Abstract

For many centuries, chemists have dedicated many labor-intensive hours to improving the quality of life for mankind by developing synthetic methods for the production of compounds which fulfill the needs and meet the demands of society. However, the innovation of such compounds has frequently come at the cost of detrimental side-effects that do not always present themselves until many years, or even decades, following their initial application. Many compounds in this category come in the form of globally-distributed halogenated molecules which are toxic to many living organisms, susceptible to bioaccumulation and resistant to biodegradation processes. Such compounds are classified as persistent organic pollutants (POPs), and require safe, sustainable and economically viable remediation techniques due to their destructive effects on organisms and the environment In the work done for this dissertation study, three particular POPs, which can be further classified as Polychlorinated Aromatic Hydrocarbons (PCAHs), were studied: pentachlorophenol (PCP), hexachlorobenzene (HCB) and pentachloroanisole (PCA). Chlorophenols are highly toxic compounds, usually found in soils, water, and effluents resulting from industrial activities. These environmentally-persistent compounds have been found to exhibit probable carcinogenic properties by the United States Environmental Protection Agency and the International Agency for Research on Cancer. The most toxic chlorophenol is PCP, which has a regulated maximum contaminant level (MCL) of 0.03 mg/L in water. Due to the high toxicity of PCP, it is necessary to treat water and soils that have tested positive for concentrations above the MCL. The aim of this work is to demonstrate the capabilities of using ball-milled zero-valent magnesium powder with various amendments, such as acetic acid (as an activator) and ethanol for the dechlorination of PCP. The dechlorination processes of these various combinations were compared in an attempt to determine the most effective system for the degradation of PCP to phenol. Three systems with powerful capabilities of treatment were studied: ball-milled magnesium powder, ball-milled magnesium carbon (Mg/C), and mechanically alloyed magnesium with palladium. The results of these studies indicate that the most rapid and complete PCP dechlorination is achieved using mechanically alloyed Mg/Pd and a matrix consisting of at least 0.02 g Mg0/mL of ethanol and 10 ?L acetic acid/mL of ethanol, in which case 20 ng/?L of PCP was dechlorinated to phenol in approximately 15 min. with a carbon mass balance of 94.89%. Hexachlorobenzene (HCB), like many chlorinated organic compounds, has accumulated in the environment from agricultural and industrial activity. After its introduction as a fungicide in 1945, the extensive use of this toxic chemical has instigated its infiltration into all food types. Prohibition from commercial use was enforced in the United States in 1966 due to animal, and possible human, carcinogenic effects. Because of the health risks and the adverse impact on various ecosystems, remediation of this contaminant is of vital concern. The objective of this study is to evaluate the proficiency of activated-magnesium metal in a protic solvent system to enhance the reductive dechlorination of HCB. Experimental results were compared with those predicted by quantum chemical calculations based on Density Functional Theory (DFT). Multivariate analysis detected complete degradation of HCB within 30 minutes, having a rate constant of 0.222 min-1, at room temperature. Dechlorination was hypothesized to proceed via an ionic mechanism, and the main dechlorination pathways of HCB in 1:1 ethanol/ethyl lactate were HCB ? PCBz ? 1,2,4,5-TCB; 1,3,4,5-TCB ? 1,2,4-TriCB; 1,3,5-TriCB ? 1,4-DiCB; 1,3-DiCB. The direct relationship between the decreasing number of Cl substituents and dechlorination reaction kinetics agrees with the ?G values predicted by the computational model. Therefore, the lowest energy pathway for C-Cl bond dissociation predicted computationally agrees with the experimentally determined kinetic data. The experimental results from these studies have helped to improve our understanding of the dechlorination mechanisms, thereby offering insight into the most efficient pathways for remediation in the environment. This methodology shows promise for the development of an economic and sustainable field application for the treatment of other chlorinated aromatic compounds. In further work, developments will be made in the modification of the system to allow for the implemetation of field-scale applications. Chloroanisoles are compounds that have similar properties to chlorophenols, but have a higher tendency to bioaccumulate and resist degradation because of their lipophilicity. They are not manufactured for commercial use, but exist in equilibrium with chlorophenols in the environment through biological transformation. Due to the toxicity of both compounds, a strategy for remediation is highly sought after. This study has served to develop an approach to meet the needs for this treatment, based on the successful treatment of PCPs using zero-valent magnesium (ZVMg) discussed in Chapter 1. The results of the method, which makes use of ZVMg/C in acidified ethanol, are compared for both target analytes. Both substrates were degraded to less-chlorinated byproducts within the first four hours; however PCP vanished at a faster rate with no detection at seven minutes. The more heavily-chlorinated byproducts showed faster degradation rates for both compounds, which also had 2,4-dichlorinated congeners in common as major byproducts. The mole balances of PCA and PCP were 92.6% and 94.8%, respectively. Further studies were done to enhance degradation kinetics by re-spiking with acetic acid after two weeks. Although complete degradation was still not achieved, a slight improvement was observed for both compounds, more so with respect to PCP. Kinetic data followed pseudo first-order trends for the degradation of both PCA and PCP.

Graduation Date

2016

Semester

Fall

Advisor

Yestrebsky, Cherie

Degree

Doctor of Philosophy (Ph.D.)

College

College of Sciences

Department

Chemistry

Degree Program

Chemistry

Format

application/pdf

Identifier

CFE0006456

URL

http://purl.fcla.edu/fcla/etd/CFE0006456

Language

English

Release Date

December 2016

Length of Campus-only Access

None

Access Status

Doctoral Dissertation (Open Access)

Included in

Chemistry Commons

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