橄榄油中农药多残留前处理方法研究及其应用于气相色谱、气质联用测定效果评估
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摘要
建立了串联双柱净化前处理方法用于橄榄油中313种农药多残留的测定。橄榄油样品采用正己烷溶解,正己烷-乙腈-盐水三相分配除去部分杂质,农药组分转移至乙腈中,经串联双柱净化后供气相色谱仪(GC)和气相色谱-质谱仪(GC-MS)分析。气相色谱法采用火焰光度检测器(FPD)和电子捕获检测器(ECD)测试,外标法定量,适用于有机磷、有机氯和拟除虫菊酯等部分农药的测定。气相色谱-质谱法采用选择离子监测方式(SIM),外标法定量,适用于本法中所有313项农药的测定。在优化后的条件下进行分析,气相色谱-质谱法的检出限(S/N≥3)为0.01～0.03 mg/kg,在加标水平为0.01、0.05、0.20 mg/kg时,平均回收率为57.5%～148.4%(百菌清为44.3%),其中回收率在70%～120%之间的占93.9%,相对标准偏差为2.1%～17.8%。方法准确、灵敏、快速,可满足橄榄油中多种农药残留的风险监控需求并可扩展到其他植物油检测。
A method was developed and applied to determine the residual amounts of 313 pesticides in olive oil by gas chromatography(GC)and gas chromatography-mass spectrometry(GC-MS).Come to mention this method,the residues were extracted from oil with acetonitrile,separated with liquid-liquid partition.The clear supernatant liquid purified by solid phase extraction(Envi-18 and PSA columns)was ready for GC and GC-MS analysis.Determinations were performed by using selected ion monitoring(SIM)mode in GC-MS method for all pesticides,and flame photometric detector(FPD)or electron capture detector(ECD)in GC method for organophosphorous,organochlorine and pyrethroid pesticides.Thence,the external standard method was used in the quantification.The methods were convenient and rapid after investigating the conditions of pretreatment and determination.Under the optimal conditions,the detection limits for the GC-MS method(S/N≥3)of pesticides were 0.01 ～0.03 mg/kg,Tests for recovery were carried by addition of standards at concentration of 0.01～0.20 mg/kg,the recoveries were 57.5% ～148.4%(Chlorothalonil 44.3%),among which the recoveries for 93.9% pesticides were between 70% and 120%,the relative standard deviations were 2.1% ～17.8%.The methods are easy,fast,and more sensitive,which are able to meet the requirement of the multiresidual analysis in olive oil.
A method was developed and applied to determine the residual amounts of 313 pesticides in olive oil by gas chromatography(GC)and gas chromatography-mass spectrometry(GC-MS).Come to mention this method,the residues were extracted from oil with acetonitrile,separated with liquid-liquid partition.The clear supernatant liquid purified by solid phase extraction(Envi-18 and PSA columns)was ready for GC and GC-MS analysis.Determinations were performed by using selected ion monitoring(SIM)mode in GC-MS method for all pesticides,and flame photometric detector(FPD)or electron capture detector(ECD)in GC method for organophosphorous,organochlorine and pyrethroid pesticides.Thence,the external standard method was used in the quantification.The methods were convenient and rapid after investigating the conditions of pretreatment and determination.Under the optimal conditions,the detection limits for the GC-MS method(S/N≥3)of pesticides were 0.01 ～0.03 mg/kg,Tests for recovery were carried by addition of standards at concentration of 0.01～0.20 mg/kg,the recoveries were 57.5% ～148.4%(Chlorothalonil 44.3%),among which the recoveries for 93.9% pesticides were between 70% and 120%,the relative standard deviations were 2.1% ～17.8%.The methods are easy,fast,and more sensitive,which are able to meet the requirement of the multiresidual analysis in olive oil.
