Disinfection By-products Research Articles

Response of dissolved organic matter and disinfection by-product precursors to algal blooms and thermal stratification in deep reservoirs.

Algal bloom contribute substantially to dissolved organic matter (DOM) and disinfection by-product (DBP) precursors in deep reservoirs, threatening drinking water safety. However, the variations in DOM and DBP precursors in deep-water reservoirs during algal bloom remain unclear. UV and fluorescence spectroscopy and chlorination experiments were used to analyze the variations in DOM and DBP precursors during algal bloom in the Sanhekou Reservoir. Before algal bloom, the DOM and DBP precursors decreased due to biodegradation. After algal bloom, the DOM and DBP precursors increased by 48.3% and 86.9% due to algae producing protein-like compounds. Notably, the algal bloom produced a range of nitrogenous compounds that significantly promote the formation of trichloronitromethane, a major contributor to the mammalian cytotoxicity associated with DBPs. In addition, the heterogeneous matrix led to the stratification of DOM and DBP precursors. The surface water (0-5 m) was more vulnerable to algae, with protein-like components being much higher than in other layers, while humic and fulvic-like components were much lower. However, high temperatures and sufficient oxygen conditions accelerated the biodegradation of DOM and DBP precursors, resulting in significantly lower levels of DOM and DBP precursors in the surface water compared to other layers (p<0.05). This study provides insights into the variations and the drivers in DOM and DBP precursors during algal bloom, essential for developing water intake strategies in similar water reservoirs.

Structure confirmation, reactivity, bacterial mutagenicity and quantification of 2,2,4-tribromo-5-hydroxycyclopent-4-ene-1,3-dione in drinking water.

The presence of two new disinfectant by-product (DBP) groups in the UK was recently shown using non-target analysis, halogenated-hydroxycyclopentenediones and halogenated-methanesulfonic acids. In this work, we confirmed the structure of 2,2,4-tribromo-5-hydroxycyclopent-4-ene-1,3-dione (TBHCD), and quantified it together with dibromomethanesulfonic acid at 122 ± 34 and 326 ± 157 ng L-1 on average in London's drinking water, respectively (n = 21). We found TBHCD to be photolabile and unstable in tap water and at alkaline pH. Furthermore, spectral and computational data for TBHCD and three other halogenated-hydroxycyclopentenediones indicated they could act as a source of radicals in water and in the body. Importantly, TBHCD was calculated to have a 14.5 kcal mol-1 lower C-Br bond dissociation enthalpy than the N-Br bond of N-bromosuccinimide, a common radical substitution reagent used in organic synthesis. TBHCD was mutagenic in Salmonella/microsome assays using strains TA98, TA100 and TA102. This work reveals the unique features, activity and toxicity of trihalogenated hydroxycyclopent-4-ene-1,3-diones, prompting a need to more comprehensively assess their risks.

Advances in environmental analysis of high molecular weight disinfection byproducts.

The disinfection of drinking water, while critical for public health, leads to the formation of disinfection byproducts (DBPs). Toxicological and epidemiological studies have demonstrated that exposure to disinfected water samples may pose adverse effects on human health. Recent research highlights the potential greater toxicity contribution of DBP fractions with high molecular weight (MW) (with more than two carbon atoms) compared to regulated low MW DBPs, emphasizing the need for advanced analytical techniques to identify and characterize these fractions. In this review, we summarize different analytical techniques for indirectly assessing DBP precursors and directly analyzing DBPs, discussing their advantages and limitations. Additionally, since identifying DBP toxicity agents in complex water mixtures is crucial for further optimizing water disinfection and controlling DBP formation, key DBP identification methods based on both chemical and bioassay metrics are also included and discussed. Finally, we highlight three important aspects for the future development of analytical methods to enhance the understanding of high MW DBP formation.

