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.

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

BACKGROUND: 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. METHODS: 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. RESULTS: 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. CONCLUSIONS: 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.

Comprehensive comparison of water quality risk and microbial ecology between new and old cast iron pipe distribution systems.

The effects of cast iron pipe corrosion on water quality risk and microbial ecology in drinking water distribution systems (DWDSs) were investigated. It was found that trihalomethane (THMs) concentration and antibiotic resistance genes (ARGs) increased sharply in the old DWDSs. Under the same residual chlorine concentration conditions, the adenosine triphosphate concentration in the effluent of old DWDSs (Eff-old) was significantly higher than that in the effluent of new DWDSs. Moreover, stronger bioflocculation ability and weaker hydrophobicity coexisted in the extracellular polymeric substances of Eff-old, meanwhile, iron particles could be well inserted into the structure of the biofilms to enhance the mechanical strength and stability of the biofilms, hence enhancing the formation of THMs. Old DWDSs significantly influenced the microbial community of bulk water and triggered stronger microbial antioxidant systems response, resulting in higher ARGs abundance. Corroded cast iron pipes induced a unique interaction system of biofilms, chlorine, and corrosion products. Therefore, as the age of cast iron pipes increases, the fluctuation of water quality and microbial ecology should be paid more attention to maintain the safety of tap water.

Efficient trihalomethane quantification in drinking water for minimally-equipped water treatment plants labs.

Chlorine is a common disinfectant used in water treatment. However, its reaction with organic matter can lead to the formation of harmful byproducts, such as trihalomethanes (THMs), which are potentially carcinogenic. To address this issue, the aim of this work was to enhance a colorimetric method capable of quantifying THMs in drinking water through UV/Vis Spectrophotometry, using cost-effective equipment, and validate this methodology for the first time according to established validation protocols. The method's innovation involved replacing the solvent pentane with the more common hexane, along with adjusting the heating ramp, elucidating the mechanisms involved in the process. This method involves the reaction between THMs, pyridine, and NaOH to produce a colored compound, which is then monitored through molecular absorption spectroscopy in the visible region. The method was thoroughly validated, achieving a limit of detection of 13.41 µg L-1 and a limit of quantification of 40.65 µg L-1. Recovery assays ranged from 86.1 % to 90.7 %, demonstrating high accuracy. The quality of the linear fit for the analytical curve exceeded R2 > 0.98. The method was applied to real samples, revealing concentrations ranging from 13.58 to 55.46 µg L-1, all way below the legal limit in Brazil (Maximum Contaminant Levels (MCL) = 100 µg L-1). This cost-effective and straightforward method is suitable for integration into water treatment plant laboratories.

Chronic exposure to drinking water nitrate and trihalomethanes in the French CONSTANCES cohort.

Trihalomethanes (THMs) and nitrate are widespread chemicals in drinking water. Chronic exposure has been associated with increased cancer risk despite inconclusive evidence, partly due to the challenges in long-term exposure assessment and potential exposure misclassification. We estimated concentrations of nitrate and THMs in drinking water using a public regulatory monitoring database (SISE-Eaux) for CONSTANCES, a French population-based prospective cohort. We obtained 26,322,366 measurements of drinking water parameters from 2000 to 2020. We excluded missing, implausible and duplicated measurements; we corrected or imputed missing geocodes of sampling locations; we calculated the annual median concentration of nitrate and THMs by surveillance area. To predict missing annual median concentrations, linear mixed models with random intercept using surveillance area as a clustering variable were developed for each region for nitrate and the four THM components (chloroform, chlorodibromomethane, bromodichloromethane and bromoform) separately. Concentrations in the nearest surveillance area from the household were merged per year among 75,462 participants with residential history geocoded for 2000-2020. Estimated concentrations resulting from this approach were compared with measured concentrations in 100 samples collected in Paris, Rennes and Saint-Brieuc in 2021. Median annual concentrations of total THMs and nitrate at study participants' homes for 2000-2020 were, respectively, 15.7 µg/l (IQR: 15.2) and 15.2 mg/l (IQR: 20.8). Among these, 35% were based on measurements for nitrate (16% for THMs), 44% (46%) were predicted using on linear mixed models, and 21% (38%) were based on distribution unit median values. Conditional R2 predictive models ranged from 0.71 to 0.91 (median: 0.85) for nitrate, and from 0.48 to 0.80 for THMs (median: 0.68). These concentrations will allow future association analyses with risk of breast and colorectal cancer. Our cleaning process introduced here could be adapted to other large drinking water monitoring data.

