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.

Drinking water source and exposure to regulated water contaminants in the California Teachers Study cohort.

BACKGROUND: Pollutants including metals/metalloids, nitrate, disinfection byproducts, and volatile organic compounds contaminate federally regulated community water systems (CWS) and unregulated domestic wells across the United States. Exposures and associated health effects, particularly at levels below regulatory limits, are understudied. OBJECTIVE: We described drinking water sources and exposures for the California Teachers Study (CTS), a prospective cohort of female California teachers and administrators. METHODS: Participants' geocoded addresses at enrollment (1995-1996) were linked to CWS service area boundaries and monitoring data (N = 115,206, 92%); we computed average (1990-2015) concentrations of arsenic, uranium, nitrate, gross alpha (GA), five haloacetic acids (HAA5), total trihalomethanes (TTHM), trichloroethylene (TCE), and tetrachloroethylene (PCE). We used generalized linear regression to estimate geometric mean ratios of CWS exposures across demographic subgroups and neighborhood characteristics. Self-reported drinking water source and consumption at follow-up (2017-2019) were also described. RESULTS: Medians (interquartile ranges) of average concentrations of all contaminants were below regulatory limits: arsenic: 1.03 (0.54,1.71) µg/L, uranium: 3.48 (1.01,6.18) µg/L, GA: 2.21 (1.32,3.67) pCi/L, nitrate: 0.54 (0.20,1.97) mg/L, HAA5: 8.67 (2.98,14.70) µg/L, and TTHM: 12.86 (4.58,21.95) µg/L. Among those who lived within a CWS boundary and self-reported drinking water information (2017-2019), approximately 74% self-reported their water source as municipal, 15% bottled, 2% private well, 4% other, and 5% did not know/missing. Spatially linked water source was largely consistent with self-reported source at follow-up (2017-2019). Relative to non-Hispanic white participants, average arsenic, uranium, GA, and nitrate concentrations were higher for Black, Hispanic and Native American participants. Relative to participants living in census block groups in the lowest socioeconomic status (SES) quartile, participants in higher SES quartiles had lower arsenic/uranium/GA/nitrate, and higher HAA5/TTHM. Non-metropolitan participants had higher arsenic/uranium/nitrate, and metropolitan participants had higher HAA5/TTHM. IMPACT: Though average water contaminant levels were mostly below regulatory limits in this large cohort of California women, we observed heterogeneity in exposures across sociodemographic subgroups and neighborhood characteristics. These data will be used to support future assessments of drinking water exposures and disease risk.

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.

Association of blood trihalomethane concentrations with diabetes mellitus in older adults in the US: a cross-sectional study of NHANES 2013-2018.

