Global modeling of heterogeneous hydroxymethanesulfonate chemistry

Abstract

Hydroxymethanesulfonate (HMS) has recently been identified as an abundant organosulfur compound in aerosols during winter haze episodes in northern China. It has also been detected in other regions although the concentrations are low. Because of the sparse field measurements, the global significance of HMS and its spatial and seasonal patterns remain unclear. Here, we modify and add to the implementation of HMS chemistry in the GEOS-Chem chemical transport model and conduct multiple global simulations. The model accounts for cloud entrainment and gas–aqueous mass transfer within the rate expressions for heterogeneous sulfur chemistry. Our simulations can generally reproduce quantitative HMS observations from Beijing and show that East Asia has the highest HMS concentration, followed by Europe and North America. The simulated HMS shows a seasonal pattern with higher values in the colder period. Photochemical oxidizing capacity affects the competition of formaldehyde with oxidants (such as ozone and hydrogen peroxide) for sulfur dioxide and is a key factor influencing the seasonality of HMS. The highest average HMS concentration (1–3 µg m−3) and HMS ∕ sulfate molar ratio (0.1–0.2) are found in northern China in winter. The simulations suggest that aqueous clouds act as the major medium for HMS chemistry while aerosol liquid water may play a role if its rate constant for HMS formation is greatly enhanced compared to cloud water.