Speciation Of Disinfection By-products Research Articles

Maternal Exposure to Tap Water Disinfection By-Products and Risk of Selected Congenital Heart Defects.

The use of chlorine to treat drinking water produces disinfection by-products (DBPs), which have been associated with congenital heart defects (CHDs) in some studies. Using National Birth Defects Prevention Study data, we linked geocoded residential addresses to public water supply measurement data for DBPs. Self-reported water consumption and filtration methods were used to estimate maternal ingestion of DBPs. We estimated adjusted odds ratios and 95% confidence intervals using logistic regression controlling for maternal age, education, body mass index (BMI), race/ethnicity, and study site to examine associations between CHDs and both household DBP level and estimated ingestion of DBPs. Household DBP exposure was assessed for 2717 participants (1495 cases and 1222 controls). We observed a broad range of positive, null, and negative estimates across eight specific CHDs and two summary exposures (trihalomethanes and haloacetic acids) plus nine individual DBP species. Examining ingestion exposure among 2488 participants (1347 cases, 1141 controls) produced similarly inconsistent results. Assessing both household DBP level and estimated ingestion of DBPs, we did not find strong evidence of an association between CHDs and DBPs. Despite a large study population, DBP measurements were available for less than half of participant addresses, limiting study power.

Formation, speciation, and temporal variability of DBPs in drinking water distribution systems in the context of ASR operations and extended storage periods

As climate change induces changes in water quality and available water quantity of drinking water supply sources, the final product water quality changes in terms of trace organics including disinfection byproducts (DBPs) formed during water treatment. In this study, the seasonal variability and speciation of DBPs across nine sample sites within a drinking water distribution system serving ∼400k people over a one-year period was investigated considering the governing parameters of water quality and treatment/transport/storage of finished water. The system considered treats surface water from a river and practices aquifer storage and recovery to address seasons water availability changes. Eighty-eight (88) sample sets were collected and held for 6-months in the laboratory to simulate extended storage scenarios associated with ASR operations, and each was analyzed at 9 different timesteps for concentration and speciation of chlorinated DBPs. Samples from groundwater influenced sites exhibited significantly lower total organic carbon (TOC) compared to other sites from the river source, and also were observed to have the lowest DBP formation. Three sites exceeded the Maximum Contaminant Level (MCL) for four total trihalomethanes (THM4) within 30–60 days of storage. Chloroform was the predominant THM4 species, even in groundwater-influenced locations, whereas di- and tri-chloroacetic acid (DCA and TCA) were the most prevalent haloacetic acids (HAA5). Extended water age at one site, coupled with low initial chlorine concentrations exhibited higher initial THM4 concentrations and flat DBP formation curves. The study results provide new insights into DBP occurrence and fate in drinking water distribution systems which consider water storage such as in ASR.

Comparative investigation of known and unknown disinfection by-product precursor removal and microbial community from biological biochar and activated carbon filters

Biological activated carbon filter (BAC) is one of the most effective technologies for removing disinfection by-product (DBP) precursors from water. Biochar is a lower-cost medium that has the potential to replace granular activated carbon in BAC applications, thus leading to the development of biological biochar filter (BCF). This study compared BCF with BAC for the removal of DBP precursors using column experiments. Both BCF and BAC achieved the removal of DBP precursors, resulting in concentrations of all DBP formation potential below the World Health Organization guideline values for drinking water. Bromodichloromethane and unknown DBP precursor removal by BCF was comparable to that by BAC. However, BAC removed more chloroform and dichloroacetontrile precursors than BCF. For microbial community analysis, cell numbers in a bottom layer (inlet) of BCF and BAC columns were higher than those in the top layer. The abundances of Nordella and a microbial genus from Burkholderiaceae at the bottom layer showed a strong correlation to the number of DBP precursors removed and were comparable in BCF and BAC. This finding likely contributes to the similarities between DBPs species removed and the removal performances of some known and unknown DBP precursors by BCF and BAC. Overall results from this study revealed that biochar can be served as a low-cost and sustainable replacement of activated carbon in water filter for DBP precursor removal.

