External liquid calibration method for iodide chemical ionization mass spectrometry enables quantification of gas-phase per- and polyfluoroalkyl substances (PFAS) dynamics in indoor air
Michael J. Davern, Gabrielle V. West, Clara M. A. Eichler, Barbara J. Turpin, Yue Zhang, Jason D. Surratt
Abstract
, 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.