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UNIVERSITY of CALIFORNIA RIVERSIDE Proxy Applications for Reconstructing Carbon and Sulfur Cycling in Ancient Marine Environment

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UNIVERSITY of CALIFORNIA RIVERSIDE Proxy Applications for Reconstructing Carbon and Sulfur Cycling in Ancient Marine Environment UNIVERSITY OF CALIFORNIA RIVERSIDE Proxy Applications for Reconstructing Carbon and Sulfur Cycling in Ancient Marine Environments A Dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Geological Sciences by Leanne Grace Hancock June 2018 Dissertation Committee: Dr. Timothy W. Lyons, Chairperson Dr. Gordon D. Love Dr. Sandra Kirtland Turner Copyright by Leanne Grace Hancock 2018 The Dissertation of Leanne Grace Hancock is approved: Committee Chairperson University of California, Riverside ACKNOWLEDGMENTS First and foremost, I would like to thank my advisor Dr. Tim Lyons for the opportunity and privilege to study with him at UC Riverside. These years have been challenging at times, but always rewarding. You never denied me an opportunity to learn or explore, and even in the deepest of my rabbit holes, you were a constant source of support and encouragement. Thank you for pushing me to do more than I could have thought possible every step of the way. To my committee, thank you for your time and effort in reviewing this dissertation and for countless conversations and feedback. Gordon Love, thank you for keeping me excited about the weirdness of the Monterey Formation, and for your infectious enthusiasm for geochemistry. Mary Droser and Sandra Kirtland-Turner, thank you for being strong female role models that seem to effortlessly do it all and for making me believe I could be even half as fierce as you are. Steve Bates, thank you for the literal hundreds of hours spent discussing my samples, but most importantly for your friendship and encouragement. This work was made possible by a number of individuals and organizations. To Hanna Ranch, thank you for providing access to the Tepee Buttes. To Dr. Richard Behl, our Monterey wizard—who provided access to samples otherwise unreachable—thank you for answering frantic emails and guiding me in the right direction. To Aera Energy and the Texas Bureau of Economic Geology, thank you for access to Monterey cores. Funding sources that made this work possible include field grants from the American Association of Petroleum Geologists, the Lewis and Clark Fund for Exploration and Field Research in Astrobiology, and the American Chemical Society Petroleum Research Fund. iv I have been truly lucky to have worked with so many people at UC Riverside on both professional and personal levels, who are now close friends and family, including Robyn Dahl, Lidya Tarhan, Chris Reinhard, Noah Planavsky, Laura Wehrmann, Natascha Riedinger, Alex and Ashley Zumberge, Carina Lee, Charlie Diamond, Kimberly Lau, Dan Gregory, Scott Evans, Kylie Caesar, Chrissy Hall, Crystal Rojas, Adam Elmahrek, Bridget Lee, Konstantine Choumiline, Stephanie Olson, Michelle Zill, and Maria Figueroa. To my family, thank you for being a strong foundation of support throughout this process. Mom, you are my inspiration and my drive to always do what is good and right. I can never repay you for all the times you talked me off a figurative ledge. To my stepfather Keith, you always encouraged, calmed, and believed, even when I wanted to quit. To my brothers Jason and Chip, thank you for thinking more highly of your little sister than I ever could of myself, and for always reminding me of who I am and where I came from, as only siblings can do. To my father, thank you for answering the countless whimsical questions of a six-year-old. You were the spark for my love of science, and our adventures were what lead me here in the first place. To my husband and favorite collaborator, Dalton Hardisty, I could never thank you enough for the countless hours of discussion, editing, and encouragement. You always know exactly when and how to push me to be the best version of myself. You inspire me every day, and you are unquestionably the best thing I got out of graduate school. v ABSTRACT OF THE DISSERTATION Proxy Applications for Reconstructing Carbon and Sulfur Cycling in Ancient Marine Environments by Leanne Grace Hancock Doctor of Philosophy, Graduate Program in Geological Sciences University of California, Riverside, June 2018 Dr. Timothy W. Lyons, Chairperson Oxygen availability in the oceans and atmosphere has been one of the primary controls on evolutionary advances on Earth, but our inability to measure oxygen concentrations directly requires the use of proxies that have been calibrated in low-oxygen settings. The biogeochemical cycles of sulfur and carbon, among many other elemental cycles, have been closely linked to oxygen concentrations through time, and many proxies for oxygen have arisen from observations of their linked cycles. This dissertation applies a number of geochemical proxies in two different types of environments to constrain the role of sulfate reduction and its relationships to organic carbon burial. First, I explore the role of hydrocarbon seep environments as a source of methane and reduced sulfur to the oceans, atmosphere, and biosphere using a system of Cretaceous- aged seeps in Colorado, U.S.A. The connection between sulfur and carbon cycling in seep settings through coupled sulfate reduction and anaerobic methane oxidation suggests that vi sulfur isotope compositions of carbonate-bound sulfate can be used to track paleo-sulfate reduction rates and methane concentrations. The next chapters focus on reconstructing local and global redox conditions in the Miocene Monterey Formation. The Miocene was a time of elevated global temperatures, and the Monterey Formation’s deposition into multiple sub-basins provides an ideal opportunity to study how preservation of geochemical signatures of basin redox conditions vary within and among basins as a function of local and global climatic and oceanic conditions. The first study presents commonly employed redox indicators, including iron speciation and redox-sensitive trace metal concentrations, to constrain paleoredox conditions from three basins with different hydrographic conditions during deposition, including degrees of restriction and intensities of upwelling. A second study builds on these interpretations, applying Mo and Tl isotope proxies to determine whether the low-oxygen conditions achieved in these basins during the Miocene were local or reflect more widespread low-O2 conditions in the global ocean. While collective data suggest that the California Margin was more reducing in the Miocene than it is today, Mo and Tl isotope results suggest this was likely localized and does not represent global-scale deoxygenation. vii TABLE OF CONTENTS Introduction and Motivation ................................................................................................ 1 References .............................................................................................................................. 8 CHAPTER 1: Carbonate-associated sulfate in methane-derived marine carbonates: A window to sulfate reduction rates and methane concentrations in ancient seep settings..... 9 Abstract................................................................................................................................. 10 Introduction........................................................................................................................... 11 Methods ................................................................................................................................ 15 Geologic Setting ................................................................................................................ 15 Sample Collection ............................................................................................................. 17 Conventional Carbonate Geochemistry ............................................................................. 18 Carbonate-Associated Sulfate (CAS) measurements ........................................................... 19 Results .................................................................................................................................. 21 Petrographic Observations ................................................................................................ 21 C-O isotopes and trace element compositions .................................................................... 24 CAS concentrations and d 34S ............................................................................................ 26 Discussion ............................................................................................................................. 27 Burial and diagenetic history of the Tepee Buttes carbonates ............................................. 27 CAS in micrites capture a sulfate reduction rate relationship ............................................. 33 A case study and model for quantifying SRR and methane concentrations .......................... 37 Conclusions........................................................................................................................... 42 Acknowledgements ............................................................................................................... 43 References ............................................................................................................................ 44 Supplemental Materials ......................................................................................................... 49 CHAPTER 2: A multi-basin redox reconstruction for the Miocene Monterey Formation, California, U.S.A. ..................................................................................................................
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