34S/32S and 18O/16O fractionation during sulfur disproportionation by Desulfobulbus propionicus

In the present study, coupled stable sulfur and oxygen isotope fractionation during elemental sulfur disproportionation according to the overall reaction: 4H(2)O + 4S degrees -> 3H(2)S + SO42- + 2H(+), was experimentally investigated for the first time using a pure culture of the sulfate reducer Desulfobulbus propionicus at 35 degrees C. Bacterial disproportionation of elemental sulfur is an important process in the sulfur cycle of natural surface sediments and leads to the simultaneous formation of sulfide and sulfate. A dual-isotope approach considering both sulfur and oxygen isotope discrimination has been shown to be most effective in evaluating specific microbial reactions. The influence of iron- and manganese bearing-solids (Fe(II) CO3, Fe(III) OOH, Mn(IV)O-2) acting in natural sediments as scavengers for hydrogen sulfide, was considered, too. Disproportionation of elemental sulfur was observed in the presence of iron solids at a cell-specific sulfur disproportionation rate of about 10(-9.5 +/- 0.4) mu mol S degrees cell(-1) h(-1). No disproportionation, however, was observed with MnO2. In the presence of iron solids, newly formed sulfate was enriched in O-18 compared to water by about +21 parts per thousand (equivalent to epsilon(H2O)), in agreement with a suggested oxygen isotope exchange via traces of intra- or extracellular sulfite that is formed as a disproportionation intermediate. Dissolved sulfate was also enriched in S-34 compared to elemental sulfur by up to + 35%. Isotope fractionation by Desulfobulbus propionicus is highest for all disproportionating bacteria investigated, so far, and may impact on the development of isotope signals at the redox boundary of surface sediments.