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Wikipedia

Per- and polyfluoroalkyl substances

Per- and polyfluoroalkyl substances (PFAS[1] or PFASs[2]) are a group of synthetic organofluorine chemical compounds that have multiple fluorine atoms attached to an alkyl chain. The PubChem database lists more than 6 million unique compounds in this group.[3] PFASs started being used in the mid-20th century to make fluoropolymer coatings and products that resist heat, oil, stains, grease, and water.[4] They are used in a variety of products including waterproof clothing, furniture, adhesives, food packaging, heat-resistant non-stick cooking surfaces, and the insulation of electrical wire.[4] They have played a key economic role for companies such as DuPont, 3M, and W. L. Gore & Associates that use them to produce widely known materials such as Teflon or Gore-Tex.

Many PFAS such as PFOS, PFOA are a health and environmental concern because they do not break down via natural processes and are commonly described as persistent organic pollutants or "forever chemicals".[4][5] They can also move through soils and contaminate drinking water sources and can build up (bioaccumulate) in fish and wildlife.[4] Residues have been detected in humans and wildlife.[4][6][7][8] Only since the start of the 21st century has the environmental impact and toxicity to human and mammalian life been studied in depth. Due to the large number of PFAS it is challenging to study and assess the potential human health and environmental risks; more research is necessary.[4][9][10] According to the United States Environmental Protection Agency, exposure to some PFAS in the environment may be linked to harmful health effects in humans and animals.[10] The International Agency for Research on Cancer (IARC) has classified PFOA as carcinogenic to humans and PFOS as possibly carcinogenic.[11] 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.[12]

Health concerns related to PFASs have resulted in numerous litigations (see Timeline of events related to per- and polyfluoroalkyl substances). PFAS producers such as 3M, Chemours, DuPont and Corteva have reached billion dollar agreements to settle claims against them. The use of PFAS is regulated in several parts of the world, with some plans to phase them out entirely from products.

Definition edit

 
Skeletal structure of PFOS, an effective, persistent and bioaccumulative fluorosurfactant
 
Space filling model of PFOS

Per- and polyfluoroalkyl substances are defined as 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–.[13][14] Beginning in 2021, the Organisation for Economic Co-operation and Development (OECD) expanded its 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."[2][15]

According to the OECD, at least 4,730 distinct PFASs that contain at least three perfluorinated carbon atoms are known.[16] The United States Environmental Protection Agency's (EPA) toxicity database, DSSTox, lists 14,735 unique PFAS chemical compounds,[17] while PubChem lists more than 6 million.[3]

Fluorosurfactants edit

 
Fluorine-containing durable water repellent makes a fabric water-resistant.

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).

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,[18] so fluorosurfactants tend to concentrate at the liquid-air interface.[19] 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.[6]

Economic role edit

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.[20] In 2022, 3M announced that it would end PFAS production by 2025.[21][22] Over the past two decades, production of certain PFASs has increasingly moved to Asia, where there is less regulatory scrutiny.[23]

Health and environmental effects edit

On their introduction in the 1940s, PFASs were considered inert.[24][25] 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.[26][27] 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.[27] 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.[24]

 
Effects of exposure to PFASs on human health[28][29][30]

Hormone-disrupting chemicals, including PFASs, are linked with rapid declines in human fertility.[31] In a meta-analysis for associations between PFASs and human clinical biomarkers for liver injury, authors considered both PFAS effects on liver biomarkers and histological data from rodent experimental studies and concluded that evidence exists showing that PFOA, perfluorohexanesulfonic acid (PFHxS), and perfluorononanoic acid (PFNA) are hepatotoxic to humans.[32]

Many comprehensive epidemiological studies linking adverse human health effects to PFASs, particularly PFOA, come from the C8 Science Panel.[33] The panel was formed as part of a contingency to a class action lawsuit brought by communities in the Ohio River Valley against DuPont in response to landfill and wastewater dumping of PFAS-laden material from DuPont's West Virginia Washington Works Plant.[33] The panel measured PFOA (also known as C8) serum concentrations in 69,000 individuals from around DuPont's Washington Works Plant and found a mean concentration of 83.0 ng/mL, compared to 4 ng/mL in a standard population of Americans.[34] This panel reported probable links between elevated PFOA blood concentration and hypercholesterolemia, ulcerative colitis, thyroid disease, testicular cancer, kidney cancer as well as pregnancy-induced hypertension and preeclampsia.[35][36][37][38][39]

Pregnancy edit

Exposure to PFAS is a risk factor for various hypertensive disorders in pregnancy, including preeclampsia and high blood pressure. It is not clear whether PFAS exposure is associated with wider cardiovascular disorders during pregnancy.[40] Human breast milk has the capability to harbor PFASs as well as be transferred from mother to infant through breastfeeding.[41]

Cancer edit

As of November 2023, the International Agency for Research on Cancer (IARC) has classified PFOA as carcinogenic to humans (Group 1) based on “sufficient” evidence for cancer in animals and “strong” mechanistic evidence in exposed humans. IARC also classified PFOS as possibly carcinogenic to humans (Group 2b) based on “strong” mechanistic evidence.[11] There is a lack of high-quality epidemiological data on the associations between many specific PFAS chemicals and specific cancer types, and research is ongoing.[42]

Prevalence in rainwater edit

In 2022, it was found that levels of at least four perfluoroalkyl acids (PFAAs) in rainwater worldwide ubiquitously and often greatly exceeded the EPA's lifetime drinking water health advisories as well as comparable Danish, Dutch, and European Union safety standards, leading to the conclusion that "the global spread of these four PFAAs in the atmosphere has led to the planetary boundary for chemical pollution being exceeded".[43] There are some moves to restrict and replace their use.[44]

Estimated contemporary costs edit

Chemical corporations that produce PFAS generate approximately US$4 billion in annual profits from the production of this chemical, but it is estimated that they impose much larger costs on taxpayers and the health of the planet's population (i.e. as external costs). Of these costs, remediation efforts fighting PFAS soil and water contamination are the most expensive, followed by the healthcare costs of treating people who develop cancer, thyroid disease, kidney dysfunction, birth defects, and other major medical conditions that have been linked to even low levels of exposure to PFAS, and the costs of monitoring of PFAS pollution in human and other life forms. Such costs to society have been estimated to amount to approximately US$17.5 trillion annually (which would be almost one fifth of the US$96 trillion global GDP in 2021[45]), according to a press release by The International Chemical Secretariat (ChemSec), a Sweden-based NGO that works with industry and policymakers to limit the use of toxic chemicals.[46]

Costs by region edit

In a report by the Nordic Council of Ministers, the total annual health-related costs associated with human exposure to PFASs were estimated to be at least €52–84 billion in the European Economic Area (EEA) countries.[47] Aggregated annual costs covering environmental screening, monitoring where contamination is found, water treatment, soil remediation and health assessment total €821 million – 170 billion in the EEA plus Switzerland.[47]

In the United States, estimated PFAS-attributable disease costs amount to 6–62 billion US$.[48] Studies have estimated the annual healthcare costs in the United States of each of some of the major diseases attributed to PFAS.[49]

Proposed mechanisms of PFAS-related adverse health outcomes edit

Hypercholesterolemia edit

A response is observed in humans where elevated PFOS levels were significantly associated with elevated total cholesterol and LDL cholesterol, highlighting significantly reduced PPAR expression and alluding to PPAR independent pathways predominating over lipid metabolism in humans compared to rodents.[50]

Ulcerative colitis edit

PFOA and PFOS have been shown to significantly alter immune and inflammatory responses in human and animal species. In particular, IgA, IgE (in females only) and C-reactive protein have been shown to decrease whereas antinuclear antibodies increase as PFOA serum concentrations increase.[51] These cytokine variations allude to immune response aberrations resulting in autoimmunity. One proposed mechanism is a shift towards anti-inflammatory M2 macrophages and/or T-helper (TH2) response in intestinal epithelial tissue which allows sulfate-reducing bacteria to flourish. Elevated levels of hydrogen sulfide result, which reduce beta-oxidation and nutrient production, leading to a breakdown of the colonic epithelial barrier.[52]

Thyroid disease edit

Hypothyroidism is the most common thyroid abnormality associated with PFAS exposure.[53] PFASs have been shown to decrease thyroid peroxidase, resulting in decreased production and activation of thyroid hormones in vivo.[54] Other proposed mechanisms include alterations in thyroid hormone signaling, metabolism and excretion as well as function of nuclear hormone receptor.[53]

Washington Post 2018 op-ed edit

Fluorosurfactants such as PFOS, PFOA, and PFNA have caught the attention of regulatory agencies because of their persistence, toxicity, and widespread occurrence in the blood of general populations[55][56] and wildlife. In 2009, PFOS, its salts, and perfluorooctanesulfonyl fluoride were listed as persistent organic pollutants under the Stockholm Convention due to their ubiquitous, persistent, bioaccumulative, and toxic nature.[57][58] PFAS chemicals were dubbed "forever chemicals" in a 2018 op-ed in the Washington Post.[59] The nickname was derived by combining the two dominant attributes of this class of chemicals: PFAS chemicals are characterized by a carbon-fluorine backbone (the "F-C" in "forever chemicals"), and the carbon-fluorine bond is one of the strongest bonds in organic chemistry, which gives these chemicals an extremely long environmental half-life. The term forever chemicals is commonly used in media outlets in addition to the more technical name of per- and polyfluorinated alkyl substances.[60][61][62] Their production has been regulated or phased out by manufacturers, such as 3M, DuPont, Daikin, and Miteni in the U.S., Japan, and Europe. In 2006 3M replaced PFOS and PFOA with short-chain PFASs,[20] such as perfluorohexanoic acid (PFHxA) and perfluorobutanesulfonic acid (PFBS). Shorter fluorosurfactants may be less prone to accumulating in mammals;[20] there is still some concern that they may be harmful to both humans[63][64][65] and the environment,[66] though the EPA states, "...research is still ongoing to determine how different levels of exposure to different PFAS can lead to a variety of health effects."[67] Many PFASs are either not covered by European legislation or are excluded from registration obligations under the EU REACH chemical regulation.[68] Several PFASs have been detected in drinking water,[69] municipal wastewater,[70] and landfill leachates[71] worldwide.

It had been thought that PFAAs would eventually end up in the oceans, where they would be diluted over decades, but a field study published in 2021 by researchers at Stockholm University found that they are significantly transferred from water to air when waves break on land, and are a significant source of air pollution, and eventually get into the rain. The researchers concluded that pollution "may impact large areas of inland Europe and other continents, in addition to coastal areas".[72][73]

Bioaccumulation and biomagnification edit

 
Bioaccumulation of PFAS: PFASs from sediments and water can accumulate in marine organisms. Animals higher up the food chain accumulate more PFAS because they absorb PFAS in prey they consume.
In marine species of the food web

Bioaccumulation controls internal concentrations of pollutants, including PFAS, in individual organisms. When bioaccumulation is looked at in the perspective of the entire food web, it is called biomagnification, which is incredibly important to track because lower concentrations of pollutants in environmental matrices such as seawater or sediments, can very quickly grow to harmful concentrations in organisms at higher trophic levels, including humans. Notably, concentrations in biota can even by >5000 times those present in water for PFOS and C10-C14 PFCAs.[74] PFAS can enter an organism by ingestion of sediment, through the water, or directly via their diet. It accumulates namely in areas with high protein content, in the blood and liver, but its also found to a lesser extent in tissues.[75]

Biomagnification can be described using the estimation of the trophic magnification factor (TMF), this describes the relationship between the contamination levels in a species and their trophic level in the food web. TMFs are determined by graphing the log transformed concentrations of PFAS against the assigned trophic level, and taking the antilog of the regression slope (10slope).[6]

In a study done on a macrotidal estuary in Gironde, SW France, TMFs were >1 for nearly all 19 PFAS compounds considered in the study and were particularly high for PFOA and PFNA (6.0 and 3.1 respectively).[6] A TMF> 1 means that accumulation in the organism is greater than that of the medium, in this case the medium being sea water.

