Document ExQ7518BR0bMvdzp6KxE1LBjL

Perfluoroalkylated substances Aquatic environmental assessment c=> O^o 5 ~ ^rn 03 T3D -tm "X -*C p* (. >j-n OK " - P O 5 . ..* ro o Report RIKZ/2002.043 Ip 000337 Ministerie van Verkeer en Waterstaat Directoraat-Generaal Rijkswaterstaat Rijksinstituut voor Kust en Zee/RIKZ Perfluoroalkylated substances Aquatic environmental assessment Report RIKZ/2002.043 1 Ju ly 2002 Authors: University of Amsterdam F.M . Hekster P. de Voogt RIKZ A .M .C .M . Pijnenburg R.W .P.M . Laane University of Amsterdam Environmental and Toxicological Chemistry Nieuwe Achtergracht 166 1018 W V Amsterdam Tel. 31 20 5256504 Fax 31 20 5256522 RIKZ Kortenaerkade 1 P.O . Box 20907 2500 EX Den Haag Tel. 31 70 3114311 Fax 31 70 3114330 P erflu o ro alkyla te d su b stan ces - Aquatic environmental assessment 000338 Perfluoroalkylated substances - Aquatic environmental assessment 2 Contents Contents Preface Summary 1 Introduction 1.1 Background 1.2 Objectives 1.3 Terminology 1.4 References 2 Physical-chemical properties 2.1 Identification 2.2 Physical-chemical characterisation 2.3 References 3 3.1 3.2 3.3 3.3.1 3.3.2 3.3.3 3 .3 .4 3 .3 .5 3 .3 .6 3 .3 .7 3 .3 .8 3 .3 .9 3.4 3.5 3 .6 Production, Use & Emissions of PFAS in the Netherlands Introduction Production Use and emissions Carpet protection Introduction Paper and board protection Textile protection Leather protection Fire-fighting foams Specialty surfactants Polymerisation aid Production sites Other sources Summary of use figures and emissions Overview of commercial names References 4 4.1 4.2 4.3 4.3.1 4 .3 .2 4 .4 4.4.1 4 .4 .2 4.4.3 4 .4 .4 4.5 4 .6 4.7 4.8 Behaviour in the aquatic environment Introduction Solubility and volatilisation Sorption Octanol water partitioning Sorption Transformation Introduction ECF-products Telomer-products Fluorinated organic polymers Bioconcentration Distribution Conclusions and recommendations References Peril uoroalkylated substances - Aquatic environmental assessment 000340 3 3 5 7 11 11 11 12 13 15 15 18 20 21 21 22 22 23 25 26 27 28 30 30 31 31 31 32 33 37 37 37 38 38 39 39 39 40 41 41 42 43 43 44 5 5.1 5.2 5.2.1 5.2.2 5.2.3 5 .2 .4 5.2.5 5 .2 .6 5.3 5.4 5.5 5.5.1 5 .5 .2 5.5.3 5.6 5.7 5.8 5.9 Occurrence in the environment Introduction Analytical techniques (based on Giesy & Kannan, 2002) General remarks Qualitative methods GC-ECD/MS HPLC-FD NMR HPLC/MS/MS Freshwater environment Marine environment Biota The Netherlands & Belgium Europe Global occurrence Air Human exposure Conclusions and recommendations References 49 49 49 49 49 49 49 50 50 50 53 53 53 54 55 59 60 62 62 6 6.1 6.1.1 6.2 6.2.1 6.2.2 6.2.3 6 .2 .4 6.3 6.3.1 6 .3 .2 6 .3 .3 6 .4 6.4.1 6 .4 .2 6 .4 .3 6.5 6 .6 Toxicity Mechanism of toxicity Metabolism Toxic effects in the aquatic environment General Toxicity to freshwater organisms Summary of freshwater toxicity data Toxic effects in the marine environment Standards and derivation of iMPCs (Based on Groshart et al., 2001) Introduction Derivation method Comparison of iMPCs to environmental concentrations Human toxicity Behaviour in humans Acute toxicity Chronic toxicity Conclusions and recommendations References 65 65 65 65 65 66 70 70 71 71 71 73 73 73 74 74 75 76 7 7.1 7.1.1 7 .1 .2 7.2 7.2.1 7.2.2 7.3 7.3.1 7 .3 .2 7.3.3 7 .4 Policy and governmental awareness National environmental policies Netherlands Other country specific policies/ governmental awareness International policy/ awareness OECD OSPAR Actions of industry 3M studies Telomer Research Program APME research program References 81 81 81 81 82 82 82 82 82 82 82 83 List of Annexes 85 Perfluoroalkylated substances - Aquatic environmental assessment 000341 4 49 49 49 49 49 49 49 50 50 50 53 53 53 54 55 59 60 62 62 001) 65 65 65 65 65 66 70 70 71 71 71 73 73 73 74 74 75 76 81 81 81 81 82 82 82 82 82 82 82 83 85 Preface In January 2002, the University of Amsterdam, Institute for Biodiversity and Ecosystem Dynamics (IBED), Department of Environmental and Toxicological Chemistry (M TC) was contracted by the RIKZ to carry out a desk study of perfluoroalkylated substances. This study is directed to the whole track of perfluoroalkylated substances in the environment, i.e .. from production and emission to immission, waste and effects. The project was coordinated by A.M .C.M . Pijnenburg and R.W .P.M . Laane from the RIKZ. The authors of the report are F.M . Hekster and P. de Voogt. The authors wish to thank Mr. Augustin (Pfleiderer), M r. Benjamins, M r. Hofman, M r. Koenings and Mr. Van Wely (DuPont), Mr. Berbee (RIZA), M r. Bonten (FNL), M r. Corpart and M r. Mast (Atofina), Mr. Cox and M r. Sinnaeve (3M ), Mr. Derra (ISEGA), Mr. Foulon (Clariant), M r. Geerdink (Schiphol Airport), M r. Gerritsen and M r. Sewekow (Bayer), Mr. Gerritzen (Daikin), Heensbergen (VTN ), M r. Hernandez (USEPA), Mrs. Hulzebos and M r. Sijm (RIVM ), M r. Ito (Asahiglass), M rs. Jones and Mrs. Watson (Grangers), Mr. Jonkers, Mrs. Krap and Mr. Waeterloos (University of Amsterdam), Mr. Mistrorigo (M iteni), Mr. Klein-Swormink (Niermans), Mr. De Ruyter (Dutch Royal Air Force), M r. Schoemaker (VEBON), M rs. Stengs (Proost & Brand), Special thanks go out to APME, M r. Buck, Mr. Korzeniowski, M r. Rurak, and Mr. De W olf (DuPont), Mr. Cahill (Canadian Environmental Modelling Centre), Mr. De Coen and Mrs. Van de Vijver (University of Antwerp), M r. Elfring (Lakatex), Mr. Hovers and Mr. Kamphuis (Ajax), Mr. JSrnberg (University Stockholm), Mr. Kannan (Michigan State University), Mr. Muir (Environment Canada), M r. Oudman (VNTF), TRP, Mr. Vankann (GuT), Perfluoroalkylated substances - Aquatic environmental assessment 000342 5 Perfluoroaikylated substances - Aquatic environmental assessment 00034<3 Summary General Perfluoroalkylated substances (PFAS) is the collective name for a group of fluorinated chemicals, including oligomers and polymers. There are two major production routes for PFAS: Electrochemical fluorination and tlomrisation. The products from the first process contain a sulfonyl group (the so-called ECFproducts). The products from the second production process contain an ethylene group (telomers). POSF (C8F17S 0 2F) is the most important production intermediate for electrochemical fluorination. 8:2 FTOH (C8F17C2H4OH) is the pivotal substance for telomer production. The most important difference between the two production processes is that ECF yields even and odd numbered, branched and straight perfluoroalkyl chains, whereas tlomrisation only yields even, linear chains. Both ECF-products and telomers have four major forms of appearance, namely monomeric, homo-polymeric, co-polymeric, and phosphate esters. Co-polymers, based on acrylates or methacrylates, are the most common form of appearance. Until the 3M company decided to phase out their PFAS production line, they were the major producer of PFAS. O ther important suppliers of PFAS chemistry are DuPont, Asahiglass, Clariant, Daikin and Ciba. For the present study 15 perfluoroalkylated substances have been selected. These substances are used in commercial products, monomers for polymers, important production intermediates or important degradation products. PFAS have special physical and chemical properties, including chemical inertness, high thermal stability, low surface energy, hydrophobicity and oleophobicity. These properties make PFAS valuable compounds for a wide variety of applications, including carpet, textile, leather and paper and board protection, fire-fighting foams, and specialty surfactants. Sources and emissions Several applications may lead to emissions of PFAS. The most importent is the emission due to wear of PFAS treated tissue (carpet, textile, leather). These emissions are polymeric substances; whether this may lead to monomeric PFAS is not known. The use of fire-fighting foams for calamities or training leads to emissions of monomeric PFAS to the environment. Furthermore, emissions from fluorochemical production sites may be a route of introduction of PFAS into the environment. Carpet 15 Polymers 10 (worst case) Paper & Board 60-105 (not In NL) Phosphates Textile N.A. Polymers 100% of the applied polymers Leather 10-20 Polymers Fire-fighting foams (mobile) 0.13-0.81 Monomers 0.13-0.81 (worst case) Fire-fighting foams (stationary) 1.0-3.0 Monomers 1.0-3.0 (worst case) Specialty surfactants N.A. Monomers - Polymerisation aid >1 Monomers > 0.77 (77%) Table S.1 Use and emissions of PFAS in the Netherlands. N.A. = not available. The use and associated emissions from these applications were assessed in the current report. The most important application of PFAS in the Netherlands is in Perfluoroalkylated substances - Aquatic environmental assessment 000344 7 paper and paper board treatment, but all this paper is imported. The carpet, leather and presumably the textile industry are the biggest users of PFAS based products in the Netherlands (see table S.1). Behaviour in the aquatic environment For a proper assessment of the behaviour of PFAS in the environment many data are lacking. The available data show that the standard concepts of environmental modelling are not applicable. PFAS distribution is not solely based on hydrophobic and hydrophilic interactions, but most likely also on electrostatic interactions. The most important accumulation positions in (aqiatic) biota are expected to be blood and liver. n-EtFOSE, n-MeFOSE and n-EtFOSA (ECF-products) and 6:2 FTOH, 8:2 FTOH and 10:2 FTOH can readily escape from the water phase to air, considering their relatively high Henry's Law constants (H LC). Some of these chemicals have been detected in air recently. This may be an important factor in the global distribution of the PFAS. Other fluorinated chemicals have lower HLC and are expected to remain in the water phase. PFOS and 8:2 FTOH exhibit a high sorption potential and desorption is difficult. Test results show that the perfluoroalkyl chain of ECF-products is not affected by biodegradation, hydrolysis or photolysis. The non-fluorinated part of ECF-products is expected to degrade to sulfonate or carboxylate. The degradation products of telomers are not known, but it is expected that the perfluorinated chain is not affected by degradation, hydrolysis or direct photolysis. Indirect photolysis by OH radicals in air may lead to the decomposition of fluorinated chemicals. 8:2 FTOH was shown to be transformed to some extent in rats to PFOA. For fluorinated organic polymers no degradation data are available. PFOS is highly bioaccumulative, considering its bioaccumulation factor of 6300125000. PFOA hardly bioconcentrates (BCF = 1.8) and 8:2 FTOH has a bioconcentration factor of 87-1100. Occurrence PFOS and to a much lesser extent PFOA have been detected in the environment on a global scale. No validated sampling or analytical method for PFAS exist as yet. Point sources may lead to elevated levels o f PFAS in biota and the abiotic environment Concentrations of PFAS are higher in more urbanised or industrialised areas, in biota and in the abiotic environment. Concentrations in biota from North America were highest, followed by biota from Europe. Concentrations in biota from remote locations such as the Arctic were much lower. All PFAS that have been detected in biota were present in blood, liver, kidney, muscle or brain. PFOS concentrations ranged from below limited of quantification to 907 ng/g wet weight. No data are available for the occurrence of telomers in the environment. In humans, PFOS and PFOA has been detected in occupationally exposed workers and in the general public. Levels in fluorochemical production workers were 0.1352.44 mg/L (PFOS) and 0.106-6.8 mg/L (PFO A); concentrations in the general public were 17-53 pg/L (PFOS) and 3-17 pg/L (PFO A). Perfluoroalkylated substances - Aquatic environmental assessment 8 00034S arpet, based many data ironmental ydrophobic rtions. The o be blood 2 FTOH :ring their lave been listribution cted to difficult. Tected by .'F-products iducts of i is not /sis by OH ::2 FTOH inated af 6300- ronment ixist as yet. c >iota from : were >lood, liver, of urrence of d workers ere 0.135meral Toxicity Toxicity tests for PFOS and PFOA have been performed, although many of them with limited reliability. Therefore the assessment of toxicity of PFAS should be considered as a first estimation. The results show that PFOS has moderate acute toxicity to freshwater fish and slight acute toxicicity to invertebrates. Toxicity to algae is practically nihil. The chronic toxicity of PFOS to freshwater fish is low and practically nihil to invertebrates. PFOS has moderate acute and slight chronic toxicity to marine invertebrates. Due to the relative data richness an assessment factor of 50 can be applied to the lowest chronic toxicity data to derive the proposed value for the Dutch quality objectives (iM PC) for PFOS of 5 pg/L. PFOS concentrations in fresh water were shown to exceed the iM PC, in case of point sources. In other freshwaters, the iMPC was approached. PFOA has slight acute toxicity to freshwater invertebrates and algae, while being practically non-toxic to freshwater fish. Due to the limited number of studies currently available, an assessment factor of 1000 has to be applied to the lowest acute toxicity data to derive the iMPC for PFOA of 3.8 pg/L. This iMPC may be approached close to point sources. For telomers no conclusions regarding their toxicity can be drawn. Both PFOS and PFOA have long half-lives (8.67 and 1-3.5 years, respectively) in the human body. Both chemicals are distributed to liver, plasma and kidney. To rodents PFOS and PFOA exhibit low acute toxicity, but they are eye irritating. In chronic feeding tests with rodents and primates the primary target was the liver for PFOS and PFOA. PFOA was found to be weakly carcinogenic. Mutagenicity testing of PFOS did not show any mutagenic effects. PFOA did induce chromosomal aberrations and polyploidy in Chinese hamster ovary cells, but did not show mutagenic effects in most mutagenicity test, including an in vivo micronudeus test. In a developmental effect study with PFOS the no observed adverse effect level (NOAEL) and the lowest observed adverse effect level (LO AEL) for the second generation of rodents were determined to be 0.1 mg/kg/day and 0.4 mg/kg/day, respectively. Policy In the Netherlands, no specific policy concerning PFAS exists. In the USA the production and import of some ECF-products is regulated and a hazard assessment on PFOA has been performed. The governments from Canada, the United Kingdom and Denmark have programmed studies on the potential risks of PFAS. Furthermore, the OECD has performed a hazard assessment on PFOS. The 3M corporation has performed various studies on the toxicology, pharmaco kinetics and environmental fate and effects of ECF-products, notably PFOS. The Association of Plastic Manufacturers in Europe, APM E, has set up a research program on the toxicology, pharmaco-kinetics and environmental fate and effects of PFOA. The manufacturers of telomers, gathered in the Telomer Research Program (TRP), have set up a research program on the toxicology, pharmaco kinetics and environmental fate and effects of 8:2 FTOH. Perfluoroalkylated substances - Aquatic environmental assessment 000046 9 Periluoroalkylated substances - Aquatic environmental assessment 000347 10 1 Introduction 1.1 Background The presence of fluorine in human blood has been reported as early as in 1968 (Taves 1968). After some initial debate (Belisle 1981), in the mid 1990s the occurrence of perfluorooctanoic acid (PFOA) in humans was confirmed (Gilliland & Mandel, 1993; Gilliland & Mandel, 1996). A few years later several publications in the environmental literature started to draw attention to perfluorolkylated substances (PFAS) (Key et al., 1997; Moody & Field, 1999). This attention was made possible by improved analytical techniques, resulting in the characterisation of this group of chemicals in environmental samples. Nowadays, perfluorooctane sulfonate (PFOS) has been detected all around the globe, both in animals and in humans (Olsen et al., 1999; Giesy & Kannan, 2001). These findings did have consequences for the chemical industry. On May 16, 2000, 3M announced that it was phasing out the perfluorooctanyl chemistry production. The decision was based on principles o f responsible environmental management.' (3M , 2000). USEPA and the OECD have classified PFOS as a PBT chemical (USEPA, 2000b, O ECD, 2002b). Although no adverse effects had been observed at the concentrations detected, this decision and its rationale resulted in international attention and awareness in scientific and non-scientific media (Atofina, 2000; Browne, 2000; USEPA, 2000a; Wood, 2000; Clarke, 2001, Renner, 2001). Furthermore international research projects were started on the environmental behaviour of fluorinated chemicals. In June 2002, draft hazard assessments are available for PFOS (O ECD, 2002a) and PFOA (USEPA, 2002). Furthermore, international research programs are executing studies on the environmental and toxicological properties of PFOA (APME, 2002) and 1H,1H,2H,2HPerfluorodecanol (8:2 FTOH, TRP, 2002). 1.2 Objectives The objectives of this study with regard to perfluoroalkylated substances are: To provide an analysis of the potential issues in the aquatic environment: a description of the loads, occurrence, behaviour and effects and an analysis of the issues which indicate how the presence of perfluoroalkylated substances may disturb the functioning of the different aquatic systems by effects on sensitive organisms. Furthermore to give an overview of the national and international policies with regard to PFAS. In this study the most recent information on perfluoroalkylated substances has been used. PFAS are under much international scientific attention. This results in continuous publications on this matter. This document tries to reflect the state of knowledge in June 2002. The study has a broad set-up. The following aspects will be handled. In chapter 2 the chemical characteristics of perfluoroalkylated substances are described. In chapter 3 the production process is clarified and the use and associated emissions of these chemicals to the environment are described. In chapter 4 the behaviour in the environment is described, followed by chapter 5, dealing with the occurrence in the environment. In chapter 6 and 7 an overview is given of toxicity data and governmental policies, respectively. Perfluoroalkylated substances - Aquatic environmental assessment 11 000348 1.3 Terminology i Fluorochemical: Fluorinated chemical: Fluorotelomer: Fluoropolymer: Fluorinated organic polymer: Perfluoro- /Perfluorinated: Perfluoroalkylated substance: Fluorinated organic surfactant: Perfluorinated surfactant: A term used to describe broadly all chemicals containing the element fluorine; Specifically, the terrn is used most commonly to describe small (1 -8 carbon length) fluorinated molecules which are most used fo, refrigeration, fire suppression and as specialty solvents a term used synonymously with "fluorochemical a term used to describe an oligomer created by reaction of tetrafluoroethylene (TFE) with perfluoroethyl iodide CF3CF2I to produce F(CF2CF2),,-| [n = 3-6, avg. 4], the term " telomer" is often used synonymously with fluorotelomer. a term used to describe a polymer which has fluorine attached to the majority of carbon atoms which comprise the polymer chain backbone. Common fluoropolymers are: polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVD F), fluorinated ethylenepropylene (FEP), etc. a term used to describe a polymer which has a hydrocarbon backbone (polyamide, polyester, polyurethane, etc.) to which is appended a fluorinate carbon chain. describes a substance where all hydrogen atoms attached to carbon atoms are replaced with fluorine atoms - CF,, - where n = 1 - 4. a substance which bears a perfluorocarbon, also known as a perfluroroalkyl, functional group. F(CF2),,R where n is an integer and R is not a halogen, or hydrogen. a term to describe a surface active, low molecular weight, substance which contains fluorinated carbons; the term fluorosurfactant is used synonymously, a term used to describe a surface active, low molecular weight, substance where all carbons bear fluorine in place of hydrogen; the term fluorosurfactant is used synonymously. Perfluoroalkylated substances - Aquatic environmental assessment * . i ; > 12 ^00349 e term :arbon sed for olvents al -F 3)n-I sed Jorine i n FE), 'lene- rinate s >rine I (CF3)nar ar rbons; lecular e in ised 1.4 References 3M, 2000, 3M Phasing out some of its specialty materials, press release. May 16, available at www.3m.com/profile/pressbox/2000_index.jhtml APME, 2002, Association of Plastic Manufacturers Europe, Presentation at DuPont, May, Dordrecht, The Netherlands Atofina, 2000, Re: 3M Phasing out of perfluorooctanyl chemistry, press release, 17/05/2000, Paris, France Belisle, J, 1981, Organic fluorine in human serum: natural versus industrial sources, Science, 212,1509-1510 Browne, A, 2000, Carpet spray cancer scare alert in US, Observer, available at w w w .o b server.co .u k /P rin t/0 ,3 8 5 8 ,4 0 3 3 5 0 3 ,00-html Clarke, T, 2001, FOC: it's everywhere, Nature, available at www.nature.com /nsu/nsu_pf/010322-6.htm l Giesy, JP, Kannan, K, 2001, Global distribution of perfluorooctane sulfonate in wildlife, Environ. Sci. Techno!., 3 5 ,1339-1342 Gilliland, FD, Mandel, JS, 1993, M ortality among employees of a perfluorooctanoic acid production plant, J. Occup. M ed., 35, 950-954 Gilliland, FD, Mandel, JS, 1996, Serum perfluorooctanoic acid and hepatic enzymes, lipoproteins, and cholesterol: a study of occupationally exposed men, Am. J. Ind. Med., 29, 560-568 Key, BD, Howell, RD, Criddle, CS, 1997, Fluorinated organics in the biosphere, Environ. Sci. Technol., 31, 2445-2454 Moody, CA, Field, JA , 1999, Determination of perfluorocarboxylates in groundwater impacted by fire-fighting activity, Environ. Sci. Technol., 33, 28002806 OECD, 2002a, Draft assessment of perfluorooctane sulfonate and its salts, ENV/JM /EXCH(2002)8, Paris, France OECD, 2002b, letter of M r. Visser to BIAC, 12 June, Paris, France Olsen, GW , Burris, JM , Mandel, JH , Zobel, LR, 1999, Serum perfluorooctane sulfonate and hepatic and lipid clinical chemistry tests in fluorochemical production employees, J. Occup. Environ. M ed., 41, 799-806 Renner, 2001, Growing concern over perfluorinated chemicals, Environ. Sci. Technol., 35, 7 ,154A-160A Taves, D, 1968, Evidence that there are two forms of fluoride in human serum, Nature, 217,1050-1051 TRP, 2002, Telomer Research Program, Presentation at DuPont, M ay, Dordrecht, The Netherlands USEPA, 2000a, United States Environmental Protection Agency, EPA and 3M , Press Release, 05/16/2000, available at www.ecco-lenox.com/newsrelsepa.htm USEPA, 2000b, United States Environmental Protection Agency, Phasing out a problem: Perfluorooctyl sulfonate (PFO S), presentation of Mrs. Dominiak , August USEPA, 2002, Draft hazard assessment of perfluorooctanoic acid and its salts, February 20, 2002, W ashington, D .C ., United States of America Wood, A , 2000, 3M to phase out PFOS, Chemical W eek, May 24, 2000 available at www.findarticles.com /m 3066/21_162/62927614/pl/artide.jhtm l Perfluoroalkylated substances - Aquatic environmental assessment ji 13 000350 Perfluoroalkylated substances - Aquatic environmental assessment V y, ' w 1 . - - o a s1 2 Physical-chemical properties 2.1 Identification Perfluoroalkylated substances (PFAS) is the collective name for a group of fluorinated chemicals, including oligomers and polymers. This group of chemicals comprises several hundreds of compounds (NCEHS, 2001), and can be divided into 23 categories (NCEHS, 2001). Important subsets are the (per)fluorinated organic surfactants and the fluorinated organic polymers. Category Substanctype - - < _ Number listed - : 1 Perfluoroalkyl sulfonates 18 2 Perfluoroalkyl sulfonyl derivatives 10 3 Perfluoroalkyl sulfonamides 60 4 Perfluoroalkyl sulfonamide alcohol derivatives 12 5 Perfluoroalkyl sulfonamide phosphate derivatives 6 6 Perfluoroalkyl sulfonamide glycine derivatives 6 7 Perfluoroalkyl sulfonamide polyethoxylate derivatives 7 8 Perfluoroalkyl sulfonamide aminopropyi derivatives 28 9 Perfluoroalkyl sulfonamide chromium complex derivatives 6 10 Perfluorocarboxylic acids 29 11 Fluorosulfonamides 1 12 Fluoroesters 5 13 Fluorothioethers 9 14 Fluorocarboxylates 3 15 Fluorourethanes 2 16 Fluoroalcohols 14 17 Fluoroacrylates 84 18 Fluorophosphates 8 19 Fluoroalcohol derivatives 5 20 Perfluorosulfonamide acrylate polymers 13 21 Fluoroacrylate polymers 10 22 Perfluoroalkyl and -alkoxy silanes 6 23 Perfluorophosphonics 4 Table 2.1. Categories of perfluoroalkylated chemicals (NCEHS, 2001) For many of these substances very few physical-chemical data are available. This study w ill focus on the most important commercial products, the primary production intermediates, and the major degradation products. PFAS can be produced via two distinct routes of synthesis: Simons Cell Electrochemical Fluorination (EC F), as used by 3M and Miteni, Tlomrisation, as used by among others Asahiglass, Atofina, Clariant, Daikin and DuPont. Perfluoroalkylated substances - Aquatic environmental assessment i t , 15 000352 The production processes will be discussed in the next chapter. The ECF process yields branched and straight chain perfiuorinated products with a sulfonyl group (see table 2 .1 , categories 1-9, 20). The products from telomerisation are not perfiuorinated, but have a linear perfluoroalkyl chain with an ethylene group followed by a functionalised group (see table 2.1, categories 12-19,21; see section 3 .2). The products that are produced via the two routes of synthesis have four major forms of appearance, being monomeric, homo-polymeric, co-polymeric and phosphates esters. The form of appearance is dependent on the application, with co-polymers as the one used most often. The majority of the fluorinated organic polymers are co-polymers of fluorinated acrylates. Table 2.1 shows that many different (per)fiuoroacrylates exist. The various applications and chemicals involved are described in more detail in chapter 3. The co-polymers of fluorinated acrylates possess surface modifying properties. Polymers exhibit an environmental behaviour totally different from low molecular weight compounds. Furthermore, very few properties are known of fluorinated organic polymers, including fluorophosphates. Therefore the polymers will be treated in a different way in this study. They will not be included in the table of primary study substances, but their production intermediates will be. Since the degradation products or production impurities from fluorinated organic polymers can be low molecular weight fluorosurfactants, these will be incorporated in this study. In commercial products the fluoroalkyl chain lengths can vary from four up to twenty carbon atoms. In general, most products have chain lengths of between six and ten. Most data are available on the chemicals with eight carbons. Therefore, this study will focus on the following products (see table 2 .2): PFOS PFHxS Perfluorooctyl sulfonate 1 Perfluorohexyl sulfonate 1 PFBS Perfluorobutyl sulfonate 1 PFOA Perfluorooctanoic acid 1,3 n -EtFO S E n-Ethylperfluoro- 2 octanesulfonamidoethanol Various salts Various salts 29420-49-3 Various salts 4W+Wr FF F F 0 --s-o " 0 FFF F FO F F SII - O - T FT F O FF 1691-99-2 F F F FO F F F F F F F FO || CH, CH, V >-- S--N F-- y F iFSsXF ' ^F V = F F F O0 \ H,--CH,--0--H Perfiuoroalkylated substances - Aquatic environmental assessment 16 000353 SS JP ction r ith ic Ived lar rs s i six H, -- O--- H n-MeFOSE n-Methylperfluorooctanesulfonamidoethanol 2 n -EtFO S EA n-Ethylperfluorooctanesulfonamidoethyl acrylate 4 24448-09-7 423-82-5 F ---- ! *v *-*''**'*ffi j SaLi r/VlT f FF FF F0 Il ----S -- \ \ F F Np F II fF NC -- C -- 0 -- H H, H, FF FF 0 n-MeFOSEA n-Methylperfluorooctane sulfonamidoethyl acrylate 3 ,4 n-EtFO SEM A n-Ethylperfluorooctane sulfonamidoethyl methacrylate 6:2 FTOH 1H,1H,2H,2Hperfluorooctanol 3 ,4 2 8:2 FTOH 1H.1H.2H.2Hperfluorodecanol 2 6:2 FTA 1H,1 H,2H,2H-perfluorooctyl acrylate 4 8:2 FTA 1H,1H,2H,2H-perfluorodecyl acrylate 4 6:2 FTMA 1H,1 H,2H ,2H-perfluorooctyl 4 methacrylate 8:2 FTMA 1H,1H,2H,2Hperfluorodecyl methacrylate 4 25268-77-3 376-14-7 FFF FIF|F F FI 0II / C H , J-- S -- hT F ---- F 1F fF | 1 F il c-- C -- O -- C -- C -- CH. H, H, || H F FFF 0 F F F FO H, IlF F I F I F / C -- CH, , ----S-- N rH F ---- F 1 F | F | F 0Il FFF c\ -- C -- 0 -- ---- M, H, || | 0 CH, 647-42-7 865-86-1 F FFH 17527-29-6 27905-45-9 F FFFH F_F F FF F-- F F FI F F F| F F F F F F H H f-- 1 F F FF F F F TH H 0 1 -s A O 2144-53-8 F FF FFF F-- F FI F F FF 1996-88-9 F F fr F 1F F I F F IH Lr n if- K| N F F f: F Tf F F - o -- c _-- ^Y CHj F 1 H 1 0 CH, Table 2.2. Primary study substances. * The selection criteria are (1) Most likely degradation product (2), Important production intermediate (3) Important commercial product (4) Important monomer for polymers 0 0 = 01 x o1 **iXlO 1 01 0 = 01 x Io fcIIoX Perfiuoroalkylated substances - Aquatic environmental assessment i.W * ' ' i 000354 17 The above-mentioned substances bear various names, but may generically be described as perfluoroalkylated substances (PFAS). Specific subclasses can be referred to as fluorinated organic surfactants, (per)fluorosurfactants, (per)fluorinated surfactants, perfluorinated chemicals or fluorochemicals. The terminology is explained in section 1.3. ECF-based products are sometimes referred to as `POSF-based' or 'POSF-related' substances, in contrast to fluorinated telomer-products. The products that are synthesised via telomerisation are also referred to as telomers. The commercial names for perfluoroalkylated substances can be found in table 3 .9. Fluorinated organic polymers are not to be confused with fluoropolymers (see section 1.3). 