Document nND81wqxxv8aZxYBoJ233o0Z1

Appendices 1. (Eco)-toxicological read across on Fluoropolymers -- GSI Environmental 2023 7 2. A Critical Review of the Application ofPolymer ofLow Concern and Regulatory Criteria to Fluoropolymers -- Henry et. al., 2018 18 3. A critical review of the application ofpolymer oflow concern regulatory criteria tofluoropoiymers II -- Korzeniowski of al 2022 37 4. Critical use offluoropolymers in thefunctioning ofmodern society -- Sales et. al.,2023 67 5. Technical report on Analysis of alternatives to fluoropolymers and potential impacts related to substitution in different sectors of use -- Chemservice, 2022 75 6. Survey ofPFOS, PFOA and other perfluoroalkyl andpolyfluoroalkyl substances -- Danish EPA, 2013 163 7. Differentiation offluoropolymersfrom other polymeric PFAS -- Chemservice, 2022 359 8. Synthesis Report on Understanding Side-Chain Fluorinated Polymers and Their Life Cycle - OECD Series on Risk Management, No. 73, 2022 385 9. Pilot-Scale Fluoropolymer incineration Study-Preliminary report -- Gehrmann et. al., 2023 445 10. Summary of the PTFE studies performed with independent laboratories to investigate Persistence, Degradation, Transformation to or Release of Substances of Concern 455 11. Contamination from a leaking geomembrane--A necessary and imminent evil? -- Tippett et. al., 2023 12. Developments in fluoropolymer manufacturing technology to remove intentional use of PFAS as polymerization aids -- Ampdari et.al., 2023 463 2966629 Integrated Environmental Assessment and Management -- Volume 14, Number 3--pp. 316-334 316 Received: 26 September 2017 I Returned for Revision: 16 January 2018 I Accepted: 30 January 2018 Critical Review A Critical Review of the Application of Polymer of Low Concern and Regulatory Criteria to Fluoropolymers Barbara J Henry, *t Joseph P Carlin,t Jon A Hammerschmidt, t Robert C Buck,: L William Buxton,: Heidelore Fiedler,ff Jennifer Seed,ll and Oscar Hernandez# fWL Gore & Associates, Elkton, Maryland, USA tChemours Company, Wilmington_ Delaware, USA MTM Research Centre School of Science and Technology, Orebro University, Orebro, Sweden I/Risk Assessment Consultant, Alexandria, Virginia, USA #Bergeson & Campbell, Washington, DC, USA ABSTRACT Per- and polyfluoroalkyl substances (PFAS) are a group of fluorinated substances that are in the focus of researchers and regulators due to widespread presence in the environment and biota, including humans, of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA). Fluoropolymers, high molecular weight polymers, have unique properties that constitute a distinct class within the PFAS group. Fluoropolymers have thermal, chemical, photochemical, hydrolytic, oxidative, and biological stability. They have negligible residual monomer and oligomer content and low to no leachables. Fluoropolymers are practically insoluble in water and not subject to long-range transport. With a molecular weight well over 100000 Da, fluoropolymers cannot cross the cell membrane. Fluoropolymers are not bioavailable or bioaccumulative, as evidenced by toxicology studies on polytetrafluoroethylene (PTFE): acute and subchronic systemic toxicity, irritation, sensitization, local toxicity on implantation, cytotoxicity, in vitro and in vivo genotoxicity, hemolysis, complement activation, and thrombogenicity. Clinical studies of patients receiving permanently implanted PTFE cardiovascular medical devices demonstrate no chronic toxicity or carcinogenicity and no reproductive, developmental, or endocrine toxicity. This paper brings together fluoropolymer toxicity data, human clinical data, and physical, chemical, thermal, and biological data for review and assessment to show that fluoropolymers satisfy widely accepted assessment criteria to be considered as "polymers of low concern" (PLC). This review concludes that fluoropolymers are distinctly different from other polymeric and nonpolymeric PFAS and should be separated from them for hazard assessment or regulatory purposes. Grouping fluoropolymers with all classes of PFAS for "read across" or structure--activity relationship assessment is not scientifically appropriate. Integr Environ Assess Manag 2018;14:316-334. 2018 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC) Keywords: Fluoropolymer International reaulation Polytetrafluoroethylene Polymer of low concern PFAS INTRODUCTION The carbon-fluorine (C-F) bond is the strongest bond ketween r anA another atom instIIII.-g sukstances that contain a majority of C--F bonds with stability, inertness, and persistence (Banks et al. 1994). Per- and polyfluoroalkyl substances (PEAS) are a large group of highly fluorinated synthetic substances with diverse properties that have been used in a wide variety of industrial and consumer applications since the 1950s (Buck et al. 2011). Within the group are This article includes online-only Supplemental Data. * Address correspondence to Mwlgore.com Published 9 February 2018 on wileyonlinelibrary.comijournaliiearn. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. distinct substances with different properties: polymers and nonpolymers; solids, liquids, and gases; persistent and nonpersistent substances; highly reactive and inert substances; mobile and insoluble substances; and toxic and nontoxic chemicals. The PFAS are a large, diverse group of substances that, in some respects, challenge easy distinction for assessment and management. A clearer understanding of the origin of PFAS found in the environment and assessment of their properties is needed to be able to determine which classes of PFAS require management action. Perand polyfluoroalkyl substances must be assessed taking into account their differences in chemical, physical, thermal, and biological properties. A single, globally harmonized system for PFAS classification has not yet been defined, resulting in a lack of distinction between PFAS. As regulatory frameworks continue to evolve, such as the Regulation (EC) No 1907/2006 of the European kitegr Environ Assess Manag 2018:316-334 DOI: 10.1002/ieam.4035 2018 The Authors 2966629 Fluoropolymers PLC--Integr Environ Assess Manag 14, 2018 321 Table 2. Fluoropolymers and PLC criteria Assessment criteria' Structure Fluoropolymers PTFE ETFE FEP PFA CAS 9002-84-0 CAS 25038-71-5, 68258-85-5 CAS 25067-11-2 CAS 26655-00-5, 31784-04-0 -CF2--CF2=n -CH2--CH2n CF2-CF2-, CF2 CF2JII CF2-CF -CF2-CF F3 m CF2-CoF Polymer composition (must hove Yes C, H, Si, S, F, CI, Br, or I covalently bound to C) Molecular weight 389 0008 900000b' (Mr, > 1000 Da and oligomer content < 1%) 520 00045 000 00064 Molecular weight distribution 2.3' MW number average Mr, (Mr, and heterogeneity of MW distribution indicate if majority are >1000 or <1000 Da, which could penetrate the cell) Wt % oligomer (see Figure 2) (<5% for <1000 Da oligomers, <2% for <500 Da oligomers) Negligible Ionic character (cationic polymers associated with aquatic toxicity; polycationic with adverse human health effect) Neutral RFGsk (some highly reactive functional groups associated with adverse human health and ecotoxicology effects, e.g., acrylates, isocyanates, anhydrides, aziridines) <1 (see section Reactive functional groups and RFG ratio to MW) FGEWk (typical value) (the lower the FGEW, the more reactive the polymer and the higher the potential for health and environmental impact) >105-107 Low molecular weight leachables (MW < 1000 Da able to enter cell) <1 ppm Residual monomers (monomers have lower MW than polymers; typically more hazardous than polymers) <1 ppm Ratio of residual monomers to molecular weight (typical value) (more low MW monomer content per mole increases bioavailability and hazard potential) -10-13 to 10-15 Structural similarities to RFG of concern (increases potential risk of adverse effects) None Reference standard see also ISO 1133 (ISO 2011), ISO 12086 (ISO 2006) ASTM D 4894 (ASTM 2015a), D 4895 (ASTM 2015b) Yes 000ef 1.4-2.7f Negligible Neutral <1 (see section Reactive functional groups and RFG ratio to MW) >105-106 No active leachables by USP class VII (121 C) <50 ppb --10-13 to 10-14 None ASTM D 2116 (ASTM 2016a) Yes 241 000575 000'9 1.55-2.099 I G. 200 000450 000'h 1.7' Negligible Neutral Negligible Neutral <1 (see section Reactive functional groups and RFG ratio to M141) >105 <1 (see section Reactive functional groups and RFG ratio to MW) >10s No active leachables by USP class VI' (121 C) <50 ppb No active leachables by USP class VI' (121C) <50 ppb 10-13 - 0-1' None ASTM D 3159 (ASTM 2015c) None ASTM D 3307 (ASTM 2016b) (Continued) integr Environ Assess Manag 2018:316-334 wileyonlinelibrary.com/joumal/ieam 2018 The Authors 2966629 26 lntegr Environ Assess Manag 00, 2022-KORZENIOWSKI ET AL. finished articles involving a wide variety of materials. Edhlund who provided valuable knowledge to accomplish Therefore, collecting and dismantling for recycling might the study, and all the reviewers