改良QuEChERS/气相色谱法测定蔬菜中35种有机磷农药的残留量
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摘要
目的建立改良QuEChERS/气相色谱法测定蔬菜中35种有机磷农药残留的快速分析方法。方法样品由乙腈提取,氯化钠盐析后,经PSA (primary secondary amine sorbent)填料和无水硫酸镁分散固相萃取净化,气相色谱火焰光度检测器(flamephotometricdetector,FDP)检测,基质匹配标准曲线校正,外标法定量。结果在50.0～1000.0μg·kg~(-1)线性范围内线性良好,相关系数(r)为0.9959～0.9998,在0.08、0.20、0.40 mg·kg~(-1) 3个添加水平下35种有机磷农药的平均回收率为75.32%～118.82%,相对标准偏差为0.46%～5.62%,方法检出限(limit of detection, LOD)为0.01～0.05 mg·kg~(-1),定量限(limit of quantitation, LOQ)为0.03～0.10 mg·kg~(-1)。结论该方法简便快速、准确灵敏,有机溶剂用量少,可满足蔬菜中35种有机磷农药残留同时快速检测的实际需要。
Objective To establish a method for simultaneous analysis of 35 organophosphorous pesticide residues in vegetables by the QuEChERS-gas chromatography(QuEChERS-GC). Methods The samples were extracted with acetonitrile and salted out with sodium chloride. The extracts was purified by dispersive solid phase extraction using PSA and magnesium sulfate as sorbents. Gas chromatography/flame photometric detector(GC/FPD) was used for detection and matrix matching standard curve was used for correction. The external standard method was used for quantitative analysis. Results Thirty-five kinds of organophosphorous pesticides had good linearity in the range of 50.0-1000.0 μg·kg~(-1) and the correlation coefficients(r) ranged from 0.9959 to 0.9998. The recoveries of 35 kinds of organophosphorus pesticides ranged from 75.32% to 118.82%, with relative standard deviations(RSDs) from 0.46% to 5.62% at 3 spiked levels of 0.08、0.20、0.40 mg·kg~(-1). The limits of detection(LOD) were in range of 0.01-0.05 mg·kg~(-1). The limit of quantitation(LOQ) were in range of 0.03-0.10 mg·kg~(-1). Conclusion This method is simple,rapid, sensitive, with a small amount of organic solvent, which can meet the demands for the simultaneous determination of multi-residue organophosphorous pesticide residues in vegetables.
Objective To establish a method for simultaneous analysis of 35 organophosphorous pesticide residues in vegetables by the QuEChERS-gas chromatography(QuEChERS-GC). Methods The samples were extracted with acetonitrile and salted out with sodium chloride. The extracts was purified by dispersive solid phase extraction using PSA and magnesium sulfate as sorbents. Gas chromatography/flame photometric detector(GC/FPD) was used for detection and matrix matching standard curve was used for correction. The external standard method was used for quantitative analysis. Results Thirty-five kinds of organophosphorous pesticides had good linearity in the range of 50.0-1000.0 μg·kg~(-1) and the correlation coefficients(r) ranged from 0.9959 to 0.9998. The recoveries of 35 kinds of organophosphorus pesticides ranged from 75.32% to 118.82%, with relative standard deviations(RSDs) from 0.46% to 5.62% at 3 spiked levels of 0.08、0.20、0.40 mg·kg~(-1). The limits of detection(LOD) were in range of 0.01-0.05 mg·kg~(-1). The limit of quantitation(LOQ) were in range of 0.03-0.10 mg·kg~(-1). Conclusion This method is simple,rapid, sensitive, with a small amount of organic solvent, which can meet the demands for the simultaneous determination of multi-residue organophosphorous pesticide residues in vegetables.
引文
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[4]徐国锋,聂继云,李海飞,等.QuEChERS净化GC/ECD测定苹果和柑橘中4种常用杀螨剂残留[J].分析测试学报,2015,(12):1387-1391.Xu GF,Nie JY,Li HF,et al.Residue analysis of four acaricides in apple and citrus by GC/ECD after QuEChERS clean-up[J].J Instrum Anal,2015,(12):1387-1391.