引文
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[6]董静,潘玉香,秦亚萍,等.气相色谱-负化学离子源质谱法同时检测蔬菜中103种农药残留[J].分析科学学报,2010,26(03):323-328DONG J,PAN Y X,QIN Y P,et al.Simultaneous determination of 103 pesticide residues using gas chromatographynegative chemical ionization mass spectrometry[J].Journal of Analytical Science,2010,26(03):323-328
[7]PANG G F,LIU Y M,FAN C L,et al.Simultaneous determination of 405 pesticide residues in grain by accelerated solvent extraction then gas chromatography-mass spectrometry or liquid chromatography-tandem mass spectrometry[J].Anal Bioanal Chem,2006,384:1366-1408
[8]黄宝勇,潘灿平,王一茹,等.气质联机分析蔬菜中农药多残留及基质效应的补偿[J].高等学校化学学报,2006,34(2):227-232HUANG B Y,PAN C P,WANG Y R,et al.Rapid determination of pesticide multiresidues in vegetable by gas chromatography-mass spectrometry and compensation for matrix effect with protectants[J].Chemical Journal of Chinese Universities,2006,34(2):227-232
[9]苏建峰,赵建晖,熊刚,等.超高效液相色谱-串联质谱法快速测定葱、姜、蒜与辣椒酱中的66种有机磷农药残留[J].分析测试学报,2011,30(10):1094-1099SU J F,ZHAO J H,XIONG G,et al.Determination of 66 organophosphrous pesticide residues in green onion,ginger,garlic and chili patse by ultra performance liquid chromatography-tandem mass spectrometry[J].Journal of Instrumental Analysis,2011,30(10):1094-1099
[10]JULIE F,FRANCOIS S,JENNIFER S.Multiresidue method for the determination of residues of 251 pesticides in fruits and vegetables by gas chromatography/mass spectrometry and liquid chromatography with fluorescence detection[J].J AOAC Int,2000,83(3):698-713
[11]张云,陈俊玉,陈泽宇,等.植物油中邻氨基苯甲二酰胺类农药残留检测技术研究[J].中国粮油学报,2017,32(8):118-122ZHANG Y,CHEN J Y,CHEN Z Y,et al.Detection technology of o-amino benzoic diamide pesticide residues in vegetable oil[J].Journal of the Chinese Cereals and Oils Association,2017,32(8):118-122
[12]史晓梅,陈士恒,章晴,等.分散固相萃取-气相色谱法快速测定食用植物油中66种农药残留[J].中国粮油学报,2016,31(7):132-137SHI X M,CHEN S H,ZHANG Q,et al.Rapid determination of 66 pesticides residues in edible vegetable oil by dispersive solid phase extraction method-gas chromatography[J].Journal of the Chinese Cereals and Oils Association,2016,31(7):132-137
[13]阮华,荣维广,宋宁慧,等.quechers-在线凝胶色谱-气相色谱-质谱法测定植物油中34种农药残留[J].分析化学,2014,42(8):1110-1116RUAN H,RONG W G,SONG N H,et al.Simultaneous determination of 34 pesticide residues in vegetable oil by quechers-on-line gel permeation chromatography-gas chromatography-mass spectrometry[J].Chinese Journal of Analytical Chemistry,2014,42(8):1110-1116
[14]颜鸿飞,张帆,陈练,等.在线凝胶渗透色谱-三重四极杆气质联用法同时测定橄榄油中72种农药残留[J].食品安全质量检测学报,2016,7(1):166-176YAN H F,ZHANG F,CHEN L,et al.Determination of 72pesticide residues in olive oil by online gel permeation chromatography gas chromatography-tandem mass spectrometry[J].Journal of Food Safety&Quality,2016,7(1):166-176
[15]史晓梅,章晴,杨永坛,等.凝胶渗透色谱净化结合气相色谱-三重四极杆质谱法测定植物油中多农药残留量[J].中国粮油学报,2017,32(10):156-162SHI X M,ZHANG Q,YANG Y T,et al.Determination of multi-pesticides residues in vegetable oil by gel permeation chromatography purifying method combined with gas chromatography tandem mass spectrometry[J].Journal of the Chinese Cereals and Oils Association,2017,32(10):156-162
[16]徐娟,王岚,黄华军,等.低温冷冻及分散固相萃取净化-超高效液相色谱-串联质谱法测定植物油中104种农药残留[J].色谱,2015,33(3):242-249XU J,WANG L,HUANG H J,et al.Low temperature freezing followed by dispersive solid phase extraction for the determination of 104 pesticide residues in vegetable oils using ultra-performance liquid chromatography-tandem mass spectrometry[J].Chinese Journal of Chromatography,2015,33(3):242-249.
