Progress in Analytical Methods of Halogenated Disinfection By-Products

Ensuring the health and safety of drinking water is crucial for both nations and their citizens.Since the 20th century,the disinfection of drinking water,effectively controlling pathogens in water sources,has become one of the significant advances in public health.However,the disinfectants used in the process,such as chlorine and chlorine dioxide,react with natural organic matter in the water to produce disinfection by-products(DBPs).Most of these DBPs contain chlorine,and if the source water contains bromine or iodine,brominated or iodinated DBPs,collectively referred to as Halogenated disinfection byproducts(X-DBPs),are formed.Numerous studies have found that X-DBPs pose potential risks to human health and the environment,leading to widespread concern.Mass spectrometry has become an important means of discovering new types of X-DBPs.This paper focuses on the study of methods for analyzing X-DBPs in drinking water using mass spectrometry.

Characterization of dissolved organic matter fractions and its relationship with the disinfection by-product formation

Dissolved organic matter （DOM） has been identified as precursor for disinfection by-products （DBPs） formation during chlorination. Recently, it has been demonstrated that the characteristics of DOM influence the DBPs formation mechanism. A study was, therefore, initiated to investigate the effects of DOM fractions on DBPs formation mechanism. In the chlorination process, organic acids are dominant precursors of total thihalomethanes （TTHM） because of the vc-o and unsaturated structures. Furthermore, the TTHM formation of organic acids was affected by pH more greatly. Based on the fluorescence spectroscopy analysis, DOM fractions contained several fluorescence substances. During chlorination, humic acid-like substances were found to exhibit high chlorine reactivity and hydrophobic organics decomposed to smaller molecules faster than hydrophilic organics even at lower chlorine dosages. Unlike hydrophobic fractions, hydrophilic organics showed no toxicity following chlorination, suggesting that the toxic structures in hydrophihc organics showed high chlorine reactivity during chlorination.

Simultaneous Control of Microorganisms and Disinfection By-products by Sequential Chlorination

Objective To introduce a new sequential chlorination disinfection process in which short-term free chlorine and chloramine are sequentially added. Methods Pilot tests of this sequential chlorination were carried out in a drinking water plant. Results The sequential chlorination disinfection process had the same or better efficiency on microbe （including virus） inactivation compared with the free chlorine disinfection process. There seemed to be some synergetic disinfection effect between free chlorine and monochloramine because they attacked different targets. The sequential chlorination disinfection process resulted in 35.7%-77.0% TTHM formation and 36.6%-54.8% THAA5 formation less than the free chlorination process. The poorer the water quality was, the more advantage the sequential chlorination disinfection had over the free chlorination. Conclusion This process takes advantages of free chlorine＇s quick inactivation of microorganisms and chloramine＇s low disinfection by-product （DBP） yield and long-term residual effect, allowing simultaneous control of microbes and DBPs in an effective and economic way.

Removal of disinfection by-products formation potential by biologically intensified process

The removal of disinfection by-products formation potential(DBPFP) in artificially intensified biological activated carbon(IBAC) process which is developed on the basis of traditional ozone granular activated carbon was evaluated. By IBAC removals of 31% and 68% for THMFP and HAAFP were obtained respectively. Under identical conditions, the removals of the same substances were 4% and 32% respectively only by the granular activated carbon(GAC) process. Compared with GAC, the high removal rates of the two formed potential substances were due to the increasing of bioactivity of the media and the synergistic capabilities of biological degradation cooperating with activated carbon adsorption of organic compounds. A clear linear correlation(R 2=0.9562 and R 2=0.9007) between DOC HAAFP removal rate and Empty Bed Contact Time(EBCT) of IBAC process was observed, while that between THMFP removal rate and EBCT of GAC was R 2=0.9782. In addition certain linear correlations between THMFP, HAAFP and UV 254 (R 2=0.855 and R 2=0.7702) were found for the treated water. For IBAC process there are also more advantages such as long backwashing cycle time, low backwashing intensity and prolonging activated carbon lifetime and so on.

