QuEChERS-超高效液相色谱-串联质谱法测定鸡蛋、鸡肉中氟虫腈及其代谢物残留
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摘要
建立一种基于QuEChERS法提取,超高效液相色谱分离,串联四极杆质谱法检测鸡蛋、鸡肉中氟虫腈及其代谢物残留量的方法。样品经加水分散后,用乙腈提取,柠檬酸缓冲盐脱水,稀释后上机测定。待测物经BEH C_(18)色谱柱分离,以甲醇-5 mmol/L乙酸铵溶液(含0.1%甲酸)进行梯度洗脱,质谱法采用电喷雾电离,负离子多反应监测模式检测。基质加标曲线定量。氟虫腈及3种代谢物的定量限为1μg/kg,在1～100μg/kg范围内线性关系良好。在鸡蛋、鸡肉基质中3个不同添加水平下,平均回收率为87.6%～117.7%,变异系数为3.6%～9.9%。该方法快速、灵敏、准确,适合作为禽蛋等动物源性食品中,氟虫腈及其代谢物残留总量的测定。
A method for the determination of fipronil and its metabolites residues in chicken eggs and meat by quick easy cheap effective rugged safe (QuEChERS) extraction coupled with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established. Samples were dispersed in water and extracted with acetonitrile, followed by dehydration with citrate buffer. The extract was diluted before being injected. The analytes were separated on a BEH C_(18) column with gradient elution using a mobile phase made up of methanol and 5 mmol/L ammonium acetate (containing 0.1% formic acid). The MS analysis was performed using an electrospray ionization (ESI) source in the negative mode with multiple reaction monitoring (MRM). Quantification was performed with matrix-matched standard calibration curves. The limits of quantitation (LOQs) of fipronil and 3 metabolites were all 1 μg/kg. In the concentration range of 1 to 100 μg/kg, all the calibration curves showed good linear correlation. The average recoveries for chicken egg and meat at three different spiked levels were 87.6%–117.7%, with relative standard deviations (RSDs) between 3.6% and 9.9%. The method is rapid, sensitive and accurate, and it is suitable for the determination of fipronil and its metabolites residues in animal-derived food s such as chicken eggs and meat.
A method for the determination of fipronil and its metabolites residues in chicken eggs and meat by quick easy cheap effective rugged safe (QuEChERS) extraction coupled with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established. Samples were dispersed in water and extracted with acetonitrile, followed by dehydration with citrate buffer. The extract was diluted before being injected. The analytes were separated on a BEH C_(18) column with gradient elution using a mobile phase made up of methanol and 5 mmol/L ammonium acetate (containing 0.1% formic acid). The MS analysis was performed using an electrospray ionization (ESI) source in the negative mode with multiple reaction monitoring (MRM). Quantification was performed with matrix-matched standard calibration curves. The limits of quantitation (LOQs) of fipronil and 3 metabolites were all 1 μg/kg. In the concentration range of 1 to 100 μg/kg, all the calibration curves showed good linear correlation. The average recoveries for chicken egg and meat at three different spiked levels were 87.6%–117.7%, with relative standard deviations (RSDs) between 3.6% and 9.9%. The method is rapid, sensitive and accurate, and it is suitable for the determination of fipronil and its metabolites residues in animal-derived food s such as chicken eggs and meat.
引文
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[19]叶倩,邓义才,梁应坤,等.气相色谱-质谱法(GC-MS)测定蔬菜水果中氟虫腈及其代谢物残留[J].农药,2017,56(3):203-206.DOI:10.16820/j.cnki.1006-0413.2017.03.013.
[20]林涛,樊建麟,杨东顺,等.固相萃取-超高效液相色谱-串联质谱法测定普洱茶中氟虫腈及其类似物残留[J].农药,2015,54(11):814-817.
[21]成婧,王美玲,朱绍华,等.固相萃取-高效液相色谱-串联质谱法测定茶叶中啶虫眯、吡虫啉和氟虫腈残留量[J].食品安全质量检测学报,2016,7(1):131-137.
[22]吴成,任海雷,赵志强,等.液相色谱-串联质谱法检测芹菜中氟虫腈及其代谢物残留[J].福建分析测试,2016,25(5):37-41.DOI:10.3969/j.issn.1009-8143.2016.05.07.