2.2 Physical-chemical characterisation Some of the substances in Table 2.2 are process intermediates, others are used themselves in formulations and some of these products only occur due to degradation processes. For the majority of these substances no physical-chemical properties are available. For the polymers no relevant data are available at ail. Furthermore, the reliability of some of the available data is doubtful. To evaluate the reliability of the data a Data Reliability Indicator (DRI) is used, as developed by Klimisch et al. (1997). In Annex II the methodology of the DRI is explained. In table 2.3 the available, reliable data are accumulated: Perfluoroalkylated substances - Aquatic environmental assessment 18 000355 PFOS (K*) 538.23 >400' 1" * 5.19 E-1" 1 3.31 E-4' 1 3.4 E-9 (calc.) 5.70 E-13 N.D. PFHxS 438.22 - -- -- -- -- PFBS 338.21 - -- - 5.1 E1b - -- PFOA (NH,,' ) 431.1 Sublimes at 130Cb Sublimes at 130Cb > 5.00 E2b <1.3 E-3b > 1.00 E26 - 9.2 E-36 <1.1 E-11 (calc) 7.8 E-11 (calc) n-EtFOSE 571.26 55-60' 2- - 1.51 E-48 1 5.04 E-1s 2 1.9 E-2 (calc) n-MeFOSE n-EtFOSEA 557.23 625.30 27-421" -2 150 at 1mm'" -2 8.9 E-41U -* 2- --- n-MeFOSEA 611.28 - -- -- -- -- n-EtFOSEMA 639.33 48-55" -- -- -- -- 6:2 FTOH 364.11 - - 88-95 at 28mm1z - 1.2-1.7 E-21J - - ~ 1 E-213 8:2 FTOH 464.12 49-51'' - 113 at 10mm1' - 1.40 E-413 - 2.931b - 9.6 E-213 6:2 FTA 418.16 - -- -- - -- 8:2 FTA 518.17 - - 90 at4mm,b -- -- -- 6:2 FTMA 432.18 - -- -- -- -- 8:2 FTMA 532.20 - - 120 at 4mm1' -- - - Table 2 .3 . Properties of selected fluorochemicals. a) DRI = Data Reliability Indicator (D 3M, 1999a (2) 3M, 2000 (3) 3M Reports, 1999 (4) 3M. 1999b (5) Miteni, 2002 (6) a p m e , 2002 (7) 3M, 1999c (8) 3M, 2001 (9) 3M, 1998, (10) 3M, 1996 (11) Fischer Scientific, 2001(12) ABCR, a (13) DuPont, 2002 (14) ABCR, b (15) TRP, 2002 (16) ABCR, c (17) ABCR, d. Calc = calculated. N.D. = not determined. Perfluoroalkylated substances- Aquatic environmental assessment 19 000356 2.3 References 3M, 1996, Determination of physico-chemical properties of sample D-1, Mitsubishi Chemical Safety Institute Ltd., Yokohama, Japan 3M, 1998, Determination of vapour pressure curve by dynamic method for U1463 (ET FO SE), St. Paul, Minnesota, United States of America I > r | ( 3M, 1999a, Determination of the melting point/ melting range of PFOS, Wildlife International, Easton, Maryland, United States of America 3M , 1999b, Determination of the vapour pressure of PFOS using the spinning rotor gauge method, W ildlife International, Easton, Maryland, United States of America t \ ! i 3M , 1999c, 3M Internal correspondence, Melting point of FM-3923 N-Ethyl FOSE Alcohol, St. Paul, Minnesota, United States of America 3M, 2000, Determination of the water solubility of PFOS by the Shake Flask Method, W ildlife International, Easton, Maryland, United States of America 3M, 2001, Characterization Study EtFOSE-OH, Test Control Reference #SE-035, Phase: solubility of EtFOSE-OH in water, methanol, and acetone, St. Paul, Minnesota, United States of America 3M Reports, 1999, The Science of Organic Fluorochemistry and Perfluorooctane Sulfonate: Current Summary of Human Sera, Health, and Toxicology Data, February 5 ,1 9 9 9 , St. Paul, Minnesota, United States of America j > i ABCR, a, Data sheet on 6:2 FTOH, available at www.abcr.de ABCR, b, Data sheet on 8:2 FTOH, available at www.abcr.de ABCR, c, Data sheet on 8:2 FTA, available at www.abcr.de ABCR, d, Data sheet on 8:2 FTM A, available at www.abcr.de APME, 2002, Association of Plastic Manufacturers Europe, Presentation at DuPont, May 2002, Dordrecht, The Netherlands DuPont, 2002, Presentation, May 2002, Dordrecht, The Netherlands Fischer Scientific, 2001, Material Safety Data Sheet for 2-(NEthylperfiuorooctanesulfonamido) ethyl methacrylate, Canada Klimisch, H-J, Andreae, M , Tillmann, U, 1997, A systematic approach for evaluating the quality of experimental toxicological and ecotoxicological data, Regulat Toxicol. Pharmacol., 2 5 ,1 -5 M iteni, 2002, Data submitted by M r. Mistrorigo, M iteni, Milano, Italy NCEHS, 2001, National Centre for Ecotoxicology & Hazardous Substances, Review of occurrence and hazards of perfluoroalkylated substances in the UK, A nonconfidential overview, Environment Agency, Wallingford, United Kingdom TRP, 2002, Telomer Research Program, Presentation at DuPont, M ay, Dordrecht, The Netherlands Perfluoroalkylated substances- Aquatic environmental assessment 20 ^00357 itsubishi U1463 ildlife ng ; of I FOSE 335, tane iPont, lew ht, 3 Production, Use & Emissions of PFAS in the Netherlands 3.1 Introduction PFAS are used in numerous applications. Because fluorinated surfactants are relatively expensive, they are only used when other products do not possess the specific requirements (Kissa, 2001). Perfluorinated surfactants have special physical and chemical properties, including chemical inertness, high thermal stability, low surface energy, hydrophobicity and oleophobicity (Smart, 1994; Kannan et al., 2001 ). These characteristics make them valuable compounds in several fields of application. The most important fields of application are (USEPA, 2002; NCEHS, 2001 ; DuPont, 2002): Carpet protection, Paper and board protection, Textile protection, Leather protection, Fire-fighting foams, Specialty surfactants, Polymerisation aid. The distribution over use categories in the Netherlands is not precisely known. A recent inventory of the use of PFAS in the United Kingdom, shown in table 3.1, shows the relative importance of the several categories in the UK. Table 3.1 also presents the breakdown in global application categories of the perfluorinated products of the 3M company. Carpet &Textile Treatment 48.8 Surface treatment 48 Paper & Board Treatment Speciality Surfactants 15.0 17.5 Paper protection 33 Performance chemicals 15 Fire-Fighting Chemicals 16.3 Fire-fighting foams 3 Chemical Intermediates 2.5 Table 3.1. Proportional breakdown of perfluorochemical use in the UK and global 3M production. From these data it is obvious that carpet and textile treatment constitute the major use category, probably followed by paper treatment. Although this breakdown may be different for the Netherlands, because of the difference in relative importance of industry branches from country to country, it is expected that at least some of these use categories will be important users of PFAS in the Netherlands. The applications and their corresponding emissions to the environment will be discussed in this chapter. Other applications such as herbicide, cosmetics, and electronics will not be discussed, because they are used in smaller quantities. Kissa (2001) reviewed most of the possible applications for fluorochemicals. Perfluoroalkylated substances- Aquatic environmental assessment 21 000358 Another possible source of fluorinated chemicals in the environment are the emissions from fluorochemical production sites. For all applications a few routes of emissions are possible. The emissions result from production, from use, from collected and uncollected waste after use (both monomeric and polymeric), as well as from waste treatments (incineration in a municipal waste incinerator, water purification in a waste water treatment plant (W W TP)). t 3.2 Production There are two major commercial production processes for PFAS: electrochemical fluorination (ECF) and tlomrisation. In the ECF process an organic compound is dissolved or dispersed in anhydrous hydrogen fluoride. A direct electric current is passed through the hydrogen fluoride, causing all the hydrogen atoms of the organic compound to be replaced by fluorine. The overall reaction is as shown in figure 3.2: O ll S - F + 17 h - F o 1-Octane sulfonyl fluoride F S - F + 17 H2 Perfluoro-1-Octane sulfonyl fluoride (P O SF) Figure 3.2. Exam ple of the EC F process In this process fragmentation of the alkyl chain can occur. Therefore, the products of this production process contain various impurities. The process, its products and its impurities are described more extensively in Annex III. W ith the ECF process also PFOA can be produced from octanyol chloride. Hydrolysis of the obtained perfluorooctanyol fluoride yields PFOA (see figure 3.3). Figure 3.3 Production of PFOA with the ECF process (Kissa, 2001) lodopentafluorethane In the tlomrisation process iodopentafluoroethane is reacted with n units of tetrafluoroethene CTFE); the reaction with 3 units is shown as an example in figure H Tetrafluoroethylene F IF F IF IF F FFF Perfluorooctyl Iodide HH Ethylene Figure 3.4. Exam ple of the tlomrisation process 3 .4 : This production process yields straight chains, with hardly any impurities, but the products are not fully perfluorinated. The ethylene group is characteristic for this production process. The process and its products are described more extensively in Annex III. 3.3 Use and emissions Many suppliers manufacture and market PFAS for a variety of applications. Until 3M decided to phase out their perfluorooctyl chemistry (3M , 2000a), they were the most important globed producer of PFAS. Recently DuPont bought the Perfluoroalkylated substances- Aquatic environmental assessment 22 0003SS lit )o th a ant cal us iced 7H :) lucts ; and 3.3). 1- HF gure _F h F IH ,, F 1H FH odecyt Iodide he iis y in fluorinated telomer division of Atofina (Atofina, 2002). Other important PFAS suppliers are Asahiglass (Japan), Daikin (Japan), Clariant (Switzerland) and Bayer (G erm any). The different commercial names for the products based on perfluoroalkylated substances of these suppliers are reported in table 3.9 at the end of this chapter. 3.3.1 Carpet protection Introduction Fluorinated surfactants are used to form a protective, soil repellent coating on carpets. The principle of soil repellence is based on the reduction of the surface energy of the fibre by the fluoroalkyl chains. These chains repel both water and oil. Therefore soil particles cannot enter the carpet. The mechanism is explained in figure 3.5: c f3 (C F 2),, (c h 2)2 o c=o c 2h 4r - CF3 (c f 2),, (C H 2) 2 o c=o c 2h 4r - CF3 (C F 2) n (C H 2) 2 o c=o c 2h 4r ///// FIBER SURFACEWWV Figure 3.5. Mechanism of carpet protection with fluorinated polymers (Tomasino, 1992). These soil repellent products for carpets are generally referred to as Scotchgard products, which is the brand name of the 3M product for this application. The commercial products for carpet protection contain approximately 15% fluoroalkyl acrylic polymers (Tomasino, 1992, 3M , 2000b, 3M , 2000c). Well-known products are Scotchgard (3M ), Zonyl (DuPont), Baygard (Bayer) and Foraperle (Atofina). In general these products are used as foam-applied emulsions for the finishing of the carpets (VN TF, 2002). Use figures The estimated use of fluorinated organic polymers in the carpet industry in the Netherlands is approximately 100 tonnes of products annually (VNTF, 2002). With an average of 15% fluorinated organic polymers this corresponds to 15 tonnes of fluorinated polymers. The amounts used are not at all constant; the (temporary) withdrawal of the 3M products of the market has an important influence on the fluctuations (see Table 3.6). Apart from carpet manufacturing in the Netherlands, also PFAS treated carpets are imported from foreign countries. For the total carpet industry 141 million m2 is produced in the Netherlands, 125 million m2is exported and 75 million m2 is imported (VN TF, 2001). Therefore in the Netherlands annually 91 million m2carpet is sold. For the production of these carpets approximately 65 tonnes PFAS-based products are used, with about 10 tonnes fluorosurfactants'. tj| ' 141-125 = 16 million mJ produced for the Dutch market. 75 million mJ imported makes 91 million mJ e used annually. It is assumed that production processes in foreign countries used approximately the same amount of PFAS for carpet protection. Therefore 91/141 * 100 tonnes makes 64.5 tonnes. 64.5 * 0.15 = 9.7 tonnes PFAS. Perfluoroalkylated substances- Aquatic environmental assessment '' v -*v 23 000360 Amount fluorinated organic polymer 102.4 136 80.9 based products used (tonnes) Table 3.6. Annual consumption of fluorinated organic polymer based products in the carpet industry in the Netherlands in 1999-2001. Em issions There are several possible routes of emission of PFAS from the use and consumption in the carpet industry. 1. Losses during application in the factory, 2. Wear from the carpet, 3. Emission of monomers from polymers, 4. Emissions from reapplication on fixed carpets, 5. Emissions from the waste phase. Ad 1) In the carpet factory the fluorosurfactant-based finishing is applied and the carpet is dried afterwards. From that application emissions may occur: these cannot be quantified in this study, because emission factors are not known (GuT, 2002). Ad 2) The durability of the protective PFAS layer on carpets has been studied. ' f..] it is expected that 50% o f the FC [fiuorochemical] treatment will be removed over the nine-year life of the carpet due to walking and vacuuming, while an additional 45% o f the FC treatment will be removed in steam cleaning throughout the carpet life (3M , 2000d).' These percentages vary with products of different producers (DuPont, 2002). The wear of the protective layer with a corresponding emission of fluorinated organic polymers to the environment does not necessarily lead to the emission of PFAS. The degradation of fluorinated organic polymers is not known (see section 4.4.4). In a worst case estimate it might be assumed that all the polymer degrades to form PFAS and that 95% of the polymer is removed. On carpets that are used in the Netherlands, 10 tonnes of fluorinated organic polymers are applied. Therefore 9.5 tonnes of PFAS may be released to the environment, due to wear of carpet protection polymers. Ad 3) The use of fluorinated organic polymers may lead to the emission of PFAS to the environment via a direct or indirect route. The direct emission of PFAS is due to impurities in the products. During the various steps of the production process, used to form functionalised products, reaction impurities are formed. The impurities represent 1-2 percent of the total production volume and will be present in the finalised product (3M , 2000e). The impurities will also be present in the monomers used for manufacturing of the polymers. It is very likely that the impurities will not polymerise. Whether the impurities will be present in the polymer as monomer is not clear. If they are, it is possible that they will be released from the polymeric product after its application to the carpet. Secondly, polymerisation is often not a fully efficient reaction. A small part of the monomer will not react and w ill be present in the final product as a low level residual (3M , 2000f). The monomers have a composition different from the impurities. They may also be released from the product, leading to the emission of fluorinated functionalised products. The indirect route of emission of PFAS from polymers originates from PFAS that are not present in the polymer. Physical or chemical degradation may lead to the formation and subsequent emission of PFAS from the polymer. Fluorinated organic polymers are said to be stable (3M , 2002; Bayer, 2002), but the degradation to PFAS has not been studied. A laboratory test with a polymeric PFAS treated tablecloth confirmed the release of monomers from a polymeric application. An extraction at moderate temperature Perfluoroalkylated substances- Aquatic environmental assessment 24 000361 and e jT, died. oved s of es orm 9.5 f : AS he sent sed e of me of (60 C) with an organic solvent showed the possible leakage of perfluorinated monomers from the treated tissue. The origin (direct or indirect) of the PFAS was not studied (Jonkers et al., 2002). If a worst-case estimate is made, all the fluorinated polymers can be degraded or transformed to form PFS. As was calculated above, this may lead to the emission of 9.5 tonnes of perfluorinated surfactants. This is the worst-case estimate of ad 2 and 3 together. Ad 4) Carpets that have been treated with fluorochemicals are sometimes re treated. This can be done after cleaning by professional carpet cleaners, or by consumers, with spray applications. The consumer application does not appear to be an important application in the Netherlands. A short survey with carpet shops showed that fluorochemical protection sprays were not available (Alto, 2002; Carpetland, 2002; NTU, 2002; ITC, 2002). Carpet cleaners do use fluorochemical- based products for the application of a new protective layer (Chem-dry, 2002). This could lead to emissions. Neither the use, nor the emissions from this application could be quantified in this study. Ad 5) Carpets that are disposed off after use w ill be added to the general waste stream. If the carpet cannot be recycled, it will be combusted or landfilled. In the Netherlands most of the non-recydable waste is combusted (5 2 % ), and an important amount of the waste is landfilled (39% )(M ilieuloket, 2001). Bond- energy calculations predict that combustion will lead to the destruction of PFAS (3M , 2001a; 3M , 2001b). In the leachate of landfill, PFOS and PFOA have been detected (3M , 2001c). The landfill of PFAS treated products may lead to the emission of PFAS to the environment. The estimation of emissions of PFAS from the use and consumption in the carpet industry appears to be complicated. The worst-case estimate for emissions of PFAS from carpets that are used in the Netherlands is 9.5 tonnes. The treatment with sprays for re-application is not taken into account. These 9.5 tonnes have been applied in polymeric form and could be released by five different ways. Quantitative information about degradation and transformation of fluorinated organic polymers is the most important remaining question, with a possibly high influence on the worst -case estimate given. 3.3.2 Paper and board protection Fluorinated chemicals are used in the paper industry to produce water and greaseproof paper. Among others, this paper is used for the wrapping of snacks, cookies and petfoods (Niermans, 2002; Pfleiderer, 2002; Proost & Brand, 2002). This type of material is generally referred to as Ersatz paper. The products that are used for this application are generally based on fluoroalkyl phosphates (3M , 1999a; Kissa, 2001; NCEHS, 2001). Proofing of paper does not take place in the Netherlands. The majority of this grade of paper that is present in the Netherlands is imported from Germany and Scandinavia (Niermans, 2002; Proost & Brand, 2002). The main suppliers of fluorochemicals in the paper industry are 3M , Atofina, Bayer, Ciba, Clariant and DuPont with respectively the following products: Scotchban, Foraperle, Baysize-S / Baysynthol, Lodyne, Cartafluor and Zonyl (Pfleiderer, 2002). Use figures No production of this grade of paper or board is known in the Netherlands (VNP, 2002). A market survey in 2000 estimated that in the Netherlands between 6000 and 7000 tonnes of Ersatz paper is used annually (Niermans, 2002). It is estimated that for these types of paper 1.0-1.5 % (based on the dry weight of the fibre) fluoroalkyl phosphate is needed (Kissa, 2001), corresponding to 60-105 tonnes of fluoroalkyl phosphate. Perfluoroalkylated substances- Aquatic environmental assessment 25 000362 Em issions Emissions of PFAS due to the use of Ersatz paper are from migration out of the paper to the wrapped product (DuPont, cited in NCEHS, 2001), and emissions from paper manufacturing plants in adjacent countries. The emissions from factories are believed to be very small (3M , 2000d). Another source of emissions is the cutting waste in the paper converting industry, leading to solid waste of PFAS treated paper. In the waste phase used paper may also lead to the emission of PFAS. During incineration all PFAS will be destroyed, but leachate from landfills may lead to emissions to the soil and water (see section 3 .3 .1 , 3M , 2001c). Quantitative data are not available for these type of emissions. 3.3.3 Textile protection Fluorinated chemicals are used extensively in the textile industry and by private consumers. The application is similar to that in the carpet industry. The products used are polymers, based on fluorinated acrylates and methacrylates, and are referred to as fluorcarbon (Lakatex, 2002). The goal of the application of fluorinated chemicals is to provide water, oil, soil, and stain repellence (NCEHS, 2001). Textiles that are used for i.e. tablecloth, upholstery, rainproof clothing and bed linen are treated with these protective chemicals. There are two stages in the textile production process that use fluorcarbon, both intended to form a fluorinated coating. Use figures The textile industry in the Netherlands comprises many small and medium enterprises. Some of these companies use fluorosurfactants in their manufacturing process. Because the industry is scattered and public data are neither available from the Vereniging Textielindustrie Nederland (Dutch Assocation for the Textile Industry, VTN, 2002), nor from the European Apparel and Textile Organisation (Euratex, 2002), it is not possible to estimate the use of fluorochemicals in the Dutch textile industry. For these applications approximately 2.0-3.0% (of the fibre weight) perfluorochemicals are necessary to obtain the water repellence (Kissa, 2001). However, the total amount of waterproof textile fabricated is not known. In the United Kingdom, textile and carpet applications together contribute for 48.8% of the fluorochemical active ingredients (NCEHS, 2001). It is likely that this industry branch in the Netherlands uses considerable amounts of fluorochemicals. Textile chemicals are obtained from various manufacturers. Information from stakeholders indicates that Bayer, DuPont, 3M and Daikin are the most important suppliers and have all together a market share of approximately 90% (VTN, 2002; B.L.W . Visser, 2002). Unfortunately, sales figures are not available from the suppliers. Emissions There are five possible routes of emissions of PFAS from the use in the textile industry and consumption: 1. Losses during application in the factory, 2. W ear from the textile, 3. Emissions of monomers from polymers, 4. Emissions during reapplication to textiles, 5. Emissions from the waste phase. Ad 1) The treatment of textiles with fluorinated chemicals in the factory leads to the emission of fluorinated polymers. There is an emission of fluorinated chemicals present in the cut-offs as solid waste. This is a very small percentage of the textile production (Lakatex, 2002). These two emissions together are estimated to form approximately 10 percent of the fluorinated chemicals used (3M , 2000d). Perfluoroalkylated substances--Aquatic environmental assessment f;' ,'.a, t ' J . > 26 000363 of the usions m ndustry, ring d to ve data 'ivate Jducts are , soil, :h, ive cturing ble rextile tion :he 1). ) the 3% of ustry n Dftant 2002; leads e of nated Od). Ad 2) The fluorinated coating on textiles is vulnerable to wear. During the lifetime of the product a considerable part of the fluorinated polymer will be removed, analogous to the wear from carpets. For textiles the intensive washing may increase the amount of the coating that is lost to the environment. This emission has not been quantified. A worst-case approximation would estimate that 100 percent of the applied fluorochemicals are released to the environment. Ad 3) The use of polymers may lead to the emission of monomers. Both product impurities and non-polymerised monomers may be a source of PFAS to the environment. This is extensively discussed for the application to carpets in section 3.3.1 and is analogously valid for the textile applications. Additionally the intensive washing of textiles may lead to the emission of monomers. In a worst- case estimation it is suggested that all the polymers degrade to form PFAS. Ad 4) On the consumer market several products are available to improve water and grease proofing of textiles. These products are available as sprays and wash-ins. Some of these products contain fluorochemicals (Bever, 2002; Denig, 2002; Grangers, 1997; Grangers, 1998). Although sales of these products are said to be considerable, no estimation of the market can be made. Both types of (re-) application of fluorinated coatings may lead directly to emissions to the environment. 3M (2001) estimated that 34% of the product that is expelled from a spray is lost to air. Evidently, the part of the wash-in application that is not properly attached to the fibre will be emitted to the sewer. It might be assumed that all the fluorinated organic polymers that are used for the protection of textile on the consumer market are released to the environment. Possible emission routes are emissions during applications and wear of the protective layer. If this worst case estimation is continued it is assumed that all the emitted fluorinated organic polymers degrade to form PFAS. Ad 5) Textiles that are not recycled will be combusted or landfilled. Presumably, combustion w ill lead to the destruction of monomeric and polymeric PFAS, whereas landfill may lead to the emissions of PFAS to the environment (see section 5.3). 