我国典型水源地N-DBPs生成势及生态风险评价

随着含氮消毒副产物(N-DBPs)的基因毒性和细胞毒性受到重视,饮用水中的N-DBPs产生和生态风险的研究成为近年的关注热点。文章基于前人研究分析,研究了我国典型水源地中N-DBPs生成势的空间分布特征,采用风险熵值法,对我国典型水源地N-DBPs的潜在生成生态风险进行了评估,还关注了有机物指标与N-DBPs生成势之间的关系。结果表明:DON与N-DBPs生成势的分布特点均存在地域差异,总体表现为在东部沿海城市呈现南北高、中部低、东部地区高于其他地区、经济发达地区高于其他地区、珠三角地区高于其他地区的特点。结合生态风险的评价方法,利用现有数据进行初步估计,发现部分城市水源地生态风险呈现低风险,水库水源N-DBPs的生态风险一般高于河流水源。UV_(254)与N-DBPs生成势相关性较好,可以作为N-DBPs生成势的替代性指标。研究结果将为做好我国水源地的修复与保护、保障居民饮水安全提供重要的支撑。

Health Risk Assessment of Employees Exposed to Chlorination By-products of Recreational Water in Large Amusement Parks in Shanghai

Objective Chlorination is often used to disinfect recreational water in large amusement parks;however,the health hazards of chlorination disinfection by-products(DBPs)to occupational populations are unknown.This study aimed to assess the exposure status of chlorinated DBPs in recreational water and the health risks to employees of large amusement parks.Methods Exposure parameters of employees of three large amusement parks in Shanghai were investigated using a questionnaire.Seven typical chlorinated DBPs in recreational water and spray samples were quantified by gas chromatography,and the health risks to amusement park employees exposed to chlorinated DBPs were evaluated according to the WHO's risk assessment framework.Results Trichloroacetic acid,dibromochloromethane,bromodichloromethane,and dichloroacetic acid were detected predominantly in recreational water.The carcinogenic and non-carcinogenic risks of the five DBPs did not exceed the risk thresholds.In addition,the carcinogenic and non-carcinogenic risks of mixed exposure to DBPs were within the acceptable risk limits.Conclusion Typical DBPs were widely detected in recreational water collected from three large amusement parks in Shanghai;however,the health risks of DBPs and their mixtures were within acceptable limits.

Removal characteristics of disinfection by-products formation potential by bioaugmentation activated carbon process

The high-active bacteria were screened from 8 dominant bacteria obtained from the natural water body,and then the bioaugmentation activated carbon was formed by hydraulic immobilization of the high-active bacteria. Plant-scale studies on removal characteristics of disinfection by-products formation potentials (DBPFP) by bioaugmentation activated carbon process were conducted for micro-polluted raw water treatment. The results show that the bioaugmentation activated carbon process has adopted better purification efficiency to THMFP and HAAFP than traditional biological activated carbon process,and that average removal efficiencies of THMFP and HAAFP can reach 35% and 39.7% during the test period,increasing by more than 10% compared with traditional biological activated carbon process. The removal efficiencies of THMFP and HAAFP are stable because of the biodegradation of the high-active bacteria and the adsorption of active carbon. The biodegradability of CHCl3 formation potential is better as compared with that of CHCl2Br and CHClBr2 formation potentials among THMFP,and high removal efficiency of CHCl3formation potential is obtained by bioaugmentation degradation of the high-active bacteria. The biodegradability of HAAFP is better in comparison with that of THMFP,and the chemical properties of HAAFP are propitious to adsorption of activated carbon. Thus,HAAFP is on predominance during the competitive removal process with THMFP.

