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.     

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.     

How well does XAD resin extraction recover halogenated disinfection byproducts for comprehensive identification and toxicity testing?

Halogenated disinfection byproducts (DBPs) are an unintended consequence of drinking water disinfection, and can have significant toxicity. XAD resins are commonly used to extract and enrich trace levels of DBPs for comprehensive, nontarget identification of DBPs and also for in vitro toxicity studies. However, XAD resin recoveries for complete classes of halogenated DBPs have not been evaluated, particularly for low, environmentally relevant levels (ng/L to low µg/L). Thus, it is not known whether levels of DBPs or the toxicity of drinking water might be underestimated. In this study, DAX-8/XAD-2 layered resins were evaluated, considering both adsorption and elution from the resins, for extracting 66 DBPs from water. Results demonstrate that among the 7 classes of DBPs investigated, trihalomethanes (THMs), including iodo-THMs, were the most efficiently adsorbed, with recovery of most THMs ranging from 50%-96%, followed by halonitromethanes (40%-90%). The adsorption ability of XAD resins for haloacetonitriles, haloacetamides, and haloacetaldehydes was highly dependent on the individual species. The adsorption capacity of XAD resins for haloacetic acids was lower (5%-48%), even after adjusting to pH 1 before extraction. Recovery efficiency for most DBPs was comparable with their adsorption, as most were eluted effectively from XAD resins by ethyl acetate. DBP polarity and molecular weight were the two most important factors that determine their recovery. Recovery of trichloromethane, iodoacetic acid, chloro- and iodo-acetonitrile, and chloroacetamide were among the lowest, which could lead to underestimation of toxicity, particularly for iodoacetic acid and iodo-acetonitrile, which are highly toxic.     

CHO cell cytotoxicity and genotoxicity analyses of disinfection by-products: An updated review

The disinfection of drinking water is an important public health service that generates high quality, safe and palatable tap water. The disinfection of drinking water to reduce waterborne disease was an outstanding public health achievement of the 20th century. An unintended consequence is the reaction of disinfectants with natural organic matter, anthropogenic contaminants and bromide/iodide to form disinfection by-products (DBPs). A large number of DBPs are cytotoxic, neurotoxic, mutagenic, genotoxic, carcinogenic and teratogenic. Epidemiological studies demonstrated low but significant associations between disinfected drinking water and adverse health effects. The distribution of DBPs in disinfected waters has been well defined by advances in high precision analytical chemistry. Progress in the analytical biology and toxicology of DBPs has been forthcoming. The objective of this review was to provide a detailed presentation of the methodology for the quantitative, comparative analyses on the induction of cytotoxicity and genotoxicity of 103 DBPs using an identical analytical biological platform and endpoints. A single Chinese hamster ovary cell line was employed in the assays. The data presented are derived from papers published in the literature as well as additional new data and represent the largest direct quantitative comparison on the toxic potency of both regulated and emerging DBPs. These data may form the foundation of novel research to define the major forcing agents of DBP-mediated toxicity in disinfected water and may play an important role in achieving the goal of making safe drinking water better.     

Do DBPs swim in salt water pools? Comparison of 60 DBPs formed by electrochemically generated chlorine vs. conventional chlorine

Disinfectants are added to swimming pools to kill harmful pathogens. Although liquid chlorine(sodium hypochlorite) is the most commonly used disinfectant, alternative disinfection techniques like electrochemically generated mixed oxidants or electrochemically generated chlorine, often referred to as salt water pools, are growing in popularity. However, these disinfectants react with natural organic matter and anthropogenic contaminants introduced to the pool water by swimmers to form disinfectio...     

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.     

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.      

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.     