Characterization of Disinfection By-Products Originating from Residual Chlorine-Based Disinfectants in Drinking Water Sources

In this study, samples from the Yangtze River, Han River, and Liangzi Lake in Wuhan City were utilized to characterize the formation of disinfection by-products (DBPs) from chlorine-based disinfection residues in drinking water sources. The results indicated that the main DBPs in drinking water sources were trichloromethane (TCM) and trichloroacetic acid (TCAA). The generation of DBPs was significantly positively correlated with oxidative substances, aromatic compounds, pH, and ammonia nitrogen (NH3-N) content in the water. The concentration of TCAA increased from 0 to 2.45 ± 0.31 mg/L when the reaction time increased to 72 h. As the NaClO concentration increased from 5 mg/L to 15 mg/L, the concentrations of TCAA, TBM, and DCAN increased from 2.03 ± 0.04 mg/L, 0 mg/L, and 0 mg/L to 2.49 ± 0.34 mg/L, 0.21 ± 0.07 mg/L, and 0.10 ± 0.04 mg/L before decreasing to 1.75 ± 0.19 mg/L, 0.17 ± 0.07 mg/L, and 0.04 ± 0.05 mg/L, respectively. The orthogonal experimental results showed that Br−, NH3-N, and pH all had significant influences on the TCM generation, whereas temperature affected the formation of TCAA in the Han River. This work reveals the factors influencing the generation of DBPs from chlorine-based disinfection residues, offering a prevention and control method for DBPs in drinking water sources from a theoretical perspective.

Modelling the impacts generated by reclaimed wastewater reuse in agriculture: From literature gaps to an integrated risk assessment in a One Health perspective

The reuse of reclaimed wastewater is increasingly recognized as a viable alternative water source for irrigation. Its application, whether direct or indirect, impacts several interconnected compartments, including groundwater, surface water, soil, crops, and humans. Reclaimed wastewater provides essential resources for crops, like water and nutrients. However, it also introduces pathogens, and contaminants of emerging concern (CECs), defined as chemicals that may pose risks to human health and ecosystems but are not yet fully regulated, such as pharmaceuticals and personal care products, among others. Additionally, reclaimed wastewater may contain antibiotic-resistant bacteria (ARBs) and disinfection by-products (DBPs), all of which present potential health and environmental risks. Therefore, regulatory bodies stress the need for preventive risk assessments to ensure safe reuse.This paper critically reviews available models for assessing the impacts of reclaimed wastewater reuse in agriculture. It identifies gaps in current modelling approaches and outlines future research directions. Key areas requiring further investigation include the fate and transfer of CECs, ARBs and DBPs, and the co-occurrence of multiple risks in such interconnected systems, especially in the indirect reuse. To address these gaps, we proposed a simplified approach to integrate three types of risk associated with CECs in indirect reuse, focusing on risks posed by antibiotics and other pharmaceuticals: human health risk, environmental risk and risk from antibiotic resistance development. This approach aids in identifying the most critical endpoints within the One Health approach, supporting (i) CECs prioritization in regulations based on their critical endpoints and (ii) the adoption of CEC-specific mitigation measures.

Study on the hydrolysis characteristics of polymeric aluminum chloride forced by fine bubbles and its key factors affecting the efficiency and capacity of forcing hydrolysis

