Apportionment of NOx and NH3 emission sources in an urban coastal airshed: Insights from stable isotopes and a novel approach to intermittent sources

Abstract

Inorganic nitrogen (IN) wet deposition flux and emission sources have been intensively investigated over the past two decades with a primary focus in rural areas and large metropolitan cities. Smaller coastal cities are often overlooked in these studies despite a substantial portion of the earth's population inhabiting these regions. Ammonia and NOx emission source apportionment estimations in these studies can be misleading without proper inspection of intermittent source (e.g., biomass burning and lightning) impacts on the airmass of rain events. This study measured the chemical composition (NH4+, NO3−, Cl−, SO42− and pH) and isotopic composition of ammonium and nitrate (δ15N–NH4+, δ15N–NO3-, and δ18O–NO3-) in rainwaters collected in a small coastal city (Corpus Christi, TX, USA) to aid in determining the emission source apportionments of NH3 and NOx. A novel approach coupling lightning and fire/smoke mapping products along with airmass back trajectories was developed to help determine the influence of biomass burning and lightning on individual rain events before applying to isotope source apportionment models. The annual IN wet deposition was 3.9 kg N·ha−1·yr−1, in which NH4+ and NO3− constituted 65% and 35%, respectively. Isotope mixing model results suggest vehicle emission contribution to NH3 can rival agriculture sources (i.e., fertilizer and livestock waste) in urban areas. Vehicles, biomass burning and lightning were significant NOx sources, while soil “biogenic” emissions increased substantially in certain rain events occurring in warmer months. This work qualified IN wet deposition flux and estimated IN emission source apportionments in a coastal small-sized city, which will inform regional N emission regulations and watershed restoration practices.