单过硫酸氢钾复合粉在饮用水消毒过程中的副产物生成特性及遗传毒性变化

以北京田村山净水厂原水和炭后出水作为试验用水,对新型消毒剂单过硫酸氢钾复合粉消毒后生成的消毒副产物(disinfection by-products,DBPs)进行定性分析.向受试水样中分别投加单过硫酸氢钾复合粉和次氯酸钠,比较了复合粉消毒和氯消毒的DBPs生成量,并通过umu试验对水样消毒后的遗传毒性变化进行测试.结果表明,测试水样投加单过硫酸氢钾复合粉消毒前后的有机物种类变化不大,但仍有新的卤代烃和卤代物生成.与氯消毒相比,单过硫酸氢钾复合粉消毒后生成的三卤甲烷(THMs)和卤乙酸(HAAs)的含量更低.另外,根据umu测试的结果,经单过硫酸氢钾复合粉消毒后原水和炭后水的遗传毒性均明显低于氯消毒.然而在水中有机物较多和消毒剂投加量较大时,单过硫酸氢钾复合粉用于消毒仍有一定安全风险.     

Change in genotoxicity of wastewater during chlorine dioxide and chlorine disinfections and the influence of ammonia nitrogen

The effects of chlorine dioxide and chlorine disinfections on the genotoxicity of different biologically treated sewage wastewater samples were studied by umu-test. The experiment results showed that when chlorine dioxide dosage was increased from 0 to 30 mg/L, the genotoxicity of wastewater first decreased rapidly and then tended to be stable, while when the chlorine dosage was increased from 0 to 30 mg/L, the genotoxicity of wastewater changed diversely for different samples. It was then found that ammonia nitrogen did not affect the change of genotoxicity during chlorine dioxide disinfection of wastewater, while it greatly affected the change of genotoxicity during chlorine disinfection of wastewater. When the concentration of ammonia nitrogen was low (< 10–20 mg/L), the genotoxicity of wastewater decreased after chlorine disinfection, and when the concentration of ammonia nitrogen was high (> 10–20 mg/L), the genotoxicity of wastewater increased after chlorine disinfection.     

Impact of disinfection on drinking water biofilm bacterial community

Disinfectants are commonly applied to control the growth of microorganisms in drinking water distribution systems. However, the effect of disinfection on drinking water microbial community remains poorly understood. The present study investigated the impacts of different disinfectants (chlorine and chloramine) and dosages on biofilm bacterial community in bench-scale pipe section reactors. Illumina MiSeq sequencing illustrated that disinfection strategy could affect both bacterial diversity and community structure of drinking water biofilm. Proteobacteria tended to predominate in chloraminated drinking water biofilms, while Firmicutes in chlorinated and unchlorinated biofilms. The major proteobacterial groups were influenced by both disinfectant type and dosage. In addition, chloramination had a more profound impact on bacterial community than chlorination.     

Evaluation of drinking water treatment combined filter backwash water recycling technology based on comet and micronucleus assay

Based on the fact that recycling of combined filter backwash water（CFBW）directly to drinking water treatment plants（WTP）is considered to be a feasible method to enhance pollutant removal efficiency,we were motivated to evaluate the genotoxicity of water samples from two pilot-scale drinking water treatment systems,one with recycling of combined backwash water,the other one with a conventional process.An integrated approach of the comet and micronucleus（MN）assays was used with zebrafish（Danio rerio）to investigate the water genotoxicity in this study.The total organic carbon（TOC）,dissolved organic carbon（DOC）,and trihalomethane formation potential（THMFP）,of the recycling process were lower than that of the conventional process.All the results showed that there was no statistically significant difference（P>0.05）between the conventional and recycling processes,and indicated that the genotoxicity of water samples from the recycling process did not accumulate in 15 day continuous recycling trial.It was worth noting that there was correlation between the concentrations of TOC,DOC,UV₂₅₄,and THMFPs in water and the DNA damage score,with corresponding R² values of 0.68,0.63,0.28,and 0.64.Nevertheless,both DNA strand breaks and MN frequency of all water samples after disinfection were higher than that of water samples from the two treatment units,which meant that the disinfection by-products（DBPs）formed by disinfection could increase the DNA damage.Both the comet and MN tests suggest that the recycling process did not increase the genotoxicity risk,compared to the traditional process.     

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.     

