QuEChERS-气相色谱-串联质谱法测定油麦菜中农药多残留的基质效应
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摘要
目的建立一种QuEChERS-气相色谱-串联质谱法(gas chrom atography-tandem mass spectrometry,GC-MS/MS)测定油麦菜中64种农药多残留基质效应的分析方法。方法样品经乙腈提取, N-丙基乙二胺(PSA)净化,配制基质标准点与溶剂标准点进行峰面积对比来评价基质效应。结果油麦菜基质对18.8%的农药多残留项目不表现基质效应,对37.5%的项目有强基质效应;当基质液稀释至50倍后,对81.3%的农药多残留项目不表现出基质效应;稀释至100倍后,有氟胺氰菊酯、氯氟氰菊酯和水胺硫磷3种处于中等基质效应。结论在使用气相色谱-串联质谱法测定油麦菜中农药多残留含量的过程中,需要通过稀释来准确定量时,要注化合物在不同稀释比例的基质下所受到的基质效应的影响。该方法快速、简单,适用于蔬菜水果中农药多残留基质效应的测定和评估。
Objective To establish a method for the determination of matrix effects of 64 pesticides multi-residue in lettuce by QuEChERS-gas chromatography-tandem mass spectrometry(GC-MS/MS). Methods Samples were extracted with acetonitrile, and purified by primary secondary amine(PSA). The matrix effects were evaluated by comparing the peak areas of the matrix standard and the solvent standard. Results The lettuce substrate did not exhibit a matrix effect on 18.8% of pesticide multi-residue projects, and had a strong matrix effect on 37.5% of the projects. When the substrate solution was diluted to 50 times, it did not exhibit a matrix effect on the 81.3% pesticide multi-residue projects. And the tau-fluvalinate, cyhalothrin and isocarbophos still showed a moderate matrix effect even when the matrix solution was diluted with 100 times. Conclusion In the process of determining the multi-residue content of pesticides in lettuce by gas chromatography-tandem mass spectrometry, it is necessary to accurately quantify by dilution, and to influence the matrix effect of the compound under different dilution ratios.This method is rapid and simple, which is suitable for determination and evaluation the matrix effects in vegetables and fruits.
Objective To establish a method for the determination of matrix effects of 64 pesticides multi-residue in lettuce by QuEChERS-gas chromatography-tandem mass spectrometry(GC-MS/MS). Methods Samples were extracted with acetonitrile, and purified by primary secondary amine(PSA). The matrix effects were evaluated by comparing the peak areas of the matrix standard and the solvent standard. Results The lettuce substrate did not exhibit a matrix effect on 18.8% of pesticide multi-residue projects, and had a strong matrix effect on 37.5% of the projects. When the substrate solution was diluted to 50 times, it did not exhibit a matrix effect on the 81.3% pesticide multi-residue projects. And the tau-fluvalinate, cyhalothrin and isocarbophos still showed a moderate matrix effect even when the matrix solution was diluted with 100 times. Conclusion In the process of determining the multi-residue content of pesticides in lettuce by gas chromatography-tandem mass spectrometry, it is necessary to accurately quantify by dilution, and to influence the matrix effect of the compound under different dilution ratios.This method is rapid and simple, which is suitable for determination and evaluation the matrix effects in vegetables and fruits.
引文
[1]Erney DR,Gillespie AM,Gilvydis DM,et al.Explanation of the matrix-induced chromatographic response enhancement of organophosphorus pesticides during open tubular column gas chromatography with splitless or hot on-column injection and flame photometric detection[J].J Chromatogr A,1993,638(1):57-63.
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[3]Sanchez-Brunete C,Albero B,Martin G,et al.Determination of pesticide residues by GC-MS using analyte protectants to counteract the matrix effect[J].Jap Soc Anal Chem,2005,21(11):1291-1296.
[4]Rahman MM,Choi JH,El-Aty AMA,et al.Pepper leaf matrix as a promising analyte protectant prior to the analysis of thermolabile terbufos and its metabolites in pepper using GC-FPD[J].Food Chem,2012,133(2):604-610.
[5]Tuzimski T,Rejczak T.Application of HPLC-DAD after SPE/QuEChERSwith ZrO2-based sorbent in D-SPE clean-up step for pesticide analysis in edible oils[J].Food Chem,2016,190:71-79.
[6]Bedassa T,Gure A,Megersa N,et al.Modified QuEChERS method for the determination of multi class pesticide residues in fruit samples utilizing high-performance liquid chromatography[J].Food Anal Methods,2015,8(8):2020-2027.
[7]Kemmerich M,Rizzetti TM,Martins ML,et al.Optimization by central composite design of a modified QuEChERS method for extraction of pesticide multiresidue in sweet pepper and analysis by ultra-high performance liquid chromatography-tandem mass spectrometry[J].Food Anal Methods,2015,8(3):728-739.
