焦炉烟气中有机污染物的GC-MS测定

以玻璃纤维滤膜采集焦炉烟气样品,比较了索氏提取和超声波提取两种前处理方法效果,用ＧＣ－ＭＳ法进行分析研究,检出苯并「ａ」芘等多种多环芳烃类有机污染物,并对部分化合物进行了定量分析。     

水中矿物元素的ICP-MS分析

用ICP－MS对地下水、地表水和饮用水中的矿物元素进行了分析测定，实验证明用ICP－MS可以同时测定地下水，地表水和饮用水中矿物元素；该法灵敏度、精密度和准确度都能满足有关标准的要求，具有多元素同时分析，样品前处理简单，干扰少，测定快速，省事省力等优点。     

一种水体中有机污染物快速筛查与半定量的方法及其应用

采用液液萃取法富集水体中的有机污染物,以气相色谱-质谱和Compound composer软件进行筛查和半定量计算,同时以气相色谱-质谱法在选择离子模式下对Compound composer软件的半定量结果进行验证,结果表明除3-氨基苯酚、豆甾醇和β-谷甾醇外,其它物质的回收率在74％～102％之间,保留时间偏差为-0.158 ～0.049 min,对添加量为1.0μg目标物的水样半定量,结果偏差在-0.48～0.62 μg之间.在无标准样品的条件下,利用Compound composer软件及其自带含近千种化合物标准曲线的数据库,对江苏省南通、苏州和无锡三市的地表水环境样品进行监测,筛查其中主要的有机污染物,并进行半定量计算.三市地表水样中共检出47种有机污染物.2,6-二叔丁基-4-甲基苯酚为检出浓度最高的化合物,其浓度达140 μg·L-1,酞酸酯类和多环芳烃类物质普遍存在,其单体浓度范围分别为1.7～48μg·L-1和0.13 ～9.6 μg· L-1.依照GB3838-2002《地表水环境质量标准》,三市地表水体中酞酸酯类严重超标,水体中总有机物污染状况应引起关注.     

地下水有机污染物质量监控样品检测数据质量评价EI北大核心CSCD

选取我国5家地下水污染调查检测实验室前后两年质量监控样品检测数据,按检测组分、检测样品类型和实验室检测技术能力3方面进行质量监控评价。两年内5家实验室的288件检测样品,累计5454个检测组分中各检测组分合格率为90.4%~100%,挥发性有机污染物(VOC)和半挥发性有机污染物(SVOC)样品的合格率为97.4%~99.4%,均满足地下水污染调查评价样品分析与质量控制技术要求;5家实验室VOC和SVOC样品检测的整体合格率为88.4%~100%。总体上我国地下水污染调查检测实验室的有机污染物测试能力有很大提高,检测数据准确可靠。     

地下水有机污染物质量监控样品检测数据质量评价

选取我国5家地下水污染调查检测实验室前后两年质量监控样品检测数据,按检测组分、检测样品类型和实验室检测技术能力3方面进行质量监控评价。两年内5家实验室的288件检测样品,累计5454个检测组分中各检测组分合格率为90.4%~100%,挥发性有机污染物(VOC)和半挥发性有机污染物(SVOC)样品的合格率为97.4%~99.4%,均满足地下水污染调查评价样品分析与质量控制技术要求;5家实验室VOC和SVOC样品检测的整体合格率为88.4%~100%。总体上我国地下水污染调查检测实验室的有机污染物测试能力有很大提高,检测数据准确可靠。     

