Despite its impact on the climate, the mechanism of methanesulfonic acid (MSA) formation in the oxidation of dimethyl sulfide (DMS) remains unclear. The DMS + OH reaction is known to form methanesulfinic acid (MSIA), methane sulfenic acid (MSEA), the methylthio radical (CH3S), and hydroperoxymethyl thioformate (HPMTF). Among them, HPMTF reacts further to form SO2 and OCS, while the other three form the CH3SO2 radical. Based on theoretical calculations, we find that the CH3SO2 radical can add O2 to form CH3S(O)2OO, which can react further to form MSA. The branching ratio is highly temperature sensitive, and the MSA yield increases with decreasing temperature. In warmer regions, SO2 is the dominant product of DMS oxidation, while in colder regions, large amounts of MSA can form. Global modeling indicates that the proposed temperature-sensitive MSA formation mechanism leads to a substantial increase in the simulated global atmospheric MSA formation and burden.
Keywords: dimethyl sulfide oxidation; global modeling; mechanism; quantum chemical computation; sulfuric acid.