As an eco-friendly and sustainable energy, solar energy has great application potential in water treatment. Herein, simulated sunlight was for the first time utilized to activate monochloramine for the degradation of environmental organic microcontaminants. Various microcontaminants could be efficiently degraded in the simulated sunlight/monochloramine system. The average innate quantum yield of monochloramine over the wavelength range of simulated sunlight was determined to be 0.068 mol/Einstein. With the determined quantum yield, a kinetic model was established. Based on the good agreement between the simulated and measured photolysis and radical contributions to the degradation of ibuprofen and carbamazepine, the major mechanism of monochloramine activation by simulated sunlight was proposed. Chlorine radical (Cl∙) and hydroxyl radical (HO∙) were major radicals responsible for microcontaminant degradation in the system. Moreover, the model facilitated a deep investigation into the effects of different reaction conditions (pH, monochloramine concentration, and water matrix components) on the degradation of ibuprofen and carbamazepine, as well as the roles of the involved radicals. The differences between simulated and measured degradation data of each microcontaminant under all conditions were less than 10 %, indicating the strong reliability of the model. The model could also make good prediction for microcontaminant degradation in the natural sunlight/monochloramine system. Furthermore, the formation of disinfection byproducts (DBPs) was evaluated at different oxidation time in simulated sunlight/monochloramine with and without post-chloramination treatment. In real waters, organic components showed more pronounced suppression on microcontaminant degradation efficiency than inorganic ions. This study provided a systematic investigation into the novel sunlight-induced monochloramine activation system for efficient microcontaminant degradation, and demonstrated the potential of the system in practical applications.

Algal blooms worldwide pose many challenges to drinking water production. Pre-oxidation with NaClO, KMnO4, or ozone is commonly used to enhance algal removal in conventional drinking water treatment processes. However, these currently utilized oxidation methods often result in significant algal cell lysis or impede the operation of the subsequent units. Higher algal removal with pre-chlorination in algal solutions prepared with natural water, compared to those prepared with ultrapure water, has been observed. In the present studies, preliminary findings indicate that ammonium in natural water alters chlorine species to NH2Cl, leading to improved treatment efficiency. NH2Cl with 1.5-3.0 mg∙L-1 as Cl2 with an oxidation time of 3-7 h significantly enhancing algal removal by coagulation. The selective oxidation of surface-absorbed organic matter (S-AOM) by NH2Cl, followed by the subsequent peeling off of this material from the algal surface, leading to an increase in zeta potential from -20.2 mV to -3.8 mV, constitutes the primary mechanism of enhanced algal removal through coagulation. These peeled S-AOM retained their large molecular weight and acted as polymer aids. Compared with NaClO and KMnO4, NH2Cl displays the best performance in improving algal removal, avoiding cell lysis, and decreasing the potential for nitrogenous disinfection byproducts formation under the reaction conditions used in this study. Notably, in major Chinese cities, water purification plants commonly rely on suburban lakes or reservoirs as water sources, necessitating the transportation of raw water over long distances for times up to several hours. These conditions favor the implementation of NH2Cl pre-oxidation. The collective results indicate the potential of NH2Cl oxidation as a viable pretreatment strategy for algal contamination during water treatment processes.

In this study, the photodegradation of 33 different DBPs (trihalomethanes, haloacetic acids, haloacetaldehydes, and haloacetonitriles) and TOX with low pressure UV light and the subsequent reformation of DBPs with chlorine and monochloramine were investigated. Results indicated that photodegradation followed the order of TOI > TOBr > TOCl, and treated surface water with low SUVA254 background did not impact the photodegradation of highly UV susceptible DBPs such as triiodomethane (TIM), diiodobromomethane (DIBM), tribromomethane (TBM). The mass balance results of chloride, bromide and iodide showed that the main photodegradation mechanism of TOBr and TOI was dehalogenation supported by halide releases (i.e., Cl-, Br- and/or I- ion). In addition, the photodegradation removal effect was higher, when brominated DBPs formation was high. Although low pressure UV light effectively removed halogenated organic DBPs, subsequent use of disinfectants (Cl2 and NH2Cl) reformed photodegraded DBPs, and the overall DBPs concentrations were increased, which suggested that the released Br- and I- ions will reform DBPs in distribution systems, with oxidants present or added (e.g., booster chlorination) in distribution systems. This study showed that although UV photodegradation will reduce halogenated organic DBPs in distribution systems, especially more toxic iodinated and brominated DBPs, it will be a more effective technology towards the end of the distribution system or a point of entry solution rather than in distribution system with post-disinfection and residence time.

