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.     

铜绿微囊藻胞内物消毒副产物生成：氯化和溴化比较

为了研究蓝藻水华期间释放的有机物给原水水质及给水处理过程带来的影响,选取优势藻种铜绿微囊藻的胞内物质(IOM)作为前驱体,分析了其结构特征.此外,分别研究了IOM在pH 6.5、7.1及8.4条件下与氯及溴反应后性质的变化及消毒副产物的生成,并进行了相关性分析.结果表明,IOM中以相对分子质量较大的组分(>30×103)为主,其溶解性有机碳(DOC)含量占总量的68.8%.三维荧光光谱(EEM)的结果表明IOM的成分主要以芳香蛋白类物质为主,其单位DOC的荧光强度为92.6 AU·L·mg-1.与氯或溴反应后,芳香蛋白类EEM峰值下降了76.6%~93.3%,且其降低值与三卤甲烷(THMs,R2=0.81)和卤乙酸(HAAs,R2=0.77)的生成量正相关.IOM与氯或溴反应生成的THMs和HAAs浓度均随着pH的增加而增加.溴相比氯与IOM反应可以生成更多的THMs和HAAs,且HAAs的卤代程度更高,但是氯及溴与IOM反应能力的差异随着pH的升高而逐渐减小,即k OBr·IOM/k OCl·IOM相似文献   

海水淡化超滤-反渗透工艺沿程溴代消毒副产物变化规律

研究了海水淡化超滤-反渗透(UF-RO)工艺沿程有机物和溴代消毒副产物(Br-DBPs)变化特征.该海水中含有较高浓度的Br-(45.6~50.9 mg·L-1)和较多的芳香类化合物[比紫外吸收值SUVA为3.6~6.0 L·(mg·m)-1];色氨酸类芳香族蛋白质、富里酸类有机物和溶解性微生物代谢产物是海水中主要的荧光特征有机物.UF-RO工艺进水海水经Na Cl O消毒后,DBPs的种类和浓度显著增加,且增加的主要为Br-DBPs,其中三溴甲烷(CHBr3)占总三卤甲烷(THMs)的70.48%~91.50%,二溴乙酸(Br2CHCO2H)占总卤乙酸(HAAs)的81.14%~100%,二溴乙腈(C2HBr2N)占总卤乙腈(HANs)的83.77%~87.45%.UF膜对THMs、HAAs和HANs的去除率分别为36.63%~40.39%、73.83%~95.38%和100%.RO膜可以完全去除HAAs,但是对THMs不能完全去除.进水海水的抗雌激素活性为0.35~0.44 mg·L-1,氯消毒后增加了32%~69%.海水淡化UF-RO系统生成的DBPs和其他生物毒性物质最终被截留到了UF浓水和RO浓水中.     

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.     

基于EEMs和DOM分离的荧光特征及DBPsFP研究 ——以南方某市水源水为例

以南方某市饮用水源地源水为研究对象,利用三维荧光-区域积分法(3D-EEMs-FRI)和DAX-8树脂富集分离技术,研究了水样各组分的溶解性有机物(DOM)组成特征、三维荧光光谱(3D-EEMs)特征;采用生成潜能测试,考察了典型消毒副产物三卤甲烷(THMs)和卤代乙酰胺(HAcAms)生成势以及其与水质指标和荧光强度...     

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.     

河北洨河溶解性有机物光谱学特性

基于荧光光谱、紫外吸收光谱与水质基本化学指标,联合主成分分析与相关性分析,对典型城市纳污河流——河北洨河的溶解性有机物(DOM)进行光谱学特性研究.结果表明,河流水体中DOM主要有类蛋白和类腐殖质两类,其中含氮化合物及DOM与水体COD之间相关性较高,尤其以氨氮对类腐殖质贡献较大.因此降低洨河水体中COD可通过减少氨氮与DOM来实现,同时此两类指标也应作为日后水体监控指标.干流水体样品中DOM下游相对上游类蛋白逐渐减少,而类腐殖质则呈现增加的趋势,并以类胡敏酸为主要存在形式.代表支流4种样品中,S1、S2水体DOM主要以类胡敏酸为重要成分,其组成有机物多为大分子量、芳香性高的有机物质,而S3、S6水体中主要为相对易降解的类蛋白,其相对分子质量相对较小、芳香性程度较低.针对代表支流的4个污水处理单位出水水体中的DOM特征,建议S1与S2应添加或改进对大分子物质有较好去除效果的膜处理设备,以加强对水体中相对难降解类腐殖质物质的去除;S3与S6应优化相关厌氧与好氧生物处理工艺,从而提高易降解的类蛋白物质的去除能力.     

