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.

Nitrification is a serious water-quality issue in chloraminated engineered water systems (EWSs). Nitrification is often remediated by a chlorine burn (i.e., a free‑chlorine conversion), a short-term switch from chloramination to chlorination in EWSs. Opportunistic pathogens (OPs) are the dominant infectious agents in EWSs. However, the responses of OPs to a chlorine burn are unknown. This study for the first time assessed how a chlorine burn affected OPs in a full-scale EWS. We determined the impact of a 1.5-month chlorine burn on four dominant OPs (Legionella, Mycobacterium, Pseudomonas, and Vermamoeba vermiformis) in a representative full-scale chloraminated EWS in the United States. Legionella and Mycobacterium were the most abundant OPs. In the water main, the summed concentration of the four OPs during the chlorine burn [3.27 ± 1.58 log10(GCN·L-1); GCN: genome or gene copy number] was lower (p ≤ 0.001) than before the burn [4.83 ± 0.50 log10(GCN·L-1)]. After the burn, the summed concentration increased to 4.27 ± 0.68 log10(GCN·L-1), comparable to before the burn (p > 0.05), indicating a transient effect of the chlorine burn in the water main. At the residential sites, the summed concentrations of the four OPs were comparable (p > 0.05) at 5.50 ± 0.84, 5.27 ± 1.44, and 5.08 ± 0.71 log10(GCN·L-1) before, during, and after the chlorine burn, respectively. Therefore, the chlorine burn was less effective in suppressing OP (re)growth in the premise plumbing. The low effectiveness might be due to more significant water stagnation and disinfectant residual decay in the premise plumbing. Indeed, for the entire sampling period, the total chlorine residual concentration in the premise plumbing (1.8 mg Cl2·L-1) was lower than in the water main (2.4 mg Cl2·L-1). Consequently, for the entire sampling period, the summed concentration of the four OPs in the premise plumbing [5.26 ± 1.08 log10(GCN·L-1)] was significantly higher (p < 0.001) than in the water main [4.04 ± 1.25 log10(GCN·L-1)]. In addition, the chlorine burn substantially increased the levels of disinfection by-products (DBPs) in the water main. Altogether, a chlorine burn is transient or even ineffective in suppressing OP (re)growth but raises DBP concentrations in chloraminated EWSs. Therefore, the practice of chlorine burns to control nitrification should be optimized, reconsidered, or even replaced.

BACKGROUND: Nitrite (NO2-) and nitrate (NO3-) can be produced in the distribution systems of chloraminated drinking water due to the nitrification of ammonia. The most applied inorganic chloramine for this purpose, namely monochloramine (NH2Cl), is also released into aquatic environments from water treatment plants\' effluent and within industrial waste streams. Within the treatment process, the continuous monitoring of disinfectant levels is necessary to limit the harmful disinfectant by-product (DBP) formation. Currently, NH2Cl can interfere with nutrient analysis in water samples, and there are no analytical techniques available for the simultaneous analysis of NH2Cl, NO2-, and NO3-.
RESULTS: A green analytical method based on mixed-mode ion chromatography, specifically ion exchange and ion exclusion modes, was developed for the simultaneous separation and detection of NH2Cl, NO2-, and NO3-. The separation was achieved using a Dionex IonPac AG15 column guard column and a step gradient elution involving deionized water and 120.0 mM NaCl. The method was developed using a benchtop HPLC with a custom-made multi-wavelength UV absorbance detector with a 50-mm flow cell to enable the sensitive detection of NH2Cl, NO2-, and NO3- at 240 nm, 220 nm, and 215 nm, respectively. The developed method was then transferred to a portable ion chromatography (IC) system, the Aquamonitrix analyser. The total run time was less than 10 min for both systems. The benchtop HPLC method had a limit of detection (LOD) of 0.07 μg mL-1 as Cl2 for NH2Cl, 0.01 μg mL-1 for NO2-, and 0.03 μg mL-1 for NO3-. The LODs obtained using the portable Aquamonitrix analyser were found to be 0.36 μg mL-1 as Cl2, 0.02 μg mL-1, and 0.11 μg mL-1 for NH2Cl, NO2-, and NO3-, respectively. Excellent linearity (r ≥ 0.9999) was achieved using the portable analyser over the studied concentration ranges. The developed system was applied to the analysis of spiked municipal drinking water samples and showed excellent repeatability for the three analytes at three different concentration levels (RSD of triplicate recovery experiments ≤ 1.9 %). Moreover, the variation in retention time was negligible for the three target analytes with RSD ≤ 0.8 % over 12 runs.
CONCLUSIONS: We are reporting the first ion chromatographic method for the simultaneous separation and detection of NH2Cl, NO2-, and NO3- in water samples. The monitoring of NH2Cl, NO2-, and NO3- is critical for the determination of disinfectant dosing, water quality, and nitrification status. The developed method can be applied using a benchtop HPLC or via the portable automated IC system to monitor for the three target compounds analysis in water treatment plants.

