顶空固相微萃取-气相色谱-质谱联用分析纺织品中挥发性有机物

建立了顶空固相微萃取（HSSPME）-气相色谱（GC）-质谱（MS）联用测定纺织品中甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯5种挥发性有机物（VOCs）的分析方法。选择聚二甲基硅氧烷（PDMS）作为萃取涂层,优化了SPME的萃取条件,包括平衡时间、萃取时间、萃取温度、顶空体积、离子强度、搅拌速度、解吸温度和时间以及GC—MS仪器条件。对于甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯方法线性范围分别为0．087～870、3．32～3320、2．28～2280、0．015～150和0．050～50．0ng／g;检出限分别为0．005、0．042、0．670、0．008和0．011ng／g。实际样品加标回收率在80．1％～122％之间,RSD在0．8％～8．6％之间。方法符合纺织品中痕量VOCs的快速分析要求。     

顶空气相色谱-质谱法测定玩具中的10种挥发性有机物

建立了检测玩具中10种挥发性有机物(VOC)残留量的顶空气相色谱-质谱(HS-GC-MS)方法。样品经140 ℃、45 min静态顶空后,通过DB-624色谱柱分离和质谱检测,外标法定量。该方法对于不同VOC的定量限(LOQ)均在0.66 mg/kg以下,线性范围为0.001～2.0 μg,平均回收率在79%～106%之间,相对标准偏差(RSD)在0.4%～5.6%之间。该方法具有准确灵敏、简单快速等特点,将其应用于实际玩具样品的检测取得了良好效果。     

气质联用法分析澳洲坚果壳的挥发性成分

分别建立了微波萃取和顶空直接进样GC/MS法对澳洲坚果壳的挥发性成分进行了分析。从澳洲坚果壳共分离鉴定了37个挥发性成分,包含烯烃、酸类、醛类、酮类、内酯类等,且澳洲坚果壳乙醇提取物具有令人愉悦的香味,其香气风格与原样迥异,具有成为香精香料来源的潜质。     

Determination of odour-causing volatile organic compounds in cork stoppers by multiple headspace solid-phase microextraction

Multiple headspace solid-phase microextraction (MHS-SPME) coupled with gas chromatography-mass spectrometry has been applied in order to determine 2,4,6-trichloroanisole (2,4,6-TCA), guaiacol, 1-octen-3-ol and 1-octen-3-one in three samples of cork stoppers. These compounds are responsible for cork taint in wine and can modify the organoleptic properties of bottled wine. Variables such as temperature, addition of water, extraction time, and amount of cork were studied. The extractions were performed with a 50/30 microm divinylbenzene-carboxen-polydimethylsiloxane (DVB-CAR-PDMS) fibre for 45 min at 100 degrees C using 20 mg of cork. For calibration, 50 microL of VOC aqueous solutions were used and the extraction were carried out for 45 min at 75 degrees C. The limits of detection of the method expressed as ng of VOC per g of cork were 0.3 for 2,4,6-TCA, 7.5 for guaiacol, 1.7 for 1-octen-3-one and 1.9 for 1-octen-3-ol. Relative standard deviation of replicate samples was less than 10%. Significant losses of analytes were observed when the samples were ground at room temperature. Finally, a recovery study was performed and the MHS-SPME results were validated using Soxhlet extraction results.     

新型水蒸气顶空富集装置在饮用水中痕量挥发性有机物非目标筛查中的应用

以饮用水中痕量挥发性有机物(VOCs)非目标筛查为目的,构建了一种新型的大体积水样高倍富集装置。对其精馏管长度、回收冷凝液体积、吸收介质等影响富集效果的关键因素进行了优化。该装置以水蒸气为吹扫气,同时以水作为吸收剂,将1 L水样富集浓缩至5 mL后,可使原有吹扫捕集-气相色谱-质谱法(P&;T-GC-MS)分析VOCs的灵敏度提高1～2个数量级。用该方法对某净水厂的源水与出厂水进行了痕量VOCs的定性分析与比较。与传统P&;T-GC-MS方法相比,本方法对两种水样的污染物检出数目由原来的无检出和5种分别提高至16种和35种。分析结果表明饮用水消毒前后污染物的种类及含量存在显著差异。     

