In-cloud formation of secondary species in iron-containing particles

Abstract

The increase in secondary species through cloud processing potentially increases aerosol iron (Fe) bioavailability. In this study, a ground-based counterflow virtual impactor coupled with a real-time single-particle aerosol mass spectrometer was used to characterize the formation of secondary species in Fe-containing cloud residues (dried cloud droplets) at a mountain site in southern China for nearly 1 month during the autumn of 2016. Fe-rich, Fe-dust, Fe-elemental carbon (Fe-EC), and Fe-vanadium (Fe-V) cloud residual types were obtained in this study. The Fe-rich particles, related to combustion sources, contributed 84 % (by number) to the Fe-containing cloud residues, and the Fe-dust particles represented 12 %. The remaining 4 % consisted of the Fe-EC and Fe-V particles. It was found that above 90 % (by number) of Fe-containing particles had already contained sulfate before cloud events, leading to no distinct change in number fraction (NF) of sulfate during cloud events. Cloud processing contributed to the enhanced NFs of nitrate, chloride, and oxalate in the Fe-containing cloud residues. However, the in-cloud formation of nitrate and chloride in the Fe-rich type was less obvious relative to the Fe-dust type. The increased NF of oxalate in the Fe-rich cloud residues was produced via aqueous oxidation of oxalate precursors (e.g., glyoxylate). Moreover, Fe-driven Fenton reactions likely increase the formation rate of aqueous-phase OH, improving the conversion of the precursors to oxalate in the Fe-rich cloud residues. During daytime, the decreased NF of oxalate in the Fe-rich cloud residues was supposed to be due to the photolysis of Fe-oxalate complexes. This work emphasizes the role of combustion Fe sources in participating in cloud processing and has important implications for evaluating Fe bioavailability from combustion sources during cloud processing.