Background: Previous studies have demonstrated that there is a correlation between trihalomethanes and disease progression, such as allergic diseases. As we know, only few studies focused on the relationship between trihalomethanes and metabolic diseases, such as diabetes mellitus. Objective: The aim of this study was to further explore the associations between blood trihalomethane concentrations and diabetes mellitus in older adults in the US. Methods: Data were collected from the National Health and Nutrition Examination Study (NHANES) database in the survey cycle during 2013 to 2018, including 2,511 older adults in the US whose blood trihalomethane concentrations were measured, involving chloroform (TCM) and brominated trihalomethanes (Br-THMs). Br-THMs include bromodichloromethane (BDCM), dibromochloromethane (DBCM), and bromoform (TBM). Meanwhile, the concentration of total trihalomethanes (TTHMs) was also measured later. A multivariate logistic regression and restricted cubic spline were used to examine the relationship between blood THMs and diabetes mellitus. Meanwhile, we performed a subgroup analysis, which aims to explore the stability of this relationship in different subgroups. In order to further consider the impact of various disinfection by-products on diabetes, we also used weighted quantile sum (WQS). To explore the correlation in trihalomethanes, we plot a correlation heatmap. Results: Adjusting for potential confounders, we found that there was a significant negative association between chloroform and diabetes mellitus [Model 1 (adjusted for covariates including age, sex, and race, OR = 0.71; 95% CI: 0.50-1.02; p = 0.068; p for trend = 0.094); Model 2 (adjusted for all covariates, OR = 0.68; 95% CI: 0.48-0.96; p = 0.029; p for trend = 0.061)]. In the bromodichloromethane, we reached a conclusion that is similar to TCM [Model 1 (adjusted for covariates including age, sex, and race, OR = 0.54; 95% CI: 0.35-0.82; p = 0.005; p for trend = 0.002); Model 2 (adjusted for all covariates, OR = 0.54; 95% CI: 0.35-0.82; p = 0.003; p for trend = 0.002)]. Meanwhile, the restricted cubic spline curve also further confirms this result (p overall = 0.0027; p overall< 0.001). Based on the analysis in the subgroups, we found that the value p for interaction in the majority of subgroups is higher than 0.1. Trihalomethanes and diabetes were inversely associated, and in the WQS, chloroform and bromodichloromethane were found to be the major contributors to this relationship. In the correlation analysis, we found that most trihalomethanes have a weak correlation, except for TBM and TCM with a strong correlation. Conclusion: Our results in this study showed that blood chloroform, bromodichloromethane concentrations, and diabetes mellitus in older adults in the US are negatively correlated, suggesting that chloroform and bromodichloromethane can be protective factors for diabetes.

Complex impact of metals on the fate of disinfection by-products in drinking water pipelines: A systematic review.

Metals in the drinking water distribution system (DWDS) play an important role on the fate of disinfection by-products (DBPs). They can increase the formation of DBPs through several mechanisms, such as enhancing the proportion of reactive halogen species (RHS), catalysing the reaction between natural organic matter (NOM) and RHS through complexation, or by increasing the conversion of NOM into DBP precursors. This review comprehensively summarizes these complex processes, focusing on the most important metals (copper, iron, manganese) in DWDS and their impact on various DBPs. It organizes the dispersed 'metals-DBPs' experimental results into an easily accessible content structure and presents their underlying common or unique mechanisms. Furthermore, the practically valuable application directions of these research findings were analysed, including the toxicity changes of DBPs in DWDS under the influence of metals and the potential enhancement of generalization in DBP model research by the introduction of metals. Overall, this review revealed that the metal environment within DWDS is a crucial factor influencing DBP levels in tap water.

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.

Haloketones: A class of unregulated priority DBPs with high contribution to drinking water cytotoxicity.

Although unregulated aliphatic disinfection byproducts (DBPs) had a much higher concentration and cytotoxicity than known aromatic DBPs, a recent study indicated that seven classes of regulated and unregulated priority DBPs (one and two-carbon-atom DBPs) just accounted for 16.2% of disinfected water cytotoxicity in the U.S., meaning some of the highly toxic aliphatic DBPs may be overlooked. Haloketones (HKs) are an essential class of priority DBPs with a 1-100 µg/L concentration in drinking water but lack cytotoxicity data. This study investigated the cytotoxicity of seven HKs using Chinese hamster ovary (CHO) cells. The order for cytotoxicity of HKs from most to least toxic was: 1,3-dichloroacetone (LC50: 1.0 ± 0.20 µM) ≈ 1,3-dibromoacetone (1.5 ± 0.19 µM) ≈ bromoacetone (1.9 ± 0.49 µM) > chloroacetone (4.3 ± 0.22 µM) > 1,1,3-trichloropropanone (6.6 ± 0.46 µM) > 1,1,1-trichloroacetone (222 ± 7.7 µM) > hexachloroacetone (3269 ± 344 µM). The cytotoxicity of HKs was higher than most regulated and priority aliphatic DBPs in mono-halogenated, di-halogenated, and tri-halogenated categories. A prediction model of HK cytotoxicity was developed based on the quantitative structure-activity relationship (QSAR), optimizing structures and computing descriptors with Gaussian 09 W. The average concentrations of HKs in representative drinking water samples from South Carolina (U.S.) and Suzhou (China) were 12.4 and 0.9 µg/L, respectively, accounting for 18.8% and 1.7% of their specific total DBPs measured (i.e. not TOX). For South Carolina drinking water, their contributions to total calculated additive cytotoxicity of aliphatic DBPs and overall drinking water cytotoxicity were 86.7% and 14.0%, respectively, demonstrating that HKs are an essential class of overlooked DBPs with a high contribution to drinking water cytotoxicity. Our study can help to explain the conflict that why regulated and priority DBPs (except HKs) just accounted for 16% of chlorinated drinking water cytotoxicity even enough they had much higher concentration and cytotoxicity than known aromatic DBPs.

