QuEChERS-气相色谱-串联质谱法测定蜂蜜中20种农药残留
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摘要
目的建立QuEChERS法与气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry,GC-MS/MS)联用快速检测蜂蜜中20种农残的分析方法。方法样品用乙腈快速提取、无水硫酸镁与乙酸钠盐析,经无水硫酸镁、N-丙基乙二胺(N-propyl ethylenediamine,PSA)和C_(18)净化后,用GC-MS/MS分析。质谱采用多反应监测模式(multiple reation monitoring, MRM),保留时间和特征离子定性,外标法定量。结果结果表明20种农药在10～400 ng/mL范围内线性良好,相关系数≥0.99,检出限为0.003～0.082μg/kg,相对标准差(n=6)为3.9%～10.6%,当样品的加标水平为40、100和200μg/kg时,除伏杀硫磷、高效氯氟氰菊酯和溴氰菊酯的回收率偏高,其他17种农药各浓度回收率为83.16%～119.88%。结论该方法操作简单,适用于蜂蜜中多种农药残留的快速检测。
Objective To establish a method for simultaneous determination of 20 kinds of pesticide residues in honey by QuEChERS-gas chromatography-tandem mass spectrometry(GC-MS/MS). Methods Honey samples were extracted into acetonitrile and salted out by anhydrous MgSO_4 and sodium acetate, then cleaned up using the mixture of anhydrous MgSO_4,N-propyl ethylenediamine(PSA) and C_(18) powder as sorbents,and detected by GC-MS/MS using multiple reaction monitoring mode. And samples was qualitied by chromatographic retention time and characteristic parent ion, and then quantified with external standard. Results The 20 pesticides had good linear relationships in the range of 10-400 ng/mL, and the correlation coefficients were not less than 0.99, the limits of detection(R_(S/N)=3) were in the range of 0.003-0.082 μg/kg,with the relative standard deviations of 3.9%-10.6%(n=6),the recoveries of the 17 pesticides at 3 spiked levels of 40, 100 and 200 μg/kg were 83.16%-119.88% except phosalone, lambda-cyhalothrin and deltamethrin. Conclusion This method is simple, which is suitable for rapid detection of pesticide residues in honey.
Objective To establish a method for simultaneous determination of 20 kinds of pesticide residues in honey by QuEChERS-gas chromatography-tandem mass spectrometry(GC-MS/MS). Methods Honey samples were extracted into acetonitrile and salted out by anhydrous MgSO_4 and sodium acetate, then cleaned up using the mixture of anhydrous MgSO_4,N-propyl ethylenediamine(PSA) and C_(18) powder as sorbents,and detected by GC-MS/MS using multiple reaction monitoring mode. And samples was qualitied by chromatographic retention time and characteristic parent ion, and then quantified with external standard. Results The 20 pesticides had good linear relationships in the range of 10-400 ng/mL, and the correlation coefficients were not less than 0.99, the limits of detection(R_(S/N)=3) were in the range of 0.003-0.082 μg/kg,with the relative standard deviations of 3.9%-10.6%(n=6),the recoveries of the 17 pesticides at 3 spiked levels of 40, 100 and 200 μg/kg were 83.16%-119.88% except phosalone, lambda-cyhalothrin and deltamethrin. Conclusion This method is simple, which is suitable for rapid detection of pesticide residues in honey.
引文
[1]中国蜂产品协会.中国蜂蜜产业的现状与发展[R]. 2013.China bee products association. Current situation and development of honey industry in China[R]. 2013.
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[3]黄霞,宋莹,张耀海,等.QuEChERS-GC/MS快速检测柑橘中50种农药残留[J].食品科学,2011,32(18):268.Huang X, Song Y, Zhang YH, et al. Rapid determination of 50 pesticide residues in citrus by QuEChERS-gas chromatography-mass spectrometry[J]. Food Sci, 2011,32(18):268
[4] Anatassiades M, Lehotay SJ, Stajnbaher D, et al. Fast and easy multi-residue method employing acetonitrile extraction/partitioning an"dispersive solid-phase extraction"for the determination of pesticide residues in produce[J]. J AOAC Int, 2003,86(2):412-431.
