Risk Management Evaluation Endosulfan

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). 37

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). 37

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. 37

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). 37

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). 37

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). 38

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). 38

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). 38

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. 38

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. 38

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). 39

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. 39

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). 39

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). 39

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). 39

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). 40

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). 40

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. 40

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). 40

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 2nd draft RME referring to Hill et al., 2017). 40

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). 41

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). 41

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). 41

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). 41

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). 41

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 3rd draft RME). 41

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 2nd 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). 42

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). 42

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. 42

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). 43