Photochemical Aging of Atmospheric Particulate Matter in the Aqueous Phase

This study focused on the photoaging of atmospheric particulate matter smaller than 2.5 μm (PM_2.5) in the aqueous phase. PM_2.5 was collected during a winter, a spring, and a summer campaign in urban and rural settings in Colorado and extracted into water. The aqueous extracts were photoirradiated using simulated sunlight, and the production rate (r_•OH) and the effects of hydroxyl radicals (^•OH) were measured as well as the optical properties as a function of the photoaging of the extracts. r_•OH was seen to have a strong seasonality with low mean values for the winter and spring extracts (4.8 and 14 fM s^-1 mg_C^-1 L, respectively) and a higher mean value for the summer extracts (65.4 fM s^-1 mg_C^-1 L). For the winter extracts, ^•OH was seen to mostly originate from nitrate photolysis while for the summer extracts, a correlation was seen between r_•OH and iron concentration. The extent of photobleaching of the extracts was correlated with r_•OH, and the correlation also indicated that non-^•OH processes took place. Using the ^•OH measurements and singlet oxygen (¹O₂) measurements, the half-life of a selection of compounds was modeled in the atmospheric aqueous phase to be between 1.9 and 434 h.