Hungary 

e-mail: audinot@lippmann.lu 

By working with a plasma reactor under gas flow conditions, it is possible to obtain a reactive gaz 

which keeps high reactivity on materials surfaces. Nowadays, these plasma reactors are commonly 

used for decontamination applications by acting on various micro-organisms (bacteria, virus, …). 

The interaction mechanism of the reactive species with microorganisms and living tissues is 

currently one of the most active fields of research in the plasma community [1]. 

Several innovative characterization methods are currently developed in order to study thoroughly the 

modifications induced by the reactive species (e.g. Reactive Oxygen Species (ROS) on plasmatreated 

microorganisms. The method used in this work consists of determining the effect of 

hydrogen, oxygen and nitrogen coming from the plasma on Escherichia coli bacteria. In order to 

follow the treatment effect on bacteria, we used isotopically labelled 15 N 2 , 18 O 2 and 2 H 2 containing- 

Ar gas mixtures to produce the plasma. To localize and quantify the amount of reactive species on 

the bacteria, we used the unique mass spectrometry technique allowing working at the cellular scale: 

the NanoSIMS50 [2]. This mass spectrometer has been developed for high-resolution imaging (with 

an optimized lateral resolution down to 50 nm) allowing the investigation of subcellular structures 

and measurement of isotopic compositions with an excellent limit of detection in the analyzed 

nanoscale volume [3-4]. 

Different exposure times (1, 5, 10 and 15 min) were used to treat the biological samples under 

different experimental plasma conditions. The NanoSIMS50 analyses deliver isotopic images of 

cellular structures and we measured gas fixation pixel by pixel in different intracellular areas for 

each individual E. coli. Once the acquisition done, we calculated the values of the isotopic ratio and 

the percentage of penetration of labelled gas for individual bacteria [5]. For example, an increase in 

isotopic oxygen incorporated into the structure as a function of the exposure time was observed, 

until a saturation time. These results were compared with other treatments performed with nitrogen 

and hydrogen labelled gases ( 15 N, 2 H). 

-105 -



(L30) 

SOLID SAMPLING TECHNIQUES FOR THE DIRECT ELEMENTAL OR ISOTOPIC 

ANALYSIS OF DRIED MATRIX SPOTS 

Martín Resano, 1 M. Aramendía, 2 L. Rello, 3 E. García-Ruiz 1 

1 Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain, 50009 

2 Centro Universitario de la Defensa-Academia General Militar de Zaragoza, Carretera de Huesca 

s/n, 50090, Zaragoza, Spain 

3 Department of Clinical Biochemistry, “Miguel Servet” Universitary Hospital, Paseo Isabel La 

Católica 1-3, 50009, Zaragoza, Spain 

e-mail: mresano@unizar.es 

The deposition of biological fluids onto clinical filter paper, producing a dried matrix spot (DMS), is 

a methodology that has become increasingly popular in the years to date and is nowadays deployed 

in a wide variety of bioanalytical contexts, such as screening for metabolic diseases in newborns, 

therapeutic drug monitoring, pharmacokinetic or toxicological and forensic studies. 1,2 This 

popularity is a consequence of the significant advantages brought by this methodology, that permits 

the development of minimally or non-invasive collection approaches, and results in specimens 

(DMS) that are very stable and can be easily transported and stored. 

However, there is still a very limited number of works exploring its potential for elemental and/or 

isotopic analysis. In part, this can be explained considering that the transformation of a liquid sample 

(e.g., blood or urine) into a solid one (DMS) often implies additional problems for the analyst, such 

as lower sensitivities or enhanced matrix effects. Fortunately, there are analytical techniques that 

permit direct analysis of these types of solid samples and are capable of offering an excellent 

performance. 

This work discusses the use of solid sampling high-resolution graphite furnace atomic absorption 

spectrometry (SS HR CS GFAAS) and laser ablation-inductively coupled plasma mass spectrometry 

(LA-ICPMS) for the direct analysis of dried blood spots and dried urine spots, and its application to 

a variety of situations, such as i) fast screening of large populations; 1 ii) monitoring of chronic 

patients, 2,3 and iii) early detection of disease associated with the metabolism of some metals. 4 

References 

1. M. Resano, L. Rello, E. García-Ruiz and M. A. Belarra, J. Anal. At. Spectrom., 2007, 22, 1250– 

1259 

2. L. Rello, A. C. Lapeña, M. Aramendía, M. A. Belarra and M. Resano, Spectrochim. Acta Part B, 

2013, 81, 11–19. 

3. M. Aramendía, L. Rello, F. Vanhaecke and M. Resano, Anal. Chem., 2012, 84, 8682−8690. 

4. M. Resano, M. Aramendía, L. Rello, M. L. Calvo, S. Bérail and C. Pécheyran, J. Anal. At. 

Spectrom., 2013, 28, 98–106 

-106 -



(L31) 

LOW RESOLUTION CONTINUUM SOURCE ELECTROTHERMAL ATOMIC 

ABSORPTION SPECTROMETRY: CLARIFICATION OF ANALYTICAL POTENTIAL 

Dmitri Katskov 1 and Svetlana Kurilko 2 

1 Department of Chemistry, Tshwane University of Technology, Private Bag X680, Pretoria 001, 

South Africa 

2 

Department of Optical Information Technologies, State Technical University, 20, K. Marx av. 

Novosibirsk 630073, Russia 

e-mail: katskovda@tut.ac.za 

The methodology of simultaneous multi-element electrothermal atomic absorption spectrometry 

(SMET AAS) [1-3] is based on pulse vaporization of the sample in a graphite tube atomizer, CCD 

detection of transitory radiation from the continuum source (CS) within broad wavelength range and 

calculation of absorption at the resonance lines of the elements to be determined. Relatively small 

number of lines in atomic absorption compared to that in respective emission spectra makes possible 

to employ low resolution (LR) spectral instrument, which can provide fast data acquisition within 

wavelength range 200-400 nm where most part of resonance lines is located. 

Providing simultaneous access to the absorption spectra of various elements LR, however, causes 

substantial sensitivity loss compared to traditional AAS and non-linearity of calibration curves. In 

SMET AAS the sensitivity loss is partially compensated by high pulse density of atomic vapor in the 

fast heated tube atomizer with narrow absorption volume. The calculation algorithm provides 

background (BG) correction, linearization of function absorption vs. concentration of atomic vapor 

and integration of the modified signals. Simultaneous determination of individual analytes is 

performed within 3-5 orders of magnitude concentration range. The methodology has been applied 

to the analysis of underground water and coal slurry [2, 3]. 

In this work the investigation of analytical potential of SMET AAS continued with focus on 

instrumental and software improvement as well as on methodology of multi-element calibration. 

The D 2 and Xe arc lamps for 190-350 and 220-410 nm ranges were employed combined with Ocean 

Optics HR4000 CCD spectrometer (3600 pixels) and fast heated tube atomizer (25 and 2.5 mm in 

length and internal diameter, respectively). High CS intensity permitted increasing of number of 

spectra collected during 1 s atomization time, from 80 to 200. Together with the increased sensitivity 

on account of longer tube this helped to reach limits of detection equal or for some elements better 

than it is claimed for ICP instruments. The calculation algorithm permits BG correction of sharp 

molecular bands using reference spectra obtained independently. The calculation results are 

presented directly in the concentration units using permanent calibration obtained for single element 

solutions or can be justified by the measurements with multi-element standard addition. Instant 

observation of 3-d or temporary integrated spectra helps to select conditions for chemical 

modification of the sample or determination of non-metals using molecular bands. 

References: 

D.A.Katskov, G.E.Kanye, S.Afr.J.Chem. 63 (2010) 45-57 

G.Jim, D.Katskov, S.Afr.J.Chem. 64 (2011)71-78 

D.Katskov, Trends in Applied Spectroscopy, 9 (2013) 17-40 

-107 -



(L32) 

TRACE DETERMINATION OF METALS BY IN-ATOMIZER HYDRIDE TRAPPING 

AAS: METHOD DEVELOPMENT, VALIDATION AND ANALYTICAL APPLICATIONS 

Libor Průša 1,2 , Stanislav Musil 1 , Miloslav Vobecký 1 , Jiří Dědina 1 and Jan Kratzer 1 

1 Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, Brno, CZ 602 00, Czech Republic 

2 Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Albertov 8, 

Prague 2, CZ 128 43 Czech Republic 

e-mail: jkratzer@biomed.cas.cz 

Hydride generation coupled to atomic absorption detector (HG-AAS) is due to its simplicity, 

selectivity and sensitivity a powerful and favorite analytical technique. Analyte conversion to the 

gaseous hydride has two advantages – firstly, the analyte is separated from the matrix and secondly, 

analyte can be preconcentrated from the gaseous phase. Employing the preconcentration step, the 

HG-AAS limit of detection (LOD) can be lowered to meet the requirements of the ultratrace analysis 

being often inevitably requested for hydride forming elements either by law regulations or by the 

customers. Providing that the preconcentration step is simple, fast and efficient, this inexpensive 

approach based on hydride trapping-AAS can substitute or even surpass conventional approaches to 

elemental and speciation analysis based on the liquid phase sampling inductively coupled plasma 

mass spectrometry (ICP-MS), which generally serves as a trademark of unparalleled sensitivity. The 

most common approach to hydride preconcentration is in-situ trapping in graphite furnaces. 

However, also quartz and metal preconcentration devices have been designed and successfully 

employed for ultratrace determination of hydride forming elements with detection by AAS. 

A compact trap-and-atomizer device based on a quartz multiatomizer has been constructed in our 

laboratory recently. It was shown to be a powerful tool for ultratrace determination of hydride 

forming elements (As, Sb, Bi, Se, Pb and Sn) since it allows rapid and efficient in-atomizer 

preconcentration of the analyte prior to its detection by AAS. Oxygen rich atmosphere is used in the 

collection step of the preconcentration procedure to remove hydrogen evolved during the chemical 

hydride generation of the analyte to reach efficient trapping. On the contrary, hydrogen rich 

atmosphere is used in the volatilization step to efficiently release trapped species. The optimum 

preconcentration conditions for individual hydride forming elements as well as the corresponding 

preconcentration efficiencies are summarized in Tab. 1. 

Optimization of generation, preconcentration and atomization conditions will be discussed using tin 

as a model analyte. Complete analyte collection followed by quantitative release of trapped tin 

species is reached under the optimum preconcentration conditions, i.e. collection temperature of 500 

°C and volatilization temperature of 800 °C. Hydrogen flow rate of 50 ml.min -1 was found to be 

optimum with respect to sensitivity and peak shape (FWHM 0.7 s). 

-108 -



Tab. 1 Optimum preconcentration conditions and corresponding preconcentration efficiencies of 

hydride forming elements in the quartz trap-and-atomizer device 

element T collection, (°C) T volatilization , (°C) H 2(volatilization) flow rate, 

(ml min -1 ) 

As 80 - 650 650 - 800 100 50 

Sb 400 - 1000 900 - 1050 75 100 

Bi 80 - 1000 800 - 1100 100 100 

Se 80 - 300 550 - 650 50 70 

Pb 100 - 300 700 - 900 100 100 

Sn 200 - 600 750 - 900 50 100 

preconcentration 

efficiency, (%) 

Analytical figures of merit reached by the proposed method for ultratrace determination of Sn by 

stannane generation in-atomizer trapping AAS will be presented. Whereas LOD for the on-line 

atomization mode (no preconcentration, 2 ml sample) reached 0.14 ng.ml -1 Sn, LOD for 30 s 

preconcentration (2 ml sample) was 0.05 ng ml -1 Sn. Preconcentration period can be further 

increased without any change in the preconcentration efficiency indicating sufficient stability of the 

trapped Sn form (no losses). Preconcentration period of 2 min (sample consumption 8 ml) was 

chosen as a compromise between sample throughput and sensitivity (LOD 0.03 ng ml -1 Sn). 

Interferences of other hydride forming elements on Sn determination were investigated employing 

analyte to interferent ratios up to 1:1000. Both the on-line atomization (no preconcentration) as well 

as the preconcentration modes have been found free of significant interferences of other hydride 

forming elements (As, Sb, Bi and Se). Analyses of real samples (tinned food) will be discussed. 

Radiotracer technique is a very effective, reliable and powerful tool to verify the newly developed 

analytical procedure independently of the detector used during the development. This fact will be 

demonstrated employing lead as model analyte. The use of radiotracers enables not only to quantify 

the efficiency of single steps (generation, collection, volatilization) of the newly developed 

procedure but also to visualize the spatial distribution of the analyte in the apparatus. Lead 

preconcentration on quartz surface after plumbane generation was studied by means of laboratory 

prepared 212 Pb radioactive indicator. Trapping capacity, preconcentration efficiency as well as Bi 

interference on Pb preconcentration were characterized by radiometry and autoradiography. The 

mechanism of Bi interference was understood thanks to the use of the radioactive indicator - it 

appears in the volatilization step of the preconcentration procedure. 

This work was supported by the Czech Science Foundation (grant No. P206/11/P002), Institute of 

Analytical Chemistry of the ASCR, v.v.i. (project no. RVO: 68081715) and the Ministry of 

Education, Youth and Sports of the Czech Republic (project MSM 0021620857). 

-109 -



(L33) 

OPTIMIZATION STUDY ON DETERMINATION OF INORGANIC ARSENIC SPECIES 

IN HOT CHILLI PEPPER AND TOMATO VARIETIES BY USING MICROWAVE 

ASSISTED DIGESTION FOLLOWED BY FLOW INJECTION-HYDRIDE GENERATION 

ATOMIC ABSORPTION SPECTROMETRY 

Nittaya Thaharn 1 , Suchila Techawongstien 2 and Saksit Chanthai 1 * 

1 Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of 

Science, Khon Kaen University, Khon Kaen, 40002 Thailand. 

2 Department of Plant Science and Agricultural resources, Faculty of Agriculture, Khon Kaen 

University, Khon Kaen, 40002 Thailand. 

*e-mail: sakcha2@kku.ac.th 

An analytical procedure for inorganic arsenic (As) species in hot chilli pepper and tomato fruits at 

red-ripe stage using microwave assisted digestion (MAD) followed by flow injection - hydride 

generation atomic absorption spectrometry (FI-HGAAS) was presented. The optimum conditions of 

both acid digestion method and arsenic hydride (AsH 3 ) determination were studied in details. The 

plant sample (0.5 g) was digested with 5 mL of concentrate nitric acid by MAD programmed at 900 

W for 25-35 min. Regarding on speciation analysis, arsenite, As(III), in the acid digests could only 

be analyzed by FI-HGAAS using 1.0% (v/v) HCl as a carrier solution and 0.5% (w/v) NaBH 4 in 

0.04% (w/v) NaOH as a reducing agent, while total As content was determined after pre-reduction 

of arsenate, As(V), to be As(III) with 2% (w/v) thiourea prior to measurement by the instrument. 

The concentration of As(V) was then calculated by the difference. Detection limits for As(III) and 

As(V) were 0.004 and 0.006 μg L -1 , respectively. Relative standard deviation (RSD) of the data was 

less than 5.32% (n = 10). Recovery study (98-103%) of the real samples spiked with 10 µg L -1 As 

was satisfactorily obtained. The proposed method was applied for the trace determination of As in 

six varieties of hot chilli pepper (0.55-0.88 µg As(III) g -1 & 0.22-0.93 µg As(V) g -1 ) and seven 

varieties of tomato (0.36-0.64 µg As(III) g -1 & As(V): 0.22-0.60 µg As(V) g -1 ) samples. 

Keywords: Arsenic speciation, Chilli, Tomato, Microwave assisted digestion, FI-HGAAS 

-110 -



(L34) 

PRECONCENTRATION OF MERCURY FROM NATURAL WATERS BY 

AMALGAMATION OF HG 2+ ON COPPER POWDER AND HG 0 ON GOLD 

NANOPARTICLES 

Nikolay Panichev, Khakhathi Mandiwana and Merimee. Kalumba 

Department of Chemistry, Tshwane University of Technology, P.O. Box 56208, Arcadia 0007, 

Pretoria, South Africa 

e-mail: PanichevN@tut.ac.za 

Determination of total amount of mercury (Hg) in natural waters is usually carried out after chemical 

restoration of Hg +2 ions to elemental mercury Hg 0 , using cold vapour generation technique with 

atomic absorption detection (CV-AAS). The limit of detection (LOD) of Hg determination in natural 

waters using CV-AAS is approximately 0.2 µg L -1 . At present, to reduce the value of LOD of Hg 

determination in natural waters is only possible by analytical methods in which a step of 

preconcentration is involved. The most promising method of preconcentration could be the sorption 

of Hg 0 on golden nanoparticles. For this, all Hg +2 ions in water samples must be reduced to 

elemental mercury. This step of chemical pretreatment is connected with additional time of analysis 

and could be the reason of either losses of Hg or contamination of samples. 

To avoid the problem of samples chemical pretreatment, we proposed the method of determination 

of Hg in water samples by preconcentration of Hg +2 on copper particles and Hg 0 on golden 

nanoparticles impregnated into membrane filters. The reaction between different chemical forms of 

mercury with Cu and Au are the following: 

Hg 2+ + Cu → Hg + Cu 2+ (1) 

Hg + Cu → CuHg AM (2) 

Hg + Au → AuHg AM (3) 

The addition of golden nanoparticles to membrane filters for Hg 0 collection was connected with their 

high efficiency for amalgamations, which in combination with high efficiency of Hg+2 collection by 

copper powder created the possibility of total Hg (Hg +2 + Hg 0 ) determination. 

Cu powder 

Cu Hg 

20000 

15000 

Intensity 

10000 

5000 

0 

20 40 60 80 

Fig.1 SEM image of copper powder on membrane filter (A) and pattern XRD of copper powder with 

accumulated Hg 0 (B) 

The measurements of Hg were carried out by thermal desorption of Hg from filters, using a RA 

915+ mercury analyzer (Lumex, Russia). The determination of Hg by thermal desorption does not 

2 

-111 -



involve any additional chemical reagents and sharply reduces risk of samples contaminations. 

The LOD calculated using the calibration graph function (y=332x + 2; R 2 = 0.9983) and 

corresponding standard deviation (3.2 %) for the calibration line was found to be 0.02 ng (absolute 

mass). It should be noted that the LOD in concentration units is inversely proportional to the sample 

volume processed. In our study, the relative LOD (0.2 ng L –1 ) was calculated for 0.1 L of water 

sample. 

The validation of method was done by analysis of several CRM’s and by the recovery test. For 

example, the result of Hg determination in CRM TORT-2 (National Research Council of Canada), 

0.28 ± 0.02 µg g-1, which was obtained after its chemical decomposition in HNO 3 + H 2 O 2 using 

microwave, Mars-5 were in a good agreement with certified value 0.27 ± 0.06 µg g-1. The results of 

recovery test, which was conducted with samples of tap water collected at in Pretoria city, were 

between 94-104 % for Hg concentrations 0.5 and 1.0 ng L -1 . 

The greatest advantage of this method is the possibility of samples collection on the sport, without 

transportation of large amounts of water for the analysis in laboratories due to high efficiency of 

simultaneous collection of mercury ions Hg +2 and elemental mercury Hg 0 from aqueous phase on 

membrane filters. 

-112 -



(L35) 

SAMPLING OF LIQUIDS IN ATOMIC EMISSION SPECTROMETRY USING A HELIUM 

ATMOSPHERIC PRESSURE GLOW DISCHARGE 

José A.C. Broekaert, Katharina K. Moß and Klaus-Georg Reinsberg 

Department of Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, D-20146 Hamburg, 

Germany 

e-mail: jose.broekaert@chemie.uni-hamburg.de 

Atmospheric pressure glow discharges (APGD) during the last years have been recognized as 

powerful radiation and ion sources for atomic emission and mass spectrometry, respectively. One of 

the many possible systems is the He operated dc APGD with hollow electrodes, as it has been 

developed and optimized with respect to its geometry and working conditions by Gielniak et al. [1]: 

Initially for this source the excitation and rotational temperatures and electron number densities were 

determined. Further, this source has been found useful to excite dry element vapours, as in the case 

of Hg vapour released in the Hg cold vapour technique, but also for the excitation of gas 

chromatography effluents, as shown for halogenated hydrocarbons [2]. The source in this 

contribution has been studied to elutriate its possibilities to take up wet aerosols for spectral analysis 

purposes. 

At a current of 40 mA and a He flow of 500 mL.min -1 the source was found to be able to accept 

aerosols generated with a conventional pneumatic nebulizer positioned in a double pass spray 

chamber according to Scott as well as with a custom built drop on demand system based on printer 

cartridges [3]. In the case of pneumatic nebulization ca. 170 µL.min -1 was consumed at an efficiency 

of some %. The current-voltage characteristics were found to be normal both in the case of dry as 

well as with wet aerosols. However, the burning voltage in the case of a change from dry to wet 

aerosols was found to considerably increase. Indeed, in the case of pneumatic nebulization the 

burning voltage at 40 mA was found to increase from 630 to 840 V but therefor in the case of the 

drop on demand nebulizer only from 630 to 750 V. Further, the influence of the water load on the 

rotational temperatures measured on OH bands and on the excitation temperatures measured with 

the aid of Fe atomic lines was studied. In the case of dry He for this purpose ferrocene vapour was 

lead into the plasma and in the case of wet aerosols aqueous solutions of Fe were used. Whereas the 

rotational temperatures were found to be at the 1500 K level and the excitation temperatures at 4500 

K both for a dry plasma, the introduction of the sample liquids was found to decrease the rotational 

temperatures by 500 K. The excitation temperatures were found to decrease by 400 K for pneumatic 

nebulization and 240 K for the drop on demand system. The electron number densities as determined 

from Stark broadening of the H ß line are of the order of 1 x 10 14 cm -3 and they were found to be 

mainly unaffected by the introduction of moisture into the plasma. 

As all influences of the introduction of wet aerosols discussed above were found to be moderate, the 

analytical figures of merit of the He APGD in the case of its use as radiation source for atomic 

emission spectrometry using both ways of sample liquid introduction were studied. For these 

experiments a 0.55 m Czerny-Turner monochromator with a 2400 lines.mm -1 grating (Triax550, 

Horiba Jobin-Yvon) equipped with a iDus 420-OE CCD camera (Andor Technology Ltd., Belfast, 

UK) was used. It was found that in the spectra almost only atomic lines and hardly any ion lines 

were found. The detection limits for the case of pneumatic nebulization for some elements were: Cd 

228.802 nm: 19; Cu 324.754 nm: 140; Mg 285.213 nm: 110; Mn 279.482 nm: 130 and Na 588.995 

nm: 10 µg.L -1 . For Na in the case of the drop on demand nebulizer a detection limit of the same 

range of concentration was found. The calibration curves with both liquid sampling systems were 

found to be linear over the range of 1 – 100 mg.L -1 . With OES using the He dc APGD a 

concentration of Na in tap water of 18.9 + 0.3 mg.L -1 was found with the drop on demand system. In 

-113 -



the case of the pneumatic nebulization system the analysis result was: 20.8 + 0.9 mg.L -1 Both values 

were in the range of the concentration determined with ICP-OES (20.2 + 0.4 mg.L -1 ). 

The results show that the He APGD developed and optimized within the frame of this work for the 

case of the introduction of minute flows of aqueous solutions, as it is e.g. the case in elementspecific 

detection in liquid chromatography, might be useful. 

[1] B. Gielniak, T. Fiedler and J.A.C. Broekaert, Spectrochim. Acta, Part B 2011, 66: 21-27. 

[2] Unpublished work. 

[3] J.O. Orlandini v. Niessen, J.N. Schaper, J.H. Petersen and N.H. Bings, J. Anal. At. Spectrom. 

2011, 26: 1781-1789. 

-114 -



(L36) 

GD TOFMS WITH PULSED COMBINED HOLLOW CATHODE FOR DIRECT 

ANALYSIS OF DIELECTRIC SAMPLES 

Alexander Ganeev 1,2 , Anna Gubal l , Ilja Ivanov 1 , Sergey Potapov 2 and Volker Hoffmann 3 

1 Faculty of Chemistry, St. Petersburg State University, Universitetsky pr., 26, St. Petergof, 

St. Petersburg, 198504, Russia 

2 Lumass Ltd., Obukhovskoy Oborony pr. 70, bld.2, St. Petersburg, 192029, Russia 

3 Institute for Complex Materials, Leibniz Institute for Solid State and Materials Research Dresden, 

Helmholtzstrasse 20, 01069 Dresden, Germany 

e-mail: Ganeev@lumex.ru 

Now GD MS is used both for bulk analysis and for depth profiling. One of the important 

applications of GD MS is the direct determination of the elements (including radioactive) in pressed 

dielectric powders (first of all oxides), nuclear fuel, spent nuclear fuel, different glasses and besides 

semiconductors with large band gap. But the analysis of non-conductors with the traditionally used 

Grimm cell is seriously more difficult than that of conductors. Using the DC mode it is impossible 

to perform the direct analysis of such non-conducting samples without a secondary (or hollow) 

cathode. The use of RF power allows the analysis of dielectric samples, but one cannot avoid 

problems with overheating of the sample and capacitive loss of voltage and consequently of the 

sensitivity. The first problem is easily solved by pulsing the RF power supply, but lower erosion 

rates and thus longer times for the analysis are caused. 

The combination of the combined hollow cathode discharge cell and pulsed powering of the 

discharge was found to overcome these limitations. From the one hand pulsed glow discharges help 

to get a significant increase of the analytical signal, do not lead to an overheating of the sample and 

besides they are easy to couple with a fast mass analyzer and have more independent parameters to 

tune for optimization. Moreover using the pulsed mode helps to reduce the accumulation of surface 

charge. At the same time by the use of the combined hollow cathode one can additionally get a 

considerable increase in sensitivity due to the so called “hollow cathode effect”. 

A number of non-conducting samples including sapphire, polycor (Al 2 O 3 ), GaN, SiC, Si, pressed 

oxides of rare elements, iron and uranium were used for investigations. GD OES and GD TOFMS 

techniques were used in the experiments. The Pulsed GD hollow cathode (PGD HC) source was 

shown to give considerably higher signal intensities comparing with the RF Grimm source. It is 

worth mentioning that the use of the hollow cathode effect does not give a considerable advantage at 

equal power. The only benefit was found at thick dielectric samples since for the HC system no 

decrease of signal with sample thickness was observed. A principle difference between sputtering 

processes in HC cell and Grimm cell was found to take place. The mechanism of sputtering of nonconductors 

in direct current mode was investigated and established to be connected with the 

formation of a thin conductive surface layer. Thus it is possible to sputter non-conducting samples 

even in DC mode and thus the signal intensity practically does not depend on sample thickness in 

contrast to the RF discharge in a Grimm type cell. Considering the nature of this layer both, cathode 

material deposition and the formation of the “enriched” surface layer produced when the component 

with high sputtering rate leaves the surface faster than the component with lower sputtering rate 

were found to take place. As for the disadvantages of the HC system it should be noted that due to 

the introduction of the additional component this system is more complicated to operate and 

optimize and is less stable than the Grimm source. Sputtering processes were found to depend 

strongly on cathode material. Aluminum, copper, and tantalum cathodes were considered and 

compared. 

The present work includes the results of the application of PGD HC TOFMS system for the analysis 

of various non-conducting sample. Possibilities and limitations of the system are discussed. 

-115 -



(L37) 

SELECTIVE EXCITATION IN ANALYTICAL GLOW DISCHARGES – ITS RELEVANCE 

IN GD-OES ANALYSIS 

Edward B. M. Steers, London Metropolitan University, 166-220 Holloway Road, London, N7 8DB, 

UK 

e-mail: e.steers@londonmet.ac.uk 

All analytical glow discharges are relatively low power sources, running in low pressure plasma 

gases (Grimm type sources: ~15 W, 5 hPa, VG9000 type sources: ~5 W, 1 hPa). Such sources are 

not in local thermodynamic equilibrium, and line intensities and ion signals depend on the excitation 

and ionization processes populating the relevant levels. 

For energy levels produced by electron excitation, the intensity will depend on the optical excitation 

function for that particular level and the electron energy distribution function (EEDF) so that 

changes in the EEDF produced by the plasma gas composition will affect the intensity of the various 

spectral lines differently. However, the main selective processes for ionisaton and excitation are 

Penning excitation (PE), Penning ionisation (PI), both resulting from collisions with metastable 

atoms of the plasma gas, and asymmetric charge transfer (ACT), caused by collisions with plasma 

gas ions. 

PE: A o + B m A* + B o + ΔE 

PI: A o + B m A + o + B o + e + ΔE 

or A o + B m A + * + B o + e + ΔE, 

ACT: A o + B + o A + * + B o + ΔE, 

A o , B o are ground state atoms, e.g. A from the sputtered sample, and B from the plasma gas 

* denotes an excited state 

B m is a metastable atom, A + 

o a ground state ion 

and ΔE is the kinetic energy released in the collision 

In all cases, ΔE must be positive, or small if negative. For PE and ACT, conservation of energy and 

momentum mean that ΔE must be small even when positive – these are resonant processes. For PI, 

the release of an electron allows the conservation laws to be satisfied for larger values of ΔE. Thus 

all the selective excitation processes depend on the arrangement of the energy levels of the colliding 

atoms and ions, and vary greatly from element to element. Moreover, the presence of foreign gases 

in the plasma gas can cause major changes in the number density of plasma gas ions and metastable 

atoms and so affect the intensities of the spectral lines. The most significant process affecting the 

intensities of spectral lines is probably ACT – not only must there be ionic states with appropriate 

energy to be excited, but spin must also be conserved, at least for the strongest interactions. Since 

the change from ionised to atomic ground state in a noble gas involves a spin change of ½, the 

element to be excited must have ionic states of appropriate energy differing in spin by ½ from the 

spin of the atomic ground state or possibly of low lying metastable atomic states – i.e the 

multiplicity must differ by 1. This latter condition is satisfied, e.g. for copper, iron and manganese 

for Ar-ACT, but not for chromium. 

ACT in particular can be seriously affected by small amounts of hydrogen or oxygen in the plasma 

gas – this may come from gas trapped in the sample or may arise from a constituent of the sample, 

e.g. an oxide or hydride. For example, the presence of hydrogen in argon causes a dramatic fall in 

the number density of Ar + ions and their replacement by ArH + ions. Oxygen also reduces the 

number of Ar + ions but to a lesser extent. In both cases the intensity of lines excited by Ar-ACT is 

-116 -



reduced. On the other hand, both hydrogen and oxygen can excite ionic levels having a total 

excitation energy (i.e. ionisation energy + excitation energy) close to but less than 13.6 eV. 

We have carried out extensive experimental work, deliberately introducing hydrogen or oxygen into 

the plasma gas at low levels ~ 0.1% v/v, corresponding to the amount that may arise e.g. from a 

hydride layer and at higher levels so that the effect may be more clearly seen. All the results to be 

presented have been obtained using a “Grimm-type” source with “standard excitation conditions”, 

i.e. constant voltage (700 V) and current (20 mA). The pressure used therefore had to be changed, 

depending on the cathode (sample) material and the plasma gas. Further, the addition of small 

amounts of molecular gases (H 2 , O 2 or N 2 ) required a change in pressure to maintain standard 

conditions. In the majority of cases, the spectra were recorded using the Imperial College high 

resolution vis-vuv Fourier transform spectrometer. 

Examples of selective excitation will be presented for various elements, including the effect of 

impurities, e.g. hydrogen, and the analytical implications discussed. For example, Figs 1 & 2 show 

effects produced by hydrogen with a manganese cathode 

5.0 – Pure Ar 

Line Intensity (AU) 

4.0 – 

Line Intensity (AU) 

250 

Ar + 0.15% H 2 

275 

Fig. 1. A section of the manganese spectrum 

excited in argon and in an argon/hydrogen plasma 

Intensity Ratio Ar+H2 / Ar 

1.8 

1.6 

1.4 

1.2 

1.0 

0.8 

0.6 

0.4 

0.2 

0.0 

257.610 12.245 eV 272.210 15.697 eV 

259.372 12.213 eV 271.003 15.427 eV 

0 0.1 0.2 0.3 0.4 0.5 

Hydrogen concentration, % 

Fig. 2 Intensities of some Mn II lines with various argon/ 

hydrogen mixtures, normalised to intensity with pure argon. 

di /h d l 

Mn II lines with total excitation energy ~ 15.8 eV are 

normally strongly excited by Ar-ACT and fall 

dramatically in intensity when hydrogen is introduced. 

-117 -



(L38) 

MOLECULAR EMISSION IN GD-OES REVISITED – STRATEGIES FOR BACKGROUND 

CORRECTION 

Arne Bengtson 1 and Mats Randelius 1 

1 Swerea KIMAB, Isafjordsgatan 28A, SE-164 07 Kista, Sweden 

e-mail: arne.bengtson@swerea.se 

Previous work has shown the existence of molecular emission in Glow Discharge Optical Emission 

Spectroscopy (GD-OES). The most prominent emission bands originate from the diatomic radicals 

CO, OH, NH and CH, but emission from C 2 and a few metal oxides has also been observed. The 

molecular emission is always present in the very beginning of the discharge, but when sputtering 

organic coatings, oxides etc. the emission often persist throughout the layer. From the analytical 

point of view, the molecular emission is a problem in compositional depth profile analysis (CDP) 

since it is a source of spectral background at several of the atomic emission lines used for elemental 

analysis. Although this problem has been well known for several years, there is not yet a well 

developed technique to perform background correction for molecular emission. In principle a 

conventional “line interference correction” algorithm is applicable, but there is no easy way to 

determine the correction factors. In most CDP work with GD-OES, the molecular emission problem 

is simply ignored, which undoubtedly gives rise to “false” depth profiles of certain elements. 

In this work, the temporal behaviour of emission lines from CO, OH, NH and CH is studied. A Leco 

GDS 850 spectrometer fitted with channels for these molecules was used. Since the spectrometer is a 

conventional multichannel instrument with PMT detectors, only the emission from single vibrational 

– rotational lines within broad “emission bands” from each molecule is detected. In addition, 

simultaneous observations of complete low – resolution spectra of the molecular bands were made 

with miniature CCD spectrometers, coupled directly to the glow discharge. The temporal profiles of 

the molecular emission signals were compared with profiles of several atomic emission lines, 

located within the spectral width of the corresponding molecular band structure. It was shown that 

while the expected correlation between the molecular channels and the spectral background of the 

atomic lines is obvious, the temporal behaviour can be different when comparing initial signals (< 2 

s) with the long-term signals through e.g. polymer coatings. This indicates that the relative 

intensities of the different parts of a molecular band are affected by the discharge conditions, which 

inevitably takes a finite time to stabilise after ignition of the discharge. Possible strategies to deal 

with this problem by implementing “dynamic” background correction for molecular emission will be 

discussed. 

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(L39) 

CHEMICAL CHARACTERIZATION OF DEKATI ® LOW PRESSURE IMPACTOR (DLPI) 

WALL DEPOSITS 

Thibaut Durand, Yves Morele, Denis Bemer, and Davy Rousset 

Institut National de Recherche et de Sécurité, Rue du Morvan CS60027, 54519 Vandoeuvre-lès- 

Nancy, France 

e-mail: Thibaut.Durand@inrs.fr 

Cascasde impactors are widely used to assess aerodynamic particle size distribution of airborne 

particles. It is possible from each impaction stage to determine mass concentration and chemical 

composition of particles according to size fractions. Geometry of these impactors however induces 

inner deposit phenomena, which can be due to particle bounce on impacting support, or to diffusion 

phenomena for fine particles, or because of the particles charges for specific impactors (for instance 

in the electrical low pressure impactor). Previous studies have highlighted wall depositions for 

several impactors but these have never been properly studied on low pressure impactors which are 

dedicated for ultrafine particles characterization and monitoring. In this study, characterization of 

wall deposits was carried out with the Dekati ® Low Pressure Impactor (DLPI), which separates 

airborne particles into 13 size fractions from < 30 nm up to > 10 μm (filter stage configuration). In 

the DLPI, many surfaces could be subjected to particles collection, in addition to impaction filter. 

Airborne particles were generated by a metal coating process, an electric arc gun with zinc wires. 

This process is widely used for coating and generates large quantities of ultrafine particles. The 

aerosol produced was bi-modal (80 nm and 5µm) and thus covered the whole DLPI collection range. 

In front of the gun spray, aerosol was driven through a tunnel at a constant flow rate. The sampling 

point was situated few meters down the tunnel from the emission point so that the aerosol stabilized. 

This sampling point was connected to a 10 fold diluter with 4 outputs among which two was 

connected to the DLPI and to a 47 mm filter holder (PVC filters) as a reference in mass 

concentration. The diluter was used because of the high particle concentration (~300 mg.m -3 ). This 

concentration would imply too short sampling duration without dilution. For the first generation, an 

additional Electrical Low Pressure Impactor (ELPI) was connected with the DLPI and the filter to 

assess the difference in collection efficiency for two similar impactors. No wall characterization was 

performed for the ELPI. 

Two different amounts of zinc were investigated (N=3) to check the influence of the particle 

concentration on the deposition phenomena for two collection duration (5 and 20 minutes). For each 

generation, gravimetric and chemical analyses were performed. Before each generation, the DLPI 

was entirely cleaned, by cleaning each part in an ultrapure water sonicated bath, then by isopropyl 

alcohol wiping. 

To quantify wall deposits, 37 mm mixed cellulose ester (MCE) membranes were wetted with 

ultrapure water to wipe inner surface of the impactor. One MCE membrane was used for each 

collection plate and one for each jet-plate. Each MCE was first cut into four parts in order to wipe 

each side of a specific piece at least twice. Once used, the four parts of the membrane were stored in 

clean tube before acid digestion. Blanks were performed before and after each run to verify cleaning 

procedure, and the wall particles collection efficiencies. Digestion of MCE membranes was 

performed directly in the storage tube with HClO 4 :HNO 3 (1:6) acid mixture. 

25 mm PVC filters were used as collection medium in the DLPI impaction stage. They were 

previously Triton-X washed, vaseline greased, and weighed before generation. After generation, 

they were weighted again and then digested with ultrapure nitric acid using a microwave digestion 

system. Chemical composition from both PVC filters and MCE membranes were determined either 

by inductively coupled plasma optical emission spectrometry (ICP-OES) or by inductively coupled 

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plasma mass spectrometry (ICP-MS), according to particle loading. 

Results showed a good repeatability between the different generations regarding the mass collected 

on the PVC impaction filters. Moreover gravimetric results and chemical analysis match well. Wall 

deposits were more scattered among generations although a similar whole trend could be noticed. 

Considering the relative amount of Zn on walls per stage, three main deposition sites could be 

distinguished. The first one was in a small size range, around the fourth and fifth collection plate 

(~200 nm), the second one in the intermediate size range (~1 µm), and the third one in a large range, 

on the thirteenth stage (~10 µm). These maximums were not related to the mode of the aerosol. 

Amounts of zinc were higher on jet-plate parts than onto corresponding collection plates, which is 

consistent regarding the surface wiped. No significant differences regarding the relative amount of 

wall deposits were observed between 5 and 20 minutes sampling duration. For the whole DLPI 

column, in average, about 13 % of the total mass collected was found on surfaces rather than onto 

the PVC impaction filters. These wall losses could be considered as negligible, but locally for some 

stages, wall losses could rise up to 30%, which could lead to an underestimation of a specific size 

fraction of the airborne particles. 

Results from the ELPI experiments showed a large difference between ELPI and DLPI: ELPI 

collected 75 and 59 % of particles less than DLPI did respectively, when comparing chemistry and 

gravimetric results. This cannot be explained only because of the charge of particles. More 

investigation should be done to explain the phenomenon. 

In conclusion, characterization of DLPI wall deposits using a zinc aerosol containing ultrafine 

particles mainly showed that: 

Wall deposits were not specifically related to aerosol modes 

Collection times were not influent on the relative quantity deposited on walls 

Main wall deposits were found on jet-plate nozzles 

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(L40) 

CHEMICAL CHARACTERIZATION AND OXIDATIVE POTENTIAL OF PM 2.5 

COLLECTED IN OFFICE BUILDINGS IN GREECE AND THE NETHERLANDS: A 

COOPERATIVE STUDY 

Tamás Szigeti 1 , Philomena M. Bluyssen 2* , Henricus J.M. Cornelissen 2 , Chrissi Dunster 3 , Krystallia 

K. Kalimeri 4 , Frank J. Kelly 3 , Yvonne de Kluizenaar 2 , Franco Lucarelli 5 , Ioannis Sakellaris 4 , Dikaia 

E. Saraga 4 , John Bartzis 4 , Gyula Záray 1 , Victor G. Mihucz 1 

1 

Department of Analytical Chemistry, Eötvös Loránd University, 1117 Budapest, Hungary 

2 TNO, PO Box 49, 2600 AA Delft, The Netherlands 

2* Current address: Department of Architectural Engineering and Technology, Delft University of 

Technology, Delft, 2628 BL, The Netherlands 

3 MRC-HPA Centre for Environment and Health, King’s College London, SE1 9NH London, UK 

4 Department of Mechanical Engineering, University of Western Macedonia, 50100 Kozani, Greece 

5 Department of Physics and Astronomy, University of Florence/INFN, 50019 Sesto Fiorentino, 

Italy 

e-mail: tamas.szigeti@yahoo.com 

Indoor air quality has a high importance in the everyday life of people of the 21 st century, as people 

spend a large proportion of their time indoors. One of the objectives of the European collaborative 

project called OFFICAIR is the characterization of indoor and outdoor PM 2.5 (particles with an 

aerodynamic diameter smaller than 2.5 μm) in and around modern office buildings. 

PM 2.5 sampling was performed in 1 office in 5 different buildings in Greece and 1 office in 2 

buildings in The Netherlands with low-volume aerosol samplers operating for about 100 hours (from 

Monday morning to Friday afternoon) onto 47 mm quartz fibre filters (Whatman QM-A) in summer 

2012 and in the same offices in winter 2012/2013. All sampling locations were < 15 km far from 

sea). Thus, in Greece the 5 office buildings were in Athens and its metropolitan area, while in The 

Netherlands, one sampling location was by the sea and the other in Delft (about 15 km far from the 

sea). Outdoor sampling was also undertaken close to the air intake of the of HVAC system (4 

buildings out of the 7) or at ground floor (3 out of the 7). Filters had been conditioned at 20 1 °C 

and 50 5% relative humidity. Field blanks were also employed. 

In summer, indoor PM 2.5 mass concentration values ranged between 5.2 μg m -3 and 16.8 

μg m -3 whereas outdoor concentrations were always higher, ranging between 10.6 μg m -3 and 31.2 

μg m -3 . In winter, indoor PM 2.5 mass concentration values ranged between 5.0 μg m -3 and 18.5 μg m - 

3 and the outdoor concentration ranged between, 6.1 μg m -3 and 33.6 μg m -3 . Indoor / outdoor (I/O) 

mass concentration ratios varied between 0.42 and 0.86. This outcome is in good agreement with 

literature data: 0.37-0.88 (Horemans et al., 2008). However, the summer and winter I/O ratios 

differed for each monitored building. 

Every one third part of the filters were subjected to microwave-assisted digestion using closed 

Teflon vessels with quartz inlets filled with 5 mL of aqua regia and immersed in a mixture of 10 mL 

hydrogen peroxide and deionized water (1: 4 v/v). After the samples were evaporated close to 

dryness, they were dissolved into 5 mL of 5 % w/v HNO 3 and subjected to inductively coupled 

plasma mass spectrometric (ICP-MS) analysis. Another third part of the samples were sonicated in 5 

mL of deionized water for 150 min. Then, the acidified samples also underwent to ICP-MS analysis. 

The anion and cation content of the filter samples subjected to water sonication were further diluted 

-121 -



five times and determined by ion chromatography equipped with suppressor columns for the 

determination of anions. Major ion sources of the samples were: SO 4 

2- 

, NH 4 + , Ca 2+ , Na + and NO 3 

- 

ions. Chloride, K + and Mg 2+ can be considered as minor ions in the samples. Generally, the major 

anion in the samples was sulphate (40.3-67.8 % of the total ions determined) in all samples 

independently of their provenance for the summer campaign. In the air-conditioned Dutch offices, 

the nitrate concentration was lower in summer than outdoor by 4-10 times when the outdoor 

temperature was lower than the indoor value. The contribution of sea-salt-sulphate to the PM 2.5 mass 

was higher in the Netherlands than in Greece. Contribution of ions to PM 2.5 mass varied between 

25% and 63%. 

Seventeen elements (Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Mo, Cd, Sn, Sb, Pt, Pd) could be 

determined in the filter samples independently of the provenance and sampling site in the 

pg m -3 - ng m -3 concentration range. The traffic density was reflected in the trace element 

concentration: the traffic-related element concentration was higher in the urban areas compared to 

rural or suburban sampling sites. Iron, Al and Zn were the major trace elements in the samples 

independently of the site of collection. Considerable differences were observed in the concentration 

of some elements in the water-soluble fraction of the samples compared to the aqua regia 

extractable part. For example, Fe concentration in the water-soluble part was 4%-24% of the aqua 

regia extractable part. For V, the same percentage varied between 59% and 99%. Some elements 

(i.e., Cr, Fe, Cu, Rb, Cd, Pb) were accumulated in the indoor environment. Generally, the water 

soluble metal concentration/aqua regia extractable metal concentration ratios were higher for indoor 

samples than for the outdoor ones. 

Samples were also subjected to oxidative potential analysis (Godri et al., 2011). This consisted of a 

4-h incubation at 37 °C of 5-mm discs cut from the loaded filters in 0.5 mL of a model respiratory 

tract lining fluid containing the antioxidants of urate (UA), ascorbate (AA) and glutathione each at 

200 µmol dm -3 . After centrifugation, the remaining amounts of UA and AA were determined by 

reversed-phase high performance liquid chromatography with electrochemical detection. 

Glutathione (GSX, GSSG, GSH) was determined by enzyme-linked 5,5'-dithio-bis(2-nitrobenzoic 

acid) (DTNB) assay by using a microplate reader. Indoor PM 2.5 generally had increased oxidative 

potential compared with the equivalent outdoor sample and this appeared to be related to the 

increased concentrations of some trace elements in the indoor PM 2.5 . 

This work was supported from the project “OFFICAIR” (On the reduction of health effects from 

combined exposure to indoor air pollutants in modern offices) funded by the European Union 7 th 

Framework (Agreement 265267) under Theme: ENV.2010.1.2.2-1. The financial support through 

grant TÁMOP-4.2.2/B-10/1-2010-0030 is also, hereby, acknowledged. 

Horemans, B., Worobiec, A., Buczynska, A., Van Meel, K. and Van Grieken, R. (2008) J. Environ. 

