Intermediate sulfur oxidation state compounds in the euxinic surface sediments of the Dvurechenskii mud volcano (Black Sea)

The deep Black Sea is known to be depleted in electron-acceptors for sulfide oxidation. This study on depth distributions of sulfur species (S(II), S(0), Sn2-, S2O32-, SO32-, SO42-) in the Dvurechenskii mud volcano, a cold seep situated in the permanently anoxic eastern Black Sea basin (Sorokin Trough, 2060m water depth), showed remarkable concentrations of sulfide oxidation products. Sulfite concentrations of up to 11μmolL^-1, thiosulfate concentrations of up to 22μmolL^-1, zero-valent sulfur concentrations of up to 150μmolL^-1 and up to five polysulfide species were measured in the upper 20cm of the sediment. Electron-acceptors found to be available in the Dvurechenskii mud volcano (DMV) for the oxidation of hydrogen sulfide to sulfide oxidation intermediates are iron-minerals, and probably also reactive manganese phases. Up to 60μmolg^-1 of reactive iron-minerals and up to 170μmolL^-1 dissolved iron was present in the central summit with the highest fluid upflow and fresh mud outflow. Thus, the source for the oxidative power in the DMV are reactive iron phases extruded with the mud from an ancient source in the deeply buried sediments, leading to the formation of various sulfur intermediates in comparably high concentrations. Another possible source of sulfide oxidation intermediates in DMV sediments could be the formation of zero-valent sulfur by sulfate dependent anaerobic microbial oxidation of methane followed by disproportionation of zero-valent sulfur. Sulfide oxidation intermediates, which are produced by these processes, do not reach thermodynamic equilibrium with rhombic sulfur, especially close to the active center of the DMV due to a short equilibration time. Thus, mud volcano sediments, such as in the DMV, can provide oxidizing niches even in a highly reduced environment like the abyssal part of the Black Sea.