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Institut für Umweltphysik und Arbeitsstelle Radiometrie
Annual Research Report
2005
Ruprecht-Karls-Universität Heidelberg
und
Heidelberger Akademie der Wissenschaften

Professor Dr. Karl Otto Münnich
(1. 1. 1925 – 26. 10. 2003)
It has been more than 25 years since the last Annual Report on the scientific work in our
Institute. We, thus, want to take this opportunity to commemorate Karl Otto Münnich,
the founding father and first Director of the Institut für Umweltphysik (Environmental
Physics), to whom we dedicate this report.
Karl Otto Münnich was born and grew up in Heidelberg. He studied Physics at the
University of Heidelberg and received his doctoral degree in 1957. During his PhD work
he established the Radiocarbon Dating Laboratory in Heidelberg which later became
part of the Heidelberger Akademie der Wissenschaften (Academy of Sciences). Karl
Otto Münnich quickly realised the universal significance of the Radiocarbon method
far beyond its application in archaeology. As one of the first topics, together with John
C. Vogel, he pioneered the ground water dating method. Also during the 1950s and 60s
Münnich became witness of the dramatic consequences of atmospheric nuclear weapon
testing on radionuclide concentrations in the environment. He was among the first
to utilise this “global tracer experiment” and study exchange processes between the
important compartments of the climate system, therewith establishing the new research
field of Environmental Physics. After a sabbatical in the US and a directorate at the
Forschungszentrum Jülich, Karl Otto Münnich was appointed director of the newly
founded Institut für Umweltphysik (Institute for Environmental Physics) in 1974. Here
he demonstrated a unique combination of abstract thinking in terms of fundamental
physics, experimental skills, and interdisciplinary insight. His excellent sense to extract
the pivotal points of the often highly complex processes in nature permitted him to
elaborate fundamental, but still simple solutions in a variety of fields. He was an
excellent and adored teacher, colleague and friend to many of us. Karl Otto Münnich
attracted a large number of students, and his work became well established world-wide
with many of his alumni now teaching this discipline themselves.
Today the various methods originally introduced by Karl Otto Münnich are applied to
all major environmental subsystems, where physics plays the central role for process
understanding. At the Heidelberg Institute his pioneering ideas have been well implemented
and are successfully pursued. The 2005 Scientific Report nicely illustrates how
we endeavour to carry Karl Otto Münnich’s early visions into the future.

Contents
1 Introduction/Overview of institute 9
2 Atmosphere and Remote Sensing 11
2.1 Tropospheric Research Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.1.1 Halogen oxide and sulphur dioxide emission of volcanoes . . . . . . . . . . . . . 19
2.1.2 Studies of Reactive Halogen Species (RHS) in the Marine and mid-Latitudinal
Boundary Layer by Active Longpath Differential Optical Absorption Spectroscopy
(DOAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.1.3 Improvement of the Detection Limit of Active-DOAS-Measurements by use of
fibre coupled light source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.1.4 New Operational Software for Automatic DOAS Measurement and Analysis . . 22
2.1.5 Ground based MAX-DOAS measurements . . . . . . . . . . . . . . . . . . . . . 23
2.1.6 Imaging DOAS. Imaging of two-dimensional trace gas distributions . . . . . . . 24
2.1.7 Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) of Trace
Gas and Aerosol Distributions . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.1.8 The flying laboratory: DOAS on board the CARIBIC aircraft project . . . . . 26
2.1.9 Heidelberg ground-based network . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.1.10 Applicability of light-emitting diodes as light sources
for active DOAS measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.1.11 Active DOAS measurements of trace gases in the free troposphere . . . . . . . 29
2.1.12 Long Term Observations of Urban Atmospheric Radical Chemistry
(TURBAN) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.2 Stratospheric Ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2.1 Investigation of Inorganic Stratospheric Bromine . . . . . . . . . . . . . . . . . 38
2.2.2 Stratospheric photochemistry of ozone, nitrogen and chlorine species . . . . . . 39
2.2.3 Photolytic lifetime of stratospheric N2O5 . . . . . . . . . . . . . . . . . . . . . 40
2.2.4 Spectroscopic measurements of halogen oxides in the marine boundary layer in
Alcântara/Brazil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.2.5 Ground-based direct Sun UV/vis spectroscopy in Timon/Northeastern Brazil:
Comparison of tropospheric air mass pollution in the dry and wet season . . . 42
2.3 Radiative Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.3.1 Development and Application of a Versatile Balloon-Borne DOAS Instrument
for Skylight Radiance and Atmospheric Trace Gas Profile Measurements . . . . 48
2.3.2 Oxygen A-band measurements for solar photon path length distribution studies 49
2.3.3 Absolutely calibrated solar irradiance measurements . . . . . . . . . . . . . . . 50
2.3.4 Atmospheric detection of water dimers and their contribution to solar shortwave
absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.4 DOAS Tomography Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2.4.1 Intercomparison of ambient in-situ Formaldehyde Measurements in urban Air . 58
2.4.2 Trace gas distributions from long-path DOAS measurements . . . . . . . . . . 59
2.4.3 Airborne measurements of the CH2O and NO2 distributions in the Po basin . 60
2.4.4 Development of a Multibeam instrument for simultaneous measurements along
multiple light paths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.4.5 An Indoor Test Campaign of the Tomography Long Path Differential Optical
Absorption Spectroscopy (DOAS) Technique . . . . . . . . . . . . . . . . . . . 62
2.4.6 2D and 3D tomographic LP-DOAS measurements of trace gas distributions in
Heidelberg over an area of 4 ∗ 4 km 2 . . . . . . . . . . . . . . . . . . . . . . . . 63
2.4.7 Two-dimensional measurement of motorway emission plumes . . . . . . . . . . 64
5

6 CONTENTS
2.4.8 Two dimensional concentration distributions of a NO2 Emission plume from a
point source derived by Airborne DOAS Tomography . . . . . . . . . . . . . . 65
2.4.9 Development of a computer tool for the inversion and optimization of airborne
tomographic DOAS measurements (Tomolab2) . . . . . . . . . . . . . . . . . . 66
2.5 Satellite Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2.5.1 Quantifying NOx from lightning using satellite data . . . . . . . . . . . . . . . 72
2.5.2 Evaluation of global tropospheric NO2 from SCIAMACHY . . . . . . . . . . . 73
2.5.3 Development of a radiative transfer model . . . . . . . . . . . . . . . . . . . . . 74
2.5.4 Retrieval of methane from SCIAMACHY onboard ENVISAT . . . . . . . . . . 75
2.5.5 Retrieval of carbon monoxide from SCIAMACHY onboard ENVISAT . . . . . 76
2.5.6 Retrieval of cloud parameters using SCIAMACHY and GOME data . . . . . . 77
2.5.7 Satellite validation using the airborne multi axis DOAS instrument . . . . . . . 78
2.5.8 Analysis of global long-term tropospheric and stratospheric BrO from GOME
measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.5.9 Enhanced SO2 Column Densities Observed Over South East Asian Region: Consequence
of El Niño . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.5.10 Retrieving vertical profiles of stratospheric trace gases from satellite observations 81
2.5.11 Comparison of OClO nadir measurements from SCIAMACHY and GOME . . 82
2.5.12 Identification of tropospheric emissions sources from satellite observations: Synergistic
use of HCHO and NO2 trace gas measurements . . . . . . . . . . . . . 83
2.5.13 Trace gas profile retrieval from SCIAMACHY limb measurements . . . . . . . 84
2.5.14 Mie theory based characterization and modeling of atmospheric aerosols . . . . 85
2.5.15 Satellite observations of the global water vapor distribution . . . . . . . . . . . 86
2.5.16 Analysis of MAXDOAS observations in various observing geometries . . . . . . 87
2.5.17 Comparison of Radiative Transfer Models . . . . . . . . . . . . . . . . . . . . . 88
2.5.18 GOME observations of stratospheric trace gas distributions during the split
vortex event in the Antarctic winter 2002 . . . . . . . . . . . . . . . . . . . . . 89
2.5.19 Comparison of GOME NO2 retrievals analysed by different scientific groups . . 90
2.6 MarHal - Modeling of marine and halogen chemistry . . . . . . . . . . . . . . . . . . . 95
2.6.1 Modeling the possible role of iodine oxides in new particle formation . . . . . . 99
2.6.2 Ozone Depletion Events in the Polar Boundary Layer in Spring: A Model Study 100
2.6.3 Modeling Organic Films on Atmospheric Aerosol Particles and their Influence
on Cloud Microphysics and Chemistry . . . . . . . . . . . . . . . . . . . . . . . 101
2.6.4 Impact of reactive bromine chemistry in the troposphere . . . . . . . . . . . . . 102
2.7 Carbon Cycle Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.7.1 Global long-term observations of Radiocarbon in atmospheric CO2, revisited . 108
2.7.2 Simulating Bomb Radiocarbon: Implications for the Global Carbon Cycle . . . 109
2.7.3 Coupling and modernisation of the Heidelberg Greenhouse Gases and CO - GC
systems for continuous measurements . . . . . . . . . . . . . . . . . . . . . . . 110
2.7.4 Investigating CO2, CO and Fossil Fuel CO2 in Heidelberg . . . . . . . . . . . . 111
3 Terrestrial Systems 115
3.1 Soil Physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
3.1.1 Estimation of effective hydraulic parameters for heterogeneous porous media . 122
3.1.2 X-ray attenuation techniques to study the dynamics of water in porous media . 123
3.1.3 Fingered Flow Through Initially Dry Porous Hele-Shaw cell . . . . . . . . . . . 124
3.1.4 Near Infrared Imaging Spectroscopy of Water States in Porous Silicate Media . 125
3.1.5 Evaporation Experiment to determine Soil Hydraulic Properties . . . . . . . . 126
3.1.6 Free Parameterisation of Soil Hydraulic Properties . . . . . . . . . . . . . . . . 127
3.1.7 Modelling water flow and solute transport in heterogeneous soil . . . . . . . . . 128
3.1.8 Unsaturated Flow in Strongly Heterogeneous Porous Media . . . . . . . . . . . 129
3.1.9 Assessing temporal changes in volumetric soil water content from ground-penetrating
radar profiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
3.1.10 Monitoring Field Tracer Experiment with Ground Penetrating Radar and Time
Domain Reflectometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
3.1.11 Efficient reconstruction of dispersive dielectric profiles using TDR . . . . . . . 132
3.1.12 3D Full-wave, electromagnetic model of ground penetrating radar systems . . . 133
3.1.13 Simulation and Observation of an Evanescent Wave in Ground Penetrating
Radar Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
3.2 Ice and Climate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137

CONTENTS 7
3.2.1 Glaciological pilot studies on a cold miniature ice cap . . . . . . . . . . . . . . 140
3.2.2 Constraining the anthropogenic fraction of carbonaceous aerosol by 14 C-analysis 141
3.2.3 Recent variability of the cosmogenic nuclides 10 Be and 7 Be in coastal Antarctica 142
3.2.4 Climatic significance of stable water isotope records from Alpine ice cores. . . 143
3.2.5 Analyses of dissolved organic carbon (DOC) at low levels in Alpine and polar
glaciers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
3.2.6 Novel tools in ice core research . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
4 Aquatic Systems 149
4.1 Groundwater and Paleoclimate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
4.1.1 A tracer study of paleoclimate and groundwater recharge in the North China
Plain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
4.1.2 A multi-tracer study of groundwater in reclamation areas south-west of the Nile
Delta, Egypt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
4.1.3 A multi tracer study to investigate the groundwater in the Odenwald region . . 156
4.1.4 A new mass spectrometric system for measurement of noble gases and first
applications to perform measurements of fluid inclusions in speleothems . . . . 157
4.1.5 Advancing the use of noble gases as palaeoclimate indicators . . . . . . . . . . 158
4.1.6 Radon as tracer for lake - groundwater interaction . . . . . . . . . . . . . . . . 159
4.2 Lake Research (Limnophysics) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
4.2.1 Sulfurhexaflourid (SF6) as tracer for transport and mixing processes in mining
lakes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
4.2.2 Vertical transport in stratified lakes . . . . . . . . . . . . . . . . . . . . . . . . 164
4.2.3 Investigation of Water Currents in Lake Willersinnweiher using Acoustic Doppler
Current Profiler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
5 Small-Scale Air-Sea Interaction 167
5.1 Small-Scale Air-Sea Interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
5.1.1 Investigation of transport processes across the sea-surface microlayer by active
thermography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
5.1.2 Water flow measurements in environmental and biological systems . . . . . . . 175
5.1.3 Time resolved Measurements of Air Water Gas Exchange . . . . . . . . . . . . 176
5.1.4 3-D flow measurements within a porous gravel layer . . . . . . . . . . . . . . . 177
5.1.5 3D fluid flow measurement close to surfaces . . . . . . . . . . . . . . . . . . . . 178
5.1.6 Imaging concentration profiles of water boundary layer by Double-Dye LIF . . 179
5.1.7 Combined slope/height measurements of short wind waves : ISHG . . . . . . . 180
5.1.8 Development of a depth resolving boundary layer visualization for gas exchange
at free water surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
6 Forschungsstelle “Radiometrie” of the Heidelberger Akademie der Wissenschaften185
6.1 Radiometric Dating of Water and Sediments . . . . . . . . . . . . . . . . . . . . . . . . 187
6.1.1 Reconstruction of the geomagnetic field strength over the past 300,000 years
derived from 10 Be data of deep sea sediments from the North and South Atlantic
Ocean . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
6.1.2 Possible solar origin of the glacial 1,470-year climate cycle demonstrated in a
coupled climate model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
6.1.3 Solar variability and rapid climate change on decadal to centennial scales . . . 193
6.1.4 Establishment of a method for measuring 231 Pa in deep-sea sediments via ICP-MS194
6.1.5 Modelling of stable isotope records of stalagmites . . . . . . . . . . . . . . . . . 195
6.1.6 Reconstruction of the 10 Be-production based on deep sea sediments from the
North Atlantic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
6.1.7 U/Th dating of deep-water corals from the North Atlantic . . . . . . . . . . . . 197
6.1.8 Isochron dating of fossil reef corals and the reconstruction of past sea level
fluctuations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
6.1.9 Dating and interpretation of the carbon and oxygen isotopes of two Holocene
stalagmites from the South of Chile (Patagonia) . . . . . . . . . . . . . . . . . 199
6.1.10 Chronostratigraphy of the Nasca culture and palaeoclimate reconstruction of
the Palpa region (Peru) by AMS- 14 C dating . . . . . . . . . . . . . . . . . . . . 200
6.1.11 Nonlinear time-series analysis of nonstationary signals . . . . . . . . . . . . . . 201
6.1.12 The authigenic 10 Be/ 9 Be ratio in deep sea sediments as a proxy for the Earth‘s
magnetic field intensity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202

8 CONTENTS
Bibliography 207
Peer Reviewed Publications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
Grey Publications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
PhD Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
Diploma Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
Invited Talks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221

Introduction
In Heidelberg, environmental physics continuously developed since the 1950s from the application of
nuclear physics methods to environmental research, mainly driven by Otto Haxel. In 1975, this led to
the foundation of the Institut für Umweltphysik (Institute of Environmental Physics), the first of its
kind in Germany, in the Fakultät für Physik und Astronomie with Karl-Otto Münnich as its founding
director.
From the start, the IUP focused on the underlying physics of a wide spectrum of environmental processes
and less on specific applications in atmospheric sciences, soil sciences, hydrology, or oceanography.
This turned out to be a major strength and it continues to distinguish the IUP from other large
environmental research institutes. With this focus, the IUP attains great flexibility in its methods
and is able to provide an environment where classical divisions between systems and disciplines can
be overcome. For instance, we investigate boundary layers between compartments which determine
the soil-atmosphere and ocean-atmosphere interactions. This direction of research is also adopted
by large international programs, like the International Geosphere Biosphere Project (IGBP), which
in recent times focus increasingly on investigation of interaction between compartments of the Earth
system. With its firm rooting in physics, the IUP sees itself in an excellent position to recognize and
investigate system properties of our environment and the interplay of its subsystems (atmosphere,
cryosphere, soil, groundwater, oceans,. . . ).
The IUP is a strongly experiment-oriented institution. Our current major fields of research are:
• physical foundations of climate research (budgets of greenhouse gases, oxidation capacity of the
atmosphere, radiation in the atmosphere),
• consequences of global change on central cycles in the earth system (water, carbon), and
• reconstruction of paleoclimate from a variety of environmental archives.
Our spectrum of methods still contains those developed from nuclear physics inheritance, specifically
the analysis of 14 C and various stable isotopes including noble gases. In addition, we employ an
array of new techniques like spectroscopy (of the atmosphere) and imaging spectroscopy, remote
sensing from ground-, air-, and space-borne platforms, time series analysis, as well as experiment- and
process-oriented modeling and simulation.
This report gives a snapshot of the research performed at the IUP by diploma students, doctoral
students, and senior scientist. It is intended as a comprehensive but concise overview for the members
of the institute as well as for the scientific community.
9

Atmosphere and Remote Sensing
2.1 Tropospheric Research Group . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2 Stratospheric Ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.3 Radiative Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.4 DOAS Tomography Group . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2.5 Satellite Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2.6 MarHal - Modeling of marine and halogen chemistry . . . . . . . . . . . 95
2.7 Carbon Cycle Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
11

Overview
Summary
Atmospheric research at the IUP concentrates on the processes governing the oxidation capacity
of the atmosphere, its physical and chemical properties and its role in the global climate system.
Central topics are release processes and the influence of reactive halogen species as well as other free
radical cycles in the stratosphere and troposphere, fundamental research related to scattering and
absorption of short-wave radiation transport in the atmosphere, and on the abundance and role of
trace and greenhouse gases in atmospheric chemistry and in the climate system. Tools of our research
are observing systems on global, continental and regional scales relying on sophisticated ground and
aircraft-based in-situ and sampling techniques as well as air-borne and space-borne remote sensing.
Observations are integrated in modeling studies of marine and stratospheric photochemistry with a
particular focus put on the chemistry of halogens, atmospheric radiation transport, and on global,
regional and trajectory models of source and sink processes of greenhouse gases.
Central topics include:
• Atmospheric composition and links to human health
• Radiation transfer processes and links to climate
• Tropospheric halogen species and their role in the oxidation capacity of the atmosphere
• Stratospheric ozone as influenced by halogen and nitrogen species
• Sources and sink processes as well as isotopic abundances of greenhouse gases
• Global observing systems
For a detailed description of the different topics see individual group reports.
Atmospheric composition and links to human health
Studies of radical processes in tropospheric chemistry were performed, free radicals determine the
oxidation capacity of the troposphere, i.e. the capacity of the atmosphere to clean itself from natural
and anthropogenic pollutants. Scientific objectives include studies of the processes governing the
oxidation capacity of the troposphere. In particular the release and activation processes of reactive
halogen species in the troposphere. Studies in this year centered on the following questions:
• The abundance of reactive halogen species (BrO, IO, I2) in the marine boundary layer in coastal
regions.
• The abundance of reactive halogen species (BrO, IO) and related compounds over the open
ocean.
• The abundance of reactive halogen species, in particular BrO, and related species like NO2, NO3
and CH2O in the free troposphere
• The rate of volcanic emissions of reactive halogen species, e.g. BrO, ClO, OClO.
• Chemical evolution of reactive halogen species in volcanic plumes, in particular what are the
processes after O2 and O3 mixes into the originally reducing plume.
For a detailed description of the different topics see individual group reports.
Future Work
Future work will encompass
1. Establishment of a large network of ground based remote sensing instruments to quantify volcanic
emissions, which will provide the first comprehensive study of volcanic sulfur and halogen
emissions (EU-project NOVAC).
2. Study of the marine halogen chemistry with particular emphasis on iodine-particle formation
(EU-project MAP), nonlinear chemistry, and emission ”hot spots”.
13

14 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
3. Spectroscopic studies of atmospheric particles will be performed within a large long-term intercomparison
exercise (EU-project ICARTT).
4. Study of the inter-annual variation of the solar radiation field including 2-D imaging spectroscopy
of the radiative properties of the atmosphere with a particular focus on the radiative properties
during the life cycle of individual clouds (DFG Forschergruppe ’life cycles of clouds’)
5. Using novel ballon-based instrumentation (Mini-DOAS), the time-dependence of ozone destroying
radicals (BrO, and OClO) and inferred reactive chlorine will be investigated from which
conclusions on the most important loss reactions for stratospheric ozone in polar winter can be
drawn.
6. Investigation of the transport and photochemical processes at the major entrance of tropospheric
air into the stratosphere, i.e. the tropical upper troposphere layer/lowermost stratosphere
(TTL/LMS) Conclusions will be drawn on the ozone depletion potential of major manmade
and naturally emitted ozone destroying chemicals passing the TTL/LMS (EU-project
SCOUT-O3).
7. Study of the European carbon balance and in particular the fossil fuel CO2 contribution (EUproject
CarboEurope-IP)
8. Within the carbon system, investigation of independent constraints on global carbon exchange
as derived from long-term high precision 14 CO2 observations in combination with model studies
(DFG project, Atmospheric 14 C).
9. Investigation of the continental European hydrogen budget (in particular the anthropogenic
source and the soil sink) using continuous and aircraft observations over Europe and Siberia
(EUROHYDROS and TCOS II, submitted EU proposals)
Instrument development will be continued, a particular topic being preparation for the new German
research aircraft HALO. In this context we are developing novel instruments based on imaging and
near-IR spectroscopy.
Literature
A total of 16 peer reviewed manuscripts where accepted by or appeared in scientific journals. Members
of the institute were invited to give 19 presentations on topics related to atmospheric research at
scientific conferences
Diploma and Doctoral Theses
A total of 4 Diploma theses and 2 Doctoral theses on topics related to atmospheric research were
completed in the reporting period.

2.1. TROPOSPHERIC RESEARCH GROUP 15
2.1 Tropospheric Research Group
Group members
Prof Dr. U. Platt, Chief of Staff
Dipl. Phys. N. Bobrowski, PhD Student
Dipl. Phys. B. Dix, PhD Student
M. Gillmann, Staff
MSc. O. Ibrahim, PhD Student
Dipl. Phys. C. Kern, PhD Student
I. Louban, Diploma Student
Dipl. Phys. A. Merten, PhD Student
Dr. C. Peters, Post Doc
K. Seitz, Diploma Student
Dipl Phys. R. Sinreich, PhD Student
T. Stein, Diploma Student
Dr. S. Trick, Staff
Dr. J. Zingler, Post Doc
Abstract
Tropospheric research in the IUP concentrates on the processes governing the oxidation capacity of the
atmosphere. Of particular interest are release processes of reactive halogen species from a multitude of
sources (marine biology, sea spray, volcanoes, etc.) into the troposphere. Consequences for the state
of the troposphere are studied together with the other atmospheric subgroups and within national
and international collaborations.
Scientific Objectives
include studies of the processes governing the oxidation capacity of the troposphere. In particular the
release and activation processes of reactive halogen species in the troposphere. the questions studied
in this year centered on the following questions:
• The abundance of reactive halogen species (BrO, IO, I2) in the marine boundary layer in coastal
regions.
• The abundance of reactive halogen species (BrO, IO) and related compounds over the open
ocean.
• The abundance of reactive halogen species, in particular BrO, and related species like NO2, NO3
and CH2O in the free troposphere.
• The rate of volcanic emissions of reactive halogen species, e.g. BrO, ClO, OClO.
• Chemical evolution of reactive halogen species in volcanic plumes, in particular what are the
processes after O2 and O3 mixes into the originally reducing plume.
Overarching topic
Studies of radical processes in tropospheric chemistry, the oxidation capacity of the troposphere, i.e.
the camacity of the atmosphere to clean itself from natural and anthropogenic pollutants.
Background
Free radicals play a pivotal role in atmospheric chemistry. Despite their exceedingly small concentration
(mixing ratios around 10-12), these species are the driving force for most chemical processes
in the atmosphere. While the role of hydrogen radicals (OH, HO2) is relatively well studied and
largely understood, other free radicals like halogen atoms or halogen oxides (e.g. IO, BrO, ClO) have
been neglected until recently. In particular, at the levels suggested by the available measurements
tropospheric halogen species can have profound effects on many aspects of tropospheric chemistry,
these include: (1) Reactive halogen species, and in particular reactive bromine and iodine can readily
destroy tropospheric ozone, which can have a multitude of consequences, both chemical and climatic
(e.g. [Roscoe et al. , 2001], [Platt & Hönninger, 2003]). Catalytic ozone destruction essentially occurs
by two distinct reaction cycles. Either (I) involving self reaction of halogen oxide radicals with other
halogen oxide radicals (XO+XO or XO+YO) or (II) reaction of halogen oxides with hydrogen radicals

16 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
XO+HO2): leading to the net result:
O3 + O3 → 3O2
Cycle (I) has been identified as the prime cause for polar boundary layer ozone destruction [Barrie
& Platt, 1997]. Since the rate of ozone destruction is usually proportional to the square of the halogen
oxide concentration, cycle (I) ineffective at low XO levels usually found in mid-latitude coastal
areas. At low RHS levels, however O3 destruction takes place by reaction cycle II, here the rate of
O3 destruction is linearly dependent on the XO concentration. (2) An important side effect of cycle
(II) the conversion of HO2 to OH and thus a reduction of the HO2/OH ratio, in particular at low
NOX levels. At a given photochemical situation (O3, H2O levels, insolation) the presence of BrO or
IO will therefore increase the OH concentration. It is interesting to note that both effects have been
observed in the upper troposphere (e.g. [Wennberg et al. , 1998]). (3) The reaction of XO with NO,
leads to conversion of NO to NO2 and thus to an increase of the Leighton ratio (L=[NO2]/[NO]). An
increase in L is thus usually regarded as an indicator for photochemical ozone production (due to the
presence of RO2 (R = organic radical)) in the troposphere. However, as already noted by [Platt &
Janssen, 1996] an increase in L due to halogen oxides will not lead to O3 production. (4) A more
subtle consequence of reactive halogen species for the ozone levels in the free troposphere is due to
the combination of the above effects (2) and (3) as pointed out by [Stutz et al. , 1999]: Photochemical
ozone production in the troposphere is limited by the reaction
(2.1)
NO + HO2 → NO2 + OH (2.2)
However, the presence of reactive bromine will reduce the concentrations of both educts of the above
reaction and thus reduce the NOX - catalysed ozone production. (5) Heterogeneous reactions of
bromine species (i.e. HOBr) with (sea salt) chloride can lead to the release of Cl-atoms. This process
constitutes a Br catalysed chlorine activation. Since Cl-atoms are highly reactive, this process directly
enhances the oxidation capacity of the troposphere, see e.g. [Platt et al. , 2004]. (6) Gas-phase iodine
species (like IO, OIO or HOI) may facilitate transport of I from the coast to inland areas and thus
contribute to our iodine supply [Cauer, 2004], [Cox et al. , 1999]. (7) Deposition of mercury was found
to be enhanced by the presence of reactive bromine species in particular in polar regions (e.g. [Barrie
& Platt, 1997]), this process appears to be linked to the oxidation of Hg0 to Hg(II), likely by reaction
with BrO [Lindberg et al. , 2002]. (8) The reaction of BrO with dimethyl sulfide (DMS) might be
important in the unpolluted remote marine boundary layer where the only other sink for DMS is
the reaction with OH radicals (e.g. [von Glasow et al. , 2004], [von Glasow & Crutzen, 2004]). (9)
Iodine species have been shown to be involved in particle formation in the marine BL ([Leck & Bigg,
1999], [Hoffmann et al. , 2001], [O’Dowd et al. , 2002], [Burkholder et al. , 2004]). (10) Evidence is
accumulating (see e.g. [Platt & Hönninger, 2003]) that there is a wide-spread ”background” level of
BrO radicals in the free troposphere, due to the processes described under (1)-(5) and (8) above there
might be an important effect of reactive halogens on the global tropospheric chemistry as summarised
by [von Glasow et al. , 2004].
Main methods
include the experimental determination of the halogen oxide distribution and the distribution of related
species in several compartments of the troposphere: 1) The marine boundary layer in coastal regions
(French Brittany). 2) The open ocean. 3) The free troposphere 4) Volcanic emissions (contents of
reactive halogen species, e.g. BrO, ClO, OClO in volcanic plumes) The measurements are made by
Differential Optical Absorption Spectroscopy (DOAS), which allows the detection of many atmospheric
trace gases at a sensitivity in the ppt - range (i.e. at mixing ratios down to 10-12ppt). For studies
in the different compartments a series of variants of the technique were applied: 1) Studies in the
marine boundary layer were performed by active DOAS (i.e. using artificial light sources), which
allows also nighttime studies, as well as by passive ”Multi-Axis” DOAS (MAX-DOAS). 2) Shipborne
measurements in the open ocean relied on MAX-DOAS observations requiring relatively little
logistic prerequisites and allowed unattended operation. 3) Aircraft-based measurements in the free
troposphere are also based on passive MAX-DOAS observations, while ground based observations
(at the Zugspitze) employ active DOAS measurements. 4) Observation at volcanoes were made by
passive MAX-DOAS and by the novel Imaging-DOAS technique recently developed in our group. In
addition to the field campaigns a number of projects is aimed at technological improvements of the
DOAS technology. Activities included studies on the reduction of the optical noise [Platt, 1994] by the
use of optical fibers and mode mixers to connect light source and transmitting telescope, the use of

2.1. TROPOSPHERIC RESEARCH GROUP 17
Light Emitting Diodes as DOAS light sources, and development of novel techniques for the inversion
of MAX-DOAS measurements to derive the aerosol optical density as well as the vertical distribution
of trace gases in the lower atmosphere.
Main activities
A large number of field campaigns were conducted:
• Expeditions to the volcanoes Etna (Italy) and ... to study emission of halogen oxide radicals
and SO2.
• Studies of nitrate radicals and related species at the Schneeferner Haus (Zugspitze, Germany)
• Ship expedition (on RV Polarstern) during ... to study the NO2, O3, and BrO from 52 o S to
72 o N.
• Studies of the oxidation capacity of the lower atmosphere in New England (USA ) within the
framework of the ICARTT project.
• Participation in the CARIBIC - Project.
• Also world wide long-term measurements of halogen oxides and related species were performed
by the ”Heidelberg Ground-Based Network”.
Funding
DORSIVA (EU)
IALSI (EU)
AFO-2000: ReHaTrop (BMBF)
CARIBIC
Two Ph.D. students are funded through the International Max-Planck Research School in ”Experimental
Atmospheric Chemistry”
Cooperation within the institute and with groups outside of the institute
Obviously there is close cooperation within the atmospheric groups.
National and international cooperation exists with the following groups:
Chalmers University, Gothenburg, Sweden (Galle)
Volcanic observatory Etna, Italy
Max-Planck Institue for Chemistry, Mainz
University of Mainz (Heumann)
University of Bayreuth
Institute for Physical Chemistry, University of Wuppertal (Barnes)
Alfred Wegener Institute for Polar Research, Bremerhafen
NOAA, Boulder
University of Cambridge (Oppenheimer)
Future Work
will encompass the establishment of a large network of volcanic stations to provide the first comprehensive
and quantitative study of volcanic sulfur and halogen emissions (EU-project NOVAC). Also
marine halogen chemistry will be studied, particular emphasis will be of iodine-particle formation (EUproject
MAP), nonlinear chemistry, and emission ”hot spots”. Spectroscopic studies of atmospheric
particles will be performed within a large long-term intercomparison exercise (EU-projcet ICARTT).
Instrument development will be continued, a particular topic being preparation for the new German
research aircraft HALO.
Peer Reviewed Publications
1. Sinreich et al. [2005]
2. von Friedeburg et al. [2005]
3. Pundt et al. [2005]

18 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
4. Zingler & Platt [2005]
5. Volkamer et al. [2005]
6. Bobrowski et al. [2005]
7. Tas et al. [2005]
8. Wenig et al. [2005]
9. Hak et al. [2005]
10. Peters et al. [2005]
11. Kern et al. [2005]
12. Lee et al. [2005]
13. Wagner et al. [2004]
14. Platt et al. [2004]
15. von Glasow et al. [2004]
Other Publications
1. Platt et al. [2005]
2. Volkamer et al. [2004]
Diploma Theses
1. Kern [2004]
2. Louban [2005]
3. Seitz [2005]
PhD Theses
1. Bobrowski [2005]
2. Peters [2005]

2.1. TROPOSPHERIC RESEARCH GROUP 19
2.1.1 Halogen oxide and sulphur dioxide emission of volcanoes
Participating scientist Nicole Bobrowski
Abstract A novel instrument, the ’Mini-MAX-DOAS’ was applied to study reactive halogen and
sulphur emissions of several volcanoes. The study was focussed on the determination of SO2 and BrO
concentrations, but also ClO and OClO could be detected for the first time in a volcanic plume. The
chemistry of volcanic plumes can give insights into volcanic processes, which could help to improve the
forecast of volcanic eruptions and is also of atmospheric relevance as the volcanic source of aerosols
and trace gases can have significant climatic impact.
Figure 2.1: The BrO/SO2 ratios for the different distances from the summit (left panel). Sketch of
processes in a volcanic plume: after emission the plume mixes with ambient air, thus ozone becomes
available and radical chemistry starts (right panel).
Background The chemistry of volcanic plumes
can give insights into volcanic processes, which
could help improving the forecast of volcanic eruptions
and is also of atmospheric relevance as the
volcanic source of aerosols and trace gases can
have a significant climatic impact. Although both
are very important aspects until now the chemical
processes are hardly understood and unfortunately
still rarely studied.
Funding IMPRS Fellowship and DORSIVA
(Development of Optical Remote Sensing for Volcanic
Applications- EU-project)
Methods and results Spectroscopic measurements
were carried out with the new Mini-MAX-
DOAS instrument combined with a Pocket PC.
The main results obtained in this work are: BrO
is formed downwind, although it is not yet clear
by what chemical processes. Nevertheless a suggested
chemistry is given in Figure 1, right panel.
Experimental studies at two volcanic sites, Mt.
Etna and Mt. Villarica, were carried out and
showed similar results. At Mt. Etna, measurements
took place from the summit up to a distance
of 19 km in downwind direction (see Figure 2.1,
left panel). ClO and OClO were detected for the
first time as further active halogen compounds in
volcanic plumes. ClO was already detected next
to the source (in contrast to BrO), and shows no
significant increase in the ClO/SO2 ratio in the
aging plume. The ClO/SO2 ratio even seems to
decrease by measuring further downwind.
The BrO/SO2 variations were studied during and
after the Mt. Etna eruption 2004. They were
compared with filter pack measurements and SO2
flux variations. This measurements show differences
of the feeding systems of Mt. Etna (North
East Crater and Voragine). The North East
Crater showed larger BrO/SO2 ratios than Voragine.
Outlook/Future work The Mini-MAX-
DOAS system will be set-up at many volcanic
sites in the frame of a new started EU-project -
NOVAC. The extension of the data set will open
the possibility of a better estimation of the volcanic
reactive bromine source and also allows the
investigation of changes in the BrO/SO2 ratio
with volcanic activity.
Main publications [Bobrowski, 2005],
[Bobrowski & Filsinger, 2005],
[Bobrowski et al. , 2005]

20 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.1.2 Studies of Reactive Halogen Species (RHS) in the Marine and mid-
Latitudinal Boundary Layer by Active Longpath Differential Optical
Absorption Spectroscopy (DOAS)
Participating scientist Christina Peters
Abstract Appearance and distribution of a variety of reactive halogen species like BrO, IO, OIO
and I2 in coastal areas was investigated within the framework of this PhD thesis.
Figure 2.2: I2 time series recorded during the Mace Head campaign in 1998. The dotted line indicates
the mean detection limit of 20 ppt. The shaded areas indicate I2 clearly identified above the detection
limit (with respect to the individual error
Background The importance of reactive halogen
species (RHS) in the troposphere is on the one
hand due to their strong effect on tropospheric
ozone levels, which was discovered during ozone
depletion events in the polar boundary layer during
polar sunrise. On the other hand recent field
and laboratory studies are indicating a great relevance
of reactive iodine in new particle formation
processes. Since particles in the marine atmosphere
affect the microphysical properties of
clouds, they have a potential impact on climate.
Funding PhD Thesis in the framework of the
AFO2000 program, funded by the BMBF.
Methods and results Within the framework
of this thesis three field campaigns using active
longpath DOAS technique for studies of the
reactive halogen species BrO, IO, OIO and I2
were conducted in different mid-latitudinal regions.
Ground based measurements in the lower
Arctic at the Hudson Bay yielded high levels
of the BrO radical up to 35 ppt in the boundary
layer, coinciding with nearly complete surface
near ozone depletion. Two field campaigns investigated
the appearance of RHS in the coastal
environments of the German North Sea and the
French Atlantic Coast, IO was the only halogen
oxide found in both locations with concentrations
reaching 7.7±0.5 ppt. BrO in the marine boundary
layer was estimated to remain below 1.5 ppt,
neither OIO nor I2 could be unequivocally identified
in the spectra. Within a re-analysis of spectra
taken during an earlier campaign in 1998 in Mace
Head, Ireland up to 61±12 ppt I2 were detected at
night during extraordinary low water levels. Most
likely the I2 was emitted by laminaria algae inhabiting
parts of the lower intertidal zone.
Outlook/Future work Further studies will be
performed within the EU project ”Marine Aerosol
Production” (MAP).
Main publications [Peters et al. , 2005],
[Peters, 2005]

2.1. TROPOSPHERIC RESEARCH GROUP 21
2.1.3 Improvement of the Detection Limit of Active-DOAS-Measurements
by use of fibre coupled light source
Participating scientist André Merten
Abstract Xenon-high-pressure lamps are commonly used in DOAS measurements. Unfortunately
these lamps show strong spectral variability, which determines the minimum detectable optical density.
A combination of a technical solution and a mathematical treatment to reduce the residual structures
and therefore the detection limit was developed.
Figure 2.3: Fibre light source prevents residual structures caused by a Xenon lamp.
Background In active DOAS meausurements
the minimum detectable optical density and thus
the detection limit for trace gases are primarily
determined by the spectral stability of the Xenonlight
source. This is particularly important in
spectral ranges where Xe-lines exist. Due to the
large temperature gradient (several 1000 K/mm)
and turbulent flow inside the arc these spectral
structures strongly vary with time and across the
arc of the Xe–high pressure lamp. When using
a ’shortcut optics’, to remove this Xe-lines by
a lamp reference, it is not guaranteed that the
same area of the arc is imaged as is used in the
measurement, causing strong residual structures
which can be misinterpreted as optical densities.
Imaging the lamp in a fibre and ’mode-mixing’ the
light improves the situation, since all light leaving
the fibre has the same spectral composition.
Funding IALSI
Methods and results After preliminary tests,
a fibre coupled Xe-lamp was installed at the White
cell (multireflection cell) at the EUPHORE smog
chamberb (CEAM Valencia / Spain). Tests before
and after the installation of this arrangement
show a clear reduction of the residual structures
and of the error in the concentration of detected
trace gases. For a long path telescope it
is even more complicated to run a short cut system
that images the lamp arc in the same way
as in the measurement mode, if the lamp is im-
aged directly into the telescope. The Xenon-lamp
was replaced by a Xenon-fibre light source, which
was mounted at the optical axis of the telescope,
instead of a Newton-like telescope set-up, which
makes the complicate alignment of the telescope
easier. Figure 2.3 shows the results of a DOAS
evaluation of NO2 and H2O from the old (left)
and the new (right) set-up. In the left graph
strong residual structures dominate the fit-result.
In the right graphs (new set-up with fibre source),
only very small residual structures are visible and
the detection of weak water absorption is possible.
Due to the easier alignment, effectively no
loss of light occurred. Xenon lamps show also a
spectral drift with time. If it is not possible to
take lamp spectra at short time periods, residual
structures arise. Fortunately the spectrum of
the lamp does not change randomly, which can be
determined by correlation analysis of lamp spectra.
A linear model can describe the variation of
the lamp spectrum. This was combined with the
DOAS-analysis. A change in the lamp spectrum is
now treated like an absorber and can removed by
the fitting procedure. The necessary mathematical
functions were integrated in a new evaluation
software, developed to perform an efficient DOAS
analysis.
Outlook/Future work Using fibre optics offers
the possibility to work with other light sources
such as LED and to design a new type of long path
telescopes.

22 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.1.4 New Operational Software for Automatic DOAS Measurement and
Analysis
Participating scientist André Merten
Abstract The opportunity offered by the DOAS method to do an automatic measurement and
analysis of atmospheric trace gases has not been used because of the leak of adequate software. The
requirements of modern measurement software were studied and a new, easier to handle DOASsoftware
was developed, which can be used to monitor trace gases.
Figure 2.4: Screen shots of the program ’LabDOAS Measurement’.
Background The DOAS method is only practicable
by use of computers. Therefore, the software
is of great importance for the quality of measurement
and data evaluation – especially for a fully
automatic measurement and analysis mode e.g.
for monitoring air quality. The DOAS method
should be an analytical tool in atmospheric science,
and instead the major content of the work.
To meet this requirements, a new software tool
was designed.
Funding IALSI
Methods and results The requirements for a
modern DOAS software were determined:
• Reliable communication with instrument
controllers
• Complete control by graphical user interface
(GUI)
• Status of the devices and the measurement
is reported by graphs
• Recording of all important information together
with the spectra (digital log-book)
• Parallel execution of measurement and data
analysis
• Automatic documentation of measurement
and analysis (as text and graphics)
According to these requirements a software package
consisting of three programs based on Lab-
VIEW was developed: The program ’LabDOAS
MEASUREMENT’ controls an active DOAS device.
It can run in an automatic measurement
and evaluation mode, completely controlled by
GUI and remote acces. Status of measurement
and analysis are exported automatically as graphics.
The easy handling supports the operator especially
in case of adjusting the DOAS device.
’LabDOAS ANALYSIS’ is designed for more intensive
data evaluation. A single spectrum as
well a whole time series of spectra can be analysed
with mathematical functions like digital filters
and Fourier transformation, including methods
to analyse residual structures of lamp spectra
like correlation analysis. ’LabDOAS CALIBRA-
TION’ offers automatic wavelength calibration of
the spectrograph with spectra of atomic emmissions.
It contains a comprehensive database of
atomic spectral lines. This calibration is used to
prepare the reference cross sections for the DOAS
evaluation.
Outlook/Future work This software package
was tested successfully at a long path telescope
and has shown its advantages also in the examination
of lamp noise and exploration of absorption
cross sections. Additional functions such as
automatic adjusting and evaluation of stray light
spectra are in preparation.

2.1. TROPOSPHERIC RESEARCH GROUP 23
2.1.5 Ground based MAX-DOAS measurements
Participating scientists Ossama Ibrahim, Thomas Wagner, Ulrich Platt
Abstract The Multi-axis DOAS technique uses scattered sunlight to obtain information about the
trace gases in the atmosphere by pointing a telescope to different elevation angles and thus receiving
light from different directions. Using Multi-axis DOAS instrument on a stable or movable ground
based platform can also be used to validate DOAS measurements done by satellite instruments.
Figure 2.5: Latitudinal distribution of Stratospheric NO2 VCDs in comparison with SCIAMACHY
results as an example of satellite data validation using ground based MAX-DOAS. The morning
measurements were taken between 5-7 AM O’clock morning and the afternoon ones are between 5-7
PM O’clock afternoon and SCIAMACHY data were collected at 10 AM local equator time.
Background The measurement of trace gases
(identification and quantification) is important for
the investigation of the chemical and physical processes
in the atmosphere. The development of the
Multi Axis DOAS was an important milestone on
the way of DOAS technique evolution. The ability
to direct telescopes to different elevation angles
(multi-axis) allows to emphasize absorption
paths from lowermost atmospheric layers onto the
stratosphere. Measurements from the ground can
provide information on the vertical profile of the
absorbing trace gases under investigation.
Funding IMPRS fellowship
Methods and results Measurements using
Multi-axis DOAS (Differential Optical Absorption
Spectroscopy) on board of a ship platform
(Polarstern research vessel of Alfred-Wegner Institute
für Polar- und Meeresforschung) were carried
out successfully in a latitudinal range between
52 ◦ N and 72 ◦ S every year in the last four years
and gave the possibility to measure several trace
gases like NO2, O3 and BrO in the stratosphere
and/or in the marine boundary layer (MBL). The
measurements showed elevated tropospheric NO2
values in the English channel area and the existence
of the tropospheric BrO in the MBL westerly
from Africa in the latitudinal range between
10 ◦ N and 30 ◦ N, which cannot be seen by satellite
instruments because of their higher detection
limit in mid-latitudes. Also a latitudinal cross sectional
distribution of the stratospheric NO2, O3
and BrO were compared to those obtained from
satellite measurements from GOME and SCIA-
MACHY (see figure 2.5). Ground based measurements
from a stable platform in Cabauw in Holland
were performed to retrieve information about
the tropospheric values of trace gases like NO2
and compare them to those obtained from satellite
OMI. Arranging the viewing geometry using
three different telescopes in three viewing planes
can provide some data on the variation of the NO2
concentrations within an OMI pixel. For information
about the satellites see satellite group report.
Outlook/Future work More investigation of
trace gas concentrations in the troposphere and
stratosphere using ground based measurements
from different platforms comparing with results
from satellite measurements for validation of especially
the newer generations SCIAMACHY and
OMI is going to be performed in the near future.
The Multi-axis DOAS will be used on a moving
platform (car) in urban areas to make estimation
of the in and out flux of trace gases from cities besides
measurements for single plumes from powerplants
or industrial activities. This is a promising
application which has already started.

24 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.1.6 Imaging DOAS. Imaging of two-dimensional trace gas distributions
Participating scientists Ilia Louban, Nicole Bobrowski
Abstract The two-dimensional trace gas distributions in volcanic plumes was quantitatively determinated.
The measurements at Mt. Etna volcano (spring 2005) and on the island Vulcano (autumn
2004) were carried out with an instrument, based on the principle of Differential Optical Absorption
Spectroscopy combined with an imaging spectrograph (I-DOAS).
Figure 2.6: Two dimensional distribution of sulphur dioxide (SO2) in volcanic plume of Mt. Etna,
measured on May 9. 2005 at 13:30 local time. The image represents a scanned solid angle of (v×h)
13.1 ◦ × 36.4 ◦ of a emission source 10 km away. The Values are slant column densities.
Background Spatial resolved data of trace gas
distributions have a wide spectrum of applications.
In many cases it is essential to be able to
determinate the location of the sources and the
strength of their emissions. Also the dynamical
development and behavior of trace gas concentrations
(trace gas clouds) are very interesting and
important for environmental sciences. The advantage
of the DOAS technique to measure several
trace gases simultaneously can be used to investigate
the chemical balances and processes within
the emissions and high spatial resolution of the
instrument allows to estimate those fluxes.
Funding The developments and investigations
took place within the Project for Development of
Optical Remote Sensing for Volcanic Applications
(DORSIVA), supported by the European Union.
Methods and results Imaging of an object
means to produce a two-dimensional dataset of
spatial information, i.e. each picture element
(pixel) of an image is assigned to a defined solid
angle of the space. In case of imaging spectroscopy
third dimension of data accrued, the spectral information
of each pixel. An imaging spectrograph
allows simultaneous imaging and dispersion of the
light, therefore a two dimensional detector, like
CCD detector is needed.
The instrument optics focus the light from a
defined solid angle (here a column) of space on
the vertical entrance slit of the spectrograph. The
grating inside the spectrograph images spatial and
spectral resolved light on the CCD matrix assigning
the vertical dimension of the detector to the
spatial information and horizontal dimension of
the detector to the spectral information. After the
readout of the CCD, the data of one space column
(”column-shot”) is acquired. Using the horizontal
scanning system a viewing angle up to 70 ◦ can
be scanned. The number of horizontally resolved
pixels is given by the number of acquired ”columnshots”.
The width of those depends on displacement
of the scanning mirror between the ”columnshots”.
The number of vertically resolved pixels
is limited by the number of detector-pixel rows of
the CCD matrix and can be scaled down by averaging
over several detector-pixels rows. After the
acquisition spectral information of each pixel has
to be evaluated with the DOAS method and the
colour coded slant column densities (SCD) can be
assembled into an image (Fig. 2.6).
During the campaigns at Mt. Etna and on
the island Vulcano two-dimensional distributions
of sulphur dioxide (SO2) were measured and the
SO2 flux of several fumaroles were estimated.
Also highly resolved SO2 time series to study the
plume dynamics were performed. Additionally,
two dimensional distributions of bromine monoxide
(BrO) were successfully retrieved. SCD up
to 2.8 · 10 14 Molecules/cm 2 were detected in the
plume of Mt. Etna volcano. By two-dimensional
distributions of SO2 and BrO, depression of the
[SO2]/[BrO] ratio from the center to the age of
the plume was identified. This allows conclusions
about possible ozone involved oxidation processes
of BrO production.
Main publication [Louban, 2005]

2.1. TROPOSPHERIC RESEARCH GROUP 25
2.1.7 Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS)
of Trace Gas and Aerosol Distributions
Participating scientist Roman Sinreich
Abstract The combination of MAX-DOAS measurements, i.e. DOAS measurements at different
elevation angles from the ground, and radiative transfer modelling is a suitable method to derive
distributions of trace gases and aerosols.
Figure 2.7: Comparison of MAX-DOAS and in-situ measurements of HCHO in Pinnacle State Park
(USA) at August 3, 2004.
Background For three decades DOAS has been
applied and can be used to measure trace gases
like e.g. NO2, SO2 or HCHO by means of sunlight
[Platt, 1994]. Sunlight passing through the atmosphere
is scattered and absorbed by gas molecules
in the air whereby the absorption occurs at wavelengths
which are characteristic for each trace gas.
The resulting sunlight spectrum contains an absorption
pattern which is suitable to detect and
quantify the according trace gases.
In this study, ground-based DOAS measurements
were performed and their spectra analysed.
One focus was to derive trace gas and aerosol
distributions, by using the measured results and
modelled data.
Methods and results The retrieval of trace
gases by means of DOAS yield Slant Column Densities
(SCDs) which depend upon the concentration
of the according trace gas and the light path.
Since scattered sunlight is measured, the light
path is not readily defined and has to be calculated
by atmospheric radiation transport models.
Furthermore, different elevation angles from the
ground have to be performed in order to get information
on the vertical profile. This method
is called Multi-Axis-DOAS (MAX-DOAS) and allows
to derive gas and aerosol distributions near
the surface.
Aerosol properties can be gained indirectly by
measurements of gas species whose 3-dimensional
distribution is already known and relatively constant.
E.g. O4, whose concentration is proportional
to the square concentration of O2, provides
these qualities. So variations in measured
SCDs are dominated by the aerosol distribution,
which causes different light paths in the atmosphere
[Wagner et al. , 2004].
In summer 2004, a MAX-DOAS network measurement
of 7 sites was performed in New England
(USA) in the framework of ICARTT (International
Consortium for Atmospheric Research on
Transport and Transformation). Thereby, SCDs
of NO2, HCHO, O4 and SO2 could be retrieved
and are in agreement in the main lines with in-situ
measurements at these sites (e.g. see figure 2.7).
Furthermore, an ozone depletion event could be
observed and Glyoxal (C2H2O2) which is a good
tracer for Volatile Organic Compounds could be
detected for the first time by a straylight DOAS
device. Radiative transfer calculations allowed an
estimation of the mixing ratio of about 100 ppt
for Glyoxal at a specific day.
Outlook/Future work Continuation of comparisons
with in-situ measurements, improvement
of the technique of deriving the gas and aerosol
distributions and a MAX-DOAS measurement
campaign in March 2006 in Mexico City.
Main publication [Sinreich et al. , 2005]

26 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.1.8 The flying laboratory: DOAS on board the CARIBIC aircraft project
Participating scientists Barbara Dix, Udo Frieß, Thomas Wagner, Ulrich Platt
Abstract CARIBIC is an innovative scientific project to study atmospheric processes on board a
passenger aircraft during long-distance flights. Besides in-situ measurements of various atmospheric
compounds, it also features a Multi-Axis DOAS instrument to detect specific trace gases.
Figure 2.8: The inlet system. Three small black holes in the upper half indicate the position of the
DOAS telescope entrance holes.
Background Halogen compounds and nitrogen
oxides have a significant impact on the global
ozone budget, e.g. reactive bromine and chlorine
compounds cause stratospheric ozone depletion.
Since anthropogenic sources of bromine
compounds are increasing, bromine compounds
are expected to have a growing impact on the
chemical balance of the lower stratosphere in the
future. Halogen species also play an important
role in the troposphere. A possible background
of reactive bromine compounds in the free troposphere
could influence the ozone budget as well
and thus global climate.
Within the frame of CARIBIC (Civil Aircraft
for the Regular Investigation of the atmosphere
Based on an Instrument Container), a new DOAS
(Differential Optical Absorption Spectroscopy) instrument
was built. Besides BrO, it is also able to
detect HCHO, OClO, O3, NO2, water vapor and
O4.
Methods and results The new DOAS instrument
is the only remote sensing instrument within
the CARIBIC project, which comprises 21 instruments
of 11 European institutions in an cargo container,
that has been successfully put into operation
on a new long-range Airbus (A340-600) of
Deutsche Lufthansa in December 2004. Since May
2005 regular flights with fully automated measurements
are performed once a month. A miniaturized
telescope system, which was especially designed
to fit into the inlet system (see Figure
2.8), collects uv-visible scattered sun light from
three different viewing directions (nadir, 10 degrees
above and below the horizon). With this
Multi-Axis technique the separation of boundary
layer, free tropospheric and stratospheric columns
is possible. Trace gases are then detected in
recorded spectra by means of their individual absorption
structures
First results show that the new instrument
performs well. Stratospheric columns of BrO,
NO2 and O3 could be detected as well as tropospheric
water vapor in the tropics. Enhanced levels
of tropospheric NO2 and HCHO during landing
and take-off in big cities such as Buenos Aires,
Guanghzou (China) or Manila were seen due to
anthropogenic pollution. Slant columns of the
oxygen dimer O4 could be derived, which yield
information on the radiative transport. So far no
indications of enhanced BrO levels in the free troposphere
could be found, yielding perhaps to an
evenly distributed BrO background, but these results
are not yet of statistical significance and future
flights have to be awaited.
Outlook/Future work The future work will
consist of exploring the full scientific potential of
this unique DOAS data set, being the first DOAS
measurements on a long-distance aircraft and taking
into account the synergy of other CARIBIC
measurements, e.g. of aerosol, water vapor, ozone
or halocarbons.

2.1. TROPOSPHERIC RESEARCH GROUP 27
2.1.9 Heidelberg ground-based network
Participating scientists Barbara Dix, Udo Frieß, Thomas Wagner, Karin Kreher(1), Ulrich Platt;
(1): National Institute of Water and Atmosphere, Lauder, New Zealand
Abstract The Heidelberg ground-based network consists of four instruments (see Figure 2.9) which
are set up for long-term monitoring. The instruments provide valuable information on global atmospheric
trends and contribute to scientific questions with respect to their individual location.
Figure 2.9: Water vapor measurements at Paramaribo; location of ground-based instruments.
Background The Heidelberg ground-based
network started with measurements in Kiruna,
Sweden, in 1996 and was soon followed by instruments
in the Antarctic. The polar regions have
always been of great scientific interest, since there
the environment is almost free of anthropogenic
influences. While the Artic has become more
polluted, the Antarctic continent still provides
a very clean troposphere, that enables accurate
studies on stratospheric chemistry and transport.
The polar DOAS (Differential Optical Absorption
Spectroscopy) measurements focus on the influence
of halogen compounds on the ozone budget,
with the Antarctic (stratospheric) ozone hole in
spring being its most prominent example. Yet the
ozone hole phenomenon is not restricted to the
southern hemisphere. Severe ozone destruction is
also observed in the Arctic, but usually of smaller
extent due to rather unstable dynamics. Both
hemispheres show also tropospheric halogen activity:
Autocatalytic processes on sea ice cause so
called bromine explosions, which often lead to the
complete destruction of near surface ozone (polar
tropospheric ozone hole).
In 2002 the DOAS instrument in Paramaribo,
Suriname, was setup within a satellite validation
project (Sciamachy validation). At the time of installation,
this instrument was - to our knowledge
- the first continuously operating DOAS instrument
in the tropics. Measurements in the tropics
allow to study global circulation since this is where
most tropospheric air enters the stratosphere.
Funding Sciamachy validation
Methods and results Both Antarctic instruments
and the one in Paramaribo use the Multi-
Axis (MAX)-DOAS technique, where different
viewing directions between zenith and horizon are
scanned sequentially, thus yielding information in
the vertical distribution of trace gases. With
the MAX-DOAS setup many bromine explosion
events were observed in detail. In contrast to measurements
in the Arctic the data base of Arrival
Heights shows no signs of a possible and suggested
global BrO background.
An example of MAX-DOAS measurements in
Paramaribo show significant amounts of water vapor
in the troposphere with rising columns at
lower elevation angles indicating the presence of
water in lower atmospheric layers (see Figure 2.9).
Water has a major impact on radiative forcing and
climate, therefore monitoring water trends is most
valuable in understanding climate change.
All stations contributed to the validation of
satellite data (O3, NO2, BrO) with the Paramaribo
data set adding one of the first BrO long
term measurements in the tropics. The instrument
at German Antarctic station Neumayer is
also part of the international Network for the Detection
of Stratospheric Change (NDSC).
Outlook/Future work Future work will consist
in continuous measurements, data analysis
and interpretation.

28 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.1.10 Applicability of light-emitting diodes as light sources
for active DOAS measurements
Participating scientists Christoph Kern, Sebastian Trick, Ulrich Platt
Abstract Light-emitting diodes (LEDs) were tested in respect to their applicability in long path
DOAS (LP-DOAS) measurements. Measurements of NO2 and NO3 were conducted in Heidelberg
using the novel method. Temperature stabilization of the LEDs was found to be essential.
Figure 2.10: (a) Estimated spectral radiance distribution of the Osram 450 W/2 XBO xenon arc lamp,
a Luxeon LXHL-LR3C high power 3W royal blue LED, and a conventional tungsten halogen lamp
(20W). Note that the halogen lamp spectrum is multiplied by 10 in this figure. (b) Spectral radiance
normalized to the electrical input power of the individual sources.
Background To date, xenon arc lamps have established
themselves as the most common light
sources for active DOAS instruments. However,
these have several disadvantages including poor
power efficiency and low lifetime resulting in high
maintenance costs. Modern LEDs potentially represent
a very advantageous alternative. [Ball et al.
, 2004] have already performed first cavity enhanced
absorption spectroscopy (CEAS) measurements
with LED light sources, and we conducted
the first LP-DOAS measurements here.
Funding Diplomarbeit therefore “not applicable”
Methods and results The radiative properties
of a variety of LEDs were characterized,
and parameters such as spectral shape, spectral
range, spectral stability, and how these could
be influenced by environmental factors were analyzed.
A study on the radiative properties of modern
high-power LEDs revealed that despite their
much lower power consumption, they posses spectral
radiances comparable to those of xenon arc
lamps at their peak wavelengths (see Figure 2.10).
The spectra of several LEDs were found to contain
Fabry-Perot etalon-induced spectral structures
that interfered with the DOAS evaluation,
in particular when a constant temperature was
not maintained. It could be shown that LEDs
can successfully be used as light sources in active
DOAS experiments measuring NO2 and NO3
around 450 and 630 nm, respectively. Average detection
limits of 0.3 ppb and 16 ppt, respectively,
were obtained using a 6 km light path in the open
atmosphere.
Outlook/Future work In future LED-DOAS
experiments, emphasis must be put on achieving
higher temperature stability. Also, LEDs are becoming
brighter and more cost-effective, and there
has been considerable recent interest in the development
of UV-LEDs. Devices with emission wavelengths
as low as 250 nm were already demonstrated
in the laboratory. Soon, these will be
available as DOAS light sources, thus enabling the
measurement of many further trace gases such as
BrO, SO2, HCHO, and aromatic hydrocarbons.
Main publications [Kern, 2004],
[Kern et al. , 2005]

2.1. TROPOSPHERIC RESEARCH GROUP 29
2.1.11 Active DOAS measurements of trace gases in the free troposphere
Participating scientist Katja Seitz
Abstract The aim of this thesis was to establish a remote controlled active long–path Differential
Optical Absorption Spectroscopy (DOAS) system with three spectrographs at the research station
Schneefernerhaus on the Zugspitze to measure atmospheric trace gases.
Figure 2.11: Umweltforschungsstation Schneefernerhaus (Zugspitze)
Background Because of its remote location
in the free troposphere the Environmental Research
Station Schneefernerhaus is of special interest
for the measurement of trace gases such as
formaldehyde and ozone. As the Schneefernerhaus
is hard to reach a remote-controlled longpath-
DOAS-system with three spectrographs was established.
Methods and results In order to make
longterm measurements of trace gases such as
ozone and formaldehyde a remote-contr olled
longpath-DOAS (Differential Optical Absorption
Spectroscopy) instrument was established. The
lightbeam of a high pres sure xenon lamp is send
to a retro reflector at a distance of two kilometers
and then back to the Schneefernerhaus. As each
trace gas has a characteristic absorp tion structure
one can determine the concentration of different
trace gases by comparing the reflected light with
a lamp spectra.
After several developements of the system first
measurements were made. It was possible to detect
o zone and formaldehyde. As two different
types of spectrographs were used, their results
were compared.
Outlook/Future work An optical shortcut
system has to be developed. Moreover light emitting
diodes (LEDs) could be used instead of the
xenon lamp, which would be much cheaper and
less effort as the lifetime of a LED is a lot longer
than that of a xenon lamp.
Main publication [Seitz, 2005]

30 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.1.12 Long Term Observations of Urban Atmospheric Radical Chemistry
(TURBAN)
Participating scientists Jutta Zingler, Christoph Kern, Daniel Pedersen, Valeri Matveev, Mordechai
Peleg, Ulrich Platt, Menachem Luria
Abstract Using Long Path DOAS and MiniDOAS, seasonal and spatial patterns in the chemistry
of NO3 in an arid urban location are investigated. Its contribution to the transformation and removal
of atmospheric compounds is evaluated. Long term measurements are validated and complemented
by a short term intensive measurement period.
Figure 2.12: Vertical NO3 profiles: Measurement geometry for the MiniDOAS part of this study.
Background The nitrate radical (NO3) is a
key component of nighttime chemistry in the
troposphere and is responsible for the nonphotochemical
production of peroxy radicals and
the transformation of important species such as
nitrogen oxides, VOCs, and ozone. It can be comparable
to the OH radical as a sink for nitrogen
oxides and VOCs. Up to this project, the only
two studies to provide long term nighttime measurements
of NO3 in the boundary layer were conducted
in Germany at a rural coastal site [Heintz
et al. , 1996] and at a rural suburban site [Geyer
et al. , 2001]. One short-term study reported daytime
measurements of NO3 [Geyer et al. , 2003].
Funding German Israeli Foundation for Scientific
Research and Development (G.I.F.)
Methods and results A long term monitoring
station has been established by the Hebrew
University of Jerusalem in the urban center of
Jerusalem, including a Long Path DOAS system
and several monitors for a variety of atmospheric
trace gases and parameters. During an intensive
one month joint field work campaign, IUP Heidelberg
has set up a high end Long Path DOAS
system aiming for quality control, high time resolution
and enhancement of species investigated.
A red LED as alternative light source and new
technology was applied successfully during some
days.
Vertical profiles of NO3 have been measured
using an advanced MiniDOAS system equipped
with a VIS mini-spectrograph (MiniTURBAN).
Stray light spectra acquired during sunrise give
an idea on the concentration profiles in higher atmospheric
layers.
Information on photolytic rates is retrieved
from solar radiation measurements with a spectral
radiometer.
Our long path measurements yielded positive
results for NO3 during almost every night, with
mixing ratios up to 300 ppt. NO3 was found during
a period of very high humidity. Good agreement
could be found comparing NO2 Long Path
DOAS data with in situ monitor results.
Outlook/Future work Evaluation improvement,
intercomparison/correlation of data, quality
control for long term data, profile modelling,
investigation of photolysis parameters.
Main publication in preparation

2.1. TROPOSPHERIC RESEARCH GROUP 31
References
Ball, S. M., Langridge, J. M., & Jones, R. L. 2004. Broadband cavity enhanced absorptions spectroscopy
using light-emitting diodes. Chem. Phys. Lett., 398, 68–74.
Barrie, L. A., & Platt, U. 1997. Arctic tropospheric chemistry. Overview to Tellus special issue, 49B,
450–454.
Bobrowski, N. 2005. Volcanic Gas Studies by MAX-DOAS. Dissertation, Universität Heidelberg.
Bobrowski, N., & Filsinger, F. 2005. Mini-MAX-DOAS Manual. Universität Heidelberg.
Bobrowski, N., Hönninger, G., Lohberger, F., & Platt, U. 2005. IDOAS: A new monitoring technique
to study the 2D distribution of volcanic gas emissions. J. Volcanol. Geotherm. Res., Accepted for
publishing.
Burkholder, J. B., Curtius, J., Ravishankara, A. R., & Lovejoy, E. R. 2004. Laboratory studies of the
homogeneous nucleation of iodine oxides. Atmos. Chem. Phys., 4, 19–34.
Cauer, H. 2004. Schwankungen der Jodmenge der Luft in Mitteleuropa, deren Ursachen und deren
Bedeutung für den Jodgehalt unserer Nahrung (Auszug). Angewandte Chemie 52, 11, 625–628.
Cox, R. A., Bloss, W. J., Jones, R. L., & Rowley, D. M. 1999. OIO and the Atmospheric Cycle of
Iodine. Geophys. Res. Lett., 26 (13), 1857–1860.
Geyer, A., Ackermann, R., Dubois, R., Lohrmann, B., Müller, T., & Platt, U. 2001. Long-term
observation of nitrate radicals in the continental boundary layer near Berlin. Atmos. Env., 35,
3619–3631.
Geyer, A., Alicke, B., Ackermann, R., Martinez, M., Harder, H., Brune, W., Carlo, Piero di, Williams,
E., Jobson, T., Hall, S., Shetter, R., & Stutz, J. 2003. Direct observations of daytime NO3:
Implications for urban boundary layer chemistry. J. Geosphys. Res., 108 (D17), 4368.
Hak, C., Pundt, I., Trick, S., Kern, C., Platt, U., Dommen, J., Ordnez, C., Prvt, A. S. H., Junkermann,
W., Astorga-Llorns, C., Larsen, B. R., Mellqvist, J., Strandberg, A., Yu, Y., Galle, B., Kleffmann,
J., Lörzer, J. C., Braathen, G. O., & Volkamer, R. 2005. Intercomparison of four different in-situ
techniques for ambient formaldehyde measurements in urban air. Atmos. Chem. Phys. Discuss., 5,
2897–2945.
Heintz, F., Platt, U., Flentje, H., & Dubois, R. 1996. Long-term observation of nitrate radicals at the
Tor Station, Kap Arkona (Rügen). J. Geophys. Res., 101 (D17), 22891–22910.
Hoffmann, T., O’Dowd, C. D., & Seinfeld, J. H. 2001. IO homogeneous nucleation. An explanation
for coastal new particle formation. Geophys. Res. Lett., 28 (10), 1949–1952.
Kern, C. 2004. Applicability of light-emitting diodes as light sources for long path DOAS measurements:
A feasibility study. Diplomarbeit, Universität Heidelberg.
Kern, C., Trick, S., Rippel, B., & Platt, U. 2005. Applicability of light-emitting diodes as light sources
for active DOAS measurements. Appl. Opt., Accepted for publishing.
Leck, C., & Bigg, E. K. 1999. Aerosol production over remote marine areas - A new route. Geophys.
Res. Lett., 26, 3577–3580.
Lee, J. S., Kim, Y. J., Kuk, B., Geyer, A., & Platt, U. 2005. Simultaneous Measurements of Atmospheric
Pollutants and Visibility with a Long-Path DOAS System in Urban Areas. Environ. Monit.
Assess., 104, 281–293.
Lindberg, S., Brooks, S., Lin, C. J., Scott, K. J., Landis, M. S., Stevens, R. K., Goodsite, M., &
Richter, A. 2002. Dynamic Oxidation of Gaseous Mercury in the Arctic Troposphere at Polar
Sunrise. Environ. Sci. Technol., 36, 1245–1256.
Louban, I. 2005. Zweidimensionale Aufnahmen von Spurenstoff-Verteilungen. Diplomarbeit, Universität
Heidelberg.
O’Dowd, C., Jimenez, J. L., Bahreini, R., Flagan, R. C., Seinfeld, J. H., Hämeri, K., Pirjola, L., ans
S. G. Jennings, M. Kulmala, & Hoffmann, T. 2002. Marine aerosol formation from biogenic iodine
emissions. Nature, 417, 632–636.

32 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
Peters, C. 2005. Studies of Reactive Halogen Species (RHS) in the Marine and mid-Latitudinal Boundary
Layer by Active Longpath Differential Optical Absorption Spectroscopy. Dissertation, Universität
Heidelberg.
Peters, C., Pechtl, S., Stutz, J., Hebestreit, K., Hönninger, G., Heumann, K. G., Schwarz, A., J.,
Winterlik, & Platt, U. 2005. Reactive and organic halogen species in three different European
coastal environments. Atm. Chem. and Phys. Disc., 5, 6077–6126.
Platt, U. 1994. Differential optical absorption spectroscopy (DOAS). In: Sigrist, M. W. (ed), Air
Monitoring by Spectroscopic Techniques. New York: John Wiley.
Platt, U., & Hönninger, G. 2003. The Role of Halogen Species in the Troposphere. Chemosphere 52,
2, 325–338.
Platt, U., & Janssen, C. 1996. Observation and role of the free radicals NO3, ClO, BrO and IO in the
Troposphere. Faraday Discuss., 100, 175–198.
Platt, U., Allan, W., & Lowe, D. 2004. Hemispheric Average Cl Atom Concentration from 13 C/ 12 C
Ratios in Atmospheric Methane. Atmos. Chem. Phys., 4, 2393–2399.
Platt, U., Pfeilsticker, K., & Vollmer, M. 2005. Chapter 24: Atmospheric Optics. In: Träger, F. (ed),
Springer Handbook of Lasers and Optics. Heidelberg: Springer.
Pundt, I., Mettendorf, K. U., Laepple, T., Knab, V., Xie, P., Lösch, J., von Friedeburg, C., Platt,
U., & Wagner, T. 2005. Measurements of trace gas distributions by Long-Path DOAS-Tomography
during the motorway campaign BAB II: experimental setup and results for NO2 (BAB II special
issue). Atmos. Environ., 39(5), 967–975.
Roscoe, H.K., Kreher, K., & Friess, U. 2001. Ozone loss episodes in the free Antarctic troposphere,
suggesting a possible climate feedback. Geophys. Res. Lett., 28, 2911–2914.
Seitz, K. 2005. Spektroskopische Langzeitmessungen von Spurengasen in der freien Troposphäre.
Diplomarbeit, Universität Heidelberg.
Sinreich, R., Frieß, U., Wagner, T., & Platt, U. 2005. Multi Axis Differential Optical Absorption
Spectroscopy (MAX-DOAS) of Gas and Aerosol Distributions. Farady Discuss., 153 – 164.
Stutz, J., Hebestreit, K., Alicke, B., & Platt, U. 1999. Chemistry of halogen oxides in the troposphere:
comparison of model calculations with recent field data. J. Atmos. Chem., 34, 65–85.
Tas, E., Peleg, M., Matveev, V., Zingler, J., & Luria, M. 2005. Frequency and extent of bromine oxide
formation over the Dead Sea, Israel. J. Geosphys. Res., 110, D11304.
Volkamer, R., Barnes, I., Platt, U., Molina, L. T., & Molina, M. J. 2004. Remote Sensing of Glyoxal
by Differential Optical Absorption Spectrosocopy (DOAS): Advancements in Simulation Chamber
and Field Experiments. In: Rudzinski, K., & Barnes, I. (eds), NATO Advanced Research Workshop
of Environmental Simulation Chambers - Application to Atmospheric Chemical Processes, vol.
NATO Sciences Series, IV. Earth and Environmental Sciences. Zakopane, Poland: Kluwer Academic
Publishers.
Volkamer, R., Spietz, P., Burrows, J. P., & Platt, U. 2005. High-resolution absorption cross-section of
Glyoxal in the UV/vis and IR spectral ranges. J. Photoch. Photobio. A: Chemistry, 172, 35 – 46.
von Friedeburg, C., Pundt, I., Mettendorf, K. U., Wagner, T., & Platt, U. 2005. Multi-AXis-(MAX)
DOAS Measurements of NO2 during the BAB II Motorway Emission Campaign, (BAB II special
issue). Atmos. Environ., 39(5), 977–985.
von Glasow, R., & Crutzen, P.J. 2004. Model study of multiphase DMS oxidation with a focus on
halogens. Atmos. Chem. Phys., 4, 589–608.
von Glasow, R., von Kuhlmann, R., Lawrence, M. G., Platt, U., & Crutzen, P.J. 2004. Impact of
reactive bromine chemistry in the troposphere. Atmos. Chem. Phys., 4, 2481 – 2497.
Wagner, T., Dix, B., v. Friedeburg, C., Frieß, U., Sanghavi, S., Sinreich, R., & Platt, U. 2004.
MAX-DOAS O4 measurements: A new technique to derive information on atmospheric aerosols -
Principles and information content. J. Geophys. Res., 109, D22205.

