Aquatic mercury (Hg) contamination caused by industrial Hg emissions, atmospheric transport and deposition to sensitive ecosystems is an ongoing concern in many parts of the world. Boreal ecosystems are particularly sensitive to Hg deposition, and large soil-Hg burdens in these regions may prolong recovery of Hg impacted surface waters for many decades. Four studies were undertaken to examine interactions between watershed characteristics, hydro-climatic variability and terrestrial-aquatic export of key chemical parameters linked to watershed Hg sensitivity. Two new quantitative techniques, hydrogeomorphic edge detection and characteristic morphology analysis, were developed to explicitly map and characterize the spatial distribution, geomorphic form and hydro-biogeochemical function of forested wetlands using airborne Light Detection and Ranging (LiDAR) surveys. The results demonstrate the critical contribution of forested wetlands and upland-wetland interactions to the production and mobilization of dissolved organic carbon (DOC) and methyl-mercury (MeHg) - respectively - to downstream surface waters. Results of strategic, event-based hydrochemical sampling also demonstrate the critical contribution of summer high-flow periods to terrestrial-aquatic MeHg export. Finally, an analysis of historical monitoring databases of streamflow volume, hydrochemistry and Hg concentrations in yearling perch in two contrasting headwater lake basins was conducted. The results indicate strong potential for short-term, hydrologically-driven shifts in terrestrial-aquatic coupling and watershed Hg sensitivity, but only for the wetland-dominated, humic lake that exhibited consistent, summertime hypolimnetic anoxia. These various findings suggest that accurate characterization of watershed structure can help researchers identify first-order limitations on whole-watershed methylation efficiency, particularly in relation to hydro-climatic drivers of terrestrial-aquatic coupling in Boreal headwater regions.

Aquatic mercury (Hg) contamination caused by industrial Hg emissions, atmospheric transport and deposition to sensitive ecosystems is an ongoing concern in many parts of the world. Boreal ecosystems are particularly sensitive to Hg deposition, and large soil-Hg burdens in these regions may prolong recovery of Hg impacted surface waters for many decades. Four studies were undertaken to examine interactions between watershed characteristics, hydro-climatic variability and terrestrial-aquatic export of key chemical parameters linked to watershed Hg sensitivity. Two new quantitative techniques, hydrogeomorphic edge detection and characteristic morphology analysis, were developed to explicitly map and characterize the spatial distribution, geomorphic form and hydro-biogeochemical function of forested wetlands using airborne Light Detection and Ranging (LiDAR) surveys. The results demonstrate the critical contribution of forested wetlands and upland-wetland interactions to the production and mobilization of dissolved organic carbon (DOC) and methyl-mercury (MeHg) - respectively - to downstream surface waters. Results of strategic, event-based hydrochemical sampling also demonstrate the critical contribution of summer high-flow periods to terrestrial-aquatic MeHg export. Finally, an analysis of historical monitoring databases of streamflow volume, hydrochemistry and Hg concentrations in yearling perch in two contrasting headwater lake basins was conducted. The results indicate strong potential for short-term, hydrologically-driven shifts in terrestrial-aquatic coupling and watershed Hg sensitivity, but only for the wetland-dominated, humic lake that exhibited consistent, summertime hypolimnetic anoxia. These various findings suggest that accurate characterization of watershed structure can help researchers identify first-order limitations on whole-watershed methylation efficiency, particularly in relation to hydro-climatic drivers of terrestrial-aquatic coupling in Boreal headwater regions.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21363号 / 工博第4522号 / 新制||工||1704(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 高岡 昌輝, 教授 米田 稔, 准教授 大下 和徹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

