Atmospheric evolution of environmentally persistent free radicals in rural North China Plain: insights into water solubility and effects on PM_2.5 oxidative potential

Abstract. Environmentally Persistent Free Radicals (EPFRs) represent a novel class of hazardous substances, posing risks to human health and the environment. In this study, we investigated the EPFRs in ambient fine, coarse, and total suspended particulate matter (PM_2.5, PM₁₀, TSP) in rural North China Plain, where local primary emissions of EPFRs were limited. We observed that the majority of EPFRs occurred in PM_2.5. Moreover, distinct seasonal patterns and higher g-factors of EPFRs were found compared to those in urban environments, suggesting unique characteristics of EPFRs in rural areas. The source apportionment analyses revealed atmospheric oxidation as the largest contributor (33.6 %) to EPFRs. A large water-soluble fraction (35.2 %) of EPFRs was determined, potentially resulting from the formation of more oxidized EPFRs through atmospheric oxidation processes during long-range/regional transport. Additionally, significant positive correlations were observed between EPFRs and the oxidative potential of water-soluble PM_2.5 measured by dithiothreitol-depletion and hydroxyl-generation assays, likely attributable to the water-soluble fractions of EPFRs. Overall, our findings reveal the prevalence of water-soluble EPFRs in rural areas and underscore atmospheric oxidation processes can modify their properties, such as increasing their water solubility. This evolution may alter their roles in contributing to the oxidative potential of PM_2.5 and potentially also influence their impact on climate-related cloud chemistry.