Risk Management Evaluation Endosulfan

Information on alternatives (products and processes)

Overview of alternatives

127.Due to concerns about the impact of long-chain perfluoroalkyl acids (PFAAs) on humans and the environment these PFAAs and their precursors are being substituted in many applications by other substances, including fluorinated alternatives which are structurally similar to the substances they replace. These fluorinated alternatives comprise particularly short-chain PFAAs and functionalized perfluoropolyethers (PFPEs), in particular per- and polyfluoroether carboxylic acids and (PFECAs) and per- and polyfluoroethersulfonic acids (PFESAs) having an acidic functional group attached to a per- or polyfluoroether chain instead of a perfluoroalkyl chain (Wang et al., 2015). An overview of some known fluorinated and non-fluorinated alternatives for different industry branches is given in the reference documents (ECHA, 2015a, Table C.1-1; see UNEP/POPS/POPRC.13/INF/6; Section 3 and UNEP, 2017).

Sector specific aspects

128.The following paragraphs discuss sector specific aspects related to alternatives. Nevertheless, several aspects related in particular to risks of the alternatives (e.g. short-chain fluorinated substances) cannot be assigned to a single sector, but apply to all of those sectors where the respective alternatives are relevant.

A. Manufacture of fluoropolymers

Functionalized perfluoropolyethers (PFPEs)

129.According to FluoroCouncil, there are various alternative polymerization processing aids (PPA) used for replacing PFOA in the manufacture of fluoropolymers (FluoroCouncil, 2016a).

130.Fluoropolymer producers used ammonium or sodium perfluorooctanoate (APFO and NaPFO) as processing aids in the (emulsion) polymerization of polytetrafluoroethylene, perfluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer and certain fluoroelastomers. In addition, ammonium perfluorononanoate (APFN) was applied in the emulsion polymerization of polyvinylidene fluoride (Prevedouros et al., 2006). Most producers have developed their own alternatives. Commercialized fluorinated alternatives are functionalized PFPEs including amongst others ADONA from 3M/Dyneon (CF₃OCF₂CF₂CF₂OCHFCF₂COO-NH₄+; CAS No: 958445-44-8; Gordon, 2011), GenX from DuPont or C₃ Dimer salt²¹(CF₃CF₂CF₂OCF(CF₃)COO-NH₄+; CAS No: 62037-80-3; Du Pont, 2010), cyclic or polymeric functionalized PFPEs from Solvay (Marchionni et al., 2010; Pieri et al., 2011; Spada and Kent, 2011) as well as EEA-NH₄from Asahi (C₂F₅OC₂F₄OCF₂COO-NH₄+; CAS No: 908020-52-0; EFSA, 2011a). Additional information on alternatives to PFOA in fluoropolymer production with emphasis on the manufacture of fluoropolymers in China and fluorinated emulsifier-free aqueous emulsion polymerization processes is compiled in section V of FOEN, 2017.

131.Three PFOA-alternatives with ether moieties (GenX,ADONA and EEA-NH₄) that are generally shorter and/or less fluorinated were assessed in the EU restriction process (ECHA, 2015a, section C3). C₃ Dimer salt, ADONA and EEA-NH₄ are applied as alternatives for the use of PFOA as polymerization processing agent where it is applied as emulsifying agent enabling reactants from the aqueous phase and reactants from the hydrophobic phase to get into contact in an emulsion and react with each other (ECHA, 2015a). According to ECHA most of the stakeholders stated that there are no technical differences between fluoropolymers produced with the alternatives and fluoropolymers produced with PFOA (or stakeholders do not know whether there are any differences) (ECHA, 2015a). Fluoropolymer manufacturers stated during the EU public consultation that the production costs varied from none to 20% increase when applying the alternatives (ECHA, 2015a). The increase is a result of higher costs of the alternatives as well as higher amounts of the alternatives needed to manufacture one unit of fluoropolymer. Some downstream users mentioned that no cost effects occurred after substitution from PFOA to alternatives.

132.Toxicokinetic data of C₃ Dimer salt indicate little or no metabolism, but rapid excretion. It is presumably cleared non-metabolized within 2-7 days (mouse), 10-11 h (monkey) and 4-48 h (rat). C₃ Dimer salt is classified as skin irritating and eye damaging. Moreover, repeated administration resulted in liver enlargement and hepatocyte hypertrophy as well as liver cell necrosis at 0.5 mg/kg/day in male mice. With respect to carcinogenicity, a two-year rat study gave tumors at higher doses (≥50 mg/kg/day). With regards to environmental risks (data were taken from the registration dossier) related to C₃ Dimer salt, it was concluded that the substance is probably not acutely toxic (LC/EC₅₀>100 mg/L) or chronically toxic (NOEC>1 mg/L) to aquatic organisms. Regarding all available information a full PBT assessment including assessment of the criteria persistence, bioaccumulation and toxicity according to the EU chemicals legislation (for guidance see ECHA, 2017a) cannot be performed. However, the registrant acknowledges in the chemical safety report (CSR) that the C₃ Dimer salt fulfils the P and the T criterion based on specific target organ toxicity after repeated exposure (STOT RE 2). The C₃ Dimer salt is likely to fulfil the PBT criteria of the European chemicals legislation, see REACH Annex XIII (ECHA, 2015a).