Maternal periconceptional exposure to drinking water disinfection by-products and neural tube defects in offspring.

Associations between maternal periconceptional exposure to disinfection by-products (DBPs) in drinking water and neural tube defects (NTDs) in offspring are inconclusive, limited in part by exposure misclassification. Maternal interview reports of drinking water sources and consumption from the National Birth Defects Prevention Study were linked with DBP concentrations in public water system monitoring data for case children with an NTD and control children delivered during 2000-2005. DBPs analyzed were total trihalomethanes, the five most common haloacetic acids combined, and individual species. Associations were estimated for all NTDs combined and selected subtypes (spina bifida, anencephaly) with maternal periconceptional exposure to DBPs in public water systems and with average daily periconceptional ingestion of DBPs accounting for individual-level consumption and filtration information. Mixed effects logistic regression models with maternal race/ethnicity and educational attainment at delivery as fixed effects and study site as a random intercept were applied. Overall, 111 case and 649 control children were eligible for analyses. Adjusted odds ratios for maternal exposure to DBPs in public water systems ranged from 0.8-1.5 for all NTDs combined, 0.6-2.0 for spina bifida, and 0.7-1.9 for anencephaly; respective ranges for average daily maternal ingestion of DBPs were 0.7-1.1, 0.5-1.5, and 0.6-1.8. Several positive estimates (≥1.2) were observed, but all confidence intervals included the null. Using community- and individual-level data from a large, US, population-based, case-control study, we observed statistically nonsignificant associations between maternal periconceptional exposure to total and individual DBP species in drinking water and NTDs and subtypes.

Spatial and seasonal variation in disinfection byproducts concentrations in a rural public drinking water system: A case study of Martin County, Kentucky, USA.

To increase our understanding of the factors that influence formation of disinfection byproducts (DBPs) in rural drinking systems, we investigated the spatial and seasonal variation in trihalomethane (THM) and haloacetic acid (HAA) concentrations in relation to various chemical and physical variables in a rural public drinking water system in Martin County, Kentucky, USA. We collected drinking water samples from 97 individual homes over the course of one year and analyzed them for temperature, electrical conductivity, pH, free chlorine, total chlorine, THMs (chloroform, bromodichloromethane, dibromochloromethane, dichlorobromomethane, and bromoform) and HAAs (monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, and dibromoacetic acid). Spatial autocorrelation analysis showed only weak overall clustering for HAA concentrations and none for THMs. The relationship between modeled water age and TTHM or HAA5 concentrations varied seasonally. In contrast, there was strong variation for both HAA and THMs, with concentrations of HAA peaking in mid-summer and THMs peaking in early fall. Multiple regression analysis revealed that THM concentrations were strongly correlated with conductivity, while HAA concentrations were more strongly correlated with water temperature. Individual DBP species that only contained chlorine halogen groups were strongly correlated with temperature, while compounds containing bromine were more strongly correlated with conductivity. Further investigation revealed that increased drinking water conductivity associated with low discharge of the Tug Fork River, the source water, is highly correlated with increased concentrations of bromide. Discharge and conductivity of the Tug Fork River changed dramatically through the year contributing to a seasonal peak in bromide concentrations in the late summer and early fall and appeared to be a driver of brominated THM concentrations. Brominated DBPs tend to have higher toxicity than DBPs containing only chlorine, therefore this study provides important insight into the seasonal factors driving risk from exposure to DBPs in rural drinking water systems impacted by bromide.

