Graduation Year

2015

Document Type

Dissertation

Degree

Ph.D.

Degree Name

Doctor of Philosophy (Ph.D.)

Degree Granting Department

Chemical Oceanography (Marine Science)

Major Professor

Edward S. Van Vleet, Ph.D.

Co-Major Professor

Mya Breitbart, Ph.D.

Committee Member

Luis Garcia-Rubio, Ph.D.

Committee Member

David Grove, Ph.D.

Committee Member

Leon Hardy, Ph.D.

Committee Member

Armando Hoare, Ph.D.

Keywords

Binding Free Energy, Electrocoagulation, Endocrine disruption, Hormones, Wastewater

Abstract

The significance of endocrine-disrupting compounds (EDCs) in the environment has only recently come to the forefront of scientific research, policy debates, water utilities management and public awareness. EDCs have the ability to interfere with the normal functioning of the endocrine system of humans and other animals. Numerous chemicals are included in the class of compounds known as EDCs, and exposure is widespread. These compounds are found in a variety of environmental matrices (e.g., marine and freshwater systems, sediment, soil), transported there primarily through sewage effluent discharge and recycling of sewage sludge for topical fertilizer use. This transport to the environment serves as the primary route of exposure for aquatic and terrestrial organisms living there. Furthermore, these compounds are also found in consumer products, food and drinking water--which serve as the exposure source for human beings. Multiple examples of endocrine disruption have been documented in humans and animals, and certain EDCs have been implicated in each case. The future of public and environmental health will depend upon mitigating the effects of these chemicals.

This purpose of this dissertation is to provide an initial understanding of EDC occurrence in the Tampa Bay region of south Florida, and to complement the existing body of EDC research with regards to marine systems. It focuses on estrogenic EDCs, specific compounds which target the estrogen axis of the endocrine system. Six estrogenic EDCs were chosen based on their documented prevalence in the environment, prevalence in sewage, and for their suspected endocrine-disrupting effects: estrone, 17β-estradiol, estriol, 17α-ethinylestradiol, bisphenol-A and nonylphenol. These compounds were verified to be amenable to and detectable by gas chromatography-mass spectrometry analysis.

Since the occurrence of EDCs in aquatic environments of the Tampa Bay region had not been previously characterized, the initial phase of the research focused on quantification of the six estrogenic EDCs in Tampa Bay area water, sediment, and sewage influent and effluent. All targeted EDCs were present in 89% of sewage samples, while 100% of the samples contained at least one or more EDCs. The concentrations of EDCs in marine aqueous and sediment samples tended to decrease with increasing distance from the wastewater treatment plant discharge site. The ubiquitous presence of these estrogenic EDCs in the Tampa Bay area is cause for concern with respect to endocrine disruption in local terrestrial and aquatic wildlife. Since the Tampa Bay region is home to a wide variety of marine organisms, constant exposure to EDCs could result in ecosystem-level effects, as these compounds can impair reproductive fitness and lead to other adverse health effects. This research also served to enlarge the existing scientific literature on EDC occurrence, as many marine and freshwater systems continue to be characterized globally.

The very basis for expecting to find EDCs in the Tampa Bay area had come from the fact that the main source of environmental contamination is typically the effluent discharge from area wastewater treatment plants. Conventional wastewater treatment plant processes are designed to reduce the amount of organic matter, pathogens and nutrients from the incoming influent. However, the processes are not as effective in removing micropollutants, including EDCs. These compounds notoriously evade traditional wastewater treatment technologies and are found even in tertiary-treated effluent. For this reason, the second phase of the research assessed an electro-chemical technique for the removal of the same six EDCs. The removal technique was tested on a laboratory scale and has a commercial-sized counterpart which can be integrated at the level of the wastewater treatment plant. In order to test the removal efficiency, samples of influent and tertiary-treated effluent were spiked with the six EDCs. The mean concentration of each EDC component was statistically lower after treatment (removal range = 42% - 98.2%), demonstrating the effectiveness of this electro-chemical process for EDC removal from both raw and treated sewage. The significance of the results lies in the fact that if this method is implemented, then future wastewater treatment plant effluent discharge (similar to that of the Tampa Bay region) could be less impacted by EDCs and therefore cleaner for the environment into which it is being discharged.

For the final phase of the research, the use of computational techniques to simulate human endogenous estrogen binding to its receptor was started as a foundation for future models to eventually predict endocrine-disrupting potential of different chemical compounds. We built an estradiol-human estrogen receptor model, and used molecular dynamic simulations to determine the binding free energy. The calculated total binding free energy of estradiol bound to the ligand binding domain of the human estrogen receptor was found to be -16.85 kcal/mol, which is in range of the experimental value of -12.40 kcal/mol. Humans are chronically exposed to low doses of EDCs every day, which makes endocrine disruption a considerable public health issue. Human exposure to EDCs is completely different from marine organism exposure, but the adverse effects are no less significant. The successful completion of this model serves as a platform for 1. Testing the human model against endocrine-disrupting compounds, 2. Subsequent models that will be developed for different species, including marine species important to Tampa Bay.

Substantial data exist regarding the exposures and health risks associated with EDCs in humans and wildlife on a global scale. As the pressing issues of climate change and carbon emissions are at the top of the list of environmental concerns, it is important to note that mitigating the effects of EDCs should not be overlooked and will be an important responsibility of regulatory agencies in the near future.

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