2.1. TROPOSPHERIC RESEARCH GROUP 33
Wenig, M., Jähne, B., & Platt, U. 2005. Operator Representation as a new differential optical absorption
spectroscopy formalism. Appl. Opt., 44(16), 3246–3253.
Wennberg, P.O., Hanisco, T. F., Jaegle, L., Jacob, D. J., Hintsa, E. J., Lanzendorf, E. J., Anderson,
J.G., Gao, R. S., Keim, E. R., Donnelly, S. G., Negro, L. A. Del, Fahey, D. W., McKeen, S. A.,
Salawitch, R. J., Webster, C. R., May, R. D., Herman, R. L., Proffitt, M. H., Margitan, J. J., Atlas,
E. L., Schauffler, S. M., Flocke, F., McElroy, C. T., & Bui, T. P. 1998. Hydrogen radicals, nitrogen
radicals, and the production of O3 in the upper troposphere. Science, 279, 49–53.
Zingler, J., & Platt, U. 2005. Iodine Oxide in the Dead Sea Valley: Evidence for inorganic sources of
boundary layer IO. J. Geosphys. Res., 110, D07307.

2.2. STRATOSPHERIC OZONE 35
2.2 Stratospheric Ozone
Participating scientists Pfeilsticker, K., A. Butz, M. Dorf, K. Grunow (*), L. Kritten, A. Lindner,
U. Reichl, J. Schwärzle, B. Simmes, and F. Weidner, (*) also with FU-Berlin
Abstract Stratospheric research at the IUP concentrates on an improved understanding of the
photochemical processes controlling stratospheric ozone and its link to climate.
Figure 2.13: Recent history of stratospheric organic (Brorg y = CH3Br, various man-made halones,
and shorter lived organo-bromines) and inorganic (Brin y ) bromine. The open square denoted Brin y
inferred from balloon-borne BrO measurements of the LPMA/DOAS balloon payload since 1996. Note
that bromine is responsible for ∼ 35% of the recent stratospheric loss in ozone with an anticipated
increasing fraction of the total in the future (adopted from M. Dorf, PhD thesis 2005).
Scientific objectives of our stratospheric ozone research include investigation on:
• the photochemistry and budget of upper tropospheric and stratospheric bromine (BrO, Bry)
and its relevance to stratospheric ozone (see figures 2.13 and 2.2.1).
• the photochemistry and budget of upper tropospheric and stratospheric iodine (IO, OIO, Iy)(see
2.2.2 and 2.2.4)
• the stratospheric chemistry and budget of odd nitrogen (NO, NO2, HNO3, ClONO2) (see
2.2.2)
• the partitioning and photochemistry of chlorine and bromine in the high latitude stratosphere
and the assessment of the instantaneous in-situ ozone loss rate (see 2.2.2)
• prominent natural and anthropogenic sources to the trace gas composition of the tropical
tropopause and lowermost stratosphere (TTL/LMS) (see 2.2.4 and 2.2.5)
• the temporal and spatial dependence of stratospheric radicals concentrations (e.g., NO2/N2O5,
BrO/OClO, . . . ) (see 2.2.3)
• the validation of remote sensing satellite instruments, such as ILAS/ADEOS, POAM II and
III, SAGE II and III, ODIN/OSIRIS, GOME/ERS-2, and SCIAMACHY/ENVISAT satellite
instruments (see 2.2.1 and 2.2.2)
Methods The research objectives imply to probe the stratosphere by high altitude (∼ 40 km)
balloon soundings. For that purpose the research group is operating (1) a lab-built two channel
UV/vis spectrometer with which direct Sun measurements are made, and (2) a novel LIMB scanning
UV/vis spectrometer. Both spectrometers are deployed on the joint French/German LPMA/DOAS
(Laboratoire de Physique Moléculaire et Applications/Differential Optical Absorption Spectroscopy)
balloon payload. Jointly with our direct Sun measurements, our French partner operates a near-IR
Fourier Transform Spectrometer with which mid-IR absorbing gases are measured. Balloon flights
are regularly performed at high (Kiruna/Sweden), mid (Aire sur l’Adour/France) and low latitudes

36 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
(Teresina/Brazil). Interpretation of the measurements also involves radiative transfer studies and 1-D
photochemical modelling on air mass trajectories provided by our partner Meteorologisches Institut,
FU-Berlin, Berlin, Germany. The model’s required initialisation is provided through outputs from a
3-D chemistry model (CTM-SLIMCAT) run by the Institute for Atmospheric Science, School of Earth
and Environment, University of Leeds, Leeds, UK.
Our scientific objectives are primarily achieved through measurements of stratospheric radicals (O3,
NO2, BrO, OClO, IO, OIO, . . . ) and related trace gases (CH4, N2O, HCl, NO, HNO3, ClONO2,
. . . ) and the interpretation of the results with respect to the photochemistry of stratospheric ozone.
Major research objectives involve studies of the processes leading to the formation of the ozone hole
in polar winter, the global decline in stratospheric ozone and since recently the photochemistry and
transport of the tropical tropopause layer (TTL) and lowermost stratosphere (LMS). The research of
the group is largely contributing to various international assessments on stratospheric ozone (WMO
report in 1998, 2002, and 2006), organized by the World Meteorological Organisation (WMO).
Field Campaigns & Studies
1. March 04: a high latitude balloon campaign at Kiruna/Sweden (67.9 o N, 21.2 o W) within the
ENVISAT/SCIAMACHY validation
2. Nov./Dec. 2004: a tropical balloon campaign at Teresina/Brazil (5.1 o S, 42.9 o W) within the
ENVISAT/SCIAMACHY validation
3. June, 2005: a tropical balloon campaign at Teresina/Brazil (5.1 o S, 42.9 o W) within the EN-
VISAT/SCIAMACHY validation
International Cooperation The research group closely cooperates with the following institutions
as e.g., documented in joint peer-reviewed publications.
(1) Forschungszentrum Jülich GmbH, Institut für Chemie und Dynamik der Geosphare ICG-I: Stratosphäre,
Jülich, Germany (2) Laboratoire de Physique Moléculaire pour l’Atmosphere et l’Astrophysique
(LPMAA), Université Pierre et Marie Curie, Paris, France (3) Harvard-Smithsonian Center for Astrophysics,
Cambridge, USA (4) Institute for Atmospheric Science, School of Earth and Environment,
University of Leeds, Leeds, UK (7) Meteorologisches Institut, Freie Universität Berlin, Berlin, Germany
(6) Service d’Aeronomie du CNRS, Verrieres le Buisson, France (7) Belgian Institute for Space
Aeronomy (BIRA-IASB), Brussels, Belgium (8) Jet Propulsion Laboratory (JPL), Pasadena, USA
(9) Institute for Atmosphere and Environment, J.W. Goethe University Frankfurt, Frankfurt, Germany
(10) European Space Agency (ESA), Nordwijk, Netherland, (11) Institut für Umweltphysik und
Fernerkundung, University of Bremen, Bremen, Germany (12) Chemistry Department, University of
Cambridge, Cambdrige, UK, (13) Institut für Meterologie und Klima (IMK) Forschungszentrum Karlsruhe,
Karlsruhe, Germany
Outlook/Future work Future work will concentrate on (1) time resolved measurements of stratospheric
radicals, and (2) to continue our budget and trend studies on stratospheric bromine and iodine.
Future studies will also be devoted to the validation of existing (ENVISAT/SCIAMCHY) and future
satellite instruments (Metop/GOME-2 and IASI).
Funding comes through research contracts with European Community (EU-EVK2-CT-2000-00059,
and 505390-GOCT-CT-2004), the BundesMinisteriumForschungs&Technologie (BMBF) through the
DLR (DLR-50FE0017) and the Deutsche Forschungsgemeinschaft (DFG PF384/3-1).
Publications
Peer reviewed publications:
1. Butz et al. [2005]
2. Canty et al. [2005]
3. Dufour et al. [2005]
4. Hendrick et al. [2004]
5. Vandaele et al. [2005]
6. Weidner et al. [2005]

2.2. STRATOSPHERIC OZONE 37
PhD theses:
1. Dorf [2005]
2. Weidner [2005]
Diploma theses:
1. Reichl [2005]
2. Schwärzle [2005]
Invited Talks
1. Butz [2005]

38 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.2.1 Investigation of Inorganic Stratospheric Bromine
Participating scientists Dorf, M., A. Butz, F. Weidner, and K. Pfeilsticker
Abstract Balloon-borne DOAS (Differential Optical Absorption Spectroscopy) bromine monoxide
(BrO) measurements and model simulations are used to investigate the inorganic stratospheric
bromine chemistry and to validate BrO limb profiling from the new SCIAMACHY instrument on the
European Envisat (ENVIronment SATellite) satellite.
Morning Evolution Evening Evolution
Time Time
Figure 2.14: Colour-coded model concentration field of BrO as a function of height and SZA, for
a DOAS balloon flight. Left and right panels show the morning and evening evolution of BrO
respectively. The black lines in the left panel represent the line-of-sight of a SCIAMACHY limb
scan. In the right panel the observation geometry of the DOAS measurements is shown. The thick
black line represents the trajectory of the balloon and the thin black lines indicate the optical path
from the Sun to the balloon instrument for measurements during ascent and solar occultation.
Background Inorganic bromine (BrY) is the
second most important halogen affecting stratospheric
ozone. Although much less abundant than
chlorine, stratospheric bromine currently contributes
about 25 % to global ozone loss. During
daylight the most abundant stratospheric bromine
species is BrO, which accounts for 60 − 70 %
of total BrY and is also the most feasible inorganic
bromine species for detection. Balloonborne
DOAS BrO measurements are used for validation
of the SCIAMACHY satellite instrument.
Funding This work was conducted within ESA
contracts AO 146 and AO 465. Funding came
from the BundesMinisterium für Bildung und
Forschung (BMBF), contract DLR-50EE0017.
Methods and results BrO is subject to considerable
diurnal variation. Validation thus requires
either perfect collocation of the validation
observation with the satellite profiling, or other
methods to account properly for temporal or spatial
mismatches between both sets of observations
and for their different viewing geometry (see
figure 2.14). Photochemical modelling along air
mass trajectories, which match the balloon with
SCIAMACHY observations are used to account
for these discrepancies and to generate a BrO
profile validation set. First comparisons of SCIA-
MACHY limb measurements with high precision
DOAS BrO profiles show poor agreement, especially
below 20 km, which is presently the most
interesting region for bromine chemistry.
Outlook/Future work
• Investigation of the upper troposphere /
lower stratosphere bromine budget
• Investigation of the composition of organic
bromine source gases
• Bromine trend in the stratosphere
• Coupling of bromine and chlorine chemistry
Main publication Dorf, M., Investigation of
Inorganic Stratospheric Bromine using Balloon-
Borne DOAS Measurements and Model Simulations,
PhD thesis at the University of Heidelberg,
Heidelberg, Germany, 2005.

2.2. STRATOSPHERIC OZONE 39
2.2.2 Stratospheric photochemistry of ozone, nitrogen and chlorine species
Participating scientists at IUP Heidelberg Butz, A., M. Dorf, F. Weidner, and K. Pfeilsticker
Abstract In the recent past the LPMA/DOAS balloon payload has conducted several stratospheric
balloon flights at various locations and in different seasons. The inferred abundances of stratospheric
ozone (O3) and nitrogen dioxide (NO2) are checked for internal consistency and compared to correlative
data measured by the satellite borne instrument SCIAMACHY.
Figure 2.15: Relative deviations between satellite (retrieved by IUP Bremen) and balloon borne measurements
of O3 (left panel) and NO2 (right panel) vertical profiles. Observation sites and conditions are indicated in the
legend. The mean deviation of all coincident data in the 20 km – 31 km altitude is 4.3% with 10.8% standard
deviation for O3 and 1.8% with 12.4% standard deviation for NO2. The grey lines indicate the mean and the
one and two times standard deviation boundaries with respect to the 20 km – 31 km altitude range. Note the
broken abscissa.
Background Nitrogen oxides dominate the catalytic
destruction of stratospheric O3 between 25
and 40 km altitude. Thus, NO2 and O3 measurements
are of primary importance to study
stratospheric photochemistry. Recent studies indicate
that for selected geophysical conditions the
agreement between measured and modeled O3 and
NO2 is better than 10%. Accordingly, measurements
of high accuracy are required to constrain
or to be compared with photochemical models.
Our study aims at estimating the accuracy of
state-of-the-art remote sensing measurements of
O3 and NO2.
Funding The present work has been supported
by ESA, BMBF, DLR and the European Union.
Methods and results Abundances of stratospheric
O3 and NO2 inferred from traditional
solar occultation measurements of the
LPMA/DOAS balloon payload are checked for internal
consistency and subsequently compared to
collocated observations of the SCanning Imaging
Absorption spectroMeter for Atmospheric CHartographY
(SCIAMACHY) onboard the European
Envisat satellite. Our comparison scheme accounts
for the temporal and spatial mismatch (airmass
trajectory modell) as well as for the differing
photochemical conditions (1D chemistry modell)
between the balloon and the satellite borne observations.
The internal agreement of the balloon borne
measurements is 10% and 20% for O3 and NO2,
respectively. Typical deviations between SCIA-
MACHY and the balloon borne data amount to
20% for both gases in the 20 to 30 km altitude
range, see figure (2.15). Below 20 km the agreement
worsens mainly due to lower sensitivity of
the satellite retrieval.
Outlook/Future work
• Extension of the O3 and NO2 validation
study to tropical latitudes
• Case studies of the stratospheric nitrogen
and chlorine budget/partitioning and implications
for ozone loss
• Abundance of iodine radicals in the tropical
upper troposphere and stratosphere
Main publication Butz, A. et al., Intercomparison
of Stratospheric O3 and NO2 abundances
retrieved from balloon borne direct sun observations
and Envisat/SCIAMACHY limb measurements,
Atmos. Chem. Phys. Disc. 5, 10747–
10797, 2005.

40 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.2.3 Photolytic lifetime of stratospheric N2O5
Participating scientists Kritten, L., F. Weidner, A. Butz, B. Simmes, M. Dorf, U. Reichl, and K.
Pfeilsticker
Abstract During one of the first international measurement campaigns in the tropics (Teresina,
Brazil), balloon borne measurements of upper tropospheric and stratospheric trace gases were made
using a recently developed UV/visible spectrometer which operates in limb viewing geometry and
allows to infer time resolved (Weidner et al., 2005) vertical profiles.
Background The amount and partitioning of
stratospheric NOx (NO, NO2 and NO3) and
NOy (NOx, N2O5, HNO3, ClONO2, HO2NO2
and BrONO2) largely govern ozone (O3) photochemistry
in the mid-stratosphere (25-40km).
During daytime, NOx is supplied by the photochemical
decay of the reservoir molecule N2O5.
Monitoring the relative diurnal increase of NO2
thus provides information on the photolytic lifetime
of N2O5.
Funding comes through ESA, BMBF, DLR,
and the European Union.
Methods and results In the framework of international
measurement campaign dedicated to
ENVISAT/SCIAMACHY validation three stratospheric
balloon flights have been performed in
tropical latitudes near Teresina, Northern Brazil,
onboard the MIPAS, LPMA/DOAS and IASI balloon
payloads. Our UV/vis spectrometer took
spectra with scanning elevation angle (0 – -6 o )
during balloon float. Slant column densities
(SCDs) of O3 and NO2 were inferred from measurements
conducted during IASI balloon flight.
Using a Radiative Transport model (Tracy, developed
at IUP Heidelberg) SCDs can be simulated
according to our viewing geometry with an appro-
priate trace gas profile as input.
Figure 2.16 shows the inferred temporal
change in measured stratospheric O3 and NO2 for
the LPMA-IASI flight at Timon/Brazil on June
30, 2005. As expected for the tropical stratosphere,
while the inferred stratospheric ozone does
not change much (< 10% ), NO2 largely increases
(a factor of 2) over the course of the day, primarily
due to the photolysis of the nighttime reservior
species N2O5 into NO2 and NO3. The observed
increase in NO2 can be used to test calculated
N2O5 photolysis frequencies as a function of the
actinic flux and the still uncertain temperature
depndence of the N2O5 absorption cross section.
Outlook/Future work
• Analysis of all three balloon flights at
Teresina for UV/vis absorbing gases such
as O3, NO2, BrO, OClO, IO, OIO, and
CH2O.
• Preparation of and participation in future
measurement campaigns (Kiruna, January
2006)
Main publication Kritten, L., et al., The photolytic
lifetime of stratospheric N2O5, GRL, (in
preparation), 2005.
Figure 2.16: Inferred temporal change stratospheric O3 and NO2 concentrations as a function of
time, solar zenith angle and height for the LPMA-IASI flight at Timon/Brazil on June 30, 2005.
Note while the ozone field is almost constant with time and space, the NO2 concentrations increase
at all altitudes with the largest increase seen in the 30 - 35 km range. Also shown are 2 collocated
SCIAMCHY/ENVISAT observations on June 29, UT 12:16 (# orbit 17412) and on July 1, UT 12:53
(# orbit 17441) which can be validated with the mini-DOAS observations.

2.2. STRATOSPHERIC OZONE 41
2.2.4 Spectroscopic measurements of halogen oxides in the marine boundary
layer in Alcântara/Brazil
Participating scientists Schwärzle, J., A. Lotter, and K. Pfeilsticker
Abstract Since the discovery of stratospheric ozone loss due to these species, the atmospheric
photochemistry of reactive halogen species has become of particular concern. Their fate and behavior
in the atmosphere is still uncertain. During a campaign carried out in Northeastern Brazil, IO was
detected for the first time in a tropical coastal region.
Figure 2.17: Mixing ratio of IO, measured at Alcântara/Brazil. Night time is indicated by grey
background, tidal height is shown in blue in order to point out a possible correlation between tidal
height, daylight and mixing ratios of IO
Background Since reactive halogens have been
detected at different sites all over the world (arctic,
mid-latitudes), the global impact of halogen
oxides on the chemistry of tropospheric ozone is
an arising question. It is of special importance in
the tropics as there is fast vertical convection of
air from the boundary layer into the lower stratosphere.
Funding came through Deutsche Forschungsgemeinschaft
(DFG-PF 384/1-2 and 2-3).
Methods and results The measurements were
conducted by active long-path Differential Optical
Absorption Spectroscopy (DOAS) near the
ocean-surface during a field campaign held in
Alcântara/Northeastern Brazil from December
2004 until January 2005.
Mixing ratios of up to 0.82 ppt of IO were determined
within the IO-absorption-bands in the
spectral range of 418–438 nm. Possible sources of
the inorganic iodine in the marine boundary layer
are the photochemical decay of short-lived organic
iodine emitted from the biologically active oceanic
shelf region (e.g. mangroves), or at lower concentrations
by long-range transport of these species
from the open ocean.
Absorption structures in the range of 320–
350 nm were analyzed for the absorption of
bromine oxide, which could not be detected.
Outlook/Future work
• Identification of iodine source gases
• Abundances of IO in the coastal and continental
tropics
• Determining possible impact of IO on tropospheric/stratospheric
ozone
Main publication Schwärzle, J., Spektroskopische
Messung von Halogenoxiden in
der marinen atmosphrischen Grenzschicht in
Alcântara/Brasilien, Staatsexamensarbeit, University
of Heidelberg, Heidelberg, Germany, 2005.

42 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.2.5 Ground-based direct Sun UV/vis spectroscopy in Timon/Northeastern
Brazil: Comparison of tropospheric air mass pollution in the dry and
wet season
Participating scientists Reichl U., A. Butz, M. Dorf, L. Kritten, A. Lindner, B. Simmes, F.
Weidner, and K. Pfeilsticker,
Abstract: The impact of biomass burning on the concentration of tropospheric pollutants is investigated
by comparisons of direct Sun UV/Vis DOAS measurements (Differential Optical Absorption
Spectroscopy) at TIMON/North Eastern Brazil (5.1 o S, 42.9 o W) at the end of dry season in Nov
2004 and after the rainy season in June 2005. Natural and anthropogenic contributions to pollutants
(e.g. CH2O and NO2) to the tropical continental troposphere are assessed and corresponding species
remotely sensed by the ENVISAT/SCIAMACHY instrument are validated. Biomass emission ratios
for NO2 and CH2O are also inferred.
Figure 2.18: Tropospheric vertical amount (VCD) of
NO2 (upper two panels) and CH2O (lower two panels)
during the dry season sunset (left panels) and end of
the wet season (right panels) at TIMON/North Eastern
Brazil (5.1 o S, 42.9 o W). The vertical lines marked
by are (1) the average NO2 at the end-of wet season,
(2) the average NO2 at the end-of dry season, (3) the
average CH2O at the end-of wet season, and (4) the
average CH2O at the end-of dry season. Considering
the most likely emission scenario for TIMON, the
difference of (2) - (1), and (4) - (3) can be ascribed
to end-of the dry season biomass burning emissions.
Accordingly, the baselines in the left panels are being
due to either CH2O formed during hydrogen carbon
related oxidation, or NOx related emission by anthropogenic
emissions.
Background In the tropics biomass burning is
a prominent source of atmospheric pollutants. For
further assessments on the potential impact of
biomass burning on tropospheric ozone and air
quality estimates of emission factors of certain
pollutants, i.e. emitted pollutant mass per mass
biomass burned, is of primary interest [Andreae
& Merlet, 2001].
Methods and results Ground-based direct
sun spectroscopy of NO2 and CH2O
were performed within the balloon-borne EN-
VISAT/SCIAMACHY validation activities in
Northeastern Brazil during the end of the dry season
(Nov. 2004) and wet season (June 2005). The
spectroscopic measurements indicate distinct features
of biomass burning on the tropospheric composition
(compare e.g. the left and right panels
in Figure 2.18) in agreement with recent observations
of ENVISAT/SCIAMACHY instrument (see
section 2.5.12). Our observations indicate typical
increases (∆) in the vertical column amounts
of ∆NO2 = 4.8 · 10 15 /cm 2 and ∆CH2O =
9.0 · 10 15 /cm 2 , respectively for the dry versus
wet season tropical boundary layer. These imply
emission ratios E(∆NOx/∆CH2O) = 1.6 ± 1,
a result being in good agreement with recent
estimates (0.64 to 1.64) for tropical forest fires
(Andreae & Merlet [2001]). The elevated baseline
concentrations (right panels in 2.18) for CH2O
indicate the important role oxidation of naturally
emitted hydrogen carbons plays and for NO2
the influence of anthropogenic activity (traffic related
fossil fuel consumption) related emissions
on the photochemistry of tropospheric ozone and
air quality.
Funding came through research contracts with
the BundesMinisteriumForschungs&Technologie
(BMBF) through the DLR (DLR-50FE0017).
Outlook/Future work will concentrate on a
more thorough characterization of biomass and
fossil fuel related emissions on the photochemistry
of tropospheric ozone and air quality in the tropics.
Validation of remotely sensed tropospheric
pollution will also be conducted.
Main publication Reichl, U., Groundbased
direct Sun UV/vis spectroscopy in Timon/Northeastern
Brazil: Comparison of tropospheric
air mass pollution in the dry and wet
season, Diploma thesis at the University of Heidelberg,
Heidelberg, Germany, 2005.

2.2. STRATOSPHERIC OZONE 43
References
Andreae, M.O., & Merlet, P. 2001. Emission of trace gases and aerosols from biomass burning. Global
Biochem. Cycles, 15, 4, 955 – 966.
Butz, A. 2005. LPMA/DOAS: Balloon based SCIAMACHY validation example: O3 and NO2 vertical
profiles. SCIAMACHY Science Advisory Group 32, Delft, Netherlands.
Butz, A., Bösch, H., Camy-Peyret, C., Chipperfield, M., Dorf, M., Dufour, G., Grunow, K., Jeseck,
P., Kühl, S., Payan, S., Pepin, I., Pukite, J., Rozanov, A., von Savigny, C., Sioris, C., Wagner, T.,
Weidner, F., & Pfeilsticker, K. 2005. Inter-comparison of Stratospheric O3 and NO2 abundances retrieved
from balloon borne direct sun observations and Envisat/SCIAMACHY limb measurements.
Atmos. Chem. Phys. Disc., 5, 10747 – 10797.
Canty, T., Salawitch, R.S., Renard, J.B., Reviere, E.D., Pfeilsticker, K., M., Dorf., Fitzenberger,
R., Bösch, H., Stimpfle, R.M., Wilmouth, D.M., Anderson, J.G., Richard, E.C., Fahey, D.W., &
Gao, R.S.and Bui, T.P. 2005. Analysis of BrO, ClO, and nighttime OClO in the arctic winter
stratosphere. J. Geophys. Res., 110, D01301, doi:10.1029-/2004JD005035.
Dorf, M. 2005. Investigation of inorganic stratospheric bromine by balloon-borne DOAS measurements
and model simulations. PhD thesis, University of Heidelberg, Heidelberg, Germany.
Dufour, G., Payan, S., Lefévre, F., Berthet, G., Eremenko, M., Butz, A., Jeseck, P., Té, Y., Pfeilsticker,
K., & Camy-Peyret, C. 2005. 4D comparison method to study the NOy partitioning in summer
polar stratosphere: Influence of aerosol burden. Atmos. Chem. Phys., 5, 919 – 926.
Hendrick, F., Barret, B., Van Roozendael, M., Boesch, H., Butz, A., De Mazière, M., Goutail, F.,
Lambert, J.-C., Pfeilsticker, K., & Pommereau, J.P. 2004. Retrieval of nitrogen dioxide stratospheric
profiles from ground-based zenith-sky UV-visible observations: Validation of the technique through
correlative comparisons. Atmos. Chem. Phys., 4, 2867 – 2904.
Organization), WMO (World Meteorological. 2003. Scientific Assessment of Ozone Depletion: 2002,
Global Ozone Research and Monitoring. Geneva, Project Report No. 47, 498 pp.
Reichl, U. 2005. Ground-based direct Sun UV/vis spectroscopy in Timon/Northeastern Brazil: Comparison
of tropospheric air mass pollution in the dry and wet season. Diploma thesis, University of
Heidelberg, Heidelberg, Germany.
Schwärzle, J. 2005. Spektroskopische Messung von Halogenoxiden in der marinen atmosphärischen
Grenzschicht in Alcântara/Brasilien. Staatsexamensarbeit, University of Heidelberg, Heidelberg,
Germany.
Vandaele, A.C., Fayt, C., Hendrick, F., Hermans, C., Humbled, F., Van Roozendael, M., Gil, M.,
Navarro, M., Puentedura, O., Yela, M., Braathen, G., Stebel, K., Tornkvist, K., Johnston, P.,
Kreher, K., Goutail, F., Mieville, A., Pommereau, J.-P., Khaikine, S., Richter, A., Oetjen, H.,
Wittrock, F., Bugarski, S., Frieß, U., Pfeilsticker, K., Sinreich, R., Wagner, T., Corlett, G., &
Leigh, R. 2005. An intercomparison campaign of ground-based UV-Visible measurements of NO2,
BrO, and OClO slant columns. Methods of analysis and results for NO2. J. Geophys. Res., 110,
D08305, doi:10.1029/2004JD005423.
Weidner, F. 2005. Development and application of a versatile balloon-borne DOAS instrument for
skylight radiance and atmospheric trace gas measurements. PhD thesis, University of Heidelberg,
Heidelberg, Germany.
Weidner, F., Bösch, H., Bovensmann, H., Burrows, J.P., Butz, A., Camy-Peyret, C., Dorf, M.,
Gerilowski, K., Gurlit, W., Platt, U., von Friedeburg, C., Wagner, T., & Pfeilsticker, K. 2005.
Balloon-borne limb profiling of UV/vis skylight radiances, O3, NO2, and BrO: Technical set-up
and validation of the method. Atmos. Chem. Phys., 5, 1409 – 1422.

2.3. RADIATIVE TRANSFER 45
2.3 Radiative Transfer
Participating scientists Pfeilsticker, K., A. Butz, M. Dorf, A. Lindner, A. Lotter, U. Reichl, T.
Scholl, and F. Weidner
Abstract Research on the radiative transfer (RT) in the Earth’s atmosphere at the IUP concentrates
on an improved understanding of the UV/vis solar irradiance, its temporal variation and the deposition
of solar radiation in the atmosphere. These studies include spectroscopic measurements from different
platforms and sophisticated radiative transfer modelling.
Figure 2.19: Upper panel: Comparison of measured (black) and simulated (red) oxygen A-band
spectrum for the observation at Cabauw (NL) on May 11, 2003 at UT 14:59. The identification of the
oxygen A-band and solar Fraunhofer lines is given next to the line. Middle panel: Residual spectrum
taken as the natural log of the ratio of measured and simulated spectra, hence the natural units of
vertically-integrated optical density (VOD) airmass. Lower panel: Inferred photon path-pdf, assuming
a Gamma-distribution for the in-cloud transfer (adopted from Scholl et al. [2005])
Background The transfer of solar radiation in the Earth’s atmosphere is one of the most complicated
issues in environmental sciences, mostly owing due to the variety and complicated nature
of atmospheric absorbers and scatters (e.g., gases, aerosols, liquid and solid cloud particles), their
spectroscopic signatures and varying spatial arrangements. Accordingly it is found that, e.g., clear
and cloudy sky RT is the major uncertainty in climate modelling and the validation of RT codes
thus appears to be necessary. Also, RT codes find applications in photochemical investigations and
in in-situ and remote sensing studies.
Scientific objectives of radiative transfer studies include the following
• the measurements of photon path length distributions of solar photons being transmitted to the
ground (see 2.3.2)

46 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
• the absolute spectral solar irradiance (320 - 650 nm) and its temporal variation (see 2.3.3)
• the measurement of UV/visible actinic fluxes (e.g., of JNO2) and of the limb radiance near
horizon
• the detection and characterization of unknown, overlooked, or yet poorly characterized atmospheric
absorbers, such as the H2O continuum absorption, meta-stable and stable H2O − H2O
dimers, or the collisional complex O2 − O2, .... (see 2.3.4)
• the measurements of the stratospheric aerosol extinction and its relation to volcanic eruptions.
• the validation of level 1 products (spectral solar irradiance, and limb radiances) of the SCIA-
MACHY instrument deployed on the European research satellite ENVISAT (see 2.3.1).
Arguably all these activities aim at a better understanding of the primary driving force of the
climate system e.g., the solar radiation and its deposition in Earth’s atmosphere. The research thus
contributes to better quantify and assess man’s impact on the past, present and future global climate.
Methods used for the investigations of the radiative transfer involve (1) spectroscopic measurements
of the absolute spectral solar irradiance in the UV/vis/near-IR and of corresponding near horizon
skylight limb radiances from different spectrometers (grating and Fourier-Transform) deployed on
high altitude (∼ 40 km) balloon platforms including on-side absolute radiometric calibration to NIST
(National Institute of Standard and Technology, USA) and PTB (Physikalische Technische Bundesanstalt)
radiometric standards (2) ground-based high spectral resolution spectroscopic measurements
of zenith scattered skylight around the oxygen A-band (767 - 771 nm) (see Figure 2.19, upper panel),
that aim at the detection of photon path length distribution of solar photons for a variety of cloudy
skies (see Figure 2.19, lower panel) and (3) long-path spectroscopic absorption measurements near
surface in wavelength intervals ranging from the UV to the near-IR. All the different instruments
are deployed on internationally organized field campaigns that address a wider range of scientific
objectives (see below). The interpretation of these measurements also involves sophisticated radiative
transfer modelling (ray-tracing, Monte Carlo, discrete ordinate models, DISORT) that e.g., account
for the sphericity of the atmosphere, refraction, time and space dependent trace gas and aerosol
concentrations and cloud cover. Activity (1) is performed within a French/German collaboration with
the Laboratoire de Physique Moléculaire et Applications, Université Pierre et Marie Curie, Paris,
France and (2) within a collaboration with the IUP at the University of Bremen, Germany.
Field Campaigns & Studies
1. March 04: a high latitude balloon campaign at Kiruna/Sweden (67.9 o N, 21.2 o W) within the
ENVISAT/SCIAMACHY validation
2. Nov./Dec./Jan. 2004/05: a tropical balloon campaign at Teresina/Brazil (5.1 o S, 42.9 o W) within
the ENVISAT/SCIAMACHY validation and at Alcantara/Sao Luis/Brazil (2.39 o S, 44.38 o W).
3. June 2005: a tropical balloon campaign at Teresina/Brazil (5.1 o S, 42.9 o W) within the EN-
VISAT/SCIAMACHY validation
International Cooperation The research group closely cooperates with the following institutions
as, e.g., documented in joint peer-review publications.
(1) Laboratoire de Physique Moléculaire pour l’Atmosphere et l’Astrophysique (LPMAA), Université
Pierre et Marie Curie, Paris, France, (2) Meteorologisches Institut, Freie Universität Berlin, Berlin,
Germany, (3) European Space Agency (ESA), Nordwijk, The Netherlands, (4) Institut für Umweltphysik
und Fernerkundung, University of Bremen, Bremen, Germany, (5) Los Alamos National Laboratory,
Space and Remote Sensing Sciences Group, Los Alamos, USA, (6) Royal Netherlands Meteorological
Institute (KNMI), De Bilt, The Netherlands, (7) Meteorological Institute, University of
Bonn, Bonn, Germany, (8) Meteorological Institute, University of Munich, Munich, Germany, (9)
GKSS Research Centre, Geesthacht, Germany.
Future work will concentrate on studies (1) of the inter annual variation of the spectral solar
irradiance and its relation to climate change, (2) improved measurements of path length distribution
of solar photons during the life-time of cloud systems, (3) high resolution spectroscopic studies of the
visible and near-IR spectrum of water vapor and (4) 2-D imaging spectroscopy of radiative properties
of the atmosphere.

2.3. RADIATIVE TRANSFER 47
Funding comes through research contracts with the BundesMinisteriumForschungs&Technologie
(BMBF), through the DLR (DLR-50FE0017) and GSF (GSF-07ATF24) and the Deutsche Forschungsgemeinschaft
(DFG PF384/2-1 and PF384/2-3).
Publications
Peer reviewed publications:
1. Crewell et al. [2004]
2. Gurlit et al. [2005]
3. Scholl et al. [2005]
4. Weidner et al. [2005]
PhD theses:
1. Weidner [2005]
Diploma theses:
1. Lindner [2005]
Invited Talks
1. Pfeilsticker et al. [2004]
2. Pfeilsticker [2005a]
3. Pfeilsticker [2005b]

48 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.3.1 Development and Application of a Versatile Balloon-Borne DOAS
Instrument for Skylight Radiance and Atmospheric Trace Gas Profile
Measurements
Participating scientists Weidner, F., H. Bösch, A. Butz, M. Dorf, U. Platt, C. von Friedeburg,
T. Wagner, and K. Pfeilsticker
Abstract A novel balloon-borne UV/vis DOAS instrument measuring limb scattered radiation was
developed, characterized in the laboratory and employed during 5 stratospheric balloon flights. Skylight
radiance and concentration profiles of O3, NO2, and BrO are retrieved and compared to radiative
transfer simulations and measurements of the same parameters.
Background In the past two decades remote
sensing of the atmosphere by optical methods
has evolved into a powerful tool for meteorology,
atmospheric photochemistry and climate studies.
Most recently, space-borne UV/vis limb observations
have also become available, e.g., through
the SME, SOLSE/LORE, Odin/OSIRIS, and EN-
VISAT/SCIAMACHY instruments. Quasi in-situ
UV/vis limb profiling from balloon may also offer
a new method for time resolved spectroscopy of
ozone harmful radicals in the stratosphere.
Scientific questions that can be tackled by
UV/vis limb measurements are:
(1) measurements of near horizon limb radiance
for different illumination conditions and validation
of radiative transfer codes.
(2) Monitoring profiles of stratospheric radical
species, such as O3, NO2, BrO, OClO, IO, ....
and studies of their photochemistry and budget,
e.g., for the systems NO2/N2O5 (see 2.2.3) or
BrO/OClO and its importance for ozone loss.
Methods UV/visible skylight radiances (330 −
550 nm) are measured from azimuth controlled
balloon payloads which are flying into the middle
stratosphere (∼ 32km). The spectra are analyzed
for along-the-sights column densities of O3,
NO2, BrO, H2O, and O4 by Differential Optical
Absorption Spectroscopy (DOAS). Radiative
Transfer (RT) calculations, e.g., with the lab programmed
Monte Carlo RT Model TRACY, are
used to (a) simulate the measured quantities and
(b) infer vertical profiles of O3, NO2, BrO and
OClO concentrations using the Maximum a Posteriori
(MAP) inversion technique. Subsequent
measurements of the profiles of these species allow
us to draw information on the temporal or
spatial variations (or both) of these species and
the related photochemistry.
Results Balloon-borne UV/vis limb scattered
measurements is tested against simultaneous measurements
of the same parameters available from
in-situ, or UV/vis/near IR solar occultation observations
performed on the same payload. Reasonable
agreement is found between (a) measured and
RT calculated limb radiances and (b) inferred limb
O3, NO2, and BrO (see Figure 2.20) and correlative
profile measurements when properly accounting
for all relevant atmospheric parameters (temperature,
pressure, aerosol extinction, and major
absorbing trace gases).
Figure 2.20: Comparison of retrieved BrO profiles
from mini-DOAS limb measurements (black line)
and direct sunlight DOAS measurements (red
line) during balloon ascent for an LPMA/DOAS
balloon flight in Kiruna, March 24 th , 2004 with a
priori profile in green.
Additionally, scanning limb observations provide
time-resolved profile information of radicals
during sunset.
Future work should concentrate on the application
of the method on photochemical studies addressing
the loss in stratospheric ozone at high,
middle, and low latitudes, including the tropical
tropopause region.
Main publication Weidner, F., Development
and Application of a Versatile Balloon-Borne
DOAS Instrument for Skylight Radiance and Atmospheric
Trace Gas Profile Measurements, Ph.D.
thesis, Universität Heidelberg, Heidelberg, 2005.

2.3. RADIATIVE TRANSFER 49
2.3.2 Oxygen A-band measurements for solar photon path length distribution
studies
Participating scientists Scholl, T., and K. Pfeilsticker
Abstract High resolution spectroscopy of the oxygen A-band (760-780 nm) in zenith scattered
skylight is a powerful tool to infer path length distributions (PDF) of solar photons transmitted to
the ground. The relation between the different moments of the PDF (〈L〉, 〈L 2 〉) and the rescaled
cloud optical depth τ ∗ is a strong indicator for 3D-effects on the radiative transfer (RT).
Height [m]
10000
8000
6000
4000
2000
0 :0
12:
:5 :10 :15 :20 :25 :30 :35 :40 :45 :50 :55
Time [UTC]
-60 -50 -40 -30 -20 -10 0 10 20
Reflectivity [dBZ]
Figure 2.21: left panel: Measured radar reflectivities from KNMI 35 GHz Radar for May 22, 2003 UT 12:00-
13:00, right panel: Mean cloud photon paths 〈Lc〉 as a function of effective cloud optical depth τ ∗ c . The black
lines are predictions for different values of the Lévy exponent α ≤ 2. The 3 data clusters (color-coded blue,
red and green) correspond to the 3 different probed cloud situations.
Background Modelling RT in cloudy skies is
one of the most challenging tasks in climate modelling.
Photon PDF is commonly a hidden property
of standard RT models, controlled by the
spatial distribution of scattering and absorption.
The distribution in the near infrared region is
very representative for the shortwave region as
a whole. The principle of equivalence allows to
draw conclusions about radiative properties of
the atmosphere from a photon PDF measured in
one wavelength band, since the scattering properties
of clouds and aerosols vary slowly and predictably
with wavelength. Here the first two moments
of the photon PDF of solar photons transmitted
through cloudy skies to the ground are
investigated. Combining the spectroscopic measurements
with other cloud properties measured
simultaneously by in-situ techniques during two
campaigns allows to test the theory of anomalous
photon diffusion through clouds.
Methods and Results The multiple of different
line strengths offered by the oxygen A-band
implicitly provide direct information on the PDF
of the photons transmitted to the ground. The
spectral retrieval is solved by forward modelling
the measured spectra with a prescribed photon
PDF (usually a Γ function) at high spectral resolution.
The free parameters of the PDF are
then iteratively calculated by using a Nonlinear
Least Square Fit leading to the searched quantities
〈L〉 and 〈L 2 〉. Davis & Marshak [2002]
inferred for the first moment of photon PDF:
〈Lc〉/∆H = (1/2 · [1 + C(ɛ)] · τ ∗ ) α−1 . α is the so
called Lévy index which ranges between 1 and 2.
In particular, the value α = 2 is attained for a homogenous
slab and for α < 2 for inhomogeneous
slab. In Figure 2.21 the enhancement of the mean
photon path length in the cloud (as a function of
τ ∗ = τ · (1 − g)) and the received Lévy index is
shown.
The findings confirm the theory of anomalous
photon diffusion through clouds and the predictions
for the values in the path length to optical
depth relations. It also provides further evidence
that cloudy sky photon path length require consideration
of non-classical photon transport theory.
Funding comes through the AFO-2000 4D
Clouds project (BMBF-07ATF24).
Outlook Photon PDFs are a central concept of
cloud RT modelling. For further improvements
imaging DOAS spectroscopy at high temporal and
spatial resolution is required.
Main publication Scholl, T., Photon path
length distributions for cloudy skies: Their first
and second-order moments inferred from high resolution
oxygen A-Band spectroscopy, PhD-Thesis,
Universität Heidelberg, Heidelberg, in preparation.

50 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.3.3 Absolutely calibrated solar irradiance measurements
Participating scientists Lindner, A., H. Bösch, A. Butz, M. Dorf, F. Weidner, and K. Pfeilsticker
Abstract Absolutely calibrated solar irradiance spectra are measured from aboard the LPMA/
DOAS balloon gondola at around 30 to 35 km altitude. After accounting for residual atmospheric extinction
the findings are compared to previous observations and discussed with respect to implications
for atmospheric photochemistry and the Earth’s climate.
Figure 2.22: Ratio of solar irradiance spectra referenced to the solar spectrum of Kurucz et al. [1984] with
recent updates of Fontenla et al. [1999] (MODTRAN 3.7) with (a) the present balloon borne measurement,
(b) SORCE/SIM Harder et al. [2000], (c) SCIAMACHY/ENVISAT in channel 1, 2, 3, and 4 using the revised
IUP-Bremen calibration.
Background Solar radiation is the driving force
for climate and thus for life on Earth. Evidently,
the extraterrestrial solar irradiance Eo and its
temporal evolution is of primary interest for atmospheric
spectroscopy, photochemistry, climate
and the solar cell industry as well. Although Eo is
monitored by a large number of space-borne, airborne
and ground-based instruments, to date, a
consensus on Eo could only be achieved within few
percents in the UV-A and visible spectral wavelength
ranges mainly due to given problems with
the absolute calibration of the radiation measurements
and long term drifts of the various sensors.
Funding The present work has been supported
by ESA, BMBF, DLR and the European Union.
Methods and results Here, direct Sun observations
from aboard the LPMA/DOAS balloon
payload are used to absolutely infer Eo in
two wavelength bands in the UV/visible spectral
range. After an on-ground spectro-radiometrical
calibration has been performed for each balloon
flight, the solar irradiance measurements are conducted
at about 30 to 35 km balloon float altitude
where the remaining atmospheric extinction
is minimal and can be accounted for easily. Thorough
tracking and removal of systematic errors
results in high-accuracy measurement of the extraterrestrial
solar irradiance.
Comparison of our balloon borne data set with
previous studies yields excellent agreement, see
Figure 2.22, and suggests that, to date, the integrated
Eo is uncertain by as much as 5 W/m 2
in the respective wavelength range Gurlit et al.
[2005].
Outlook/Future work
• Quality check of the standard Eo recommendation
by further refinement of the calibration
procedure
• Long term validation, monitoring and recalibration
of satellite-borne Eo measurements
• Monitoring of natural solar variability
Main publications Lindner A., Ballongestütze
Messungen der extraterrestrischen spektralen solaren
Irradianz, Diploma thesis, University of Heidelberg,
Germany, 2005.

2.3. RADIATIVE TRANSFER 51
2.3.4 Atmospheric detection of water dimers and their contribution to
solar shortwave absorption
Participating scientists Lotter, A., C . Peters, J. Schwärzle, and K. Pfeilsticker
Abstract The cause of the water vapor continuum and possible contributions to it by water dimers
is one of the most challenging question in atmospheric spectroscopy. Field measurements by means
of active long-path differential optical absorption spectroscopy (DOAS) were performed to probe the
atmosphere for water vapor continuum and dimer absorption.
Figure 2.23: Absorption cross section for water monomer (WM) and water dimer (WD). Due to the overlap,
WD absorption is masked by strong WM absorption, except for the three marked regions, where detection
may be possible.
Background Disagreement in Earth’s radiation
budget between observations and radiative transfer
models has been a major concern for several
decades, as there exists a significant level of solar
shortwave (SW) cloudy-sky absorption, commonly
referred to as excess absorption, beyond the
ability of any model to predict. Many attempts
have been made to explain the observed excess of
solar SW absorption, but all potential mechanisms
on their own fall far short of explaining a possible
absorption deficit as much as 30 W/m 2 . One
mechanism of the required additional absorption
was suggested to come from a combined contribution
of the water continuum and water dimers
(WD). WDs may also play an important role in atmospheric
physics by e.g., initiating homogeneous
nucleation of water and photo-chemistry by catalyzing
chemical reactions (e.g., in the formation
of H2SO4).
Methods Possible atmospheric WD absorption
was investigated by extreme long path (up to
29 km) near ocean surface absorption measurements
during 3 field campaigns conducted in
Northern Germany in May 2002, France in June
2003, tropical Brazil in Dec./Jan. 2004. Since the
near-IR absorption spectrum of WD is predicted
to largely overlap with that of WM, 3 almost interference
free WD lines were selected for the study
(see Figure 2.23). Here, the dependance of WD
absorption on the WM pressure squared is used
as an indicator for WD detection.
Results Although a WD absorption line at
13340 cm −1 was tentatively identified to be due to
WD absorption (Pfeilsticker et al. [2003]), subsequent
campaigns involving a larger WM concentration
(e.g., in Brazil) could not confirm its existence.
However, the latter measurements indicate
a possible WD absorption band at 16312 cm −1 .
Uncertainties, however, still remain in WD identification
due to uncertainties in the predicted WD
line position (up to 200 cm −1 ) and width (10–
200 cm −1 FWHM). The latter being a function
as to whether WD are truly bound, meta-stable
or simply free pair states. WD detection is also
hindered by uncertainties in the WM data bases
in particular for the WM weak lines.
Funding comes through the Deutsche ForschungsGemeinschaft
(PF 384/1-2 and 2-3).
Outlook More sensitive detection of WD absorption
will require higher quality WM and WD
data than existing.
Main publication Lotter A., Field measurements
of water continuum and water dimer absorption
by active long-path Differential Optical
Absorption Spectroscopy (DOAS), PhD thesis,
Universität Heidelberg, Heidelberg, Germany, in
preparation.

52 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
References
Coheur, P.-F., Fally, S., Carleer, M., Clerbaux, C., Colin, R., Jenouvrier, A., Mérienne, M.-F., Hermans,
C., & Vandaele, A. C. 2002. New water vapor line parameters in the 26000 - 13000 cm −1
region. J. Quant. Spec. and Rad. Transf., 74, 493 – 510.
Crewell, S., Bloemink, H., Feijt, A., García, S.G., Jolivet, D., Krasnov, O.A., van Lammeren, A.,
Löhnert, U., van Meijgaard, E., Meywerk, J., Quante, M., Pfeilsticker, K., Schmidt, S., Scholl, T.,
Simmer, C., Schröder, M., Trautmann, T., Venema, V., Wendisch, M., & Willén, U. 2004. The
BALTEX Bridge Campaign - An integrated approach for a better understanding of clouds. Bull.
Am. Met. Soc., 85, 1565 – 1584.
Davis, A. B., & Marshak, A. 2002. Space-time characteristics of light transmitted by dense clouds: A
Green function analysis. J. Atmos. Sci., 59, 2713 – 2727.
Fally, S., Coheur, P.-F., Carleer, M., Clerbaux, C., Colin, R., Jenouvrier, A., Mérienne, M.-F., Hermans,
C., & Vandaele, A. C. 2003. Water vapor line broadening and shifting by air in the 26000 -
13000 cm −1 region. J. Quant. Spec. and Rad. Transf., 82, 119 – 131.
Fontenla, J., White, O. R., Fox, P. A., Avrett, E. H., & Kurucz, R. L. 1999. Calculation of solar
irradiances, I. Synthesis of the solar spectrum. Astrophys. J., 518, 480 – 500.
Gurlit, W., Bösch, H., Bovensmann, H., Burrows, J. P., Butz, A., Camy-Peyret, C., Dorf, M., Gerilowski,
K., Lindner, A., Noël, S., Platt, U., Weidner, F., & Pfeilsticker, K. 2005. The UV-A
and visible solar irradiance spectrum: Inter-comparison of absolutely calibrated, spectrally medium
resolved solar irradiance spectra from balloon-, and satellite-borne measurements. Atmos. Chem.
Phys., 5, 1879 – 1890.
Harder, J., Lawrence, G., Rottman, G., & Woods, T. 2000. The Spectral Irradiance Monitor (SIM)
for the SORCE Mission. Proc. SPIE, 4135, 204 – 214.
Kurucz, R. L., Furenlid, I., Brault, J., & Testerman, L. 1984. Solar Flux Atlas from 296 to 1300 nm.
National Solar Observatory, Atlas No. 1. ftp://ftp.noao.edu/fts/fluxatl.
Lindner, A. 2005. Ballongestütze Messungen der extraterrestrischen spektralen solaren Irradianz.
Diploma thesis, University of Heidelberg, Heidelberg, Germany.
Partridge, H., & Schwenke, D. W. 1997. The determination of an accurate isotope dependent potential
energy surface for water from extensive ab initio calculations and experimental data. J. Chem. Phys.,
106, 4618 – 4639.
Pfeilsticker, K. 2005a. Collisional complexes, metastable, and stable complexes in the atmosphere, and
their potential importance for the absorption of solar radiation. Gordon Research Conference on
Radiation & Climate, Colby College, Waterville, ME, USA, July 24-29.
Pfeilsticker, K. 2005b. Recent cloudy sky photon path pdf measurements from Heidelberg. 3rd I3RC
Workshop, IFM Kiel, October 11-14.
Pfeilsticker, K., Lotter, A., Peters, C., & Bösch, H. 2003. Atmospheric detection of water dimer via
near-infrared absorption. Science, 300, 2078 – 2080.
Pfeilsticker, K., Lotter, A., Boesch, H., & Peters, C. 2004. Collisional complexes, metastable and stable
dimers in the atmosphere, and their potential importance for the absorption of solar radiation. 228th
National ACS Meeting, Philadelphia, PA, USA, August 22-26.
Rothman, L. S., Barbe, A., Benner, D. C., Brown, L. R., Camy-Peyret, C., Carleer, M. R., Chance,
K., Clerbaux, C., Dana, V., Devi, V. M., Fayt, A., Flaud, J.-M., Gamache, R. R., Goldman, A.,
Jacquemart, D., Jucks, K. W., Lafferty, W. J., Mandin, J.-Y., Massie, S. T., Nemtchinov, V.,
Newnham, D. A., Perrin, A., Rinsland, C. P., Schroeder, J., Smith, K. M., Smith, M. A. H., Tang,
K., Toth, R. A., Vander Auwera, J., Varanasi, P., & Yoshino, K. 2003. The HITRAN molecular
spectroscopic database: edition of 2000 including updates through 2001. J. Quant. Spec. and Rad.
Transf., 82, 5 – 44.

2.3. RADIATIVE TRANSFER 53
Rothman, L. S., Jacquemart, D., Barbe, A., Benner, D. C., Birk, M., Brown, L. R., Carleer, M. R.,
Chackerian Jr., C., Chance, K., Coudert, L. H., Dana, V., Devi, V. M., Flaud, J.-M., Gamache,
R. R., Goldman, A., Hartmann, J.-M., Jucks, K. W., Maki, A. G., Mandin, J.-Y., Massie, S. T.,
Orphal, J., Perrin, A., Rinsland, C. P., Smith, M. A. H., Tennyson, J., Tolchenov, R. N., Toth, R. A.,
Vander Auwera, J., Varanasi, P., & Wagner, G. 2005. The HITRAN 2004 molecular spectroscopic
database. J. Quant. Spec. and Rad. Transf., 96, 139 – 204.
Scholl, T., Pfeilsticker, K., Davis, A.B., Klein Baltink, H., Crewell, S., Löhnert, U., Simmer, C.,
Meywerk, J., & Quante, M. 2005. Path length distributions for solar photons under cloudy skies:
Comparison of measured first and second moments with predictions from classical and anomalous
diffusion theories. J. Geophys. Res., revised.
Weidner, F. 2005. Development and application of a versatile balloon-borne DOAS instrument for
skylight radiance and atmospheric trace gas measurements. PhD thesis, University of Heidelberg,
Heidelberg, Germany.
Weidner, F., Bösch, H., Bovensmann, H., Burrows, J.P., Butz, A., Camy-Peyret, C., Dorf, M.,
Gerilowski, K., Gurlit, W., Platt, U., von Friedeburg, C., Wagner, T., & Pfeilsticker, K. 2005.
Balloon-borne limb profiling of UV/vis skylight radiances, O3, NO2, and BrO: Technical set-up
and validation of the method. Atmos. Chem. Phys., 5, 1409 – 1422.

2.4. DOAS TOMOGRAPHY GROUP 55
2.4 DOAS Tomography Group
Group members
Dr. Irene Pundt, head of group
Dipl. Met. Claudia Hak, PhD student
Dipl. Phys. Andreas Hartl, PhD student
Dipl. Phys. Klaus-Peter Heue, PhD student
Dipl. Phys. Kai-Uwe Mettendorf, PhD student
MPhys. Denis Pöhler, PhD student
Bing-Chao Song, Research assistant
Alexander Stelzer, Diploma Student
Abstract The DOAS tomography group is a junior research group of the BMBF atmospheric research
program 2000 (AFO 2000). The group started in August 2000 as part of the research group
Atmospheric Physics of Prof. Dr. Ulrich Platt. DOAS Tomography is a novel technique developed
for spatially resolved measurements of trace gas distributions. In the framework of the Tom-DOAS
project, first tomographic measurements from ground and aircraft were carried out. New instruments
were developed and the method was validated during an indoor campaign. In addition computer tools
were developed to optimise instrumental configurations and to invert the measurements. The quality
of the localization and quantification of atmospheric emission plumes was estimated by numerical
studies.
Figure 2.24: Left: Groundbased tomographic setup using Longpath DOAS instruments. From each
telescope (houses) light beams are directed towards the four retro reflector arrays (yellow circles). The
light travels back to the initial telescopes, where it is spectrally analysed. Right: Airborne tomographic
measurements. Here the sunlight is captured by several telescopes from different directions. Using
measurements from different aircraft positions, a large number of intersecting light paths can be
achieved. The resulting trace gas column densities are subsequently inverted to obtain 2D-distributions
of trace gas concentrations.
Overarching topic and Background
Air pollution due to anthropogenic trace gas emissions can cause serious environmental and medical
problems. For example, for human beings air pollutants like ozone, nitrogen dioxide (NO2), sulphur
dioxide (SO2) and benzene cause respiratory diseases. The predictability of their spatial distributions
is subject to numerous uncertainties. For continuous concentration records some wide meshed networks
of in situ measurement stations were installed. However, single-point measurements are often not
sufficient in order to explain differences between models since small-scale characteristics of the models
are not taken into account. In contrast, spatially resolved measurements can provide this type of
information.
Differential optical absorption spectroscopy (DOAS) is a path-integrating measurement technique
for atmospheric trace gases like ozone, nitrogen oxides, SO2, halogen oxides (BrO, IO, OClO) and many
hydrocarbons. For DOAS, a continuous artificial or natural light source (sun, moon, ) is used. Because
of the characteristic absorption features it is possible to measure several trace gases simultaneously
(e.g. NO2, SO2, HCHO, HONO, and ozone in the UV region). In a typical so-called long-path (LP)
setup a beam of white light, emitted by a telescope, travels through the atmosphere to a retro-reflector
and back to the telescope. Absorption patterns in the received light allow determining the column
density (the integrated concentration) of the trace gases along the light path.
Our DOAS tomography setups consist of a number of intersecting light paths (left figure). Column
densities of one or several trace gases measured by the DOAS technique along the light paths are

56 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
inverted to obtain concentration distributions by tomographic techniques.
In contrast, the Airborne Multi AXis (AMAX) DOAS instrument measures passively the sunlight
which is scattered in the earths atmosphere and/or reflected on the ground (right figure). Several small
telescopes are used which are directed in various directions and which capture the light simultaneously.
Each measurement provides results from several different paths throughout the atmosphere. As the
aircraft moves on from measurement to measurement, data of many intersecting light paths is recorded.
First tomographic line-integrating indoor measurements of 2D trace gas distributions were realized
in the 1990s by using open-path Fourier infrared absorption spectroscopy. There have been improvements
in speed and spatial resolution since, but all experiments have been restricted to the laboratory
environment so far.
Main methods
During the last five years, for the first time DOAS two-dimensional tomographic experiments using a
larger number (10-90) of intersecting light paths have been carried out (e.g., Pundt [2005b]). At the
ground, long path active instruments were used to measure 2D emission plumes from road traffic or
horizontal distributions of trace gases (e.g. Pundt et al. [2005c], Lösch [2001], Kunz [2001], Bäuerle
[2004], Rippel [2005], Poehler et al. [2005]). Instruments which are more suitable for tomographic
applications were developed (Pundt & Mettendorf [2005], Mettendorf [2005]) and the reconstruction
methods were validated during an indoor campaign (Mettendorf et al. [2005]). From aircraft, passive
instruments were used to measure 2D distributions of a power plant emission plume (Pundt et al.
[2005a], Heue et al. [2005]). The quality of the localization and quantification of atmospheric emission
plumes has been estimated by means of numerical studies (Knab [2004], Laepple et al. [2004], Hartl
et al. [2005a]). In addition, the group participated in two measurement campaigns in the Po-Valley
region in the framework of the EU FORMAT project (e.g., Hak et al. [2005]).
Subprojects
Groundbased DOAS tomography
Airborne DOAS tomography
Theoretical studies
FORMAT: Formaldehyde as a Tracer of Photo oxidation in the Troposphere (EU project)
Funding
BMBF (TomDOAS)
EU (FORMAT)
Cooperation
University of Bremen
FZK Karlsruhe (IMK Karlsruhe)
IFU Garmisch-Partenkirchen (IMK Karlsruhe)
NILU (Norway)
IASB (Belgium)
PSI (Switzerland)
Anhui Institute (Hefei, China)
Publications
Peer reviewed Publications
1. Bruns et al. [2004]
2. Fix et al. [2005]
3. Hak et al. [2005]
4. Heckel et al. [2005]
5. Heue et al. [2005]
6. Laepple et al. [2004]
7. Pundt & Mettendorf [2005]

2.4. DOAS TOMOGRAPHY GROUP 57
8. Pundt [2005b]
9. Pundt et al. [2005c]
10. von Friedeburg et al. [2005]
11. Wang et al. [2005b]
Other Publications
1. Bruns et al. [2005]
2. Hartl et al. [2005b]
3. Hartl et al. [2005a]
4. Heue et al. [2004]
5. Poehler et al. [2005]
6. Pundt et al. [2005b]
7. Wang et al. [2005a]
Doctoral Thesis
1. Heue [2005]
2. Mettendorf [2005]
Diploma Thesis
1. Stelzer [2005]
2. Rippel [2005]
3. Knab [2004]
4. Bäuerle [2004]
Invited talks
1. Pundt [2005a]
2. I. et al. [2005]

58 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.4.1 Intercomparison of ambient in-situ Formaldehyde Measurements in
urban Air
Participating scientist Claudia Hak et al.
Abstract An intercomparison of in-situ formaldehyde (CH2O) measurements, including four different
techniques, is presented. Formaldehyde levels between 1 and 13 ppbv were measured in an urban
environment in Milano, Italy. By using only point measurement methods, it was ensured that all
instruments probed the same air volume.
Figure 2.25: Fractional difference histograms, calculated relative to a reference Hantzsch instrument
Background Previous intercomparisons revealed
significant disagreement among the techniques
used. However, there was no general pattern
in the deviations. Since formaldehyde is an
important intermediate in the oxidation of VOCs
and a source of HOx radicals, it was a major
objective of the FORMAT (FORMAldehyde as
a Tracer of photooxidation in the troposphere)
project to intercompare the different available
measurement techniques. These involved the wet
chemical Hantzsch method (five instruments), the
DNPH method with HPLC separation, DOAS
and FTIR. For the optical methods DOAS and
FTIR, White-multireflection systems were used.
In contrast to long path integrating optical methods
which average horizontally and vertically,
they measure the absorption of trace gases along
a short base path of a few metres.
Funding FORMAT, European Union
Methods and results Two methods were applied
for the intercomparison of the measurement
results. Firstly, an orthogonal regression analysis
was performed, comparing the individual results
of all instrument pairs with each other. The
correlation analysis showed a very good agreement
among the Hantzsch results, however the
slopes and intercepts from the regression analysis
revealed some systematic differences. The optical
techniques showed larger scattering. The second
method was the analysis of fractional differ-
ences, i.e. the difference between the results of
each instrument and an (arbitrarily chosen) reference
instrument according to δ=([CH2O]instr.-
[CH2O]ref.)/[CH2O]ref.. Because of its long and
continuous time series, the BUW Hantzsch results
were chosen as the reference. The figure depicts
the results of the fractional difference analysis.
The nearly collocation of mode, median and average
for most distributions suggests symmetry
in the distribution and therefore mostly random
differences. In summary, a ±11% agreement was
found among the Hantzsch results. The observed
discrepancies were partly attributed to different
calibration standards. The agreement of the two
optical methods was within 5%, which is within
the uncertainties of the UV and IR absorption
cross-sections (both 5%). Hantzsch and spectroscopic
techniques agreed within 15%. DNPH results
were generally lower than the measurements
of the continuous techniques by up to 25%. A
more detailed description of the methods as well
as the discussion of the problems and the uncertainties
of the Hantzsch and the optical methods
can be found in Hak et al. [2005].
Outlook/Future work This work is finished.
The discrepancies in liquid calibration standards
of Hantzsch instruments form a task which is currently
under investigation by other groups.
Main publication Hak et al. [2005]

2.4. DOAS TOMOGRAPHY GROUP 59
2.4.2 Trace gas distributions from long-path DOAS measurements
Participating scientist Andreas Hartl
Abstract The possibility to retrieve 2D trace gas concentration fields from a limited number of longpath
DOAS measurements was studied theoretically. Using a discrete approach it was found that the
reconstruction can be tremendously improved by using optimal parametrisation of the unknown field,
but its resolution is restricted by the number of light paths.
100
y
0
x
100
1
conc.
0.5
0
50
x
100
50 y
100
conc.
0.5
Figure 2.26: (Left) Geometric arrangement with 3 telescopes and 36 light paths, (centre) 2D test
distribution of 4 Gaussian concentration peaks and (right) its reconstruction by averaging over several
bilinear discretisation grids.
Background Experiments designed to give information
on the spatial distribution of concentration
fields are limited to certain scales and, if there
are not enough measurements, they are sometimes
hard to interpret. Point measurements are subject
to all sorts of flucuations, path integrating
absorption measuremts only provide average concentrations.
While special processes, like plume
development from a single point source or pollution
in a street canyon, have been studied intensively,
there is only little data available for others,
e.g. distributions over a city region.
This work examines 2D retrieval of concentration
fields from ground-based DOAS measurements
with artificial light sources on scales of a
few km by techniques very similar to the ones used
in conventional computerised tomography. These
experimental concentration maps eventually can
be used for the validation of chemical transport
models, escpecially in cases where different model
scales play a role.
Funding BMBF through project 07 ATC-03
(Young researchers fellowship program for research
groups, AFO 2000-C).
Methods and results The unknown concentration
field is expressed in terms of a limited
number of “basis” functions with local support
and the discrete set of parameters is fit to the
measurement data using a least squares principle.
For the box and bilinear basis considered here, the
1
0
50
x
100
50 y
100
parameters represent values in the boxes and on
the nodes of the discretisation grid, respectively.
In the simulations, Gaussian peaks of varying half
width serve as test distributions, motivated by the
semi-empirical approach that describes turbulent
transport and advection in the atmosphere by a
diffusion model.
We found that formulation of the problem, i.e.
its parametrisation in terms of type and number
of basis functions, plays a paramount role for the
reconstruction quality. It turns out that the narrower
the peaks, the finer the discretisation grid
can be chosen, leading to systems with as many as
four times unknowns than knowns - provided additional
(physical or ad hoc) information is added.
Bilinear function allow not only better discretisation,
but also improved inversion of the problem
and taking into account different discretisation
grids can further reduce reconstruction errors.
Reconstruction quality strongly depends on
the light path geometry, Fig. 2.26 shows an example
for one of the geometries exmamined.
Outlook/Future work Application to high
resolution model data for a heavily polluted
area over Hannover, reconstruction from measurements
in Heidelberg, further theoretical work on
the estimation of the reconstruction error field,
the inclusion of point measurements and the 3D
case.
Main Publication Hartl et al. [2005a]

60 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.4.3 Airborne measurements of the CH2O and NO2 distributions in the
Po basin
Participating scientists Klaus-Peter Heue, Ping Wang 2 and Irene Pundt
2 Institut für Umweltphysisk, Universität Bremen
Abstract During two FORMAT campaigns the Airborne Multi AXis DOAS (AMAXDOAS) instrument
was used to determine the two dimensional formaldehyde and nitrogen dioxide distributions
around Milano. Vertical distributions were retrieved from observed slant column densities from the
spectra of six telescopes directed at different viewing angles.
Figure 2.27: Formaldehyde average mixing ratio at 0-1000 m altitude along the flight track
Background One of the major aims of the
FORMAT project (FORMAldehyde as a tracer
of photooxidation in the Troposphere) was to
observe the different sources of photooxidating
traces gases in the atmosphere. Fossil fuel combustion
is known to be a source of NOx and
VOCs. Other source of VOCs are biogenic emissions
and natural fires. Formaldehyde is an important
intermediate in the oxidation of VOCs.
The AMAXDOAS observation results in differential
slant column densities (dSCDs) for each of
the ten telescopes. For the reference location the
observed dSCD vanishes. In total 20 flights were
performed during two campaigns in 2002 and 2003
and the slant column of HCHO, NO2, O4 and
SO2 were retrieved.
Funding FORMAT, DOAS Tomography,
SCIAMACHY validation
Methods and results The observed signal of
passive DOAS systems like the AMAXDOAS is
strongly influenced by the aerosol content. Based
on the O4 observations of all ten telescopes the
aerosol content can be approximated for several
measurement locations including the reference.
The different telescopes have different sensibilities
for O4 absorptions if the aerosol content
changes. Using a radiative transfer model we
modelled the O4 SCDs for several aerosol contents
and compared them with the observations.
The aerosol content affects the sensitivity of the
different lines of sight. Based on the observations
form five downward directed lines of sight
the CH2O vertical columns along the flight can
be deduced. However, the measurement principle
requires some approximations about the CH2O
concentration at the reference location. Assuming
a standard profile, based on independent measurements,
an average mixing ratio for the lowest 1000
m can be retrieved. Figure 2.27 shows the average
CH2O mixing ratio distribution around Milano
on 16/08/2002. On this day the wind blew
from south east, therefore in the north west of the
town an enhanced HCHO concentration is observed.
The emission plume of Milano was found
to be 20 km wide and the net CH2O production
is estimated at 0.6 tons/hour.
Outlook/Future work Publication is in
preparation.
Main publications Heue [2005]

2.4. DOAS TOMOGRAPHY GROUP 61
2.4.4 Development of a Multibeam instrument for simultaneous measurements
along multiple light paths
Participating scientists Kai Uwe Mettendorf and Irene Pundt
Abstract Long path DOAS tomography uses multiple Long path DOAS instruments and intersecting
light paths to retrieve the concentration distributions of certain trace gases. For these measurements
a new DOAS instrument was developed. Three instruments were build.
Figure 2.28: Instrumental setup of the entire Multibeam system (including, A, telescope; B, lamp
housing; C, mode mixer; D, spectrograph; E, CCD detector; F, stepper motor controller; G, mirror
tower with four mirror units; H, rotating disk retroreflector; I, retroreflector array at a distance
between 500 and 5000 m). The distance between the telescope and the mirror tower is usually 10-15
m. The distance between the rotating retroreflector and the tower is also 10-15 m. The rotating disk
can be placed close to the telescope.
Background Conventional Long-path DOAS
Instruments emit a single light beam. For two
dimensional DOAS-tomographic-measurements,
however at least 10-40 light paths are necessary.
The Multibeam DOAS instrument, which emits
one to six light paths was developed for this purpose.
Funding DOAS Tomography (BMBF)
Methods and results A novel long-path differential
optical absorption spectroscopy (DOAS)
apparatus for measuring tropospheric trace gases
the ”Multibeam” instrument was developed. It is
the first active DOAS device that emits several
light beams simultaneously through only one telescope
and with only one lamp as a light source,
allowing simultaneous measurement along multiple
light paths. In contrast to conventional
DOAS instruments, several small mirrors are positioned
near the lamp, creating multiple virtual
light sources that emit one light beam each in one
specific direction. The possibility of error due to
scattering between the light beams is negligible.
The trace-gas detection limits of NO2, SO2, O3,
and H2CO are similar to those of the traditional
long-path DOAS instrument. However, the received
light intensity is reduced by a factor of 3
compared to a traditional long-path DOAS instrument
with a similar main mirror.
Main publication Pundt & Mettendorf [2005],
Mettendorf [2005]

62 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.4.5 An Indoor Test Campaign of the Tomography Long Path Differential
Optical Absorption Spectroscopy (DOAS) Technique
Participating scientists Kai Uwe Mettendorf, Andreas Hartl and Irene Pundt
Abstract For the validation of the LP-DOAS-tomography method and the test of the Multibeam
DOAS instrument an indoor validation campaign was performed. Known concentration distributions
were successfully measured by 39 intersecting light paths and reconstructed using the SIRT-method.
Figure 2.29: Reconstruction of a concentration distribution by SIRT on a 12×12 pixel grid and with
additional grid shifting. The upper panel shows the original concentration distribution, the lower left
panel the result from modelled column densities and the lower right panel the result from measured
column densities.
Background Long path DOAS tomography is
a novel application of the DOAS-method which
was not been validated before.
Funding DOAS Tomography (BMBF)
Methods and results In this study the twodimensional
long path DOAS tomography measurement
technique was validated by an indoor experiment
with well-known concentration distributions.
The experiment was conducted over an area
of 10m×15m using one and two cylindrical containers
of diameter 2 m, respectively, filled with
NO2. The setup was realized with three of the recently
developed Multibeam instruments (Pundt
and Mettendorf, 2005), which allow the simultaneous
measurement along at least four light paths
each. The configuration consisted of twelve simultaneous
light beams, 39 horizontal light paths in
total, and 16 different cylinder positions inside the
field. It was found that for the discretization and
inversion technique shown here reconstructions of
the concentration distributions from experimental
data agree well with simulated reconstructions. In
order to draw conclusions for atmospheric applications,
numerical studies including instrumental errors
were carried out. It was concluded that with
the presented measurement setup it should be possible
to measure and reconstruct one or two NO2
plumes of 600 m diameter and average concentrations
above 4.2 ppbv each, to a scale of 13.5 km 2 .
Theoretical investigations show that it should be
possible to localize and quantify 600 m diameter
plumes of SO2 > 1.5 ppbv, H2CO > 6.3 ppbv,
HONO > 3.2 ppbv, and O3 > 46.2 ppbv.
Main publication Mettendorf [2005]

2.4. DOAS TOMOGRAPHY GROUP 63
2.4.6 2D and 3D tomographic LP-DOAS measurements of trace gas distributions
in Heidelberg over an area of 4 ∗ 4 km 2
Participating scientists Denis Poehler, Alexander Stelzer, Irene Pundt
Abstract A configuration of three Multibeam LP-DOAS Instruments and 20 different light paths
to retro reflector arrays was established for long term 2D and 3D measurements of NO2, SO2, O3,
HCHO, and HONO over an area of a 4 ∗ 4 km 2 above the city centre of Heidelberg.
Figure 2.30: 3 Dimensional view on all light paths of the measurement over an area of 4 ∗ 4 km 2 with
three telescope locations: IUP, SAS and HD-Druck.
Background LP-DOAS (Long Path Differential
Absorption Spectroscopy) is a well known
technique for measuring average concentrations of
tropospheric trace gases along a light path extending
between a telescope and a retro reflector. But
single path measurements are often not sufficient
(as well as single point measurements), if smallscale
variations exist or transport is important.
To obtain informations of the dispersion, it is necessary
to measure along a couple of light paths.
The development of the ”Multibeam LP-DOAS
telescope” (Pundt and Mettendorf, 2005), allows
the measurement along up to 6 light paths simultaneously.
With the suitable combination of
two or more Multibeam LP-DOAS telescopes and
the use of tomographic reconstruction techniques
good quality 2D and 3D reconstructions of the
measured trace gases can be achieved.
Funding German Ministry of Research and Education
, AFO 2000-C, project 07 ATC-03
Methods and results The experimental setup
consists of 3 Multibeam telescopes located on top
of high buildings in the city (IUP, HD-Druck and
SAS) and 20 retro reflector arrays. This work focuses
on the one hand on the telescope location
HD-Druck, where a Multibeam Instrument was
installed and modified, to allow automatic measurements
from this place.
Each of the three telescopes uses a Xe-Arc lamp as
light source, which creates up to 6 parallel light
beams using different mirrors. Each light beam
can be redirected to different retro reflector arrays
which reflect parts of the light back into the
telescope. The received light is measured with a
Czerny Turner Spectrograph and contains information’s
of the trace gas absorptions. With the
measurement between 285 nm and 365 nm and
the use of the DOAS technique reconstruction of
NO2, SO2, O3, HCHO, and HONO are made
along each light path.
During the first measurements it was mostly impossible
to run all three telescopes simultaneously,
due to many breakdowns of the sensitive experimental
setup. But since simultaneous measurements
of all light paths are necessary for tomographic
inversions, the hardware was modified and
new controller software was coded to improve the
stability. First simultaneous measurements were
performed in September 2005, but are not completely
analysed yet.
Outlook/Future work The system will be run
continuously over a time scale of several months.
For the periods of simultaneous measurement
data, 2 dimensional trace gas distributions will
be reconstructed.
Main publication Poehler et al. [2005]

64 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.4.7 Two-dimensional measurement of motorway emission plumes
Participating scientist Irene Pundt, Kai Uwe Mettendorf
Abstract A first Long-path Tom-DOAS experiment was carried out in April/May 2001 next to
the German motorway A656 (between Heidelberg and Mannheim), as part of the BAB II campaign
(Fiedler et al., 2001). From the measurements along 16 different light paths vertical profiles on both
sides of the motorway as well as two-dimensional maps of the NO2, SO2 and ozone concentration
distributions could be derived. Emission factors were calculated and compared to model simulations.
Figure 2.31: Left: Tomographic setup used during a motorway emission campaign. From each telescope
one light beam is directed successively towards the eight retro reflectors (circles). Right: NO2
motor vehicle emission plume perpendicular to a motorway (in ppbv). Black bar: Location of the
motorway, chequered area: Experiment towers, wind direction: coming from the left.
Background Traffic emissions are among the
major sources for anthropogenic air pollution.
Volatile compounds and nitrogen oxides (NOx)
are, besides others, important components of
these emissions. Vehicle emission factors are generally
estimated by means of dynamometric test
measurements, but they may change under real
world conditions. Therefore, a couple of field studies,
mostly performed inside tunnels, have been
conducted. However, the air flow through tunnels
is influenced by the moving cars, causing an artificial
wind, which changes the traffic emissions. A
more realistic approach to evaluate emission factors
is to carry out measurements at an open road.
Knowledge of vertical profiles on both sides of the
road is necessary to calculate emission rates (in
molecules s −1 m −1 ). Taking 2D images of the
emission plume perpendicular to the line source
can provide even more information than emission
rates. 2D images can be used to validate 2D
dispersion models, or in the case of short lived
species, to validate 2D chemical transport models.
Funding TOMDOAS (BMBF)
Methods and results The tomographic arrangement
consisted of two long path telescope
sites (one at each side of the motorway), and eight
retro reflector arrays (four on each side at different
heights). Each of the telescopes emitted
one light beam, which was successively directed to
the different retro-reflectors. Altogether 16 different
light paths were realised. 2D NO2 concentration
distributions perpendicular to the motorway
were derived for several time spans (right figure).
Concentrations on the left-hand side of the figure
represent the NO2 background abundance and
the right-hand side the background concentration
plus emissions. For the inversion, an algebraic reconstruction
technique was used in combination
with bilinear basis functions describing the distribution.
The derived emission plumes are, within
the errors, in good agreement with model expectations.
To our knowledge, these are the first measurements
of two dimensional sections of an emission
plume from a line source. Using multibeam
telescopes will increase the time resolution of the
images from hours to minute ranges in the future.
Outlook/Future work SO2 and HCHO emission
rates are currently evaluated and compared
to model simulations. Ozone distributions seem to
be not consistent with model expectations. Further
work is needed to understand the discrepancies.
Main publication Pundt et al. [2005c], Laepple
et al. [2004], Mettendorf [2005]

2.4. DOAS TOMOGRAPHY GROUP 65
2.4.8 Two dimensional concentration distributions of a NO2 Emission plume
from a point source derived by Airborne DOAS Tomography
Participating scientists Irene Pundt, Klaus-Peter Heue, Bing-Chao Song
Abstract First airborne DOAS tomography measurements of two-dimensional concentration crosssections
of a plume from a point source have been carried out. The measurements were performed
with an AMAXDOAS (Airborne Multi-AXis Differential Optical Absorption Spectroscopy) instrument
onboard a small aircraft during the second campaign of the European FORMAT project in August /
September 2003.
Figure 2.32: Left: Lines of sight of the flight track as function of the geographic position of the Sermide
power plant plume. X is the latitudinal, y the longitudinal and z the vertical direction. For clearness,
only the downward looking viewing directions are shown neglecting the scattering of light. The colors
of the lines indicate the NO2 slant column densities along each of them. Right: NO2 2D mixing ratio
distributions of the Sermide plume after tomographic inversion, first pass (distance from the plant: 5
km).
Background The focus of this study is the first
application of the Airborne DOAS Tomography
technique to provide concentration distributions
of NO2 along cross sections of a plume from a
point source. A technique to formulate a two dimensional
inversion problem with weighting matrices
from single scattering radiative transfer simulations,
which can be used for tomographic inversions,
is presented.
Funding TomDOAS (BMBF), FORMAT (EU)
Methods and results As part of the second
campaign of the European FORMAT project
(FORMAldehyde as a tracer of photo oxidation
in the Troposphere), the instrument was installed
on board a Partenavia PA 68 aircraft. During one
occasion, on 26 September 2003, it was possible to
derive the information for two-dimensional reconstructions
of an emission plume of a point source.
Three over flights were performed across the emission
plume of the NO2 emitting Sermide power
plant, located at 45.02 degree N 11.25 degree E.
Three reconstructions have been performed, one
for each overpass. It is assumed that the plume
has not changed during the course of the measurement.
Therefore 5, 6 and 9 aircraft positions, re-
sulting in 50, 60 and 90 lines of sight were included
for the 1st, 2nd and 3rd overpass, respectively (left
figure). For each overpass, the area of interest
is divided into rectangular boxes with 16 vertical
segments of 133 m height and horizontal segments
of 1.5 km length. For each inversion, the weighting
matrix was calculated for the respective 2D
grid. Then the inversion is performed using the
Simultaneous Iterative Reconstruction Technique
(SIRT) method. The right Figure presents the resulting
NO2 mixing ratio maps for the first overpass.
Interestingly the first and the third overpass,
which were conducted very close by, show
similar shapes, indicating only small changes of
the plume during the 12 minutes flight interval.
From this finding we conclude that the quality of
the reconstruction is reproducible and consistent.
NOX emissions of 4.1-9.6 10 24 molec s −1 were
derived, in agreement with the information given
by the power plant company.
Outlook/Future work The analysis of the
FORMAT flights is ongoing.
Main publication Pundt et al. [2005a], Heue
[2005]

66 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.4.9 Development of a computer tool for the inversion and optimization
of airborne tomographic DOAS measurements (Tomolab2)
Participating scientist Bing-Chao Song, Andreas Hartl and Irene Pundt
Abstract The tomographic DOAS software project Tomolab [Laepple et al., 2004] is further developed
for Airborne Multi Axis DOAS (AMAXDOAS) measurements. With its ability to include
scattered light paths it can be used to optimize airborne measurements, optimize measurement geometries
and for the reconstruction of 2D/3D concentration fields.
Figure 2.33: Flight track with ground-reflected light paths (left), 2D single scattering light path
geometry and reconstruction (right) in Tomolab2.
Background The Tomolab software was originally
created especially for ground-based active
measurements, i.e. light paths clearly defined by
source and reflector. While it is efficient for analyzing
and displaying simple geometries, it does
not include scattering processes, neither in its
graphics nor in its inversion part. Tomolab was
designed as a Windows project and runs on personal
computers only. The enhanced version Tomolab2
removes the dependency of the Windows
system and, for intensive calculations, can be run
on any UNIX workstation. Very flexible scripting
support simplifies case studies for different geometric
settings and atmospheric conditions.
Funding DOAS Tomography, BMBF
Method Single scattering processes, usually
dominating the atmospheric radiative transfer,
are simulated by defining a group of partial light
paths which all enter the telescope and add up to
the same measurement signal. Their individual
contributions to the total absorption captured by
the telescope are weighted by their relative light
intensities from radiative transfer calculation for
the layer where the scattering event took place.
We finally obtain box air mass factors (AMFs)
for cases where single scattering dominates. Measurements
where multiple scattering is not negligi-
ble can also be simulated and reconstructed, but
the corresponding 2D or 3D box AMFs have to
be calculated by suitable radiative transfer models.
The modular structure of Tomolab2 makes
exchange of platform dependent code easier. The
visualization part is currently implemented for the
Windows system. The scripting support layer for
Windows is implemented using the so called COM
technique. Essential and common functions are
encapsulated into binary components to ensure
the stability of the project. Varying case studies
can be done by scripting components without
modifying Tomolab2’s code.
Results The Tomolab2 project was developed
for passive airborne DOAS measurements and
designed aiming at a flexible and platformindependent
structure. 2D box AMFs have been
calculated for lightly polluted scenarios and compare
well with those from a radiative transfer
model. The program also has been tested on
UNIX platforms. Thanks to its modular structure,
Tomolab2 can easily be updated and maintained.
Outlook/Future work 3D reconstruction.
Embedding of radiative transfer models for operational
usage.

