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The evolution of the photosynthetic carbon isotope fractionation {(_e63_1tnp) [(epsilon p)] of marine phytoplankton during the Devonian to Permian time interval [Elektronische Ressource] / vorgelegt von Thomas Kuhn

De
236 pages
The evolution of the photosynthetic carbon isotope fractionation ( ε ) of marine phytoplankton pduring the Devonian to Permian time interval Den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades vorgelegt von Thomas Kuhn aus Stuttgart Institut für Geologie und Mineralogie Friedrich-Alexander-Universität Erlangen-Nürnberg Erlangen 2007 Als Dissertation genehmigt von den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 16. Juli 2007 Vorsitzender der Promotionskommission: Prof. Dr. E. Bänsch Erstberichterstatter: PD Dr. M. Joachimski (Friedrich-Alexander-Universität Erlangen-Nürnberg) Zweitberichterstatter: Prof. Dr. Katherine H. Freeman (Pennsylvania State University, State College, PA, U.S.A.) vAcknowledgements Of the many people to whom I am grateful for their scientific support, collaborations, contributions, and discussions, I owe by far the most to Michael Joachimski and Werner Buggisch (Department of Geology, University of Erlangen-Nürnberg, Germany).
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The evolution of the photosynthetic
carbon isotope fractionation ( ε ) of marine phytoplankton p
during the Devonian to Permian time interval


Den Naturwissenschaftlichen Fakultäten
der Friedrich-Alexander-Universität Erlangen-Nürnberg

zur

Erlangung des Doktorgrades









vorgelegt von

Thomas Kuhn
aus Stuttgart



Institut für Geologie und Mineralogie
Friedrich-Alexander-Universität Erlangen-Nürnberg
Erlangen 2007










































Als Dissertation genehmigt von den
Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen-Nürnberg

























Tag der mündlichen Prüfung: 16. Juli 2007

Vorsitzender der Promotionskommission: Prof. Dr. E. Bänsch

Erstberichterstatter: PD Dr. M. Joachimski
(Friedrich-Alexander-Universität
Erlangen-Nürnberg)

Zweitberichterstatter: Prof. Dr. Katherine H. Freeman
(Pennsylvania State University,
State College, PA, U.S.A.)






v
Acknowledgements

Of the many people to whom I am grateful for their scientific support, collaborations,
contributions, and discussions, I owe by far the most to Michael Joachimski and Werner
Buggisch (Department of Geology, University of Erlangen-Nürnberg, Germany). With their
devotion to sedimentary geology, stable isotope biogeochemistry, paleoocenaography, and
paleoclimatology, and their lectures and field trips, they have greatly stimulated and promoted
my interest in these disciplines. Both have accompanied my entire geoscientific education and
development with continuous support, encouragement, precious advice, and constructive
criticism. I am deeply indebted to Michael Joachimski, the mental farther of this study and my
primary advisor, also for his patience, discreet guidance, and continuous belief in me and for
allowing me to proceed in my own way, even though this way was an exceptionally long one.
This work was funded by the German Research Foundation (DFG) as grant Jo 219/6 (to
Michael Joachimski) within the framework of the priority programme (SPP) 1054 (Evolution
of the System Earth in the Late Paleozoic - Clues from Sediment Geochemistry), which was
coordinated by Werner Buggisch.

I am also indebted to Christian Ostertag-Henning (formerly Department of Geology,
University of Erlangen-Nürnberg, Germany, now Bundesanstalt für Geowissenschaften und
Rohstoffe [BGR], Hannover, Germany) for his thorough and patient introduction into the
laboratory methods of organic geochemistry, conducting the GC-MS-analyses for and
together with me, innumerable precious discussions about all aspects of this study, and giving
me unrestricted insight into his Devonian to Permian nitrogen isotope results. The
implications of these results contributed significantly to the interpretation of the ε -data of this p
study.

My thanks also go to Daniele Lutz, the lab technician of Michael Joachimski’s stable isotope
laboratory, for her help with the sample preparation for carbon isotope analyses of total
organic carbon.

