Significant production of ClNO2 and possible source of Cl-2 from N2O5 uptake at a suburban site in eastern China

Abstract

ClNO2 and Cl-2 can affect atmospheric oxidation and thereby the formation of ozone and secondary aerosols, yet their sources and production mechanisms are not well understood or quantified. In this study we present field observations of ClNO2 and Cl-2 at a suburban site in eastern China during April 2018. Persistent high levels of ClNO2 (maximum: similar to 3.7 ppbv; 1 min average) were frequently observed at night, due to the high ClNO2 yield (phi (ClNO2), 0.56 +/- 0.20) inferred from the measurements. The phi (ClNO2) value showed a positive correlation with the [Cl-]/[H2O] ratio, and its parameterization was improved at low to median yields (0-0.75) by the incorporation of [Cl-]/[H2O] and the suppression effect of aerosol organics. ClNO2 and Cl-2 showed a significant correlation on most nights. We show that the Cl-2 at our site was more likely a co-product with ClNO2 from N2O5 uptake on acidic aerosols that contain chloride than being produced by ClNO2 uptake as previously suggested. We propose a mechanism in which NO2+ can react with Cl- to produce Cl-2 and ClNO2 simultaneously. Under a new framework which regards Cl-2, ClNO2, and nitrate as products of N2O5 uptake, the Cl-2 yield (phi (Cl-2)) was derived using ambient data. phi (Cl-2) exhibited significant correlations with [Cl-] and [H+], based on which a parameterization of phi (Cl-2) was developed. The derived parameterizations of phi (ClNO2) and phi (Cl-2) can be used in models to evaluate the nighttime production of ClNO2 and Cl-2 and their impact on the next day's photochemistry.