Chlorinated Disinfection Byproducts Research Articles

Potent Oxidation of DNA by Haloquinoid Disinfection Byproducts to the More Mutagenic Imidazolone dIz via an Unprecedented Haloquinone-Enoxy Radical-Mediated Mechanism.

Halogenated quinones are a class of carcinogenic intermediates and newly identified chlorination disinfection byproducts in drinking water. We found recently that halogenated quinones could enhance the decomposition of hydroperoxides independent of transition-metal ions and formation of the novel quinone enoxy/ketoxy radicals. Here, we show that the major oxidation product was 2-amino-5-[(2-deoxy-β-d-erythro-pentofuranosyl)amino]-4H-imidazol-4-one (dIz) when the nucleoside 2'-deoxyguanosine (dG) was treated with tetrachloro-1,4-benzoquinone (TCBQ) and t-butyl hydroperoxide (t-BuOOH). The formation of dIz was markedly inhibited by typical radical spin-trapping agents. Interestingly and unexpectedly, we found that the generated quinone enoxy radical played a critical role in dIz formation. Using [15N5]-8-oxodG, dIz was found to be produced either directly from dG or through the transient formation of 8-oxodG. Based on these data, we proposed that the production of dIz might be through an unusual haloquinone-enoxy radical-mediated mechanism. Analogous results were observed in the oxidation of ctDNA by TCBQ/t-BuOOH and when t-BuOOH was substituted by the endogenously generated physiologically relevant hydroperoxide 13S-hydroperoxy-9Z,11E-octadecadienoic acid. This is the first report that halogenated quinoid carcinogens and hydroperoxides can induce potent oxidation of dG to the more mutagenic product dIz via an unprecedented quinone-enoxy radical-mediated mechanism, which may partly explain their potential carcinogenicity.

Effect of organic load on the efficacy of activated persulfate in inactivating Escherichia coli O157:H7 and the production of halogenated by-products

Activated persulfate is highly effective in inactivating foodborne pathogens. There is great potential to use this chemical in fresh produce sanitation. The present study evaluated the potential effect of organic load in fresh produce wash water on the bactericidal efficacy of activated persulfate. Romaine lettuce, iceberg lettuce, strawberries, and grapes were used to prepare the produce extracts which were later diluted with water to simulate produce wash water containing different levels of organic matters, represented by the Chemical Oxygen Demand (COD, 100–2000 mg/L). Ferrous activated persulfate (PS/Fe2+) and alkaline activated persulfate (PS/OH−) were prepared in simulated wash water. A five-strain cocktail of Escherichia coli O157:H7 was added to the activated persulfate solution and treated for 2 min. Water properties, including COD, phenolics, protein content, UV254 absorbance, turbidity, pH, and oxidation reduction potential (ORP), were measured and correlated to the microbial reductions. Trihalomethanes, one of the major types of chlorinated disinfection byproducts, were also monitored. Romaine lettuce inoculated with E. coli O157:H7 was used to validate the organic load effect. The results showed that the organic loads in wash water significantly reduced the effectiveness of bacterial inactivation. The microbial reduction decreased from over 8.0 log CFU/mL to near 2.0 log CFU/mL. The organic load had a significantly larger effect on PS/Fe2+ than on PS/OH−. Based on the correlation coefficients, COD, phenolics, and UV254 were found to be the major indicators to predict the organic load effect. However, since UV254 measurement was quicker, UV254 was used as the primary indicator for real produce (romaine lettuce) application. When UV254 was adjusted to 0.75 in the simulated wash water, lower reductions of E. coli O157:H7 on romaine lettuce and higher cross-contamination potentials were observed during washing with PS/Fe2+, PS/OH−, and NaOCl as compared with the lettuce in wash water without additional organic load. In addition, no significant amount of THMs was generated in simulated wash water spiked with produce extracts during activated persulfate treatment. In conclusion, to maintain a high efficacy of activated persulfate for fresh produce washing, the organic load of wash water must be carefully monitored. Activated persulfate is advantageous to traditional chlorine sanitizers as no toxic chlorinated disinfection by-products will be generated.

