Comprehensive review of combustion ion chromatography for the analysis of total, adsorbable, and extractable organic fluorine

Poly- and perfluoroalkyl substances (PFAS) are a class of persistent organic pollutants whose high stability and appreciable water solubility have led to near-global contamination. PFAS are bioaccumulative toxins that have been linked to a myriad of disorders and have been detected nearly universally in human blood. Liquid chromatography-tandem mass spectrometry is the most frequent method used for quantitation, though this typically only measures a few dozen of the >14 000 known PFAS and has been shown to account for a small portion of the total organic fluorine present. Sum parameter methods such as total, extractable, and adsorbable organic fluorine have emerged as alternative measurements for PFAS determination. Combustion ion chromatography has become the preferred method for organofluorine measurement where the sorbent or extract containing PFAS is combusted and the emitted hydrofluoric acid (HF) is a measure of the cumulative organofluorine present. Herein we critically review the types of organofluorine measurement, their separation from the sample matrix, and key parameters of the analytical instrument that affect sensitivity, reproducibility, and recovery with regards to PFAS analysis.