133.With respect to ADONA, it turned out that the substance is persistent. No data related to carcinogenicity were available. Concerning environmental risks (data were taken from the registration dossier under the REACH regulation) related to ADONA it was concluded that the substance is probably not acutely toxic (LC/EC₅₀>100 mg/L) or chronically toxic (NOEC>1 mg/L) to aquatic organisms. Regarding all available information a full PBT assessment cannot be performed. The substance will most probably fulfil the P criterion of REACH Annex XIII. Based on the data for environmental toxicity, the substance does not fulfil the T criterion. The registration dossier lacks toxicological information relevant to humans. Thus the data are not sufficient to conclude or to refute on the PBT-properties of the substance (ECHA, 2015a). Based on a document from the European Food Safety Authority from 2011, 3M reported that the elimination half-life of ADONA was between 12 and 34 days from the bodies of three workers, while it takes about four years in humans to clear half of the PFOA (see The Intercept, 2016 and EFSA 2011b).

134.In another study (Gordon, 2011) the toxicity of ADONA was evaluated in acute and
repeated-dose studies of up to 90 days, in eye and skin irritation, dermal sensitization, genotoxicity, and developmental toxicity studies. The substance was evaluated as a peroxisome
proliferator-activated receptor alpha (PPARα) agonist in rats, moderately toxic orally and practically non-toxic dermally in acute rat studies. In rabbits ADONA turned out to be a mild skin irritant and a moderate to severe eye irritant as well as a weak dermal sensitizer in local lymph node assays in mice. Based on the weight of evidence from five assays, ADONA was not considered genotoxic. No developmental toxicity was observed except at maternally toxic doses. Regarding ADONA as a PPARα agonist the liver was the primary target organ in male rats and the kidney in female rats. It was concluded by the author that the toxicity profile for ADONA is acceptable for its intended use as PPA and is superior to the one of APFO.

135.EEA-NH₄ is considered persistent. Provided data is not sufficient to conclude on not bioaccumulating (B). Regarding environmental risks (data were taken from the registration dossier) related to EEA-NH₄ no acute toxicity (LC/EC₅₀>100 mg/L) to aquatic organisms was determined. On the basis of all available information a full PBT assessment with consideration of the knowledge from the PFOA-PBT assessment cannot be performed. The substance will most probably fulfil the P criterion of REACH Annex XIII. Based on the data for environmental toxicity, the substance does not fulfil the T criterion. Toxicity data on human health were provided in the registration. The registrant points out that the substance is classified as toxic for reproduction category 2. Thus the substance fulfils the T-criterion of Annex XIII and it remains a PBT suspect. (ECHA, 2015a).

136.Serum elimination half-lives of the two PFECAs, GenX (in rats and mice) and ADONA (in rats and humans), were reported (ECHA, 2014b; EFSA, 2011b). Provided elimination half-lives were shorter compared to the one for PFOA, but it was considered impossible to draw a conclusion on the bioaccumulation potential of PFECAs and PFESAs due to the fact that no quantitative serum elimination half-life threshold is defined in regulations as a criterion for bioaccumulation, the interspecies variation has not been elucidated and the studies were often conducted with different dosing methods (e.g. oral vs. intravenous, single vs. repeated dose). As a consequence reported serum elimination half-lives between substances cannot be directly compared (Wang et al., 2015).

B. Textile and carpet sector

137.The properties, performance and associated hazards of fluorinated and non-fluorinated durable water repellent (DWR) chemistry for textile finishing have recently been reviewed (Holmquist et al., 2016); the following sub-sections present an overview of individual chemistry.

Short-chain fluorinated alternatives

138.Short-chain fluorotelomer-based substances replacing their long-chain equivalents have been identified as alternatives for a variety of uses including, amongst others, textile and carpet uses (USEPA, 2012).

139.Side-chain fluorinated polymers comprising non-fluorinated carbon backbones and side chains containing a mixture of 6:2-14:2 fluorotelomer moieties or moieties derived from PFOSF were used in surface treatment products to give water- and oil-resistance to textile, leather and carpets (Buck et al., 2011). A trend to use shorter-chain homologues to replace long-chain fluorotelomer- or PFOSF-based derivatives on side-chains can be observed (Ritter, 2010). Several surface treatment products containing C₄ side-chain fluorinated polymers derived from perfluorobutane sulfonyl fluoride (PBSF) have been commercialized (Renner, 2006). In addition, products mostly based on highly purified fluorotelomer raw materials (mostly 6:2), including copolymers derived from 6:2 fluorotelomers and organosiloxane (Dow Corning, 2007), have been developed by fluorotelomer manufacturers (Ritter, 2010). Short-chain polyfluoroalkyl alcohols such as 3:1 and 5:1 fluorotelomer alcohols (FTOHs) have been commercialized and can be used as building blocks for side-chain fluorinated polymers (Wang et al., 2013).

140.Chemical alternatives to PFOA-related compounds used for stain- and water-repellency are available and include textile and carpet surface treatment applications based on acrylate, methacrylate adipate and urethane polymers. With regard to short-chain PFASs, PBSF-based and

6:2 fluorotelomer-based substances, including polymers, have been applied. According to a variety of scientific studies, and the Madrid Statement(Madrid Statement, 2015) , an international scientific consensus statement, these compounds have raised concerns with regards to persistency and bioaccumulation and should not be regarded as acceptable alternatives considering criteria outlined in the POPRC Alternatives Guidance document (see UNEP/POPS/POPRC.13/INF/6; Section 3).

