Ammonium (NH4+) is one of the most important inorganic components in PM2.5, and plays key roles in increasing the concentration of PM2.5. Understanding the sources and formation processes of NH4+ is an effective way to control PM2.5. In this study, daily PM2.5 samples were collected from September 01 to November 30, 2017 in Tianjin, and water-soluble ion concentrations and δ15N-NH4+ in PM2.5 were analyzed. The results showed that (NH4)2SO4 and NH4NO3 were the major chemical forms of NH4+. In particular, NH4NO3 dominated the liquid water content (ALWC) increase on haze days, leading to more NH3 partitioning into the particle phase, and this formation mechanism of NH4NO3 might be self-amplified with an increase in ALWC concentrations. The mean values of δ15N-NH4+ were 14.7 ± 5.2‰, and the estimated initial ambient δ15N-NH3 was −15.6 ± 9.3‰. The mean fractional contributions of volatilization sources, fossil fuel-related sources and biomass burning were 31.9 ± 15.8%, 45.9 ± 12.6% and 22.2 ± 18.3%, respectively, which were estimated by the stable isotope mixing model. Obviously, the NH3 related to combustion emissions (68.1 ± 15.9%) dominated the source of aerosol NH4+ during autumn in Tianjin in this study. We also found that the fractional contributions of these sources have varied during different pollution periods, and the contributions of biomass burning emissions increased to 60% on haze days in November. Our results highlight that fossil fuel related source emissions of NH3 dominate the formation of NH4NO3 in autumn, leading to the occurrence of haze in autumn in Tianjin. Nevertheless, the biomass burning emissions were non-ignorable.
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