Fractionation of multiple sulfur isotopes during phototrophic oxidation of sulfide and elemental sulfur by a green sulfur bacterium

We present multiple sulfur isotope measurements of sulfur compounds associated with the oxidation of H(2)S and S(0) by the anoxygenic phototrophic S-oxidizing bacterium Chlorobium tepidum. Discrimination between (34)S and (32)S was +1.8 +/- 0.5%, during the oxidation of H(2)S to S(0), and -1.9 +/- 0.8 parts per thousand during the oxidation of S(0) to SO(4)(2-), consistent with previous studies. The accompanying Delta(33)S and Delta(36)S values of sulfide, elemental sulfur, and sulfate formed during these experiments were very small, less than 0.1 parts per thousand for Delta(33)S and 0.97 parts per thousand for Delta(36)S, supporting mass conservation principles. Examination of these isotope effects within a framework of the metabolic pathways for S oxidation suggests that the observed effects are due to the flow of sulfur through the metabolisms, rather than abiotic equilibrium isotope exchange alone, as previously suggested. The metabolic network comparison also indicates that these metabolisms work to express some isotope effects (between sulfide, polysulfides, and elemental sulfur in the periplasm) and suppress others (kinetic isotope effects related to pathways for oxidation of sulfide to sulfate via the same enzymes involved in sulfate reduction acting in reverse). Additionally, utilizing fractionation factors for phototrophic S oxidation calculated from our experiments and for other oxidation processes calculated from the literature (chemotrophic and inorganic S oxidation), we constructed a set of ecosystem-scale sulfur isotope box models to examine the isotopic consequences of including sulfide oxidation pathways in a model system. These models demonstrate how the small delta(34)S effects associated with S oxidation combined with large delta(34)S effects associated with sulfate reduction (by SRP) and sulfur disproportionation (by SDP) can produce large (and measurable) effects in the Delta(33)S of sulfur reservoirs. Specifically, redistribution of material along the pathways for sulfide oxidation diminishes the net isotope effect of SRP and SDP, and can mask the isotopic signal for sulfur disproportionation if significant recycling of S intermediates occurs. We show that the different sulfide oxidation processes produce different isotopic fields for identical proportions of oxidation, and discuss the ecological implications of these results to interpreting minor S isotope patterns in modern systems and in the geologic record. (C) 2008 Elsevier Ltd. All rights reserved.