污水再生利用微生物控制标准及其制定方法探讨

污水再生利用的关键是水质安全保障和风险控制.微生物风险是再生水安全利用过程中需要优先控制的重要问题.本文系统探讨了我国现行污水再生利用标准中的病原微生物控制要求,分析了基于病原微生物指示指标浓度控制的必要性与不足,提出了引入微生物去除能力保障控制的必要性,并详细介绍了其制定方法与保障措施.今后,需进一步深入探讨基于浓度控制与保障能力控制相结合的污水再生利用微生物控制方法,以期为我国再生水安全利用提供技术支撑.     

再生水消毒副产物去除技术研究进展

三卤甲烷、卤乙酸、卤乙腈、三氯硝基甲烷以及N-亚硝基二甲胺是再生水氯/氯胺消毒中主要的消毒副产物,具有较强的毒性和致癌性,严重威胁生态安全及人体健康。目前难以通过改变消毒条件来减少其生成量,而去除其前驱物可有效降低消毒副产物的生成。文章介绍了氧化法、混凝沉淀法、离子交换法以及膜过滤等方法去除消毒副产物前驱物的研究,重点分析了臭氧氧化法去除消毒副产物前驱物的影响因素,对已生成的消毒副产物的去除也进行了简述。     

AAO-MBR工艺污水处理系统中消毒副产物前体物变化规律

为探究DBPs（消毒副产物）前体物在污水处理过程中的变化情况,采用超滤膜和XAD大孔吸附树脂将AAO-MBR工艺沿程出水中DOM（溶解性有机物）进行分离,并利用3D-EEM（三维荧光光谱）对分离前后水样进行表征,同时测定DBPFP（消毒副产物生成势）.结果表明:①沉砂池出水具有较低的C-DBPFP（含碳消毒副产物生成势）;经过AAO和MBR后,由于微生物代谢作用生成的疏水性SMPs（微生物代谢产物）类物质（为主要的C-DBPs前体物质）包含较多不饱和键,导致C-DBPFP增加.②沉砂池出水的N-DBPFP（含氮消毒副产物生成势）较低,但经过AAO后生成的小分子物质（为主要的N-DBPs前体物）导致N-DBPFP增加;经过MBR后由于SRT（污泥停留时间）和污泥浓度的增加造成小分子物质减少,致使N-DBPFP降低.③市政污水经过AAO后,C-DBPs和N-DBPs前体物分别增加了90.9%和7.3%;而MBR具有较高的DOC去除率（74.4%）,去除了56.8%的C-DBPs前体物和78.1%的N-DBPs前体物.研究显示,AAO-MBR工艺对市政污水中C-DBPs和N-DBPs前体物有较好地去除效果.      

澳大利亚污水处理与再生水利用现状分析及经验

对澳大利亚水资源赋存现状、污水处理和再生水利用的历史与现状进行了详细整理与分析,梳理了澳大利亚污水处理与再生水利用发展历程、相关标准、政策和法律法规以及再生水利用典型案例。该经验可为我国开展再生水循环利用研究和工程实践提供重要指导和技术支撑。借鉴澳大利亚水回用技术与管理方法,我国可进一步发展污水再生深度处理技术与工艺,提高再生水生产品质,拓展再生水利用途径,通过浓度控制与处理工艺要求相结合提升再生水水质安全保障能力,建立健全污水资源化利用技术和管理标准体系。     

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.     

饮用水含氮与含碳消毒副产物的生成潜能及其毒性

消毒副产物生成潜能测试常用于表征水中消毒副产物的前体物含量.不同于三氯甲烷等含碳消毒副产物,二卤代乙腈（DHANs）与二卤代乙酰胺（DHAcAms）等含氮消毒副产物在氯消毒的余氯存在下易分解,并且在氯胺消毒过程中可由氯胺提供氮源生成,因此常用于含碳消毒副产物的生成潜能测试方法（如Krasner提出的测试法）可能无法有效揭示DHANs与DHAcAms的前体物水平.本研究以三氯甲烷和氯醛两种含碳消毒副产物为对比,考察DHANs与DHAcAms在饮用水氯消毒与氯胺消毒过程中不同投氯量与反应时间下的生成量,识别最大生成量对应的消毒条件,以便更好地评估水样中DHANs与DHAcAms的前体物浓度.同时,对消毒过程中生成的这些挥发性消毒副产物进行毒性评价.结果显示,两个水样氯消毒的DHANs与DHAcAms生成量分别为6.19~40.08、1.34~15.75 nmol·mg^-1（mg^-1以TOC计）;氯胺消毒的DHANs与DHAcAms生成量分别为2.63~21.46、18.43~49.99 nmol·mg^-1.Krasner测试法条件下的DHANs与DHAcAms生成量均最低.在投氯量为TOC+8×NH₃-N、反应时间为24 h的氯消毒条件下,氯胺投加量20×TOC、反应时间为3 d的氯胺消毒条件下,两个水样具有最高水平的DHANs与DHAcAms生成量,并且消毒副产物毒性也高于Krasner法测试条件下的毒性水平.因此,氯消毒采用投氯量TOC+8×NH₃-N、反应时间24 h,氯胺消毒采用投加量20×TOC、反应时间3 d的生成潜能测试条件可能更好地揭示水中DHANs和DHAcAms的前体物浓度水平.     

