Perfluorooctane Sulfonate (PFOS) Production and Use: Past and Current Evidence

Perfluorooctane Sulfonate (PFOS) Production and Use: Past and Current Evidence Prepared for UNIDO Dorian Carloni Research Fellow UNIDO Regional Office in China E-mail: d.carloni@unido.org December 2009 1

Table of Contents 1. Introduction 3 2. PFOS Production 3 2.1 3M s Production 3 2.2 European Union (EU) countries 5 2.3 on-eu European countries 7 2.4 orth America 8 2.5 Latin America 8 2.6 Asia 8 2.7 Oceania 9 2.8 Africa 9 3. PFOS Use 10 3.1 European Union (EU) Countries 10 3.2 on-eu European Countries 18 3.3 orth America 20 3.4 Latin America 21 3.5 Asia 21 3.6 Oceania 22 3.7 Africa 23 4. PFOS Imports/Exports 25 5. Patterns in PFOS Production and Use 27 5.1 PFOS Cumulative Production and Use by Country from 2003 to 2008 27 5.2 Essential Uses 29 5.2.1 Legislation 30 5.2.2 Main Producers and Users by Sector (Essential Uses) 31 5.2.3 Evidence from the United ations Data 33 5.3 Problems 36 6. Conclusions 36 References 37 Appendix 1 39 Appendix 2 48 Appendix 3 50 Appendix 4 52 Appendix 5 55 2

1. Introduction Perfluorooctane Sulfonate (PFOS) is a fully fluorinated anion used as a surface active agent in a wide range of applications. For example it is used on the surface of paper and paperboard as a water and oil repellant, and on the surface of metals (mostly chromium) to provide chemical stability. PFOS can be formed by degradation from a large group of related substances, referred to as PFOS related substances, and is a member of a larger family of perflouroalkyl sulfonate (PFAS). In May of 2009 PFOS was added to the Annex B of the Stockholm Convention and classified as a Persistent Organic Pollutant (POP). This decision was the result of a decade of research and analyses accompanied by increasing concerns about its toxicity. The first actions against PFOS production and use were taken in the United States in the end of the 1990s. 3M, a US company and the major global producer of PFOS until 2003, received increasing pressure from the US Environmental Protection Agency (EPA) in the last years of the 90s, and the accumulating evidence of the toxicity of PFOS pushed 3M to announce on May 16, 2000 that it would begin to phase out PFOS production. After this decision, several other OECD countries began working together to further research the effects of PFOS. The meeting of the Task Force on Existing Chemicals on May 29-30, 2000 produced a Hazard Assessment on PFOS, and PFOS was officially recognized to be a concern for both human and environmental health. In the following years, an increasing number of documents were published on PFOS production and its uses. While some came from national Environmental Protection Agencies and national Chemical Registers, others were cross-country studies carried out by international institutions such as the OECD. This paper intends to collect all of the publicly available information on PFOS production and its uses. It is aimed at showing patterns in these areas, both by country and by sector of use, in order to present a complete and clear picture from the multiple studies that have been published on PFOS. 2. PFOS Production 2.1 3M s Production Available information indicates that 3M was the main producer of PFOS and its related substances until 2003, and that the production before 2003 was mostly for surface treatment 1 and for paper protection. Paul et al. (2009) 2 report that 3M started its production of perfluorochemicals (PFCs) in 1949, and that the production increased over time. This includes Perfluorooctane Sulfonate Flouride (POSF), a precursor of PFOS, whose production both at 3M and globally grew significantly from 1966 to 1990, peaking between 1990 and 2000. Figure 1 below shows the global POSF production in 1970-2002 according to the estimates of different authors: Paul et al. (green line: global production; purple line: 3M s production), Smithwick et al. (red line) and Prevedouros et al. (blue line). Despite their differences, all estimates clearly indicate that the peak in POSF production was reached in the end of the 90s. 1 i.e. for the protection of apparel and leather, for fabric/upholstery and for carpets. 2 Paul, A.G., Jones, K.C., Sweetman, A.J. (2009). A first global production, emission, and environmental inventory for perfluorooctane sulfonate. Environmental Science and Technology 43, 386-392 3

Figure 1 Estimated total global POSF production volumes (1970-2002) Source: Paul, A.G., Jones, K.C., Sweetman, A.J. (2009). A first global production, emission, and environmental inventory for perfluorooctane sulfonate. Environmental Science and Technology 43, 386-392. In addition, the data in Figure 2, provided by 3M, confirm that large quantities of POSF were produced by the company between 1984 and 2000: Figure 2 3M POSF production after 1984 3M historical POSF production 4000 3500 3000 Production (tons) 2500 2000 1500 1000 500 3M 0 1984-1989 1990-1994 1995-1999 1999 2000 2001 2002 Year Source: 3M (converting 1 kg=2.2 pounds) 4

Thirdly, Tables 1 and 2 include data from the Danish Environmental Protection Agency (EPA) and the OECD (2002) and show that almost a half of 3M s total PFOS production was for surface treatment applications. About 2160 metric tons, corresponding to 48% of total PFOS production, were used for soil, oil and water resistance on apparel and leather, fabric/upholstery and carpets. Table 1 Application areas Application area Former global 3M production of PFOS, 2000 (in percent) Surface treatment 48 Paper protection 33 Performance chemicals 15 Fire fighting foams 3 Source: Danish Ministry of the Environment, EPA (2005). More environmentally friendly alternatives to PFOScompounds and PFOA. Environmental Project No. 1013. Table 2 - Global Production of PFOS related chemicals in 2000 (based on data from 3M) Application Category Production (metric tonnes) Surface treatment applications 2,160 Paper protection applications 1,490 Performance chemical applications 891 (of which 151 in fire fighting foams) Source: OECD (2002). Cooperation on existing chemicals, Hazard assessment of Perfluorooctane Sulfonate (PFOS) and its salts, ENV/JM/RD(2002)17/FINAL. The tables also show that the second most important use, after surface treatment, was paper protection. In the paper and paperboard industries PFOS was used as a grease, oil and water repellent, and served both in food and non-food applications. About 1490 metric tons (33% of the total) were produced for paper protection applications in 2000. The third and final category of use was performance chemicals, including mining and oil well surfactants, acid mist suppressants for metal plating and electronic etching baths, photolithography, electronic chemicals, hydraulic fluid additives, alkaline cleaners, floor polishes, photographic film, denture cleaners, shampoos, chemical intermediates, coating additives, carpet spot cleaners, and as an insecticide in bait stations. About 891 metric tons of PFOS (18% of the total) were produced for these applications in 2000. 2.2 European Union (EU) Countries The OECD s Results of survey on production and use of PFOS, PFAS and PFOA, related substances and products/mixtures containing these substances (2005) 3 is the most comprehensive source available on the production of PFOS and PFOS related substances. It can be summarized as follows: - EU: combined manufactured and imported quantity from 1996 to <10000 tons (10 chemicals, each <1000 tons); - Belgium: combined manufactured and imported quantity for photographic industry in 2000: 5 tons 4 ; - Germany: manufactured quantity for mist suppressants in electroplating industry and surfactant in photographic processing solutions in 10-30 tons; 3 OECD (2005) Results of survey on production and use of PFOS, PFAS and PFOA, related substances and products/mixtures containing these substances, ENV/JM/MONO(2005)1. 4 For Belgium all PFOS, PFAS and PFOA related substances are pooled. 5