Alternate disinfection approaches or raise disinfectant dosages for sewage treatment plants to address the COVID-19 pandemic?From disinfection efficiency,DBP formation,and toxicity perspectives

During the COVID-19 pandemic,most sewage treatment plants increased disinfectant dosages to inactivate pathogenic viruses and microorganisms more effectively.However,this approach also led to the production of more disinfection by-products(DBPs).To ensure both disinfection efficiency and a reduction in DBP formation,new disinfection protocols are required.In this study,the disinfection efficiency,DBP amounts,and toxicity changes resulting from ozone(O_(3)),ultraviolet(UV),chlorine(Cl_(2)),and their combined processes were examined.The results demonstrated that the O_(3)/UV/Cl_(2)combination achieved the highest disinfection efficiency.Chlorination produced the most DBPs,whereas UV treatment reduced the formation of trihalomethane(THM),halogenated ketones(HKs),haloacetic acids(HAA),dichloroacetonitrile(DCAN)and N-nitrosodimethylamine(NDMA)by 45.9%,52.6%,82.0%,67.95%,and 47%,respectively.O_(3)also significantly reduced their production by 99.1%,91.1%,99.5%,100%,and 35%.Intracellular organic matter(IOM)was identified as the primary DBP precursors,producing 2.94 times more DBPs than extracellular organic matter(EOM).The increased DBP formation during chlorination was attributed to IOM leakage and cell membrane damage,which was verified using scanning electron microscopy(SEM).The toxicities of DBPs were evaluated for six disinfection methods,revealing inconsistent results.The overall toxicities were assessed using zebrafish embryo experiments.Both evaluations indicated that chlorination alone was the least favorable method.In addition,the toxicities followed a sequence:Cl_(2)≈O_(3)/Cl_(2)>O_(3)>O_(3)/UV/Cl_(2)>UV>UV/Cl_(2).These findings can serve as a reference for sewage treatment plants in selecting appropriate disinfection methods to manage the COVID-19 epidemic from comprehensive perspective.

Less pressure contributes to gravity-driven membrane ultrafiltration with greater performance:Enhanced driving efficiency and reduced disinfection by-products formation potential

Gravity-driven membrane(GDM)systems have been well developed previously;however,impacts of driving(i.e.,transmembrane)pressure on their performance received little attention,which may infuence GDM performance.In this study,we evaluated 4 GDM systems via altering the transmembrane pressure from 50 mbar to 150 mbar with 2 groups,treating surface water in Beijing,China.Results showed that less driving pressure was more favorable.Specifically,compared to groups(150 mbar),groups under a pressure of 50 mbar were found to have greater normalized permeability and lower total resistance.During the whole operation period,the quality of effuents was gradually improved.For example,the removal efficiency of UV254was significantly improved;particularly,under low driving pressure,the removal efficiency of UV254in PES GDM system increased by 11.91%,as compared to the corresponding system under high driving pressure.This observation was consistent with the reduction on disinfection by-products(DBPs)formation potential;groups under 50 mbar achieved better DBPs potential control,indicating the advantages of lower driving pressure.Biofilms were analyzed and responsible for these differences,and distinct distributions of bacteria communities of two GDM systems under 50 and 150 mbar may be responsible for various humic-like substances removal efficiency.Overall,GDM systems under less pressure should be considered and expected to provide suggestions on the design of GDM systems in real applications.

Waste Water Disinfection During SARS Epidemic for Microbiological and Toxicological Control

Objective To evaluate the disinfection of wastewater in China. Methods During the SARS epidemic occurred in Beijing, a study of different disinfection methods used in the main local wastewater plants including means of chlorine, chlorine dioxide, ozone, and ultraviolet was carried out in our laboratory. The residual coliform, bacteria and trihalomethanes, haloacetic acids were determined after disinfection. Results Chlorine had fairly better efficiency on microorganism inactivation than chlorine dioxide with the same dosage. Formation of THMs and HAAs does not exceed the drinking water standard. UV irradiation had good efficiency on microorganism inactivation and good future of application in China. Organic material and ammonia nitrogen was found to be significant on inactivation and DBPs formation. Conclusion Chlorine disinfection seems to be the best available technology for coliform and bacteria inactivation. And it is of fairly low toxicological hazard due to the transformation of monochloramine.

