Investigation of Real-Time Gaseous Thermal Decomposition Products of Representative Per- and Polyfluoroalkyl Substances (PFAS)

The thermal decomposition of per- and poly fluoroalkyl substances (PFAS) is poorly understood. Here, we present an innovative, comprehensive analytical method to investigate their thermal decomposition, including perfluorocarboxylic acids (PFCAs), alcohol, sulfonates, and GenX (acid dimer), focusing on identifying their breakdown products. In this study, evolved gas analysis-mass spectrometry (EGA-MS) was used for fast real-time screening to determine the significant temperatures to be investigated with the thermal desorption-pyrolysis coupled with gas chromatography-mass spectrometry (TD-Py-GC-MS), which provided detailed information about evolved PFAS and their breakdown products. This approach enabled a systematic study of perfluorocarboxylic acids (PFCAs) ranging from C₃ to C₉ and GenX showing volatilization, followed by degradation and formation of respective perfluorinated-1-alkenes and C₅F₁₀O perfluorinated ether (from GenX). At elevated temperatures (e.g., 600 °C), the products observed included perfluorinated butene and higher molecular-weight products, likely formed by pyrolytic polymerization of perfluorinated radicals. 1H,1H,2H,2H-perfluoro-1-decanol, i.e., 8:2 FTOH, volatilized at 100 °C; however, at higher temperatures, several novel decomposition products were observed, including perfluoro-1-decene and perfluorinated compounds suggesting the presence of the hydroxylic group. Our method offers an alternative approach to studying the thermal behavior of currently regulated and emerging PFAS with a focus on application to a wide range of matrices (laboratory grade standards or environmental samples).