[17]吴凤琪,靳保辉,吴卫东,等.分散固相萃取-气相色谱串联质谱法同时测定食用植物油中的8种农药[J].中国油脂,2014,39(6):95-97WU F Q,JIN B H,WU W D,et al.Determination of 8 pesticide residues in edible vegetable oil by gas chromatography-tandem mass spectrometry combined with dispersive solid phase extraction[J].China Oils and Fats,2014,39(6):95-97
[18]赵俊虹,周陶忆.气相色谱法同时测定氢化植物油中六种有机磷农药[J].食品科学,2008,29(12):533-535ZHAO J H,ZHOU T Y.Simultaneous detection of six organophosphorus pesticides in hydrogenated vegetable oil with gas chromatography[J].Food Science,2008,29(12):533-535
[19]程景,李培武,张文,等.基质固相分散-气相色谱法测定植物油中多种拟除虫菊酯类及有机磷类农药残留[J].中国油料作物学报,2008,30(3):346-352CHENG J,LI P W,ZHANG W,et al.Multiresidue determination of pesticides in vegetable oil by matrix solid-phase dispersion and gas chromatography[J].Chinese Journal of Oil Crop Science,2008,30(3):346-352
[20]谢刚,叶金,吴宇,等.超高效液相色谱-四级杆/静电场轨道阱高分辨质谱快速同时测定玉米中多种真菌毒素和农药残留[J].中国粮油学报,2018,33(3):126-133XIE G,YE J,WU Y,et al.Fast determination of mycotoxins and pesticide residues in maize by UPLC-Quadrupole/Orbitrap HRMS[J].Journal of the Chinese Cereals and Oils Association,2018,33(3):126-133
[21]POOLE C F.Matrix-induced response enhancement in pesticide residue analysis by gas chromatography[J].J Chromatogr A,2007,1158:241-250
[22]KRUVE A,KUNNAPAS A,HERODES K,et al.Matrix effects in pesticide multi-residue analysis by liquid chromatography-mass spectrometry[J].J Chromatogr A,2008,1187:58-66.
[2]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):625-638SU J F,ZHONG M S,CHEN J,et al.Multi-residue determination of 295 pesticides in tea and its products by gas chromatography-mass spectrometry and gas chromatography[J].Journal of Instrumental Analysis,2015,34(6):625-638
[3]ZHANG H,CHEN Z L,YANG G S,et al.Microwave pretreatment and gas chromatography-mass spectrometry determination of herbicide residues in onion[J].Food Chemistry,2008,108(1):322-328
[4]PANG G F,CAO Y Z,ZHANG J L,et al.Validation study on660 pesticide residues in animal tissues by gel permeation chromatography cleanup/gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry[J].J Chromatogr:A,2006,1125(1):1-30
[5]苏建峰,卢声宇,陈晶,等.溶剂转移-气相色谱-质谱法和选择洗脱-气相色谱法测定大蒜中289种农药多残留[J].色谱,2011,29(7):643-655SU J F,LU S Y,CHEN J,et al.Multi-residue determination of 289 pesticides in garlic by gas chromatography and gaschromatography/mass spectrometry[J].Chinese Journal of Chromatography,2011,29(7):643-655
[6]董静,潘玉香,秦亚萍,等.气相色谱-负化学离子源质谱法同时检测蔬菜中103种农药残留[J].分析科学学报,2010,26(03):323-328DONG J,PAN Y X,QIN Y P,et al.Simultaneous determination of 103 pesticide residues using gas chromatographynegative chemical ionization mass spectrometry[J].Journal of Analytical Science,2010,26(03):323-328
[7]PANG G F,LIU Y M,FAN C L,et al.Simultaneous determination of 405 pesticide residues in grain by accelerated solvent extraction then gas chromatography-mass spectrometry or liquid chromatography-tandem mass spectrometry[J].Anal Bioanal Chem,2006,384:1366-1408
[8]黄宝勇,潘灿平,王一茹,等.气质联机分析蔬菜中农药多残留及基质效应的补偿[J].高等学校化学学报,2006,34(2):227-232HUANG B Y,PAN C P,WANG Y R,et al.Rapid determination of pesticide multiresidues in vegetable by gas chromatography-mass spectrometry and compensation for matrix effect with protectants[J].Chemical Journal of Chinese Universities,2006,34(2):227-232
[9]苏建峰,赵建晖,熊刚,等.超高效液相色谱-串联质谱法快速测定葱、姜、蒜与辣椒酱中的66种有机磷农药残留[J].分析测试学报,2011,30(10):1094-1099SU J F,ZHAO J H,XIONG G,et al.Determination of 66 organophosphrous pesticide residues in green onion,ginger,garlic and chili patse by ultra performance liquid chromatography-tandem mass spectrometry[J].Journal of Instrumental Analysis,2011,30(10):1094-1099