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.     

饮用水消毒副产物分析及相关研究进展

饮用水消毒副产物（DBPs）是消毒剂和一些天然有机物（NOM）反应生成的化合物,主要包括三卤甲烷（THMs）、卤代G@（HAAs）、卤代乙腈（HANs）和致诱变化舍物（MX）4类。本文针对氯、氯胺、二氧化氯、臭氧4种主要消毒方式产生的消毒副产物,讨论了有关分析技术的发展过程,从DBPs的前处理技术、分析技术等角度,介绍了DBPs研究领域近期所取得的进展,并展望了今后研究的发展方向。     

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.     

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.     

Formation potentials of typical disinfection byproducts and changes of genotoxicity for chlorinated tertiary e uent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

铜绿微囊藻胞内DOM光降解及其对芘结合能力的影响

利用紫外可见吸收光谱法及荧光光谱法研究有氧和缺氧条件下紫外线A波段(UV-A)辐照对铜绿微囊藻(Microcystis aeruginosa)胞内溶解性有机质(IDOM)(M. aeruginosa-IDOM)光降解行为,并考察光降解对其与芘结合能力的影响.结果表明,M. aeruginosa-IDOM经6d光降解后,有氧组中溶解性有机碳(DOC)浓度及其吸收系数a₃₅₅降解幅度均高于缺氧组.有氧及缺氧状态下M. aeruginosa-IDOM光降解过程中吸光度比值E2/E3(250nm/365nm)变化相似,但254nm处比紫外吸收值(SUVA₂₅₄)变化不同.激发–发射三维荧光光谱法(EEMs)结合平行因子(PARAFAC)分析,结果显示, M. aeruginosa-IDOM中类蛋白C1、长波激发类腐殖质C2及短波激发类腐殖质C3荧光强度在两种光降解条件下变化趋势不同. M. aeruginosa-IDOM光降解过程符合一级降解动力学特征的参数,在有氧组中降解半衰期均短于缺氧组.此外,光降解过程中,有氧组M. aeruginosa-IDOM与芘结合能力降低,但缺氧组M. aeruginosa-IDOM与芘结合能力先下降后增加.     

西安市大气棕碳污染特性及发色团种类

为探究西安市大气棕碳（BrC）的光学特性及化学组成,利用大气颗粒物采样器和吸附剂同时采集了颗粒相和气相大气样品,并运用紫外-可见分光光度计和三维荧光光度计测定了样品中BrC的吸光和荧光特性,基于平行因子分析（PARAFAC）法解析三维荧光光谱得到BrC的种类和组成信息.结果表明,在波长为365 nm时,颗粒相和气相BrC的吸光度分别为（13.8±7.9）Mm^-1和（8.0±3.1）Mm^-1,两者占比分别为63%和37%.本研究并未发现气相和颗粒相BrC吸光度之间有显著的相关性.PARAFAC结果表明,西安市大气BrC含有类腐殖质发色团、类酚类发色团和类蛋白发色团,而它们分别在气相和颗粒相BrC中的占比是不同的,类腐殖质发色团和类蛋白发色团在颗粒相中分布较多,分别为41%和36%,而气相中主要包含酚类发色团,其占比为78%.本研究结果揭示了气相BrC也可能是贡献大气正辐射强迫的重要因子,以及参与大气光化学反应的重要大气组分,将来的研究需要给予足够重视和关注.     

Formation potentials of typical DBPs and changes of genotoxicity for chlorinated tertiary effluent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

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.     