地下水中102种酸性、碱性和中性有机污染物的气相色谱-质谱法同时快速测定

建立了同时快速检测地下水中102种酸性、碱性和中性有机污染物的气相色谱－质谱（GC－MS）分析方法,所建方法涉及苯酚、苯胺、苯基醚、多氯萘、联苯等10类污染物。考察了酸性、碱性和中性有机污染物的同时提取条件,结果显示采用先中性、再酸性、后碱性三步液液萃取方式可以改善污染物的提取回收率,提高分析准确度和精密度。在优化条件下,除五氯苯酚外,101种目标物在各自的质量浓度范围内呈良好线性关系,相关系数（r）为0.995 0～0.999 9。地下水样品在低、中、高3个浓度水平的加标回收率分别为47.2%～126%、43.0%～117%、38.8%～120%,相对标准偏差（RSD,n = 7）分别为1.1%～27%、2.6%～33%、2.9%～30%,方法检出限为1.8～19.7 ng/L（五氯苯酚、邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯、邻苯二甲酸二（2-乙基）己酯除外）。方法应用于山西、河南等部分典型污染场地的地下水样品筛查,检出苯酚、苯胺、多环芳烃及其衍生物等24种酸、碱和中性有机污染物,点位检出率达到46.7%,水质明显呈点源污染特征。该方法灵敏、准确、简单、快速,可实现多目标物同时检测,有助于地下水中有机污染物快速筛查。     

固相萃取-衍生化-气相色谱质谱法测定水中9种烷基酚类化合物

针对地表水、地下水及饮用水中9种烷基酚类化合物的含量检测，建立了一种适合于气相色谱-质谱分析的衍生化方法。分别对样品预处理的衍生化温度、反应时间、水体样品pH、洗脱溶剂类型及用量进行优化。优化结果表明，烷基酚类化合物的质量浓度在20.0～1 000μg/L范围内与色谱峰面积具有良好的线性关系，线性相关系数均不低于0.999 1，方法检出限为4.49～9.46 ng/L。地表水、地下水及饮用水样品加标回收率为77.6%～98.8%，测定结果的相对标准偏差不大于11.4%(n=7)。该方法适用于地表水、地下水及饮用水中烷基酚类化合物的检测。     

高效液相色谱-串联质谱法同时测定水中13种有机污染物北大核心CSCD

以地表水环境质量标准严格控制的特定项目为依据,建立了直接进样-高效液相色谱-串联质谱同时测定水中13种化学性质差异较大的有机污染物的分析方法,这13种有机污染物为乐果、敌敌畏、敌百虫、对硫磷、甲基对硫磷、马拉硫磷、内吸磷、丙烯酰胺、苯胺、联苯胺、甲萘威、微囊藻毒素-LR、阿特拉津。水样经0.22μm 尼龙66滤膜过滤后,采用 Kromasil 100-5 C18柱（150 mm×2.1 mm,5μm）分离,以甲醇-0.01％甲酸水溶液为流动相进行梯度洗脱,流速0.5 mL／min,柱温40℃,电喷雾正离子模式（ESI＋）电离,多反应监测模式（MRM）进行检测,外标法定量。13种化合物的浓度与其峰面积在一定浓度范围内均呈现良好的线性关系（ r≥0.9995）,方法检出限为0.02～0.1μg／L。测定低、中、高浓度的加标样品,13种化合物的相对标准偏差为0.5％～5.0％（ n＝6）,实际样品加标平均回收率为81.2％～112％。此方法灵敏度高、干扰小、分析速度快,可适用于地表水、地下水中这13种有机污染物的同时分析。     

高效液相色谱-串联质谱法同时测定水中13种有机污染物

以地表水环境质量标准严格控制的特定项目为依据,建立了直接进样-高效液相色谱-串联质谱同时测定水中13种化学性质差异较大的有机污染物的分析方法,这13种有机污染物为乐果、敌敌畏、敌百虫、对硫磷、甲基对硫磷、马拉硫磷、内吸磷、丙烯酰胺、苯胺、联苯胺、甲萘威、微囊藻毒素-LR、阿特拉津。水样经0.22 μm尼龙66滤膜过滤后,采用Kromasil 100-5 C18柱(150 mm×2.1 mm, 5 μm)分离,以甲醇-0.01%甲酸水溶液为流动相进行梯度洗脱,流速0.5 mL/min,柱温40 ℃,电喷雾正离子模式(ESI⁺)电离,多反应监测模式(MRM)进行检测,外标法定量。13种化合物的浓度与其峰面积在一定浓度范围内均呈现良好的线性关系(r≥0.9995),方法检出限为0.02~0.1 μg/L。测定低、中、高浓度的加标样品,13种化合物的相对标准偏差为0.5%~5.0%(n=6),实际样品加标平均回收率为81.2%~112%。此方法灵敏度高、干扰小、分析速度快,可适用于地表水、地下水中这13种有机污染物的同时分析。     