Enhanced coagulation is an important way to remove natural organic matter and reduce disinfection by-products in traditional water treatment processes, in which the micromolecular organic matter that is difficult to be removed during conventional coagulation can be enhanced more conveniently by modulating the dominant Al species in the traditional metal salt coagulants (e.g., polymeric aluminum chloride, PACl). Based on the forcing hydrolysis characteristics of fine bubbles due to the adsorption of hydroxide ions on their surfaces, this study verified the adaptability of the forced PACl hydrolysis by fine bubbles under different operating conditions objectively and comprehensively. The morphological changes of PACl before and after forced hydrolysis by fine bubbles were characterized figuratively, and the evolution of the dominant Al species before and after forced hydrolysis by fine bubbles was reasonably elaborated. The experimental results showed that fine bubbles had the effect of forcing the hydrolysis of PACl with different degrees of alkalinity and modulating the dominant Al species. It was innovatively found that the mass transfer efficiency of the fine bubbles determined their efficiency in forcing PACl hydrolysis (Pearson's r = -0.9423) and the concentration of fine bubbles affected their capacity to force PACl hydrolysis (Pearson's r = 0.8189). At pH = 7 and an air flow rate of 20 mL/min, the DOC concentration of micromolecular organics and the DOC removal efficiency of total organics could be reduced by 0.54 mg/L and enhanced by 12.6 %, respectively, after forced PACl hydrolysis by fine bubbles. While deepening the mechanism of forced PACl hydrolysis by fine bubbles, the above results preliminarily verified the relevance and feasibility of modulating the dominant Al species through forced PACl hydrolysis by fine bubbles to improve the coagulation efficiency, which provided theoretical and data support for the construction of a fine bubble-enhanced coagulation process for drinking water treatment plants.

Unveiling the optical and molecular characteristics of aging microplastics derived dissolved organic matter transformed by UV/chlor(am)ine oxidation and its potential for disinfection byproducts formation

The investigations into the existence and behavior of microplastics (MPs) in water environment were widely conducted, while the characteristics of dissolved organic matter derived from MPs (MPs-DOM) during advanced oxidation have garnered comparatively little attention. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was employed along with multiple statistical analyses to gain a deeper understanding of the conversion of MPs-DOM in UV/chlor(am)ine advanced oxidation processes (AOPs). The diverse treatments exhibited varying degrees of augmentation in both aging and fragmentation of MPs with the order of UV/Cl2 > UV > UV/NH2Cl. The fragmentation degree of MPs upon two UV-based AOPs (UV-AOPs) was dependent on their monomer chemical structure. The highest TOC values of three MPs-DOM were observed after UV/Cl2 AOP and the lowest after UV/NH2Cl AOP. Polyvinyl chloride (PVC) displayed a greater release of MPs-DOM under varying leaching conditions. UV/Cl₂ AOP favored the reaction with saturated MPs-DOM, while UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating disinfection byproducts (DBPs) formation after chlorination. The precursors generated by UV/Cl₂ AOP owned lower H/C, higher modified aromatic index (AImod), and lower molecular weight (MW) products after chlorination. PVC-DOM with fewer CH₂ groups was more reactive. -H₂O, +O and -CH₂ reactions dominated in PVC-DOM (CHO compounds), while -2H, +O, -CH₂ did in PVC-DOM (CHON compounds). The dominant chlorine addition/substitution reactions occurred in PVC-DOM treated by UV/Cl₂ AOP, identifying 195 Cl-DBPs with 220 precursor-product pairs. Mass difference analyses showed that +2H and +O reactions were the most frequent of the 24 reaction types. Environmental ImplicationMicroplastics derived dissolved organic matters (MPs-DOM) transformed into disinfection byproducts (DBPs) under advanced oxidation processes (AOPs), heightening environmental risks. In this study, Fourier transform ion cyclotron resonance mass spectrometry was employed to gain a deeper understanding of MPs-DOM conversion in UV/chlor(am)ine AOPs. MPs fragmentation and fluorescent components varied with monomer chemistry and polymers. UV/Cl₂ AOP reacted with saturated MPs-DOM. UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating DBPs formation. DBPs precursors generated by UV/Cl₂ AOP owned higher modified aromatic index, lower H/C and molecular weight. Unveiling the MPs-DOM transformation during AOPs can mitigate the negative environmental impacts of MPs and their derivatives.

Regulated 1-2 Carbon Disinfection Byproducts do not Correlate with Cytotoxicity with Increasing Disinfectant Contact Time During Chlorination, Chlorination Followed by Chloramination or Granular Activated Carbon Followed by Chlorination.

