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To understand the characteristics of winter fine aerosol pollution in Beijing, we conducted continuous measurements of the atmospheric trace gas ammonia (NH3), PM2.5, and inorganic ions in PM2.5 at an urban site in Beijing from February 13 to March 17, 2015. The hourly average concentration of NH3 throughout the campaign was 15.4 ± 17.5 ppb. NH3 concentrations correlated well with NH4+ in PM2.5, indicating the dominant precursor role of NH3 on NH4+ formation. The diurnal profile indicated an increase in NH3 concentrations during the morning rush hours, which was likely due to vehicle emissions. The mean ammonium conversion ratio (NHR) was 0.26, with the highest value of 0.32 in the afternoon. Elevated NHR, nitrate oxidation ratio (NOR), and NH4+ coincided with the significant increase in O3 levels in the afternoon, indicating the large daytime formation of NH4NO3 via photochemical reactions. Moreover, higher NHR values occurred under higher relative humidity (RH >60%) and lower temperature (0–10 °C). NHR increased during the nighttime and correlated well with RH, indicating the dominant role of heterogeneous reactions on gas-particle partitioning. The sulfate oxidation ratio (SOR) and NOR showed positive correlations with RH, which suggests that the conversions of SO2 to SO42− and NO2 to NO3− were sensitive to changes in RH. The sustained increase in SO42− concentrations at RH >60% suggests that RH had a higher influence on SO42− formation than on NO3− formation. As the sole precursor of NH4+, NH3 significantly enhanced daytime NH4NO3 formation via homogeneous gas-phase reactions and also promoted sulfate formation via both homogeneous and heterogeneous reactions. Moreover, the back trajectory results inferred a high contribution of southwestern air masses to atmospheric NH3 and NH4+ aerosol variations in Beijing. The result suggests the need for controlling the vehicle emissions to reduce the high levels of NH3 and alleviate PM2.5 pollution in winter in Beijing.

Severe PM2.5 pollution was observed frequently in Beijing. We conducted highly time-resolved measurements of inorganic ions associated with PM2.5 at an urban site in Beijing from 10 February to 19 March, 2015. The average PM2.5 mass concentrations during the six haze episodes ranged from 113.0 μg/m3 to 182.6 μg/m3, which were more than 8 times higher than those observed in clean periods. The secondary inorganic species (NH4+, SO42− and NO3−) in PM2.5 sharply increased during the haze episodes, indicating more extensive formation of SO42− and NO3−. The sulfur oxidation ratios (SOR) and the nitrogen oxidation ratios (NOR) in haze episodes were higher than those in clean periods, which indicated that secondary transformation in haze episodes was more significant than those in clean periods. No correlations between SOR and the oxidants (O3 and HONO) and the temperature were found, whereas a high correlation between SOR and relative humidity (RH) was found in haze episodes, which implied that sulfate was mainly produced by the aqueous-phase oxidation of SO2 rather than the gas-phase conversion of SO2 to sulfate. The conversion of SO2 to SO42− was observed to be sensitive to changes in RH. Furthermore, the SOR sharply increased at RH > 60% with the highest value of 0.88 at RH around 80% during complicated pollution. NO2 played an important role in the rapid sulfate formation with high RH and NH3 neutralization conditions in haze episodes in Beijing. The impact of RH was less apparent for nitrate than for sulfate. Nitrate was found to be produced mainly by photochemical and heterogeneous reactions, while heterogeneous reactions had a greater influence on NOR at nighttime. The NO3−/SO42− ratio indicated that mobile sources contributed more to the formation of PM2.5 than stationary sources. The result suggested the need for control of vehicle emissions to reduce the high levels of NOx and nitrate and the severe PM2.5 pollution in Beijing.