Significantly Accelerated Hydroxyl Radical Generation by Fe(III)–Oxalate Photochemistry in Aerosol Droplets

Abstract

Fe(III)–oxalate complexes are ubiquitous in atmospheric environments, which can release reactive oxygen species (ROS) such as H₂O₂, O^?2–, and OH^? under light irradiation. Although Fe(III)–oxalate photochemistry has been investigated extensively, the understanding of its involvement in authentic atmospheric environments such as aerosol droplets is far from enough, since the current available knowledge has mainly been obtained in bulk-phase studies. Here, we find that the production of OH^? by Fe(III)–oxalate in aerosol microdroplets is about 10-fold greater than that of its bulk-phase counterpart. In addition, in the presence of Fe(III)–oxalate complexes, the rate of photo-oxidation from SO₂ to sulfate in microdroplets was about 19-fold faster than that in the bulk phase. The availability of efficient reactants and mass transfer due to droplet effects made dominant contributions to the accelerated OH^? and SO₄^2– formation. This work highlights the necessary consideration of droplet effects in atmospheric laboratory studies and model simulations.