Per- and polyfluoroalkyl substances (PFAS or PFASs) are a group of synthetic organofluorine chemical compounds that have multiple fluorine atoms attached to an alkyl chain. An early definition, from 2011, required that they contain at least one perfluoroalkyl moiety, –CnF2n+1–. Beginning in 2021, the Organisation for Economic Co-operation and Development (OECD) expanded their terminology, stating that "PFASs are defined as fluorinated substances that contain at least one fully fluorinated methyl or methylene carbon atom (without any H/Cl/Br/I atom attached to it), i.e., with a few noted exceptions, any chemical with at least a perfluorinated methyl group (–CF3) or a perfluorinated methylene group (–CF2–) is a PFAS."
According to the OECD, at least 4,730 distinct PFASs that contain at least three perfluorinated carbon atoms are known. The United States Environmental Protection Agency's (EPA) toxicity database, DSSTox, lists 14,735 unique PFAS chemical compounds, while PubChem lists approximately 6 million. The fluorinated surfactants or fluorosurfactants subgroup has a fluorinated "tail" and a hydrophilic "head" and are thus considered surfactants. These are more effective at reducing the surface tension of water than comparable hydrocarbon surfactants. They include the perfluorosulfonic acids, such as perfluorooctanesulfonic acid (PFOS), and the perfluorocarboxylic acids like perfluorooctanoic acid (PFOA).
Many PFASs were used in the mid-20th century in products and on materials due to their enhanced water-resistant properties, such as within Teflon or aqueous film forming foam. Only since the start of the 21st century has the environmental impact and toxicity to human and mammalian life been studied in depth. PFOS, PFOA and other PFASs are commonly described as persistent organic pollutants or "forever chemicals" because they remain in the environment for long periods of time. Residues have been detected in humans and wildlife, prompting concern about impacts to health. According to the National Academies of Sciences, Engineering, and Medicine, PFAS exposure is linked to increased risk of dyslipidemia (abnormally high cholesterol), suboptimal antibody response, reduced infant and fetal growth, and higher rates of kidney cancer.
Fluorosurfactants
Fluorosurfactants are surfactants containing fluorocarbon chains such as those in PFASs. Their hydrophobic nature can reduce the surface tension of water below what is attainable by using hydrocarbon surfactants, so fluorosurfactants tend to concentrate at the liquid-air interface. Fluorocarbons are both lipophobic and hydrophobic, which allows them to repel both oil and water. Their lipophobicity results from the relative lack of London dispersion forces when compared to hydrocarbons, a consequence of fluorine's large electronegativity and small bond length, which reduce the polarizability of the surfactants' fluorinated molecular surface. Fluorosurfactants are more stable and fit for harsher conditions than hydrocarbon surfactants because of the stability of the carbon–fluorine bond. Perfluorinated surfactants persist in the environment for the same reason.
Economic role
PFASs play a key economic role for companies such as DuPont, 3M, and W. L. Gore & Associates because they are used in emulsion polymerization to produce fluoropolymers. They have two main markets: a $1 billion annual market for use in stain repellents, and a $100 million annual market for use in polishes, paints, and coatings. In 2022, 3M announced that it will end PFAS production by 2025.
Health and environmental effects
On their introduction in the 1940s, PFASs were considered inert. Early occupational studies revealed elevated levels of fluorochemicals, including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA, C8), in the blood of exposed industrial workers, but cited no ill health effects. These results were consistent with the measured serum concentrations of PFOS and PFOA in 3M plant workers ranging from 0.04 to 10.06 ppm and 0.01 to 12.70 ppm, respectively, well below toxic and carcinogenic levels cited in animal studies. Given, however, the "forever chemical" property of PFASs (serum elimination half-life of 4–5 years) and widespread environmental contamination, molecules have been shown to accumulate in humans to such a degree that adverse health outcomes have resulted.