Search

Haloacetic acids (HAAs) are ubiquitous in drinking water and have been associated with impaired male reproductive health. However, epidemiological evidence exploring the associations between HAA exposure and reproductive hormones among males is scarce. In the current study, the urinary concentrations of dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA), the internal exposure markers of HAAs, as well as sex hormones (testosterone [T], progesterone [P], and estradiol [E 2 ]) were measured among 449 Chinese men. Moreover, in vitro experiments, designed to simulate the real-world scenarios of human exposure, were conducted to assess testosterone synthesis in the Leydig cell line MLTC-1 and testosterone metabolism in the hepatic cell line HepG2 in response to low-dose HAA exposure. The DCAA and TCAA urinary concentrations were found to be positively associated with urinary T, P, and E 2 levels (all p < 0.001), but negatively associated with the ratio of urinary T to E 2 (p < 0.05). Combined with in vitro experiments, the results suggest that environmentally-relevant doses of HAA stimulate sex hormone synthesis and steroidogenesis pathway gene expression in MLTC-1 cells. In addition, the inhibition of the key gene CYP3A4 involved in the testosterone phase Ⅰ catabolism, and induction of the gene UGT2B15 involved in testosterone phase Ⅱ glucuronide conjugation metabolism along with the ATP-binding cassette (ABC) transport genes (ABCC4 and ABCG2) in HepG2 cells could play a role in elevation of urinary hormone excretion upon low-dose exposure to HAAs. Our novel findings highlight that exposure to HAAs at environmentally-relevant concentrations is associated with increased synthesis and excretion of sex hormones in males, which potentially provides an alternative approach involving urinary hormones for the noninvasive evaluation of male reproductive health following exposure to DBPs. [Display omitted] • Positive association was observed between the urinary excretion of HAAs and sex hormones in males. • Toxicological experiments involving HAA exposure validated the epidemiological data. • Dose-specific effects of HAA were observed on male endocrine disruption. • Environmentally-relevant doses of HAAs stimulated steroidogenesis and testosterone excretion. [ABSTRACT FROM AUTHOR]

Chlorine activation-inefficient and the generation of disinfection by-products (DBPs) has indeed limited the application of UV/chlorine process. In this study, the typical metal-organic frameworks (MOFs) NH 2 -MIL53(Fe) were successfully modified with organic ligands containing sulfur functional groups and applied to construct a novel UV-LED-driven heterogeneous chlorine activation system. The generation of intermediate energy levels and the charge redistribution effect on Fe-S bond facilitated the excitation of electrons and realized the effective separation of photohole (h vb + ) and photoelectron (e cb - ). The involvement of S-NH 2 -MIL53(Fe) improved the efficiency of UV-LED/chlorine process by 6 times. The effective activation of HOCl/OCl- by h vb + and e cb - significantly enhanced the yield of HO · and Cl ·. More importantly, HOCl/OCl- played a dual role in UV-LED/chlorine/S-NH 2 -MIL53(Fe) process as a precursor for the generation of free radicals and a catalyst for the enhancement of HO · yield, which could achieve efficient removal of the target pollutants at lower chlorine doses. In addition, the presence of low-valent sulfur species and e cb - accelerated the cycle of Fe(II)/Fe(III) and in-situ generation of HO · and Cl ·. The known generation of DBPs in UV-LED/chlorine/S-NH 2 -MIL53(Fe) process decreased by 37.9% compared to UV-LED/chlorine process. Developing novel UV-LED/chlorine/S-NH 2 -MIL53(Fe) processes provided a reliable strategy to efficiently purify actual micro-polluted water bodies. [Display omitted] • A novel UV-LED-driven heterogeneous chlorine activation process was proposed. • Intermediate energy levels and charge redistribution acted as electronic modulation. • Efficient separation of h vb + and e cb - played a crucial role in chlorine activation. • HOCl/OCl- played the dual role of precursor to radicals and catalyst to increase HO ·. • UV-LED/chlorine/S-NH 2 -MIL53(Fe) process effectively controlled the generation of DBPs. [ABSTRACT FROM AUTHOR]

Since trihalomethanes were discovered in 1974, disinfection by-products (DBPs) in drinking water have attracted extensive attention. In 2011, more than 600 known DBPs were compiled; however, newly reported DBPs have not been integrated. The rapid development of mass spectrometry has led to a significant increase in the number of DBPs, therefore, there is a need to develop a database of all DBPs and their properties. Herein, a database including 6310 DBPs (651 confirmed, 1478 identified and 4142 proposed) reported between 1974 and 2022 was constructed and made available for public use at https://dbps.com.cn/main. This database can be a tool in screening new DBPs, comprehensively reviewing, and developing predictive models. In this paper, to demonstrate the functions of the database and provide useful information for this area, the origin of the collected DBPs was presented, and some basic information, including elemental composition, molecular weight, functional groups, and carbon frameworks, were comparatively analyzed. The results showed that the proportion of DBPs verified by standard compounds and frequently detected in real water is less than 7.0%, and most of DBPs remained to be identified. Approximately 88% of DBPs contain halogens, and brominated -DBPs occupied a similar ratio to chlorinated -DBPs in real water. Acids were the main functional groups of DBPs, aliphatic and aromatic compounds are the two major carbon frameworks, and the molecular weights of most DBPs ranged from 200 to 400 Da. In addition, 4142 proposed DBPs as obtained using high-resolution mass spectrometry, were characterized based on the modified van Krevelen diagram and adjusted indexes with halogens. Most of the proposed DBPs featured lignin and tannin structures, and phenolic/highly unsaturated DBPs account for the majority. [Display omitted] • A web database of DBPs was constructed and some applications were depicted. • The basic information of 6310 reported DBPs since 1974 was reviewed. • Only 10% of reported DBPs are verified by chemical standards. • Acids are the largest category among all functional groups of reported DBPs. • Structures of proposed DBPs were characterized based on adjusted indexes. [ABSTRACT FROM AUTHOR]

Halogenated benzoquinones (HBQs) are frequently detected in tap water. HBQ levels are correlated with water age. As the water–transmission distance (water age) increases, the levels of bromo-benzoquinones (Br-BQs) decreased and those of chloro-benzoquinones (Cl-BQs) remained relatively stable in drinking water–distribution system in the presence of residual chlorine. 2,3,5,6-Tetrachloro-1,4-benzoquinone (TCBQ) and 2,6-dibromo-1,4-benzoquinone (DBBQ) were the most abundant Cl-BQ and Br-BQ, with maximum concentrations of 60.2 and 181.4 ng/L, respectively. TCBQ and DBBQ were chosen as representatives of HBQs to investigate their reactions with chlorine, including kinetics, pathways, and changes in toxicity. The hydrolysis and chlorination rates of HBQs were significantly pH-dependent, and the kinetic rates of DBBQ were faster than TCBQ in the pH range of 5–10. Chlorination converted highly toxic TCBQ and DBBQ to less-toxic chlorinated/brominated aliphatic disinfection by-products (DBPs), thereby reducing the overall toxicity of water bodies. This study provides comprehensive insights into the distinct life cycles of TCBQ and DBBQ in drinking water, covering formation, transformation, and toxicity. These findings provide a nuanced understanding of the risks posed by HBQs at various locations within the drinking water distribution system, offering valuable guidance for improving the control of DBPs in drinking water. [Display omitted] • Evolution of HBQs and aliphatic DBPs with age of drinking water was investigated. • Uncovering the reasons for the differ trends in the conversion of Cl-BQs and Br-BQs. • Formation and transformation mechanisms of HBQs were studied. • Chlorine conversion of HBQs reduced the toxicity of water samples. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Cl 2 decreased algae fluorescence but cells size do not remarkably varied. • O 3 led to more cells with decreased size but less reduction in fluorescence. • Pre-chlorination increased DBP yields detected after coagulation-filtration. • Pre-ozonation decreased total DBP yields detected after coagulation-filtration. • Pre-oxidation affected HAA&chloral precursors more greatly than THM precursors. Abstract Effect of pre-chlorination and pre-ozonation on Microcystis aeruginosa (MA) and Coccomyxa subellipsoidea (CS) as disinfection by-products (DBPs) precursors was investigated after coagulation-filtration. Pre-chlorination considerably decreased the autofluorescence of algae cells but barely influenced cell granularity. In comparison, after pre-ozonation more algae cells were associated with decreased cell size; yet less reduction in the autofluorescence was observed. In MA case, pre-chlorination increased the residual algae density after coagulation-filtration by 132%–146% while pre-ozonation enhanced the algae removal by 26%–28%. In CS case, algae removal was improved by pre-chlorination (32%–45%) and pre-ozonation (7%–45%). Pre-chlorination enhanced the removal of algogenic organic matters (AOM) by coagulation-filtration, especially for tryptophan-like and soluble microbial products. Effect of pre-ozonation on the fluorescence intensity of AOM after coauglation-filtration depended on AOM species and the ratio of [ozone dose]:[algae density]. In both MA and CS cases, chlorine increased the yields of trihalomethane (THM, 25%–78% and 51%–103%), haloacetic acid (HAA, 140%–360% and 167%–233%) and chloral (50%–161% and 68%–108%), respectively. Pre-ozonation decreased the total DBPs yields. For MA-added suspensions, ozone decreased the production of THM, HAA and chloral by 15%–37%, 28%–39% and 60%, respectively. In CS case, chloral yield was decreased by 12%–31% while THM formation was largely unchanged. HAA production varied by ± 1.5 μg/L. [ABSTRACT FROM AUTHOR]