[23]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.
[24]CHENG Y P,DONG F S,LIU X G,et al.Simultaneous determination of fipronil and its major metabolites in corn and soil by ultraperformance liquid chromatography-tandem mass spectrometry[J].Analytical Methods,2014,6(6):1788-1795.DOI:10.1039/c3ay41742e.
[25]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.DOI:10.3724/SP.J.1123.2011.00656.
[26]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 Agricultural and Food Chemistry,2006,54(26):9741-9746.DOI:10.1021/jf062035.
[27]TOMASINI D,SAMPAIO M R F,CARDOSO L V,et al.Comparison of dispersive liquid-liquid microextraction and the modified QuEChERS method for the determination of fipronil in honey by high performance liquid chromatography with diode-array detection[J].Analytical Methods,2011,3:1893-1900.DOI:10.1039/C1AY05221G.
[28]LI M H,LI P Y,WANG L,et al.Determination and dissipation of fipronil and its metabolites in peanut and soil[J].Journal of Agricultural and Food Chemistry,2014,63(18):4435-4443.DOI:10.1021/jf5054589.
[29]ZHANG M Y,BIAN K,ZHOU T,et al.Determination of residual fipronil in chicken egg and muscle by LC-MS/MS[J].Journal of Chromatography B,2016,1014:31-36.DOI:10.1016/j.jchromb.2016.01.041.
[30]ANASTASSIADES M,LEHOTAY S J.Fast and easy multiresidue method employing acetonitrile extraction/partitioning and“dispersive solid-phase extraction”for the determination of pesticide residues in produce[J].Journal of AOAC International,2003,86(2):412-431.
[31]GOSETTI F,MAZZUCCO E,ZAMPIERI D,et al.Signal suppression/enhancement in high-performance liquid chromatography tandem mass spectrometry[J].Journal of Chromatography A,2010,1217:3929-3937.DOI:10.1016/j.chroma.2009.11.060.
[32]国家质量监督检验检疫总局.实验室质量控制规范食品理化检验:GB/T 27404-2008[S].北京:中国标准出版社,2008:26-27.
[2]张芳芳,孙建析,朱勇,等.氟虫腈原药的毒性鉴定[J].毒理学杂志,2008,22(3):246-247.
[3]BOBE A,COSTE C M,COOPER J F.Factors influencing the adsorption of fipronil on soils[J].Journal of Agricultural and Food Chemistry,1997,45(12):4861-4865.DOI:10.1021/jf970362z.
[4]徐广春,顾中言,杨玉清,等.氟虫腈的应用和风险研究进展[J].现代农药,2008,7(2):1-5.
[5]陈叶娜.杀虫剂氟虫腈的合成研究进展[J].广州华工,2009,37(2):48-49.
[6]BOBE A,MEALLIER P,COOPER J F,et al.Kinetics and mechanisms of abiotic degradation of fipronil[J].Journal of Agricultural and Food Chemistry,1998,46(7):2834-2839.DOI:10.1021/jf970874d.
[7]AAJOUD A,RAVANEL P,TISSUT M.Fipronil metabolism and dissipation in a simplified aquatic ecosystem[J].Journal of Agricultural and Food Chemistry,2003,51(5):1347-1352.DOI:10.1021/jf025843j.
[8]杨莉,房晓敏,陈伟,等.5-氨基吡唑类农药的研究进展[J].世界农药,2013,35(4):10-15.
[9]张祥丹,刘国光.锐劲特在环境中的降解及其毒理学研究进展[J].环境与健康杂志,2009,26(8):749-751.DOI:10.16241/j.cnki.1001-5914.2009.08.008.
[10]崔新仪,储晓刚,王大宁.氟虫腈及其代谢物的研究进展[J].农药,2008,47(2):87-89.
[11]农业部.中华人民共和国农业部公告第1157号[EB/OL].(2009-02-08)[2017-08-23].http://www.moa.gov.cn/zwllm/tzgg/gg/200902/t20090227_1226994.htm.
[12]国家卫生和计划生育委员会.食品中农药最大残留限量:G B2763-2016[S].北京:中国标准出版社,2016:71.