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[6]徐国锋,聂继云,李海飞,等.QuEChERS/气相色谱法测定水果中31种有机磷农药残留[J].分析测试学报,2016,(8):1021-1025.Xu GF,Nie JY,Li HF,et al.Determination of 31 organophosphorous pesticide residues in fruits by gas chromatography with QuEChERSsample preparation[J].J Instru Anal,2016,(8):1021-1025.
[7]宋利军,刘瑞弘,李腾根,等.QuEChERS提取-气相色谱法测定蔬菜中的10种有机磷类和氨基甲酸酯类农药残留量[J].中国卫生检验杂志,2017,(16):2304-2307.Song LJ,Liu RH,Li TG,et al.Residues determination of 10organophosphorus and carbamate pesticides in vegetables by QuEChERS-gas chromatography[J].Chin J Health Lab Technol,2017,(16):2304-2307.
[8]张仙,王小飞,彭西甜,等.改良QuEChERS-气相色谱法测定韭菜中15种有机磷农药残留[J].湖北农业科学,2017,(10):1941-1944.Zhang X,Wang XF,Peng XT,et al.Improvement analysis of 15organophosphoru pesticide residues in leeks using QuEChERS-GCmethod[J].Hubei Agric Sci,2017,(10):1941-1944.
[9]邹昀,何明辉,周锦,等.基于QuEChERS净化-气相色谱法检测蔬菜中16种有机磷农药残留[J].湖北农业科学,2017,(4):736-739.Zou Y,He MH,Zhou J,et al.GC determination of 16 organophosphoru pesticide residues in vegetables using QuEChERS purification[J].Hubei Agric Sci,2017,(4):736-739.
[10]杜艳,马萍,张建玲.气质联用法同时测定青稞中11种有机磷农药[J].粮油食品科技,2017,(1):48-50.Du Y,Ma P,Zhang JL,et al.Determination of 11 kinds of organophosphoru pesticide residue in highland barley by GC-MS[J].Sci Technol Cere Oils Foods,2017,(1):48-50.
[11]王海凤,王俊斌,刘海学,等.气质联用法同时测定果蔬中多种有机磷农药残留[J].食品与机械,2013,(1):92-94.Wang HF,Wang JB,Liu HX,et al.Determination of multiple organophosphoru pesticide residues simultaneously in fruit and vegetable by gas chromatography-mass spectrometry[J].Food Mach,2013,(1):92-94.
[12]李润岩,原现瑞,李挥,等.顶空固相微萃取-气质联用快速测定草莓中5种有机磷农药[J].食品科学,2009,(14):191-193.Li RY,Yuan XR,Li H,et al.Headspace solid-phase microextraction and gas chromatography-mass spectrometry for the rapid detection of 5organosphosphorus pesticide residues in strawberries[J].Food Sci,2009,(14):191-193.
[13]刘庆斌,张睿,王海涛,等.高效液相色谱串联质谱法对栀子中11种有机磷农药残留的检测[J].分析测试学报,2010,(1):73.Liu QB,Zhang R,Wang HT,et al.Determination of multi-residues of organophosphorus pesticides in gardenia jasminoides ellis by hplc tandem MS/MS[J].J Instrum Anal,2010,(1):73.
[14]赵风年,石梦琪,李辉,等.分散固相萃取-液质联用法检测玉米中4种农药[J].食品研究与开发,2016,(7):128-132.Zhao FN,Shi MQ,Li H,et al.Determination of pesticides in corns by liquid chromatography-tandem mass spectrometry with dispersive solid phase extraction[J].Food Res Dev,2016,(7):28-132.