Statistical modeling for iodinated trihalomethanes: Preformed chloramination versus prechlorination followed by ammonia addition.

Developing predictive models for iodo-trihalomethane (I-THM) formation in water is needed and valuable to minimize extensive and costly analysis. The main objective of this study was to develop a statistical model for the formation of six types of I-THMs under uniform formation conditions. Prediction of I-THM formation in two different water sources (natural organic matter [NOM] and algal organic matter [AOM]) were comprehensively evaluated during both preformed chloramination and prechlorination followed by ammonia addition conditions. In addition, the prediction of THM10 (sum of six I-THM and THM4) formation was conducted during both oxidation strategies for NOM waters. In total, 460 experimental results were compiled from the literature and our own database. The results showed the coefficient of determination (R2) values for the six I-THM species ranged between 0.53-0.68 and 0.35-0.79 in the preformed NH2Cl and perchlorinated NOM waters, respectively. Among all independent variables, the I- exhibited the most significant influence on the formation of all I-THM species in the preformed NH2Cl, while SUVA254 was the most influential parameter for perchlorinated NOM water. When the preformed chloramination was compared with prechlorination followed by ammonia addition, the R2 value for I-THMs (0.93) was higher than for THM4 formation (0.79) in preformed chloramination. In the prechlorination followed by ammonia addition condition, the model prediction of I-THMs (R2= 0.45) formation was lower than THM4 (R2= 0.96). Overall, the pH, I-, SUVA254, and oxidant type are all played crucial roles in determining the I-THM formation, impacting the overall effectiveness and predictability of the models.

Point-of-use chlorine residuals and disinfection byproduct occurrences in rural households served by public water utilities in Appalachian Virginia.

We characterized concentrations of trihalomethanes (THMs), a measure of disinfection byproducts (DBPs), in tap water samples collected from households with utility-supplied water in two rural counties in Appalachian Virginia, and assessed associations with pH, free chlorine, and metal ions which can impact THM formation. Free chlorine concentrations in all samples (n = 27 homes) complied with EPA drinking water guidelines, though 7% (n = 2) of first draw samples and 11% (n = 3) of 5-min flushed-tap water samples exceeded the US Safe Drinking Water Act (SDWA) maximum contaminant level (MCL) for THM (80 ppb). Regression analyses showed that free chlorine and pH were positively associated with the formation of THM levels above SDWA MCLs (OR = 1.04, p = 0.97 and OR = 1.74, p = 0.79, respectively), while temperature was negatively associated (OR = 0.78, p = 0.38). Of the eight utilities serving study households, samples from water served by three different utilities exceeded the EPA MCL for THM. Overall, these findings do not indicate substantial exposures to DBPs for rural households with utility-supplied water in this region of southwest Virginia. However, given the observed variability in THM concentrations between and across utilities, and established adverse health impacts associated with chronic and acute DBP exposure, more research on DBPs in rural Central Appalachia is warranted.

Disinfection by-product formation potential in response to variability in dissolved organic matter and nutrient inputs: Insights from a mesocosm study.

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

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

BACKGROUND: 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. METHODS: 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. RESULTS: 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. CONCLUSIONS: 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.

Non-target screening and prioritization of organic contaminants in seawater desalination and their ecological risk assessment.

The impact of desalination brine on the marine environment is a global concern. Regarding this, salinity is generally accepted as the major environmental factor in desalination concentrate. However, recent studies have shown that the influence of organic contaminants in brine cannot be ignored. Therefore, a non-targeted screening method based on comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GC × GC-qMS) was developed for identifying organic contaminants in the desalination brine. A total of 404 compounds were tentatively identified from four seawater desalination plants (three reverse osmosis plants and one multiple effect distillation plant) in China. The identified compounds were prioritized based on their persistence, bioaccumulation, ecotoxicity, usage, and detection frequency. Twenty-one (21) compounds (seven phthalates, ten pesticides, four trihalomethanes) were then selected for further quantitative analysis and ecological risk assessment, including compounds from the priority list along with substances from the same chemical classes. Ecologically risky substances in brine include diisobutylphthalate and bis(2-Ethylhexyl) phthalate, atrazine and acetochlor, and bromoform. Most of the contaminants come from raw seawater, and no high risk contaminants introduced by the desalination process have been found except for disinfection by-products. In brine discharge management, people believed that all pollution in raw seawater was concentrated by desalination process. This study shows that not all pollutants are concentrated during the desalination process. In this study, the total concentration of pesticide in the brine increased by 58.42%. The concentration of ∑PAEs decreased by 13.65% in reverse osmosis desalination plants and increased by 10.96% in the multi-effect distillation plant. The concentration of trihalomethane increased significantly in the desalination concentrate. The change in the concentration of pollutants in the desalination concentrate was related to the pretreatment method and the chemical characteristics of the contaminants. The method and results given in this study hinted a new idea to identify and control the environmental impact factors of brine.