for providing valuable not be feasible for all products (FPG, 2021a; Hintzer & comments on this manuscript. There are no funders to re- Schwertfeger, 2014; Pro-K Fluoropolymer Group, 2018). port for this submission. a However, it should be noted that upcycling treatment is applicable to some articles containing fluoropolymers, CONFLICT OF INTEREST 5- such as pipe liners in chemical plants, as well as other plant The authors are employed by companies that commer- components such as pumps, tank liners, seals, hoses, cially manufacture fluoropolymers. SHK is an independent compensators, and many other fluoropolymer compo- fluorotechnology consultant working on behalf of AGC illIO.I002/Searn.4646 by Cochrane Germany, Wiley Online Library on [28/10/20221, See the Terms and Conditions (httprefionlinelihrary.wiley.eorniterms.anrnoonditiong) on Wiley Online Library for rule, of use; OA articles arc governed by nents and systems. These are the products for which the Chemicals Americas Inc. and principal of BeachEdge Con- high quantities of fluoropolymers are used offering sulting LLC. significant recycling potential. DATA AVAILABILITY STATEMENT SUMMARY Data gathered for this paper is presented in the paper itself This study has described the composition, uses, per- and the Supporting Information: Data file provided. Addi- formance properties, and functionalities of 14 commercially tional data are available upon request from the corresponding available fluoropolymers, including fluoroplastics and author Stephen Korzeniowski ( gmail.com). fluoroelastomers. Fluoropolymers are the preferred material of choice because of their unique combination of proper- SUPPORTING INFORMATION ties, which are not achievable from other materials or via The Supplement contains a glossary of terms as well as other functions. As a result, fluoropolymers have become a additional information on the study of fluoropolymers critical mainstay for society and are useful to modern living, properties and functionalities, polymer of low concern (PLC) as they provide vital, reliable functionality to a broad range background and criteria, references and methods for the of industrial and consumer products. Further, the study has PLC data for the study of fluoropolymers, benefits, features presented data demonstrating the subject fluoropolymers and alternatives assessment for the study of fluoropolymers, satisfy the widely accepted polymer hazard assessment cri- the differences between fluoropolymers and side-chain flu- teria to be considered PLC. The data presented demon- orinated polymers, fluoropolymer bioavailability and toxicity strate the fluoropolymers in the study are thermally, studies, fluoropolymer global market information, fluo- biologically, and chemically stable, negligibly soluble in ropolymer socioeconomic analyses and risk-management water, nonmobile, nonbioavailable, nonbioaccumulative, options analysis (RMOA). and nontoxic, and contain low levels of impurities. These results further demonstrate that the fluoropolymer class ORCID should be considered distinctly different and should not be Robert C. Buck co http://orcid.org/0000-0002-2604-8905 grouped with other PFAS for hazard assessment or regu- latory purposes. When combined with earlier work (Henry REFERENCES et al., 2018), the study demonstrates that commercial fluo- ropolymers are available that meet the criteria to be con- sidered PLC, which represent approximately 96% of the global fluoropolymer market. Lastly, emissions from fluoropolymer manufacture and disposal at end-of-use are a 3M. (2021). Up-cycling. Closing the loop. httpsiimultimedia.3m.comirmws/ media/907323O/up-cycling-fluoropolymers-brochure.pdf?fn=Up-Cyding_ Brochure_EN.pdf AGC Chemicals Company. (2021a). FEVE WMIFLONbrochure. https://www. agcchem.corn/wp-adminiadmin-ajax.php?juwpfisadmin=false&action= wpfd&task=file.download&wpfd_categoiy_id=170&wpfd_file_id=1927& product life-cycle focus. Emissions may include nonpolymer PEAS such as fluorinated PAs, unreacted monomers, oligomers, or other unintended by-products formed during manufacturing. Fluoropolymer manufacturers recently committed voluntarily to responsible manufacturing principles by continuously improving and/or developing the best preview--18(embedded=true AGC Chemicals Company. (20216). Cytop amorphous fluoropolymers. https:// www.agc-chemicals.com6p/entfluorine/productsrdetailfindex.html?pCode= JP-EN-F019 AGC Chemicals Company. (2021c). ForbluerM FlemionrM fluorinated ionexchange membranes. https://www.agc-chemicals.comilpien/fluorine/ productsicategoryiresult.html?c_id=11 available techniques in the manufacturing process, managing environmental emissions, developing R&D programs for the advancement of technologies allowing for the replacement of fluorinated PAs, and/or increasing recyclability and reusing fluoropolymers in line with the objectives of AGC Chemicals Company. (2021d). AFLAS fluoroelastomers. https:ilwww. agcchem.comfwp-adminfadmin-ajax.php?juwpfisadmin=false&action= wpfd&task=file.download&wpfd_category_id=172&wpfd_file_id=1901& preview=1&embedded=true Aleksandrov, K., Gehrmann, H. J., Hauser, M., Matzing, H., Pigeon, D., Stapf, D., & Wexler, M. (2019). Waste incineration of polytetrafluoroethylene circular economy. (FIFE) to evaluate potential formation of per- and poly-fluorinated alkyl substances (PEAS) in flue gas. Chemosphere, 226, 898-906. https:iidoi. ACKNOWLEDGMENT The authors thank GSI Environmental for assisting with this study as well as the many colleagues, including Thomas orgil 0.1016fj.chemosphere.2019.03.191 Allied Market Research (AMR). (2022). Fluoropolymers market by product type. https://www.alliedmarketresearch.com/fluoropolymers-market American Chamber of Commerce in Europe (Arncham). (2020a). Grouping of Labour, Florence Churlaud, Catherine Savary, and Betsy PFAS: Regulation by distinct PFAS classes is scientifically superior to Integr Environ Assess Manag 2022:1-30 wileyonlinelibrary.com/journalneam O 2022 The Authors 34 I Critical Use of Fluoropolymers in the Functioning of Modern Society ICRL 112023 5. Comfort Certain products that use fluoropolymers and are in direct contact with consumers are marketed for enhanced performance while this seems a disguise for better comfort. Waterproof apparel, cosmetics, ski waxes, bicycle chain lubricants would fall under that category Frequently there is a thin line separating 'comfort' and 'safety'; for example, heating systems for seats in vehicles are based on fluoropolymer insulated electric cables. It could be argued if this feature is truly necessary for the functioning of society (a question that would likely need to be answered from the perspective that the feature is already available in most cars -- hence population would need to face a downgraded in this option); but if the feature is to be maintained, efficient insulation for such cables is necessary in order to avoid fire and to prevent passengers from electrocuting. Similarly, again referring to the automotive industry, fluoropolymers are used for the manufacture of different parts of car equipment, such as door hinges and seat height adjustment bearings. These parts can be regarded as pivot points which are subject to sporadic demand while cars are running, requiring high reliability and very low friction conditions. Not providing an efficient material for this application would take car technology probably different years back and consumers would need to face squeaking and noisy driving experiences, in addition to increased maintenance, reparations and break-downs. While this property may not be necessarily linked to safety, it could be questioned whether European society is ready to accept reduced functionality in these applications which would lead to significantly reduced comfort when driving or traveling by car - or other means of transport. Where comfort is truly the only reason for use of fluoropolymers (i.e., a 'nice to have' feature), there could be room for debate if society wishes to maintain those uses or not. The most renowned example is the use of fluoropolymers as anti-stick material in frying pans. Again, for this use it could be argued if 'comfort' alone is truly the only reason for use. Frying pans with highly anti-stick coatings allow for reduced use of oil during cooking (linked to a healthier and safer life-style), reduced use of cleaning agents (less chemicals in the environment) and improved durability of the article (helping circularity objec- tives). Furthermore, uses of frying pans coated with fluoropolymer are safe, because the temperatures required for decomposition of PTFE will not be reached during normal use, and food will burn before such temperatures are reached. In addition to this, in the event that small particles of PTFE may be released due to excessive use, there is no risk for health because such particles will be eliminated by the human body