[15]晏利芝,赵永彪,刘宁,等.UPLC-MS/MS法同时测定蔬菜中34种农药残留[J].食品研究与开发,2015,(3):100-103.Yan LZ,Zhao YB,Liu N,et al.Simultaneous determination of 34 kinds of pesticide residues in vegetables by UPLC-MS/MS[J].Food Res Dev,2015,(3):100-103.
[16]倪永付,闫秋成,朱莉萍.搅拌棒吸附萃取-液相色谱-串联质谱法测定微山湖水中的有机磷农药残留[J].理化检验(化学分册),2016,(7):766-769.Ni YF,Yan QC,Zhu LP.Determination of organophosphorus pesticide residues in weishan lake waters by LC-MS/MS combined with stir bar sorptive extraction[J].Phys Test Chem Anal Part B Chem Anal,2016,(7):766-769.
[17]王玉健,黄惠玲,董存柱,等.超高效液相色谱-串联质谱法同时测定水产品中9种有机磷农药残留量[J].理化检验(化学分册),2013,(4):398-404.Wang YJ,Huang HL,Dong CZ,et al.Simultaneous UHPLC-MS/MSdetermination of residual amounts of 9 organophosphorus pesticides in aquatic products[J].Phys Test Chem Anal Part B Chem Anal,2013,(4):398-404.
[18]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 for pesticides in food[S].
[2]张秀尧,蔡欣欣,陈珞洛,等.缓冲Qu EChERS法提取气相色谱火焰光度检测法快速测定水果蔬菜中39种有机磷农药残留[J].中国卫生检验杂志,2007,(12):2133-2135.Zhang XR,Cai XX,Chen LL,et al.GC-FPD determination of 39organophosphorus pesticide residues in fruits and vegetables using buffered QuEChERS[J].Chin J Health Lab Technol,2007,(12):2133-2135.
[3]房宁,李倩,巩俐彤,等.QuEChERS净化-气相色谱双柱法测定果蔬中25种有机磷农药[J].中国卫生检验杂志,2013,(11):2462-2464.Fang N,Li Q,Gong LT,et al.Determination of 25 organophosphorus pesticides in fruits and vegetables by QuEChERS purification-double column gas chromatography[J].Chin J Health Lab Technol,2013,(11):2462-2464.
[4]徐国锋,聂继云,李海飞,等.QuEChERS净化GC/ECD测定苹果和柑橘中4种常用杀螨剂残留[J].分析测试学报,2015,(12):1387-1391.Xu GF,Nie JY,Li HF,et al.Residue analysis of four acaricides in apple and citrus by GC/ECD after QuEChERS clean-up[J].J Instrum Anal,2015,(12):1387-1391.
[5]叶永丽,赫欣睿,陈士恩,等.QuEChERS-气相色谱分析高原夏菜中有机磷农药残留[J].食品安全质量检测学报,2015,(6):2164-2170.Ye YL,He XR,Chen SE,et al.Determination of organophosphorus pesticide residues in plateau summer vegetables by QuEChERS-gas chromatography[J].J Food Saf Qual,2015,(6):2164-2170.
[6]徐国锋,聂继云,李海飞,等.QuEChERS/气相色谱法测定水果中31种有机磷农药残留[J].分析测试学报,2016,(8):1021-1025.Xu GF,Nie JY,Li HF,et al.Determination of 31 organophosphorous pesticide residues in fruits by gas chromatography with QuEChERSsample preparation[J].J Instru Anal,2016,(8):1021-1025.
[7]宋利军,刘瑞弘,李腾根,等.QuEChERS提取-气相色谱法测定蔬菜中的10种有机磷类和氨基甲酸酯类农药残留量[J].中国卫生检验杂志,2017,(16):2304-2307.Song LJ,Liu RH,Li TG,et al.Residues determination of 10organophosphorus and carbamate pesticides in vegetables by QuEChERS-gas chromatography[J].Chin J Health Lab Technol,2017,(16):2304-2307.
