超高效液相色谱-串联质谱法同时检测鸡蛋和猪肉中9种双酚-二缩水甘油醚类内分泌干扰物

Simultaneous determination of 9 kinds of bisphenol-diglycidyl ethers endocrine disruptors in egg and pork by ultra performance liquid chromatography-tandem mass spectrometry

目的建立可同时检测鸡蛋和猪肉中9种双酚-二缩水甘油醚(bisphenol-diglycidyl ethers,BDGEs)类内分泌干扰物的超高效液相色谱-串联质谱法(ultra performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS)。方法样品经磷酸盐缓冲液稀释后,用0.1%甲酸乙腈溶液进行提取,然后用正己烷除脂,Oasis PRiME HLB固相萃取柱净化,在电喷雾电离正离子模式下使用超高效液相色谱-串联质谱仪进行检测,内标法定量。结果鸡蛋和猪肉样品中9种BDGEs类物质在0.5~100.0μg/kg浓度范围内线性关系良好,相关系数(r^(2))大于0.99。方法的检出限为0.1~0.5μg/kg,定量限为0.5~1.0μg/kg;在定量限、2.0、10.0μg/kg 3个添加水平下,鸡蛋和猪肉样品中9种BDGEs类物质的平均回收率为80.16%~115.27%,日内变异系数为2.13%~11.15%,日间变异系数为7.24%~18.62%。采用该方法对28份市售鸡蛋样品进行分析,10批次样品中检出BADGE·2H2O,检出率为35.71%,浓度范围为0.020~6.450μg/kg。4批次样品中检出BADGE·H2O·HCl,检出率为14.29%,浓度范围为0.26~0.42μg/kg。结论本方法具有较高的灵敏度和准确度,适用于动物性食品中9种BDGEs类内分泌干扰物残留量的同时检测和准确定量。

Objective To establish a method for the simultaneous detection of 9 kinds of bisphenol-diglycidyl ethers(BDGEs)endocrine disruptors in egg and pork by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).Methods The samples were diluted with phosphate buffer solution and extracted with 0.1%formic acid-acetonitrile solution,and the samples were degreased by n-hexane,purified by Oasis PRiME HLB solid phase extraction column,and detected by ultra performance liquid chromatography-tandem mass spectrometry in positive ion mode of electrospray ionization using internal standard method for quantification.Results The linear relationships of the 9 kinds of BDGEs in egg and pork samples were good within the concentration range of 0.5-100.0μg/kg,and the correlation coefficient(r^(2))was greater than 0.99.The limits of detection were 0.1-0.5μg/kg,and the limits of quantitation were 0.5-1.0μg/kg;at the limits of quantitation,2.0 and 10.0μg/kg levels,the average recoveries of the 9 kinds of BDGEs in egg and pork samples were 80.16%-115.27%,the intra-day coefficient of variation were 2.13%-11.15%,and the intra-day coefficient of variation were 7.24%-18.62%.A total of 28 commercial egg samples were analyzed by this method,BADGE·2H2O was detected in 10 batches of samples,with the detection rate of 35.71%and the concentration ranges were 0.020-6.450μg/kg.BADGE·H2O·HCl was detected in 4 batches of samples,with the detection rate of 14.29%and the concentration ranges were 0.26-0.42μg/kg.Conclusion This method has high sensitivity and accuracy,and is suitable for simultaneous detection and accurate quantification of 9 kinds of BDGEs endocrine disruptors residues in animal food.