Occurrence of Haloacetic Acids in Drinking Water in Certain Cities of China

Objective Since haloacetic acids (HAAs), which are nonvolatile and of high carcinogenic risk, are common species of chlorinated disinfection by-products(DBPs) in drinking water, and little has been known in China, it is necessary to make a survey about the kinds and levels of HAAs in drinking water of the nation. Method HAAs were analyzed using gas chromatography with electron capture detector(GC/ECD) and relatively complex pretreatment process of sample was applied. Five main cities in different areas of China were chosen in the survey. Results Studies showed that the main species of HAAs in drinking water in China were DCAA and TCAA, ranging from 0.4 礸/L to 12.85 礸/L and from 0.56 礸/L to 10.98 礸/L, respectively. MBAA and DBAA were also detected in one city, ranging from 2.20 礸/L to 4.95 礸/L and 1.10 礸/L to 2.81 礸/L, respectively. Therefore, the contents of HAAs varied, usually no more than 25 礸/L. Based on the acquired data to date, it is known that the concentrations of HAAs in drinking water in China were surely under the limits of Sanitary Standard for Drinking Water Quality (China, 2001). Conclusion A wider survey of HAAs in drinking water should be conducted throughout the nation to get adequate data and information, the ultimate aim of which is to control HAAs pollution and keep the balance between microbiological safety insurance and chemical risk control, minimize the formation of DBPs and ensure the safety of water supply at the same time.

Researches on Formation of Haloacetic Acids in Chlorination of Drinking Water by a Novel Technique

Haloacetic acids(HAAs) are formed during the chlorination of drinking water,which are harmful to people′s health due to their carcinogenic and mutagenic effects. In the present study,a detection method combining methyl tert -butyl ether(MtBE) extraction with acid catalysis and gas chromatography coupled with an electron capture detector(GC/ECD) was developed for determining HAAs. The detection limit of this method(MDL) and relative standard deviation(RSD) were below 0.37 μg/L and 6.2%,respectively. The laboratory chlorination experiments were conducted with the purpose of investigating the influences of reaction time,temperature,UV_ 254 ,bromide and ammonia-nitrogen on the formation of HAAs. The results show that the formation amount of HAAs increases with increasing reaction time and temperature,respectively;and there exists a linear relationship between the formation of HAAs and UV_ 254 . The formation amount of HAAs decreases first and then increases as the bromide ion concentration increases,and adding NH +_4 is a possible way to control the formation of HAAs.

Determination of haloacetic acids in hospital effuent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction （SPE） method was developed for the analysis of low concentration haloacetic acids （HAAs）, a class of disinfection by-products formed from chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 ml/min, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples＇ turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μg/L and 1.30 μg/L, respectively, and the other three acids are ranging from 0.48 to 0.82μg/L under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid was the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.

Effects of halobenzoquinone and haloacetic acid water disinfection byproducts on human neural stem cells

Human neural stem cells（h NSCs） are a useful tool to assess the developmental effects of various environmental contaminants; however, the application of h NSCs to evaluate water disinfection byproducts（DBPs） is scarce. Comprehensive toxicological results are essential to the prioritization of DBPs for further testing and regulation. Therefore, this study examines the effects of DBPs on the proliferation and differentiation of h NSCs. Prior to DBP treatment, characteristic protein markers of h NSCs from passages 3 to 6 were carefully examined and it was determined that h NSCs passaged 3 or 4 times maintained stem cell characteristics and can be used for DBP analysis. Two regulated DBPs, monobromoacetic acid（BAA） and monochloroacetic acid（CAA）, and two emerging DBPs, 2,6-dibromo-1,4-benzoquinone（2,6-DBBQ） and 2,6-dichloro-1,4-benzoquinone（2,6-DCBQ）, were chosen for h NSC treatment. Both 2,6-DBBQ and 2,6-DCBQ induced cell cycle arrest at S-phase at concentrations up to 1 μmol/L. Comparatively, BAA and CAA at 0.5 μmol/L affected neural differentiation. These results suggest DBP-dependent effects on h NSC proliferation and differentiation. The DBP-induced cell cycle arrest and inhibition of normal h NSC differentiation demonstrate the need to assess the developmental neurotoxicity of DBPs.

