Department of Civil and Environmental Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, P. R. China.
Hong Kong Branch of Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, P. R. China.
Environ Sci Technol. 2023 Nov 28;57(47):18867-18876. doi: 10.1021/acs.est.3c00255. Epub 2023 May 9.
Increasing the radical yield and reducing energy consumption would enhance the sustainability and competitiveness of advanced oxidation processes (AOPs) for micropollutant degradation in water. We herein report a novel AOP coupling far-UVC radiation at 222 nm with chlorinated cyanurates (termed the UV/Cl-cyanurates AOP) for radical generation and micropollutant abatement in water. We experimentally determined the concentrations of HO, Cl, and ClO in the UV/Cl-cyanurates AOP in deionized water and swimming pool water. The radical concentrations are 10-27 times and 4-13 times, respectively, higher than those in the UV/Cl-cyanurates AOP and the well-documented UV/chlorine AOP under comparable conditions (e.g., same UV fluence and oxidant dosing). We determined the molar absorption coefficients and innate quantum yields of two chlorine species and two Cl-cyanurates at 222 nm and incorporated these parameters into a kinetic model. The model enables accurate prediction of oxidant photodecay rates as well as the pH impact on radical generation in the UV/Cl-cyanurates AOP. We predicted the pseudo-first-order degradation rate constants of 25 micropollutants in the UV/Cl-cyanurates AOP and demonstrated that many micropollutants can be degraded by >80% with a low UV fluence of 25 mJ cm. This work advances the fundamental photochemistry of chlorine and Cl-cyanurates at 222 nm and offers a highly effective engineering tool in combating micropollutants in water where Cl-cyanurates are suitable to use.
提高自由基产量和降低能耗将提高高级氧化工艺(AOP)在水中降解微量污染物的可持续性和竞争力。我们在此报告一种新型 AOP,即将 222nm 的远紫外线辐射与氯化氰尿酸酯(称为 UV/Cl-氰尿酸酯 AOP)相结合,用于水中自由基生成和微量污染物去除。我们在去离子水和游泳池水中实验确定了 UV/Cl-氰尿酸酯 AOP 中的 HO、Cl 和 ClO 的浓度。在可比条件下(例如,相同的 UV 通量和氧化剂剂量),自由基浓度分别比 UV/Cl-氰尿酸酯 AOP 和记录良好的 UV/氯 AOP 高 10-27 倍和 4-13 倍。我们确定了两种氯物种和两种 Cl-氰尿酸酯在 222nm 处的摩尔吸收系数和固有量子产率,并将这些参数纳入动力学模型。该模型能够准确预测氧化剂光解速率以及 pH 对 UV/Cl-氰尿酸酯 AOP 中自由基生成的影响。我们预测了 25 种微量污染物在 UV/Cl-氰尿酸酯 AOP 中的准一级降解速率常数,并证明许多微量污染物可以在低 UV 通量 25mJ cm 下降解 80%以上。这项工作推进了 222nm 下氯和 Cl-氰尿酸酯的基本光化学,并为在使用 Cl-氰尿酸酯的水中去除微量污染物提供了一种高效的工程工具。