A novel strategy based on solar photo-Fenton mediated by ferric nitrilotriacetate (Fe3+-NTA) combined with NaOCl in continuous flow mode for wastewater reclamation has been studied. Escherichia coli (E. coli) inactivation attained ≥ 5 log10-units, meeting the most restrictive EU 2020/741 target (10 CFU/100 mL), and 75% of organic microcontaminant total load was removed. As a remarkable finding, trihalomethanes (THMs) concentration was insignificant, complying by far with the Italian legislation limit. To attain these results, first the effect of liquid depth on E. coli inactivation and imidacloprid (IMD) removal from spiked municipal effluents was evaluated in continuous flow pilot-scale raceway pond reactors at 60-min hydraulic residence time with low reagent concentrations (0.10 mM Fe3+-NTA, 0.73 mM H 2 O 2 and 0.13 mM NaOCl). Disinfection was due to the bactericidal effect of chlorine. In contrast, liquid depth notably influenced microcontaminant removal, highlighting that operation at 10-cm liquid depth allows achieving treatment capacities higher than at 5 cm (16.50 vs 28.20 mg IMD/m2∙day). Next, the monitoring of THMs was carried out to evaluate the generation and degradation of disinfection by-products, along with the removal of actual microcontaminants. These promising results draw attention to the treatment potential and open the way for its commercial application. [Display omitted] • Continuous flow operation of solar photo-Fenton combined with NaOCl was assessed. • Liquid depth affected microcontaminant removal; disinfection was due to NaOCl. • > 75% microcontaminants were removed in 10-cm deep reactor at 60 min of HRT. • E. coli inactivation was ≥ 5 log-units meeting EU 2020/741 target. • Trihalomethanes' concentration was 7.5–10 fold below the mandatory limit regulated. [ABSTRACT FROM AUTHOR]

Membrane fouling, primarily resulting from natural organic matter (NOM) widely existing in water sources, has always been a chief hindrance for the prevalent application of ultrafiltration (UF). Thus, vacuum ultraviolet (VUV)/chlorine process was proposed as a strategy for UF membrane fouling control and ultraviolet (UV)/chlorine process was used for comparison. VUV/chlorine process exhibited more excellent performance on NOM removal than UV/chlorine process. [HO•]ss and [Cl•]ss were calculated as 1.26 × 10−13 and 3.06 × 10−14 M, respectively, and ClO• might not exist under the conditions of 0.08 mM chlorine and 30 min VUV irradiation. [HO•]ss, [Cl•]ss and [ClO•]ss were not available and the formation of reactive radicals was unsustainable in UV/chlorine system. Moreover, VUV/chlorine pretreatment also showed better performance on the reversible and irreversible membrane fouling control than UV/chlorine pretreatment. The dominated fouling mechanism in the final stage of filtration was cake filtration. Additionally, the amount of detected disinfection by-products (DBPs) in VUV/chlorine system was significantly lower than that in UV/chlorine system. During subsequent chlorination disinfection, the yield of DBPs with VUV/chorine pretreatment was higher than that with UV/chlorine pretreatment. VUV/chlorine pretreatment could effectively control DBPs formation when the pretreatment time was extended to 120 min. In summary, VUV/chlorine system presented a most excellent performance on membrane fouling control, NOM degradation and DBPs control. [Display omitted] • VUV/chlorine process can control membrane fouling more effectively than UV/chlorine. • VUV/chlorine pretreatment can effectively remove NOM and control DBPs formation. • Cake filtration was the dominated fouling mechanism in the final stage of filtration. • Formation of radicals is closely related to chlorine content in UV/chlorine system. • HO• and Cl• were produced and [HO•]ss was higher than [Cl•]ss in VUV/chlorine system. [ABSTRACT FROM AUTHOR]

The objective of this study is to evaluate the influence of water distribution system conditions (pH, total organic carbon, residual chlorine, and phosphate) on haloacetic acids (HAAs) biodegradation. A series of batch microcosm tests were conducted to determine biodegradation kinetics and collected biomass was used for real time quantitative reverse transcription polymerase chain reaction analyses to monitor how these drinking water distribution system conditions affect the relative expression of bacterial dehalogenase genes. It was observed that tested water distribution system conditions affected HAA biodegradation with different removal efficiencies (0–100%). HAA biodegradation was improved in tested samples with TOC (3 mg/L) and pH 8.5 compared to those of TOC (0 mg/L) and pH 7, respectively. However, slight improvement was observed with the increased PO 4 concentration (3.5 mg/L), and the presence of residual chlorine even at low concentration prohibited biodegradation of HAAs. The observed trend in the relative expression of dehII genes was compatible with the HAA biodegradation trend. Overall relative expression ratio of dehII genes was lower at pH 7, phosphate (0.5 mg/L), and TOC (0 mg/L) in comparison with pH 8.5, phosphate (3.5 mg/L), and TOC (3 mg/L) in the same experimental conditions. [ABSTRACT FROM AUTHOR]

The carcinogenic nitrogenous disinfection by-product, N -nitrosodimethylamine (NDMA), is challenging to adsorb due to its high polarity and solubility. Our previous research demonstrated that the adsorptive removal of NDMA can be improved using surface-modified activated carbon (AC800). The current study evaluated the efficacy of AC800 in removing NDMA in a continuous-flow column over 75 days, using both granular activated carbon (GAC) and biologically activated carbon (BAC) columns. The AC800 GAC column demonstrated extended breakthrough and exhaustion times of 10 days and 22 days, respectively, compared to the conventional GAC column at 4 days and 10.5 days. The surface modification effect persisted for 25 days before the removal trends became indistinguishable. The AC800 BAC column outperformed the conventional BAC column with a longer breakthrough time of 11.3 days compared to 7.4 days. BAC columns consistently showed greater NDMA removal, emphasizing the role of biodegradation in NDMA removal on carbon. The higher NDMA removal in the inoculated columns was attributed to increased microbial diversity and the dominance of six specific genera, Methylobacterium, Phyllobacterium, Curvibacter, Acidovorax, Variovorax, and Rhodoferax. This study provides new insights into using modified activated carbon as GAC and BAC media in a real-world continuous-flow setup. [Display omitted] • Thermally modified BAC performed well in removing NDMA in a continuous flow system. • The advantage of the thermally modified media persisted for 25 days. • Inoculated columns yielded higher NDMA removal (p < 0.05) than non-inoculated columns. • Some nitro-aromatic compounds-degraders likely contributed to NDMA biodegradation. [ABSTRACT FROM AUTHOR]

