On August 3, 2020, the European Union (EU) notified the World Trade Organization of its intention to amend the REACH Restriction List (Annex XVII) to include restriction of perfluorocarboxylic acids containing 9 to 14 carbon atoms in the chain (C9-C14 PFCAs), their salts and related substances. The term C9-C14 PFCAs covers the following six substances: perfluorononan-1-oic acid (PFNA (C9), CAS 375-95-1), nonadecafluorodecanoic acid (PFDA (C10), CAS 335-76-2), henicosafluoroundecanoic acid (PFUnDA (C11), CAS 2058-94-8), tricosafluorododecanoic acid (PFDoDA (C12), CAS 307-55-1), pentacosafluorotridecanoic acid (PFTrDA (C13), CAS 72629-94-8), and heptacosafluorotetradecanoic acid (PFTDA (C14), CAS 376-06-7). C9-C14 PFCA-related substances are defined as “substances that, based on their molecular structure, are considered to have the potential to degrade or be transformed to C9-C14 PFCAs.” The proposed restriction will replace the existing entry 68 to Annex XVII of REACH, which previously covered perfluorooctaonic acid (PFOA (C8), CAS 335-67-1) and its salts. The PFOA entry in the REACH Restriction list is being deleted because since July 4, 2020, this substance group is being regulated under the EU’s persistent organic pollutants (POP) recast regulation, i.e., Regulation (EU) 2019/1021 (FPF reported).
Relevance for food contact materials
Several studies have reported on the presence and migration of C9-C14 PFCAs and related substances from food contact materials (FCMs), but the available knowledge is rather scarce. Since the early 2000’s, the industry has been voluntarily phasing out the production and use of two long-chain per- and polyfluorinated substances (PFASs) in FCMs, i.e., C8 compounds perfluorooctanoic sulfonate (PFOS, CAS 1763-23-1) and PFOA. (Nonetheless, one PFOA salt, ammonium perfluorooctanoate (CAS 3825-26-1), is still included on the Annex I of the Regulation (EU) 10/2011 and thus authorized for use in food contact plastics in the EU.) The C8 substances are often assumed to be replaced by shorter-chain alternatives, but application of longer-chain alternatives also cannot be completely ruled out. For example, a 2012 study by Glynn and colleagues reported that a decrease of PFOS in women blood serum, observed since its phase out in 2002, has been accompanied by an increase in several of its substitutes, including not only perfluorobutanesulfnoic acid (PFBS, CAS 375-73-5) and perfluorohexane sulfonic acid (PFHxS, CAS 335-46-4) (both short-chain), but also PFNA and PFDA (longer-chain). Similarly, a 2015 study by Schlummer and colleagues found that overheated polytetrafluoroethylene (PTFE)-coated pans emitted not only short-chain but also long-chain PFCAs, with concentrations reaching up to 698 ng/h for PFOA, up to 869 ng/h for PFNA, up to 744 ng/h for PFDA, up to 499 ng/h for PFUnDA, and up to 199 ng/h for PFDoDA.
Furthermore, while the use of PFCAs has been declining in general, the use of other PFASs such as fluorotelomer alcohols (FTOHs) has continued and may even be on the rise. This is particularly problematic because FTOHs can degrade into PFCAs with respective chain lengths. A 2016 study by Yuan and colleagues detected high levels of long-chain FTOHs in a set of paper- and pulp-based food contact articles, including popcorn bags and ‘eco-friendly’ tableware sourced in China and the US, with Chinese samples displaying more types and higher concentrations of longer-chain substances (FPF reported). For example, concentrations of up to 1110 ng/g were measured for 6:2 FTOH, up to 8490 ng/g for 8:2 FTOH, up to 9350 ng/g for 10:2 FTOH, up to 8450 ng/g for 12:2 FTOH, and up to 1640 ng/g for 14:2 FTOH. Several PFCAs, including C9-C14 congeners, were also detected, but at lower concentrations (sum of all PFCAs at 119 ng/g for paper tableware and 112 ng/g for microwave popcorn bags). This study has also demonstrated migration of PFASs into food simulants and thus concluded that humans are “not only exposed to FTOHs and PFCAs via drinking water and air but also via the ingestion of food products to which FTOHs and PFCAs had migrated from FCMs.” A detailed overview of PFASs in FCMs analyzed within 22 academic studies, provided in a 2018 report by the RIVM (Danish National Institute for Public Health and Environment), also demonstrates frequent detection of C9-C14 PFCAs as well as long-chain FTOH in various FCMs.
C9-C14 PFCAs have been frequently detected in diverse food products, as for example a 2012 report by the EFSA (European Food Safety Authority) has summarized. The 2017 restriction report which accompanied the original proposal for the restriction of C9-C14 PFCAs, states that “food is the major source of exposure [to C9-C14 PFCAs] for the general population.” This document also lists “paper and food-packaging” among the potential sources of exposure to these substances. Overall, it can be assumed that the C9-C14 PFCAs themselves are probably not used in FCMs intentionally but may be present as impurities or be generated from precursor compounds such as long-chain FTOHs, for which a stronger evidence of intentional use exists. Thus, further targeted research may be necessary to gain a better understanding of the scope of use and quantities of C9-C14 PFCAs and related substances in FCMs in order to assess the resulting exposures and possible human health risks (FPF reported).
Details of the proposed restriction
The draft regulation for introduction of C9-C14 PFCAs’ restriction states that C9-C14 PFCAs, their salts and related substances currently mainly occur in the EU “as unavoidable by-products during the manufacture of perfluorinated and polyfluorinated substances containing a carbon chain of less than nine carbon atoms,” such as PFOA. In addition, “it is possible that companies may consider the use of C9-C14 PFCAs, their salts and related substances as substitutes for PFOA, its salts and related substances in the future, especially after the Union Law restrictions on PFOA become applicable.” Therefore, the European Commission (EC) deems it “necessary to prevent future possible manufacturing and use resulting in increasing releases into the environment.” The EC further explains that most of the C9-C14 PFCAs are by now placed on the REACH Candidate list of substances of very high concern (SVHCs) for authorization as persistent, bioaccumulative and toxic (PBT) and/or very persistent and very bioaccumulative (vPvB) substances, and that related substances are also to be regarded as PBT or vPvB substances “due to their transformation or degradation in the environment to C9-C14 PFCAs.” A restriction on “manufacture, use and placing on the market of C9-C14 PFCAs, their salts and related substances” is seen as “the most appropriate Union-wide measure to address the identified risks in terms of effectiveness in reducing those risks.”
The annex specifies that C9-C14 PFCAs, their salts and related substances “shall not be manufactured, or placed on the market as substances on their own,” or “be used in, or placed on the market in (a) another substances, as a constituent; (b) a mixture; (c) an article, except if the concentration in the substance, the mixture, or the article is below 25 ppb for the sum of C9-C14 PFCAs and their salts or 260 ppb for the sum of C9-C14 PFCA-related substances.”
The proposed restriction contains multiple derogations. For example, “the exemptions which apply to the use of PFOA, its salts and PFOA-related compounds . . . should also apply to C9-C14 PFCAs and related substances under the same conditions because of the manufacturing process of fluorochemicals in which both group of substances are present as impurities.” Specifically, the set restrictions “shall not apply to (a) the manufacture of a substance where this occurs as an unavoidable by-product of the manufacture of fluorochemicals with a perfluoro carbon chain equal to or shorter than 6 atoms; (b) a substance that is to be used, or is used as a transported isolated intermediate.” These exemptions may be relevant for the presence of C9-C14 PFCAs in FCMs as impurity. If and how the new restriction will affect the use of long-chain fluorotelomers in FCMs is currently unclear, particularly due to the scarcity of available data on the occurrence and levels of relevant substances.