- Italy: manufactured quantity in <22 tons (<20 tons as chemical intermediate, <2 tons as acid mist suppressant); - Cyprus, Finland, Poland, Sweden and the UK: no production of PFOS and PFOS related substances in 2003; - Bulgaria: some production in 2002, but specific data are not available. Besides the document by the OECD, other sources supply information about EU countries: - Germany: according to the Annex F information submitted by Germany to the Persistent Organic Pollutants Review Committee (POPRC) on the 7 th of February, 2007 5, Germany did not produce PFOS in 2007; - the UK: a document by the RPA & BRE (2004) argues that with regard to the UK, it is accepted that no production of PFOS related substances have taken place in the UK, at least in volumes allowing commercial marketing of such substances 6 ; - Czech Republic: according to the Annex F information submitted on the 6 th of February, 2007, Czech Republic did not produce PFOS in 2007; - Romania: according to the Annex F information submitted on the 29 th of April, 2008, PFOS was not produced in Romania in 2008. Finally the aforementioned document by the RPA & BRE identifies some areas outside the UK where PFOS was produced before 2004 and from which it was then imported to the UK: - textile industry: a large number of UK suppliers of textile auxiliaries have manufacturing plants in various parts of Europe, where most of the production takes place; - metal plating: available information supports the idea that PFOS is not produced in the UK but in the EU and by 3M, and that UK platers are predominantly served by UK suppliers of imported chemical preparations containing PFOS; - fire fighting foams: companies from the US, Japan and Israel have been indicated as possible sources of PFOS-based fire fighting foams; - coatings: the major market for this product is outside the EU (Asia and US); - aviation hydraulic fluids: the majority of these fluids are manufactured outside Europe. Table 3 is taken from the same document 7 and lists producers that are relevant to the UK market: Table 3 Producers relevant to the UK market for PFOS related substances Location Links to other companies USA Supplies products to UK company Italy Supplies products to CAS number (if known) 307-35-7 4151-50-2 307-35-7 1691-99-2 Quantities N/A N/A otes Also produces other PFCs. The company essentially serves laboratories and research and development divisions. Active in following sectors: -pharmaceutical 5 Annex F information submitted by countries can be downloaded on the Stockholm Convention website at: http://chm.pops.int/convention/popsreviewcommittee/hrpoprcmeetings/poprc2/annexfinformationyear2007/ta bid/466/language/en-us/default.aspx 6 Risk & Policy Analysts Limited (RPA) in association with BRE Environment (2004). Perfluorooctane Sulphonate Risk reduction strategy and analysis of advantages and drawbacks. Final Report prepared for Department for Environment, Food and Rural Affairs and the Environment Agency for England and Wales. 7 See Table 2.18 of RPA&BRE (2004). 6

UK company Germany Appears to supply products to UK company Germany Supplies chemicals to several UK companies Japan Supplies chemicals to several UK companies 2795-39-3 4151-50-2 29457-72-5 30381-98-7 -agrochemicals (insecticides) -performance chemicals (AFFFs, Cr plating) Pharmaceuticals and agrochemicals account for more than 75% of production. The company has emphasized that they are active only in the production of intermediates. Greatest market for products in Europe (this including Italy accounts for more than 50% of total sales). - N/A Small company that produces PFOS related substances; these are used by the semiconductor industry (the relevant data have been incorporated in the submission by SEMI) 56773-42-3 >100 kg/y Supplies PFOS related substance(s) to at least one UK formulator of mist suppressants; product information suggests possible downstream uses: -chromium electroplating -wetting and flow control agent for coating photographic paper and film -antistatic agent for photographic paper and film -wetting agent for etching and opacification baths -wetting agent for acid baths for metal surface treatment, e.g. anodizing baths and chromatising baths - N/A Appears to be active in the textiles auxiliaries sector and photographic sector Source: RPA&BRE (2004) 2.3 on-eu European Countries - Norway: according to the OECD (2005), Norway has not manufactured any PFOS or PFOS related substance in 2003. Annex F information submitted by Norway to the POPRC on the 27 th of January, 2006 also reports no production of PFOS nor of its salts; - Switzerland: according to the Annex F information submitted to the POPRC on the 6 th of February, 2007, PFOS was not produced in Switzerland in 2006. The OECD (2005) adds that no production of PFOS and its related substances was reported in Switzerland in 2003; - Monaco: according to the Annex F information submitted recently, PFOS is not produced by Monaco. 7