3.3.4 Leather protection Perfluoroalkylated substances are used for the treatment of leather. The main function is to provide waterproofing. For this application polymeric fluorochemicals are used (Kissa, 2001). The water repellents are used in the finishing process. W ater repellent consumer sprays are also available for leather products. Use figures The Dutch Federation of Tanneries (FN L, Federatie van Nederlandse Lederfabrikanten) is currently executing an inventory of the use of various products in the leather industry. Fluorinated chemicals are incorporated in this survey. Results are forthcoming (FN L, 2002). According to Kissa (2001), concentrations of fluorochemical in leather industry products are very low (0.025-0.05% on leather w eig h t). Furthermore, much of the leather used in the Netherlands is imported, and much of the produced leather is exported. In 1998 the production of leather in the Netherlands was approximately 7 million m2, export was 5 million m2, and import was 3 .6 million m2(FN L, 2000). The average mass of leather is approximately 6 kilograms per m2 (U N IDO , 2000). If we assume that all the leather has been treated with 0.025-0.05% PFAS (being a worst-case estimate), the total use in the Dutch leather production industry would be 10 - 20 tonnes of polymeric PFAS. The corresponding total consumption of PFAS for leather that is used in the Netherlands amounts to 8.4-16.8 tonnes3. 2 7 E6 m2 - 5 E6 m2 + 3.6 E6 m2 - 5.6 E6 m2. 5.6 E6 m2 * 6 kg/m2 - 33.6 E6 kg. 33.6 E6 kg *0.025% = 8.4 tonnes. 33.6 E6 kg *0.0 5 % * 16.8 tonnes. Perfluoroalkylated substances- Aquatic environmental assessment 27 000364 Emissions No emission estimates have been made for this branch of industry. Emissions are possible from the application in the tannery, from fluorinated chemicals on leather waste and wear from leather during use. Land filling of leather waste may lead to the emission of PFAS to the environment. Furthermore, the spraying of leather might lead to direct emissions of PFAS to the environment. 3.3.5 Fire-fighting foams Introduction Flammable liquid fuel fires form a serious threat to life. Aqueous film forming foams (AFFF) were developed in the 1960s as fire-extinguishing agent for this type of fires (Moody and Field, 2000). The AFFF, when mixed with water and air, provides a fire-extinguishing film consisting of a foam. PFAS contribute to the performance of AFFF, but comprise only a relatively small fraction of the formulation (0.5-1.5% , Moody & Field, 2000; 3M, 1999b; Solberg Scandinavian, 2001). For this application monomeric perfluorinated salts are used (Moody & Field, 2000). A detailed description of the mechanism of fire-fighting foam can be found in annex IV. In the Netherlands no foam-forming agents are produced; these are imported (Luttmer, 1998; Ajax, 2002). The use of foam-forming fire extinguishers can be divided in two groups: 1. Mobile fire extinguishers, 2. Stationary fire-fighting systems. The first group comprises the mobile hand-held extinguishing equipment; the second group comprises stationary fire-fighting systems. The latter may contain large stocks of foam-forming concentrate. Mobile fire extinguishers Three types of mobile fire extinguishers exist, of which foam-forming extinguishers are becoming more and more important (Ajax, 2002): Powder, - Carbon dioxide, Foam. The last few years more environmentally friendly mobile foam fire extinguishers have been introduced, and a Dutch certification scheme `Milieukeur" has been established. There are two suppliers that have products that comply with the scheme (M ilieukeur, 2002). These extinguishers contain little or no PFAS and have a large market share with at least one supplier; this company sells approximately 95% so-called 'Eco-foam' (Ajax, 2002). Use figures It is estimated that in the Netherlands annually 150,000 mobile foam fire extinguishers are sold, with an average size of 6 litres (Ajax, 2002). For these extinguishers 54,000 litres foam forming concentrate is used annually, with 0.51.5% perfluorinated chemicals, corresponding to 270-810 kg PFAS. Due to the use of eco-foam this use has diminished with approximately 50% (135-405 kg PFAS). Apart for new extinguishers, an important part of the foam concentrate is used for the refilling of used extinguishers and for the standardised five-yearly revision. No data are available for the estimation of quantities of this application. Perfluoroalkylated substances- Aquatic environmental assessment i ' '> ' ' 28 000365 ms are | leather lead to >to the ig -his type small olberg : used 'ting ;d i be e :ain Jishers rs l have )ly 5e use \S). i for No I Em issions There are two important emissions due to the use of fire-fighting foam in mobile equipment: the emission during use and the emission from the disposal of old filling when refilled. Both are non-controlled (Ajax, 2002). The emission during use, for both training and real accidents is inevitable. Dependent on the place of fire, the fire-fighting foam, with the PFAS, is emitted to the environment. Foam extinguishers have to be refilled every five year. Although presumably not all extinguisher owners do follow this standard, most of the equipment is refilled. On revision the entire filling has to be replaced with a new one. The old filling, with diluted foam-forming concentrate, is disposed to the sewer and treated in a sewage treatment plant. From an environmental monitoring study (3M , 2001c) it is known that PFOS is still present in the W W TP effluent. Moody & Field (2000) state that analytical methods are not accurate enough to estimate the removal efficiency for fluorinated surfactants. Furthermore, the use of AFFF may lead to problems at the W W TP. Excess foaming may occur from large discharges of AFFF. Other constituents of AFFF may lead to significant higher BODs and CODs (Moody & Field, 2000). A worst-case approximation would estimate the release to the environment of all the AFFF purchased. This would lead to the emission of 135-810 kilograms PFAS annually, without the PFAS used for the refilling of fire-fighting equipment. Stationary fire-fighting systems Five types of fire-fighting agents are available for stationary systems (Ajax, 2002): Extinguishing powder Extinguishing gas (C 0 2, Argon) Protein foam Fluoroprotein foam Synthetic foam For these applications no eco-foam is available so far. Many standards have been set for these systems, including various tests; the eco-foam concentrate has not been subjected to these tests (Ajax, 2002). In contrast with the mobile fire extinguishers, the emissions from stationary systems are much more controlled by regulation. Foam-forming concentrate, which has expired is not disposed to the sewer, but has to be collected and transported to a waste incineration plant. It was not possible to retrieve disposal data (LM A, 2002). Use figures At this moment no data for the total use are available. In the Royal Dutch Air Force approximately 3,200 litres AFFF concentrate are used for calamities or prevention annually. These are emitted to the environment. Until 2000 another 2,800 litres AFFF concentrate was used annually for fire-fighting training. Nowadays water is used for training (Koninklijke Luchtmacht, 2002). The fire brigade of Amsterdam International Airport Schiphol, used AFFF for training facilities until December 2001. Nowadays they train with water. The last use of AFFF in non-military aviation in the Netherlands for calamities was in 1998. The current annual use is estimated to be close to zero. The stock of AFFF at Schiphol Airport is about 1200 litres, the filling in the equipment excluded (Schiphol Airport Fire Brigade, 2002). A large conglomerate of companies in the Rotterdam Harbour Area `Rijnmond' has an annual substitution of expired AFFF of 75,000 litres concentrate. For the protection of the newly constructed railroad route `BetuweUjn' 150,000 litres of AFFF concentrate was purchase by the Dutch government (Ajax, 2002). The latter is an incidental purchase and is not characteristic for the normal annual sales. Perfluoroalkylated substances- Aquatic environmental assessment vr ' * - 29 000366 Calculated guesses estimate an order of magnitude of 200 tonnes of concentrate bought annually with 0.5-1.5% PFAS, equivalent to 1.0-3.0 tonnes of PFAS. Em issions The use of foam-forming concentrate for the extinction of fires obviously leads to the emission of PFAS to the environment, dependent on the location. The collection of emissions from stationary systems is regulated. Most indoor locations are obliged to have a collection system for used fire-fighting foam. For many applications this is not possible; fire extinction will then lead to PFAS emission (A jax, 2002). Well-known examples are an accidental release at the International Airport of Toronto, Canada and use of AFFF on fire-fighting training sites (Moody & Field, 2000; Moody et al., 2002). Since 2000, PFAS containing fire-extinguishing agents are no longer used in Dutch military air force training sites (Koninklijke Luchtmacht, 2002). AFFF concentrate has a long lifetime. If this lifetime has expired, the AFFF can be disposed as chemical waste, and is incinerated (Ajax, 2002). Incineration will presumably lead to the destruction of PFAS. A worst-case approximation would estimate the release to the environment of all the AFFF purchased. This would lead to the emission of 1-3 tonnes PFAS annually. 3.3.6 Specialty surfactants PFAS are used as surfactants in various industrial applications. In total this group comprises a considerable amount of the PFAS used, but it consists of various low volume applications. In the United Kingdom these applications accounted for 17.5% of the use of fluorinated chemicals as active ingredient (NCEHS, 2001). No generally valid remarks can be made on the separate use figures and possible emissions. 3.3.7 Polymerisation aid For the production of fluoropolymers, such as polytetrafluoroethylene (PTFE) a polymerisation aid is necessary. PFOA, or APFO (ammonium perfluoro-octanoate), improve physical properties of the polymer and increase the rate of polymerisation (Klssa, 2001). Use figures In the Netherlands only one production plant for fluoropolymers is present, where more than one ton PFOA Is used annually (DuPont, 2002). In 1999 the worldwide use was 213 tonnes PFOA annually (APM E, 2002). Emissions The emissions from this application have been studied by the Association of Plastic Manufacturers Europe (APM E). The global mass balance for polymerisation aid for fluoropolymers is shown in table 3.7. This table shows that 77% of the PFOA may be emitted to the environment, via emissions from the plant or from products. Emitted 61 W ater 65 Air 23 Land 12 Reprocessed 14 In products 16 Destroyed 7 Table 3.7 Emission routes of PFOA in fluoropolymer production (APM E, 2002) Perfluoroalkylated substances- Aquatic environmental assessment 'r ? " f 30 V .O O J6 7 ntrate S. ?ads to rations y in tional Aoody Dutch in be of all lually. oup low ). No a oate), ation here wide astic ! for nay ) 3.3.8 Production sites In the Netherlands no PFAS is produced. The nearest production plants are situated in Antwerp, Belgium (3M ), and Villiers-St-Paul, France (presently Atofina, in the near future DuPont (Atofina, 2002. It is possible that emissions occur from these sites, resulting in the presence of PFAS in the Netherlands, either by aerial or riverine transport. Environmental monitoring has been executed upstream and downstream of a river to which the effluent of a fluorochemical production site is discharged in Decatur, Alabama, USA (3M ). This study pointed out that `effluent from a fluorochemical manufacturing faculty may be one route of introduction in the environment of some environmentally prevalent organic fluorochemicals (Hansen et al., 2002).' Moreover, preliminary results of an environmental monitoring study revealed elevated concentrations of PFOS in aquatic organisms downstream of a manufacturing plant in Antwerp, Belgium (Van de Vijver et al., 2002). 3.3.9 Other sources Apart from other uses with corresponding possible emissions, one study revealed the formation of perfluorinated chemicals by thermolysis of fluoropolymers, such as PTFE. Possible products were longer chain polyfluoro (C3-C14) carboxylic acids (Ellis et al., 2001). A major producer of fluoropolymers questions the reliability of these results (DuPont, 2002). 3.4 Summary of use figures and emissions In table 3.8 the use figures from the preceding sections are summarised. It becomes clear that the major application is in paper and paper board, followed by carpet, leather and presumably textile and specialty surfactants. For the latter two no reliable data are available. Data from the UK suggest that these two applications take an important share of the PFAS use. To estimate the emissions from use in the carpet, textile and leather industry a worst case calculation was used. Hence, it was assumed that all the fluorinated organic polymer degrades to form PFAS. Also for fire-fighting foam a worst case estimate of 100% was made. From the use as polymerisation aid about three quarters of the used PFOA may be emitted. Carpet 15 Polymers 10 (worst case) Paper & Board 60-105 (not in NL) Phosphates ? Textile N.A. Polymers 100% of the applied polymers Leather 10-20 Polymers ? Fire-fighting foams (mobile) 0.13-0.81 Monomers 0.13-0.81 (worst case) Fire-fighting foams (stationary) 1.0-3.0 Monomers 1.0-3.0 (worst case) Specialty surfactants N.A. Monomers ? Polymerisation aid >1 Monomers >0.77 Table 3.8. Use and emissions of PFAS in the Netherlands. N.A. = not available Perfluoroalkylated substances- Aquatic environmental assessment *V-' jh\' #v%'-' 000368 31 3.5 Overview of commercial names All suppliers use different names for the same type of products. Not all suppliers offer products for all applications. This overview is not complete, but contains all major suppliers for the Dutch market. Carpet Scotchgard Baygard Paper & board Textile AFFF Leather Specialty surfactants Polymerisation aid Scotchban Baysize-S, Baysynthol Foraperie FC brand textile Baygard-K AFFF - Scotchgard Xeroderm Various commercial names per supplier No commercial names Table 3.9. Commercial names of PFAS products Lodyne Oleophobol - Cartafluor Pekophob - Zonyl Asahiguard Unidyne 000363 Perfluoroalkylated substances - Aquatic environmental assessment 32 3.6 References 3M , 1999a, Material Safety data sheet of FC-3175 Scotchban Brand Paper Protector, St. Paul, Minnesota, United States of America 3M , 1999b, Material Safety data sheet of FC-603F 3M AR-AFFF 3% , St. Paul, Minnesota, United States of America 3M , 2000a, 3M Phasing out some of its specialty materials, available at www.3m .com /profile/pressbox/2000Jndex.jhtm l 3M , 2000b, Material Safety data sheet of FC-3611 Scotchgard Brand Carpet Protector, St. Paul, Minnesota, United States of America 3M , 2000c, Material Safety data sheet of FC-3615 Scotchgard Brand Carpet Protector, St. Paul, Minnesota, United States of America 3M , 2000d, Sulfonated perfluorochemicals: U.S. release estimation - 1997. Part 1: Life-cycle waste stream estimates, Final report, Battelle Memorial Institute, Columbus, Ohio, United States of America 3M , 2000e, letter of William A. Weppner to Dr. Hernandez, USEPA, April 28, 2000 3M , 2000f, Voluntary Use and Exposure Information Profile rr{ Perfluorooctanesulfonyl fluoride (POSF), St. Paul, Minnesota, United States of America. 3M , 2001a, Fluorochemical decomposition processes, W illiam R. W iley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington, United States of America 3M , 2001b, letter from Focus Environmental Inc., to Mrs. Schnobrich on thermal stability of perfluorinated alkyl sulfonyl compounds, Knoxville, Tennessee, United States of America 3M , 2001c, Environmental Monitoring - M ulti-City Study. W ater, Sludge, Sediment, POTW Effluent and Landfill Leachate Samples. Executive Summary, 3M Environmental Laboratory, St. Paul, Minnesota, United States of America 3M , 2002, personal communication with Dr. Sinnaeve, European toxicological manager, Antwerp, Belgium Ajax, 2002, interview with M r. Kamphuis, EHS manager (Ajax fire), M r. Hovers, senior sales engineer (Ajax Fire Protection Systems), April, 2002, Amsterdam, The Netherlands Alto, 2002, interview with sales manager, Amsterdam, The Netherlands, APM E, 2002, Association of Plastic Manufacturers Europe, Presentation at DuPont, May 2002, Dordrecht, The Netherlands Atofina, 2002, TotalFinaElf to sell its fluorinated telomers business to DuPont, press release of 30 April, 2002, available at w w w .atofina.com .groupe/gb/com m /detail.cfm ?ID = 6882 B.L.W . Visser, 2002, Interview with sales manager, Enschede, The Netherlands Bayer. 2002, personal communication with Dr. Sewekow, European Toxicological Manager, Leverkusen, Germany. Bever, 2002, interview with general manager Amsterdam, Amsterdam, The Netherlands Carpetland, 2002, interview with general manager Amsterdam, Amsterdam, The Netherlands Chem-dry, 2002, information from website www.chem-dry.nl Denig, 2002, interview with general manager Amsterdam, Amsterdam, The Netherlands Perfluoroalkylated substances - Aquatic environmental assessment Perfluoroalkylated substances - Aquatic environmental assessment 000370 33 DuPont, 2002, Presentation, May 2002, Dordrecht, The Netherlands Ellis, DA, Mabury, SA, Martin, JW , M uir, DCG, 2001, Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment, Nature, 412, 321-324 Euratex, 2002, interview with Roberta Adinolfi, responsible for Textile and Clothing Information Centre, Brussels, Belgium FNL, 2000, Federatie Nederlandse Lederfabrikanten, annual report 1999, available at http://www.lederfabrikanten.nl/download/Jaarverslag99.doc FNL, 2002, Federatie Nederlandse Lederfabrikanten, personal communication with Mr. Bonten, secretariat, Tilburg, The Netherlands Grangers, 1997, Material Safety Data Sheet for `extreme waterproofing for synthetics - wash-in', Alfreton, Derbyshire, United Kingdom Grangers, 1998, Material Safety Data Sheet `extreme waterproofing for naturals wash-in', Alfreton, Derbyshire, United Kingdom GuT, 2002, Gemeinschaft umweltfreundlicher Teppichboden e .V ., personal communication with Dr. Vankann Hansen, KJ, Johnson, HO, Eldridge, JS, Butenhoff, JL, Dick , LA, 2002, Quantitative Characterization of Trace Levels of PFOS and PFOA in the Tennessee River, Environ. Sci. Technol., 3 6 ,1681-1685 ITC, 2002, Interview with the general manager, Amsterdam, The Netherlands Jonkers, N, Krap, L, de Voogt, P, 2002, Optimisation of analytical methods for surveying the occurrence of perfluorinated surfactants in various matrices, poster presentation at SETAC Europe 2002, Vienna, Austria Kannan, K, Franson, JC , Bowerman, W W , Hansen, KJ, Jones, PD, Giesy, JP, 2001, Perfluorooctane sulfonate in fish-eating water birds including bald eagles and albatrosses, Environ. Sci. Technol., 35, 3065-3070 Kissa, E, 2001, Fluorinated surfactants and repellents, 2nd edition, revised and expanded, Marcel Dekker, Inc. New York, USA Koninklijke Luchtmacht, 2002, Letter and telephone conversation with Major De Ruyter, May 2002, The Hague, The Netherlands Lakatex, 2002, Interview with Leon Elfring, coating specialist, Goor, The Netherlands LM A, 2002, Landelijk Meldpunt Afvalstoffen, personal communication with Mrs. Meyer, Lelystad, The Netherlands Luttmer, W J, 1998, Waterbezwaarlijkheid van blusschuimen (in Dutch), RIZA, Lelystad, The Netherlands Milieukeur, 2002, Certificatieschema blusschuimen voor blusinstallaties, Stichting Milieukeur, The Hague, The Netherlands Milieuloket, 2001, information from website, www.milieuloket.nl Moody, CA , Field, JA , 2000, Perfluorinated surfactants and the environmental implications of their use in fire-fighting foams, Environ. Sci. Technol., 34, 38643870 Moody, CA, M artin, JW , Kwan, W C , M uir, DCG, Mabury, SA, 2002, Monitoring Perfluorinated Surfactants in Biota and Surface W ater Samples Following an Accidental Release of Fire-Fighting Foam into Etobicoke Creek, Environ. Sci. Technol.-, 36, 545-551. NCEHS, National Centre for Ecotoxicology & Hazardous Substances, 2001, Review of occurrence and hazards of perfluoroalkylated substances in the UK, A nonconfidential overview, UK Perfluoroalkylated substances - Aquatic environmental assessment 34 000371 Available on with turis - inessee ds for oster 2001, d id r De Mrs. ing 4ing view Niermans, 2002, personal communication with Mr. Klein-Swormink, sales manager, Castricum, The Netherlands NTU, 2002, interview with sales manager, Amsterdam, The Netherlands OECD, 2001, Organisation for Economic Co-operation and Development, Draft assessment of perfluorooctane sulfonate and its salts, July 2001 version , Paris, France Pfleiderer, 2002, telephone conversation with Mr. Augustin, general manager, Tiesnach, Germany Proost & Brand, 2002, telephone conversation with Ms. Stengs, product manager, Diemen, The Netherlands Schiphol Airport Fire Brigade, 2002, telephone conversation with Mr. Geerdink, operational services, Schiphol Airport, The Netherlands Smart, BE, 1994, Characteristics of C-F systems, in Banks, RE et al. (Ed.), 1994, Organofluorine chemistry: principles and commercial applications, Plenum Press, New York, USA, Chapter 3 Solberg Scandinavian, 2001, Several MSDSs of arctic foams, different concentrations, received on demand from M r. Ladehaug, production manager, solscand@online.no Tomasino, C , 1992, Chemistry & technology of fabric preparation & finishing, Department of textile engineering, chemistry and science, College of textiles, North Carolina state university, USA UNIDO, 2000, United Nations Industrial Development Organisation, Mass balance in leather processing, US/RAS/92/120 USEPA, 2002, United States Environmental Protection Agency, Perfluoroalkyl Sulfonates; Final Rule and Supplemental Proposed Rule, Federal Register, Volume 67, No. 47, Washington, DC, United States of America Van de Vijver, K, Hoff, P, Van Dongen, W , Esmans, E, Blust, R, De Coen, W , 2002, PFOS in marine and estuarine organisms from the Belgian North Sea and Western Scheldt estuary, poster presentation at SETAC Europe 2002, Vienna, Austria VNP, 2002, Vereniging van Nederlands papier- en kartonfabrieken, interview with general secretary, Hoofddorp, The Netherlands VNTF, 2001, Vereniging van Nederlandse Tapijtfabrikanten, production data Dutch carpet industry, available at www.tapijtnet.nl/indu/indu.htm l VNTF, 2002, Vereniging van Nederlandse Tapijtfabrikanten, inventory of use of perfluorinated surfactants in the Dutch carpet industry, Arnhem, The Netherlands VTN, 2002, Vereniging Textielfabrikanten Nederland, interview with general secretary, VeenendaaJ, The Netherlands Perfluoroalkylated substances - Aquatic environmental assessment 000372 35 Periluoroalkylated substances - Aquatic environmental assessment 36 000373 4 Behaviour in the aquatic environment 4.1 Introduction The behaviour of organic micropollutants in the aquatic environment is determined by the properties of the compound (solubility, bydrophobicity, volatility) and by the characteristics of the water system of concern (residence time of the water, sedimentation area, organic matter content, etcetera). These compound and system properties also determine to what extent a compound will accumulate in organisms. 4.2 Solubility and volatilisation The water solubility of a compound is a good indication of the extent to which the compound will be transported with water. In general, poorly soluble compounds have a high affinity for the organic matrix of silt particles in a water system. Solubility and vapour pressure determine together whether a compound will evaporate out of the water. The volatility of a compound is characterised by its Henry constant (H). Since no Henry constants were available for PFAS, they have been calculated from the values for solubility and vapour pressure (Van Leeuwen & Hermens, 1995). For PFAS there is a large variation in solubilities, vapour pressures and Henry constants (see table 4 .1 ). Substances for which no data were available are excluded from table 4.1. PFOS (K+) 5.19 E-1 3.31 E-4 3.4 E-9 PFBS 5.1 E1 N.A. - PFOA (H+) 9.5 7.0 E1 4.6 E-6 PFOA (NH4+) > 5.00 E2 < 1.3 E-3/9.2 E-3 <1.1 E-11/ 7.8 E-11 n -EtFO S E 1.51 E-4 5.04 E-1 1.9 E-2 n -EtFO S EA 8.9 E-4 N.A. - 6:2 FTOH 1.2-1.7E-2 N.A. - 1 E-2 8:2 FTOH 1.40 E-4 2.93 9.6 E-2 Table 4 .1. Environmental relevant properties of selected fluorosurfactants For PFOS the vapour pressure was determined to be 3.31 E-4 Pa. Although the vapour pressure determination study was rated with a Klimisch factor of 1 (see Annex II), there is discussion about the reliability of the result (Cahill, 2002). The hydrogen-salt of PFOA is relatively volatile (70 Pa); the ammonium-salt is not (<1.3 mPa) (M iteni, 2002). For PFOS and PFOA the combination of the good solubility, and their low vapour pressure, resulting in low Henry constants, makes it unlikely that they will be transported by air over large distances (Renner, 2001; Martin et al., 2002). N-EtFOSE, 6:2 FTOH and 8:2 FTOH have low water solubilities. Combined with a moderately low vapour pressure, these chemicals could have the tendency to escape from the water phase to air. Martin and co-workers (2002) verified this suggestion in a preliminary study with only a few samples. They detected the P e riluoroalkylated substances - Aquatic environmental assessment 000374 37 presence in air of six fluorinated chemicals, of which at least three can be degraded (after deposition) into PFOS (see section 4 .4 .2 ); these chemicals (n-EtFOSE, nMeFOSE and n-EtFOSA) may thus play a role in the dissemination of perfluorinated chemicals in general and PFOS in particular (Martin et al., 2002). The other three chemicals were telomers; their degradation products are largely unknown hitherto (see, however, section 4 .4.3). The results of this initial investigation by Martin and co-workers, combined with the volatility of some perfluorinated chemicals and the presence of PFOS in remote locations (Kannan et al., 2001a; Kannan et al., 2001b) indicate the potential of some PFAS species to be transported over long distances. 