141.Compounds based on ≤C₆-based fluorotelomer chemistry are used to manufacture fluorotelomer-based products indicating the technical feasibility of this alternative. Higher volumes must be applied to achieve the same technical performance and costs of ≤C₆-based fluorotelomer products are higher (ECHA, 2015a).

142.For fluorotelomer products based on 8:2 fluorotelomer alcohol (8:2 FTOH), the short-chain 6:2 FTOH is used as an alternative. This substance will not degrade to PFOA, but rather to other acids, such as perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), and 2H,2H,3H,3H-undecafluoro octanoic acid (5:3 fluorotelomer acid) (ECHA, 2015a). According to another study (Ellis et al., 2004) perfluoroheptanoic acid (PFHpA) is formed as well upon the atmospheric degradation of 6:2 FTOH, and it is stated that PFHpA and PFHxA are the most abundantly formed PFCAs upon the atmospheric oxidation of 6:2 FTOH. In soil-bound residues, 5:3 acid may not be available for further biodegradation (Liu et al., 2010a; Liu et al., 2010b). In activated sludge, 6:2 FTOH also undergoes rapid primary biotransformation, and more than 97 % of 6:2 FTOH may be converted to at least 9 transformation products within 3 days. Major biotransformation products include 5:3 acid, PFHxA, and PFPeA (Zhao et al., 2013b). Similar biotransformation products were also found in a study using an aerobic river sediment system (Zhao et al., 2013a). More information regarding the transformation/degradation of 6:2 fluorotelomers can be found in section II of FOEN, (2017).

143.According to a study sponsored by FluoroCouncil considering data from published and unpublished scientific studies, the fluorinated chemical alternatives to PFOA (6:2 FTOH, PFHxA/PFHx, 6:2 methacrylate and 6:2 acrylate) do not meet the overall Stockholm Convention POPs criteria. The study concludes that 6:2 FTOH meets one of the POP criteria of the Stockholm Convention (meets criteria based on atmospheric transport, but additional information is necessary to determine if concentrations in remote environments are of potential concern according to Annex D paragraph 1 (d) (i). persistence, bioaccumulation, ecotoxicity and toxicity to humans not fulfilled). PFHxA and its anion PFHx meet the criteria of persistence, because they are likely to be environmentally persistent even though data on the degradation half-life of PFHxA in soil, sediment and water are not available. The criteria of bioaccumulation, long-range environmental transport, ecotoxicity and toxicity to humans are not fulfilled (FluoroCouncil, 2014a). A more recent report based on the previous assessment considered newly published studies and supports the initial conclusion that none of the analyzed short-chain PFASs (6:2 FTOH, PFHxA/PFHx, 6:2 methacrylate and 6:2 acrylate) meet the Stockholm Convention POP criteria (FluoroCouncil, 2016b). Nevertheless, the alternatives and alternative mixtures may still exhibit hazardous characteristics that should be assessed before considering such substances to be suitable alternatives.

144.Risks related to short-chain chemistry are described in detail in sections C.2.2 (human health risks) and C.2.3 (environmental risks) of (ECHA, 2015a). Main findings related to 6:2 FTOH based on several studies (Lindeman et al., 2012; Maras et al., 2006; Martin et al., 2009; Mukerji et al., 2015; Oda et al., 2007; Ishibashi et al., 2007; Vanparys et al., 2006; all cited by ECHA, 2015a) are outlined in the background document of this risk management evaluation (UNEP/POPS/POPRC.13/INF/6; Section 4). Further available studies on short-chain PFASs have been compiled by FluoroCouncil.²²

145.6:2 FTOH will undergo biotransformation, resulting in PFCAs containing 3 to 5 fluorinated carbon atoms. These PFCAs are structurally similar to PFOA, only differing in the number of fluorinated carbon atoms. These short-chain PFCAs are equally persistent in the environment and cannot be further degraded under biotic or abiotic conditions (ECHA, 2015a). However, the bioaccumulation potential of PFCAs with <7 fluorinated carbons is expected to be lower than that of PFOA (Conder et al., 2008).

146.Metabolites of 6:2 FTOH are expected to be persistent, to have a lower bioaccumulation potential in wildlife and humans and a lower toxicity to aquatic organisms compared to PFOA (ECHA 2015a). However, short-chain PFCAs are more mobile than PFOA in an aqueous environment, and can potentially contaminate drinking water (Eschauzier et al., 2013; Gellrich et al., 2012). Also, they may accumulate more in vegetables, which can be a different route of exposure (Krippner et al. 2015; Blaine et al. 2014). Results of another study indicate that fluorotelomer carboxylic acids are more acutely toxic to aquatic invertebrate and plant species compared to their corresponding PFCAs (Mitchell et al., 2011). However, it should be considered that environmental concentration may change over time, especially if used in higher amounts due to a phase out of PFOA, its salts and PFOA-related substances.

147.POPs characteristics raise concerns about the suitability of a number of fluorinated chemical alternatives to PFOA including PFHxS, PFHpA, PFHxA, PFBS, PFBA, 4:2 FTOH, 6:2 FTOH, 6:2 fluorotelomer acid (6:2 FTA) and 6:2 fluorotelomer sulfonate (6:2 FTS). Due to its very persistent and very bioaccumulative (vPvB) properties, PFHxS was recently unanimously added by the EU member states to the REACH list of substances of very high concern (SVHC) (ECHA, 2017b). In addition, Norway recently nominated PFHxS for addition to the Stockholm Convention. These characteristics raise concerns regarding implementation of Article 3 paragraphs 3 and 4. Specific information and corresponding references related to adverse effects of these alternatives are available (UNEP/POPS/POPRC.13/INF/6; Section 5).

