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UC Santa Barbara UC Santa Barbara Electronic Theses and Dissertations UC Santa Barbara UC Santa Barbara Electronic Theses and Dissertations Title Geochemistry of Molybdenum and Other Variably Chalcophile Elements Permalink https://escholarship.org/uc/item/2cq885fk Author Greaney, Allison Talbott Publication Date 2018 Peer reviewed|Thesis/dissertation eScholarship.org Powered by the California Digital Library University of California UNIVERSITY OF CALIFORNIA Santa Barbara Geochemistry of Molybdenum and Other Variably Chalcophile Elements A dissertation submitted in partial satisfaction of the requirements for the degree Doctor of Philosophy in Earth Science by Allison Talbott Greaney Committee in charge: Professor Roberta L. Rudnick, Chair Professor Matthew G. Jackson Professor Frank J. Spera December 2018 The dissertation of Allison Talbott Greaney is approved. __________________________________________ Frank J. Spera __________________________________________ Matthew G. Jackson __________________________________________ Roberta L. Rudnick, Committee Chair December 2018 ACKNOWLEDGEMENTS I dedicate this dissertation to my mom and dad, Melissa Talbott and Dennis Greaney, who instilled a sense of curiosity and independence in me from an early age. From talking me through my first elementary school homework assignments that left me in tears, to sharing words of encouragement when grad school finances got tight (“When I was in grad school I just shared peanut butter with the dog at the end of the month when I ran out of money”), my mom and dad taught me the persistence and resilience needed to be successful in a PhD program. They have shaped me into the person I am today, and I truly could not have gotten to where I am without them. Similarly, I’ve treasured the support and comedic relief from my sister Sam throughout the years. I met John during my first year of graduate school at Maryland, and although our relationship took a turn we didn’t anticipate as I moved across the country, he has been my constant motivator and support system. From striking up our first conversation over a pallasite meteorite to proposing to me on the Old Rag Granite, he has graciously allowed geology to permeate his life. I am so grateful for his patience as I pursued my PhD 2700 miles away, and for being my rock when things got tough. Roberta has been a wonderful advisor and mentor who expertly guided me through the world of geochemistry while letting me maintain independence in my research. She has always been supportive, whether analyses went right or wrong, and she always had ideas for the “next step” whenever I got stuck. Under her guidance I developed from a very green researcher, fresh out of undergrad, into an established scientist with the ability to independently design and execute a research project. I also want to thank her for allowing me to attend conferences (and dance at conference banquets) all over the world, which were all iii unforgettable experiences. I mostly appreciated that she let me be a normal human throughout grad school – from supporting me to take weekends off, to encouraging my science outreach efforts, to betting bottles of wine on research outcomes. I am forever grateful to her for guiding my scientific and professional development. My committee members: Matt Jackson and Frank Spera, my collaborators Rich Gaschnig, Steve Romaneillo, Ariel Anbar, and Aleisha Johnson, and my co-authors from around the world all provided crucial lab training and feedback to this research. Their suggestions for project ideas, modeling calculations, and writing tips helped me develop into a better scientist. I learned a great deal from everyone involved in these projects. Finally, I would like to thank the staff, faculty, and graduate students at the University of Maryland and the University of Santa Barbara. This includes the lab managers Richard Ash, Phil Piccoli, Igor Puchtel, Andrew Kylander-Clark, and Gareth Seward who contributed significantly to the analytical portion of these studies. Additionally, the professional support from the administrative staff at both institutions was crucial for my success. Lastly, I want to personally acknowledge the “first years” at UMD who got me through my first two years of graduate school, and my dear friends at UCSB: Julie, Mareike, Drew, and many others who helped me temporarily forget molybdenum with an episode of the Bachelor or bottle of champagne on the Mesa. This work was financially supported by NSF EAR Grants #133810 and #1757313, the Flagship Fellowship from the University of Maryland, the Graduate Division Dissertation Fellowship from UC Santa Barbara, and multiple travel grants from both universities and outside institutions as listed in the CV below. iv “But what are young men to rocks and mountains?” - Jane Austen v VITA OF ALLISON TALBOTT GREANEY December 2018 EDUCATION Doctor of Philosophy in Earth Science December 2018 University of California Santa Barbara Advisor: Dr. Roberta Rudnick Dissertation: “Geochemistry of Molybdenum and Other Variably Chalcophile Elements” Bachelor of Science in Geology August 2014 University of Illinois Urbana – Champaign