饮水中三卤甲烷形成机理与处理技术现状

综述了水中腐酸氯化产物及其形成三卤甲烷的反应历程及各种环境条件如ｐＨ值，光照及自由基对ＴＨＭｓ形成的影响，并提出控制和去除饮水ＴＨＭｓ的方法。     

活性炭对水中有机物去除的研究

活性炭吸附是受污染水源水深度处理的有效手段，本文较系统地研究和阐述了颗粒活性炭对水中有机物吸附的选择性。活性炭可有效降低水的致突变活性，有时能使Ａｍｅｓ试验的阳性水转化为阴性水；活性炭对分子量小于３０００，尤其是分子量５００￣１０００的有机物能较好的去除；活性炭对消毒副产物卤乙酸（ＨＡＡｓ）的控制周期较三卤甲烷（ＴＨＭｓ）更长。     

氯化消毒时三卤甲烷的形成（1）──形成机理及影响因素

７０年代发现氯消毒饮水中含有机致癌物三卤甲烷（ＴＨＭｓ）．其后人们对ＴＨＭｓ的形成机理及影响因素进行了广泛的研究．本文对近年报道的有关ＴＨＭｓ形成机理及影响因素进行了较详细的评述．     

2,4—二氯苯基荧光酮与铬显色反应的研究与其应用

研究了铬（Ⅳ）－２，４－二氯苯基荧光酮（ＤＣＩＰＥ）－溴化十六烷基三甲胺（ＣＴＭＡＢ）体系的显色条件，试验结果表明，在ｐＨ５．２～７．０范围内，铬与ＤＣＩＰＦ及ＣＴＭＡＢ形成红色三元胶束配合物，其最大吸收波长为５７８ｎｍ，表现摩尔吸光系数为１．４０×１０＾５Ｉ．ｍｏｌ＾－１．ｃｍ＾－１，铬（Ⅵ）含量在０～９．０μｇ／２５ｍｌ范围内符合比耳定律，配合物的组成为Ｃｒ（Ⅵ）：ＤＣＩＰＦ＝１：２，拟定方法     

水加氯处理时NHCl2与溴化物的反应特性研究

含氨水进行氯化处理时会产生ＮＨ２Ｃｌ和ＮＨＣｌ２,当水中含有溴化物时,氯胺类会与会中的Ｂｒ＾－反应,ＮＨ２Ｃｌ与Ｂｒ＾－的反应速度随ｐＨ增加和Ｂｒ＾－浓度降低而减慢;ＮＨＣｌ２与溴化物的反应比较复杂,２者的反应存在着一个诱导期,诱导期的长短与Ｂｒ＾－浓度对数成反比,ＮＨＣｌ２与Ｂｒ＾－的反应速度对ＮＨＣｌ２为一级反应;用紫外光谱,气相色谱和疏水微孔渗透法研究了该反应产物,确认反应产物为Ｂｒ＾－的反     

单柱离子色谱法测定水中微量阴离子及其在测定水中吸附有机氯…

本文介绍用一般高效液相色谱仪，不用抑制柱：分析柱为ＩＣ－ＰＡＫ阴离子交换柱，用电导检测器检测，测定水中Ｃｌ＾－，ＮＯ２＾－，Ｂｒ＾－，ＮＯ３＾－，ＳＯ４＾－离子。试验了淋洗液不同浓度和ＰＨ对阴离子分离的影响，并与另一组淋洗液比较各阴离子的最低检测浓度，及测定自来水中阴离子含量。检测限在０．１ｍｇ／Ｌ－０．８３ｍｇ／Ｌ间。用邻苯二甲酸氢钾淋洗液测定的变异系数＜５．１０％。单柱离子色谱法用于水中吸附有     

