TIC-Tox: A preliminary discussion on identifying the forcing agents of DBP-mediated toxicity of disinfected water

The disinfection of drinking water is a major public health achievement; however, an unintended consequence of disinfection is the generation of disinfection by-products (DBPs). Many of the identified DBPs exhibit in vitro and in vivo toxicity, generate a diversity of adverse biological effects, and may be hazards to the public health and the environment. Only a few DBPs are regulated by several national and international agencies and it is not clear if these regulated DBPs are the forcing agents that drive the observed toxicity and their associated health effects. In this study, we combine analytical chemical and biological data to resolve the forcing agents associated with mammalian cell cytotoxicity of drinking water samples from three cities. These data suggest that the trihalomethanes (THMs) and haloacetic acids may be a small component of the overall cytotoxicity of the organic material isolated from disinfected drinking water. Chemical classes of nitrogen-containing DBPs, such as the haloacetonitriles and haloacetamides, appear to be the major forcing agents of toxicity in these samples. These findings may have important implications for the design of epidemiological studies that primarily rely on the levels of THMs to define DBP exposure among populations. The TIC-Tox approach constitutes a beginning step in the process of identifying the forcing agents of toxicity in disinfected water.     

饮用水消毒技术发展趋势的文献计量学分析

消毒过程是饮用水安全保障研究的热点,本文采用文献计量学的方法对2000—2012年间的学术论文和发明专利进行了分析,明确了全球在饮用水消毒领域的研究动态和趋势以及我国存在的主要差距.结果表明全球对该领域研究的关注度持续增加,其研究热点主要集中在消毒技术工艺和消毒副产物两方面,其中氯化、臭氧氧化、氯化消毒副产物是近十余年的关注焦点.美国和瑞士作为本领域研究的主要领先国家分别在文章产出量和研究水平上位列第一,值得注意的是瑞士在本领域的研究偏重于高级氧化技术和新型消毒副产物.我国的发文量仅次于美国而专利申请量仅次于日本,但研究水平远落后于世界领先国家.我国的研究工作主要集中在氯氧化消毒工艺和常规消毒副产物生成与控制,原创性研究有待加强.本研究对明确我国饮用水消毒技术的发展趋势和研究人员选题具有重要意义.     

Disinfection by-product (DBP) research in China: Are we on the track?

Disinfection by-products (DBPs) formed during water disinfection has drawn significant public concern due to its toxicity. Since the first discovery of the trihalomethanes in 1974, continued effort has been devoted on DBPs worldwide to investigate the formation mechanism, levels, toxicity and control measures in drinking water. This review summarizes the main achievements on DBP research in China, which included: (1) the investigation of known DBP occurrence in drinking water of China; (2) the enhanced removal of DBP precursor by water treatment process; (3) the disinfection optimization to minimize DBP formation; and (4) the identification of unknown DBPs in drinking water. Although the research of DBPs in China cover the whole formation process of DBPs, there is still a challenge in effectively controlling the drinking water quality risk induced by DBPs, an integrated research framework including chemistry, toxicology, engineering, and epidemiology is especially crucial.     

Zebrafish embryo toxicity of 15 chlorinated, brominated, and iodinated disinfection by-products

Disinfection to protect human health occurs at drinking water and wastewater facilities through application of non-selective oxidants including chlorine. Oxidants also transform organic material and form disinfection by-products (DBPs), many of which are halogenated and cyto- and genotoxic. Only a handful of assays have been used to compare DBP toxicity, and researchers are unsure which DBP(s) drive the increased cancer risk associated with drinking chlorinated water. The most extensive data set employs an in vitro model cell, Chinese hamster ovary cells. Traditionally, most DBP research focuses on the threat to human health, but the effects on aquatic species exposed to DBPs in wastewater effluents remain ill defined. We present the developmental toxicity for 15 DBPs and a chlorinated wastewater to a model aquatic vertebrate, zebrafish. Mono-halogenated DBPs followed the in vivo toxicity rank order: acetamides > acetic acids > acetonitriles ~ nitrosamines, which agrees well with previously published mammalian in vitro data. Di- and tri-halogenated acetonitriles were more toxic than their mono-halogenated analogues, and bromine- and iodine-substituted DBPs tended to be more toxic than chlorinated analogues. No zebrafish development effects were observed after exposure to undiluted or non-concentrated, chlorinated wastewater. We find zebrafish development to be a viable in vivo alternative or confirmatory assay to mammalian in vitro cell assays.     

