Disinfection Byproducts of Haloacetaldehydes Disrupt Hepatic Lipid Metabolism and Induce Lipotoxicity in High-Fat Culture Conditions.

Unhealthy lifestyles, obesity, and environmental pollutants are strongly correlated with the development of nonalcoholic fatty liver disease (NAFLD). Haloacetaldehyde-associated disinfection byproducts (HAL-DBPs) at various multiples of concentrations found in finished drinking water together with high-fat (HF) were examined to gauge their mixed effects on hepatic lipid metabolism. Using new alternative methods (NAMs), studying effects in human cells in vitro for risk assessment, we investigated the combined effects of HF and HAL-DBPs on hepatic lipid metabolism and lipotoxicity in immortalized LO-2 human hepatocytes. Coexposure of HAL-DBPs at various multiples of environmental exposure levels with HF increased the levels of triglycerides, interfered with de novo lipogenesis, enhanced fatty acid oxidation, and inhibited the secretion of very low-density lipoproteins. Lipid accumulation caused by the coexposure of HAL-DBPs and HF also resulted in more severe lipotoxicity in these cells. Our results using an in vitro NAM-based method provide novel insights into metabolic reprogramming in hepatocytes due to coexposure of HF and HAL-DBPs and strongly suggest that the risk of NAFLD in sensitive populations due to HAL-DBPs and poor lifestyle deserves further investigation both with laboratory and epidemiological tools. We also discuss how results from our studies could be used in health risk assessments for HAL-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.

Relationships between regulated DBPs and emerging DBPs of health concern in U.S. drinking water.

A survey was conducted at eight U.S. drinking water plants, that spanned a wide range of water qualities and treatment/disinfection practices. Plants that treated heavily-wastewater-impacted source waters had lower trihalomethane to dihaloacetonitrile ratios due to the presence of more organic nitrogen and HAN precursors. As the bromide to total organic carbon ratio increased, there was more bromine incorporation into DBPs. This has been shown in other studies for THMs and selected emerging DBPs (HANs), whereas this study examined bromine incorporation for a wider group of emerging DBPs (haloacetaldehydes, halonitromethanes). Moreover, bromine incorporation into the emerging DBPs was, in general, similar to that of the THMs. Epidemiology studies that show an association between adverse health effects and brominated THMs may be due to the formation of brominated emerging DBPs of heath concern. Plants with higher free chlorine contact times before ammonia addition to form chloramines had less iodinated DBP formation in chloraminated distribution systems, where there was more oxidation of the iodide to iodate (a sink for the iodide) by the chlorine. This has been shown in many bench-scale studies (primarily for iodinated THMs), but seldom in full-scale studies (where this study also showed the impact on total organic iodine. Collectively, the THMs, haloacetic acids, and emerging DBPs accounted for a significant portion of the TOCl, TOBr, and TOI; however, ∼50% of the TOCl and TOBr is still unknown. The correlation of the sum of detected DBPs with the TOCl and TOBr suggests that they can be used as reliable surrogates.

[Determination of 25 disinfection by-products in drinking water using liquid-liquid extraction and gas chromatography].

OBJECTIVE: To establish a liquid-liquid extraction and gas chromatography method for the determination of 7 kinds of haloacetaldehydes, 7 kinds of haloacetonitriles, 7 kinds of halonitromethanes and 4 kinds of haloacetamides in drinking water. METHODS: A liquid-liquid extraction gas chromatography technique was employed. Experimental parameters, such as capillary column type, inlet temperature, concentration of salting out reagent and sample pH were optimized to develop an analytical method, and then method validation was conducted. RESULTS: HP-5 MS UI column(30 m×0.25 mm, 0.25 µm), inlet temperature at 180 ℃, addition of 8 g sodium chloride in 50 mL water sample and pH 4-5 were chosen as the final parameters. Good correlation coefficients were obtained in the linear range of 0.20-15 µg/L, with r greater than 0.999.Methods detection limits were between 0.008-0.088 µg/L. When spiked concentration was 1.0 µg/L for pure water and tap water, the recoveries were 81%-106% and 75%-117%, respectively, and relative standard deviations were both less than 4%. When spiked concentration was 12 µg/L for pure water and tap water, the recoveries were 92%-101% and 86%-106%, respectively, and relative standard deviations were less than 4% and 2%, respectively. CONCLUSION: This method is simple, sensitive, and effective. It is suitable for simultaneous determination of 25 disinfection byproducts in drinking water.

