饮用水消毒副产物研究状况

本文介绍了饮用水中消毒副产物的研究状况。其中重点介绍了饮用水的消毒方式及四类消毒副产物的产生、浓度、存在形态及影响因素等。简单介绍了饮用水中消毒副产物的采集、前处理方法及污染控制对策等     

基于不同水厂水质调查的消毒副产物生成趋势及模型预测

以南方某市具有代表性的7个自来水厂为研究对象,对不同季节和不同处理工艺下的原水、出厂水和管网水的9个常规水质参数和2类含碳消毒副产物进行了检测,考察了水质指标随季节的变化规律和处理工艺对不同水质指标的影响,分析了常规水质参数与消毒副产物生成量之间的关系。结果表明：7个自来水厂出厂水均检出三卤甲烷(trihalomethanes,THMs)和卤乙酸(haloacetic acids,HAAs);THMs平均质量浓度为8.70~29.35 μg·L⁻¹,HAAs平均质量浓度为13.22~39.06 μg·L⁻¹;管网水中2类消毒副产物浓度水平较出厂水略有增加;THMs的季节变化规律为冬季>春季≈秋季>夏季,HAAs的季节变化性不强。利用IBM SPSS Statistics 20进行了Spearman秩相关系数分析,并分别以原水和出厂水水质参数来建立出厂水THMs或HAAs生成量的回归方程。结果表明：THMs质量浓度预测效果良好,可用于自来水厂水质的化学安全性预警;但对于HAAs质量浓度预测,无论采用原水还是出厂水水质参数所建立的预测方程,预测结果均不理想。     

Trends of organochlorine compounds in Finnish inland waters

Caged common lake mussels (Anodonta piscinalis) have been used in the monitoring of organochlorine compounds in pulp and paper mill recipient watercourses of Finland annually from 1984 to 1998. Statistically significant decreasing trends of chlorophenols and chloroguaiacols originating from chlorobleaching were observed in all recipients in parallel with the decreasing discharges from the mills. Metabolites of chlorophenols, chloroanisoles and chloroveratroles had no or slightly increasing trends. Elevated PCB concentrations were measured in four watercourses. In two areas, PCBs were found to be significantly increasing, in two other cases they showed no trend. A mill producing recycled paper was apparently responsible for an increase of PCBs and DDE in recipient watercourses. Overall decreases were observed for other chlorohydrocarbons except for DDT. Material flows of chlorohydrocarbons were positively correlated with waterflows (Q) in some cases.     

管道分质供水消毒副产物及其安全性评价

消毒副产物是饮用水中应主要控制的毒害物。然而，管道分质供水中消毒副产物特征及污染水平很少研究。以某一管道分质供水工程为例，对其中消毒副产物进行了详细研究。研究结果表明，管道分质供水消毒副产物在量与质上与其源水自来水存在很大差别。在管道分质供水中消毒副产物量少，一般不到自来水的1／10，且主要是一些毒性较低、与供水管材有关的溶出物。据此计算出管道分质供水由消毒副产物引起的致癌风险性一般不到其源水的1／10，其安全性大大提高。     

多水源供水管网中消毒副产物风险分析

通过调研北方某大型城市多水源供水格局下管网水中三卤甲烷(THMs)和卤乙酸(HAAs)这2类消毒副产物(DBPs)的质量浓度水平,对管网中各类DBPs的超标风险、风险点的时空分布及影响因素进行了分析,从确定管网指示性DBPs、检测频率及管网采样点布设3个方面提出了关于管网DBPs风险分析方法的建议.研究结果表明,该市D...     

Modeling the formation of chlorination by-products in river waters with different quality

Water chlorination results in formation of a variety of organic compounds, known as chlorination by-products (CBPs), mainly trihalomethanes (THMs) and haloacetic acids (HAAs). Factors affecting their concentrations have been found to be organic matter content of water, pH, temperature, chlorine dose, contact time and bromide concentration, but the mechanisms of their formation are still under investigation. Within this scope, chlorination experiments have been conducted with river waters from Lesvos island, Greece, with different water quality regarding bromide concentration and organic matter content. The factors studied were pH, time and chlorine dose. The determination of CBPs was carried out by gas chromatography techniques. Statistical analysis of the results was focused on the development of multiple regression models for predicting the concentrations of total trihalomethanes and total HAAs based on the use of pH, reaction time and chlorine dose. The developed models, although providing satisfactory estimations of the concentrations of the CBPs, showed lower correlation coefficients than the multiple regression models developed for THMs only during previous study. It seems that the different water quality characteristics of the two river waters in the present study is responsible for this phenomenon. The results indicate that under these conditions the formation of THMs and HAAs in water has a more stochastic character, which is difficult to be described by the conventional regression techniques.     

