Enhanced wintertime oxidation of VOCs via sustained radical sources in the urban atmosphere. (1st April 2021)

• Record Type: Journal Article
• Authors: Sommariva, Roberto; Crilley, Leigh R.; Ball, Stephen M.; Cordell, Rebecca L.; Hollis, Lloyd D.J.; Bloss, William J.; Monks, Paul S.
• Is Part Of: Environmental pollution. Volume 274(2021)
• Publication Date: 2021-04-01
• Subjects: Nitryl chloride -- Nitrous acid -- Chlorine -- OH radical -- Tropospheric ozone; Pollution -- Periodicals; Pollution -- Environmental aspects -- Periodicals; Environmental Pollution -- Periodicals; Pollution -- Périodiques; Pollution -- Aspect de l'environnement -- Périodiques; Pollution -- Effets physiologiques -- Périodiques; Pollution; Pollution -- Environmental aspects; Periodicals; Electronic journals; 363.73
• DOI: 10.1016/j.envpol.2021.116563
• Languages: English
• ISSNs: 0269-7491

Abstract

Abstract: Daytime atmospheric oxidation chemistry is conventionally considered to be driven primarily by the OH radical, formed via photolytic sources. In this paper we examine how, during winter when photolytic processes are slow, chlorine chemistry can have a significant impact on oxidative processes in the urban boundary layer. Photolysis of nitryl chloride (ClNO2 ) provides a significant source of chlorine atoms, which enhances the oxidation of volatile organic compounds (VOCs) and the production of atmospheric pollutants. We present a set of observations of ClNO2 and HONO made at urban locations in central England in December 2014 and February 2016. While direct emissions and in-situ chemical formation of HONO continue throughout the day, ClNO2 is only formed at night and is usually completely photolyzed by midday. Our data show that, during winter, ClNO2 often persists through the daylight hours at mixing ratios above 10–20 ppt (on average). In addition, relatively high mixing ratios of daytime HONO ( > 65 ppt) provide a strong source of OH radicals throughout the day. The combined effects of ClNO2 and HONO result in sustained sources of Cl and OH radicals from sunrise to sunset, which form additional ozone, PAN, oxygenated VOCs, and secondary organic aerosol. We show that radical sources such as ClNO2 and HONO can lead to a surprisingly photoactive urban atmosphere during winter and should therefore be included in atmospheric chemical models. Graphical abstract: Image 1 Highlights: High ClNO2 concentrations at sunrise cause it to persist until sunset above 10–20 ppt. Daytime HONO accounts for over 90% of OH formation in the winter urban atmosphere. Sustained sources of Cl and OH throughout the day enhance the oxidation of VOCs. Production of O3 and secondary pollutants increases and continues into the afternoon.