[5] Majors RE. QuEChERS-a new technique for multi-residue analysis of pesticides in foods and agricultural samples[J]. LC-GC Asia Pacific, 2008,11(1):22-31.
[6]刘亚伟,董一威,孙宝利,等.QuEChERS在食品中农药多残留检测的应用研究进展[J].食品科学,2009, 30(9):288.Liu YW, Dong YW, Sun BL, et al. Summary of application of QuEChERS method in multi-residue determination of pesticides in food[J]. Food Sci, 2009, 30(9):288.
[7]胡西洲,程运斌,胡定金.农药多残留分析中的QuEChERS方法介绍[J].现代农药,2006, 5(4):24-29.Hu XZ, Cheng YB, Hu DJ. Introduce of quick, easy, cheap, effective,rugged and safe(QuEChERS)approach for determination pesticide residues[J]. Mod Pest, 2006,5(4):24-29.
[8] Schenck FJ, Hobb JE. Evaluation of the quick, easy, cheap, effective,rugged, and safe(QuEChERS)approach to pesticide residue analysis[J].Environ Contam Toxicol,2004,73:24-30.
[9]陈舒舒,许凯,徐彦军,等.蜂蜜中氯霉素残留的检测及净化方法研究[J].安全与环境学报,2006, 6(2):92-96.Chen SS, Xu K,Xu YJ,et al. Determination of honey chioramphenicol residue by monolithic column liquid chromatography-mass spectrometry and QuEChERS purifying method[J]. J Saf Environ, 2006,6(2):92-96.
[10]高晓昇,张艳,王松雪,等.牛奶中拟除虫菊酯类农药残留的检测—QuEChERS-气相色谱分析方法的研究与建立[J].中国奶牛,2010,(8):56-60.Gao XS, Zhang Y, Wang SX, et al. Determination of pyrethoid pesicide residues in milk by QuEChERS-gas chromatography[J]. China Dairy Cattle, 2010,(8):56-60.
[11] Antonio V, Luis P, Ana A. Analysis and residue levels of forchlorfenuron(CPPU)in watermelons[J]. J Environ Sci Health B, 2007,(42):801-807.
[12] Lee JM, Park JM, Jang GC. Comparative study of pesticide multi-residue extraction in tobacco for gas chromatography-triple quadrupole mass spectrometry[J]. J Chromatogr A, 2008,1187(1-2):25-33.
[13]郭卫芸,李光辉,杨旗,等.蜂蜜中农药残留研究进展[J].食品研究与开发,2017, 38(23):201-205.Guo WY, Li GH, Yang Q, et al. Progress in the pesticides residue of honey[J]. Food Res Dev, 2017, 38(23):201-205.
[14] Martinez-Vidal JL, Arrebola FJ, et al. Validation of a gas chromatographic-tandem mass spectrometric method for analysis of pesticide residues in six commodities selection of a reference matrix for calibration[J]. Chromatographia, 2004,59(5-6):321-327.
[15] Michelle L, Hladik Kelly L, et al. A multi-residue method for the analysis of pesticides and pesticide degradates in water using HLB solid-phase extraction and gas chromatography-ion trap mass spectrometry[J]. Bull Environ Contam Toxicol, 2008,80(2):139-144.
[16] Sanchez A, Millan S. Quantification of fenitrothion and its main metabolites in poplar leaves by isotope dilution gas chromatography-mass spectrometry coupled with solid-phase microextraction[J]. J Chromatography A, 2008, 1177(1):880-885.
