Heterogeneous formation of particulate nitrate under ammonium-rich regimes during the high-PM_2.5 events in Nanjing, China

Abstract

Particulate nitrate (NO3-) not only influences regional climates but also contributes to the acidification of terrestrial and aquatic ecosystems. In 2016 and 2017, four intensive online measurements of water-soluble ions in PM2.5 were conducted in Nanjing City in order to investigate the potential formation mechanisms of particulate nitrate. During the sampling periods, NO3- was the predominant species, accounting approximately for 35 % of the total water-soluble inorganic ions, followed by SO42- (33 %) and NH4+ (24 %). Significant enhancements of nitrate aerosols in terms of both absolute concentrations and relative abundances suggested that NO3- was a major contributing species to high-PM2.5 events (hourly PM2.5≥150 µg m−3). High NO3- concentrations mainly occurred under NH4+-rich conditions, implying that the formation of nitrate aerosols in Nanjing involved NH3. During the high-PM2.5 events, the nitrogen conversion ratios (Fn) were positively correlated with the aerosol liquid water content (ALWC; R>0.72 and p<0.05). Meanwhile, increasing NO3- concentrations regularly coincided with increasing ALWC and decreasing Ox (Ox=O3+NO2). These results suggested that the heterogeneous reaction was probably a major mechanism of nitrate formation during the high-PM2.5 events. Moreover, the average production rate of NO3- by heterogeneous processes was estimated to be 12.6 % h−1 (4.1 µg m−3 h−1), which was much higher than that (2.5 % h−1; 0.8 µg m−3 h−1) of gas-phase reactions. This can also explain the abrupt increases in nitrate concentrations during the high-PM2.5 events. Utilizing the ISORROPIA II model, we found that nitrate aerosol formation in Nanjing during the high-PM2.5 events was HNO3 limited. This indicated that control of NOx emissions will be able to efficiently reduce airborne particulate nitrate concentrations and improve the air quality in this industrial city.