Disinfection performance and mechanism of the carbon fiber-based flow-through electrode system (FES) towards Gram-negative and Gram-positive bacteria

The disinfection performance of a carbon fiber-based flow-through electrode system (FES) towards Gram-negative bacteria (Escherichia coli and fecal coliform) and Gram-positive bacteria (Enterococcus faecalis and Bacillus subtilis) in normal saline was systematically investigated over a wide range of applied voltages (1–5 V) and hydraulic retention times (HRTs) (1–10 s). It was revealed that the Gram-negative bacteria were more vulnerable to FES for their thinner cell walls, and over 6.5 log removal (no live bacteria detected) was achieved at the applied voltage of 2 V and HRT of 2 s; while Gram-positive bacteria were inactivated at slightly higher voltages (3 V, 2 s) or longer HRTs (2 V, 5 s). Bacterial inactivation was attributed to the change and rupture of cell membrane mainly by anode direct oxidation without bacterial regrowth/reactivation. In addition, negligible generation of the free chlorine at low voltages (≤2 V) can avoid the formation of potential chlorinated disinfection byproducts (DBPs). Hence, FES can offer a potential alternative to conventional disinfection methods for bacterial inactivation in natural and contaminated water.

Novel Chlorination Byproducts of Tryptophan: Initial High-Yield Transformation Products versus Small Molecule Disinfection Byproducts

Because of the difficulty of carbon–carbon bond cleavage needed to liberate the small molecule chlorine disinfection byproducts (DBPs; e.g., trihalomethanes), they typically form at <1% yields. By ...

Nonhalogenated Aromatic DBPs in Drinking Water Chlorination: A Gap between NOM and Halogenated Aromatic DBPs.

Halogenated disinfection byproducts (DBPs) are generated via reactions with natural organic matter (NOM) in chlorine disinfection of drinking water. How large NOM molecules are converted to halogenated aliphatic DBPs during chlorination remains a fascinating yet largely unresolved issue. Recently, many relatively toxic halogenated aromatic DBPs have been identified in chlorinated drinking waters, and they behave as intermediate DBPs to decompose to halogenated aliphatic DBPs. There is still one gap between NOM and halogenated aromatic DBPs. In this study, nine nonhalogenated aromatic compounds were identified as new intermediate DBPs in chlorination, including 4-hydroxybenzaldehyde, 4-hydroxybenzoic acid, 3-formyl-4-hydroxybenzoic acid, salicylic acid, 5-formyl-2-hydroxybenzoic acid, 4-hydroxyphthalic acid, 4'-hydroxyacetophenone, 4-methylbenzoic acid, and 4-hydroxy-3-methylbenzaldehyde. These nonhalogenated aromatic DBPs formed quickly and reached the maximum levels at relatively low chlorine doses within a short contact time, and their formation pathways were proposed. The formation kinetics of three nonhalogenated aromatic DBPs and their corresponding monochloro-/dichloro-substitutes during chlorination were then modeled. The nonhalogenated aromatic DBPs contributed up to 84% of the formed monochloro-substitutes and 22% of the formed dichloro-substitutes, demonstrating that they somewhat acted as intermediates between NOM and halogenated aromatic DBPs. Furthermore, the formed nonhalogenated aromatic DBPs were found to be removed by >50% by granular activated carbon adsorption.

