基于平行反应监测模式的液相色谱-四极杆-静电场轨道阱质谱测定生鲜牛乳中氟虫腈及其代谢物残留
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摘要
目的:建立一种测定生鲜牛乳中氟虫腈及其3种代谢物(氟甲腈、氟虫腈硫醚及氟虫腈砜)残留的液相色谱-四极杆-静电场轨道阱质谱方法。方法:样品经乙腈提取后,经Captiva ND lipids净化柱去除基质中的脂质干扰物,液相色谱分离,四极杆-静电场轨道阱质谱定性定量测定,平行反应监测模式检测。结果:4种待测组分均获得足够的色谱保留和分离,各化合物在0.5～10.0μg·kg~(-1)范围内呈现良好的线性关系,日内日间精密度小于15%,方法回收率在85%～115%之间,方法的定量下限为0.5μg·kg~(-1)。结论:此方法快速、准确且灵敏度高,为监测生鲜牛乳中的氟虫腈提供了有效的技术手段。
Objective:To establish a quantitative method of LC-quadrupole-Orbitrap MS for the determination of fipronil and its metabolites(fipronil-desulfinyl,fipronil sulfide,and fipronil sulfone)residues in raw milk. Methods:Milk samples were exacted with acetonitrile.Then the supernatant was purified by Captiva ND lipids solid phase extraction prior to being separated by liquid chromatography and analyzed by quadrupole-orbitrap mass spectrometry.The analytes were determined with parallel reaction monitoring mode.Results:The four analytes had sufficiently chromatography retention and separation.The calibration curve of each object showed a good linear within the concentration range from 0.5-10.0 μg·kg~(-1).The intra-and inter-day precisions were less than 15%.The average recoveries ranged from 85% to 115%.And the limit of detection was 0.5 μg·kg~(-1).Conclusion:The method is rapid and highly sensitive,which provides an accurate and effective solution for the determination of fipronil in raw milk.
Objective:To establish a quantitative method of LC-quadrupole-Orbitrap MS for the determination of fipronil and its metabolites(fipronil-desulfinyl,fipronil sulfide,and fipronil sulfone)residues in raw milk. Methods:Milk samples were exacted with acetonitrile.Then the supernatant was purified by Captiva ND lipids solid phase extraction prior to being separated by liquid chromatography and analyzed by quadrupole-orbitrap mass spectrometry.The analytes were determined with parallel reaction monitoring mode.Results:The four analytes had sufficiently chromatography retention and separation.The calibration curve of each object showed a good linear within the concentration range from 0.5-10.0 μg·kg~(-1).The intra-and inter-day precisions were less than 15%.The average recoveries ranged from 85% to 115%.And the limit of detection was 0.5 μg·kg~(-1).Conclusion:The method is rapid and highly sensitive,which provides an accurate and effective solution for the determination of fipronil in raw milk.
引文
[1]崔新仪,储晓刚,王大宁.氟虫腈及其代谢物的研究进展[J].农药,2008,47(2):81CUI XY,CHU XG,WANG DN.Research development of fipronil and its metabolites[J].Chin J Pestic,2008,47(2):81
[2]徐广春,顾中言,杨玉清,等.氟虫腈的应用和风险研究进展[J].现代农药,2008,7(2):1XU GC,GU ZY,YANG YQ,et al.Progress in research on risks of pesticide fipronil and its application[J].Mod Agrochem,2008,7(2):1
[3]吴长兴.毒死蜱和氟虫腈的环境毒理与风险[D].杭州:浙江大学,2010WU CQ.The Environmental Toxicity and Risk of Chlorpyrifos and Fipronil[D].Hangzhou:Zhejiang University,2010
[4]卢中秋,杜园园.新型吡唑类杀虫剂-锐劲特急性中毒2例报告[J].中国急救医学,2002,22(3):175LU ZQ,DU YY.The report of 2 cases on acute poisoning of pyrazole insecticide fipronil[J].Chin J Critical Care Med,2002,22(3):175
[5]GB 2763-2016食品安全国家标准-食品中农药最大残留限量[S].2016:71GB 2763-2016 National Food Safety Standard--Maximum Residue Limits for Pesticides in Food[S].2016:71
[6]Commission Regulations(EC)No.396/2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC[S].2005:921
[7]Commission Regulations(EU)No 1127/2014 of 20 October 2014,Amending Annexes II and III to Regulation(EC)No 396/2005 of the European Parliament and of the Council as Regards Maximum Residue Levels for Amitrole,Dinocap,Fipronil,Flufenacet,Pendimethalin,Propyzamide,and Pyridate in or on Certain Products[S].2014:79