A balancing act: Optimizing free chlorine contact time to minimize iodo-DBPs, NDMA, and regulated DBPs in chloraminated drinking water

Many drinking water treatment plants in the U.S. have switched from chlorination to chloramination to lower levels of regulated trihalomethane (THM) and haloacetic acid (HAA) disinfection byproducts (DBPs) in drinking water and meet the current regulations. However, chloramination can also produce other highly toxic/carcinogenic, unregulated DBPs: iodo-acids, iodo-THMs, and N-nitrosodimethylamine (NDMA). In practice, chloramines are generated by the addition of chlorine with ammonia, and plants use varying amounts of free chlorine contact time prior to ammonia addition to effectively kill pathogens and meet DBP regulations. However, iodo-DBPs and nitrosamines are generally not considered in this balancing of free chlorine contact time. The goal of our work was to determine whether an optimal free chlorine contact time could be established in which iodo-DBPs and NDMA could be minimized, while keeping regulated THMs and HAAs below their regulatory limits. The effect of free chlorine contact time was evaluated for the formation of six iodo-trihalomethanes (iodo-THMs), six iodo-acids, and NDMA during the chloramination of drinking water. Ten different free chlorine contact times were examined for two source waters with different dissolved organic carbon (DOC) and bromide/iodide. For the low DOC water at pH 7 and 8, an optimized free chlorine contact time of up to 1 h could control regulated THMs and HAAs, as well as iodo-DBPs and NDMA. For the high DOC water, a free chlorine contact time of 5 min could control iodo-DBPs and NDMA at both pHs, but the regulated DBPs could exceed the regulations at pH 7.     

城市污水生物脱氮系统出水经氯胺消毒形成NDMA的影响因素研究

为了考察城市污水回用时氯消毒过程中NDMA的形成,以2套生物脱氮实验装置厌氧/缺氧/好氧(A/A/O)和缺氧/好氧(A/O)的二沉池出水为对象,研究了氯胺消毒过程中氯胺剂量、pH、NO2--N和NO3--N浓度对N-亚硝基二甲胺(NDMA)形成的影响.结果表明,二沉池出水中仍然含有微量的NDMA前体物,导致了氯胺消毒过程中NDMA的形成,而且NDMA的浓度会随氯胺浓度的增加呈线性增加;在中性或稍偏碱性(pH 7～8)的条件下,NDMA生成量最大;二沉池出水中NO2--N和NO3--N的浓度对NDMA的含量皆不会产生明显影响.     

给水管网中耐氯性细菌的灭活特性研究

使用4种常见消毒剂对从实际管网中分离出来的7株耐氯性细菌进行消毒实验.结果表明,这7株细菌均具有较高的耐氯性,其中1株耐氯性最高的类龟分支杆菌自由氯99.9%灭活的CT值为120 mg.(L.min)-1,另外2株血红鞘氨醇单胞菌和甲基杆菌99.9%灭活的CT值分别为7 mg.(L.min)-1和4 mg.(L.min)-1.比较4种消毒剂的消毒效果发现,二氧化氯和单过硫酸氢钾的消毒效果较好,能够在30 min内使分支杆菌的灭活率达到5个数量级.自由氯由于衰减较快,消毒效果不佳.一氯胺能够维持一定的消毒剂浓度,但由于其氧化性较弱,因此需要提高浓度,才能满足消毒要求.能在1 h内灭活3个数量级以上分支杆菌的消毒剂投加量为:3.0 mg/L一氯胺、1.0 mg/L二氧化氯(以Cl2计)和1.0 mg/L单过硫酸氢钾(以Cl2计).考虑到我国水厂消毒的实际情况,建议采用间歇性提高一氯胺浓度或改换二氧化氯消毒的方法,提高对耐氯性细菌的灭活效果.     

One representative water supply system in China with nitrosamine concern: Challenges and treatment strategies

Four sampling campaigns were conducted in two years to understand the fluctuation of N-Nitrosamines (NAs) and their precursors in one drinking water treatment plant (DWTP) in East China in different seasons. This water supply system has been facing several nitrosamine challenges related with source water, including the switch of water source, high concentration of ammonium, formed NAs and NA formation potential (FP) in source water. Besides, the use of ozonation in the DWTP and chloramination in networks will increase the NDMA concentration in tap water. To address these challenges, the bio-pretreatment was applied in this DWTP to decrease the concentration of ammonium and NAs. The following biological activated carbon (BAC) will neutralize the nitrosamine increase brought by ozonation. The use of free chlorine in disinfection process will also decrease the NDMA formation compared with chloramination. The results will benefit other cities in China and other countries with similar impacted water sources.     

污水氯、二氧化氯消毒处理中水质及毒性变化的比较

分别从水质和毒性2方面比较了氯、二氧化氯消毒对污水的影响.结果表明:在水质特性方面,氯消毒对污水色度影响不大,而二氧化氯消毒明显降低了污水的色度;氯、二氧化氯消毒前后污水的DOC基本没有变化;氯消毒后污水的UV₂₃₀明显增加,二氧化氯消毒后污水的UV₂₃₀略有降低,当二者投加量均为30mg/L时,氯消毒使污水的UV₂₃₀增加约0.7cm^-1,二氧化氯消毒使污水的UV₂₃₀降低约0.05cm^-1.在毒性生成方面,氯、二氧化氯消毒产生的急性毒性均随消毒剂投加量的增加而增大,氯消毒产生的急性毒性明显高于二氧化氯消毒;氯消毒在一定程度上增大了污水的遗传毒性,而二氧化氯消毒在一定程度上降低了污水的遗传毒性.     

