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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
281

Determinação de compostos organoclorados e hidrocarbonetos poliaromáticos na Lagoa de Carapicuíba - SP / Determination of organochlorine compounds and polycyclic aromatic hidrocarbons in Lagoa de Carapicuiba- SP

Allan Patrick dos Santos 20 April 2007 (has links)
Em 2002, deu-se início na região metropolitana de São Paulo às obras de alargamento e rebaixamento da calha do rio Tietê, como um instrumento para evitar as periódicas enchentes que acontecem nesta região. O andamento da obra contou com a retirada de grande quantidade de sedimentos, rochas e lixo de dentro do rio e com o depósito deste mesmo material na lagoa de Carapicuíba que deveria ser parcialmente aterrada segundo o projeto que prevê a implantação de um parque público no local. Compostos organoclorados e hidrocarbonetos poliaromáticos são classificados como micropoluentes para ecossistemas. Seus impactos sobre o meio ambiente e toxicidade aos seres humanos têm sido amplamente discutidos pela comunidade científica nas últimas décadas. Neste trabalho obtiveram-se dados ambientais referentes ao diagnóstico de organoclorados e hidrocarbonetos poliaromáticos em amostras retiradas da lagoa de Carapicuíba. O método de extração dos compostos estudados (gama-BHC, Heptacloro, Aldrin, Heptacloro-epóxido; Benzo(a)pireno, Fluoreno, Naftaleno) dos sedimentos foi realizado por aparelho Soxhlet e de amostras de lixiviados e solubilizados por Extração em Fase Sólida. Uma etapa de \"clean-up\" se mostrou necessária para a remoção de interferentes. Para a identificação de organoclorados e hidrocarbonetos poliaromáticos nos extratos de lixiviados e solubilizados foi utilizada a cromatografia gasosa acoplada a espectrometria de massas. Os extratos dos sedimentos foram injetados em um cromatógrafo a gás com detector de captura de elétrons para a identificação e quantificação de organoclorados. A metodologia para extração e quantificação se mostrou satisfatória com índices de recuperação e desvio padrão relativo aceitos internacionalmente. Os valores de concentração dos organoclorados encontrados nos extratos de lixiviados e solubilizados ficaram abaixo do limite de detecção do aparelho. Os valores de concentração de organoclorados encontrados nos extratos dos sedimentos variaram de 9 a 175 µg kg-1. Foram identificados resíduos de hidrocarbonetos poliaromáticos em poucos extratos de lixiviados e solubilizados. / In 2002, started the workmanships of widening and deepening of the gutter of the river Tietê in the metropolitan area of Sao Paulo, as a tool to prevent the periodic floods that happen in this region. A large amount of sediment, rocks and garbage have been removed from the river and this same material has been deposited in the lagoa de Carapicuíba, which should be partially filled with earth according to a project that foresees the implement of a public park in the place. Organochlorine compounds and polycyclic aromatic hydrocarbons are classified as micropollutants to the ecosystems. Their impacts on the environment have been widely discussed by the scientific community in the past decades. Environmental data were obtained from the diagnosis of organochlorine compounds and polycyclic aromatic hydrocarbons in samples of water and sediment from this lagoon. The extraction method of the studied compounds (gama-BHC, Heptachlor, Aldrin, Heptachlor epoxid, Benzo(a)Pirene, Fluorine, Naphatalene) of the sediments has been made by Soxhlet apparatus and Solid Phase Extraction method were used for the leached and solubilizated extracts. A stage of clean-up was necessary to remove substances which could modify results. Gas Chromatography/Mass Spectrometry has been used to identify organochlorine compounds and polycyclic aromatic hydrocarbons in the leached and solubilizated extracts. The extracts of the sediment have been injected in a Gas Chromatograph apparatus with detector of eletron capture for the identification and quantification of organochlorine compounds. The methodology used in the extraction and quantification was considered satisfactory, with recovery indexes and relative standard deviation values internationally accepted. The concentration values of the organochlorines obtained in the leached and solubilizated extracts were under the chromatograph detection limits. The concentration of organoclhorine compounds found in extracts of the sediments values varied from 9 to 175 ?g kg-1. Polycyclic aromatic hydrocarbons were identified in few leached and solubilizated extracts.
282

