Mercury (Hg) is a toxic heavy metal that poses significant human and environmental health risks. Mineral-associated Hg is the largest reservoir of Hg in the environment where it can account for nearly 60% of the global Hg mass inventory. A large fraction of this pool is comprised of mercury sulfide (HgS) minerals, including metacinnabar (beta-HgS). HgS minerals have long been considered insignificant sources of Hg to aqueous or atmospheric pools in all but severely acidic environments due to their low solubility and slow abiotic dissolution kinetics. Little previous work has been conducted investigating the bacterial colonization of HgS minerals and the potential role of these mineral-associated communities in impacting the mobility of mineral-hosted Hg. To address this gap in knowledge, the studies within this dissertation employed a combination of field- and laboratory-based methods. Using culture-independent techniques, this work revealed that sulfur-oxidizing bacteria can extensively colonize metacinnabar within aerobic, near neutral pH, creek sediments, suggesting a potential role for chemolithotrophic bacteria in metacinnabar weathering. Within laboratory incubations, the dominant bacterial colonizer (Thiobacillus thioparus), induced extensive release and volatilization of metacinnabar-hosted Hg. These findings expose a new pathway for metacinnabar dissolution and point to mineral-hosted Hg as an underappreciated source of elemental Hg that may contribute to global atmospheric Hg budgets. In addition, this work elucidates the importance of thiosulfate, a major intermediate sulfur species in the environment, in stimulating metacinnabar dissolution. Therefore, the work within this dissertation shows that authigenic HgS minerals are not merely a sink for Hg within non-acidic natural environments and instead are a source of dissolved and gaseous Hg. This work provides critical information for predicting the transport of Hg in the environment and for developing appropriate management and remediation strategies for Hg-contaminated systems. / Engineering and Applied Sciences

Microorganisms control many processes pertinent to the stability of radwaste inventories in nuclear storage and disposal facilities. Furthermore, numerous subsurface bacteria, such as Shewanella spp. have the ability to couple the oxidation of organic matter to the reduction of a range of metals, anions and radionuclides, thus providing the potential for the use of such versatile species in the bioremediation of radionuclide contaminated land. However, the organisms promoting these processes will likely be subject to significant radiation doses. Hence, the impact of acute doses of ionizing radiation on the physiological status of a key Fe(III)-reducing organism, Shewanella oneidensis, was assessed. FT-IR spectroscopy and MALDI-TOF-MS suggested that the metabolic response to radiation is underpinned by alterations to proteins and lipids. Multivariate statistical analysis indicated that the phenotypic response was somewhat predictable although dependent upon radiation dose and stage of recovery. In addition to the cellular environment, the impact of radiation on the extracellular environment was also assessed. Gamma radiation activated ferrihydrite and the usually recalcitrant hematite for reduction by S. oneidensis. TEM, SAED and Mössbauer spectroscopy revealed that this was a result of radiation induced changes to crystallinity. Despite these observations, environments exposed to radiation fluxes will be much more complex, with a range of electron acceptors, electron donors and a diverse microbial community. In addition, environmental dose rates will be much lower than those used in previous experiments. Sediment microcosms irradiated over a two month period at chronic dose rates exhibited enhanced Fe(III)-reduction despite receiving potentially lethal doses. The microbial ecology was probed throughout irradiations using pyrosequencing to reveal significant shifts in the microbial communities, dependent on dose and availability of organic electron donors. The radiation tolerance of an algal contaminant of a spent nuclear fuel pond was also assessed. FT-IR spectroscopy revealed a resistant phenotype of Haematococcus pluvialis, whose metabolism may be protected by the radiation induced production of an astaxanthin carotenoid. The experiments of this thesis provide evidence for a range of impacts of ionizing radiation on microorganisms, including the potential for radiation to provide the basis for novel ecosystems. These results have important implications to the long-term storage of nuclear waste and the geomicrobiology of nuclear environments.

