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FOG Freiberg Online Geoscience FOG is an electronic journal registered under ISSN 1434-7512 2020, VOL 57 Nadja Schmidt Genesis and distribution of lithium enriched pore brines at the Salar de Uyuni, Bolivia 156 pages, 66 figures, 28 tables, 186 references Table of contents I Acknowledgements ......................................................................................................... III II Abstract .......................................................................................................................... IV III Zusammenfassung ....................................................................................................... VI IV Resumen ..................................................................................................................... VIII V List of figures ................................................................................................................. X VI List of tables ............................................................................................................... XIV VII Abbreviations ............................................................................................................. XV 1 Introduction ...................................................................................................................... 1 1.1 Lithium market and availability .................................................................................... 1 1.2 Contribution of TU Bergakademie Freiberg ................................................................. 5 1.3 Aim of work ................................................................................................................. 6 2 Region of interest ............................................................................................................ 7 2.1 Geographical and hydrological situation ...................................................................... 7 2.2 Geological situation and evolution from paleolakes ................................................... 10 2.3 Climate ..................................................................................................................... 13 2.4 Geochemistry and hydrochemistry ............................................................................ 14 3 Fundamentals ................................................................................................................ 17 3.1 Lithium geochemistry ................................................................................................ 17 3.1.1 Lithium in the sedimentary cycle .................................................................... 18 3.1.2 Lithium in salt lake brines .............................................................................. 19 3.2 Mineral sources ......................................................................................................... 21 3.2.1 Leaching of volcanic rocks ............................................................................. 21 3.2.2 Hydrothermal and magmatic fluids ................................................................. 21 3.2.3 Ancient evaporites ......................................................................................... 22 3.2.4 Atmospheric contribution ............................................................................... 22 3.3 Processes of enrichment ........................................................................................... 23 3.3.1 Evaporative concentration ............................................................................. 23 3.3.2 Sorption on clay minerals .............................................................................. 23 4 Methods .......................................................................................................................... 25 4.1 Field works / methods ............................................................................................... 25 4.1.1 Drilling procedure and well installation ........................................................... 25 4.1.2 Sampling and field measurements ................................................................. 29 4.2 Laboratory methods .................................................................................................. 33 4.2.1 Chemical digestion ........................................................................................ 33 4.2.2 Element analysis ........................................................................................... 35 4.2.3 Mineralogic composition ................................................................................ 37 4.2.4 Isotope analysis ............................................................................................. 37 4.3 Application of GIS ..................................................................................................... 39 4.3.1 Watershed delineation ................................................................................... 39 4.3.2 Interpolation maps ......................................................................................... 41 4.3.3 Seasonal variability ........................................................................................ 41 4.4 Quality control ........................................................................................................... 42 5 Results and interpretation ............................................................................................. 44 5.1 Hydrochemical characterization ................................................................................ 44 5.1.1 Field parameters ............................................................................................ 45 5.1.2 Lithium distribution ......................................................................................... 49 5.1.3 Variation with depth and seasonal effects ...................................................... 52 5.1.4 Isotopic contribution ....................................................................................... 54 5.2 Solute input from the catchment ................................................................................ 62 5.2.1 Outline of the catchment ................................................................................ 62 5.2.2 Hydrological connection between Salars of Uyuni and Coipasa ..................... 65 5.2.3 Chemical composition of inflows .................................................................... 70 5.2.4 Geochemical aspects .................................................................................... 74 5.2.5 Recent annual salt and sediment input to the salar ........................................ 80 5.3 Evolution of brine ...................................................................................................... 84 5.3.1 Enrichment of lithium along the flow path ....................................................... 84 5.3.2 Concentration during evaporation .................................................................. 87 5.3.3 Evaporation on the salt crust ......................................................................... 92 5.4 Quality assessment ................................................................................................... 98 5.4.1 Correction of field parameters ........................................................................ 98 5.4.2 Quality of analytical data ................................................................................ 99 5.4.3 Analysis of saturated brines ........................................................................... 99 5.4.4 Comparison of IC and ICP-MS .................................................................... 100 6 Summary, discussion and outlook ............................................................................. 102 6.1 Comparison to other salt lakes ................................................................................ 106 6.2 Environmental issues .............................................................................................. 108 6.3 Recommendations for future research .................................................................... 110 7 Literature ...................................................................................................................... 111 Appendix ........................................................................................................................... 124 II I Acknowledgements A project at the scale of a doctoral thesis is rarely completed on its own, but rather, the support, help and encouragement of many people is involved. So it was in this case. That's why I want to thank everyone who was involved, directly or indirectly, and I would like to highlight some people personally. In the first place there is my PhD supervisor Prof. Dr. Broder Merkel, who has always encouraged me during my studies and diploma thesis and also accompanied the dissertation critically from the beginning. Thank you for your patient guidance and enriching scientific discussions during the course of the thesis. I would like to express my sincere gratitude to Dr. habil. Jörg Hammer, Federal Institute of Geosciences and Natural Resources (BGR), for taking the task of second reviewer. Sadly, Mr. Hammer passed away in February 2019 and thus did not have the opportunity to accompany this work until its end. My sympathy goes to the bereaved family members and colleagues. The more thankful I am to his colleague Dr.