2.4 orth America The OECD report Results of survey on production and use of PFOS, PFAS and PFOA, related substances and products/mixtures containing these substances (2005) shows that neither the US nor Canada produced any PFOS and PFOS related substances in 2003. Information is also available from other sources: - US: the Annex F information submitted by the US on the 9 th of February, 2007 reports that the production of PFOS and PFOS related chemicals in the US ceased in 2002 (essentially after 3M had completely phased out its PFOS production); - Canada: a survey published by the Canadian Environmental Protection Agency 8 that targeted manufacturers, exporters and importers of PFOS in amounts exceeding 100 kg with concentration higher than 10g/kg, shows that there were no manufacturers of PFOS and its related substances in 2004. 2.5 Latin America The only Latin American country for which there is positive information on PFOS production is Brazil. Based on the Annex E information submitted by Brazil on the 27 th of January, 2006, the PFOS-related lithium perfluorooctane sulfonate was produced in Brazil in 2006, although no data are available on production levels. In addition, the Annex F information published on the 2 nd of February, 2007 reports that the estimated Brazilian production of sulfuramid, an insecticide containing PFOS, was around 30 tons per year. On the other hand, Chili and the Dominican Republic report in the Annex F information submitted to the POPRC that PFOS and its related substances were not identified or registered in their country. 2.6 Asia Information on PFOS production in Asia comes from China and Japan: - China: the Chinese Ministry of Environment 9 maintains that China started large scale production of PFOS in 2003 and that before 2004 total PFOS production was less than 50 tons per year. Since 2005 China s annual output has grown rapidly due to the increase of the applications of PFOS and overseas demand. In 2006, 15 Chinese enterprises produced more than 200 tons of PFOSF, about 100 tons of which were exported to Brazil, the EU and Japan. Production by industry is difficult to estimate, but use by industry can be taken as a good indicator of the amount of PFOS produced, as shown later in this document; - Japan: the OECD (2005) reports that Japan was manufacturing less than 100 tons of PFOS and PFOS related substances for semiconductors and other uses in 2003. The Annex F information submitted by Japan to the POPRC on the 9 th of February, 2007 explains that surface treatment materials used in the metal plating industry are produced and sold by around ten companies in Japan. In addition, Japanese companies play a major role in photomask production, and have more than a 50% share of the worldwide market (50 kg produced and used in Japan). Some production is also reported in the fire fighting foams industry. Considering the information that has been submitted by one manufacturer on its 8 Canada Gazette (2006). Perfluorooctane Sulfonate and its Salts and Certain Other Compounds Regulations, Regulatory Impact Analysis Statement, Vol. 140, No. 50, December 16, 2006. 9 Ministry of Environmental Protection of China (2008). Additional information on production and use of PFOS. 8

2.7 Oceania sales between 1981 and 2005, it is estimated that the total amount of PFOS in the market for fire fighting foams is less than 200 tons. However, there is no data on annual production. - Australia: data published by the OECD (2005) show that in 2003 Australia did not manufacture any PFOS and PFOS related substances. The National Industrial Chemicals Notification and Assessment (NICNAS) Alert No. 5 from the Australia Government 10 reports that PFOS and PFAS related chemicals were not manufactured in Australia in 2004 and 2005. NICNAS Alert No. 8 11 affirms that there was not any production of PFOS or PFOS related chemicals in Australia in 2006 and 2007. - New Zealand: according to the OECD (2005) New Zealand did not manufacture any PFOS or PFOS related substances in 2003. 2.8 Africa - Algeria: no data on PFOS production is contained in the information submitted by Algeria to the POPRC on the 11 th of January, 2007. - Congo: according to the OECD (2005), PFOS and its related substances were not identified or registered in Congo in 2003. - Zambia: the Annex F information submitted by Zambia to the POPRC on the 31 st of January, 2007 reports that there is no data on either current or historical PFOS production in Zambia. 10 Australian Government, Department of Health and Ageing (2007). IC AS o.5, Perfluorooctane sulfonate (PFOS) and Perfluoroalkyl sulfonate (PFAS), February 2007. 11 Australian Government, Department of Health and Ageing (2008). IC AS o.8, Perfluorooctane Sulfonate (PFOS) and Perfluoroalkyl Sulfonate (PFAS), December 2008. 9

3 PFOS Use 3.1 European Union (EU) Countries Table 4 below, including data from the Scientific Committee on Health and Environmental Risks (SCHER) 12 and from Brooke et al. 13, shows that the main uses of PFOS in the EU in 2000 were for fabric and paper treatment: Table 4 EU uses of PFOS related substances in 2000 Use area Quanti Substance Percentage of otes ty (t/y) type total use (%) Fabric treatment 240 polymer 41.7 From UK estimate of 48 tonnes, assuming UK is 20% of EU Paper treatment 160 substance 31.8 From UK estimate of 32 tonnes, assuming UK is 20% of EU Coatings 90 substance 17.9 From UK estimate of 18 tonnes, assuming UK is 20% of EU Chromium plating 10 acid 0.02 Estimate from German company Photography 0.85 acid 0.002 EPCI estimate, production of film 0.75 polymers EPCI estimate, use of film Photolithography 0.47 substance 0.001 ESIA/SEMI estimate Aviation (h. fluids) 0.73 acid 0.001 One third of world use estimate Fire fighting foams 0.57 acid 0.001 From UK estimate of foam use The SCHER also adds that the use of PFOS and PFOS related substances in consumers applications such as carpets, leather/apparel, textiles/upholstery, paper and packaging, coatings, industrial and PFOS household cleaning products, pesticides and insecticides has been largely abandoned following the announcement of the main global producer (3M) to voluntarily phase out manufacture and use of PFOS consumer applications. It illustrates this point by listing PFOS ongoing uses in the EU in 2004, shown in Table 5. Table 5 - Ongoing industrial/professional usage of PFOS and PFOS-related substances Metal (chromium) plating Fire fighting foams Photographic industry Semiconductor industry Aviation industry 8,600-10,000 kg/year Estimated quantity held in current stock: 122 tons Approximately 850 kg PFOS-related substances/year 436 kg/year Hydraulic fluids; approximately 730 kg/year Clearly, applications of PFOS no longer included surface treatment and paper protection. Instead, the main application of PFOS in the EU in 2004 was in metal plating 14. 12 Scientific Committee on Health and Environmental Risks (SCHER) (2004) Opinion on RPA s report Perfluorooctane Sulphonate Risk reduction strategy and analysis of advantages and drawbacks, final report (table 1). 13 Brooke D., A.Footitt, T.A.Nwaogu (2004) Environmental risk evaluation report: Perfluorooctanesulphonate (PFOS), Building Research Establishment Ltd Risk and Policy Analysts Ltd (figure 2.2). 10

