Assessing the transformation kinetics of 2- and 4-nitrophenol in the atmospheric aqueous phase. Implications for the distribution of both nitroisomers in the atmosphere

Abstract

Different transformation processes for nitrophenols in the atmospheric aqueous phase were considered to assess their relative importance, and their ability to account for the higher occurrence of 4-nitrophenol (4NP) compared to 2-nitrophenol (2NP) in the atmosphere. The importance of the different processes was in the order •OH > •NO 3 > direct photolysis > nitration to 2,4-dinitrophenol. 2NP is more reactive than 4NP with the hydroxyl radical, but the difference is low. Accordingly, such a process could account for the higher atmospheric occurrence of 4NP only if the observed atmospheric nitrophenols were what was left of an almost complete degradation by •OH. This would imply the unlikely scenario that the known nitrophenol sources to the atmosphere were only a limited fraction of the actual ones. A more likely, tentative possibility would be connected with the higher occurrence of 4NP on particles. If the reactivity order of nitrophenols in the atmospheric compartments was water droplets > gas phase > particles, particulate matter could act as a reservoir of 4NP. 2NP would undergo degradation in gas phase or solution at a higher rate than 4NP on particles, which could decrease the atmospheric levels of 2NP below those of 4NP.