二恶英类分析研究进展及展望

通过综合介绍国内外二恶英类物质分析研究的最新动态,包括二恶英类的前处理和气相色谱法（GC）、液相色谱法（LC）、胶束电动色谱法（MEKC）、质谱法（MS）、气相色谱/质谱（GC/MS）联用和生物分析法等多种分析技术及其改进方法,指出了二恶英类分析研究工作中现存的问题,对今后的发展动向提出了一些建议。     

全二维气相色谱/飞行时间质谱法快速定性分析飞灰样品中的二噁英

建立了全二维气相色谱/飞行时间质谱法 (GC×GC-TOFMS) 快速定性分析飞灰样品中17种二(噁)英的方法.实验证明,采用GC×GC二维特征谱图、TOFMS谱图库检索(自建谱库和NIST库)以及丰度比的定性手段,能在42.5 min内快速分离和定性17种二(噁)英的同分异构体.本方法对大于 0.5 pg/μL (TCDD) 的样品有较好的灵敏度.因此,在二(噁)英分析领域,GC×GC/TOFMS技术可以作为高分辨气相色谱/质谱(HRGC/HRMS)技术的补充和替代.     

盐酸二甲双胍药物中杂质测定方法研究进展

对近年来盐酸二甲双胍类药物中杂质的测定方法进行综述.盐酸二甲双胍类药物中的杂质主要有双氰胺、二甲胺以及由二甲胺形成的亚硝胺类基因毒性杂质等.测定方法主要有高效液相色谱(HPLC)法、离子色谱(IC)法、高效液相色谱–串联质谱(HPLC–MS/MS)法和气相色谱–串联质谱(GC–MS/MS)法,其中高效液相色谱法主要用于...     

同时裂解甲基化气相色谱法鉴别合成胶粘剂

 应用同时裂解甲基化气相色谱法 (Py Me GC)对合成胶粘剂进行了鉴别。采用热丝型裂解器、氢火焰离子化气相色谱仪、FFAP毛细管柱、程序升温方式及季铵盐甲基化试剂 ,对刑事案件中常见的丙烯酸酯类及其改性体、醋酸乙烯酯、聚乙烯醇等合成胶粘剂进行了测定 ,并对样品裂解各主要组分峰进行了GC/MS定性分析 ,同时比较了相同样本用常规裂解气相色谱法 (Py GC)测定的结果。结果表明 :Py Me GC法比Py GC法可获得更多的物质组分信息 ,是一种适用于法庭科学鉴定的方法。     

薄层色谱法分析环十五内酯

环十五内酯是一种珍贵的大环麝香类香料,对其定性和定量分析通常使用气相色谱法(GC)和气相色谱一质谱联用法(GC—MS)。但对于以15—羟基十五烷酸为底物经脂肪酶催化合成的环十五内酯,由于产物中残留长链的脂肪酸和脂肪酶。采用溶剂萃取分离有一定难度,尤其是对反应的跟踪测定,GC和GC—MS难以应用。薄层色谱法(TLC)能定性分析环十五内酯。但展开剂、显色剂等的影响没有得到关注。限制了TLC的应用范围。本文建立了一种为酶催化合成环十五内酯提供快速、简便的TLC分析方法。     

2,4,6-三氯酚纯品原料纯度定值方法研究

对用于溶液标准物质制备的纯品原料2,4,6-三氯酚纯度定值方法进行了探讨。采用气相色谱质谱法(GC–MS)对主成分和杂质进行定性鉴定。用高效液相色谱法(HPLC–DAD)、气相色谱法(GC–FID)和差示扫描量热法(DSC)3种不同原理的方法对主成分定值。卡尔费休法测量水分,电感耦合等离子体质谱(ICP–MS)测量无机杂质。2,4,6-三氯酚纯度定值结果为99.3%,扩展不确定度为0.6%(k=2)。     