Monitor. 10, 867-876. 

Godri, K.J., Harrison, R.M., Evans, T., Baker, T., Dunster, C., Mudway, I.S., Kelly, F.J. (2011) 

PLoS ONE 6, e21961. doi:10.1371 

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(L41) 

FTIR (DRIFT) SPECTROSCOPIC ANALYSIS OF ACCUMULATION AND STRUCTURAL 

FEATURES OF POLY-3-HYDROXYBUTYRATE IN CELLS OF AZOSPIRILLUM 

BRASILENSE: EFFECTS OF COPPER(II) 

Anna V. Tugarova 1 , Alexander A. Kamnev 1 , Petros A. Tarantilis 2 , Olga P. Grigoryeva 3 and 

Alexander M. Fainleib 3 

1 Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and 


2 Laboratory of Chemistry, Department of Science, Agricultural University of Athens, 11855 Athens, 

Greece 

3 Department of Heterochain Polymers and Interpenetrating Polymer Networks, Institute of 

Macromolecular Chemistry, National Academy of Sciences of Ukraine, Kyiv 02160, Ukraine 

e-mail: tugarova_anna@mail.ru; a.a.kamnev@mail.ru 

Unfavourable environmental factors can induce the accumulation of polyhydroxyalkanoates (PHAs) 

in many bacteria in the form of intracellular granules serving as energy and carbon reserve materials. 

In the agriculturally important phytostimulating rhizobacteria of the genus Azospirillum, PHAs are 

known to be represented by a homopolymer, poly-3-hydroxybutyrate (PHB). This biopolyester, 

playing a role in bacterial stress endurance, is also of industrial and biotechnological significance as 

an environmentally friendly biodegradable plastic. 

For the last decade, we have been studying metabolic responses of Azospirillum brasilense, one of 

the most widely studied species, to various stresses using Fourier transform infrared (FTIR) 

spectroscopy. Using this technique in the diffuse reflectance mode (DRIFT), which is sensitive to 

fine structural modifications of major cellular biomacromolecules, PHB accumulation was analysed 

in cells of A. brasilense (strain Sp7). Stress conditions included bound nitrogen limitation (high C:N 

ratio inducing PHB accumulation) and, as an additional stress factor, the presence of 0.1 mM Cu 2+ in 

the medium. It has been found that Cu 2+ induced a 1.6-fold increase in PHB accumulation (up to 40 

wt.% of dry biomass) at an earlier phase of growth (after 2 days). By the 9 th day, in both cases PHB 

content reached ca. 50 wt.%. Analysis of DRIFT spectra has shown that prolonged stressed 

conditions induced a shift in some main PHB-related vibrational bands reflecting the accumulation 

of PHB of lower crystallinity. A more amorphous PHB fraction is known to be more rapidly 

enzymatically hydrolysed (i.e., more readily ‘digestible’ by starving cells). In the presence of Cu 2+ , 

this effect was already noticeable after 2 days of PHB accumulation, reflecting cellular response to 

the double stress. 

PHB samples extracted with CHCl 3 from biomasses after 9 days of growth (with and without Cu 2+ ) 

were also comparatively studied as dried films using FTIR spectroscopy, differential scanning 

calorimetry (DSC) and thermogravimetric analysis (TGA). Some differences in the PHB structure, 

lower thermostability of the PHB sample obtained from Cu 2+ -stressed cells and its lower degree of 

crystallinity (partly remaining after extraction and film formation) were detected. The results 

obtained show the possibility to regulate PHB accumulation and its structural features by varying the 

nature, severity, duration and combination of stress factors. 

This work was supported in part by a research grant from The Siberian Health International LLC 

(Novosibirsk, Russia; Call for Projects, 2012). 

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(L42) 

A NEW HYBRID FLUOROMETER-SPECTROPHOTOMETER FOR WATER QUALITY 

ANALYSIS OF OIL, CHROMOPHORIC DISSOLVED ORGANIC MATTER, 

CHLOROPHYLL AND -NH X 

Adam M. Gilmore 1 

1 HORIBA Instruments Inc., 3880 Park Avenue, Edison, NJ 08820 

e-mail: adam.gilmore@horiba.com 

This presentation describes a new water quality analysis instrument that can continuously and 

simultaneously measure the absorbance spectrum and fluorescence excitation-emission matrix 

(EEM). Key applications include oils and polycyclic aromatic hyrdocarbons, chromophoric 

dissolved organic matter (CDOM), chlorophyll and –NH x containing compounds as well as oxygen 

demand parameters. The concentration of CDOM compounds in the humic and fulvic acid classes 

are globally regulated for drinking water treatment because they represent disinfection by-product 

precursors (DBPPs) that can generate toxic disinfection by-products during halogen disinfection 

treatments for microorganisms such as Giardia spp. CDOM thus plays an important role in the new 

Stage 2 USEPA regulations for drinking water sterilization. The instrument allows for continuous 

and rapid (seconds to minutes) monitoring of the DBPPs to facilitate accurate prediction of the 

trihalomethane formation potential (THMFP) and dissolved organic carbon (DOC) concentrations. 

Conventional tests for THMFP and DOC require long and tedious protocols that are prone to errors 

and prevent rapid responses to the natural dynamics of CDOM concentrations. Further, 

conventional total organic carbon meters and online ultraviolet absorbance methods have proven to 

indicate THFMP with poor correlative capacity due to lack of specific information on key DBPPs. 

The fluorescence data corrections for the spectral response, sample concentration-dependent 

absorption and for both the excitation beam and fluorescence signals are certified by standard 

reference materials and protocols that are either NIST and or ISO traceable. The data collection and 

processing is fully automated through to a component ID and concentration table by means of a 

selection of validated multivariate tools including principal components analysis (PCA), parallel 

factor analysis (PARAFAC) and classical least squares (CLS). Notably the wavelength range of the 

instrument is also compatible with USEPA approved absorbance and fluorescence methods for 

monitoring chlorophyll concentrations as these relate algae that produce odor and taste compounds 

as well as toxins associated with algal blooms. The absorbance data further can be used to quantify 

concentrations of N –NH 2 and N–NH 3 compounds simultaneously to the fluorescence EEM 

information. The system also has proven potential to quantify oxygen demand parameters as well as 

identify and quantify a wide range of pollutants. 

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(L43) 

OCCURRENCE OF POLYCHLORINATED BIPHENYLS (PCBS) AND 

POLYBROMINATED DIPHENYLETHERS (PBDES) IN DIFFERENT FISH SPECIES 

FROM ILHA GRANDE BAY, SOUTHEASTERN BRAZIL 

Ricardo Lavandier 1 , Natalia Quinete 2 , Rachel Ann Hauser-Davis 1 , Patrick Simões Dias 3 , Satie Taniguchi 3 , 

Rosalinda Montone 3 and Isabel Moreira 1 

1 

Department of Chemistry, Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rua Marquês de 

São Vicente, 225, Gávea – Rio de Janeiro, RJ 22453-900, Brazil 

2 Environmental Analysis Research Laboratory, Southeast Environmental Research Center (SERC), Florida 

International University, Biscayne Bay Campus, Marine Sciences Building, 3000 NE 151st, North Miami, FL 

33181, USA 

3 Institute of Oceanography, São Paulo University (USP), Praça do Oceanográfico 191, Butantã, São Paulo, 

SP 05508-900, Brazil 

e-mail: isabel@puc-rio.br 

Polybrominated Diphenyls Ethers (PBDEs) and Polychlorinated biphenyls (PCBs) are 

environmental contaminants that have been the aim of several recent investigations. They have 

similar physicochemical properties and may present up to 209 different congeners. These 

compounds bioaccumulate throughout the food web. Both are endocrine disrupters and can cause 

reproductive alterations, as well as neurotoxic and carcinogenic effects. Humans are subject to a 

high risk of contamination by these compounds. PBDEs and PCBs have been increasingly studied in 

the northern hemisphere, but few studies have been conducted in the southern hemisphere. In the 

present study, PBDEs and PCBs levels were determined in three different fish species from the Ilha 

Grande Bay, located in the state of Rio de Janeiro, Brazil. This area is considered a reference area, 

since previous investigations have indicated no sources of contamination regarding organochlorine 

pesticides and metals. The analyzed fish species were Mugil liza - mullet (n=15), Micropogonias 

furnieri - croaker (n=25) and Trichiurus lepturus - scabbardfish (n=21), the latter in two different 

seasons (dry and wet). Fish were sexed, individually measured (±1.0 mm), weighed (±0.01 g) and 

dissected to obtain muscle and liver samples. Samples were immediately frozen at -80 ºC, freezedried 

and stored until analysis. Sample extraction consisted of four different steps: saponification, 

extraction, clean-up and chromatographic analysis by GC-MS. Lipid content was also determined. 

The GC–MS analyses was conducted in an electron capture negative ionization mode (GC/MS- 

ECNI) and operated in selected ion monitoring (SIM) mode. PCB-53 was used as an internal 

standard. The carrier gas was helium with a constant flow of 1.1 mL min -1 and 1 μL of sample 

extract was injected in the splitless mode. The conditions for PCBs determination were the 

following: the column oven was programmed for an initial temperature of 75 ºC for 3 min and a rate 

of increase of 15 ºC min -1 from 75 to 150 ºC, then at a rate of 2 ºC min -1 the temperature was raised 

to 260 ºC. Finally, the temperature was increased at a rate of 20 ºC min -1 –300 ºC and was held for 10 

min. The conditions for PBDE determination were the following: the column oven was programmed 

for an initial temperature of 70 ºC for 1 min and a rate of 12 ºC min -1 from 75 to 154 ºC, then at a 

rate of 2 ºC min -1 the temperature was raised to 210 ºC. Finally, the temperature was increased at a 

rate of 3 ºC min -1 –300 ºC and was held for 5 min. PBDEs levels were very low, with values below 

the limit of quantification. PCBs concentrations ranged from 2.29 to 27.60 ng g -1 ww in muscle and 

from 3.41 to 34.22 ng g -1 ww in liver of the three investigated fish species. Values for the daily 

intake of fish by the human population around the Ilha Grande area were calculated and levels of 

PCBs were above the maximum allowed under Brazilian law, the FDA/EPA norms and the Italian 

legislation, therefore raising great concern regarding PCB contamination of fish products consumed 

in the area. Correlations were established between the concentration of PCBs and biometric 

variables of the fish individuals, such as length and fat content, and a statistical variation due 

seasonality was also observed only for croaker, with higher PCBs concentrations during the wet 

season. 

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(L44) 

APPLICATION OF MULTI-REFLECTION, HIGH RESOLUTION TIME-OF-FLIGHT- 

MASS SPECTROMETRY AS DETECTOR FOR ONE- AND TWO-DIMENSIONAL GAS 

CHROMATOGRAPHY: CHARACTERIZATION OF COMPLEX MIXTURES 

Ralf Zimmermann a , Thomas Gröger a , Marie Schäffer a , Benedikt Weggler a , Jürgen Wendt b , 

Martin Sklorz a , Theo Schwemer a 

Joint Mass Spectrometry Centre of University of Rostock, Chair of Analytical Chemistry, 

Rostock/Germany and Helmholtz Zentrum München,CMA, Neuherberg/Germany 

Contact: ralf.zimmermann@uni-rostock.de 

LECO Instrumente GmbH/Mönchengladbach/Germany 

Complex samples e.g of petrochemical origin require highly selective analytical methods for 

comprehensive analysis. Gas chromatography-mass spectrometry (GC-MS) and comprehensive twodimensional 

gas chromatography-time-of-flight mass spectrometry (GCxGC-TOFMS) are current 

standard approaches for resolving the “petrochemical complexity”. On the other hand, ultra-high 

mass resolution mass spectrometry became prominent in elucidating the complexity of 

petrochemical samples (e.g. by direct infusion FTICR- or Orbitrap-MS measurements) by 

determination of elemental compositions via exact mass measurement. This approach, however, 

usually has limitations in generality (AP ionization selectivities/matrix effects) and discrimination of 

isomeric compounds. By coupling of high resolution (gas-) chromatography and high massresolution 

mass spectrometry, the knowledge e.g. on the “chemical space” of SVOC in petroleum 

fractions can be increased. A novel TOFMS-system with a multi-reflection-time-of-flight 

technology using periodic ion focusing lenses (HRT, LECO Inc, St. Joseph, USA), allows the 

detection of gas chromatographic transients at high mass-resolution (R = 50.000) with good mass 

accuracy (< 1 ppm) and at a very fast acquisition rate (200 Hz) without compromising the detection 

sensitivity. As the HRT-TOFMS is capable to follow accurately very fast changing chromatographic 

transients it is particularly well suited for coupling to comprehensive two-dimensional gas 

chromatography (GCxGC, GC: Agilent Inc., USA, Modulator: Zoex Inc., USA). The HRT-TOFMS 

(electron ionization, 70 eV) was applied e.g. to the analysis of petrochemical samples (one- and 

two-dimensional comprehensive gas chromatography), including a B5 biodiesel (~ 5 % fatty acid 

methyl esters (FAME) content). The high-resolution mass spectra can be used for target compound 

identification/verifications in the case of one dimensional gas chromatography. For comprehensive 

two-dimensional gas chromatography the high resolution MS mode was used to improve the 

selectivity of a no-targeted compounds-class identification scheme, called “scripting” [1]. The 

scripting approach uses on the one hand two-dimensional retention-time information (i.e. specific 

“areas” in the GCxGC - 2D-retention time-space, which can be translated into a physical-chemical 

parameter-space characterizing e.g. polarity and volatility of compounds) and on the other hand 

substance-class specific EI-fragmentation pattern rules for classification of peaks to substance 

classes. The high mass resolution enables an improved scripting approach, using the exact massvalues 

of specific fragments to suppress the any accidental contribution of matrix (fragment-)peaks 

with different elemental composition. Note that this interfering “matrix”-peak contribution is usually 

quite large in complex samples. It is demonstrated that the “exact mass filtering” in combination 

with the high chromatographic resolution of GCxGC can have significant impact on a better 

understanding of complex molecular mixtures. Finally the approach is also compared to another GC- 

HRMS technique using FT-ICR. 

[1] W. Welthagen, J. Schnelle-Kreis, R.Zimmermann; J. Chromatography A 1019 (2003) 233-249 

-126 -



(L45) 

NEW IMAGING CAPABILITIES USING LA-ICPTOF MASS SPECTROMETRY 

H.A.O. Wang, 1,3 C. Giesen, 2 D. Grolimund, 3 B. Bodenmiller, 2 D. Günther 1 

1 Trace Element and Micro Analysis Group, ETH Zurich, 8093 Zurich 

2 

Institute of Molecular Life Sciences, University of Zürich, 8057 Zürich 

3 

microXAS Beamline Project, Swiss Light Source, PSI, 5232 Villigen PSI 

e-mail: guenther@inorg.chem.ethz.ch 

This work demonstrates an advanced multiplexing imaging setup based on Laser Ablation (LA) 

coupled to a sector field-ICP-MS and a commercial Mass Cytometer. The current measurements 

successfully demonstrate sub-cellular (~1 μm) spatial resolution imaging of biological tissue thin 

sections. One of the key improvements is attributed to a laser ablation cell. 1 This novel LA cell has a 

short washout time and enhances the signal to noise ratio of the LA transient signal. It enables 

complete separation of single shot signals generated by high frequency (>20 Hz) laser ablation and 

furthermore acquisition of analytes in the sample aerosol produced by 1 μm laser single shot. As 

shown in a case study, multiplexing biomarkers with metal-tagged antibodies were imaged in thin 

sections of breast cancer tissue. The resulted high spatial resolution high sensitivity biomarker 

images were acquired simultaneously by the mass cytometer (CyTOF®). Finally, the experimental 

setup helps biologists investigate various breast cancer sub-types, and better understand cancer 

metastasis mechanisms. The presented imaging setup will open new research opportunities for 

pathologists and pharmacologists and some of the potential applications will be discussed. 

1 Wang, H.A.O. et al. Fast Chemical Imaging at High Spatial Resolution by Laser Ablation 

Inductively Coupled Plasma Mass Spectrometry. Submitted to Analytical Chemistry (2013). 

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(L46) 

FURTHER DEVELOPMENTS OF AN ENERGY- AND POSITION-SENSITIVE XRF 

IMAGING SYSTEM BASED ON A THCOBRA DETECTOR 

A.L.M. Silva 1 , M.L. Carvalho 2 , J.M.F. dos Santos 3 , J.F.C.A. Veloso 1 

1 I3N – Physics Department of University of Aveiro, 3810-193 Aveiro, Portugal 

2 Atomic Physics Centre, University of Lisbon, 1649-003 Lisboa, Portugal 

3 GIAN—Physics Department of University of Coimbra, 3004-516, Coimbra, Portugal 

e-mail: analuisa.silva@ua.pt 

New developments of a full-field and large area energy dispersive X-ray fluorescence (XRF) 

imaging system for elemental analysis, are presented. The system offers an alternative instrument 

for today's X-ray fluorescence imaging needs in different fields of science. The system presents 

moderate both energy and spatial resolution which are sufficient for many applications which 

require the combination of these two detector modes and large detection area. 

The XRF imaging system is based on a new Micropattern Gaseous Detector called 2D-THCOBRA. 

The 2D-THCOBRA is a combination of the THGEM with the 2D-MHSP, benefiting from the 

robustness and low cost of the first structure and from the position discrimination, together with the 

two charge multiplication stages of the second structure The micropatterned structure uses a simple 

position readout based on resistive lines and has an active area of about 10x10 cm2 allowing large 

area of analysis. 

The sample is excited by a broad X-ray beam and the resulting X-ray fluorescence photons are 

detected, through a pin-hole lens, by the full-field energy dispersive detector, the 2D-THCOBRA. 

The single-photon counting detector allows for energy resolved X-ray imaging (22% FWHM for 5.9 

keV X-rays) with a spatial resolution of about 0.5 mm (FWHM), and a counting rate capability of up 

to 0.5 MHz limited by the present electronic readout configuration. 

Results will be presented and discussed concerning the XRF system performance and the different 

analyzed samples. 

Acknowledgements: This work was partially supported by projects CERN/FP/123604/2011 and 

PTDC/FIS/110925/2009 through COMPETE, FEDER and FCT (Lisbon) programs. A.L.M. Silva, 

was supported by a doctoral grant from FCT (Lisbon) with the reference SFRH/BD/61862/2009. 

-128 -



(L47) 

PHARMACEUTICAL IMAGES HARVESTING AND COMPARISON 

Tomáš Pekárek 1 , Martina Mudrová 2 , Tomáš Chvojka 1 and Aleš Procházka 2 

1 Development Dept., Zenitva, k.s., CZ-10237 Prague 10, Czech Republic 

2 Department of Computing and Control Engineering, Institute of Cemical Technology Prague, CZ- 

16628 Prague 6, Czech Republic 

e-mail: Tomas.Pekarek@zentiva.cz 

Infrared and Raman mapping and imaging can result in very valuable information, not only in the 

generic pharmaceutical development for originator’s manufacturing procedure estimation, but also 

for counterfeit detection, as many counterfeits have different particles’ size and/or their distribution. 

Obtained images are currently usually evaluated and compared manually. In order to make the 

comparison and evaluation more objective, reliable and person independent, a new approach 

employing the in-house build software was developed. 

Firstly, it is necessary to extract as much information as possible from the initial map (Fig. 1) 

obtained by IR or Raman mapping or imaging of pharmaceutical tablet cross-section. Such crucial 

information is the individual components’ area, number and size of individual components and the 

neighborhood of individual components. 

Fig. 1. IR map – different colors represent individual components of a pharmaceutical tablet. 

Once the data mentioned above are known, two or more maps can be simple compared in selected 

parameters (Fig. 2) to see how (dis)similar are the maps, which parameter contributes the most to the 

map differentiation, etc. Up to five parameters can be easily displayed: three axes, mark size, mark 

color. As there is a large amount of observed properties, Principal Component Analysis can be used 

for dimension reduction (Fig. 3). The influence of each parameter to the map differentiation can be 

investigated, as well. 

Using such method it is possible to make the generic backward-engineering easier and cheaper and 

to detect counterfeits in case of originators’ litigation. 

-129 -



Selected Properties - Comp. No.2 

Mark Size ~ Particle Size (8-con.) 

Component Occurence 

30 

20 

10 

100 0 

8 

80 

60 

8-Neighbour - Comp. No.3 

40 

11 

7 

20 

0 

10 

10 

Fig. 2. Comparison of different maps in selected parameters: Properties of the investigated 

component are marked (Component’s occurrence, its neighborhood with other two selected 

components and average particle size). 

20 

3 

2 4 

30 

9 

40 

5 

6 

50 

1 

60 

8-Neighbour - Comp. No.1 

70 

100 

(a) Original Data 

50 

(b) Data Transformed 

50 

0 

0 

2 4 6 8 10 

(c) PCA Result 

-50 

2 4 6 8 10 

Marker Size ~ 4th PC 

10 

3rd PC 

5 

0 

20 

-5 

10 

2nd PC 

0 

-10 

8 

7 

-60 

11 

-40 

5 

1 3 

-20 

9 

6 

10 

2 

4 

0 

1st PC 

20 

Fig. 3. Example of reduction of a number of observed parameters by means of PCA: Six selected 

properties (a) were transformed into four new parameters (b). Result obtained is presented in (c). 

-130 -



(L48) 

NOVEL MULTISPECTRAL IMAGING APPROACHES FOR RECOVERING OF 

DEGRADED ARCHAEOLOGICAL WALL PAINTINGS 

S. Legnaioli 1 , G. Lorenzetti 1 , G.H. Cavalcanti 2 , E. Grifoni 3 , L. Marras 3 , A. Tonazzini 4 , E. Salerno 4 , 

P. Pallecchi 5 , G. Giachi 5 and V. Palleschi 1,6 

1 

Institute of Chemistry of Organometallic Compounds 

Research Area of National Research Council 

Via G. Moruzzi, 1 – 56124 Pisa (ITALY) 

2 

Instituto de Fìsica, Universidade Federal Fluminense 

Av. Gal. Milton Tavares de Souza, s/nº - Campus da Praia Vermelha - CEP 24210-346 - Niterói – 

Rio de Janeiro (BRAZIL) 

3 

Art-Test s.a.s. 

Via del Martello, 14 - 56121 Pisa (ITALY) 

4 

Institute of Sciences and Technology of Information 

Research Area of National Research Council 


5 

Soprintendenza per i Beni Archeologici della Toscana 

Via della Pergola, 65 - 50121 Firenze (ITALY) 

6 

Department of Civilizations and Forms of Knowledge 

University of Pisa Via G. Galvani, 1 – 56126 Pisa (ITALY) 

e-mail: vincenzo.palleschi@cnr.it 

New approaches in the application of multispectral imaging to the recovery of archeological wall 

paintings are presented, based on blind deconvolution techniques and on a novel method of image 

treatment (Chromatic Derivative Imaging – ChromaDI) which offers a way of visualizing in color 

the information coming from more than three spectral bands. The methods are applied to the 

recovery of some wall paintings from the Tomb of the Monkey, an Etruscan tomb in the necropolis 

of Poggio Renzo, near the city of Chiusi (Siena), dated around 480-470 BC. It is shown that a 

number of otherwise invisible details emerge from the multispectral image set, which can be 

enhanced and evidenced using the techniques described. 

-131 -



(L49) 

LA-ICPMS IMAGING AND NUCLEAR FORENSICS: PU ISOTOPE RATIOS IN 

SEDIMENTS FROM MAYAK PA, RUSSIA 

Simone Cagno 1,2 , Kevin Hellemans 2 , Ole Christian Lind 1 , Lindis Skipperud 1 , Koen Janssens 2 , Brit 

Salbu 1 

1 CERAD, Department of Plant and Environmental Science, Norwegian University of Life Sciences, 

P.O. Box 5003, N-1432 Ås, Norway 

2 Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerpen, 

Belgium 

e-mail: simone.cagno@umb.no 

Laser Ablation – Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) was initially 

intended as the combination of a well-established trace-ultra trace analytical technique (ICPMS), 

plus a tool for representative solid sampling, i.e. the laser ablation system. The development of fast 

washout ablation cells has recently allowed great advances in 2D and 3D isotope mapping [1]. 

In this paper we focus on the application of LA-ICPMS on reservoir sediments originating from the 

MAYAK Production Association, Ural region, Russia. There, weapon production took place from 

1948, and reprocessing of civil sources took place from mid 1980s. Both sources generated d vast 

radioactive contamination at the site, downstream the river and in the surrounding region [2]. The 

samples of investigation originate from the 1996 joint Russian-Norwegian monitoring campaign. At 

that time, the activity concentrations of plutonium isotopes ( 239,240 Pu) were determined using by 

alpha spectrometry (AS). Sediments were ashed and radiochemical separations were performed prior 

to electrodeposition of Pu on steel planchettes [3]. In alpha spectrometry, 239 Pu and 240 Pu cannot be 

distinguished due to similar alpha energies. However, the 240 Pu/ 239 Pu ratio is a highly useful tool for 

source identification, i.e. to distinguish civil sources (high ratio, e.g. reprocessing), global fallout 

(intermediate ratios) and weapon grade material (low ratio). Large archives of electrodeposited alpha 

sources, usually planchettes, are stored worldwide. With the development of new techniques such as 

LA-ICPMS, these samples could be subject to further measurements, allowing information on 

individual Pu isotopes. The MAYAK samples have therefore been reanalysed with the aim of 

demonstrating the feasibility of LA-ICPMS mapping of Pu isotopes, allowing the comparison of the 

LA-ICPMS results with those previously obtained by AS and AMS on the same samples [4-5]. 

The LA-ICPMS analyses were performed at the University of Antwerp, with a NWR193 ArF 

excimer laser, combined with an Agilent 7700X and a Varian 820 ICPMS. The results show 

minimal or no presence of other elements in the electrodeposited samples, thus confirming high 

efficiency of the separation procedure. The Pu electrodeposition was fairly inhomogeneously 

distributed on the steel surface, however, LA-ICP-MS allowed the measurements of individual Pu 

isotopes, and the obtained 240 Pu/ 239 Pu ratios demonstrated the presence of global fallout Pu as well 

as weapon grade Pu. Based on a series of planchettes from the Mayak reservoir 10, the 240 Pu/ 239 Pu 

ratios in the deep sediments were low, reflecting the Pu weapon production activities of MAYAK 

PA in the 1940-50s. 

[1] Van Elteren JT et al. (2013) J Anal Atom Spectrom DOI: 10.1039/C3JA30362D 

[2] Christensen, GC et al. (1997) Sci Total Environm 202: 237-248 

[3] Ketterer ME et al. (2004) J Anal Atom Spectrom 19:241–245 

[4] Skipperud L et al. (2005) Health Physics 89: 255-266 

[5] Oughton DH et al. (2000) Environ. Sci. Technol. 34: 1938–1945 

-132 -



(L50) 

PHYSICOCHEMICAL INVESTIGATION OF THE WALL PAINTINGS OF PETROS 

PAULOS CHURCH, ETHIOPIA 

Kidane Fanta Gebremariam, 

Norwegian University of Science and Technology, Trondheim, Norway 

-133 -



(L51) 

COMPARISON BETWEEN SR-XRF AND ICP-AES 

Jun Kawai 

Kyoto University, Department of Materials Science and Engineering, Sakyo-ku, Kyoto 606-8501, 

Japan 

e-mail: kawai.jun.3x@kyoto-u.ac.jp 

Sensitivity of elemental analysis between SR-XRF (synchrotron radiation X-ray fluorescence) and 

ICP-AES (inductively coupled plasma atomic emission spectrometry) is compared using data 

submitted to court for the arsenic poisoning case in Japan. The key evidence was that Sn, Sb, and Bi 

were found as impurity elements in the arsenic stored at kitchen of a saleswoman (she used it as 

pesticide), and paper cup near the poisoned curry pot. It was generally accepted that the Sn, Sb, and 

Bi were trace impurities and thus were possible to be detected only by the SR-XRF method. 

However when I compared SR-XRF and ICP-AES results, the concentration of Sn, and Sb were 20 

ppm levels, and Bi 50 ppm level. Additionally ICP-AES could detect Ca, Fe, Zn, Se, and Pb. Ca 

(>10000 ppm) was not detected by SR-XRF; Fe (30 ppm) and Zn (200 ppm) were too weak in SR- 

XRF spectra; Se (100 ppm) was overlapped by major element As (74 wt%) in XRF; Pb (200 ppm) 

was high blank intensity because of the shielding material of the synchrotron beamline. SR-XRF 

found Mo as a key element of murder (ICP-AES did not analyse Mo), and thus finally the 

saleswoman was sentenced to death due to the SR-XRF analysis. However, if I include Fe, Zn, and 

Ba for identification, the saleswoman’s arsenic was significantly different from that found in the 

paper cup. The saleswoman is now in the death row and this issue is now discussed in Japanese 

journalism. 

-134 -



(L52) 

SPECTROSCOPIC ANALYSIS OF BONES FOR FORENSIC STUDIES 

A. D’Ulivo 1 , L. Pardini 2 , M. Borrini 3 , L. Marchesini 3 , M. Tofanelli 1 , F. Bartoli 4 , 

E. Pitzalis 1 , M.C. Mascherpa 1 , S. Legnaioli 1 , G. Lorenzetti 1 , G.H. Cavalcanti 5 and V.Palleschi 1 

1 

Institute of Chemistry of Organometallic Compounds, CNR 

Area della Ricerca del CNR di Pisa 

Via G. Moruzzi, 1 – 56124 PISA (Italy) 

2 

Institut für Physik und IRIS Adlershof 

Humboldt-Universität zu Berlin 

Zum Großen Windkanal 6, 12489 Berlin (Germany) 

3 

Italian Accademy of Forensic Sciences 

Viale Regina Margherita 9/D - 42124 REGGIO EMILIA (Italy) 

4 

Department of Biology 

Via A. Volta, 4 - 56126 PISA (Italy) 

5 


Av. Gal. Milton Tavares de Souza, s/nº 

Campus da Praia Vermelha - CEP 24210-346 - Niterói – RIO DE JANEIRO (Brazil) 


The elemental analysis of human bones can give information about the dietary habits of the 

deceased, especially in the last years of their lives, which can be useful for forensic studies. The 

most important requirement that must be satisfied for this kind of analysis is that the concentrations 

of analyzed elements is the same as ante mortem. In this work, a set of bones was analyzed using 

Laser-Induced Breakdown Spectroscopy (LIBS) and validated using Inductively Coupled Plasma – 

Optical Emission Spectroscopy (ICP-OES), in order to compare those two techniques and to 

investigate the effect of possible alterations in the elemental concentrations' proportion resulting 

from the treatment usually applied for preparing the bones for traditional forensic analysis. The 

possibility that elemental concentrations’ changes would occur after accidental or intentional 

burning of the bones was also studied. 

-135 -



(L53) 

PRINTABLE SURFACE ENHANCED RAMAN SCATTERING STRIPS WITH IN-SITU 

GROWTH OF GOLD NANOPARTICLES 

Wei Ju, Liao and Surojit Chattopadhyay* 

Institute of Biophotonics, National Yang-Ming University, Taiwan (ROC) 

* Corresponding author: e-mail: sur@ym.edu.tw 

Surface enhanced Raman scattering (SERS) is being developed to challenge existing conventional 

technologies used for biomolecular sensing. SERS strips are printed on paper with in-situ growth of 

gold nanoparticles (AuNPs) on printed patterns. Plasmons generated in these AuNPs when irradiated 

with suitable light increase the scattering cross-section for Raman spectroscopy of selected analytes. 

Components of human sweat were used as a bio-ink to reduce HAuCl 4 forming the AuNPs on paper. 

These AuNPs on the strip’s surface enhances the local electric field to increase the Raman signal. 

SERS strips are capable of absorbing analyte molecules readily and firmly. Development of this 

inexpensive SERS strips for detection of toxic chemical will be important for health applications. 

We demonstrate detection of Rhodamine 6G, a standard Raman analyte, at μM levels, on these strips 

to show its efficacy in sensor applications. 

Figure 1. (A) UV-Vis absorption spectrum on the AuNP printed pattern (Black) and bare paper 

(RED) showing the surface plasmon absorption of AuNPs at 530 nm only for the black curve. Inset 

shows a camera image of the SERS strip with printed patterns of AuNPs (purple). (B) Raman 

spectra of R6G (M) on the AuNP pattern (black) and bare paper (Red), showing strong signals 

originating from the AuNP patterns. 

-136 -



(L54) 

SPECIATION AND COBALT TOXICITY ON HUMAN LUNG CELLS: AN 

INTERDISCIPLINARY STUDY 

Carole Bresson, 1 Carine Darolles, 2 Asuncion Carmona, 3, 4 Céline Gautier, 5 Nicole Sage, 2 

Stéphane Roudeau, 3, 4 Richard Ortega, 3, 4 Eric Ansoborlo, 6 Véronique Malard. 2 

1 

CEA, DEN, DPC, SEARS, Laboratoire de développement Analytique Nucléaire, Isotopique et Elémentaire, F-91191 

Gif-sur-Yvette, France. 

2 

CEA, DSV, IBEB, Lab Biochim System Perturb, Bagnols-sur-Cèze, F-30207, France. 

3 Univ. Bordeaux, CENBG, UMR 5797, F-33170 Gradignan, France. 

4 CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan, France. 

5 

CEA, DEN, DPC, SEARS, Laboratoire d’Analyse en Soutien aux Exploitants, F-91191 Gif-sur-Yvette, France. 

6 

CEA, DEN, DRCP, CETAMA, Marcoule F-30207, Bagnols-sur-Cèze, France. 

e-mail: carole.bresson@cea.fr 

Understanding the toxicity mechanisms of radionuclides towards living organisms in case of 

contamination is crucial, in order to develop strategies for prevention, diagnosis and design efficient 

and selective decorporants. Cobalt is used in industrial and nuclear sectors and occupational risks of 

exposure, particularly by inhalation, are known. In this framework, we investigated the impact of a 

soluble cobalt compound, CoCl 2 .6H 2 O, on the BEAS-2B lung epithelial cell line, as well as its 

impact on metal homeostasis. Cobalt speciation study in various culture media was performed by 

modeling and experimentally, highlighting the influence of the culture medium composition on the 

precipitation level of cobalt. The cytotoxic effects of cobalt on the cells were also assessed. Upon in 

vitro exposure of BEAS-2B cells to cobalt, intracellular accumulation of cobalt and zinc was shown 

using in situ microchemical analysis based on ion micro-beam techniques and analysis after cell 

lysis by inductively coupled plasma mass spectrometry (ICP-MS). Microchemical imaging revealed 

that cobalt was rather homogeneously distributed in the nucleus and in the cytoplasm whereas zinc 

was more abundant in the nucleus. Combined in vitro exposure of the cells to zinc and cobalt 

induced a clear synergistic increase in toxicity and a substantial increase in intracellular zinc 

amount. A decrease in ZnT1 expression, involved in zinc efflux, seems to be the origin of this 

significant increase. This work highlights the considerable contribution of analytical techniques to 

the understanding of complex toxicity mechanisms at the cellular and molecular level. 

-137 -



(L55) 

FAST AND NON-DESTRUCTIVE QUANTIFICATION OF DAPIVIRINE IN HIV 

PREVENTIVE INTRAVAGINAL RINGS BY RAMAN SPECTROSCOPY 

Lotte B. Lyndgaard 1) , Rolf Spångenberg 2) , Ann-Charlotte Jägervall 2) Christopher Gilmour 3) and 

Frans van den Berg 1) 

1 Department of Food Science, Faculty of Science, University of Copenhagen, DK-1958 

Frederiksberg, Denmark 

2 Qpharma, Malmø, Sweden 

3 International Partnership for Microbicides (IPM), Silver Spring, MD, USA 

e-mail: lottebs@life.ku.dk 

An intravaginal ring (IVR) is a polymeric delivery device designed to provide controlled release of 

drugs to the vagina over an extended period of time. The international partnership for microbicides 

(IPM) is investigating the use of the active pharmaceutical ingredient (API) Dapivirine in a silicone 

matrix vaginal ring delivery system, with the potential to reduce female vaginal HIV infection rates. 

Several phase I and II studies have proved the ring as a safe viable drug method. The ring is intended 

as a 28 day use device for women as a complementary prevention technology to safer sex practices. 

The ring formulation will be used continuously by HIV-uninfected women for the prevention of 

male to female vaginal transmission of HIV-1 infection. 

The objective of the study was to test Raman spectroscopy as a fast alternative to the current 

standard reference method (High-performance liquid chromatography) for quantifying Dapivirine in 

IVRs. By Raman spectroscopy IVRs can be measured directly, without any tedious and time 

consuming sample preparation, and non-destructively. The Raman signal of Dapivirine is strong, but 

the silicone-based polymer matrix also has a high signal which interferes with the quantification. 

Measurements on rotating rings using a wide area illumination probe with a spot size of 6 mm 

allowed that almost the entire ring were sampled. Both reference rings containing 50-150% of the 

nominal concentrations of Dapivirine and rings from six different production batches were 

evaluated. Raman spectra were baseline corrected using asymmetric least squares smoothing. 

We demonstrate how a calibration model for Dapivirine concentration can be conducted and used 

for the prediction of concentrations in rings collected from the production. The task turned out to not 

be a straight forward partial least squares (PLS) regression on the Raman signals, predominantly 

due to batch-to-batch variations in the silicone sample matrix. Different data analytical approaches 

proved to be more of less effective and will be discussed: spectroscopic knowledge based 

quantification using the ratios of selected band heights, band fitting using Cauchy-Lorentz functions, 

interval based normalization, orthogonalization according to silicone elastomer and estimation of 

interference using multivariate curve resolution (MCR). 

-138 -



(L56) 

TITANIUM MEASUREMENT IN BIOFLUIDS BY ICP-OES (SIMULTANEOUS 

INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION) AND HE-CC KED 

QUADRUPOLE ICP-MS 

Balázs Berlinger 2 , Dr. Lee Blum 1 , Nathaniel Rieders 1 and János Fucskó 1 

1 NMS Labs, 3701 Welsh Road, Willow Grove, PA 19090 

2 National Institute of Occupational Health, Gydas vei 8., N-0363 Oslo, Norway 


Titanium measurement in biofluids by ICP-MS – the preferred way for trace metal analysis in 

biological matrices - involves multiple challenges: interferences from polyatomic species like PO + , 

SO + ClC + , direct isobaric overlap of 48 Ca with the major isotope of 48 Ti, and typically very low 

concentration of Ti in urine, serum and blood. While titanium is not known to be particularly toxic, 

quantification at concentrations of < 20 ng/mL is desirable. These challenges have been 

acknowledged by many clinical laboratories during the last decade, and sector field ICP-MS 

appeared to be the most accurate way to measure Ti below the 2 ng/mL typical levels in bio-fluids. 

Experiment 

A He-CC KED quadrupole ICP-MS method on Agilent 7700 ICP-MS and a simultaneous ICP-OES 

method on Thermo iCAP6500Duo ICP-OES were developed to measure and confirm Ti levels in 

urine, serum and blood at > 2 ng/mL concentrations. Multiple internal standards – Sc, Ga, Y, Rh, In, 

Zr - were evaluated and compared. 

While good tuning conditions would suppress polyatomic interference from S and below the 1 

ng/mL Ti BEC level in urine, serum and blood samples, an interference correction method for PO + 

and SO + interferences using S and P calibration with the He-CC KED ICP-MS and subsequent 

measurement of P and S in biofluids was developed and used to obtain more accurate data. The 

interference correction provided good spike recovery down to and below 10 ng/mL Ti 

concentrations. The urine, serum and blood blank and spike levels measured by He-KED ICP-MS 

and simultaneous ICP-OES were also compared to sector field ICP-MS data, at the National Institute 

of Occupational Health in Norway, for more accurate quantitative determination of interferences of 

major components, like P, S, Cl, C, Li, Be, alkali and alkaline earth metals. 

Summary 

Both the He-KED-quadrupole ICP-MS method and the simultaneous ICP-OES method are adequate 

for measurement of >5-10 ng/mL Ti concentration in biofluids. Thus, a higher cost sector field ICP- 

MS instrument may not be needed for routine analysis if appropriate interference correction is used 

for the quadrupole ICP-MS method. The ICP-OES method is particularly promising for urine 

measurement, due to the higher available sample volume, lower dilution ratio required and the lack 

of polyatomic interferences causing elevated BEC by ICP-MS. 

-139 -



(L57) 

DISTRIBUTION AND SOURCE OF METALS IN CONTAMINATED SEDIMENTS FROM 

RIVERS IN COAL FIELDS 

Rob McCrindle 1 , Stanley Moyo 1 , Ntebogeng Mokgalaka 1 and Jan G Myburgh 2 

1 Department of Chemistry, Tshwane University of Technology, Pvt. Bag X680, Pretoria 0001, 

Republic of South Africa. 

2 

Department of Paraclinical Sciences, Faculty of Veterinary Science, University of Pretoria, P Bag 

X04, Onderstepoort, 0110, South Africa 

E-mail: mccrindleri@ tut.ac.za 

A sequential extraction procedure was applied to identify the species of Cd, Co, Cr, Pb, Ti, V and 

Fe-Mn-oxides present in sediments from the Olifants, Klein Olifants and Wilge Rivers, South 

Africa. The three rivers pass through the most active coal fields in the country. A four step 

sequential extraction procedure partitioned the metals into CH 3 COOH exchangeable/extractable; 

NH 2 OH HCI carbonate extractable and easily reducible; H 2 O 2 -HNO 3 organic extractable/oxidisable 

and HF, HNO 3 residual/acid soluble. Most of the elements were found to exist in the residual 

fraction, characterized by stable compounds in the sediments. The non-residual fractions, total of the 

first three fractions, were analyzed since they are more bioavailable than the residual amount. 

Correlation analysis and two multivariate analysis techniques (factor and cluster analysis) were 

applied to understand the associations between the non-residual phase of the trace metals and Fe-and 

Mn-oxides within the sediments, since Fe-and Mn-oxides play a critical role in the adsorption of 

trace metals within aquatic environment. 

-140 -



(L58) 

INTERPRETATION OF THE PLASTIC LIFE CYCLE USING FTIR-ATR AND ICP-OES 

SPECTROMETRY 

Van Oyen, Albert 1 and Oppermann, Uwe 2 

1 CARAT GmbH, Harderhook, D-46395 Bocholt, Germany 

2 Shimadzu Europa GmbH, Albert- Hahn- Str. 6-10, D-47269 Duisburg, Germany 

e-mail: Albert.van.oyen@carat-lab.com 

The worldwide production of plastics in 2008 was 245 million tons and has reached an all-time high 

[1]. It is estimated that in the European Union (incl. 27 member states) around 25 Mt of plastic waste 

was generated in 2008; 12.1 Mt (48.7%) was landfilled while 12.8 Mt (51.3%) went to recovery [2], 

and only 5.3 Mt (21.3%) was recycled [3]. 

On the waste management side, collection and sorting of waste from electric and electronic 

equipment (WEEE) and plastics provide the greatest job opportunities, with a total of 40 and 15.6 

jobs respectively being created per 1 000 tons of material processed. Plastic recycling alone has the 

potential to create 162 018 jobs in the EU if the recycling rate increases up to a level of 70% by 

2020 [4]. 

Plastic is mostly used in packaging as a low-cost one-way product that is most often not reusable or 

not foreseen for reuse. The plastics converting market is dominated by plastic packaging (40.1%) 

followed by the building and construction sector (20.4%). The plastics industry expects a long-term 

growth of around 4% globally, well ahead of expected global GDP growth [5]. Europe is still a net 

exporter of plastic products with a value of 13 billion Euro in 2009, but Chinese production has 

reached similar levels since 2008 [6]. 

There are hundreds different kinds of plastic [7]. Most of these plastics aren’t mixable, this means 

that the plastic varieties have to be separated before the recycling process cab start. Furthermore the 

additives are playing an important role in the quality of the recyclates, especially the presence of 

heavy metals and flame retardants. 

Another problem is degradation. Plastics are not inert but degrade under influence of UV-radiation, 

heat and other external influences. From a thermodynamic point of view plastics are meta-stable, 

which means that after extra energy exposure (e.g. heat), the plastic will degrade in unknown rest 

products. 

FTIR spectrometry is a useful tool for determination and identification the kind of plastic. 

Experimental work has been done using the Shimadzu IRPrestige-21 FTIR spectrometer in 

combination with commercial libraries, which are available on the market, containing usually the 

spectra of most used plastics. For identifying the kind of plastic from pre-consumer waste this 

method is quick and accurate. 

Identifying post-consumer plastic is more difficult because the plastic could have several signs of 

degradation. This becomes visible only by some extra peaks in the spectrum. Furthermore the heavy 

metal concentration in plastics is of interest, as it is nowadays restricted by RoHS and the European 

packaging directive. This requires precise analytical systems such as X-ray fluorescence, ICP-OES-, 

and atomic absorption spectrometers. For the quantitative determination of hazardous substances 

such as cadmium and lead the EDX-720P energy dispersive x-ray fluorescence spectrometer and 

-141 -



ICPE-9000 simultaneous ICP-OES spectrometer have been used. 

Experimental data for post consumer recyclate samples will be presented – advantages and 

limitations will be discussed. 

References 

[1] BIOIS, Plastic waste in the environment, Final Report EU Commission 2010 

http://ec.europa.eu/environment/waste/studies/pdf/plastics.pdf 

[2] Member State's statistics do generally only report on plastic packaging. The actual amount of 

plastic waste can be assumed to be higher. See: FORWAST, 2010, Policy recommendations, p. 43. 

(http://forwast.brgm.fr/Documents/Deliverables/Forwast_D63.pdf). 

[3] (BIOIS) Plastic waste in the Environment, loc. cit., p. 73. 

[4] Friends of the Earth, Report of September 2010, more jobs, less waste, p. 16, p. 31 

[5] Plastic Europe, plastics – the facts, 2012 p.5. 

[6] Plastic Europe, plastics – the facts, 2012 p.12. 

[7] Wikipedia: plastics http://en.wikipedia.org/wiki/Plastic 

-142 -



(L59) 

ADVANCED TECHNIQUES FOR ENVIRONMENTAL ANALYSIS USING ICP-MS 

Jianfeng Cui, Daniel Kutscher, Shona McSheehy Ducos, Lothar Rottmann, Tomoko Vincent, Julian 

Wills 

Thermo Scientific, Bremen, Germany 

e-mail: shona.mcsheehy@thermofisher.com 

Environmental monitoring has become a key strategy in determining how industrial activities and 

pollution affect our water supplies and ecosystems. Policies for example, such as the Water 

Framework Directive and Cleaner Air for Europe (CAFÉ) provide the framework for standards and 

objectives for pollutants that can damage health and the environment. Additionally, research 

activities investigate other activities or analytes that could have detrimental effects. Analytically 

meeting the requirements in legislation and research can be challenging due to sampling, sample 

handling, matrix effects and the ever decreasing levels of analytes that need to be measured. 

