Photodissociation of particulate nitrate as a source of daytime tropospheric Cl<sub>2</sub>.

Peng, Xiang; Wang, Tao; Wang, Weihao; Ravishankara, A R; George, Christian; Xia, Men; Cai, Min; Li, Qinyi et al. · Nat Commun · 2022

basic_science · Level V

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Abstract

Chlorine atoms (Cl) are highly reactive and can strongly influence the abundances of climate and air quality-relevant trace gases. Despite extensive research on molecular chlorine (Cl<sub>2</sub>), a Cl precursor, in the polar atmosphere, its sources in other regions are still poorly understood. Here we report the daytime Cl<sub>2</sub> concentrations of up to 1 ppbv observed in a coastal area of Hong Kong, revealing a large daytime source of Cl<sub>2</sub> (2.7 pptv s<sup>-1</sup> at noon). Field and laboratory experiments indicate that photodissociation of particulate nitrate by sunlight under acidic conditions (pH < 3.0) can activate chloride and account for the observed daytime Cl<sub>2</sub> production. The high Cl<sub>2</sub> concentrations significantly increased atmospheric oxidation. Given the ubiquitous existence of chloride, nitrate, and acidic aerosols, we propose that nitrate photolysis is a significant daytime chlorine source globally. This so far unaccounted for source of chlorine can have substantial impacts on atmospheric chemistry.