2.4. DOAS TOMOGRAPHY GROUP 67
References
Bäuerle, A. 2004. Messung von Spurenstoffverteilungen in Mailand mit Hilfe eines Multistrahl-
Langpfad Teleskops. Staatsexamensarbeit, Institut für Umweltphysik, Universität Heidelberg, Germany.
Bruns, M., Buehler, S. A., Burrows, J. P., Heue, K.-P., Platt, U., Pundt, I., Richter, A., Rozanov, A.,
Wagner, T., & Wang, P. 2004. Retrieval of profile information from Airborne Multi Axis UV/visible
skylight absorption measurements. Appl.Opt., 43(22), 4415 – 4426.
Bruns, M., Buehler, S. A., Burrows, J. P., Richter, A., Rozanov, A., Wang, P., Heue, K.-P., Platt, U.,
Pundt, I., & Wagner, T. 2005. NO2 Profile retrieval using airborne multi axis UV-visible skylight
absorption measurements over central Europe. Atmos. Chem. Phys. Discuss. accepted.
Fix, A., Ehret, G., Flentje, H., Poberaj, G., Gottwald, M., Finkenzeller, H., Bremer, H., Bruns, M.,
Burrows, J. P., Kleinbhl, A., Kllmann, H., Kuttippurath, J., Richter, A., Wang, P., Heue, K.-
P., Platt, U., Pundt, I., & Wagner, T. 2005. SCIAMACHY validation by aircraft remote sensing:
design, execution, and first measurement results of the SCIA-VALUE mission. Atmos. Chem. Phys.,
5, 1273 – 1289.
Hak, C., Pundt, I., Trick, S., Kern, C., Platt, U., Dommen, J., Ordóˆnez, C., Prévôt, A. S. H.,
Junkermann, W., Astorga-Lloréns, C., Larsen, B. R., Mellqvist, J., Strandberg, A., Yu, Y., Galle,
B., Kleffmann, J., Lörzer, J., Braathen, G. O., & Volkamer, R. 2005. Intercomparison of four
different in-situ techniques for ambient formaldehyde measurements in urban air. Atmos. Chem.
Phys., 5, 2881 – 2900.
Hartl, A., Song, B.-C., & Pundt, I. 2005a. Reconstructing 2d-Concentration Peaks from Long Path
DOAS-Tomographic measurements: Parametrisation and Geometry within a Discrete Approach.
Atmos. Chem. Phys. Discuss., 5, 11781 – 11819.
Hartl, A., Mettenorf, K. U., Song, B. C., & Pundt, I. 2005b. Reconstruction of 2D-Trace Gas
Concentration Distributions from Long-path DOAS Measurements: General Approach, Validation
and Simulations for an Experiment on an Urban Site. In: Proceedings of the 31st ”International
Symposium of Remote Sensing of the Environment”, June 20-24, 2005, in St. Petersburg, Russia.
ISPRS-publication(CD-ROM).
Heckel, A., Richter, A., Tarsu, T., Wittrock, F., Hak, C., Pundt, I., Junkermann, W., & Burrows,
J. P. 2005. MAX-DOAS measurements of formaldehyde in the Po-Valley. Atmos. Chem. Phys., 5,
909 – 918.
Heue, K.-P. 2005. Airborne Multi Axis DOAS instrument and measurements of two dimensional
tropospheric trace gas distributions. Ph.D. thesis, Institut für Umweltphysik, Universität Heidelberg,
Germany.
Heue, K.-P., Beirle, S., Bruns, M., Burrows, J. P., Platt, U., Pundt, I., Richter, A., Wagner, T., &
P. Wang, P. 2004. SCIAMACHY validation using the AMAXDOAS instrument. In: Proceedings
of the ENVISAT & ERS Symposium, 6-10 September 2004, Salzburg, Austria. ESA-publication
SP-572 (CD-ROM).
Heue, K.-P., Richter, A., Bruns, M., Burrows, J. P., Friedeburg, C. von, Platt, U., Pundt, I., Wang,
P., & Wagner, T. 2005. Validation of SCIAMACHY tropospheric NO2-columns with AMAXDOAS
measurements. Atmos. Chem. Phys., 5, 1039 – 1051.
I., I. Pundt, Mettendorf, K.U., & v. Friedeburg, C. 2005. Emissionsmessung von NO2, SO2 und O2
mittels DOAS Fernerkundung. Invited talk at the workshop ”Validierung von Kfz-Emissionsdaten:
Das Karlsruher Autobahnprojekt BAB II”, Karlsruhe, 01.12.2005.
Knab, V. 2004. Basic theory on DOAS tomography, Reconstruction of 2D trace gas distributions by
discrete linear inversion techniques. Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg,
Germany.
Kunz, C. 2001. Charakterisierung eines Multi-Strahl-Langpfad-DOAS-Systems zur Messung von
Spurenstoff-Konzentrationen in der Atmosphre. Staatsexamensarbeit, Institut für Umweltphysik,
Universität Heidelberg, Germany.

68 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
Laepple, T., Knab, V., Mettendorf, K.-U., & Pundt, I. 2004. Longpath DOAS tomography on a
motorway exhaust plume: Numerical studies and application to data from the BAB II campaign.
Atmos. Chem. Phys., 4, 1323 – 1342.
Lösch, J. 2001. Bestimmung von NO2 und SO2 Emissionen von Kraftfahrzeugen mittels DOAS-
Tomographie. Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg, Germany.
Mettendorf, K. U. 2005. Aufbau und Einsatz eines Multibeam Instrumentes zur DOAStomographischen
Messung zweidimensionaler Konzentrationsverteilungen. Ph.D. thesis, Institut
für Umweltphysik, Universität Heidelberg, Germany.
Mettendorf, K. U., Hartl, A., & Pundt, I. 2005. An indoor test campaign of the Tomography Long
Path Differential Absorption Spectroscopy (DOAS). J. Environ. Monit. accepted.
Poehler, D., Rippel, B., Stelzer, A., Mettendorf, K. U., Hartl, A., Platt, U., & Pundt, I. 2005.
Instrumental setup and measurement configuration for 2D-tomographic DOAS measurements of
trace gas distributions over an area of a few square km. In: Proceedings of the 31st ”International
Symposium of Remote Sensing of the Environment”, June 20-24, 2005, in St. Petersburg, Russia.
ISPRS-publication(CD-ROM).
Pundt, I. 2005a. DOAS (Differentielle Optische Absorptions- Spektroskopie)Messungen mit neuester
Technologie. Invited talk at the DECHEMA/GDCH/DGB-Gemeinschaftsausschuss Chemie der
Atmosphre, Frankfurt, 22.04.2005.
Pundt, I. 2005b. DOAS tomography for the localisation and quantification of anthropogenic air
pollution. Anal. Bioanal. Chem. accepted.
Pundt, I., & Mettendorf, K. U. 2005. Multibeam long-path differential optical absorption spectroscopy
instrument: a device for simultaneous measurements along multiple light paths. Appl. Opt., 44(23),
4985 – 4994.
Pundt, I., Heue, K.-P., Song, B.-C., Wagner, T., Bruns, M., Burrows, J. P., Richter, A., & Wang, P.
2005a. Airborne tomographic measurements of NO2 Plumes from point sources using the AMAX-
DOAS instrument. J. Geophys. Res. submitted.
Pundt, I., Hak, C., Hartl, A., Heue, K.-P., Mettendorf, K. U., Platt, U., Poehler, D., Rippel, B.,
Song, B.-C., Stelzer, A., Wagner, T., Bruns, M., Burrows, J. P., Richter, A., & Wang, P. 2005b.
Mapping of tropospheric trace gas concentration distributions from ground and aircraft by DOAStomography
(Tom-DOAS). In: Proceedings of the 31st ”International Symposium of Remote Sensing
of the Environment”, June 20-24, 2005, in St. Petersburg, Russia. ISPRS-publication(CD-ROM).
Pundt, I., Mettendorf, K. U., Laepple, T., Knab, V., Xie, P., Lösch, J., Friedeburg, C. von, Platt, U.,
& Wagner, T. 2005c. Measurements of trace gas distributions using Long-path DOAS-Tomography
during the motorway campaign BAB II: experimental setup and results for NO2. J. Atmos. Environ.,
39(5), 967 – 975.
Rippel, B. 2005. Vorarbeiten für Langpfad DOAS Tomographische Messungen über der Stadt Heidelberg.
Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg, Germany.
Stelzer, A. 2005. Horizontale tomographische Langpfad-DOAS Spurengasmessungen in Heidelberg.
Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg, Germany.
von Friedeburg, C., Pundt, I., Mettendorf, K. U., Wagner, T., & Platt, U. 2005. Multi-axis-DOAS
measurements of NO2 during the BAB II motorway emission campaign. J. Atmos. Environ., 39(5),
977 – 985.
Wang, P., Richter, A., Bruns, M., Burrows, J. P., Junkermann, W., Heue, K.-P., Wagner, T., Platt,
U., & Pundt, I. 2005a. Airborne multi-axis DOAS measurements of tropospheric SO2 plumes in
the Po-valley, Italy. Atmos. Chem. Phys. Discuss, 5, 2017 – 2045.
Wang, P., Richter, A., Bruns, M., Rozanov, V., Burrows, J. P., Heue, K.-P., Wagner, T., Pundt, I., &
Platt, U. 2005b. Measurements of tropospheric NO2 with an airborne multi-axis DOAS instrument.
Atmos. Chem. Phys., 5, 337 – 343.

2.5. SATELLITE GROUP 69
2.5 Satellite Group
Participating scientist Steffen Beirle, Tim Deutschmann, Barbara Dix, Ossama Ibrahim, Christian
Frankenberg, Michael Grzegorski, Klaus-Peter Heue, Jens Hollwedel, Muhammad Fahim Khokhar,
Sven Kühl, Thiery Marbach, Janis Pukite, Suniti Sanghavi, Thomas Wagner, and Walburga Wilms-
Grabe
Abstract The Satellitegroup is part of the researchgroup Atmospheric Physics of Prof. Dr. Ulrich
Platt. The satellite born remote sensing of the Earth’s atmosphere at the University of Heidelberg
started in 1996 with the retrieval of atmospheric trace gases, namely NO2 and BrO. Today a wide variety
of trace gases and other atmospheric parameters (Aerosols, Clouds, Radiative Transfer) from different
satellite instruments are investigated at the IUP (see also http://satellite.iup.uni-heidelberg.de).
Figure 2.34: Satellite measurement of the reflected and scattered sun light (yellow). The spectral
signatures of several atmospheric trace gases are analysed in selected spectral ranges using the DOAS
method. Displayed are the fitting results for various species analysed in the satellite group.
Overarching topic and Background For about 10 years now, a new generation of UV/vis/NIR
satellite instruments (GOME, SCIAMACHY, OMI) with moderate spectral resolution allows the
retrieval of a large variety of atmospheric trace gases. In particular, global maps of several tropospheric
trace gases like O3, BrO, NO2, CO, CH4, CO2, HCHO, SO2, H2O, O2, O4, and cloud properties can
be analysed from observations in nadir viewing mode. The most important advantage of such satellite
observations is their spatial (horizontal) coverage and resolution. The latest generation of nadir looking
UV/vis satellite instruments (e.g. OMI) achieves global coverage within one day and has a horizontal
resolution of about 13 x 24 km 2 . From such satellite observations, various individual sources like large
cities can be identified. In addition, the observation of scattered sun light in limb geometry allows to
retrieve vertical profiles of several stratospheric trace gases like O3, NO2, BrO and OClO.
Funding The group activities are funded through various national and international projects, e.g.
SCIAMACHY validation, FORMAT, STAR, Tropische Tropopause, NOXTRAM, EVERGREEN, AC-
CENT
Main methods From the measured spectra, the narowband absorption features of several trace
gases are analysed using the DOAS method (see Figure). The result of the spectral analysis represents
the trace gas absorption integrated along the absorption path. In addition, also the broad band
spectral features are analysed; they yield information in particular on the cloud cover, aerosol load and
ground albedo. Various algorithms for the analysis of satellite spectra were developed in the satellite
group within the last years. For the detailed interpretation of the analysed spectral information,
radiative transfer modelling is needed. A 3-D Monte-Carlo radiative transfer model (TRACY) was
developed in our group, which allows to simulate various complex viewing geometries and atmospheric
properties. The retrieved global data sets are further investigated using image sequence techniques.

70 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
Subprojects The various projects can be classified according to their spectral range, viewing geometry,
and analysis method.
UV/vis DOAS for Nadir viewing geometry: The main target is the determination of global maps of
tropospheric trace gas distributions like NO2, BrO, H2O, HCHO, SO2. Curently measurements of
GOME and SCIAMACHY are under investigation.
NIR DOAS for Nadir viewing geometry: The main target is the determination of global maps of
tropospheric trace gas distributions like CH4, CO2, and CO. Measurements in the near IR spectral
range are caried out only by SCIAMACHY.
Cloud retrieval for Nadir viewing geometry: The main target is the determination of global maps of
cloud cover (effective cloud fraction) from broad band spectral measurements. From the combination
with narow band absorption measurements of O4 and O2, also additional parameters like cloud top
height can be retrieved.
UV/vis DOAS for limb viewing geometry: The main target is the determination of vertical profiles of
stratospheric trace gases like O3, NO2, BrO, and OClO. Measurements in limb viewing geometry are
caried out only by SCIAMACHY.
3-D radiative transfer modelling: Detailed radiative transfer modelling is the prerequisite for the corect
interpretation of the results of the spectral analysis. The full spherical 3-dimensional Monte Carlo
model is developed and operated in our group. Also a detailed scheme for the simulation of radiative
properties of aerosols is developed.
Validation of satellite data with independent DOAS observations are caried out from several ground
based stations (Kiruna, Paramaribo, Neumayer) as well as from aircrafts and ships.
Intensive interaction and cooperation exists with various international groups, e.g. Uni Bremen, IASB
Brussels, Uni München, SRON Utrecht, KNMI Utrecht, EUMETSAT
Publications
Peer Reviewed Publications
1. Frankenberg et al. [2005a]
2. Frankenberg et al. [2005c]
3. Frankenberg et al. [2005b]
4. Heue et al. [2005]
5. Hollwedel et al. [2004]
6. Khokhar et al. [2005]
7. Kühl et al. [2004]
8. Richter et al. [2005]
9. Wagner et al. [2005a]
10. Wagner et al. [2004]
11. Wagner et al. [2005b]
Grey Publications
1. Grzegorski et al. [2004]
2. Heue et al. [2004]
3. Marbach et al. [2004]
4. ACCENT [2005]
5. Wilms-Grabe et al. [2004]

2.5. SATELLITE GROUP 71
PhD Theses
1. Beirle [2004]
2. Frankenberg [2005]
3. Heue [2005]
4. Hollwedel [2005]
5. Kühl [2005]
Diploma Theses
1. Halasia [2004]
Invited Talks
1. Wagner [2004a]
2. Wagner [2004b]
3. Wagner [2004c]
4. Wagner [2004d]
5. Wagner [2005a]
6. Wagner [2005c]
7. Wagner [2005b]

72 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.1 Quantifying NOx from lightning using satellite data
Participating scientists Steffen Beirle, Thomas Wagner, Ulrich Platt
Abstract A strong lightning event in the Gulf of Mexico was investigated. Using satellite based
measurements of NO2, combined with ground based flash counts, the direct observation of freshly
produced lightning NOx could be demonstrated, and the amount of the produced NOx has been
estimated.
Figure 2.35: Lightning event on 30 August in the Gulf of Mexico. (a) NO2 TVCD from GOME (10 15
molec/cm 2 ). (b) Time of flashes detected by NLDN
Background Nitrogen oxides (NOx=
NO+NO2) play an important role in tropospheric
chemistry, in particular in catalytic ozone production.
Lightning provides a natural source of
nitrogen oxides, dominating the production in the
tropical upper troposphere, with strong impact
on tropospheric ozone and the atmosphere’s oxidizing
capacity. Recent estimates of lightning
produced NOx (LNOx) are of the order of 5 Tg
[N] per year with still high uncertainties in the
range of one order of magnitude. The Global
Ozone Monitoring Experiment (GOME) on board
the ESA–satellite ERS–2 allows the retrieval of
tropospheric vertical column densities (TVCDs)
of NO2 on a global scale. Here we present the
GOME NO2 measurement directly over a large
convective system over the Gulf of Mexico.
Funding See satellite group overview.
Methods and results A unique event of
GOME capturing LNOx just produced is found
on 30 August 2000 over the Gulf of Mexico: A
sequence of about 14 pixels, measured at 16:47-
16:48 UTC, shows high tropospheric NO2 TCDs
(Fig. 1a) that by far exceed normal levels over
ocean.
These high TVCDs coincide with a strong convective
system causing high lightning activity.
Fig. 1b depicts the flashes detected by the U.S.
National Lightning Detection Network (NLDN)
on 30 August 2000 before the ERS–2 overpass,
while the time of the flash occurence is colorcoded.
This particular event is unprecedented as the
lightning activity coincides perfectly with the
GOME measurement both in space and in time.
The enhanced NO2 TVCDs can not be explained
with transport of anthropogenic emissions and
must be thus due to freshly produced LNOx. As
far as we know, such a clear and direct detection
of LNOx from satellite has never been reported
before.
A quantitative analysis yields a LNOx production
of 77 (27-230) moles of NOx, or 1.1 (0.4-3.2) kg
[N], per flash. If simply extrapolated, this coresponds
to a global LNOx production of 1.5 (0.5-
4.5) Tg [N]/yr.
Outlook/Future work The analysis of lightning
NOx from satellite data will be continued
with particular focus on radiative transfer in thunderstorm
clouds.
Main publication Beirle et al. [2005]

2.5. SATELLITE GROUP 73
2.5.2 Evaluation of global tropospheric NO2 from SCIAMACHY
Participating scientists Steffen Beirle, Thomas Wagner, Ulrich Platt
Abstract Spectral measurements from the satellite instrument SCIAMACHY allow to determine
tropospheric column densities of NO2 with improved spatial resolution compared to its predecessor
GOME. The time series of global measurements provide valuable information on the spatial distribution
of NOx pollution, allowing to identify and quantify the different sources of NOx.
Figure 2.36: Mean NO2 TVCD (10 15 molec/cm 2 ) from SCIAMACHY (January 2003 - June 2004).
Background Spectral measurements from
satellite platforms allow to determine slant column
densities of several trace gases, e.g. NO2,
by applying Differential Optical Absorption Spectroscopy
(DOAS). By estimating and subtracting
the stratospheric column, and accounting for
radiative transfer, tropospheric vertical column
densities (TVCDs) can be retrieved. Time series
of global NO2 TVCDs are available from the
satellite instrument GOME since 1996, but the
rather coarse spatial resolution of 320×40 km 2
leads to a smoothed image of the spatial distribution
of tropospheric NO2, often complicating
the interpretation of the measurements. Since
2002, spectral measurements with higher spatial
resolution (60×30 km 2 ) are available from the
SCanning Imaging Absorption SpectroMeter for
Atmospheric CHartographY (SCIAMACHY), resolving
several features of the spatial distribution
of tropospheric NO2.
Funding See satellite group overview.
Methods and results The DOAS fit has been
implemented for the evaluation of SCIAMACHY
data. The processing of NO2 TVCDs is analogue
to the GOME implementation.
Fig. 1 shows the resulting mean of the global
distribution of tropospheric NO2. Several hot
spots, in particular several large cities, show up
that have been smeared out in GOME data. The
accurate measurement of spatial patterns allow
the reliable identification of NOx sources and enables
us to quantify NOx emissions as well as
lifetime. Furthermore, the continuation of the
GOME time series holds information on trends
in emission strenghts, revealing a strong increase
in China.
Outlook/Future work Future improvements
in DOAS fit, stratospheric estimation, radiative
transfer modeling (in particular handling of
clouds) will lead to high quality tropospheric data
products that allow to assess several scientific
questions.
Main publication Beirle [2004]

74 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.3 Development of a radiative transfer model
Participating scientist Tim Deutschmann, Suniti Sanghavi, Thomas Wagner
Abstract A three-dimensional fully spherical Monte-Carlo model which provides realistic lightpath
information in a scattering atmosphere is being implemented. The retrieved model data plays a keyrole
in corect interpretation of spectroscopical measurements for estimation of spatially distributed tracegas
concentrations.
Figure 2.37: traced photons of λ = 411nm for a cloud layer with maximum extinction coefficient of
3.5 in 3.0km altitude. Scattering events: air molecules (rayleigh, red), aerosols (mie, green) ground
hits (isotropic, yellow), inter-voxel transitions (refraction, grey), TOA hit (turquoise).
Background When using spectroscopy for the
estimation of the amount of spatially distributed
absorbing matter in the atmosphere, the information
is needed, on which paths the photons of
the measured spectrum propagated from the light
source to the detector. The pathlengths through
certain strongly absorbing regions of the atmosphere
can susceptibly influence the observed intensity
of the detecting instrument. Radiative
transfer modelling can provide these key informations
to inverting algorithms in order to retrieve
spatially resolused tracegas concentrations.
Existing models are limited under several points
of view and cannot follow the progress in sensoring
precision. Due to that the development of a new
model is necessary and will also allow promising
reprocessing of old data.
Funding See satellite group overview.
Methods and results Based on the work of
Axel Morgner (2000) and mainly Christoph von
Friedeburg (2003), the new program is being implemented
under aspects of scalability, portability
to different os and adaptability to various
measurement geometries. The present algorithm
uses a numerical method to generate realistic light
paths in consideration of rayleigh scattering on
air molecules, mie scattering on aerosols and so
far isotropic ground scattering. The physically
relevant properties air density, pressure, temperature,
humidity, refractive index, tracegas and
aerosol concentrations and ground albedo of the
full spherical atmosphere are mapped into a 3D
grid. Using the Backward Monte Carlo technique
the simulated photons are emitted by the detector
and traced through the grid until they leave the
atmosphere (TOA, Figure 2.37). Then the generated
paths are weighted for a certain sun position,
by their possibility using a method called
“forcing”.
The flexibility of the new program allows the application
of the model data in a wide range, not
only in spectrosopy but also in atmospherical dynamics
and chemistry by regarding forward traced
photons, which is already possible.
Outlook/Future work
• more realistic mie scattering in clouds with
droplet size distribution function
• more realistic modellation of ground scattering
by using BRDF
• raman scattering and polarisation
• investigation of the energy budget for certain
conditions
• web interface for remote model data retrieval
• implementation of tomographic inversion
• parallelisation
Main publication von Friedeburg [2003]

2.5. SATELLITE GROUP 75
2.5.4 Retrieval of methane from SCIAMACHY onboard ENVISAT
Participating scientist Christian Frankenberg, Ulrich Platt, Thomas Wagner
Abstract SCIAMACHY onboard ENVISAT features three near infrared spectrometers and thereby
enables the retrieval of atmospheric methane with high sensitivity to the lowermost atmospheric layers.
Using concurent retrievals of carbon dioxide and the application of atmospheric models, precise maps
of the global distribution of column averaged methane mixing ratios are derived.
Figure 2.38: Column averaged mixing ratio of methane averaged from August through November
2003.
Background Methane (CH4) is, after carbon
dioxide, the second most important anthropogenic
greenhouse gas, contributing directly 0.48 W m −2
to the total anthropogenic radiative forcing of
2.43 W m −2 by well-mixed greenhouse gases
(IPCC, 2001). In addition, it exhibits an indirect
effect of about 0.13 W m −2 through formation
of other greenhouse gases, most notably
tropospheric ozone and stratospheric water vapor
(Lelieveld et al., 1998).
A major limitation of present top-down methane
emissions inventories is the limited number of atmospheric
observation sites. SCIAMACHY now
offers the unique possibility of sensing methane
globally, retrieving methane abundances also in
remote areas.
Funding See satellite group overview.
Methods and results An algorithm (IMAP-
DOAS) was developed based on the principles
of differential optical absorption spectroscopy
(DOAS), that deals with the peculiarities of retrieving
strong absorbers in the near infrared,
thus allowing a precise retrieval of the respective
trace gases. It was shown that nonlinear iterative
schemes are necessary to account for saturation effects
and to avoid interdependencies of spectrally
overlapping strong absorbers.
Global measurements of the total columns of
methane with high precision were made possible
by use of concurent retrievals of the relatively homogenously
distributed carbon dioxide as proxy
for the light path of the recorded photons. The
highest abundances were found over areas of rice
cultivation in South-East Asia and can be considered
a direct proof of large scale methane emissions
in Asia.
In the time-period from August through November
2003, large discrepancies between measurements
and model were discovered over tropical
rainforest areas. Measured abundances showed
persistently higher abundances than those predicted
by the model. This led to the conclusion
that the tropical regions as methane source have
been hitherto underestimated in curent emissions
inventories.
An extension of the analysis to the years 2003 and
2004 showed that the discrepancies are highest
during the months of August through October.
The precision of these measurements now allows
their use in inversion models to quantify the temporal
and geographical distribution of methane
sources.
Main publications Frankenberg et al. [2005b],
Frankenberg et al. [2005a]

76 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.5 Retrieval of carbon monoxide from SCIAMACHY onboard ENVISAT
Participating scientist Christian Frankenberg, Ulrich Platt, Thomas Wagner
Abstract SCIAMACHY onboard ENVISAT features three near infrared spectrometers and thereby
enables the retrieval of atmospheric carbon monoxide which holds interest from several perspectives.
Despite severe instrumental problems first global retrievals from SCIAMACHY have become feasible.
Figure 2.39: Maximum CO vertical column densities as seen by SCIAMACHY.
Background The global distribution of carbon
monoxide (CO) holds interest from several perspectives:
as a primary and secondary determinant
of air quality, as the leading sink of hydroxyl
radicals, and as an atmospheric tracer with
a relatively long lifetime, that is, an indicator of
how transport redistributes pollutants on a global
scale. High CO concentrations can directly affect
human health. Indirectly, CO plays a role in the
catalytic production and destruction of ozone. In
case of high NOx abundance, CO oxidation by
OH radicals leads to ozone production. Global
measurements with high sensitivity towards the
ground are thus very valuable for the quantification
of its impact on air quality and OH radical
abundances.
Funding See satellite group overview.
Methods and results The IMAP-DOAS algorithm,
which was developed at IUP Heidelberg,
was applied to account for saturation effects and
to avoid interdependencies of spectrally overlapping
strong absorbers. Further, additional spectral
calibrations for the SCIAMACHY instrument
haven been elaborated to enable the retrieval from
channel 8 spectra that are deteriorated due to an
ice-layer and low signal to noise ratio.
Since SCIAMACHY cannot be considered a dedicated
greenhouse gas mission but a prototype with
respect to near infrared spectroscopy, several instrumental
shortcomings had to be solved. An
extensive analysis of these effects enabled the retrieval
of and carbon monoxide.
In the retrievals, enhancements of carbon monoxide
in biomass-burning regions could be clearly
identified. In addition, the seasonal and geographical
patterns of typical biomass burning regions
could be observed. Only in the industrial regions
of China, high carbon monoxide abundances were
found to be persistent over the year.
Main publications Frankenberg et al. [2005c],
Frankenberg et al. [2005b]

2.5. SATELLITE GROUP 77
2.5.6 Retrieval of cloud parameters using SCIAMACHY and GOME data
Participating scientist Michael Grzegorski, Thomas Wagner, Christian Frankenberg, Mark Wenig 1 ,
Nicolas Fournier 2 , Piet Stammes 2
1 NASA Goddard Space Flight Center, Greenbelt, Maryland, USA
2 Royal Meteorological Institute of the Netherlands, KNMI, Utrecht, The Netherlands
Abstract The retrieval of cloud parameters like cloud coverage, cloud top pressure or cloud optical
thickness from satellite is an important issue both for climatology and the analysis of tropospheric
trace gases. The HICRU algorithm improves retrieval of effective cloud fraction using data from
SCIAMACHY on ENVISAT and GOME on ERS-2. HICRU also allows an accurate cloud retrieval
over deserts, which is usually difficult for cloud algorithms.
Figure 2.40: case study (08/27/2003): Results of HICRU compared with the corespondent image from
Meteosat (2 hours after ENVISAT, taken from www.eumetsat.de, c○Eumetsat)
Background The detection of cloud parameters
like cloud coverage, cloud top pressure or
cloud optical thickness from satellite is an important
issue: 1.) for meteorology and the investigation
of climate change and 2.) for the analysis of
tropospheric trace gases from space relevant to environmental
and climatological issues. Although
the retrieval of different cloud parameters is useful
for trace gas retrievals, especially the accurate
identification of completely cloud free regions is
crucial due to the shielding effect, which causes
an underestimation of the vertical column density
of tropospheric trace gases measured by satellite.
Funding See satellite group overview.
Methods and results The Heidelberg Iterative
Cloud Retrieval Utilities (HICRU) retrieve effective
cloud fraction by applying the widely used
threshold method to the so-called Polarization
Monitoring Devices (PMDs) with higher spatial
resolution compared to the channels used for trace
gas retrievals. The results are validated through
intercomparison with different other cloud algorithms.
The intercomparisons show the reliability
of the HICRU algorithm. The sophisticated
retrieval of the HICRU thresholds also allows an
accurate retrieval over deserts, which is usually
difficult for for GOME/SCIAMACHY cloud algorithms.
Cloud fraction retrieved by HICRU using
data both from SCIAMACHY and GOME is
available free of charge on http://satellite.iup.uniheidelberg.de.
Outlook/Future work The results of HICRU
will be combined with the DOAS evaluation of O 2
and O 4 and the results from the radiation transfer
model TRACY to retrieve further cloud parameters,
especially cloud top height.
Main publication Grzegorski et al. [2004]

78 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.7 Satellite validation using the airborne multi axis DOAS instrument
Participating scientists Klaus-Peter Heue, Thomas Wagner, Andreas Richter 2 , Marco Bruns 2
Ping Wang 2 ( 2 Institut für Umweltphyisk, Universität Bremen)
Abstract The Airborne Multi AXis DOAS instrument designed to separate the tropospheric from
stratospheric absorptions of several Trace gases e.g. NO2. Due to the long range of the aeroplane
it is ideal for validation measurements of tropospheric NO2 observed by the new satellite instrument
SCIAMACHY on ENVISAT.
Figure 2.41: AMAXDOAS measurements along the flight track on 19/02/2003 overlaid to SCIA-
MACHY observations from the same day. The scientific SCIAMACHY data from the IUP in Bremen
were taken.
Background With the SCIAMACHY instruments
slant and vertical columns of many trace
gases can be measured. Here we concentrate on
tropospheric NO2. Based on the observed spectra
from SCIAMACHY several scientific DOAS
products exist at different scientific groups (e.g.
in Heidelberg, Bremen, Harvard). Nitrogen dioxide
is known to be harmful and plays an important
role in the tropospheric chemistry of ozone. Most
of the tropospheric NO2 is produced by anthropogenic
emissions.
Funding See satellite group overview.
Methods and results Tropospheric NO2 vertical
and slant columns from the new satellite instrument
SCIAMACHY on ENVISAT are validated
by measurements of the AMAXDOAS instrument
on board the DLR Falcon. The results
presented here were obtained in February
2003 on a flight over the Alps, the Po-Valley and
the Mediterranean ( figure 2.41). Due to the
similar measurement system of AMAXDOAS and
SCIAMACHY both tropospheric slant and ver-
tical columns can be compared. However, the
stratospheric absorption has to be separated from
the tropospheric signal first. In the Troposphere
the local variation in the NO2 columns are very
high caused by the anthropogenic emissions. The
stratospheric signal shows rather smooth spatial
variations. Different methods for the separation
of tropospheric and stratospheric signal for both
instruments were investigated. Independent information
about aerosol optical thickness and mixing
layer height were considered for the calculation of
the AMF. The TVCD measured by AMAXDOAS
varied between 16.2 and 35.2·10 15 molec/cm 2 over
the Po-Valley where SCIAMACHY data resulted
in 19.9 to 37·10 15 molec/cm 2 . Over less polluted
areas a similarly good agreement was found. The
linear correlation between the two datasets results
in a slope of 0.93. The slight differences observed
can be attributed to the different spatial resolution
and the temporal mismatch between the measurements
over the Po-Valley.
Main publications Heue [2005], Heue et al.
[2005]

2.5. SATELLITE GROUP 79
2.5.8 Analysis of global long-term tropospheric and stratospheric BrO
from GOME measurements
Participating scientist Jens Hollwedel, Thomas Wagner, Roland von Glasow, Lars Kaleschke 2 ,
William Simpson 3 , Ulrich Platt ( 2 University of Bremen, 3 University of Alaska)
Abstract BrO leads to ozone depletion, both in the stratosphere and troposphere. The global
distribution and yearly cycle of stratospheric and tropospheric BrO has been analysed. Transport
events and an increase in tropospheric source strength have been discussed.
Figure 2.42: Global mean BrO distribution derived from GOME for the time period 1996 - 2001.
Background The importance of BrO for the
ozone depletion in the stratosphere is well known.
BrO can also be liberated by heterogenous reactions
on the surfaces of halogen rich aerosols, especially
over the one year old sea ice. This mechanism
is known as the Bromine explosion leading
to the tropospheric ozone hole in polar spring.
Funding See satellite group overview.
Methods and results Column densities of
bromine monoxide have been derived from GOME
for the time period from 1996 to 2001 on a global
scale. Two methods for the separation of the
stratospheric and tropospheric fractions of the total
column density have been used (a fixed SZA
interval and a reference site method). The average
stratospheric BrO load has increased slightly
during the time period under investigation. Investigation
of sources and source strengths of boundary
layer BrO show that enhanced boundary layer
BrO is released in bromine explosion events during
polar spring leading to tropospheric ozone holes.
The sea-ice and especially frost flowers are the
sources for these events. The area covered by
’clouds’ of enhanced BrO in the northern hemisphere
has increased by about 10% per year from
1996 to 2001. Thus the source strength has increased
which is probably due to changes in the
Arctic sea-ice cover. Strong evidence for a free
tropospheric BrO background of about 2pptv BrO
in the free troposphere with a lower boundary of
its lifetime of about four days has been gathered.
Transport events of polar tropospheric Bro towards
mid-latitudes and into the free troposphere
have been discovered.
Outlook/Future work A corelation analysis
of stratospheric BrO and NO2 will be performed
discussing the stratospheric yearly cycle of BrO.
Transport events from the polar troposphere towards
mid-latitudes and into the free troposphere
will be further investigated.
Main publication Hollwedel et al. [2004],
Hollwedel [2005]

80 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.9 Enhanced SO2 Column Densities Observed Over South East Asian
Region: Consequence of El Niño
Participating scientist M. F. Khokhar
Abstract Changes in the global atmospheric circulation patterns caused by El Niño bring about
weather extremes in various parts of the world. Especially, inhibiting rainfall over the western pacific
equatorial region, resulting in a lot of biomass burning events and droughty conditions. GOME data
showed enhanced SO2 column densities over South East Asian region which strongly corelate to the
strong El Niño event in the year 1997-98.
Figure 2.43: Comparison of monthly mean maps of fire data (ATSR fire counts /pixel), in the left
panel, GOME SO2 SCDs (centre) and HCHO SCDs (right panel) for the month of September from
1996 to 1998. The HCHO and SO2 emissions over S.E. Asia resulted from relatively enhanced Biomass
burning events as consequences of strong El Niño 1997-98 in this region. The GOME observations are
averaged on a 0.5 ◦ latitude/longitude grid.
Background The satellite remote sensing provides
information about various atmospheric trace
gas emissions and their distribution on a global
scale. Sulfur Dioxide (SO2) is an important trace
gas in the atmosphere. It is released to the troposphere
from both human activities and natural
sources (mainly from volcanic eruptions and
Biomass burning). We investigated the Biomass
burning in S. E. Asia for the time period 1996-
2001. We find an enhancement in the SO2 SCDs
for the year 1997 and 98.
Funding See satellite group overview.
Methods and results GOME is a nadirscanning
UV/Vis. spectrometer covering the
wavelength range from 240nm to 790 nm. A key
feature of GOME is its ability to detect, besides
ozone, several chemically active atmospheric trace
gases such as SO2, CH2O NO2, BrO etc. From the
ratio of earthshine radiance and solar iradiance
measurements, slant column densities (SCDs) of
the respective absorbers can be derived by applying
the technique of differential optical absorption
spectroscopy (DOAS). Satellite remote sensing is
a power full tool along with several advantages
over the conventional measurement techniques.
Especially, to monitor the volcanic eruptions and
biomass burning events resulting from forest fire
which very often occur in remote and inaccessible
area. Biomass burnings are also an important
source of tropospheric NO2 and HCHO, results
compared with SO2 column densities showed a
good agreement (see figure). Enhanced SO2 SCDs
for 1997 and 98 over S. E Asian region are coupled
to El Niño consequences. Satellites provide
the best opportunity to quantify the impact of
biomass burning on global atmospheric chemistry.
Outlook/Future work Synergistic use of
satellite observations for different trace gases e.g.
HCHO and NO2 and CO, from biomass burning
and to compare their results.
Main publication Khokhar et al. [2005]

2.5. SATELLITE GROUP 81
2.5.10 Retrieving vertical profiles of stratospheric trace gases from satellite
observations
Participating scientist Sven Kühl, Janis Pukite, Thomas Wagner, and Walburga Wilms-Grabe
Abstract Vertical profiles of ozone, NO2, BrO and OClO were retrieved from measurements of
SCIAMACHY in limb geometry. The retrieved profiles were compared to balloon measurements and
SCIAMACHY products from other institutes.
Figure 2.44: Averaging kernels for typical retrievals, revealing the altitude range for which information
on the trace gas distribution can be retrieved.
Background It is well established that the major
cause for the ozone hole, the massive depletion
of ozone in the polar lower stratosphere
in springtime, is the heterogeneous processing of
chlorine species during polar winter, the stratospheric
chlorine activation. Despite their immense
effect on the ozone layer, daily and global measurements
of active chlorine compounds like ClO
and ClOOCl are rare. On the other hand, chlorine
dioxide (OClO), an important indicator for
chlorine activation, can be measured by remote
sensing methods more easily than ClO or ClOOCl.
GOME measurements of OClO have been applied
in the long term monitoring of stratospheric chlorine
activation [Wagner et al. , 2001] as well as
in case studies [Kühl et al. , 2004; Richter et al. ,
2005]. However, the interpretation of column densities
(obtained from observations in nadir geometry)
in many cases has to remain on a qualitative
level, while the knowledge about 3-dimensional
trace gas distributions allows also quantitative
studies. Thus, the vertical profiles of ozone, NO2,
BrO and OClO, retrieved from the SCIAMACHY
limb measurements, will lead to a better understanding
of processes relevant for polar ozone loss
and can be applied for investigating contemporary
open questions of stratospheric chemistry.
Funding See satellite group overview.
Methods and results For the retrieval of the
vertical trace gas profiles a two step approach is
used: First, SCDs as function of tangent height
are determined by DOAS, then inversion to profiles
by applying the box AMFs calculated by
RTM. This two step approach enables us to study
separately the impact of spectroscopy and radiative
transfer modeling on the retrieved profile.
The retrieved profile is always a combination of
the measured SCDs, the measurement eror, the
applied AMFs, and the a priori. Therefore, the
retrieved SCDs and the calculated AMFs should
be of little uncertainty. Also, the a priori should
describe the mean value and the variance of the
state to be retrieved as good as possible. The last
point is especially important for species with a
strong annual or diurnal cycle, like e.g. OClO.
First results are in good agreement with expectations
from stratospheric chemistry, as well as
the seasonal and latitudinal dependency of the respective
trace gas abundances. Also, first comparisons
with other profile retrievals from SCIA-
MACHY limb measurements [Kühl et al. , 2005]
and with balloon borne observations [Butz et al.
, 2005] are very promising. The averaging kernels
of our NO2, BrO and OClO retrieval algorithms
(shown in 2.44) reveal that information about the
vertical profile can be obtained for NO2 in the altitude
range from 15-40 km, for BrO from 15-28
km and for OClO from 15-25 km. The vertical
resolution of the retrieved profile in this altitude
range is 3 km.
Outlook/Future work Improving the profile
retrieval in terms of spectroscopy, radiative transfer
simulation and inversion approach. Application
of the retrived profiles in scientific studies on
open questions of stratospheric chemistry.
Main publication Kühl [2005]

82 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.11 Comparison of OClO nadir measurements from SCIAMACHY and
GOME
Participating scientist Sven Kühl, Walburga Wilms-Grabe, Thomas Wagner
Abstract Total columns of OClO were retrieved from SCIAMACHY nadir observations and compared
to the longterm dataset of GOME, the predecessor of SCIAMACHY. The retrieved SCDs are
in good qualitative and quantitative agreement.
Figure 2.45: Maximum OClO SCD at SZA = 90 ◦ for the southern hemisphere derived from SCIA-
MACHY measurements during May to October 2003 and 2004 in comparison to the coresponding
minimum and maximum values derived from GOME measurements during 1996 to 2001.
Background In the polar winter, temperatures
inside the polar vortex can drop below the threshold
for formation of polar stratospheric clouds
(PSCs) which is e.g. 195 K at an altitude of approx.
19 km. Heterogeneous reactions on PSCparticles
convert the ozone-inert chlorine reservoirs
(mainly ClONO2 and HCl) into ozone destroying
species (active chlorine, mainly Cl, ClO
and ClOOCl), see e.g. Solomon [1999]. This
chlorine activation is the prerequisite for massive
ozone destruction by catalytic cycles. ClO (chlorine
monoxide) absorbs strongly at wavelengths
below 310 nm, which is in the region where also
the strong ozone absorptions of the Hartley bands
are situated. Therefore, the absorption by ClO
is masked by the much stronger O3 absorption
and unambiguous detection of stratospheric ClO
by UV-Spectroscopy was not possible so far. On
the other hand, OClO (chlorine dioxide) shows
strong differential absorption features in the spectral
range from 280 to 450 nm, and therefore can
be detected by means of DOAS.
Funding See satellite group overview.
Methods and results For the OClO DOAS
analysis of SCIAMACHY spectra we use the
wavelength range from 363 to 391 nm, the same as
for GOME. Included reference spectra are: OClO,
NO2, O3, O4, Ring, and the Eta and Zeta Spectrum
(from calbration key data) for corection of
polarisation features. From various tests it turned
out that the inclusion of the polarisation corection
spectra is essential for a corect retrieval of OClO.
Other parameters that were tested are the wavelength
range used for the analysis, the degree of
the polynomial, and the inclusion of the reciprocal
of the Fraunhofer Reference (1/I0) in the fit.
While the OClO fit converges for different wavelength
ranges, we finally chose the same fit window
as for GOME, for reason of consistency. The
OClO SCDs derived from SCIAMACHY spectra
by the DOAS method are consistent with expectations
from stratospheric chlorine chemistry.
Large OClO SCDs are observed only for regions
inside the polar vortex, their magnitude is in good
agreement with independent measurements from
GOME, see Figure.
Outlook/Future work Improvement of retrieval,
monitoring of chlorine activation, case
studies (e.g. mountain wave-induced chlorine activation).
Investigating OClO photochemistry by
combination of measurements in limb, nadir and
occultation geometry.
Main publication Kühl et al. [2005]

2.5. SATELLITE GROUP 83
2.5.12 Identification of tropospheric emissions sources from satellite observations:
Synergistic use of HCHO and NO2 trace gas measurements
Participating scientist Thiery Marbach
Abstract Many uncertainties remain in the distribution and characteristic of the tropospheric
sources of trace gases. The satellites data sets allow to compare global trace gas maps providing
unique opportunities to determine more precisely the tropospheric sources. We present case studies
for combined HCHO and NO2 satellite observations, derived from GOME measurements.
Figure 2.46: Case study of trace gas comparison: HCHO is produced from biogenic isoprenes and
during biomass burning. Yellow box: HCHO only from isoprenes. Red box: Both, isoprenes and
biomass burning. The HCHO biogenic isoprene emissions could be separated from the HCHO due to
biomass burning using the NO2-fires corelation.
Background We present case studies for the
combined GOME observations for 1997 of HCHO
SCDs and NO2 VCDs. Additional global data sets
of quantities (forest fires) measured from ATSR
have been compared to the tropospheric trace gas
columns.
Funding See satellite group overview.
Methods and results The principal biomass
burning areas (intense source of HCHO) can be
observed in the Amazon basin region and in central
Africa. Other high HCHO emissions can be
corelated with climatic events like El Nino in 1997,
which induced dry conditions in Indonesia causing
many forest fires. Tree isoprene emissions contribute
also to high HCHO concentrations especially
in southeast United States, northern part
of the Amazon basin, and in the African tropical
rain forest region. The HCHO data can be compared
with NO2 results to identify more precisely
the tropospheric sources (biomass burning events,
human activities). NO2 corelate with HCHO over
Africa (grassland fires) but not over Indonesia
(forest fires). In south America, an augmentation
of the NO2 concentrations can be observed
with the fire shift from the forest to grassland
vegetation. So there seems to be a dependence
between the NO2 emissions during biomass burning
and the vegetation type (grassland or forest),
which could influence the fire temperature (so the
NO2 production) through parameters like vegetation
density (oxidation capacity) or humidity. The
NO2-fires corelation can also be an helpful tool to
discriminate more precisely the part of the HCHO
emissions coming from the biomass burning and
the part issue from the tree isoprene emissions.
This case studie is illustrated in the figure with an
example over the Amazon basin (also illustrated
by the work of Ulrike Reichl).
Outlook/Future work The HCHO and NO2
data can also be compared with SO2 results to
identify more precisely the tropospheric sources
(biomass burning events, human activities, additional
sources like volcanoes emissions). Comparison
with CH4 and CO will also be possible
by using the SCIAMACHY data sets, and could
contribute to the identification of sources due to
biomass burning, fossil fuel combustion or agriculture.
Main publication Marbach et al. [2004], Reichl
[2005]

84 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.13 Trace gas profile retrieval from SCIAMACHY limb measurements
Participating scientist Janis Pukite, Sven Kühl, Thomas Wagner, and Walburga Wilms-Grabe
Abstract Trace gas profile retrieval of ozone, NO2, BrO and OClO is performed. This can be done
in two successive steps. First, slant column densities (SCDs) of trace gas are retrieved by DOAS from
SCIAMACHY measurements at different elevations. Second, profile is derived by inverting the SCDs.
For that purpose radiative transfer modelling is performed.
Figure 2.47: Latitudinal cross-sections of concentrations of ozone, NO2, BrO and OClO according to
an orbit on 24.08.2004.
Background The SCIAMACHY (Scanning
Imaging Absorption Spectrometer for Atmospheric
Chartography) on ENVISAT measures solar
UV-VIS-NIR radiation transmitted, backscattered
and reflected by the atmosphere and the
ground. The limb-scanning mode (tangential
view) is implemented by the instrument allowing
to perform measurements at different elevation
angles. In this way the atmosphere is probed
at different geometrical configurations that make
instrument more or less sensitive to substances located
at different altitudes in the atmosphere. To
connect the measurements with atmospheric profile
of a trace gas the radiative transfer properties
of the atmosphere should be applied.
Funding See satellite group overview.
Methods and results The retrieval of profiles
is done in two successive steps. First, SCDs for
the trace gases are derived from the SCIAMACHY
limb measurements by DOAS method. In the second
step the trace gases SCDs are converted into
vertical concentration profiles by means of radiative
transfer modelling (RTM). For the RTM the
full spherical 3D model ”Tracy”, (von Friedeburg,
2003) is used. Inversion is constrained by linear
optimal estimation method (Rodgers, 2000).
The method demonstrates possibility to retrieve
trace gas concentrations for altitudes 15 - 28 km
(BrO), 15 - 40 km (ozone and NO2), 15 - 25 km
(OClO). There are still uncertainties in retrieval
at polar regions probably caused by ozone absorption
cross-section dependence from temperature
or RTM shortages. Retrieved profiles of NO2 and
BrO show good agreement with retrieval done by
IUP Bremen and with balloon measurements for
NO2.
Outlook/Future work An improvement is
necessary especially for measurements made at solar
zenith angles ≥ 90 ◦ as well as for retrieval
of BrO and OClO. Model studies should be performed.
Improvement in RTM is required.
Main publication Pukite et al. [2005], Butz
et al. [2005]

2.5. SATELLITE GROUP 85
2.5.14 Mie theory based characterization and modeling of atmospheric
aerosols
Participating scientist Suniti Sanghavi
Abstract We have developed a Mie model to generate the single scattering properties of a particle
given its size and complex refractive index. We put up a set of 24 aerosol scenarios to represent most
aerosols in the atmosphere. The Mie theory can be used to simulate these scenarios and thus examine
the optical behavior of most atmospheric aerosols.
Figure 2.48: Phase functions of different aerosol particles
Background Aerosols have gained increasing
importance in atmospheric sciences due to the
key role they play in regard to, amongst others,
the earth’s radiative budget, convective processes
and precipitation, and stratospheric chemistry
leading, eg., to the formation of the ozone
hole. They remain, however, difficult to quantify
due to their varied sources, lifetimes and transport
mechanisms. Thus they may occur over land or
water surfaces and at different heights in the atmosphere.
They also display inherent variations
in size, shape and chemical composition, leading
to different optical properties. We classify aerosols
to represent most situations found in the atmosphere
and characterize their optical properties
using the Mie theory. This can be used to simulate
the radiative properties of aerosols occuring in nature.
We intend to use the TRACY MC RTM for
this purpose. This should especially help quantify
the radiative effects of aerosols on the retrieval of
trace gas species from the satellite DOAS instrument
SCIAMACHY. Work is ongoing for other
applications that may include, in conjunction with
aerosol climatologies now available at sites such
as AERONET, aerosol inversion products from
SCIAMACHY radiances.
Funding See satellite group overview.
Methods and results We have adapted a compilation
of 24 distinct aerosol scenarios, consisting
of 5 main aerosol types, viz. urban industrial,
biomass burning, desert dust, marine and
volcanic, each associated with a typical complex
refractive index and vertical profile. Each is further
subclassified according to coarseness, absorptivity,
nonsphericity or height of occurence in the
atmosphere(km a.s.l.).
We obtain the optical properties, viz. extinction
cross section, single scattering albedo and phase
function of an aerosol particle of given size and
complex refractive index, using the Mie theory
(See figure). The Mie theory is a special case
of the Maxwell equations with boundary conditions
given by the interaction of electromagnetic
radiation of given wavelength at the surface of a
spherical particle.
Using the characteristic complex refractive indices,
size distributions and vertical profiles provided
by the the scenarios mentioned above, we
can use the Mie theory to determine bulk properties,
e.g. the Aerosol Optical Thickness (AOT)
at a given location. Adding surface reflection,
Rayleigh scattering, and molecular absorption allows
us to simulate fluctuations in radiances measured
by satellite due to variations in the aerosol
loading of the atmosphere.
Outlook/Future work Implementing aerosols
in TRACY RTM (Quantification of the effect
of aerosols on SCDs/AMFs in different spectral
regions), Aerosol retrieval/inversion from satellite/ground
based measurements.
Main publication Sanghavi [2003]

86 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.15 Satellite observations of the global water vapor distribution
Participating scientist Thomas Wagner, Steffen Beirle, Michael Grzegorski
Abstract From modern UV/vis satellite instruments, the integrated water vapor concentration
(often refered to as vertical column density or total column precipitable water) can be observed on
a global scale. In contrast to previous satellite observations in the infrared and microwave spectral
range our observations include both ocean and land surfaces with similar sensitivity.
Figure 2.49: Global anomalies of the water vapor distribution during the strong ENSO event in
1997/98.
Background Atmospheric water vapor is the
most important greenhouse gas contributing
about 2/3 of the natural greenhouse effect. In
contrast to other greenhouse gases like CO2 and
CH4 it has a much higher temporal and spatial
variability. The corect understanding and assessment
of atmospheric water vapor with respect to
the Earths energy budget is further complicated
by its role in cloud formation and transport of
latent heat. Today, many details of how the hydrological
cycle reacts to climate change (water
vapor feedback) are still not understood. Especially
for the tropics, which contribute strongest
to the water vapor greenhouse effect, the strength
of the water vapor feedback is under intense debate.
In our studies we investigate the dependence
of the global distribution of water vapor on surface
temperature. Particular studies focussed on
the response to the strong ENSO in 1997/98 and
on the trends from 1996-2003.
Funding See satellite group overview.
Methods and results The GOME instrument
is one of several instruments aboard the European
research satellite ERS-2. It consists of a set of four
spectrometers that simultaneously measure sunlight
reflected from the Earth’s atmosphere and
ground in total of 4096 spectral channels covering
the wavelength range between 240 and 790 nm
with moderate spectral resolutions. The satellite
operates in a nearly polar, sun-synchronous orbit
at an altitude of 780 km with an equator crossing
time at approximately 10:30 local time. The
Earth’s surface is totally covered within 3 days,
and poleward from about 70 latitude within 1 day.
Our water vapor algorithm is based on Differential
Optical Absorption Spectroscopy (DOAS)
performed in the wavelength interval 611-673 nm.
It consists of three basic steps (described in detail
in Wagner et al. [2003]): in the first step, the spectral
DOAS fitting is caried out, taking into consideration
cross sections of O2 and O4 in addition
to that of water vapor. From the DOAS analysis,
the water vapor slant column density (the
concentration integrated along the light path) is
derived. In the second step, the water vapor slant
column density is corected for the non-linearity
arising from the fact that the fine structure water
vapor absorption lines are not spectrally resolved
by the GOME instrument. In the last step, the
corected water vapor slant column density is divided
by a ’measured’ air mass factor which is
derived from the simultaneously retrieved O4 or
O2 absorptions [Wagner et al., 2003, 2005b,b].
Outlook/Future work The work will be continued
by applying the method to new satellite
instruments like SCIAMACHY and the GOME-
2-series. It can be expected that the time series
can be continued until 2020.
Main publication Wagner et al. [2003], Wagner
et al. [2005a], Wagner et al. [2005b]

2.5. SATELLITE GROUP 87
2.5.16 Analysis of MAXDOAS observations in various observing geometries
Participating scientist Thomas Wagner, Nicole Bobrowski, Barbara Dix, Erna Frins, Ossama
Ibrahim, Roman Sinreich
Abstract MAX-DOAS measurements were caried out at various locations including ship borne
measurements. Sophisticated analysis strategies were developed which can yield vertical profiles not
only of the trace gases of interest, but also of aerosol properties. In addition, a new tomographic
MAX-DOAS technique was developed which allows to determined three-dimensional trace gas fields.
Figure 2.50: General dependence of the measured O4 absorption on various parameters of MAXDOAS
observations. From MAXDOAS O4 measurements, the atmospheric aerosol properties can be derived
(Wagner et al., 2004)
Background The Multi AXis Differential Optical
Absorption Spectroscopy (MAX-DOAS) technique
allows to separate the absorptions taken
place at different altitudes in the atmosphere by
observing scattered sun light from a variety of
viewing directions. This is possible because for
most measurement conditions, the observed light
is scattered in the free troposphere. Thus air
masses located close to the ground are traversed
on a slant absorption path determined by the
viewing direction; in contrast, stratospheric air
masses are traversed on a slant absorption path
determined by solar zenith angle. In addition to
the partial columns of various trace gases (like
NO2, BrO, HCHO, etc.) also information on the
aerosol profile can be retrieved (see figure).
Funding See satellite group overview.
Methods and results MAX-DOAS observations
were caried out during coordinated compar-
ison campaigns at Milano (September 2003) and
Cabauw (July 2005). In addition, permanent instruments
are installed at Paramaribo (Suriname)
since 2002. MAXDOAS observations were also
caried out during several cruises of the German research
vessel Polarstern. Thes observations were
used for the validation of the SCIAMACHY instrument
on board of the European research satellite
ENVISAT. In addition to the classical MAX-
DOAS geometry, also MAX-DOAS observations
of sun-illuminated targets were proposed (Frins
et al., 2005). Thus measurements over well defined
light paths are possible which will allow tomographic
inversion of horizontal gradients.
Outlook/Future work The full potential of
the various MAXDOAS geometries will be further
examined. Inversion schemes for trace gas
and aerosol profiles will be optimised.
Main publication Wagner et al. [2004]

88 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.17 Comparison of Radiative Transfer Models
Participating scientist Thomas Wagner, Barbara Dix, Tim Deutschmann, Klaus-Peter Heue,
Suniti Sanghavi
Abstract For the interpretation of UV/vis remote sensing observations from different platforms
(ground, aircraft, satellite) the atmospheric radiative transfer has to be numerically modeled. In June
2005 a workshop was held at Heidelberg in order to compare the various models developed in different
international research groups.
Figure 2.51: MAXDOAS Box AMF for an elevation angle of 3 ◦ (360nm, no aerosol).
Background During recent years the requirements
on numerical models for the simulation of
the atmospheric radiative transfer have been substantially
increased. This is first, because complex
measurement geometries have evolved, like
e.g. Multi-Axis-(MAX-) DOAS observations or
satellite observations over a large ground pixel.
Since on the other hand, computer power has
also largely increased, today’s radiative transfer
models often include three dimensions and
can describe complex geometries. The Heidelberg
radiative transfer workshop compared Boxair
mass factors (AMF) and normalised radiances
for MAXDOAS geometries for various aerosol scenarios.
Funding See satellite group overview.
Methods and results The Heidelberg RTM
workshop focused on the comparison of the results
of curent RTM for DOAS observations of
scattered radiation. The main focus was the modeling
of various MAXDOAS geometries. Accurate
modeling of MAXDOAS observations is important
for satellite observations because of two
main reasons: first, from the radiative transfer
modeling of the rather complex MAXDOAS geometries,
important and detailed conclusions on
the quality of the different models can be drawn.
These conclusions can be directly applied to the
various satellite viewing geometries. Second, accurate
atmospheric trace gas products are very
important for the validation of satellite measurements,
especially for tropospheric trace gases. Besides
the normalise radiances, also Box-AMF for
various altitudes were compared (see Figure). In
general, good agreement was found. However, also
discrepancies were detected, some of which could
be related to the treatment of sphericity. More
details on the selected comparison exercises and
results can be found at http://satellite.iup.uniheidelberg.de/.
Outlook/Future work Further improvements
of the various model results is foreseen for the near
future. Additional exercises were already selected
to investigate specific dependencies like the influence
of the aerosol phase function and the ground
albedo. It is planned to publish the results.
Main publication ACCENT [2005]

2.5. SATELLITE GROUP 89
2.5.18 GOME observations of stratospheric trace gas distributions during
the split vortex event in the Antarctic winter 2002
Participating scientists: Walburga Wilms-Grabe, Steffen Beirle, Sven Kühl, Ulrich Platt, and
Thomas Wagner
Abstract In the austral winter/spring 2002, an unusual major stratospheric warming led to an early
split of the south polar vortex, combined with a partly filling up of the Antarctic ozone hole. This
study is dealing with distributions of ozone related trace gases (O3, NO2 and OClO) measured by
GOME during the split vortex event.
GOME O 3, 2002/09/27
500 >
DU
450
400
350
300
250
200
150
100
ESA / DLR / IUP Bremen eichmann@iup.physik.uni-bremen.de <
Figure 2.52: O3, NO2 and OClO-distributions above the south pole at 27 Sep. 2002, measured by
GOME, retrievals of IUP Bremen (O3) and IUP Heidelberg (NO2, OClO).
Background Unusual high activity of planetary
waves in the southern hemisphere led to the
early weakening and splitting of the south polar
vortex in winter/spring 2002 and strongly affected
also chemical conditions in the Antarctic atmosphere.
This could be clearly seen from the premature
break up of the ozone hole in the last third
of September [Richter et al., 2005]. The stratospheric
ozone chemistry is related to the nitrogen
and to the halogene chemistry. Therefore, it
is of interest to investigate the evolution of O3,
NO2 and OClO during this abnormal situation,
whereas OClO serves as indicator for the degree
of stratospheric chlorine activation.
Funding See satellite group overview.
Methods and results The stratospheric ozone
chemistry is closely connected to shape and
strength of the vortex. Therefore, the polar
ozone distribution reproduces precisely the actual
state of the vortex. The break up starts at Sep.
21st/22nd. Simultaneously with the weakening of
the ozone hole NO2 is increasing inside the vortex.
At 26/27 Sep. NO2 shows unusual high
SCDs above the pole, although the ozone concentration
is still relatively low in the same area
(see figure). As well dynamical as chemical processes
can be responsible for the increased NO2
concentrations. One important aspect is the vertical
misalignment and realignment of the vortex
during the weakening period. Also thermal decay
and rapid photolysis of NO2 reservoirs of warm
mid-latitude air transported to polar regions may
contribute to the NO2-enrichment. OClO evinces
high chlorine activation inside the vortex at 20
Sep. and is rapidly decreasing after 22 Sep. At 27
Sep. GOME does not find OClO any more (figure).
Even after the re-establishing of one vortex
fragment by mid October over the pole no OClO
was observed. The rapidity of the OClO reduction
in the austral spring 2002 is anomalous. In
contrary to the north pole where high yearly variability
of OClO is typical, the chlorine activation
above the south pole varies only slightly from year
to year. In the year 2002 however the decrease of
OClO starts about 10 days earlier as usual and
continues for approximately 7 days only.
Outlook/Future work Including measurements
of polar stratospheric clouds (e.g. from
ENVISAT-MIPAS) and limb observations of different
trace gases by SCIAMACHY during the
split vortex event can provide new insights in the
chemical and dynamical interactions also with vertically
resolved information.
Main publication Wilms-Grabe et al. [2004],
Richter et al. [2005]

90 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.5.19 Comparison of GOME NO2 retrievals analysed by different scientific
groups
Participating scientists: Walburga Wilms-Grabe, Steffen Beirle, Randall Martin, Andreas Richter,
Michel van Roozendael, and Thomas Wagner
Abstract In order to improve nonuniform GOME NO2 products of differing analysis tools applied
at several institutes, NO2 SCDs have been compared for selected GOME orbits. The results show
principal agreement between retrievals of IASB in Brussels, IUP Bremen and IUP Heidelberg, but in
some extent clear discrepancies to retrievals of Dalhousie University in Halifax.
Figure 2.53: NO2 SCDs of one GOME orbit crossing north-east of the United States and the Pacific,
analysed for 03 February 1996 (left) and 06 February 2000 (right) by Heidelberg (blue), Bremen
(black), Brussels (green) and Halifax (red)
Background Several scientific groups are occupied
with the analysis of GOME trace gas measurements.
In dependence of the used retrieval
tools, the resulting trace gas distributions differ
from each other, though they were analyzed for
the same location and time. Therefore, a comparison
study is performed in order to assess the
discrepancies and to evaluate the reliability of
GOME products. The study is concentrated on
NO2, an important trace gas for both the troposphere
and stratosphere. The assessment of NO2
retrievals can help all GOME data users to choose
the most appropriate data set and particularly
helps the provider of evaluated GOME data to
unify the different existing analyzing algorithms.
Funding See satellite group overview.
Methods and results For the whole GOME
measurement period, two GOME orbits per year
have been selected as case studies: one orbit in
the winter time (February) and one in the summer
time (July). The chosen orbits are all located
above nearly the same region, including high polluted
areas in north-east of the United States and
clean areas above the Pacific. This choice allows
to compare NO2 retrievals for the complete orbit,
but also to consider separately polluted and
non-polluted parts of the orbit. In order to obtain
really basic information about reasons for the
variability of GOME NO2 products, in a first step
pure SCDs were compared.
The figure shows two examples of several NO2 retrievals.
The principal agreement of all participating
groups is existing. However, all selected
orbits indicate better agreement between the NO2
distributions of Bremen, Brussels and Heidelberg
and more obvious deviations in the NO2 results
of Halifax. The deviations of Halifax are related
as well to the absolute SCD values (positive offset)
as to the scattering of the data. In the figure,
the differing scatter patterns of Halifax can
be seen clearly in the region between −50 ◦ and
−10 ◦ latitude. Correlations between NO2 results
of Bremen, Brussels and Heidelberg lie around
0.97 and 0.99 in both polluted and unpolluted regions.
Correlations between data of one of these
groups and data of Halifax are around 0.97 in
polluted areas and about 0.55 in the less NO2enriched
region between −50 ◦ and −10 ◦ latitude.
Outlook/Future work Level 2 data of the
DLR have to be included in the comparison study.
Also VCDs and air mass factors have to be considered,
the number of selected orbits has to be
extended.
Main publication Publication is planned later
on in an advanced stage of the comparison study.