ICP-MS is a highly sensitive, accurate and rapid technique that efficiently meets the demands of 

environmental analysis. This paper outlines some approaches for ICP-MS analysis that offer 

flexibility for the analysis of challenging samples and environmental compartments. Trace elemental 

speciation is a growing field that offers information about the chemical forms of analytes in the 

environment and thus information on pathways and cycling of elements. The IC-ICP-MS approach 

presented for speciation is based on a completely metal free flow path that enables contamination 

free speciation in natural waters, fauna and flora. For handling of high matrix samples, an 

autodilution system is presented that enables prescriptive and intelligent dilution of samples as well 

as on-line preparation of calibration standards. Challenges in air monitoring are overcome using a 

Gas Exchange Device (GED). The GED substitutes atmospheric gases from air samples with argon 

for direct introduction of particulate matter in the air or direct analysis of toxic gases in air after an 

on-line chemical reaction. 

-143 -



(L60) 

QUANTITATIVE ANALYSIS OF HEAVY ELEMENTS AND SEMI-QUANTITATIVE 

EVALUATION OF HEAVY MINERAL COMPOSITIONS OF STREAM SEDIMENTS IN 

JAPAN FOR CONSTRUCTION OF A FORENSIC SOIL DATABASE USING 

SYNCHROTRON RADIATION X-RAY ANALYSES 

Izumi Nakai 1 , Shunsuke Furuya 1 ,Willy Shun Kai Bong 1 , Yoshinari Abe 1 , Keiichi Osaka 2 , Takuya 

Matsumoto 2 , Masayoshi Itou 2 , Atsuyuki Ohta 3 , and Toshio Ninomiya 2 

a. Department of Applied Chemistry, Tokyo University of Science, Shinjuku,Tokyo 162-8601 

b. Japan Synchrotron Radiation Research Institute(JASRI), SPring-8,Kouto,Hyo-go 679-5198 

c. Institute of Geology and Geoinformation, National Institute of Advanced Industrial Science and 

Technology (AIST), Higashi, Tsukuba, Ibaraki 305-8567, Japan 

e-mail: inakai@rs.kagu.tus.ac.jp 

Soil materials are routinely encountered in a crime scene and used as evidence by police and 

forensic staff, and thus the forensic analysis of soils has a long history. However, characterization of 

soil materials requires high level of training and expertise. We have therefore started to construct a 

nationwide forensic soil sediment database for Japan, which can be used by non-expert forensic 

staff. The database is based on the heavy mineral and trace heavy element compositions of stream 

sediments collected at 3,024 points across Japan. 

Heavy element compositions of the samples were determined by high-energy synchrotron X-ray 

fluorescence analysis (HE-SR-XRF) utilising 116keV X-rays from Wiggler source (Fig.1). Heavy 

mineral compositions were determined by high-resolution synchrotron X-ray powder diffraction 

(SR-XRD) utilizing a Deby-Scherrer camera with a radius of 286.5mm (Fig. 2). After optimization 

of the measurement conditions, the measurements were carried out at SPring-8, JASRI in Japan. The 

automated sampling systems allow the measurements of 130 powder diffraction patterns and 100 

XRF spectra per day using sediment samples of 2 milligrams, which enabled us to construct a 

database of a large number of samples. 

The concentrations of heavy elements such as rare earth elements, Cs, and W from 1 ppm to 

500 ppm levels in a soil sediment can be determined by the calibration curve method using HE-SR- 

XRF. A heavy element concentration map superimposed on a geographical map of Japan was 

successfully prepared from these analytical data. The powder diffraction data were recorded on IP. 

The heavy mineral compositions were quantitatively evaluated using the peak intensity of 

characteristic X-ray diffraction peaks of the component minerals. The obtained data have been 

expressed by heavy mineral map. This study demonstrates that XRF and XRD data collected from 

the sediments of Shizuoka Prefecture closely reflect the geological and geographical signature of the 

sediment samples, which can be used for the provenance determination of soil evidence from a 

crime scene. This will 

become the first forensic 

database constructed by SR 

X-ray analyses. 

Fig.1 HE-SR-XRF system at BL08W 

Fig.2 SR-XRD system at BL19B2 

-144 -



(L61) 

EFFECT OF METAL STRESS ON PIGMENTS IN COPPER-HYPERACCUMULATING 

LICHENS 

Hiromitsu Nakajima and Kiminori Itoh 

Graduate School of Environment and Information Sciences, Yokohama National University, 

Tokiwadai 79-7, Hodogayaku, Yokohama 240-8501, Japan 

e-mail: h-nakaji@ynu.ac.jp 

To understand the ecology and physiology of metal-accumulating lichens growing in Cu-polluted 

sites, we investigated lichens near temple and shrine buildings with Cu roofs in Japan and found that 

Stereocaulon japonicum (Fig. 1) and Cladonia humilis (Fig. 2) grow in Cu-polluted sites. Metal 

concentrations in the lichen samples collected at some of these sites were determined by inductively 

coupled plasma mass spectroscopy (ICP-MS). UV-vis absorption spectra of pigments extracted from 

the lichen samples were measured, and the pigment concentrations were estimated from the spectral 

data using equations from the literature. We found that S. japonicum and C. humilis are Cuhyperaccumulating 

lichens. Differences in pigment concentrations and their absorption spectra were 

observed between the Cu-polluted and control samples of the 2 lichens. However, no correlation was 

found between Cu and pigment concentrations. We observed a positive correlation between Al and 

Fe concentrations and unexpectedly found high negative correlations between Al and pigment 

concentrations. This suggests that Al stress reduces pigment concentrations. 

Fig. 1. Stereocaulon japonicum on rockwall. 

Fig. 2. Cladonia humilis on soil. 

-145 -



(L62) 

HIGH SENSITIVITY AND EXTENDED SCAN SPEED FOR DEDICATED ISOTOPE 

RATIO DETERMINATIONS 

René Chemnitzer 1 and Meike Hamester 1 

1 Bruker Daltonics, Fahrenheitstrasse 4, 28359 Bremen, Germany 

e-mail: Rene.Chemnitzer@bruker.com 

Scientific disciplines like Food Chemistry, Geochemistry, environmental sciences and Paleontology 

are not only interested in the total concentration of an element but also in the isotope ratio of either 

two or more isotopes of the same element or isotopes of different elements. Researchers are 

interested in isotope ratios of elements such as Selenium, Strontium/Rubidium, Lead and Uranium. 

ICP-MS is a powerful technique for the determination of trace elements in various matrices. Beyond 

that ICP-MS is able to determine isotope ratios with high accuracy and precision. The sensitivity of 

an ICP-MS is an indispensable performance characteristic and will enable the instrument to achieve 

highest isotope ratio precisions even at low, down to single digit ppt levels. On the other hand high 

sensitivity is important for single collector instrumentation to enable short integration times without 

sacrificing precision due to counting statistical limitations. 

An additional challenge is the isotope ratio measurement of spectrally interfered isotopes. Effective 

interference management with high sensitivity in interference mode is required to ensure precision 

and accuracy of spectrally interfered isotope ratios. 

The presentation will illustrate the layout of a high sensitive ICP-MS instrumentation (Bruker 

Daltonics). With a 90° reflecting ion optic and an optimized ion extraction the instrument is capable 

to obtain sensitivities of > 10 6 cps/ppb - without plasma shielding, and > 10 5 cps/ppb in collision 

mode for spectrally interfered isotopes. The key parameters to improve the precision for isotope 

ratio analysis with ICP-QMS are discussed. Geochemical applications using Laserablation-ICP-MS 

as well as the isotope ratio analysis of liquid samples will be presented. 

-146 -



(L63) 

DETERMINATION OF HEAVY METALS AT ULTRALOW CONCENTRATION LEVELS 

IN PRISTINE POLAR SNOW AND ICE 

Claude F. BOUTRON 

Honoray Professor at University Joseph Fourier of Grenoble ( Laboratory of Glaciology and 

Geophysics of the Environment ) , 13 rue Messidor , 05000 Gap , France . 

E-mail : claudeboutron@orange.fr 

Dated snow and ice layers deposited in Antarctica and Greenland are unique archives of the 

changing occurrence of heavy metals in the atmosphere . Ancient ice allows to assess past natural 

levels of these metals and their changes during the successive glacial - interglacial periods . More 

recent ice and snow allow to evaluate man - induced changes during the Greek-Roman Antiquity 

and from the Industrial Revolution to present . Deciphering these frozen archives is unfortunately 

extremely difficult especially because of the extreme purity of polar snow and ice . As an illustration 

, Pb concentration in Antarctic ice dated 130 000 years ago is about 0.4 picogram per gram , while 

Ir concentration in Greenland ice dated 5000 years ago is about 0.3 femtogram per gram . Such 

extremely low concentrations make it mandatory to carefully control contamination problems from 

field sampling to laboratory analysis , and use highly sensitive analytical techniques . 

Surface and shallow depth samples can be collected cleanly from the walls of snow pits hand dug by 

operators wearing clean room clothing far away from local contamination sources such as scientific 

stations , using sampling tools extensively cleaned with ultrapure water and acids . Deep ice ( depths 

up to several kilometers ) can only be obtained as ice cores whose outside is heavily contaminated 

during drilling operations , especially because of the use of wall-retaining fluids which are necessary 

to counterbalance the enormous pressure encountered at great depths . The core sections must then 

be decontaminated by chiselling successive veneer layers of ice from the contaminated outside to the 

pristine inner part of the core . The efficiency of the decontamination procedure has to be assessed 

by determining changes in concentrations from the outside to the center of each core section . A 

clear plateau of concentrations in the central part of the core section will indicate that concentrations 

measured in the center of the core do represent the original concentrations in the ice . 

Special clean laboratories flushed with air filtered through high efficiency particle air filters have to 

be used for the analysis of these very valuable samples . Ultrapure water and acids are required , 

together with the use of sophisticated cleaning procedures . It is also essential to perform extensive 

blank determinations in order to accurately determine the amount of each heavy metal added to the 

samples during each successive step of the analytical procedure , especially by processing artificial 

ice cores made by freezing ultrapure water whose composition is known beforehand . 

The analytical techniques used for the determination of heavy metals in these very valuable samples 

include Isotope Dilution with Thermal Ionization Mass spectrometry ( IDMS ) , Laser Excited 

Atomic Fluorescence Spectrometry ( LEAFS ) and Inductively Coupled Plasma Sector Field Mass 

Spectrometry ( ICP - SFMS ) . 

As an illustration , some examples of the data obtained so far will be presented . Especially , Pb and 

Pb isotopes data obtained for Greenland ice dated from the Greek-Roman Antiquity , which show 

evidence of an early large scale pollution of the atmosphere of the Northern Hemisphere 2000 years 

ago at the time of the flourishing of the Roman Republic and Empire . Also , past natural changes of 

various heavy metals in Antarctic ice during the past 600 000 years , with pronounced natural 

variations during the successive interglacial and glacial periods . 

-147 -



(L64) 

CHARACTERIZATION OF DECOMPOSITION PRODUCTS IN ENERGY STORAGE 

MATERIALS BY CHROMATOGRAPHIC METHODS 

Sascha Nowak*, Lydia Terborg and Martin Winter 

* (sascha.nowak@uni-muenster.de) 


The electrolyte system in lithium ion batteries consists of organic carbonates and a conducting salt. 

For most commercial available batteries lithium hexafluorophosphate (LiPF 6 ) is established as the 

conducting salt. Based on the high hygroscopicity of LiPF 6 , such systems are always contaminated 

with a certain amount of water that causes decomposition of the conducting salt to LiF and PF 5 , 

which subsequently may release hydrofluoric acid (HF). The decomposition products, especially HF 

and PF 5 , have a negative influence on the performance of the lithium ion batteries, such as the 

deterioration of the SEI and can further act as catalysts for the decomposition of the electrolyte. Due 

to the fact, that the reaction mechanism of the hydrolysis of LiPF 6 in the system is still not fully 

understood, this work focuses on the decomposition of the conducting salt and additionally its 

interaction with the organic carbonates. 

Therefore, the decomposition products were analyzed by ion chromatography coupled with 

inductively coupled plasma optical emission spectrometry (IC/ICP-OES) and verified by ion 

chromatography coupled with electrospray ionisation mass spectrometry (IC/ESI-MS). Furthermore, 

the interaction of the decomposition products of the conducting salt with the organic carbonates was 

investigated by means of GC-MS and Headspace-GC-MS. 

-148 -



(L65) 

LOCK-IN THERMOGRAPHY – A NOVEL IN-SITU MEASURMENT METHODE TO 

SUPPORT SURFACE SPECTROSCOPY FOR LITHIUM-ION CELLS 

Mathias Reichert, Christian Wendt, Chrisitan Herkt-Bruns, Falko Schappacher, Stefano Passerini 

and Martin Winter 

University of Muenster, MEET Battery Research Centre, Corrensstraße 46, 48149 Muenster, 

Germany 

e-mail: mathias.reichert@uni-muenster.de 

Surface spectroscopy methods and imaging techniques like SEM, EDX, XPS and Raman are 

important tools to investigate aging and failure mechanism in lithium-ion cells. Usually the cell is 

dismantled in a contamination free environment and samples were taken from the electrolyte, the 

electrodes and the separator. This proceeding is called “post-mortem analysis”. One drawback of 

this procedure is the decisions were to take the sample, because in most cases it is not possible to 

spot interesting areas by optical survey, so samples were taken randomly or by a fix pattern. 

To identify areas of interest for the post-mortem analysis of lithium-ion cells we are introducing the 

highly sensitive Lock-In (IR-) Thermography as a new non-destructive and non-contacting (in-situ) 

measurement method. This method is already known and used in the semiconductor technology to 

detect failures, like short circuits and oxide-pinholes in integrated circuits. 

Fig. 1: Left: Adapted Lock-In Thermography measurement setup. 

Right: Detailed amplitude picture with the active part marked as (A) and the inactive 

electrode site marked as (B). Electrode size: 5 x 5 cm. 

The principle of lock-in thermography consists of introducing periodically modulated current into an 

object and monitoring only the periodic surface temperature modulation phase-referred to the 

modulated heat supply. The information of each pixel of the IR image is processed as if it were fed 

into a lock-in amplifier. 

Measurement Setup – We adapted and optimized this method for the use in lithium-ion 

battery research. Our measurement setup is described in Fig. 1. The measurements were carried out 

with an InSb IR camera. 

The sample was a standard pouch cell design with a lithium-nickel-manganese-cobalt-dioxide 

(NMC) / cathode and a graphite anode in a full cell arrangement. The pouch cell surface was 

blackened with beamless graphite paint (Graphit 33 from Kontakt Chemie). 

The lock-in measurement was carried out with an electric excitation frequency of 1 Hz between 

4.2 V and 2.8 V; 300 single experiments were carried out during a five minute measurement time. 

-149 -



Fig. 2: Left: 3D-SEM picture taken from a sample from inactive area (B) of the separator 

between anode and cathode. 

Centre: SEM picture taken from a sample from active area (A) of the graphite 

anode. 

Right: SEM picture taken from a sample from inactive area (B) of the graphite 

anode. 

Results – The received amplitude image from the lock-in thermography measurement is 

shown in (Fig. 1 / Left). The amplitude image correlate with the temperature change in the cell, were 

the bright spots represent the highest temperature rise (max. 1.2 mK) and the dark blue areas no 

temperature increase. 

The inhomogeneity of the temperature distribution in the active material is clearly visible in the 

amplitude picture (Fig. 2 / Centre). In the middle of the squared electrode an area with no heat 

production and therefore also electrochemical inactive is detected. Samples are taken from the active 

(A) and inactive (B) areas from the electrodes. 

The samples were analyzed with a scanning electron microscope (SEM). The thermal active site 

(Fig. 2 / Centre) of the anode has normal graphite composite electrode morphology, were the 

inactive part (Fig. 2 / Right) is covered with a dense and thick surface film. Parts of this film are 

found on the anode facing side of the separator, as shown in the 3D-SEM picture (Fig. 2 / Left). 

This heavy coating can lead to a very high charge-transfer resistance, which can explain the 

inactivity of area B, as shown in the thermal amplitude picture (Fig. 1 / Left). 

Conclusion – The lock-in thermography as a novel in-situ measurement method for lithium-ion cells 

is a good addition to existing analyse methods, by detecting the areas of interest for the sample 

preparation for various surface spectroscopy methods. It is also a promising tool to investigate the 

local conductivity, electrolyte wetting, electrode quality and aging / abuse mechanism. 

-150 -



(L66) 

CHARACTERIZATION OF THE DECOMPOSITION PRODUCTS OF A UTILIZED 

BATTERY ELECTROLYTE FROM A COMMERCIAL AVAILABLE HYBRID VEHICLE 

WITH PURPOSEFUL ANALYTICAL METHODS 

Martin Grützke, Vadim Kraft, Britta Vortmann, Björn Hoffmann, Martin Winter and Sascha Nowak 

University of Münster, MEET - Battery Research Centre, Corrensstr. 46, 48149 Germany 

Email: martin.gruetzke@uni-muenster.de, sascha.nowak@uni-muenster.de 

In consideration of the global warming and delimited fossil fuels, alternative sources of energy and 

new techniques for mobility are required. One possibility are regenerative energies like wind, water 

and solar energy. However all this technologies have one main drawback: they are not constantly 

available. Therefore a temporary storage of the energy is necessary. Furthermore the mobility based 

on fossil fuels as we know it nowadays could be replaced by electric vehicles or at least reduced by 

hybrid vehicles fueled by electricity from regenerative energies. The lithium-ion battery is a 

promising energy storage device to implement this revolution because of its high energy density and 

high reversibility without a memory effect. 

Unfortunately also lithium-ion batteries have their disadvantages. The lifetime is limited due to 

internal decomposition reactions of the electrolyte solvent, the conducting salt, the active materials 

and other battery parts during the electrochemical cyclization. It is necessary to identify the 

decomposition products of the different battery parts and to clarify the interactions between them to 

understand how the cell works and why its lifetime is limited. Not till then it is possible to improve 

the battery performance and the lifetime. 

The investigations were focused on the ion conducting liquid, the electrolyte. Usually the electrolyte 

of commercial available lithium-ion batteries is a solution of different linear and cyclic organic 

carbonates like for example dimethyl carbonate and ethylene carbonate, the conducting salt LiPF 6 

and some additives. 

In this study the decomposition products of a utilized battery electrolyte solution from a commercial 

available hybrid vehicle were characterized. The whole battery pack was dismounted into single 

cells. We drilled up one cell and collected the electrolyte which showed a lightly yellow color. 

The organic carbonates and other volatile compounds were identified and quantified with GC and 

GC-MS. The electrolyte solution consists of (37.5 ± 2.1) % dimethyl carbonate, (27.5 ± 1.4) % ethyl 

methyl carbonate, (32.6 ± 0.6) % ethylene carbonate and (2.3 ± 1.0) % cyclohexyl benzene. 

Furthermore, the decomposition product PO(OMe) 3 could be detected with this method. 

The only cation found with IC (ion chromatography) was Li + in a concentration of (1.32 ± 0.02) 

- 

mol/L. PF 6 and its degradation and decomposition products were investigated with the anion 

column of the IC system and a coupled ESI-MS. Beside PF - 6 , F - and H 2 PO - 4 , a series of fluoro- and 

alkyl phosphates could be identified with MS/MS fragmentation experiments. 

To complete the squad of decomposition products, further investigations with coupled IC-ICP-OES 

and IC-ICP-MS systems were carried out. 

-151 -



(L67) 

ANALYSIS OF THE MANGANESE DISSOLUTION AND DEPOSITION IN 

LIMN 2 O 4 /LI 4 TI 5 O 12 BASED LITHIUM ION BATTERIES 

Markus Börner, Sebastian Klamor, Björn Hoffmann, Melanie Schroeder, Martin Winter, Falko 

Schappacher 


E-Mail: markus.boerner@uni-muenster.de 

Lithium ion batteries have been extensively investigated in the last decade due to the steadily 

increasing demands for the application in portable electric devices and the use in electric vehicles. 

Among the various cathode materials, LiMn 2 O 4 (LMO) is one of most promising candidates for the 

use in commercial lithium ion batteries. Apart from its high potential of 4 V vs. Li/Li + its benefits 

are the low costs and the environmental benignity compared to other cathode materials containing 

for example Cobalt and Nickel. However it suffers from capacity fading during cycling due to the 

dissolution of Manganese into the electrolyte. 

Several research groups investigated this fading mechanism and ascribed the dissolution of the 

active material to different effects. Therefore various theoretical and experimental approaches have 

been reported to clarify the dependence of the Manganese dissolution on the discharge/charge rate 

and the temperature. To overcome the issues of these complex theoretical models and experimental 

setups, the most suitable approach was found to be the use of a Li 4 Ti 5 O 12 (LTO) anode material. 

With its potential of 1.5 V vs. Li/Li + it does not feature the formation of a solid electrolyte interface 

(SEI) compared to carbonaceous anodes. Thus the Manganese dissolution was investigated by 

analyzing the deposition of the dissolved Manganese on the LTO anode. 

The dissolved Manganese ions migrate to the anode and do not form a surface layer but discrete 

particles as shown in Fig. 1. Scanning electron microscopy (SEM) and Energy-dispersive X-ray 

spectroscopy (EDX) revealed the particles to consist of Manganese and Oxygen. Further 

investigations were performed to determine the structure and composition of the Manganese oxide 

particles. Since single crystal XRD measurements did not yield a diffraction pattern, the particles 

seem to be either amorphous or show a short range order. The corresponding Raman spectrum 

features different bands that can be attributed to Manganese oxide vibration modes and besides 

clearly deviate from the LTO spectrum. Potential Manganese oxide compositions were analyzed by 

Raman spectroscopy to create a database of Raman spectra to determine the exact composition of 

the deposited Manganese oxide particles. 

EDX mappings of larger areas of the sample showed that Manganese oxide particles grow at several 

spots on the LTO anode. The comparison of the EDX mappings for samples cycled with different 

discharge/charge rates at 23°C, 35°C and 45°C suggest general tendencies concerning the quantity 

and size of the particles. Therefore Raman mappings were performed to examine the temperature 

dependence of the amount of deposited Manganese oxide particles. However, since SEM, EDX and 

Raman spectroscopy are very surface sensitive, the measurements do not give information about the 

actual amount of deposited Manganese oxide. Thus flat particles and tower-shaped particles with the 

same cross section would yield the same result. The analysis of the amount of deposited Manganese 

was accomplished by Laser Ablation measurements coupled with ICP-MS. These Laser Ablation 

mapping experiments clarified the discharge/charge rate dependence of the Manganese dissolution at 

the LMO cathode as well as the deposition behavior at the LTO anode. Moreover the different 

shapes of the Manganese oxide particles were confirmed by three-dimensional SEM images. 

-152 -



Fig. 1: SEM image of a Manganese oxide particle on a LTO anode. 

-153 -



(L67B) 

UV-PHOTOCHEMICAL VOLATILE SPECIES GENERATION EMPLOYED AS A 

DERIVATIZATION TECHNIQUE BETWEEN HPLC SEPARATION AND AAS 

DETECTION WITHIN SPECIATION ANALYSIS OF MERCURY(II), 

METHYLMERCURY(I), ETHYLMERCURY(I) AND PHENYLMERCURY(I) 

Vaclav Cerveny 1 , Ondrej Linhart 1 , Jan Kratzer 2 , Jakub Hranicek 1 and Petr Rychlovsky 1 

1 Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Albertov 6, 

CZ-12843 Prague 2, Czech Republic 

2 Institute of Analytical Chemistry of the AS CR, v.v.i., detached workplace - Department of Trace 

Element Analysis, Videnska 1083, CZ-14220 Prague 4, Czech Republic 

e-mail: vaclav.cerveny@natur.cuni.cz 

After some ecological accidents, increased mercury concentration can be found not only in water but 

also in living organisms, e.g. fishes. Consequently, toxic effects can be caused by drinking of 

contaminated water or by eating of poisoned food. The information about content of individual 

mercury species in a sample is important from the point of view of toxicity and can be obtained also 

by employing a connection of cheap and easy available analytical techniques as it will be explained 

in this contribution. 

HPLC on reverse phases on a GEMINI column was chosen for separation of inorganic mercury(II), 

methylmercury(I), ethylmercury(I) and phenylmercury(I). Separated mercury species needed to be 

transformed from a liquid phase in the effluent into gaseous phase in which atomic mercury 

absorption at 254 nm can be measured using atomic absorption spectrometer. A derivatization stepvolatile 

species generation was needed between these two common analytical techniques. 

Therefore, a derivatization unit was made in our laboratory by wrapping of Teflon tubing around a 

mercury fluorescent lamp without inner luminofor layer. This fluorescent lamp was fixed in a cheap 

kitchen light source. Additionally, other tubing materials like quartz tubing of various wall 

thicknesses with different transmittance at 254 nm were tested. Mercury volatile species generation 

(derivatization) occurs in this UV-photochemical generator in media of acetic acid solution. 

Comparable signals were obtained for all the four compounds selected for this study when gaseous 

hydrogen was added prior to the atomizer. This addition could be eliminated when using some other 

additives directly in the generation electrolyte. 

It was found that some additives like e.g., 2-mercaptoethanol and/or ethanol in the mobile phase 

caused positive effects like higher signal measured and better resolution of peaks obtained. On the 

other hand, some (mostly of) other substances tested caused signal depression or changes in 

individual species content ratio in a sample. 

Detection limits of proposed method for four selected species are between 25 and 50 ng/ml, 

quantification limits were found around 0.1 mg/ml and the linear dynamic range finished at 2 mg/ml 

for inorganic mercury (II) and 2.5 mg/ml for other species. 

Proposed method was tested also on real samples of two types: tap water with unknown mercury 

content and fish tissue which contained methylmercury without doubt and for which the total 

mercury content was determined by Advanced Mercury Analyzer AMA 254. Unfortunately, the 

extraction of mercury species from these samples was not carried out satisfactory because used 

extraction agents speeded up species degradation or decreased signals of standards too much when 

considering for routine use. Many of these tested insufficient extraction ways were assumed from 

literature. 

For sure, the total mercury content was determined very sensitively by AMA 254. Unfortunately, 

this device equipped with combustion cell, amalgamator and two absorption cells can not resolute 

between individual mercury species and it also does not allow measurements in real time. 

-154 -



Improving of the extraction step will be the aim of future studies. 

Acknowledgements: 

The authors thank for financial support to the Ministry of Education, Youth and Sports for project 

MSM 0021620857, to the Charles University in Prague (projects SVV267215 and UNCE 

204025/2012). 

-155 -



(L68) 

CHEMICAL VAPOR GENERATION FOR TRACE ANALYSIS. 

RECENT DEVELOPMENTS 

Alessandro D’Ulivo 1 , Massimo Onor 1 , Enea Pagliano 2 , Emanuela Pitzalis 1 , Emilia Bramanti 1 

1 C.N.R., Institute of Chemistry of Organometallic Compounds, U.O.S. of Pisa, 

Via G. Moruzzi, 1, 56124 Pisa, Italy. 

2 National Research Council Canada, Ottawa, Ontario K1A 0R9, Canada 

e-mail: dulivo@pi.iccom.cnr.it 

Chemical vapor generation (CVG) coupled with atomic and mass spectrometry is one of the most 

powerful analytical tools for determination and speciation of trace elements. The most popular 

applications are those concerning the determination of volatile hydrides and mercury but in the last 

few years its scope has been expanded to many other elements, such as Cu, Zn, Ag, Au, Ni and 

several transition and noble metals. This presentation will be focused on some recent developments 

concerning both fundamental and applicative aspects of CVG for trace analysis. 

The mechanisms of generation of volatile hydrides and volatile species by using aqueous NaBH 4 has 

reached a reasonable degree of rationalization, which is confirmed by recent experimental evidence 

which have been achieved on the CVG of arsane, methylarsane and dimethylarsane. 

Concerning with analytical applications, the scope of CVG has been expanded to determination of 

ultra trace amounts of simple inorganic anionic species such as chloride, bromide, iodide, cyanide, 

thiocyanide, sulfide, nitrite and nitrate, by gas chromatography mass spectrometry (GC-MS). In this 

case the derivatizing reaction is the aqueous phase alkylation with trialkyloxonium salts, R 3 O + [X] 

(R = Me, Et; X = BF 4 ), which converts the anionic species to their volatile, stable alkyl derivatives 

RX (X=Cl, Br, I, CN, SCN), R 2 S, RO-NO and RO-NO 2 . More recently, the use of Et 3 O + [FeCl 4 ] 

allowed the CVG of fluoride as a stable, volatile ethyl fluoride derivative, which can be determined 

by GC-MS at sub-micromolar level. 

Mechanistic aspect of CVG of anionic species, at trace level, by aqueous phase alkylation with R 3 O + 

salts has not been investigated, but their knowledge is important for the optimization of reaction 

conditions and for the control of interferences. The first approach is to identify all the possible 

reactions involved in the generation and in the liquid-vapor phase transfer of the volatile analytical 

derivative, RX. They can be classified as analytical reactions, competitive reactions and interfering 

reactions according to the scheme reported below. 

Analytical reactions 

R 3 O + + X RX(aq) + R 2 O (1) primary derivatization reaction 

RX(aq) ⇌ RX(g) (2) phase transfer of analytical derivative 

Competitive reactions 

R 3 O + + H 2 O ROH + R 2 O + H + (3) reagent hydrolysis 

X + H + ⇌ HX(aq) (4) protonation of analytical substrate 

HX(aq) ⇌ HX(g) (5) phase transfer of protonated analyte 

RX + R 3 O + R 2 X + + R 2 O (6) alkylation of analytical derivative 

Interfering reactions 

X + M n+ ⇌ MX (n-1)+ (7) metal complex formation 

R 3 O + + Y RY + R 2 O (8) alkylation of anionic species other than X 

R 3 O + + L RL + + R 2 O (9) alkylation of ligand/donor species 

-156 -



The optimization of experimental conditions should take into account the those experimental 

parameters which play a role in controlling all the possible reactions above mentioned. The first 

approach is to consider temperature, time, acidity and amount of reagent as the most critical 

parameters which play a major role in controlling the analytical reaction system. The choice of 

chemical additives (buffers, masking agents) represents a critical aspect of this derivatization 

procedure due to the reactivity of trialkyloxonium salts with other anionic species or ligand/donor 

species. 

-157 -



(L69) 

INFLUENCE OF SELENIUM SPECIES IN AQUACULTURE FEEDS ON THE SELENIUM 

STATUS OF FARMED RAINBOW TROUT FRY 

Simon Godin 1 , Stéphanie FONTAGNE-DICHARRY 2 , Maïté BUENO 1 , Philippe TACON 3 , Brice 

BOUYSSIERE 1 , Françoise MEDALE 2 

1 

LCABIE, Université de Pau et des Pays de l’Adour, IPREM UMR CNRS 5254, Technopôle 

Hélioparc Pau Pyrénées. 2, avenue du Président Angot, F- 64053 Pau Cedex 09, France 

2 INRA, UR1067 Nutrition, Métabolisme, Aquaculture, F-64310 Saint-Pée-sur-Nivelle, France 

3 Lesaffre Feed Additives, F-59700 Marcq-en-Barœul, France 

e-mail : simon.godin@univ-pau 

Nowadays, the extensive use of material from marine origin in aquaculture feeds takes a nonnegligible 

part in threatening marine resources [1]. Thus, the development of a sustainable 

aquaculture calls for new fish feeds mainly based on plant-ingredients, but also requires that the 

nutritional value of the final product is kept. Indeed, compounds such as polyunsaturated fatty acids 

(PUFAs), which are commonly found in fish, are proved to efficiently protect against cardiovascular 

diseases and breast cancer [2,3]. Also, selenium is a micronutrient essential to animals and has a 

decisive role in the regulation of the antioxidative capacity of the body. Therefore, there is a growing 

interest in the supplementation of plant-based diets with selenium, which would offer an alternative 

to marine-based feeds, and are moreover expected to fulfill the requirements of fish during its 

growth, especially during the early developmental stages. 

In this study, a 12-week feeding trial has been conducted with Se supplemented (selenite or Seyeast) 

and non-supplemented diets from marine or vegetal origin. The determination of major 

selenium species in two experimental diets has been carried out using anion exchange 

chromatography - inductively coupled plasma mass spectrometry (LC - ICP MS). Significant 

increase was observed in the total selenium level of rainbow trout fry depending on the Se diet level. 

After enzymatic digestion, the selenoaminoacids levels in fry fed with each diet have been 

investigated at the end of the trial. Growth rate and mortality were also monitored during the feeding 

trial, and the activity of some antioxidant enzymes was measured. 

References 

[1] L. Deutsch, S. Gräslund, C. Folke, M. Troell, M. Huitric, N. Kautsky, L. Lebel, Global 

Environmental Change 17 (2006) 238 

[2] H. Bartsch, J. Nair, R. Wyn Owen, Carcinogenesis 20 (1999), 2209 

[3] P. C. Calder, Clinical Science 107 (2004), 1 

-158 -


Poster Abstracts 

(P1) 

DETERMINATION OF TRACE SULFUR IN BIODIESEL AND DIESEL STANDARD 

REFERENCE MATERIALS BY ISOTOPE DILUTION SECTOR FIELD INDUCTIVELY 

COUPLED PLASMA MASS SPECTROMETRY 

Renata S. Amais 1 , Stephen E. Long 2 , Joaquim A. Nóbrega 1 and Steven J. Christopher 2 * 

1 Group of Applied Instrumental Analysis, Department of Chemistry, Federal University of São 

Carlos, 13565-905, São Carlos, SP, Brazil 

2 Chemical Sciences Division, National Institute of Standards and Technology, Charleston, SC, 

United States 

* e-mail: steven.christopher@nist.gov 

Sulfur emissions are related to the formation of acid rain and atmospheric pollution, and 

environmental concerns about sulfur emissions from the combustion of fossil fuels, have resulted 

in governmental agencies regulating the maximum sulfur content in biodiesel and diesel fuel. 1 The 

US Environmental Protection Agency (EPA) denominated low sulfur diesel with a sulfur content 

less than 500 mg kg -1 and, more recently in 2010 mandated the use of ultra low sulfur diesel 

(ULSD) which must have less than 15 mg kg -1 sulfur. 2 In addition, biodiesel has been added to 

diesel as an alternative to reduce S and other pollutant emissions, and the maximum sulfur content 

allowed in biodiesel can be as low as 10 mg kg -1 such as that established by the Brazilian 

Government Petroleum, Natural Gas and Biofuels Agency (ANP) and the European Union (EU) 

Euro V standard. In this work, a method is described for quantification of sulfur at low mass 

fractions in the order of µg g -1 in biodiesel and diesel fuels using double isotope dilution and 

sector field inductively coupled plasma mass spectrometry (ID-SF-ICP-MS). A SF-ICP–MS 

(Element XR, Thermo Scientific, Waltham, MA, USA) was used for all isotope ratio 

measurements. The sample introduction system comprised a concentric nebulizer and an ESI 

(Elemental Scientific, Omaha, NE, USA) stable sample introduction spray chamber which 

combines cyclonic and double-pass Peltier-cooled spray chamber. The radio frequency applied 

power was 1.35 kW, the monitored isotopes were 32 S and 34 S, and the number of spectra per 

sample was 250. All data for samples, blanks and calibration solutions were corrected for 

experimental mass bias, typically about 1.5 % per amu. The correction factor applied was based 

on comparing measured 32/34 ratios to an isotopic standard generated from SRM 3154 (Sulfur 

Standard Solution) having known isotopic abundances. Medium resolution conditions were 

employed to eliminate isobaric interferences at 32 S and 34 S related to polyatomic phosphorus and 

oxygen species. Closed vessel microwave digestion was employed using a diluted nitric acid and 

hydrogen peroxide decomposition medium to reduce sample dilution volumes. Biodiesel and 

diesel fuel digestion was performed using a high-pressure microwave oven (Microwave 3000, 

Anton Paar, Graz, Austria). A volume of 5.0 mL of nitric acid with a concentration of 7 or 14 mol 

L -1 , plus 3.0 mL hydrogen peroxide was added to each vessel containing 0.25 g fuel sample and an 

accurately weighed aliquot of the spike solution. The heating program consisted of one power 

ramp step (40 min to 1.4 kW) and a hold step for 30 min at the maximum pressure setting of 80 

bar. A conservative 35 W/min ramp rate was used to avoid a rapid increase of pressure. The same 

analytical process was applied for the procedure blanks. The final volume of all digests was made 

up to 50 mL with deionized water. The limit of detection (LOD) and the limit of quantification 

(LOQ) were calculated as three times and ten times the standard deviation of the mean 

concentration of S determined in 10 procedure blanks, respectively. The analytical method yielded 

LOD and LOQ values of 0.7 and 2.5 µg g -1 (in the fuel sample), respectively. Digests obtained 

using 7 and 14 mol L -1 nitric acid presented accurate results in both systems, 10.64 ± 0.13 mg kg -1 

and 10.73 ± 0.17 mg kg -1 respectively, by comparing with the certified value 10.81 ± 0.47 mg kg -1 . 

-159 -



No statistically significant difference at a 95 % confidence level could be observed between the 

certified value and both results using diluted and concentrated HNO 3 . Thus, 7 mol L -1 nitric acid 

was used in all further determinations. As can be seen in Table 2, the measured sulfur values for 

B100 Biodiesel (Animal-Based) and NIST SRM 2723a Sulfur in Diesel Fuel Oil agree well with 

certified data and no statistically significant difference at a 95 % confidence level was observed 

between measured and certified values for control samples confirming method accuracy. In 

addition, the analysis of the DRM-272b Sulfur in Diesel demonstrates that the proposed method is 

also feasible to measure high sulfur content in diesel (Table 2). 

Table 2. Sulfur determination in SRMs using diluted nitric acid at sample preparation step. The 

values are expressed as mean ± expanded uncertainty (n = 6). 

Sample Certified value (µg g -1 ) Found (µg g -1 ) 

B100 Biodiesel animal-based (SRM 2773) 7.39 ± 0.39 7.42 ± 0.32 

Sulfur in diesel fuel oil (SRM (2723a) 10.91 ± 0.32 10.85 ± 0.30 

Sulfur in diesel fuel oil (DRM 272b) 409.2 ± 8.6 412.7 ± 4.1 a 

a n=5 

SRM 2723a was used as a control for the candidate SRM 2723b value assignment measurement 

process. Both the control and the candidate SRM were measured in the same analytical sequence 

and the same spike solution (9.9110 µg g -1 ± 0.0076 µg g -1 34 S, n=4, mean ± standard deviation) 

was added to each. The individual components of uncertainty for S in each sample were 

determined according to ISO guidelines. 3 The total sulfur measured in the material was 9.05 µg g -1 

± 0.13 µg g -1 , and the expanded uncertainty is under 1.5 % relative. 

It was demonstrated in this work that it is feasible to use diluted nitric acid solution and 

microwave-assisted digestion, followed by ID-SF-ICP-MS for biodiesel and diesel fuel 

measurements of sulfur. Accurate results were obtained for SRM control materials and it was 

possible to make accurate total sulfur measurements in candidate SRM 2723b Sulfur in Diesel 

Fuel Oil. 

Acknowledgement 

The authors would like to thank the Fundação de Amparo à Pesquisa do Estado de São Paulo 

(FAPESP) for scholarship and fellowship provided (2010/17387-7 and 2012/00920-0). The 

authors are also grateful to the Conselho Nacional de Desenvolvimento Científico e Tecnológico 

(CNPq). 

References 

1 S. F. Boulyga, J. Heilmann, K. G. Heumann. Anal. Bioanal. Chem., 382: 1808. 2005. 

2 Environmental Protection Agency. www.epa.gov Access March, 2013. 

3 Guide to the Expression of Uncertainty in Measurement”, ISBN 92-67-10188-9, 1st ed. ISO, 

Geneva, Switzerland, 1993. 

-160 -



(P2) 

DETERMINATION OF CHROMIUM SPECIES IN THE WORKPLACE AIR 

M. Stanisławska, B. Janasik; R. Brodzka; W. Wąsowicz 

Nofer Institute Of Occupational Medicine, Department of Toxicology and Carcinogenesis, 

Biomonitoring Laboratory, 91-348, Lodz, Poland; 

e-mail:beatajan@imp.lodz.pl 

Occupational exposure to welding fumes is a known health hazard. There is substantial 

evidence that some chromium (Cr) containing substances are toxic for humans; furthermore 

hexavalent chromium is known to be carcinogenic. IARC has classified chromium VI (CrVI) as 

carcinogenic to humans (group 1). Exposure to Cr VI has been known to be responsible for the 

damage to the airways, irritating skin disease, asthma, bronchopulmonary cancer. According to the 

welding process, stainless steel welders may be exposed to all chemical species of chromium 

(metallic chromium, chromium III and chromium VI compounds). The toxicity depends on the 

chemical forms in which the chromium is present. It is necessary to quantify the individual 

oxidation states of chromium for an accurate assessment of their impact. 

The objective of this work was to application of high performance liquid chromatography 

(HPLC) coupled to inductively plasma mass spectrometry (ICP-MS) to measure the chromium 

species in the workplace air. 

The study was carried out in two plants in Poland performing welding operations. Stainless 

steel welders chosen for the study had worked in welding using three processes: manual metal arc 

(MMA), metal inert gas (MIG) and tungsten inert gas (TIG). Personal samples (one sample per 

shift) to assess time-weighted average (TWA) concentrations were continuously collected from 

the welders’ breathing zone. All the samples covered 6-7 hours out of the 8-hr work shift 

(including breaks). Airborne particulate sampling was performed on glass filters (Whatman GF/A, 

diameter 37mm), and membrane filters (Sartorius 11304, 0,8 µm, diameter 37 mm). 

The concentration of welding fumes (total particulate) were determined by weighing the filter 

and calculated in milligrams per cubic meter. Concentration the total chromium was determination 

by ICP-MS. The total hexavalent chromium were analyzed by visible absorption 

spectrophotometry with the diphenyl carbazide (DPC). The water-soluble chromium species were 

analyzed by HPLC-ICP-MS. The content of water-insoluble chromium (VI) species in a sample 

was determined from the difference of total chromium (VI) content and content of water-soluble 

chromium (VI). 

Detection of chromium species was accomplished with ELAN DRC-e (Perkin Elmer, SCIEX, 

USA). Methane was used in the Dynamic Reaction Cell (DRC) to reduce potential polyatomic 

interferences on Cr + at m/z 52. Separation was accomplished using HPLC Series 

200(PerkinElmer, SCIEX, USA). A 3 cm pecosphere column with 3µm C8 packing (Perkin 

Elmer) was used for separation. The mobile phase consisted of 1mM tetrabutyloammonium 

hydroxide (TBAH) and 0.6 mM ethylenediaminetetraaceticacid dipotassium salt (EDTA) and 5% 

methanol. Total chromium concentrations were measured using conventional nebulization into the 

ICP-MS. 

Linear regression analysis established the response function from the reagent blank and the 

series of five standard solutions (0.05; 0.1; 0.5; 0.75 and 1.0 µg/ml). Each species yielded an 

r>0.999. 

Time weighted average concentrations of the welding fumes and its elements at the worker’s 

breathing zone were respectively (mg/m 3 ): dust 0.14–10.7; iron 0.004–2.9; manganese 0.001– 

1.12; nickel < 0.001–0.2; chromium < 0.002–0.85 (mainly Cr (III) and insoluble Cr (VI)). The 

maximum admissible limits for workplace pollutants (TLV®-TWA) were exceeded for 

-161 -



manganese and for insoluble chromium Cr (VI). For Cr (III) the limit was exceeded in individual 

cases. The concentration of MIG/ total Cr fumes in air was, arithmetic mean 317µg/m 3 . It is also 

known that MIG welding generates more particulate matter than TIG welding. The percent 

contenof iron in welding fumes at workplace of the stainless steel welders was about 30 percent 

(MIG) and 15 percent (MMA) and 5 percent (TIG). The contribution of manganese in the welding 

fumes was about 10 percent (MIG) and 5 percent (MMA) and 1 percent (TIG). The nickel was at 

the level of about 1 – 2 percent (MIG, TIG). The contributions of the chromium compounds in the 

welding fumes was about 6 percent (MIG) and 1 percent (TIG), while those of hexavalent 

chromium was below 1 percent including water-soluble chromium(VI). In the MIG process the 

proportion of total soluble chromium is low; almost 100% of total chromium emitted in MIG 

process is the water-insoluble chromium compounds. 

The results from this work demonstrated that HPLC-ICP-DRC-MS technique can serve as a 

rapid, sensitive, precision system to determined chromium species in the workplace air samples. 

-162 -



(P3) 

A NEW APPROACH FOR THE DETERMINATION OF ARSENIC IN THE 

WORKPLACE AIR. THE POSSIBILITY OF USING LA-ICP-MS TECHNIQUE 

R. Brodzka, B. Janasik, M. Stanisławska, M. Trzcinka-Ochocka, W. Wąsowicz 

Nofer Institute of Occupational Medicine, Department of Toxicology and Carcinogenesis, 

Laboratory of Biological Monitoring, St. Teresy 8, 91-348 Lodz. 

e-mail: brodzka@imp.lodz.pl 

Assessment of occupational exposure to trace elements occurring in the workplace is based on the 

determination of metals concentrations in the air in the breathing zone of the employee. Arsenic, 

lead, cadmium and chromium are particularly harmful to health. They may pose carcinogenic 

effects to the human body. Currently, the method most commonly used to assess the exposure in 

the workplace is based on analyzing individual air samples collected on filters in the breathing 

zone of the workers (Polish Norm PN-Z-04008-7). Air filter samples are then mineralized in 

mixtures of acids. The ways of digestion depend mostly on the type of a filter used for air 

sampling (e.g. membrane filters). Therefore in present paper, a fast, easy and reliable qualitative 

and quantitative analysis of the content of metals in air samples from the workplace should be 

developed. 

The introduction of the LA-ICP-MS (mass spectrometry with inductively coupled plasma 

combined with laser ablation) technique for determination of air samples offers great opportunities 

for eliminating pretreatment steps, like mineralization process. Reducing execution time and low 

cost saving necessary to conduct research of environmental work would be possible. 

