Munoz Gabriel, Labadie Pierre, Geneste Emmanuel, Pardon Patrick, Tartu Sabrina, Chastel Olivier, Budzinski Hélène
University of Bordeaux, EPOC, UMR 5805, LPTC Research Group, Talence F-33400, France.
CNRS, EPOC, UMR 5805, LPTC Research Group, Talence F-33400, France.
J Chromatogr A. 2017 Sep 1;1513:107-117. doi: 10.1016/j.chroma.2017.07.024. Epub 2017 Jul 10.
We report on a fast, accurate and rugged analytical procedure to determine a wide span of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in seabird plasma. The 26 investigated compounds included perfluoroalkyl carboxylates (C-C PFCAs), perfluoroalkyl sulfonates (C, C, C, C, C PFSAs), perfluorooctane sulfonamide (FOSA) and N-alkyl derivatives (MeFOSA, EtFOSA), N-alkyl perfluorooctane sulfonamido acetic acids (MeFOSAA, EtFOSAA), fluorotelomer sulfonates (4:2 FTSA, 6:2 FTSA, 8:2 FTSA), polyfluoroalkyl phosphate diesters (diPAPs) and perfluorooctane sulfonamide phosphate diester (diSAmPAP). The method described herein requires a reduced sample amount (25μL) and involves rapid and simple sample preparation (protein precipitation with acetonitrile but without acidification) prior to analysis by on-line solid phase extraction (Oasis HLB sorbent) coupled to high performance liquid chromatography negative electrospray ionization tandem mass spectrometry. The optimization was conducted using experimental designs to account for potential interactions between variables. Out of the 26 target analytes, 23 compounds showed excellent accuracy (±25% of the expected values). Intermediate precision and matrix effects remained acceptable for most analytes thanks to efficient internal standardization. A human serum standard reference material (NIST SRM 1957) was included in the validation scheme to evaluate method trueness, which proved satisfactory (│Z-scores│<2 for most compounds). Notwithstanding the small initial sample intake, limits of detection as low as 0.003-0.1ngg plasma were obtained. This allowed the determination of 11 target PFASs in Antarctic seabird plasma samples. ΣPFASs in Antarctic seabird plasma ranged from 0.37 to 19ngg, with a predominance of PFOS (>54% of ΣPFASs on average). The reduced plasma amount required implies that the present method could also be applied to the analysis of PFASs in the plasma of smaller biological models.
我们报告了一种快速、准确且耐用的分析方法，用于测定海鸟血浆中多种全氟烷基和多氟烷基物质（PFASs）。所研究的26种化合物包括全氟烷基羧酸盐（C-C PFCAs）、全氟烷基磺酸盐（C、C、C、C、C PFSAs）、全氟辛烷磺酰胺（FOSA）及其N-烷基衍生物（MeFOSA、EtFOSA）、N-烷基全氟辛烷磺酰胺基乙酸（MeFOSAA、EtFOSAA）、氟调聚物磺酸盐（4:2 FTSA、6:2 FTSA、8:2 FTSA）、多氟烷基磷酸二酯（diPAPs）和全氟辛烷磺酰胺磷酸二酯（diSAmPAP）。本文所述方法所需样品量减少（25μL），在通过在线固相萃取（Oasis HLB吸附剂）与高效液相色谱-负电喷雾电离串联质谱联用进行分析之前，涉及快速简单的样品制备（用乙腈进行蛋白沉淀但不酸化）。使用实验设计进行优化以考虑变量之间的潜在相互作用。在26种目标分析物中，23种化合物显示出优异的准确度（±预期值的25%）。由于有效的内标法，大多数分析物的中间精密度和基质效应仍可接受。在验证方案中纳入了一种人血清标准参考物质（NIST SRM 1957）以评估方法的准确性，结果证明是令人满意的（大多数化合物的│Z分数│<2）。尽管初始进样量小，但检测限低至0.003 - 0.1ng/g血浆。这使得能够测定南极海鸟血浆样品中的11种目标PFASs。南极海鸟血浆中的ΣPFASs范围为0.37至19ng/g，其中全氟辛烷磺酸（PFOS）占主导（平均占ΣPFASs的>54%）。所需血浆量的减少意味着本方法也可应用于较小生物模型血浆中PFASs的分析。
