Molecular chemodiversity of water-soluble organic matter in atmospheric particulate matter and their associations with atmospheric conditions

Water-soluble organic matter (WSOM) is a complex mixture of organic compounds affecting global climate change and carbon cycle. Herein, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used for identification of WSOM molecular compositions in annual atmospheric particulate matter with diameters ≤10 μm (PM10). Totally 6538 unambiguous monoisotopic molecular formulas were assigned to WSOM with m/z values concentrating in 150-600 Da. The CHO compounds with high unsaturation degrees contributed most (51.7-52.1%) to WSOM in spring and summer. However, the S-containing compounds (CHOS and CHNOS) with higher O/C and H/C ratios accounted for 56.8-63.2% of WSOM in autumn and winter. Temperature (r = 0.82) and O3 (r = 0.89) showed higher correlation with CHO compounds, which were mainly aliphatics and highly unsaturated structures with high oxygen compounds (80.7-90.8%). The concentrations of SO42- (r = 0.33) and NO3- (r = 0.46) in PM10 both showed a positive correlation with the abundances of the S-containing compounds due to their direct participation in atmospheric reactions. Among them, 96-100% and 78-96% of the CHOS and CHNOS compounds were confirmed to be organosulfates (OSs) and nitrooxy-organosulfates (NOSs) by MS/MS analysis, respectively. These findings illustrate the strong association of atmospheric conditions with molecular chemodiversity of WSOM.