For further insight into the situation, we can consider PFOS use by individual country: - Germany: the Annex F information submitted by Germany to the POPRC on the 7 th of February, 2007 indicates the following uses at that time: - fire fighting foams - photographic industry - photolithography and semiconductors - hydraulic fluids - metal plating It then lists as historically (before 2006) dominating uses: - textiles - apparels - home furnishing and upholstery - carpet and leather products Furthermore the OECD (2005) reports that Germany manufactured products/mixtures containing PFOS and its related substances in - electroplating industry: 20-60 tons (50% concentration) - fire fighting foams: <2 tons (12 % concentration) - photolithography: 0.1 tons (2.6% concentration) Considering PFOS concentration in such products, it can be estimated that up to 30.24 tons of PFOS and its related substances were used in Germany in 2003. - Sweden : the Swedish Chemicals Agency 15 (KemI) published data on manufacturing and imports of PFOS/PFAS for Sweden from 1999 to 2004 using the information collected in the Swedish products register 16, as shown in Figure 3. It demonstrates that the overall quantity of PFOS/PFAS in manufactured/imported products went from 23 tons in 2000 to 0.684 tons in 2004, and that the amount of PFOS/PFAS used in the textile industry, the traditionally dominant sector of use in Sweden, decreased substantially as well (Figure 4). Figure 3 Quantities of PFCA, PFOS/PFAS in Swedish products register 1999-2004 14 122 tons of PFOS are estimated in stocked fire fighting foams, but the foams are only for emergency use. PFOS was therefore used in a much smaller quantity for such application. 15 Swedish Chemicals Agency (KemI) (2006). Perfluorinated substances and their uses in Sweden, Report No. 7/06. 16 All companies that manufacture or import a chemical product to Sweden must register the product at the products register kept by KemI. This holds for chemical products over 100 kg, and for all substances contained in the product with a concentration higher than five per cent. 11

Figure 4 Textile goods manufacturing Although PFOS/PFAS use in the textile industry decreased significantly in Sweden by 2004, according to the KemI it was still one of the main uses of PFOS in Sweden. KemI s list includes the following PFOS uses: - textiles - metal coatings - cleaning agents - printing inks - developers (semiconductor industry) - leather tanning - flooring materials - paints and varnishes About the remaining areas of use: - paper industry: PFOS related compounds have not been used in Sweden since 1999; - fire fighting foams: - telomer sulphonates have replaced PFOS in fire fighting foams; - there may still exist stocks of foam containing PFOS with end-users, but manufacturers do of fire fighting foams no longer use PFOS; - there is probably no foam containing PFOS left at the fire prevention services, since they generally do not keep large stocks; - estimation is that current figures are probably the same as in 2003 concerning quantities of foam in stock at different end-users. At that time it was calculated that approximately 1000 m 3 of concentrated extinguisher foam was stored in Sweden; - other: PFOS have a minor use in pesticides, products for graphics processing, and floor paints, but PFOS use in such products might well be hidden because of very low concentrations (therefore there was no need to register the product at KemI). A document published by the Danish Environmental Agency in 2005 17 gives additional information on the percentage of total PFOS use in each sector in 2002 (percent calculations are based on data from the Swedish Product Register): - 28% of the total PFOS related substances were used as impregnating agents for textiles and leather, but this ended by 2004; - 6% was used within cleaning agents and floor polishing products; 17 Danish Ministry of the Environment, EPA (2005). More environmentally friendly alternatives to PFOS-compounds and PFOA. Environmental Project No. 1013. 12

- an unspecified but large amount of PFOS was used within the paint and varnish industry, but in 2004 there was no more such use; - about 3% was used for metal surface treatment. Finally, the OECD (2005) reports that in - 36.3 tons of galvano-technical agents and raw materials containing PFOS and its related substances were manufactured/imported to Sweden (0.001-50% concentration) - 622 tons of wax and other polishing preparation cleaning agents containing PFOS and its related substances were manufactured/imported to Sweden (0.002-0.24% concentration). Considering PFOS concentration in such products, it can be estimated that up to 19.64 tons of PFOS and its related substances were used in Sweden in 2003. - The Netherlands: a study carried out in January 2002 by the University of Amsterdam s Institute for Biodiversity and Ecosystem Dynamics (IBED) outlines the consumption of PFAS by sector in the Netherlands 18, as shown in Table 6. It demonstrates that in 2002 the main use was for paper and board protection, followed by leather protection and carpet protection. Table 6 Markets for PFAS in the etherlands (estimates for 2002) Source: RPA&BRE (2004) Denmark: the RPA & BRE (2004) reports that, according to a study held by the Danish EPA in 2001-2002, the most common uses of PFOS related substances in Denmark were in: - impregnation agents for textiles, leather and paper; - wax and other polishes; - paint, varnish and reprographic agents; - cleaning products; - flame retardants; - mould release agents 18 Risk & Policy Analysts Limited (RPA) in association with BRE Environment (2004). Perfluorooctane Sulphonate Risk reduction strategy and analysis of advantages and drawbacks. Final Report prepared for Department for Environment, Food and Rural Affairs and the Environment Agency for England and Wales (paragraph 2.2.3) 13

It also adds that the total estimated Danish consumption (registered and non-registered) may have been as high as 50 tons per year (and as low as 5 tons per year). This information is confirmed by the document published by the Danish Environmental Agency in March 2005 19, which shows the uses of PFOS and PFOS-related substances in Denmark in 2000. The table below summarizes the results of a study carried out in 2001 and based on the Danish Product Register of 2000 20 : Table 7 PFOS use in Denmark 19 Danish Ministry of the Environment, EPA (2005). More environmentally friendly alternatives to PFOS-compounds and PFOA. Environmental Project No. 1013. 20 The Danish Product Register does not take into account imported products and products with a content of PFOSrelated substances that are not labelled as dangerous substances. 14

The same report also states that the most common uses of PFOS-based compounds in Denmark in 2005 were in: - cleaning agents for glass cleaning waxes and floor polishes - photographic industry - manufacturing of semiconductors - metal surface treatment. - Belgium: as reported by the OECD (2005), in - <50 tons of fire fighting forms containing PFOS and its related substances were manufactured/imported to Belgium (18% concentration); - <125 tons of molded goods containing PFOS and its related substances were manufactured/imported to Belgium (0.5% concentration); Considering PFOS concentration in such products, it can be estimated that up to 9.625 tons of PFOS and its related substances were used in Belgium in 2003. - other uses of PFOS in Belgium in 2003 included: - photographic industry - electronics industry (semiconductors) - aviation hydraulic fluids - United Kingdom: the main reference for the United Kingdom is the document published by the RPA & BRE (2004), which argues that the main historical uses of PFOS related substances in the UK (and in the EU) were for: - carpets - leather/apparel - textiles/upholstery - paper and packaging - coatings and coating additives - industrial and household cleaning products - pesticides and insecticides This information is demonstrated in Table 8. The table also shows that before 2000 the UK market was consuming over 100 tons of PFOS related substances each year, the majority of which were used for the protection of paper and packaging, and the protection of carpets. The least common uses were as chemical intermediates and as surfactants for baths used in the electrical and electronics industries. Table 8 - Summary Data on Applications of PFOS Related Substances Imported in the UK Prior to 2000 Application Type Paper & packaging Carpet Protection Coatings (additives) Apparel and leather protection Percentage of Total Number of Products Percentage of all CAS Nos. Available in the Market PFOS Tonnage Range 7% 9% >25 t/y 32% 10% 13% >25 t/y 23% 17% 30% >10 t/y 18% 25% 37% >10 t/y 15% Approximate Percentage of Total PFOS Imports 15

