Summertime diurnal variations in the isotopic composition of atmospheric nitrogen dioxide at a small midwestern United States city

The nitrogen and oxygen stable isotopes (δ15N & δ18O) of nitrogen oxides (NOx = nitric oxide (NO) + nitrogen dioxide (NO2)) may be a useful tool for partitioning NOx emission sources and for evaluating NOx photochemical cycling, but few measurements of in situ NOx exist. In this study, we have collected and characterized the diurnal variability in δ15N and δ18O of NO2 from ambient air at a small Midwestern city (West Lafayette, IN, USA, 40.426° N, 86.908° W) between July 7 to August 5, 2016, using an active sampling technique. Large variations were observed in both δ15N(NO2) and δ18O(NO2) that ranged from −31.4 to 0.4‰ and 41.5-112.5‰, respectively. Daytime averages were −9.2 ± 5.7‰ (x̅ ± 1σ) and 86.5 ± 14.1‰ (n = 11), while nighttime averages were −13.4 ± 7.3‰ and 56.3 ± 7.1‰ (n = 12) for δ15N(NO2) and δ18O(NO2), respectively. The large variability observed in δ15N(NO2) is predicted to be driven by changing contributions of local NOx emission sources, as calculated isotope effects predict a minor impact on δ15N(NO2) relative to δ15N(NOx) that is generally less than 2.5‰ under the sample collection conditions of high ozone concentration ([O3]) relative to [NOx]. A statistical δ15N mass-balance model suggests that traffic-derived NOx is the main contributor to the sampling site (0.52 ± 0.22) with higher relative contribution during the daytime (0.58 ± 0.19) likely due to higher traffic volume than during the nighttime (0.47 ± 0.22). The diurnal cycle observed in δ18O(NO2) is hypothesized to be a result of the photochemical cycling of NOx that elevates δ18O(NO2) during the daytime relative to the nighttime. Overall, this data suggests the potential to use δ15N(NO2) for NOx source partitioning under environmental conditions of high [O3] relative to [NOx] and δ18O(NO2) for evaluating VOC-NOx-O3 chemistry.