Microcystins (MCs) in drinking water have gained much attention due to their adverse health effects. However, little is known about the impact of pre-oxidation in the formation of disinfection by-products (DBPs) during the downstream chlorination of MCs. The present study examined the formation of both carbonaceous and nitrogenous DBPs from chlorination of MC-LR (the most abundant MC species) and evaluated the impact of permanganate (PM), hydrogen peroxide (H 2 O 2 ) and chlorine dioxide (ClO 2 ) pre-oxidation on the DBP formation in chlorination. Higher yields of chloroform (CF) (maximum 43.0%) were observed from chlorination of MC-LR than free amino acids which are included in MC-LR structure. Chloral hydrate (CH) and dichloroacetonitrile (DCAN) were also produced from the chlorination of MC-LR, and the latter one was formed probably due to the chlorination of peptide bonds. A high pH favored the production of CF and CH, but inhibited the formation of DCAN. In the presence of bromide, bromo-DBPs could be produced to pose a threat. For example, 0.58 μg/L of tribromoacetaldehyde was produced from the chlorination of MC-LR at Br − = 200 μg/L. PM and ClO 2 pre-oxidation could both reduce the DBP formation from MC-LR. In contrast, H 2 O 2 appeared not to significantly control the DBP formation. [ABSTRACT FROM AUTHOR]

The performance of UV-activated persulfate (UV/PS) technology as preoxidation process to enhance Microcystis aeruginosa removal by subsequent coagulation-sedimentation was firstly evaluated. The results demonstrate that UV/PS preoxidation could successfully promote coagulation of algae cells through the effective neutralization of zeta potential, which was caused by the changes of cell morphology, size distribution and surface properties after simultaneous UV irradiation and formed reactive species (i.e. SO 4 − and HO ) oxidation. Since excessive oxidation would cause cell rupture along with the release of organics, which could deteriorate coagulation efficiency, optimal PS dose (60 mg/L) and UV dose (375 mJ/cm 2 ) were proposed to exist in this study. The concentrations of extracellular algal organic matter (AOM) sharply increased by 48.2% during the preoxidation period, while gradually decreased in the following coagulation and sedimentation. Most of the concerned disinfection by-products (DBPs) monotonically decreased or followed fluctuant reduction with increasing PS doses, whereas the trichloromethane, trichloroacetic acid and dichloroacetonitrile persistently increased, which was inferred to be related to the variation of AOM. This study suggests that UV/PS might be a potential pretreatment process to assist coagulation on the removal of algae. [ABSTRACT FROM AUTHOR]

The discovery of new disinfection by-products (DBPs) is still a rarely investigated research area in past studies. In particular, compared to freshwater pools, therapeutic pools with their unique chemical composition have rarely been investigated for novel DBPs. Here we have developed a semi-automated workflow that combines data from target and non-target screening, calculated and measured toxicities into a heat map using hierarchical clustering to assess the pool's overall potential chemical risk. In addition, we used complementary analytical techniques such as positive and negative chemical ionization to demonstrate how novel DBPs can be better identified in future studies. We identified two representatives of the haloketones (pentachloroacetone, and pentabromoacetone) and tribromo furoic acid detected for the first time in swimming pools. Non-target screening combined with target analysis and toxicity assessment may help to define risk-based monitoring strategies in the future, as required by regulatory frameworks for swimming pool operations worldwide. [Display omitted] • Use of EI, PCI and NCI as complementary analytical methods. • Identification of potential toxic DBPs by GC/LC-HRMS. • Hierarchical clustering for analysis of non-target features. • Application of suspect and non-target screening approaches to detect DBPs. • Identification of two new haloketones and tribromo furoic acid in swimming pools. [ABSTRACT FROM AUTHOR]

As a vital freshwater resource, rainwater is usually stored in water cellars in arid regions to solve the daily drinking water problems of the population. However, the status of disinfection by-products (DBPs) generation in cellar water under intermittent disinfection conditions is unclear. Therefore, we investigated the formation and distribution characteristics of DBPs in cellar water under intermittent disinfection conditions for the first time. The results demonstrated that six categories of DBPs were selected for detection after chlorination, including trihalomethanes (THMs), haloacetic acids (HAAs), haloketones (HKs), haloacetonitriles (HANs), halonitromethanes (HNMs), and nitrosamines (NAs), among which HAAs, HKs, and HANs were the major DBPs. Only bromoacetic acid (MBAA), dichloroacetic acid (DCAA), and trichloroacetic acid (TCAA) showed an increasing trend of accumulation as the number of disinfections increased. Meanwhile, the precursor composition was gradually transformed from humic substances to amino acids, and both organic substances were the main precursors of HAAs. The health risk assessment showed that the main carcinogenic and non-carcinogenic risks of cellar water were contributed by NAs and HAAs, respectively, and children are more susceptible to the risks than adults. The best time to drink cellar water is after approximately 12 days of storage, when the total carcinogenic risk is the minimum. [Display omitted] • Higher carbon- than nitrogen-containing DBPs are formed in disinfected rainwater. • Intermittent disinfection leads to accumulation of MBAA, DCAA and TCAA. • pH attenuation in the stored rainwater facilitates the formation of HAAs. • NAs and HAAs are the major contributors to the carcinogenic risk. [ABSTRACT FROM AUTHOR]

Bromide ions (Br-) affected non-brominated nitroso-dimethylamine (NDMA) formation during ozonation, but the mechanism is still unclear. 1,1,1′,1′-tetramethyl-4,4′-(methylene-di- p -phenylene) di-semicarbazide (TMDS) was chosen to further probe this problem. The results indicated that low levels of Br- (≤20 μM) enhanced NDMA from 3.27 to 7.56 μg/L, while its amount slightly dropped to 6.22 μg/L raising Br- to 100 μM. It was experimentally verified that intermediates 1,1-dimethylsemicarbazide (DMSC) and 1,1-dimethylhydrazine (UDMH) played important roles on promoting NDMA generation, whose contribution rates were 40.2% and 32.2%, respectively. The brominated substances with higher NDMA molar yields were detected. ∙OH reduced NDMA formation without Br-, while it played promotion role with Br-; the corresponding contribution rates were − 26.9% and 29.2%, respectively. No matter with or without Br-, both ∙O 2 - and lO 2 brought a boost to NDMA formation, their contribution ratios were 34.9% and 58.1% without Br-, while raised significantly to 64.6% and 81.5% when Br- existed. Br- not only facilitated NDMA formation, but also benefited the degradation of TMDS. Based on the calculation results and intermediates detected, the influence mechanisms of Br- were proposed. The results would provide theoretical basis and technical guarantee for treating NDMA precursors and bromide co-existing water in the future. [Display omitted] • Trace Br- facilitated while high levels inhibited NDMA formation during ozonation of TMDS. • Brominated substances were experimentally verified to be the culprit for Br- promoting NDMA formation. • Br- promoted the conversion of TMDS was the other non-ignorable reason for more NDMA generation. • The bromine substitution position was proved to be the H atom connecting to N besides benzene rings of TMDS. • Reactive oxygen species played more promotion roles on NDMA formation with Br- than that without Br-. [ABSTRACT FROM AUTHOR]

Potential genotoxic effects of chlorinated drinking water now are of a great concern. In this study, raw water, finished water, and tap water from a water plant in Wuhan, China were collected in two different sampling times of the year (January and July). Genotoxic effects of water extracts were evaluated using a combination of three different bioassays: SOS/umu test, HGPRT gene mutation assay, and micronucleus assay, which were separately used to detect DNA damage, gene mutation, and chromosome aberration. The results of three different bioassays showed that all water samples in January and July induced at least one types of genotoxic effects, of which the DNA-damage effects were all detectable. The levels of DNA-damage effects and gene-mutation effects of finished water and tap water in January were higher than those in July. Chlorination could increase the DNA-damage effects of drinking water in January and the gene-mutation effects of drinking water in both January and July, but did not increase the chromosome-aberration effects of drinking water in both January and July. Our results highlighted the importance of using a combination of different bioassays to evaluate the genotoxicity of water samples in different seasons. [ABSTRACT FROM AUTHOR]

This study investigated the effect of disinfection by-products (DBPs) formation in pre-oxidation with ferrate(VI) (Fe VI O 4 2− , Fe(VI)) and relationship between subsequent chlorination of Suwannee river natural organic matter (SRNOM) and eight model compounds containing moieties of alcohol, aldehyde, amines, amino acids, and phenol. The DBPs studied were trihalomethanes (THMs), chloral hydrate (CH), haloacetonitriles (HANs), and trichloronitromethane (TCNM). When the interaction of Fe(VI) and SRNOM was independently examined at pH 7.0, a decrease was seen in dissolved organic carbon and in the hydrophobic and hydrophilic fractions of NOM. With the model compounds, the results showed that Fe(VI) pre-oxidation and subsequent chlorination decreased the formation of THMs with most of the compounds except amines and glycine. The effect of Fe(VI) preoxidation on CH and HANs formation from model compounds varied and was dependent on ferrate doses. Fe(VI) pre-oxidation significantly enhanced TCNM formation, compared to without pre-oxidation, from subsequent chlorination of methylamine, dimethylamine and glycine and the formation increased with increasing doses of ferrate. Correlations of DBPs formation between SRNOM and model compounds were sought to identify the moieties involved in influencing the formation of DBPs. The generation of DBPs is described using the parent molecules and the kinetics and reaction products of Fe(VI)/chlorine oxidation. [ABSTRACT FROM AUTHOR]