高效液相色谱-串联质谱法同时测定水中18种酚类污染物

建立了一种同时测定地表水、地下水环境样品中18种酚类污染物的分析方法。样品经0.22μm聚四氟乙烯滤膜过滤后,采用Thermo Hypersil ODS柱(100 mm×2.1 mm,5.0μm)分离,以甲醇-0.01 mol/L甲酸铵/甲酸水溶液(p H 4.0)为流动相,柱温30℃,流速0.2 m L/min进行梯度洗脱,电喷雾负离子模式(ESI-)电离、多反应监测模式(MRM)进行检测,外标法定量。18种酚类化合物的浓度与其峰面积在一定浓度范围内均呈良好线性关系(r2≥0.999 1),方法检出限为0.02~0.51μg/L。18种酚类化合物在低、中、高浓度的平均加标回收率为84.5%~112%,相对标准偏差(n=6)为0.6%~4.3%。此方法灵敏度高、干扰小、分析速度快,适用于地表水、地下水等较洁净水环境样品中18种酚类污染物的同时分析。     

A Comprehensive Review for Groundwater Contamination and Remediation: Occurrence,Migration and Adsorption Modelling

The provision of safe water for people is a human right; historically, a major number of people depend on groundwater as a source of water for their needs, such as agricultural, industrial or human activities. Water resources have recently been affected by organic and/or inorganic contaminants as a result of population growth and increased anthropogenic activity, soil leaching and pollution. Water resource remediation has become a serious environmental concern, since it has a direct impact on many aspects of people’s lives. For decades, the pump-and-treat method has been considered the predominant treatment process for the remediation of contaminated groundwater with organic and inorganic contaminants. On the other side, this technique missed sustainability and the new concept of using renewable energy. Permeable reactive barriers (PRBs) have been implemented as an alternative to conventional pump-and-treat systems for remediating polluted groundwater because of their effectiveness and ease of implementation. In this paper, a review of the importance of groundwater, contamination and biological, physical as well as chemical remediation techniques have been discussed. In this review, the principles of the permeable reactive barrier’s use as a remediation technique have been introduced along with commonly used reactive materials and the recent applications of the permeable reactive barrier in the remediation of different contaminants, such as heavy metals, chlorinated solvents and pesticides. This paper also discusses the characteristics of reactive media and contaminants’ uptake mechanisms. Finally, remediation isotherms, the breakthrough curves and kinetic sorption models are also being presented. It has been found that groundwater could be contaminated by different pollutants and must be remediated to fit human, agricultural and industrial needs. The PRB technique is an efficient treatment process that is an inexpensive alternative for the pump-and-treat procedure and represents a promising technique to treat groundwater pollution.     

Chemometric analysis of groundwater quality data of alluvial aquifer of Gangetic plain, North India

