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.

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In Canada, perfluoroalkyl acids (PFAAs) have been the focus of several monitoring programs and research and surveillance studies. Here, we integrate recent data and perform a multi-media assessment to examine the current status and ongoing trends of PFAAs in Canada. Concentrations of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other long-chain perfluorocarboxylates (PFCAs) in air, water, sediment, fish, and birds across Canada are generally related to urbanization, with elevated concentrations observed around cities, especially in southern Ontario. PFOS levels in water, fish tissue, and bird eggs were below their respective Draft Federal Environmental Quality Guidelines, suggesting there is low potential for adverse effects to the environment/organisms examined. However, PFOS in fish and bird eggs tended to exceed guidelines for the protection of mammalian and avian consumers, suggesting a potential risk to their wildlife predators, although wildlife population health assessments are needed to determine whether negative impacts are actually occurring. Long-term temporal trends of PFOS in suspended sediment, sediment cores, Lake Trout (Salvelinus namaycush), and Herring Gull (Larus argentatus) eggs collected from Lake Ontario increased consistently from the start of data collection until the 1990s. However, after this time, the trends varied by media, with concentrations stabilizing in Lake Trout and Herring Gull eggs, and decreasing and increasing in suspended sediment and the sediment cores, respectively. For PFCAs, concentrations in suspended sediment, sediment cores, and Herring Gulls generally increased from the start of data collection until present and concentrations in Lake Trout increased until the late 1990s and subsequently stabilized. A multimedia comparison of PFAA profiles provided evidence that unexpected patterns in biota of some of the lakes were due to unique source patterns rather than internal lake processes. High concentrations of PFAAs in the leachate and air of landfill sites, in the wastewater influent/effluent, biosolids, and air at wastewater treatment plants, and in indoor air and dust highlight the waste sector and current-use products (used primarily indoors) as ongoing sources of PFAAs to the Canadian environment. The results of this study demonstrate the utility of integrating data from different media. Simultaneous evaluation of spatial and temporal trends in multiple media allows inferences that would be impossible with data on only one medium. As such, more co-ordination among monitoring sites for different media is suggested for future sampling, especially at the northern sites. We emphasize the importance of continued monitoring of multiple-media for determining future responses of environmental PFAA concentrations to voluntary and regulatory actions.

Little is known of the atmospheric fate(s) of fluorotelomer alcohols (FTOHs), a class of high-production-volume chemicals used in the production of water- and oil-repelling surface coatings and which have been detected in a wide variety of urban and remote environmental matrices. In the present study, we investigated the uptake and photochemistry of FTOHs at the surface of TiO2, Fe2O3, Mauritanian sand, and Icelandic volcanic ash. Gas-phase 3,3,3-trifluoropropanol, 4:2 FTOH, and 6:2 FTOH exhibited significant uptake to each of the surfaces under study. The sand- and ash-catalyzed heterogeneous photooxidation of 6:2 FTOH resulted in the rapid production and subsequent slow degradation of surface-sorbed perfluorinated carboxylic acids (PFCAs). We suggest that this transformation, which proceeds via saturated and unsaturated fluorotelomer carboxylic acid intermediates (6:2 FTCA/FTUCA), is catalyzed by Fe and Ti contained within the samples. These results provide the first evidence that the heterogeneous oxidation of FTOHs at metal-rich atmospheric surfaces may provide a significant loss mechanism for these chemicals and also act as a source of aerosol-phase PFCAs close to source regions. Subsequent long-range transport of these aerosol-sorbed PFCAs has the potential to join oceanic transport and local gas-phase FTOH oxidation as a source of PFCAs to Arctic regions.

Bromo-chloro alkenes (Br-Cl PXAs) have been used for over 30 years as flame retardants and are listed on several national chemical inventories. Very little publicly available information is available on Br-Cl PXAs, and thus preliminary ecological risk screening is challenging due to the lack of basic information such as molecular structure and associated physicochemical properties. Due to their likely similarity with chlorinated paraffins (CPs), Br-Cl PXAs may pose a similar environmental hazard. Several structural databases list such substances as "alkenes", although the industrial synthesis involves halogenation of linear alphaolefins and would be expected to produce linear alkanes. In this study, a combination of high-resolution separation and mass spectrometric techniques were used to characterize a Br-Cl PXA industrial technical product, C 12−30 bromo-chloro alphaalkenes (CAS RN 68527-01-5). The results show this product is dominated by C 18 carbon chain lengths, substituted with 3−7 chlorine atoms and 1−3 bromine atoms on an alkane chain. Long-chain C 18 chlorinated paraffins are also present, although they represent a relatively minor component. Experimental log K OW (6.9 to 8.6) and estimated log K OA (10.5 to 13.5) and log K AW (−5.1 to −0.6) partition coefficients suggest that this chemical will behave similarly to medium-and long-chain CPs as well as other persistent organic pollutants, such as highly chlorinated pesticides and polychlorinated biphenyls. The results of this study provide an initial step toward understanding the environmental behavior and persistence of Br-Cl PXAs, highlighting the need for further assessment and re-evaluation of the current structure(s) assigned to these compounds.