A review of sample collection and analytical methods for detecting per- and polyfluoroalkyl substances in indoor and outdoor air.

Per- and polyfluoroalkyl substances (PFAS) are a unique class of chemicals synthesized to aid in industrial processes, fire-fighting products, and to benefit consumer products such as clothing, cosmetics, textiles, carpets, and coatings. The widespread use of PFAS and their strong carbon-fluorine bonds has led to their ubiquitous presence throughout the world. Airborne transport of PFAS throughout the atmosphere has also contributed to environmental pollution. Due to the potential environmental and human exposure concerns of some PFAS, research has extensively focused on water, soil, and organismal detection, but the presence of PFAS in the air has become an area of growing concern. Methods to measure polar PFAS in various matrices have been established, while the investigation of polar and nonpolar PFAS in air is still in its early development. This literature review aims to present the last two decades of research characterizing PFAS in outdoor and indoor air, focusing on active and passive air sampling and analytical methods. The PFAS classes targeted and detected in air samples include fluorotelomer alcohols (FTOHs), perfluoroalkane sulfonamides (FASAs), perfluoroalkane sulfonamido ethanols (FASEs), perfluorinated carboxylic acids (PFCAs), and perfluorinated sulfonic acids (PFSAs). Although the manufacturing of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) has been largely phased out, these two PFAS are still often detected in air samples. Additionally, recent estimates indicate that there are thousands of PFAS that are likely present in the air that are not currently monitored in air methods. Advances in air sampling methods are needed to fully characterize the atmospheric transport of PFAS.

Low temperature destruction of gas-phase per- and polyfluoroalkyl substances using an alumina-based catalyst.

Per- 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.

Characterization of PFAS air emissions from thermal application of fluoropolymer dispersions on fabrics.

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.

Pilot-Scale Thermal Destruction of Per- and Polyfluoroalkyl Substances in a Legacy Aqueous Film Forming Foam.

The destruction of per- and polyfluoroalkyl substances (PFAS) is critical to ensure effective remediation of PFAS contaminated matrices. The destruction of hazardous chemicals within incinerators and other thermal treatment processes has historically been determined by calculating the destruction efficiency (DE) or the destruction and removal efficiency (DRE). While high DEs, >99.99%, are deemed acceptable for most hazardous compounds, many PFAS can be converted to other PFAS at low temperatures resulting in high DEs without full mineralization and the potential release of the remaining fluorocarbon portions to the environment. Many of these products of incomplete combustion (PICs) are greenhouse gases, most have unknown toxicity, and some can react to create new perfluorocarboxylic acids. Experiments using aqueous film forming foam (AFFF) and a pilot-scale research combustor varied the combustion environment to determine if DEs indicate PFAS mineralization. Several operating conditions above 1090 °C resulted in high DEs and few detectable fluorinated PIC emissions. However, several conditions below 1000 °C produced DEs >99.99% for the quantifiable PFAS and mg/m3 emission concentrations of several non-polar PFAS PICs. These results suggest that DE alone may not be the best indication of total PFAS destruction, and additional PIC characterization may be warranted.

Developing innovative treatment technologies for PFAS-containing wastes.

The release of persistent per- and polyfluoroalkyl substances (PFAS) into the environment is a major concern for the United States Environmental Protection Agency (U.S. EPA). To complement its ongoing research efforts addressing PFAS contamination, the U.S. EPA's Office of Research and Development (ORD) commissioned the PFAS Innovative Treatment Team (PITT) to provide new perspectives on treatment and disposal of high priority PFAS-containing wastes. During its six-month tenure, the team was charged with identifying and developing promising solutions to destroy PFAS. The PITT examined emerging technologies for PFAS waste treatment and selected four technologies for further investigation. These technologies included mechanochemical treatment, electrochemical oxidation, gasification and pyrolysis, and supercritical water oxidation. This paper highlights these four technologies and discusses their prospects and the development needed before potentially becoming available solutions to address PFAS-contaminated waste.Implications: This paper examines four novel, non-combustion technologies or applications for the treatment of persistent per- and polyfluoroalkyl substances (PFAS) wastes. These technologies are introduced to the reader along with their current state of development and areas for further development. This information will be useful for developers, policy makers, and facility managers that are facing increasing issues with disposal of PFAS wastes.

Combustion of C1 and C2 PFAS: Kinetic modeling and experiments.

A combustion model, originally developed to simulate the destruction of chemical warfare agents, was modified to include C1-C3 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 C1 and C2 per- and poly-fluorinated alkyl substances (PFAS) (CF4, CHF3, and C2F6) 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 CF4 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, CHF3 and C2F6 were easier to destroy, exhibiting DEs >99% even when introduced post-flame. However, these lower bond energies may also lead to the formation of CF2 and CF3 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 CHF3 and C2F6 but overpredicted DEs at high temperatures and underpredicted DEs at low temperatures for CF4. 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.

Low Temperature Thermal Treatment of Gas-Phase Fluorotelomer Alcohols by Calcium Oxide.

Given the extent to which per- and polyfluoroalkyl substances (PFAS) are used in commercial and industrial applications, the need to evaluate treatment options that reduce environmental emissions and human and ecological exposures of PFAS is becoming more necessary. One specific chemical class of PFAS, fluorotelomer alcohols (FTOHs), have vapor pressures such that a significant fraction is expected to be present in the gas-phase even at ambient temperatures. FTOHs are used in a variety of PFAS applications, including synthesis and material coatings. Using two complementary mass spectrometric methods, the use of calcium oxide (CaO) was examined as a low temperature and potentially low-cost thermal treatment media for removal and destruction of four gas-phase FTOHs of varying molecular weights. This was accomplished by assessing the removal/destruction efficiency of the FTOHs and the formation of fluorinated byproducts as a function of treatment temperature (200 - 800 °C) in the presence of CaO compared to thermal-only destruction. During the treatment process, there is evidence that other PFAS compounds are produced at low temperatures (200 - 600 °C) as the primary FTOH partially degrades. At temperatures above 600 °C, thermal treatment with CaO prevented the formation or removed nearly all these secondary products.

