Renai Lapo, Del Bubba Massimo, Gargano Andrea F G, Samanipour Saer
van't Hoff Institute for Molecular Science, University of Amsterdam, Amsterdam, the Netherlands; Department of Chemistry, University of Florence, Sesto Fiorentino, Florence, Italy.
van't Hoff Institute for Molecular Science, University of Amsterdam, Amsterdam, the Netherlands.
Sci Total Environ. 2024 Nov 20;952:175908. doi: 10.1016/j.scitotenv.2024.175908. Epub 2024 Aug 30.
To date, poly- and perfluoroalkyl substances (PFAS) represent a real threat for their environmental persistence, wide physicochemical variability, and their potential toxicity. Thus far a large portion of these chemicals remain structurally unknown. These chemicals, therefore, require the implementation of complex non-targeted analysis workflows using liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) for their comprehensive detection and monitoring. This approach, even though comprehensive, does not always provide the much-needed analytical resolution for the analysis of complex PFAS mixtures such as fire-fighting aqueous film-forming foams (AFFFs). This study consolidates the advantages of the LC×LC technique hyphenated with high-resolution tandem mass spectrometry (HRMS/MS) for the identification of PFAS in AFFF mixtures. A total of 57 PFAS homolog series (HS) were identified in 3M and Orchidee AFFF mixtures thanks to the (i) high chromatographic peak capacity (n' ~ 300) and the (i) increased mass domain resolution provided by the "remainder of Kendrick Mass" (RKM) analysis on the HRMS data. Then, we attempted to annotate the PFAS of each HS by exploiting the available reference standards and the FluoroMatch workflow in combination with the RKM defect by different fluorine repeating units, such as CF, CFO, and CFO. This approach resulted in 12 identified PFAS HS, including compounds belonging to the HS of perfluoroalkyl carboxylic acids (PFACAs), perfluoroalkyl sulfonic acids (PFASAs), (N-pentafluoro(5)sulfide)-perfluoroalkane sulfonates (SF5-PFASAs), N-sulfopropyldimethylammoniopropyl perfluoroalkane sulfonamides (N-SPAmP-FASA), and N-carboxymethyldimethylammoniopropyl perfluoroalkane sulfonamide (N-CMAmP-FASA). The annotated categories of perfluoroalkyl aldehydes and chlorinated PFASAs represent the first record of PFAS HS in the investigated AFFF samples.
迄今为止，多氟和全氟烷基物质（PFAS）因其环境持久性、广泛的物理化学变异性以及潜在毒性而构成了真正的威胁。到目前为止，这些化学物质中的很大一部分在结构上仍然未知。因此，对于这些化学物质，需要采用复杂的非靶向分析工作流程，即使用液相色谱与高分辨率质谱联用（LC-HRMS）来进行全面的检测和监测。这种方法虽然全面，但对于分析复杂的PFAS混合物（如消防水成膜泡沫（AFFFs）），并不总能提供急需的分析分辨率。本研究整合了液相色谱二维分离（LC×LC）技术与高分辨率串联质谱（HRMS/MS）联用的优势，用于鉴定AFFF混合物中的PFAS。由于（i）高色谱峰容量（n'~300）以及（ii）通过对HRMS数据进行“肯德里克质量余数”（RKM）分析提供的更高质量域分辨率，在3M和兰花牌AFFF混合物中总共鉴定出了57个PFAS同系物系列（HS）。然后，我们尝试通过利用可用的参考标准以及FluoroMatch工作流程，并结合不同氟重复单元（如CF、CFO和CFO）的RKM缺陷，来注释每个HS的PFAS。这种方法鉴定出了12个PFAS HS，包括属于全氟烷基羧酸（PFACAs）、全氟烷基磺酸（PFASAs）、（N-五氟（5）硫化物）-全氟烷磺酸酯（SF5-PFASAs）、N-磺丙基二甲基氨丙基全氟烷磺酰胺（N-SPAmP-FASA）以及N-羧甲基二甲基氨丙基全氟烷磺酰胺（N-CMAmP-FASA）同系物系列的化合物。全氟烷基醛和氯化PFASAs的注释类别代表了在所研究的AFFF样品中PFAS HS的首次记录。
