高效液相色谱-电喷雾电离串联质谱法测定植物性食品中氟虫腈及其代谢物的残留
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摘要
建立了高效液相色谱-串联质谱测定植物源食品(菠菜、苹果、香蕉、大米、大豆、茶叶)中的氟虫腈及其代谢物(氟虫腈砜,氟虫腈硫醚,氟甲腈)残留量的检测方法。以QuEChERS(Quick、Easy、Cheap、Effective、Rugged、Safe)提取盐包(CEN EN-15662)提取目标化合物,借助分散固相萃取或固相萃取(GCB/PSA)作为净化手段,经Thermo Accucore aQ(2.6μm,2.1×150 mm)进行高效液相色谱分离,以电喷雾电离串联质谱多反应监测负离子模式进行检测,外标法定量。结果表明:4种分析物在0.1～5.0μg/L范围内线性关系良好,相关系数(R~2)均大于0.999。6种样品基质在3个添加水平(1、2、4μg/kg)下的回收率为91.5%～101.5%,相对标准偏差为0.47%～3.88%;定量限(LOQ)均为0.1μg/kg。该方法步骤简便、可靠、稳定,能满足于目前我国主要贸易国和地区的限量要求。
A methods was developed for the simultaneous determination of fipronil and its metabolites residues in various vegetative foods( such as spinach,apple,banana,rice,soybean and tea) by HPLC-MS/MS. The sample was extracted with acetronitrile by QuEChERS extraction tube( CEN EN-15662),cleaned-up with an d SPE or GCB/PSA solid phase extraction cartridge prior to separate on a Thermo Accucore aQ( 2.6 μm,2.1 × 150 mm),detected by HPLC-MS/MS with multiple reaction monitoring mode. The analyte was quantified by matrix-matched external standard method for fipronil and its metabolites.The results showed that good linearity was obtained when the concentration of the method was within 0.1～5 μg/L.The correlation coefficients( R~2) were greater than 0.999.The average recoveries ranged from 91.5% ～101.5% with the relative standard deviations of 0.47% ～ 3.88% at the spiked levels of 1,2,4 μg/kg for fipronil and its metabolites. The limites of quantitation( LOQ) were 0.1 μg/kg.The methods were simple,sensitive and reliable,and had been applied successfully for the residue determination of fipronil in the real samples.
A methods was developed for the simultaneous determination of fipronil and its metabolites residues in various vegetative foods( such as spinach,apple,banana,rice,soybean and tea) by HPLC-MS/MS. The sample was extracted with acetronitrile by QuEChERS extraction tube( CEN EN-15662),cleaned-up with an d SPE or GCB/PSA solid phase extraction cartridge prior to separate on a Thermo Accucore aQ( 2.6 μm,2.1 × 150 mm),detected by HPLC-MS/MS with multiple reaction monitoring mode. The analyte was quantified by matrix-matched external standard method for fipronil and its metabolites.The results showed that good linearity was obtained when the concentration of the method was within 0.1～5 μg/L.The correlation coefficients( R~2) were greater than 0.999.The average recoveries ranged from 91.5% ～101.5% with the relative standard deviations of 0.47% ～ 3.88% at the spiked levels of 1,2,4 μg/kg for fipronil and its metabolites. The limites of quantitation( LOQ) were 0.1 μg/kg.The methods were simple,sensitive and reliable,and had been applied successfully for the residue determination of fipronil in the real samples.
引文
[1]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.
[2]荣杰峰,韦航,李亦军,等.食品中氟虫腈残留量的检测方法研究进展[J].广州化工,2013,41(8):16-17.
[3]堵燕钰,罗漪涟,王洁琼,等.在线净化-液相色谱串联质谱技术测定蔬菜中氟虫腈及其代谢物残留[J].环境化学,2017,36(4):928-930
[4]中国香港法,食物内除害剂残余规例[S].HK:2014.
[5]中国台湾法,农药残留容许量标准[S].TWN:2013.
