Molecular characterization of organic aerosol in winter from Beijing using UHPLC-Orbitrap MS

The urban organic aerosol (OA) may pose a serious threat to human health and ecological environment. In order to understand the molecular characteristics of organic compounds in aerosols, atmospheric PM2.5 samples were collected in Beijing and the extracts were analyzed by liquid chromatography-Orbitrap mass spectrometry combined with negative-ion electrospray ionization, positive-ion electrospray ionization, and positive-ion atmospheric pressure photoionization sources. The combination of multiple ionization sources realized the comprehensive molecular characterization of organic compounds in OA, and 1976 (+APPI), 3038 (−ESI), and 4376 (+ESI) molecular formulas were identified in this study. Significant differences in the species, abundance, and number of subgroups (CHO, CHN, CHON, CHONS, CHOS, and CH compounds) were clarified. Chemical fingerprinting of organics in the PM2.5 extract were investigated by high-throughput non-target compound analytical methods. Structure induction of organic compounds was realized through fragmentation prediction of MS/MS spectra with Sirius software. Furthermore, a total of 50 nitroaromatic formulas, 285 organosulfates (OS) formulas, 57 nitrooxy-OS formulas, 228 CHO- formulas with carboxyl groups, and 36 monoketone formulas were determined based on diagnostic fragmentation filtering. Our results provide important insights into the molecular composition and structural characteristics of OA, and establish foundation for exploring the interaction between composition and physicochemical properties.