Disinfecting Water with the Carbon Fiber-Based Flow-Through Electrode System (FES): Towards Axial Dispersion and Velocity Profile

Electrochemical technology for the killing of pathogens has been largely investigated. Lately, Ni et al. [1] published excellent research on the disinfection efficiency of a carbon fiber-based flow-through electrode system (FES) versus Gram-negative bacteria (Escherichia coli and fecal coliform) and Gram-positive bacteria (Enterococcus faecalis and Bacillus subtilis) in normal saline over a large span of applied voltages (1 - 5 V) and hydraulic retention times (HRTs) (1 - 10 s). They established that the Gram-negative microbes were more susceptible to FES for their thinner cell walls and over 6.5 log reduction (no live bacteria found) was obtained at the applied voltage of 2 V and HRT of 2 s; however, Gram-positive microbes were demobilized at slightly bigger voltages (3 V, 2 s) or longer HRTs (2 V, 5 s). Demobilizing microorganisms was related to the alteration and laceration of cell membranes mostly via anode direct oxidation in the absence of bacterial regrowth. Further, the disregarding formation of the free chlorine at low voltages (≤2 V) could avert the production of possible chlorinated disinfection by-products. Therefore, FES could furnish an undeveloped substitute to traditional disinfection processes for eliminating pathogens in water. This work concludes that focusing on axial dispersion and velocity profile inside anode will be very useful in comprehending the transport phenomena and proposing a fresh model that merges the axial dispersion and velocity profile for the FES. Such a research trend will more encourage the FES implementation at the large industrial level for disinfecting water.

Strengths of correlations with formation of chlorination disinfection byproducts: effects of predictor type and other factors

Measurements of the UV-Vis absorbance (Abs) and intensity of fluorescence emission (Fluor), as well as of concentrations of total or dissolved organic carbon (OC) in aqueous samples are commonly used to estimate the potential for disinfection byproducts (DBPs) formation during water chlorination. In this work, based on 574 linear associations collected from 70 experimental research papers published over the period of 1997-2019, the strengths of the correlations of Abs, Fluor, and OC with DBPs concentrations are compared. The correlations were expressed as approximately normally distributed Z-scores using Fisher variance-stabilizing transformation. The effects of specific prediction method, chlorination agent, water source, and DBPs type, with consideration of possible effects due to the presence of bromide, are examined against Z-scores by ANOVA, testing main effects and some variables interactions. The performed analysis is a first attempt to expose differences and patterns in correlation strengths associated with DBPs formation, based on systematically covered broad existing literature. Abs and OC concentration of water samples tend to demonstrate the strongest correlations with DBPs formation as compared with specific UV absorbance (SUVA) or intensity of fluorescence emission. Correlations of DBPs formation during chloramination demonstrated weaker strengths as compared with other chlorination agents, suggesting more caution in predicting DBPs concentrations, based on simple descriptors such as Abs, OC, and Fluor. In a series of different water types, the correlations with DBPs formation are expected to be enhanced, when wastewater is chlorinated. Non-fluorescent matter may be an important contributor to DBPs formation during water chlorination. When fluorescence intensity is considered as a predicting tool, choosing humic-like rather than proteinaceous fluorescence may enhance the strengths of the correlations with DBPs formation. Different performances of Abs, OC, and Fluor in correlating with DBPs formation may be beneficial for their concurrent use helping to optimize removal of different DBPs precursors.

Disinfection By-products and the Relevant Health Risk in the Water Supply System in H City of Zhejiang Province

