Measurement report: Size-resolved secondary organic aerosol formation modulated by aerosol water uptake in wintertime haze

Abstract

This study investigated the potential effects of changes in inorganics on aerosol water uptake and, thus, on secondary organic aerosol (SOA) formation in wintertime haze based on the size-resolved measurements of non-refractory fine particulate matter (NR-PM2.5) in Xi'an, northwestern China. The composition of inorganic aerosol showed significant changes in winter 2018–2019 compared to winter 2013–2014, shifting from a sulfate-rich profile to a nitrate-rich profile. In particular, the fraction of sulfate and chloride decreased, but that of nitrate increased in the entire size range, while ammonium mainly increased at larger particle sizes. These changes thus resulted in a size-dependent evolution in water uptake. Increased water uptake was observed in most cases, mainly associated with enhanced contributions of both nitrate and ammonium, with the highest increase ratio reaching 5 %–35 % at larger particle sizes and higher relative humidity (RH>70 %). The non-negligible influence of chloride on aerosol water uptake was also emphasized. The random forest analysis coupled with a Shapley additive explanation algorithm (SHAP) further showed an enhanced relative importance of aerosol water in impacting SOA formation. Aerosol water exhibited a significant contribution to SOA formation during winter 2018–2019, particularly at larger particle sizes. The SHAP value of aerosol water increased alongside higher levels of aerosol water, indicating an enhanced contribution of aerosol water to SOA formation. This implies that the majority of enhanced aerosol water uptake at larger particle sizes and high RH might facilitate the efficient aqueous-phase SOA formation. This study highlights the key role of aerosol water as a medium to link inorganics and organics in their multiphase processes. As challenges to further improve China's air quality remain and because SOA plays an increasing role in haze pollution, these results provide insight into the size-resolved evolution characteristics and offer guidance for future controls.