PFOS, a long chain sulfonic acid, was found at the highest concentrations relative to other PFASs measured in fish and birds in Northern seas such as the Barents Sea and the Canadian Arctic.[76] A study and an interactive map by the EWG using its results showed freshwater fish in the U.S.[globalize] ubiquitously contain high levels of harmful PFAS, with a single serving typically significantly increasing the blood PFOS level.[77][78]

Bioaccumulation and biomagnification of PFASs in marine species throughout the food web, particularly frequently consumed fish and shellfish, can have important impacts on human populations.[79] PFASs have been frequently documented in both fish and shellfish that are commonly consumed by human populations,[80] which poses health risks to humans and studies on the bioaccumulation in certain species are important to determine daily tolerable limits for human consumption, and where those limits may be exceeded causing potential health risks.[81] This has particular implications for populations that consume larger numbers of wild fish and shellfish species.[80] In addition to health risks, populations may be impacted by advisories, limits of fishing closures for certain species that are put in place to help mitigate health risks from potential consumption of species with higher levels of accumulated PFASs, but result in a loss of food sources and important subsistence species depended on by local communities. There is research being done in this area, including into spatial patterns of PFAS bioaccumulation in fish and crustaceans.[82]

Corporate and federal government suppression of information edit

Since the 1970s, forty years before the public health community, DuPont and 3M were aware that PFAS was “highly toxic when inhaled and moderately toxic when ingested.”[83] Producers used several strategies to influence science and regulation – most notably, suppressing unfavorable research and distorting public discourse.[83]

In 2018 White House staff and the EPA pressured the U.S. Agency for Toxic Substances and Disease Registry to suppress a study that showed PFASs to be even more dangerous than previously thought.[84][85]

Concerns, litigation and regulations in specific countries and regions edit

Australia edit

In 2017, the ABC's current affairs program Four Corners reported that the storage and use of firefighting foams containing perfluorinated surfactants at Australian Defence Force facilities around Australia had contaminated nearby water resources.[86] In 2019, remediation efforts at RAAF Base Tindal and the adjacent town of Katherine were ongoing.[87] In the 2022 Australian federal budget $428 million was allocated for works at HMAS Albatross, RAAF Base Amberley, RAAF Base Pearce and RAAF Base Richmond including funding to remediate PFAS contamination.[88]

Canada edit

Although PFASs are not manufactured in Canada, they may be present in imported goods and products. In 2008, products containing PFOS as well as PFOS were banned in Canada, with exceptions for products used in firefighting, the military, and some forms of ink and photo media.[89]

Health Canada has published drinking water guidelines for maximum concentrations of PFOS and PFOA to protect the health of Canadians, including children, over a lifetime's exposure to these substances. The maximum allowable concentration for PFOS under the guidelines is 0.0002 milligrams per litre. The maximum allowable concentration for PFOA is 0.0006 milligrams per litre.[90]

New Zealand edit

The New Zealand Environmental Protection Agency (EPA) has banned the use of per- and polyfluoroalkyl substances (PFAS) in cosmetic products starting from 31 December 2026. This will make the country one of the first in the world to take this step on PFAS to protect people and the environment.[91]

United Kingdom edit

The environmental consequences of PFAS, especially from firefighting activities, has been recognized since the mid-1990s and came to prominence after the Buncefield explosion on 11 December 2005. In recent years the Environment Agency has undertaken a series of projects to understand the scale and nature of PFAS in the environment. The Drinking Water Inspectorate requires water companies to report concentrations of 47 PFAS.[92]

European Union edit

In 2019, the European Council requested the European Commission to develop an action plan to eliminate all non-essential uses of PFAS due to the growing evidence of adverse effects caused by exposure to these substances; the evidence for the widespread occurrence of PFAS in water, soil, articles, and waste; and the threat it can pose to drinking water.[93] Germany, the Netherlands, Denmark, Norway, and Sweden submitted a so-called restriction proposal based on the REACH regulation to achieve a European ban on the production, use, sale and import of PFAS.[94] The proposal states that a ban is necessary for all use of PFAS, with different periods for different applications when the ban takes effect (immediately after the restriction comes into force, 5 years afterwards, or 12 years afterwards), depending on the function and the availability of alternatives. The proposal has not assessed the use of PFAS in medicines, plant protection products and biocides because specific regulations apply to those substances (Biocidal Products Regulation, Plant Protection Products Regulation, Medicinal Products Regulation) that have an explicit authorization procedure that focuses on risk for health and the environment.

The proposal was submitted on 13 January 2023 and published by the European Chemicals Agency (ECHA) on 7 February. From 22 March to 21 September, citizens, companies and other organizations can comment on the proposal during a public consultation.[95] Based on the information in the restriction proposal and the consultation, two committees from ECHA formulate an opinion on the risk and socio-economic aspects of the proposed restriction. Within a year of publication, the opinions are sent to the European Commission, which makes a final proposal that is submitted to the EU Member States for discussion and decision.[96] Eighteen months after the publication of the restriction decision (which may differ from the original proposal), it will enter the ban.[95]

Italy edit

Over 350,000 residents in the Veneto region are estimated to have been exposed to contamination through tap water, and it is thought to be Europe's biggest PFAS-related environmental disaster.[who?] While Italy's National Health Institute (ISS, Istituto Superiore di Sanità) set the threshold limit of PFOA in the bloodstream at 8 nanograms per milliliter (ng/mL), some residents had reached 262 and some industrial employees reach 91,900 ng/mL. In 2021 some data was disclosed by Greenpeace and local citizens after a long legal battle against the Veneto Region and ISS, which for years has denied access to data, despite values known since or even before 2017. The Veneto region has not carried out further monitoring or taken resolutive actions to eliminate pollution and reduce, at least gradually, the contamination of non-potable water. Although in 2020 the European Food Safety Agency (EFSA) has reduced by more than four times the maximum tolerable limit of PSAS that can be taken through the diet, the region has not carried out new assessments or implemented concrete actions to protect the population and the agri-food and livestock sectors. Some limits were added to monitoring the geographical area, which does not include the orange zone and other areas affected by contamination, as well as the insufficiency of analysis on important productions widespread in the areas concerned: eggs (up to 37,100 ng/kg), fish (18,600 ng/kg) spinach and radicchio (only one sampling carried out), kiwis, melons, watermelons, cereals (only one sample was analyzed), soy, wines and apples.[97]

Sweden edit

Highly contaminated drinking water has been detected at several locations in Sweden. Such locations include Arvidsjaur, Lulnäset, Uppsala and Visby.[98][99] In 2013, PFAS were detected at high concentrations in one of the two municipality drinking water treatment plants in the town of Ronneby, in southern Sweden. Concentrations of PFHxS and PFOS were found at 1700 ng/L and 8000 ng/L, respectively.[100] The source of contamination was later found to be a military fire-fighting exercise site in which PFAS containing fire-fighting foam had been used since the mid-1980s.[101]

Additionally, low-level contaminated drinking water has also been shown to be a significant exposure source of PFOA, PFNA, PFHxS and PFOS for Swedish adolescents (ages 10–21). Even though the median concentrations in the municipality drinking water were below <1 ng individual PFAS/L, positive associations were found between adolescent serum PFAS concentrations and PFAS concentrations in drinking water.[102]

United States edit

An estimated 26,000 U.S. sites are contaminated with PFASs. At least six million Americans are estimated to have drinking water containing PFASs above the safe limit published prior to 2022 by the U.S. Environmental Protection Agency (EPA).[103][104] More than 200 million Americans are estimated to live in places where the tap water PFAS level (a combination of PFOA and PFOS levels) exceeds the 1 ppt (part per trillion) limit set in 2022 by the EPA.[105]

Between 2016 and 2021 the U.S. Geological Survey (USGS) tested tap water from 716 locations across the United States, and reported in 2023 that the PFAS levels exceeded the EPA advisories in approximately 75% of the samples from urban areas and in approximately 25% of the rural area samples.[106]

Industry edit

Certain PFASs are no longer manufactured in the United States as a result of phase-outs including the PFOA Stewardship Program (2010-2015), in which eight major chemical manufacturers agreed to eliminate the use of PFOA and PFOA-related chemicals in their products and emissions from their facilities.[107] Although PFOA and PFOS are no longer manufactured in the United States, they are still produced internationally and are imported into the U.S. in consumer goods such as carpet, leather and apparel, textiles, paper and packaging, coatings, rubber, and plastics.[108]

In 2020, manufacturers and the Food and Drug Administration announced an agreement to phase out some types of PFAS that are used in food packaging by 2024.[109]

PFASs are also used by major companies of the cosmetics industry in a wide range of cosmetics, including lipstick, eye liner, mascara, foundation, concealer, lip balm, blush, and nail polish. A 2021 study tested 231 makeup and personal care products and found organic fluorine, an indicator of PFASs, in more than half of the samples. High levels of fluorine were most commonly identified in waterproof mascara (82% of brands tested), foundations (63%), and liquid lipstick (62%).[110][111] As many as 13 types of individual PFAS compounds were found in each product.[110] Since PFAS compounds are highly mobile, they are readily absorbed through human skin and through tear ducts, and such products on lips are often unwittingly ingested. Manufacturers often fail to label their products as containing PFASs, which makes it difficult for cosmetics consumers to avoid products containing PFASs.[112] In response, Senators Susan Collins of Maine and Richard Blumenthal of Connecticut proposed the No PFAS in Cosmetics Act in the United States Senate.[113] It was also introduced in the United States House of Representatives by Michigan Representative Debbie Dingell,[114] but the U.S. chemical industry lobby has killed efforts to regulate this.[115]

Military bases edit

The water in and around at least 126 U.S. military bases has been contaminated by high levels of PFASs because of their use of firefighting foams since the 1970s, according to a study by the U.S. Department of Defense. Of these, 90 bases reported PFAS contamination that had spread to drinking water or groundwater off the base.[116][117] A 2022 Pentagon report acknowledged that approximately 175,000 U.S. military personnel at two dozen American military facilities drank water contaminated by PFAS that exceeded the U.S. EPA limit. However, according to an analysis of the Pentagon report by the non-partisan Environmental Working Group, the Pentagon report downplayed the number of people exposed to PFAS, which was much higher, probably in excess of 640,000 at 116 military facilities, than the number advanced by the Pentagon report. The EWG found that the Pentagon also omitted from its report some types of diseases that are likely to be caused by PFAS exposure, such as testicular cancer, kidney disease, and fetal abnormalities.[118]

Environmental Protection Agency actions edit

EPA published non-enforceable drinking water health advisories for PFOA and PFOS in 2016.[119][120] In March 2021 EPA announced that it would develop national drinking water standards for PFOA and PFOS.[121] On December 27, 2021, EPA published a regulation requiring drinking water utilities to conduct monitoring for 29 compounds. The data are to be collected during 2023 to 2025. EPA will pay for the monitoring costs for small drinking water systems (those serving a population of 10,000 or fewer). The agency may use the monitoring data to develop additional regulations.[122][123]

In mid-2021 EPA announced plans to revise federal wastewater regulations (effluent guidelines) for several industries that manufacture PFASs or use PFASs in fabricating various products.[124][125]

In October 2021 EPA announced the PFAS Strategic Roadmap. It is a "whole-of-EPA" strategy and considers the full lifecycle of PFAS—including drinking water monitoring and risk assessment for PFOA and PFOS in biosolids (processed wastewater sludge used as fertilizer).[126][127]

The EPA issued health advisories for four specific PFASs in June 2022, significantly lowering their safe threshold levels for drinking water. PFOA was reduced from 70 ppt to 0.004 ppt, while PFOS was reduced from 70 ppt to 0.02 ppt. GenX's safe levels were set at 10 ppt, while PFBS were set to 2000 ppt. While not enforceable, these health advisories are intended to be acted on by states in setting their own drinking water standards.[128]

A formal EPA rule to add PFOA and PFAS as hazardous chemicals was first issued for comment in August 2022, which would require anyone discharging waste to monitor and restrict the release of these PFAS to set levels, and report when the wastewater exceeds it. It would also make grounds affected by high levels of PFIA or PFAS to be considered Superfund cleanup sites.[129] The EPA formally established rules for establishing these two chemicals as hazardous chemicals in April 2024.[130]

EPA has listed recommended steps that consumers may take to reduce possible exposure to PFAS chemicals.[131]

 
USGS map showing the number of PFAS detections in tap water samples from select sites across the US.

