Contribution of hydroxymethanesulfonate (HMS) to severe winter haze in the North China Plain

Abstract

Severe winter haze accompanied by high concentrations of fine particulate matter (PM2.5) occurs frequently in the North China Plain and threatens public health. Organic matter (OM) and sulfate are recognized as major components of PM2.5, while atmospheric models often fail to predict their high concentrations during severe winter haze due to incomplete understanding of secondary aerosol formation mechanisms. By using a novel combination of single-particle mass spectrometry and an optimized ion chromatography method, here we show that hydroxymethanesulfonate (HMS), formed by the reaction between formaldehyde (HCHO) and dissolved SO2 in aerosol water, is ubiquitous in Beijing during winter. The HMS concentration and the molar ratio of HMS to sulfate increased with the deterioration of winter haze. High concentrations of precursors (SO2 and HCHO) coupled with low oxidant levels, low temperature, high relative humidity, and moderately acidic pH facilitate the heterogeneous formation of HMS, which could account for up to 15 % of OM in winter haze and lead to up to 36 % overestimates of sulfate when using traditional ion chromatography. Despite the clean air actions having substantially reduced SO2 emissions, the HMS concentration and molar ratio of HMS to sulfate during severe winter haze increased from 2015 to 2016 with the growth in HCHO concentration. Our findings illustrate the significant contribution of heterogeneous HMS chemistry to severe winter haze in Beijing, which helps to improve the prediction of OM and sulfate and suggests that the reduction in HCHO can help to mitigate haze pollution.