污水再生过程中消毒副产物前体物转化规律

采用大孔吸附树脂将污水中的消毒副产物(DBP)前体物分离为亲水性物质(HPI)、强疏水性物质(HPO)和弱疏水性物质(TPI)这3个组分,通过三维荧光光谱、傅里叶红外光谱和核磁共振对再生水处理各沿程前体物进行表征,并测定各沿程出水的消毒副产物生成势(DBPFP).结果表明,生活污水中DBPs前体物主要组分为腐殖质和脂肪烃,以HPI为主.一级处理(沉淀)基于HPO与水互斥的物理性能对疏水性腐殖质有较好的去除效果,腐殖质的去除会导致含碳消毒副产物生成势(CDBPFP)的降低.此外由于DON/DOC的增加,含氮消毒副产物生成势(N-DBPFP)有所增加.二级处理(生物处理)对腐殖质和脂类均有较好的去除效果,但会产生大量疏水性的溶解性微生物产物(SMP),因此生物处理后DBPs前体物主要表现为疏水性.SMP的累积会导致C-DBPFP和N-DBPFP的大幅增加.深度处理(滤布滤池)能截留部分腐殖质和疏水性的SMP,因此前体物HPO占比减少,HPI占比增加.深度处理可以通过对SMP的去除来降低C-DBPFP和N-DBPFP.     

微生物对饮用水典型消毒副产物前体物的降解效能及其群落特征

相对于CF（氯仿）等C-DBPs（含碳消毒副产物）,DCAN（二氯乙腈）等N-DBPs（含氮消毒副产物）具有更高的毒性.控制DBPs（消毒副产物）的前体物是抑制DBPs产生的最有效方法之一.为考察微生物降解DBPs前体物对生成DBPs的影响,分别选取C-DBPs和N-DBPs的典型代表物CF和DCAN及其相应的典型前体物Tyr（酪氨酸）和Asp（天冬氨酸）为研究对象,采用微生物培养前体物的方式,探究微生物对典型前体物Tyr和Asp的降解效果及其对生成CF和DCAN的控制效果.结果表明:①Tyr和Asp两种前体物经微生物降解后,DOC（溶解性有机碳）的去除率分别为94.0%和85.6%,DON（溶解性有机氮）的去除率分别为69.0%和81.0%.②在前体物经微生物降解后的水样中,氯化或氯胺化消毒后生成CF和DCAN的量较降解前均大大减少.以Tyr为前体物,水样经微生物降解、氯化消毒后生成CF和DCAN的量分别降低了56.1%和89.5%,氯胺化消毒后生成CF的量降低了68.5%;以Asp为前体物,水样经微生物降解、氯化消毒后生成DCAN的量最高可降低99.9%,经微生物降解、氯胺化消毒后生成的CF可降低50.7%.③对水样中微生物菌群分析发现,在门水平上的菌群主要有变形菌门（Proteobacteria）、放线菌门（Actinobacteria）和拟杆菌门（Bacteroidetes）,在属水平上的菌属主要有伯克氏菌属（Burkholderia-paraburkholderia）、半角藻属（Haliangium）、分枝杆菌属（Mycobacterium）、沉积小杆菌属（Sediminibacterium）、norank_f_Chitinophagaceae和动胶菌属（Zoogloea）.研究显示,微生物降解对DBPs典型前体物Tyr和Asp的去除,以及对生成CF和DCAN的控制具有较大的潜力,变形菌和放线菌在降解DBPs前体物中起到了重要作用.      

水中典型含氮有机物氯化生成消毒副产物的潜能研究

选取了受污染原水中广泛存在的12种含氮有机物（除草剂、杀虫剂、氨基酸、工业品等）,开展了氯化和氯胺化培养生成典型消毒副产物的实验,目的是通过对水中脲类除草剂、嗪类除草剂和其他含氮化合物培养生成不同消毒副产物的生成量,讨论不同种类含氮化合物生成含碳和含氮消毒副产物规律以及考察不同消毒副产物的可能前体物.研究发现,脲类除草...     

组合氯化消毒工艺的卤代消毒副产物生成特性

比较4种单独使用氯或组合氯化消毒工艺在较长管网停留时的卤代消毒副产物生成情况.4种工艺为单独游离氯消毒、氯胺消毒、清水池游离氯消毒后转氯胺的先氯后氨消毒、短时游离氯后转氯胺的顺序氯化消毒工艺.结果表明,游离氯消毒工艺在管网停留时间长时,卤代消毒副产物会持续大量的生成,而一氯胺消毒工艺生成的卤代消毒副产物量很低.目前使用较为普遍的先氯后氨消毒工艺与游离氯消毒相比,可以降低卤代消毒副产物的生成量,管网停留24 h时,三卤甲烷的生成量降低了9.6%,卤乙酸的生成量减低了42%.但是先氯后氨消毒工艺由于游离氯接触时间约为2 h,卤代消毒副产物已经大量生成.短时游离氯后转氯胺的顺序氯化消毒工艺,由于控制了游离氯的接触时间,可以在保障消毒工艺灭活微生物效果的同时更为有效地控制卤代消毒副产物,管网停留24 h时,三卤甲烷的生成量与单独游离氯消毒工艺相比降低了48%,卤乙酸的生成量减低了72%.因此,顺序氯化消毒工艺可以更好地控制卤代消毒副产物的生成,提高水质安全性.     