DEIP中微量杂质的GC/MS分析

研究了间苯二甲酸二乙酯(DEIP)中微量杂质的化学成分,用减压精馏的方法对样品进行分离浓缩,用气相色谱-质谱法(GC/MS)进行分析,结合生产工艺,谱库检索及人工解谱进行鉴定,鉴定出DEIP中主要11种杂质,用归一化法进行定量,建立了用GC/MS方法检测DEIP中微量杂质的方法。     

体液中-叶萩碱检测方法的研究

本文报道了用气相色谱(GC)及气相色谱-质谱联用(GC/MS)检出人体液中一叶萩碱的方法.尿样经碱化后用乙醚直接萃取,回收率为72.1％;血浆样品用Sep-pak小柱提取,回收率为 43.9％,GC/MS的检测限为 20ng.方法快速、简便、准确.     

气相色谱-质谱联用在农药残留检测方面的应用进展

气相色谱-质谱联用(GC-MS)既具有气相色谱高分离效能,又具有质谱准确鉴定化合物结构的特点,可达到同时准确快速测定食品中微量的多种农药残留及衍生物,因此已被很多国家研究者开发和应用.GC/MS/MS,二维气相色谱、惰性离子源等是气相色谱-质谱联用新的进展.     

快速气相色谱法分析石油饱和烃

提出了一种快速分析原油和岩石抽提物中饱和烃组分的毛细管气相色谱(GC)方法。由于在该方法中采用了细内径毛细管柱,故饱和烃的GC分析周期由原来的80~90 min缩短至15 min,分析速度加快约5倍,大大提高了工作效率和仪器通量,使石油饱和烃得到了很好的分离分析。该方法符合中华人民共和国石油天然气行业标准SY/T5120-1997的要求。20万理论塔板数的细径柱的应用,可供石油中异构烷烃,尤其是甾烷、萜烷类的气相色谱/质谱(GC/MS)快速分析方法及芳烃的GC快速分析方法借鉴。     

Recent applications of gas chromatography with high‐resolution mass spectrometry

Gas chromatography coupled to high‐resolution mass spectrometry is a powerful analytical method that combines excellent separation power of gas chromatography with improved identification based on an accurate mass measurement. These features designate gas chromatography with high‐resolution mass spectrometry as the first choice for identification and structure elucidation of unknown volatile and semi‐volatile organic compounds. Gas chromatography with high‐resolution mass spectrometry quantitative analyses was previously focused on the determination of dioxins and related compounds using magnetic sector type analyzers, a standing requirement of many international standards. The introduction of a quadrupole high‐resolution time‐of‐flight mass analyzer broadened interest in this method and novel applications were developed, especially for multi‐target screening purposes. This review is focused on the development and the most interesting applications of gas chromatography coupled to high‐resolution mass spectrometry towards analysis of environmental matrices, biological fluids, and food safety since 2010. The main attention is paid to various approaches and applications of gas chromatography coupled to high‐resolution mass spectrometry for non‐target screening to identify contaminants and to characterize the chemical composition of environmental, food, and biological samples. The most interesting quantitative applications, where a significant contribution of gas chromatography with high‐resolution mass spectrometry over the currently used methods is expected, will be discussed as well.     

Recent advances in mass spectrometric measurement of dioxins

Past years, many efforts have been dedicated to the development of alternative analytical methods for the measurement of dioxins in various types of matrices. Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) are compounds that are present in samples at part-per-billion (ppb) or part-per-trillion (ppt) level. Their measurement requires the use of very sensitive analytical methods. Gas chromatography (GC) coupled to quadrupole ion storage mass spectrometry (QISTMS), fast GC (FGC) coupled to time-of-flight mass spectrometry (TOFMS) and comprehensive two-dimensional gas chromatography (GC x GC) coupled to TOFMS are the more promising tools challenging the reference GC high resolution mass spectrometry (HRMS) based on sector instruments. We report herein some of the advances we achieved in the past years in our laboratory on the development of alternative measurement methods for those compounds.     