有机肥施用下稻田田面水中消毒副产物前体物的赋存规律

稻田有机肥输入会使田面水含有含量的溶解性有机碳(DOC).溶解性有机物(DOM)是具有三致效应的消毒副产物(DBPs)的前体物,而DOC是用于表征DOM浓度的一个指标.本研究旨在评估水稻田田面水的三卤甲烷(THMs)前体物的生成反应性,解析猪粪有机肥对于THMs前体物从水稻田输出的潜在影响.于水稻种植季选取4个猪粪施用梯度(以C计,下同)(0[对照],714.1[低],1428.2[中]与2142.3[高]kg·hm-2),检测了稻田田面水中的DOC,UVA254与三卤甲烷生成潜能(THMFP).结果表明,3个指标两两之间呈线性相关性.田面水中以上3个指标都与有机肥施用量呈正相关性.在施肥后的7d内,DOC的输出潜能降低了32.9%至47.5%.有机肥施用与预期的降雨或灌溉之间的时间间隔相隔一周以上,将能在满足作物营养需求的条件下降低消毒副产物前体物输出的风险,使稻田土壤成为DOC的汇而非DOC输出至周边水体的源.     

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.     

Impact of pre-oxidation on the formation of byproducts in algae-laden water disinfection: Insights from fluorescent and molecular weight

Pre-oxidation has been reported to be an effective way to remove algal cells in water, but the released algal organic matter (AOM) could be oxidized and lead to the increment in disinfection by-product (DBP) formation. The relationship between pre-oxidation and AOM-derived DBP formation needs to be approached more precisely. This study compared the impact of four pre-oxidants, ozone (O₃), chlorine dioxide (ClO₂), potassium permanganate (KMnO₄) and sodium hypochlorite (NaClO), on the formation of nitrogenous (N-) and carbonaceous (C-) DBPs in AOM chlorination. The characterization (fluorescent properties, molecular weight distribution and amino acids concentration) on AOM samples showed that the characterization properties variations after pre-oxidation were highly dependent on the oxidizing ability of oxidants. The disinfection experiments showed that O₃ increased DBP formation most significantly, which was consistent with the result of characterization properties variations. Then canonical correspondent analysis (CCA) and Pearson's correlation analysis were conducted based on the characterization data and DBP formation. CCA indicated that C-DBPs formation was highly dependent on fluorescent data. The formation of haloacetic acids (HAAs) had a positive correlation with aromatic protein-like component while trichloromethane (TCM) had a positive correlation with fulvic acid-like component. Pearson's correlation analysis showed that low molecular weight fractions were favorable to form N-DBPs. Therefore, characterization data could provide the advantages in the control of DBP formation, which further revealed that KMnO₄ and ClO₂ were better options for removing algal cells as well as limiting DBP formation.     

紫外老化微塑料衍生DOM理化特性及其与磺胺嘧啶、铜的络合机制

微塑料在老化过程中所释放的溶解性有机质(MPDOM)可与有机污染物、重金属等污染物发生络合反应,影响污染物的迁移转化.选取聚对苯二甲酸乙二醇酯(PET)和聚苯乙烯(PS)两种微塑料,利用荧光猝灭法及多种光谱分析技术和方法,同时结合Ryan-Weber模型,探究了MPDOM的光谱特性以及MPDOM与磺胺嘧啶(SDZ)、铜离子(Cu²⁺)的络合机制.紫外-可见吸收光谱分析结果表明,老化后两种MPDOM的相对分子量减小、芳香性及腐殖化程度增加,芳环上的羧基、羰基、羟基及酯类取代基增多.MPDOM与SDZ、 Cu²⁺的荧光猝灭均属于静态猝灭,猝灭后两种MPDOM的芳香性和腐殖化程度相近,相对分子质量相当.三维荧光光谱结合平行因子分析法共鉴定出两种类腐殖质组分和一种类蛋白质组分.同步荧光光谱分析结果表明,两种MPDOM均以类蛋白组分优先与SDZ发生反应,与Cu²⁺反应时更为敏感.结合Ryan-Weber模型可知,两种猝灭体系均以类腐殖质组分与PET-DOM的结合能力更高,但总体来说SDZ猝灭体系中MPDOM的结合能力要强于Cu