Biogeochemistry of the deep microbial ecosystem in the Mallik 5L-38 Gas Hydrate Production Research Well Vorgelegt von Dipl.-Geologin Raingard Maria Haberer aus St. Ingbert Von der Fakultät VI – Planen Bauen Umwelt der Technischen Universität Berlin zur Erlangung des akademischen Grades einer Doktorin der Naturwissenschaften -Dr.rer.nat.- genehmigte Dissertation Promotionsausschuss: Vorsitzender: 1. Prof. Dr. W. Dominik Berichter: 2. Prof. Dr. B. Horsfield Berichter: 3. Prof. Dr. V. Thiel Berichter: 4. Dr. habil H. Wilkes Tag der wissenschaftlichen Aussprache: 22. Juni 2007 Berlin 2007 D 83 Zwei Dinge sind zu unserer Arbeit nötig: Unermüdliche Ausdauer und die Bereitschaft, etwas, in das man viel Zeit und Arbeit gesteckt hat, wieder wegzuwerfen. Albert Einstein CONTENTS Contents CONTENTS........................................................................................................................................................... 1 DANKSAGUNG.................................................................................................................................................... 5 INDEX OF FIGURES .......................................................................................................................................... 7 INDEX OF TABLES .......................................................................................................................................... 13 LIST OF ABBREVIATIONS............................................................................................................................. 15 LIST OF PUBLICATIONS AND PRESENTATIONS.................................................................................... 17 PUBLICATIONS .................................................................................................................................................. 17 ORAL PRESENTATIONS ...................................................................................................................................... 18 POSTER PRESENTATIONS ................................................................................................................................... 19 KURZFASSUNG ................................................................................................................................................ 21 ABSTRACT......................................................................................................................................................... 23 1 INTRODUCTION ..................................................................................................................................... 25 1.1 CHARACTERISTICS OF GAS HYDRATES ................................................................................................ 25 1.2 ROLE OF GAS HYDRATES FOR MICROBIAL COMMUNITIES IN EXTREME ENVIRONMENTS ...................... 29 1.3 OBJECTIVES OF THE MALLIK 5L-38 GAS HYDRATE PRODUCTION RESEARCH WELL .......................... 32 1.4 CHARACTERISTICS OF TERRESTRIAL ORGANIC MATTER ...................................................................... 35 1.5 SEDIMENTARY PROCESSES IN A DELTA SYSTEM .................................................................................. 37 2 STUDY AREA ........................................................................................................................................... 39 2.1 GEOGRAPHICAL SETTING .................................................................................................................... 39 2.2 GEOLOGICAL SETTING ........................................................................................................................ 39 2.2.1 Tectonic structures at the Beaufort-Mackenzie Basin................................................................... 40 2.2.2 Sedimentary development of the Mackenzie Delta........................................................................ 43 2.2.3 Geological characteristics of the Mallik site................................................................................. 44 2.3 PALEOCLIMATIC CONDITIONS DURING THE TERTIARY IN THE MACKENZIE DELTA REGION ................ 47 3 METHODS................................................................................................................................................. 49 3.1 SAMPLING AND SAMPLE LABELLING ................................................................................................... 49 3.2 ANALYTICAL METHODS (SAMPLE PREPARATION AND MEASUREMENT) .............................................. 51 3.2.1 Freeze drying and grounding........................................................................................................ 51 3.2.2 Rock-Eval-Pyrolysis...................................................................................................................... 51 13 3.2.3 δ Corg-analysis of the bulk organic matter ................................................................................... 52 3.2.4 Open System-pyrolysis .................................................................................................................. 52 3.2.5 Organic petrology ......................................................................................................................... 53 1 CONTENTS 3.2.6 Lipid analysis ................................................................................................................................ 54 3.2.7 Compound specific carbon isotope analysis (GC-IR-MS)............................................................. 58 3.2.8 Phospholipid analysis ................................................................................................................... 58 3.2.9 Glycerol etherlipid analysis .......................................................................................................... 61 4 CHARACTERISATION OF THE ORGANIC MATTER IN LIGNITE LAYERS OF THE KUGMALLIT FORMATION (OLIGOCENE) AT THE JAPEX/JNOC/GSC ET AL. MALLIK 5L-38 GAS HYDRATE PRODUCTION RESEARCH WELL* ............................................................................... 63 4.1 INTRODUCTION ................................................................................................................................... 63 4.2 STUDY AREA....................................................................................................................................... 64 4.3 SAMPLES AND METHODS..................................................................................................................... 65 4.3.1 Sampling........................................................................................................................................ 65 4.3.2 Methods......................................................................................................................................... 66 4.4 RESULTS AND DISCUSSION .................................................................................................................. 70 4.4.1 Bulk characteristics....................................................................................................................... 70 4.4.2 Microscopic studies....................................................................................................................... 72 4.4.3 Open-system pyrolysis-GC............................................................................................................ 74 4.4.4 Molecular investigations............................................................................................................... 79 4.5 CONCLUSIONS..................................................................................................................................... 81 4.6 ACKNOWLEDGMENTS ......................................................................................................................... 82 5 CHARACTERISATION OF THE ORGANIC MATTER IN SAMPLES FROM DIFFERENT LITHOLOGIES OF THE MACKENZIE BAY AND THE KUGMALLIT SEQUENCE AT THE JAPEX/JNOC/GSC ET AL. MALLIK 5L-38 GAS HYDRATE PRODUCTION RESEARCH WELL - SUPPLEMENT TO CHAPTER 4 ..................................................................................................................... 83 5.1 MICROSCOPIC STUDIES – A QUANTITATIVE MACERAL ANALYSIS ........................................................ 83 5.2 LIPID ANALYSIS OF THE EXTRACTABLE ORGANIC MATTER FROM THE MALLIK WELL ......................... 87 5.2.1 Aliphatic hydrocarbon fractions ................................................................................................... 87 5.2.2 Neutral polar hydrocarbon fractions ............................................................................................ 88 5.2.3 Fatty acid fractions ....................................................................................................................... 94 5.3 CONCLUSIONS..................................................................................................................................... 97 6 OCCURRENCE AND PALEOENVIRONMENTAL SIGNIFICANCE OF AROMATIC HYDROCARBON BIOMARKERS IN OLIGOCENE SEDIMENTS FROM THE MALLIK 5L-38 GAS HYDRATE RESEARCH WELL (CANADA)*................................................................................................ 99 6.1 INTRODUCTION ................................................................................................................................... 99 6.2 STUDY AREA....................................................................................................................................