[6]Positive list system maximum residue limits(MRLs)list of agricultural chemicals in foods[S].JPN:2006.
[7]付晓芳,林雁飞,李晶,等.茶叶中氟虫腈残留量的检测[J].食品科学,2010,31(10):279-282.
[8]荣杰峰,韦航,许美珠,等.气相色谱-电子轰击源质谱法测定茶叶中氟虫腈残留量[J].分析试验室,2014,33(1):69-72.
[9]胡贝贞,蔡海江,宋伟华,等.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.
[10]达晶,王钢力,曹进,等.QuEChERS-液相色谱-串联质谱法测定植物性食品中30种氨基甲酸酯类农药残留[J].色谱,2015,33(8):830-837.
[11]闫震,聂继云,徐国锋,等.超高效液相色谱-串联质谱法对比4种净化方式对不同色素含量基质中19种农药残留检测的影响[J].分析测试学报,2014(9):1000-1009.
[12]Kadar A,Faucon J P.Determination of traces of fipronil and its metabolites in pollen by liquid chromatography with electrospray ionization-tandem mass spectrometry[J]. Journal of Agriculture Food Chemistry,2005,54:9741-9746.
[13]NEN EN 15662-2008.Foods of plant origin-determination of pesticides residues using gc-ms and/or lc-ms(/ms)following acetonitrile extraction/partitioning and clean-up by dispersive spe-quechers-method[S].EU:2008.
[14]林峰,奚星林,陈捷,等.食品安全分析检测技术[M].北京:化学工业出版社,2015.
[15]SANTE/11945/2015.Guidance document on analytical quality control and method validation procedures for pesticides[S].EU:2015.
[16]GB2763-2016.食品安全国家标准食品中农药最大残留限量[S].CHN:2016.
[2]荣杰峰,韦航,李亦军,等.食品中氟虫腈残留量的检测方法研究进展[J].广州化工,2013,41(8):16-17.
[3]堵燕钰,罗漪涟,王洁琼,等.在线净化-液相色谱串联质谱技术测定蔬菜中氟虫腈及其代谢物残留[J].环境化学,2017,36(4):928-930
[4]中国香港法,食物内除害剂残余规例[S].HK:2014.
[5]中国台湾法,农药残留容许量标准[S].TWN:2013.
[6]Positive list system maximum residue limits(MRLs)list of agricultural chemicals in foods[S].JPN:2006.
[7]付晓芳,林雁飞,李晶,等.茶叶中氟虫腈残留量的检测[J].食品科学,2010,31(10):279-282.
[8]荣杰峰,韦航,许美珠,等.气相色谱-电子轰击源质谱法测定茶叶中氟虫腈残留量[J].分析试验室,2014,33(1):69-72.
[9]胡贝贞,蔡海江,宋伟华,等.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.
[10]达晶,王钢力,曹进,等.QuEChERS-液相色谱-串联质谱法测定植物性食品中30种氨基甲酸酯类农药残留[J].色谱,2015,33(8):830-837.
[11]闫震,聂继云,徐国锋,等.超高效液相色谱-串联质谱法对比4种净化方式对不同色素含量基质中19种农药残留检测的影响[J].分析测试学报,2014(9):1000-1009.
[12]Kadar A,Faucon J P.Determination of traces of fipronil and its metabolites in pollen by liquid chromatography with electrospray ionization-tandem mass spectrometry[J]. Journal of Agriculture Food Chemistry,2005,54:9741-9746.
[13]NEN EN 15662-2008.Foods of plant origin-determination of pesticides residues using gc-ms and/or lc-ms(/ms)following acetonitrile extraction/partitioning and clean-up by dispersive spe-quechers-method[S].EU:2008.
[14]林峰,奚星林,陈捷,等.食品安全分析检测技术[M].北京:化学工业出版社,2015.
[15]SANTE/11945/2015.Guidance document on analytical quality control and method validation procedures for pesticides[S].EU:2015.
[16]GB2763-2016.食品安全国家标准食品中农药最大残留限量[S].CHN:2016.