Spatial and temporal patterns of nitrogen isotopic composition of ammonia at U.S. ammonia monitoring network sites

Ammonia (NH3) emissions and ammonium (NH4+) deposition can have harmful effects on the environment and human health but remain generally unregulated in the U.S. PM2.5 regulations require that an area not exceed an annual average PM2.5 value of 12 μg/m3 (averaged over three years), and since NH3 is a significant precursor to PM2.5 formation these are the closest indirect regulations of NH3 emissions in the U.S. If the U.S. elects to adopt NH3 emission regulations similar to those applied by the European Union, it will be imperative to first adequately quantify NH3 emission sources and transport, and also understand the factors causing varying emissions from each source. To further investigate NH3 emission sources and transport at a regional scale, NH3 was sampled monthly at a subset of nine Ammonia Monitoring Network (AMoN) sites and analyzed for nitrogen isotopic composition of NH3 (δ15N-NH3). The observed δ15N-NH3 values ranged from −42.4 to +7.1‰ with an average of −15.1 ± 9.7. The observed δ15N-NH3 values reported here provide insight into the spatial and temporal trends of the NH3 sources that contribute to ambient [NH3] in the U.S. In regions where agriculture is prevalent (i.e., U.S. Midwest), low and seasonally variable δ15N-NH3 values are observed and are associated with varying agricultural sources. In comparison, rural nonagricultural areas have higher and more seasonally consistent δ15N-NH3 values associated with a constant “natural” (e.g. soil, vegetation, bi-directional flux, ocean) NH3 source. With regards to temporal variation, the peak in U.S. spring agricultural activity (e.g. fertilizer application, livestock waste volatilization) is accompanied by a decrease in δ15N-NH3 values at a majority of the sites, whereas higher δ15N-NH3 values in other seasons could be due to shifting sources (e.g. coal-fired power plants) and/or fractionation scenarios. Fractionation processes that may mask NH3 source signatures are discussed and require further investigation to optimize the utility of the nitrogen isotopic composition to determine NH3 sources and dynamics.