PROFESSIONAL APPOINTMENTS Graduate Student Researcher, University of California Santa Barbara 2016-2018 Graduate Student Researcher, University of Maryland College Park 2014-2016 Undergraduate Research Assistant, University of Illinois Urbana – Champaign 2013-2014 PUBLICATIONS Greaney A.T., Rudnick R.L, Helz R.T., Gaschnig R.M., Ash R.D., Piccoli P. (2017) The behavior of chalcophile elements during magmatic differentiation as observed in Kilauea Iki lava lake, Geochimica et Cosmochimica Acta, 210, 71-96 Greaney A.T., Rudnick R.L, Gaschnig R.M., Whalen J.B., Luais B., Clemens J.D. (2018) The Geochemistry of Molybdenum in the Continental Crust, Geochimica et Cosmochimica Acta 238, 36-54 CONFERENCE ORAL PRESENTATIONS Greaney A.T. and Rudnick R.L. (2018) Completing the molybdenum isotope mass balance in subduction zones, Goldschmidt Conference Abstract #1568 Greaney A.T., Rudnick R.L., Romaniello S.J., Johnson A.C., Gaschnig R.G., Anbar A.D. (2017) Molybdenum isotopes reveal oxidation of Earth’s continental crust during the 2.4 Ga Great Oxidation Event, AGU Fall Meeting Abstract #210147 Johnson A.C., Reinhard C.T., Romaniello S.J., Greaney A.T., Garcia-Robledo E., Revsbach N.P., Canfield D.E., Lyons T.W., Anbar A.D. (2017) Quantifying Archean Oxygenation – Insights from Sulfide Oxidation Experiments at Low PO2, GSA Abstract #294-3 vi Greaney A.T., Rudnick R.L, Gaschnig R.M. (2016) “Crustal Sources of Molybdenum” Goldschmidt Conference Abstract #1754 Greaney A.T., Rudnick R.L, Helz R.T., Gaschnig R.M. Ash, R.D. Piccoli, P. (2015) “The behavior of chalcophile elements during magmatic differentiation as observed in Kilauea Iki Lava Lake”, AGU Fall Meeting Abstract #70008 CONFERENCE POSTER PRESENTATIONS Toc M., Rudnick R.L., Greaney A.T. (2018) Causes of Molybdenum Depletion in Granites, Goldschmidt Conference Abstract Greaney A.T., Rudnick R.L (2017) Chalcophile elements in the mantle, International Kimberlite Conference, Abstract #4473 Greaney A.T., Rudnick R.L., Gaschnig R.M. (2016) Molybdenum cycling during Crust Formation and Destruction, AGU Fall Meeting Abstract #134671 Johnson A.C., Reinhard C.T., Romaniello S.J., Greaney A.T., Garcia-Robledo E., Revsbach N.P., Canfield D.E., Lyons T.W., Anbar A.D. (2016) Reconciling “Whiffs” of O2 with the Archean MIF S Record: Insights from Sulfide Oxidation Experiments, AGU Fall Meeting Greaney A.T., Rudnick, R.L Helz R.T., Gaschnig R.M., Ash R.D., Piccoli P. (2015) “The behavior of chalcophile elements during magmatic differentiation as observed in Kilauea Iki Lava Lake”, GSA Fall Meeting Abstract #262233 TEACHING Instructor, Physical Geology, EARTH 2, UCSB, Summer 2018 TA, Physical Geology, EARTH 2, UCSB, Winter 2017 TA, High Temperature Geochemistry, GEOL 445, UMD, Fall 2015 TA, Igneous and Metamorphic Petrology, GEOL 443, UMD, Spring 2015 AWARDS AND GRANTS G.K. Gilbert Award for Best Department Seminar, UCSB, 2018 Harry Glicken Award for Volcanology, UCSB, 2018 Alumni Graduate Award for Research Excellence, UCSB, 2017 Doctoral Student Travel Grant, UCSB, 2017 International Kimberlite Conference Student Travel Grant, 2017 NSF Graduate Research Fellowship – Honorable Mention, 2016 Best Graduate Talk Award, UMD, 2016 Earth Research Institute Travel Grant, UCSB, 2016 Graduate Student Assoc. Travel Grant, UCSB, 2016 Goldschmidt-NASA Student Travel Grant, 2016 International Conference Student Support Award, UMD, 2016 vii Earth System Science Interdisciplinary Center (ESSIC) Travel Grant, 2016 Jacob K. Goldhaber Travel Grant, UMD, 2015 Flagship Fellowship, UMD, 2014 Outstanding Senior in Geology, UIUC, 2014 Franklin Fund Award, UIUC 2014 National Association of Geoscience Teachers Field Study Scholarship, 2014 L. Austin Weeks Undergraduate Grant, AAPG, 2014 viii ABSTRACT “Geochemistry of Molybdenum and Other Variably Chalcophile Elements” by Allison Talbott Greaney This research began with a simple question: Is molybdenum a chalcophile element – i.e., is it hosted in sulfides? I began to answer this question with three granites at the University of Maryland, then followed Mo through the Archean continental crust, Hawaiian lavas, subducted oceanic crust, the lithospheric mantle, glacial sediments, and ultimately weathering profiles at the University of California Santa Barbara. Each measurement prompted new questions about the geochemical behavior of Mo in different reservoirs. Along the way, we explored other nominally chalcophile elements like Ga, Ge, Mo, Ag, Cd, In, Sn, Sb, W, Tl, and Bi. Partitioning and isotope fractionation studies of several of these elements (e.g., Cd, Sn, Tl, W) are some of the newest frontiers in geochemistry, as their behavior has the potential to inform us of geological processes that shape our crust and mantle. Nevertheless, molybdenum remained the central theme of these research projects. Using a combination of laser ablation ICP-MS, standard addition single collector ICP-MS and isotope dilution multi collector ICP-MS, I present six studies on the geochemistry of Mo. In the first two chapters we establish that Mo is not hosted in sulfides in the granitic upper crust and in basaltic to intermediate magmas of Kilauea Iki lava lake in Hawaii.
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