选择性螯合滴定法测定钙镁

用知量Ｔａｒｔｒａｔｅ、ＴＥＡ和ＤＬ－Ｃｙｓｔｅｉｎｅ掩蔽Ｆｅ＾３＋、Ａｌ＾３＋、Ｃｕ＾２＋、Ｎｉ＾２＋、Ｚｒ＾４＋、Ｃｄ＾２＋、Ｐｂ＾２＋和Ｍｎ＾２＋等离子，在ＰＨ为１０左右用ＥＤＴＡ滴定钙镁含量。然后另入Ｏｘｉｎｅ分解Ｍｇ－ＥＤＴＡ螯合物，用Ｃａ＾２＋标准溶液滴定释放出的ＥＤＴＡ。用ＭＴＢ－ＸＯ－ＣＰＢ为混合指示剂，终点颜色变化敏税，一般常见金属离了均不干扰。可用于测定水和工业废水钙，镁含量。     

石墨炉原子吸收法测定污水中溶解的Cr^＋3和Cr^＋6

本文采用在０．４５μｍ滤膜过滤后的水样中加Ｍｇ（ＮＯ３）２作为基体改进剂，测定溶解的总Ｃｒ；另取过滤后的水样在ＰＨ４．５的醋酸盐缓冲液中以ＡＰＤＣ０－ＭＩＢＫ萃取测定溶解的Ｃｒ＾＿６，并用差减法求出溶解的Ｃｒ＾＋３，总Ｃｒ与Ｃｒ＾＋６的检出限分别为０；７１和０．６９μｇ／Ｌ。     

铁改性海泡石对水中有害阴离子的吸附

海泡石经Ｆｅ＾３＋改性后，吸附阴离子的能力大幅度提高，可有效地吸附去除水中的Ｃｒ（Ⅵ）、Ａｓ（Ⅴ）离子，Ｆｅ＾３＋改性时的ｐＨ条件和Ｆｅ＾３＋的用量对改性海泡石的吸附能力有明显影响。ｐＨ＝１．４￣１．５，饱和吸附Ｆｅ＾３＋的改性海泡石对Ｃｒ（Ⅵ）、Ａｓ（Ⅴ）离子具有最强的吸附能力。     

藻类－卤虫－对虾系统深度处理含盐含汞化工废水的模拟试验研究

利用藻类－卤虫－对虾系统深度处理含盐含汞化工废水的模拟试验研究表明，该系统对ＢＯＤ５和ＣＯＤ去除率分别达９５．５％和８０．０％，对ＰＯ４＾２－和Ｈｇ＾２＋去除率都在９８％以上。在卤虫密度５２．１个／Ｌ和３６．０个／Ｌ，藻类密度２５７２５．８万个／Ｌ和２０９２４．９万个／Ｌ，水中汞能被不同营养等级的生物累积，在水中汞浓度１．０×１０＾２－７．８×１０＾３和２．１０×１０＾２－１．０４×１０＾４；卤虫     

Effect of ferric and bromide ions on the formation and speciation of disinfection byproducts during chlorination

The e ects of ferric ion, pH, and bromide on the formation and distribution of disinfection byproducts (DBPs) during chlorination were studied. Two raw water samples from Huangpu River and Yangtze River, two typical drinking water sources of Shanghai, were used for the investigation. Compared with the samples from Huangpu River, the raw water samples from Yangtze River had lower content of total organic carbon (TOC) and ferric ions, but higher bromide concentrations. Under controlled chlorination conditions, four trihalomethanes (THMs), nine haloacetic acids (HAAs), total organic halogen (TOX) and its halogen species fractions, including total organic chlorine (TOCl) and total organic bromide (TOBr), were determined. The results showed that co-existent ferric and bromide ions significantly promoted the formation of total THMs and HAAs for both raw water samples. Higher concentration of bromide ions significantly changed the speciation of the formed THMs and HAAs. There was an obvious shift to brominated species, which might result in a more adverse influence on the safety of drinking water. The results also indicated that high levels of bromide ions in raw water samples produced higher percentages of unknown TOBr.     

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.     

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.     

