改进的QuEChERS方法结合在线凝胶色谱-气相色谱-串联质谱法测定茶叶中39种有机磷农药的含量
Determination of 39 Organophosphorus Pesticides in Tea by Online Gel Permeation Chromatography-Gas Chromatography Tandem Mass Spectrometry Coupled with Modified QuEChERS Method
摘 要
将茶叶样品4.000 0 g、乙腈10.0 mL和4.00 mg·L-1环氧七氯内标溶液400 μL涡漩混合1 min，超声提取15 min，离心后取上清液1.0 mL，加入甲苯1 mL，经含N-丙基乙二胺（PSA）30 mg、C18 30 mg、石墨化炭黑（GCB）15 mg和无水硫酸镁150 mg的分散固相萃取吸附剂净化后，采用在线凝胶色谱-气相色谱-串联质谱法（Online GPC-GC-MS/MS）测定净化溶液中39种有机磷农药残留量。结果表明：39种有机磷农药在一定范围内呈线性关系，检出限（3S/N）为0.5~4.3 μg·kg-1。按标准加入法进行回收试验，回收率为83.1%~105%，相对标准偏差（n=6）均小于9.0%。
在线凝胶色谱-气相色谱-串联质谱法
有机磷农药
茶叶
QuEChERS
online gel permeation chromatography-gas chromatography tandem mass spectrometry (Online GPC-GC-MS/MS)
organophosphorus pesticide
tea
Abstract
The tea sample of 4.000 0 g, acetonitrile of 10.0 mL and 4.00 mg·L-1 heptachlor epoxide internal standard solution of 400 μL were swirled for 1 min, and extracted ultrasonically for 15 min. After centrifugation, the supernatant of 1.0 mL was taken and toluene of 1 mL was added. The mixture was purified with dispersive solid phase extraction adsorbents containing PSA of 30 mg, C18 of 30 mg, GCB of 15 mg, and anhydrous magnesium sulfate of 150 mg, and 39 organophosphorus pesticides in the purified solution were determined by online gel permeation chromatography-gas chromatography tandem mass spectrometry (Online GPC-GC-MS/MS). As shown by the results, linear relationships of 39 organophosphorus pesticides were found in definite ranges, with detection limits (3S/N) in the range of 0.5-4.3 μg·kg-1. Test for recovery was made by standard addition method, giving results in the range of 83.1%-105%, with RSDs (n=6) all less than 9.0%.
中图分类号 O657.63 DOI 10.11973/lhjy-hx201804013
所属栏目 工作简报
基金项目 浙江省食品药品检验研究院科研项目（2015-024）；浙江省科技计划公益技术应用研究项目（2017C37013）
收稿日期 2017/4/1
修改稿日期
网络出版日期
作者单位点击查看
联系人作者罗金文(luojw31@163.com)
备注朱炳祺,工程师,博士,研究方向为食品安全检测
引用该论文: ZHU Bingqi,JIN Shaoqiang,XU Xiaoying,HU Fan,TIAN Chunxia,ZHANG Miao,LUO Jinwen. Determination of 39 Organophosphorus Pesticides in Tea by Online Gel Permeation Chromatography-Gas Chromatography Tandem Mass Spectrometry Coupled with Modified QuEChERS Method[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2018, 54(4): 433～442
朱炳祺,金绍强,徐潇颖,胡帆,田春霞,张淼,罗金文. 改进的QuEChERS方法结合在线凝胶色谱-气相色谱-串联质谱法测定茶叶中39种有机磷农药的含量[J]. 理化检验－化学分册, 2018, 54(4): 433～442
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参考文献
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【2】YANG C S, WANG H, LI G X, et al. Cancer prevention by tea:Evidence from laboratory studies[J]. Pharmacological Research the Official Journal of the Italian Pharmacological Society, 2011,64(2):113-122.
【3】BI W, HE C, MA Y, et al. Investigation of free amino acid, total phenolics, antioxidant activity and purine alkaloids to assess the health properties of non-Camellia tea[J]. Acta Pharmaceutica Sinica B, 2016,6(2):170-181.
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【9】曹艳平,杨路平,邵立君.气相色谱-质谱法测定茶叶中23种农药残留量[J].理化检验-化学分册, 2015,51(5):647-650.
【10】刘敏,端裕树,宋苑苑,等.分散固相萃取-液相色谱-质谱检测蔬菜水果中氨基甲酸酯和有机磷农药[J].分析化学, 2006,34(7):941-945.
【11】刘海芳,马军辉,冯海强,等.固相微萃取法(SPME)在茶叶农残检测上的应用[J].茶叶, 2007,33(3):136-139.
【12】杨晓凤,谢淋,韩梅,等.凝胶渗透色谱净化-气相色谱法测定茶叶中30种有机氯及菊酯类农药残留量[J].理化检验-化学分册, 2011,47(6):698-700.
