The role of sulfur in the formation of humic polymers in marine sediments
- Brookhaven National Lab., Upton, NY (United States)
In anoxic marine sediments, hydrogen sulfide formed from bacterial sulfate reduction significantly impacts the diagenesis and preservation of organic matter through incorporating sulfur into the latter; however, the underlying geochemical mechanisms are still unclear. We used XANES spectroscopy to investigate whether di- and poly-sulfide linkages are involved in the formation of humic polymers in anaerobic marine sediments. The approach was to treat the humic acids with tributyl phosphine, that cleaves di- and polysulfide linkages, and to examine the changes in XANES spectra before and after such treatment. With simple di- and polysulfide linkages, and to examine the changes in XANES spectra before and after such treatment. With simple di- and poly-sulfide compounds (benzyl disulfide and trisulfide), the shape of the XANES spectra changed when treated with tributyl phosphine because of the formation of sulfhydryl groups. A similar effect was observed for sedimentary humic acids isolated from a salt marsh in Shelter Island, suggesting that di- and poly-sulfide linkages are indeed involved in forming humic polymers. We determined by liquid chromatography, two major low-molecular-weight thiols, 3-mercatopropionate and methane thiol, among the compounds released from tributyl phosphine treated humics. These thiols can be easily degraded by sedimentary bacteria when they are present in solution. However, both thiols were present as components of the humic substances throughout the sediment column, down to the 22-cm depth sampled, suggesting that incorporation into humic polymers, in fact, provides a mechanism for preventing mineralization of the bound organic matter. In general, humic polymers resist microbial degradation because of their randomly polymerized structure.
- OSTI ID:
- 539017
- Report Number(s):
- CONF-960807--
- Country of Publication:
- United States
- Language:
- English
Similar Records
Sulfur and nitrogen speciation in humic substances by x-ray absorption near-edge structure spectroscopy
XANES studies of oxidation states of sulfur in aquatic and soil humic substances