[8]RAMASUBRAMANIAN T,PARAMASIVAM M,JAYANTHI R,et al.Asimple and sensitive single-step method for gas chromatography-mass spectrometric determination of fipronil and its metabolites in sugarcane juice,jaggery and sugar[J].Food Chem,2014,150(1):408
[9]白宝清,李美萍,张生万,等.QuEChERS-DLLME-高效液相色谱法测定蔬菜中溴虫腈和氟虫腈残留[J].食品科学,2014,35(24):254BAI BQ,LI MP,ZHANG SW,et al.Determination of chlorfenapyr and fipronil residues in vegetables by QuEChERS combined with dispersive liquid-liquid microextraction and high performance liquid chromatography[J].Food Sci,2014,35(24):254
[10]HINGMIRE S,DASHARATH PO,SAGAR CU,et al.Residue analysis of fipronil and difenoconazole in okra by liquid chromatography tandem mass spectrometry and their food safety evaluation[J].Food Chem,2015,176(1):145
[11]ZHANG MY,BIAN K,ZHOU T,et al.Determination of residue fipronil in chicken egg and muscle by LC-MS/MS[J].J Chromatogr B,2016,1014(1):31
[12]European Community(EC)No 657/2002:Commission Decision of Implementing Council Directive 96/23/EC Concerning the Performance of Analytical Methods and the Interpretation of Results[S].2002:17
[13]张艳欣,杨鑫,邹攀,等.优化流动相提高代谢组学尿液样品中代谢物覆盖率的方法[J].分析实验室,2017,36(1):1ZHANG YX,YANG X,ZOU P,et al.Increasing metabolite coverage by selecting optimal mobile-phase modifiers in HPLC-QTOF-MS of urine[J].Chin J Anal Lab,2017,36(1):1
[2]徐广春,顾中言,杨玉清,等.氟虫腈的应用和风险研究进展[J].现代农药,2008,7(2):1XU GC,GU ZY,YANG YQ,et al.Progress in research on risks of pesticide fipronil and its application[J].Mod Agrochem,2008,7(2):1
[3]吴长兴.毒死蜱和氟虫腈的环境毒理与风险[D].杭州:浙江大学,2010WU CQ.The Environmental Toxicity and Risk of Chlorpyrifos and Fipronil[D].Hangzhou:Zhejiang University,2010
[4]卢中秋,杜园园.新型吡唑类杀虫剂-锐劲特急性中毒2例报告[J].中国急救医学,2002,22(3):175LU ZQ,DU YY.The report of 2 cases on acute poisoning of pyrazole insecticide fipronil[J].Chin J Critical Care Med,2002,22(3):175
[5]GB 2763-2016食品安全国家标准-食品中农药最大残留限量[S].2016:71GB 2763-2016 National Food Safety Standard--Maximum Residue Limits for Pesticides in Food[S].2016:71
[6]Commission Regulations(EC)No.396/2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC[S].2005:921
[7]Commission Regulations(EU)No 1127/2014 of 20 October 2014,Amending Annexes II and III to Regulation(EC)No 396/2005 of the European Parliament and of the Council as Regards Maximum Residue Levels for Amitrole,Dinocap,Fipronil,Flufenacet,Pendimethalin,Propyzamide,and Pyridate in or on Certain Products[S].2014:79
[8]RAMASUBRAMANIAN T,PARAMASIVAM M,JAYANTHI R,et al.Asimple and sensitive single-step method for gas chromatography-mass spectrometric determination of fipronil and its metabolites in sugarcane juice,jaggery and sugar[J].Food Chem,2014,150(1):408
[9]白宝清,李美萍,张生万,等.QuEChERS-DLLME-高效液相色谱法测定蔬菜中溴虫腈和氟虫腈残留[J].食品科学,2014,35(24):254BAI BQ,LI MP,ZHANG SW,et al.Determination of chlorfenapyr and fipronil residues in vegetables by QuEChERS combined with dispersive liquid-liquid microextraction and high performance liquid chromatography[J].Food Sci,2014,35(24):254
[10]HINGMIRE S,DASHARATH PO,SAGAR CU,et al.Residue analysis of fipronil and difenoconazole in okra by liquid chromatography tandem mass spectrometry and their food safety evaluation[J].Food Chem,2015,176(1):145
[11]ZHANG MY,BIAN K,ZHOU T,et al.Determination of residue fipronil in chicken egg and muscle by LC-MS/MS[J].J Chromatogr B,2016,1014(1):31
[12]European Community(EC)No 657/2002:Commission Decision of Implementing Council Directive 96/23/EC Concerning the Performance of Analytical Methods and the Interpretation of Results[S].2002:17
[13]张艳欣,杨鑫,邹攀,等.优化流动相提高代谢组学尿液样品中代谢物覆盖率的方法[J].分析实验室,2017,36(1):1ZHANG YX,YANG X,ZOU P,et al.Increasing metabolite coverage by selecting optimal mobile-phase modifiers in HPLC-QTOF-MS of urine[J].Chin J Anal Lab,2017,36(1):1