Abstract Dissimilatory microbial sulfate reduction (MSR) The specific objectives of the study were to provide the first measurements of sulfur isotope fractionation associated with acidophilic sulfate reducing-microorganisms, and to examine whether pH influences sulfur fractionation during MSR. The fractionation associated with the strains investigated was comparable to that of neutrophilic strains with similar metabolisms (4-12‰), but varied with pH. Two fractionation regimes were identified: one regime is consistent with fractionation during exponential growth, while the other – not identified previously - is not linked to active sulfate reduction and may result from internal sulfate accumulation. This would represent the first measurement of sulfur fractionation during sulfate uptake, the first step of MSR. Geological processes at the Cretaceous-Paleogene (KPg) boundary The KPg boundary is associated with one of the largest biological extinctions in the history of our planet. Two major geologic events - the Chicxulub bolide impact with evaporite terrane and the eruption of the Deccan continental flood basalts - coincide with the KPg boundary and have been identified as possible triggers for the extinctions, but their relative timing remains unresolved. The objectives of this study were to identify the contribution of these processes to the sulfur burden in the sedimentary environment of two freshwater KPg sections, and to determine their relative timing. The results demonstrate that the peak of Deccan volcanism post-dates the Chicxulub impact and the associated abrupt KPg mass extinction, thus precluding a direct volcanic causal mechanism, but shedding light on the underlying causes for the delayed recovery of ecosystems in the early Paleogene.

Abstract Dissimilatory microbial sulfate reduction (MSR) The specific objectives of the study were to provide the first measurements of sulfur isotope fractionation associated with acidophilic sulfate reducing-microorganisms, and to examine whether pH influences sulfur fractionation during MSR. The fractionation associated with the strains investigated was comparable to that of neutrophilic strains with similar metabolisms (4-12‰), but varied with pH. Two fractionation regimes were identified: one regime is consistent with fractionation during exponential growth, while the other – not identified previously - is not linked to active sulfate reduction and may result from internal sulfate accumulation. This would represent the first measurement of sulfur fractionation during sulfate uptake, the first step of MSR. Geological processes at the Cretaceous-Paleogene (KPg) boundary The KPg boundary is associated with one of the largest biological extinctions in the history of our planet. Two major geologic events - the Chicxulub bolide impact with evaporite terrane and the eruption of the Deccan continental flood basalts - coincide with the KPg boundary and have been identified as possible triggers for the extinctions, but their relative timing remains unresolved. The objectives of this study were to identify the contribution of these processes to the sulfur burden in the sedimentary environment of two freshwater KPg sections, and to determine their relative timing. The results demonstrate that the peak of Deccan volcanism post-dates the Chicxulub impact and the associated abrupt KPg mass extinction, thus precluding a direct volcanic causal mechanism, but shedding light on the underlying causes for the delayed recovery of ecosystems in the early Paleogene.

Underlying all applications of sulfur isotope analyses is our understanding of isotope systematics. This dissertation tests some fundamental assumptions and assertions, drawn from equilibrium theory and a diverse body of empirical work on biochemical kinetics, as applied to the multiple sulfur isotope systematics of microbial sulfate reduction. I take a reductionist approach, both in the questions addressed and experimental approaches employed. This allows for a mechanistic, physically consistent interpretation of geological and biological sulfur isotope records. The goal of my work here is to allow interpreters a more biologically, chemically and physically parsimonious framework to decipher the signals coded in modern and ancient sulfur isotope records. / Earth and Planetary Sciences

On retrouve des contaminations d’aquifèr à l’arsenic dans touts les deltaï de l'Asie du Sud-Est, y compris dans le delta du Mékong, ce qui affecte la santé de millions de personnes. L’arsenic est très sensible aux fluctuations des conditions redox qui sont générés par les cycles alternés humides/secs pendant la saison de mousson. Une étude sur les caractéristiques géophysiques et chimiques du sol et des eaux souterraines dans le district de An Phu, dans le haut du delta du Mékong au Vietnam, suggère une forté contamination à l’As dans cette région. Les données chimiques et géophysiques indiquent une forte corrélation entre concentrations dans les eaux souterraines anoxiques et conductivité des sols. La liberation de l’arsenic est associée à la dissolution réductrice induih par des microorganisms des colloïdes et (oxyhydr)oxydes de fer dans des conditions d'oxydo-réduction oscillantes. La présence de bactéries sulforéductrices a le potentiel de stabiliser l’arsenic dans la phase solide et de l’atténuer dans la phase aqueuse par adsorption / désorption de l’arsenic sur les (oxyhydr)oxydes, et / ou sulfures de fer via la formation de complexes thiols. En raison de la teneur en pyrite élevée dans les sédiments, l'oxydation de la pyrite peut abaisser le pH et conduire à l'inhibition de la réduction microbienne du sulfate et aime empêcher la séquestration de l’arsenic dissous. Bien que le cycle biogéochimique de l’arsenic dans un système dynamique d’oxydoréduction soit une problématique complexe, il a été possible de renforcer notre compréhension de ce système / Aquifer arsenic (As) contamination is occuring throughout deltaic areas of Southeast Asia, including the Mekong Delta, and affects the health of millions of people. As is highly sensitive to fluctuations of redox conditions which are generated by the alternating wet-dry cycles during the monsoonal seasons. A survey of geophysical and chemical characteristics of soil and groundwater in the An Phu district, located in the vicinity of the Mekong Delta in Vietnam, shows the occurrence high As aqueous concentration in this region. Chemical and geophysical data indicate a strong positive correlation between As concentrations in the anoxic groundwater and conductivity of soils. In addition, mechanisms of As release are shown to be associated with colloidal and iron (oxyhydr)oxides which undergo microbial mediated reductive dissolution under redox oscilatting conditions. The presence of sulfate microbial reduction potentially stabilizes As in the solid phase and diminish As in the aqueous phase through the adsorption/desorption of As onto iron (oxyhydr)oxides and/ or sulfides with formation of thiols complexes in solid phase. Because of the high pyrite content in sediment, pyrite oxidation may drop in pH values, leads to inhibition of sulfate reducing bacteria and reduces sequestration of dissolved As. Although the biogeochemical cycling of redox sensitive species such as As in dynamic systems is challenging, it has been possible to strengthen our collective understanding of such system.