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A decades-long drinking-water disinfection mystery ends with a potentially toxic surprise.

Inorganic chloramines are commonly used drinking water disinfectants intended to safeguard public health and curb regulated disinfection by-product formation. However, inorganic chloramines themselves produce by-products that are poorly characterized. We report chloronitramide anion (Cl-N-NO 2 - ) as a previously unidentified end product of inorganic chloramine decomposition. Analysis of chloraminated US drinking waters found Cl-N-NO 2 - in all samples tested ( n = 40), with a median concentration of 23 micrograms per liter and first and third quartiles of 1.3 and 92 micrograms per liter, respectively. Cl-N-NO 2 - warrants occurrence and toxicity studies in chloraminated water systems that serve more than 113 million people in the US alone.

Disinfection is critical for ensuring water safety; however, the potential risks posed by disinfection byproducts (DBPs) have raised public concern. Previous studies have largely focused on low-molecular-weight DBPs with one or two carbon atoms, leaving the formation of high-molecular-weight DBPs (HMW DBPs, with more than two carbon atoms) less understood. This study explores the formation of HMW DBPs during the chloramination of phenolic compounds using a novel approach that combines high-resolution mass spectrometry with density functional theory (DFT) calculations. For the first time, we identified nearly 100 previously unreported HMW nitrogenous DBPs (N-DBPs), with nearly half of those being halogenated N-DBPs. These N-DBPs were tentatively identified as heterocyclic (e.g., pyrrole and pyridine analogs) and coupling heterocyclic N-DBPs. Through detailed structure analysis and DFT calculations, the key formation steps of heterocyclic N-DBPs (monochloramine-mediated ring-opening reactions of halobenzoquinones) and new bonding mechanisms (C-N, C-O, and C-C bonding) of the coupling heterocyclic N-DBPs were elucidated. The selective formation of these novel N-DBPs was significantly influenced by factors such as contact time, monochloramine dosage, pH, and bromide concentration. Our findings emphasize the occurrence of diverse HMW heterocyclic N-DBPs, which are likely toxicologically significant, underscoring the need for further research to evaluate and mitigate their potential health risks in water disinfection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Regulations typically use four trihalomethanes (THM4) and five haloacetic acids (HAA5) as metrics of consumer exposure to disinfection byproducts (DBPs) and their chronic health risks. Their use as exposure metrics assumes that their concentrations correlate with DBP-associated toxicity. For a chlorine-disinfected surface water, this study demonstrates that increasing chlorine contact time from 1 to 7 days was associated with a 62-76% increase in THM4 and HAA5 but a 40-47% decrease in total cytotoxicity. Thus, the use of THM4 and HAA5 may divert regulatory attention away from the low water age sections of distribution systems near treatment facilities that may feature the highest cytotoxicity but lowest THM4/HAA5 concentrations. Among common options to reduce THM4/HAA5, this study also shows that chlorine disinfection followed by chloramines for maintaining a distribution system residual did not substantially reduce cytotoxicity. Granular activated carbon followed by chlorine reduced cytotoxicity by 28-80%, even at the lowest water ages where cytotoxicity was maximized. These findings highlight the need to identify DBPs that better correlate with toxicity than THM4/HAA5 to serve as metrics of exposure. These metrics could help identify distribution system locations exhibiting higher consumer risk and develop modifications to disinfection systems that effectively reduce consumer risk.

Neutrophils orchestrate a coordinated attack on bacteria, combining phagocytosis with a potent cocktail of oxidants, including the highly toxic hypochlorous acid (HOCl), renowned for its deleterious effects on proteins. Here, we examined the occurrence of lipid N-chloramines in vivo, their biological activity, and their neutralization. Using a chemical probe for N-chloramines, we demonstrate their formation in the membranes of bacteria and monocytic cells exposed to physiologically relevant concentrations of HOCl. N-chlorinated model membranes composed of phosphatidylethanolamine, the major membrane lipid in Escherichia coli and an important component of eukaryotic membranes, exhibited oxidative activity towards the redox-sensitive protein roGFP2, suggesting a role for lipid N-chloramines in protein oxidation. Conversely, glutathione a cellular antioxidant neutralized lipid N-chloramines by removing the chlorine moiety. In line with that, N-chloramine stability was drastically decreased in bacterial cells compared to model membranes. We propose that lipid N-chloramines, like protein N-chloramines, are involved in inflammation and accelerate the host immune response., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Galvanic corrosion of lead-tin solder in copper plumbing can be a major contributor to water lead contamination. Here, we report the electrochemical reversal of the copper-solder galvanic couple, in which the normally anodic solder becomes cathodic to copper via a reaction with free chlorine. This reversal occurred after a few months of exposure to continuously circulating water with relatively low pH and low alkalinity, causing dramatically decreased lead release and the formation of a Pb(IV) scale. Chloramine did not similarly inhibit solder corrosion over the 4-9 month test duration, resulting in up to 100 times more lead contamination of the water relative to free chlorine. These findings have major implications for corrosion control and public health and can help explain anomalously low levels of lead contamination in some waters with free chlorine that are normally considered corrosive to solder.