Petrogenic Hydrocarbons in the Peace-Athabasca Delta and their Potential for Microbial Degradation

Roy, Michelle-Claire 25 January 2019 (has links)
Microbial biodegradation is the primary mechanism by which petrogenic hydrocarbons (PHCs) are removed from the environment. Though hydrocarbon biodegradation is widely studied in marine systems, knowledge of how it occurs in freshwater systems is still lacking. The Peace-Athabasca Delta (PAD), located in northeastern Alberta, is an ideal location to study microbial hydrocarbon degradation since it has a long history of exposure to PHCs. What’s more, these PHCs are predominately sourced from bituminous deposits and are therefore relevant to the Canadian Oil Sands Industry. This thesis investigated the genetic potential for hydrocarbon degradation of PHCs via metagenomic reconstruction of microbial communities in lakes of the Peace and Athabasca Deltas, as well as reference lakes in the nearby boreal uplands. In order to properly evaluate the microbial community and its potential for hydrocarbon degradation, a comprehensive analysis of PHCs (including n-alkanes, polycyclic aromatic compounds (PACs), and petroleum biomarkers of terpanes, hopanes, and steranes) was performed. PHC analysis showed that n-alkanes in lake sediments from all three regions were highly similar and predominately biogenic, while PAC composition was significantly different in each region. Restricted-drainage lakes of the Athabasca Delta had the highest concentrations of PACs from petrogenic sources. Closed-drainage lakes in the Peace Delta had lower concentrations of PACs that likely originated from a mixture of pyrogenic and petrogenic sources. Closed-drainage lakes in the boreal upland region had the lowest concentrations of PACs likely sourced from pyrogenic wood combustion with traces of petrogenic PACs, possibly from atmospheric deposition of dust. Petroleum biomarkers of terpanes, hopanes, and steranes were successfully used to identify the long-range fluvial, and possibly atmospheric, transport of bituminous compounds more than one hundred kilometers from their potential source. This validates the future use of these biomarkers in environmental forensics. Microbial communities in all three regions under study were highly diverse, and their composition was significantly different in both sediment and water. Targeted gene analysis identified a total of 3885 genes involved in the degradation of n-alkanes and PACs in sediment and water. The results show that organic carbon, nitrogen, and sulfur content, as well as PAC and short-chain alkane concentrations were important chemical predictors of change in degradation gene composition. Furthermore, genes for anaerobic degradation of PHCs were identified in syntrophic bacteria, methanogens, nitrate and sulfate reducers, demonstrating the potential for syntrophic hydrocarbon degradation in PAD lakes. Though this thesis confirms the genetic potential for hydrocarbon degradation in PAD and boreal upland lakes, further research is necessary to determine whether these microbial communities can actively degrade the PHCs present in these lakes.
283

I. Contorted Polycyclic Aromatic Hydrocarbons: Attempted Synthesis Of [12]circulene Derivatives Ii. Synthesis And Characterization Of Novel [1]benzothieno[3,2-B][1]benzothiophene Derivatives