On 14 March 2023, EPA announced the proposed National Primary Drinking Water Regulation (NPDWR). This proposal includes new maximum contaminant levels (MCLs) in drinking water for six well-known PFAS: PFOA, PFOS, GenX, PFBS, PFNA, and PFHxS. While the proposal does not require any actions until its finalization, the EPA believes it will be implemented by late 2023. If these new restrictions are put into place, the EPA expects that they will prevent thousands of deaths and tens of thousands of PFAS-attributable illnesses. Along with legally enforceable MCLs, the EPA proposal will also require public water systems to actively monitor for the 6 PFAS, notify the public about the level of PFAS in the water supply, and take measures to reduce the level of PFAS in drinking water if they exceed the MCLs.[132] In April 2024, the EPA issued its final ruling, requireing that within 3 years, these six PFAS must be removed to near-zero levels in drinking water supplies. States would be given up to $1 billion in aid to help with the initial testing and treatment of water for this purpose.[133]

The EPA has stated that while some companies have reached certain conclusions related to PFASs, the EPA research is still ongoing and as of 2023, remains inconclusive as it relates to the certainty of detrimental effects on humans, according to the EPA:

Current scientific research suggests that exposure to certain PFAS may lead to adverse health outcomes. However, research is still ongoing to determine how different levels of exposure to different PFAS can lead to a variety of health effects. Research is also underway to better understand the health effects associated with low levels of exposure to PFAS over long periods of time, especially in children.[67]

Legal actions edit

In February 2017, DuPont and Chemours (a DuPont spin-off) agreed to pay $671 million to settle lawsuits arising from 3,550 personal injury claims related to releasing of PFASs from their Parkersburg, West Virginia, plant into the drinking water of several thousand residents.[134] This was after a court-created independent scientific panel—the C8 Science Panel—found a "probable link" between C8 exposure and six illnesses: kidney and testicular cancer, ulcerative colitis, thyroid disease, pregnancy-induced hypertension and high cholesterol.[33][135]

In October 2018, a class action suit was filed by an Ohio firefighter against several producers of fluorosurfactants, including the 3M and DuPont corporations, on behalf of all U.S. residents who may have adverse health effects from exposure to PFASs.[136] The story is told in the film Dark Waters.[137]

In 2023, the American multinational 3M reached a US$10.3 billion settlement with a host of US public water systems to resolve water pollution claims tied to PFAS.[138] Three other major chemicals companies – Chemours, DuPont and Corteva – have reached an agreement in principle for US$1.19 bn to settle claims they contaminated US public water systems with PFAS.[138]

In December, 2023, as part of a four-year legal battle,[139] the EPA banned Inhance—a Houston, Texas-based manufacturer that produces an estimated 200m containers annually with a process that creates, among other chemicals, PFOA—from using the manufacturing process.[140] In March, 2024, the Fifth Circuit federal appeals court overturned the ban. While the court did not deny the containers’ health risks, it said that the EPA could not regulate the manufactured containers under the statute it used.

State actions edit

In 2021, Maine became the first U.S. state to ban these compounds in all products by 2030, except for instances deemed "currently unavoidable".[141][142]

As of October 2020, the states of California, Connecticut, Massachusetts, Michigan, Minnesota, New Hampshire, New Jersey, New York, Vermont, and Wisconsin had enforceable drinking water standards for between two and six types of PFAS. The six chemicals (termed by the Massachusetts Department of Environmental Protection as PFAS6) are measured either individually or summed as a group depending on the standard; they are:[143]

California edit

In 2021 California banned PFASs for use in food packaging and from infant and children's products and also required PFAS cookware in the state to carry a warning label.[144]

Maine edit

A program licensed and promoted by the Maine Department of Environmental Protection that provided free municipal wastewater sludge (biosolids) to farmers as fertilizer has resulted in PFAS contamination of local drinking water and farm-grown produce.[145][146]

Michigan edit

The Michigan PFAS Action Response Team (MPART) was launched in 2017 and is the first multi-agency action team of its kind in the nation. Agencies representing health, environment, and other branches of state government have joined together to investigate sources and locations of PFAS contamination in the state, take action to protect people's drinking water, and keep the public informed.[147]

Groundwater is tested at locations throughout the state by various parties to ensure safety, compliance with regulations, and proactively detect and remedy potential problems. In 2010, the Michigan Department of Environmental Quality (MDEQ) discovered levels of PFASs in groundwater monitoring wells at the former Wurtsmith Air Force Base. As additional information became available from other national testing, Michigan expanded its investigations into other locations where PFAS compounds were potentially used.[147]

In 2018, the MDEQ's Remediation and Redevelopment Division (RRD) established cleanup criteria for groundwater used as drinking water of 70 ppt of PFOA and PFOS, individually or combined. The RRD staff are responsible for implementing these criteria as part of their ongoing efforts to clean up sites of environmental contamination. The RRD staff are the lead investigators at most of the PFAS sites on the MPART website and also conduct interim response activities, such as coordinating bottled water or filter installations with local health departments at sites under investigation or with known PFAS concerns. Most of the groundwater sampling at PFAS sites under RRD's lead is conducted by contractors familiar with PFAS sampling techniques. The RRD also has a Geologic Services Unit, with staff who install monitoring wells and are also well versed with PFAS sampling techniques.[147]

The MDEQ has been conducting environmental clean-up of regulated contaminants for decades. Due to the evolving nature of PFAS regulations as new science becomes available, the RRD is evaluating the need for regular PFAS sampling at Superfund sites and is including an evaluation of PFAS sampling needs as part of a Baseline Environmental Assessment review.[147]

Earlier in 2018, the RRD purchased lab equipment that will allow the MDEQ Environmental Lab to conduct analyses of certain PFAS samples. (Currently, most samples are shipped to one of the few labs in the country that conduct PFAS analysis, in California, although private labs in other parts of the country, including Michigan, are starting to offer these services.) As of August 2018, RRD has hired additional staff to work on developing the methodology and conducting PFAS analyses.[147]

In 2020 Michigan Attorney General Dana Nessel filed a lawsuit against 17 companies, including 3M, Chemours, and DuPont, for hiding known health and environmental risks from the state and its residents. Nessel's complaint identifies 37 sites with known contamination.[148] The Michigan Department of Environment, Great Lakes, and Energy introduced some of the strictest drinking water standards in the country for PFAS, setting maximum contaminant levels (MCLs) for PFOA and PFOS to 8 and 16 ppt respectively (down from previous existing groundwater cleanup standards of 70 ppt for both), and introducing MCLs for 5 other previously unregulated PFAS compounds, limiting PFNA to 6 ppt, PFHxA to 400,000 ppt, PFHxS to 51 ppt, PFBS to 420 ppt and HFPO-DA to 370 ppt.[149] The change adds 38 additional sites to the state's list of known PFAS contaminated areas, bringing the total number of known sites to 137. About half of these sites are landfills and 13 are former plating facilities.[150]

In 2022 PFOS was found in beef produced at a Michigan farm: the cattle had been fed crops fertilized with contaminated biosolids. State agencies issued a consumption advisory, but did not order a recall, because there currently is no PFOS contamination in beef government standards.[151]

Minnesota edit

In February 2018, 3M settled a lawsuit for $850 million related to contaminated drinking water in Minnesota.[152]

New Jersey edit

In 2018 the New Jersey Department of Environmental Protection (NJDEP) published a drinking water standard for PFNA. Public water systems in New Jersey are required to meet an MCL standard of 13 ppt.[153][154] In 2020 the state set a PFOA standard at 14 ppt and a PFOS standard at 13 ppt.[155]

In 2019 NJDEP filed lawsuits against the owners of two plants that had manufactured PFASs, and two plants that were cited for water pollution from other chemicals. The companies cited are DuPont, Chemours and 3M.[156] NJDEP also declared five companies to be financially responsible for statewide remediation of the chemicals. Among the companies accused were Arkema and Solvay regarding a West Deptford Facility in Gloucester County, where Arkema manufactured PFASs, but Solvay claims to have never manufactured but only handled PFASs.[157] The companies denied liability and contested the directive.[158] In June 2020, the U.S. Environmental Protection Agency and New Jersey Department of Environmental Protection published a paper reporting that a unique family of PFAS used by Solvay, chloroperfluoropolyether carboxylates (ClPFPECAs), were contaminating the soils of New Jersey as far from the Solvay facility as 150 km.[159] and the ClPFPECAs were found in water as well.[160]

Later in 2020, the New Jersey state attorney general filed suit in the New Jersey Superior Court against Solvay regarding PFAS contamination of the state's environment.[161] In May 2021, Solvay issued a press release that the company is "discontinuing the use of fluorosurfactants in the U.S.".[162]

New York edit

In 2016, New York, along with Vermont and New Hampshire, acknowledged PFOA contamination by requesting the EPA to release water quality guidance measures. Contamination has been observed by the New York State Department of Environmental Conservation in Hoosick Falls, Newburgh, Petersburgh, Poestenkill, Mahopac, and Armonk.[163]

The village of Hoosick Falls has received a $65.25 million dollar settlement from Saint-Gobain Performance Plastics, Honeywell, 3M, and DuPont companies through a class action lawsuit in 2021, due to the disposal of PFAS chemicals into the groundwater of the local water treatment plant.[164]

Washington edit

Five military installations in Washington State have been identified by the U.S. Senate Committee on Environment and Public Works as having PFAS contamination. Toward environmental and consumer protections, the Washington State Department of Ecology published a Chemical Action Plan in November 2021, and in June 2022 the governor tasked the Washington State Department of Ecology with phasing out manufacture and import of products containing PFASs. Initial steps taken by the Washington State Department of Health to protect the public from exposure through drinking water have included setting State Action Levels for five PFASs (PFOA, PFOS, PFNA, PFHxS, and PFBS), which were implemented in November 2021.[165][166][167]

United Nations edit

PFOS, its salts and perfluorooctanesulfonyl fluoride, as well as PFOA and PFHxS including their salts and precursors have been listed as persistent organic pollutants (POPs) in the Stockholm Convention.[168] The long-chain (C9–C21) PFCAs are currently under review for listing.[169]

Occupational exposure edit

Occupational exposure to PFASs occurs in numerous industries due to the widespread use of the chemicals in products and as an element of industrial process streams.[170] PFASs are used in more than 200 different ways in industries as diverse as electronics and equipment manufacturing, plastic and rubber production, food and textile production, and building and construction.[171] Occupational exposure to PFASs can occur at fluorochemical facilities that produce them and other manufacturing facilities that use them for industrial processing like the chrome plating industry.[170] Workers who handle PFAS-containing products can also be exposed during their work, such as people who install PFAS-containing carpets and leather furniture with PFAS coatings, professional ski-waxers using PFAS-based waxes, and fire-fighters using PFAS-containing foam and wear flame-resistant protective gear made with PFASs.[170][172][173]

Exposure pathways edit

People who are exposed to PFASs through their jobs typically have higher levels of PFASs in their blood than the general population.[170][174][175] While the general population is exposed to PFASs through ingested food and water, occupational exposure includes accidental ingestion, inhalation exposure, and skin contact in settings where PFAS become volatile.[176][13] The severity of PFAS-associated health effects can vary based on the length of exposure, level of exposure, and health status.[170]

Professional ski wax technicians edit

Compared to the general public exposed to contaminated drinking water, professional ski wax technicians are more strongly exposed to PFASs (PFOA, PFNA, PFDA, PFHpA, PFDoDA) from the glide wax used to coat the bottom of skis to reduce the friction between the skis and snow.[177] During the coating process, the wax is heated, which releases fumes and airborne particles.[177] Compared to all other reported occupational and residential exposures, ski waxing had the highest total PFAS air concentrations.[178]

