Formation of Disinfection Byproducts (DBPs) in Surface Water Sources: Differential Ultraviolet (UV) Absorbance Approach

Chlorination for drinking water forms various disinfection byproducts (DBPs) of trihalomethanes (THMs) and haloacetic acids (HAAs). Chlorination has been attributed to the destruction of activated aromatic sites of the natural organic matter (NOM) predominantly at electron rich sites. Experiments with Istanbul surface waters showed that the magnitude of the decrease in the ultraviolet (UV) absorbance at 272 nm (UV₂₇₂) was an excellent indicator of destruction of these sites by chlorine. The main objective of the present study is to develop the differential UV₂₇₂ absorbance (ΔUV₂₇₂) related models for the prediction of the formation of THM, HAA, and their species in raw water samples from Terkos, Buyukcekmece, and Omerli lakes under different chlorination conditions. Significant factors affecting DBP formation in the raw waters were identified through numerical and graphical techniques. The R² values of the models varied between 0.94 and 0.97, indicating excellent predictive ability for THM₄ and HAA₉ in the raw waters. The models were validated using additional data. The results of this study concluded that addition of ΔUV₂₇₂ parameter into THM₄ and HAA₉ models make the prediction of these DBP compounds more precisely than those of DBP models developed in the past. A better understanding of these modeling systems will help the water treatment plant operators to minimize the DBP formation, providing a healthier and better drinking water quality as well as identifying strategies to improve water treatment and disinfection processes.     

高强UV/SO32-体系高效降解一氯乙酸

为有效解决饮用水中卤代乙酸（HAAs）污染问题,选取水中典型HAAs一氯乙酸（MCAA）作为目标污染物,系统研究了高强UV/SO₃^2-体系对其降解效能及影响因素.结果表明,高强UV/SO₃^2-体系可高效降解MCAA,50s内初始浓度为50 μmol/L的MCAA可被完全降解.与已报导的还原法降解MCAA的文献相比,本研究中MCAA降解速率提高了1000倍以上.提高SO₃^2-浓度、溶液初始pH以及紫外光强均有利于体系中MCAA降解率的提高.水中共存物质研究表明,NH₄⁺可促进MCAA降解,而NO₃^-、HCO₃^-、NOM均会抑制MCAA降解,其中,HCO₃^-影响较小.     

MBR处理医院污水后续氯消毒及其消毒副产物研究

针对医院污水中致病微生物的特殊排放要求,研究了膜生物反应器（MBR）应用于医院污水处理中的预消毒及其后续氯消毒特性.结果表明,在工程应用中MBR具有显著的预消毒作用,对医院污水中的细菌总数和粪大肠杆菌的去除率分别达到2.0～3.1 lg和2.8～4.0 lg;对于MBR出水中残留的微生物,采用次氯酸钠进行后续消毒,当接触时间为1 h,在有效氯浓度为0.8 　mg/L时,可检测不出粪大肠杆菌,且放置6 h未见再生长,相应的THMs和HAAs分别为16.94 μg/L和32.10 μg/L;固定接触时间,随着Cl₂/DOC值的增加,MBR出水中THMs和HAAs均近似呈线性增长趋势（r²分别为0.941?5和 0.965?2）,且HAAs的增长速率高于THMs.     

Determination of haloacetic acids in hospital effuent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction (SPE) method was developed for the analysis of low concentration haloacetic acids (HAAs), a class of disinfection by-products formed from chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 mlmin, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples' turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μgL and 1.30 μgL, respectively, and the other three acids are ranging from 0.48 to 0.82 μgL under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid was the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.     

水体中卤乙酸(HAAs)的产生、测定方法与控制途径

对饮用水中普遍存在的消毒副产物形式HAAs的产生、测定方法以及控制途径进行了阐述.并对影响HAAs生成的主要因素投氯量、溴的影响以及卤乙酸副产物(HAAFP)含量等进行了分析.生物活性炭技术是一种非常有效的控制HAAs含量和减少HAAFP含量的方法,对于保障饮用水安全性具有重要意义.     