Control of chlorination disinfection by-products in drinking water by combined nanofiltration process: A case study with trihalomethanes and haloacetic acids.

Disinfection by-products (DBPs) are prevalent contaminants in drinking water and are primarily linked to issues regarding water quality. These contaminants have been associated with various adverse health effects. Among different treatment processes, nanofiltration (NF) has demonstrated superior performance in effectively reducing the levels of DBPs compared to conventional processes and ozone-biological activated carbon (O3-BAC) processes. In this experiment, we systematically investigated the performance of three advanced membrane filtration treatment schemes, namely "sand filter + nanofiltration" (SF + NF), "sand filter + ozone-biological activated carbon + nanofiltration" (SF + O3-BAC + NF), and "ultrafiltration + nanofiltration" (UF + NF), in terms of their ability to control disinfection by-product (DBP) formation in treated water, analyzed the source and fate of DBP precursors during chlorination, and elucidated the role of precursor molecular weight distribution during membrane filtration in relation to DBP formation potential (DBPFP). The results indicated that each treatment process reduced DBPFP, as measured by trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP), with the SF + O3-BAC + NF process being the most effective (14.27 µg/L and 14.88 µg/L), followed by the SF + NF process (21.04 µg/L and 16.29 µg/L) and the UF + NF process (26.26 µg/L and 21.75 µg/L). Tyrosine, tryptophan, and soluble microbial products were identified as the major DBP precursors during chlorination, with their fluorescence intensity decreasing gradually as water treatment progressed. Additionally, while large molecular weight organics (60-100,000 KDa) played a minor role in DBPFP, small molecular weight organics (0.2-5 KDa) were highlighted as key contributors to DBPFP, and medium molecular weight organics (5-60 KDa) could adhere to the membrane surface and reduce DBPFP. Based on these findings, the combined NF process can be reasonably selected for controlling DBP formation, with potential long-term benefits for human health.

Formation potential of disinfection byproducts during chlorination of petroleum hydrocarbon-contaminated drinking water.

Recent leaks of underground fuel storage tanks in the Pearl Harbor region have led to direct release of un-weathered petroleum hydrocarbons (PHCs) into drinking water sources, which then directly underwent chlorination disinfection treatment. Since the control of disinfection byproducts (DBPs) traditionally focuses natural organic matters (NOM) from source water and little is known about the interactions between free chlorine and un-weathered PHCs, laboratory chlorination experiments in batch reactors were conducted to determine the formation potential of DBPs during chlorination of PHC-contaminated drinking water. Quantitative analysis of regulated DBPs showed that significant quantities of THM4 (average 3,498 µg/L) and HAA5 (average 355.4 µg/L) compounds were formed as the result of chlorination of un-weathered PHCs. Amongst the regulated DBPs, THM4, which were comprised primarily of chloroform and bromodichloromethane, were more abundant than HAA5. Numerous unregulated DBPs and a large diversity of unidentified potentially halogenated organic compounds were also produced, with the most abundant being 1,1-dichloroacetone, 1,2-dibromo-3-chloropropane, chloropicrin, dichloroacetonitrile, and trichloracetonitrile. Together, the results demonstrated the DBP formation potential when PHC-contaminated water undergoes chlorination treatment. Further studies are needed to confirm the regulated DBP production and health risks under field relevant conditions.

Trihalomethanes in global drinking water: Distributions, risk assessments, and attributable disease burden of bladder cancer.

