超高效液相色谱-串联质谱法测定人体血清中49种全氟和多氟烷基物质的含量  

Determination of 49 Perfluoroalkyl and Polyfluoroalkyl Substances in Human Serum by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

作　　者：陈泽元 施静 戴宁彬 杨海兵 张小刚[3] 赵刘清 夏瑜 CHEN Zeyuan;SHI Jing;DAI Ningbin;YANG Haibing;ZHANG Xiaogang;ZHAO Liuqing;XIA Yu(School of Public Health,Nanjing Medical University,Nanjing 211112,China;Inspection Department,Suzhou Municipal Center for Disease Control and Prevention,Suzhou 215000,China;SCIEX Analytical Instrument Trading Co.,Ltd.,Shanghai 200050,China)

机构地区：[1]南京医科大学公共卫生学院,南京211112 [2]苏州市疾病预防控制中心理化检验科,苏州215000 [3]SCIEX分析仪器贸易有限公司,上海200050

出　　处：《理化检验(化学分册)》2025年第4期381-391,共11页Physical Testing and Chemical Analysis(Part B:Chemical Analysis)

基　　金：苏州市卫健委科教强卫面上项目(MSXM2024035);苏州市科技局发展项目(2023ssd45);江苏省预防医学及血地寄防科研课题面上项目(Ym2023076)。

摘　　要：取50μL健康人体血清样品置于1.5 m L离心管中,加入3.125μg·L^(-1)混合内标使用液200μL,涡旋60 s,于4℃超声10 min,于-20℃冷冻保存1 h,于4℃离心15 min。取100μL上清液置于含150μL水的1.5 m L离心管中,涡旋60 s,于4℃超声5 min,离心10 min,采用超高效液相色谱-串联质谱法(UHPLC-MS/MS)测定上清液中49种全氟和多氟烷基物质(PFASs)的含量。以Poroshell 120 EC-C18色谱柱为固定相,以不同体积比的4 mmol·L^(-1)甲酸铵溶液-乙腈混合液为流动相进行梯度洗脱,质谱分析采用电喷雾离子(ESI)源,在负离子(ESI-)扫描模式下采用多反应监测(MRM)模式检测。结果表明,49种PFASs和内标的质量浓度比值与其峰面积比值均在一定范围内呈线性关系,检出限(3S/N)为0.000 2~0.166 7μg·L^(-1)。按照标准加入法进行回收试验,回收率为80.5%~118%,测定值的相对标准偏差(n=6)为0.80%~12%。方法用于200份健康人体血清样品的分析,49种PFASs均被检出,其中检出量中位数排在前五的PFASs依次为全氟辛烷磺酸、9-氯全氟三氧代壬烷磺酸、全氟己烷磺酸、全氟辛酸、全氟癸酸,检出量中位数分别为107.188,68.838,51.810,44.381,12.507μg·L^(-1)。The healthy human serum sample(50μL)was taken and placed in a 1.5 mL-centrifuge tube.200μL of 3.125μg·L^(-1) mixed internal standard solution was added,and the solution was vortexed for 60 s and sonicated at 4℃for 10 min.The mixture was frozen at-20℃for 1 h and centrifuged for 15 min at 4℃.100μL of supernatant was taken and placed in a 1.5 mL-centrifuge tube containing 150μL of water,and the solution was vortexed for 60 s,sonicated for 5 min and centrifuged for 10 min at 4℃.49 perfluoroalkyl and polyfluoroalkyl substances(PFASs)in the supernatant were determined by ultra-high performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS).Poroshell 120 EC-C18 column was used as the stationary phase and the mixed solution composed of 4 mmol·L^(-1) ammonium formate solution and acetonitrile at different volume ratios was used as the mobile phase for gradient elution.Electrospray ion(ESI)source was used for mass spectrometry.The targets were analyzed by multiple reaction monitoring(MRM)mode in negative ion(ESI-)scanning mode.As shown by the results,linear relationships between values of the mass concentration ratio and the peak area ratio of the 49 PFASs to internal standard were kept in definite ranges,with detection limits(3S/N)in the range of 0.0002-0.1667μg·L^(-1).Test for recovery was made by the standard addition method,giving results in the range of 80.5%-118%,with RSDs(n=6)of the determined values in the range of 0.80%-12%.This method was used for the analysis of 200 healthy human serum samples,and 49 PFASs were detected.Among them,the top five PFASs with medians of detection amounts were perfluorooctane sulfonic acid,9-chloroperfluorotrioxynonanesulfonic acid,perfluorohexane sulfonic acid,perfluorooctanoic acid,and perfluorodecanoic acid,with medians of detection amounts of 107.188,68.838,51.810,44.381,and 12.507μg·L^(-1),respectively.

关 键 词：超高效液相色谱-串联质谱法(UHPLC-MS/MS) 人体血清 全氟和多氟烷基物质 

分 类 号：O657.63[理学—分析化学]