Abstracts This study aimed to compare the toxicity reduction performance of conventional drinking water treatment (CT) and a treatment (NT) with quaternized magnetic microspheres (NDMP) based on chemical analyses. Fluorescence excitation–emission–matrix combined with parallel factor analysis identified four components in source water of different rivers or lake, and the abundance of each component differed greatly among the different samples. Compared with the CT, the NT evidently reduced the concentrations of dissolved organic carbon, adsorbable organic halogens (AOX), bromide and disinfection by-products. Toxicological evaluation indicated that the NT completely eliminated the cytotoxicity, and greatly reduced the genotoxicity and oxidative stress of all raw water. In contrast, the CT increased the cytotoxicity of Taihu Lake and the Zhongshan River water, genotoxicity of Taihu Lake and the Mangshe River water, as well as the levels of superoxide dismutase and malondialdehyde of the Mangshe River water. Correlation analysis indicated that the AOX of the treated samples was significantly correlated with the genotoxicity and glutathione concentration, but exhibited no correlation with either of them for all the samples. As it can effectively reduce pollutant levels and the toxicities of drinking water, NDMP might be widely used for drinking water treatment in future. [ABSTRACT FROM AUTHOR]

Chlorine dioxide (ClO 2) has emerged as a broad-spectrum, safe, and effective disinfectant due to its high oxidation efficiency and reduced formation of organochlorinated by-products during application. This article provides an updated overview of ClO 2 -based oxidation processes used in water treatment. A systematic review of scientific information and experimental data on ClO 2 -based water purification procedures is presented. Concerning ClO 2 -based oxidation derivative problems, the pros and cons of ClO 2 -based combined processes are assessed and disinfection by-product (DBP) control approaches are proposed. The kinetic and mechanistic data on ClO 2 reactivity towards micropollutants are discussed. ClO 2 selectively reacts with electron-rich moieties (anilines, phenols, olefins, and amines) and eliminates certain inorganic ions and microorganisms with high efficiency. The formation of chlorite and chlorate during the oxidation process is a crucial concern when utilizing ClO 2. Future applications include the combination of ClO 2 with ferrous ions, activated carbon, ozone, UV, visible light, or persulfate processes. The combined process can reduce by-product generation while still ensuring ClO 2 sterilization and disinfection. Overall, this research could provide useful information and new insights into the application of ClO 2 -based technologies. [Display omitted] • ClO 2 application derivative problems and DBPs control methods are discussed. • UV/ClO 2 process can achieve high-efficiency disinfection and reuse ClO 2 -. • The mechanistic information on combination process based on ClO 2 is analyzed. • The pros and cons of ClO 2 -based treatments are evaluated. • Challenges and perspectives for future development are proposed. [ABSTRACT FROM AUTHOR]

1,3-diphenylguanidine (DPG) is a commonly used rubber and polymer additive, that has been found to be one of the main leachate products of tire wear particles and from HDPE pipes. Its introduction to aquatic environments and potentially water supplies lead to further questions regarding the effects of disinfection by-products potentially formed. Using different bioassay approaches and NGS RNA-sequencing, we show that some of the chlorinated by-products of DPG exert significant toxicity. DPG and its chlorinated by-products also can alter cell bioenergetic processes, affecting cellular basal respiration rates and ATP production, moreover, DPG and its two chlorination products, 1,3-bis-(4-chlorophenyl)guanidine (CC04) and 1-(4-chlorophenyl)−3-(2,4-dichlorophenyl)guanidine (CC11), have an impact on mitochondrial proton leak, which is an indicator of mitochondria damage. Evidence of genotoxic effects in the form of DNA double strand breaks (DSBs) was suggested by RNA-sequencing results and further validated by an increased expression of genes associated with DNA damage response (DDR), specifically the canonical non-homologous end joining (c-NHEJ) pathway, as determined by qPCR analysis of different pathway specific genes (XRCC6, PRKDC, LIG4 and XRCC4). Immunofluorescence analysis of phosphorylated histone H2AX, another DSB biomarker, also confirmed the potential genotoxic effects observed for the chlorinated products. In addition, chlorination of DPG leads to the formation of different chlorinated products (CC04, CC05 and CC15), with analysed compounds representing up to 42% of formed products, monochloramine is not able to effectively react with DPG. These findings indicate that DPG reaction with free chlorine doses commonly applied during drinking water treatment or in water distribution networks (0.2–0.5 mg/L) can lead to the formation of toxic and genotoxic chlorinated products. [Display omitted] • Five chlorination by-products of DPG were synthetized and purified for toxicity evaluation. • Five chlorinated products show higher cytotoxicity than DPG in long term exposure. • Two of the chlorinated by-products, CC04 and CC11, show potential genotoxic effects in-vitro. • Chlorinated products studied represent up to 42% of products formed from of DPG. • DPG produces more chlorinated by-products during chlorination than chloramination. [ABSTRACT FROM AUTHOR]

In this study, a novel adsorbent of graphene oxide (GO) incorporated ferrihydrite (FH) was fabricated and integrated with ultrafiltration (UF) to remove natural organic matter (NOM), the crucial cause of membrane fouling and major precursor of disinfection by-products (DBPs). Compared with FH and powdered activated carbon (PAC), GO/FH exhibited superior removal for high molecular weight (HMW) humic- and fulvic-like substances and low molecular weight (LMW) protein. The cake layer formed by GO/FH alleviated the deposition of NOM on membrane surface or inside membrane pores. Therefore, GO/FH reduced 89% and 95% total fouling resistance and irreversible membrane resistance, respectively, together with the lowest increment of transmembrane pressure. Pearson correlation analysis indicated that DOC, rather than specific ultraviolet absorbance (SUVA) and UV 254 , was significantly correlated to the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) when SUVA was below 4 L/mg-C.m. Whilst the HMW NOM (1–20 kDa) was highly related to dibromochloromethane (DBCM) (r = 0.98–1), the LMW fraction (< 1 kDa) was correlated with dibromochloromethane (TCAA) and dichloroacetic acid (DCAA) (r = 0.88–0.98). Inspiringly, GO/FH-UF reduced 90% of carbonaceous DBPs, the concentrations of which well met the WHO Guidelines. In summary, GO/FH-UF substantially alleviated membrane fouling and dramatically reduced DBP formation potential. [Display omitted] • GO/FH-UF reduced > 80% of DOC and UV 254 , while UF alone removed <40%. • GO/FH removed both HMW and LMW NOM, thus mitigated external and internal fouling. • DOC better indicated DBPFP than SUVA and UV 254 for water with SUVA <4 L/mg-C/m. • LMW NOM highly correlated to TCAA and DCAA, while HMW NOM tightly related to DBCM. [ABSTRACT FROM AUTHOR]

The cancer risks from exposure to trihalomethanes (THMs) and haloacetic acids (HAAs) through multiple pathways were assessed based on the result of a water quality survey in 35 major cities of China. To express the risks in disability-adjusted life years (DALYs), the excess cancer incidence estimates were combined with a two-stage disease model for calculation. The median total cancer risk of THMs and HAAs was calculated as 7.34 × 10 −7 DALYs per person-year (ppy), lower than the reference level of risk (10 −6 DALYs ppy) set by WHO. The risk from ingestion and inhalation exposures contributed 93.6% and 6.3% of the total risk respectively, while dermal contact made a negligible contribution. The median risk of trichloroacetic acid (TCAA) (2.12 × 10 −7 DALYs ppy) was highest among the disinfection by-products (DBPs) considered. The risk ratio of total HAAs (THAA) to total THMs (TTHM) was 1.12. The risk was highest in northeast China while lowest in northwest China. As for the 35 cities, Tianjin had the highest risk while Yinchuan had the lowest. This study attempted to use DALYs for the risk assessment of DBPs, which will provide useful information for risk comparison and prioritization of hazards in drinking water. [ABSTRACT FROM AUTHOR]