环境水体中无机砷现场分析方法研究进展

砷是一种环境中普遍存在的类金属元素,并与人类健康息息相关.砷被列为一类致癌物,地下水中砷导致的慢性中毒是全球性健康问题.环境水体中砷的形态多样和毒性不尽相同,且在采样和运输过程中易于转化,而使实验室分析结果出现误差.因此开发砷的现场分析方法和获得准确的数据是研究砷的形态转化和生物吸收过程和准确判断其毒性的基础.在过去的几十年中,砷的实验室内分析方法迅速发展并逐渐成熟,但砷的现场分析仍然存在着巨大的困难和挑战.总结归纳了近10年来（2011~2022年）环境水体中砷分析方法相关的综述,讨论了砷的比色法、发光法和电化学法等现场分析方法的研究进展,并展望未来环境水体中砷现场分析方法的发展方向,为新方法的建立与应用提供参考.     

Formation and control of disinfection byproducts and toxicity during reclaimed water chlorination: A review

Chlorination is essential to the safety of reclaimed water; however, this process leads to concern regarding the formation of disinfection byproducts (DBPs) and toxicity. This study reviewed the formation and control strategies for DBPs and toxicity in reclaimed water during chlorination. Both regulated and emerging DBPs have been frequently detected in reclaimed water during chlorination at a higher level than those in drinking water, indicating they pose a greater risk to humans. Luminescent bacteria and Daphnia magna acute toxicity, anti-estrogenic activity and cytotoxicity generally increased after chlorination because of the formation of DBPs. Genotoxicity by umu-test and estrogenic activity were decreased after chlorination because of destruction of toxic chemicals. During chlorination, water quality significantly impacted changes in toxicity. Ammonium tended to attenuate toxicity changes by reacting with chlorine to form chloramine, while bromide tended to aggravate toxicity changes by forming hypobromous acid. During pretreatment by ozonation and coagulation, disinfection byproduct formation potential (DBPFP) and toxicity formation potential (TFP) occasionally increase, which is accompanied by DOC removal; thus, the decrease of DOC was limited to indicate the decrease of DBPFP and TFP. It is more important to eliminate the key fraction of precursors such as hydrophobic acid and hydrophilic neutrals. During chlorination, toxicities can increase with the increasing chlorine dose and contact time. To control the excessive toxicity formation, a relatively low chlorine dose and short contact time were required. Quenching chlorine residual with reductive reagents also effectively abated the formation of toxic compounds.     

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...     

Disinfection byproducts in chlorinated or brominated swimming pools and spas: Role of brominated DBPs and association with mutagenicity

Although the health benefits of swimming are well-documented, health effects such as asthma and bladder cancer are linked to disinfection by-products (DBPs) in pool water. DBPs are formed from the reaction of disinfectants such as chlorine (Cl) or bromine (Br) with organics in the water. Our previous study (Daiber et al., Environ. Sci. Technol. 50, 6652; 2016) found correlations between the concentrations of classes of DBPs and the mutagenic potencies of waters from chlorinated or brominated swimming pools and spas. We extended this study by identifying significantly different concentrations of 21 individual DBPs in brominated or chlorinated pool and spa waters as well as identifying which DBPs and additional DBP classes were most associated with the mutagenicity of these waters. Using data from our previous study, we found that among 21 DBPs analyzed in 21 pool and spa waters, the concentration of bromoacetic acid was significantly higher in Br-waters versus Cl-waters, whereas the concentration of trichloroacetic acid was significantly higher in Cl-waters. Five Br-DBPs (tribromomethane, dibromochloroacetic acid, dibromoacetonitrile, bromoacetic acid, and tribromoacetic acid) had significantly higher concentrations in Br-spa versus Cl-spa waters. Cl-pools had significantly higher concentrations of Cl-DBPs (trichloroacetaldehyde, trichloromethane, dichloroacetic acid, and chloroacetic acid), whereas Br-pools had significantly higher concentrations of Br-DBPs (tribromomethane, dibromoacetic acid, dibromoacetonitrile, and tribromoacetic acid). The concentrations of the sum of all 4 trihalomethanes, all 11 Br-DBPs, and all 5 nitrogen-containing DBPs were each significantly higher in brominated than in chlorinated pools and spas. The 8 Br-DBPs were the only DBPs whose individual concentrations were significantly correlated with the mutagenic potencies of the pool and spa waters. These results, along with those from our earlier study, highlight the importance of Br-DBPs in the mutagenicity of these recreational waters.     

