Oceanic emissions of dimethyl sulfide and methanethiol and their contribution to sulfur dioxide production in the marine atmosphere

Oceanic emissions of dimethyl sulfide (CH3SCH3, DMS) have long been recognized to impact aerosol particle composition and size, the concentration of cloud condensation nuclei (CCN), and Earth's radiation balance. The impact of oceanic emissions of methanethiol (CH3SH, MeSH), which is produced by the same oceanic precursor as DMS, on the volatile sulfur budget of the marine atmosphere is largely unconstrained. Here we present direct flux measurements of MeSH oceanic emissions using the eddy covariance (EC) method with a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToFMS) detector and compare them to simultaneous flux measurements of DMS emissions from a coastal ocean site. Campaign mean mixing ratios of DMS and MeSH were 72 ppt (28-90 ppt interquartile range) and 19.1 ppt (7.6-24.5 ppt interquartile range), respectively. Campaign mean emission fluxes of DMS (F-DMS) and MeSH (F-MeSH) were 1.13 ppt m s(-1)(0.53-1.61 ppt m s(-1) interquartile range) and 0.21 ppt m s -1 (0.10-0.31 ppt m s(-1) interquartile range), respectively. Linear least squares regression of observed MeSH and DMS flux indicates the emissions are highly correlated with each other (R-2 = 0.65) over the course of the campaign, consistent with a shared oceanic source. The campaign mean DMS to MeSH flux ratio (F-DMS : F-MeSH) was 5.5 +/- 3.0, calculated from the ratio of 304 individual coincident measurements of F-DMS : F-MeSH. Measured F-DMS : F-MeSH was weakly correlated (R-2 = 0.15) with ocean chlorophyll concentrations, with F-DMS : F-MeSH reaching a maximum of 10.8 +/- 4.4 during a phytoplankton bloom period. No other volatile sulfur compounds were observed by PTR-ToFMS to have a resolvable emission flux above their flux limit of detection or to have a gas-phase mixing ratio consistently above their limit of detection during the study period, suggesting DMS and MeSH are the dominant volatile organic sulfur compounds emitted from the ocean at this site. The impact of this MeSH emission source on atmospheric budgets of sulfur dioxide (SO2) was evaluated by implementing observed emissions in a coupled ocean-atmosphere chemical box model using a newly compiled MeSH oxidation mechanism. Model results suggest that MeSH emissions lead to afternoon instantaneous SO2 production of 2.5 ppt h(-1), which results in a 43 % increase in total SO2 production compared to a case where only DMS emissions are considered and accounts for 30% of the instantaneous SO2 production in the marine boundary layer at the mean measured F-DMS and F-MeSH. This contribution of MeSH to SO2 production is driven by a higher effective yield of SO2 from MeSH oxidation and the shorter oxidation lifetime of MeSH compared to DMS. This large additional source of marine SO2 has not been previously considered in global models of marine sulfur cycling. The field measurements and modeling results presented here demonstrate that MeSH is an important contributor to volatile sulfur budgets in the marine atmosphere and must be measured along with DMS in order to constrain marine sulfur budgets. This large additional source of marine-reduced sulfur from MeSH will contribute to particle formation and growth and CCN abundance in the marine atmosphere, with subsequent impacts on climate.