2.5. SATELLITE GROUP 91
References
ACCENT. 2005. Workshop on Radiative Transfer Modeling, Heidelberg.
Beirle, S. 2004. Estimating source strengths and lifetime of Nitrogen Oxides from satellite data. Ph.D.
thesis, Institut für Umweltphysik, Universität Heidelberg, Germany.
Beirle, S., Spichtinger, N., Stohl, A., Cummins, K. L., Turner, T., Boccippio, D., Cooper, O. R.,
Wenig, M., Grzegorski, M., Platt, U., & Wagner, T. 2005. Estimating the NOx produced by
lightning from GOME and NLDN data: A case study in the (Gulf) of (Mexico). Atmos. Chem.
Phys. Disc., 5, 11295 – 11329.
Butz, A., Bösch, H., Camy-Peyret, C., Chipperfield, M., Dorf, M., Dufour, G., Grunow, K., Jeseck,
P., Kühl, S., Payan, S., Pepin, I., Pukite, J., Rozanov, A., von Savigny, C., Sioris, C., Wagner, T.,
Weidner, F., & Pfeilsticker, K. 2005. Inter-comparison of Stratospheric O3 and NO2 Abundances
Retrieved from Balloon Borne Direct Sun Observations and Envisat/SCIAMACHY Limb Measurements.
Atmos. Chem. Phys. Discuss., 5, 10747 – 10797. SRef-ID:1680-7375/acpd/2005-5-10747.
Frankenberg, C. 2005. Retrieval of Methane and Carbon Monoxide using near infrared spectra recorded
by SCIAMACHY onboard ENVISAT - Algorithm development and data analysis. Ph.D. thesis,
Institut für Umweltphysik, Universität Heidelberg, Germany.
Frankenberg, C., Meirink, J. F., van Weele, M., Platt, U., & Wagner, T. 2005a. Assessing Methane
Emissions from Global Space-Borne Observations. Science, 308(5724), 1010–1014.
Frankenberg, C., Platt, U., & Wagner, T. 2005b. Iterative maximum a posteriori (IMAP)-DOAS for
retrieval of strongly absorbing trace gases: Model studies for CH4 and CO2 retrieval from near
infrared spectra of SCIAMACHY onboard ENVISAT. Atmos. Chem. Phys., 5, 9–22.
Frankenberg, C., Platt, U., & Wagner, T. 2005c. Retrieval of CO from SCIAMACHY onboard
ENVISAT: detection of strongly polluted areas and seasonal patterns in global CO abundances.
Atmos. Chem. Phys., 5, 1639–1644.
Grzegorski, M., Frankenberg, C., Platt, U., Wenig, M., Fournier, N., Stammes, P., & Wagner, T. 2004.
Determination of cloud parameters from SCIAMACHY data for the correction of tropospheric trace
gases. In: Proceedings of the ENVISAT & ERS Symposium, 6-10 September 2004, Salzburg, Austria.
ESA-publication SP-572, (CD-ROM).
Halasia, M.-A. 2004. SMAX-DOAS observation of atmospheric trace gases on the Polarstern
ANT/XX-expedition from October 2002 until February 2003. Diplomarbeit, Institut für Umweltphysik,
Universität Heidelberg.
Heue, K.-P. 2005. Airborne multi axis DOAS instrument and measurements of two dimensional
tropospheric trace gas distributions. Ph.D. thesis, Institut für Umweltphysik, Universität Heidelberg,
Germany.
Heue, K.-P., Beirle, S., Bruns, M., Burrows, J. P., Platt, U., Pundt, I., Richter, A., Wagner, T., &
P. Wang, P. 2004. SCIAMACHY validation using the AMAXDOAS instrument. In: Proceedings
of the ENVISAT & ERS Symposium, 6-10 September 2004, Salzburg, Austria. ESA-publication
SP-572 (CD-ROM).
Heue, K.-P., Richter, A., Bruns, M., Burrows, J. P., v.Friedeburg, C., Platt, U., Pundt, I., Wang,
P., & Wagner, T. 2005. Validation of SCIAMACHY tropospheric NO2-columns with AMAXDOAS
measurements. Atmos. Chem. Phys., 5, 1039–1051.
Hollwedel, J. 2005. Observations of tropospheric and stratospheric Bromine Monoxide from satellite.
Ph.D. thesis, Institut für Umweltphysik, Universität Heidelberg, Germany.
Hollwedel, J., Wenig, M., Beirle, S., Kraus, S., Kühl, S., Wilms-Grabe, W., Platt, U., & Wagner, T.
2004. Year-to-Year Variations of Spring Time Polar Tropospheric BrO as seen by GOME. Adv.
Space Res., 34, 804–808. doi:10.1016/j.asr.2003.08.060.
Khokhar, M.F., Frankenberg, C., Roozendael, M. Van, Beirle, S., Kühl, S., Richter, A., Platt, U.,
& Wagner, T. 2005. Satellite observations of atmospheric SO2 from volcanic eruptions during the
time period of 1996 to 2002. Adv. Space Res., 36, 879–887. doi:10.1016/j.asr.2005.04.114.

92 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
Kühl, S. 2005. Quantifying stratospheric chlorine chemistry by the satellite spectrometers GOME and
SCIAMACHY. Ph.D. thesis, Institut für Umweltphysik, Universität Heidelberg, Germany.
Kühl, S., Dörnbrack, A., Sinnhuber, B.-M., Wilms-Grabe, W., Platt, U., & Wagner, T. 2004. Observational
evidence of rapid chlorine activation by mountain waves above Northern Scandinavia. J.
Geophys. Res., 109. doi:10.1029/2004JD004797.
Kühl, S., Wilms-Grabe, W., Frankenberg, C., Grzegorski, M., Platt, U., & Wagner, T. 2005. Comparison
of OClO Nadir measurements from SCIAMACHY and GOME. J. Adv. Space Res. in
press.
Marbach, T., Beirle, S., Hollwedel, J., Platt, U., & Wagner, T. 2004. Identification of tropospheric
emission sources from satellite observations: Synergistic use of trace gas measurements of formaldehyde
(HCHO), and nitrogen dioxide (NO2). In: Proceedings of the ENVISAT & ERS Symposium,
6-10 September 2004, Salzburg, Austria. ESA publication SP-572, (CD-ROM).
Pukite, J., Kühl, S., Wilms-Grabe, W., von Friedeburg, C., Deutschmann, T., Sanghavi, S., Hollwedel,
J., Beirle, S., Frankenberg, C., Khokhar, M. F., Grzegorski, M., Marbach, T., Kirchof, B., Kraus, S.,
Platt, U., & Wagner, T. 2005. SCIAMACHYLimb Measurements as a New Tool for Stratospheric
Ozone Studies. Proceedings of the int. conference ”Integrative Approaches Towards Sustainability
”Sharing””, May 11 - 14, 2005. in Jurmala, Latvia. in press.
Reichl, U. 2005. Ground based spectroscopic direct Sun measurements at Timon/Northeast Brazil:
Comparison of tropospheric air mass pollution during the dry and rainy season. M.Phil. thesis,
University of Heidelberg, Heidelberg, Germany.
Richter, A., Wittrock, F., Weber., M., Beirle, S., Kühl, S., Platt, U., Wagner, T., Wilms-Grabe, W., &
Burrows, J.P. 2005. GOME observations of stratospheric trace gas distributions during the splitting
vortex event in the Antarctic winter 2002 Part I: Measurements. J. Atmos. Sci., 62, 778 – 785.
Sanghavi, S. 2003. An efficient Implementation of the Mie Theory to investigate the influence of
Aerosols on Radiative Transfer. M.Phil. thesis, University of Heidelberg, Heidelberg, Germany.
Solomon, S. 1999. Stratospheric ozone depletion: A review of concepts and History. Rev. Geophys.,
37(3), 275 – 316.
von Friedeburg, C. 2003. Derivation of Trace Gas Information combining Differential Optical Absorption
Spectroscopy with Radiative Transfer Modelling. Ph.D. thesis, Institut für Umweltphysik,
Universität Heidelberg, Germany.
Wagner, T. 2004a. Current status and future perspectives of atmospheric trace gas observations from
space. Invited talk, Institute Colloquium, MPI Mainz, Germany.
Wagner, T. 2004b. Global monitoring of atmospheric trace gases, clouds and aerosols from
UV/vis/NIR satellite instruments: Currents status and near future perspectives. Invited talk, SO-
LAS Science conference, Halifax, Canada.
Wagner, T. 2004c. Global monitoring of atmospheric trace gases, clouds and aerosols from
UV/vis/NIR satellite instruments: Currents status and near future perspectives. Invited talk,
WMO/GAW Expert Workshop, Tutzing, Germany.
Wagner, T. 2004d. Moderne Methoden der Satellitenbildverarbeitung: Spektroskopie, Reflektions-,
Streu-, und Absorptionsprozesse. Invited talk, WMO/GAW Expert Workshop, Tutzing, Germany.
Wagner, T. 2005a. 7.5-year global trends in GOME cloud cover and humidity - a signal of climate
change? Invited talk, KNMI, Utrecht, The Netherlands.
Wagner, T. 2005b. Troposphärische Spurengasmessungen vom Satelliten aus. Invited talk,
DECHEMA, Frankfurt, Germany.
Wagner, T. 2005c. Wasserdampf-Fernerkundung mit dem ERS-2/GOME Sensor und seinen Nachfolgern.
Invited talk, DWD, Offenbach, Germany.
Wagner, T., Leue, C., Pfeilsticker, K., & Platt, U. 2001. Monitoring of the stratospheric chlorine
activation by Global Ozone Monitoring Experiment GOME OClO measurements in the austral and
boreal winters 1995 through 1999. J. Geophys. Res., 106, 4971–4986.

2.5. SATELLITE GROUP 93
Wagner, T., Heland, J., M., Zöger, & U., Platt. 2003. A fast H2O total column density product from
GOME - validation with in-situ aircraft measurements. Atmos. Chem. Phys., 3, 651 – 663.
Wagner, T., Dix, B., von Friedeburg, C., Frieß, U., Sanghavi, S., Sinreich, R., & Platt, U. 2004.
MAX-DOAS O4 measurements - a new technique to derive information on atmospheric aerosols:
(I) Principles and information content. J. Geophys. Res., 109(D22205).
Wagner, T., Beirle, S., Grzegorski, M., Sanghavi, S., & U., Platt. 2005a. El-Niño induced anomalies
in global data sets of water vapour and cloud cover derived from GOME on ERS-2. J. Geophys.
Res., 110(D15104).
Wagner, T., Beirle, S., Grzegorski, M., & Platt, U. 2005b. Global trends (1996 to 2003) of total
column precipitable water observed by GOME on ERS-2 and their relation to surface temperature.
J. Geophys. Res. (accepted).
Wilms-Grabe, W., Kühl, S., Beirle, S., Platt, U., & Wagner, T. 2004. GOME observations of stratospheric
trace gas distributions during the split vortex event in the Antarctic winter 2002. Pages
1053–1054 of: Proceedings Quadrennial Ozone Symposium, 1-8 June 2004, Kos, Greece.

2.6. MARHAL - MODELING OF MARINE AND HALOGEN CHEMISTRY 95
2.6 MarHal - Modeling of marine and halogen chemistry
MarHal is an independent Junior Research Group that is funded by the Deutsche Forschungsgemeinschaft
in the Emmy-Noether program. The main research foci of our group are the investigation
of photochemical and microphysical processes in the troposphere, especially in the marine boundary
layer using numerical models.
Group members
Dr. Roland von Glasow, head of group
Dr. Susanne Pechtl (b. Marquart), PostDoc
Matthias Piot, DEA in oceanography and meteorology, PhD student
Dipl. Met. Linda Smoydzin, PhD student
Figure 2.54: Overview of the research topics of MarHal.
Research field Seventy percent of the Earth’s surface is covered by oceans. Particles and gases are
released from the ocean and have an influence on atmospheric chemistry and climate via changes of
the oxidation power of the atmosphere. Furthermore, feedbacks between chemistry and, for example,
cloud microphysical properties occur, that change the albedo and therefore alter the energy budget
of the Earth (e.g. sulfate and sea salt aerosol particles and their role as cloud condensation nuclei).
Measurements in the marine troposphere and in seawater have shown that exchanges of climatically
relevant gases like dimethyl sulfide (DMS) and non-methane hydrocarbons occur which can have a
significant impact on regional and even global photochemistry and climate. Furthermore, sea salt
aerosol particles are produced that contain chlorine and bromine. Numerous aerosol samples have
shown that marine aerosol is depleted in bromine compared to sea water. Once released to the gas
phase bromine participates in ozone destruction cycles and also oxidizes dimethyl sulfide (DMS).
Iodine is being released via biological processes in dramatic amounts from several coastal regions but
also from the open ocean. Iodine is very efficient in destroying ozone and if concentrations of iodine
oxides are high enough, new particle formation can occur.
The role of halogens in tropospheric chemistry is not restricted to the marine environment. Very
high mixing ratios of the radical bromine oxide have been measured during strong surface Ozone
Depletion Events in polar regions in springtime and over saltlakes. In the Arctic BrO has also been
implicated in so-called Mercury Depletion Events with an increase in the deposition of bioavailable,
toxic mercury. Various measurements indicate that there is a significant background of the bromine

96 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
oxide radical in the troposphere, most likely in the free troposphere, which would significantly impact
the background photochemistry in this sensitive environment (see 2.6.4).
Although the mentioned domains appear to be very different they have striking similarities when
halogen release and cycling are considered. This makes it feasible to address the associated research
questions in one research group to benefit from synergies. Figure 2.54 shows schematically our research
topics, making the interconnections more obvious.
Methods Our research tools are numerical models. The main model is the one-dimensional model
of the marine boundary layer MISTRA [von Glasow et al. , 2002a,b; von Glasow & Crutzen, 2004]
that treats chemical processes in the gas phase, in and on aerosol particles, and cloud droplets. The
microphysical module includes the growth of particles due to water vapor and uptake of other gases
and a two-way feedback with radiation. Aqueous phase chemistry is calculated in sulfate and sea salt
aerosol and - if a cloud is present - in cloud droplets that grew on each type of aerosol. The chemical
mechanism comprises about 170 reactions in the gas phase and 270 reactions in and on aqueous
particles for each of the four chemical bins. For some applications the model is run in Lagrangian box
model mode where the relevant meteorological parameters (temperature, relative humidity, particle
radius and liquid water content) are adjusted to the problem under investigation.
We are developing an improved microphysical/microchemical module that will allow us to make
more detailed studies of the microphysical (mainly growth) and chemical interactions of a particle
population.
Furthermore we have been using the global three-dimensional model MATCH-MPIC [Lawrence
et al. , 1999; von Kuhlmann et al. , 2003] that uses meteorological data from numerical weather
forecast reanalyses and allows to adjust the chemical mechanisms for the question in mind.
Main activities All group members actively take part in model development and application.
Polar halogen chemistry is being investigated by Matthias Piot (see 2.6.2) focusing on the effects
of various chemical and meteorological parameters for the development of ozone depletion events.
The effects of esp. organic surfactants on sea salt aerosol on particle growth and chemical processes
like uptake or scavenging of gas phase compounds is the subject of Linda Smoydzin (see 2.6.3).
Susanne Pechtl (b. Marquart) has developed and applied a parameterization for the nucleation of
new aerosol particle from iodine vapors (see 2.6.1, Pechtl et al. [2005]). Data from a field campaign
in Brittany (see C. Peters, Peters et al. [2005]) has been analysed with our model MISTRA. Together
with Roland von Glasow she participated in a field campaign off the coast of New England on Appledore
Island to collect data for the ongoing comparison and interpretation with numerical models.
Currently, we are making comparisons focusing on iodine and chlorine chemistry and the effects on
ozone and new particle formation (together with J. Stutz and O. Pikelnaya, Univ. of California, Los
Angeles, W. Keene, Univ. Virginia, A. Pszenny, Univ. New Hampshire and other participants of the
Appledore campaign). She is also developing the core routines of the new microphysical/microchemical
model.
The first global assessment of bromine chemistry in the free troposphere has been made by von
Glasow et al. [2004] (see 2.6.4), showing that potentially very large sinks for ozone and DMS have
been observed in previous studies. First comparisons with measurements are being made to help chose
which model scenario fits best in the southern hemisphere (Schofield et al., in prep.).
Effects of surface reactions on sea salt aerosol had been proposed in the literature to be of potentially
great importance for the marine sulfur cycle, model results of Roland von Glasow showed,
however, that the effects had been overestimated and are unlikely to be of importance (von Glasow
2005, in prep.).
A volcanic plume version of MISTRA was developed by Roland von Glasow and compared with
measurements at Mt. Etna (see Bobrowski). With the help of Alessandro Aiuppa (Univ. of Palermo,
Italy) several potential sets of initial plume conditions have been evaluated, showing that measurements
of BrO and SO2 columns can very easily be reproduced by the model encouraging us to use
the model to interpret the plume chemistry in this regard. The column densities of chlorine oxides,
however, could not be reproduced satisfactorily, we did manage to reduce the mismatch from four
orders of magnitude to a still very large factor of 30 (Bobrowski et al., submitted, von Glasow, in
prep.).
Colleagues from the National Institute for Water and Atmospheric Research (NIWA) in Wellington,
New Zealand, initiated a collaboration to investigate if observed seasonal variations in the δ 13 C concentrations
as measured at their baseline station at Baring Head can be explained by known chlorine
chemistry. Roland von Glasow has visited their group twice, the final model runs and a publication
are in preparation.

2.6. MARHAL - MODELING OF MARINE AND HALOGEN CHEMISTRY 97
Collaboration with the satellite group at the IUP include work of the detection of ship tracks in
NO2 retrievals from GOME (Beirle et al. [2004]) and the spill-out of BrO from polar ODEs (Hollwedel
et al., in prep., section 2.5.8).
Collaborations
Alfred-Wegener-Institut, Bremerhaven
Cape Grim Baseline Air Pollution Station, Tasmanien, Australia
Dipartimento CFTA, Università di Palermo, Italy
Forschungszentrum Karlsruhe
Max-Planck-Institut für Chemie, Mainz (MPI-C)
National Institute of Water and Atmospheric Research (NIWA), New Zealand
National Oceanic and Atmospheric Administration, NOAA, Boulder, USA
Scripps Inst. of Ocanography, University of California, San Diego (SIO), USA
Universität Bremen
University of California, Los Angeles (UCLA), USA
University of New Hampshire, USA
University of Virginia, USA
Funding
Deutsche Forschungsgemeinschaft, Emmy-Noether Junior Research Group MarHal
Travel funds from National Science Foundation (USA), International Science and Technology
Linkages Fund (New Zealand)
Publications
Peer Reviewed Publications
1. Beirle et al. [2004]
2. Fichter et al. [2005]
3. Marquart et al. [2005]
4. Peters et al. [2005]
5. Ponater et al. [2005]
6. von Glasow & Crutzen [2004]
7. von Glasow et al. [2004]
Grey Publications
1. von Glasow [2005e]
Invited Talks
1. Piot & von Glasow [2005]
2. von Glasow [2005f]
3. von Glasow [2005d]
4. von Glasow [2005c]
5. von Glasow [2005b]
6. von Glasow [2005g]
7. von Glasow [2005h]
8. von Glasow [2005i]
9. von Glasow [2004a]

98 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
10. von Glasow [2004e]
11. von Glasow [2004b]
12. von Glasow [2004c]
13. von Glasow [2004d]
14. von Glasow [2005a]
15. Pechtl [2005]

2.6. MARHAL - MODELING OF MARINE AND HALOGEN CHEMISTRY 99
2.6.1 Modeling the possible role of iodine oxides in new particle formation
Participating scientists Susanne Pechtl (b. Marquart), R. Lovejoy (NOAA), J. B. Burkholder
(NOAA), and R. von Glasow
Abstract The possible role of iodine oxides in new particle formation was investigated using the onedimensional
marine boundary layer model MISTRA, extended by a parameterization for nucleation.
While in a clean marine background atmosphere, OIO can be important for homogeneous nuclei
formation, in a more polluted atmosphere it can only contribute to nuclei growth.
Figure 2.55: Scetch of the scenarios: The model column is conditioned over different ennvironments
and then moves over coastal regions with emissions of iodine compounds and later over the ocean.
Background During the last years it became
more and more evident that particle bursts observed
in coastal regions were caused by iodine
compounds that originate from marine alegae
fields being exposed during low tide. It was suggested
that nuclei may form via self-reaction of
OIO, but the exact mechanism of particle formation
and its atmospheric relevance is still uncertain.
The 1D model MISTRA was used to exploit
the nucleation potential of OIO under different environmental
conditions, the importance compared
to another nucleation mechanism, and the potential
of OIO to contribute to the early growth of
freshly nucleated particles.
Funding DFG: Emmy Noether Junior Research
Group MarHal Gl 353/1-1
Methods and results The one-dimensional
marine boundary layer model MISTRA includes
chemistry in the gas and aerosol phase as well
as aerosol microphysics. A two-step nucleation
parameterization was implemented, where in the
first step, the “real” nucleation process is parameterized,
i.e., the formation of cluster-sized nuclei
via condensation of gases. Both ternary sulfuric
acid - ammonia - water nucleation and homomolecular
homogeneous OIO nucleation were considered.
For the latter, a parameterization was derived
based on combined laboratory - model studies.
The second step of the nucleation parameterization
treats the “apparent” nucleation rate,
i.e., the growth of clusters into the model’s lowest
size bin by condensable vapors such as OIO.
Different scenarios for a clean marine versus a
polluted continental background atmosphere were
compared. In every scenario, the air was assumed
to move, independent of its origin, first over a
coastal region (where it is exposed to fluxes of
iodine compounds) and later over the open ocean
(Figure 2.55).
According to these sensitivity studies, in the
clean marine background atmosphere OIO can be
responsible for both homogeneous nuclei formation
and the subsequent growth of the clusters to
detectable sizes. In contrast to this, in the continental
case with its higher levels of pollutants, gas
phase OIO mixing ratios, and hence related nucleation
rates, are significantly lower. Compared
to ternary H2SO4-NH3-H2O nucleation, homogeneous
OIO nucleation can be neglected for new
particle formation in this case, but OIO can contribute
to early particle growth, i.e., to apparent
nucleation rates. In general, OIO was found to be
more important for the growth of newly formed
particles than for the formation of new nuclei itself.
According to our studies, observations of particle
“bursts” can only be explained by hot spotlike,
not by homogeneously distributed emissions.
Outlook/Future work The sensitivity studies
were set up for ambient conditions encountered
during the ICARTT 2004 field campaign. A detailed
comparison with ICARTT results (regarding
iodine oxides, nucleation, etc.) will be done in
the future.
Main publication Pechtl et al. [2005]

100 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.6.2 Ozone Depletion Events in the Polar Boundary Layer in Spring: A
Model Study
Participating scientists Matthias Piot and Roland von Glasow
Abstract For more than 20 years, events with almost complete loss of ozone have been observed
in the Arctic in spring. The importance of several species and meteorological parameters for these
depletions have been investigated with sensitivity studies using a numerical box model.
Figure 2.56: Schematic depiction of the most important processes included in the MISTRA model, applied
for Arctic conditions. Fluxes over ice and sea salt production are switched ON/OFF, depending
on the air composition we study.
Background Reactive halogens play a major
role in polar ozone depletion events (ODE): the
reaction of bromine atoms with ozone, followed
by the self-reaction of bromine oxides (BrO) represents
a catalytic loss mechanism for ozone in the
polar boundary layer (PBL). However, the triggering
of the so-called ”bromine explosion” remains
unclear. I present model results where prescribed
bromine or chlorine fluxes are used to reproduce
ODEs. I investigated the importance of several
compounds for the chemistry of the PBL as well as
meteorological parameters and focused on species
which influence the occurrence of an ODE. This
study allows us to better understand which species
are important in the process of depleting ozone.
Funding DFG: Emmy Noether Junior Research
Group MarHal GL 353/1-1
Methods and results I used the chemical and
microphysical model MISTRA in the lagrangian
box-model mode to study the mechanisms influencing
these observed depletions in the polar
boundary layer. My sensitivity studies consisted
of a set of four-day runs where I changed initial
mixing ratios or fluxes (or both) of 19 different
species (including halogens, NOx, NOy,
DMS, H2O2, HCHO...) and compared the results
with base runs. The influence of temperature
and humidity have also been examined. High
HCHO concentrations result via increases in HO2
in a redistribution of bromine species involving
the aerosol phase, slowing ODEs down. Elevated
DMS leads to an increase in HCHO, therefore also
slowing ODEs down. By a similar production of
HOx, hydrogen peroxyde (H2O2) also oxidizes Brx
compounds inducing an ODE slow down. The
presence of both Cl2 and Br2 in the air may lead
to an unexpected decrease in the destruction process,
depending on their relative mixing ratios. Increasing
the mixing ratio of ethane by a factor of
2 reduces the ozone mixing ratio from a partial
ODE to a major ODE. For cases with low Br,
ethene emphasizes the ozone loss. With high Br,
it reduces the destruction process. An increase in
HONO led to different eventual ozone mixing ratios,
depending on its use by Brx-Clx compounds.
A change in temperature or humidity modifies the
liquid water content of aerosols and therefore the
uptake coefficients. The recycling of halogens via
the liquid phase is modified.
Outlook/Future work This sensitivity study
will help us investigate the potential triggers like
frost flowers for the bromine explosion, using MIS-
TRA in the lagrangian 1D mode.
Main publication Piot and von Glasow, presentations
at EGU, Vienna, 2005 and OASIS
workshop, Toronto, 2005

2.6. MARHAL - MODELING OF MARINE AND HALOGEN CHEMISTRY 101
2.6.3 Modeling Organic Films on Atmospheric Aerosol Particles and their
Influence on Cloud Microphysics and Chemistry
Participating scientists Linda Smoydzin, Roland von Glasow
Abstract It is well known that organic material from the ocean’s surface can be incorporated into
sea salt aerosols and that they often produce surface films. The relevance of these films for the gas
phase and sea salt chemistry as well as for potential changes in the microphysical properties in cloud
condensation nuclei is investigated.
Figure 2.57: Daily course of aqueous phase concentration of HCl and HNO3 (black: organic free
case, red: case with organics)
Background In the last years more and more
field experiments took place to characterize the
chemical composition of sea salt aerosols but due
to the large number and complexity of organic
compounds it is only possible to determine functional
groups present in the aerosol. Despite these
uncertainties the measurements have shown that
the organic mass fraction in fresh sea salt aerosols
might be large enough to have a significant influence
on cloud microphysics and atmospheric
chemistry. It is assumed that surface-active organic
matter of biogenic origin is enriched in the
oceanic surface layer and gets into the atmosphere
by bubble bursting. Surface active organic matter
present in sea salt aerosols can lead to a decrease
of the aerosol’s surface tension which reduces the
mass transfer between the gas phase and liquid
phase as well as water uptake into the aerosol.
Funding DFG: Emmy Noether Junior Research
Group MarHal GL 353/1-1
Methods and results For studying the effect
of organic surfactants a one-dimensional numerical
model which contains a microphysics scheme
and a detailed description of chemistry in the gas
phase, in aerosol particles and in cloud droplets
is used. Chemical composition and hygroscopic
properties of aerosols are important aspects when
regarding droplet formation and droplet growth.
With simple assumptions simulating an organic
film on the aerosol we tested how strong the influence
of surfactants on cloud microphysics in
our model is. The decrease in water uptake and
a decreased solubility of the aerosol due to the
organic mass fraction leads to an increase in the
number of small aerosol particles. The observed
changes in the aerosol size distribution, however,
were small and might be negligible when considering
droplet growth and cloud cover.
Regarding the influence of organic matter on
chemistry it is assumed that sea salt aerosols emitted
from the ocean contain fatty acids which are
known to be film forming compounds. The organic
coating which hinders mass transfer between
the gas and liquid phase is destroyed by reaction
of the fatty acid with ozone. In fig. 2.57 the daily
course of HNO3 and HCl for a three days model
run is shown. Measurements have shown that an
average organic mass fraction of 5-10% can be assumed.
Although the organic mass fraction in this
model run is less than 5% the uptake into the liquid
phase is decreased as can be seen in lower
concentrations in the case where organics were
present in the aerosol. Coupled with the lower
uptake into the liquid phase might be a change in
the aerosol’s pH which also changes the chemical
properties of the aerosol.
Outlook/Future work Further investigation
needs to be done to verify the uncertainties regarding
the question of how strong the influence
of organics really is and which chemical processes
are affected exactly.

102 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.6.4 Impact of reactive bromine chemistry in the troposphere
Participating scientists Roland von Glasow, R. von Kuhlmann (MPI-C), M. G. Lawrence (MPI-
C), U. Platt, and P. J. Crutzen (MPI-C, SIO)
Abstract The potential impact of 0.5 - 2 pmol mol −1 BrO on the photochemistry in the free
troposphere was investigated with the help of a global three-dimensional transport model. Annual
zonal mean ozone mixing ratios are reduced by up to 20 % pointing to a potentially very significant
ozone loss process that has been ignored so far.
Figure 2.58: Annually and zonally averaged ratio of O3 in a model run with bromine chemistry to O3
in a run without bromine. The ordinate is the σ-level multiplied by 1000 which is approximately the
pressure in hPa and the abscissa is latitude in degrees.
Background Satellite observations suggest the
widespread presence of BrO in the troposphere
also outside the polar regions with global background
vertical columns of about 1-3 × 10 13
molec cm −2 , corresponding to BrO mixing ratios
of 0.5-2 pmol mol −1 if uniformly mixed in the
troposphere. The synopsis of the various measurmenets
indicates that the tropospheric BrO
was mainly located within the free troposphere
(FT). The sources for reactive bromine in the free
troposphere are thought to include the decomposition
of organic bromine compounds, release from
sea salt aerosol and upward transport, downward
transport from the stratosphere, upward transport
from ”ozone depletion events” in the polar
boundary layers during spring (”spillout”), and
release from slowly erupting volcanoes but a quantification
of these processes remains to be made.
Funding DFG: Emmy Noether Junior Research
Group MarHal Gl 353/1-1
Methods and results We used the global atmospheric
chemistry transport model MATCH-
MPIC and prescribed bromine sources to reproduce
the observed BrO vertical columns taking
inorganic gas phase chemistry and recycling on
sulfate aerosol surfaces into account. Our vertical
tropospheric columns are 0.3 - 2.4 x 10 13
molec cm −2 corresponding to BrO mixing ratios
of >0.1 to 2 pmol mol −1 . This amount of reactive
bromine lead to a reduction in the zonal annual
mean O3 mixing ratio of up to 18% in widespread
areas, and regionally up to 40% compared to a
model run without bromine chemistry. The lifetime
of inorganic bromine was increased due to the
recycling on sulfate aerosol and ranged from about
ten days in the lower troposphere to 20 days in the
upper troposphere. According to the model the
changes in ozone were not only due to photochemical
ozone destruction but also due to a reduction
of ozone production as evident by changes in the
HO2 : OH ratio that also affected the mixing ratios
of NOx and PAN. Our lower limit estimate
of the effect of BrO on dimethyl sulfide (DMS) in
the marine boundary layer showed that the effect
was even larger than on ozone, with up to 60%
reduction of DMS tropospheric column. This is
accompanied by dramatic changes in DMS oxidation
pathways, reducing sulphate production and
hence its cooling effect on climate. These results
highlight a significant missing component in the
tropospheric budgets of ozone and DMS.
Outlook/Future work We will use our experience
from the process modeling to developing
parameterizations for the sources of inorganic
bromine as well as a reduced reaction mechanism.
Main publication von Glasow et al. [2004]

2.6. MARHAL - MODELING OF MARINE AND HALOGEN CHEMISTRY 103
References
Beirle, S., Platt, U., von Glasow, R., Wenig, M., & Wagner, T. 2004. Estimate of nitrogen
oxide emissions from shipping by satellite remote sensing. Geophys. Res. Lett., 31, L18102,
doi:10.1029/2004GL020312.
Fichter, C., Marquart, S., Sausen, R., & Lee, D. S. 2005. The impact of cruise altitude on contrails
and related radiative forcing. Met. Zeitsch., 14, 563 – 572.
Lawrence, M. G., Crutzen, P. J., Rasch, P. J., Eaton, B. E., & Mahowald, N. M. 1999. A model
for studies of tropospheric photochemistry: Description, global distributions, and evaluation. J.
Geophys. Res., 104, 26245 – 26277.
Marquart, S., Ponater, M., Ström, L., & Gierens, K. 2005. An upgraded estimate of the radiative
forcing of cryoplane contrails. Met. Zeitsch., 14, 573 – 582.
Pechtl, S. 2005. Halogenchemie in der Troposphäre: Überblick und Beispiele für Prozessstudien mit
numerischen Modellen. Invited talk at the DLR, Oberpfaffenhofen, 15.11.2005.
Pechtl, S., Lovejoy, E. R., Burkholder, J. B., & von Glasow, R. 2005. Modeling the possible role of
iodine oxides in atmospheric new particle formation. Atmos. Chem. Phys. Discuss., 5, 9907 – 9952.
Peters, C., Pechtl, S., Stutz, J., Hebestreit, K., Hönninger, G., Heumann, K. G., Schwarz, A., Winterlik,
J., & Platt, U. 2005. Reactive and organic halogen species in three different European coastal
environments. Atmos. Chem. Phys., 5, accepted.
Piot, M., & von Glasow, R. 2005. Sensitivity studies of ODEs and frost flowers with a numerical
model. Invited talk at the OASIS workshop, Toronto, Canada, 20.09.2005.
Ponater, M., Marquart, S., Sausen, R., & Schumann, U. 2005. On contrail climate sensitivity. Geophys.
Res. Lett., 32, L10706, doi: 10.1029/2005GL02258.
von Glasow, R. 2004a. Halogenchemie in der Troposphäre - Untersuchungen mit numerischen Modellen.
Invited talk at the Insitut für Meteorologie und Klimaforschung, Karlsruhe, 02.11.2004.
von Glasow, R. 2004b. Links between sulfur and halogen chemistry and implications for our climate.
Invited talk at the Afred-Wegener-Institut für Meeresforschung, Bremerhaven, 05.02.2004.
von Glasow, R. 2004c. Modeling of halogen chemistry: Overview and impact on sulfur cycle. Invited
talk at the EGU meeting, Nice, 2004.
von Glasow, R. 2004d. Sea salt aerosol chemistry: Brief overview and recent modeling results. Invited
talk at the AAAR meeting, Atlanta, 2004.
von Glasow, R. 2004e. Tropospheric halogen chemistry and its implications for O3 and sulfur in
the boundary layer and free troposphere. Invited talk at the Institut für Umweltphysik, Bremen,
06.02.2004.
von Glasow, R. 2005a. Invited talk at the AGU meeting, San Francisco, 2005.
von Glasow, R. 2005b. Halogenchemie in der Troposphäre - Untersuchungen der Wechselwirkungen
mit Ozon und Schwefel in Prozess- und globalen Modellstudien. Invited talk at the Institut für
Troposphärenforschung, Leipzig, 12.05.2005.
von Glasow, R. 2005c. Impact of bromine on tropospheric photochemistry. Invited talk at the
IGAC/SPARC workshop, Mainz, 19.05.2005.
von Glasow, R. 2005d. Importance of the surface reaction OH + Cl- on sea salt aerosol for the
chemistry of the MBL - a model study. Invited talk at the EMSI Workshop on Ions and Molecules
at Aqueous Interfaces, Prague, Czech Republic, 27.06.2005.
von Glasow, R. 2005e. Lead Essay - Research Front Iodine. Env. Chem., 2, in press.
von Glasow, R. 2005f. Reactive halogen chemistry in the troposphere - Using numerical models for
detailed process studies of the marine boundary layer and a first global assessment. Invited talk at
NIWA, Lauder, New Zealand, 15.09.2005.

104 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
von Glasow, R. 2005g. Reactive halogen chemistry in the troposphere - Using numerical models for
detailed process studies of the marine boundary layer and a first global assessment. Invited talk at
Harvard Univ., Cambridge, MA, USA, 08.04.2005.
von Glasow, R. 2005h. Reactive halogen chemistry in the troposphere - Using numerical models for
detailed process studies of the marine boundary layer and a first global assessment. Invited talk at
the Univ. New Hampshire, Durham, USA, 07.04.2005.
von Glasow, R. 2005i. Reactive halogen chemistry in the troposphere - Using numerical models for
detailed process studies of the marine boundary layer and a first global assessment. Invited talk at
the Univ. of East Anglia, Norwich, UK, 28.02.05.
von Glasow, R., & Crutzen, P. J. 2004. Model study of multiphase DMS oxidation with a focus on
halogens. Atmos. Chem. Phys., 4, 589 – 608.
von Glasow, R., Sander, R., Bott, A., & Crutzen, P. J. 2002a. Modeling halogen chemistry in the marine
boundary layer. 1. Cloud-free MBL. J. Geophys. Res., 107, 4341, doi: 10.1029/2001JD000942.
von Glasow, R., Sander, R., Bott, A., & Crutzen, P. J. 2002b. Modeling halogen chemistry in the
marine boundary layer. 2. Interactions with sulfur and cloud-covered MBL. J. Geophys. Res., 107,
4323, doi: 10.1029/2001JD000943.
von Glasow, R., von Kuhlmann, R., Lawrence, M. G., Platt, U., & Crutzen, P. J. 2004. Impact of
reactive bromine chemistry in the troposphere. Atmos. Chem. Phys., 4, 2481 – 2497.
von Kuhlmann, R., Lawrence, M. G., Crutzen, P. J., & Rasch, P. J. 2003. A Model for Studies of
Tropospheric Ozone and Non-Methane Hydrocarbons: Model Description and Ozone Results. J.
Geophys. Res., 108, 4294, doi:10.1029/2002JD002893.

2.7. CARBON CYCLE GROUP 105
2.7 Carbon Cycle Group
Christel Facklam (Techn.), Samuel Hammer (PhD), Renate Heinz (Techn.), Ingeborg
Levin (GL), Tobias Naegler (Post Doc), Christoph Schönherr (Dipl.), Cordelia Veidt
(PhD, since Oct. 2005).
High precision greenhouse gases observations (CO2, CH4, N2O, H2O), together with their isotope
ratios as well as related tracer (CO, H2, SF6, 222 Radon) measurements are performed on the global,
continental and regional scale. These measurements are used in combination with regional and trajectory
models to study respective source and sink processes and with global box models to investigate
their biogeochemical cycles.
Figure 2.59: Map of monitoring stations and measurement platforms where trace gas and isotope
samples are collected for analysis
Overarching topic: Investigation of the regional and global biogeochemical cycles of CO2, CH4,
N2O and H2
Background: Increasing greenhouse gases in the atmosphere are a major player in Earth climate
change; quantitatively understanding the causes of this increase is an indispensable pre-requisite for
future climate prognoses. The most reliable information on the bio-geochemical cycles of greenhouse
gases come from long term atmospheric observations combined with modelling. The Heidelberg Carbon
Cycle Group is significantly contributing to this international effort by providing unique (isotopic)
measurements as well as validation tracer techniques and budget modelling.
Main methods: The Group is running a high-precision gas chromatography (GC) laboratory (see
Hammer, article 2.7.3, this issue) and is responsible for the stable isotope ratio mass spectrometry
(IRMS) laboratory of the Institute. Deuterium measurements in atmospheric methane samples are
made by IRMS and - in addition - by Tunable Laser Spectroskopy in co-operation with the MPI
für Kernphysik, Heidelberg (Prof. T. Röckmann). A unique global network for continuous 14 CO2
observations is maintained in collaboration with the Radiocarbon Laboratory [Levin & Hesshaimer,
2000, see also article 2.7.1 from Levin & Kromer, this issue, and section 6.1, this issue]. Atmospheric
transport tracers such as 222 Radon [Levin et al. , 2002] and SF6, analysed in collaboration with the
Limnology group (Ilmberger, section 4.2, this issue) are measured at global and European sites for
transport model validation and source estimates with the Radon-Tracer-Method [Levin et al. , 1999].
A global box model for CO2 and its isotopes was developed in the last years (Naegler, article 2.7.2,
this issue) which is currently adapted for other greenhouse gases budgets as well as tracers such as
Beryllium isotopes in collaboration with the Glaciology Group (Wagenbach, section 3.2, this issue).
Major activities of the year: As most of our work strongly relies on the precise measurement of
mixing ratios by gas chromatography, and as there was no funding available for investment of a new

106 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
instrument (the GC for greenhouse gases has been purchased in 1994 and that for CO measurements
is a permanent loan from Forschungszentrum Jülich (Dr. A. Volz-Thomas)) we made a special effort
to modernise and couple these two systems including completely new hard- and software for data
acquisition and evaluation. This work has been finalised in 2005 (see Hammer, article 2.7.3, this issue
and Schönherr [2005]) and led to a significant improvement of measurement precision in addition to
the capability to now also analyse atmospheric Hydrogen mixing ratios at high precision.
The scientific highlight of the last year concerns a question on which the group has worked now
since more than one decade, namely quantitatively closing the global budget of bomb radiocarbon
in the carbon system. The problem of a serious mismatch in the budget was first presented by
Hesshaimer et al. [1994] in Nature, suggesting an over-estimate of the bomb 14 C inventory of the
world oceans. This problem was furtheron discussed in the scientific literature and has now finally
come to a solution after new (reduced) oceanic 14 C inventories had been published in 2004 for two
points in time [Peacock, 2004; Key et al. , 2004]. In his PhD thesis, Tobias Naegler was now able
to derive a quantitatively consistent bomb 14 C budget with help of the GRACE model, and could
estimate the total bomb 14 C inventory in the carbon system [Naegler, 2005]. This now serves as the
main tool for future modelling of 14 CO2 in the global atmosphere on the basis of our unique highprecision
world-wide 14 CO2 observations (Levin and Kromer, article 2.7.1, this issue) to use 14 C as a
quantitative constraint to determine exchange rates and turnover times in the global carbon cycle.
Besides the projects performed by individual scientists of the group we have been part of two
EU-funded projects, MethMonitEUr and TCOS-Siberia. MethMonitEUr aimed at harmonising and
evaluating continuous CH4 observations in Europe which are used to determine the European budget of
CH4 emissions. MethMonitEUr also supported our CH4 isotope measurements at Alert (discontinued
in 2004) and Neumayer station. TCOS-Siberia aims at determining the carbon budget of Western
Russia and Siberia. Here we contribute with trace gas and CO2 stable isotope measurements of flask
samples collected during regular aircraft profiling at Syktyvkar (Ural Mountains) and Cherskii (Polar
Eastern part of Siberia). Both projects end in 2005 but extension is applied for at the EU.
How are single projects linked? Projects are linked by common measurement techniques and
monitoring stations (i.e. Heidelberg, Schauinsland, Neumayer, Alert etc.). Data evaluation and
interpretation on different scales is naturally linked through common source and sink distributions
of the different greenhouse gases, such as biospheric, anthropogenic, chemical oxidation/destruction.
Common modelling techniques and using tracers such as 222 Radon or trajectories are applied in the
different projects.
External Collaborations:
MPI for Biogeochemistry, Jena (Prof. Martin Heimann, Dr. Armin Jordan, Dr. Ute Karstens, Olaf
Kolle, Prof. Detlef Schulze, Dr. Axel Steinhof), German Umweltbundesamt (Prof. Ruprecht Schleyer,
Frank Meinhardt), Forschungszentrum Jülich (Dr. Andreas Volz-Thomas), MPI für Kernphysik, Heidelberg
(Prof. Thomas Röckmann), AWI Bremerhaven (Dr. Rolf Weller), Univ. Frankfurt, Inst. für
Meteorologie (Dr. Andreas Engel), LSCE, Gif-sur-Yvette, France, (Dr. Philippe Ciais, Dr. Martina
Schmidt), Royal Holloway, Univ. of London, Egham, UK (Prof. Euan Nisbet), Meteorological Service
of Canada, Toronto (Douglas Worthy), Krakow University (Prof. Kazimierz Rozanski), and many
others.
Funding: The scientific work of the group is mainly funded by research grants from the EU (TACOS,
MethMonitEUr, TCOS-Siberia and CarboEurope-IP) and DFG (Atmospheric Radiocarbon).
Publications
Peer Revied Publications
1. Levin & Kromer [2004]
2. Röckmann & Levin [2005]
Doctoral Theses
1. Naegler [2005]

2.7. CARBON CYCLE GROUP 107
Diploma Theses
1. Schönherr [2005]
2. Schell [2004]
Invited Talks
1. Levin [2004b]
2. Levin [2004a]
3. Levin [2005a]
4. Levin [2005b]

108 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.7.1 Global long-term observations of Radiocarbon in atmospheric CO2,
revisited
Participating scientist Ingeborg Levin, the Radiocarbon Laboratory, Bernd Kromer
Abstract A global network of high-precision atmospheric 14 CO2 observations is maintained, providing
an independent constraint for carbon cycle modelling. Apart from this innovative application
important in research of the anthropogenic CO2 problematic also various modern dating techniques
make use of our unique 14 C records [Mayorga et al. , 2005; Spalding et al. , 2005].
Figure 2.60: Observed ∆ 14 C in atmospheric CO2 and tree rings
Background Initiated by the late Karl Otto
Münnich, Heidelberg was among the first laboratories
involved in precise long-term observations of
bomb 14 C perturbations in the global carbon system.
Related atmospheric 14 CO2 monitoring extended
globally and carried into the present time
constitutes a world-wide unique exercise [Levin
& Hesshaimer, 2000]. This long-term and sometimes
painful effort of the Carbon Cycle Group at
IUP now offers a wealth of intriguing applications
which range from environmental issues like studying
global carbon cycle dynamics to life science
and forensic aspects.
Methods and results Continuous bi-weekly
integrated CO2 samples are collected at eight
globally distributed background stations as well
as in Germany in the Black Forest (Schauinsland)
and in Heidelberg (Schönherr, article 2.7.4, this
issue) and are analysed at high precision for their
14 C activity by conventional radioactive counting
(Kromer, section 6.1, this issue). The long term
trend of ∆ 14 C in CO2 in the Northern Hemisphere
troposphere from 1959 until 2005 is displayed in
Figure 2.60 [Levin & Kromer, 2004]. Due to atmospheric
nuclear weapon testing in the 1950s and
early 1960s the atmospheric 14 CO2 level increased
by about a factor of two (∆ 14 C≈1000�) compared
to the natural reference level. The present
steady decline which is mainly driven by the ex-
change with oceanic CO2 and by input of 14 C-free
fossil fuel CO2 into the atmosphere are underlain
relatively weak perturbations. These secondary
variations reflect interesting processes, for example
the very regular seasonal cycle of 14 CO2 at mid
latitude northern hemispheric sites today (inlay of
Figure 2.60) are mainly caused by stratospheretroposphere
exchange and by the seasonal release
of bomb 14 C stored in the biosphere for the last
50 years now re-entering the atmosphere (Naegler,
article 2.7.2, this issue). This recent net source of
bomb 14 C to the atmosphere is also reflected in
a tropical 14 CO2 maximum while a relative minimum
is observed in mid-to-high southern latitude
which is caused by disequilibrium fluxes between
ocean surface water and the atmosphere [Levin &
Hesshaimer, 2000].
Outlook/Future work The small but significant
signals observed in atmospheric 14 CO2 are
used in combination with the GRACE model
(Naegler, article 2.7.2, this issue) and more sophisticated
global 3-dimensional models to put independent
constraints on carbon exchange on earth.
Main publication: Levin & Kromer [2004]
Funding Funding: CarboEurope-IP, DFG (Atmospheric
Radiocarbon).

2.7. CARBON CYCLE GROUP 109
2.7.2 Simulating Bomb Radiocarbon: Implications for the Global Carbon
Cycle
Participating scientist Tobias Naegler, Vago Hesshaimer, Ingeborg Levin, Philippe Ciais (LSCE,
Gif-Sur-Yvette, France), Keith Rodgers (LODYC, Paris, France)
Abstract With the help of the two-dimensional global (radio-)carbon cycle model GRACE, we
estimated the total production of bomb 14 C and simulated bomb 14 C inventories in the main carbon
cycle reservoirs. Furthermore, we exploited the constraints that observed bomb 14 C inventories impose
on stratosphere-troposphere and air-sea gas exchange.
Figure 2.61: Observed (symbols) and simulated
(lines) bomb 14 C inventories in the troposphere,
stratosphere, biosphere and ocean. The black
line denotes the total simulated accumulated
bomb 14 C production, the black symbols the
”observation-based” total inventory.
Background Bomb radiocarbon has been produced
in atmospheric nuclear bomb tests. It
is injected mainly into the stratosphere. Oxydised
to 14 CO2, it takes part in the global carbon
cycle. The production of bomb radiocarbon
peaks sharply in the late 1950s and early 1960s.
Due to this pulse-like injection, bomb radiocarbon
acts like a one-time release of a dye-tracer
into the stratosphere. The analysis of the subsequent
distribution of bomb 14 C in the earth system
allows to constrain exchange times between
the main carbon reservoirs stratosphere, troposphere,
biosphere and ocean, e.g. to quantify
stratosphere-troposphere exchange (STE), the atmospheric
interhemispheric exchange time, air-sea
gas exchange and turnover times of biospheric carbon
pools.
Methods and results We simulated the
global bomb radiocarbon cycle with the Global
RAdioCarbon Exploration model GRACE, consisting
of a 22-box zonally averaged twodimensional
atmosphere coupled to a well-mixed
4-reservoir biosphere. Radiocarbon exchange between
atmosphere and the ocean was calculated
according to observed tropospheric and ocean surface
∆ 14 C . The model comprises all relevant
sources of radiocarbon (natural, bomb and industrial
production). The seasonal air mass exchange
between model boxes was calibrated with stratospheric
and tropospheric 14 CO2 observations as
well as tropospheric observations of SF6 and the
10 Be/ 7 Be ratio. The simulated air mass transport
across the tropopause then gives an estimate
of the effective STE necessary to reproduce the
observed tracer distributions. The total radiocarbon
production by atmospheric nuclear bomb
tests was determined with the help of the model
and available stratospheric and tropospheric radiocarbon
observations. The model simulated
the distribution of bomb radiocarbon among the
carbon reservoirs stratosphere, troposphere, biosphere,
and ocean. Simulated bomb radiocarbon
inventories turned out to be in very good agreement
with all available stratospheric and tropospheric
radiocarbon observations as well as with
the latest estimates of the ocean bomb radiocarbon
inventories during the GEOSECS and WOCE
surveys [Peacock, 2004; Key et al. , 2004]. For
the very first time, the GRACE model is thus capable
of closing the bomb radiocarbon budget in
the global carbon system. Using the available latest
atmospheric and oceanic (radio-) carbon data,
we developed a new, improved parameterisation
of air-sea gas exchange which is easily adaptable
to new estimates of the ocean bomb 14 C inventory
and the global wind speeds, two significant sources
of uncertainty in this approach. Furthermore, we
estimated an observation-based biospheric bomb
14 C inventory which can be used to constrain the
setup and parameterisation of biosphere models.
Outlook/Future work We will analyse in detail
bomb 14 C constraints on biospheric parameters.
Furthermore, the GRACE model will be
improved by adding an ocean module, allowing
carbon isotope simulations in the coupled
atmosphere-ocean-biosphere system.
Main publication: Naegler [2005]
Funding This PhD thesis was a close collaboration
with the LSCE, Gif-sur-Yvette, France and
has been funded by the EU projects AEROCARB
and CarboEurope-IP and by the DFG.

110 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
2.7.3 Coupling and modernisation of the Heidelberg Greenhouse Gases
and CO - GC systems for continuous measurements
Participating scientists Samuel Hammer, Christoph Schönherr, Christl Facklam, Ingeborg Levin
Abstract Two separate GC instruments were combined via one sample inlet system. The data
acquisition and evaluation software was modernised. In addition, it is now possible to determine
molecular hydrogen mixing ratios. The rebuilding led to higher measurement precision and a reduction
of sample volume and analysis time, both by a factor of two, and the data output is now homogenised
for all sample components.
Background The radiative forcing due to anthropogenic
Greenhouse Gases released into the
atmosphere accounts for approximately 1.5 W/m 2
and is therefore the main contributor to global
warming [Hansen et al. , n.d.]. Long term greenhouse
gas records of high quality are important
to determine the temporal change of these trace
gases. Combined with isotopic data and regional
or global models, the respective budgets can be
investigated. In combination with 222 Rn data, local
source and sink studies for greenhouse gases
can be carried out.
Funding This PhD work is funded by the EU
projects TCOS - Siberia and CarboEurope-IP.
Methods and results In order to couple the
GCs by connecting the sample loops of both GCs
in series, it was necessary to rebuild the sample
inlet system. In addition, the capacity for
flask sample measurements was doubled using a
separate flask valve. It is now possible to measure
twelve flasks within one sequence. To improve
the CO reproducibility, a dedicated system
of a backflush valve and resistances was developed
and successfully installed. Along with the installation
of these additional valves, the electronics
devices were improved. The two former separate
data acquisition systems were replaced by a new,
state of the art, ChemStation Chromatography
software. The rebuilding led to reduced sample
volume and analysis time, which is particularly
important for flask measurements. For the semicontinuous
measurements in Heidelberg we gained
a homogenised dataset. Since the rebuilding of
the GC it is possible to determine H2 mixing ratios
without further needs. The combined instrument
now performs measurements of CO2, CH4,
CO, N2O, SF6 and H2 every five minutes. Outside
air is measured semi-continuously via two separate
air intake lines, each of which is sampled at least
once every 30 minutes. An example of the time
series and the correlations between the different
gas species is given in Figure 2.62.
Figure 2.62: Half hourly mixing ratios of CO2,
CO, CH4, N2O and H2 in Heidelberg. SW and
SE mark the south-west and south-east air intake
lines. Additionally 222 Rn daughter concentration
and meteorological parameters are shown.
Outlook/Future work It is now planned to
apply the radon tracer method to the continuous
H2 data to assess the sink strength of local soils.
Furthermore, a detailed study on the vertical H2
profile in soil air is planned to be performed by
a diploma student. The long and extensive N2O
records from worldwide monitoring stations will
be analysed in a simple 2D model (Naegler, article
2.7.2 this issue) to improve our understanding
of the global N2O budget.

2.7. CARBON CYCLE GROUP 111
2.7.4 Investigating CO2, CO and Fossil Fuel CO2 in Heidelberg
Participating scientists Christoph Schönherr, Samuel Hammer, Bernd Kromer, Ulrike Gamnitzer,
Ingeborg Levin
Abstract In order to calibrate CO as a proxy for fossil fuel CO2 (CO2(fossil)), atmospheric CO
mixing ratios in Heidelberg are being related to (CO2(fossil)) mixing ratios derived from 14 CO2 measurements.
For extension of these investigations to sites without continuous gas chromatographic
measurements, a device for integrated air sampling in a large bag was set up and tested.
Figure 2.63: Integrated samples of CO2, CO, and 14 CO2 taken in Heidelberg for determination of the
ratio CO/CO2(fossil). Blue symbols represent winter months, red symbols summer months; dotted
lines are background mixing ratios. (a) Average CO2(total) mixing ratios during the respective
sampling periods. (b) Same as (a), but for CO mixing ratios. (c) 14 CO2 depletions of the integrated
samples, relative to the continental background. (d) CO2(fossil) mixing ratio as calculated from the
CO2(total) mixing ratio and the 14 CO2 depletion. (e) CO/CO2(fossil) ratios for each sample, and
the average ratio for all samples (solid black line).
Background The global atmospheric mixing
ratio of CO2 has been rising from about 280 ppm
at the beginning of the 19th century to 378 ppm
by the end of 2004, mainly due to the combustion
of fossil fuels. This influences the Earth’s climate
at present and very likely in the future. In order
to estimate fluxes of CO2 into the atmosphere,
it is necessary to separate the share originating
from fossil fuel combustion. This can be achieved
by radiocarbon ( 14 C) observations [Levin et al. ,
2003], or by observation of another proxy, like carbon
monoxide [Gamnitzer, 2003]. This proxy then
has to be calibrated first by parallel 14 C measurements.
Methods and results In a first part of my
Diploma Thesis, the local gas chromatographic
system (GC) was modernised for easier operation
and more convenient data output. Second, using
CO and 14 CO2 data from the years 2001 to
2005, the CO/CO2(fossil) ratio for Heidelberg was
studied. Samples taken during atmospheric inver-
sion situations (events) with high local emissions
signals yielded CO/CO2(fossil)=(1.06±0.33)%.
Weekly and two-weekly integrated 14 CO2 samples
influenced by a larger catchment area yielded a
mean CO/CO2(fossil) ratio of (1.33 ± 0.29) %.
Both methods can be used to assess fossil fuel
CO2 for differently sized catchment areas. For
determination of CO/CO2(fossil) at sites without
continuous GC measurements, a device for integrated
air sampling was set up and tested. This
device is suited for non-biased sampling of CO2,
CO, CH4, N2O, and SF6 during one week.
Outlook/Future work The devices for integrated
air sampling will now be set up in Paris and
Krakow in the frame of the CarboEurope-IP to be
run in parallel to integrated 14 CO2 measurements,
in order to determine the regional CO/CO2(fossil)
ratio with different emission characteristics.
Main publication: Schönherr [2005]

112 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING
References
Gamnitzer, U. 2003. Bilanzierung der Kohlendioxidemissionen in der Region Heidelberg mit Hilfe
atmosphärischer CO2-, 14 CO2- und CO-Messungen. Diploma thesis, University of Heidelberg.
Hansen, J., Sato, M., Ruedy, R., Nazarenko, L., Lacis, A., Schmidt, G.A., Russell, G., Aleinov, I.,
Bauer, M., Bauer, S., Bell, N., Cairns, B., Canuto, V., Chandler, M., Cheng, Y., Del Genio, A.,
Faluvegi, G., Fleming, E., Friend, A., Hall, T., Jackman, C., Kelley, M., Kiang, N., Koch, D., Lean,
J., Lerner, J., Lo, K., Menon, S., Miller, R., Minnis, P., Novakov, T., Oinas, V., Perlwitza, J.,
Perlwitz, J., Rind, D., Romanou, A., Shindell, D., Stone, P., Sun, S., Tausnev, N., Thresher, D.,
Wielicki, B., Wong, T., Yao, M., & Zhang, S. Efficacy of climate forcings), journal = JGR, year =
2005, volume = 110, pages = doi:10.1029/2005JD005776,.
Hesshaimer, V., Heimann, M., & Levin, I. 1994. Radiocarbon evidence for a smaller oceanic carbon
dioxide sink than previously believed. Nature, 370, 201–203.
Key, R. M., Kozyr, A., Sabine, C. L., Lee, K., Wanninkhof, R., Bullister, J. L., Feely, R. A., Millero,
F. J., Mordy, C., & Peng, T.-H. 2004. A global ocean carbon climatology: Results from Global
Data Analysis Project (GLODAP). Global Biogeoch. Cycl., 18(4), doi:10.1029/2004GB002247.
Levin, I. 2004a. Greenhouse Gases Trends in Europe and at the German Antarctic Station. Invited
talk, WMO WMO/GAW Expert Workshop on The Quality and Applications of European GAW
Measurements. Tutzing, Germany.
Levin, I. 2004b. Quantification of Exchange Rates in the Global Carbon Cycle by Radiocarbon Observations.
Invited talk, Physical Colloquium. University of Groningen, The Netherlands.
Levin, I. 2005a. Quantifying fossil fuel CO2 over Europe. Invited talk, Workshop on A Blueprint for
a GHG monitoring system in Europe. Amsterdam, The Netherlands.
Levin, I. 2005b. Recent Heidelberg Radiocarbon Observations in Atmospheric CO2. Invited talk,
13th International WMO Experts Meeting on atmospheric CO2 and Related Tracer Measurement
Techniques. Boulder (CO) USA.
Levin, I., & Hesshaimer, V. 2000. Radiocarbon - a unique tracer of global carbon cycle dynamics.
Radiocarbon, 42(1), 69–80.
Levin, I., & Kromer, B. 2004. The tropospheric 14 CO2 level in mid-latitudes of the Northern Hemisphere
(1959-2003). Radiocarbon, 46(3), 1 261–1 272.
Levin, I., Glatzel-Mattheier, H., Marik, T., Cuntz, M., Schmidt, M., & Worthy, D.E. 1999. Verification
of German methane emission inventories and their recent changes based on atmospheric
observations. J. Geophys. Res., 104(D3), 3447–3456.
Levin, I., Born, M., Cuntz, M., Langendörfer, U., Mantsch, S., Naegler, T., Schmidt, M., Varlagin,
A., Verclas, S., & Wagenbach, D. 2002. Observations of atmospheric variability and soil exhalation
rate of Radon-222 at a Russian forest site: Technical approach and deployment for boundary layer
studies. Tellus, 54(5), 462–475.
Levin, I., B. Kromer, M. Schmidt, & H. Sartorius. 2003. A novel approach for independent budgeting
of fossil fuel CO2 over Europe by 14 CO2 observations. Geophysical Research Letters, 30(23), doi:
10.1029/2003GL018477.
Mayorga, E., Aufdenkampe, A. K., Masiello, C. A., Krusche, A. V., Hedges, J. I., Quay, P. D., Richey,
J. E., & Brown, T. A. 2005. Young organic matter as a source of carbon dioxide outgassing from
Amazonian rivers. Nature, 436, 538–541.
Naegler, T. 2005 (June). Simulating Bomb Radiocarbon: Consequences for the Global Carbon Cycle.
Ph.D. thesis, Insititut für Umweltphysik, University of Heidelberg, Heidelberg, Germany.
Peacock, S. 2004. Debate over the ocean bomb radiocarbon sink: Closing the gap. Global Biogeoch.
Cycl., 18, GB2022, doi:10.1029/2003GB002211.
Röckmann, T., & Levin, I. 2005. High-precision determination of the changing isotopic composition
of atmospheric N2O from 1990 to 2002. J. Geophys. Res. accepted.

2.7. CARBON CYCLE GROUP 113
Schell, S. 2004. 222 Radon-Profil-Messungen in Süd- und Ostdeutschland, Anwendung der Radon-
Tracer-Methode zur Berechnung von CO2- und CH4-Flüssen. Diplomarbeit, Insititut für Umweltphysik,
University of Heidelberg. in German.
Schönherr, C. 2005 (October). Investigating Carbon Dioxide, Carbon Monoxide and Fossil Fuel CO2
in Heidelberg. Diplomarbeit, Insititut für Umweltphysik, University of Heidelberg.
Spalding, K. L., Buchholz, B. A., Bergman, L.-E., Druid, H., & Frisén, J. 2005. Age written in teeth
by nuclear tests. Nature, 437, 333–334.

Terrestrial Systems
3.1 Soil Physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
3.2 Ice and Climate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
115

3.1. SOIL PHYSICS 117
Overview
We study the whole range of physical processes in near-surface land systems, including the land
cryosphere, at spatial scales ranging from sub-millimeter to hundreds of kilometers. These processes
are relevant for a spectrum of hot environmental issues including water resources in arid and semi-arid
regions, contamination of groundwater by agrochemicals and waste disposal site, as well as past and
present climate changes. Current main research fields are
1. movement of water and contaminants through soils into groundwater
2. geophysical near-surface exploration and monitoring
3. thermal and hydraulic dynamics of permafrost in a changing environment
4. climate and environmental archives of glaciers and ice shields
The group is organized in two major subgroups: “Soil Physics” covering research fields 1. . . 3 and “Ice
and Climate” covering research field 4. An overview of their current research activities is given on
pages 118ff and 137ff, respectively.
Future Work
Important perspectives for the next reporting period include
1. extension of the Grenzhof test site to include electrical resistivity tomography (ERT) and additional
ground-penetrating radar (GPR) measurements,
2. investigation of frequency-dependent dielectric properties of soils as a basis for accurate measurements
of soil water content at the field scale,
3. setup of several monitoring stations on the Qinghai-Tibet plateau (China) to study the dynamics
low-latitude permafrost and the impact of climatic warming,
4. participation in the EPICA project (European Ice Core Drilling in Antarctica) through 10 Beinvestigations
at the deep DML (Dronning Maud Land) ice core,
5. attempts to date the basal layer of Alpine glaciers.
More details are again given in the respective summaries.
3.1 Soil Physics
Members
Dr. Andreas Bayer, PhD student
Cand. Phys. Alexandra Herzog, diploma student
Angelika Gassama, lab technician
Dipl. Phys. Holger Gerhards, PhD student
Dr. Olaf Ippisch, postdoctoral researcher
Cand. Phys. Patrick Leidenberger, student
Dr. Ing. Benedikt Oswald, senior scientist
Dipl. Phys. Fereidoun Rezanezhad, PhD student
Prof. Dr. Kurt Roth, group leader
Dr. Anatja Samouëlian, postdoctoral researcher
Cand. Phys. Klaus Schneider, diploma student
Dr. Nadiya Smoljar, postdoctoral researcher
Dipl. Phys. Carolin Ulbrich, PhD student
PD Dr. Hans-Jörg Vogel, senior scientist
Dr. Ute Wollschläger, senior scientist

118 CHAPTER 3. TERRESTRIAL SYSTEMS
Background
Transport of water, dissolved chemicals, and heat are intimately linked in soils and they are an important
aspect of many environmental issues like quantity and quality of groundwater, irrigation and
soil salinization, coupling of soil and atmosphere, and stability of permafrost soils. Major challenges
are (i) the understanding of the physical basis of these highly nonlinear processes and (ii) the quantitative
understanding of their manifestation at the scale of eventual interest. While the fundamental
understanding typically refers to spatial scales of millimeters to meters, the scale of interest ranges
from hundreds of meters, e.g., for optimized irrigation, to tens or hundreds of kilometers, e.g., for the
impact of landuse changes on climate.
Research Focus
Our primary focus lies on understanding the physical basis of transport processes in soils, specifically
the movement of water, of non-reactive solutes, and of thermal energy. We cover the range from
detailed studies in the laboratory to monitoring at the field scale and from conceptual modeling to
numerical simulation.
A secondary focus is the development of novel approaches to (i) exploring subsurface structures
and (ii) non-invasive measurements of state variables and material properties. Both are prerequisites
for simulating large systems with time scales beyond reasonable experimentation and for monitoring
transport processes.
Project Clusters and Links
Cluster A: Transport Processes
At the lab scale, we study fundamentals of transport in porous media, currently water movement
in coarse-textured media which may become unstable and lead to so-called flow fingers. These have
been shown to be inconsistent with Richards’ equation which underlies most current models of water
movement in soils. We study these instabilities in Hele-Shaw cells. Water saturation and dye
distributions are determined by light transmission (project 3.1.3) which was previously calibrated by
X-ray transmission (project 3.1.2). To improve the quality beyond that achieved with the white light
transmission measurements, we look, with support from the image analysis group of Prof. Dr. Bernd
Jähne, into near-infrared measurements within the absorption bands of water (project 3.1.4).
Concurrent with our experimental studies, Sreejith Kuttanikkad in the parallel computing group
of Prof. Dr. Peter Bastian at IWR develops a high-resolution solver for Stokes’ equation at the pore
scale.
At the small field scale, we investigate the impact of soil structures on water and solute movement.
Of particular importance here are macropores – cracks and wormholes – which may lead to
the bypassing of the biologically active layers. This has an impact on the availability of water for
plants and on the decay of contaminants. An experimental study of so-called preferential flow was
performed in cooperation with INRA at Orleans, Frankreich (Dr. Isabelle Cousin) (project 3.1.7) and
successfully simulated numerically (project 3.1.8).
At the large field scale, we operate test and monitoring sites at Grenzhof, Heidelberg, and near
Ny-˚Alesund, Svalbard. Further sites are planned on the Qinghai-Tibet plateau, China.
The Grenzhof site, located a few kilometers from Heidelberg, is dedicated to exploring transport
processes in natural soils, eventually also the coupling between soil and atmosphere, and to developing
and testing new measuring methods and instruments. Its primary advantages are easy access and
vicinity to the institute.
The site is 20 m × 10 m in size. It is equipped with an automated weather station (air temperature,
humidity, and pressure, wind speed and direction, precipitation, radiation components), a profile of
ground temperature sensors down to 1.6 m, and two profiles of time-domain reflectometry (TDR)
probes for measuring liquid water content down to 1.4 m.
During the installation of the ground instruments, large soil cores where extracted whose hydraulic
properties are measured in the lab as described below on “Inverse Determination of Soil Hydraulic
Properties”.
Weekly measurements with ground-penetrating radar (GPR) yield novel information on the dynamics
of soil water content at the field scale which is compared with the point measurements provided
by TDR (project 3.1.9).

3.1. SOIL PHYSICS 119
In November 2004, a tracer experiment was started and monitored with soil coring, TDR, GPR,
and electrical tomography, the later by our cooperation partners from the Dresdner Grundwasserforschungszentrum
(DGFZ). The experiment was sampled, in the classical destructive way, in April
2005 (project 3.1.10).
Funding for this site is provided primarily by DFG through a joint project with DGFZ (Dr. Frank
Börner), and TU Freiberg (Prof. Dr. Bernhard Forkmann) and supplementary by IUP.
Future The Grenzhof site is currently expanded to 200 m × 10 m to allow for large-scale
measurements, primarily with GPR. In addition, we plan to install our own and permanent electrical
resistivity tomography (ERT) equipment early 2006. This will be used to monitor a new tracer
experiment with high temporal resolution. In addition, we want to explore the feasibility of monitoring
the dynamics of soil water content with ERT.
The two sites near Ny-˚Alesund, Svalbard are aimed at understanding the thermal and hydraulic
dynamics of arctic permafrost. They are equipped with two-dimensional arrays of temperature- and
TDR-sensors, some 30 of each at both sites, and Bayelva in addition has a weather station as already
described for the Grenzhof site. The NP site is very near to the corresponding station at Ny-˚Alesund.
Both sites were installed and are operated in cooperation with the Alfred Wegener Institute (AWI),
Potsdam (Dr. Julia Boike). They deliver data since September 1998, with some interruptions due to
damage by reindeer.
The original installation and operation of the sites was funded by DFG, the corresponding project
was completed in 2001. The current operation and maintenance is covered by AWI and the stream of
data is collected and processed at IUP. The original goal of understanding the thermal and hydraulic
dynamics was achieved. The two stations are now oriented towards monitoring the response to climatic
changes.
Future We plan to set up four monitoring stations similar to those installed on Svalbard on the
Qinghai-Tibet plateau, China. They will be aimed at understanding the dynamics of low-latitude
permafrost, which is characteristically different from arctic permafrost due to the different radiation
regime. Besides the local dynamics, we also want to study the impact of the current climatic warming
on the decay of the permafrost. The major tool for this second aspect will be GPR explorations
(project 3.1.13) on long lines in the vicinity of the stations.
This project is funded by DFG and Chinese Academy of Sciences (CAS). Cooperation partners
are Dr. Yu Qihao and Dr. Jin Huijun of the Cold and Arid Regions Environmental and Engineering
Research Institute (CAREERI) and CAS, Lanzhou.
Cluster B: Geophysical Exploration and Monitoring
Geophysical instruments are increasingly used for near-surface investigations of soils, permafrost,
and glaciers and for the non-destructive semi-quantitative monitoring of transport processes. Our
interest is currently focused on electromagnetic waves in the frequency range between 50 MHz and
2 GHz which allow the mapping and monitoring of dielectric structures. These in turn are strongly
influenced by the volume fraction of liquid water which has a dielectric number εw ≈ 80 that is
about an order of magnitude larger than that of other relevant constituents. Since soil and geologic
formations typically differ in texture, and thus in equilibrium water content, the dielectric structure
of the subsurface typically also reveals its architecture. We employ two classes of instruments, timedomain
reflectometry (TDR) which operates with guided waves and ground-penetrating radar (GPR)
which is based on free waves. Our primary aim here is to develop a hierarchy of instruments and
methods to measure the volumetric water content at scales from a few centimeters to a few kilometers.
TDR has been developed and used for a long time to measure average volumetric water content
within the sampling volume of the probe, typically a cylinder some 50 mm in diameter and 200 mm
long [Roth et al. , 1990]. A new development is the use of much longer probes in conjunction with
the inversion of the time-domain signal to obtain the spatial variation of the dielectric number along
the probe instead of its average (project 3.1.11). Such an instrument is particularly attractive near
the soil surface since the water content there changes very rapidly both in space and in time.
GPR has the advantage that no installations are required – the antennas are just pulled across
the soil surface – and thus facilitates measurements on long transects with lengths of hundreds of
meters to a few kilometers. Two groups of waves may be distinguished in a typical GPR application,
the ground wave which propagates as an evanescent wave along the soil-air interface, and the reflected
waves that originate at dielectric discontinuities. Both yield valuable information on the water content
and, to a limited degree, on solute distributions. Besides the heuristic analysis of GPR and comparison
with TDR (project 3.1.9), we investigate the inversion of the signals. As a first step, semi-analytical
(project 3.1.13) and numerical (project 3.1.12) forward solutions are developed and their performance
is explored. The associated calculations are rather time-consuming and run on our Linux-cluster.