[13]EU Pesticide database.Current MRL values fipronil[EB/OL].(2016-07-04)[2017-08-23].http://ec.europa.eu/food/plant/pesticides/eupesticides-database/public/?event=pesticide.residue.CurrentMRL&lan guage=EN&pestResidueId=302.
[14]任彦,暨佩娟.欧洲“毒鸡蛋”风波持续发酵[N].人民日报,2017-08-14(021).
[15]SANCHEZ-BRUNETE C,MIGUEL E,ALBERO B,et al.Determination of fipronil residues in honey and pollen by gas chromatography[J].Spanish Journal of Agricultural Research,2008,6(Special issue):7-14.DOI:10.5424/sjar/200806S1-368.
[16]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定西氟虫腈的残留[J].农药,2014,53(12):904-905.
[17]KAUR R,MANDAL K KUMAR R,et al.Analytical method for determination of fipronil and its metabolites in vegetables using the QuEChERS method and gas chromatography/mass spectrometry[J].Jouranl of AOAC International,2015,98(2):464-471.DOI:10.5740/jaoacint.13-066.
[18]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.DOI:10.3724/SP.J.1123.2012.10003.
[19]叶倩,邓义才,梁应坤,等.气相色谱-质谱法(GC-MS)测定蔬菜水果中氟虫腈及其代谢物残留[J].农药,2017,56(3):203-206.DOI:10.16820/j.cnki.1006-0413.2017.03.013.
[20]林涛,樊建麟,杨东顺,等.固相萃取-超高效液相色谱-串联质谱法测定普洱茶中氟虫腈及其类似物残留[J].农药,2015,54(11):814-817.
[21]成婧,王美玲,朱绍华,等.固相萃取-高效液相色谱-串联质谱法测定茶叶中啶虫眯、吡虫啉和氟虫腈残留量[J].食品安全质量检测学报,2016,7(1):131-137.
[22]吴成,任海雷,赵志强,等.液相色谱-串联质谱法检测芹菜中氟虫腈及其代谢物残留[J].福建分析测试,2016,25(5):37-41.DOI:10.3969/j.issn.1009-8143.2016.05.07.
[23]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.
[24]CHENG Y P,DONG F S,LIU X G,et al.Simultaneous determination of fipronil and its major metabolites in corn and soil by ultraperformance liquid chromatography-tandem mass spectrometry[J].Analytical Methods,2014,6(6):1788-1795.DOI:10.1039/c3ay41742e.
[25]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.DOI:10.3724/SP.J.1123.2011.00656.
[26]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 Agricultural and Food Chemistry,2006,54(26):9741-9746.DOI:10.1021/jf062035.
[27]TOMASINI D,SAMPAIO M R F,CARDOSO L V,et al.Comparison of dispersive liquid-liquid microextraction and the modified QuEChERS method for the determination of fipronil in honey by high performance liquid chromatography with diode-array detection[J].Analytical Methods,2011,3:1893-1900.DOI:10.1039/C1AY05221G.
[28]LI M H,LI P Y,WANG L,et al.Determination and dissipation of fipronil and its metabolites in peanut and soil[J].Journal of Agricultural and Food Chemistry,2014,63(18):4435-4443.DOI:10.1021/jf5054589.
[29]ZHANG M Y,BIAN K,ZHOU T,et al.Determination of residual fipronil in chicken egg and muscle by LC-MS/MS[J].Journal of Chromatography B,2016,1014:31-36.DOI:10.1016/j.jchromb.2016.01.041.
[30]ANASTASSIADES M,LEHOTAY S J.Fast and easy multiresidue method employing acetonitrile extraction/partitioning and“dispersive solid-phase extraction”for the determination of pesticide residues in produce[J].Journal of AOAC International,2003,86(2):412-431.
[31]GOSETTI F,MAZZUCCO E,ZAMPIERI D,et al.Signal suppression/enhancement in high-performance liquid chromatography tandem mass spectrometry[J].Journal of Chromatography A,2010,1217:3929-3937.DOI:10.1016/j.chroma.2009.11.060.
[32]国家质量监督检验检疫总局.实验室质量控制规范食品理化检验:GB/T 27404-2008[S].北京:中国标准出版社,2008:26-27.