同位素稀释高分辨气相色谱-高分辨质谱法测定土壤样品中二恶英类化合物的等价毒性当量不确定度的评定

采用同位素稀释高分辨气相色谱-高分辨质谱法（isotope dilution high resolution gas chromatography and high resolution mass spectrometry,ID-HRGC-HRMS）测定土壤样品中二恶英类化合物（polychlorinated dibenzo-p-dioxins and dibenzofurans,PCDD/Fs）的等价毒性当量（toxic equivalent quantity,TEQ）。讨论并确定了测定土壤样品中二恶英类化合物2,3,7,8位异构体不确定度的来源并合成了各异构体的相对标准不确定度;在此基础上,计算了3种等价毒性当量因子（toxic equivalent factor,TEF）框架下土壤样品中PCDD/Fs的TEQ浓度及其合成不确定度和扩展不确定度。     

同位素稀释气相色谱/三重四极质谱法测定二(噁)英同类物

建立了同位素稀释气相色谱/三重四极质谱法测定17种2,3,7,8位氯取代的二(噁)英同类物的痕量分析方法.使用Agilent 7000B三重四极气质联用仪,通过对色谱、质谱条件的优化,建立了高灵敏度和高选择性的二(噁)英同类物分析方法,17种二(噁)英毒性同类物的平均相对响应因子的相对标准偏差均小于11％;校正曲线在0...     

高分辨气相色谱/质谱法分析新闻纸和复印纸中的二(口恶)(口英)

随机选择空白的和经过印刷的新闻纸和复印纸,粉碎后用溶剂提取并经多步色谱柱纯化,采用同位素稀释、高分辨气相色谱/高分辨质谱(HRGC/HRMS)联用技术分析了其中的二(口恶)(口英)含量.结果表明:新闻纸中二(口恶)(口英)的总量高于复印纸,但是毒性当量却低于复印纸;经过印刷的新闻纸和复印纸中二(口恶)(口英)的含量均高于空白的新闻纸和复印纸;新闻纸和复印纸中相同二(口恶)(口英)异构体的含量是不同的.空白的和经过印刷的新闻纸中二(口恶)(口英)毒性当量分别为0.48 ng/kg和0.61 ng/kg,而空白的和经过印刷的复印纸中二(口恶)(口英)毒性当量分别为0.74 ng/kg和0.79 ng/kg.所有样品中添加的13C标记的2,3,7,8位取代的二(口恶)(口英)回收率均在49.82%至131.34%之间.     

大体积进样技术在气相色谱-质谱法测定 二英类化合物中的应用

利用大体积进样技术(large volume injection,LVI),结合气相色谱-质谱方法对二英的测定效果进行了研究。同时与传统分流/不分流进样技术进行了对比。对进样体积为1,5,10,25,50和100 μL的色谱图进行了分析。研究表明使用大体积进样方式,在不影响色谱分离度的同时,大幅度提高了分析灵敏度。通过对土壤样品的检测,证明该方法可以用于环境样品的实际测定。     

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。     

中药材中有机磷类农药残留量的GC-PCI-MS法测定(Ⅰ)

采用气相色谱-正化学电离-质谱法对中药材中有机磷农药残留进行检测方法的研究；应用选择离子监测(SIM)技术，排除了杂质的干扰，提高了分析灵敏度；建立了有效、实用的有机磷农药残留量的检测方法。     

(9Z,12Z,15Z)-十八碳三烯醛的GC-MS分析

（9Z，12Z，15Z）－十八碳三烯醛是美国白蛾信息素的主要成效成分之一，在其合成的过程中，采用气相色谱监测分离提纯效果；提纯的样品成分在化学方法、IR、^1H NMR波谱分析基础上用气相色谱－质谱鉴定为该化合物，并用气相色谱的面积归一化法测得其含量大于99％；该法简单、准确可靠、无需标样。     

交互移动窗口因子分析法(AMWFA)用于二维数据重叠色谱峰的比较分析

采用交互移动窗口因子分析法(AMWFA), 通过挖掘两个体系中的选择性信息, 获得了不同样本间的共有组分数, 还同时得到了各物质对应的光谱或质谱信息. 详细阐述了本法的原理和计算方法, 并用一个模拟的GC-MS 数据对方法进行了验证.     

