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Open AccessArticle

Aqueous-Phase Brown Carbon Formation from Aromatic Precursors under Sunlight Conditions

Department of Analytical Chemistry, National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia
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Atmosphere 2020, 11(2), 131; https://doi.org/10.3390/atmos11020131
Received: 22 November 2019 / Revised: 19 December 2019 / Accepted: 22 January 2020 / Published: 24 January 2020
(This article belongs to the Special Issue Atmospheric Aqueous-Phase Chemistry)
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.
Keywords: brown carbon chromophores; biomass burning; photooxidation; nitration; nitrophenols; methylnitrocatechols; mass absorption coefficient brown carbon chromophores; biomass burning; photooxidation; nitration; nitrophenols; methylnitrocatechols; mass absorption coefficient
MDPI and ACS Style

Vidović, K.; Kroflič, A.; Šala, M.; Grgić, I. Aqueous-Phase Brown Carbon Formation from Aromatic Precursors under Sunlight Conditions. Atmosphere 2020, 11, 131.

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