Most S-nitrosothiols (RSNO) are unstable in aqueous solution and decompose to release nitric oxide. This is catalysed by copper ions. A mechanistic study of NO formation from S-nitrosoglutathione (GSNO), the nitroso derivative of the most abundant thiol in the body, was carried out. This relatively stable S-nitrosothiol decomposed in the presence of reduced glutathione and copper ions. The products were identified as nitric oxide and oxidised glutathione, observed as a complex of copper. The role of reduced glutathione was two fold. Firstly, it reduced Cu(^2+) to produce the active Cu(^+) catalytic species and regenerated the catalyst from the oxidised glutathione complex. Spectrophotometric kinetic measurements, under pseudo first order conditions ([GSNO]»[Cu(^2+)]) showed no conventional order with respect to nitrosothiol. This was attributed to the inconstant concentration of available copper during reaction due to the ability of reduced glutathione to complex Cu(^+) and oxidised glutathione to complex Cu(^2+). An investigation of thiol induced decomposition of GSNO and other more stable nitrosothiols showed the reaction to be first order with respect to thiol and nitrosothiol. The rate equation was determined and has been explained in terms of a radical mechanism involving rate limiting attack of the thiyl radical on the RS-NO bond. The decomposition of S-nitrosothiols via the mercuric ion was also investigated. Reactions were stoichiometric rather than catalytic, and the products determined to be H(_2)NO(_2)(^+) and RSHg(^+). The rate equation was established and the reaction found to be first order in S-nitrosothiol and Hg(^2+). Second order rate constants obtained for a variety of nitrosothiols showed no dependency of the rate of the reaction on the structure of R. A mechanism was proposed involving direct attact of the Hg(^2+) ion on S of the nitroso group, reflecting the high affinity of the metal ion for the sulfur atom. Similarly, an investigation into Ag(^+) mediated S-nitrosothiol decomposition showed the reaction to be stoichiometric. Nitric oxide was not a product of this reaction.

Mercury (Hg)-contaminated freshwater fisheries are a global toxicological concern. Previous research suggests that the slow release of Hg in runoff from upland soils may delay the recovery of Hg-contaminated aquatic systems. Four complementary studies were undertaken in a small boreal Shield headwater catchment as part of the Mercury Experiment to Assess Atmospheric Loading in Canada and the U.S. (METAALICUS) to assess the controls on the retention and release of historically-deposited Hg (ambient Hg) and newly-deposited (spike Hg) in the soil landscape. In the first study, hydrometric and GIS-based methods were used to quantify thresholds in terrestrial water storage and their relationship to observed rainfall-runoff response. It was found that event-scale hydrologic response displayed a threshold relationship with antecedent storage in the terminal depression and predictions of event runoff improved when storage excesses from upslope depressions were explicitly routed through the catchment. In the second study, it was shown that the dominant source of ambient Hg to the lake was likely derived from shallow soil-water flowing through the lower, well-humified organic soil horizon. Throughout the catchment, ambient Hg to soil organic carbon (SOC) ratios increased with depth and the experimentally-applied spike Hg was concentrated in the surface litter layer, suggesting that the vertical redistribution of Hg in the soil profile is a function of the rate of decomposition of SOC. In the third study, canopy type was found to be a good predictor of ambient Hg and spike Hg stocks in the lower organic horizon, while drainage conditions were not, suggesting that vertical fluxes of Hg dominate over lateral fluxes in topographically-complex landscapes. Lastly, it was shown that catchment discharge, antecedent depression storage and antecedent precipitation were the best predictors of dissolved organic carbon (DOC), ambient Hg and spike Hg concentrations in catchment runoff. A comparison of DOC, ambient Hg and spike Hg dynamics for two storm events showed that distinct shifts occurred in the concentration-discharge relationship as a result of differences in antecedent moisture conditions. Combined, the results of the four studies demonstrate the need to incorporate hydrological, biogeochemical and landscape controls into predictive models of terrestrial-aquatic Hg export.

