质谱及其联用技术在水中消毒副产物识别和分析中的应用

水中消毒副产物(DBPs)是在水消毒过程中消毒剂与水中溶解性有机物以及无机离子发生反应而产生,其对水环境生态安全和人体健康有不利影响。简述了DBPs的生成、种类、毒性和分析方法等,重点综述了气相色谱-质谱联用(GC-MS)、液相色谱-质谱联用(LC-MS)、离子色谱-质谱联用(IC-MS)以及超高分辨率质谱(UPMS)等质谱(MS)及其联用技术在水中DBPs识别和分析中的应用,分析了不同MS技术的特点和应用实例,提出了MS技术在DBPs研究领域的发展方向与挑战。     

水中消毒副产物的监测方法研究进展

含氯、含氧等杀菌类消毒剂在饮用水生产、废水排放、再生水利用等环节应用广泛,会与水中的前驱物通过取代、氧化还原、水解、加成等反应形成种类繁多的消毒副产物(DBPs).DBPs的靶标监测基于已知DBPs的特性如挥发性、半挥发性、不挥发性等,采取相应的前处理和仪器分析方法;非靶标鉴别可对大量未知的DBPs进行筛查.综述了三卤...     

Trihalomethane formation potential in treated water supplies in urban metro city

Trihalomethane (THM) formation potential (TFP) is very useful test to assess the level of the formation of trihalomethanes in worst case scenario. Organics in water have the potential to generate harmful disinfection by-products (DBPs) such as THMs, as a result of their reaction with disinfectant chlorine used in drinking water. DBPs are increasingly recognized as cancerous agents. TFP of postchlorinated treated water were investigated at six water treatment plants (WTPs) in Delhi City (India). The present paper presents the current trends of TFP so that prevention and control measures can be initiated by the regulating agencies responsible for drinking water supply. Liquid–liquid extraction method, followed by qualitative and quantitative estimation by gas chromatograph equipped with electron capture detector, had been used for the determination of THMs in water samples collected at the outlet just before supplying to the consumers during 2000–2007. The TFP values from 2004 onward of all WTPs did not exceed the WHO guideline value of ≤1.     

Ascorbic acid reduction of active chlorine prior to determining Ames mutagenicity of chlorinated natural organic matter (NOM)

Many potable water disinfection byproducts (DBPs) that result from the reaction of natural organic matter (NOM) with oxidizing chlorine are known or suspected to be carcinogenic and mutagenic. The Ames assay is routinely used to assess an overall level of mutagenicity for all compounds in samples from potable water supplies or laboratory studies of DBP formation. Reduction of oxidizing disinfectants is required since these compounds can kill the bacteria or react with the agar, producing chlorinated byproducts. When mutagens are collected by passing potable water through adsorbing resins, active chlorine compounds react with the resin, producing undesirable mutagenic artifacts. The bioanalytical and chemoanalytical needs of drinking water DBP studies required a suitable reductant. Many of the candidate compounds failed to meet those needs, including 2,4-hexadienoic (sorbic) acid, 2,4-pentanedione (acetylacetone), 2-butenoic (crotonic) acid, 2-butenedioic (maleic and fumaric) acids and buten-2-ol (crotyl alcohol). Candidates were rejected if they (1) reacted too slowly with active chlorine, (2) formed mutagenic byproducts, or (3) interfered in the quantitation of known chlorination DBPs. L-Ascorbic acid reacts rapidly and stoichiometrically with active chlorine and has limited interactions with halogenated DBPs. In this work, we found no interference from L-ascorbic acid or its oxidation product (dehydroascorbic acid) in mutagenicity assays of chlorinated NOM using Salmonella typhimurium TA100, with or without metabolic activation (S9). This was demonstrated for both aqueous solutions of chlorinated NOM and concentrates derived from the involatile, ether-extractable chlorinated byproducts of those solutions.     