Hollin, Jonathan 01 January 2019 (has links)
There has been increasing interest in the development of organic materials due to their unique structural and electronic properties. Organic compounds have the advantage of being able to be deposited from solution, leading to low-cost, high-area electronics production. Contorted polycyclic aromatic hydrocarbons have been shown to have potential for use in organic field-effect transistors (OFETs) and organic photovoltaic devices (OPVs) due to their supramolecular properties and charge carrier mobilities. Thiophene-based materials have also shown great promise in OFETs due to their high charge carrier mobilities, stability during device operation, solubility in organic solvents, and structural versatility. [n]Circulenes are a class of polycyclic aromatic compounds whose shape depends on the central n-membered ring. These range from bowl-shaped when n < 6, planar when n = 6, and saddle-shaped when n > 6. The shapes of these molecules, especially for the contorted circulenes, imparts interesting and useful properties such as a polarizable π-system and coordination to fullerenes. Using methods developed in our group, synthesis of [12]circulene derivatives was attempted. Synthetic difficulties, results, and a synthetic plan to overcome these problems are presented herein. 2,7-Dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) is a thiophene-based p-type semiconducting material with one of the highest reported OFET mobility to date. Alterations to BTBT have been made to improve device processing and tune the electronic structure. However, structural alterations have generally been limited to functionalization with electron-donating groups and extension of the π-system. The lack of electron deficient derivatives has prevented further tuning of the electronic structure. Additionally, installation of strongly electron-withdrawing substituents could give BTBT n-type character as seen with perylene diimides. Several synthetic strategies to develop BTBTs with electron-withdrawing groups were explored. Limitations to developing electron deficient BTBTs as well as synthesis and characterization of novel imide-functionalized derivatives are described.
284

Using Ecosystem-Based Modeling to Describe an Oil Spill and Assess the Long-Term Effects

Dornberger, Lindsey N. 15 July 2018 (has links)
The goal of the research conducted in this dissertation was to define and test methods to incorporate oil spill effects into an ecosystem-based assessment model. It was instigated by the Deepwater Horizon oil spill, an unprecedented oil spill in the United States for both depth and volume, with unknown implications for the health of the region. Using an ecosystem-based assessment model like Atlantis, with integrated oil spill dynamics, was the ideal candidate to predict long-term impacts such as decreased abundance or population recovery time. However no previous methodology existed for doing so in any ecosystem-based assessment model. Therefore, first I conducted a literature review to gather data across fish species on lesion frequency and fish body growth impacts from oil exposure. The two data sets were then fitted to four different dose-response models, and an effect threshold log-linear “hockey-stick” model was selected as the best fit and most parsimonious for both lesions and growth. Next, I conducted a similar analysis comparing macrofaunal and meiofaunal abundances to oil exposure concentrations in the Gulf of Mexico collected after Deepwater Horizon. I confirmed that these data had the domed relationship between invertebrate abundances and oil concentration observed in previous invertebrate oil studies. This domed relationship indicates that abundance increases at low to moderate oil levels, and declines at high oil levels. To drive this relationship in an Atlantis ecosystem model, three scenarios were tested in combination with oil toxicity: 1) Mississippi nutrient loading, 2) increased detritus from marine oil snow sedimentation and flocculent accumulation, and 3) predators altering their behavior to avoid oil exposure. At the Atlantis polygon resolution, only scenario 2, increased detritus from marine oil snow sedimentation and flocculent accumulation, generated the domed relationship for invertebrate abundances. Lastly, the “hockey-stick” model for fish mortality and growth was applied to both fishes and invertebrates in combination with scenario 2 for an integrated long-term assessment of the Gulf of Mexico. Newly available fish exposure data were used to generate an uptake-depuration model for this assessment. The combined effect forcings on vertebrates and invertebrates proved to have more severe long-term implications on population size and recovery than simulations with only fish forcings. Large demersal fishes, including elasmobranchs, were the most severely impacted by large biomass declines in the model spill region. Sensitivity analyses indicated that there was the potential for no recovery during 50 years of simulation in the spill region for many functional groups. Analysis of the synergy between fishing mortality F and toxicity from an oil spill identified that some guilds are more sensitive in an oil spill simulation to varied F than others. Snappers are the most sensitive to increased fishing mortality, while groupers respond the most to a reduction in fishing mortality. The invertebrate guild and small pelagic fishes responded the least to different values of F. Changing F also had implications for guild recovery – some guilds only fully recovered to control scenario biomass when F was reduced. A few functional groups were unable to survive with the combined effects of oil toxicity and increased F, and went extinct before the end of the 50-year simulation. Overall, this work provided the first framework for initial integrated modeling of oil spill impacts in an ecosystem-based assessment model, a potentially important component to future ecosystem-based fisheries management. The “hockey-stick” dose response model is applicable beyond Atlantis modeling, and can be tuned to fit specific events based on available data. I have also identified the importance of including marine oil snow sedimentation and flocculent accumulation to accurately drive the response of benthic invertebrates. Findings from the combined vertebrate and invertebrate simulations should help inform research efforts in the Gulf of Mexico and future oil spill response efforts.
285

