水体硝酸盐检测方法的研究进展

硝酸盐是活性氮中导致水体富营养化以及危害人体健康的重要形式,因此水体硝酸盐的检测在水体质量表征中一直备受关注。水体硝酸盐的常规检测主要是借助传统的分光光度法,这类方法经典权威,分析结果可靠,然而大都破坏样品、耗时、成本高,并且在硝酸盐定量分析中的干扰因素也较多。近年来,现代光谱技术的应用得到迅速发展,也已经在水体硝酸盐检测中有了较好的尝试,为海量水体质量信息的获取提供新的技术支撑。在介绍了水体硝酸盐检测方法的基础上,就水体硝酸盐检测方法的研究进展以及现代光谱技术在水体硝酸盐检测中的应用前景进行了归纳、分析和介绍,并指出傅里叶变换衰减全反射光谱(FTIR-ATR)可以实现快速适时的水体信息定量传感和质量监测,在水体硝酸盐的分析实践中具有广阔的应用空间。     

水体硝酸盐检测方法的研究进展

硝酸盐是活性氮中导致水体富营养化以及危害人体健康的重要形式,因此水体硝酸盐的检测在水体质量表征中一直备受关注。水体硝酸盐的常规检测主要是借助传统的分光光度法,这类方法经典权威,分析结果可靠,然而大都破坏样品、耗时、成本高,并且在硝酸盐定量分析中的干扰因素也较多。近年来,现代光谱技术的应用得到迅速发展,也已经在水体硝酸盐检测中有了较好的尝试,为海量水体质量信息的获取提供新的技术支撑。在介绍了水体硝酸盐检测方法的基础上,就水体硝酸盐检测方法的研究进展以及现代光谱技术在水体硝酸盐检测中的应用前景进行了归纳、分析和介绍,并指出傅里叶变换衰减全反射光谱(FTIR-ATR)可以实现快速适时的水体信息定量传感和质量监测,在水体硝酸盐的分析实践中具有广阔的应用空间。     

水体中环氧氯丙烷监测方法研究进展

介绍环境水体中的环氧氯丙烷监测分析方法及相关的研究进展。相关文献显示,用盐酸溶液（1+1）酸化样品有利于样品保存,采用全自动吹扫捕集处理技术,对吹扫时间、温度、色谱柱和检测器等参数进行优化。如吹扫时间设定为13 min,吹扫温度设定为35℃,经DB-624毛细管色谱柱分离,质量选择检测器进行检测,可以更好实现对水体中痕量环氧氯丙烷的富集、解析和检测。在各种环氧氯丙烷的测定方法中,选择吹扫捕集–气相色谱和质谱联用法,可实现全自动的样品前处理,其高效而且不用接触有机溶剂,检测方法步骤简单、准确性高、选择性好,在水质环氧氯丙烷测定方面具有广阔的应用前景。     

适体荧光分析法检测养殖废水中四环素类抗生素

建立了核酸适体识别-荧光探针技术检测养殖废水中土霉素、四环素、金霉素及强力霉素4种四环素类抗生素(TCs)总残留量的新方法。两段DNA对TCs共同识别后折叠成稳定的"发卡型"双链结构,核酸染料4'-6-二脒基-2-苯基吲哚(DAPI)能插入"发卡"部位产生荧光信号发射,据此可实现对TCs的定量检测。在最优实验条件下,以土霉素为目标分子建立工作曲线,在10~50 nmol/L范围内,荧光强度与对应浓度呈良好线性关系,土霉素的检出限为2.3 nmol/L。用四环素、土霉素、金霉素和强力霉素分别进行加标回收实验,平均回收率为88.5%~102.3%,相对标准偏差(n=5)为3.2%~6.7%。5个养殖场水样中均有TCs检出,检出量在7.6~42.7 nmol/L之间。该方法简单、灵敏、快速,可满足养殖场废水中TCs总残留量的测定要求。     

典型卤代阻燃剂的样品处理技术及分析检测研究进展

卤代阻燃剂被广泛用作油漆、纺织品、电子器件的添加剂,由于其具有挥发性,能渗入并长久存在于环境中,在环境和食物链中积累,对人类和其他生物健康造成危害,现已被禁止或限制使用。因此,急需建立更加灵敏、准确的卤代阻燃剂残留分析方法。本文系统介绍了卤代阻燃剂的污染途径,以及近年来关于卤代阻燃剂残留样品前处理方法和检测技术,污染途径包括：土壤、水体、空气、灰尘和生物样品污染途径等;样品前处理方法包括：固相萃取、搅拌棒萃取、分子印迹萃取、磁性固相萃取、超临界流体萃取、加压液体萃取等;检测技术包括：气相色谱-质谱检测法、液相色谱-质谱检测法、免疫分析检测法、X射线荧光法等,并对卤代阻燃剂的分析检测技术进行了总结和展望。     

