气相色谱-串联质谱法测定蛋和蛋制品中氟虫腈及其代谢物残留量
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摘要
建立了气相色谱-串联质谱法(GC-MS/MS)检测蛋和蛋制品中氟虫腈及其代谢物氟甲腈、氟虫腈硫醚和氟虫腈砜的残留量。蛋和蛋制品经水稀释,涡旋混合均匀;加入0.1%冰醋酸-乙腈溶液和氯化钠,经充分涡旋和振摇后,对样品进行超声提取、离心、提取上层清液;残渣用0.1%冰醋酸-乙腈溶液再提取1次,合并2次提取得到的上清液,浓缩;用乙腈溶解残渣,分散固相萃取(N-丙基乙二胺、石墨化碳黑和十八烷基硅烷)净化后,用气相色谱-串联质谱法测定,外标法定量;同时对提取溶剂、提取方式和分散固相萃取剂进行了优化。结果表明:4种化合物在2～100μg/L范围内的线性关系良好,相关系数R2大于0.99,定量限为1.0μg/kg。在1.0、2.0、4.0、20.0μg/kg加标水平下,氟虫腈及其代谢物的回收率为72.0%～109.5%,相对标准偏差小于16.0%。该方法准确、简单、快速,可用于蛋及蛋制品中氟虫腈及其代谢物的同时测定。
Fipronil and its metabolite residues(fipronil-desulfinyl,fipronil sulfide and fipronil sulfone)in eggs and egg products were detected by gas chromatography-tandem mass spectrometry(GC-MS/MS).The samples were diluted by water,and vortexed to mix uniformity.Then acetonitrile containing 0.1% acetic acid was added,followed by sodium chloride.After vortexing and shaking vigorously,the samples were ultrasonic extracted.Then the samples were centrifuged,and the supernatant layer was taken.Then residues were extracted by acetonitrile containing 0.1% acetic acid again.The supernatant layer of twice extraction was put together and evaporated to dryness.Then acetonitrile was added to dissolve the residue.This solution was cleaned up by dispersive solid phase extraction powder(primary secondary amine,graphitized carbon black and eighteen alkyl silane),then was analyzed by GC-MS/MS.The extraction solvent(ethyl acetate,acetone,acetonitrile and acetonitrile containing 0.1%glacial acetic acid)and extraction mode(shaking,vortexing ultrasonic and oscillation)were optimized.The optimization of dispersive-solid phase extraction powders was carried out by orthogonal experiment.The matrix effects of four compounds in eggs and egg products were definitely declined by the purification of dispersive-solid phase extraction.The quantification was carried out by external standard method of matrix calibration curve.The linear ranges of four compounds are 2-100μg/L with the correlation coefficients more than0.99.The limits of quantification of four compounds are 1.0μg/kg.At four spiked concentration levels of 1.0,2.0,4.0 and 20.0μg/kg,the recoveries are 72.0%-109.5% with the relative standard deviations(RSDs)less than 16.0%.This method is accurate,simple,quick,and suitable for simultaneous determination of fipronil and its metabolite residues in eggs and egg products.
Fipronil and its metabolite residues(fipronil-desulfinyl,fipronil sulfide and fipronil sulfone)in eggs and egg products were detected by gas chromatography-tandem mass spectrometry(GC-MS/MS).The samples were diluted by water,and vortexed to mix uniformity.Then acetonitrile containing 0.1% acetic acid was added,followed by sodium chloride.After vortexing and shaking vigorously,the samples were ultrasonic extracted.Then the samples were centrifuged,and the supernatant layer was taken.Then residues were extracted by acetonitrile containing 0.1% acetic acid again.The supernatant layer of twice extraction was put together and evaporated to dryness.Then acetonitrile was added to dissolve the residue.This solution was cleaned up by dispersive solid phase extraction powder(primary secondary amine,graphitized carbon black and eighteen alkyl silane),then was analyzed by GC-MS/MS.The extraction solvent(ethyl acetate,acetone,acetonitrile and acetonitrile containing 0.1%glacial acetic acid)and extraction mode(shaking,vortexing ultrasonic and oscillation)were optimized.The optimization of dispersive-solid phase extraction powders was carried out by orthogonal experiment.The matrix effects of four compounds in eggs and egg products were definitely declined by the purification of dispersive-solid phase extraction.The quantification was carried out by external standard method of matrix calibration curve.The linear ranges of four compounds are 2-100μg/L with the correlation coefficients more than0.99.The limits of quantification of four compounds are 1.0μg/kg.At four spiked concentration levels of 1.0,2.0,4.0 and 20.0μg/kg,the recoveries are 72.0%-109.5% with the relative standard deviations(RSDs)less than 16.0%.This method is accurate,simple,quick,and suitable for simultaneous determination of fipronil and its metabolite residues in eggs and egg products.