Non-fluorine containing alternatives

148.According to representatives of the textile industry (VTB SWT, 2016), non-fluorine containing alternatives including paraffins, alpha olefin modified siloxanes, fatty-acid modified melamine resins and fatty-acid modified polyurethanes exist for standard- and outdoor clothing with low-level of repellency (VTB SWT, 2016). In some cases, when applying fluorine-free alternatives, quality requirements of professional, technical and protective textiles cannot be fulfilled due to, for example, a lack of chemical-, oil- and/or dirt-repellent properties, inadequate abrasion and/or wash resistance especially in industrial and chemical cleaning applications, poor dry soil-repellency, a lack of weather resistance and UV-stability, blocking of breathable membranes (e.g. in protective clothing after short wash-cycles) or limited options related to further processing (VTB SWT, 2016).

149.A range of fluorocarbon-free, water-repellent finishing agents for textiles include commercial products such as BIONIC-FINISH®ECO and RUCO-DRY® ECO marketed by Rudolf Chemie Ltd., Geretsried/Germany; Purtex® WR, Purtex® WA, Purtex® AP marketed by the Freudenberg Group, Weinheim/Germany; and ecorepel® marketed by SchoellerTechologies AG, Sevelen/Switzerland (Stockholm Convention, 2014).

150.Concerning water-repellant properties, there are several substances that can be applied instead of highly fluorinated substances, whereas alternatives for grease- and dirt-repellent agents are rare. Most prominent

water-repellent alternatives are silicone-based agents. These include high molecular weight polydimethylsiloxanes (PDMS), mixtures of silicones and stearamidomethylpryriden chloride (sometimes in combination with carbamide (urea) and melamine resins), waxes and paraffins (usually consisting of modified melamine-based resins) and dendrimers that are being developed to imitate the ability of the lotus blossom to repel water (Swedish Chemicals Agency, 2015).

151.Paraffin repellents are liquid emulsions that should not be classified as hazardous to health according to the producers. However, some of the identified ingredients seem to be harmful. The main ingredient in most products is paraffin oil/wax (mixtures of long chain alkanes), which is considered harmless in pure form. Some products also contain isocyanates, dipropylene glycol, metal salts or other unknown substances, which may be harmful. Most components are readily biodegradable and do not bioconcentrate or accumulate in organisms and food chains, and the toxicity to aquatic and terrestrial organisms is insignificant, even when regarding concentrations above the water solubility (Danish EPA, 2015b).

152.Most silicones applied in textile impregnation agents are based on PDMS which are inert and have in general no adverse effects. Various siloxanes, especially the cyclic siloxanes known as D4, D5 and D6 and specific linear siloxanes are intermediates for the synthesis of silicone polymers used for textile impregnation. Siloxanes are persistent and widespread in the environment. Mostly, they are detected in urban areas and in the aquatic environment. High levels have been found in livers of fish, which were caught close to outlets of sewage treatment plants. Siloxanes are generally removed from the aqueous phase by sedimentation, and exhibit a long half-life in sediments. In soils, siloxanes are transformed depending on the conditions into hydroxylated forms, which still may be persistent (Danish EPA, 2015b; further information see also P05, 2012 and Davies, 2014). In Canada, it is concluded that D4 is entering the environment in a quantity or concentration or under conditions that have or may have an immediate or long-term harmful effect on the environment or its biological diversity.

153.With regards to dendrimer-based repellents there are no data on health properties of the active substances and other components, but producers of commercial products have provided health data in the MSDSs and made some proposals for classification of the product. According to information from producers these products should not be classified as harmful for the environment, but it is not possible to evaluate these statements on the basis of available information (Danish EPA, 2015b) The compositions of the products were not specified sufficiently for an assessment, but some of the products include unknown siloxanes, cationic polymers, isocyanates, or irritating organic acids. In summary, the health assessment information for this group of chemicals is insufficient for an assessment of the possible health effects of the impregnation agents (further information see also P05, 2012 and Davies, 2014).

154.A recent study noted that non-fluorinated chemical alternatives can meet water repellency requirements for outdoor apparel. The authors propose that the use of PFAS chemistry for outdoor apparel is over-engineering and that significant environmental and toxicological benefits could be achieved by switching outdoor apparel to
non-fluorinated chemistry (IPEN Comments on 2^nd draft RME referring to Hill et al., 2017).

Non-chemical alternatives

155.With regards to textiles, tightly woven fabric is one of the alternative non-chemical technologies. Another technology is the so-called reverse osmosis membrane comprising extremely thin films made of polymer materials and constructed in a way that it is highly impermeable to water in liquid form, but permeable to water vapor, which leads to a breathable fabric. An alternative to PTFE is a composite of a hydrophobic polyester and a hydrophilic polymer forming a microstructure, which allows the fabric to breathe (Swedish Chemicals Agency, 2015).