新型潜香类化合物N-(2,3-吡嗪二甲酰基)-丙氨酸甲酯热裂解气相色谱-质谱分析

采用在线热裂解-气相色谱-质谱联用技术(Py-GC-MS)分析了潜香吡嗪类化合物N-(2,3-吡嗪二甲酰基)-丙氨酸甲酯的热裂解行为。首先通过对2,3-吡嗪二羧酸酰胺化反应合成了新型目标化合物N-(2,3-吡嗪二甲酰基)-丙氨酸甲酯,其结构经X射线单晶衍射(XRD),1H NMR,13C NMR,IR和HR-MS证实,然后在空气氛围中,对目标化合物分别在300,600,900℃下进行热裂解,并通过GC-MS对其挥发性热裂解产物进行定性和半定量分析。结果表明:1裂解形成了包括具有香味特征的吡嗪类、大茴香醇和大茴香醛在内的裂解产物共48种。不同温度下挥发性热裂解产物的类型和相对含量不同,300℃和600℃时相对含量最高的均为乙酸,而900℃时相对含量最高的为吡嗪,且与300℃和600℃裂解条件相比所形成的吡嗪类衍生物种类较多,相对含量较高。2在具有香味特征的裂解产物中,大茴香醇的相对含量随温度升高而升高,而大茴香醛和苯甲醛的相对含量则呈现随着温度升高而降低的趋势。基于目标化合物的热裂解产物的定性及定量变化情况,初步探讨了该物质可能的裂解机理。     

溴代二噁英的分析方法研究进展

溴代二噁英(PBDD/Fs)属于潜在的持久性有机污染物,是一种平面三环芳香化合物,具有致畸、致癌、致突变等特性。目前,国际上对PBDD/Fs分析检测的研究是一大热点,但国内对PBDD/Fs的研究却较少。因此,探究PBDD/Fs的分析检测方法,对进一步控制PBDD/Fs污染具有重要科学意义。本文介绍了PBDD/Fs的特性及其分析方法,着重探讨了PBDD/Fs的提取、净化、仪器分析以及质量控制这四个方面,通过对PBDD/Fs的研究能够更好地了解我国当前对PBDD/Fs的分析检测能力,为后续开展PBDD/Fs的分析检测提供科学有效的方法参考。     

同位素稀释-气相色谱-质谱法测定白酒中23种邻苯二甲酸酯类化合物

提出了同位素稀释-气相色谱-质谱法测定白酒中23种邻苯二甲酸酯类化合物含量的方法。样品用正己烷-乙酸乙酯(1+1)混合液提取后,经DB-5MS毛细管色谱柱分离,采用电子轰击离子源选择离子反应监测模式进行质谱测定,同位素内标法进行定量分析。23种邻苯二甲酸酯类化合物的线性范围在0.2~3.0mg·L-1之间,测定下限(10S/N)在0.05~0.1mg·kg-1之间。加标回收率在73.2%~122%之间,相对标准偏差(n=6)在0.49%~11%之间。     

二英类分析研究进展及展望

通过综合介绍国内外二英类物质分析研究的最新动态,包括二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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.     

倾动式阳极炉冶炼废杂铜二噁英排放特征研究

再生铜行业是我国二噁英排放的重点行业之一,研究再生铜行业不同冶炼方式下二噁英的排放特征对我国再生铜行业二噁英的污染防治具有重要意义。本文以再生铜倾动式阳极炉为对象,研究了倾动式阳极炉冶炼废杂铜在除尘设施前后的二噁英排放特征,并提出了其二噁英的产生机理。     

Analysis of acrylamide in food by isotope-dilution liquid chromatography coupled with electrospray ionization tandem mass spectrometry

A confirmatory method for the determination of low levels of acrylamide in different food products is presented. The method entails extraction of acrylamide with water, precipitation of matrix constituents with acetonitrile, and two clean-up steps consecutively over Isolute Multimode and cation-exchange cartridges. The final extract is analyzed by liquid chromatography (LC) coupled to positive electrospray ionization tandem mass spectrometry employing [13C3]-acrylamide as internal standard. For the chromatographic step, a LC column based on a polymethacrylate gel is employed which shows good retention of acrylamide under isocratic flow conditions (k' = 1.2). Mass spectral acquisition is done by selected reaction monitoring, choosing the characteristic transitions m/z 72-->55, 72-->54 and 72-->27. In-house validation data for breakfast cereals and crackers show good precision of the method, with intra- and interassay variation below 10%. The limits of detection for crackers and breakfast cereals, respectively are estimated at 15 and 20 microg/kg, and recoveries of fortified samples ranged between 58 and 76%. Furthermore, the method is applicable to a number of different food products, including biscuits, crisp bread, wafers, confectionery cocoa liquor, and nuts. Finally, the good results obtained in several small-scale interlaboratory tests provided additional confidence in the performance of the method.     

