Comment on acp-2022-309

Abstract

Fires emit sufficient sulfur to affect local and regional air quality and climate. This study analyzes SO2 emission factors and variability in smoke plumes from US wild and agricultural fires, and their relationship to sulfate and hydroxymethanesulfonate (HMS) formation. Observed SO2 emission factors for various fuel types show good agreement with the latest reviews of biomass burning emission factors, producing an emission factor range of 0.47–1.2 g SO2 kg-1 C in the emissions. These emission factors vary with geographic location in a way that suggests that deposition of coal burning emissions and application of sulfur-containing fertilizers likely play a role in the larger observed values, which are primarily associated with agricultural burning. A 0-D box model generally reproduces the observed trends of SO2 and total sulfate (inorganic + organic) in aging wildfire plumes. In many cases, modeled HMS is consistent with the observed organosulfur concentrations. However, a comparison of observed organosulfur and modeled HMS suggests that multiple organosulfur compounds are likely responsible for the observations, but that the chemistry of these compounds yield similar production and loss rates to that of HMS, resulting in good agreement with the modeled results. We provide suggestions for constraining the organosulfur compounds observed during these flights and we show that the chemistry of HMS can allow for organosulfur to act as a S(IV) reservoir under conditions of increased pH (>6) and liquid water content (>10-7 g m-3). This can facilitate long-range transport of sulfur emissions resulting in increased SO2 and eventually sulfate in transported smoke.