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Table 7: Prices of selected basic polyfluorinated laboratory chemicals85

Chemical

CAS no.

Molecular weight

Price in €

per 100 g

Perfluorobutane sulfonyl fluoride (PFBSF)

375-72-4

303.09

136

Perfluorobutane sulfonic acid (PFBS)

59933-66-3

300.10

1,800

Perfluorooctane sulfonic acid (PFOS)

1763-23-1

500.13

1,122

Perfluorooctane sulfonyl fluoride (PFOSF)

307-35-7

502.12

92

Fluorotelomer 6:2 alcohol

647-42-7

364.10

130

Fluorotelomer 8:2 alcohol

678-39-7

464.12

187

Fluorotelomer 10:2 alcohol

865-86-1

564.14

1,440

Methyl nonafluorobutyl ether

163702-07-6

250.06

745



  1. Although the table shows the opposite, C6-fluorochemistry alternatives may often be more expensive than C8-fluorochemistry alternatives, which are subject to a phase-out and therefore obsolete.

  2. Especially at the beginning, alternatives might be more expensive to purchase or use; however, this increased cost could be an acceptable side effect of eliminating a very hazardous chemical. The prices of substitutes will decrease in the long run with a growing market and increasing competition.

  3. The necessity or “public good” of a use could also be a factor in determining whether it should continue or be phased out even in the absence of apparently good alternatives. Of course PFOS has useful applications, but none for which feasible alternatives appear to be lacking.

VI. Conclusions, recommendations and future developments

Low surface tension is the key



  1. In addition to stability, a key factor in the performance of fluorosurfactants is their extremely low surface tension, which currently cannot be matched with other surfactants. PFOS is the optimal substance with regard to that property. Owing to environmental and health concerns, however, surfactants without fluorine content could be used as alternatives if such low surface tension levels are not needed. Given the relatively high prices of fluorosurfactants, switching can in some cases also have economic benefits.

Substitutes for PFOS are available

  1. Fluorinated or non-fluorinated alternatives exist for nearly all current uses of PFOS. While the alternatives may be slightly more expensive and less effective, they will normally be less hazardous. In Japan only three essential applications are left for PFOS: 1) etching agent for semiconductors, 2) semiconductor resists and 3) photo films for industrial purposes.86

  2. The most common PFOS alternatives in use are fluorotelomers, which are precursors for PFCA. Formerly, C8-fluorotelomers were a frequent choice; they have been shown, however, to degrade into PFOA, which also has hazardous properties. For that reason the major global producers of fluorochemicals have agreed with the United States Environmental Protection Agency to phase out C8-fluorotelomers before 2015. As a result, there has been a shift to the less hazardous C6-, C4- and C3 perfluoroalkylated chemicals.

Need for better alternatives

  1. For some uses non-fluorinated chemicals have been introduced as alternatives; examples include silicones, aliphatic alcohols and sulfosuccinates. It might also be that a particular use or product is no longer essential, or that a process could be changed to eliminate the need for PFOS, as has happened in the photographic industry and in chrome plating.

Need for incentives

  1. There is a need for incentives to develop safe, affordable and technologically feasible alternative substances and processes and to identify the driving forces for their development. The international requirements applying to all parties to the Stockholm Convention, which must be implemented in national law, constitute one such incentive. The development of national law is an important tool for promoting incentives to identify and use alternative substances and processes. Postponing the development of national law until perfect alternatives are available is not wise because manufacturers may not develop alternatives if they are not forced to do so.

Complex assessment

  1. A comparative assessment of PFOS and its possible alternatives with regard to technical, socio-economic, environmental, health and safety considerations is a very complex process requiring a large amount of data and other information, and more than is normally available. Often the information available about PFOS is much more extensive than information about the possible alternatives, which may be newly developed substances or formulations covered by trade secrets. Furthermore, information on the alternatives will also often be non-peer-reviewed and of lower scientific quality. There may be a need for a mechanism for continuously updating information regarding the alternatives’ substitution properties and hazards. Such a mechanism should be consistent with Article 9, subparagraph 1 (b), of the Convention regarding the exchange of information on alternatives to persistent organic pollutants.