顶空气相色谱法测定化妆品中15种挥发性有机溶剂残留

建立了化妆品中15种挥发性有机溶剂残留的顶空气相色谱测定方法。样品经60 ℃、30 min静态顶空后,采用气相色谱-氢火焰离子化检测器进行检测,外标法定量。加标回收试验结果表明: 15种挥发性有机溶剂残留平均回收率为62.8%～116%,相对标准偏差均小于5%。方法的检出限为0.09～0.68 mg/kg。该方法可有效克服基体干扰,一次进样可同时分离和测定化妆品中15种挥发性有机溶剂,准确灵敏,简单快速,适用于化妆品中挥发性有机溶剂残留的检测。     

Static headspace analysis of volatile organic compounds in soil and vegetation samples for site characterization

Traditional methodologies for the characterization of volatile organic compounds (VOCs) in subsurface soil are expensive, time-consuming processes that are often conducted on samples collected at random. The determination of VOCs in near-surface soils and vegetation is the foundation for a more efficient sampling strategy to characterize subsurface soil and improve understanding of environmental problems.In the absence of a standard methodology for the determination of VOCs in vegetation and in view of the high detection limits of the method for soils, we developed a methodology using headspace gas chromatography with an electron capture detector for the determination of low levels (parts-per-billion to parts-per-trillion) of VOCs in soils and vegetation. The technique demonstrates good sensitivity, good recoveries of internal standards and surrogate compounds, good performance, and minimal waste. A case study involving application of this technique as a first-step vadose-zone characterization methodology is presented.     

火棘叶挥发油化学成分的GC-MS分析

采用水蒸气蒸馏法从火棘叶中提取挥发油,利用气相色谱-质谱(GC-MS)联用方法分析火棘叶挥发油化学成分,并以面积归一法测定各成分的相对含量。从火棘叶挥发油中共鉴定出69种化合物,占挥发油总量的80.52%,主要成分为(-)-b-杜松烯(22.62%)、植物醇(19.90%)、二环倍半水芹烯(5.95%)、β-桉叶醇(5.78%)、1,2,3,4,4a,7-六氢-1,6-二甲基-4-(1-甲基乙基)-萘(2.78%)、表圆线藻烯(2.34%)等。     

饮用水中挥发性有机物(VOCs)的GC-MS分析

用顶空－毛细管气相色谱－质谱联用仪测定了北京主要区域的自来水,北京目前市场销售的瓶装饮用水（包括天然矿泉水,纯净水等）中２３种挥发性有机物（ＶＯＣｓ）（包括有机氯化物,有机溴代物及苯系物等）的浓度,并与其它城市（如天津,上海,兰州等地）的自来水中ＶＯＣｓ的浓度进行了比较,结果表明北京市区内自来水及大多数市售瓶瓶饮用水中ＶＯＣｓ含量很低。     

Urinary metabolic profiling of volatile organic compounds in acute exposed volunteers after an oil spill in Republic of Korea

The Herbei Spirit oil spill occurred in western Korea. A large number of people who participated in the cleanup tasks of the contaminated area were exposed to crude oil component. We developed a method to monitor volatile organic compound (VOC) metabolites in urine, and evaluate the acute exposure caused by the oil spill in exposed volunteer workers (n = 100, 20.7 ± 2.1 years, mean ± SD). Acidified urine samples were extracted by SPE, derivatized with trimethylsilyl, and analyzed using gas chromatography–mass spectrometry. Calibration curves were found to be linear from 3 to 1000 ng/mL (r² > 0.993). Accuracy was over 82.4%, and precision was less than 24.8%. Using this method, the VOC metabolites, except hippuric acid, were present at higher levels in the urine samples of volunteers after cleanup work. The levels of mandelic acid (MA) and trans,trans‐muconic acid (t,t‐MU) were increased significantly (p < 0.001). The exposure effect was greater in women than in men. The effect of smoking was analyzed in all exposed and non‐exposed groups, with non‐smokers showing increased MA and t,t‐MU levels related to exposure. The present method was reliable to determine VOC metabolites in urine and could be useful for biomonitoring of acute exposure effects of VOCs. Copyright © 2009 John Wiley & Sons, Ltd.     

