固相萃取/超高效液相色谱-串联质谱法测定尿液中6种双酚类及烷基酚类物质

Determination of 6 Bisphenols and Alkylphenols in Human Urine by Solid Phase Extraction/Ultra High Performance Liquid Chromatography-Tandem Mass Spectrometry

建立了超高效液相色谱-串联质谱测定人体尿液中双酚A(BPA)、双酚F(BPF)、四氯双酚A(TCBPA)、四溴双酚A(TBBPA)、壬基酚(NP)、4-正辛基苯酚(4-n-OP)的检测方法。尿液样品通过酶解和固相萃取法进行前处理,采用Acquity UPLC HSS T3色谱柱(2.1 mm×100 mm,1.8μm)分离,负离子电喷雾多反应监测模式检测,同位素内标法定量。6种待测物在0.5~50μg/L范围内线性关系良好,相关系数均大于0.995,检出限为0.05~0.60μg/L,定量下限为0.17~2.00μg/L,2、10、50μg/L加标水平下的回收率为81.4%~112%,相对标准偏差(RSD,n=6)为6.8%~30%。应用此方法测定160份人体尿液样品,双酚A的检出率为93.8%,检出范围为0.24~29.54μg/L,其余目标物未检出。该方法操作简便、重现性好、定量准确,适用于人体尿液中双酚类及烷基酚类物质的测定。

An ultra high performance liquid chromatography-tandem mass spectrometry with solid phase extraction was developed for the determination of bisphenol A(BPA),bisphenol F(BPF),tetrachlorobisphenol A(TCBPA),tetrabromobisphenol A(TBBPA),4-nonylphenol(NP),4-octylphenol(4-n-OP) in human urine.Human urine sample was purified by solid phase extraction after glucuronidase,then separated on an Acquity UPLC HSS T3 column(2.1 mm×100 mm,1.8 μm).The 6 analytes were determined in negative electrospray(ESI-) under multiple reaction monitoring(MRM) mode,and quantified by isotope-labeled internal standard method.There were good linear relationships for 6 analytes in the range of 0.5-50 μg/L with their correlation coefficients larger than 0.995.The limits of detection and the limits of quantitation were in the ranges of 0.05-0.60 μg/L and 0.17-2.00 μg/L,respectively.Recoveries at three spiked levels of 2,10 and 50 μg/L ranged from 81.4% to 112% with relative standard deviations(RSD) of 6.8%-30%.The method was utilized in the determination of 160 human urine samples with a detection rate of 93.8% for BPA in the range of 0.24-29.54 μg/L,and other substances were not detected.With the advantages of convenient operation,good accuracy and stability,this method is suitable for the determination of bisphenols and alkylphenols in human urine.