Quaternary ammonium compounds (QACs) are widely detected in the aquatic environment due to their extensive use in a wide array of antibacterial products during the pandemic. In the current study, UV/monochloramine (UV/NH 2 Cl) was used to degrade three typical QACs, namely benzalkonium compounds (BACs), dialkyl dimethyl ammonium compounds (DADMACs), and alkyl trimethyl ammonium compounds (ATMACs). This process achieved high efficiency in removing BACs from water samples. The transformation products of QACs treated with UV/NH 2 Cl were identified and characterized using a high-resolution mass spectrometer, and transformation pathways were proposed. The formation of N-nitroso-N-methyl-N-alkylamines (NMAs) and N-nitrosodimethylamine (NDMA) were observed during QAC degradation. The molar formation yield of NDMA from C 12 -BAC was 0.04 %, while yields of NMAs reached 1.05 %. The ecotoxicity of NMAs derived from QACs was predicted using ECOSAR software. The increased toxicity could be attributed to the formation of NMAs with longer alkyl chains; these NMAs, exhibited a one order of magnitude increase in toxicity compared to their parent QACs. This study provides evidence that QACs are the specific and significant precursors of NMAs. Greater attention should be given to NMA formation and its potential threat to the ecosystem, including humans., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The UV/monochloramine (UV/NH 2 Cl) process, while efficiently eliminating micropollutants, produces toxic byproducts. This study utilized Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to investigate molecular-level changes in natural organic matter (NOM) and to disclose formation pathways of nitro(so) and chloro byproducts in the UV/NH 2 Cl process. The UV/NH 2 Cl process significantly increased the saturation and oxidation levels and altered the elemental composition of NOM. Using 15 N labeling and a screening workflow, nitro(so) byproducts with nitrogen originating from inorganic sources (i.e., reactive nitrogen species (RNS) and/or NH 2 Cl) were found to exhibit total intensities comparable to those from NOM. RNS, rather than NH 2 Cl, played a significant role in incorporating nitrogen into NOM. Through linkage analysis, nitro(so) addition emerged as an important reaction type among the 25 reaction types applied. By using phenol as a representative model compound, the nitro byproducts were confirmed to be mainly generated through the oxidation of nitroso byproducts instead of nitration. Machine learning and SHAP analysis further identified the major molecular indices distinguishing nitro(so) and chloro precursors from non-precursors. This study enhances our fundamental understanding of the mechanisms driving the generation of nitro(so) and chloro byproducts from their precursors in complex NOM during the UV/NH 2 Cl process., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Developing predictive models for iodo-trihalomethane (I-THM) formation in water is needed and valuable to minimize extensive and costly analysis. The main objective of this study was to develop a statistical model for the formation of six types of I-THMs under uniform formation conditions. Prediction of I-THM formation in two different water sources (natural organic matter [NOM] and algal organic matter [AOM]) were comprehensively evaluated during both preformed chloramination and prechlorination followed by ammonia addition conditions. In addition, the prediction of THM10 (sum of six I-THM and THM4) formation was conducted during both oxidation strategies for NOM waters. In total, 460 experimental results were compiled from the literature and our own database. The results showed the coefficient of determination (R 2 ) values for the six I-THM species ranged between 0.53-0.68 and 0.35-0.79 in the preformed NH 2 Cl and perchlorinated NOM waters, respectively. Among all independent variables, the I - exhibited the most significant influence on the formation of all I-THM species in the preformed NH 2 Cl, while SUVA 254 was the most influential parameter for perchlorinated NOM water. When the preformed chloramination was compared with prechlorination followed by ammonia addition, the R 2 value for I-THMs (0.93) was higher than for THM4 formation (0.79) in preformed chloramination. In the prechlorination followed by ammonia addition condition, the model prediction of I-THMs (R 2 = 0.45) formation was lower than THM4 (R 2 = 0.96). Overall, the pH, I - , SUVA 254 , and oxidant type are all played crucial roles in determining the I-THM formation, impacting the overall effectiveness and predictability of the models., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Algal blooms have become a significant challenge in water treatment all over the world. In chlorination of drinking water, algal organic matter (AOM) leads to the formation of organic chloramines. The objectives of this review are to comprehensively summarize and discuss the up-to-date researches on AOM-derived organic chloramines and their chemical activities and toxicity, thereby drawing attention to the potentially chemical and hygienic risks of organic chloramines. The predominant algal species in water sources varied with location and season. AOM from cyanobacteria, green algae, and diatoms are composed of diverse composition. AOM-derived amino acids take a low portion of the precursors of organic chloramines. Both experimental kinetic data and quantum chemical calculation demonstrate the preferential formation of organic chloramines in the chlorination of model compounds (amino acids and peptides). Organic chloramines are persistent in water and can transform into dichloro- and trichloro-organic chloramines, unknown low-molecular-weight organic chloramines, and nitrogenous disinfection byproducts with the excess of free chlorine. The active chlorine (Cl + ) in organic chloramines can lead to the formation of chlorinated phenolic compounds. Organic chloramines influence the generation and species of radicals and subsequent products in UV disinfection. Theoretical predictions and toxicological tests suggest that organic chloramines may cause oxidative or toxic pressure to bacteria or cells. Overall, organic chloramines, as one group of high-molecular-weight disinfection byproducts, have relatively long lifetimes, moderate chemical activities, and high hygienic risks to the public. Future perspectives of organic chloramines are suggested in terms of quantitative detection methods, the precursors from various predominant algal species, chemical activities of organic chloramines, and toxicity/impact., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The presence of CECs in aquatic systems has raised significant concern since they are potentially harmful to the environment and human health. Eliminating CECs has led to the development of alternatives to treat wastewater, such as advanced oxidation processes (AOPs). The ultraviolet-mediated activation of monochloramine (UV/NH 2 Cl) is a novel and relatively unexplored AOPs for treating pollutants in wastewater systems. This process involves the production of amino radicals ( • NH 2 ) and chlorine radicals (Cl • ) from the UV irradiation of NH 2 Cl. Studies have demonstrated its effectiveness in mitigating various CECs, exhibiting advantages, such as the potential to control the amount of toxic disinfection byproducts (TDBPs) formed, low costs of reagents, and low energy consumption. However, the strong influence of operating parameters in the degradation efficiency and existence of NH 2 Cl, the lack of studies of its use in real matrices and techno-economic assessments, low selectivity, and prolonged treatment periods must be overcome to make this technology more competitive with more mature AOPs. This review article revisits the state-of-the-art of the UV/NH 2 Cl technology to eliminate pharmaceutical and personal care products (PPCPs), micropollutants from the food industry, pesticides, and industrial products in aqueous media. The reactions involved in the production of radicals and the influence of operating parameters are covered to understand the formation of TDBPs and the main challenges and limitations of the UV/NH 2 Cl to degrade CECs. This review article generates critical knowledge about the UV/NH 2 Cl process, expanding the horizon for a better application of this technology in treating water contaminated with CECs., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Chlorine-resistant bacteria (CRB) in drinking water treatment plants (DWTPs) jeopardize water quality and pose a potential risk to human health. However, the specific response of CRB to chlorination and chloramination remains uncharacterized. Therefore, we analyzed 16 S rRNA sequencing data from water samples before and after chlorination and chloramination taken between January and December 2020. Proteobacteria and Firmicutes dominated all finished water samples. After chloramination, Acinetobacter, Pseudomonas, Methylobacterium, Ralstonia, and Sphingomonas were the dominant CRB, whereas Ralstonia, Bacillus, Acinetobacter, Pseudomonas, and Enterococcus were prevalent after chlorination. Over 75% of the CRB e.g. Acinetobacter, Pseudomonas, Bacillus, and Enterococcus were shared between the chlorination and chloramination, involving potentially pathogens, such as Acinetobacter baumannii and Pseudomonas aeruginosa. Notably, certain genera such as Faecalibacterium, Geobacter, and Megasphaera were enriched as strong CRB after chloramination, whereas Vogesella, Flavobacterium, Thalassolituus, Pseudoalteromonas, and others were enriched after chlorination according to LEfSe analysis. The shared CRB correlated with temperature, pH, and turbidity, displaying a seasonal pattern with varying sensitivity to chlorination and chloramination in cold and warm seasons. These findings enhance our knowledge of the drinking water microbiome and microbial health risks, thus enabling better infectious disease control through enhanced disinfection strategies in DWTPs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Chloramination is an effective strategy for eliminating pathogens from drinking water and repressing their regrowth in water distribution systems. However, the inevitable release of NH 4 + potentially promotes nitrification and associated ammonia-oxidizing bacteria (AOB) contamination. In this study, AOB (Nitrosomona eutropha) were isolated from environmental water and treated with two disinfection stages (chloramine disinfection and chloramine residues) to investigate the occurrence mechanisms of AOB in chloramination. The results showed that N. eutropha had considerable resistance to monochloramine compared to Escherichia coli, whose inactivation rate constant was 19.4-fold lower. The higher resistance was attributed to high levels of extracellular polymer substances (EPS) in AOB, which contribute to AOB surviving disinfection and entering the distribution system. In AOB response to the chloramine residues stage, the respiratory activity of N. eutropha remained at a high level after three days of continuous exposure to high chloramine residue concentrations (0.5-1.5 mg/L). Reverse transcription-quantitative polymerase chain reaction (RT-qPCR) suggested that the mechanism of N. eutropha tolerance involved a significantly high expression of the intracellular oxidative stress-regulating (sodB, txrA) and protein-related (NE1545, NE1546) genes. Additionally, this process enhanced EPS secretion and promoted biofilm formation. Adhesion predictions based on the XDLVO theory corroborated the trend of biofilm formation. Overall, the naturally higher resistance contributed to the survival of AOB in primary disinfection; the enhanced antioxidant response of surviving N. eutropha accompanied by biofilm formation was responsible for their increased resistance to the residual chloramines., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

In drinking water chloramination, monochloramine autodecomposition occurs in the presence of excess free ammonia through dichloramine, the decay of which was implicated in N -nitrosodimethylamine (NDMA) formation by (i) dichloramine hydrolysis to nitroxyl which reacts with itself to nitrous oxide (N 2 O), (ii) nitroxyl reaction with dissolved oxygen (DO) to peroxynitrite or mono/dichloramine to nitrogen gas (N 2 ), and (iii) peroxynitrite reaction with total dimethylamine (TOTDMA) to NDMA or decomposition to nitrite/nitrate. Here, the yields of nitrogen and oxygen-containing end-products were quantified at pH 9 from NHCl 2 decomposition at 200, 400, or 800 μeq Cl 2 ·L -1 with and without 10 μM-N TOTDMA under ambient DO (∼500 μM-O) and, to limit peroxynitrite formation, low DO (≤40 μM-O). Without TOTDMA, the sum of free ammonia, monochloramine, dichloramine, N 2 , N 2 O, nitrite, and nitrate indicated nitrogen recoveries ±95% confidence intervals were not significantly different under ambient (90 ± 6%) and low (93 ± 7%) DO. With TOTDMA, nitrogen recoveries were less under ambient (82 ± 5%) than low (97 ± 7%) DO. Oxygen recoveries under ambient DO were 88-97%, and the so-called unidentified product of dichloramine decomposition formed at about three-fold greater concentration under ambient compared to low DO, like NDMA, consistent with a DO limitation. Unidentified product formation stemmed from peroxynitrite decomposition products reacting with mono/dichloramine. For a 2:2:1 nitrogen/oxygen/chlorine atom ratio and its estimated molar absorptivity, unidentified product inclusion with uncertainty may close oxygen recoveries and increase nitrogen recoveries to 98% (ambient DO) and 100% (low DO).

