Efficient control of atmospheric sulfate production based on three formation regimes

Abstract

The formation of sulfate (SO42−) in the atmosphere is linked chemically to its direct precursor, sulfur dioxide (SO2), through several key oxidation paths for which nitrogen oxides or NOx (NO and NO2) play essential roles. Here we present a coherent description of the dependence of SO42– formation on SO2 and NOx under haze-fog conditions, in which fog events are accompanied by high aerosol loadings and fog-water pH in the range of 4.7–6.9. Three SO42– formation regimes emerge as defined by the role played by NOx. In the low-NOx regime, NOx act as catalyst for HOx, which is a major oxidant for SO2, whereas in the high-NOx regime, NO2 is a sink for HOx. Moreover, at highly elevated NOx levels, a so-called NO2-oxidant regime exists in which aqueous NO2 serves as the dominant oxidant of SO2. This regime also exists under clean fog conditions but is less prominent. Sensitivity calculations using an emission-driven box model show that the reduction of SO42– is comparably sensitive to the reduction of SO2 and NOx emissions in the NO2-oxidant regime, suggesting a co-reduction strategy. Formation of SO42− is relatively insensitive to NOx reduction in the low-NOx regime, whereas reduction of NOx actually leads to increased SO42– production in the intermediate high-NOx regime. Distinct dependence of atmospheric SO42– formation on NOx levels in haze-fog events is revealed by SO42– production isopleths that are obtained through simulations of atmospheric chemistry with a box model.