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

Metabolite identification of emerging disinfection byproduct dibromo-benzoquinone in vivo and in vitro: Multi-strategy mass-spectrometry annotation and toxicity characterization

Halobenzoquinones (HBQs) are emerging disinfection byproducts (DBPs) of high toxicity and also are shared active toxic intermediates of multiple halogenated organic pollutants. Due to the strong oxidizing property and electrophilicity, HBQs exhibit extremely diverse metabolism pathways in organisms. The identification of toxic-decisive metabolites is pivotal, albeit challenging, for understanding the toxicity mechanisms of HBQs. We employed dibromo-benzoquinone (DBBQ) as a representative HBQ, and established a systematic analytical strategy using high-resolution mass spectrometry, which collectively coupled suspect screening (SS), mass defect filtering (MDF), product ion filtering (PIF), isotopic signature filtering (ISF), and molecular networking (MN). As a result, 20 biotransformation products of DBBQ were identified in vivo and in vitro, involving metabolism reactions such as hydroxylation, methylation, methoxylation, acetylation, sulfonation, glucuronidation, glutathionylation, dimerization, and conjugation with amino acids or fatty acids. Quantitative structure-activity relationship (QSAR) analysis and cytotoxicity experiments consistently demonstrated the significantly high toxicity of the fatty acid conjugate compared to the parent compound DBBQ and other metabolites, pinpointing the important role of the fatty acid conjugation in determining the metabolism and toxicity of HBQs. The research conducted a comprehensive evaluation of the metabolism of a typical HBQ with the combination of multiple analytical and toxicity characterization methods, therefore screen out the most important metabolism pathway of HBQs.

Magnesium Bicarbonate-Walnut Shell Dual-Template Synthesis of Multifunctional Layered Porous Carbon for Enhanced Adsorption of Aqueous Chlorinated Organic Compounds.

Chloride ions readily react with organic matter and other ions, resulting in the formation of disinfection by-products (DBPs) that exhibit heightened levels of toxicity, carcinogenicity, and mutagenicity. This study creatively employed waste walnut shells as self-templates and low-cost magnesium bicarbonate as a rigid template to successfully synthesize multifunctional porous carbon derived from walnut shells. Employing a series of characterization techniques, it was ascertained that the porous carbon material (WSC/Mg) synthesized via the dual-template method exhibited a distinct layered microscopic surface structure, with a predominance of C and O elements on the surface. The material displayed a high degree of graphitization, significant specific surface area, and abundant oxygen-containing surface functional groups. The incorporation of magnesium bicarbonate as a hard template improved the structure of the walnut shell porous carbon, resulting in a significant enhancement in mass transfer efficiency for the target product on the adsorbent and a substantial improvement in removal efficiency. In comparison with walnut shell-derived carbon using only self-templating, WSC/Mg exhibited a 17.26-fold increase in adsorption capacity for 2,4-dichlorophenol. Furthermore, even after four adsorption-desorption cycles, WSC/Mg-12 maintained an adsorption efficiency above 90%. It is remarkable that WSC/Mg-12 demonstrated exceptional resistance to interference from natural organic matter and pH variations. Moreover, the adsorbed saturated WSC/Mg-12 effectively treated real coke wastewater, resulting in an 80% color removal rate, 20% COD removal rate, and 15% ammonia nitrogen removal rate. In conclusion, this study presents an innovative approach for cost-effective and versatile porous carbon materials with extensive applications in water environment purification and biomass utilization.

Ethylhexyl triazone sunscreen and its disinfection byproducts obtained after chlorine treatment: Ecofriendliness or ecotoxicity?