Formation of iodo-trihalomethanes, iodo-haloacetic acids, and haloacetaldehydes during chlorination and chloramination of iodine containing waters in laboratory controlled reactions.

Iodine containing disinfection by-products (I-DBPs) and haloacetaldehydes (HALs) are emerging disinfection by-product (DBP) classes of concern. The former due to its increased potential toxicity and the latter because it was found to be the third most relevant DBP class in mass in a U.S. nationwide drinking water study. These DBP classes have been scarcely investigated, and this work was performed to further explore their formation in drinking water under chlorination and chloramination scenarios. In order to do this, iodo-trihalomethanes (I-THMs), iodo-haloacetic acids (I-HAAs) and selected HALs (mono-HALs and di-HALs species, including iodoacetaldehyde) were investigated in DBP mixtures generated after chlorination and chloramination of different water matrices containing different levels of bromide and iodide in laboratory controlled reactions. Results confirmed the enhancement of I-DBP formation in the presence of monochloramine. While I-THMs and I-HAAs contributed almost equally to total I-DBP concentrations in chlorinated water, I-THMs contributed the most to total I-DBP levels in the case of chloraminated water. The most abundant and common I-THM species generated were bromochloroiodomethane, dichloroiodomethane, and chlorodiiodomethane. Iodoacetic acid and chloroiodoacetic acid contributed the most to the total I-HAA concentrations measured in the investigated disinfected water. As for the studied HALs, dihalogenated species were the compounds that predominantly formed under both investigated treatments.

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.

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.

Coexisting oxidation and reduction of chloroacetaldehydes in water by UV/VUV irradiation.

Haloacetaldehydes (HALs) are the third largest disinfection by-product (DBP) ubiquitously detected in finished drinking water and have relatively higher toxicity than currently regulated DBPs. To efficiently alleviate them, this study investigated a green, chemical-free technology by using ultraviolet/vacuum ultraviolet (UV/VUV) on degrading three refractory chlorinated HALs (Cl-HALs). The results indicate that the rates of Cl-HALs decomposition in tap water irradiated by UV/VUV were 23-70 times higher than those irradiated by UV, proving that VUV instead of UV played the key role in degrading Cl-HALs. Increasing Cl-HALs dosage, pH, and dissolved oxygen (DO) all decreased the Cl-HALs degradations significantly, and the rates in tap water were apparently lower than those in ultrapure water. Unlike previous studies, this study proved that both oxidation and reduction were present during the VUV process. Photooxidation via oxidative radicals like •OH mineralized Cl-HALs, leading to substantial drops of total organic carbon; photoreduction via reductive radicals like •H dehalogenated Cl-HALs, resulting in formation of considerable intermediate organics (e.g., formic acid and acetic acid). No matter what pathway, the mass balances of chlorine were always maintained, meaning that dehalogenation occurred instantaneously rather than sequentially. Although the overall photodegradation rates dropped with rising pH and DO, photoreduction was increased with rising pH while photooxidation was elevated with rising DO. The results hence provide insights to better understand the VUV technology in controlling micropollutants in water.

Kinetics and mechanism of haloacetaldehyde formation from the reaction of acetaldehyde and chlorine.