The identification and quantitation of complex polycyclic aromatic hydrocarbon mixtures in environmental samples using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry

Manzano, Carlos A. (Carlos Andres) 27 June 2013 (has links)
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants and are mostly products of the incomplete combustion of organic material. PAHs are often found in environmental samples as a complex mixture of isomers. In addition, the same sources that produce complex PAH mixtures also produce other poorly characterized mixtures of organic compounds, commonly referred to as an unresolved complex mixture (UCM), that act as matrix interferences in the chromatographic analysis of samples. Conventional one-dimensional chromatographic techniques, such as gas chromatography coupled to mass spectrometry (GC/MS), are not sufficient for the analysis and quantitation of complex PAH mixtures present in environmental samples due to the high degree of overlap in compound vapor pressures, boiling points, and mass spectral fragmentation patterns. Therefore, the separation and quantitation of complex mixtures of individual PAH compounds in environmental samples requires high chromatographic resolution. Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC��GC/ToF-MS) was used for this study. GC��GC/ToF-MS uses two different gas chromatographic columns, with different separation mechanisms, for the analysis of complex environmental samples. In theory, the peak capacity in GC��GC/ToF-MS is equivalent to the product of the individual peak capacities of each column used. However, in practice, this is rarely obtained because of the existing correlation between the two GC columns used. This dissertation is a compilation of three studies related to analytical method development for the identification and quantitation of complex PAH mixtures (including parent-PAHs, alkyl-PAHs, oxy-PAHs, nitro-PAHs, thio-PAHs, chloro-PAHs, bromo-PAHs and PAHs with molecular weight higher than 300 Da) that may be present in environmental samples using novel column combinations in GC��GC/ToF-MS. The use of a liquid crystal column (LC-50) in the first dimension, followed by a nano-stationary phase column (NSP-35) in the second dimension, was evaluated for the separation of a standard PAH mixture containing 97 different PAHs. Two standard reference materials purchased from NIST (NIST SRM1650b ��� Diesel Particulate Matter and NIST SRM1975 ��� Diesel Extract) were used, after extraction and cleanup, for method validation and comparison between the commonly used non-polar �� polar column combination and the LC-50 �� NSP-35 column combination with high orthogonality. As part of the method validation, an aliquot of NIST SRM1975 (Diesel extract), without sample cleanup was also analyzed for PAHs, showing that the LC-50 �� NSP-35 column combination was accurate (with an average absolute percent difference of approximately 30%) for the identification and quantitation of complex PAH mixtures in environmental samples, with reduced sample preparation prior to analysis. In addition, the LC-50 �� NSP-35 column combination was used for the analysis of PAHs sorbed to polystyrene pellets deployed in an urban bay area as passive water samplers because one-dimensional GC/MS was ineffective due to the presence of a strong unresolved complex mixture (UCM) and matrix interferences. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Dec. 27, 2012 - June 27, 2013
286