<p>Coal fired power plants generate approximately 45% of the electricity produced in the United States every year, and each year, over 100 million tons of coal ash are produced as a by-product of electricity generation. Coal ash is a solid waste made up principally of bottom ash, fly ash, and flue gas desulfurization materials. The chemical composition of coal ash varies depending on the feed coal source, combustion parameters, and the presence and type of air pollution control devices that remove contaminants from the flue gas into the solid waste stream. Although a significant portion of coal ash waste is recycled, the majority of coal ash is disposed in landfills and holding ponds. Coal ash impoundments have a long history of environmental degradation, which includes: contaminant leaching into groundwater, the discharge of contaminant-laden effluent into surface waters, and catastrophic impoundment failures and ash spills. Despite these known problems, coal ash is not considered a hazardous waste, and thus is not subject to stringent disposal requirements. The current coal ash management system is based on risk assessments of coal ash that do not include environmental parameters that have a profound impact on coal ash contaminant mobility, particularly for the toxic elements such as mercury, arsenic, and selenium. This dissertation research focused on the biogeochemical transformations of mercury, arsenic, and selenium associated with coal ash materials in an effort to: (1) define the key environmental parameters controlling mercury, arsenic, and selenium fate during disposal and ash spills; and (2) delineate the relationship between coal ash characteristics, environmental parameters, and leaching potential. </p><p> The impact of coal ash on mercury transformations in anaerobic systems was assessed using anaerobic sediment-ash microcosms to mimic an ash spill into a benthic aquatic system. Anaerobic sediments are the primary zones for the microbial conversion of inorganic mercury to methyl mercury (MeHg), a process that is mediated by anaerobic bacteria, particularly sulfate reducing bacteria (SRB). MeHg is a potent neurotoxin that biomagnifies up the aquatic food chain, presenting a human health risk-- especially to children and pregnant women. The results of the sediment-ash microcosm experiments indicated negligible net production of MeHg in microcosms with no ash and in microcosms amended with the low-sulfate/low-Hg ash. In contrast, microcosms amended with sulfate and mercury-rich ash showed increases in MeHg concentrations that were two to three times greater than control microcosms without ash. The enhancement MeHg production in the microcosms was likely due to large quantities of leachable sulfate that stimulated the activity of methylating bacteria. Overall, these results highlight the importance of considering both the geochemical conditions of the receiving environment and the chemical composition of the coal ash in assessing the MeHg potential of coal ash. </p><p> The hypothesis that sulfate-rich coal ash can change sediment microbial communities, enhancing MeHg production, was tested by analyzing coal ash impacts on the SRB community in the sediment-ash microcosms using Terminal Restriction Fragment Length Polymorphism (T-RFLP), Quantitative Polymerase Chain Reaction (q-PCR), and Reverse Transcription-qPCR (RT-qPCR). Coal ash did not appear to cause significant changes to the structure of the overall bacterial community, though results showed that it may have caused a decrease in the evenness for species distribution for both SRB and the overall microbial community. During the five-day incubation experiment, the coal ash had a temporary significant effect on SRB abundance during the first one to two days of the experiment and a more sustained effect on SRB activity. This stimulation of SRB population growth and activity also corresponded with increasing net MeHg production. Overall, results indicate that coal ash amendments do not cause large shifts in the overall microbial community or the SRB community, but results indicate that there are connections between SRB abundance/activity and MeHg production. More research is needed to determine how coal ash directly impacts Hg methylating microorganisms, which include diverse array of microorganisms outside of SRB.</p><p> The effect of aerobic and anaerobic conditions on arsenic and selenium leaching from coal ash in an ash spill scenario was also assessed using sediment-ash microcosms. The fate of arsenic and selenium associated with coal ash is of particular concern due to the leachability of these elements at neutral pH and their tendency to bioaccumulate in aquatic organisms. Both the redox speciation of arsenic and selenium, and the pH of the aquatic system, are known to influence leaching into the environment, yet current environmental risk assessments of coal ash focus on pH alone as the primary driving force for arsenic and selenium leaching from coal ash and do not take into account the effects of anaerobic conditions and microbial activity. In this research, total dissolved concentrations of arsenic and selenium, dissolved speciation of arsenic, and solid phase speciation of selenium were monitored to determine the biogeochemical transformations and leaching of arsenic and selenium under differing redox conditions. The results from the sediment-ash microcosm studies showed that redox potential was the major determinant of arsenic and selenium mobility in the microcosm systems with greater arsenic leaching occurring in anaerobic microcosms and greater selenium leaching occurring in aerobic microcosms. Furthermore, the experiments provided clues to how coal ash influences the geochemistry of the benthic environment and how these influences affect the speciation and longer term solubility of arsenic and selenium. </p><p> Finally, experiments were conducted to determine how differing CaO, SO3, and Fe2O3 concentrations in coal ash affect the release of arsenic and selenium from sediment-ash mixtures in a simulated ash spill environment. Aerobic and anaerobic sediment-ash microcosms were constructed to mimic an ash spill into a benthic aquatic system, and a variety of coal ash materials were tested as amendments, including seven fly ashes, one lime-treated fly ash sample, and two FGD samples. Results showed that, in most cases, the sediment in the microcosm buffered the system at neutral, which counteracted leaching impacts of differing CaO and SO3 concentrations in the microcosms. Regardless of ash material, leaching of selenium was greater under aerobic conditions and was correlated with the total selenium content of the microcosm. Maximum leaching of arsenic occurred in anaerobic microcosms for some ash materials and in aerobic microcosms for other materials, suggesting that ash material chemistry played a significant role in controlling arsenic mobility. In both aerobic and anaerobic microcosms, dissolved arsenic concentration was correlated with total arsenic content of the ash material and in anaerobic microcosms, dissolved arsenic concentrations also correlated with the total iron content of the ash material. Overall, the results of these experiments showed that arsenic and selenium release under environmentally relevant conditions cannot be predicted by the CaO and SO3 content of the ash material. Rather, the total arsenic, total selenium content, and total iron content of the ash material are good predictors of the worst case environmental leaching scenario.</p><p> These investigations illuminated two major conclusions: (1) microbial activity and differing redox conditions are key in determining the impact of coal ash on the environment and in determining the mobility of coal ash contaminants, and (2) coal ash characteristics, such as sulfate and iron content, can change the redox chemistry and microbial activity of the surrounding environment, further influencing the fate of ash contaminants. This work will be useful in designing a framework that accurately predicts the leaching potential of ash contaminants under environmentally relevant conditions. The results will also be helpful in developing treatment technologies for ash impoundment effluent, guiding decisions on ash pond closure and remediation, and in designing long-term monitoring plans and remediation strategies for ash-impacted sites.</p> / Dissertation