  2. Available useful economic data may also be scarce and biased. The sparse information received to date, however, suggests that the alternatives are in general priced comparably to the PFOS-related compounds. Specifically in the coatings and paints area, the non-fluorinated alternatives are cheaper. Higher costs of alternatives are not always a problem; in fact, sometimes the high cost of not continuing the use of small amounts of PFOS can be a problem for the industry.

Need for more public data and information on alternatives

  1. Much fewer data are currently available publicly on the alternatives than on PFOS. Much of the information is from patent literature, and the identities of actual chemicals used are often not disclosed. This reinforces the need for implementation of paragraph 1 of Article 9 on the information exchange regarding alternatives to persistent organic pollutants.

  2. Chemicals with structures similar to those of the listed PFOS substances could cause concerns similar to those related to the latter substances. This should be considered in evaluating alternatives.

  3. Increasing effort will be needed to study the toxicological and environmental properties of alternatives and to make the resulting information public and trustworthy by publishing it in peer reviewed scientific journals.

  4. A strategic integrated approach to testing is needed to speed development of the data required to understand the issues and concerns relating to the various types of alternatives. According to the United States Environmental Protection Agency, testing can be done scientifically without necessarily testing every alternative chemical for every endpoint.

Need for better communication in the value chain

  1. It is important that the issues associated with PFOS as a globally recognized persistent organic pollutant, including the health and environmental risks, be made fully known to suppliers and industries. Producers need to have better knowledge about the use of PFOS in processes, products and articles. It is also important to provide information to customers and consumers so that they can develop informed opinions about the possible need to change products or processes. Industries that are proactive in phasing out the use of a very hazardous chemical such as PFOS are likely to reap future market advantages.

Need for more international cooperation

  1. PFOS and its substitutes are being studied and evaluated in parallel by authorities in many countries. More international cooperation can save resources and speed up processes. The OECD Parallel Process for the Notification of New Chemicals is one useful approach (for new chemicals) to consider in developing international collaboration on assessing potential alternatives to PFOS and other polyfluorinated chemicals of concern.

Other sources consulted

  1. Bruinen de Bruin Y, Zweers P, Bakker J, Beekman M. 2009. Estimation of emissions and exposures to PFOS used in industry. A PFOS use inventory in metal plating and fire fighting. Bilthoven: RIVM Report 601780002.

  2. Perfluorinated substances and their uses in Sweden. 2006. www.kemi.se/upload/Trycksaker/Pdf/Rapporter/Report7_06.pdf

  3. PFOA in Norway. 2007. Survey of national sources, Report 2354, SFT. www.sft.no/publikasjoner/2354/ta2354.pdf

  4. PFOS Regulatory Impact Analysis Statement. 2008. Canada Gazette, part II (Vol. 142, No. 12), 11 June 2008. www.ec.gc.ca/ceparegistry/documents/regs/g2-14212_rias1.pdf

  5. 2007 OECD workshop on perfluorocarboxylic acids (PFCAs) and precursors report 2007. www.olis.oecd.org/olis/2007doc.nsf/LinkTo/NT00002AB6/$FILE/JT03229256.PDF

  6. Fluorosurfactants Conference. June 2008. http://pft.fh-fresenius.de/

  7. OECD. [supply date] Perfluorooctane sulfonate (PFOS) and related chemical products. www.oecd.org/document/58/0,,en_2649_34375_2384378_1_1_1_1,00

  8. Shuji Tamura presentation. 2008. “Substitution and alternatives”. POPRC4, October 2008.

  9. Ryo Usami presentation: 2008. “Case study on PFOS”. POPRC4, October 2008.

  10. Presentations at the International Workshop on Managing Perfluorinated Chemicals and Transitioning to Safer Alternatives, 12–13 February 2009, Geneva, Switzerland.