Organic chloramines in water would pose both chemical and microbiological risks. It is essential to remove the precursors of organic chloramine (amino acids and decomposed peptides/proteins) to limit its formation in disinfection. In our work, nanofiltration was chosen to remove organic chloramines precursors. To solve the "trade-off" effect and low rejection of small molecules in algae organic matter, we synthesized a thin film composite (TFC) nanofiltration (NF) membrane with a crumpled polyamide (PA) layer via interfacial polymerization on polyacrylonitrile (PAN) composite support loaded with covalent organic framework (COF) nanoparticles (TpPa-SO 3 H). The obtained NF membrane (PA-TpPa-SO 3 H/PAN) increased the permeance from 10.2 to 28.2 L m -2 h -1 bar -1 and the amino acid rejection from 24% to 69% compared to the control NF membrane. The addition of TpPa-SO 3 H nanoparticles decreased the thickness of PA layers, increased the hydrophilicity of the membrane, and increased the transition energy barrier for amino acids transferring through the membrane, which was identified by scanning electron microscope, contact angle test, and density functional theory computations, respectively. Finally, pre-oxidation coupled with PA-TpPa-SO 3 H/PAN membrane nanofiltration on the limitation of organic chloramines formation was evaluated. We found that the combined application of KMnO 4 pre-oxidation and PA-TpPa-SO 3 H/PAN membranes nanofiltration in algae-containing water treatment could minimize the formation of organic chloramines in subsequent chlorination and maintain a high flux during filtration. Our work provides an effective way for algae-containing water treatment and organic chloramines control., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The formation characteristics of trihalomethanes (THMs) and haloacetamides (HAcAms) from dissolved organic matter and its fractions were investigated during chlorine-based disinfection processes. The relationships between water quality parameters, fluorescence parameters, and the formation levels of THMs and HAcAms were analyzed. The fractions contributing most to the acute toxicity were identified. The trichloromethane (TCM) generation level (72 h) generally followed the order of Cl 2  > NH 2 Cl > NHCl 2 process. The NHCl 2 process was superior to the NH 2 Cl process in controlling TCM formation. Hydrophobic acidic substance (HOA), hydrophobic neutral substance (HON), and hydrophilic substance (HIS) were identified as primary precursors of 2,2-dichloroacetamide and trichloroacetamide during chlorination and chloramination. The formation of TCM mainly resulted from HOA, HON and HIS fractions relatively uniformly, while HOA and HIS fractions contributed more to the formation of bromodichloromethane and dibromomonochloromethane. UV 254 could be used as an alternative indicator for the amount of ΣTHMs formed during chlorination and chloramination processes. Dissolved organic nitrogen was a potential precursor of 2,2-dichloroacetamide during chlorination process. The fractions with the highest potential acute toxicity after the chlorination were water-dependent., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

We studied the properties of N6-chloroadenosine phosphates (ATP, ADP, and AMP chloramines) as compounds with potentially increased antiplatelet efficacy determined by their binding to the plasma membrane of platelets. Chloramine derivatives of ATP, ADP, and AMP do not differ in their optical absorption characteristics: their absorption spectra are in the range of 220-340 nm with a maximum at 264 nm. Chloramines of adenosine phosphates are characterized by high reactivity with respect to thiol compounds. In particular, the rate constants of the reaction of N6-chloroadenosine-5'-diphosphate with N-acetylcysteine, reduced glutathione, dithiothreitol, and cysteine reach 59,000, 250,000, 340,000, and 1,250,000 M -1 ×sec -1 , respectively, and only 1.10±0.02 M -1 ×sec -1 with methionine. It has been found that N6-chloradenosine-5'-triphosphate is a strong inhibitor of platelet functions: it effectively suppresses ADP-induced cell aggregation (IC 50 in the whole blood is 5 μM) and inhibits aggregation of preactivated platelets and induces dissociation of their aggregates., (© 2023. Springer Science+Business Media, LLC, part of Springer Nature.)

A rising outbreak of waterborne diseases caused by global warming requires higher microbial stability in the drinking water distribution system (DWDS). Chloramine disinfection is gaining popularity in this context due to its good persistent stability and fewer disinfection byproducts. However, the microbiological risks may be significantly magnified by ammonia-oxidizing bacteria (AOB) in distribution systems during global warming, which is rarely noticed. Hence, this work mainly focuses on AOB to explore its impact on water quality biosafety in the context of global warming. Research indicates that global warming-induced high temperatures can directly or indirectly promote the growth of AOB, thus leading to nitrification. Further, its metabolites or cellular residues can be used as substrates for the growth of heterotrophic bacteria (e.g., waterborne pathogens). Thus, biofilm may be more persistent in the pipelines due to the presence of AOB. Breakpoint chlorination is usually applied to control such situations. However, switching between this strategy and chloramine disinfection would result in even more severe nitrification and other adverse effects. Based on the elevated microbiological risks in DWDS, the following aspects should be paid attention to in future research: (1) to understand the response of nitrifying bacteria to high temperatures and the possible association between AOB and pathogenic growth, (2) to reveal the mechanisms of AOB-mediated biofilm formation under high-temperature stress, and (3) to develop new technologies to prevent and control the occurrence of nitrification in drinking water distribution system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Mask wearing and bleach disinfectants became commonplace during the COVID-19 pandemic. Bleach generates toxic species including hypochlorous acid (HOCl), chlorine (Cl 2 ), and chloramines. Their reaction with organic species can generate additional toxic compounds. To understand interactions between masks and bleach disinfection, bleach was injected into a ventilated chamber containing a manikin with a breathing system and wearing a surgical or KN95 mask. Concentrations inside the chamber and behind the mask were measured by a chemical ionization mass spectrometer (CIMS) and a Vocus proton transfer reaction mass spectrometer (Vocus PTRMS). HOCl, Cl 2 , and chloramines were observed during disinfection and concentrations inside the chamber are 2-20 times greater than those behind the mask, driven by losses to the mask surface. After bleach injection, many species decay more slowly behind the mask by a factor of 0.5-0.7 as they desorb or form on the mask. Mass transfer modeling confirms the transition of the mask from a sink during disinfection to a source persisting >4 h after disinfection. Humidifying the mask increases reactive formation of chloramines, likely related to uptake of ammonia and HOCl. These experiments indicate that masks are a source of chemical exposure after cleaning events occur.

Chlorine reactions with peptide-bound amino acids form disinfection byproducts and contribute to pathogen inactivation by degrading protein structure and function. Peptide-bound lysine and arginine are two of the seven chlorine-reactive amino acids, but their reactions with chlorine are poorly characterized. Using N -acetylated lysine and arginine as models for peptide-bound amino acids and authentic small peptides, this study demonstrated conversion of the lysine side chain to mono- and dichloramines and the arginine side chain to mono-, di-, and trichloramines in ≤0.5 h. The lysine chloramines formed lysine nitrile and lysine aldehyde at ∼6% yield over ∼1 week. The arginine chloramines formed ornithine nitrile at ∼3% yield over ∼1 week but not the corresponding aldehyde. While researchers hypothesized that the protein aggregation observed during chlorination arises from covalent Schiff base cross-links between lysine aldehyde and lysine on different proteins, no evidence for Schiff base formation was observed. The rapid formation of chloramines and their slow decay indicate that they are more relevant than the aldehydes and nitriles to byproduct formation and pathogen inactivation over timescales relevant to drinking water distribution. Previous research has indicated that lysine chloramines are cytotoxic and genotoxic to human cells. The conversion of lysine and arginine cationic side chains to neutral chloramines should alter protein structure and function and enhance protein aggregation by hydrophobic interactions, contributing to pathogen inactivation.