羧基化多壁碳纳米管固相萃取-液相色谱-串联质谱法测定环境水体中四溴双酚A和双酚A

建立了羧基化碳纳米管固相萃取-液相色谱-串联质谱联用检测环境水体中四溴双酚A和双酚A的方法。比较了多壁碳纳米管、C60和羧基化多壁碳纳米管作为固相吸附剂对水体中四溴双酚A和双酚A的吸附效率。固相萃取浓缩后的样品经Thermo Scientific Hypersil C18色谱柱（150 mm×4.6 mm,3 μm）分离,采用串联质谱负离子模式进行检测。结果表明,四溴双酚A和双酚A在0.02~1.0 mg/L范围内具有良好的线性关系（r²≥0.99）,空白样品中的检出限（S/N=3）分别为0.04 μg/L和0.2 μg/L。将所建立的方法应用于实际环境水体中四溴双酚A和双酚A的检测,添加回收率在82%~99%之间,精密度小于5.0%,该方法可用于复杂环境样品中痕量四溴双酚A和双酚A的检测。     

Research progress of rapid detection of typical environmental pollutants based on chromatographic technologiesEI北大核心CSCD

对复杂环境介质中的典型污染物进行快速、精准甚至远程连续自动的检测,是控制环境污染、确保环境和生态安全的重要前提。近年来,基于色谱技术的典型环境污染物快速检测方法发展迅猛,主要包括样品快速制备和目标物快速检测两方面。辅助萃取、快速液相萃取、QuEChERS等样品前处理方法具有萃取效率高、溶剂消耗少、操作简便快速等优点。快速检测技术可在几秒到半小时内提供检测结果,主要包括实验室和现场检测。本文综述了2019年以来基于色谱技术的典型环境污染物快速检测研究新进展。介绍了萃取技术和基于试验设计的样品快速制备,实验室快速检测、便携仪器现场检测及遥感技术远程检测,提出了色谱技术快速检测环境污染物的挑战和展望。     

基于适配体-杂交链式反应比色检测生鲜牛乳中四环素类抗生素

以特异性识别四环素类抗生素(TCs)的广谱型适配体为识别元件,结合杂交链式反应(HCR)信号放大策略,提出了一种TCs多残留比色检测方法,并优化了检测条件和进行了方法学考察。取40 nmol·L^-1生物素化检测探针(bio-DP)溶液加入到包被有亲和素的酶标板中,室温孵育后加入牛血清白蛋白(BSA)溶液,封闭反应1 h。加入生鲜牛乳样品稀释液,室温孵育20 min,如果样品中含有TCs, TCs与bio-DP的适配体序列结合,其发夹结构被打开。加入200 nmol·L^-1生物素化发夹DNA1(bio-H1)溶液和200 nmol·L^-1生物素化发夹DNA2(bio-H2)溶液,室温下进行HCR 40 min,从而形成具有多个重复单元的双链DNA(dsDNA)纳米线。加入辣根过氧化物酶(HRP)标记链霉亲和素(SA-HRP),室温孵育标记dsDNA。加入显色剂[含3,3′,5,5′-四甲基联苯胺(TMB)],HRP催化TMB生成蓝色物质,显色5～8 min后终止反应,在酶标仪中于450 nm测量上述体系的吸光度。结果显示,...     

固相萃取-超高效液相色谱-串联质谱法测定农田回用再生水中的9种雌激素

建立了水体中9种雌激素的固相萃取-超高效液相色谱-串联质谱检测方法。利用HLB固相萃取柱富集水体中的痕量雌激素,以0.05%氨水/甲醇为流动相,经C18色谱柱分离,采用电喷雾离子源、质谱多反应监测和负离子扫描模式,实现了水体中9种雌激素的同时检测,方法分析速度为6 min,RSD在4.7%~9.5%之间,回收率范围为73%~116%,检出限在0.001~0.024μg/L之间。利用该方法对北京市某再生水灌区出水口、灌溉渠、农田灌溉点的再生水中雌激素进行了检测分析,未检出天然雌激素(雌酮、雌二醇、雌三醇)和人工合成雌激素(炔雌醇、己烷雌酚、己烯雌酚)等,但检出了壬基酚、辛基酚和双酚A等3种类环境雌激素,浓度范围为31~748 ng/L。     

