Using mass defect plots as a discovery tool to identify novel fluoropolymer thermal decomposition products

Fire events involving halogenated materials, such as plastics and electronics, produce complex mixtures that include unidentified toxic and environmentally persistent contaminants. Ultrahigh‐resolution mass spectrometry and mass defect filtering can facilitate compound identification within these complex mixtures. In this study, thermal decomposition products of polychlorotrifluoroethylene (PCTFE, [–CClF–CF₂–]_n), a common commercial polymer, were analyzed by Fourier transform ion cyclotron resonance mass spectrometry. Using the mass defect plot as a guide, novel PCTFE thermal decomposition products were identified, including 29 perhalogenated carboxylic acid (PXCA, X = Cl,F) congener classes and 21 chlorine/fluorine substituted polycyclic aromatic hydrocarbon (X‐PAH, X = Cl,F) congener classes. This study showcases the complexity of fluoropolymer thermal decomposition and the potential of mass defect filtering to characterize complex environmental samples. Copyright © 2014 John Wiley & Sons, Ltd.