Enhanced Chlorine and Bromine Atom Activation by Hydrolysis of Halogen Nitrates from Marine Aerosols at Polluted Coastal Areas. 2019

Erik H Hoffmann, and Andreas Tilgner, and Ralf Wolke, and Hartmut Herrmann
Leibniz Institute for Tropospheric Research (TROPOS) , Permoserstrasse 15 , D-04318 Leipzig , Germany.

Detailed multiphase chemistry box model studies are carried out, investigating halogen radical activation at polluted coastal areas. Simulations are performed for a nonpermanent cloud and a cloud-free scenario and reveal that ClNO2 photolysis and ICl photolysis are crucial for gas-phase Cl atom activation. In the cloud scenario, the integrated ClNO2 and ICl photolysis rates are 3.7 × 107 and 3.1 × 107 molecules cm-3 s-1. In the cloud-free scenario, the integrated ClNO2 and ICl photolysis rates are 8.1 × 107 and 3.6 × 107 molecules cm-3 s-1. The simulations show larger contributions of ClNO2 photolysis in the morning and higher ones of ICl photolysis during afternoon. Throughout the simulation, average contributions to Cl atom activation in the cloud and cloud-free scenarios by ClNO2 photolysis are 42% and 62% and by ICl photolysis 35% and 28%, respectively. ICl is formed through an aqueous-phase reaction of HOI with chloride. Two thirds of the formed ICl is released into the gas phase. The residual third reacts with bromide, creating IBr. Overall, the simulations emphasize the crucial role of INO3 hydrolysis for Cl and Br atom activation in polluted coastal areas. Therefore, it needs to be considered in chemical transport models to improve air quality predictions.

UI MeSH Term Description Entries
D009566 Nitrates Inorganic or organic salts and esters of nitric acid. These compounds contain the NO3- radical. Nitrate
D001966 Bromine A halogen with the atomic symbol Br, atomic number 35, and atomic weight 79.904. It is a volatile reddish-brown liquid that gives off suffocating vapors, is corrosive to the skin, and may cause severe gastroenteritis if ingested. Bromine-79,Bromine 79
D002713 Chlorine An element with atomic symbol Cl, atomic number 17, and atomic weight 35, and member of the halogen family. Chlorine Gas,Chlorine-35,Cl2 Gas,Chlorine 35,Gas, Chlorine,Gas, Cl2
D006219 Halogens A family of nonmetallic, generally electronegative, elements that form group 17 (formerly group VIIa) of the periodic table. Halogen,Group 17 Elements,Elements, Group 17
D006868 Hydrolysis The process of cleaving a chemical compound by the addition of a molecule of water.
D000336 Aerosols Colloids with a gaseous dispersing phase and either liquid (fog) or solid (smoke) dispersed phase; used in fumigation or in inhalation therapy; may contain propellant agents. Aerosol

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