Urinary haloacetic acid concentrations in relation to sex and thyroid hormones among reproductive-aged men.

Sex and thyroid hormones are critical for male reproductive health. However, the associations between haloacetic acid (HAA) exposure - a known endocrine disruptor - and sex and thyroid hormones in humans remains unclear. We thus recruited 502 male participants seeking fertility evaluation from a reproductive center. We measured concentrations of sex and thyroid hormones in a single blood sample and dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) in repeated urine samples. Multivariable linear regression models were constructed to evaluate the associations between HAA concentrations and hormone measurements. After adjusting for potential confounders and urinary creatinine concentrations, urinary concentrations of TCAA were inversely associated with serum levels of sex hormone-binding globulin (SHBG), testosterone (T), T/luteinizing hormone ratio (T/LH), and thyroid stimulating hormone (TSH) (all P for trend < 0.10). Compared with participants in the lowest quartile of TCAA concentrations, those in the highest quartile had reduced serum levels of SHGB by 14.2 % (95% CI: -26.7, -3.0 %), T by 11.1 % (95% CI: -21.7, -1.3 %), T/LH by 21.0 % (95% CI: -36.7, -7.1 %), and TSH by 19.1 % (95% CI: -39.7, -1.5 %). Additionally, we observed inverse associations between continuous measurements of urinary HAAs and serum levels of free T, bioactive T, and estradiol. Our findings suggest that male HAA exposure may be associated with disrupted sex and thyroid function.

Impact of ozonation on disinfection byproducts formation from phenylalanine during chlorination.

As a strong oxidizing agent, ozone is used in some water treatment facilities for disinfection, taste and odor control, and removal of organic micropollutants. Phenylalanine (Phe) was used as the target amino acid to comprehensively investigate variability of disinfection byproducts (DBPs) formation during chlorine disinfection and residual chlorine conditions subsequent to ozonation. The results showed that subsequent to ozonation, the typical regulated and unregulated DBPs formation potential (DBPsFP), including trichloromethane (TCM), dichloroacetonitrile (DCAN), chloral hydrate (CH), dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), and trichloroacetamide (TCAcAm) increased substantially, by 2.4, 3.3, 5.6, 1.2, 2.5, and 6.0 times, respectively, compared with only chlorination. Ozonation also significantly increased the DBPs yield under a 2 day simulated residual chlorine condition that mimicked the water distribution system. DBPs formations followed pseudo first order kinetics. The formation rates of DBPs in the first 6 hr were higher for TCM (0.214 hr-1), DCAN (0.244 hr-1), CH (0.105 hr-1), TCAcAm (0.234 hr-1), DCAA (0.375 hr-1) and TCAA (0.190 hr-1) than thereafter. The peak DBPsFP of TCM, DCAN, CH, TCAcAm, DCAA, and TCAA were obtained when that ozonation time was set at 5-15 min. Ozonation times > 30 min increased the mineralization of Phe and decreased the formation of DBPs upon chlorination. Increasing bromine ion (Br-) concentration increased production of bromine- DBPs and decreased chlorine-DBPs formation by 59.3%-92.2% . Higher ozone dosages and slight alkaline favored to reduce DBP formation and cytotoxicity. The ozonation conditions should be optimized for all application purposes including DBPs reduction.

