水中消毒副产物的监测方法研究进展

含氯、含氧等杀菌类消毒剂在饮用水生产、废水排放、再生水利用等环节应用广泛,会与水中的前驱物通过取代、氧化还原、水解、加成等反应形成种类繁多的消毒副产物(DBPs).DBPs的靶标监测基于已知DBPs的特性如挥发性、半挥发性、不挥发性等,采取相应的前处理和仪器分析方法;非靶标鉴别可对大量未知的DBPs进行筛查.综述了三卤...     

质谱及其联用技术在水中消毒副产物识别和分析中的应用

水中消毒副产物(DBPs)是在水消毒过程中消毒剂与水中溶解性有机物以及无机离子发生反应而产生,其对水环境生态安全和人体健康有不利影响。简述了DBPs的生成、种类、毒性和分析方法等,重点综述了气相色谱-质谱联用(GC-MS)、液相色谱-质谱联用(LC-MS)、离子色谱-质谱联用(IC-MS)以及超高分辨率质谱(UPMS)等质谱(MS)及其联用技术在水中DBPs识别和分析中的应用,分析了不同MS技术的特点和应用实例,提出了MS技术在DBPs研究领域的发展方向与挑战。     

在线生物毒性监测系统在饮用水源地水质监测中的应用

通过对汞、镉、铬、铅和砷的生物毒性剂量效应分析，评估生物毒性监测方法在饮用水源地水质监测中的预警作用，结果显示，几种元素的生物毒性大小依次为：汞〉砷〉铅〉镉〉铬。结合南京上坝饮用水源地的生物毒性监测数据，建立动态报警限，用于评价水质安全。     

氮氧化物遗传毒性和致癌性研究进展

综述了氮氧化物遗传毒性及致癌性的研究近况。体外实验结果，用气体暴露法ＮＯ２可诱发沙门氏菌，大肠杆菌及枯草杆菌基因突变，可诱发Ｖ７９细胞染色体畸变和ＳＣＥ率升高；体内实验结果，可诱发大鼠肺细胞哇巴因抗性突变和染色体畸变。ＮＯ２与多环芳烃类大气污染物具有联合诱变作用，ＮＯ２可增强多环芳烃的诱变性。动物致癌实验结果不一致，但促癌实验结果表明ＮＯ２可促进Ｏ３的致癌性。     

全自动Ｃ１８膜萃取－气相色谱法测定水中卤代醚

使用全自动固相萃取仪、C18膜-毛细管气相色谱-电子捕获检测器的分析方法检测水中具有致癌性的卤代醚，回收率范围71．8％～126％，检出限0．5～1．5μg／L，与EPA611相比，更加快速、准确，能够满足我国饮用水和废水的分析要求。     

大型蚤在线生物监测系统研究

近年来,世界范围内突发性废水泄漏事件频发,在引起人们对水质问题恐慌的同时,也促进了饮用水在线监测与早期污染预警系统的发展。生物监测可以对污染环境下多污染物的联合毒性进行有效评估,具有传统化学监测所不具备的优点,已成为判定水质是否对水生生物存在影响、是否符合人类安全饮用的有效依据和手段。介绍了大型蚤在线生物监测系统的多通道流通生物测试室和生物传感器系统,并对世界范围内的研究与应用情况做了研究综述。目前,采用大型蚤作为指示生物的在线监测系统已在饮用水水质监测方面成功实现,但其在工业废水接管过程中毒性评估和早期预警的研究和应用上尚有不足,有待更加深入地探讨与研究。     

晴隆锑矿和煤矿矿集区岩溶地下水环境质量评估

锑是环境中广泛分布、具有慢性毒性和潜在致癌性的典型毒害重金属,是一种新兴的全球性环境污染物。过去对锑的地球化学行为研究较多,但对岩溶地下水的环境质量影响的研究较少。选择锑矿和煤矿分布广泛的贵州晴隆县境内龙摆尾地下河为研究对象,对研究区的地表水和地下水的水化学特征和污染特征进行研究,以《生活饮用水卫生标准》(GB 5749—2006)和《地表水环境质量标准》(GB 3838—2002)中的Ⅲ类标准值为评价标准对该地区水质予以评价。结果表明:在锑矿未开采情况下,第四系碧痕营组地下水中锑的浓度较高,平均值为1.55μg/L,最高为6.32μg/L;锑、砷的迁移受氧化还原条件的控制;岩溶地下水整体来说水质符合生活饮用水标准,但碧痕营组水中锑、锰超标,龙潭组中节理裂隙水存在pH、锰超标情况;而煤矿开采污染的地表水中锰、铁的污染具有普遍性,含量均超过地表水环境质量标准的限值,且超标倍数较大。因此,该研究区岩溶地下水可直接作为饮用水源,而碧痕营组和龙潭组中地下水须做处理后才可饮用。     

饮用水中氯仿与四氯化碳含量测定的几个问题

氯仿、四氯化碳对实验动物和人类健康的损害已被公认,其致癌性也被多次实验所证实.本文阐述了气相色谱—气液平衡法测定饮用水中氯仿、四氯化碳含量的几个主要问题:诸如方法空白值.气液平衡时间及温度.方法回收率、精密度和最低检测限,样品的采集和保存等.此外还列举了饮用水样品的实测情况.作者在饮用水监测和研究工作中对气相色谱—气液平衡法的测定进行了一些改进使之更为灵敏、简便、可靠.     

