固相微萃取-脉冲火焰光度法测定大气及水中的路易氏剂

建立了固相微萃取（SPME）与气相色谱/脉冲火焰光度检测器（GC／PFPD）联用测定大气和水中路易氏剂及其水解产物的方法。探讨了影响SPME萃取效率的萃取头类型、萃取时间、解吸时间等因素。优化了PFPD的条件参数、衍生化试剂及衍生条件。在优化的条件下，路易氏剂衍生产物的响应值与浓度有良好的线性关系。本方法对水中路易氏剂及其水解产物的检出限为0．1μg/L；气体中路易氏剂的检出限为10ng／m^3；水样的加标回收率为96．7％-102．1％；气体样品的加标回收率为94．9％-103．0％；RSD为2．06％。     

水中芥子气水解产物硫二甘醇的分析

建立了水中芥子气水解产物硫二甘醇HLB－H104固相萃取法,应用GC－GC－MS分析鉴定,该法操作简便,灵敏度高,方法回收率可达74％,检出限为0．002mg/L。     

衍生化气相色谱—质谱法测定水中的路易氏剂及砷酸

本文研究了用气相色谱－质谱法测定水中微量路易氏剂及砷。在酸性条件下，路易氏剂及水解产物２，３－二巯基丙醇迅速反应形成挥发性的衍生物，大大提高了测定灵敏度。用选择性离子检测定量，最小检测量为每升水中１μｇ，路易氏剂的加标回收率为９５．６２％～１０５．８８％之间，砷的加标回收率为９６．３５％～１０６．０３％之间。     

固相萃取-气相色谱法测定水中毒死蜱

水样中的毒死蜱经全自动固相萃取仪萃取、乙酸乙酯洗脱后,用气相色谱火焰光度检测法测定,以保留时间定性,外标法定量．结果表明：选用ENVI-18小柱萃取、乙酸乙酯洗脱,在2mL／min的过水速率下取得了良好的回收率．方法的线性范围为0．25～4．0mg／L．r为0．9998,回收率为88．6％～100．6％,相对标准偏差为2．58％～7．34％,最低定量浓度为2．5μg／L．本方法快速、灵敏、准确,并能够很好的排除干扰,可以满足水中痕量毒死蜱的测定．     

气相色谱—原子发射光谱法测定水中微量路易氏剂的水解产物

本文用气相色谱－微波诱导等离子体原子发射光谱检测器（ＧＣ－ＭＩＰ－ＡＥＤ）对水中微量路易氏剂的水解产物的测定方法进行了研究，在酸性条件下，路易氏剂的水解产物与２，３－二巯基丙醇（ＢＡＬ）迅速反应形成挥发性的衍生物，在４８０．１９２，１８１．３７９和１８９．０４２ｎｍ波长下分别检测了衍生物的氯，硫，砷元素的发射信号，最小检测量为０．１μｇ／Ｌ。回收率为８７．２％～９７．４％。     

气相色谱-原子发射光谱法测定水中微量路易氏剂的水解产物

本文用气相色谱-微波诱导等离子体原子发射光谱检测器（GC－MIP－AED）对水中微量路易氏剂的水解产物的测定方法进行了研究。在酸性条件下，路易氏剂的水解产物与2，3－二巯基丙醇（BAL）迅速反应形成挥发性的衍生物。在480．192、181．379和189．042nm波长下分别检测了衍生物的氯、硫、砷元素的发射信号。最小检测量为0．1μg／L。回收率为87．2％～97．4％。     

固相微萃取-气相色谱-质谱联用分析水中的痕量扑草净

研究了固相微萃取－气相色谱－质谱联用测定水中扑草净的方法，采用聚丙烯酸酯（PA）萃取头，对影响固相微萃取萃取效率的萃取时间、搅拌速度、pH值以及盐度等进行了优化。在优化实验条件下，方法线性范围在0．1mg/mL-1000ng/mL之间，检出限为1．5ng/L。用该法分析了合成井水、自来水和湖水样品，回收率在85．4％－89．1％之间，相对标准偏差在1．8％－5．2％之间。本方法适合于水中痕量扑草净的分析。     

固相萃取-气相色谱法测定地下水中痕量酞酸酯的研究

本文建立了固相萃取-气相色谱法定量分析地下水中酞酸酯类（PAEs）有机污染物的方法。利用正交试验和单因素实验对影响回收率的4个主要因素（洗脱溶剂种类、水样体积、洗脱溶剂体积、固相萃取小柱填料量）进行了萃取条件的优化。综合考虑各方面因素后确定的最佳萃取条件为：二氯甲烷和丙酮为洗脱剂,体积8mL、0．5L水样、柱填料500mg。方法线性范围0．05～10．00μg／L,检出限0．05～0．341ng／L,相对标准偏差0．038％～1．107％。该方法应用于江汉平原地下水中PAEs测定,取得满意结果。     