Mercury (Hg)-contaminated freshwater fisheries are a global toxicological concern. Previous research suggests that the slow release of Hg in runoff from upland soils may delay the recovery of Hg-contaminated aquatic systems. Four complementary studies were undertaken in a small boreal Shield headwater catchment as part of the Mercury Experiment to Assess Atmospheric Loading in Canada and the U.S. (METAALICUS) to assess the controls on the retention and release of historically-deposited Hg (ambient Hg) and newly-deposited (spike Hg) in the soil landscape. In the first study, hydrometric and GIS-based methods were used to quantify thresholds in terrestrial water storage and their relationship to observed rainfall-runoff response. It was found that event-scale hydrologic response displayed a threshold relationship with antecedent storage in the terminal depression and predictions of event runoff improved when storage excesses from upslope depressions were explicitly routed through the catchment. In the second study, it was shown that the dominant source of ambient Hg to the lake was likely derived from shallow soil-water flowing through the lower, well-humified organic soil horizon. Throughout the catchment, ambient Hg to soil organic carbon (SOC) ratios increased with depth and the experimentally-applied spike Hg was concentrated in the surface litter layer, suggesting that the vertical redistribution of Hg in the soil profile is a function of the rate of decomposition of SOC. In the third study, canopy type was found to be a good predictor of ambient Hg and spike Hg stocks in the lower organic horizon, while drainage conditions were not, suggesting that vertical fluxes of Hg dominate over lateral fluxes in topographically-complex landscapes. Lastly, it was shown that catchment discharge, antecedent depression storage and antecedent precipitation were the best predictors of dissolved organic carbon (DOC), ambient Hg and spike Hg concentrations in catchment runoff. A comparison of DOC, ambient Hg and spike Hg dynamics for two storm events showed that distinct shifts occurred in the concentration-discharge relationship as a result of differences in antecedent moisture conditions. Combined, the results of the four studies demonstrate the need to incorporate hydrological, biogeochemical and landscape controls into predictive models of terrestrial-aquatic Hg export.

Eutrophication of freshwater lakes has led to an increase in the occurrence of harmful cyanobacterial blooms, and it is expected that a warming climate will further exacerbate the frequency and duration of such blooms. Microcystin is a cyanobacterial hepatotoxin that is found worldwide, and poses a serious threat to the ecological communities in which it is found as well as to those who use these waters for drinking, recreation, or as a food source. Although microcystin is known to accumulate in fish and other aquatic biota, the prevalence of microcystin in fish tissue and the human health risks posed by microcystin exposure through fish consumption remain poorly resolved. Very few studies have quantified microcystin (a broadly present cyanotoxin) in water from East African lakes, despite the large human and animal populations that rely on these lakes for both water and food, and to date there is very little information available on the accumulation of microcystin in fish from these lakes. A comprehensive set of water and fish samples was collected on a monthly basis between September 2008 and February 2009 from several lakes in Uganda. The study sites included two embayments in northern Lake Victoria (Murchison Bay and Napoleon Gulf), Lake Edward, Lake George, Lake Mburo, and the crater lakes Saka and Nkuruba. The large lakes sampled all support substantial commercially important fisheries, while the smaller lakes support subsistence fisheries that provide a critically important source of protein and income for riparian communities. Microcystin concentrations in water were determined in addition to chlorophyll and nutrient concentrations, phytoplankton community composition, mixing dynamics and light conditions. At all study sites except Lake Nkuruba, microcystin concentrations in water regularly exceeded the WHO guideline for microcystin in drinking water of 1.0 µg/L. Microcystis spp. emerged as the cyanobacterial taxa that is primarily responsible for microcystin production in these lakes, and as such, microcystin concentrations were closely linked to environmental factors that favour the development of high Microcystis biomass, including high nutrient concentrations, as well as shallow mixing depth which acts to increase mean mixed layer light intensity. Because of the importance of understanding the underlying food web when considering the accumulation and trophic transfer of a compound, stable carbon and nitrogen isotope analysis was used to characterize the food webs at the previously mentioned Ugandan study sites as well as in the East African great lake Albert. Omnivory was found to be common at all study sites, and based on δ13C values, the food webs in these lakes were strongly based on pelagic primary production, with no strong evidence of substantial benthic contribution to these food webs, likely as a result of reduced benthic primary productivity in these generally low-transparency eutrophic lakes. The distribution and trophic transfer of mercury was also characterized in the Ugandan study lakes (including Lake Albert) in order to provide a contrast for the trophic transfer of microcystin in the same lakes. Furthermore, relatively little is known about the behaviour of mercury in tropical hypereutrophic lakes, and the study sites included in the current study provided an opportunity for the exploration of this topic. Consistent biomagnification of mercury was observed at all study sites; however, mercury concentrations in fish were generally low, and would not be expected to pose a risk to consumers. Mercury dynamics were strongly linked to lake trophic status, with biomagnification rates significantly lower at the hypereutrophic study sites than at the mesotrophic and eutrophic study sites. I found evidence that growth and possibly biomass dilution can reduce mercury concentrations at the base of the food web, while growth dilution of mercury at consumer trophic levels might effectively reduce the biomagnification rate of mercury in these hypereutrophic lakes. Microcystin was prevalent in fish muscle tissue from all study sites and at all trophic levels. In contrast to mercury, for which consistent biomagnification was observed, neither biomagnification nor biodilution was observed for microcystin; and concentrations were relatively consistent throughout the fish food web, including in top predators, indicating that efficient trophic transfer of microcystin is occurring in these lakes. Microcystin concentrations in fish from several study sites followed seasonal trends that were similar to those observed for microcystin concentrations in water at these sites, suggesting that fish can rapidly respond to changes in microcystin concentrations in water through accumulation and depuration of this toxin. Microcystin concentrations in water and fish from all Ugandan study sites (including Lake Albert) in addition to data from two temperate eutrophic embayments (Maumee Bay in Lake Erie, and the Bay of Quinte in Lake Ontario) were compiled and used to estimate potential microcystin exposure to human consumers of both water and fish from these study sites. Microcystin was pervasive in water and fish from both the tropical and temperate study sites. Also, these results establish that fish consumption can be an important and even dominant source of microcystin to humans, and can cause consumers to exceed recommended total daily intake guidelines for microcystin. These results highlight the need to consider potential exposure to microcystin through fish consumption in addition to water consumption in order to adequately assess human exposure and risk.