The occurrence of 18 types of disinfection by-products (DBPs) in two waterworks and the corresponding water supply networks of H City in Zhejiang Province was determined by gas chromatography coupled with electron capture detector (GC-ECD). The correlation between DBPs and organic precursors, and health risks caused by DBPs, were discussed. Results showed that the disinfection by-products detected in drinking water in H City mainly include trihalomethanes (THMs), haloacetic acid (HAAs), haloacetonitrile (HANs) and trichloronitromethane (HNMs), with highest concentrations of THMs followed by HAAs. In the finish water of CX Waterworks and tap water supplied by CX Water works, concentrations of THMs ranged from 7.70 to 32.73μg·L-1and 9.00 to 51.42μg·L-1, respectively, and those of HAAs 3.05 to 21.30μg·L-1 and 6.00 to 26.79μg·L-1, respectively. The THMs in finished water and tap water of TH Waterworks were in the range 8.65-38.76μg·L-1 and 12.09-42.04μg·L-1, respectively, and those of HAAs were 2.42-14.79μg·L-1 and 2.80-33.40μg·L-1, respectively. The DBPs in the finished and tap water of the two waterworks were at lower levels than the limitations regulated by the Sanitary Standard for Drinking Water (GB 5749-2006). The index of dissolved organic carbon (DOC) and UV254 were adopted to describe the organic compounds, and it was found that trichloromethane (TCM) was significantly negatively correlated with DOC and UV254in tap water. Based on the EPA recommended health risk assessment model, the carcinogenic and non-carcinogenic risks of chlorine disinfection by-products in the oral intake route were calculated. It was found that the carcinogenic risks caused by the disinfection by-products in the finished water and tap water of H City were 5.94×10-6-4.76×10-5 and 5.94×10-6-5.56×10-5, respectively, while the non-carcinogenic risks were 0.91×10-2-4.20×10-2 and 1.26×10-2-4.72×10-2, respectively. The carcinogenic risk is mainly from THMs:bromodichloromethane (BDCM) contributes the highest cancer risk, and the non-carcinogenic risk is mainly from TCM.

Synchronous Reduction-Oxidation Process for Efficient Removal of Trichloroacetic Acid: H* Initiates Dechlorination and ·OH Is Responsible for Removal Efficiency.

Degradation of chlorinated disinfection by-products using the electroreduction process has been considered as a promising approach for advanced water treatment, while the removal efficiency is restricted by a high barrier for dechlorination of intermediates only by reductive atomic hydrogen (H*) and excessive cost required for reducing atmosphere. In this paper, we predict that the dechlorination efficiency for trichloroacetic acid (TCA), a typical chlorinated disinfection by-product, can be accelerated via a synchronous reduction-oxidation process, where the dechlorination barrier can be lowered by the oxidation reactions toward the critical intermediates using hydroxyl radicals (·OH). Based on scientific findings, we constructed a synchronous reduction-oxidation platform using a Pd-loaded Cu/Cu2O/CuO array as the core component. According to the combined results of theoretical and experimental analyses, we found that the high dispersion of nano-sized Pd on a photocathode was beneficial for the production of a high concentration of H* at low overpotential, a perquisite for initiating the dechlorination reaction. Simultaneously, excess H* has the potential to convert O2 to H2O2 in ambient conditions (air condition), and H2O2 can be further activated by a Cu-containing substrate to ·OH for attacking the critical intermediates. In this system, ∼89.1% of TCA was completely dechlorinated and ∼26.8% mineralization was achieved in 60 min, which was in contrast to the value of ∼65.7% and mineralization efficiency of only ∼1.7% achieved through the reduction process (Ar condition).

UV-assisted chlorination of algae-laden water: Cell lysis and disinfection byproducts formation

Chlorination of algae-laden water under UV irradiation was studied in bench scale. An obvious synergistic effect between UV light (at 254 nm) and chlorine was obtained due to the formation of HO, which promoted the degradation of Microcystis aeruginosa. During this process, sequential UV/chlorine and UV irradiation were included, and UV/chlorine stage accounted for 86% of total algae removal with 50 mg/L chlorine. The removal performance was positively related to the chlorine dose in the range of 5–50 mg/L. The presence of chloride had little influence, whereas ammonia significantly inhibited the algae removal as chlorine was quickly transformed to chloramine. The integrity of algae cells was disrupted immediately, along with an instant release of algal organic matter which was synchronously degraded by UV/chlorine. The emission scanning electron microscopy results further confirm the occurrence of serious cell lysis. Moreover, a large amount of chlorinated disinfection byproducts (DBPs) produced during the UV/chlorine process. But the final yields of DBPs from chlorination of algae suspension over a period of 23 h storing in dark surpassed that after UV/chlorine treatment. This work suggests a promising technique for the treatment of algae-laden water by using UV/chlorine.