This study aimed to assess the global spatiotemporal variations of trihalomethanes (THMs) in drinking water, evaluate their cancer and non-cancer risks, and THM-attributable bladder cancer burden. THM concentrations in drinking water around fifty years on a global scale were integrated. Health risks were assessed using Monte Carlo simulations and attributable bladder cancer burden was estimated by comparative risk assessment methodology. The results showed that global mean THM concentrations in drinking water significantly decreased from 78.37 µg/L (1973-1983) to 51.99 µg/L (1984-2004) and to 21.90 µg/L (after 2004). The lifestage-integrative cancer risk and hazard index of THMs through all exposure pathways were acceptable with the average level of 6.45 × 10-5 and 7.63 × 10-2, respectively. The global attributable disability adjusted of life years (DALYs) and the age-standardized DALYs rate (ASDR) dropped by 16% and 56% from 1990-1994 to 2015-2019, respectively. A big decline in the attributable ASDR was observed in the United Kingdom (62%) and the United States (27%), while China experienced a nearly 3-fold increase due to the expanded water supply coverage and increased life expectancy. However, China also benefited from the spread of chlorination, which helped reduce nearly 90% of unsafe-water-caused mortality from 1998 to 2018.

The insightful water quality analysis and predictive model establishment via machine learning in dual-source drinking water distribution system.

Dual-source drinking water distribution systems (DWDS) over single-source water supply systems are becoming more practical in providing water for megacities. However, the more complex water supply problems are also generated, especially at the hydraulic junction. Herein, we have sampled for a one-year and analyzed the water quality at the hydraulic junction of a dual-source DWDS. The results show that visible changes in drinking water quality, including turbidity, pH, UV254, DOC, residual chlorine, and trihalomethanes (TMHs), are observed at the sample point between 10 and 12 km to one drinking water plant. The average concentration of residual chlorine decreases from 0.74 ± 0.05 mg/L to 0.31 ± 0.11 mg/L during the water supplied from 0 to 10 km and then increases to 0.75 ± 0.05 mg/L at the end of 22 km. Whereas the THMs shows an opposite trend, the concentration reaches to a peak level at hydraulic junction area (10-12 km). According to parallel factor (PARAFAC) and high-performance size-exclusion chromatography (HPSEC) analysis, organic matters vary significantly during water distribution, and tryptophan-like substances and amino acids are closely related to the level of THMs. The hydraulic junction area is confirmed to be located at 10-12 km based on the water quality variation. Furthermore, data-driven models are established by machine learning (ML) with test R2 higher than 0.8 for THMs prediction. And the SHAP analysis explains the model results and identifies the positive (water temperature and water supply distance) and negative (residual chlorine and pH) key factors influencing the THMs formation. This study conducts a deep understanding of water quality at the hydraulic junction areas and establishes predictive models for THMs formation in dual-sources DWDS.

Climate change and future water demand: Implications for chlorine and trihalomethanes management in water distribution systems.

The global change in surface water quality calls for increased preparedness of drinking water utilities. The increasing frequency of extreme climatic events combined with global warming can impact source and treated water characteristics such as temperature and natural organic matter. On the other hand, water saving policies in response to water and energy crisis in some countries can aggravate the situation by increasing the water residence time in the drinking water distribution system (DWDS). This study investigates the individual and combined effect of increased dissolved organic carbon (DOC), increased temperature, and reduced water demand on fate and transport of chlorine and trihalomethanes (THMs) within a full-scale DWDS in Canada. Chlorine and THM prediction models were calibrated with laboratory experiments and implemented in EPANET-MATLAB toolkit for prediction in the DWDS under different combinations of DOC, temperature, and demand. The duration of low chlorine residuals (<0.2 mg/L) and high THM (>80 µg/L) periods within a day in each scenario was reported using a reliability index. Low-reliability zones prone to microbial regrowth or high THM exposure were then delineated geographically on the city DWDS. Results revealed that water demand reduction primarily affects chlorine availability, with less concern for THM formation. The reduction in nodal chlorine reliability was gradual with rising temperature and DOC of the treated water and reducing water demand. Nodal THM reliability remained unchanged until certain thresholds were reached, i.e., temperature >25 °C for waters with DOC <1.52 mg/L, and DOC >2.2 mg/L for waters with temperature = 17 °C. At these critical thresholds, an abrupt network-wide THM exceedance of 80 µg/L occurred. Under higher DOC and temperature levels in future, employing the proposed approach revealed that increasing the applied chlorine dosage (which is a conventional method used to ensure sufficient chlorine coverage) results in elevated exposure toTHMs and is not recommended. This approach aids water utilities in assessing the effectiveness of different intervention measures to solve water quality problems, identify site-specific thresholds leading to major decreases in system reliability, and integrate climate adaptation into water safety management.

Formation and control of disinfection by-products during the trichloroisocyanuric acid disinfection in swimming pool water.