二恶英类化学物质的检测方法

本文介绍了20世纪60年代以来二恶英类化学物质的检测方法。重点介绍了色谱法、免疫法和生物法，并对各种分析方法的优缺点进行了评述，提出了各方法运用的适用范围，为建立二恶英类化学物质分析方法提供了依据。     

Use of Carbon-13 Labelled Dioxins Mixture for Analysis of Polychlorinated Dibenzo-p-Dioxins in Environmental Samples by GC-MS

Abstract

Positive identification and quantitation of polychlorinated dibenzo-p-dioxins (PCDD) in complicated environmental samples is described using a C-13 labelled dioxin mixture as an internal reference standard. Environmental samples are spiked with the C-13 labelled dioxin mixture and monitored for labelled and unlabelled dioxins using GC-MS in the electron impact selected ion monitoring (EISIM) mode. The C-13 labelled dioxin mixture and a municipal solid waste (MSW) incinerator fly ash extract show the same number of isomers in each tetra to octa-chlorodioxin congener groups. Quantitation of the C-13 labelled dioxin mixture was carried out using a reference standard mixture of unlabelled dioxins consisting of at least one isomer for each congener group. The C-13 labelled dioxin standard is highly useful for the determination of retention windows for tetra- to octa-chlorodioxins, identification of dioxins in each congener group, and calculation of the recovery of dioxins in samples that require extensive sample clean-up prior to GC-MS analysis. Its application for retention time window determination and as an internal reference standard for quantitation of dioxins in MSW incinerator fly ash extract and identification of dioxins in a complex sample from a PCB fire is demonstrated.     

痕量铼的同位素稀释中子活化分析

将同位素稀释法的准确性与中子活性分析（ＮＡＡ）的高灵敏度相结合，建立了一种新的痕量铼的测试方法，实验中对Ｒｅ的检出限为０．００４ｎｇ，全流程空白为０．０５ｎｇ，地于Ｒｅ含量为６４ｎｇ／ｇ的样品，在取样量为５０ｍｇ时，单次测定误差（２σ）为３．１％，测定Ｒｅ一为３０ｎｇ／ｇ的样品，本方法的２σ在３％以内，４次分析的ＲＳＤ为４．１％，而采用一般的ＮＡＡ，结果偏低约２０％，并且ＲＳＤ大于５％。     

Development and application of an ultratrace method for speciation of organotin compounds in cryogenically archived and homogenized biological materials

An accurate, ultra-sensitive and robust method for speciation of mono, di, and tributyltin (MBT, DBT, and TBT) by speciated isotope-dilution gas chromatography-inductively coupled plasma-mass spectrometry (SID-GC-ICPMS) has been developed for quantification of butyltin concentrations in cryogenic biological materials maintained in an uninterrupted cryo-chain from storage conditions through homogenization and bottling. The method significantly reduces the detection limits, to the low pg g(-1) level (as Sn), and was validated by using the European reference material (ERM) CE477, mussel tissue, produced by the Institute for Reference Materials and Measurements. It was applied to three different cryogenic biological materials-a fresh-frozen mussel tissue (SRM 1974b) together with complex materials, a protein-rich material (whale liver control material, QC03LH03), and a lipid-rich material (whale blubber, SRM 1945) containing up to 72% lipids. The commutability between frozen and freeze-dried materials with regard to spike equilibration/interaction, extraction efficiency, and the absence of detectable transformations was carefully investigated by applying complementary methods and by varying extraction conditions and spiking strategies. The inter-method results enabled assignment of reference concentrations of butyltins in cryogenic SRMs and control materials for the first time. The reference concentrations of MBT, DBT, and TBT in SRM 1974b were 0.92 +/- 0.06, 2.7 +/- 0.4, and 6.58 +/- 0.19 ng g(-1) as Sn (wet-mass), respectively; in SRM 1945 they were 0.38 +/- 0.06, 1.19 +/- 0.26, and 3.55 +/- 0.44 ng g(-1), respectively, as Sn (wet-mass). In QC03LH03, DBT and TBT concentrations were 30.0 +/- 2.7 and 2.26 +/- 0.38 ng g(-1) as Sn (wet-mass). The concentration range of butyltins in these materials is one to three orders of magnitude lower than in ERM CE477. This study demonstrated that cryogenically processed and stored biological materials are a promising alternative to conventional freeze-dried materials for organotin speciation analysis, because these are, at present, the best conditions for minimizing degradation of thermolabile species and for long-term archival. Finally, the potential of the analytical method was illustrated by analysis of polar bear (Ursus maritimus) and beluga whale (Delphinapterus leuca) liver samples that had been collected in the Arctic and archived at the Marine Environmental Specimen Bank. Significant concentrations of butyltin compounds were found in the samples and provide the first evidence of the presence of this class of contaminant in the Arctic marine ecosystem. Figure Eye catch image.