156. The Swedish Chemicals Agency presents one example of an international initiative to find fluorine-free alternatives (Swedish Chemicals Agency, 2015). Huntsman Textile Effects, which is a global supplier of dyes and other chemicals for the textile industry, has started to collaborate with DuPont with the aim to develop a new product with water-repellent properties. Based on information provided by the companies, this is the sector’s first
water-repellent treatment agent consisting totally of renewable material, 63% of which is obtained from plant-based raw materials (Ecotextile News, 2015; cited by Swedish Chemicals Agency, 2015). According to the manufacturer, the finish is up to three times more durable than existing non-fluorinated repellents, maintains fabric breathability for maximum comfort, is compatible with common finishing auxiliaries (including resins and cross-linking agents) and is not made with genetically modified organisms (Chemours, 2017).

157.The company Pyua has developed a technology (CLIMALOOPTM), which is

fluorocarbon-free and promises highest performance with respect to impermeability, breathability and wind impermeability. The technology is based on recycled material and developed for long lasting outdoor applications. Moreover, each Pyua product is completely recyclable and produced in an ecologically and socially sustainable manner (Pyua, 2017).

C. Firefighting foams

Short-chain fluorinated alternatives

158.During the last several years, manufacturers of fluorotelomer-based AFFFs have been replacing long-chain fluorinated surfactants with short-chain fluorinated surfactants (UNEP, 2017). AFFFs based on pure 6:2 fluorotelomers were developed to replace early products based on a mixture of mainly 6:2 and 8:2 fluorotelomers (Klein, 2012; Kleiner and Jho, 2009). DuPont, for example, commercialized two AFFFs based on 6:2 fluorotelomer sulfonamidealkylbetaine (6:2 FTAB) or 6:2 fluorotelomer sulfonamideaminoxide (Wang et al., 2013). Suppliers offering a portfolio of

short-chain fluorotelomer-based surfactants include Chemguard, Chemours and Dynax (UNEP, 2017).

159.Chemical alternatives include C₆-fluorotelomers such as 6:2 fluorotelomer sulfonyl betaine, sometimes combined with hydrocarbons and the 3M product dodecafluoro-2-methylpentan-3-one. The direct release of substances to the environment and the detection of C₆ compounds in the environment including the Arctic, human and wildlife make this use of fluorinated alternatives undesirable (see UNEP/POPS/POPRC.13/INF/6) (IPEN, 2016).

Non-fluorine containing alternatives

160.A variety of fluorine-free Class B foams are on the Swedish market indicating the technical feasibility of this alternative. The firefighting foam Moussoll-FF 3/6 was introduced at a Swedish airport and is degraded to carbon dioxide and water in the environment. It is considered effective in fire suppression required at airports where high safety standards have to be fulfilled. Swedavia, which owns ten Swedish airports, including Arlanda and Landvetter, had previously used fluorine-based firefighting foams but in June 2011 switched to a fluorine-free alternative. The Swedish Armed Forces began phasing out the use of perfluorinated substances in firefighting foam in Sweden in 2011. Nowadays the Swedish Armed Forces use a fluorotelomer-based firefighting foam, i.e. the substance that is broken down to perfluorinated substances (further details see Swedish Chemicals Agency, 2015). Norwegian airports, military properties and several offshore companies have also introduced fluorine-free foams (Norway Comments on 3^rd draft RME).

161.With respect to firefighting foams, it is estimated in a study (RPA, 2004) that the cost for fluorine-free alternatives is approximately 5-10% higher than the one for fluorosurfactant foams. Based on information provided by a manufacturer of the fluorine-free alternatives, the cost would fall in case of an increased market size (Poulsen et al., 2005). This study does not consider the internalized costs of continued reliance on fluorosurfactant foams, including the costs of groundwater remediation, contamination of aquatic environments, subsistence and commercial fishers, and environmental and public health (IPEN Comments on 2^nd draft RME).Lifetime costs for using AFFF, fluoroprotein (FP), or film forming fluoroproteins (FFFP) far outweigh those of fluorine-free foams just because of legal and financial liabilities of using a fluorochemical based foam (see Queensland Gov., 2016a and 2016b) as indicated above which include infringement of operating license conditions, reputational and brand image damage (see Klein 2013). Increasing evidence suggests that fluorochemical contamination of groundwater is an ongoing serious issue impacting agriculture, fisheries, property prices, with considerable political and public concern fallout resulting in hugely expensive and damaging and legal challenges. Remediation costs are still substantial, especially off-site, compounded by high analytical and consultancy costs in the case of environmental contamination with fluorinated breakdown products from an AFFF, FP or FFFP (see e.g. Klein 2013).

162.The BAT/BEP Guidance for use of PFOS and related chemicals under the Stockholm Convention on POPs (UNEP, 2017) confirms that non-fluorinated foams exist and are in use. According to a review undertaken by the Queensland Government in Australia, many fluorine-free foams are acknowledged as meeting the toughest amongst the firefighting standards and exceeding film-forming fluorinated foam performance in various circumstances and that fluorine-free foams are widely used by airports and other facilities including oil and gas platforms (see Queensland Gov., 2016b). According to the Swedish Armed Forces it is difficult to find fluorine-free alternatives which meet specific safety requirements (see Swedish Chemicals Agency, 2016).