顶空气相色谱-质谱法同时测定蜂蜜中57种挥发性有机溶剂残留

建立了顶空气相色谱-质谱(HS-GC/MS)同时测定蜂蜜中57种挥发性有机溶剂(包括烷烃类、芳香烃类、醇类、酮类、酯类、醚类)残留量的分析方法。蜂蜜样品在密封的顶空瓶中用水溶解后,在顶空仪中于80 ℃下平衡30 min,使气-液两相达到动态平衡。采用DB-624毛细管色谱柱(60 m×0.25 mm×1.40 μm)对57种有机溶剂进行分离,GC/MS测定,外标法定量。该方法对于烷烃类、芳香烃类和醚类挥发性有机溶剂在0.005～0.2 μg、酯类0.05～2.0 μg、酮类0.5～20 μg、醇类2.5～100 μg范围内线性关系良好,相关系数均大于0.996。对于烷烃类、芳香烃类和醚类挥发性有机溶剂在1.0～20 μg/kg、酯类10～200 μg/kg、酮类100～2000 μg/kg、醇类500～10000 μg/kg添加范围内的平均添加回收率为61.0%～113.1%,相对标准偏差为1.9%～9.8%。对于烷烃类、芳香烃类和醚类挥发性有机溶剂的检出限为1.0 μg/kg、酯类10 μg/kg、酮类100 μg/kg、醇类500 μg/kg。该方法操作简单、快速,灵敏度和准确度高,适用于蜂蜜样品中多种挥发性有机溶剂残留量的同时检测。     

Detection of volatile organic sulfur compounds in water by headspace gas chromatography and membrane inlet mass spectrometry

Two gas chromatographic methods, GC-FID (flame ionization detection) and GC-ELCD (electrolytic conductivity detector) are compared in tlie analysis of volatile organic sulfur compounds (VOSCs) in water samples with a membrane inlet mass spectrometry (MIMS) technique. Carbon disulfide, ethanethiol, dimethyl sulfide, ethyl-methyl sulfide, thiophene, and dimethyl disulfide were used as test compounds. Linear dynamic ranges were found to be two decades with the GC-ELCD method and four decades with the GC-FID and MIMS methods. Detection limits were at low (μg/1 levels with the two gas chromatographic methods and clearly below μg/1 level with the MIMS method. Analysis of one sample takes 40 min with the gas chromatographic methods and five minutes with the MIMS method. The selectivity was good, especially with the GC-ELCD and the MIMS method. In addition, quantitative results obtained with spiked water samples by the three methods are compared.     

便携式气相色谱-质谱仪测定空气中挥发性有机污染物的准确性

便携式气相色谱-质谱仪(便携式GC-MS)能同时对多组分复杂有机物进行定性定量分析,在环境监测尤其是事故现场应急监测中发挥越来越重要的作用。本文比较了便携式GC-MS与EPATO-14A方法分析测定环境空气中低浓度挥发性有机物(VOCs)的性能,并探讨了利用定量环(loop环)模式测定高浓度VOCs的准确度。结果表明,采用内标标准曲线定量,HAPSITE便携式GC-MS测定空气中VOCs的检出限与EPATO-14A方法相当,准确度和精密度略低,但均符合环境监测分析的要求。利用loop环可对大部分10-6级的高浓度VOCs样品进行较为准确的测定,在突发性环境污染事故中可以得到基本准确的结果。     

Analysis of volatile components from Melipona beecheii geopropolis from Southeast Mexico by headspace solid-phase microextraction

A head space solid-phase microextraction method combined with gas chromatography–mass spectrometry was developed and optimised to extract and analyse volatile compounds of Melipona beecheii geopropolis. Seventy-three constituents were identified using this technique in the sample of geopropolis collected. The main compounds detected include β-fenchene (14.53–15.45%), styrene (8.72–9.98%), benzaldehyde (7.44–7.82%) and the most relevant volatile components presents at high level in the geopropolis were terpenoids (58.17%).     

Determination of very volatile organic compounds in environmental water by injection of a large amount of headspace gas into a gas chromatograph

An injection method for a large amount of headspace gas which enables determination of trace amounts of very volatile organic compounds (VVOCs), dichlorodifluoromethane, chloromethane, vinyl chloride, bromomethane, chloroethane and trichlorofluoromethane in all kinds of environmental water was developed. A gas phase equilibrated with the water phase in a vial was purged with helium for a short time. The VVOCs were then introduced into a trapping tube packed with Tenax TA, which had been cooled using carbon dioxide. After trapping, the VVOCs were thermally desorbed and put into a GC–MS system for subsequent analysis. This method is applicable to various types of samples.     