The increasing demand for trichloroisocyanuric acid (TCCA) in swimming pool disinfection highlights the need to evaluate its applicability in terms of disinfection by-product (DBP) formation. Nevertheless, there is limited understanding of DBP formation and control during TCCA disinfection, particularly concerning the effects of various management parameters. This study aimed to fill this knowledge gap by comprehensively investigating DBP formation during TCCA chlorination, with a particular focus on assessing the contribution and interaction of influencing factors using Box-Behnken Design and response surface methodology. Results indicated that the concentrations of trichloroacetaldehyde, chloroform, dichloroacetic acid, trichloroacetic acid, and dichloroacetonitrile produced by TCCA disinfectant were 42.5%, 74.0%, 48.1%, 94.7% and 42.6% of those by the conventional sodium hypochlorite disinfectant, respectively. Temperature exhibited the most significant impact on chloroform formation (49%), while pH played a major role in trichloroacetaldehyde formation (44%). pH2 emerged as the primary contributor to dichloroacetic acid (90%) and trichloroacetic acid (93%) formation. The optimum water quality conditions were determined based on the minimum total DBPs (pH = 7.32, Temperature = 23.7 °C, [Cl-] = 437 mg/L). Chlorine dosage and contact time exhibited greater influence than precursor concentration on chloroform, dichloroacetonitrile, trichloroacetaldehyde, trichloroacetic acid, and total DBPs. Although the interaction between water quality parameters was weak, the interaction between disinfection operating parameters demonstrated substantial effects on DBP formation (8.56-19.06%). Furthermore, the DBP predictive models during TCCA disinfection were provided for the first time, which provides valuable insights for DBP control and early warning programs.

Rapid degradation of brominated haloacetaldehydes at elevated temperature: Kinetics and newly discovered mechanisms.

As an important class of disinfection byproducts (DBPs) of emerging concern, haloacetaldehydes (HALs) undergo degradation and transformation under environmentally relevant conditions. In this study, the stability of chlorinated and brominated HALs was investigated at different pHs and water temperatures. Results indicated that the degradation of HALs followed second-order kinetics. Surprisingly, rapid degradation of Br-HALs at elevated temperature was newly discovered in this study. At 50 °C and pH 7.5, over 90 % of TBAL degraded in 8 min, while the degradation of TCAL was ∼1 %. Moreover, increasing pH also facilitated the degradation of HALs and the alkaline degradation rate constants ( [Formula: see text] ) were found to be 7-9 orders of magnitude higher than their neutral degradation rate constants ( [Formula: see text] ). Under conditions relevant to environment and DBP measurement, HALs mainly degraded to form corresponding trihalomethanes and formate via decarburization pathway, which accounted for 70-93 % of HALs loss. The remaining 7-30 % of HAL loss was attributed to the dehalogenation pathway newly proposed in this study, successfully closing halogen balance during HAL degradation. In addition, a quantitative structure-activity relationship (QSAR) model was established for HAL degradation and the degradation rate constants for three mono-HALs were predicted at different temperature. The kinetic models and reaction rate constants obtained in this study can be used for quantitative predictions of HAL concentrations in drinking water, which is beneficial for monitoring and control of these emerging DBPs. Furthermore, considering the rapid degradation of Br-HALs into corresponding products, the temperature during sample pre-treatment can have a significant impact on DBP analysis.

Exposure to disinfection by-products and risk of cancer: A systematic review and dose-response meta-analysis.