The great help and support I received from Lynn Watney (Kansas Geological Survey,
Lawrence, U.S.A.), Jeffrey Over (Department of Geological Sciences, State University of
New York, Geneseo, U.S.A.), and Grzegorz Racki (Department of Earth Sciences, Silesian
University, Sosnowiec, Poland) during my field sampling campaigns in the US-Midcontinent
area, western New York State (U.S.A.), and the Holy Cross Mountains in Poland deserve
especially cordial thanks. Lynn Watney granted access to the core library of the Kansas
Geological Survey, enabling me to obtain many valuable samples from several cores of the
Permocarboniferous cyclothems of the US-Midcontinent Basin. Besides, he kindly took the
time and effort to accompany me to several fine outcrops in Kansas to give me the
opportunity to complement my collection of Permocarboniferous samples with excellent vi
outcrop material. Finally, Lynn Watney and the Kansas Geological Survey generously
provided me with valuable geological back ground information, literature, and maps. Jeffrey
Over organized access to the core facility of the Akzo Nobel Salt Company (near Geneseo,
western New York State, U.S.A.), which allowed me to take excellent samples from some
Middle Devonian black and grey shales of the Appalachian Basin. Moreover, he readily spent
considerable time with me in the field to show me many great outcrops of the Middle to Late
Devonian black and grey shales in the western part of New York State, where I were able to
collect additional samples for this study. Jeffrey Over also supplied me with valuable
geological and paleontological information and literature. I want to thank him and his family
heartily for their hospitality and for letting me stay at their home during my visit to western
New York State. During my field stay in the Holy Cross Mountains in southeastern Poland,
Grzegorz Racki enabled me to obtain valuable sample material from the Early Carboniferous
Zareby Beds by his profound knowledge of the local geology and biostratigraphy and by
organizing the excavation of a sampling trench near the quarry of the village of Kowala.

I also wish to thank Stefan Piasecki from the Geological Survey of Denmark and Greenland
(Copenhagen, Denmark) and Brian Horsfield from the GeoForschungsZentrum (Potsdam,
Germany) for providing me with samples of the Late Permian Ravnefjeld Formation from
eastern Greenland and the Middle Devonian Lower Keg River Member from northeastern
Alberta, respectively.

This study would not have been possible without the cooperation of Katherine Freeman of the
Pennsylvania State University (PSU, Department of Geosciences, University Park, U.S.A.)
and her working group. Katherine Freeman generously granted me access to her GC-IRMS-
instrument during four extended stays to let me conduct all compound-specific carbon isotope
analyses for this study. Moreover, I greatly profited from excellent and thought-provoking
discussions with Kate, her profound expertise in the field of isotope biogeochemistry, and the
participation in her weekly group meetings. I want to tank Katherine Freeman and her entire
working group for their great collegiality, helpfulness, and hospitality. Among the members
of Kate’s working group, the following people deserve particularly cordial thanks:

Mindy Foland (now at Thermo Electron™) gave me a thorough introduction and training on
the methodology of compound-specific carbon isotope analyses and the use of the GC-IRMS-
instrument. She patiently answered all of my questions and helped me with precious advice
during my first weeks at the GC-IRMS. This enabled me to work largely independently with
the instrument already rather soon and still within the course of my first stay at Kate’s
laboratory. Moreover, I will not forget the hospitality of Mindy and Mary Jo Alfano, who let
me live in their apartment during my first stay at PSU in January/February 2001.

Margaret Ricci (now Department of Biological Sciences, University of Idaho, Moscow,
Idaho, U.S.A.) completed my training on the GC-IRMS-instrument by patiently explaining vii
me the structure and functions of the Isodat NT software (Thermo Electron™) and
introducing me into the art of evaluating and processing the peak and isotope data in the raw
files. I very much liked the instructive, relaxed, and pragmatic way of Margaret’s training.

I really enjoyed the company and congenial personality of Nikolai Pedentchouk (now
Department of Geology and Geophysics, University of Calgary, Canada), the numerous
excellent geoscientific discussions with him, and our many interesting non-geoscientific
conversations. The regular lunches together with Nikolai were always welcome, social breaks
from the daily isotope lab work in “Research West” during my stays at PSU.

I also enjoyed and profited from stimulating and lively discussions with Jen Eigenbrode (now
Geophysical Laboratory, Carnegie Institution, Washington, DC, U.S.A.), whose pragmatism,
humour, and helpfulness I appreciated a lot.

Dennis Walizer is truly a technical wizard in the field of mass spectrometry. Occasionally, the
GC-IRMS-instrument seemed to take delight in challenging me with a technical problem
beyond my so far gained experience. However, this was never a reason to despair, as Denny
was always helping me out quickly and competently with his immense experience.

Tracy Michele Henninger assisted me with the compound-specific isotope analyses during my
last stay at PSU in October 2002. However, the duration of this stay was too short, so that
many prepared samples were still not analysed at its end. It was due to Tracy’s initiative and
personal commitment, and Kate’s approval, that all of the remaining samples could still be
analysed in the weeks after my return to Germany. Tracy therefore deserves my special
thanks.

