Old Dominion University ODU Digital Commons OES Theses and Dissertations Ocean & Earth Sciences Summer 1987 The Geochemistry of Selenium and Sulfur in a Coastal Salt Marsh David Jay Velinsky Old Dominion University Follow this and additional works at: https://digitalcommons.odu.edu/oeas_etds Part of the Biogeochemistry Commons, and the Oceanography Commons Recommended Citation Velinsky, David J.. "The Geochemistry of Selenium and Sulfur in a Coastal Salt Marsh" (1987). Doctor of Philosophy (PhD), Dissertation, Ocean & Earth Sciences, Old Dominion University, DOI: 10.25777/z5cp- zc86 https://digitalcommons.odu.edu/oeas_etds/157 This Dissertation is brought to you for free and open access by the Ocean & Earth Sciences at ODU Digital Commons. It has been accepted for inclusion in OES Theses and Dissertations by an authorized administrator of ODU Digital Commons. For more information, please contact [email protected]. THE GEOCHEMISTRY OF SELENIUM AND SULFUR IN A COASTAL SALT MARSH by David Jay Velinsky B.S. June 1977, Florida Institute of Technology A Dissertation Submitted to the Faculty of Old Dominion University in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY OCEANOGRAPHY OLD DOMINION UNIVERSITY AUGUST, 1987 Approved by: Dr ;ter (Director) Dr.L • David* A U V/J. • ADu^cdige - » U W C l J. g j Dr ^ ----- " Dr. Wiliam M. Dunstan Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Copyright by David Jay Velinsky 1987 All Rights Reserved Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This dissertation is dedicated in memory of my father Irving H. Velinsky ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS I would like to express my sincere appreciation to Dr. Gregory A. Cutter, for his financial support, guidance, inspiration and "kicks in the butt" throughout this study. Greg was a real life saver when the chips were down. The expertise, critical suggestions and support provided by my thesis committee, Dr. David Burdige, Dr. Thomas Church, Dr. William Dunstan, and Dr. George Wong were invaluable. A special thanks goes to Dr. Terry Wade whose initial support and guidance provided me with a goal that I have finally reached. I would like to thank Dr. Tom Church for use of his facilities at University of Delaware and Joseph Scudlark for sweating it out in the field, laboratory and at the Rose 'n Crown. Joe sacrificed many hours for this study and it surely benefited from his help. Thanks to Dr. George Luther III for providing me with various ancillary data needed for this research. Chris Krahforst and Jeff Busa provided valuable field assistance and Bob Kluckhohn for his greigite analyses. I am grateful to Dr. David Burdige for his assistance in helping me with data interpretation, diagenetic modeling, ancillary information and writing the "great" paper of 1983. I would like to thank Lynda A. Cutter for her help in the laboratory and proofreading various parts of this dissertation. iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Over the past 7 long years, I have benefited from my association with many students at ODU. Through all the ups and downs they have all provided support and encouragement that made my stay at ODU bearable and most often fun. I am especially indebted to Tom Oatts for his laboratory help and friendship while at ODU. I would also like to thank my other colleagues in the initial Chemical Oceanography Group, Jim Todd, Kazufumi Takayanagi, Charlie Farmer and Robb Brown for their laboratory and field assistance in the various projects I undertook. Their intellectual stimulation and friendship made chemical oceanography interesting and exciting. To Mario Paula, Kimberley G. Davis, E.A. Stern, Chris Krahforst, Darrin Mann, and many others for help along the way. Marcia Berman provided unimaginable physical and mental feats that, even today, cannot and should not be fully described. A special thanks to Maria Lourdes Casino San Diego McGlone whose help, moral support and friendship will undoubtedly last a lifetime. My surfing buddies, Dave Timpy, Rusty Butt and Alan Friedlander helped in keeping my sanity and priorities straight at times of frustration and self destruction. Thanks to Ken, Sarah and Jason Petroske for making my life a little nicer and providing me a home while in Norfolk. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Finally, I a special thanks to my mother whose support, both moral and financial, was deeply appreciated. "If only you were a real doctor!". I am grateful to the Department of Oceanography, ODU for various financial support throughout my graduate career. v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS Page DEDICATION................................................ ii ACKNOWLEDGEMENTS ........................................ iii TABLE OF CONTENTS ....................................... vi LIST OF TABLES .......................................... ix LIST OF FIGURES ......................................... xi CHAPTER 1: GENERAL INTRODUCTION ...................... 1 Scientific Background........................ 9 Chemistry of Selenium in the Environment. 9 Selenium in Oceanic Waters ............... 13 Selenium in Geologic Material ............. 16 Study Area .................................... 30 CHAPTER 2: THE DETERMINATION OF SELENIUM AND SULFUR SPECIATION IN MARINE SEDIMENTS ........... 35 Introduction ................................. 35 Sampling Methods ............................. 35 Water Sample Analyses... ..................... 37 Experimental ............................... 37 Discussion ................................. 45 Sediment Analyses ........................... 47 Experimental ............................... 47 Discussion ................................. 60 CHAPTER 3: SULFUR GEOCHEMISTRY IN THE GREAT MARSH .. 74 Introduction ................................. 74 vi Reproduced with permission of the copyright owner. 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TABLE OF CONTENTS (continued) PAGE Results and Discussion ...................... 77 Total carbon, nitrogen, and sulfur ...... 77 Iron Monosulfides ......................... 81 Greigite ................................... 85 Elemental Sulfur .......................... 87 Pyrite ...................................... 88 A Quantitative Assessment of Pyritization 95 Conclusions .................................. 100 CHAPTER 4: SELENIUM GEOCHEMISTRY IN THE GREAT MARSH. 102 Introduction ................................. 102 Results and Discussions .................... 102 Dissolved Selenium in Pore and Creek Waters ...................................... 109 Chemical Forms of Sediemntary Selenium .. 114 Input of Selenium to the Marsh .......... 130 Internal Cycling of Selenium in Marsh Sediments .................................. 136 Export of Selenium from the Marsh ....... 139 Summary and Conclusions .................... 156 CHAPTER 5: COMPARATIVE GEOCCHEMISTRIES OF SELENIUM AND SULFUR ................................. 159 Introduction ................................. 159 Discussion ................................... 159 Compartive Chemistries of Selenium and Sulfur ..................................... 159 vii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS (continued) PAGE Geochemical Behavior of Selenium and Sulfur in Marine Sediments ............... 167 Conclusions ................................... 174 CHAPTER 6: SUMMARY AND CONCLUSIONS .................. 177 REFERENCES .............................................. 181 viii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES TABLE PAGE 1.1 Free energy change for some bacterial reactions......................................... 4 1.2a Selected physical properties for selenium and sulfur compounds................................. 10 1.2b Reduction potentials for some analogous selenium and sulfur compoundss................. 11 1.3 Solubility products of some metal selenides... 14 1.4 Concentrations of selenium in selected rock types............................................. 18 1.5 Various selenium minerals....................... 20 1.6 Selenium concentrations in minerals of diagenetic origins............................... 22 2.1 List of parameters measured for this study.... 38 2.2 Recovery of elemental selenium using sodium sulfite........................................... 63 2.3 Recovery of elemental selenium from marsh sediment using a sodium sulfite leach and nitric-perchloric digest........................ 65 2.4 Sodium sulfite leach results of marsh sediment at pH 7 and 9 .................................... 67 2.5 Carbon, nitrogen, and sulfur recoveries after sodium sulfite leach............................ 69 3.1 Concentrations of sedimentary sulfur species, organic carbon, total nitrogen, total sulfur, and iron oxides from the Great Marsh.......... 78 4.1 Seasonal marsh redox cycle...................... 104 4.2 Pore water ancillary data in the Great Marsh.. 106 4.3 Pore water selenium data in the Great Marsh... 110 4.4 Creek water total dissolved selenium data 113 ix Reproduced with permission of the copyright