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Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S-depletions associated with the lowest rates of sulfate reduction and the lowest 34S-depletions with the highest rates. However, at high sulfate reduction rates (>10 micromoles cm-3 d-1) the lowest fractionation was 20% independent of the rates. Overall, there was a similarity between the fractionation obtained by the natural populations of sulfate reducers and previous measurements from pure cultures. This was somewhat surprising given the extremely high rates of sulfate reduction in the experiments. Our results are explained if we conclude that the fractionation was mainly controlled by the specific rate of sulfate reduction (mass cell-1 time-1) and not by the absolute rate (mass volume-1 time-1). Sedimentary sulfides (mainly FeS2) were on average 40% depleted in 34S compared to seawater sulfate. This amount of depletion was more than could be explained by the isotopic fractionations that we measured during bacterial sulfate reduction. Therefore, additional processes contributing to the fractionation of sulfur isotopes in the sediments are indicated. From both Solar Lake and Logten Lagoon we were able to enrich cultures of elemental sulfur-disproportionating bacteria. We suggest that isotope fractionation accompanying elemental sulfur disproportionation contributes to the 34S depletion of sedimentary sulfides at our study sites.

The evolution of non-photosynthetic sulphide-oxidizing bacteria was contemporaneous with a large shift in the isotopic composition of biogenic sedimentary sulphides between 0.64 and 1.05 billion years ago. Both events were probably driven by a rise in atmospheric oxygen concentrations to greater than 5-18% of present levels--a change that may also have triggered the evolution of animals.

Bacteria that disproportionate elemental sulfur fractionate sulfur isotopes such that sulfate is enriched in sulfur-34 by 12.6 to 15.3 per mil and sulfide is depleted in sulfur-34 by 7.3 to 8.6 per mil. Through a repeated cycle of sulfide oxidation to S0 and subsequent disproportionation, these bacteria can deplete sedimentary sulfides in sulfur-34. A prediction, borne out by observation, is that more extensive sulfide oxidation will lead to sulfides that are more depleted in sulfur-34. Thus, the oxidative part of the sulfur cycle creates circumstances by which sulfides become more depleted in sulfur-34 than would be possible with sulfate-reducing bacteria alone.

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works located in Guerrero Negro, Baja California Sur, Mexico. Included in the budget are measured rates of O2 production, sulfate reduction, and elemental exchange across the mat/brine interface, day and night, at various temperatures and times of the year. We infer from this data the various sinks for O2, as well as the sources of carbon for primary production. To summarize, although seasonal variability exists, a major percentage of the O2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O2 that diffused into the mat was used to oxidize sulfide, with O2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Also, oxygenic photosynthesis was the most important process of carbon fixation, although anoxygenic photosynthesis may have been important at low light levels during some times of the year. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount. These mats are thus closely coupled systems where rapid rates of photosynthesis both require and fuel rapid rates of heterotrophic carbon oxidation.

The search for life can only be as successful as our understanding of the tools we use to search for it. Here we present new sulphur isotope data (32S, 33S, 34S, 36S) from a variety of modern marine environments and use these observations, along with previously published work, to contribute to this search. Specifically, we use these new data to gain a sense of life's influences on the sulphur isotope record and to distinguish these biologically influenced signatures from their non-biological counterparts. This treatment extends sulphur isotope analyses beyond traditional (34S/32S) measures and employs trace isotope relationships (33S/32S, 36S/32S), as the inclusion of these isotopes provides unique information about biology and its role in the sulphur cycle through time. In the current study we compare and contrast isotope effects produced by sulphur-utilizing microorganisms (experimental), modern and ancient sedimentary records (observational) and non-biological reactions (theoretical). With our collective search for life now extending to neighbouring planets, we present this study as a first step towards more fully understanding the capability of the sulphur isotope system as a viable tool for life detection, both on Earth and beyond. [ABSTRACT FROM AUTHOR]

The surface sulfur reservoir is in intimate contact with the mantle. Over long time scales, exchange with the mantle has influenced the surface reservoir size and possibly its isotopic composition. Processes delivering sulfur to the Earth surface from the mantle include volcanic outgassing, hydrothermal input, and ocean crust weathering. The sulfide fixed in ocean crust as a consequence of hydrothermal sulfate reduction, and subduction of sedimentary sulfides, represent return pathways of sulfur to the mantle. The importance of these different pathways in influencing the size of the surface sulfur reservoir depends on the particulars of ocean and atmosphere chemistry. During times of banded iron formation when the oceans contained dissolved iron, sulfide from submarine hydrothermal activity was precipitated on the seafloor and subsequently subducted back into the mantle and, therefore, had little impact on the surface sulfur reservoir size. With sulfidic ocean bottom water conditions, which may have occurred through long stretches of the Mesoproterozoic and Neoproterozoic, significant amounts of sulfide is subducted into the mantle. When the oceans are oxic, sulfide subduction is unimportant, and an additional source, ocean crust weathering, delivers sulfur to the Earth surface. Thus, under oxic conditions the surface environment accumulates sulfur, and probably has for most of the last 700 million years. Mass balance modeling suggests that the surface sulfur reservoir may have peaked in size in the early Mesoproterozoic, declined to a minimum in the Neoproterozoic, and increased to its present size through the Phanerozoic. The exchange of sulfur between the mantle and the surface environment can also influence the isotopic composition of the surface reservoir. Modeling shows that the subduction of 34S-depleted sulfur through the Mesoproterzoic could have significantly increased the average δ34S of the surface reservoir into the late Neoproterozoic. The preserved isotope record through the Neoproterozoic is well out of balance, with the average δ34S for sulfate and sulfide both exceeding the modern crustal average. This imbalance could be explained, at least partly, if the crustal average was more 34S-enriched than at present, as the modeling presented here suggests. [ABSTRACT FROM AUTHOR]