Molecularly imprinted polymers and porous organic frameworks based analytical methods for disinfection by-products in water and wastewater.

Disinfection by-products (DBPs) with heritage toxicity, mutagenicity and carcinogenicity are one kind of important new pollutants, and their detection and removal in water and wastewater has become a common challenge facing mankind. Advanced functional materials with ideal selectivity, adsorption capacity and regeneration capacity provide hope for the determination of DBPs with low concentration levels and inherent molecular structural similarity. Among them, molecularly imprinted polymers (MIPs) are favored, owing to their predictable structure, specific recognition and wide applicability. Also, metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs) with unique pore structure, large specific surface area and easy functionalization, attract increasing interest. Herein, we review recent advances in analytical methods based on the above-mentioned three functional materials for DBPs in water and wastewater. Firstly, MIPs, MOFs and COFs are briefly introduced. Secondly, MIPs, MOFs and COFs as extractants, recognition element and adsorbents, are comprehensively discussed. Combining the latest research progress of solid-phase extraction (SPE), sensor, adsorption and nanofiltration, typical examples on MIPs and MOFs/COFs based analytical and removal applications in water and wastewater are summarized. Finally, the application prospects and challenges of the three functional materials in DBPs analysis are proposed to promote the development of corresponding analytical methods.

CdS-Based Hydrothermal Photocatalysts for Complete Reductive Dehalogenation of a Chlorinated Propionic Acid in Water by Visible Light.

Cadmium sulfide (CdS)-based photocatalysts are prepared following a hydrothermal procedure (with CdCl2 and thiourea as precursors). The HydroThermal material annealed (CdS-HTa) is crystalline with a band gap of 2.31 eV. Photoelectrochemical investigation indicates a very reducing photo-potential of -0.9 V, which is very similar to that of commercial CdS. CdS-HTa, albeit having similar reducing properties, is more active than commercial CdS in the reductive dehalogenation of 2,2-dichloropropionic acid (dalapon) to propionic acid. Spectroscopic, electro-, and photoelectrochemical investigation show that photocatalytic properties of CdS are correlated to its electronic structure. The reductive dehalogenation of dalapon has a double significance: on one hand, it represents a demanding reductive process for a photocatalyst, and on the other hand, it has a peculiar interest in water treatment because dalapon can be considered a representative molecule of persistent organic pollutants and is one of the most important disinfection by products, whose removal from the water is the final obstacle to its complete reuse. HPLC-MS investigation points out that complete disappearance of dalapon passes through 2-monochloropropionic acid and leads to propionic acid as the final product. CdS-HTa requires very mild working conditions (room temperature, atmospheric pressure, natural pH), and it is stable and recyclable without significant loss of activity.

Urinary haloacetic acid concentrations and thyroid function among women: Results from the TREE study.

BACKGROUND: Disinfection byproducts (DBPs) have been shown to impair thyroid function in experimental models. However, epidemiological evidence is scarce. METHODS: This study included 1190 women undergoing assisted reproductive technology (ART) treatment from the Tongji Reproductive and Environmental (TREE) cohort from December 2018 to August 2021. Serum thyrotropin (TSH), free triiodothyronine (FT3), and free thyroxine (FT4) were measured as indicators of thyroid function. FT4/FT3 and TSH/FT4 ratios were calculated as markers of thyroid hormone homeostasis. Dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA), the two most abundant HAAs, in urine were detected to assess individual DBP exposures. RESULTS: After adjusting for relevant covariates, positive associations were observed between urinary TCAA concentrations and serum TSH and TSH/FT4 levels (e.g., percent change = 5.82 %, 95 % CI: 0.70 %, 11.21 % for TSH), whereas inverse associations were found for serum FT3 and FT4 (e.g., percent change = -1.29 %, 95 % CI: -2.49 %, -0.07 % for FT3). There also was a negative association between urinary DCAA concentration and serum FT4/FT3 (percent change = -2.49 %, 95 % CI: -4.71 %, -0.23 %). These associations were further confirmed in the restricted cubic spline and generalized additive models with linear or U-shaped dose-response relationships. CONCLUSION: Urinary HAAs were associated with altered thyroid hormone homeostasis among women undergoing ART treatment.