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.     

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.     

Synergistic cytotoxicity of binary combinations of inorganic and organic disinfection byproducts assessed by real-time cell analysis

Chlorine, chlorine dioxide, and ozone are widely used as disinfectants in drinking water treatments. However, the combined use of different disinfectants can result in the formation of various organic and inorganic disinfection byproducts (DBPs). The toxic interactions, including synergism, addition, and antagonism, among the complex DBPs are still unclear. In this study, we established and verified a real-time cell analysis (RTCA) method for cytotoxicity measurement on Chinese hamster ovary (CHO) cell. Using this convenient and accurate method, we assessed the cytotoxicity of a series of binary combinations consisting of one of the 3 inorganic DBPs (chlorite, chlorate, and bromate) and one of the 32 regulated and emerging organic DBPs. The combination index (CI) of each combination was calculated and evaluated by isobolographic analysis to reflect the toxic interactions. The results confirmed the synergistic effect on cytotoxicity in the binary combinations consisting of chlorite and one of the 5 organic DBPs (2 iodinated DBPs (I-DBPs) and 3 brominated DBPs (Br-DBPs)), chlorate and one of the 4 organic DBPs (3 aromatic DBPs and dibromoacetonitrile), and bromate and one of the 3 organic DBPs (2 I-DBPs and dibromoacetic acid). The possible synergism mechanism of organic DBPs on the inorganic ones may be attributed to the influence of organic DBPs on cell membrane and cell antioxidant system. This study revealed the toxic interactions among organic and inorganic DBPs, and emphasized the latent adverse outcomes in the combined use of different disinfectants.     

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.     

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.     

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.     

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 disinfection byproducts (DBPs). DBPs have been linked to several adverse health effects, such as bladder cancer, adverse birth outcomes, and asthma. In this study, we quantified 60 DBPs using gas chromatography-mass spectrometry and assessed the calculated cytotoxicity and genotoxicity of an indoor community swimming pool before and after switching to a salt water pool with electrochemically generated chlorine. Interestingly, the total DBPs increased by 15% upon implementation of the salt water pool, but the calculated cytotoxicity and genotoxicity decreased by 45% and 15%, respectively. Predominant DBP classes formed were haloacetic acids, with trichloroacetic acid and dichloroacetic acid contributing 57% of the average total DBPs formed. Haloacetonitriles, haloacetic acids, and haloacetaldehydes were the primary drivers of calculated cytotoxicity, and haloacetic acids were the primary driver of calculated genotoxicity. Diiodoacetic acid, a highly toxic iodinated DBP, is reported for the first time in swimming pool water. Bromide impurities in sodium chloride used to electrochemically generate chlorine led to a 73% increase in brominated DBPs, primarily driven by bromochloroacetic acid. This study presents the most extensive DBP study to-date for salt water pools.     

南水北调丹江口水库水氯(胺)化消毒副产物产生特性与消毒工艺对比

系统研究了南水北调中线工程水源——丹江口水库水在氯(胺)化消毒条件下,常规消毒副产物的产生特性,考察了消毒方式、消毒剂投加量、接触时间、p H和溴离子浓度等因素的影响,并对消毒工艺参数进行了优化.结果发现,丹江口水库水经氯化消毒可产生三氯甲烷、二氯一溴甲烷等常规含碳和较低浓度二氯乙腈、三氯硝基甲烷等含氮消毒副产物,而氯胺化消毒仅产生三氯甲烷和三氯硝基甲烷等消毒副产物(disinfection by-products,DBPs).自由氯消毒过程产生的各类型DBPs浓度约为氯胺消毒的7.5倍,短时自由氯转氯胺方式DBPs产生量介于两者之间;随着自由氯投加量增加,各类型消毒副产物均呈现增加趋势,投加量大于2 mg·L-1后DBPs增加量较少.随氯胺投加量增加,三氯甲烷生成量变化不大,投加量大于2mg·L-1后可产生三氯硝基甲烷等副产物.随反应时间延长,自由氯的衰减速率明显大于氯胺,同时消毒副产物增长量明显快于氯胺消毒.随着p H升高,自由氯消毒后三卤甲烷含量呈现增加趋势,而氯胺消毒后变化不明显.随溴离子浓度的增加,自由氯和氯胺消毒后副产物类型均向溴代DBPs转变,同时总生成量明显增加,自由氯消毒DBPs增长量明显大于氯胺消毒过程.丹江口水库水采用氯胺化消毒可以降低消毒副产物的生成风险,如采用自由氯消毒方式,水厂需根据实际常规处理工艺重点控制自由氯的投加量等参数.     

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.