Nitrogen isotope composition of ammonium in PM2.5 in the Xiamen, China: impact of non-agricultural ammonia.

Since NH3 is a significant precursor to ammonium in PM2.5 and contributes significantly to atmospheric nitrogen deposition but largely remains unregulated in China, the insight into the source of NH3 emissions by the isotopic investigation is important in controlling NH3 emissions. In this study, atmospheric concentrations of NH3 and water-soluble ion composition in PM2.5 as well as nitrogen isotope ratios in NH4+ (δ15N-NH4+) in Xiamen, China, were measured. Results showed that average NH3 concentration for the five sites in Xiamen was 7.9 μg m-3 with distinct higher values in the warm season and lower values in the cold season, and PM2.5 concentration for the two sites (urban and suburban) was 59.2 μg m-3 with lowest values in summer. In the PM2.5, NH4+ concentrations were much lower than NH3 and showed a stronger positive correlation with NO3- than that with SO42- suggesting the formation of NH4NO3 and equilibrium between NH3 and NH4+. Although the concentrations of NH3 at the urban site were significantly higher than those at the suburban site, no significant spatial difference in NH4+ and δ15N-NH4+ was obtained. The distinct heavier δ15N-NH4+ values in summer than in other seasons correlated well with the equilibrium isotopic effects between NH3 and NH4+ which depend on temperature. The initial δ15N-NH3 values were in the range of waste treatment (- 25.42‰) and fossil fuel combustion (- 2.5‰) after accounting for the isotope fractionation. The stable isotope mixing model showed that fossil fuel-related NH3 emissions (fossil fuel combustion and NH3 slip) contributed more than 70% to aerosol NH4+. This finding suggested that the reduction of NH3 emissions from urban transportation and coal combustion should be a priority in the abatement of PM2.5 pollution in Xiamen.