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NORTHWESTERN UNIVERSITY Marine Sulfur and Strontium NORTHWESTERN UNIVERSITY Marine Sulfur and Strontium Cycling During the Transition from a Cool to Warm Greenhouse in the Early Cretaceous A DISSERTATION SUBMITTED TO THE GRADUATE SCHOOL IN PARTIAL FULFILLMENT OF THE REQUIREMENTS for the degree DOCTOR OF PHILOSOPHY Field of Earth and Planetary Sciences By Brian Michael Kristall EVANSTON, ILLINOIS December 2016 2 © Copyright by Brian Michael Kristall 2016 All Rights Reserved 3 Abstract Marine Sulfur and Strontium Cycling During the Transition from a Cool to Warm Greenhouse in the Early Cretaceous Brian Michael Kristall This dissertation develops and applies coupled marine sulfur and strontium cycle modeling to the highly dynamic Early Cretaceous demonstrating the value of increased model constraint from linkage of biogeochemical cycles with shared forcing factors. A foundation for this work is first provided by review of relevant geochemical, sedimentological, and paleontological evidence for the climatic shift from a cool to warm greenhouse in the Early Cretaceous, along with information about the timing (Geologic Time Scale 2012) of emplacement for several large igneous provinces, and the deposition of South Atlantic basinal evaporites. The coupling of the strontium and sulfur cycles first relies on a new iterative method developed here for modeling the Phanerozoic composite marine radiogenic strontium isotope record. Unlike previous strontium cycle models, variable strontium isotope ratios for the total weathering and diagenetic input fluxes are used instead of assuming that modern ratios were constant throughout the Phanerozoic. Despite the dominance of the linked hydrothermal and weathering input fluxes driving changes in both isotope records, this coupling enables a more detailed examination of the sulfur cycle, indicating that a complex interplay of changes to multiple sulfur cycle parameters is necessary to reproduce the seawater sulfate sulfur isotope record of the Early Cretaceous. Coupled strontium-sulfur modeling enables clear distinction of the Aptian-Albian (~20 Ma) isotopically light sulfate ocean as an alternate state requiring changes to multiple sulfur cycle parameters instead of the persistence of a negative excursion. The geologically rapid return to more 34S enriched sulfate values following the newly observed 4 minor negative excursion at the Albian-Cenomanian boundary is thought to be caused by fluctuations in the pyrite burial flux driven by sea level changes in a low sulfate ocean. The model results presented here also suggest a distinctly different range of values for the sulfur isotope composition of the weathering flux, weathered evaporite:pyrite ratios, pyrite burial fraction and integrated fractionation associated with pyrite burial compared to previous models as well as the importance of estimating major changes in concentration for both strontium and sulfur. 5 Acknowledgements I would like to begin by thanking my advisor, Matt Hurtgen, who was willing to give me a second chance in the academic world. I will always be grateful for his willingness to take a chance on me and reaffirming that I am a capable scientist and researcher. I would also like to thank Matt for his support, encouragement, flexibility, understanding, and guidance both professionally and personally throughout my time at Northwestern. It has been enjoyable working together and challenging one another over the years. As a member of my committee I would also like to thank Brad Sageman for all his support, encouragement and guidance along with being a great scientific mentor, professor, and department chair. I always appreciated his direct and constructive criticism. All of our conversations whether scientific or personal were always enlightening, enjoyable, and helpful. As the third and final member of my committee I would like to thank Andy Jacobson for all his valuable input, editing, and support throughout my time here. Especially in the final several months when I gave him an extreme headache with all the revised strontium equations. During my time here at Northwestern I have learned much from the faculty. I would like to thank Yarrow Axford, Trish Beddows, Craig Bina, Neal Blair, Dan Horton, Steve Jacobsen Cesca McInerney, Maggie Osburn, Matt Rossi, and Suzan van der Lee for all that I have learned from each and every one of you both in and out of the classroom as well as scientifically and personally. An additional special thank you to Trish Beddows for leading amazing field trip to the Yucatan. Similarly, an additional special thank you to Craig Bina for letting us all tag along on an amazing field trip to the UP and especially for indulging me in trying to find the Sudbury ejecta layer. 