Haloacetic acids in swimming pool and spa water in the United States and China

The objective of this study is to investigate the occurrence of haloacetic acids （HAAs）, a group of disinfection byproducts, in swimming pool and spa water. The samples were collected from six indoor pools, six outdoor pools and three spas in Pennsylvania, the United States, and from five outdoor pools and nine indoor pools in Beijing, China. Five HAAs （HAA5）, including monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid were analyzed. Total chlorine, pH and total organic carbon concentration were analyzed as well. Results indicated that the levels of HAA5 in swimming pools and spas in the United States ranged from 70 to 3980μg·L^-1, with an arithmetic average at 1440μg·L^-1 and a median level at 1150μg·L^-1. These levels are much higher than the levels reported in chlorinated drinking water and are likely due to organic matters released from swimmers＇ bodies. The levels of HAA5 in swimming pools in China ranged from 13 to 332μg·L^-1, with an arithmetic average at 117μg·L^-1 and a median level at 114μg·L^-1. The lower HAA levels in swimming pools in China were due to the lower chlorine residuals. Results from this study can help water professionals to better understand the formation and stability of HAAs in chlorinated water and assess risks associated with exposures to HAAs in swimming pools and spas.

Sensitive Determination of Five Priority Haloacetic Acids by Electromembrane Extraction with Capillary Electrophoresis

A method for sensitive determination of five priority haloacetic acids in drinking water has been developed for the first time based on electromembrane extraction(EME)prior to CZE with capacitively coupled contactless conductivity detection(CZE-C^(4)D).The target analytes were extracted from 10 mL of the sample solution(donor phase),through the supported liquid membrane(using a polypropylene membrane supporting 1-octanol),and into 10μL of 50 mmol/L NaAc solution(acceptor phase).The extracted solution was directly analyzed by CZE-C^(4)D without de-rivatization.Several factors that affect separation,detection and extraction efficiency were investigated.Under the optimum conditions,five haloacetic acids(monochloroacetic acid,dichloroacetic acid,trichloroacetic acid,mono-bromoacetic acid,and dibromoacetic acid)could be well separated from other components coexisting in water samples within 23 min,exhibiting a linear calibration over two orders of magnitude(r≥0.9943);the enrichment factors at 430-671 were obtained in a 30 min of extraction,and the limits of detection were in the range of 0.17-0.61 ng/mL.The intraday relative standard deviations for peak areas investigated at 10 ng/mL were between 1.2%and 9.7%for the combined EME-CZE-C^(4)D procedure.This approach offers an attractive alternative to the officially proposed method for purified drinking water analysis,which requires derivatization procedure prior to gas chromatography analysis.

Advanced oxidation processes of decomposing dichloroacetic acid and trichloroacetic acid in water

We studied the decomposition of two haloacetic acids (HAAs),dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA),in water by single oxidants ozone (O3) and ultraviolet radiation (UV) and the advanced oxidation processes (AOPs) constituted by the combinations of O3/UV,H2O2/UV,O3 /H2O2,and O3/H2O2/UV. The concentrations of HAAs were analyzed at specified time intervals to track their decomposition. Except for O3 and UV,the four combined oxidation processes remarkably enhance the decomposition of DCAA and TCAA owing to the generated very reactive hydroxyl radicals. The fastest decomposition process is O3/H2O2/UV,closely followed by O3/UV. DCAA is much easier to decompose than TCAA. The kinetics of HAA decomposition by O3/UV can be described well by a pseudo first-order reaction model under a constant initial dissolved O3 concentration and fixed UV radiation. Humic acids and HCO3-in the reaction system both decrease the decomposition rate constants for DCAA and TCAA. The amount of H2O2 accumulates in the presence of humic acids in the O3/UV process.

Removal of disinfection by-product formation potentials by biologically assisted GAC treatment

The object of this paper is to evaluate the removal of disinfection by-products formation potential by artificially intensified biological activated carbon（BAC） process which is developed on the basis of traditional ozone granular activated carbon （GAC）. The results show that 23.1% of trihalomethane formation potential （THMFP） and 68% of haloacetic acid formation potential （HAAFP） can be removed by BAC, respectively. Under the same conditions, the removal rates of the same substances were 12.2% and 13-25% respectively only by GAC process. Compared with GAC, the high removal rates of the two formed potential substances were due to the increasing of bioactivity of the media and the synergistic capabilities of biological degradation cooperating with activated carbon adsorption of organic compounds. BAC process has some advantages such as long backwashing cycle time, low backwashing intensity and prolonged activated carbon lifetime, etc.

Characterization of disinfection byproduct formation potential in 13 source waters in China

The formation potential of four trihalomethanes （THMFP） and seven haloacetic acids （HAA7FP） in 13 source waters taken from four major water basin areas in China was evaluated using the simulated distribution system （SDS） chlorination method. The specific ultraviolet absorbance （SUVA254： the ratio of UV254 to dissolved organic carbon （DOC））, which ranged between 0.9 and 5.0 L/（mg.m）, showed that the organic compounds in different source waters exhibited different reactivities with chlorine. The HAA7FP of source waters ranged from 20 to 448 μg/L and the THMFP ranged from 29 to 259 μg/L. The HAA7FP concentrations were higher than the THMFP concentrations in all but one of the samples. Therefore, the risks of haloacetic acids （HAAs） should be of concern in some source waters. TCM （chloroform） and BDCM （bromodichloromethane） were the major THM constituents, while TCAA （trichloroacetic acid） and DCAA （dichloroacetic acid） were the major HAA species. Br-THM （brominated THM species） were much higher than Br- HAA （brominated HAA species）, and the formation of Br-DBP （Br-THM and Br-HAA） should be of concern when the bromide concentration is over 100 μg/L.