163.Manufacturers and some users mention that fluorine-free firefighting foams do not have comparable extinguishing effects as foams with fluorosurfactants. Compared to fluorine-based firefighting foams approximately twice as much water and foam concentrate are needed when extinguishing liquid fires. According to some fluoro surfactants foam manufacturers, some analysis confirmed that fluorine-free firefighting foams may offer less protection against re-ignition, which makes it impossible to apply this alternative for some operations (Swedish Chemicals Agency, 2015). According to the Fire Fighting Foam Coalition (FFFC) AFFF agents containing fluorotelomer-based fluorosurfactants are the most effective foam agents currently available to fight flammable liquid fires in military, industrial, aviation and municipal applications. Test data provided by the United States Naval Research Laboratories (NRL) (NRL, 2016) showed that, in pool fire tests, an AFFF agent achieved extinguishment in 18 seconds compared to 40 seconds of the fluorine-free foam. In foam degradation tests, fluorine-free foam degraded after 1-2 minutes, while the AFFF lasted 35 minutes before it has been degraded. The FFFC does not support the opinion that AFFF agents are no longer needed and recommends the use of AFFF only in specific circumstances where a significant flammable liquid hazard occurs and that all available measures to minimize emissions to the lowest possible level should be implemented when using AFFF agents (FFFC, 2017). However, blockage factors (i.e. vapour suppression) were indistinguishable between a fluorine-free-foam and two AFFFs tested (Williams et al. 2011). Airports and offshore companies around the world have introduced fluorine-free foam and are satisfied by the performance.

164.A Spanish foam manufacturer presented results from a series of new fire tests (Wilson, 2016) run on five commercially available short-chain (C₆) AFFF agents and five commercially available fluorine-free foams (tests were run with the four different fuels gasoline, heptane, jet A1 and diesel). It was shown that the short-chain AFFF foams performed significantly better compared with

fluorine-free foams on all fuels except diesel. None of the fluorine-free foams managed to extinguish the jet A1 fire (the fuel used in the International Civil Aviation Organization (ICAO) fire tests that determine the acceptability of foams for airport use in many countries) (FFFC, 2017). However, fluorine-free foams certified to different ICAO levels (required for use at civilian airports) are available on the market (see FFFP, 2017) and are already introduced at airports in practice (see above).

165.The institute for fire and disaster control Heyrothsberge in Germany tested six fluorine free alcohol resistant firefighting foams and one PFAS containing foam for their ability to extinguish fires of five different polar liquids. The authors conclude that there are fluorine-free foams available which show a similar performance compared with PFAS containing foams (see Keutel and Koch, 2016).

D. Paper and food packaging

Short-chain fluorinated alternatives

166.Products based on 6:2 fluorotelomers have been developed by fluorotelomer manufacturers with the aim to replace earlier products such as side-chain fluorinated polymers and phosphate diesters that were based on longer-chain fluorotelomer derivatives (Loi et al., 2013). For example, several 6:2 fluorotelomer-based side chain fluorinated polymers have been registered in the Inventory of Effective Food Contact Substance (FCS) Notifications of the United States Food and Drug Administration including e.g. products from Asahi or Daikin (Wang et al., 2013). However, according to the information submitted by IPEN, there is a lack of publicly available information on toxicity and POPs properties.

167.A global manufacturer in specialty chemicals, received in 2015 US Food and Drug Administration (FDA) food contact approval for an oil- and grease-resistance additive, which is PFOA-free and provides high levels of
oil-, grease- and water-resistance to paper and board. The additive is also compliant with the recommendations or use as a surface refining and coating agent in paper and board, which is intended for food contact applications. The additive is based on a cationic 6:2 fluorotelomer-based side-chain fluorinated polymer and provides a strong and long lasting barrier to both grease and water. According to the manufacturer, due to its performance properties and environmental profile the additive is considered particularly suitable for the use in both size press and wet-end applications to produce fast food boxes and wrappers, soup cube boxes, butter wrap and oil bottle labels. It can as well be used in the production of molded pulp plates and cups and in pet food packaging (AMR, 2015).

168.FDA currently does not allow long-chain fluorinated substances in food packaging applications. FDA removed the last legacy long-chain PFOA-related substances from 21 CFR 176.170 in 2016 (see 81 Fed. Reg. 5–8). Any 2015 FDA approvals for a resistance coating applied to paper and board would have been for a short-chain alternative, and would have been done through the Food Contact Notification (FCN) process.

Non-fluorine containing alternatives

169.At least one manufacturer from Norway has developed a fluorine-free alternative using a

high-density paper, which prevents the passage of grease (Swedish Chemicals Agency, 2015). The Norwegian paper producer Nordic Paper is using mechanical processes to produce, without using any persistent chemical, extra-dense paper that inhibits leakage of grease through the paper.²³

170.More information is available in Norden 2013, SFT 2007 and Nordic Ecolabelling 2014. Nordic Ecolabelling 2014 indicates that for impregnation and coating paper can be surface treated using starch, alginates, CMC (carboxylmethylcellulose), chromium compounds, fluoride chemicals or silicone. Organotin compounds are used as catalysts in the silicone coating of grease-proof paper and may migrate into food in contact with paper. Butyltin is specifically mentioned as catalyst in the paper. The Ecolabel contains requirements to prevent the presence of chromium, fluoride compounds, whereas solvent-based painting/coating agents, D4 and D5 and organotin catalysts may not be used in the silicone treatment. These substances may still be used elsewhere and thus be imported into Europe.