Chloramines (NH 2 Cl, NHCl 2 , and NCl 3 ) are toxic compounds that can be created during the use of bleach-based disinfectants that contain hypochlorous acid (HOCl) and the hypochlorite ion (OCl - ) as their active ingredients. Chloramines can then readily transfer from the aqueous-phase to the gas-phase. Atmospheric chemical ionization mass spectrometry using iodide adduct chemistry (I-CIMS) made observations across two periods (2014 and 2016) at an urban background site on the University of Leicester campus (Leicester, UK). Both monochloramine (NH 2 Cl) and molecular chlorine (Cl 2 ) were detected and positively identified from calibrated mass spectra during both sampling periods and to our knowledge, this is the first detection of NH 2 Cl outdoors. Mixing ratios of NH 2 Cl reached up to 2.2 and 4.0 parts per billion by volume (ppbv), with median mixing ratios of 30 and 120 parts per trillion by volume (pptv) during the 2014 and 2016 sampling periods, respectively. Levels of Cl 2 were observed to reach up to 220 and 320 pptv. Analysis of the NH 2 Cl and Cl 2 data pointed to the same local source, a nearby indoor sports complex with a swimming pool and a cleaning product storage shed. No appreciable levels of NHCl 2 and NCl 3 were observed outdoors, suggesting the indoor pool was not likely to be the primary source of the observed ambient chloramines, as prior measurements made in indoor pool atmospheres indicate that NCl 3 would be expected to dominate. Instead, these observations point to indoor cleaning and/or cleaning product emissions as the probable source of NH 2 Cl and Cl 2 where the measured levels provide indirect evidence for substantial amounts transported from indoors to outdoors. Our upper estimate for total NH 2 Cl emissions from the University of Leicester indoor sports complexes scaled for similar sports complexes across the UK is 3.4 × 10 5 ± 1.1 × 10 5 μg h -1 and 0.0017 ± 0.00034 Gg yr -1 , respectively. The Cl-equivalent emissions in HCl are only an order of magnitude less to those from hazardous waste incineration and iron and steel sinter production in the UK National Atmospheric Emissions Inventory (NAEI).

Nitrogenous disinfection by-products (N-DBPs) raise increasing concerns because of their high genotoxicity, cytotoxicity, and carcinogenicity compared to carbonaceous disinfection by-products (C-DBPs). Nitrogen-containing disinfectants, dissolved organic nitrogen (DON), and inorganic nitrogen may all promote the formation of N-DBPs. Therefore, it is urgent to explore the dominant nitrogen source of N-DBPs under the coexistence of multiple nitrogen sources. In this study, the effects of amino acids, nitrate, ammonia, and chloramine as different types of nitrogen sources on the formation of five N-DBPs were investigated systematically, including chloroacetonitrile (CAN), dichloroacetonitrile (DCAN), bromochloroacetonitrile (BCAN), dibromoacetonitrile (DBAN) and dichloroacetamide (DCAcAm). L-Aspartic acid (L-Asp) as the organic nitrogen source showed a high potential on the formation of N-DBPs by forming acetonitrile intermediates. Ammonia as the inorganic nitrogen source consumed oxidants and changed the existing form of chloramine, thus inhibiting the formation of N-DBPs. Instead of providing nitrogen to N-DBPs, nitrate as a salt promoted the volatilization of N-DBPs, thereby reducing the detected N-DBPs. Furthermore, an isotope labeling method was applied to clearly trace the nitrogen sources of N-DBPs via GC-MS with electron ionization. 15 N-chloramine, 15 N-amino acid, 15 N-nitrate and 15 N-ammonia were selected as the corresponding isotopic nitrogen sources. The results indicated that chloramine was the major nitrogen contributor to five N-DBPs during the chloramination of L-Asp under the coexistence of multiple nitrogen sources, ranging from 61 % to 79 %. The influence of environmental factors (reaction time, pH, and bromide) on the formation of N-DBPs during chloramination was also investigated. There was competition between brominated N-DBPs and chlorinated N-DBPs in chloramination. With the increase of reaction time or bromine, the formation potentials of chlorinated N-DBPs gradually decreased, while brominated N-DBPs gradually increased. Moreover, higher pH inhibited the generation of N-DBPs., Competing Interests: Declaration of competing interest The authors declare that they have no conflicts of interest to this work. The authors declare that they do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Organic chloramines (OCs) have become one of the research focuses in the field of drinking water treatment due to its limited oxidation and sterilization ability as well as potential cytotoxicity and genetic toxicity to the public. Among widespread OCs, produced by chlorinating cytosine are a typical one exists during chlorine disinfection. OCs degradation during UV, chlorination and UV/chlorine processes were systematically investigated. UV irradiation at 254 nm could effectively degrade OCs by 96.6% after 60 min, mainly because N-Cl bond had significant UV absorption at 250-280 nm leading to the generation of Cl• and HO•. Direct chlorination had poor removal of OCs with the OCs concentration increased first and then decreased as time went by. On the other hand, the removal of OCs during UV/chlorination was much higher than that during chlorination, but was worse than that during UV alone. pH had a minor effect on OCs decomposition via UV irradiation, whereas the effect was pronounced in the chlorination and UV chlorine processes. UV wavelength can affect the degradation of OCs with efficiency decreased in the order of UV 254 > UV 265 > UV 275. The total yields of disinfection by-products (DBPs) during the degradation of OCs followed UV/chlorine > UV > chlorination. CH and DCAA were the two dominant types of DBPs among detected 7 DBPs. DBPs yield followed the order of UV254 > UV265 > UV275 at pH 6.0 and 7.0. After UV 265 irradiation, DBPs yield slightly decreased by 2.4%, 3.0% and 6.6% with the pH increased from 6.0 to 9.0. The results can provide theoretical basis for effective control of OCs in drinking water., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The formation of disinfection byproducts (DBPs) during UV/chlorine treatment, especially nitrogenous DBPs, is not well understood. This study investigated the formation mechanisms for dichloroacetonitrile (DCAN) from typical amino compounds during UV/chlorine treatment. Compared to chlorination, the yields of DCAN increase by 88-240% during UV/chlorine treatment from real waters, while the yields of DCAN from amino compounds increase by 3.3-5724 times. Amino compounds with electron-withdrawing side chains show much higher DCAN formation than those with electron-donating side chains. Phenylethylamine, l- phenylalanine, and l-phenylalanyl-l-phenylalanine were selected to represent amines, amino acids, and peptides, respectively, to investigate the formation pathways for DCAN during UV/chlorine treatment. First, chlorination of amines, amino acids, and peptides rapidly forms N -chloramines via chlorine substitution. Then, UV photolysis but not radicals promotes the transformation from N -chloramines to N -chloroaldimines and then to phenylacetonitrile, with yields of 5.4, 51.0, and 19.8% from chlorinated phenylethylamine, l-phenylalanine, and l-phenylalanyl-l-phenylalanine to phenylacetonitrile, respectively. Finally, phenylacetonitrile is transformed to DCAN with conversion ratios of 14.2-25.6%, which is attributed to radical oxidation, as indicated by scavenging experiments and density functional theory calculations. This study elucidates the pathways and mechanisms for DCAN formation from typical amino compounds during UV/chlorine treatment.

