Unraveling Urban NOx Emission Sources in Polluted Arctic Wintertime Using NO2 Nitrogen Isotopes

Nitrogen (N) isotopic fractionation during nitrogen oxides (NOx) cycling and conversion into atmospheric nitrate alters the original N isotopic composition (δ15N) of NOx emissions. Limited quantification of these isotopic effects in urban settings hampers the δ15N-based identification and apportionment of NOx sources. δ15N of nitrogen dioxide (NO2) measured during winter in downtown Fairbanks, Alaska, displayed a large temporal variability, from −10.2 to 24.1‰. δ15N(NO2) records are found to be driven by equilibrium isotopic fractionation, at a rate in very close agreement with theoretical predictions. This result confirms that N isotopic partitioning between NO and NO2 can be accurately predicted over a wide range of conditions. This represents an important step for inferring NOx emission sources from isotopic composition measurement of reactive nitrogen species. After correcting our δ15N(NO2) measurements for N fractionation effects, a δ15N-based source apportionment analysis identifies vehicle and space heating oil emissions as the dominant sources of breathing-level NOx at this urban site. Despite their large NOx emissions, coal-fired power plants with elevated chimney stacks (>26 m) appear to make a small contribution to surface NOx levels in downtown Fairbanks (likely less than 18% on average). The combined uncertainties of the δ15N of NOx from heating oil combustion and of the influence of low temperatures on the δ15N of NOx emitted by vehicle exhaust prevent a more detailed partitioning of surface NOx sources in Fairbanks.