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.     

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.     

微囊藻毒素去除技术研究进展

简述了微囊藻毒素的结构、性质,重点综述和分析了国内外微囊藻毒素去除的技术和方法,并对未来的发展趋势进行了展望.     

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...     

新型溴代苯酚类消毒副产物的氯化降解机制

最近,13种新型极性卤代苯酚类消毒副产物在氯化消毒后的饮用水中被发现,它们按结构被分成4组,分别是二卤-4-羟基苯甲醛、二卤-4-羟基苯甲酸、二卤水杨酸和三卤苯酚.为研究它们在氯化消毒过程中的降解机制,选取了其中的4种全溴代种类,即3,5-二溴-4-羟基苯甲醛、3,5-二溴-4-羟基苯甲酸、3,5-二溴水杨酸以及2,4,6-三溴苯酚,利用UPLC/ESI-tq MS中的前体离子扫描,多反应监测和子离子扫描,鉴定了这几种消毒副产物在氯化消毒过程中的中间产物以及终产物,并根据这些中间产物和终产物与消毒时间的关系推测了其降解路径.结果表明,除了3,5-二溴水杨酸相对较稳定外,其余3种消毒副产物在氯化消毒过程中不稳定,通过取代、水解以及氧化等过程最终降解为卤乙酸等脂肪族小分子消毒副产物.在降解过程中有许多中间产物被检测并鉴定出来,其中包含一组具有五元环结构的新型消毒副产物(三卤代-羟基环戊烯二酮).     

Chloramination of wastewater effluent: Toxicity and formation of disinfection byproducts

The reclamation and disinfection of waters impacted by human activities (e.g., wastewater effluent discharges) are of growing interest for various applications but has been associated with the formation of toxic nitrogenous disinfection byproducts (N-DBPs). Monochloramine used as an alternative disinfectant to chlorine can be an additional source of nitrogen in the formation of N-DBPs. Individual toxicity assays have been performed on many DBPs, but few studies have been conducted with complex mixtures such as wastewater effluents. In this work, we compared the cytotoxicity and genotoxicity of wastewater effluent organic matter (EfOM) before and after chloramination. The toxicity of chloraminated EfOM was significantly higher than the toxicity of raw EfOM, and the more hydrophobic fraction (HPO) isolated on XAD-8 resin was more toxic than the fraction isolated on XAD-4 resin. More DBPs were also isolated on the XAD-8 resin. N-DBPs (i.e., haloacetonitriles or haloacetamides) were responsible for the majority of the cytotoxicity estimated from DBP concentrations measured in the XAD-8 and XAD-4 fractions (99.4% and 78.5%, respectively). Measured DBPs accounted for minor proportions of total brominated and chlorinated products, which means that many unknown halogenated compounds were formed and can be responsible for a significant part of the toxicity. Other non-halogenated byproducts (e.g., nitrosamines) may contribute to the toxicity of chloraminated effluents as well.     

城市大气颗粒物毒性效应及机制的研究进展

大气颗粒物（PM）严重影响人体的健康,其与人类多种疾病的发生存在着明显的暴露-效应关系.本文简述了大气颗粒物的组分和来源,从大气颗粒物的呼吸系统毒性、心血管毒性、免疫毒性、神经毒性、遗传毒性等方面,系统地阐述了其对人体健康的危害,并对大气颗粒物的毒性机制进行了总结和讨论,指出了目前相关研究中存在的问题,展望了该领域的研究趋势,为后续研究和控制大气颗粒物的健康危害提供相应的科学参考依据.