The inactivation efficacy by monochloramine for disinfecting gastroenteritis-causing rotaviruses (RV) and Tulane viruses (TV), a surrogate for noroviruses, were evaluated in this study. In addition, the strategies for improving the disinfection efficiency of monochloramine by raising the temperature and sequentially implementing UV irradiation were investigated. The results showed that monochloramine was more effective in the inactivation of TV than RV. Additionally, the inactivation rate constants of RV and TV by monochloramine at 35 °C were improved approximately by 46% and 100%, respectively, compared to those at 25 °C. Moreover, applying UV irradiation before monochloramine enhanced the inactivation efficacy of RV and TV by 63% and 72% compared to monochloramine alone (UV: 6 mJ/cm2, NH2Cl: 60 ppm × min). Furthermore, the synergistic effect was observed during the RV inactivation by the sequential process. Especially, higher than 0.5 log10 reductions of RV VP1 genome contributed to the synergistic effect in sequential treatment, while less than 0.1 log10 reductions of RV VP1 genome were observed during UV alone (13 mJ/cm2) or monochloramine alone (94 ppm × min). The genome damage might be the primary mechanism of generating synergy in sequential treatment for the inactivation of RV. By comparison, no synergistic effect was discovered for the inactivation of TV due to high susceptibility to monochloramine and UV. The findings on the inactivation efficacy and mechanism for improvement will contribute to a wide application of monochloramine for virus inactivation in water treatment and distribution systems.

Copper ion (Cu2+), a common corrosion product released from copper pipes, is widely present in water distribution system (WDS). Cu2+ was confirmed to be capable to catalyze the decay of monochloramine (NH2Cl), which is a commonly used disinfectant and need to maintain a minimum concentration in WDS. Cu2+ and NH2Cl form a system in WDS and their interaction with other substances in WDS is unclear. In this study, the performance of Cu2+/NH2Cl system on degradation of trace pollutants, taking carbamazepine (CBZ) as an example, in WDS was investigated, and significant promotion on CBZ degradation was observed. The acceleration was due to the generation of Cl, OH and other oxidants, which were identified by scavenge experiments. CBZ degradation in Cu2+/NH2Cl system was highly pH-dependent, because the catalytic effect of Cu2+ can only work at low pH (Cu2+ precipitating at pH > 6.0). The removal of CBZ increased with the concentration of Cu2+ increasing. Water matrix (NOM, HCO3- and Br-) can inhibit the removal of CBZ in Cu2+/NH2Cl system. Further, five disinfection byproducts (DBPs), namely, trichloromethane (TCM), dichloroacetonitrile (DCAN), dichloroacetone (DCP), trichloronitromethane (TCNM) and trichloroacetone (TCP), were detected in chloramination in the presence/absence of Cu2+. Compared with chloramination without Cu2+, the cytotoxicity and genotoxicity of formed DBPs increased significantly in the presence of Cu2+, indicating that the chemical safety in WDS deserves more attention.

Although drinking water disinfection proved to be an effective strategy to eliminate many pathogens, bacteria can still show disinfection tolerance in drinking water distribution systems. To date, the molecular mechanisms on how environmental stress affects the tolerance of Pseudomonas aeruginosa to monochloramine are not well understood. Here, we investigated how three stress conditions, namely starvation, low temperature, and starvation combined with low temperature, affected the monochloramine tolerance of Pseudomonas aeruginosa, an opportunistic pathogen commonly found in drinking water distribution systems. All stress conditions significantly promoted monochloramine tolerance, among which starvation had the most drastic effects. Proteomic analyses suggested that the three conditions not only triggered a positive antioxidant defense against oxidative damages but also prepared the bacteria to employ a passive defense mechanism against disinfectants via dormancy. Moreover, the expression of antioxidant enzymes reached the maximum under the starvation condition and further low temperature treatment had little effect on bacterial response to oxidative stress. Instead, we found further treatment of the starved cells with low temperature decreased the osmotic stress response and the stringent response, which generally play pivotal roles in disinfection tolerance. Taken together, these findings shed light on how abiotic factors influence the bacterial disinfection tolerance and will aid design of efficient strategies to eliminate Pseudomonas aeruginosa from drinking water.

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.