This study was aimed to assess of the applicability of LA-ICP-MS technique (LXS-500, Cetac, 

USA, ELAN DRC-e, Perkin Elmer, SCIEX) for the determination of metals in air samples in the 

occupational settings and compare techniques: LA-ICP-MS (quartz filters) and ICP-MS (by 

extraction from quartz filters and digestion membrane filters). 

Air samples were collected via the individual dosimetry method in the workers’ breathing zone 

continuously throughout a 6 – 7-hour period of time in accordance with the sample collecting 

strategy contained in the Polish Norm PN-Z-04008-7 (PN-Z-04008-7:2002). 

All analysis were conducted using three methods: LA-ICP-MS in quartz filters, ICP-MS in quartz 

filters after extraction 10ml 1% HNO 3 and LA-ICP-MS in membrane filters after mineralization. 

The study included 16 air quartz filters collected at work stations in Copper Smelter. 

Methods for metals determination in quartz filters by LA-ICP-MS and ICP-MS were developed 

and optimized. Validation parameters: linearity, range, limit of detection, limit of quantification, 

precision, accuracy, repeatability and recovery for maximum admissible concentration (MAC) 

levels in Poland were evaluated. 

After comparing this method with the mineralization method (regarded as a our reference analysis) 

adapted by NIOSH No. 7303, it can be concluded that the examined LA-ICP-MS method could be 

used for rapid pre-monitoring of the work environment based on the determination of metals in the 

workplace air. 

On the basis of analysis by LA-ICP-MS and validation set of parameters can be considered that 

analytical methodologies are correct. Results indicate that, LA-ICP-MS can be used in the future 

to monitoring of work environment. Application of this technique would be more promising when 

appropriate reference materials are available and technical problems (e.g. heterogeneity of dust 

covering the surface of the filter or lability of dust on the filter) would be established by 

appropriate of analytical strategy. 

-163 -



(P4) 

DETERMINATION OF MERCURY SPECIES IN FISH USING HPLC-ICP/MS 

Syr-Song Chen, Che-Lun Hsu, Wei-Min Fu, Cheng-Ming, Chu, 

Su-Hsiang Tseng, Ya-Min Kao, Lih-Ching Chiueh and Yang-Chih Shih 

Food and Drug Administration Department of Health 

No.161-2, Kunyang St, Nangang District, Taipei City 115-61, Taiwan (R.O.C) 

e-mail: jerlun@fda.gov.tw 

A method was developed for determination of inorganic, methy-, ethyl- and propylmercury in 

seafood. Mercury species were extracted from 1.0 g of edible seafood by adding 5 mL of alkaline 

solution (20% tetramethyl ammonium hydroxide in H 2 O) and using focused microwave digestion 

system. The condition of irradiation temperature of 70℃ and heating time of 8 min could have the 

optimal extraction efficiency without decomposing methy-, ethyl- and propyl mercury mercury. 

Mercury species in filtered extract were separated by reverse-phase high performance liquid 

chromatograph using a Phenomenex Synergi Hydro-RP column with gradient elution by aqueous 

(0.1% cysteine + 0.1% cysteine-HCl) and organic(methanol) mobile phase at room temperature 

and were detected by inductively coupled plasma/mass spectrometer at mass-to-charge 202. 

Optimum conditions allowed sample through out to be controlled by increasing the organic 

composition of the mobile phase, and the instrumental analysis time was near 10 min per sample. 

The recoveries of inorganic, methy-, ethyl- and propylmercury were 94.0 - 113.3%, 102.5 - 

107.2%, 85.6 - 87.8% and 98.9 - 110.8%, respectively. The limits of quantitation of mercury 

species were found 0.01 ppm for inorganic and methylmercury, and 0.005 ppm for ethyl- and 

propylmercury. The proposed method was finally validated by the analysis of biological certified 

reference material DORM-3 fish protein. The detected and certified value of methylmercury were 

0.329 ± 0.019 mg/kg and 0.355 ± 0.056 mg/kg respectively. It indicated that the method was well 

available to detect the mercury species in fish. Twelve samples of fish muscle purchased from 

markets were analyzed. The results showed the levels of methylmercury were in the range of ND - 

0.924 mg/kg, those of inorganic mercury were ND - 0.011 mg/kg, and ethyl- and propylmercury 

were not detected. 

Key words:seafood, mercury species, high performance liquid chromatograph, inductively 

coupled plasma mass spectrometer 

-164 -



(P5) 

DEVELOPMENT OF A QUANTUM DOT-BASED IMMUNOASSAY FOR SCREENING 

OF TETRACYCLINES IN BOVINE MUSCLE 

Jenifer García-Fernández, Laura Trapiella-Alfonso, José M. Costa, Rosario Pereiro, Alfredo Sanz- 

Medel. 

Department of Physical and Analytical Chemistry, University of Oviedo, Avd. Julián Clavería 8, 

33006 Oviedo, Spain. 

e-mail: trapiellalaura@uniovi.es 

The family of tetracyclines, (TC: tetracycline, chlortetracycline, oxytetracycline and 

doxytetracycline) is a group of antibiotics that have been widely used in human and veterinary 

medicine. These drugs have also been applied as growth promoters in animal husbandry. 

However, the presence of TC residues in food has harmful effects in human health, so maximum 

residue levels have been set, being 100 µg/Kg in bovine muscle 1 . Although up to date, there are 

different analytical strategies available for the determination of TC (based on chromatography, 

capillary electrophoresis, photoluminescence or immunochemical techniques), nowadays exists a 

great demand of developing simple, fast and low cost screening methodologies for the 

discrimination of such contaminants. Immunoassays with its inherent selective recognition and 

binding of the analyte and simple sample treatment are specially indicated for such 

determinations. 

In this communication we present the development of a new screening strategy for tetracyclines 

based on a quantum dot (QD) fluorescent competitive immunoassay. In this format of assay the 

antigen (analyte) and the labeled antigen (tracer) compete for the limited binding sites of the 

immobilized antibody. We will present our work in the following steps: 

Synthesis and characterization of the label: CdSe/ZnS QDs. 

Preparation of the TC-BSA conjugate and further bio-conjugation with QDs to obtain the tracer 

TC-BSA-QDs that gives the analytical signal in the immunoassay. Characterization of the tracer. 

Development of the immunoassay and the screening curve; here, unspecific absorptions, cross 

reactivity, and additive studies are evaluated. 

Application to muscle tissue by extraction of TC from the bovine muscle. 

The results obtained showed the positive discrimination between non-contaminated and 

potentially TCs contaminated meat samples. Moreover, the cut-off level for the screening curve 

turned out to be about two orders of magnitude lower than the permitted legislation levels. Finally, 

it should be stressed that the strategy proposed in this contribution could be expanded easily to the 

adventageous analysis of other food contaminants or other food samples of interest. 

1 Commission Regulation (EU) Nº 37/2010 on pharmacologically active substances and their classification regarding 

maximum residue limits in food stuffs of animal origin. 

-165 -



(P6) 

ICP-MS-BASED ISOTOPIC MEASUREMENTS OF ATMOSPHERIC LEAD IN POLAR 

REGIONS 

Marco Grotti 1 , Andrea Bazzano 1 and Mery Malandrino 2 

1 Department of Chemistry and Industrial Chemistry, University of Genoa, Italy 

2 Department of Chemistry, University of Turin, Italy 

e-mail: grotti@unige.it 

The lead isotopic composition of aerosols reaching the polar regions potentially contains valuable 

information on the source and long-range transport of atmospheric particulate and associated 

contaminants, which will complement that from meteorological and elemental composition 

studies. In the frame of the Italian polar research programmes, samples of atmospheric aerosols 

have been systematically collected in both Norwegian Arctic (Ny Älesund, Svalbard Islands) and 

Antarctica (Terra Nova Bay, Victoria Land) and analysed for elemental composition and stable 

lead isotope ratios ( 206 Pb/ 207 Pb, 208 Pb/ 207 Pb). 

Accurate and precise determination of lead isotope ratios in digests of particulate samples has 

been achieved by inductively coupled plasma mass spectrometry (ICP-MS), using the dynamic 

reaction cell to improve the precision. The relevant operating parameters have been optimized in a 

multivariate way, according to the empirical modelling and experimental design concepts. This 

allowed the full consideration of mutual interactions among the factors and simultaneous 

minimization of %RSD-values and mass discrimination effects. 

After determining the detector dead time, the following instrumental parameters have been 

studied: settling time, the rod offset voltages of both the quadrupole and the reaction cell, the 

Mathieu stability parameters of the cell’s quadrupole, the cell path and the axial field voltages, 

dwell time and number of sweeps. Moreover, the use of argon, methane and ammonia as the 

collision gas was explored and the measured isotope ratio precision compared to that attainable 

with standard quadrupole-based ICP-MS and theoretical values. 

The main figures of merit of the optimized method have been determined according to the IUPAC 

recommendations, with special attention to the limit of quantification at a given precision 

threshold and robustness. 

The main results of the method optimization and validation and preliminary data for the analysis 

of particulate samples will be reported and discussed. 

-166 -



(P7) 

SIGNS OF SPATIAL HETEROGENEITIES WITHIN XLPE CABLE INSULATION 

PROBED BY SOLID STATE 1 H-NMR 

Jobby Paul 1 , Eddy W. Hansen 1 , Sissel Jørgensen 1 , Bjørnar Arstad 2 and Aud Bouzga 2 

1 

Department of Chemistry, UiO, P. O. Box 1033 Blindern, N-0315 Oslo, Norway 

2 SINTEF Materials and Chemistry, P.O. Box 124 Blindern, N-0314 Oslo, Norway 

e-mail: eddywh@kjemi.uio.no 

A number of cylindrical samples were drilled out from the inner-, middle- and outer regions of a 

commercial cross-linked polyethylene (XLPE) cable insulation material as illustrated: 

Inner 

Middle 

Outer 

r 

During ageing in an air circulating oven at 130 o C for a period of 2 months samples were taken out 

regularly from the oven, cooled to 55 0 C, and analyzed by NMR. As can be inferred from 

18 days 

22 days 

26 days 

34 days 

Inner 

Middle 

Outer 

Figure 1. The colour of the inner, middle and outer layers of the XLPE cable insulation disc aged 

in air at 130 0 C for 18, 22, 26 and 34 days, respectively. Images are taken at room temperature. 

the sample color in Figure 1, a significant change in some (unspecified) properties of the polymer 

occurs during ageing. More specifically, 1 H-NMR analysis of the Free Induction Decays (FID) 

during ageing of the outer region of the samples demonstrates the crystalline (C) component and 

the two amorphous components – the amorphous soft (A S ) and the amorphous rigid (A r ) - change 

during ageing at 130 0 C, as noted on Figure 2 [1] . 

-167 -



Figure 2. Fractional intensity as a function of ageing time within the outer layer of the XLPE 

cable insulation. C, A r and A s represent the crystalline, the amorphous rigid and the amorphous 

solid fractions, respectively. The vertical, dotted lines represent the start (t I ) and the end (t II ) of the 

fast oxidation time period (period II), as determined for the C-fraction. 

Of particular interest is the spatial dependence of the spin-lattice relaxation rate R 1 =1/T 1 which 

occurs during ageing, as suggested by the results presented in Figure 3. 

Figure 3. Spin lattice relaxation rate R 1 (=1/T 1 ) as a function of ageing time within the inner-, 

middle- and outer layers of the XLPE cable insulation. The measurements were all performed at 

55 o C, after cooling the sample from 130 o C to room temperature. 

Also, NMR spin-spin relaxation time measurements (not shown) together with sample mass 

measurements are all consistent and suggest that the native cable insulation material is spatially 

inhomogeneous. These spatial inhomogeneities are believed to originate during the processing of 

the material. 

Acknowledgement. A PhD-grant (Jobby Paul) financed through the project "Demanding 

Polyolefin Applications" (project partners Nexans, Bredero Shaw SINTEF, Norner, NTNU and 

UiO) is greatly acknowledged. The project is financed by Nexans, Bredero Shaw, Borealis and 

the Research Council of Norway (179945/I40). 

[1]. Hansen EW, Roots J. Determination of crystallinity in polyethylene from 1 H-NMR FID 

analysis. Effect of non-curie temperature behaviour. International Journal of Research and 

Reviews in Applied Sciences. 2010 (5) 207-212. 

-168 -



(P8) 

DELTA ( 13 C) DETERMINATION ON BIOFUELS AND BIOPLASTIC APPLYING 

CAVITY RING-DOWN SPECTROSCOPY 

Gisele Birman Tonietto 1, 2 , Jose M. Godoy 1 , Julianna M. Martins 1 , Walquiria R. S. Ribeiro 1 , Mara 

A. Silva 1 

1 Pontifícia Universidade Católica do Rio de Janeiro – Chemistry Department 

2 Petrobras – Research Center – Cenpes - Chemistry Department 

email: giselebt@puc-rio.br 

Cavity ring-down (CRDS) spectroscopy is a direct absorption technique, which can be performed 

with pulsed or continuous light sources and has a significantly higher sensitivity than obtainable in 

conventional absorption spectroscopy. The CRDS technique is based upon the measurement of the 

rate of absorption rather than the magnitude of absorption of a light pulse confined in a closed 

optical cavity with a high Q factor. The advantage over normal absorption spectroscopy results 

from, firstly, the intrinsic insensitivity to light source intensity fluctuations and, secondly, the 

extremely long effective path lengths (many kilometres) that can be realized in stable optical 

cavities. In the last decade, it has been shown that the CRDS technique is especially powerful in 

gas-phase spectroscopy for measurements of either strong absorptions of species present in trace 

amounts or weak absorptions of abundant species. 

Cavity ring-down spectroscopy (CRDS) is a laser-based absorption spectroscopy technique that is 

starting to and extensive application as a consequence of the very high sensitivity of the method 

compared with more traditional absorption spectroscopy techniques. 

The present study aimed to obtain the 13 C/ 12 C isotopic signature in solid and liquid samples using 

a laser analyzer. An isotopic analysis method using a total organic carbon analyzer coupled to a 

cavity ring-down spectrometer (iTOC-CRDS) was developed and implemented. The results were 

compared with those obtained by IRMS. The method performance was evaluated by the 

parameters of linearity; accuracy, using standard reference materials; precision, using parameters 

of repeatability and reproducibility and by calculating the associated uncertainties. The analyzed 

samples were biofuel and bio-plastic. 

We determined stable carbon isotopic compositions (δ13C) of plastics to discriminate between 

plant- and petroleum-derived plastics. The δ13C values of plastics derived from C4 plants are 

significantly higher than those of petroleum-derived plastics. These results suggest that the stable 

isotope analysis would be useful in discrimination of plant-derived plastics from petroleumderived 

plastics. 

-169 -



(P9) 

THE STRUCTURAL AND MAGNETO-RESONANCE PROPERTIES OF THE POR-INP 

Suchikova Y. 1 

1 Berdyansk State Pedagogical University, str. Schmidt 4, Berdyansk, Ukraine 

e-mail: yanasuchikova@mail.ru 

Low-dimensional semiconductors are a subject of intensive investigations due to their modified 

optical and electric properties caused by the quantum-dimensional effects being inherent to 

nanostructures. Among such the semiconductors a special attention is given to the indium 

phosphite (InP) as the technologically impotent material in manufacturing the lasers, diodes, solar 

batteries etc. The single-crystal InP plates are used as the substrates in growing different 

heterostructures in making the effective radiation sources (injection lasers, light-emitting diodes) 

and high-speed photodetectors for fiber-optics communication lines. Today, the indium phosphite 

is the most probable material for chips mass-production. The properties of porous InP are 

interesting since in contrast to the cilicon, for example, the indium phosphite is the direct gap 

semiconductor that allows one to use such semiconductor for manufacturing the high-performance 

light-emitting devices. Finally, the InP is sufficiently inert material, oxidize weakly in the open air 

and does not interact virtually with acids. Due to that one can expect that the porous based layers 

will be more stable ones and less subjected to the environmental activity than the porous cilicon. 

In this paper the structural and magneto-resonance properties of the InP samples doped by the 

sulfur or zinс with n- and p- polarity of conductivity and the charge carries concentration 

N=2.3*10 18 cm -3 are investigated. 

The InP samples with n- and p- polarity of conductivity with different surface orientation and with 

charge carries concentration N=2.3*10 18 cm -3 were selected by us the subject under test. The 

crystal lattice of those is similar to the zinc blende structure. The atom coupling in the lattice has 

mainly the covalent nature with some part (up to 15%) of the ion component. The samples are 

doped by sulfur (S) or zinc (Zn). 

The single-crystalls of InP have been produced by Chohralskii method in the Laboratory of 

«Molecular Technology GmbH» company (Berlin, Germany). The sample thickness is 1mm. The 

plates were cut out perpendicularly to the axis growth and polished with both sides. 

Electrochemical etching was performed on the standard set up in the electrolytic cell with a 

platinum on the cathode. In this case the hydrofluoric and hydrochloric acid solutions with 

different concentration were employed as the electrolyte. The morphology of the porous samples 

under test has been investigated by means of the scanning electron microscope JSM-6490. 

The analysis of sample's morphology has shown that the active cavitation was observed in all the 

cases virtually. It has been revealed that a steady-state configuration of the porous layer surface is 

formed at the current density maximization under conditions when the cavitation becomes as 

dominating electrochemical process leaking at the given value of the polarizing voltage on the 

single-crystal semiconductor anode. In the row of halogenide-ions the minimum voltage value of 

beginning the structure formation corresponds always to the fluorine anion. The morphology of 

porous samples being obtained by employing the hydrofluoric acid demonstrates a grid of mesoor 

macropores. The formation of such pores is explained frequently by the emergence of defects 

and dislocations on the crystall surface. Here, the substantial surface over-pickling is observed 

(Fig.1a). As can be seen from the Figure, the re-etching areas are clearly visible that is evidence of 

strongly “hard” etching conditions. The porous surface demonstrates the extended morphology 

with generated massive etching holes. The surface like that has the dangerous effective area as 

compared with the single-crystal analogue. However, the aforementioned surface is not to be 

-170 -



sufficiently perfect for the heterostructure substrate employing. Therefore, it seems to be advisable 

to change the etching regime. 

HCl-based etching agents allow one to obtain a layer composed basically of the nanopores (Fig. 

1b) demonstrates the ordered assembly of pores formed on the substrate from the single-crystal 

InP under etching conditions in 5% hydrochloric acid solution. In this case the pores inter-grow 

along the full ingot surface. The pore size is about 40nm that is evidence of that the given structure 

is the nanostructure. The wall size between the pores is in the limits of 5-10nm. The result like that 

is technologically important since a quality of the porous films is determined by the nanostructure 

dimensions, by the range of porosity and by the uniform pores distribution along the sample 

surface. Here, the smaller pores size and more porosity ratio the porous structure is more perfect. 

porosity ratio. The range of porosity is about 60% from the total sample are. 

Figure 1. Morphology of n-InP (111), electrolyte HF: H2O=1:1, j=80 mА/сm2, t=10min (a); 

and of the porous n-InP (100) being obtained in the 5% HCl, t=5min (b) 

The measured EPR spectra are sufficienty broad (200 -300 Gauss). They undergo minor changes 

in the temperature range from 300К to 77К. Here, g-factor is changed within the limits 1.97-1.98 

for different samples. The observable differences in the EPR spectra of single-crystal samples and 

porous ones are caused by changing in the surface properties as a result of electrochemical 

treatment of the crystals. Among the most probable reasons can be next factors: 

the partial disorder of the crystal lattice; the fast phosphorus sublattice etching leads to the 

stoichiometry shifting towards the excess of indium atoms; due to the nanocrystallites formation 

the surface becomes more "relief", i.e. the surface loses both the homogeneity and the uniformity; 

quite possible the formation of additional disturbed bonds which can also effect on the EPR 

spectra. 

The results of investigations of the structural and magneto-resonance properties of both the singlecrystals 

and porous InP samples doped by S and Zn with the charge carries concentration 

N=2.3*10 18 cm -3 have been presented in this paper. As it follows from the ample's morphology the 

active cavitation was observed for all the samples under test. It has been shown that in order to 

decrease the electrolyte effect on the porous surface formation it is advisable to change the etching 

regime (the time and the current density) on a more soft one or to use the more diluted solution of 

the etching agent. Really, the HCl-based etching agents allow one to obtain a layer composed 

basically of the nanopores that determines in the final analysis the porous films quality. 

-171 -



(P11) 

57 FE-MÖSSBAUER, XANES AND HR-TEM STUDIES OF ELECTRICALLY 

CONDUCTIVE BAO-FE 2 O 3 -V 2 O 5 GLASES 

Satoru Yoshioka 1 , Shiro Kubuki 2 , Hitomi Masuda 2 , Kazuhiko Akiyama 2 , Kazuhiro Hara 1 

Testuaki Nishida 3 

and 

1 Department of Applied Quantum Physics and Nuclear Engineering, Graduate School of 

Engineering, Kyushu University, Moto-oka 744, Nishi-ku, Fukuoka 819-0395, JAPAN 

2 Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan 

University, Minami-Osawa 1-1 Hachi-Oji, Tokyo 192-0397, JAPAN 

3 Department of Biological and Environmental Chemistry, Faculty of Humanity-Oriented Science 

and Engineering, Kinki University, Kayanomori 11-6, Iizuka, Fukuoka 820-8555, JAPAN 

e-mail: kubuki@tmu.ac.jp 

Vanadate glass having electrical conductivity () of 10 -7 -10 -5 Scm -1 is classified as a semi-conductor. 

Kubuki et al. revealed that 20BaO•10Fe 2 O 3 •70V 2 O 5 glass showed larger value of 10 0 Scm -1 when it 

was annealed at around the crystallization temperature (T c ) of 500 o C [1]. Vanadate glass could be a 

fascinating candidate for cathode active material of secondary battery [2]. Structural change 

occurring in vanadate glass, i.e., a decrease in the local distortion of Fe III O 4 and VO 4 tetrahedra was 

elucidated by 57 Fe-Mössbauer study [1,2]. In this study, 57 Fe-Mössbauer, X-ray absorption near edge 

structure (XANES) and high-resolution transmitting electron microscopy (HR-TEM) were carried 

out, in order to reveal the structural change of xBaO•10Fe 2 O 3 •(90-x)V 2 O 5 glass, abbreviated as xBFV 

glass, caused by isothermal annealing. 

Elemental mapping obtained from HR-TEM images of 20BFV glass showed that Ba 2+ , V IV and V V 

ions were homogeneously dispersed in the glass matrix before and after isothermal annealing at 500 

o C for 100 min, as shown in Fig. 1 (left and center). On the other hand, it proved that Fe III was 

aggregated after annealing at 500 o C for 100 min (Fig. 1, right). From DTA study, activation energy 

for crystallization (E a ) of 20BFV glass was estimated to be 2.3 eV [1], which is comparable to Fe-O 

chemical bond energy of 2.6 eV [3]. These results suggest that Fe III primarily migrated during the 

partial crystallization of 20BFV glass. In order to estimate the dimension of crystallization, Johnson- 

Mehl-Avrami (JMA) equation [4] was applied to the change of quadrupole splitting () in the 

Mössbauer spectra due to isothermal annealing, i.e. 

Ba 

V 

Fe 

Figure 1. Elemental mapping obtained from TEM image of 20BaO•10Fe 2 O 3 •70V 2 O 5 glass 

after annealing at 500 o C for 100 min. 

-172 -



ln [−ln(1 − x)] = n ln t + ln k (1), 

1− x = ( − t ) / (2), 

where, x, n, t, k and t are fraction of crystallization, Avrami index, annealing time, rate constant 

and quadrupole splitting value obtained after isothermal annealing for t min, respectively. As a result 

of JMA plot with obtained for 20BaO•10Fe 2 O 3 •70V 2 O 5 glass annealed at 450 o C, n value was 

estimated to be 1.5, indicating that the crystallization proceeded three dimensionally. This result is 

consistent with the result of elemental mapping of Fe (Fig. 1, right). 

(a) 

(b) 

(c) 

(d) 

(e) 

V 2 O 5 

VO 2 

V 2 O 3 

(a) 

(b) 

(c) 

(d) 

(e) 

Fe 2 O 3 

Fe 3 O 4 

FeO 

(A) 

(B) 

Photon energy / eV 

Photon energy / eV 

Figure 2. (A) V-K and (B) Fe-K edges of XANES profiles of xBaO•10Fe 2 O 3 •(90-x)V 2 O 5 

glass with ‘x’ of (a) 40, (b) 35, (c) 30, (d) 25 and (e) 20 after annealing at 500 

o C for 100 min. Dashed lines are guide to the eyes. 

XANES profiles of xBFV glass before annealing compose of a shoulder peak of 5483 eV for V-K 

edge and two peaks of 7128 and 7135 eV for Fe-K edge. As shown in Fig. 2, V-K edge XANES 

profiles of xBFVglass after the annealing became similar to that of VO 2 , having a shoulder peaks at 

the photon energy of 5483 eV, with an increase of V 2 O 5 content (Fig. 2(A) (a)→(e)). On the other 

hand, Fe-K edge profiles showed a decrease in the peak intensity of 7135 eV and became similar to 

that of Fe 3 O 4 , having a characteristic peak at the photon energy of 7128 eV (see Fig. 2(B) (a)→(e)). 

These results indicate that high electrical conductivity of xBFV glass is associated with the mixed 

valence states of V IV , V V , Fe II and Fe III , affected by isothermal annealing. 

References 

[1] S. Kubuki, H. Sakka, K. Tsuge, Z. Homonnay, K. Sinkó, E. Kuzmann, H. Yasumitsu and T. 

Nishida, J. Ceram. Soc. Jpn., 115 [11], 776-779 (2007). 

[2] T. Nishida, Y. Yoshida, Y. Takahashi, S. Okada and J. Yamaki, J. Radioanal. Nucl. Chem., 

275[2], 417-422 (2008). 

[3] K. H. Sun, J. Am. Ceram. Soc., 30, 277-281 (1947). 

[4] M. Avrami, J. Chem. Phys., 7, 1103-1112 (1939). 

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(P11) 

MEASUREMENT OF ELEMENTAL CONTENTS IN HEMOLYMPH, MALPIGHIAN 

TUBULES, GUT AND URINE OF RHODNIUS PROLIXUS INVESTIGATED BY SR- 

TXRF 

Andrea Mantuano 1 , Arissa Pickler 1 , Regina C. Barroso 1 , Liebert P. Nogueira 1 , Carla L. Mota 2 , 

André P. de Almeida 2 , Delson Braz 2 , Simone C. Cardoso 3 , Marcelo S. Gonzalez 4 , Eloi S. 

Garcia 5 and Patricia Azambuja 5 

1 

Physics Institute/State University of Rio de Janeiro, Rua São Francisco Xavier 524/3007B, Zip 

code: 20550-900, Rio de Janeiro, RJ, Brazil 

2 Nuclear Engineering Program/COPPE/Federal University of Rio de Janeiro, Brazil. 

3 

Physics Institute/Federal University of Rio de Janeiro, Brazil 

4 Departamento de Biologia Geral/Federal Fluminense University, Rio de Janeiro, Brazil 

5 Laboratory of Biochemistry and Physiology of Insects/Oswaldo Cruz Foundation, Rio de 

Janeiro, Brazil 

e-mail: mantuanoandrea@gmail.com 

Rhodnius prolixus is a blood-sucking insect well known by its importance as vector of 

Trypanosoma cruzi (parasite causative agent of Chagas’ disease) principally in Latin America. 

The insect feeds on blood infected with trypomastigote forms which transform into epimastigotes 

and spheromastigotes in stomach. The gut of triatomines is the first environment for the 

transformation of the Trypanosoma cruzi where the epimastigote multiply increasing the 

population of parasites. In the rectum, the epimastigotes transform into metacyclic trypomastigotes 

which are eliminated with the faeces and urine [1] . 

The establishment of Trypanosoma cruzi infection in the gut of the insect vector may be 

dependent on, and possibly regulated by, a range of biochemical and physiological factors. 

Some nutrients contained in the body of Rhodnius prolixus can influence on the parasite 

development. 

In this work, special attention is given to the elemental contents in fluid secretion by Malpighian 

tubules and gut of the uninfected control insects. The Malpighian tubules filter hemolymph and 

secrete a liquid that is often compared with the primary urine in vertebrates. The transport 

regulation of Malpighian tubules is certainly one of the key points for insect homeostasis and, 

certainly, it is also important for Trypanosoma cruzi transmission. We have investigated Cl, Ca 

and K elemental changes observed in gut, Malpighian tubules, hemolymph and urine of fifth-stage 

Rhodnius prolixus on different days after feeding rabbit blood. The analytical approach of 

Synchrotron Radiation Total Reflection X-ray Fluorescence (SR-TXRF) technique was used to 

investigate trace elements of these parts of the insect. It was facility at the X-ray Fluorescence 

beamline in Brazilian Synchrotron Light Laboratory LNLS/Brazil. 

The point to note from the results is that basically, largest part of Ca and K is deposited in the 

Malpighian tubules, some is retained in the hemolymph and relatively little is eliminated from the 

body. The results agree in showing that much the greater part of the Ca in the diet is retained in the 

body. 

Our results reveal that the concentrations, in µg mL -1 , of Cl, K and Ca in the gut, in comparison 

with hemolymph, urine and Malpighian tubules, are low statistically significative. We concluded 

that the Cl and K are extremely excreted in the first two days. The accumulation of K and Ca 

increased (P



[1] E. S. Garcia, Journal of Insect Physiology, 53, 11–21, 2007. 

(P12) 

CHARACTERIZATION OF SILVER NANOPARTICLES BY PAGE-LA-ICP-MS 

Maria S. Jimenez 1 , Maria T. Gomez 1 , Carmen Diez 1 , Lluis Arola 2 , M.Josepa Salvadó 2 , Cinta 

Bladé 2 , Juan R. Castillo 1 

1 

Analytical Spectroscopy and Sensors Group, Institute of Environmental Sciences, University of 

Zaragoza, Zaragoza, Spain 

2 Group of Nutrigenomics, University Rovira i Virgili, Campus Sescelades, Tarragona, Spain. 

e-mail: jimenezm@unizar.es 

The numerous possibilities of engineered nanomaterials (ENMs) have led to fast growth of 

industries utilizing ENMs. This creates a need to determine physicochemical properties of each 

material and to evaluate the biological response due to exposure to the developed ENMs. In 

particular, Silver nanoparticles (Ag NPs) are of interest because of the unique properties which 

can be incorporated into anti microbial applications, biosensor materials, composite fibers, 

cryogenic superconducting materials, cosmetic products and electronic components. 

When NPs enter a biological fluid, proteins and other biomolecules rapidly compete for binding to 

the nanoparticle surface, leading to the formation of a dynamic protein corona that critically 

defines the biological identity of the particle. The biophysical properties of such a particle-protein 

complex often differ significantly from those of the formulated particle. Hence, the further 

biological responses of the body as well as the particle´s biodistribution are significantly 

influenced by the nanoparticle-protein complex, potentially contributing also to unwanted 

biological side-effects. There are many factors influencing the detailed nature of the NP 

biomolecule corona, with NP size, shape, surface charge, and solubility all playing a role in the 

interaction of the NPs with proteins. 

In this study, characterization of different AgNPs in a biological culture media by applying 

electrophoretic techniques (1D-PAGE and Agarose Gel Electrophoresis ) and detection of Ag 

species associated to proteins by Laser Ablation(LA)-ICP-MS will be shown. AgNPs standards of 

different sizes and market products were used as Ag NPs; Dulbecco’s Modified Eagle’s Medium 

supplemented with Fetal Bovine Serum was used as biological culture media. Based on our 

previous research [1], different electrophoretic methods have been applied for protein separation 

and NPs characterization. Evaluation of protein corona formation has been studied and 

investigations for successful detection of Ag forms by LA-ICP-MS have been carried out. 

[1] M. S.Jiménez, L. Rodríguez L, Juan R. Bertolin, M.T. Gomez MT, J.R. Castillo JR, Anal. Bioanal. 

Chem. 405 (2013) 359-368. 

Acknowledgement This work was sponsored by the by Spanish Ministry of Science and 

Technology, project no CTQ 2012-38091-CO2. 

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(P13) 

MERCURY LEVELS IN A POLLUTED RIVER ECOSYSTEM IN EAST BOHEMIA: 

FROM LONG-TERM MONITORING OF TOTAL CONTENT TO SPECIATION 

ANALYSIS 

Miroslav Soukup 1,2 , Inga Petry-Podgórska 1 , Stanislav Lusk 3 , Lukáš Vetešník 3 , Jan Zíka 1,4 , Vlasta 

Korunová 1 and Jan Kratzer 1 

1 Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, 602 00 Brno, Czech Republic 

2 Secondary Industrial School, Havlíčkova 426, 470 01 Česká Lípa, Czech Republic 

3 Institute of Vertebrate Biology of the ASCR, v.v.i., Květná 8, 603 65 Brno, Czech Republic 

4 Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Albertov 

8, Prague 2, CZ 128 43 Czech Republic 

e-mail: jkratzer@biomed.cas.cz 

Total mercury content in fish samples (muscle and liver tissue) have been yearly monitored in the 

river Tichá Orlice in the vicinity of the town Králíky (East Bohemia) for almost 20 years. This 

region was selected because there had been a factory producing fluorescent lamps since 1970´s till 

1987. Moreover, there is a disposal of the fluorescent lamps wasters and other dangerous waste 

originating from the factory located about two kilometers far from the former factory. 

Undoubtedly, both the factory and the disposal area had significantly contributed to the 

environmental pollution by mercury in the past as demonstrated in this study. Whereas the 

mercury level in the vicinity of the factory has decreased by an order of magnitude in last 20 years 

thanks to its closure, the disposal is still a local source of pollution. 

Brown trout (salmo trutta) species were collected annually in autumn and were characterized in 

terms of age, sex, body weight and length. Samples of liver and muscle tissue were taken and 

stored frozen (-20 °C). Frozen samples were found stable for at least one year as verified 

experimentally, no mercury losses or cross-contamination was observed. Total mercury content 

was determined without any sample pretreatment employing advanced mercury analyzer (AMA 

254) produced by Altec Czech Republic. This single purpose atomic absorption spectrometer 

AMA 254 is based on in situ dry ashing of the sample in the stream of oxygen followed by 

amalgamation of Hg cold vapors on gold surface with subsequent detection by AAS. 

Natural (background) levels of mercury content in fish samples were estimated to be between 0.1 

and 0.2 mg.kg -1 . Samples of brown trout species were collected in Czech rivers Divoká Orlice and 

Punkva in localities were neither industrial, nor agricultural influence was expected. This 

estimated level of natural Hg content in river ecosystem is in a good agreement with other studies. 

The average mercury content in muscle and liver tissue in trouts living in the vicinity of the 

factory is compared in years 1995 (7 years after its closure) and 2012 (25 years after its closure), 

respectively. A 15 km long part of the river downstream the factory was monitored and the results 

are summarized in Tab. 1. The results in Tab. 1 demonstrate that average mercury level in fish 

muscle tissue has significantly decreased between years 1995 and 2012, i.e. after the closure of the 

factory. The decrease by a factor of ten was observed in the factory neighbourhood. At least 15 km 

of the river downstream the factory was significantly influenced by the factory in 1995. 

Interestingly, Czech limit for Hg content in muscle tissue of predatory fish was 0.5 mg.kg -1 at that 

time (EU limit 1.0 mg.kg -1 ). As a result, the trout muscle tissue was not safe to eat in 1995. 

Nowadays, 25 years after the closure of the factory, the mercury content in the monitored area is 

not significantly higher than natural background in the Czech Republic. The only exception is the 

locality Borikovice (see Tab. 1), 2 km far from the former factory, where the ground water from 

-176 -



the disposal area merges the river stream. Whereas the factory does not contribute to the 

environmental pollution 25 years after its closure, the nearby disposal of Hg-containing wastes is 

still the source from where mercury leaks in to the river ecosystem. 

Tab. 1 Average total mercury content in muscle and liver tissue in 1995 and 2012 in the 

longitudinal river profile from 0 to 15 km downstream the factory 

Average Hg content (mg.kg -1 ) 

year 1995 2012 

Locality/distance downstream muscle liver muscle liver 

the factory (km) 

Králíky/ 0 1.44 2.83 0.13 0.14 

Boříkovice/2.2 0.52 0.82 0.31 0.46 

Celné/11.4 0.87 2.10 0.14 0.20 

Těchonín/14.4 0.44 0.83 0.11 0.17 

A method for mercury speciation analysis was validated for fish tissue. Mercury species can be 

completely extracted from the sample by 0.2 % L-Cystein hydrochloride solution (2 hours at 60 

°C). Chromatographic separation was carried out with Agilent 1200 HPLC setup using Agilent 

Zorbax Eclipse XDB-C18 column (4.6 x 150 mm, 5 m) and 0.1 % L-Cystein hydrochloride with 

2% methanol as a mobile phase. An Agilent 7700 Series ICP-MS was employed as a detector. 

Applicability of this method will be demonstrated on analysis of certified reference material 

DOLT-4 (dogfish liver). Results of speciation analysis of selected brown trout samples will be 

discussed. 

Further monitoring in this area will continue since remediation of the disposal is planned in the 

near future. The effect of the remediation works on the mobility and concentration levels of 

mercury species in the ecosystem (during the works and after the remediation) will be 

investigated. 

This work was supported by Institute of Analytical Chemistry of the ASCR, v.v.i. (project no. 

RVO: 68081715), the Ministry of Education, Youth and Sports of the Czech Republic (project 

MSM 0021620857) and Academy of Sciences of the Czech Republic (project Orlice). 

Miroslav Soukup is grateful to “The Open Science III Project“ (registration number 

CZ.1.07/2.3.00/35.0023) – the systematic integration of talented secondary-school students in 

scientific-research activities. This project was approved within the Operational Programme 

Education for Competitiveness, Support Area 2.3, co-financed from the state budget of the Czech 

Republic and the European Social Funds. 

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(P14) 

METAL, METALLOTHIONEIN AND REDUCED GLUTATHIONE LEVELS 

INDICATING OXIDATIVE STRESS IN BLUE CRABS (CALLINECTES SP.) AND 

NOVEL DATA REGARDING OXIDATIVE STRESS IN EGGS 

Raquel Teixeira Lavradas 1 ; Rachel Ann Hauser-Davis 2 ; Ricardo Lavandier 1 ; Rafael Christian 

Chávez Rocha 1 ; Tatiana D. Saint’ Pierre 1 ; Tércia Seixas 1 ; Helena Kehrig 1 ; Isabel Moreira 1 

1 Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Departamento de Química, 

Laboratório de Bioanalítica, Rua Marquês de São Vicente, 225, Gávea, CEP: 22453-900, Rio de 

Janeiro, RJ, Brazil. 

2 

Universidade Estadual de Campinas (UNICAMP), Instituto de Química, Grupo de 

Espectrometria, Preparo de amostras e Mecanização - GEPAM, C.Postal 6154, Campinas, CEP: 

13084-971, São Paulo, SP, Brazil. 

e-mail: isabel@puc-rio.br 

Metal concentrations were determined in muscle, gills, soft tissues and eggs in Callinectes sp. 

(n=26) from a reference site in Southeastern Brazil in males, ovigerous and non-ovigerous 

females, by inductively coupled plasma mass spectrometry (ICP-MS). Metallothionein (MT) and 

reduced glutathione (GSH) levels were also determined in all tissues and, to the best of our 

knowledge, this is the first study regarding both MT and GSH levels in Callinectes sp. eggs. For 

metal determination, samples were decomposed in an acid medium using a digestion block, by 

weighing 0.250 g of each composite sample in 5 mL of subboiled bidistilled nitric acid at 100 ° C 

for 5 h. After cooling, the volume was adjusted to 20 mL with ultrapure water. A 2 mL aliquot 

was removed and diluted with 2 mL of ultrapure water for subsequent mass spectrometry analysis 

using inductively coupled plasma mass spectrometry (ICP-MS). Metals were quantified using an 

ICP-MS in the standard mode, without the use of a reaction cell. For metallothionein 

determination, approximately 100 mg of each tissue were extracted according to the thermal 

extraction procedure described by Erk et al. (Erk et al., 2002). Metallothioneins were quantified 

using a spectrophotometric method conducting an Ellman's reaction, treated with 1 mol L -1 HCl 

containing 0.004 mol L -1 EDTA and 2M NaCl containing 0.00043 mol L -1 5,5'-dithiobis-2- 

nitrobenzoic acid (DTNB) buffered with 0.2 mol L -1 sodium phosphate, pH 8 and centrifuged at 

3000 xg for 5 min. The supernatant absorbance was then measured at 412 nm in a microplate 

reader and the MT concentration was estimated using a calibration curve plotted with GSH as 

external standard. MT levels were then estimated assuming a ratio of 1 mol MT corresponds to 20 

mol GH as described by Kagi (Kagi, 1991). For GSH determination, each sample (approximately 

200 mg) was homogenized in 2 mL of sodium phosphate buffer 0.1 mol L -1 pH 7 containing 

sucrose 0.25 mol L -1 . The samples were then centrifuged at 13,500 rpm for 30 min at 4 °C. The 

supernatants were then carefully removed and transferred to other sterile 2 mL tubes. DTNB 0.1 

mol L -1 in phosphate buffer pH 8.0 was then added to the sample supernatant at a 1:1 ratio. The 

samples were incubated for 15 min in the dark and their absorbance was measured in a microplate 

reader at 412 nm. Results demonstrated a significant trophic transfer of Zn and Cd from ovigerous 

females to eggs. Metallothionein showed increasing levels in the following order: muscle > gills > 

soft tissues > eggs, indicating higher oxidative stress and metal detoxification in the latter. GSH 

followed the same trend as MT, further corroborating the higher oxidative stress in eggs. 

Regarding human consumption, metal concentrations were lower than the maximum permissible 

levels established by international and Brazilian regulatory agencies, indicating that this species is 

safe for human consumption concerning this parameter. The presence of metals in Callinectes sp., 

however, is of great importance considering that this is a key species within the studied ecosystem 

and, therefore, plays a major role in the transference of pollutants to higher trophic levels. In 

-178 -



addition, the presence of significant metals concentrations found in eggs must be considered in 

this context, since crab eggs are eaten by several other species, such as shorebirds, seabirds, and 

fish. The increasing oxidative stress levels observed in eggs are also of concern since they may be 

related to developmental issues in this species. 

-179 -



(P15) 

ICP-MS METHODOLOGY FOR BLOOD TRACE ELEMENTS COMPOSITION 

ANALYSIS FOR PATIENTS WITH DIFFERENT STAGES OF TUMOR 

O.V. Kovalenko 1 , I.V. Boltina 1 , E.O. Pisarev 1 , G. A.Liubchenko 2 , L.S. Kyolodna 2 , N.Ya. Gridina 3 

, I.V. Kalinitchenko 4 

1 Medved`s Institute of Ecohygiene and Toxicology, Ministry of Health, Kyiv, Ukraine 

2 Taras Shevchenko National University of Kyiv, Ukraine 

3 

Institute of Neurosurgery, National Academy of Medical Science, Ukraine 

4 Bruker, 3500 West Warren Ave, Fremont, CA, USA 

e-mail: Kovalenko.Olesya@gmail.com 

It is known that about 8% of total tumors have genetic origins. The rest (about 92%) could be 

related to poor habits such as smoking, drinking, unhealthy life style, iatrogenic and environment 

factors. Deviations in optimal chemical elemental composition of blood could be a reason for or 

consequence of different health disorders, particularly cancerous tumors. 

We have been researching trace elements composition deviation between reference group of 

people - healthy patients and groups of those with a compromised medical history (oncologic 

pathology) and brain tumors (meningioma of different malignancy grades). 

Bruker 820 ICP-MS equipped with Ion Mirror optics and CRI mini-Collision Cell technology has 

been used for the trace element analysis due to its superior sensitivity and excellent interference 

suppression. One of the requirements for this work was to setup a reliable method for 

microelements quantitative and qualitative determination based on minimal sample preparation 

routine due to extra-large number of samples. 

The ICP-MS results obtained were compared to parallel cytogenetic study of peripheral blood 

lymphocytes in all chosen groups of patients. Lymphocytes cultivation and chromosome specimen 

preparation was carried out by a standard semi-micromethod. 

Samples and materials: Blood samples taken from group (aged 29 -55y.o.) treated for benign and 

malignant meningioma at Romodanov Institute of Neurosurgery (Ukraine) were analyzed at the 

ICP-MS trace element laboratory at Medved`s Institute of Ecohygiene and Toxicology. 

Results: 

Benign meningioma patients: increase [times] in concentration for Se-3.2, Fe-1.2 , Cr-6, Ni-4, Al- 

6, and I-3.2 and decrease for Zn-1.7, Mn-4, Sr-1.6, Ca-1.7 compared to the reference group. 

Malignant meningioma patients: increase [times] in concentration: Se-4.8, Cr-5, Ni-2.7, Al-9.6, 

Fe-1.7, I- 6.7, Mn-4 and decrease Cu-1.4, Zn-6, Sr-1.8, Ca-1.8 found in blood serum under the 

conditions of malignant meningioma development. 

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(P16) 

THE ISAS- X-RAY FLUORESCENCE BEAM LINE AT DELTA: POSSIBILITIES AND 

APPLICATIONS 

Roland Hergenröder, Alex von Bohlen and Martin Brücher 

Leibniz-Institut für Analytische Wissenschaften-ISAS, Interface Processes, Bunsen-Kichhoff 

Str.11, 44139 Dortmund, Germany 

e-mail: roland.hergenroeder@isas.de 

Recently, the Leibniz Institut für Analytische Wissenschaften started to maintain an X-ray 

fluorescence beam line at Delta a synchrotron located at the Technical University Dortmund. The 

experiment is set-up at a bending magnet. The double crystal monochromator equipped with either 

InSb(111) or Si(111) has a usable energy range from 1.5keV to 8keV. The beam line is designed 

for X-ray experiments under grazing incidence geometry and is equipped for experiments like X- 

ray fluorescence, X-ray absorption, X-ray reflectivity, XANES, etc. 

Spectrum of the polychromatic beam of BL2-the ISAS line. 

This contribution presents the principles and the possibilities of synchrotron-based X-ray grazing 

incidence for the measurements of element distribution profiles at surfaces and interfaces. 

Different experiments are presented ranging from element-specific nanoparticle size distribution 

measurements to elucidate element distribution along model bio-membranes. 

This presentation is an invitation to colleagues from all disciplines to use the possibilities of the 

ISAS beamline. 