Disinfection of swimming pools with chlorine and derivatives: formation of organochlorinated and organobrominated compounds and exposure of pool personnel and swimmers

Chlorination of pool water leads to the forma-tion of many by-products, chloroform usually being the most abundant. The paper reports the results of a study evaluating exposure of bath-ers and pool employees to trihalomethanes (chloroform, bromodichloromethane, dibromo-chloromethane, bromoform) in four indoor swimming pools with chlorinated water. Chlo-roform concentrations in environmental air samples when the pool was in use (about 9 h), in the range 1-182 μg/m3, were greater near the pool than in the change rooms, passageways and offices. Chloroform concentrations in per-sonal air samples of pool employees were in the range 18-138 μg/m3. Urinary concentrations of chloroform averaged (geometric means) 0.123 and 0.165 μg/l and 0.404 and 0.342 μg/l prior and at the end of exposure during in water and out of water activities, respectively. The significant increase in urinary excretion of chloroform confirms that the source of the contaminant was pool water. Absorption of chloroform, estimated from airborne and water concentrations, was significantly correlated with delta chloroform (after/before exposure) and urinary concentra-tions of chloroform at the end of exposure. As chloroform is a toxic and possibly carcinogenic substance, these observations pose a problem principally for the general population of pool users.

水源水Fe(Ⅵ)与Mn(Ⅶ)预氧化对天然有机物的组成特征及消毒副产物生成势的影响

溶解有机物(DOM)普遍存在于地表水源中,是饮用水消毒副产物的重要前驱物.本研究考察了Fe(Ⅵ)与Mn(Ⅶ)预氧化对浙江东部某水源水中DOM的组成特征及消毒副产物生成势的影响.运用三维荧光光谱(3D-EEMs)分析了两种氧化剂在不同的浓度梯度下对水样进行预氧化后,水样DOM的荧光光谱特性、荧光特征参数和荧光组分等的变化情况,及氯化后消毒副产物(DBPs)的生成情况.结果表明,水源水水样DOM的来源主要为陆源与内源混合且具有一定的腐殖质化程度,Mn(Ⅶ)和Fe(Ⅵ)预氧化不仅对荧光DOM具有较好的降解效果,对腐殖质类DOM也具有一定的降解作用.在DBPs的生成势方面,Mn(Ⅶ)预氧化对三氯甲烷(TCM)生成势的变化呈现出先增强后减弱的现象,对二氯乙腈(DCAN)的生成势具有一定的减弱作用.而Fe(Ⅵ)预氧化对三氯丙酮(1,1,1-TCP)、溴氯乙腈(BCAN)、二溴乙腈(DBAN)和DCAN的生成势均具有明显的降低作用,对二氯一溴甲烷(DCBM)、二溴一氯甲烷(DBCM)和三溴甲烷(TBM)生成势的变化呈现出先增强后减弱的现象.研究结果推动了水源水氧化消毒工艺的发展并为相关研究提供理论指导.

强化絮凝去除水中 DBP 先质研究(Ⅰ)

分析探讨了水中ＤＢＰ的产生、消除方法及去除ＤＢＰ先质的絮凝机理，认为在传统水净化工艺中，通过强化絮凝可进一步去除水中的ＤＢＰ先质．实验研究了强化絮凝条件下，去除水中腐殖酸类有机质的适宜操作控制条件，求得了该条件下的最优ｐＨ值及最佳投药量．

