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Metformin, a first-line drug used to treat type 2 diabetes, is not metabolised in the body and discharged into the environment in the form of prototype drugs. Compounds C (C 4 H 6 ClN 3 ) and Y (C 4 H 6 ClN 5 ) are the main disinfection byproducts of metformin in urban sewage treatment; however, their potential toxicity is unclear. In this study, absorption, distribution, metabolism, elimination, and toxicity (ADMET) prediction indicated that compounds C and Y had potential hepatotoxicity and could cross the blood-brain-barrier. Toxicity verification tests indicated a sex difference in the acute toxicity of compound C, with an LD 50 value of 253.269 mg kg -1 for male mice and 728.908 mg kg -1 for female mice. The subacute toxicity of compounds C and Y was evaluated to study the toxicity mechanism via the gut-liver-brain axis, which indicated that they could cause damage to the liver and brain, change the composition of the gut microbiota, and disturb the levels of metabolites in mice. Neuron-like magnetic N-doped biochar (NiFe-LDOs/N-BC) was synthesised using hydrothermal and calcination methods, and the optimised d-MSPE-HPLC-UV method was proven to be applicable for the trace detection of compound C in real water samples. The simultaneous presentation of toxicity evaluation and trace detection of compound C is intended to make the monitoring system for compound C more comprehensive., 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.)

• BrCl instead of HOBr dominates benzotriazoles degradation during seawater chlorination. • BrCl reacts with benzotriazole at a rate constant 30,000 times higher than HOBr. • Ten brominated products including mono-, di-, and tribrominated derivatives were identified. • BrCl significantly increases the generation and toxicity of brominated products. A common understanding attributes the formation of brominated disinfection by-products (Br-DBPs) in seawater chlorination to the conversion of hypochlorous acid to hypobromous acid (HOBr) by bromide. In this study, we reveal that bromine chloride (BrCl), mediated by both chloride and bromide in seawater, plays a dominant role in the transformation of 1H-benzotriazole (BTA) and 5-methyl-1H-benzotriazole (MBTA) and in the formation of brominated DBPs. Using anisole as a reference compound, the second-order rate constant for the reaction of BrCl with BTA was determined to be (2.65 ± 0.13) × 105 L mol−1 s−1, which is over 30,000 times higher than that for the reaction between HOBr and BTA. Ten brominated products were identified and showed a successive bromination pattern. The bromination reaction mechanism was elucidated through theoretical calculations, and the pathways were proposed. The concentrations of brominated BTA and MBTA in seawater were 5.7 and 7.9 times higher than in bromide-only solutions, respectively. BrCl significantly promoted brominated product generation and increased the toxicity of blended DBPs. These results suggest that focusing solely on bromide's effect on brominated product generation may significantly underestimate the potential for DBP formation during seawater chlorination. [Display omitted] [ABSTRACT FROM AUTHOR]

• The fate of DBPs induced by metals in the drinking water distribution system is reviewed. • Copper, iron, and manganese significantly promote the formation and transformation of DBPs in the DWDS. • These metals critically impact the occurrence of high DBP segments in pipelines. • A comprehensive index map among different metals and DBPs inside the DWDS is summarized. Metals in the drinking water distribution system (DWDS) play an important role on the fate of disinfection by-products (DBPs). They can increase the formation of DBPs through several mechanisms, such as enhancing the proportion of reactive halogen species (RHS), catalysing the reaction between natural organic matter (NOM) and RHS through complexation, or by increasing the conversion of NOM into DBP precursors. This review comprehensively summarizes these complex processes, focusing on the most important metals (copper, iron, manganese) in DWDS and their impact on various DBPs. It organizes the dispersed 'metals-DBPs' experimental results into an easily accessible content structure and presents their underlying common or unique mechanisms. Furthermore, the practically valuable application directions of these research findings were analysed, including the toxicity changes of DBPs in DWDS under the influence of metals and the potential enhancement of generalization in DBP model research by the introduction of metals. Overall, this review revealed that the metal environment within DWDS is a crucial factor influencing DBP levels in tap water. [Display omitted] [ABSTRACT FROM AUTHOR]

• CHO cytotoxicity of HKs were comparable with other priority aliphatic DBPs. • HK cytotoxicity followed the order of mono- > di- > tri-haloHKs. • HKs in drinking water samples of South Carolina and Suzhou were 12.4 and 0.9 µg/L. • HKs contributed about 14% of ovearll drinking water cytotoxicity of South Carolina. Although unregulated aliphatic disinfection byproducts (DBPs) had a much higher concentration and cytotoxicity than known aromatic DBPs, a recent study indicated that seven classes of regulated and unregulated priority DBPs (one and two-carbon-atom DBPs) just accounted for 16.2% of disinfected water cytotoxicity in the U.S., meaning some of the highly toxic aliphatic DBPs may be overlooked. Haloketones (HKs) are an essential class of priority DBPs with a 1–100 µg/L concentration in drinking water but lack cytotoxicity data. This study investigated the cytotoxicity of seven HKs using Chinese hamster ovary (CHO) cells. The order for cytotoxicity of HKs from most to least toxic was: 1,3-dichloroacetone (LC 50 : 1.0 ± 0.20 μM) ≈ 1,3-dibromoacetone (1.5 ± 0.19 μM) ≈ bromoacetone (1.9 ± 0.49 μM) > chloroacetone (4.3 ± 0.22 μM) > 1,1,3-trichloropropanone (6.6 ± 0.46 μM) > 1,1,1-trichloroacetone (222 ± 7.7 μM) > hexachloroacetone (3269 ± 344 μM). The cytotoxicity of HKs was higher than most regulated and priority aliphatic DBPs in mono-halogenated, di-halogenated, and tri-halogenated categories. A prediction model of HK cytotoxicity was developed based on the quantitative structure-activity relationship (QSAR), optimizing structures and computing descriptors with Gaussian 09 W. The average concentrations of HKs in representative drinking water samples from South Carolina (U.S.) and Suzhou (China) were 12.4 and 0.9 μg/L, respectively, accounting for 18.8% and 1.7% of their specific total DBPs measured (i.e. not TOX). For South Carolina drinking water, their contributions to total calculated additive cytotoxicity of aliphatic DBPs and overall drinking water cytotoxicity were 86.7% and 14.0%, respectively, demonstrating that HKs are an essential class of overlooked DBPs with a high contribution to drinking water cytotoxicity. Our study can help to explain the conflict that why regulated and priority DBPs (except HKs) just accounted for 16% of chlorinated drinking water cytotoxicity even enough they had much higher concentration and cytotoxicity than known aromatic DBPs. [Display omitted] [ABSTRACT FROM AUTHOR]

• A novel mesocosm approach was used to study DBP precursors in boreal lakes. • Humic mesocosms resisted better the changes induced by DOM and nutrient additions. • Higher frequency of additions and light availability enhanced N-DBP precursors. • Strategies to monitor DBP precursors in drinking water sources are discussed. Changes in rainfall patterns driven by climate change affect the transport of dissolved organic matter (DOM) and nutrients through runoff to freshwater systems. This presents challenges for drinking water providers. DOM, which is a heterogeneous mix of organic molecules, serves as a critical precursor for disinfection by-products (DBPs) which are associated with adverse health effects. Predicting DBP formation is complex due to changes in DOM concentration and composition in source waters, intensified by altered rainfall frequency and intensity. We employed a novel mesocosm approach to investigate the response of DBP precursors to variability in DOM composition and inorganic nutrients, such as nitrogen and phosphorus, export to lakes. Three distinct pulse event scenarios, mimicking extreme, intermittent, and continuous runoff were studied. Simultaneous experiments were conducted at two boreal lakes with distinct DOM composition, as reflected in their color (brown and clear lakes), and bromide content, using standardized methods. Results showed primarily site-specific changes in DBP precursors, some heavily influenced by runoff variability. Intermittent and daily pulse events in the clear-water mesocosms exhibited higher haloacetonitriles (HANs) formation potential linked to freshly produced protein-like DOM enhanced by light availability. In contrast, trihalomethanes (THMs), associated with humic-like DOM, showed no significant differences between pulse events in the brown-water mesocosms. Elevated bromide concentration in the clear mesocosms critically influenced THMs speciation and concentrations. These findings contribute to understanding how changing precipitation patterns impact the dynamics of DBP formation, thereby offering insights for monitoring the mobilization and alterations of DBP precursors within catchment areas and lake ecosystems. [Display omitted] [ABSTRACT FROM AUTHOR]

• Direct photolysis of iohexol had significant dependence of UV wavelength spectral. • Distinctive photogenerated intermediates were observed with different photosensitizers. • Reactive sites and transformation pathways of iohexol were proposed. • Iohexol elimination and DBP yields by UV-LED irradiation followed the order of 255 > 265 > 275 > 285 nm. Iodinated X-ray contrast media (ICM) are ubiquitously present in water sources and challenging to eliminate using conventional processes, posing a significant risk to aquatic ecosystems. Ultraviolet light-emitting diodes (UV-LED) emerge as a promising technology for transforming micropollutants in water, boasting advantages such as diverse wavelengths, elimination of chemical additives, and no induction of microorganisms' resistance to disinfectants. The research reveals that iohexol (IOX) degradation escalates as UV wavelength decreases, attributed to enhanced photon utilization efficiency. Pseudo-first-order rate constants (k obs) were determined as 3.70, 2.60, 1.31 and 0.65 cm2 J−1 at UV-LED wavelengths of 255, 265, 275 and 285 nm, respectively. The optical properties of dissolved organic matter (DOM) and anions undeniably influence the UV-LED photolysis process through photon competition and the generation of reactive substances. The influence of Cl− on IOX degradation was insignificant at UV-LED 255, but it promoted IOX degradation at 265, 275 and 285 nm. IOX degradation was accelerated by ClO 2 −, NO 3 −and HA due to the formation of various reactive species. In the presence of NO 3 −, the k obs of IOX followed the order: 265 > 255 > 275 > 285 nm. Photosensitizers altered the spectral dependence of IOX, and the intermediate photoactivity products were detected using electron spin resonance. The transformation pathways of IOX were determined through density functional theory calculations and experiments. Disinfection by-products (DBPs) yields of IOX during UV-LED irradiation decreased as the wavelength increased: 255 > 265 > 275 > 285 nm. The cytotoxicity index value decreased as the UV-LED wavelength increased from 255 to 285 nm. These findings are crucial for selecting the most efficient wavelength for UV-LED degradation of ICM and will benefit future water purification design. [Display omitted] [ABSTRACT FROM AUTHOR]