Applicability of advanced oxidation processes in removing anthropogenically influenced chlorination disinfection byproduct precursors in a developing country

The studies on occurrence of contaminants of emerging concern in drinking water treatment plants or even wastewater treatment plants in developing country like India, are very limited. Trihalomethanes (THMs) is one such contaminant of concern in drinking water treatment sector. THMs are the major disinfection byproducts (DBPs) formed during the widely used chlorination process. Their identification and removal is of utmost importance in developed as well as developing nations. This study is first of its kind to assess the removal of mixture of urban run-off driven organic matter, agricultural run-off driven organic matter, untreated sewage effluent driven organic matter and little natural organic matter (NOM) (altogether NefOM) (major DBP precursors) using advanced oxidation processes (AOPs) in the Indian region. Since, NOM vary geographically, this study will add up to applicability of generally utilized AOPs for removal of site explicit (Indian) NefOM. Trihalomethanes at a conventional water treatment plant at Mathura and a moving bed biofilm based non-conventional water treatment plant at Agra were monitored over a year, demonstrating the inability of the water treatment plants to limit formation of DBPs from Yamuna inlet water at any time of the year. Various AOPs (UV–H2O2, O3–H2O2, O3) and UV (ultraviolet) photolysis were assessed for their ability to decrease the trihalomethane forming potential (THMFP) by degrading the contaminants in the waters of Yamuna. Kinetic studies were conducted to evaluate the selected AOPs based on their ability to mineralize dissolved organic carbon (DOC), and decrease UV254 at various pH, UV intensities, and ozone and hydrogen peroxide concentrations. UV-L/H2O2 at an intensity of 47 mJ/cm2/min, pH = 7, and at hydrogen peroxide concentration of 0.5 mM provided an optimum reduction of DOC (64%) and UV254 (87%). Fractionation studies indicated that treatment by UV-L/H2O2 leads to the most significant decrease in the hydrophobic fraction of the water, while further study indicated that UV-L/H2O2 also showed maximum attenuation of THMFP.

Investigation of the effective factors on the mutagen X formation in drinking water by response surface methodology

Mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) is known as a potent factor in inducing DNA damage and increasing cancer risk. MX is a chlorination disinfection byproduct that comes from the reaction of humic acids and chlorine in drinking water. The purpose of this study was to evaluate the effects of significant factors (including pH, reaction time, chlorine and the concentration of organic materials (TOC)) and their interactions on the MX formation rate in chlorinated drinking water using Box-Behnken Design (BBD) and response surface method (RSM). For this purpose, the simulation of water chlorination disinfection process was carried out in a laboratory scale. A quadratic model was chosen to determine the mathematical relations between the response and the effective factors. All linear parameters, as well as second-degree components except chlorine, were statistically significant. Also, the interactions of contact time with TOC, free chlorine residual with TOC, and chlorine with pH were also statistically significant. Statistical results showed that the pH had a great effect on the potential of MX formation, and then the factors of TOC, chlorine and contact time were effective, respectively. The percentage of contribution (PC) of each component in the formation of MX. The highest significant percentage of contribution (48.36%) was allocated to the pH. Under the optimum conditions (contact time of 48.38 min, chlorine concentration of 0.79 mg/L, TOC concentration of 0.53 mg/L, and pH of 7.98), minimum value of MX was equal to 28.6.

Aqueous Chlorination Kinetics of Cyclic Alkenes-Is HOCl the Only Chlorinating Agent that Matters?

