1. Updates on international efforts for risk reduction of PFCs
Kei Ohno
Secretariat of the Stockholm Convention

2. Stockholm Convention Objective:
To protect human health and the environment from persistent organic pollutants (POPs).

3. Listed 21 POPs Annex A (Elimination) Annex B (Restriction)
Pesticides: Aldrin, alpha HCH, beta HCH, chlordane, chlordecone, dieldrin, endrin, heptachlor, lindane, mirex, toxaphene
Industrial chemicals: hexachlorobenzene, PCBs, hexabromobiphenyl, hexa and hepta BDEs, tetra and penta BDEs, pentachlorobenzene,
Annex B (Restriction)
Pesticides: DDT
Industrial chemicals: Perfluorooctane sulfonic acid (PFOS), its salts and perfluorooctane sulfonyl fluoride (PFOSF)
Annex C (Unintentional production)
Dioxins and furans, PCBs, hexachlorobenzene, pentachlorobenzene

4. Obligations for listed POPs
Implement control measures
If no alternatives, register specific exemptions, acceptable purposes
Develop and implement Action Plans for unintentional POPs
Develop inventories of the stockpiles
Review and update National Implementation Plan
Conduct monitoring for effectiveness evaluation

5. Acceptable purposes for PFOS
Photo imaging
Photo resist and anti-reflective coatings for semi-conductors
Etching agent for compound semi-conductors and ceramic filters
Aviation hydraulic fluids
Metal plating only in closed-loop systems
Certain medical devices (e.g. ETFE layers, radio-opaque ETFE, in vitro diagnostic medical devices, CCD colour filters)
Fire fighting foam
Insect baits for control of leaf-cutting ants.

6. Specific exemptions for PFOS
Photo masks in the semiconductor and LCD industries
Metal plating (decorative and hard)
Electric and electronic parts for some colour printers and colour copy machines
Insecticides for control of red imported fire ants and termites
Chemically driven oil production
Carpets
Leather and apparel
Textiles and upholstery
Paper and packaging
Coatings and coating additives
Rubber and plastics

7. Risk management evaluation document for PFOS (2007 and 2008)
UNEP/POPS/POPRC.3/20/Add.5 and UNEP/POPS/POPRC.4/15/Add.6
Information gathered in accordance with Annex F
Efficacy and efficiency of possible control measures
Alternatives (costs, risks, efficacy, accessibility)
Positive/negative impacts of control measures on health, agriculture, biota, economic aspects, social costs
Waste, disposal implications, stockpiles
Access to information and public education
Status of control and monitoring capacity
Any national or regional control actions

8. General guidance on consideration for identification of alternatives (2009)
UNEP/POPS/POPRC.5/10/Add.1
Collection of use and emission information on chemicals
Consultation to define a chemical’s use
Description of the chemical’s existing use and functionality
Information on release into the environment
Identification of alternatives
Identification of potential alternatives
Assessment of availability, technical feasibility, accessibility and efficacy of alternatives
Assessment of risk related to alternatives
POPs screening criteria
Hazardous properties
Non-chemical alternatives
Verification of controls in other jurisdictions
Social and economic assessment of alternatives
Evaluation of alternatives

9. Guidance on alternatives to perfluorooctane sulfonate and its derivatives (2010)
To be published in UNEP/POPS/POPRC.6/13/Add.3 (UNEP/POPS/POPRC.6/INF/8 revised at POPRC6)
Objectives of the study:
To summarize what is currently known about alternatives to PFOS, its salts, and PFOSF
To enhance the capacity of developing countries and countries with economies in transition to phase-out PFOS

10. Section II. Characteristics of PFOS and its derivatives
PFOS substances mentioned in Annex B
CAS No:
Perfluorooctane sulfonic acid
Potassium perfluorooctane sulfonate
Lithium perfluorooctane sulfonate
Ammonium perfluorooctane sulfonate
Diethanolammonium perfluorooctane sulfonate
Perfluorooctane sulfonyl fluoride
Tetraethylammonium perfluorooctane sulfonate
Di(decyl)di(methyl)ammonium perfluorooctane sulfonate
PFOSF is an intermediate material for production of all C8-perfluorinated alkyl sulfo compounds. Production and use of PFOSF and consequently also of all other C8-perfluorinated alkyl sulfo compounds is restricted to acceptable purposes and specific exemptions.
More complex PFOS precursors are often used.
These derivatives are covered through the listing of PFOSF, the basic material for their manufacture.

