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.

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.

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.

Rapid Determination of HAAs Formation Potential of the Reaction of Humic Acid with Chlorine or Chlorine Dioxide

On the basis of gas chromatography（GC） coupled with a short capillary column and an electron capture detector （ ECD）, a simple and rapid method for the determination of five haloaceric acids （ HAAs ） in drinking water was developed by the optimization of derivation conditions and the modification of gas chromatographic program. HAAs formarion potential（HAAFP） of the reaction of humic acid with chlorine was determined via this method. The major advantages of the method are the simplicity of chromatographic temperature program and the short run time of GC. Dichloroaceric acid（DCAA） and Trichloroacetic acid（TCAA）, which were detected in the determination of HAAFP, were rapidly formed in the first 72 h of the reaction of humic acid with chlorine. HAAFP of the reaction of humic acid with chlorine increased with the increase in the concentrations of humic acid and chlorine. The average HAAFP of the reaction of humic acid with chlorine was 39.9μg/mg TOC under the experimental conditions. When the concentration of humic acid was 4 mg/L, the concentration of HAAs, which were produced in the reaction of humic acid with choline, may exceed MCL of 60μg/L HAAs as the water quality standards for urban water supply of China and the first stage of US EPA disinfecrion/disinfection by-products（D/DBP） rule; when the concentration of humic acid was 2 mg/L, the concentration of HAAs may exceed MCL of 30 μg/L HAAs for the second stage of US EPA D/DBP rule. When humic acid was reacted with chlorine dioxide, only DCAA was detected with a maximum concentration of 3.3 μg/L at a humic acid content of 5 mg/L. It was demonstrated that the substitution of chlorine dioxide for chorine may entirely or partly control the formation of HAAs and effectively reduce the health risk associated with disinfected drinking water.

Behaviour of Haloacetic Acids in Drinking Water Distribution Systems

To guarantee the safety of drinking water quality after chlorination, the formation, distribution and factors influencing the concentrations of haloacetic acids (HAAs) in a water distribution system (WDS) were investigated both on a full-scale WDS (FWDS) and pilot-scale WDS (PWDS) within a city in northern China. The results of both investigations showed that trichloroacetic acid (TCAA) and dichloroacetic acid (DCAA) were the dominating types of HAAs. In the FWDS, variations in the HAA content showed negative correlations with total residual chlorine, pH and non-purgeable organic carbon (NPOC) and positive correlations with temperature and UV254. In the PWDS, the concentration of HAAs after rechlorination followed the rule of ‘first rise and then fall’; therefore, locating an appropriate rechlorination point and lowering the single chlorine dosage could be used as effective measures to control the HAA content in WDSs. © 2016, Tianjin University and Springer-Verlag Berlin Heidelberg.

Evolution and Fate of Haloacetic Acids before and after Chlorination within the Treatment Plant Using SPE-GC-MS

The previous research on the occurrence of disinfection by-products (DBPs) in drinking water has focused on trihalomethane (THMs) formation and evolution, in particular within distribution systems. In this study, the variability of occurrence of haloacetic acids (HAAs) before and after treatment was investigated. The investigation focused on point–to-point fluctuations of HAAs in different treatment stages within the treatment plant. The research was also carried out to find out the possible sources for the presence of HAAs before chlorination in the raw water. The results showed that the presence of HAAs from the raw water point until the filtered water occurred due to industrial waste and sewages. Subsequent formation of HAAs from treated point until service reservoir due to disinfection. The HAAs concentration was the highest and most variable in the plant where level of DBP precursor indicators and the chlorine dose were both higher. However, HAAs level and in particular dichloroacetic acids (DCAA) (the preponderant HAAs species in the waters under study), trichloroacetic acids (TCAA) decreased dramatically during filtration, very probably because of the biodegradation within the filter. An ANNOVA test was used to evaluate the level of significance of HAAs between treated water and service reservoir outlet water.

氯消毒过程中水中色氨酸产生THMs和HAAs的特征研究

以氨基酸为代表的溶解性含氮有机物在水源水中广泛存在,成为制水工艺消毒副产物的主要前体物之一.选取色氨酸(Trp)为含氮前体物模型,考察了其在消毒工艺中产生受控消毒副产物的途径及影响因素.结果表明,Trp氯化过程经取代,脱羧,水解等一系列反应,可生成卤乙酸(HAAs),三卤甲烷(THMs)等消毒副产物.THMs和HAAs的生成量随加氯量增加;随接触时间的延长逐渐增加.温度的升高,HAAs的生成量先增大后减少;碱性条件有利于THMs和HAAs的生成.氯胺消毒和遮光条件下可明显减少THMs和HAAs的产生.

饮用水水质标准升级带来的消毒副产物挑战与对策

随着国家和地方饮用水水质标准提升,标准中增加了消毒副产物指标、提高了标准限值和检测频率。加之水源水中有机物浓度居高不下,使得消毒副产物成为我国供水行业面临的重要水质挑战。以三卤甲烷、卤乙酸、亚硝胺为代表,汇总了公开文献报道中我国典型城市饮用水中消毒副产物浓度。介绍了上述消毒副产物的前体物成分、来源和解析方法。基于中试和生产运行数据,提出了水源调控、厂内控制的消毒副产物控制策略。其中,强化混凝沉淀、增加臭氧-活性炭深度处理和优化消毒工艺是控制上述消毒副产物的关键处理工艺。

水体中卤乙酸(HAA s)的产生、测定方法与控制途径

对饮用水中普遍存在的消毒副产物形式HAAs的产生、测定方法以及控制途径进行了阐述。并对影响HAAs生成的主要因素投氯量、溴的影响以及卤乙酸副产物(HAAFP)含量等进行了分析。生物活性炭技术是一种非常有效的控制HAAs含量和减少HAAFP含量的方法,对于保障饮用水安全性具有重要意义。

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.