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<p>This doctoral research comparatively assesses the biogeochemical properties of suspended aquatic flocs through a integrated field-laboratory approach; providing new insight into the linkages among floc associated bacteria, floc-reactive solid phases and trace metal uptake.</p> <p>Results show flocs to possess a distinct geochemistry, microbiology and composition from bed sedimentary materials in close proximity (III-oxyhydroxide minerals (FeOOH); resulting in localized floc-Fe-mineral precipitates and enhanced reactivity. Further, the Fe-enrichment of floc and of floc bio-mineral constituents in turn provides an important and novel lens through which to examine how environmental microbial communities, microbial metabolism and Fe^III/Fe^IIredox transformations interact. The results were the discovery of floc-hosted, Fe^III/II-redox cycling bacterial consortia across diverse oxygenated (O₂^Sat.=1-103%) aquatic systems, which were not predicted to sustain bacterial Fe-metabolism. Both environmental<em> </em>and experimentally-developed consortial aggregates constituted multiple genera of aero-intolerant Fe^III-reducing and Fe^II-oxidizing bacteria together with oxygen consuming organotrophic species. These findings highlight that the implementation of geochemical thermodynamic constraints alone as a guide to investigating and interpreting microbe-geosphere interactions may not accurately capture processes occurring <em>in situ.</em></p> <p><em> </em> Seasonal investigation of microbial Fe^III/II-redox transformations highlighted the interdependence of floc Fe-redox cycling consortia members, revealing that cold conditions and a turnover in putative Fe-reducing community membership extinguishes the potential for coupled Fe-redox cycling by wintertime floc bacteria. Further, the observed summer-winter seasonal turnover of <em>in situ</em> floc community membership corresponded with an overall shift from dominant Fe to S redox cycling bacterial communities. This significantly impacted observable floc Fe and TE (Cd, Pb) geochemistry, resulting in a shift in floc associated Fe-phases from dominantly Fe^(III)_(s) to Fe^(II)_(s), and, in turn, corresponded to a large decrease of TE uptake by flocs under ice.</p> / Doctor of Science (PhD)

With rising concentrations of CO₂ in the Earth's atmosphere causing concern about climate change, many solutions are being presented to decrease emissions. One of the proposed solutions is to sequester excess CO₂ in geological formations such as basalt. The deep subsurface is known to harbor much of the microbial biomass on earth and questions abound as to how this deep life is going to respond to the injection of CO₂. Many studies have used model microorganisms to demonstrate the ability of microbes to aid in the safe, permanent sequestration of CO₂ in the subsurface. The objective of this research is to characterize the microbial community present in the basalts at the Wallula pilot carbon sequestration well prior to the injection of CO₂ and then perform laboratory studies to determine how the native microbial community will respond to carbon sequestration conditions. Six samples were collected from the Wallula pilot well prior to the injection of CO₂ into the system. The microorganisms in these samples were characterized by pyrosequencing of 16S rRNA genes, revealing a community dominated by the Proteobacteria, Firmicutes, and Actinobacteria. The organisms detected were related to microbes known to metabolize hydrogen, sulfur, and single carbon compounds. These microorganisms may be stimulated in formations located at the fringe of the pool of injected CO₂. Laboratory studies revealed that the native microbial community suffered a two order of magnitude loss of population upon exposure to CO₂ under carbon sequestration conditions. The community also shifted from being dominated by Proteobacteria prior to CO₂ exposure to being dominated by Firmicutes after exposure. Specifically, the genus Alkaliphilus, which was previously undetected, appeared after CO₂ exposure and became dominant. The dominance of Alkaliphilus, along with other rare organisms which did not compose a majority of the population prior to the introduction of CO₂ to the system, indicates that members of the rare biosphere may be better adapted to changing environmental conditions specific to CO₂ sequestration than other indigenous cells. Thus, the rare biosphere should be examined closely as part of any environmental study, as these minority microorganisms may be the first indication of perturbation or impact. / Graduation date: 2013

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