[8]Fernandes VC,Freitas M,Pacheco JPG,et al.Magnetic dispersive micro solid-phase extraction and gas chromatography determination of organophosphorus pesticides in strawberries[J].J Chromatogr A,2018,1566:1-12.
[9]Martins ML,Kemmerich M,Prestes OD,et al.Evaluation of an alternative fluorinated sorbent for dispersive solid-phase extraction clean-up of the quick,easy,cheap,effective,rugged,and safe method for pesticide residues analysis[J].J Chromatogr A,2017,1514:36-43.
[10]Qin YH,Zhang JR,Li YF,et al.Automated multi-filtration cleanup with nitrogen-enriched activated carbon material as pesticide multi-residue analysis method in representative crop commodities[J].J Chromatogr A,2017,1515:62-68.
[11]Bresin B,Piol M,Fabbro D,et al.Analysis of organo-chlorine pesticides residue in raw coffee with amodified"quick easy cheap effective rugged and safe"extraction/clean up procedure for reducing the impact of caffeine on the gas chromatography-mass spectrometry measurement[J].JChromatogr A,2015,1376:167-171.
[12]Sapozhnikova Y.High-throughput analytical method for 265 pesticides and environmental contaminants in meats and poultry by fast low pressure gas chromatography and ultra-high performance liquid chromatography tandem mass spectrometry[J].J Chromatogr A,2018,1572:203-211.
[13]Mastovska K,Lehotay SJ,Anastassiades M.Combination of analyte protectants to overcome matrix effects in routine GC analysis of pesticide residues in food matrixes[J].Anal Chem,2005,77(24):8129-8137.
[14]Parrilla VP,Hakme E,Ucles S,et al.Large multiresidue analysis of pesticides in edible vegetable oils by using efficient solid-phase extraction sorbents based on quick,easy,cheap,effective,rugged and safe methodology followed by gas chromatography-tandem mass spectrometry[J].J Chromatogr A,2016,1463:20-31.
[15]Trevisan MTS,Owen RW,Calatayud-Vernich P,et al.Pesticide analysis in coffee leaves using a quick,easy,cheap,effective,rugged and safe approach and liquid chromatography tandem mass spectrometry:Optimization of the clean-up step[J].J Chromatogr A,2017,1512:98-106.
[16]Wang JS,He ZY,Wang L,et al.Automatic single-step quick,easy,cheap,effective,rugged and safe sample preparation devices for analysis of pesticide residues in foods[J].J Chromatogr A,2017,1521:10-18.
[17]GB 2763-2016食品安全国家标准食品中农药最大残留限量[S].GB 2763-2016 National food safety standard-Maximum residue limits of pesticides in food[S].
[18]Besil N,Cesio V,Heinzen H,et al.Matrix effects and interferences of different citrus fruit co-extractives in pesticide residue analysis using ultra-high-performance liquid chromatography-high-resolution mass spectrometry[J].J Agric Food Chem,2017,65:4819-4829.
[19]Arias JLDO,Rombaldi C,Caldas SS,et al.Alternative sorbents for the dispersive solid-phase extraction step in quick,easy,cheap,effective,rugged and safe method for extraction of pesticides from rice paddy soils with determination by liquid chromatography tandem mass spectrometry[J].J Chromatogr A,2014,1360:66-75.
[20]Ferrer C,Lozano A,Aguera A,et al.Overcoming matrix effects using the dilution approach in multiresidue methods for fruits and vegetables[J].JChromatogr A,2011,1218:7634-7639.
[21]Poole CF.Matrix-induced response enhancement in pesticide residue analysis by gas chromatography[J].J Chromatogr A,2007,1158:241-250.
[22]Jiao WT,Xiao Y,Qian XS,et al.Optimized combination of dilution and refined QuEChERS to overcome matrix effects of six types of tea for determination eight neonicotinoid insecticides by ultra performance liquid chromatography-electrospray tandem mass spectrometry[J].Food Chem,2016,210:26-34.
[2]Rimayi C,Odusanya D,Mtunzi F,et al.Alternative calibration techniques for counteracting the matrix effects in GCMS-SPE pesticide residue analysis-astatistical approach[J].Chemosphere,2015,118:35-43.
[3]Sanchez-Brunete C,Albero B,Martin G,et al.Determination of pesticide residues by GC-MS using analyte protectants to counteract the matrix effect[J].Jap Soc Anal Chem,2005,21(11):1291-1296.
[4]Rahman MM,Choi JH,El-Aty AMA,et al.Pepper leaf matrix as a promising analyte protectant prior to the analysis of thermolabile terbufos and its metabolites in pepper using GC-FPD[J].Food Chem,2012,133(2):604-610.