Highlights: [•] Factors affecting I-THM formation during oxidation using ClO2 were evaluated. [•] CHI3 yields correlated moderately with SUVA values (R 2 =0.79). [•] CHI3 yields were the highest at I−/ClO2 molar ratio of 1–2. [•] CHI3 was predominant even in the presence of high concentrations of bromide. [•] CHI3 yields were the highest at pH 8. [Copyright &y& Elsevier]

Highlights: [•] Subject to chlorination, MCLR was transformed into 5 types of MCLR-DBPs. [•] MS/MS analysis indicated that the conjugated diene in Adda was a major target site. [•] Most MCLR-DBPs had lower toxicity on protein phosphatase 1 than MCLR. [•] MCLR-DBPs still possessed certain biological toxicity and environmental risk. [•] The secondary pollution of MCLR-DBPs in drinking water deserves further attention. [ABSTRACT FROM AUTHOR]

Abstract: In pristine watersheds, natural organic matter is the main source of disinfection by-product (DBP) precursors. However, the presence of point or non-point pollution sources in watersheds may lead to increased levels of DBP precursors which in turn form DBPs in the drinking water treatment plant upon chlorination or chloramination. In this study, water samples were collected from a lake used to obtain drinking water for Istanbul as well as its tributaries to investigate the presence of the precursors of two disinfection by-products, trihalomethanes (THM) and N-nitrosodimethylamine (NDMA). In addition, the effect of seasons and the possible relationships between these precursors and water quality parameters were evaluated. The concentrations of THM and NDMA precursors measured as total THM formation potential (TTHMFP) and NDMA formation potential (NDMAFP) ranged between 126 and 1523μg/L THM and <2 and 1648ng/L NDMA, respectively. Such wide ranges imply that some of the tributaries are affected by anthropogenic pollution sources, which is also supported by high DOC, Cl− and NH3 concentrations. No significant correlation was found between the water quality parameters and DBP formation potential, except for a weak correlation between NDMAFP and DOC concentrations. The effect of the sampling location was more pronounced than the seasonal variation due to anthropogenic pollution in some tributaries and no significant correlation was obtained between the seasons and water quality parameters. [Copyright &y& Elsevier]

Abstract: Drinking water must be disinfected prior to its distribution for human consumption. This water treatment process generates disinfection by-products (DBPs), formed by the interaction of the disinfectant with organic matter, anthropogenic contaminants and inorganic (bromide/iodide) matter naturally present in source water. Due to the potential genotoxic/carcinogenic risk of these DBPs, we have investigated the mutagenic potential of six of such compounds on the thymidine kinase (Tk) gene in the well-validated mouse lymphoma assay (MLA). The MLA quantifies a wide range of genetic alterations affecting the expression of this gene in L5178Y/Tk +/−-3.7.2C cells. In this study we selected six emerging DBPs, corresponding to three different chemical classes: halonitromethanes (bromonitromethane and trichloronitromethane), halogenated acetaldehydes (tribromoacetaldehyde and chloral hydrate) and hydroxyfuranones (mucobromic and mucochloric acids), each class including one chlorinated and one brominated form. The results showed that after 4h of treatment, only mucobromic acid increased the frequency of mutant colonies, with a higher proportion of small colonies, which would indicate a clastogenic potential. This is the first study reporting mutagenicity data in mammalian cells for the six selected DBPs. [Copyright &y& Elsevier]

Abstract: This paper provides an overview of all current issues that are connected to the presence of nitrosamines in water technology. N-nitrosodimethylamine (NDMA) is the most frequently detected member of this family. Nitrosamines became the hottest topic in drinking water science when they were identified as disinfection by-products (DBPs) in chloraminated waters. The danger that they pose to consumer health seems to be much higher than that from chlorinated DBPs. This review summarizes our contemporary knowledge of these compounds in water, their occurrence, and precursors of nitrosamines in drinking and wastewaters, in addition to attempts to remove nitrosamines from water. The paper also reviews our knowledge of the mechanisms of nitrosamine formation in water technology. The current, commonly accepted mechanism of NDMA formation during chloramination of drinking waters assumes that dichloramine reacts with dimethylamine, forms unsymmetrical dimethylhydrazine and further oxidizes to NDMA. The question to answer is which precursors are responsible for delivering the DMA moiety for the reaction since the presence of DMA in water cannot explain the quantities of NDMA that are formed. There are also reports that other oxidants that are commonly used in water technology may generate NDMA. However, the mechanisms of such transformations are unknown. Methods for the removal of nitrosamines from water are described briefly. However, the research that has been undertaken on such methods seems to be at an early stage of development. It is predicted that photolytic methods may have the greatest potential for technological application. [Copyright &y& Elsevier]

Abstract: Disinfection by-products (DBPs) are chemicals that are produced as a result of chlorine being added to water for disinfection. As well as the halogenated DBPs, N-nitrosamines have recently been identified as DBPs, especially when amines and ammonia ions are present in raw water. In this work, the genotoxicity of two nitrosamines, namely nitrosodimethylamine (NDMA) and nitrosodiethylamine (NDEA), has been studied in cultured human cells. To evaluate their genotoxic potential two assays were used, the comet assay and the micronucleus test. The comet assay measures the induction of single and double-strand breaks, and also reveals the induced oxidative DNA damage by using endoIII and FPG enzymes. Chromosomal damage was evaluated by means of the cytokinesis-blocked micronucleus test. The results of the comet assay show that both compounds are slightly genotoxic but only at high concentrations, NDEA being more effective than NDMA. Enzyme treatments revealed that only NDEA was able to produce increased levels of oxidized bases, mainly in purine sites. The results obtained in the micronucleus assay, which measures the capacity of the tested agents to induce clastogenic and/or aneugenic effects, are negative for both of the nitrosamines evaluated, either using TK6 cells or human peripheral blood lymphocytes. Taking into account the very high concentrations needed to produce DNA damage, our data suggest a low, if existent, genotoxic risk associated with the presence of these compounds in drinking water. [ABSTRACT FROM AUTHOR]

Abstract: The main objective of this work was to study the effectiveness of iron oxide-coated pumice and volcanic slag particles in removing disinfection by-product (DBP) precursors from a raw drinking water source with high specific UV absorbance (SUVA254) value. Iron oxide coating of particles significantly increased dissolved organic carbon (DOC) uptakes and decreased DBP formation after chlorination compared to uncoated particles. pH values close to neutral levels during adsorption and chlorination provided DOC, trihalomethane and haloacetic acid reductions around 60–75% employing 6g/L coated particle dosage. Higher degree of DOC and DBP reductions (>85%) were obtained with increasing particle dose. The uptake of bromide by iron oxide surfaces was negligible and increasing bromide concentrations (up to 550μg/L) did not negatively impact the DOC uptake. However, due to competition between natural organic matter (NOM) and bicarbonate for the iron oxide surfaces, increasing bicarbonate alkalinity levels reduced DOC uptakes. Overall, the results indicated that the iron oxide-coated pumice/slag particles are effective adsorbents to remove NOM and control DBP formation in waters with relatively high DOC and SUVA254 levels. However, they may not be effective for waters with alkalinity levels above 250mg CaCO3/L. [Copyright &y& Elsevier]

Abstract: Dissolved organic matter (DOM) influences many aspects of drinking water treatment, including the formation of harmful disinfection by-products (DBPs) when disinfectants are applied. DOM was isolated and fractionated using membrane ultra-filtration (UF) and reverse osmosis (RO) to eight individual fractions based on molecular weight cut-offs from a conventional surface water treatment plant (WTP) in Guangzhou of PR China. Molecular weights of these eight fractions were further calibrated using high performance size exclusion chromatography (HPSEC) and they ranged from 0.36 to 182.6kDa. Fractions with molecular weight <0.80kDa obtained by YC-05 UF membrane and RO were the major ones in all four stages of the water treatment processes; both ZM-500 and YM-100 membranes showed the highest removal efficiency when coupling with conventional coagulation and sedimentation processes. The elemental analysis showed that YC-05 fraction had greater polarity and aromaticity than any of the others. Furthermore, disinfection characteristics and trihalomethane formation potential (THMFP) were determined for all DOM fractions obtained in this study. YC-05 fraction was the major precursor for trihalomethane (THMs) formation among the samples tested and could be removed effectively by particulate activated carbon (PAC) adsorption. RO fraction could not be removed by PAC adsorption and, as a result, consumed more chlorine in the disinfection process. The results suggested that advanced drinking water treatment should focus on the removal of low molecular weight DOM in the source water. [Copyright &y& Elsevier]

