This Special Issue of Atmosphere, “Atmospheric Aqueous-Phase Chemistry”, comprises ten original articles dealing with different aspects of chemistry in atmospheric liquid water. Liquid water in cloud ...and fog droplets and in moist aerosol particles is ubiquitous in the atmosphere. Dissolved species from the soluble aerosol fraction, as well as soluble trace gases, undergo chemical reactions in the aqueous phase via different mechanisms, usually yielding different products from those in the gas phase. In addition to their different reactivity, the chemical species solubility determines their fate in the atmosphere, i.e., their involvement in gas-phase or aqueous-phase chemistry.The articles of this Special Issue can be divided into three groups: (i) the first is mostly based on field measurements and/or combined field and modeling studies giving insights into the chemical characterization of different atmospheric liquid water samples from various environments; (ii) the second group is focused on studies of aqueous-phase reactivity of some important atmospheric organic compounds; and (iii) the final group comprises articles based on predictive modeling and/or combined modeling and laboratory studies providing insight into aqueous secondary organic aerosol (SOA) formation.
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.
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