Role of ambient ammonia in particulate ammonium formation at a rural site in the North China Plain

Abstract

The real-time measurements of NH3 and trace gases were conducted, in conjunction with semi-continuous measurements of water-soluble ions in PM2.5 at a rural site in the North China Plain (NCP) from May to September 2013 in order to better understand chemical characteristics of ammonia and the impact of secondary ammonium aerosols on formation in the NCP. Extremely high NH3 and NH4+ concentrations were observed after a precipitation event within 7–10 days following urea application. Elevated NH3 levels coincided with elevated NH4+, indicating that NH3 likely influenced particulate ammonium mass. For the sampling period, the average conversion ∕ oxidation ratios for NH4+ (NHR), SO42− (SOR), and NO3− (NOR) were estimated to be 0.30, 0.64, and 0.24, respectively. The increased NH3 concentrations, mainly from agricultural activities and regional transport, coincided with the prevailing meteorological conditions. The high NH3 level with NHR of about 0.30 indicates that the emission of NH3 in the NCP is much higher than needed for aerosol acid neutralisation, and NH3 plays an important role in the formation of secondary aerosols as a key neutraliser. The hourly data obtained were used to investigate gas–aerosol partitioning characteristics using the thermodynamic equilibrium model ISORROPIA-II. Modelled SO42−, NO3−, and NH3 values agree well with the measurements, while the modelled NH4+ values largely underestimate the measurements. Our observation and modelling results indicate that strong acids in aerosol are completely neutralised. Additional NH4+ exists in aerosol, probably a result of the presence of a substantial amount of oxalic and other diacids.