Nontargeted identification of peptides and disinfection byproducts in water

A broad range of organic compounds are known to exist in drinking water sources and serve as precursors of disinfection byproducts(DBPs).Epidemiological findings of an association of increased risk of bladder cancer with the consumption of chlorinated water has resulted in health concerns about DBPs.Peptides are thought to be an important category of DBP precursors in water.However,little is known about the actual presence of peptides and their DBPs in drinking water because of their high sample complexity and low concentrations.To address this challenge and identify peptides and non-chlorinated/chlorinated peptide DBPs from large sets of organic compounds in water,we developed a novel high throughput analysis strategy,which integrated multiple solid phase extraction(SPE),high performance liquid chromatography(HPLC)separation,and non-target identification using precursor ion exclusion(PIE)high resolution mass spectrometry(MS).After MS analysis,structures of candidate compounds,particularly peptides,were obtained by searching against the Human Metabolome Database(HMDB).Using this strategy,we successfully detected 625 peptides(out of 17,205 putative compounds)and 617 peptides(out of 13,297)respectively in source and finished water samples.The source and finished water samples had 501 peptides and amino acids in common.The remaining 116 peptides and amino acids were unique to the finished water.From a subset of 30 putative compounds for which standards were available,25 were confirmed using HPLC-MS analysis.By analyzing the peptides identified in source and finished water,we successfully confirmed three disinfection reaction pathways that convert peptides into toxic DBPs.     

Identification of unknown disinfection byproducts in drinking water produced from Taihu Lake source water

Although disinfection byproducts(DBPs) in drinking water have been suggested as a cancer causing factor, the causative compounds have not yet been clarified. In this study, we used liquid chromatography quadrupole-time-of-flight spectrometry(LC-QTOF MS) to identify the unknown disinfection byproducts(DBPs) in drinking water produced from Taihu Lake source water, which is known as a convergence point for the anthropogenic pollutants discharged from intensive industrial activities in the surroundi...     

Research progress of disinfection and disinfection by-products in China

Disinfection is an indispensable water treatment process for killing harmful pathogens and protecting human health. However, the disinfection has caused significant public concern due to the formation of toxic disinfection by-products(DBPs). Lots of studies on disinfection and DBPs have been performed in the world since 1974. Although related studies in China started in1980 s, a great progress has been achieved during the last three decades. Therefore, this review summarized the main achievements on disinfection and DPBs studies in China, which included:(1) the occurrence of DBPs in water of China,(2) the identification and detection methods of DBPs,(3) the formation mechanisms of DBPs during disinfection process,(4) the toxicological effects and epidemiological surveys of DBPs,(5) the control and management countermeasures of DBPs in water disinfection, and(6) the challenges and chances of DBPs studies in future. It is expected that this review would provide useful information and reference for optimizing disinfection process, reducing DBPs formation and protecting human health.     

辐照降解饮用水氯化消毒副产物的研究

以60Co-γ和高能电子束为辐照源,对TCA和DCA水溶液以及模拟水加氯消毒后的水溶液进行了辐照降解研究。结果表明:辐照技术能有效地降解饮用水氯化消毒副产物,并且还能够抑制消毒副产物的进一步生成,这对于消毒后饮用水质量的保持有着十分重要的意义。     

饮用水氯消毒副产物控制技术研究进展

依据新颁布的《生活饮用水卫生标准》对饮用水氯消毒副产物控制技术进行了具体的论述,介绍了替代消毒剂、前体物去除和副产物去除等控制技术的应用效果和局限性,分析了安全高效的多级屏障组合消毒工艺在控制消毒副产物中的应用前景。     

