Rapid Redox Cycling of Fe(II)/Fe(III) in Microdroplets during Iron–Citric Acid Photochemistry

Fe(III) and carboxylic acids are common compositions in atmospheric microdroplet systems like clouds, fogs, and aerosols. Although photochemical processes of Fe(III)-carboxylate complexes have been extensively studied in bulk aqueous solution, relevant information on the dynamic microdroplet system, which may be largely different from the bulk phase, is rare. With the help of the custom-made ultrasonic-based dynamic microdroplet photochemical system, this study examines the photochemical process of Fe(III)-citric acid complexes in microdroplets for the first time. We find that when the degradation extent of citric acid is similar between the microdroplet system and the bulk solution, the significantly lower Fe(II) ratio is present in microdroplet samples due to the rapider reoxidation of photogenerated Fe(II). However, by replacing citric acid with benzoic acid, no much difference in the Fe(II) ratio between microdroplets and bulk solution is observed, which indicates distinct reoxidation pathways of Fe(II). Moreover, the presence of ^•OH scavenger, namely, methanol, greatly accelerates the reoxidation of photogenerated Fe(II) in both citric acid and benzoic acid situations. Further experiments reveal that the high availability of O₂ and the citric acid- or methanol-derived carbon-centered radicals are responsible for the rapider reoxidation of Fe(II) in iron-citric acid microdroplets by prolonging the length of HO₂^•- and H₂O₂-involved radical reaction chains. The results in this study may provide a new understanding about iron-citric acid photochemistry in atmospheric liquid particles, which can further influence the photoactivity of particles and the formation of secondary organic aerosols.