农村饮用水健康风险评价

通过对某农村饮用水中化学污染物的健康风险评价,初步探讨了目前农村居民饮用水水质状况对人体健康的影响。选取2010~2014年饮用水源地水质检测数据,运用健康风险评价模型对饮水途径所引起的健康风险进行评价。结果表明该区域主要水质指标的暴露风险均低于国际辐射防护委员会(ICRP)推荐的通过饮水途径最大可接受风险水平,饮用水中化学致癌物所致健康风险度大小顺序为:Cr6+AsCd,非致癌性污染物所致风险度大小顺序为NH3-NPbHgCN-挥发酚。该村饮用水中化学致癌物有一定的风险度,应加以优先检测与控制。     

饮用水的安全性影响因素及相关处理措施

介绍了饮用水源地水质和饮用水消毒的方法，从饮用水的来源、输送方面解释生活饮用水受污染的原因，并简单介绍了新型饮用水．提出饮用水的安全消毒处理措施．     

The role of GC-MS and LC-MS in the discovery of drinking water disinfection by-products

Gas chromatography-mass spectrometry (GC-MS) has played a pivotal role in the discovery of disinfection by-products (DBPs) in drinking water. DBPs are formed when disinfectants, such as chlorine, ozone, chlorine dioxide or chloramine, react with natural organic matter in the water. The first DBP known--chloroform--was identified by Rook in 1974 using GC-MS. Soon thereafter, chloroform and other trihalomethanes were found to be ubiquitous in chlorinated drinking water. In 1976, the National Cancer Institute published results linking chloroform to cancer in laboratory animals, and an important public health issue was born. Mass spectrometry and, specifically, GC-MS became the key tool used for measuring these DBPs in water and for discovering other DBPs that were formed. Over the last 25 years, hundreds of DBPs have been identified, mostly through the use of GC-MS, which has spawned additional health effects studies and regulations. Early on, GC with low resolution electron ionization (EI)-MS was used, together with confirmation with chemical standards, for identification work. Later, researchers utilized chemical ionization (CI)-MS to provide molecular weight information and high resolution El-MS to aid in the determination of empirical formulae for the molecular ions and fragments. More recently, liquid chromatography-mass spectrometry (LC-MS) with either electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) has been used to try to uncover highly polar DBPs that most experts believe have been missed by earlier GC-MS studies. Despite 25 years of research in the identification of new DBPs, new ones are being discovered every year, even for chlorine which has been the most extensively studied.     

Trihalomethane formation potential in treated water supplies in urban metro city

Trihalomethane (THM) formation potential (TFP) is very useful test to assess the level of the formation of trihalomethanes in worst case scenario. Organics in water have the potential to generate harmful disinfection by-products (DBPs) such as THMs, as a result of their reaction with disinfectant chlorine used in drinking water. DBPs are increasingly recognized as cancerous agents. TFP of postchlorinated treated water were investigated at six water treatment plants (WTPs) in Delhi City (India). The present paper presents the current trends of TFP so that prevention and control measures can be initiated by the regulating agencies responsible for drinking water supply. Liquid–liquid extraction method, followed by qualitative and quantitative estimation by gas chromatograph equipped with electron capture detector, had been used for the determination of THMs in water samples collected at the outlet just before supplying to the consumers during 2000–2007. The TFP values from 2004 onward of all WTPs did not exceed the WHO guideline value of ≤1.     

Penetration of polar brominated DBPs through the activated carbon columns during total organic bromine analysis

Total organic bromine (TOBr) is a collective parameter representing all the brominated organic disinfection byproducts (DBPs) in water samples. TOBr can be measured using the adsorption-pyrolysis method according to Standard Method 5320B. This method involves that brominated organic DBPs are separated from inorganic halides and concentrated from aqueous solution by adsorption onto the activated carbon (AC). Previous studies have reported that some commonly known brominated DBPs can partially penetrate through the AC during this adsorption step. In this work, the penetration of polar brominated DBPs through AC and ozone-modified AC was explored with two simulated drinking water samples and one chlorinated wastewater effluent sample. Polar brominated DBPs were selectively detected with a novel precursor ion scan method using electrospray ionization-triple quadrupole mass spectrometry. The results show that 3.4% and 10.4% of polar brominated DBPs (in terms of total ion intensity) in the chlorinated Suwannee River fulvic acid and humic acid samples, respectively, penetrated through the AC, and 19.6% of polar brominated DBPs in the chlorinated secondary wastewater effluent sample penetrated through the AC. The ozone-modification of AC minimized the penetration of polar brominated DBPs during the TOBr analysis.     

