Quantifying primary and secondary humic-like substances in urban aerosol based on emission source characterization and a source-oriented air quality model

摘要

Humic-like substances (HULIS) are a mixture of high-molecular-weight, water-soluble organic compounds that are widely distributed in atmospheric aerosol. Their sources are rarely studied quantitatively. Biomass burning is generally accepted as a major primary source of ambient humic-like substances (HULIS) with additional secondary material formed in the atmosphere. However, the present study provides direct evidence that residential coal burning is also a significant source of ambient HULIS, especially in the heating season in northern China based on source measurements, ambient sampling and analysis, and apportionment with source-oriented CMAQ modeling. Emission tests show that residential coal combustion produces 5% to 24% of the emitted organic carbon (OC) as HULIS carbon (HULISc). Estimation of primary emissions of HULIS in Beijing indicated that residential biofuel and coal burning contribute about 70% and 25% of annual primary HULIS, respectively. Vehicle exhaust, industry, and power plant contributions are negligible. The average concentration of ambient HULIS in PM2.5 was 7.5 mu g m(-3) in urban Beijing and HULIS exhibited obvious seasonal variations with the highest concentrations in winter. HULISc accounts for 7.2% of PM2.5 mass, 24.5% of OC, and 59.5% of water-soluble organic carbon. HULIS are found to correlate well with K+, Cl-, sulfate, and secondary organic aerosol, suggesting its sources include biomass burning, coal combustion, and secondary aerosol formation. Source apportionment based on CMAQ modeling shows residential biofuel and coal burning and secondary formation are important sources of ambient HULIS, contributing 47.1 %, 15.1 %, and 38.9 %, respectively.