Kinetics of the nitrate-mediated photooxidation of monocarboxylic acids in the aqueous phase

Abstract

The photooxidation of organic compounds by hydroxyl radicals (·OH) in atmospheric aqueous phases contributes to both the formation and aging of secondary organic aerosols (SOAs), which usually include carboxylic acids. Hydrogen peroxide (H₂O₂) and inorganic nitrate are two important ·OH photochemical sources in atmospheric aqueous phases. The aqueous phase pH is an important factor that not only controls the dissociation of carboxylic acids and consequently their ·OH reactivities, but also the production of ·OH and other reactive species from the photolysis of some ·OH photochemical precursors, particularly inorganic nitrate. While many studies have reported on the aqueous pH-dependent photodegradation rates of carboxylic acids with ·OH produced by H₂O₂ photolysis, the aqueous pH-dependent photodegradation rates of carboxylic acids with ·OH produced by inorganic nitrate photolysis have not been studied. In this work, we investigated the pH-dependent (pH 2 to 7) aqueous photooxidation of formic acid (FA), glycolic acid (GA), and pyruvic acid (PA) initiated by the photolysis of ammonium nitrate (NH₄NO₃). The observed reaction rates of the three carboxylic acids were controlled by the [NH₄NO₃]/[carboxylic acid] concentration ratio. Higher [NH₄NO₃]/[carboxylic acid] concentration ratios resulted in faster photodegradation rates, which could be attributed to the higher concentrations of ·OH produced from the photolysis of higher concentrations of NH₄NO₃. In addition, the observed photodegradation rates of the three carboxylic acids strongly depended on the pH. The highest photodegradation rate was observed at pH 4 for FA, whereas the highest photodegradation rates were observed at pH 2 for GA and PA. The observed pH-dependent FA and GA photodegradation rates were due to the combined effects of the pH-dependent ·OH formation from NH₄NO₃ photolysis and the differences in ·OH reactivities of dissociated vs. undissociated FA and GA. In contrast, the observed pH-dependent PA photodegradation rate was due primarily to the pH-dependent decarboxylation of PA initiated by light. These results highlight how the aqueous phase pH and inorganic nitrate photolysis can combine to influence the degradation rates of carboxylic acids, which can have significant implications for how the atmospheric fates of carboxylic acids are modeled for regions with substantial concentrations of inorganic nitrate in cloud water and aqueous aerosols.