Chamber studies of OH + dimethyl sulfoxide and dimethyl disulfide: insights into the dimethyl sulfide oxidation mechanism

Abstract. The oxidation of dimethyl sulfide (DMS) in the marine atmosphere represents an important natural source of non-sea-salt sulfate aerosol, but the chemical mechanisms underlying this process remain uncertain. While recent studies have focused on the role of the peroxy-radical isomerization channel in DMS oxidation, this work revisits the impact of the other channels (OH addition, OH abstraction followed by bimolecular RO2 reaction) on aerosol formation from DMS. Due to the presence of common intermediate species, the oxidation of dimethyl sulfoxide (DMSO) and dimethyl disulfide (DMDS) can shed light on these two DMS reaction channels; they are also both atmospherically relevant species in their own right. This work examines the OH-oxidation of DMSO and DMDS, using chamber experiments monitored by chemical ionization mass spectrometry and aerosol mass spectrometry to study the full-range of sulfur-containing products under low- and high-NO conditions. The oxidation of both compounds is found to lead to rapid aerosol formation (which does not involve the intermediate formation of SO2), with a substantial fraction (14–47 % S yield for DMSO, and 5–21 % for DMDS) of reacted sulfur ending up in the particle phase, and the highest yields observed under elevated NO conditions. Aerosol is observed to consist mainly of sulfate, methanesulfonic acid, and methanesulfinic acid. In the gas phase, the NOX dependence of several products, including SO2 and S2-containing organosulfur species, suggest reaction pathways not included in current mechanisms. Based on the commonalities with the DMS oxidation mechanism, DMSO and DMDS results are used to reconstruct DMS aerosol yields; these reconstructions roughly match DMS aerosol yield measurements from the literature but differ in composition, underscoring remaining uncertainties in sulfur chemistry. This work indicates that both the abstraction and addition channels contribute substantially to rapid aerosol formation from DMS, and highlights the need for more study into the fate of small sulfur radical intermediates (e.g., CH3S, CH3SO2, CH3SO3) that play central roles in the DMS oxidation mechanism.