Consistency Between Measurements and Theory for Sulfur Gases and Oxidants During the Pacific Atmospheric Sulfur Experiment

Airborne gas phase measurements of sulfur dioxide, dimethylsulfide, dimethylsulfoxide, methane sulfonic acid, sulfuric acid, hydroxyl, perhydroxyl, hydrogen peroxide, methylhydroperoxide, ozone, and carbon monoxide together with aerosol microphysical properties and bulk and size-dependent aerosol composition are examined for consistency with photochemical theory. The observations come from 14 research flights using the NCAR C-130 flown mostly southeast of Kiritimati in relatively cloud-free marine boundary layer air. This region was chosen because of its extremely low nitrogen oxide mixing ratios and minimal horizontal gradients in composition. A size-dependent gas-particle mass-transfer model is used to calculate the exchange rates of dimethylsulfoxide, methanesulfonic acid and sulfuric acid between the gas and aerosol. Gas kinetic reactions, aqueous reactions, and heterogeneous processes are used in the evaluation. Mass accommodation coefficients, Henry's Law solubilities, and the effective yields of methanesulfonic acid, sulfur dioxide, sulfuric acid and dimethylsulfoxide from dimethylsulfide are estimated and consistent with the literature. Gas phase hydroxyl chemistry alone is sufficient to explain observed methanesulfonic acid and sulfuric acid vapor concentrations.