Far-UVC (UV222) based photolysis, photooxidation, and photoreduction of chlorophenols using a KrCl-excimer lamp: Degradation, dechlorination, and detoxification.

The KrCl-excimer lamp, emitting far-UVC light at 222 nm (UV222), offers a promising alternative to conventional UVC light at 254 nm (UV254) for the photolysis of organic pollutants and the activation of radical sensitizers. This study was aimed to investigate the efficiencies of UV222 in the treatment of halogenated aromatics, focusing on its performance in degradation, dechlorination and detoxification. Chlorophenols, representative recalcitrant and toxic halogenated aromatics, were used as target pollutants. The pathways of direct photolysis, photooxidation and photoreduction under UV222 illumination were compared. UV222 outperformed UV254 in photolyzing chlorophenols (1.4-34.1 times faster), especially protonated chlorophenols, due to substantially higher UV absorption (17.1-108.0 times) and quantum yields (2.1-3.4 times). The quantum yields of chlorophenols were influenced by the inducive electron-withdrawing effect of Cl-substitutes. Moreover, UV222 improved the dechlorination of chlorophenols to 95 % compared to 60 % by UV254. The introduction of radical sensitizer (e.g., HO, nitrate, and sulfite) reduced 4-chlorophenol photolysis by competing for UV222 absorption, though the sensitizers partially increased radical oxidation via generating OH or e. UV222 photolysis of 4-chlorophenol increased the toxicity by 88.6 times through forming toxic intermediates (e.g., hydroquinone and resorcinol). Notably, OH and e (i.e., UV222/HO and UV222/sulfite) increased the dechlorination and OH (i.e., UV222/HO) detoxified the mixture solution. Moreover, UV222 photolysis remained effective for 4-chlorophenol removal in real paper-mill wastewater, indicating the potential application of KrCl* lamp UV222.