DBP Levels in Chlorinated Drinking Water: Effect of Humic Substances

Chlorination is the most widely used technique for disinfection of drinking water. A consequence of chlorination is the formation of Disinfection By-Products (DBPs). The formation of DBPs in drinking water results from the reaction of chlorine with naturally occurring organic materials, principally humic and fulvic acids. This paper focuses on the effect of humic substances on the formation of twenty-four compounds belonging to different categories of DBPs. This investigation was conducted in two water treatment plants in Greece, Menidi and Galatsi, from July 1999 to April 2000. Humic substances were determined by the diethylaminoethyl (DEAE) method with subsequent UV measurement. The techniques used for the determination of DBPs were liquid-liquid extraction, gas chromatography and mass spectrometry. The concentrations of DBPs were generally low. Total trihalomethanes (TTHMs) ranged from 5.1 to 24.6 microg L(-1), and total haloacetic acids (HAAs) concentration ranged from 8.6 to 28.4 microg L(-1), while haloaketones (HKs) and chloral hydrate (CH) occurred below 1 microg L(-1). The content of humic substances was found to influence the formation of DBPs and especially TTHMs, trichloroacetic acid (TCA), dibromoacetic acid (DBA), CH, 1,1-dichloropropanone (1.1-DCP) and 1,1,1-trichloropropanone (1,1,1-TCP). Seasonal variation of TTHMs and HAAs generally followed that of humic substances content with peaks occurring in autumn and spring. The trends of 1,1-DCP, 1,1,1-TCP and CH formation seemed to be in contrast to TTHMs and HAAs. Trends of formation of individual compounds varied in some cases, probably due to influence of parameters other than humic substances content. Statistical analysis of the results showed that the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DBA are strongly affected from humic substances content (at 0.01 confidence level). The opposite is true for dichloroacetic acid (DCA) concentration. Humic substances also vary to a statistically significant degree during different months, as well as the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DCA. The variance of DBA was not statistically significant. Regarding the effect of sampling station, humic substances content showed no statistically significant difference between the two raw water sources studied.     

中国沿海三省主要饮用水源有机物监测

采用固相萃取、吹扫捕集和气相色谱-质谱联用仪(GC-MS)对江苏、浙江、山东省的21个主要地表饮用水源、126份水样中的25种VOCs、38种SVOCs进行定量检测。结果有19种VOCs、10种SVOCs至少在一个水源地多次被检出,其中挥发性氯代烃、苯系物、氯代苯类、酚类、硝基苯类、酞酸酯类、农药为中国或美国环境保护局提出的"水中优先控制污染物",最高检出量为27.79μg/L。三省主要地表水受到有机物轻度污染,水体中VOCs、SVOCs含量尚未超过《地表水环境质量标准》(GB 3838-2002)和《生活饮用水卫生标准》(GB 5749-2006)限值,工业废水排放及农田雨水径流是地表水有机物的重要来源。     

Evaluation of biological stability and corrosion potential in drinking water distribution systems: a case study

The appearance of assimilable organic carbon (AOC), microbial regrowth, disinfection by-products (DBPs), and pipe corrosion in drinking water distribution systems are among those major safe drinking water issues in many countries. The water distribution system of Cheng-Ching Lake Water Treatment Plant (CCLWTP) was selected in this study to evaluate the: (1) fate and transport of AOC, DBPs [e.g., trihalomethanes (THMs), haloacetic acids (HAAs)], and other organic carbon indicators in the selected distribution system, (2) correlations between AOC (or DBPs) and major water quality parameters [e.g. dissolved oxygen (DO), free residual chlorine, and bacteria, and (3) causes and significance of corrosion problems of the water pipes in this system. In this study, seasonal water samples were collected from 13 representative locations in the distribution system for analyses of AOC, DBPs, and other water quality indicators. Results indicate that residual free chlorine concentrations in the distribution system met the drinking water standards (0.2 to 1 mg l(-1)) established by Taiwan Environmental Protection Administration (TEPA). Results show that AOC measurements correlated positively with total organic carbon (TOC) and UV-254 (an organic indicator) values in this system. Moreover, AOC concentrations at some locations were higher than the 50 microg acetate-C l(-1) standard established by Taiwan Water Company. This indicates that the microbial regrowth might be a potential water quality problem in this system. Higher DO measurements (>5.7 mg l(-1)) might cause the aerobic biodegradation of THMs and HAAs in the system, and thus, low THMs (<0.035 mg l(-1)) and HAAs (<0.019 mg l(-1)) concentrations were observed at all sampling locations. Results from the observed negative Langelier Saturation Index (LSI) values, higher Ryznar Stability Index (RSI) values, and high Fe3+ concentrations at some pipe-end locations indicate that highly oxidative and corrosive conditions occurred. This reveals that pipe replacement should be considered at these locations. These findings would be helpful in managing the water distribution system for maintaining a safe drinking water quality.     

