活性炭固相微萃取-气质联用对海水中痕量-丁基三氯锡的测定

利用自制的活性炭纤维结合固相微萃取-气质联用技术（ACF—SPME／GC～MS）分析了水相中的一丁基三氯锡（MBT,monobutyltin trichloride）。对实验影响因素如萃取温度、离子强度、萃取时间进行了研究。结果表明,该方法的线性范围为0．1～100μg/L,检出限为4．5ng/L,相对标准偏差为8．6％。将ACF—SPME／GC—MS技术用于实际海水样品的分析,取得了理想的效果。     

固相微萃取(SPME)/GC/MS测定灌溉水中的残留甲胺磷

农药残留是当前农产品出口及内销中的最大卫生质量问题，由水携带是农药残留的来源之一。本文利用SPME／GC／MS技术对灌溉用水农药残留进行了分析研究，对固相微萃取条件进行了选择，并作了加入回收实验，测定了水中的甲胺磷含量。     

固相微萃取-气相色谱/质谱法建立烟用香精指纹图谱

采用固相微萃取法(SPME)对6批次的烟用HMT-4香精成分进行提取,GC/MS对其进行分析,建立了该香精的GC/MS指纹图谱的研究方法。通过参兑实验考察了色谱指纹图谱用于香精质量控制的可行性。结果表明:SPME法具有操作简便、快速、节能、萃取效率高等特点,适合于烟用香精成分的提取。6批次的HMT-4香精的指纹图谱稳定性好,相似度高,具有很强的特征性和唯一性。通过参兑实验发现色谱指纹图谱能全面、综合、准确地反映烟用香精的质量情况,可以成为烟用香精质量控制的有效手段。     

固相微萃取-气/质联用法测定尿中的海洛因代谢物

Shima dzu QP5050AGC／MS仪,EI源(70eV),GC-17A AFC流量控制,分流／不分流进样口,GC Solution软件工作站。固相微萃取(SPME)手柄,7μm和100μm PDMS纤维头与85μm PA纤维头(Supelco公司)。吗啡、6-单乙酰吗啡、可待因、乙酰可待因及海洛因标准品均购自公安部物证鉴定中心,用甲醇配成lg／L标准储备液,冷藏备用。     

大兴安岭地区细叶杜香挥发性成分的研究

1　实验部分1.1　仪器与样品　　固相微萃取(SPME)手柄及100μm聚二甲基硅氧烷(PDMS)萃取头(美国Supelco),恒温磁力搅拌装置,GC 17A QP5050GC/MS仪(日本Shimadzu)。　　细叶杜香2002年8月采于内蒙古大兴安岭,在避光处将其自然晾干后,将其嫩枝和叶剪成细末,待用。1.2　杜香挥发性成分的提取　　水蒸气蒸馏:取细叶杜香样品100g,按常规方法进行水蒸气蒸馏,提取6h,水层用氯化钠饱和后,用乙醚萃取,回收乙醚,得棕黄色透明油状物0 6g,将其用乙醚稀释后用于气相色谱 质谱(GC/MS)分析。　　SPME:将SPME纤维在GC/MS仪进样口250℃下老化2…     

调味品中氯丙醇的GC/ECD和GC/MS/MS衍生化检测方法研究及应用

报道了调味品中氯丙醇的衍生化气相色谱(GC／ECD)和衍生化气相色谱双串联质谱法(GC／MS／MS)测定。GC／ECD测定酱油中3—氯—1，2—丙二醇(3—MCPD)的检出限达到0．01mg／kg，回收率为91％～104％，变异系数为2．27％～7．96％；GC／MS／MS同时测定酱油中1，3—二氯—2—丙醇、2，3—二氯—1—丙醇和3—氯—1，2—丙二醇，1，3—二氯—2—丙醇、2，3—二氯—1—丙醇的检出限为0．02mg／kg，3—氯—1，2—丙二醇的检出限为0．01mg／kg，回收率在92％～106％，变异系数为3．51％～13．33％。     

聚丙烯酸树脂涂层HS-SPME-GC-MS监测城市污水中的芳香烃化合物

采用聚丙烯酸树脂涂层-固相微萃取-气相色谱-质谱(PA—SPME—GC—MS)联用技术,在优化的萃取条件下检测了城市污水中的苯系物和多环芳烃等芳香烃化合物．该方法的最低检出限达12ng／L水平,相对标准偏差为1．7％～9．8％．     

GC/MS/MS分析物体表面上粘附的痕量呋喃丹

呋喃丹是一种广谱内吸性杀虫剂,具有胃毒、触杀等作用~([1]).呋喃丹的检验方法主要有TLC、GC、GC/MS、HPLC、HPLC/MS/MS~([2～4])等,而采用GC/MS/MS方法定性分析复杂基体上痕量呋喃丹及其水解产物呋喃酚未见报道,本研究采用GC/MS/MS方法检测物体表面粘附的呋喃丹及其水解产物呋喃酚.     

