A light - Driven acidic positive feedback mechanism of sulfate formation.

As the main source of atmospheric sulfate aerosol, the aqueous-phase oxidation of SO 2 has been of great concern. Traditionally, the aqueous-phase oxidation of SO 2 is considered a consumption process of atmospheric oxidation capacity; however, we report here that •OH radicals and other reactive oxygen species (ROS) can be generated in the photochemical reactions of bulk HSO 3 − solution. This •OH production pathway results in the fast sulfate formation in the photooxidation of dissolved SO 2. The photochemical process is determined to be pH-dependent in which sulfate formation is promoted by decreasing pH. Hence, a light - driven acidic positive feedback mechanism is proposed that the oxidation of dissolved SO 2 and the formation of •OH radicals have a synergistic promoting effect. These results indicate that the photochemistry of dissolved SO 2 could be a missing source of aqueous •OH radicals as well as sulfate at regional to global scales. [Display omitted] • Aqueous-phase photooxidation of SO 2 is an important sulfate formation pathway. • Acidity promotes rather than inhibits the aqueous-phase photooxidation of SO 2. • SO 2 is not only a consumer but also an initiator of reactive oxygen species. [ABSTRACT FROM AUTHOR]