Changes in light absorption by brown carbon in soot particles due to heterogeneous ozone aging in a smog chamber

Light absorption by brown carbon (BrC) is dynamic due to atmospheric aging processes, leading to complex and poorly constrained effects on photochemistry and climate. In this study, a smog chamber was used to simulate the heterogeneous ozone (O₃) aging of soot particles. Twelve aging times and seven O₃ concentrations were set to investigate the effects of aging degree on BrC light absorption. The results showed that light absorption by BrC was enhanced after O₃ aging, but followed a non-monotonic trend with an initial increase and subsequent decrease. An aging time of 60 min and O₃ concentration of 1.2 ppm were optimal for enhancing BrC absorption, where the contribution of BrC to total absorption and the contribution of BrC relative to black carbon absorption at 370 nm of ozonized soot were 23.0 ± 1.8% and 30.0 ± 3.0%, respectively, much greater than those of fresh soot (8.1 ± 1.1% and 8.8 ± 1.3%, respectively). The absorption Ångström exponent (AAE) and delta C (ΔC) of ozonized soot at 60 min ranged from 1.18 ± 0.01 to 1.31 ± 0.03 and from 13.5 ± 7.0 to 24.3 ± 13.5 μg m^-3, respectively, and were greater than those of fresh soot (1.12 ± 0.02 and 8.0 ± 0.8 μg m^-3), but also showed non-monotonic trends, suggesting the formation of BrC during O₃ aging. Comparative results indicated that AAE might be a better BrC indicator for soot than ΔC. The non-monotonic trend was tentatively explained by changes in organic carbon, oxygenated functional groups and conjugated structures, as well as polycyclic aromatic hydrocarbon (PAH) degradation and oxygenated PAH formation. The relative intensities of oxidative formation and degradation of chromophores may determine BrC evolution during O₃ aging. This study will be useful for clarifying BrC evolution in the atmosphere and estimating its radiative forcing.