University of Kentucky UKnowledge University of Kentucky Doctoral Dissertations Graduate School 2010 IMMOBILIZATION OF MERCURY AND ARSENIC THROUGH COVALENT THIOLATE BONDING FOR THE PURPOSE OF ENVIRONMENTAL REMEDIATION Lisa Y. Blue University of Kentucky, [email protected] Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation Blue, Lisa Y., "IMMOBILIZATION OF MERCURY AND ARSENIC THROUGH COVALENT THIOLATE BONDING FOR THE PURPOSE OF ENVIRONMENTAL REMEDIATION" (2010). University of Kentucky Doctoral Dissertations. 785. https://uknowledge.uky.edu/gradschool_diss/785 This Dissertation is brought to you for free and open access by the Graduate School at UKnowledge. It has been accepted for inclusion in University of Kentucky Doctoral Dissertations by an authorized administrator of UKnowledge. For more information, please contact [email protected]. ABSTRACT OF DISSERTATION Lisa Y. Blue The Graduate School University of Kentucky 2010 IMMOBILIZATION OF MERCURY AND ARSENIC THROUGH COVALENT THIOLATE BONDING FOR THE PURPOSE OF ENVIRONMENTAL REMEDIATION ABSTRACT OF DISSERTATION A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the College of Arts and Sciences at the University of Kentucky By Lisa Y. Blue Lexington, Kentucky Director: Dr. David A. Atwood, Professor of Chemistry Lexington, Kentucky 2010 Copyright © Lisa Y. Blue 2010 ABSTRACT OF DISSERTATION IMMOBILIZATION OF MERCURY AND ARSENIC THROUGH COVALENT THIOLATE BONDING FOR THE PURPOSE OF ENVIRONMENTAL REMEDIATION Mercury and arsenic are widespread contaminants in aqueous environments throughout the world. The elements arise from multiple sources including mercury from coal-fired power plants and wells placed in natural geological deposits of arsenic- containing minerals. Both elements have significant negative health impacts on humans as they are cumulative toxins that bind to the sulfhydryl groups in proteins, disrupting many biological functions. There are currently no effective, economical techniques for removing either mercury or arsenic from aqueous sources. This thesis will demonstrate a superior removal method for both elements by formation of covalent bonds with the sulfur atoms in N,N’-Bis(2-mercaptoethyl)isophthalamide (commonly called “B9”). That B9 can precipitate both elements from water is unusual since aqueous mercury exists primarily as a metal(II) dication while aqueous arsenic exists as As(III) and As(V) oxyanions. KEYWORDS: Arsenic, Covalent Bonding, Mercury, Remediation, Sulfur Lisa Y Blue November 30, 2009 IMMOBILIZATION OF MERCURY AND ARSENIC THROUGH COVALENT THIOLATE BONDING FOR THE PURPOSE OF ENVIRONMENTAL REMEDIATION By Lisa Y. Blue Dr. David Atwood Director of Dissertation Dr. Mark Meier Director of Graduate Studies November 30, 2009 RULES FOR USE OF DISSERTATIONS Unpublished dissertations submitted for the Doctor’s degree and deposited in the University of Kentucky Library are as a rule open for inspection, but are to be used only with due regard to the rights of the authors. Bibliographical references may be noted, but quotations or summaries of parts may be published only with the permission of the author, and with the usual scholarly acknowledgements. Extensive copying or publication of the dissertation in whole or in part also requires the written consent of the Dean of the Graduate School of the University of Kentucky. A library which borrows this dissertation for use by its patrons is expected to secure the signature of each user. Name Date ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ DISSERTATION Lisa Y. Blue The Graduate School University of Kentucky 2010 IMMOBILIZATION OF MERCURY AND ARSENIC THROUGH COVALENT THIOLATE BONDING FOR THE PURPOSE OF ENVIRONMENTAL REMEDIATION DISSERTATION A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the College of Arts and Sciences at the University of Kentucky By Lisa Y. Blue Lexington, Kentucky Director: Dr. David A. Atwood, Professor of Chemistry Lexington, Kentucky 2010 Copyright © Lisa Y. Blue 2010 This work is dedicated to my boys: Spencer and Benjamin, I hope to one day inspire you as much as you’ve inspired me. Jesse, thanks for being my rock. Education is not the filling of a pail, but the lighting of a fire. —William Butler Yeats ACKNOWLEDGEMENTS David, I must start my acknowledgements by thanking you for encouraging