[5]Tuzimski T,Rejczak T.Application of HPLC-DAD after SPE/QuEChERSwith ZrO2-based sorbent in D-SPE clean-up step for pesticide analysis in edible oils[J].Food Chem,2016,190:71-79.
[6]Bedassa T,Gure A,Megersa N,et al.Modified QuEChERS method for the determination of multi class pesticide residues in fruit samples utilizing high-performance liquid chromatography[J].Food Anal Methods,2015,8(8):2020-2027.
[7]Kemmerich M,Rizzetti TM,Martins ML,et al.Optimization by central composite design of a modified QuEChERS method for extraction of pesticide multiresidue in sweet pepper and analysis by ultra-high performance liquid chromatography-tandem mass spectrometry[J].Food Anal Methods,2015,8(3):728-739.
[8]Fernandes VC,Freitas M,Pacheco JPG,et al.Magnetic dispersive micro solid-phase extraction and gas chromatography determination of organophosphorus pesticides in strawberries[J].J Chromatogr A,2018,1566:1-12.
[9]Martins ML,Kemmerich M,Prestes OD,et al.Evaluation of an alternative fluorinated sorbent for dispersive solid-phase extraction clean-up of the quick,easy,cheap,effective,rugged,and safe method for pesticide residues analysis[J].J Chromatogr A,2017,1514:36-43.
[10]Qin YH,Zhang JR,Li YF,et al.Automated multi-filtration cleanup with nitrogen-enriched activated carbon material as pesticide multi-residue analysis method in representative crop commodities[J].J Chromatogr A,2017,1515:62-68.
[11]Bresin B,Piol M,Fabbro D,et al.Analysis of organo-chlorine pesticides residue in raw coffee with amodified"quick easy cheap effective rugged and safe"extraction/clean up procedure for reducing the impact of caffeine on the gas chromatography-mass spectrometry measurement[J].JChromatogr A,2015,1376:167-171.
[12]Sapozhnikova Y.High-throughput analytical method for 265 pesticides and environmental contaminants in meats and poultry by fast low pressure gas chromatography and ultra-high performance liquid chromatography tandem mass spectrometry[J].J Chromatogr A,2018,1572:203-211.
[13]Mastovska K,Lehotay SJ,Anastassiades M.Combination of analyte protectants to overcome matrix effects in routine GC analysis of pesticide residues in food matrixes[J].Anal Chem,2005,77(24):8129-8137.
[14]Parrilla VP,Hakme E,Ucles S,et al.Large multiresidue analysis of pesticides in edible vegetable oils by using efficient solid-phase extraction sorbents based on quick,easy,cheap,effective,rugged and safe methodology followed by gas chromatography-tandem mass spectrometry[J].J Chromatogr A,2016,1463:20-31.
[15]Trevisan MTS,Owen RW,Calatayud-Vernich P,et al.Pesticide analysis in coffee leaves using a quick,easy,cheap,effective,rugged and safe approach and liquid chromatography tandem mass spectrometry:Optimization of the clean-up step[J].J Chromatogr A,2017,1512:98-106.
[16]Wang JS,He ZY,Wang L,et al.Automatic single-step quick,easy,cheap,effective,rugged and safe sample preparation devices for analysis of pesticide residues in foods[J].J Chromatogr A,2017,1521:10-18.
[17]GB 2763-2016食品安全国家标准食品中农药最大残留限量[S].GB 2763-2016 National food safety standard-Maximum residue limits of pesticides in food[S].
[18]Besil N,Cesio V,Heinzen H,et al.Matrix effects and interferences of different citrus fruit co-extractives in pesticide residue analysis using ultra-high-performance liquid chromatography-high-resolution mass spectrometry[J].J Agric Food Chem,2017,65:4819-4829.
[19]Arias JLDO,Rombaldi C,Caldas SS,et al.Alternative sorbents for the dispersive solid-phase extraction step in quick,easy,cheap,effective,rugged and safe method for extraction of pesticides from rice paddy soils with determination by liquid chromatography tandem mass spectrometry[J].J Chromatogr A,2014,1360:66-75.
[20]Ferrer C,Lozano A,Aguera A,et al.Overcoming matrix effects using the dilution approach in multiresidue methods for fruits and vegetables[J].JChromatogr A,2011,1218:7634-7639.
[21]Poole CF.Matrix-induced response enhancement in pesticide residue analysis by gas chromatography[J].J Chromatogr A,2007,1158:241-250.
[22]Jiao WT,Xiao Y,Qian XS,et al.Optimized combination of dilution and refined QuEChERS to overcome matrix effects of six types of tea for determination eight neonicotinoid insecticides by ultra performance liquid chromatography-electrospray tandem mass spectrometry[J].Food Chem,2016,210:26-34.