In recent years, there has been a growing demand for high-quality sunscreens that combine high efficacy with ecological characteristics. This trend has led to an increased use of triazine compounds, which represent an emerging class of UV filters. While it is well-established that sunscreens can have significant environmental impacts, there is limited data on the degradation of triazine UV filters, despite available information on their environmental persistence, particularly in relation to disinfection processes. This study investigates the chemical fate of ethylhexyl triazone (EHT) under chlorination conditions, typical of swimming pools. Twelve disinfection byproducts (DBPs) were isolated and fully identified using nuclear magnetic resonance and mass spectrometry, with three of these byproducts being identified for the first time. DBP1–DBP12 were isolated at relative percentages of 1.26, 9.68, 1.05, 0.42, 0.84, 3.37, 3.58, 1.89, 0.84, 1.47, 0.42, and 0.63. Additionally, a mechanism for their formation was proposed. The ecotoxicological assessment of EHT and of byproducts (DBP1-DBP4) was conducted using acute, sub-chronic or chronic toxicity tests in producers and primary consumers of the freshwater trophic chain. The organisms included the alga Raphidocelis subcapitata, the rotifer Brachionus calyciflorus, the crustacean anostracan Thamnocephalus platyurus and the benthic ostracod Heterocypris incongruens. EHT caused a lethal median concentration in rotifers, with values in the range of tens of mg/L. EHT, DBP1, and DBP4 exhibited sub-chronic effects in ostracods at concentrations in the μg/L range, with EC50s of 210, 9, 20 μg/L, respectively. Rotifers were slightly affected by DBP3 with a chronic EC50 of 200 μg/L. Algae were not affected by either EHT or byproducts.

Estro-Androgenic Disrupting Effects of Halogenated Disinfection Byproducts: A Comprehensive Evaluation and Comparison.

Drinking water halogenated disinfection byproducts (DBPs) have become an increasing health concern. However, the endocrine-disrupting effects of DBPs have not been well evaluated, and the limited available data have inhibited a comprehensive understanding of their health risks. In this study, a total of 43 DBPs were evaluated for their estro-androgenic effects using two types of human breast cancer cells. Among the tested DBPs, 16 exhibited estrogenic/antiestrogenic/androgenic/antiandrogenic effects, and the effects could be observed even at concentrations typically detected in drinking water. Iodinated and polyhalogenated DBPs generally showed higher effects than other species. For a broader comparison, DBP endocrine-disrupting effect data from this study and previous studies were summarized. It was found that the endocrine disruption efficacy of DBPs followed the rank order of iodinated > brominated > chlorinated species, and halophenolic DBPs were potential endocrine-disrupting compounds. Moreover, molecular docking results demonstrated that the binding of DBPs to estro-androgenic receptors was dominated by hydrophobic bonding, hydrogen bonding, halogen bonding, and van der Waals forces. The force strength and molecular volume were related to the magnitude of the estro-androgenic effects. Iodinated DBPs and polyhalogenated DBPs tended to have larger binding forces than other analogues and thus exhibited stronger effects.

Chlorination of Biopterin in Water: Deciphering the Kinetics, Disinfection Byproducts, and Toxicity.

Pterins, including biopterin prevalent during cyanobacterial blooms, are nitrogen-containing heterocyclic compounds ubiquitous in both natural and engineered environments. However, their roles and associated human risks in water treatment remain poorly understood. This study systematically investigated the kinetics, disinfection byproducts (DBPs), and toxicity of biopterin in chlorination. For deciphering the reaction kinetics, 1,3,5-trimethoxybenzene proved to be a more effective chlorine quencher than the commonly used reducing agents, as it preserved N-chlorinated intermediates without reversing them back to biopterin. The pH-dependent kinetics demonstrated that both chlorine and biopterin species had a significant influence on the reaction rates, with deprotonated biopterin exhibiting a markedly higher reactivity toward HClO/ClO-. Based on time-of-flight mass spectrometry, ten transformation products (TPs) including seven halogenated N-Cl ones, have been identified for the first time. These cyclic TPs were transformed into various aliphatic carbonaceous and nitrogenous DBPs during the subsequent chlorination process. Notably, theoretical predictions and the luminescent bacteria assay confirmed potential higher toxicities of these products than biopterin. These findings highlight the potential risks of pterins during water disinfection and provide a reference framework for accurately revealing the chlorination behavior of emerging nitrogenous chemicals.