• The presence of the "fast" chromophores in DAS is mainly associated with substitution during chlorination of DOM. • The "slow" chromophores in DAS are associated with ring-opening reactions that result in high DBP yields. • The heterogeneity of the A 3 band structure determines the diverses DBP yield of various water sources. • Formation of the THMs and HAAs during chlorination can be predicted by DAS method. Differential absorption spectroscopy (DAS) quantifies changes in the UV–Visible absorbance of dissolved organic matter (DOM) caused by reactions of its chromophores. As a result of its precision and sensitvity, DAS serves as a powerful tool for characterizing the formation of disinfection by-products (DBPs) in generated in DOM chlorination reactions. However, the nonlinear relationship between the intensity of DAS and DBP concentrations as well as the need to develop site-specific fitting parameters limit its practical applications. This study investigated the physico-chemical nature of DAS of chlorinated DOM through experimental measurements and theoretical calculations. Results of this study provide molecular-level evidence that electrophilic substitution reactions involving DOM reactive sites result in the emergence of DAS feaures ascribed to the "fast" chromophores. The ring opening in the cyclic enones-like structures which can be present either in the original DOM or are generated as intermediates in its chlorination, leads to the emergence of DAS features associated with the "slow" chromophores and high yields of DBPs. The kinetic study of chlorination of real waters reveals a strong linear relationship (R2 > 0.91) between ln([DBP]) and the long-wavelength (λ > 325 nm) parameter of the DAS, notably (ln(-DA 350)). This relationship varies among different water sources due to the differences in the heterogeneity of Band A 3 whose maximum is near 350 nm. Band A 3 is one of the Gaussian bands that comprise the overall UV–Visible spectrum of DOM. A new function (f (− D A 350)) is proposed in this study to quantify DBP formation. This function, which is determined by the Band A 3 's area, allows establishing a universal linear relationship between f (− D A 350) and ln([THMs]), as well as f (− D A 350) and ln([HAAs]), across various water sources. The findings of this study will stimulate further development of spectroscopy-based DBP monitoring technology for monitoring and optimization of water disinfection processes. [Display omitted] [ABSTRACT FROM AUTHOR]

• Two-step chlorination formed less DBPs than one-step for wastewater effluent. • Decomposition of organic chloramines was responsible for the lower HAN formation. • High and medium MW DON tend to form organic chloramines during first chlorination. • The low MW DON were the predominate precursors of decomposable organic chloramines. • Two-step chlorination lowers the microbiological impacts of receiving water. With the increasing discharge of wastewater effluent to natural waters, there is an urgent need to achieve both pathogenic microorganism inactivation and the mitigation of disinfection by-products (DBPs) during disinfection. Studies have shown that two-step chlorination, which injected chlorine disinfectant by splitting into two portions, was more effective in inactivating Escherichia coli than one-step chlorination under same total chlorine consumption and contact time. In this study, we observed a substantial reduction in the formation of five classes of CX 3 R-type DBPs, especially highly toxic haloacetonitriles (HANs), during two-step chlorination of secondary effluent when the mass ratio of chlorine-to-nitrogen exceeded 2. The shift of different chlorine species (free chlorine, monochloramine and organic chloramine) verified the decomposition of organic chloramines into monochloramine during second chlorination stage. Notably, the organic chloramines generated from the low molecular weight (< 1 kDa) fraction of dissolved organic nitrogen in effluent organic matter tended to decompose during the second step chlorination leading to the mitigation of HAN formation. Furthermore, the microbiological analysis showed that two-step chlorinated effluent had a slightly lower ecological impact on surface water compared to one-step chlorination. This work provided more information about the two-step chlorination for secondary effluent, especially in terms of organic chloramine transformation and HAN control. [Display omitted] [ABSTRACT FROM AUTHOR]

• AI can capture complex variations and give an immediate response during disinfection. • Application of AI in novel disinfection processes was conducted. • A combination of AI techniques is needed to cope with unregulated DBPs control. • AI shows excellent performance for predicting disinfection residues including FRC. • Fuzzy logic-based neuro systems show superior control performance in disinfection. Water/wastewater ((waste)water) disinfection, as a critical process during drinking water or wastewater treatment, can simultaneously inactivate pathogens and remove emerging organic contaminants. Due to fluctuations of (waste)water quantity and quality during the disinfection process, conventional disinfection models cannot handle intricate nonlinear situations and provide immediate responses. Artificial intelligence (AI) techniques, which can capture complex variations and accurately predict/adjust outputs on time, exhibit excellent performance for (waste)water disinfection. In this review, AI application data within the disinfection domain were searched and analyzed using CiteSpace. Then, the application of AI in the (waste)water disinfection process was comprehensively reviewed, and in addition to conventional disinfection processes, novel disinfection processes were also examined. Then, the application of AI in disinfection by-products (DBPs) formation control and disinfection residues prediction was discussed, and unregulated DBPs were also examined. Current studies have suggested that among AI techniques, fuzzy logic-based neuro systems exhibit superior control performance in (waste)water disinfection, while single AI technology is insufficient to support their applications in full-scale (waste)water treatment plants. Thus, attention should be paid to the development of hybrid AI technologies, which can give full play to the characteristics of different AI technologies and achieve a more refined effectiveness. This review provides comprehensive information for an in-depth understanding of AI application in (waste)water disinfection and reducing undesirable risks caused by disinfection processes. [Display omitted] [ABSTRACT FROM AUTHOR]

• Magnetic quaternized β-cyclodextrin polymer was prepared in an ionic liquid system. • The polymer exhibits excellent adsorption and antibacterial performance. • A combined process of polymer treatment and chlorine disinfection was established. • The process shows higher disinfection efficiency than the chlorine disinfection. • The process greatly reduces the dosage of disinfectant and the generation of DBPs. Disinfection is vital in ensuring water safety. However, the traditional chlorine disinfection process is prone to producing toxic and harmful disinfection by-products (DBPs). The combination of quaternary ammonium polymer and the chlorine disinfection process can solve this shortcoming. Currently, research on the control of DBPs through the combined process is not systematic and the control effect between reducing the dosage of disinfectants and DBPs remains to be studied. Quaternized cyclodextrin polymers have attracted increasing attention due to their excellent adsorption and antibacterial properties, but their synergistic effect with chlorine disinfection is still unclear. In this study, a magnetic quaternized cyclodextrin polymer (MQCDP) is synthesized in an ionic liquid green system, and a combined process of MQCDP treatment and chlorine disinfection is established. The disinfection performance of the combined process on the actual water body along with its reducing effect on the amount of chlorine disinfectant as well as the trihalomethanes (THMs) and haloacetic acids (HAAs) DBPs are explored. MQCDP has a porous structure with a specific surface area of 825 m2 g−1 and is easily magnetically separated. MQCDP can remove most of the natural organic matter (UV 254 absorbance decreased by 97 %) in the water at the dosage of 1 g L−1 and kill bacteria with a sterilization rate of 85 %. Compared with disinfection using chlorine alone, the combined process has higher disinfection efficiency and significantly reduces the amount of disinfectant used. A concentration of 5 mg/L of NaClO was needed to meet the standard by chlorine disinfectant alone, while only 2 mg/L of NaClO can meet the standard for the combined process, indicating 60 % of the chlorine demand was reduced. More importantly, the combined process can significantly reduce the generation potential of DBPs. When 10 mg/L of NaClO is added, the THMs and HAAs generated by the combined process decreased by 65 % and 34 %, respectively, compared with the levels produced by single chlorine disinfection. The combined process can reduce the dosage of chlorine disinfectant and MQCDP can adsorb humic acid DBP precursors in raw water, thus lowering the generation of DBPs during disinfection. In summary, MQCDP has excellent separation and antibacterial ability, and its synergistic effects combined with the chlorine disinfection process are of great significance for controlling the amount of disinfectant and the formation potential of DBPs, which has potential applications in actual water treatment. [Display omitted] [ABSTRACT FROM AUTHOR]

Chlorine dioxide (ClO 2) has been used as an alternative to chlorine in water purification to reduce the formation of halogenated by-products and give superior inactivation of microorganisms. However, the formation of chlorite (ClO 2 −) is a major consideration in the application of ClO 2. In order to improve understanding in ClO 2 − formation kinetics and mechanisms, this study investigated the reactions of ClO 2 with 30 model compounds, 10 humic substances and 2 surface waters. ClO 2 − yields were found to be dependent on the distribution of functional groups. ClO 2 oxidation of amines, di- and tri-hydroxybenzenes at pH 7.0 had ClO 2 − yields >50%, while oxidation of olefins, thiols and benzoquinones had ClO 2 − yields <50%. ClO 2 − yields from humic substances depended on the ClO 2 dose, pH and varied with different reaction intervals, which mirrored the behavior of the model compounds. Phenolic moieties served as dominant fast-reacting precursors (during the first 5 min of disinfection). Aromatic precursors (e.g., non-phenolic lignins or benzoquinones) contributed to ClO 2 − formation over longer reaction time (up to 24 h). The total antioxidant capacity (indication of the amount of electron-donating moieties) determined by the Folin-Ciocalteu method was a good indicator of ClO 2 -reactive precursors in waters, which correlated with the ClO 2 demand of waters. Waters bearing high total antioxidant capacity tended to generate more ClO 2 − at equivalent ClO 2 exposure, but the prediction in natural water should be conservative. • ClO 2 − formation from ClO 2 oxidation of models and humic substances were studied. • ClO 2 oxidation of amines, di- and tri-hydroxybenzenes had ClO 2 − yields >50%. • ClO 2 oxidation of olefins, thiols and benzoquinones had ClO 2 − yields <50%. • Phenolic moieties served as dominant fast-reacting precursors for ClO 2 − formation. • Total antioxidant capacity of humic substances correlated with ClO 2 consumption. [ABSTRACT FROM AUTHOR]

