Superoxide Formation from Aqueous Reactions of Biogenic Secondary Organic Aerosols.

Reactive oxygen species (ROS) play a central role in aqueous-phase processing and health effects of atmospheric aerosols. Although hydroxyl radical (•OH) and hydrogen peroxide (H2O2) are regarded as major oxidants associated with secondary organic aerosols (SOA), the kinetics and reaction mechanisms of superoxide (O2•-) formation are rarely quantified and poorly understood. Here, we demonstrate a dominant formation of O2•- with molar yields of 0.01-0.03% from aqueous reactions of biogenic SOA generated by •OH photooxidation of isoprene, β-pinene, α-terpineol, and d-limonene. The temporal evolution of •OH and O2•- formation is elucidated by kinetic modeling with a cascade of aqueous reactions including the decomposition of organic hydroperoxides, •OH oxidation of primary or secondary alcohols, and unimolecular decomposition of α-hydroxyperoxyl radicals. Relative yields of various types of ROS reflect a relative abundance of organic hydroperoxides and alcohols contained in SOA. These findings and mechanistic understanding have important implications on the atmospheric fate of SOA and particle-phase reactions of highly oxygenated organic molecules as well as oxidative stress upon respiratory deposition.