Per- and polyfluoroalkyl substances (PFAS) are high-profile environmental contaminants, many having long persistence in the environment and widespread presence in humans and wildlife. While liquid chromatography (LC)-mass spectrometry (MS) is typically used for measurement, much of the PFAS is missed. To more comprehensively capture organic fluorine, we developed two new sensitive and robust methods using adsorbable organic fluorine (AOF) and extractable organic fluorine (EOF) with combustion ion chromatography (CIC) to measure total organic fluorine (TOF) in industrial wastewaters, river water, and air. Compared to previous methods, we achieved higher recoveries for a larger mix of 39 PFAS compounds, and our AOF method utilizes commercial pre-packed ACs rather than manual packing in a clean room. Our EOF method also utilizes a new type of SPE cartridge, which combines benefits of a WAX phase with graphitized carbon black (GCB) to more efficiently extract a wide range of PFAS classes with varying size and polarity. Our AOF method achieves 64-112% and 87% recovery for individual PFAS and PFAS mixtures, respectively, with 0.5 µg/L limit of detection (LOD). Our EOF method achieves 72-99% and 91% recovery for individual PFAS and PFAS mixtures, respectively, with 0.2 µg/L LOD. Substantially higher TOF values were measured in industrial wastewater, river water, and air samples compared to LC-MS/MS, demonstrating how TOF methods provided a more comprehensive measurement of the total PFAS present, capturing known <i>and unknown</i> organic fluorine.

Improved total organic fluorine methods for more comprehensive measurement of PFAS in industrial wastewater, river water, and air

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