Evidence for the biological turnover of thiols in anoxic marine sediments

The concentrations of methanethiol (MSH) and 3-mercaptopropionate (3-MPA) increased for a period of up to 24 h in fresh slurries of anoxic Biscayne Bay sediments. Other endogenous thiols such as glutathione (GSH) deceased immediately after slurry preparation or were not detectable at all. The maximum concentrations reached by 3-MPA and MSH were sometimes as high as 1 M, but were usually in the 100 to 300 nM range. After the initial increases, the concentrations of these thiols decreased rapidly to nearly constant levels of 20 nM for MSH and < 1nM for 3-MPA. In pre-incubated slurries, which had constant levels of thiols, the addition of microbial inhibitors including tungstate, molybdate, chloroform, and a mixture of chloramphenicol plus tetracycline caused MSH and 3-MPA to accumulate steadily. In the presence of inhibitors, accumulation rates of MSH ranged from 18 to 730 nM · d^-1 and those of 3-MPA ranged from 0 to 185 nM · d^-1. Tungstate and chloroform generally gave the highest accumulation rates, while molybdate gave the lowest, possibly due to its complexation with sulfhydryl compounds. BES (2-Bromoethanesulfonate) was also tested for its effects, but no 3-MPA and only trace amounts (19 nM · d^-1) of MSH accumulated with this treatment. However, additions of BES (10 mM) to sulfidic sediments caused significant (8 M · d^-1) production of 2-mercaptoethanesulfonate (HS-CoM). Formation of HS-CoM was abiotic and was due to sulfide attack on the bromine atom in BES. The accumulations of 3-MPA and MSH in the presence of several different microbial inhibitors, suggests that these thiols may turn over in anoxic sediments. The relatively low concentrations of thiols observed in pore water profiles may be due to continuous microbial removal of these compounds. Much larger amounts of thiols were associated with sediment particles than present in the pore water. Evidence is presented which suggests that bound thiols may be exchangeable with the porewater, and therefore potentially available for microbial consumption.