Manufacturing workers edit

People who work at fluorochemical production plants and in manufacturing industries that use PFASs in the industrial process can be exposed to PFASs in the workplace. Much of what we know about PFASs exposure and health effects began with medical surveillance studies of workers exposed to PFASs at fluorochemical production facilities. These studies began in the 1940s and were conducted primarily at U.S. and European manufacturing sites. Between the 1940s and 2000s, thousands of workers exposed to PFASs participated in research studies that advanced scientific understanding of exposure pathways, toxicokinetic properties, and adverse health effects associated with exposure.[26][179][180]

The first research study to report elevated organic fluorine levels in the blood of fluorochemical workers was published in 1980.[26] It established inhalation as a potential route of occupational PFAS exposure by reporting measurable levels of organic fluorine in air samples at the facility.[26] Workers at fluorochemical production facilities have higher levels of PFOA and PFOS in their blood than the general population. Serum PFOA levels in fluorochemical workers are generally below 20,000 ng/mL but have been reported as high as 100,000 ng/mL, whereas the mean PFOA concentration among non-occupationally exposed cohorts in the same time frame was 4.9 ng/mL.[181][27] Among fluorochemical workers, those with direct contact with PFASs have higher PFAS concentrations in their blood than those with intermittent contact or no direct PFAS contact.[179][181] Blood PFAS levels have been shown to decline when direct contact ceases.[181][182] PFOA and PFOS levels have declined in U.S. and European fluorochemical workers due to improved facilities, increased usage of personal protective equipment, and the discontinuation of these chemicals from production.[179][183] Occupational exposure to PFASs in manufacturing continues to be an active area of study in China with numerous investigations linking worker exposure to various PFASs.[184][185][186]

Firefighters edit

 
Firefighters using aqueous film forming foam (AFFF)

PFASs are commonly used in Class B firefighting foams due to their hydrophobic and lipophobic properties, as well as the stability of the chemicals when exposed to high heat.[187]

Research into occupational exposure for firefighters is emergent, though frequently limited by underpowered study designs. A 2011 cross-sectional analysis of the C8 Health Studies found higher levels of PFHxS in firefighters compared to the sample group of the region, with other PFASs at elevated levels, without reaching statistical significance.[188] A 2014 study in Finland studying eight firefighters over three training sessions observed select PFASs (PFHxS and PFNA) increase in blood samples following each training event.[187] Due to this small sample size, a test of significance was not conducted. A 2015 cross-sectional study conducted in Australia found that PFOS and PFHxS accumulation was positively associated with years of occupational AFFF exposure through firefighting.[174]

Due to their use in training and testing, recent studies indicate occupational risk for military members and firefighters, as higher levels of PFASs in exposure were indicated in military members and firefighters when compared to the general population.[189] PFAS exposure is prevalent among firefighters not only due to its use in emergencies, but also because it is used in personal protective equipment. In support of these findings, states like Washington and Colorado have moved to restrict and penalize the use of Class B firefighting foam for firefighter training and testing.[190][191]

Exposure after World Trade Center terrorist attacks edit

The 11 September 2001 collapse of the World Trade Center buildings in New York City resulted in the release of chemicals from the destruction of construction and electrical material and long-term chemical fires. This collapse caused the release of several toxic chemicals, including fluorinated surfactants used as soil- and stain-resistant coatings on various materials.[192] First responders to this incident were exposed to PFOA, PFNA, and PFHxS through inhalation of dust and smoke released during and after the collapse of the World Trade Center.[192]

Fire responders who were working at or near ground zero were assessed for respiratory and other health effects from exposure to emissions at the World Trade Center. Early clinical testing showed a high prevalence of respiratory health effects. Early symptoms of exposure often presented with persistent coughing and wheezing. PFOA and PFHxS levels were present in both smoke and dust exposure, but first responders exposed to smoke had higher concentrations of PFOA and PFHxS than those exposed to dust.[192]

Mitigation measures edit

Several strategies have been proposed as a way to protect those who are at greatest risk of occupational exposure to PFAS, including exposure monitoring, regular blood testing, and the use of PFAS-free alternatives. For example, fluorine-free firefighting foam and plant-based ski wax contain no PFAS and greatly reduce the occupational hazards associated with certain professions.[193]

Remediation edit

Water treatment edit

Several technologies are currently available for remediating PFASs in liquids. These technologies can be applied to drinking water supplies, groundwater, industrial wastewater, surface water, and other applications such as landfill leachate. Influent concentrations of PFASs can vary by orders of magnitude for specific media or applications. These influent values, along with other general water quality parameters (for example, pH) can influence the performance and operating costs of the treatment technologies. The technologies are:

Private and public sector applications of one or more of these methodologies above are being applied to remediation sites throughout the United States and other international locations.[197] Most solutions involve on-site treatment systems, while others are leveraging off-site infrastructure and facilities, such as a centralized waste treatment facility, to treat and dispose of the PFAS pool of compounds.

The US based Interstate Technology and Regulatory Council (ITRC)[198] has undertaken extensive evaluation of ex situ and in situ treatment technologies for PFAS impacted liquid matrices. These technologies are divided into field implemented technologies, limited application technologies and developing technologies and typically fit into one of three technology types:

  • Separation,
  • Concentration, and
  • Destruction

The type of PFAS remediation technology selected is often a reflection of the PFAS contamination levels and the PFAS signature (i.e. the combination of short and long chain PFAS substances present) in conjunction with the site specific water chemistry and cross contaminants present in the liquid stream. More complex waters such as landfill leachates and WWTP waters require more robust treatment solutions which are less vulnerable to blockage.

Stripping and Enrichment

Foam Fractionation utilises the air/water interface of a rising air bubble to collect and harvest PFAS molecules. The hydrophobic tail of many long chain criteria PFAS compounds adhere to this interface and rise to the water surface with the air bubble where they present as a foam for harvesting and further concentration. The foam fractionation technique is a derivation of traditional absorptive bubble separation techniques used by industries for decades to extract amphiphilic contaminants. The absence of a solid absorptive surface reduces consumables and waste byproducts and produces a liquid hyper-concentrate which can be fed into one of the various PFAS destruction technologies. Across various full scale trials and field applications, this technique provides a simplistic and low operational cost alternative for complex PFAS impacted waters.[199]

Destruction

Most recently, a 2022 study published in the Journal of Environmental Engineering found that a heat-and pressure-based technique known as supercritical water oxidation destroyed 99% of the PFASs present in a water sample. During this process, oxidizing substances are added to PFAS-contaminated water and then the liquid is heated above its critical temperature of 374 degrees Celsius at a pressure of more than 220 bars. The water becomes supercritical, and, in this state, water-repellent substances such as PFASs dissolve much more readily.[196]

Theoretical and early-stage solutions edit

A possible solution for PFAS-contaminated wastewater treatment has been developed by the Michigan State University-Fraunhofer team. Boron-doped diamond electrodes are used for the electrochemical oxidation system where it is capable of breaking PFAS molecular bonds which essentially eliminates the contaminates, leaving fresh water.[200] Cory Rusinek, an electrochemist at MSU-Fraunhofer stated:

"EO, or electrochemical oxidation, is a simple, clean, and effective method for destruction of PFASs and other co-contaminants as a complementary procedure to other wastewater treatment processes. If we can remove it from wastewater, we can reduce its occurrence in surface waters.[200]

Acidimicrobium sp. strain A6 has been shown to be a PFAS and PFOS remediator.[201] PFAS with unsaturated bonds are easier to break down: the commercial dechlorination culture KB1 (contains Dehalococcoides) is capable of breaking down such substances, but not saturated PFAS. When alternative, easier-to-digest substrates are present, microbes may prefer them over PFAS.[202]

Chemical treatment edit

A study published in Science in August 2022 indicated that perfluoroalkyl carboxylic acids (PFCAs) can be mineralized via heating in a polar aprotic solvent such as dimethyl sulfoxide. It reported that heating PFCAs in an 8 to 1 mixture of dimethyl sulfoxide and water at 80–120 °C (176–248 °F) in the presence of sodium hydroxide caused the removal of the carboxylic acid group at the end of the carbon chain, creating a perfluoroanion that mineralizes into sodium fluoride and other salts such as sodium trifluoroacetate, formate, carbonate, oxalate, and glycolate. The process does not work on perfluorosulfonic acids such as PFOS.[203] A more recent study published in Chemical Science shows breakdown of C-F bonds and their mineralization as YF3 or YF6 clusters.[204] Another study in the Journal of the American Chemical Society described the PFASs breakdown using metal-organic frameworks (MOFs).[205]

Analytical methods edit

Analytical methods for specific PFASs in environmental matrices and food and food have generally improved in sensitivity and selectivity in recent years, e.g. to meet lower regulatory limit values. However, sensitive and accurate targeted methods using isotope-labeled internal standards still only cover just over 50 PFASs, mostly PFCAs and PFSAs with perfluorinated alkyl chains of four or more carbon atoms.[206][23] Sum parameter methods, such as total organic fluorine assays (e.g., adsorbable organic fluorine, AOF; extractable organic fluorine, EOF), and the total oxidizable precursor (TOP) assay, are increasingly being used across matrices to quantify the proportion of PFASs not captured by typical targeted analyses.[23][207][208]

Sample chemicals edit

Some common per- and polyfluoroalkyl substances include:[209][210]

Name Abbreviation Structural formula Molecular weight (g/mol) CAS No.
Perfluorobutane sulfonamide H-FBSA C4F9SO2NH2 299.12 30334-69-1
Perfluoropentanesulfonamide PFPSA C5F11SO2NH2 349.12 82765-76-2
Perfluorohexanesulfonamide PFHxSA C6F13SO2NH2 399.13 41997-13-1
Perfluoroheptanesulfonamide PFHpSA C7F15SO2NH2 449.14 82765-77-3
Perfluorooctanesulfonamide PFOSA C8F17SO2NH2 499.14 754-91-6
Perfluorobutanesulfonyl fluoride PFBSF C4F9SO2F 302.09 375-72-4
Perfluorooctanesulfonyl fluoride PFOSF C8F17SO2F 502.12 307-35-7

Films edit

See also edit

References edit

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Further reading edit

  • Lindstrom AB, Strynar MJ, Libelo EL (October 2011). "Polyfluorinated compounds: past, present, and future". Environmental Science & Technology. 45 (19): 7954–7961. Bibcode:2011EnST...45.7954L. doi:10.1021/es2011622. PMID 21866930. S2CID 206946893.
  • Ritter SK (2015). "The Shrinking Case For Fluorochemicals". Chemical & Engineering News. 93 (28): 27–29. doi:10.1021/cen-09328-scitech1. from the original on 18 August 2016. Retrieved 3 August 2016.
  • Lehmler HJ (March 2005). "Synthesis of environmentally relevant fluorinated surfactants—a review". Chemosphere. 58 (11): 1471–1496. Bibcode:2005Chmsp..58.1471L. doi:10.1016/j.chemosphere.2004.11.078. PMID 15694468.

