Methanethiol Concentrations and Sea-Air Fluxes in the Subarctic NE Pacific Ocean

Exchange of volatile organic sulfur from the ocean to the atmosphere impacts the global sulfur cycle and the climate system and is thought to occur mainly via the gas dimethylsulfide (DMS). DMS is produced during degradation of the abundant phytoplankton osmolyte dimethylsulfoniopropionate (DMSP) but bacteria can also convert dissolved DMSP into the sulfur gas methanethiol (MeSH). MeSH has been difficult to measure in seawater because of its high chemical and biological reactivity and, thus, information on MeSH concentrations, distribution and sea-air fluxes is limited. We measured MeSH in the northeast subarctic Pacific Ocean in July 2016, along transects with strong phytoplankton abundance gradients. Water samples obtained with Niskin bottles were analyzed for MeSH by purge-and-trap gas chromatography. Depth profiles showed that MeSH concentrations were high near the surface and declined with depth. Surface waters (5 m depth) had an average MeSH concentration of 0.75 nM with concentrations reaching up to 3nM. MeSH concentrations were correlated (r = 0.47) with microbial turnover of dissolved DMSP which ranged up to 236 nM per day. MeSH was also correlated with total DMSP (r = 0.93) and dissolved DMS (r = 0.63), supporting the conclusion that DMSP was a major precursor of MeSH. Surface water MeSH:DMS concentration ratios averaged 0.19 and ranged up to 0.50 indicating that MeSH was a significant fraction of the volatile sulfur pool in surface waters. Sea-air fluxes of MeSH averaged 15% of the combined DMS+MeSH flux, therefore MeSH contributed an important fraction of the sulfur emitted to the atmosphere from the subarctic NE Pacific Ocean.