without any possibility of biological interaction, due to its inertness and the fact that they cannot cross biological membranes.13 Also, those frying pans will eventually end-up in waste plants where they will be treated as metallic waste, therefore under conditions that should not result in environmental concerns. In summary, this use cannot be considered as very dispersive. In contrast to designed functional or constructive fluoropolymer parts, dispersive uses of fluoropolymers by consumers (e.g., cosmetics, ski waxes, lubricants for bicycle chains), may eventually result in some releases of fluoropolymers to the environment. Again, the key factor is that those polymers are safe due to their nature and not pose a risk to humans or the environment. Still, if the aspiration of society is to not have these materials in the environment, it should be possible to remove such applications from the market without necessarily placing limits to the relevant industrial applications where fluoropolymers are extremely valuable for society, and where they play a significant role in enhancing safety, decarbonization, circularity, innovation and progress. For example, the already existing microplastics restriction under REACH could be a good instrument to force reduction and eventually elimination of such uses. Key Sectors of Application of Fluoropolymers The true value of fluoropolymers becomes apparent when they are used in industrial applications. Concerns expressed in the PFAS restriction proposal in relation to fluoropolymers are mainly related to low 13 Barbara I Henry, Joseph P Carlin, Jon A Hammerschmidt, Robert C Buck, L William Buxton, Heidelore Fiedler, Jennifer Seed and Oscar Hernandez, 'A critical review of the application of polymer of low concern and regulatory criteria to fluoropolymers' (2022) 14 Integrated Environmental Assessment and Management 13, 316-1.1 2966629 CHEMSERVICE Regulatory Advisors Chemservice Iberia S.L. C/ Ruiz Zorrilla 2 12001 Castellon Spain Tel: Fax: milelildElfil I rchemservice-group.com www.chemservice-group.com (PFUnA). However, some whale species show relatively high levels ofperfluorooctane sulfonamide (PFOSA) and seabirds are typically characterized by high proportions of the Cu--C15 PFCAs. PFOA is generally infrequently detected and is present in low concentrations in Arctic biota. Food web studies show high bioaccumulation in the upper trophic-level animals, although the mechanism of PFC biomagnification is not understood. Spatial trend studies show some differences between populations, although there are inconsistencies between PFC trends. The majority of temporal trend studies arefrom the Northern American Arctic and Greenland. Studies show generally increa sing levels ofPFCsfrom the19705, although some studiesfrom the Canadian Arcticshow recent declines in PFOS Ievels. In contrast, ringed seals and polar bearsfrom Greenland continue to show increasing PFOS concentrations. The inconsistent temporal trends between regions may be representative ofdffferences in emissionsfrom source regions." Houde et al. (2011) notes in a review of monitoring of PFCs in aquatic biota, that the most notable observation made was the preponderance of long-chain PFCAs found in organisms, particularly from East Asia and northern latitudes. PFCs detected in livers of tuna collected from the Pacific rim were predominantly PFOS and PFUnA, whereas PFDA and perfluorododecanoate (PFDoA) were also commonly identified (please find original references in the review). The predominance of PFUnA was also observed in livers of dolphins and porpoises, fish, and water bird eggs from several sites in Asia. In addition to Asian sites, the long-chain PFCA profile was also observed in Arctic regions. High proportion of C11-C15 PFCAs were found in Arctic seabirds and PFCA concentrations in polar bear liver were composed largely of C9- Cri with much lesser amounts of PFOA, PFDoA, and perfluorotridecanoate (PFTrA). The contamination profile may suggest specific sources of emission in East Asia dominated by long-chainPFCAs followed by long-range transport via ocean and atmrtepharip pathwaye to Tsirtrtharri racrirtns of than gird-ta apprtraing to tha alithrtre Thin nvarall rth- servations made in aquatic wildlife worldwide seem to indicate that PFCA levels may surpass those of PFSAs in the future. However, this prediction also depends on trends in use and emissions (Houde et al., 2011). A recent study supported by the Nordic Council of Ministers analysed 18 PFASs in tissues of different marine mammals from the Arctic (Dam et al., 2011). PFOS was generally found in the highest concentrations. A significant decrease in PFOS was found in hooded seals (1990-2007). On the other hand, increasing trends of one or more PFASs were found in samples of ringed seals, in pilot whales, white-sided dolphins and harbour porpoises. For PFUnA, a significantly increasing trend was found for ringed seals, pilot whales and white-sided dolphins, indicating that levels of the longer-chained PFASs are still increasing. The results are in accordance with the other results reviewed by Houde et al. (2011) and mentioned above. 7 -1=5 PFUS anti glithpr innlvilimbrinated Quhatanepa nnint Cryaired.c In point sources such as wastewater treatment plants, industrial plants and landfills, significant differences in concentration levels have been observed among the different facilities. The most recent monitoring data are shown in Table 22. The available data suggests that wastewater treatment plants may be local sources of PFOS substances, as these substances were found not only in inlet water and sludge, but also in outlet water (Strand et al., 2007). By far the highest concentrations of PFOS were found in the outlet water from an industrial facility. However, it was concluded in the study that the concentrations of PFAS in the outlet water were below the critical value where a risk to aquatic oreanisms is presented. For data on effluents from landfills please see section 4.2.1. Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances 7.1.6 FFASs in groundwater PFASs are not monitored in groundwater in Denmark. A pan-European survey of the occurrence of other selected polar organic persistent pollutants in groundwater from 2011 presents data for PFOS, PFOA and PFHxS, PFHpA. The survey includes groundwater samples from Denmark and 22 other EU Member States from a total of 164 locations, but the data are not presented by country. The maximum and average concentrations of PFOS were higher than the concentration of the three other substances, whereas the median concentration is highest for PFOA. Median concentrations are presented without decimals which make the data difficult to interpret. TABLE 23 OCCURENCE OF PFOS, PFOA AND PFHXS, PFHPA IN GROUNDWATER ACROSS THE EU (LOOS ETAL., 2010) Chemical PFOS PFOA PFHxS PFHpA Limit of detection, ng/I. 0.4 0.4 0.4 0.4 Freq. of detection (%), ng/L 48.2 65.9 34.8 29.9 Max ng/L 135 39 19 21 Average ng/L Median ng/L 900 percentile 4 0 11 3 1 6 1 0 5 1 0 1 7-1-7 Environmental risk limits The National Institute for Public Health (RIVM) in the Netherlands have developed environmental risk limits for PFOS and proposed water quality standards in accordance with the Water Framework Directive (RIVM, 2010). TABLE 24 DERIVED MPC, MACEco, NC, AND SRCEco VALUES FOR PFOS (RIVM, 2010) ERL MPC g/L Freshwater 6.5 X 10 4 Surface water intended for drinking water abstraction 0.53 Marine water I 5.33c " n.a. = not applicable ng/L 0.65 530 0-53 MACO g/L c NC SRC. pg/L 6.5 A ILI ng/L I - - I l/ .1-1LAJO Pg/1930 n.a. n.a. n.a. n.a. 7.2 5.3 x 10-6 930 I 0.0053 I 7.2 Human exposure and biomonitoring Human exposure to PFASs was reviewed in the 2008 survey of fluorinated substances in impreg- nated consumer products and impregnating agents (Poulsen et al. 2008). The following review focuses on newer findings. 