固相萃取/高效液相色谱-串联质谱法同时测定氟橡胶、氟树脂及其制品中多种全氟和多氟烷基化合物  

Simultaneous Determination of Per-and Polyfluoroalkyl Compounds in Fluoroelastomer and Fluoroplastic Products by Solid Phase Extraction/High Performance Liquid Chromatography-Tandem Mass Spectrometry

作　　者：周鑫月 卢瑶 罗雅丹 黎娟 王亚韡 ZHOU Xin-yue;LU Yao;LUO Ya-dan;LI Juan;WANG Ya-wei(Henan Institute of Advanced Technology,Zhengzhou University,Zhengzhou 450001,China;Research Center for Eco-environmental Science,Chinese Academy of Sciences,Beijing 100085,China)

机构地区：[1]郑州大学河南先进技术研究院,河南郑州450001 [2]中国科学院生态环境研究中心,北京100085

出　　处：《分析测试学报》2024年第8期1166-1179,共14页Journal of Instrumental Analysis

基　　金：国家自然科学基金资助项目(22136006,22106169)。

摘　　要：基于固相萃取/高效液相色谱-串联质谱(HPLC-MS/MS)技术,建立了氟橡胶、氟树脂及其制品中37种全氟和多氟烷基化合物(PFASs)的定量分析方法和19种PFASs的定性分析方法。采用25 mmol·L^(-1)乙酸铵甲醇/乙腈(1∶1,体积比)溶液对氟橡胶类、氟树脂固体类和氟树脂纺织类样品进行超声振荡提取;采用四甲基叔丁基醚(MTBE)对氟树脂液体类样品进行超声振荡提取,提取液经Envi-carb和Oasis WAX柱固相萃取,并用甲醇和0.1%氨水甲醇洗脱。在10 mmol·L^(-1)乙酸铵溶液-乙腈流动相下采用Acquity UPLC BEH C18(2.1 mm×100 mm,1.7μm)色谱柱对目标化合物进行梯度洗脱分离,多反应监测模式(MRM)进行采集,内标法定量。结果表明,在5、10、20 ng·g^(-1)(氟橡胶类)和2.5、5、10 ng·g^(-1)(氟树脂类)加标水平下,氟橡胶类、氟树脂固体类、氟树脂纺织类和氟树脂液体类样品中37种PFASs的回收率分别为81.3%~109%、60.9%~111%、87.8%~125%和88.7%~140%;相对标准偏差(RSD)分别为1.4%~28%、1.5%~22%、1.8%~27%和1.4%~19%;检出限(LOD)分别为0.03~0.3 ng·g^(-1)、0.03~0.8 ng·g^(-1)、0.02~2 ng·g^(-1)和0.04~1 ng·g^(-1);定量下限(LOQ)分别为0.07~0.9 ng·g^(-1)、0.08~2 ng·g^(-1)、0.06~6 ng·g^(-1)和0.1~4 ng·g^(-1)。19种PFASs的回收率为0.300%~208%,适于半定量和定性分析。使用该方法测定10个氟橡胶和氟树脂样品,Σ_(37)PFASs含量为9.73~66.17 ng·g^(-1)。该方法操作简便、灵敏度高且定量准确,可为研究氟橡胶、氟树脂及其制品中PFASs的残留情况及完善我国出口贸易和国内履约执法监测提供技术支撑。In this study,a method for quantitative analysis of 37 PFASs(per-and polyfluoroalkyl compounds)and qualitative analysis of 19 PFASs in fluoroelastomer and fluoroplastic products was developed based on solid phase extraction/high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS).The samples of fluoroelastomers,fluoroplastic solids and fluoroplas⁃tic textiles were extracted by ultrasonication and oscillation using 25 mmol·L−1 ammonium acetate methanol/acetonitrile(1∶1,volume ratio)solution.The samples of fluoroplastic liquids were ex⁃tracted by ultrasonication and oscillation using methyltert-butylether(MTBE).And then extract was extracted by Envi-carb and Oasis WAX cartridges,and eluted with methanol and 0.1%ammonia methanol.The target compounds were analyzed by a Acquity UPLC BEH C18 column(2.1 mm×100 mm,1.7μm)with mobile phase consisted of 10 mmol·L−1 ammonium acetate solution and acetoni⁃trile.The samples were detected by tandem mass spectrometry under multiple reaction monitoring(MRM)mode and quantified by internal standard method.The results showed that at spiked levels of 5 ng·g^(-1),10 ng·g^(-1) and 20 ng·g^(-1)(fluoroelastomer samples)and 2.5 ng·g^(-1),5 ng·g^(-1) and 10 ng·g^(-1)(fluoroplastic samples),the recoveries of 37 PFASs in fluoroelastomers,fluoroplastic solids,fluo⁃roplastic textiles and fluoroplastic liquids were in the ranges of 81.3%-109%,60.9%-111%,87.8%-125%,and 88.7%-140%,and the relative standard deviations(RSDs)were 1.4%-28%,1.5%-22%,1.8%-27%and 1.4%-19%,and the method detection limits(LOD)were 0.03-0.3 ng·g^(-1),0.03-0.8 ng·g^(-1),0.02-2 ng·g^(-1) and 0.04-1 ng·g^(-1),and the method quantitation limits(LOQ)were 0.07-0.9 ng·g^(-1),0.08-2 ng·g^(-1),0.06-6 ng·g^(-1) and 0.1-4 ng·g^(-1).The recoveries of 19 PFASs ranged from 0.300%-208%,which are suitable for semi-quantitative and qualitative analy⁃sis.The method was used to detect 10 fluoroelastomer and fluoroplastic samples,and the content range ofΣ_(37)PFASs was 9.73-66.17 ng·g^(-1)

关 键 词：氟橡胶 氟树脂 全氟及多氟烷基化合物 高效液相色谱-串联质谱 固相萃取 

分 类 号：O657.7[理学—分析化学] X132[理学—化学]