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This thesis investigates the relationships between mercury (Hg) and stable isotope of carbon (δ13C) in marine pelagic zooplankton (Calanus spp., Themisto spp. and Euchaeta spp.) with water mass characteristics in the North Water Polynya (NOW) and in the Mackenzie shelf – Amundsen Gulf area. Two ship based sampling field expeditions were carried out in late summer of 2005 and 2006 in both regions on board the CCGS Amundsen. In the North Water (NOW) polynya, higher levels of water Hg, depleted δ18O, lower salinity and lower nitrate levels were measured at sampling locations near the Prince of Wales glacier (POW) on the eastern coast of Ellesmere Island in the Smith Sound area. These results suggest that the glacier may be a source of Hg to this region which, in turn, is responsible for the correspondingly high concentrations of THg and MMHg measured in Calanus spp. and Euchaeta spp. at the same locations. The Mackenzie shelf – Amundsen Gulf region was characterized by fresher surface water properties (low salinity and depleted δ18O) in the western part and was strongly linked to the influence of the Mackenzie River. Higher THg concentrations in zooplankton were associated with larger fractions of both meteoric water and sea-ice melt. These findings suggest that in the western Arctic, inorganic Hg uptake in zooplankton via-absorption near surface water was highly driven by freshwater inputs into the system. Based on the analysis of three main genus Calanus spp. (mostly adult females Calanus hyperboreus), Euchaeta spp. and Themisto spp. (mostly adult Themisto libellula), THg and MMHg concentrations were the highest in the carnivorous copepod Euchaeta spp. in the North Water polynya followed by the omnivorous hyperiid amphipod Themisto spp. The herbivorous copepod Calanus spp. had both the lowest THg and MMHg concentrations in the Eastern and the Western Arctic. In addition, the Western Arctic is the area in which each zooplankton genus had the most depleted carbon and the most enriched nitrogen. The highest concentrations of THg in Calanus spp., Euchaeta spp. and Themisto spp. were measured in the Western Arctic as well as the highest MMHg in Calanus spp. and Themisto spp. The highest %MMHg was calculated in the Archipelago for Themisto spp., in the Eastern Arctic for Euchaeta spp. and in the Western Arctic for Calanus spp. The relationships observed between THg, MMHg, %MMHg and δ13C in all three major zooplankton taxa and water mass properties were in agreement with what have been previously described in the literature. Our findings suggested that both Hg and δ13C can be used as tracers to help understand zooplankton vertical distribution, feeding ecology and ultimately to predict climate changes impact at lower trophic level in the pelagic food web. The implications for marine mammals foraging in these regions are also discussed. / October 2008

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.

The objective of this study was to determine the dominant biogeochemical controls on mercury partitioning in super-permafrost groundwater at Truelove Lowland, Devon Island, Nunavut. Mercury partitioning in snow, ephemeral standing water, and super-permafrost groundwater was investigated. <p>Results indicate that partitioning differs between matrices, and that particulate mercury is spatially and temporally dynamic in Truelove Lowland groundwater. Particulate mercury in groundwater was 73 % of total mercury, while snow had only 22 % particulate mercury. Particulate mercury in groundwater rose by over 20 % from Julian day 181 to 189, and decreased slightly on Julian day 191. No single geochemical parameter was a good predictor of particulate mercury concentrations. To expand upon the findings of the field study a laboratory microcosm study was conducted to determine whether certain biogeochemical processes influence mercury partitioning in super-permafrost groundwater. Particulate mercury in the dissimilatory iron reducing bacteria inhibited microcosm was 61 % of total mercury, approximately 18 % lower than in all other treatments. Iron (III) concentrations had a positive correlation with particulate mercury while chloride concentrations had a negative correlation with particulate mercury. Sulfate reducing bacteria were not found to influence mercury partitioning.

No description available.