[8]张仙,王小飞,彭西甜,等.改良QuEChERS-气相色谱法测定韭菜中15种有机磷农药残留[J].湖北农业科学,2017,(10):1941-1944.Zhang X,Wang XF,Peng XT,et al.Improvement analysis of 15organophosphoru pesticide residues in leeks using QuEChERS-GCmethod[J].Hubei Agric Sci,2017,(10):1941-1944.
[9]邹昀,何明辉,周锦,等.基于QuEChERS净化-气相色谱法检测蔬菜中16种有机磷农药残留[J].湖北农业科学,2017,(4):736-739.Zou Y,He MH,Zhou J,et al.GC determination of 16 organophosphoru pesticide residues in vegetables using QuEChERS purification[J].Hubei Agric Sci,2017,(4):736-739.
[10]杜艳,马萍,张建玲.气质联用法同时测定青稞中11种有机磷农药[J].粮油食品科技,2017,(1):48-50.Du Y,Ma P,Zhang JL,et al.Determination of 11 kinds of organophosphoru pesticide residue in highland barley by GC-MS[J].Sci Technol Cere Oils Foods,2017,(1):48-50.
[11]王海凤,王俊斌,刘海学,等.气质联用法同时测定果蔬中多种有机磷农药残留[J].食品与机械,2013,(1):92-94.Wang HF,Wang JB,Liu HX,et al.Determination of multiple organophosphoru pesticide residues simultaneously in fruit and vegetable by gas chromatography-mass spectrometry[J].Food Mach,2013,(1):92-94.
[12]李润岩,原现瑞,李挥,等.顶空固相微萃取-气质联用快速测定草莓中5种有机磷农药[J].食品科学,2009,(14):191-193.Li RY,Yuan XR,Li H,et al.Headspace solid-phase microextraction and gas chromatography-mass spectrometry for the rapid detection of 5organosphosphorus pesticide residues in strawberries[J].Food Sci,2009,(14):191-193.
[13]刘庆斌,张睿,王海涛,等.高效液相色谱串联质谱法对栀子中11种有机磷农药残留的检测[J].分析测试学报,2010,(1):73.Liu QB,Zhang R,Wang HT,et al.Determination of multi-residues of organophosphorus pesticides in gardenia jasminoides ellis by hplc tandem MS/MS[J].J Instrum Anal,2010,(1):73.
[14]赵风年,石梦琪,李辉,等.分散固相萃取-液质联用法检测玉米中4种农药[J].食品研究与开发,2016,(7):128-132.Zhao FN,Shi MQ,Li H,et al.Determination of pesticides in corns by liquid chromatography-tandem mass spectrometry with dispersive solid phase extraction[J].Food Res Dev,2016,(7):28-132.
[15]晏利芝,赵永彪,刘宁,等.UPLC-MS/MS法同时测定蔬菜中34种农药残留[J].食品研究与开发,2015,(3):100-103.Yan LZ,Zhao YB,Liu N,et al.Simultaneous determination of 34 kinds of pesticide residues in vegetables by UPLC-MS/MS[J].Food Res Dev,2015,(3):100-103.
[16]倪永付,闫秋成,朱莉萍.搅拌棒吸附萃取-液相色谱-串联质谱法测定微山湖水中的有机磷农药残留[J].理化检验(化学分册),2016,(7):766-769.Ni YF,Yan QC,Zhu LP.Determination of organophosphorus pesticide residues in weishan lake waters by LC-MS/MS combined with stir bar sorptive extraction[J].Phys Test Chem Anal Part B Chem Anal,2016,(7):766-769.
[17]王玉健,黄惠玲,董存柱,等.超高效液相色谱-串联质谱法同时测定水产品中9种有机磷农药残留量[J].理化检验(化学分册),2013,(4):398-404.Wang YJ,Huang HL,Dong CZ,et al.Simultaneous UHPLC-MS/MSdetermination of residual amounts of 9 organophosphorus pesticides in aquatic products[J].Phys Test Chem Anal Part B Chem Anal,2013,(4):398-404.
[18]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 for pesticides in food[S].