A. Vairavamurthy et al., OXIDATION-STATE OF SULFUR IN THIOSULFATE AND IMPLICATIONS FOR ANAEROBIC ENERGY-METABOLISM, Geochimica et cosmochimica acta, 57(7), 1993, pp. 1619-1623
Disproportionation of thiosulfate is an important pathway in bacterial
energy metabolism in anoxic sediments. It has been described as an in
organic fermentation process in which a part of the molecule is oxidiz
ed to sulfate, while the other stoichiometrically equivalent part is u
sed as electron acceptor and reduced to sulfide. However, an intramole
cular redox change is difficult to envisage because, according to the
currently held view, the two sulfur atoms of thiosulfate exist in the
oxidation state of sulfate (+6) and sulfide (-2) and do not change the
ir respective oxidation states upon disproportionation. Our results ba
sed on XANES spectroscopy indicate that the two different sulfur atoms
in thiosulfate have charge densities corresponding to +5 and -1 oxida
tion states which support a redox mechanism in the disproportionation
of thiosulfate to sulfate and sulfide.