Effect of exposure to disinfection by-products during swimming exercise on asthma-related immune responses.

Swimming is a widely practiced exercise in modern society, where there is a heightened interest in health. The exceptional benefits of swimming are well-known, yet the issue of water quality management inevitably arises due to its nature as an aquatic exercise. Several studies reported that chlorine disinfectants commonly used in swimming pool water disinfection could degrade into toxic disinfection by-products (DBPs) and suggested that the DBPs might induce respiratory disorders, including asthma. Conversely, there were also reports that the DBPs had no significant effects on respiratory conditions. In this study, we investigated the influence of swimming exercise and DBPs on asthma. The decomposition products had little effect on the number of T cells in various immune organs. However, swimming exercise was found to increase the cell count in proportion to the exercise duration. Nevertheless, there were no significant changes in other immune cells and the secretion of asthma-related cytokines. These findings indicate that the effects of swimming pool DBPs on respiratory conditions during swimming exercise are either negligible or absent, and instead, the immunological benefits gained through consistent swimming exercise outweigh any potential drawbacks.

Research progress on the generation of NDMA by typical PPCPs in disinfection treatment of water environment in China: A review.

The drugs and personal care products in water sources are potential threats to the ecological environment and drinking water quality. In recent years, the presence of PPCPs has been detected in multiple drinking water sources in China. PPCPs are usually stable and resistant to degradation in aquatic environments. During chlorination, chloramination, and ozonation disinfection processes, PPCPs can act as precursor substances to generate N-nitrosodimethylamine (NDMA) which is the most widely detected nitrosamine byproduct in drinking water. This review provides a comprehensive overview of the impact of PPCPs in China's water environment on the generation of NDMA during disinfection processes to better understand the correlation between PPCPs and NDMA generation. Chloramine is the most likely to form NDMA with different disinfection methods, so chloramine disinfection may be the main pathway for NDMA generation. Activated carbon adsorption and UV photolysis are widely used in the removal of NDMA and its precursor PPCPs, and biological treatment is found to be a low-cost and high removal rate method for controlling the generation of NDMA. However, there are still certain regional limitations in the investigation and research on PPCPs, and other nitrosamine by-products such as NMEA, NDEA and NDBA should also be studied to investigate the formation mechanism and removal methods.

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.

Mixed exposure to haloacetaldehyde disinfection by-products exacerbates lipid aggregation in the liver of mice.

Haloacetaldehyde disinfection by-products (HAL-DBPs) are among the top three unregulated DBPs found in drinking water. The cytotoxicity and genotoxicity of HALs are much higher than that of the regulated trihalomethanes and haloacetic acids. Previous studies have mainly focused on the toxic effects of single HAL, with few examining the toxic effects of mixed exposures to HALs. The study aimed to observe the effects of mixed exposures of 1∼1000X the realistic level of HALs on the hepatotoxicity and lipid metabolism of C57BL/6J mice, based on the component and concentration of HALs detected in the finished water of Shanghai. Exposure to realistic levels of HALs led to a significant increase in phosphorated acetyl CoA carboxylase 1 (p-ACC1) in the hepatic de novo lipogenesis (DNL) pathway. Additionally, exposure to 100X realistic levels of HALs resulted in significant alterations to key enzymes of DNL pathway, including ACC1, fatty acid synthase (FAS), and diacylglycerol acyltransferase 2 (DGAT2), as well as key proteins of lipid disposal such as carnitine palmitoyltransferase 1 (CPT-1) and peroxisome proliferator activated receptor α (PPARα). Exposure to 1000X realistic levels of HALs significantly increased hepatic and serum triglyceride levels, as well as total cholesterol, low-density lipoprotein, alanine aminotransferase, aspartate transaminase, alkaline phosphatase, and lactate dehydrogenase levels, significantly decreased high-density lipoprotein. Meanwhile, histopathological analysis demonstrated that HALs exacerbated tissue vacuolization and inflammatory cell infiltration in mice livers, which showed the typical phenotypes of non-alcoholic fatty liver disease (NAFLD). These results suggested that the HALs mixture is a critical risk factor for NAFLD and is significantly highly toxic to C57BL/6J mice.