Haloacetaldehydes (HALs) are the third prevalent group of disinfection by-products (DBPs) by weight in drinking water, and their cytotoxicity and genotoxicity are higher than regulated DBPs. In order to understand their formation mechanism during chlorination and ozonation-chlorination, this study examined the reaction kinetics of chloral hydrate (CH), dichloroacetaldehyde (DCA), chloroacetaldehyde (CA) and acetaldehyde by chlorine at different pH values and chlorine doses. The results showed that the reaction rate constants increased with pH and chlorine dose, except that the degradation of CH would not be affected by the presence of free chlorine. At the same pH and chlorine dose, the half-lives of CH, DCA, CA and acetaldehyde were in the order of CH > acetaldehyde â‰« DCA > CA. A kinetic model used to predict the formation of HALs and chloroform during chlorination of acetaldehyde was developed, and the predicted data fitted well with the measured data. As pre-ozonation could oxidize natural organic matter to acetaldehydes, the concentration of acetaldehyde formed after pre-ozonation was used to calculate the HAL yields during ozonation-chlorination by the kinetic model, which fitted the experimental results well. The kinetic model elucidated that the formation mechanism of HALs was a stepwise substitution process on the α-hydrogen of acetaldehyde during chlorination.

Removing chlorinated haloacetaldehydes from drinking water by household heating devices with and without chlorine: Efficiency, influencing factors, and mechanisms.

Haloacetaldehyde (HAL) is a type of disinfection byproduct (DBP) commonly detected in disinfected drinking water, and concerns toward its cytotoxic effects have promoted numerous efforts to control it. Given that household water treatment (HWT) process is a promising approach to polish drinking water quality and has been widely used by public, we herein evaluated the performances of two household heating devices (electric kettle and microwave oven) on the removals of three types of chlorinated haloacetaldehydes (Cl-HALs) under varying operating and water conditions. Results showed that the removals of HALs by boiling water to 100 °C were not very efficient (<20%) under automatic switch-off mode when chlorine was absent. The key mechanism responsible for Cl-HALs loss was likely volatilization because altering heating or cooling time did not enhance Cl-HALs' attenuations significantly. In contrast, Cl-HALs were readily transformed (>80%) when 1.0 mg/L chlorine was present without prolonging boiling time. Adding chlorine quencher (ascorbic acid) inhibited Cl-HALs' removals substantially, confirming that chlorine played a key role in the transformation process. The reactions between Cl-HALs and chlorine can be accelerated by raising water temperature and chlorine dosage. Stepwisely, monochloroacetaldehyde was transformed into dichloroacetaldehyde (DCAL), then DCAL was converted into trichloroacetaldehyde (TCAL), and eventually the C-C bond of TCAL was cleaved to form trichloromethane and formic acid. The study hence explains the differences on the removals of Cl-HALs between with and without adding chlorine and meanwhile identifies the limits of domestic heating devices in removing Cl-HALs from drinking water.

Mechanism of ozonation enhanced formation of haloacetaldehydes during subsequent chlorination.

Haloacetaldehydes (HAs) are the third prevalent group of disinfection by-products of great health concern. A bench-scale study was performed to investigate the formation and speciation of HAs in raw and treated waters after chlorination and ozonation-chlorination. Pre-ozonation resulted in enhanced HA formation during subsequent chlorination, and the HA yields from ozonation-chlorination were 1.66 and 1.63 times higher than that from chlorination of raw and treated waters. The mechanism about the increase of HA formation during ozonation-chlorination was systematically investigated in this study. The results showed that acetaldehyde formed after ozonation was the dominant precursor for the enhanced HA formation during subsequent chlorination. Increase in pH and chlorine dose increased HA formation during acetaldehyde chlorination. Based on the kinetic studies on the HA formation during acetaldehyde chlorination and the HA stabilities with and without free chlorine, it was found that chlorine was incorporated into the α-hydrogen in acetaldehyde to form a sequence of mono-, di- and tri-chloroacetaldehyde. During this process, these three chlorinated acetaldehydes would also undergo base-catalyzed hydrolysis through decarburization and dehalogenation pathways. This study elucidated that acetaldehyde formed after ozonation resulted in the increase of HA formation during subsequent chlorination. This study also revealed the formation pathway of HA during chlorination of acetaldehyde, which would help to minimize HA formation at drinking water plants.

Occurrence of nitrogenous and carbonaceous disinfection byproducts in drinking water distributed in Shenzhen, China.