  11. Overview of Existing Information on PFOS Production, Use, Emissions and Pathways to the Environment and Cost/Benefits with alternatives/substitutes. 25 January 2006.87

____________________

1 UNEP/POPS/POPRC.1/9 and UNEP/POPS/POPRC.1/INF/9.

2 UNEP/POPS/POPRC.2/17/Add.5.

3 UNEP/POPS/POPRC.3/20/Add.5.

4 UNEP/POPS/POPRC.4/15/Add.6.

5 UNEP/POPS/COP.4/38.

6 Risk and Policy Analysts and Building Research Environment. 2004. Perfluorooctane sulphonate: risk reduction strategy and analysis of advantages and drawbacks. United Kingdom Department for Environment, Food and Rural Affairs and Environment Agency for England and Wales.

7 Jensen, A.A., Poulsen, P.B., Bossi, R. 2008. Survey and environmental/health assessment of fluorinated substances in impregnated consumer products and impregnating agents. Survey of Chemical Substances in Consumer Products, 99. Danish Environmental Protection Agency.

8 Document ENV/JM/MONO (2006) 15 (not available online).

9 Government of Canada. Completed Assessments of Existing Substances: www.chemicalsubstanceschimiques.gc.ca/about-apropos/assess-eval/caes-ecse/caes-pp-eng.php.

10 Alternative CAS name: 1-Octanesulfonamide, N,N'- [phosphinicobis(oxy-2,1-ethanediyl)]bis[N-ethyl]- 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-, ammonium salt.

11 UNEP/POPS/POPRC.2/17/Add.5.

12 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.

13 www.epa.gov/oppt/pfoa/pubs/stewardship/index.html and www.epa.gov/oppt/existing chemicals/pubs/actionsplans/pfcs.html.

14 http://solutions.3m.com/wps/portal/3M/en_US/Scotchgard/Home/.

15 www2.dupont.com/Zonyl_Foraperle/en_US/products/zonyl_pgs/zonyl.html.

16 Information from Norwegian Pollution Control Authority (former Statens Forurensningstilsyn), 2009.

17 www.mst.dk/Nyheder/Pressemeddelelser/Nanospray.htm.

18 www.advantex-textiles.com/.

19 www.rudolf.de/innovations/hydrophobic-future/bionic-finish/self-organisation.htm.

20 www.ciba.com/pf/default.asp?search=1&DApname=lodyne.

21 www.paper.clariant.com/businesses/paper/internet.nsf/vwWebPagesByID/65137D7B8419F6EDC12571E0003D5C16.

22 Information from Norwegian Pollution Control Authority (former Statens Forurensningstilsyn), 2009.

23 Poulsen, P.B., Jensen. A.A., Wallström, E. 2005. More environmentally friendly alternatives to PFOS compounds and PFOA. Environmental Project no. 1013. Danish Environmental Protection Agency. www2.mst.dk/Udgiv/publications/2005/87-7614-668-5/pdf/87-7614-669-3.pdf.

24 Organization for Economic Cooperation and Development. 2006. Results of the 2006 OECD Survey on Production and Use of PFOS, PFAS, PFOA, PFCA, Their Related Substances and Products/Mixtures Containing These Substances. ENV/JM/MONO(2006)36. Available at www.oecd.org/officialdocuments/displaydocumentpdf/?cote=ENV/JM/MONO(2006)36&doclanguage=en.

25 www2.dupont.com/Capstone/en_US/uses_apps/Fluorosurfactants/oil_field_services.html.

26 Information from the United States Environmental Protection Agency, 2009.

27

www.oecd.org/officialdocuments/displaydocumentpdf/?cote=ENV/JM/MONO(2006)36&doclanguage=en.



28 Photo masks are optically transparent fused quartz blanks imprinted with a pattern defined with chrome metal and are the templates used to inscribe the circuit pattern into the photo resist.

29 Information provided by the European Semiconductor Industry Association.

30 UNEP/POPS/POPRC.4/INF/17.

31 www.freepatentsonline.com/6319423.html and www.freepatentsonline.com/WO2006138081.html.