-181 -



(P17) 

CHEMICAL SPECIATION OF INORGANIC BERYLLIUM FOR WORKING AREAS 

PARTICULATE MATTER SAMPLES: SEQUENTIAL EXTRACTION PROCEDURE 

DEVELOPMENT AND APPLICATION 

Thibaut Durand and Davy Rousset 

Institut National de Recherche et de Sécurité, Rue du Morvan CS60027, 54519 Vandoeuvre-lès- 

Nancy, France 

e-mail: Thibaut.Durand@inrs.fr 

It is well known that beryllium (Be) exposure is a concern in working areas and can lead to Be 

sensitization and chronic Be disease (CBD). Usually the method for determining occupational 

beryllium exposure requires to collect airborne particles by sampling a known volume of air 

through a filter disposed in a sampling device, for instance a closed-faced-cassette (CFC). 

Collected matter is digested in acid mixture prior to analysis of beryllium by spectrometry: 

electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma atomic 

emission spectrometry (ICP-AES) or inductively coupled plasma mass spectrometry (ICP-MS). 

ICP-MS is particularly useful due to its very low detection limit capability with regards to low 

beryllium occupational exposure limits (50 ng.m -3 , ACGIH 2010). However this method only 

allows total beryllium quantification, whereas Be-induced toxicity may be not only related to total 

concentration but also to particle size, surface area, number and chemical form 1,2 . In occupational 

environments, different beryllium species with various solubility could be encountered, from 

easily soluble beryllium salts to poorly soluble beryllium oxides. Difference in solubility will lead 

in different residence time in the body and different toxicity. It is then of prime importance to 

assess the proportion of beryllium species according to their solubility in occupational atmosphere. 

A four step sequential extraction procedure has been already developed for beryllium speciation 4 : 

it allows the separation of soluble salts, metallic beryllium, oxides and residual Be-containing 

silicates, using different extraction solutions. This procedure has been developed on bulk sample 

but it would not be directly applicable to CFC because it would require the removal of the filter 

from the cassette which could induce a bias by loosing material during transfer and by not taking 

into account cassette wall deposits. In this study, an improvement of the leaching procedure was 

proposed to have a direct and quick analytical method to perform speciation in solubility of 

inorganic beryllium collected on mixed cellulose ester (MCE) membranes disposed in CFC. The 

protocol consists on separating soluble salts, metal, oxides, and residual species with four specific 

extraction solutions (10 mL HCl 0.01M, 10 mL CuSO 4 0.1M (in HCl 0.1M), 10 mL NH 4 HF 2 1% 

(ABF), 15 mL HCLO 4 :HNO 3 :HCl:HF mixture) directly introduced subsequently into the CFC to 

take into account wall deposits. Four different beryllium species were investigated: soluble 

beryllium salts (BeF 2 and BeSO 4 ), beryllium metal (Be(0)), and beryllium oxide. These species, 

except for BeSO 4 , were tested separately, then in mixture. BeSO 4 were only tested in mixture to 

highlight some problems of selectivity. After reaction with the corresponding extraction solution 

introduced in CFC, the solution is filtered with an adapted filtration device and the quantification 

of beryllium is performed by ICP-MS with matrix-matched calibration solutions. Influence of 

parameters such as solid/liquid ratio, extraction duration, temperature, solution concentration, was 

also investigated. 

Limits of detection were calculated for the four extraction solution-induced matrices by repeated 

analyses of blank solutions which have gone through the whole extraction procedure. Obtained 

LODs are low, ≤ 4.6 ng.m -3 , (calculated for sampling duration of 8 h at flowrate of 2 L.min -1 ), 

lower than the tenth of the ACGIH limit value of 50 ng.m -3 . Single specie tests have led to good 

-182 -



recovery rates with at least 90% for each extraction solution, while mixture tests exhibited 

recoveries depending on the beryllium specie ratio initially introduced. Statistical analysis results 

for mixture have showed influence of each specie on the final result. 

Optimized method has been tested on samples from French factories for which a potential risk of 

beryllium exposure is suspected. Inhalable and respirable sampling devices have been used. 

Results were consistent regarding processes investigated. 

1 KENT M.S., ROBINS T.G., MADL A.K. - Is total mass or mass of alveolar-deposited airborne 

particles of beryllium a better predictor of disease? A preliminary study of a beryllium processing 

facility. Applied Occupational and Environmental Hygiene, 2001, 16, pp. 539-558. 

2 KELLEHER P.C., MARTYNY J.W., MROZ M.M., MAIER L.A., RUTTENBER A.J., YOUNG 

D.A., NEWMAN L.S - beryllium particulate exposure and disease relations in a beryllium 

machining plant. Journal of Occupational and Environmental Medicine, 2001, 43, pp. 238-249 

3 

PAUSTENBACH D.J., MADL A.K., GREENE J.F. - Identifying an appropriate occupational 

exposure limit (OEL) for beryllium: data gaps and current research initiatives. Applied 

Occupational and Environmental Hygiene, 2001, 16, pp. 527-538. 

4 

PROFUMO A., SPINI G., CUCCA L., PESAVENTO M. – Determination of inorganic beryllium 

species in the particulate matter of emissions and working areas. Talanta, 2002, 57, pp. 929-934. 

-183 -



(P18) 

SELECTIVE AND NON-SELECTIVE EXCITATION/IONIZATION PROCESSES IN AR/HE 

MIXED PLASMAS 

Sohail Mushtaq 1 , Edward B. M. Steers 1 , Juliet C. Pickering 2 and Karol Putyera 3 

1 London Metropolitan University, 166-220 Holloway Road, London, N7 8DB, UK 

2 Blackett Laboratory, Imperial College London, London SW7 2BW, UK 

3 Evans Analytical Group, 103 Commerce Blvd, Liverpool, NY 13088, USA 

E-mail: s.mushtaq@londonmet.ac.uk 

In low pressure analytical glow discharges (GD) such as Grimm-type sources, the plasma gas plays a 

vital role in the excitation and ionization processes in the discharge. As part of a wide study to 

identify unusual excitation processes affecting particular lines in GD, helium was added up to 60 % 

v/v to an argon plasma. The additional gas can drastically influence the emission intensities of the 

main plasma gas and sputtered analyte (Cu or Fe) due to selective excitation processes which are 

mainly dependant on the nature of the plasma gas and analyte. In order to understand better the 

excitation processes occurring, we have investigated the effect of Ar/He mixed plasmas on the 

electrical parameters, pressure required, sputter rate and emission intensities of sample (cathode) 

material and plasma gas. ‘Standard conditions’ (20 mA & 700 V with a 4 mm inner diam. anode 

tube) were used throughout. Spectral measurements were made using the Imperial College high 

resolution uv-vis Fourier transform spectrometer and involved over 370 spectral lines in the spectral 

range 200-900 nm. We discuss here the significance of the intensity changes recorded as the amount 

of helium in the plasma was varied. 

Ar I emission lines: It is shown in Fig. 1 that 

when helium is added to the plasma gas, 

significant changes in the normalized profiles 

of the Ar I 811.531 nm line occur, clearly due 

to an increase in self-absorption. In general, as 

the helium concentration is increased, argon 

atomic lines in the 600 – 900 nm region 

(transitions to the 4s levels) show increasing 

amounts of self-absorption and self reversal 

suggesting an increase in the population of the 

metastable 4s levels. A significant increase in 

the number density of argon atoms in these 

states would cause major changes in the 

excitation processes in the discharge. 

Ar II emission lines: 53 argon ionic lines between 345 – 510 nm were studied in various 

argon/helium mixtures. In Fig. 2 the intensity ratios of argon ionic lines (I Ar+He /I Ar ) are plotted 

against the Ar II excitation energy for 70% Ar + 30% He. The enhanced intensities of argon ionic 

emission lines with excitation energy ~ 20 eV are excited selectively by Penning excitation of 

ground state argon ions by helium metastable atoms, viz 

Ar o + + He m → Ar + * + He o + ΔE (1) 

Normalised intensity 

1.0 

Pure Ar 

90Ar + 10e 

0.8 

70 Ar + 30e 

Ar I 811.531 nm 

40 Ar + 60e 

0.6 

0.4 

0.2 

0.0 

12318.50 12318.75 12319.00 12319.25 12319.50 

Wavenumber/ cm -1 

Fig. 1 Normalized line profiles showing 

changes in self-reversal for various He 

-184 -



As there are two particles before and after the 

collision, conservation of energy and momentum 

can only be satisfied if the kinetic energy change, 

ΔE is small, so Penning excitation is a resonant 

reaction. The intensity of argon ionic lines from this 

energy group in particular strongly increases with 

the increase of helium concentration in the plasma. 

Fe II emission lines: 90 iron ionic lines between 230 

and 285 nm were identified. In general their 

intensity does not change greatly, but Fig. 3 shows 

that a group of iron ionic lines, upper energy near to 

19 eV, are excited by the non-selective Penning 

ionization by helium metastable atoms of ground 

state iron atoms, viz: 

Fe o + He m → Fe + * + He o + e - + ΔE (2) 

In this case, the additional particle produced allows 

energy and momentum conservation for a large 

range of positive values of ΔE. The process appears 

selective in Fig. 3 as the only lines emitted from 

levels closer to the helium metastable level are in 

VUV region below the lower wavelength limit of 

the Fourier transform spectrometer and therefore 

could not observed in this work. 

Fig. 2 Intensity ratios for argon ionic lines 

measured in 70%Ar + 30% He as a 

function of excitation energy (Cu sample). 

0 

12 13 14 15 16 17 18 19 2 

Excitation energy/ eV 

Cu II emission lines: With a copper cathode, 64 

copper ionic lines were studied in the range 200 – 

900 nm; a large number within 460 – 580 nm range 

were observable in Ar-He plasmas. It is suggested 

that these lines are predominately excited by 

asymmetric charge transfer between helium ions 

and ground state copper atoms (He-ACT) which is again a selective process. 

Fig. 3 Intensity ratios for iron ionic 

emission lines measured in 40%Ar + 

60% He as a function of excitation 

energy using Fe sample. 

Cu o + He + → Cu + * + He o + ΔE (3) 

Several intense copper ionic lines with upper energies in the range 16.2 – 16.5 e\V were also 

recorded using Ar-He mixtures. It appears that these intense copper ionic lines may be the results of 

cascade effects. The increase in the population of highly excited levels of copper ionic lines by He- 

ACT strongly affects the intensity of lines from lower levels. 

It was expected that these selective and non-selective processes would have significant effects on 

analytical applications of GD mass spectrometry. However, our MS studies using a Thermo Fisher 

Element GD MS showed a gradual increase in ion signal intensities of various minor and major 

constituents of matrix in Ar/He mixtures. The changes in intensities were not as dramatic as was 

expected from the considerable signal enhancements due to changes in excitation and ionization 

processes shown by our OES studies. 

Intensity ratio (I Ar+He / I Ar ) 

10 

8 

6 

4 

2 

(b) 

Fe II emission lines 

He m 

-185 -



(P19) 

THE MICROWAVE PHOTOCHEMICAL REACTOR FOR THE ON-LINE OXIDATIVE 

DECOMPOSITION OF P-HYDROXYMERCURYBENZOATE (PHMB)-TAGGED 

PROTEINS AND THEIR DETERMINATION BY LC-COLD VAPOUR GENERATION 

ATOMIC FLUORESCENCE DETECTION 

Beatrice Campanella 1 , Jose González Rivera 2 , Carlo Ferrari 3 , Massimo Onor 1 , Emanuela Pitzalis 1 , 

Alessandro D’Ulivo 1 and Emilia Bramanti 1 

1 C.N.R., Institute of Chemistry of Organometallic Compounds, UOS of Pisa, Via Moruzzi, 1, 

56124 Pisa, Italy. 

2 Chemical Engineering Department, University of Guanajuato, Noria Alta s/n 36050, Guanajuato, 

Gto. Mexico. 

3 National Research Council of Italy, C.N.R., Istituto Nazionale di Ottica, INO – UOS Pisa, Area 

di Ricerca, Via G. Moruzzi 1, 56124 Pisa (Italy). 

e-mail: dulivo@pi.iccom.cnr.it 

Chemical labelling in combination with mass spectrometry is appointed as a modern approach for 

quantifying biopolymers, especially proteins. Protein labelling approaches are generally based on 

elemental mass spectrometry techniques, specifically inductively coupled plasma-mass 

spectrometry (ICP-MS). 

In this work we present a novel method for the characterization and determination of proteins 

labeled with p-hydroxymercurybenzoate (pHMB, an organic mercury species widely used for 

mercaptan and thiolic compound labeling), based on the on line oxidation of pHMB-labelled 

proteins with a novel on-line UV/microwave (MW) photochemical reactor, followed by cold 

vapour generation atomic fluorescence spectrometry (CVG-AFS) detection [1,2]. MW/UV 

process leaded to the quantitative conversion of pHMB and protein-pHMB complexes to Hg(II), 

with a yield between 89±0.5% without using chemical oxidating reagents and avoiding the use of 

toxic carcinogenic compounds. The MW/UV oxidation system and the CVGAFS detection 

system has been hyphenated with reversed phase (RP) and size exclusion (SEC) liquid 

chromatography. Acetonitrile (ACN), one of the typical organic eluents in RPC, does not affect 

sensitivity when MW/UV oxidation system is used. 

LC-MW/UV-CVGAFS method has been applied to the characterization, separation and 

determination of several thiolic proteins (albumins, beta-lactoglobulin and k-casein) using SEC 

and RPC. Several denaturation systems (8 M urea, 3 M GdmSCN, 0.2% SDS, thermal 

denaturation, 20% methanol, 50% trifluoroethanol) have been employed to study pHMBovalbumin 

complexes, using ovalbumin as a model protein. The maximum number of titrated SHgroups 

for OVA has been obtained denaturing the protein with 0.2% SDS at room temperature 

(2.7 ±0.3 SH- groups). 

SEC-MW/UV-CVGAFS has also been applied to the study of thiolic proteins in human plasma 

from normal donors and from patients affectd by amyloidosis. Finally, the potentialities of RPC- 

MW/UV-CVGAFS have been explored for the characterization of proteic tryptic digests. 

REFERENCES 

[1] V. Angeli, C Ferrari, I. Longo, M. Onor, A. D’Ulivo and E. Bramanti. Analytical Chemistry 83 

(2011) 338-343. 

[2] Valeria Angeli, Simona Biagi, Silvia Ghimenti, Massimo Onor, Alessandro D'Ulivo, Emilia 

Bramanti. Spectrochimica Acta B, 66 (2011) 799–804. 

-186 -



(P20) 

STUDY OF THE INTERACTION OF CHLORINATED AND SULFOCHLORINATED 

PARAFFINS WITH GELATIN B AND SKIN POWDER. A MODEL FOR FATTENING IN 

THE LEATHER TANNING PROCESS 1 

Valentina Della Porta 1 , Susanna Monti 1 , Massimo Onor 1 , Alessandro D’Ulivo 1 , Emanuela 

Pitzalis 1 , Alice D’Allara 2 and Emilia Bramanti 1 

1 C.N.R., Institute of Chemistry of Organometallic Compounds, UOS of Pisa, Via Moruzzi, 1, 56124 Pisa, Italy. 

2 ENEA, UTTMATF, Via Ravegnana 186 48018 Faenza. 

e-mail: pitzalis@pi.iccom.cnr.it 

Fattening is crucial to confer exceptional softness, smoothness and elasticity on leather. Indeed, at 

the end of the tanning process leather does not contain enough lubricant to prevent it from drying 

into a hard mass. Fatting agents have the role of lubricating both the surface of collagen fibers and 

interfibrillar spaces by replacing water. 

Chlorinated and sulfo chlorinated paraffins (CPs and SCPs) are common fatting agents employed 

in the leather industry because it is supposed that they interact effectively with the collagen 

matrix. 

The most abundant collagen type consists of three polypeptide chains arranged in tight triplehelical 

structures where the conformation of each chain depends on the presence of glycine (GLY) 

and the high content of proline (PRO) and hydroxyproline (HPR). Fibrillar collagens contain 

uninterrupted sequences of GLY-X-Y triplets which are flanked by terminal globular domains 

(telopeptides). A careful analysis of the primary structure of collagen reveals the presence of some 

patterns and motifs, which may consist of a periodic distribution of certain sequences or features. 

For example, polar and hydrophobic residues are periodically clustered along the sequence of 

collagen I every 234 residues. 

Differently from fibrillar collagen, gelatin is a heterogeneous mixture of water-soluble proteins of 

high average molecular masses. These proteins are extracted by boiling skin, tendons, ligaments, 

bones, etc. in water. 

Little is known about the interactions of CPs/SCPs with collagen and gelatin. 

In this work we have performed experimental (FTIR spectroscopy) and computational (MD 

simulations) studies of the interaction of collagen, gelatin and skin powder with CPs and SCPs. 

The investigation of the reaction mechanisms involved in CPs/SCPs action on collagen can be a 

good starting point for the development of natural environmental-friend fatting agents1 and the 

definition of more effective and efficient industrial processes. 

(1) Life + EU Project ENV/IT/364 “ECOFATTING” 

-187 -



(P21) 

OPTIMIZATION OF ANALYTICAL TESTS FOR THE CHARACTERIZATION AND 

VALIDATION OF MERCURY-SORBENT MATRICES 1 

Massimo Onor, Emanuela Pitzalis, Alessandro D’Ulivo, Valentina Della Porta, Marco Carlo 

Mascherpa and Emilia Bramanti 


56124 Pisa, Italy. 

e-mail: onor@pi.iccom.cnr.it 

Atomic absorption spectrometry (AAS) and atomic fluorescence spectrometry (AFS) apparata 

were optimized to fast characterize the metal mercury adsorption capacity of carbon-based 

sorbents in the gas phase and in solution. These apparata was developed in the framework of an 

European project devoted to the optimization and production of a novel sorbent deriving from the 

pyrolitic conversion of waste tyres into activated carbon for the removal of mercury from gas 

streams impregnated with a sodium sulfide solution in order to improve its mercury binding 

capacity. 

In order to test the sorption properties in the gas phase, a selected amount of mercury released in 

an argon flow by a permeation tube kept thermostated at selected temperatures was delivered 

directly to the AAS or through a cartridge preloaded with activated carbon materials to be tested 

by switching two position six-port inert automated valve. In each experiment, accurately weighted 

amount of sorbents (in function of its capacity toward mercury determined in preliminary 

experiments) were charged into the fixed-bed reactor. The sorbent bed was maintained in place 

between two plugs of quartz wool tested, to be inert toward mercury. Prior to each adsorption 

experiment, the reactor was fully equilibrated at the desired temperature. Each sorption test was 

repeated at least three times and was reproducible to provide results within 3% for homogeneous 

samples. The gas flow rate was kept constant during the experiments by a mass flow controller 

(Brooks). AAS was used as mercury analyzer to continuously measure the elemental mercury Hg 0 

at the outlet. This instrumental set up allowed us the study of adsorption kinetic and the capacity 

of the sorbents. 

The mercury adsorption/binding capacity was also evaluated in solution in the perspective of an 

employment of the sorbent also for mercury removal from waste waters. For these experiments 

flow injection analysis coupled to Atomic Fluorescence Detector (FIA-AFS) was carried out in 

batch on samples (0.6-1 mg/mL) suspended and vortexed in Ultrapure water/4% methanol with 

0.5 mM Hg(II) at different times. After centrifugation the surnatant was diluted 10 times and 

analyzed by FIA-AFS. 

The characterization of sorbents was completed with the analysis by a DMA-80 mercury analyser 

(FKV) of sorbents after the adsorption of mercury for closing the mass-balance of entire process. 

1 EU project LIFE+2011 ENV/IT/109 “Low cost sorbent for reducing mercury emissions” 

-188 -



(P22) 

IMPROVEMENTS IN THE DETERMINATION OF SULFIDE, CYANIDE AND 

THIOCYANATE BY CHEMICAL VAPOR GENERATION COUPLED WITH HS-GC-MS 

Massimo Onor 1 , Sara Ammazzini 1,2 , Enea Pagliano 3 , Emanuela Pitzalis 1 , Emilia Bramanti 1 and 

Alessandro D’Ulivo 1 


56124 Pisa, Italy 

2 University of Pisa, Department of Chemistry and Industrial Chemistry, Via Risorgimento, 35 

56125 Pisa, Italy 

3 

National Research Council Canada, Ottawa, Ontario K1A 0R9, Canada 

e-mail: onor@pi.iccom.cnr.it 

The use of trialkyloxonium salts has been recently proposed for the determination of anionic 

species by chemical vapour generation (CVG) coupled with head-space gas chromatography mass 

spectrometry (HS-GC-MS). 

In particular the use of aqueous Et 3 O + BF 4 reagent is attractive because it is able to generate 

volatile ethyl derivatives of chloride, bromide, iodide, sulfide, cyanide, thiocyanate, nitrite and 

nitrate [1]. Fluoride can be also determined by using aqueous Et 3 O + FeCl 4 [2] 

Some anions such as sulfide, cyanide and thiocyanate show detection limits in the range of 200- 

400 ng/mL, which are more than two orders of magnitude worse than those obtained for the other 

anions. In the present work is reported a study for the optimization of the reaction conditions with 

the aims to get significative improvements in the sensitivity of CVG-HS-GC-MS determination of 

these anions. 

The experimental parameters, which are considered to play a role in the generation efficiency of 

volatile ethyl derivatives are: the reaction temperature, the amount of ethylating agent and the 

concentration of ammonia buffering solution. All experiments were performed by using a GC-MS 

system (Agilent 5975c mass spectrometer and 6850 gas-chromatograph equipped with head space 

autosampler and incubating tool (Combi PAL CTC .). 

Temperature was varied in the range of 30-90 °C, the concentration of Et 3 O + BF 4 

 

was varied in 

the range of 1-1000 mM and the concentration of ammonia in the range of 2.5-2500 mM. 

The optimized reaction conditions are 70 °C , Et 3 O + BF 4 

 

= 250 mM , NH 3 = 500 mM, 

respectively for sulfide and cyanide, 70 °C , Et 3 O + BF 4 

 

= 250 mM , NH 3 = 750 mM for 

thiocyanate. Under optimized conditions the detection limits (3s) are 0.08, 35 and 1.7 ng/mL for 

sulfide, cyanide and thiocyanate, respectively (1 mL headspace injected, 2 ml of sample plus 3 ml 

of reagents and internal standards in 10 ml vial), which represent improvement factors of 

410 3 ,10, 160 with respect to the previously reported figures [1]. 

Application to biological samples (thiocyanate and other anions in human saliva and plasma) and 

certified reference material (free cyanide and sulfide in 0.1% NaOH RTC-Fluka) are reported. 

[1] A. D’Ulivo, E. Pagliano, M. Onor, E. Pitzalis, R. Zamboni, Anal. Chem., 2009, 81 (15), pp 

6399–6406 

[2] E. Pagliano, J. Meija, J. Ding, R. E. Sturgeon, A. D’Ulivo, Z. Mester, Anal. Chem., 2013, 85 

(2), pp 877–881 

-189 -



(P23) 

DEVELOPMENT AND EVALUATION OF DESOLVATION SYSTEM FOR DROPLET 

DIRECT INJECTION NEBULIZER 

Yuki Kaburaki 1 , Tomokazu Kozuma 1 , Akito Nomura 1 , Takahiro Iwai 1 , Hidekazu Miyahara 1 , 

Akitoshi Okino 1 

1 Department of Energy Sciences, Tokyo Institute of Technology, Japan 

e-mail: kaburaki@plasma.es.titech.ac.jp 

In recent years, there is growing interesting in trace element analysis for single cell or single 

nano-particle. For example, cause of cancer or Alzheimer disease is hoped to be figured out by 

trace element in single cell [1] . Inductively Coupled Plasma Mass Spectrometry (ICP-MS) has been 

widely used for trace element analysis because of analytical figure of merit. However, 

conventional sample introduction system for ICP-MS consumes large amount of sample solution. 

So, it is difficult to realize individual single cell analysis. In our previous research, droplet direct 

injection nebulizer (D-DIN) was developed. D-DIN can introduce into the ICP droplet of diameter 

30 to 70 μm. By including cells in a droplet, this system enables to introduce single call to ICP. 

In 2012, we applied D-DIN system to ICP Time of Flight Mass Spectrometry (ICP-TOFMS) to 

realize multi-element analysis in a droplet sample. But, signal intensity of small droplet was higher 

than that of larger droplet. From this result, it was suggested that desolvation was not enough so 

the droplet size was too large. Thus, we developed desolvation system for D-DIN. Schematic of 

the system is shown in Fig. 1. Heating part is 150 mm of length and the gas temperature was 

measured by a thermocouple. Cooling part is used copper pipe spiral of 80 mm in length and 

cooled through water inside the pipe. 

Droplet has heated by around 200℃ heating 

carrier gas before introducing to ICP. The 

temperature in cooling part was around 10℃ for 

working as a condenser. To investigate effect of 

the heating system, we applied the system to ICP- 

Atomic Emission Spectrometry (AES). By using 

the droplet desolvation system, emission intensity 

of Ca ion enhanced about 10 times compare with 

normal system. Excitation temperature and 

electron number density was measured when 

droplet was introduced into the plasma. 

Excitation temperature was decrease of about 150 

℃ and electron number density did not change. 

These results show that stability of the plasma 

was not affect. To remove the water vapor, 

Fig. 1 Schematic of droplet desolvation 

cooling system was applied after the heating system. The spectroscopic characteristics 

such as emission intensity, excitation temperature and electron density will be presented. 

References 

H. Haraguchi et al., J. Anal. At. Spectrom., 19, 4 (2004). 

-190 -



(P24) 

STUDY OF THE EXCITATION PROCESSES INVOLVING OXYGEN AS AN ADDED 

GAS IN A NEON ANALYTICAL GLOW DISCHARGE PLASMA 

Sohail Mushtaq 1 , Edward B. M. Steers 1 and Juliet C. Pickering 2 

1 London Metropolitan University, 166-220 Holloway Road, London, N7 8DB, UK 

2 Blackett Laboratory, Imperial College London, London SW7 2BW, UK 


Investigations of the effects of oxygen as an added gas in a neon analytical glow discharge plasma 

with various samples (cathodes) over a wide spectral range have been undertaken using a Grimmtype 

Glow Discharge (GD) source and Fourier Transform Optical Emission Spectroscopy (FT- 

OES). Significant variations to the relative spectral line intensities of both the sputtered matrix and 

plasma gas are observed in presence of oxygen. Penning ionisation and Asymmetric Charge 

Transfer (ACT) are shown to be involved. 

Energy /eV 

22 

20 

18 

16 

14 

12 

O + 

 

 

Energy level of various elements 

Ne + o 

Nem 

 

 

Penning Ionization 

 

Ne-ACT 

 

 

 

 

10 

O 

Ne 

Cu 

Fig. 1 Schematic representation of some energy levels of 

relevant elements (atomic in blue, ionic in red). Only the 

region of interest from 10 eV up to 22 eV is shown. 

1.2 

Cu II 272.168 nm, 21.380 eV 

Cu II 242.443 nm, 21.378 eV 

1.0 

Cu II 246.850 nm, 21.410 eV 

Cu II 248.579 nm, 21.378 eV 

Cu II 252.930 nm, 21.410 eV 

0.8 

Cu II 270.096 nm, 21.410 eV 

EY(Ne + O2) / EY(Ne) 

0.6 

0.4 

0.2 

0.0 

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 

Oxygen concentration in Ne (%, v/v) 

Fig. 2 Emission yield ratios against various oxygen 

concentrations for selected Cu II lines (700 V & 20 mA.) 

It is obvious from Fig. 1 that there are 

several copper ionic energy levels close to 

the ionization energy of neon 

(~ 21.564 eV), which are suitable for 

asymmetric charge transfer, viz: 

Cu o + Ne + → Cu + * + Ne o + ΔE, (1) 

where the subscript o and superscript * 

represent ground and excited states 

respectively, and ΔE is the small energy 

difference which can be either positive 

(exoergic) or negative (endoergic). Both 

exoergic Ne-ACT and endoergic Ne-ACT 

are possible in case of copper sample. 

Copper ionic emission lines which are 

selectively excited by Ne-ACT can be 

identified in 240 – 275 nm range. Added 

gas can also be involved in ACT excitation; 

however, copper does not possess ionic 

energy levels suitable for ACT involving 

oxygen ions. 

The presence of oxygen in a neon plasma 

reduces the sputter rate, therefore, 

‘emission yield’ (EY), i.e., the intensity 

divided by the sputter rate and the 

concentration of analyte in the sample, of 

analyte lines have also been determined. 

In Fig. 2 the emission yield ratios 

(EY Ne+O2 /EY Ne ) of selected Cu II lines 

excited by Ne-ACT are plotted against 

various oxygen concentrations in neon. It 

is appeared that in neon/oxygen mixed 

plasmas, Cu II lines excited by Ne-ACT 

are reasonably weaker, probably due to 

-191 -



quenching of neon ions and respectively reduction of Ne- 

ACT. It is evident in Fig. 3 that 

by OES studies that there is significant decrease in Ne II spectral lines with the addition 

of oxygen in plasma gas. This 

is first thorough OES study of 

Ne/O 2 plasmas in Grimm-type 

glow discharges. So far no 

systematic MS studies on 

Ne/O 2 mixed plasmas have 

been carried out with similar 

sources and discharge 

conditions. 

The Cu ionic energy levels 

close to the neon metastable 

levels (16.62 & 16.72 eV) 

(see Fig. 1) may be populated 

by Penning ionization viz: 

Cu o + Ne m * → Cu + * + Ne o + e - 

+ ΔE (2) 

and also by cascade processes 

from higher levels. The 

corresponding Cu II emission 

lines occur in the 213 – 

Intensity ratio (I Ne + O2 / I Ne ) 

1.2 

1.0 

0.8 

0.6 

0.4 

0.2 

Ne II 321.819 nm, 56.301 eV - 52.449 eV 

Ne II 319.858 nm, 56.366 eV - 52.491 eV 

Ne II 338.842 nm, 56.406 eV - 52.748 eV 

Ne II 421.974 nm, 59.110 eV - 56.172 eV 

Ne II 439.199 nm, 59.123 eV - 56.301 eV 

Ne II 440.930 nm, 59.123 eV - 56.312 eV 

0.0 

0.0 0.2 0.4 0.6 

Oxygen concentration (% v/v) 

Fig. 3 Intensity ratios of selected neon ionic lines vs oxygen 

concentrations. (700 V, 20 mA, 4 mm diam anode tube). 

230 nm wavelength range. These Cu II lines are decreased with the addition of oxygen to the 

plasma, probably due to quenching of Ne m atoms. However, the decreases in intensities of these 

emission lines are less than those for the lines excited by Ne-ACT. 

A comprehensive investigation of Ne I 

spectral line profiles has been carried out 

in pure Ne and Ne/O 2 mixed plasmas. It 

appears that the large increase in the 

observed intensities of Ne I lines is 

occurred due to reduction of selfabsorption, 

when oxygen is added to 

plasma gas (see Fig 4). 

Intensity (a.u.) 

6 

5 

4 

3 

2 

Ne I 640.225 nm, 16.619 eV - 18.555 eV 

Pure Ne 

0.20% O 2 

0.40% O 2 

0.80% O 2 

Results of neon/oxygen are also 

compared with the case of argon/oxygen 

mixtures. In presence of oxygen, it is 

observed that sputter rate decreases 

significantly more in neon than in argon. 

The energy transfer collisions of Ne m 

atoms play a dominant role to both 

1 

0 

15614.8 15615.0 15615.2 15615.4 15615.6 

Wavenumber / cm -1 

Fig. 4 Lines profiles of Ne I 640.225 nm, showing 

self-reversal in some cases self-absorption for 

various oxygen concentration in neon discharge. 

dissociate the oxygen molecule and excite directly one of the dissociative products to energy 

levels which emit a group of intense oxygen lines in near-infrared region. Such a resonant energy 

transfer between Ar m atoms and the ground state molecules of oxygen in these particular levels is 

not possible in argon/oxygen mixtures. 

-192 -



(P25) 

INVESTIGATIONS ON THE USE OF AMMONIA AS A REACTION GAS TO 

OVERCOME INTERFERENCES IN RARE EARTH ELEMENTS BY ICP-MS 

Jessee Severo Azevedo Silva 1 , Tatiane de Andrade Maranhão 2 , Daniel L. Galindo Borges 1 , Vera 

Lucia A. Frescura 1 and Adilson José Curtius 1 

1 Universidade Federal de Santa Catarina, Florianópolis, SC, Brazil 

2 Universidade Federal do Rio Grande do Norte, Natal, RN, Brazil 

e-mail: jesseesevero@yahoo.com.br 

The interest in rare earth elements (REE) research in different areas has grown significantly since 

China, in 2009, decided to reduce the amount of REE exported to foreign countries. For many 

years China had been the greatest supplier and detainer of the technologies for the production of 

REE. After China’s restriction, many countries started to establish policies to increase REE 

production, which requires investment in specific research fields. 

Analyses of samples containing REE require sensitive and multielement techniques and, in this 

case, the most attractive technique is ICP-MS. However, REE determination by ICP-MS can be 

difficult, since these elements are susceptible to polyatomic interferences. The use of a 

reaction/collision cell, in which a reactive or collisional gas is used, is well reported as a solution 

to overcome polyatomic interferences. 

In this work, a study to evaluate the effect of NH 3 in reducing polyatomic interferences and on the 

signal of four REE was carried out. Blank solutions, containing only the interfering elements, and 

solutions containing the analytes and interfering elements were analyzed using different gas flow 

rates. All isotopic signals were monitored for each of the analytes (Gd, Lu, Nd ad Yb) in both 

solutions. The signal for possible secondary ions formed with the analytes (IO + or INH 3 ) was also 

monitored. The study showed an important formation of polyatomic interfering ions in the plasma 

environment, which could cause an increasing in the signal of the analytes, as can be seen in 

Figures 1 to 4 (A) . The use of NH 3 is effective in reducing these interferences. 

The effect of ammonia on the analyte signal was investigated and the results showed that NH 3 

causes a significant decrease in the signal for all analytes. Overall, as shown Figures 1 to 4 (B), 

ammonia gas flows ranging between 0.4 and 0.6 mL min -1 were proven effective in reducing 

interference effects of polyatomic ions over REE signals, which leads to the assumption that 

interference-free determination of the REE is feasible under these conditions. 

The monitoring of secondary ions formation with the analytes revealed that for Lu the use of NH 3 

contributes significantly to the formation of the ion mass 191, at low flow rate, but at higher flow 

rate the signal for this ion decreases (Figure 1 C). For Yb the formation of secondary ions was not 

observed. The monitoring of Gd secondary ions showed that the signal for the ion mass 171,172, 

173, 174 and 176 is significantly high at absence of NH 3 and at low gas flow rate a slight increase 

in the signal occurs (Figure 3 C). This suggests that the secondary ions formation occurs mostly in 

the plasma environment. For Nd the behavior is very similar, but no one contribution of the NH 3 

gas on the signal increasing is observed (Figure 4 C). 

-193 -



Intensity, s -1 

60000 

50000 

A 

700000 

600000 

40000 

500000 

191 

4800 

192 

400000 

193 

30000 

3600 

300000 

20000 

2400 

175 200000 

Lu 

1200 

10000 

176 Lu 

100000 

0 

0 

0.00 0.15 0.30 0.45 0.60 0.75 

0.00 0.15 0.30 0.45 0.60 0.75 

0.00 0.15 0.30 0.45 0.60 0.75 

NH NH 3 

flow rate, mL min -1 

3 

flow rate, mL min -1 NH 3 


Figure 1. Effect of NH 3 in the Lu signal for: (A) 10 µg L -1 Gd and Tb blank solution; (B) 10 µg L -1 Lu, Gd and Tb 

solution; and (C) in the signal of LuO + or LuNH 3 + . 

B 

175 

Lu 

176 

Lu 

7200 

6000 

C 


48000 

42000 

36000 

30000 

24000 

18000 

12000 

6000 

A 

170 

Yb 

171 

Yb 

172 

Yb 

173 

Yb 

174 

Yb 

176 

Yb 


180000 

150000 

120000 

90000 

60000 

30000 

B 

170 

Yb 

171 

Yb 

172 

Yb 

173 

Yb 

174 

Yb 

176 

Yb 

0 

0.00 0.15 0.30 0.45 0.60 0.75 

NH 3 


0 

0.00 0.15 0.30 0.45 0.60 0.75 

NH 3 



Figure 2. Effect of NH 3 in the Yb signal for: (A) 10 µg L -1 Gd and Dy blank solution and (B) 10 µg L -1 Yb, Gd and 

Dy solution. 

420000 

350000 

280000 

210000 

140000 

70000 

0 

0.00 0.15 0.30 0.45 0.60 0.75 

NH 3 


A 

154 

Gd 

155 

Gd 

156 

Gd 

157 

Gd 

158 

Gd 

160 

Gd 

700000 

600000 

500000 

400000 

300000 

200000 

100000 

0 

0.00 0.15 0.30 0.45 0.60 0.75 

NH 3 


Figure 3. Effect of NH 3 in the Gd signal for: (A) 10 µg L -1 Nd, Ce, Pr and La blank solution; (B) 10 µg L -1 Gd, Nd, 

Ce, Pr and La solution; and (C) in the signal of GdO + or GdNH 3 + . 

B 

154 

Gd 

155 

Gd 

156 

Gd 

157 

Gd 

158 

Gd 

160 

Gd 

42000 

36000 

30000 

24000 

18000 

12000 

6000 

0 

C 

170 

171 

172 

173 

174 

175 

176 

177 

0.00 0.15 0.30 0.45 0.60 0.75 0.90 

NH 3 



200 

160 

120 

80 

40 

142 Nd; 

144 

Nd; 

146 

Nd; 

150 

Nd 

A 

143 

Nd; 

145 

Nd 

148 

Nd; 

150000 

125000 

100000 

75000 

50000 

25000 

B 

142 

Nd 

143 

Nd 

144 

Nd 

145 

Nd 

146 

Nd 

148 

Nd 

150 

Nd 

30000 

25000 

20000 

15000 

10000 

5000 

158 

159 

160 

161 

162 

163 

164 

165 

166 

167 

C 

0 

0.0 0.1 0.2 0.3 0.4 

NH 3 


0 

0.00 0.15 0.30 0.45 0.60 0.75 

NH 3 


0 

0.00 0.15 0.30 0.45 0.60 0.75 

NH 3 


Figure 4. Effect of NH 3 in the Nd signal for: (A) 10 µg L -1 Ru and Te blank solution; (B) 10 µg L -1 Nd, Ru and Te 

solution; and (C) in the signal of NdO + or NdNH 3 + . 

-194 -



(P26) 

STUDY OF TETRACYCLINE FRAGMENTATION WITH LC-MS 

Martin Šala, 1 Drago Kočar, 2 Tadeja Lukežič, 3 Gregor Kosec 3 and Hrvoje Petkovič 3 

1 National Institute of Chemistry, Laboratory for analitical chemistry, Hajdrihova 19, 1000 

Ljubljana, Slovenia 

2 University of Ljubljana, Faculty of chemistry and chemical technology, , Aškerčeva 5, 1000 


3 Acies Bio, d.o.o., Tehnološki park 21, 1000 Ljubljana Slovenia 

e-mail: Martin.Sala@ki.si 

Tetracyclines are a class of medically important broad spectrum antibiotics that were discovered 

more than 60 years ago as fermentation products of soil bacteria from the group of actinomycetes. 

The core structure of tetracyclines consists of four rings, of which one is usually aromatic and 

their biosynthesis is is catalysed by complex enzymatic systems termed polyketide synthases. 

Massive use of this class of antibiotics led to wide-spread occurrence of resistance genes, thus 

there is immense need to develop new antibiotics with novel mode of action. In addition to the 

typical TCs, which bind strongly to bacterial ribosomes and inhibit translation, second group of 

TCs, the so-called atypical TCs, with yet unknown mode of action, such as anhydrotetracycline, 6- 

thiatetracycline and chelocardin (CHD). Considering CHD displays unusual tetracycline backbone 

and potent antibacterial activity with a mode of action fundamentally different from other TCs, 

CHD backbone can serve as suitable scaffold for biosynthetic engineering of novel antibacterials, 

which could be further derivatised through semi-synthetic efforts in order to develop compounds 

active against multi resistant pathogen strains. In search for new potentially medically useful 

tetracyclines, fast and simple identification and determination of their structure is of great 

importance. MS/MS determination of these class of compounds is based on the most abundant 

MRM transitions, where neutral loss of amino group, water or in some cases both occurs. Up to 

now fragmentation of tetracyclines was not studied in detail. We have investigated the 

fragmentation pathways of the most common clinically used tetracyclines as well as some 

structurally unusual tetracyclines. We also discuss the different fragmentation patterns of 

epimeres. 

-195 -



(P27) 

METHOD DEVELOPMENT FOR THE ANALYSIS OF ORGANOPHOSPHORUS 

COMPOUNDS IN LIPF 6 -BASED ELECTROLYTES 

Vadim Kraft, Martin Grützke, Martin Winter and Sascha Nowak* 


*e-mail: sascha.nowak@uni-muenster.de 

Lithium-ion batteries are widely used in modern consumer electronics and are increasingly used 

for electric vehicles. Due to the high energy density and good cycling stability these energy 

storage systems become more and more important for the economy. The main disadvantage of the 

batteries is limited cycle life due to unwanted chemical reactions for example of the electrolytes. 

Furthermore the high temperature accelerates the decomposition. To increase the efficiency of Liion 

batteries and understanding of the degradation steps is necessary. 

A series of experiments with commercially available non-aqueous LiPF 6 -based electrolytes has 

been carried out. The samples were stored at various temperatures for several weeks and analysed 

to investigate the thermal influence on the decomposition reactions. 

The separation of the decomposition products was performed by an ion chromatography system 

(IC). For improving of the separation different columns were used. Also a gradient step for the 

reduction of the retention time was applied. For the elucidation of the structural formula of the 

compounds the IC was coupled to electrospray ionization (ESI-MS). 

-196 -



(P28) 

IN-SITU MÖSSBAUER SPECTROSCOPY AS A NON-DESTRUCTIVE TOOL TO 

ANALYZE LITHIUM-ION BATTERY AGING 

Sascha Weber 1 , Thorsten Langer 1,2 , Falko Schappacher 1 , Rainer Pöttgen 2 and Martin Winter 1 

1 MEET Battery Research Center, University of Münster, Corrensstr. 46, 48149 Muenster, 

Germany 

2 Institute of Inorganic and Analytical Chemistry, University of Münster, Corrensstr. 28/30, 48149 

Muenster, Germany 

e-mail: Sascha.Weber@uni-muenster.de 

Lithium ion batteries suffer from capacity loss effects that shorten their lifetime. This is commonly 

called battery aging. To analyze the processes that occur in the cell and lead to the capacity loss it 

is important to develop analytical methods that can not only be applied under post-mortem 

conditions but also in-situ to a lithium ion full cell. 

Commonly Mössbauer spectroscopy is used to characterize new materials synthesized to be used 

as the electrochemically active part of lithium ion battery electrodes. Several groups have 

developed special in-situ cells to characterize e.g. LiFePO 4 electrodes. 

We present the application of Mössbauer spectroscopy on a lithium ion full cell in pouch bag 

design. The cell consists of a LiFePO 4 cathode and a graphite anode and uses organic electrolyte. 

Mössbauer spectra were recorded at several state of charge (SOC) levels and at several state of 

health (SOH) levels of the battery. 

From the recorded spectra the ratio of lithiated (LiFePO 4 ) and delithiated (FePO 4 ) active material 

was extracted and could be attributed to a certain SOC. Furthermore a shift of the phase ratio in 

dependence of the cell’s lifetime has been detected. This is correlated with the loss of capacity. So 

it is possible to assume that the amount of available lithium ions in the cell is too low to recharge 

all particles of the active material. 

-197 -



(P29) 

COMPARISON OF VARIOUS SPECTROSCOPIC IMAGING TECHNIQUES FOR 

INVESTIGATION OF HG AND SE METABOLISM IN PLANT TISSUES 

Marta Debeljak 1 , Johannes Teun van Elteren 1 , Katarina Vogel-Mikuš 2 , Alessandra Gianoncelli 3 , 

David Jezeršek 3 

1 National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia 

2 

Department of Biology, Biotechnical Faculty, University of Ljubljana, Večna pot 111, 1000 


3 

Synchrotrone Elettra, Strada Statale 14, 34149 Basovizza, Trieste, Italy 

e-mail: marta.frlic@ki.si 

Mercury (Hg) is one of the most toxic metals found in the environment, known to accumulate in 

food webs with a biomagnification pattern at successive trophic levels. Uptake, transport and 

transformation of Hg in plants depend on the soil properties as well as the plants metabolic 

processes. Since selenium (Se) resembles the chemical properties of sulphur and has a high 

affinity to bind Hg, Se could play an important role in mercury detoxification. Therefore, 

knowledge on the behaviour of Hg and Se in plant organisms might help us to characterize Hg and 

Se uptake and distribution in plant tissues and additionally aid in the development of 

phytoremediation techniques and lowering of Hg uptake into food webs. 

This work focused on the development/application of imaging of spatial distribution of Hg and Se 

in plants at the macro (organ/tissue) and micro (tissue/cellular) level. Plants (Zea mays L. and 

Helianthus annuus L.) were grown in hydroponic nutrient solution with 0.8 mg/kg Se(IV) or 

Se(VI) in commercial pot substrate amended with 50 mg/kg of HgCl 2 . The samples were prepared 

using cryo-fixation/microtoming. For elemental imaging both laser ablation-ICPMS and 

synchrotron radiation-based micro-X-ray fluorescence spectrometry techniques were used for fast, 

low-resolution (> 8 μm) mapping of large areas (≥ 1 mm 2 ) and high-resolution (sub-μm) mapping 

of small areas (≤ 0.05 mm 2 ), respectively. 

A) B) 

Figure 2: Microscopic image (Nikon Eclipse TE200 inverted microscope) of a maize root sample cross-section 

subjected to laser ablation (A) and the mercury distribution (mg/kg) in this section (B). 

Laser ablation-ICPMS mapping was conducted with a 213 nm Nd:YAG laser interfaced with a 

quadrupole ICPMS instrument; calibration was realized with Se and Hg-spiked Tissue freezing 

medium ® embedding resin. 2D mapping via conventional parallel line scanning protocols was 

found to be unusable due to sorption of mercury onto the internal parts of the LA device, giving 

-198 -



rising to memory effects resulting in serious loss of resolution and inaccurate quantification. Spot 

analysis on a virtual grid on the surface of the sample using washout times of 10 s in between 

spots greatly alleviated problems related to these memory effects. 