Wane-and-wax mechanism of nitrogenous disinfection byproducts with constant Cl/N peak under UV/chlorine treatment: Implication for new drinking water disinfection strategy

Nitrogenous disinfection byproducts (N-DBPs) are notorious for their serious health risks, yet nitrate (NO3-) mediates N-DBPs generation during UV/chlorine treatment remains unexplored. This study investigated the interaction of chlorine and NO3- on N-DBPs formation and developed a specific fragment-based screening method using UPLC-QTOF-MS to explore the underlying mechanism. Results showed that the chlorine-to-nitrogen (Cl/NO3--N) molar ratio significantly affects dichloroacetonitrile (DCAN) and dichloroacetamide (DCAM) generation, with peak concentrations at a Cl/NO3--N molar ratio of around 15. NO3- promotes the production of HO•, which positively correlates with DCAN and DCAM concentrations, also peaking at this ratio. Utilizing our developed method, three key hydroxyl-substituted intermediates that circumvent the previously reported “limiting-steps” in DCAN formation were identified. This reaction proceeds via a stepwise mechanism involving hydroxylation and chlorine substitution to produce hydroxyl-phenylacetonitrile and hydroxyl-chlorine-phenylacetonitrile. The conversion rate of hydroxyl-chlorine-phenylacetonitrile to DCAN was 8.6 times higher at Cl/NO3--N molar ratio of 15 compared to conditions without NO3-, attributed to the weakened bond strength of the side chain, as supported by density functional theory calculations. This study provides novel insights into the mechanistic pathways of DCAN and DCAM formation, critical for developing more effective drinking water disinfection technologies to control N-DBPs.

Trihalomethane Formation Potential at the Barekese Water Treatment Plant and the Related Cancer Risk to Consumers in the Kumasi Metropolis of Ghana

The prevalence of disinfection by-products in drinking water supplies is a global concern due to their carcinogenicity. However, the monitoring of DBPs such as trihalomethanes (THMs) and haloacetic acids (HAAs) in drinking water supplies is non-existent in many developing Asian, South American, and African countries. The formation of THMs during disinfection arises from a reaction between the disinfectant and natural organic matter in the water, particularly, dissolved organic carbon (DOC). This reaction is hastened by increases in temperature, high levels of disinfectant doses or residual, elevated water pH, long disinfection contact times, and high DOC concentrations. However, the inclusion of a granular activated carbon adsorption process in the water treatment process is the most effective method for the removal of the main precursor (DOC) for the formation of THMs in treated water. The Barekese WTP, which disinfects with chlorine, has no adsorption process for DOC removal, and supplies over 80% of pipe-borne water to the city of Kumasi in Ghana, was assessed for the THM formation potential (THMFP). A THM predictive model was used to determine the potential THM concentration in the final water. The THMFP at the Barekese WTP ranged between 22.42 and 38.94 µg/L, which was below the 100 µg/L threshold set by the WHO. The lifetime average daily doses were 3.9494 × 10−4 µg/Kg/d and 3.9294 × 10−4 µg/Kg/d for male and female consumers, respectively. The lifetime integrative cancer risks associated with consumption of the water were 1.817 × 10−5 and 1.808 × 10−5 for males and females, respectively. The cancer risk posed was acceptably low. However, direct measurement of DBPs is required to corroborate these findings and verify the cancer risk posed to the consumers of treated water from the Barekese WTP to inform policies, regulations, public health interventions, and investment.