气相色谱/质谱与气相色谱/原子发射光谱联用分析多氯邻羟基二苯醚类化合物

利用气相色谱／质谱(GC／MS)确定三氯新经多相催化加氢后所得的氯代邻羟基二苯醚类化合物的分子组成和结构;以正二十烷为内标物利用气相色谱／原子发射光谱(GC／AED)碳元素(496nm)检测通道,直接得到氯代邻羟基二苯醚类化合物中碳元素的质量,再根据分子式对组分定量。同时选择氯(479nm)和氧(171nm)通道,以三氯新为内标物定量组分中的氯和氧元素的质量。不同检测通道和不同内标物对同一组分所得定量结果基本一致。因而,对难以全部获得标准样品的复杂体系(如含有多种杂原子、同分异构体以及化学反应过程产物),GC／MS和GC／AED联用能够得到准确、可靠的定性和定量结果。     

自制的SPME装置与GC-MS联用测定室内空气中的挥发性有机化合物

用直接进样、固相萃取进样和自制的固相微萃取（SPME）装置进样与气相色谱（GC）及GC—MS联用检测了室内空气中的挥发性有机污染物，对影响SPME操作条件进行了优化。使用的方法在所测范围内具有良好的线性（相关系数为0．968～0．991），检出限达0．3—2、3μg/L，相对标准偏差均小于7％，回收牢为95％～111％。结果表明：自制的SPME装置操作简单、快速、安全，准确度、灵敏度优于其它两种方法。     

Selected ion storage versus tandem MS/MS for organochlorine pesticides determination in drinking waters with SPME and GC-MS

The use of two modes for mass spectrometry (MS) detection with an ion trap instrument, selected ion storage (SIS) and tandem mass spectrometry (MS/MS), are compared for the solid-phase microextraction (SPME)–gas chromatography (GC) coupled to mass spectrometry (GC-MS) determination of 16 priority organochlorine pesticides (OCPs) in drinking water samples at the ultratrace levels (ng?L^?1) required by official guidelines in the European legislation. Experimental parameters investigated for the SPME sample preparation were: the type of coating (100?µm polydimethylsiloxane, PDMS, and 65?µm poly(dimethylsiloxane)–divinylbenzene, PDMS/DVB), SPME modality, extraction and desorption times and desorption temperature and the methanol percentage in the SPME working solution. Under the calculated optimal conditions two methodologies were developed, one for SIS and the other for MS/MS modes. The detection limits, precision and accuracy were evaluated for both alternatives and were appropriate to the official guidelines requirements. The SPME–GC-MS(SIS) methodology offered LODs from 0.2–6.6?ng?L^?1, precision below 13% and recoveries between 83 and 110%. The SPME–GC–MS/MS methodology provided limits of detection (LODs) ranging from 0.3 to 7.6 ng?L^?1, % RSD were ≤14% and recoveries of 79–108% were achieved. After the results observed within an Interlaboratory Exercise, the latest MS methodology was selected for the pursued analysis in real drinking water samples. Also, the good results in this round-robin exercise validate the proposed SPME–GC–MS/MS methodology.     

Analysis of odorous trichlorobromophenols in water by in-sample derivatization/solid-phase microextraction GC/MS

The simultaneous determination of several odorous trichlorobromophenols in water has been carried out by an in-sample derivatization headspace solid-phase microextraction method (HS-SPME).The analytical procedure involved their derivatization to methyl ethers with dimethyl sulfate/NaOH and further HS-SPME and gas chromatography-mass spectrometry (GC/MS) determination. Parameters affecting both the derivatization efficiency and headspace SPME procedures, such as the selection of the SPME fiber coating, derivatization–extraction time and temperature, were studied. The commercially available polydimethylsiloxane (PDMS) 100 μm and Carboxen-polydimethylsiloxane-divinylbenzene (CAR-PDMS-DVB) fibers appeared to be the most suitable for the simultaneous determination of these compounds. The precision of the HS-SPME/GC/MS method gave good relative standard deviations (RSDs) run-to-run between 9% and 19% for most of them, except for 2,5-diCl-6-Br-phenol, 2,6-diCl-3-Br-phenol and-2,3,6-triBr-phenol (22%, 25% and 23%, respectively). The method was linear over two orders of magnitude, and detection limits were compound dependent but ranged from 0.22 ng/l to 0.95 ng/l. The results obtained for water samples using the proposed SPME procedure were compared with those found with the EPA 625 method, and good agreement was achieved. Therefore, the in-sample derivatization HS-SPME/GC/MS procedure here proposed is a suitable method for the simultaneous determination of odorous trichlorobromophenols in water.     

