Simultaneous Measurement of Gaseous HONO and NO2− in Solutions from Aqueous Nitrate Photolysis Mediated by Organics

Field studies suggest that NO3− photolysis may play a more significant role than previously thought. In this study, we concurrently measured HONO, NO2, and NO2− in situ to gain a deeper understanding of the photogenerated HONO transfer to air and to better constrain the rate constants of NO3− photolysis. The presence of fatty acids (e.g., nonanoic acid, NA), which are naturally present in the environment, significantly increases the production of photogenerated HONO and NO2. With an increase in oxygen percentage, the release rate of photoinduced HONO slowed, while the release rate of NO2 accelerated. The measured JNO3− value averaged 1.65 × 10−5 s−1, which is two orders of magnitude higher than values reported in similar systems. The HONO transfer rate from the solutions increased from 2.3 × 10−4 s−1 to 5.6 × 10−4 s−1 as the NA concentration increased from 0.1 to 20 mM. This can be attributed to the accumulation of NO2− induced by NA at the interface. Within this interfacial region, NO2− in the solutions becomes more prone to transfer into gaseous HONO, suggesting that photogenerated NO2− hosted in atmospheric droplets may serve as a temporary reservoir of atmospheric HONO without illumination, influencing the atmospheric oxidizing capacity in the region for hours. Therefore, simultaneous measurements of both gas and particle phase photoproducts are recommended to better constrain the rate constants of NO3− photolysis, thereby enhancing the accuracy of predicting the photochemical production of HONO in the atmosphere.