Quantifying the importance of vehicle ammonia emissions in an urban area of northeastern USA utilizing nitrogen isotopes

Abstract. Atmospheric ammonia (NH3) is a critical component of our atmosphere that contributes to air quality degradation and reactive nitrogen deposition; however, our knowledge of NH3 in urban environments remains limited. Year-long ambient NH3 and related species were measured for concentrations and the nitrogen isotopic compositions (δ15N) of NH3 and particulate ammonium (pNH4+) were measured to understand the temporal sources and chemistry of NH3 in a northeastern US urban environment. We found that urban NH3 and pNH4+ concentrations were elevated compared to regional rural background monitoring stations, with seasonally significant variations. Local and transported sources of NHx (NH3+ pNH4+) were identified using polar bivariate and statistical back trajectory analysis, which suggested the importance of vehicles, volatilization, industry, and stationary fuel combustion emissions. Utilizing a uniquely positive δ15N(NH3) emission source signature from vehicles, a Bayesian stable isotope mixing model (SIMMR) indicates that vehicles contribute 46.8±3.5 % (mean ±1σ) to the annual background level of urban NHx, with a strong seasonal pattern with higher relative contribution during winter (56.4±7.6 %) compared to summer (34.1±5.5 %). The decrease in the relative importance of vehicle emissions during the summer was suggested to be driven by temperature-dependent NH3 emissions from volatilization sources, seasonal fuel-combustion emissions related to energy generation, and change in seasonal transport patterns based on wind direction, back trajectory, and NH3 emission inventory analysis. This work highlights that reducing vehicle NH3 emissions should be considered to improve wintertime air quality in this region.