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。     

北京市饮用水中溴酸盐、卤代乙酸及高氯酸盐研究

调查了北京市饮用水厂源水及出厂水中消毒副产物溴酸盐、卤代乙酸及典型污染物高氯酸盐的污染现状,研究了其来源及环境影响因素.结果表明,北京市饮用水中基本不含溴酸盐;含有5种卤代乙酸和高氯酸盐.饮用水加氯消毒是产生卤代乙酸的主要原因.在所调查水厂出厂水中卤代乙酸的平均浓度为42.1～149.5μg/L;其中含氯卤代乙酸占总量的90%以上.5种卤代乙酸的含量顺序为三氯乙酸>二氯乙酸>氯溴乙酸>二溴乙酸>一溴二氯乙酸.饮用水中卤代乙酸受季节影响较大,9月份浓度最高,4月份浓度最低.高氯酸盐主要存在于以地下水为源水的水厂中,受地下水污染影响较大.各水厂出厂水中高氯酸盐含量为0.1～6.8μg/L.饮用水中高氯酸盐在11月份含量最高,7月份含量最低.     

臭氧预氧化对藻细胞及胞外分泌物消毒副产物生成势的影响

以处于对数生长期后期的悦目颤藻为研究对象,研究了藻细胞及胞外分泌物对氯化消毒副产物生成势(DBPFP)的贡献,以及臭氧预氧化对DBPFP的影响规律,即不同臭氧投量及预氧化时间对DBPFP的影响,并探讨臭氧预氧化控制消毒副产物生成势的原因.研究表明,藻细胞和胞外分泌物的三卤甲烷类副产物都主要是氯仿和一溴二氯甲烷,卤乙酸类副产物都主要是二氯乙酸和三氯乙酸.颤藻细胞和其EOM本身及经臭氧预氧化混凝后形成卤乙酸的能力基本都高于形成三卤甲烷的能力,在实际含藻水的处理中,应该更加重视对卤乙酸的控制.臭氧预氧化可以降低胞外分泌物形成氯化消毒副产物(DBP)的能力,且随着反应时间延长,DBPFP降低越多.在本试验条件下,0.975 mg/L臭氧预氧化10min后混凝,可比单纯混凝降低胞外分泌物DBPFP 31%,其中HAAFP降低52.6%,而THMFP却升高12.5%,可见臭氧预氧化控制胞外分泌物DBPFP主要原因是其可以很好地控制卤乙酸生成势.同时臭氧预氧化会使含藻细胞水样的DBPFP大幅度升高,且随着氧化时间延长,各种氯化消毒副产物生成势几乎呈线性增加.在实际水处理中,应在去除藻细胞之后再进行臭氧氧化以控制DBPFP.     

饮用水消毒副产物-卤乙酸的分析检测

卤乙酸是氯化消毒饮用水中一类主要的消毒副产物 ,由于存在的广泛性和潜在的健康危害 ,许多国家和卫生组织相继将其列为饮用水常规监测项目 ,而我国至今还没有相关规定 ;为更好地控制饮用水中卤乙酸的形成 ,世界各国科研人员先后研究和开发出了性能逐趋完善的多种分析检测方法 ;在大量国内外文献调研的基础上 ,对卤乙酸的各种分析检测方法进行系统的介绍 ,并指明今后的发展方向     

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.     

厦门海域有机磷农药污染现状与来源分析

对北方某城市自来水厂水体中的4种卤乙酸浓度水平进行了检测.以黄河水作为原水,经常规工艺处理后的饮用水中卤乙酸的最大浓度水平为79.31μg·L-1,超出美国EPA提出的饮用水中卤乙酸浓度水平的限定值;进而对常规工艺的氯化作用做了进一步调查研究,结果表明,预氯化对卤乙酸的产生起主导作用,增大了饮用水中卤乙酸的含量.探讨了由高锰酸钾预氧化、气浮、过滤、臭氧氧化、活性炭吸附、氯氨消毒组成的深度处理工艺对卤乙酸的削减效果.结果表明,经深度处理后的出厂水中卤乙酸含量从常规工艺的79.31μg·L-1降为3.92μg·L-1,有效地控制了卤乙酸的形成.     

