色谱

色谱 ›› 2017, Vol. 35 ›› Issue (11): 1177-1183.DOI: 10.3724/SP.J.1123.2017.07011

• 研究论文 • 上一篇    下一篇

气相色谱-电子轰击电离/正化学电离质谱法测定白菜和苹果中3种有机锡类农药残留

蔡理胜1,2, 沈伟健2, 王正萍1, 张睿2, 丁涛2, 余可垚2, 王红2, 张文俊2, 龚玉霞2   

  1. 1. 南京理工大学, 江苏 南京 210094;
    2. 江苏出入境检验检疫局, 江苏 南京 210001
  • 收稿日期:2017-07-13 出版日期:2017-11-08 发布日期:2014-01-17
  • 通讯作者: 沈伟健,E-mail:shenwj18@jsciq.gov.cn
  • 基金资助:

    上海市长三角科技合作项目（15395810100）.

Determination of three organotin pesticide residues in apples and cabbages by gas chromatography-electron impact/positive chemical ionization mass spectrometry

CAI Lisheng1,2, SHEN Weijian2, WANG Zhengping1, ZHANG Rui2, DING Tao2, YU Keyao2, WANG Hong2, ZHANG Wenjun2, GONG Yuxia2   

  1. 1. Nanjing University of Science and Technology, Nanjing 210094, China;
    2. Jiangsu Entry-Exit Inspection and Quarantine Bureau, Nanjing 210001, China
  • Received:2017-07-13 Online:2017-11-08 Published:2014-01-17
  • Supported by:

    Shanghai Yangtze River Delta Science and Technology Cooperation Project (No. 15395810100).

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摘要：

分别采用电子轰击电离（EI）源和正化学电离（PCI）源两种离子源技术建立了气相色谱-质谱（GC-MS）同时测定白菜和苹果中苯丁锡、三苯锡和三环锡含量的方法，并对这两种方法进行了比较。样品经氢溴酸消解、丙酮-正己烷（1：2，v/v）提取，四乙基硼化钠衍生后用Florisil固相萃取柱净化，分别在EI源和PCI源下以选择离子监测模式进行测定。结果表明，方法的检出限（S/N=3）分别为0.01~0.05 mg/kg（EI源）和0.01~0.02 mg/kg（PCI源），定量限（S/N=10）分别为0.03~0.16 mg/kg（EI源）和0.02~0.06 mg/kg（PCI源）。三苯锡、三环锡和苯丁锡分别在各自的线性范围内线性关系良好，相关系数（r2）≥ 0.997。在50、100、200 μg/kg 3个添加水平下，采用GC-EI/MS和GC-PCI/MS时，阴性样品中3种有机锡的平均回收率分别为59.24%~97.36%（苹果）、50.54%~94.54%（白菜）和65.38%~95.86%（苹果）、62.56%~90.44%（白菜），相对标准偏差（RSD）均不超过6.9%（n=6）。该方法简单、灵敏，PCI源的选择性优于EI源，两种方法可以相互结合提高检测结果的可靠性。

关键词: 苯丁锡, 电子轰击电离源, 气相色谱-质谱, 三苯锡, 三环锡, 正化学电离源

Abstract:

A method for the simultaneous determination of fenbutatin oxide, triphenyltin and cyhexatin in apples and cabbages was developed by gas chromatography-mass spectrometry coupled with two different ionization techniques, electron impact (EI) ionization and positive chemical ionization (PCI). At first, the samples were digested by hydrobromic acid, and extracted by acetone-hexane (1:2, v/v). The extracts were derivatized by sodium tetraethylborate as the derivatization reagent, and cleaned up by the Florisil SPE columns. Finally, the samples were analyzed by GC-EI/MS and GC-PCI/MS in selected ion monitoring (SIM) mode. The results showed that good linearities were obtained with correlation coefficients (r2) greater than 0.997 for fenbutatin oxide in the range of 75-500 μg/L in both foods, triphenyltin in the range of 50-1000 μg/L in cabbages and 50-500 μg/L in apples and cyhexatin in the range of 50-1000 μg/L in the two foods. The accuracy was checked at three spiked levels (50, 100 and 200 μg/kg) in cabbages and apples. The limits of detection (LODs, S/N=3) were 0.01-0.05 mg/kg (EI) and 0.01-0.02 mg/kg (PCI), and the limits of quantifications (LOQs, S/N=10) were 0.03-0.16 mg/kg (EI) and 0.02-0.06 mg/kg (PCI). The average recoveries ranged from 59.24%-97.36% (apples) and 50.54%-94.54% (cabbages) in the mode of EI, and the corresponding values were 65.38%-95.86% and 62.56%-90.44% in the mode of PCI. The relative standard deviations (RSDs) were all less than 6.9% (n=6). The PCI method can be used to improve the accuracy in comparing with the EI, in terms of good selectivity and high sensitivity.

Key words: cyhexatin, electron impact ionization (EI), fentutatin oxide, gas chromatography-mass spectrometry (GC-MS), positive chemical ionization (PCI), triphenyltin

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