Iron-Facilitated Organic Radical Formation from Secondary Organic Aerosols in Surrogate Lung Fluid

Respiratory deposition of secondary organic aerosols (SOA) and iron may lead to the generation of reactive oxygen species and free radicals in lung fluid to cause oxidative stress, but their underlying mechanism and formation kinetics are not well understood. Here we demonstrate substantial formation of organic radicals in surrogate lung fluid (SLF) by mixtures of Fe²⁺ and SOA generated from photooxidation of isoprene, α-terpineol, and toluene. The molar yields of organic radicals by SOA are measured to be 0.03-0.5% in SLF, which are 5-10 times higher than in water. We observe that Fe²⁺ enhances organic radical yields dramatically by a factor of 20-80, which can be attributed to Fe²⁺-facilitated decomposition of organic peroxides, in consistency with a positive correlation between peroxide contents and organic radical yields. Ascorbate mediates redox cycling of iron ions to sustain organic peroxide decomposition, as supported by kinetic modeling reproducing time- and concentration-dependence of organic radical formation as well as additional experiments observing the formation of Fe²⁺ and ascorbate radicals in mixtures of ascorbate and Fe³⁺. ^•OH and superoxide are found to be scavenged by antioxidants efficiently. These findings have implications on the role of organic radicals in oxidative damage and lipid peroxidation.