Heterogeneous photochemical uptake of SO2 on typical brown carbon species: A significant sulfate source

Abstract

The heterogeneous reactions of SO2 on organic aerosols (OA) have been proposed as a significant source of sulfates. The photochemical conversion of SO2 to sulfates on the surface of light-absorbing OA, i.e., brown carbon (BrC), remained slight understanding. Herein, the photochemical uptake of SO2 on typical BrC species, including aromatic carbonyl compounds (ACs), polycyclic aromatic hydrocarbons (PAHs) and phenols (PHs), was systematically investigated by a flow tube reactor. Light can significantly promote the uptake of SO2 on all BrC species used here, especially for ACs. The initial and steady-state uptake coefficients (γi and γss) of SO2 exhibited positive relationships with the light intensity, whereas they negatively correlated with the initial SO2 concentration. Significant sulfate formation was clearly observed with in situ attenuated total internal reflection infrared (ATR-IR) spectrometer, and H2O and O2 had obvious enhancement effects on the sulfate production. Photoinduced •OH, which primarily originated from •O2− that was generated through an electron transfer process on BrC under irradiation, was determined to be a key driver for the oxidation of SO2 to sulfates. Finally, SO2 lifetime and sulfate formation rate were evaluated on the basis of experimental results, highlighting potential contributions of BrC photochemistry to atmospheric SO2 loss and sulfate sources.