Estimating airborne trichloramine levels in indoor swimming pools using the well-mixed box model.

Exposure to airborne disinfection by-products, especially trichloramine (TCA), could cause various occupational health effects in indoor swimming pools. However, TCA concentration measurements involve specialized analysis conducted in specific laboratories, which can result in significant costs and time constraints. As an alternative, modeling techniques for estimating exposures are promising in addressing these challenges. This study aims to predict airborne TCA concentrations in indoor swimming pools using a mathematical model, the well-mixed box model, found in the IHMOD tool, freely available on the American Industrial Hygiene Association website. The model's predictions are compared with TCA concentrations measured during various bather load scenarios. The research involved conducting 2-hr successive workplace measurements over 16- to 18-hr periods in four indoor swimming pools in Quebec, Canada. TCA concentrations were estimated using the well-mixed box model, assuming a homogeneous mixing of air within the swimming pool environment. A novel approach was developed to estimate the TCA generation rate from swimming pool water, incorporating the number of swimmers in the model. Average measured concentrations of TCA were 0.24, 0.26, 0.14, and 0.34 mg/m3 for swimming pools 1, 2, 3, and 4, respectively. The ratio of these measured average concentrations to their corresponding predicted values ranged from 0.51 to 1.30, 0.67 to 1.04, 0.57 to 1.14, and 0.68 to 1.49 for the respective swimming pools. In a worst-case scenario simulating the swimming pool at full capacity (maximum bathers allowed), TCA concentrations were estimated as 0.23, 0.36, 0.14, and 0.37 mg/m3 for swimming pools 1, 2, 3, and 4. Recalculated concentrations by adjusting the number of swimmers so as not to exceed the recommended occupational limit concentration of 0.35 mg/m3 gives a maximum number of swimmers of 63 and 335 instead of currently 80 and 424 for swimming pools 2 and 4, respectively. Similarly, for swimming pools 1 and 3, the maximum number of swimmers could be 173 and 398 (instead of the current 160 and 225, respectively). These results demonstrated that the model could be used to estimate and anticipate airborne TCA levels in indoor swimming pools across various scenarios.

Preparation of MIL-101(Cr)-NH2@TAPB-DVA-COF based membrane solid-phase extraction for efficient enrichment and sensitive determination of trace aromatic disinfection by-products in juice drinks.

Aromatic disinfection by-products (DBPs) have garnered considerable interest in recent years for their potential carcinogenicity. However, efficient separation and enrichment of DBPs in complex samples is a challenge due to the extremely low content of aromatic DBPs and the complexity of sample matrices. In this study, a MIL-101(Cr)-NH2@TAPB-DVA-COF hybrid material was prepared as the enrichment medium of membrane solid-phase extraction (M-SPE) to efficiently determine trace emerging aromatic DBPs. This medium exhibited excellent enrichment capacity and selectivity for aromatic DBPs because of the strong hydrogen bonding, π-π stacking and hydrophobic interactions. An efficient analytical method for five aromatic DBPs in juice drinks was successfully established by use of this hybrid material as the enrichment medium for M-SPE in combination with liquid chromatography tandem mass spectrometry (LC-MS/MS). The limits of detection of the established method were from 0.50 to 3.00 ng/L. Moreover, the method had been successfully used in real juice drinks to determine trace five aromatic DBPs with the spiked recoveries ranging from 84.1% to 125%. The method possessed high analytical sensitivity and accuracy for these five aromatic DBPs in juice drinks with the aid of the efficient M-SPE technology proposed.

