Size-Segregated Atmospheric Humic-Like Substances (HULIS) in Shanghai: Abundance, Seasonal Variation, and Source Identification

Abstract

Humic-like substances (HULIS) are of great interest due to their optical and chemical characteristics. In this study, a total of 180 samples of atmospheric particulate matter (PM) of different sizes were collected from summer 2018 to spring 2019, in order to analyze the size distribution, to investigate the seasonal variation and then to identify the key sources of HULIS. The annual mean concentration of HULIS in the total suspended particulates reached 5.12 ± 1.42 μg/m3. The HULIS concentration was extremely higher in winter (8.35 ± 2.06 μg/m3) than in autumn (4.88 ± 0.95 μg/m3), in summer (3.62 ± 1.68 μg/m3) and in spring (3.36 ± 0.99 μg/m3). The average annual ratio of water-soluble organic carbon (WSOC) to OC and the ratio of HULIS to WSOC reached 0.546 ± 0.092 and 0.56 ± 0.06, respectively. Throughout the whole year, the size distributions of WSOC and HULIS-C were relatively smooth. The peaks of WSOC appeared at 1.8~3.2 μm and 0.56~1.0 μm, while the peaks of HULIS-C were located at 3.2~5.6 μm, 1.0~1.8 μm and 0.18~0.32 μm. The distribution of the HULIS particle mode was similar in spring, summer and autumn, while there was a lower proportion of the coarse mode and a higher proportion of the condensation mode in winter. By using the comprehensive analysis of principal component analysis (PCA), air mass backward trajectories (AMBTs) and fire point maps, key sources of WSOC and HULIS in Shanghai were identified as biomass combustion (48.42%), coal combustion (17.49%), secondary formation (16.07%) and vehicle exhaust (5.37%). The remaining part might be contributed by crustal dust sources, marine sources and/or other possible sources. This study provides new insight into the characteristics and size distribution of HULIS in Shanghai, thereby providing a practical base for further modeling.