µ-XRF measurements of the Hg and Se distribution were performed at the ID22 beamline, ESRF, 

Grenoble (France); the energy was set at 13 keV and the beam was focused using a Kirkpatrick- 

Baez mirror to generate a 3.5 1.5 µm 2 spot size. µ-XRF measurements of the Se distribution 

were also performed at the TwinMic beamline, synchrotron Elettra, Trieste (Italy); the energy was 

set at 1.64 keV and the beam was focused using a zone plate to generate a 1.2 µm 2 spot size. 

A) 

Figure 3: Microscopic image (Nikon Eclipse TE200 inverted microscope) of a maize root sample cross-section with 

the marked region of interest (A) and the mercury distribution (counts/sec) in a maize root by µ-XRF at the ID22 

beamline, Grenoble, showing retention of Hg in the endodermis and cortex (B), where it is colocalized with sulphur 

(C). 

Imaging with the mentioned techniques led to the following findings: i) Hg was localized 

mainly in root epidermis and endodermis (Figure 1); ii) High-resolution imaging showed that Hg 

was also present in the cortex and that it was colocalized with sulphur, hereby confirming that Hg 

preferentially binds to sulphur ligands (Figure 2); iii) In Se(IV)-treated plants, Se was mainly 

localized in epidermal and sub-epidermal root tissues, while in Se(VI)-treated plants higher 

concentrations were seen in root cortex, indicating that Se(VI) is more mobile than Se(IV); iv) In 

Se(VI)-treated plants Se was readily translocated to the leaves, where it mainly accumulated in 

leaf mesophyll (Figure 3). 

Figure 4: X-ray absorption image (A) and distribution of selenium (counts/sec) in sunflower leaf sample by µ-XRF at 

the TwinMic beamline, Trieste, showing Se accumulation in leaf palisade mesophyll (B). 

All imaging techniques proved to be suitable for Se localization in plant tissues. Although the SR- 

µ-XRF techniques generated higher resolution image maps, laser ablation-ICPMS is a technique 

which is better accessible and less time consuming. 

-199 -



(P30) 

SIZE CHARACTERISATION OF METALS IN TUNNEL WASH WATER AS A 

FUNCTION OF TIME AND DETERGENT 

Jon-Henning Aasum 1 , Elin Gjengedal 1 and Sondre Meland 1, 2 

1 Department of Plant and Environmental Sciences, Norwegian University of Life Sciences, PO 

Box 5003, N-1432 Ås, Norway 

2 Norwegian Public Roads Administration, Environmental Assessment Section, PO Box 8142 

Dep, N-0033 Oslo, Norway 

e-mail: jon-henning.assum@student.umb.no 

Contaminated water from roads, including water from washing of tunnels, can be a threat to 

lakes and rivers. The tunnels in Norway are regularly cleaned in the form of sweeping and 

washing with water to avoid unfavourable conditions in the tunnel such as bad air quality, 

accumulation of dirt, and corrosion on the tunnel walls and other technical infrastructure. The 

washing frequency is dependent on the traffic. Hence, tunnels with annual average daily traffic 

(ADT) above 15 000 vehicles are washed at least 6 times/year while tunnels with ADT below 

4000 vehicles are washed once every fifth year. In brief, tunnels are washed by using detergent 

and high pressure cleaning leading to large volumes of highly contaminated water. The detergent 

concentrations in the discharged tunnel wash water typically ranges between 0.2 % and 0.5 % 

volume concentration. The washing process often leads to emissions of partly highly polluted 

wastewater. Due to the high pollutant content in the tunnel wash water there is now common 

practice to treat the wash water before it is discharged to a nearby recipient. The most frequent 

applied method is to build sedimentation basin inside or outside the tunnel. This is reasoned by the 

fact that a lot of the contaminants are associated to particles. Hence, the treatment of tunnel wash 

water is based on sedimentation processes removing particle-associated contaminants, and 

therefore, the removal of dissolved contaminants, i.e. the mobile and assumed bioavailable 

fraction, is considered low. Currently there is little information on how the detergent affects the 

sedimentation processes, and the present study aimed to investigate how the detergent influenced 

this process by size fractionating metals in tunnel washing water as a function of time and 

detergent concentrations. It is important to obtain knowledge of the effect of detergent on 

fractionation of metal in tunnel wash water to optimize procedures for operation of the 

sedimentation basin and thereby minimize the impact on the natural environment. The cleaning 

process was simulated in a lab and the metals were separated depending on particular and 

molecular size using filters and a centrifuge. 

The conditions of the sedimentation basin used to remove contaminates from the wash water 

was simulated in the laboratory using 15 L rectangular plastic water tanks (Asaklitt) stored at 3 – 4 

°C for three weeks. Wash water was obtained during washing of the 3.8 km long Nordby tunnel 

situated along E6 south of City of Oslo (Akershus county). The tunnel has two separate tubes with 

four lanes. The ADT is approximately 40 000 vehicles/day. Varying amounts of the detergent (TK 

601, Teknisk Kjemisk Produksjon AS) was added to the wash water, resulting in 0, 0.5 and 3.0 % 

volume concentrations. Each treatment was conducted in triplicates. There were therefore a total 

of 10 water tanks, including a water tank with distilled water. 

-200 -



A sampling system was constructed in the cooling room to avoid contamination of the water 

during the experiment. This system included two pumps, which pumped water from the water 

tanks at a set depth, half the depth of the tank, to a three-way valve. This sent the water through 

for sample collection, or to a 0.45 μm filter (GWV High Capacity Groundwater Sampling 

Capsules with 0.45 μm Versapor membrane, Pall Life Sciences). The filtered samples were then 

further processed by using a centrifugal tube with a 10 kDa filter (Amicon® Ultra-15 10K 

Centrifugal Filter Devices, Merck Millipore Ltd.) and centrifuged at 5000g for 15 minutes. Thus, 

the following size fractions were obtained: particulate (>0.45 µm), colloidal (0.45 µm – 10 kDa) 

and low molecular mass fractions (< 10 kDa). 

The water tanks were left still for 21 days after the addition of the detergent to allow 

sedimentation. Using the sampling system, water samples were collected after 0, 30 minutes, 1 

day, 3 days, 9 days and 21 days after the start time. The total, filtered and centrifuged samples 

were then analysed for concentrations of metals using ICP-MS (AGILENT 8800 QQQ 

instrument). 

In addition to metals, the pH, conductivity, TOC, DOC, concentrations of anions and the 

concentrations of tensides in the water were determined. 

Currently, the water samples are being analysed and the results will be presented at the 

conference. 

-201 -



(P31) 

DIRECT DETERMINATION OF BROMINE IN PLASTIC MATERIALS BY MEANS OF 

SOLID SAMPLING HIGH-RESOLUTION CONTINUUM SOURCE GRAPHITE 

FURNACE MOLECULAR ABSORPTION SPECTROMETRY 

María R. Flórez, E. García-Ruiz, Martín Resano 

Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain, 50009 

e-mail: garciae@unizar.es 

The ubiquity of plastic materials and the huge amount of plastic waste generated in the modern 

world has led to a growing concern in terms of the environmental impact. In this context, special 

attention is being paid to the variety of different inorganic and organic additives incorporated to 

the structure of the polymers to enhance their qualities and their leakage to the environment. Most 

polymeric materials, and particularly those aiming to be employed in the production of electronic 

devices, electrical appliances, clothing and furniture, are very often protected against ignition by 

the addition of the so-called brominated flame retardants (BFRs). 

While new environmentally safe flame-retardants alternatives are being investigated, regulations 

and restrictions in the use of organo-BFRs are being implemented in order to lower the impact by 

legally banning or setting maximum limits to total contents. It is essential then to have robust 

analytical methods for monitoring the presence of these compounds in raw plastic materials. 

Whenever the purpose is to have information about total BFRs content (most legal limits are 

established regarding this parameter) rather than or prior to gather information for each isolated 

compound, determination of total Br content in the sample becomes a reliable indicative. 

Most usual methods for determining Br in BFRs require extensive sample preparation steps to 

have the sample in an appropriate liquid form. This step needs to be thoroughly controlled in order 

to minimize the risk of Br losses due to its high volatility. Few approaches have been made up to 

date focusing on the development of methods for the direct determination of the solid materials, 

Thus, some more work stills to be needed regarding the development of simple and fast 

methodological approaches with enough sensitivity to fulfil the requirements of the current EU 

regulations concerning the use of BFRs in electrical and electronic equipment. 

It is the goal of this paper to develop a simple procedure for the direct determination of total Br 

content in plastic samples by means of high-resolution continuum source graphite furnace 

molecular absorption spectroscopy. This method is based in the formation of the diatomic 

molecule CaBr, 1 stable in gas phase at relatively high temperature, and the recording of its 

molecular spectra in the vicinity of 625.315 nm, using aqueous standards for calibration. 

References 

1. M. D. Huang, H. Becker-Ross, S. Florek, U. Heitmann, M. Okruss, Spectrochim. Acta Part B, 

2013, 63, 566–570 

-202 -



(P32) 

CHANGES IN CHEMICAL COMPOSITION OF URBAN PM 2.5 BETWEEN 2010 AND 

2013 IN HUNGARY 

Tamás Szigeti 1 , Mihály Óvári 1 , Franco Lucarelli 2 , Gyula Záray 1 , Victor G. Mihucz 1 

1 

Department of Analytical Chemistry, Eötvös Loránd University, 1117 Budapest, Hungary 

2 Department of Physics and Astronomy, University of Florence/INFN, 50019 Sesto Fiorentino, 

Italy 

e-mail: tamas.szigeti@yahoo.com 

Aerosol particles play a key role in urban air quality because their adverse effects on human health 

and local environment. In the new EU Directive (2008/50/EC), an annual mean PM 2.5 (particles 

with aerodynamic diameter smaller than 2.5 μm) concentration of 25 μg/m 3 has been set as target 

value as of 1 st of January 2010. However, the monitoring of the chemical composition of PM 2.5 is 

still not regulated. 

PM 2.5 sampling was performed about 15 m away from a busy road in the city centre of Budapest, 

Hungary. High-volume aerosol sampler (30 m 3 /h) was used for the collection of the aerosol 

particles for 96 hours (from Monday morning to Friday morning) in the first week of each month 

from June 2010 onto 150 mm quartz fibre filters (Whatman QM-A). Field blanks were also 

employed. 

The analyses included (i) gravimetric determination of PM 2.5 mass concentration; (ii) trace element 

determination (Bi, Cd, Co, Cr, Cu, Fe, Ga, Li, Mn, Mo, Ni, Pb, Pt, Rb, Sb, Sn, Te, Tl, U, V, Zn) 

after microwave‐assisted aqua regia and sonication‐assisted water extraction by inductively 

coupled plasma sector field mass spectrometry; (iii) evaluation of major ion concentrations in the 

aerosol samples subjected to sonication‐assisted water extraction by ion chromatography; (iv) 

assessment of total carbon and its water soluble part by a C/N analyzer; (v) determination of 

organic and elemental carbon by a thermal-optical transmission technique using a Sunset 

Laboratory OC/EC analyser. 

Seasonal variation was observed in: 

(i) the PM 2.5 mass concentration; 

(ii) some trace element concentration (i.e., Fe, Zn, Pb, Cd and Tl); 

(iii) the major anion content (sulphate vs nitrate). 

The financial support through grant TÁMOP-4.2.2/B-10/1-2010-0030 is hereby acknowledged. 

-203 -



(P33) 

DETERMINATION OF FLUORINE USING HIGH RESOLUTION CONTINUUM 

SOURCE MOLECULAR ABSORPTION SPECTROMETRY (HR-CS MAS) 

René Nowka and Heike Gleisner 

Analytik Jena AG, Konrad Zuse Straße 1, 07745 Jena, Germany 

e-mail: R.Nowka@analytik-jena.de 

For the first time, state of the art atomic absorption technology (HR-CS AAS) allows the 

determination of non-metals with an AAS instrument, contrAA Analytik Jena AG Germany. 

The spectrometer used is equipped with a high intense continuum radiation source (Xe short arc 

lamp), a high resolution double Echele monochromator and a CCD array detector. 

By converting the analytes not into atoms like in conventional line source AAS but into 

characteristic molecules allows the determination of nonmetals eg fluorine by molecular 

absorption spectrometry (MAS). 

HR-CS MAS is a new, sensitive method for the analysis of the total content of fluorine and other 

non metals in aqueous and organic solutions as well as directly in solids – independent of the 

bonding form. 

This study shows the determination of fluorine in concentrated nitric and sulfuric acid without 

complicated sample preparation. Both, free as well as organically or inorganically bound fluoride 

is converted to the target molecule gallium mono fluoride (GaF) in a graphite furnace for 

subsequent spectrometric determination. 

This means, for the first time, a simple, fast and reliable spectrometric method is available for 

fluorine determination in almost every matrix and over a wide concentration range. 

Graphite furnace HR-CS MAS is a precise, robust and interference free as graphite furnace AAS 

and is not subject to any restrictions with regard to the pH value and the sample matrix, so that 

sample preparation is reduced to a minimum. 

-204 -



(P34) 

DETERMINATION OF TRACE ELEMENTS IN BLACK AND WHITE PEPPERS BY 

XRF SPECTROMETER EQUIPPED WITH POLARIZATION OPTICS AND ITS 

DEVELOPMENT TO IDENTIFICATION OF THEIR PRODUCTION AREA 

Akiko Hokura 1 , Megumi Shibasawa 1 and Noriko Kuze 2 

1 Department of Green and Sustainable Chemistry, Tokyo Denki University 

Senju-Asahicho, Adachi, Tokyo 120-8551 Japan 

2 Kaneka Sun Spice Co., Ltd, Juso-higashi, Yodogawa, Osaka 532-0023 Japan 

e-mail: hokura@mail.dendai.ac.jp 

Agricultural products are increasingly labeled with their geographical origin in many countries. 

Geographical identification can be useful for branding strategy purposes and to help consumers in 

their selection of foodstuffs. Spices are commonly used all over the world. The large quantities of 

spices are imported from Asian countries to Japan. The technique for determination of the 

geographic origin of agricultural products is needed. Mineral composition is one of the useful 

factors for that. The aim of this study is to develop the analytical method for determination of 

trace elements in spices such as black and white peppers by XRF. The chemometrics analyses 

using the data are conducted for determination of their geographic origin. 

Black and white peppers produced in south-eastern Asia were used in this study. The pepper 

sample was milled and homogenized. The weighed amount of 0.5 g was pressed into a tablet and 

subjected to XRF analysis. An XRF spectrometer equipped with polarization optics, Epsilon 5 

(PANalytical), was used to determine the elemental concentration. 

Figure 1: Linear Discriminant Analysis plot showing excellent 

separation of the different production area of black pepper. 

Eq. 1 y = - 0.0071[Cl] + 0.0008[K] - 0.0205[Ca] + 0.1098[Mn] - 0.7333[Cu] - 

0.7581[Rb] + 0.0042[Sr] + 75.4225 

Eq. 2 y = 0.0087[Cl] - 0.0028[K] - 0.0493[Ca] + 0.561[Mn] - 1.2705[Cu] + 

1.0703[Rb] + 2.2167[Sr] - 4.6172 

Eq. 3 y = - 0.5431[Cl] + 0.0242[K] + 0.0617[Ca] - 9.3196[Fe] + 

2.757[Mn]+4.4237[Cu] - 41.9998[Rb] + 1675.75 

-205 -



We successfully demonstrated to determine the multielement concentrations in spices with a rapid 

and easy way using the XRF spectrometer. The minimum detection limits for 11 elements (Cl, K, 

Ca, Mn, Fe, Cu, Zn, Br, Rb, Sr, Cd) were sub-ppm levels. The principal component analysis 

(PCA) and the linear discriminant analysis were carried out by using the elemental concentration 

of peppers to determine their geographic origin. Black peppers of south-eastern Asia were 

characterized based on their elemental composition (Fig. 1). The presented method demonstrated 

the effectiveness of determining the geographic origin of spices. 

[1] M. Shibasawa, N. Kuze, K. Inagaki, I. Nakai, A. Hokura, Adv. X-Ray. Chem. Anal., Japan, 43, 

369-380 (2012). 

This work was partially supported by Research Institute for Science and Technology of Tokyo 

Denki University. Grant Number Q11E‐05/ Japan. 

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(P35) 

DETERMINATION OF SELENIUM USING CHEMICAL AND PHOTOCHEMICAL 

VOLATILE COUMPOUNDS GENERATION COUPLED WITH ATOMIC ABSORPTION 

SPECTROMETRY 

Marcela Rybinova 1 , Vaclav Cerveny 1 and Petr Rychlovsky 1 

1 

Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Albertov 

6, CZ-128 43 Prague 2, Czech Republic 

e-mail: rybinova.marcela@seznam.cz 

Selenium is one of the elements for which there is a thin border between their essential and toxic 

concentrations in environmental system; therefore it is necessary to pay attention to their 

determination. Presented study was focused on the determination of selenium in aqueous samples 

using two methods of its volatile compounds generation. First, newly emerging technique of UVphotochemical 

generation was used and then conventional chemical generation was applied for 

comparison. Atomic absorption spectrometry with the externally heated quartz tube (QF-AAS) 

was chosen for the detection with both approaches. 

The principle of conversion of nonvolatile precursors (inorganic selenium(IV)) from the 

condensed phase to volatile species is different. To be specific, in the case of UV-photochemical 

generation, volatile compounds are formed by the effect of UV irradiation in the presence of a low 

molecular weight organic acid (formic, acetic, propionic or malonic). Reaction mechanism 

remains the subject of discussion. In contrast to UV-photochemical generation, chemical 

generation is based on reaction with a reducing agent, most commonly NaBH 4 , with the 

involvement of high-purity mineral acid (generation according to ”hydrogen transfer theory”). 

For UV-photochemical generation, attention was first paid to the construction of the photoreactor. 

Photoreactor was realized by attaching reaction coil to the surface of low-pressure Hg vapor UV 

lamp (20 W, 254 nm). The subject of interest was the material and the length of the coil. PTFE 

and quartz tubes of different diameters were tested. Optimum experimental conditions for UVphotochemical 

volatile compounds generation using formic acid were found after the completion 

of the apparatus. Formic acid was chosen for the study as a representative of simple organic acids. 

Following key parameters were optimized: the sample flow rate, the carrier gas flow rate as well 

as the auxiliary hydrogen flow, the concentration of formic acid or the concentration of additives. 

Analyte response was significantly increased by adding HNO 3 . With the instrumental setup and 

the optimum analytical conditions, a detection limit of 39 ng L –1 Se(IV) with a repeatability of 1.7 

% (RSD, n = 10) was obtained. 

Similarly, optimum experimental conditions for more frequently used chemical generation were 

studied. Some of the tested parameters were the same, e.g. the sample flow rate or the carrier gas 

flow rate, others were logically different. Namely the concentration and the flow rate of the 

reducing agent NaBH 4 or the concentration of HCl, which was required for acidification of the 

reaction mixture. A detection limit of 105 ng L –1 Se(IV) with a repeatability of 1.3 % (RSD, n = 

10) was achieved by chemical volatile compounds generation. 

As the results show, UV-photochemical generation is a useful alternative to the conventional 

chemical generation technique. Not only because of its low detection limits obtained but also 

because of high sensitivity (comparison of slopes of calibration curves). 

Acknowledgments 

This work was supported by MSMT (project No. MSM 0021620857), Charles University in 

Prague (project SVV267215 and project UNCE 204025/2012). 

-207 -



(P36) 

EFFECT OF ZINC IN HISTORICAL IRON BASED INK CONTAINING DOCUMENTS: 

A MULTI-SPECTROSCOPIC APPROACH 

Marta Manso 1 , Ana Mafalda Cardeira 1,2 , Tânia Rosado 3 , Mara Silva 3 , Agnès Le Gac 1,4 , Sofia 

Pessanha 1 , Mauro Guerra 1 , Stéphane Longelin 1 , Ana Teresa Caldeira 3 , António Candeias 3,5 and 

Maria Luísa Carvalho 1 

1 Centro de Física Atómica da Universidade de Lisboa, Av. Professor Gama Pinto 2, 1649-003 

Lisboa, Portugal 

2 Faculdade de Belas-Artes da Universidade de Lisboa, Largo da Academia Nacional de Belas 

Artes, 1249-058 Lisboa, Portugal 

3 Laboratório HERCULES e Centro de Química de Évora, Universidade de Évora, Largo Marquês 

de Marialva 8, 7000 Évora, Portugal 

4 Departamento de Conservação e Restauro, Faculdade de Ciências e Tecnologia, Universidade 

Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal 

5 

Laboratório José de Figueiredo, Direção Geral do Património Cultural, Rua das Janelas Verdes 

37, 1249-018 Lisboa, Portugal 

e-mail: luisa@cii.fc.ul.pt 

Biodeterioration phenomena represent a complex of physical and chemical alteration processes in 

various materials, such as those constituting the objects that represent our cultural heritage [1]. 

Storage documents inside structures intended for their preservation has created new manmade 

environments for microbial species such as fungi and bacteria to inhabit [2]. Microorganisms such 

as fungi and bacteria are the most important agents of biodeterioration in museums, storage rooms, 

libraries, collections and restoration studios. Historical material made of paper and parchment with 

high amounts of organic binders is especially susceptible to fungal deterioration [3, 4]. 

In this work, X-ray fluorescence analyses were carried out on documents from the 13th to the 16th 

century to infer the inks potential effect on their preservation. Two types of iron-based inks were 

identified on each document, one containing mainly iron and the other one, iron and zinc. These 

documents, either on parchment or paper support, were all strongly attacked by microorganisms 

exhibiting dark brownish stains all over them. Nevertheless, this biological alteration was not 

observed in the adjacent areas to inks containing zinc. In fact the presence of a light aureole 

around the written text may confirm the assumption that this element inhibits the degradation 

process of both support and ink. 

Microbiologic assays were performed aseptically, collecting several samples from the areas of the 

document with significant contamination and degradation. The samples were inoculated in a 

selective culture media and identified according to the macroscopic and microscopic features. 

For the evaluation of microflora proliferation a combination of spectroscopic approach using 

scanning electron microscopy (SEM), scanning electron microscopy coupled with energy 

dispersive X-ray spectrometry (SEM-EDS) and also Raman microscopy to detect alteration 

products were used. 

The microbiological study allowed the identification of filamentous fungi, yeast strains (mainly 

Rhodotorula sp.) and a few bacterial strains. 

-208 -



Keywords: biodeterioration; historical documents; metal based inks; spectroscopy techniques 

References: 

[1] F. Pinzari, G. Pasquariello, A. De Mico. Biodeterioration of Paper: A SEM Study of Fungal 

Spoilage Reproduced Under Controlled Conditions. Macromolecular Symposia 238 (1), 2006, pp. 

57-66. 

[2] M. Montanari, V. Melloni, F. Pinzari, G. Innocenti.Fungal biodeterioration of historical library 

materials stored in Compactus movable shelves." International Biodeterioration & Biodegradation 

75 (0), 2012, pp. 83-88. 

[3] K. Sterflinger, F. Pinzari. The revenge of time: fungal deterioration of cultural heritage with 

particular reference to books, paper and parchment. Environmental Microbiology 14 (3), 2012, pp. 

559-566. 

[4] L. K. Kraková, S.A. Chovanová, A. Selim, A. Šimonovičová, A. Puškarová, A. Maková, D. 

Pangallo. A multiphasic approach for investigation of the microbial diversity and its 

biodegradative abilities in historical paper and parchment documents. International 

Biodeterioration & Biodegradation 70 (0), 2012, pp. 117-125. 

Acknowledgments: 

This work was partially supported by the Fundação para a Ciência e Tecnologia – The Awakening 

of the Manuelin foral charters: science and technology insights into the masterpiece - 

SPTDC/EAT-EAT/112662/2009. Marta Manso and Sofia Pessanha acknowledge the support of 

Fundação para a Ciência e Tecnologia for the grants SFRH/BPD/70031/2010 and 

SFRH/BD/60778/2009, respectively. Authors would like to thank Silvestre Lacerda, Director of 

the National Archive Torre do Tombo, Sónia Domingues, Anabela Ribeiro and Mário Costa for 

the support, the suggestions, and the fruitful discussions. 

-209 -



(P37) 

EVALUATION OF CALCIUM AND PHOSPHORUS IN TOOTH ENAMEL EXPOSED 

TO BLEACHING GEL 

Godinho J. 1 , Pessanha S. 2 , Silveira J 1 , Mata A. 1 , Carvalho M.L. 2 

1 

Grupo de investigação em Bioquímica e Biologia Oral, Unidade de Investigação em Ciências 

Orais e Biomédicas da Faculdade de Medicina Dentária da Universidade de Lisboa, Cidade 

Universitária 1649-003 Lisboa, Portugal 

2 

Centro de Física Atómica da Universidade de Lisboa, Av. Professor Gama Pinto 2 1649-003 

Lisboa, Portugal 

The purpose of this work is to assess whether the elemental content of Ca and P in tooth enamel is 

altered when bleaching the teeth with a bleaching gel containing 10 % (w/w) of carbamide 

peroxide. 

Ten anterior healthy teeth, extracted for periodontal or orthodontic reasons, were selected and 

preserved in a 0.5% (w/w) chloramine solution for no longer than 6 months. After confirming that 

there were no irregularities in the vestibular surfaces of the teeth, cuts were made in order to 

obtain 8 mm x 2 mm samples. The samples were then treated with the bleaching product through 

8-hour periods during 14 days accordingly to manufacturer instructions and placed in artificial 

saliva between each application to simulate the oral environment. 

The elemental content of the teeth before and during treatment was determined by means of micro 

Energy Dispersive X-Ray Spectrometry (-EDXRF). The equipment used consists on an X-ray 

tube OXFORD XTF5011 with a Mo anode and a Silicon Drift Detector (SDD) Vortex-60EX® 

with an active area of 50 mm 2 and a 12.5 μm thickness Be window. The radiation emitted by the 

X-ray tube is focused by means of polycapillary optics, allowing a focal spot of 100 μm. 

The quantitative analysis of the samples was carried out using WinAXIL software package 

(Canberra, Belgium) and statistical treatment performed by SPSS V.21 (IBM, USA). In this 

preliminary study a tendency for a decrease in Ca and P concentrations after bleaching treatment 

was observed. 

-210 -



(P38) 

ASSESSMENT OF ESSENTIAL ELEMENTS AND HEAVY METALS CONTENT ON 

MYTILUS GALLOPROVINCIALIS FROM RIVER TAGUS ESTUARY 

I. Santos 1 , M. Diniz 2 , M. L. Carvalho 3 , J. P. Santos 1 

1 CFA, Departamento de Física, Faculdade de Ciências e Tecnologia, FCT, Universidade Nova de 

Lisboa, 2829-516 Caparica, Portugal 

2 REQUIMTE, Departamento de Química, Centro de Química Fina e Biotecnologia, Faculdade de 

Ciências e Tecnologia, Universidade Nova de Lisboa, Quinta da Torre 2829-516, Caparica, 

Portugal 

3 Centro de Física Atómica Universidade de Lisboa, Av. Prof. Gama Pinto 2, 1649-003, Lisboa, 

Portugal 


European countries are one of the largest producers and consumers of mussels whether collected 

in the open sea or produced in aquaculture. In this work we analyze the trace elemental content in 

edible tissue of Mytilus galloprovincialis collected in 4 different sampling areas in the mouth of 

river Tagus estuary in Lisbon. One of the sampling points was considered clean and it was at the 

sea coast in Cascais. The other three regions were closer to the city and may include contaminated 

areas: Trafaria, Cacilhas on the south and Belem on the north. 

The concentrations of essential elements (S, K, Ca, Fe, Cu, Zn, As, Br and Sr) were obtained by 

energy dispersive x-ray fluorescence spectrometry, while toxic elements (Cr, Cd, Hg, Se and Pb) 

were obtained by inductively coupled plasma mass spectrometry (ICP-MS). The latter technique 

was used owing to its higher sensitivity, since these elements were not detected by the first 

technique. 

Potassium and S are present at the highest concentration in all the studied samples reaching 4520 

ug.g -1 and 2500 ug.g -1 (fresh weight) respectively in the sea coast samples. 

The highest levels for toxic elements were found in two areas close to the city: 0.09 ug.g -1 and 

0.33 ug.g -1 for Cd and Pb (fresh weight) respectively, both exceeding the maximum allowed 

values (0.05 ug.g -1 and 0.30 ug.g -1 respectively). Concerning the other toxic elements no values 

above the recommended regulations were found. 

The results obtained for toxic elements were submitted to the Kruskall Wallis test in order to 

check significant difference between the elemental concentrations in mussel tissues from clean 

and contaminated sampling sites. The difference was significant to Pb, Cd and Se (p



(P39) 

CHARACTERIZATION OF CALCIUM SULPHATE AND GLUE SIZING UNDER 

CALCIUM CARBONATE GROUND LAYERS IN FLEMISH AND LUSO-FLEMISH 

PAINTINGS - ANALISYS BY SEM-EDS AND µXRD 

Vanessa Antunes 1 , Maria José Oliveira 2 , Helena Vargas 2 , António Candeias 2 , Maria Luísa 

Carvalho 3 , Ana Isabel Seruya 3 , João Coroado 5 , Luís Dias 4 , José Mirão 4 , Vitor Serrão 1 

1 

Instituto História da Arte da Faculdade de Letras da Universidade de Lisboa (IHA-FLUL) , 

Alameda da Universidade, 1600-214 Lisboa, Portugal 

2 Laboratório José de Figueiredo / Direcção-Geral do Património Cultural (LJF-DGPC), Rua das 

Janelas Verdes 37, 1249-018 Lisboa, Portugal 

3 

Centro de Física Atómica da Universidade de Lisboa (CFA-FCUL), Av. Prof. Gama Pinto, 2. 

1649-003 Lisboa, Portugal 

4 

Laboratório HERCULES, Universidade de Évora, Largo Marquês de Marialva 8, 7000-676 

Évora, Portugal 

5 

Instituto Politécnico de Tomar (IPT)/GeoBioTec ID&T unit, , 2300-313 Tomar, Portugal 

e-mail: vanessahantunes@gmail.com,mjoseoliveira@gmail.com, lena_na_gabela@yahoo.com 


This work regards the study of painting techniques, specifically addressing the methodology used 

on the preparation of ground layers in Portuguese workshops. The invisible ground layer and its 

influence in Portuguese paintings of the 15th and16th centuries, is a question to be settled in this 

study. The influence of the Flemish painting in Portugal is evident in stylistic and iconographic 

themes during 15 th and the earlier 16 th centuries. Regarding the painting materials, we confirmed 

that this influence was extended to ground layers technique. The use of a sizing with specific 

sulphate compounds to render an impermeable layer between the support and the calcium 

carbonate layer was verified by SEM-EDS and confirmed by µXRD. 

Pictorial corpus in study 

In this study of calcium carbonate ground layers in painting, it was studied a set of two series of 

the same altarpiece from early16 th century, assigned to a Bruges Flemish painting workshop. Both 

series were ordered by D. Afonso of Portugal, bishop of the city of Évora between 1485-1522 to 

the renovation of the main chapel of the city´s Cathedral, started in 1495. The altarpiece has a 

series of thirteen paintings dedicated to the life and glorification of Virgin Mary and a series of six 

paintings dedicated to the Passion of Christ. 

Of the set of luso-flemish paintings with calcium carbonate ground layers two paintings were 

analysed from the circle of followers of the regius painter Nuno Gonçalves, both dated from the 

second half of the 15 th century .The Adoração dos Magos e Santos Franciscanos (S. Francisco e 

Sto. António) [1-3], from Santa Helena do Monte Calvário monastery, was totally covered in the 

17 th century by other painting. After being uncovered in the 20 th century by a deep restoration, is 

nowadays in Évora’s Cathedral Museu de Arte Sacra ; Santo Franciscano from Funchal Cathedral 

[3-7] was also partially repainted and was uncovered in the 21 st century. 

The painting Nossa Senhora da Rosa , also dated from the second half of the 15th century, 

-212 -



originally from the College of St. Jerónimo de Coimbra and nowadays in Museu Nacional de 

Machado de Castro, Coimbra, is connected to Coimbra's workshop. Attributable to mestre 

Delirante de Guimarães [8], this painting is also a remarkable case study in the history of 

conservation and restoration in Portugal. After institutional discussion it was decided in the 20 th 

century to totally uncover the painting of the 16 th century that overlapped it [9]. 

From the last quarter of the 16 th century was also studied the painting Incredulidade de S.Tomé, 

nowadays in Museu Nacional de Arte Antiga, and assigned to Anthonis Blocklandt, dutch painter 

and master of the spanish painter Fernão Gomes, between 1570 and 1572 [10]. 

Experimental 

A first multianalytical study published in 2009 by Instituto Português de Conservação e Restauro 

on the Évora’s flemish altarpiece, allowed to identify traces of calcium sulphate under calcium 

carbonate ground layers [11]. After this identification, these and other paintings with calcium 

carbonate ground layers were analysed by different techniques, in order to confirm and compare 

the results. 

SEM imaging (SE and BSE modes) using an Hitachi 3700N scanning electron microscope 

coupled with a Bruker XFlash 5010 SDD detector was used to identify different layers of size and 

calcium carbonate in ground layers. With this technique it was confirmed the exact location of the 

size layer between the support and the ground layer. 

SEM-EDS was also used to identify elemental composition of calcium carbonate inorganic 

compounds. The samples, coated with a conductive film of carbon, allowed refined measurement 

of relevant parameters of calcium carbonate and sizing. The technique allowed to verify the 

inorganic compounds existent in the sizing layers, such as Ca and vestigial S. 

Micro X-ray diffraction (µXRD), performed on a Bruker AXS D8 Discovery 

diffractometer with Cu K radiation and Gadds detector, allowed the identification of crystalline 

phases through the EVA code.This technique confirmed the existence of trace Gypsum (dihydrated 

calcium sulphate) on sizing layer of Calcite rich (calcium carbonate) ground layers. 

Conclusion 

The microanalytical approach applied in this study allowed to improve the knowledge on the 

technical options of Flemish and Luso-Flemish paintings from 15 th to 16 th centuries. Critical 

analysis of the results obtained for inorganic materials existing in sizing layers, brought novel 

conclusions relatively to its characterization. 

Acknowledgements 

This work has been financially supported by Fundação para a Ciência e Tecnologia 

(FCT/MCTES - PIDDAC) through project “The invisible ground layer and its influence in 

Portuguese paintings of the 15th and16th centuries: a question to be settled” (PTDC/EAT- 

HAT/100868/2008) program Ciência e Inovação 2010 (POCI 2010) and PhD grant (SFRH / BD / 

37929 / 2007) POCI2010 e QREN-POPH – typology 4.1 (co-participated by the European Social 

Fund (ESF) and national funds MCTES). The authors acknowledge also the institutions 

MNMC,IHA-FLUL, LJF-DGPC,IPT, CFA-FCUL and Hercules Lab-UEvora. 

1. Markl, D., O Painel da Igreja do Calvário de Évora e a pintura portuguesa do século XV. A Cidade de 

Évora: Boletim de Cultura da Câmara Municipal (1ª Série), 1973. 56: p. 5-11. 

2. Serrão, V., O maneirismo e o estatuto social dos pintores portugueses. Arte e artistas. 1983, Lisboa: 

Imprensa Nacional-Casa da Moeda. 480p. 

3. Baptista Pereira, F.A., Imagens e Histórias de Devoção. Espaço, Tempo e Narrativa na Pintura Portuguesa 

do Renascimento (1450-1550). 2001, Faculdade de Belas-Artes da Universidade de Lisboa: Lisboa. 

-213 -



4. Rodrigues, D., A pintura num século de excepção,1450-1550. Arte portuguesa da pré-história ao século XX 

ed. D. Rodrigues. Vol. 6. 2009, Lisboa: Fubu editores,Sa. 

5. Fraga, R., O painel quatrocentista da Sé do Funchal: novos dados para o estudo material, in Artis, revista do 

Instituto de História da Arte da Faculdade de Letras da Universidade de Lisboa, L.A.G. Barbosa & Xavier, Editor. 

2007, Instituto de História da Arte da Faculdade de Letras da Universidade de Lisboa: Lisboa. p. 93-120. 

6. Fraga, R., Notável painel quatrocentista da escola de nuno Gonçalves descoberto no Funchal. Islenha: temas 

culturais das sociedades insulares, 2000. 27: p. 40-59. 

7. Carvalho, J.A.S., Problemas da pintura quatrocentista. Obras isoladas e oficinas regionais, in História da 

Arte Portuguesa,Da Pré-História ao «Modo» Gótico Temas e Debates, P. Pereira, Editor. 1995, Círculo de Leitores e 

Autores: Lisboa. p. 473-485. 

8. Carvalho, J.A.S., O mestre delirante de Guimarães, in A colecção de pintura do Museu de Alberto Sampaio: 

séculos XVI-XVIII. 1996, Instituto Português de Museus. p. 17-39. 

9. Santos, M.R., Solução adoptada no preenchimento de lacunas num retábulo do sec. XV pertencente à capela 

da Misericordia de Coimbra-texto para a comunicação num congresso luso-espanhol realizado em Lisboa, Lisboa 31 

Março-4 abril 1970, Processo de restauro nº 81/69, Editor. 1970, Instituto José de Figueiredo: Lisboa. p. 4. 

10. Dacos-Crifó, N., Incredulidade de São Tomé, in A Pintura Maneirista em Portugal. Arte no tempo de 

Camões, Catálogo, V. Serrão, Editor. 1995, Comissão Nacional para as Comemorações dos Descobrimentos 

Portugueses: Lisboa. p. 245-247. 

11. Isabel Ribeiro, L.E., Maria José Oliveira,José Carlos Frade, Estudo material do retábulo de Évora. 

Conservação e restauro: cadernos 2009. 6/7. 

-214 -



(P40) 

TRACE ELEMENT ENRICHMENT OF LIVING NOURISHMENT AQUATIC 

ORGANISMS AND DETERMINATION OF THEIR UPTAKE BY ATOMIC 

ABSORPTION SPECTROMETRY 

Milán Fehér 1 , Edina Baranyai 2 , Edina Simon 3 , István Szűcs 1 , Péter Bársony 1 , József Posta 2 , László 

Stündl 1 

1 Institute of Animal Husbandry, University of Debrecen, 4032 Böszörményi street 138., Debrecen, 

HUNGARY 

2 Department of Inorganic and Analytical Chemistry, University of Debrecen, 4032 Egyetem 

square 1, Debrecen, HUNGARY 

3 Department of Ecology, University of Debrecen, 4032 Egyetem square 1, Debrecen, HUNGARY 

email: feherm@agr.unideb.hu 

Barramundi (Lates calcarifer) is a predatory fish species native in Southeast Asia and Australia. 

Cobalt, manganese and zinc are essential in fish nutrition since they are vital in trace amount for 

many living functions of vertebrates. The main aim of recent study is to investigate the 

accumulation and interactive effect of Co, Mn and Zn on the larval growth of barramundi, when 

the uptake occurs through a nourishment organism. 

In our experiment newly hatched Artemia nauplii was enriched with cobalt chloride, zinc sulphate 

and manganese chloride. Concentrations were 50 and 100 mg L -1 for CoCl 2 (Co-1 and Co-2) and 

for MnCl 2 (Mn-1 and Mn-2) individually, as well as for CoCl 2 along with ZnSO 4 (Co-Zn-1 and 

Co-Zn-2) and for CoCl 2 along with MnCl 2 (Co-Mn-1 and Co-Mn-2) in combination. A total of 

1900 barramundi larvae from 15-30 day post hatching were fed supplemented Artemia in 9 groups 

of treatments in duplicate. Artemia was sampled, washed by ultrapure water then centrifuged. 

Moisture content was determined by gravimetric method. Samples were digested on a hot plate 

with the mixture of 65 % (m/m) HNO 3 and 30 % (m/m) H 2 O 2 prior to analysis. The Co, Zn and 

Mn concentration of Artemia and 40 larvae from each treatments were determined by FAAS and 

GFAAS method. Blank samples were set to verify the purity of applied reagents. 

All treatments had significant effect (p



(P41) 

ATION OF NON-MEMBRANE ELECTROLYTIC CELL FOR ELECTROCHEMICAL 

VOLATILE SPECIES GENERATION OF TRANSITION METALS 

Jakub Hraníček 1 , Andrea Kobrlová 1 , Václav Červený 1 , Tomáš Vacek 1 , Tomáš Matoušek 2 and Petr 

Rychlovský 1 

1 Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Hlavova 

2030, CZ-12843 Prague 2, Czech Republic 

2 Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, 602 00 Brno, Czech Republic 

e-mail: jakub.hranicek@natur.cuni.cz 

Electrochemical generation (EcG) technique is one of significant approaches for a gaseous phase 

sampling technique in AAS, which is nowadays sufficiently examined for typical hydride forming 

elements (such as As, Se, Sb, Te, ...). On the other hand, there are many other analytical useful 

volatile compounds (including transition and noble metals) for electrochemical generation, which 

have not been sufficiently investigated. This study is focused on the possibilities of continuous 

electrochemical generation of gold and silver volatile species with on-line quartz atomizer-AAS 

detection including novel non-membrane electrolytic cell. 

Experimental setup used for electrochemical generation of volatile species of transition metals was 

the same as it is common for electrochemical hydride generation used for typical hydride forming 

elements determination. This setup consisted mainly of electrolytic cell, whose construction 

parameters strongly influenced the analytical signal (absorbance). Furthermore the experimental 

setup included carrier gas – argon (inserted upstream and downstream the cell) , transporting 

system made of Teflon tubing of different inner diameters, hydrostatic gas/liquid separator and 

externally heated quartz tube atomizer, which was placed in an optical path of atomic absorption 

spectrometer. 

In this work, novel design of electrolytic cell (non-membrane electrolytic cell) was tested. This 

type of cell, unlike of other commonly used for electrochemical hydride generation, does not 

include an ion exchange membrane, which separated liquid and gaseous product of electrode 

reaction from both electrode chambers. The result of this is that particularly the gaseous products 

released from the anode chamber are introduced directly with a volatile species of transition 

metals into the atomization/detection system. The body of non-membrane electrolytic cell was 

made from the Teflon with diameter 70 x 30 x 15 mm. The scheme of this cell with inserted 

electrodes is show below. 

Preliminary experiments were performed to optimize relevant working parameters for both 

transition metals. These parameters included shape and type of cathode material, type and 

concentration of common electrolyte, carrier gas flow rate (upstream/downstream the cell), 

electrolyte flow rate, value of generation electric current and atomization temperature. Under the 

optimal working conditions, calibration and other characteristics were found for both metals. The 

limit of detection 0.81 / 0.19 µg ml –1 and sensitivity 3.0 · 10 −3 / 5.1 · 10 −3 were obtained under the 

optimal conditions for gold / silver, respectively. About 5 times sensitivity enhancement was 

observed after addition of small amount of Triton X-100 and DDTC (sodium 

diethyldithiocarbamate) into the electrolyte stream. Atomic absorption spectrometry with flame 

atomization was used for determination of the analyte concentration in the waste solution to 

estimate the conversion efficiency from the liquid form (nearly 65%). As in other cases, even for 

this cell construction it was observed that appreciable amount of the analyte was reduced on the 

cathode surface. 

-216 -



Non-membrane electrolytic cell 

1 – Pt (Cu, Pb/Sn) electrode (cathode), 2 – Pt electrode (anode), 3 – electrolyte inlet, 4 – to 

gas/liquid separator, 5 – Teflon block, 6 – gasket, 7 – Plexiglas cover 

To discover the assumed mechanism of electrochemical generation of volatile gold species, the 

technique ICP-MS was used instead of AAS. For this sensitive technique the calculated detection 

limit was about 0.040 µg ml –1 for gold determination. 

This work was financially supported by the Ministry of Education, Youth and Sports of the Czech 

Republic (project MSM0021620857) and by the Charles University in Prague (project UNCE 

204025/2012). 

-217 -



(P42) 

ASSESSMENT OF NUTRIENTS OF ESCAMOLES ANT EGGS LIMOTEPUM 

APICULATUM M BY SPECTROSCOPY METHODS 

Virginia Melo 1 , Tomas Quirino 1 , Concepción Calvo 2 , Karina Sánchez 1 and Horacio Sandoval 1 

1 Universidad Autónoma Metropolitana, Calz. Del Hueso 1100, México, 04960 D.F. México 

2 Instituto Nacional de Ciencias Médicas y Nutrición Salvador Zubirán, Vasco de Quiroga 15, 

México 14000 D.F. México 

e-mail: vmelo@correo.xoc.uam.mx 

ABSTRACT 

Edible insects, escamoles ant eggs of the Formicidae family are consumed by cultural tradition at 

rural communities and by sensory characteristics at high class restaurants of Mexico, however 

people ignore the importance of insect consumption in the nutrition of humans and the benefits of 

spectroscopy methods in food analysis. The aim of this study is to analyze nutrients of escamoles 

ant eggs by spectroscopy methods and investigate the benefits of their use can provide at 

laboratory work. Escamoles were gather the second week of March 2012, at Hidalgo state and 

analyze moisture and macronutrients by AOAC methods (2002), amino acids by cation exchange 

chromatography, tryptophan was determined by a colorimeter method, fatty acids by gas 

chromatography using helium as a carrier (AOAC, 2002), fat soluble vitamins A, D, and E by high 

performance liquid chromatography resolution (Manual Waters Acc-QTAG), and minerals by 

atomic absorption spectrophotometers and phosphorus by colorimeter (AOAC, 2002). 

Data obtained: 

Moisture: 48.54% Dry sample: 51.46% 

Macronutrients dry basis (%): 

Proteins: Lipids: Minerals: Crude fiber Soluble 

carbohydrates: 

42.25 32.96 7.85 1.51 14.23 

Aminoacids (g/16 g Nitrogen): 

Isoleucine: 4.6 Leucine: 7.2 Lysine: 5.7 

Methionine: 3.2 Cysteine: 1.4 Phenylalanine: 6.2 

Tyrosine: 7.1 Threonine: 4.1 Tryptophan: 0.8 

Valine: 6.3 Histidine: 2.9 Aspartic acid: 8.5 

Serine: 4.7 Glutamic acid: 15.2 Proline: 6.3 

Glycine: 6.5 Alanine: 7.5 Arginine: 5.7 

Fatty Acids (%): 

C16:0 Palmitic acid: 20.18 C18:0 Stearic acid: 2.785 

C18:1 Oleic acid: 0.26 C18:2 Linoleic acid: 67.66 

C18:3 linolenic acid: 4.61 C20:5 Araquidonic acid: 1.16 

-218 -



Fat soluble vitamins: 

Vitamin A, Retinol 

Vitamin D, cholecalciferol 

Vitamin E, alpha tocopherol 

505.15 mcg/100g 

3.61 mcg/100g 

2.22 mg/100g 

Minerals (%): 

Sodium: 0.069 Potassium: 0.085 Calcium: 0.97 

Phosphorus: 0.83 Iron: 0.023 Zinc: 0.29 

Copper: 0.01 Magnesium: 0.973 Manganesum: 0.003 

Nutrients value might change due to biotic and abiotic conditions of the environment and maturity 

of insect eggs, nevertheless the value of escamoles has an adequate amount of nutrients. 