Body Burden of PAHs and Cardiovascular Disease in the United States

Clark III, John Davis 31 July 2008 (has links)
Polycyclic aromatic hydrocarbons (PAHs) are environmental and occupational carcinogens that are produced by the incomplete combustion of organic material, such as from the burning of tobacco, coal, and petroleum products. In addition to causing cancer, exposure to PAHs is hypothesized to contribute to atherosclerosis and to lead to increased incidence rates of cardiovascular disease in populations. Considering the number of deaths attributable to tobacco smoke exposure, ambient air pollution, and occupational hazards, PAHs may be a significant contributor to the prevalence of cardiovascular disease in human populations. However, a clear exposure-response relationship between PAHs and measures of cardiovascular disease has not been demonstrated. While PAH exposure has been shown to be associated with indicators of cardiovascular disease in research animals, this relationship has not been studied comprehensively in human populations. Using data from the continuous National Health and Nutrition Examination Surveys (NHANES) 1999 - 2004 of a representative sample of the entire US civilian population, this study investigated predictors of total body burden of PAHs and associations between urinary metabolites of PAHs and biomarkers of cardiovascular disease in 4,492 study participants aged 20 years and older. Using various analytic approaches, this research project identified tobacco smoke exposure as a significant predictor of urinary levels of low molecular weight PAHs but not as a predictor of urinary levels of high molecular weight PAHs in a large population of individuals without known occupational exposure to PAHs. Worker occupational category was not associated with urinary levels of any PAH metabolites. The results of this study also indicate a possible association between exposure to PAHs and the development of cardiovascular disease in humans. Levels of multiple metabolites of specific PAHs, naphthalene, fluorene, and phenanthrene were significantly associated with increases in total cholesterol, triglycerides, WBC count, and C-reactive protein levels. Additionally, this study examined the utility of factor analysis for data reduction of 23 urinary PAH metabolites to two latent factors representing low and high molecular weight PAHs to streamline investigations of the associations of PAH exposures with various health outcomes. Results of this study suggest mechanisms by which PAH exposure contributes to the burden of cardiovascular disease on human populations and the methods by which human body burden on PAHs can be measured.
287

Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils in a roller baffled bioreactor

Yu, Ruihong 26 July 2006
Contamination of soil with Polycyclic Aromatic Hydrocarbons (PAHs) is a serious environmental issue because some PAHs are toxic, carcinogenic and mutagenic. Bioremediation is a promising option to completely remove PAHs from the environment or convert them to less harmful compounds. One of the main challenges in bioremediation of PAHs in a conventional roller bioreactor is the limitation on mass transfer due to the strong hydrophobicity and low water solubility of these compounds. To address this challenge, a novel bead mill bioreactor (BMB) was developed by Riess et al. (2005) which demonstrated a significant improvement in the rates of mass transfer and biodegradation of PAHs. <p> In this study, to further improve mass transfer rates, baffles have been installed in both the conventional and bead mill bioreactors. Mass transfer rates of 1000 mg L-1 suspended naphthalene, 2-methylnaphthalene and 1,5-dimethylnaphthalene, three model compounds of PAHs, have been investigated in four bioreactors: conventional (control), baffled, BMB and baffled bead mill bioreactors. The baffled bioreactor provided mass transfer coefficients (KLa) that were up to 7 times higher than those of the control bioreactor. <p> Bioremediation of suspended naphthalene or 2-methylnaphthalene as a single substrate and their mixtures was studied using the bacterium <i>Pseudomonas putida </i>ATCC 17484. Both baffled and bead mill bioreactors provided maximum bioremediation rates that were 2 times higher than the control bioreactor. The maximum bioremediation rates of 2-methylnaphthalene were further increased in the presence of naphthalene by a factor of 1.5 to 2 compared to the single substrate. <p> Another rate-limiting step for bioremediation of PAH-contaminated soil is the strong sorption between the contaminant and soil. To find out the effect of sorption on the bioavailability of naphthalene, the appropriate sorption isotherms for three types of soils (sand, silt and clay) have been determined. It was observed that the sorption capacity of soils for naphthalene was proportional to the organic carbon content of the soils. The mass transfer of soil-bound naphthalene from the artificially prepared contaminated soils with short contamination history to the aqueous phase was studied in both the control and bead mill bioreactors. It was observed that the mass transfer was unexpectedly fast due to the increased interfacial surface area of naphthalene particles and the weak sorption between naphthalene and soils. It was concluded that artificially, naphthalene contaminated soils would likely not be any more difficult to bioremediate than pure naphthalene particles.
288