MIEX resin and enhanced coagulation treatment of high-bromide natural water: Chlorine reactivity and DBP precursors removal

Both organic and inorganic constituents play a major role in the formation and speciation of disinfection by-products (DBPs) under chlorination. In this study, the removal of organic and inorganic precursors to DBPs by ion exchange and coagulation was examined, and the relationships between characteristics of dissolved organic matter (DOM), chlorine reactivity, and the formation of DBPs in high-bromide natural water were investigated. Formation potential tests were conducted for trihalomethanes (THMs) and haloacetronitriles (HANs) before and after the different treatments (coagulation, magnetic ion exchange (MIEX) resin, and combined MIEX/coagulation). At a low resin dose, MIEX was more effective than coagulation for DOM removal. The advantages of the MIEX resin were more prominent at a high resin dose because substantial amounts of DOM and bromide were simultaneously removed. The maximum bromide uptake on the MIEX resin was 0.02 mg-Br/mL. A 4-component PARAFAC model was developed using a dataset of 148 fluorescence excitation-emission matrices (EEMs) generated from pre-chlorinated and post-chlorinated samples. The maximum fluorescence intensities of humic-like components were found to be strongly correlated to THMs formation (R2 = 0.79–0.89). The MIEX treatment substantially lowered the formation of THMs (19–51%) and HANs (70–95%) due to its ability to remove humic-like DOM and bromide. The fluorescence loss for humic-like DOM was found to increase over a chlorination time of 3 days, suggesting that these compounds had stronger reactivity to chlorine compared to protein-like DOM. The chlorine reactivity of protein-like DOM increased after treatments as the residual chlorine was able to react with the less reactive fractions of DOM after chlorine-reactive compounds were removed.

Fluorescent Dissolved Organic Matter Components as Surrogates for Disinfection Byproduct Formation in Drinking Water: A Critical Review.

Disinfection byproduct (DBP) formation, prediction, and minimization are critical challenges facing the drinking water treatment industry worldwide where chemical disinfection is required to inactivate pathogenic microorganisms. Fluorescence excitation-emission matrices-parallel factor analysis (EEM-PARAFAC) is used to characterize and quantify fluorescent dissolved organic matter (FDOM) components in aquatic systems and may offer considerable promise as a low-cost optical surrogate for DBP formation in treated drinking waters. However, the global utility of this approach for quantification and prediction of specific DBP classes or species has not been widely explored to date. Hence, this critical review aims to elucidate recurring empirical relationships between common environmental fluorophores (identified by PARAFAC) and DBP concentrations produced during water disinfection. From 45 selected peer-reviewed articles, 218 statistically significant linear relationships (R2 ≥ 0.5) with one or more DBP classes or species were established. Trihalomethanes (THMs) and haloacetic acids (HAAs), as key regulated classes, were extensively investigated and exhibited strong, recurrent relationships with ubiquitous humic/fulvic-like FDOM components, highlighting their potential as surrogates for carbonaceous DBP formation. Conversely, observed relationships between nitrogenous DBP classes, such as haloacetonitriles (HANs), halonitromethanes (HNMs), and N-nitrosamines (NAs), and PARAFAC fluorophores were more ambiguous, but preferential relationships with protein-like components in the case of algal/microbial FDOM sources were noted. This review highlights the challenges of transposing site-specific or FDOM source-specific empirical relationships between PARAFAC component and DBP formation potential to a global model.

Comparative cytotoxicity analyses of disinfection byproducts in drinking water using dimensionless parameter scaling method: Effect of halogen substitution type and number

Up to date, over 700 disinfection byproducts (DBPs) have been detected and identified in drinking water. It has been recognized that cytotoxicity of DBPs varied significantly among groups. Even within the same group, cytotoxicity of different DBP species was also different due to different halogen substitution types and numbers. However, it is still difficult to quantitatively determine the inter-group cytotoxicity relationships of DBPs under the effect of halogen substitution in different cell lines, especially when a large number of DBP groups and multiple cytotoxicity cell lines are involved. In this study, a powerful dimensionless parameter scaling method was adopted to quantitatively determine the relationship of halogen substitution and the cytotoxicity of various DBP groups in three cell lines (i.e., the human breast carcinoma (MVLN), Chinese hamster ovary (CHO), and human hepatoma (Hep G2) cell cytotoxicity) with no need to consider their absolute values and other influences. By introducing the dimensionless parameters Dx−orn−speciescellline and D¯x−orn−speciescellline, as well as their corresponding linear regression equation coefficients ktypeornumbercellline and k¯typeornumbercellline, the strength and trend of halogen substitution influences on the relative cytotoxic potency could be determined. It was found that the effect of halogen substitution type and number on the cytotoxicity of DBPs followed the same patterns in the three cell lines. The CHO cell cytotoxicity was the most sensitive cell line to evaluate the effect of halogen substitution on the aliphatic DBPs, whereas the MVLN cell cytotoxicity was the most sensitive cell line to evaluate the effect of halogen substitution on the cyclic DBPs. Notably, seven quantitative structure activity relationship (QSAR) models were established, which could not only predict the cytotoxicity data of DBPs, but also help to explain and verify the patterns of halogen substitution effect on cytotoxicity of DBPs.

