At present, there are still numerous unresolved questions concerning the mechanisms of light-absorbing organic aerosol (brown carbon, BrC) formation in the atmosphere. Moreover, there is growing evidence that chemical processes in the atmospheric aqueous phase can be important. In this work, we investigate the aqueous-phase formation of BrC from 3-methylcatechol (3MC) under simulated sunlight conditions. The influence of different HNO2/NO2− concentrations on the kinetics of 3MC degradation and BrC formation was investigated. Under illumination, the degradation of 3MC is faster (k2nd(global) = 0.075 M−1·s−1) in comparison to its degradation in the dark under the same solution conditions (k2nd = 0.032 M−1·s−1). On the other hand, the yield of the main two products of the dark reaction (3-methyl-5-nitrocatechol, 3M5NC, and 3-methyl-4-nitrocatechol, 3M4NC) is low, suggesting different degradation pathways of 3MC in the sunlight. Besides the known primary reaction products with distinct absorption at 350 nm, second-generation products responsible for the absorption above 400 nm (e.g., hydroxy-3-methyl-5-nitrocatechol, 3M5NC-OH, and the oxidative cleavage products of 3M4NC) were also confirmed in the reaction mixture. The characteristic mass absorption coefficient (MAC) values were found to increase with the increase of NO2−/3MC concentration ratio (at the concentration ratio of 50, MAC is greater than 4 m2·g−1 at 350 nm) and decrease with the increasing wavelength, which is characteristic for BrC. Yet, in the dark, roughly 50% more BrC is produced at comparable solution conditions (in terms of MAC values). Our findings reveal that the aqueous-phase processing of 3MC in the presence of HNO2/NO2−, both under the sunlight and in the dark, may significantly contribute to secondary organic aerosol (SOA) light absorption.
Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects
