PFAS here. . .PFAS there. . .PFAS is everywhere we turn in the first few months of 2024. PFAS (per- and polyfluoroalkyl substances) is the latest buzzword in the global specialty chemicals industry. It has come into universal usage when invoking any chemical included in a family of fluorine-containing chemical compounds that are used by a nearly endless list of manufacturers producing a staggering number of products for a seemingly infinite number of applications in virtually all market and product segments.

Thanks to their unique properties and unmatched performance, various types of PFAS are used across all sectors of the global economy, including numerous cutting-edge applications. Driven by global megatrends such as the energy transition and digitalization, they are key enablers of major innovations across a wide range of critical industries.¹ All of this notwithstanding, in early 2024, PFAS is a problem—and it is a problem for four principal reasons:

• Some types of PFAS are found nearly everywhere and are virtually indestructible, hence the term “forever chemicals,” and they “are impossible to avoid. They are found in our homes, our offices, our supermarkets—practically everywhere.”² Many public officials, NGOs, and private citizens believe that certain PFAS are “extremely toxic” at extraordinarily low levels—parts per quadrillion.³ But, if true, which ones?
• A significant body of evidence has been generated that suggests that a small number of chemical compounds in the PFAS family are both bio-accumulative and hazardous to the human body.
• Consequently, there is a disturbingly diverse call from many different interest groups, including regulators, NGOs, manufacturers, the media, and the public, to ban all PFAS. This “call to ban” is not dissimilar to the call initiated by Greenpeace in 1992 to ban the use of chlorine worldwide because of a small number of toxic and/or problematic chemicals that contained chlorine.
• Certain PFAS are absolutely critical in the production of microchips by companies such as Intel, Infineon, BASF, and others. “Without some PFAS, semiconductor manufacturing is simply not possible,” says a leading European chip executive. “There are no alternatives in the market yet.”⁴

While it seems to many members of both industry and the public as though PFAS came out of nowhere in 2022-2023, this is not strictly the case. Certain substances classified as being PFAS have been studied and discussed at least as long ago as the year 2000, resulting in abundant knowledge about the two most-studied members of the PFAS family, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Nonetheless, it appears that such discussions and studies were merely serving to initiate an induction period to help prepare us for the assault now being conducted on PFAS from all sides. 

Multiple sources maintain that there are anywhere between 3,700-14,000 members in the PFAS family of fluorine-containing chemical compounds, depending upon which study one consults. The most consistently quoted number is 4,730; it is, however, of great importance that all parties recognize that the major issue is not the total number of family members that are contained within the definition of PFAS, but rather: 

• How many of them are potentially harmful, and
• How producers, users, and regulatory bodies are going to determine which chemicals included in the term “PFAS” must be eliminated from use—and which may continue to be used, possibly with additional safety measures and safeguards to prevent escape into the environment.

In 2021, the Society of Environmental Toxicology and Chemistry (SETAC) published a study⁵ that identified a subset of the 4,730 PFAS chemicals numbering 256 (5.5% of the total) that are “commercially relevant” in various countries and regions of the globe. While this author is not in a position to pass judgement regarding the accuracy of this work, if it is accurate it suggests that grouping PFAS using fundamental classification criteria based on composition and structure can be used to identify individual PFAS—or groups of PFAS—that are appropriate candidates for subjection to risk assessment protocols. This would go a long way toward enabling timely and appropriate regulatory risk assessments for the commercially relevant substances.

Of particular importance is that SETAC has determined that only 241 of the 256 commercially relevant substances meet the definition of PFAS. Of these, 52 were polymers, which are of great importance to the paint and coatings—and many other—industries and are, in this author’s personal opinion, unlikely to prove hazardous to either human health or to the environment. Proving this, however, is difficult when they are currently being lumped together with thousands of other PFAS in North America, the EU, and China.

Grouping and Evaluation of PFAS

The conclusion of the Organization for Economic Co-operation and Development (OECD) and the United Nations Environment Programme (UNEP), as stated in their 2018 joint report, is that it is generally seen as an impossible task to evaluate 4,730+ chemicals. As a result, a number of regulatory bodies are lumping all fluorine compounds together as PFAS, even if they are not PFAS and do not fit the current European definition (Figure 1).⁶ 

The U.S. definition of PFAS is slightly different; PFAS is defined as a chemical substance that structurally contains at least one of the following three substructures:

    (1) R-(CF2)-CF(R’)R’’, where both the CF2 and CF moieties are saturated carbons;

    (2) R-CF2OCF2-R’, where R and R’ can either be F, O, or saturated carbons;

    (3) CF3C(CF3)R’R’’, where R’ and R”” can either be F or saturated carbons.

Regional and global regulatory bodies are busy discussing PFAS, and their focus on this topic has the effect of forcing all producers of PFAS-containing chemical products, as well as manufacturers of articles that incorporate these chemical products, to not only discuss PFAS but to give serious thought to either how to rid their products of PFAS or to why their PFAS-containing products must be protected at all costs. This is not a trivial task, because this is not a trivial topic—it is a topic of great importance that has potential impact upon some of the industries that the global community is counting upon for future growth and advancement of technology and living standards. According to Rich Czarnecki, Vice President of Micro Powders, Inc., in 2023, “Predictions of the market shifting away from PFAS additives held true, with dramatically increased attention on PTFE-free alternative and bio-based additives. We have been developing and honing this technology for years in preparation to meet the market’s demands.”⁷

The great English essayist, historian, philosopher, and translator, Thomas Carlyle, placed a striking metaphor firmly into the English vernacular when he translated the German proverb, “Das Kind mit dem Bade ausschütten,” as “Don’t throw the baby out with the bathwater.” This is precisely what would be accomplished by banning all PFAS—and this is why the current clamor to do so is a problem of global scientific, technological, industrial, governmental, and societal magnitude.

PFAS Fundamentals

Everywhere we look, we find a variety of PFAS products fulfilling critical roles in a broad range of industrial- and consumer-facing applications. Examples range from non-stick cookware; firefighting foams; stain-resistant fabric and carpets; water-, stain-, and grease-resistant consumer goods; food packaging; dental floss; and waterproof clothing to propellants; refrigerants; pharmaceuticals (both packaging and contents); blowing agents; highly durable building products for exterior cladding; and myriad other applications (Figures 2-4 and 6).

Without wishing to be reductive, it is nonetheless helpful, when attempting to assess the overall PFAS issue in light of the paint and coatings market space, to think of both the “pros” and “cons” of using PFAS additives and especially PFAS polymers in products across multiple market sectors (Figure 5).

Global Regulatory Approaches

Regulatory agencies do not always give an appropriate level of consideration—or take the most logical steps—when dealing with the information obtained from even the most carefully controlled studies. It’s unfortunate, but let’s face it, “We have too many linear thinkers, but we live in a three-dimensional world.”⁹ With regard to PFAS, this is likely to be multiplied as a result of the different perspectives from which various countries and regions of the globe are viewing this subject.

The EU, for example, is evaluating the PFAS issue under the purview of REACH/ECHA (European Chemicals Agency), with particular emphasis on the following four chemicals but still within the context of banning all PFAS: 

• Perfluorooctanoic acid (PFOA—of significant concern in the U.S., China, and EU) that, along with PFOS, was the earliest PFAS to cause a red flag to be raised, as well as the most extensively studied. 
• Perfluorooctane sulfonic acid (PFOS—of significant concern in the U.S., China, and EU), subject in the United States to significant federal regulatory activity, along with PFOA, during the period 2000-2010. 
• In 2006, the EU Directive 2006/122/EC restricted the use of perfluorooctane sulfonic acid, and in 2019 the EU signed the International Stockholm Convention on Persistent Organic Pollutants, which banned the production and use of PFOA, its salts, and PFOA-related compounds, with exemptions only for medical textiles and certain firefighting foams. This was later followed by the restriction of perfluorooctanoic acid (PFOA) by EU Regulation 2020/784.
• Perfluorohexane-1-sulphonic acid (PFHxS), its salts, and related substances (principally of concern in EU, at least currently).
• Undecafluorohexanoic acid (PFHxA), its salts, and related substances (principally of concern in EU, at least currently).
• There will be others—possibly even by the date this article is published.

As of early 2024, the goal of ECHA is to ban, or restrict to only a few critical uses, PFAS substances. The basis for this is the EU’s 2020 “Chemicals Strategy for Sustainability—Towards a Toxin-Free Environment.” ECHA conducted a “six-month consultation” on the proposal that started on March 22, 2023, with public comments accepted until September 25.¹⁰ The response was overwhelming, with in excess of 5,500 comments submitted by 4,400 organizations, companies, and individuals. These are being evaluated, but this process will probably take a fair amount of time and is likely to delay decisions on any individual PFAS for months or even years.

In contrast, despite the January 2024, ruling by the U.S. Environmental Protection Agency (EPA) that removed the de minimis exemption that allowed manufacturing facilities and importers of record to avoid reporting information on PFAS when those chemicals were used in small concentrations, the U.S. federal government appears to be satisfied that the regulatory activity during the period 2000-2010, centered principally on PFOS and PFOA, was sufficient and is currently disinclined to pursue additional inquiries. Instead, it has indicated that this should be an issue for the individual states, which promises to cause no end of confusion, leading to a patchwork of potentially contradictory state regulations. 

Leading the way, the State of Minnesota has enacted what is currently the broadest PFAS policy in the country. “Beginning on January 1, 2025, it will be illegal to sell or distribute some products with intentionally added PFAS within Minnesota,”¹¹ except those that are necessary for public health. It also requires manufacturers to report their use of PFAS in products to the state by 2026. The bill eliminates PFAS from 13 product categories: menstrual products, cleaning ingredients, cookware, dental floss, firefighting foam, food packaging, cosmetics, textiles, carpets, fabric treatments, upholstered furniture, children’s products, and ski wax.¹²

Six other states—California, Colorado, Indiana, Maryland, Maine, and Michigan—have already enacted legislation banning PFAS in firefighting foam and equipment, and they are in the process of either passing or considering additional legislative action. New Hampshire, New Jersey, New York, and Wisconsin are all proposing new legislative action, and there may be a few others by the time this article is published. Additionally, New York now requires consumer notices for the presence of PFAS in children’s products. While “state-by-state regulation” may or may not be the ultimate course of action pursued in the United States, it clearly indicates one of the many ways in which the EU and the United States differ with regard to their approach to the PFAS issue.

China will certainly take action affecting either certain or possibly all PFAS, but current activity is less specific than what we are seeing in either the EU or North America. In 2008, the Ministry of Environmental Protection (MEP) listed a product believed to contain PFOA in the “High Pollution, High Environmental Risk Product Catalogue.”¹³ In 2011, the National Development and Reform Commission issued the “Catalogue for Guiding Industry Restructuring,” in which the production of both PFOA and PFOS were restricted, and in 2014 banned “production, transportation, application, imports and exports of PFOS, its salts, and perfluorooctanesulfonyl fluoride¹⁴ (PFOSF [also PFOS, which was formerly a key ingredient in Scotchgard™])¹⁵ except for specific exemptions and acceptable use.” 

A 2020-21 study on the presence and levels of PFAS, including 66 cities in China, with a combined population of 450MM people, indicated that PFOA, PFOS, and PFBA (perfluorobutanoic acid) were the dominant PFAS species in Chinese drinking water. The study concluded that “Drinking water in many cities and regions in China is contaminated with PFASs [sic] at levels of concern. PFAS elimination from drinking water in contaminated cities and affected regions in China is urgently needed.”¹⁶ Whether or not the regulatory agencies are considering the results of this study, however, does not appear to be a matter of public record, as far as the author is able to ascertain.

PFAS in the Future?

Uncertainty about PFAS reigns around the globe, despite the fact that they are of critical importance for a variety of applications in a number of vitally important global industries. It is likely that certain PFAS materials (particularly polymers) will be found to be of low concern, but requirements that the producers of such polymers take additional protective actions similar to those that were put in place for the production of polyvinylchloride (PVC) many years ago seem likely. 

Despite the concern that anything is possible in today’s volatile, unpredictable, and sometimes irrational world, it seems unlikely that PFAS will be unilaterally banned, because it truly makes no sense to throw the baby out with the bathwater. Once all is said and done, Aristotle will probably be smiling, because it is more than passingly likely that his “Golden Mean” (the midpoint between extremes) will prevail, and we will have neither the best nor the worst outcome with regard to the global PFAS issue.

That is in the future, however. At present, companies or entire industries based on chemicals that are on the PFAS list can ill afford to do nothing while the PFAS issues work themselves out. Both producers and users of PFAS chemicals in a huge array of highly diverse industries are wrestling with the wisdom of replacing current PFAS-containing systems with equal- (or more likely, lower-) performance products. Some will certainly succeed; most will not. Ultimately, the marketplace has to determine whether or not the substitute products are both affordable and acceptable—and if they are not, the race will be on to find alternative materials that will meet the requirements. The cleverest and most driven competitor with access to the greatest level of knowledge and experience will win. 

The best way for any raw material or coatings supplier to make sure that success can be achieved will be to eviscerate the “NIH” Syndrome (“not invented here”) from the organization and seek expertise outside of the corporate walls to help achieve PFAS replacement goals. This is not typically an easy decision, but it will be a necessary one to enable manufacturing companies to embrace a wider world of technological experience and know-how. 