Control of Pre-formed Halogenated Disinfection Byproducts with Reuse Biofiltration.

Disinfection byproduct (DBP) pre-formation is a major issue when prechlorination is used before or during advanced treatment of impacted drinking water sources. Control strategies for pre-formed DBPs before final disinfection, especially for currently nonregulated although highly toxic DBP species, are not yet established. This study evaluated the biodegradation potential of pre-formed DBPs, including haloacetonitriles (HANs), haloacetamides (HAMs), and haloacetaldehydes (HALs), during biofiltration with sand, anthracite, and biological activated carbon of three wastewater effluents under potable reuse conditions. Up to 90%+ removal of di- and trihalogenated HANs, HAMs, and HALs was observed, and removal was associated with active heterotrophic biomass and removal of biodegradable organic carbon. Unlike the microbial dehalogenation pathway of haloacetic acids (HAAs), removal of HANs and HAMs appeared to result from a biologically mediated hydrolysis pathway (i.e., HANs to HAMs and HAAs) that may be prone to inhibition. After prechlorination, biofiltration effectively controlled pre-formed DBP concentrations (e.g., from 271 μg/L to as low as 22 μg/L in total) and DBP-associated calculated toxicity (e.g., 96%+ reduction). Abiotic residual adsorption capacity in biological activated carbon media was important for controlling trihalomethanes. Overall, the toxicity-driving DBP species exhibited high biodegradation potential and biofiltration showed significant promise as a pre-formed DBP control technology.

Effect of iodoacetic acid on the reproductive system of male mice.

Iodoacetic acid (IAA) is one of the most common water disinfection byproducts (DBPs). Humans and animals are widely and continuously exposed to it. Many species of water DBPs are harmful to the reproductive system of organisms. Nevertheless, the potential effects of IAA exposure on testosterone and spermatogenesis in vivo remain ambiguous. Spermatogenous cells are the site of spermatogenesis, Leydig cells are the site of testosterone synthesis, and Sertoli cells build the blood–testis barrier (BTB), providing a stable environment for the aforementioned important physiological functions in testicular tissue. Therefore, we observed the effects of IAA on spermatogenic cells, Leydig cells, and Sertoli cells in the testis. In this study, we found that oral administration of IAA (35 mg/kg body weight per day for 28 days) in male mice increased serum LH levels and reduced sperm motility, affecting average path velocity and straight line velocity of sperm. In addition, IAA promoted the expression of γH2AX, a marker for DNA double-strand breaks. Moreover, IAA downregulated the protein expression of the scavenger receptor class B type 1 (SRB1), and decreased lipid droplet transport into Leydig cells, which reduced the storage of testosterone synthesis raw materials and might cause a drop in testosterone production. Furthermore, IAA did not affect the function of BTB. Thus, our results indicated that IAA exposure affected spermatogenesis and testosterone synthesis by inducing DNA damage and reducing lipid droplet transport.