引文
[1]任彦.“毒鸡蛋”风波敲响欧洲食品安全警钟[EB/OL].[2017-08-05].http:∥m.people.cn/n4/2017/0805/c3549-9658138.html.
[2]刘长令.世界农药大全杀虫剂卷[M].北京:化学工业出版社,2012.
[3]朱国念,吴金涛,刘乾开,等.氟虫腈在模拟稻田渗透系中降解途径的研究[J].农药学学报,2000,2(6):52-56.ZHU Guonian,WU Jintao,LIU Qiankai,et al.Degradative routes of fipronil in the model paddy field ecosystem[J].Chinese Journal of Pesticide Science,2000,2(6):52-56(in Chinese).
[4]EU Pesticides database[EB/OL].[2018-03-12].http:∥ec.europa.eu/food/plant/pesticides/eupesticides-database/public/?event=pesticide.residue.selection&language=EN.
[5]Positive list system for agricultural chemical residues in foods[EB/OL].[2018-03-12].http:∥www.m5.ws001.squarestart.ne.jp/foundation/search.html.
[6]中华人民共和国农业部工业和信息化部环境保护部第1157号公告[EB/OL].http:∥jiuban.moa.gov.cn/zwllm/tzgg/gg/200902/t20090227_1226994.html.
[7]GB 2763-2016.食品安全国家标准食品中农药最大残留限量[S].北京:中国标准出版社,2016.
[8]SN/T 1982-2007.进出口食品中氟虫腈残留量检测方法气相色谱-质谱法[S].北京:中国标准出版社,2007.
[9]SN/T 4039-2014.出口食品中萘乙酰胺、吡草醚、乙虫腈、氟虫腈残留量的测定方法液相色谱-质谱/质谱法[S].北京:中国标准出版社,2014.
[10]GB 23200.8-2016.水果和蔬菜中500种农药及相关化学品残留量的测定气相色谱-质谱法[S].北京:中国标准出版社,2016.
[11]GB 23200.9-2016.粮谷中475种农药及相关化学品残留量的测定气相色谱-质谱法[S].北京:中国标准出版社,2016.
[12]GB 23200.7-2016.蜂蜜、果汁和果酒中497种农药及相关化学品残留量的测定气相色谱-质谱法[S].北京:中国标准出版社,2016.
[13]ZHOU P,LU Y T,LIU B F,et al.Dynamics of fipronil residue in vegetable-field ecosystem[J].Chemosphere,2004,57(11):1 691-1 696.
[14]周昱,徐敦明,陈达捷,等.固相微萃取-气相色谱法和气相色谱-质谱法测定茶叶中氟虫腈及其代谢物残留[J].色谱,2011,29(7):656-661.ZHOU Yu,XU Dunming,CHEN Dajie,et al.Determination of fipronil and its metabolites in tea by solid-phase microextraction coupled with gas chromatography and gas chromatographymass spectrometry[J].Chinese Journal of Chromatography,2011,29(7):656-661(in Chinese).
[15]徐敦明,卢声宇,陈达捷,等.加速溶剂萃取-气相色谱-串联质谱法测定茶叶中10种吡唑和吡咯类农药的残留量[J].色谱,2013,31(3):218-222.XU Dunming,LU Shengyu,CHEN Dajie,et al.Determination of ten pesticides of pyrazoles and pyrroles in tea by accelerated solvent extraction coupled with gas chromatography-tandem mass spectrometry[J].Chinese Journal of Chromatography,2013,31(3):218-222(in Chinese).
