Measurement report: Optical characterization, seasonality, and sources of brown carbon in fine aerosols from Tianjin, North China: Year-round observations

Abstract

To investigate the optical characteristics and sources of brown carbon (BrC) in North China, where the atmospheric aerosol loadings are high and have severe impacts on Earth's climate system, we collected fine aerosols (PM2.5) at an urban site in Tianjin over a 1-year period. We measured the ultraviolet (UV) light absorption and excitation emission matrix (EEM) fluorescence of the water-soluble BrC (WSBrC) and the water-insoluble but methanol-soluble BrC (WI-MSBrC) in the PM2.5 using a three-dimensional fluorescence spectrometer. The average light absorption efficiency of both WSBrC (Abs365,gWSBrC) and WI-MSBrC (Abs365,gWI-MSBrC) at 365gnm was found to be highest in winter (10.4g±g6.76 and 10.0g±g5.13gMm-1, respectively) and distinct from season to season. The averages of the fluorescence index (FI) and the biological index (BIX) of WSBrC were lower in summer than in the other seasons and opposite to that of the humification index (HIX), which implied that the secondary formation and further chemical processing of aerosols were more intensive during the summer period than in the other seasons. However, in winter, the higher HIX together with the higher FI and BIX of WI-MSBrC suggested that the BrC loading was mainly influenced by primary emissions from biomass burning and coal combustion. Based on the EEM, the types of fluorophores in WSBrC were divided into humic-like substances (HULIS), including low-oxygenated and high-oxygenated species and protein-like compounds (PLOM), though mostly PLOM in the WI-MSBrC. The direct radiation absorption by both WSBrC and WI-MSBrC in the range of 300-400gnm accounted for g1/4g40g% of that (SFEAbs, 4.97g±g2.71 and 7.58g±g5.75gWg-1, respectively) in the range 300-700gnm.