Study of personal–indoor–ambient fine particulate matters among school communities in mixed urban–industrial environment in India

A sampling program was conducted to investigate the formation of disinfection by-products (DBPs) and dissolved organic carbon (DOC) at two advanced water treatment plants in Kaohsiung City, Taiwan. The results in this study can be used as a reference for the operational control of water treatment plants and the setting of regulations in Taiwan. Samples of drinking water were collected from two advanced water treatment plants from June 2007 to April 2008. Changes in the concentration of dissolved organic carbon, the trihalomethane formation potential, and the haloacetic acids formation potential were measured in raw water samples. Variations in the concentrations of trihalomethanes (THMs) and haloacetic acids (HAA₅) in finished drinking water were evaluated. The major species of HAA₅ were in the order of dichloroacetic acid and trichloroacetic acid and the THM was of trichloromethane. DOC was strongly related to DBPs in raw water. In this investigation, the removal efficiency of DBPs in Plant A (ultrafiltration/reverse osmosis system) exceeded that in Plant B (ozonation/biological activated carbon system). Both advanced water treatment plants greatly improved the quality of drinking water.     

DBP Levels in Chlorinated Drinking Water: Effect of Humic Substances

Chlorination is the most widely used technique for disinfection of drinking water. A consequence of chlorination is the formation of Disinfection By-Products (DBPs). The formation of DBPs in drinking water results from the reaction of chlorine with naturally occurring organic materials, principally humic and fulvic acids. This paper focuses on the effect of humic substances on the formation of twenty-four compounds belonging to different categories of DBPs. This investigation was conducted in two water treatment plants in Greece, Menidi and Galatsi, from July 1999 to April 2000. Humic substances were determined by the diethylaminoethyl (DEAE) method with subsequent UV measurement. The techniques used for the determination of DBPs were liquid-liquid extraction, gas chromatography and mass spectrometry. The concentrations of DBPs were generally low. Total trihalomethanes (TTHMs) ranged from 5.1 to 24.6 microg L(-1), and total haloacetic acids (HAAs) concentration ranged from 8.6 to 28.4 microg L(-1), while haloaketones (HKs) and chloral hydrate (CH) occurred below 1 microg L(-1). The content of humic substances was found to influence the formation of DBPs and especially TTHMs, trichloroacetic acid (TCA), dibromoacetic acid (DBA), CH, 1,1-dichloropropanone (1.1-DCP) and 1,1,1-trichloropropanone (1,1,1-TCP). Seasonal variation of TTHMs and HAAs generally followed that of humic substances content with peaks occurring in autumn and spring. The trends of 1,1-DCP, 1,1,1-TCP and CH formation seemed to be in contrast to TTHMs and HAAs. Trends of formation of individual compounds varied in some cases, probably due to influence of parameters other than humic substances content. Statistical analysis of the results showed that the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DBA are strongly affected from humic substances content (at 0.01 confidence level). The opposite is true for dichloroacetic acid (DCA) concentration. Humic substances also vary to a statistically significant degree during different months, as well as the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DCA. The variance of DBA was not statistically significant. Regarding the effect of sampling station, humic substances content showed no statistically significant difference between the two raw water sources studied.     

Evaluation of biological stability and corrosion potential in drinking water distribution systems: a case study

The appearance of assimilable organic carbon (AOC), microbial regrowth, disinfection by-products (DBPs), and pipe corrosion in drinking water distribution systems are among those major safe drinking water issues in many countries. The water distribution system of Cheng-Ching Lake Water Treatment Plant (CCLWTP) was selected in this study to evaluate the: (1) fate and transport of AOC, DBPs [e.g., trihalomethanes (THMs), haloacetic acids (HAAs)], and other organic carbon indicators in the selected distribution system, (2) correlations between AOC (or DBPs) and major water quality parameters [e.g. dissolved oxygen (DO), free residual chlorine, and bacteria, and (3) causes and significance of corrosion problems of the water pipes in this system. In this study, seasonal water samples were collected from 13 representative locations in the distribution system for analyses of AOC, DBPs, and other water quality indicators. Results indicate that residual free chlorine concentrations in the distribution system met the drinking water standards (0.2 to 1 mg l(-1)) established by Taiwan Environmental Protection Administration (TEPA). Results show that AOC measurements correlated positively with total organic carbon (TOC) and UV-254 (an organic indicator) values in this system. Moreover, AOC concentrations at some locations were higher than the 50 microg acetate-C l(-1) standard established by Taiwan Water Company. This indicates that the microbial regrowth might be a potential water quality problem in this system. Higher DO measurements (>5.7 mg l(-1)) might cause the aerobic biodegradation of THMs and HAAs in the system, and thus, low THMs (<0.035 mg l(-1)) and HAAs (<0.019 mg l(-1)) concentrations were observed at all sampling locations. Results from the observed negative Langelier Saturation Index (LSI) values, higher Ryznar Stability Index (RSI) values, and high Fe3+ concentrations at some pipe-end locations indicate that highly oxidative and corrosive conditions occurred. This reveals that pipe replacement should be considered at these locations. These findings would be helpful in managing the water distribution system for maintaining a safe drinking water quality.     

