UV/Chlorine Process: An Efficient Advanced Oxidation Process with Multiple Radicals and Functions in Water Treatment

Because of the deterioration of global water quality, the occurrence of chemical and microbial contaminants in water raises serious concerns for the health of the population. Identifying and developing effective and environmentally friendly water treatment technologies are critical to obtain clean water. Among the various technologies for the purification of water, ultraviolet photolysis of chlorine (UV/chlorine), an emerging advanced oxidation process (AOP), has multiple functions for the control of contaminants via the production of hydroxyl radicals (HO·) and reactive chlorine species (RCS), such as Cl·, ClO·, and Cl₂·^-.This Account centers around the radical chemistry of RCS and HO· in different water matrices and their roles and mechanisms in the abatement of contaminants. The concentrations of Cl·, ClO·, and Cl₂·^- are comparable to or higher than those of HO· (10^-14 to 10^-13 M). The reactivities of RCS are more selective than HO· with a broader range of second-order rate constants (k). The k values of Cl· toward most aromatics are higher or similar as compared to those of HO·, while those of Cl₂·^- and ClO· are less reactive but more selective toward aromatics containing electron-donating functional groups. Their major reaction mechanisms with Cl· are electron transfer and addition, while those with ClO· and Cl₂·^- primarily involve electron transfer. As for aliphatics, their reactivities with both HO· and RCS are much lower than those of aromatics. The reaction mechanisms for most of them with Cl· and Cl₂·^- are hydrogen abstraction, except for olefins, which are addition. In addition, RCS greatly contribute to the inactivation of microbial contaminants.Toward future application, the UV/chlorine process has both pros and cons. Compared with the traditional HO·-based AOP of UV/H₂O₂, UV/chlorine is more efficient and energy-saving for oxidation and disinfection, and its efficiency is less affected by water matrix components. However, the formation of toxic byproducts in UV/chlorine limits its application scenarios. In dissolved organic matter (DOM)-rich water, the formation of halogenated byproducts is enhanced in UV/chlorine. In the presence of ammonia, reactive nitrogen species (RNS) (e.g., ·NO and ·NO₂) are involved, and highly toxic nitro(so) products such as nitro(so)-phenolics and N-nitrosodimethylamine are generated. For a niche application, the UV/chlorine process is recommended to be utilized in water with low levels of DOM and ammonia.Strategies should be developed to make full use of highly reactive species (RCS and HO·) for the abatement of target contaminants and to reduce the formation of toxic byproducts. For example, the UV/chlorine process can be used in tandem with other treatments to create multiple barriers for the production of safe water. In addition, halogen radicals are very important in ecosystems as well as other areas such as medical therapy and organic synthesis. UV/chlorine is the most efficient homogeneous system to generate halogen radicals, and thus it provides a perfect system to investigate the fates of halogen radicals for interdisciplinary research.