固相萃取-液相色谱-四极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

Rapid screening of fipronil and its metabolites in egg and egg products by solid phase extraction-liquid chromatography-quadrupole time-of-flight mass spectrometry

建立了液相色谱-四极杆飞行时间质谱(LC-QTOF MS)测定禽蛋及蛋制品中氟虫腈及其代谢物的快速筛查方法。样品经酸性乙腈提取,PRiME HLB SPE柱净化,Poroshell 120 EC C18色谱柱(150 mm×3 mm,2.7μm)分离,以水-乙腈为流动相,梯度洗脱,负离子模式下测定,以乙虫腈为内标定量。实验中建立了一级精确质量和二级碎片离子质谱数据库,并且对4种禽蛋及蛋制品的基质效应进行了考察。结果表明,氟虫腈及其代谢物在0.1~5μg/L范围内线性关系良好,相关系数(r2)均大于0.99。方法的检出限(LOD,S/N>3)和定量限(LOQ,S/N>10)分别为0.2μg/kg和1μg/kg。在不同基质中,氟虫腈及其代谢物在1、2和5μg/kg的添加水平下平均加标回收率为82.6%~98.1%,相对标准偏差为3.8%~9.9%(n=6)。该方法有效消除了液相色谱-四极杆飞行时间质谱检测过程中的离子化抑制效应,灵敏度和准确度高,适用于鸡蛋、鸡蛋面、蛋糕和蛋黄酱中氟虫腈、氟虫腈砜、氟虫腈亚砜和氟甲腈的快速筛查。

A method for rapid screening of fipronil and its metabolites in egg and egg products was developed by liquid chromatography coupled with quadrupole time-of-flight mass spectrometry(LC-QTOF MS).The samples were extracted by acid-acetonitrile,cleaned up by PRiME HLB SPE.The separation was performed on a Poroshell120EC C18column(150mmx3mm,2.7pm)with gradient elution using water and acetonitrile as mobile phases.The target compounds were monitored under negative ionization mode with electrospray ionization(ESI)source and two databases of accurate mass and fragment ions were created.The matrix effects in four kinds of egg and egg products were considered and the quantification was carried out by internal standard method.The results demonstrated that the linear ranges were from0.1to5pg/L with good correlation coefficients(r2>0.99).The limits of detection(LODs,S/N>3)and limits of quantitation(LOQs,S/N>10)were0.2pg/kg and1pg/k g,respectively.The recoveriesof fipronil and its metabolites in different matrixes spiked with1,2and5pg/kg varied from82.6%-98.1%,and the relative standard deviations(RSDs)were between3.8%-9.9%(n=6).The method can effectively correct the ionization suppression.It is sensitive,accurate and suitable for the rapid screening of fipronil,fipronil sulfide,fipronil sulfone and fipronil desulfinylin egg,egg noodle,cake and mayonnaise.