In conclusion, spectroscopy methods are a good tool to assess nutrients in foods, a little amount of 

sample is need, save chemical reagents and time, the operation with spectroscopy methods are 

cheap, however equipment is very expensive and should be handled by special trained staff. 

Bibliography 

AOAC Association of Official Analytical Chemists. Official Methods of Analysis of the 

Association of Official Analytical Chemists. 17 th Edited by W. Horwitz AOAC, Arlington. USA. 

(2002). 

Fling, S.D. and Gregerson, D.S. Peptide and Protein Molecular Weight Determination by 

Electrophoresis using a High Molarity Tris Buffer System without Ureas. Anal Biochem 155:83- 

88 (1986). 

Gehrke, C.W., Rexroad, P.R., Schisla, R.M., Absheer, J.S., and Zumwalt. Quantitative Analysis of 

Cysteine, Methionine, Lysine and Nine Other Amino Acids by a Single Oxidation. 4 th Hydrolysis 

Method. J. Assoc. Off. Anal. Chem. 70:171-174 (1987). 

Manual Waters Acc-QTAG, Manual No. WAT052874. (1993). 

Spies, J.R., Chambers, D.C. Chemical Determination of Tryptophan in Proteins and Protein 

Containing Plant Products with Dimethylaminocinnamaldehyde. Landwirsch, Frosch. Sonderb. 

27:96-109 (1972). 

-219 -



(P43) 

SPECTROSCOPIC STUDY OF THE AGEING PROCESSES IN TANNIN DYED 

TEXTILES 

S. Legnaioli 1 , G.H. Cavalcanti 2 , G. Lorenzetti 1 , V. Palleschi 1 , E. Grifoni 1 , I. Degano 3 , M. P. 

Colombini 3 , E. Ribechini 3 

1 

Institute of Chemistry of Organometallic Compounds, CNR 

Area della Ricerca del CNR di Pisa, Via G. Moruzzi, 1 - 56124 Pisa ITALY 

2 



Campus da Praia Vermelha - CEP 24210-346 - Niterói – Rio de Janeiro BRAZIL 

3 Department of Chemistry and Industrial Chemistry, University of Pisa, 

Via Risorgimento, 35 - 56126 Pisa ITALY 

e-mail: s.legnaioli@pi.iccom.cnr.it 

The study here presented aims at modelling the ageing processes undergone by textile fibres dyed 

with iron-galls and at identifying suitable conservation protocols. Tannins are natural polyphenols, 

contained into several kind of plant; they are mordant dyestuff, applied principally on wool and 

silk, whose application is divided into four steps: 1) application of the mordant (FeSO 4 ) to the 

fibre 2) preparation of the colour bath with raw material containing hydrolysable tannins 3) 

immersion of the mordanted fibre in the dye bath 4) formation of a black insoluble complex 

between tannins, mordant and fibres. This specific chemical system is subjected to different kind 

of degradation processes, which have been compared with those observed for iron-gall inks on the 

basis of LIBS, micro-Raman and GC/MS analysis. 

-220 -



(P44) 

SPECTROSCOPIC STUDIES OF XII-XIV CENTURY ITALIAN GOLD COINS BY X- 

RAY FLUORESCENCE 

M. Baldassarri 1 , G.H. Cavalcanti 2 , M. Ferretti 3 , A. Gorghinian 4 , E. Grifoni 5 , S. Legnaioli 6 , G. 

Lorenzetti 6 , L. Marras 5 , E. Violano 6 and V. Palleschi 6,7 

1 

Museo Civico di Montopoli in Val d'Arno 

Via Guicciardini, 55 - Montopoli V/A - Pisa (ITALY) 

2 Instituto de Fìsica, Universidade Federal Fluminense 


Campus da Praia Vermelha - CEP 24210-346 - Niterói – Rio de Janeiro (BRAZIL) 

3 Institute for Technologies applied to Cultural Heritage 

Area della Ricerca Roma 1 - Montelibretti 

Via Salaria Km. 29.300, C.P. 10 - 00016 Monterotondo St. – Roma (ITALY) 

4 

National Institute of Nuclear Physics, National Laboratories of Frascati (INFN-LNF) 

Via Enrico Fermi, 40 - 00044 Frascati – Roma (ITALY) 

5 Art-Test s.a.s 

Via del Martello,14 – 56121 Pisa (ITALY) 

6 Institute of Chemistry of Organometallic Compounds, CNR 



7 Department of Civilizations and Forms of Knowledge 

Via Galvani, 1 – 56126 Pisa (ITALY) 


An extensive analytical study has been performed on a large number of gold coins (Norman- 

Swabian Augustalis and Tarì, Grosso of Lucca, Florin of Florence, ‘Genovino’ of Genoa and their 

fractions) minted in Italy from the end of XII century to XIV century. The X-Ray fluorescence 

(XRF) technique was used for verifying the composition of the coins. XRF is a non-destructive 

technique particularly suited for in-situ quantitative analysis of gold and minor elements in the 

precious alloy. The study sheds some light on the sudden diffusion of gold coins in Italy around 

the first half of XIII century, allowing some hypotheses on the provenience of the gold used for 

such an extensive coinage that dominated the economic trades from that period on. 

-221 -



(P45) 

SPECTROSCOPIC STUDIES ON ETRUSCAN ARCHAEOLOGICAL FINDINGS 

G. Sorrentino 1 , S. Giuntoli 1 , M. Lezzerini 2 , S. Legnaioli 3 , G. Lorenzetti 3 , G.H. Cavalcanti 4 and 

V.Palleschi 4,5 

1 

Center for Ancient Mediterranean and Near Eastern Studies (CAMNES) 

Via del Giglio, 15 – 50123– FLORENCE (Italy) 

2 Department of Earth Sciences, Pisa University 

Via S. Maria, 53 - 56126 PISA (ITALY) 

3 Institute of Chemistry of Organometallic Compounds, CNR 


Via G. Moruzzi, 1 – 56124 PISA (Italy) 

4 



Campus da Praia Vermelha - CEP 24210-346 - Niterói – RIO DE JANEIRO (Brazil) 

5 

Department of Civilization and Forms of Knowledge, Pisa University 

Via Galvani, 1 – 56126 PISA (Italy) 


The excavation and study of the Bosco della Riserva archaeological site of Tuscania (Italy) has 

been granted to the Lorenzo de' Medici Italian International Institute (LdM) in 2005. Since 2011, 

the activity is directed by the Center for Ancient Mediterranean and Near Eastern Studies 

(CAMNES). In this communication are presented the results of an extensive study developed in 

collaboration with CAMNES and the Italian National Research Council, for the non-destructive 

analysis of the findings from the “Pratino” Etruscan necropolis. Hundreds of ceramic, bronze and 

iron objects were analysed using X-Ray Fluorescence (XRF) and Laser-Induced Breakdown 

Spectroscopy (LIBS), along with a few soil samples found inside and on the vessels. A special 

attention was devoted to the study of the elemental exchanges between the archaeological findings 

and the environment, in view of a possible use in situ of both XRF and LIBS mobile 

instrumentation. 

-222 -



(P46) 

DETERMINATION OF METALS IN THE FOOD CHAIN USING THE HIGH SPEED 

SELF REVERSAL METHOD FOR BACKGROUND COMPENSATION 

Oppermann, Uwe 1 and van Oyen, Albert 2 



e-mail: uo@shimadzu.eu 

Heavy metals such as cadmium, chromium, and lead are natural components of the earth's crust 

and typically present in our environment in higher or lower concentration levels. They are entering 

the human body via food, and drinks, and air. Some of those heavy metals, so called trace 

elements such as Chromium, Iron, Cobalt, Copper, Manganese, Zinc, and Tin in low concentration 

levels are essential to the human body, as they are important for the metabolism. At higher 

concentrations however they are harmful to the human body and causing poisoning. Typical heavy 

metal poisoning are coming from drinking water contamination by lead pipes, air contamination 

from industrial emission sources, or intake via the food chain in form of contaminated vegetables, 

meat and fish. 

Typically the control of elements at the trace and ultra-trace concentration levels are carried out 

using atomic absorption spectrometers, like the Shimadzu AA-7000 which is a fully automatic 

double beam dual atomizer system in combination with the graphite furnace GFA-7000 with 

digital control and the sample preparation station ASC-7000.The concept of AA-7000 allows the 

fully automatic changeover from flame to graphite furnace mode and element specific 

optimisation of the atomizer position. The system is including two methods of background 

correction for the determination of heavy metals in samples with complex matrices when using 

flame and graphite furnace atomization. The Deuterium background correction is useful for 

compensation of spectral interferences generated by molecular absorption and particulate caused 

scattering. Additionally the high speed self reversal technique (high current pulse technique) is 

useful for the compensation of interferences caused by overlapping absorption lines and structured 

background. 

In order to analyze food and soil samples the analytical procedure starts with the sample digestion 

using a microwave digestion system with a typical sample weight of approximately 250 mg in a 

mixture of 1.5 ml nitric acid (70%) and 4.5 ml sulphuric acid (70%). The sample solutions are 

transferred in a 10 ml flask and filled up to volume accurately. The quantitative determination of 

cadmium is done using a fully automatic sequence programmed on AA-7000, with a calibration 

curve (see figure 2) from a stock standard solution with matrix matched acid concentration using 

the sample preparation station ASC-7000 in combination with the autodiluter. 

Since the list of contaminants and their maximum contaminant level is expected to be even more 

stringently controlled in future, there is a real need for system configurations with lowest detection 

limits and highest precision. Shimadzu offers total hardware and software for the accurate 

determination of contaminants in water, food and soil samples demonstrating competence and 

know-how of a market leader in spectroscopy. 

-223 -



(P47) 

LO-RAY-LIGH ® DIFFRACTION GRATINGS IN UV-VIS SPECTROSCOPY 

U. Oppermann a , M. Egelkraut-Holtus a , and T. Fujiwara b 


b Shimadzu Device Corporation, Kanda-Nishikicho 1-Chome, 101-8448 Tokyo, Japan 


It has been more than half a century since the release of the first Shimadzu UV-VIS spectrophotometer 

QB-50 in 1952 and during this time more than 160.000 UV-VIS spectrometers have 

been produced and installed in a wide variety of different applications. A lot of technical 

innovations have been implemented to improve the performance and significantly reduce the stray 

light levels. The latest innovation during development of sophisticated spectrophotometers is 

based on a new holographic exposure method and optimized etching process which has made it 

possible to produce both high-efficient and exceptionally low stray light gratings. 

These LO-RAY-LIGH ® gratings have guaranteed values of stray light at the intermediate position 

between zero- order and first-order lights. The values are measured by Shimadzu's laser straylight-measuring 

system. 

The latest development in the series of UV-VIS spectrophotometers is the UV-2700 which is a 

true double beam double monochromator system in a compact design for high-precision spectral 

analysis of a wide range of samples including organic and inorganic compounds, biological 

samples, optical materials and photovoltaics. The high performance optical system 

is designed with “LO-RAY-LIGH ® ” diffraction gratings, featuring highest efficiency 

and exceptionally low stray light. The spectrophotometer operates in the wavelength range of 185 

to 900 nm and allows highly sophisticated applications such as direct measurement of high density 

samples up to 8 absorbance units without dilution. 

A typical example for high density measurements are KMnO 4 solutions in different concentrations 

which show an excellent linearity of up to 8 absorbance units. A variety of possible system 

configurations will be discussed on recent application examples and advantages of the new 

spectrophotometer series will be explained. 

-224 -



(P48) 

PLASTC WASTE IN THE ENVIRONMENT – A NEW CHALLENGE IN 

SPECTROSCOPY 

Oppermann, Uwe 1 and van Oyen, Albert 2 




The production of plastic has reached an all-time high, for instance in 2008 there has been 245 

million ton produced worldwide. According to the United Nations Environment Program it is 

estimated that annually 6.4 Mt plastic ends in our seas and oceans worldwide. Estimates of the 

total volume in our oceans exceed more than 100 Mt but more and more research assumes this is 

an underestimation [1]. 

In the environment degradation of plastic takes place. Under influence of UV-radiation and the 

ocean waves, big pieces of plastic are grinded into microplastics (< 5 mm). A large amount of 

these plastics will land on the beaches where the sand is abrasive. The sand stores a lot of heat and 

exchanges this with the plastics, which will accelerate the degradation. 

A FTIR spectrum of a PE-pellet or granule in the environment differs strongly from the virgin 

state of PE as it was produced. As a result of degradation a lot of new peaks are developing in the 

FTIR spectrum. At this time, it’s a well adopted opinion that degradation mainly takes place on 

the surface of the granules. The plastic granules on beaches getting sanded and small pieces 

released of the surface, are forming an invisible pollution. The plastic soup is becoming a plastic 

bouillon. Experimental work is in progress for analyzing the micro or nano size of these invisible 

plastic particles on a Shimadzu laser diffraction particle size analyzer SALD-2201. 

The release of toxic additives raises another problem of the plastic in our environment. Especially 

in the past heavy metals like Cd and Pb were used for stabilizing and coloring the plastic. 

Nowadays Cd and Pb are restricted by environmental laws like: RoHS, CONEG, European 

packaging norm and others. However these evil elements from the past are now contaminating our 

beaches. Recently yellow PE pellets have been found, containing more than 5000 ppm Cd. 

Another problem is that marine life mistakes plastic for food. Well known are the pictures of Chris 

Jordan [2] of albatross chicks which died of hunger but having a full stomach with plastic. 

Nowadays more and more researches are concentrating on the stomach content of fish and birds. 

Jan Andries van Franker, Wageningen University [3], who kindly provided samples, has spend 

decades researching plastic in fulmars. Over 90% of the North sea fulmars have plastic in their 

stomach. Most of these plastics found, origins from plastic commodities, like PE. 

When a stomach of a bird, fish or seal is opened you’ll also see the undigested remains of the 

food. PE and many other plastics are insolvable in stomach-acid, as are fibrous fibers, like keratin. 

The peptide structure of keratin has strong similarities with the amide structure found in the plastic 

nylon. 

The majority of FTIR-users don’t have the time and experience and therefore trust the polymer 

libraries available in the market. At this time the majority of the polymer- or plastic libraries are 

using spectra of prime materials for the libraries. These spectra are very useful for prime materials, 

polymer production waste, pre-consumer recyclates but are insufficient for post consumers 

recyclates and plastic found in the environment. 

-225 -



Plastics are not inert but change overtime. Plastics are thermodynamically metastable. Over time 

plastic are losing their preferred and desired mechanical properties as well as their thermal 

properties. Therefore the plastic recycle market is limited by the thermo dynamical state of the 

waste plastics. Also the identification of plastic in our environment needs an updated determining 

method. 

FTIR-ATR is a strong tool for identifying plastic over a long period of time, or even better over a 

degradation period. With the right library, FTIR-ATR is a helpful tool for polymer industry as 

well as for pre- and post- consumer plastic waste recycler, and for the researchers who are 

describing the plastic waste in our environment. 

References 

[1] UNEP, year book 2012 

[2] Midway: Message from the Gyre, http://www.chrisjordan.com/gallery/midway/ 

[3] Wageningen University, Plastic waste in the Sea, http://www.wageningenur.nl/en/Expertise- 

Services/Research-Institutes/imares/show-2/Plastic-waste-in-the-Sea.htm 

-226 -



(P49) 

XRF DETERMINATION OF SILICON IN ALUMINA 

Michele Cowley 1 and Johann Fischer 1 

1 Sasol Technology Research and Development, P.O. Box 1, Sasolburg, South Africa 

e-mail: Michele.cowley@sasol.com 

Several analytical techniques are known for the determination of silicon in catalysts, e.g. zeolites. 

These include: Flame atomic absorption spectrometry (FAAS), inductively coupled plasma atomic 

emission spectrometry (ICP-AES), wet chemical methods such as gravimetric determination of Si, 

nuclear magnetic resonance (NMR) and XRF. 

In the work reported here, X-ray fluorescence spectrometry (XRF) was used to determine the 

silicon content in modified alumina support. The focus was on comparing different sample 

preparation methods, i.e. pressed powders and fused beads, for calibration. 

Exploratory work indicated that preparation of standards for the calibration by milling together 

powders of metal oxides and subsequent pressing into pellets gave varying results when measuring 

pressed powder samples against this calibration curve. 

The preparation of standards for calibration by fusion of silicon dioxide and alumina was 

investigated further. The XRF results reported were obtained by both standardless/semiquantitative 

and quantitative methods. 

-227 -



(P50) 

XRF DETERMINATION OF SULPHUR IN IRON OXIDE 

Michele Cowley 1 , Johann Fischer and Willemien van Schalkwyk 1 

1 Sasol Technology Research and Development, P.O. Box 1, Sasolburg, South Africa 

e-mail: Michele.cowley@sasol.com 

In catalytic studies it is often required to analyse volatile and light elements like sulphur at lower 

and lower levels on solid substrates. Traditionally sulphur is analysed by combustive techniques 

but these have limitations when applied to refractive matrices. Dissolution techniques as applied 

in ICP are also problematic as sulphur is easily volatilized and lost during dissolution. The power 

of XRF with solid matrices is well recognised but it has limitations for light elements like S. Also, 

the preferred method for XRF analysis is fused beads but with a volatile analyte at low 

concentrations this is not a feasible approach. This works aims to show the value that can still be 

derived from XRF using pressed pellets of powdered samples as a means of analysis. 

XRF was applied in determining the sulphur content in iron-based Fischer-Tropsch catalyst. 

Standards were prepared by milling catalyst and a powder sulphur standard. Measurement of a 30 

mg/kg standard reference material (S in iron ore) against this calibration curve gave a result of 31 

mg/kg. This is not yet the detection limit of the technique but is still quite a useful low 

concentration range for many studies. 

The sulphur concentration for the iron oxide obtained with the semi-quantitative/standardless 

analysis programme differed from that obtained with the quantitative programme in which a 

specific calibration curve was used. This confirms the importance of matrix matching for accurate 

quantitative results especially when using powdered samples. 

-228 -



(P51) 

ELEMENTAL MAPPING OF MOROCCAN ENAMELED TERRACOTTA TILE WORKS 

(ZELLIJ) BASED ON X-RAY MICRO-ANALYSES 

R. Bendaoud 1 , A. Guilherme 2 , A. Zegzouti 1 , M. Elaatmani 1 , J. Coroado 3 , A. Le Gac 1 ,4, S. 

Pessanha 1 , M. Manso 1 , M. L. Carvalho 1, * and I. Queralt 5 

1 Faculté des Sciences Semlalia, Université Cadi Ayyad Marrakech, BP 2390, Marrakech, Morocco 

2 Centro de Física Atómica, Universidade de Lisboa, 1649-003 Lisboa, Portugal. 

3 Dept. Arts, Conservation & Restoration, Polytechnic Institute of Tomar, 2300-313 Tomar, 

Portugal 

4 Departamento de Conservação e Restauro, FCT, Universidade Nova de Lisboa 

5 Laboratory of X-Ray Analytical Applications, Institute of Earth Sciences “Jaume Almera”, CSIC, 

Solé Sabarís s/n, 08028 Barcelona, Spain 


In this work the elemental mapping of enamelled terracotta samples (Zellij), produced between the 

13th and 20th centuries in Morocco, collected from five different monuments from Marrakech, are 

presented. These pieces were analyzed by two non-destructive micro X-Ray Fluorescence (XRF) 

spectrometers, aiming to obtain elemental distribution and elemental composition. The type of 

samples studied, Zellij, are typically Moroccan. They are characterized by a terracotta body with 

an enamelled surface. This sort of objects was prepared manually. The craftsman unified the paste 

with his arms and feet, making it less stiff, and then the pieces were split into blocks and hardened 

again under sun light and flattened with a bat. Then, parts of 10 x 10 cm were obtained and placed 

under sun light for as long as it took to fully dry, which corresponded to the first burnt stage. 

Afterwards, these pieces were submersed into a colouring, containing a mixture of lead, sand and 

other oxides that promote the desired colour after what the pieces were submitted to a second 

firing process. 

From the obtained spectra we have identified the main elements present in the tin-opacified lead 

glaze. The modern samples reveal different mixture components, such as Ba, and a much lower 

content in Pb, when compared to the older samples. Ba is not found in the glaze composition of 

old samples. Actually the use of Ba as a substitute of Ca as a network modifier in the glassy 

matrix is recent. The identification of the decoration colors is based on the different ratios between 

the fluorescence line of the main component of the glaze (Pb-L line) and the fluorescence lines 

of the main components of the pigment (Co-K, Mn-K, Ni-K,…lines). The semi-quantitative 

calculations based on these ratios revealed significant differences between modern and ancient 

samples. Furthermore, and in what concerns the green, in the older samples it is a Cu- based green, 

while in the modern ones it is a Cr-based. 

Differences were found as well in the composition of the ceramic body. 

-229 -



(P52) 

DETERMINATION OF METALS IN LARVAE USING ICP-OES 

Blanca Paz 1 ,.Ciro Márquez. 1 , Olga Cabrera 2 ; Lydia Romero 2 , Carlos Enrique Díaz 3 

1 .Facultad de Química, Universidad Nacional Autónoma de México. Ciudad Universitaria D.F. C. 

P. 15020, México 

2 .Departamento de Química Forense. Procuraduría General de Justicia del Estado de México. C. P. 

50090, Toluca, Estado de México. 

3 .Laboratorio de Química Forense. Procuraduría General de Justicia del Distrito Federal. 

Coordinación General de Servicios Periciales. C. P. 03100, México 

e-mail: ciromar@unam.mx 

Forensic entomology is a science that studies insects to acquire information about a crime and aid 

in legal cases. The insects found in a decomposed body can provide data to clarify a crime. The 

cadaver microfauna are of the order Diptera and Coleptera and they are referred to as 

necrophagous insects. Historically, insects have been used to determine the Post-Mortem Interval 

(PMI). The stage and the generations of insects found at the scene are the aspects considered to set 

the PMI. Nowadays there has been progress in entomotoxicology, which is dedicated to the 

detection and identification of drugs of abuse in larvae. The quantification of metals in insects is 

another area to explore in forensic entomology with a variety of applications. Metals could be 

used as environmental markers, indicators of poisoning or indicators of gunshot wounds. 

In this work, a methodology for the detection and quantification of metals in larvae using optical 

emission spectroscopy with inductive coupled plasma is proposed. The procedure was done with 

two samples, one from a chicken in decomposition (reference sample) and a test sample from a 

human corpse. 

Samples were digested in a microwave digestion unit (Anton Paar Multiwave 3000). The test 

sample was done by duplicate and the reference by triplicate. Two reagent blanks were prepared. 

The weight of the samples was approximately 0.3-0.45g. The digestion mix was 4ml HNO 3 and 

1ml of H 2 O 2 . The digestion program was 800W of power, a ramp of 10 minutes to be held for 

another 10 minutes. The maximum temperature reached was 170°C at a pressure of 8.0 bar. The 

digested samples were taken to a volume of 25ml with deionized water. The equipment used for 

the analysis was an ICP-OES PerkinElmer Optima 4300 DV. 

The results show that the standards kept a lineal relation throughout the analysis. Most of the 

elements were detected in both samples. However, there are elements that are found in greater 

quantities in the test sample: Al, Ca, Cu, Fe, Mg, Mn, Na, Si, Ti and Zn. Other elements are 

present in equal or less amount in said sample. The elements that are in higher concentrations are 

Al, Ca, Fe, Mg, Na and Si. The results are shown in Table 1 and are expressed in ppm (mg/Kg). 

-230 -



Element 

Concentration mg/Kg 

Reference sample Test sample 

Al 28.31-53.27 421.68-427.58 

B 2.41-34.33 17.66-18.57 

Ba 1.93-2.01 3.47-3.51 

Ca 287.77-361.97 852.27-918.97 

Cu 1.52-1.72 3.12-3.73 

Fe 76.64-289.09 313.49-330.29 

Mg 239.56-252.46 398.46-421.36 

Mn 1.15-1.40 6.29-6.83 

Na 1692.4-1746.4 1991.4-2164.4 

Pb 1.41-2.95 .



(P53) 

CHALLENGING SPATIAL RESOLUTION LIMITS OF LASER ABLATION 

INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY (LA-ICP-MS) IN 

ELEMENTAL DISTRIBUTION MAPPING APPLICATIONS EMPLOYING ACTIVE 2- 

VOLUME CELL TECHNOLOGY 

Dhinesh Asogan 1 , Damon Green 1 , John Roy 2 , Stephen Shuttleworth 2 , Bill Spence 1 and Peter 

Winship 1 

1 CETAC Technologies, 14306 Industrial Road, Omaha, Nebraska 68144, USA 

2 Photon Machines, 366 Gallatin Park Dr., Bozeman, Montana 59715, USA 

E-mail: pwinship@cetac.com 

The marriage of laser ablation technology with inductively coupled plasma mass spectrometry 

instrumentation (LA-ICP-MS) provides the analyst with a powerful tool in the study of elemental 

distribution over a sample surface (i.e. sample mapping or imaging) across a gamut of sample 

types in numerous scientific disciplines. The growing interest in elemental distribution 

measurement in the scientific community, and the demand for the study of smaller and smaller 

sample surfaces and/or features in the greatest detail possible, has been met with research and 

development in laser ablation sample cell technology that allows spatial resolution at < 10 µm. 

The key to achieving such spatial resolution in laser ablation mapping and imaging experiments – 

and therefore in generating data that exhibits the greatest level of analytical detail – lies in the 

efficient capture and transfer of ablated particulate material between the sample surface and the 

associated analytical instrumentation (in this case ICP-MS) and in the sample cell washout time. 

Historically, the efficient capture of particulate sample material, in the ‘ablation plume’, that is 

generated following laser ablation has been difficult and, as a general rule, sample cell washout 

was dictated by cell volume. More recently, such issues have been addressed by an innovative 

approach to sample cell design. Such an approach has led to the development of 2-volume cell 

technology whereby large samples may be accommodated in a large ‘outer cell’ volume whilst the 

ablation process is controlled within a low volume ‘inner cell’ or ‘cup’. The most documented - 

through peer reviewed articles - and developed cell of this type is the HelEx cell. The HelEx 

captures and entrains ablated material within a vortex in the inner cell, generated by a series of 

helium and argon gas flows, and allows efficient transfer of such material for elemental and 

isotopic measurement. Sample cell washout time is kept to an absolute minimum (typically in the 

millisecond timescale) as ablation occurs within the low volume inner cell. 

We present sample surface elemental distribution maps for geological and oceanographic sample 

types that have been generated following LA-ICP-MS study. These maps exhibit distribution 

resolution of the order of 10 µm and show what is possible in terms of the imaging of 

microscopically small sample surface areas and features. 

-232 -



(P54) 

LOW VOLUME SAMPLE INJECTION FOR TRACE ELEMENT ANALYSIS 

EMPLOYING INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY (ICP-MS) 

David Clarke, Bill Spence and Peter Winship 

CETAC Technologies, 14306 Industrial Road, Omaha, Nebraska 68144, USA 


With the growth of application of trace element analysis across the scientific disciplines, the 

requirement to sample and inject decreasingly low liquid volumes is increasingly prevalent, 

particularly for analytical techniques such as inductively coupled plasma mass spectrometry (ICP- 

MS). In a number of scientific fields, notably clinical and nano-particulate fields, sample size or 

volume can be such that traditional sample introduction to ICP-MS is not practical or even 

possible. Sample dilution may also not be a practical alternative to direct introduction particularly 

when analyte concentration is at trace or ultra-trace levels. Biological cells, dust particles and 

atmospheric condensates are just a few examples of sample types that would present a low size or 

volume challenge to the analyst that illustrates the need for an ICP-MS autosampler that can 

precisely sample and inject microlitre and nanolitre sized aliquots to an ICP. 

We present such an autosampler that is akin to the type of system that allows low volume sample 

introduction to high performance liquid chromatography (HPLC) instrumentation in terms of 

design and manufacture. A key difference, however, is that, with trace element analysis in mind, 

each of the wetted components have been manufactured from non-metallic materials so to avoid 

sample contamination and ensuring data quality, i.e. making this autosampler applicable to trace 

and ultra-trace level elemental and isotopic measurement with ICP-MS. In addition this system 

takes aliquots of sample and injects it in its entirety ensuring that no sample is wasted. In this 

proof-of-principal study, we show that full loop sample aliquots of 50 µl and partial loop aliquots 

(captured between air-gaps) of 10 µl can be successfully taken and injected into an ICP prior to 

successful measurement of data by an ICP-MS system. We show that this low volume 

autosampler allows the accurate and precise measurement of elements with ICP-MS with linear 

standard calibration at low volume. When monitoring the peak area of ICP-MS signals this 

autosampler will allow the study and measurement of liquid samples down to 100 nl in volume. 

In addition to its sampling capability, this system also exhibits fine movement control such that it 

can sample liquid volumes from 96, 384 and 1536 well plates, therefore opening up new 

possibilities in trace element analysis in scientific disciplines that have previously been difficult to 

explore. 

-233 -



(P55) 

APPLICATION OF LEAD ISOTOPE RATIO MEASUREMENTS FOR THE ORIGIN 

ASSESSMENT OF MARINE POLLUTION 

Emilia Vassileva and Anna Maria Orani 

International Atomic Energy Agency, Environment Laboratories, Department of Nuclear Sciences 

Applications, 4 Quai Antoine 1er MC 98000, Principality of Monaco 

e-mail: e.vasileva-veleva@iaea.org 

Lead is a non-essential toxic element and at high levels of human exposure, is causing damage to 

almost all organs and organ systems. Despite the fact that it has been the most widely investigated 

element over the last decades, the precise and accurate determination of lead isotope ratios is still 

important for different application fields, especially for the investigation of lead isotope variation 

for environmental monitoring in order to trace the sources, the fate and effects of eventual 

pollution or contamination. 

The capabilities of inductively coupled plasma mass spectrometry (ICP-MS) for performing 

precise isotope ratios measurements are nowadays well known. Instrumental progress in this field 

has permitted to obtain highly reliable isotope ratio data useful for many environmental 

applications. 

The aim of this work was to enhance the capabilities of HR ICP-MS for accurate and precise lead 

isotope ratios measurements in marine environmental samples – sediments and biota. 

An analytical protocol for the measurement of isotope ratios in marine samples using the Nu 

Attom single collector-ICP-MS was developed. The precision of the measured Pb isotope ratios 

obtained (for equivalent total Pb quantities) was comparable to multi-collector methodologies, 

using either an array of ion counters or conventional Faraday collectors coupled with a high 

efficiency sample cone. 

The accuracy of the measured Pb isotope ratios and the effect of the sample matrix were evaluated 

for a series of sediment and biota digests and doped solutions of the NIST SRM 982 standard. For 

concentrations up to 20 μgmL −1 of matrix elements (i.e. Ca and Mg) and low lead concentration, 

matrix effects were resolvable at the level of precision reported. 

Significant matrix effects at higher level of the matrix concentration were associated with sample 

compositions typical for sediment and biota samples. In these cases for accurate isotope ratio 

measurements, the removal of (at least) the major cations was required. For this purpose, several 

separation methods, based on the selective separation of lead from the sample matrix by sorption 

or complexation were developed and evaluated. 

The proposed procedure allows the reliable determination of Pb isotope ratio in marine samples, 

which is an important tool in environment studies. 

Discrimination of anthropogenic and geogenic lead sources requires both precise and accurate 

isotope ratio determination and also high versatility due to the complex matrix, which is typical 

for marine sediments . In order to differentiate between anthropogenic and geogenic sources of 

lead in sediments, both lead concentration and isotopic composition were determined by ICP SMS 

along a soil profile collected from a Caribbean region. Along the sediment profile, a significant 

change of lead isotopic composition could be detected, showing the difference between 

anthropogenic (surface) and geogenic sources. Along with the total concentration of lead and other 

sediment properties, the contribution of anthropogenic sources to the lead concentration of 

sediments and their participation in lead mobilization can be estimated. 

-234 -



(P56) 

APPLICATION OF HIGH RESOLUTION SECTOR FIELD ICP- MS FOR 

DETERMINATION OF LOW LEVEL PLUTONIUM IN MARINE SAMPLES 

Emilia Vassileva, Eunmi Han and Isabel Levy 

International Atomic Energy Agency, Environment Laboratories, Department of Nuclear Sciences 

Applications, 4 Quai Antoine 1er MC 98000, Principality of Monaco 

e-mail: e.vasileva-veleva@iaea.org 

Sources of plutonium isotopes to the marine environment are well defined, both spatially and 

temporally which makes Plutonium is a potential tracer for oceanic processes. This study presents 

the selection, optimisation and validation of a analytical procedure for the ultra-trace 

determination of Pu isotopes ( 240 Pu and 239 Pu) in marine samples by High Resolution (HR) ICP- 

MS. The method was optimised for the removal of the interference from 238 U and the chemical 

recovery of Pu. 

Comparisons of various separation strategies using AG1-X8 and TEVA resins to determine Pu in 

marine sea water and marine sediments are reported. A combination of anion-exchange (AG1-X8) 

and extraction chromatography (TEVA) was the most suitable, with a radiochemical Pu yield 

87±5% and a U decontamination factor of 1.2×10 4 . 

The validation of the measurement process encompassed: 1.Using CRMs for method development 

and isotopic CRM for mass discrimination corrections, 2. Identification of the majority of 

potentially significant factors influencing the results (ICP-MS parameters, the procedural blank, 

spectral interferences, separation efficiency, memory effect, the isotopic ratio stability, dead time), 

3. Mathematical modelling of the entire measurements process and demonstrating the traceability 

to the mole or kilogram SI units, 4. Estimation of combined uncertainty according to the 

ISO/GUM guide, 5. Comparative studies of the different analytical procedures by applying two 

types of methods (SF-HR-ICP-MS and α spectrometry). The adequate results obtained by 

applying different analytical approaches were identical within the range of the expended 

uncertainty. 

The estimated HR ICP-MS instrumental limit of detection for 239 Pu and 240 Pu was 0.05 

fgmL -1 , with an absolute limit of quantification of 0.09 fg. The proposed method allows the 

determination of Pu in marine samples at ultra-trace levels. Finally, the analytical method was 

applied to determining the Pu isotopic signature in sediment samples – IAEA-385, IAEA-405 

IAEA-356 and 240 Pu/ 239 Pu atom ratios in the IAEA – 418 seawater 

-235 -



(P57) 

FTIR EMISSION SPECTROSCOPIC STUDY OF 

ALUMINA-SILICATE BASED BLACK POWDER WITH PECULIAR PROPERTIES 

J. Mink 1,2 , J. Mihály 1 , Cs. Németh 1 

1 Institute of Molecular Pharmacology, Research Centre of Natural Sciences, Hungarian Academy 

of Sciences, H-1525 Budapest, Hungary 

2 Research Institute of Chemical and Process Engineering, Faculty of Information Technology, 

University of Pannonia, H-8201 Veszprém, Hungary, 

e-mail: jmink@chemres.hu 

Spectroscopic characterization of black powdered materials is vital for understanding the basic 

properties and structure. Typically all black powdered samples are highly absorbing, badly 

reflecting the infrared (IR) radiation. It has turned out, that infrared emission spectroscopy is 

applicable to measure infrared emission spectra of black powder samples. 

The originally discovered black volcanic mineral in Hokkaido Island in Japan has exhibited 

enhanced emissivity in infrared region at rather low temperatures (30-60°C) [our laboratory 

measurements]. This natural product today can be synthesized in laboratory conditions with 

various quantities of finely divided carbon nanoparticles. 

The aim of our study was the comparison of the infrared emissivity of different product 

synthesized by different methods. A broad variety of FTIR emission spectroscopy has been 

developed and applied in our laboratory [1-3]. 

Bomem MB-102 Michaelson type FTIR spectrometer was used to record emission IR spectra. The 

spectrometer is equipped with CsI beamsplitter and room temperature DTGS detector. The 

measured spectral range was 4000-200 cm -1 . 256 scans were accumulated at 4 cm -1 resolution. A 

Specac 20-100 type temperature controller was used and a home made emission cell, optics and 

sample holders [2] were adopted to produce emission spectra. The temperature stability was about 

±1°C. 

Perfectly homogenized by a vibrating mill for sample with KBr powder of mixture was pressed 

into a 13 mm diameter pellet. The emissivity of the samples was compared in temperature range 

between 30 and 70°C. The integrated emission intensity was than related to those of the blackbody 

radiation. The surprising conclusion was that the following order of relative intensities was 

established with respect to the blackbody radiation: 

A (88%) 

It was clearly seen that samples C and D exhibit higher emissivity at 40 °C then the calibrated 

reference blackbody. That is why we call these samples as “Magic” Black Powders. The 

explanation of the above unexpected properties will be discussed together with their very 

promising applications in medicine and therapeutics. 

J. Mink, G. Keresztury, Spectroscopy, Emission in Encyclopedia of Pharmaceutical Technology, 

(J. Swarbrick, J. C. Boylan eds.), Vol. 14, Marcel Dekker, Inc., New York-Basel-Hong Kong, 

1996, pp. 123-179 

J. Mink, Infrared Emission Spectroscopy in Handbook of Vibrational Spectroscopy, J.M. 

Chalmers and P.R. Griffiths (Eds), John Wiley & Sons, Ltd, Volume 2, pp.1193-1214 (2002) 

T. I. Korányi, J. Mihály, É. Pfeifer, Cs. Németh, T. Yuzhakova, J. Mink, J. Phys. Chem. A, 110 

(2006) 1817-1823 

-236 -



(P58) 

NEW IMAGING CAPABILITIES USING LA-ICPTOF MASS SPECTROMETRY 

H.A.O. Wang, 1,3 C. Giesen, 2 D. Grolimund, 3 B. Bodenmiller, 2 D. Günther 1 

1 Trace Element and Micro Analysis Group, ETH Zurich, 8093 Zurich 

2 Institute of Molecular Life Sciences, University of Zürich, 8057 Zürich 

3 microXAS Beamline Project, Swiss Light Source, PSI, 5232 Villigen PSI 

e-mail: guenther@inorg.chem.ethz.ch 

This work demonstrates an advanced multiplexing imaging setup based on Laser Ablation (LA) 

coupled to a sector field-ICP-MS and a commercial Mass Cytometer. The current measurements 

successfully demonstrate sub-cellular (~1 μm) spatial resolution imaging of biological tissue thin 

sections. One of the key improvements is attributed to a laser ablation cell. 1 This novel LA cell has 

a short washout time and enhances the signal to noise ratio of the LA transient signal. It enables 

complete separation of single shot signals generated by high frequency (>20 Hz) laser ablation and 

furthermore acquisition of analytes in the sample aerosol produced by 1 μm laser single shot. As 

shown in a case study, multiplexing biomarkers with metal-tagged antibodies were imaged in thin 

sections of breast cancer tissue. The resulted high spatial resolution high sensitivity biomarker 

images were acquired simultaneously by the mass cytometer (CyTOF®). Finally, the experimental 

setup helps biologists investigate various breast cancer sub-types, and better understand cancer 

metastasis mechanisms. The presented imaging setup will open new research opportunities for 

pathologists and pharmacologists and some of the potential applications will be discussed. 

1 Wang, H.A.O. et al. Fast Chemical Imaging at High Spatial Resolution by Laser Ablation 

Inductively Coupled Plasma Mass Spectrometry. Submitted to Analytical Chemistry (2013). 

-237 -



(P59) 

TRACE ELEMENT DISTRIBUTION OF EXTRACELLULAR PROTEINS 

DETERMINED IN HUMAN SERUM BY MP-AES AND GFAAS 

Edina Baranyai 1 , Csilla Noémi Tóth 1 , Mihály Braun 1 , Tünde Tarr 2 , István Csípő 2 , Margit Zeher 2 , 

József Posta 1 

1 Department of Inorganic and Analytical Chemistry, University of Debrecen, 4032 Egyetem 

square 1, Debrecen, Hungary 

2 3rd Department of Internal Medicine, University of Debrecen, 4032 Móricz Zs. 22., Debrecen, 

Hungary 

email: baranyai.edina@science.unideb.hu 

The elemental concentration of human blood is often used for building up diagnosis in the clinical 

practice. However, only a few studies are in the literature concerning the trace element and protein 

level of blood serum in case of autoimmune diseases and no information is available about the 

quantity of these essential trace elements binded to the main transport proteins. Therefore the aim 

of recent study was to determine the concentration of K, Ca, Mg, Zn, Cu, Fe and Mn in whole 

blood serum and to further investigate the quantitative distribution of these elements between 

Immunoglobulin G and three other high abundant protein fractions in blood serum of patients with 

Systemic lupus erythematosus (SLE) and Sjögren syndrome (SS). 

Anion exchange chromatography was used to separate blood serum samples into protein fractions 

and high abundant protein components were identified by UV-VIS spectrophotometry. Both 

whole blood serum samples and diluted protein fractions were digested by a microwave assisted 

system prior to analysis. K, Ca, Mg and Zn concentration of samples were determined by flame 

atomic absorption spectrometry (FAAS) and microwave induced plasma atomic emission 

spectrometry (MIP-AES) while Cu and Fe concentration were measured by graphite furnace 

atomic absorption spectrometry (GFAAS). Statistical analysis was carried out to evaluate the 

results. The distribution of trace elements among the gained protein fractions are calculated in 

percentage. 

There were no significant difference (p>0.05) in Mg and Fe concentration between the control, SS 

and SLE groups. Significantly lower concentration (p



(P60) 

THE ANALYSIS OF DDTS AND CHLORDANES AND THEIR METABOLITES BY GAS 

CHROMATOGRAPHY TANDEM MASS SPECTROMETRY: COMPARING 

ATMOSPHERIC PRESSURE IONISATION WITH ELECTRON IMPACT AND 

CHEMICAL IONISATION 

Sandra Huber 1,2 , Nicholas A. Warner 2 , Therese Haugdahl Nøst 1,2 , Ole-Martin Fuskevåg 2 and Jan 

Brox 2 

1 University Hospital of North Norway, Department of Laboratory Medicine, N-9019 Tromsø, 

Norway 

2 NILU – Norwegian Institute for Air Research, Fram Centre, N-9007 Tromsø, Norway 

e-mail: sandra.huber@unn.no 

Dichlorodiphenyltrichloroethane- (DDT) and chlordane-mixtures and their metabolites are still of 

interest for a broad community of scientists, researchers and authorities. As DDT-use is still 

permitted in parts of the southern hemisphere and Asia for malaria control, current emission 

sources of DDT exists. The use of chlordanes has stopped by the end of the 1980ies due to 

harmful side effects on environmental and human health. However, due to their persistence in the 

environment and potential for bioaccumulation in organisms, they are still included in many 

research projects and screening-programmes. 

Traditional analysis of DDTs and their metabolites has been done by gas chromatography (GC) 

coupled to mass spectrometry (MS) using electron impact ionisation mode (EI). For enhanced 

sensitivity for the analysis of chlordanes and their metabolites analysis with negative chemical 

ionisation (NCI) is necessary. The most common instruments for analysis of these compounds are 

single-quadrupole-MSs. GC-tandem-mass spectrometers (GC-MS/MS) recently introduced have 

helped enhance analysis for environmental applications by minimizing the influence of the 

background and matrix response on the analytical signal through multiple reaction mode (MRM), 

which cannot be performed on single-quadrupole-MS instruments. Novel innovation in analytical 

technology has combined atmospheric pressure ionisation (AP) with GC-MS/MS. The APGC- 

MS/MS instrument offers the advantage of ionisation at atmospheric pressure conditions together 

with reduced fragmentation. AP is a relative soft ionisation process compared to EI and has two 

possible processes, charge transfer or protonation. Mass spectra can be dominated by M +• , [M+H] + 

or [M-H] + , offering extensive capabilities for selection of precursor ions for targeted quantification 

in MRM. 

In the present work, the APGC-MS/MS has been tested for capability in residue analysis of DDTs 

and chlordanes and their metabolites. Two different instrumental set-ups (i.e. APGC-MS/MS and 

GC-EI/NCI-MS/MS) were compared regarding their fragmentation characteristics and sensitivity. 

First results will be presented. 

-239 -



(P61) 

PALM-TOP EPMA USING PYROELECTRIC ELECTRON BEAM FOR 100 

MICROMETER BEAM SIZE 

Jun Kawai, Akira Imanishi, Susumu Imashuku 

Kyoto University, Department of Materials Science and Engineering, Sakyo-ku, Kyoto 606-8501, 

Japan 

e-mail: kawai.jun.3x@kyoto-u.ac.jp 

We have developed palm-top size EPMA (electron probe X-ray microanalyzer) operated by 3 V 

electric battery except for a rotary vacuum pump. The electron beam is generated by a 

pyroelectric single crystal (LiTaO 3 ) with the size of 3 mm x 3 mm x 5 mm. A needle is put on the 

top of the crystal to produce focused electron beam (Fig.1). When the temperature is changed 

from room temperature to 80 o C, a high voltage is generated at the top of the needle (20 kV) and 

electron beam is focused on the sample with the spot size of 100 m (Fig.2c). The electric 

insulation of the edge of the pyroelectric crystal is a key issue to generate the focused electron 

beam from the top of the needle (thin Au or W wire). Without insulation, the beam is not focused 

(Fig.2b). The electron beam continues for a few minutes depending on the rate of temperature rise 

and vacuum. The temperature is controlled by a Peltier device, driven by an electric battery, and a 

rotary pump (2 Pa) is enough for the vacuum. 

Fig.1 Schematic illustration 

of palm-top EPMA. 

Fig.2 Spectra measured by (a) pyroelectric crystal, (b) 

needle without insulation, (c) needle with insulation. 