南方某水源水中天然有机物的特点及氯胺对氯化消毒副产物的控制

在对天然有机物分类的基础上进行了水体中有机物的特性研究，并采用氯胺对不同特性有机物的氯化消毒副产物进行了控制研究。结果表明，疏水酸占有机物总量的24％，疏水中性物质占41％，疏水性有机物占67％；对于三卤甲烷类消毒副产物生成势，疏水酸所产生的最多，疏水碱次之，亲水酸最少；对于卤乙酸类消毒副产物生成势，疏水碱产生的三卤乙酸最多，其次为疏水酸，亲水酸最少。氯胺对不同类有机物氯化消毒副产物控制程度不同，氯胺对疏水中性物质控制三卤甲烷类消毒副产物最好，其次是疏水碱和亲水碱；对疏水酸的三卤甲烷生成量控制较弱，对亲水酸的控制效果最差；氯胺对亲水碱氯化产生卤乙酸的控制效果最好，其次是疏水碱，控制效果最差的为疏水中性物质。     

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.     

饮用水中卤乙酸致癌性的研究进展

目前饮用水中主要氯化消毒副产物卤乙酸由于难挥发和难降解,其危害研究特别是致癌性越来越引起人们的重视,为此笔者对饮用水中卤乙酸(主要包括二氯乙酸、三氯乙酸、二溴乙酸)的暴露水平、代谢、致癌性、致癌机制、流行病学研究等方面的研究工作进行了综述,并指出了今后研究的方向.     

煮沸对氯、氯胺模拟消毒饮用水中六大类DBPs的去除规律研究

以陆生来源有机物为原料制备了模拟氯、氯胺消毒饮用水,系统研究了煮沸对六大类46种消毒副产物（disinfection by-products, DBPs）的去除规律.结果显示,相比氯消毒,氯胺消毒可有效减少三卤甲烷（THMs）、卤乙酸（HAAs）、卤乙醛（HALs）、卤代硝基甲烷（HNMs）、卤乙腈（HANs）等DBPs的生成,但会提高碘代DBPs (I-DBPs)、卤乙酰胺（HAcAms）的生成.煮沸对于绝大多数DBPs （除了二卤乙酸）有良好的去除效果,并发现如下规律：(1)就单种DBP而言,消毒方式对煮沸去除DBPs并无显著影响;(2)在同类型的DBPs中,取代程度高的DBPs普遍比取代程度低的DBPs容易去除;(3)取代程度相同的同类型DBPs,煮沸后DBPs去除率大部分遵循I-DBPs> Br-DBPs> Cl-DBPs的规律;(4)少部分DBPs （如Cl/Br-THMs、二卤乙腈）,煮沸去除率表现出沸点或亨利常数依赖性.总体来看,DBPs去除率排序为THMs≈HANs≈HALs≈HNMs> HAcAms>>HAAs.此外,煮沸后各类DBPs的...     

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.     

Formation of regulated and unregulated disinfection byproducts during chlorination and chloramination: Roles of dissolved organic matter type, bromide, and iodide

Algal blooms and wastewater effluents can introduce algal organic matter (AOM) and effluent organic matter (EfOM) into surface waters, respectively. In this study, the impact of bromide and iodide on the formation of halogenated disinfection byproducts (DBPs) during chlorination and chloramination from various types of dissolved organic matter (DOM, e.g., natural organic matter (NOM), AOM, and EfOM) were investigated based on the data collected from literature. In general, higher formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was observed in NOM than AOM and EfOM, indicating high reactivities of phenolic moieties with both chlorine and monochloramine. The formation of haloacetaldehydes (HALs), haloacetonitriles (HANs) and haloacetamides (HAMs) was much lower than THMs and HAAs. Increasing initial bromide concentrations increased the formation of THMs, HAAs, HANs, and HAMs, but not HALs. Bromine substitution factor (BSF) values of DBPs formed in chlorination decreased as specific ultraviolet absorbance (SUVA) increased. AOM favored the formation of iodinated THMs (I-THMs) during chloramination using preformed chloramines and chlorination-chloramination processes. Increasing prechlorination time can reduce the I-THM concentrations because of the conversion of iodide to iodate, but this increased the formation of chlorinated and brominated DBPs. In an analogous way, iodine substitution factor (ISF) values of I-THMs formed in chloramination decreased as SUVA values of DOM increased. Compared to chlorination, the formation of noniodinated DBPs is low in chloramination.     