Abstract: Based on the measured chemical and physical data in drinking water from six cities in China, the factors including total organic carbon (TOC), ultraviolet absorbance at 254nm (UV254), pH, applied chlorine dosage, temperature, concentrations of bromide ion and several chemical elements which possibly affect the formation of trihalomethane (THM) and haloacetic acid (HAA) have been studied. The results showed that: in all factors, TOC and UV254 have definite correlations with total THM, but have nonsignificant relationships with total HAA. In the studied pH range of 6.5–8.5 for drinking water, the total THM concentration increased with the increasing of pH value, but the total HAA concentration slightly decreased. A low but significant relationship (r =0.26, p <0.01) occurred between total THM and applied chlorine dosage. Similar relationship (r =0.21, p <0.01) was found between total HAA and applied chlorine dosage. When the water temperature was low, the variation of THMs and HAAs was little, but in warmer water, the concentration of THMs and HAAs varied quickly. The extent of bromine incorporation into the DBPs increases with increasing bromide ion concentration. Based on the effect of chemical elements for the DBPs remove effect, the polyferric chloride could be a preferred flocculant agent in waterworks. [Copyright &y& Elsevier]

Dissolved organic matter (DOM) in effluent from a conventional sewage treatment plant was isolated using resin adsorbents into six classes: hydrophobic bases (HoB), hydrophobic acids (HoA) and hydrophobic neutrals (HoN); hydrophilic bases (HiB), hydrophilic acids (HiA) and hydrophilic neutrals (HiN). Organic acids were the most abundant fractions of DOM. Hydrophobic organics especially hydrophobic acids were found to have higher overall disinfection by-products formation potential (DBPFP). Moreover, the potential decreased as the sequence of acids, neutrals and bases. Ultraviolet spectrophotometry at 254nm (UV254), fluorescence spectroscopy, size exclusion chromatography and Fourier transform infrared spectroscopy (FTIR) were employed to characterize DOM fractions. And the relationship between the characteristics of DOM fractions and the related DBPFP was discussed in detail. It was found that UV254 to DOC ratio (SUVA) exhibited a positive correlation with haloacetic acids (HAAs) formation potential whereas distinctive linear correlation was not observed between SUVA and trihalomethanes (THMs) formation potential. Of the fluorescence organics contained in DOM, humic acids exhibited higher chlorine reactivity than fulvic acids. Smaller molecules of humic acids produced more DBPs. Furthermore, a combination of aromatic moieties and aliphatic structures with ν(C contributed largely to the formation of DBPs. [Copyright &y& Elsevier]

Nitrosamine by-products in drinking water are designated as probable human carcinogens by the IARC, but the health effects of simultaneous exposure to multiple nitrosamines in drinking water remain unknown. Genotoxicity assays were used to assess the effects of both individual and mixed nitrosamines in finished drinking water produced by a large water treatment plant in Shanghai, China. Cytotoxicity and genotoxicity were measured at 1, 10-, 100- and 1000-fold actual concentrations by the Ames test, Comet assay, γ -H2AX assay, and the cytokinesis-block micronuclei assay; oxidative stress and the Nrf2 pathway were also assessed. Nitrosamines detected in drinking water included NDMA (36.45 ng/L), NDPA (44.68 ng/L), and NEMA (37.27 ng/L). Treatment with a mixture of the three nitrosamines at 1000-fold actual drinking-water concentration induced a doubling of revertants in Salmonella typhimurium strain TA100, DNA and chromosome damage in HepG2 cells, while 1–1000-fold concentrations of compounds applied singly lacked these effects. Treatment with 100- and 1000-fold concentrations increased ROS, GSH, and MDA and decreased SOD activity. Thus, nitrosamine mixtures showed greater genotoxic potential than that of the individual compounds. N -Acetylcysteine protected against the nitrosamine-induced chromosome damage, and Nrf2 pathway activation suggested that oxidative stress played pivotal roles in the genotoxic property of the nitrosamine mixtures. [Display omitted] • Nitrosamines (NAms) like NDMA, NDPA & NEMA, were found in finished drinking water. • Mixed vs single NAms increased genotoxic potential, even at low concentrations. • Oxidative stress and NRF2 pathway activation played key roles in genotoxic effects. • NDMA, the priority NAms compound, was the main risk component for carcinogenesis. [ABSTRACT FROM AUTHOR]

Abstract: Bromo-DBPs (disinfection by-products) are generated by bromide and disinfectant in drinking water disinfection, which have adverse effects on human health. In this study, effects of coexisting anions on removal of bromide by aluminium coagulation were investigated. It was observed that bromide was removed of 62.1–87.0% in raw water, while the removal efficiency of bromide was achieved 82.8–99.2% in deionized water through the combination of Br− with Al(III) in various pathways. The coexisting anions in raw water significantly affected the removal of bromide. Removal efficiency decreased by 11.5, 21.2, 14.6, 8.0 and 40.8% with the addition of HCO3 −, SO4 2−, Cl−, NO3 − and H2PO4 −, respectively, for their affinities with Al(III) or accelerating the formation of Al(OH)3(am). These results demonstrated that bromo-DBPs in drinking water could be controlled though removing bromide by enhanced coagulation. [Copyright &y& Elsevier]

A total of 29 surface waters from different regions of Turkey were sampled once a month during 2004. Filtered raw water samples were characterized, chlorinated and the concentrations of disinfection by-products (DBPs) were measured. All waters were low in DOC ranging from 0. 91 to 4. 42mg/L. The range of annual average trihalomethanes (THMs) and haloacetic acids (HAAs) concentrations in all waters was 21–189 and 18–149μg/L, respectively. Total mass contributions of halides in THMs and HAAs to absorbable organic halides (AOX) ranged between 10 and 56% in all waters on annual average basis, indicating that significant amounts of other DBPs are being formed in the majority of the tested waters. A strong linear correlation was obtained between the concentrations of THMs and HAAs. Rather poor correlations were found for THMs–AOX and HAAs–AOX levels. For both THMs and HAAs, chlorinated species dominated over brominated ones since the majority of water sources had very low bromide levels. While chloroform and trichloroacetic acid were the major THM and HAA compounds, respectively; the extent of formation and speciation of DBPs varied greatly by season and water source. No consistent general trends were observed in terms of seasonal variations in DBP levels, suggesting that the characteristics of NOM moieties and their chlorine reactivity vary by season in almost all waters tested. [Copyright &y& Elsevier]

Abstract: This work investigated the formation potential of haloacetic acid (HAA) compounds in the raw water for the Bangkhen water treatment plant (Bangkok, Thailand). The resin adsorption technique (with three different types of resins, i.e. DAX-8, AG-MP-50 and WA-10) was employed to characterize the organic content in the raw water into six fractions, i.e. hydrophobic neutral (HPON), hydrophobic acid (HPOA), hydrophobic base (HPOB), hydrophilic neutral (HPIN), hydrophilic acid (HPIA) and hydrophilic base (HPIB). Hydrophilic species appeared to be the predominant organic species in this water source (approximately 60%) with the neutral fraction being the most abundant (approximately 40%). Hydrophobic species, on the other hand, played the most important role in the formation of haloacetic acids as they contributed to as much as approximately 56% of total HAA formation potential. Among the three hydrophobic species, the hydrophobic base exhibited the highest specific HAA formation with 208μgHAAs/mg of dissolved organic carbon (DOC). Each organic fraction was examined for its associated functional groups by Fourier transform infrared (FTIR). The investigation of the formation of HAAs was achieved by tracking the changes in the FTIR results of the same water sample before and after the chlorination reaction. Based on the results obtained from this study, carboxylic acids, ketone, amide, amino acids and aromatic characteristic organics seemed to be the main precursors to HAA formation. [Copyright &y& Elsevier]