The degradation of N,N-diethyl-meta-toluamide (DEET) in aqueous solution by the UV/monochloramine (UV/NH2Cl) process was examined systematically in this study. DEET was resistant to UV photolysis and chloramination, while the synchronous combination of UV irradiation and NH2Cl can effectively eliminate DEET, which was caused by the generation of hydroxyl radicals and reactive chlorine species. The former played the critical role in DEET degradation, while the contribution of the latter can be ignored. Under all investigated experimental conditions, DEET degradation in the UV/NH2Cl process followed the pseudo-first-order kinetic model. The water quality parameters exerted the complicated impact. Reducing solution pH and raising water temperature both favored the DEET removal. The presence of sulfate, humic acid and fulvic acid accelerated the degradation, while the introduction of bicarbonate and high-concentration chloride retarded the removal. The plausible degradation pathways of DEET in the UV/NH2Cl process were proposed through the combination of QTOF/MS analysis and DFT calculation, and mainly involved in the cleavage of C-N bond, dealkylation, mono- and polyhydroxylation. The acute toxicity of reacted solution underwent a trend of first increasing and then decreasing with the prolonged irradiation time, which can be well illustrated by quantitative structure-activity relationship analysis. Electrical energy per order was employed to determine the energy consumption and the optimal conditions were determined as UV fluence of 369.9-493.2 mJ cm-2 and NH2Cl dosage of 5-20 mg L-1.

This study investigated the formation of toxic iodinated trihalomethanes (I-THMs) during breakpoint chlorination of iodide-containing water. Impact factors including I- concentration, natural organic matter (NOM) concentration and type, pH as well as Br-/I- molar ratio were systematically investigated. Moreover, the incorporation of I- into I-THM formation was also calculated. The results showed that I-THM formation varied in different zones of the breakpoint curves. I-THMs increased with increasing chlorine dosage to breakpoint value and then dropped significantly beyond it. Iodoform (CHI3) and chlorodiiodomethane (CHClI2) were the major I-THMs in the pre-breakpoint zone, while dichloroiodomethane (CHCl2I) was the dominant one in the post-breakpoint zone. The formation of I-THMs increased remarkably with I- and dissolved organic carbon (DOC) concentrations. More bromine-containing species were formed as Br-/I- molar ratio increased from 0.5 to 5. In addition, the major I-THM compound shifted from CHCl2I to the more toxic CHClBrI. As pH increased from 6.0 to 8.0, I-THM formation kept increasing in the pre-breakpoint zone and the speciation of I-THMs changed alongside the breakpoint curves. The incorporation of I- during breakpoint chlorination was highly dependent on chlorine, I-, and NOM concentrations, NOM type, solution pH and Br-/I- molar ratio.

The Co(II)/peroxymonosulfate (Co(II)/PMS) process, producing sulfate radicals (SO4•-), effectively removes organic pollutants in water, while producing a significant amount of bromate (BrO3-) in the presence of bromide (Br-). This paper investigates the ammonia (NH3) addition, chlorine-ammonia (Cl2-NH3) and ammonia-chlorine (NH3-Cl2) pretreatment strategies in controlling BrO3- formation in 20 min in the Co(II)/PMS process at pH 4.0. The addition of NH3 retarded the BrO3- formation, but only at a reduction level of about 9.5% for NH3 concentration of 50 μM, and was mainly attributed to the protonation of NH3 at pH 4 (99.99% as NH4+, did not react with HOBr). Both the Cl2-NH3 and NH3-Cl2 pretreatment strategies at HOCl and NH3 dosages of 15 and 50 μM, respectively, reduced 95% or more of the overall BrO3- formation and retarded the BrO3- formation, with the NH3-Cl2 pretreatment strategy outperforming Cl2-NH3. The reduction of the BrO3- formation was mainly attributed to the formation of monochloramine (NH2Cl) in both pretreatment strategies. NH2Cl effectively outcompetes SO4•- to react with HOBr and forms NHBrCl, with the apparent reaction rate constant between NH2Cl and HOBr more than 100 times faster than that between SO4•- and HOBr. However, the oxidation/degradation of NHBrCl in the Co(II)/PMS process reforms HOBr, and, although less in quantity, is oxidized to BrO3- at higher Co(II) and Br- concentrations. Thus, the NH3-Cl2 and Cl2-NH3 pretreatment strategies inhibit the BrO3- formation more significantly at lower Co(II) and Br- concentrations. In all cases, the generation of SO4•- in 20 min was not affected by the implementation of the three BrO3- pretreatment strategies.