Preparation and characterization of plasma-fluorinated epitaxial graphene

Sherpa, Sonam Dorje 14 March 2013 (has links)
The discovery of unique properties of graphene has led to the development of graphene for a variety of applications like integrated circuits, organic electronic devices, supercapacitors, sensors, and composite materials. Fluorination of graphene enables control of its physical, chemical, and electronic properties. Our initial studies demonstrated the viability of sulfur hexafluoride plasmas to fluorinate epitaxial graphene as a safer alternative to the commonly reported techniques of fluorination that include exposures to fluorine and xenon difluoride gas. Formation of carbon-fluorine bonds after SF6 plasma-treatment was confirmed by x-ray photoelectron spectroscopy. Raman spectroscopy and low-energy electron diffraction studies suggest that the framework of sp2-hybridized carbon atoms remains intact after the plasma-treatment. Increase in work function after the fluorination was determined by ultra-violet photoelectron spectroscopy. The findings of our subsequent investigation to controllably modify the work function of epitaxial graphene via plasma-fluorination indicate that the work function of fluorinated epitaxial graphene is controlled by the polarity of carbon-fluorine bonds. Further studies to investigate the effect of the surface topography of epitaxial graphene on the work function of plasma-fluorinated epitaxial graphene were performed using scanning Kelvin probe microscopy (SKPM). The results of SKPM characterization of plasma-fluorinated epitaxial graphene demonstrated that the increase in the work function of epitaxial graphene after plasma-treatment is independent of its surface topography, but non-uniform fluorination may result from non-uniformities in plasma density.
289

Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils in a roller baffled bioreactor

Yu, Ruihong 26 July 2006 (has links)
Contamination of soil with Polycyclic Aromatic Hydrocarbons (PAHs) is a serious environmental issue because some PAHs are toxic, carcinogenic and mutagenic. Bioremediation is a promising option to completely remove PAHs from the environment or convert them to less harmful compounds. One of the main challenges in bioremediation of PAHs in a conventional roller bioreactor is the limitation on mass transfer due to the strong hydrophobicity and low water solubility of these compounds. To address this challenge, a novel bead mill bioreactor (BMB) was developed by Riess et al. (2005) which demonstrated a significant improvement in the rates of mass transfer and biodegradation of PAHs. <p> In this study, to further improve mass transfer rates, baffles have been installed in both the conventional and bead mill bioreactors. Mass transfer rates of 1000 mg L-1 suspended naphthalene, 2-methylnaphthalene and 1,5-dimethylnaphthalene, three model compounds of PAHs, have been investigated in four bioreactors: conventional (control), baffled, BMB and baffled bead mill bioreactors. The baffled bioreactor provided mass transfer coefficients (KLa) that were up to 7 times higher than those of the control bioreactor. <p> Bioremediation of suspended naphthalene or 2-methylnaphthalene as a single substrate and their mixtures was studied using the bacterium <i>Pseudomonas putida </i>ATCC 17484. Both baffled and bead mill bioreactors provided maximum bioremediation rates that were 2 times higher than the control bioreactor. The maximum bioremediation rates of 2-methylnaphthalene were further increased in the presence of naphthalene by a factor of 1.5 to 2 compared to the single substrate. <p> Another rate-limiting step for bioremediation of PAH-contaminated soil is the strong sorption between the contaminant and soil. To find out the effect of sorption on the bioavailability of naphthalene, the appropriate sorption isotherms for three types of soils (sand, silt and clay) have been determined. It was observed that the sorption capacity of soils for naphthalene was proportional to the organic carbon content of the soils. The mass transfer of soil-bound naphthalene from the artificially prepared contaminated soils with short contamination history to the aqueous phase was studied in both the control and bead mill bioreactors. It was observed that the mass transfer was unexpectedly fast due to the increased interfacial surface area of naphthalene particles and the weak sorption between naphthalene and soils. It was concluded that artificially, naphthalene contaminated soils would likely not be any more difficult to bioremediate than pure naphthalene particles.
290

Mitochondria as a Target of Benzo[a]pyrene Toxicity in a PAH-adapted and Naive Population of the Atlantic Killifish (Fundulus Heteroclitus)