4.3 Sorption 4.3.1 Octanol water partitioning The distribution of a compound over n-octanol and water, commonly expressed by the partition coefficient K ,, is often used to predict or mimic the partitioning between hydrophobic phases and water. K, has been proposed as a model for the partitioning between the body fat of biota and water (bioaccumulation), between the sediment and water (sorption) and to estimate the soil sorption coefficient for organic compounds (Sabljic et al., 1995). This derivation of properties is based on the assumption that the hydrophobic and hydrophilic interactions between compound and substrate are the main mechanisms for the partitioning. This assumption has been shown to hold for non polar and slightly polar organic chemicals. There are two reasons why this concept is not applicable for fluorosurfactants. First, fluorosurfactants do not behave like traditional organic chemicals, due to the p e r flu o rin a tio n :hydrocarbon chains are oleophilic and hydrophobic, perfluorinated chains are both oleophobic and hydrophobic' (Key et al., 1997). Therefore, PFAS do not accumulate in fatty substances or adsorb to organic matter solely due to hydrophobic interactions. The oleophobic repellence prevents the accumulation of PFAS in fat (Kannnan et al., 2001a). Second, fluorosurfactants are polar chemicals, intrinsically. PFOS is present in the environment as the dissociated salt (3M , 2001a) Therefore electrostatic interactions may play an important role in the distribution. Both biota and sediment have various polar parts with which interaction is plausible. This 'theoretical' rejection of QSARs based on the octanol/ water partitioning is confirmed by the observation that PFAS accumulate in blood plasma and liver, rather than in adipose tissue (Ylinen & Auriola, 1990; Olsen et al., 1999). PFOA is shown to bind to macromolecules in the tissue (USEPA, 2002). This is different from several persistent neutral lipophilic compounds (Kannan et al., 2001a), which accumulate in fat. The suggestion that hydrophobic interactions are not the primary sorption mechanism is supported by the assumption that PFOS binds to sediment via chemisorption (3M , 2001b). Therefore, the K ,,, is not suitable for the prediction of sorption of surfactants. Although the significance of the partitioning between octanol and water is limited for environmental behaviour on PFAS, there have been several studies that tried to determine the K ,,, experimentally. Due to the surfactant properties of the substance it was not possible to obtain reliable results with the standard `shake flask' method (3M , 2000a). Experiments with HPLC retention times made it possible to obtain more reliable K. results for n-EtFOSE and n-MeFOSEA (see table 4 .2 ). Perfluoroalkylated substances - Aquatic environmental assessment 38 000375 e degraded >SE, n- 2002). largely sd with in remote itial of tressed by in g lei for the Detween :ient for Dbic and for non- mts. e to the 997). c matter the in the factions ig is er, : OA is ?nt which on of mited ied to <e e n -EtFO S E 4.4 3M, 1994a n-MeFOSEA 5.6 3M, 1994b Table 4.2. Available values for partitioning n-octanol/water 4.3.2 Sorption The partitioning between sediment and water is an important factor in the fate of chemicals. Often, the partitioning octanol/water is used to predict this factor. In the preceding section it was argued that this would not give correct predictions for perfluorinated compounds. Direct measurements of the sorption to soil and sludge gave contradictory results for PFOS. Only two reliable studies are available (3M , 1978a; 3M , 2001b), with a Klimisch factor of respectively 2 and 1 (see annex II). The first study predicts a high mobility of PFOS in Brill sandy loam soil (3M , 1978a). In the second study a strong adsorption to ail soils tested was observed, including sludge and river sediment. Once adsorbed, PFOS does not desorb readily (3M , 2001b). The latter study suggests that the primary sorption process is chemisorption. In chemisorption the substance forms a chemical bond with the phase it is adsorbed to. For other perfluorinated surfactants only less reliable study results are available, having a Klimisch factor of 3. Two studies suggest that n-EtFOSE is very likely to adsorb to soil (3M , 1978a; 3M , 1978b). For PFOA two totally contradictory conclusions were drawn from one study (3M , 1978c). The results of a monitoring study near a fluorochemical plant show that PFOS, PFOA, FOSA and PFHS do occur in the sediment (3M , 2001c). These findings are supported by the detection of PFOS in various sediments and sewage sludge in a multi-city environmental monitoring study (3M , 2001 d). Therefore it is unlikely that these fluorinated chemicals have a high mobility in sediment. There are no data available on telomers. However, laboratory experiments show that 8:2 FTOH is rapidly sorbed from aqueous solutions. Specific recovery methods have been developed to be able to make accurate measurement. Experts state that the sorption of telomers onto various types of surfaces is very high and that desorption is very difficult (TRP, 2002). 4.4 Transformation 4.4.1 Introduction The fluorine-carbon bond is the strongest single bond with carbon, but its strength is very much dependent on the actual molecular structure. Given the high-energy content of the C-F bond, it is expected that many fluorinated organic compounds will be resistant to hydrolysis, photolysis and biodegradation (Smart, 1994). Indeed transformation rates (see table 4 .3) suggest that the perfluorinated part of PFAS are relatively persistent in the environment. The available data on transfrmation of PFAS are presented in table 4.3. Perfluoroalkylated substances - Aquatic environmental assessment T /' ' - 000376 39 PFOS (K+) PFOA (NH4+) n-MeFOSE n -EtFO S E 0% 0%2ilu To PFOS/ PFOA23' n-MeFOSEA n-EtFOSEA 8:2 FTOH To PFOA2U o v ..... -q%TC12 "o% ,s No direct photolysis expected21 T1/24 > 41 years'* TM T1/2 >92 years M T1/2 = 6.3 years1' T1/2 = 7.3 years'0 92% after 24 hours to PFOS (alkaline)17 T1/2 = 99 days @ pH 7, 25 C (extrapolate! T1/2 35 days @ pH7, 25 Cw half-life, (1) 3M, 1976 (2) 3M , 2001e (3) 3M, 2000b (4) 3M, 2000c (5) 3M. 2000d (6) 3M, 2000e (7) 3M, 1979a (8) 3M, 2001f (9) 3M , 2001g (10) 3M, 1978d (11) 3M, 1979b (12) 3M, 2001h (13) 3M, 2001i (14) 3M , 2 001j(15)3M , 1981 (16) 3M, 2001k (17) 3M, 1977 (18) 3M, 1999a (19) 3M, 1996 (20) Hagen et al,, 1981 (21) TRP, 2002 4.4.2 ECF-products Biodegradation Many of the substances under study undergo primary degradation3. In this degradation step the non-fluorinated part of the molecule is transformed. The degradation pathway for n-EtFOSE in wastewater sludge is suggested to be as shown in figure 4.4. FFFF N-EtFOSE -* M556 FOSA P FO S u lfin a te PFO A (abiotic pathway) Figure 4 .4. Degradation pathway of n-EtFOSE to PFOS and PFOA (3M, 2000b, 3M, 2001 e). 3A compound is considered to be primary biodegradable if the original compound is altered, due to biodegradation processes. The degradation products can be persistent With ultimate biodegradation, the original compound is completely transformed into C 0 2 and H2O and inorganic salts. Perfluoroalkylated substances - Aquatic environmental assessment 40 000377 dation M . 2000e (7) (13) 3M, ' M , 1996 IS The be as O -=0 y y 3M, 3tO ation, It is likely that the degradation of n-MeFOSE will follow an analogous pathway, because n-MeFOSE contains the same reactive structures that appear to be vulnerable to microbial (biodegradation) attacks. N-EtFOSE and n-MeFOSE are the two main building blocks of the ECF-based fluorochemistry (3M , 2000h). No research has been published on the transformation of other functional groups, but it is expected that they may also be transformed to n-EtFOSE or n-MeFOSE. The likely endpoints of aerobic degradation of ECF-products are PFOS and PFOA (3M , 2001 e). In both compounds the perfluoroalkyl chain is not affected by biodegradation. PFOS is non-degradable under both aerobic (3M , 1976; 3M, 2001 e; 3M , 2000b; 3M , 2000c; 3M , 2000e) and anaeroDic circumstances (3M , 2000d). PFOA is non-degradable under aerobic circumstances (3M , 1978d; 3M , 2001 e); no anaerobic degradation test results are available. Hydrolysis and photolysis The available studies on photolysis show that this transformation mechanism will be of no importance in the breakdown of perfluorinated chemicals. The tests with PFOS, PFOA, POSF and n-EtFOSE show no photodegradation at all (see table 4 .3 ). Experiments show stability toward hydrolysis for all chemicals tested, with exception of the acrylates (see table 4 .3). Both n-EtFOSEA and n-MeFOSEA are vulnerable to hydrolytic attack under environmental conditions. The transformation products are not known, but n-EtFOSE and n-MeFOSE, respectively, and acrylic acid are the most logical products. This transformation does not affect the perfluoroalkyl chain. Therefore, hydrolytic products of both acrylates will presumably not be affected by further hydrolysis, photolysis or biodegradation. 4.4.3 Telomer-products Only one source dealing with the degradation of telomer-products in the environment is available. This study (Key et al., 1998) showed the degradation of 1H,1H,2H,2H-perfluorooctane sulfonate under sulfur limiting conditions by Pseudomonas sp. Strain D2. Volatile degradation products were formed, containing carbon, oxygen, hydrogen and fluorine. Furthermore, the detection of fluoride indicated defluorination (Key et al., 1998). The biotransformation in rodents of a telomer has been investigated and published. This study suggests that biotransformation of 8:2 FTOH to PFOA does occur in rats (Hagen et al., 1981). In this transformation two fluorine-carbon bonds are broken. W hether the same route of degradation is likely to occur in the environment is not known. If 8:2 FTOH is absorbed by biota in the environment, the same transformation might take place, leading to PFOA. Current research is dedicated to the biodegradation of telomer-products (Renner, 2001; TRP, 2002). Although few experimental supporting data are available, there are various suggestions that the perfluoroalkyl chain of telomerisation products cannot be biodegraded, which is supported by the high binding energy of the fluorine-carbon bond (Smart, 1994; Key et al., 1997; Renner, 2001). However, the research by Key et al. (1998) suggests that fluorinated alkyl chains are vulnerable to biodegradation, presumably yielding biodegradation products that are different than those originating from ECF-products (PFOS, PFOA). Although direct photolysis is not expected to occur as an abiotic degradation route, there is evidence that decomposition of fluorinated chemicals may occur via indirect photolysis in air with OH radical reactions (Vesine et a l., 2000; TRP, 2002). 4.4.4 Fluorinated organic polymers The vast majority of the fluorochemicals are applied in polymeric form. Hence, most emissions will be in (co-)polymeric form. Until now, no research has been done on the degradation or transformation of fluorinated organic polymers. This is an important subject, since, in general, polymers cannot cross membranes, and Perfluoroalkylated substances - Aquatic environmental assessment 000378 41 therefore will not have toxic effects. If monomeric PFAS may be formed from H fluorinated organic polymers, these could cross biotic membranes. V In interviews with manufacturers, it was suggested that fluorinated organic t polymers are very stable (3M , 2002; Bayer, 2002). 3M states that they '[..] have I data demonstrating the stability o f high molecular weight fluorochemical F polymers and phosphate esters to various mechanisms o f degradation. ' (3M , | 2000f). One study, predicting the hydrolytic stability, is available. Although the t data of this study have to be treated with caution, due to limited reliability, they } showed that fluorinated organic polymers are rather stable to hydrolysis, resulting I in half-lives ranging from 1-5 years for acrylates and esters to 500 years for f fluorinated urethanes (3M , 2000g). | From a chemical point of view it seems possible to hydrolyse the ester bond in \ polyacrylates and polymethacrylates, leading to the formation of PFAS. Also the I ester bond in the fluoroalkyl phosphates might be vulnerable. These aspects have jr to be investigated in a reliable study. An initial study with PFAS treated textile has been performed. The organic extraction of polymer treated textile lead to the release of monomeric perfluorinated compounds. The origin of these monomers can be different than from transformation of the polymers (see section 3.3.1) (Jonkers et a!., 2002). 4.5 Bioconcentration Bioaccumulation is a process in which a substance accumulates in an organism. There are two possible routes: biomagnification (uptake through food) and bioconcentration (uptake directly from the water). Usually, for many organic compounds the bioaccumulation may be derived from the octanol/water partitioning coefficient, because most organic chemicals accumulate in lipids. Since perfluorinated surfactants likely elicit a different partitioning behaviour, the is not a suitable predictor for the bioaccumulation (see section 4.3.1). PFO S (K+) 6300-1250001 484 (edible), 1124 (nonedible), 859 (whole) < 1J clearance >130d2 PFOA (NH4+) 8:2 FTOH 1.8' 2s <9.4* Clearance > 15d6 200-1100 (10 pg/L)' < 1A 87-310 (1pg/L)7 Table 4.5. Available data on bioaccumulation, bioconcentration and biomagnification of PFAS (1) Moody et al,, 2002 (2) 3M, 20011 (3) Martin et al,, 2001 (4) 3M in APME, 2002 (5) APME, 2002 (6) 3M, 1995 (7) MET! cited in TRP, 2002. The available, reliable studies on bioaccumulation show that PFOS bioaccumulates, and is hardly excreted (see table 4 .5 ). In an in situ bioaccumulation study in Canada a very high experimental bioaccumulation factors (BAF) for PFOS were observed: between 6300-125000 (Moody et a l., 2002). This BAF is high in comparison with the BCF and BMF data available. Moody et al. (2002) suggest that accumulated perfluorinated derivatives are metabolised to form PFOS, thus overestimating the BAF of PFOS. In a laboratory experiment the BCF fo r PFOA (N H /) was determined to be 1.8 for fish (fathead minnows), 2 for fish (Rainbow trout) and < 9.4 (Carp). The fathead minnows experiment is believed to have limited reliability (USEPA, 2002). Perfluoroalkylated substances - Aquatic environmental assessment 42 000379 ! from tnic [..] have al (3M , /gh the ty, they resulting for >nd in \lso the cts have c tthan 02). lism . i I from ilation 3M in jlates, re 3t US for ad For 8:2 FTOH a water concentration depedent bioconcentration factor was determined by M ETI. The Telomer Research Program is currently investigating the reliability of this study (TRP, 2002). For other perfluorinated substances no bioaccumulation data are available. 4.6 Distribution Research on the environmental fate of fluorinated chemicals is ongoing, including multi-species fate modelling (Cahill, 2002). Only one fate study using a fugacity model is available; this is qualified by the researcher as 'a small first step' (3M , 1999b). Although the preliminary fugacity modelling was tentative, and the Klimisch rating was 3, it is believed to give a rough approximation of PFOS behaviour (Cahill, 2002). For this exercise the equilibrium criterion model (EQ C) developed by Mackay et al. (1996) was used. In this model there are three different levels, with increasing complexity (see figure 4.6). o-- This ECQ modelling predicts an 80/20 % partitioning over water and soil in level I and level II calculations. In level II, advection is the main removal mechanism. In level III calculations discharges to air and soil are predicted to partition to soil, whereas discharges to water are predicted to stay in the water and are subject to removal by adjective flow (3M , 1999b). 4.7 Conclusions and recommendations t> ! i th i Typa !!i tM M U M tfl LM M Figure 4.6 Schematic representation of the different levels in the EQC model (M ackay et al., 1996) From this chapter it is evident that many data on the behaviour of PFAS in the environment are not available. For telomers and fluorinated organic polymers, no data are available on sorption, degradation and distribution. It is recommended to fill these gaps of knowledge. It was suggested that n-EtFOSE, n-MeFOSE and n-EtFOSA (ECF products) and 6:2 FTO H, 8:2FTOH and 10:2 FTOH (telomers) may escape from the water phase to air, as they have been detected in air. For n-EtFOSE, 6:2 FTOH and 8:2 FTOH this tendency to leave the water phase is supported by relatively high Henry constants. These products may be transported over long range. It is likely that the ECF products may degrade to form PFOS or PFOA. This mechanism may be an important factor in the global spreading of PFAS. The sorption of PFAS cannot be modelled with Kow. Hydrophobic and hydrophilic interactions are not the primary partitioning mechanisms; electrostatic interactions may be important. It has been suggested that PFOS adsorbs via chemisorption. For PFOA no conclusions could be drawn considering the sorption potential. Laboratory experiment show that 8:2 FTOH is rapidly adsorbed from aqueous solutions and desorption is very difficult. These preliminary results are supported by expert judgements. The perfluoroalkyl chain of ECF products is not affected by degradation, photolysis or hydrolysis. The most likely end products of degradation are PFOS and PFOA. PFOS is not degraded under aerobic or anaerobic circumstances, for PFOA only aerobic results are available, showing the persistence of this substance. None of Perfluoroalkylated substances - Aquatic environmental assessment 43 000380 the tested chemicals could be transformed by light. Only the acrylates n-MeFOSEA and n-EtFOSEA can be transformed by hydrolysis, forming n-MeFOSE and n- EtFOSE, respectively, and acrylic acid. The perfluoroalkyl chain of 6:2 perfluorooctane sulfonate was degraded in a study under sulfur limiting conditions, resulting in unidentified, volatile degradation products. In rats 8:2 FTOH is partially transformed to PFOA. 8:2 FTOH is not vulnerable to direct photolysis, but indirect photolysis in air via OH radicals might I result in the complete breakdown. There are various suggestions that the perfluoroalkyl chain of telomers cannot be biodegraded. No reliable data are available on the degradation or transformation of fluorinated f f j! organic polymers. j The bioaccumulation factor for PFOS is 6300-125000; its bioconcentration factor is S 859 (whole fish). PFOA hardly bioconcentrates, with a BCF of 1.8 - <9.4. The \ telomer alcohol 8:2 FTOH a bioconcentration factor of between 87 and 1100 has been reported. When discharged to water, PFOS will partially adsorb to soil and sediment; bioaccumulation of PFOS will take place. Therefore, water, sediment and organic matter are believed to be the most important environmental compartments. PFOA will not evaporate from the water phase, and the sorption potential is not clear. PFOA does not bioaccumulate. Therefore, water is believed to be the primary compartment for PFOA. 4.8 References 3M , 1976, Biodegradation studies of fluorocarbons, 3M , St. Paul, Minnesota, United States of America 3M , 1977, Alkaline hydrolysis of FM 3422, 3M , St. Paul, Minnesota, United States of America 3M , 1978a, "Soil Thin Layer Chromatography FC-95, FC-143, FM -3422, 3M , St. Paul, Minnesota, United States of America 3M , 1978b, Adsorption of FM -3422, 3M , St. Paul, Minnesota, United States of Am erica 3M , 1978c, Adsorption of FC-95 and FC-143 on soil, 3M , St. Paul, Minnesota, United States of America 3M , 1978d, Biodegradation studies o f fluorocarbons III, 3M , St. Paul, Minnesota, United States of America 3M , 1979a, FC-95, Photolysis study using simulated sunlight, 3M , St. Paul, Minnesota, United States of America 3M , 1979b, FC-143, Photolysis study using simulated sunlight, 3M , St. Paul, Minnesota, United States of America 3M , 1981, FM 3422, Photolysis study using simulated sunlight, 3M , St. Paul, Minnesota, United States of America 3M , 1994a, Determination of the partition coefficient (n-octanol/water) of T-5874 by high performance liquid chromatography (H PLC), NOTOX, `s Hertogenbosch, The Netherlands 3M , 1994b, determination of the partition coefficient (n-octanol/water) of T-5869, by high performance liquid chromatography (H PLC), NOTOX, `s Hertogenbosch, The Netherlands Perfluoroalkylated substances - Aquatic environmental assessment 44 oooasi n-MeFOSEA and ni in a study Jation is not :aJs might e uorinated on factor is L The 1100 has it; I organic its. il is not he ota, id States 3M, St. :es of ;ota, lesota. T-5874 osch, -5869, is c h . 3M , 1995, Assessment of bioaccumulation properties of ammonium perfluorooctanoic acid: static fish test, 3M , St. Paul, Minnesota, United States of America 3M, 1996, Determination of physico-chemical properties of sample D-1 (English version), Mitsubishi Chemical Safety Institute, Ltd., Yokohama, Japan 3M, 1999a, Study of the stability of M eFOSEA in aqueous buffers using gas chromatography with atomic emission detection, 3M Environmental Laboratory, St. Paul, Minnesota, United States of America 3M , 1999b, Transport between environmental compartments (fugacity modeling)included in letter from Don Mackay on the air/water partitioning coefficient calculations, Mackay Environmental Research Ltd., Peterborough, Ontario, Canada 3M , 2000a, PFOS: Determination of the n-octanol/Water Partition Coefficient by the Shake Flask Method, W ildlife International, Ltd., Easton, Maryland, United States of America 3M , 2000b, The aerobic biodegradation of N-EtFOSE alcohol by the microbial activity present in municipal wastewater treatment sludge, Pace Analytical Services Inc. Minneapolis, Minnesota, United States of America 3M , 2000c, Microbial metabolism (Biodegradation). Studies of perfluorooctane sulfonate (PFO S). II. Aerobic soil biodegradation, Springbom Laboratories, Inc., Wareham, Massachusetts, United States of America 3M , 2000d, Microbial metabolism (Biodegradation). Studies of perfluorooctane sulfonate (PFO S). III. Anaerobic sludge biodegradtion, Springborn Laboratories, Inc., Wareham, Massachusetts, United States of America 3M , 2000e, Microbial metabolism (Biodegradation). Studies of perfluorooctane sulfonate (PFO S). IV . Pure culture study, Springborn Laboratories, Inc., Wareham, Massachusetts, United States of America 3M , 2000f, letter of William A. Weppner to Dr. Hernandez, USEPA, April 28, 2000 3M , 2000g, work in progress on environmental fate and transport, 3M , St. Paul, Minnesota, United States of America 3M , 2000h, Voluntary Use and Exposure Information Profile Perfluorooctanesulfonyl fluoride (PO SF), St. Paul, Minnesota, United States of America. 3M , 2001 a, comments of 3m on OECD's September 2001 'draft assessment of perfluorooctane sulfonate and its salts', 3M , St. Paul, Minnesota, United States of America 3M , 2001b, Soil adsorption/desorption study of potassium perfluorooctanesulfonate (PFO S), 3M Environmental Laboratory, St. Paul, Minnesota, United States of America 3M , 2001c, Selected fluorochemicals in the Decatur, Alabam a area, Entrix Inc., East Lansing, Michigan, United States of America 3M , 2001d, Environmental Monitoring - M ulti-City Study. W ater, Sludge, Sediment, POTW Effluent and Landfill Leachate Samples. Executive Summary, 3M Environmental Laboratory, St. Paul, Minnesota, United States of America 3M , 2001 e, The 18-day aerobic biodegradation study of perfluorooctanesulfonylbased chemistries, Pace Analytical Services Inc. Minneapolis, Minnesota, United States of America Perfluoroalkylated substances - Aquatic environmental assessment r> k 45 000382 3M , 2001f, Screening studies on the aqueous photolytic degradation of perfluorooctane sulfonate (PFO S), 3M Environmental Laboratory, St. Paul, Minnesota, United States of America 3M , 2001 g, Hydrolysis reactions of perfluorooctane sulfonate (PFOS), 3M Environmental Laboratory, St. Paul, Minnesota, United States of America 3M , 2001 h, Screening studies on the aqueous photolytic degradation of perfluorooctanoic acid (PFO A), 3M Environmental Laboratory, St. Paul, Minnesota f United States of America 3M , 2001 i, Hydrolysis reactions of perfluorooctanoic acid (PFO A), 3M i Environmental Laboratory, St. Paul, Minnesota, United States of America 3M , 2001j, Hydrolysis reactions of 2-(N-Methylperfluorooctanesulfonamido)-Ethy| t alcohol (N-MeFOSE Alcohol), 3M Environmental Laboratory, St. Paul, Minnesota, United States of America 3M , 2001 k, Hydrolysis reactions of 2-(N-Ethylperfluorooctanesulfonamido)-Ethy| alcohol (N-EtFOSE Alcohol), 3M Environmental Laboratory, St. Paul, Minnesota, United States of America * ; 3M , 20011, Perfluoroctanesulfonate, potassium salt (PFOS). A flow-through bioconcentration test with the bluegill (Lepomis macrochirus), Wildlife International, Easton, M aryland, United States of America 3M , 2002, personal communication with Dr. Sinnaeve, European Toxicological Manager, Antwerp, Belgium APM E, 2002, Association of Plastic Manufacturers Europe, Presentation at DuPont, M ay 2002, Dordrecht, The Netherlands Bayer, 2002, personal communication with Dr. Sewekow, European Toxicological Manager, Leverkusen, Germany. Cahill, 2002, personal communication with Dr. T. Cahill, Trent University, Peterborough, Ontario, Canada Hagen, DF, Belisle, J, Johnson, JD , Venkateswarlu, P, 1981, Characterization of fluorinated metabolites by a gas chromatographic-helium microwave-plasma detector - The biotransformation of 1 H .1H , 2H, 2H-perfluorodecanol to perfluorooctanoate, Anal. Biochem., 118, 336-343 Jonkers, N, Krap, L, de Voogt, P, 2002, Optimisation of analytical methods for surveying the occurrence of perfluorinated surfactants in various matrices, poster presentation at SETAC Europe 2002, Vienna, Austria Kannan, K, Koistinen, J, Beckmen, K, Evans, T , Gorzelany, JF, Hansen, KJ, Jones, PD, Helle, E, Nyman, M , Giesy, JP, 2001a, Accumulation of perfluorooctane sulfonate in marine mammals, Environ. Sci. Techno!., 35,1593-1598 Kannan, K, Franson, JC , Bowerman, W W , Hansen, KJ, Jones, PD, Giesy, JP, 2001b, Perfluorooctane sulfonate in fish-eating water birds including bald eagles and albatrosses, Environ. Sci. Technol., 35, 3065-3070 Key, BD, Howell, RD, Criddle, CS, 1997, Fluorinated organics in the biosphere, Environ. Sci. Technol., 31,2445-2454 Key, BD, Howell, RD, Criddle ,CS, 1998, Defluorination of organofluorine sulfur compounds by Pseudomonas Sp. Strain D2, Environ. Sci. Technol., 32, 2283-2287 M ackay, D, Di Guardo, A , Paterson, S, Cowan, CE, 1996. Evaluating the environmental fate of a variety of types of chemicals using the EQC model, Env. Tox. Chem., 15, 1627-1637 Perfluoroalkylated substances - Aquatic environmental assessment 46 000383 Jl, v\ Minnesota, do)-Ethy| inesota, 3)-Ethyl esota, ;h gical DuPont, logical n of a for oster nes, !001b, e, fur 2287 Martin, J, Mabury, S, Solomon, K, M uir, D, 2001, Dietary accumulation and bioconcentration of perfluorinated surfactants on rainbow trout, presentation abstract of SETAC World, 22ndAnnual Meeting Martin, JW , Muir, DCG, Moody, CA , Ellis, DA, Kwan, W C, Solomon, KR, Mabury, SA, 2002, collection of airborne fluorinated organics and analysis by gas chromatography/chemical ionization mass spectrometry, Anal. Chem., 74, 584590 Miteni, 2002, Data submitted by M r. Mistrorigo, M iteni, Milano, Italy Moody, CA, Martin, JW , Kwan, W C, M uir, DCG, M abury, SA, 2002, Monitoring Perfluorinated Surfactants in Biota and Surface W ater Samples Following an Accidental Release of Fire-Fighting Foam into Etobicoke Creek, Environ. Sei. Techno!.; 36, 545-551 Olsen, GW , Burris, JM , Mandel, JH, Zobel, LR, 1999, Serum perfiuorooctane sulfonate and hepatic and lipid clinical chemistry tests in fluorochemical production employees, J. Occup. Environ. M ed., 41, 799-806 Renner, 2001, Growing concern over perfluorinated chemicals, Environ. Sei. Techn., 35, 7, 154A-160A Sabljic, A , Gsten, H, Verhaar, H, Hermens, J, 1995, QSAR modelling of soil sorption. Improvement and systematics of Log Kk vs. Log correlations, Chemosphere, 31, 4489-4514 Smart, BE, 1994, Characteristics of C-F systems, in Banks, RE et al. (Ed.), 1994, Organofluorine chemistry: principles and commercial applications, Plenum Press, New York, USA, Chapter 3 TRP, 2002, Telomer Research Program, Presentation at DuPont, May, Dordrecht, The Netherlands USEPA, 2002, Draft hazard assessment of perfluorooctanoic acid and its salts, February 20, 2002, Washington, D .C ., United States of America Van Leeuwen, CJ, Hermens, JLM , 1995, Risk assessment of chemicals. An Introduction. Kluwer Academic Press, Amsterdam, The Netherlands Vsine, E, Bossoutrot, V , Mellouki, A, Le Bras, G, W enger, J, Sidebottom, H, 2000, Kinetics and mechanistic study of OH- and Cl-initiated oxidation of two unsaturated HFCs: C4F9CH=CH2and CSF13CH=CH2, J. Phys. Chem. A, 104, 85128520 Ylinen, M , Auriola, S, 1990, Tissue distribution and elimination of perfluorodecanoic acid in the rat after single intraperitoneal administration, Pharmacol. Toxicol., 66, January 1990, 45-48 Perfluoroalkylated substances - Aquatic environmental assessment 47 000384 Perfluoroalkylated substances - Aquatic environmental assessment 48 000385 5 Occurrence in the environment 5.1 Introduction The perfluoroalkyl chain of fluorinated chemicals is persistent (see section 4.4.1). Therefore they will be present in the environment. As was shown in chapter 4, their behaviour in the environment is not well known. It was shown that PFAS accumulate in blood plasma and liver of biota. Various publications on the occurrence in the environment have been published. Most of these publications concern the occurrence in Northern American biota. Very few data on the Western European situation are available and with regards to the occurrence of PFAS in the Netherlands only the preliminary, non-reviewed results of one study are available. 