Search

Aqueous film-forming foams (AFFFs) are used in firefighting applications and often contain per- and polyfluoroalkyl substances (PFAS), which can detrimentally impact environmental and biological health. Incineration is a potential disposal method for AFFFs, which may produce secondary PFAS and other air pollutants. We used online chemical ionization mass spectrometry (CIMS) to measure volatile PFAS emissions from incinerating AFFF concentrate solutions. We quantified perfluorinated carboxylic acids (PFCAs) during the incineration of legacy and contemporary AFFFs. These included trifluoroacetic acid, which reached mg m -3 quantities in the incinerator exhaust. These PFCAs likely arose as products of incomplete combustion of AFFF fluorosurfactants with lower peak furnace temperatures yielding higher PFCA concentrations. We also detected other short-chain PFAS, and other novel chemical products in AFFF combustion emissions. The volatile headspace above AFFF solutions contained larger ( C ≥ 8), less oxidized PFAS detected by CIMS. We identified neutral PFAS resembling fluorotelomer surfactants (e.g., fluorotelomer sulfonamide alkylbetaines and fluorotelomer thioether amido sulfonates) and fluorotelomer alcohols in contemporary AFFF headspaces. Directly comparing the distinct chemical spaces of AFFF volatile headspace and combustion byproducts as measured by CIMS provides insight toward the chemistry of PFAS during thermal treatment of AFFFs.

During 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.

A combustion model, originally developed to simulate the destruction of chemical warfare agents, was modified to include C 1 -C 3 fluorinated organic reactions and kinetics compiled by the National Institute of Standards and Technology (NIST). A simplified plug flow reactor version of this model was used to predict the destruction efficiency (DE) and formation of products of incomplete combustion (PICs) for three C 1 and C 2 per- and poly-fluorinated alkyl substances (PFAS) (CF 4 , CHF 3 , and C 2 F 6 ) and compare predicted values to Fourier Transform Infrared spectroscopy (FTIR)-based measurements made from a pilot-scale EPA research combustor (40-64 kW, natural gas-fired, 20% excess air). PFAS were introduced through the flame, and at post-flame locations along a time-temperature profile allowing for simulation of direct flame and non-flame injection, and examination of the sensitivity of PFAS destruction on temperature and free radical flame chemistry. Results indicate that CF 4 is particularly difficult to destroy with DEs ranging from ~60 to 95% when introduced through the flame at increasing furnace loads. Due to the presence of lower energy C-H and C-C bonds to initiate molecular dissociation reactions, CHF 3 and C 2 F 6 were easier to destroy, exhibiting DEs >99% even when introduced post-flame. However, these lower bond energies may also lead to the formation of CF 2 and CF 3 radicals at thermal conditions unable to fully de-fluorinate these species and formation of fluorinated PICs. DEs determined by the model agreed well with the measurements for CHF 3 and C 2 F 6 but overpredicted DEs at high temperatures and underpredicted DEs at low temperatures for CF 4 . However, high DEs do not necessarily mean absence of PICs, with both model predictions and limited FTIR measurements indicating the presence of similar fluorinated PICs in the combustion emissions. The FTIR was able to provide real-time emission measurements and additional model development may improve prediction of PFAS destruction and PIC formation. Implications: The widespread use of PFAS for over 70 years has led to their presence in multiple environmental matrixes including human tissues. While the chemical and thermal stability of PFAS are related to their desirable properties, this stability means that PFAS are very slow to degrade naturally and potentially difficult to destroy completely through thermal treatment processes often used for organic waste destruction. In this applied combustion study, model PFAS compounds were introduced to a pilot-scale EPA research furnace. Real-time FTIR measurements were performed of the injected compound and trace products of incomplete combustion (PICs) at operationally relevant conditions, and the results were successfully compared to kinetic model predictions of those same PFAS destruction efficiencies and trace gas-phase PIC constituents. This study represents a significant potential enhancement in available tools to support effective management of PFAS-containing wastes.