Different formation pathways of nitrogen-containing organic compounds in aerosols and fog water in northern China

Abstract

Abstract. While aqueous-phase processing is known to contribute to the formation of nitrogen-containing organic compounds (NOCs), the specific pathways involved remain poorly understood. In this study, we aimed to characterize the NOCs present in both pre-fog aerosols and fog water collected at a suburban site in northern China. Fourier-transform ion cyclotron resonance mass spectrometry was utilized to analyze the molecular composition of NOCs in both negative and positive modes of electrospray ionization (ESI− and ESI+). In both pre-fog aerosols and fog water samples, NOCs constituted a significant portion, accounting for over 60 % of all assigned formulas in ESI− and more than 80 % in ESI+. By comparing the molecular composition of NOCs originating from biomass burning, coal combustion, and vehicle emissions, we identified that 72.3 % of NOCs in pre-fog aerosols were attributed to primary anthropogenic sources (pNOCs), while the remaining NOCs were categorized as secondary NOCs formed within the aerosols (saNOCs). Unique NOCs found in fog water were classified as secondary NOCs formed within the fog water (sfNOCs). Through a comprehensive “precursor–product pair” screening involving 39 reaction pathways, we observed that the nitration reaction, the amine pathway, and the intramolecular N-heterocycle pathway of NH3 addition reactions contributed 43.6 %, 22.1 %, and 11.6 % of saNOCs, respectively. In contrast, these pathways contributed 26.8 %, 28.4 %, and 29.7 % of sfNOCs, respectively. This disparity in formation pathways is likely influenced by the diverse precursors, the aqueous acidity, and the gas-phase species partitioning. Correspondingly, saNOCs were found to contain a higher abundance of carbohydrate-like and highly oxygenated compounds with two nitrogen atoms compared to pNOCs. Conversely, sfNOCs exhibited a higher content of lipid-like compounds with fewer oxygen atoms. These results underscore the distinct secondary processes contributing to the diversity of NOCs in aerosols and fog water, which may lead to their different climate effects.