5.2 Analytical techniques (based on Ciesy & Kannan, 2002) 5.2.1 General remarks General remarks The interest in perfluoroalkylated substances has started relatively recently. The analytical methods for these chemicals are currently under development and their optimisation is the subject of many ongoing studies. In particular the validation and quality assurance of analytical methods for PFAS needs further work. Until now interlaboratory exercises on PFAS analysis have not been carried out. Currently there is no (certified/standard) reference material available on the market for any of the perfluoroalkylated substances. Below a short description is presented of analytical methods for PFAS described in the literature. 5.2.2 Qualitative methods The fluorine content of organic molecules can be determined by destructive and nondestructive methods, such as neutron activation and X-ray fluorescence. These are low-sensitivity techniques that do not enable identification or quantification of individual organofluorine compounds. It is important to note that all biologically produced fluorinated organics contain only one fluorine atom (Key et a!., 1997) Fluorine in organic compounds can also be determined by combustion, converting it to an inorganic fluoride; however, rigorous conditions are required for quantitative mineralisation. These techniques have been used for determining total fluorine in environmental and biological samples (Sweetser, 1965; Kissa, 1986). In environmental matrices, tests that measure methylene-blue-active substances have been used to detect anionic PFAS, but the approach is non-specific (Levine et al.. 1997). 5.2.3 GC-ECD/MS Perfluorinated surfactants can be determined using derivatisation techniques coupled with gas chromatography followed by electron capture detection (Hagen et al., 1981) and mass spectrometric detection (Moody & Field, 1999; Moody & Field, 2000). PFOS has a low vapour pressure, and its derivatives are unstable. 5.2.4 HPLC-FD Perfluorocarboxylic acid concentrations in biological samples have been measured using high-performance liquid chromatography (HPLC) and fluorescence detection (O hya et al., 1998). The application of this method is limited to environmental samples. Perfluoroalkylated substances - Aquatic environmental assessment 49 000386 5.2.5 NMR Nuclear magnetic resonance (19F NMR) can be used to determine the concentrations of fluorinated chemicals in biological samples. NMR techniques have been used to measure PFAS in contaminated water samples (Moody et al., 2001). The 19F NMR-results were compared with LC/MS-data. It was suggested that the 19F NMR technique overestimated the actual concentrations (see also section 5 .3). In the 1970s, PFAS in human blood were analysed using nonquantitative NMR techniques (Hagen et al., 1981). Preconcentration is generally required with additional rigorous cleanup procedures. 5.2.6 HPLC/MS/MS Compound-specific methods for analysing PFAS using HPLC-negative ion electrospray tandem mass spectrometry (HPLC/M S/M S) (Hansen et al., 2001) enable surveys of the environmental distribution of PFAS in wildlife at global scales t (Giesy & Kannan, 2001; Kannan et al. 2001a; Kannan et al., 2001b). Further method improvements are needed to accommodate the range of PFAS concentrations in biological and environmental matrices and for monitoring PFAS in atmospheric media. 5.3 Freshwater environment PFOS, PFOA and FOSA have been analysed in a variety of media in six cities in the United States of America including drinking water, surface water column, sediment, publicly-owned treatment works (PO TW ) sludge, POTW effluent and landfill leachate samples. Decatur, Mobile, Colombus and Pensacola are so-called supply chain cities. In these cities perfluorinated chemicals are either manufactured or industrially used. Cleveland and Port St. Lucie are control cities. Results are listed in table 5.1. I t { f r Perfluoroalkylated substances - Aquatic environmental assessment 50 000387 1^ iniques 'dy et al., Jggested ;e also ongenerally >n 2001) obal scales ther ng PFAS ties In the nt and o-called jfactured are listed POTW effluent POTW sludge (dry wt) Drinking water influent Drinking water treated Drinking water tap Landfill leachate Surface water Sediment (dry wt) Quiet water Sample POTW effluent POTW sludge (dry wt) Drinking water influent Drinking water treated Drinking water tap Landfill leachate Surface water Sediment (dry wt) Quiet water POTW effluent POTW sludge (dry wt) Drinking water influent Drinking water treated Drinking water tap Landfill leachate Surface water Sediment (dry wt) Quiet water PFOS (ng/L or ng/kg) 4.98 0.436 0.048 0.427 0.896 0.069 2980 123 58.9 158 125 61.6 N.D. N.D N.D. 0.057 N.D. N.D. N.D N.D N.D. 0.063 N.D. N.D. N.D N.D N.D. 0.058 0.045/N.D. N.D. 52.7 N.C N.D N.D. N.D. 0.382 N.D/N.Q N.D/N.Q 0.039 0.066 0.029/N.Q. 0.138/N.Q. 0.452 N.D/N.Q 0.523 0.437 0.325/ N.D. 10.2 0.111 N.C 0.033 N.D. N.Q. 2.19 Decatur Cleveland Mobile Columbus Pensacola Port St. Lucie PFOA (ng/L or ug/kg 2.28 0.665 0.078 0.143 0.087 0.042 173 0.297 N.Q. 16.4 2.46 N.D. N.D. N.D. N.D. 0.026/N.Q. N.D. N.D. N.D. N.D. N.D. 0.027 N.D. N.D. N.D N.D. N.D. 0.026/N.Q. N.D. N.D. 47.5 N.C. N.D. 0.028/N.Q. N.D. 0.946 N.D./N.Q. N.D. 0.056 0.026 N.D. N.D N.D./N.Q. N.D. N.D7N.Q. N.D. N.D. 0.79 0.060 N .C . 0.027/N.Q N.D. N.D. 0.749 FOSA (ug/L or ug/kg) 0.056 N.Q. N.Q. 0.085 N.Q. N.Q. 102.4 1.69 N.Q. 42.4 1.28 N.Q. N.D. N.D. N.D. N.Q. N.D. N.D. N.D. N.D. N.D. N.Q. N.D. N.D. N.D. N.D. N.D. N.Q. N.D. N.D. 0.254 N.C. N.D. N.D. N.D. N.Q. N.D. N.D. N.Q. N.Q. N.D. N.D. N.Q. N.D. 0.445 N.Q. N.D. N.Q./N.D. N.Q. N.C. N.Q. N.D. N.D. 0.090 Table 5.1 PFOS, PFOA and FOSA In several media from six cities (average of duplicates; drinking water, surface water and sediment are averages of three different samples). N.D. = not detected, N.Q. * not quantifiable, N .C. = not collected (3M , 2001). PFOS was detected most often, followed by PFOA and FOSA, all in relatively low concentrations. The highest concentrations were found in POTW sludge. The POTW effluent and landfill leachate were other important media (3M , 2001). The highest concentrations were observed in Decatur. There is a fluorochemical manufacturing plant in this city. PFAS was also present in the control cities, showing a general distribution of PFAS. Perfluoroalkylated substances - Aquatic environmental assessment 51 000388 Site 1.1 3 372 149 6570 7090 Site 1.2 5 57 18 460 540 Site 1.3 3 N.D. N.D. N.D. N.D. Site 1.4 3 N.D. N.D. N.D. N.D. Site 2.1 2 144 38 116 298 Site 2.2 2 73 22 64 159 Site 2.3 5 64 19 42 124 Site 2.4 2 N.D. N.D. N.D. N.D. Table 5.2 Concentrations of perfluorocarboxylates in groundwater at two fire fighting training sites (pg/L). N.D.= not detected above detection limit (Moody & Field, 1999). The concentration of perfluorocarboxylates in groundwater near two airport fire fighting training sites has been analysed (Moody & Field, 1999). The results listed in table 5.2 do not represent general groundwater concentrations. Both sites showed contamination with PFAS. Sites that were closer to the trainingsite were more heavily contaminated. PFOA is the quantitatively most important fluorochemical present. The surface water concentrations of perfluorinated surfactants after an AFFF spill have been analysed with two different analytical methods (Moody et al., 2001; Moody et al., 2002). Results are listed in table 5.3. Perfluoroalkylated substances - Aquatic environmental assessment !.. ' 52 000389 /o fire1oody & ort fireIts listed training>ortant FF spill '001; MA MA ` . A l ! l 60 (n=3) 49 il 28 513 (n=3) lotes No PFAS was detected upstream of the airport. The contamination is spread downstream overtim e. PFOS was the quantitatively most important fluorochemical present. The surface water of a river upstream and downstream of a fluorochemical manufacturing facility in the USA has been analysed for perfluorinated surfactants. Both PFOS and PFOA levels increased downstream from the plant as can be seen in figure 5.4 (Hansen et al., 2002). FFOsl PFOAI PFOS and PFOA Levels in the TN River Milt Marker Figure 5.4 PFOS and PFOA Levels in the Tennessee River. The line at 301 mile indicates the location of the incoming effluent from the fluorochemical manufacturing plant (Hansen et a l.r 2002). The occurrence of telomers in the freshwater environment has not been reported. 5.4 Marine environment No data are available on the occurrence of perfluoroalkylated substances in the marine abiotic environment. 5.5 Biota 5.5.1 The Netherlands & Belgium Until now only one study on the occurrence of PFAS in the Dutch environment has been performed (Van de V ijver et al., 2002). This study revealed the presence of PFOS in various marine and estuarine organisms in the Western Scheldt estuary and the Belgian North Sea. All samples that were analysed contained detectable amounts of PFOS. The highest average concentrations (1.7 pg/g tissue) were observed in plaice (Pleuronectus platessa) from the estuary. Samples of shrimp and crab in the North Sea and the estuary showed concentrations between 40-320 ng/g tissue. Concentrations in Trisopterus Luscus (pouting) were the lowest: between 36 (North Sea) and 132 ng/g tissue (estuary) (Van de Vijver et al., 2002). Presumably, these results are not representative for the entire Netherlands. Upstream of the Western Scheldt estuary, along the river Scheldt, a factory producing fluorochemicals is operating. Sampling near a fluorochemical plant in the United States showed that the plant is a possible source of emissions of PFAS to the environment (see section 5.3) (Hansen et al., 2002). Therefore, concentrations downstream of the production site are expected to be higher than elsewhere. There are no data available for telomers in biota from the Netherlands. 5.5.2 Europe Giesy & Kannan (2001) and Kannan and co-workers (2001 a; ASAP) have published data on PFAS in European seals, dolphins, whales, cormorants, eagles swordfish, tuna and salmon. Results are shown in table 5.5. PFOS concentration^ were well above detection limits and PFOS was found in all samples analysed. Concentrations were higher in the more urbanised areas. Only few samples contained PFOA and PFHxS above LO Q . The highest PFOA concentrations were observed in Cormorant livers (29-450). None of the salmon samples and the muscle of a fin whale contained fluorochemicals above LO Q . PFOS concentration in seal livers were high. Concentrations in individual organisms varied within about an order of magnitude Livers of eagles from Eastern Germany and Poland have been analysed for PFOs from 1979 to 2000. PFOS was quantifiable in almost all samples. There was a statistically significant increase in the concentration of PFOS with time, but no dear temporal trend could be observed (Kannan et aJ., ASAP). Therefore two values are presented of samples from 1979-1989 and from 1990-1999. A t least one monitoring study is underway in Sweden. The preliminary results of that study showed low background concentrations in fish from unpolluted areas (1-2 ng/g fresh weight). Elevated PFOS levels were observed in fish from urbanised areas and a point source where fire-fighting foams had been used. Detailed resuits are not yet available (Jarnberg, 2002). No data for the occurrence of telomers in biota in Europe are available. M M M |i Bottlenose dolphin I Riccione Blood 4 143 (42-210) 223 (190-270^ Bottlenose dolphin Striped dolphin 1 Liver Liver 6 76 (<1.4-108) 4 26 (16.3-40) 63 (3 0 - 1 3 9 )]| <LOQ I Common Dolphin Giglio island Liver 1 940 878 Common Dolphin Giglio island Muscle 1 77 142 Fin whale Livorno Muscle 1 <LOQ <LOQ Long-finned pilot whale Elba island Liver 1 270 50 Long-finned pilot whale Elba island Muscle 1 52 48 Grey seal Baltic sea Liver 27 214 (140-360) 42 Grey seal Ringed seal Baltic sea Baltic sea Whole blood 26 38.3 (14-76) - i Liver 25 454(130-1100) <LOQ Ringed seal Cormorant Baltic sea Cabras lagoon Whole blood 29 158 Liver 12 61 (32-150) - !89 (<LOQ-89) White-tailed Sea eagle 1979-1989 Liver 7 22 (<LOQ-49.5) - White-tailed Sea eagle 1990-1999 Liver 36 40 (<LOQ-127) - Bluefin tuna Palizzi Blood 6 40 (27-52) 15(13-19) Tuna Liver 8 47 (21-87) <LOQ Swordfish Stretto Messina Blood 7 7.2 (4-14) 15(1.1-28) Swordfish Stretto Messina Liver 5 6 (<1-13) <LOQ Atlantic salmon Baltic sea Liver 22 <LOQ <LOQ 1PFOS and FOSA in various animals from Europe. Mean concentrations are given in Ing/g wet weight for liver, and ng/mL for blood . Values in parentheses indicate range. Values below LOQ are denoted by <. (Giesy &. Kannan, 2001 ; Kannan et V al., 2001a; Kannan et a l., ASAP). 5.5.3 Global occurrence Several publications are available on the global occurrence of PFAS in biota. Most information is available on concentrations of PFOS in wildlife from North America. In~table$ 5,^ -S lii'te lii'b liS e rv e d in biota from North America and other parts of the world are presented. As can be seen from table 5.6 large differences could be observed between individuals. Concentrations in eggs were higher than concentrations in liver and muscle. Concentrations of PFOS in whole blood of birds were less than those in blood plasma (see table 5.7). Large differences between individual animals were observed. Concentrations of PFOS were much higher in species from more urbanised areas: PFOS concentrations are 10-100 fold less in species from the Midway Atoll than concentrations in species from the Mid Western USA. In mustelids (table 5.8), invariably, PFOS was found above the LO Q . FOSA was the second most detected fluorinated chemical. Concentrations of PFOS in adults were higher than in juvenile mink. The suggested reason is a difference in feeding pattern (Kannan et al., 2002a). Another possible explanation is the bioaccumulation potential of PFOS. Concentrations of PFOS in mink and otter from more urbanised and industrialised areas were significantly higher than from more remote areas (Kannan et a l., 2002a). In marine mammals (table 5.9) several patterns in PFOS concentrations could be observed. The most plausible explanations for differences in concentrations are location of feeding (closer to shore gives higher concentrations) and habitat (more remote locations give lower exposure) (Kannan et a l., 2001a). Within species a high variability in PFOS concentrations between individual organisms was observed. Few samples of amphibians and reptiles have been analysed. From the data in table 5.10 it can be concluded that for turtles and frogs large differences in PFOS concentrations between individuals are possible. The data presented in table 5.11 show that PFOS concentrations in biota from remote locations were considerably lower than those observed from Europe and North America. Concentrations could not be quantified for many samples. Large differences are observed between the same species from different locations: polar bear in the Beaufort Sea has tenfold lower concentrations on average than polar bear from several other locations (see table 5.11). Many more data are available from the United States of America than from the rest of the world. However, a comparison of the available data (see Figure 5.12) shows that PFOS concentrations are highest in biota from North America, followed by biota from Europe. However, the PFOS concentration in liver from seals is higher in the European seals. PFOS concentrations in remote locations are much lower. No data on the occurrence of telomers in biota are available. Perfluoroalkylated substances - Aquatic environmental assessment 000392 55 Lake whitefish Michigan waters Eggs 2 2bU (16 0 -3 8 0 )^ Lake whitefish Michigan waters Liver 5 67(33-81) Lake whitefish Michigan waters Muscle 5 130 (97-170') n ; Brown trout Michigan waters Eggs 3 64(49-75) > Brown trout Michigan waters Liver 10 <LOQ-26 - Brown trout Michigan waters Muscle 10 <LOQ-46 Chinook salmon Michigan waters Liver 6 110(33-170) "x Chinook salmon Michigan waters Muscle 6 110(7-190) x Carp Saginaw Bay, Muscle 10 120(60-300) H Michigan Oysters North America Whole Oyster 77 312 (<LOQ-1225)' Table 5.6 PFOS in fish and invertebrates from Northern America. Mean concentrations are given in ng/g wet w t for egg yolk, liver and muscle and ng/g dry weight for oyster. Values in parentheses indicate range. Values below LOQ are denoted by <. Means are calculated only for the detectable observations (Giesy & Kannan, 2001, Kannan et al. 2002b). Double Crested Cormorant ormorant Double Crested Cormorant Double Crested Cormorant Double Crested cormorant Herring Gull Herring Gull Herring gull Ring-Billed Gull Bald eagle Bald eagle Black-crowned night heron Brandt's cormorant Brown pelican Common loon Franklin's gull Great black-backed gull Great blue heron Great egret Northern gannet Osprey Red-throated loon Snowy egret Whole blood 6 105 (34-188) St. Martin Is., Great Lakes Whole blood 2 184(124-243f Blood plasma 2 185(63-372) ' Lake Winnipegosis, Manitoba, Canada Egg Yolk 4 157(21-220) ' St. Martinville, LA Liver 2 169(51-288) Little Charity Is., Lake Huron Whole blood 2 63 (57-68) Little Charity Is., Lake Huron Blood plasma 2 315(239-391) Liver 5 186 (16-353) Sulphur Is., Thunder Bay, Lake Huron Egg Yolk 3 67 (30-126) Blood plasma 33 320 (<LOQ-222! Liver 4 192 (24-467) San Diego, CA Liver 5 393 (32-648) San Diego, CA Liver 2 907(46-1780) Liver 2 302 (118-533) Liver 14 129 (<12-595) Red Rock Lakes, Beaverhead County, MT Liver 4 40 (<12-61 ) Carteret County, NC Liver 2 608 (187-841) St. Martinville, LA Liver 2 539 (162-916) Liver 7 404 (27-1030) 1 Carteret County, NC Liver 1 85 Liver 4 377 (42-959) Liver 3 585(34-1120) Liver 3 185 (43-413) Perfluoroalkylated substances - Aquatic environmental assessment 56 000393 White pelican White-faced ibis Wood stork ____ ca f&, Sacramento Valley, CA Charleston County, SC Liver Liver Liver 6 270 (30-1120) 1 17 1 158 Table 5.7 PFOS in piscivorous birds from North America. Mean concentrations are given in ng/mL for blood plasma and whole blood and in ng/g wet w t for egg yolk and livers. Values in parentheses indicate range. Values below LO Q are denoted by <. Means are calculated only for the detectable observations (Kannan e ta l., 2001b). Mink Illinois 65 1177 (47-5140) 138 18 20 Mink Massachusetts 31 298 (20-1100) 92 10 8 Mink South Carolina 9 2081 (650-3110) 0 25 0 Mink Louisiana 7 140 (40-320) 0 00 River Otter Bremerton 1 286 22 <4 <7.5 River Otter Eglon 2 297 (173-422) 60 <4 <7.5 River Otter Fort Ward 3 156(139-189) 55 (40-72) <4-76 <7.5-19 River Otter Silverdale 2 199 (151-248) 33 (27-39) <4-52 <7.5-11 River Otter Soleduck River 2 43 (25-62) <4-4 <4 <7.5 River Otter Willamette River 7 579 (97-994) 23 (4.4-44) <4-68 <7.5-19 River Otter Yaquina River River Otter Nehalem River 2 39 (34-45) 1 82.8 <4-7.4 13 <4 <4 <7.5-9.9 <7.5 Table 5.8 Concentrations of Perfiuorochemicals in livers of Mink and otter in North America. Mean concentrations are given in ng/g wet wt. Values in parentheses indicate range. Values below LOQ are denoted by <. Means are calculated only for the detectable observations (Kannan et al., 2002a). Species Location Tissue n PFO S Pygmy sperm whale Short-snouted spinner dolphin Liver Gulf of Mexico Liver 2 14.8 (6.6-23.0) 3 123 (78.7-168) Striped dolphin Liver 2 212 (36.6-388) Rough-toothed dolphin Liver 2 54.2 (42.8-65.6) Bottlenose dolphin Liver 20 489 (48.2-1520) California sea lion Liver 6 26.6 (4.6-49.4) Elephant seal Liver 5 9.3 (<5-9.8) Harbor seal Liver 3 27.1 (10.3-57.1) Northern fur seal Liver 5 329 Sea otter Liver 8 8.9 (<5-14.3) Sea otter Brain 2 <35 Sea otter Kidney 3 <35 Table 5.9 Concentrations o f PFOS in Livers, kidney and brain of marine mammals in North America. Mean concentrations are given in ng/g w et w t. Values below LOQ are denoted by <. Means are calculated only for the detectable observations (Kannan et al., 2001a). Perfluoroalkylated substances - Aquatic environmental assessment 57 000394 Yellow-blotched map turtle Green frogs ' .T Mississippi Southwest Michigan >* n -, `-'i Liver Liver nr* 6 1 9 0 (39-7, ~4~ <35-290 Snapping turtle Lake St. Clair, Michigan Plasma ~5~ 72 CM7^ Table 5.10 Concentrations of PFOS in Liver and plasma of turtles and frogs from ^ North America. Mean concentrations are given in ng/m l for blood plasma and in ng/g wet wt for liver. Values in parentheses indicate range. Values below LOQ are denoted by <. Means are calculated only for the detectable observations. (Giesy & Kannan, 2001) Weddel seal Polar skua Terra Nova Bay Terra Nova Bay Liver Plasma <35 ^ f L !____ 2 <1-1.4 ^ Black-footed albatross Midway Atol, North Pacific Ocean Liver 5 <30 ^ Black-footed albatross Midway Atol, North Pacific Ocean Kidney 5 <30 "N Black-footed albatross Midway Atol, North Pacific Ocean Serum 8 6.2 (3.0-17 p Laysan Albatross Midway Atol, North Pacific Ocean Liver 3 <30 Laysan Albatross Midway Atol, North Pacific Ocean Kidney 3 <30 Laysan Albatross Midway Atol, North Pacific Ocean Serum 7 14(5.7-34)^ Yellow-fin tuna Northern fur seal Northern North Pacific ocean Pribilof Island Liver Liver 12 ~1 13 <10-122 [3 8 f Northern fur seal pup Pribilof Island Whole blood 19 <6-12 [5] ^ Northern fur seal adult Northern fur seal subadult Pribilof Island Pribilof Island Whole blood 10 <6 - - -- _ i Whole blood 7 <6 Northern fur seal Polar bear Pribilof Island Beaufort Sea Whole blood Whole blood 8 ! <6 14 34 (26-52) ' Barrow; Nuiqsut; Point Lay; Polar bear Gambell; Shishmaref; Little Diomede; Savoonga Liver 350(175-678) 17 Steller sea lion Ringed seal Southeast Alaska Spitsbergen Whole blood 12 <6 Whole blood 18 9.0 Ringed seal Norwegian Arctic Plasma 18 9 (5-14) Gray seal Sable Island Whole blood 12 27.7 11 Black-tailed gull Korea Liver 150 (70-500) 15 ! Black-tailed gull Hokkaido, Japan Plasma 24 6 (2-12) Ganges river dolphin 1Ganges River, India Liver i_______________________________________ 2 <35-81 Table 5.11 Concentrations of PFOS in biota from locations outside North America and Europe. Mean concentrations are given in ng/mL for blood plasma and whole blood and in ng/g wet w t for liver and kidney. Values in parentheses indicate range. Values below LO Q are denoted by <. Means are calculated only for the detectable observations. Values in brackets [ ] indicate the percentage of detectable observations (Giesy & Kannan, 2001; Kannan e ta )., 2001a; Kannan et a l., 2001b). Perfjuoroalkylated substances - Aquatic environmental assessment 58 000395 600- / ' Dolphin liver Seal liver S eal blood Tuna liver Cormorant liver . North America s Sirop e Remote Eagle liver Figure 5.12 Comparison of PFOS concentrations between North America, Europe and remote concentrations. Mean concentrations are given in ng/mL for blood and in ng/g wet w t for liver. (Giesy & Kannan, 2001; Kannan et al., 2001 a; Kannan et al., 2001b) 5.6 Air Martin et al. (2002) have studied the occurrence of several perfluoroalkylated substances in air. These authors detected fluorinated substances in samples collected at a highly urbanised site (Toronto) and a rural site (Long Point). (ng L'1) N-MeFOSE 101 35 N-EtFOSE 205 76 N-EtFOSA 14 (n=2) Not measured 4:2 FTOH < LOD < LOD 6:2 FTOH 87 29 8:2 FTOH 55 32 10:2 FTOH 29 17 Table 5.13 Concentrations of PFAS in Canadian air samples (Martin et a l., 2002). LOD = Limit of detection Three ECF products and three telomers were detected and quantified in Toronto air. Samples from the rural site showed considerably lower concentrations, but still five out of six attempted measurements demonstrated the occurrence of fluorinated chemicals in air. Perfluoroalkylated substances - Aquatic environmental assessment 59 000396 5.7 Human exposure Human exposure to organic fluorine has been observed as early as 1968. Taves (1968) concluded th a t'[..] if in fact there is a non-exchangeable fluoride in serum it did not break down or diffuse under these conditions, implying a large stable molecule. These findings are consistent with the presence o f a fluorocarbon molecule.' With the development of analytical methods in recent years, the identification of organic fluorine compounds has improved. Although there has been some debate on the origin of organic fluorine in humans (Belisle, 1981), nowadays it is generally accepted that there is an anthropogenic, non-functional origin. Since 1993, several studies have been performed on the occurrence of PFAS in humans. Olsen and co-workers and Gilliland and Mandel published both two studies on levels of PFOS and PFOA in production workers with an occupational exposure (Gilliland & Mandel, 1993; Gilliland & Mandel, 1996; Olsen et al., 1999; Olsen et al., 2000). They reported that PFOS and PFOA accumulated in human serum and liver. | PFOS and PFOA serum concentrations in occupationally exposed workers are in the 1-2 mg/L range. Only the levels in workers from the Cottage Grove plant are higher. In order to compare these data with the general population, also blood from people non occupationally exposed was analysed for PFOS and PFOA. Pooled serum samples from blood dated as far back as 1957 showed concentrations of several tens of pg/L (O ECD, 2002). Samples from 1998-2000 showed average serum levels between 17-53 pg/L for PFOS and 3-17 pg/L for PFOA. No ; differences could be observed between children (37.5 pg/L) and elderly people (31 f pg/L). Table 5.14 summarises the findings from these studies; ; i Perfluoroalkylated substances - Aquatic environmental assessment 60 000397 Cottage Grove Plant (USA) Decatur plant (USA) Antwerp plant (Belgium) Building 236 (USA) Sagamihara (Japan) 1993 1995 1997 1995 1997 1998 2000 1995 1997 2000 2000 1999 111 80 74 90 84 126 263 93 65 258 45 32 2.19 1.75 2.44 1.96 1.51 1.32 1.93 1.48 0.80 0.182 0.135 0.00-12.83 0.10-9.93 0.25-12.83 0.10-9.93 0.09-10.6 0.06-10.06 0.10-9.93 0.1-4.8 0.04-6.24 <0.037-1.036 0.0475-0.628 5.0 6.8 6.4 1.46 1.57 1.54 1.78 1.13 0.84 0.106 - 0.0-80.0 0.0-114.1 0.1-81.3 0.02-6.76 0.04-12.70 0.00-13.2 0.01-7.04 0.008-0.668 - Origin Commercial sources (USA) (pooled) Blood banks (USA) (pooled) American Red Cross blood banks (USA) Children (2-12y) (USA) 3M Corporate managers (USA) Year 1999 1998 2000 1999 1998 n 35 18 652 599 31 Mean (ug/L) 35 29.7 34.9 37.5 47 Range (ug/L) Mean (ug/L) 5-85 3 9-56 17*' 4.3-1656 5.6 6.7-515 5.6 28-96 l2 T 5 rn Range (ug/L) 1-13 12-22 4.27-52.3 4.27-56.1 Not reported Plant management Sagamihara (Japan) 1999 32 40.3 31.9-56.6 Plant management Tokyo (Japan) 1999 30 52.3 33-96.7 Commercial sources, Intergen (USA) 1998 -5 0 0 44 43-44 Commercial sources, Sigma (USA) 1998 -200 33 26-45 Blood banks (the Netherlands) (pooled) 1999 5 53 39-61 Blood banks (Belgium) (pooled) 1999 6 17 4.9-22.2 Blood banks (Germany) (pooled) 1999 6 37 32-45.6 Samples Seattle (65-96y) (USA) 1999 238 31 3.4-175 Table 5.14 PFOS and PFOA serum concentration of production workers and general population (Olsen et a l., 1999; Olsen et a l., 2000; O ECD, 2002; USEPA, 2002). A) PFOA detected in about 1/3 of the pooled samples but quantifiable in only two. B) Only 4 employees were above LOO of 10 ug/L. Perfluoroalkylated substances - Aquatic environmental assessment 000398 61 5.8 Conclusions and recommendations No validated sampling or analysis method yet exists for the measurement of PFAS. i The data observed in the freshwater environment show that point sources of I fluorochemicals lead to relatively higher levels of PFAS in the nearby environment. I Investigated point sources are a manufacturing plant, AFFF spills and industrial use. However, freshwater samples from cities that served as control site also contained PFAS. The highest concentrations of PFAS were observed in sewage sludge and to a lesser extent in effluent and sediment. PFOS was detected in liver, blood, muscle, kidney and brain of organisms around the globe, even in remote locations. Concentrations are higher in more urbanised or industrialised areas. Within species, sometimes, large differences are observed between individual organisms. Other perfluoroalkylated substances are less often detected. f f I * A single study on the occurrence of PFAS in the Dutch environment showed the presence of PFOS in several marine and estuarine biota. All available data on occurrence of PFOS in European biota show concentrations far above LO Q . PFOS concentrations in biota from North America exceed concentrations in biota from Europe. Concentrations in biota from remote regions were much lower. No data are available for telomers in biota or water compartments. Both ECF products and telomere have been detected in air in samples. Compared to an urban area, concentrations in samples from a more rural sampling site were considerably less. PFOS and PFOA have been detected in human blood samples. Concentrations in professionally exposed persons were about 50 (PFOS) to 250 times higher than concentrations in the general public. 