11. Use of PFOS-related substances
Section III. Alternatives to the use of PFOS
(1)
Use area
Use of PFOS-related substances
Alternatives used
Impregnation of textiles, leather and carpets
PFOS-related substances have been phased out in most OECD countries.
Other fluorinated compounds, like C6-fluorotelomers and PFBS, silicone-based products, stearamidomethyl pyridine chloride
Impregnation of paper and cardboard
Fluorotelomer-based substances and phosphates, mechanical processes
Cleaning agents, waxes/ polishes for cars and floors
Fluorotelomer-based substances, fluorinated polyethers, C4-perfluorinated compounds
Surface coatings, paint and varnish
Telomer-based compounds, fluorinated polyethers, PFBS, propylated aromatics, silicone surfactants, sulfosuccinates, polypropylene glycol ethers
Oil production and mining
PFOS derivatives may occasionally be used as surfactants in the oil and mining industries.
PFBS, telomer-based fluorosurfactants, perfluoroalkyl-substituted amines, acids, amino acids and thioether acids

12. Use of PFOS-related substances
Section III. Alternatives to the use of PFOS
(2)
Use area
Use of PFOS-related substances
Alternatives used
Photographic industry
A shift to digital techniques has reduced the use drastically.
Telomer-based surfactants products, hydrocarbon surfactants, silicone products, C3-C4-fluorinated chemicals
Electrical and electronic parts
PFOS-based chemicals are or have been used in the manufacturing of digital cameras, mobile phones, printers, scanners, satellite communication and radar systems, etc.
For most of these uses, alternatives are available or are under development.
Semiconductor industry
PFOS is still used but in lower concentrations.
No substitutes with comparable effectiveness have been identified, and doing so may take up to 5 years, according to the industry. It should be possible to use PFBS, fluorinated polyethers or telomers.
Pesticides
Sulfluramid is used in some countries as an active substance and surfactant in pesticide products for termites, cockroaches and other insects. Other fluorosurfactants may be used as “inert” surfactants in other pesticide products.
Synthetic piperonyl compounds such as S‑Methoprene, Pyriproxyfen, Fipronil and Chlorpyrifos are alternative active substances, sometimes used in combination.
Alternative surfactants may exist.

13. Use of PFOS-related substances
Section III. Alternatives to the use of PFOS
(3)
Use area
Use of PFOS-related substances
Alternatives used
Aviation hydraulic oils
PFOS-related compounds may still be used.
Other fluorinated substances and phosphate compounds could be used.
Medical devices
Old video endoscopes at hospitals contain a CCD colour filter that contains a small amount of PFOS.
PFOS is also used as an effective dispersant for contrast agents in radio-opaque catheters.
Repairing such video endoscopes requires a CCD colour filter containing PFOS. New CCD filters are PFOS-free. For radio-opaque ethylene tetrafluoroethylene, PFBS can replace PFOS.
Metal plating
PFOS-compounds are still used in hard chrome plating.
Cr-III has replaced Cr-VI in decorative chrome plating.
Some non-fluorinated alternatives are marketed but they are not considered equally effective in hard chrome plating. A C6-fluortelomer is used as a substitute and may be effective. PFBS derivatives may also be used. Physical barriers may also apply.
Fire-fighting foams
The use of PFOS-related substances in new products has been phased out in most OECD countries. Stocks are still being used up.
C6– fluorotelomers are used as substitutes in new products; fluorine-free alternatives are used for training exercises and possibly in other settings than offshore.