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.

Monochloramine (NH2Cl) is applied upstream of reverse osmosis (RO) membranes for biofouling control. Residual NH2Cl can undergo UV photolysis downstream, generating reactive species for an AOP to occur. At the bench-scale, NH2Cl is typically generated from combining sodium hypochlorite and ammonium chloride or sulfate. This study investigated the degradation of four compounds of interest - acetaminophen, caffeine, sucralose and 1,4-dioxane - in UV/NH2Cl at the bench scale to study their reactivity with reactive chlorine species (RCS) and reactive nitrogen species (RNS). With methanol acting as a scavenger of •OH radicals, the performance of UV/NH2Cl was compared to UV/H2O2 and UV/HOCl. In UV/H2O2, dioxane was severely inhibited at 1-2 mg/L H2O2 and comparable at 5 mg/L to UV/NH2Cl. When ammonium sulfate ((NH4)2SO4) was used as the ammonia source over ammonium chloride (NH4Cl), the overall degradation of micropollutants was higher and caffeine was exclusively degraded. At 1-2 mg/L NH2Cl, dioxane degraded by 16.2-17.8% and 2.92-5.29% from (NH4)2SO4 and NH4Cl respectively while caffeine degraded by 7.45-9.61% with NH2Cl ((NH4)2SO4), but not degrade with NH2Cl (NH4Cl). The higher concentration of chloride ions from NH4Cl significantly influenced the speciation of generated radicals and impacted micropollutant degradation. This suggests that the reactivity of more selective RCS (Cl2•-, •ClO, ClOH•-) and RNS (•NH2, •NO, •NO2, etc.) varies with micropollutants of interest. The presence of higher chloride concentration from the ammonia source inhibited the generation of •OH radicals with •OH consumed by RNS to form NO3- (μg/L levels), showing the impact of the choice of ammonia source and the water matrix on UV/NH2Cl performance.

As a widely used secondary vulcanization accelerator in the rubber industry, 1,3-diphenylguanidine (DPG) poses risks to human health and the environment. To compare and comprehend the disinfection process of DPG, this work investigates the reaction kinetics, toxicity, and transformation products (TPs) of DPG during chlorination and monochloramination. It has been revealed that the reactivity of monochloramine is significantly slower compared to chlorination of DPG, with the maximum efficiency observed at pH 7 to pH 8. Cytotoxicity assessment using HepG2 and THP-1 cells reveals that cytotoxicity hierarchy is as follows: chlorine TPs > monochloramine TPs > DPG. Moreover, oxidant-to-DPG molar ratios 10 and 20 lead to higher cytotoxicity in both chlorination and monochloramination compared to ratio 5 and 100. Additionally, cell bioenergetics experiments demonstrate that chlorine and monochloramine TPs induce mitochondrial dysfunction and enhance glycolytic function in HepG2 cells. The genotoxic response from p53 signaling further suggested genotoxic effects of certain TPs. Furthermore, analysis of TPs using high-resolution mass spectrometry (HRMS) identifies ten TPs, with chlorination yielding more TPs than monochloramination. Generally, a chlorine or monochloramine molar ratio to DPG of 10-20 results in an increased formation of TPs and heightened cytotoxicity. Notably, higher oxidant molar ratios increased the formation of monoguanidine TPs and DPG hydroxylation during chlorination, whereas monochloramination lead to DPG substitution predominantly generating chlorinated DPG due to weaker oxidation effects. These findings provide valuable information for the appropriate treatment of DPG and disinfection processes in water facilities to mitigate potential risks to human health and the ecosystem.

