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.

[1]  Karl J. Jobst,et al.  The use of mass defect plots for the identification of (novel) halogenated contaminants in the environment , 2013, Analytical and Bioanalytical Chemistry.

[2]  A. Marshall,et al.  Two- and three-dimensional van krevelen diagrams: a graphical analysis complementary to the kendrick mass plot for sorting elemental compositions of complex organic mixtures based on ultrahigh-resolution broadband fourier transform ion cyclotron resonance mass measurements. , 2004, Analytical chemistry.

[3]  Y. Tondeur,et al.  Bromo- and bromochloro-polynuclear aromatic hydrocarbons, dioxins and dibenzofurans in municipal incinerator fly ash. , 1988, Biomedical & environmental mass spectrometry.

[4]  Senar Ozcan,et al.  Ultrasonic Solvent Extraction of Persistent Organic Pollutants from Airborne Particles , 2007 .

[5]  S. Mabury,et al.  The use of 19F NMR and mass spectrometry for the elucidation of novel fluorinated acids and atmospheric fluoroacid precursors evolved in the thermolysis of fluoropolymers. , 2003, The Analyst.

[6]  V. Taguchi,et al.  Dioxin analysis by gas chromatography-Fourier transform ion cyclotron resonance mass spectrometry (GC-FTICRMS) , 2010, Journal of the American Society for Mass Spectrometry.

[7]  A. Marshall,et al.  Petroleomics: The Next Grand Challenge for Chemical Analysis , 2004 .

[8]  R. Chambers,et al.  Fluorine in organic chemistry , 1973 .

[9]  王祖浩 孙丹儿 杨惠仙.  Chemistry:The Molecular Nature of Matter and Change评述 , 2007 .

[10]  Qing X. Li,et al.  Polychlorinated naphthalenes and other chlorinated tricyclic aromatic hydrocarbons emitted from combustion of polyvinylchloride. , 2006, Journal of hazardous materials.

[11]  E. Kendrick.  A Mass Scale Based on CH2 = 14.0000 for High Resolution Mass Spectrometry of Organic Compounds. , 1963 .

[12]  E. Zeng,et al.  Environmental and human exposure to soil chlorinated and brominated polycyclic aromatic hydrocarbons in an urbanized region , 2012, Environmental toxicology and chemistry.

[13]  A G Marshall,et al.  Kendrick mass defect spectrum: a compact visual analysis for ultrahigh-resolution broadband mass spectra. , 2001, Analytical chemistry.

[14]  P. Howard,et al.  Identifying new persistent and bioaccumulative organics among chemicals in commerce. , 2010, Environmental science & technology.

[15]  S. Mabury,et al.  Chlorodifluoroacetic acid fate and toxicity to the macrophytes Lemna gibba, Myriophyllum spicatum, and Myriophyllum sibiricum in aquatic microcosms , 2001, Environmental toxicology and chemistry.

[16]  K. Solomon,et al.  Haloacetic acids in the aquatic environment. Part I: macrophyte toxicity. , 2004, Environmental pollution.

[17]  Hong-Gang Ni,et al.  Halogenated polycyclic aromatic hydrocarbons in the environment. , 2013, Chemosphere.

[18]  K. Solomon,et al.  Haloacetic acids in the aquatic environment. Part II: ecological risk assessment. , 2004, Environmental pollution.

[19]  Nobuyoshi Yamashita,et al.  Analysis of trifluoroacetic acid and other short-chain perfluorinated acids (C2-C4) in precipitation by liquid chromatography-tandem mass spectrometry: comparison to patterns of long-chain perfluorinated acids (C5-C18). , 2008, Analytica chimica acta.

[20]  T. Ohura,et al.  Environmental analysis of chlorinated and brominated polycyclic aromatic hydrocarbons by comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry. , 2011, Journal of chromatography. A.

[21]  M. Zulfiqar,et al.  Study of the thermal degradation of polychlorotrifluoroethylene, poly(vinylidene fluoride) and copolymers of chlorotrifluoroethylene and vinylidene fluoride , 1994 .

[22]  R. Letcher,et al.  Monitoring of perfluorinated compounds in aquatic biota: an updated review. , 2011, Environmental science & technology.

[23]  Can Bruce,et al.  Probabilistic enrichment of phosphopeptides by their mass defect. , 2006, Analytical chemistry.

[24]  Scott A. Mabury,et al.  Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment , 2001, Nature.

[25]  L. Sleno,et al.  The use of mass defect in modern mass spectrometry. , 2012, Journal of mass spectrometry : JMS.

[26]  Lutz Ahrens,et al.  Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate. , 2011, Journal of environmental monitoring : JEM.