超分子溶剂萃取–气相色谱–质谱法测定水中神经性毒剂及其模拟剂

建立了水中神经性毒剂沙林、梭曼及其模拟剂甲基磷酸二甲酯的超分子溶剂萃取–气相色谱–质谱分析方法。以聚氧乙烯单叔辛苯基醚在水中自组装形成水相胶束的超分子溶剂为萃取剂,对水样中的沙林、梭曼及其模拟剂甲基磷酸二甲酯进行液液微萃取,再通过异辛烷进行微波萃取分析。采用单因素试验考察了超分子溶液组成、用量、涡旋时间、离子强度等参数对萃取率的影响。实验结果表明：沙林、梭曼、甲基磷酸二甲酯的质量浓度在0.040～50 μg/mL范围内与色谱峰面积线性关系良好,相关系数均大于0.999,检出限为0.2～0.8 ng/mL,定量限为0.4～2.0 ng/mL,样品加标回收率为80.7%～89.3%,测定结果的相对标准偏差为5.87%～9.26%(n=6)。该方法有机溶剂用量少、环境友好、准确可靠、快速稳定,可用于水中神经性毒剂的测定。     

衍生化气相色谱－质谱法测定水中的路易氏剂及砷酸

本文研究了用气相色谱－质谱法测定水中微量路易氏剂及砷。在酸性条件下，路易氏剂及水解产物２，３－二巯基丙醇迅速反应形成挥发性的衍生物，大大提高了测定灵敏度。用选择性离子检测定量，最小检测量为每升水中１μｇ。路易氏剂的加标回收率为９５．６２％～１０５．８８％之间，砷的加标回收率为９６．３５％～１０６．０３％之间。     

气相色谱近年的发展

简要阐述了近几年气相色谱(GC)的发展和特点。GC是一个成熟的技术,广泛地应用于各个领域,近几年GC的发展除了继续研究新的固定相和高性能的毛细管色谱柱之外,主要在全二维气相色谱(GC×GC)、快速GC、便携式GC仪和微型GC仪几个方面。近几年新研究的GC固定相主要集中在常温离子液体和各种环糊精的衍生物。现在GC研究者趋向于使用商品化的GC毛细管柱,而商品化的GC毛细管柱应用最多的是以含5%苯基的聚甲基硅氧烷为固定相的色谱柱。GC×GC发展迅猛,特别是关于调制器的研究,已开发出十多种调制模式,并广泛地应用于各个领域。为了适应大量样品的分析和现场分析,研究和开发了多种快速GC方法和仪器以及便携式GC仪。为了仪器的小型化和专属性检测,μGC仪的研究也稳步地发展起来。     

Radio gas chromatography on capillary columns using a multi-column system (column-switching)

Summary A gas chromatographic system with capillary columns (fused silica) for the analysis of radiolabelled compounds is described. The system presented is based on a dual column gas chromatograph equipped with column switching facllity and a variable splitter at the column outlet combined with a dead-volume free adapter for the radioactivity monitor for continous measurement of radioactivity in the column effluent. The first column works as a separation column and the second is roughly shortened and used as a feed to the mass detector. The adjustment of the split ratio is regulated by the inlet pressures for the carrier gas supplying both columns. For mass detection all conventional systems can be used. Detection of radioactivity by a gas proportional counter (system based on a combustion technique). Three flow modes can be adjusted: a) total column effluent to the mass detector or b) to the radioactivity monitor, and c) simultaneous flow (dependent on the chosen split ratio) to mass-and radioactivity detectors. The system was developed for use in clinical chemistry and tested with labelled and unlabelled steroids. The method for peak identification by means of relative retention times and methylene units was possible also for radioactive peaks when a heart cutting technique was used. The radio gas chromatographic system presented allows the development of radiochromatograms with the same peak characteristics as in conventional capillary gas chromatography.Presented at the 14th International Symposium on Chromatography London, September, 1982     

非晶硅太阳能电池生产工艺用氣分析方法研究

本文对非晶硅太阳能电池制造工艺过程所用的无机氢化物烷类气体硅烷、硼烷、磷烷、甲烷和氢及其混合气的配制与分析方法进行了研究,以微机控制配气、检测程序、气相色谱法分成分析杂质,电容法测水分,方法已应用于工艺过程分析。     

Reaction gas chromatography: Hydrogenation cracking of hydrocarbons

Summary Hydrogenation degradation of hexane, 2-methylpentane, 2,2-dimethylbutane, trans 2-hexene, cyclohexane and benzene on a nickel catalyst was studied. The degradation products were separated in a capillary column with squalane and identified using the appropriate retention indices. The results obtained (the degree of conversion and the relative content of the individual products) are discussed in connection with the thermal degradation of these substances in an inert atmosphere.     