External links edit

polyfluoroalkyl, substances, pfas, redirects, here, other, uses, pfas, disambiguation, this, article, needs, more, reliable, medical, references, verification, relies, heavily, primary, sources, please, review, contents, article, appropriate, references, unsou. PFAS redirects here For other uses see PFAS disambiguation This article needs more reliable medical references for verification or relies too heavily on primary sources Please review the contents of the article and add the appropriate references if you can Unsourced or poorly sourced material may be challenged and removed Find sources Per and polyfluoroalkyl substances news newspapers books scholar JSTOR October 2023 Per and polyfluoroalkyl substances PFAS 1 or PFASs 2 are a group of synthetic organofluorine chemical compounds that have multiple fluorine atoms attached to an alkyl chain The PubChem database lists more than 6 million unique compounds in this group 3 PFASs started being used in the mid 20th century to make fluoropolymer coatings and products that resist heat oil stains grease and water 4 They are used in a variety of products including waterproof clothing furniture adhesives food packaging heat resistant non stick cooking surfaces and the insulation of electrical wire 4 They have played a key economic role for companies such as DuPont 3M and W L Gore amp Associates that use them to produce widely known materials such as Teflon or Gore Tex Many PFAS such as PFOS PFOA are a health and environmental concern because they do not break down via natural processes and are commonly described as persistent organic pollutants or forever chemicals 4 5 They can also move through soils and contaminate drinking water sources and can build up bioaccumulate in fish and wildlife 4 Residues have been detected in humans and wildlife 4 6 7 8 Only since the start of the 21st century has the environmental impact and toxicity to human and mammalian life been studied in depth Due to the large number of PFAS it is challenging to study and assess the potential human health and environmental risks more research is necessary 4 9 10 According to the United States Environmental Protection Agency exposure to some PFAS in the environment may be linked to harmful health effects in humans and animals 10 The International Agency for Research on Cancer IARC has classified PFOA as carcinogenic to humans and PFOS as possibly carcinogenic 11 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 12 Health concerns related to PFASs have resulted in numerous litigations see Timeline of events related to per and polyfluoroalkyl substances PFAS producers such as 3M Chemours DuPont and Corteva have reached billion dollar agreements to settle claims against them The use of PFAS is regulated in several parts of the world with some plans to phase them out entirely from products Contents 1 Definition 1 1 Fluorosurfactants 2 Economic role 3 Health and environmental effects 3 1 Pregnancy 3 2 Cancer 3 3 Prevalence in rainwater 3 4 Estimated contemporary costs 3 4 1 Costs by region 3 5 Proposed mechanisms of PFAS related adverse health outcomes 3 5 1 Hypercholesterolemia 3 5 2 Ulcerative colitis 3 5 3 Thyroid disease 3 6 Washington Post 2018 op ed 3 7 Bioaccumulation and biomagnification 3 8 Corporate and federal government suppression of information 4 Concerns litigation and regulations in specific countries and regions 4 1 Australia 4 2 Canada 4 3 New Zealand 4 4 United Kingdom 4 5 European Union 4 6 Italy 4 7 Sweden 4 8 United States 4 8 1 Industry 4 8 2 Military bases 4 8 3 Environmental Protection Agency actions 4 8 4 Legal actions 4 8 5 State actions 4 8 5 1 California 4 8 5 2 Maine 4 8 5 3 Michigan 4 8 5 4 Minnesota 4 8 5 5 New Jersey 4 8 5 6 New York 4 8 5 7 Washington 4 9 United Nations 5 Occupational exposure 5 1 Exposure pathways 5 2 Professional ski wax technicians 5 3 Manufacturing workers 5 4 Firefighters 5 5 Exposure after World Trade Center terrorist attacks 5 6 Mitigation measures 6 Remediation 6 1 Water treatment 6 1 1 Theoretical and early stage solutions 6 2 Chemical treatment 7 Analytical methods 8 Sample chemicals 9 Films 10 See also 11 References 12 Further reading 13 External linksDefinition edit nbsp Skeletal structure of PFOS an effective persistent and bioaccumulative fluorosurfactant nbsp Space filling model of PFOS Per and polyfluoroalkyl substances are defined as 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 13 14 Beginning in 2021 the Organisation for Economic Co operation and Development OECD expanded its 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 2 15 According to the OECD at least 4 730 distinct PFASs that contain at least three perfluorinated carbon atoms are known 16 The United States Environmental Protection Agency s EPA toxicity database DSSTox lists 14 735 unique PFAS chemical compounds 17 while PubChem lists more than 6 million 3 Fluorosurfactants edit nbsp Fluorine containing durable water repellent makes a fabric water resistant 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 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 18 so fluorosurfactants tend to concentrate at the liquid air interface 19 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 6 Economic role editPFASs play a key economic role for companies such as DuPont 3M and W L Gore amp 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 20 In 2022 3M announced that it would end PFAS production by 2025 21 22 Over the past two decades production of certain PFASs has increasingly moved to Asia where there is less regulatory scrutiny 23 Health and environmental effects editOn their introduction in the 1940s PFASs were considered inert 24 25 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 26 27 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 27 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 24 nbsp Effects of exposure to PFASs on human health 28 29 30 Hormone disrupting chemicals including PFASs are linked with rapid declines in human fertility 31 In a meta analysis for associations between PFASs and human clinical biomarkers for liver injury authors considered both PFAS effects on liver biomarkers and histological data from rodent experimental studies and concluded that evidence exists showing that PFOA perfluorohexanesulfonic acid PFHxS and perfluorononanoic acid PFNA are hepatotoxic to humans 32 Many comprehensive epidemiological studies linking adverse human health effects to PFASs particularly PFOA come from the C8 Science Panel 33 The panel was formed as part of a contingency to a class action lawsuit brought by communities in the Ohio River Valley against DuPont in response to landfill and wastewater dumping of PFAS laden material from DuPont s West Virginia Washington Works Plant 33 The panel measured PFOA also known as C8 serum concentrations in 69 000 individuals from around DuPont s Washington Works Plant and found a mean concentration of 83 0 ng mL compared to 4 ng mL in a standard population of Americans 34 This panel reported probable links between elevated PFOA blood concentration and hypercholesterolemia ulcerative colitis thyroid disease testicular cancer kidney cancer as well as pregnancy induced hypertension and preeclampsia 35 36 37 38 39 Pregnancy edit Exposure to PFAS is a risk factor for various hypertensive disorders in pregnancy including preeclampsia and high blood pressure It is not clear whether PFAS exposure is associated with wider cardiovascular disorders during pregnancy 40 Human breast milk has the capability to harbor PFASs as well as be transferred from mother to infant through breastfeeding 41 Cancer edit As of November 2023 the International Agency for Research on Cancer IARC has classified PFOA as carcinogenic to humans Group 1 based on sufficient evidence for cancer in animals and strong mechanistic evidence in exposed humans IARC also classified PFOS as possibly carcinogenic to humans Group 2b based on strong mechanistic evidence 11 There is a lack of high quality epidemiological data on the associations between many specific PFAS chemicals and specific cancer types and research is ongoing 42 Prevalence in rainwater edit In 2022 it was found that levels of at least four perfluoroalkyl acids PFAAs in rainwater worldwide ubiquitously and often greatly exceeded the EPA s lifetime drinking water health advisories as well as comparable Danish Dutch and European Union safety standards leading to the conclusion that the global spread of these four PFAAs in the atmosphere has led to the planetary boundary for chemical pollution being exceeded 43 There are some moves to restrict and replace their use 44 Estimated contemporary costs edit Chemical corporations that produce PFAS generate approximately US 4 billion in annual profits from the production of this chemical but it is estimated that they impose much larger costs on taxpayers and the health of the planet s population i e as external costs Of these costs remediation efforts fighting PFAS soil and water contamination are the most expensive followed by the healthcare costs of treating people who develop cancer thyroid disease kidney dysfunction birth defects and other major medical conditions that have been linked to even low levels of exposure to PFAS and the costs of monitoring of PFAS pollution in human and other life forms Such costs to society have been estimated to amount to approximately US 17 5 trillion annually which would be almost one fifth of the US 96 trillion global GDP in 2021 45 according to a press release by The International Chemical Secretariat ChemSec a Sweden based NGO that works with industry and policymakers to limit the use of toxic chemicals 46 Costs by region edit In a report by the Nordic Council of Ministers the total annual health related costs associated with human exposure to PFASs were estimated to be at least 52 84 billion in the European Economic Area EEA countries 47 Aggregated annual costs covering environmental screening monitoring where contamination is found water treatment soil remediation and health assessment total 821 million 170 billion in the EEA plus Switzerland 47 In the United States estimated PFAS attributable disease costs amount to 6 62 billion US 48 Studies have estimated the annual healthcare costs in the United States of each of some of the major diseases attributed to PFAS 49 Proposed mechanisms of PFAS related adverse health outcomes edit Hypercholesterolemia edit A response is observed in humans where elevated PFOS levels were significantly associated with elevated total cholesterol and LDL cholesterol highlighting significantly reduced PPAR expression and alluding to PPAR independent pathways predominating over lipid metabolism in humans compared to rodents 50 Ulcerative colitis edit PFOA and PFOS have been shown to significantly alter immune and inflammatory responses in human and animal species In particular IgA IgE in females only and C reactive protein have been shown to decrease whereas antinuclear antibodies increase as PFOA serum concentrations increase 51 These cytokine variations allude to immune response aberrations resulting in autoimmunity One proposed mechanism is a shift towards anti inflammatory M2 macrophages and or T helper TH2 response in intestinal epithelial tissue which allows sulfate reducing bacteria to flourish Elevated levels of hydrogen sulfide result which reduce beta oxidation and nutrient production leading to a breakdown of the colonic epithelial barrier 52 Thyroid disease edit Hypothyroidism is the most common thyroid abnormality associated with PFAS exposure 53 PFASs have been shown to decrease thyroid peroxidase resulting in decreased production and activation of thyroid hormones in vivo 54 Other proposed mechanisms include alterations in thyroid hormone signaling metabolism and excretion as well as function of nuclear hormone receptor 53 Washington Post 2018 op ed edit Fluorosurfactants such as PFOS PFOA and PFNA have caught the attention of regulatory agencies because of their persistence toxicity and widespread occurrence in the blood of general populations 55 56 and wildlife In 2009 PFOS its salts and perfluorooctanesulfonyl fluoride were listed as persistent organic pollutants under the Stockholm Convention due to their ubiquitous persistent bioaccumulative and toxic nature 57 58 PFAS chemicals were dubbed forever chemicals in a 2018 op ed in the Washington Post 59 The nickname was derived by combining the two dominant attributes of this class of chemicals PFAS chemicals are characterized by a carbon fluorine backbone the F C in forever chemicals and the carbon fluorine bond is one of the strongest bonds in organic chemistry which gives these chemicals an extremely long environmental half life The term forever chemicals is commonly used in media outlets in addition to the more technical name of per and polyfluorinated alkyl substances 60 61 62 Their production has been regulated or phased out by manufacturers such as 3M DuPont Daikin and Miteni in the U S Japan and Europe In 2006 3M replaced PFOS and PFOA with short chain PFASs 20 such as perfluorohexanoic acid PFHxA and perfluorobutanesulfonic acid PFBS Shorter fluorosurfactants may be less prone to accumulating in mammals 20 there is still some concern that they may be harmful to both humans 63 64 65 and the environment 66 though the EPA states research is still ongoing to determine how different levels of exposure to different PFAS can lead to a variety of health effects 67 Many PFASs are either not covered by European legislation or are excluded from registration obligations under the EU REACH chemical regulation 68 Several PFASs have been detected in drinking water 69 municipal wastewater 70 and landfill leachates 71 worldwide It had been thought that PFAAs would eventually end up in the oceans where they would be diluted over decades but a field study published in 2021 by researchers at Stockholm University found that they are significantly transferred from water to air when waves break on land and are a significant source of air pollution and eventually get into the rain The researchers concluded that pollution may impact large areas of inland Europe and other continents in addition to coastal areas 72 73 Bioaccumulation and biomagnification edit nbsp Bioaccumulation of PFAS PFASs from sediments and water can accumulate in marine organisms Animals higher up the food chain accumulate more PFAS because they absorb PFAS in prey they consume In marine species of the food web Bioaccumulation controls internal concentrations of pollutants including PFAS in individual organisms When bioaccumulation is looked at in the perspective of the entire food web it is called biomagnification which is incredibly important to track because