Water quality data set from the alluvial region in the Gangetic plain in northern India, which is known for high fluoride levels in soil and groundwater, has been analysed by chemometric techniques, such as principal component analysis (PCA), discriminant analysis (DA) and partial least squares (PLS) in order to investigate the compositional differences between surface and groundwater samples, spatial variations in groundwater composition and influence of natural and anthropogenic factors. Trilinear plots of major ions showed that the groundwater in this region is mainly of Na/K-bicarbonate type. PCA performed on complete data matrix yielded six significant PCs explaining 65% of the data variance. Although, PCA rendered considerable data reduction, it could not clearly group and distinguish the sample types (dug well, hand-pump and surface water). However, a visible differentiation between the water samples pertaining to two watersheds (Khar and Loni) was obtained. DA identified six discriminating variables between surface and groundwater and also between different types of samples (dug well, hand pump and surface water). Distinct grouping of the surface and groundwater samples was achieved using the PLS technique. It further showed that the groundwater samples are dominated by variables having origin both in natural and anthropogenic sources in the region, whereas, variables of industrial origin dominate the surface water samples. It also suggested that the groundwater sources are contaminated with various industrial contaminants in the region.     

Determination of trace elements in surface water by neutron activation analysis

In order to assure the public health, simple and relibable analytical methods must be established for effective surveillance of polluted surface water. Since the pollutants in surface water are usually found at ultratrace levels, preconcentration is generally required to ensure the quality of the analytical results. An analytical procedure consisting of preconcentration using hydrous magnesium oxide followed by neutron activation analysis has been proposed and applied to the determinations of trace elements in surface water.     

Methodical investigation of interactions between organic pollutants and humic organic material in coal wastewaters

Summary Coal wastewaters taken from a pond near Leipzig have been analyzed quantitatively and qualitatively by GC-MS. Most of the organic constituents were pollutants; they included mainly phenol and alkylphenols. Whereas the identities of the main organic contaminants varied little between surface and deep water, the concentration of pollutants in the deeper water was considerably higher. Methodical investigation of interactions between organic pollutants of differentpolarity and aquatic humic substances showed that phenols, among them highly chlorinated and nitrated derivatives, were bound by humic matter. On changing the pH value from ca 7 to 2, all the adsorbed pollutants were released.     

The Choice of Internal Standards for Measuring Volatile Pollutants in Water

54 volatile pollutants have been examined by static headspace-gas chromatography-mass selective detection in order to find the proper internal standard for each of the pollutants examined. The applicability of the internal standards has been assessed mathematically. For modelling, we prepared 2 × 4 × 4 solutions using blank water with added sodium sulphate and humic acid at four different concentrations for each. These solutions were spiked with two different concentrations of dilute standard solutions. We also examined 44 real water samples for traces of the 54 volatile pollutants, spiking them with dilute standard solutions. The results of a single measurement were 54 quotients for relative extraction efficiency: the area of the pollutant divided by the corresponding area of the spiked blank water measurement. For each pair of pollutants, the Pearson correlation coefficients were calculated for both the model and real water samples. We regarded two pollutants as being the same, if their Pearson correlation coefficient was greater than 0.95. Among similar pollutants we selected candidates for being suitable internal standards based on the highest correlation coefficients. We found, that five compounds are sufficient to cover 49 pollutants. Two pollutants did not exhibit a matrix effect and for these only the external calibration method can be used. For three pollutants, special considerations apply.The measurement data generally verified that structurally similar compounds have high correlation coefficients, but there were exceptions among similar compounds and unexpected similarities were also found. Nothing was found in the literature on determining the proper internal standard using Pearson correlation coefficients.     

In-situ methylation of strongly polar organic acids in natural waters supported by ion-pairing agents for headspace GC-MSD analysis

Strongly polar organic substances like halogenated acetic acids have been analyzed in surface water and groundwater in the catchment area of the upper Elbe river in Saxony since 1992. Coming directly from anthropogenic sources like industry, agriculture and indirectly by rainfall, their concentrations can increase up to 100 μg/L in the aquatic environment of this catchment area. A new static headspace GC-MSD method without a manual pre-concentration step is presented to analyze the chlorinated acetic acids relevant to the Elbe river as their volatile methyl esters. Using an ion-pairing agent as modifier for the in-situ methylation of the analytes by dimethylsulfate, a minimal detection limit of 1 μg/L can be achieved. Problems like the thermal degradation of chlorinated acetic acids to halogenated hydrocarbons and changing reaction yields during the headspace methylation, could be effectively reduced. The method has been successfully applied to monitoring bank infiltrate, surface water, groundwater and water works pumped raw water according to health provision principles.     