Characteristics of molecular weight distribution of dissolved organic matter in bromide-containing water and disinfection by-product formation properties during treatment processes

The characteristics of dissolved organic matter (DOM) and bromide ion concentration have a significant influence on the formation of disinfection by-products (DBPs). In order to identify the main DBP precursors, DOM was divided into five fractions based on molecular weight (MW), trihalomethane formation potential and haloacetic acid formation potential were determined for fractions, and the change in contents of different fractions and total DBPs during treatment processes (pre-chlorination, coagulation, sand filtration, disinfection) were studied. Moreover, the relationship between bromide concentration and DBP generation characteristics in processes was also analyzed. The results showed that the main DBP precursors were the fraction with MW < 1 kDa and fraction with MW 3−10 kDa, and the DBP''s generation ability of lower molecular weight DOM (< 10 kDa) was higher than that of higher molecular weight DOM. During different processes, pre-chlorination and disinfection had limited effect on removing organics but could alter the MW distribution, and coagulation and filtration could effectively remove organics with higher MW. For DBPs, trihalomethanes (THMs) were mainly generated in pre-chlorination and disinfection, while haloacetic acids (HAAs) were mostly generated during pre-chlorination; coagulation and sand filtration had little effect on THMs but resulted in a slight removal of HAAs. In addition, the results of ANOVA tests suggested that molecular sizes and treatment processes have significant influence on DBP formation. With increasing bromide concentration, the brominated DBPs significantly increased, but the bromine incorporation factor in the processes was basically consistent at each concentration.     

配水管网中生物稳定性和消毒副产物的变化及相关性

研究了上海市2条不同水源水厂配水管网中可同化有机碳（AOC）、三卤甲烷（THMs）和卤乙酸（HAAs）的变化情况,并对饮用水生物稳定性和消毒副产物间的相关性进行了分析.结果表明,管网中AOC和HAAs含量受余氯和微生物活动双重作用的影响,在距水厂较近、余氯较高的管网中,可能因氯与有机物继续反应出现上升,在余氯较低的管网末梢则因为微生物降解作用使含量下降;THMs含量则只受余氯的影响,随管网延伸持续增长.HAAs与AOC含量间存在较好的线形关系,前体物间具有相似性,THMs与AOC含量间呈正相关性;作为饮用水安全性的2个重要方面,生物稳定性和消毒副产物间具有内在的关联性.     

饮用水中卤乙酸生成的影响因素及检测方法

卤乙酸作为已检出的氯化消毒副产物中最具致癌性的一类物质,在饮用水的研究中得到了越来越多的重视。本文从卤乙酸的生成机理及其影响因素、检测方法入手,对卤乙酸的研究进行了概述,并着重分析了影响卤乙酸生成的各种影响因素以及其检测方法的优化。     

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.     

Impact of combining chlorine dioxide and chlorine on DBP formation in simulated indoor swimming pools

The main objective of this study was to assess the combined use of chlorine dioxide (ClO2) and chlorine (Cl2) on the speciation and kinetics of disinfection by-product (DBP) formation in swimming pools using synthetic pool waters prepared with a body fluid analog (BFA) and/or fresh natural water. At 1:25 (mass ratio) of ClO2 to Cl2, there was no significant reduction in the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) for both BFA solution and natural water compared to the application of Cl2 alone. When the mass ratio of ClO2 to Cl2 increased to 1:1, substantial decreases in both THMs and HAAs were observed in the natural water, while there was almost no change of DBP formations in the BFA solution. Haloacetonitriles and halonitromethanes levels in both water matrices remained similar. In the presence of bromide, the overall DBP formation increased in both BFA solution and natural water. For the DBP formation kinetics, after 72 hr of contact time, very low formation of THMs and HAAs was observed for the use of ClO2 only. Compared to Cl2 control, however, applying the 1:1 mixture of ClO2/Cl2 reduced THMs by > 60% and HAAs by > 50%. Chlorite was maintained below 1.0 mg/L, while the formation of chlorate significantly increased over the reaction time. Finally, in a bench-scale indoor pool experiment, applying ClO2 and Cl2 simultaneously produced less THMs compared to Cl2 control and kept chlorite at < 0.4 mg/L, while HAAs and chlorate accumulated over 4-week operation period.     

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.     

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.