【13】胡贝贞,宋伟华,谢丽萍,等.加速溶剂萃取/凝胶渗透色谱-固相萃取净化/气相色谱-质谱法测定茶叶中残留的33种农药[J].色谱, 2008,26(1):22-28.
【14】刘妍慧,于常红,刘岩,等.基质固相分散萃取-高效液相色谱串联质谱法(HPLC-MS-MS)同时测定茶叶中11种农药的残留量[J].茶叶科学, 2014,(3):271-278.
【15】苏建峰,钟茂生,陈晶,等.气相色谱-质谱法与气相色谱法测定茶叶及茶叶加工品中295种农药多残留[J].分析测试学报, 2015,34(6):625-638.
【16】楼正云,陈宗懋,罗逢健,等.固相萃取-气相色谱法测定茶叶中残留的92种农药[J].色谱, 2008,26(5):568-576.
【17】GB/T 23204-2008茶叶中519种农药及相关化学品残留量的测定气相色谱-质谱法[S].
【18】GB/T 23205-2008茶叶中448种农药及相关化学品残留量的测定液相色谱-串联质谱法[S].
【19】ANASTASSIADES M, LEHOTAY S J, STAJNBAHER D, et al. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid-phase extraction" for the determination of pesticide residues in produce[J]. Journal of AOAC International, 2003,86(2):412-431.
【20】卢大胜,熊丽蓓,温忆敏,等.QuEChERS前处理方法联合GPC-GC/MS在测定蔬菜水果农药残留中的应用[J].质谱学报, 2011,32(4):229-235.
【21】李军明,钟读波,王亚琴,等.在线凝胶渗透色谱-气相色谱/质谱法检测茶叶中的153种农药残留[J].色谱, 2010,28(9):840-848.
【22】李春艳,孔祥虹,何强,等.改进的QuEChERS-GC-MS法快速分析茶叶中30种农药残留[J].中国食物与营养, 2010,2010(2):57-60.
【23】余璐,宋伟,吕亚宁,等.超高效液相色谱-四极杆-飞行时间质谱法快速筛查茶叶中的204种农药残留[J].色谱, 2015,33(6):597-612.
【24】贾玮,黄峻榕,凌云,等.高效液相色谱-串联质谱法同时测定茶叶中290种农药残留组分[J].分析测试学报, 2013,32(1):9-22.
【25】张媛媛,张卓,陈忠正,等.QuEChERS方法在茶叶农药残留检测中的应用研究进展[J].食品安全质量检测学报, 2014,5(9):2711-2716.
【26】周利,罗逢健,张新忠,等.纳米竹炭分散固相萃取/超高效液相色谱-串联质谱法测定绿茶中的农药多残留[J].分析测试学报, 2014,33(6):642-647.
【27】HAN Y, ZOU N, SONG L, et al. Simultaneous determination of 70 pesticide residues in leek, leaf lettuce and garland chrysanthemum using modified QuEChERS method with multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction materials[J]. Journal of Chromatography B, 2015,1005:56-64.
【28】HUO F, TANG H, WU X, et al. Utilizing a novel sorbent in the solid phase extraction for simultaneous determination of 15 pesticide residues in green tea by GC/MS[J]. Journal Chromatography B, 2016,1023-1024(15):44-54.
【29】庞国芳,范春林,李岩,等.茶叶中653种农药化学品残留GC-MS、GC-MS/MS与LC-MS/MS分析方法:国际AOAC方法评价预研究[J].分析测试学报, 2012,31(9):1017-1030.
【2】YANG C S, WANG H, LI G X, et al. Cancer prevention by tea:Evidence from laboratory studies[J]. Pharmacological Research the Official Journal of the Italian Pharmacological Society, 2011,64(2):113-122.
【3】BI W, HE C, MA Y, et al. Investigation of free amino acid, total phenolics, antioxidant activity and purine alkaloids to assess the health properties of non-Camellia tea[J]. Acta Pharmaceutica Sinica B, 2016,6(2):170-181.
【4】SOOD C, JAGGI S, KUMAR V, et al. How manufacturing processes affect the level of pesticide residues in tea[J]. Jouanal of the Science Food & Agriculture, 2005,84(15):2123-2127.
【5】SHARMA D, NAGPAL A, PAKADE Y B, et al. Analytical methods for estimation of organophosphorus pesticide residues in fruits and vegetables:A review[J]. Talanta, 2010,82(4):1077-1089.
【6】HUANG Z, LI Y, CHEN B, et al. Simultaneous determination of 102 pesticide residues in Chinese teas by gas chromatography-mass spectrometry[J]. Journal of Chromatography B Analytical Technologies in the Biomedical & Life Sciences, 2007,853(1/2):154-162.