7.2.1 PFAS in food and dietary exposure EU In 2010, the European food safety authority EFSA issued a call for data on PFASs in food with a closing date of 31 January 2012. Thirteen countries have submitted 56,862 analytical results on 27 Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances Fromme et al. (2009) and Trudel et al. (2008) have reviewed the current knowledge of PFAS monitoring data in environmental media relevant for human exposure. In this context, PFAS concentrations in indoor and ambient air, house dust, drinking water and food were outlined. Furthermore, the papers summarized human biomonitoring data of PFAS levels in blood, breast milk, and human tissues. The estimated adult daily intake of PFOS, PFOA, IFTOH and IFOSE/FOSA for the general population is shown in Table 28 (Fromme et al., 2009). As seen from the table, dietary exposure is the dominant intake pathway for PFOS and PFOA FOSE/FOSA, responsible for 91% and 99%, respectively, of the total intake of the general adult population using mean intake data. Using high daily intake data, house dust may be a significant source of PFOA exposure. A scoring by the authors using a simple one-compartment toxicokinetic model showed that the dietary intake corresponds well with the blood plasma level of the same population. The total estimated intake of PFOS and PFOA were well below the TDI values recommended by the EFSA Scientific Panel on Contaminants in the Food Chain of 150 ng/kg body weight for PFOS and 1500 ng/kg bw per clay for PFOA. For IFTOH and IFOSE/FOSA, in the mean exposure scenario, house dust is the the main source of exposure while in the high exposure scenario the diet may be the major exposure source for I FOSE/FOSA. The study did not specifically estimate the exposure of children. According to the Fromme et al. (2009), it is obvious from biomonitoring data that the internal exposure of children is comparable to that of adults, but the exposure situation of children is not well understood, and therefore the authors do not make any statements on the risks of children's exposure to PFAS using the data available. Trudel et al. (2008) notes that children tend to experience higher total uptake doses (on a body weight basis) than teenagers and adults because of higher relative uptake via food consumption and hand-to-mouth transfer of chemical from treated carpets and ingestion of dust. Furthermore the authors conclude that besides this background exposure of the general population, a specific additional exposure may occur which causes an increased PFAS body burden. This has been observed in populations living near PFAS production facilities or in areas with environmental contamination of PFASs. The consumption of highly contaminated fish products may also cause an increase in PFAS body burdens. In accordance with the results of Fromme et al. (2009), Trudel et al. (2008) concludes that the greatest portion of the chronic exposure to PFOS and PFOA is likely to result from the intake of contaminated foods, including drinking water. Consumer products cause a minor portion of the consumer exposure to PFOS and PFOA. Of these, it is mainly impregnation sprays, treated carpets in homes, and coated food contact materials that may lead to consumer exposure to PFOS and PFOA. Haug et al. (2011) estimated individual PFC intakes from multiple exposure sources for a study group of 41 Norwegian women using measured PFC concentrations in indoor air and house dust as well as information from food frequency questionnaires and PFC concentrations in Norwegian food. Food -was generally the .u.Lajul cA.puoulc auult...c, reel cavniti.E, 6/ - 34 4% of the median toted intake for PFOA and 88-99% for PFOS using different dust ingestion rates and biotransformation factors of 'precursor' compounds. However, on an individual basis, the indoor environment accounted for up to 5o% of the total intake for several women. Significant positive associations between concentrations of PFCs in house dust and the corresponding serum concentrations underline the importance Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances 111 Human blood Poulsen et al. (2008) reviewed existing information on PFOS and PFOA in blood. As mentioned in the review, in blood the perfluorinated chemicals are mainly bound to serum proteins, especially albumin. In most studies blood serum is analysed but other studies analyse whole blood or blood plasma. When comparing such studies it is important to take into account that results will depend on what medium is analysed. The levels in serum or plasma are approximately two to three times the levels in whole blood. A summary of the PFOS and PFOA levels in serum/plasma samples across the world showed a wide range in concentration, with PFOS typically three to ten times higher than the concentration of PFOA (Figure 10). In a similar figure summarising the data on whole blood samples, the difference between PFOS and PFOA was less distinctive. The levels shown are well in accordance with an overview prepared by OECD (2002) of PFOS and PFOA levels in human blood sampled in various countries from 1998-2000. The average levels ranged from 17 to 53 ng/mL for PFOS and 3 to 17 ng/mL for PFOA (OECD, 2002, as cited by Jensen et al., 2008). Mean and median concentrations for some PFASs, such as PFOS, from North American populations appear to be slightly higher than European, Asian, and Australian populations studied (Fromme et al., 2009). Another commonly found substance that appeared to vary amongst populations was PFHxS. Concentrations reported were <0.4-40.0 mg/L for Europe, 0.1-20.9 mg/L for Asia and OO.4-712 mg/L for North America (Fromme et al., 2009). MI Pl ",,,S PFMA 60 50 40 E 30 y. 20 n n n 0 -2 II I I tiI I im I e 4.. .6cs ., e,,,.- ,P ,,ob. .0 ,,14.?",)4'" sfyl" i' 5' 0# ,,;*,,,,..\ ,9"..,..,,k 4- , ,LP k6, 4,..6 e 06 ,,.kF c,t, 4,- ,:ts .,3 c., ..6, e se ce ,, * 4" V. .,,' . ' 0 6% .,.# j` #6" 60 # \ass N'i" +c,4 sc.,1" A,.. ")" 0' 04' CP,P. i # 44,' .," V `-' As'>.1 cf., c, c g,N. " "C0` R;F\'" RibAt' \ ,65'''' AO -# Dec .4, 0 1' g g , _04' ,..# ..gb`" ,,,,,K, 4,1, i}N''' \ .\,' q's 0 4" J 4" FIGURE 10 AVERAGE CONCENTRATIONS OF PFOS AND PFOA IN HUMAN BLOOD SERUM/PLASMA FROM VARIOUS COUNTRIES (POULSEN ETAL.,2008 ) Vestergren and Cousins (2009) have reviewed a wide range of studies of PFOA in human blood sera from all over the world. The data show that the background-exposed population in the industrialized countries worldwide exhibits a narrow concentration range; arithmetic means of published studies range between 2 and 8 pg/L PFOA, with the exception of a few outlier studies. Significantly higher concentrations were found in ammonium perfluorooctanoate (APFO) production workers and elevated serum concentrations of PFOA (mean 27.4-423 Ng/L) in non-occupationally exposed populations have been reported from areas where use of contaminated soil conditioner and a fluoropolymer production site, respectively, were identified as sources of contamination. The authors conclude that food intake is the major contemporary exposure pathway for the background popula- Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances TABLE 30 STATUS OF SUBSTITUTION OF PFOS AND PFOS-RELATED SUBSTANCES FOR THE DIFFERENT APPLICATION AREAS Use area Aviation hydraulic oils Fire-fighting foams Pesticides Metal plating Electrical and electronic parts Use status for PFOSrelated substances PFOS-related compounds may still be used. The use of PFOS-related substances in new products has been phased out in most OECD countries. Stocks are still being used up. Sulfluoramid is used in some countries as an active substance and surfactant in pesticide products for termites, cockroaches and other insects. Other fluorosurfactants may be used as "inert" surfactants in other pesticide products. PFOS-compounds are still used in hard chrome plating. Cr-Ill has replaced Cr-VI in decorative chrome plating. PFOS-based chemicals are or have been used in the manufacturing of digital cameras, mobile phones, printers, scanners, satellite communication and radar systems, etc. Alternatives used Other fluorinated substances and non-fluorinated phosphate compounds other fluorMated substances and nonfluorinaed phosphate compounds could be use after considering hazards/risk characteristics C6-- fluorotelomers are used as substitutes in new products; fluorine-free alternatives are used for training exercises and possibly in other settings than offshore. Synthetic insecticides such as S-Methoprene, Pyriproxyfen, Fipronil, Imidacloprid, Chlorpyrifos, Cypermethrin, Deltamethrin, Fenitrothion, Abamectin (commercial mixture) and their mixtures are alternative active substances, sometimes used in combinalion. Alternative surfactants may exist. There are also a number of alternative nonchemical methods, mainly biological controls Some non-fluorinated alternaLives are marketed but they are not considered equally effective in hard chrome plating. A C6-fluortelomer is used as a substitute and may be effective. PFBS derivatives may also be used. Physical barriers may also apply. For most of these uses, alternatives are available or are under development. Remarks Considerable information gaps though there are several products established on the market for years. Alternatives to PFOS are widely used and easily accessible on several markets in North America, Europe and Asia (China). Costs for the alternatives are assessed as equal to PFOS with the exception of China that states that the alternative is slightly more expensive than PFOS. Some or all chemical alternatives to PFOS are easily available in South America (Argentina, Brazil) and Asia (China). These substances are mostly systemic insecticides that are in the range from highly toxic to humans and environment to less toxic to humans" and moderately or highly toxic to environment. Some of the alternatives are considered as less effective