Characteristics of ambient ammonia and its effects on particulate ammonium in winter of urban Beijing, China

Abstract

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.