5.9 References 3M , 2001, Environmental Monitoring - M ulti-City Study. W ater, Sludge, Sediment, POTW Effluent and Landfill Leachate Samples. Executive Summary, 3M Environmental Laboratory, St. Paul, Minnesota, United States of America Belisle, J, 1981, Organic fluorine in human serum: natural versus industrial sources, Science, 212,1509-1510 Giesy, JP, Kannan, K, 2001, Global distribution of perfluorooctane sulfonate in wildlife. Environ. Sci. Technol., 35,1339-1342 Giesy, JP, Kannan, K, 2002, Perfluorochemical surfactants in the environment, Environ. Sci. Technol., 3 6 ,146A-152A Gilliland, FD, Mandel, JS, 1993, Mortality among employees of a perfluorooctanoic acid production plant, J. Occup. Med., 35, 950-954 Gilliland, FD, Mandel, JS, 1996, Serum perfluorooctanoic acid and hepatic enzymes, lipoproteins, and cholesterol: a study of occupationally exposed men. Am. J. Ind. M ed., 29, 560-568 Hagen, DF, Belisle, J, Johnson, JD, Venkateswarlu, P, 1981, Characterization of fluorinated metabolites by a gas chromatographic-helium microwave-plasma d etecto r-The biotransformation of 1 H .1H , 2H, 2H-perfluorodecanol to perfluorooctanoate, Anal. Biochem., 118, 336-343 Perfluoroalkylated substances - Aquatic environmental assessment 62 000399 Hansen, KJ, Clemen, LA, Ellefson, M E, Johnson, HA, 2001, Compound-Specific, Quantitative Characterization of Organic Fluorochemicals in Biological Matrices, Environ. Sci. Techno!., 35, 766-770. Hansen, KJ, Johnson, HO, Eldridge, JS, Butenhoff, JL, Dick , LA, 2002, Quantitative Characterization of Trace Levels of PFOS and PFOA in the Tennessee River, Environ. Sci. Techno!., 36, 1681-1685 Jarnberg, U, 2002, personal communication, Stockholm University, Sweden Kannan, K, Koistinen, J, Beckmen, K, Evans, T, Gorzelany, JF, Hansen, KJ, Jones, PD, Helle, E, Nyman, M, Giesy, JP, 2001a, Accumulation of perfluorooctane sulfonate in marine mammals, Environ. Sci. Techno!., 35,1593-1598 Kannan, K, Franson, JC , Bowerman, W W , Hansen, KJ, Jones, PD, Giesy, JP, 2001b, Perfluorooctane sulfonate in fish-eating water birds including bald eagles and albatrosses, Environ. Sci. Techno!., 35, 3065-3070 Kannan, K, Newsted, JN, Halbrook, RS, Giesy, JP, 2002a, Perfluorooctanesulfonate and related fluorinated hydrocarbons in mink and river otters from the United States, Environ. Sci. Techno!., 36, 2566-2571 Kannan, K, Hansen, KJ, W ade, T L, Giesy, JP, 2002b, Perfluorooctane sulfonate in oysters, Crassostrea virginica, from the Gulf of Mexico and the Chesapeake Bay, USA, Arch. Environ. Contam. Toxicol., 42, 313-318 Kannan, K, Corsolini, S, Falandysz, J, Oehme, G , Focardi, S, Giesy, JP, submitted, Perfluoroctanesulfonate and related fluorinated hydrocarbons in marine mammals, fishes, and birds from coasts of the Baltic and Mediterranean Seas, Environ. Sci. Techno!., ASAP Key, BD, Howell, RD, Criddle, CS, 1997, Fluorinated organics in the biosphere, Environ. Sci. Techno!., 31, 2445-2454 Kissa, E, 1986, Determination of organofluorine in air, Environ. Sci. Techno!., 20, 1254-1257 Levine, AD, Libelo, EL, Bugna, G, Shelley, T, M ayfield, H, Stauffer, TB, 1997, Biochemical assessment of natural attenuation of JP-4-contaminated ground water in the presence of fluorinated surfactants, Sci. Total Environ., 2 0 8 ,179-195 M artin, JW , M uir, DCG, Moody, C A , Ellis, DA, Kwan, W C, Solomon, KR, Mabury, SA, 2002, collection of airborne fluorinated organics and analysis by gas chromatography/chemical ionization mass spectrometry, Anal. Chem., 74, 584590 Moody, CA , Field, JA , 1999, Determination of perfluorocarboxylates in groundwater impacted by fire-fighting activity, Environ. Sci. Technol., 33, 28002806 Moody, CA, Field, JA , 2000, Perfluorinated surfactants and the environmental implications of their use in fire-fighting foams, Environ. Sci. Technol., 34,38643870 Moody, CA, Kwan.W C, M artin, JW , M uir,DCG, Mabury, SA, 2001, Determination of Perfluorinated Surfactants in Surface W ater Samples by Two Independent Analytical Techniques: Liquid Chromatography/Tandem Mass Spectrometry and 19F NMR, Anal. Chem., 73, 2200-2206 Moody, CA, M artin, JW , Kw an, W C, Muir, DCG, M abury, SA , 2002, Monitoring Perfluorinated S u rfactan ts in Biota and Surface W ater Sam ples Following an Accidental R elease o f Fire-Fighting Foam into Etobicoke C reek, Environ. Sci. Technol.; 3 6 , 545-551 O ECD, 2002, Draft assessment of perfluorooctane sulfonate and its salts, ENV/JM /EXCH(2002)8, Paris, France P erflu o ro aikyla ted su b sta n ce s - Aquatic environmental assessment 63 000400 Ohya, T , Kudo, N, Suzuki, E, Kawashima, Y , 1998, Determination of perfiuorinat^ I carboxylic acids in biological samples by high-performance liquid chromatography 1 J. Chromatogr. B, 72 0 ,1 -7 Olsen, GW , Burris, JM , Mandel, JH , Zobel, LR, 1999, Serum perfluorooctane sulfonate and hepatic and lipid clinical chemistry tests in fluorochemical production employees, J. Occup. Environ. M ed., 41, 799-806 Olsen, G W , Burris, JM , Burlew, M M, Mandel, JH, 2000, Plasma cholecystokinin and hepatic enzymes, cholesterol and lipoproteins in ammonium perfluorooctanoate production workers, Drug Chem. Toxicol., 23, 603-620 I Sweetser, PB, 1965, Separation and determination of arsenic trichloride and stannic f chloride by gas chromatography, Anal. Chem., 2 8 ,1766-1768 Taves, D, 1968, Evidence that there are two forms of fluoride in human serum, Nature, 217,1050-1051 USEPA, 2002, Draft hazard assessment of perfluorooctanoic acid and its salts, February 20, 2002, Washington, D .C ., United States of America j Van de Vijver, K, Hoff, P, Van Dongen, W , Esmans, E, Blust, R, De Coen, W , 2002, I PFOS in marine and estuarine organisms from the Belgian North Sea and Western \ Scheldt estuary, poster presentation at SETAC Europe 2002 Van de Vijver et al., submitted, article on the occurrence of PFOS in biota in Belgian and Dutch waters. ) Perfluoroalkylated substances - Aquatic environmental assessment 64 000401 rfluon'nate^ atography> tane 3roduction tokinin 20 nd stannic erum, alts, W, 2002, Western in 6 Toxicity 6.1 Mechanism of toxicity The mechanism of toxicity of individual perfluoroalkylated substances is not well understood. The perfiuorocarboxylates (including PFOA) are peroxisome proliferators (Intrasuksri et a)., 1998). Several other PFAS are hypothesised to exhibit the same mechanism of toxicity (Giesy & Kannan, 2002). 6.1.1 Metabolism The scarcely available information on metabolism of PFAS shows that PFOS and PFOA are not transformed in biota (O ECD, 2002; USEPA, 2002). 8:2 FTOH is transformed to some extend in rats into PFOA (Hagen et a l., 1981). 6.2 Toxic effects in the aquatic environment 6.2.1 General The toxicity to aquatic organisms of several PFAS has been investigated in several studies. For the telomer products few data are available. For the ECF products, many data are available. There are several reasons why the assessment of the aquatic toxicity of these products from these data is difficult (USEPA, 2002). 1) A variety of different lot numbers with different exact composition and impurities were tested. Impurities may affect toxicity. Moreover, the purity of the test material was not sufficiently tested. For some tests formulated products have been used, with varying concentrations of PFAS. Other tests have been executed with impure chemicals, with as low as 19% of the test chemical present. 2) Tests are performed during a long period of time. During this period the exact composition of the commercial substance may have changed, which makes the comparability of test results more difficult. 3) In many of the toxicity tests isopropanol is added, presumably as a carrier solvent. In tests where the test substance was not 100% pure, the toxicity values were corrected for the purity percentage. 4) In many of the tests only nominal test chemical concentrations were used. Measured test concentrations are always recommended, especially since it is known that PFAS have a high sorption potential. Actual concentrations have indeed been observed that were significantly below nominal (OECD, 2002). Some tests have been performed at levels above the aqueous solubility. Results from these tests have not been included in the present evaluation. 5) For PFOS, tests have been performed with various counterions. It was assumed that the test results with different salts are comparable, since PFOS dissociates immediately to its anion and the according counterion. It is unlikely that these counterions are toxicologically significant, except for the dodecyldimethylammonium salt (DDA) (O EC D , 2002). Following the methodology of Traas (2001), test chemical purity has to be over 80% . If the concentration is between 20-80% , the test protocols are called deviating. The methodology accepts test concentrations up to ten times the limit of solubility. In the present evaluation only studies that had a Klimisch value of 1 or 2 are included. The algae species Selenastrum capricornutum has been renamed Pseudokirchneriella subcapitata (O ECD, 2002). In this report the old name has been maintained. No tests results are available for sediment dwelling organisms. These organisms could be exposed to elevated concentrations in sediment. Perfluoroalkylated substances - Aquatic environmental assessment 000402 65 For the classification of the toxicity data, the categorisation as developed by van Rijn and co-workers (1995) has been used. This categorisation is shown in table 6. 1. I w-- s'* Acute toxicity (L C in mo/LV Chronictoxicitv (LGso irim i Extremely toxic <0.1 < 0.001 ^ Highly toxic <1 < 0.01 Moderately toxic 1-10 0.01-0.1 Slightly toxic 10-100 0.1-1 Practically non-toxic >100 >1 Table 6.1 Classification of toxicity data (Van Rijn et al., 1995) 6.2.2 Toxicity to freshwater organisms Most of the reliable data that are available refer to PFOS and PFOA. Some reliable data are available for 8:2 FTOH, N-perfluorooctylsulfonyl-n-ethylglycinate (PFOSGE), N-EtFOSA, N-EtFOSE, N-EtFOSEA and POSF. Many of the data available are from test using protocols deviating from the standards and are reported separately. PFOS Acute toxicity In table 6.2 the freshwater acute toxicity values for PFOS are summarised. The data in table 6.2a show that PFOS is practically non-toxic to freshwater algae and higher plants (Duckweed). Growth rate was used as end-point for the evaluation of toxicity to algae (USEPA, 2002). Towards invertebrates PFOS exhibits only slight toxicity. The lowest reliable toxicity value for fish is an LC, of 7 .8 mg/L (Rainbow trout). The acute toxicity results from tests with deviating protocols are presented in table 6.2b. Algae PFOS-K Algae PFOS-K Algae PFOS-K Algae PFOS-K Algae PFOS-K Higher plants PFOS-K Invertebrates PFOS-K Invertebrates PFOS-K Invertebrates PFOS-K Fish PFOS-K Fish PFOS-K Fish PFOS-K 126 96h EC50 growth rate Selenastrum OECD 201 120 72h caoricomutum 82 96h EC50 cell density Selenastrum OECD 201 caoricomutum 82 96h EC50 cell-count Selenastrum OECD 201 caoricomutum 176 96h EC50 growth rate Anabaena OPPTS 94 NOEC growth rate flosaqua 850.5400 305 96h EC50 growth rate Navicula OPPTS 206 NOEC growth rate pelliculosa 850.5400 108 7d IC50 Duckweed OPPTS 15.1 NOEC 850.4400 61 48h EC50 Daphnia magna OECD 202 33 NOEC 58 48h EC50 Daphnia magna ISO . 1982 59 96h LC50 Freshwater OECD 203 20 NOEC mussel 9.5 96h LC50 Fathead minnow OECD 203 3.3 NOEC 7.8 96h LC50 Rainbow trout Env. Canada 22 96h LC50 Rainbow trout OECD 203 Table 6.2a Acute toxicity of PFOS to freshwater organisms (standardised protocols) 11 12 13 12 14 15 6 5 10 1 5 5 Perfluoroalkyfated substances - Aquatic environmental assessment 66 000403 d by van in table te ita are The 'gae and duation >nly slight tain bow I in table )1 11 )1 12 )1 13 12 14 15 >6 5 t 10 1 fa 5 5 Invertebrates Invertebrates Fish Fish Fish PFOS-Li PFOS-DDA PFOS-Li PFOS-DDA PFOS-DEA 210 48h EC50 Daphnia magna Not noted 100 NOEC 4.0 48h EL50 Daphnia magna OECD 202 2.2 NOEC 4.7 96h LC50 Fathead minnow Not noted 200 96h LL50 Fathead minnow OECD 203 <170 NOEL 7.8 96h LC50 Bluegill sunfish OECD 203 4.5 NOEC Table 6.2b Test results for acute toxicity of PFOS to freshwater organisms obtained from tests with deviating protocols 8 9 2 3 4 Sub-chronic/chronic toxicity Fish appear to be much more sensitive them invertebrates and algae to sub chronic/ chronic exposure to PFOS (see table 6 .3 ). The same pattern was found with acute toxicity. The NOEC of 0.30 mg/L is consistent with results from a bioconcentration study. In that study no effects were measured at 0.086 mg/L during 62 days uptake, but 100% mortality occurred at an exposure concentration of 0.87 mg/L during 35 days. The two available studies for daphnids show consistent results and practically no chronic toxicity. Invertebrates PFOS-K Invertebrates PFOS-K Fish PFOS-K Fish PFOS-K Fish PFOS-K 12 21d NOEC Daphnia OECD 211 reproduction, magna survival, growth 12 21d EC50reproduction Daphnia ASTM/OECD, 7 28d NOECreproduction magna 1981 11 28d EC50reproduction 0.30 42d NOECsurvival Fathead OECD 210 0.30 42d NOECgrowth minnow >4.6 5d NOEChatch 1 30d NOECeariy-life Fathead Not standard stages minnow >0.086 <0.87 62d NOECmortality Bluegill OECD 305 sunfish Table 6.3. Sub-chronic/chronic toxicity of PFOS to freshwater organisms 19 7 16 17 18 PFOA Acute and sub-chronic/chronic toxicity In table 6.4a the acute freshwater toxicity values for PFOA are summarised. Only studies that had a Klimisch value of 1 or 2 are reported. In the draft hazard assessment of the USEPA (2002) several other ecotoxicity data are reported. However, the reliability of some of these studies was limited. Only studies for which the reliability could be assessed were included in the present review. The results of the reliable tests that are presented in table 6.4a indicate practically no acute toxicity of PFOA to all species tested. The results obtained from tests with deviating protocols, presented in table 6.4b , show that PFOA is moderately toxic to algae and slightly toxic to fish. The few available sub-chronic/chronic values for PFOA indicate practically no subchronic/chronic toxicity of this compound to algae or fish. Perfluoroalkylated substances - Aquatic environmental assessment t 000404 67 Table 6.4a Toxicity of PFOA to freshwater organisms (standardised protocols) Sludge Sludge Sludge Bacteria Bacteria Bacteria Bacteria Algae Algae Algae Fish Fish Fish Fish Fish Fish Fish PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA PFOA >450 3h EC50 - OECD 209 41 >664 3h EC50 >450 3h EC50 - OECD 209 OECD 209 42 43 iS >450 30 min EC50 Photobacterium Microbics 36 * ! phosphoreum microtox 630 30 min EC50 Photobacterium Microbics 38 ' ! phosphoreum microtox 390 30 min EC50 Photobacterium Microbics 39 phosphoreum microtox 117 30 min EC50 Photobacterium Microbics 40 phosphoreum microtox 2.2 96h EC50 Selenastrum EPA/TSCA 31 0.45 NOEC capricomutum 979.1050 1.3 96h EC50cell density Selenastrum EPA/TSCA 32 3.8 EC50growth rate capricomutum 979.1050 396 96h EC50 Selenastrum EPA/TSCA 33 666 EC50growth rate capricomutum 979.1050 42 NOECcell count 86 NOECgrowth rate 86 LOECcell count 166 LOECgrowth rate >450 96h LC50 Fathead minnow OECD 203 22 494 96h LC50 Fathead minnow EPA/TSCA 23 1993 432 96h LC50 Fathead minnow EPA/TSCA 25 284 NOEC 797.1400 400 96h NOEC Fathead minnow EPA/TSCA 26 270 NOEC 797.1050 263 48h EC50 Fathead minnow OECD 202 27 240 48h EC50 Fathead minnow EPA/TSCA 28 146 NOEC 797.1300 15/35 48h EC50/LC50 Fathead minnow EPA/TSCA 30 6 NOEC 797.1300 Table 6.4b Results from deviating test protocols for the acute toxicity of PFOA to freshwater organisms Perfluoroaikylated substances - Aquatic environmental assessment 68 000405 jfc Algae PFOA Fish PFOA 43 >100 14d EC50cell count Selenastrum Modified capricomutum EPA/ASTM/OECD 30d NOEC Fathead minnow Adapted EPA, 1972 Table 6.5 Chronic toxicity of PFOA to freshwater organisms 45 44 8:2 FTOH Acute and chronic toxicity Acute no effects concentrations have been observed in toxicity tests with 8:2 FTOH (see table 6 .6 ). Test results were based on nominal concentrations. It is not possible to appropriately judge the toxicity of this telomer from these data. Several chronic toxicity studies are underway (TRP, 2002). Algae Invertebrates Fish 8:2 FTOH 8:2 FTOH 8:2 FTOH 0.20 0.16 0.18 Table 6.6 72h NOEC Scenedesmus OECD 201 46 subspicatus 48h NOEC Daphnia magna OECD 202 46 96h NOEC Dario rerio OECD 203 46 Acute freshwater toxicity of 8:2 FTOH to freshwater organisms Other PFAS For the remaining PFAS discussed in the present study the toxicity data set is far from complete (see table 6.7). N-EtFOSA exhibits slight toxicity towards invertebrates, all other tests indicate practically no toxicity. The results of tests with deviating protocols show slight toxicity of PFOSGE to fish. PFDS is slightly toxic to invertebrates and moderately toxic to fish. Fish Fish Fish Sludge Invertebrates Fish n-EtFOSE n -EtFO SEA POSF n-EtFOSA n-EtFOSA n-EtFOSA > 20pg/L Chronic NOEC Fathead minnow USEPA, 1972 >1000 96h LC50 Fathead minnow Not noted >1000 96h LC50 Fathead minnow Not noted >1000 3h EC50 - OECD 209 14.5 48h EL50 Daphnia magna Adapted OECD 202 206 96h LL50 Fathead minnow Adapted OECD 203 Table 6.7a Acute and chronic toxicity data of several PFAS to freshwater organisms (standardised test protocols) 51 52 53 56 55 54 Bacteria Algae PFOSGE PFOSGE Fish PFOSGE Fish Sludge PFOSGE PFDS Bacteria PFDS Invertebrates PFDS Invertebrates PFDS Fish PFDS 115 30 min EC50 Photobacterium Microbics 50 phosphoreum microtox 125 96h EC50cell count Selenastrum OECD 201 49 254 EC50growth rate capricomutum 91 NOEC 41 96h LC50 Fathead minnow OECD 201 47 23 NOEC 362 96h LC50 Fathead minnow EPA 48 327 30 min EC50 - Microbics 61 microtoxs 250 - 17.3% inhibition Photobacterium OECD 209 60 phosphoreum 32 48h EC50 Daphnia magna EPA 660/3 59 11 48h EC50 Daphnia magna OECD 202 58 4.8 96h LC50 Fathead minnow OECD 203 57 Table 6.7b Results for acute toxicity data of several PFAS to freshwater organisms from deviating test protocols Perfluoroalkylated substances - Aquatic environmental assessment 000406 69 6.2.3 Summary of freshwater toxicity data The lowest effect concentrations and NOECs that have been published in the literature have been summarised in table 6.8. PFOS PFOA 8:2 FTOH N-EtFOSA Acute Algae Selenastrum capricomutum Invertebrates Oaphnia magna 72h ECso= 120 48h ECso = 58 1? s ~ \ Fish Rainbow trout 96h ECso = 7.8 Chronic Invertebrates Daphnids 28d NOEC = 7 Fish Fathead minnow 42d NOEC = 0.30 Acute Bacteria Photobacterium phosphoreum 30 min ECso = 722 Algae Selenastrum capricomutum 96h ECso >1000 Fish Fathead minnow 96h LC50= 300 Chronic Algae Selenastrum capricomutum 14d ECso = 43 Fish Fathead minnows 30d NOEC >100 Acute Algae Scenedesmus subspicatus 72h NOEC = 0.20 Invertebrates Daphnids 48h NOEC = 0.16 Fish Danio rerio 96h NOEC = 0.18 Acute Invertebrates Daphnids 48h EL50 = 14.5 Fish Fathead minnow 96h LLso = 206 Table 6.8 Lowest observed U EJC and NOECs of PFAS in freshwater organisms. 6.2.4 Toxic effects in the marine environment For the marine environment toxicity data are only available for PFOS. Table 6.9 presents the published toxicity data for marine organisms. The few data that are available for the toxicity of PFOS to marine organisms show moderate toxicity to invertebrates. For algae and fish no conclusions could be drawn in this present study, because no effects were observed at the highest concentration tested. The chronic study with shrimps showed NOECs between 0.25-0.55 mg/L for reproduction, survival and growth. Algae PFOS Invertebrates PFOS Invertebrates PFOS Invertebrates PFOS Fish PFOS >3.2 96h EC50growth rate Skeletonema OPPTS >3.2 NOECgrowth rate costatum 850.5400 3.6 96h LC50 Mysid shrimp OPPTS 1.1 NOEC 850.1035 >3.0 96h EC50 Eastern oyster OPPTS 1.9 NOEC 850.1025 0.25 35d NOECreproduction Mysid shrimp OPPTS 0.55 NOECsurvival 850.1350 0.25 NOECgrowth >15 96h LC50 Sheepshead OECD 203 minnow Table 6.9. Toxicity of PFOS to marine organisms. 65 63 64 66 62 Perfluoroalkylated substances - Aquatic environmental assessment 70 000407 6.3 Standards and derivation of iMPCs (Based on Groshart et al., 2001) 6.3.1 Introduction In the Netherlands, harmonised standards for several environmental compartments are derived for a number of chemicals (MilBoWa, 1999). The purpose of MilBoWa (1999) is to create a system of limit- and target values for soil and surface water. A limit value is a quality level that minimally should be achieved or maintained. A target value is a quality level at which no adverse effects are expected. The limit value is based upon the `maximal permissible concentration' (M PC), the target value on the 'negligible concentration' (N C). In 2001 the procedure for the derivation of MPCs for the setting of environmental risk limits was updated (Traas, 2001). The MPC is defined as the concentration at which at least 95% of the species in the ecosystem will be protected (method of Aldenberg & Jaworska (2000)). The negligible risk level is defined as 1% of the M PC. For PFAS there are no standards derived yet in the Netherlands. 6.3.2 Derivation method For the derivation of M PCs directly from ecotoxicological endpoints two different methods are used: the refined effect assessment method and the preliminary effect assessment method. Long-term chronic data are preferred to short term acute data. The refined effect assessment method is preferable. However, application of this method is based on data availability: at least four NOEC values are needed for four different taxonomic groups. If these data are not available the preliminary effect assessment method is applied. In this case in principle the EU TGD (ECB, 1996) is applied (table 6 .11). In figure 6.10 the direct method for MPC derivation is presented. At least 4 long term NOECs no / Less than 4 long term NOECs but at least a complete base set \ yes Apply refined effect assessment according to Aldenberg & Slob Incomplete base set at least 1 short term L(E)C50/NOEC yes 1i____________________________ no Apply the modified EPA method according to the OECD Apply the TGD method according to the EU ' No MPC i MPC value for water, soil and sediment Figure 6.10 Scheme for the derivation of the M PC: direct method There are two exceptions to the use of the TGD method: 1. Only when long term NOECs on three trophic levels are available, a comparison with data from the (complete) base se t4is no longer demanded. 4 The complete base set for toxicology data exists of acute UE)Q o for each of three trophic levels (fish, daphnia, algae). Perfluoroalkylated substances - Aquatic environmental assessment 000408 71 2. It is inferred that for more hydrophobic compounds, short term toxicity data may not be representative, since the time span of an acute test may be too short to reach a toxic internal level. In those cases, base set completeness is not demanded and an assessment factor of 100 may be applied to a chronic test, which should not be an alga test if this is the only chronic test available If the base set is incomplete, the TCD method cannot be applied, and other arbitrary safety factors are used (the modified EPA-method (OECD, 1992)): a factor 10 and/or 1000 will be applied to the NOEC and/or l(E)C 50, respectively, to derive the M PC. It should be stressed here that this exception may only be used if the TGD can not be applied. In table 6.11 the safety factors of the modified EP/\ method, dependent on the number of available toxicity data, are presented. At least one short-term L(E)C50 from each of 3 trophic 1000 ^ levels of the base-set (fish, daphnia and algae) One long-term NOEC (either fish or daphnia) 100 ^4 Two long-term NOECs from species representing two 100 ^4 trophic levels (fish and/or daphnia and/or algae) Long-term NOECs from at least 3 species (normally fish, daphnia and algae) representing three trophic levels Field data or model ecosystems 50 ! 50 I 10 1 Reviewed on a case by easel basis 1 L----------------- -- --------if Table 6.11 Assessment factors for aquatic toxicity data following EU/TDG (ECB, 1996) according to EUSES (EC , 1996) The calculated MPC in the present report will be defined as `indicative M PC' (iM PC). Contrary to the limit and target values the derived iM PCs have only a technical status and no environmental policy value. They are not legally set and may change as soon as more toxicity data become available and/or an MPC is derived by the INS-project. Lowest acute L(E)C or QSAR estimation for acute toxicity 1000 Lowest acute L(E)C*> or QSAR estimation for acute toxicity for at 100 least algae, crustaceans and fish Lowest NOEC or QSAR estimation for chronic toxicity 10' Lowest NOEC or QSAR estimation for chronic toxicity for at least 10 algae, crustaceans and fish Table 6.12 Safety factors for the derivation of iM PCs in surface water (modified EPA method) th is value will be compared with the value based on acute L(E )C M values. The lowest value will be selected Based on the toxicity data presented in this study, the iMPCs are derived using the procedure described by Traas (2001). The derivation is explained in annex V . To derive the iMPC for sediment it is generally advised to use the equilibrium partition (EP) method, which relies on (see Slooff, 1992; Beek, 1993; Kalf, Perfluoroalkylated substances - Aquatic environmental assessment 72 000409 xidty cfata Jy be too eteness is i a chronic t available. ther '2)): a oectively, >ly be used dified EPa ted. 1999; Traas, 2001). In this study this advice has not been followed, because not a suitable predictor for the environmental behaviour (see section 4.3.1). Furthermore, the M PC,,dimentcould not be derived direct from effect concentrations, because no data were available on toxic effects in the soil or sediment. In the present study iMPCs for PFOS, PFOA and PFOSGE were derived. For all other PFAS insufficient data were available. The results of this derivation are presented in table 6.13. is Only for PFOS many data were available, making it possible to use a relatively small assessment factor of 50. The other data have been derived using an assessment factor of 1000 (see annex V ). PFOA 300 n-EtFOSA 14.5 Table 6.13 iMPCs for PFOS, PFOA and n-EtFOSA. 6.3.3 Comparison of iMPCs to environmental concentrations The PFAS concentrations that are observed in the environment can be compared to the indicative M PC. No occurrence data are available for n-EtFOSA, therefore this comparison will be limited to PFOS and PFOA. PFOS The highest freshwater concentrations that were observed in the multi-city environmental monitoring study (see section 5.3) were 4.98 pg/L for PFOS in POTW effluent from Decatur (3M , 2001). In quiet water from Decatur 0.111 pg/L PFOS was observed. The highest PFOS water concentration from control cities is 2.19 pg/L (Port St. Lucie). The highest PFOS water concentration after an AFFF spill (see section 5.3) was 2210 pg/L. These values indicate that the MPC for PFOS may be approached close to point sources of PFAS. However, also PFOS concentrations in a non-point sourced city could approach the iM PC. PFOA The highest freshwater concentrations that were observed In the multi-city environmental monitoring study (see section 5.3) were 2.28 pg/L for PFOA in POTW effluent from Decatur. In quiet water from Decatur 0.060 pg/L PFOA was observed. The highest PFOA water concentration from control cities is 0.749 pg/L (Port St. Lucie). The highest PFOA water concentration in groundwater at a fire fighting training site is 6570 pg/L; after an AFFF spill the highest observed PFOA concentration was 11.3 pg/L. These values indicate that the iMPC for PFOA might only be exceeded after spills. 