摘要
研究建立了一种超高效液相色谱-串联质谱法(UPLC-MS/MS)同时测定人尿中12种典型个人护理品(PCPs)的分析方法,其中包括5种对羟基苯甲酸酯类防腐剂(PBs)、5种二苯酮类紫外吸收剂(BPs)和2种抗菌剂。1 mL尿样中加入β-葡萄糖醛酸酶-乙酸铵缓冲溶液和混合内标工作液置于37℃水浴酶解过夜(≥16 h)。样品采用Oasis HLB固相萃取柱富集净化,在乙腈-水流动相体系下采用Acquity BEH C_(18)色谱柱进行色谱分离,负离子电喷雾(ESI-)多反应监测(MRM)模式检测,稳定同位素内标法定量。实验通过优化仪器质谱参数、流动相和色谱柱等色谱条件以及酶解和固相萃取柱等前处理条件,获得了最佳实验结果。在优化条件下,羟苯甲酯(MeP)和二苯酮-3(BP-3)在4.00~800μg/L,三氯生(TCS)在5.00~200μg/L,其余9种PCPs在1.00~200μg/L范围内线性关系良好,相关系数大于0.999,方法检出限(MDL)为0.06~1.09μg/L,方法定量限(MQL)为0.08~3.63μg/L。12种分析物的加标回收率为89.5%~111.8%,日内精密度为3.7%~8.9%,日间精密度为2.0%~10.6%。采用稳定同位素内标法校正后12种分析物的基质效应为91.9%~110.1%。该方法成功应用于127份实际尿液样品的测定。结果表明,除羟苯苄酯(BzP)和二苯酮-8(BP-8)未检出外,其余10种典型PCPs均可检出,总体检出率为1.7%~99.7%,其中MeP、羟苯乙酯(EtP)和羟苯丙酯(PrP)检出率和浓度水平处于较高水平。该方法简便灵敏,可为人群尿液样本PCPs的生物监测工作提供可靠的技术支持。
A rapid and sensitive method based on ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)was developed for the simultaneous determination of 12 typical personal care products(PCPs)in human urine.These PCPs included five paraben preservatives(PBs),five benzophenone UV absorbers(BPs),and two antibacterial agents.Accordingly,1 mL of the urine sample was mixed with 500μL ofβ-glucuronidase-ammonium acetate buffer solution(enzymatic activities are 500 units/mL)and 75μL of a mixed internal standard working solution(internal standard contents are 7.5 ng),followed by enzymatic hydrolysis overnight(≥16 h)at 37℃in a water bath.The 12 targeted analytes were enriched and cleaned up using an Oasis HLB solid phase extraction column.Separation was performed on an Acquity BEH C_(18)column(100 mm×2.1 mm,1.7μm)using an acetonitrile-water system as the mobile phase,in negative electrospray ionization(ESI-)multiple reaction monitoring(MRM)mode,for target detection and stable isotope internal standard quantification.The optimal MS conditions were established by optimizing the instrument parameters and comparing two analytical columns(Acquity BEH C_(18)and Acquity UPLC HSS T 3)as well as different types of mobile phases(methanol or acetonitrile as the organic phase)to achieve better chromatographic separation.In order to obtain higher enzymatic and extraction efficiency,different enzymatic conditions,solid phase extraction columns,and elution conditions were investigated.The final results showed that methyl parabens(MeP),benzophenone-3(BP-3),and triclosan(TCS)showed good linearities in the ranges of 4.00-800,4.00-800 and 5.00-200μg/L,respectively,the other targeted compounds showed good linearities in the ranges of 1.00-200μg/L.The correlation coefficients were all greater than 0.999.The method detection limits(MDLs)were in the range of 0.06-1.09μg/L,and the method quantification limits(MQLs)ranged from 0.08 to 3.63μg/L.At three spiked levels,the average recoveries of the 12 targeted analytes range
作者
韩林学
张续
胡小键
张海婧
邱天
林潇
朱英
HAN Linxue;ZHANG Xu;HU Xiaojian;ZHANG Haijing;QIU Tian;LIN Xiao;ZHU Ying(China CDC Key Laboratory of Environment and Population Health,National Institute of Environmental Health,Chinese Center for Disease Control and Prevention,Beijing 100021,China)
出处
《色谱》
CAS
CSCD
北大核心
2023年第4期312-322,共11页
Chinese Journal of Chromatography
基金
中央财政经费项目(131031108000150003).
关键词
固相萃取
超高效液相色谱-串联质谱
个人护理品
尿液
生物监测
solid phase extraction(SPE)
ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)
personal care products(PCPs)
urine
biomonitoring
