Ubiquity of ClNO2 in the urban boundary layer of Calgary, AB, Canada

Abstract

The role of nitryl chloride (ClNO2) as a nocturnal nitrogen oxide reservoir species and chlorine atom precursor is well established for polluted coastal areas, but its role at mid-continental locations is less clear. In this manuscript, intermittent measurements over the course of several seasons of ClNO2 mixing ratios by iodide ion chemical ionization mass spectrometry (CIMS) in Calgary, AB, Canada, are presented. Mixing ratios were highly variable between nights and seasons and depended on the abundances of precursors and meteorological conditions. The lowest ClNO2 mixing ratios (nocturnal maximum of 30 parts-per-trillion by volume, pptv) were observed in the summer, rationalized by losses of the nitrate radical (NO3) that were more efficient than in the other months. Higher ClNO2 mixing ratios (up to 330 pptv) were observed in the winter and spring months, but varied between nights. In the fall, ClNO2 mixing ratios increased from night to night following the application of salt to roads. The ClNO2 yield relative to the amount of NO3 produced from oxidation of NO2 by O3 ranged from 0.1% to 4.5% (10th and 90th percentiles; median 1.0%). The ClNO2 yield relative to consumed N2O5 consumed by heterogeneous reactions was estimated using a time-integrated box model and ranged from 0.5% to 12.1% (10th and 90th percentiles; median 3.4%). The ubiquity of ClNO2 implies that the Cl atom needs to be considered as an oxidant in high-latitude urban environments in winter.