臭氧对饮用水中氯化消毒副产物生成的影响

以北京市某水厂砂滤池出水为实验原水,研究了臭氧曝气时间对实验原水中天然有机物（NOM）性质、结构及氯化消毒副产物生成的影响。通过高效凝胶色谱、三维荧光光谱、红外光谱等检测分析方法对水中NOM进行表征后发现,经臭氧作用后水样DOC浓度升高、亲水性增加、芳香性及重均分子量下降。有机物中羟基、碳碳双键或碳氮双键及其共轭体系、脱质子羧基官能团与氯反应活性较强。综合考虑臭氧作用后NOM性质、结构变化及氯化消毒副产物生成量的改变,选择最佳臭氧接触时间为12 min。     

挥发性溴代消毒副产物在不同水处理工艺过程中的变化

对中国沿海某市2个自来水厂的常规和深度水处理工艺过程中挥发性溴代消毒副产物的变化规律进行了研究。在选取的7种挥发性溴代消毒副产物中,只有一溴二氯甲烷、二溴一氯甲烷、二溴甲烷和三溴甲烷这4种被检出,除二溴甲烷只在深度水处理工艺过程中被检出外,其余3种化合物在2种不同水处理工艺过程中均有检出。一溴二氯甲烷和二溴一氯甲烷在常规和深度水处理工艺过程中的部分工艺段出水中的检出浓度超过了GB 5749-2006中规定的限值（饮用水中一溴二氯甲烷和二溴一氯甲烷的的浓度限值分别为60 μg·L-1和100 μg·L-1）,应被给予足够的重视。挥发性溴代消毒副产物在常规水处理工艺过程中的检出浓度随水处理工艺流程而逐渐升高,而在深度水处理工艺过程中检出的挥发性溴代消毒副产物（除二溴甲烷外）浓度变化则表现为随水处理工艺流程先轻微降低后大幅升高的趋势。与常规水处理工艺相比,挥发性溴代消毒副产物在深度水处理工艺过程中的检出浓度明显低于其在常规水处理工艺过程中对应工艺段出水中的检出浓度,但对于在常规和深度水处理工艺过程中均被检出的3种挥发性溴代消毒副产物来说,它们的最大值均出现在加氯后出厂水中。     

饮用水源水无机金属污染的应急处理

根据密云水库供水现状,针对突发性无机金属污染事件,采用聚合氯化铝辅助化学沉淀法进行应急处理。选用Cu2＋、Fe2＋、Zn2＋和Cd2＋ 4种金属离子为目标污染物,首先通过小试实验确立了最佳混凝处理条件。结果表明,调节pH值为8．0左右,可使初始浓度为5mg／L和10mg／L的Cu2＋浓度降至0．96mg／L和0．67mg／L;初始浓度为1．5mg／L和3mg／L的Fe2＋浓度降至0．27mg／L和0．24mg／L;初始浓度为0．05mg／L和0．1mg／L的Cd2＋浓度降为0．0089mg／L和0．0078mg／L;调节pH值为9．0时,可使初始浓度为5mg／L和10mg／L的Zn2＋浓度降至0．57mg／L和0．48mg／L。4种污染物出水浓度均低于国家饮用水标准。在小试基础上,在北京第九水厂开展无机金属污染处理的中试实验,结果表明所选用的聚合氯化铝辅助化学沉淀法简便易行,可实现污染物快速、有效去除。     

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.     

再生水做景观用水使用含氯消毒剂消毒的副产物及安全性

再生水消毒后主要作为城市杂用水利用,消毒副产物及其毒性的研究非常重要.在浓度为 5～8 mg/L 的消毒剂(ClO2、HClO)量下,灭菌率能够达到 100%.2 种消毒体系均产生少量ClO2-、ClO3-和CHCl3,对检验用水生生物未产生毒性.适当的选择消毒剂浓度,控制反应条件,能够实现再生水的安全回用.     

