Light-absorbing and fluorescent properties of atmospheric brown carbon: A case study in Nanjing, China

Brown carbon (BrC), a significant wavelength-dependent atmospheric absorber of solar radiation, plays a key role in photochemistry and long-lasting haze episodes. Herein, two types of BrC extracted from one-year PM_2.5 samples (June 2017-May 2018 in Nanjing), i.e. methanol-extracted organic carbon (MSOC) and ultrapure water-extracted organic carbon (WSOC), were obtained to investigate distinct optical properties of atmospheric BrC. The extraction efficiency of BrC was as high as 91% in methanol solution, and the corresponding light absorption coefficient (Abs) of MSOC at 365 nm (Abs_365-MSOC, 7.75 ± 3.95 Mm^-1) was approximately 1.6 times that of WSOC (Abs_365-WSOC, 4.84 ± 2.97 Mm^-1), indicating that the water-insoluble compounds mostly affected the light absorption of BrC. The seasonal variations of Abs_365-WSOC and Abs_365-MSOC were followed the sequence of winter > spring > autumn > summer, due to the dominated emissions from fossil fuel combustion and biomass burning in the cooling seasons. Additionally, four fluorescent chromophores in WSOC and MSOC, containing three humic-like chromophores and one protein-like chromophore, exhibited the highest fluorescent intensities in winter but weakest in summer. The lower humification index (HIX) in MSOC reflects that humic-like chromophores were preferentially water-soluble, in coordination with high degree of photo-oxidation and aromaticity. Fluorescence index (FI) of BrC was also higher in winter because of the effects of photo-bleaching, whereas biological index (BIX) remained stable throughout a year. Considering the correlation between primary organic carbon (POC) and secondary organic carbon (SOC), aside from the contribution of primary emissions, secondary formation has become another major source to atmospheric BrC in Nanjing.