Approaches to dioxin analysis by HRGC-HRMS and hybrid HRGC-MS-MS

A hybrid mass spectrometer with an EBQQ configuration was used to investigate two approaches to trace dioxin analysis: high resolution gas chromatography – high resolution mass spectrometry (HRGC-HRMS) and high resolution gas chromatography – mass spectrometry – mass spectrometry (HRGC-MS-MS). It is shown that selected ion monitoring (SIM) HRGC-HRMS exhibits better selectivity for dioxins separated on a cyanopropyl column than is otherwise obtained under medium resolution mass spectrometry (3,000 resolution), while optimization of conditions for HRGC-MS-MS allowed the observation of 350 femtograms of the highly toxic 2,3,7,8-TCDF at a S/N ratio of 5:1. Both methods were applied to environmental samples with good results.     

Application of a novel large-volume injection method using a stomach-shaped inlet liner in capillary gas chromatographic trace analysis of dioxins in human milk and plasma.

A newly developed large-volume injection (LVI) technique that employs a unique stomach-shaped inlet liner (SSIL) inside of a programmable temperature vaporizer was used for the determination of trace amounts of dioxins in human milk and plasma. The initial temperature and the initial dwelling time of the inlet and the kind of solvent used were found to be critical in determining the analytical sensitivity of dioxins due to the loss of these relatively volatile compounds during solvent vaporization. Human milk and plasma were purified and fractionated by pre-packed multi-layered silica-gel chromatography and activated carbon silica-gel column chromatography. A 20-microL aliquot of the fraction collected from the chromatography with toluene was directly applied to the LVI system in high-resolution gas chromatography/high-resolution mass spectrometry. Excellent correlation (r > 0.97) between the values obtained by the LVI method using the SSIL device and those by the conventional regular-volume splitless injection method was obtained for PCDDs, PCDFs and non-ortho PCBs in human milk and plasma samples.     

Simultaneous determination of planar chlorobiphenyls and polychlorinated dibenzo-p-dioxins and -furans in Dutch milk using isotope dilution and gas chromatography—high-resolution mass spectrometry

A method is described for the simultaneous determination of planar chlorobiphenyls and dioxins in milk using isotope dilution and gas chromatography—high-resolution mass spectrometry (GC-MS). The method is based on gel permeation chromatography, alumina clean-up and carbon chromatography and is highly automated, making a high sample throughput possible. Data on recovery, accuracy and reproducibility of results obtained with quality control samples are presented. Data for both dioxins and planar chlorbiphenyls from the analysis of samples of Dutch milk from several areas in the Netherlands are also presented. Possible interference of the chlorobiphenyls in the determination of the dioxins in the GC-MS method is discussed.     

Mass spectrometry applied to the analysis of estrogens in the environment

Environmental analytical chemistry has recently changed focus from analysis of non-polar, persistent contaminants (e.g. polychlorinated biphenyls and dioxins) to more polar and labile compounds that interfere with biological processes. For example, natural and synthetic estrogens and their metabolites have been detected in sewage treatment plant effluents at nanogram/liter concentrations that are similar to those at which both total sex reversal and intersex (containing both testes and ova) is induced in fish exposed to these compounds in laboratory experiments. The development of techniques for the analysis of natural and synthetic estrogens in biological fluids (i.e. serum and urine) has been a priority in the biomedical field. However, the recent recognition that estrogen hormones are contaminants in the environment that may contribute to endocrine disruption has focused attention on the need for highly sensitive and specific techniques that are applicable for trace analysis in complex environmental matrices. Three optimized mass spectrometric protocols have been developed for the determination and quantitation of steroid hormones in environmental matrices using gas chromatography/tandem mass spectrometry (GC/MS/MS), liquid chromatography/mass spectrometry selected ion monitoring, (LC/MS - SIM) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). The advantages and disadvantages of each method are presented.     