Knowledge of mercury concentrations in fish is essential for human health protection. Mercury is a naturally occurring element that acts as a neurotoxin to humans and other species. The biologically available mercury form, methylmercury (MeHg), bio accumulates from small benthic invertebrates to large pelagic fish, and therefore high end consumers and terminal predators have elevated Hg concentrations. The main pathway of MeHg exposure in humans is by consumption of contaminated fish. In this study total Hg concentrations were measured in 10 Gulf of Mexico pelagic fish species using a DMA 80 analyzer. Total Hg concentrations ranged from 0.004 to 3.55 ppm (wet wt). The highest mean concentration (1.04 ppm, wet wt) recorded in king mackerel (Scomberomorus cavalla) exceeded FDA recommended criteria of 1ppm. Dolphinfish (Coryphaena hippurus) and vermilion snapper (Rhomboplites aurorubens) had lowest mean Hg concentrations (<0.3 ppm). The rest of the species were above the EPA advisory level of 0.3 ppm. Wahoo (Acanthocybium solandri), greater amberjack (Seriola dumerili) and gag grouper (Mysteroperca microlepsis) had high Hg concentrations of approximately 0.7 ppm wet wt. Blackfin tuna (Thunnus atlanticus) and yellowfin tuna (Thunnus albacores) had moderate Hg concentrations (0.39 and 0.36 ppm wet wt respectively). Little tunny (Euthynnus alletteratus) and blacktip shark (Carcharhinus limbatus) had mean concentrations of 0.69 and 0.51 ppm respectively. The relationship between fish length and Hg concentrations was significant for four species.

Typescript. / Thesis (Ph. D.)--University of Hawaii at Manoa, 1983. / Bibliography: leaves 252-259. / Microfiche. / xv, 259 leaves, bound ill. 29 cm

Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references.

Thesis (M.S.)--Ohio University, November, 2007. / Title from PDF t.p. Includes bibliographical references.

Thesis (M.S.)--Ohio University, August, 2003. / Title from PDF t.p. Includes bibliographical references (leaves 44-45).

Thesis (Ph.D.)--University of Western Australia, 2005.