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.     

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。     

饮用水中含氮消毒副产物卤代腈(氰)的生成特性与控制研究进展

卤代腈(氰)是水处理过程中产生的一类含氮的氯化消毒副产物。鉴于这种物质有极强的致畸和致突变性,其细胞毒性也远大于三卤甲烷和卤乙酸等常规消毒副产物,因此成为近年来饮用水中颇受关注的含氮消毒副产物种类之一。卤代腈(氰)在水厂出厂水中被大量检出,其质量浓度基本维持在μg/L,而采用氯胺消毒的出厂水中其浓度明显高于自由氯消毒方式。重点对卤代腈(氰)的物质种类、理化特性、遗传毒性、生产机制、检测方法及控制方法进行综述。鉴于多数卤代腈(氰)类消毒副产物均具有含量低、亲水性强等特点,若生成将难以在饮用水处理工艺中有效去除,因此如何有效控制其生成是卤代腈(氰)研究的主要发展方向。     

预氯化及常规工艺对消毒副产物的影响

以天津市某给水厂的水源水为实验对象,通过在实验室规模上模拟的给水处理厂工艺流程,比较了3种不同工艺流程中各单元出水的三卤甲烷(THMs)、卤乙酸(HAAs)和总有机物(TOC)浓度变化,分析了水处理单元工艺和TOC浓度对消毒副产物的影响。结果表明,预氯化生成的三卤甲烷和卤乙酸分别占最终出水中三卤甲烷和卤乙酸浓度的55.7%和66.7%,说明预氯化对出厂水中消毒副产物的产生有显著影响;混凝沉淀和过滤对三卤甲烷的去除率分别为17.2%和19.6%,而卤乙酸在水处理过程中变化不大,仅在过滤之后降低了3.32μg/L,说明过滤对三卤甲烷和卤乙酸均有一定的去除作用,而混凝沉淀仅对三卤甲烷有一定的去除作用;TOC浓度经过水处理工艺后整体呈下降趋势,但分析表明,其浓度对三卤甲烷和卤乙酸的生成影响很小,而氯则是三卤甲烷和卤乙酸生成的重要限制因素。     

河流型水源地源水典型氯化消毒副产物及其前体物的强化去除工艺

以长三角某典型河流型水源地源水为研究对象,设计了传统工艺及基于凹凸棒土处理单元的6种强化工艺,对各工艺及其处理单元应用于典型氯化消毒副产物(三卤甲烷和卤乙酸)及其前体物控制的技术和经济可行性进行了系统分析。结果表明,预O3+凹土强化混凝+O3-GAC强化的工艺对上述2种消毒副产物及其前体物的控制效果最佳;在传统工艺中单纯增加O3处理也能在一定程度上提高其对消毒副产物前体物的去除效果;KMnO4控制消毒副产物的效果一般,但KMnO4处理可强化后续单元对消毒副产物前体物的去除效果。各工艺处理出水中三卤甲烷和卤乙酸单项指标均能达标,但传统工艺和经凹土强化混凝+GAC强化的工艺出水三卤甲烷4种化合物的实测浓度与其各自限值的比值之和均大于1.0,不能满足水质要求,必须进行强化处理。凹土强化混凝单元在6种强化工艺条件下对三卤甲烷生成潜能(THMFP)和卤乙酸生成潜能(HAAFP)的去除率较传统混凝单元平均提高15.99%和4.92%;各强化工艺对THMFP和HAAFP的去除率较传统工艺均提高20%以上(除凹土强化混凝+GAC强化的工艺外),消毒副产物产生量降低40%以上,工艺成本降低20%以上。     

城市污水再生氯消毒过程中HAAs生成及迁移转化

针对城市污水再生处理工艺中卤乙酸类(HAAs)消毒副产物和卤乙酸生成潜能(HAAFP),结合三维荧光光谱,分析HAAs及其前体物的变化规律。结果表明,二级出水经2次加氯过程后,再生出水中的总卤乙酸浓度增加了90%,其中溴代乙酸的增幅最大,占增加量的82%。卤乙酸生成潜能较大的为氯代乙酸类物质,说明水中存在大量的氯代乙酸前体物。从工艺过程来看,总卤乙酸生成潜能与总有机物荧光强度分别下降了32%和28%,表明该再生处理工艺对HAAs前体物有一定的去除作用。     

