External liquid calibration method for iodide chemical ionization mass spectrometry enables quantification of gas-phase per- and polyfluoroalkyl substances (PFAS) dynamics in indoor air.

Per- and polyfluoroalkyl substances (PFAS) are manufactured chemicals that have been detected across the globe. Fluorotelomer alcohols (FTOHs) are one PFAS class commonly found in indoor air due to emissions from consumer products ( e.g. , textiles and food packaging) and are human metabolic, atmospheric oxidative, and industrial precursors of perfluoroalkyl carboxylic acids (PFCAs). We developed a quantitative method for real-time analysis of gas-phase FTOHs, perfluoroalkyl acids (PFCAs and GenX), one perfluorooctane sulfonamide (EtFOSA), one fluorotelomer diol (FTdiOH), and one fluorinated ether (E2) using high-resolution time-of-flight chemical ionization mass spectrometry equipped with iodide reagent ion chemistry (I-HR-ToF-CIMS). Herein, we present a direct liquid injection method for external calibration, providing detection limits of 0.19-3.1 pptv for 3 s averaging and 0.02-0.44 pptv for 120 s averaging, with the exception of E2, which had detection limits of 1700 and 220 pptv for 3- and 120 s averaging, respectively. These calibrations enabled real-time gas-phase quantification of 6 : 2 FTOH in room air while microwaving popcorn, with an average peak air concentration of 31.6 ± 4.5 pptv measured 2 meters from a closed microwave. Additionally, 8 : 2 and 10 : 2 FTOH concentrations in indoor air were measured in the presence and absence of a rain jacket, with observed peak concentrations of 110 and 25 pptv, respectively. Our work demonstrates the ability of I-HR-ToF-CIMS to provide real-time air measurements of PFAS relevant to indoor human exposure settings and allow for PFAS source identification. We expect that real-time quantification of other gas-phase PFAS classes is possible, enabling advances in understanding PFAS sources, chemistry, and partitioning.