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

被引:40
作者
Mielke, Levi H. [1 ,2 ]
Furgeson, Amanda [1 ]
Odame-Ankrah, Charles A. [1 ]
Osthoff, Hans D. [1 ]
机构
[1] Univ Calgary, Dept Chem, 2500 Univ Dr NW, Calgary, AB T2N 1N4, Canada
[2] Univ Indianapolis, Dept Chem, 1400 East Hanna Ave, Indianapolis, IN 46227 USA
基金
加拿大自然科学与工程研究理事会;
关键词
nitryl chloride; urban boundary layer; seasonal dependence; chlorine activation; SECONDARY ORGANIC AEROSOL; SEA-SALT AEROSOL; NITRYL CHLORIDE; REACTIVE UPTAKE; TEMPERATURE-DEPENDENCE; DINITROGEN PENTOXIDE; N2O5; REACTIVITY; OZONE FORMATION; PARTICLE PHASE; GASEOUS N2O5;
D O I
10.1139/cjc-2015-0426
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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 O-3 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.
引用
收藏
页码:414 / 423
页数:10
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