Drinking water treatment is not associated with an observed increase in neural tube defects in mice

Disinfection by-products (DBPs) arise when natural organic matter in source water reacts with disinfectants used in the water treatment process. Studies have suggested an association between DBPs and birth defects. Neural tube defects (NTDs) in embryos of untreated control mice were first observed in-house in May 2006 and have continued to date. The source of the NTD-inducing agent was previously determined to be a component of drinking water. Tap water samples from a variety of sources were analyzed for trihalomethanes (THMs) to determine if they were causing the malformations. NTDs were observed in CD-1 mice provided with treated and untreated surface water. Occurrence of NTDs varied by water source and treatment regimens. THMs were detected in tap water derived from surface water but not detected in tap water derived from a groundwater source. THMs were absent in untreated river water and laboratory purified waters, yet the percentage of NTDs in untreated river water were similar to the treated water counterpart. These findings indicate that THMs were not the primary cause of NTDs in the mice since the occurrence of NTDs was unrelated to drinking water disinfection.     

Ascorbic acid reduction of active chlorine prior to determining Ames mutagenicity of chlorinated natural organic matter (NOM)

Many potable water disinfection byproducts (DBPs) that result from the reaction of natural organic matter (NOM) with oxidizing chlorine are known or suspected to be carcinogenic and mutagenic. The Ames assay is routinely used to assess an overall level of mutagenicity for all compounds in samples from potable water supplies or laboratory studies of DBP formation. Reduction of oxidizing disinfectants is required since these compounds can kill the bacteria or react with the agar, producing chlorinated byproducts. When mutagens are collected by passing potable water through adsorbing resins, active chlorine compounds react with the resin, producing undesirable mutagenic artifacts. The bioanalytical and chemoanalytical needs of drinking water DBP studies required a suitable reductant. Many of the candidate compounds failed to meet those needs, including 2,4-hexadienoic (sorbic) acid, 2,4-pentanedione (acetylacetone), 2-butenoic (crotonic) acid, 2-butenedioic (maleic and fumaric) acids and buten-2-ol (crotyl alcohol). Candidates were rejected if they (1) reacted too slowly with active chlorine, (2) formed mutagenic byproducts, or (3) interfered in the quantitation of known chlorination DBPs. L-Ascorbic acid reacts rapidly and stoichiometrically with active chlorine and has limited interactions with halogenated DBPs. In this work, we found no interference from L-ascorbic acid or its oxidation product (dehydroascorbic acid) in mutagenicity assays of chlorinated NOM using Salmonella typhimurium TA100, with or without metabolic activation (S9). This was demonstrated for both aqueous solutions of chlorinated NOM and concentrates derived from the involatile, ether-extractable chlorinated byproducts of those solutions.     

Disinfection By-Products in Water Produced by Ozonation and Chlorination

Water produced by advanced treatment of a groundwater was evaluated to determine the amount of DBPs (Disinfection By-Products) including trihalomethanes (THMs). Both Gas Chromatography (GC) and Gas Chromatography/Mass Spectrometry (GS/MS) were adopted for detection and identification of DBPs such as trihalomethanes (THMs), halo-acetic acids (HAAs) and aldehydes. Two disinfection modes (ozonation followed by chlorination and chlorination alone) were compared to determine the DBPs generation. The mutagenitic acivity of ozonated water, chlorinated water after ozonation and potable water was assessed using the Ames test. Chloroform, dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) were the main constituents of THMs and HAAs, respectively. THMs accounted for more than 85% of all DBPs measured, whereas haloacetic acids accounted for around 14%. Ozonation followed by chlorination proved to be better in terms of THMs and HAAs control. The combined system produced 28.3% less DBPs compared to chlorination alone. Ozonation was found capable of reducing mutagenic matter in the groundwater by 54.7%. The combined system also resulted in water with no mutagenicity.