Cancer incidence associations with drinking water arsenic levels and disinfection methods in Maine, USA

ABSTRACT Maine is a largely rural state where nearly half of the population uses drinking water from private wells. Arsenic (As) is present in some groundwater in the state and has been linked to cancer, and a lack of testing and treatment may expose people with private wells to elevated As levels. Disinfection byproducts (DBPs) include known and suspected carcinogens that form when chlorine or chloramines are added to water. People served by public water systems may be exposed to elevated levels of regulated DBPs such as trihalomethanes and haloacetic acids associated with chlorine and/or unregulated nitrogenous DBPs, or N-DBPs, such as nitrite and N-nitrosodimethylamine associated with chloramines. Contrary to initial expectations, there were no significant associations between median town As in well water and bladder, lung, kidney, or skin cancer incidence. Furthermore, bladder, melanoma, and other skin cancer incidence rates were negatively correlated with the percent of the town population using private wells. Analysis of cancer incidence associated with chlorine and chloramine disinfection showed elevated melanoma, and other skin cancer with chloramine use and elevated bladder and non-melanoma skin cancer with chlorine use compared to the no disinfectant case. We recommend more research on the links between disinfectant use and cancer.

A convenient reduction method for the detection of low concentration free available chlorine——utilizing sodium sulfite as a quencher

Chlorine, serving as the mainstream disinfectant, can react with dissolved organic matter (DOM) to form undeserved disinfection by-products (DBPs). Free available chlorine (FAC) concentration is crucial to ensure effective disinfection while minimizing the formation of toxic DBPs. In this study, we propose a convenient method using sodium sulfite (Na2SO3) to reduce oxidized chlorine in FAC. The molar concentration of reduced chloride ion (Cl−) was quantified directly by ion chromatography to reflect FAC concentration. Compared with common FAC detection techniques including DPD colorimetry, iodometric, and UV methods, this novel reduction method exhibits a lower detection limit and is more resistant to interference. Common water matrices, such as DOM and anions did not affect the method accuracy (< 3.6%). Furthermore, carbonaceous DBPs (C-DBPs) like regulated trihalomethanes and halogenacetic acids, unregulated aromatic chlorophenols, did not interfere with the determination of FAC by using this reduction method. This lack of interference can be attributed to the low redox potential of Na2SO3, which does not readily react with these C-DBPs. However, nitrogenated DBPs (N-DBPs) like dichloroacetonitrile displayed slight interference (the effect of common dichloroacetonitrile concentration in water on FAC was less than 0.0007 μM). This suggests that this method is well-suited for determining FAC in chlorination processes where the C-DBPs predominated. Overall, the reduction method enables precise determination of FAC and proves valuable in assessing residual chlorine levels in both laboratory and real disinfected water samples dominated by C-DBPs.

The key to 2,6-dichloro-1,4-benzoquinone reproductive toxicity and green tea detoxification: Covalent binding and competitive binding

Halobenzoquinones (HBQs) are ubiquitous disinfection by-products (DBPs) in chlorinated drinking water with various health risks including reproductive toxicity, while the potential mechanisms are still unclear. Although green tea exhibits common detoxifying properties, its ability to mitigate the toxicity of HBQs still needs to be further deepened and explored. This study attempted to investigate the possible mechanism of the most common HBQ, 2,6-dichloro-1,4-benzoquinone (2,6-DCBQ) induced reproductive toxicity and elucidate the protective effect of green tea using a series of liquid chromatography-tandem mass spectrometry (LC-MS) approaches. Firstly, in vivo experiments showed that 2,6-DCBQ could induce testicular damage in male rats via significantly decreasing sperm-associated Leydig cells and seminiferous tubules. Then, in vitro incubation of 2,6-DCBQ with amino acids suggested that 2,6-DCBQ could bind to proteins via residues of cysteine or lysine and provided five additional modification patterns. Following, proteomics analysis revealed that at least 42 proteins were modified by 2,6-DCBQ, which were mainly enriched in the reproductive system. These results highlighted the significance of covalent protein modification in 2,6-DCBQ reproductive toxicity. Fortunately, we found that catechins (a class of major components of green tea) could competitively bind to 2,6-DCBQ in vivo and in vitro, reducing the amount and type of 2,6-DCBQ-protein adducts, thereby attenuating the reproductive system damage caused by 2,6-DCBQ. This study provides new insights into 2,6-DCBQ-induced reproductive system damage and reveals a new mechanism of green tea detoxification. Moreover, these findings offer potential strategies for alleviating the harmful impacts of environmental toxicants on human health.