快速气相色谱研究

近年来快速气相色谱(HSGC)技术备受关注。本文根据色谱理论和实际应用中的特点对其进行了系统的分类和评价,阐述了如何针对具体样品选择分析方法和通过调整仪器的配置、参数以及性能来实现特定的快速分析。最后提出了HSGC未来的发展趋势。     

用台式色谱-质谱仪同时进行原油芳烃色谱和色谱-质谱分析

用ＨＰ６８９０ＧＣ／５９７３ＭＳＤ仪器,一次进样同时测定原油、烃源岩抽提物中芳烃馏分的芳烃色谱和色谱－质谱信息,效果良好,在有机地球化学研究工作中很有实用价值,方法具有高效、经济等优点。     

气相色谱法测定榄香烯含量

以正己醇为内标,用气相色谱法测定榄香烯及其制剂,方法简便、快速,结果准确,可作为控制质量的方法。     

气相色谱法测定异氟烷含量

The isoflurane content was determined by using a 93mm × 2.1m glass GC column packed with 25%PEG-20M/Chromosorb P AW-DMCS(80～100 mesh)and flame ionization detector,and the column temperature was 70℃.The quantitative determination was performed with trichloromethane as internal standard.     

Flow of the carrier gas in open-tubular capillary columns in temperature-programmed gas chromatography

A second-order non-linear partial different equation was derived to describe the dependence of carrier gas pressure in the column on the column distance and the time under temperature programmed conditions. This equation was solved numerically by the modified finite difference method for various column parameters. Constant inlet and outlet pressures were used as boundary conditions. The retention times calculated on assumption of a constant pressure profile along the column. Significant differences between retention times of corresponding solutes calculated by the two methods were found, especially when relatively long columns(L>50m) with small internal diameter(d<0.3mm)and high temperature program rates (r>5°/min)are used.     

Analysis of the Sulfonylurea Herbicide Metsulfuron-Methyl and Its Metabolites in the Soil of Cereal Crops. Comparative Analytical Chemistry of the Sulfonylureas

Abstract

For the analysis of metsulfuron-methyl in the crop soils with a sensitivity limit of 0.3 μg kg^?1 dry soil, in the soil extract metsulfuron-methyl was separated from its soil metabolites and the soil impurities by repeated thin-layer chromatographies (TLC). In the cleaned soil extract, diazomethane transformed metsulfuron-methyl 1 into N,N′ -dimethyl metsulfuron-methyl 2 (methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)methylamino]carbonyl]methylamino]sulfonyl]benzoate). In the gas-liquid chromatograph with detection by electron capture (GC-EC) and in the combined gas chromatograph-mass spectrometer (GC-MS), 2 was transformed into 1-dioxy-2-N-methyl-3-keto-1,2-benzisothiazole 3 which was measured by GC-EC with confirmation by GC-MS. The metsulfuron-methyl soil metabolites 2-sulfonamido-methylbenzoate 6, 1-dioxy-3-keto-1,2-benzisothiazole (saccharin) 7 and 2-sulfonamidobenzoic acid 8 were analyzed in the soil of winter wheat crops by a procedure similar to the one for metsulfuron-methyl. After their separation and purification in the soil extracts by TLC, 7 and 8 were methylated, and analyzed as 3 in the GC-EC and GC-MS apparatus where the generated 6 was quantitatively transformed into 3; 6 was analyzed as such with the GC and GC-MS apparatus wherein it was transformed into 3. The sensitivity limit for each metabolite was 0.3 μg of equivalents of metsulfuron-methyl kg^?1dry soil. The syntheses of the analysis standards of the metsulfuron-methyl derivatives 2 and 3, and of the metsulfuron-methyl metabolites 6, 7 and 8 are described. The transformation pathways of metsulfuron-methyl and of its derivatives are different from those of the pyridine-pyrimidine sulfonylurea herbicides flupyrsulfuron-methyl and rimsulfuron. The soil analysis of a sulfonylurea -by means of one of its transformation product- needs a previous study of the chemical reactivity of the sulfonylurea. This leads to the analysis procedures for the main soil metabolites of the sulfonylurea.