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We investigated the modifying effects of ultraviolet (UV) light and chemical dispersant (Corexit 9500A) on crude oil toxicity in juvenile mysids (≤ 24 h) (Americamysis bahia) and larval red drum (24-72 hpf) (Sciaenops ocellatus). These results demonstrate that crude oil toxicity significantly increases with co-exposure to environmentally relevant UV levels in both species, indicating photo-induced toxicity. This toxicity was further exacerbated by the application of chemical dispersants which increased the dissolution and concentration of oil-derived polycyclic aromatic hydrocarbons (PAHs) in test solutions. To better understand the mechanisms and initiating events of this observed photo-induced toxicity, the incidence of apoptotic cell death and global transcriptomic changes were assessed in larval red drum (24-72 hpf) following co-exposure to crude oil and UV. These results showed that co-exposure to UV and low concentrations of crude oil (<1 µg/L ∑PAH50) induced apoptotic cell death in skin and eye tissue and altered transcriptomic pathways related to visual processing and dermatological disease. To link these cellular and molecular impacts of photo-induced toxicity to apical endpoints of ecological performance, sublethal impacts to growth, metabolic rate, and visually mediated behaviors were explored in larval red drum at 2 developmental stages. These results suggested that earlier life stages may be more sensitive to photo-induced toxicity and that growth and development, particularly of sensory systems, can be sensitive targets of photo-induced toxicity. Together, these studies provide novel insights into the photo-induced toxicity of crude oil in aquatic organisms and can be used to inform future ecological risk assessments.

Oil spills have long been recognized as a significant threat to wildlife. Historically, mortality estimates have served as the basis for assessing impact to natural resources. However, these mortality estimates alone neglect the more wide-spread impact of oil spills on wildlife including birds, many of which may not immediately succumb to exposure, but instead suffer sublethal injury that may negatively affect physiological homeostasis, reproduction, and long-term survival. Therefore, there is a need to improve our understanding of the risk of exposure and effect of sublethal oiling during damage assessments. In this dissertation I evaluated the extent of sublethal oil exposure in the immediate aftermath of the Deepwater Horizon spill on American oystercatchers (Haematopus palliatus), black skimmers (Rynchops niger), brown pelicans (Pelecanus occidentalis), clapper rails (Rallus crepitans), and seaside sparrows (Ammodramus maritimus) through both visual evaluation of and under the application of ultraviolet light to individual birds potentially exposed to oil. I found that there were many individual birds with modest oil exposure, demonstrating that more birds are exposed to oil than are accounted for by mortality estimates. Additionally, I developed a field-adapted technique using an in vitro method in brown pelicans that was effective in determining oxidative hematologic injury as measured by a suite of parameters including a reduction in circulating erythrocytes and hemoglobin, formation of Heinz bodies, and an increase in reticulocytes, in birds exposed to oil. I then applied this suite of parameters to individual birds affected in the aftermath of the Deepwater Horizon spill, and found that birds with modest visible or UV-detectible oil exposure suffer hematologic injury, a quantifiable adverse sublethal effect of modest oil exposure. Finally, I used an experimental approach to evaluate the pathologic effects of crude oil exposure in zebra finches (Taeniopygia guttata), evaluating the same suite of hematologic parameters as well as gross pathology, histopathology, and electron microscopy. This controlled study provided evidence that there may be significant variability in the response of birds to oil exposure that may be attributable to species-specific sensitivity and/or other factors such as the use of dispersants after oil spills. Collectively, this body of work demonstrated that many more birds are exposed to oil during spill events than are accounted for by mortality estimates alone, and that these birds can suffer quantifiable sublethal hematologic injury. The ability to accurately assess the extent of exposure and hematologic damage caused by oil spills is critical to determine the appropriate approach to management needed to offset impacts to fisheries, wildlife, habitats, and economic resources impacted by oil spills. / Doctor of Philosophy / Fossil fuels are the world's primary energy source and are an important part of everyday life. Our reliance on petroleum requires extraction, transportation, storage, and refinement of millions of gallons of crude oil each day. As an unintended consequence, some of this oil is inadvertently spilled into the environment, and