In the troposphere, nitryl chloride (ClNO₂), produced from uptake of dinitrogen pentoxide (N₂O₅) on chloride containing aerosol, can be an important nocturnal reservoir of NO(x) (= NO + NO₂) and a source of atomic Cl, particularly in polluted coastal environments. Here, we present measurements of ClNO₂ mixing ratios by chemical ionization mass spectrometry (CIMS) in Calgary, Alberta, Canada over a 3-day period. The observed ClNO₂ mixing ratios exhibited a strong diurnal profile, with nocturnal maxima in the range of 80 to 250 parts-per-trillion by volume (pptv) and minima below the detection limit of 5 pptv in the early afternoon. At night, ClNO₂ constituted up to 2% of odd nitrogen, or NO(y). The peak mixing ratios of ClNO₂ observed were considerably below the modeled integrated heterogeneous losses of N₂O₅, indicating that ClNO₂ production was a minor pathway compared to heterogeneous hydrolysis of N₂O₅. Back trajectory analysis using HYSPLIT showed that the study region was not influenced by fresh injections of marine aerosol, implying that aerosol chloride was derived from anthropogenic sources. Molecular chlorine (Cl₂), derived from local anthropogenic sources, was observed at mixing ratios of up to 65 pptv and possibly contributed to formation of aerosol chloride and hence the formation of ClNO₂.

Trace gas measurements using optically resonant cavities and quantum cascade lasers operating at room temperature J. Appl. Phys.

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 midcontinental locations is less clear. In this paper, intermittent measurements over the course of several seasons of ClNO2 mixing ratios by iodide ion chemical ionization mass spectrometry in Calgary, Alberta, 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 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 chlorine atom needs to be considered as an oxidant in high-latitude urban environments in winter.

No abstract