Per- and polyfluoroalkyl substances (PFAS) are a large group of more than 4700 individual compounds which are applied in a wide range of applications in industrial processes and consumer products due to their water and oil repellency and surfactant properties. Concerns on PFAS arise from the very high stability, bioaccumulation potential and toxicity and the ubiquitous occurrence in humans, animals, soils, sediments, surface, ground and drinking waters. Advanced analytical methods are needed to investigate the input and fate of PFAS and potential transformation products in the environment and the exposure pathways for humans and wildlife. Therefore, nontarget screening (NTS) methods by high-resolution mass spectrometry (HRMS) coupled to chromatography are often applied to meet the analytical challenges arising from the high number and chemical diversity of individual compounds, the lack of authentic standards and information on identity and application areas. In this critical review we discuss the recent advances of NTS workflows applied to detect and identify PFAS based on the intrinsic information contained in data from chromatography and HRMS data on the MS¹ and MS² level. This includes retention time and peak shape characteristics, data on accurate mass and isotopologues, and high-resolution mass fragments. Successful approaches for prioritization and identification of PFAS are mostly based on mass defect filtering, Kendrick mass defect analysis, mass matches with suspect lists, assignment of chemical formulas, mass fragmentation patterns, diagnostic fragments and fragment mass differences. So far NTS approaches for PFAS were able to identify more than 750 compounds. However, still limited applicability of chromatography and ionization methods and limited mass resolving power and accuracy largely restrict a complete identification of a high number of unknown PFAS in complex samples from environmental compartments and biota.

全氟烷基物质和多氟烷基物质 (PFAS) 是由 4700 多种单独化合物组成的一大类化合物，由于其防水、防油和表面活性剂特性，在工业过程和消费品中得到广泛应用。人们对 PFAS 的担忧源于其极高的稳定性、生物蓄积潜力和毒性，以及在人类、动物、土壤、沉积物、地表水、地下水和饮用水中的普遍存在。需要先进的分析方法来研究环境中 PFAS 和潜在转化产物的输入和归宿以及人类和野生动物的暴露途径。因此，通常采用高分辨率质谱 (HRMS) 与色谱相结合的非目标筛选 (NTS) 方法来应对因单个化合物的数量和化学多样性高、缺乏可靠的标准和有关身份和信息的信息而带来的分析挑战。应用领域。在这篇批判性评论中，我们讨论了 NTS 工作流程的最新进展，该工作流程用于根据 MS 1 和 MS 2 级别的色谱数据和 HRMS 数据中包含的内在信息来检测^和识别^PFAS。这包括保留时间和峰形特征、精确质量和同位素体数据以及高分辨率质量片段。PFAS 优先级排序和识别的成功方法主要基于质量缺陷过滤、Kendrick 质量缺陷分析、与可疑列表的质量匹配、化学式分配、质量碎片模式、诊断碎片和碎片质量差异。到目前为止，针对 PFAS 的 NTS 方法能够识别出 750 多种化合物。然而，色谱和电离方法的适用性仍然有限，质量分辨能力和准确性有限，在很大程度上限制了对来自环境区划和生物群的复杂样品中大量未知 PFAS 的完全鉴定。