[16]丁立平,刘微,方光伟,等.改进QuChERS-气质联用法测定蔬菜中氟虫腈和丁烯氟虫腈残留量[J].分析试验室,2013,32(8):117-120.DING Liping,LIU Wei,FANG Guangwei,et al.Determination of fipronil and butane-fipronil residues in vegetable by improved QuChERS-GC/MS[J].Chinese Journal of Analysis Laboratory,2013,32(8):117-120(in Chinese).
[17]胡贝贞,蔡海江,宋伟华.茶叶中氟虫腈等8种农药残留的液相色谱-串联质谱法测定及不确定度评定[J].色谱,2012,30(9):889-895.HU Beizhen,CAI Haijiang,SONG Weihua.Determination of eight pesticide residues in tea by liquid chromatography-tandem mass spectrometry and its uncertainty evaluation[J].Chinese Journal of Chromatography,2012,30(9):889-895(in Chinese).
[18]林涛,樊建麟,杨东顺,等.低温液液萃取/超高效液相色谱-串联质谱法快速测定鲜枣中氟虫腈及代谢物[J].分析测试学报,2015,34(12):1 360-1 365.LIN Tao,FAN Jianlin,YANG Dongshun,et al.Determination of fipronil and its metabolites in fresh jujube by low temperature liquid-liquid extraction/ultra high liquid chromatography-tandem mass spectrometry[J].Journal of Instrumentan Analysis,2015,34(12):1 360-1 365(in Chinese).
[19]LACROIX M Z,PUEL S,TOUTAN P L,et al.Quantification of fipronil and its metabolite fipronil sulfone in rat plasma over a wide range of concentrations by LC/UV/MS[J].Journal of Chromatography B,2010,878(22):1 934-1 938.
[20]MCMAHEN R L,STRYNAR M J,DAGNINOS,et al.Identification of fipronil metabolites by time-of-flight mass spectrometry for application in a human exposure study[J].Environment International,2015,78:16-23.
[21]陈志涛,丁立平,吴文凡,等.分散固相萃取-气相色谱法测定水产品中氟虫腈和丁烯氟虫腈的残留[J].农药,2014,53(12):904-906.CHEN Zhitao,DING Liping,WU Wenfan,et al.Determination of fipronil and flufiprole residues in aquatic products by GC with dispersive solid phase extraction[J].Agrochemicals,2014,53(12):904-906(in Chinese).
[22]陈珊珊,丁丞,郭立新,等.气相色谱-负化学电离-质谱联用技术检测痕量氟虫腈及代谢物的漂移对池塘水和虾体的影响[J].质谱学报,2013,34(5):274-281.CHEN Shanshan,DING Cheng,GUO Lixin,et al.The influence of fipronil and its metabolites drift in water pond and shrimp using GC-NCI/MS[J].Journal of Chinese Mass Spectrometry Society,2013,34(5):274-281(in Chinese).
[23]时逸吟,李优,伊雄海,等.液相色谱-串联质谱法测定蛋及蛋制品中氟虫腈及其代谢物的残留量[J].检验检疫学刊,2017,27(5):1-7.SHI Yiyin,LI You,YI Xionghai,et al.Determination of fipronil and its metabolites in egg and egg products by liquid chromatography-tandem mass spectrometry[J].Journal of Inspection and Quarantine,2017,27(5):1-7(in Chinese).
[24]沈伟健,柳菡,张睿,等.气相色谱-负化学源质谱法测定禽蛋及蛋制品中氟虫腈及其代谢物[J].色谱,2017,35(12):1 224-1 228.SHEN Weijian,LIU Han,ZHANG Rui,et al.Determination of fipronil and its metabolites in eggs and egg products with gas chromatographynegative chemical ionization-mass spectrometry[J].Chinese Journal of Chromatography,2017,35(12):1 224-1 228(in Chinese).
[25]郭德华,时逸吟,李优,等.固相萃取-液相色谱-四级杆飞行时间质谱法快速筛查禽蛋及蛋制品中氟虫腈及其代谢物[J].色谱,2017,35(12):1 216-1 223.GUO Dehua,SHI Yiyin,LI You,et al.Rapid screening of fipronil and its metabolites in egg and egg productis by solid phase extraction-liquid chromatography-quadrupole time-of-flight mass spectrometry[J].Chinese Journal of Chromatography,2017,35(12):1 216-1 223(in Chinese).