Evaluation of groundwater tritium content and mixing behavior of Tatapani geothermal systems,Chhattisgarh, India

Isotopic investigations were carried out on hot springs, groundwater and surface water to evaluate the mixing processes within the geothermal system. Physico-chemical parameter (EC, pH, Temp.) and tritium content of groundwater, hot springs and surface water were measured. The temperature of the hot springs were varied from 60 to 98.8 °C and EC from 674 to 728 μS/cm. The tritium content of groundwater varies from 1.5 to 5 TU whereas, geothermal water have slightly less tritium and their values ranges from 1.4 to 4.4 TU. Low tritium, higher EC and high temperature of a few hot springs indicate insignificant mixing whereas high tritium, lower EC and low temperature indicates significant mixing of thermal and non-thermal water. The degree of mixing for geothermal springs is estimated. It is found that the groundwater components present in the diluted thermal waters are about 25–80%. It is also observed that mixing process is prominent along the fault and in the area where groundwater exploitation is more. Extensive pumping of groundwater causes an increase in the rate of mixing of thermal and non-thermal water. The tritium content of groundwater, surface water and hot springs are indicating, it is of modern recharge.     

Optimization of an immunoassay of 2,6-dichlorobenzamide (BAM) and development of regenerative surfaces by immunosorbent modification with newly synthesised BAM hapten library

Dichlobenil is an extensively used herbicide worldwide which is transformed to the mobile 2,6-dichlorobenzamide (BAM) in soil. BAM has been found in many European groundwater resources that are exploited for drinking water. Currently, immunoassay based monitoring technique (plate based ELISA) is being employed to quantitatively detect BAM in water samples. In this work, as a starting step of developing immunoassay based on-site monitoring systems for pesticide analysis, the heterogeneous BAM immunoassay is optimised in terms of surface (polymer) regeneration. We have synthesised a small library of BAM haptens which are slightly different in chemical structures, immobilised them on surfaces and compared the affinity constants of the monoclonal antibody HYB 273 towards them. By using ELISA technology, we also have checked the regeneration potentials of the haptens, correlated these results to the affinity constants and found that BAM hapten with an intermediate affinity has better regeneration potential.     

A new method for studying the influence of pollution and soil nature on the radon emanation from water samples by using solid state nuclear track detectors

Radon emanation from surface water and groundwater samples has been studied by using CR-39 and LR-115 solid state nuclear track detectors (SSNTD). A calibration method for determining the thoron and radon concentrations of the water samples studied has been developed. The effect of pollution due to coal fly ashes, cement and granite dusts on the radon emanation from water samples has been investigated. The influence of the radon source on the radon emanation rates from water samples has been studied.     

In-situ methylation of strongly polar organic acids in natural waters supported by ion-pairing agents for headspace GC-MSD analysis

Strongly polar organic substances like halogenated acetic acids have been analyzed in surface water and groundwater in the catchment area of the upper Elbe river in Saxony since 1992. Coming directly from anthropogenic sources like industry, agriculture and indirectly by rainfall, their concentrations can increase up to 100 μg/L in the aquatic environment of this catchment area. A new static headspace GC-MSD method without a manual pre-concentration step is presented to analyze the chlorinated acetic acids relevant to the Elbe river as their volatile methyl esters. Using an ion-pairing agent as modifier for the in-situ methylation of the analytes by dimethylsulfate, a minimal detection limit of 1 μg/L can be achieved. Problems like the thermal degradation of chlorinated acetic acids to halogenated hydrocarbons and changing reaction yields during the headspace methylation, could be effectively reduced. The method has been successfully applied to monitoring bank infiltrate, surface water, groundwater and water works pumped raw water according to health provision principles. Received: 17 July 1997 / Revised: 29 September 1997 / Accepted: 2 October 1997