Multiphase interactions between sulfur dioxide and secondary organic aerosol from the photooxidation of toluene: Reactivity and sulfate formation

There is growing evidence that the interactions between sulfur dioxide (SO2) and organic peroxides (POs) in aerosol and clouds play an important role in atmospheric sulfate formation and aerosol aging, yet the reactivity of POs arising from anthropogenic precursors toward SO2 remains unknown. In this study, we investigate the multiphase reactions of SO2 with secondary organic aerosol (SOA) formed from the photooxidation of toluene, a major type of anthropogenic SOA in the atmosphere. The reactive uptake coefficient of SO2 on toluene SOA was determined to be on the order of 10−4, depending strikingly on aerosol water content. POs contribute significantly to the multiphase reactivity of toluene SOA, but they can only explain a portion of the measured SO2 uptake, suggesting the presence of other reactive species in SOA that also contribute to the particle reactivity toward SO2. The second-order reaction rate constant (kII) between S(IV) and toluene-derived POs was estimated to be in the range of the kII values previously reported for commercially available POs (e.g., 2-butanone peroxide and 2-tert-butyl hydroperoxide) and the smallest (C1-C2) and biogenic POs. In addition, unlike commercial POs that can efficiently convert S(IV) into both inorganic sulfate and organosulfates, toluene-derived POs appear to mainly oxidize S(IV) to inorganic sulfate. Our study reveals the multiphase reactivity of typical anthropogenic SOA and POs toward SO2 and will help to develop a better understanding of the formation and evolution of atmospheric secondary aerosol. [Display omitted] •Multiphase reactivity of SOA toward SO2 depends markedly on aerosol water content.•Organic peroxides only explain a portion of the measured SO2 uptake on SOA.•Toluene-derived peroxides react with SO2 as efficiently as biogenic peroxides.•Toluene-derived peroxides mainly oxidize SO2 to inorganic sulfate.