水源地生态工程对消毒副产物生成的影响

水源地生态工程可改善饮用水水源水质,但其中的水生生物代谢物可能是消毒副产物(DBPs)前体物的来源。本文构建现场实验装置探究了水源地生态工程对原水水质的影响及原水中主要消毒副产物前体物的来源,考察了氯投量、温度以及pH对香蒲根分泌物、菰根分泌物和鲢鱼排泄物氯化后消毒副产物生成的影响。结果表明,实验装置对NH₄⁺-N、TN和TP的平均总去除率分别为74.93%、53.98%和73.02%,总DOC沿程增加。溶解性有机物(DOM)中分子质量分布在<500 Da的DOC含量总体上呈沿程减少的趋势,>3 000 Da的DOC沿程有所增加。总三卤甲烷生成势(TTHMFP)和总卤乙酸生成势(THAAFP)沿程呈现增加的趋势,分子质量<3000Da的有机物中TTHMFP和THAAFP沿程有所下降,分子质量>3 000 Da的TTHMFP和THAAFP呈沿程增加的趋势。考察了装置中3种水生生物代谢物经氯化后得到的二氯乙酸(DCAA)、三氯乙酸(TCAA)、三氯甲烷(TCM)和二氯乙腈(DCAN)4种消毒副产物生成势,均随着氯投量和温度...     

芳香类有机物氯化生成消毒副产物的特性研究

选择有代表性的芳香类有机物,在含有腐殖酸的水溶液中进行氯化试验.测定三卤甲烷和卤乙酸的生成特性.并分析有机物的化学结构对生成消毒副产物的影响.结果表明.各受试物氯化生成消毒副产物的活性和反应速率排序为间苯二酚>对苯二酚>邻苯二酚>苯酚>苯胺>苯甲酸>硝基苯;芳香类有机物苯环上官能团的性质、数量和位置等影响消毒副产物的生成;间苯二酚的氯化反应可分为快速反应阶段和慢速反应阶段.     

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.     

加压混凝沉淀对蓝藻水处理中消毒副产物的控制

为了降低蓝藻水处理中消毒副产物的产生,采用物理加压法取代传统化学氧化法进行预处理,从而减少新的化学物质的产生,降低消毒副产物风险,实验对比研究了加压混凝沉淀和预氧化混凝沉淀除藻工艺中消毒副产物及其前驱物的浓度。结果表明,经0.7 MPa加压1 min后混凝沉淀处理,藻类去除率达到95.8%,浊度0.58 NTU,均比原水混凝沉淀和预氧化混凝沉淀后效果大幅度提高。蓝藻水加压后三卤甲烷前驱物降低26.2%,卤乙酸前驱物无变化,混凝沉淀处理后前驱物比原水混凝沉淀后略有减少。加压水过滤消毒后消毒副产物与原水处理后持平。而经1~2 mg/L的Na Cl O预氧化水混凝沉淀过滤消毒后,三卤甲烷和卤乙酸浓度分别比原水处理后增加了3~4倍和1.7~2.5倍。加压混凝沉淀工艺处理蓝藻水,比传统预氧化工艺更有效控制了消毒副产物的产生。     

The occurrence of disinfection by-products in the drinking water of Athens,Greece

Application of chlorination for the disinfection of drinking water results in the formation of a wide range of organic compounds, called disinfection by-products (DBPs), which occur due to the reaction of chlorine with natural organic materials. The occurrence of DBPs was studied in samples from four drinking-water treatment plants (WTPs) and from the distribution network of Athens, Greece. Twenty-four compounds, which belong to different categories of DBPs, were monitored, including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), haloketones (HAKs), chloral hydrate (CH) and chloropicrin (CP). Sampling was performed monthly for a period of two years, from three different points at each WTP and from eight points atthe distribution network. Samples were analyzed by GC-ECD methods, which included pretreatment with liquid-liquid extraction for volatile DBPs and acidic methanol esterification for HAAs. The results of the analyses have shown the presence of disinfection by-products belonging to all categories studied in all water samples collected after prechlorination. The major categories of DBPs detected were THMs and HAAs, while the other volatile DBPs occurred at lower concentrations. The concentrations of DBPs did not in any case exceed the maximum contaminant levels (MCL) set by USEPA and WHO. However, monitoring these compounds needs to be continued, because their levels could increase due to changes in the quality of water entering the water treatment plants. Reduction of the concentrations of DBPs could be achieved by optimization of the chlorination conditions, taking into account the effect of time. Moreover, research on alternative disinfection methods (e.g. ozone, chlorine dioxide, chloramines) and their by-products should be conducted to evaluate their applicability in the case of the drinking water of Greece.     