These acknowledgements would be incomplete without mentioning my friends, office mates,
and fellow PhD students Robert van Geldern, Stephan Breisig, Dirk Keller, Johannes Masszi,
Marion Hoch, Alexander Weh, Janet Zulauf, Stefan Rüttinger, Sandra Romano, and Ahren
Bichler. They constituted my social network at the Department of Geology in Erlangen and
thus made an indirect but yet significant contribution to the completion of this work.

Lastly, I want to express my deep gratitude to my parents for their unconditional and
unending mental support, kindness, and firm belief in me during the many years of this work.

1
Table of contents

Acknowledgements v
Table of contents 1
Summary 5
Zusammenfassung (Summary in German) 9

1 Introduction 13
1.1 The Devonian to Permian interval - a time of profound global changes 13
1.2 Working hypothesis and objectives of the study 15
1.3 The photosynthetic carbon isotope fractionation ( ε ) of marine phytoplankton 17 p

2 Introduction to the biogeochemistry of n-alkanes and isoprenoids 33
2.1 Introduction 33
2.2 n-alknes 34
2.3 Isoprenoids (terpenoids) 35
2.3.1 Acyclic isoprenoids and archaeal GDGTs 36
2.3.2 Cyclic isoprenoids 49
2.3.2.1 Steranes 50
2.3.2.2 Hopanes 51
2.3.2.3 Gammacerane 57
2.3.2.4 Lupanes, oleananes, ursanes 57
2.3.2.5 Cheilanthanes 58

3 Methods 61
3.1 Bulk parameters 61
3.2 Extraction of soluble organic matter (Bitumen) 61
3.3 Separation of individual organic fractions 62
3.4 Separation of n-alkanes and isoprenoids by urea adduction 63
3.5 Gas Chromatography - Mass Spectrometry (GCMS) 64
3.6 Gas Chromatography - Isotope Ratio Mass Spectrometry (GC-IRMS) 64

4 Principles of the reconstruction of the photosynthetic carbon isotope
fractionation ( ε ) of phytoplankton in ancient marine sediments 67 p

5 Sample material and geologic time scale 71
5.1 General information and characteristics 71
5.2 Late Eifelian to early Famennian sample material 73
5.2.1 Late Eifelian: Lower Keg River Member
(northeastern Alberta, Canada) 73

2
5.2.2 Late Eifelian to earliest Givetian: Union Springs and Oatka
Creek Formations (western New York State, U.S.A.) 73
5.2.3 Middle Givetian: Wanakah Shale
(western New York State, U.S.A.) 74
5.2.4 Late Frasnian and early Famennian: Hanover Shale and
Dunkirk Shale (western New York State, U.S.A.) 74
5.2.5 Late Frasnian and early Famennian: Büdesheimer Goniatitenschiefer
And Neu-Oos Cypridinenschiefer (Rheinland-Pfalz, Germany) 75
5.3 Late Famennian to early Mississippian 76
5.3.1 Latest Famennian to earliest Tournaisian: Cleveland Member of Ohio
Shale and Sunbury Shale (central and south-central Ohio, U.S.A.) 76
5.3.2 Middle to late Tournaisian: Zareby Beds
(Holy Cross Mountains, Poland) 77
5.4 Late Pennsylvanian - Early Permian: core shales of Permocarboniferous
cyclothems (Kansas, Missouri, Oklahoma, U.S.A) 77
5.5 Middle to Late Permian: Ravnefjeld Formation (East Greenland) 79

6 Results 81
6.1 Bulk rock geochemical parameters 81
6.1.1 Total, inorganic, and organic carbon (TC, TIC, TOC) 81
6.1.2 Extractable organic matter (EOM) 81
136.1.3 Carbon isotopic composition of total organic carbon (δ C ) 84 org
6.2 Organic geochemistry 86
6.2.1 n-alkanes 94
6.2.2 Acyclic isoprenoids 106
6.2.3 Cyclic Isoprenoids 109
6.2.3.1 Steranes
6.2.3.2 Hopanoids 110
6.2.3.3 Gammacerane 114
6.2.3.4 Tricyclic terpanes (cheilanthanes) 115
6.3 Carbon isotopic compositions of individual compounds 116
6.3.1 n-alkanes 116
6.3.2 Acyclic isoprenoids 125
6.4 Carbon isotopic compositions of dissolved aqueous CO ( δ ) and 2 d
phytoplankton biomass ( δ) 134 p
6.5 Photosynthetic carbon isotope fractionation ( ε ) 135 p