Naturally-Occurring DMSP Analogs as Potential Precursors of Dimethyl Sulfide (DMS) and Methanethiol (MeSH) in Coastal Seawater

Dimethylsulfoniopropionate (DMSP) is an osmolyte produced by various macroalgae and phytoplankton in the marine environment. DMSP is known to be the main precursor for dimethyl sulfide (DMS), the major natural sulfur gas emitted from the oceans to the atmosphere. DMS contributes to formation and growth of sulfur-containing aerosols in our stratosphere. These aerosols influence Earth’s solar radiation balance and potentially affect the formation of clouds, which could function as a counter-effect to global warming. Bacterioplankton are capable of converting DMSP into DMS via the enzyme DMSP lyase. But not all DMSP in the ocean is converted into DMS. A significant fraction of the DMSP available in the ocean is converted to methanethiol (MeSH) via the bacterial demethylation/demethiolation pathway, with a portion of the MeSH being assimilated as both a carbon and sulfur source. Here we test whether several other naturally-occurring dimethyl sulfonium compounds could be precursors of DMS and MeSH. To test this, we carried out experiments with estuarine water samples from Mobile Bay in the Northern Gulf of Mexico. After collection, unfiltered seawater and seawater filtrate samples, the later containing bacteria only, were treated with 50 nM additions of either 2-dimethylsulfononioacetate (DMSA) or S-Methylmethionine (SMM). After addition of the dimethyl sulfonium compounds, samples were analyzed for sulfur gases with Gas Chromatography-Flame Photometric Detection, using cryogenic-trapping techniques. Addition of DMSA resulted in an immediate increase in MeSH production in both seawater and seawater filtrate containing bacteria only, producing even more MeSH than DMSP. This suggests that DMSA is potentially a significant precursor for MeSH. DMS was not produced in significant amounts from DMSA. Addition of SMM resulted in low rates of both DMS and MeSH accumulation in both seawater samples, indicating that SMM may be a minor precursor for both gases compared to DMSP.