171.The German BfR (BundesinstitutfürRisikobewertung) maintains a database concerning recommendations on Food Contact Materials including fluorinated and non-fluorinated substances.²⁴

Uses where no alternatives are currently identified for all uses

A. Technical textiles with high performance requirements

172.Industry associations noted that especially in the field of professional, technical and protective textiles and other advanced textiles (e.g. for fuel cell separators for e-mobility innovations), no alternatives meeting the high demand by legal requirements and by customers are currently available. However, it is admitted that those textile products that must only fulfil low-performance requirements (e.g. standard clothing, standard outdoor textiles), which were formerly treated with PFOA-related compounds, may be treated by C₆-products or even fluorine-free alternatives (VTB SWT, 2016; Euratex, 2016).

173.Stakeholders state that protective textiles finished with the C₆-chemistry need large amounts of C₆-products for the initial finishing and repeated professional re-impregnation with further C₆-products after each washing step in order to meet high safety standards; this will result in additional emissions of PFASs due to the larger amounts of used chemicals compared to the C₈-chemistry (VTB SWT, 2016). In this context, it was mentioned that over the life-cycle technical textiles treated with 6:2 fluorotelomer-based finishes often exhibit 4-8 times more PFAS total emissions compared to the observed emissions using the C₈-chemistry (Euratex, 2016).

174.The textile industry reported that the C₈-chemistry is able to fulfill the high requirements related to repellency of dangerous liquids and dusts while having a minor detrimental effect on flame retardations. This preferable combination of the two effects cannot be obtained by C₆-based products. Moreover, it was stated that technical protective textiles protect workers from being contaminated by liquids or dangerous substances (e.g. infectious liquids). Thus, serious health issues might occur in case of neglected re-impregnation, which is required due to a decrease in protection performance over time (VTB SWT, 2016), (TM, 2016).

B. Imaging and printing industry

175.According to I&P Europe, PFOA-related compounds were successfully replaced by

non-perfluorinated chemicals, chemicals with short (C₃-C₄) perfluorinated chains, telomers, and reformulations. However, a small number of relevant uses remain. PFOA-related compounds are considered necessary for the application of coating layers during manufacture of some remaining conventional photographic products (i.e. products in which the image formation is based on silver halide technology). They serve as surfactants, static control agents (important for preventing employee injury, operating equipment and product damage and fire and explosion hazards (I&P Europe, 2016b), dirt repellents during coating operations, friction control agents and provide adhesion control for coated layers and are considered unique, as they combine all these properties in one molecule without showing adverse effects on photographic performance (I&P Europe, 2016a).

176.An estimation of costs with regards to the replacement of the remaining relevant uses of PFOA-related substances in the photo and printing industry cannot be estimated. The formulas of imaging coatings are proprietary and differ from company to company and from product to product. Thus, each company will identify different costs when changing formulation compositions, which may take several years of effort with respect to research and development (not only the performance of substances is evaluated when developing alternatives, but also environmental, health and safety issues). Economic costs associated with substitution of PFOA-related substances concerning few remaining critical relevant uses in the imaging and photographic sector are considered prohibitive by the industry. The remaining critical uses are described as niche products in markets that I&P Europe members plan to diminish (I&P Europe, 2016a).

C. Semiconductor industry

177.Non-PFOA-based alternatives appear to be available in the semiconductor industry for some applications, such as the uses as surfactants. However, some uses with respect to PFOA-related substances as a constituent material in process, chemical formulations for very specialized application steps (e.g. for the photo-lithographic applications) remain. In a study from 2010, it was found that for those companies using PFOA within their photo-lithographic applications derogations will be necessary in order to be able to continue production (van der Putte et al., 2010). According to representatives of the semiconductor industry, alternatives for some applications may not be available, and the industry requires a significant amount of time to identify, test, and qualify substitutes before they are introduced into commercial production. A specific time frame needed for transition is not indicated (see SIA, 2017). A time limited exemption could provide the time needed to enable to continue the transition to appropriate alternatives in semiconductor manufacturing processes. SEMI further states, that this exemption should take the form of an acceptable purpose (see SEMI, 2017).

D. Use of sulfluramide

178.Currently, the active ingredients registered in Brazil for producing bait to control leaf-cutting ants are sulfluramid, fipronil and chlorpyrifos. Chlorpyrifos as insect baits is no longer used in Brazil for control leaf cutting ants (UNEP/POPS/POPRC.12/INF/15/Rev.1). The effectiveness of these substances has been questioned; thus new alternatives are being studied in Brazil. According to the Brazilian Annex F information, sulfluramid cannot currently be efficiently replaced in Brazil by any other registered products commercialized for the same purpose (UNEP/POPS/POPRC.12/INF/15/Rev.1, UNEP/POPS/COP.7/INF/21).

179.According to Brazil, fenoxycarb, pyriproxyfen, diflubenzuron, teflubenzuron, silaneafone, thidiazuron, tefluron, prodrone, abamectin, methoprene, hydramethylnon, boric acid, some insecticides from the group of neonicotinoids, pyrethroids, Spinosyns, etc., had been tested for leaf-cutting ants, but they were not effective (UNEP/POPS/POPRC.12/INF/15/Rev.1).

