Ocean Ridge Hydrothermal Vent Fluids Alison Marie Bray University of New Hampshire, Durham

Ocean Ridge Hydrothermal Vent Fluids Alison Marie Bray University of New Hampshire, Durham

University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Winter 2001 The geochemistry of boron and lithium in mid - ocean ridge hydrothermal vent fluids Alison Marie Bray University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Bray, Alison Marie, "The eg ochemistry of boron and lithium in mid -ocean ridge hydrothermal vent fluids" (2001). Doctoral Dissertations. 46. https://scholars.unh.edu/dissertation/46 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. NOTE TO USERS This reproduction is the best copy available. __ ® UMI Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. THE GEOCHEMISTRY OF BORON AND LITHIUM IN MID-OCEAN RIDGE HYDROTHERMAL VENT FLUIDS by Alison Marie Bray Bachelor of Arts, University of San Diego, 1995 Master of Science, University of New Hampshire, 1998 Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy In Earth Sciences December 2001 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: 3030597 ___ ® UMI UMI Microform 3030597 Copyright 2002 by Bell & Howell Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. Bell & Howell Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This dissertation has been examined and approved ----- Dissertation Director, Dr. Karen L. Von Damm Professor of Geochemistry and Earth, Oceans and Space _____ -A__________ Dr. Jo Laird Associate Professor of Geology Dr. Susan Humphris Senior Scientist Department of Geology and Geophysics Woods Hole Oceanographic Institution Dr. flfegdry Ravizza Associate Scientist Department of Geology and Geophysics Woods Hole Oceanographic Institution Dr. Lui-Heung 1 Professor Department of Geology and Geophysics Louisiana Sate University 1 2 0 0 1 Date Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. The lure of the sea has enticed explorers to probe the mysteries of that vast, sparkling wilderness, probably for as long as there have been human beings. Our origins are there, reflected in the briny solution coursing through our veins and in the underlying chemistry that links us to all other life. Dr. Sylvia A. Earle Sea Change: A Message of the Oceans iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS I am grateful to Professor Karen Von Damm for her supervision over the past six years. As my advisor, she has provided me with amazing opportunities and has helped me to learn about the process of scientific research and discovery. I would also like to thank Professor Jo Laird, Dr. Susan Humphris and Dr. Greg Ravizza for many helpful discussions, advice and encouragement during my residence as a graduate student. I also gratefully acknowledge Dr. Lui-Heung Chan who devoted endless hours to coaxing Li results from the mass spectrometer. Without her dedication, patience and expertise, this project would never have been completed. Many people have provided scientific assistance and much needed camaraderie, both on land and at sea. Among the many are: M. Ferguson, K. O’Grady, R. Gallant, T. Blanchard, D. Fomari and E. Olsen. Dr. E. Rose is acknowledged for providing the boron ion chromatography method and Dr. M. Perfit is thanked for providing the fresh basalt samples. Mid-ocean ridge research is fundamentally the work of a team and these people have been vital to my education as a scientist. In addition, the officers, crew and Alvin group of the R/V Atlantis are acknowledged for their dedication and expertise that makes work at the bottom of the sea possible. This work was supported by the National Science Foundation (OCE-9911612) and a Hubbard Grant from the University of New Hampshire. I thank my family (Mom, Dad and Andrew) for instilling in me a spirit of debate and love for science and most of all for constant encouragement. Finally, I express my deepest gratitude to my husband Tim who has very patiently stood by me. His support and faith in me have been essential to my success. iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS ACKNOWLEDGEMENTS................................................................................ iv LIST OF TABLES.............................................................................................. vii LIST OF FIGURES........................................................................................... viii ABSTRACT..........................................................................................................ix CHAPTER I. INTRODUCTION........................................................................................... 1 1.1 Geochemistry of Boron and Lithium .......................................................2 1.2 Hydrothermal Processes ............................................................................3 1.3 Previous Studies .........................................................................................6 1.4 Objectives of this Study ...........................................................................13 1.5 Study Site Descriptions .................................. 14 II. THE ROLE OF PHASE SEPARATION AND WATER-ROCK REACTION IN CONTROLLING THE BORON CONTENT OF MID-OCEAN RIDGE HYDROTHERMAL VENT FLUIDS Abstract.......................................................................................................... 21 2.1 Introduction .............................................................................................. 22 2.2 Methods .................................................................................................... 23 2.3 Results and Discussion ............................................................................28 2.4 Implications for the Hydrothermal Flux of Boron ................................ 39 2.5 Conclusions ..............................................................................................42 III. CONTROLS ON LITHIUM IN HIGH AND LOW TEMPERATURE AXIAL HYDROTHERMAL FLUIDS: INSIGHTS FROM LITHIUM ISOTOPES Abstract.......................................................................................................... 44 3.1 Introduction .............................................................................................. 46 3.2 Methods .....................................................................................................50 3.3 Lithium Isotopes in Solid Samples ......................................................... 53 3.4 Lithium Isotopes in High Temperature Hydrothermal Fluids .............. 55 3.5 Lithium Isotopes in Diffuse Hydrothermal Fluids ................................ 69 3.6 Hydrothermal Fluids and the Balance of Lithium Isotopes in the Ocean ..................................................................................................79 3.7 Conclusions ..................................:........................................................... 82 IV. CONCLUDING REMARKS Summary of Conclusions ............................................................................84 Future Study .................................................................................................88 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Appendix A Boron Ion Chromatography Method Description ...................................... 91 Appendix B Analytical D ata ..............................................................................................94 Appendix C Lithium Isotope Method Comparison ........................................................ 108 Appendix D Calculations for Mixing of Seawater and Basaltic Lithium: Effects of Down Flow Reactions ...........................................................................I ll REFERENCES.................................................................................................. 118 vi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES 1-1. Previous Determinations of Boron in Hydrothermal Fluids ....................8 1-2. Previous Determinations of Lithium Isotopes in Hydrothermal Fluids. 12 2-1. Boron and Chloride End Members ......................................................... 26 2-2. Sources and Sinks of Boron in the Oceans ............................................. 41 3-1. End Member Compositions for Lithium Isotopes ..................................48 n 3-2. Lithium Concentrations and 8 Li for Solid Samples ............................. 49 3-3. Diffuse Flow 87Li Results ........................................................................49

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