[26]LEHOTAY S J.Quick,easy,cheap,effective,rugged and safe approach for determining pesticide residues[J].Methods in Biotechnology,2006,19:239-260.
[2]刘长令.世界农药大全杀虫剂卷[M].北京:化学工业出版社,2012.
[3]朱国念,吴金涛,刘乾开,等.氟虫腈在模拟稻田渗透系中降解途径的研究[J].农药学学报,2000,2(6):52-56.ZHU Guonian,WU Jintao,LIU Qiankai,et al.Degradative routes of fipronil in the model paddy field ecosystem[J].Chinese Journal of Pesticide Science,2000,2(6):52-56(in Chinese).
[4]EU Pesticides database[EB/OL].[2018-03-12].http:∥ec.europa.eu/food/plant/pesticides/eupesticides-database/public/?event=pesticide.residue.selection&language=EN.
[5]Positive list system for agricultural chemical residues in foods[EB/OL].[2018-03-12].http:∥www.m5.ws001.squarestart.ne.jp/foundation/search.html.
[6]中华人民共和国农业部工业和信息化部环境保护部第1157号公告[EB/OL].http:∥jiuban.moa.gov.cn/zwllm/tzgg/gg/200902/t20090227_1226994.html.
[7]GB 2763-2016.食品安全国家标准食品中农药最大残留限量[S].北京:中国标准出版社,2016.
[8]SN/T 1982-2007.进出口食品中氟虫腈残留量检测方法气相色谱-质谱法[S].北京:中国标准出版社,2007.
[9]SN/T 4039-2014.出口食品中萘乙酰胺、吡草醚、乙虫腈、氟虫腈残留量的测定方法液相色谱-质谱/质谱法[S].北京:中国标准出版社,2014.
[10]GB 23200.8-2016.水果和蔬菜中500种农药及相关化学品残留量的测定气相色谱-质谱法[S].北京:中国标准出版社,2016.
[11]GB 23200.9-2016.粮谷中475种农药及相关化学品残留量的测定气相色谱-质谱法[S].北京:中国标准出版社,2016.
[12]GB 23200.7-2016.蜂蜜、果汁和果酒中497种农药及相关化学品残留量的测定气相色谱-质谱法[S].北京:中国标准出版社,2016.
[13]ZHOU P,LU Y T,LIU B F,et al.Dynamics of fipronil residue in vegetable-field ecosystem[J].Chemosphere,2004,57(11):1 691-1 696.
[14]周昱,徐敦明,陈达捷,等.固相微萃取-气相色谱法和气相色谱-质谱法测定茶叶中氟虫腈及其代谢物残留[J].色谱,2011,29(7):656-661.ZHOU Yu,XU Dunming,CHEN Dajie,et al.Determination of fipronil and its metabolites in tea by solid-phase microextraction coupled with gas chromatography and gas chromatographymass spectrometry[J].Chinese Journal of Chromatography,2011,29(7):656-661(in Chinese).
[15]徐敦明,卢声宇,陈达捷,等.加速溶剂萃取-气相色谱-串联质谱法测定茶叶中10种吡唑和吡咯类农药的残留量[J].色谱,2013,31(3):218-222.XU Dunming,LU Shengyu,CHEN Dajie,et al.Determination of ten pesticides of pyrazoles and pyrroles in tea by accelerated solvent extraction coupled with gas chromatography-tandem mass spectrometry[J].Chinese Journal of Chromatography,2013,31(3):218-222(in Chinese).
[16]丁立平,刘微,方光伟,等.改进QuChERS-气质联用法测定蔬菜中氟虫腈和丁烯氟虫腈残留量[J].分析试验室,2013,32(8):117-120.DING Liping,LIU Wei,FANG Guangwei,et al.Determination of fipronil and butane-fipronil residues in vegetable by improved QuChERS-GC/MS[J].Chinese Journal of Analysis Laboratory,2013,32(8):117-120(in Chinese).
