固相萃取-液相色谱/串联质谱法测定尿中10种双酚类物质和壬基酚及辛基酚化合物

Determination of Nonylphenol,Octylphenol and 10 Bisphenols in Urine by Solid Phase Extraction-Liquid Chromatography/Tandem Mass Spectrometry

目的建立高相液相色谱/串联四级杆质谱法测定尿中10种双酚类物质和壬基酚、辛基酚的方法。方法尿样通过β-葡糖苷酸酶水解后,经过瓦里安Bond Elut Plexa固相萃取小柱浓缩、净化后,用甲醇-乙腈:水为流动相进行梯度洗脱,使用串联质谱负离子电喷雾多反应监测模式进行检测分析。结果12种目标物质在0.50~100.00μg/L质量浓度范围内线性关系良好,线性相关系数(r)≥0.9991,方法检出限为0.01~0.38μg/L,定量限为0.03~1.27μg/L,加标回收率为72%~109%,批内相对标准偏差为1.26%~12.7%,批间相对标准偏差为1.44%~12.3%。对2018年采集的80份儿童尿样进行检测双酚A、双酚F、双酚S、双酚AF的检出率分别为96.2%、28.7%、46.2%、15.0%。未检出双酚B、双酚E、双酚Z、双酚AP、四氯双酚A、四溴双酚A、辛基酚、壬基酚。结论本方法操作简单、快速、灵敏度高、选择性好,可作为检测尿中10种双酚类物质和壬基酚、辛基酚的有效方法。

Objective To establish a method for the determination of 10 bisphenols,nonylphenol and octylphenol in urine by high performance liquid chromatography/tandem quadrupole mass spectrometry.Methods Urine samples were hydrolyzed by β-glucuronidase,and it was concentrated and purified by Varian Bond Elut Plexa solid phase extraction cartridge,and eluted with a gradient of methanolacetonitrile as the mobile phase.Monitoring mode was used for detection analysis.Results The linearity of the 12 target substances in the range of 0.50~100.00μg/L was linear with the linear correlation coefficient(r)≥0.9991.The detection limit was 0.01~0.38μg/L and the limit of quantification was 0.03~1.27μg/L.The recoveries for spiked samples ranged from 72% to 109%.The relative standard deviations within the batch ranged from 1.26% to 12.7%,and the relative standard deviations among batches were 1.44%~12.3%.The detection rates of 80 children’s urine samples collected in 2018 were 96.2%,28.7%,46.2% and 15% for bisphenol A,bisphenol F,bisphenol S and bisphenol AF,respectively.Bisphenol B,bisphenol E,bisphenol Z,bisphenol AP,tetrachlorobisphenol A,tetrabromobisphenol A,octylphenol and nonylphenol were not detected.Conclusion This method was simple,rapid,sensitive and selective.It could be used as an effective method for the detection of 10 bisphenols and nonylphenol and octylphenol in urine.