PFAS producers and users will not only need to bring their finest and most dedicated R&D efforts to bear on the PFAS issue, but they will need all the help that they can get from independent technology organizations, strategic consulting firms, and independent subject matter experts. There is no other way in which both raw material suppliers and coatings producers will be able to access the most expansive knowledge base and extensive cross-fertilization in multiple fields of specialty chemicals that will be called for in dealing with the PFAS issue. One way or the other, the questions surrounding PFAS must be addressed and resolved if we are to move technology forward, not backward. 

To learn more, contact the author at gpilcher@chemquest.com or visit https://chemquest.com.

References

¹ Bushard, B. 3M Will Discontinue Use of Hazardous PFAS ‘Forever Chemicals’ by 2025. Forbes, December 20, 2022, https://www.forbes.com/sites/brianbushard/2022/12/20/3m-will-discontinue-use-of-hazardous-pfas-forever-chemicals-by-2025/?sh=404d929031d0K. 

² McGinty, M.M.; Lindwall, C. ‘Forever Chemicals’ Called PFAS Show Up in Your Food, Clothes, and Home. National Resources Defense Council (NRDC), April 13, 2023, https://www.nrdc.org/stories/forever-chemicals-called-pfas-show-your-food-clothes-and-home.

³ Ibid.

⁴ The Crackdown on Risky Chemicals that Could Derail the Chip Industry. Financial Times, 2023, https://www.ft.com/content/76979768-59c0-436f-b731-40ba329a7544.

⁵ Buck, R.C.; Korzeniowski, E.L.; Adamsky, F. Integrated Environmental Assessment and Management. Society of Environmental Toxicology and Chemistry, May 14, 2021, 17(5), 1045-1055, https://setac.onlinelibrary.wiley.com/doi/10.1002/ieam.4450.

⁶ Averbeck, F. PFAS under REACH Universal Restriction Proposal. Bundesanstalt für Arbeitsschutz und Arbeitsmedizin (BAUA), 2022, https://www.asercom.org/wp-content/uploads/2022/05/Averbeck.pdf.

⁷ Pianoforte, K. Additives Market Update. Coatings World, 2024, 29(1), 36-37.

⁸ Scott, A. The Battle Over PFAS in Europe: Industry Pushes Back on Government Proposal to Ban Fluoropolymers. C&EN Weekly Journal, September 18, 2023, https://cen.acs.org/policy/chemical-regulation/battle-over-PFAS-Europe/101/i31#:~:text=The%20European%20Commission%20(EC)%20is,a%20major%20subset%20of%20PFAS.

⁹ McCracken, E. Personal correspondence, 2024.

¹⁰ Per- and Polyfluoroalkyl Substances (PFAS). European Chemicals Agency, 2023, https://echa.europa.eu/hot-topics/perfluoroalkyl-chemicals-pfas.

¹¹ Tarter, S.; Beck, N.B.; Wall, G.R.; Leopold, M.Z.; Nyffeler, P.T. Minnesota Becomes Second State to Pass Sweeping PFAS Ban and Reporting Law Targeting All Products. The Nickel Report, Hunton Andrews Kurth LLP, May, 2023, https://www.huntonnickelreportblog.com/2023/06/minnesota-becomes-second-state-to-pass-sweeping-pfas-ban-and-reporting-law-targeting-all-products/#:~:text=In%20May%202023%2C%20Minnesota's%20Governor,containing%20PFAS%20starting%20in%20 2026. 

¹² Legislation to Affect Cookware, Dental Products, Menstrual Products. Nonwovens Industry, May 26, 2023, https://www.nonwovens-industry.com/contents/view_breaking-news/2023-05-26/minnesota-signs-pfas-ban-in-consumer-products/.

¹³ Portal on Per- and Poly Fluorinated Chemicals, People’s Republic of China. Organisation for Economic Co-operation and Development (OECD), https://www.oecd.org/chemicalsafety/portal-perfluorinated-chemicals/countryinformation/china.htm.

¹⁴ OECD, loc. cit.

¹⁵ Scotchgard™, Wikipedia, https://en.wikipedia.org/wiki/Scotchgard#:~:text=3M%20reformulated%20Scotchgard%20and%20since,utilizes%20a%20proprietary%20fluorinated%20urethane.

¹⁶ Liu, L.; Qu, Y.; Huang, J.; et al. Per- and Polyfluoroalkyl Substances (PFASs) in Chinese Drinking Water: Risk Assessment and Geographical Distribution. Environ Sci Eur, 2021, 33(6), https://doi.org/10.1186/s12302-020-00425-3.