Photoenhanced sulfate formation by the heterogeneous uptake of SO₂ on non-photoactive mineral dust

Abstract

Heterogeneous uptake of SO2 on mineral dust is a predominant formation pathway of sulfates, whereas the contribution of photo-induced SO2 oxidation to sulfates on the dust interfaces still remains unclear. Here, we investigated heterogeneous photochemical reactions of SO2 on five mineral oxides (SiO2, kaolinite, Al2O3, MgO, and CaO) without photocatalytic activity. Light enhanced the uptake of SO2, and its enhancement effects negatively depended on the basicity of mineral oxides. The initial uptake coefficient (γ0,BET) and the steady-state uptake coefficient (γs,BET) of SO2 positively relied on light intensity, relative humidity (RH), and O2 content, while they exhibited a negative relationship with the initial SO2 concentration. Rapid sulfate formation during photo-induced heterogeneous reactions of SO2 with all mineral oxides was confirmed to be ubiquitous, and H2O and O2 played key roles in the conversion of SO2 to sulfates. In particular, triplet states of SO2 (3SO2) were suggested to be the trigger for photochemical sulfate formation. Atmospheric implications supported a potential contribution of interfacial SO2 photochemistry on non-photoactive mineral dust to atmospheric sulfate sources.