Tubing material considerably affects measurement delays of gas-phase oxygenated per- and polyfluoroalkyl substances.

Abstract

Per- and polyfluoroalkyl substances (PFAS) are persistent environmental pollutants associated with negative health impacts. Assessments of tubing-related measurement bias for volatile PFAS are lacking, as gas-wall interactions with tubing can delay quantification of gas-phase analytes. We use online iodide chemical ionization mass spectrometry measurements to characterize tubing delays for three gas-phase oxygenated PFAS - 4:2 fluorotelomer alcohol (4:2 FTOH), perfluorobutanoic acid (PFBA), and hexafluoropropylene oxide dimer acid (HFPO-DA). Perfluoroalkoxy alkane and high-density polyethylene tubing yielded relatively short absorptive measurement delays, with no clear dependence on tubing temperature or sampled humidity. Sampling through stainless steel tubing led to prolonged measurement delays due to reversible adsorption of PFAS to the tubing surface, with strong dependence on tubing temperature and sample humidification. Silcosteel tubing afforded shorter measurement delays than stainless steel due to diminished surface adsorption of PFAS. Characterizing and mitigating these tubing delays is crucial for reliable quantification of airborne PFAS.Implications: Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants. Many PFAS are sufficiently volatile to exist as airborne pollutants. Measurements and quantification of airborne PFAS can be biased from material-dependent gas-wall interactions with sampling inlet tubing. Thus, characterizing these gas-wall interactions are crucial for reliably investigating emissions, environmental transport, and fates of airborne PFAS.