immobilization of mercury and arsenic through covalent thiolate bonding for the purpose of ...

185 Pages·2016·2.3 MB·English

by  Lisa Y. Blue

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University of Kentucky Doctoral Dissertations Graduate School
2010
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Lisa Y. Blue
University of Kentucky, [email protected]
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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
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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
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