Impacts of carbon-based advanced treatment processes on disinfection byproduct formation and speciation for potable reuse

For the potable reuse of municipal wastewater effluent, carbon based advanced treatment (CBAT) using coagulation, ozonation, biofiltration and/or granular activated carbon (GAC) adsorption is a promising approach for controlling disinfection byproduct (DBP) formation. However, CBAT can also favor a shift in DBP formation to more toxic brominated DBP species. To protect public health, treatment-specific DBP formation and speciation trends need to be identified and understood. First, this study systematically evaluated the treatment of six wastewater effluents with four CBAT process trains (experimental n was 55) and measured DBP formation and speciation trends. Overall, CBAT decreased DBP formation by >90% and GAC preferentially removed highly-reactive effluent organic matter as indicated by lower yields of both highly-forming and highly-toxic classes of carbonaceous and nitrogenous DBPs. Since GAC treatment also induced systematic speciation changes by increasing the ratio of bromide to dissolved organic matter, the second part of this study focused on understanding the health impacts of DBP speciation changes on calculated additive toxicity (CAT). Based on the evaluation of 20 DBPs, measured using established methods, the CAT values from cyto- and genotoxicity metrics decreased by as much as 85% due to high levels of precursor removal by GAC. Expanding the evaluation to include 52 DBPs, measured using more extensive analytical methods, resulted in the same conclusions. This study also developed a “speciation potency” metric, that re-scales class-by-class speciation trends using toxic potency factors (e.g., cytotoxicity [LC50]). The observed shifts in DBP speciation after treatment increased the class-level toxic potency factors by up to a factor of 4; a greater amount of precursor removal is required for treatment to reduce toxicity, which was achieved with CBAT trains. This proposed approach of combining speciation potency with DBP yields enables evaluation of DBP-associated risk with easily measured surrogates (i.e., bromide and dissolved organic carbon [DOC]). By identifying and quantitatively comparing DBP formation and speciation trends over multiple wastewater effluents and treatment trains, this study demonstrates that CBAT can be a robust approach to DBP precursor removal for potable reuse.

Multivariate experimental design provides insights for the optimisation of rechloramination conditions and water age to control disinfectant decay and disinfection by-product formation in treated drinking water

The stability of drinking water disinfectant residuals is known to be influenced by multiple variables. To evaluate the effects of various influencing variables on disinfectant stability, a multivariate analysis of chloramine decay and associated disinfection by-products (DBPs) formation was investigated in a series of bench-scale experiments. Of nine water quality variables previously identified, monochloramine dose, pH, and bromide concentration were selected as key water quality variables based on previous investigations and modelling. Co-effects of these key variables on monochloramine decay and formation of 33 halogenated and nitrogen-containing DBPs were investigated using response surface experimental design.Rechloramination conditions, including monochloramine dose, pH and bromide concentration, were optimised via a 3-factorial multivariate analysis of monochloramine stability in post-treatment drinking water. Effects of influencing variables on disinfectant decay and DBP formation were assessed and graphically presented as response surfaces with minimal experiments using Doehlert matrix experimental design compared to other multivariate experimental designs. Concentrations of trihalomethanes (THMs), haloacetic acids (HAAs), and N-nitrosamines were found to increase with water age, whereas opposite phenomenon was observed in the net production of haloacetonitriles (HANs). Increasing pH was found to stabilise monochloramine but it could cause DBP speciation to shift. Furthermore, increasing bromide concentration elevated Br-DBP formation. In bromide-containing water, pH = 7.8–8.0 should be considered as higher pH increases Br-THMs formations and lower pH increases formations of Br-HAAs and Br-HANs. However, water age or pH has insignificant impacts on DBP formation after significant monochloramine decay or at low initial monochloramine dose.These findings indicate that effective combined control measures to maintain monochloramine stability should include the application of high monochloramine dose (>1.5 mg-Cl2.L−1) under conditions of moderate to high pH (pH = 7.8–8.0) and minimal bromide concentration. This study provides relevant insights to water utilities aiming to design effective disinfectant residual management strategies for controlling monochloramine decay and DBP formation.

