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 Palaeozoic ................................................................................................54 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 6.3.3 Isotope ratio determination of δD and δ13C 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 6.5 Discussion ........................................................................................................ 69 6.5.1 General distribution of δD values of n-alkanes in Late Palaeozoic and Early Mesozoic sediments ..................................................................................................69 6.5.1.1 Reconstructed δD values of source water n-alkanes in coals of the Saar- Nahe Basin and Döhlen Basin..................................................................................... 70 6.5.2 Reconstruction of the δDc value of source water in individual sedimentary