Solid phase extraction with pyrenebutyric acid-bonded silica for analysis of polychlorinated biphenyls in sewage water by gas chromatography-mass spectrometry

A solid phase extraction (SPE) method using pyrenebutyric acid-bonded silica (PYB) as sorbent was developed to determine 23 polychlorinated biphenyls (PCBs) in sewage water by gas chromatography-mass spectrometry (GC-MS). Factors were optimized in SPE procedures including elution solvent, pH, and cartridge burden. The recoveries of 23 PCB congeners were 69.44-111.91% under optimized conditions. Comparisons were also conducted among PYB-SPE, C(18)-SPE and United States Environmental Protection Agency 608 (USEPA608) methods in the analysis of PCBs in sewage water samples. The results showed that the performance of PYB-SPE method was similar with USEPA608 method and better than C(18)-SPE method. Both PYB-SPE and USEPA608 methods were then employed to analyze PCBs in real spiked sewage water samples. The recoveries of PCB congeners determined by PYB-SPE method ranged from 70.6% to 92.4% in real spiked sewage water samples which were identified to be in accordance with USEPA608 method. Limits of detection (LOD) were in the range of 0.06-0.22ngL(-1) for PCB congeners. The optimized PYB-SPE method was successfully applied to the determination of PCBs in sewage water samples.     

Spatial and Seasonal Variations of Disinfection Byproducts (DBPs) in Drinking Water Distribution Systems of Istanbul City,Turkey

This study presents the seasonal and spatial variations of trihalomethanes (THMs) and haloacetic acids (HAAs) in 30 sampling points within three water distribution systems of Istanbul City, Turkey. The effects of surface water quality, seasonal variation, and species differences were examined. The occurrence of chlorinated THMs and HAAs levels was considerably lower in the system in which raw water is subjected to pre-ozonation versus pre-chlorination. Seasonal analysis of the data indicated that the median concentration of four THMs (THM₄) was higher than nine HAAs (HAA₉) concentrations in all three distribution systems sampling points. For all distribution systems monitored, the highest median THM₄ and HAA₉ concentrations were observed in the spring and summer season, while the lowest concentrations of these disinfection byproduct (DBP) compounds were obtained in the fall and winter period. Due to the higher level of bromide in supplying waters of these two systems, moderate levels of brominated DBP species have been observed in the Kagithane and Buyukcekmece distribution systems districts. In fact, Spearman partial correlations (Spearman rank correlation coefficients [rs]) tend to be higher among analogues in terms of number and types of substituent, especially TCAA with TCM (rs 0.91), and DBAA with DBCM (rs 0.90). In contrast, the hydraulic (residence time and flow rate) and chemical mechanisms (hydrolysis, volatilization, and adsorption) affect the fate and transport of DBPs in distribution systems. Seasonal and spatial variations of DBPs presented in this study have important implications on regulatory issues and from an epidemiological point of view.     

固相萃取—气相色谱—质谱测定再生水中邻苯二甲酸酯类物质

探讨了一种再生水中邻苯二甲酸酯类物质的测定方法——固相萃取—气相色谱—质谱,检测了相关再生水标准中涉及的邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)两类物质。在质量浓度为20～1 000μg/L时,两类物质的回归方程的相关系数均大于0.999,检出限分别是0.060、0.002μg/L,DBP、DEHP的相对标准偏差分别为4.1%～7.4%、5.1%～6.1%。利用固相萃取技术进行预处理,平均加标回收率为96.6%、89.6%。检测了北京市4座再生水厂出水中DBP和DEHP含量,其中,DBP在1.74～5.59μg/L,低于《城市污水再生利用景观环境用水水质》(GB/T 18921—2002)规定的限值(不超过0.1mg/L),但高于《城市污水再生利用地下水回灌水质》(GB/T 19772—2005)规定的限值(不超过3μg/L);DEHP在0.42～4.93μg/L,满足GB/T 19772—2005要求(不超过8μg/L)。     

Minimization of the formation of disinfection by-products

The drinking water industry is required to minimize DBPs levels while ensuring adequate disinfection. In this study, efficient and appropriate treatment scheme for the reduction of disinfection by-product (DBPs) formation in drinking water containing natural organic matter has been established. This was carried out by the investigation of different treatment schemes consisting of enhanced coagulation, sedimentation, disinfection by using chlorine dioxide/ozone, filtration by sand filter, or granular activated carbon (GAC). Bench scale treatment schemes were applied on actual samples from different selected sites to identify the best conditions for the treatment of water. Samples were collected from effluent of each step in the treatment train in order to analyze pH, UV absorbance at 254 nm (UVA₂₅₄), specific UV absorbance at 254 nm (SUVA₂₅₄), dissolved organic carbon (DOC), haloacetic acids (HAAs) and trihalomethanes (THMs). The obtained results indicated that using pre-ozonation/enhanced coagulation/activated carbon filtration treatment train appears to be the most effective method for reducing DBPs precursors in drinking water treatment.     