Formation potential and analysis of 32 regulated and unregulated disinfection by-products: Two new simplified methods

Water disinfection is an essential process that provides safe water by inactivating pathogens that cause waterborne diseases. However, disinfectants react with organic matter naturally present in water, leading to the formation of disinfection by-products (DBPs). Multi-analyte methods based on mass spectrometry (MS) are preferred to quantify multiple DBP classes at once however, most require extensive sample pre-treatment and significant resources. In this study, two analytical methods were developed for the quantification of 32 regulated and unregulated DBPs. A purge and trap (P&T) coupled with gas chromatography mass spectrometry (GC-MS) method was optimized that automated sample pre-treatment and analyzed volatile and semi-volatile compounds, including trihalomethanes (THMs), iodinated trihalomethanes (I-THMs), haloacetonitriles (HANs), haloketones (HKTs) and halonitromethanes (HNMs). LOQs were between 0.02-0.4 µg/L for most DBPs except for 8 analytes that were in the low µg/L range. A second method with liquid chromatography (LC) tandem mass spectrometry (MS/MS) was developed for the quantification of 10 haloacetic acids (HAAs) with a simple clean-up and direct injection. The LC-MS/MS direct injection method has the lowest detection limits reported (0.2-0.5 µg/L). Both methods have a simple sample pre-treatment, which make it possible for routine analysis. Hyperchlorination and uniform formation conditions (UFC) formation potential tests with chlorine were evaluated with water samples containing high and low TOC. Hyperchlorination formation potential test maximized THMs and HAAs while UFC maximized HANs. Ascorbic acid was found to be an appropriate quencher for both analytical methods. Disinfected drinking water from four water utilities in Alberta, Canada were also evaluated.     

溶解性有机氮乙酰胺氯化生成饮用水THMs的影响因素研究

氯化消毒可以有效杀灭细菌,但同时会产生危害人体健康的消毒副产物(DBPs).溶解性有机氮(DON)是DBPs的重要前体物,为考察DON对THMs的影响,首次选取乙酰胺(AcAm)作为前体物DON的代表物质,采用Plackett-Burman和Box-Behnken方法设计试验,考察了AcAm初始浓度、加氯量、pH、温度、溴离子浓度和反应时间等因素对三卤甲烷(THMs)生成的影响.结果表明,在AcAm生成THMs的过程中,AcAm初始浓度、pH和反应温度3个因素的影响程度较小,溴离子、有效氯和反应时间3因素的影响较大,其中溴离子的影响最为显著.溴离子浓度一定时,改变有效氯的含量,生成的THMs总量变化不大,溴离子对THMs的生成有一定的催化作用,控制溴离子的浓度是减少AcAm生成THMs的有效措施.在有效氯为8.77 mg/Ｌ、溴离子为0.77 mg/Ｌ及接触时间为6.20 h的条件下,THMs存在最大生成量为45.82 μg/L.随着反应时间的推移,溴分配系数n呈上升趋势,控制消毒反应时间,是减少THMs致癌风险的有效方法.同时探讨了AcAm生成THMs的反应路径,表述了溴离子的催化作用机制.     

全球饮用水标准中消毒副产物管控指标对比与启示

饮用水水质安全是关乎千家万户的重大民生问题,其中消毒工艺是保障饮用水微生物安全不可或缺的重要措施,然而由消毒剂与前体物反应生成的DBPs（消毒副产物）被发现具有潜在的健康风险,如致癌及引起发育副作用等.随着对饮用水中DBPs的重视程度不断提高,世界上多个国家、地区或组织将DBPs指标纳入标准.为对我国饮用水水质标准中DBPs指标的制定和修订提出可参考的建议,比较了国内外饮用水和再生水饮用回用水质标准中的DBPs指标,包括DBPs种类、对应的浓度限值和监测要求等.结果表明:①我国饮用水水质标准中涵盖的DBPs种类较多,其中地方标准相较于国标而言对DBPs指标的要求更为严格,但较少考虑综合性指标（如总有机卤素）和高毒性含氮DBPs（如卤乙腈）;②国外多部饮用水水质标准或准则中包含一些无浓度限值规定但已知具有较高健康风险的DBPs,此举可指导有关部门进一步开展浓度调研和毒性试验,为未来水质标准的制定提供参考依据.研究显示,我国饮用水标准中DBPs指标需要考虑综合性指标的选取与管控以及高风险指标的甄别和筛查,另外还需因地制宜加强地方性标准的建设工作.      

