Source apportionment of atmospheric ammonia before, during, and after the 2014 APEC summit in Beijing using stable nitrogen isotope signatures

Abstract

Abstract. Stable nitrogen isotope composition (δ15N) offers new opportunities to address the long-standing and ongoing controversy regarding the origins of ambient ammonia (NH3), a vital precursor of PM2.5 (particulate matters with aerodynamic diameter equal or less than 2.5 µm) inorganic components, in the urban atmosphere. In this study, the δ15N values of NH3 samples collected from various sources were constrained using a novel and robust chemical method coupled with standard elemental analysis procedures. Independent of the wide variation in mass concentrations (ranging from 33 (vehicle) to over 6000 (human excreta) µg m−3), different NH3 sources have generally different δ15N values (ranging from −52.0 to −9.6 ‰). Significantly high δ15N values are seen as a characteristic feature of all vehicle-derived NH3 samples (−14.2 ± 2.8 ‰), which can be distinguished from other sources emitted at environmental temperature (−29.1 ± 1.7, −37.8 ± 3.6, and −50.0 ± 1.8 ‰ for livestock, waste, and fertilizer, respectively). The isotope δ15N signatures for a range of NH3 emission sources were used to evaluate the contributions of the different sources within measured ambient NH3 in Beijing, using an isotope mixing model (IsoSource). The method was used to quantify the sources of ambient NH3 before, during and after the 2014 Asia-Pacific Economic Cooperation (APEC) summit, when a set of stringent air quality control measures were implemented. Results show that the average NH3 concentrations (the overall contributions of traffic, waste, livestock, and fertilizer) during the three periods were 9.1 (20.3, 28.3, 23.6, and 27.7 %), 7.3 (8.8, 24.9, 14.3, and 52.0 %), and 12.7 (29.4, 23.6, 31.7, and 15.4 %) µg m−3, respectively, representing a 20.0 % decrease first and then a 74.5 % increase in overall NH3 mass concentrations. During (after) the summit, the contributions of traffic, waste, livestock, and fertilizer decreased (increased) by 56.7 (234.2), 12.0 (−5.0), 39.4 (120.8), and −87.7 % (−70.5 %) when compared with periods before (during) the summit, respectively, signifying that future NH3 control efforts in megacities like Beijing should prioritize traffic sector as well as livestock breeding. The results show that isotope ratio measurements of NH3 to be a valuable tool to quantify the atmospheric sources of NH3 in urban atmospheres.