Abstract: Toxic organic compounds detected generally in source water could combine with chlorine and contribute significantly to chlorination disinfection by-products (CDBPs). The effects of pH on species distribution of CDBPs and the kinetics of chlorination were investigated using phenol as a model of ionizable toxic organic compounds in the pH range of 6.0–9.0. It was found that five chlorination products including 2-monochlorophenol (2-MCP), 4-monochlorophenol (4-MCP), 2,6-dichlorophenol (2,6-DCP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (TCP) were produced by successive chlorination substitution. MCP (2-MCP and 4-MCP) were the dominant products and phenol partly remained in acid media, while TCP and DCP (2,6-DCP and 2,4-DCP) were the main components in neutral and alkaline media. A steady equilibrium of phenol and its chlorination products was reached in 20–30min in acid-, neutral- and slightly alkaline media, and was delayed to 60–180min in alkaline media. The difference in properties between phenols and phenolates, and those between HOCl and ClO− should be considered simultaneously in explaining the effects of pH on the chlorination process with the theory of electrophilic substitution. These results show that pH plays an important regulating role in the species distribution of CDBPs and the kinetics of chlorination for ionizable toxic organic compounds in chlorination. [Copyright &y& Elsevier]

Abstract: Resin adsorption techniques using three types of resin (DAX-8, AG-MP-50, and WA-10) were employed to characterize the raw water (RW) from the major 3 million m3/day (793 million gal/day) drinking water treatment plant in Bangkok, Thailand. The dissolved organic carbon (DOC) mass distribution sequences of the six organic fractions in raw water, from high to low, were hydrophilic neutral (HPIN), hydrophobic acid (HPOA), hydrophilic acid (HPIA), hydrophobic neutral (HPON), hydrophilic base (HPIB), and hydrophobic base (HPOB). HPIN and HPOA were the two main precursors for trihalomethanes formation (THMFP) in this water source following chlorination. The chlorination of HPON and HPIN fractions only led to the formation of mostly chloroform, while other organic fractions formed both chloroform and bromodichloromethane. The linear dependency between each organic fraction concentration and THMFP indicated that the reactions of each organic fraction with chlorine were first-order. [Copyright &y& Elsevier]

Coagulation is well-established for controlling regulated disinfection by-products (DBPs), but its effectiveness for controlling unregulated DBPs remains unclear. The efficiency of coagulation in controlling unregulated DBPs requires clarification owing to their relatively high toxicity. In this study, three Al-based coagulants, aluminum sulfate (Alum), polyaluminum chloride (PAC), and a novel type of covalently bond hybrid coagulant (CBC, synthesized using AlCl 3) were selected, and the coagulation performance of these Al-based coagulants in controlling DBPs and DBP-associated toxicity was compared over 5 classes of DBPs, including trihalomethanes, haloacetic acids, haloacetaldehydes, haloacetonitriles, and halonitromethanes. The results showed that Alum was the least efficient in removing DBP precursors among the three coagulants. The effectiveness of CBC and PAC for DBP control varied with the characteristics of source waters. CBC had an advantage in water with a low content of humic acids, and reduced DBP concentration and DBP-associated toxicity by 47% and 25%, respectively. For water rich in aromatic organics, CBC might serve as DBP precursors at a high-required dosage, suggesting that a trade-off between enhanced DBP control and serving as DBP precursors should be considered for CBC coagulation; PAC achieved the most reduction in DBP concentration and DBP-associated toxicity by 50% and 34%, respectively. [Display omitted] • Coagulation performance and DBP control of three Al-based coagulants were evaluated. • CBC showed higher removal of turbidity and UV 245 compared to PAC and Alum. • CBC outperformed Alum and PAC in the control of nitrogenous DBP formation. • A trade-off between enhanced DBP control and being DBP precursors is required for CBC. • Effectiveness of CBC and PAC for DBP control varied with the characteristics of source waters. [ABSTRACT FROM AUTHOR]

As a well known endocrine-disrupting and model chemical, bisphenol A (BPA) may pose a serious threat to human health, since it and its disinfection by-products (DBPs) have been detected in drinking water, urine, human colostrum, adipose tissue, and placenta samples. Although chlorinated BPAs (Cl-BPAs) and iodinated BPAs (I-BPAs) have been well studied, brominated BPAs (Br-BPAs), and mixed halogenated DBPs like bromo-iodo-BPAs (Br-I-BPAs), and bromo-chloro-iodo-BPAs (Cl-Br-I-BPAs) are less well understood. Notably, the role of iodide (I-) during chlorination is not well understood, since the studies of the I-DBPs mainly focus on their genotoxicity and cytotoxicity. To understand the formation mechanisms of halogenated bisphenol A (HBPs) during chlorination with bromide (Br-) and/or I-, and the role of I- during chlorination, three set of reactions were performed in the laboratory ("BPA + chlorine + Br-", "BPA + chlorine + I-" and "BPA + chlorine + Br- +I-" assigned as group A, B and C respectively). Thirty HBPs were identified and 18 of them were never reported before. I- increases the transformation rate of BPA into HBPs as I-BPAs act as intermediate HBPs during chlorination that easily react with HClO/ClO- and HBrO/BrO- to form Cl-BPAs and Br-BPAs. HIO/IO- showed higher reactivity towards BPA and HBPs than that of HBrO/BrO- and HClO/ClO-. The recycling of I- was observed in the reactions of "BPA + chlorine + I-" and "BPA + chlorine + Br- +I-", which may explain why I- can induce BPA to transform into HBPs and suggests that I- may act as a catalyst during the BPA chlorination reactions. The reaction pathways are proposed which present the reactions of BPA and HBPs with HClO/ClO-, HBrO/BrO-, and HIO/IO-, as well as the recycling of I-. This study describes the potential DBP formation and transformation mechanisms of BPA and its 16 alternatives, as well as the role of I- on the transformation of phenol compounds during chlorination. [Display omitted] • The halogenation of BPA during chlorination was researched. • Thirty HBPs were identified and some of them were never reported before. • I-BPAs act as intermediate HBPs during chlorination. • Transformation pathways of BPA and HBPs during chlorination were proposed. • The recycling and role of I- during chlorination were highlighted. [ABSTRACT FROM AUTHOR]

Tetrabromobisphenol A (TBBPA) is one of the most widely applied brominated flame retardants and has been widely detected in water environment, which might pose risks of brominated disinfection by-products formation in water treatment system. Ferrate(VI)-CaSO 3 (Fe(VI)-CaSO 3) system could effectively degrade TBBPA at pH 7.0–9.0 but the decomposition rate of TBBPA dropped with increasing pH. The presence of 0.5 mg C/L humic acid (HA) had negligible impact on TBBPA removal, but the removal of TBBPA decreased to ~87% and 80% at pH 7.0 and 8.0, respectively, in the presence of 5.0 mg C/L HA. The transformation products of TBBPA detected in Fe(VI)-CaSO 3 process revealed that TBBPA degradation mainly proceeded via electron abstraction, debromination, and ring-opening pathways and Br− was released. In the presence of TBBPA, Fe(VI)-CaSO 3 pre-oxidation decreased the generation of all determined DBPs during chlorination at pH 8.0 but it lessened the generation of some DBPs and slightly increased the formation of the other DBPs at pH 7.0. The toxic risk analysis showed that Fe(VI)-CaSO 3 pre-oxidation of TBBPA could reduce the toxic risk of DBPs in both synthetic water and natural water at pH 8.0, indicating that Fe(VI)-CaSO 3 process has the potential to be applied in practical water treatment. [Display omitted] • TBBPA could be efficiently degraded by Fe(VI)-CaSO 3 technology at pH 7.0–9.0. • TBBPA was degraded via electron abstraction, debromination, and ring-opening steps. • Two mg C/L HA inhibited Br− release during TBBPA removal in Fe(VI)-CaSO 3 process. • With TBBPA, Fe(VI)-CaSO 3 process inhibited DBPs formed in chlorination at pH 8.0. • With TBBPA, Fe(VI)-CaSO 3 pre-oxidation reduced the toxic risk of DBPs at pH 8.0. [ABSTRACT FROM AUTHOR]