The impact of UV treatment on microbial control and DBPs formation in full-scale drinking water systems in northern China

To manage potential microbial risks and meet increasingly strict drinking water health standards, UV treatment has attracted increasing attention for use in drinking water systems in China. However, the effects of UV treatment on microbial control and disinfection by-products (DBPs) formation in real municipal drinking water systems are poorly understood. Here, we collected water samples from three real drinking water systems in Beijing and Tianjin to investigate the impacts of UV treatment on microbial control and DBP formation. We employed heterotrophic plate count (HPC), flow cytometry (FCM), quantitative PCR analysis, and high-throughput sequencing to measure microorganisms in the samples. Different trends were observed between HPC and total cell count (measured by FCM), indicating that a single indicator could not reflect the real degree of biological re-growth in drinking water distribution systems (DWDSs). A significant increase in the 16S rRNA gene concentration was observed when the UV system was stopped. Besides, the bacterial community composition was similar at the phylum level but differed markedly at the genera level among the three DWDSs. Some chlorine-resistant bacteria, including potential pathogens (e.g., Acinetobacter) showed a high relative abundance when the UV system was turned off. It can be concluded that UV treatment can mitigate microbial re-growth to some extent. Finally, UV treatment had a limited influence on the formation of DBPs, including trihalomethanes, haloacetic acids, and nitrogenated DBPs. The findings of this study may help to understand the performance of UV treatment in real drinking water systems.     

Occurrence and formation of disinfection by-products in the swimming pool environment: A critical review

Disinfection of water for human use is essential to protect against microbial disease; however, disinfection also leads to formation of disinfection by-products (DBPs), some of which are of health concern. From a chemical perspective, swimming pools are a complex matrix, with continual addition of a wide range of natural and anthropogenic chemicals via filling waters, disinfectant addition, pharmaceuticals and personal care products and human body excretions. Natural organic matter, trace amounts of DBPs and chlorine or chloramines may be introduced by the filling water, which is commonly disinfected distributed drinking water. Chlorine and/or bromine is continually introduced via the addition of chemical disinfectants to the pool. Human body excretions (sweat, urine and saliva) and pharmaceuticals and personal care products (sunscreens, cosmetics, hair products and lotions) are introduced by swimmers. High addition of disinfectant leads to a high formation of DBPs from reaction of some of the chemicals with the disinfectant. Swimming pool air is also of concern as volatile DBPs partition into the air above the pool. The presence of bromine leads to the formation of a wide range of bromo- and bromo/chloro-DBPs, and Br-DBPs are more toxic than their chlorinated analogues. This is particularly important for seawater-filled pools or pools using a bromine-based disinfectant. This review summarises chemical contaminants and DBPs in swimming pool waters, as well as in the air above pools. Factors that have been found to affect DBP formation in pools are discussed. The impact of the swimming pool environment on human health is reviewed.     

微污染水源水ClO_2消毒中ClO_2~-的来源与控制技术

综述了ClO2消毒微污染水源水的主要无机副产物ClO2-的来源,ClO2-的产生前控制和生成后去除等方法,以减少ClO2-在饮用水中的含量。并提出了氯气氧化控制饮用水中ClO2-含量的新方法。     

蓝藻AOM特征与DBPs生成关系的研究进展

蓝藻水华期间,藻细胞因自然生长或受水处理工艺影响(如预氧化和混凝),会向水中释放大量藻源有机物(AOM),能够与氯消毒剂反应生成大量消毒副产物(DBPs),增加了饮用水安全风险.了解AOM的特征及其对DBPs生成的影响对于AOM的控制和饮用水安全保障至关重要.本文综述了蓝藻AOM的主要理化特征(溶解性有机碳、溶解性有机氮、亲疏水性、光学特性、分子量、化学结构)及其对饮用水处理过程中AOM的削减转化规律和DBPs生成的影响,并讨论了AOM前体表征技术在蓝藻水处理过程中追踪AOM变化和预测DBPs的应用前景,最后展望了未来的研究方向.     