Optimizing a GC-MS method for screening of Stachybotrys mycotoxins in indoor environments

Presence of Stachybotrys chartarum in indoor environments has been linked to building-associated disease, however, the causative agents are unknown. Verrucarol (VER) and trichodermol (TRID) are hydrolysis products of some major S. chartarum mycotoxins, i.e. macrocyclic trichothecenes and trichodermin. We optimized gas chromatography-mass spectrometry (GC-MS) methods for detecting VER and TRID in S. chartarum-contaminated indoor environmental samples. Heptafluorobutyryl derivatives of both VER and TRID exhibited little MS fragmentation and gave much higher detection sensitivity (sub-picogram injected onto the GC column), both in GC-MS and GC-MSMS, than trimethylsilyl derivatives. Optimal detection sensitivity and specificity was achieved by combining chemical ionization and negative ion (NICI) detection with MSMS. With this method, VER and TRID were detected in building materials colonized by S. chartarum and TRID was demonstrated in dust settled in the breathing zone in a house where an inner wall was colonized. In summary, we have shown that NICI-GC-MSMS can be used to demonstrate mycotoxins in house dust in S. chartarum-contaminated dwellings.     

Techniques and methods for the determination of haloacetic acids in potable water

Haloethanoic (haloacetic) acids (HAAs) are formed as disinfection byproducts (DBPs) during the chlorination of natural water to make it fit for consumption. Sundry analytical techniques have been applied in order to determine the concentrations of the HAAs in potable water supplies: gas chromatography (GC-MS, GC-ECD); capillary electrophoresis (CE); liquid chromatography (LC), including ion chromatography (IC); and electrospray ionization mass spectrometry (ESI-MS). Detection limits required to analyze potable water samples can be regularly achieved only by GC-ECD and ESI-MS. Without improvements in preconcentration or detector sensitivity, CE and LC will not find application to potable water supplies. The predominant GC-ECD methods use either diazomethane or acidified methanol to esterify (methylate) the carboxylic acid moiety. For HAA5 analytes, regulated under the EPA's Stage 1 DBP Rule, diazomethane is satisfactory. For HAA9 data gathered under the Information Collection Rule, acidified methanol outperforms diazomethane, which suffers from photo-promoted side reactions, especially for the brominated trihaloacetic acids. Although ESI-MS can meet sensitivity and selectivity requirements, limited instrumentation availability means this technique will not be widely used for the time being. However, ESI-MS can provide valuable confirmatory information when coupled with GC-ECD in a research setting.     

SPE-GC-MS法测定地下水中26种有机氯农药

采用固相萃取(SPE)技术,结合气相色谱/质谱(GC-MS)选择离子检测法(SIM)对水样中26种有机氯农药(OCPs)进行提取、净化、浓缩前处理,优选了固相萃取小柱填料及萃取、净化条件,优化了GC-MS的工作参数,建立了地下水中26种有机氯农药的SPE-GC-MS分析方法。针对不同的组分,本法加标回收率为76.422%~112.512%,相对标准偏差为4.905%~15.524%,检出限为0.014~0.089μg/L。该方法操作简单,消耗费用低,分析速度快,具有较高的灵敏度和回收率。     

Penetration of polar brominated DBPs through the activated carbon columns during total organic bromine analysis

Total organic bromine (TOBr) is a collective parameter representing all the brominated organic disinfection byproducts (DBPs) in water samples. TOBr can be measured using the adsorption-pyrolysis method according to Standard Method 5320B. This method involves that brominated organic DBPs are separated from inorganic halides and concentrated from aqueous solution by adsorption onto the activated carbon (AC). Previous studies have reported that some commonly known brominated DBPs can partially penetrate through the AC during this adsorption step. In this work, the penetration of polar brominated DBPs through AC and ozone-modified AC was explored with two simulated drinking water samples and one chlorinated wastewater effluent sample. Polar brominated DBPs were selectively detected with a novel precursor ion scan method using electrospray ionization-triple quadrupole mass spectrometry. The results show that 3.4% and 10.4% of polar brominated DBPs (in terms of total ion intensity) in the chlorinated Suwannee River fulvic acid and humic acid samples, respectively, penetrated through the AC, and 19.6% of polar brominated DBPs in the chlorinated secondary wastewater effluent sample penetrated through the AC. The ozone-modification of AC minimized the penetration of polar brominated DBPs during the TOBr analysis.     

Assessing regulatory violations of disinfection by-products in water distribution networks using a non-compliance potential index

Inactivating pathogens is essential to eradicate waterborne diseases. However, disinfection forms undesirable disinfection by-products (DBPs) in the presence of natural organic matter. Many regulations and guidelines exist to limit DBP exposure for eliminating possible health impacts such as bladder cancer, reproductive effects, and child development effects. In this paper, an index named non-compliance potential (NCP) index is proposed to evaluate regulatory violations by DBPs. The index can serve to evaluate water quality in distribution networks using the Bayesian Belief Network (BBN). BBN is a graphical model to represent contributing variables and their probabilistic relationships. Total trihalomethanes (TTHM), haloacetic acids (HAA5), and free residual chlorine (FRC) are selected as the variables to predict the NCP index. A methodology has been proposed to implement the index using either monitored data, empirical model results (e.g., multiple linear regression), and disinfectant kinetics through EPANET simulations. The index’s usefulness is demonstrated through two case studies on municipal distribution systems using both full-scale monitoring and modeled data. The proposed approach can be implemented for data-sparse conditions, making it especially useful for smaller municipal drinking water systems.     

