鸡蛋中高氯酸盐和氯酸盐残留量的高效液相色谱-串联质谱同时测定法

Simultaneous determination of perchlorate and chlorate residues in egg by high-performance liquid chromatography-tandem mass spectrometric method

目的建立高效液相色谱-串联质谱测定鸡蛋中高氯酸盐和氯酸盐残留量的检测方法。方法取适量样品于50 mL聚丙烯离心管中,加入0.1%(V/V)甲酸水提取液,涡旋混匀,超声提取20 min,加入乙腈沉淀蛋白,涡旋混匀,离心半径=6 cm,10000 r/min(4℃)离心10 min。取上清液过PRiME HLB固相萃取柱净化,净化液直接过0.22μm再生纤维素滤膜,供高效液相色谱-串联质谱仪测定,采用负离子多反应监测(multiple reaction monitoring,MRM)模式,内标法定量。结果在优化后的色谱和质谱条件下,高氯酸盐浓度为0.0~100.0 ng/mL和氯酸盐浓度为0.0~200.0 ng/mL范围内,线性关系良好,相关系数(r2)≥0.9981,方法检出限≤0.9μg/kg,基质加标平均回收率为91.3%~106.4%,相对标准偏差(relative standard deviation,RSD)为2.8%~9.9%。结论该方法样品前处理简单,分析效率高,净化效果好,操作时间短,可广泛适用于同时测定鸡蛋中高氯酸盐和氯酸盐的残留量。

Objective To establish a high-performance liquid chromatography-tandem mass spectrometric method(HPLC-MS/MS)for the simultaneous determination of perchlorate and chlorate residues in egg.Methods An appropriate amount of sample was taken into a 50 mL polypropylene centrifuge tube,adding 0.1%(V/V)formic acid-water.The sample was mixed by vortex and extracted by ultrasonic oscillation for 20 min,adding acetonitrile to precipitate protein,then was mixed by vortex and centrifuged for 10 min at 10000 r/min(4℃)with the centrifugal radius of 6 cm.The supernatant was cleaned up by PRiME HLB solid phase extraction column,and the purified solution was directly purified by 0.22μm regenerated cellulose filter membrane.The quantification of perchlorate and chlorate residues was achieved by HPLC-MS/MS with the negative ion modes and multiple reaction monitoring(MRM)using internal standard method.Results Under the conditions of optimized chromatographic and mass spectrometry,the calibration curves were linear in the range of 0.0-100.0 ng/mL for perchlorate and 0.0-200.0 ng/mL for chlorate,with the correlation coefficient(r2)≥0.9981,and the the detection limits of the method were≤0.9μg/kg.The average recovery rates of perchlorate and chlorate residues were 91.3%-106.4%,with relative standard deviation(RSD)of 2.8%-9.9%.Conclusion The method has the advantages of simple sample pretreatment,high analytical efficiency,good purification effect and short operation time,and it can be widely used for the simultaneous determination of perchlorate and chlorate residues in eggs.