32 Risk and Policy Analysts and Building Research Environment. 2004. Perfluorooctane sulphonate: risk reduction strategy and analysis of advantages and drawbacks. United Kingdom Department for Environment, Food and Rural Affairs and Environment Agency for England and Wales.

33 www.fluoridealert.org/pesticides/pfos.pfoas-page.htm.

34 www.epa.gov/fedrgstr/EPA-PEST/2008/May/Day-16/p10919.htm.

35 UNEP/POPS/POPRC.3/20/Add.5.

36 Cameron 1990; Forti et al. 2007; Nagamoto et al. 2007.

37 Forti et al. 1998; Nagamoto et al. 2004.

38 Forti et al. 1998.

39 Forti et al. 1998.

40 Charge-coupled device (technology for capturing digital images).

41 Personal communication from Pia B. Poulsen, FORCE Technology, August 2010.

42 Personal communication from Carsten Ree Jørgensen, CEO, Nichro, 2009.

43 Personal communication from Per Møller, Technical University of Denmark, 16 March 2009.

44 Personal communication from Frank Jensen, Danish Environmental Protection Agency, 17 March 2009.

45 Renner R. 2009. EPA finds record PFOS, PFOA levels in Alabama grazing fields. Environmental Science and Technology 43: 1246–1247.

46 Personal communication from Christoph Matheis, Zentralverbandes Oberflächentechnik e. V. (ZVO), 6 March 2009.

47 European Commission. 29 January 2010. Implementation of the restriction on PFOS under the Directive 2006/122/EC – electroplating applications and fire fighting foams containing PFOS stocks.

48 Presentation by Jun Huang, Tsinghua University, at the national workshop on nine new persistent organic pollutants and the implementation of the Stockholm Convention in China, Beijing, 1–2 July 2010.

49 www.epa.gov/r5water/npdestek/pdf/pfoschromeplaterstudypdf_final.pdf.

50 Personal communication from Christoph Matheis, Zentralverbandes Oberflächentechnik e. V. (ZVO), 6 March 2009.

51 Personal communication from Jutta Hildenbrand, University ofWuppertal, 15 October 2009.

52 Information from Norwegian Pollution Control Authority (former Statens Forurensningstilsyn), 2009.

53 Personal communication from Roland Weber, March 2010.

54 Pabon M, Corpart JM. 2002. Fluorinated surfactants: synthesis, properties, effluent treatment. Journal of Fluorine Chemistry 114: 149–156.

55 Climate and Pollution Agency (former SFT), Norwegian Ministry of the Environment. 2005. Kartleggning av PFOS in brannskum [Survey of PFOS use in fire-fighting foam]. TA-2139.

56 Buser, A., Morf, L. 2009. Substance flow analysis of PFOS and PFOA in Switzerland. Environmental Studies 0922. Federal Office for the Environment, Bern.

57 www.fffc.org/.

58 Asia Pacific Fire Magazine 26: 2008.

59 www.kiddecanada.com/utcfs/Templates/Pages/Template-50/0,8061,pageId%3D2587&siteId%3D463,00.html.

60 Information from Norwegian Pollution Control Authority (former Statens Forurensningstilsyn), 2009.

61 Risk and Policy Analysts and Building Research Environment. 2004. Perfluorooctane sulphonate: risk reduction strategy and analysis of advantages and drawbacks. United Kingdom Department for Environment, Food and Rural Affairs and Environment Agency for England and Wales.

62 www.epa.gov/oppt/pfoa/pubs/stewardship/index.html.

63 Newsted JL, Beach SA, Gallagher SP, Giesy JP. 2008. Acute and chronic effects of perfluorobutane sulfonate (PFBS) on the Mallard and Northern Bobwhite quail. Archives of Environmental Contamination and Toxicology 54: 535–545.

64 Presentation by Jun Huang, Tsinghua University, at the national workshop on nine new persistent organic pollutants and the implementation of the Stockholm Convention in China, Beijing, 1–2 July 2010.

