Multiphase Oxidation of Sulfur Dioxide in Aerosol Particles: Implications for Sulfate Formation in Polluted Environments.

ABSTRACT

Atmospheric oxidation of sulfur dioxide (SO2) forms sulfate-containing aerosol particles that impact air quality, climate, and human and ecosystem health. It is well-known that in-cloud oxidation of SO2 frequently dominates over gas-phase oxidation on regional and global scales. Multiphase oxidation involving aerosol particles, fog, and cloud droplets has been generally thought to scale with liquid water content (LWC) so multiphase oxidation would be negligible for aerosol particles due to their low aerosol LWC. However, recent field evidence, particularly from East Asia, shows that fast sulfate formation prevails in cloud-free environments that are characterized by high aerosol loadings. By assuming that the kinetics of cloud water chemistry prevails for aerosol particles, most atmospheric models do not capture this phenomenon. Therefore, the field of aerosol SO2 multiphase chemistry has blossomed in the past decade, with many oxidation processes proposed to bridge the difference between modeled and observed sulfate mass loadings. This review summarizes recent advances in the fundamental understanding of the aerosol multiphase oxidation of SO2, with a focus on environmental conditions that affect the oxidation rate, experimental challenges, mechanisms and kinetics results for individual reaction pathways, and future research directions. Compared to dilute cloud water conditions, this paper highlights the differences that arise at the molecular level with the extremely high solute strengths present in aerosol particles.