This study demonstrated the tracking of ulcerative colitis, which is considered a stressful immune disease. Although there are many ways to test for this disease including dependence on gases, dyes, and painful anal endoscopy, these treatment modalities have many disadvantages. Hence, it is the utmost need of time to discover new methods to detect this chronic immune disease and to avoid the defects of traditional methodologies. Sulfasalazine (SSD) was labeled with iodine-131 (half-life: 8 days, Energy: 971 keV) under optimum reaction conditions including the amount of reducing agent, pH factor, chloramine-T (Ch-T) amount, and incubation period. Characterization was performed using 1 H/ 13 C-NMR, ESI-MS, and HPLC (UV/ Radio) techniques. The biodistribution study was performed in normal and ulcerative mice models, and in silico molecular docking study was performed to evaluate the possible mechanism of action to target peroxisome proliferator-activated receptor gamma (PPARγ). The high radiolabeling yield of [ 131 I]-sulfasalazine ([ 131 I]-SSD) was achieved ≥90% through the direct labeling method with radioactive iodine-131 in the presence of chloramine-T (100 μg). The radiotracer [ 131 I]-SSD was observed to be stable in normal saline and freshly eluted serum up to 12 hr at ambient temperature (37℃ ± 2℃). The radiotracer [ 131 I]-SSD showed the highest uptake in the targeted organ (i.e., ulcerative colon) which was observed to be ≥75% injected dose per gram (% ID/g) organ for 24 hr postinjection (p.i). Furthermore, in silico data collected from molecular modeling analysis of SSD and [ 131 I]-SSD with antimicrobial protein (PDB code: 3KEG) and peroxisome proliferator-activated receptor gamma (PPARγ) (PDB code: 4XTA) showed azoreductase activity and high binding potential for PPAR-γ site, respectively. The results of biological studies obtained in this study enlighten the usefulness of radiotracer [ 131 I]-SSD as a potential imaging agent for ulcerative colitis., (© 2021 John Wiley & Sons Ltd.)

Radioiodine labeling of peptides and proteins is routinely performed by using various oxidizing agents such as Chloramine T, Iodobeads, and Iodogen reagent and radioactive iodide (I - ), although some other oxidizing agents were also investigated. The main objective of the present study was to develop and test a novel reagent, inorganic monochloramine (NH 2 Cl), for radioiodine labeling of new chemical entities and biomolecules which is cost-effective, easy to make and handle, and is selective to label amino acids, peptides, and proteins. The data presented in this report demonstrate that the yields of the non-radioactive iodine labeling reactions using monochloramine are >70% for an amino acid (tyrosine) and a cyclic peptide (cyclo Arg-Gly-Asp-d-Tyr-Lys, cRGDyK). No evidence of the formation of N -chloro derivatives in cRGDyK was observed, suggesting that the reagent is selective in iodinating the tyrosine residue in the biomolecules. The method was successfully translated into radioiodine labeling of amino acid, a peptide, and a protein, Bovine Serum Albumin (BSA).

Covalent modifications by reactive oxygen species can modulate the function and stability of proteins. Thermal unfolding experiments in solution are a standard tool for probing oxidation-induced stability changes. Complementary to such solution investigations, the stability of electrosprayed protein ions can be assessed in the gas phase by collision-induced unfolding (CIU) and ion-mobility spectrometry. A question that remains to be explored is whether oxidation-induced stability alterations in solution are mirrored by the CIU behavior of gaseous protein ions. Here, we address this question using chloramine-T-oxidized cytochrome c (CT-cyt c ) as a model system. CT-cyt c comprises various proteoforms that have undergone MetO formation (+16 Da) and Lys carbonylation (LysCH 2 -NH 2 → LysCHO, -1 Da). We found that CT-cyt c in solution was destabilized, with a ∼5 °C reduced melting temperature compared to unmodified controls. Surprisingly, CIU experiments revealed the opposite trend, i.e., a stabilization of CT-cyt c in the gas phase. To pinpoint the source of this effect, we performed proteoform-resolved CIU on CT-cyt c fractions that had been separated by cation exchange chromatography. In this way, it was possible to identify MetO formation at residue 80 as the key modification responsible for stabilization in the gas phase. Possibly, this effect is caused by newly formed contacts of the sulfoxide with aromatic residues in the protein core. Overall, our results demonstrate that oxidative modifications can affect protein stability in solution and in the gas phase very differently.

Electron-deficient chlorine covalently immobilised on an amido group of hyaluronic acid (HA) can be potentially exceptional for applications requiring biodegradable and biocompatible polymers with enhanced antibacterial or antiviral activity. This expectation is supported by the assumption that a small amount of HA chloramide (HACl) is formed in the extracellular matrix under inflammatory conditions by a reaction of endogenous HA with hypochlorous acid (HClO) generated by a myeloperoxidase/H 2 O 2 /Cl - system. HACl synthesis optimisation showed significant limitations of HClO as an oxidative agent where only lower degrees of substitution (DS) was achieved. Commercially available oxidative agents based on chlorinated isocyanuric acid were successfully tested, producing the HA chain with almost entirely chlorinated amidic groups. The structure of the final HACl was thoroughly studied using advanced 2-dimensional NMR methodologies and LC/MS. Stability of HACl at different temperatures was monitored over 12 months. Preliminary antimicrobial and antiviral tests demonstrated the potential of HACl for applications in biomedicine., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Herein, we demonstrate the on-demand synthesis of chloramine from aqueous ammonia and sodium hypochlorite solutions, and its subsequent utilization as an ambiphilic nitrogen source in continuous-flow synthesis. Despite its advantages in cost and atom economy, chloramine has not seen widespread use in batch synthesis due to its unstable and hazardous nature. Continuous-flow chemistry, however, provides an excellent platform for generating and handling chloramine in a safe, reliable, and inexpensive manner. Unsaturated aldehydes are converted to valuable aziridines and nitriles, and thioethers are converted to sulfoxides, in moderate to good yields and exceedingly short reaction times. In this telescoped process, chloramine is generated in situ and immediately used, providing safe and efficient conditions for reaction scale-up while mitigating the issue of its decomposition over time.

This study examined the potential of six aliphatic and aromatic amides, commonly found in natural waters or used as chemical aids in water treatment, to act as organic precursors for nine haloacetamides (HAcAms), five haloacetonitriles (HANs), regulated trihalomethanes (THMs) and haloacetic acids (HAAs) upon chlorination and chloramination. The impact of key experimental conditions, representative of drinking water, including pH (7 & 8), retention time (4 & 24 h) and bromide levels (0 & 100 μg/L), on the generation of the target DBPs was investigated. The highest aggregate DBP yields upon chlor(am)ination were reported for the aromatic and hydrophobic hydroxybenzamide; 2.7% ± 0.1% M/M (chlorination) and 1.7% M/M (chloramination). Increased reactivity was observed in aliphatic and hydrophilic compounds, acrylamide (2.5 ± 0.2% M/M) and acetamide (1.3 ± 0.2% M/M), in chlorination and chloramination, respectively. The addition of bromide increased average DBP yields by 50-70%. Relative to chlorination, the application of chloramines reduced DBP formation by 66.5% (without Br - ) and by 46.4% (with Br - ). However, bromine incorporation in HAAs and HAcAms was enhanced following chloramination, of concern due to the higher toxicological potency of brominated compounds., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