• PMS activation with novel FeOCl was efficient for removal of NASIDs. • Key role of ·OH and 1O 2 were confirmed at acid and basic pH. • Cycles of Fe2+ /Fe3+ were answerable for ROS generation. • The calculated toxicity of DBPs decreased with pH increase. Iron oxychloride (FeOCl) is utilized as a activator of peroxymonosulfate (PMS) for the degradation of paracetamol (APAP) and phenacetin (PNCT) in response to the water pollution by persistent pharmaceuticals. The degradation process was well fitted with a pseudo-first order kinetic pattern, and the excellent catalytic performance towards APAP (100 % removal) and PNCT (86.5 % removal) was obtained in the presence of 0.2 g/L FeOCl and 2.0 mM PMS at pH 7.0 in 30 min. In-situ electron spin resonance (ESR) and scavenging tests revealed the generation of a series of ROS (· OH, SO 4 −, O 2 −, 1O 2), which was highly dependent on pH. Besides, the non-radical pathways process involved 1O 2 was dominant in APAP oxidation, while both · OH and 1O 2 are significant in PNCT removal. Furthermore, the formation of disinfection by-products (DBPs) during post-chlorination showed neglectable increment at neutral and alkaline condition with FeOCl/PMS pre-oxidation, and the calculated cytotoxicity would experience a continuous deterioration with pH increase. These results displayed high efficiency of FeOCl/PMS system in micropollutants degradation and a relatively comprehensive activation process of PMS, which may promote practical application in environmental remediation. [ABSTRACT FROM AUTHOR]

• Microextraction of 18 DPBs with spiral hollow fiber (SHF) in HS. • Modular extraction support device was performed using a 3D printer. • Support device allowed long length of fiber and reduce errors source. • The effervescence effect improves the extraction efficiency. • BNM, BCAN, DBAN DCAN and 1,3 DCA were detected in supply water. A new analytical method was optimized to determine 18 disinfection by-products (DBPs) in drinking water, including four different chemical groups. For this purpose, spiral-shaped hollow-fibre liquid phase microextraction with 1-octanol as the acceptor solvent assisted by effervescence was applied using a homemade supporting device that was specifically designed for this application. The device was printed in a 3D printer and allows for an increased fibre surface even with a low sample volume, which significantly facilitates the extraction. The samples were analysed by gas chromatography coupled to both an electron capture detector and a mass spectrometer for the quantification and unequivocal identification of the analytes, respectively. Effervescence was generated using citric acid and bicarbonate at a molar ratio 1:2, which significantly improves the extraction efficiency and reduces mechanical operations, since stirring and modifiers are not required. The results showed enrichment factors ranging from 13.1 to 140.1. Satisfactory recoveries (80-113 %) were obtained, with relative standard deviations from 3 to 15 % and good linearity. The detection limits (ng L-1) ranged from 10 to 35 (trihalomethanes), 12 to 220 (halonitromethanes), 17 to 79 (haloacetonitriles) and 10 to 16 (haloketones). The applicability of the method was assessed in 6 local water distribution systems. [ABSTRACT FROM AUTHOR]

• Precise exposure assessment were peformed by parameters from "swimming habits" investigation. • The swimmers between 9 and 17 years of age had higher ADD of DBPs than swimmers ≥ 18 years of age. • The LCR of DBPs exceeded NRL (10−6), and inhalation exposure was the most important pathway for the total risk. • Annual disease burden was 19.0 person-years attributed to exposure of DBPs in swimming pool water in Shanghai. Swimming pool disinfection byproducts (DBPs) are becoming increasingly common worldwide. Precise exposure and health risk assessment for DBPs in swimming pool water with optimized parameters for local and specific population is more urgently needed. This study aimed to determine the levels of trihalomethanes (THMs) and haloacetic acids (HAAs) in 16 public indoor swimming pools in Shanghai, China. Swimming habits were also investigated to obtain more accurate exposure assessment parameters. Precise exposure assessment through multiple pathways, resulting cancer risk, and disability-adjusted life years (DALYs) were assessed. Results indicated that the highest total level of THMs and HAAs occurred in autumn. The surveyed swimmers 9–17 years of age had higher average daily dose (ADD) of DBPs than swimmers ≥18 years of age. The total lifetime cancer risk (LCR) attributable to THMs and HAAs exceeded 10−6, which represents a negligible risk level (NRL). The cancer risk from inhalation exposure predominantly by THMs contributed more than 99% of the total risk. Annual disease burden was 19.0 person-years attributed to exposure of DBPs in swimming pool water in Shanghai. This study provides a paradigm and strategic reference of precise exposure assessments, risk assessments, and disease burden estimation of hazards in swimming pool water for other regions. [ABSTRACT FROM AUTHOR]

• Chlorination triggered a distinct DEGs pattern in AOM that is different from SOM. • 22 differentially expressed genes were specifically identified under chlorinated AOM. • AHR and ARNT are key regulators modulating gene expression in chlorinated AOM. • CYP1A1 and CYP1B1 are potential biomarkers of DBPs derived from chlorinating AOM. Disinfection by-products (DBPs) are generated during chlorination of drinking water. Previous studies demonstrate that DBPs are cytotoxic, genotoxic and associated with an increased risk of human cancer. However, the molecular basis of DBPs-induced toxic effects remains unclear. Here, we chlorinated samples of algal-derived organic matter (AOM) and sediment organic matter (SOM) from a local drinking water reservoir. Chemical properties, toxicities and transcriptomic profiles of human Caco-2 cell exposed to AOM and SOM were compared before and after chlorination. We analyzed chlorination-caused distinct gene expression patterns between AOM and SOM, and identified a set of 22 differentially expressed genes under chlorination of AOM that are different from chlorinated SOM. Consequent network analysis indicates that differential CYP1A1 , CYP1B1 , ID1 and ID2 are common targets of the upstream regulators predicted in the AOM group, but not the SOM group. Through experimental validation and data integration from previous reports related to DBPs or environmental stressors, we found that CYP1A1 and CYP1B1 are specifically up-regulated after chlorinating AOM. Our study demonstrates that the two CYP1 genes likely act as novel biomarkers of AOM derived DBPs, and this would be helpful for testing drinking water DBPs toxicity and further monitoring drinking water safety. [ABSTRACT FROM AUTHOR]

• DPG and DTG react rapidly with chlorine and bromine. • The pH dependance of the reaction was modelled. • Several transformation products were identified by LC-QTOF. • Chloroform and dichloroacetonitrile are also produced. • TPs are more toxic than DPG and DTG. This works investigates the chlorination and bromination of two rubber and polymer related chemicals, which have emerged as relevant water contaminants, i.e. 1,3- di - o -tolylguanidine (DTG) and 1,3-diphenylguanidine (DPG). Kinetic constants at different pH values were obtained and modelled, taking into account the pK a values of DTG/DPG and HClO, showing that the maximum reaction rate (k app > 104 M−1 s−1) is obtained at pH values 8.8 for DPG and 9.1 for DTG. Bromination is also very fast, although unlike chlorination, deviation from the model was observed at neutral pH, which was attributed to formation of metastable transformation product (TP). A total of 35 TPs, corresponding to halogenation, hydroxylation, formation of monophenylguanidine derivatives and cyclization reactions, were tentatively identified. Furthermore it was found that chloroform can be formed up to a 25% molar yield, while dichloroacetonitrile was formed into less than a 3% yield. Several ecotoxicological endpoints were predicted by quantitative structure–activity relationship models (QSAR) for the TPs, some of which were predicted to be more toxic than DPG/DTG. Also a chlorinated solution investigated by a Vibrio Fisheri acute toxicity test, confirmed that toxicity increases with chlorination. [ABSTRACT FROM AUTHOR]

Pharmaceuticals are emerging contaminants of concern and are widespread in the environment. While the levels of these substances in finished drinking waters are generally considered too low for human health concern, there are now concerns about their disinfection by-products (DBPs) that can form during drinking water treatment, which in some cases have been proven to be more toxic than the parent compounds. The present manuscript reviews the transformation products of pharmaceuticals generated in water during different disinfection processes, i.e. chlorination, ozonation, chloramination, chlorine dioxide, UV, and UV/hydrogen peroxide, and the main reaction pathways taking place. Most of the findings considered for this review come from controlled laboratory studies involving reactions of pharmaceuticals with these oxidants used in drinking water treatment., (Copyright © 2014 Elsevier B.V. All rights reserved.)