lower concentrations of pollutants in environmental matrices such as seawater or sediments can very quickly grow to harmful concentrations in organisms at higher trophic levels including humans Notably concentrations in biota can even by gt 5000 times those present in water for PFOS and C10 C14 PFCAs 74 PFAS can enter an organism by ingestion of sediment through the water or directly via their diet It accumulates namely in areas with high protein content in the blood and liver but its also found to a lesser extent in tissues 75 Biomagnification can be described using the estimation of the trophic magnification factor TMF this describes the relationship between the contamination levels in a species and their trophic level in the food web TMFs are determined by graphing the log transformed concentrations of PFAS against the assigned trophic level and taking the antilog of the regression slope 10slope 6 In a study done on a macrotidal estuary in Gironde SW France TMFs were gt 1 for nearly all 19 PFAS compounds considered in the study and were particularly high for PFOA and PFNA 6 0 and 3 1 respectively 6 A TMF gt 1 means that accumulation in the organism is greater than that of the medium in this case the medium being sea water PFOS a long chain sulfonic acid was found at the highest concentrations relative to other PFASs measured in fish and birds in Northern seas such as the Barents Sea and the Canadian Arctic 76 A study and an interactive map by the EWG using its results showed freshwater fish in the U S globalize ubiquitously contain high levels of harmful PFAS with a single serving typically significantly increasing the blood PFOS level 77 78 Bioaccumulation and biomagnification of PFASs in marine species throughout the food web particularly frequently consumed fish and shellfish can have important impacts on human populations 79 PFASs have been frequently documented in both fish and shellfish that are commonly consumed by human populations 80 which poses health risks to humans and studies on the bioaccumulation in certain species are important to determine daily tolerable limits for human consumption and where those limits may be exceeded causing potential health risks 81 This has particular implications for populations that consume larger numbers of wild fish and shellfish species 80 In addition to health risks populations may be impacted by advisories limits of fishing closures for certain species that are put in place to help mitigate health risks from potential consumption of species with higher levels of accumulated PFASs but result in a loss of food sources and important subsistence species depended on by local communities There is research being done in this area including into spatial patterns of PFAS bioaccumulation in fish and crustaceans 82 Corporate and federal government suppression of information edit Since the 1970s forty years before the public health community DuPont and 3M were aware that PFAS was highly toxic when inhaled and moderately toxic when ingested 83 Producers used several strategies to influence science and regulation most notably suppressing unfavorable research and distorting public discourse 83 In 2018 White House staff and the EPA pressured the U S Agency for Toxic Substances and Disease Registry to suppress a study that showed PFASs to be even more dangerous than previously thought 84 85 Concerns litigation and regulations in specific countries and regions editAustralia edit In 2017 the ABC s current affairs program Four Corners reported that the storage and use of firefighting foams containing perfluorinated surfactants at Australian Defence Force facilities around Australia had contaminated nearby water resources 86 In 2019 remediation efforts at RAAF Base Tindal and the adjacent town of Katherine were ongoing 87 In the 2022 Australian federal budget 428 million was allocated for works at HMAS Albatross RAAF Base Amberley RAAF Base Pearce and RAAF Base Richmond including funding to remediate PFAS contamination 88 Canada edit Although PFASs are not manufactured in Canada they may be present in imported goods and products In 2008 products containing PFOS as well as PFOS were banned in Canada with exceptions for products used in firefighting the military and some forms of ink and photo media 89 Health Canada has published drinking water guidelines for maximum concentrations of PFOS and PFOA to protect the health of Canadians including children over a lifetime s exposure to these substances The maximum allowable concentration for PFOS under the guidelines is 0 0002 milligrams per litre The maximum allowable concentration for PFOA is 0 0006 milligrams per litre 90 New Zealand edit The New Zealand Environmental Protection Agency EPA has banned the use of per and polyfluoroalkyl substances PFAS in cosmetic products starting from 31 December 2026 This will make the country one of the first in the world to take this step on PFAS to protect people and the environment 91 United Kingdom edit The environmental consequences of PFAS especially from firefighting activities has been recognized since the mid 1990s and came to prominence after the Buncefield explosion on 11 December 2005 In recent years the Environment Agency has undertaken a series of projects to understand the scale and nature of PFAS in the environment The Drinking Water Inspectorate requires water companies to report concentrations of 47 PFAS 92 European Union edit In 2019 the European Council requested the European Commission to develop an action plan to eliminate all non essential uses of PFAS due to the growing evidence of adverse effects caused by exposure to these substances the evidence for the widespread occurrence of PFAS in water soil articles and waste and the threat it can pose to drinking water 93 Germany the Netherlands Denmark Norway and Sweden submitted a so called restriction proposal based on the REACH regulation to achieve a European ban on the production use sale and import of PFAS 94 The proposal states that a ban is necessary for all use of PFAS with different periods for different applications when the ban takes effect immediately after the restriction comes into force 5 years afterwards or 12 years afterwards depending on the function and the availability of alternatives The proposal has not assessed the use of PFAS in medicines plant protection products and biocides because specific regulations apply to those substances Biocidal Products Regulation Plant Protection Products Regulation Medicinal Products Regulation that have an explicit authorization procedure that focuses on risk for health and the environment The proposal was submitted on 13 January 2023 and published by the European Chemicals Agency ECHA on 7 February From 22 March to 21 September citizens companies and other organizations can comment on the proposal during a public consultation 95 Based on the information in the restriction proposal and the consultation two committees from ECHA formulate an opinion on the risk and socio economic aspects of the proposed restriction Within a year of publication the opinions are sent to the European Commission which makes a final proposal that is submitted to the EU Member States for discussion and decision 96 Eighteen months after the publication of the restriction decision which may differ from the original proposal it will enter the ban 95 Italy edit Over 350 000 residents in the Veneto region are estimated to have been exposed to contamination through tap water and it is thought to be Europe s biggest PFAS related environmental disaster who While Italy s National Health Institute ISS Istituto Superiore di Sanita set the threshold limit of PFOA in the bloodstream at 8 nanograms per milliliter ng mL some residents had reached 262 and some industrial employees reach 91 900 ng mL In 2021 some data was disclosed by Greenpeace and local citizens after a long legal battle against the Veneto Region and ISS which for years has denied access to data despite values known since or even before 2017 The Veneto region has not carried out further monitoring or taken resolutive actions to eliminate pollution and reduce at least gradually the contamination of non potable water Although in 2020 the European Food Safety Agency EFSA has reduced by more than four times the maximum tolerable limit of PSAS that can be taken through the diet the region has not carried out new assessments or implemented concrete actions to protect the population and the agri food and livestock sectors Some limits were added to monitoring the geographical area which does not include the orange zone and other areas affected by contamination as well as the insufficiency of analysis on important productions widespread in the areas concerned eggs up to 37 100 ng kg fish 18 600 ng kg spinach and radicchio only one sampling carried out kiwis melons watermelons cereals only one sample was analyzed soy wines and apples 97 Sweden edit Highly contaminated drinking water has been detected at several locations in Sweden Such locations include Arvidsjaur Lulnaset Uppsala and Visby 98 99 In 2013 PFAS were detected at high concentrations in one of the two municipality drinking water treatment plants in the town of Ronneby in southern Sweden Concentrations of PFHxS and PFOS were found at 1700 ng L and 8000 ng L respectively 100 The source of contamination was later found to be a military fire fighting exercise site in which PFAS containing fire fighting foam had been used since the mid 1980s 101 Additionally low level contaminated drinking water has also been shown to be a significant exposure source of PFOA PFNA PFHxS and PFOS for Swedish adolescents ages 10 21 Even though the median concentrations in the municipality drinking water were below lt 1 ng individual PFAS L positive associations were found between adolescent serum PFAS concentrations and PFAS concentrations in drinking water 102 United States edit An estimated 26 000 U S sites are contaminated with PFASs At least six million Americans are estimated to have drinking water containing PFASs above the safe limit published prior to 2022 by the U S Environmental Protection Agency EPA 103 104 More than 200 million Americans are estimated to live in places where the tap water PFAS level a combination of PFOA and PFOS levels exceeds the 1 ppt part per trillion limit set in 2022 by the EPA 105 Between 2016 and 2021 the U S Geological Survey USGS tested tap water from 716 locations across the United States and reported in 2023 that the PFAS levels exceeded the EPA advisories in approximately 75 of the samples from urban areas and in approximately 25 of the rural area samples 106 Industry edit Certain PFASs are no longer manufactured in the United States as a result of phase outs including the PFOA Stewardship Program 2010 2015 in which eight major chemical manufacturers agreed to eliminate the use of PFOA and PFOA related chemicals in their products and emissions from their facilities 107 Although PFOA and PFOS are no longer manufactured in the United States they are still produced internationally and are imported into the U S in consumer goods such as carpet leather and apparel textiles paper and packaging coatings rubber and plastics 108 In 2020 manufacturers and the Food and Drug Administration announced an agreement to phase out some types of PFAS that are used in food packaging by 2024 109 PFASs are also used by major companies of the cosmetics industry in a wide range of cosmetics including lipstick eye liner mascara foundation concealer lip balm blush and nail polish A 2021 study tested 231 makeup and personal care products and found organic fluorine an indicator of PFASs in more than half of the samples High levels of fluorine were most commonly identified in waterproof mascara 82 of brands tested foundations 63 and liquid lipstick 62 110 111 As many as 13 types of individual PFAS compounds were found in each product 110 Since PFAS compounds are highly mobile they are readily absorbed through human skin and through tear ducts and such products on lips are often unwittingly ingested Manufacturers often fail to label their products as containing PFASs which makes it difficult for cosmetics consumers to avoid products containing PFASs 112 In response Senators Susan Collins of Maine and Richard Blumenthal of Connecticut proposed the No PFAS in Cosmetics Act in the United States Senate 113 It was also introduced in the United States House of Representatives by Michigan Representative Debbie Dingell 114 but the U S chemical industry lobby has killed efforts to regulate this 115 Military bases edit The water in and around at least 126 U S military bases has been contaminated by high levels of PFASs because of their use of firefighting foams since the 1970s according to a study by the U S Department of Defense Of these 90 bases reported PFAS contamination that had spread to drinking water or groundwater off the base 116 117 A 2022 Pentagon report acknowledged that approximately 175 000 U S military personnel at two dozen American military facilities drank water contaminated by PFAS that exceeded the U S EPA limit However according to an analysis of the Pentagon report by the non partisan Environmental Working Group the Pentagon report downplayed the number of people exposed to PFAS which was much higher probably in excess of 640 000 at 116 military facilities than the number advanced by the Pentagon report The EWG found that the Pentagon also omitted from its report some types of diseases that are likely to be caused by PFAS exposure such as testicular cancer kidney disease and fetal abnormalities 118 Environmental Protection Agency actions edit EPA published non enforceable drinking water health advisories for PFOA and PFOS in 2016 119 120 In March 2021 EPA announced that it would develop national drinking water standards for PFOA and PFOS 121 On December 27 2021 EPA published a regulation requiring drinking water utilities to conduct monitoring for 29 compounds The data are to be collected during 2023 to 2025 EPA will pay for the monitoring costs for small drinking water systems those serving a population of 10 000 or fewer The agency may use the monitoring data to develop additional regulations 122 123 In mid 2021 EPA announced plans to revise federal wastewater regulations effluent guidelines for several industries that manufacture PFASs or use PFASs in fabricating various products 124 125 In October 2021 EPA announced the PFAS Strategic Roadmap It is a whole of EPA strategy and considers the full lifecycle of PFAS including drinking water monitoring and risk assessment for PFOA and PFOS in biosolids processed wastewater sludge used as fertilizer 126 127 The EPA issued health advisories for four specific PFASs in June 2022 