Optimizing natural organic matter removal at the Koka water treatment plant, Ethiopia, using soil–alum composite material

ABSTRACT Conventional water treatment methods often fail to remove natural organic matter (NOM), leading to the formation of harmful disinfection by-products in chlorinated water. This study aimed to develop a synergistic, local soil–aluminum sulfate (alum) composite material to enhance NOM removal from real water samples. Locally derived soil (Chalaltu) samples were collected from selected locations and subjected to thermal treatment at elevated temperatures. The thermally treated soil was then combined with alum at varying mixing percentages to create the composite material. The synthesized composite materials were thoroughly characterized using X-ray diffraction, X-ray fluorescence, scanning electron microscopy, Fourier transform infrared, and Brunauer–Emmett–Teller techniques. The alum-treated soil, obtained through thermal treatment at 500 °C with a mixing ratio of 50%, a dosage of 25 mg/L, and a settling time of 25 min, exhibited impressive removal efficiencies. The composite material increased removal efficiency by 1.5 times for both UV254 absorbance (91.1%) and dissolved organic carbon (90%), while reducing the alum dose by 58% compared to the existing Koka water treatment plant process. Reducing alum usage could lead to cost savings and alleviate concerns about its association with Alzheimer's disease. This technique is essential within the context of water treatment technology.

The Generation of ROS by Exposure to Trihalomethanes Promotes the IκBα/NF-κB/p65 Complex Dissociation in Human Lung Fibroblast.

Background: Disinfection by-products used to obtain drinking water, including halomethanes (HMs) such as CH2Cl2, CHCl3, and BrCHCl2, induce cytotoxicity and hyperproliferation in human lung fibroblasts (MRC-5). Enzymes such as superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx) modulate these damages through their biotransformation processes, potentially generating toxic metabolites. However, the role of the oxidative stress response in cellular hyperproliferation, modulated by nuclear factor-kappa B (NF-κB), remains unclear. Methods: In this study, MRC-5 cells were treated with these compounds to evaluate reactive oxygen species (ROS) production, lipid peroxidation, phospho-NF-κB/p65 (Ser536) levels, and the activities of SOD, CAT, and GPx. Additionally, the interactions between HMs and ROS with the IκBα/NF-κB/p65 complex were analyzed using molecular docking. Results: Correlation analysis among biomarkers revealed positive relationships between pro-oxidant damage and antioxidant responses, particularly in cells treated with CH2Cl2 and BrCHCl2. Conversely, negative relationships were observed between ROS levels and NF-κB/p65 levels in cells treated with CH2Cl2 and CHCl3. The estimated relative free energy of binding using thermodynamic integration with the p65 subunit of NF-κB was -3.3 kcal/mol for BrCHCl2, -3.5 kcal/mol for both CHCl3 and O2•, and -3.6 kcal/mol for H2O2. Conclusions: Chloride and bromide atoms were found in close contact with IPT domain residues, particularly in the RHD region involved in DNA binding. Ser281 is located within this domain, facilitating the phosphorylation of this protein. Similarly, both ROS interacted with the IPT domain in the RHD region, with H2O2 forming a side-chain oxygen interaction with Leu280 adjacent to the phosphorylation site of p65. However, the negative correlation between ROS and phospho-NF-κB/p65 suggests that steric hindrance by ROS on the C-terminal domain of NF-κB/p65 may play a role in the antioxidant response.