[17]何丽君,陈豪,翁淑琴,等.分散固相萃取技术结合超高效液相色谱-高分辨质谱法测定蜂蜜中三嗪类农药残留[J].中国实验方剂学杂志,2016,(22):71-76.He LJ, Chen H, Weng SQ, et al. Simultaneous determination of triazinc pesticides in honey by using UHPLC-HRMS combined with DSPE[J].Chin J Exp Tradit Med Formul, 2016,(12):71-76.
[18]张烁,陈达炜,赵云峰.超高效液相色谱-高分辨质谱法测定蜂蜜中14种农药残留[J].卫生研究,2015,44(3):422-426,430.Zhang S, Chen DW, Zhao YF. Determination of 14 pesticide residues in honey by ultra high performance liquid chromatography-high resolution mass spectrometry[J]. J Hyg Res, 2015,44(3):422-426,430.
[19]王东,侯传金,赵尔成,等.分散液液微萃取/气相色谱-质谱法测定蜂蜜中六六六和滴滴涕类农药残留[J].色谱,2015,33(1):40-45.Wang D, Hou CJ, Zhao EC, et al. Determination of hexachlorocyclohexane and dichlorodiphenyltrichloroethane residues in honey by gas chromatography-mass spectrometry combined with dispersive liquid-liquid microextraction[J]. Chin J Chromatogr, 2015,33(1):40-45.
[20]王晶.固相微萃取法测定葡萄酒及蜂蜜中多种农药残留的研究[D].秦皇岛:燕山大学,2017.Wang J. Study on the determination of pesticide residues in wine and honey by SPME[D]. Qinhuangdao:Yanshan University, 2017.
[21]范君,刘腾飞,杨代凤,等.不同基质效应对蔬菜种有机磷农药残留检测的影响[J].食品安全质量检测学报,2017, 8(9):3543-3548.Fan J, Liu TF, Yang DF, et al. Influence of different matrix effects on determination of organophosphorus pesticide residues in vegetables[J]. J Food Saf Qual, 2017, 8(9):3543-3548.
[22] Emey DR, Pawlowski TM,Poole CF. Matrix-induced peak enhancement of pesticides in gas chromatogrtaphy:Is there a solution?[J]. J High Resolut Chromatogr, 1997,20(7):375.
[23]陈丽.气相色谱法测定茶叶种有机磷农药残留基质效应的研究及其控制[D].杭州:浙江工业大学,2015.Chen L. The research and control of matrix effects to detect the residues of organophosphorus pesticides in tea by gas chromatography[D]. Hangzhou:Zhejiang University of Technology, 2015
[24] Schenck F, Hobbs J. Evaluation of t he quick, easy, cheap, effective,rugged and safe(QuEChERS)approach to pesticide residue analysis[J].Bull Environ Contam Toxico, 2004, 73(1):24-30.
[25]欧菊芳.蔬菜中农药多残留气相色谱-质谱法测定中的基质效应研究[D].北京:中国农业科学院,2008.Ou JF. Matrix effects in determination of multiresidues of pesticides in vegetables using gas chromatography-mass spectrometry[D]. Beijing:Chinese Academy of Agricultural Sciences, 2008.
[26]张丽莉.茶叶中有机磷农药残留检测技术的改进以及基质效应的研究[D].福州:福建农林大学,2010.Zhang LL. Multiresidue determination of pesticides in tea by gas chromatography and examination on matrix effects[D]. Fuzhou:Fujian Agriculture and Forestry University, 2010.
[27] Urania MS, Ageliki F. Matrix effect in gas chromatographic determination of insecticides and fungicides in vegetables[J]. J Environ Chem, 2004,84(1-3):15-27.
[28] Emey DR, Gillespie AM, Poole CF 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, 1993, 638(1):57-63.
[2]黄永舜.蜂蜜中农药残留的研究进展[J].现代食品,2018,13(24):67.Huang YS. Research progress of pesticide residues in honey[J]. Mod Food, 2018,13(24):67.