【7】VILLAVERDE J J, SEVILLA-MORÁN B, LÓPEZ-GOTI C, et al. Trends in analysis of pesticide residues to fulfil the European Regulation (EC)[J]. TrAC Trends Analytical Chemistry, 2016,80:568-580.
【8】AUTHORITY E F S. The 2013 European Union report on pesticide residues in food[J]. Efsa Journal, 2015,13(3):4038-4038.
【9】曹艳平,杨路平,邵立君.气相色谱-质谱法测定茶叶中23种农药残留量[J].理化检验-化学分册, 2015,51(5):647-650.
【10】刘敏,端裕树,宋苑苑,等.分散固相萃取-液相色谱-质谱检测蔬菜水果中氨基甲酸酯和有机磷农药[J].分析化学, 2006,34(7):941-945.
【11】刘海芳,马军辉,冯海强,等.固相微萃取法(SPME)在茶叶农残检测上的应用[J].茶叶, 2007,33(3):136-139.
【12】杨晓凤,谢淋,韩梅,等.凝胶渗透色谱净化-气相色谱法测定茶叶中30种有机氯及菊酯类农药残留量[J].理化检验-化学分册, 2011,47(6):698-700.
【13】胡贝贞,宋伟华,谢丽萍,等.加速溶剂萃取/凝胶渗透色谱-固相萃取净化/气相色谱-质谱法测定茶叶中残留的33种农药[J].色谱, 2008,26(1):22-28.
【14】刘妍慧,于常红,刘岩,等.基质固相分散萃取-高效液相色谱串联质谱法(HPLC-MS-MS)同时测定茶叶中11种农药的残留量[J].茶叶科学, 2014,(3):271-278.
【15】苏建峰,钟茂生,陈晶,等.气相色谱-质谱法与气相色谱法测定茶叶及茶叶加工品中295种农药多残留[J].分析测试学报, 2015,34(6):625-638.
【16】楼正云,陈宗懋,罗逢健,等.固相萃取-气相色谱法测定茶叶中残留的92种农药[J].色谱, 2008,26(5):568-576.
【17】GB/T 23204-2008茶叶中519种农药及相关化学品残留量的测定气相色谱-质谱法[S].
【18】GB/T 23205-2008茶叶中448种农药及相关化学品残留量的测定液相色谱-串联质谱法[S].
【19】ANASTASSIADES M, LEHOTAY S J, STAJNBAHER D, et al. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid-phase extraction" for the determination of pesticide residues in produce[J]. Journal of AOAC International, 2003,86(2):412-431.
【20】卢大胜,熊丽蓓,温忆敏,等.QuEChERS前处理方法联合GPC-GC/MS在测定蔬菜水果农药残留中的应用[J].质谱学报, 2011,32(4):229-235.
【21】李军明,钟读波,王亚琴,等.在线凝胶渗透色谱-气相色谱/质谱法检测茶叶中的153种农药残留[J].色谱, 2010,28(9):840-848.
【22】李春艳,孔祥虹,何强,等.改进的QuEChERS-GC-MS法快速分析茶叶中30种农药残留[J].中国食物与营养, 2010,2010(2):57-60.
【23】余璐,宋伟,吕亚宁,等.超高效液相色谱-四极杆-飞行时间质谱法快速筛查茶叶中的204种农药残留[J].色谱, 2015,33(6):597-612.
【24】贾玮,黄峻榕,凌云,等.高效液相色谱-串联质谱法同时测定茶叶中290种农药残留组分[J].分析测试学报, 2013,32(1):9-22.
【25】张媛媛,张卓,陈忠正,等.QuEChERS方法在茶叶农药残留检测中的应用研究进展[J].食品安全质量检测学报, 2014,5(9):2711-2716.
【26】周利,罗逢健,张新忠,等.纳米竹炭分散固相萃取/超高效液相色谱-串联质谱法测定绿茶中的农药多残留[J].分析测试学报, 2014,33(6):642-647.
【27】HAN Y, ZOU N, SONG L, et al. Simultaneous determination of 70 pesticide residues in leek, leaf lettuce and garland chrysanthemum using modified QuEChERS method with multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction materials[J]. Journal of Chromatography B, 2015,1005:56-64.
【28】HUO F, TANG H, WU X, et al. Utilizing a novel sorbent in the solid phase extraction for simultaneous determination of 15 pesticide residues in green tea by GC/MS[J]. Journal Chromatography B, 2016,1023-1024(15):44-54.
【29】庞国芳,范春林,李岩,等.茶叶中653种农药化学品残留GC-MS、GC-MS/MS与LC-MS/MS分析方法:国际AOAC方法评价预研究[J].分析测试学报, 2012,31(9):1017-1030.
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