固相萃取结合高效液相色谱-串联质谱测定胎便中14种全氟和多氟烷基化合物

Determination of 14 kinds of perfluorinated and polyfluoroalkyl compounds in meconium by solid phase extraction-high performance liquid chromatography-tandem mass spectrometry

全氟和多氟烷基化合物(PFASs)是一类人工合成的物质,由于其热稳定、疏水、疏油等优良性质而被广泛使用于生活和生产中.PFASs具有环境持久性、生物累积性、多种毒性等特性,且可以通过胎盘屏障进入到胎儿体内,进而对胎儿健康产生潜在危害.胎便中积累了妊娠期间暴露于胎儿的外源性化合物,可用于监测PFASs对胎儿的宫内暴露特征.本研究基于固相萃取结合高效液相色谱-串联质谱技术,建立了胎便中14种PFASs的分析方法.采用乙腈/水(9∶1,V/V)对0.2 g冻干胎便样品进行超声提取,提取液经Envi-carb和Oasis WAX小柱固相萃取,0.1%氨甲醇洗脱.以10 mmol·L^(−1)乙酸铵水溶液和乙腈作为流动相对目标化合物进行梯度洗脱,采用Acquity UPLC BEH C18色谱柱进行分离,基于多反应监测负离子模式采集,内标法定量.结果表明,在2、5、20 ng·g^(−1)的加标浓度下,14种PFASs的回收率为65%—149%,相对标准偏差为3%—22%,方法检出限(MDLs)为0.001—0.149 ng·g^(−1),方法定量限(MQLs)为0.003—0.495 ng·g^(−1).使用该方法测定了10个胎便样品,ΣPFASs浓度范围为<MDLs—2.49 ng·g^(−1).该方法操作简单、便捷、灵敏度高且定量准确,为系统性研究胎便中PFASs的赋存特征及暴露风险提供了技术基础.

Perfluorinated and polyfluoroalkyl compounds(PFASs)are a kind of synthetic substances,which have been widely used in daily life and production because of their excellent properties such as heat stability,hydrophobic and oleophobic.PFASs have the characteristics of environmental persistence,bioaccumulation,and multiple toxicity,and can pass across the placental barrier into the fetal,thus posing potential exposure risk to fetal health.Generally,the meconium accumulates exogenous compounds that were exposed to the fetus during pregnancy,as such,the meconium can be used to monitor the exposure characteristics of PFASs to the fetus.A method was established for the determination of 14 kinds of PFASs in meconium by solid phase extraction high performance liquid chromatography-tandem mass spectrometry(SPE HPLC-MS/MS).The freeze-drying meconium sample(0.2 g)was ultrasonically extracted by acetonitrile(ACN)/water(9:1,V/V)and then was extracted by Envi-carb and Oasis WAX cartridges,eluted with 0.1%ammonia in methanol.The sample was separated by using an Acquity UPLC BEH C18 column and eluted gradiently with 10 mmol·L^(−1)ammonium acetate and acetonitrile as the mobile phase.The samples were detected by tandem mass spectrometry under multiple reaction monitoring(MRM)mode with negative electrospray ionization,and quantified by internal standard method.Results showed that the recoveries of PFASs were 65%-149%at spiked levels of 2,5,and 20 ng·g^(−1),and the relative standard deviations(RSD)were 3%-22%.The method detection limits(MDLs)and the method quantitation limits(MQLs)were in the range of 0.001-0.149 ng·g^(−1)and 0.003-0.495 ng·g^(−1),respectively.The method was used to detect 10 meconium samples,and the concentrations ranged from<MDLs to 2.49 ng·g^(−1).This established method is simple,convenient,sensitive and accurate,which will provide a technical basis for the systematic study of the occurrence as well as exposure risk of PFASs in meconium.