120 CHAPTER 3. TERRESTRIAL SYSTEMS
Future Activities at the Grenzhof site will be expanded along two lines: (i) We will explore the
potential of GPR-trains (multiple coupled antennas) to yield concurrent information on the depth of
reflectors and on soil water content. (ii) We want to perform a comparative study of different methods
for measuring near-surface soil water content. Methods used will be soil sampling, vertical TDR, GPR
groundwave, and GPR reflection. This study is a prerequisite for the accurate interpretation of data
obtained satellite instruments (synthetic apperture radar (SAR) and radiometry as it will be available
from SMOS after 2007).
Cluster C: Effective Material Properties
Soils contain relevant structures on many scales, from a few micrometers all the way up to the landscape.
Effective material properties which summarize the impact of physical processes below some
particular scale are a convenient approach to limit the complexity of models and simulations at scales
of practical interest. These effective properties are of fundamental interest in their own right – under
what circumstances do they exist and how can they be defined objectively? – but the immediate
interest is typically to get hands on optimal estimates of their functional form and the corresponding
parameters.
Hydraulic properties, the soil water characteristic θ(ψm) and the hydraulic conductivity function
K(θ) are prerequisites for the numerical simulation of water movement through soils. We employ
the traditional multi-step outflow (MSO) method to (i) routinely estimate these functions and (ii) investigate
effective properties of heterogeneous media (projects 3.1.2 and 3.1.1). In this method, an
initially completely saturated soil column is drained by reducing the pressure at its lower end in a
number of discrete steps. Pressure and outflow are recorded and inverted to obtain highly nonlinear
functions θ(ψm) and K(θ).
The MSO method is limited to rather high potentials – pressure cannot be reduced below the
vapor pressure – and does not yield useful information for fine-textured soils. To obtain a much more
extended range, we develop a new method where water is evaporated from the sample’s surface. This
allows very low potentials by simply reducing the humidity of the incoming air. The vapor flux is
measured spectroscopically (project 3.1.5) and again inverted numerically with a code developed by
Olaf Ippisch (IWR and IUP).
A crucial aspect of the inversion procedure, both for the traditional MSO and for the evaporation
experiment, is the parameterization of θ(ψm) and K(θ). The current approaches are almost universally
based on the Mualem-van Genuchten parameterization. In cooperation with IWR (Prof. Dr. Hans-
Georg Bock) a free parameterization based on monotone spline functions is developed (project 3.1.6)
and implemented in the inversion code by Olaf Ippisch (IWR and IUP).
Funding for the projects on effective hydraulic properties is provided in part by BMBF (“Sickerwasserprognose”)
and by DFG.
Dielectric properties, the soil’s complex dielectric number ε, depend strongly on liquid water
content and moderately on temperature, frequency, solute concentration, and soil composition. They
provide the link between the electromagnetic measurements and the quantities of interest, primarily
soil water content and secondarily solute concentration.
The traditional approaches consists in identifying a regression relation between the quantities of
interest [Topp et al. , 1980] or in postulating a dielectric mixing model εc = f({θi, εi}), where εc
the measured (composite) dielectric number and {θi, εi} are volume fraction and (known) dielectric
number of the set of constituents i [Roth et al. , 1990]. Both approaches are used for the direct analysis
of the type of broadband signals used in TDR and GPR. In some earlier work in cooperation with
Prof. Dr. Markus Flury, Washington State University, Pullman, USA, and Dr. Marco Bittelli, now
at University of Bologna, Italy, we showed that narrow-band measurements (dielectric spectroscopy)
yield more information on different soil constituents and in particular allow the distinction between
liquid and frozen water [Bittelli et al. , 2004].
For the next step, we developed a large coaxial cell for dielectric measurements of geologic samples
for frequencies 0.3. . . 3’000 MHz using a network analyzer together with the required robust inversion
code [Oswald et al. , 2006]. A first series of calibration runs with different liquids and partly saturated
sands have been completed successfully.
Future Preliminary studies of soil samples from the Grenzhof site revealed a rather strong
frequency-dependence of dielectric properties. This has a strong impact on water content measurements
with electromagnetic methods and requires further detailed investigation.

3.1. SOIL PHYSICS 121
Major Achievements
1. Demonstration that water content profiles can be obtained from GPR measurements and their
accuracy rivals that of TDR (project 3.1.9).
2. Modeling and numerical simulation of solute transport through a soil with macropores (projects 3.1.7
and 3.1.8).
Publications
Peer Reviewed Publications
1. Oswald et al. [2006]
2. Roth et al. [2005]
3. Stöhr & Roth [2005]
4. Bayer et al. [2005]
5. Yu et al. [2005]
6. Vogel et al. [2005a]
7. Vogel et al. [2005d]
8. Vogel et al. [2005e]
9. Wollschläger & Roth [2005]
10. Braun et al. [2005]
PhD Theses
1. Bayer [2005]
Diploma Theses
1. Herzog [2005]
2. Ulbrich [2005]
3. Herzog [2005]
Invited Talks
1. Vogel [2005b]
2. Vogel et al. [2005c]
3. Vogel [2005c]
4. Vogel [2005a]
5. Oswald & Roth [2005c]
6. Roth & Wollschläger [2005]
7. Roth [2005a]
8. Roth [2005b]
9. Roth [2005c]

122 CHAPTER 3. TERRESTRIAL SYSTEMS
3.1.1 Estimation of effective hydraulic parameters for heterogeneous porous
media
Participating scientist Anatja Samouëlian, Hans Jörg Vogel
Abstract Through numerical simulations and experimentations, the influence of small scale heterogeneity
on large scale hydraulic properties of soil was investigated. The effective water capacity
is directly related to the probability densities function for the texture of the composites, while the
hydraulic conductivity additionally depends on its topology.
Figure 3.1: a) Three types of heterogenous media where the grey value corresponds to characteristic length
of subscale porous medium, b) effective water retention curve for the three fields (predicted in yellow, grey
area represents the small scale heterogeneity), c) the regression between hydraulic conductivity exponent and
topological variable.
Background Soil hydraulic properties can be
estimated using multi-step-outflow experiments
(MSO) in combination with inverse modeling.
One assumption implied, is that the sample is
large enough to contain all microscopic heterogeneities
in the sense of a representative elementary
volume (REV). Hence, the measured properties
are considered as an ‘effective‘ description.
However these ideal conditions are rarely met,
since soil is typically heterogeneous at various hierarchical
scales.
The question for this project is: Given the
measured effective properties together with the
entire 3D structure of the composites (measured
by X-ray tomography) is it possible to estimate
the properties of each single component?
As a first step we investigate the functional
relation between structural features and the effective
hydraulic properties through numerical simulations
using well defined random fields.
Funding DFG project 2004-2005 VO 566/5-1
Methods and results Numerical experiments
were performed on heterogeneous media: (i) a
standard Gaussian field, (ii) a field where the fine
textured material is highly connected and (iii) a
field where the coarse textured material is connected
(fig.1a). The hydraulic properties are described
assuming Miller-similarity. Their topol-
ogy, quantified by the Euler number is different,
however, the first two moments, mean and covariance,
are identical for the three random fields.
The simulated water retention curves for the
three fields are identical and can be directly calculated
from the histogram of the components by
θeff (ψ) = �
i [ωiθi(ψ)] for i materials and their
probability density ωi (fig. 1b).
Concerning the hydraulic conductivity, the
topology of the structure is a key to predict the
effective behaviour. It can be approached by
Keff (ψ) q = �
i [ωiKi(ψ) q ] with q an exponent
related to the topology of the conductivity field.
The first results indicate a polynomial regression
between the calculated exponent q and the measured
topology (fig. 1c).
Outlook/Future work The quantitative link
between structural quantities and effective hydraulic
properties, both accessible through direct
measurement, will greatly facilitate the estimation
of the subscale parameter field. Based on this information
the phenomenology of water flow and
solute transport can be predicted for natural heterogeneous
soil.
Main publication Samouëlian et al., Averaging
of hydraulic properties in heterogeneous
porous media (to be submited)

3.1. SOIL PHYSICS 123
3.1.2 X-ray attenuation techniques to study the dynamics of water in
porous media
Participating scientist Andreas Bayer, Hans-Jörg Vogel, Kurt Roth
Abstract X-ray attenuation was used as non-invasive method to monitore the distribution of water
in samples of porous media during a multistep-outflow experiment. Differences between the data and
a numerical inversion that aimed at effective material properties reveal the impact of soil structures
at different scales.
0 1
40 50 60 70
time [h]
0
−20
−15
cumulative outflow [cm]
1
−10
2
−5
boundary condition [cmWC]
0
3
−0.5
5
diff. [cm]
0
0.5
sample height [cm]
10
8
6
4
2
0
0 0.1 0.2 0.3 0.4
water content [-]
sample height [cm]
10
8
6
4
2
0
0 0.1 0.2 0.3 0.4
water content [-]
Figure 3.2: Left: Measured cumulative outflow (black circles) and results of inverse modeling (black
lines). Red lines shows predicted outflow assuming layered material model. Green symbols and lines
represent outflow obtained for layered material model turned upside down with effective properties
again obtained by inversion. Center: Measured (symbols) and simulated (solid lines) vertical water
distribution at hydrostatic equlibrium for different outflow steps assuming uniform sample. Right:
Same as the center but simulation based on layered model.
Background The description of the dynamics
of water in soil leads to the introduction of effective
properties. For large scales, order of 1 m and
beyond, soils and aquifers have a distinctive heterogeneous
architecture of soil layers and sedimentary
units, respectively. These units are presumed
to be uniform and are represented by a set of effective
material properties which in turn are measured
in the lab, typically by multistep-outflow
experiments. This approach does not explicitly
address the well-documented multiscale heterogeneity
of natural porous media which extends to
scales much smaller than 1 m. In this project, the
impact of heterogeneity on the typical analysis of
a multistep-outflow experiment is explored.
Funding BMBF (“Sickerwasserprognose”)
Project 02WP0261
Methods and results A non-invasive method
to obtain information about the assumed sample
structure is X-ray attenuation and tomography.
It was combined with a multistep-outflow setup
to assess the sample’s structure and to monitor
the distribution of water during the experiment.
Vertical water content profiles extraxted from
X-ray attenuation data were compared with
profiles simulated based on Richards equation
(fig. 3.2, middle). The simulation used hydraulic
parameters estimated from the inversion of measured
outflow data (fig. 3.2, left). The dramatic
differences between measured and predicted profiles
are typically not observed because the corresponding
instrumentation is not available. The
origin of the difference is a weak layering produced
during sample preparation and is representative
for a rather uniform natural porous medium. Inversion
of the data did not hint at this complication:
the fit represents the outflow data very well.
To investigate the issue, we set up a layered
model based on the X-ray attenuation profiles
and hydraulic parameters obtained from forward
simulations. The modeled outflow fits both, the
measured outflow and the vertical water content
distribution, reasonably well. Notice that there
was no inversion used in this approach. This illuminates
the difficulties to estimate effective hydraulic
properties in a “blind experiment” where
the internal structure is not represented. We
demonstrated that X-ray measurements provide
the crucial additional information required for
a faithful model of the hydraulic behavior of a
porous material, at least for the simple case studied
here.
Main publication Bayer, A., PhD thesis 2005;
Bayer et al. [2004]; Bayer et al. [2005]

124 CHAPTER 3. TERRESTRIAL SYSTEMS
3.1.3 Fingered Flow Through Initially Dry Porous Hele-Shaw cell
Participating scientist Fereidoun Rezanezhad, Hans-Jörg Vogel, Kurt Roth
Abstract Fingered flow is an instability that occurs during infiltration into dry, coarse-textured,
and uniform porous media. We study the dynamics of such fingers in porous Hele-Shaw cells with
dimensions 1.6 × 0.6 × 0.003 [m]. High-resolution measurements of the water saturation are obtained
from light transmission images that have been calibrated by X-ray transmission.
Background Unstable flow of water during infiltration
into unsaturated porous media belongs
to the class of preferential flow. It has been studied
for many years and we have a quite complete
description of the general phenomena. Glass and
Nicholl (1996) reviewed the classical understanding
and DiCarlo (2004) summarizes the newer
developments which focus on the nature of the
saturation overshoot in the finger tip. Fingered
flow is important for some practical issues, e.g.,
for rapid contaminant transport with irrigation in
many arid regions. However, it also illuminates
our very understanding of the physics of multiphase
flow in porous media. Indeed, the current
theory – Richards equation – cannot explain the
existence of such fingers.
Funding DFG RO 1080/9-1&2
Methods and Results The key to understanding
fingered flow are rapid high-resolution measurements
of the water saturation. To facilitate
this, we work with Hele-Shaw cells – two parallel
glass plates separated by a few millimeters –
that are filled with sand. Light transmission is
the used as a proxy for water saturation. A simple
digital camera then yields the required rapid measurements.
Since the relation between transmission
and saturation is nonlinear, it is calibrated
with X-ray transmission which is accurate but too
slow and also too expensive for routine measurements.
In our experiments, fingers are initiated
at the transition from a fine-textured layer, where
the flow is very uniform, to a coarse-textured
Figure 3.3: Experimental setup for X-ray and
light transmission measurements. The front
view shows the highly localized flow paths that
originate from the flow instability in the uniform
part of the medium.
layer. They eventually disappear into the simulated
groundwater at the lower end of the cell. At
different stages, a dye tracer is added to the flow in
order to study the flow field behind the finger tip.
Finally, pressure sensors are installed to monitor
the potential energy of the water.
First, a number of experimental findings of
other groups were reproduced. These are in particular
(i) the maximum saturation that occurs in
the finger tip, (ii) the stability of the resulting flow
channel on short time scales and its diffusive decay
on very long time scales, and (iii) the existence of a
mobile core and an immobile fringe. Some newer
findings include (i) the demonstration that flow
channels are destroyed when they encounter heterogeneous
layers, (ii) the detection of pressure
drops in the overlaying fine-textured layer upon
initialization of a new finger, and (iii) the detection
of correlated intermittency between different
fingers.
Outlook/Future Work The future work will
concentrate on the theoretical understanding of
the experiments. This necessitates a still higher
spatial resolution, however, which in turn requires
a more detailed representation of the light transmission
through the porous medium. Measurements
of the point spread function in the nearinfrared
as well as in the visible region are under
way (project 3.1.4). On another route, a microscope
was installed that allows the resolution of
the pore space and the detailed observation of the
water phase during the passage of a finger tip.

3.1. SOIL PHYSICS 125
3.1.4 Near Infrared Imaging Spectroscopy of Water States in Porous Silicate
Media
Participating scientist Nadiya Smolyar, Kurt Roth, Bernd Jähne
Abstract We have examined capillary and adsorbed water in porous silicates (quartz sand, clay,
silica gel) by using of Near Infrared Image Spectroscopy, NIRIS. The interaction of water with the
porous media, the spatial distribution of water content, and the physics of different water states, as
well as their transformation will be studied.
Figure 3.4: Spectral transmission images of capillary water in sand at different times t1(a) < t2(b),
showing the distribution of water content and state.
Background NIRIS examinations are important
for understanding the molecular mechanisms
of water interacting with porous silicate media.
Even today, the role water plays in the quality of
soils and in further environmental effects is not
unterstood in many aspects.
Methods and results Capillary and adsorbed
water is examined spectrally in both dry and
saturated silica specimens. The frequency spectra
are measured in near infrared (ν = 3300 −
11000cm −1 ; λ = 700 − 3000nm) with a UV-NIR
spectrometer Scan 500 (Varian,USA).
The frequency values, the characteristic intensities,
and appearance of new spectral bands of water
in SiO2 media yield numerous data as elasticity
constants, bond geometries, and adsorption
mechanisms. The analysis of OH vibration
modi permits the determination of water content
along with changes of water states in the silicate
medium. We have found that the water content
can be determined best by using the intensive
bands 2νOH and νOH + ν2, and the water state
according to the bands 3νOH and 2νOH+ν2.
A new innovative NIRIS method has been developed
for investigations on the spectral optical
qualities of water in porous specimens with spatial
resolution. To this end, an imaging multispectral
32-channel CCD spectrometer has been set up.
The corresponding CCD camera takes sequences
of spectral images at certain wavelengths using
band pass filters. The images are by spectral digital
image processing analyzed.
Outlook/Future work The NIRIS concept
permits the determination of molecular interaction
forces of water on solid boundaries and micro
pores together with the physics of water states and
measuring the water distribution on porous silicates.
The results will aid in gaining deeper understanding
of the thermodynamical, structural,
and dynamic characteristics of water in silicate
media. We are planning the following investigations
of water in porous silicate media:
-Relation of multiple light scattering for determination
of true values of water absorption; -
Investigation of different water states, their spatial
distribution and concentration; -Investigation
of the stationary and dynamic water regimes; -
Spectral analysis of the influence of physical factors
on the interaction of water and medium; -
Investigation of multi-phase systems with various
kinds of intermolecular interaction.
Main publication Smolyar N., M. Korniyenko
and K. Roth (2005) Near Infrared imaging spectroscopy:
A new tool for studying water states
and movement in porous media, ’Geophysical Research
Abstracts’, EGU05-A-07910.
Smolyar N. (2003) Bildgebende Spektroskopie
an Pflanzenblättern. Dissertation, Universität
Heidelberg, Interdisziplinäres Zentrum für Wissenschaftliches
Rechnen (IWR), 195 S.
Garbe C., N. Smolyar, M. Korniyenko and
U. Schurr (2003) Water relations in plant leaves,
Springer Verlag. Lecture Notes in Computer Science,
LNCS 19: 377-401.

126 CHAPTER 3. TERRESTRIAL SYSTEMS
3.1.5 Evaporation Experiment to determine Soil Hydraulic Properties
Participating scientist Klaus Schneider, Kurt Roth
Abstract A new enhanced evaporation experiment has been set up to measure soil hydraulic properties.
The water flux and the potential at the upper boundary are measured precisely using infrared
absorption. Hydraulic properties are determined by inverse numeric modelling, thereby explicitely
simulating the diffusive water transport at the surface.
air conditioning
pressure sensor
capillary
vacuum pump
IR gas analyser evaporation chamber
Cell A
Cell B
temperature sensor
TDR
soil
pressure sensor
Figure 3.5: Schematic of the experimental setup of the evaporation experiment. IR spectroscopy
allows precise potential and water flux measurement at the upper boundary.
Background An important issue in soil physics
is the determination of the hydraulic parameters
of soils. If the soil water characteristic θ(ψm)
and the conductivity function K(θ) of a soil are
known, its hydraulic dynamics can be simulated
using Richard’s equation.
Several methods exist to determine the hydraulic
properties in the laboratory. As these
are highly non-linear functions, numeric simulation
and inverse modelling provide a flexible tool
to determine them with reasonable accuracy.
It is generally desireable to know the hydraulic
properties in a wide range of potential and water
content. However, methods are always limited to
a certain range, and hydraulic properties normally
are not valid outside the measured range.
For the wet range with potentials up to about
ψm = −1.8 · 10 4 J/m 3 (corresponding to a water
column of −1.8 m), the multistep-outflow (MSO)
method is already well established. To obtain
valid hydraulic properties also for the dry range,
an evaporation method is developed. It will be
used after an MSO experiment. Ideally this allows
to obtain the desired functions in one run.
Problems of traditional experiments The
traditional setup for evaporation method uses a
balance to measure the cumulative outflow at
the upper boundary and tensiometers at different
heights to measure potentials. The soil is initally
saturated and free evaporation is allowed to start
(Wendroth et al 1993).
The major drawbacks of this setup are:
• With free evaporation, the boundary condition
at the upper boundary is not well defined.
• The potential at the upper boundary is not
known.
• The range is limited, because tensiometers only
work until ψm ≈ −5 · 10 4 J/m 3
• Weighting to determine the flow at the upper
boundary is problematic in the dry region, because
water content change is very small.
Methods and results To avoid these problems,
a new design of experimental setup was
used, which is shown schematically in figure 3.5. A
gas-tight chamber is placed on top of the soil sample,
and air with defined water vapour contents is
flowing through the chamber. As the potential
of the air is determined by its relative humidity,
the upper boundary condition can be controlled
precisely. The water vapour content of the air
is measured before and after the chamber by infrared
absorption. This allows very precise flux
and potential measurements, while at the same
time abandoning the usage of tensiometers and
balance. The method is thus applicable even in
the very dry region.
Additionally, numerical simulation allows explicit
modelling of the diffusive water transport in
the boundary layer, enhancing the results and the
insight into the physical processes.
Outlook / Future work The setup is currently
in its test phase, but first data look promising.
The numerical inversion must still be completed.
Main publication Diplomarbeit planned for
December 2005.
evaporation

3.1. SOIL PHYSICS 127
3.1.6 Free Parameterisation of Soil Hydraulic Properties
Participating scientists A. Herzog, O. Ippisch, S. Körkel, E. Kostina, K. Roth, J. Schlöder
Abstract In order to cope with multi-modal soil water characteristic and permeability functions a
local parameterisation based on piecewise cubic Hermite polynomials is used.
volumetric water content
Mualem−van Genuchten parametrisation
original bimodal soil water characteristic
applied suction pressure [Pa]
Figure 3.6: Sketch of a bimodal soil water characteristic together with Mualem-van Genuchten
parametrisation.
Background It is expected that soils with
multi-modal hydraulic functions (i.e. soil water
characteristic and permeability function) exist in
nature. As the hydraulic functions are mainly
obtained by inverse modelling and not by direct
measurement a parameterisation is needed that is
flexible enough to handle all cases. Specifically,
the widely-used Mualem-van Genuchten parameterisation
is too restrictive to describe the actual
functions satisfactorily. With these problem specifications
water transport through these materials
cannot be described accurately.
Different approaches have been proposed in
the last ten years. Among those are a piecewise
linear parameterisation introduced by Chardaire-
Riviere et al. (1990) and a piecewise cubic Hermite
parameterisation introduced by Knabner et
al. (Aug. 2004).
Also in this thesis piecewise cubic Hermite
parametrisation is investigated in the context
of a simulation programme for water transport
through soil.
Funding Diplomarbeit
Methods and results In this thesis a simulation
programme for water transport is used (Ippisch,
2001). The deviation between model response
and measured values is to be minimised.
The hydraulic functions are part of the model response
in parameterised form.
The simulation programme includes a minimisation
routine for solving for the unknown soil parameters.
The hydraulic functions are parameterised
by piecewise cubic Hermite polynomials.
This parameterisation guarantees C 1 continuity.
Mainly, two different modifications of the parameterisation
of Knabner et al. are tested:
1. A piecewise cubic Hermite parameterisation
using approximated derivatives according to the
formulas of Butland and Brodlie. This parameterisation
is local, in contrast to the one of Knabner
et al..
2. The derivatives themselves are not approximated
but also treated as parameters. parameterisation.
This approach leads to the best results
when started with rather good initial values,
which are gained by solving the inverse problem
with the parameterisation described in (1). However,
this parameterisation is again non-local.
For bimodal hydraulic functions it could be
demonstrated that the used piecewise Hermite parameterisation
is much more convenient than the
Mualem-van Genuchten parameterisation.
With the derivatives as additional parameters
a new problem arises: Some plateaus appeare in
the hydraulic functions where, physically, they are
not expected. They might be artefacts of the revision
of derivatives.
Outlook/Future work In order to avoid these
plateaus it is intended to create a parameterisation
that has still the C 1 continuity but resembles
more closely a piecewise linear interpolation. This
can be achieved by a much more restrictive selection
of the allowed derivatives.
Main publication Herzog, Alexandra, Diplomarbeit,
Interdisziplinäres Zentrum für wissenschaftliches
Rechnen/Institut für Umweltphysik,
Universität Heidelberg, 2005

128 CHAPTER 3. TERRESTRIAL SYSTEMS
3.1.7 Modelling water flow and solute transport in heterogeneous soil
Participating scientist Hans-Jörg Vogel, Isabelle Cousin, Olaf Ippisch
Abstract Flow and transport in soil is governed by the heterogeneous structure of the material.
In this project we consider the structure using different concepts: direct measurement, statistical
description and modelling structure formation. Based on this rough representation we estimate water
flow and solute transport. This is possible because the processes are dissipative.
A
B
C
Figure 3.7: Soil profile with three horizons (A, B, C) and the distribution of a dye tracer (left),
modelled structural components: correlated random fields and earthworm burrows (middle), and
predicted tracer distribution (right).
Background The quantitative understanding
of flow and transport in soil is hampered by
the heterogeneous structure of the material which
cannot be represented by a meaningful average
value. This is typically true at any spatial scale.
To predict the movement of chemicals between the
soil surface and groundwater this structure has to
be represented adequately.
Funding Deutscher Akademische Auslandsdienst
(DAAD, PROCOPE project).
Methods and results In this project we used
a dye tracer in a field experiment on arable soil to
visualize the tracer distribution after a cumulative
infiltration of 50 mm of water. To model this experiment,
the structure of the soil was represented
using three different approaches: i) direct measurement
of the soil horizons in the field (A,B,and
C in the figure) and the measurement of the related
hydraulic properties in lab experiments; ii)
description of the mesoscopic heterogeneity inside
the horizons by an estimated covariance function
in the A and C horizon; iii) modelling earthworm
burrows in the middle, compacted horizon (B)
by a model which mimics the formation of these
macropores.
As a result we obtain the continuous parameter
field (hydraulic properties) of the entire
experimental domain. Hence, the 3D velocity
field of water could be calculated by
solving Richards’ Equation numerically. Subsequently,
solute transport was simulated assuming
a convection-dispersion type of transport locally.
Our model predicted the main characteristics
of the experiment. It demonstrates that a rough
description of the structure together with a rough
measurement/estimation of the related material
properties can be sufficient to come up with reliable
predictions.
Outlook/Future work The further development
of non-invasive techniques to measure the
heterogeneous structure of the subsurface, together
with an better understanding of structure
forming processes will improve our ability to quantitatively
understand water flow and solute transport
in soil.
Main publication Vogel et al. [2005b]

3.1. SOIL PHYSICS 129
3.1.8 Unsaturated Flow in Strongly Heterogeneous Porous Media
Participating scientist Olaf Ippisch, Interdisciplinary Center for Scientific Computing
Abstract Numerical models for the simulation of flow and transport in strongly heterogeneous
porous media have been developed and optimized for speed, robustness and usability. The models
were used to simulate laboratory and field experiments and were used for parameter estimation from
multi-step outflow experiments.
Figure 3.8: Simulation of water infiltration in a macroporous soil
Background Natural porous media are often
strongly heterogeneous. This can influence the
flow patterns considerably, resulting in preferential
flow or macropore flow which have to be taken
into account to get reliable predictions of solute
transport. One way to handle this problem is the
use of homogenization approaches to get a set of
effective parameters for the porous medium as a
whole. However, if the heterogeneous structures
are large in comparison to the scale of interest this
is no longer possible. An alternative strategy is
the determination of the soil structure (e.g. with
x-ray tomography, geoelectrics, georadar) and the
direct simulation of the flow field. Special numerical
problems arise for parameter fields changing on
a very small scale with sometimes highly nonlinear
parameter functions resulting in poor convergence
of the linear and nonlinear solvers.
Funding Institute for Informatics, University of
Heidelberg
Methods and results The developed model
µϕ uses the Levenberg-Marquardt-Algorithm for
parameter estimation with sensitivities derived by
external numerical differentiation. The forward
model solves Richards’ equation or twophaseflow
equations using a cell-centered finite-volume
scheme with full-upwinding in space and an implicit
Euler scheme in time. Linearization of the
nonlinear equations is done by an inexact Newton-
Method with line search. The linear equations are
solved with an algebraic multigrid solver. For the
time solver the time step is adopted automatically.
Brooks-Corey and van Genuchten parametrizations
as well as cubic splines can be used for the
hydraulic functions. Solute transport was discretized
using a higher-order Godonov method
with a minmod slope limiter for the convective
part and a finite-volume scheme for the diffusive
term. It is currently limited to steady-state flow
conditions.
Outlook/Future work The model will be
ported to the new base library Dune which facilitates
the parallelization and the use of different
grid types. Parameter estimation is currently expanded
to evaporation experiments. The stability
and usability of the twophase will be improved
and the solute transport model expanded to nonsteady-state
flow conditions.
Main publications Vogel et al. [2005b]

130 CHAPTER 3. TERRESTRIAL SYSTEMS
3.1.9 Assessing temporal changes in volumetric soil water content from
ground-penetrating radar profiles
Participating scientists Ute Wollschläger, Kurt Roth
Abstract We investigated the applicability of ground-penetrating radar (GPR) to estimate temporal
changes of volumetric soil water content at the field scale. Water contents calculated from a time series
of GPR reflections are compared to values derived independently from time domain reflectometry
(TDR) measurements. We found that the results of both methods are well comparable.
volumetric water content
0.4
0.3
0.2
0.1
0
-0.1
-0.2
-0.3
-0.4
2
1
Feb. March April May June July August Sept.
50 100 150
day of year 2004
200 250
0 m...0.8 m, calc. GPR
0 m...0.8 m, calc. TDR
0.8 m...1.65 m, calc. GPR
0.8 m...1.65 m, calc. TDR
1 0 m...0.8 m, meas. mean TDR
2 0.8 m...1.65 m, meas. mean TDR
Figure 3.9: Mean volumetric water contents of the sections 0...0.80 m (1) and 0.80...1.65 m (2)
calculated from TDR data and temporal changes calculated from GPR and TDR measurements for a
1D soil profile. Changes in water content derived from both methods coincide well for both soil sections
demonstrating the potential of the GPR method to estimate volumetric water contents non-invasively
at much larger scales.
Background Measurements of volumetric soil
water content are essential for many scientific,
agricultural and economic questions since it is an
important parameter for plant growth, groundwater
recharge calculations and the local climate. In
contrast to classical methods like TDR or thermogravimetric
measurements, GPR surveys are noninvasive
and can easily be applied on scales of a
few hundreds of meters.
Funding DFG, project RO 1080/8-2
Methods and results At the Grenzhof Test
Site, a time series of GPR reflection measurements
was taken along a fixed transect to determine temporal
changes in volumetric soil water content at
the field scale. For one single trace volumetric
water contents were calculated from the two-way
travel times of two reflections at known depths
of 0.80 m and 1.65 m using the Complex Refractive
Index Method (CRIM). The measurements
were compared to volumetric water contents derived
from independent TDR measurements from
several depths at nearby soil profiles (fig. 1). During
summer 2004 several wetting and drying cycles
were observed in the upper soil section. The corresponding
changes in volumetric soil water content
were detected equally well by both methods.
In the lower soil section water content remains
quite stable which is again shown by both methods.
This investigation demonstrates the power
of GPR to determine volumetric water contents
in soils at the field scale down to a depth of several
meters.
Outlook/Future work GPR time series will
be measured at a scale of a few 100 m. We will use
an array of two GPR antennas which allows to determine
the depth of occuring reflections without
the necessity of ground-truth information from
soil profiles or drillings. The gained data will be
used as important information for the modelling
of the water dynamics in the vadose zone.
Main publication Wollschläger & Roth [2005]

3.1. SOIL PHYSICS 131
3.1.10 Monitoring Field Tracer Experiment with Ground Penetrating Radar
and Time Domain Reflectometry
Participating scientist Carolin Ulbrich, Ute Wollschläger, Kurt Roth
Abstract We explored the feasibility of Ground Penetrating Radar to non-destructively monitor
solute movement in natural soils at the field scale. In a weekly radar time series the displacement
of a CaCl2-tracer was monitored. The test site was instrumented with Time Domain Reflectometry
probes in several depths to measure soil water content and electric conductivity.
Background On its way down from the soil surface
to aquifers, water passes through soil that
acts as a filter. The transport and decomposition
of fertilizers and contaminants determines the
quality of groundwater.
The interaction of this complex system cannot
be calculated exactly. So appropriate restrictions
have to be chosen and abstract models developed
in order to get a quantitative description of a
few important aspects which can be used for estimations.
To assess the applicability of a certain
model one has to verify its predictions with experiments.
At small scales (O(1 m)) there exist numerous validation
methods, but most of them cannot be
implemented at larger scales (O(100 m)) because
they are destructive or too time-consuming.
The aim of this work was to test Ground Penetrating
Radar (GPR) as a new technique to
non-destructively monitor subsurface solute transport
processes. It was compared with Time Domain
Reflectometry (TDR) measurements and
with data from soil sampling. Model predictions
of solute transport on this scale were applied.
Methods and results At the Grenzhof Test
Site, a conservative tracer fluid that absorbs the
radar wave was spread on a streak that crosses
GPR transects vertically. The transport of the
absorbing fluid was monitored weekly with a GPR
antenna along these transects. At the end of the
experiment a trench was excavated and sampled
along the streak. The samples were analyzed with
traditional methods to verify the radar data set.
In addition, a TDR time series was acquired in
the same area in three depths. The comparison to
the excavation samples showed that TDR can be
used to monitor tracer concentration at the instru-
Figure 3.10: GPR radargram. Amplitudes of
single radar pulses are plotted versus their travel
times at the distances where they have been
acquired. The recorded signals before ≈ 15 ns
originate from air- and ground-waves that travel
through the air and along the soil surface, respectively.
The salt tracer was applied between
5.8 m and 7.8 m. It absorbs the radar signal.
mented depth in a semi-quantitative approach.
The absorption effect of the highly concentrated
salt tracer was clearly visible in the GPR surveys.
Figure 3.10 shows a radargram acquired
one month after the application of the tracer. Reflections
at layer borders, visible in the GPR surveys
that were taken before the application of the
tracer, disappeared when the signal was absorbed
by the tracer pulse. The reflections could be detected
again when the tracer pulse passed the reflector.
Obviously, the spatial resolution and accuracy is
much better in traditional sampling experiments,
but the effort there is enormous and the destructive
manner impedes large scale surveys. TDR
provides point measurements with good accuracy
and excellent temporal resolution. GPR holds the
promise to large scale experiments with good temporal
resolution but coarse spatial resolution. A
significant further effort is required to make it
quantitative, however.
Outlook/Future work A solute transport experiment
is planned to be performed on the Grenzhof
Test Site. At a scale of about 300 m tracer
will be applied on small areas and the displacement
will be monitored with GPR and TDR. The
tracer distribution will be tracked in addition by
permanent electric resistivity measurements. This
will help to achieve a better understanding of
transport processes and to further develop the
methods of GPR and TDR monitoring of tracer
movement.
Main publication Ulbrich, Carolin, Diplomarbeit,
Institut für Umweltphysik, Universität
Heidelberg, October 2005

132 CHAPTER 3. TERRESTRIAL SYSTEMS
3.1.11 Efficient reconstruction of dispersive dielectric profiles using TDR
Student assistant Patrick Leidenberger, Benedikt Oswald, Kurt Roth
Abstract Time Domain Reflectometry (TDR) has become an indispensable technique for measuring
the water content of soils. We use a numerical model for TDR signal propagation in dispersive dielectric
materials. We couple this model with a genetic algorithm to invert measured TDR traces. To make
this approach more efficient we use hierarchical spatial resolution.
Figure 3.11: Reconstruction of a measured TDR trace (Grenzhof test site, Heidelberg; 30cm three-rod
probe); reflection coefficient ρ vs. time. The ohmic and dispersive dielectric profiles (spatial resolution
3.75cm) for the calculated trace are generated with a hierarchical genetic algorithm.
Background A TDR instrument transmits a
fast rise time pulse on a TDR probe. The probe
usually consists of parallel conductors. Variations
of impedance along the probe causes a partial
reflection of the signal, which is measured.
Furthermore the conductivity and the frequencydependent
dielectric properties between the conductors
of the probe have an affect on the measured
signal.
In this study we want to extract the dielectric
parameters from TDR traces measured at the
Grenzhof test site at Heidelberg to get the water
content. Therefore we reconstruct hierarchical the
spatial distributed dielectric parameters along the
probe with a genetic algorithm.
Funding Deutsche Forschungsgemeinschaft
(Project No. 1080-8/2)
Methods and results We have implemented
a explicite time domain solver for the transmission
line equations (3.3) and (3.4) that uses Debye
model for dispersive media.
∂v
∂x
∂i
∂x
�
= − R ′ �
′ ∂
+ L i (3.3)
∂t
�
= − G ′ �
′ ∂
+ C v (3.4)
∂t
The transmission line equations with piecewise
constant parameters describes a TDR probe. We
couple this solver with a genetic algorithm, in order
to reconstruct the dispersive dielectric and
ohmic profiles along the TDR probe. The genetic
algorithm generates a population with different individuals
(a number of different sets of profiles).
For every individual we calculate a synthetic TDR
trace and compare it with the measured trace.
Then the new population is created from the old
one by crossing the best individuals and random
mutation. We use the genetic approach here, because
the error landscape contains a lot of local
minima.
We implement a hierarchical spatial reconstruction
of the profiles for more efficiency. Therefor
we start with a coarse spatial resolution of the
parameter profile. If the calculated TDR traces
from new individuals do not match better to the
measured trace for a while we increase the spatial
resolution, by cutting old intervals into halves.
This method does not only speed up the profile reconstruction
process but also leads to a smoother
parameter profile.
Outlook/Future work The code will be tested
on TDR traces measured with long probes (1m or
more). Such a long, vertical installed TDR probe
will provide a lot of informations about grounds
properties in a simple way.
Main publication Leidenberger, P., Oswald,
B. and Roth, K. (2005). Efficient reconstruction
of dispersive dielectric profiles using time domain
reflectometry (TDR). Hydrology and Earth System
Sciences Discussions, 2 (4), 1449-1502.

3.1. SOIL PHYSICS 133
3.1.12 3D Full-wave, electromagnetic model of ground penetrating radar
systems
Participating scientist Benedikt Oswald
Abstract Ground penetrating radar (GPR) has been increasingly used in hydrological applications
for subsurface structure investigation. The size of structures that can be resolved is intimately related
to the relevant wavelength of the GPR signal. A finite element time domain 3-dimensional
electrodynamics code has been implemented for studying GPR signal propagation.
+Y[m]
+Y[m]
3
3
2
2
1
1
+Z[m]
2
1
0 0
+Z[m]
2
1
0 0
1
1
2
2
3
+X[m]
-6.08
-12.83
-19.59
-26.34
-33.10
+X[m]
3 -39.85
-46.61
-53.36
pdelta_310_340tsno1400.job.cmp
Figure 3.12: An electromagnetic wave is launched
from a horizontal dipole antenne on the soil surface
(upper side of green regon) and scattered
off 2 dielectric objects (2 yellow regions) buried
in the underground (inside green region); lower
plot: dielectric parameter distribution modeling
two spheres; upper plot: contour plot of the normalized
electric field intensity [dB] for timestep
1400 of the simulation.
Background Increasing GPR resolution requires
shorter wavelength λ which demands higher
frequency f. Due to attenuation of the GPR signal
proportional to frequency, there is a tradeoff
between resolution and penetration depth. For
increasing resolution a full-wave electromagnetic
analysis of GPR signal propagation is essential.
There is evidence that sub-wavelength structures
may be manifest in the radargram. We will use
a 3-dimensional, full-wave model of a simplified
GPR system. We adopt a near field electromag-
8.99
7.86
6.74
5.61
4.49
3.36
2.24
1.11
[dB]
[-]
netic approach, originally [Ohtsu & Kobayashi,
2004] employed in scanning near field optical microscopy
(SNOM). We study the GPR’s response
to sub-wavelength sized objects and investigate
the capability of GPR to resolve those structures.
Funding IUP
Methods and results We have implemented a
3-dimensional finite element code to solve the electric
field vector wave equation (3.5) in the time
domain [Oswald & Roth, 2005a].
∇ × 1
µ ∇ × E + σ ∂E
∂t + ɛ∂2 E
∂2 = −∂J
t ∂t
(3.5)
Locally refined, tetrahedral grids are used to describe
the geometry of the GPR configuration;
this allows for detailed models of delicate geometrical
features. In order to model open region
problems we employ an absorbing boundary
condition (ABC). The code has been validated
on a Hertzian dipole radiating into free space.
We study a simplified GPR configuration of two
spherical objects separated by a sub-wavelength
distance, 0.3 m in the shown example, buried in
the subsurface. The distance between the sphericals
is small with respect to the dominang wavelength
λ. The dielectric structure of the buried
spheres is mapped into the electric field observed
on the surface.
Outlook/Future work The code will be used
in order to study more complicated underground
structures; in particular we want to investigate
synthetical radargram generation in order to compare
those to measured radargrams. We will use
dielectric material properties measured from real
soil [Oswald et al. , 2006] to obtain a realistic
model. This will be one of the first steps towards
the challenge of GPR full-wave inversion.
Main publication Oswald et al. [2006]

134 CHAPTER 3. TERRESTRIAL SYSTEMS
3.1.13 Simulation and Observation of an Evanescent Wave in Ground Penetrating
Radar Applications
Participating scientist Holger Gerhards, Benedikt Oswald
Abstract A radiating dipole near a single boundary layer was simulated to observe air and ground
wave occurring in Ground Penetrating Radar applications. A semi-analytical approach to solve
Maxwell’s equations in frequency domain with Green’s functions was used. The evanescent characteristic
of the ground wave in air was demonstrated theoretically and experimentally.
x
air
soil
(4)
(3)
(1)
antenna
z
(2)
Background Ground Penetrating Radar
(GPR) is a fast and nondestructive electromagnetic
method to do near subsurface explorations
to estimate soil water content. Reflections are
measured, which occur at boundaries with a dielectric
contrast. Because the relative dielectric
permittivity (εw ≈ 81) of water is much higher
than the soil matrix (εs ≈ 3) in the used frequency
range between 0.1 to 1.0 GHz and assuming that
high water content changes coincides with soil
layers, temporal changes of water content can be
easily detected analyzing travel times.
As shown in Fig. 3.13 for a two layer (air/soil)
model a direct wave from transmitter to receiver
in air and another in the soil can be observed. The
measured ground wave in the air has an evanescent
character, which means, that its amplitude
decays exponentially with the height of the receiving
antenna over the soil. The knowledge about
this phenomena can help to separate the interfering
air and ground waves or to obtain information
about the dielectric properties of the soil surface.
Funding DFG RO 1080 / 10-1
Methods and results A radiating dipole
within a two layer medium was modeled using a
semi-analytical approach based on a spectral decomposition
of the Green’s functions in frequency
domain. The obtained electric field components
were transformed into time domain to be able to
compare the simulation with field measurements.
Figure 3.13: Propagation modes at a single
boundary layer; (1) and (2) spherical wave like
propagation modes in the according material,
(3) ground wave coupling in air (evanescent
wave), (4) air wave coupling in soil (lateral/head
wave)
The exponential decay and its frequency dependence
can be shown by analyzing the amplitudes
of the ground wave wavelet and its shape with
increasing height above the soil.
Analogous to the simulation experiments were
arranged, where the evanescent behavior of the
ground wave was verified and therefore validates
the semi-analytical approach. Furthermore, it was
shown, how far the ground wave interferes with
the air wave.
To obtain insight on the parameters that determine
the attenuation, an equation was derived
from the plane wave approach used in optics. The
dependency on frequency and dielectric contrast
was obtained, which can be qualitatively shown
with the simulated and measured time signals.
Outlook/Future work A frequency analysis
must be applied to check the derived frequency
dependence for experimental data. If air and
ground waves interfere with each other, a quantitative
separation must be developed, such as using
a wavelet analysis. Furthermore, the semianalytical
approach will be extended to simulated
multilayered models, which may help to understand
the depth-dependency of the ground wave
when a near subsurface water content gradient exists.
Main publication Gerhards, Holger, Diplomarbeit,
Universität Jena, 2004

3.1. SOIL PHYSICS 135
References
Bayer, A. 2005. X-ray attenuation techniques to explore the dynamics of water in porous media. PhD
thesis, University of Heidelberg.
Bayer, A., Vogel, H.-J., & Roth, K. 2004. Direct measurement of the soil water retention curve
using X-ray absorption. Hydrology and Earth System Sciences Discussion, 8(1), 2–7, SRef–ID:
1607–7938/hess/2004–8–2.
Bayer, A., Vogel, H.-J., Ippisch, O., & Roth, K. 2005. Do effective properties for unsaturated weakly
layered porous media exist? An experimental study. Hydrology and Earth System Sciences Discussion,
2, 1087–1105, SRef–ID: 1812–2116/hessd/2005–2–1087.
Bittelli, M., Flury, M., & Roth, K. 2004. Use of dielectric spectroscopy to estimate ice content in
frozen porous media. Water Resour. Res., 40, W04212, doi:10.1029/2003WR002343.
Braun, H., Christl, M., Rahmstorf, S., Ganopolski, A., Mangini, A., Kubatzki, C., Roth, K., &
Kromer, B. 2005. Possible solar origin of the 1,470-year glacial climate cycle demonstrated in a
coupled model. Nature, in press, doi: 10.1038/nature04121.
Herzog, A. 2005. Free Parameterisation of Soil Hydraulic Properties. Diplomarbeit, University of
Heidelberg.
Leidenberger, P., Oswald, B., & Roth, K. 2005. Efficient Reconstruction of dispersive dielectric profiles
using Time Domain Reflectometry (TDR). Hydrology and Earth System Sciences Discussion, 1449–
1502.
Ohtsu, M, & Kobayashi, K. 2004. Optical Near Fields. 1 edn. Advanced Texts in Physics. Berlin -
Heidelberg: Springer.
Oswald, B., & Roth, K. 2005a. Electromagnetic full wave analysis of sub-wavelength sized objects in
ground penetrating radar (GPR). Page 04437 of: Geophysical Research Abstracts, vol. 7. European
Geosciences Union, EGU, Vienna.
Oswald, B., & Roth, K. 2005b. A full-wave numerical model for the interaction of L-band electromagnetic
radiation with a simplified forest-like vegetation. Page 06741 of: Geophysical Research
Abstracts, vol. 7. European Geosciences Union, EGU, Vienna.
Oswald, B., Doetsch, J., & Roth, K. 2006. A new computational technique for procesing transmission
line measurements to determine dispersive dielectric properties. Geophysics. accepted for
publication.
Oswald, Benedikt, & Roth, Kurt. 2005c. Parallel 3D Finite Element Time Domain Maxwell Solver
- Investigation of Ground Penetrating Radar Sub-Wavelength Resolution. Paul Scherrer Institut,
Villigen. 2005, August, 25.
Roth, K. 2005a. Bodenwasser: Bedeutung – Herausforderung – Messung. Eröffnungsvortrag, Soil
Moisture Group, Universität Karlsruhe, 8. Juni.
Roth, K. 2005b. GPR zur Quantifizierung von Transportprozessen in Böden? Institut für Geophysik,
Universität Kiel, 20. Mai.
Roth, K. 2005c. Measurement and Modeling of Thermal and Hydraulic Dynamics of Permafrost Soils.
Dept. of Earth Sciences, Uppsala University, March 31.
Roth, K., & Wollschläger, U. 2005. Field-Scale Measurement of Soil Water Content. Plenary Session
at International Conference on Human Impacts on Soil Quality Attributes, Isfahan, Iran, September
12–16.
Roth, K., Schulin, R., Flühler, H., & Attinger, W. 1990. Calibration of time domain reflectometry
for water content measurement using a composite dielectric approach. Water Resour. Res., 26(10),
2267–2273.
Roth, K., Wollschläger, U., Cheng, Z., & Zhang, J. 2004. Exploring Soil Layers and Water Tables
with Ground-Penetrating Radar. Pedosphere, 14(3), 273–282.

136 CHAPTER 3. TERRESTRIAL SYSTEMS
Roth, K., Boike, J., & Vogel, H.-J. 2005. Quantifying Permafrost Patterns using Minkowski Densities.
Permafrost and Periglacial Processes, 16, 277–290, doi: 10.1002/ppp.531.
Stöhr, M., & Roth, K. 2005. Gradient-based estimation of local parameters for flow and transport in
heterogeneous porous media. Water Resour. Res., 41, 1–14, W08401, doi:10.1029/2004WR003768.
Topp, G. C., Davis, J. L., & Annan, A. P. 1980. Electromagnetic determination of soil water content:
Measurement in coaxial transmission lines. Water Resour. Res., 16, 574–582.
Ulbrich, C. 2005. Monitoring Field Tracer Experiment with Ground Penetrating Radar and Time
Domain Reflectometry. Diplomarbeit, University of Heidelberg.
Vogel, H.-J. 2005a. From Pore- to Continuum-Scale Understanding of Flow and Transport Processes
in Porous Media. Keynote paper, SSSA-Annual Meeting, November 7-11, 2005, Salt Lake City,
USA.
Vogel, H.-J. 2005b. Hierarchies of flow and transport in soil. Keynote paper, GFHN, 29emes journees,
November 24-25, 2004, Grenoble, France.
Vogel, H.-J. 2005c. Modeling the heterogeneous structure of soil to predict flow and transport. SIAM
Conference on Mathematical and Computational Issues in the Geosciences, June 7-10, 2005, Avignon,
France.
Vogel, H.-J., Tölke, J., Schulz, V. P., Krafczyk, M., & Roth, K. 2005a. Comparison of a Lattice-
Boltzmann Model, a Full-Morphology Model, and a Pore Network Model for Determining Capillary
Pressure-Saturation Relationships. Vadose Zone J., 4, 380–388, doi: 10.2136/vzj2004.0114.
Vogel, H.-J., Cousin, I., Ippisch, O., & Bastian, P. 2005b. The dominant role of structure for
solute transport in soil: Experimental evidence and modelling of structure and transport in a
field experiment. Hydrology and Earth System Sciences Discussion, 2, 2153–2181, SRef–ID: 1812–
2116/hessd/2005–2–1.
Vogel, H.-J., Samouelian, A., & Ippisch, O. 2005c. Modeling structure to predict flow and transport.
Gesellschaft für Angewandte Mathematik und Mechanik, 76th Annual Scientific Conference, March
28 - April 1, 2005, Luxembourg.
Vogel, H.-J., Hoffmann, H., & Roth, K. 2005d. Studies of crack dynamics in clay soil. I. Experimental
methods, results, and morphological quantification. Geoderma, 125, 203–211.
Vogel, H.-J., Hoffmann, H., Leopold, A., & Roth, K. 2005e. Studies of crack dynamics in clay soil.
II. A physically based model for crack formation. Geoderma, 125, 213–223.
Wollschläger, U., & Roth, K. 2004. Estimating the three-dimensional hydraulic structure of soils from
ground-penetrating radar measurements. Pages 501–504 of: Proceedings of the 10th International
Conference on Ground Penetrating Radar, Delft.
Wollschläger, U., & Roth, K. 2005. Estimation of temporal changes of volumetric soil water content
from ground-penetrating radar reflections. Subsurf. Sens. Technol. Appl., 6(2), doi: 10.1007/s11220–
005–0007–y.
Yu, Q., Shi, C., Niu, F., He, N., & Roth, K. 2005. Analysis of temperature controlled ventilated
embankment. Cold Reg. Sci. Technol., 42, 17–24, doi:10.1016/j.coldregions.2004.11.004.

3.2. ICE AND CLIMATE 137
3.2 Ice and Climate
Names of group members
Isabel Bengel, diploma student
Felix Jahn, diploma student
Barbara May, diploma student
Christine Offermann, diploma student
Dipl.Phys. Markus Pettinger, PhD student
Dipl.Phys. Martin Schock, PhD student
Dr. Dietmar Wagenbach, head of group
Overarching topic, main methods and specific objectives Among all paleo-archives, only
non-temperated glaciers basically allow the reconstruction of climate as well as of environmental
records. Appropriate ice core studies may thus allow to tackle the crucial problem about the mutual
relationships between changes of climate and bio-geochemical cycles through a retrospective approach.
Figure 3.14: Drilling down to bedrock at Colle Gnifetti (Monte Rosa 4500m a.s.l.) September 2005.
View on the exposed situation of the drill camp near the ice-cliff (dome drilling tent at upper right
rim). Picture: Olaf Eisen
In this context, the ’Ice and Climate’ group concentrates on ice core investigations by deploying the
following species, backed up by standard physical ice properties:
• water-isotopomeres δ 18 O- δD (thermometry)
• various particulate key species as mineral dust, major ions, organic carbon (bio-geochemical
cycles),
• natural radionuclides as terrestrial 210 Pb, cosmogenic 10 Be, 3 H, 36 Cl (solar variability)and on
3 He, 4 He isotopes (basal layer dynamics).
Apart from joint activities within polar ice core studies, emphasis is thereby on the independent
exploration of non-temperated alpine glaciers. Such small scale drill sites are unique in supplementing
high latitude ice core findings, though reliable atmospheric signals would be much more difficult
to elucidate here (Preunkert et al., 2000). In addition to ice core analyses, deserving application
of novel techniques and species (Ruth et al., 2003), also process-oriented field studies are regularly
performed. These specific activities are aimed at understanding the transfer of the atmospheric signals
into the glacier archive as well as at constraining their basic glaciological embedding conditions (as e.g.

138 CHAPTER 3. TERRESTRIAL SYSTEMS
controlled by the near surface and near bed-rock glacier dynamics). Based on external collaborations,
dedicated atmospheric observations are deployed here at various alpine (Preunkert and Wagenbach,
1998) and Antarctic sites (Wagenbach et al. 1998, Piel et al. 2005, which also include isotopic
fingerprints of aerosol samples ( 15 N, 14 C, 26 Al). Within the glaciological issue, joint efforts range
from ground penetrating radar soundings of the internal stratigraphy in alpine glaciers (Eisen et al.
2003) and related glacio-meterological and glacio-chemical surveys, to the prospection of novel dating
techniques ( 3 He/ 4 He (Friedrich, 2003), 14 C, 26 Al/ 10 Be).
Overview on principal activities and achievements
Alpine research
a) EU- ALP-IMP related: Long term isotope records from two deep Mt. Blanc cores could be added
to the already existing array of respective Monte Rosa records, enhancing the significance in the
reconstruction of climate related changes (see 3.2.4). Site selection study of ideal drill site for high
resolution records back to 1000 years by radar tracking of the internal layering by University Zürich
(Böhlert, 2005) and drilling there to bedrock in collaboration with KUP of University Bern could be
successfully achieved. First estimates indicate a net surface accumulation of the new site, significantly
lower than 15 cm water per year, which may offer a relatively high time resolution in the bottom
core section. A further intensive field campaign for sampling a special non-temperated ice cap at
lower altitude was performed in collaboration with university Zürich, in order to prospect the basic
stratigraphycal properties of this ice body (see 3.2.1) .
b) EU-CARBOSOL project related: The first continuous records into the pre-industrial area of dissolved
organic carbon (DOC) could be established (partly in seasonal resolution) (see 3.2.5). Also
aimed at the long term change of the organic fraction of the aerosol body, the first radiocarbon investigations
on european wide aerosol samples could be accomplished after final revision of the sample
preparation line (see 3.2.2).
Antarctica
a) Related to EPICA: Field sampling of bottom core for He-isotope analyses could be accomplished
at Berkner Island and at EPICA Dome C (actually the oldest ice available) drill sites. Respective
mass spectrometric analyses by the ”Groundwater and Paleoclimate” group, along with noble gas ice
core samples obtained from the previous campaigns are expected to come up in the near future.
Investigation of the air firn transfer of 10 Be (and associated host particles) were extended from investigations
at the central EPICA DML drill site(Piel et al. 2005) by a bi-annual record from a recent
firn core obtained from coastal Berkner Island. In this context long term observations of atmospheric
radionuclides at Neumayer Station were regularly continued (see 3.2.3).
b)The Lake Vostok: Additional ice samples of the Vostok bottom ice core (accreted from Lake Vostok)
as well as meteoric reference ice were obtained from LGGE-CRNS. Grenoble and analysed for dissolved
organic Carbon, confirming the outstanding low DOC level, already obtained in previous pilot analyses
(Bulat et al.2004) (see 3.2.5)
c) New developments focussed on the extension of automatic aerosol sampling in central Antarctica
and on the prospection of the 26 Al/ 10 Be dating tool, to be deployed for very old ice. (see 3.2.6)
Novel activities envisaged in the following year Launching a radiocarbon dating project focussing
on various non-temperated Alpine ice bodies (with VERA and University Zürich).
Supplementing continuous flow ice core analyses by a screening method for the total gas content, as
to infer the melt-layer stratigraphy (with Groundwater and Paleoclimate Group)
Pilot studies on the Little Ice Age variability of 10 Be possibly archived in a new sediment core recovered
from the well explored high alpine Schwarzsee ob Sölden (with University Innsbruck and Heidelberg
Academy of Sciences)
Re-designing of the Air Chemistry Observatory at the Antarctic Neumayer Station III (with AWI and
the Carbon Cycle Group)
Funding and major cooperations Funding relayed on the EU-projects CARBOSOL (Anthropogenic
change of organic carbon aerosol in West- Europe)and ALP-IMP (Climate variability in the
greater Alpine region), the AWI-Cooperation contract (Investigation of ice cores and aerosol of polar

3.2. ICE AND CLIMATE 139
regions) and on an Austrian Research Fund project jointly with VERA ( 26 Al- 10 Be investigations). Important
logistical support was obtained from the ESF-EU core project EPICA (European Ice Drilling
in Antarctica).
Vital long term collaborations (also operating outside funding projects) comprised joint activities
with:
• Alfred Wegener Institute for Polar and Marine Research (various polar investigations),
• Laboratoire de Glaciolocique et Geophisique-CRNS, Grenoble (alpine ice cores and Lake Vostok),
• Geographical Institute of the University Zürich (alpine glaciology and glacio-meteorology)
• Klima und Umweltphysik, University Bern (ice core drilling and analyses),
• VERA-laboratory, Institut für Isotopenforschung und Kernphysik der Universität Wien (AMSanalyses)
• Institute for Zoology and Limnology, University Innsbruck (ice biology and high alpine lake
sediments),
• British Antarctic Survey, Cambridge (Berkner Island Project)
• Institute for Environmental Geochemistry, University Heidelberg (trace element analyses)
Internal collaboration concentrates on: the Neumayer Observatory, 14 C and radon investigations
(Carbon Cycle Group), noble gas and tritium analyses (Groundwater and Paleoclimate Group) as
well as on long term marine 10 Be sediment records (Heidelberger Academy of Sciences).
Publications
Peer Reviewed Publications
1. Bulath et al. [2004]
2. Legrand et al. [2005]
3. Piel et al. [accepted]
Other Publications
1. Auer et al. [2005]
2. Bigler et al. [2005]
3. Dombrowski-Etchevers et al. [2005]
4. Pettinger et al. [2005]
5. Schock et al. [2005]
6. Steier et al. [2005]
7. Wegner et al. [2005]
Diploma Theses
1. Bengel [2005]
2. May [2005]
Invited Talks
1. Schock et al. [2005]
2. Pettinger et al. [2005]
3. Wagenbach [2004]

140 CHAPTER 3. TERRESTRIAL SYSTEMS
3.2.1 Glaciological pilot studies on a cold miniature ice cap
Participating scientist Isabel Bengel and Wilfried Haeberli ∗
∗ Glaciology and Geomorphodynamics Group, Geography Department, University of Zürich
Abstract The study deals with the glacio-chemical characterisation of a high alpine miniature ice
cap (Piz Murtèl, 3433 m a.s.l., Oberengadin). Inside an ice tunnel the 210 Pb and 3 H point to
ice, surprisingly less than 50 years old. On the whole, the ice body of Piz Murtèl exhibits a dust
stratigraphy and distinct age distribution, but less regular than in sedimentary ice.
Figure 3.15: Above: Northwest flank of Piz
Murtèl (3300 m a.s.l.) seen after an intense summer
ablation period with indicated 2004 samplings.
Below: Shallow profile of 3 H (T 1/2 =
10.3 a) and 210 Pb (T 1/2 = 22 a) obtained in the
interior tunnel floor, showing surprisingly modern
ice conditions.
Background Different to high alpine cold
glaciers (above 4000 m a.s.l.) the environmental
information, which maybe contained in lower elevation
miniature ice caps remained virtually unknown.
Because of a small mass turnover and low
ice motions in such ice caps a relatively high age
in the order of some 1000 years may be expected
(Haeberli et al., 2004). An alpine prime example
for a miniature ice cap provides the Piz Murtèl
(Oberengadin, Suisse) which is analysed in this
study. Being non-temperate despite its low elevation,
the ice cap might be used as an archive
containing the history of past minimum glacier
extend. The primary aim of this study was to
gather basic information on the internal stratigraphy,
age structure and accumulation processes
by screening the isotope and chemical ice properties.
Methods and results In October 2004, a continous
50 m profile at the northwest flank and a
shallow ice core in an artifical ice tunnel were sampled
in collaboration with University of Zürich.
First measurements of the variability of ice impurities
have been carried out based on fast standard
methods including continous profiling of particles,
liquid conductivity and electrical ice conductivity.
Thereby it turned out, that the mineral dust variability
in the samples – although partly consisting
of superimposed ice and containing ablation
dirt– could be measured without essential modifications.
Also the electrical method generated
reproducible profiles, allowing to record the ice
stratigraphy at a sub-cm resolution. Exemplary
radionuclide analyses gave (as expected) a 210 Pb
down slope increase but surprisingly young ice
of less than 50 years ( 210 Pb and 3 H) inside the
calotte. Although soluble ion components appeared
to be strongly affected by elution, a DOC
level around 200 ppb was found, making dating by
14 C analyses possible. On the whole, the ice of
Piz Murtèl exhibits a dust stratigraphy and spatial
age distribution which is, however, modified
by the untypical properties of the miniature ice
cap, governed by complicated ablation / accumulation
processes.
Outlook/Future work Drilling into and dating
of the basal layer.
Main publication Bengel [2005]

3.2. ICE AND CLIMATE 141
3.2.2 Constraining the anthropogenic fraction of carbonaceous aerosol by
14 C-analysis
Participating scientists Barbara May, Samuel Hammer and Peter Steier ∗
∗ VERA Laboratory, Institut für Isotopenforschung und Kernphysik, Universität Wien
Abstract A sample preparation line for 14 C analysis of aerosol filters for AMS has been revised
and characterised. First analyses revealed that the European carbonaceous aerosol is of mainly recent
origin, while the free tropospheric clean air condition indicates a more fossil contribution.
Figure 3.16: Range of the relative contribution of
fossil carbon seen in aerosol sampled during winter
and summer half years at various mountain sites
(Sonnblick, Austria; Schauinsland, Germany; Puy
de Dôme, France). Note the significantly higher
fossil carbon fraction during the relatively clean
winter conditions.
Background While inorganic aerosols, like sulphate,
are relatively well understood regarding
their anthropogenic sources and related radiative
forcing implications, anthropogenic change of carbonaceous
aerosol and its radiative influence are
virtually unknown. Therefore, we attempted to
quantify the recent versus fossil fraction of total
organic carbon from European wide sampled
aerosol filters by the 14 C approach. Here, 14 C
measurements may allow to quantitatively distinguish
between the fossil fraction, completely free
of 14 C, and the recent one, carrying the present
day 14 C signature of biogenic carbon. The low
carbon mass and various fractionation processes
associated with aerosol sample combustion make
however thorough experimental efforts necessary
to achieve reliable 14 C results.
Funding EU CARBOSOL-project: Present
and retrospective state of organic versus inorganic
aerosol over Europe: Implications for climate
Methods and results For analysing the 14 C
signature of aerosol filters, a pilot system for controlled
sample combustion in a gas stream and
subsequent purification and extraction of the CO2
(designed by Hammer (2003)) for δ 13 C and AMS
14 C analysis (Steier et al, 2004) was optimised and
characterised. It was shown, that the combustion
process efficiency increases when pure oxygen is
used as combustion gas. Furthermore a water cold
trap is necessary in excess as well as a second combustion
step (assuring the total combustion of the
organic matter). The system allows to reasonably
quantify a minimal carbon amount of 65 µgC
with an accuracy of 10 %. The typical blank level
of the entire process is found to be 63 µgC with
a 14 C content close to 80 pmC (percent modern
Carbon).
A first systematic investigation of CARBOSOL
aerosol filters, specifically selected by 210 Pb data,
indicated: (1) Around 75 % of the carbonaceous
aerosol is released by non-fossil sources, which appear
to be rather uniformly distributed over Western
Europe. (2) Under free tropospheric clean air
conditions nearly one third of the carbonaceous
aerosol may be ascribed to fossil sources (see Figure).
An attempt to interpret these results in
terms of anthropogenic emissions, considering the
variable amount of bomb 14 C added by biomass
burning, proved to be difficult.
Outlook/Future work The system basically
allows the separation of BC (black carbon) and
OC (organic carbon), which may improve the interpretation
in terms of anthropogenic emissions.
Furthermore, upcoming ice core based CAR-
BOSOL results of pre-industrial organic aerosol
concentrations may allow an independent comparison
of the anthropogenic contribution to present
day organic aerosol levels.
Main publication May [2005]

142 CHAPTER 3. TERRESTRIAL SYSTEMS
3.2.3 Recent variability of the cosmogenic nuclides 10 Be and 7 Be in coastal
Antarctica
Participating scientists Christine Offermann, Matthias Auer ∗ and Robert Mulvaney ∗∗
∗ VERA Laboratory, Institut für Isotopenforschung und Kernphysik, Universität Wien
∗∗ British Antarctic Survey, Cambridge
Abstract The solar activity proxy 10 Be is investigated in a firn core of coastal Antarctica (Berkner
Island) along with the 10 Be and 7 Be activities, obtained from aerosol filters at Neumayer station.
Data evaluation is aimed at assessing the air-firn transfer of 10 Be.
Background Cosmogenic 10 Be archived in polar
ice sheets provides an unique tool in reconstructing
solar activity changes. Dueto various
glacio-meteorological noise, the interpretation of
those, latitude dependant, records remained however
ambiguous . Moreover only very few 10 Be ice
core findings are available from the recent (preinstrumental)
era. In this context IUP started investigating
10 Be in relatively recent ice-cores from
different Antarctic drill sites, focussing on the 11year
solar cycle and the outstanding solar minima
of the last 500 years.
As the influence of meteorological noise on 10 Be
is barely understood and strongly depends on the
drill site, investigations at the central Antarctic
EPICA-DML drill site (Wegner 2003, Wegner
et al. 2005) were extended to a coastal site at
Berkner Island (BI) (Rohlfs, 2004). In the coastal
area, also atmospheric long term observations of
7 Be and 10 Be are performed by IUP at Neumayer
(NM) Station, allowing comparison with concurrent
10 Be firn core data with respect to the 11-year
cycle.
Methods and results In this thesis the still
missing high resolution 10 Be firn record from
coastal Antarctica should be provided by establishing
a continuous bi-annual 10 Be profile from a
firn core drilled for this purpose at BI. To study
the glacio-meteorological influence on the air-firn
transfer of 10 Be, the aerosol time series from NM
was extended by the 2004 values of 7 Be concentrations
and completed by missing 10 Be data of
the previous years. The challenge to gain an absolute
core chronology was accomplished by combining
δ 18 O and Electric Conductivity Measurement(ECM)
based acidity profiling, taking advantage
of the seasonal variation of the data. Moreover,
to employ the VERA (AMS) facility, our
10 Be target-preparation procedure has been revised
with respect to the final BeO handling.
∆ 7 Be [fCi/scm]
100
50
0
-50
7 Be at Neumayer Station, Antarctica
1985 1990 1995 2000 2005
year
Figure 3.17: Deviation of monthly mean atmospheric
7 Be activity from the total mean of 112
fCi/m 3 . Note the regular variation related to the
seasonal cycle. Black line: SSA derived extraction
of the underlying Schwabe cycle.
While inspection of the atmospheric 7 Be record
reveals the expected Schwabe cycle, also found
at EPICA-DML, very recently obtained 10 Be raw
data from BI does not show such prominent regular
changes for the first 30 years. The reason for
this discrepancy is not elucidated yet.
Final work Correction for interannual snow accumulation
and revision of the core chronology is
envisaged to gain a useful record of the short term
10 Be variability at BI. Only then comparison with
concurrent changes at EPICA-DML, NM and neutron
monitor data would be possible. Thus, subsequent
analysis for recent trends may show if the
expected decrease (Solanki et al, 2004) due to high
solar activity can be found in the 10 Be record.
Main publications Upcoming diploma thesis

3.2. ICE AND CLIMATE 143
3.2.4 Climatic significance of stable water isotope records from Alpine ice
cores.
Participating scientists Markus Pettinger, Susanne Preunkert ∗ , Ralph Böhlert ∗∗ and Reinhard
Böhm ∗∗∗
∗ LGGS - CNRS, Grenoble
∗∗ Glaciology and Geomorphodynamics Group, Department of Geography, University of Zürich
∗∗∗ ZAMG, Wien
Abstract Upstream effects associated with local variations in snow deposition that influence long
term isotopic trends recorded in Alpine ice cores were investigated. Isotope records of two Mont Blanc
ice show the recent warming trend with high isotope sensitivity, whereas long term records show only
weak correlation with instrumental temperature data.
Figure 3.18: δ 18 O- records of a low
(0.2 m w.e./yr, middle) and a high
(1.1 m w.e./yr, bottom) accumulation core
from the Mont Blanc summit range.
Background Isotope δ 18 O and δD records from
high Alpine cold glaciers may provide complementary
records to polar cores, including the unique
possibility to extend the 250 years instrumental
climate time series only available from western
Europe (Schöner et al., 2002). On the other
side various glaciological constrains hamper the
straightforward interpretation of alpine isotope
records in terms of temperature changes. A multicore
study was therefore set up to partly compensate
for this basic shortcoming.
Funding EU-project ALP-IMP (Multicentennial
climate variability in the Alps based on
Instrumental data, Model simulations and Proxy
data)
Methods and results To determine systematic
upstream effects in the cachment area of
Monte Rosa deep ice cores three shallow firn cores
have been drilled along their flow line down to a
reflection layer determined by radio echo sounding
(as to guarantee an common time span). The
systematic change in the core mean δ 18 O value
along the flow line has been used to improve the
overall upstream corrections. The new data exhibit
in the upper region of the flowline a linear
δ 18 O-accumulation relation of 1.9 � per m water
equivalent. Thus, additional corrections up to
0.4� to those of Keck (2001) are necessary for
the long term trends recorded in Monte Rosa ice
cores. A different approach was chosen for the
Mont Blanc ice core in flank position. In this case,
the changes with depth of the winter snow fraction
induced by wind erosion was determined, but
only an insignificant dependance with depth could
be found.
In the time span of 1920 to 1995 both new Mont
Blanc ice cores show no clear correlation with instrumental
temperature, wich may be due to poor
dating. In contrast the recorded recent warming
trend (1980-2000) exhibits ∆δ 18 O/∆T relations
between 1.5 and 3 �/ ◦ C with high significance
in all ice cores. Previous studies show a relation
of 1.7 �/ ◦ C in the period of 1920 to 1995. Different
to existing Monte Rosa records showing an
odd long term trend towards lower isotope values
into the medieval era, the new Mont Blanc ice divide
core exhibits no such trend, but, if any, only
a weak δ 18 O increase by 0.6�. The respective
ice core chronology as based on a flow only model
(Raymond, 1983) is however still uncertain.
Future work Dating and isotopic analysis of
the new Monte Rosa ice core, drilled to get high
resolution records. In addition the model based
dating of the low accumulation Mont Blanc ice
core has to be improved by matching with known
dust and volcanic horizons.
Main publication Pettinger et al. [2005]

144 CHAPTER 3. TERRESTRIAL SYSTEMS
3.2.5 Analyses of dissolved organic carbon (DOC) at low levels in Alpine
and polar glaciers
Participating scientists Martin Schock, Steffen Greilich ∗ and Jean-Robert Petit ∗∗
∗ Heidelberger Akademie der Wissenschaften, Forschungsstelle Archaeometrie
∗∗ LGGE-CNRS, Grenoble
Abstract Deploying a novel method for ultra-low DOC analysis, DOC in high Alpine precipitation
was found to be increased by a factor of 2-4 (to up to 4 · 10 −7 gC/g) since preindustrial times, wheras
DOC level less than about 10 −8 gC/g are seen in Antarctic ice cores.
Background The bulk quantity DOC constitutes
an important part of the impurity content
of non-temperated glaciers. Related retrospective
studies would be highly relevant therefore in terms
of radiative forcing, past atmospheric carbon cycles
and englacial microbial activity. However no
systematic ice core analyses of DOC were available,
yet, due to unsolved contamination problems
and insufficient sensitivity of conventional TOC
analysers. In this context a dedicated flow injection
system, based on UV induced DOC degregation
has been developed (along with an appropriate
decontamination procedure as to cope with the
challenge to analyse ice cores, drilled in kerosene
filled bore holes).
Funding EU-CARBOSOL project : ”Present
and Retrospective State of Organic versus Inorganic
Aerosol over Europe : Implications for Climate”
Methods and results Sample decontamination,
(deploying partial melting or a melting
probe) is shown to control the precision and
quantitative detection limit (presently around
5 · 10 −9 gC/g). Extensive comparison with a high
temperature combustion method revealed that the
UV degradation efficiency for most of the relevant
DOC species seems to be close to 90% .
Various high Alpine ice cores have been systematically
analysed for DOC (partly in seasonal resolution),
indicating a significant change by typically
a factor of 2 to 4 since the pre industrial era.
This presumably anthropogenic effect is however
clearly lower, compared to concurrent changes of
man made inorganic species, like sulphate (Preunkert
et al., 2001).
DOC-surveys of a cold, low elevation Alpine ice
cap (Bengel, 2005), in view of radiocarbon dating
of the ice body genesis via DOC indicated, that
about 1 kg ice would be needed for this purpose.
Most difficult in terms of reliable measurements
have been Antarctic ice cores, where DOC levels
approach the limit of detection. Including polar
ice cores, no big difference is seen in the pre
industrial DOC level between Alpine and Greenland
sites, wheras an interhemispheric difference
by one order of magnitude shows up with respect
to Antarctica. Here, DOC analyses in accreted ice
from Lake Vostok gave a mean DOC level lower
by roughly a factor of 50, than previously reported
by Priscu et al., (1999), giving much less room for
viable micro biological activities, than hitherto assumed
(Bulat et al 2004).
Figure 3.19: Range of dissolved organic carbon
(DOC) content in various ice bodies (including accreted
ice from Lake Vostok), displayed by median
as well as by 25% and 75% percentils, respectively
Outlook/Future work Radiocarbon dating of
the DOC fraction in Alpine ice.
Main publication J.-R. Petit , J. Flückiger, M.
Leuenberger, W. Haeberli, R. Psenner , Dissolved
organic carbon (DOC) in ice samples from nontemperated,
polar and Alpine glaciers. Geophysical
Research Abstracts, Vol. 7, 08671, 2005
Schock et al. [2005]

3.2. ICE AND CLIMATE 145
3.2.6 Novel tools in ice core research
Participating scientists Dietmar Wagenbach, Rolf Weller ∗ and Matthias Auer ∗∗
∗ AWI-Bremerhaven
∗∗ VERA Laboratory, Institut für Isotopenforschung und Kernphysik, Universität Wien
Abstract New developments on automatic aerosol sampling in central Antarctica and on the prospection
of the 26 Al/ 10 Be dating tool are reported along with their futur application.
Figure 3.20: Seasonal cycle of biogenic sulfate in central Antarctica obtained by automatic aerosol
samplings (left), first tropospheric 26 Al/ 10 Be ratios derived from Antarctica Neumayer (Ant), alpine
Sonnblick (SBO) and Schauinsland (SIL) Station (right).
Background Among various shortcomings in
the interpretation of Antartic ice core records,
the air-firn transfer of aerosol species as well as
the age and stratigraphical properties of the basal
core sections continue to provide outstanding challenges.
On the one hand, this is mainly due to
missing year round atmospheric aerosol observations
at central Antartic drill sites and on the
other, due to the missing of appropriate dating
tools reaching back beyond several 100ka. a) In
order to reduce the first deficit IUP developed an
autonomous aerosol sampling device (ROBERTA)
(Preunkert and Wagenbach 1998) to be deployed
year round at the EPICA-DML drill site in the
Atlantic sector of east Antartica. b) In close collaboration
with the University of Vienna AMS facility
(VERA) the dating deficit of very old ice
samples has been tackled by exploring the feasibility
of the 26 Al/ 10 Be ratio (apparent T 1/2 =1.3
10 −6 a) as a radiometric chronometer.
Fundings a) AWI-Cooperation Contract, b)
joint project within the Austrian Research
Fund(FWF).
First results a) Year round, unattended running
of the aerosol sampling system could be successfully
achieved in close collaboration with AWI-
Bremnerhaven, providing first records on the seasonal
change of major ion in central Antarctica.
26 Al/ 10 Be
3x10 -3
2x10 -3
1x10 -3
0
ANT
SBO
Adding ion concentration data in sub-seasonal resolution
from concurrent firn deposits along with
automatic snow hight recordings may now allow to
elucidate the drill site specific air-firn transfer of
the ionic aerosol species. A second sampler version
substantially improved with respect to the
consecutive activation of the sampling units has
been put in operation.
b) After establishing and optimizing the 26 Alanalysis,
first tropospheric 26 Al/ 10 Be ratios could
be obtained from Antarctic and mid-latitude
aerosol samples. The reasonable constant ratios
indicate a control by atmospheric production,
rather than by terrestrial or cosmic dust inputs
(which is a pre-requisite for the dating application).
Future work a) Possibly deploying one of the
two devices at a high altitude drill site in the western
Himalayans (Pamir).
b) 26 Al/ 10 Be analyses will be extended to recent
polar snow and glacial ice core samples and supplemented
by 53 Mn (solely derived from interplanatary
dust) as to obtain a quantative estimate
of the IPD influence on the 26 Al variability in polar
ice cores. If successful 26 Al/ 10 Be dating might
be applied the first time on ice core samples (e.g.
on the basal section of the EPICA Dome C core,
which comprises the oldest ice recovered so far).
Main publication Auer et al. [2005]
SIL

146 CHAPTER 3. TERRESTRIAL SYSTEMS
References
Auer, M., Kutschera, W., Priller, A., Wagenbach, D., Wallner, A., & Wild, E. M. 2005 (September
5-10). Atmospheric 26 Al and 10 Be as a dating tool for climate archives (Abstract). vol. The 10th
International Conference on Accelerator Mass Spectrometry Berkeley, California.
Bengel, I. 2005. Spurenstoffglaziologische Pilotuntersuchungen an einer kalten Miniatureiskappe.
Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg.
Bigler, M., Röthlisberger, R., Ruth, U., Siggaard-Andersen, M.-L., Steffensen, J. P., Hansson, M. E.,
Goto-Azuma, K., Fischer, H., & Wagenbach, D. 2005. A new high-resolution chemical ice core
record over the last glacial period from NGRIP. Geophysical Research Abstracts, Vol 7, 05616.
Böhlert, R. 2005. Diplomarbeit, Institut für Geographie, Universität Zürich.
Böhm, R., Brunetti, M., Maugeri, M., Nanni, T., & Schöner, W. 2001. Regional temperature variability
in the European Alps: 1760-1998 from homogenized instrumental time series. International
Journal of Climatology, 21, 1779 – 1801.
Bulath, S., Alekhina, I., Blot, M., Petit, J.-R., de Angelis, M., Wagenbach, D., Lipenkov, V., Valilyeva,
L., Wloch, D., Raynaud, D., & Lukin, V. 2004. DNA singature of thermophilic bacteria from the
aged accretion ice of Lake Vostok, Antarctica: implications for searching for life in extreme icy
environments. International Journal of Astrobiology, 3(1), 1–12.
Dombrowski-Etchevers, I., Peuch, V.-H., Wagenbach, D., & Legrand, M. 2005. Validation of concentrations
of lead-210 in high altitude simulated by MOCAGE. Geophysical Research Abstracts, Vol
7, 09009.
Eisen, O., Nixdorf, U., Keck, L., & Wagenbach, D. 2003. Alpine Ice Cores and Ground Penetrating
Radar: Combined Investigations for Glaciological and Climatic Interpretations of a Cold Alpine Ice
Body. Tellus, 55B(5), 1007–1017.
Friedrich, R. 2003. Helium in polaren Eisschilden. Diplomarbeit, Instiut für Umweltphysik, Universität
Heidelberg.
Haeberli, W., Frauenfelder, R., Kääb, A., & Wagner, S. 2004. Characteristics and potential climatic
significance of ”miniature ice caps” (crest- and cornice-type low-altitude ice archives. Journal of
Glaciology, 50(168), 129–136.
Hammer, S. 2003. Einsatz von Radioisotopen zur Interpretation der raum-zeitlichen Variabilität von
organischem Aerosol. Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg.
Keck, L. 2001. Climate significance of stable isotope records from Alpine ice cores. Ph.D. thesis,
Institut für Umweltphysik, Universität Heidelberg.
Legrand, M., Preunkert, S., Galy-Lacaux, C., Liousse, C., & Wagenbach, D. 2005. Atmospheric yearround
records of dicarboxylic acids and sulfate at three French sites located between 630 and 4360
m elevation. Journal of Geophysical Research, 110, D13302, doi:10.1029/2004JD005515.
May, B. 2005. Quantification of the fossile fraction of carbonaceous aerosol by radiocarbon analysis.
Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg.
Pettinger, M., Keck, L., Fischer, H., Wagenbach, D., Preunkert, S., Böhm, R., Hoelzle, M., & Hoffmann,
M. Leuenbergerand G. 2005. Cenntennial scale isotope thermometry from Alpine ice core
records: shortcomings and challenge. Geophysical Research Abstracts, Vol 7, 07941.
Piel, C., Weller, R., M.Huke, & Wagenbach, D. accepted. Atmospheric methane sulfonate and non-sea
salt sulfate records at the EPICA deep-drilling site in Dronning Maud Land. Journal of Geophysical
Research, 2005JD006213.
Preunkert, S., & Wagenbach, D. 1998. An automatic recorder for air/firn transfer studies of chemical
aerosol species at remote glacier sites. Atmospheric Environment, 23, 4021–4030(10).
Preunkert, S., Wagenbach, D., Legrand, M., & Vincent, C. 2000. Col du Dome (Mont Blanc Massif,
French Alps) suitability for ice core studies in relation with past atmospheric chemistry over Europe.
Tellus, 52B, (3), 993–1012.

