Leibniz Institute for Tropospheric Research (TROPOS) , Permoserstrasse 15 , D-04318 Leipzig , Germany.
Environ Sci Technol. 2019 Jan 15;53(2):771-778. doi: 10.1021/acs.est.8b05165. Epub 2018 Dec 28.
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 ClNO photolysis and ICl photolysis are crucial for gas-phase Cl atom activation. In the cloud scenario, the integrated ClNO and ICl photolysis rates are 3.7 × 10 and 3.1 × 10 molecules cm s. In the cloud-free scenario, the integrated ClNO and ICl photolysis rates are 8.1 × 10 and 3.6 × 10 molecules cm s. The simulations show larger contributions of ClNO 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 ClNO 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 INO 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.
开展了详细的多相化学箱模型研究，调查了污染沿海地区卤族自由基的活化。针对非永久性云和无云两种情况进行了模拟，结果表明 ClNO 光解和 ICl 光解对气相 Cl 原子的活化至关重要。在云场景中，整合的 ClNO 和 ICl 光解速率分别为 3.7×10 和 3.1×10 分子 cm s。在无云场景中，整合的 ClNO 和 ICl 光解速率分别为 8.1×10 和 3.6×10 分子 cm s。模拟结果表明，ClNO 光解在早晨的贡献更大，而 ICl 光解在下午的贡献更高。在整个模拟过程中，ClNO 光解对云中和无云情况下 Cl 原子活化的平均贡献分别为 42%和 62%，ICl 光解的平均贡献分别为 35%和 28%。ICl 是通过 HOI 与氯化物在水相中的反应形成的。形成的 ICl 中有三分之二释放到气相中。剩余的三分之一与溴化物反应，生成 IBr。总的来说，模拟结果强调了 INO 水解在污染沿海地区 Cl 和 Br 原子活化中的关键作用。因此，在化学输运模型中需要考虑这一点，以提高空气质量预测的准确性。