Nitrogenous disinfection by-products (N-DBPs) in chlorinated drinking water are receiving increasing attention due to their elevated toxicities. An effective strategy to control the formation of N-DBPs is to reduce their nitrogenous precursors (e.g., amino acids [AAs], believed to be the important N-DBP precursors) before disinfection. So far, little information is available about the effectiveness of conventional microbial degradation at controlling the formation of N-DBPs. In this study, the biodegradability of 20 AAs was investigated, and the impacts of microbial degradation for the selected 6 typical AAs on the formation of N-DBPs (haloacetonitriles and haloacetamides) and traditional carbonaceous DBP (chloroform) were investigated. The results indicated that glycine, arginine, aspartic acid, asparagine, alanine and serine were susceptible to biodegradation, and the formation potentials (FPs) of DBPs were remarkably reduced after biodegradation. The highest chloroform FP reduction rates from tryptophan and tyrosine were 85.4% and 56.2%, respectively. The FPs of dichloroacetonitrile and trichloroacetamide were also reduced after biodegradation of the all selected AA samples during chlor(am)ination. Dichloroacetamide FPs decreased continuously with incubation time during chlorination for phenylalanine, asparagine, aspartic acid, and the mixed AAs, and the highest reduction rates were 78.7%, 74.6%, 46.7% and 35.3% respectively. The results of integrated toxicity analysis indicated that the pre-treatment of microbial degradation significantly decreased the integrated toxicity of DBPs formed from AAs. Moreover, the microbial community analysis revealed that Proteobacteria was predominant at phylum level in the mixed AA sample, and the dominant genera were Acinetobacter and Pseudomonas. Proteobacteria may play an important role in controlling DBP precursor. Image 1 • Biodegradability of amino acids (AAs) and its impact on DBP formation was investigated. • Microbial degradation of AAs significantly decreased dichloroacetonitrile formation. • The integrated toxicity of DBPs decreased with the pre-treatment of microbial degradation. • Proteobacteria was predominant in AA samples and may contribute to reduce DBPs. [ABSTRACT FROM AUTHOR]

Differential UV absorbance (ΔA) is an important indicator that could allow operators and utility managers to routinely monitor disinfection by-product (DBP) concentrations, even in real-time applications, without the limitations of regulatory sampling and analyses. While determination coefficients between differential UV absorbance at a single wavelength (often 272 nm) and chlorination DBP concentrations are usually very high (R2 > 0,90), the fitting parameters of these relationships vary from one water source to another, or vary within the same water source depending on the time of year. The objectives of this study are to apply multiple regression models to a rich database of ΔA and DBPs (trihalomethanes (THMs) and haloacetic acids (HAAs)) that was generated from lab experiments using multiple waters with low bromide concentrations, in order to identify wavelengths that improve the applicability of DBP-ΔA relationships, as well as develop a widely applicable multi-wavelength DBP-ΔA relationship. The results show that using ΔA at two wavelengths, in addition to initial absorbance (A) at one wavelength, greatly improves the determination coefficients of the relationships, when compared with the best possible single-wavelength relationships. The significant predictors identified are A 270, ΔA270 and ΔA425 for THMs; A 255, ΔA255 and ΔA425 for DCAA; A 250, ΔA250 and ΔA425 for TCAA; and A 250, ΔA250 and ΔA425 for HAA6. This paper also discusses the applicability of the models developed for predicting DBPs in treatment plants and drinking water, as well as their limitations and the required future research to improve their performance. • Differential absorbance spectra and DBP database were generated in the lab. • Multilinear regression produced widely applicable DBP-ΔA relationships. • Initial and differential absorbances are significant predictors of THMs and HAAs. • Differential absorbance at 425 nm complement the usual predictors. [ABSTRACT FROM AUTHOR]

The removal of bromide (Br−) and iodide (I−) from source waters mitigates the formation of brominated and iodinated disinfection by-products (DBPs), which are more toxic than their chlorinated analogues. In this study, we report on our recently developed environmental-friendly method for the preparation of novel silver chloride/superfine activated carbon composite (AgCl-SPAC) to rapidly and selectively remove Br− and I− from surface waters. The material characteristics were tracked, before and after treatment, using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectra (XPS) spectroscopies. The results showed very fast removal kinetics of Br− and I− by AgCl-SPAC with equilibrium times at 150 s and <10 s, respectively (i.e., 2–3 orders of magnitudes faster than previously tested Ag-based composites). In addition, AgCl-SPAC was evaluated under eight different Cl− concentrations up to 400 mg/L and exhibited high removal efficiencies for I− (i.e., >90% at all tested conditions) and Br− (i.e, >80% at Cl− = 0.5–200 mg/L, and 60–75% at extreme Cl− conditions = 300–400 mg/L). Unlike previous Ag-based composites, AgCl-SPAC performance was not affected by elevated concentrations of two types of natural organic matter (2–16 mg-NOM/L). The superior performance was further confirmed in four different surface waters and one groundwater. After the removal of Br− and I− from all waters by AgCl-SPAC, the subsequent DBPs formation (trihalomethanes, haloacetic acids, and haloacetonitriles), total organic halogens (TOX), bromine substitution factor (BSF), and calculated cytotoxicity under the uniform formation conditions (UFC) decreased significantly. Overall, this novel composite represents a promising alternative approach, to be integrated continuously or seasonally, for controlling the formation of brominated and/or iodinated DBPs at water treatment plants. Image 1 • Novel AgCl-SPAC composite was prepared with environmental-friendly method. • Rapid and selective removal of Br- and I- was demonstrated. • The composite removed Br- and I- from 5 different surface waters and groundwater. • AgCl-SPAC treatment dropped the formation of Br-DBP and I-DBP. [ABSTRACT FROM AUTHOR]

Algal-derived dissolved organic matter (ADOM) originating from lysed Microcystis aeruginosa cells was investigated as precursor material to form disinfection by-products upon disinfection with free chlorine. Non-targeted ultrahigh resolution 12 T negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) revealed high molecular diversity in solid-phase extracted and ionizable components of Microcystis aeruginosa ADOM. The toxin microcystin LR was effectively degraded by free chlorine, which was expected. However, we found a high diversity of disinfection by-products associated with the addition of free chlorine to the water-soluble and solid-phase extractable fraction of ADOM and of double-bond moieties in abundant and known unsaturated fatty acids. Aromatic DOM precursors were absent from known metabolites of Microcystis aeruginosa and no evidence for aromatic disinfection by-products (DBPs) was found, despite N-containing compounds. A large diversification of N-containing molecular formulas was observed after chlorination, which seems indicative for the breakdown and oxidation of larger peptides. Additionally, a diverse group of N-compounds with presumed chloramine functional groups was observed. This study highlights the importance to evaluate ADOM and its ability to form different DBPs when compared to allochthonous or terrestrially-derived DOM. Highlights • Solid-phase extracted Microcystis aeruginosa DOM (ADOM) is susceptible to chlorination. • Diverse chlorinated fatty acids with up to 5 chlorine atoms were found as DBPs. • The reaction of free chlorine with ADOM drastically increased the diversity of N-DBPs. [ABSTRACT FROM AUTHOR]

Biofiltration has been shown to be effective for disinfection by-product (DBP) precursor control, however few studies have considered its role in the potential formation of DBPs. Biofilm is composed of heterogeneous bacteria as well as extracellular polymeric substances (EPS). The objective of this study was to determine the contribution of biofilm-related materials such as EPS to form nitrogen-containing DBPs upon chloramination, and to determine the influence of cyclical (scheduled on-off) biofilter operation on DBP precursor removal. Biologically active media was sampled from a full-scale biofilter operating under cold-water conditions (3.6 ± 0.5 °C) and extracted using a cation exchange resin into a phosphate buffer solution. Biomass concentrations, as determined using adenosine triphosphate (ATP) measurements, remained stable at 298 ± 55 ng ATP/g media over the trial period. N-nitrosodimethylamine (NDMA) and haloacetonitrile (HAN 4) formation potential (FP) tests conducted under uniform formation conditions (UFC) using extracted biofilm yielded 0.80 ± 0.27 ng NDMA/g media and 18.7 ± 3.3 ng dichloroacetonitrile (DCAN)/g media. Further analyses of extracted biofilm using fluorescence spectroscopy and liquid chromatography-organic carbon detection indicated the presence of proteins above 20 kDa and humic-like substances. Extracted proteins (93.5 ± 8.1 μg/g media) correlated well (R = 0.90) with UV 280 measurements, indicating that spectrophotometry may serve as a valuable tool to quantify proteins in extracted biofilms. While substances in biofilms can serve as NDMA and DCAN precursors, the full-scale cyclically-operated biofilter that was examined did not show release of NDMA precursors during start-up following stagnation periods of 6 h or more. These biofilters consistently removed 6.9 ± 4.3 ng/L of NDMA precursors; typical NDMA UFC-FP of biofilter effluent was 8.5 ± 2.6 ng/L. Graphical abstract Image 1 Highlights • Biofilm extracted from filter media contained 93.5 ± 8.1 μg proteins/g media. • Extracted biofilm produced 0.80 ± 0.27 ng NDMA and 18.7 ± 3.3 ng DCAN per g media. • Biofiltration removed ∼50% of NDMA precursors during typical steady-state operation. [ABSTRACT FROM AUTHOR]