[3]黄霞,宋莹,张耀海,等.QuEChERS-GC/MS快速检测柑橘中50种农药残留[J].食品科学,2011,32(18):268.Huang X, Song Y, Zhang YH, et al. Rapid determination of 50 pesticide residues in citrus by QuEChERS-gas chromatography-mass spectrometry[J]. Food Sci, 2011,32(18):268
[4] Anatassiades M, Lehotay SJ, Stajnbaher D, et al. Fast and easy multi-residue method employing acetonitrile extraction/partitioning an"dispersive solid-phase extraction"for the determination of pesticide residues in produce[J]. J AOAC Int, 2003,86(2):412-431.
[5] Majors RE. QuEChERS-a new technique for multi-residue analysis of pesticides in foods and agricultural samples[J]. LC-GC Asia Pacific, 2008,11(1):22-31.
[6]刘亚伟,董一威,孙宝利,等.QuEChERS在食品中农药多残留检测的应用研究进展[J].食品科学,2009, 30(9):288.Liu YW, Dong YW, Sun BL, et al. Summary of application of QuEChERS method in multi-residue determination of pesticides in food[J]. Food Sci, 2009, 30(9):288.
[7]胡西洲,程运斌,胡定金.农药多残留分析中的QuEChERS方法介绍[J].现代农药,2006, 5(4):24-29.Hu XZ, Cheng YB, Hu DJ. Introduce of quick, easy, cheap, effective,rugged and safe(QuEChERS)approach for determination pesticide residues[J]. Mod Pest, 2006,5(4):24-29.
[8] Schenck FJ, Hobb JE. Evaluation of the quick, easy, cheap, effective,rugged, and safe(QuEChERS)approach to pesticide residue analysis[J].Environ Contam Toxicol,2004,73:24-30.
[9]陈舒舒,许凯,徐彦军,等.蜂蜜中氯霉素残留的检测及净化方法研究[J].安全与环境学报,2006, 6(2):92-96.Chen SS, Xu K,Xu YJ,et al. Determination of honey chioramphenicol residue by monolithic column liquid chromatography-mass spectrometry and QuEChERS purifying method[J]. J Saf Environ, 2006,6(2):92-96.
[10]高晓昇,张艳,王松雪,等.牛奶中拟除虫菊酯类农药残留的检测—QuEChERS-气相色谱分析方法的研究与建立[J].中国奶牛,2010,(8):56-60.Gao XS, Zhang Y, Wang SX, et al. Determination of pyrethoid pesicide residues in milk by QuEChERS-gas chromatography[J]. China Dairy Cattle, 2010,(8):56-60.
[11] Antonio V, Luis P, Ana A. Analysis and residue levels of forchlorfenuron(CPPU)in watermelons[J]. J Environ Sci Health B, 2007,(42):801-807.
[12] Lee JM, Park JM, Jang GC. Comparative study of pesticide multi-residue extraction in tobacco for gas chromatography-triple quadrupole mass spectrometry[J]. J Chromatogr A, 2008,1187(1-2):25-33.
[13]郭卫芸,李光辉,杨旗,等.蜂蜜中农药残留研究进展[J].食品研究与开发,2017, 38(23):201-205.Guo WY, Li GH, Yang Q, et al. Progress in the pesticides residue of honey[J]. Food Res Dev, 2017, 38(23):201-205.
[14] Martinez-Vidal JL, Arrebola FJ, et al. Validation of a gas chromatographic-tandem mass spectrometric method for analysis of pesticide residues in six commodities selection of a reference matrix for calibration[J]. Chromatographia, 2004,59(5-6):321-327.
[15] Michelle L, Hladik Kelly L, et al. A multi-residue method for the analysis of pesticides and pesticide degradates in water using HLB solid-phase extraction and gas chromatography-ion trap mass spectrometry[J]. Bull Environ Contam Toxicol, 2008,80(2):139-144.