Maternal behaviours are those that increase offspring survival. Estrogens affect maternal behaviour by activating Estrogen Receptors (ER) in the brain. Maternal brain plasticity was explored by characterizing the effects of exposure to a mixture of environmental pollutants on number of ERs. Following exposure to the toxicants during pregnancy and lactation, brains of female rats were collected, sectioned at 30 μm and immunohistochemistry for ERα performed. Immuno-positive cells in the mPOA, VTA and NAc were counted. A two way ANOVA revealed no main effect of Treatment on the number of immunopositive cells for all three brain regions. However, a significant difference between the High and Low Doses with the high dose reducing the number of ERα+ cells in the mPOA and VTA. Our work showcases the importance of studying the effects of multiple chemical co-exposures on the mother's brain, as maternal brain changes impact maternal behaviour consequently affecting offspring neurodevelopment.

Recent research has shown that the Arctic may be a sink for mercury, however, the fate of this deposited mercury in the environment is not known. The objective of this project was to determine the factors affecting methyl mercury (MeHg) production in Arctic organic soil on the Truelove Lowlands, Devon Island, Canada. In the field we observed a steady decrease in MeHg over time, with MeHg concentration at many sampling locations declining below detection limits. This decrease did not correlate to any chemical or biophysical parameter measured. During the study the Lowlands appeared to be mildly reducing with dissolved Fe(II) being present in the porewater, however, no correlation was observed between MeHg production and the variables measured. The dissolved organic matter concentration of the porewater was quite high, the pH was circumneutral and it would seem that in the absence of more highly reducing conditions that mercury would be unavailable for methylation.<p> It seems likely under field conditions MeHg was much more bioavailable then inorganic mercury. This would lead to a higher rate of demethylation then methylation and a net decrease in MeHg. Little research has been done on demethylation and the effect of environmental conditions on demethylation, especially in arctic environments. However, it is possible that the rate of demethylation was not affected by changes in temperature or any other parameter measured over the course of the field study. <p> Laboratory microcosm studies using saturated soil from the organic horizons demonstrated little potential for unspiked organic soil to produce significant amounts of MeHg. The spiked treatment, however, had an eight fold increase in MeHg concentration and the sterile treatment showed no change in MeHg concentration over 40 days of freeze (-5 0C) and 59 days of thaw (4 oC). <p> Our data suggests that a combination of atmospheric and in-situ processes maintain a cycle of MeHg production (spring) and loss (summer) in arctic soils. It would seem that Arctic wetland soils are not a significant source of MeHg to the Arctic ecosystem and that snowmelt is the dominant source.

Recent research has shown that the Arctic may be a sink for mercury, however, the fate of this deposited mercury in the environment is not known. The objective of this project was to determine the factors affecting methyl mercury (MeHg) production in Arctic organic soil on the Truelove Lowlands, Devon Island, Canada. In the field we observed a steady decrease in MeHg over time, with MeHg concentration at many sampling locations declining below detection limits. This decrease did not correlate to any chemical or biophysical parameter measured. During the study the Lowlands appeared to be mildly reducing with dissolved Fe(II) being present in the porewater, however, no correlation was observed between MeHg production and the variables measured. The dissolved organic matter concentration of the porewater was quite high, the pH was circumneutral and it would seem that in the absence of more highly reducing conditions that mercury would be unavailable for methylation.<p> It seems likely under field conditions MeHg was much more bioavailable then inorganic mercury. This would lead to a higher rate of demethylation then methylation and a net decrease in MeHg. Little research has been done on demethylation and the effect of environmental conditions on demethylation, especially in arctic environments. However, it is possible that the rate of demethylation was not affected by changes in temperature or any other parameter measured over the course of the field study. <p> Laboratory microcosm studies using saturated soil from the organic horizons demonstrated little potential for unspiked organic soil to produce significant amounts of MeHg. The spiked treatment, however, had an eight fold increase in MeHg concentration and the sterile treatment showed no change in MeHg concentration over 40 days of freeze (-5 0C) and 59 days of thaw (4 oC). <p> Our data suggests that a combination of atmospheric and in-situ processes maintain a cycle of MeHg production (spring) and loss (summer) in arctic soils. It would seem that Arctic wetland soils are not a significant source of MeHg to the Arctic ecosystem and that snowmelt is the dominant source.