The efficiency of the ultraviolet (UV)/chlorine process strongly depends on UV wavelength because chlorine photolysis and its subsequent radical formation are highly wavelength-dependent. This study compared the degradation of humic acid (HA) during the UV/chlorine process by low pressure mercury lamp (LPUV, 254 nm) and ultraviolet light-emitting diode (UV-LED, 275 and 310 nm). The results indicated that HA degradation followed the pseudo-first-order kinetics, and the fluence-based degradation rate constants (k obs) were significantly affected by UV wavelength and solution pH. HA degradation decreased greatly with increasing solution pH during the UV/chlorine process at 254 nm, while the opposite trend was observed at 275 and 310 nm. In the meantime, k obs decreased in the order of 275 nm > 254 nm > 310 nm at pH > 7.0. The changes of chlorine molar absorption coefficients at different UV wavelengths resulted in the variation of chlorine photodecay rates (k obs, chlorine), and the synergistic effects of k obs, chlorine and chlorine quantum yields (Φ chlorine) affected HA reduction. The formation of disinfection by-products (DBPs) during the UV/chlorine process was also evaluated. A significant suppression on DBP formation and DBP-associated calculated theoretical cytotoxicity were observed at 275 nm high UV fluence and alkaline pHs. These findings in this study demonstrate that UV wavelength at 275 nm is more suitable for HA degradation by the UV/chlorine advanced oxidation process in practical applications. Image 1 • HA degradation rate constants were significantly affected by UV wavelength in the UV/chlorine process. • The UV/chlorine process was more efficient at 275 nm than 254 and 310 nm at alkaline conditions. • Effective mitigation of DBPs and toxicity was achieved at 275 nm at high UV fluence. • DBP-associated cytotoxicity decreased in the order of 254 > 310 > 275 nm at high UV fluence in the presence of Br−. [ABSTRACT FROM AUTHOR]

Abstract Disinfected drinking water contains hundreds of disinfection by-products (DBPs) that are formed by the reaction of disinfectants with natural and anthropogenic organic matter, bromide, and iodide. Understanding what these DBPs are is important because millions of people worldwide consume drinking water every day, and human epidemiologic studies have reported cancer, miscarriage, and birth defects from consuming such waters. While more than 600 DBPs are reported in the literature, very few studies quantify complete classes of chlorinated, brominated, and iodinated DBPs. Also, very few studies conduct comprehensive non-target analyses of unknown DBPs to characterize the complete DBP exposure (the exposome). We developed a new gas chromatography (GC)-mass spectrometry (MS) method that simultaneously quantifies 39 priority unregulated DBPs from six different chemical classes (haloacetaldehydes, haloketones, haloacetamides, haloacetonitriles, halonitromethanes, and iodinated-trihalomethanes) and analyzes unknown DBPs with mass accuracy <600 ppm under full-scan conditions. Using a new type of time-of-flight (TOF) mass spectrometer, which combines selected ion monitoring (SIM)-level sensitivity with mass accuracy of ±0.05 Da, method detection limits of 3–61 ng/L were achieved. These levels were found to be quite comparable to those of a widely used single quadrupole mass spectrometer (2–90 ng/L) operated in SIM mode. However, analysis using this TOF mass spectrometer offers two additional advantages over traditional quadrupole-MS: (1) full-scan data, which provides additional confidence for target analytes, as well as complete mass spectra for unknown analysis, and (2) two decimal place mass accuracy, which allows additional confidence for target analytes and importantly, molecular formula indication for unknowns. High resolution accurate mass TOF was also used to validate identification of selected compounds. This new method was demonstrated on finished drinking waters from three different drinking water plants, where target quantification and non-target unknown analyses were performed simultaneously during the same run. This enabled the quantification of 39 DBPs, along with the non-target identification of many other drinking water contaminants, including two additional non-target DBPs: N,N -dimethylacetamide and N -nitrosodibutylamine. Graphical abstract Image 1 Highlights • New target and non-target GC-MS method that quantifies 6 different classes of DBPs. • Non-target unknown analysis at two decimal place mass accuracy. • Method detection limits between 3 and 67 ng/L for 39 priority unregulated DBPs. • New method was demonstrated on chlorinated and chloraminated drinking water samples. • Haloacetaldehydes were found to be the largest DBP class by weight of priority DBPs. [ABSTRACT FROM AUTHOR]

• The main photodegradation mechanism of 33 different DBPs was dehalogenation. • Photodegradation efficiency followed the order of I-DBP > Br-DBPs > Cl-DBPs. • UV 254 treatment effectively removed halogenated organic DBPs. • The subsequent use of disinfectants (Cl 2 and NH 2 Cl) reformed photodegraded DBPs. 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 SUVA 254 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 (Cl 2 and NH 2 Cl) 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. [Display omitted] [ABSTRACT FROM AUTHOR]

Sandstorms, a natural meteorological event, occur repeatedly during the dry season and can accumulate large amounts of natural/anthropogenic pollutants during the deposition process, potentially introducing disinfection by-product (DBP) precursors into surface waters. In this study, the characteristics of sandstorm-derived dissolved organic matter (DOM) and its DBP formation potential were elucidated. Overall, sandstorm-derived DOM mainly consisted of low-molecular-weight, low-aromaticity, high-nitrogen organic matter, with a dissolved organic carbon (DOC) release yield of 14.4 mg-DOC/g. The halogenated DBP formation potential (calculated as total organic halogen) of sandstorm-derived DOM was comparable to that of surface water, while the normalized DBP-associated toxicity was 1.96 times higher. Similar to DOM introduced by other depositional pathways, sandstorm-derived DOM also had higher yields of highly cytotoxic DBPs (haloacetaldehydes [HALs], haloacetonitriles [HANs] and halonitromethanes [HNMs]). The average atmospheric deposition flux for DOM during the sandstorm event (50.4 ± 2.1 kg km -2 day -1 ) was 6.95 times higher than that of dry deposition, indicating a higher probability of contaminant input. Simultaneously, the estimation revealed that the sandstorm will increase the formation potential of toxicity forcing agents, such as HALs, HANs and HNMs, in surface water by 3.87%, 2.39% and 9.04%, respectively. Considering the high frequency of sandstorm events and the sorption of other organic pollutants by sand and dust, the impact of sandstorms on surface water quality should be of concern., 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.)

Abstract Chlorine is the most frequently used disinfectant and oxidant for maintaining swimming pool water quality; however, it reacts continuously with dissolved organic matter to produce disinfection by-products (DBPs), which are a health risk for pool users. UV treatment is used widely to remove chloramines, which are the most prevalent group of DBPs, albeit chloro-organic DBP concentrations often increase during post-UV chlorination. In this work, UV and ozone treatments were investigated as additional technologies to eliminate DBP formation and their precursors. Batch experiments were conducted under controlled conditions, using realistic UV and ozone dosages and real pool water samples collected from a public swimming pool. A gradual increase in all investigated DBP concentrations and predicted toxicity was observed during chlorination after repeated UV treatments, and concentrations of certain DBPs also increased during post-ozone chlorination. Based on ozone and chlorine's similar reactivity, ozone was used directly after UV treatment to decrease the induction of DBP formation. Most DBP concentrations decreased during repeated combined treatments. It was also observed that DBP formed by post-ozone chlorination was removed by photolysis, thereby indicating synergy between the treatments. Repeated treatments using realistic UV and ozone dosages predicted that water quality will improve as a result of continuous combined UV and ozone treatments. Graphical abstract Image 1 Highlights • Repeated UV treatment with chlorination increases formation of chloro-organic DBPs. • Ozone oxidises chlorine-reactive DBP precursors but forms other uncommon DBPs. • Continuous combined UV treatment followed by ozonation decreases DBP formation. • Synergy, as ozone removes UV-formed reactivity, and UV photolyses ozone-induced DBP. • Pool water quality is predicted to improve with continuous combined treatments. [ABSTRACT FROM AUTHOR]

Abstract The formation of odorous aldehydes and N -chloraldimines, and also nitriles, which are potentially hazardous to human health, was investigated in studies of the chlorination of amino acids (AAs) in both operational drinking water treatment plants and laboratory-based experiments. In the drinking water treatment plants studied, the concentration of total free AAs did not significantly change after treatment, even though good removal of DOC was observed. However, free AAs still contributed less than 3% of total nitrogen in the treated drinking waters, and no aldehydes, N -chloraldimines or nitriles of interest were detected in the treated waters, presumably due to the low concentrations of the precursor AAs in these water samples. Laboratory formation potential experiments showed that carboxylic acids can form from the degradation of aldehydes and nitriles. Volatile carboxylic acids could result in odour issues and some carboxylic acids may be of potential health concern. Therefore, carboxylic acids should also be considered as potential by-products of interest in distribution systems with long contact times of ≥ 7days. A higher proportion of nitrile formation, and promotion of carboxylic acid formation, was observed when the chlorine to AA ratio was greater than 4 compared to when this ratio was 2.8, indicating that the Cl:AA ratio is an important factor in DBP formation pathways. This suggests that results from laboratory formation studies undertaken at these low Cl:AA ratios cannot be directly applied to 'real' water systems, which typically have Cl:AA ratios that are orders of magnitude higher than 4. Laboratory formation potential experiments also showed that the short-term rate of formation of aldehydes and N -chloraldimines was reduced in the presence of ammonia, although formation over longer timescales (e.g. 7 days) was not significantly different between chlorination and chloramination experiments. Therefore, the use of chloramination instead of chlorination does not appear to reduce the formation of these by-products from AAs. Graphical abstract Image 1 Highlights • Odorous by-products were not detected in the drinking water systems studied. • Carboxylic acids also formed in laboratory experiments of amino acid chlorination. • Carboxylic acids should be tested in systems with chlorine contact times >7 days. • Higher chlorine to amino acid ratios increased nitrile and carboxylic acid formation. • Chloramination and chlorination produced similar by-product formation over 7 days. [ABSTRACT FROM AUTHOR]

Abstract Dissolved organic carbon (DOC) removal from a river water source was investigated using ion exchange (IEX), coagulation and membrane filtration. This research linked the variable charge characteristics of the organic compounds present in the source water with removal by IEX and coagulation. The raw water charge density fluctuated considerably (between 5.4 and 10.7 meq mg DOC −1) and controlled removal of the charge loading. Importantly, charge density was not correlated with the organic carbon concentration. The combined IEX and coagulation process reduced the specific DBP-FP (sDBP-FP) of the final water, with values as low as 18 μg mg DOC −1 for both haloacetic acids and trihalomethanes. IEX removed a particular fraction of NOM that 1) enhanced coagulation efficiency, providing increased removal of overall DOC; and 2) enabled coagulation to subsequently remove higher levels of specific components of NOM that have a high DBP-FP. The component of NOM removed by IEX that had a positive impact on coagulation was identified to be charged low molecular weight organic compounds of all hydrophobicity levels, resulting in a reduced specific DBP-FP compared to coagulation alone. Graphical abstract Image 1 Highlights • Ion exchange (IEX) selectively removed organic precursors that improved coagulation. • IEX removed charged organics of low molecular weight, regardless of their hydrophobicity. • IEX combined with coagulation resulted in very low disinfection by-product formation. • Charge density was an effective way to track organic matter removal. [ABSTRACT FROM AUTHOR]