饮用水消毒副产物基因毒性与致癌性研究进展

简述了饮用水消毒副产物（DBPs）的基因毒性与致癌性的研究进展。从Ames试验、SOS/umu试验、彗星试验、微核试验及一些新颖的致突变试验结果对DBPs基因的毒性，以及从毒理学实验、流行病学研究和致癌风险评估3个方面对DBPs的致癌性进行了分析和总结，以期为今后饮用水DBPs毒性效应及其致毒机理研究提供参考，进而促进饮用水质量管理与立法的发展。     

Predictive model for chloroform during disinfection of water for consumption,city of Montevideo

The objective of this study was to predict chloroform formation resulting from the process of disinfecting water, particularly trihalomethane which is most frequently produced. A statistical model was used which included repeated measurements of water parameters used for monitoring water quality at 51 sites covering the municipal water system of Montevideo. Samples were taken considering different seasons from June 2009 to July 2011 in Montevideo. Total samples (n?=?330) were analytically studied using the headspace-gas chromatography method coupled with mass spectrometry. Chloroform was the dependent variable and the covariables were pH, temperature, free chlorine, and total chlorine. A Tobit analysis with an unstructured correlation matrix was performed, and a significant interaction was found between pH and free chlorine for the prediction of chloroform formation. We concluded that parameters for the continuous control of water quality for consumption can be used to predict the levels of chloroform that may be present. Given the large measurement to variability found in the repeated measurements, the use of averages that include more than one season is not recommended to determine the degree of compliance with acceptable levels established by norms.     

Monochloramine loss in the presence of humic acid

Free chlorine has been used extensively as a primary and secondary disinfectant for potable water. Where it is difficult to maintain a free chlorine residual or when disinfection by-products (DBPs) are of concern, monochloramine has been used to provide a stable disinfectant residual in distributions systems. Reactions of disinfectants, free chlorine or monochloramine, with natural organic matter (NOM) consequently result in the formation of DBPs such as trihalomethanes and haloacetic acids. However, few studies have focused on the fate and kinetics of monochloramine loss in the presence of reactive constituents such as NOM. Monochloramine is inherently unstable and decays even without reactive constituents present via a mechanism known as autodecomposition. Therefore, to predict monochloramine concentrations in the presence of NOM is clearly associated with the ability to adequately model autodecomposition. This study presents the results of a semi-mechanisiic model capable of predicting the loss of monochloramine in the presence of humic material in the pH range of 6.55-8.33. The model accounts for both fast and a slow monochloramine demand to explain the loss of monochloramine over the pH range of this study. The formation of dichloroacetic acid was also predicted due to the ability of the model to differentiate monochloramine reaction pathways in the presence NOM. The results shown here demonstrate the ability of a semi-mechanistic model to predict monochloramine residuals and DBP formation in the presence of humic material.     

Study of personal–indoor–ambient fine particulate matters among school communities in mixed urban–industrial environment in India

A sampling program was conducted to investigate the formation of disinfection by-products (DBPs) and dissolved organic carbon (DOC) at two advanced water treatment plants in Kaohsiung City, Taiwan. The results in this study can be used as a reference for the operational control of water treatment plants and the setting of regulations in Taiwan. Samples of drinking water were collected from two advanced water treatment plants from June 2007 to April 2008. Changes in the concentration of dissolved organic carbon, the trihalomethane formation potential, and the haloacetic acids formation potential were measured in raw water samples. Variations in the concentrations of trihalomethanes (THMs) and haloacetic acids (HAA₅) in finished drinking water were evaluated. The major species of HAA₅ were in the order of dichloroacetic acid and trichloroacetic acid and the THM was of trichloromethane. DOC was strongly related to DBPs in raw water. In this investigation, the removal efficiency of DBPs in Plant A (ultrafiltration/reverse osmosis system) exceeded that in Plant B (ozonation/biological activated carbon system). Both advanced water treatment plants greatly improved the quality of drinking water.     

