再生水消毒副产物的检测、生成与控制

在水资源紧缺的当下,污水再生利用是一项重要的环保战略更是资源战略.消毒能有效杀灭病菌和阻断介水疾病的传播,是保障再生水用水安全的重要手段.然而,消毒剂会不可避免地与水中有机物发生反应形成具有毒害效应的消毒副产物.围绕污水在再生消毒过程中所产生的消毒副产物,针对其检测识别方法、生成条件（前体物、消毒工艺及水质条件对消毒副产物生成的影响）以及控制方法（源头控制、过程控制及末端控制）进行综述.在此基础上,对再生水消毒副产物的未来研究动态进行了探讨,可为保障再生水的安全利用提供依据.     

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.     

饮用水中溴酸盐、亚氯酸盐、氯酸盐、溴离子的离子色谱测定法

本文选用DIONEX ICS-2000型离子色谱仪,进样量100μL。水样中的阴离子随氢氧根淋洗液进入阴离子交换分离系统,根据分析柱对各离子的亲和力不同进行分离。结果溴酸盐、亚氯酸盐、氯酸盐、溴离子的检出限分别为：5.0μg/L、4.0μg/L、5.0μg/L、4.4μg/L;标准偏差〈5%;样品加标回收率在87.5%-95.5%。结论该方法操作简单,分析快速,灵敏度高,重现性好,能够准确检测水中卤氧化物。     

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...     

The role of metal oxides on oxidant decay and disinfection byproduct formation in drinking waters: Relevance to distribution systems

Maintaining a residual disinfectant/oxidant (e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, such as hypobromous acid (HOBr), can be formed during chlorination of bromide-containing waters. The decay of oxidants and formation of disinfection byproducts (DBPs) due to the interaction between oxidants and selected metal oxides were studied. Selected metal oxides generally enhanced the decay of these halogen-containing oxidants via three pathways: (1) catalytic disproportionation to yield an oxidized form of halogen (i.e., halate) and reduced form (halide for chlorine and bromine or chlorite for chlorine dioxide), (2) oxygen formation, and (3) oxidation of a metal in a reduced form (e.g., cuprous oxide) to a higher oxidation state. Cupric oxide (CuO) and nickel oxide (NiO) showed significantly strong abilities for the first pathway, and oxygen formation was a side reaction. Cuprous oxide can react with oxidants via the third pathway, while goethite was not involved in these reactions. The ability of CuO on catalytic disproportionation of HOBr remained stable up to four cycles. In chlorination process, bromate formation tends to be important (exceeding 10 µg/L) when initial bromide concentration is above 400 µg/L in the presence of dissolved organic matter. Increasing initial bromide concentrations increased the formation of DBPs and calculated cytotoxicity, and the maximum was observed at pH 8.6 during chlorination process. Therefore, the possible disinfectant loss and DBP formation should be carefully considered in drinking water distribution systems.     

Evaluation of N-acetylcysteine and glutathione as quenching agents for the analysis of halogenated disinfection by-products

Disinfection by-products(DBPs), formed from the reactions of disinfectants with natural organic matter and halides in drinking water, were considered to be cytotoxic and genotoxic, and might trigger various cancers. The relatively low concentration of DBPs in finished water(low μg/L or even ng/L levels) and the interference from water matrix inhibited in situ determination of DBPs. Moreover, the further formation and degradation of DBPs by disinfectants during the holding time(several hours to s...     

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...     

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.     

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.      

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.     

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.     

氯、氯胺消毒下钱江源水源水消毒副产物形成特征研究

以钱江源水源水为研究对象,以氯、氯胺为消毒方式,研究了不同消毒条件下,三卤甲烷(THMs)、卤乙腈(HANs)、氯代酮(CKs)、二卤乙酸(DHAAs)、三卤乙酸(THAAs)等消毒副产物(DBPs)的形成情况,以便为水务工作者监测钱江源建库前后水质、DBPs形成的变化提供基础数据.结果显示,氯消毒下DBPs的产量比氯胺消毒高出3~7倍甚至1个数量级,但不管是氯消毒还是氯胺消毒,THMs、HAAs形成量均在我国饮用水标准范围内.氯消毒下,大部分DBPs产量为中、碱性条件酸性条件(除了CKs),氯胺消毒则呈现不同的情况(所有DBPs的产量均为p H=6、p H=7p H=8).消毒剂量对所有DBPs形成具有明显的促进作用;溴离子对THMs、DHANs、DHAAs的形成有明显的促进作用.进一步研究表明,钱江源水源水的水质比钱塘江下游九溪水源水好,DBPs形成也较低,某些指标(如有机碳、有机氮、HANs形成量等)甚至比同省水质较好的金兰水库还要好;而且由于其较高的比紫外吸收值(SUVA),DBPs的溴嵌入能力均比九溪水源水、金兰水库低.此外,就目前的钱江源水源水来说,控制消毒剂量(氯、或氯胺)是控制DBPs形成的有效策略.     

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.     

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.     

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.     