-240 -


Address List 

ADDRESS LIST 

Aaserud, Bjørn 

Holger Hartmann AS 

Liakollveien 1a 

1259 

Oslo 

Norway 

Tel: 40857287 

E-mail: b.h.aaserud@holger.no 

* * * * * * * * 

Aasoldsen, Terje 

SAMSI / BRUKER 

Nustadveien 75 

3970 

Langesund 

Norway 

Tel: 4795909112 

E-mail: terje@samsi.no 

* * * * * * * * 

Aasum, Jon-Henning 

Norwegian University of Life Sciences 

Postboks 978 

1432 

Ås 

Norway 

Tel: 47685858 

E-mail: jon-henning.aasum@student.umb.no 

* * * * * * * * 

Adams, Freddy 

University of Antwerp 

Campus Drie Eiken 

2610 

Wilrijk 

Belgium 

Tel: 0032 92 211954 

E-mail: freddy.adams@ua.ac.be 

* * * * * * * * 

Alfonso, Laura Trapiella 

Universidad de Oviedo, Departement de Quimica 

Fisica y Analitica 

C/Julian Claveria 8 

ES-33006 

Oviedo 

Spain 

Tel: 985105001 

E-mail: trapiellalaura@uniovi.es 

-241 - 

Anatoly, Snigirev 

ESRF 

6 rue Jules Horowitz 

38043 

Grenoble 

France 

Tel: 33476882627 

E-mail: snigirev@esrf.fr 

* * * * * * * * 

Åsheim, Arne 

Molab as 

Postboks 611 

8607 

Mo i Rana 

Norway 

Tel: +47 397 67 390 

E-mail: arne.aasheim@molab.no 

* * * * * * * * 

Audinot, Jean-Nicolas 

CRP - Gabriel Lippmann 

41 rue du Brill 

L-4422 

Belvaux 

Luxembourg 

Tel: +352 47 02 61 521 

E-mail: audinot@lippmann.lu 

* * * * * * * * 

Bambuch, Yvonna 

Tel: 492315890789 

E-mail: yvonna.bambuch@telekom.de 

* * * * * * * * 

Barbante, Carlo 

IDPA-CNR, University of Venice 

Dorsoduro 2137 

30123 

Venice 

Italy 

Tel: 390412348942 

E-mail: barbante@unive.it 

* * * * * * * *


Address List 

Barnes, Ramon 

ICP Information Newsletter Inc. 

18241 Beauty Berry Court 

3397207525 

Lehigh Acres 

USA 

Tel: 2396749430 

E-mail: barnes@chemistry.umass.edu 

* * * * * * * * 

Bean, Victoria 

RSC 

Thomas Graham House 

CB4 0WF 

Cambridge 

UK 

Tel: 1223432680 

E-mail: eyleyv@rsc.org 

* * * * * * * * 

Becher, Georg 

Norwegian Institute of Public Health 

P.O.Box 4404 Nydalen 

403 

Oslo 

Norway 

Tel: 21076242 

E-mail: georg.becher@fhi.no 

* * * * * * * * 

Bengtson, Arne 

Swerea KIMAB AB 

Isafjordsgatan 28A 

164 40 

Kista 

Sweden 

Tel: 46704616418 

E-mail: arne.bengtson@swerea.se 

* * * * * * * * 

Berlinger, Balazs 

National Institute of Occupational Health 

P.O.Box 8149 

33 

Oslo 

Norway 

Tel: 23195353 

E-mail: bbe@stami.no 

* * * * * * * * 

Bierla, Katarzyna 

LCABIE CNRS/UPPA 

2 Av. President Angot 

64053 

Pau 

France 

Tel: 33559407758 

E-mail: katarzynabierla@wp.pl 

* * * * * * * * 

Bøifot, Kari Oline 

FFI 

Postboks 25 

2007 

Tromsø 

Norway 

Tel: 99291409 

E-mail: kari-oline.boifot@ffi.no 

* * * * * * * * 

Bolshov, Michael 

Institute of Spectroscopy, Russian Academy of 

Sciences 

Fizicheskaya 5 

142190 

Moscow, Troitzk 

Russia 

Tel: 74958510227 

E-mail: mbolshov@mail.ru 

* * * * * * * * 

Börner, Markus 

Institute of Physical Chemistry, University of 

Münster 

Corrensstr. 46 

48149 

Münster 

Germany 

Tel: 492518336736 

E-mail: markus.boerner@uni-muenster.de 

* * * * * * * * 

Boutron, Claude 

University Joseph Fourier of Grenoble 

13 rue Messidor 

F-05000 

Gap 

France 

Tel: +33 4 92 51 32 40 

E-mail: claudeboutron@orange.fr 

* * * * * * * * 

-242 -


Bresson, Carole 

CEA Saclay 

DEN/DPC/SEARS/LANIE Bât 391 

91191 

Gif sur Yvette cedex 

France 

Tel: +33169 08 83 48 

E-mail: carole.bresson@cea.fr 

* * * * * * * * 

Brodzka, Renata 

Nofer Institute of Occupational Medicine 

st. 8 Teresy 

91-348 

Lodz 

Poland 

Tel: 48426314814 

E-mail: brodzka@imp.lodz.pl 

* * * * * * * * 

Broekaert, José 

University of Hamburg 

Martin-Luther-King-Platz 6 

D20146 

Hamburg 

Germany 

Tel: 4940428383111 

E-mail: jose.broekaert@chemie.uni-hamburg.de 

* * * * * * * * 

Buseth, Erik 

PerkinElmer 

Pb. 4468 

403 

Oslo 

Norway 

Tel: 4792428301 

E-mail: erik.buseth@perkinelmer.com 

* * * * * * * * 

Bye, Ragnar 

University of Oslo 

P.O. Box 1068, Blindern 

316 

Oslo 

Norway 

Tel: 22856579 

E-mail: ragnar.bye@farmasi.uio.no 

Bye, Sidsel 

Tel: 91383087 

E-mail: ragnar.bye@farmasi.uio.no 

* * * * * * * * 

Cagno, Simone 


PO Box 5003 

1432 

Aas 

Norway 

Tel: 393470350285 

E-mail: simone.cagno@umb.no 

* * * * * * * * 

Carvalho, Maria-Luisa 

University of Lisbon 

Av. Prof. Gama Pinto 2 

1649-003 

Lisboa 

Portugal 

Tel: 351961051293 

E-mail: luisa@cii.fc.ul.pt 

* * * * * * * * 

Address List 

Cerveny, Vaclav 

Charles University in Prague, Faculty of Science, 

Department of Analytical Chemistry 

Albertov 6 

CZ-12843 

Prague 2 

Czech Republic 

Tel: 420221951233 

E-mail: cerveny2@natur.cuni.cz 

* * * * * * * * 

Chanthai, Saksit 

Khon Kaen University 

Department of Chemistry, Faculty of Science, 

40002 

Khon Kaen 

Thailand 

Tel: 660815455388 

E-mail: sakcha2@kku.ac.th 

* * * * * * * * 

* * * * * * * * 

-243 -


Address List 

Chemnitzer, Rene 

Bruker Daltonik GmbH 

Fahrenheitstrasse 4 

28359 

Bremen 

Germany 

Tel: 4915111358488 

E-mail: rene.chemnitzer@bruker.com 

* * * * * * * * 

Cowley, Michele 

Sasol Shared Services a Division of SGS 

Private Bag X1000 

2302 

Secunda 

South Africa 

Tel: 27169603133 

E-mail: tanya.cerva@sasol.com 

* * * * * * * * 

Dalby, Søren 

Bruker 

Kallerupvej 39 D 

2640 

Hedehusene 

Danmark 

Tel: 4529360888 

E-mail: sd@bruker.se 

* * * * * * * * 

De Monte, Emanuela 

Tel: 390572476682 

E-mail: manu.demonte@alice.it 

* * * * * * * * 

Debeljak, Marta 

National Institute of Chemistry 

Hajdrihova 19 

1000 

Ljubljana 

Slovenia 

Tel: 14760382 

E-mail: marta.frlic@ki.si 

* * * * * * * * 

Deshayes, Ludivine 

Kaiser Optical System 

5 Allee Moulin Berger 

69130 

Ecully 

FRANCE 

Tel: 33689150550 

E-mail: deshayes@kosi.com 

* * * * * * * * 

Dos Santos, Joaquim M F 

Physics Department, University of Coimbra 

Rua Larga 

3004 - 516 

Coimbra 

Portugal 

Tel: 351239410667 

E-mail: jmf@gian.fis.uc.pt 

* * * * * * * * 

D'ulivo, Alessandro 

CNR-ICCOM 

Via Moruzzi, 1 

56124 

Pisa 

Italy 

Tel: 393493579149 

E-mail: dulivo@pi.iccom.cnr.it 

* * * * * * * * 

Dundas, Siv Hjorth 

University of Bergen, Dep. of Earth Sciences 

Allegaten 41 

5007 

Bergen 

Norway 

Tel: 97631393 

E-mail: siv.dundas@geo.uib.no 

* * * * * * * * 

Durand, Thibaut 

INRS 

1 rue du Morvan 

54519 

Vandoeuvre les Nancy 

France 

Tel: 383508592 

E-mail: thibaut.durand@inrs.fr 

* * * * * * * * 

-244 -


Eberlin, Marcos 

University of Campinas 

Sala A6-111 

13083-970 

Campinas 

Brazil 

Tel: + 55 19 35213073 

E-mail: eberlin@iqm.unicamp.br 

* * * * * * * * 

Egenolf, Heiko 

BASF SE 

GMC/E - M320 

67056 

Ludwigshafen 

Germany 

Tel: 496216079788 

E-mail: heiko.egenolf@basf.com 

* * * * * * * * 

Ek, Paul 

Åbo Akademi Univ. 

Biskopsgatan 8 

20500 

Turku 

Finland 

Tel: 35822154432 

E-mail: pek@abo.fi 

* * * * * * * * 

Espeseth, Ørjan 

Matriks AS 

GAustadalleen 21 

349 

Oslo 

Norway 

Tel: 4797553812 

E-mail: oe@matriks.no 

* * * * * * * * 

Fehér, Milán 

University of Debrecen 

Böszörményi street 138. 

4032 

Debrecen 

Hungary 

Tel: 365250844488185 

E-mail: feherm@agr.unideb.hu 

* * * * * * * * 

Address List 

Fehérné Baranyai, Edina 


Egyetem square 1. 

4032 

Debrecen 

Hungary 

Tel: 365251290022426 

E-mail: baranyai.edina@science.unideb.hu 

* * * * * * * * 

Feofanov, Alexey 

Shemyakin-Ovchinnikov Institute of Bioorganic 

Chemistry 

ul. Miklukho-Maklaya, 16/10 

117997 

Moscow 

Russia 

Tel: 79262150501 

E-mail: avfeofanov@yandex.ru 

* * * * * * * * 

Fongen, Torfinn 

Holger Hartmann AS 

Berghagan 3 

1405 

Langhus 

Norge 

Tel: 90894920 

E-mail: t.fongen@holgerhartmann.no 

* * * * * * * * 

Fredheim, Bjarne 

PANalytical 

Pb 498 

1411 

Kolbotn 

Norway 

Tel: 4793280062 

E-mail: bjarne.fredheim@panalytical.com 

* * * * * * * * 

Fucsko, Janos 

NMS Labs 

3701 Welsh Road 

19090 

Willow Grove 

United States 

Tel: 12083453765 

E-mail: janos.fucsko@nmslabs.com 

* * * * * * * * 

-245 -


Fujiwara, Tatsuyoshi 

SHIMADZU 

1-3,Kanda-Nishikicho, Chiyoda-Ku 

101-8448 

Tokyo 

Japan 

Tel: 81332195797 

E-mail: fujiwara@shimadzu.co.jp 

* * * * * * * * 

Ganeev, Aleksandr 

Sankt-Petersburg State University 

Universitetsky pr.26 

198504 

Sankt-Petersburg, Petergoff 

Russia 

Tel: 79219070801 

E-mail: ganeev@lumex.ru 

* * * * * * * * 

Garcia Ruiz, Esperanza 

UNIVERSIDAD DE ZARAGOZA 

Calle Pedro Cerbuna 12 

50009 

ZARAGOZA 

SPAIN 

Tel: 34876553503 

E-mail: garciae@unizar.es 

* * * * * * * * 

Gebremariam, Kidane Fanta 

NTNU 

Høgskoleringen 5 

7491 

Trondheim 

Norway 

Tel: 73596225 

E-mail: fanta@ntnu.no 

* * * * * * * * 

Gjengedal, Elin Lovise 


P.O.Box 5003 

1432 

Aas 

Norway 

Tel: 4764965533 

E-mail: elin.gjengedal@umb.no 

* * * * * * * * 

Godin, Simon 

LCABIE CNRS/UPPA 

2 Av. President Angot 

64053 

Pau 

France 

Tel: 33559407762 

E-mail: simon.godin@univ-pau.fr 

* * * * * * * * 

Govaert, Willem 

CPI International 

Spuistraat 9 

1012SP 

Amsterdam 

The Netherlands 

Tel: 31206380597 

E-mail: govaertw@cpiinternational.com 

* * * * * * * * 

Grechnikov, Alexander 

GEOKHI RAS 

Kosygin str., 19 

119991 

Moscow 

Russia 

Tel: 79162002871 

E-mail: grechnikov@geokhi.ru 

* * * * * * * * 

Griffiths, Richard 

NASA 

300 E St SW 

20546 

Washington DC 

USA 

Tel: 12022516454 

E-mail: richard.e.griffiths@nasa.gov 

* * * * * * * * 

Grotti, Marco 

University of Genoa 

Via Dodecaneso 31 

16146 

Genova 

Italy 

Tel: 393492958454 

E-mail: grotti@unige.it 

* * * * * * * * 

Address List 

-246 -


Grützke, Martin 

University of Münster, Institute of Physical 

Chemistry, MEET - Battery Research Centre 

Corrensstraße 46 

48149 

Münster 

Germany 

Tel: 4917663057055 

E-mail: martin.gruetzke@uni-muenster.de 

* * * * * * * * 

Guldhav, Alf Yngve 

Elkem Technology 

Fiskaaveien 100 

4675 

Kristiansand 

Norway 

Tel: 90016381 

E-mail: alf-yngve.guldhav@elkem.no 

* * * * * * * * 

Gundersen, Eirik 

Gammadata 

Weidemannsgate 6 

No-3080 

Holmestrand 

Norge 

Tel: 92615001 

E-mail: eirik.gundersen@gammadata.no 

* * * * * * * * 

Günther, Detlef 

ETH Zürich, D-CHAB 

Wolfgang-Pauli-Str. 10 

8093 

Zürich 


Tel: 41446333475 

E-mail: guenther@inorg.chem.ethz.ch 

* * * * * * * * 

Günther, Helen 

Tel: 41446333475 

E-mail: nbachmann@inorg.chem.ethz.ch 

* * * * * * * * 

Guttormsen, Yngve 


Stalheimveien 10 

9012 

Tromsø 

Norway 

Tel: 4797099695 

E-mail: ygu000@post.uit.no 

* * * * * * * * 

Gysin, Tobias 

Agilent Technologies 

Lautengartenstrasse 6 

4052 

Basel 


Tel: 41793223528 

E-mail: tobias_gysin@agilent.com 

* * * * * * * * 

Hamester, Meike 

Bruker Daltonic 

Fahrenheitstrasse 4 

28359 

Bremen 

Germany 

Tel: 491622925747 

E-mail: meike.hamester@bdal.de 

* * * * * * * * 

Address List 

Hergenröder, Roland 

Leibniz-Institut für Analytische Wissenschaften- 

ISAS 

Bunsen-Kirchhoff Str. 11 

44139 

Dortmund 

Germany 

Tel: 492311392178 

E-mail: roland.hergenroeder@isas.de 

* * * * * * * * 

Heumann, Klaus 

University of Mainz 

Die Lange Schneise 5 

64673 

Zwingenberg 

Germany 

Tel: 496251787637 

E-mail: heumann@uni-mainz.de 

* * * * * * * * 

-247 -


Address List 

Hieftje, Gary 

Indiana University 

800 E Kirkwood Avenue 

47405 

Bloomington, IN 

USA 

Tel: 8128552189 

E-mail: hieftje@indiana.edu 

* * * * * * * * 

Hieftje, Susan 

Tel: 8128552189 

E-mail: hieftje@indiana.edu 

* * * * * * * * 

Hoffmann, Volker 

IFW Dresden 

Helmholtzstrasse 20 

1069 

Dresden 

Germany 

Tel: 493514659691 

E-mail: v.hoffmann@ifw-dresden.de 

* * * * * * * * 

Hoffmann, Björn 

University of Muenster/MEET 


D-48149 

Muenster 

Germany 

Tel: 492518336097 

E-mail: bjoern.hoffmann@wwu.de 

* * * * * * * * 

Höglund, Ann-Cathrine 

Metrohm Nordic AB 

Box 11065 

16111 

Bromma 

Sverige 

Tel: 46856484497 

E-mail: ann-cathrine.hoglund@metrohm.se 

* * * * * * * * 

Hokura, Akiko 

Tokyo Denki University 

Senju-Asahicho, Adachi 

120-8551 

Tokyo 

Japan 

Tel: +81 3 5284 5445 

E-mail: hokura@mail.dendai.ac.jp 

* * * * * * * * 

Hove, Kristin Ellinor 

Apotekproduksjon AS 

Postboks 23 Høybråten 

1005 

Oslo 

Norway 

Tel: 21608731 41920924 

E-mail: kristin.hove@farmaholding.com 

* * * * * * * * 

Hranicek, Jakub 

Charles University in Prague, Faculty of Science 

Albertov 6 

CZ12843 

Prague 2 


Tel: 420777889193 

E-mail: jakub.hranicek@natur.cuni.cz 

* * * * * * * * 

Hsu, Che Lun 

Food and Drug Administration Department of 

Health 

No.161-2, Kunyang St, Nangang District 

11561 

Taipei 

Taiwan 

Tel: 882227877711 

E-mail: jerlun@fda.gov.tw 

* * * * * * * * 

Hu, Yunfei 

Norut Narvik 

Lodve Langesgate 4 

8504 

Narvik 

Norway 

Tel: 4794814256 

E-mail: yunfei.hu@norut.no 

* * * * * * * * 

-248 -


Huber, Sandra 

University Hospital of North Norway / Norwegian 

Institute for Air Research 

Sykehusveien 35 

9038 

Tromsø 

Norway 

Tel: 4746480615 

E-mail: sandra.huber@unn.no 

* * * * * * * * 

Irina, Snigireva 

ESRF 

6 rue Jules Horowitz 

38043 

Grenoble 

France 

Tel: 33476882360 

E-mail: irina@esrf.fr 

* * * * * * * * 

Janasik, Beata 

Nofer Institute of Occupational Medicine 

St. Teresy 8 

91-348 

LODZ 

POLAND 

Tel: 48426314806 

E-mail: beatajan@imp.lodz.pl 

* * * * * * * * 

Jensen, Karl Andreas 


Fougnerbakken 3 

1430 

Ås 

Norway 

Tel: 90564917 

E-mail: karl.jensen@umb.no 

* * * * * * * * 

Jimenez, Maria S. 

University of Zaragoza. GEAS 

Pedro Cerbuna, 12 

50009 

Zaragoza 

Spain 

Tel: 34976762257 

E-mail: jimenezm@unizar.es 

* * * * * * * * 

Jitaru, Petru 

Institut Polytechnique LaSalle Beauvais 

19 rue Pierre Waguet 

60000 

Beauvais 

France 

Tel: + 33 3 44 06 89 72 

E-mail: petru.jitaru@lasalle-beauvais.fr 

* * * * * * * * 

Johnsen, Ida Vaa 

Forsvarets forskningsinstitutt 

postboks 25 

2007 

Kjeller 

Norge 

Tel: 92486953 

E-mail: ida-vaa.johnsen@ffi.no 

* * * * * * * * 

Kaburaki, Yuki 

Tokyo Institute of Technology 

4259-J2-32, Nagatsuta, Midori-ku 

226-8502 

Yokohama 

Japan 

Tel: 81459245689 

E-mail: kaburaki@plasma.es.titech.ac.jp 

* * * * * * * * 

Address List 

Kamnev, Alexander A. 

Institute of Biochemistry and Physiology of Plants 

and Microorganisms, Russian Academy of 

Sciences 

13 Prosp. Entuziastov 

410049 

Saratov 

Russia 

Tel: 78452480549 

E-mail: a.a.kamnev@mail.ru 

* * * * * * * * 

Katskov, Dmitri 

Tshwane University of Technology 

175 N.Mandela dr. 

1 

Pretoria 

South Africa 

Tel: 27123826369 

E-mail: katskovda@tut.ac.za 

* * * * * * * * 

-249 -


Kawai, Jun 

Kyoto University 

Department of Materials Science and 

Engineering 

6,068,501 

Sakyo-ku, Kyoto 

Japan 

Tel: +81 75 753 5442 

E-mail: kawai.jun.3x@kyoto-u.ac.jp 

* * * * * * * * 

Kiefer, Desiree 

Tel: 4917670028179 

E-mail: desiree-kiefer@gmx.de 

* * * * * * * * 

Kiseleva, Liudmila 

Tel: 79219070801 

E-mail: ganeev@lumex.ru 

* * * * * * * * 

Kolz, Jürgen 

Magritek GmbH 

Pauwelsstraße 19 

52074 

Aachen 

Germany 

Tel: 492419631423 

E-mail: juergen@magritek.com 

* * * * * * * * 

Kovalenko, Olesia 

Medved`s Institute of Ecohygiene and Toxicology, 

Ministry of Health, Kyiv, Ukraine 

6 Heroiv Oborony street 

3680 

Kyiv 

Ukraine 

Tel: 61487821754 

E-mail: iouri.kalinitchenko@bruker.com 

* * * * * * * * 

Kraft, Vadim 

University of Münster 

Corrensstrasse 46 

48149 

Münster 

Germany 

Tel: 492518336763 

E-mail: vadim.kraft@uni-muenster.de 

Address List 

Kratzer, Jan 

Academy of Sciences of the Czech Republic, 

Institute of Analytical Chemistry 

Videnska 1083 

14220 

Prague 


Tel: 420241062487 

E-mail: jkratzer@biomed.cas.cz 

* * * * * * * * 

Kubuki, Shiro 

Tokyo Metropolitan University 

Minami-Osawa 1-1 

1920397 

Hachi-Oji 

Japan 

Tel: 81426772432 

E-mail: kubuki@tmu.ac.jp 

* * * * * * * * 

Kudryasheva, Nadezhda 

Inst.of Biophysics SB RAS 

Akademgorodok, 50/50 

660036 

Krasnoyarsk 

Russia 

Tel: 79135613315 

E-mail: n_qdr@yahoo.com 

* * * * * * * * 

Laserna, Javier 

University of Málaga 

Campus de Teatinos 

29071 

Málaga 

Spain 

Tel: 34952131881 

E-mail: laserna@uma.es 

* * * * * * * * 

Laukas, Monica 

Shimadzu/Bergman AS 

Slynga 2 

2005 

Rælingen 

Norge 

Tel: 4740440960 

E-mail: mla@bergman.no 

* * * * * * * * 

* * * * * * * * 

-250 -


Li, Xue 

ETH Zürich 

Wolfgang-Pauli-Strasse 10 

8093 

Zürich 


Tel: +41 44 6334668 

E-mail: xue.li@org.chem.ethz.ch 

* * * * * * * * 

Liao, Wei Ju 

National Yang-Ming University 

No.155, Sec.2, Linong Street, Taipei, 112 Taiwan 

(ROC) 

112 

Taipei 

Taiwan 

Tel: 886932282808 

E-mail: w84344@yahoo.com.tw 

* * * * * * * * 

Lichtenthaler, Thor 

Matriks AS 

Gaustadalleen 21 

349 

Oslo 

Norway 

Tel: 4740068402 

E-mail: tl@matriks.no 

* * * * * * * * 

Lohne, Solfrid 

Norwegian University Of Life Siences 

Boks 5003 

1432 

Ås 

Norway 

Tel: 90097978 

E-mail: solfrid.lohne@umb.no 

* * * * * * * * 

Lund, Walter 


Department of Chemistry, Blindern 

315 

Oslo 

Norway 

Tel: 92400084 

E-mail: walter.lund@kjemi.uio.no 

Lund, Tone 

Tel: 92400084 

E-mail: walter.lund@kjemi.uio.no 

* * * * * * * * 

Lyndgaard, Lotte 

University of Copenhagen 

Rolighedsvej 30, 4.floor 

1958 

Frederiksberg C 

Denmark 

Tel: 4551261227 

E-mail: lottebs@hotmail.com 

* * * * * * * * 

Maiti, Kiran Sankar 

University of Gothenburg 

Medicinaregatan 9E, Box 462 

SE-405 30 

Gothenbuer 

Sweden 

Tel: 46317863941 

E-mail: kiransankar.maiti@gmail.com 

* * * * * * * * 

Address List 

Marquez, Ciro 

UNIVERSIDAD NACIONAL AUTONOMA DE MEXICO 

FACULTAD DE QUIMICA EDIFICIO D CIRCUITO 

EXTERIOR CIUDAD UNIVERSITARIA 

4510 

MEXICO 

MEXICO 

Tel: 525554375465 

E-mail: ciromar@unam.mx 

* * * * * * * * 

Marshall, Kim 

LECO Corporation 

3000 Lakeview Avenue 

49085 

Saint Joseph 

United States 

Tel: 2699825430 

E-mail: kim_marshall@lecotc.com 

* * * * * * * * 

* * * * * * * * 

-251 -


Address List 

Martinsen, Ivar 

GE Healthcare 

P.O. Box 4220 Nydalen 

401 

Oslo 

Norway 

Tel: +47 23185559 

E-mail: ivar.martinsen@ge.com 

* * * * * * * * 

Mccrindle, Robert 


P/B X680 

1 

Pretoria 

South Africa 

Tel: +27 12 3826290 

E-mail: mccrindleri@tut.ac.za 

* * * * * * * * 

Mcsheehy, Shona 

Thermo Fisher Scientific 

Hanna-Kunath-Str. 11 

28199 

Bremen 

Deutschland 

Tel: 4942154930 

E-mail: 

shona.mcsheehyducos@thermofisher.com 

* * * * * * * * 

Melo, Virgninia 

Universidad Autonoma Metropolitana 

Calz. del Hueso 1100, Col Villa Quietud, Del. 

Coyoacan 

4960 

Mexico City 

México 

Tel: 525554837402 

E-mail: vmelo@correo.xoc.uam.mx 

* * * * * * * * 

Metouge Serge, Soume 

International Research Group and Consultancy 

Nouvelle Route Omnisport 

4004 

Yaounde 

Cameroon 

Tel: 23790675305 

E-mail: interres_groupcon@yahoo.com 

* * * * * * * * 

Mihucz, Victor G. 

Elte Kkkk 

Pazmany Peter Stny 1/A 

1117 

Budapest 

Hungary 

Tel: 36705221977 

E-mail: vigami72@yahoo.es 

* * * * * * * * 

Minami, Takeshi 

Kinki University 

3-4-1 Kowakae 

577-8502 

Higashi-osaka 

JAPAN 

Tel: 81667212332 

E-mail: minamita@life.kindai.ac.jp 

* * * * * * * * 

Mink, János 

Research Centre for Natural Sciences, Hungarian 

Academy of Sciences 

Pusztaszeri út 59-67 

1025 

Budapest 

Hungary 

Tel: 36204699006 

E-mail: jmink@chemres.hu 

* * * * * * * * 

Monteiro, Cristina M B 

Physics Department, University of Coimbra 

Rua Larga 

3004 - 516 

Coimbra 

Portugal 

Tel: 351239410667 

E-mail: cristina@gian.fis.uc.pt 

* * * * * * * * 

Montes-Bayon, Maria 

University of Oviedo 

Julian Claveria 8 

33006 

Oviedo 

Spain 

Tel: 985103478 

E-mail: montesmaria@uniovi.es 

* * * * * * * * 

-252 -


Moreira, Isabel 

Pontifícia Universidade Catolica do Rio de Janeiro 

Rua Marques de Sao Vicente, 225 - Gavea 

22453-900 

Rio de Janeiro 

Brazil 

Tel: +55 21 35271810 

E-mail: isabel@puc-rio.br 

* * * * * * * * 

Mushtaq, Sohail 

London Metropolitan University 

166-220 Holloway Road 

N7 8DB 

London 

UK 

Tel: 447501182573 


* * * * * * * * 

Nakai, Izumi 

Tokyo University of Science 

Kagurazaka, Shinjuku 

162-8601 

Tokyo 

Japan 

Tel: 819088557905 

E-mail: inakai@rs.kagu.tus.ac.jp 

* * * * * * * * 

Nakajima, Hiromitsu 

Yokohama National University 

79-7 Tokiwadai 

240-8501 

Yokohama 

Japan 

Tel: 81453394369 

E-mail: h-nakaji@ynu.ac.jp 

* * * * * * * * 

Nickel, Hubertus 

Research Centre Juelich and University of 

Technology Aachen 

Am Waldeck 5 

52428 

Juelich 

Germany 

Tel: 49246153424 

E-mail: h.nickel@fz-juelich.de 

Nickel-Peltzer, Gabriele 

Tel: 49246153424 

E-mail: h.nickel@fz-juelich.de 

* * * * * * * * 

Nielsen, Claus 


Department of Chemistry 

316 

Oslo 

Norway 

Tel: 91103760 

E-mail: clausn@kjemi.uio.no 

* * * * * * * * 

Nizkorodov, Sergey 

Univeristy of California, Irvine 

377 Rowland Hall 

92697-2025 

Irvine, CA 

USA 

Tel: 19498241262 

E-mail: nizkorod@uci.edu 

* * * * * * * * 

Address List 

Njemo, Chah Fritz 

Department of Chemistry, University of Yaounde I 

Gumuspala Mah Palmiye SK Haci Elmas No.8, 

D.17 Avcilar 

34310 

Istanbul 

Turkey 

Tel: 905396484405 

E-mail: njemofritz@yahoo.fr 

* * * * * * * * 

Noetzel, Uwe 


Hewlett-Packard-Str. 8 

76337 

Waldbronn 

Germany 

Tel: 4915114758830 

E-mail: uwe_noetzel@agilent.com 

* * * * * * * * 

* * * * * * * * 

-253 -


Address List 

Norris, Vic 

University of Rouen 

rue Thomas Becket 

76230 

Mont Saint Aignan 

France 

Tel: 33235710791 

E-mail: victor.norris@univ-rouen.fr 

* * * * * * * * 

Nowak, Sascha 

University of Münster 


48149 

Münster 

Germany 

Tel: 492518336735 

E-mail: sascha.nowak@uni-muenster.de 

* * * * * * * * 

Nowka, Rene 

Analytik Jena AG 

Konrad Zuse Straße 1 

7745 

Jena 

Germany 

Tel: 4917617777021 

E-mail: r.nowka@analytik-jena.de 

* * * * * * * * 

Odland, Jon Øyvind 

Department of Community Medicine 


9019 

Tromsø 

Norway 

Tel: 4777646407 

E-mail: jon.oyvind.odland@ism.uit.no 

* * * * * * * * 

Okajima, Toshihiro 

Kyushu Synchrotron Light Research Center 

8-7 Yayoigaoka, Tosu 

841-0005 

Saga 

Japan 

Tel: 81942835017 

E-mail: okajima@saga-ls.jp 

* * * * * * * * 

Omang, Sverre Havig 

Arr. komite 

Munkedamsveien 86 A 

N-0270 

Oslo 

Norway 

Tel: 4795163594 

E-mail: sverre@omang.com 

* * * * * * * * 

Onor, Massimo 

CNR-ICCOM-PISA 

Via Moruzzi, 1 

56124 

Pisa 

ITALY 

Tel: 393389639041 

E-mail: onor@pi.iccom.cnr.it 

* * * * * * * * 

Oppermann, Uwe 

Shimadzu Europa GmbH 

Albert-Hahn-Str. 6-10 

47269 

Duisburg 

Germany 

Tel: 492037687423 

E-mail: uo@shimadzu.eu 

* * * * * * * * 

Ossipov, Konstantin 

Lomonosov Moscow State University 

1-3 Leninskie Gory 

119991 

Moscow 

Russian Federation 

Tel: +7 926 950 66 13 

E-mail: ossipovk@yandex.ru 

* * * * * * * * 

Ottesen, Siri 

Apotekproduksjon AS 

Postboks 23 Høybråten 

1005 

Oslo 

Norway 

Tel: 2160879590968130 

E-mail: siri.ottesen@farmaholding.com 

* * * * * * * * 

-254 -


Paggio, Stefano 

Milestone Srl 

Via Fatebenefratelli 

24010 

Sorisole Bergamo 

Italy 

Tel: 39035573857 

E-mail: s.paggio@milestonesrl.com 

* * * * * * * * 

Palleschi, Vincenzo 

ICCOM-CNR 

via moruzzi 1 

56124 

Pisa 

Italy 

Tel: 390503152224 

E-mail: vincenzo.palleschi@cnr.it 

* * * * * * * * 

Palu, Michel 

Postnova 

Ainontie 64 

1630 

Vantaa 

Finland 

Tel: 358500853166 

E-mail: michel.palu@norlab.fi 

* * * * * * * * 

Panichev, Nikolay 


Nelson Mandela Drive 

2 

Pretoria 

South Africa 

Tel: +27 73 661 6061 

E-mail: panichevn@tut.ac.za 

* * * * * * * * 

Panicheva, Svetlana 

Tel: +27 73 661 6061 

E-mail: panichevn@tut.ac.za 

* * * * * * * * 

Address List 

Payehghadr, Mahmood 

Payame Noor University 

Nakhl Street, Lashgarak Road 

1955883133 

Tehran 

Iran 

Tel: 982188082147 

E-mail: mahmood_payehghadr@yahoo.com 

* * * * * * * * 

Pekárek, Tomás 

Zentiva, k.s. 

U Kabelovny 130 

10237 

Prague 10 


Tel: 420724305996 

E-mail: tomas.pekarek@zentiva.cz 

* * * * * * * * 

Pereira, Fabiola 

Embrapa Instrumentation 

Rua Quinze de Novembro, 1452 

13561-206 

São Carlos 

Brazil 

Tel: 551621072821 

E-mail: fmverbi@uol.com.br 

* * * * * * * * 

Pereiro, Rosario 

Department of Physical and Analytical Chemistry, 

Faculty of Chemistry, University of Oviedo 

C/ Julian Claveria, 8. 

ES-33006 

Oviedo 

Spain 

Tel: 34985103512 

E-mail: mrpereiro@uniovi.es 

* * * * * * * * 

Perinu, Cristina 

Telemark University College 

Kjølnes Ring 56 

N-3901 

Porsgrunn 

Norway 

Tel: 4794262212 

E-mail: cristina.perinu@hit.no 

* * * * * * * * 

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Petersen, Jan Bjørk 

Thermo Scientific 

Stamholmes 193 

2650 

Hvidovre 

Denmark 

Tel: 40256435 

E-mail: jan.petersen@thermo.com 

* * * * * * * * 

Pitzalis, Emanuela 

CNR ICCOM 

via Moruzzi 1 

56124 

Pisa 

Italy 

Tel: 390503152558 

E-mail: pitzalis@pi.iccom.cnr.it 

* * * * * * * * 

Posta, József 


Egyetem tér 1. 

H-4032 

Debrecen 

HUNGARY 

Tel: 3652782985 

E-mail: posta.jozsef@science.unideb.hu 

* * * * * * * * 

Prange, Andreas 

Helmholtz Zentrum Geesthacht 

Max-Planck-Str. 1 

21502 

Geesthacht 

Germany 

Tel: 0049 4152 87 1858 

E-mail: andreas.prange@hzg.de 

* * * * * * * * 

Proskurin, Mikhail 

Department of Analytical Chemistry, M.V. 

Lomonosov Moscow State University 

Vorob`evy Hills, d. 1, Str. 3 

119991 

Moscow, GSP-2, V-234 

Russia 

Tel: 74959393514 

E-mail: proskurnin@gmail.com 

* * * * * * * * 

Pulkkinen, Raine 

Rigaku 

Am Hardtwald 11 

76275 

Ettlingen 

Deutschland 

Tel: 49724394936 

E-mail: raine.pulkkinen@rigaku.com 

* * * * * * * * 

Ramstad, Hanne 

Bergman AS/Shimadzu 

Slynga 2 

2007 

Rælingen 

Norway 

Tel: 4741479591 

E-mail: hra@bergman.no 

* * * * * * * * 

Ray, Steven 

Indiana University 


47405 

Bloomington, IN 

USA 

Tel: 8123455021 

E-mail: sjray@indiana.edu 

* * * * * * * * 

Reich, Tobias 

Johannes Gutenberg University Mainz 

Institute of Nuclear Chemistry 

55099 

Mainz 

Germany 

Tel: 4961313925250 

E-mail: tobias.reich@uni-mainz.de 

* * * * * * * * 

Address List 

Reichert, Matthias Johannes 

University of Muenster 


48149 

Muenster 

Germany 

Tel: 492518336748 

E-mail: mathias.reichert@uni-muenster.de 

* * * * * * * * 

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Address List 

Reiersen, Lars-Otto 

AMAP 


349 

Oslo 

Norway 

Tel: 22958343 

E-mail: lars-otto.reiersen@amap.no 

* * * * * * * * 

Resano, Martín 

Universidad de Zaragoza 

Pedro Cerbuna 12 

50009 

Zaragoza 

España 

Tel: 645983990 

E-mail: mresano@unizar.es 

* * * * * * * * 

Rodin, Igor 

Moscow State University 

Leninsky Gory 1-3 

119992 

Moscow 

Russia 

Tel: 79104507092 

E-mail: igorrodin@yandex.ru 

* * * * * * * * 

Rodrigues Pereira Filho, Edenir 

UFSCar 

Rodovia Washington Luiz, km 235 

CEP 13565-905 

São Carlos 

Brazil 

Tel: 55 16 33518092 

E-mail: erpf@uol.com.br 

* * * * * * * * 

Roempp, Andreas 

Justus Liebig University 

Schubertstrasse 60 

35392 

Giessen 

Germany 

Tel: 496419934802 

E-mail: andreas.roempp@anorg.chemie.unigiessen.de 

* * * * * * * * 

Romachevskiy, Kirill 

RITVERC GmbH 

Kurchatova str 10 

195030 

Saint-Petersburg 

Russia 

Tel: 79312883046 

E-mail: kirill-allianz@yandex.com 

* * * * * * * * 

Ronander, Inger 

Nerliens Meszansky A/S 

Økernveien 121 

NO-0579 

Oslo 

Norway 

Tel: 4791771366 

E-mail: inger.ronander@nmas.no 

* * * * * * * * 

Rosland, Eivind 

Borregard AS 

Hjalmar Wesselsvei 10 

1701 

Sarpsborg 

Norway 

Tel: 4799692941 

E-mail: eivind.rosland@borregaard.com 

* * * * * * * * 

Roy, Susmita 

University of Gothenburg 

Medicinaregatan 9E, Box 462 

SE-405 30 

Gothenburg 

Sweden 

Tel: 46317863915 

E-mail: sushrits@gmail.com 

* * * * * * * * 

Røyset, Oddvar Kjell 

NIVA 


349 

OSLO 

Norway 

Tel: 4790149541 

E-mail: oddvar.roeyset@niva.no 

* * * * * * * * 

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Rybinova, Marcela 

Charles University in Prague, Faculty of Science 

Albertov 6 

CZ12843 

Prague 2 


Tel: 420723225094 

E-mail: rybinova.marcela@seznam.cz 

* * * * * * * * 

Sala, Martin 

National institute of chemistry Slovenia 

Hajdrihova 19 

1000 

Ljubljana 

Slovenia 

Tel: 38651393537 

E-mail: martin.sala@ki.si 

* * * * * * * * 

Samin, Tahereh 

Tel: 982188082147 

E-mail: ladansamin@yahoo.com 

* * * * * * * * 

Sarkar, Nirmal Kumar 

Karimganj College 

Karimganj 

788710(Assam) 

Karimganj 

India 

Tel: 919435375599 

E-mail: nksarkar49@gmail.com 

* * * * * * * * 

Selih, Vid Simon 

National Institute of Chemistry Slovenia 

Hajdrihova ulica 19 

SI-1000 

Ljubljana 

Slovenija 

Tel: 38614760214 

E-mail: vid.selih@ki.si 

* * * * * * * * 

Address List 

Seren, Gulay 

Trakya University 

Trakya University, Faculty of Pharmacy, 

Department of Analytical Chemistry, Balkan 

Campus 

22030 

Edirne 

Turkey 

Tel: 00 90 2842359213 

E-mail: gulayseren@trakya.edu.tr 

* * * * * * * * 

Seren, Ilsu 

Tel: 902842359213 

E-mail: gulayseren@trakya.edu.tr 

* * * * * * * * 

Severo Azevedo Silva, Jessee 

Universidade Federal de Santa Catarina 

Rua Jose francisco pereira,134 

88047240 

Florianopolis 

Brasil 

Tel: 5504832263727 

E-mail: jesseesevero@yahoo.com.br 

* * * * * * * * 

Silva, Andrea 

University of State of Rio de Janeiro 

Rua São Francisco Xavier 524/ sala 3007F 

20550-900 


Brazil 

Tel: +55 21 81992493 

E-mail: mantuanoandrea@gmail.com 

* * * * * * * * 

Skarpeid, Kate 

Elkem AS Technology Lab 

P.O. box 8040 Vaagsbygd 

4675 


Norway 

Tel: 4790195801 

E-mail: kate.skarpeid@elkem.no 

* * * * * * * * 

Sohail, Misbah 

Tel: 447501182573 


* * * * * * * * 

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Address List 

Sramon, Modhu Barua 

wat ton sai onnut 29 

sukhumvit 77 suanluang 

bangkok 10250 

bangkok 

Thailand 

Tel: 6681564182 

E-mail: modhubarua@yahoo.com 

* * * * * * * * 

Stabile Amais, Renata 

Federal University of Sao Carlos 

Rodovia Washington Luis, km 235. SP-310 

676 

Sao Carlos - SP 

Brazil 

Tel: 55 16 33518058 

E-mail: renata_amais@yahoo.com.br 

* * * * * * * * 

Stefano, Legnaioli 

ICCOM-CNR 

via Moruzzi 1 

56124 

Pisa 

Italy 

Tel: 390503152221 

E-mail: s.legnaioli@pi.iccom.cnr.it 

* * * * * * * * 

Steinnes, Eiliv 

NTNU 


NO-7491 

Trondheim 

Norway 

Tel: 22754320 

E-mail: eiliv.steinnes@ntnu.no 

* * * * * * * * 

Suchikova, Yana 

BSPU 

Bach 45, fl. 39 

71100 

Berdyansk 

Ukraine 

Tel: 380663387864 

E-mail: yanasuchikova@mail.ru 

Szigeti, Tamás 

Eötvös Loránd University 

Pázmány Péter stny. 1/A 

H-1117 

Budapest 

Hungary 

Tel: 36309084346 

E-mail: tamas.szigeti@yahoo.com 

* * * * * * * * 

Thisted, Elke 

Elkem AS Technology 

P.O.box 8040 Vaagsbygd 

4675 


Norway 

Tel: 4792808482 

E-mail: elke.thisted@elkem.no 

* * * * * * * * 

Thomassen, Yngvar 

National Institute of Occupational Health 

P.O. Box 8149 DEP 

N-0033 

Oslo 

Norway 

Tel: 4723195320 

E-mail: yngvar.thomassen@stami.no 

* * * * * * * * 

Thomassen, Magny 

Tel: 4799510521 

E-mail: magny.thomassen@umb.no 

* * * * * * * * 

Tonietto, Gisele Birman 

PUC-Rio 

Rua Marques de S Vicente, 225 

22451-900 


Brasil 

Tel: 55 21 99412561 

E-mail: giselebt@puc-rio.br 

* * * * * * * * 

* * * * * * * * 

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Török, Szabina 

HAS Eneregy Research Centre 

Konkoly-Thege ut 29. 

1121 

Budapest 

Hungary 

Tel: 36323922298 

E-mail: sztorok@aeki.kfki.hu 

* * * * * * * * 

Tugarova, Anna 

Institute of Biochemistry and Physiology of Plants 

and Microorganisms RAS 

13 Prospekt Entuziastov 

410049 

Saratov 

Russia 

Tel: 79173076316 

E-mail: tugarova_anna@mail.ru 

* * * * * * * * 

Van Oijen, Albert 

Carat GmbH 

Harderhook 20 

46395 

Bocholt 

Germany 

Tel: 4928712399220 

E-mail: albert.van.oyen@carat-lab.com 

* * * * * * * * 

Varilova, Tereza 

Tel: 420724869492 

E-mail: tereza.varilova@seznam.cz 

* * * * * * * * 

Vasileva-Veleva, Emiliya 

IAEA Environment Laboratories 

4 Quai Antoine 1 er 

98000 

Monaco 

Monaco 

Tel: 37797977237 

E-mail: e.vasileva-veleva@iaea.org 

* * * * * * * * 

Vieskar, Rune 

PerkinElmer Norway 

P.O. Box 4468 Nydalen 

403 

Oslo 

Norway 

Tel: 4792665138 

E-mail: rune.vieskar@perkinelmer.com 

* * * * * * * * 

Address List 

Volkov, Dmitry 

Moscow State University, Chemical Department 

Leninskie gori, 1, str. 3 

119991 

Moscow 

Russia 

Tel: 79164176761 

E-mail: dmsvolkov@gmail.com 

* * * * * * * * 

Weber, Sascha 

University of Muenster 


48149 

Muenster 

Germany 

Tel: 492518336707 

E-mail: sascha.weber@uni-muenster.de 

* * * * * * * * 

Weinbruch, Stephan 

Technical University Darmstadt 

Schnittspahnstrasse 9 

DE-64287 

Darmstadt 

Germany 

Tel: 496151165280 

E-mail: weinbruch@geo.tu-darmstadt.de 

* * * * * * * * 

Wendt, Jarrett 

CPI International 

5580 Skylane Boulevard 

95403 

Santa Rosa 

United States 

Tel: 17075255788 

E-mail: wendtj@cpiinternational.com 

* * * * * * * * 

-260 -


Address List 

Winship, Peter David 

CETAC Technologies 

8 Merivale Way 

CB74GQ 

Ely 

United Kingdom 

Tel: 447788242230 


* * * * * * * * 

Woywod, Clemens 

UiT 

CTCC, chem. dept. UiT 

9037 

Tromso 

Norway 

Tel: 4777623105 

E-mail: woywod@ch.tum.de 

* * * * * * * * 

Wuelfken, Jan 


Hewlett Packard Straße 8 

76337 

Waldbronn 

Germany 

Tel: 4915114079696 

E-mail: jan.wuelfken@agilent.com 

* * * * * * * * 

Zenobi, Renato 

ETH Zurich 

HCI E 329 

CH-8093 

Zurich 


Tel: +41 44 632 43 76 

E-mail: zenobi@org.chem.ethz.ch 

* * * * * * * * 

Zimmermann, Ralf 

JMSC (HMGU/University of Rostock) 

Ingolst. Landstr. 1 

85764 

Neuherberg 

Germany 

Tel: 4015112288259 

E-mail: ralf.zimmermann@gsf.de 

* * * * * * * * 

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