Precursors and Pathways Leading to Enhanced Secondary Organic Aerosol Formation during Severe Haze Episodes

Molecular analyses help to investigate the key precursors and chemical processes of secondary organic aerosol (SOA) formation. We obtained the sources and molecular compositions of organic aerosol in PM2.5 in winter in Beijing by online and offline mass spectrometer measurements. Photochemical and aqueous processing were both involved in producing SOA during the haze events. Aromatics, isoprene, long-chain alkanes or alkenes, and carbonyls such as glyoxal and methylglyoxal were all important precursors. The enhanced SOA formation during the severe haze event was predominantly contributed by aqueous processing that was promoted by elevated amounts of aerosol water for which multifunctional organic nitrates contributed the most followed by organic compounds having four oxygen atoms in their formulae. The latter included dicarboxylic acids and various oxidation products from isoprene and aromatics as well as products or oligomers from methylglyoxal aqueous uptake. Nitrated phenols, organosulfates, and methanesulfonic acid were also important SOA products but their contributions to the elevated SOA mass during the severe haze event were minor. Our results highlight the importance of reducing nitrogen oxides and nitrate for future SOA control. Additionally, the formation of highly oxygenated long-chain molecules with a low degree of unsaturation in polluted urban environments requires further research.

Automated summary

This study used molecular analyses to investigate the key precursors and chemical processes of secondary organic aerosol formation in Beijing's winter PM2.5. Results showed that both photochemical and aqueous processing were involved in producing SOA during haze events, with important precursors including aromatics, isoprene, long-chain alkanes or alkenes, and carbonyls such as glyoxal and methylglyoxal. The enhanced SOA formation during severe haze events was mainly attributed to aqueous processing, highlighting the importance of reducing nitrogen oxides for future SOA control. Further research is needed on the formation of highly oxygenated long-chain molecules in polluted urban environments.