than PFOS by Brazil. Biological control agents are available in a number of countries including South America, USA, and China (Taiwan). Only Canada and China report that alternatives to PFOS are used for years with success. They are easily available on their markets. There is little or no health environmental data available for the chemical alternatives from the parties. Costs for the alternatives are slightly higher than PFOS. Considerable information gaps Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances Use area Use status for PFOSrelated substances Alternatives used Remarks Semiconductor industry *2 PFOS is still used but in lower concentrations. No substitutes with compara- ble effectiveness have been identified, and doing so may take up to 5 years, according to the industry. It should be possible to use PFBS, fluorinated polyethers or telomers. Medical devices * 2 Old video endoscopes at hospitals contain a CCD colour filter that contains a small amount of PFOS. PFOS is also used as an effective dispersant for contrast agents in radioopaque catheters. Repairing such video endo- - scopes requires a CCD colour filter containing PFOS. New CCD filters are PFOS-free. For radio-opaque ethylene tetra- fluoroethylene, PFBS can replace PFOS. Others (Cleaning agents, waxes and polishes for cars and floors) PFOS-related substances have been phased out in most OECD countries. Fluorotelomer-based substances, fluorinated polyethers, C4-perfluorinated cornpounds Note that these applications are banned. *1 The majority of table is derived from UNEP, 2012. Applications marked with *2 are derived from UNEP, 2010. 8.2 Non-fluoro or low-fluoro alternatives to long-chain PFAA sub- stances The technological best alternatives to the long-chain C8) fluorinated chemicals are most often other less hazardous fluorinated chemicals with a fluorinated alkyl chain length of 5 C6 or fluoropolymers. Most of these substances have been discussed above. The others, which are fluoroalkyl polyether, fluorinated ethers, ketones etc., will be discussed in the following parag,raphs together with some non-fluorinated alternatives, such as s- ilicone TI -Joly-mers, siloxanes, propylated aromatics, sulfosuccinates, etc. Where PFOS derivatives had very broad application areas, many of the non-fluorinated alternatives only can be used to specific applications. The following review of substitutes to long-chain polyfluorinated chemicals not already discussed in the paper is based on the "Draft Guidance document on Alternatives to perfluorooctane sulfonic acid (PFOS) and its derivatives" as drafted by Allan Astrup Jensen for the Stockholm Convention in 2010 (UNEP, 2010). Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances the full impact of the present levels in humans is available. EFSA concludes that, based on further results from toxicological evaluations, the relevance of various PFASs to human health could be better established, thus allowing for the definition of a set of priority PFASs for future monitoring. The use of analytical methods with improved sensitivity would be required to monitor such priority PFASs in order to increase the proportion of quantified results and thereby the reliability of exposure assessments. Population studies have discovered positive associations between a number of adverse effects at commonly prevalent exposures to the PFCs. More knowlegde on adverse effects at actual exposure leves and a better understanding og which substance contribute to the effects is needed. Many of the non-fluorinated alternatives are not very persistent and bioaccumulative, but are some of them are more toxic than the PFCs. However, there is a lack of public data on the properties of the non-fluorine alternatives to the PFCs, which often are protected by commercial secrecy, and because most academic research has been on the polyfluorinated chemicals. Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances EtFASAs EtFASEs EtFBSE EtFBSE EtFOSA EtFOSAA EtFOSAC EtFOSE EUSES FASAAs FASAs FASEs FC-807 FOSA Hie FTCA 170 FTOH FTS FTUCA GJIC HCB HFP il MnQ HPA ICCM MeFASA MPC KPFO Kd LC L-FABP LOAEL LOUS MACeco: monoPAPS NHANES NOAEL NOEC NOVANA MCF-7 MSWI MTBE MWWTP n:2 FTIs n:2 FTOHs NC NCP NEt4-PFOS OECD OSPAR PAFs N-ethyl perfluoroalkane sulfonamides N-Ethyl perfluoroalkane sulfonamidoethanol N-Ethyl perfluoro-butane sulfonamidoethanol N-Ethyl perfluoro-butane sulfonamidoethanol N-ethylperfluorooctane sulfonamide N-Ethyl perfluorooctane sulfonamidoacetic acid N-Ethyl perfluoro-octane sulfonamidoethyl acrylate N-Ethyl perfluorooctane sulfonamidoethanol European Union System for the Evaluation of Substances Perfluoroalkane sulfonamidoaceticacids Perfluoroalkane sulfonamides Perfluoroalkane sulfonanaidoethanols Perfluoroalkyl phosphate Perfluorooctane sulfonamide Fluorotelomer based polymer Fluorotelomer carboxylates Fluorotelomer olefin Fluorotelomer alcohols Fluorotelomer sulfonates Fluorotelomer unsaturated carboxylic acids Gap junction intercellular communication Hexachlorobenzene Hexafluoropropylene ma+hylrlicilnvana Health Protection Agency International Conference on Chemicals Management N-methyl perfluoroalkane sulfonamides Maximum permissible concentration PFOA potassium salt Soil/water distribution coefficient Lethal effect concentration Liver-fatty acid binding protein Lowest observable adverse effect level List of Undesirable Substances Maximum Acceptable Concentration for ecosystems polyfluoroalkyl-mono phosphates National Health and Nutrition Examination Survey (in the USA) No observable adverse effect level No observable effect concentration Danish national surveillance programme for the aquatic environment Michigan Cancer Foundation -- 7 breast cancer cell line Municipal solid waste incinerator Methyl tertiary butyl ether Municipal waste water treatment plant n:2 Fluorotelomer iodides n:2 Fluorotelomer alcohols Negligible Concentration New Chemicals Program Tetraethylammonium perfluorooctane sulfonate Organisation for Economic Co-operation and Development Convention for the Protection of the Marine Environment of the North-East Atlantic Perfluoroalkanoyl fluorides Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances PTFE PVDF PVF REACH RME ROS SAICM SRCeco SFAenes SFAs SVHC TDI TDS TFE TSCA UNEP UNIDO USEPA vPvB w.w. WWTP Polytetrafluoroethylene Polyvinylidene fluoride Polyvinylfluoride Registration, Evaluation, Authorisation and Restriction of Chemicals ((Regulation (EC) No 1907/2006) Reasonable Maximum Exposure Reactive oxygen species Strategic Approach to International Chemicals Management Serious Risk Concentration for ecosystems Semifluorinated n-alkenes Semifluorinated n-alkanes Substances of Very High Concern Tolerable daily intake Testicular dysgenesis syndrome Copolymers of tetrafluoroethylene Toxic Substances Control Act The United Nations Environment Programme The United Nations Industrial Development Organization United States Environmental Protection Agency Very persistent and very bioaccumulative Wet weight Waste water treatment plant Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances Dupont (2002). DuPont"' Krytox Performance Lubricants. Product Overview. E.I, du Pont de Nemours and Company. DVFA (2012a). Fluorerede forbindelser i animalske produkter, jf. henstilling 2010/161 [Fluorinated compounds in animal products, according to recommendation 2010/161]. Danish Veterinary and Food Administration. (In Danish) DVFA (2012b). Fluorerede forbindelser i vilde fisk -- 2011 jf. henstilling 2010/161 [Fluorinated compounds in wild fish, according to recommendation 2010/161]. Danish Veterinary and Food Administration. DVFA (2012c). Screening for fluorerede stoffer i fodevarekontaktmaterialer af pap og papir [Screening of fluorinated compounds in food stuff contact materials consisting of cardboard and paper]. Danish Veterinary and Food Administration. (In Danish) DVFA (2012d). Migration af fluorerede stoffer fra fodevarekontaktmaterialer af pap og papir [Migration of fluorinated substances from food contact materials of paper and cardboard]. Danish Veterinary and Food Administration. (In Danish) EC (2012). Draft Commission Staff Working Document presenting a draft of the second European Union Implementation Plan (UIP) on Persistent Organic Pollutants (POPs) in the context of the consultation on the Community Implementation Plan of the Stockholm Convention on Persistent Organic Pollutants. The consultation was closed on 10 October 2012, Brussels. ECHA (2012a). Community Rolling Action Plan (CoRAP). European Chemical Agency, Helsinki. ECHA (2012b). Pre-registered substances. European Chemical Agency, Helsinki. Available online at: http://echa.europa.eu/web/guest/information-on-chemicals/pre-registered-substances (Accessed 08/2012). ECHA (2012c). Guidance for monomers and polymers. Version 2.0 April 2012. European Chemical Agency, Helsinki. ECHA (2012d). Annex XV -- Identification of henicosafluoroundecanoic acid as SVHC. Submitted by BAuA, Federal Institute for Occupational Safety and Health, Germany. ECHA (2012e). Annex XV -- Identification of tricosafluorododecanoic acid as SVHC. Submitted by BAuA, Federal Institute for Occupational Safety and Health, Germany. ECHA (2012O. Annex XV -- Identification of pentacosafluorotridecanoic acid as SVHC. Submitted by BAuA, Federal Institute for Occupational Safety and Health, Germany. ECHA (2012g). Annex XV -- Identification of heptacosafluorotetradecanoic acid as SVHC. Submitted by BAuA, Federal Institute for Occupational Safety and Health, Germany. ECHA (2012h). Registered substances. Information available in public part of registrations at ECHA's website at: http://echa.europa.eu/web/guest/information-on-chemicals/registeredsubstances. EFSA (2008). Opinion of the Scientific Panel on Contaminants in the Food chain on Perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and their salts. EFSA Journal 653:1-131. European Food Safety Authority, Parma. EFSA (2011). Results of the monitoring of perfluoroalkylated substances in food in the period 2000 - 2009. EFSA Journal 2011; 9(2):2016. European Food Safety Authority, Parma. Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances Luebker, D.J., Case, M.T., York, R.G., Moore, J.A., Hansen, K.J., Butenhoff, J.L. (2005). Twogeneration reproduction and cross-foster studies of perfluorooctanesulfonate (PFOS) in rats. Toxicology, 215:126-148. Luo, Z., Shi, X., Hu, Q., Zhao, B., Huang, M. (2012). Structural evidence of perfluorooctane sulfonate transport by human serum albumin. Chemical Research in Toxicology, 25 (5): 990-992. Maisonet, M., Terrell, M.L., McGeehin, M.A., Christensen, K.Y., Holmes, A., Calafat, A.M., Marcus, M. (2012). Maternal concentrations of polyfluoroalkyl compounds during pregnancy and fetal and postnatal growth in british girls. Environ Health Perspect. 120(1O1432-1437. Maras, M., Vanparys, C., Muylle, F., Robbens, J., Berger, U., Barber, J.L., Blust, R., De Coen, W. (2006). Estrogen-like properties of fluorotelomer alcohols as revealed by MCF-7 breast cancer cell proliferation. Environ Health Perspec, 114: 100-105. Martin, J.W., Mabury, SA., O'Brien, P.J. (2005). Metabolic products and pathways of tluorotelomer alcohols in isolated rat hepatocytes. Chern Biol Interact, 155:165-180. Martin, J.W., Asher, B.J., Beesoon, S., Benskin, J,P., Ross, M,S. (2010). PFOS or PreFOS? Are perfluorooctane sulfonate precursors (PreFOS) important determinants of human and environmental perfluorooctane sulfonate (PFOS) exposure? J. Environ. Monit; 12, 1979-2 004. Melzer, D., Rice, N., Depledge, M.H., Henley, W.E., Galloway, T.S. (2010). Association between serum perfluorooctanoic acid (PFOA) and thyroid disease in the U.S. National Health and Nutrition Examination Survey. Environ Health Perspect 118:686-692. Mondal, D., Lopez-Espinosa, M-J., Armstrong, B., Stein, C.R., Fletcher, T. (2012). Relationships of perfluorooctanoate and perfluorooctane sulfonate serum concentrations between mother-child pairs in a population with perfluorooctanoate exposure from drinking water. Environ Health Perspect, 120:752-757. Needham, L.L., Grandjean, P., Heinzow, B., Jorgensen, P.J., Nielsen, F., Patterson, D.G. Jr. (2011). Partition of environmental chemicals between maternal and fetal blood and tissues. Environ Sci Technol 45(3):1121-1126. Nelson, J.W., Fraser, A.J., Hatch, E.E., Scammell, M.K., Webster, T.F. (2010a). Fast food consumption and other dietary measures predict PFC serum concentrations in the U.S. population. Reproductive Toxicology. 33 (4): 616. Nelson, J.W., Hatch, E.E., Webster, T.F. (2010b). Exposure to polyfluoroalkyl chemicals and cholesterol, body weight, and insulin resistance in the general US population. Environ Health Perspect, 118:197-202. NICHAS (2005). Potassium perfluorbutane sulphonate. Existing Chemical Hazard Assessment Report. 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Biol Reprod, 84:1016-1023. Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances Annex 2: OECD 2007 substance groups Grouping of PFCs used in the OECD surveys (OECD, 2007). Annex 1, 2 and 3 include substances that may be potentially degrade to PFOS, other PFASs and PFOA, respectively. Annex 1 Annex 2 Annex 3 Annex 4 Fluorinated chemicals that potentially degrade to PFCA Perfluorooctane sulfonate (PFOS) and related compounds. Perfluoroalkyl sulfonate (PFAS) and related compounds (other than the substances included in Annex 1) List of perfluorooctanoic acid (PFOA) and related compounds. P1: Perfluoro alcohol compounds P2: Perfluoro amine compounds P3: Perfluoro carboxylic compounds (some overlap with annex 3) P4: Perfluoro ester compounds P5: Perfluoro ether compounds P6: Perfluoro iodide compounds P7: Perfluoro phosphonic/phosphinic compounds P8: Partial perfluoro & miscellaneous perfluoro compounds Ft: Fluoro alcohol compounds F2: Fluoro ammonium compounds F3: Fluoro amine compounds F4: Fluoro carboxylic compounds F5: Fluoro ester compounds F6: Fluoro ether compounds F7: Fluoro iodide compounds F8: Fluoro phosphate compounds Fg: Fluoro sulfate compounds Fio: Fluoroalkvl silicate compounds Fit: Fluoro sulfonate/sulfonamide/stilfonyl compounds F12: Fluoro siloxane/silicone/silane coin pound,, F13: Fluoro thiols compounds F14: Fluoro thioether compounds F15: Fluoro thioester compounds F16: Fluoro urethane compounds F17: Partial fluoro & miscellaneous fluoro compounds Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances CAS No. Substance name OECD class Chain length 24448-09-7 1-Octanesulfonamide,1,1,2,2,3,3,4,4,5,5,6,6, 7,7,8,8,8- PFOS 8 heptadecafluoro-N- (2-hydroxyethyl)-N-methyl- (TSCA, DSL, AICS) (MeFOSE) 65530-70-3 Poly(difluoromethylene), a, a'-[phosphinicobis(oxy- Fluoro phos- n 2,1-ethanediy1)]bis[w-fluoro-, ammonium salt phate (F8) (TSCA, DSL) 68298-62-4 2-Propenoic acid, 2- [butyl [(heptadecafluorooc- PFOS, PFAS 7-8 tyl)sulfonyl]amino]ethyl ester, telomer with 2- [butyl[(pentadecafluoroheptyl) sulfonyllamino]ethyl 2-propenoate, methyloxirane polymer with oxirane di- 2-propenoate, methyloxirane polymer with oxirane mono-2-propenoate and i-octanethiol (TSCA, DSL, AICS) 65530-74-7 Ethanol, 2,2'-iminobis-, compd. With a -fluoro-w-[2- Fluoro phos- n (phosphonooxy)ethyl] poly(difluoromethylene) (1:1) phate (F8) (TSCA, DSL) 65530-69-0 Poly(difluoromethylene), a -[2-[(2carboxyethyl)thio]ethyl]- w-fluoro-, lithium salt (TSCA, DSL, AICS) Fluoro thi- n oether (F14) 68391-08-2 Alcohols, C8-14, g-w-perfluoro (TSCA, DSL, EINECS, AICS) Fluoro alco- 6-12 hols (F1) 68391-08-2 Alcohols, C8-14, y-w-perfluoro Fluoro alco- 8-14 hols (Fi) 65530-72-5 Poly(difluoromethylene), a-fluoro-u-[2- Fluoro phos- n (phosphonooxy)ethyl]-, diammonium salt (TSCA,DSL) phate 2991-51-7 Glycine, N-ethyl-N-[(heptadecafluorooctyl)sulfonyll- PFOS 8 potassium salt (TS(A TOT ENCS AICS) 65530-71-4 Poly(difluoromethylene), a -fluoro-w-[2(phosphonooxy)ethyl]-, monoammonium salt (TSCA, DSL) Fluoro phos- n phate (F8) 6J530-74-7 Ethanol, 2,2'-iminobis-, compd. With a -fluoro-co-[2- Fluoro phos- n (phosphonooxy)ethyl] poly(difluoromethylene) (1:1) phate (F8) (TSCA, DSL) 54950- 05-9 Butanedioic acid, sulfo-, 1,4- Fluoro ester 6 bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) ester, (F5) sodium salt (TSCA, NDSL, AICS) 65530-63-4 Ethanol, 2,2'-iminobis-, compd. With a -fluoro-61[2- Fluoro phos- n (phosphonooxy)ethyl] poly (difluoromethylene) (2:1) phate (F8) (TSCA, DSL) 65530-64-5 Ethanol, 2,2'-iminobis-, compd. With a, a'[phosphinicobis(oxy-2,1-ethanediyl)] bis[wfluoropoly(difluoromethylene)] (1:1) (TSCA, DSL) Fluoro phos- n phate (F8) 65530-63-4 Ethanol, 2,2'-iminobis-, compd. With a -fluoro-6)-[2- Fluoro phos- n (phosphonooxy)ethyl] poly (difluoromethylene) (2:1) phate (F8) (TSCA, DSL) Total amount in tonnes 2006 2012 > 1 0.4 Number of preparations 21 < 1 0.3 19 < 0.1 0.03 32 < at 0.003 8 < 0.1 0.1 17 < 0.1 0.02 8 n.i. 0.02 8 < 1 0.01 19 < 0.1 0.01 11 < 0.1 0.004 18 < 0.1 0.003 8 < 0.1 0.003 11 < 0.1 0.001 7 < 0.1 0.001 7 < 0.1 0.001 7 Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances Ili  to promote shared responsibility and cooperative efforts among Parties in the international trade of certain hazardous chemicals in order to protect human health and the environment from potential harm; to contribute to the environmentally sound use of those hazardous chemicals, by facilitating information exchange about their characteristics, by providing for a national decision-making process on their import and export and by disseminating these decisions to Parties. The Convention creates legally binding obligations for the implementation of the Prior Informed Consent (PIC) procedure. It built on the voluntary PIC procedure, initiated by UNEP and FAO in 1989 and ceased on 24 February 2006. The Convention covers pesticides and industrial chemicals that have been banned or severely restricted