Jung, Dawoon January 2009 (has links)
<p>Polycyclic aromatic hydrocarbons (PAHs) are important contaminants that are found in increasing amounts in aquatic ecosystems. One of the sites that that is contaminated by extremely high levels of PAHs is the Atlantic Wood Industries Superfund Site on the Elizabeth River, VA. The Atlantic killifish (<italic>Fundulus heteroclitus</italic>) from this site exhibit increased levels of antioxidants, increased sensitivity to hypoxia, and increased expression of enzymes involved in glycolytic metabolism, suggesting that exposure to PAHs in the environment may induce changes in mitochondrial function and energy metabolism. Normal mitochondrial activity is crucial to an organism's survival. Therefore, gaining a better understanding of how mitochondria are affected by environmental contaminants such as PAHs is a pressing research objective. As a first step in understanding changes in cellular bioenergetics of aquatic organisms in response to PAHs, this research focused on the effect of benzo[a]pyrene (BaP), a representative PAH, on mitochondria the killifish model and on comparison of the mitochondria of the PAH-adapted killifish from the Elizabeth River Superfund Site to reference site fish. In order to assess the extent of mitochondrial DNA damage in the killifish, a PCR-based assay (LA-QPCR) for nuclear and mitochondrial DNA (nDNA, mtDNA) damage was adapted to this model and validated in with UV exposure and BaP exposure studies, as well as with <italic>ex situ</italic> study examining DNA damage in killifish inhabiting the Elizabeth River Superfund site. With the newly adapted LA-QPCR, mtDNA and nDNA damage in the killifish from the Elizabeth River Superfund site and from a reference site (King's Creek, VA) that were treated with BaP were examined. Similar increases in mitochondrial and nuclear DNA damage were observed in King's Creek fish treated with BaP. Killifish from the Elizabeth River showed high levels of basal nDNA and mtDNA damage compared to fish from the reference site, but the level of damage induced due to BaP treatment was much lower in Elizabeth River killifish. Laboratory-reared offspring from both populations showed increased BaP-induced damage in mtDNA, relative to nDNA. Similar to the adult experiment, the Elizabeth River larvae had higher levels of basal DNA damage than those from the reference site, but were less impacted by BaP exposure. Results suggest that BaP exposure can have important energetic consequences and that multi-generational exposure in the wild may lead to adaptation that dampens DNA damage arising from BaP exposure. Since the toxic effects of many PAHs are the result of bioactivation by cytochrome P4501A (CYP1A), the existence of enzymes that can potentially metabolize PAHs in mitochondria was verified. Using Western blot, protein similar in size to microsomal CYP1A was identified with monoclonal antibody against scup CYP1A in the mitochondrial fraction from adult male killifish livers. The size of the protein in the mitochondria was the similar to that of microsomal CYP1A. Fish dosed with BaP had increased EROD activity in the liver mitochondrial fraction compared to controls. In killifish larvae dosed with BaP and benzo[k]fluoranthene (BkF), CYP1A protein levels as well as enzyme activity were elevated. However, fish from the Elizabeth River Superfund site showed recalcitrant mitochondrial CYP1A protein levels and enzyme activity in a similar manner to microsomal CYP1A. Finally, the hypothesis that energy metabolism of BaP-treated fish may be different from the control group and that killifish from the Elizabeth River Superfund site may also have altered energy metabolism compared to reference site fish was tested. Respiration of killifish embryos treated with BaP from both populations was measured. Compared to the King's Creek control fish, all other treatment groups showed decrease in oxygen consumption, indicating lower respiration rate. However, when activities of key enzymes involved in glycolysis (PK) and anaerobic metabolism (LDH) in adult killifish liver and muscle were measured, no differences in the enzyme activities were observed in BaP-treated group compared to the control group. Moreover, metabolomic analysis on BaP treated King's Creek and Elizabeth River killifish showed no difference in the profile in all four treatment groups. The findings in this thesis contribute to the understanding of how BaP, a common environmental pollutant in the aquatic ecosystem, targets the mitochondria in fish model. Nevertheless, deeper examination of how BaP may impact mitochondrial function in killifish and potentially influence adaptation of killifish at a highly contaminated site is necessary. Further studies will elucidate whether such impacts can potentially affect the energy budget and organism level fitness in populations in the wild.</p> / Dissertation

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