控制饮用水消毒副产物的研究状况与评述

论文简述了科学界对饮水消毒副产物问题的认识过程，对当前控制消毒副产物的主要途径和主要研究成果进行了综合评述。     

Disinfection byproduct regulatory compliance surrogates and bromide-associated risk

Natural and anthropogenic factors can alter bromide concentrations in drinking water sources. Increasing source water bromide concentrations increases the formation and alters the speciation of disinfection byproducts (DBPs) formed during drinking water treatment. Brominated DBPs are more toxic than their chlorinated analogs, and thus have a greater impact on human health. However, DBPs are regulated based on the mass sum of DBPs within a given class (e.g., trihalomethanes and haloacetic acids), not based on species-specific risk or extent of bromine incorporation. The regulated surrogate measures are intended to protect against not only the species they directly represent, but also against unregulated DBPs that are not routinely measured. Surrogates that do not incorporate effects of increasing bromide may not adequately capture human health risk associated with drinking water when source water bromide is elevated. The present study analyzes trihalomethanes (THMs), measured as TTHM, with varying source water bromide concentrations, and assesses its correlation with brominated THM, TTHM risk and species-specific THM concentrations and associated risk. Alternative potential surrogates are evaluated to assess their ability to capture THM risk under different source water bromide concentration conditions. The results of the present study indicate that TTHM does not adequately capture risk of the regulated species when source water bromide concentrations are elevated, and thus would also likely be an inadequate surrogate for many unregulated brominated species. Alternative surrogate measures, including THM3 and the bromodichloromethane concentration, are more robust surrogates for species-specific THM risk at varying source water bromide concentrations.     

饮用水中的消毒副产物及其控制策略

消毒副产物（disinfection by-products,DBPs）是在饮用水消毒时由消毒剂与有机或无机前体物反应生成的一类次生污染物,其由于具有致癌、致畸和致突变的三致特性在全球范围内广受关注.聚焦于饮用水中的DBPs,介绍了DBPs的主要分类和研究历程,汇总了多地饮用水中常见DBPs的浓度水平以及全球饮用水水质标准对DBP指标的管控要求.随后系统介绍了饮用水中DBPs的控制策略,包括源头控制、过程控制、末端控制以及协同控制这4大类,并对各类控制方法的优缺点进行了分析.评述了中国的DBPs研究的现有水平和未来趋势,并展望了未来有关DBPs控制方法的研究方向.一方面,在评价某种工艺或技术对DBPs的控制效果时需要考虑DBPs浓度和水质综合毒性的变化,另一方面,建议关注耦合源头、过程和末端控制技术的协同控制方法,兼顾从源头到龙头每个节点,实现对饮用水中各类DBPs的高效控制.     

评价饮水DBPs致HepG2细胞损伤的2种试验方法

应用结晶紫染色法细胞毒性试验和胞质分裂阻滞法微核试验(CBMNT)评价饮水消毒副产物(DBPs)的HepG2细胞毒性和遗传毒性,探讨该2种试验方法纳入饮水安全性评价体系的可行性.根据遗传毒性和致癌性选用了5种DBPs,分别对HepG2细胞进行染毒,结果表明,5种DBPs的细胞毒性大小排序为3-氯-4-二氯甲基-5-羟基-2(5氢)-呋喃酮(MX)>二氯乙腈>二溴乙酸>二氯乙酸>三氯乙酸,其细胞毒性潜力(%C?值)分别为89.74,283.81,1217.02,5066.81,9335.38μmol/L,该5种DBPs在一定浓度下均可致HepG2细胞微核率显著增加,表现出明显的遗传毒性,其遗传损伤能力排序与细胞毒性大小相同.可考虑将这两种实验方法纳入到饮水安全性评价体系中.