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 (k_2nd(global) = 0.075 M⁻¹·s⁻¹) in comparison to its degradation in the dark under the same solution conditions (k_2nd = 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.

The characterization of organic matter (OM) and trace elements (TEs) was conducted in bulk precipitation samples collected in an urban area of Croatia (Zagreb center), from January 2009 to October 2011 (N = 31). Characterization of OM was performed by measurement of dissolved (DOC) and particulate forms of organic carbon (POC), as well as surface-active substances, copper complexing capacity and reduced sulfur species which were determined electrochemically. Concentrations of TEs (Al, Fe, Zn, Cr, Ba, Mn, Cu, Sr, Ti, Pb, V, Ni, Rb, Sb, As, Sn, Se, Co, Cd, Mo) were analyzed by HR ICP-MS. The most important outcome of this study is confirmed relatively low concentrations of DOC (0.69–4.86 mgC L⁻¹) and TEs. Daily fluxes of Zn, Pb, Ni, As, and Cd were two to three times lower than that of those reported for an urban industrial site in Europe. Additionally, this study shows that the value and reactivity of rainwater DOC has not considerably changed if compared with the results from the 1998–1999 study (0.78–4.39 mgC L⁻¹). High traffic density and thermal power plants are assumed to be the main local sources of pollutants in Zagreb. Using Al as a reference element, it was found that Cd, Sb, and Cu were associated with anthropogenic sources. The solubility of Sr, Zn, Cd, Ni, Cr, As, and Rb was higher than 70%. Another critical characteristic of precipitation composition is episodic variation in POC concentration because of Saharan dust transport. Obtained data can be valuable for environmental quality assessment, as well as for insight into atmospheric deposition processes.

The ultimate goal in the understanding of complex chemical processes is a complete description of the underlying reaction mechanism. In the present study and for this purpose, a novel experimental platform is introduced that builds upon electrochemistry being able of generating reactive intermediate species at the electrode surface. The atmospherically relevant nitration of catechols is taken as a case example. First, we confirm the recently proposed nitration mechanism, advancing the understanding of atmospheric brown carbon formation in the dark. We are able to selectively quantify aromatic isomers, which is beyond the limits of conventional electroanalysis. Second, we identify a new pathway of nitrocatechol hydroxylation, which proceeds simply by oxidation and the addition of water and can be environmentally significant in the dark aqueous-phase formation of secondary organic aerosols. Third, the developed methodology is capable of selectively detecting a wide range of nitroaromatics; a possible application in environmental monitoring is proposed.