Identification of the key biochemical component contributing to disinfection byproducts in chlorinating algogenic organic matter

Disinfection byproducts (DBPs) remains an ongoing issue because of their widespread occurrence and toxicity. Various organic substances in Algogenic organic matter (AOM) can produce DBPs in the chlorination process. To provide specific suggestions for the targeted removal of DBP precursors in AOM, the main biochemical components in AOM were qualitatively and quantitatively analyzed. An accurate model for predicting the DBP formation potentials (DBPFPs) of AOM was herein developed based on the dissolved organic carbon of the five main biochemical components in AOM and the DBPFPs of their corresponding surrogates. The contributions of each biochemical component to the three DBP species were evaluated, and the key components were identified. The results showed that lipids, proteins, carbohydrates, humic acid-like substances, and fulvic acid-like substances were the main biochemical components in AOM. Thereof, proteins (71.2 ± 2.1%) and carbohydrates (53.1 ± 2.1%) were the major contributor to the carbon content in intracellular organic matter and extracellular organic matter, respectively. The contribution results of biochemical components to the formation of DBPs showed that proteins were the key contributor to DBPs, suggesting that the targeted removal of proteins before the chlorination process would effectively reduce DBPs from AOM.

Application of convolutional neural networks for prediction of disinfection by-products

Fluorescence spectroscopy can provide high-level chemical characterization and quantification that is suitable for use in online process monitoring and control. However, the high-dimensionality of excitation–emission matrices and superposition of underlying signals is a major challenge to implementation. Herein the use of Convolutional Neural Networks (CNNs) is investigated to interpret fluorescence spectra and predict the formation of disinfection by-products during drinking water treatment. Using deep CNNs, mean absolute prediction error on a test set of data for total trihalomethanes, total haloacetic acids, and the major individual species were all < 6 µg/L and represent a significant difference improved by 39–62% compared to multi-layer perceptron type networks. Heat maps that identify spectral areas of importance for prediction showed unique humic-like and protein-like regions for individual disinfection by-product species that can be used to validate models and provide insight into precursor characteristics. The use of fluorescence spectroscopy coupled with deep CNNs shows promise to be used for rapid estimation of DBP formation potentials without the need for extensive data pre-processing or dimensionality reduction. Knowledge of DBP formation potentials in near real-time can enable tighter treatment controls and management efforts to minimize the exposure of the public to DBPs.

Understanding the influence of pre-ozonation on the formation of disinfection byproducts and cytotoxicity during post-chlorination of natural organic matter: UV absorbance and electron-donating-moiety of molecular weight fractions.

Pre-ozonation can reduce the formation of disinfection byproducts (DBPs) and related adverse effects during subsequent chlorination, but the change of each molecular weight (MW) fraction during each step of combined pre-ozonation and post-chlorination has not been well illustrated. In this study, it was investigated in terms of electron-donating-moieties (EDMs) and UVA254 for a representative natural organic matter from Suwanee river (SRNOM). Pre-ozonation suppressed the post-chlorination of SRNOM through oxidation of almost all EDMs (>85%) and UVA254 (>90%) in high MW fractions (HMW, >3.2kDa) and moderate EDMs (43%) and UVA254 (72%) in medium MW fractions (MMW, 1.0-3.2kDa). Furthermore, pre-ozonation led to comparable abatements of EDMs and UVA254 for HMW fractions, but lower abatement of EDMs than UVA254 for MMW fractions. However, when t-BuOH was used as an •OH-quencher, pre-ozonation led to a few instances in which there were higher abatements of EDMs than UVA254 for the MMW fraction. These findings suggested that the HMW fraction dominantly underwent ring-cleavage of phenols via O3- or •OH-oxidation. Differently, the MMW fraction underwent ring-cleavage of phenols and quinones-formation via O3-oxidation, but occasionally underwent hydroxylation and hydro-phenol formation via •OH-oxidation. Because of forehand elimination of reactive moieties (e.g. EDMs), pre-ozonation obviously inhibited the formation of representative DBPs (67%-84% inhibition), total organic chloride (51% inhibition) and cytotoxicity (31% inhibition), but may have promoted the formation of carbonyl-DBPs (trichloroacetone and chloral hydrate). When compared with UVA254, EDMs would better for surrogate of DBPs formation. EDM abatement surrogated the formation of total organic chlorine (TOCl) and cytotoxicity following a two-stage phase, possibly because the speciation of DBPs and transformation products varied with the abatement of EDMs.