for health or environmental reasons by Parties and which have been notified by Parties for inclusion in the PIC procedure. One notification from each of two specified regions triggers consideration of addition of a chemical to Annex III of the Convention. Severely hazardous pesticide formulations that present a risk under conditions of use in developing countries or countries with economies in transition may also be proposed for inclusion in Annex III. Basel Convention The Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and their Disposal was adopted on 22 March 1989 by the Conference of Plenipotentiaries in Basel, Switzerland, in response to a public outcry following the discovery, in the 1980s, in Africa and other parts of the developing world of deposits of toxic wastes imported from abroad. Tha rivararrhing nhiartiva of tha Racal rrtnyantirm is to prntarthiiman haalth and tha anvirrtprriant against the adverse effects of hazardous wastes. Its scope of application covers a wide range of wastes defined as "hazardous wastes" based on their origin and/or composition and their characteristics, as well as two types of wastes defined as "other wastes" - household waste and incinerator ash. The provisions of the Convention center around the following principal aims: the reduction of hazardous waste generation and the promotion of environmentally sound management of hazardous wastes, wherever the place of disposal; the restriction of transboundary movements of hazardous wastes except where it is perceived to be in accordance with the principles of environmentally sound management; and a regulatory system applying to cases where transboundary movements are permissible. Eco-labels Eco-label schemes are voluntary schemes where industry can apply for the right to use the eco-label on their products if these fulfil the ecolabelling criteria for that type of product. An EU scheme (the flower) and various national/regional schemes exist. In this project we have focused on the three most common schemes encountered on Danish products. EU flower The EU ecolabelling Regulation lays out the general rules and conditions for the EU ecolabel; the flower. Criteria for new product groups are gradually added to the scheme via 'decisions'; e.g. the Commission Decision of 21 June 2007 establishing the ecological criteria for the award of the Community eco-label to soaps, shampoos and hair conditioners. Nordic Swan The Nordic Swan is a cooperation between Denmark, Iceland, Norway, Sweden and Finland. The Nordic Ecolabelling Board consists of members from each national Ecolabelling Board and decides on Nordic criteria requirements for products and services. In Denmark, the practical implementation of the rules, applications and approval process related to the EU flower and Nordic Swan is Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances 2966629 CHEMSERVICE 6. References Banerjee S., Tawade B.V., Ladmiral V., Dupuy L.X., MacDonal M.P., and Ameduri B. Poly(fluoroacrylate)s with tunable surface hydrophobicity via radical copolymerization of 2,2,2-trifluoroethyl a-fluoroacrylate and 2-(trifluoromethyl)acrylic acid. Polymer Chemistry, 2017, 8, 1978. Buck R.C., Korzeniowski S.H., Laganis E., and Adamsky F. Identification and classification of commercially relevant per- and poly-fluoroalkyl substances (PFAS). Integrated Environmental Assessment and Management. Volume 17, Number, pp. 1045-1055. 2021. Buck R.C., Franklin J., Berger U., Conder J.M., Cousins I.T., de Voogt P., Jensen A.A., Kannan K., Mabury S.A., and van Leeuwenkk S.PJ. Perfluoroalkyl and polyfluoroalkyl substances in the environment: terminology, classification, and origins. Integrated Environmental Assessment and Management. Volume 7, Number 4, pp. COM, 2020. Scientific and technical support for the development of criteria to identify and group polymers for Registration/Evaluation under REACH and their impact assessment. European Commission. June 2020. Danish EPA, 2013. Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances. The Danish Environment Protection Agency. Part of the LOUS review, Environmental Project No. 1475, 2013. Dhanumalayan E., Joshi G.M. Performance properties and applications of polytetrafluoroethylene (PTFE) - a review. Advanced Composites and Hybrid Materials. 2018. Fiedler H., Kennedy T., and Henry B.J. A critical review of a recommended analytical and classification approach for organic fluorinated compounds with an emphasis on per- and polyfluoroalkyl substances. Integrated Environmental Assessment and Management. Volume 17, Number 2, pp. FPr: 7n77 Flunrc,pnlymars vc cirla chain fliinrirptori pnlyrnors Fbirirripnimpfs prnrbict Group. Plastics Europe. Available at: https://fluoropolymers.plasticseurope.org/application/files/353.6/393.3/3.778/Fluorpolymers vs. side chain fl uorinated polymers final.pdf. Last access: May 2022. FPG, 2017. Understanding FluoroTechnology. Fluoropolymers Product Group. PlasticsEurope. 2017. Gluge J., Scheringer M., Cousins I.T., DeWitt J.C., Goldenman G., Herzke D., Lohmann R., Carla A., Ng C., Trieri X., and Wangj Z. An overview of the uses ot per- and polyfluoroalkyl substances (PEAS). Environmental Science: Processes & Impacts, 2020, 22, 2345. Henry B.J., Carlin J.P., Hammerschmidt J.A., Buck R.C., Buxton L.W., Fiedler H., Seed J., and Hernandez O. A Critical Review of the Application of Polymer of Low Concern and Regulatory CS I 12 2966629 CHEMSERVICE Criteria to Fluoropolymers. Integrated Environmental Assessment and Management. Volume 14, Number 3, pp. Honda K., Morita M., Otsuka H., and Takahara A. Molecular aggregation structure and surface properties of poly(fluoroalkyl acrylate) thin films. Macromolecules 2005, 38, 5699-5705. Huskey, 2005. Applications and benefits of perfluoropolyether (PFPE) lubricants. HUSK-ITT Corporation 7005. ITRC, 2020. Naming Conventions and Physical and Chemical Properties of Per- and Polyfluoroalkyl Substances (PEAS). Interstate Technology Regulatory Council (ITRC). 2020. IUPAC, 2022. What are polymers? International Union of Pure and Applied Chemistry. Available at: https://iupac.org/polymer-edu/what-are-polymers/. Last access: May 2022. Jensen W.B. The origin of the polymer concept. Journal of Chemical Education. 2008. Jones W.R. Properties of perfluoropolyethers for space applications. NASA Technical Memorandum 106616. National Aeronautics and Space Administration. 1994. Korzeniowski S.H., Buck R.C., Newkold R.M., El kassmi A., Laganis E., Matsuoka Y., Dinelli B., Beauchet S., Adan-isky F., Vv'eilandt K., Soni V.K., napuut D., Gunasekar P., Malvasi Brinati G., and Musio S. A. Critical Review of the Application of Polymer of Low Concern Regulatory Criteria to Fluoropolymers II: Fluoroplastics and Fluoroelastomers. Integrated Environmental Assessment and Management. 2022. Lee J., Chun S.W., Kang H.J., and Talke F.E. The effect of UV stabilizer on the photo degradation of perfluoropolyether lubricants used in hard disk. Tribology Letters. 28. NIOSH, 2022. The National Institute for Occupational Safety and Health (NIOSH). Per- and polyfluoroalkyl substances (PEAS). Available at: https://www.cdc.gov/niosh/topics/pfas/default.html. Last access: May 2022. OECD, 2018. Toward a new comprehensive global database of per- and polyfluoroalkyl substances (PFASs). Series on Risk Management No. 39. Organisation for Economic Cooperation and Development. 2018. OECD, 2009. Data analysis of the identification of correlations between polymer characteristics and potential for health or ecotoxicological concern. Available at: http://www.oecd.orgichemicalsafetvirisk-assessment/42081261.0df. Last access: May 2022. Wahlstr0m M., Pohjalainen E., Yli-Rantala E., Behringer D., Herzke D., Mudge S.M., Beekman M., de Blaeij A., Devilee J., Gabbert S., van Kuppevelt M., Zare Jeddi M., Gabrielsen P., and Trier X. Fluorinated polymers in a low carbon, circular and toxic-free economy. Technical report. Eionet Report. European Topic Centre Waste and Materials in a Green Economy. European Environment Agency. 