3.2. ICE AND CLIMATE 147
Preunkert, S., Legrand, M., & Wagenbach, D. 2001. Sulfate trends in a Col du Dome (French Alps) ice
core : A record of anthropogenic sulfate levels in the European midtroposphere over the twentieth
century. Journal of Geophysical Research, 106, 31991–32004.
Priscu, J., Adams, E., Lyons, W., Voytek, M., Mogk, D., Brown, R., McKay, C., Takacs, C., Welch,
K., Wolf, C., Kirshtein, J., & Avci, R. 1999. Geomicrobiology of Subglacial Ice Above Lake Vostok,
Antarctica.
Raymond, C. F. 1983. Deformation in the vicinity of divides. Journal of Glaciology, 34, 357–373.
Rohlfs, J. 2004. Zeitliche Variation von 10 Be in der Küstenantarktis - Eine Eiskernzeitreihe von
Berkner Island. Diplomarbeit. Institut für Umweltphysik, Universität Heidelberg.
Schock, M., Greilich, S., Wagenbach, D., Preunkert, S., Legrand, M., Petit, J. R., Flückiger, J.,
Leuenberger, M., Haeberli, W., & Psenner, R. 2005. Dissolved organic carbon (DOC) in ice samples
from non-temperated, polar and Alpine glaciers. Geophysical Research Abstracts, Vol. 7, 08671.
Schöner, W., Auer, I., Böhm, R., Keck, L., & Wagenbach, D. 2002. Spatial representativity of air
temperature information from instrumental and ice core based isotope records in the European
Alps. Annals of Glaciology, 35, 157–161.
Solanki, S. K., Usoskin, I. G., Kromer, B., Schüssler, M., & Beer, J. 2004. Unusual activity of the
Sun during recent decades compared to the previous 11,000 years. Nature.
Steier, P., Dellinger, F., Kutschera, W., Rom, W., & Wild, E. M. 2004. Pushing the precision limit
of C14 measurements with AMS. Radiocarbon, 46, 969–978.
Steier, P., Drosg, R., Kutschera, W., Wild, E. M., Fedi, M., Wagenbach, D., & Schock, M. 2005.
Radiocarbon determination of particulate organic carbon (POC) in non-temperated, Alpine glacier
ice (Abstract). The 10th International Conference on Accelerator Mass Spectrometry Berkeley,
California, September 5-10, 2005.
Wagenbach, D. 2004. Potential and restrictions of Alpine (mid-latitude) ice cores. Invited talk, SCIEM
2000 (The synchronisation of civilization in the eastern Mediterranean in the 2nd Millenium BC)
Workshop: Ashes and Ice, Vienna.
Wagenbach, D., Ducroz, F., Mulvaney, R., Keck, L., Minikin, A., Legrand, M., Hall, J. S., & Wolff,
E. W. 1998. Sea-salt aerosol in coastal Antarctic regions. Journal of Geophysical Research, 103(D9),
10961–10974, 10.1029/97JD01804.
Wegner, A. 2003. Die Geschichte der Sonnenaktivität im Antarktischen Eis Nachweis produktionsbedingter
10 Be - Schwankungen. Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg.
Wegner, A., Rohlfs, J., Huke, M., Stanzick, A., Wagenbach, D., Oerter, H., Sommer, S., Mulvaney,
R., & Kubik, P. 2005. Bi-annual to decadal 10 Be variability in firn cores from Dronning Maud Land
(DML) and Berkner Island (BI), Antarctica. Geophysical Research Abstracts, Vol 7, 08396.

Aquatic Systems
4.1 Groundwater and Paleoclimate . . . . . . . . . . . . . . . . . . . . . . . . 151
4.2 Lake Research (Limnophysics) . . . . . . . . . . . . . . . . . . . . . . . . 161
149

4.1. GROUNDWATER AND PALEOCLIMATE 151
Overview
The research group ”Aquatic Systems” investigates freshwater systems, in particular lakes and groundwater,
using direct measurements of physical parameters as wells as tracer and isotope methods. The
fundamental goal of this research is to obtain a better understanding of the physical processes in these
systems. Examples of studied processes are vertical turbulent mixing, currents, and tracer transport
in stratified lakes, or recharge, flow, dispersion and contaminant transport in aquifers. A further important
field is the use of aquifers as paleoclimate archives. The wider context of our research includes
the issues of water resources protection and management, and assessment of past and present climate
change.
The group is divided in two subgroups: ”Groundwater and Paleoclimate” and ”Limnophysics”.
4.1 Groundwater and Paleoclimate
Names of group members
Prof. Werner Aeschbach-Hertig, head of group
Dr. Reinhold Bayer, administration
Dr. Hany El-Gamal, PhD-student (completed June 2005)
Dipl. Phys. Ronny Friedrich, PhD-student
Dipl. Phys. Rainer Klement, diploma student (completed February 2005)
Dipl. Phys. Tobias Kluge, PhD-student
Dipl. Phys. Andreas Kreuzer, PhD-student
Dr. Laszlo Palcsu, postdoc
M. Sc. Sarah Rice, master student (completed December 2004)
Dipl. Phys. Katja Träumner, diploma student (completed November 2005)
Martin Wieser, diploma student
Dipl. Ing. Gerhard Zimmek, technician
Abstract The research group ”Groundwater and Paleoclimate” deals with applications of isotope
and environmental tracers, in particular noble gases, in groundwater (and lakes in collaboration with
the Limnophysics group). With theses methods, the group pursues two main aims: 1. To provide foundations
for a sustainable management of groundwater resources, 2. Reconstruction of the paleoclimate
since the last ice age.
Background The overarching topic of our research may be summarized as ”isotope hydrology and
climatology”, more specifically the use of isotopes and other environmental tracers (in particular noble
gases) to study the functioning of groundwater systems and to extract paleoclimatic information from
them.
Isotope and tracer techniques have a long tradition in environmental physics. In addition to the widely
used stable isotopes, dissolved noble gases in groundwater have been established as a reliable paleotemperature
proxy. Furthermore, 3 H, He isotopes and other transient gas tracers are important tools
in groundwater dating and recharge assessment [e.g. Kipfer et al. , 2002]. Groundwaters constitute
by far the largest global reservoir of available fresh water. For the sustainable management of these
resources, particularly in arid and semi-arid regions, it is essential to understand on what time-scales
these resources are renewed and how they react to global climate change. Climate change and the
limited availability of water resources are interrelated issues of increasing global importance. Isotopic
studies of groundwaters yield information on both past climatic conditions such as temperature or
aridity and on physical parameters such as residence time or recharge rate. Thus, issues of past climatic
conditions and future availability of groundwater resources can be addressed in an integrated
approach.
Methods A central facility of the group is the newly built mass spectrometric system for the analysis
of noble gases dissolved in water. It is currently becoming operational and will allow measurements
of all stable noble gases from groundwaters for paleotemperature studies as well as the analysis of
He isotopes for 3 H- 3 He dating. This facility is also being used to study new sample types such as
stalagmites. It is complemented by an older system for He isotope analysis and a radiometric 3 H
lab. Furthermore, the group conducts gas chromatographic SF6 analyses in cooperation with the
limnophysics group, and uses the stable isotope and 14 C laboratories of the institute.

152 CHAPTER 4. AQUATIC SYSTEMS
Main activities Projects of the group are related either to questions of water resources or paleoclimate,
or both. Some projects are mainly applications of established methods, whereas others intend
to develop new methods and approaches.
The main goal of a project studying groundwater in the North China Plain is to obtain a noble gas
paleotemperature record from a formerly little studied part of the world (see section 4.1.1). However,
it also involves an investigation of the current recharge to the heavily exploited groundwater resources
of this semi-arid area. Preliminary results of this study showing a clear paleoclimatic signal are being
published in the framework of the IAEA isotope hydrology series [Kreuzer et al. , in press 2005].
Similarly, a project on groundwater in Egypt focusses on the renewal rate of these resources that are
used to sustain new agricultural developments outside the Nile Delta (see section 4.1.2). The study
clearly shows that the regional groundwater originates from the Nile water, but the renewal is very
slow. This project has been a cornerstone of the thesis of Hany El-Gamal [El-Gamal, 2005]. A paper
is in preparation.
Recharge rates and processes are also central to a project focussing on groundwater in the nearby
Odenwald region (see section 4.1.3). However, the main problem in this case is not the overexploitation
of the resource but the incomplete understanding of the connection between recharge in the mountains
and water levels in the valley, where large water works are operating. Progress in this project has
been and will again be reported at meetings of the hydrogeology section of the German Geological
Society [Friedrich et al. , 2004].
A new idea is to try and use microscopic water inclusions in speleothems (stalagmites and other
carbonate sinters) to extract noble gas concentrations and temperatures (see section 4.1.4). After
some preliminary studies in the form of diploma theses [Rice, 2004; Träumner, 2005], this issue is now
studied in the framework of a DFG research unit in collaboration with the Radiometry Group of the
”Heidelberger Akademie der Wissenschaften” (see section 5.1.8). The issue of the analysis of noble
gases on very small samples and in new archives is also central to the project of our Marie Curie
fellow Laszlo Palcsu (see section 4.1.5). However, the scope of this project is wider, trying to advance
our general understanding of the ways in which noble gases in different archives can help us to gain
paleoclimatic information.
Another area of research that is currently developed is the study of interactions between groundwater
and lakes, where a strong link between the two subgroups of the aquatic systems section becomes
apparent (see section 4.1.6). A just completed diploma thesis investigated and validated the use of
Radon as a tracer to study this interaction [Kluge, 2005].
Funding The China project is funded by the DFG and its Chinese counterpart NSFC. The speleothem
project is part of a DFG research unit (”Dated speleothems as archives of the paleo-environment”).
The Odenwald project is a collaboration with the ”Hessisches Landesamt für Umwelt und Geologie”
and the tracer analyses are funded by the State of Hessen. Hany El-Gamal was supported by a longterm
mission fellowship of the Egyptian government. Laszlo Palcsu is supported by a Marie Curie
EIF fellowship of the EU (project ”ADNOGAPALIN”).
Cooperations In the above mentioned projects we cooperate with other groups of the institute,
in particular with the carbon cycle group for stable isotope analyses on groundwaters and with the
radiometry group for the preparation of 14 C samples for AMS analysis as well as on the study of
fluid inclusions in speleothems. There exists also a cooperation with the ice and climate group on
the analysis of He isotopes in ice. Cooperations outside the institute include local project partners
in China, Egypt and Hessen. Furthermore, close links exist to the noble gas and AMS labs at ETH
Zurich, where some of our samples are analysed, as well as to the isotope hydrology group at the
University of Bern. Several links exist to scientists at the UFZ in Leipzig and Halle, and many new
national and international cooperations will be forged in the framework of the upcoming DFG research
unit.
The institutions of our main cooperation partners are listed in the following (with shortcuts as used
for author affiliations in the project reports):
Institute of Hydrogeology and Environmental Geology, Chinese academy of geological sciences, Zhengding,
China (IHEG),
Geology Department, Faculty of Science, Minufiya University, Shebin El-Kom, Egypt (MINUF),
Hessisches Landesamt für Umwelt und Geologie, Wiesbaden, Germany (HLUG),
Institut für Isotopengeologie und Mineralische Rohstoffe, ETH Zürich, Switzerland (ETHZ).

4.1. GROUNDWATER AND PALEOCLIMATE 153
Publications
Peer reviewed
1. Aeschbach-Hertig [2005a]
2. Corcho Alvarado et al. [2004]
3. Peeters et al. [2004]
Other publications
1. Kreuzer et al. [in press 2005]
Doctoral theses
1. El-Gamal [2005]
Diploma theses
1. Klement [2005]
2. Kluge [2005]
3. Rice [2004]
4. Träumner [2005]
Invited Talks
1. Aeschbach-Hertig [2005b]
2. Aeschbach-Hertig [2004c]
3. Aeschbach-Hertig [2004a]
4. Aeschbach-Hertig [2004d]
5. Aeschbach-Hertig [2004b]

154 CHAPTER 4. AQUATIC SYSTEMS
4.1.1 A tracer study of paleoclimate and groundwater recharge in the
North China Plain
Participating scientists Andreas M. Kreuzer, Christoph v. Rohden, Werner Aeschbach-Hertig,
Chen Zongyu (IHEG), Rolf Kipfer (ETHZ)
Abstract Noble gas temperatures (NGTs), stable isotope ratios and 14 C-ages from old groundwater
in the North China Plain (NCP) are used to reconstruct a paleoclimate record. This is the first NGT
record from East Asia. Preliminary results indicate a glacial cooling of about 4 ◦ C .
NGT (°C)
15.5
15.0
14.5
14.0
13.5
13.0
12.5
12.0
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
2.6
Noble Gas Temperatures of different wells
Avg. 12.8°C
7
15.5
13
10
12
0 50 100 150 200 250 300 350 400
12
18
11
Avg. 9.0°C
Approx. distance from well #1 (km)
Numbers below points
indicate age of
specific well in ka.
(Data from Zongyu, 2003)
Figure 4.1: The figure shows the noble gas temperatures for the samples from 2004. There are warm temperatures
of about 13 ◦ C in the infiltration area (on the left end), which correspond to the local annual air temperatures. The
transition from the holocene to the last glacial occurs at about 100 km from well no.1 accompanied by a clear signal in
temperature.
Background Noble gas concentrations in water
vary with temperature as the solubilities are temperature
dependent. Measurements of noble gases
in paleo-groundwater can therefore be used to calculate
paleo-recharge temperatures [Kipfer et al.
, 2002]. The importance of this method lies in
reliable determination of glacial-interglacial temperature
differences. The age of the groundwater
in the NCP reaches from very young water to
20 kyr old water in the deeper parts of the aquifers
[Zongyu et al. , 2003].
The goal of this study is to complement isotope
data from this aquifer system with NGTs in order
to quantify the climatic signal of the transition
from the last glacial maximum (LGM) to the
holocene.
Methods and results Last years measurements
showed a clear temperature signal at about
100 km from well #1 as shown in the figure. This
year a second sampling campaign was conducted
in April to sample a short distance where the transition
from the last glacial to the holocene was
expected.
A clear climatic signal is also present in the sta-
ble isotope data corroborating previous results of
Zongyu et al. [2003].
For radiocarbon dating of groundwater a new
extraction-line was developed and built. A total
amount of about 200ml of water is needed, which
is then acidified under vacuum to release the dissolved
inorganic carbon from the water. The carbon
dioxide is then trapped in a special volume
in liquid nitrogen and is further treated and prepared
for accelerator mass spectrometry.
Funding This work is financially supported by
the DFG (DFG grant AE 93/1) and by the
National Natural Science Foundation of China
(NSFC grant No. 40472125)
Outlook/Future work The dating with 14 C
will be done by the end of this year and also the
measurement of the new noble gas samples will be
finished this year. It is planned to present the results
at international conferences and to prepare
publications.
Main publication Kreuzer et al. [in press
2005]

4.1. GROUNDWATER AND PALEOCLIMATE 155
4.1.2 A multi-tracer study of groundwater in reclamation areas south-west
of the Nile Delta, Egypt
Participating scientists Werner Aeschbach-Hertig, Hany El-Gamal, Kamal Dahab (MINUF), Rolf
Kipfer (ETHZ)
Abstract The origin and renewal rate of groundwater used for irrigation in Egypt was investigated
using a variety of isotope and tracer techniques ( 2 H, 18 O, 14 C, SF6, 3 H- 3 He, noble gases). The main
result is that the groundwater is recharged from the Nile river, albeit at a slow rate. Water younger
than 50 yr is found only in the vicinity of surface water features in the Nile Delta.
� � ���per mil�
20
0
-20
-40
-60
-80
GMWL
A
Paleowater
Pre-1969 Nile water
Precipitation
-12 -10 -8 -6 -4 -2 0 2 4
�
� 18
O [per mil]
Figure 4.2: Mixing trend lines in stable isotope data. Squares A, B, and C indicate endmembers, dots
represent precipitation data, and triangles represent data from the wells. The latter lie on mixing lines
(dashed) between regional paleogroundwater and Nile water from before and after the completion of
the Aswan High Dam in 1969. These data clearly show that the groundwater is mainly recharged
from the surface water, but at a slow rate, such that most of the water infiltrated before 1969.
Background Egypt develops new agricultural
areas outside the overpopulated Nile Delta and
Valley. Such so-called reclamation areas depend
almost exclusively on groundwater as water resource.
For the long-term sustainability of these
developments it is of central importance to understand
the processes and rates of recharge of the
groundwater resources.
Methods and results The transient environmental
tracers SF6 and 3 H- 3 He have been used
to date the shallow groundwater, whereas dating
of the old groundwater by 14 C is currently
in progress. Noble gases and stable isotopes have
been analysed to obtain information on the conditions
during recharge. The results of the SF6
and 3 H- 3 He dating show that only the wells that
are located within a few kilometers of the artificial
irrigation canals in the delta have young ages of
between 1 and 25 years, indicating direct recharge
by water derived from the river. At larger distance
from the surface water, the age of the groundwater
exceeds the detection limit of these methods
B
C
Recent
Nile
water
(30 - 50 yr). The 14 C-analyses will provide information
on the age of the groundwater in the
reclamation areas, some tens of kilometers apart
from the surface water. The stable isotope data
provide clear indications of the on origin and age
of the groundwater, due to the change (enrichment
by evaporation) of the isotopic signature of
the Nile water resulting from the construction of
the Aswan High Dam in 1969 (see figure). Only
groundwater samples from the vicinity of the river
lie close to the the recent Nile water composition.
Most of the data lie close to the former Nile composition
but not the local precipitation, indicating
paleo-recharge derived from the river.
Outlook/Future work The 14 C ages should
enable us to further constrain the renewal rate
of the groundwater and thus to contribute crucial
information for a sustainable management of this
resource. A publication is in preparation.
Main publication El-Gamal [2005]

156 CHAPTER 4. AQUATIC SYSTEMS
4.1.3 A multi tracer study to investigate the groundwater in the Odenwald
region
Participating scientists Ronny Friedrich, Werner Aeschbach-Hertig, Bernhard Leßmann (HLUG),
Guido Vero (HLUG)
Abstract Three sampling campaigns where performed during 2003, 2004 and 2005 in the Odenwald
region. With this multi tracer study (noble gases, 3 H, δ 18 O, δ 2 H, SF6, CFCs) we want to investigate
the age structure, mixing ratios and recharge areas of the groundwater in this region. First results
show groundwater ages of a few years up to older than 40 years.
Figure 4.3: Stable isotope data (δ 18 O, δ 2 H) of the campaign in 2003. Isotopic signatures of samples
from the crystalline part (1), the sandstone part (2) and from the ”Hanau-Seeligenstädter-Senke” (4)
are concentrated in separate groups, whereas samples from ”Hessisches Ried” (3) scatter over the
whole range.
Background The Odenwald region is one of
the main recharge areas for groundwater of
the surrounding areas (Hessisches Ried, Hanau-
Seligenstädter Senke). These areas are very important
for freshwater extraction. Therefore we
want to investigate the groundwater in the Odenwald
to study residence times and mixing ratios
of the groundwater, define regions of groundwater
recharge and understand the groundwater inflow
from the Odenwald to the surrounding areas.
Funding This work is done in cooperation with
the ”Hessisches Landesamt für Umwelt und Geologie”
Wiesbaden.
Methods and results To study the groundwater
we use different stable and radioactive gasand
isotope tracers summarized as ”environmental
tracers” such as 2 H, 18 O, 3 H, noble gases and
SF6. Noble gases (He, Ne, Ar, Kr, Xe) can be
used in principle to calculate recharge temperatures
or the infiltration altitudes (above sea level)
of recharge areas. Furthermore noble gases give
important information to correct other gas tracers
for so called ”excess air” that oversaturates
gases in groundwater (see Kipfer et al. [2002] for
a review of the methods). SF6 and 3 H- 3 He are
used to date the groundwater.
Comparing the results of these two independent
dating methods we see that dating with SF6 is not
possible in the crystalline region of the Odenwald.
We assume that SF6 is influenced by a natural
source in the subsurface. Data from the 3 H- 3 He
method give robust groundwater ages in the range
of some years to values higher than 40 years. By
using the stable isotope data it is possible to distinguish
between groundwater from different areas
of the Odenwald. That will help us to define flow
paths of the groundwater from the Odenwald to
the surrounding areas. Additionally the isotopic
signatures show that the groundwater was formed
by ”annual” precipitation and not only in winteror
summertime.
Outlook/Future work Until today we have
analyzed all samples from the campaign in 2003.
Measuring the samples from 2004 and 2005 should
give us information about seasonal changes in
groundwater flow.
Main publication Friedrich et al. [2004]

4.1. GROUNDWATER AND PALEOCLIMATE 157
4.1.4 A new mass spectrometric system for measurement of noble gases
and first applications to perform measurements of fluid inclusions in
speleothems
Participating scientists Katja Träumner, Werner Aeschbach-Hertig, Ronny Friedrich, Laszlo Palcsu
and Gerhard Zimmek
Abstract A new mass spectrometric system for purification and measurement of noble gases from
groundwater and stalagmite samples was put into operation and tested for its behavior. The first
application was a successful testing of a new extraction method for stalagmite samples.
Desorption
120%
100%
80%
60%
40%
20%
Desorption characteristic charcoal trap
0%
0 20 40 60 80 100 120 140
-20%
Temperature [K]
Helium
Neon
Figure 4.4: The desorption of helium and neon from the charcoal trap as a function of temperature is
shown. The decrease of the Helium-signal is a result of the gas consumption of the Quadrupol mass
spectrometer which was used for measurement. On account of this characteristic curves a separation
of helium and neon is possible, which is necessary for an exact measurement in the mass spectrometer.
Background The characteristic temperature
dependence of the solubility of noble gases and
their property of being chemically and biologically
inert, make noble gases an ideal proxy for
paleotemperatures [Kipfer et al. , 2002]. By measuring
noble gas concentrations of small fluid inclusions
in stalagmite samples, we try to combine
this thermometer with the possibility to precisely
date the speleothem archive.
Methods and results After first experiences
with the extraction of fluid inclusions in the institute
by a master thesis in the last year [Rice,
2004], now the development of a new mass spectrometric
system was the next step. This system
consists of an inlet part to attach several kinds
of samples, a system of cold traps for purification
and separation (one trap cooled by dry ice
for removal of water, one nude metal trap to condense
all gases except helium and neon and a charcoal
trap for separating helium and neon) and a
commercial mass spectrometer, which is especially
designed for measuring noble gases (see section
4.1.5).
During the diploma thesis the software to control
all valves and to supervise the pressure in the line
was written; software, tests and the parameters
for temperature control of the traps were developed
and several volumes (pipettes, standards, expansion
and splitting volumes) of the system were
determined. The new system was tested for the
temporal behavior of the cool down processes and
the desorption properties of the cold traps.
The results of these tests were used to develop a
new measurement routine. To continue the work
with fluid inclusions in speleothems a new crushing
method was tested. First measurements show
that good results depend on the kind of samples.
The composition of noble gases from stalagmites
is a mixture of gases from air and from water.
Outlook/Future work An automated measurement
of samples will soon be possible. We
will obtain a sample throughput of at least two to
three samples a day. The work with the stalagmite
samples will be continued by a Ph.D. thesis.
Main publication Träumner [2005]

158 CHAPTER 4. AQUATIC SYSTEMS
4.1.5 Advancing the use of noble gases as palaeoclimate indicators
Participating scientists Laszlo Palcsu, Werner Aeschbach-Hertig
Abstract A better understanding of gas partitioning during groundwater infiltration is a prerequisite
for the reliable use of noble gases as palaeoclimate proxies. The primary goal of the present project
is to obtain a detailed understanding of the physical mechanisms linking climate and soil parameters
to the noble gas patterns imprinted during groundwater recharge.
Figure 4.5: Results of stability tests of the new noble gas system, showing the deviation of different
noble gas measurements from the average (X-axis: number of measurements, Y-axis: deviation in %).
Background The analysis of dissolved noble
gas concentrations in groundwater has proven to
be a reliable method to determine quantitative
palaeotemperatures [Kipfer et al. , 2002]. Noble
gas studies in semi-arid regions have shown that
in addition to recharge temperatures, the ”excess
air” phenomenon may be useful as a proxy for
the important climate parameter humidity [Beyerle
et al. , 2003]. The present project aims at
advancing and broadening the scope and applicability
of noble gases in palaeoclimatology and hydrology,
in particular at establishing the palaeoclimatic
significance of excess air. This objective
shall be achieved by careful analysis of noble gas,
climate, and soil data from several semi-arid regions,
complemented by experiments on the scale
of laboratory soil columns and test-fields.
Methods and results To interpret the dissolved
noble gases in water as noble gas temperature
and excess air component with low error it is
necessary to achieve a very precise measurement
of noble gases. Therefore, the accuracy of each
noble gas measurement should be around 1 % or
better. Noble gas measurents are performed by a
new GV 5400 noble gas mass spectrometer which
was purchased and installed in 2004. The GV
5400 is an all-metal, statically operated, double focused,
90 ◦ sector field mass spectrometer with 57
cm extended geometry. So far, sensitivities and reproducibilities
were determined. According to the
acceptance specification, the achieved sensitivities
are 7.52·10 −4 Amps/Torr for 40 Ar, and 3.47·10 −4
Amps/Torr for 4 He, respectively. Stability and
reproducibility measurements were performed on
normal air samples. An individual sample could
be measured within a few permil relative error,
while the results of several measurements differed
from each other by 1-2 %. The standard deviation
of the 4 He and 3 He measurement were 0.6 %
and 1.2 %, whilst the measured data were varying
within the range of ±1 % and ±3 % around the
average (see Figure). The standard deviation of
the heavier noble gases were 0.3 % for neon, 0.5 %
for argon, 1.0 % for krypton, and 0.9 % for xenon.
These accuracies allow us to determine noble gas
temperatures with an error of about 0.5 ◦ C and
very precise excess air components.
Outlook/Future work Laboratory and field
experiments will be started in the next months
in order to investigate the mechanisms which are
responsible for the excess air formation. Furthermore,
using the ability for precise noble gas measurements,
the potential of fluid inclusions in stalagmites
and other carbonate deposits from caves
as palaeoclimate archives will also be investigated
(see section 4.1.4).
Funding This project is supported by the Marie
Curie Intra-European Fellowships program (reference
number: 009562).

4.1. GROUNDWATER AND PALEOCLIMATE 159
4.1.6 Radon as tracer for lake - groundwater interaction
Participating scientists Tobias Kluge, Werner Aeschbach-Hertig, Christoph v. Rohden, Johann
Ilmberger
Abstract Using the radioactive noble gas radon-222, the groundwater inflow into a lake is calculated
from vertical profiles. With the aid of a newly developed sensitive technique, a clear groundwater signal
has been detected in the lake.
depth (m)
0
5
10
15
epilimnion
thermocline
hypolimnion
typ. error
0 5 10 15 20 25 30
Bq/m 3
20.June
4.July
12.July
19.July
26.July
Figure 4.6: Vertical radon profile in Lake Willersinnweiher, a lake with significant groundwater inflow
in the upper part. This inflow produces a radon maximum in the thermocline. In the epilimnion,
outgassing into the atmosphere reduces the radon activity.
Background In this study we investigated the
lake - groundwater interaction at a lake in the
Rhine-Valley without surface inflow from rivers.
One focus was to quantify the groundwater inflow.
This inflow is used to calculate the replacement
time of the lake water, which is of great ecological
and hydrological significance.
Rn-222 is a suitable tool to detect even a very
small amount of groundwater inflow, because the
activity difference between groundwater and lake
- or surface water is very high. In the study area
the activity concentration of radon in the groundwater
is between 5 000 and 10 000 Bq/m 3 and in
the lake water it is < 50 Bq/m 3 .
Methods and results The measurements are
done with an alpha-spectrometer (RAD7). This
spectrometer detects the decay products of radon
in the gas phase. To evaluate the radon activity
of water, radon in sample water is brought into
equilibrium with radon in a closed air loop. The
activity in the air loop is only controlled by the
amount of radon in water and its solubility. A new
technique with large (12 l) water samples was de-
veloped to reduce the detection limit.
To explain the results, the sources of radon have
to be known. The first possibility is the dissolved
radium, that can decay directly into radon. Another
source is the emanation from the lake sediments
and the inflow of dissolved radon with the
groundwater. Loss is caused by decay and outgassing
into the atmosphere. The vertical profile
can only be explained by a strong groundwater
inflow in the epilimnion and a negligible inflow in
the hypolimnion.
By dividing the lake in different boxes according
to the structure of stratification, a water balance
was calculated. The replacement time for the epilimnion
is (4.7 ± 1.2) years, for the hypolimnion
ca. 21 years. In addition to previous studies,
statements about depth-dependent groundwater
inflow are possible. Due to the large number of
constraints an exact calculation of the smallest
and greatest possible groundwater inflow can be
made.
Main publication Kluge [2005]

160 CHAPTER 4. AQUATIC SYSTEMS
References
Aeschbach-Hertig, W. 2004a. Climate of the Past as a Basis for an Assessment of the Future. Invited
talk, GSI-Kolloquium, Darmstadt, Germany.
Aeschbach-Hertig, W. 2004b. Environmental Tracers in Groundwater Studies - Water Resources and
Paleoclimate. Invited talk, Institute of Hydrogeology and Environmental Geology, Chinese Academy
of Geological Sciences, Zhengding, China.
Aeschbach-Hertig, W. 2004c. Excess Air in Groundwater: Problems and Opportunities. Invited
keynote presentation, Annual Meeting of the Geological Society of America (GSA), Denver, USA.
Aeschbach-Hertig, W. 2004d. Noble Gases and Excess Air in Groundwater: Review and Outlook.
Invited talk, KUP-Seminar, University of Bern, Switzerland.
Aeschbach-Hertig, W. 2005a. A comment on ”Helium sources in passive margin aquifers-new evidence
for a significant mantle 3 He source in aquifers with unexpectedly low in situ 3 He/ 4 He production”
by M. C. Castro [Earth Planet. Sci. Lett. 222 (2004) 897-913]. Earth Planet. Sci. Lett., in press.
Aeschbach-Hertig, W. 2005b. Surface and Subsurface Waters. Invited lecture, WE-Heraeus summerschool
”Physics of the Environment”, Bad Honnef, Germany.
Beyerle, U., Rüedi, J., Leuenberger, M., Aeschbach-Hertig, W., Peeters, F., Kipfer, R., & Dodo, A.
2003. Evidence for periods of wetter and cooler climate in the Sahel between 6 and 40 kyr BP
derived from groundwater. Geophys. Res. Lett., 30(4), 1173, doi:10.1029/2002GL016310.
Corcho Alvarado, J. A., Purtschert, R., Hinsby, K., Troldborg, L., Hofer, M., Kipfer, R., Aeschbach-
Hertig, W., & Synal, H.-A. 2004. 36 Cl in modern groundwater dated by a multi tracer approach
( 3 H/ 3 He, SF6, CFC-12 and 85 Kr): A case study in quaternary sand aquifers in the Odense Pilot
River Basin, Denmark. Appl. Geochem., 20, 599–609.
El-Gamal, H. 2005. Environmental tracers in groundwater as tools to study hydrological questions in
arid regions. PhD thesis, University of Heidelberg.
Friedrich, R., Aeschbach-Hertig, W., Vero, G., & Leßmann, B. 2004. Einsatz von Umwelttracern zur
Erkundung des Grundwassers der Odenwald-Region. Page 35 of: Schiedek, T., Kaufmann-Knoke,
R., & Ebhardt, G. (eds), Hydrogeologie regionaler Aquifersysteme (FH-DGG-Tagung). Schriftenreihe
der Deutschen Geologischen Gesellschaft, vol. 32. Darmstadt: Deutsche Geologische Gesellschaft.
Kipfer, R., Aeschbach-Hertig, W., Peeters, F., & Stute, M. 2002. Noble gases in lakes and ground waters.
Pages 615–700 of: Porcelli, D., Ballentine, C., & Wieler, R. (eds), Noble gases in geochemistry
and cosmochemistry. Rev. Mineral. Geochem., vol. 47. Washington, DC: Mineralogical Society of
America, Geochemical Society.
Klement, R. 2005. Optimierung von SF6-Grundwasserprobenahme-Methoden. Diplomarbeit, Universität
Heidelberg.
Kluge, T. 2005. Radon als Tracer in aquatischen Systemen. Diplomarbeit, Universität Heidelberg.
Kreuzer, A. M., Zongyu, C., Kipfer, R., & Aeschbach-Hertig, W. in press 2005. Environmental Tracers
in Groundwater of the North China Plain. In: IAEA (ed), International Conference on Isotopes in
Environmental Studies - Aquatic Forum 2004. Monte-Carlo, Monaco: IAEA.
Peeters, F., Beyerle, U., Aeschbach-Hertig, W., Brennwald, M. S., & Kipfer, R. 2004. Response to
the comment by G. Favreau, A. Guero, and J. Seidel on Improving noble gas based paleoclimate
reconstruction and groundwater dating using 20 Ne/ 22 Ne ratios (2003) Geochim. Cosmochim. Acta,
67, 587 - 600. Geochim. Cosmochim. Acta, 68(6), 1437–1438.
Rice, S. 2004. The development of a method for the extraction and measurement of noble gases from
fluid inclusions in samples of calcium carbonate. Master thesis, University of Heidelberg.
Träumner, K. 2005. Inbetriebnahme, Tests und erste Anwendung einer neuen Aufbereitungslinie zur
massenspektrometrischen Messung von Edelgasen aus Grundwasser - und Stalagmitproben. Diplomarbeit,
Universität Heidelberg.
Zongyu, C., Jixiang, Q., Jianming, X., Jiaming, X., Hao, Y., & Yunju, N. 2003. Paleoclimatic
interpretation of the past 30 ka from isotopic studies of the deep confined aquifer of the North
China plain. Appl. Geochem., 18, 997–1009.

4.2. LAKE RESEARCH (LIMNOPHYSICS) 161
4.2 Lake Research (Limnophysics)
Names of group members
Dr. Johann Ilmberger, head of group
Dr. Christoph von Rohden, postdoc
Dipl. Phys. Karl Wunderle, diploma student (completed April 2005)
Abstract Water quality of lake waters is, among other factors, affected by mixing and transport
processes in the interior, as well as by the exchange with the ambient ground water. These internal
processes and the ground water exchange are the main subjects of our investigations.
Figure 4.7: Schematic diagramm of transport processes in lakes.
Background Transport processes in lakes are important for the lake water quality. Especially
mining lakes tend to have a poor quality because of the disturbed landscape due to the mining
activities.
Methods The investigations are based on tracers and direct measurements. Mainly we are using
the tracer SF6, but also stable isotopes and now upcoming Radon (see section 4.1.6).
The background level of SF6 can be used to study the interaction of ground water with lake water.
This is based on the equilibration of rain and surface waters with atmospheric gases and the increase
of the atmospheric level of the man made SF6 during the last decades. Therefore ground water -as it
normally infiltrated a few decades ago- has a low SF6 content, while the lake water SF6 concentration
is, at least during overturn, close to the (higher) atmospheric concentration. This difference of the
signals can be used to study ground water - lake water exchange. We will try to apply this method
to the mining lake RL117.
We use SF6 spike experiments to investigate vertical mixing and ground water exchange. There we
inject a small amount SF6 (few hundred mg) into the (hypolimnic) water body and trace the vertical
spread and the balance by profile measurements (see section 4.2.1). We applied this method to Lake
Constance, Lake Hufeisensee, Lake Merseburg Ost 1a and 1b. We will apply it at Lake Waldsee.
Direct measurements include the profile measurements of temperature and electrical conductivity with
a CTD-probe at a vertical resolution of ∼2cm (see section 4.2.2), continuous temperature measurements
at different water depths using logging temperature probes and measurements of water currents
with an Acoustic Doppler Current Profiler (see section 4.2.3).
Lakes in investigation: Mining lake Merseburg Ost 1a, Mining lake Merseburg Ost 1b, Lake Willersinnweiher,
Lake Waldsee, Lake RL117.
The tracer methods, especially the spike experiments, are very well suited for the transport investigations.
Projects and funding
Our work at Willersinnweiher, where we did current measurements, continuous temperature and CTD-

162 CHAPTER 4. AQUATIC SYSTEMS
profile measurements, was funded by the SFB 359: ”Reaktive Strömungen, Diffusion und Transport”,
Teilprojekt D2 (see section 4.2.3).
The SF6 spike measurements at the mining lakes Merseburg 1a and 1b were funded by the Centre
of Environmental Research Leipzig-Halle and performed in close collaboration with B. Böhrer (UFZ-
Leipzig/Halle, Section Gewässerforschung, Magdeburg).
In the future we will intensify the research using radon as limnic tracer, as the work of Tobias Kluge
has shown its potential as tracer for the groundwater exchange of gravel lakes (see section 4.1.6).
In a joined project, funded by the German Research Foundation, we will investigate vertical transport
and groundwater exchange at two mining lakes (Lake Waldsee and Lake RL117).
Collaborations
UFZ Leipzig-Halle, Dept. of Lake Research Magdeburg and Dept. of Isotope Hydrology
BTU Cottbus, Lehrstuhl Gewässerschutz
Institute for Biodiversity and Ecosystem Dynamics / Aquatic Microbiology, University of Amsterdam
Limnologisches Institut, Universität Konstanz
Institut für Seenforschung, Langenargen, LfU
Publications
Other publications
1. Ilmberger & von Rohden [2005]
2. Ilmberger et al. [2005]
3. von Rohden et al. [2005]
Diploma theses
1. Wunderle [2005]

4.2. LAKE RESEARCH (LIMNOPHYSICS) 163
4.2.1 Sulfurhexaflourid (SF6) as tracer for transport and mixing processes
in mining lakes
Participating scientists Johann Ilmberger, Christoph von Rohden
Abstract To study transport and mixing processes in the monimolimnion of mining lakes we released
a small quantity of the trace gas in the monimolimnion of two mining lakes. The vertical spread and
the mass balance were used to gain information about the vertical diffusion and the ground water
exchange.
Figure 4.8: SF6 - quantity in the monimolimnion (the water mass below 56.55 m asl) of the mining
lake Merseburg-Ost 1a versus time. The experiment was started in 1997 and today we still can balance
the trace gas by measuring a vertical profile. The SF6 decreases at a rate of 0.12 yr −1 , which is mainly
due to ground water exchange.
Background Because of their geometry, which
is the result of the mining activities, mining lakes
tend to have a water body which is not involved
in the yearly cycle of mixing, a monimolimnion.
These monimolimnia usually have a very poor water
quality and might be enriched by heavy metals
and other toxicities. Therefore one would like to
know how persistent they are, or how high the
risk is to contaminate the lake water and/or the
ambient ground water.
Funding This work was funded by the Centre
of Environmental Research Leipzig-Halle.
Methods and results The man made and industrially
used gas sulfur hexaflouride (SF6) is
very well suited to trace transport processes in
strongly stratified waters, because it is chemically
inert much as a noble gas. So far no other than
the (very slow) degradation in the higher atmosphere
is reported. And, because of its high electronegativity,
it can be detectet very sensitively
by an ECD detector after separation by gas chromatography.
Our detection limit is ∼ 10 −17 Mol
(10 aMol). For comparison: water, in equilibrium
with the modern atmosphere ( 6 pptv), has a concentration
of 2 fMol/l (= 2 · 10 −15 Mol/l). In
1997 we started a tracer experiment in the monimolimnion
of the open pit mining lake Merseburg-
Ost 1a [von Rohden & Ilmberger, 2001]. To investigate
the transport processes we injected 0.1
mMol (15 mg) of SF6 into the interior of the monimolimnion.
The monimolimnion has a salinity of
about 40�, is about 2 m high and within a distance
of 20 cm it changes to the hypolimnic salinity
of 4�. The figure shows the total SF6 content
of the monimolimnion calculated from profiles
sampled at a vertical distance of 20 cm. The
SF6 content of the monimolimnion changed from
the initial 100 Mol down to 45 Mol at the beginning
of 2004. A logarithmic fit to the values
leads to a loss rate of 0.12 yr −1 . So 12% of the
content leaves the monimolimnion per year. As
we find only very little SF6 escaping into the hypolimnion
and even a decrease in concentration
directly above the lake floor, the loss is mainly
due to ground water exchange.
Outlook/Future work Though we do not
have further funding for this research we will try
to continue these very interesting investigations.
Main publication Ilmberger & von Rohden
[2005]

164 CHAPTER 4. AQUATIC SYSTEMS
4.2.2 Vertical transport in stratified lakes
Participating scientists Christoph von Rohden
Abstract Based on measurements of the environmental tracers temperature and sulfur hexafluoride,
effective vertical exchange coefficients Kz in density stratified lakes were calculated using budget
methods. The heat transport in summer stratification can be limited to conduction. Molecular
diffusion was found to be the only exchange process in lakes with strong chemical stratification.
height [m asl]
88
86
84
s u r f a c e
82
80
78
76
74
72
70
68
5 10 15 20 25 10 -5
10 -4
10 -3
2004
t h e r m o c l i n e
05.11.
22.10.
24.09.
14.09.
03.09.
25.08.
10.08.
30.07.
16.07.
06.07.
25.06.
07.06.
08.06.
27.05.
a)
17.05.
07.05.
b o t t o m
b)
temperature [°C]
stratification stability N 2 [s -1 stability N
]
2
10 -2
heat conduction
10 -7
10 -6
c)
10 -5
diffusion coefficient K z [m 2 /s]
Figure 4.9: a) Temperature profiles during the summer stratification, b) mean stability (acting against
vertical exchange) due to temperature gradients, c) calculated parameter Kz (average) representing
the intensity of exchange.
Background In density stratified lakes, the extent
of the redistribution of geochemically relevant
species caused by the wind driven internal
dynamics is of interest. On time scales of weeks
to months, the vertical transport during stratification
is a result of small scale turbulent motions.
It can be quantified by calculating Kz as effective
vertical exchange coefficients.
Funding The work was supported by the SFB
359 “Reaktive Strömungen, Diffusion und Transport”,
University of Heidelberg and the Centre
for Environmental Research (UFZ) Leipzig-Halle,
Department of Lake Research, Magdeburg.
Methods and results The investigations are
based on high resolution profiles of temperature
and conductivity (taken with an automatic probe)
and gas chromatographic measurements of the artificial
tracer sulfur hexafluoride. Assuming horizontal
homogeneity, which is reasonable in small
lakes, the experimental setup was one dimensional
taking into account the morphology of the lakes.
The transport intensity was quantitatively estimated
by budgeting of these tracers. The flux
gradient method connects changes in the tracer
concentrations in distinct lake layers (budgeting)
to the vertical fluxes. Turbulent diffusion coefficients
are calculated from the fluxes using Fick’s
law.
The results show that the vertical exchange is suppressed
by the stratification. In a small quarry
pond, the heat fluxes are reduced to the conduction
level (∼ 10 −7 m 2 /s) during summer in the
stratified region (high temperature gradients, see
figure). This gives room for even lower transport
rates of solutes.
In a mining lake with a strong permanent salt
stratification we found the molecular diffusion
(∼ 10 −9 m 2 /s) to be the dominant transport process
within the stratified region.
Outlook/Future work A new project will
start in 2006 to investigate the interaction of
groundwater connection, vertical transport and
stratification in a mining lake with a permanent
density gradient maintained by hydrochemical
processes.
Main publication von Rohden [2002]

4.2. LAKE RESEARCH (LIMNOPHYSICS) 165
4.2.3 Investigation of Water Currents in Lake Willersinnweiher using Acoustic
Doppler Current Profiler
Participating scientists Karl Wunderle, Christoph von Rohden, Johann Ilmberger
Abstract In a small stratified lake currents were measured with a bottom mounted 1200 kHz Acoustic
Doppler Current Profiler, ADCP. Currents are measured with an accuracy of ∼1 mm/s and a
vertical resolution of 20-40 cm. Typical current speeds in Lake Willersinnweiher are very low in the
range of several mm/s (especially in the hypolimnion), occasionally reaching a few cm/s during wind
incidents.
Figure 4.10: Short Time Fourier Transformation (STFT) of the east - west component of water
currents at a depth of 10 m. The time series, used for these calculations, startet at the 6th July 2004.
The window for the individual spectrum is 21 h (256 5-minute values) at an overlap of 80%. The color
indicates the spectral intensity of the signal on a logarithmic scale from high (red) to low (blue).
Background Transport and mixing in the interior
of lakes is due to wind driven internal motion.
To investigate the internal dynamics, fluctuations
of water temperature as indirect indicator of motion
and direct water current measurements can
be used.
Funding The work was supported by the SFB
359 “Reaktive Strömungen, Diffusion und Transport”,
University of Heidelberg.
Methods and results Current measurements
were performed with the ADCP (RD Instruments)
mounted at the bottom of the lake. 800 pings were
averaged and recorded every 5 minutes. To keep
the inclination angles below 2 ◦ , it was mounted
in a cardanic suspension. The ADCP was powered
through a cable from ashore, using low cost
rechargeable 60 V battery pack. The cable was
also used to check the operation and download the
stored data once a week. In addition to the current
measurements weekly vertical profiles of temperature
and electrical conductivity were taken
and temperature data were continuosly recorded
at several depths at different sites in the lake.
Long term Fourier transform does not show significant
peaks in the spectra i.e. there are no distinct
eigenfrequencies on a longer timescale. In order to
resolve the dynamics of the watercurrents Short
Time Fourier Transform (STFT) was used. Figure
1 shows an example of a STFT calculation
of the east-west component of the watercurrent
from 6th to 13th July 2004 using a window of 21h
(256 5min values) and an overlap of 80The STFT
computations reveal the transient character of the
currents with peaks at ∼3h.
Main publication Wunderle [2005]

166 CHAPTER 4. AQUATIC SYSTEMS
References
Ilmberger, J., & von Rohden, C. 2005. Abschlußbericht zum Forschungsvorhaben: ”SF6 als Tracer
für Transport- und Mischungsprozesse in Tagebaurestseen.
Ilmberger, J., von Rohden, C., & Wunderle, K. 2005. Observation of Multilayer Structures in a Small
Lake. In: In A. Folkard and I. Jones,editors, 9th workshop on physical processes in natural waters.
von Rohden, C. 2002. Tracerstudie zur Quantifizierung des Vertikaltransports in meromiktischen Seen.
PhD thesis, University of Heidelberg.
von Rohden, C., & Ilmberger, J. 2001. Tracer experiment with sulfur hexafluoride to quantify the
vertical transport in a meromictic pit lake. aquatic sciences, 63, 417–431.
von Rohden, C., Hauser, A., Wunderle, K., Ilmberger, J., Wittum, G., & Roth, K. 2005. Lake
dynamics: observation and high-resolution numerical simulation. In Rannacher editor. Springer.
Wunderle, K. 2005. Untersuchungen der Strömungen im Willersinnweiher mit einem akustischen
Strömungsmessgerät. Diplomarbeit, University of Heidelberg.

Small-Scale Air-Sea Interaction
5.1 Small-Scale Air-Sea Interaction . . . . . . . . . . . . . . . . . . . . . . . . 169
167

5.1. SMALL-SCALE AIR-SEA INTERACTION 169
5.1 Small-Scale Air-Sea Interaction
Names of group members
Prof. Dr. B. Jähne, head of group
Dr. G. Balschbach, staff
Dipl.Phys. K. Degreif, PhD student
Dipl.Chem. A. Falkenroth, PhD student
Dr. C. S. Garbe, Postdoc
Dipl.Phys. M. Jehle, PhD student
Dipl.Phys. M. Klar, PhD student
Dipl.Phys. C. Popp, PhD student
R. Rocholz, diploma student
Dipl.Phys. M. Schmidt, PhD student
Dr. U. Schimpf, Postdoc
T. Schwarz, diploma student
Abstract Research in small-scale air-sea interaction at the IUP concentrates on air-sea gas exchange
and the dynamics of wind waves. The basic mechanisms are studied in laboratory experiments in a
unique annular wind-wave facility (The Heidelberg Aeolotron) and field experiments using imaging
techniques for quantitative visualization of the water surface structure (wind waves), the flow field,
concentration fields by laser-induced fluorescence, and the water surface temperature by passive and
active thermography.
Scientific Objectives The basic scientific objective is a better physical understanding of air-sea
gas transfer, the dynamics of short wind waves, and the micro turbulence at the ocean surface.
Currently the following topics are investigated:
1. The influence of the diffusion coefficient (or the Schmidt number Sc) on the transfer velocity
of gases. Together with the transfer velocity itself, this is a sensitive measure to distinguish
different models.
2. The influence of wind waves on air-sea gas transfer by enhancing the turbulence near the water
surface.
3. The influence of chemical reactivity on gas transfer. Here the hydration reaction of CO2 is
currently of most interest, because today only some model computations but no detailed measurements
are available.
4. Analysis of the spatial and temporal structure of the turbulence in the water-sided viscous
boundary layer as the driving force for air-water gas exchange.
Overarching topic is the study of small-scale air-sea interaction, especially the mechanisms of
air-sea gas exchange and the dynamics of wind waves.
Background Despite intensive research, knowledge about air-sea interaction processes has not been
significantly improved during the last decade. Many basic questions are still open. The relation of
the air-sea gas exchange rate with wind speed is discussed controversial. Both field and laboratory
experiments show large deviations up to a factor of two from a simple relation between the wind
speed and the gas transfer velocity [Jähne & Haußecker, 1998; Jähne, 2001]. It is obvious that
other parameters, especially wave-induced near-surface turbulence and surface active films are of
importance, but detailed modeling of these processes is still lacking. Therefore, despite their known
significant limitations, semi-empirical relations between the wind speed and the gas transfer velocity,
as established by Liss & Merlivat [1986] or Wanninkhof [1992], are still the state of the art.
Another uncertainty in the estimation of transfer velocity is the dependence on the Schmidt number
Sc. It is common to assume that the transfer velocity k is proportional to Sc −1/2 . However, for quite
some time it has been known [Jähne, 1980] that the exponent is about 2/3 for a smooth water surface
at low wind speeds and gradually decreases to 1/2 for a rough and wavy water surface. The exact
shape of this transition, and especially how it is influenced by surface films in coastal zones and on
which parameters it depends, is not known. This lack of knowledge causes a considerable uncertainty
in estimating the transfer velocity. A change of the exponent from 2/3 to 1/2 without a change of
other parameters causes an increase of the transfer velocity by about a factor of two.

170 CHAPTER 5. SMALL-SCALE AIR-SEA INTERACTION
Recently, the intermittent nature of the gas exchange process has come into the focus of research.
Of particular interest is the microscale wave breaking, a process that causes enhanced near-surface
turbulence. It is known that microscale wave breaking enhances gas transfer. Zappa et al. [2001]
found, e. g., a good correlation between the measured transfer velocity and the fraction of the water
surface at which surface renewal occurred by microscale wave breaking. Details of the mechanisms
that allow a physically-based parameterization are, however, not yet known. The intermittency of the
gas transfer is of much importance when integrating gas transfer rates form short time and spatial
scales as determined by active thermography to larger scales. Because the relation between wind
speed and the transfer velocity and possible other parameters is certainly nonlinear, not only the
mean values but also the variations must be known for a proper integration.
A particularly difficult and interdisciplinary problem is the influence of organic films on air-sea gas
transfer [Frew, 1997]. Surfactants attenuate short wind waves and thus changes the hydrodynamic
boundary conditions at the water surface. In effect, the gas transfer rate is significantly reduced.
Interestingly this complex process can be modeled by simply relating the gas transfer rate to the
mean square wave slope [Frew, 1997; Bock et al. , 1999; Frew et al. , 2004]. This close correlation
between the mean square slope and the gas transfer rate was already pointed out by Jähne et al.
[1987] long before systematic studies of the influence of surface films on gas transfer were performed.
However, a more detailed modeling is still lacking.
Main methods By using novel visualization techniques and image sequence processing techniques,
the complex small-scale air-sea interaction processes can be tackled experimentally for the first time
in both laboratory and field experiments. Equally important are spectroscopic techniques that allow
simultaneous gas exchange measurements with many tracer. The techniques are briefly described in
the following.
UV-spectroscopy for volatile species dissolved in water UV-spectroscopy in contrast to IRspectroscopy
offers the significant advantage that it is not required to degas water samples in
order to measure gases and volatile species dissolved in water, because water is transparent in
the required wavelength range from 200–300 nm. Thus this technique can be used to measure
concentrations both the water and air space. The technique adds a number of volatile species for
gas exchange measurements, especially species containing aromatic rings, such as fluorobenzenes,
thiophenes, and pyrenes. For further details see section 5.1.3.
Wave slope and height imaging A detailed investigation of the dynamics of short wind waves
required simultaneous imaging of the wave height and slope. This is because the energy of
gravity waves is contained in the wave height whereas the energy of the capillary waves is
proportional to the wave slope. Therefore a novel instrumentation was developed that is capable
to measure the wave slope and height simultaneously by making use of the fact that light at
different wavelengths in the near infrared shows significant differences in absorption. In this way
the imaging wave slope gauge could be extended for simultaneous wave height measurements
(section 5.1.7 and Jähne et al. [2005c]).
Active thermography Using heat as a proxy tracer for gases has two significant advantages. Firstly,
the concentration of the tracer at the water surface can directly be measured with infrared cameras.
Secondly, the heat flux can be controlled by applying infrared radiation onto the water
surface. Periodically varying infrared radiation was applied to the water surface to create a corresponding
variation in the surface temperature of the water. For slow variations of the infrared
radiation - slower than the time constant for the exchange process - the transfer velocity can be
measured directly by dividing the known flux density by the measured temperature variation.
If the heat flux is switched off, the temperature increase will decay with the characteristic time
constant t⋆ (surface renewal time) for the transport process across the aqueous heat boundary
layer. From this time constant the transfer velocity k can be computed directly using the relation
t⋆ = D/k 2 , where D is the diffusion coefficient for heat [Jähne et al. , 1989]. By measuring
the phase shift and amplitude damping of the thermal boundary to periodically changing IR
radiation, it is also possible to distinguish between different models for the exchange process
and to investigate the intermittency of the process. Because the infrared image sequences contain
significant contrast, the surface flow field including its vorticity and local convergence and
divergence zones can also be computed from image sequences [Garbe et al. , 2003]. Moreover,
the spatial structure of the micro-turbulence at the water surface can be studied [Schimpf et al.
, 2004].