2,4-diaminobutyric acid (DAB), a newly identified algal toxins in water, pose a great threat to human health. DAB may react with chlorine or chloramine to produce CX 3 R-type disinfection by-products (DBPs) during water treatment processes. This study mainly investigated the formation and speciation of DBPs from chlor(am)ination of DAB. The results revealed that haloacetic acids (HAAs), trihalomethanes (THMs) and haloacetonitriles (HANs) were the main kinds of CX 3 R-type DBPs generated from DAB during chlor(am)ination, of which dichloroacetic acid yielded the highest. The formation and total toxicity of four CX 3 R-type DBPs from DAB during chloramination was significantly lower than that during chlorination at each Cl 2 :N molar ratio. However, more formation of Br-THMs and I-THMs were observed during chloramination in the presence of Br - /I - . Futhermore, the effects of chlor(am)ine dosage, solution pH, reaction time, and the concentration of Br - and I - on the formation and speciation of CX 3 R-type DBPs were also evaluated during chlor(am)ination. The plausible formation pathways of CX 3 R-type DBPs from DAB were proposed and verified by theoretical calculation. The quantum chemistry calculations indicate that 1N in DAB and 8N in 2,4-diaminochlorobutyric acid (C 4 H 9 O 2 N 2 Cl) were more likely to be attacked by electrophiles, supporting the proposed pathway schemes., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Rhodium(III) octahedral complexes with amine and chloride ligands are the most common starting compounds for preparing catalytically active rhodium(I) and rhodium(III) species. Despite intensive study during the last 100 years, synthesis and crystal structures of rhodium(III) complexes were described only briefly. Some [RhCl x (NH 3 ) 6- x ] compounds are still unknown. In this study, available information about synthetic protocols and the crystal structures of possible [RhCl x (NH 3 ) 6 - x ] octahedral species are summarized and critically analyzed. Unknown crystal structures of (NH 4 ) 2 [Rh(NH 3 )Cl 5 ], trans- [Rh(NH 3 ) 4 Cl 2 ]ClH 2 O, and cis- [Rh(NH 3 ) 4 Cl 2 ]Cl are reported based on high quality single crystal X-ray diffraction data. The crystal structure of [Rh(NH 3 ) 5 Cl]Cl 2 was redetermined. All available crystal structures with octahedral complexes [RhCl x (NH 3 ) 6- x ] were analyzed in terms of their packings and pseudo-translational sublattices. Pseudo-translation lattices suggest face-centered cubic and hexagonal closed-packed sub-cells, where Rh atoms occupy nearly ideal lattices., Competing Interests: The authors declare no conflict of interest.

Aripiprazole (ARP) is one of antipsychotics and binds to human serum albumin (HSA) with a high affinity. In this study, we investigated the binding characteristics of ARP to oxidized HSA as observed in chronic disease conditions. Oxidized HSAs were prepared using chloramine-T (CT-HSA) or metal-catalyzed oxidation system (MCO-HSA) in vitro, respectively. An increase in the carbonyl content was confirmed in oxidized HSAs. From the results of circular dichroism (CD) and tryptophan fluorescence spectra, no significant structural change of oxidized HSAs was observed. These results indicate that prepared HSAs are mildly oxidized and well reflects the status of HSA during chronic diseases. However, oxidized HSAs were observed to have a significant decrease in binding to ARP. The results of the induced CD spectrum suggested that ARP bound to oxidized HSAs with a similar orientation. These results suggest that oxidation of HSA during chronic disease state significantly affected the microenvironment of the binding site for ARP and binding capacity of HSA to ARP.

Thermosensitive transient receptor potential (TRP) ion channels detect changes in ambient temperature to regulate body temperature and temperature-dependent cellular activity. Rodent orthologs of TRP vanilloid 2 (TRPV2) are activated by nonphysiological heat exceeding 50 °C, and human TRPV2 is heat-insensitive. TRPV2 is required for phagocytic activity of macrophages which are rarely exposed to excessive heat, but what activates TRPV2 in vivo remains elusive. Here we describe the molecular mechanism of an oxidation-induced temperature-dependent gating of TRPV2. While high concentrations of H 2 O 2 induce a modest sensitization of heat-induced inward currents, the oxidant chloramine-T (ChT), ultraviolet A light, and photosensitizing agents producing reactive oxygen species (ROS) activate and sensitize TRPV2. This oxidation-induced activation also occurs in excised inside-out membrane patches, indicating a direct effect on TRPV2. The reducing agent dithiothreitol (DTT) in combination with methionine sulfoxide reductase partially reverses ChT-induced sensitization, and the substitution of the methionine (M) residues M528 and M607 to isoleucine almost abolishes oxidation-induced gating of rat TRPV2. Mass spectrometry on purified rat TRPV2 protein confirms oxidation of these residues. Finally, macrophages generate TRPV2-like heat-induced inward currents upon oxidation and exhibit reduced phagocytosis when exposed to the TRP channel inhibitor ruthenium red (RR) or to DTT. In summary, our data reveal a methionine-dependent redox sensitivity of TRPV2 which may be an important endogenous mechanism for regulation of TRPV2 activity and account for its pivotal role for phagocytosis in macrophages., Competing Interests: The authors declare no competing interest.

The residues of pharmaceuticals and personal care products (PPCPs) in environmental waters have been widespread concerned. Metronidazole (MNZ), normally employed to treat inflammation and infection, was chosen as one model PPCP. The degradation of MNZ by chlorination could be fitted by pseudo-first-order kinetics as the observed pseudo-first-order rate constants increasing from 0.0302 min -1 to 0.2872 min -1 . However, the kinetics during chloramination of MNZ followed pseudo-second-order reaction, whose estimated half-live was approximately 6-8 times longer than chlorination. The chlor(am)ination of MNZ especially formed chloroform (CF), dicholoacetamide (DCAcAm), tricholoacetamide (TCAcAm) and dichloroacetonitrile (DCAN), and their yields were overall lower under chloramination than chlorination. During chlorination, the yield of CF was increased from 0.35 ± 0.02% to 2.06 ± 0.12% with 1-20 chlorine/MNZ molar ratio, whereas the formations of DCAcAm, TCAcAm and DCAN increased firstly and then decreased. Increasing chloramine dosage promoted the concentrations of scheduled disinfection byproducts (DBPs). CF and TCAcAm kept continuous generation in chlor(am)ination versus reaction time. Compared with the chlorination, the chloramination of MNZ was more dependent on pH value due to the self-degradation of chloramine. Faintly acidic condition favored N-DBPs' formation in MNZ when it was subjected to chlor(am)ination. The chloramination of MNZ produced cytotoxicity and genotoxicity by 10-15 folds lower than chlorination, and DCAN formed during chloramination dominated both DBPs' yields and toxicity contribution. Opposite to chlorination, the integrated toxicity of MNZ during chloramination varied linearly versus N-DBPs' yields., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Functionalized polysulfone (PSf) membranes with combined antibacterial and antifouling properties were fabricated by incorporating a poly(ethyleneoxide)-grafted (PEO-grafted) amphiliic polymer. Both antifouling and antibacterial groups were easily introduced onto the membrane surfaces through non-solvent induced phase separon process and a simple chlorination process. It was observed that the functionalized membranes were effectivatie in resisting both protein absorption and bacterial adhesion. Furthermore, the functionalized membrane (M3-Cl) showed mostly suppressed irreversible flux decline and a 97% flux recovery ratio after simple washing during the separation process, indicating excellent antifouling properties. Meanwhile, the functionalized PSf membrane exhibited efficient biocidal activity against E. coli and S. aureus. These modified functionalized PSf membranes also displayed outstanding properties in inhibiting the formation of biofilm. Moreover, the antibacterial feature was renewable by a simple process., (Copyright © 2019. Published by Elsevier Inc.)

Biochar (BC) is as an emerging and promising adsorbent for the removal of pollutants from aqueous solutions in water treatment given its porous structure, large surface area, and numerous O-functional groups. However, the effects of BC on the formation of disinfection byproducts (DBPs) during the disinfection process of water treatment remains largely unknown. This study investigated the influence of aqueous solution chemistry on DBP formation in the presence of BC during chlorination. BC samples prepared from different biomass precursors (wheat straw, peanut shells, and shaddock peel) with different pyrolysis temperatures were compared, and the effects of aqueous solution chemistry were systematically investigated. Results indicated that DBPs could be formed during disinfection with BC. Certain intermediate DBP products would undergo base catalysis to form trichloromethane (TCM) via hydrolysis as pH increased. This phenomenon would increase TCM content, as well as decrease chloral hydrate and 1,1-dichloro-2-propanone content. The increment in inorganic ion (NaCl) content showed negligible effects on DBP formation during BC chlorination. DBP formation was restrained in the presence of humic acid (HA) because the number of active sites on BC that participated in the reaction decreased when BC adsorbed HA., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