不同预氧化剂对长江原水氯(胺)化DBPs生成潜能的影响

以取自上海市杨树浦水厂的长江原水为研究对象,对比分析了3种常见预氧化剂二氧化氯(ClO2)、高锰酸钾(KMnO4)及氯(Cl2)预氧化对削减氯化和氯胺化消毒副产物(DBPs)生成潜能的效果情况.氯化培养实验结果表明,3种预氧化剂的处理对DBPs总量的去除效果均不显著,经ClO2、Cl2及KMnO4作用后可分别削减8.4%、5.7%及3.9%,效果为ClO2>Cl2>KMnO4.对于长江原水使用氯化消毒时,采用ClO2作为预氧化剂可取得对消毒副产物较好的去除效果.氯胺化培养实验结果表明,3种预氧化剂处理对长江原水氯胺化DBPs的生成潜能影响有较大差异,经ClO2和KMnO4作用后可分别削减18.1%及4.1%,而预氯化后则增高12.3%,对于长江原水使用氯胺化消毒时,采用ClO2作为预氧化剂可取得对消毒副产物较为明显的去除效果.同时,应尽量避免使用预氯化后加氯胺化的组合,以防止在水处理过程中生成更多的DBPs而影响出水水质.     

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.     

污水二氧化氯和氯消毒过程中遗传毒性的变化及氨氮的影响

采用umu遗传毒性测试方法考察了二氧化氯和氯消毒对几种城市污水生物处理出水遗传毒性的影响,发现当二氧化氯消毒剂从0　mg/L增加到30　mg/L时,几种污水的遗传毒性均先迅速降低后趋于稳定,而当氯消毒剂从0　mg/L增加到30　mg/L时,几种污水的遗传毒性的变化规律不同.进一步研究氨氮对污水消毒过程中遗传毒性变化的影响,发现氨氮对污水二氧化氯消毒过程中遗传毒性的变化规律没有显著影响,但是对污水氯消毒过程中遗传毒性的变化规律却起着至关重要的作用.当氨氮含量较小（<10～20　mg/L）时,污水氯消毒后的遗传毒性小于消毒前;当氨氮含量较大时（>10～20　mg/L）,污水氯消毒后的遗传毒性大于消毒前.     

Formation and speciation of disinfection byproducts during chlor(am)ination of aquarium seawater

The chemistry associated with the disinfection of aquarium seawater is more complicated than that of freshwater, therefore limited information is available on the formation and speciation of disinfection byproducts(DBPs) in marine aquaria. In this study, the effects of organic precursors, bromide(Br-) and pre-ozonation on the formation and speciation of several typical classes of DBPs, including trihalomethanes(THM4), haloacetic acids(HAAs),iodinated trihalomethanes(I-THMs), and haloacetamides(HAc Ams), were investigated during the chlorination/chloramination of aquarium seawater. Results indicate that with an increase in dissolved organic carbon concentration from 4.5 to 9.4 mg/L, the concentrations of THM4 and HAAs increased by 3.2–7.8 times under chlorination and by 1.1–2.3 times under chloramination. An increase in Br-concentration from 3 to 68 mg/L generally enhanced the formation of THM4, I-THMs and HAc Ams and increased the bromine substitution factors of all studied DBPs as well, whereas it impacted insignificantly on the yield of HAAs. Pre-ozonation with 1 mg/L O3 dose substantially reduced the formation of all studied DBPs in the subsequent chlorination and I-THMs in the subsequent chloramination. Because chloramination produces much lower amounts of DBPs than chlorination, it tends to be more suitable for disinfection of aquarium seawater.     

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.     

Effects of disinfection efficiency on microbial communities and corrosion processes in drinking water distribution systems simulated with actual running conditions

The effects of disinfection efficiency on microbial communities and the corrosion of cast iron pipes in drinking water distribution systems (DWDSs) were studied. Two annular reactors (ARs) that simulated actual running conditions with UV/Cl₂ disinfection and chlorination alone were used. High chlorine consumption and corrosion rate were found in the AR with UV/Cl₂. According to functional genes and pyrosequencing tests, a high percentage of iron recycling bacteria was detected within the biofilm of the AR with Cl₂ at early running stage, whereas siderophore-producing bacteria were dominant in the biofilm of the AR with UV/Cl_2. At the early running stage, the sequential use of UV light and an initial high chlorine dosage suppressed the biomass and iron-recycling bacteria in both bulk water and biofilms, thereby forming less protective scales against further corrosion, which enhanced chlorine consumption. Non-metric multidimensional scaling analysis showed that the bacterial communities in the ARs shaped from within rather than being imported by influents. These results indicate that the initial high disinfection efficiency within the distribution system had not contributed to the accumulation of iron-recycling bacteria at the early running stages. This study offer certain implications for controlling corrosion and water quality in DWDSs.     