65 www.epa.gov/oppt/existingchemicals/pubs/pfcs_action_plan1230_09.pdf.

66 www2.dupont.com/Forafac/en_US/index.html.

67 D’eon JC, Crozier PW, Furdui VI, Reiner EJ, Libelo EL, Mabury SA. 2009. Observation of a commercial fluorinated material, the polyfluoroalkyl phosphoric acid diesters, in human sera, wastewater treatment plant sludge, and paper fibers. Environmental Science and Technology 43: 4589–4594.

68 Personal communication from Richard Thomas, January 2010.

69 www.nicnas.gov.au/publications/CAR/new/NA/NAFULLR/NA0600FR/NA651FR.pdf;

www.epa.gov/r5water/npdestek/pdf/pfoschromeplaterstudypdf_final.pdf.

70 Personal communication from Richard Thomas, OMNOVA, January 2010.

71 Cousins AP, Kaj L, Broström-Lundén E. 2009. Siloxanes in the Nordic environment. Norman Bulletin no. 1. www.norman-network.net.

72 Kaj L, Schlabach M, Andersson J, Cousins AP, Schmidbauer N, Brorström-Lundén E. 2005. Siloxanes in the Nordic Environment. TemaNord 2005:593.

73 Lassen C, Hansen CL, Mikkelsen SH, Maag J. 2005. Siloxanes – consumption, toxicity and alternatives. Environmental Project no. 1031. Danish Environmental Protection Agency.

74 ABCR 2006–2007 catalogue: Fluorochemicals. Karlsruhe, Germany.

75 Greve K, Nielsen E, Ladefoged O. 2008. Toxic effects of siloxanes: group evaluation of D3, D4, D5, D6 and HMDS in order to set a health-based quality criterion in ambient air. Toxicology Letters 180: S67.

76 Personal communication from Pascal-Louis Caillaut, Bluestar Silicones, 11 February 2010.

77 European Centre for Ecotoxicology and Toxicology of Chemicals. 1994. Joint Assessment of Commodity Chemicals 026 - Linear Polydimethylsiloxanes (CAS no. 63148-62-9) available at www.ecetoc.org/index.php?mact=MCSoap,cntnt01,details,0&cntnt01by_category=3&cntnt01order_by=Reference%20Desc&cntnt01template=display_list_v2&cntnt01display_template=display_details_v2&cntnt01document_id=96&cntnt01returnid=91; updating of this report is in progress.

78 http://ec.europa.eu/health/ph_risk/committees/04_sccp/docs/sccp_o_035.pdf.

79 The draft amended final safety assessment can be accessed at www.cir-safety.org/staff_files/blue.pdf.

80 Nørgaard AW, LarsenST, Hammer M, Poulsen SS, Jensen KA, Nielsen GD, Wolkoff P. 2010. Lung damage in mice after inhalation of nanofilm spray products: the role of perfluorination and free hydroxyl groups. Toxicological Sciences 116 (1): 216–224.

81 www.chemicalsubstanceschimiques.gc.ca.

82 www.cyclosiloxanes.eu.

83 www.enthone.com/pwb/index.aspx.

84 Poulsen PB, Jensen AA, Wallström E. 2005. More environmentally friendly alternatives to PFOS compounds and PFOA. Environmental Project 1013. Danish Environmental Protection Agency. www.mst.dk/Udgivelser/Publications/2005/06/87-7614-668-5.htm.

85 ABCR 2006–2007 catalogue: Fluorochemicals. Karlsruhe, Germany.

86 Presentation by Takashi Fukushima, Japanese Ministry of Economy, Trade and Industry, at the national workshop on nine new persistent organic pollutants subject to the Stockholm Convention and the implementation of the Convention in China, Beijing, 1–2 July 2010.

87 www.unece.org/env/lrtap/TaskForce/popsxg/2006/Overview%20of%20existing%20information%20on%20PFOS%20emissions%20and%20pat..pdf.

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