Disinfection by-products (DBPs), including trihalomethanes (THMs) and haloacetic acids (HAAs), have attracted attention due to their carcinogenic properties, leading to varying conclusions. This meta-analysis aimed to evaluate the dose-response relationship and the dose-dependent effect of DBPs on cancer risk. We performed a selective search in PubMed, Web of Science, and Embase databases for articles published up to September 15th, 2023. Our meta-analysis eventually included 25 articles, encompassing 8 cohort studies with 6038,525 participants and 10,668 cases, and 17 case-control studies with 10,847 cases and 20,702 controls. We observed a positive correlation between increased cancer risk and higher concentrations of total trihalomethanes (TTHM) in water, longer exposure durations, and higher cumulative TTHM intake. These associations showed a linear trend, with relative risks (RRs) and 95 % confidence intervals (CIs) being 1.02 (1.01-1.03), 1.04 (1.02-1.06), and 1.02 (1.00-1.03), respectively. Gender-specific analyses revealed slightly U-shaped relationships in both males and females, with males exhibiting higher risks. The threshold dose for TTHM in relation to cancer risk was determined to be 55 µg/L for females and 40 µg/L for males. A linear association was also identified between bladder cancer risk and TTHM exposure, with an RR and 95 % CI of 1.08 (1.05-1.11). Positive linear associations were observed between cancer risk and exposure to chloroform, bromodichloromethane (BDCM), and HAA5, with RRs and 95 % CIs of 1.02 (1.01-1.03), 1.33 (1.18-1.50), and 1.07 (1.03-1.12), respectively. Positive dose-dependent effects were noted for brominated THMs above 35 µg/L and chloroform above 75 µg/L. While heterogeneity was observed in the studies for quantitative synthesis, no publication bias was detected. Exposure to TTHM, chloroform, BDCM, or HAA5 may contribute to carcinogenesis, and the risk of cancer appears to be dose-dependent on DBP exposure levels. A cumulative effect is suggested by the positive correlation between TTHM exposure and cancer risk. Bladder cancer and endocrine-related cancers show dose-dependent and positive associations with TTHM exposure. Males may be more susceptible to TTHM compared to females.

Adsorption, boiling or membrane filtration for disinfection by-product removal: How to make our drinking water safer?

Disinfection by-products (DBPs) generated in drinking water have become a global concern due to their potential harm to human health. Nevertheless, there are few studies about different point-of-use water treatments in household drinking water. The study aims to compare the effectiveness of three point-of-use water treatments: adsorption, boiling, and membrane filtration. The experimental results showed that the initial average concentration of volatile DBPs and non-volatile DBPs for tap water were 63.71 µg/L and 6.33 µg/L. The removal efficiency of DBPs for adsorption which were 75.6 % (the filter volumes from 0 L to 20 L) and 45.4 % (the filter volumes from 20 L to 50 L) during the service life of the filter element (50 L). Boiling had a high removal efficiency for volatile DBPs like trihalomethanes (THMs), haloacetaldehydes (HALs), haloacetonitriles (HANs), and haloketones (HKs) (90.5 %, 100 %, 100 %, and 100 %, respectively). However, boiling had a low removal efficiency which was 15 % in removing non-volatile DBPs like haloacetic acids (HAAs). Membrane filtration had a middle removal efficiency for THMs, HAAs, HALs, HKs, and HANs (45.3 %, 75.2 %, 46.5 %, 47.6 %, and 100 %, respectively). Through analysis of the correlation between dissolved organic matter (DOM) removal efficacy and DBP removal efficiency, it was found that the strongest correlation was observed between UV254 and DBP removal efficiency. Boiling showed a lower estimated cytotoxicity of DBPs compared to adsorption and membrane filtration. Cancer risk assessment of DBPs was below the specified risk range for three point-of-use water treatments. This study provides a reference for choosing point-of-use water treatments in household drinking water.

Low Parts Per Trillion Detection of Iodinated Disinfection Byproducts in Drinking Water and Urine using Vacuum-Assisted Sorbent Extraction and GC-MS/MS.

Disinfection byproducts (DBPs) are ubiquitous environmental contaminants, which are present in virtually all drinking water and linked to detrimental health effects. Iodinated-DBPs are more cytotoxic and genotoxic than chloro- and bromo-DBPs and are formed during disinfection of iodide-containing source water. Liquid-liquid extraction (LLE) paired with gas chromatography (GC)-mass spectrometry (MS) has been the method of choice in the study of low molecular weight iodinated-DBPs; however, this method is laborious and time-consuming and struggles with complex matrices. We developed an environmentally friendly method utilizing headspace solid phase extraction with the application of vacuum to measure six iodinated-trihalomethanes (I-THMs) in drinking water and urine. Vacuum-assisted sorbent extraction (VASE) has the ability to exhaustively and rapidly extract volatile and semivolatile compounds from liquid matrices without the use of solvent. Using VASE with GC-MS/MS provides improved analyte recovery and reduced matrix interference compared to LLE. Additionally, VASE enables extraction of 30 samples simultaneously with minimal sample handling and improved method reproducibility. Using VASE with GC-MS/MS, we achieved quantification limits of 3-4 ng/L. This technique was demonstrated on drinking water from four cities, where five I-THMs were quantified at levels 10-33 times below comparable LLE methods with 10 times lower volumes of sample (10 mL vs 100 mL).