Comments on the WTO notification are accepted until October 2, 2020. The amendment is expected to be adopted in the early 2021, will enter into force 20 days after its publication in the Official Journal of the European Union, and will become effective in 18 months after this date.
In an article published on August 12, 2020, by regulatory news provider Chemical Watch, reporter Kathryn Carlson summarized the comments given by the non-governmental organization (NGO) International Pollutants Elimination Network (IPEN), who criticized the proposed restriction’s “high concentration limits, long phase-out times and range of derogations.” IPEN holds that the action on PFAS “needs to be taken through a wider grouping approach” instead of having different pieces of legislations address individual members of the family. In the leaked draft of the EC’s chemicals strategy for sustainability, the action plan to limit PFAS to “essential uses” only, proposed by the Directorate-General for Environment, has been strongly opposed to by the Directorate-General for Internal Market, Industry, Entrepreneurship and SMEs (DG Grow) (FPF reported). The IPEN further commented that the currently proposed limits of 25 ppb for the sum of C9-C14 PFCAs and 260 ppb for the sum of C9-C14 PFCA-related substances, with limits up to 2000 ppb proposed for certain applications, are “based on current contamination limits reported by industry, rather than on health and environmental factors.” Therefore, “to make the restrictions truly effective,” the IPEN recommends “a limit of 3 ppb or less.”
European Commission (August 3, 2020). “Notification Detail. Draft Commission Regulation amending Annex XVII to Regulation (EC) No 1907/2006 of the European Parliament and of the Council as regards perfluorocarboxylic acids containing 9 to 14 carbon atoms in the chain (C9-C14 PFCAs), their salts and related substances (5 pages(s), in English; 4 page(s), in English).” Internal Market, Industry, Entrepreneurship and SMEs Reference: G/TBT/N/EU/731
Hingwo Tsang (August 11, 2020). “EU proposes to regulate C9-C14 perfluorocarboxylic acids under Annex XVII of REACH.” SafeGuardS 121/20
Kathryn Carlson (August 12, 2020). “Proposed Commission PFCA restriction ‘substantially weakens’ action on PFASs.” Chemical Watch
Andrew Turley (August 12, 2020). “Hazard index method is ‘most appropriate’ for assessing PFAS mixtures risk.” Chemical Watch
WTO (August 3, 2020). “Notification G/TBT/N/EU/731.” (pdf)
EC (2020). “COMMISSION REGULATION (EU) …/… of XXX amending Annex XVII to Regulation (EC) No 1907/2006 of the European Parliament and of the Council as regards perfluorocarboxylic acids containing 9 to 14 carbon atoms in the chain (C9-C14 PFCAs), their salts and related substances.” (pdf)
EC (2020). “ANNEX to the COMMISSION REGULATION (EU) …/… of XXX amending Annex XVII to Regulation (EC) No 1907/2006 of the European Parliament and of the Council as regards perfluorocarboxylic acids containing 9 to 14 carbon atoms in the chain (C9-C14 PFCAs), their salts and related substances.” (pdf)
Glynn, A., et al. (2012). “Perfluorinated alkyl acids in blood serum from primiparous women in Sweden: Serial sampling during pregnancy and nursing, and temporal trends 1996-2010.” Environmental Science & Technology 46: 9071-9079.
Schlummer, M., et al. (2015). “Emission of perfluoroalkyl carboxylic acids (PFCA) from heated surfaces made of polytetrafluoroethylene (PTFE) applied in food contact materials and consumer products.” Chemosphere 129: 46-53.
Yuan, G., et al. (2016). “Ubiquitous occurrence of fluorotelomer alcohols in eco-friendly paper-made food-contact materials and their implication for human exposure.” Environmental Science & Technology 50: 942-950.
EFSA (2012). “Perfluoroalkylated substances in food: occurrence and dietary exposure.” EFSA Journal 10: 2743.
Bokkers, B. G. H., et al. (2019). “Per- and polyfluoroalkyl substances (PFASs) in food contact materials.” RIVM Letter report 2018-0181 (pdf)