This dissertation focuses on the phosphorescence of organic chromophores using perfluoro-ortho-phenylene mercury (1) and bis(pentafluorophenyl)mercury (2) as external heavy atom effect inducers. To ascertain the suitability of these luminescent adducts for OLED applications, several research objectives have been investigated. To further shorten the triplet lifetimes of adducts involving 1, a strategy was developed which combines both internal and external heavy atom effects. Specifically, complexes involving 1 and N-methylcarbazole, N-methylindole and the 1- halonaphthalenes were investigated. The existence and stability of the complexes could be confirmed in solution by fluorescence spectroscopy. In the solid state, these adducts form supramolecular binary stacks where the molecules of 1 alternate with the aromatic substrate. As a result of the mercury external heavy atom effect, all of these adducts display intense room temperature phosphorescence of the free arene. With the Nheterocycles, the triplet lifetimes were drastically reduced to below 100 mu-s. To appreciate the origin of the unusual heavy atom effects observed in arene adducts with 1, 2 was studied as a monofunctional analog to 1. By utilizing fluorescence spectroscopy, naphthalene, biphenyl, and fluorene complexes of 1 and 2 have been detected in solution. The solid state structure of the adducts with 2 reveal supramolecular binary stacks. Comparison of the photophysical results supports the occurrence of cooperative effects between the Lewis acidic mercury centers of 1, which make it a more efficient external heavy-atom effect inducer. Polymeric materials which are amenable to deposition in thin layers were investigated as substrates for 1 and 2. Both poly(vinyl-2-naphthalene) and poly(vinylcarbazole) interact with 1 and 2 in solution as evidenced by fluorescence spectroscopy. With the solid blend 1•PVK, a small doping percentage of 1 results in white emission, while larger percentages of 1 yield bright orange emission. This dissertation presents the first structurally characterized ternary complex with 1, carbazole, and coordinating solvents THF and triethylamine. IR spectroscopy and short N···O and N···N distances in the solid state indicates that the acidic N-H moiety of carbazole interacts with the solvent by hydrogen bonding. In the extended structure, molecules of 1 and the hydrogen bonded complex alternate to form supramolecules.

The overall goal of this study is to evaluate the ability of novel nanostructured adsorbent media (NTAs, iron sulfides (FeS2 and FeS)) to remove arsenic, selenium and mercury from ash and scrubber pond effluents. The NTAs aim to enhance arsenic removal from solution compared to conventional adsorbents. The iron sulfides are expected to produce stable residuals for ultimate disposal after removing As, Se and Hg from solution, so that removal of these compounds from wastewaters will not result in contamination of soils and groundwaters. Methods for reliably and economically producing these materials were developed. The synthesized NTAs and iron sulfides were characterized by surface analysis techniques such as XRD, FT-IR, SEM-EDS, TEM, XPS, AFM and N2-adsorption. These analyses indicated that Ti(25)-SBA-15 has highly ordered hexagonal mesopores, MT has interparticle mesopores, pyrite (FeS2) forms crystalline, nonporous rectangular nanoparticles (<500 nm), and mackinawite (FeS) forms amorphous, nonporous nanoparticles (<100 nm). Kinetic and equilibrium tests for As(III, V) removal were conducted with NTAs over a range of pH (4, 7, 9.5). The rates of arsenic uptake were very fast and followed a bi-phasic sorption pattern, where sorption was fast for the first 10 minutes, and then slowed and was almost completed within 200 minutes. Distinct sorption maxima for As(III) removal were observed between pH 7 and pH 9.5 for MT and between pH 4 and pH 7 for Ti(25)-SBA-15. The amount of As(V) adsorbed generally decreased as pH increased. In addition, a surface complexation model (SCM) based on the diffuse layer model (DLM) was used to predict arsenic adsorption envelopes by NTAs under various environmental conditions. The SCM for As(III, V) adsorption by NTAs demonstrated the role of mono- and bidentate surface complexes in arsenic adsorption. A batch reactor system was employed in an anaerobic chamber to conduct experiments to characterize both the removal of As, Se, Hg from solution and their subsequent reactions with iron sulfides. Experiment variables for removal experiments included: contaminant valence state (As(V), As(III), Se(VI), Se(IV), Hg(II)); adsorbent/reactant type (FeS, FeS2); adsorbent/reactant concentration; pH (7, 8, 9, 10); and competing ion (SO42-) concentration (0, 1, 10 mM). Experimental variables for reaction experiments were reaction time (up to 30 days) at pH 8 and oxidation states of contaminants. In addition, the stability of iron sulfides (FeS2, FeS) combined with target compounds was investigated by measuring the ability of the target compounds to resist release to the aqueous phase after removal. These experiments showed that iron sulfides were good adsorbent/reactants for target contaminants in spite of the presence of sulfate. This was particularly true at intermediate concentrations of target compounds. The experiments also demonstrated that iron sulfides interacted with target contaminants in such a way to improve their resistance to being released back to solution as pH was changed. Therefore, this study demonstrates the ability of novel nanostructured adsorbent media to remove arsenic, selenium and mercury from ash and scrubber pond effluents and the ability of iron sulfides to produce residuals that are stable when disposed in landfills.

Thesis (Ph. D.)--Rutgers University, 2008. / "Graduate Program in Microbiology and Molecular Genetics." Includes bibliographical references (p. 140-151).

Thesis (Ph. D.) in Chemistry--University of Maine, 2003. / Includes vita. Includes bibliographical references (leaves 181-196).

Inaug.-Diss.--Kaiser Wilhelms Universität. / Includes bibliographical references.