6.4 Human toxicity The human toxicity of PFOA and to a lesser extent PFOS have been and still are the subject of many studies (USEPA, 2002; O ECD, 2002). For 8:2 FTOH few data are available, but many studies are underway. Results are expected by the end of 2002 (TRP, 2002). 6.4.1 Behaviour in humans PFOS PFOS was shown to be distributed in humans to serum and liver, where it is not metabolised. The excretion from the body is slow and occurs via urine and faeces Perfluoroalkylated su b stan ce s - Aquatic environmental assessment 000410 73 (OECD, 2002) PFOS has an estimated excretion half-life in humans of 8.67 yea^ W This is high compared to adult rats (100 days) and Cynomolgus monkeys (200 1 days). PFOS is well absorbed orally. 1 PFOA PFOA has an estimated half-life between 1 and 3.5 years in humans. PFOA is well absorbed following oral and inhalation exposure and to a lesser extent following dermal exposure. As was observed in other biota, PFOA does not partition to the body fat, but covalently binds to macromolecules. In liver, plasma and kidney PFOA is not metabolised in the human body. Urine and faeces are the primary routes of excretion for PFOA; female rats possess an unidentified extra mechanism for the excretion of PFOA. Therefore this chemical is excreted much faster in female rats than in male rats. The difference between sexes has also been observed in dogs, but not in primates and humans (USEPA, 2002). For perfluorocarboxylic acids the length of the perfluoroalkyl chain is important for the excretion. Perfluorocarboxylic acids with longer chain length are less eliminated (Kudo et al., 2001). I j | 6.4.2 Acute toxicity PFOS The available rodent toxicity data of PFOS have been summarised in table 6.14. Oral Rats L D ,, = 251 Rats 1h LCW= 5.2 Eye irritation Rabbits M ildly irritating Skin irritation Rabbits Non-irritating Table 6.14 Acute toxicity data of PFOS to rodents PFOA The available rodent toxicity data of PFOA have been summarised in table 6.15. Oral CD Rats LD ,,, > 500 (male) LDm 250-500 (female) W istar rats LDW< 1000 (female) Inhalation Rats 1h NOEC > 18,6 mg/L Dermal Rabbits LDm > 2000 mg/kg Eye irritation Rabbits Irritating Skin irritation Rabbits Irreversible tissue damage Rabbits Non-irritating Table 6.15. Acute toxicity of PFOA to rodents 6.4.3 Chronic toxicity PFOS In repeat-dose oral toxicity studies with PFOS using rats and primates the exposure resulted in hepatotoxicity and mortality. A t an exposure level of from 2mg/kg/day observed effects in rats are increases in liver enzymes, hepatic vacuolisation and hepatocellular hypertrophy, gastrointestinal effects, haematological abnormalities, weight loss, convulsions and death. These effects were confirmed by a 2-year test with rats. The lowest observed adverse effect level (LO AEL) in female rats was 5 mg/L; the associated no observed adverse effect level (NOAEL) was 2 mg/L. In male rats the LOAEL was 0.5 mg/L; no NOAEL could be determined. In a developmental effect study the NOAEL and the LOAEL for the second generation of rats were determined to be 0.1 mg/kg/day and 0 .4 mg/kg/day, respectively (OECD, 2002). Perfluoroalkylated substances - Aquatic environmental assessment 74 0004X1 f 8-67 years eys (200 PFOA is vve|| : following ition to the kidney rats possess this lifference 1 humans oalkyl chain iin length ale 6.14. le6.15. exposure /kg/day n and nalities, ear test was 5 1. In eration vely In repeat-dose oral toxicity studies with PFOS using Rhesus monkeys the effects observed included anorexia, emesis, diarrhoea, hypoactivity, prostration, convulsions, atrophy of the salivary glands and the pancreas, marked decreases in serum cholesterol, and lipid depletion in the adrenals. These effects were observed at levels from 1.5 mg/kg/day and above. No survival was reported after three weeks treatment with 10 mg/kg/day and after seven weeks with 4.5 mg/kg/day. In a six-month study no effects were observed at doses of 0.15 or 0.03 mg/kg/day (O ECD, 2002). In mutagenicity test with bacteria (S. typhimurium, E. coli), human lymphocytes, rat hepatocytes and mouse micronucleus, PFOS was found to be non mutagenic (OECD, 2002). In a 2-year carcinogenicity assay with Sprague-Dawley rats significant increase in the incidence of hepatocellular adenomas was observed at the highest dose of 20 mg/L of PFOS (OECD, 2002). PFOA In various studies with bacteria (S. Typhimurium, E. Coli) and human lymphocytes PFOA was found to be non-mutagenic. PFOA did induce chromosomal aberrations and polyploidy in Chinese hamster ovaries (USEPA, 2002). However, PFOA was negative in an essay with mouse embryo fibroblasts and in an in vivo mouse micronucleus assay. Sub-chronic studies in rats and mice showed that the liver is the primary target organ. Observed effects are increased liver and kidney weight, hepatocellular hypertrophy, at 1000 mg/L for female rats (76.5 mg/kg/day) and 100 mg/L for male rats (5 mg/kg/day). Studies with rhesus monkeys resulted in death, lipid depletion in the adrenals, hypoplasia of the bone marrow, and moderate atrophy of the lymphoid follicles in the spleen and lymph nodes at 30 mg/kg/day or higher (USEPA, 2002). Rats fed with 300 mg/L PFOA showed increased liver and kidney weight, haematological effects and liver lesions in males and females. In addition, increases in testicular masses (males at 300 m g/L) and ovarian tubular hyperplasia (females at 30 mg/L) were observed (USEPA, 2002). Carcinogenity studies with rats showed that PFOA is weakly carcinogenic, inducing Leydig cell adenomas in the males and mammary fibroadenomas in the females following 2-year exposure to 300 m g/L. At that level PFOA has also been reported to be carcinogenic to the liver and pancreas of male CD Rats (USEPA, 2002). The results of several key studies on PFOA (90-day primate, two generation, kinetics) are ungoing (APM E, 2002). Telomere (based on DuPont 2002) For a mixture of 6:2 FTOH, 8:2 FTO H , 10:2 FTOH and 12:2 FTOH three NOELs have been determined. The repeated dose and the reproductive toxicity NOEL was 25 mg/kg/day. No developmental toxicity was observed at 200 mg/kg/day. Furthermore these substances reacted negative in the AMES, Chrom Ab genotoxicity tests. 6.5 Conclusions and recommendations Various data were available to evaluate the toxicity of PFOS and PFOA. The reliability of many of these tests must be considered as limited, because nominal concentrations were used. Due to the special, high sorptive behaviour, the actual concentration may have been significantly reduced. Furthermore, many of the test Perfluoroalkylated substances - Aquatic environmental assessment 75 000412 were performed at low test chemical purity, and were therefore deviating from the standard methodology. Many of the results are therefore of limited reliability, but can very well serve as a first indication. PFOS is moderately acute toxic to freshwater fish and slightly toxic to invertebrates. PFOS is practically non-toxic to algae. PFOS is slightly chronic toxic to freshwater fish and practically non-toxic to invertebrates. PFOS is moderately (acute) and slightly (chronic) toxic to marine invertebrates. For PFOS the derived iMPC is 5 pg/L. PFOS concentrations were shown to equal the iMPC in freshwater receiving wastewater effluents from a production site. In other freshwaters, the concentrations observed are usully far below, although the iMPC may be approached to within a factor of 4. The acute toxicity of PFOA to freshwater algae, invertebrates and fish is practically nil. For PFOA an iMPC of 300 pg/L has been derived. It is unlikely that this iMPC will be exceeded for longer periods. N-EtFOSA exhibits slight acute toxicity to invertebrates. No effects have been observed for 8:2 FTOH. No conclusions regarding the toxicity of this substance can be drawn, since nominal concentrations have been used in tests. Concerning humans, both PFOS and PFOA have long half-lives (8.67 and 1-3.5 years, respectively) in the human body. Both chemicals are distributed to liver, plasma and kidney. To rodents PFOS and PFOA exhibit low acute toxicity, but they are eye irritating. In chronic feeding tests with rodents and primates the primary target was the liver for PFOS and PFOA. PFOA was found to be weakly carcinogenic. Mutagenicity testing of PFOS did not show any mutagenic effects. PFOA induced chromosomal aberrations and polyploidy in CHO cells, but did not show mutagenic effects in most mutagenicity tests, including an in vivo micronucleus test. In a developmental effect study with PFOS the NOAEL and the LO AEL for the second generation of rodents were determined to be 0.1 mg/kg/day and 0.4 mg/kg/day, respectively. 6.6 References 3M , 2001, Environmental Monitoring - M ulti-City Study. W ater, Sludge, Sediment, POTW Effluent and Landfill Leachate Samples. Executive Summary, 3M Environmental Laboratory, St. Paul, Minnesota, United States of America Aldenberg.T, Jaworska, J, 2000, Uncertainty of the hazardous concentration and fraction affected for normal species sensitivity distributions, Ecotoxicology and Environmental Safety, 4 6,1-18 Beek, M A, 1993, Het maximal toelaatbaar risiconiveau (M TR): Uitgangspunten en berekeningsmethode, RIZA, werkdocum ent93.150X, Lelystad, The Netherlands DuPont, 2002, Presentation May 2002, Dordrecht, The Netherlands ECB, 1996, European Chemicals Bureau, Technical Guidance Document in support of commission directive 93/67/EEC on risk assessment for new notified substances and commission regulation (EC) No 1488/94 on risk assessment for existing substances Part I to IV, Ispra, Italy EC, 1996, European Commission, EUSES, The European Union System for the Evaluation of Substances, RIVM Bilthoven, The Netherlands Giesy, JP, Kannan, K, 2002, Perfluorochemical surfactants in the environment, Environ. Sci. Techno!.,3 6 ,146A-152A Perfluoroalkylated substances - Aquatic environmental assessment 76 0G0413 n from the ab'ty, but rnic toxic derately ie derived freshwater ers, the e practically his MPC the re been i 1-3.5 liver, but the liver anicity nosomal :cts in ' the ).4 iry, 3M i and nd ten en mds ipport anees Groshart, CP, Okkerman, PC, Pijnenburg, AM CM , 2001, Chemical study on Bisphenol A , RIKZ report 2001.027, The Hague, The Netherlands Hagen, DF, Bellsle, J, Johnson, JD, Venkateswarlu, P, 1981, Characterization of fluorinated metabolites by a gas chromatographic-helium microwave-plasma detector-The biotransformation of 1 H, 1H, 2H, 2H-perfluorodecanol to perftuorooctanoate, Anal. Biochem., 118, 336-343 Intrasuksri, U, Rangwala, SM, O 'Brien, M , Noonan, DJ, Feller, DR, 1998, Mechanisms of peroxisome proliferation by perfluorooctanoic acid and endogenous fatty acids, Gen. Pharmac., 31,187-197 Kalf, DF, M ensink, BJWG, Montforts, M HMM, 1999, Protocol for derivation of Harmonised Maximum Permissible Concentrations (M PCs), RIVM report 601506001, Bilthoven, The Netherlands Kudo, N, Suzuki, E, Katakura, M , Ohmori, K, Noshiro, R, Kawashima, Y, 2001, Comparison of the elimination between perfluorinated fatty acids with different carbon chain length in rats, Chem.-Biol. Interact., 134, 203-216 MilBoWa, 1999, Milieukwaliteitsdoelstellingen Bodem en W ater. Kamerstukken II, 1990-1991, 21 990, n r.1 ,1991, The Hague, The Netherlands OECD, 1992, Report of the workshop on the extrapolation of laboratory aquatic toxicity data to the real environment. Organisation for economic co-operation and development, OECD Environmental Monographs No 59, Paris, France OECD, 2002, Draft assessment of perfluorooctane sulfonate and its salts, ENV/JM /EXCH(2002)8, Paris, France Slooff, W , 1992, RIVM guidance document, Ecotoxicological effect assessment: Deriving maximum tolerable concentrations (M TC) from single-species toxicity data. RIVM -report no. 719102018, Bilthoven, The Netherlands Traas, TP (Ed .), 2001, Guidance document on deriving environmental risk limits, RIVM report 601501012, Bilthoven, The Netherlands TRP, 2002, Telomer Research Program, Presentation at DuPont, May, Dordrecht, The Netherlands USEPA, 2002, Draft hazard assessment of perfluorooctanoic acid and its salts, February 20, 2002, Washington, D .C ., United States of America Van Rijn, JP, Van Straalen, NM, Willems, J, 1995, Handboek bestrijdingsmiddelen, gebruik en milieu-effecten, VU Uitgeverij, Amsterdam, The Netherlands Van Straalen, NM, Denneman, CAJ, 1989, Ecotoxicological evaluation of soil quality criteria, Ecotox. Environ. Saf., 18, 241-251 References of toxicity tests 1. 3M , 1999, PFOS: a 96-hour static acute toxicity test with the fathead minnow (pimephales promelas), W ildlife International Ltd., Easton, Maryland, United States of America 2. 3M , 1994a, 96-hour toxicity test data summary Pimephales Promelas, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 3. 3M , 1997a, Acute toxicity of P 3025 developmental material to Fathead minnow (Pimephales promelas), Asd corporation, Duluth, Minnesota, United States of America 4. 3M , 1979, 96-Hour acute toxicity test to Bluegill Sunfish (FC-99, DEA salt of PFOS), Analytical Biochemistry Laboratories, Inc., Columbia, Missouri, United States of America 5. Panarctic oil, 1986, Potential for environmental impact of AFA-6 surfactant, Beak consultants Ltd., Mississauga, Ontario, Canada Perfluoroalkylated substances - Aquatic environmental assessment 000414 77 6. 3M, 2000a, PFOS: a 48-hour static acute toxicity test with the cladoceran (Daphnia magna), Wildlife International Ltd., Easton, M aryland, United States of America 7. 3M, 1984a, Effect of Potassium Perfluorooctane sulfonate on Survival, etc., 3^ Environmental Laboratory, St. Paul, Minnesota, United States of America 8. 3M, 1994, Acute toxicity test to Daphnia, Daphnia Magna, 94-X (Li salt of PFOS), 3M Environmental laboratory, St. Paul, Minnesota, United States of America 9. 3M , 1997b, Acute toxicity of P 3025 developmental material to Daphnia magna, Asd corporation, Duluth, Minnesota, United States of America 1 0 .3M , 2000b, PFOS: a 96-hour static acute toxicity test with the freshwater mussel (Unio complamatus), W ildlife International Ltd., Easton, Maryland, United States of America 1 1 .3M , 2000c, PFOS: a 96-hour static acute toxicity test with the freshwater alga (Selenastrum capricornutum), W ildlife International Ltd., Easton, Maryland, United States of America 1 2 .3M , 2001a, PFOS: a 96-hour toxicity test with the Freshwater alga (Anabaena flos-aquae), W ildlife International Ltd., Easton, Maryland, United States of America 1 3 .3M , 1981a, Multi-phase exposure/ Recovery Algal assay test method, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 1 4 .3M , 2001 b, PFOS: a 96-hour toxicity test with the Freshwater diatom (Navicula peliculosa), Wildlife International Ltd., Easton, M aryland, United States of America 1 5 .3M , 2001 c, PFOS: a 7-day toxicity test with duckweed (Lemna gibba g3), Wildlife International Ltd., Easton, M aryland, United States of America 16.3M , 2000d, PFOS: an early life-stage toxicity test with the fathead minnow Pimephales promelas), Wildlife International Ltd., Easton, M aryland, United States of America 17.3M , 2001d, Perfluorooctanesulfonate, potassium salt (PFO S): A flow-through bioconcentration test with the Bluegill (lepomis macrochirus), W ildlife International Ltd., Easton, Maryland, United States of America 1 8 .3M , 1978a, The effects of continuous aqueous exposure to 14C-78.02 on hatchability of eggs and growth and survival of fry of Fathead minnow (Pimephales promelas), EG&G, Wareham, Massachusetts, United States of America 19. M , 2000e, PFO S: a semi-static life-cycle toxicity test with the cladoceran (Daphnia magna), Wildlife International Ltd., Easton, M aryland, United States of America 20.3M , 1980, Acute toxicity testing: FC-143, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 2 1 .3M , 1987a, 96h acute static toxicity of FC-1210 to Fathead minnow (Pimephales promelas), 3M Environmental laboratory, St. Paul, Minnesota, United States of America 2 2 .3M , 1990a, Static AcuteToxicity of FI-1003 to the Fathead M innow, Pimephales promelas, Envirosystem Division, Hampton, New Hampshire, United States of America 2 3 .3M , 1996a, Acute toxicity of FC-1015 to the Fathead minnow, Pimephales promelas, T .R . W ilbury laboratories Inc., Marblehead, Massachusetts, United States of America 2 4 .3M , 1985, 96h acute static toxicity of FX-1001 to Fathead minnow (Pimephales promelas), 3M Environmental laboratory, St. Paul, Minnesota, United States of America 2 5 .3M , 1995a, Acute toxicity of L-13492 to the Fathead minnow, Pimephales promelas, , T .R . W ilbury laboratories Inc., Marblehead, Massachusetts, United States of America* Perfluoroalkylated substances - Aquatic environmental assessment '> i . ,, , , 78 000415 * ceran ted States **' etc- 3m arica salt of ites of i nia :a /ater land, ater alga /land, nabaena as of 3M :a I ilted 53). now nited trough on ; of states St. es ted i, s ted 2 6 .3M , 1995b, Acute toxicity of N-2803-2 to the Fathead minnow, Pimephales prometas, , T.R . Wilbury laboratories Inc., Marblehead, Massachusetts, United States of America 2 7 .3M , 1990b, Static acute toxicity of FX-1003 to the Daphnid, Daphnia magna, Envirosystem Division, Hampton, New Hampshire, United States of America 2 8 .3M , 1996b, Acute toxicity of FC-1015 to the Daphnid, Daphnia magna, T.R . Wilbury laboratories Inc., Marblehead, Massachusetts, United States of America 2 9 .3M , 1995c, Acute toxicity of N-2803-4 to the Daphnid, Daphnia Magna, T.R . Wilbury laboratories Inc., Marblehead, Massachusetts, United States of America 3 0 .3M , 1995d, Acute toxicity of N-2803-2 to the Daphnid, Daphnia Magna, T.R. Wilbury laboratories Inc., Marblehead, Massachusetts, United States of America 3 1 .3M , 1995e, Growth and Reproduction Toxicity Test with L-13492 and the Freshwater Alga, Selenastrum capricornutum, T.R . W ilbury laboratories Inc., Marblehead, Massachusetts, United States of America 3 2 .3M , 1995f, Growth and Reproduction Toxicity Test with N2803-2 and the Freshwater Alga Selenastrum capricornutum, T.R. W ilbury laboratories Inc., Marblehead, Massachusetts, United States of America 3 3 .3M , 1996c, Growth and reproduction toxicity Test with FC-1015 and the freshwater Alga, Selenastrum capricornutum, T.R. W ilbury laboratories Inc., Marblehead, Massachusetts, United States of America 3 4 .3M , 1996d, Growth and Reproduction Toxicity Test with N-2803-4 and the Freshwater Alga, Selenastrum capricornutum, T.R . W ilbury laboratories Inc., Marblehead, Massachusetts, United States of America 3 5 .3M , 1987b, Microbios m icrotoxtest with FC-126, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 3 6 .3M , 1990c, Microbios microtox test with FX-1003, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 3 7 .3M , 1996e, Microbios microtox test with FC-143, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 3 8 .3M , 1996f, Microbics microtox test with FC-118, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 3 9 .3M , 1996g, Microbics microtox test with FC-1015-x, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 40.3M , 1995g, (inhibitory effect of L-13492 to microbics microtox toxicity analyzer system, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 4 1 .3M , 1990d, Activated sludge respiration inhibition test with FX-1003, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 4 2 .3M , 1996h, Activated sludge respiration inhibition test with FC-1015-X, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 4 3 .3M , 1995h, Inhibitory effects of L-13492 on activated sludge respiration, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 4 4 .3M , 1978b, The effects of continuous aqueous exposure to 78.03 on hatchability of eggs and growth and survival of fry of Fathead minnow (Pimephales prometas), EG & G, Wareham, Massachusetts, United States of America 4 5 .3M , 1981b, Multi-phase exposure/ Recovery Algal assay test method, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 46. DuPont, 2002, Presentation May 2002, Dordrecht, The Netherlands 4 7 .3M , 1997c, Acute toxicity of R1904 to Fathead minnow (Pimephales prometas), Asd corporation, Duluth, Minnesota, United States of America 4 8 .3M , 1981c, 96 hour acute static toxicity of FC-128 to Fathead minnow (Pimephales prometas), 3M Environmental laboratory, St. Paul, Minnesota, United States of America Perfluoroalkylated substances - Aquatic environmental assessment x ->' t ' 000416 79 4 9 .3M , 1997d, Growth inhibition of R1904 for Green alga (Selenastrum capricornutum). Asci corporation, Duluth, Minnesota, United States of Ameri^ 5 0 .3M , 1997d, Microbios microtox test with R1904, Asci corporation, Duluth, Minnesota, United States of America 5 1 .3M , 1978c, The effects of continuous aqueous exposure to 78.01 on hatchability of eggs and growth and survival of fry of Fathead minnow (Pimephales prometas), EG&G, Wareham, Massachusetts, United States of America 5 2 .3M , 1984b, Acute toxicity to Fathead minnow (Pimephales prometas) of FX13, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 5 3 .3M , 1984c, Acute toxicity to Fathead minnow (Pimephales promelas) of PO$F, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 54.3M , 1998a, Acute toxicity of u1464 to larval Fathead minnow (Pimephales promelas), Asci corporation, Duluth, Minnesota, United States of America 5 5 .3M , 1998b, Acute toxicity of U1464 to Daphnia magna, Asci corporation, Duluth, Minnesota, United States of America 5 6 .3M , 1998c, Inhibition of U1464 for activated sludge respiration, Asci corporation, Duluth, Minnesota, United States of America 5 7 .3M , 1992a, Static Acute Toxicity of FC-120 to the Fathead Minnow, Pimephales promelas, Envirosystem Division, Hampton, New Hampshire, United States of America 5 8 .3M , 1992b, Static Acute Toxicity of FC-120 to the Daphnid, Daphnia magna, Envirosystem Division, Hampton, New Hampshire, United States of America 5 9 .3M , 1988c, Acute Toxicity O f E2566-1 to Daphnia magna, Analytical Biochemistry Laboratories, Inc., Columbia, Missouri, United States of America 6 0 .3M , 1992c, Microbics microtox test with FC-120, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 6 1 .3M , 1992d, Activated sludge respiration inhibition test with FC-120, 3M Environmental laboratory, St. Paul, Minnesota, United States of America 62. O ECD, 2002, Draft assessment of perfluorooctane sulfonate and its salts, ENV/JM /EXCH(2002)8, Paris, France 6 3 .3M , 2000f, PFOS: a 96-hour static acute toxicity test with the saltwater mysid (Mysidopsis baha), W ildlife International Ltd., Easton, Maryland, United States of America 6 4 .3M , 2000g, PFOS: a 96-hour shell deposition test with the eastern oyster (Crassostrea virginica), W ildlife International Ltd., Easton, Maryland, United States of America 6 5 .3M , 2001 e, PFOS: a 96-hour toxicity test with the marine diatom (Skeletonema costatum), W ildlife International Ltd., Easton, Maryland, United States of America 6 6 .3M , 2000h, PFOS: a flow-through life-cycle toxicity test with the saltwater mysid (Mysidopsis baha), W ildlife International Ltd., Easton, Maryland, United States of America Perfluoroalkylated substances - Aquatic environmental assessment 80 000417 7 of Arrieirica 'uluth. w tes of ) of FXof of POSF, merica hales -`rica rion, re, nagna, erica merica 1 i >, mysid I States ted nited er Jnited 7 Policy and governmental awareness 7.1 National environmental policies 7.1.1 Netherlands In the National Environmental Policy Plan (NMP, 1989) and the more recently published National Environmental Policy Plan-4 (NMP-4, 2001) the general environmental policy of the Netherlands is described. By the year 2010 the environmental targets and target values must have been reached. Concerning the reduction of the risks caused by high concentrations of chemicals, specific policy targets have been set in the National Environmental Policy Plan of 1989. The targets imply the aim to not exceed the Maximum Permissible Concentrations (MPCs) and the Negligible Concentrations (NCs) in 2010, by means of prevention and reconstruction of production processes. While these values are guidelines they are not legally binding. When the environmental quality standards are set, other aspects, such as political and technical feasibility, are also taken into account. Target values are either set at the NC or at the background value. In the report on integral standardisation on substances (INS, 1997) environmental quality standards have been derived. For PFAS no specific quality standards, MPCs or NCs have been set. The current water policy is reflected in the Fourth Note on Watermanagement (4th NW 1997). In this note the targets and headlines of the policy for the national water management are given. 7.1.2 Other country specific policies/ governmental awareness United States of America Significant new use rule The United States of America Environmental Protection Agency (USEPA) has initiated a significant new use rule (SNUR) for perfluoroalkyl sulfonates. It concerns 13 chemicals5, including polymers that are derived from perfluorooctanesulfonic acid and its higher and lower homologues. The rule requires manufacturers and importers to notify the new use of these chemicals to USEPA, giving the USEPA the opportunity to evaluate the intended new use and associates activities (USEPA, 2002b). Hazard Assessment PFOA The USEPA has performed a hazard assessment on PFOA. The corrected draft version has been released on April 15, 2002 and is under discussion (USEPA, 2002a). Canada The Canadian government is performing a environmental screening assessment on perfluoroalkyl substances for possible priority chemicals. This assessment is to be completed in Autumn 2002 (Windle e ta l., 2002). 5The CAS-numbers of the concerning chemicals are: 2250-98-8, 30381-98-7, 57589-85-2, S1660-12-6, 67969-69-1,68608-14-0, 70776-36-2,127133-66-8, 148240-78-2, 14868-79-1, 178535-22-3, P-942205. P-96-1645 306974-63-0 Perfluoroalkylated substances - Aquatic environmental assessment I * > ; | 000418 81 United Kingdom The National Centre for Ecotoxicology & Hazardous Substances of the United Kingdom has reviewed the occurrence and hazards of perfluoroalkylated substances in the UK in 2001. It has been initiated as a response to the decision of 3M to phase out the perfluorooctanyl chemistry. This study takes a broader perspective and tries to incorporate the telomers as well (NCEHS, 2001). Denmark The Danish EPA has performed a survey of perfluorooctyl substances in consumer products. In three out of 21 purchased consumer products fluorinated chemicals were detected (PFDS, FOSA and n-EtFOSE) (NERI, 2002). 7.2 International policy/ awareness 7.2.1 OECD The Organisation for Economic Co-operation and Development (OECD) is carrying out a hazard assessment on PFOS and its salts. The draft version of M ay, 13, 2002 is being discussed in the OECD task force of existing chemicals (OECD, 2002). Once the information is available, this will be followed by a risk assessment. Accordingly decisions will be taken on the need for international risk management (NCEHS, 2001). 7.2.2 OSPAR The OSPAR Convention for the Protection of the Marine Environment of the Northeast Atlantic has performed a selection process for possible bioaccumulative, persistent and ecotoxic substances. Candidates were selected from a Danish QSAR database (Tyle et al., 2001, Tyle et at., 2002). About 60 perfluorinated chemicals were selected, out of a total of 92 possible substances (NCEHS, 2001). 