significantly lowering their safe threshold levels for drinking water PFOA was reduced from 70 ppt to 0 004 ppt while PFOS was reduced from 70 ppt to 0 02 ppt GenX s safe levels were set at 10 ppt while PFBS were set to 2000 ppt While not enforceable these health advisories are intended to be acted on by states in setting their own drinking water standards 128 A formal EPA rule to add PFOA and PFAS as hazardous chemicals was first issued for comment in August 2022 which would require anyone discharging waste to monitor and restrict the release of these PFAS to set levels and report when the wastewater exceeds it It would also make grounds affected by high levels of PFIA or PFAS to be considered Superfund cleanup sites 129 The EPA formally established rules for establishing these two chemicals as hazardous chemicals in April 2024 130 EPA has listed recommended steps that consumers may take to reduce possible exposure to PFAS chemicals 131 nbsp USGS map showing the number of PFAS detections in tap water samples from select sites across the US On 14 March 2023 EPA announced the proposed National Primary Drinking Water Regulation NPDWR This proposal includes new maximum contaminant levels MCLs in drinking water for six well known PFAS PFOA PFOS GenX PFBS PFNA and PFHxS While the proposal does not require any actions until its finalization the EPA believes it will be implemented by late 2023 If these new restrictions are put into place the EPA expects that they will prevent thousands of deaths and tens of thousands of PFAS attributable illnesses Along with legally enforceable MCLs the EPA proposal will also require public water systems to actively monitor for the 6 PFAS notify the public about the level of PFAS in the water supply and take measures to reduce the level of PFAS in drinking water if they exceed the MCLs 132 In April 2024 the EPA issued its final ruling requireing that within 3 years these six PFAS must be removed to near zero levels in drinking water supplies States would be given up to 1 billion in aid to help with the initial testing and treatment of water for this purpose 133 The EPA has stated that while some companies have reached certain conclusions related to PFASs the EPA research is still ongoing and as of 2023 remains inconclusive as it relates to the certainty of detrimental effects on humans according to the EPA Current scientific research suggests that exposure to certain PFAS may lead to adverse health outcomes However research is still ongoing to determine how different levels of exposure to different PFAS can lead to a variety of health effects Research is also underway to better understand the health effects associated with low levels of exposure to PFAS over long periods of time especially in children 67 Legal actions edit In February 2017 DuPont and Chemours a DuPont spin off agreed to pay 671 million to settle lawsuits arising from 3 550 personal injury claims related to releasing of PFASs from their Parkersburg West Virginia plant into the drinking water of several thousand residents 134 This was after a court created independent scientific panel the C8 Science Panel found a probable link between C8 exposure and six illnesses kidney and testicular cancer ulcerative colitis thyroid disease pregnancy induced hypertension and high cholesterol 33 135 In October 2018 a class action suit was filed by an Ohio firefighter against several producers of fluorosurfactants including the 3M and DuPont corporations on behalf of all U S residents who may have adverse health effects from exposure to PFASs 136 The story is told in the film Dark Waters 137 In 2023 the American multinational 3M reached a US 10 3 billion settlement with a host of US public water systems to resolve water pollution claims tied to PFAS 138 Three other major chemicals companies Chemours DuPont and Corteva have reached an agreement in principle for US 1 19 bn to settle claims they contaminated US public water systems with PFAS 138 In December 2023 as part of a four year legal battle 139 the EPA banned Inhance a Houston Texas based manufacturer that produces an estimated 200m containers annually with a process that creates among other chemicals PFOA from using the manufacturing process 140 In March 2024 the Fifth Circuit federal appeals court overturned the ban While the court did not deny the containers health risks it said that the EPA could not regulate the manufactured containers under the statute it used State actions edit In 2021 Maine became the first U S state to ban these compounds in all products by 2030 except for instances deemed currently unavoidable 141 142 As of October 2020 update the states of California Connecticut Massachusetts Michigan Minnesota New Hampshire New Jersey New York Vermont and Wisconsin had enforceable drinking water standards for between two and six types of PFAS The six chemicals termed by the Massachusetts Department of Environmental Protection as PFAS6 are measured either individually or summed as a group depending on the standard they are 143 Perfluorooctanesulfonic acid PFOS Perfluorooctanoic acid PFOA Perfluorohexanesulfonic acid PFHxS Perfluorononanoic acid PFNA Perfluoroheptanoic acid PFHpA Perfluorodecanoic acid PFDA California edit In 2021 California banned PFASs for use in food packaging and from infant and children s products and also required PFAS cookware in the state to carry a warning label 144 Maine edit A program licensed and promoted by the Maine Department of Environmental Protection that provided free municipal wastewater sludge biosolids to farmers as fertilizer has resulted in PFAS contamination of local drinking water and farm grown produce 145 146 Michigan edit The Michigan PFAS Action Response Team MPART was launched in 2017 and is the first multi agency action team of its kind in the nation Agencies representing health environment and other branches of state government have joined together to investigate sources and locations of PFAS contamination in the state take action to protect people s drinking water and keep the public informed 147 Groundwater is tested at locations throughout the state by various parties to ensure safety compliance with regulations and proactively detect and remedy potential problems In 2010 the Michigan Department of Environmental Quality MDEQ discovered levels of PFASs in groundwater monitoring wells at the former Wurtsmith Air Force Base As additional information became available from other national testing Michigan expanded its investigations into other locations where PFAS compounds were potentially used 147 In 2018 the MDEQ s Remediation and Redevelopment Division RRD established cleanup criteria for groundwater used as drinking water of 70 ppt of PFOA and PFOS individually or combined The RRD staff are responsible for implementing these criteria as part of their ongoing efforts to clean up sites of environmental contamination The RRD staff are the lead investigators at most of the PFAS sites on the MPART website and also conduct interim response activities such as coordinating bottled water or filter installations with local health departments at sites under investigation or with known PFAS concerns Most of the groundwater sampling at PFAS sites under RRD s lead is conducted by contractors familiar with PFAS sampling techniques The RRD also has a Geologic Services Unit with staff who install monitoring wells and are also well versed with PFAS sampling techniques 147 The MDEQ has been conducting environmental clean up of regulated contaminants for decades Due to the evolving nature of PFAS regulations as new science becomes available the RRD is evaluating the need for regular PFAS sampling at Superfund sites and is including an evaluation of PFAS sampling needs as part of a Baseline Environmental Assessment review 147 Earlier in 2018 the RRD purchased lab equipment that will allow the MDEQ Environmental Lab to conduct analyses of certain PFAS samples Currently most samples are shipped to one of the few labs in the country that conduct PFAS analysis in California although private labs in other parts of the country including Michigan are starting to offer these services As of August 2018 RRD has hired additional staff to work on developing the methodology and conducting PFAS analyses 147 In 2020 Michigan Attorney General Dana Nessel filed a lawsuit against 17 companies including 3M Chemours and DuPont for hiding known health and environmental risks from the state and its residents Nessel s complaint identifies 37 sites with known contamination 148 The Michigan Department of Environment Great Lakes and Energy introduced some of the strictest drinking water standards in the country for PFAS setting maximum contaminant levels MCLs for PFOA and PFOS to 8 and 16 ppt respectively down from previous existing groundwater cleanup standards of 70 ppt for both and introducing MCLs for 5 other previously unregulated PFAS compounds limiting PFNA to 6 ppt PFHxA to 400 000 ppt PFHxS to 51 ppt PFBS to 420 ppt and HFPO DA to 370 ppt 149 The change adds 38 additional sites to the state s list of known PFAS contaminated areas bringing the total number of known sites to 137 About half of these sites are landfills and 13 are former plating facilities 150 In 2022 PFOS was found in beef produced at a Michigan farm the cattle had been fed crops fertilized with contaminated biosolids State agencies issued a consumption advisory but did not order a recall because there currently is no PFOS contamination in beef government standards 151 Minnesota edit In February 2018 3M settled a lawsuit for 850 million related to contaminated drinking water in Minnesota 152 New Jersey edit In 2018 the New Jersey Department of Environmental Protection NJDEP published a drinking water standard for PFNA Public water systems in New Jersey are required to meet an MCL standard of 13 ppt 153 154 In 2020 the state set a PFOA standard at 14 ppt and a PFOS standard at 13 ppt 155 In 2019 NJDEP filed lawsuits against the owners of two plants that had manufactured PFASs and two plants that were cited for water pollution from other chemicals The companies cited are DuPont Chemours and 3M 156 NJDEP also declared five companies to be financially responsible for statewide remediation of the chemicals Among the companies accused were Arkema and Solvay regarding a West Deptford Facility in Gloucester County where Arkema manufactured PFASs but Solvay claims to have never manufactured but only handled PFASs 157 The companies denied liability and contested the directive 158 In June 2020 the U S Environmental Protection Agency and New Jersey Department of Environmental Protection published a paper reporting that a unique family of PFAS used by Solvay chloroperfluoropolyether carboxylates ClPFPECAs were contaminating the soils of New Jersey as far from the Solvay facility as 150 km 159 and the ClPFPECAs were found in water as well 160 Later in 2020 the New Jersey state attorney general filed suit in the New Jersey Superior Court against Solvay regarding PFAS contamination of the state s environment 161 In May 2021 Solvay issued a press release that the company is discontinuing the use of fluorosurfactants in the U S 162 New York edit In 2016 New York along with Vermont and New Hampshire acknowledged PFOA contamination by requesting the EPA to release water quality guidance measures Contamination has been observed by the New York State Department of Environmental Conservation in Hoosick Falls Newburgh Petersburgh Poestenkill Mahopac and Armonk 163 The village of Hoosick Falls has received a 65 25 million dollar settlement from Saint Gobain Performance Plastics Honeywell 3M and DuPont companies through a class action lawsuit in 2021 due to the disposal of PFAS chemicals into the groundwater of the local water treatment plant 164 Washington edit Five military installations in Washington State have been identified by the U S Senate Committee on Environment and Public Works as having PFAS contamination Toward environmental and consumer protections the Washington State Department of Ecology published a Chemical Action Plan in November 2021 and in June 2022 the governor tasked the Washington State Department of Ecology with phasing out manufacture and import of products containing PFASs Initial steps taken by the Washington State Department of Health to protect the public from exposure through drinking water have included setting State Action Levels for five PFASs PFOA PFOS PFNA PFHxS and PFBS which were implemented in November 2021 165 166 167 United Nations edit PFOS its salts and perfluorooctanesulfonyl fluoride as well as PFOA and PFHxS including their salts and precursors have been listed as persistent organic pollutants POPs in the Stockholm Convention 168 The long chain C9 C21 PFCAs are currently under review for listing 169 Occupational exposure editOccupational exposure to PFASs occurs in numerous industries due to the widespread use of the chemicals in products and as an element of industrial process streams 170 PFASs are used in more than 200 different ways in industries as diverse as electronics and equipment manufacturing plastic and rubber production food and textile production and building and construction 171 Occupational exposure to PFASs can occur at fluorochemical facilities that produce them and other manufacturing facilities that use them for industrial processing like the chrome plating industry 170 Workers who handle PFAS containing products can also be exposed during their work such as people who install PFAS containing carpets and leather furniture with PFAS coatings professional ski waxers using PFAS based waxes and fire fighters using PFAS containing foam and wear flame resistant protective gear made with PFASs 170 172 173 Exposure pathways edit People who are exposed to PFASs through their jobs typically have higher levels of PFASs in their blood than the general population 170 174 175 While the general population is exposed to PFASs through ingested food and water occupational exposure includes accidental ingestion inhalation exposure and skin contact in settings where PFAS become volatile 176 13 The severity of PFAS associated health effects can vary based on the length of exposure level of exposure and health status 170 Professional ski wax technicians edit Compared to the general public exposed to contaminated drinking water professional ski wax technicians are more strongly exposed to PFASs PFOA PFNA PFDA PFHpA PFDoDA from the glide wax used to coat the bottom of skis to reduce the friction between the skis and snow 177 During the coating process the wax is heated which releases fumes and airborne particles 177 Compared to all other reported occupational and residential exposures ski waxing had the highest