Multiresidue procedures for the determination of chlorinated dibenzodioxins and dibenzofurans in a variety of foods using capillary gas chromatography-electron-capture detection

Multiresidue digestion-extraction procedures for the determination of chlorinated dioxins and furans in a wide variety of products are presented. Procedure selection is dependent upon the residue(s) of interest, and on the fat content of the product. Additional cleanup is accomplished using column chromatography and a Florisil trap. The separation of residues is achieved by fraction collection off of two high-performance liquid chromatographic systems. Capillary gas chromatography employing electron-capture detection is used for quantitation. The extracts are suitable for gas chromatography mass spectrometry or gas chromatography with Hall electrolytic conductivity detection. Results of analysis, recovery data, and interlaboratory comparisons are presented. Spike recoveries will typically average 90% +/- 10%.     

Overview of Analytical Methodologies for Dioxin Analysis

Abstract

Poly(chlorinated) dibenzo‐p‐dioxins and dibenzofurans (PCDDs/PCDFs) are persistent organic pollutants which are globally distributed in practically all environmental compartments and which exert a broad spectrum of toxic and biochemical effects. Humans are exposed to these compounds mainly through the diet with food of animal origin usually being the predominant source.

Multiple step isolation and clean up procedures are necessary to determine trace levels of these analytes in complex environmental and biological samples. This article reviews some of the recent developments in the extraction procedures, such as SFE, PLE, HS‐SPME, MAE, SCWE, ASE; clean‐up areas and instrumental analysis of dioxins in biological/environmental samples. Due to its specificity and sensitivity gas chromatography coupled with high resolution mass spectrometry (GC–HRMS), high‐resolution gas chromatography high‐resolution mass spectrometry (HRGC‐HRMS), or GC‐MS/GC techniques have been extensively applied to environmental, medicinal, and biological studies.     

Recently developed GC/MS and LC/MS methods for determining NSAIDs in water samples

Pharmaceuticals have become major targets in environmental chemistry due to their presence in aquatic environments (following incomplete removal in wastewater treatment or point-source contaminations), threat to drinking water sources and concern about their possible effects to wildlife and humans. Recently several methods have been developed for the determination of drugs and their metabolites in the lower nanogram per litre range, most of them using solid-phase extraction (SPE) or solid-phase microextraction (SPME), derivatisation and finally gas chromatography mass spectrometry (GC-MS), gas chromatography tandem mass spectrometry (GC-MS/MS) and liquid chromatography electrospray tandem mass spectrometry (LC-ES/MS/MS). Due to the elevated polarity of non-steroidal anti-inflamatory drugs (NSAIDs), analytical techniques based on either liquid chromatography coupled to mass spectrometry (LC-MS) and gas chromatography coupled to mass spectrometry (GC-MS) after a previous derivatisation step are essential. The most advanced aspects of current GC-MS, GC-MS/MS and LC-MS/MS methodologies for NSAID analysis are presented.     

GC-MS ultra trace analysis of dioxins produced through hydrothermal gasification of biowastes

Hydrogen gas and the valuable material hydroxylapatite have successfully been produced from biomass wastes by hydrothermal gasification. However, it was expected that toxic compounds might be produced through the reaction. It was therefore important to clarify whether toxic compounds were synthesized in hydrothermal gasification of biowastes since dioxins are categorized among the most toxic compounds for humans. This is particularly true of biomass wastes containing hetero-atoms in organic matrices. In this study, formation of the dioxins polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and certain dioxin-like polychlorinated biphenyls (PCBs) were examined. Chicken manure and cattle manure were tested as real biowastes for hydrothermal gasification and the produced compounds in the liquid and solid phases were analyzed for detection of dioxins by gas chromatography/mass spectrometry (GC/MS). The total toxic equivalent quantities (the total TEQ) of dioxins produced by the hydrothermal gasification were found to be much lower than regulation levels in Japan require and therefore the products require no additional post treatments.