饮用水中卤氧化物离子色谱分析方法研究

直接大体积进样,建立生活饮用水中卤氧化物溴酸盐(BrO3-)、亚氯酸盐(ClO2-)、氯酸盐(ClO3-)含量的离子色谱(IC)法。优化的色谱条件为:Metrosep A Supp 7(250 mm)色谱柱配以Metrosep A Supp1保护柱,淋洗液为3.6 mmol/L Na2CO3与1.0 mmol/L NaHCO3;流速为0.6mL/min;进样量为100μL,抑制型电导检测器。方法结果显示:卤氧化物与常见共存阴离子完全分离,标准曲线在(5.0～400)μg/L范围内具有良好的线性关系(r>0.999),精密度高(相对标准偏差RSD<5.0%),样品加标平均回收率在90.8%~105%之间。按S/N=3,BrO3-、ClO2-、ClO3-的检出限分别为(0.9、0.7、1.0)μg/L。该方法操作简单、分离效果好,可与常见阴离子实现同时分析,灵敏度高,重现性好,适合于饮用水中消毒副产物中溴酸盐、亚氯酸盐、氯酸盐的同时测定。     

臭氧对生物活性炭中微生物及出水消毒副产物的影响

为探究饮用水处理过程中臭氧(O_3)对生物活性炭(BAC)中微生物及出水消毒副产物(DBPs)的影响,以饮用水小试装置的O_3-BAC工段开展研究,系统分析在不同O_3浓度下的水质变化,溶解性有机物(DOM)特征,微生物活性和DBPs产生情况.结果表明,O_3对BAC过滤的影响主要表现为提升微生物对DOM的利用效率,但O_3浓度过高会导致出水中蛋白质和微生物代谢产物(SMPs)等有机物增加.当O_3浓度从0 mg·L~(-1)提升到2. 0 mg·L~(-1)时,BAC中微生物存活率从95. 10%降至62. 60%,但O_3将出水中难降解有机物转变为易生物降解物质,使得微生物活性提高了62. 52%,BAC的生物过滤得到强化;当O_3浓度增加到4. 0 mg·L~(-1)时,微生物存活率降至49. 90%,同时微生物产生的蛋白质和SMPs增加,导致含碳消毒副产物(CDBPs)和含氮消毒副产物(N-DBPs)的生成浓度与不通O_3相比分别上升41. 93%和7. 18%,大大增加水体潜在危险.综上,合适O_3浓度有利于O_3-BAC对DOM的去除,O_3浓度过高会导致BAC过滤效果变差并产生新的DBPs前体物.     

预臭氧与后臭氧-生物活性炭联用工艺研究

利用静态批量和动态连续试验初步研究了预臭氧及预臭氧与后臭氧-BAC组合工艺对南方某含溴离子水库水的处理效果和相应的处理条件.静态实验结果表明,预臭氧反应量在0.5～1.0mg/L范围内,在有效去除消毒副产物(DBPFP,主要包括THMFP和HAAFP)的同时,臭氧副产物溴酸可以控制在10μg/L以下,而继续增加臭氧反应量则会导致DBPFP的增加.当水中溴离子浓度达到96μg/L时,使用臭氧必须采取溴酸控制措施.连续动态实验结果表明,预臭氧与臭氧-生物活性炭组合工艺对于2μm以上颗粒物、COD_Mn、TOC等的去除均有明显的效果,可以进一步抑制DBPs的形成.     

二氧化氯消毒无机消毒副产物控制技术进展研究

日常生活、生产中,饮用水消毒剂受到广泛关注.中国《生活饮用水卫生标准》(GB 5749-2006)规定二氧化氯可作为饮用水消毒剂,但其在消毒过程中所产生的无机消毒副产物,对人类健康存在潜在的危害.随着检测和控制技术水平的发展,对饮用水中无机消毒副产物的研究已成为热点.文章参考大量文献,对饮用水中无机消毒副产物的控制技术进行了详细讨论.     

The impact of iodinated X-ray contrast agents on formation and toxicity of disinfection by-products in drinking water

The presence of iodinated X-ray contrast media (ICM) in source waters is of high concern to public health because of their potential to generate highly toxic disinfection by-products (DBPs). The objective of this study was to determine the impact of ICM in source waters and the type of disinfectant on the overall toxicity of DBP mixtures and to determine which ICM and reaction conditions give rise to toxic by-products. Source waters collected from Akron, OH were treated with five different ICMs, including iopamidol, iopromide, iohexol, diatrizoate and iomeprol, with or without chlorine or chloramine disinfection. The reaction product mixtures were concentrated with XAD resins and the mammalian cell cytotoxicity and genotoxicity of the reaction mixture concentrates was measured. Water containing iopamidol generated an enhanced level of mammalian cell cytotoxicity and genotoxicity after disinfection. While chlorine disinfection with iopamidol resulted in the highest cytotoxicity overall, the relative iopamidol-mediated increase in toxicity was greater when chloramine was used as the disinfectant compared with chlorine. Four other ICMs (iopromide, iohexol, diatrizoate, and iomeprol) expressed some cytotoxicity over the control without any disinfection, and induced higher cytotoxicity when chlorinated. Only iohexol enhanced genotoxicity compared to the chlorinated source water.