[16] Sanchez A, Millan S. Quantification of fenitrothion and its main metabolites in poplar leaves by isotope dilution gas chromatography-mass spectrometry coupled with solid-phase microextraction[J]. J Chromatography A, 2008, 1177(1):880-885.
[17]何丽君,陈豪,翁淑琴,等.分散固相萃取技术结合超高效液相色谱-高分辨质谱法测定蜂蜜中三嗪类农药残留[J].中国实验方剂学杂志,2016,(22):71-76.He LJ, Chen H, Weng SQ, et al. Simultaneous determination of triazinc pesticides in honey by using UHPLC-HRMS combined with DSPE[J].Chin J Exp Tradit Med Formul, 2016,(12):71-76.
[18]张烁,陈达炜,赵云峰.超高效液相色谱-高分辨质谱法测定蜂蜜中14种农药残留[J].卫生研究,2015,44(3):422-426,430.Zhang S, Chen DW, Zhao YF. Determination of 14 pesticide residues in honey by ultra high performance liquid chromatography-high resolution mass spectrometry[J]. J Hyg Res, 2015,44(3):422-426,430.
[19]王东,侯传金,赵尔成,等.分散液液微萃取/气相色谱-质谱法测定蜂蜜中六六六和滴滴涕类农药残留[J].色谱,2015,33(1):40-45.Wang D, Hou CJ, Zhao EC, et al. Determination of hexachlorocyclohexane and dichlorodiphenyltrichloroethane residues in honey by gas chromatography-mass spectrometry combined with dispersive liquid-liquid microextraction[J]. Chin J Chromatogr, 2015,33(1):40-45.
[20]王晶.固相微萃取法测定葡萄酒及蜂蜜中多种农药残留的研究[D].秦皇岛:燕山大学,2017.Wang J. Study on the determination of pesticide residues in wine and honey by SPME[D]. Qinhuangdao:Yanshan University, 2017.
[21]范君,刘腾飞,杨代凤,等.不同基质效应对蔬菜种有机磷农药残留检测的影响[J].食品安全质量检测学报,2017, 8(9):3543-3548.Fan J, Liu TF, Yang DF, et al. Influence of different matrix effects on determination of organophosphorus pesticide residues in vegetables[J]. J Food Saf Qual, 2017, 8(9):3543-3548.
[22] Emey DR, Pawlowski TM,Poole CF. Matrix-induced peak enhancement of pesticides in gas chromatogrtaphy:Is there a solution?[J]. J High Resolut Chromatogr, 1997,20(7):375.
[23]陈丽.气相色谱法测定茶叶种有机磷农药残留基质效应的研究及其控制[D].杭州:浙江工业大学,2015.Chen L. The research and control of matrix effects to detect the residues of organophosphorus pesticides in tea by gas chromatography[D]. Hangzhou:Zhejiang University of Technology, 2015
[24] Schenck F, Hobbs J. Evaluation of t he quick, easy, cheap, effective,rugged and safe(QuEChERS)approach to pesticide residue analysis[J].Bull Environ Contam Toxico, 2004, 73(1):24-30.
[25]欧菊芳.蔬菜中农药多残留气相色谱-质谱法测定中的基质效应研究[D].北京:中国农业科学院,2008.Ou JF. Matrix effects in determination of multiresidues of pesticides in vegetables using gas chromatography-mass spectrometry[D]. Beijing:Chinese Academy of Agricultural Sciences, 2008.
[26]张丽莉.茶叶中有机磷农药残留检测技术的改进以及基质效应的研究[D].福州:福建农林大学,2010.Zhang LL. Multiresidue determination of pesticides in tea by gas chromatography and examination on matrix effects[D]. Fuzhou:Fujian Agriculture and Forestry University, 2010.
[27] Urania MS, Ageliki F. Matrix effect in gas chromatographic determination of insecticides and fungicides in vegetables[J]. J Environ Chem, 2004,84(1-3):15-27.
[28] Emey DR, Gillespie AM, Poole CF 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, 1993, 638(1):57-63.