2021. CS I 13 2966629 CHEMSERVICE CHEMSERVICE Regulatory Advisors Chemservice Iberia S.L. C/ Ruiz Zorrilla 2 12001 Castellon Spain Tel: Fax: irchemservice-group.com www.chemservice-group.com 2966629 Please cite this publication as: OECD (2022), Synthesis Report on Understanding Side-Chain Fluorinated Polymers and Their Life Cycle, OECD Series on Risk Management, No. 73, Environment, Health and Safety, Environment Directorate, OECD. re) Dhntn rrndife ernicr ArtFish/qhutt,=rQtr,cki-r,rn OECD 2022 imp Applications for permission to reproduce or translate all or part of this material should be made to: Head of Publications Service, @oecd.org, OECD, 2 rue Andre-Pascal, 75775 Paris Cedex 16, France 18 I Developments in Fluoropolymer Manufacturing Technology ICRL 1 12023 2966629 Developments in Fluoropolymer Manufacturing Technology to Remove Intentional Use of PFAS as Polymerization Aids Bruno Ameduri, Jaime Sales and Michael Schlipf* Fluoropolymers are heavily impacted by the restriction proposal on per- and polyfluoroalkyl substances (PFAS) that has been recently published under the EU REACH Regulation.' While matching the definition ofPEAS due to their chemical composition and structure,fluoropolymers are significantly differentfrom other substances in the PFASfamily. The only substantial reason for concern associated to fluoropolymers is the use of non-polymeric PFAS as polymerization aids during the manufacturing process. In the past, environmental pollution caused by PFOA and PFOS, which are prominent non-polymer substances in the PFASfamily, has attracted regulatory attention. PFOS has been restricted and PFOA has been banned under the EURegulation on Persistent Organic Pollutants. This article highlights the progress that industry has made over the last years in relation to control of PFAS emissions due to their use influoropolymer production. Such a progress is based on the improvement ofabatement techniques, but more importantly, on the removal of PFAS polymerization aids, introducing alternative technologies that do not require using such chemicals. It is expected that most of thefluoropolymer production will be developed completelyfreefrom PFAS polymerization aids in a relatively short timeframe. Thus, it appears reasonable to claim thatfluoropolymers that are manufactured without the use of PFAS polymerization aids should be exemptedfrom any regulatory initiative, and that their uses should be allowed without any unjustified restriction. I. Introduction The PFAS family of chemicals is currently under strong regulatory scrutiny globally. Some of the substances covered by this group are known for being highly harmful to the environment and human health, due to their persistency, bioaccumulation/mobility and other toxic effects. However, the broad definition that is frequently used to describe PFAS, which was not originally introduced to be used for regulatory purposes2, results in a very large number of substances covered jointly in this family of chemicals, more than 4,700 according to the OECD3 as being present on the global market. There have been significant efforts to group and classify the different substances that can be regarded as meeting the definition of PFAS (Figure 1). One such group is that of fluoropolymers.4 Bruno Ameduri, Senior Researcher at ICGM, University of Montpellier, CNRS, ENSCM, Montpellier, France; Jaime Sales, Managing Director at Chemservice Iberia, Castellon, Spain; Michael Schlipf, Chairman of the Fluoropolymer group at pro-K industrial association for semi-finished and consumer products made of plastic, Frankfurt am Main, Germany. For Correspondence: <Olichemservice-group.com>. 1 ECHA, 'Registry of restriction intentions until outcome - Per- and polyfluoroalkyl substances (PEAS)' (2023). 2 J K Anderson, R W Brecher, I T Cousins, J DeWitt, H Fiedler, K Kannan, C R Kirman, J Lipscomb, B Priestly, R Schoeny, J Seed, M Verner, 5 M Hays, 'Grouping of PFAS for human health risk assessment: Findings from an independent panel of experts' (2022) Regulatory Toxicology and Phamacology, 134. 3 OECD, 'Toward a new comprehensive global database of per- and polyfluoroalkyl substances (PFASs)' (2018) Series on Risk Management No. 39. Organisation for Economic Co-operation and Development. 4 Bruno Ameduri 'Huoropnlyrners: A special class of per- and polfluoroyalkyl substances (PFASs) essential for our daily life' (2023) Journal of Fluorine Chemistry 267, 110117. 20 I Developments in Fluoropolymer Manufacturing Technology ICRL 112023 Aqueous emulsions are required to produce high performance grades of some fluoropolymers.13 Surfactants are highly soluble in water, but the final fluoropolymer substances are not; hence after separation, the residual water contains amounts of dissolved surfactant, which may lead to PFAS emissions when FPAs are used.t4 Another consequence of the use of these surfactants is that sometimes the final fluoropolymer product may carry residuals of such non-polymeric PFAS, which can be also emitted to the environment during the life cycle of fluoropolymers. Again, in this case there is an indirect pollution associated to fluoropolymers, not related to the intrinsic specific properties of these substances. As a final step in the life cycle of fluoropolymers, disposal and waste treatment has been frequently flagged as a reason for concern of these products. However, recent studies have demonstrated that the waste generation of fluoropolymers is insignificant compared to that of other plastics,15 and that the most common waste treatment technique for fluoropolymers - incineration - will not result in any PFAS species of concern.' In addition to this, fluoropolymers do not degrade during normal use or environmental conditions17 and do not pose any significant risk if they are landfilled.18 In summary, it can be established that the only real source of concern for human health or the environment related to fluoropolymers is the use of PFAS as polymerization aids in the manufacture of these polymers of low concern. Providing efficient solutions that would completely neutralize such concerns would result in completely safe manufacture, use and disposal of fluoropolymers. III. How to Avoid PFAS Emissions (Polymerization Aids) from the Fluoropolymer Value Chain? For many years, industry has placed significant efforts to reduce emissions of PFAS from the manufacturing process of fluoropolymers. In order to achieve this goal, there are basically two options available: i. To improve the abatement techniques and recov- ery of PFAS surfactants from the manufacture of fluoropolymers. 2. To develop alternative processes that do not require the use of such PFAS polymerization aids for the production of fluoropolymers. In the case of item i above, significant improvements have occurred over the last years that have allowed for reduction of 99% of emissions of fluorinated surfactants since the 199os.19 More recent research brings that value as high as 99.99%.20 Extensive literature exists in relation to control and treatment of emitted PFAS from industrial processes.21 The strategies of containment involve the recovery, removal, purification, sorption techniques, microbial degradability and recyclability of the polymerization aids 13 Oleg N. Primachenko, Alexey S. Odinoko, Elena A. Marinenko, Yuri V. Kulvelis, Valerij G. Barabanov and Svetlana V. Kononova, 'Influence of suIfonyl fluoride monomers on the mechanism of emulsion copolymerization with the preparation of protonconducting membrane precursors' (2021) Journal of Fluorine Chemistry 244, 109736. 14 Ebnesajjad, Fluoroplastics, Volume 1: Non-Melt Processible Flooropolymers - The Definitive User's Guide and Data Book (Elsevier, 2014). 15 Conversio, 'Fluoropolymer waste in Europe 2020-- End-of-life (EOL) analysis of fluoropolymer applications, products and associated waste streams' (2022). 16 Krasimir Aleksandrov, Hans-Joachim Gehrmann, Manuela Hauser, Hartmut Matzing, Daniel Pigeon, Dieter Stapf and Manuela Wexler, Waste incineration of Polytetrafluoroethylene (PTFE) to evaluate potential formation of per- and Poly-Fluorinated Alkyl Substances (PEAS) in flue gas' (2019) 226 Chemosphere; RIVM, 'Per- and polyfluorinated substances in waste incinerator flue gases. Rijksinstituut your Volksgezondheid en Milieu' (2021). 17 Danish EPA, 'Survey of PFOS, PFOA and other perfluoroalkyl and polyfluoroalkyl substances The Danish Environment Protection Agency' (2013) LOUS Review, Environmental Project No. 1475, 2013. 18 Stephen H. Korzeniowski, Robert C. Suck, Robin M. Newkold, Ahmed El kassmi, Evan Laganis, Yasuhiko Matsuoka, Bertrand Dinelli, Severine Beauchet, Frank Adamsky, Karl Weilandt, Vijay Kumar Soni, Deepak Kapoor, Priyanga Gunasekar, Marco Malvasi, Giulio Brinati and Stefana Musio, 'A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers' (2022) Integptorl Fnvirnnrmania I Ascasamnnt and Management 19 Daikin Chemicals, 'Measures concerning environment emission of PFAS' (2022) <https//www.daikinchemicals.com/company/ sustainahility/pfas.html> accessed 1 May 2023. Chemours, 'Our Commitment to Responsible Chemistry' <https://www.chemours .com/en/corporate-responsibility/sustainability-safety/our -commitment-to-pfas-stewardship> accessed 1 May 2023. 20 Rebecca DiStefano, Tony Feliciano, Richard A. Mimna, Adam M. Redding and John Matthis, 'Thermal destruction of PFAS during full-scale reactivation of PFAS-laden granular activated carbon' (2022) Remediation 32, 231-238. 21 ITRC, 'PEAS Technical and Regulatory Guidance Document and Fact Sheets: 12. Treatment Technologies' (2022) Interstate Technology and Regulatory Council; Jinxia Liu and Sandra Mejia Avendano 'Microbial degradation of polyfluoroalkyl chemicals in the environment: A review' (2013) Environment International 61, 98-110