these oil spills have long been recognized as a threat to wildlife. Assessing the impact of oil spills on wildlife is a major concern to industries, government, and the general public. Historically, mortality estimates have served as the basis for assessing impact to natural resources. However, these mortality estimates alone neglect the more wide-spread impact of oil spills on wildlife including birds, many of which may not immediately succumb to exposure, but instead suffer sublethal physiologic injury that negatively affects physiology, reproduction, and long-term survival. Therefore, there is a need to improve our understanding of the risk of exposure and effects of sublethal oiling during damage assessments. In this dissertation, I evaluated the extent of sublethal exposure to oil from The Deepwater Horizon spill for several species of birds through both visual evaluation of and under the application of ultraviolet light. This demonstrated that many more birds are affected by oil exposure than are accounted for by mortality estimates. Additionally, I developed a field-adapted technique in a controlled setting that is effective in determining oxidative injury to red blood cells in birds exposed to oil, and applied this approach to several species in the field during the aftermath of the Deepwater Horizon spill. Finally, I used an experimental approach to evaluate the extent of pathologic effects of Deepwater Horizon crude oil exposure in individuals under controlled dosages. The ability to accurately assess the extent of damage caused by oil spills is critical to determine the appropriate approach to management needed to offset impacts to fisheries, wildlife, habitats, and economic resources impacted by oil spills.

Target shooting in the United States has become an increasingly popular sport in the last century. In addition to the large quantity of lead pellets littering range grounds and surrounding land, considerable amounts of clay target fragments cover shooting range areas as well as adjoining habitats. Polycyclic aromatic hydrocarbons (PAHs) within the target, as well as lead pellets from shotguns pose multiple threats to a variety of wildlife. To determine the effects of clay target and lead pellet ingestion on wildlife, I conducted controlled experiments on Coturnix quail exposed to clay targets in the lab, and collected wild birds and mammals exposed to lead pellets at a shooting range. The first Coturnix study determined whether quail voluntarily consumed target fragments or limestone fragments. In both fall (F=29.2, P<0.01) and spring (F=6.45, P=0.02) experiments, I found that quail consistently selected limestone fragments, but almost completely rejected clay target fragments. In the second study, quail were force-fed varying amounts of target dust on a weekly basis to simulate sporadic exposure to clay target dust. In both summer (F=1.63, P=0.23) and winter (F=0.34, P=0.8) trials, male quail did not have significant weight loss. Female quail had insignificant weight losses in summer trials (F=1.63, P=0.23) but experienced weight gains in winter trials (F=3.53, P=0.04). In the third and final Coturnix study, varying amounts of target dust were incorporated into daily feed rations to simulate frequent exposure to clay target dust. Male quail experienced weight loss in both summer (F=16.13, P<0.01) and winter (F=8.47, P<0.01) trials. Female quail also suffered weight loss in both summer (F=15.62, P<0.01) and winter (F=17.50, P<0.01) trials. Weight loss likely resulted from inadequate nutrition as opposed to target poisoning. However, because there were no biochemical analyses performed to test for PAH presence, no definite conclusions can be made. The second study focused on lead contamination in Passeriformes, perching birds, and small mammals. Seventeen of 20 birds (85%) (Passerine spp) captured at the shooting range had elevated lead levels (F=5.21, P<0.028), when compared to birds (n=20) at the control site. Nine of 26 (35%) white-footed mice (Peromyscous leucopus), trapped at the shooting range had elevated liver (F=9.78, P=0.0029) and kidney (F=22.49, P<0.01) lead levels. These results indicate that Passerine species as well as Peromyscous species around shooting ranges inadvertently consume lead, either as lead pellets, mistaking them for grit or dietary items, or through environmental sources such as water, soil, and vegetation. / Master of Science