Fecal shedding of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) by infected persons into wastewater was documented early during the COVID-19 pandemic, thereby stimulating inquiries into the effectiveness of municipal wastewater treatment processes for the reduction of infectious viruses. In wastewater treatment plants, free chlorine has traditionally been the disinfectant utilized due to its low cost and high efficacy. However, regulations limiting disinfection by-products have prompted a shift to chloramination in many areas of the United States. While studies regarding the effectiveness of free chlorine against many viral agents are abundant, the efficacy of monochloramine (NH2Cl) has been less well researched. This study aimed to determine the effectiveness of pre-formed monochloramine for disinfection of human coronavirus 229E (HCoV-229E) in both phosphate-buffered saline (PBS) and reclaimed water from a water reclamation plant in Tucson, Arizona. Reclaimed water was sampled over the course of six months (August 2020 to November 2020), and dosed with monochloramine at 3 mg/L. An additional 1 mg/L free ammonia was added to simulate the operational conditions of the treatment plant. Viability was determined using MRC-5 host cell monolayers, using the TCID50 assay method. An average Ct99.9 (concentration of disinfectant multiplied by the contact time to achieve a 99.9 % reduction of the target organism) of 176 mg*min/L monochloramine was determined. No significant difference in inactivation rate was observed between the dosed reclaimed water and phosphate buffered saline (PBS). These data indicate that monochloramine is an effective disinfectant for coronaviruses. They also indicate that the water matrix type did not significantly impact the disinfection efficacy of monochloramine against HCoV-229E in reclaimed wastewater compared to PBS.

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.

Legionella contamination control is crucial in healthcare settings where patients suffer an increased risk of disease and fatal outcome. To ensure an effective management of this health hazard, the accurate application of a hospital-specific Water Safety Plan (WSP), the choice of a suitable water disinfection system and an extensive monitoring program are required. Here, the ten-year experience of an Italian hospital is reported: since its commissioning, Legionellosis risk management has been entrusted to a multi-disciplinary Working Group, applying the principles of the World Health Organization\'s WSP. The disinfection strategy to prevent Legionella and other waterborne pathogens relies on the treatment of domestic hot water with a system ensuring the in situ production and dosage of monochloramine. An average of 250 samples/year were collected and analyzed to allow an accurate assessment of the microbiological status of water network. With the aim of increasing the monitoring sensitivity, in addition to the standard culture method, an optimized MALDI-ToF MS-based strategy was applied, allowing the identification of Legionella species and other relevant opportunistic pathogens. Data collected so far confirmed the effectiveness of this multidisciplinary approach: the fraction of positive samples never overcame 1% on a yearly basis and Legionnaires\' Disease cases never occurred.

Thirty-two short term (∼7.5 h) abiotic experiments were conducted with new ductile iron and copper coupons exposed to various water qualities, including pH (7 or 9), dissolved inorganic carbon (DIC, 10 or 50 mg C L-1) and phosphate (0 or 3 mg P L-1) concentrations and 4 mg Cl2 L-1 free chlorine or monochloramine. To quantify oxidant reactivity with the new metal coupons, microelectrodes were used to obtain oxidant (free chlorine or monochloramine and dissolved oxygen (DO)) concentration and pH microprofiles from the bulk water to near the metal coupon surface. From the microprofiles, apparent surface reaction rate constants (k) were determined for each oxidant. An ANOVA analysis evaluated if the five variables (Material, Oxidant, Phosphate, DIC, and pH) significantly affected estimates of k, finding that the Material and Oxidant variables and their interaction were statistically significant (p<0.05), but the effect of variables of Phosphate, DIC, and pH on k values were not significant in this study. In general, both ductile iron and copper coupons showed significant surface reactivity towards free chlorine and monochloramine. For ductile iron, DO consumption was greater than for copper, which showed minimal DO reactivity, and DO was less reactive towards the copper surface than either free chlorine or monochloramine. Furthermore, pH microprofiles provided insight into the complexity that might exist near corroding metal surfaces where the bulk water pH may be substantially different from that measured near metal surfaces which is significant as pH is a controlling variable in terms of scale formation and metal solubility. This study represents an important first step towards using microelectrodes to (1) understand and provide direct measurement of oxidant microprofiles from the bulk water to the metal surface; (2) determine pipe wall reactivity using the directly measured concentrations profiles versus estimated pipe wall reactivity from bulk water measurements, and (3) understand how variables measured by bulk water samples (e.g., pH) may be drastically different from what is occurring at and near the metal surface. Together, these insights will assist in understanding disinfectant residual maintenance, corrosion, and metal release.