Identification of surfactant degradation products as toxic organic compounds present in sewage sludge

A cost-effective strategy combining chemical analysis and bioassays for the identification of polar toxic compounds in sewage sludge is reported. ToxAlert 100 bioluminescence inhibition assay was used in combination with chemical analysis involving extraction, clean-up, chromatographic separation and mass spectrometry detection. This methodology was applied to real samples of sludge from three wastewater treatment plants (WWTP) located in Catalonia (Spain) during a 3 month period. In the first step, sewage sludge was lyophilized, treated by sonication with a mixture of methanol and chloroform and finally cleaned up using a sequential solid phase extraction (SSPE) with an octadecylsilica cartridge (C18) in series with a polymeric Lichrolut EN cartridge (Lic EN). In the second step, the toxicity of each fraction of the sludge sample was investigated using the ToxAlert 100. The unequivocal identification and quantification of polar organic cytotoxic substances present in the fractionated extracts were determined by liquid chromatography-mass spectrometry (LC-MS). Major toxic compounds identified were: non-ionic polyethoxylated surfactants (nonylphenol polyethoxylates, alcohol polyethoxylates), their intermediates (polyethylene glycol polyethoxylated, nonylphenol carboxylates and polyethoxylated alcohol carboxylates), linear alkylbenzenesulfonates and heavy metals. The toxic response (in terms of bioluminescence inhibition using ToxAlert 100), defined by the 50% effective concentration (EC50), and the toxicity units (TU) for every standard non-ionic surfactant were calculated. The results provided the identification of polar cytotoxic compounds as well as the evaluation of their contribution to the total toxicity observed in sewage sludge.     

Three years monitoring survey of pesticide residues in Sardinia wines following integrated pest management strategies

This paper reports the results of a pesticide monitoring survey on wine grapes from the 2008–2010 vintage from vineyards grown according to integrated pest management strategies. A multi-residue gas chromatography-mass spectrometry method in electron ionization and chemical ionization mode has been used for the determination of 30 pesticides in wine samples. The analytical method showed good recoveries and allowed a good separation of the selected pesticides. Repeatability and intermediate precision showed good results with CV?<?20 %. The instrumental method limits of determination (LOD) and of quantification (LOQ) were below the maximum residue levels set in wine. The analysis of the wines showed that pesticide residues were below the instrumental LOQ, and most of them were undetectable (<LOD). Only the 38 % of the pesticide applied has been detected in at least one cultivar. Metalaxil, myclobutanil, and penconazole were the pesticides most frequently found, while carignano and vermentino were the cultivars with the higher number of residues.     

Formation and modeling of disinfection by-products in drinking water of six cities in China

Water quality parameters including TOC, UV(254), pH, chlorine dosage, bromide concentration and disinfection by-products were measured in water samples from 41 water treatment plants of six selected cities in China. Chloroform, bromodichloromethane, dibromochloromethane, dichloroacetic acid and trichloroacetic acid were the major disinfection by-products in the drinking water of China. Bromoform and dibromoacetic acid were also detected in many water samples. Higher concentrations of trihalomethanes and haloacetic acids were measured in summer compared to winter. The geographical variations in DBPs showed that TTHM levels were higher in Zhengzhou and Tianjin than other selected cities. And the HAA5 levels were highest in Changsha and Tianjin. The modeling procedure that predicts disinfection by-products formation was studied and developed using artificial neural networks. The performance of the artificial neural networks model was excellent (r > 0.84).     

Determination of volatile organic compounds pollution sources in malaysian drinking water using multivariate analysis

A field investigation was conducted at all water treatment plants throughout 11 states and Federal Territory in Peninsular Malaysia. The sampling points in this study include treatment plant operation, service reservoir outlet and auxiliary outlet point at the water pipelines. Analysis was performed by solid phase micro-extraction technique with a 100 μm polydimethylsiloxane fibre using gas chromatography with mass spectrometry detection to analyse 54 volatile organic compounds (VOCs) of different chemical families in drinking water. The concentration of VOCs ranged from undetectable to 230.2 μg/l. Among all of the VOCs species, chloroform has the highest concentration and was detected in all drinking water samples. Average concentrations of total trihalomethanes (THMs) were almost similar among all states which were in the range of 28.4--33.0 μg/l. Apart from THMs, other abundant compounds detected were cis and trans-1,2-dichloroethylene, trichloroethylene, 1,2-dibromoethane, benzene, toluene, ethylbenzene, chlorobenzene, 1,4-dichlorobenzene and 1,2-dichloro - benzene. Principal component analysis (PCA) with the aid of varimax rotation, and parallel factor analysis (PARAFAC) method were used to statistically verify the correlation between VOCs and the source of pollution. The multivariate analysis pointed out that the maintenance of auxiliary pipelines in the distribution systems is vital as it can become significant point source pollution to Malaysian drinking water.