A MCM modeling study of the effects of nitryl chloride on oxidant budgets, ozone production, VOC lifetimes, and halogen recycling in polluted regions
Abstract
Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing particles. Nitryl chloride is photolyzed during the day to liberate highly reactive chlorine atoms. This chemistry takes place primarily in urban environments where the concentrations of N2O5 precursors (NOx and ozone) are high, though it can likely occur in remote regions at lower intensity. Recent field measurements have illustrated the potential importance of ClNO2 as a chlorine atom source and a NOx reservoir. However, the fate of these chlorine atoms and the overall impact of ClNO2 remain unclear. To this end we have incorporated ClNO2 production, photolysis, and subsequent Cl-atom reactions into an existing Master Chemical Mechanism (MCM version 3.2) based model framework. Cl-atom reactions with alkenes and alcohols not presently part of the MCM have also been added. Using observational constraints from the CalNex 2010 field study, we assess the dominant reactive sinks and sources of chlorine atoms over the course of a model day. Relative to model runs excluding ClNO2 formation, the presence of ClNO2 produces marked changes on a variety of species important to tropospheric chemistry and air quality (e.g. O3, RO2, OH, HO2, ClOx). For example a 50% yield of ClNO2 (max ClNO2 of 1.5 ppb) from nighttime N2O5 reactions leads to a ~10% enhancement in integrated ozone production. VOC and NOx lifetimes are shorter due primarily to enhanced OH from propagation of RO2 produced by Cl-atom chemistry under high NOx. The impact of ClNO2 on daytime halogen atom recycling is substantial, with order of magnitude higher daytime Cl2 production predicted with ClNO2 chemistry than without. In fact, incorporation of ClNO2 could help explain daytime levels of Cl2 observed in polluted coastal regions. Additionally, we highlight a set of chlorinated VOC oxidation products that are predicted to form at small, but potentially detectable levels in regions with similar VOC mixtures as Los Angeles. These species could act as tracers of this chemistry.
- Publication:
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AGU Fall Meeting Abstracts
- Pub Date:
- December 2012
- Bibcode:
- 2012AGUFM.A33K0293R
- Keywords:
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- 0365 ATMOSPHERIC COMPOSITION AND STRUCTURE / Troposphere: composition and chemistry