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ABSTRACTPer- and polyfluoroalkyl substances (PFAS) pose a major health and environmental problem. Methods are needed to ensure that PFAS are not released into the environment during their use or disposal. Alumina-based catalysts have been used for the abatement of small perfluorocarbons, e.g. tetrafluoromethane and perfluoropropane, emitted during the silicon etching process. Here, an alumina-based catalyst was tested to determine if these catalysts may facilitate the destruction of gas-phase PFAS. The catalyst was challenged with two nonionic surfactants with eight fluorinated carbons, 8:2 fluorotelomer alcohol and N-Ethyl-N-(2-hydroxyethyl)perfluorooctylsulfonamide. The catalyst helped decrease the temperatures needed for the destruction of the parent PFAS relative to a thermal-only treatment. Temperatures of 200°C were sufficient to destroy the parent PFAS using the catalyst, although a significant number of fluorinated products of incomplete destruction (PIDs) were observed. The PIDs were no longer observed by about 500°C with catalyst treatment. Alumina-based catalysts are a promising PFAS pollution control technology that could eliminate both perfluorocarbons and longer chain PFAS from gas streams.Implications:The release of per- and polyfluoroalkyl substances (PFAS) into the atmosphere can cause problems for human health and the environment. It is critical to reduce and eliminate PFAS emissions from potential sources, such as manufacturers, destruction technologies, and fluoropolymer processing and application sites. Here, an alumina-based catalyst was used to eliminate the emissions of two gas-phase PFAS with eight fully fluorinated carbons. No PFAS were observed in the emissions when the catalyst was at 500°C, lowering the energy requirements for PFAS destruction. This shows that alumina-based catalysts are a promising area for research for PFAS pollution controls and the elimination of PFAS emissions into the atmosphere.

ABSTRACTDuring thermal processes utilized in affixing fluoropolymer coatings dispersion to fibers and fabrics, coating components are vaporized. It is suspected that per- and polyfluoroalkyl substances (PFAS) from the dispersions may undergo chemical transformations at the temperatures used, leading to additional emitted PFAS thermal byproducts. It is important to characterize these emissions to support evaluation of the resulting environmental and health impacts. In this study, a bench-scale system was built to simulate this industrial process via thermal application of dispersions to fiberglass utilizing relevant temperatures and residence times in sequential drying, baking, and sintering steps. Experiments were performed with two commercially available dispersions and a simple model mixture containing a single PFAS (6:2 fluorotelomer alcohol [6:2 FTOH]). Vapor-phase emissions were sampled and characterized by several off-line and real-time mass spectrometry techniques for targeted and nontargeted PFAS. Results indicate that multiple PFAS thermal transformation products and multiple nonhalogenated organic species were emitted from the exit of the high temperature third (sintering) furnace when 6:2 FTOH was the only PFAS present in the aqueous mixture. This finding supports the hypothesis that temperatures typical of these industrial furnaces may also induce chemical transformations within the fluorinated air emissions. Experiments using the two commercial fluoropolymer dispersions indicate air emissions of part-per-million by volume (ppmv) concentrations of heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether (Fluoroether E1), as well as other PFAS at operationally relevant temperatures. We suspect that E1 is a direct thermal decomposition product (via decarboxylation) of 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoic acid (commonly referred to as HFPO-DA) present in the dispersions. Other thermal decomposition products, including the monomer, tetrafluoroethene, may originate from the PFAS used to stabilize the dispersion or from the polymer particles in suspension. This study represents the first researcher-built coating application simulator to report nontargeted PFAS emission characterization, real-time analyses, and the quantification of 30 volatile target PFAS.Implications: Thermal processes used to affix fluoropolymers to fabrics are believed to be a source of PFAS air emissions. These coating operations are used by many large and small manufacturers and typically do not currently require any air emissions control. This research designed and constructed a bench-scale system that simulates these processes and used several off-line and advanced real-time mass spectroscopy techniques to characterize PFAS air emissions from two commercial fluoropolymer dispersions. Further, as the compositions of commercial dispersions are largely unknown, a model three-component solution containing a single PFAS was used to characterize emissions of multiple PFAS thermal transformation products at operationally relevant conditions. This research shows that fluoropolymer fabric coating facilities can be sources of complex mixtures of PFAS air emissions that include volatile and semivolatile PFAS present in the dispersions, as well as PFAS byproducts formed by the thermal transformation of fluorocarbon and hydrocarbon species present in these dispersions.

To better understand the absorption of combustion byproducts during firefighting, we performed biological monitoring (breath and urine) on firefighters who responded to controlled residential fires and examined the results by job assignment and fire attack tactic. Urine was analyzed for metabolites of polycyclic aromatic hydrocarbons (PAHs) and breath was analyzed for volatile organic compounds (VOCs) including benzene. Median concentrations of PAH metabolites in urine increased from pre-firefighting to 3-h post firefighting for all job assignments. This change was greatest for firefighters assigned to attack and search with 2.3, 5.6, 3.9, and 1.4-fold median increases in pyrene, phenanthrene, naphthalene, and fluorene metabolites. Median exhaled breath concentrations of benzene increased 2-fold for attack and search firefighters (p< 0.01) and 1.4-fold for outside vent firefighters (p= 0.02). Compared to interior attack, transitional attack resulted in 50% less uptake of pyrene (p= 0.09), 36% less uptake phenanthrene (p= 0.052), and 20% less uptake of fluorene (p< 0.01). Dermal absorption likely contributed to firefighters’ exposures in this study. Firefighters’ exposures will vary by job assignment and can be reduced by employing a transitional fire attack when feasible.

AbstractBackground:The human exposome, defined as ‘…everything that is not the genome’, comprises all chemicals in the body interacting with life processes. The exposome drives genes x environment (GxE) interactions that can cause long-term latency and chronic diseases. The exposome constantly changes in response to external exposures and internal metabolism. Different types of compounds are found in different biological media.Objective:Measure polar volatile organic compounds (PVOCs) excreted in urine to document endogenous metabolites and exogenous compounds from environmental exposures.Methods:Use headspace collection and sorbent tube thermal desorption coupled with bench-top gas chromatography-mass spectrometry (GC-MS) for targeted and non-targeted approaches. Identify and categorize PVOCs that may distinguish among healthy and affected individuals.Results:Method is successfully demonstrated to tabulate a series of 28 PVOCs detected in human urine across 120 samples from 28 human subjects. Median concentrations range from below detect to 165 ng/mL. Certain PVOCs have potential health implications.Conclusions:Headspace collection with sorbent tubes is an effective method for documenting PVOCs in urine that are otherwise difficult to measure. This methodology can provide probative information regarding biochemical processes and adverse outcome pathways (AOPs) for toxicity testing.