Critical contribution of chemically diverse carbonyl molecules to the oxidative potential of atmospheric aerosols

Abstract

Carbonyls have an important effect on atmospheric chemistry and human health because of their high electrophilicity. Here, high-throughput screening of carbonyl molecules in complex aerosol samples was achieved by combining targeted derivatization with non-targeted analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Results showed that water-soluble organic matter (WSOM) in PM2.5 contains a large variety of carbonyls (5147 in total), accounting for 17.6 % of all identified organic molecules. Compared with non-carbonyl molecules, carbonyl molecules are more abundant in winter than in summer and have unique molecular composition and chemical parameters. For the first time, a significant positive correlation was found between the abundance of carbonyl molecules and the dithiothreitol (DTT) activities of WSOM, and the elimination of the carbonyl group remarkably reduced the DTT activities, highlighting the pivotal role of carbonyls in determining the oxidative potential (OP) of organic aerosol. Among various molecules, oxidized aromatic compounds containing the carbonyl group produced in winter contributed more to the enhancement of DTT activity, which could be used as potential markers of atmospheric oxidative stress. This study improves our understanding of the chemical diversity and environmental health effects of atmospheric carbonyls, emphasizing the need for targeted strategies to mitigate the health risks associated with carbonyl-rich aerosols.