7.3 Actions of industry 7.3.1 3M studies 3M has performed many studies on toxicology, pharmaco-kinetics and environmental fate and effects of perfluorinated chemicals. They have submitted the results of these studies to the USEPA, and discussed the results with them (3M, 2000). These data are available from USEPA (USEPA, 2001). 7.3.2 Teiomer Research Program The united perfluorinated teiomer manufacturers (Asahi Glass, Atofina, Clariant, Daikin and DuPont) have set up a research program on the principal raw material common amongst the TRP members: 8:2 FTOH. The program focuses on three parallel work streams: toxicology, pharmaco-kinetics and environmental date and effect studies. Publication in the open literature of study results is encouraged. Environmental fate and effect studies that are included in the research are hydrolysis, adsorption/desorption, aerobic and anaerobic degradation, photolysis and chronic toxicity to fish and daphnids. It is anticipated that the current research plan will take two more years to complete (TRP, 2002). 7.3.3 APME research program Asahi Glass, Atofina, Ausimont, Daikin, DuPont, Dyneon, M iteni, 3M and Solvay have set up a research program on PFOA under the umbrella of the Association of Plastics Manufacturers in Europe (APM E). The program focuses on two parallel work streams: pharmaco-kinetics and environmental date and effect studies. Environmental fate and effects studies that are included in the research program are adsorption/desorption, chronic toxicity to fish, daphnia and algae. It is anticipated that the current research plan will take another year to complete (APM E, 2002). Perfluoroalkylated substances - Aquatic environmental assessment 82 000419 nited vision of 1er nsum er imicals carrying 3, 2002 02). t. gement e -ilative, i QSAR nicals tted n (3M , in t, terial ee and I. ysis arch /ay >n of I m 7.4 References 3M , 2000, letter of Mr. Zobel to the USEPA, April 20, 2000 4th NW, 1997, Fourth Note on Watermanagement, Vierde Nota Waterhuishouding Regeringsvoornemen, The Hague, The Netherlands APM E, 2002, Association of Plastic Manufacturers Europe, Presentation at DuPont, M ay, Dordrecht, The Netherlands INS, 1997, Intgrale Normstelling Stoffen - Milieukwaliteitsnormen bodem, water, lucht, Interdpartementale Werkgroep Intgrale Normstelling Stoffen, The Hague, The Netherlands NERI, 2002, National Environmetal Research Institute, Denmark, PFOS in consumer products, submitted to OECD PFOS Electronic Discussion Group NMP (1989) Nationaal Milieubeleidsplan, VRO M , The Hague, The Netherlands NMP-4 (2001) Nationaal Milieubeleidsplan 4, VROM 2001047767, The Hague, The Netherlands NCEHS, 2001, National Centre for Ecotoxicology & Hazardous Substances, Review of occurrence and hazards of perfluoroalkylated substances in the UK, A nonconfidential overview, Environment Agency, W allingford, United Kingdom O ECD, 2002, Draft assessment of perfluorooctane sulfonate and its salts, ENV/JM /EXCH(2002)8, Paris, France TRP, 2002, Telomer Research Program, Presentation at DuPont, M ay, Dordrecht, The Netherlands Tyle, H, Larsen, HS, Wedebye, EB, Niemel, J, 2001, Identification of potential PBTs and VPvPs by use of QSARs, submitted to OSPAR, Copenhagen, Denmark Tyle, H, Larsen, HS, Wedebye, EB, Sijm, D, Pedersen Krog, T , Niemel, J, 2002, Identification of potential PBTs and vPvBs by use of QSARs, submitted to OSPAR, Copenhagen, Denmark USEPA, 2001, United States Environmental Protection Agency, personal communication with M r. Hernandez, Washington, DC, United States of America USEPA, 2002a, United States Environmental Protection Agency, Draft Hazard Assessment of Perfluoroctanoic acid and its salts, Washington, DC, United States of America USEPA, 2002b, United States Environmental Protection Agency, Perfluoroalkyl Sulfonates; Final Rule and Supplemental Proposed Rule, Federal Register, Volume 67, No. 47, Washington, DC, United States of America W indle, W , Purdy, R, Cureton, P, Miettunen, A, 2002, Preliminary environmental screening assessment of perfluorooctane sulfonate (PFO S) and related compounds, Discussion paper, Environment Canada, Quebec, Canada Perfluoroalkylated substances - Aquatic environmental assessment * s - *. r 000420 83 Perfluoroaikylated substances - Aquatic environmental assessment 84 000421 List of Annexes Annex 1 Annex II Annex III Annex IV Annex V List of Abbreviations Data Reliability Indicator Production processes Mechanism of AFFF Derivation of iMPCs Perfluoroalkylated substances - Aquatic environmental assessment 000422 85 Perfluoroalkylated substances - Aquatic environmental assessment 86 000423 Annex 1 List of abbreviations 6:2 FTA 6:2 FTMA 6:2 FTOH 8:2 FTA 8:2 FTMA 8:2 FTOH 10:2 FTOH 12:2 FTOH AFFF APME BAF BCF BMF BOD COD DDA DRI EC*, ECD ECF EL*, EP EQC FD FOSA GC HPLC IC iM PC LC LC50 LL*, LOAEL LOD LOQ MPC MS n-EtFOSA n-EtFOSE n-EtFOSEA n-EtFO SEM A n-MeFOSE n-M eFO SEA NMR NOAEL NOEC NOEL OECD PFAS PFBS PFDS 1H,1H,2H,2H perfluorooctyl acrylate 1H,1H,2H,2H perfluorooctyl methacrylate 1H,1H,2H,2H perfluorooctanol 1H,1H,2H,2H perfluorodecyl acrylate 1H,1H,2H,2H perfluorodecyl methacrylate 1H,1H,2H,2H perfluorodecanol 1H,1H,2H,2H perfluorododecanol 1H,1H,2Hr2H perfluorotetradecanol Aqueous Film Forming Foam Association of Plastic Manufacturers Europe Bioaccumulation Factor Bioconcentration Factor Biomagnification Factor Biological Oxygen Demand Chemical Oxygen Demand Dodecyldemethylammonium salt Data Reliability Indicator Concentration that causes an effect for 50% of the tested organisms Electron Capture Detection Electrochemical Fluorination Level that causes an effect for 50% of the tested organisms Equilibrium partition Equilibrium Criterion (Model) Fluorescence detection Perfluorooctane sulfonamid Gas Chromatography High-performance Liquid Chromatography Concentration that inhibits 50% of the tested organisms Indicative Maximal Permissible Concentration Liquid Chromatography Concentration that is lethal for 50% of the tested organisms Level that is lethal for 50% of the tested organisms Lowest Observed Adverse Effect Level Limit of Detection Limit of Quantification Maximal Permissible Concentration Mass Spectrometry n-Ethyl perfluorooctane sulfonamid n-Ethyl perfluorooctane sulfonamidoethanol n-Ethyl perfluorooctane sulfonamidethyl acrylate n-Ethyl perfluorooctane sulfonamidethyl methacrylate n-Methyl perfluorooctane sulfonamidethanol n-Methyl perfluorooctane sulfonamidethyl acrylate Nuclear Magnetic Resonance No observed Adverse Effect Concentration No observed Effect Concentration No observed Effect Level Organisation for Economic Co-operation and Development Perfluoroalkylated substances Perfluorobutyl sulfonate Perfluorodecyl sulfonate P e rflu o ro a lky la te d su b sta n ces - Aquatic environmental assessment AJ \ 000424 87 PFHpA PFHxA PFHxS PFOA PFOS PFOSGE PFS POSF POTW PPb ppm PTFE QSAR RIKZ SNUR TFE TGD TRP USEPA VNTF VTN WWTP Perfluoroheptanoic acid Perfluorohexanoic acid Perflluorohexyl sulfonate Perfluorooctanoic acid Perfluorooctyl sulfonate n-perfluorooctylsulfonyl-N-ethylglycinate Perfluorinated surfactants Perfluorooctane sulfonyl fluoride Publicly owned treatment plant Parts per billion Parts per million Polytetrafluorethylene Quantitative Structure-Activity Relationship Rijksinstituut voor Kust en Zee (Insititute for Coastal and Marine Management) Significant New Use Rule Tetrafluoroethylene Technical Guidance Document Telomer Research Project United States Environmental Protection Agency Vereniging van Nederlandse Tapijt Fabrikanten (Association of Netherlands Carpet Manufacturers) Vereniging Textielindustrie Nederland (Dutch Association for the Textile Industry) W astewater Treatment Plant Perfluoroalkylated substances - Aquatic environmental assessment 88 000425 'acturers) Annex II Data reliability Indicator Data Reliability Indicator In the data that were gathered for this study large discrepancies were found in values for comparable properties. Although different test methods mostly result in different outcome, well-conducted experiments should give values in the similar range. Several researchers have tried to develop indicators for data quality. For the present study two important publications on this subject have been used: Kollig (1988) and Klimisch et al. (1997). Both researchers describe indicators for evaluating data reliability. Kollig (1998) divides the indicator in four categories: 1. Analytical information, 2. Experimental information, 3. Statistical information, 4. Corroborative information. Ad 1. Was the analytical method appropriate and suitable for the particular compound? If no standard method has been used, is the method sufficiently described? Ad 2. Are ail experimental parameters (temperature, pH, purity, etc.) well stated? Is the chemical identified by testing? Ad 3. Is the uncertainty and the reproducibility of the test mentioned? Ad 4. Are the data in accordance with the results of another independently conducted study? Each category contains subcriteria that are developed for various properties in order to enable the estimation of the reliability of the measurement within one category. The Data Reliability Indicator (D RI) consists of the relative reliability for all four categories. Klimisch et al. (1997) use four reliability scores for experimental data-generating studies: 1. Reliable without restrictions, 2. Reliable with restrictions, 3. Not reliable, 4. Not assignable. Ad 1. The tests are performed according to internationally accepted test guidelines and preferably in compliance with Good Laboratory Practice (GLP). Ad 2. The tests are not entirely performed according to internationally accepted test guidelines. Nevertheless the conditions are acceptable. This category also includes investigations that have no official testing guideline, but that are scientifically acceptable. Ad 3. The test designs that are assigned to this category may have interference between the test substance and the measuring system or the test system is not relevant in relation to the exposure or the test method is not acceptable. Ad 4. No reliability can be assigned if insufficient experimental details are given. For various tests subcriteria are supplied for the evaluation of tests that were executed not according to internationally accepted test guidelines to be assigned 'reliable with restrictions'. Nevertheless, data in category 3 or 4 can very well be P e rflu o ro a lk y la te d su b stan ces - Aquatic environmental assessment V* `7 000426 89 used as corroborative information, or as a 'first estimation' if no other data are available. Both methods can be useful in the assessment of reliability. The Kollig method does not supply a final judgement of reliability; the Klimisch method does not gjVe a detailed set of criteria. All data that are supplied by the 3M company have been evaluated with the Klimisch ranking system. Furthermore, most of the datagenerating experiments in the present study have been performed (partially) according to ISO, OECD or EPA testing. Therefore it will more practical to use the Klimisch ranking system. References Klimisch, H-J, Andreae, M, Tillmann, U, 1997, A systematic approach for evaluating the quality of experimental toxicological and ecotoxicological data, Regulatory Toxicology and Pharmacology, 2 5 ,1 -5 Kollig, HP, 1988, Criteria for Evaluating the Reliability of Literature Data On Environmental Process Constants, Toxicological and Environmental Chemistry, 17, 287-311 Perfluoroalkylated substances - Aquatic environmental assessment J 90 000427 * tF. 1dat* On m'^ y. 1, HI Production processes Introduction Perfluoroalkylated substances can be produced by two routes of synthesis; fluorination of organic compounds, in which hydrogen atoms of non-fluorinated or partially fluorinated organic compounds are substituted by fluorine atoms (Moldavsky et al., 1999), or reactions with perfluorinated compounds to form PFAS. Two important routes of production are used commercially: 1) electrochemical fluorination and 2) tlomrisation. Also methods of fluorination using high-valence metal fluorides (CoF3, M nF3, AgF2) or elemental fluorine (F2) are known (Field, 1994; M oilliet, 2001), but these techniques are not important for the commercial synthesis of surfactants. In the following sections the first two routes of synthesis of perfluoroalkylated substances will be discussed. Electrochemical fluorination The electrochemical fluorination is being used by the 3M company, and will be terminated for the largest part by 2003 (3M , 2000a). In this reaction an organic compound is introduced in liquid anhydrous hydrogen fluorine (aHF) at nickel anodes. An electric current is led over these electrodes, resulting in the substitution of the hydrogen atoms of the organic compound by fluorine atoms. This method was developed by Simons et al. in 1944 (3M , 2002). 3M bought the patent immediately, but did not have any commercial application until 1956 (Riecher, 2000). Since then it has been used as a commercial process by 3M for more than 40 years (Noel et al., 1996). The overall reaction is the following: HH H H H H H H H HH HH HH H C8H17S 0 2F + 17 HF 1-Octanesulfonyl fluoride (POSF) + 17 HF -> f F. F F F F FF FF FF C8F17S 0 2F + 17 H2 Perfluorooctanesulfonyl fluoride and exists of two subreactions, at the anode and cathode (Alsmeyer et al., 1994): anode: CraH,,X + nHF - CmF,,X + 2nH* + 2ne' cathode: 2nH* + 2ne' -> nH2 POSF is further reacted with methyl or ethyl amine, resulting in N-ethyl (and methyl) perfluorooctane sulfonamide (N-EtFOSA), and subsequently with ethylene carbonate to form either N-methyl or N-ethylperfluorooctanesulfonamidoethanol (N-EtFOSE). N-EtFOSE and N-MeFOSE are the principal building blocks of 3M 's product lines (3M , 1999). tafluoroalkylated substances - Aquatic environmental assessment 91 000428 Various sources provide estimations of the yield of the fluorination of 1octanesulfonyl fluoride (3M, 1999; 3M , 2000b; 3M , 2001). 35-40% n-POSF 20-25% Perfluorinated alkanes and ethers 18-20% Branched non-C8 perfluorinated sulfonyl fluorides 10-15% Tars (high molecular weight fluorochemical byproducts) and molecular hydTog^ 7% Linear non C8-perfluorinated sulfonates Table 111.1 Impurities in POSF production These percentages may vary from plant to plant, due to differences in raw materials, equipment and process conditions. The tars and non functional molecules are easily removed from the reaction mixture. The final product will contain approximately 70% n-POSF and 30% branched impurities with odd and even chain length (3M , 2000b). The impurities can be due to impurities in the reactant or rearrangement during fluorination. Although n-octanesulfonyl fluoride is used, there are always traces of other C8 compounds, leading to non-linear POSF. However, their presence does not affect the application properties (M oldavsky & Furin, 1998). Similar impurities can be expected in PFOA production. The PFOA production process is as follows: C8H17COCI + 18HF ------- . C8F ,7CO F + 17H2 + HCI; C8F17CO F + H20 ------- C8F17COOH + HF Figure III.2 Production of PFOA with the ECF process (Kissa, 2001) Other impurities may be partially fluorinated. This is due to the production process itself: Simons processes [is] a step by step fluorination process which leads to the formation o f all possible partially fluorinated compounds [..]' (Sartori & Ignatiev, 1998). According to severed sources (Moldavsky & Furin, 1998; Moldavsky et al., 1999; 3M , 1999, 3M , 2001) also non-C8 compounds can be found: fragmentation and rearrangement o f the carbon skeleton can also occur and significant amounts o f cleaved, branched and cyclic structures may be formed.' (3M , 1999). Fragmentation of the carbon framework is to be expected, because the energy of the C-F bond formation exceeds that of the C-C bond (Moldavsky et al., 1999). W ith electrochemical fluorination perfluorinated compounds with even and odd numbers of perfluorocarbon atoms are generated (Kauck & Diesslin, 1951 cited in Moody & Field, 2000; Kissa, 2001). The commercially available POSF contains more than 90% of C8-molecules, of which approximately 25% is branched. The perfluorinated C6 compounds constitute 5-10% of the POSF product and the remainder is C7 (2-3% ) and C5 (3M , 2001). The distribution of chain length is assumed to be comparable for the fluorination of octanoic acid to form PFOA. Perfluoroalkylated substances - Aquatic environmental assessment 92 000429 /ill I and ing ces of foes rities ows: + HF ocess fs to 9; on mts of ). d I in e Tlomrisation The second important route of synthesis of PFS is tlomrisation. This process is used by Atofina, DuPont, Clariant, Daikan and Asahi Glass (Wakselman & Lantz, 1994; Atofina, 2001). Tlomrisation is a process in which '[..] a polymeric product [is] formed from a monomer and an initiator, R, obtained by a chain-transfer reaction between a radical from a catalyst and some other compound, called a telogen.' (Kirk & Othmer, 1954). In the first stage of this production process perfluoroalkyl iodides are synthesised. In the second the iodide is substituted by a functional group, depending on the application. The first stage of the process, the manufacturing process for the perfluoroalkyl iodide, involves two steps: 1) 5 C2F4+ IF , (from l2+ F2) + 2I2 -- C 2F, I 2) C2F,I + nC2F4 C2F,(C 2F4),,I The second step uses a radical-initiated mechanism. This can be initiated using heat, UV light or radical sources (Wakselman & Lantz, 1994). This manufacturing process is developed by Haszeldine in 1949 and adapted by the DuPont company in the 1960s (Rao & Baker, 1994). The price of compounds produced via this production route is high. The main reasons are the properties of the starting materials. The l2and IF, are highly aggressive and the tetrafluorethylene is expensive and potentially explosive (Wakselman & Lantz, 1994). In the second stage of production the iodide has to be substituted with a functional group. Only two important commercial products can be produced directly from CnF J , being perfiuorocarboxylic acid (using oleum as reactant) and perfluoroalkanesulfonyl chloride (using S 0 2/Zn and Cl2). Indirectly products can be produced by ethylenation, followed by substitution of the iodide by a functional group of choice, thus forming RFC2H4X (Wakselman & Lantz, 1994), where RF represents a perfluorinated alkyl group. The compounds that are produced via this indirect route are the most important intermediates for perfluorinated surfactant production, with 1H,1 H,2H,2H-perfiuorodecanol (8:2 FTOH, see figure III.2) as primary building block. During the tlomrisation also C4 and C6 iodide can be formed by the radical reaction. Two other important possible by-products can be formed with this production process, due to the following reactions (Rao & Baker, 1994): 1) RfI -r- IF, --RfF 2) 2 RfI -> RfRf F F F F FF/ OH / F FFFFFF F Figure III.2. 8:2 FTOH All undesired products are removed by distillation. This is a simple process. Because of the radical mechanism, only linear perfluoro-n-alkyl compounds are to be expected. Perfluoroalkylated substances - Aquatic environmental assessment 93 000430 Comparison of production processes The most important difference between the two major production processes of PFS, is the final product. Electrochemical fluorination can produce all types of PFS and will be largely dependent on the starting organic material that is used, and its purity. ECF was used by 3M to produce POSF and PFOA. Almost all products that are synthesised using tlomrisation have RFC2H4X as an intermediate, in which X represents any functional group. When electrochemical fluorination and tlomrisation are compared, also the purity of the final products is an important difference. The products from the tlomrisation process are more pure than the products formed via electrochemical fluorination. The tlomrisation process gives fewer by-products and furthermore it is easier to separate those from the desired product, so that relatively pure products are obtained. The perfluorinated products from the electrochemical process yield both even and odd numbered perfluorinated carbons, in contrast to the perfluorochemicals that are synthesised via tlomrisation, which have only even numbers of perfluorinated carbon atoms. Approximately 30% of the ECFproduct will be branched, whereas the telomers will have a straight alkyl chain (Kissa, 2001). Last, there is a price difference between the two processes. Telomers are exceptionally expensive products (Wakselman & Lantz, 1994), whereas the electrochemical fluorination process is relatively cheap (Hudlicky & Pavlath, 1995; cited in Moody & Field, 2000). Exact figures are not available. References 3M , 1999, Fluorochemical use, distribution and release overview,company sanitized version, St Paul, Minnesota, USA 3M , 2000a, 3M Phasing out some of its specialty materials, press release, May 16, available at www.3m .com /profile/pressbox/2000Jndex.jhtm l 3M , 2000b, Voluntary Use and Exposure Information Profile Perfluorooctanesulfonyl fluoride (PO SF), St. Paul, Minnesota, United States of America. 3M , 2001, Interview with M r. Cox, European Toxicological Manager, Antwerp, Belgium 3M , 2002, cm s.3m .com /cm s/DK/da/1-20/zzirEY/view.jhtm l, US Patent 2,519,983 Alsmeyer, YW , Childs, W V, Flynn, RM , Moore, GGI, Smeltzer, JC , 1994, Electrochemical fluorination and Its applications, in Banks, RE et al. (Ed.), 1994, Organofluorine chemistry: principles and commercial applications, Plenum Press, New York, USA, chapter 5 Atofina, 2001, several internal documents Field, P, 1994, The Fluorochemical lidustry b. Organofluorine products and companies in Western Europe,, in Banks, RE et al. (Ed.), 1994, Organofluorine chemistry: principles and commercial applications. Plenum Press, New York, USA, Chapter 27B Kirk, RE, Othmer, DF, 1954, Encyclopedia of chemical technology, Volume 13, The Interscience encyclopedia, Inc., New York, USA Kissa, E, 2001, Fluorinated surfactants and repellents, 2nd edition, revised and expanded, Marcel Dekker, Inc. New York, USA Perfluoroalkylated substances - Aquatic environmental assessment 94 000431 ss Of of PFS and its ctsthat hich X le ie Gemicai rmore it I ist to nly CFin 995; '1 6 , 983 S, A, he Moiliet, JS, 2001, The use of elemental fluorine for selective direct fluorinations, J. Fluorine Chem., 109, 13-17 Moldavsky, DD, Furin, GG, 1998, The purification of perfluorinated compounds for commercial use, J. Fluorine Chem., 87,111-121 Moldavsky, DD, Bispen, TA, Kaurova, G l, Furin, GG, 1999, Technology for the preparation of perfluoro-organic compounds, J. Fluorine Chem., 94, 157-167 Moody, CA , Field, JA , 2000, Perfluorinated surfactants and the environmental implications of their use in fire-fighting foams, Environ. Sci. Technol., 34, 38643870 Noel, M , Suryanarayanan, V , Chellammal, S, 1996, A review of recent developments in the selective electrochemical fluorination of organic compounds, J. Fluorine Chem., 83, 31-40 Rao, NS, Baker, BE, 1994, Textile finishes and fluorosurfactants, in Banks, RE et at. (Ed.), 1994, Organofluorine chemistry: principles and commercial applications, Plenum Press, New York, USA, Chapter 14 Riecher A , 2000, The day the bubble burst, W hy 3M decided to quit making AFFF ATC industrial fire fighting foam, International Fire World, available at http://www.fireworld.com/maga2ine/afff_2 .htm Sartori, P, Ignatiev, N, 1998, The actual state of our knowledge about mechanism of electrochemical fluorination in anhydrous hydrogen fluoride (Simons process), J. Fluorine Chem., 87,157-162 Wakselman, C, Lanz, A , 1994, Perfluoroalkyl bromides and iodides, in Banks, RE et al. (Ed.), 1994, Organofluorine chemistry: principles and commercial applications, Plenum Press, New York, USA, Chapter 8 P e rflu o ro alkyla te d su b sta n ces - Aquatic environmental assessment 000432 95 Perfluoroalkylated substances - Aquatic environmental assessment 96 000433 ANNEX IV Mechanism of AFFF AFFF is used by several tv r * .............................................................. military, chemical plants andoffre fighters' '"eluding fire departments at airports, Field, 2000). The products are also c a iu H r"^ platforms (3M - 1999*- Moody & the burning fluid. d lght water, because they form a film on The fire fighting mechanism of foam is basPH 1. The capability to seal the surfarp f ur Pnnc'p!es (Luttmer, 1998): atmospheric oxygen, 2. Thermal stability, and lsolate 't from contact with 3. Low density, 4. Cooling by the water that percolates through the foam The first two principles are partially based on the properties of fluorochemicals As stated earlier surfactants form micelles in water. Perfluorinated surfactants f' lamellar micelles, thus perfectly covering the burning fluid with the foam Corpart, 1999; Moody & Field, 2000). on The foam provides better grip to the material in flames, producing a continuous cover (Figueredo et al., 1999). The combination of hydrocarbon and perfluorinated surfactants is responsible for the covering. `The films formed by fluorocarbon and hydrocarbon solutions A lf ^.. J).. n Aqueout Surfactant Solution FluSourrofaccatrabnotn consist of two mixed monolayers of f - i O - surfactants where the air-aqueous phase n X? Iro cM o n monolayer is dominated by the fluorocarbon surfactant and the aqueoushydrocarbon phase is dominated by the hydrocarbon surfactant (see figure IV .1) Figure IV.1. The mechanism of fire fighting foams (Moody & Field, 2000) (Moody & Field, 2000).' The film that is formed is less permeable for heptane vapours than the films formed by hydrocarbons surfactants, thus preventing re-ignition of the fuel (Pabon & Corpart, 1999; Moody & Field, 2000). References 3M , 1999a, Fluorochemical use, distribution and release overview, company sanitized version, St. Paul, Minnesota, USA Figueredo, RCR, Ribeiro, AL, Sabadini, E, 1999, Science of foams, application in fire-fighting (Cincia de espumas - Aplicaao na extinao de incndios, Quimica nova, 22,126-130, partly translated using babel fish (world.altavista.com) Luttmer, W J, 1998, Waterbezwaarlijkheid van blusschuimen (in Dutch), RIZA, Lelystad, The Netherlands Moody, CA , Field, JA , 2000, Perfluorinated surfactants and the environmental implications of their use in fire-fighting foams, Environ. Sci. Techno!., 34, 38643870 Pabon, M , Corpart, JM , 1999, Fluorinated surfactants in fire fighting foams (Les tensioactifs fluors dans les mousses extinctrices), Actual Chimique, July 1999, 3-9 Perfluoroalkylated substances - Aquatic environmental assessment ts < ( * v<. 000434 97 Perfluoroalkylated substances - Aquatic environmental assessment 98 000435 Annex V Derivation of MPC PFOS For PFOS for two trophic levels chronic NOFC-: aro , i ui levels that showed the lowest accuuttee uL(tE))CC M. iThe! re,fore, flollowcinogvetnhneSTtChDe method (ECB, 1996), an assessment factor of 50 is applied to the lowest mg/L (marine mysid shrimp) NOEC, being 0.25 Therefore, the iMPC,re!hvv,, ,, is 5 pg/L. PFOA For PFOA no reliable chronic NOECs for fish or daphnia are available. Therefore the iMPC has to be derived from the reported K E K * ,. The lowest acute L(E)C is 300 mg/L for fish. Applying an assessment factor of 1000, this results in an iMPC of 300 pg/L. 8:2 FTOH For 8:2 FTOH insufficient data area available to derive an iMPC. N-EtFOSA For N-EtFOSA sufficient data are available to derive the iM PC, following the modified EPA method. Two acute L(E)CMs are available; the lowest is 14.5 mg/L for Daphnia. Applying an assessment factor of 1000, the freshwater iMPC = 14.5 Pg/L. References ECB, 1996, European Chemicals Bureau, Technical Guidance Document in support of commission directive 93/67/EEC on risk assessment for new notified substances and commission regulation (EC) No 1488/94 on risk assessment for existing substances Part I to IV, Ispra, Italy PerfluoroalkyIated substances - Aquatic environmental assessment 00043 99