Abstract. Vanillin (VL), a phenolic aromatic carbonyl abundant in biomass burning emissions, forms triplet excited states (3VL∗) under
simulated sunlight leading to aqueous secondary organic aerosol (aqSOA)
formation. Nitrate and ammonium are among the main components of biomass
burning aerosols and cloud or fog water. Under atmospherically relevant cloud and fog conditions, solutions composed of either VL only or VL with ammonium nitrate were subjected to simulated sunlight irradiation to compare aqSOA formation via the direct photosensitized oxidation of VL in the absence and presence of ammonium nitrate. The reactions were characterized by examining the VL decay kinetics, product compositions, and light absorbance changes. Both conditions generated oligomers, functionalized monomers, and oxygenated ring-opening products, and ammonium nitrate promoted functionalization and nitration, likely due to its photolysis products (⚫OH, ⚫NO2, and NO2- or HONO). Moreover, a potential imidazole derivative observed in the presence of ammonium nitrate suggested that ammonium participated in the reactions. The majority of the most abundant products from both conditions were potential brown carbon (BrC) chromophores. The effects of oxygen (O2), pH, and reactants concentration and molar ratios on the reactions were also explored. Our findings show that O2 plays an essential role in the reactions, and oligomer formation was enhanced at pH <4. Also, functionalization was dominant at low VL concentrations, whereas oligomerization was favored at high VL concentrations. Furthermore, oligomers and hydroxylated products were
detected from the oxidation of guaiacol (a non-carbonyl phenol) via VL
photosensitized reactions. Last, potential aqSOA formation pathways via
the direct photosensitized oxidation of VL in the absence and presence of
ammonium nitrate were proposed. This study indicates that the direct
photosensitized oxidation of VL may be an important aqSOA source in areas
influenced by biomass burning and underscores the importance of nitrate in
the aqueous-phase processing of aromatic carbonyls.