Abstract Oxidation processes are impacted by the type, concentration and reactivity of the dissolved organic matter (DOM). In this study, the reactions between various types of DOM (Suwannee River fulvic acid (SRFA), Nordic Reservoir NOM (NNOM) and Pony Lake fulvic acid (PLFA)) and two oxidants (ozone and chlorine) were studied in the pH range 2–9 by using a combination of optical measurements and electron donating capacities. The relationships between residual electron donating capacity (EDC) and residual absorbance showed a strong pH dependence for the ozone-DOM reactions with phenolic functional groups being the main reacting moieties. Relative EDC and absorbance abatements (UV 254 or UV 280) were similar at pH 2. At pH 7 or 9, the relative abatement of EDC was more pronounced than for absorbance, which could be explained by the formation of UV-absorbing products such as benzoquinone from the transformation of phenolic moieties. An increase in fluorescence abatement with increasing pH was also observed during ozonation. The increase in fluorescence quantum yields could not be attributed to formation of benzoquinone, but related to a faster abatement of phenolic moieties relative to fluorophores with low ozone reactivity. The overall •OH yields as a result of DOM-induced ozone consumption increased significantly with increasing pH, which could be related to the higher reactivity of phenolic moieties at higher pH. The •OH yields for SRFA and PLFA were proportional to the phenolic contents, whereas for NNOM, the •OH yield was about 30% higher. During chlorination of DOM at pH 7 an efficient relative EDC abatement was observed whereas the relative absorbance abatement was much less pronounced. This is due to the formation of chlorophenolic moieties, which exert a significant absorbance, and partly lose their electron donating capacity. Pre-ozonation of SRFA leads to a decrease of chloroform and haloacetic acid formation, however, only after a threshold of > ∼50% abatement of the EDC and under conditions which are not precursor limited. The decrease in chloroform and haloacetic acid formation after the threshold EDC abatement was proportional to the relative residual EDC. Graphical abstract Image 1 Highlights • Ozone (O 3)- and chlorine-DOM reactions were assessed in the pH range 2–9. • For O 3 , the relationship between EDC and absorbance is pH dependent. • For O 3 , benzoquinone formation explained low absorbance/high EDC loss at pH > 7. • For chlorine, UV-absorbing chlorophenols were formed while EDC decreased. • CHCl 3 formation during chlorination of DOM decreased for > ∼50% EDC abatement. [ABSTRACT FROM AUTHOR]

The effective removal of haloacetamides (HAMs) as a group of emerging disinfection by-products is essential for drinking water safety. This study investigated the degradation of 10 HAMs, including chlorinated, brominated, and iodinated analogues, by sodium sulfite (S(IV)) and the mechanism behind it. The results indicated that all HAMs, excluding chlorinated HAMs, decomposed immediately when exposed to S(IV). The reductive dehalogenation kinetics were well described by a second-order kinetics model, first-order in S(IV) and first-order in HAMs. The degradation rates of HAMs increased with the increase of pH and they were positively correlated with sulfite concentration, indicating that the reaction of S(IV) with HAMs mainly depends on sulfite. The rank order and relative activity of the reaction of sulfite with HAMs depends on bimolecular nucleophilic substitution reaction reactivity. The order of the reductive dehalogenation rates of HAMs versus the substitution of halogen atoms was iodo- > bromo- >> chloro-. During reductive dehalogenation of HAMs by sulfite, the α-carbon bound to the amide group underwent nucleophilic attack at 180° to the leaving group (halide). As a consequence, the halide was pushed off the opposite side, generating a transition state pentacoordinate. The breaking of the C-X bond and the formation of the new C-S bond occurred simultaneously and HAM sulfonate formed as the immediate product. Results suggest that S(IV) can be used to degrade brominated and iodinated HAMs in drinking water and therefore should not be added as a quenching agent before HAM analysis to accurately determine the HAM concentrations produced during water disinfection. [ABSTRACT FROM AUTHOR]

N -nitrosodimethylamine (NDMA), a probable human carcinogen disinfection by-product, has been detected in chloraminated drinking water systems. Understanding its formation over time is important to control NDMA levels in distribution systems. The main objectives of this study were to investigate the role of chloramine species (i.e., monochloramine and dichloramine); and the factors such as pH, sulfate, and natural organic matter (NOM) influencing the formation of NDMA. Five NDMA precursors (i.e., dimethylamine (DMA), trimethylamine (TMA), N,N -dimethylisopropylamine (DMiPA), N,N- dimethylbenzylamine (DMBzA), and ranitidine (RNTD)) were carefully selected based on their chemical structures and exposed to varying ratios of monochloramine and dichloramine. All amine precursors reacted relatively fast to form NDMA and reached their maximum NDMA yields within 24 h in the presence of excess levels of chloramines (both mono– and dichloramine) or excess levels of dichloramine conditions (with limited monochloramine). When the formation of dichloramine was suppressed (i.e., only monochloramine existed in the system) over the 5 day contact time, NDMA formation from DMA, TMA, and DMiPA was drastically reduced (∼0%). Under monochloramine abundant conditions, however, DMBzA and RNTD showed 40% and 90% NDMA conversions at the end of 5 day contact time, respectively, with slow formation rates, indicating that while these amine precursors react preferentially with dichloramine to form NDMA, they can also react with monochloramine in the absence of dichloramine. NOM and pH influenced dichloramine levels that affected NDMA yields. NOM had an adverse effect on NDMA formation as it created a competition with NDMA precursors for dichloramine. Sulfate did not increase the NDMA formation from the two selected NDMA precursors. pH played a key role as it influenced both chloramine speciation and protonation state of amine precursors and the highest NDMA formation was observed at the pH range where dichloramine and deprotonated amines coexisted. In selected natural water and wastewater samples, dichloramine led to the formation of more NDMA than monochloramine. [ABSTRACT FROM AUTHOR]

The effects of ozone-biologically activated carbon (O 3 -BAC) treatment with various phosphate doses (0, 0.3 or 0.6 mg/L) were investigated on the formation of disinfection by-products (DBPs) and occurrence of opportunistic pathogens (OPs) in drinking water distribution systems (DWDSs) simulated by annular reactors (ARs). It was found that the lowest DBPs and the highest inactivation of OPs such as Mycobacterium spp. , Mycobacterium avium , Aeromonas spp. , Pseudomonas aeruginosa and Hartmanella vermiformis , occurred in the effluent of the AR with 0.6 mg/L phosphate addition. Based on the results of different characterization techniques, for the AR with 0.6 mg/L phosphate-enhanced O 3 -BAC treatment, dissolved organic carbon in the influent exhibited the lowest concentration and most stable fraction due to the improved biodegradation effect. Moreover, the total amount of suspended extracellular polymeric substances (EPS) in the bulk water of the AR decreased greatly, resulting in the lowest chlorine consumption and DBPs formation in the AR. In Fourier transform infrared spectra of the suspended EPS, the amide II band (1600-1500 cm −1 ) disappeared and the protein/polysaccharide ratio decreased remarkably, indicating the destruction of protein and a decrease in hydrophobicity. Moreover, β-sheets and α-helices in the protein secondary structures were degraded while the random coils increased sharply as phosphate addition increased to 0.6 mg/L, inhibiting microbial aggregation and hence weakening the chlorine-resistance capability. Thus, most of the OPs in suspended biofilms were more easily inactivated by residual chlorine, resulting in the lowest OPs occurrence in the effluent of the AR. Our findings indicated that enhancing the efficiency of the BAC filter by adding phosphate is a promising method for improving water quality in DWDSs. [ABSTRACT FROM AUTHOR]

The use of fluorescence data coupled with neural networks for improved predictability of drinking water disinfection by-products (DBPs) was investigated. Novel application of autoencoders to process high-dimensional fluorescence data was related to common dimensionality reduction techniques of parallel factors analysis (PARAFAC) and principal component analysis (PCA). The proposed method was assessed based on component interpretability as well as for prediction of organic matter reactivity to formation of DBPs. Optimal prediction accuracies on a validation dataset were observed with an autoencoder-neural network approach or by utilizing the full spectrum without pre-processing. Latent representation by an autoencoder appeared to mitigate overfitting when compared to other methods. Although DBP prediction error was minimized by other pre-processing techniques, PARAFAC yielded interpretable components which resemble fluorescence expected from individual organic fluorophores. Through analysis of the network weights, fluorescence regions associated with DBP formation can be identified, representing a potential method to distinguish reactivity between fluorophore groupings. However, distinct results due to the applied dimensionality reduction approaches were observed, dictating a need for considering the role of data pre-processing in the interpretability of the results. In comparison to common organic measures currently used for DBP formation prediction, fluorescence was shown to improve prediction accuracies, with improvements to DBP prediction best realized when appropriate pre-processing and regression techniques were applied. The results of this study show promise for the potential application of neural networks to best utilize fluorescence EEM data for prediction of organic matter reactivity. [ABSTRACT FROM AUTHOR]

Differential UV spectroscopy, defined as the difference in UV absorbance spectra before and after chlorination, has shown great potential to predict disinfection by-product (DBP) concentrations at laboratory scale. However, so far, no results have been reported on the full scale application of differential UV spectroscopy in drinking water treatment facilities. The objectives of this study are to determine if relationships can be developed between differential UV absorbance and DBP concentrations, for both regulated and unregulated DBPs, in a full-scale facility and to determine if these relationships vary throughout the year with variations in raw water quality and treatment conditions. The results show that linear and power relationships between differential UV absorbance and DBP concentrations can be developed (0.62 ≤ R 2  ≤ 0.99), although differences between relationships obtained in lab- and full-scale conditions need further investigation. Finally, the relationships obtained are different from one sampling campaign to another, which raises the question of whether it is possible to determine relationships that are stable enough to be used as adequate feedback on DBP concentrations. [ABSTRACT FROM AUTHOR]

