Observation of ClNO₂ in a mid-continental urban environment

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.