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(Title of the Thesis)* ANALYSIS OF CLAY MINERALS IN THE MUDFLATS OF SULFATE-RICH SALINE LAKES by Jennifer Lynn Bentz A thesis submitted to the Department of Geological Sciences and Geological Engineering In conformity with the requirements for the degree of Doctor of Philosophy Queen’s University Kingston, Ontario, Canada (September 28, 2017) Copyright ©Jennifer L. Bentz, 2017 Abstract Clay minerals are important targets for interpreting past environments due to their ubiquity on the surface of terrestrial planets, sensitivity to the prevailing geochemical conditions, and ability to preserve biosignatures. Modern saline lakes that develop sulfate-rich brines are less extensively analyzed due to their relative scarcity compared to those that develop bicarbonate- rich brines. Moreover, most modern sulfate-rich systems are small in area (<100 km2), playa dominated, and rich in detritus making them difficult to sample and to study. Yet, the number and diversity of these lakes makes them important for understanding authigenic mineral formation. The goal of this study was to evaluate authigenic and detrital minerals in the mudflats of sulfate- rich saline lakes. This research focused on microscale (cm) investigations of the mudflats from 23 lakes from the Great Plains of southern Saskatchewan, Canada, and Andean Plateau, Bolivia for a total of 407 sediment samples. For detrital-rich sediments, authigenic illite was consistently found within sand lenses of the mudflats, was rich in Al, Mg, and Fe, and displayed lath-like morphologies. Uncommon minerals were also found containing elements usually in minor/trace quantities that concentrate in the closed-basins. In Laguna Chiar Khota, Bolivia for example, the arsenic-rich minerals realgar and hörnesite were found within the mudflats. Lastly, this thesis demonstrates that the biologically-mediated uptake of silica by diatoms can shift the geochemical parameters within the lakes, where Mg-smectite form instead of sepiolite in an otherwise silica- rich environment. Overall, this research contributes to our understanding of authigenic clay formation recognizing similarities between these highly diverse environments. In detrital-rich environments where authigenic minerals are difficult to identify, such as the deltaic-lacustrine deposits in Gale crater, Mars, this study shows that authigenic illite can be found within the sand-lenses of the i mudflats. Moreover, this study also shows that we need to consider the factors of diatom dissolution with respect to dissolved silica. The influence of diatoms on the phyllosilicates in brackish lakes suggests we may need to examine the modes of formation for sepiolite in ancient deposits, which may be forming from post depositional alteration of the lacustrine sediments. ii Co-Authorship This dissertation contains the following manuscripts: Chapter 3: Bentz, J.L. and Peterson, R.C. (2017) Realgar and hörnesite precipitation in an iron- poor, sulfate-rich mudflat, Laguna Chiar Khota, Bolivia (Submitted to The Canadian Mineralogist: Accepted subject to revision). Chapter 4: Bentz, J.L. and Peterson R.C. (2017) The formation of clay minerals in the mudflats of Bolivian salars. (Submitted to Clays and Clay Minerals: accepted subject to revision). This thesis is my original work. I was responsible for selecting field sites, implementation of the analytical procedures, and writing of all manuscripts. Ronald C. Peterson, my thesis supervisor, provided scientific guidance and offered intellectual advice for the analysis and editing of all manuscripts. Chapter 3 has been peer reviewed by anonymous reviewers, while chapter 4 has been peer reviewed by an anonymous reviewer, Jenny Huggett, and Joseph Stucki. The Analytical Services Unit, Queen’s University, performed all chemical digestions and inductively coupled optical emission spectroscopic analyses. iii Acknowledgements First and foremost I would like to thank my supervisor, Dr. Ronald Peterson, for his continued advice and support throughout this project. I will never forget our adventures in Bolivia or hunting sulfate deposits in Nunavut. You have truly been a great mentor and friend over the years. I would also like to acknowledge the amazing fiends and fellow graduate students I had the pleasure of working with that made Kingston my home for four years. Sarah McLaren, Rachel Smail-Crevier, and Cortney Palleske, I would not have made it without you (or eaten half as well)! Thanks to Bart Warren, Alex Bailey, Tyler Nash, Ian Little, Alexis Armstrong, Jordan Vervaeke, Ryan Dhillon, Lindsey Waffle, Zoe Braden, Becky Edwards, Colleen Kurcinka, Carl Nagy, Laura and John O’Connell, Ashley Rudy, Sarah Cain, Marina Joury, Justin Drummond, Will Carlson, Colin and Kate Lussier Purdy, Chris Schuh, Gabiel Walton, Micheal Gadd, and many others for all the beer and all the science. Special thanks to Vivian and Gordan Basaraba, to Len and Debbie Chelack, and to Bev and John Bentz for their hospitality during my fieldwork in southern Saskatchewan. Last but certainly not least, I am so grateful for my family, who have been loving and supportive of me in all of my endeavours and have always encouraged me to pursue my love of science. To my soul mate and partner in crime Rob Chelack—Thank-you for sticking by me through thick and thin. You will forever be the silent rock holding me up. iv Statement of Originality I hereby certify that all of the work described within this thesis is the original work of the author. Any published (or unpublished) ideas and/or techniques from the work of others are fully acknowledged in accordance with the standard referencing practices. (Jennifer L. Bentz) (September 28, 2017) v Table of Contents Abstract ............................................................................................................................................. i Co-Authorship ................................................................................................................................ iii Acknowledgements ......................................................................................................................... iv Statement of Originality ................................................................................................................... v List of Figures .................................................................................................................................. x List of Tables ................................................................................................................................ xxi List of Abbreviations .................................................................................................................. xxiii Chapter 1 General Introduction ....................................................................................................... 1 1.1 Saline Lakes ........................................................................................................................... 3 1.2 Relevance to Mars.................................................................................................................. 7 1.3 Clay Minerals ......................................................................................................................... 9 1.4 Geology of the Great Plains ................................................................................................. 13 1.5 Geology of the Andean Plateau ........................................................................................... 21 1.6 Purpose of Study .................................................................................................................. 25 References .................................................................................................................................. 26 Chapter 2 Authigenic Phyllosilicates in Sand Layers from the Mudflats of Saline Lakes in the Northern Great Prairies, Saskatchewan ......................................................................................... 32 Abstract ...................................................................................................................................... 32 2.1 Introduction .......................................................................................................................... 33 2.2 Methods ............................................................................................................................... 37 2.2.1 Sampling ....................................................................................................................... 37 2.2.2 Particle Size Separation and X-ray Diffraction ............................................................. 40 2.2.3 Chemical Analysis and Sediment Characteristics ......................................................... 42 2.2.4 Scanning Electron Microscopy ..................................................................................... 43 2.2.5 Near Infrared Spectroscopy .......................................................................................... 45 2.2.6 Statistical Analysis ........................................................................................................ 45 2.3 Results .................................................................................................................................. 46 2.3.1 Sediment Classification ................................................................................................ 46 2.3.2 Mudflat Sediment Characteristics ................................................................................
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