The electro-peroxone (E-peroxone) process is an emerging ozone-based electrochemical advanced oxidation process that combines conventional ozonation with in-situ cathodic hydrogen peroxide (H 2 O 2 ) production for oxidative water treatment. In this study, the effects of the E-peroxone pretreatment on disinfection by-product (DBP) formation from chlorination of a synthetic surface water were investigated and compared to conventional ozonation. Results show that due to the enhanced transformation of ozone (O 3 ) to hydroxyl radicals ( OH) by electro-generated H 2 O 2 , the E-peroxone process considerably enhanced dissolved organic carbon (DOC) abatement and significantly reduced bromate (BrO 3 − ) formation compared to conventional ozonation. However, natural organic matter (NOM) with high UV 254 absorbance, which is the major precursors of chlorination DBPs, was less efficiently abated during the E-peroxone process than conventional ozonation. Consequently, while both conventional ozonation and the E-peroxone process substantially reduced the formation of DBPs (trihalomethanes and haloacetic acids) during post-chlorination, higher DBP concentrations were generally observed during chlorination of the E-peroxone pretreated waters than conventional ozonation treated. In addition, because of conventional ozonation or the E-peroxone treatment, DBPs formed during post-chlorination shifted to more brominated species. The overall yields of brominated DBPs exhibited strong correlations with the bromide concentrations in water. Therefore, while the E-peroxone process can effectively suppress bromide transformation to bromate, it may lead to higher formation of brominated DBPs during post-chlorination compared to conventional ozonation. These results suggest that the E-peroxone process can lead to different DBP formation and speciation during water treatment trains compared to conventional ozonation. [ABSTRACT FROM AUTHOR]

• The non-fluorescent group of DOM contributed to the formation of HKs, HANs and HNMs. • Lower ratios of UTOX/TOX obtained in UV-LED/chlorine process than chlorination. • The formation and toxicity of N-DBPs and Br-DBPs increased at high UV fluence. Ultraviolet light-emitting diode (UV-LED) is a promising option for the traditional low-pressure UV lamp, but the evolutions of DOM composition, the formation of disinfection by-products (DBPs) and their toxicity need further study in raw water during UV-LED/chlorine process. In UV-LED (275 nm)/chlorine process, two-dimensional correlation spectroscopy (2DCOS) analysis on synchronous fluorescence and UV–vis spectra indicated the protein-like fractions responded faster than the humic-like components, the reactive sequence of peaks for DOM followed the order: 340 nm→240 nm→410 nm→205 nm→290 nm. Compared to chlorination for 30 mins, the UV-LED/chlorine process enhanced the degradation efficiency of three fluorescent components (humic-like, tryptophan-like, tyrosine-like) by 5.1%-46.1%, and the formation of carbonaceous DBPs (C-DBPs) significantly reduced by 43.8% while the formation of nitrogenous DBPs (N-DBPs) increased by 27.3%. The concentrations of C-DBPs increased by 17.8% whereas that of N-DBPs reduced by 30.4% in 24 h post-chlorination. The concentrations of brominated DBPs increased by 17.2% during UV-LED/chlorine process, and further increased by 18.5% in 24 h post-chlorination. According to the results of principal component analysis, the non-fluorescent components of DOM might be important precursors in the formation of haloketones, haloacetonitriles and halonitromethanes during UV-LED/chlorine process. Unlike chlorine treatment, the reaction of DOM in UV-LED/chlorine treatment generated fewer unknown DBPs. Compared with chlorination, the cytotoxicity of C-DBPs reduced but the cytotoxicity of both N-DBPs and Br-DBPs increased during UV-LED/chlorine process. Dichloroacetonitrile had the highest cytotoxicity, followed by monobromoacetic acid, bromochloroacetonitrile and trichloroacetic acid during 30 mins of UV-LED/chlorine process. Therefore, besides N-DBPs, the more toxic Br-DBPs formation in bromide-containing water is also not negligible in the practical applications of UV-LED (275 nm)/chlorine process. [Display omitted] [ABSTRACT FROM AUTHOR]

An array of similar halogenated nitrogen-containing compounds with elemental composition C n H 2n NO 2 X, C n H 2n–2 NO 2 X and C n H 2n-1 NOX 2 (X = Cl, Br; n = 16, 18, 22) was detected in drinking water with high performance liquid chromatography – high resolution mass spectrometry (HPLC-HRMS) method. Compounds of this type were never mentioned among disinfection by-products. Tandem mass spectrometry allowed referring them to halohydrines or dihalogenated fatty amides, the products of conjugated electrophilic addition of halogens to the double bonds of unsaturated fatty amides. The proposed structures were confirmed by conducting aqueous chlorination with standard solution of oleamide. These compounds may be considered as a brand new class of disinfection by products, while their toxicities require special study. [ABSTRACT FROM AUTHOR]

As one of the most oestrogenic synthetic compounds in water environment, diethylstilbestrol (DES) has been studied for decades. Some studies showed that DES can be removed by ultraviolet (UV) irradiation. However, no one has paid attention to the formation of oestrogenic disinfection by-products (DBPs) and the persistence of DES in surface water remains a mystery. In this study, UV was found to be very effective in removing oestrogenic activity regardless of water quality. Three oestrogenic DBPs were specifically isolated by oestrogen receptor-based affinity chromatography and identified as 9,10-diethylphenanthrene-3,6-diol, cis -DES and Z,Z-dienestrol. Among them, 9,10-diethylphenanthrene-3,6-diol was proved to have stronger oestrogenic activity than E2, but it can be further photodegraded. In addition, DES was also demonstrated to be a photochromic compound, whose UV-induced intermediates can be transformed back to DES under sunlight, which significantly slows down the photodegradation of DES. This study solves the question as to why UV-degradable DES is still detectable in the ambient water and provides a deep understanding of DES removal during UV disinfection. [ABSTRACT FROM AUTHOR]

Drinking water utilities are relying more than ever on water sources impacted by wastewater effluents. Disinfection/oxidation of these waters during water treatment may lead to the formation of several disinfection by-products, including the probable human carcinogen N -nitrosodimethylamine (NDMA) and the regulated trihalomethanes (THMs). In this study, the potential of ion exchange resins to control both NDMA and THMs precursors in a single treatment is presented. Two ion exchange resins were examined, a cation exchange resin (Plus) to target NDMA precursors and an anion exchange resin (MIEX) for THMs precursors control. We applied the resins, individually and combined, in the treatment of surface and wastewater effluent samples. The treatment with both resins removed simultaneously NDMA (43–85%) and THMs (39–65%) precursors. However, no removal of NDMA precursors was observed in the surface water with low initial NDMA FP (14 ng/L). The removals of NDMA FP and THMs FP with Plus and MIEX resins applied alone were (49–90%) and (41–69%), respectively. These results suggest no interaction between the resins, and thus the feasibility of effectively controlling NDMA and THMs precursors concomitantly. Additionally, the effects of the wastewater impact and the natural attenuation of precursors were studied. The results showed that neither the wastewater content nor the attenuation of the precursor affected the removals of NDMA and THMs precursors. Finally, experiments using a wastewater effluent sample showed that an increase in the calcium concentration resulted in a reduction in the removal of NDMA precursors of about 50%. [ABSTRACT FROM AUTHOR]

In this work, the reaction of four benzodiazepines (diazepam, oxazepam, nordazepam and temazepam) during water chlorination was studied by means of liquid chromatography-quadrupole-time of flight-mass spectrometry (LC-QTOF-MS). For those compounds that showed a significant degradation, i.e. diazepam, oxazepam and nordazepam, parameters affecting to the reaction kinetics (pH, chlorine and bromide level) were studied in detail and transformation products were tentatively identified. The oxidation reactions followed pseudofirst-order kinetics with rate constants in the range of 1.8–42.5 M −1 s −1 , 0.13–1.16 M −1 s −1 and 0.04–20.4 M −1 s −1 corresponding to half-life values in the range of 1.9–146 min, 1.8–87 h and 2.5–637 h for oxazepam, nordazepam and diazepam, respectively, depending of the levels of studied parameters. Chlorine and pH affected significantly the reaction kinetics, where an increase of the pH resulted into a decrease of the reaction rate, whereas higher chlorine dosages led to faster kinetics, as expected in this case. The transformation of the studied benzodiazepines occurs mainly at the 1,4-diazepine 7-membered-ring, resulting in ring opening to form benzophenone derivatives or the formation of a 6-membered pyrimidine ring, leading to quinazoline derivatives. The formation of these by-products was also tested in real surface water samples observing kinetics of oxazepam degradation slower in river than in creek water, while the degradation of the two other benzodiazepines occurred only in the simpler sample (creek water). Finally, the acute and chronical toxicity and mutagenicity of precursors and transformation products were estimated using quantitative structure-activity relationship (QSAR) software tools: Ecological Structure Activity Relationships (ECOSAR) and Toxicity Estimation Software Tool (TEST), finding that some transformation products could be more toxic/mutagenic than the precursor drug, but additional test would be needed to confirm this fact. [ABSTRACT FROM AUTHOR]

Acesulfame (ACE) is one of the most commonly used artificial sweeteners. Because it is not metabolized in the human gut, it reaches the aquatic environment unchanged. In the present study, the reactivity of ACE in free chlorine-containing water was investigated for the first time. The degradation of ACE was found to follow pseudo-first-order kinetics. The first-order rate increased with decreasing pH from 9.4 to 4.8 with estimated half-lives from 693 min to 2 min. Structural elucidation of the detected transformation products (TPs) was performed by ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry. Integration of MS/MS fragments, isotopic pattern and exact mass allowed the characterization of up to 5 different TPs in the ultrapure water extracts analyzed, including two proposed new chlorinated compounds reported for the first time. Unexpectedly, several known and regulated disinfection by-products (DBPs) were present in the ACE chlorinated solution. In addition, two of the six DBPs are proposed as N-DBPs. Time-course profiles of ACE and the identified by-products in tap water and wastewater samples were followed in order to simulate the actual disinfection process. Tap water did not significantly affect degradation, but wastewater did; it reacted with the ACE to produce several brominated-DBPs. A preliminary assessment of chlorinated mixtures by luminescence inhibition of Vibrio fischeri showed that these by-products were up to 1.8-fold more toxic than the parent compound. The generation of these DBPs, both regulated and not, representing enhanced toxicity, make chlorine disinfection a controversial treatment for ACE. Further efforts are urgently needed to both assess the consequences of current water treatment processes on ACE and to develop new processes that will safely treat ACE. Human health and the health of our aquatic ecosystems are at stake. [ABSTRACT FROM AUTHOR]