柱前衍生化超高效液相色谱-串联质谱法检测水体中代森锰锌残留量

建立了柱前衍生化超高效液相色谱-串联质谱(UPLC-MS/MS)检测水体中代森锰锌残留的分析方法。样品在碱性条件下用EDTA溶液配位反应后,以碘甲烷进行柱前衍生化,以Cleanrt?-PEP固相萃取柱进行富集浓缩和净化,结合UPLC-MS/MS检测,外标法定量。检测结果表明,代森锰锌在10～1 000 ng/L浓度范围内线性关系良好,线性相关系数R~2=0.9991;在10 ng/L、100 ng/L和1 000 ng/L三个添加水平下,平均回收率在79.2%～101.5%范围内,相对标准偏差(RSDs,n=5)在2.1%～6.9%之间;定量限为10 ng/L。该方法具有灵敏度高、稳定性好和准确度高等优点,将方法应用于泰安市区周围河流和水库水体检测,检测结果显示均未超标。方法适用于水体中痕量代森锰锌检测。     

Reversed migration micellar electrokinetic chromatography with off-line and on-line concentration analysis of phenylurea herbicides

Three environmentally important phenylurea herbicides (monuron, isoproturon, diuron) were separated in reversed migration micellar electrokinetic chromatography (RM-MEKC) using 50 mM sodium dodecyl sulfate, 50 mM phosphoric acid, and 15 mM gamma-cyclodextrin. Three on-line concentration techniques are then evaluated to increase the detection sensitivity of the RM-MEKC system. Stacking with reverse migrating micelles (SRMM, water as the sample solvent) provided the best results among the focusing techniques studied. Using a z-shaped detection cell, more than 500-fold increase in peak height is obtained. As a sample preparation and off-line concentration method, solid-phase extraction (SPE) that further improved detection sensitivity was used in the analysis of spiked tap and pond water. For example, 1 parts per billion of each herbicide spiked in tap or pond water was detected by MEKC after SPE and SRMM.     

Ultrapure water for liquid chromatography-mass spectrometry studies

Improvements in trace enrichment techniques combined with the sensitivity of mass spectrometry offer enhanced opportunities to analyze ever lower concentrations of drugs, metabolites, pesticides or environmental pollutants. To perform HPLC and liquid chromatography-mass spectrometry (LC-MS) analyses under optimum conditions, the water used for mobile phase preparation needs to be highly purified and delivered on demand. Indeed, both UV photodiode array detection and MS detection methods are sensitive to organic contaminants (total organic carbon, TOC), and the water quality has a direct impact on the achievable detection limits. The benefits of UV photooxidation on TOC reduction for LC-MS studies were highlighted using electrospray ionization MS detection by comparing HPLC-grade bottled water, freshly produced UV185/254-treated water, and freshly produced non-UV-treated water.     

Room temperature phosphorescence as a liquid chromatographic detection method for polychlorinated naphthalenes and biphenyls in complex matrices

Quenched and sensitized room temperature phosphorescence techniques have been used for the detection of PCNs and PCBs after liquid chromatographic separation. The usefulness of these techniques to fingerprinting of commercial Aroclor and Halowax mixtures in complex matrices has been shown. The complementary nature of these detection modes yield valuable information in addition to UV detection. a signal inverter is proposed for linearization of the quenched RTPL signals. In this way linear calibration plots over more than two orders can be obtained. Detection limits are generally in the low nanogram or subnanogram concentration region. The application of RTPL detection techniques to the analysis of commercial PCN and PCB mixtures in surface water and urine is demonstrated. Pre-columns can be used to advantage for pre-concentration and clean-up of this type of samples.     

Detection of analyte binding to microarrays using gold nanoparticle labels and a desktop scanner

Microarray hybridization or antibody binding can be detected by many techniques, however, only a few are suitable for widespread use since many of these detection techniques rely on bulky and expensive instruments. Here, we describe the usefulness of a simple and inexpensive detection method based on gold nanoparticle labeled antibodies visualized by a commercial, office desktop flatbed scanner. Scanning electron microscopy studies showed that the signal from the flatbed scanner was proportional to the surface density of the bound antibody-gold conjugates, and that the flatbed scanner could detect six attomoles of antibody-gold conjugates. This detection system was used in a competitive immunoassay to measure the concentration of the pesticide metabolite 2,6-dichlorobenzamide (BAM) in water samples. The results showed that the gold labeled antibodies functioned comparably with a fluorescent based immunoassay for detecting BAM in water. A qualitative immunoassay based on gold-labeled antibodies could determine if a water sample contained BAM above and below 60-70 ng L(-1), which is below the maximum allowed BAM concentration for drinking water (100 ng L(-1)) according to European Union legislation.     

Application of Capillary Electrophoresis for Determination of Inorganic Analytes in Waters

Aside from HPLC and GC, capillary electrophoresis (CE) is one of the most important techniques for high-performance separations in modern analytical chemistry. Its main advantages are the possibility of using different detection techniques, the possibility of in-capillary sample processing for preconcentration or derivatization, and ease of instrumental miniaturization down to the microfluidic scale. Those features are utilized in the separation of macromolecules in biochemistry and in genetic investigations, but they can be also used in determinations of inorganic ions in water analysis. This review, based on about 100 original research works, presents applications of CE methods in water analysis reported in recent decade, mostly regarding conductivity detection or indirect UV detection. The developed applications include analysis of high salinity sea waters, as well as analysis of other surface waters and drinking waters.     