Final publication is available at http://www.tandfonline.com/doi/full/10.1080/19393210.2014.968808 / 京都大学 / 0048 / 新制・課程博士 / 博士(社会健康医学) / 甲第19637号 / 社医博第70号 / 新制||社医||9(附属図書館) / 32673 / 京都大学大学院医学研究科社会健康医学系専攻 / (主査)教授 木原 正博, 教授 小杉 眞司, 教授 YOUSSEFIAN Shohab / 学位規則第4条第1項該当 / Doctor of Public Health / Kyoto University / DFAM

<p>The aquatic plant <i>Ipomoea aquatica</i> is a popular vegetable in Southeast Asia, often cultivated in nutrient rich and polluted waters. The overall aim of this thesis was to estimate potential risks for human health and reduced plant growth due to accumulation and toxicity of total-Hg, methyl-Hg, Cd and Pb.</p><p>In plants from cultivations in Thailand, the concentrations of Cd and Pb in the shoots were well beneath recommended maximum values for human consumption, but at some sites the Hg concentrations were high. It was demonstrated that <i>I. aquatica</i> has the capacity to accumulate much higher Cd and Pb concentrations in the shoots than found in field-cultivations, before exhibiting toxic symptoms. The Hg concentrations, however, occasionally reached levels that are toxic for the plant. Up to11% of total-Hg was methyl-Hg, the most toxic Hg species, though at one site it was 50-100%. To study if methyl-Hg is formed in <i>I.</i> <i>aquatica</i>, plants were exposed to inorganic Hg through the roots. Of the Hg that reached the young, metabolically active parts of the shoots, a part was transformed to methyl-Hg. A major proportion of absorbed metals was retained in the roots, which had a high tolerance for high internal metal concentrations. </p><p>The nutrient level did influence accumulation and effects of Hg, Cd and Pb in<i> I. aquatica</i>. Low external nutrient levels resulted in increased metal accumulation in the shoots and in metal-induced toxic effects in the plant at low external metal levels. A generous supply of sulphur or nitrogen induced formation of thiol-rich peptides in <i>I. aquatica</i>, compounds that have a metal detoxifying effect in plants. </p><p>To conclude, the levels of Cd and Pb in field cultivated <i>I. aquatica</i> do not pose any apparent threat to human health or risk for reduced plant growth. The levels of Hg however, were high at some sites and could be a health threat, for children and foetuses in particular, and especially considering the presence of methyl-Hg. The use of fertilizers is favourable as it reduces the risk for increased metal concentrations in <i>I.</i> <i>aquatica</i> and for reduced crop yields. </p>

The aquatic plant Ipomoea aquatica is a popular vegetable in Southeast Asia, often cultivated in nutrient rich and polluted waters. The overall aim of this thesis was to estimate potential risks for human health and reduced plant growth due to accumulation and toxicity of total-Hg, methyl-Hg, Cd and Pb. In plants from cultivations in Thailand, the concentrations of Cd and Pb in the shoots were well beneath recommended maximum values for human consumption, but at some sites the Hg concentrations were high. It was demonstrated that I. aquatica has the capacity to accumulate much higher Cd and Pb concentrations in the shoots than found in field-cultivations, before exhibiting toxic symptoms. The Hg concentrations, however, occasionally reached levels that are toxic for the plant. Up to11% of total-Hg was methyl-Hg, the most toxic Hg species, though at one site it was 50-100%. To study if methyl-Hg is formed in I. aquatica, plants were exposed to inorganic Hg through the roots. Of the Hg that reached the young, metabolically active parts of the shoots, a part was transformed to methyl-Hg. A major proportion of absorbed metals was retained in the roots, which had a high tolerance for high internal metal concentrations. The nutrient level did influence accumulation and effects of Hg, Cd and Pb in I. aquatica. Low external nutrient levels resulted in increased metal accumulation in the shoots and in metal-induced toxic effects in the plant at low external metal levels. A generous supply of sulphur or nitrogen induced formation of thiol-rich peptides in I. aquatica, compounds that have a metal detoxifying effect in plants. To conclude, the levels of Cd and Pb in field cultivated I. aquatica do not pose any apparent threat to human health or risk for reduced plant growth. The levels of Hg however, were high at some sites and could be a health threat, for children and foetuses in particular, and especially considering the presence of methyl-Hg. The use of fertilizers is favourable as it reduces the risk for increased metal concentrations in I. aquatica and for reduced crop yields.