Multi-route human health risk assessment from trihalomethanes in drinking and non-drinking water in Abadan,Iran

Natural organic matter reacted with chlorine used for disinfection, and finally, trihalomethanes (THMs) are formatted. The main purpose of this study was to determine four THM concentrations and human health cancer risk and non-cancer risk assessment from exposure through oral ingestion, dermal contact, and inhalation for males and females in Abadan. Two sampling sites were selected, and five samples before and after treatment by two different water treatment systems (RO and ion exchange) were collected every week. Results showed that total THM concentrations before and after treatment by RO were 98.1 and 8.88 μg/L, and ion exchange ranged between 101.9 and 14.96 μg/L, respectively, that before treatment was upper than the maximum of 80 mg/L recommended by USEPA. Inhalation was the primary route of exposure by around 80–90% of cancer risk. Total cancer risk was higher than the USEPA acceptable limit of 10^?6 via three exposure routes. Oral route has the higher hazard index values than dermal ways.

     

Fate of disinfection by-products in groundwater during aquifer storage and recovery with reclaimed water

Knowledge on the behaviour of disinfection by-products (DBPs) during aquifer storage and recovery (ASR) is limited even though this can be an important consideration where recovered waters are used for potable purposes. A reclaimed water ASR trial in an anoxic aquifer in South Australia has provided some of the first quantitative information at field-scale on the fate and transport of trihalomethanes (THMs) and haloacetic acids (HAAs). The results revealed that THM half-lives varied from <1 to 65 days, with persistence of chloroform being highest and bromoform lowest. HAA attenuation was rapid (<1 day). Rates of THM attenuation were shown to be highly dependent on the geochemical environment as evidenced by the 2-5 fold reduction in half-lives at the ASR well which became methanogenic during the storage phase of the trial, as compared to an observation well situated 4 m away, which remained nitrate-reducing. These findings agree with previous laboratory-based studies which also show persistence declining with increased bromination of THMs and reducing redox conditions. Modelling suggests that the chlorinated injectant has sufficient residual chlorine and natural organic matter for substantial increases in THMs to occur within the aquifer, however this is masked in some of the field observations due to concurrent attenuation, particularly for the more rapidly attenuated brominated compounds. The model is based on data taken from water distribution systems and may not be representative for ASR since bromide and ammonia concentrations in the injected water and the possible role of organic carbon in the aquifer were not taken into consideration. During the storage phase DBP formation potentials were reduced as a result of the removal of precursor material despite an increase in the THM formation potential per unit weight of total organic carbon. This suggests that water quality improvements with respect to THMs and HAAs can be achieved through ASR in anoxic aquifers.     

Fate of disinfection by-products in groundwater during aquifer storage and recovery with reclaimed water

Knowledge on the behaviour of disinfection by-products (DBPs) during aquifer storage and recovery (ASR) is limited even though this can be an important consideration where recovered waters are used for potable purposes. A reclaimed water ASR trial in an anoxic aquifer in South Australia has provided some of the first quantitative information at field-scale on the fate and transport of trihalomethanes (THMs) and haloacetic acids (HAAs). The results revealed that THM half-lives varied from <1 to 65 days, with persistence of chloroform being highest and bromoform lowest. HAA attenuation was rapid (<1 day). Rates of THM attenuation were shown to be highly dependent on the geochemical environment as evidenced by the 2-5 fold reduction in half-lives at the ASR well which became methanogenic during the storage phase of the trial, as compared to an observation well situated 4 m away, which remained nitrate-reducing. These findings agree with previous laboratory-based studies which also show persistence declining with increased bromination of THMs and reducing redox conditions. Modelling suggests that the chlorinated injectant has sufficient residual chlorine and natural organic matter for substantial increases in THMs to occur within the aquifer, however this is masked in some of the field observations due to concurrent attenuation, particularly for the more rapidly attenuated brominated compounds. The model is based on data taken from water distribution systems and may not be representative for ASR since bromide and ammonia concentrations in the injected water and the possible role of organic carbon in the aquifer were not taken into consideration. During the storage phase DBP formation potentials were reduced as a result of the removal of precursor material despite an increase in the THM formation potential per unit weight of total organic carbon. This suggests that water quality improvements with respect to THMs and HAAs can be achieved through ASR in anoxic aquifers.