饮用水中有机污染物检测方法研究进展

介绍水中有机污染物的富集方法如顶空法、萃取法、固相微萃取法、液相微萃取法、棒吸附萃取等,对饮用水中有机污染物的检测技术如气相色谱法、气相色谱–质谱联用法、液相色谱法、液相色谱–质联用法等进行了综述并对检测技术的发展趋势进行了展望。     

Comparaison de Differentes Methodes Analytiques Appliquees au Dosage des Hydrocarbures Dissousdans L'Eaua L'etatde Traces

Abstract

Many physical-chemical methods are employed for the evaluation of trace hydrocarbons dissolved, in underground or surface waters.

Comparison is done of three techniques chosen amongst the most commonly used in the studies conducted on water pollution caused by oil products:

infrared spectroscopy;

ultraviolet spectrofluorimetry;

gas chromatography.

To enable the application of these techniques to very low concentrations of hydrocarbon all these techniques require a concentration step.

This can be carried out, either by the liquid-liquid extraction of the hydrocarbons with the assistance of an organic solvent and in this case, the concentration ratios are poor, or by the trapping technique, where the hydrocarbon concentration is effected by adsorption on a resin, followed by desorption by a relatively small amount of an appropriate organic solvent. The water amounts so treated can be 10 to 100 larger than those treated by a liquid-liquid extraction.

A trapping system is described which has been used in an initial phase for the detection and quantitation of aromatic hydrocarbons up to C₉. The operational conditions are described for the measurement of heavier hydrocarbons (sampled water quantity and flow, desorption solvent, amount of resin).

The importance of the concentration method and of the sensitivity of the analytical techniques chosen for the definition of the detection threshold of the dissolved hydrocarbons is pointed out.

In addition to the detection level problems for certain types of hydrocarbons, the selectivity of these techniques is considered.

In conclusion, the various methods are compared amongst themselves from the point of view of their application, of the quality of the results which are obtained and of their applicability to the different real water samples polluted by hydrocarbons.     

Analysis of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) in water, particularly waste water

Summary Two chromatographic techniques can be considered for the detection of the complexing agents NTA, EDTA and DTPA in water: gas chromatography (GC) and liquid chromatography (HPLC). GC is capable of detecting all three compounds in concentrations of as little as 0.001 mg/l. However, this requires a complex and time-consuming sample preparation (enrichment, derivatization). HPLC represents a possible alternative for detecting EDTA and DTPA. Without enrichment it is possible to reach a detection limit of 0.1 mg/l, i.e., while this method is rather less sensitive, it provides results in a much shorter time. If the sample concentrations are high enough, this method is more suitable for conducting routine monitoring of emissions of EDTA and DTPA in waste water. Simple matrices such as surface water or drinking water can be enriched on a pre-column to reduce the detection limit.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Isotachophoretic focusing and mass spectrometry detection as tools for improving the determination of aromatic sulfonates in capillary electrophoresis

We explored isotachophoresis-capillary zone electrophoresis (ITP-CZE) with diode array detection on a single capillary to find out how to increase the injection volume and decrease the detection limits of aromatic sulfonates in CZE. The ITP was performed by applying a negative voltage in conjunction with hydrodynamic backpressure programming, and the terminating buffer was removed before the CZE separation, which resulted in highly sensitive determinations. The ITP increased the signal response of conventional hydrodynamic injection by a factor of 100, whereas the separation efficiency was unaffected. The limits of detection of the method were between 3 and 5 nugL(-1). The method was successfully used to determine these compounds in water samples. Experimental conditions for capillary electrophoresis-mass spectrometry were optimized and applied to determine aromatic sulfonates in water samples. These techniques enables the 2-naphthalenesulfonate to be determined in water samples.     

水体中硝基芳烃类有机污染物分析方法研究进展

硝基芳烃类有机物是一类重要的化工原料,也是性质相对稳定、难以降解的高毒污染物。其检测技术主要有分光光度法、电化学法、液相色谱法、气相色谱-电子捕获检测器法(GC/ECD)、气相色谱-质谱法(GC-MS)等。其中GC/ECD法和GC-MS法因测定准确、灵敏、适用范围广而得到广泛应用。该文从不同类型水体中硝基芳烃类有机物样品的采集、前处理以及检测分析技术的选择角度,对硝基芳烃类有机物检测技术的发展进行了简要评述,同时对其分析方法进行了展望。