Although Cl2 and Cl2O have been recognized as highly reactive constituents of free available chlorine (FAC), robust rate constants for Cl2 and Cl2O remain scarce in the environmental literature. In this work, we explored the chlorination kinetics of three structurally related alkenes (α-ionone, β-ionone, and dehydro-β-ionone), a class of compounds whose reactivities with Cl2 and Cl2O have not been previously investigated. Second-order rate constants for Cl2, Cl2O, and HOCl were computed from experimental rate constants obtained at various pH values, [Cl-], and [FAC]. Our results show that while HOCl is the predominant chlorinating agent for the most reactive alkene, Cl2 and Cl2O can dominate the chlorination kinetics of the less reactive alkenes at high [Cl-] and high [FAC], respectively. The tradeoff between overall reactivity with FAC and selectivity for Cl2 and Cl2O previously observed for aromatic compounds also applies to the alkenes examined. In laboratory experiments in which high [FAC] may be used, omission of Cl2O in data modeling could yield second-order rate constants of dubious validity. In chlorinating real waters with elevated [Cl-], formation of Cl2 may enhance the formation kinetics of chlorinated disinfection byproducts (DBPs) and exacerbate the burden of DBP control for water utilities.

Assessment of the chlorine demand and disinfection byproduct formation potential of surface waters via satellite remote sensing

The ability of satellites to assess surface water quality indicators such as colored dissolved organic matter (CDOM) suggests that remote sensing could be a useful tool for evaluating water treatability metrics in considering potential drinking water supplies. To explore this possibility, 24 surface water samples were collected throughout Minnesota, USA with wide ranging values of CDOM (a440; 0.41–27.9 m-1), dissolved organic carbon (DOC; 5.5–47.6 mg/L) and specific ultraviolet absorbance at 254 nm (SUVA254; 1.3–5.1 L/mg-M). Laboratory experiments were performed to quantify chlorine demand and the formation of two classes of halogenated disinfection byproducts (DBPs), trihalomethanes (THMs) and haloacetic acids (HAAs), using the uniform formation conditions (UFC) test. Chlorine demand and THMUFC were linearly correlated with CDOM (R2 = 0.97 and 0.91, respectively), indicating that CDOM is a useful predictor of these parameters. On the other hand, data comparing di- and tri-HAAUFC with CDOM were better fit by a logarithmic relationship (R2 = 0.73 and 0.87, respectively), while mono-HAAUFC was linearly correlated with CDOM (R2 = 0.46) but only for low-to moderately-colored waters (a440 ≤ 11 m−1). The correlations relating chlorine demand and DBPUFC values with CDOM were coupled with satellite CDOM assessments to estimate chlorine demand and DBPUFC values for all surface waters larger than 0.05 km2 in the state of Minnesota, USA. The resulting maps suggest that only 21.8% of Minnesota lakes would meet both the THM and HAA maximum contaminant levels, but only when pre-disinfection treatment removes 75% of DBP precursors. There are limitations to determining CDOM using satellites for high color surface waters (a440 > 11 m−1), however, leading to underpredicted values for CDOM, chlorine demand, and DBPUFC. Overall, the results demonstrate the potential benefits of satellite remote sensing for assessing potential drinking water sources and water treatability metrics.

Evidence-based analysis on the toxicity of disinfection byproducts in vivo and in vitro for disinfection selection

Disinfection is a key step in drinking water treatment process to prevent water-borne infections. However, reactions between chlorine, one of the most common disinfectants, and natural organic matter (NOM) often lead to the formation of hazardous disinfection byproducts (DBPs). However, the cytotoxicity of some DBPs is still poorly understood. Such knowledge is critical for proper selection of disinfection processes. We investigated the effects of DBPs on mouse acute liver injury. The exacerbation of liver damage increased with the DBPs concentrations, likely due to the increased hepatic macrophages. Haloacetonitriles (HANs) and haloketones (HKs) are more toxic to Human Hepatocellular (Hep3B) cells than trihalomethanes (THMs). Cytotoxicity of DBPs were governed by the halogen type (brominated DBPs > chlorinated DBPs) and the numbers of halogen atoms per molecule. Then, we used the pilot-scale WDS to study the best conditions for reducing the formation of DBPs. The result showed that the formation of DBPs followed the order: stainless-steel (SS) > ductile iron (DI) > polyethylene (PE) pipe. Higher flowrate promoted the formation of DBPs in all three pipes. The results suggest that the formation of DBPs in chlorine disinfection can be reduced by using PE pipes and low flow rate in water distribution systems (WDS).

