Production of Atmospheric Organosulfates via Mineral-Mediated Photochemistry

Although organosulfates (ROSO₃^–) comprise a significant component of secondary organic aerosol (SOA) mass, their atmospheric formation mechanisms are not fully understood. Here, using methacrolein as a model organosulfate precursor, we present a new, mineral-mediated photochemical pathway for organosulfate formation. First, we describe studies of TiO₂-catalyzed formation of the atmospherically important organosulfate hydroxyacetone sulfate from methacrolein as a function of illumination time, catalyst loading, sulfate concentration, counterion identity, and methacrolein concentration. Then, we propose a sulfate radical-mediated mechanism for organosulfate formation consistent with these observations. Finally, we show that natural Ti-containing minerals and road dust not only catalyze the formation of comparable amounts of hydroxyacetone sulfate to those formed in the presence of commercial TiO₂ but also facilitate the production of additional organosulfate species. These results highlight the complex nature of photochemistry at the surface of natural mineral samples and underscore the need for further study of the role of mineral–organic interactions in atmospheric organosulfate formation.