Summertime and wintertime atmospheric processes of secondary aerosol in Beijing

Secondary aerosol constitutes a large fraction of fine particles in urban air of China. However, its formation mechanisms and atmospheric processes remain largely uncertain despite considerable study in recent years. To elucidate the seasonal variations in fine-particle composition and secondary aerosol formation, an Aerodyne quadrupole aerosol chemical speciation monitor (Q-ACSM), combined with other online instruments, was used to characterize the sub-micrometer particulate matter (diameter < 1 mu m, PM1) in Beijing during summer and winter 2015. Our results suggest that photochemical oxidation was the major pathway for sulfate formation during summer, whereas aqueous-phase reaction became an important process for sulfate formation during winter. High concentrations of nitrate (17% of the PM1 mass) were found during winter, explained by enhanced gas-to-particle partitioning at low temperature, while high nitrate concentrations (19 %) were also observed under the conditions of high relative humidity (RH) during summer, likely due to the hydrophilic property of NH4NO3 and hydrolysis of N2O5. As for organic aerosol (OA) sources, secondary OA (SOA) dominated the OA mass (74 %) during summer, while the SOA contribution decreased to 39% during winter due to enhanced primary emissions in the heating season. In terms of the SOA formation, photochemical oxidation perhaps played an important role for summertime oxygenated OA (OOA) formation and less-oxidized wintertime OOA (LO-OOA) formation. The wintertime more-oxidized OOA (MO-OOA) showed a good correlation with aerosol liquid water content (ALWC), indicating a more important contribution of aqueous-phase processing over photochemical production to MO-OOA. Meanwhile, the dependence of LO-OOA and the mass ratio of LO-OOA to MO-OOA on atmospheric oxidative tracer (i.e., O-x) both degraded when RH was greater than 60 %, suggesting that RH or aerosol liquid water may also affect LO-OOA formation.