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Triple Oxygen Isotope Composition of Carbonates

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Triple Oxygen Isotope Composition of Carbonates University of New Mexico UNM Digital Repository Earth and Planetary Sciences ETDs Electronic Theses and Dissertations Summer 7-13-2020 Triple Oxygen Isotope Composition of Carbonates Jordan A.G. Wostbrock University of New Mexico - Main Campus Follow this and additional works at: https://digitalrepository.unm.edu/eps_etds Part of the Geochemistry Commons, and the Geology Commons Recommended Citation Wostbrock, Jordan A.G.. "Triple Oxygen Isotope Composition of Carbonates." (2020). https://digitalrepository.unm.edu/eps_etds/274 This Dissertation is brought to you for free and open access by the Electronic Theses and Dissertations at UNM Digital Repository. It has been accepted for inclusion in Earth and Planetary Sciences ETDs by an authorized administrator of UNM Digital Repository. For more information, please contact [email protected], [email protected], [email protected]. Jordan Anne Gibbons Wostbrock Candidate Earth and Planetary Sciences Department This dissertation is approved, and it is acceptable in quality and form for publication: Approved by the Dissertation Committee: Zachary Sharp, Chairperson Maya Elrick Peter Fawcett Viorel Atudorei Peter Swart i TRIPLE OXYGEN ISOTOPE COMPOSITION OF CARBONATES by JORDAN ANNE GIBBONS WOSTBROCK M.S, Earth and Planetary Sciences, University of New Mexico, 2014 B.S, Environmental Sciences, Westfield State University, 2010 DISSERTATION Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Earth and Planetary Sciences The University of New Mexico Albuquerque, New Mexico July 2020 ii ACKNOWLEDGEMENTS While completing a PhD might appear as a huge personal achievement, it is by no means a lonely one. It took an amazing community to help me through this process and I would like to thank everyone who helped me along the way. Zach – It is difficult to put into words the gratitude I have for the many roles you have served as an advisor. Thank you for your patience and generosity in advice, planning, research, everything about a mass spec, lab use, etc. If I were to put into words just one of the many important things you have taught me, I would say you have taught me to be very comfortable with what I do not know. Whether it is standing over a broken mass spec or staring at unexplainable data, it isn’t that the problem doesn’t make sense, it is just that we don’t understand it yet. Karen, Chris, and Jim – Thank you for teaching me so much about lab maintenance and repair. Viorel and Laura – Thank you for the open lab use and always making room for my random sporadic samples. I know, “can I just throw a couple on the back of that tray” adds up to a lot of samples over four years and I thank you for all of your help. My co-authors, committee members, and all the faculty at UNM – Thank you for your generosity in supplying samples and your patience answering all my, sometimes quite basic, questions. I tend to be a pop in, don’t make an appointment type of person and I thank everyone for their willingness to meet and UNM’s general open-door policy. It makes for such a great research atmosphere between graduate students and faculty. Thank you, Cori and James for the crash course about cephalopods. Also, thank you Peter Swart for being willing to jump onto my committee with short notice and serve as an outside committee member. All the graduate students and lab mates current and former – You all make grad school better. Thanks for all the happy, sad, and for no reason at all beers and get togethers. Thanks to Tony and Erick for listening to all my presentations that really haven’t changed that much over four years, but you keep showing up. Thanks to Jeff and Oleg, the first years of grad school were awesome with you guys and kept me motivated to keep pursuing my PhD. Thanks to Lauren Wheeler for so many dog walks and conversations. The list can go on and on but a few more names to thank are Marisa, Margaret, Cato, etc. etc. Friends and family near and far – Thank you reminding me that there is a whole big world outside this small academic bubble. You keep me grounded. Lastly, I would be completely remiss if I didn’t thank the other half of my team – Neal. Thank you for packing up and moving with me to NM to pursue my career and supporting me the whole way. You have made this process infinitely easier with your unwavering support. iii TRIPLE OXGEN ISOTOPE COMPOSITIONS OF CARBONATES by Jordan Anne Gibbons Wostbrock B.S, Environmental Sciences, Westfield State University, 2010 M.S, Earth and Planetary Sciences, University of New Mexico, 2014 PhD, Earth and Planetary Sciences University of New Mexico, 2020 ABSTRACT This dissertation presents a method of analyzing the triple oxygen isotope compositions of carbonates, presents an empirical calibration of the carbonate-water equilibrium fractionation line, presents a triple oxygen isotope equipped fluid-rock mixing model for carbonates to see-through diagenesis, and applies all these findings to ancient carbonate samples. Using modern carbonates and associate water, the following equations are calculated to describe equilibrium triple oxygen isotope fractionation of carbonates: 2.84(±× 0.02) 106 1000lnα18 O = – 2.96(± 0.19) 1), cc–wt T 2 –1.39(± 0.01) θ = + 0.5305 2). cc–wt T Using these fractionation equations provides an extremely useful tool to determine whether a carbonate sample is altered or preserves its original isotopic composition. In samples that are altered, a fluid-rock mixing model is used to see-through the diagenesis. Applying these tools to ancient carbonate rocks shows that many samples thought to be pristine are altered and are confusing paleoenvironmental interpretations. This work shows that seawater temperature and isotopic composition is unchanged over the Phanerozoic, an important consideration when reconstruction paleoenvironments. iv TABLE OF CONTENTS LIST OF FIGURES .......................................................................................................... x LIST OF TABLES ......................................................................................................... xiii PREFACE ....................................................................................................................... xiv 1. INTRODUCTION......................................................................................................... 1 2. AN INTERNALLY CONSISTENT TRIPLE OXYGEN ISOTOPE CALIBRATION OF STANDARDS FOR SILICATES, CARBONATES AND AIR RELATIVE TO VSMOW2 AND SLAP2 ....................................................................... 5 2.1 Introduction ............................................................................................................. 5 2.2 Isotope Systematics ................................................................................................. 9 2.3 Methods .................................................................................................................. 10 2.3.1 Waters .............................................................................................................. 10 2.3.2 Silicates ............................................................................................................ 11 2.3.3 Carbonates ....................................................................................................... 11 2.3.4 CO2 gas ............................................................................................................ 12 2.3.5 Oxygen gas purification and O2 analysis ......................................................... 12 2.3.6 Air .................................................................................................................... 13 2.4 Results/Discussion ................................................................................................. 14 2.4.1 Water standards ............................................................................................... 14 2.4.2 Calcite standards ............................................................................................. 17 2.4.3 CO2 from calcite .............................................................................................. 21 2.4.4 Silicate standards ............................................................................................. 22 2.4.5 Air .................................................................................................................... 25 v 2.5 Conclusion .............................................................................................................. 26 2.6 Acknowledgements ................................................................................................ 27 3. CALIBRATION OF CARBONATE-WATER TRIPLE OXYGEN ISOTOPE FRACTIONATION: SEEING THROUGH DIAGENESIS IN ANCIENT CARBONATES ............................................................................................................... 28 3.1 Introduction ........................................................................................................... 28 3.2 Methods .................................................................................................................. 32 3.2.1 Inorganic precipitation .................................................................................... 32 3.2.2 Natural Carbonates ......................................................................................... 34 3.2.3 Isotopic analyses .............................................................................................. 35 3.3 Results ...................................................................................................................
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