As a widely used antiepileptic drug, carbamazepine (CBZ) has been frequently detected in aquatic environments, even in drinking water. Chloramine is a widely used alternative disinfectant due to its low-level formation of regulated disinfection byproducts (DBPs). However, there is previous evidence linking product mixtures of chloraminated CBZ to stronger DNA damage effects than those caused by CBZ itself. The present study further investigated the reaction rate, transformation mechanism and multi-endpoint toxicity of transformation products (TPs) of CBZ treated with NH 2 Cl under different pH conditions. The results showed that the reaction between CBZ and NH 2 Cl at pH 8.5, where NH 2 Cl is stable, is a second-order reaction with a rate of 4.2 M -1  h -1 . Compared to both alkaline and acidic conditions, CBZ was quickly degraded at pH 7. This indicated that HOCl produced from NH 2 Cl hydrolysis is more effective in degrading CBZ than NH 2 Cl and NHCl 2 . Furthermore, the concentration variation of four TPs formed during the chloramination of CBZ under different pH conditions was investigate by quantitative analysis, and the transformation pathway from CBZ to 9(10H)-acridone was confirmed. Three of the detected TPs showed cytotoxicity, DNA damage effects or chromosome damage effects. Acridine and 9(10H)-acridone, which accumulated with increasing time, showed higher cytotoxic or genotoxic effects than CBZ itself. In addition, a similar transformation mechanism was observed in real ambient water during simulated chloramination with a low level of CBZ. These results suggested that despite the chloramination of CBZ being slower than chlorination, TPs with higher cytotoxicity or genotoxicity may lead to greater toxic risks., (Copyright © 2019 Elsevier B.V. All rights reserved.)

As the first identified category of disinfection byproducts (DBPs), trihalomethanes (THMs) have received continuous attention. Previous studies have demonstrated that the transformation of aromatic halogenated DBPs during chlor (am)ination resulted in the formation of THMs, which may occur in both water treatment plants and drinking water distribution systems. In this study, THM yields from aromatic chlorinated/brominated DBPs during chlorination and aromatic iodinated DBPs during chloramination were investigated. The trichloromethane (TCM) yields from 3,5-dichloro-4-hydroxybenzaldehyde, 3,5-dichlorosalicylic acid, 2,6-dichloro-4-nitrophenol, and 2,4,6-trichlorophenol were in the range of 0-11.4%, 0-8.4%, 0-6.4%, and 0-17.8%, respectively. The THM 4 (TCM, bromodichloromethane (BDCM), dibromochloromethane (DBCM), and tribromomethane (TBM)) yields from 3,5-dibromo-4-hydroxybenzaldehyde, 3,5-dibromosalicylic acid, 2,6-dibromo-4-nitrophenol, and 2,4,6-tribromophenol were in the range of 0-12.9%, 0-27.0%, 0-8.6%, and 0-29.4%, respectively. The TCM and triiodomethane (TIM) yields from 3,5-diiodo-4-hydroxybenzaldehyde, 3,5-diiodosalicylic acid, 2,6-diiodo-4-nitrophenol, and 2,4,6-triiodophenol were in the range of 0-5.2%, 0-7.0%, 0-2.2%, and 0-10.6%, respectively. After 72 h, TCM yields from aromatic chlorinated DBPs were generally higher than that from their brominated analogues; TBM yields from aromatic brominated DBPs were significantly lower than TCM yields, BDCM yields, and DBCM yields; and among aromatic halogenated DBPs, 2,4,6-trihalophenol had the highest THM yields while 2,6-dihalo-4-nitrophenol had the lowest THM yields. Moreover, the results revealed that alkaline conditions and higher temperatures favored the THM yields from the twelve aromatic halogenated DBPs during chlor (am)ination, and chlorine/monochloramine dose affected the yields and speciation of THMs from the aromatic halogenated DBPs., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Chloramines are commonly used as secondary disinfectants in drinking water treatment, providing a residual for disinfection as drinking water moves to consumers. Chloramines are inherently unstable, undergoing autodecomposition reactions even in the absence of reactive substances. In the presence of natural organic matter (NOM), chloramine loss accelerates due to additional reaction pathways. In this study, batch reaction models for chloramine loss due to autodecomposition and the presence of NOM were developed. A case study was carried out for the Town of Cary, North Carolina. A hydraulic model of Cary's distribution system was developed and calibrated using the EPANET toolkit with operational and water demand data supplied by Cary. Then, water age from the hydraulic model was used together with the batch model of chloramine decay to successfully predict chloramine concentrations spatially and temporally throughout the network. The capabilities of the EPANET-MSX toolkit to model chloramine loss in a distribution network are explored. PRACTITIONER POINTS: A batch reaction model of chloramine decay over time due to autodecomposition reactions and additional reactions with NOM was developed and validated. A hydraulic model of the Town of Cary's water distribution network was developed and calibrated using operational and water demand data. Water age reported by the calibrated hydraulic model was used in conjunction with the batch reaction model of chloramine decay to successfully predict chloramine concentrations spatially and temporally throughout the network., (© 2019 Water Environment Federation.)

Hypochlorous acid (HOCl) is a highly reactive, toxic species generated by neutrophils via the action of myeloperoxidase in order to destroy invading pathogens. However, when HOCl is produced inappropriately, it can damage host tissue and proteins and plays a role in the initiation and progression of disease. Carnosine, a peptide of β-alanine and histidine, has been shown to react rapidly with HOCl yielding monochloramines and can undergo intramolecular transchlorination. The current study examines the kinetics and pH dependence of the reactions of carnosine and novel structural derivatives with HOCl and the occurrence of intra- and intermolecular transchlorination processes. We demonstrate that the transchlorination reactions of carnosine are pH dependent, with intramolecular transfer favored at higher pH. Carcinine, having a structure identical to carnosine though lacking the carboxylic acid group of the histidine residue, reacts with HOCl and forms monochloramines though intramolecular transfer reactions are not observed, and this is supported by computational modeling. Novel analogues with one (carnosine+1) and two (carnosine+2) methylene groups in the alkyl chain of the β-alanine react with HOCl to yield monochloramines that undergo transchlorinations to yield a mixture of mono- and dichloramines. The latter are stable over 24 h. The ability of carnosine and derivatives to react rapidly with HOCl to give long-lived, poorly reactive, species may prevent damage to proteins and other targets at sites of inflammation.

