摘要:

Glyoxal and methylglyoxal are vital carbonyl compounds in the atmosphere and play substantial roles in radical cycling and ozone formation. The partitioning process of glyoxal and methylglyoxal between the gas and particle phase via reversible and irreversible pathways could efficiently contribute to secondary organic aerosol (SOA) formation. However, the relative importance of two partitioning pathways still remains elusive, especially in the real atmosphere. In this study, we launched five field observations in different seasons and simultaneously measured glyoxal and methylglyoxal in the gas and particle phase. The field-measured gas-particle partitioning coefficients were 5–7 magnitudes higher than the theoretical ones, indicating the significant roles of reversible and irreversible pathways in the partitioning process. The particulate concentration of dicarbonyls and product distribution via the two pathways were further investigated using a box model coupled with the corresponding kinetic mechanisms. We recommended the irreversible reactive uptake coefficient γ for glyoxal and methylglyoxal in different seasons in the real atmosphere, and the average value of 8.0×10-3 for glyoxal and 2.0×10-3 for methylglyoxal best represented the loss of gaseous dicarbonyls by irreversible gas-particle partitioning processes. Compared to the reversible pathways, the irreversible pathways played a dominant role, with a proportion of more than 90% in the gas-particle partitioning process in the real atmosphere and the proportion was significantly influenced by relative humidity and inorganic components in aerosols. However, the reversible pathways were also substantial, especially in winter, with a proportion of more than 10%. The partitioning processes of dicarbonyls in reversible and irreversible pathways jointly contributed to more than 25% of SOA formation in the real atmosphere. To our knowledge, this study is the first to systemically examine both reversible and irreversible pathways in the ambient atmosphere, strives to narrow the gap between model simulations and field-measured gas-particle partitioning coefficients, and reveals the importance of gas-particle processes for dicarbonyls in SOA formation.

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