Analysis of volatile organic compounds in polymers by dynamic headspace and gas chromatography/mass spectrometry

An experimental method for the analysis of volatile organic compounds in polymers is described. The technique involves dynamic headspace sampling, collection, and concentration of the volatiles in a cold trap, followed by capillary column gas chromatography/mass spectometry. Flow switching is carried out by the Deans switching technique. Four technical polymers used as pharmaceutical packaging materials have been analyzed in order to demonstrate the method.     

顶空气相色谱-质谱联用技术的应用进展

顶空分析作为一种无有机溶剂萃取的样品处理技术,通常与气相色谱-质谱（GC-MS）技术结合用来分析复杂基质中的挥发性有机物。顶空气相色谱-质谱（HS-GC-MS）技术具有快速、高效、环保、灵敏度高等特点,在常规分析中发挥着重要作用。该文简要概述了静态顶空、动态顶空、顶空固相微萃取分析以及GC-MS联用技术,并介绍了整个顶空分析系统的影响因素和优化过程。根据基质类型的分类,综述了HS-GC-MS在食品和饮料、环境、生物等样品中的应用实例。HS-GC-MS的研究非常活跃,不断出现新应用,在分析挥发性有机物方面具有广阔前景。     

热脱附-气相色谱-三重四极杆串联质谱法测定环境空气中的挥发性有机物

采用热脱附(TD)结合气相色谱-三重四极杆串联质谱(GC-MS/MS)建立了环境空气中23种挥发性有机物(VOCs)同时检测的分析方法。空气样品通过主动采样的方式富集到装有Tenax-TA填料的热脱附管中,热解吸后在选择反应监测(SRM)模式下用GC-MS/MS进行检测,内标法定量。结果表明,23种VOCs在0.01~1 ng和1~100 ng低、高两个范围内线性关系良好,相关系数(r²)均大于0.99,方法定量限为0.00008~1 μ g/m³。加标水平为2、10和50 ng时,23种VOCs的平均回收率为77%~124%。除了最低加标水平的氯苯,相对标准偏差(RSD, n=6)均小于20%。对市内3个采样点的环境空气进行测定,其中苯、甲苯、乙苯、二甲苯、苯乙烯、1,2,4-三甲基苯和六氯丁二烯均有检出。实验证明,该TD和GC-MS/MS相结合的检测方法具有准确、可靠、灵敏度高等优点,适用于环境空气中VOCs的同时测定。     

化妆品中挥发性有机溶剂的通用检测方法

以化妆品配方中常见及禁用的36种有机溶剂为研究模板,建立了化妆品中挥发性有机溶剂残留评价初筛知识库、确证知识库和定量方法。初筛知识库包括双柱保留指数知识库和NIST质谱库。双柱保留指数知识库以保留指数为定性指标,选择极性的VF-1301ms和非极性的DB-5ms两根色谱柱,用顶空气相色谱-质谱法考察了36种有机溶剂在两种色谱分离系统中的保留特性。利用NIST MS search 2.0作为检索工具,同时建立了36种挥发性有机溶剂的顶空气相色谱-质谱定量方法。样品经60 ℃、30 min静态顶空后以连接了VF-1301ms石英毛细管色谱柱的气相色谱-质谱仪检测,外标法定量。方法检出限为0.01~3.3 μg/g,加标回收率为60.77%~126.60%。该方法从通用性的角度,为化妆品中挥发性有机溶剂残留的筛查、鉴别和定量提供方法,部分解决了测定化妆品中挥发性有机溶剂时需要针对不同检测目标建立不同方法以及潜在溶剂存在备选筛查的问题。     

水性涂料中挥发性有机化合物的气相色谱-质谱法测定

建立了内墙涂料中24种挥发性有机化合物(VOCs)的GC-MS检测方法,重点研究了现有检测方法分离度差和回收率低的问题,采用无水硫酸钠净化、二氯甲烷超声和膜过滤提取体系,改善了各种化合物的回收率,特别是提高了二元醇类化合物的回收率,优化后的实验条件下,样品的加标回收率为70%~94%,相对标准偏差不大于6.8%,检出限为3.1~10.6 mg/L。在30~300 mg/L范围内,方法的线性关系良好,相关系数大于0.99。该方法简便、快速、灵敏、精密度好,完全满足进出口水性涂料中常见的24种挥发性有机化合物的检测要求。