Fabric & 10% 22% >10 t/y 10% upholstery Protection Fire Fighting 18% 7% >1 t/y 1% Foams Additives for 2% 2% >1 t/y 1% household products Chemical 7% 15% >1 t/y 1% intermediates E&E* bath 5% 7% >1 t/y <1% surfactants TOTAL 100% N/A 100% Source: RPA&BRE (2004) (table 2.18) *E&E: electroplating and etching Table 9 shows the estimated demand of PFOS related substances in the UK in 2004. Table 9 - Estimated Current Demand for PFOS Related Substances Industry Sector UK Use (kg/year) Photographic industry 270 Photolithography and semi-conductors 94* Hydraulic fluids 146* Metal plating 500 to 2,500* Storage for Emergency Use (note not annual usage) UK Total Storage (kg) Fire fighting foam storage for emergency use 24,434 *Assuming the UK represents 20% of the EU Source: RPA&BRE (2004) (table 2.17) We can also consider individual tables of data for each sector of use: - metal plating: Table 9 shows the estimated demand for PFOS in metal plating production was 500-2,500 kg/year. This upper bound is based on the assumption that the UK market represents 20% of the EU market, whereas the lower bound is taken from Table 10, which considers statistics from four UK companies. Table 10 - Overview of Use of PFOS Related Substances in Mist Suppressants by UK Suppliers (used by the chromium plating industry) Company Quantities Used (t/y) PFOS Substances Used (CAS No.) Concentratio n of PFOS Substance(s) Quantity of Suppressan ts sold (t/y) Origin of PFOS Shelflife (y) UK sales trend A 56773-42-3 5-7% 0.25 2 B 0.12 56773-42-3 10% 1.23 EU 2 Stable C 0.15 56773-42-3 50% 0.3 EU 1 Stable D 3M Totals <0.5 Stable Source: RPA&BRE (2004) (table 2.8) 16

- fire fighting foams: Table 11 shows the stocks of fire fighting foams containing PFOS held in the UK in 2004. It concludes that 24.4 tons of PFOS related substances were contained in existing stocks that year. Table 11 - Estimates of Quantities and Use of Fire Fighting Foams in the UK Estimated current quantities in Fire Authority (FA) Inventories Estimated current Emergency stores at industrial complexes as part of Mutual Aid All Foams Concentrates (Litres) PFOS based Foam Concentrates (Litres) 986,350 76,190 762 2,959,040 2,367,220 23,672 agreements Total 3,945,390 2,443,420 24,434 *Based on relative density of 1 and 1% PFOS content. Source: RPA&BRE (2004) (table 2.10) Quantities of PFOS-related* Substances (kg) - photographic industry: Table 12 gives a breakdown of the information on the UK photographic sector contained in Table 9, showing a total demand of PFOS as 270 kg per year. Table 12 Photographic sector in the UK Source: RPA&BRE (2004) Finally the OECD (2005) report confirms that PFOS was used in these same sectors in the UK in 2003, namely: - chromium plating (mist suppressants) - photolithography and semiconductors - aviation hydraulic fluids - photographic industry - Finland: the OECD (2005) reports that the main PFOS uses in Finland in 2003 were in: - metal plating 17

- photolithography and semiconductors - aviation hydraulic fluids However, it also states that no products/mixtures containing PFOS or its related substances were produced in Finland in 2003. This paradox may simply be due to companies not declaring that they used PFOS related substances in producing their goods. - Italy, Slovenia, Poland and Cyprus reported no production of products/mixtures containing PFOS and its related substances in 2003 (OECD). - Bulgaria: the OECD (2005) indicates that data are not available for Bulgaria in 2003. 3.2 on-eu European Countries - Norway: a document available on the EFTA Surveillance Authority website 21 illustrates the main application areas of PFOS in Norway in 2005 and 2006: - fire fighting foams: the largest application area of PFOS in Norway (more than 90% of overall use), specifically in AFFF (Aqueous Film Forming Foams). Although fire fighting foams containing PFOS are no longer sold in the market 22, in 2005 the Pollution Control Authority of Norway estimated that 57 tons of PFOS and its related substances had been emitted from unmixed fire fighting foams (with 3% concentration of PFOS) and that in the remaining fire fighting foams there were 22 tons of PFOS. In 2006 it was estimated that there were only 8 tons of PFOS substances left in fire fighting foams. Table 13 - Compilation of responses concerning remaining quantities and previous emissions of fire fighting foam with PFOS content Type of enterprise Remaining quantity of foam with PFOS content, litres Quantity of PFOS substances in remaining foam, kg Previous emissions of PFOS substances, kg Offshore operators 122,845 2,550 54,000 Mobile rigs 12,500 330 500 Ships and ferries 23,000 300 100 Land-based petroleum enterprises Petrochemical and other relevant industries 154,300 2,180 2,300 31,000 530 < 100 Tank farms 24,000 400 160 Airports 2,000 34 unkn. Armed forces 90,000 1,500 unkn. 21 EFTA Surveillance Authority, Assessment of need for ban/use restrictions on PFOS (perfluorooctyl sulphonate) and PFOS-related substances Environmental Impact assessment. 22 It is also clearly stated that fire-fighting foam containing PFOS is neither produced in nor imported into Norway anymore. 18