5.1. SMALL-SCALE AIR-SEA INTERACTION 171
Fluorescence imaging of gas tracer concentration fields The fluorescence spectrum of dissolved
dyes generally shows a bandwidth between 30 and 100 nm. A second dye is used to attenuate
the emitted fluorescent light in this wavelength range differently for different wavelengths. With
this double-dye technique, the shape of the observed fluorescence spectrum depends on the path
length the light travels through the water before it is measured. Because the fluorescence is
excited from the air space, the path length directly corresponds to the distance from the water
surface.
For a given wavelength, the fluorescent light received is then integrated over a characteristic
depth ˆz = α −1 (λ), where α(λ) is the wavelength-dependent absorption coefficient of the absorbing
dye solution. If α(λ) is known, the depth-dependent concentration can be computed from
the measured spectra as a linear inverse problem.
This technique is investigated for the quenching of the fluorescence of a organic rutheniumcomplex
by oxygen (section 5.1.6) and pH-dependent fluorescent dyes (section 5.1.8).
3-D flow measurements close to and at the water surface The aqueous viscous boundary layer
at a wind-driven water surface has a thickness of at most a millimeter. Therefore almost no flow
measurements are available from this layer at a free water surface. We try to tackle this difficult
experimental problem with two techniques. First, thermal image sequences from the water surface
contain enough structures to computed 2-D flow fields (section 5.1.2). Secondly, a modified
particle tracking technique is used for depth-resolved flow measurements. Again an absorbing
dye is used to code the depth of the tracked particles and to measure the velocity component
perpendicular to the water surface from the brightness change of the particle (section 5.1.5).
Main activities Our current main activities include
1. the development of a novel optic technique for simultaneous imaging of the height and slope of
short wind waves (section 5.1.7),
2. the development of depth-resolving imaging technique to measure concentration fields of gases
close to the water surface by using a double dye laser induced fluorescence techniques (sections
5.1.6 and 5.1.8),
3. detailed studies of the Schmidt number dependency of air-water gas transfer (section 5.1.3),
4. investigations of the air-sea gas exchange by active thermography (section 5.1.1),
5. analysis of flow fields by passive and active thermography thermography (section 5.1.2),
6. 3-D flow measurements within the aqueous viscous boundary layer (section 5.1.5), and
7. 3-D flow measurements within porous gravel layers (section 5.1.4).
Funding
1. DFG-Schwerpunktprogramm 1114 “Mathematische Methoden der Zeitreihenanalyse und digitalen
Bildverarbeitung”
2. DFG-Schwerpunktprogramm 1147 “Bildgebende Strömungsmesstechnik”
3. Graduiertenkolleg 1114 “Optische Messtechniken für die Charakterisierung von Transportprozessen
an Grenzflächen” (TU Darmstadt and U Heidelberg)
4. DFG Ja395/10: ”Mechanismen des Gasaustausches zwischen Atmosphäre und Ozean: Laborversuche
und Modellierung”
5. DFG Ja395/13: ”Impact of Wind, Rain, and Surface Slicks on Air-Sea CO2 Transfer Velocity -
Tank Experiments”
6. Bundesanstalt für Wasserbau

172 CHAPTER 5. SMALL-SCALE AIR-SEA INTERACTION
Cooperation
1. Prof. T. Aach, Institut für Signalverarbeitung und Prozessrechentechnik, Universität Lübeck
2. Prof. Dr. Klaus Affeld, Dr. Ulrich Kertzscher, Labor für Biofluidmechanik, Universitätsklinikum
Charite Berlin, Humboldt Universität Berlin
3. Dr. Erhardt Barth, Institut für Neuro- und Bioinformatik, Universität Lübeck
4. Dr. Volker Beushausen, Laser-Laboratorium Göttingen e.V.
5. Dr. Nelson M. Frew, Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution
(WHOI), USA
6. Prof. Dr. Tetsu Hara, Graduate School of Oceanography (GSO), University of Rhode Island,
USA
7. Dr. V. Kudryavtsev, Marine Hydrophysical Institute, Sebastopol, Ukraine
8. Dr. V. K. Makin, Royal Netherlands Meteorological Institute, de Bilt, Niederlande
9. Prof. R. Mester, Digitale Bildverarbeitung, Institut für Angewandte Physik, Universität Frankfurt
10. Dr. Bernd Schneider, Dr. Joachim Kuss, Institut für Ostseeforschung, Warnemünde
11. Prof. Dr. Detlef Stammer, Dr. Martin Gade, Institut für Meeresforschung, Universität Hamburg
12. Prof. Christoph Schnörr, Bildverarbeitung, Mustererkennung & Computergrafik Universität
Mannheim
13. Prof. Jürgen Wolfrum, PD Dr. Volker Ebert, Physikalische Chemie, Universität Heidelberg
Future Work Future work in the coming year will include extension laboratory measurements in the
Heidelberg Aeolotron and the Hamburg wind-wave facility that combine gas exchange, wave imaging
and flow measurements.
The second focus will be further development of the depth-resolving measurements of concentration
fields and 3-D flow fields within the aqueous viscous boundary layer.
Publications
Peer Reviewed Publications
1. Frew et al. [2004]
2. Garbe et al. [2004a]
3. Jähne et al. [2005c]
4. Schimpf et al. [2004]
5. Zhang & Garbe [2004]
Other Publications
1. Jähne [2004]
2. Jähne [2005a]
3. Jähne [2005b]
Doctoral Theses
1. Fuß [2004]
2. Hilsenstein [2004]
3. Klar [2005]
4. Nielsen [2004]

5.1. SMALL-SCALE AIR-SEA INTERACTION 173
Diploma Theses
1. Rocholz [2005]
2. Schwarz [2005]
Invited Talks
1. Jähne [2004]
2. Jähne [2004]
3. Jähne & Garbe [2004]
4. Jähne et al. [2005]

174 CHAPTER 5. SMALL-SCALE AIR-SEA INTERACTION
5.1.1 Investigation of transport processes across the sea-surface microlayer
by active thermography
Participating scientist Uwe Schimpf and Christopher Popp
Abstract The thermal boundary layer is considered as a black box in linear system theory. The
input is a periodically varying heat flux forced onto the water surface by a carbon dioxide laser, the
output is the amplitude and phase shift of the water surface temperature measured by an infrared
camera.
100 Watts CO 2 laser (10.6 µm)
IR camera
(3-5 µm)
240 cm
100 cm
Paddle
temperature probe
humidity probe
temperature probe
62 cm
X-Y scan unit
flow meter
wind direction
wind speed 1.4 m/s
wind speed 3.2 m/s
wind speed 8.2 m/s
Figure 5.1: Setup of the controlled flux technique in the AEOLOTRON wind-wave facility. A carbon
dioxide laser forces a periodic heat flux onto the water surface. The temperature response of the water
surface is measured by an infrared imager. From the image sequences the amplitude damping and the
phase shift of the temperature signal is calculated.
Background In order to improve the parameterizations
and the models of air-gas exchange,
the transport mechanisms in the boundary layer
and their space and time scales have to be understood
in detail. The active controlled flux technique
[Jähne et al. , 1989] gives a detailed insight
into the turbulent processes controlling the transport
across the sea surface microlayer.
Funding Aktives Thermografie System, HBFG-
125-667 (Hardware), DFG Ja395/13-1 (Joint
project with Detlef Stammer, Insitut für
Meereskunde, Universität Hamburg)
Methods and results Heat is used as a proxy
tracer for gases. The heat flux is controlled by
forcing infrared radiation onto the water surface
and the temperature variation is directly measured
with an infrared imager. For slow temporal
variations of the infrared radiation the transfer velocity
is given by the ratio of the heat flux density
and the temperature variation at the water surface.
If the heat flux is switched off, the temperature
increase will decay with a characteristic time
constant of the transport across the thermal sublayer.
The measured phase shifts clearly indicate
that the transfer process is strongly intermittent.
Outlook/Future work The developed system
will be deploy in the DFG project ”Impact of
Wind, Rain, and Surface Slicks on Air-Sea CO2
Transfer Velocity - Tank Experiments” in cooperation
with the Institute of Oceanography, University
of Hamburg. The goal is to improve the
understanding of the parameterization of air-sea
gas exchange with emphasis on CO2.
Main publication Schimpf et al. [2004]

5.1. SMALL-SCALE AIR-SEA INTERACTION 175
5.1.2 Water flow measurements in environmental and biological systems
Participating scientist Christoph S. Garbe
Abstract Novel measurement techniques are developed for accurately determining water flows in
biological and environmental systems. These techniques are closely linked to the development of refined
image processing techniques, making temporally and spatially highly resolved field measurements
feasible.
a) b) c)
Figure 5.2: In a) a thermal image of the air-water interface is shown with the extracted motion field.
In b) the motion of a microfluidic application is shown, and in c) the flow velocity of Xylem in a plant
leaf can be seen.
Background For a number of exchange processes
both in environmental and life sciences, the
transport of water plays a fundamental role. Systems
of interest are turbulent transport at water
surfaces for air sea heat and gas exchange, water
flow in plant leaves, and microfluids. Density
distributions of tracers are visualized with modern
cameras and their motion as well as density
changes estimated from digital image processing
techniques. Examples of such tracers are heat
which can be applied with lasers and visualized
with highly resolved thermographic imagers or
caged dyes for microfluidic applications. Results
of these flow measurements can be used for modelling
physical transport processes, deepening our
understanding of the systems analyzed.
Funding Research Centre Jülich (Forschungszentrum
Jülich), Jülich
DFG SPP 1147, “Bildgebende Messverfahren für
die Strömungsanalyse”
DFG SPP 1114, “Mathematische Methoden
der Zeitreihenanalyse und digitalen Bildverarbeitung”
Methods and results A fluid is visualized using
density distributions as tracers. These can be
heat or dyes. At the air-water interface, usually
a net heat flux is present which allows visualizing
turbulences directly without additional tracers.
The motion of density distributions is then
modelled as a linear partial differential equation
(PDE). These PDEs can be solved from the image
sequences with techniques developed in digital
image processing. This allows to estimate the
motion as well as density changes in the image
sequences. Through estimating motion as well as
other parameters of the transport model, a deeper
understanding of the transport processes involved
can be reached. Through this technique, the net
heat flux at the air-water interface was estimated
directly for the first time, both temporally and
spatially highly resolved. Furthermore, the flow
of water in plant leaves was also measured in a
relatively simple set-up.
Outlook/Future work The developed techniques
will be used for studying transport processes
for shear driven as well as convective driven
exchange of heat and mass at the air-water interface.
Furthermore, the transport of Xylem in
plant leaves will be measured under varying environmental
forcings. This will make spatially resolved
measurements of water flows in plant leaves
possible for the first time, closing a missing link
in the understanding of water relations in plants.
The low Reynolds number flows in microfluidic
mixing machines will also be measured, allowing
to improve the design and mixing capabilities for
such devices.
Main publication Garbe et al. [2004a]; Zhang
& Garbe [2004]; Garbe et al. [2004b]

176 CHAPTER 5. SMALL-SCALE AIR-SEA INTERACTION
5.1.3 Time resolved Measurements of Air Water Gas Exchange
Participating scientist Kai Degreif
Abstract Laboratory measurements are performed to determine the influence of short wind waves
on air-sea gas exchange. UV-spectroscopy is introduced as a powerful method for tracking the fate
of gaseous and volatile tracers simultaneously both in the gas and water phase. The “controlled
leakage technique”, a new measurement technique that permits the calculation of time resolved flux
rates exclusively from the air-side concentration, could be validated within the scope of the UVmeasurements.
Reliable gas flux measurements of dissolved trace gases for a broad range of species
without the need for extraction are now feasible.
a b
d e
wind speed [m/s]
relative concentration
5
4
3
2
1
0
0 1 2 3
time[h]
4 5 6
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
measured concentration
calculated concentration
0
0 1 2 3
time [h]
4 5 6
c
f
relative concentration
transfer velocity k [cm/h]
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0 1 2 3
time [h]
4 5 6
25
20
15
10
5
0
0 1 2 3
time [h]
4 5 6
Figure 5.3: Time resolved gas exchange measurements at the small Heidelberg Wind Wave Facility. a
Experiments are performed in a small circular water channel of 1.2 m diameter. b Rotating windpaddles
produce controlled wind speeds. c The investigated trace gases are dissolved in the water phase.
The air-volume being constantly flushed with fresh air, the air-side concentration of the released tracers
is proportional to the gas transfer and the water concentration. d Concentration measurements of
volatile aromatics are performed using UV-spectroscopy simultaneously in the air and water phase. e
The calculated water concentration is in good agreement with the measured water concentration. f
Gas transfer velocities are achieved with a high time resolution.
Background The oceans can act as a source
or sink for climate relevant gases such as carbon
dioxide, methane or dimethylsulphide. As hydrodynamics
at the free oceans surface is not well
understood yet, the estimation of total flux rates
of those gases has to rely on empiric parameterizations.
Precise and systematic laboratory measurements
can help us to get a better understanding
of the gas transfer rates dependence on tracer
parameters like Schmidt number and solubility or
hydrodynamic parameters like wind stress, waviness
of the water surface and turbulence intensity.
Methods and results Conventional gas exchange
measurements rely on the knowledge of
concentration gradients across the water surface.
Therefore the information about the concentration
of the dissolved species is indispensable. UVspectroscopy
provides the possibility for direct
and fast measurement of multiple tracer concentrations
both in the water and the atmosphere.
Volatile aromatic hydrocarbons such as benzene,
thiophene, pyridine and derivates, and some other
species can be measured.
The “controlled leakage technique” permits the reconstruction
of the water concentration from gases
that are released by the water body only by measuring
the air concentration. Therefore flux rates
of tracers with a wide range of physicochemical
parameters, i.e. Schmidt number and solubility
can be measured simultaneously so that a detailed
experimental study of the influence of these parameters
on air-water gas exchange has now become
feasible and will be presented within the
work.
Funding Project funded by the DFG
Main publication Degreif, Kai, Doktorarbeit,
Institut für Umweltphysik und Interdisziplinäres
Zentrum für Wissenschaftliches Rechnen, Universität
Heidelberg, 01/2006

5.1. SMALL-SCALE AIR-SEA INTERACTION 177
5.1.4 3-D flow measurements within a porous gravel layer
Participating scientist Michael Klar
Abstract A novel technique for 3-D flow measurements within a permeable gravel layer is developed.
Two fiberoptic endoscopes are used in a stereoscopic arrangement to acquire image sequences of
the flow field within a single gravel pore. The images are processed by a 3-D Particle-Tracking
Velocimetry (3-D PTV) algorithm, which yields the three-dimensional reconstruction of Lagrangian
particle trajectories.
Figure 5.4: Left: Experimental setup with two fiberoptic endoscopes observing the flow field within a
specially prepared artificial gravel pore. Right: 3-D flow trajectories of the pore flow, obtained from
the recorded stereo image sequences.
Background Bed stability of rivers and waterways
is one of the major issues of geotechnical and
hydraulic engineering. The design of erosion protection
structures, e.g. filter layers of noncohesive
gravel, is based on empirical design criteria and
numerical, analytical and phenomenological models
for flow and sediment transport. There is a
lack of experimental data that can be used to validate
and improve these models. A detailed examination
of the hydrodynamic processes that cause
instability of single grains requires flow measurements
with a high temporal and spatial resolution.
Funding Federal Waterways Engineering and
Research Institute (Bundesanstalt für Wasserbau,
BAW), Karlsruhe.
Methods and results The core of the experimental
setup is an artificial gravel pore made up
of grains fixed to each other. Optical access to the
pore volume is given by two flexible fiberoptic endoscopes.
The artificial pore is embedded within a
gravel bed at the bottom wall of an open-channel
flow. Tracer particles are added to visualize the
pore flow, and image sequences of the flow field
inside the artificial pore are recorded.
Analysis of the image sequences by digital image
processing techniques, namely a 3-D PTV algorithm,
yields the Lagrangian flow velocities of the
tracer particles along their trajectories. The algorithm
is based on stereo correlation of the particle
trajectories. The 3-D coordinates are calculated
by triangulation of corresponding optical
rays. Correlating 2-D trajectories instead of the
positions of single particles allows for a simple
setup with a minimum number of two cameras
resp. endoscopes.
Experiments have been conducted in cooperation
with the Federal Waterways Engineering and Research
Institute (Bundesanstalt für Wasserbau,
BAW) in Karlruhe and the Institute for Hydromechanics
of the University of Karlsruhe. Extensive
flow measurements under different flow conditions
have been carried out in an experimental flume located
at the BAW. The impact of the turbulent
free surface flow on the pore flow inside the gravel
bed is clearly reflected in the measurement results.
These studies are part of an international research
project initiated by the BAW, with the objective
to quantify the influence of turbulent velocity and
pressure fluctuations on the stability of river beds.
Outlook/Future work The main subject of
further work will be the comprehensive hydromechanic
analysis of the flow data obtained in the
experiments at the BAW.
Main publication Klar [2005]

178 CHAPTER 5. SMALL-SCALE AIR-SEA INTERACTION
5.1.5 3D fluid flow measurement close to surfaces
Participating scientist Markus Jehle
Abstract A novel measurement technique for 3D reconstruction of Eulerian velocity vector fields
and Lagrangian trajectories at water-side boundary layers in wavy free surfaces is developed. In a
first step, the method is applied in a falling film with known velocity profile.
intensity [arbitrary units]
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
absorption of dye (tartracine)
emission of LED 1 ("royal blue")
emission of LED 2 ("blue")
380 400 420 440 460 480 500 520 540
wavelength [nm]
Figure 5.5: Top: Experimental setup. Bottom:
The emitted light of the two types of LEDs
(“blue” and “royal blue”) is absorbed by the dye
(tartracine acid yellow) unequally. Thus, with
known penetration depths, a reconstruction of the
depth of the observed particle is possible.
Background In order to examine the air-water
gas exchange, a detailed knowledge of the waterside
flow-field is needed. Therefore important
quantities like wall-shear stresses, velocity profiles,
dissipation rates and Lagrangian trajectories,
have to be determined. Because the flow
is 3D, instationary and close to the wave-driven
(curved and moving) water-surface, conventional
techniques like Particle Imaging Velocimetry using
laser light sections are not applicable. A technique
that is similar to the one proposed here is
applied in the field of biofluidmechanics succesfully,
where it is important to get knowledge about
the flow in (artificial) blood vessels.
Methods and results A fluid volume is illuminated
by LEDs. Small glas hollow spheres (mean
diameter 30µm) are added to the fluid, working as
tracer. A high speed camera pointing to the water
surface from above records the image sequences.
The depth of an individual fluid particle is coded
by a supplemented dye, which absorbs the light of
the LEDs obeying Beer-Lambert’s law. By using
LEDs flashing with two different wavelengths it is
possible to use particles variable in size:
The depth of a particle, which appears to the camera
under the intensities (gray values) g1 and g2
is calculated according to
z(g1, g2) = z∗1z∗2
z∗1 − z∗2
�
ln
� g1
g2
�
+ ln
� g02
g01
��
,
where z∗1 and z∗2 are the penetration depths of
LED-light of two distinct wavelengths into the
dyed fluid, and g01/g02 is the ratio of the intensities
of the two light sources. All of these quantities
can be obtained by means of calibration.
The velocity vectors of the flow are obtained using
an extension of the method of optical flow,
allowing for exponential brightness changes.
First results obtained in a laminar falling film
with known hydrodynamics show the feasibility
of this measurement technique: the measurement
reproduces the theoretical velocity profile in good
agreement.
Outlook/Future work The method will be extended
to higher particle densities, coping with
the problem of overlapping of the motion of individual
particles. Further, the technique will be
applied both at curved and at moving free surfaces.
Simultaneous measurements using active
thermography and imaging slope gauge will be
conducted.
Funding DFG-Schwerpunktprogramm 1147

5.1. SMALL-SCALE AIR-SEA INTERACTION 179
5.1.6 Imaging concentration profiles of water boundary layer by Double-
Dye LIF
Participating scientist Achim Falkenroth
Abstract Laser-Induced Fluorescence (LIF) is applied to directly observe and understand the mechanism
of gas exchange in the upper 500 µm boundary layer. The luminescent dye used (Ru-complex)
is sensitive to a given in-situ oxygen concentration that quenches the phosphorescence. The new
Double-Dye LIF technique strives for a 2-D spatial resolution of 200x50 µm 2 .
Figure 5.6: The camera looks through a prism on the surface to measure a wavelength spectrum for
every point of a laser line. Spectra with and without the second dye are shown on the left.
Background The difficulty in studying the
inter-phase exchange processes is due to the small
interacting thickness of approximately 30 µm to
1 mm on both sides of a boundary layer z∗. Therefore,
none of the traditional fixed sampling methods
are applicable.
A non invasive optical method using luminescent
dyes is chosen to determine the gas concentration.
Especially phosphorescent dyes are advantageously
sensitive to quenching because of the long
live time of their excitation states. In regions of
high oxygen concentration, the amount of light
emitted will be significantly lower.
Fluorescent pH indicators may also be used, as
they are able to quantitatively visualise acid or
basic gases like HCl, NH3, or CO2. In former
studies, the boundary layer of the water was monitored
sideways. This way, it is difficult to get a
high resolution with a wavy and agitated surface.
Methods and results The idea of this work is
to reconstruct the concentration profile by looking
from the top on the surface using the spectral
information of all points illuminated by a visible
laser system. The light emitted by the luminescent
dye travels back to the surface through the
water body.
A second dye is dissolved which absorbs certain
wavelengths of the emission spectrum. Therefore,
the deepness information is concealed in the light
spectra. By applying an inverse modelling approach,
the concentration depths can be evaluated
over the whole depth profile.
The time resolution aimed for is naturally predetermined
by the demanding task to catch the
micrometer waves and turbulence events like, for
example, surface renewal. Finally, a temporal resolution
of 30 − 100 Hz should be reached.
First results are luminescence spectra of about 300
pixels acquired with a low noise camera. The signal
appears to be adequate as an input for the
inverse calculation in order to gain the concentration
profiles.
Outlook/Future work The consistent next
steps will be to improve the resolution and stability
of the reconstruction. The application of this
method for measurements in a water tank with
wind generated waves lies ahead.
Funding DFG-Research-Training-Group
(Graduiertenkolleg 1114)

180 CHAPTER 5. SMALL-SCALE AIR-SEA INTERACTION
5.1.7 Combined slope/height measurements of short wind waves : ISHG
Participating scientists Roland Rocholz, Martin Schmidt
Abstract A new technique for the simultaneous measurement of wave height and wave slope of
water surface waves has been developed. The Imaging Slope/Height Gauge (ISHG) is an imaging
system that is designed to measure waves at different length scales. Using a high speed camera, the
high spatiotemporal resolution provides an insight into hydrodynamic processes such as microscale
wave breaking and small scale wave-wave interaction.
f 2
high speed camera
(lens set to infinity)
lens (L 2 ) for telecentric
imaging (f 2 = 50 cm)
water body
lens (L 1 ) for telecentric
illumination (f 1 = 25 cm)
diffusing screen
rays are only
for illustration
(entrance pupil of the
camera lies at the focal
point of lens L 2 )
f 2 (mean water height is at
focal distance to L 2 )
water height
(6 to 16 cm)
f 1 (diffusing screen is at
focal distance to L 1 )
programmable LED-array
(320x1W, λ = 880nm)
Figure 5.7: Sketch of the wave imaging system
for the simultaneous measurement of waves height
and slope.
Background Since water surface waves
strongly influence transfer velocities due to the
induced turbulence, such wave measurements are
used for monitoring the conditions in gas exchange
experiments. Unfortunately, the slope calibration
of typical imaging wave measurement techniques
like the color imaging slope gauge used at the
Heidelberg Aeolotron so far is depending on the
wave height of larger waves. To overcome this
source of systematic errors, a new technique is
under development with the following aims:
• The slope of the waves should be measured
without biases due to the wave height
• The image size should not change with wave
height
• The wave slope and height should be measured
simultaneously
• Simple set-up with a single camera
Funding DFG, Ja395/13: ”Mechanismen des
Gasaustausches zwischen Atmosphäre und Ozean:
Laborversuche und Modellierung”
Methods and results Like the color imaging
slope gauge the slope measurement of the new
Imaging Slope/Height Gauge (ISHG) is based on
light refraction (shape from refraction) and makes
use of an area-extended light source with defined
spatial variation of radiance, produced by a programmable
LED array. This Imaging Slope Gauge
gives a 2-D slope map of the water surface. The
Imaging Height Gauge gives the 2-D height map.
This is also used to correct the slope map for
height dependencies. The method is based on
light absorption and works with light in the near
infrared range. The optical setup provides a telecentric
imaging. The camera is virtually located
at infinity so that height variations of the water
surface do not affect the image scaling.
Outlook/Future work The ISHG system at
our small wind wave flume is still under construction.
The calibration and first wave measurements
are expected to take place at the end of year 2005.
It is planned to assemble the same system at the
wind-wave tank of the University of Hamburg and
at the wind-wave facility AEOLOTRON, University
of Heidelberg. Combining the ISHG with infrared
imaging will be the next step of extending
the system.
Main publication Jähne et al. [2005c]

5.1. SMALL-SCALE AIR-SEA INTERACTION 181
5.1.8 Development of a depth resolving boundary layer visualization for
gas exchange at free water surfaces
Participating scientist Tobias Schwarz
Abstract To directly visualize gas concentration transport in the water-sided boundary layer, a
combined LIF-measurement system consisting of a laser scanning unit and a confocal microscope has
been developed and constructed. Furthermore, methods to reconstruct a 2-D depth profile had been
investigated.
Figure 5.8: An example of the fluorescence intensity changes through local gas concentrations, illuminated
with the laser scanning system.
Background As detailed knowledge of gas exchange
between atmosphere and ocean is of great
importance for predicting and modeling future
climate situations, this diploma thesis aimed at
the development of a measurement system for improved
gas exchange measurements.
Funding Graduiertenkolleg 1114 “Optische
Messtechniken für die Charakterisierung von
Transportprozessen an Grenzflächen” (TU Darmstadt
and U Heidelberg)
Methods and results A measurement setup
is introduced which makes it possible to directly
measure two-dimensional, vertical concentration
profiles of gases in the water sided boundary layer
using Laser-Induced Fluorescence (LIF). While it
is impossible to gain knowledge of the physical
processes involved in gas exchange using measurements
of transfer rates and mass balances, the introduced
method makes it possible to directly visualize
the physical processes of matter transport
in the layer. The measurement method is based on
two basic principles: First, a fluorescence indicator
is used, whose fluorescence intensity is proportional
to the local pH-value, thus allowing a spa-
tial resolved measurement of the concentrations of
dissolved alkaline or acidic gases. Second, to create
a depth resolution, a second, absorbing dye is
added, whose absorption maximum lies inside the
fluorescence spectrum, so that spectra from different
depths show changes in their spectral shape
due to the different light path lengths through the
absorber. Thus the measured spectrum is the superposition
of all depth spectra, which provide the
basis of a linear inverse problem. Models for the
reconstruction of the depth information will be introduced
in the course of this thesis, and the solvability
will be analyzed. As the stability of the
solution of the inverse problem is almost exclusively
determined by the invertibility of the basis
function matrix, a confocal microscope was constructed,
which allowed the direct measurement of
depth spectra. Thereby it was made possible to
numerically analyze and evaluate the conditioning
of the matrix invertibility.
Outlook/Future work Work to be continued
within Graduiertenkolleg 1114
Main publication Schwarz [2005]

182 CHAPTER 5. SMALL-SCALE AIR-SEA INTERACTION
References
Bock, E. J., Hara, T., Frew, N. M., & McGilles, W. R. 1999. Relationship between air-sea gas transfer
and short wind waves. J. Gephys. Res., 104, 25 821–25 831.
Frew, N. M. 1997. The role of organic films in air-sea gas exchange. Pages 121–172 of: Liss, Peter S., &
Duce, Robert S. (eds), The Sea Surface and Global Change. Cambridge, UK: Cambridge University
Press.
Frew, N. M., Bock, E. J., Schimpf, U., Hara, T., Haußecker, H., Edson, J. B., McGillis, W. R., Nelson,
R. K., McKeanna, B. M., Uz, B. M., & Jähne, B. 2004. Air-sea gas transfer: its dependence on wind
stress, small-scale roughness and surface films Small-Scale Air-Sea Interaction with Thermography.
Journal of Geophysical Research, C8(109). C08S17, doi:10.1029/2003JC002131.
Fuß, D. 2004. Kombinierte Höhen- und Neigungsmessung von winderzeugten Wasserwellen am Heidelberger
Aeolotron. PhD Thesis, Universität Heidelberg.
Garbe, C. S., Spies, H., & Jähne, B. 2003. Estimation of Surface Flow and Net Heat Flux from
Infrared Image Sequences. J. Mathematical Imaging and Vision, 19, 159–174.
Garbe, C. S., Schimpf, U., & Jähne, B. 2004a. A Surface Renewal Model to Analyze Infrared Image
Sequences of the Ocean Surface for the Study of Air-Sea Heat and Gas Exchange. Journal of
Geophysical Research, C8(109). C08S15, doi:10.1029/2003JC001802.
Garbe, C. S., Smoljar, N., Korniyenko, M., & Schurr, U. 2004b. Water relations in plant leaves. Chap.
19 of: Image Sequence Analysis to Investigate Dynamic Processes. Lecture Notes in Computer
Science. Springer.
Hilsenstein, V. 2004. Design and Implementation of a Passive Stereo-Infrared Imaging System for the
Surface Reconstruction of Water Waves. Ph.D. thesis, Universität Heidelberg.
Jähne, B. 1980. Zur Parameterisierung des Gasaustausches mit Hilfe von Laborexperimenten. Diss.,
Univ. Heidelberg. D-200.
Jähne, B. 2001. Air-Sea Interaction: Gas Exchange. In: Steele, J., Thorpe, S., & Turekian, K. (eds),
Encyclopedia of Ocean Sciences. Academic Press, London.
Jähne, B. 2004. Exchange Processes at the Ocean Surface: Their Role in Coupling Atmosphere and
Ocean, A Contribution to the SOLAS Project. Invited talk, Hauptvortrag Fachverband Umweltphysik,
DPG Frühjahrstagung München, 22. Mrz 2004.
Jähne, B. 2004. Handbook of Digital Image Processing for Scientific and Technical Applications. 2nd
edn. Boca Raton: CRC Press.
Jähne, B. 2004. New Insight into the Mechanisms of Air-Sea Gas Transfer. Invited talk, IOW-
Kolloquium, Leibniz-Institut fr Ostseeforschung, Warnemünde, Januar 2004.
Jähne, B. 2005a. Digital Image Processing. 6th edn. Berlin: Springer.
Jähne, B. 2005b. Digitale Bildverarbeitung. 6th edn. Berlin: Springer.
Jähne, B., & Garbe, C. S. 2004. Spatiotemporal Active Thermography. Invited talk, 7th International
Conference on Quantitative Infrared Thermography, von Karman Institute for Fluid Dynamics in
Rhode Saint Genèse, Belgium, 08. July 2004.
Jähne, B., & Haußecker, H. 1998. Air-Water Gas Exchange. Annual Rev. Fluid Mech., 30, 443–468.
Jähne, B., Münnich, K. O., Bösinger, R., Dutzi, A., Huber, W., & Libner, P. 1987. On the parameters
influencing air/water gas exchange. J. Geophys. Res, 92, 1937–1949.
Jähne, B., Libner, P., Fischer, R., Billen, T., & Plate, E. J. 1989. Investigating the transfer processes
across the free aqueous viscous boundary layer by the controlled flux method. Tellus, 41B, 177–195.
Jähne, B., Nielsen, R., Popp, C., Schimpf, U., & Garbe, C. S. 2005. Air-Sea Gas Transfer: Schmidt
Number Dependency and Intermittency. Invited talk, 37th International Liège Colloquium on Ocean
Dynamics Gas Transfer at Water Surfaces, 2–6 May 2005.

5.1. SMALL-SCALE AIR-SEA INTERACTION 183
Jähne, B., Schmidt, M., & Rocholz, R. 2005c. Combined optical slope/height measurements of short
wind waves: principle and calibration. Meas. Sci. Technol., 16, 1937–1944.
Klar, M. 2005. Design of an endoscopic 3-D Particle-Tracking Velocimetry system and its application
in flow measurements within a gravel layer. Ph.D. thesis, Universität Heidelberg.
Liss, P. S., & Merlivat, L. 1986. Air-sea gas exchange rates: introduction and synthesis. Pages 113–127
of: Buat-Menard, P. (ed), The Role of Air-Sea Exchange in Geochemical Cycling. Dordrecht, The
Netherlands: Reidel.
Nielsen, R. 2004. Hochgenaue Messung der Schmidtzahlabhängigkeit des Gasaustausches an einer
wind- und wellenbewegten Wasseroberfläche. Ph.D. thesis, Universität Heidelberg.
Rocholz, R. 2005. Bildgebendes System zur simultanen Neigungs- und Höhenmessung an kleinskaligen
Wind-Wasser-Wellen. diploma thesis, Universität Heidelberg.
Schimpf, U., Garbe, C. S., & Jähne, B. 2004. Investigation of transport processes across the seasurface
microlayer by infrared imagery. Journal of Geophysical Research, C8(109). C08S13,
doi:10.1029/2003JC001803.
Schwarz, T. 2005. Development of a depth resolving boundary layer visualization for gas exchange at
free water surfaces. diploma thesis, Universität Heidelberg.
Wanninkhof, R. 1992. Relationship between wind speed and gas exchange over the ocean. J. Gephys.
Res., 97, 7373–7382.
Zappa, C. J., Asher, W. E., Jessup, A. T., Klinke, J., & Long, S. R. 2001. Effect of microscale wave
breaking on air-water gas transfer. Pages 23–29 of: Donelan, M. A., Drennan, W. M., Saltzman,
E. S., & Wanninkhof, R. (eds), Gas Transfer at Water Surfaces. Geophysical Monograph, vol. 127.
Washington, DC: American Geophysical Union.
Zhang, X., & Garbe, C. S. 2004. Studying dynamical processes of air-sea exchanges with air-water inerface
image techniques. Chap. 3, pages 57–88 of: Recent Research Developments in Fluid Dynamics,
vol. 5. Transworld Research Network.

Forschungsstelle “Radiometrie” of
the Heidelberger Akademie der
Wissenschaften
6.1 Radiometric Dating of Water and Sediments . . . . . . . . . . . . . . . . 187
185

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 187
6.1 Radiometric Dating of Water and Sediments
The Forschungsstelle is an independent research unit funded by the Heidelberger Akademie der Wissenschaften.
Funding began in the year 1958 and will run until the end of 2010.
Personnel :
Prof. Dr. Augusto Mangini
Dr. Bernd Kromer
Dr. Marcus Christl
Dr. Denis Scholz
René Eichstätter, Technician
Maleen Gillmann, Technician
Sebastian Welk, Technician
Karoline Thomas, Secretary
Additional funding from the DFG, BMBF and EU (CarboEurope-IP):
Scientists: Pablo Verdes, Marcus Christl, Denis Scholz, Andrea Schröder-Ritzrau, Sahra Talamo,
Michael Friedrich,
PhD-students: Frank Bernsdorff, Holger Braun, Nicolas Latuske, Jörg Lippold, Marga-rita Koroleva,
Ingmar Unkel,
Technicians: Helga Baus, Maleen Gillmann, Sabine Kühr, Eva Gier and 4 student assistants
Master-students: Kerstin Bohn, Daniel Schimpf, Boris Schulze, Nicole Vollweiler, Patrick Wenderoth
The task of the Forschungsstelle ”Radiometrie”of the Heidelberger Akademie der Wissenschaften is
the dating and interpretation of climate archives. The research unit consists of two groups, the 14 C
Lab (Bernd Kromer) and the Th/U-Lab (Augusto Mangini).
14 C Lab The focus of the 14 C Lab are highly precise 14 C-dating and the construction of a calibration
curve for radiocarbon that reaches far back into the last Glacial. Furthermore this Lab delivers 14 Cdatings
for several archeological groups.
Methods We use both the conventional gas-counting technique and AMS. The gas counters were
developed to highest precision (better than 2 �). For AMS we prepare graphite targets, to be
measured at one of the European AMS facilities.
Extension of tree-ring based 14 C calibration into the Late Glacial In collaboration with
the tree-ring laboratories of the University Stuttgart-Hohenheim and the University of Zürich/WSL
Birmensdorf we extend the tree-ring based 14 C calibration into the past. Presently, the absolutely
(annually) dated oak and pine chronology starts at 12.400 years BP (before AD 1950) [Friedrich et
al., 2004; Reimer et al. 2004]. In the Late Glacial two independent chronologies were built in the two
tree-ring labs, assisted by numerous 14 C predating in our laboratory [Kromer et al., 2004; Schaub et
al., 2005]. Based on a comparison to the marine 14 C of [Hughen et al., 2004] the chronologies cover
the mid-Bølling, all of the Allerød and the initial 150 years of Younger Dryas (ca. 14,100 to 12,800
cal BP). The trees were recovered from gravel pits at the Danube river and its tributaries, the lignite
area south-east of Berlin, and construction sites in Zürich. Beyond the range of these chronologies we
assembled several floating 14 C sections from trees found in Northern Italy and Romania.
The 14 C data sets are evaluated to infer solar activity variability [Bond et al., 2001; Solanki et al.
2004, Usoskin et al., 2005] as well as ocean thermohaline circulation changes. Combined with 10 Be
time series from Greenland they may serve to link tree-ring and ice-core time-scales. From dendroclimatological
parameters of tree-rings, such as ring-widths, frost damage and growth patterns climate
anomalies can be reconstructed.
14 C dating, archaeology and geosciences We maintain extensive collaborations with archaeologists
to date key sites, such as Troy [Kromer et al. 2002] or the Nasca sites in Peru [Eitel et al.
2005], and to anchor floating tree-ring sections by 14 C wiggle-matching to the absolute scale. In the
’Roman Gap Project’ (http://www.arts.cornell.edu/dendro/2004News/ADP2004.html) we assist in
the extension of the Eastern Mediterranean chronologies into the first millennium AD, to link the
absolute part to the 2300-year long Bronze Age chronology [Manning et al., 2003]. The date of the
eruption of Thera remains a crucial and still controversial time marker of the Late Bronze Age in the
Eastern Mediterranean. In long-standing collaborations with colleagues in archaeology we contribute
to a high-precision 14 C date of this event [Manning et al., 2001].

188 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
14 C in the present-day carbon cycle The present-day 14 C level is largely determined by the
re-equilibration of the atmosphere following strong 14 C input during the bomb testing up to 1962,
and the dilution of the natural 14 C level by anthropogenic, 14 C free, CO2 emissions (see contribution
by I. Levin in this report). In our laboratory continuous 14 C times series from several sites around
the globe have been measured up to today, now covering more than 40 years [Levin & Kromer, 2004].
Recently, 14 C has become an important marker to determine the ratio of fossil to present-day sources
of carbon, e.g. in the emissions trading. Here we are involved in pilot studies to establish legislative
procedures.
Th/U-Lab The Th/U-Lab works on continental archives, such as speleothems and travertines, as
well as on marine samples, such as deep sea sediments, Mn-nodules and corals.
One principal focus is the determination of the natural variations of Holocene and Late Pleistocene
climate using the stable isotopic composition of speleothems. Furthermore, we determine the magnitude,
timing, and duration of past sea level fluctuations from the position and age of fossil coral reefs
as well as the intensity of the Earths magnetic field during the past 350,000 years from 10 Berecords.
These studies deliver a precise time scale for the variations of past climate. This is a basic requirement
for the understanding of the causal relationships and the complex interplay between the forcing and
feedback mechanisms in the climate system during the past 350,000 years and during the Holocene. We
work in close cooperation with climate modelers from Hamburg and Berlin in the DEKLIM program
(through 5/2006). With modelers from Potsdam we apply their CLIMBER2 model to study the
abrupt climate changes that occurred during the Last Glacial (Dansgaard/Oeschger events).
Methods We use dating methods, relying on the disequilibrium of the natural decay chains (TIMS-
230 Th/U and 231 Pa/U). In addition, we use the decay of 10 Be, a radioactive product of cosmic rays.
Speleothems, an archive of paleoclimate Speleothems are an excellent climate archive because
they can be dated very precisely with the Th/U method. Stable isotope signals recorded in these
stalagmites can be measured at a resolution of 100 µm and hence provide a climate signal of one-yearresolution.
Most isotope signals in stalagmites display significant kinetic effects. These kinetic signals have been
related to the intensity of precipitation within the last ten years. For example, periods of enhanced
kinetic were ascribed to periods of less intense precipitation in speleothems from Oman and from
Central Germany [Burns et al.,2002; Fleitmann et al., 2003; Neff et al., 2001; Niggemann et al,2003].
The combination of this high resolution proxy for precipitation and the precise Th/U dating lead to
a number of internationally regarded publications. For example, we found a very good correlation
between the intensity of precipitation in Oman and the intensity of solar irradiation [Neff, 2001].
This relationship has been confirmed by a number of following studies [e.g. Holzkämper et al., 2004;
Mangini et al., 2005].
In November 2005 we were granted by the DFG for a Forschergruppe (www.fg-Daphne.de) to study the
basic processes affecting speleothem formation as well as the isotopic and the chemical signals. These
studies will establish and improve the applicability of speleothems as archives for past precipitation
and temperature. The DAPHNE project is funded for the next three years, with an option for funding
for three additional years. We will work in close collaboration with groups from Bochum, Trento (Italy)
and Innsbruck (Austria).
Reconstruction of Sea level from fossil corals Reconstructions of past sea level allow to determine
the magnitude, timing and duration of interglacial periods. which are essential for the understanding
of the causal relationships and the complex interplay between the forcing and feedback
mechanisms in the climate system.
Some reef coral genera grow in upper 5m below sea surface only and record past sea level fluctuations.
Thus, the determination of accurate U-series ages provides a direct method for sea level reconstruction.
Unfortunately, many fossil reef corals show clear evidence for post-depositional open-system behaviour.
There-fore, conventional Th/U-ages obtained from such corals cannot be considered as strictly reliable.
We dealt with this problem (i) by identifying corals that have not been altered [Scholz and Mangini,
in press] and (ii) by developing an appropriate correction technique [Scholz et al., 2004]. The results
enabled to reconstruct sea level during Marine Isotope Substage 6.5 (∼175,000 years before present).
The intensity of the Earth’s magnetic field in the past Accumulating evidence suggests that
solar activity is responsible for at least some climatic variability. These include correlations between

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 189
solar activity and either direct climatic variables or indirect climate proxies over time scales ranging
from days to millennia [Eddy, 1976; Labitzke & van Loon, 1992; Svensmark & Friis-Christensen, 1997;
Soon et al., 1996, 2000; Beer et al., 2000; Hodell et al., 2001]. A very notable correlation was that
obtained in our group in Heidelberg [Neff et al., 2001]. However, the climatic variability attributable
to solar activity is larger than could be expected from the typical 0.1% changes in the solar irradiance
observed over the decadal to centennial time scale [Beer et al., 2000; Soon et al., 2000]. Thus, an
amplifier is required unless the sensitivity to changes in the radiative forcing is uncomfortably high.
The first suggestion for an amplifier of solar activity was suggested by Ney [1959], who pointed out
that if climate is sensitive to the amount of tropospheric ionization, it would be sensitive the intensity
of the Earth’s magnetic field as well as to solar activity since the solar wind modulates the cosmic ray
flux (CRF), and with it, the amount of tropospheric ionization.
We are studying 10 Be in marine sediments to determine the timing and the intensity of the Earth’s
magnetic field in the past. The cosmogenic nuclide 10 Be is mainly produced in the lower stratosphere
by interaction of galactic cosmic rays with oxygen and nitrogen atoms, and its production is known
to be strongly anti-correlated with the solar- and/or geomagnetic field strength. In addition, highly
resolved profiles of 10 Be in marine sediments may be used to synchronize the marine to the ice core
ones.
Cooperations The Forschungsstelle Radiometrie of the Heidelberger Akademie der Wissenschaften
cooperates in the following projects with these institutions.
Germany: Research Centre Ocean Margins, University of Bremen; Geosciences, University of Trier;
Institute for Paleontology, University of Erlangen; Institute of Mineralogy, University of Frankfurt
a.M.; Institute of Environmental Geochemistry, University of Heidelberg; Potsdam Institute for Climate
Impact Research, Potsdam; Alfred-Wegener Institute, Bremerhaven; ICG-V, Research-Centre
Jülich; Faculty of Natural Sciences, University of Hohenheim, Stuttgart
Foreign Countries: Paul-Scheerer Institut, ETH-Zürich, Switzerland Geology and Paleontology, University
of Innsbruck, Austria
Publications
Peer Reviewed Publications
1. Braun [in press]
2. Christl et al. [2004]
3. Eitel et al. [2005]
4. Felis et al. [2004]
5. Fleitmann et al. [2004]
6. Friedrich et al. [2004]
7. Holzkämper et al. [2004]
8. Holzkämper et al. [2005]
9. Hughen et al. [2004a]
10. Hughen et al. [2004b]
11. Kromer et al. [2004]
12. Levin & Kromer [2004]
13. Mangini et al. [2005]
14. McHargue & Donahue [2005]
15. McManus et al. [2004]
16. Reimer et al. [2004]
17. Schaub et al. [2005]

190 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
18. Scholz et al. [2004]
19. Solanski et al. [2004]
20. Usoskin & Kromer [2005]
21. Verdes et al. [in pressa]
22. Verdes et al. [in pressb]
23. Wurth et al. [2004]
Other Publications
1. Christl et al. [2005]
2. Scholz & Mangini [in press]
3. Schröder Ritzrau et al. [2005]
4. Spötl et al. [2004]
Doctoral Theses
1. Scholz [2005]
Diploma Theses
1. Bohn [2005]
2. Schimpf [2005]
3. Schulze [2005]
4. Wenderoth [2005]

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 191
6.1.1 Reconstruction of the geomagnetic field strength over the past 300,000
years derived from 10 Be data of deep sea sediments from the North
and South Atlantic Ocean
Participating scientists Frank Bernsdorff, M. Christl, P. Wenderoth, B. Schulze, A. Mangini, D.
Wagenbach, G. Brey (Frankfurt), P. Kubik (Zürich)
Abstract In this project we use the anti correlation between the 10 Be production in the Earth’s
stratosphere via galactic cosmic rays and the strength of the geomagnetic field to determine its variation
over a time period of 300,000 years. Two deep sea sediment cores (ODP) from the Atlantic
Ocean, which act as 10 Be archives are investigated.
Background The cosmogenic nuclide 10 Be is
mainly produced in the lower stratosphere by interaction
of galactic cosmic rays with oxygen and
nitrogen atoms, and its production is known to
be strongly anti-correlated with the solar- and/or
geomagnetic field strength. After a short atmospheric
residence time of about 1 year 10 Be is
removed from this part of the atmosphere and
deposited onto land, ice sheets and (mainly) the
ocean surface. Therefore, it should be possible
to extract a record of geomagnetic paleointensity
(GPI) from depositional profiles of these radionuclides
in marine, terrestrial and ice core archives.
In this study we are investigating two deep sea
sediment cores from the North and South Atlantic
Ocean (ODP-Site 983 and ODP-Site 1089)
for highly resolved 10 Be profiles. The application
of a special correction procedure (involving uranium
and thorium measurements) is indispensable
to quantify the transport of 10 Be in the ocean, so
that the global 10 Be-production can be extracted
from marine records. Based on these profiles, a
marine 10 Be stratigraphy will be developed that
can be matched with 10 Be records from Greenland
(GRIP, GISP II) and Antarctic (EPICA) ice cores.
In particular, enhanced global 10 Be-production
during geomagnetic events (Lachamp, Blake, Jamaica)
can be used as global time marker for the
synchronization of marine and ice core chronologies.
Based on the 10 Be stratigraphy a record of
relative paleointensity will be calculated independently
from the magnetization data
Funding DFG Schwerpunktprogramm: Antarktisforschung
mit vergleichenden Untersuchungen
in arktischen Eisgebieten (SPP 1158)
Methods and results Besides the measurement
of 10 Be in Zürich, we are implementing the
new technique of ICPMS for the precise determination
of thorium and uranium isotopes in sediments.
During initial tests we analyzed a number
of different standard solutions and deep sea
sediment samples of known isotopic composition.
First samples of ODP 983 sediments are presently
studied.
Outlook/Future work According to the goals
of this project, the future work will mainly comprise
10 Be measurements of the deep sea sediments
from ODP site 983, its normalization to
230 T hxs(0) and comparison to the data set of ODP
site 1089 (South Atlantic).
Main publication Christl et al. [2005]

192 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
6.1.2 Possible solar origin of the glacial 1,470-year climate cycle demonstrated
in a coupled climate model
Participating scientists H.Braun, M.Christl, A.Mangini, B.Kromer (AdW Heidelberg), K.Roth
(IUP Heidelberg), S.Rahmstorf, A.Ganopolski (PIK Potsdam), C.Kubatzki (AWI Bremerhaven)
Abstract It is shown that an intermediate-complexity climate model reproduces abrupt glacial
warmings (Dansgaard-Oeschger events) with a spacing of 1470 years when forced by freshwater cycles
of about 87 and 210 years, i.e. with periods close to known solar cycles. Thus, the glacial 1470-year
climate cycle could be caused by the Sun despite the lack of a 1470-year solar period.
Figure 6.1: Forcing and model response. The applied freshwater forcing (left panel, in mSv [1 Sv =
106 m 3 /s]) is the sum of two sinusoidal cycles with periods of 210 years and 86.5 years, respectively.
These periods are close to well-known solar cycles. In response to this forcing, the applied climate
model can show abrupt warm events in Greenland (Dansgaard-Oeschger events) with a period of 1470
years (right panel, in ◦ C). The dashed lines in both panels are spaced by 1470 years.
Background Many paleoclimatic archives show
a quasi-cycle of about 1470 years in the Last
Glacial. This pattern is manifested in rapid
climate shifts, the so-called Dansgaard-Oeschger
(DO) events. To explain these, various concepts
have been proposed, including internal oscillations
in the climate system and external (e.g. solar)
forcing. However, while pronounced solar cycles
of about 87 and 210 years are well-known [Peristykh
and Damon 2003, Wagner et al. 2001], a
1470-year cycle has not been found [Stuiver and
Braziunas 1993]. This has been considered as a
main argument against solar origin of the glacial
1470-year climate cycle.
Funding This work was funded by the Heidelberg
Academy of Sciences.
Methods and results To test if the lack of
a 1470-year solar cycle indeed argues against solar
origin of the DO events, we used the climate
system model CLIMBER-2 of the Potsdam Institute
for Climate Impact Research (PIK). In earlier
simulations with the model, abrupt glacial warming
events were already simulated which reproduce
many features of the observed DO events
[Ganopolski and Rahmstorf 2001, Ganopolski and
Rahmstorf 2002]. In the model, DO events represent
rapid transitions between a stadial (cold)
and an interstadial (warm) mode of the North Atlantic
thermohaline circulation (THC), triggered
by a threshold process.
In our model study, a freshwater forcing was applied
which is the sum of two sinusoidal components
with periods 1470/7 (=210) and 1470/17
(about 86.5) years (left panel in figure 1). The amplitudes
of both forcing components are small (10
mSv, i.e 10.000 m 3 /s), that is, about 5 cm/year
in the surface freshwater flux. Although the total
forcing does not explicitly have a spectral component
of 1470 years, it repeats with this period due
to the combined effect of the applied cycles.
The forcing can excite DO-like events in the North
Atlantic region (right panel in 6.1). Within a large
forcing-parameter range, these events are spaced
by 1470 years. This timescale is robust when
the phases, amplitudes, and periods of the two
forcing cycles are changed over some range. If
instead of two sinusoidal cycles a more realistic
forcing is applied with spectral properties close
to that observed in solar proxies, a regular 1470year
model response is still found. The stability
of the simulated 1470-year cycle results from two
well-known properties of the THC: its long characteristic
timescale, and the non-linearity (i.e. the
threshold character) inherent in the transitions
between the two modes of the THC. For Holocene
conditions, DO events do not occur in the model.
To conclude, our results show that the lack of
a 1470-year solar cycle does not by itself argue
against a solar origin of the glacial 1470-year climate
cycle.
Main publication Braun et al. [in press]

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 193
6.1.3 Solar variability and rapid climate change on decadal to centennial
scales
Participating scientist Michael Friedrich (Universität Hohenheim), Bernd Kromer, Nicolas Latuske,
Sabine Remmele (Universität Hohenheim), Gerd Schleser (Forschungszentrum Jülich)
Abstract The relation between solar variability and climate variations in the Holocene was investigated.
The heliomagnetic variations were derived from fluctuations of the production of 14 C,
calculated from the atmospheric 14 C activity using a carbon box model. Statistical parameters obtained
from tree ring widths were correlated with the 14 C production at two intervals of low solar
activity where previously cooling in the North Atlantic has been documented. Generally only weak
correlations were found, probably pointing to a low climate sensitivity of riverine oaks in the Holocene.
Figure 6.2: Spectral features in the detrended ∆ 14 C data (upper curve); and band-pass-filtered ∆ 14 C.
Center band-pass wavelength are of 88, 210, 500 and 950 years (top to bottom).
Background The sun is the most important
driving force in the climate system, but only little
is know how the climate system reacts to changes
of the solar magnetic activity on decadal to multicentennial
scales. It is known that the Little Ice
Age coincided with the decrease of solar activity
in the Maunder Minimum (1645-1715) but the
mechanism remains unclear. To investigate how
the variation of the climate system responses to
the variability of solar activity, we used the atmospheric
14 C signal (∆ 14 C) recorded in tree rings
as proxy of solar activity.
In this study we investigated the variation of
∆ 14 C changes in the time period of the Holocene
on time scales from decades to centennial and
correlated statistic parameters as calculated from
tree rings with selected maxima of 14 C production
(minima of solar activity).
Funding Deutsches Klimaforschungsprogramm
(DEKLIM)
Methods and results The fluctuations in
the 14 C production were calculated from the
atmospheric 14 C (∆ 14 C) using a Oeschger-
Siegenthaler-type box-diffusion model of the carbon
cycle. Model experiments were done to investigate
the influence of changes in diffusive deepocean
ventilation, air-sea gas exchange rate and
14 C production. Furthermore, the atmospheric
14 C was spectrally analyzed with various methods
(Singular Spectrum Analysis, Maximum Entropy
Method and Multi Taper Method, Digital Filters
(IIR) and Wavelets) to obtain solar variability periods
(Fig. 6.2). Finally, statistical parameters of
tree ring chronologies in southern Germany were
calculated, and they were correlated to the 14 C
production changes at intervals of low solar activity
(∆ 14 C maximum).
In two intervals of low solar activity, centered
at 2800 BC and 800 BC, respectively, the treering
parameters (derived from the ring widths) are
weakly correlated with the 14 C production. The
tree-ring parameters indicate that in these intervals
the precipitation increased and the temperature
decreased at times of solar minimum, pointing
to a role of solar forcing of climate variability.
Model experiments to explain instances and observed
decrease of ∆ 14 C about 10 � over 20 years
are compatible with an increase of the ocean circulation
and gas exchange rate at a factor of 2 and
a decrease at 25 % for the 14 C production.
The results of spectral analysis ∆ 14 C are shown
in Figure 6.2.
Outlook/Future work none in this case
Main publication in preparation

194 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
6.1.4 Establishment of a method for measuring 231 Pa in deep-sea sediments
via ICP-MS
Participating scientist Jörg Lippold, M. Christl, A. Mangini, G. Brey (Frankfurt).
Abstract Using ICP-MS, the 231 Pa / 230 Th ratio of deep-sea sediments can be estimated more
efficiently and precisely than by α-spectrometry. The measurement of the tracers 231 Pa and 230 Th
allows a high resolution for paleoproductivity and ocean circulation studies on glacial to interglacial
timescales.
Background 231 Pa and 230 Th are natural radionuclides,
which are continously produced in
seawater by in situ decay of their dissolved progenitors
234 U and 235 U. As a result, both are produced
at a constant rate with an initial 231 Pa and
230 Th activity ratio of 0.093. Variable 231 Pa and
230 Th ratios in sediments indicate that both radionuclides
follow different pathways of removal
from the water column. The flux of 230 Th to
the seafloor is nearly identical to its rate of production.
In contrast, the longer oceanic residence
time for dissolved 231 Pa due to lower particle reactivity
allows a large scale diffusive transport over
basin-wide distances prior to scavenging, resulting
in its preferential removal in high particle flux
regions.
Particularly in the North Atlantic region radioisotope
signals may be significantly influenced by
changes in Ocean circulation. Up to now, the
231 Pa and 230 Th-ratio is the best kinematic proxy
to quantify the strength of the meridional overturning
circulation. A high resolution study of
the sedimentary 231 Pa and 230 Th-ratio showed
that North Atlantic meridional overturning was
highly variable, switching very fast from an offmode
(during Heinrich Event H1) to almost modern
conditions (Bølling-Allerød) during the past
20 kyr. Thus, 231 Pa and 230 Th-data, that provide
the best estimate of ocean circulation in the
past, can be used as input for model calculations
to quantify the transport of other tracers (e.g. 10
Figure 6.3: Planktonic foraminifera δ 18 O (upper
curve) plotted with sedimentary 231 Pa and
230 Th (lower curve) against age, sediment core
at 33 ◦ N, 57 ◦ W, [McManus et al., 2004].
Be) in the North Atlantic Ocean. Because of the
32.5 kyr half life of 231 Pa, this method is restricted
to the last about 90 kyr [McManus et al., 2004],
[Walter, 1998].
Funding DFG Schwerpunktprogramm 527 and
1158.
Methods and results The accurate and precise
determination of the very low 231 Pa content
in marine sediments requires the application of
a new analytical technique. ICP-MS is currently
the most suitable analytical tool for high precision
measurements of heavy isotope ratios. A cooperation
with the Institute of Mineralogy at the University
of Frankfurt to develop the appropriate analytical
techniques for the determination of Th/U,
and Pa- isotope-ratios with Inductively Coupled
Plasma Mass Spectrometry (ICP-MS) was initiated.
Outlook/Future work In combination with
published 231 Pa and 230 Th-data from the North
Atlantic region, these records will help to greatly
improve our understanding of past Ocean circulation
in this region. Once established, the 231 Pa
measurement method can be applied to further
paleoclimate records, e.g. corals.
Main publication in preparation

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 195
6.1.5 Modelling of stable isotope records of stalagmites
Participating scientist Christian Mühlinghaus, D. Scholz, D. Schimpf, A. Mangini
Abstract Speleothems can be precisely dated with the Th/U method. Climate variations are
recorded in the δ 18 O and δ 13 C of their calcium carbonate. We are developing models to evaluate
drip rates (and other parameters) at the time of growth from the isotopic enrichment of δ 13 C from
the stable isotope records of close-by stalagmites.
1200
1000
Tropfabstand dT [s]
800
600
400
200
T: 6.5
Ma2
0
0 0.5 1 1.5 2 2.5
Alter [ka]
3 3.5 4 4.5
Figure 6.4: Drip rate of stalagmites from Chile calculated by the I model.
Background The isotopic composition of stalagmites
growing under kinetic conditions has
barely been interpretable. Only under equilibrium
formation a temperature signal of δ 18 O could
be deduced. Understanding of the process of kinetic
fractionation, would deliver information on
the drip rate and, therefore, precipitation.
Funding Diplomarbeit, therefore ”not applicable”
Methods and results Drip rate, cave temperature,
calcium concentration, the isotopic composition
of the drop as well as mixing parameters
affect the stable isotope composition of
speleothems.
Three different models were developed to determine
past drip rates. And the sensitivity to these
parameters was tested.
A-Model The age-height-model is based upon
the considerations of W. Dreybrodt [1999] and G.
Kaufmann [2003]. Through a comparison of ages
and heights of different growth layers, drip rates,
calcium concentration and mixing parameter can
be obtained. Hence, the outer form of a stalagmite
can be modeled by given parameters.
I-Model The isotopic model is based on isotopic
enrichment of δ 13 C along the growth axis of
Ma1
a stalagmite due to kinetic fractionation. By comparing
the intersections of modeled drip rate and
isotopic curves of two close-by stalagmites, drip
rates, the isotopic composition of the drop and the
mixing parameter can be determined. Calibrating
the A-Model with these results yields more
information about the calcium concentration of
the drop. This has been done for two close-by
stalagmites from a cave in South Chile.
H-Model The Hendy-Model uses measured
Hendy tests to determine drip rates more accurately.
It is similar to the I-Model, but it is coupled
with an additional box model. Using isotopic
fractionation, one can obtain the range of
drip rate and temperature from the isotopic enrichment
along a growth layer. The correlation
between the drip rate and ∆δ 18 O/∆δ 13 C was constructed.
Outlook/Future work Aim of this work is to
correct for the kinetic effect using the slope of
∆δ 18 O/∆δ 13 C and to determine temperatures in
the cave from the δ 18 O signals of speleothems.
These models are used in the DFG-Project
Forschergruppe 668 (www.FG-daphne.de).
Main publication in preparation

196 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
6.1.6 Reconstruction of the 10 Be-production based on deep sea sediments
from the North Atlantic
Participating scientist Boris Schulze, M. Christl, F. Bernsdorff, A. Mangini, D. Wagenbach, P.
W. Kubik (Zürich)
Abstract The 10 Be-production is inversely related with the Earth‘s magnetic field strength. A
highly resolved record of 10 Be-production is produced based on highly accumulating deep sea sediments
from Bermuda Rise. The data support the idea of using 10 Be as a global matching-tool and as
a proxy for geomagnetic paleointensity.
Figure 6.5: 10 Be deposition rate, transport corrected by 230 Th-normalization. Compared are data from
ODP Sites 1063 (North Atlantik; red) and 1089 (South Atlantic; blue).
Background Cosmogenic 10 Be is produced by
the interaction of galactic cosmic rays with oxygen
and nitrogen atoms in the upper atmosphere
of the Earth. Thus, 10 Be-production is inversely
related with the Earth‘s magnetic field strength.
After different processes of transport, the variations
of the 10 Be-production eventually are conserved
as varying 10 Be-deposition fluxes in different
archives (ice cores, marine and terrestrial
sediments). Knowing the past production rate
of 10 Be, it should be possible to synchronize
chronologies of different archives by comparison
of the reconstructed 10 Be-deposition fluxes.
Funding DFG Schwerpunktprogramm: Antarktisforschung
mit vergleichenden Untersuchungen
in arktischen Gebieten (SPP 1158)
Methods and results A high-resolution record
of 10 Be-production is produced based on highly
accumulating deep sea sediments from Bermuda
Rise (ODP Site 1063). To correct for marine
transport signals, the 230 T hexcess normalisation
technique is applied. The 10 Be -concentration
(measured at the ETH-Zürich) and the activity of
Th/U-isotopes (by alpha-spectroscopy) were determined
in sediments of the past 100 kyr. The
comparison of the 230 T h-normalized 10 Be-flux at
Site 1063 with other records ( 10 Be-fluxes, atmospheric
∆ 14 C, and paleointensity) revealed a very
good interhemispheric correlation. Thus, the results
of this work strongly support the idea of using
10 Be as a global matching-tool for the synchronisation
of marine, terrestrial, and ice-core
chronologies and as a proxy for geomagnetic paleointensity.
Outlook/Future work The 10 Be and U/Thdataset
of the deep sea sediments from ODP Site
1063 will be further expanded and compared to
the data from ODP Sites 983 (North Atlantic) and
1089 (South Atlantic).
Main publication Schulze [2005]; Christl et al.
[2005]

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 197
6.1.7 U/Th dating of deep-water corals from the North Atlantic
Participating scientist Andrea Schröder-Ritzrau, A. Mangini, A. Freiwald (Tübingen), G. Hoffman
(Zürich)
Abstract Coupled uranium-series and radiocarbon measurements on deep-water corals are a proxy
to estimate intermediate water ages. 17 intermediate water ages were estimated on deep-water corals
from the eastern North Atlantic. These data give strong evidence for periodic reduced ventilation in
the North Atlantic during the LGM/Holocene transition.
600
400
� 14 C ‰
200
0
� C Cariaco Basin; Hughen et al. 2004
14
� 14
C model/atm; Laj et al. 2002
� 14
C atm INTCAL; Reimer et al. 2004
� 14
C marin INTCAL; Hughen et al. 2004
-200
0 4000 8000 12000 16000 20000 24000
age (years BP)
Figure 6.6: ∆ 14 Cintermediate water (red data points) compared to various ∆ 14 C records and models (see
references in the Fig.). Data are plotted without error bars for clarity - except for the deep-water coral
data.
Background Thermohaline circulation in the
world ocean has a major influence on climate.
Hence, changes of thermohaline circulation and
water mass distribution especially in the North
Atlantic during climate transitions are of major
interest for paleoceanographic and climatic reconstructions.
It is suggested that at terminations
the intermediate water has a larger component of
poorly ventilated SSW (Southern Source Water)
compared to interglacials and full glacials.
The 14 C/ 12 C ratio of dissolved inorganic carbon
is a powerful tracer for reconstructing the
pathways of deep- and intermediate water in the
ocean. Coupled AMS- 14 C- and Th/U- (TIMS)
measurements on coral carbonate, deliver a snapshot
of the 14 C-concentration of deep- or intermediate
water at the time and place the coral lived
[Mangini et al. 1998].
Funding DFG and EU
Methods and results Intermediate water ages
were calculated via the method of 14 C projection
ages [Adkins and Boyle, 1997]. Radiocarbon
dates (measured at the ETH-Zurich and at
the Leibniz-Laboratory in Kiel) and uranium series
ages (via TIMS in HD) were used to calculate
the ∆ 14 Cintermediate water of the former sur-
rounding intermediate water the coral lived in.
Assuming closed system radiocarbon decay and
no further exchange with atmospheric radiocarbon,
the calculated ∆ 14 Cintermediate water of the
coral (Fig. 6.6) can be backtracked to the crossover-point
with the (∆ 14 C past/atm) [Reimer et al.,
2004]. This ratio (∆ 14 C past/coral) is the ratio of
the water that had equilibrated with the past atmosphere.
This value was applied in the equation
for the ventilation age [Mangini et al., 1998] where
non-reservoir-corrected ventilation ages (intermediate
water ages) are determined.
A total of 69 deep-water corals were investigated
and 17 intermediate water ages were calculated.
Our data document short periods of reduced conveyor
circulation associated with increasing influence
of SSW at intermediate water depth at the
end of Heinrich I and the end of the Younger Dryas
event. These periods are associated with meltwater
discharge (MPIA and B). A similar event in
the early Holocene has to be verified.
Outlook/Future work none in this case, the
project is finished
Main publication Schröder-Ritzrau et al.
[2003]; Schröder-Ritzrau et al. [2005]

198 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
6.1.8 Isochron dating of fossil reef corals and the reconstruction of past
sea level fluctuations
Participating scientist Denis Scholz, A. Mangini, K. Bohn, T. Felis (Bremen), D. Meischner
(Göttingen)
Abstract We developed an isochron dating approach that enables to derive reliable ages for fossil
reef corals that cannot be dated by the conventional Th/U-method. Isochron dating was applied to
Porites corals from Aqaba and Baja California. In addition, we reconstructed magnitude,timing, and
duration of the Marine Isotope Substage (MIS) 6.5 ( 175,000 years before present) sea level peak by
U-series dating of fossil Acropora palmata corals from Barbados.
Figure 6.7: Isochron dating of coral AQB 3A from
Aqaba. The isochron age is calculated from the intersection
point, the age error is estimated from
the intersection points of the confidence bands.
Background Reconstructions of past sea level
fluctuations allow to determine the magnitude,
timing and duration of glacial/interglacial periods.
This is essential for the understanding of the
causal relationships and the complex interplay between
the forcing and feedback mechanisms in the
climate system.
Some reef coral genera grow in upper 5m below
sea surface only and record past sea level fluctuations.
Thus, the determination of accurate
U-series ages provides a direct method for sea
level reconstruction. Unfortunately, many fossil
reef corals show elevated ( 234 U/ 238 U) activity ratios
which are clear evidence for post-depositional
open-system behaviour. Therefore, conventional
Th/U-ages obtained from such corals cannot be
considered as strictly reliable. There are two possibilities
to deal with this problem: (i) to identify
corals that have not been altered and (ii)
to develop and apply appropriate correction techniques.
Funding BMBF (DEKLIM project)
Methods and results We analysed five fossil
Porites corals from Aqaba, Jordan, by
thermal ionisation mass spectrometry (TIMS).
( 234 U/ 238 U) and ( 230 T h/ 238 U) activity ratios of
Figure 6.8: Sea level reconstruction for MIS 6.5.
Black squares are our coral data from Barbados.
Red and yellow symbols are coral data from other
studies, straight curves are based on oxygen isotopes.
different sub-samples from one coral specimen
show a high linear correlation (Fig. 6.7). This
can be explained by a model assuming different
degree of U addition and subsequent loss for different
sub-samples. The model predicts that the
true coral age can be calculated from the intersection
point of the isochron with the seawater
evolution curve (Fig. 6.7). Isochron dating was
also successfully applied to corals from Baja California,
Mexico [Bohn, 2005].
Detailed investigation of Acropora palmata corals
from Barbados, West Indies, showed that
these corals suffered U-redistribution [Scholz and
Mangini, in press]. Thus, isochron dating cannot
be applied. Careful selection of reliable Th/Uages
by application of strict reliability criteria
suggests that MIS 6.5 sea level ranged from -
50±11 to -47±11 m relative to present sea level
between 176,100±2,800 and 168,900±1,400 years
before present (Fig. 6.8). At present, this reconstruction
is one of the most accurate for MIS 6.5.
Outlook/Future work publication of results
Main publication Scholz et al. [2004], Felis et
al. [2004], Scholz [2005], Bohn [2005], Scholz and
Mangini [in press]

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 199
6.1.9 Dating and interpretation of the carbon and oxygen isotopes of two
Holocene stalagmites from the South of Chile (Patagonia)
Participating scientist Daniel Schimpf, C. Mühlinghaus, D. Scholz, A. Schröder-Ritzrau, A.
Mangini, R. Kilian (Trier), C. Spötl (Innsbruck)
Abstract Two Holocene stalagmites (MA-1 and MA-2) from the Marcelo-Arevalo cave, which is
located in the South of Chile (53 ◦ S) in the vicinity of the Pacific coast, were dated with the 230 T h/ 234 U
method and analyzed with respect to their oxygen and carbon isotopes. We find that the Westwind
drift, which controls precipitation, is strongly influenced by the El Nino Southern Oscillation.
age (ka BP)
5
4
3
2
1
Stalagmite MA-1
Akima fit
0
0 50 100 150 200 250
distance from top (mm)
Background For the first time stalagmites
from a cave of the southernmost Andes were analyzed
at high resolution. The intensity of precipitation
at this location reflects the shifts of the
position of the Westwind drift.
Funding Diploma thesis, therefore not applicable.
Methods and results The 230 T h/ 234 U dating
method was used to establish a depth-age model
for the two stalagmites (MA-1 and MA-2). The
measurements were performed with a Thermal
Ionization Mass Spectrometer (TIMS). Figure 6.9
shows the depth-age model for stalagmite MA-1
including all reliable data points. An Akima fit
was implemented to get a continuous depth-age
Figure 6.9: Depth-age model of stalagmite MA-1.
relation. It shows an almost linear relation between
age and depth.
The comparison of the dated δ 13 C and δ 18 O profiles
with a record of the ENSO intensity, derived
from a sediment record off the coast of Peru, reveals
that the ENSO strongly influenced the intensity
of precipitation, probably causing North-
South-shifts of the Southern Westerlies.
Outlook/Future work Further stalagmites
from the Marcelo-Arevalo cave will be analysed.
The stable isotope profiles are modeled by C.
Mühlinghaus. We have applied for a DFG -
Project to continue this study.
Main publication Schimpf [2005]

200 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
6.1.10 Chronostratigraphy of the Nasca culture and palaeoclimate reconstruction
of the Palpa region (Peru) by AMS- 14 C dating
Participating scientist Ingmar Unkel, B. Kromer, G. Wagner, B. Eitel, L. Wacker (Zürich)
Abstract Research on the enigmatic Nasca culture in South-Peru is driven by two major questions:
when did the Nasca people live, and did changing climate have an influence on the rise and fall of this
Pre-Columbian civilisation? AMS- 14 C-dating and investigations in an multi-disciplinary project help
to get the first answers.
Figure 6.10: (left) Preparation line for AMS- 14 C-targets built at the IUP during this project. (right)
A trapezoid, one of the famous Nasca-geoglyphs, in the research area near Palpa (S-Peru).
Background The chronology of the Nasca culture,
which created the world famous geoglyphs
(giant diagrams etched into the desert ground)
and spanning from approximately 200 BC to 600
AD, in the plain between the Peruvian Andes and
the Pacific Ocean, is presently based almost exclusively
on a ceramic typology without any extensive
chronometric dating. An absolute chronology
of this culture had to be created via radiocarbon
dating on organic samples from settlement and
tomb relics as well as on organic material derived
from geoglyph sites in the Nasca/Palpa region.
Furthermore, the question is under investigation,
if changing climate had influence on the rise and
fall of the Pre-Columbian cultures in South-Peru.
Funding BMBF focus programme ”New technologies
in humanities”, project No. 03WAX3VP
- title: ”Nasca: development and adaptation of
archaeometric techniques for the investigation of
the cultural history of the Palpa region, S-Peru”
Methods and results The main focus of the
archaeological investigations was on the Nascaperiod
settlement centres near Palpa, Los Molinos
und La Mua. In co-operation with the geomorphological
investigations within the parent
project, palaeoclimatic reconstruction of the re-
spective region was undertaken. The material to
be dated consisted mainly of loess molluscs and
charred plant remains, sampled from river terraces
and debris flows which originated in more humid
phases in this presently hyper-arid area.
During the course of the project a semi-automated
AMS-target preparation line was built in the
radiocarbon laboratory. Using AMS (Accelerator
Mass Spectrometry), dating of extremely
small amounts of archaeological material is possible.
For the first time in Peruvian archaeology
straw fragments found within adobes (clay
bricks), which do not provide a sufficient amount
of material for conventional measurement, have
been dated.
The dating of the samples appears to confirm so
far the archaeological timeframe of the Nasca culture.
The chronology will be completed and statistically
analysed towards the end of this year.
Some surprising new evidence of climate change
has been found in the studies of the river sediments,
showing a pronounced wet phase from 15 th
to 17 th century in that region. The analysis is still
in progress.
Outlook/Future work none in this case
Main publication in preparation

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 201
6.1.11 Nonlinear time-series analysis of nonstationary signals
Participating scientists Pablo Verdes, A. Mangini
Abstract The purpose of my research is to develop new tools for the analysis of nonstationary
complex systems. I explore them using a natural decomposition into intrinsic dynamics and external
component, using a previously developed technique to estimate the latter from measured data. In
particular, I investigate how modeling and forecasting can be improved in this framework.
Background One of the main goals of Physics
has always been prediction. The most satisfactory
situation arises when the system of interest
can be completely understood and modeled from
first principles, so that its equations of motion
can be derived and solved for all times. However,
real-world dynamical systems have often so many
degrees of freedom that the traditional approach
proves intractable. In such a case, an alternative
path is to measure the evolution of any given
system property by recording time series, which
are a set of observations collected at regular intervals
of time, and then recurr to the theory of
time-series analysis. The vast literature on this
subject mostly rely on the condition of stationarity,
because a solid mathematical foundation can
be built in this case. As a result, nonstationary
time-series analysis is an almost unexplored
branch of science. However, the stationarity condition
is very stringent because most real-world
time series have some degree of nonstationarity
due to external perturbations acting on the observed
system.
Funding Alexander von Humboldt postdoctoral
fellowship.
Methods and results I have investigated the
problem of modeling and forecasting of nonstationary
time series. More precisely, I have studied
an over-embedding method that constitutes a general
framework for modeling nonstationary systems,
basically enlarging the standard time-delay
embedding space by inclusion of the unknown slow
driving signal. I have developed a variant in which
this external driving force can be estimated simultaneously
with the intrinsic stationary dynamics.
This method is general and can be implemented
with any modeling tool; using in particular artificial
neural networks, I have found that it is highly
efficient both on synthetic and real-world time series.
In particular, in noiseless artificial cases this
approach is more than one order of magnitude
better than the second best method. As a realworld
application, I have considered the problem
of modeling the sunspot number record. In this
case a 30% error reduction was obtained, which is
a remarkable number within the vast literature on
this benchmark, particularly for an already very
competitive modeling methodology like ensembles
of artificial neural networks. In the case of nstep-ahead
predictions, this approach also leads
to much more accurate results and longer prediction
horizons than other existing overembedding
methods in the literature.
We have also studied a time series of temperatures
in the Central Alps during the past 2000 years reconstructed
from a δ 18 O stalagmite record. The
isotopic composition of this stalagmite could be
precisely dated and translated into a highlyresolved
record of temperature during the last 2
millenia. The variability of this time series was
analysed and compared to other reconstructions
of past temperatures in the literature, and the role
of the solar signal as a possible driver of its dynamics
was assessed in comparison with carbon
dioxide. The fractions of temperature variance
that are explained by each of these forcing factors
were analysed in a nonlinear framework, by studying
the relevance of the solar and greenhouse gas
inputs in a feed-forward neural network model of
the temperature behaviour.
I have also participated in a time series prediction
competition organised by the International Joint
Conference on Neural Networks. The goal of this
competition was to provide a new benchmark for
the problem of time series prediction and to compare
the different methods or models that can be
used for the prediction. An artificial time series
with 5000 data was given and, within those, 100
values were missing and had to be predicted. Selected
papers were considered for publication in
Neurocomputing.
Main publications Verdes et al. [pub.];
Mangini et al. [2005]; Verdes et al. [in press]

202 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
6.1.12 The authigenic 10 Be/ 9 Be ratio in deep sea sediments as a proxy for
the Earth‘s magnetic field intensity
Participating scientists Patrick Wenderoth, M. Christl, F. Bernsdorff, A. Mangini, P. Kubik
(Zürich)
Abstract We tested if the authigenic 10 Be/ 9 Be ratio in deep sea sediments could be used for the
reconstruction of the relative Earth’s magnetic field.
Reconstruction of the relative Earth’s magnetic field strength for the last 580 ka
relative Earth magnetic field,
determined with 10 Be Titan corrected / 9 Be(auth.)/g sed
from 10 Be Titancorrected / 9 Be(auth.)/g sed
Relative Paleointensity from Sint800
2,5
2,0
1,5
1,0
0,5
0,0
1 2 3 4 5 6 7 8
Relative Paleointensity
1,4
1,2
1,0
0,8
0,6
0,4
9 10 11 12 13 14 15 16 0,2
0 0 100 200 200 300 400 400 500 600
600
Age (ka)
Figure 6.11: The Relative Earth’s magnetic field, determined with 10 BeT itan corrected/ 9 Be(auth.)/gsed
(blue curve) compared with the relative intensity derived from paleomagnetic data (SINT 800), (black
curve).
Background The production rate of the radionuclide
10 Be in the stratosphere, induced by
interaction of cosmic rays with atmospheric O
and N, depends on the intensity of the Earth’s
magnetic field. The production rate of 10 Be increases
when the Earth’s magnetic field strength
decreases and vice versa. Therefore, the 10 Beflux
in the deep sea sediments is a proxy for the
longterm variation of the relative Earth’s magnetic
field. However, the 10 Be-flux into sediments
has to be normalized with 230 T h to account for
processes that redistribute the sediments on the
sea floor. This normalization is limited to the last
350 ky. Here, a new method was investigated,
based on the normalization to the stable isotope
9 Be. The 10 Be/ 9 Be ratio depends only on the
half life of 10 Be (1.5 Ma). Deep sea sediments
have a detritic and an authigenic (i.e sea water signature)
component. Both 10 Be and 9 Be detritic
fluxes may be influenced by climate [McHargue et
al., 2005], whereas the normalization of 10 Be on
authigenic 9 Be is not.
Funding Diplomathesis, non in this case.
1,6
Methods and results In this study a procedure
based on sequential extraction steps was developed
to separate the authigenic and the terrigenous
components of sediments from ODP Leg
177 Site 1089. In addition, Ti in the authigenic
fraction was measured to quantify the amount of
extracted detritic fraction.
The 10 Be-flux normalized to the 10 Be/ 9 Be ratio
was compared with that derived from the 230 T h
normalization. Best matching was obtained when
the 10 Be-flux was normalized to authigenic 9 Be
and additionally using a ”Ti-correction”. The
magnetic field reconstruction determined by the
”Ti corrected” authigenic 10 Be/ 9 Be ratio correlates
well with the record from paleomagnetic data
(SINT 800) for the last 580ka (Fig. 6.11). Furthermore,
we could show that the signal of paleomagnetic
intensity of Site 1089 is partially an artifact
of supply of terrigenuos material and, therefore,
not as appropriate as the 10 Be-flux for reconstructing
the Earth’s magnetic field
Main publication Wenderoth [2005]

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 203
References
Adkins, J.F., & Boyle, E.A. 1997. Changing atmospheric ∆ 14 C and the record of deep water paleoventilation
ages. Paleoceanography, 12(3), 337–344.
Beer, J., Mende, W., & Stellmacher, R. 2000. The role of the sun in climate forcing. Quaternary
Science Reviews, 19, 403–415.
Bohn, K. 2005. Datierung von fossilen Riffkorallen aus Baja California mit der 230 Th/ 234 U-Methode.
unpublished Master Thesis, University of Heidelberg, Institute of Environmental Physics.
Bond, G., Kromer, B., Beer, J., Muscheler, R., Evans, M.N., Showers, W., Hoffmann, S., Lotti Bond,
R., Hajdas, I., & Bonani, G. 2001. Persistent solar influence on North Atlantic climate during the
Holocene. Science, 294(5549).
Braun, H. in press. Possible solar origin of the glacial 1,470-year climate cycle demonstrated in a
coupled model. Nature.
Burns, S.J., Fleitmann, D., Mudelsee, M., Neff, U., Matter, A., & Mangini, A. 2002. A 780-year
annually resolved record of Indian Ocean monsoon precipitation from a speleothem from south
Oman. Journal of Geophysical Research, 107(D20), doi:10.1029/2001JD001281.
Christl, M., Mangini, A., Holzkämper, S., & Spötl, C. 2004. Evidence for a link between the flux
of galactic cosmic rays and Earths climate during the past 200,000 years. J. Atmospheric and
Solar-Terrestrial Physics, 66, 313–322.
Christl, M., Schulze, B., Wenderothr, P., Bernsdorff, F., & Mangini, A. 2005. Geomagnetic variability
over the past 300,000 years from cosmogenic beryllium-10 in deep-sea sediments - a potential global
matching tool. 22. Internationale Polartagung, 18.24.09.2005, Poster.
Dreybrodt, W. 1999. Chemical kinetics, speleothem growth and climate. Boreas, 28, 347–356.
Eddy, J. 1976. The mounder minimum. Science, 192, 1189–1202.
Eitel, B., Hecht, S., Mächtle, B., Schukraft, G., Kadereit, A., Wagner, G.A., Kromer, B., Unkel, I., &
Reindel, M. 2005. Geoarchaeological evidence from desert loess in the Nazca/Palpa region, Southern
Peru: Palaeoenvironmental changes and their impact on Pre-Columbian cultures. Archaeometry,
47(1), 137–158.
Felis, T., Lohmann, G., Kuhnert, H., Lorenz, S.J., Scholz, D., Pätzold, J., Al Rousan, S.A., & Al
Moghrabi, S.M. 2004. Increased seasonality in Middle East temperatures during the last interglacial
period. Nature, 429, 164–168.
Fleitmann, D., Burns, S.J., Mudelsee, M., Neff, U., Kramers, J., Mangini, A., & Matter, A. 2003.
Holocene Forcing of the Indian Monsoon Recorded in a Stalagmite from Southern Oman. Science,
300(5626), 1737–1739.
Fleitmann, D., Burns, S.J., Neff, U., Mudelsee, M., Mangini, A., & Matter, A. 2004. Palaeoclimatic interpretation
of high-resolution oxygen isotope profiles derived from annually laminated speleothems
from Southern Oman. Quaternary Science Reviews, 23, 935–945.
Friedrich, M., Remmele, S., Kromer, B., Hofmann, J., Spurk, M., Kaiser, K.F., Orcel, C., & Küppers,
M. 2004. The 12,460-Year Hohenheim Oak and Pine Tree-Ring Chronology from Central Europe
- a Unique Annual Record for Radiocarbon Calibration and Paleoenvironment Reconstructions.
Radiocarbon, 46(3), 1111–1122.
Ganopolski, A., & Rahmstorf, S. 2001. Rapid changes of glacial climate simulated in a coupled climate
model. Nature, 409, 153–158.
Ganopolski, A., & Rahmstorf, S. 2002. Abrupt glacial climate changes due to stochastic resonance.
Physical Review Letters, 88(3), 038501.
Hodell, D.A., Brenner, M., Curtis, J.H., & Guilderson, T. 2001. Solar Forcing of Drought Frequency
in the Maya Lowlands. Science, 292, 1367–1370.
Holzkämper, S., Mangini, A., Spötl, C., & Mudelsee, M. 2004. Timing and progression of the Last
Interglacial derived from a high alpine stalagmite. Geophysical Research Letters, 31(L07201), 1–4.