Poly(arylene ether phosphine oxide)s (PEPO) are a recently identified subset of an important macromolecular series which includes industrially important high performance thermoplastics, such as the polysulfones, e.g. UDEL@ and polyether ketones, e.g. PEEK@, PEKK@, etc. The PEPO materials show an elevated glass transition temperature, high thermal and oxidative stability, improved solubility, and increased flame resistance. It has been demonstrated that a variety of metal salts including metals such as iron, zinc, cobalt, and copper, can be complexed at a molecular level with the phosphoryl group in films of these polymers producing novel transparent metal/polymer "composites". A procedure for obtaining homogeneous films from solutions of the metal halide complexed polymers has been developed. FTIR experiments as well as Tl phosphorus (31 P) NMR measurements were conducted to demonstrate the existance of metal complexation in the solid state. The effect of the chemical composition of the chain, type of metal salt, molar concentration of the metal salt, and heating cycle were investigated and found to influence properties of the films such as solubility, glass transition temperature, thermal stability, and storage mexiulus. Additionally, linear poly(arylene ether phosphine oxide)s were reduced to different extents to the corresponding phosphine containing polymers. Properties such as intrinsic One of these phosphine polymers was subsequently used in the generation of a rhodium catalyst for the hydroformylation of octene-l. The utilization of polymer-supported catalysts has important advantages such as catalyst recovery and the ease of separation of the product. The catalyst activity of the polymeric rhodium complex was studied as a function of reaction time as well as ligand to rhodium ratio. For a phosphorus/rhodium ratio of two these heterogeneous catalysts suffer in tenns of reaction rate in relation to their homogeneous counterparts. However, at phosphorus/rhodium ratios of approximately eight the reaction is almost quantitative after three hours, and the selectivity is greatly improved over that of monomeric homogeneous catalysts for the same P/Rh ratio. / Master of Science

In 1997, a phytoremediation program began at a creosote-contaminated former railroad tie yard in Oneida, Tennessee with the planting of over 1000 hybrid poplar trees onsite. Creosote, a mixture of hazardous chemicals composed of 85% polycyclic aromatic hydrocarbons (PAH) had entered the site soil and ground water. After planting, a seasonal ground water testing program began that monitored the progress of remediation by measuring the concentration of the 10 predominant PAHs in the contaminant plume: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, and benzo(b)fluoranthene. The concentrations of these compounds steadily decreased over time, but the role the trees played in the remediation was unclear. In order to gain a clearer understanding of the role the trees played in contaminant remediation, chemical analysis of tree tissue began. It was not known whether the trees were taking up PAH contaminants or their metabolites or if the rhizosphere zone created by the trees simply enhanced the ability of the site microflora to degrade the PAH. The objectives of this research were to (1) develop a suitable method for the chemical analysis of tree tissue collected from a field site, (2) determine if there were any chemicals not usually found in poplar trees that occurred in the trees growing over contamination, (3) determine if bud, bark, and twig tissue differed in their ability to predict ground water contamination, and (4) determine if a spatial correlation existed between the aromatic compounds in the tree tissue and the ground water total PAH plume. Two types of tree tissue/ground water comparisons were performed: spatial distribution of isoeugenol concentration in tree tissue with spatial distribution of total PAH in ground water over the area of interest; and the spatial distribution of the quantity of aromatic compounds in tree tissue with the spatial distribution of total PAH concentration in ground water. Due to unit discrepancies between the quantities of interest, all comparisons were made on a percentile basis. Initial tree sampling revealed that several compounds not usually present in poplar trees occurred only in those trees growing over contamination. In the first part of this study, the concentration of one of these chemicals, the substituted phenol isoeugenol, was compared with the concentration of total PAH in ground water from samples collected from February-March 2002. The bark tissue percentiles fell within 20 percentiles of ground water total PAH concentrations in 60% of the study area. The twig tissue showed slightly better agreement, with 67% of the study area differing from ground water by twenty percentiles or less. The second comparison took place over three sampling events: March 2001, July 2001, and February-March 2002. The number of unique aromatic compounds in bark, bud, and twig tissue was compared with the total PAH concentration in ground water. Twig tissue aromatic compound content was the most accurate predictor of ground water contamination among the tissue types. After excluding those chemicals likely to be interferences from consideration, twig tissue aromatic content agreed with ground water total PAH concentration to within 20 percentiles over 2/3 or more of the study area during each sampling event, suggesting the potential uptake of PAHs or their microbial metabolites as a mechanism of phytoremediation at the site. / Master of Science