Brown Carbon Aerosol Formation by Multiphase Catechol Photooxidation in the Presence of Soluble Iron

Catechol (1,2-benzenediol), a common phenolic species emitted during biomass burning, is both redox active and metal chelating. When oxidized by OH radicals in the aqueous phase, it rapidly forms brown carbon (BrC). Here, we report chamber studies of the multiphase chemistry of catechol using HOOH as an OH radical source, soluble iron, simulated sunlight, and either deliquesced or solid-phase seed particles. BrC of remarkable similarity ( MAC 365 = 1.7 ±0.2 m 2 g –1, “medium-BrC” category) was produced whenever gas-phase catechol was photolyzed in the chamber, with or without the presence of an OH radical source, soluble iron, or deliquesced aerosol. The speed and quantity of BrC formation varied, however. While BrC production was slower in the absence of an OH radical source, multiple lines of evidence suggest that OH generation via photosensitization by surface-adsorbed catechol can still generate BrC. Fenton chemistry actively occurred in surface-adsorbed water layers even below the seed particle deliquescence point, leading to significant production of gas-phase benzoquinone. Ratios of BrC and secondary organic aerosol (SOA) relative to catechol concentrations were highest in the presence of trace amounts of soluble iron, HOOH, and simulated sunlight, indicating that photo-Fenton chemistry contributed substantially to BrC and SOA formation by catechol. Finally, we observed that BrC and SOA formation by catechol/photo-Fenton chemistry can occur efficiently even at 40% RH. These results are consistent with catechol being a major source of secondary BrC in biomass burning plumes, even at moderate relative humidity.