Size-fractionated water-soluble ions during autumn and winter: Insights into volatile ammonium formation mechanisms in Shanghai, a megacity of China

Size-fractionated aerosols were collected by a Micro-Orifice Uniform Deposit Impactor at an urban site in Shanghai during the autumn and winter of 2014. The results showed that the average concentration of PM1.8 increased from 49 μg m−3 in autumn to 74 μg m−3 in winter. By contrast, the relative contribution of the water-soluble inorganic species decreased from 40% in autumn to 31% in winter. This finding suggests that the increase of organic matter (OM) greatly contributed to the deterioration of particle pollution in winter. Compared to autumn, the concentration of sulfate decreased whereas the concentration of NH4Cl increased significantly and became an important constituent of the fine particles in winter. The formation of nitrate in autumn became significant at [NH4+]/[SO42−] > 2, indicating that H2SO4 was fully neutralized by NH3 to form (NH4)2SO4. Our results showed that the regression between [NO3−]/[SO42−] and [NH4+]/[SO42−] drawn an unrealistic nitrate formation mechanism when the particulate NH4Cl was abundant. Replacing [NO3−] with {[NO3−]+[Cl−]} in the regression between [NO3−]/[SO42−] and [NH4+]/[SO42−], it is established that (NH4)2SO4 is preferentially formed before the excess available NH3 can react with HNO3 and HCl to form NH4NO3 and NH4Cl during wintertime. The concentrations of particulate sulfate and nitrate were not positively correlated with the ambient relative humidity, indicating that heterogeneous reactions on wet particles were not the key to haze formation in Shanghai during winter. Our results suggest that more studies are needed to understand the complex haze formation mechanisms in China. Keywords: Ammonium formation, Size distribution, Haze pollution, Yangtze River Delta