Development of compound-specific hydrogen isotope ratio analysis of biomarkers and their application as new proxy for reconstruction of palaeoenvironment and palaoclimate [Elektronische Ressource] = Entwicklung komponentenspezifischer Wasserstoffisotopen-Analyse von Biomarkern und deren Anwendung als neuartiger Proxy zur Rekonstruktion von Paläoumwelt und Paläoklima / von Jens Radke

Jens Radke

Informations

• Publié par: friedrich-schiller-universitat_jena
• Publié le: 01 janvier 2006
• Nombre de lectures: 18
• Langue: English
• Poids de l'ouvrage: 2 Mo

Extrait

Development of Compound-Specific Hydrogen Isotope Ratio
Analysis of Biomarkers and their Application as New Proxy
for Reconstruction of Palaeoenvironment and Palaeoclimate


Entwicklung komponentenspezifischer Wasserstoffisotopen-
Analyse von Biomarkern und deren Anwendung als
neuartiger Proxy zur Rekonstruktion von Paläoumwelt und
Paläoklima






Dissertation
zur Erlangung des akademischen Grades doctor rerum naturalium
(Dr. rer. nat.)









vorgelegt dem Rat der Chemisch-Geowissenschaftlichen Fakultät der
Friedrich-Schiller-Universität Jena
von Diplom Geologe Jens Radke
geboren am 20.2.1967 in Bremerhaven





























Gutachter:
1. Prof.Dr.R.Gaupp
2. PD.Dr.G.Gleixner
Tag der öffentlichen Verteidigung: 18.1.2006






























Printed on 100% recycled paper (after ISO9706, 133 CIE, DIN 6738 LDK 24-85)
Content
Content
ABSTRACT
KURZFASSUNG
ABBREVIATIONS
1 INTRODUCTION ......................................................................................................... 1
2 FRACTIONATION OF WATER ISOTOPES IN THE ENVIRONMENT ........................................ 2
2.1 Fractionation of water isotopes in the climate system......................................... 2
2.2 Fractionation of hydrogen in the biosynthesis of plant biomass.......................... 3
3 SEDIMENTS AND METHODS........................................................................................ 6
3.1 Sediment samples and stratigraphic framework ................................................. 6
3.2 Sample preparation for bulk and compound specific analysis ............................ 8
3.2.1 Sample preparation .....................................................................................................8
3.2.2 Extraction method........................................................................................................8
3.2.3 Chemical treatment to reduce sample matrix ..............................................................9
3.3 Elemental analysis - organic C, N, S and inorganic C ...................................... 10
3.3.1 Elemental analysis of C, N, S ....................................................................................10
3.3.2 Determination of the inorganic carbon and organic carbon .......................................10
3.4 Elemental analysis of individual compounds (C, N, H, Si) ................................ 11
3.5 Isotope ratio mass spectrometry....................................................................... 11
3.5.1 Referencing strategy for gas isotope ratios ...............................................................13
3.5.1.1 Hydrogen, carbon, nitrogen isotope referencing .................................................... 13
3.5.2 Carbon and hydrogen isotope determination of biomarkers......................................16
3.5.3 External standardization in compound specific isotope analysis ...............................17
4 DEVELOPMENT OF ISOTOPE ANALYSIS OF BIOMARKERS IN SEDIMENTS ........................ 19
4.1 Development of compound specific hydrogen isotope analysis 19
4.1.1 Ion Source stability and linearity for reporting hydrogen isotope ratios .....................19
4.1.2 Formation of hydrogen gas by pyrolysis ....................................................................20
4.1.3 Precision and accuracy of hydrogen isotope analysis ...............................................22
4.1.4 Hydrogen isotope effects in sample preparation........................................................29
4.1.4.1 Lipid extraction........................................................................................................ 29
4.1.4.2 Chemical clean-up procedure................................................................................. 30
5 CORRELATION BETWEEN HYDROGEN ISOTOPE RATIOS OF LIPID BIOMARKERS AND
SEDIMENT MATURITY ............................................................................................... 31
5.1 Introduction....................................................................................................... 31
5.1.1 Geological setting ......................................................................................................32
5.1.2 Samples.....................................................................................................................33
5.2 Methods............................................................................................................ 35
I Content
5.3 Results.............................................................................................................. 36
5.4 Discussion ........................................................................................................ 39
5.4.1 Correlation of hydrogen isotope ratios of hydrocarbons with thermal maturation......39
5.4.2 δD of isoprenoids during maturation and their synthesis ...........................................45
5.4.3 Possible mechanisms for observed hydrogen isotope enrichment in
hydrocarbons of matured sediments..........................................................................46
5.4.3.1 Thermal methanogenesis ....................................................................................... 46
5.4.3.2 Hydrogen exchange in equilibrium ......................................................................... 48
5.4.3.3 Influence of clay minerals on the δD value of hydrocarbons.................................. 48
5.4.3.4 Influence of heat transfer on D enrichment in hydrocarbons.................................. 49
5.4.4 Reconstruction of δD values of initial source water ...................................................50
5.5 Conclusions ...................................................................................................... 51
6 HYDROGEN ISOTOPE RECONSTRUCTION OF THE WATER CYCLE OF EQUATORIAL,
CONTINENTAL DEPOSITS OF THE UPPER CARBONIFEROUS TO THE LOWER PERMIAN
AND IN MARINE DEPOSITS OF THE UPPER PERMIAN AND MIDDLE MESOZOIC
(CENTRAL EUROPE)................................................................................................ 53
6.1 Introduction....................................................................................................... 53
6.1.1 Palaeogeography and palaeoclimate during icehouse-greenhouse conditions in
the Upper Palaeozoic54
6.1.2 Palaeogeography and palaeoclimate ........................................................................57
6.1.2.1 Continental climate reconstruction from Permo-Carboniferous deposits ............... 57
6.1.2.2 Palaeozoic-Mesozoic marine deposits ................................................................... 57
6.2 Geological setting of the marine and continental deposits................................ 58
6.2.1 Intermontane basins of Central Europe from the Late Carboniferous to the
Early Permian ............................................................................................................58
6.2.1.1 Saar-Nahe Basin .................................................................................................... 60
6.2.1.2 Döhlen Basin .......................................................................................................... 60
6.2.1.3 Lodève Basin 61
6.2.2 Late Palaeozoic and Middle Mesozoic marine deposits ............................................61
6.2.2.1 The Kupferschiefer ................................................................................................. 61
6.2.2.2 The Posidonienschiefer .......................................................................................... 61
6.3 Methods............................................................................................................ 63
6.3.1 Sample preparation ...................................................................................................63
6.3.2 Quantification of elements .........................................................................................63
136.3.3 Isotope ratio determination of δD and δ C values.....................................................64
6.3.4 Maturity correction and hydrogen isotope ratio modelling of source water................65
6.4 Results.............................................................................................................. 65
6.4.1 δD values of n-alkanes in Late Palaeozoic and Early Jurassic sediments in
relation to environmental parameters ........................................................................65
II Content
6.4.1.1 Lateral and intra-coal seam variations of δD values from hydrocarbons in the
Saar-Nahe Basin and Döhlen Basin............................................................................ 66
6.4.1.2 δD values of n-alkanes in marine sediments.......................................................... 68