A 12-month sampling program was conducted throughout a drinking water distribution system in Shenzhen and the data from 251 samples provide a comprehensive picture of the spatial and seasonal variability of 17 species disinfection by-products (DBPs) in a city with subtropical monsoon climate. The carbonaceous disinfection by-product (C-DBPs) included four trihalomethanes (THMs), three trihaloacetaldehydes (THAs) and two haloketones (HKs). Their median concentrations over the entire period were 19.9 µg/L, 3.4 µg/L and 1.4 µg/L, respectively. The nitrogenous DBPs (N-DBPs) monitored were four haloacetonitriles (HANs) and four haloacetamides (HAcAms). Their median levels were 2.0 µg/L and 1.5 µg/L, respectively. Low levels of brominated DBP species (bromine substitution factors ≤ 0.5) were observed. The BSF of each DBP class followed the trend: THMs ≈ DHAcAms > DHANs > THAs. All the DBP concentrations showed clear seasonal variations with the highest average concentrations in spring. Correlation analyses showed that the THMs and CH levels in Shenzhen drinking water could be used as statistical indicators of the levels of unregulated N-DBPs (0.4 < r < 0.7, p < 0.5). The results supplement the database of DBP occurrence in drinking water in China, and provide an important reference data set for DBP occurrence in cities with a subtropical monsoon climate around the world.

Production of trihalomethanes, haloacetaldehydes and haloacetonitriles during chlorination of microcystin-LR and impacts of pre-oxidation on their formation.

Microcystins (MCs) in drinking water have gained much attention due to their adverse health effects. However, little is known about the impact of pre-oxidation in the formation of disinfection by-products (DBPs) during the downstream chlorination of MCs. The present study examined the formation of both carbonaceous and nitrogenous DBPs from chlorination of MC-LR (the most abundant MC species) and evaluated the impact of permanganate (PM), hydrogen peroxide (H2O2) and chlorine dioxide (ClO2) pre-oxidation on the DBP formation in chlorination. Higher yields of chloroform (CF) (maximum 43.0%) were observed from chlorination of MC-LR than free amino acids which are included in MC-LR structure. Chloral hydrate (CH) and dichloroacetonitrile (DCAN) were also produced from the chlorination of MC-LR, and the latter one was formed probably due to the chlorination of peptide bonds. A high pH favored the production of CF and CH, but inhibited the formation of DCAN. In the presence of bromide, bromo-DBPs could be produced to pose a threat. For example, 0.58µg/L of tribromoacetaldehyde was produced from the chlorination of MC-LR at Br-=200µg/L. PM and ClO2 pre-oxidation could both reduce the DBP formation from MC-LR. In contrast, H2O2 appeared not to significantly control the DBP formation.

Characterization of haloacetaldehyde and trihalomethane formation potentials during drinking water treatment.

Haloacetaldehydes (HAs) are the third prevalent group of disinfection by-products (DBPs) of great health concern. In this study, their formation and speciation during chlorination were investigated for raw and process waters collected at three O3-biological activated carbon (BAC) advanced drinking water treatment plants. The results showed that all HA formation potentials (HAFPs) were highly enhanced whenever ozone was applied before or after conventional treatment. Sand filtration and BAC filtration could substantially reduce HAFPs. Trihalomethanes (THMs) were also measured to better understand the role of HAs in DBPs. Very different from HAFPs, THMFPs kept decreasing with the progress of treatment steps, which was mainly attributed to the different precursors for HAs and THMs. Brominated HAs were detected in bromide-containing waters. Chloral hydrate (CH) contributed from 25% to 48% to the total HAs formed in waters containing 100-150 µg L(-1) bromide, indicating the wide existence of other HAs after chlorination besides CH production. In addition, bromide incorporation factor (BIF) in HAs and THMs increased with the progress of treatment steps and the BIF values of THMs were generally higher than those of HAs. The BAC filtration following ozonation could significantly reduce HA precursors produced from ozonation but without complete removal. The brominated HAFPs in the outflow of BAC were still higher than their levels in the raw water. As a result, O3-BAC combined treatment was effective at controlling the total HAs, whereas it should be cautious for waters with high bromide levels.