Publication Details (including relevant citation information):
Condensed-phase chemistry plays a significant role in the formation and evolution of atmospheric organic aerosols. Past studies of the aqueous photoformation of secondary organic aerosol (SOA) have largely focused on hydroxyl radical oxidation, but here we show that triplet excited states of organic compounds (3C*) can also be important aqueous oxidants. We studied the aqueous photoreactions of three phenols (phenol, guaiacol, and syringol) with the aromatic carbonyl 3,4-dimethoxybenzaldehyde (DMB); all of these species are emitted by biomass burning. Under simulated sunlight, DMB forms a triplet excited state that rapidly oxidizes phenols to form low-volatility SOA. Rate constants for these reactions are fast and increase with decreasing pH and increasing methoxy substitution of the phenols. Mass yields of aqueous SOA are near 100% for all three phenols. For typical ambient conditions in areas with biomass combustion, the aqueous oxidation of phenols by 3C* is faster than by hydroxyl radical, although rates depend strongly on pH, oxidant concentrations, and the identity of the phenol. Our results suggest that 3C* can be the dominant aqueous oxidant of phenols in areas impacted by biomass combustion and that this is a significant pathway for forming SOA.
Address (URL): http://pubs.acs.org/doi/abs/10.1021/es4045715