The effect of coagulation on the removal of algogenic organic matter and the optical parameters for predicting disinfection byproducts

Algae-derived disinfection byproducts (DBPs) are receiving increasing attention. Coagulation is the first water treatment section in removing algogenic organic matter (AOM). However, there is a significant knowledge gap in the effects of coagulation on DBPs produced from AOM. In this study, in view of the multi-component AOM, several analysis methods were combined to investigate the changes in AOM of Microcystic aeruginosa during the coagulation treatment, including ultraviolet–visible absorbance, multi-peaks Gaussian fitting method based on differential absorption spectroscopy, Excitation-emission matrix, and Fourier transform infrared spectroscopic analysis. To identify the characteristic parameters that could indicate the formation of DBPs, the yields of twenty-one DBP species produced from the residual AOM after the coagulation treatment were investigated. The correlations between DBPs and the spectral parameters were also analyzed. The results showed that aluminum salt coagulant could significantly remove protein-like compounds, chlorophyll, and phycocyanin in AOM, but it had a limited ability to precipitate AOM. With the increase of aluminum sulfate coagulant, the yields of DBPs produced from the residual extracellular organic matter decreased, while those produced from the residual intracellular organic matter decreased firstly and then gradually increased. The Pearson’s correlation results showed that the combination of fluorescent regions of protein-like and humic acid-like could be used as an optical surrogate for predicting the formation of DBPs.

Identification of unknown disinfection byproducts in drinking water produced from Taihu Lake source water

Although disinfection byproducts (DBPs) in drinking water have been suggested as a cancer causing factor, the causative compounds have not yet been clarified. In this study, we used liquid chromatography quadrupole-time-of-flight spectrometry (LC-QTOF MS) to identify the unknown disinfection byproducts (DBPs) in drinking water produced from Taihu Lake source water, which is known as a convergence point for the anthropogenic pollutants discharged from intensive industrial activities in the surrounding regions. In total, 91 formulas of DBPs were discovered through LC-QTOF MS nontarget screen, 81 of which have not yet been reported. Among the 91 molecules, 56 only contain bromine, 15 only contain chlorine and 20 DBPs have both bromine and chlorine atoms. Finally, five DBPs including 2,4,6-tribromophenol, 2,6-dibromo-4-chlorophenol, 2,6-dichloro-4-bromophenol, 4-bromo-2,6-di-tert-butylphenol and 3,6-dibromocarbazole were confirmed using standards. The former three compounds mainly formed in the predisinfection step (maximum concentration, 0.2-2.6 µg/L), while the latter two formed in the disinfection step (maximum concentration, 18.2-33.6 ng/L). In addition, 19 possible precursors of the discovered DBPs were detected, with the aromatic compounds being a major group. 2,6-di-tert-butylphenol as the precursor of 4-bromo-2,6-di-tert-butylphenol was confirmed with standard, with a concentration of 20.3 µg/L in raw water. The results of this study show that brominated DBPs which are possibly formed from industrial pollutants are relevant DBP species in drinking water produced form Taihu source water, suggesting protection of Taihu Lake source water is important to control the DBP risks.

Parallel factor analysis of fluorescence excitation emissions to identify seasonal and watershed differences in trihalomethane precursors

Concentration and chemical composition of dissolved organic matter (DOM) play a major role in formation and speciation of disinfection by-products, such as trihalomethanes (THMs), in water treatment plants (WTPs) during disinfection. This study characterized DOM across the process trains of WTPs using fluorescence excitation emission matrices (EEMs) together with parallel factor analysis (PARAFAC). The PARAFAC model was developed from 216 EEMs of bimonthly water samples from three WTPs in Khon Kaen, Thailand, from May 2018 to Mar 2019. Three PARAFAC components identified were humic-like DOM of terrestrial, and microbial or agricultural origin, while the one protein-like component was previously defined as tryptophan-like fluorophore. The relationships between water quality parameters, including the maximum fluorescent intensities (Fmax) of PARAFAC components and THM formation potential (THM-FP) were investigated using Spearman's rank correlation. The Fmax of PARAFAC components, UVA254, DOC, and THM-FP were greater in dry season. Chloroform was the primary THM formed at two sites using surface water as their water source, while the site using surface water with saline groundwater intrusion had higher concentration of brominated THMs. Results indicated that Fmax of humic-like components extracted by PARAFAC analysis were the most accurate THM-FP surrogate parameter assessed for the water samples tested and the correlations between Fmax and THM-FP were site specific (ρ = 0.81–0.85). The result demonstrates that fluorescence spectroscopy analysis has yielded insights into relationships between the DOM optical characteristics and their total THM-FP even at sites with different speciation of THMs.

