Abstract
Over 300 daily PM2.5 filter samples were collected in two western Chinese megacities, Xi'an and Chongqing, from October 2019 to May 2020. Their aqueous extracts were nebulized simultaneously to an aerosol mass spectrometer (AMS) and a recently developed extractive electrospray ionization (EESI) mass spectrometer, for bulk and near-molecular organic aerosol (OA) composition, respectively. Carbonate was quantified using EESI and a total organic carbon analyzer to separate inorganic carbon from dust. Via isotopically-labelled internal standards and positive matrix factorization, seven water-soluble sources were quantified separately using the AMS- and EESI-based analyses, with consistent types, concentrations, and correlations. These include dust, solid fuel combustion (SFC)-related, nitrogen- (and sulfur-) containing, summer/winter oxygenated OAs, and a cigarette-related OA only in EESI. When accounting for water-solubility, SFC-related OAs were the largest (53%) sources in Chongqing, while dust (consisting of 77% OA and 23% carbonates) was the largest (30%) source in Xi'an. Overall, this study presents one of the first times that complementary mass spectrometric techniques independently resolved consistent OA sources-with added chemical information-over multiple seasons and locations of complex pollution. The methods and quantified sources are essential for subsequent chemical, modelling, and health studies, and policy making for air pollution mitigation.