Abstract
The formation process of in-cloud aqueous-phase secondary organic matter (aqSOM) and its characteristics are unclear. Herein, water-soluble inorganic ions, oxalate, and water-soluble organic carbon (WSOC) were determined in cloud water and aerosol (PM2.5) samples simultaneously collected at a remote mountain site in southern China during spring 2018 and winter 2020. The molecular compositions of water-soluble organic matter (WSOM) in cloud water and aerosols were analyzed by a Fourier transform ion cyclotron resonance mass spectrometer in negative electrospray ionization (ESI-) mode. The results showed that the mean concentration of WSOC was 6.27–8.54 mg C L−1 in cloud water and 0.60–1.37 μg C m−3 in aerosols. The strong correlation observed between WSOM and aqueous secondary matter (e.g., NO3
− and oxalate), the positive matrix factorization results, and the elevated WSOM/K+ ratios observed in cloud water suggested enhanced aqSOM formation in cloud water. According to random forest analysis, the factors related to in-cloud WSOM variation mainly included secondary ions, K+, cloud water pH, and atmospheric NOx. Additionally, 37 characteristic in-cloud aqSOM molecules, classified as -Ox, -NOx, -N2Ox, and -N1-2OxS, mainly consisting of dicarboxylic acids, nitrophenols, and dinitrophenols, were identified using linear discriminant analysis effect size (LefSe). The characteristic N- and S-containing molecules in in-cloud aqSOM with carbon numbers >10 had low or extremely low volatility; therefore, they might contribute to secondary organic aerosol formation after droplet evaporation. The results revealed the modifying effects of in-cloud processes on aerosol organic composition at the molecular level and could improve our understanding of aerosol–cloud interactions.