首页|血清中53种全氟和多氟烷基化合物的高通量液质联用检测方法的建立

血清中53种全氟和多氟烷基化合物的高通量液质联用检测方法的建立

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  • 国家科技期刊平台
  • NETL
  • NSTL
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[背景]全氟和多氟烷基化合物(PFAS)广泛用于防油防水剂和涂层，人群接触更广泛，是一类对人体有潜在毒性的持久性有机污染物。建立覆盖范围更广的PFAS定量检测方法对全面反映人体PFAS的暴露负荷具有重要意义。[目的]建立基于超高效液相色谱串联四极杆/静电场轨道离子阱高分辨质谱(UPLC-Q Exactive HRMS)同时测定人血清中53种PFAS的高通量定量检测方法。[方法]比较亲水亲脂(HLB)柱、弱阴离子交换(WAX)柱以及 96孔WAX μElution板三种不同SPE柱对PFAS的提取回收率，选取最适预处理条件;比较ACQUITY UPLC BEH C18 色谱柱和Accucore aQ色谱柱以及流动相中甲酸铵浓度(0、2、5和 10 mmol·L-1)对目标物的保留时间、峰形和响应的影响，选择最适液相条件;比较喷雾电压(-2 kV和-4 kV)对目标物响应的影响，选择合适的质谱条件;从选择性、标准曲线、检出限、精密度、准确度和基质效应等方面对所建方法进行验证;并将所建立的方法应用于142份脐带血清的检测。[结果]三种不同SPE柱比较结果显示，用 96孔WAX μElution板对样品预处理，可以获得最好的提取回收率(64%～118%)。目标物用Accucore aQ色谱柱在含 5 mmol·L-1 甲酸铵的水-甲醇流动相体系下梯度洗脱可以获得最好的分离效果和色谱峰形。离子源喷雾电压设置为-2 kV时目标物源内裂解更少，响应更高。所有目标物在标准曲线范围内具有良好的线性关系，R2>0。99。方法检出限在 0。01～0。50 μg·L-1 之间，回收率为 69%～127%，精密度小于 26%。在142份实际样品中检出了 31种PFAS，其中 14种PFAS的检出率大于 50%，中位浓度最高的是全氟辛酸，达 4。16 μg·L-1，其次是 6:2氯代多氟烷基醚磺酸和全氟辛烷磺酸，中位浓度分别为3。50 μg·L-1 和1。59 μg·L-1。[结论]本研究基于UPLC-Q Exactive HRMS技术建立的血清中 53种PFAS浓度的高通量检测方法具有覆盖范围广，选择性好，操作简便等优点，适用于大样本量的PFAS检测。
Establishment of high-throughput liquid chromatography tandem mass spectrometry method for determination of 53 per-and polyfluoroalkyl substances in serum
[Background]Per-and polyfluoroalkyl substances(PFAS)are a class of persistent organic pollu-tants that possess potential toxicity to the human body.The production and utilization of diverse emerging PFAS have resulted in widespread human exposure.Therefore,it is imperative to es-tablish a quantitative methodology encompassing a wide range of PFAS for a comprehensive as-sessment of human exposure to these compounds.[Objective]To establish a high-throughput quantitative method for the simultaneous determina-tion of 53 PFAS in human serum based on ultra-high-performance liquid chromatography-Q Ex-active high resolution mass spectrometry(UPLC-Q Exactive HRMS).[Methods]The extraction recoveries of hydrophilic-lipophilic balance(HLB)column,weak anion exchange(WAX)column,and 96-well WAX μElution plate were compared to select the SPE column with the highest recovery.The retention time and peak shape of the target compounds were compared between ACQUITY UPLC BEH C18 column and Accucore aQ column,and the more cost-effective column was chosen.The effects of adding different levels of ammonium formate(0,2,5 and 10 mmol·L-1)in mobile phase on peak shape and target response were compared to determine the optimal buffer salt concentration.The optimal spray voltage was obtained by comparing-2 kV and-4 kV.The proposed method was validated from the aspects of selectivity,standard curve,limits of detection,precision,accuracy,and matrix effect.The method was applied to 142 umbilical serum samples.[Results]The best recovery rate(64%-118%)was achieved by using 96-well WAX μElution plate.The optimal separation and peak shape were obtained by utilizing Accucore aQ column with H2O-methanol(containing 5 mmol·L-1 ammonium formate)as the mobile phase.Less in-source collision and better target response were observed when the spray voltage was set to-2 kV.All target analytes had a good linearity,with R2>0.99.The limits of detection ranged from 0.01 to 0.50 μg·L-1,and the recovery ranged from 69%to 127%with the precision less than 26%.A total of 31 PFAS were detected in the 142 actual samples,among which 14 PFAS had a detection frequency over 50%.Perfluorooctanoic acid showed the highest median concentration of 4.16 μg·L-1,followed by 6:2 chlorinated polyfluorinated ether sulfonate and perfluorooctane sulfonates(3.50 μg·L-1 and 1.59 μg·L-1,respectively).[Conclusion]In this study,we establish a UPLC-Q Excative HRMS method for simutanious determination of 53 PFAS concentrations in serum.This method has the advantages of wide coverage of PFAS,good selectivity,and easy operation,and is suitable for biological de-tection with a large sample size.

per-and polyfluoroalkyl substancesserumhigh resolution mass spectrometrysolid phase extractionhigh throughput

王铮、张博雅、张济明、冯超、林元杰、邬春华、卢大胜、周志俊

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复旦大学,公共卫生学院/公共卫生安全教育部重点实验室,上海 200032

上海市疾病预防控制中心,上海 200336

全氟和多氟烷基化合物 血清 高分辨质谱 固相萃取 高通量

上海市加强公共卫生体系建设三年行动计划重点学科建设项目上海市加强公共卫生体系建设三年行动计划重点学科建设项目上海市加强公共卫生体系建设三年行动计划重点学科建设项目上海市"科技创新行动计划"社会发展科技攻关计划(2021)

GWVI-4GWVI-11.1-37GWVI-11.1-4121DZ1202100

2024

10.11836/JEOM23362

环境与职业医学
上海市疾病预防控制中心 中华预防医学会

环境与职业医学

CSTPCD北大核心
影响因子：0.71
ISSN：1006-3617
年,卷(期)：2024.41(4)
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