204 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
Holzkämper, S., Spötl, C., & Mangini, A. 2005. High-precision constrains on timing of Alpine warm
periods during the middle to late Pleistocene using speleothem growth. Earth and Planetary Science
Letters, 236, 751–764.
Hughen, K., Lehman, S., Southon, J., Overpeck, J., Marchal, O., & Herring, C. 2004a. 14C activity
and Global Carbon Cycle changes over the last 50,000 years. Science, 303, 202–207.
Hughen, K.A., Baillie, M.G.L., Bard, E., Beck, J.W., Bertrand, C.J.H., J.H., Chanda, Blackwell, P.G.,
Buck, C.E., Burr, G.S., Cutler, K.B., Damon, P.E., Edwards, R.L., Fairbanks, R.G., Richard, G.,
Friedrich, M., Guilderson, T.P., Kromer, B., McCormac, G., Manning, S., Ramsey, C.B., Reimer,
P.J., Reimer, R.W., Remmele, S., Southon, J.R., Stuiver, M, Talamo, S., Taylor, F.W., van der
Plicht, J., & Weyhenmeyer, C.E. 2004b. Marine04 Marine Radiocarbon Age Calibration, 0-26 Cal
Kyr BP. Radiocarbon, 46(3), 1059–1086.
Kaufmann, G. 2003. Stalagmite Growth and palaeo-climate: the numerical perspective. Earth and
Planetary Science Letters, 214, 251–266.
Kromer, B., Korfmann, M., & Jablonka, P. 2002. Heidelberg radiocarbon dates for Troia I to VIII
and Kumtepe. Pages 43–54 of: Wagner, G. (ed), Troia and the Troad. Heidelberg: Springer.
Kromer, B., Friedrich, M., Hughen, K.A., Kaiser, F., Remmele, S., Schaub, M., & Talamo, S. 2004.
Late Glacial 14C ages from a floating 1382-ring pine chronology. Radiocarbon, 46(3), 1203–1209.
Labitzke, K., & Loon, H. 1992. Association between the 11-Year Solar Cycle and the Atmosphere.
Part V: Summer. Journal of Climate, 5, 240–251.
Laj, C., Kissel, C., Mazaud, A., Michel, E., Muscheler, R., & Beer, J. 2002. Geomagnetic field
intensity, North Atlantic Deep Water circulation and atmospheric ∆ 14 C during the last 50kyr.
Earth and Planetary Science Letters, 200, 177–190.
Levin, I., & Kromer, B. 2004. The tropospheric 14 CO2 level in Mid-Latitudes of the Northern Hemisphere
(1959-2003). Radiocarbon, 46(3), 1261–1272.
Mangini, A., Lomitschka, M., Eichstädter, R., Frank, N., Vogler, S., Bonani, G., Hajdas, I., & Pätzold,
J. 1998. Coral provides way to age deep water. Nature, 392, 347–348.
Mangini, A., Spötl, C., & Verdes, P.F. 2005. Reconstruction of temperature in the Central Alps
during the past 2,000 years from a δ 18 O stalagmite record. Earth and Planetary Science Letters,
235, 741–751.
Manning, S.W., Kromer, B., Kuniholm, P.I., & Newton, M.W. 2001. Anatolian tree-rings and a new
chronology for the east Mediterranean Bronze-Iron Ages. Science, 295, 2532–2535.
Manning, S.W., Kromer, B., Kuniholm, P.I., & Newton, M.W. 2003. Confirmation of near-absolute
dating of east Mediterranean Bronze-Iron Dendrochronology. Antiquity, 77, 295.
McHargue, L.R., & Donahue, D.J. 2005. Effects of climate and the cosmic-ray flux on the 10 Be content
of marine sediment. Earth and Planetary Science Letters, 232, 193–207.
McManus, J.F., Francois, R., Keigwin, L.D., & Brown Leger, S. 2004. Collapse and rapid resumption
of Atlantic meridional circulation linked to deglacial climate changes. Nature, 428, 834–837.
Neff, U., Burns, S.J., Mangini, A., Mudelsee, M., Fleitmann, D., & Matter, A. 2001. Strong coherence
between solar variability and the monsoon. Nature, 411, 290–293.
Ney, E.P. 1959. Cosmic radiation and weather. Nature, 183, 451.
Niggemann, S., Mangini, A., Mudelsee, M., Richter, D.K., & Wurth, G. 2003. Sub-Milankovitch
climatic cycles in Holocene stalagmites from Sauerland, Germany. Earth and Planetary Science
Letters, 6844, 1–9.
Peristykh, A.N., & Damon, P.E. 2003. Persistence of the Gleissberg 88-year solar cycle over the last
12,000 years: Evidence from cosmogenic isotopes. Journal of Geophysical Research, 108(A1), 1003,
doi:10.1029/2002JA009390.

6.1. RADIOMETRIC DATING OF WATER AND SEDIMENTS 205
Reimer, P.J., Baillie, M.G.L., Bard, E., Bayliss, A., Beck, J.W., Bertrand, C.J.H., Blackwell, P.G.,
Buck, C.E., Burr, G.S., Cutler, K.B., Damon, P.E., Edwards, R.L., Fairbanks, R.G., Friedrich, M.,
Guilderson, T.P., Hogg, A.G., Hughen, K.A., Kromer, B., McCormac, G., Manning, S., Ramsey,
C.B., Reimer, R.W., Remmele, S., Southon, J.R., Stuiver, M., Talamo, S., Taylor, F.W., van der
Plicht, J., & Weyhenmeyer, C.E. 2004. INTCAL04 terrestrial radiocarbon age calibration, 0-26 cal
kyr BP. Radiocarbon, 46(3), 1029–1058.
Schaub, M., Kaiser, K.F., Kromer, B., & Talamo, S. 2005. Extension of the Swiss Lateglacial tree-ring
chronologies. Dendrochronologia, doi:10.1016.
Schimpf, D. 2005. Datierung und Interpretation der Kohlenstoff- und Sauerstoffisotopie zweier
holozäner Stalagmiten aus dem Süden Chiles (Patagonien). unpublished Master Thesis, University
of Heidelberg, Institute of Environmental Physics.
Scholz, D. 2005. U-series dating of diagenetically altered fossil reef corals and the application for sea
level reconstruction. unpublished PhD Thesis, University of Heidelberg, Heidelberger Akademie der
Wissenschaften.
Scholz, D., & Mangini, A. in press. U-redistribution in fossil reef corals from Barbados, West Indies,
and sea level reconstruction for MIS 6.5. In: Sirocko, F., Litt, T., Claussen, M., & Sanchez Goni,
M.-F. (eds), The climate of past interglacials.
Scholz, D., Mangini, A., & Felis, T. 2004. U-series dating of diagenetically altered fossil reef corals.
Earth and Planetary Science Letters, 218, 163–178.
Schröder Ritzrau, A., Lomitschka, M., & Mangini, A. 2003. Deep-sea corals evidence periodic reduced
ventilation in the North Atlantic during LGM/Holocene transition. Earth and Planetary Science
Letters, 216, 399–410.
Schröder Ritzrau, A., Freiwald, A., & Mangini, A. 2005. U/Th dating of deep-water corals from the
eastern North Atlantic and the western Mediterranean Sea. In: Freiwald, A., & Roberts, J.M.
(eds), Cold-water corals and ecosystems. Berlin Heidelberg: Springer-Verlag.
Schulze, B. 2005. Hochaufgelöste Rekonstruktion der 10Be-Produktionsrate aus Tiefseesedimentkernen
des Bermuda Rise über die letzten 70.000 Jahre. unpublished Master Thesis, University of
Heidelberg, Institute of Environmental Physics.
Solanski, S.K., Usoskin, I.G., Kromer, B., Schüssler, M., & Beer, J. 2004. Unsusual activity of the
sun during recent decades compared to the previous 11,000 years. Nature, 431, 1084–1087.
Soon, W.H., Posmentier, E.S., & Baliunas, S.L. 2000. Climate hypersensitivity to solar forcing?
Annales Geophysicae, 18, 583–588.
Spötl, C., Mangini, A., Burns, S.J., Frank, N., & Pavuza, R. 2004. Speleothems from high alpine
Spannagel Cave, Zillertal Alps (Austria). Page 329 of: Sasowsky, I., & MyIroie, J. (eds), Studies of
Cave Sediments. New York: Kluwer Academic.
Stuiver, M., & Braziunas, T.F. 1993. Sun, ocean, climate and atmospheric 14 CO2: an evaluation of
causal and spectral relationships. The Holocene, 3(4), 289–305.
Svensmark, H., & Friis Christensen, E. 1997. Variation of cosmic ray flux and global cloud coverage-a
missing link in solar-climate relationships. J. Atmos. Terr. Phys, 59, 1225–1232.
Usoskin, I.G., & Kromer, B. 2005. Reconstruction of the 14 C production rate from measured relative
abundance. Radiocarbon, 47(1), 31–37.
Verdes, P.F., Granitto, P.M., & Ceccatto, H.A. in pressa. An overembedding method for modeling
nonstationary systems. Physical Review Letters.
Verdes, P.F., Granitto, P.M., Szeliga, M. I., Rebola, A., & Ceccatto, H.A. in pressb. Symmetric-
Embedding Prediction of the CATS Benchmark. Neurocomputing.
Wagner, G. 2001. Presence of the solar de Vries cycle (∼205 years) during the last ice-age. Geophysical
Research Letters, 28(2), 303–306.
Walter, H.J. 1998. Scavening of 231 Pa and 230 Th in the South Atlantic: Implications for the use of
the 231Pa/230Th ratio as a paleoproductivity proxy. Berichte zur Polarforschung, 282, 1–82.

206 CHAPTER 6. FORSCHUNGSSTELLE “RADIOMETRIE”
Wenderoth, P. 2005. Untersuchung der Anwendbarkeit des authigenen 10 Be/ 9 Be-Verhältnisses in Tiefseesedimenten
als Proxy zur Rekonstruktion der Erdmagnetfeldstärke. unpublished Master Thesis,
University of Heidelberg, Institute of Environmental Physics.
Wurth, G., Niggemann, S., Richter, D.K., & Mangini, A. 2004. The Younger Dryas and Holocene
climate record of a stalagmite from Hölloch Cave (Bavarian Alps, Germany). Journal of Quaternary
Science, 19, 291–298.

Bibliography
Peer Reviewed Publications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
Grey Publications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
PhD Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
Diploma Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
Invited Talks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
207

7.1. PEER REVIEWED PUBLICATIONS 209
Peer Reviewed Publications
Aeschbach-Hertig, W. 2005. A comment on ”Helium sources in passive margin aquifers-new evidence
for a significant mantle 3 He source in aquifers with unexpectedly low in situ 3 He/ 4 He production”
by M. C. Castro [Earth Planet. Sci. Lett. 222 (2004) 897-913]. Earth Planet. Sci. Lett., in press.
Bayer, A., Vogel, H.-J., Ippisch, O., & Roth, K. 2005. Do effective properties for unsaturated weakly
layered porous media exist? An experimental study. Hydrology and Earth System Sci., 9, 517–522,
SRef–ID: 1607–7938/hess/2005–9–517.
Beirle, S., Platt, U., von Glasow, R., Wenig, M., & Wagner, T. 2004. Estimate of nitrogen
oxide emissions from shipping by satellite remote sensing. Geophys. Res. Lett., 31, L18102,
doi:10.1029/2004GL020312.
Bobrowski, N., Hönninger, G., Lohberger, F., & Platt, U. 2005. IDOAS: A new monitoring technique
to study the 2D distribution of volcanic gas emissions. J. Volcanol. Geotherm. Res., Accepted for
publishing.
Braun, H. in press. Possible solar origin of the glacial 1,470-year climate cycle demonstrated in a
coupled model. Nature.
Braun, H., Christl, M., Rahmstorf, S., Ganopolski, A., Mangini, A., Kubatzki, C., Roth, K., &
Kromer, B. 2005. Possible solar origin of the 1,470-year glacial climate cycle demonstrated in a
coupled model. Nature, 438, doi: 10.1038/nature04121.
Bruns, M., Buehler, S. A., Burrows, J. P., Heue, K.-P., Platt, U., Pundt, I., Richter, A., Rozanov, A.,
Wagner, T., & Wang, P. 2004. Retrieval of profile information from Airborne Multi Axis UV/visible
skylight absorption measurements. Appl.Opt., 43(22), 4415 – 4426.
Bulath, S., Alekhina, I., Blot, M., Petit, J.-R., de Angelis, M., Wagenbach, D., Lipenkov, V., Valilyeva,
L., Wloch, D., Raynaud, D., & Lukin, V. 2004. DNA singature of thermophilic bacteria from the
aged accretion ice of Lake Vostok, Antarctica: implications for searching for life in extreme icy
environments. International Journal of Astrobiology, 3(1), 1–12.
Butz, A., Bösch, H., Camy-Peyret, C., Chipperfield, M., Dorf, M., Dufour, G., Grunow, K., Jeseck,
P., Kühl, S., Payan, S., Pepin, I., Pukite, J., Rozanov, A., von Savigny, C., Sioris, C., Wagner, T.,
Weidner, F., & Pfeilsticker, K. 2005. Inter-comparison of Stratospheric O3 and NO2 abundances retrieved
from balloon borne direct sun observations and Envisat/SCIAMACHY limb measurements.
Atmos. Chem. Phys. Disc., 5, 10747 – 10797.
Canty, T., Salawitch, R.S., Renard, J.B., Reviere, E.D., Pfeilsticker, K., M., Dorf., Fitzenberger,
R., Bösch, H., Stimpfle, R.M., Wilmouth, D.M., Anderson, J.G., Richard, E.C., Fahey, D.W., &
Gao, R.S.and Bui, T.P. 2005. Analysis of BrO, ClO, and nighttime OClO in the arctic winter
stratosphere. J. Geophys. Res., 110, D01301, doi:10.1029-/2004JD005035.
Christl, M., Mangini, A., Holzkämper, S., & Spötl, C. 2004. Evidence for a link between the flux
of galactic cosmic rays and Earths climate during the past 200,000 years. J. Atmospheric and
Solar-Terrestrial Physics, 66, 313–322.
Corcho Alvarado, J. A., Purtschert, R., Hinsby, K., Troldborg, L., Hofer, M., Kipfer, R., Aeschbach-
Hertig, W., & Synal, H.-A. 2004. 36 Cl in modern groundwater dated by a multi tracer approach
( 3 H/ 3 He, SF6, CFC-12 and 85 Kr): A case study in quaternary sand aquifers in the Odense Pilot
River Basin, Denmark. Appl. Geochem., 20, 599–609.
Corsmeier, U., Kohler, M., Vogel, B., Vogel, H., & Fiedler, F. 2005. BAB II: a project to evaluate the
accuracy of real-world traffic emissions for a motorway. Atmos. Environ., 39, 5627–5641.
Crewell, S., Bloemink, H., Feijt, A., García, S.G., Jolivet, D., Krasnov, O.A., van Lammeren, A.,
Löhnert, U., van Meijgaard, E., Meywerk, J., Quante, M., Pfeilsticker, K., Schmidt, S., Scholl, T.,
Simmer, C., Schröder, M., Trautmann, T., Venema, V., Wendisch, M., & Willén, U. 2004. The
BALTEX Bridge Campaign - An integrated approach for a better understanding of clouds. Bull.
Am. Met. Soc., 85, 1565 – 1584.
Dufour, G., Payan, S., Lefévre, F., Berthet, G., Eremenko, M., Butz, A., Jeseck, P., Té, Y., Pfeilsticker,
K., & Camy-Peyret, C. 2005. 4D comparison method to study the NOy partitioning in summer
polar stratosphere: Influence of aerosol burden. Atmos. Chem. Phys., 5, 919 – 926.

210 CHAPTER 7. BIBLIOGRAPHY
Eitel, B., Hecht, S., Mächtle, B., Schukraft, G., Kadereit, A., Wagner, G.A., Kromer, B., Unkel, I., &
Reindel, M. 2005. Geoarchaeological evidence from desert loess in the Nazca/Palpa region, Southern
Peru: Palaeoenvironmental changes and their impact on Pre-Columbian cultures. Archaeometry,
47(1), 137–158.
Felis, T., Lohmann, G., Kuhnert, H., Lorenz, S.J., Scholz, D., Pätzold, J., Al Rousan, S.A., & Al
Moghrabi, S.M. 2004. Increased seasonality in Middle East temperatures during the last interglacial
period. Nature, 429, 164–168.
Fichter, C., Marquart, S., Sausen, R., & Lee, D. S. 2005. The impact of cruise altitude on contrails
and related radiative forcing. Met. Zeitsch., 14, 563 – 572.
Fix, A., Ehret, G., Flentje, H., Poberaj, G., Gottwald, M., Finkenzeller, H., Bremer, H., Bruns, M.,
Burrows, J. P., Kleinbhl, A., Kllmann, H., Kuttippurath, J., Richter, A., Wang, P., Heue, K.-
P., Platt, U., Pundt, I., & Wagner, T. 2005. SCIAMACHY validation by aircraft remote sensing:
design, execution, and first measurement results of the SCIA-VALUE mission. Atmos. Chem. Phys.,
5, 1273 – 1289.
Fleitmann, D., Burns, S.J., Neff, U., Mudelsee, M., Mangini, A., & Matter, A. 2004. Palaeoclimatic interpretation
of high-resolution oxygen isotope profiles derived from annually laminated speleothems
from Southern Oman. Quaternary Science Reviews, 23, 935–945.
Frankenberg, C., Meirink, J. F., van Weele, M., Platt, U., & Wagner, T. 2005a. Assessing Methane
Emissions from Global Space-Borne Observations. Science, 308(5724), 1010–1014.
Frankenberg, C., Platt, U., & Wagner, T. 2005b. Iterative maximum a posteriori (IMAP)-DOAS for
retrieval of strongly absorbing trace gases: Model studies for CH4 and CO2 retrieval from near
infrared spectra of SCIAMACHY onboard ENVISAT. Atmos. Chem. Phys., 5, 9–22.
Frankenberg, C., Platt, U., & Wagner, T. 2005c. Retrieval of CO from SCIAMACHY onboard
ENVISAT: detection of strongly polluted areas and seasonal patterns in global CO abundances.
Atmos. Chem. Phys., 5, 1639–1644.
Frew, N. M., Bock, E. J., Schimpf, U., Hara, T., Haußecker, H., Edson, J. B., McGillis, W. R., Nelson,
R. K., McKeanna, B. M., Uz, B. M., & Jähne, B. 2004. Air-sea gas transfer: its dependence on wind
stress, small-scale roughness and surface films Small-Scale Air-Sea Interaction with Thermography.
Journal of Geophysical Research, C8(109). C08S17, doi:10.1029/2003JC002131.
Friedrich, M., Remmele, S., Kromer, B., Hofmann, J., Spurk, M., Kaiser, K.F., Orcel, C., & Küppers,
M. 2004. The 12,460-Year Hohenheim Oak and Pine Tree-Ring Chronology from Central Europe
- a Unique Annual Record for Radiocarbon Calibration and Paleoenvironment Reconstructions.
Radiocarbon, 46(3), 1111–1122.
Garbe, C. S., Schimpf, U., & Jähne, B. 2004. A Surface Renewal Model to Analyze Infrared Image
Sequences of the Ocean Surface for the Study of Air-Sea Heat and Gas Exchange. Journal of
Geophysical Research, C8(109). C08S15, doi:10.1029/2003JC001802.
Gurlit, W., Bösch, H., Bovensmann, H., Burrows, J. P., Butz, A., Camy-Peyret, C., Dorf, M., Gerilowski,
K., Lindner, A., Noël, S., Platt, U., Weidner, F., & Pfeilsticker, K. 2005. The UV-A
and visible solar irradiance spectrum: Inter-comparison of absolutely calibrated, spectrally medium
resolved solar irradiance spectra from balloon-, and satellite-borne measurements. Atmos. Chem.
Phys., 5, 1879 – 1890.
Hak, C., Pundt, I., Trick, S., Kern, C., Platt, U., Dommen, J., Ordonez, C., Prevot, A. S. H.,
Junkermann, W., Astorga-Llorens, C., Larsen, B. R., Mellqvist, J., Strandberg, A., Yu, Y., Galle,
B., Kleffmann, J., Lörzer, J. C., Braathen, G. O., & Volkamer, R. 2005. Intercomparison of four
different in-situ techniques for ambient formaldehyde measurements in urban air. Atmos. Chem.
Phys. Discuss., 5, 2897–2945.
Heckel, A., Richter, A., Tarsu, T., Wittrock, F., Hak, C., Pundt, I., Junkermann, W., & Burrows,
J. P. 2005. MAX-DOAS measurements of formaldehyde in the Po-Valley. Atmos. Chem. Phys., 5,
909 – 918.

7.1. PEER REVIEWED PUBLICATIONS 211
Hendrick, F., Barret, B., Van Roozendael, M., Boesch, H., Butz, A., De Mazière, M., Goutail, F.,
Lambert, J.-C., Pfeilsticker, K., & Pommereau, J.P. 2004. Retrieval of nitrogen dioxide stratospheric
profiles from ground-based zenith-sky UV-visible observations: Validation of the technique through
correlative comparisons. Atmos. Chem. Phys., 4, 2867 – 2904.
Heue, K.-P., Richter, A., Bruns, M., Burrows, J. P., Friedeburg, C. von, Platt, U., Pundt, I., Wang,
P., & Wagner, T. 2005a. Validation of SCIAMACHY tropospheric NO2-columns with AMAXDOAS
measurements. Atmos. Chem. Phys., 5, 1039 – 1051.
Heue, K.-P., Richter, A., Bruns, M., Burrows, J. P., v.Friedeburg, C., Platt, U., Pundt, I., Wang, P.,
& Wagner, T. 2005b. Validation of SCIAMACHY tropospheric NO2-columns with AMAXDOAS
measurements. Atmos. Chem. Phys., 5, 1039–1051.
Hollwedel, J., Wenig, M., Beirle, S., Kraus, S., Kühl, S., Wilms-Grabe, W., Platt, U., & Wagner, T.
2004. Year-to-Year Variations of Spring Time Polar Tropospheric BrO as seen by GOME. Adv.
Space Res., 34, 804–808. doi:10.1016/j.asr.2003.08.060.
Holzkämper, S., Mangini, A., Spötl, C., & Mudelsee, M. 2004. Timing and progression of the Last
Interglacial derived from a high alpine stalagmite. Geophysical Research Letters, 31(L07201), 1–4.
Holzkämper, S., Spötl, C., & Mangini, A. 2005. High-precision constrains on timing of Alpine warm
periods during the middle to late Pleistocene using speleothem growth. Earth and Planetary Science
Letters, 236, 751–764.
Hughen, K., Lehman, S., Southon, J., Overpeck, J., Marchal, O., & Herring, C. 2004a. 14C activity
and Global Carbon Cycle changes over the last 50,000 years. Science, 303, 202–207.
Hughen, K.A., Baillie, M.G.L., Bard, E., Beck, J.W., Bertrand, C.J.H., J.H., Chanda, Blackwell, P.G.,
Buck, C.E., Burr, G.S., Cutler, K.B., Damon, P.E., Edwards, R.L., Fairbanks, R.G., Richard, G.,
Friedrich, M., Guilderson, T.P., Kromer, B., McCormac, G., Manning, S., Ramsey, C.B., Reimer,
P.J., Reimer, R.W., Remmele, S., Southon, J.R., Stuiver, M, Talamo, S., Taylor, F.W., van der
Plicht, J., & Weyhenmeyer, C.E. 2004b. Marine04 Marine Radiocarbon Age Calibration, 0-26 Cal
Kyr BP. Radiocarbon, 46(3), 1059–1086.
Jähne, B., Schmidt, M., & Rocholz, R. 2005c. Combined optical slope/height measurements of short
wind waves: principle and calibration. Meas. Sci. Technol., 16, 1937–1944.
Kern, C., Trick, S., Rippel, B., & Platt, U. 2005. Applicability of light-emitting diodes as light sources
for active DOAS measurements. Appl. Opt., Accepted for publishing.
Khokhar, M.F., Frankenberg, C., Roozendael, M. Van, Beirle, S., Kühl, S., Richter, A., Platt, U.,
& Wagner, T. 2005. Satellite observations of atmospheric SO2 from volcanic eruptions during the
time period of 1996 to 2002. Adv. Space Res., 36, 879–887. doi:10.1016/j.asr.2005.04.114.
Kromer, B., Friedrich, M., Hughen, K.A., Kaiser, F., Remmele, S., Schaub, M., & Talamo, S. 2004.
Late Glacial 14C ages from a floating 1382-ring pine chronology. Radiocarbon, 46(3), 1203–1209.
Kühl, S., D”ornbrack, A., Sinnhuber, B.-M., Wilms-Grabe, W., Platt, U., & Wagner, T. 2004. Observational
evidence of rapid chlorine activation by mountain waves above Northern Scandinavia.
J. Geophys. Res., 109. doi:10.1029/2004JD004797.
Laepple, T., Knab, V., Mettendorf, K.-U., & Pundt, I. 2004. Longpath DOAS tomography on a
motorway exhaust plume: Numerical studies and application to data from the BAB II campaign.
Atmos. Chem. Phys., 4, 1323 – 1342.
Lee, J. S., Kim, Y. J., Kuk, B., Geyer, A., & Platt, U. 2005. Simultaneous Measurements of Atmospheric
Pollutants and Visibility with a Long-Path DOAS System in Urban Areas. Environ. Monit.
Assess., 104, 281–293.
Legrand, M., Preunkert, S., Galy-Lacaux, C., Liousse, C., & Wagenbach, D. 2005. Atmospheric yearround
records of dicarboxylic acids and sulfate at three French sites located between 630 and 4360
m elevation. Journal of Geophysical Research, 110, D13302, doi:10.1029/2004JD005515.
Levin, I., & Kromer, B. 2004. The tropospheric 14 CO2 level in mid-latitudes of the Northern Hemisphere
(1959-2003). Radiocarbon, 46(3), 1 261–1 272.

212 CHAPTER 7. BIBLIOGRAPHY
Mangini, A., Spötl, C., & Verdes, P.F. 2005. Reconstruction of temperature in the Central Alps
during the past 2,000 years from a δ 18 O stalagmite record. Earth and Planetary Science Letters,
235, 741–751.
Marquart, S., Ponater, M., Ström, L., & Gierens, K. 2005. An upgraded estimate of the radiative
forcing of cryoplane contrails. Met. Zeitsch., 14, 573 – 582.
McHargue, L.R., & Donahue, D.J. 2005. Effects of climate and the cosmic-ray flux on the 10 Be content
of marine sediment. Earth and Planetary Science Letters, 232, 193–207.
McManus, J.F., Francois, R., Keigwin, L.D., & Brown Leger, S. 2004. Collapse and rapid resumption
of Atlantic meridional circulation linked to deglacial climate changes. Nature, 428, 834–837.
Oswald, B., Doetsch, J., & Roth, K. 2006. A new computational technique for procesing transmission
line measurements to determine dispersive dielectric properties. Geophysics, in print.
Peeters, F., Beyerle, U., Aeschbach-Hertig, W., Brennwald, M. S., & Kipfer, R. 2004. Response to
the comment by G. Favreau, A. Guero, and J. Seidel on Improving noble gas based paleoclimate
reconstruction and groundwater dating using 20 Ne/ 22 Ne ratios (2003) Geochim. Cosmochim. Acta,
67, 587 - 600. Geochim. Cosmochim. Acta, 68(6), 1437–1438.
Peters, C., Pechtl, S., Stutz, J., Hebestreit, K., Hönninger, G., Heumann, K. G., Schwarz, A., Winterlik,
J., & Platt, U. 2005. Reactive and organic halogen species in three different European coastal
environments. Atmos. Chem. Phys., 5, accepted.
Piel, C., Weller, R., M.Huke, & Wagenbach, D. accepted. Atmospheric methane sulfonate and non-sea
salt sulfate records at the EPICA deep-drilling site in Dronning Maud Land. Journal of Geophysical
Research, 2005JD006213.
Platt, U., Allan, W., & Lowe, D. 2004. Hemispheric Average Cl Atom Concentration from 13 C/ 12 C
Ratios in Atmospheric Methane. Atmos. Chem. Phys., 4, 2393–2399.
Ponater, M., Marquart, S., Sausen, R., & Schumann, U. 2005. On contrail climate sensitivity. Geophys.
Res. Lett., 32, L10706, doi: 10.1029/2005GL02258.
Pundt, I. 2005. DOAS tomography for the localisation and quantification of anthropogenic air pollution.
Anal. Bioanal. Chem. accepted.
Pundt, I., & Mettendorf, K. U. 2005. Multibeam long-path differential optical absorption spectroscopy
instrument: a device for simultaneous measurements along multiple light paths. Appl. Opt., 44(23),
4985 – 4994.
Pundt, I., Mettendorf, K. U., Laepple, T., Knab, V., Xie, P., Lösch, J., von Friedeburg, C., Platt,
U., & Wagner, T. 2005. Measurements of trace gas distributions by Long-Path DOAS-Tomography
during the motorway campaign BAB II: experimental setup and results for NO2 (BAB II special
issue). Atmos. Environ., 39(5), 967–975.
Reimer, P.J., Baillie, M.G.L., Bard, E., Bayliss, A., Beck, J.W., Bertrand, C.J.H., Blackwell, P.G.,
Buck, C.E., Burr, G.S., Cutler, K.B., Damon, P.E., Edwards, R.L., Fairbanks, R.G., Friedrich, M.,
Guilderson, T.P., Hogg, A.G., Hughen, K.A., Kromer, B., McCormac, G., Manning, S., Ramsey,
C.B., Reimer, R.W., Remmele, S., Southon, J.R., Stuiver, M., Talamo, S., Taylor, F.W., van der
Plicht, J., & Weyhenmeyer, C.E. 2004. INTCAL04 terrestrial radiocarbon age calibration, 0-26 cal
kyr BP. Radiocarbon, 46(3), 1029–1058.
Richter, A., Wittrock, F., Weber., M., Beirle, S., Kühl, S., Platt, U., Wagner, T., Wilms-Grabe, W., &
Burrows, J.P. 2005. GOME observations of stratospheric trace gas distributions during the splitting
vortex event in the Antarctic winter 2002 Part I: Measurements. J. Atmos. Sci., 62, 778 – 785.
Röckmann, T., & Levin, I. 2005. High-precision determination of the changing isotopic composition
of atmospheric N2O from 1990 to 2002. J. Geophys. Res. accepted.
Roth, K., Boike, J., & Vogel, H.-J. 2005. Quantifying Permafrost Patterns using Minkowski Densities.
Permafrost and Periglacial Processes, 16, 277–290, doi: 10.1002/ppp.531.
Schaub, M., Kaiser, K.F., Kromer, B., & Talamo, S. 2005. Extension of the Swiss Lateglacial tree-ring
chronologies. Dendrochronologia, doi:10.1016.

7.1. PEER REVIEWED PUBLICATIONS 213
Schimpf, U., Garbe, C. S., & Jähne, B. 2004. Investigation of transport processes across the seasurface
microlayer by infrared imagery. Journal of Geophysical Research, C8(109). C08S13,
doi:10.1029/2003JC001803.
Scholl, T., Pfeilsticker, K., Davis, A.B., Klein Baltink, H., Crewell, S., Löhnert, U., Simmer, C.,
Meywerk, J., & Quante, M. 2005. Path length distributions for solar photons under cloudy skies:
Comparison of measured first and second moments with predictions from classical and anomalous
diffusion theories. J. Geophys. Res., revised.
Scholz, D., Mangini, A., & Felis, T. 2004. U-series dating of diagenetically altered fossil reef corals.
Earth and Planetary Science Letters, 218, 163–178.
Sinreich, R., Frieß, U., Wagner, T., & Platt, U. 2005. Multi Axis Differential Optical Absorption
Spectroscopy (MAX-DOAS) of Gas and Aerosol Distributions. Farady Discuss., 153 – 164.
Solanski, S.K., Usoskin, I.G., Kromer, B., Schüssler, M., & Beer, J. 2004. Unsusual activity of the
sun during recent decades compared to the previous 11,000 years. Nature, 431, 1084–1087.
Stöhr, M., & Roth, K. 2005. Gradient-based estimation of local parameters for flow and transport in
heterogeneous porous media. Water Resour. Res., 41, 1–14, W08401, doi:10.1029/2004WR003768.
Tas, E., Peleg, M., Matveev, V., Zingler, J., & Luria, M. 2005. Frequency and extent of bromine oxide
formation over the Dead Sea, Israel. J. Geosphys. Res., 110, D11304.
Usoskin, I.G., & Kromer, B. 2005. Reconstruction of the 14 C production rate from measured relative
abundance. Radiocarbon, 47(1), 31–37.
Vandaele, A.C., Fayt, C., Hendrick, F., Hermans, C., Humbled, F., Van Roozendael, M., Gil, M.,
Navarro, M., Puentedura, O., Yela, M., Braathen, G., Stebel, K., Tornkvist, K., Johnston, P.,
Kreher, K., Goutail, F., Mieville, A., Pommereau, J.-P., Khaikine, S., Richter, A., Oetjen, H.,
Wittrock, F., Bugarski, S., Frieß, U., Pfeilsticker, K., Sinreich, R., Wagner, T., Corlett, G., &
Leigh, R. 2005. An intercomparison campaign of ground-based UV-Visible measurements of NO2,
BrO, and OClO slant columns. Methods of analysis and results for NO2. J. Geophys. Res., 110,
D08305, doi:10.1029/2004JD005423.
Verdes, P.F., Granitto, P.M., & Ceccatto, H.A. in pressa. An overembedding method for modeling
nonstationary systems. Physical Review Letters.
Verdes, P.F., Granitto, P.M., Szeliga, M. I., Rebola, A., & Ceccatto, H.A. in pressb. Symmetric-
Embedding Prediction of the CATS Benchmark. Neurocomputing.
Vogel, H.-J., Tölke, J., Schulz, V. P., Krafczyk, M., & Roth, K. 2005a. Comparison of a Lattice-
Boltzmann Model, a Full-Morphology Model, and a Pore Network Model for Determining Capillary
Pressure-Saturation Relationships. Vadose Zone J., 4, 380–388, doi: 10.2136/vzj2004.0114.
Vogel, H.-J., Hoffmann, H., & Roth, K. 2005b. Studies of crack dynamics in clay soil. I. Experimental
methods, results, and morphological quantification. Geoderma, 125, 203–211.
Vogel, H.-J., Hoffmann, H., Leopold, A., & Roth, K. 2005c. Studies of crack dynamics in clay soil.
II. A physically based model for crack formation. Geoderma, 125, 213–223.
Volkamer, R., Spietz, P., Burrows, J. P., & Platt, U. 2005. High-resolution absorption cross-section of
Glyoxal in the UV/vis and IR spectral ranges. J. Photoch. Photobio. A: Chemistry, 172, 35 – 46.
von Friedeburg, C., Pundt, I., Mettendorf, K. U., Wagner, T., & Platt, U. 2005. Multi-AXis-(MAX)
DOAS Measurements of NO2 during the BAB II Motorway Emission Campaign, (BAB II special
issue). Atmos. Environ., 39(5), 977–985.
von Glasow, R., & Crutzen, P. J. 2004. Model study of multiphase DMS oxidation with a focus on
halogens. Atmos. Chem. Phys., 4, 589 – 608.
von Glasow, R., von Kuhlmann, R., Lawrence, M. G., Platt, U., & Crutzen, P. J. 2004. Impact of
reactive bromine chemistry in the troposphere. Atmos. Chem. Phys., 4, 2481 – 2497.
Wagner, T., Dix, B., von Friedeburg, C., Frieß, U., Sanghavi, S., Sinreich, R., & Platt, U. 2004.
MAX-DOAS O4 measurements - a new technique to derive information on atmospheric aerosols:
(I) Principles and information content. J. Geophys. Res., 109(D22205).

214 CHAPTER 7. BIBLIOGRAPHY
Wagner, T., Beirle, S., Grzegorski, M., Sanghavi, S., & U., Platt. 2005a. El-Niño induced anomalies
in global data sets of water vapour and cloud cover derived from GOME on ERS-2. J. Geophys.
Res., 110(D15104).
Wagner, T., Beirle, S., Grzegorski, M., & Platt, U. 2005b. Global trends (1996 to 2003) of total
column precipitable water observed by GOME on ERS-2 and their relation to surface temperature.
J. Geophys. Res. (accepted).
Wang, P., Richter, A., Bruns, M., Rozanov, V., Burrows, J. P., Heue, K.-P., Wagner, T., Pundt, I., &
Platt, U. 2005. Measurements of tropospheric NO2 with an airborne multi-axis DOAS instrument.
Atmos. Chem. Phys., 5, 337 – 343.
Weidner, F., Bösch, H., Bovensmann, H., Burrows, J.P., Butz, A., Camy-Peyret, C., Dorf, M.,
Gerilowski, K., Gurlit, W., Platt, U., von Friedeburg, C., Wagner, T., & Pfeilsticker, K. 2005.
Balloon-borne limb profiling of UV/vis skylight radiances, O3, NO2, and BrO: Technical set-up
and validation of the method. Atmos. Chem. Phys., 5, 1409 – 1422.
Wenig, M., Jähne, B., & Platt, U. 2005. Operator Representation as a new differential optical absorption
spectroscopy formalism. Appl. Opt., 44(16), 3246–3253.
Wollschläger, U., & Roth, K. 2005. Estimation of temporal changes of volumetric soil water content
from ground-penetrating radar reflections. Subsurf. Sens. Technol. Appl., 6(2), doi: 10.1007/s11220–
005–0007–y.
Wurth, G., Niggemann, S., Richter, D.K., & Mangini, A. 2004. The Younger Dryas and Holocene
climate record of a stalagmite from Hölloch Cave (Bavarian Alps, Germany). Journal of Quaternary
Science, 19, 291–298.
Yu, Q., Shi, C., Niu, F., He, N., & Roth, K. 2005. Analysis of temperature controlled ventilated
embankment. Cold Reg. Sci. Technol., 42, 17–24, doi:10.1016/j.coldregions.2004.11.004.
Zhang, X., & Garbe, C. S. 2004. Studying dynamical processes of air-sea exchanges with air-water inerface
image techniques. Chap. 3, pages 57–88 of: Recent Research Developments in Fluid Dynamics,
vol. 5. Transworld Research Network.
Zingler, J., & Platt, U. 2005. Iodine Oxide in the Dead Sea Valley: Evidence for inorganic sources of
boundary layer IO. J. Geosphys. Res., 110, D07307.

7.2. GREY PUBLICATIONS 215
Grey Publications
ACCENT. 2005. Workshop on Radiative Transfer Modeling, Heidelberg.
Auer, M., Kutschera, W., Priller, A., Wagenbach, D., Wallner, A., & Wild, E. M. 2005 (September
5-10). Atmospheric 26 Al and 10 Be as a dating tool for climate archives (Abstract). vol. The 10th
International Conference on Accelerator Mass Spectrometry Berkeley, California.
Bigler, M., Röthlisberger, R., Ruth, U., Siggaard-Andersen, M.-L., Steffensen, J. P., Hansson, M. E.,
Goto-Azuma, K., Fischer, H., & Wagenbach, D. 2005. A new high-resolution chemical ice core
record over the last glacial period from NGRIP. Geophysical Research Abstracts, Vol 7, 05616.
Christl, M., Schulze, B., Wenderothr, P., Bernsdorff, F., & Mangini, A. 2005. Geomagnetic variability
over the past 300,000 years from cosmogenic beryllium-10 in deep-sea sediments - a potential global
matching tool. 22. Internationale Polartagung, 18.24.09.2005, Poster.
Dombrowski-Etchevers, I., Peuch, V.-H., Wagenbach, D., & Legrand, M. 2005. Validation of concentrations
of lead-210 in high altitude simulated by MOCAGE. Geophysical Research Abstracts, Vol
7, 09009.
Grzegorski, M., Frankenberg, C., Platt, U., Wenig, M., Fournier, N., Stammes, P., & Wagner, T. 2004.
Determination of cloud parameters from SCIAMACHY data for the correction of tropospheric trace
gases. In: Proceedings of the ENVISAT & ERS Symposium, 6-10 September 2004, Salzburg, Austria.
ESA-publication SP-572, (CD-ROM).
Hartl, A., Mettenorf, K. U., Song, B. C., & Pundt, I. 2005. Reconstruction of 2D-Trace Gas Concentration
Distributions from Long-path DOAS Measurements: General Approach, Validation and
Simulations for an Experiment on an Urban Site. In: Proceedings of the 31st ”International Symposium
of Remote Sensing of the Environment”, June 20-24, 2005, in St. Petersburg, Russia. ISPRSpublication(CD-ROM).
Heue, K.-P., Beirle, S., Bruns, M., Burrows, J. P., Platt, U., Pundt, I., Richter, A., Wagner, T., &
P. Wang, P. 2004. SCIAMACHY validation using the AMAXDOAS instrument. In: Proceedings
of the ENVISAT & ERS Symposium, 6-10 September 2004, Salzburg, Austria. ESA-publication
SP-572 (CD-ROM).
Ilmberger, J., & von Rohden, C. 2005. Abschlußbericht zum Forschungsvorhaben: ”SF6 als Tracer
für Transport- und Mischungsprozesse in Tagebaurestseen.
Ilmberger, J., von Rohden, C., & Wunderle, K. 2005. Observation of Multilayer Structures in a Small
Lake. In: In A. Folkard and I. Jones,editors, 9th workshop on physical processes in natural waters.
Jähne, B. 2004. Handbook of Digital Image Processing for Scientific and Technical Applications. 2nd
edn. Boca Raton: CRC Press.
Jähne, B. 2005a. Digital Image Processing. 6th edn. Berlin: Springer.
Jähne, B. 2005b. Digitale Bildverarbeitung. 6th edn. Berlin: Springer.
Kreuzer, A. M., Zongyu, C., Kipfer, R., & Aeschbach-Hertig, W. in press 2005. Environmental Tracers
in Groundwater of the North China Plain. In: IAEA (ed), International Conference on Isotopes in
Environmental Studies - Aquatic Forum 2004. Monte-Carlo, Monaco: IAEA.
Marbach, T., Beirle, S., Hollwedel, J., Platt, U., & Wagner, T. 2004. Identification of tropospheric
emission sources from satellite observations: Synergistic use of trace gas measurements of formaldehyde
(HCHO), and nitrogen dioxide (NO2). In: Proceedings of the ENVISAT & ERS Symposium,
6-10 September 2004, Salzburg, Austria. ESA publication SP-572, (CD-ROM).
Pettinger, M., Keck, L., Fischer, H., Wagenbach, D., Preunkert, S., Böhm, R., Hoelzle, M., & Hoffmann,
M. Leuenbergerand G. 2005. Cenntennial scale isotope thermometry from Alpine ice core
records: shortcomings and challenge. Geophysical Research Abstracts, Vol 7, 07941.
Platt, U., Pfeilsticker, K., & Vollmer, M. 2005. Chapter 24: Atmospheric Optics. In: Träger, F. (ed),
Springer Handbook of Lasers and Optics. Heidelberg: Springer.

216 CHAPTER 7. BIBLIOGRAPHY
Poehler, D., Rippel, B., Stelzer, A., Mettendorf, K. U., Hartl, A., Platt, U., & Pundt, I. 2005.
Instrumental setup and measurement configuration for 2D-tomographic DOAS measurements of
trace gas distributions over an area of a few square km. In: Proceedings of the 31st ”International
Symposium of Remote Sensing of the Environment”, June 20-24, 2005, in St. Petersburg, Russia.
ISPRS-publication(CD-ROM).
Pundt, I., Hak, C., Hartl, A., Heue, K.-P., Mettendorf, K. U., Platt, U., Poehler, D., Rippel, B., Song,
B.-C., Stelzer, A., Wagner, T., Bruns, M., Burrows, J. P., Richter, A., & Wang, P. 2005. Mapping of
tropospheric trace gas concentration distributions from ground and aircraft by DOAS-tomography
(Tom-DOAS). In: Proceedings of the 31st ”International Symposium of Remote Sensing of the
Environment”, June 20-24, 2005, in St. Petersburg, Russia. ISPRS-publication(CD-ROM).
Schock, M., Greilich, S., Wagenbach, D., Preunkert, S., Legrand, M., Petit, J. R., Flückiger, J.,
Leuenberger, M., Haeberli, W., & Psenner, R. 2005. Dissolved organic carbon (DOC) in ice samples
from non-temperated, polar and Alpine glaciers. Geophysical Research Abstracts, Vol. 7, 08671.
Scholz, D., & Mangini, A. in press. U-redistribution in fossil reef corals from Barbados, West Indies,
and sea level reconstruction for MIS 6.5. In: Sirocko, F., Litt, T., Claussen, M., & Sanchez Goni,
M.-F. (eds), The climate of past interglacials.
Schröder Ritzrau, A., Freiwald, A., & Mangini, A. 2005. U/Th dating of deep-water corals from the
eastern North Atlantic and the western Mediterranean Sea. In: Freiwald, A., & Roberts, J.M.
(eds), Cold-water corals and ecosystems. Berlin Heidelberg: Springer-Verlag.
Spötl, C., Mangini, A., Burns, S.J., Frank, N., & Pavuza, R. 2004. Speleothems from high alpine
Spannagel Cave, Zillertal Alps (Austria). Page 329 of: Sasowsky, I., & MyIroie, J. (eds), Studies of
Cave Sediments. New York: Kluwer Academic.
Steier, P., Drosg, R., Kutschera, W., Wild, E. M., Fedi, M., Wagenbach, D., & Schock, M. 2005.
Radiocarbon determination of particulate organic carbon (POC) in non-temperated, Alpine glacier
ice (Abstract). The 10th International Conference on Accelerator Mass Spectrometry Berkeley,
California, September 5-10, 2005.
Volkamer, R., Barnes, I., Platt, U., Molina, L. T., & Molina, M. J. 2004. Remote Sensing of Glyoxal
by Differential Optical Absorption Spectrosocopy (DOAS): Advancements in Simulation Chamber
and Field Experiments. In: Rudzinski, K., & Barnes, I. (eds), NATO Advanced Research Workshop
of Environmental Simulation Chambers - Application to Atmospheric Chemical Processes, vol.
NATO Sciences Series, IV. Earth and Environmental Sciences. Zakopane, Poland: Kluwer Academic
Publishers.
von Glasow, R. 2005. Lead Essay - Research Front Iodine. Env. Chem., 2, in press.
von Rohden, C., Hauser, A., Wunderle, K., Ilmberger, J., Wittum, G., & Roth, K. 2005. Lake
dynamics: observation and high-resolution numerical simulation. In Rannacher editor. Springer.
Wegner, A., Rohlfs, J., Huke, M., Stanzick, A., Wagenbach, D., Oerter, H., Sommer, S., Mulvaney,
R., & Kubik, P. 2005. Bi-annual to decadal 10 Be variability in firn cores from Dronning Maud Land
(DML) and Berkner Island (BI), Antarctica. Geophysical Research Abstracts, Vol 7, 08396.
Wilms-Grabe, W., Kühl, S., Beirle, S., Platt, U., & Wagner, T. 2004. GOME observations of stratospheric
trace gas distributions during the split vortex event in the Antarctic winter 2002. Pages
1053–1054 of: Proceedings Quadrennial Ozone Symposium, 1-8 June 2004, Kos, Greece.

7.3. PHD THESES 217
PhD Theses
Bayer, A. 2005. X-ray attenuation techniques to explore the dynamics of water in porous media. PhD
thesis, University of Heidelberg.
Beirle, S. 2004. Estimating source strengths and lifetime of Nitrogen Oxides from satellite data. Ph.D.
thesis, Institut für Umweltphysik, Universität Heidelberg, Germany.
Bobrowski, N. 2005. Volcanic Gas Studies by MAX-DOAS. Dissertation, Universität Heidelberg.
Dorf, M. 2005. Investigation of inorganic stratospheric bromine by balloon-borne DOAS measurements
and model simulations. PhD thesis, University of Heidelberg, Heidelberg, Germany.
El-Gamal, H. 2005. Environmental tracers in groundwater as tools to study hydrological questions in
arid regions. PhD thesis, University of Heidelberg.
Frankenberg, C. 2005. Retrieval of Methane and Carbon Monoxide using near infrared spectra recorded
by SCIAMACHY onboard ENVISAT - Algorithm development and data analysis. Ph.D. thesis,
Institut für Umweltphysik, Universität Heidelberg, Germany.
Fuß, D. 2004. Kombinierte Höhen- und Neigungsmessung von winderzeugten Wasserwellen am Heidelberger
Aeolotron. PhD Thesis, Universität Heidelberg.
Heue, K.-P. 2005a. Airborne Multi Axis DOAS instrument and measurements of two dimensional
tropospheric trace gas distributions. Ph.D. thesis, Institut für Umweltphysik, Universität Heidelberg,
Germany.
Heue, K.-P. 2005b. Airborne multi axis DOAS instrument and measurements of two dimensional
tropospheric trace gas distributions. Ph.D. thesis, Institut für Umweltphysik, Universität Heidelberg,
Germany.
Hilsenstein, V. 2004. Design and Implementation of a Passive Stereo-Infrared Imaging System for the
Surface Reconstruction of Water Waves. Ph.D. thesis, Universität Heidelberg.
Hollwedel, J. 2005. Observations of tropospheric and stratospheric Bromine Monoxide from satellite.
Ph.D. thesis, Institut für Umweltphysik, Universität Heidelberg, Germany.
Klar, M. 2005. Design of an endoscopic 3-D Particle-Tracking Velocimetry system and its application
in flow measurements within a gravel layer. Ph.D. thesis, Universität Heidelberg.
Kühl, S. 2005. Quantifying stratospheric chlorine chemistry by the satellite spectrometers GOME and
SCIAMACHY. Ph.D. thesis, Institut für Umweltphysik, Universität Heidelberg, Germany.
Mettendorf, K. U. 2005. Aufbau und Einsatz eines Multibeam Instrumentes zur DOAStomographischen
Messung zweidimensionaler Konzentrationsverteilungen. Ph.D. thesis, Institut
für Umweltphysik, Universität Heidelberg, Germany.
Naegler, T. 2005 (June). Simulating Bomb Radiocarbon: Consequences for the Global Carbon Cycle.
Ph.D. thesis, Insititut für Umweltphysik, University of Heidelberg, Heidelberg, Germany.
Nielsen, R. 2004. Hochgenaue Messung der Schmidtzahlabhängigkeit des Gasaustausches an einer
wind- und wellenbewegten Wasseroberfläche. Ph.D. thesis, Universität Heidelberg.
Peters, C. 2005. Studies of Reactive Halogen Species (RHS) in the Marine and mid-Latitudinal Boundary
Layer by Active Longpath Differential Optical Absorption Spectroscopy. Dissertation, Universität
Heidelberg.
Schimpf, D. 2005. Datierung und Interpretation der Kohlenstoff- und Sauerstoffisotopie zweier
holozäner Stalagmiten aus dem Süden Chiles (Patagonien). unpublished Master Thesis, University
of Heidelberg, Institute of Environmental Physics.
Scholz, D. 2005. U-series dating of diagenetically altered fossil reef corals and the application for sea
level reconstruction. unpublished PhD Thesis, University of Heidelberg, Heidelberger Akademie der
Wissenschaften.
Schulze, B. 2005. Hochaufgelöste Rekonstruktion der 10Be-Produktionsrate aus Tiefseesedimentkernen
des Bermuda Rise über die letzten 70.000 Jahre. unpublished Master Thesis, University of
Heidelberg, Institute of Environmental Physics.

218 CHAPTER 7. BIBLIOGRAPHY
Weidner, F. 2005. Development and application of a versatile balloon-borne DOAS instrument for
skylight radiance and atmospheric trace gas measurements. PhD thesis, University of Heidelberg,
Heidelberg, Germany.
Wenderoth, P. 2005. Untersuchung der Anwendbarkeit des authigenen 10 Be/ 9 Be-Verhältnisses in Tiefseesedimenten
als Proxy zur Rekonstruktion der Erdmagnetfeldstärke. unpublished Master Thesis,
University of Heidelberg, Institute of Environmental Physics.

7.4. DIPLOMA THESES 219
Diploma Theses
Bäuerle, A. 2004. Messung von Spurenstoffverteilungen in Mailand mit Hilfe eines Multistrahl-
Langpfad Teleskops. Staatsexamensarbeit, Institut für Umweltphysik, Universität Heidelberg, Germany.
Bengel, I. 2005. Spurenstoffglaziologische Pilotuntersuchungen an einer kalten Miniatureiskappe.
Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg.
Bobrowski, N., & Filsinger, F. 2005. Mini-MAX-DOAS Manual. Universität Heidelberg.
Halasia, M.-A. 2004. SMAX-DOAS observation of atmospheric trace gases on the Polarstern
ANT/XX-expedition from October 2002 until February 2003. Diplomarbeit, Institut für Umweltphysik,
Universität Heidelberg.
Herzog, A. 2005. Free Parameterisation of Soil Hydraulic Properties. Diplomarbeit, University of
Heidelberg.
Kern, C. 2004. Applicability of light-emitting diodes as light sources for long path DOAS measurements:
A feasibility study. Diplomarbeit, Universität Heidelberg.
Klement, R. 2005. Optimierung von SF6-Grundwasserprobenahme-Methoden. Diplomarbeit, Universität
Heidelberg.
Kluge, T. 2005. Radon als Tracer in aquatischen Systemen. Diplomarbeit, Universität Heidelberg.
Knab, V. 2004. Basic theory on DOAS tomography, Reconstruction of 2D trace gas distributions by
discrete linear inversion techniques. Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg,
Germany.
Lindner, A. 2005. Ballongestütze Messungen der extraterrestrischen spektralen solaren Irradianz.
Diploma thesis, University of Heidelberg, Heidelberg, Germany.
Louban, I. 2005. Zweidimensionale Aufnahmen von Spurenstoff-Verteilungen. Diplomarbeit, Universität
Heidelberg.
May, B. 2005. Quantification of the fossile fraction of carbonaceous aerosol by radiocarbon analysis.
Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg.
Reichl, U. 2005. Ground-based direct Sun UV/vis spectroscopy in Timon/Northeastern Brazil: Comparison
of tropospheric air mass pollution in the dry and wet season. Diploma thesis, University of
Heidelberg, Heidelberg, Germany.
Rice, S. 2004. The development of a method for the extraction and measurement of noble gases from
fluid inclusions in samples of calcium carbonate. Master thesis, University of Heidelberg.
Rippel, B. 2005. Vorarbeiten für Langpfad DOAS Tomographische Messungen über der Stadt Heidelberg.
Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg, Germany.
Rocholz, R. 2005. Bildgebendes System zur simultanen Neigungs- und Höhenmessung an kleinskaligen
Wind-Wasser-Wellen. diploma thesis, Universität Heidelberg.
Schell, S. 2004. 222 Radon-Profil-Messungen in Süd- und Ostdeutschland, Anwendung der Radon-
Tracer-Methode zur Berechnung von CO2- und CH4-Flüssen. Diplomarbeit, Insititut für Umweltphysik,
University of Heidelberg. in German.
Schönherr, C. 2005 (October). Investigating Carbon Dioxide, Carbon Monoxide and Fossil Fuel CO2
in Heidelberg. Diplomarbeit, Insititut für Umweltphysik, University of Heidelberg.
Schwarz, T. 2005. Development of a depth resolving boundary layer visualization for gas exchange at
free water surfaces. diploma thesis, Universität Heidelberg.
Schwärzle, J. 2005. Spektroskopische Messung von Halogenoxiden in der marinen atmosphärischen
Grenzschicht in Alcântara/Brasilien. Staatsexamensarbeit, University of Heidelberg, Heidelberg,
Germany.
Seitz, K. 2005. Spektroskopische Langzeitmessungen von Spurengasen in der freien Troposphäre.
Diplomarbeit, Universität Heidelberg.

220 CHAPTER 7. BIBLIOGRAPHY
Stelzer, A. 2005. Horizontale tomographische Langpfad-DOAS Spurengasmessungen in Heidelberg.
Diplomarbeit, Institut für Umweltphysik, Universität Heidelberg, Germany.
Träumner, K. 2005. Inbetriebnahme, Tests und erste Anwendung einer neuen Aufbereitungslinie zur
massenspektrometrischen Messung von Edelgasen aus Grundwasser - und Stalagmitproben. Diplomarbeit,
Universität Heidelberg.
Ulbrich, C. 2005. Monitoring Field Tracer Experiment with Ground Penetrating Radar and Time
Domain Reflectometry. Diplomarbeit, University of Heidelberg.
Wunderle, K. 2005. Untersuchungen der Strömungen im Willersinnweiher mit einem akustischen
Strömungsmessgerät. Diplomarbeit, University of Heidelberg.

7.5. INVITED TALKS 221
Invited Talks
Aeschbach-Hertig, W. 2004a. Climate of the Past as a Basis for an Assessment of the Future. Invited
talk, GSI-Kolloquium, Darmstadt, Germany.
Aeschbach-Hertig, W. 2004b. Environmental Tracers in Groundwater Studies - Water Resources and
Paleoclimate. Invited talk, Institute of Hydrogeology and Environmental Geology, Chinese Academy
of Geological Sciences, Zhengding, China.
Aeschbach-Hertig, W. 2004c. Excess Air in Groundwater: Problems and Opportunities. Invited
keynote presentation, Annual Meeting of the Geological Society of America (GSA), Denver, USA.
Aeschbach-Hertig, W. 2004d. Noble Gases and Excess Air in Groundwater: Review and Outlook.
Invited talk, KUP-Seminar, University of Bern, Switzerland.
Aeschbach-Hertig, W. 2005. Surface and Subsurface Waters. Invited lecture, WE-Heraeus summerschool
”Physics of the Environment”, Bad Honnef, Germany.
Bobrowski, N. 2004. The DOAS (Differential Optical Absorption Spectroscopy) principle - experimental
setups and mathematical description of the DOAS problem and Development of the Mini-MAX-
DOAS (Multi-AXis Differntial Optical Absorption Spectroscopy) and examples of applications at
three Italian volcanoes - Stromboli, Vulcano, Etna. Invited talk, Seminar INGV Palermo.
Bobrowski, N. 2005a. DOAS evaluation basics. Invited talk, IAVCEI Gas workshop 9th, Nicolosi.
Bobrowski, N. 2005b. The DOAS technique and the analyses of gas emissions of active volcanoes.
Invited talk, Seminar ”Stoffbestand und Entwicklung von Mantel und Kruste”, Mainz.
Bobrowski, N. 2005c. Volcanic research carried out with the DOAS technique - an overview. Invited
talk, Seminar at CAI Pedara.
Butz, A. 2005. LPMA/DOAS: Balloon based SCIAMACHY validation example: O3 and NO2 vertical
profiles. Invited talk, SCIAMACHY Science Advisory Group 32, Delft, Netherlands.
Jähne, B. 2004a. Exchange Processes at the Ocean Surface: Their Role in Coupling Atmosphere and
Ocean, A Contribution to the SOLAS Project. Invited talk, Hauptvortrag Fachverband Umweltphysik,
DPG Frühjahrstagung München, 22. Mrz 2004.
Jähne, B. 2004b. New Insight into the Mechanisms of Air-Sea Gas Transfer. Invited talk, IOW-
Kolloquium, Leibniz-Institut fr Ostseeforschung, Warnemünde, Januar 2004.
Jähne, B., & Garbe, C. S. 2004. Spatiotemporal Active Thermography. Invited talk, 7th International
Conference on Quantitative Infrared Thermography, von Karman Institute for Fluid Dynamics in
Rhode Saint Genèse, Belgium, 08. July 2004.
Jähne, B., Nielsen, R., Popp, C., Schimpf, U., & Garbe, C. S. 2005. Air-Sea Gas Transfer: Schmidt
Number Dependency and Intermittency. Invited talk, 37th International Liège Colloquium on Ocean
Dynamics Gas Transfer at Water Surfaces, 2–6 May 2005.
Levin, I. 2004a. Greenhouse Gases Trends in Europe and at the German Antarctic Station. Invited
talk, WMO WMO/GAW Expert Workshop on The Quality and Applications of European GAW
Measurements. Tutzing, Germany.
Levin, I. 2004b. Quantification of Exchange Rates in the Global Carbon Cycle by Radiocarbon Observations.
Invited talk, Physical Colloquium. University of Groningen, The Netherlands.
Levin, I. 2005a. Quantifying fossil fuel CO2 over Europe. Invited talk, Workshop on A Blueprint for
a GHG monitoring system in Europe. Amsterdam, The Netherlands.
Levin, I. 2005b. Recent Heidelberg Radiocarbon Observations in Atmospheric CO2. Invited talk,
13th International WMO Experts Meeting on atmospheric CO2 and Related Tracer Measurement
Techniques. Boulder (CO) USA.
Oswald, Benedikt, & Roth, Kurt. 2005. Parallel 3D Finite Element Time Domain Maxwell Solver
- Investigation of Ground Penetrating Radar Sub-Wavelength Resolution. Paul Scherrer Institut,
Villigen. 2005, August, 25.

222 CHAPTER 7. BIBLIOGRAPHY
Pechtl, S. 2005. Halogenchemie in der Troposphäre: Überblick und Beispiele für Prozessstudien mit
numerischen Modellen. Invited talk, the DLR, Oberpfaffenhofen, 15.11.2005.
Pfeilsticker, K. 2005a. Collisional complexes, metastable, and stable complexes in the atmosphere,
and their potential importance for the absorption of solar radiation. Invited talk, Gordon Research
Conference on Radiation & Climate, Colby College, Waterville, ME, USA, July 24-29.
Pfeilsticker, K. 2005b. Recent cloudy sky photon path pdf measurements from Heidelberg. Invited talk,
3rd I3RC Workshop, IFM Kiel, October 11-14.
Pfeilsticker, K., Lotter, A., Boesch, H., & Peters, C. 2004. Collisional complexes, metastable and stable
dimers in the atmosphere, and their potential importance for the absorption of solar radiation. 228th
National ACS Meeting, Philadelphia, PA, USA, August 22-26.
Piot, M., & von Glasow, R. 2005. Sensitivity studies of ODEs and frost flowers with a numerical
model. Invited talk, the OASIS workshop, Toronto, Canada, 20.09.2005.
Platt, U. 2004a. Atmospheric Chemistry and Global Change. Invited talk, Reading, United Kingdom.
Platt, U. 2004b. German SCIAMACHY Validation. Invited talk, SCIAMACHY Validation project
final workshop, Bremen.
Platt, U. 2004c. Reactive Halogen Species in the Troposphere. Invited talk, AFO-2000 Abschluß
Workshop, Bad Tölz, 22.-2. März.
Platt, U. 2004d. Spectroscopic Mapping of Trace Gases by Differential Optical Absorption Spectroscopy
(DOAS). Invited talk, Massachusetts Institute of Technology, Boston, Mass, USA.
Platt, U. 2005a. Atmospheric Chemistry and Global Change. Invited talk, Advanced Environmental
Monitoring Research Center, K-JIST, Kwangju, S. Korea.
Platt, U. 2005b. Atmospheric Gas Phase Reactions. Invited talk, SOLAS Summer School, Cargese,
Corsica, France.
Platt, U. 2005c. The Determination of Reactive Halogen Species in the Troposphere and their Relevance
for Atmospheric Chemistry. Invited talk, Workshop des DFG-Graduiertenkollegs 826,
Elementspeziation: Methodenentwicklung und ihre Anwendung in den Umwelt- und Lebenswissenschaften,
Mainz.
Platt, U. 2005d. Neue Entwicklungen der atmosphärischen Spektroskopie - wie BERLIOZ II aussehen
könnte. Invited talk, Seminar, Bergische Universität Wuppertal.
Platt, U. 2005e. Observation of Spatial Distributions of Air Pollutants. Plenary lecture, Royal Meteorological
Society Conference 2005, 12th-16th Sept. 2005, at the University of Exeter.
Platt, U. 2005f. Ocean - Atmosphere Exchanges and Interactions. Invited talk, IGAC/WMO WORK-
SHOP: From Chemical Weather Forecast to Climate Change in South America: the challenges and
opportunities of integration and collaboration, Centro de Modelamiento Matemático, Universidad
de Chile, Santiago de Chile.
Platt, U. 2005g. Probing the Atmosphere with Differential Optical Absorption Spectroscopy - DOAS.
Invited talk, Advanced Environmental Monitoring Research Center, K-JIST, Kwangju, S. Korea.
Platt, U., & Burrows, J. P. 2005. The Remote Sensing of Atmospheric Constituents From Space,
ACCENT-TROPOSAT-2 (AT2): An ACCENT Integration Task. Invited talk, ACCENT General
Assembly, Clermont Ferrant, 9-11 Februar.
Platt, U., & Zingler, J. 2006. Spatial Distribution of Halogen Oxides in the Dead Sea Basin, Israel
Society for Ecology and Environmental Quality Sciences. Invited talk, Conference on ”Living with
Global Change: Challenges in Environmental Sciences”, May 30 - June 1, 2005, Weizmann Institute
of Science, Israel.
Platt, U., Sinreich, R., Friesß, U., & Wagner, T. 2005. Multi Axis Differential Optical Absorption Spectroscopy
(MAX-DOAS) of Gas and Aerosol Distributions. Invited talk, 130th Faraday Discussion
Meeting ”Atmospheric Chemistry”, Leeds, United Kingdom.

7.5. INVITED TALKS 223
Pundt, I. 2005. DOAS (Differentielle Optische Absorptions- Spektroskopie) Messungen mit neuester
Technologie. Invited talk, DECHEMA/GDCH/DGB-Gemeinschaftsausschuss Chemie der Atmosphre,
Frankfurt, 22.04.2005.
Pundt, I., Mettendorf, K.U., & v. Friedeburg, C. 2005. Emissionsmessung von NO2, SO2 und O3
mittels DOAS Fernerkundung. Invited talk, workshop ”Validierung von Kfz-Emissionsdaten: Das
Karlsruher Autobahnprojekt BAB II”, Karlsruhe, 01.12.2005.
Roth, K. 2005a. Bodenwasser: Bedeutung – Herausforderung – Messung. Eröffnungsvortrag, Soil
Moisture Group, Universität Karlsruhe, 8. Juni.
Roth, K. 2005b. GPR zur Quantifizierung von Transportprozessen in Böden? Institut für Geophysik,
Universität Kiel, 20. Mai.
Roth, K. 2005c. Measurement and Modeling of Thermal and Hydraulic Dynamics of Permafrost Soils.
Dept. of Earth Sciences, Uppsala University, March 31.
Roth, K., & Wollschläger, U. 2005. Field-Scale Measurement of Soil Water Content. Plenary Session
at International Conference on Human Impacts on Soil Quality Attributes, Isfahan, Iran, September
12–16.
Vogel, H.-J. 2005a. From Pore- to Continuum-Scale Understanding of Flow and Transport Processes
in Porous Media. Keynote paper, SSSA-Annual Meeting, November 7-11, 2005, Salt Lake City,
USA.
Vogel, H.-J. 2005b. Hierarchies of flow and transport in soil. Keynote paper, GFHN, 29emes journees,
November 24-25, 2004, Grenoble, France.
Vogel, H.-J. 2005c. Modeling the heterogeneous structure of soil to predict flow and transport. SIAM
Conference on Mathematical and Computational Issues in the Geosciences, June 7-10, 2005, Avignon,
France.
Vogel, H.-J., Samouelian, A., & Ippisch, O. 2005. Modeling structure to predict flow and transport.
Gesellschaft für Angewandte Mathematik und Mechanik, 76th Annual Scientific Conference, March
28 - April 1, 2005, Luxembourg.
von Glasow, R. 2004a. Halogenchemie in der Troposphäre - Untersuchungen mit numerischen Modellen.
Invited talk, the Insitut für Meteorologie und Klimaforschung, Karlsruhe, 02.11.2004.
von Glasow, R. 2004b. Links between sulfur and halogen chemistry and implications for our climate.
Invited talk, the Afred-Wegener-Institut für Meeresforschung, Bremerhaven, 05.02.2004.
von Glasow, R. 2004c. Modeling of halogen chemistry: Overview and impact on sulfur cycle. Invited
talk, the EGU meeting, Nice, 2004.
von Glasow, R. 2004d. Sea salt aerosol chemistry: Brief overview and recent modeling results. Invited
talk, the AAAR meeting, Atlanta, 2004.
von Glasow, R. 2004e. Tropospheric halogen chemistry and its implications for O3 and sulfur in
the boundary layer and free troposphere. Invited talk, the Institut für Umweltphysik, Bremen,
06.02.2004.
von Glasow, R. 2005a. Invited talk, the AGU meeting, San Francisco, 2005.
von Glasow, R. 2005b. Halogenchemie in der Troposphäre - Untersuchungen der Wechselwirkungen
mit Ozon und Schwefel in Prozess- und globalen Modellstudien. Invited talk, the Institut für
Troposphärenforschung, Leipzig, 12.05.2005.
von Glasow, R. 2005c. Impact of bromine on tropospheric photochemistry. Invited talk, the
IGAC/SPARC workshop, Mainz, 19.05.2005.
von Glasow, R. 2005d. Importance of the surface reaction OH + Cl- on sea salt aerosol for the
chemistry of the MBL - a model study. Invited talk, the EMSI Workshop on Ions and Molecules at
Aqueous Interfaces, Prague, Czech Republic, 27.06.2005.
von Glasow, R. 2005e. Reactive halogen chemistry in the troposphere - Using numerical models for
detailed process studies of the marine boundary layer and a first global assessment. Invited talk,
NIWA, Lauder, New Zealand, 15.09.2005.

224 CHAPTER 7. BIBLIOGRAPHY
von Glasow, R. 2005f. Reactive halogen chemistry in the troposphere - Using numerical models for
detailed process studies of the marine boundary layer and a first global assessment. Invited talk,
Harvard Univ., Cambridge, MA, USA, 08.04.2005.
von Glasow, R. 2005g. Reactive halogen chemistry in the troposphere - Using numerical models for
detailed process studies of the marine boundary layer and a first global assessment. Invited talk, the
Univ. New Hampshire, Durham, USA, 07.04.2005.
von Glasow, R. 2005h. Reactive halogen chemistry in the troposphere - Using numerical models for
detailed process studies of the marine boundary layer and a first global assessment. Invited talk, the
Univ. of East Anglia, Norwich, UK, 28.02.05.
Wagenbach, D. 2004. Potential and restrictions of Alpine (mid-latitude) ice cores. Invited talk, SCIEM
2000 (The synchronisation of civilization in the eastern Mediterranean in the 2nd Millenium BC)
Workshop: Ashes and Ice, Vienna.
Wagner, T. 2004a. Current status and future perspectives of atmospheric trace gas observations from
space. Invited talk, Institute Colloquium, MPI Mainz, Germany.
Wagner, T. 2004b. Global monitoring of atmospheric trace gases, clouds and aerosols from
UV/vis/NIR satellite instruments: Currents status and near future perspectives. Invited talk, SO-
LAS Science conference, Halifax, Canada.
Wagner, T. 2004c. Global monitoring of atmospheric trace gases, clouds and aerosols from
UV/vis/NIR satellite instruments: Currents status and near future perspectives. Invited talk,
WMO/GAW Expert Workshop, Tutzing, Germany.
Wagner, T. 2004d. Moderne Methoden der Satellitenbildverarbeitung: Spektroskopie, Reflektions-,
Streu-, und Absorptionsprozesse. Invited talk, WMO/GAW Expert Workshop, Tutzing, Germany.
Wagner, T. 2005a. 7.5-year global trends in GOME cloud cover and humidity - a signal of climate
change? Invited talk, KNMI, Utrecht, The Netherlands.
Wagner, T. 2005b. Troposphärische Spurengasmessungen vom Satelliten aus. Invited talk,
DECHEMA, Frankfurt, Germany.
Wagner, T. 2005c. Wasserdampf-Fernerkundung mit dem ERS-2/GOME Sensor und seinen Nachfolgern.
Invited talk, DWD, Offenbach, Germany.
Zingler, J. 2005. Eine kurze Geschichte von Messungen zur Halogenchemie am Toten Meer, Israel.
Invited talk, Seminar über aktuelle Forschungsthemen der Meteorologie, Institut für Meteorologie
und Klimaforschung, Forschungszentrum Karlsruhe, Karlsruhe, Germany.

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