芳香类有机物生成氯化消毒副产物特性及其与化学结构的关系

选择与腐殖酸有相似芳香结构的有机物进行氯化试验,测定其卤乙酸及三卤甲烷生成量,研究前体物化学结构与氯化消毒副产物生成特性的关系.结果表明:①主要卤乙酸生成活性排序为:对羟基苯甲酸>4-氨基苯乙酮>邻苯二酚>间苯二酚;主要三卤甲烷生成活性排序为:间苯二酚>4-氨基苯乙酮>2-羟基-4-氨基甲苯>对羟基苯甲酸.②卤乙酸的前期氯化反应速度排序为:间苯二酚>4-氨基苯乙酮>对羟基苯甲酸>邻苯二酚;三卤甲烷的前期氯化反应速度排序为:对羟基苯甲酸>2-羟基-4-氨基甲苯>间苯二酚>4-氨基苯乙酮.③对位或邻位取代基结构物质以生成卤乙酸为主;间位取代基结构物质以生成三卤甲烷为主.④苯环上羟基官能团生成消毒副产物的活性最高,酮基官能团次之;氨基官能团主要起到与其它活性官能团形成对位、邻位或间位结构的辅助作用;醛基和羧基官能团为惰性官能团;甲基官能团的作用有待深入考察.     

温度对生物活性炭降解卤乙酸的影响

卤乙酸(HAAs)是饮用水中常见的氯和氯胺消毒副产物,具有较高的亲水性与致癌性,为了保证水质与人体健康,各国均对其制定了相关规定。考察了生物活性碳(BAC)对9种HAA的去除性能,并探讨HAA生物降解效果随温度的变化情况与生物反应的去除机理,反应动力学与热力学。结果显示,BAC可有效去除水体中的一卤代与二卤代乙酸,难以去除三卤代乙酸。BAC的生物降解性能明显可分为2个部分:低温(5~15℃)基本不发生生物降解;高温(25~35℃)生物降解性能显著。在不同温度下,HAA的生物降解均符合一级反应动力学,反应速率常数为0.01~0.40 min-1;BAC降解HAA的过程不是逐级氢取代卤而是同时脱去所有卤素的反应,卤代乙酸生物反应的活化能为63.5~89.2 kJ/mol。     

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.     

几种模型物质在氯化中形成THMs、HAAs的特性研究

以胃蛋白酶(蛋白质)、谷胱甘肽(氨基酸多肽)、葡萄糖(糖类)作为模型物质代表藻来源有机物,并以Fluka腐殖酸为对照,研究其耗氯量、三卤甲烷(主要是氯仿)、卤乙酸(主要是二氯乙酸(DCAA)、三氯乙酸(TCAA))的形成情况.结果显示4种模型物质在氯化后,其余氯在前2 h迅速降低,6 h后则下降速度渐缓;其中耗氯量最大的是谷胱甘肽(96 h:7.1 mg·mg^-1(以每毫克碳计,下同)),其次是胃蛋白酶(96 h:4.2 mg·mg^-1)、腐殖酸(96 h:3.0 mg·mg^-1),而葡萄糖最小(96 h:0.7 mg·mg^-1).4种模型物质氯仿、DCAA、TCAA的生成速度也是在起初的2 h较快,随后渐缓;但从单位碳的产量来看,腐殖酸和胃蛋白酶形成氯仿(96h: 15.1~55.2 μg·mg^-1(以每毫克碳计,下同))、DCAA(96 h: 15.1~55.2 μg·mg^-1)、TCAA(96h: 15.1~55.2 μg·mg^-1)均较多,而谷胱甘肽、葡萄糖则相对较少(氯仿-96 h:2.5~5.1 μg·mg^-1;DCAA-96 h:0.6~8.0 μg·mg^-1;TCAA-96 h:0.12~3.8 μg·mg^-1);而从前驱物特性来说,氯仿、TCAA的前驱物具有较高的芳香度(即高的SUV₂₅₄值),而DCAA前驱物的SUV₂₅₄相对较低.对于富含蛋白质、多肽、糖类等的富营养化饮用水源,则要格外注意饮用水中DCAA所带来的健康风险.     

氯消毒再生水中4种卤乙酸的测定和影响因素分析

再生水在回用过程中氯消毒副产物对人体产生的危害逐渐引起人们的关注.在USEPA552.3(2003)标准方法的基础上,建立了适用于检测再生水中氯消毒副产物4种卤乙酸(haloacetic acids,HAAs)的分析方法,并对加氯量、UV254、氨氮浓度等影响因素及控制方法进行了研究.研究表明,方法前处理过程简单、安全,内标、HAAs组分峰在谱图分辨良好;4种HAAs在浓度范围1～150 μg/L内呈线性关系,校准曲线相关系数均大于0.999;加标回收率在82.27％～119.9％之间,满足标准方法的要求;HAAs浓度随加氯量的增大而增大,随氨氮浓度的增大而减小,随UV254的变化不明显;先加氨后加氯的消毒方式产生的HAAs浓度最低,两点加氯产生的HAAs总量要少于单一点加氯.