Changes of characteristics and disinfection by-products formation potential of intracellular organic matter with different molecular weight in metalimnetic oxygen minimum.

Metalimnetic oxygen minimum (MOM) occurs in reservoirs or lakes due to stratification and algal blooms, which has low dissolved oxygen (DO) levels and leads to the deterioration of water quality. The transformation mechanism and the impact on the water quality of intracellular organic matter (IOM) derived from algae are poorly understood under MOM conditions. In this study, IOM extracted by Microcystis aeruginosa was divided into five components according to molecular weight (MW), and the changes of characteristics and correlated disinfection by-products formation potential (DBPFP) were analyzed and compared under MOM conditions. The removal efficiency of dissolved organic carbon (DOC) in the <5 kDa fraction (66.6%) was higher than that in the >100 kDa fraction (41.8%) after a 14-day incubation under MOM conditions. The same tendency also occurred in Fmax and DBPFP. The decrease in Fmax was mainly due to the decline in tryptophan-like and tyrosine-like for all IOM fractions. The diversity of microorganisms degrading the MW > 100 kDa fraction was lower than others. Besides low MW fractions, these findings indicated that more attention should be paid to high MW fractions which were resistant to biodegradation under MOM conditions during water treatment.

Degrading surface-water-based natural organic matter and mitigating haloacetonitrile formation during chlorination: Comparison of UV/persulfate and UV/hydrogen peroxide pre-treatments.

Haloacetonitriles (HANs) are unregulated disinfection by-products that are more toxic than regulated species. Therefore, efficient decomposition of HAN precursors prior to disinfection is crucial for allaying the potential HAN-induced health risks. This study investigated the key roles of ultraviolet-activated persulfate (UV/PS) treatment in alleviating HAN formation. The effects of UV/PS treatment were evaluated by correlating with the characteristics of organic matter in surface water and comparing with conventional UV/H2O2 treatment. Upon irradiating raw water samples and a Suwannee River humic acid solution spiked with 10 mM PS or H2O2 with 254 nm UV light, UV/PS treatment was found to be more potent than UV/H2O2 in mitigating the HAN production and degrading organic substances; moreover, UV/PS treatment effectively decreased the dissolved organic nitrogen (DON) content. In contrast, UV/H2O2 treatment did not induce any noticeable reduction in DON level. Furthermore, both UV/PS and UV/H2O2 treatments reduced the dichloroacetonitrile (DCAN) formation potential (FP), leading to strong correlations with the degradation of aromatic and humic-acid-like compounds. Notably, UV/PS treatment efficiently decreased the FP of bromochloroacetonitrile (BCAN) and dramatically reduced that of dibromoacetonitrile (DBAN) after a sharp increase; however, UV/H2O2 treatment gradually increased the DBAN-FP. Bromide was activated by sulfate radicals during UV/PS treatment, negatively correlating with the BCAN-FP and DBAN-FP, indicating that the formation of reactive bromine species increased the DBAN-FP; however, excessive oxidation possibly led to the recovery of inorganic bromine for decreasing the BCAN-FP and DBAN-FP. Additionally, UV/PS treatment effectively suppressed toxicity owing to its high reduction rate for brominated HANs; in contrast, UV/H2O2 treatment resulted in less significant BCAN and DBAN reductions, leading to minimal net reduction in toxicity. Overall, UV/PS treatment was remarkably effective at diminishing the toxicity of brominated HANs, underscoring its potential to mitigate drinking-water-related health risks.