Amorphous nickel phosphide as a noble metal-free cathode for electrochemical dechlorination

Nickel phosphide (Ni2P) is an emerging efficient catalyst for the hydrogen evolution and water splitting. Herein, we report that Ni2P is also a promising catalyst for enhancing electrochemical dechlorination of chlorinated disinfection byproducts (DBPs). Amorphous Ni2P (ANP) mini-nanorod arrays were in-situ fabricated on nickel foam (NF) via a facile phosphidation process, and then used as a binder-free cathode for electrochemical dechlorination of trichloroacetic acid (TCAA). Results showed that ANP exhibited superior performance on electrochemical dechlorination of TCAA than other metal cathodes (e.g., NF and Pd/C). Scavenging experiments and electron spin resonance (ESR) technique indicated that atomic H* was generated from water reduction through ANP catalysis, and primarily contributed to TCAA dechlorination. Indeed, the superhydrophilic surface of ANP favored electrocatalyst/electrolyte contact, and its low impedance further afforded rapid electron transport from the electrode to water or protons for atomic H* generation. The kinetic modelling and mass balance evaluation revealed the transformation mechanism of TCAA dechlorination. This study is among the first to develop ANP as a binder-free cathode for electrochemical dechlorination, and have important implications for eliminating chlorinated DBPs in water.

Cytotoxic comparison of macrolide antibiotics and their chlorinated disinfection byproduct mixtures

Erythromycin (ERY), azithromycin (AZI) and telithromycin (TEL) are widely-used macrolide antibiotics that are frequently detected in various water environments, including resource water and drinking water. In the performed chlorination disinfection process, at least 10, 20 and 200 new disinfection byproducts of ERY, AZI and TEL, respectively, were observed (the mixtures of the disinfection byproducts of ERY, AZI and TEL were named ERY-M, AZI-M and TEL-M, respectively). There is limited information available regarding their comparative toxicities, and their potential health risks are still unknown. In this study, the Jurkat cell line was used to compare the toxicities of the disinfection byproduct mixtures and their precursor compounds. The cell viability results indicated that the toxicity of ERY-M may not be enhanced after disinfection by chlorination. In contrast, at the same concentrations, AZI-M and TEL-M induced more significant inhibitory effects on cell viability than their parent compounds. Additionally, the total antioxidant capacity (T-AOC) and cell cytokine release (including interleukin-2, interleukin-8 and tumor necrosis factor-α) analyses of AZI-M and TEL-M further verified these results. Our findings demonstrate that the cytotoxicity of AZI and TEL was enhanced during the chlorination disinfection process. This investigation will provide substantial new details related to the toxicity of the mixed disinfection byproducts (DBPs) of ERY, AZI and TEL generated in the chlorination disinfection process.

Decomposition of β-N-methylamino-L-alanine (BMAA) and 2,4-diaminobutyric acid (DAB) during chlorination and consequent disinfection byproducts formation

