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Photodissociation of particulate nitrate as a source of daytime tropospheric Cl2

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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 2 ), a Cl… Click to show full 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 2 ), a Cl precursor, in the polar atmosphere, its sources in other regions are still poorly understood. Here we report the daytime Cl 2 concentrations of up to 1 ppbv observed in a coastal area of Hong Kong, revealing a large daytime source of Cl 2 (2.7 pptv s −1 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 2 production. The high Cl 2 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. This study unravels an important daytime Cl 2 source in the extra-polar atmosphere and shows that photolysis of particle nitrate at high acidity produced unprecedented levels of Cl 2 , boosting the oxidative power and air pollutants like O 3 .

Keywords: chlorine; nitrate; photodissociation particulate; daytime; particulate nitrate; source

Journal Title: Nature Communications
Year Published: 2022

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