Photooxidation of atrazine and its influence on disinfection byproducts formation during post-chlorination: effect of solution pH and mechanism

Partial photooxidation of micropollutants may lead to various degradation intermediates, obviously affecting disinfection byproducts (DBPs) formation during the post-chlorination process. The photooxidation of atrazine (ATZ) in aqueous solutions with low-pressure mercury UV lamps in UV, UV/H2O2 and UV/TiO2 treatment system and the formation of chlorinated disinfection byproducts (DBPs) during subsequent chlorination processes including dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), 1,1,1-trichloro-2-propanone (TCP), trichloromethane (TCM) and chloropicrin (CHP) were investigated in this study. The effect of solution pH on the oxidation pathway of ATZ in three UV photooxidation treatment process and the impact of photooxidation on the DBPs formations were assessed. Based on UPLC-ESI–MS/MS analyses, identification of main oxidation intermediates was performed and the plausible degradation pathways of ATZ in photooxidation system were proposed, indicating that photooxidation of ATZ in UV/H2O2 and UV/TiO2 process system was significantly pH-dependent processes. Dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), 1,1,1-trichloro-2-propanone (TCP), trichloromethane (TCM) and chloropicrin (CHP) were detected in photooxidized ATZ solutions. Compared to the other three DBPs, TCM and TCP were the main DBPs formed. The DBPs formations were greatly promoted in oxidized ATZ solutions. Solution pH and UV irradiation time exhibited obvious impact on the DBPs formation on the basis of DBP species. The variation tendency of DBPs observed relates to the combustion of ATZ in photooxidation system and the production oxidation intermediates.

Removal of the precursors of regulated DBPs and TOX from surface waters and wastewater effluents using mixed anion exchange resins

Both organic and inorganic precursors play important roles in the formation and speciation of disinfection by-products (DBPs). This study aimed to investigate the efficacy of three different anion exchange resins for removing both organic and inorganic DBP precursors simultaneously in a single treatment system. Resins in the single (Purolite®-Br, MIEX®-Br, and MIEX®-Gold) and mixed (Purolite®-Br with MIEX®-Gold and MIEX®-Br with MIEX®-Gold) application modes were tested and compared for the removal of dissolved organic carbon (DOC), bromide (Br−), and iodide (I−) from a raw source water and a treated wastewater effluent. Uniform formation condition (UFC) tests were conducted to measure the concentrations of trihalomethanes (THM4), haloacetic acids (HAA9), haloacetonitriles (HAN6), and total organic halides (TOX): total organic chlorine (TOCl), total organic bromine (TOBr), and total organic iodine (TOI) before and after the anion exchange resin treatments. The anion exchange treatment substantially lowered the DOC, UV254 absorbing matter, dissolved nitrogen (DN), Br−, and I−. Consequently, the formation of THM4, HAA9, HAN6, and TOX in the examined chlorinated water samples were reduced significantly. The maximum reduction in THM4 and TOX (66–69% and 61%, respectively) from wastewater effluent was achieved by the mixed resin system, which also reduced the THM4 and TOX by 77% and 77%, respectively, from raw source water. Overall, mixed resin systems (a DOC-selective and a Br-selective resin) resulted in lower amounts of THM4 and HAA9 formation during subsequent chlorination with lower bromine incorporation as compared to single resin systems. Furthermore, they exhibited lower TOBr formation, while TOI formation was not detected.