me to pursue every project and opportunity that has ever piqued my interest and for hanging in there with me while I followed a rather non-linear path to a Ph.D. under your guidance. I’ve always appreciated your indefatigable optimism and the freedoms allowed to me while in your group. You’ve taught me an incredible amount of self-reliance in research. Gail, first of all, I must thank you for the quote underneath the signature line of your emails. Those few words have bothered me and goaded me into action more than I would have thought possible, especially on the tough days, when I hear that quote resounding in my head and find the courage to keep moving. Thank you, too, for serving as the reality check I needed, even when I was not necessarily receptive to said reality check. Thanks for creating a wonderful learning environment in the lab and for allowing me to participate so fully in the ERTL mission. Thanks, too, for the bracing insight into my future aspirations and potential career paths. You have inspired me for a lifetime. The main thrust of my research efforts were supported by the fine folks at ERTL, especially Tricia Coakley, John May, James Ward and Katy Ward. These four were in the trenches with me almost from the beginning and I am in their debt for the endless constructive critiques of experimental methods, results, and written research products, for training on various instruments and techniques, for their friendship, and for their constant encouragement. These four quickly became personally invested in my success as a doctoral candidate and it was always a pleasure to share my triumphs with them. I must also thank each of you charged with the duty of serving on my doctoral committee for your support during this process. Chris, I still swear that all I ever knew about soil chemistry I learned from you. Thanks for such a solid grounding in soil chemistry which I continue to build upon today. Who knew I could get so much mileage out of a single course? Dr. Bramwell, I appreciate your support, your professionalism and your kind words of encouragement before my qualifying exam when it was delayed. Dr. Lovell, thanks for coming in so late in the game to see me to the finish line. In the Atwood lab, I’d like to thank all of my predecessors for laying the groundwork for the research described in this dissertation. I’d like to thank my contemporaries in the group, especially Eduardo Santillán-Jiménez and Christopher iii Preece for the excellent discussions of inorganic chemistry, uranium, zinc, arsenic, mercury, and all things graduate school. I was also fortunate enough to work with many wonderfully talented undergraduate researchers including Railey White and Kristen Bird, with whom I worked most extensively, and several others including J. David Clem, Shaun Masters, Kyle Slone, Laura Fletcher, Chrissy Minton, Crystal Holcomb, Jared Daughetry and Kateland Beals. This group was affectionately known as the “Blue Crew” and the semester that I had nine of them in the lab was one of the most amazing and productive times I can recall. Thanks for the fun, Blue Crew! You are sorely missed. I must extend thanks to all of my collaborators on various projects throughout my research career at the University of Kentucky. On the arsenic in poultry litter amended soils project, E. Glynn Beck of the Kentucky Geological Survey in western Kentucky and Greg Henson from the McLean County Extension office were a great help for coordination of the field work, the selection of fields, sample collection, sample transportation to the lab, and enlightened discussions concerning the project. It was a pleasure working on the thimerosal in vaccines project with Dr. Laura Hewiston of the Magee Women’s Research Institute in Pittsburgh and Dr. Andy Wakefield from the Thoughtful House for Children based in Austin, Texas. I appreciate the use of Dr. Boyd Haley’s instrument for analysis of the project’s samples as well. I’m very appreciative for Abhijit Mukerjee and Alan Fryar testing my arsenic remediation columns in West Bengal. I also appreciate the hospitality of Evan Granite when visiting him at the Pittsburgh DOE NETL laboratory to discuss his research on gas phase mercury capture and the possibility of testing our compounds in his lab-scale simulated coal-fired power plant