不同消毒方式供水管网中消毒副产物的分布特征

针对我国东南沿海地区4个使用不同类型二次消毒剂(氯、氯胺、二氧化氯)的局部管网水样的中三卤甲烷(THMs)、卤乙酸(HAAs)、卤乙腈(HANs)的分布特征及影响因素进行了分析。结果表明,3座城市DBPs的超标风险整体较低,采集的117份水样中有10份水样THMs超过国标限值,其余DBPs均符合标准。以氯为消毒剂的管网水样中THMs浓度和HANs浓度远高于其他管网,以二氧化氯为消毒剂可以减少消毒副产物THMs的生成,但以氯胺为消毒剂的上海地区HAAs浓度较高,是其他3个系统的5~19倍,可能与原水中HAAs前体物含量较高有关。在SH-NH_(2)Cl系统中,消毒剂浓度与输配距离成反比(r=-0.57),同时该系统中硝酸盐、亚硝酸盐及氨氮浓度也随距离变化,说明饮用水在管网输送过程中余氯被逐渐消耗,同时管网中发生了硝化反应,氨氮被氧化为亚硝酸盐和硝酸盐。WJ-Cl2系统中DBPs与输配距离相关,HANs浓度沿程减少(r=-0.49),HAAs浓度沿程增加(r=0.45)。此外,建筑管网中长停滞时间也会影响水样理化指标。该研究揭示了不同类型二次消毒剂的管网水中DBPs浓度水平和变化规律,研究结果可为不同地区水质安全评价和风险控制提供依据。

生姜对烘烤猪肉饼品质及杂环胺形成的影响

选取猪肉与生姜为研究对象,探究不同生姜浓度(0.5%、1.0%、1.5%)对烘烤猪肉饼品质及杂环胺(heterocyclic aromatic amines,HAAs)生成的影响。结果表明,生姜能够降低猪肉饼的质量损失率并且改善色泽。生姜对8种HAAs(MeIQ、MeIQx、4,8-DiMeIQx、PhIP、IQx、IQ、AαC、Trp-P-2)均具有很好的抑制效果。浓度为1.5%的生姜对烘烤猪肉饼的总HAAs含量抑制率为55.45%。随着生姜浓度的增加,对游离氨基酸的消耗减少。因此生姜对烘烤猪肉饼中的HAAs有很好的抑制活性。

液相色谱-串联质谱法测定生活饮用水中4种卤代乙酸的含量

提出了液相色谱-串联质谱法测定生活饮用水中二氯乙酸、三氯乙酸、一碘乙酸和二碘乙酸等4种卤代乙酸含量的方法。取0.5 mL过滤后的水样,与0.5 mL乙腈混合。以Torus DEA色谱柱为固定相,以体积比10∶90的含1.0 mmol·L^(-1)乙酸铵的2.0%(体积分数)氨水溶液-乙腈混合液为流动相进行等度洗脱。分离后的4种目标物经电喷雾离子源负离子模式扫描,采用多反应监测模式进行检测,外标法定量。结果显示:4种卤代乙酸的质量浓度在5~100μg·L^(-1)内与定量离子峰面积呈线性关系,检出限(3S/N)为0.3~3.0μg·L^(-1);对自来水水样进行3个浓度水平的加标回收试验,回收率为70.1%~114%,测定值的相对标准偏差为(n=6)为0.90%~5.8%;方法用于10份末梢水分析,其中一碘乙酸、二碘乙酸和三氯乙酸均未检出,有8份样品检出二氯乙酸,检出量为2.0~4.4μg·L^(-1)。

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.

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.

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.

Ab initio studies on the pyrolysis mechanism of 2-haloacetic acids in the gas phase

The dehydrohalogenation mechanism of 2-haloacetic acids (XCH2CO2H, X=F, Cl and Br) has been studied theoretically by HF/3-21G and AM1 methods. The results indicate that these reactions are most probably proceeded in terms of a polar five-membered cyclic transition state in the gas phase. Their microscopic processes are beleived to be a stepwise reaction and the rate-determining step is the first one. By comparing the energy barriers of different 2-haloacetic acids, it can be realized that 2-fluoroacetic acid is easier to react than 2-chloroacetic and 2-bromoacetic acids.

饮用水处理中氯化消毒副产物三卤甲烷和卤代乙酸研究进展

三卤甲烷和卤代乙酸是饮用水氯化消毒的典型副产物。该文结合国内外学者对三卤甲烷和卤代乙酸的研究成果对这两类物质的形成的影响因素、主要检测方法及控制方法进行了总结。

供水管网中AOC、消毒副产物的变化规律

以西南L市的供水管网为研究对象 ,以可同化有机碳 (AOC)、三卤甲烷 (THMs)、卤乙酸 (HAAs)为评价指标 ,研究了不同季节给水管网中水质的变化情况。结果表明 :三卤甲烷在管网中只受余氯的影响 ,其含量一般随管道长度的增加而增加 ;卤乙酸和AOC在管网中的变化受余氯和微生物活性的影响 ,其含量一般随管网延伸而先增加后减少 ,温度越高则下降越快。温度和余氯是管网中控制消毒副产物和AOC浓度的重要因素。