Fire-fighting training sites 0 0 unkn. Fire and rescue corps 1,000 13 unkn. Total 460,645 7,837 Min. 57,160 Source: EFTA Surveillance Authority, Assessment of need for ban/use restrictions on PFOS (perfluorooctyl sulphonate) and PFOS-related substances Environmental Impact assessment. Moreover, the Annex F information submitted by Norway to the POPRC on the 27 th of January, 2007 adds that the 57 tons of estimated emissions of PFOS substances are uncertain and refer to the period between 1980 and 2003. It also points out that the estimates of previous emissions for offshore platforms and mobile rigs are most reliable. - textiles and impregnation agents: in 2006 they contained a very small amount of PFOS and PFOS related substances, although in the past this quantity was larger. - metal plating: PFOS was used in metal plating as mist suppressants for chromium plating. It is estimated that PFOS use in metal plating in Norway was 3-5 litres per year. Finally, while the above information indicates the existence of stocks of fire fighting foam, the OECD (2005) records no product ion of substances containing PFOS or its related substances in Norway in 2003. - Switzerland: some information is provided by the Annex F submitted to the POPRC on the 6 th of February, 2007. It is estimated that before 3M stopped its production in 2001 the use of PFOS and PFOS precursors was 15 tons per year 23 (5 tons for textile, carpet and leather industries), and that its use in 2004 24 was only 1 ton. Data from the OECD (2005), however, shows a much different conclusion. As Table 14 demonstrates, the OECD puts the use of PFOS in 2000 at only 0.23 tons: Table 14 Switzerland Source: OECD(2005) 23 Morf L. (2004). Substance flow analysis for perfluorinated chemicals, for the Federal Office for the Environment, Bern, Switzerland. 24 In an optimistic scenario assuming a 100% reduction except for fire fighting foams (use of stocks) and coating products. 19

3.3 orth America - US: the Annex F information submitted by the US to the POPRC on the 9 th of February, 2007 explains that, although usage volumes are not available, the only possible uses continuing within the US are 25 : - in aviation hydraulic fluids; - as a component of a photoresist substance, including a photo acid generator or surfactant, or as a component of an anti-reflective coating, used in a photomicrolithography process to produce semiconductors or similar components of electronic or other miniaturized devices; - in coatings for surface tension, static discharge, and adhesion control for analog and digital imaging films, papers, and printing plates, or as a surfactant in mixtures used to process imaging films; - as an intermediate only to produce other chemical substances to be used solely for these uses. In the same document it is also stated that the regulation of the use of PFOS and PFOS related substances caused a large decrease in the volume of these chemicals produced and/or used in the US, from approximately 2.9 million kg in 2000 to less than 7,983 kg in 2006. Additionally, the OECD (2005) reports no manufacturing of products/mixtures containing PFOS and its related substances in 2003. - Canada: according to the CEPA Environmental Registry 26 in the period 1997-2000 the primary uses of PFOS and PFOS related substances were as: - grease repellents for fabric, leather, packaging and rugs and carpets; - additives in fire fighting foams, aviation hydraulic fluids, photographic photofinishing, paints and coatings 27. But after 3M phased out its PFOS production in 2003, imports to Canada of PFOS related substances virtually ceased (historically the United States and the EU represented the major source of Canadian imports). A survey 28 published by the CEPA in January 2005 shows that: - there were no exporters and manufacturers of PFOS related substances in Canada; - only 3 tons of PFOS were imported to Canada in 2004 for the electroplating sector; - although there was no production of PFOS in 2006, there were still approximately 3 tons of PFOS contained in fire fighting foams (AFFF) stocks 29, which could potentially be used and generate PFOS emissions. 25 Other uses have been prohibited by the U.S. EPA s Toxic Substances Control Act (TSCA) Significant New Use Rule (SNUR) regulations. 26 CEPA Environmental Registry (2006). Proposed Risk Management Strategy for Perfluorooctane Sulfonate (PFOS), Its Salts and Its Precursors. 27 In a document published by Sweden ( Exploration of management options for PFOS ) it is reported that the majority of PFOS imported into Canada was used in applications involving packaging (56%), rugs and carpets (20%), fire fighting foams (10%), paint and coating additives (8%), chemical formulation, (3%) and water, oil, soil and grease repellents for fabrics (1%). Small quantities of PFOS were also used in the photographic/photofinishing and semiconductor sector. 28 Companies were asked to report manufactured, imported or exported quantities of PFOS alone, in a mixture or in a product, and in a concentration greater than 10 grams per kilogram in a mixture or in a product", and only when the overall quantity of the substance was more than 100 kg. 29 Mostly stocked in Canadian airports, military installations and industrial facilities. 20

A document published on the Canada Gazette 30 elaborates on the results of the survey: - PFOS are mostly used in metal plating (in particular chromium electroplating, anodizing and reverse etching), and there are approximately 219 users of this substance in the sector 31 ; - fire fighting foams containing PFOS (AFFF) are still used in Canada; - there is concern about imports of manufactured items that are produced in developing Asian countries, which may contain PFOS and PFOS related substances. 3.4 Latin America - Brazil: PFOS and PFOS related substances in Brazil are mostly used in pesticides. The main use is in sulfuramid, which was introduced in Brazil in 1993, and serves as an active ingredient in the manufacturing of ant baits for the control of leaf-cutting ants. The Annex E information submitted by Brazil records the consumption of 20.58 tons of sulfuramid in 2004. The information reported in the Annex F submitted by Brazil to the POPRC in 2007 records about 30 tons/year of sulfuramid used in the manufacturing of ant baits. It is however difficult to estimate how much PFOS was used. - Chili: according to the OECD Survey (2005) PFOS and PFOS related substances have not been identified or registered in Chili. - Dominican Republic: according to the OECD Survey (2005) PFOS and PFOS related substances have not been identified or registered in the Dominican Republic. 3.5 Asia - China: according to the information on PFOS production and use submitted by the Ministry of Environmental Protection of China, PFOS was used in several industries in China in 2008: - textiles: more than 10,000 tons of fluorine containing textile finishing agents imported in China each year for the treatment of high quality clothing; - pesticides: 3 tons of PFOS used each year by 3 companies producing sulfuramid; - fire fighting foams: PFOS consumption is >100 tons per year (50 companies); - semiconductors (IC industry): 0.03-0.04 tons per year (mainly imported); - metal plating: about 25 tons of PFOS containing chromium fog inhibitor used each year in chrome plating industry; PFOS is also likely to be used in the following industries for which we do not have data on production and use, and that need further investigation: - oil exploitation: mainly used in chemical driven oil production of the old oil field - cleaning products (solvent application) - leather - photographic industry - aviation hydraulic fluids 30 Canada Gazette (2006). Perfluorooctane Sulfonate and its Salts and Certain Other Compounds Regulations, Regulatory Impact Analysis Statement, Vol. 140, No. 50, December 16, 2006. 31 They are located in British Columbia (29), the Prairie Provinces (43), Ontario (91), Quebec (48), and Atlantic Canada (8). 21

