Investigating Geochemistry and Habitability at Continental Sites of Serpentinization
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Investigating Geochemistry and Habitability at Continental Sites of Serpentinization: The Cedars, California, USA and the Tablelands, Newfoundland, CAN by © Amanda Rietze, B.Sc. (Hons) A Thesis submitted to the School of Graduate Studies in partial fulfillment of the requirements for the degree of Master of Science Department of Earth Sciences Memorial University of Newfoundland May 2015 St. John’s Newfoundland ABSTRACT This study investigates the geochemistry and habitability of spring fluids associated with active continental serpentinization at The Cedars, California, USA and the Tablelands, Newfoundland, CAN. These ophiolite complexes were host to several springs discharging ultra-basic (>11) and highly reducing (<-400 mV) fluids rich in H2 gas that were geochemically distinct from the surrounding groundwater. C2+ hydrocarbons at both ophiolite complexes suggest hydrocarbons were thermogenic in origin; however, an abiogenic contribution could not be ruled out. Methane at The Cedars was dominated by a microbial origin with a contribution of non- microbial sources, while methane at the Tablelands was dominated by a non-microbial source (i.e. thermogenic or abiogenic or mixture of the two). Spring fluids lacked electron acceptors and nutrients which adds further complications to the already unusually high pH and limited carbon fixation possibilities in this extreme environment. ii ACKNOWLEDGEMENTS I would like to express my sincere gratitude to all of those who have offered intellectual, emotional, and physical help over the past few years. Above all else I would like to thank my supervisor Penny Morrill for being a tremendous mentor for me and for introducing me to the topic of serpentinization and the amazing sites where I had the pleasure to work on a number of occasions. I have expanded my skills as a research scientist and have become a more critical thinker because of you. Your compassion and support throughout this thesis will never be forgotten. I would also like to thank my committee member James Macquaker for encouraging my research and always reminding me of the big picture and overall aim of my project. I always had a new and clearer perspective on my research after our meetings that have helped me to develop and focus on my research goals. This research was funded by a National Sciences and Engineering Research Council (NSERC) Discovery grant awarded to Penny Morrill and a National Science Foundation (NSF) grant awarded to Ken Nealson. I also gratefully acknowledge the financial support from Memorial University. Additionally I would like the thank lab technicians Geert van Biesen, Jamie Warren, Helen Gillespie and Alison Pye for all their analytical instructions and teachings throughout this thesis work. Collaborators Shino Suzuki and Billy Brazelton, thank you for your intellectual input and willingness to share data and ideas. I also want to thank the biogeochemistry lab group for listening to endless practise talks and providing support through numerous discussions. In particular I would like to thank Natalie for her guidance and friendship, Emily for her instrumental role in the iii creation of the maps used in this thesis, and Heidi, Lukas and Mark for their assistance in the field. A special thanks to my family (Mom, Dad, Mark and Courtney) for all their support and love over the past few years. This thesis would not have materialized without your encouragement and support in all shapes and forms especially during the rough periods. Bazey, it was the best of times it was the blusrt of times, but no matter what times they were you saw me through it all. Without your love and friendship I dare say I am not sure where I would be today. You have made my time in Newfoundland an adventure that I will not soon forget. iv Table of Contents ABSTRACT........................................................................................................................ii ACKNOWLEDGEMENTS............................................................................................... iii List of Tables ................................................................................................................... viii List of Figures.................................................................................................................... xi List of Symbols, Nomenclature or Abbreviations .......................................................... xvii List of Appendices......................................................................................................... xviii Chapter 1: Introduction..................................................................................................... 19 1.1 Study Significance .................................................................................................. 19 1.2 Serpentinization Reaction ....................................................................................... 20 1.3 Sites of Serpentinization ......................................................................................... 22 1.4 Serpentinization Occurring in Phanerozoic Ophiolite Complexes Found at The Cedars, CA, USA and the Tablelands, NL, CAN......................................................... 26 1.4.1 The Cedars, CA, USA...................................................................................... 26 1.4.2 Tablelands, NL, CAN ...................................................................................... 27 1.5 Hydrocarbon Sources.............................................................................................. 29 1.6 Hydrocarbon Production at Continental Ophiolite Hosted Springs Associated with Serpentinization ............................................................................................................ 30 1.7 Distinguishing Between Hydrocarbon Sources ...................................................... 36 1.8 Objectives and Outline of Study............................................................................. 40 1.9 Contributions to the Field of Natural Science......................................................... 41 1.10 Tables and Figures ................................................................................................ 43 Chapter 2: Sampling and Analytical Methods.................................................................. 47 2.1 Sampling Locations and Dates................................................................................ 47 2.1.1 The Cedars ....................................................................................................... 47 2.1.2 The Tablelands................................................................................................. 49 2.2 Aqueous Geochemistry........................................................................................... 51 2.3 H2, CO2, and C1-C6 Gas Sampling and Analysis.................................................... 57 2.3.1 Sampling of Gases ........................................................................................... 57 2.3.2 Analysis of Gases............................................................................................. 59 2.4 Volatile and Semi Volatile Organic Compound Sampling and Analysis............... 61 2.4.1 Sampling of Volatile and Semi Volatile Organic Compounds........................ 62 2.4.2 Analysis of Volatile and Semi Volatile Organic Compounds ......................... 62 2.5 Sedimentary Organic Matter Sampling and Analysis............................................. 65 2.5.1 Sampling for Sedimentary Organic Matter...................................................... 66 2.5.2 Analysis of Sedimentary Organic Matter ........................................................ 66 2.6 Mixing Models........................................................................................................ 67 2.7 Tables and Figures .................................................................................................. 69 v Chapter 3: Results............................................................................................................. 80 3.1 The Cedars .............................................................................................................. 80 3.1.1 Aqueous Geochemistry of Ultra-Basic Springs............................................... 80 3.1.2 Gaseous Composition of Spring Waters and Austin Creek Water .................. 90 3.1.3 Isotopic Composition of Gaseous Hydrocarbons ............................................ 94 3.1.4 Volatile and Semi Volatile Organic Compound Composition ........................ 96 3.1.5 Sedimentary Organic Matter Composition ...................................................... 99 3.2 The Tablelands...................................................................................................... 100 3.2.1 Aqueous Geochemistry of ultra-basic springs ............................................... 100 3.2.2 Gaseous Composition of Spring Waters and Winter House Brook Waters... 112 3.2.3 Isotopic Composition of Gaseous Hydrocarbons .......................................... 114 3.2.4 Volatile and Semi Volatile Organic Compound Composition ...................... 115 3.2.5 Sedimentary Organic Matter Composition .................................................... 118 3.3 Tables and Figures ................................................................................................ 120 Chapter 4: Discussion 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