β-N-methylamino-L-alanine (BMAA) and 2,4-diaminobutyric acid (DAB) are two newly identified algal toxins, and they may react with chlorine to undergo decomposition and generate disinfection byproducts (DBPs) during pre-chlorination as well as chlorine disinfection. In this study, the decomposition of BMAA and DAB during chlorination and the consequent DBPs formation were investigated. The BMAA and DAB concentrations in source waters were determined, the decomposition kinetics of BMAA and DAB and the formation of DBPs during chlorination were studied, the formation pathways of DBPs from BMAA and DAB were explored, and the factors which may affect the decomposition and DBPs formation were examined. The results revealed that BMAA and DAB were commonly detected in source waters from Taihu Lake, and the highest level of BMAA reached 230.8 ng/L, while the concentrations of DAB were generally around 2.0 ng/L. The decomposition of BMAA and DAB during chlorination both followed pseudo-first-order decay while the decomposition rate constant of DAB was significantly higher than that of BMAA. Trihalomethanes (THMs), haloacetic acids (HAAs), and haloacetonitriles (HANs) were all generated during the chlorination of BMAA and DAB with relatively high yields. Notably, the THMs, HAAs, and HANs yields of each carbon atom from BMAA and DAB were significantly higher than that from other organic precursors, and the formation of HANs from DAB was significantly higher than that from BMAA. The formation pathways of DBPs from BMAA and DAB were tentatively proposed and verified through theoretical calculations. Of note, the proposed formation pathways of THMs and HAAs from BMAA were similar to that from DAB, while the proposed formation pathways of HANs from BMAA and DAB showed some differences. Chlorine dose, pH and temperature all affected the decomposition of BMAA and DAB and DBPs formation during chlorination.

Multi-wavelength models expand the validity of DBP-differential absorbance relationships in drinking water.

Differential UV absorbance (ΔA) is an important indicator that could allow operators and utility managers to routinely monitor disinfection by-product (DBP) concentrations, even in real-time applications, without the limitations of regulatory sampling and analyses. While determination coefficients between differential UV absorbance at a single wavelength (often 272 nm) and chlorination DBP concentrations are usually very high (R2 > 0,90), the fitting parameters of these relationships vary from one water source to another, or vary within the same water source depending on the time of year. The objectives of this study are to apply multiple regression models to a rich database of ΔA and DBPs (trihalomethanes (THMs) and haloacetic acids (HAAs)) that was generated from lab experiments using multiple waters with low bromide concentrations, in order to identify wavelengths that improve the applicability of DBP-ΔA relationships, as well as develop a widely applicable multi-wavelength DBP-ΔA relationship. The results show that using ΔA at two wavelengths, in addition to initial absorbance (A) at one wavelength, greatly improves the determination coefficients of the relationships, when compared with the best possible single-wavelength relationships. The significant predictors identified are A270, ΔA270 and ΔA425 for THMs; A255, ΔA255 and ΔA425 for DCAA; A250, ΔA250 and ΔA425 for TCAA; and A250, ΔA250 and ΔA425 for HAA6. This paper also discusses the applicability of the models developed for predicting DBPs in treatment plants and drinking water, as well as their limitations and the required future research to improve their performance.

Synergetic effects of novel aromatic brominated and chlorinated disinfection byproducts on Vibrio qinghaiensis sp.-Q67

Aromatic halogenated chemicals are an unregulated class of byproducts (DBPs) generated from disinfection processes in the water environment. Information on the toxicological interactions, such as antagonism and synergism, present in DBP mixtures remains limited. This study aimed to determine the toxicological effects of aromatic halogenated DBP mixtures on the freshwater bacterium Vibrio qinghaiensis sp.-Q67. The acute toxicities of seven DBPs and their binary mixtures toward V. qinghaiensis sp.-Q67 were determined through microplate toxicity analysis. The toxicities of single DBPs were ranked as follows: 2,5-dibromohydroquinone > 2,4-dibromophenol > 4-bromo-2-chlorophenol ≈ 2,6-dibromo-4-nitrophenol > 2,6-dichloro-4-nitrophenol > 2-bromo-4-chlorophenol > 4-bromophenol. The percentages of synergism (experimental values higher than the predicted concentration addition) on the levels of 50%, 20%, and 10% effective concentrations reached 61%, 41%, and 31%, respectively. These results indicated that the probability of synergism decreased as concentration levels decreased. The synergetic effects of the compounds were dependent on concentration levels and concentration ratios. The proposed quantitative structure–activity relationship model can be used to predict the interactive toxicities exerted by 105 binary DBP mixture rays of 21 DBP mixture systems.