饮用水新型N-DBPs类别及毒理学评价

基于国外最新文献,系统划分了新近发现的饮用水含氮消毒副产物(N-DBPs),包括卤代乙腈(HANs)、亚硝胺(以亚硝基二甲胺为代表,简称NDMA)和卤代硝基甲烷(HNMs)三大类物质。详细归纳了各N-DBPs的毒理性质,并将N-DBPs的慢性细胞毒性、急性遗传毒性以及致癌性与三卤甲烷(THMs)和卤乙酸(HAAs)等饮用水常见DBPs进行对比,发现HANs和HNMs的慢性细胞毒性以及急性遗传毒性均远高于HAAs,NDMA的致癌性也远高于THMs和HAAs,饮用水N-DBPs亟待进一步研究。最后展望了今后的研究方向。

紫外消毒技术在水厂的应用及工程实例

与氯消毒、臭氧消毒等化学消毒相比,紫外线(ultraviolet,UV)消毒具有广谱灭菌、消毒接触时间短、不使用化学药剂、不会产生消毒副产物、便于实现自动化控制等优点。浙江某水厂供水能力为20万m^(3)/d,工艺采用UV+次氯酸钠联合消毒工艺,充分利用UV消毒技术无消毒副产物的优势以及次氯酸钠消毒的持续消毒能力。工程应用中设定UV剂量为40.00 mJ/cm^(2),UV穿透率为90.00%,实际UV剂量为48.99 mJ/cm^(2)。UV消毒后,菌落总数为未检出。补加氯量与常规投量相比下降约30%,UV消毒的应用可以在降低化学药剂投加成本的同时兼顾饮用水化学和生物安全性。工程的成功应用为相同类型的水厂消毒工艺的升级改造提供经验。

纳滤膜工艺在太仓某水厂深度处理工程中的应用

为向太仓市民供应“优质”饮用水,太仓市某水厂选用国内自主研发的低压纳滤膜产品与技术进行深度处理改造,规模为5万m^(3)/d,于2019年12月投产运行。对纳滤系统连续监测的数据显示,在设计回收率为85%的情况下,纳滤膜产水TOC平均质量浓度为0.10 mg/L,残留铝质量浓度低于0.02 mg/L,对色氨酸类蛋白质、微生物代谢产物等溶解性有机质的去除效果显著;对TDS和总硬度平均去除率为24.78%和30.64%,说明纳滤膜在高效截留有毒有害物质的同时,保留了一部分对人体有益的天然矿物质。纳滤系统运行稳定、抗污染性能较好,运行电费和药剂费仅为0.236元/m^(3),经济可行,是一种优质的饮用水深度处理技术。该水厂为国内首座采用国产纳滤膜去除有机物的饮用水净化工程,验证了国产纳滤饮用水处理技术的安全性、稳定性和经济性。

吹扫捕集-三重四级杆气质联用测定生活饮用水中9种含氮消毒副产物

建立吹扫捕集-三重四级气质联用测定饮用水中6种卤乙腈、3种卤代硝基甲烷消毒副产物(DBPs)的方法,并了解本市饮用水中目标DBPs的浓度水平。优化吹扫捕集条件,气质联用条件建立检测方法,并对日常饮用水、原水样品进行检测,选用10#捕集阱(2,6-二苯基对苯醚/硅胶/碳分子筛),选用DB-VRX色谱柱,对比25 mL吹扫管与5 mL吹扫管前处理灵敏度,确定吹脱时间为11 min,捕集阱温度为40℃,捕集阱热脱附温度为190℃,传输线温度为115℃,烘烤时间为10 min,吹扫流量为40 mL/min。在多反应监测(SRM)模式下检测,外标法定量。结果表明,各个物质线性范围良好,r>0.996,方法检出限(LODs)为0.051~0.14μg/L,定量限为0.25~0.56μg/L,两种不同浓度加标回收率为70.2%~117.0%,相对标准偏差为2.45%~10.50%。该方法高效、灵敏、操作简单,对卤乙腈、卤代硝基甲烷等DBPs能进行有效检测。对出厂水、管网水进行检测,不同消毒工艺次氯酸钠、液氯和二氧化氯消毒时,卤乙腈检出质量浓度不同,为ND~3.20μg/L,卤代硝基甲烷未检出。