- photoelectricity - nanophase materials - medical appliance - printing ink - paper making According to the research currently in progress at UNIDO, it seems that China no longer uses PFOS in paper making, and that organic silicon is an alternative used for paper protection. - Japan: the information of the Annex F submitted by Japan to the POPRC on the 9 th of February, 2007 indicates that the main uses of PFOS and its related substances in Japan were: - semiconductors: PFOS consumption in the semiconductor industry has decreased substantially from 2003 to 2005: 2.9 tons in 2003 (1 ton critical use 32, 1.9 ton noncritical use), 2.7 tons in 2004 (1 ton critical use, 1.7 ton non-critical use), 1.2 tons (almost all critical use) in 2005; - metal plating: the total amount of PFOS use (PFOS detergent is diluted around 0.01-0.0001%) is estimated to be 2-3 tons per year. About 1000 companies use these surface treatment materials, half of which are in the plating industry, but only 10 companies are producers; - chrome masks for LCDs: amount of PFOS use in Japan is estimated to be around 50 kg per year (50% of world use, 100 kg); - photographic industry: 3.6 tons of PFOS were used in 2004; - fire fighting foams: total amount of PFOS in the market estimated to be <200 tons. The OECD (2005) additionally reports that Japan used PFOS and its related substances in 2003 while manufacturing products/mixtures. The exact amount of PFOS used, however, is unknown. 3.5 Oceania For both Australia and New Zealand the OECD (2005) reports no manufacturing of products/mixtures containing PFOS and its related substances in 2003. Other sources give the following information for these two countries: - Australia: - NICNAS Alert No.1 33 : the first of four alerts published by the Australian government on PFOS. It was published in 2000 and reported that PFOS had been used in fire fighting foams (AFFF and ATC) in the Scotchgard brand of products and was still being used as textiles and leather protecting agents of the same brand. It added that the use of PFOS for textiles protection would be phased out by September 2002, for leather protection by March 2003 and for all other uses by December 2003. 32 See definition of critical use on the Annex F submitted by Japan to the Persistent Pollutant Review Committee on the 9 th of February 2007. 33 Australian Government, Department of Health and Ageing (2001). IC AS Alert o.1, Existing chemicals, Perfluorooctanyl sulfonate (PFOS). 22

- NICNAS Alert No.2 34 : states that since 2000 there has been a rapid decrease in the use of PFOS chemicals in Australia, especially thanks to the voluntary phase out efforts carried out by Australian industries. The only two remaining uses were: - in Class B fire-fighting foam - in specialized industrial products used for processing rubber, and in the production of paints and coatings It also pointed out that these PFOS products would be phased out by December 2003. - NICNAS Alert No.5: it states that PFOS were no longer being used in leather treatment in 2006, although a PFOS containing product was imported prior to 2003 and had been used in leather treatment in 2004 (47 kg) and 2005 (13 kg). The only registered use of PFOS substances in 2006 in Australia is in fire fighting foams: about 180,000 litres of Class B fire fighting foam products purchased before 2003 and containing 0.1-7% PFOS-related substances are stocked at some end-user sites. - NICNAS Alert No.8: it reports that PFOS-based and related PFAS-based chemicals continue to be restricted to only essential uses, i.e. if there are no suitable alternatives available. Imports increased from 2006 to 2008, mostly for essential uses such as mist suppressants in the metal plating industry (99%), aviation (hydraulic fluid, 1%), photography and photolithography (surfactants, 0.002%). PFOS stocks (approximately 7.8 tons) have instead decreased from 2005 (9.36 tons) and are mostly used in the fire fighting foams industry (97%) and metal plating industry (3%). - New Zealand: according to the OECD (2005) the main PFOS uses in New Zealand in 2003 were in: - aviation hydraulic fluids - photographic industry - electronic applications 3.7 Africa - Algeria: a document published submitted by the Algerian Government to the POPRC 35 records the main uses of PFOS in Algeria: - fire fighting foams - photolithography and semiconductors - photographic industry - hydraulic fluids - metal plating - Congo: according to the OECD Survey (2005) PFOS and PFOS related substances have not been identified or registered in Congo. - Zambia: according to the Annex F information submitted by Zambia to the POPRC on the 31 st of January, 2007, PFOS is used in Zambia in: - fire fighting foams - photographic industry 34 Australian Government, Department of Health and Ageing (2001). IC AS Alert o.2, Perfluorooctane sulfonate (PFOS), April 2003. 35 Collecte des informations au titre des Annexes E et F de la Convention de Stockholm, submitted on the 11 th January 2007. 23

- photolithography and semiconductors - hydraulic fluids - metal plating - as a surface active agent 24

4 PFOS Imports/Exports Data for imports and exports of PFOS and its related substances are very limited. However it is useful to add these data to the analysis as imported quantities might be good indicators of amounts of PFOS and related substances consumed within a country. As it was shown previously, the OECD (2005) aggregates data for some countries on manufactured and imported quantities of PFOS and its related substances. Since these data have already been listed above in section 2 on PFOS production, they will not be listed again here. Instead, we will focus here on those countries for which OECD has not pooled the imported and exported quantities. A comprehensive table including all data on PFOS production, use, imports and exports can be found in appendix 1 at the end of this report. According to the OECD (2005), data on imports/exports of PFOS and its related substances show the following: - Germany: imports of intermediates for the production of PFOS related substances in 10-30 tons; - Finland, Poland, Norway, Japan, Australia: no imports for 2003; - Bulgaria: 63.666 tons imported in 2002, 62.75 tons imported in 2003; - Switzerland: imports were registered for the photographic industry and for metal plating, but no quantities are available; - Italy, Canada: there were some imports in 2003, but no quantities are available; - US: imports in 2000 for: - paper packaging applications: 1213.955 tons - textile, leather and carpet treatment: 1071.227 tons - industrial surfactants, additives and coatings: 572.273 tons - fire fighting foams: 92.5 tons Data from sources besides the OECD show the following: - Canada: - CEPA Environmental Registry 36 : approximately 258 37 tons of PFOS and its precursors were imported into Canada during 1997-2000, with PFOS and its precursors accounting for 43% of imported perfluorinated alkyl compounds 38. The same document also reports that imports of PFOS, its salts and its precursors essentially ceased in 2002, after 3M phased out production of PFOS. This source also refers to a survey published by the Canadian Environmental Protection Agency in January 2005 that targeted manufacturers, exporters and importers of PFOS in amounts exceeding 100 kg with concentration higher than 10 g/kg, and shows that: 1. approximately 3 tons of PFOS were imported to Canada in 2004 for use as a surfactant in the electroplating industry. 2. there were no exporters of PFOS and its related substances in 2004. - Brazil: - From the Annex E information submitted by Brazil to the POPRC on the 27 th of January, 2006: 36 CEPA Environmental Registry (2006). Proposed Risk Management Strategy for Perfluorooctane Sulfonate (PFOS), Its Salts and Its Precursors. 37 43% of 600 tons imports of perfluorinated alkyl compounds imported to Canada in 1997-2000 38 It is specified that PFOS alone accounted for <2% of imported perfluorinated alkyl compounds, i.e <258*0.02=5.16 tons and that the most significant Canadian imports of PFOS itself were in the form of the potassium salt, used for firefighting foams. 25