180.According to the decision SC-6/7, Brazil undertake studies to obtain peer-reviewed information on the feasibility of using alternatives to PFOS, its salts, PFOSF and their related chemicals within an integrated pest management approach and to submitted to Secretariat. This study conclude that, based on technical feasibility, humans and environment effects, cost/effectiveness, availability and viability, that there are no alternatives to replace sulfluramid to control leaf-cutting ants (Information from Brazil, 2016).²⁵

181.Information on volumes is contained in UNEP/POPS/POPRC.12/INF/15/Rev.1. It was noted that there are some reports indicating that sulfluramid may degrade to PFOA and is in the list of precursors of PFOA (UNEP/POPS/POPRC.13/INF/6/Add.1).

Summary of alternatives

182.The following paragraphs summarize information on alternatives from sections 2.3.1 to 2.3.3.

Summary of risks related to short-chain fluorinated alternatives

183.There is an increasing concern among authorities in Europe regarding risks for health and the environment exhibited by short-chain PFASs. These concerns are due to their persistence, high mobility in water and soil and potential toxic properties of these substances. Although some of the short-chain PFAS may not formally fulfil the current PBT-criteria under Europe’s REACH legislation, they are extremely persistent, very mobile in aquatic systems and in soil, and their increasing use may lead to a continuous exposure that could be of equal concern as bioaccumulation (Norway Comments on 2^nd draft RME). Already now short-chain PFAS are ubiquitously present in the environment, even in the remote areas (see e.g. Zhao et al., 2012).

184.The higher solubility in water compared to long-chain PFASs with more hydrophobic alkyl chains also contributes to the fact that some short-chain PFASs, in particular short-chain PFCAs and PFSAs, do enter drinking water reservoirs faster and certain tend to accumulate in water-rich edible plant tissues like leaves and fruits. The presence in groundwater and drinking water might lead to a continuous exposure of organisms to certain short-chain PFASs, currently still at a relatively low level, but given the high persistence and the increasing use of these substances a temporal increase in environmental concentrations may be expected. This is even more valid as removal of short-chain PFASs from water cannot be performed effectively, not even with modern expensive technologies (e.g. using granular activated carbon or nano-filtration), due to their low adsorption potential (see German Environment Agency, 2016b).

185.It should be noted, that Germany is proposing to identify substances having such properties related to mobility and persistency as substances of very high concern under REACH in a similar manner as substances being very persistent and very bioaccumulative (see German Environment Agency, 2017). As described in chapter 2.3.2 these substances are considered alternatives to PFOA for several applications (e.g. textile sector, firefighting foams, paper and food packaging). Often, these short-chain alternatives are less effective and higher quantities are required. This data suggests that the replacement of PFOA, its salts and related compounds by short-chain fluorinated substances may be identified as a regrettable substitution.

186.In this context it should be noted that that pollution with short-chain PFAS is a heavy burden for the community/society. In Germany more than 450 ha of agricultural fields were polluted with PFAS most probably by intermixing paper sludge with compost. PFAS have been found in elevated concentrations in soil and groundwater. Short-chain PFAS are the main contaminants in this area. As a consequence, two drinking water wells were closed. Because shortchain PFAS can be taken up in the edible part of the plants and crops have been shown elevated levels of short-chain PFAS, before harvesting PFAS levels in crops need to be analysed in this area. Only crops not enriching PFAS can be cultivated and harvests showing elevated levels of short-chain PFAS cannot be consumed by humans or used as feed. A solution to purify the soil or to stop short-chain PFAS reaching the groundwater has not been found yet. Because of the large polluted area, excavation does not seem to be appropriate. The overall consequences for the inhabitants, the public and the farmers are immense. The costs for remediation and water purification and the supply for clean drinking water are high.²⁶ The local water supply company has invested three million euros during the last two years for the supply of clean drinking water in the region. This investment is going to rise to 8 million euros until 2018 because a new purification plant based on activated carbon is being built and because operating costs will increase. Due to the properties of short-chain PFAS, the activated carbon has to be exchanged frequently, to avoid breakthrough of the chemicals. As a consequence the price for drinking water increased by 13.4% in this area in 2017. A further increase of the costs is possible (Germany Comments on 3^rd draft RME).²⁷

Summary of the availability of appropriate alternatives for specific sectors and uses

187.Based on the analysis of alternatives, the following table summarizes for which sectors and specific uses alternatives to the use of PFOA, its salts and PFOA-related compounds are available or not.

Table : Availability of alternatives to the use of PFOA, its salts and PFOA-related compounds for specific sectors and uses

Sector	Use	Appropriate alternative available	Type of alternative
Textile sector	Standard performance requirements (e.g. standard clothing)	Yes	Non-fluorine containing products (e.g. paraffins); Non-chemical alternatives Short-chain fluorinated products (e.g. C6-based)
	High performance requirements (e.g. protective textiles for professional use)	No
Polymer manufacturing	Polymerization processing aid	Yes	Substances with ether linkage(s) between perfluoroalkyl moieties (e.g. ADONA)
Firefighting foams	Fighting against liquid fires	Yes	Protein-based or detergent-based firefighting foams Short-chain fluorinated products (e.g. C6-based)
Paper and food packaging	Food packaging	Yes	Non-fluorine containing products (e.g. high-density paper) Short-chain fluorinated products (e.g. C6-based)
Imaging and printing industry	Manufacture of small number of remaining conventional photographic products	No
Semiconductor industry	Constituent material in process chemical formulations for very specialised application steps (e.g. for photo-lithographic applications)	No