Impact of ozonation on disinfection byproducts formation from phenylalanine during chlorination

As a strong oxidizing agent,ozone is used in some water treatment facilities for disinfection,taste and odor control,and removal of organic micropollutants.Phenylalanine(Phe)was used as the target amino acid to comprehensively investigate variability of disinfection byproducts(DBPs)formation during chlorine disinfection and residual chlorine conditions subsequent to ozonation.The results showed that subsequent to ozonation,the typical regulated and unregulated DBPs formation potential(DBPsFP),including trichloromethane(TCM),dichloroacetonitrile(DCAN),chloral hydrate(CH),dichloroacetic acid(DCAA),trichloroacetic acid(TCAA),and trichloroacetamide(TCAcAm)increased substantially,by 2.4,3.3,5.6,1.2,2.5,and 6.0 times,respectively,compared with only chlorination.Ozonation also significantly increased the DBPs yield under a 2 day simulated residual chlorine condition that mimicked the water distribution system.DBPs formations followed pseudo first order kinetics.The formation rates of DBPs in the first 6 hr were higher for TCM(0.214 hr^(−1)),DCAN(0.244 hr^(−1)),CH(0.105 hr^(−1)),TCAcAm(0.234 hr^(−1)),DCAA(0.375 hr^(−1))and TCAA(0.190 hr^(−1))than thereafter.The peak DBPsFP of TCM,DCAN,CH,TCAcAm,DCAA,and TCAA were obtained when that ozonation time was set at 5–15 min.Ozonation times>30 min increased the mineralization of Phe and decreased the formation of DBPs upon chlorination.Increasing bromine ion(Br^(−1))concentration increased production of bromine-DBPs and decreased chlorine-DBPs formation by 59.3%–92.2%.Higher ozone dosages and slight alkaline favored to reduce DBP formation and cytotoxicity.The ozonation conditions should be optimized for all application purposes including DBPs reduction.

饮用水氯消毒生成DBPs的影响因素及其控制工艺

阐述了饮用水消毒副产物(DBPs)产生的影响因素,分析了天然有机物(NOM)、温度、pH、接触时间、氯用量和余氯浓度等各种因素对产生DBPs种类和数量的影响,提出了控制DBPs应从去除其前体物NOM,改变消毒工艺或采用新的消毒剂以及去除已生成的DBPs三方面入手。

Identification of key precursors contributing to the formation of CX_(3)R-type disinfection by-products along the typical full-scale drinking water treatment processes

Identification and characterization of disinfection by-product(DBP)precursors could help optimize drinkingwater treatment processes and improve the quality of finishedwater.This study comprehensively investigated the characteristics of dissolved organic matter(DOM),the hydrophilicity and molecule weight(MW)of DBP precursor and DBP-associated toxicity along the typical full-scale treatment processes.The results showed that dissolved organic carbon and dissolved organic nitrogen content,the fluorescence intensity and the SUVA254 value in raw water significantly decreased after the whole treatment processes.Conventional treatment processes were in favor of the removal of high-MW and hydrophobic DOM,which are important precursors of trihalomethane and haloacetic acid.Compared with conventional treatment processes,Ozone integrated with biological activated carbon(O3-BAC)processes enhanced the removal efficiencies of DOM with different MW and hydrophobic fractions,leading to a further decrease in almost all DBP formation potential and DBP-associated toxicity.However,almost 50%of the detected DBP precursors in raw water has not been removed after the coagulation-sedimentation-filtration integrated with O3-BAC advanced treatment processes.These remaining precursors were found to be mainly hydrophilic and low-MW(<1.0 kDa)organics.Moreover,they would largely contribute to the formation of haloacetaldehydes and haloacetonitriles,which dominated the calculated cytotoxicity.Since current drinking water treatment process could not effectively control the highly toxic DBPs,the removal of hydrophilic and low-MW organics in drinking water treatment plants should be focused on in the future.