Nitrite-Mediated Photooxidation of Vanillin in the Atmospheric Aqueous Phase

Nitrite (NO₂^-) and its conjugate acid, nitrous acid (HNO₂), have long been recognized as a ubiquitous atmospheric pollutant as well as an important photochemical source of hydroxyl radicals (·OH) and reactive nitrogen species (·NO, ·NO₂, ·N₂O₃, etc.) in both the gas phase and aqueous phase. Although NO₂^-/HNO₂ plays an important role in atmospheric chemistry, our understanding on its role in the chemical evolution of organic components in atmospheric waters is rather incomplete and is still in dispute. In this study, the nitrite-mediated photooxidation of vanillin (VL), a phenolic compound abundant in biomass burning emissions, was investigated under pH conditions relevant for atmospheric waters. The influence of solution pH, dissolved oxygen, and ·OH scavengers on the nitrite-mediated photooxidation of VL was discussed in detail. Our study reveals that the molecular composition of the products is dependent on the molar ratio of NO₂^-/VL in the solution and that nitrophenols are the major reaction products. We also found that the light absorbance of the oxidative products increases with increasing pH in the visible region, which can be attributed to the deprotonation of the nitrophenols formed. These results contribute to a better understanding of methoxyphenol photooxidation mediated by nitrite as a source of toxic nitrophenols and climatically important brown carbon in atmospheric waters.