Both UV treatment and ozonation are used to reduce different types of disinfection by-products (DBPs) in swimming pools. UV treatment is the most common approach, as it is particularly efficient at removing combined chlorine. However, the UV treatment of pool water increases chlorine reactivity and the formation of chloro-organic DBPs such as trihalomethanes. Based on the similar selective reactivity of ozone and chlorine, we hypothesised that the created reactivity to chlorine, as a result of the UV treatment of dissolved organic matter in swimming pool water, might also be expressed as increased reactivity to ozone. Moreover, ozonation might saturate the chlorine reactivity created by UV treatment and mitigate increased formation of a range of volatile DBPs. We found that UV treatment makes pool water highly reactive to ozone. The subsequent reactivity to chlorine decreases with increasing ozone dosage prior to contact with chlorine. Furthermore, ozone had a half-life of 5 min in non-UV treated pool water whereas complete consumption of ozone was obtained in less than 2 min in UV treated pool water. The ozonation of UV-treated pool water induced the formation of some DBPs that are not commonly reported in this medium, in particular trichloronitromethane, which is noteworthy for its genotoxicity, though this issue was removed by UV treatment when repeated combined UV/ozone treatment interchanging with chlorination was conducted over a 24-h period. The discovered reaction could form the basis for a new treatment method for swimming pools. [ABSTRACT FROM AUTHOR]

• Fourteen PHCZs were identified from the chlorination of seawater containing carbazole. • The formation of PHCZs followed a successive halogenation pattern. • The formation of PHCZs was dominated by bromocarbazoles. • Carbazole derivatives could be transformed into PHCZs during seawater chlorination. Although polyhalogenated carbazoles (PHCZs) have been widely detected in the marine environment, their origin is far from clear. In this study, the formation of PHCZs in the chlorination of seawater containing carbazole and its derivatives was investigated. A total of 14 PHCZs including six commonly found and eight unknown congeners were identified in the chlorination of seawater with carbazole. In addition, this study for the first time demonstrated the production of common PHCZs from the chlorination of seawater with 3-methyl carbazole and 3-formyl carbazole, especially 1,8-dibromo-3,6-dichlorocarbazole from 3-methyl carbazole. The formation of PHCZs in the reaction resulted from the halogenation of carbazole by reactive chlorine species (RCS) and mainly reactive bromine species (RBS), forming from the oxidation of bromide by RCS. Results also indicated that the reaction followed a successive halogenation pattern. A higher content of free chlorine and bromide facilitated the generation of RBS, while a higher concentration of DOC exhibited an inhibitory effect. The effects of free chlorine, bromide, DOC, and temperature on the formation of PHCZs were congener-specific. Given the widespread use of chlorination in seawater disinfection, seawater chlorination might be a potential source of PHCZs in the marine environment. [Display omitted] [ABSTRACT FROM AUTHOR]

• Overlooked contribution of PBMs towards the DBP formation was critically reviewed. • Elastomers, tire waste, polyelectrolytes, and MPs serve as potent DBP precursors. • Leached DOC and dissolved nitrogen from PBMs play a key role in DBP formation. • DBPs formation potential of polyelectrolytes was found as high as ∼2 mg/L. • DBPs formation potential of different microplastics ranged from 1.9 to 15,990 µg/L. Disinfection by-products (DBPs) are formed through the disinfection of water containing precursors such as natural organic matter or anthropogenic compounds (e.g., pharmaceuticals and pesticides). Due to the ever increasing use of plastics, elastomers, and other polymers in our daily lives, polymer-based materials (PBMs) are detected more frequently and at higher concentrations in water and wastewater. The present review provides a comprehensive and systematic analysis of the contribution of PBMs - including elastomers, tire waste, polyelectrolytes, and microplastics - as precursors of DBPs in water and wastewater. Literature shows that the presence of PBMs can lead to the leaching of dissolved organic matter (DOM) and subsequent formation of DBPs upon disinfection in aqueous media. The quantity and type of DBPs formed strongly depends on the type of polymer, its concentration, its age, water salinity, and disinfection conditions such as oxidant dosage, pH, temperature, and contact time. DOM leaching from elastomers and tire waste was shown to form N -nitrosodimethylamine up to concerning levels of 930 ng/L and 466,715 ng/L, respectively upon chemical disinfection under laboratory conditions. Polyelectrolytes can also react with chemical disinfectants to form toxic DBPs. Recent findings indicate trihalomethanes formation potential of plastics can be as high as 15,990 µg/L based on the maximum formation potential under extreme conditions. Our analysis highlights an overlooked contribution of DOM leaching from PBMs as DBP precursors during disinfection of water and wastewater. Further studies need to be conducted to ascertain the extent of this contribution in real water and wastewater treatment plants. [Display omitted] [ABSTRACT FROM AUTHOR]

Dichloroacetamide (DCAcAm) is an important type of nitrogenous disinfection byproduct. This study is the first to report that DCAcAm can be formed in the absence of chlorinated disinfectants (chlorine and chloramines). This can occur through reduction of three chloramphenicol (CAP) antibiotics by zero valent iron (ZVI). The effects of key experimental parameters, including reaction time, ZVI dose, pH, temperature, water type, and the presence of humic acid (HA) on the formation of DCAcAm were ascertained. The DCAcAm yields from three CAPs all presented the trend of increasing first and then decreasing with time and also increased with increasing ZVI dosage. DCAcAm yields from the ZVI reduction route were higher than those resulting from the chlorination of some previously identified DCAcAm precursors. Acidic conditions favored the formation of DCAcAm by the ZVI route. In addition, lower temperatures increased DCAcAm yields at extended contact times (>12 h). DCAcAm formed from the three CAPs in the presence of HA was lower than in the absence of HA. The formation potential of DCAcAm from the reduction of authentic waters spiked with CAPs by ZVI showed good linear correlations with initial concentrations of the three CAPs. This allows the formation of DCAcAm from the reduction of CAPs by ZVI to be predicted. Given that many wastewater and drinking water distribution networks contain unlined cast iron pipes, reactions between CAPs and ZVI may contribute to the formation of DCAcAm in such systems. [ABSTRACT FROM AUTHOR]

Biofilms are ubiquitous in the pipes of drinking water distribution systems (DWDSs), and recent experimental studies revealed that the chlorination of the microbial carbon associated with the biofilm contributes to the total disinfection by-products (DBPs) formation with distinct mechanisms from those formed from precursors derived from natural organic matter (NOM). A multiple species reactive-transport model was developed to explain the role of biofilms in DBPs formation by accounting for the simultaneous transport and interactions of disinfectants, organic compounds, and biomass. Using parameter values from experimental studies in the literature, the model equations were solved to predict chlorine decay and microbial regrowth dynamics in an actual DWDS, and trihalomethanes (THMs) formation in a pilot-scale distribution system simulator. The model's capability of reproducing the measured concentrations of free chlorine, suspended biomass, and THMs under different hydrodynamic and temperature conditions was demonstrated. The contribution of bacteria-derived precursors to the total THMs production was found to have a significant dependence on the system's hydraulics, seasonal variables, and the quality of the treated drinking water. Under system conditions that promoted fast bacterial re-growth, the transformation of non-microbial into microbial carbon DBP precursors by the biofilms showed a noticeable effect on the kinetics of THMs formation, especially when a high initial chlorine dose was applied. These conditions included elevated water temperature and high concentrations of nutrients in the influent water. The fraction of THMs formed from microbial sources was found to reach a peak of 12% of the total produced THMs under the investigated scenarios. The results demonstrated the importance of integrating bacterial regrowth dynamics in predictive DBPs formation models. [ABSTRACT FROM AUTHOR]

Disinfection by-products (DBPs) are an ever-increasing occurrence in water networks, particularly those which abstract water from peatland areas. Although much research has been carried out to discover novel methods to remove specific DBPs, the removal of natural organic matter (NOM) from source water may provide a more sustainable solution in many areas. This study focuses on the removal of NOM by novel filters, which could be retrospectively fitted to any conventional water treatment facility. The filters comprised stratified layers of a variety of media, including sand, Bayer residue, granular activated carbon (GAC), and pyritic fill. The filters were operated under two loading regimes, continuous and intermittent, at loading rates similar to recognised design standards. The most successful filter design comprised stratified layers of sand, GAC, and pyritic fill. Over the duration of a 240 day study, these filters obtained average dissolved organic carbon removal rates of 40%, and achieved average specific ultra-violet absorbance reductions from 2.9 to 2.4 L mg −1 m −1 . The study demonstrates that these novel filters may be used to reduce NOM levels, thus reducing the potential for DBP formation. Such designs can incorporate the use of waste media, making the overall design more sustainable and robust. [ABSTRACT FROM AUTHOR]

Water quality remains one of the greatest concerns with regards to human health. Advances in science and technology have resulted in highly efficient water treatment plants, significantly reducing diseases related to waterborne pathogenic microorganisms. While disinfection is critical to mitigate pathogen risk to humans, the reactions between the disinfectant and dissolved organic compounds can lead to the formation of chemical contaminants called disinfection by-products (DBPs). DBPs have been related to numerous health issues including birth defects and cancer. The formation of disinfection by-products occurs due to the reaction of oxidants and natural organic matter. DBP precursors are derived from anthropogenic sources including pharmaceuticals and chemical waste, the breakdown of vegetation from external catchment sources (allochthonous) and internally derived sources including phytoplankton (autochthonous). Current literature focuses on the contribution of allochthonous sources towards the formation of DBPs, however, the recalcitrant nature of hydrophilic phytoplankton derived organic matter indicates that autochthonous derived organic carbon can significantly contribute to total DBP concentrations. The contribution of phytoplankton to the formation of DBPs is also influenced by cellular exudation rates, chemical composition, environmental conditions and the physical and chemical conditions of the solution upon disinfection. Formation of DBPs is further influenced by the presence of cyanobacteria phyla due to their notoriety for forming dense blooms. Management of DBP formation can potentially be improved by reducing cyanobacteria as well as DBP precursors derived from other phytoplankton. [ABSTRACT FROM AUTHOR]