6 A special thank you to the lab managers and technicians in the IRMS and SedGeo labs over the years that have made this work possible – Petra Sheaffova, Kelly Peeler, Alexa Socianu, Koushik Dutta, and Grace Schellinger. I would like to thank the administrative staff for all that they have done in keeping this department running and organizing all of our events. Thanks to Reid Wellensiek, Shelley Levine, Alison Witt-Jansen, Ben Rice, Lisa Collins, Gina Allen and Alexis McAdams. A special thank you to Ben, Lisa, Alexis, and Gina for keeping me stocked in free candy as I would stress eat while writing my thesis, publications, and proposals. I must give a special big thank you to all the past graduate students in the Hurtgen- Sageman group that helped me out in the beginning providing fruitful scientific discussions, guidance, advice, support, lab training, and answered all my questions small and big even when they were furiously trying to finish up – Richard Barclay, Derek Adams, Young Ji Joo, Maya Gomes, and Jeremy Gouldey. I would also like to thank current Hurtgen-Sageman graduate students Matt Jones and Jiuyuan Wang for their support and discussions both scientific and non- scientific. In addition, I would like to give a special thank you to Greg Lehn and Grace Andrews for all their helpful discussions regarding isotopes and geochemistry as well as expanding our research group by dragging Andy back in time even if it was kicking and screaming a little. Of course there were many other graduate students that came before and after me that helped, supported, provided insight both scientifically and personally, and challenged me along the way that deserve my gratitude and thanks: Allie Baczynski, Rosemary Bush (everyone’s favorite paleobotanist), Dan Li, Laurel Childress, Josh Townsend, Ashley Gilliam, Jamie McFarlin, Miguel Merino, Emily Wolin, Trevor Bollmann, Renee French, Jessica Lodewyk, Michelle 7 Wenz, Yun-Yuan Chang, Kim Adams, Simon Lloyd, Carl Ebeling, Xiaoting Lou, Amir Salaree, Nooshin Saloor, Mike Witek, John Lazarz, Eddie Brooks, Everett Lasher, and Fei Wang. A very big special thank to all of my family and friends new, old, gone, big and small for all their love and support over the years as none of this could have been done without them. Especially my parents who have supported and encouraged me no matter what through all the ups and downs on this long journey. Finally, the biggest and most important thank you to my wonderful wife, Rebecca. Thank you for all your loving support, encouragement, understanding, and tolerance especially these last few months. But most of all thank you for saying yes and being my original silly girl willing to join me on this crazy adventure. 8 Table of Contents Abstract …………………………………………………………………………………………...3 Acknowledgements ……………………………………………………………………………….5 Table of Contents ………………………………………………………………………………....8 Table of Figures …………………………………………………………………………………..9 Table of Tables ………………………………………………………………………………….11 CHAPTER 1: Introduction ……………………………………………………………………...15 CHAPTER 2: Updating the temporal framework of the Early Cretaceous: review of major geologic events and updated age models for the seawater sulfate isotopic record ……………...22 CHAPTER 3: Modeling the Phanerozoic seawater radiogenic strontium isotope record: a case study of the Late Jurassic-Early Cretaceous …………………………………………………….83 CHAPTER 4: Coupled strontium-sulfur cycle modeling and the Early Cretaceous sulfur isotope record …………………………………………………………………………………………..128 CHAPTER 5: Conclusions …………………………………………………………………….193 References ……………………………………………………………………………………...198 Appendix I: Published radiometric dates for Cretaceous LIPs ………………………………...243 Appendix II: GTS2012 ages and S isotope data ……………………………………………….251 Appendix III: Carbonate associated sulfate S isotope data from ODP Hole 866A Resolution Guyot and DSDP Hole 511 Falkland Plateau …………………………………………………257 9 Table of Figures Figure 1-1 Marine sulfur cycle cartoon …………………………………………………………17 Figure 2-1 Late Jurassic-Early Cretaceous paleogeographic maps ……………………………..23 Figure 2-2 Early Cretaceous drop stones from Australia ……………………………………….26 Figure 2-3 Ontong Java-Manihiki-Hikurangi Plateau maps ……………………………………38 Figure 2-4 Cretaceous Carbon isotope record and OAEs ………………………………………50 Figure 2-5 Cretaceous seawater S isotope curve age update …………………………………...81 Figure 3-1 Late Jurassic-Early Cretaceous seawater 87Sr/86Sr curve …………………………...85 Figure 3-2 Aligning magnitude of perturbation factor ………………………………………...112 Figure 3-3 Calculated total weathering Sr isotope ratio ……………………………………….115 Figure 3-4 Phanerozoic and Neoproterozoic seawater Sr isotope record ……………………...117 Figure 3-5 Single prescribed R87,tw value ………………………………………………………118 Figure 3-6 Multiple prescribed R87,tw values …………………………………………………...120 Figure 3-7 Initial versus
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