Evaluate HAA removal in biologically active carbon filters using the ICR database

The effects of biologically active carbon (BAC) filtration on haloacetic acid (HAA) levels in plant effluents and distribution systems were investigated using the United States Environmental Protection Agency’s Information Collection Rule (ICR) database. The results showed that average HAA5 concentrations in all locations were 20.4 μg·L⁻¹ and 29.6 μg·L⁻¹ in ICR plants with granular activated carbon (GAC) and ICR plants without GAC process, respectively. For plants without GAC, the highest HAA levels were observed in the quarters of April to June and July to September. However, for plants with GAC, the highest HAA levels were observed in the quarters of April to June and January to March. This HAA level profile inversely correlated well with water temperature, or biologic activity. For GAC plants, simulated distribution samples matched well with distribution system equivalent samples for Cl₃AA and THMs. For plants with and without GAC, simulated distribution samples overestimated readily biodegradable HAAs in distribution systems. The study indicated that through HAA biodegradation, GAC process plays an important role in lowering HAA levels in finished drinking water.     

给水管网中耐氯分枝杆菌的灭活特性及机制研究

近年来,在饮用水管网中检测到耐受消毒剂的微生物,对于饮用水安全造成威胁.课题组由南方某城市自来水管网中分离出1株耐氯的产黏液分枝杆菌(Mycobacteria mucogenicum),并对其灭活特性和耐氯机制进行了研究.使用自由氯、一氯胺和二氧化氯对其进行消毒实验,测定CT值.99.9%灭活产黏液分枝杆菌时,自由氯的CT值为(76.25±47.55)mg·min·L-1,一氯胺为(1 396±382)mg·min·L-1,二氧化氯为(13.5±4.9)mg·min·L-1.采用透射电镜对产黏液分枝杆菌的消毒过程进行观察,发现消毒后细菌结构疏松,细胞器层次变得不清晰,核心肿胀溶解.产黏液分枝杆菌具有较好的疏水性,测定其表面疏水率为37.2%,远高于其他细菌,使得亲水性消毒剂不易进入细菌内部,是其耐受含氯消毒剂的原因之一.     

Effects of O3/Cl2 disinfection on corrosion and opportunistic pathogens growth in drinking water distribution systems

The effects of O_3/Cl_2 disinfection on corrosion and the growth of opportunistic pathogens in drinking water distribution systems were studied using annular reactors(ARs).The corrosion process and most probable number(MPN) analysis indicated that the higher content of iron-oxidizing bacteria and iron-reducing bacteria in biofilms of the AR treated with O_3/Cl_2 induced higher Fe_3O_4 formation in corrosion scales.These corrosion scales became more stable than the ones that formed in the AR treated with Cl_2 alone.O_3/Cl_2 disinfection inhibited corrosion and iron release efficiently by changing the content of corrosion-related bacteria.Moreover,ozone disinfection inactivated or damaged the opportunistic pathogens due to its strong oxidizing properties.The damaged bacteria resulting from initial ozone treatment were inactivated by the subsequent chlorine disinfection.Compared with the AR treated with Cl_2 alone,the opportunistic pathogens M.avium and L.pneumophila were not detectable in effluents of the AR treated with O_3/Cl_2,and decreased to(4.60 ± 0.14) and(3.09 ± 0.12) log10(gene copies/g corrosion scales) in biofilms,respectively.The amoeba counts were also lower in the AR treated with O_3/Cl_2.Therefore,O_3/C_l2 disinfection can effectively control opportunistic pathogens in effluents and biofilms of an AR used as a model for a drinking water distribution system.     

Variation in assimilable organic carbon formation during chlorination of Microcystis aeruginosa extracellular organic matter solutions

This study investigated the chlorination of Microcystis aeruginosa extracellular organic matter(EOM) solutions under different conditions, to determine how the metabolites produced by these organisms affect water safety and the formation of assimilable organic carbon(AOC). The effects of chlorine dosages, coagulant dosage, reaction time and temperature on the formation of AOC were investigated during the disinfection of M.aeruginosa metabolite solutions. The concentration of AOC followed a decreasing and then increasing pattern with increasing temperature and reaction time. The concentration of AOC decreased and then increased with increasing chlorination dosage, followed by a slight decrease at the highest level of chlorination. However, the concentration of AOC decreased continuously with increasing coagulant dosage. The formation of AOC can be suppressed under appropriate conditions. In this study, chlorination at 4 mg/L, combined with a coagulant dose of 40 mg/L at 20°C over a reaction time of 12 hr, produced the minimum AOC.