[10]JULIE F,FRANCOIS S,JENNIFER S.Multiresidue method for the determination of residues of 251 pesticides in fruits and vegetables by gas chromatography/mass spectrometry and liquid chromatography with fluorescence detection[J].J AOAC Int,2000,83(3):698-713
[11]张云,陈俊玉,陈泽宇,等.植物油中邻氨基苯甲二酰胺类农药残留检测技术研究[J].中国粮油学报,2017,32(8):118-122ZHANG Y,CHEN J Y,CHEN Z Y,et al.Detection technology of o-amino benzoic diamide pesticide residues in vegetable oil[J].Journal of the Chinese Cereals and Oils Association,2017,32(8):118-122
[12]史晓梅,陈士恒,章晴,等.分散固相萃取-气相色谱法快速测定食用植物油中66种农药残留[J].中国粮油学报,2016,31(7):132-137SHI X M,CHEN S H,ZHANG Q,et al.Rapid determination of 66 pesticides residues in edible vegetable oil by dispersive solid phase extraction method-gas chromatography[J].Journal of the Chinese Cereals and Oils Association,2016,31(7):132-137
[13]阮华,荣维广,宋宁慧,等.quechers-在线凝胶色谱-气相色谱-质谱法测定植物油中34种农药残留[J].分析化学,2014,42(8):1110-1116RUAN H,RONG W G,SONG N H,et al.Simultaneous determination of 34 pesticide residues in vegetable oil by quechers-on-line gel permeation chromatography-gas chromatography-mass spectrometry[J].Chinese Journal of Analytical Chemistry,2014,42(8):1110-1116
[14]颜鸿飞,张帆,陈练,等.在线凝胶渗透色谱-三重四极杆气质联用法同时测定橄榄油中72种农药残留[J].食品安全质量检测学报,2016,7(1):166-176YAN H F,ZHANG F,CHEN L,et al.Determination of 72pesticide residues in olive oil by online gel permeation chromatography gas chromatography-tandem mass spectrometry[J].Journal of Food Safety&Quality,2016,7(1):166-176
[15]史晓梅,章晴,杨永坛,等.凝胶渗透色谱净化结合气相色谱-三重四极杆质谱法测定植物油中多农药残留量[J].中国粮油学报,2017,32(10):156-162SHI X M,ZHANG Q,YANG Y T,et al.Determination of multi-pesticides residues in vegetable oil by gel permeation chromatography purifying method combined with gas chromatography tandem mass spectrometry[J].Journal of the Chinese Cereals and Oils Association,2017,32(10):156-162
[16]徐娟,王岚,黄华军,等.低温冷冻及分散固相萃取净化-超高效液相色谱-串联质谱法测定植物油中104种农药残留[J].色谱,2015,33(3):242-249XU J,WANG L,HUANG H J,et al.Low temperature freezing followed by dispersive solid phase extraction for the determination of 104 pesticide residues in vegetable oils using ultra-performance liquid chromatography-tandem mass spectrometry[J].Chinese Journal of Chromatography,2015,33(3):242-249.
[17]吴凤琪,靳保辉,吴卫东,等.分散固相萃取-气相色谱串联质谱法同时测定食用植物油中的8种农药[J].中国油脂,2014,39(6):95-97WU F Q,JIN B H,WU W D,et al.Determination of 8 pesticide residues in edible vegetable oil by gas chromatography-tandem mass spectrometry combined with dispersive solid phase extraction[J].China Oils and Fats,2014,39(6):95-97
[18]赵俊虹,周陶忆.气相色谱法同时测定氢化植物油中六种有机磷农药[J].食品科学,2008,29(12):533-535ZHAO J H,ZHOU T Y.Simultaneous detection of six organophosphorus pesticides in hydrogenated vegetable oil with gas chromatography[J].Food Science,2008,29(12):533-535
[19]程景,李培武,张文,等.基质固相分散-气相色谱法测定植物油中多种拟除虫菊酯类及有机磷类农药残留[J].中国油料作物学报,2008,30(3):346-352CHENG J,LI P W,ZHANG W,et al.Multiresidue determination of pesticides in vegetable oil by matrix solid-phase dispersion and gas chromatography[J].Chinese Journal of Oil Crop Science,2008,30(3):346-352
[20]谢刚,叶金,吴宇,等.超高效液相色谱-四级杆/静电场轨道阱高分辨质谱快速同时测定玉米中多种真菌毒素和农药残留[J].中国粮油学报,2018,33(3):126-133XIE G,YE J,WU Y,et al.Fast determination of mycotoxins and pesticide residues in maize by UPLC-Quadrupole/Orbitrap HRMS[J].Journal of the Chinese Cereals and Oils Association,2018,33(3):126-133
[21]POOLE C F.Matrix-induced response enhancement in pesticide residue analysis by gas chromatography[J].J Chromatogr A,2007,1158:241-250
[22]KRUVE A,KUNNAPAS A,HERODES K,et al.Matrix effects in pesticide multi-residue analysis by liquid chromatography-mass spectrometry[J].J Chromatogr A,2008,1187:58-66.
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