Comparison of three-dimensional fluorescence analysis methods for predicting formation of trihalomethanes and haloacetic acids

This work investigated the application of several fluorescence excitation-emission matrix analysis methods as natural organic matter (NOM) indicators for use in predicting the formation of trihalomethanes (THMs) and haloacetic acids (HAAs). Waters from four different sources (two rivers and two lakes) were subjected to jar testing followed by 24 hr disinfection by-product formation tests using chlorine. NOM was quantified using three common measures: dissolved organic carbon, ultraviolet absorbance at 254 nm, and specific ultraviolet absorbance as well as by principal component analysis, peak picking, and parallel factor analysis of fluorescence spectra. Based on multi-linear modeling of THMs and HAAs, principle component (PC) scores resulted in the lowest mean squared prediction error of cross-folded test sets (THMs: 43.7 (μg/L)², HAAs: 233.3 (μg/L)²). Inclusion of principle components representative of protein-like material significantly decreased prediction error for both THMs and HAAs. Parallel factor analysis did not identify a protein-like component and resulted in prediction errors similar to traditional NOM surrogates as well as fluorescence peak picking. These results support the value of fluorescence excitation-emission matrix-principal component analysis as a suitable NOM indicator in predicting the formation of THMs and HAAs for the water sources studied.     

臭氧活性炭工艺中卤乙酸生成潜能与相对分子质量分布关系的研究

通过臭氧生物活性炭和微曝气生物活性炭(O₃/BAC和micro-aeration/BAC)2套工艺研究其对不同相对分子质量有机物去除特点和不同相对分子量有机物生成的卤乙酸及其去除特性.结果表明,O₃/BAC工艺对相对分子质量区间>30×10³的有机物去除率超过90%.O₃/BAC与micro-aeration/BAC出水中,UV₂₅₄值表示相对分子质量<103的有机物超过50%,相对分子量区间在10×10³～30×10³的有机物占20%～30%;在O₃/BAC和微曝气/BAC工艺出水中,以相对分子质量<10³的有机物生成的卤乙酸最多,生成DCAA、TCAA、DBAA分别为97.00、38.55、2.10μg/L和104.00、42.75和2.92μg/L;采用各处理单元不同分子量有机物与氯反应生成的DCAA、TCAA、DBAA和THAAs与相对应的UV₂₅₄值进行线性拟合,相关系数分别为0.827、0.851 3、0.815 7和0.878.UV₂₅₄与臭氧生物活性炭处理工艺出水中的卤乙酸生成潜能具有较好的线性关系.     

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.     

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.     

Effects of Ca(OH)2 assisted aluminum sulfate coagulation on the removal of humic acid and the formation potentials of tri-halomethanes and haloacetic acids in chlorination

The effects of addition of calcium hydroxide on aluminum sulphate(or alum) coagulation for removal of natural organic matter(NOM) and its subsequent effect on the formation potentials of two major types of regulated disinfection byproducts(DBPs),haloacetic acids(HAAs) and trihalomethanes(THMs),have been examined.The results revealed several noteworthy phenomena.At the optimal coagulation pH(i.e.6),the coagulation behavior of NOM water solutions versus alum dose,showed large variation and a consequent great change in the formation potentials of the DBPs at certain coagulant doses.However,with addition of a relatively small amount of Ca(OH) 2,although the zeta potential of coagulated flocs remained almost the same,NOM removal became more consistent with alum dose.Importantly,also the detrimental effect of charge reversal on NOM removal at the low coagulant dose disappeared.This resulted in a steady decrease in the formation potentials of DBPs as a function of the coagulant dose.Moreover,the addition of Ca(OH) 2 broadened the pH range of alum coagulation and promoted further reduction of the formation potentials of the DBPs.The enhancement effects of Ca(OH) 2 assisted alum coagulation are especially pronounced at pH 7 and 8.Finally,synchronous fluorescence spectra showed that the reduction in DBPs formation potential by Ca(OH) 2-assisted alum coagulation was connected to an enhanced removal of small hydrophobic and hydrophilic HA molecules.Ca(OH) 2-assistance of alum coagulation appeared to increase substantially the removal of the hydrophilic HA fraction responsible for HAAs formation,prompting further reduction of HAA formation potentials.