total PFAS air concentrations 178 Manufacturing workers edit People who work at fluorochemical production plants and in manufacturing industries that use PFASs in the industrial process can be exposed to PFASs in the workplace Much of what we know about PFASs exposure and health effects began with medical surveillance studies of workers exposed to PFASs at fluorochemical production facilities These studies began in the 1940s and were conducted primarily at U S and European manufacturing sites Between the 1940s and 2000s thousands of workers exposed to PFASs participated in research studies that advanced scientific understanding of exposure pathways toxicokinetic properties and adverse health effects associated with exposure 26 179 180 The first research study to report elevated organic fluorine levels in the blood of fluorochemical workers was published in 1980 26 It established inhalation as a potential route of occupational PFAS exposure by reporting measurable levels of organic fluorine in air samples at the facility 26 Workers at fluorochemical production facilities have higher levels of PFOA and PFOS in their blood than the general population Serum PFOA levels in fluorochemical workers are generally below 20 000 ng mL but have been reported as high as 100 000 ng mL whereas the mean PFOA concentration among non occupationally exposed cohorts in the same time frame was 4 9 ng mL 181 27 Among fluorochemical workers those with direct contact with PFASs have higher PFAS concentrations in their blood than those with intermittent contact or no direct PFAS contact 179 181 Blood PFAS levels have been shown to decline when direct contact ceases 181 182 PFOA and PFOS levels have declined in U S and European fluorochemical workers due to improved facilities increased usage of personal protective equipment and the discontinuation of these chemicals from production 179 183 Occupational exposure to PFASs in manufacturing continues to be an active area of study in China with numerous investigations linking worker exposure to various PFASs 184 185 186 Firefighters edit nbsp Firefighters using aqueous film forming foam AFFF PFASs are commonly used in Class B firefighting foams due to their hydrophobic and lipophobic properties as well as the stability of the chemicals when exposed to high heat 187 Research into occupational exposure for firefighters is emergent though frequently limited by underpowered study designs A 2011 cross sectional analysis of the C8 Health Studies found higher levels of PFHxS in firefighters compared to the sample group of the region with other PFASs at elevated levels without reaching statistical significance 188 A 2014 study in Finland studying eight firefighters over three training sessions observed select PFASs PFHxS and PFNA increase in blood samples following each training event 187 Due to this small sample size a test of significance was not conducted A 2015 cross sectional study conducted in Australia found that PFOS and PFHxS accumulation was positively associated with years of occupational AFFF exposure through firefighting 174 Due to their use in training and testing recent studies indicate occupational risk for military members and firefighters as higher levels of PFASs in exposure were indicated in military members and firefighters when compared to the general population 189 PFAS exposure is prevalent among firefighters not only due to its use in emergencies but also because it is used in personal protective equipment In support of these findings states like Washington and Colorado have moved to restrict and penalize the use of Class B firefighting foam for firefighter training and testing 190 191 Exposure after World Trade Center terrorist attacks edit The 11 September 2001 collapse of the World Trade Center buildings in New York City resulted in the release of chemicals from the destruction of construction and electrical material and long term chemical fires This collapse caused the release of several toxic chemicals including fluorinated surfactants used as soil and stain resistant coatings on various materials 192 First responders to this incident were exposed to PFOA PFNA and PFHxS through inhalation of dust and smoke released during and after the collapse of the World Trade Center 192 Fire responders who were working at or near ground zero were assessed for respiratory and other health effects from exposure to emissions at the World Trade Center Early clinical testing showed a high prevalence of respiratory health effects Early symptoms of exposure often presented with persistent coughing and wheezing PFOA and PFHxS levels were present in both smoke and dust exposure but first responders exposed to smoke had higher concentrations of PFOA and PFHxS than those exposed to dust 192 Mitigation measures edit Several strategies have been proposed as a way to protect those who are at greatest risk of occupational exposure to PFAS including exposure monitoring regular blood testing and the use of PFAS free alternatives For example fluorine free firefighting foam and plant based ski wax contain no PFAS and greatly reduce the occupational hazards associated with certain professions 193 Remediation editMain article Remediation of per and polyfluoroalkyl substances Water treatment edit Several technologies are currently available for remediating PFASs in liquids These technologies can be applied to drinking water supplies groundwater industrial wastewater surface water and other applications such as landfill leachate Influent concentrations of PFASs can vary by orders of magnitude for specific media or applications These influent values along with other general water quality parameters for example pH can influence the performance and operating costs of the treatment technologies The technologies are Foam fractionation 194 Sorption Granular activated carbon Biochar Ion exchange Precipitation flocculation coagulation Redox manipulation chemical oxidation and reduction technologies Membrane filtration Reverse osmosis Nanofiltration 195 Supercritical water oxidation 196 Low Energy Electrochemical Oxidation EOx Private and public sector applications of one or more of these methodologies above are being applied to remediation sites throughout the United States and other international locations 197 Most solutions involve on site treatment systems while others are leveraging off site infrastructure and facilities such as a centralized waste treatment facility to treat and dispose of the PFAS pool of compounds The US based Interstate Technology and Regulatory Council ITRC 198 has undertaken extensive evaluation of ex situ and in situ treatment technologies for PFAS impacted liquid matrices These technologies are divided into field implemented technologies limited application technologies and developing technologies and typically fit into one of three technology types Separation Concentration and Destruction The type of PFAS remediation technology selected is often a reflection of the PFAS contamination levels and the PFAS signature i e the combination of short and long chain PFAS substances present in conjunction with the site specific water chemistry and cross contaminants present in the liquid stream More complex waters such as landfill leachates and WWTP waters require more robust treatment solutions which are less vulnerable to blockage Stripping and EnrichmentFoam Fractionation utilises the air water interface of a rising air bubble to collect and harvest PFAS molecules The hydrophobic tail of many long chain criteria PFAS compounds adhere to this interface and rise to the water surface with the air bubble where they present as a foam for harvesting and further concentration The foam fractionation technique is a derivation of traditional absorptive bubble separation techniques used by industries for decades to extract amphiphilic contaminants The absence of a solid absorptive surface reduces consumables and waste byproducts and produces a liquid hyper concentrate which can be fed into one of the various PFAS destruction technologies Across various full scale trials and field applications this technique provides a simplistic and low operational cost alternative for complex PFAS impacted waters 199 DestructionMost recently a 2022 study published in the Journal of Environmental Engineering found that a heat and pressure based technique known as supercritical water oxidation destroyed 99 of the PFASs present in a water sample During this process oxidizing substances are added to PFAS contaminated water and then the liquid is heated above its critical temperature of 374 degrees Celsius at a pressure of more than 220 bars The water becomes supercritical and in this state water repellent substances such as PFASs dissolve much more readily 196 Theoretical and early stage solutions edit A possible solution for PFAS contaminated wastewater treatment has been developed by the Michigan State University Fraunhofer team Boron doped diamond electrodes are used for the electrochemical oxidation system where it is capable of breaking PFAS molecular bonds which essentially eliminates the contaminates leaving fresh water 200 Cory Rusinek an electrochemist at MSU Fraunhofer stated EO or electrochemical oxidation is a simple clean and effective method for destruction of PFASs and other co contaminants as a complementary procedure to other wastewater treatment processes If we can remove it from wastewater we can reduce its occurrence in surface waters 200 Acidimicrobium sp strain A6 has been shown to be a PFAS and PFOS remediator 201 PFAS with unsaturated bonds are easier to break down the commercial dechlorination culture KB1 contains Dehalococcoides is capable of breaking down such substances but not saturated PFAS When alternative easier to digest substrates are present microbes may prefer them over PFAS 202 Chemical treatment edit A study published in Science in August 2022 indicated that perfluoroalkyl carboxylic acids PFCAs can be mineralized via heating in a polar aprotic solvent such as dimethyl sulfoxide It reported that heating PFCAs in an 8 to 1 mixture of dimethyl sulfoxide and water at 80 120 C 176 248 F in the presence of sodium hydroxide caused the removal of the carboxylic acid group at the end of the carbon chain creating a perfluoroanion that mineralizes into sodium fluoride and other salts such as sodium trifluoroacetate formate carbonate oxalate and glycolate The process does not work on perfluorosulfonic acids such as PFOS 203 A more recent study published in Chemical Science shows breakdown of C F bonds and their mineralization as YF3 or YF6 clusters 204 Another study in the Journal of the American Chemical Society described the PFASs breakdown using metal organic frameworks MOFs 205 Analytical methods editAnalytical methods for specific PFASs in environmental matrices and food and food have generally improved in sensitivity and selectivity in recent years e g to meet lower regulatory limit values However sensitive and accurate targeted methods using isotope labeled internal standards still only cover just over 50 PFASs mostly PFCAs and PFSAs with perfluorinated alkyl chains of four or more carbon atoms 206 23 Sum parameter methods such as total organic fluorine assays e g adsorbable organic fluorine AOF extractable organic fluorine EOF and the total oxidizable precursor TOP assay are increasingly being used across matrices to quantify the proportion of PFASs not captured by typical targeted analyses 23 207 208 Sample chemicals editSome common per and polyfluoroalkyl substances include 209 210 Polytetrafluoroethylene aka PTFE or Teflon Perfluoroalkyl carboxylic acids PFCAs Perfluorosulfonic acids PFSAs Fluorotelomers FTOHs Name Abbreviation Structural formula Molecular weight g mol CAS No Perfluorobutane sulfonamide H FBSA C4F9SO2NH2 299 12 30334 69 1 Perfluoropentanesulfonamide PFPSA C5F11SO2NH2 349 12 82765 76 2 Perfluorohexanesulfonamide PFHxSA C6F13SO2NH2 399 13 41997 13 1 Perfluoroheptanesulfonamide PFHpSA C7F15SO2NH2 449 14 82765 77 3 Perfluorooctanesulfonamide PFOSA C8F17SO2NH2 499 14 754 91 6 Perfluorobutanesulfonyl fluoride PFBSF C4F9SO2F 302 09 375 72 4 Perfluorooctanesulfonyl fluoride PFOSF C8F17SO2F 502 12 307 35 7Films editThe Devil We Know 2018 Dark Waters 2019 See also editTimeline of events related to per and polyfluoroalkyl substances Entegris formerly Fluoroware of Chaska MN manufacturer of teflon components for health and semiconductor Fabs FSI International now TEL FSI Polytetrafluoroethylene PTFE Fluoropolymer subclass of per and polyfluoroalkyl substances Euthenics as the general category for policy interventions aiming to mitigate associated effects on human populationsReferences edit Per and Polyfluoroalkyl Substances PFAS 30 March 2016 a b OECD 2021 Reconciling Terminology of the Universe of Per and Polyfluoroalkyl Substances Recommendations and Practical Guidance PDF OECD Series on Risk Management Paris OECD Publishing p 23 Archived from the original PDF on 13 July 2021 a b PubChem Classification Browser PFAS and Fluorinated Compounds in PubChem Tree pubchem ncbi nlm nih gov NBCI Retrieved 12 November 2023 a b c d e f Per and Polyfluorinated Substances PFAS Factsheet National Biomonitoring 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August 2019 Further reading editLindstrom AB Strynar MJ Libelo EL October 2011 Polyfluorinated compounds past present and future Environmental Science amp Technology 45 19 7954 7961 Bibcode 2011EnST 45 7954L doi 10 1021 es2011622 PMID 21866930 S2CID 206946893 Ritter SK 2015 The Shrinking Case For Fluorochemicals Chemical amp Engineering News 93 28 27 29 doi 10 1021 cen 09328 scitech1 Archived from the original on 18 August 2016 Retrieved 3 August 2016 Lehmler HJ March 2005 Synthesis of environmentally relevant fluorinated surfactants a review Chemosphere 58 11 1471 1496 Bibcode 2005Chmsp 58 1471L doi 10 1016 j chemosphere 2004 11 078 PMID 15694468 External links editPer and Polyfluoroalkyl Substances PFAS at the National Toxicology Program Per and Polyfluoroalkyl Substances and Your Health at the Agency for Toxic Substances and Disease Registry Per and Polyfluoroalkyl Substances PFAS at the United States Environmental Protection Agency Per and polyfluoroalkyl substances PFASs at the European Chemicals Agency PFAS contamination map of Europe Per and Polyfluoroalkyl substances National Institute for Occupational Safety and Health The Forever Pollution Project Journalists tracking PFAS across Europe PFAS contamination in Queensland Australia State Library of Queensland Retrieved from https en wikipedia org w index php title Per and polyfluoroalkyl substances amp oldid 1221558432, wikipedia, wiki, book, books, library,

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