A comprehensive investigation of aqueous-phase photochemical oxidation of 4-ethylphenol.

Secondary organic aerosol (SOA) species formed in atmospheric aqueous phases is recently recognized as an important contributor to fine aerosols, which is known to be a prominent human health risk factor internationally. This work, for the first time, systematically investigated aqueous-phase photochemical oxidation of 4-ethylphenol (4-EP) - a model compound from biomass burning and a surrogate of intermediate volatility organic compounds, under both ultraviolet (UV) (Hg lamp) and simulated sunlight (Xe lamp). We found that 4-EP could degrade upon hydroxal radical (OH) oxidation under UV light nearly 15 times faster than that under simulated sunlight, but large aqueous SOA (aqSOA) yields (108%-122%) were observed under both situations. AqSOA masses and oxidation states continuously increased under simulated sunlight, yet they increased first then decreased quickly under UV light. We proposed a reaction scheme based on identified products, showing that oligomerization, functionalization and fragmentation all can occur during 4-EP oxidation. Our results demonstrate that OH radical may suppress oligomerization and functionalization, but is favorable for fragmentation. Under UV light with HO (high OH), fragmentation was dominant, producing more volatile and smaller molecules, and less aqSOA in later oxidation; Under simulated sunlight with HO (moderate OH), functionalization that can form hydroxylated monomer was more important. Moreover, 4-EP oxidation by the organic triplet excited state (C*) could form species with stronger visible light absorptivity than those from OH-mediated oxidation, and the absorptivity showed positive link with contents of humic-like substances.