[17]胡贝贞,蔡海江,宋伟华.茶叶中氟虫腈等8种农药残留的液相色谱-串联质谱法测定及不确定度评定[J].色谱,2012,30(9):889-895.HU Beizhen,CAI Haijiang,SONG Weihua.Determination of eight pesticide residues in tea by liquid chromatography-tandem mass spectrometry and its uncertainty evaluation[J].Chinese Journal of Chromatography,2012,30(9):889-895(in Chinese).
[18]林涛,樊建麟,杨东顺,等.低温液液萃取/超高效液相色谱-串联质谱法快速测定鲜枣中氟虫腈及代谢物[J].分析测试学报,2015,34(12):1 360-1 365.LIN Tao,FAN Jianlin,YANG Dongshun,et al.Determination of fipronil and its metabolites in fresh jujube by low temperature liquid-liquid extraction/ultra high liquid chromatography-tandem mass spectrometry[J].Journal of Instrumentan Analysis,2015,34(12):1 360-1 365(in Chinese).
[19]LACROIX M Z,PUEL S,TOUTAN P L,et al.Quantification of fipronil and its metabolite fipronil sulfone in rat plasma over a wide range of concentrations by LC/UV/MS[J].Journal of Chromatography B,2010,878(22):1 934-1 938.
[20]MCMAHEN R L,STRYNAR M J,DAGNINOS,et al.Identification of fipronil metabolites by time-of-flight mass spectrometry for application in a human exposure study[J].Environment International,2015,78:16-23.
[21]陈志涛,丁立平,吴文凡,等.分散固相萃取-气相色谱法测定水产品中氟虫腈和丁烯氟虫腈的残留[J].农药,2014,53(12):904-906.CHEN Zhitao,DING Liping,WU Wenfan,et al.Determination of fipronil and flufiprole residues in aquatic products by GC with dispersive solid phase extraction[J].Agrochemicals,2014,53(12):904-906(in Chinese).
[22]陈珊珊,丁丞,郭立新,等.气相色谱-负化学电离-质谱联用技术检测痕量氟虫腈及代谢物的漂移对池塘水和虾体的影响[J].质谱学报,2013,34(5):274-281.CHEN Shanshan,DING Cheng,GUO Lixin,et al.The influence of fipronil and its metabolites drift in water pond and shrimp using GC-NCI/MS[J].Journal of Chinese Mass Spectrometry Society,2013,34(5):274-281(in Chinese).
[23]时逸吟,李优,伊雄海,等.液相色谱-串联质谱法测定蛋及蛋制品中氟虫腈及其代谢物的残留量[J].检验检疫学刊,2017,27(5):1-7.SHI Yiyin,LI You,YI Xionghai,et al.Determination of fipronil and its metabolites in egg and egg products by liquid chromatography-tandem mass spectrometry[J].Journal of Inspection and Quarantine,2017,27(5):1-7(in Chinese).
[24]沈伟健,柳菡,张睿,等.气相色谱-负化学源质谱法测定禽蛋及蛋制品中氟虫腈及其代谢物[J].色谱,2017,35(12):1 224-1 228.SHEN Weijian,LIU Han,ZHANG Rui,et al.Determination of fipronil and its metabolites in eggs and egg products with gas chromatographynegative chemical ionization-mass spectrometry[J].Chinese Journal of Chromatography,2017,35(12):1 224-1 228(in Chinese).
[25]郭德华,时逸吟,李优,等.固相萃取-液相色谱-四级杆飞行时间质谱法快速筛查禽蛋及蛋制品中氟虫腈及其代谢物[J].色谱,2017,35(12):1 216-1 223.GUO Dehua,SHI Yiyin,LI You,et al.Rapid screening of fipronil and its metabolites in egg and egg productis by solid phase extraction-liquid chromatography-quadrupole time-of-flight mass spectrometry[J].Chinese Journal of Chromatography,2017,35(12):1 216-1 223(in Chinese).
[26]LEHOTAY S J.Quick,easy,cheap,effective,rugged and safe approach for determining pesticide residues[J].Methods in Biotechnology,2006,19:239-260.