The Amino acid Derivative Reactivity Assay (ADRA) is an in chemico alternative to animal testing for skin sensitization potential that uses two different nucleophilic reagents and it is known that ADRA hardly exhibts co-elution compared with the Direct Peptide Reactivity Assay (DPRA) based on the same scientific principles. In this study, we have analyzed the factors underlying why co-elution, which is sometimes an issue during DPRA testing, virtually never occurs during ADRA testing. Chloramine T and dimethyl isophthalate both exhibited co-elution during DPRA testing, but when quantified at both DPRA's 220 nm and ADRA's 281 nm, we found that when the later detection wavelength was used, these test chemicals produced extremely small peaks that did not interfere with quantification of the peptides. And although both salicylic acid and penicillin G exhibited co-elution during DPRA testing, when tested at a concentration just 1% of that used in DPRA, the very broad peak produced at the higher concentration was reduced significantly. However, both these test chemicals exhibited very sharp peaks when the pH of the injection sample was adjusted to be acidic. Based on these results, we were able to clarify that the reasons why nucleophlic reagents hardly co-elute with test chemicals during ADRA testing are depend on the following three major reasons: (1)differences in the detection wavelength, (2)differences in test chemical concentrations in the injection sample, (3)differences in composition of the injection solvent., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Disinfection byproducts (DBPs) have attracted extensive attention due to their cytotoxicity and genotoxicity. This study investigates the effects of different ions on DBP formation during chlorination and chloramination in artificial and real water samples. Compared with chlorination, chloramination can reduce the formation of DBPs. K + only reduce the formation of DBPs during chloramination. Ca 2+ forms less DBPs than Mg 2+ does during chlorination and chloramination due to the stronger binding effect. Al 3+ and their hydroxide colloids have a significant effect on DBP formation. Anions have no significant effect on DBP formation. Due to the difference between the real and artificial water samples, the large amount of NH 4 + in the real water will form chloramine during chlorination. Furthermore, the effects of different ion in the chlorination will have the same tendency during chlorination. In the wastewater with high ionic strength, the effects of salts are mostly ignored. Studying the effects of different ions on DBP formation is important in controlling the content of DBPs in the disinfection process., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The objective of this research was to explore the fundamental reactions between chlorine/chloramine and 2-hydroxyl-4-methoxyl benzophenone (BP3)/2-hydroxyl-4-methoxyl benzophenone-sulfonic acid (BP4), which were the most common reactions in benzophenone-type UV filters during drinking water treatment processes. Both BP3 and BP4 could react with free chlorine and chloramine, with reactions following pseudo-first-order kinetics in excess of chlorine (HClO) and chloramine (NH 2 Cl). Generally, chlorination was more rapid than chloramination. BP4 was less reactive than BP3 toward both chlorine and chloramine, due to the presence of an electron-accepting sulfonate group. Therefore, BP3 had a significantly higher disinfection by-products (DBP) formation potential than BP4. Chlorination of BP3 and BP4 generated remarkably higher levels of DBPs than chloramination, with high pH conditions facilitating the formation of chloroform but inhibiting the formation of haloacetic acid (HAAs). Comparison of the reaction behavior of two different BP-type UV filters, i.e., BP3 and BP4, revealed that certain functional groups significantly affected the reactivity of BP-type UV filters in chlorination and chloramination processes. This contribution may provide new insights into the reaction behavior of UV filters during drinking water disinfection process using chlorine and/or chloramine as disinfectant, and provide guidelines for drinking water safety management., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Treatment of fully nitrified municipal wastewater effluents with chlorine followed by chloramines (i.e., sequential chlorine disinfection) upstream of advanced treatment trains can contribute pathogen inactivation credits for potable reuse while leaving a chloramine residual to control biofouling on membrane units in the advanced treatment train. However, free chlorine exposures must be optimized to maximize pathogen inactivation while minimizing the formation of disinfection byproducts (DBPs) that are challenging to remove in the advanced treatment train. Using a pilot-scale disinfection contactor receiving fully-nitrified, tertiary municipal wastewater effluent, this study found that a 3 mg × min/L free chlorine CT (i.e., the product of the chlorine residual "C" and the contact time "T") followed by a 140 mg × min/L chloramine CT could reliably achieve 5-log inactivation of MS2 bacteriophage and reduce median total coliform concentrations below 2.2 MPN/100 mL. Free chlorine disinfection was equally effective when chlorine was dosed to exceed the breakpoint for 1 mg/L of ammonia as N. At this free chlorine exposure, regulated trihalomethane (THM) and haloacetic acid (HAA) formation remained below their Maximum Contaminant Levels (MCLs), but NDMA concentrations of ∼30 ng/L were above the 10 ng/L California Notification Level. Increasing the free chlorine exposure to ∼30 mg × min/L increased THM and HAA formation, with regulated THMs approaching or exceeding the MCL. Although this free chlorine exposure prevented NDMA formation during chloramination, the ∼10 ng/L background NDMA formation in the tertiary effluent remained. Increasing the free chlorine exposure also increased the formation of unregulated halogenated DBP classes that may be significant contributors to the DBP-associated toxicity of the disinfected wastewater. The results indicate that sequential chlorination can be used to optimize the benefits of free chlorine (virus and NDMA control) and chloramine disinfection (THM, HAA, and coliform control)., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this work, the disinfection of highly faecal-polluted surface water was studied using a new electrochemical cell (CabECO ® cell, manufactured by CONDIAS) specifically designed to produce ozone in water with very low conductivity. The disinfection tests were carried out in a discontinuous mode to evaluate the influence of the electrode current charge passed. The effect of the current density was also studied in order to optimize the disinfection conditions and to simultaneously prevent the formation of undesirable by-products (chlorates and perchlorates) during the electrolysis. The results demonstrate that this technology is robust and efficient, and it can suitably disinfect water. During electrolysis, the chloride contained in the water was oxidized to hypochlorite, and this compound was combined with ammonia to form chloramines. Both hypochlorite and chloramines (formed by the well-known break point reaction) promoted persistent disinfection and seemed to be mainly responsible for the disinfection attained during the electrochemical process. Chlorate and perchlorate could also be produced, although the low concentrations of chloride in the tested water made them irrelevant. The removal of the total organic carbon under the applied operating conditions was not very efficient (although it reached 50% in 2 h) and the production of trihalomethanes was very low, below 100 ppb for all tests., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Haloacetamides (HAMs), a group of nitrogenous disinfection byproducts (N-DBPs), can decompose to form corresponding intermediate products and other DBPs. The stability of ten different HAMs, including two chlorinated, five brominated, and three iodinated species was investigated with and without the presence of chlorine, chloramines, and reactive solutes such as quenching agents. The HAM basic hydrolysis and chlorination kinetics were well described by a second-order kinetics model, including first-order in HAM and hydroxide and first-order in HAM and hypochlorite, respectively, whereas the HAM neutral hydrolysis kinetic was first-order in HAM. Furthermore, HAMs decompose instantaneously when exposed to hypochlorite, which was almost two and nine orders of magnitude faster than HAM basic and neutral hydrolysis, respectively. In general, HAM hydrolysis and chlorination rates both increased with increasing pH and the number of halogens substituted on the methyl group. Moreover, chlorinated HAMs are more unstable than their brominated analogs, followed by the iodinated ones, due to the decrease in the electron-withdrawing inductive effect from chlorine to iodine atom. During hydrolysis, HAMs mainly directly decompose into the corresponding haloacetic acids (HAAs) via a nucleophilic reaction between the carbonyl carbon and hydroxide. For HAM chlorination reactions, hypochlorite reacts with HAMs to form the N-chloro-HAMs (N-Cl-HAMs) via Cl + transfer from chlorine to the amide nitrogen. N-Cl-HAMs can further degrade to form HAAs via hypochlorous acid addition. In contrast, the reactions between chloramines and HAMs were found to be insignificant. Additionally, four common quenching agents, including sodium sulfite, sodium thiosulfate, ascorbic acid, and ammonium chloride, were demonstrated to expedite HAM degradation, whereas ammonium chloride was the least influential among the four. Taft linear free energy relationships were established for both HAM hydrolysis and chlorination reactions, based on which the hydrolysis and chlorination rate constants for three monohaloacetamides were estimated. The hydrolysis and chlorination rates of 13 HAMs decreased in the following order: TCAM > BDCAM > DBCAM > TBAM > DCAM > BCAM > DBAM > CIAM > BIAM > DIAM > MCAM > MBAM > MIAM (where C = chloro, B = bromo, I = iodo, T = tri, D = di, M = mono). Lastly, using the HAM kinetic model established in this study, HAM half-lifes in drinking water distribution systems can be predicted on the basis of pH and residual chlorine concentration., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Present study aimed to generate multiple regression models to estimate the formation of trihalomethanes (THMs), haloacetonitriles (HANs) and haloacetic acids (HAAs) during chloramination of source water obtained from Yangtze River Delta Region, China. The results showed that the regression models for trichloromethane (TCM), dichloroacetonitrile (DCAN), dichloroacetic acid (DCAA), dihaloacetic acids (DHAAs), 5 HAAs species regulated by U.S. EPA (HAA 5 ) and total haloacetic acids (HAA 9 ) have good evaluation ability (prediction accuracy reached 81-94%), while the models for total haloacetonitriles (HAN 4 ), trichloroacetic acid (TCAA), trihaloacetic acids (THAAs) and total trihalomethanes (THM 4 ), they appeared relative low prediction accuracy (58-72%). For THMs, dissolved organic nitrogen (DON) was their key organic precursor, yet for HAN, DHAAs and THAAs, UVA 254 played the dominant role. The other key factors influencing DBP formation included the bromide (THM 4 , DHAAs and HAA 9 ), reaction time (DCAN, HAN 4 ), chloramine dose (TCM, DCAA, TCAA, HAA 5 and THAAs). These results provided important information for water works to optimize the water treatment process to control DBPs, and give an evaluating method for DBPs levels when estimating the health risks related with DBP exposure during chloramination., (Copyright © 2018 Elsevier Inc. All rights reserved.)