Solid phase microextraction/gas chromatography/mass spectrometry integrated with chemometrics for detection of Salmonella typhimurium contamination in a packaged fresh vegetable

A rapid method for detection of Salmonella typhimurium contamination in packaged alfalfa sprouts using solid phase microextraction/gas chromatography/mass spectrometry (SPME/GC/MS) integrated with chemometrics was investigated. Alfalfa sprouts were inoculated with S. typhimurium, packed into commercial LDPE bags and stored at 10 + 2 °C for 0, 1, 2 and 3 days. Uninoculated sprouts were used as control samples. A SPME device was used to collect the volatiles from the headspace above the samples and the volatiles were identified using GC/MS. Chemometric techniques including linear discriminant analysis (LDA) and artificial neural network (ANN) were used as data processing tools. Numbers of Salmonella were followed using a colony counting method. From LDA, it was able to differentiate control samples from sprouts contaminated with S. typhimurium. The potential to predict the number of contaminated S. typhimurium from the SPME/GC/MS data was investigated using multilayer perceptron (MLP) neural network with back propagation training. The MLP comprised an input layer, one hidden layer, and an output layer, with a hyperbolic tangent sigmoidal transfer function in the hidden layer and a linear transfer function in the output layer. The MLP neural network with a back propagation algorithm could predict number of S. typhimurium in unknown samples using the volatile fingerprints. Good prediction was found as measured by a regression coefficient (R² = 0.99) between actual and predicted data.     

Determination of Se4+ in drinkable water by solid-phase microextraction and gas chromatography/mass spectrometry

A method was developed for the selective determination of Se4+ in drinkable water by solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS). Se4+ was selectively derivatized to ethane, 1,1'-selenobis by reaction with sodium tetraethylborate, extracted by the SPME fiber, and determined by GC/MS. Both headspace (HS)-SPME and direct SPME were studied. The method requires only a few milliliters of sample and 20 min for completion. At 2.0 microg/L concentration, the relative standard deviation was 10.1% for HS-SPME and 9.1% for direct SPME. For HS-SPME, the theoretical detection limit was 81 ng/L and 166 ng/L for direct SPME. The recovery rate was 95%. The method was used to determine Se4+ in 10 tap water samples.     

A simple, rapid and sensitive method for determination of aldehydes in human blood by gas chromatography/mass spectrometry and solid-phase microextraction with on-fiber derivatization

Aldehydes are considered potential markers for enhanced oxidative stress and have been proposed as a diagnostic measure of cancer status. Do to their volatility and activity, it is very difficult to accurately measure aldehydes in human blood. In the present work, gas chromatography/mass spectrometry (GC/MS) and solid-phase microextraction (SPME) with on-fiber derivatization was developed for determination of aldehydes in human blood. O-(2,3,4,5,6-Pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) in aqueous solution was first adsorbed by a SPME fiber, and then the aldehydes in blood samples were headspace extracted by the SPME fiber and rapidly derivatized with PFBHA on the SPME fiber. Finally, the oximes formed were desorbed and detected by GC/MS in electron ionization (EI) mode. Validation of the present method was carried out, and the method was applied to quantitative analysis of the aldehydes in lung cancer blood. The results demonstrated that GC/MS and SPME with on-fiber derivatization is a simple, rapid, sensitive and solvent-free method for the determination of aldehydes in human blood.     

Selective Determination of Se4+ and Se6+ Using SPME and GC/MS

A method for the selective determination of Se⁴⁺ and Se⁶⁺ using solid phase microextraction (SPME) and GC/MS analysis is presented. Se⁴⁺ is selectively derivatized by reaction with 4,5-dichloro-1,2-phenylenediamine to form the corresponding piazselenolo complex, extracted by the SPME fiber, and determined by GC/MS. The RSD at a 5 μg/L concentration was 9.88% and the theoretical detection limit 6 ng/L. The method was employed to test real matrices; tap and river water were analyzed before and after spiking giving a recovery rate of 102% in river water and 97% in tap water.     

固相微萃取-气相色谱/质谱分析栀子花的头香成分

 分别用固相微萃取和动态顶空法分离栀子鲜花的头香成分,用GC/MS技术分析鉴定,并用GC/MS总离子流色谱峰的峰面积进行归一化定量。在固相微萃取方法中,共鉴定了54种化学成分,占总峰面积的99.98%。主要成分(质量分数)依次为金合欢烯（64.86%）、罗勒烯（29.33%）、芳樟醇（2.74%）、惕各酸顺式叶醇酯（1.34%）和苯甲酸甲酯（0.25%）等。经与动态顶空法的分析结果比较发现,固相微萃取法不仅操作简便,而且具有较高的采样灵敏度,获得的化学成分的信息量多于动态顶空法。     

固相微萃取/气相色谱/质谱联用测定水中的2,4-二硝基苯酚

研究了水中痕量2,4-二硝基苯酚的固相微萃取（SPME）方法,得到了2,4-二硝基苯酚的SPME最佳萃取条件：水溶液调pH2,并用NaCl他和,在室温下直接萃取30min,气相色谱／质谱分析时,纤维探针在270℃下脱附3min。所建立的方法适于快速、方便地测定水中2,4-二硝基苯酚,不需浓缩和预处理。     

气相色谱-质谱指纹图谱在甄别真假卷烟上的应用

运用固相微萃取／气相色谱-质谱法建立卷烟挥发性和半挥发性物质的指纹图谱。通过指纹图谱相似度评价软件,对12批正品卷烟和1个假冒品卷烟的指纹图谱进行了相似度计算,结果表明：12批样品间相似度很好,而假冒品卷烟与正品卷烟的相似度很低,该方法为探讨卷烟质量稳定和甄别真假卷烟提供了一种简便易行的方法模式。