Emerging contaminants represent a wide group of the most different compounds. They appear in the environment at trace levels due to human activity. Most of these compounds are not yet regulated. Sunscreen UV-filters play an important role among these emerging contaminants. In the present research the reactions of 4- tert -butyl-4’-methoxydibenzoylmethane (avobenzone), the most common UV filter in the formulation of sunscreens, were studied under the combined influence of active chlorine and UV-irradiation. Twenty five compounds were identified by GC/MS as transformation products of avobenzone in reactions of aquatic UV-irradiation and chlorination with sodium hypochlorite. A complete scheme of transformation of avobenzone covering all the semivolatile products is proposed. The identification of the two primary chlorination products (2-chloro-1-(4- tert -butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione and 2,2-dichloro-1-(4- tert -butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione) was confirmed by their synthesis and GC/MS and NMR analysis. Although the toxicities of the majority of these products remain unknown substituted chlorinated phenols and acetophenones are known to be rather toxic. Combined action of active chlorine and UV-irradiation results in the formation of some products (chloroanhydrides, chlorophenols) not forming in conditions of separate application of these disinfection methods. Therefore caring for people «well-being» it is of great importance to apply the most appropriate disinfection method. Since the primary transformation products partially resist powerful UV-C irradiation they may be treated as stable and persistent pollutants. [ABSTRACT FROM AUTHOR]

Sodium hypochlorite (NaClO) is the most commonly used disinfectant in pool treatment system. Outdoor pools usually suffer from the strong sunlight irradiation which degrades the free chlorine rapidly. In addition, more pools start to adopt the recirculation of swimming pool water, which intensifies the disinfection by-product (DBP) accumulation issue. Given these potential drawbacks of using NaClO in the tropical environment, two alternative organic-based disinfectants, trichloroisocyanuric acid (TCCA, C 3 Cl 3 N 3 O 3 ) and bromochlorodimethylhydantoin (BCDMH, C 5 H 6 BrClN 2 O 2 ), were investigated and compared to NaClO in terms of their self-degradation and the formation of DBPs, including trihalomethanes (THMs) and haloacetic acids (HAAs), under simulated tropical climate conditions. The result reveals that halogen stabilizer, TCCA, had the advantages of slower free chlorine degradation and lower DBP concentration compared to NaClO, which makes it a good alternative disinfectant. BCDMH was not recommended mainly due to the highly reactive disinfecting ingredient, hypobromous acid (HBrO), which fails to sustain the continuous disinfection requirement. Total disinfectant dosage was the main factor that affects residual chlorine/bromine and THM/HAA formation regardless of different disinfectant dosing methods, e.g. shock dosing (one-time spiking) in the beginning, and continuous dosing during the whole experimental period. Two-stage second-order-kinetic-based models demonstrate a good correlation between the measured and predicted data for chlorine decay ( R 2 ≥ 0.95), THM ( R 2 ≥ 0.99) and HAA ( R 2 ≥ 0.83) formation. Higher temperature was found to enhance the DBP formation due to the temperature dependence of reaction rates. Thus, temperature control of pools, especially for those preferring higher temperatures (e.g. hydrotherapy and spa), should take both bather comfort and DBP formation potential into consideration. It is also observed that chlorine competition existed between different precursors from natural organic matters (NOM) in filling water and body fluid analogue (BFA). Among the composition of BFA, uric acid, citric acid and hippuric acid were found to be the main precursors for HAA formation. [ABSTRACT FROM AUTHOR]

Reclaimed water has recently become an important water source for urban use, but the composition of dissolved organic matter (DOM) in reclaimed water has rarely been characterized at the compound level because of its complexity. In this study, the transformation and changes in composition of low molecular weight DOM in water reclamation processes, where secondary effluent of the municipal wastewater treatment plant was further treated by biofiltration, ozonation and chlorination, were investigated by “unknown” screening analysis using Orbitrap mass spectrometry (Orbitrap MS). The intense ions were detected over an m / z range from 100 to 450. In total, 2412 formulae with various heteroatoms were assigned, and formulae with carbon (C), hydrogen (H) and oxygen (O) only and C, H, O and sulfur (S) were the most abundant species. During biofiltration, CHO-only compounds with relatively high hydrogen to carbon (H/C) ratio or with saturated structure were preferentially removed, while CHOS compounds were mostly removed. Ozonation induced the greatest changes in DOM composition. CHOS compounds were mostly decreased after ozonation while ozone selectively removed CHO compounds with relatively unsaturated structure and produced compounds that were more saturated and with a higher degree of oxidation. After chlorination, 168 chlorine-containing formulae, chlorinated disinfection by-products (DBPs), were additionally detected. Candidate DBP precursors were determined by tracking chlorinated DBPs formed via electrophilic substitution, half of which were generated during the ozonation. [ABSTRACT FROM AUTHOR]

N -Nitrosamines (NAs) in drinking water have attracted considerable attention in recent years due to their high carcinogenicity, frequent occurrence, and their potential regulation. During the past three years, we have collected about 164 water samples of finished water, tap water, and source water from 23 provinces, 44 cities from large cities to small towns, and 155 sampling points all over China. The occurrence of NAs in the finished and tap water was much higher in China than that in the U.S. Nine NAs were measured and NDMA had the highest concentration. The occurrence of NDMA was in 33% of the finished waters of water treatment plants and in 41% of the tap waters. The average NDMA concentration in finished and tap waters was 11 and 13 ng/L, respectively. Formation potentials (FPs) of source waters were examined with an average NDMA FP of 66 ng/L. Large variations in NA occurrence were observed geographically in China and temporally in different seasons. The Yangtze River Delta area, one sub-area in East China, had the highest concentrations of NAs, where the average NDMA concentrations in the finished and tap water were 27 and 28.5 ng/L, respectively, and the average NDMA FP in the source water was 204 ng/L. NA control may be achieved by applying breakpoint free chlorination and/or advanced treatment of ozone – granular activated carbon process to remove the NA precursors before disinfection. [ABSTRACT FROM AUTHOR]

Although organic chloramines are known to form during the disinfection of drinking water with chlorine, little information is currently available on their occurrence or toxicity. In a recent in vitro study, some organic chloramines (e.g. N -chloroglycine) were found to be cytotoxic and genotoxic even at micromolar concentrations. In this paper, the formation and stability of 21 different organic chloramines, from chlorination of simple amines and amino acids, were studied, and the competition between 20 amino acids during chlorination was also investigated. For comparison, chlorination of two amides was also conducted. The formation and degradation of selected organic chloramines were measured using either direct UV spectroscopic or colorimetric detection. Although cysteine, methionine and tryptophan were the most reactive amino acids towards chlorination, they did not form organic chloramines at the chlorine to precursor molar ratios that were tested. Only 6 out of the 21 organic chloramines formed had a half-life of more than 3 h, although this group included all organic chloramines formed from amines. A health risk assessment relating stability and reactivity data from this study to toxicity and precursor abundance data from the literature indicated that only N -chloroglycine is likely to be of concern due to its stability, toxicity and abundance in water. However, given the stability of organic chloramines formed from amines, more information about the toxicity and precursor abundance for these chloramines is desirable. [ABSTRACT FROM AUTHOR]

N -Nitrosodimethylamine (NDMA) is a disinfection by-product (DBP) that is potentially carcinogenic and has been found to occur in drinking water treatment systems impacted with treated wastewater. A major gap in NDMA research is an understanding of the persistence of wastewater-derived precursors within the natural environment. This research sought to fill this knowledge gap by surveying NDMA precursors across the length of a wastewater effluent-dominated wash. Significant precursor reduction (17%) was found to occur from introduction into the wash to a point 9 h downstream. This reduction translates into a half-life of roughly 32 h for bulk NDMA precursors. Further laboratory experiments examining rates of photolysis, biodegradation and loss to sediments, illustrated that both photolytic and biological degradation were effective removal mechanisms for NDMA precursors. Loss to sediments that were acquired from the wash did not appear to reduce NDMA precursors in the water column, although a control conducted with DI water provided evidence that significant NDMA precursors could be released from autoclaved sediments (suggesting that sorption does occur). Microbial experiments revealed that microbes associated with sediments were much more effective at degrading precursors than microbes within the water column. Overall, this study demonstrated that natural processes are capable of attenuating NDMA precursors relatively quickly within the environment, and that utilities might benefit from maximizing source water residency time in the environment, prior to introduction into treatment plants. [ABSTRACT FROM AUTHOR]

After coagulation of high salinity reverse osmosis concentrate (ROC) with either alum or ferric chloride followed by UVC/H 2 O 2 treatment, biological activated carbon (BAC) was investigated for the removal of DOC. BAC treatment mainly removed low molecular weight (LMW) neutral molecules indicating that biodegradation was the predominant mechanism of organic matter removal. Coagulation with ferric chloride gave greater DOC reductions than alum both as a stand-alone treatment and after the sequence of UVC/H 2 O 2 and BAC treatment. However, overall reduction after the sequence of coagulation, UVC/H 2 O 2 and BAC treatment was only marginally greater for ferric chloride (68%) than for alum (62%). Trihalomethane formation potential and N-Nitrosodimethylamine concentration decreased markedly after UVC/H 2 O 2 treatment. UVC/H 2 O 2 treatment of the ROC led to the generation of extreme toxicity according to the Microtox assay, but no toxicity was observed after BAC, demonstrating its advantage for enabling safe disposal of the treated ROC. Implementation of coagulation as a pre-treatment and BAC as a post-treatment markedly reduced (6–8 times) the electrical energy dose ( E ED) required for the UVC/H 2 O 2 process. The sequence of coagulation, UVC/H 2 O 2 and BAC treatment was demonstrated as a potential process for the removal of organic matter from high salinity municipal ROC. [ABSTRACT FROM AUTHOR]