A crosslinked, low pH-stable, mixed-mode cation-exchange like stationary phase made using the thiol-yne click reaction.

Mixed-mode cation-exchange stationary phases are useful for the separation of mixtures containing hydrophobic, acidic, and basic molecules. To ensure that weak organic bases are protonated and carboxylic acids are neutral low pH mobile phases are required. Mixed-mode stationary phases that are stable at pH < 3 are needed. We synthesized a crosslinked structure along the surface of thiol functionalized silica gel particles using the thiol-yne click reaction. The alkyne, 1,7-octadiyne, was added to the 3-mercaptopropyl silica gel, then crosslinked using 1,6-hexanedithiol. Elemental analysis showed low octadiyne ligand surface coverage, but, stoichiometrically, three sulfurs were added to each octadiyne ligand during the crosslinking step, indicating that crosslinking occurred. The effect of the crosslinking on the stability was tested with a 50:50 (v/v) pH 0.50 5% TFA aqueous:acetonitrile mobile phase at 70 °C for six days, over 35,000 column volumes. The stationary phase showed good stability with the retention of triphenylene decreasing only 20% during that time. The Tanaka test showed that the phase has a methylene selectivity of 1.20 ± 0.04, a high shape selectivity of 2.71 ± 0.03, and a 3.98 ± 0.05 cation-exchange factor at pH 2.70. The phase has a selectivity factor for nitrobenzene and benzene of 1.41 ± 0.01, indicating the electron donating charge transfer characteristic of the phase. The mixed-mode characteristics of the phase were investigated using a mixture of the monoamine neurotransmitters norepinephrine, dopamine, and serotonin. Baseline resolution of the monoamines could be obtained using a simple 20 mM potassium phosphate (pH 2.70)/methanol mobile phase. Altering both the methanol content and the potassium ion concentration altered the retention of the monoamines indicating mixed-mode cation exchange characteristic of the crosslinked stationary phase.

A liquid chromatographic charge transfer stationary phase based on the thiol-yne reaction.

In the process of developing a pH-stable, highly crosslinked stationary phase using the thiol-yne reaction, a new charge transfer stationary phase was discovered. The first step in the preparation of the crosslinked phase is to attach 1,4-diethynylbenzene (DEB) to thiol functionalized silica particles using the thiol-yne reaction. Upon preparation of that phase, we noticed that the color of the particles was different when the modified particles were wet with aromatic solvents in comparison to wetting with nonaromatic or aqueous solvents. This color change was still apparent upon crosslinking the DEB with 1,6-hexanedithiol to create the crosslinked stationary phase. The chromatographic selectivity for the flat triphenylene over the bulkier o-terphenyl, αT/OT is an indicator of shape selectivity. The crosslinked phase⬢s αT/OT is 4.91 ± 0.08, almost twice that of the most shape-selective reversed phase column. The difference of the entropy contributions to retention free energy between the two compounds, ΝTΝS° at 298⬰K, is statistically indistinguishable from zero, (↙0.1⬰±â¬°0.9⬰kJ/mol) leading us to believe that the observed shape selectivity is not consistent with the slot model. To test the hypothesis that the DEB-thiol adduct, a 4-ethynyl styryl sulfide (ESS), was responsible for the observed behavior, we prepared a low coverage ESS-containing phase which, unlike higher density, crosslinked, or polymeric phases, should not display shape selectivity based on ⬓slots⬽. With the ESS phase the shape selectivity remained high, with αT/OT⬰=⬰3.23⬰±â¬°0.01. The ESS ligand has electron donating characteristics based on the selectivity for nitrobenzene compared to benzene: 1.83⬰±â¬°0.10 on the ESS phase vs 0.64 ± 0.01 on a commercial C18 stationary phase. This shows that the thiol-yne based ESS stationary phase has electron donating charge transfer characteristics.

A pH-stable, crosslinked stationary phase based on the thiol-yne reaction.

Stationary phases that can withstand extremes of pH and temperature are needed to allow a single column to accommodate a wider set of solutes and separation criteria. We used a simple multi-step process using the thiol-yne reaction following the modification of the silica surface with a thiol-containing silane. The monomers 1,4-diethynylbenzene (DEB) and 1,6-hexanedithiol were used to create a crosslinked thiol-yne (CTY) stationary phase along the surface of the thiol functionalized silica. In the Tanaka test characterization, the CTY phase showed a low phase ratio, methylene selectivity typical of a reversed phase, and extremely high shape selectivity compared to commercial reversed phases. The hydrophobic subtraction model characterization showed a high positive steric resistance, a low hydrogen bond acidity, and a high cation-exchange capacity compared to most reversed phases. At pH 0.5 with an 85% aqueous mobile phase the phase showed no significant change over 114 h. With a 50% aqueous mobile phase the phase took four more days than a sterically protected C18 phase for the k' to decline 25%. At pH 12.6, 50% aqueous mobile phase, a sterically protected C18 phase showed a 20% decrease in k' and more than a 60% decrease in theoretical plates per meter in three hours. The CTY phase actually showed modest increases in k' and theoretical plates per meter after three hours.