离子色谱在饮用水消毒副产物及高氯酸盐分析中的应用

介绍了离子色谱在饮用水中消毒副产物及高氯酸盐分析中的应用。重点介绍了离子色谱测定饮用水中溴酸盐和高氯酸盐的方法。简单介绍了卤代乙酸和氯酸盐的离子色谱测定法及离子色谱-质谱联用技术在饮用水消毒副产物及高氯酸盐分析中的应用。     

Suitability of passive sampling for the monitoring of pharmaceuticals in Finnish surface waters

The occurrence of five pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was studied by passive sampling and grab sampling in northern Lake Päijänne and River Vantaa. The passive sampling was performed by using Chemcatcher® sampler with a SDB-RPS Empore disk as a receiving phase. In Lake Päijänne, the sampling was conducted during summer 2013 at four locations near the discharge point of a wastewater treatment plant and in the years 2013 and 2015 at four locations along River Vantaa. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne determined by passive sampling ranged between 1.4–2.9 ng L^?1, 15–35 ng L^?1, 13–31 ng L^?1, 16–27 ng L^?1, and 3.3–32 ng L^?1, respectively. Similarly, the results in River Vantaa ranged between 1.2–40 ng L^?1, 15–65 ng L^?1, 13–33 ng L^?1, 16–31 ng L^?1, and 3.3–6.4 ng L^?1. The results suggest that the Chemcatcher passive samplers are suitable for detecting pharmaceuticals in lake and river waters.     

Survey of the occurrence of pharmaceuticals in Spanish finished drinking waters

Fifty samples of finished drinking waters (FDWs) from Spain covering 12 million inhabitants were tested for 53 pharmaceuticals pertaining to 12 different Anatomical Therapeutic Chemical (ATC) classification system codes. The studied compounds are a combination of most commonly consumed pharmaceuticals with other barely reported in the literature. Five compounds, azithromycin, clarithromycin, erythromycin, sulfamethoxazole, and ibuprofen were tentatively identified by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in some samples (2 to 15 %), but only ibuprofen and azithromycin could be confirmed when analyzed by liquid chromatography–high-resolution mass spectrometry (LC-HRMS) with a quadrupole-Orbitrap instrument. Concentration levels of ibuprofen in the positive samples ranged from 12 to 17 ng/L (n?=?6) while for azithromycin values from 5 to 9.5 ng/L (n?=?3) were found. Ibuprofen fragmentation behaviour in different mass spectrometry instrument configurations (triple quadrupole, quadrupole-ion trap, and quadrupole-Orbitrap) was evaluated.     

饮用水中典型含氮消毒副产物的生成与控制研究进展

含氮消毒副产物作为一类具有强“三致”作用的高毒性新兴消毒副产物,其生成和控制等相关问题是饮用水处理领域研究的重点和难点。典型的含氮消毒副产物有卤乙腈、亚硝胺、卤代硝基甲烷及卤乙酰胺,在总结这类消毒副产物的生成机制和去除手段的基础上,针对其浓度低、极性强造成富集难、去除率低的瓶颈问题,分别从新材料、新技术研发及工艺优化组合方向提出了消除含氮消毒副产物问题的研究重点,展望了新型纳米功能材料耦合电化学技术处理含氮消毒副产物的发展前景,为解决强“三致”作用的高毒性新兴含氮消毒副产物问题提供参考。     

Molecular size distribution of natural organic matter in raw and drinking waters.

The purpose of this study was to compare the molecular size distribution (MSD) of natural organic matter (NOM) in raw waters (RW) and drinking waters (DW), and to find out the differences between MSD after different water treatment processes. The MSD of NOM of 34 RW and DW of Finnish waterworks were determined with high-performance size-exclusion chromatography (HPSEC). Six distinct fractions were generally separated from water samples with the TSK G3000SW column, using sodium acetate at pH 7 as an eluent. Large and intermediate humic fractions were the most dominant fractions in surface waters (lakes and rivers), while in artificially recharged groundwaters and natural groundwaters intermediate and small fractions predominated. Water treatment processes removed the two largest fractions almost completely shifting the MSD towards smaller molecular size in DW. Granular activated carbon (GAC) filtration, ozonation, and their combination reduced all humic fractions compared to the conventional treatment. Humic fractions correlated with total organic carbon (TOC) content and chemical oxygen demand, this being especially true in RW. The results demonstrate that the HPSEC method can be applied for a qualitative and also for rough estimate quantitative analyzes of NOM directly from RW and DW samples without sample pretreatment.     

天然水与28种市售饮用水中"三氮"和磷的调查

2004年8月,测定了海水、黄河水、小清河水、雨水、地下水以及17种瓶装矿泉水、9种瓶装纯净水和北京市、青岛市自来水中的"三氮" (NH 4-N、NO-2-N、NO-3-N) 、无机磷、pH、DO等,发现天然水中NO-3-N过高,水体氮负荷增加,N/P最高达697,雨水pH最低为3.98,部分矿泉水NO-3-N比青岛市自来水还高,北京市自来水的NO-3-N高达8.53 mg/L,为所测饮用水之首.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.