- Sulfuramid imports in 2005 amounted to 34 kg; - Sulfuramid exports in 2005 amounted to 690 kg of technical product and 54 tons of formulated product. - From the Annex F information submitted by Brazil to the POPRC on the 2 nd of February, 2007: - In 2006, around 400 tons of ant baits (sulfluramid 0.3%) were exported to 13 countries in South and Central America. Twelve tons of sulfuramid were therefore exported. - Australia: - NICNAS Alert No. 5: no imports of PFOS and PFOS related substances occurred in 2004 or 2005. - NICNAS Alert No. 8: imports of PFOS increased from 2006 to 2008, and it was mainly for uses such as mist suppressants in the metal plating industry (99%), aviation (hydraulic fluid,1%), photography and photolithography (surfactants, 0.002%). Approximately 760 kg in 2006 and 1350 kg in 2007 of PFOS both as technical grade and in products were imported into Australia. 26

5 Patterns in PFOS Production and Use Using the above data, this analysis tries to identify patterns in global PFOS production and use between 2003 and 2008. It does not include data on PFOS production and use before 2003 since we know that 3M was responsible for most of the global PFOS production until 2003. In addition, PFOS use was highly concentrated in a limited number of countries. After 2003 the situation changed because 3M had completely phased out its PFOS production, and a larger number of countries started to report data on PFOS production and use. With increased data, we can see that some patterns in production and use of PFOS emerge. In my research I relied on some strong but necessary assumptions: 1) When data are estimated in a range, the upper bound value is taken; 2) PFOS imported quantities are assumed to be for national consumption; 3) When the unit of measurement is tons/year and no time span is specified, the quantity produced or used was considered for only one year; 4) PFOS is considered together with its related substances. The first assumption is reasonable if we consider that global PFOS production and use is likely to be under-reported, given that the data are released only on a voluntary basis. By taking the upper bounds of PFOS production and use, we should get closer to the real (not reported) PFOS production and use. This assumption is however a little more problematic while comparing countries or sectors of use, because it exacerbates the difference between countries/sectors for which there are data and those in which there was some PFOS production/use, but there are no data. The second assumption is consistent with the conclusion of several reports on PFOS production and use, which consider imported PFOS for national consumption. Its weakness is that it does not consider that part of the imported PFOS might be re-exported. The third assumption is also reasonable because, if we extended the quantity of PFOS produced/used per year to an arbitrary number of years, the comparison between countries would be even more distorted than it is already. The fourth assumption is necessary because most of the sources report data on PFOS and its related substances as a single entity. It would be very difficult to estimate PFOS production/use separately, especially because it would be an additional estimation step on data that are themselves estimates. Keeping these assumptions in mind, the analysis is divided into three steps: 1) Investigate the distribution of PFOS production and use between countries, trying to illustrate the main differences between developed countries such as the UK and developing countries such as China; 2) Focus on the so-called essential uses of PFOS, combined with information on national legislation, UN data on goods production, and data on PFOS production and use; 3) Show the main problems in the analysis and any issues that need to be further addressed. 5.1 PFOS Cumulative Production and Use by Country from 2003 to 2008 Figure 5 below shows how different countries have contributed to the reported global PFOS production and use in the period of 2003-2008. The overall estimate for the manufacturing of PFOS 27

in 2005 was up to 175 tons 39. In addition, the consumption of all European Union countries in 2004 was estimated to be 12.23 tons 40. This aggregate data is not included in the table because they cover more than one country. The remaining country-specific data produce the following chart: Figure 5 PFOS cumulative production and use (2003-2008) The first interesting point of this figure is the overwhelming role of China. In fact it was both the main global producer and the main user of PFOS substances between 2003 and 2008. As shown above in section 2, less than 50 tons of PFOS were produced in 2004, while over 200 tons of PFOSF were produced in 2006. Additionally, given the data in section 3 on PFOS use in metal plating, pesticides, semiconductors and fire fighting foams, and data in section 2 on PFOS produced and not exported in 2006, China consumed around 200 tons of PFOS between 2003 and 2008. Secondly, this chart shows that Germany and Japan were the leading producers and users of PFOS among developed countries in the period of 2003-2008. As it will be shown in the second part of the analysis, metal plating along with the photographic and the semiconductor industries largely account for the high production and use of PFOS in these countries. Thirdly, we see that Brazil is a rather large consumer of PFOS. As mentioned earlier, PFOS is a component of sulfuramid, an insecticide that has been used in Brazil largely to combat leaf-cutting ants. In the chart, data for Brazil is a measurement of the amount of sulfuramid produced and consumed, since the concentration of PFOS in sulfuramid is unknown. If we then include the aggregate data 41 with the data by country, making sure data points do not 39 According to the OECD (2006) 74-175 tonnes of PFOS were manufactured/imported in 2005 in OECD countries. 40 As shown section 3.1. 41 Data from the OECD (2006) refer to pooled manufactured and imported PFOS in 2005. We can for example assume an equal amount of PFOS in each category: 87.5 tons were manufactured, 87.5 tons were imported in 2005. 28