Bridging the fluorine gap: A review of a decade of analytical developments for perfluoroalkyl and polyfluoroalkyl in environmental, food, and human matrices

Perfluoroalkyl and Polyfluoroalkyl substances (PFAS) constitute a broad class of persistent contaminants whose detection and quantification remain a significant challenge for analytical and environmental sciences. This review integrates recent evidence (2015–2025) on techniques applied to the determination of PFAS in water, soil, food, biota, and human matrices, encompassing targeted methods based on liquid chromatography–tandem mass spectrometry (LC–MS/MS), non-targeted strategies employing high-resolution mass spectrometry and ion mobility spectrometry (HRMS/IMS), and sum-parameter approaches, including total fluorine (TF), extractable organic fluorine (EOF), adsorbable organic fluorine (AOF), and total organic fluorine (TOF). The literature shows that these sum parameters often exceed the sum of targeted PFAS by one to three orders of magnitude, reflecting a substantial pool of unidentified organofluorine compounds. Recent advances include increased analytical sensitivity, with limits of detection of 0.05–1 ng/L for ultra-short-chain PFAS achieved using high-resolution liquid chromatography–mass spectrometry (LC–HRMS), the growing use of two-dimensional chromatography (LC×LC–HRMS), and improvements in combustion–ion chromatography (CIC) protocols, which currently reach 2–20 ng F/L for EOF. These developments rely heavily on robust sample-preparation strategies, including weak anion-exchange solid-phase extraction (SPE-WAX), QuEChERS-based protocols, and the removal of inorganic interferents, all of which are essential for minimizing contamination from polytetrafluoroethylene (PTFE) and reducing matrix effects. Despite these analytical improvements, limitations persist related to the scarcity of authentic standards, methodological heterogeneity, and uncertainties in quantification limits, particularly in food matrices and regulated waters. Harmonization of protocols and integration across targeted, non-targeted, and total organic fluorine–based metrics remain critical for achieving more comprehensive and consistent risk assessments.