Degradation of odorous 2,4,6-trichloroanisole in chlorinated water by UV-LED/chlorination: kinetics and influence factors.

2,4,6-Trichloroanisole (2,4,6-TCA) has aroused a special concern for their odor problem and potential threats. In this study, the degradation of 2,4,6-TCA by UV/chlorination with different UV sources was compared, including low-pressure mercury lamp (LPUV, 254 nm) and ultraviolet light-emitting diode (UV-LED, 275 and 285 nm). The maximum removal of 2,4,6-TCA can be achieved by 275-nm UV-LED/chlorination in neutral and alkaline conditions which was 80.0%. The reaction, kinetics, and water matrix parameters on 2,4,6-TCA degradation were also evaluated. During UV-LED (275 nm)/chlorination, 2,4,6-TCA degradation was mainly caused by direct UV photolysis and indirect hydroxyl radical (HO·) oxidation, while reactive chlorine radicals (RCSs) had a negligible contribution. The second-order rate constant between HO· and 2,4,6-TCA was determined as 3.1 × 109 M-1 s-1. Increasing initial chlorine dosage and decreasing 2,4,6-TCA concentration or pH value significantly promoted 2,4,6-TCA degradation during UV/chlorination process. The presence of natural organic matter (NOM) and bicarbonate (HCO3-) can inhibit 2,4,6-TCA degradation, while chloride ion (Cl-) had a negligible effect. The kinetic model for 2,4,6-TCA degradation was established and validated, and the degradation pathways were proposed based on the identified intermediates. Furthermore, UV-LED (275 nm)/chlorination also exhibited a promising effect on 2,4,6-TCA removal in real water, which can be used to control 2,4,6-TCA pollution and odor problems.

Micropollutant removal and disinfection byproduct control by sequential peroxymonosulfate-UV treatment in water: A case study with sulfamethoxazole.

UV/peroxymonosulfate (UV/PMS) advanced oxidation process has attracted significant attention for removal of micropollutants in water. However, during practical water treatment applications, the PMS treatment must be performed before the UV treatment to achieve full contact. In this study, sulfamethoxazole (SMX) was selected as the target micropollutant. Four different operational approaches, including UV alone, PMS alone, simultaneous UV/PMS and sequential PMS-UV, were compared for their differences in SMX removal and disinfection by-product (DBP) formation potentials during chlorine-driven disinfection. Among the four approaches, UV/PMS and PMS-UV achieved over 90% removal efficiencies for SMX without substantial differences. For raw water, the trichloronitromethane (TCNM) formation potential after treatment with PMS-UV was lower than that after UV/PMS treatment. The time interval over which the PMS-UV process was conducted had little effect on the final removal efficiency for SMX. However, a brief (5 min) pre-PMS treatment significantly reduced the TCNM formation potential and the genotoxicity from DBPs. The formation risk for TCNM during chlorination increased markedly with increasing PMS dosages, and the appropriate dosage under these experimental conditions was suggested to be 0.5-1.0 mmol/L. Under alkaline conditions, PMS-UV treatment can enhance SMX degradation as well as dramatically reduced the formation potentials for haloketones, haloacetonitriles and halonitromethanes. This study suggests that proper optimization of UV/PMS processes can remove SMX and reduce its DBP formation.

Mechanistic study on chlorine/nitrogen transformation and disinfection by-product generation in a UV-activated mixed chlorine/chloramines system.

The conversion mechanisms of chlorine species (including free chlorine, monochloramine (NH2Cl), dichloramine, and total chlorine), nitrogen species (including ammonium (NH4+), nitrate (NO3-), and nitrite (NO2-)) as well as the formation of disinfection by-products (DBPs) in a UV-activated mixed chlorine/chloramines system in water were investigated in this work. The consumption rates of free chlorine and NH2Cl were significantly promoted in a HOCl/NH2Cl coexisting system, especially in the presence of UV irradiation. Moreover, the transformation forms of nitrogen in both ultrapure and HA-containing waters were considerably affected by UV irradiation and the mass ratio of free chlorine to NH2Cl. NO3- and NO2- can be easily produced under UV irradiation, and the removal efficiency of total nitrogen with UV was obvious higher than that without UV when the initial ratio of HOCl/NH2Cl was less than 1. The roles of different radicals in the degradation of free chlorine, NH2Cl and NH4+ were also considered in such a UV-activated mixed chlorine/chloramines system. The results indicated that OH• was important to the consumption of free chlorine and NH2Cl, and showed negligible influence on the consumption of NH4+. Besides, the changes of DOC and UV254 in HA-containing water in UV-activated mixed chlorine/chloramines system indicated that the removal efficiency of DOC (24%) was much lower than that of UV254 (94%). The formation of DBPs in a mixed chlorine/chloramines system was also evaluated. The yields of DBPs decreased significantly as the mass ratio of HOCl/NH2Cl varied from 1 : 0 to 0 : 1. Moreover, compared to the conditions without UV irradiation, higher DBPs yields and DBP-associated calculated toxicity were observed during the UV-activated mixed chlorine/chloramine process.