Disinfection byproduct precursor removal by enhanced coagulation and their distribution in chemical fractions

Raw water from the Songhua River was treated by four types of coagulants, ferric chloride （FeC13）, aluminum sulfate （A12（504）3）, polyaluminum chloride （PACl） and composite polyaluminum （HPAC）, in order to remove dissolved organic matter （DOM）. Considering the disinfection byproduct （DBP） precursor treatability, DOM was divided into five chemical fractions based on resin adsorption. Trihalomethane formation potential （THMFP） and haloacetic acid formation potential （HAAFP） were measured for each fraction. The results showed that hydrophobic acids （HoA）, hydrophilic matter （HIM） and hydrophobic neutral （HoN） were the dominant fractions. Although both HoN and HoA were the main THM precursors, the contribution for THMFP changed after coagulation. Additionally, HoA and HiM were the main HAA precursors, while the contribution of HoN to HAAFP significantly increased after coagulation. HoM was more easily removed than HiM, no matter which coagulant was used, especially under enhanced coagulation conditions. DOC removal was highest for enhanced coagulation using FeCl3 while DBPFP was lowest using PAC1. This could indicate that not all DOC fractions contained the precursors of DBPs. Reduction of THMFP and HAAFP by PAC1 under enhanced coagulation could reach 51% and 59% respectively.

Formation of disinfection byproducts in typical Chinese drinking water

Eight typical drinking water supplies in China were selected in this study.Both source and tap water were used to investigate the occurrence of chlorinated disinfection byproducts（DBPs）,and seasonal variation in the concentrations of trihalomethanes（THMs） of seven water sources was compared.The results showed that the pollution level for source water in China,as shown by DBP formation potential,was low.The most encountered DBPs were chloroform,dichloroacetic acid,trichloroacetic acid,and chlorodibromoacetic acid.The concentration of every THMs and haloacetic acid（HAA） compound was under the limit of standards for drinking water quality.The highest total THMs concentrations were detected in spring.

Evaluate HAA removal in biologically active carbon filters using the ICR database

The effects of biologically active carbon(BAC)filtration on haloacetic acid(HAA)levels in plant effluents and distribution systems were investigated using the United States Environmental Protection Agency’s Information Collection Rule(ICR)database.The results showed that average HAA5 concentrations in all locations were 20.4μg·L^(-1)and 29.6μg·L^(-1)in ICR plants with granular activated carbon(GAC)and ICR plants without GAC process,respectively.For plants without GAC,the highest HAA levels were observed in the quarters of April to June and July to September.However,for plants with GAC,the highest HAA levels were observed in the quarters of April to June and January to March.This HAA level profile inversely correlated well with water temperature,or biologic activity.For GAC plants,simulated distribution samples matched well with distribution system equivalent samples for Cl3AA and THMs.For plants with and without GAC,simulated distribution samples overestimated readily biodegradable HAAs in distribution systems.The study indicated that through HAA biodegradation,GAC process plays an important role in lowering HAA levels in finished drinking water.

Case study approach to modeling historical disinfection by-product exposure in Iowa drinking waters

In the 1980 s, a case–control epidemiologic study was conducted in Iowa（USA） to analyze the association between exposure to disinfection by-products（DBPs） and bladder cancer risk. Trihalomethanes（THMs）, the most commonly measured and dominant class of DBPs in drinking water, served as a primary metric and surrogate for the full DBP mixture.Average THM exposure was calculated, based on rough estimates of past levels in Iowa. To reduce misclassification, a follow-up study was undertaken to improve estimates of past THM levels and to re-evaluate their association with cancer risk. In addition, the risk associated with haloacetic acids, another class of DBPs, was examined. In the original analysis, surface water treatment plants were assigned one of two possible THM levels depending on the point of chlorination. The re-assessment considered each utility treating surface or groundwater on a case-by-case basis. Multiple treatment/disinfection scenarios and water quality parameters were considered with actual DBP measurements to develop estimates of past levels. The highest annual average THM level in the re-analysis was156 μg/L compared to 74 μg/L for the original analysis. This allowed the analysis of subjects exposed at higher levels（〉 96 μg/L）. The re-analysis established a new approach, based on case studies and an understanding of the water quality and operational parameters that impact DBP formation, for determining historical exposure.