Effect of ozone aging on light absorption and fluorescence of brown carbon in soot particles: The important role of polycyclic aromatic hydrocarbons

Abstract

The evolution of brown carbon (BrC) during atmospheric aging, including the changes in optical properties and chemical compositions, is still unclear. Light absorption and fluorescence of BrC fraction extracted from fresh and ozonized propane soot particles by methanol were systematically measured, which showed that (1) the mass absorption efficiencies (MAE) sharply decreased by ozone (O₃) aging (e.g., 1.2 ± 0.3–0.8 ± 0.1 m² g⁻¹ for MAE₃₆₅), but changed slowly with increased O₃ concentration (e.g., from 0.7 ± 0.2–0.8 ± 0.1 m² g⁻¹ for MAE₃₆₅); (2) the fluorescence emission peaks were blue shifted, implying a loss of conjugated structures; (3) excitation–emission matrix analysis suggested that humic-like substances, charge transfer complexes, and polycyclic aromatic hydrocarbon (PAH)-like substances were the main chromophores. The PAH loss, accompanied by the decline of surface C˭C content, contributed more to the change of optical properties than the oxygenated PAH formation, thereby leading to the decrease in light absorption and fluorescence with O₃ aging. This research reveals the importance of identifying the components responsible for optical properties in investigating the evolution of BrC during atmospheric aging, and is benefit for improving the evaluation of BrC’s radiative forcing.