14. Section IV: Properties of alternative substances and hazard assessment
Brief description of the environmental, safety and health properties of PFOS alternatives:
Shorter-chain perfluoroalkyl sulfonates
Shorter-chain perfluoroalkyl ketones and ethers
Polyfluorodialkyl ether sulfonates
Fluorotelomers and fluorophosphates
Fluorinated co-polymers
Fluorinated polyethers
Siloxanes and silicone polymers
Propylated aromatics
Sulfosuccinates
Stearamidomethyl pyridine chloride
Polypropylene glycol ether, amines, and sulfates

15. Section V: Comparative assessment of PFOS and possible alternatives
Prices of selected basic polyfluorinated laboratory chemicals
Chemical
CAS No:
Molecular weight
Price in €
per 100 g
Perfluorobutane sulfonyl fluoride (PFBSF)
303.09
136
Perfluorobutane sulfonic acid (PFBS)
300.10
1,800
Perfluorooctane sulfonic acid (PFOS)
500.13
1,122
Perfluorooctane sulfonyl fluoride (PFOSF)
502.12 92
Fluorotelomer 6:2 alcohol
364.10
130
Fluorotelomer 8:2 alcohol
464.12
187
Fluorotelomer 10:2 alcohol
564.14
1,440
Methyl nonafluorobutyl ether
250.06
745
ABCR 2006–2007 catalogue: Fluorochemicals. Karlsruhe, Germany

16. Section VI: Conclusions, recommendations and future developments
Low surface tension is the key
Substitutes for PFOS are available
Need for better alternatives
Need for incentives
Complex assessment
Need for more public data and information on alternatives
Need for better communication in the value chain

17. Work programme on newly listed persistent organic pollutants (SC-4/19)

18. Collected information
Types and quantities of articles containing PFOS etc., concentrations in articles
Types of processes using PFOS etc., concentrations, options for the environmental management
Types of articles recycled, the extent of recycling, articles produced from recycling, options for the environmental management
Cost effectiveness of different management options
Sampling and analysis methods
Remediation methods for contaminated sites

19. Recommendations on risk reduction for PFOS, its salts, and PFOSF by the POPs Review Committee (POPRC6)
To be published in UNEP/POPS/POPRC.6/13
Recommendations are given in chronological order of the life cycle, provided in short, medium, and long term framework.
For industrial production, use, and releases and deposits
For use of PFOS
For PFOS in existing stocks
For recycling of PFOS containing articles
For PFOS in consumer products deposited on municipal landfills
For releases of PFOS from contaminated sites
Given that PFOS precursors may contribute to the overall presence of PFOS in the environment, the recommendations below consider, as appropriate, the management of PFOS and PFOS-related chemicals.
Countries in the position to do so, are encouraged to take up these recommendations as soon as possible and exchange their experiences and success stories with other countries. Transfer of knowledge and technology, including capacity strengthening to identify PFOS in articles/applications and monitor PFOS in the environment, should be promoted in support of full participation in the global effort to reduce risk from PFOS.

20. Short-term recommendations in summary:
Identify disposal options in compliance with Stockholm Convention guidelines for the destruction of PFOS containing waste including sludge and prevent depositing in landfills;
Establish safely storage for indicative PFOS-containing materials and articles as well as existing stocks;
Conduct monitoring of PFOS contamination in the surrounding waters of landfills with deposits from PFOS producers/users;
Assess occupational exposures of staff working in facilities where articles and wastes potentially containing PFOS are handled;
Identify and introduce alternatives to PFOS in open applications and promote use in closed-loop systems and BAT/BEP in treatment;
Gather information on the experiences of the use of PFOS alternatives including risk assessment of the alternatives;
Raise awareness on environmental and human health effects of PFOS and provide training on appropriate handling of PFOS, including risks caused by misuse of PFOS containing carpets;
Establish a strategy for identifying and monitoring of sites contaminated with PFOS in accordance with Article 6.

21. What’s next?
COP 5
25-29 April 2011 in Geneva

22. For more information: http://www.pops.int Contact: Kei Ohno
Secretariat of the Stockholm Convention

23. NOTE: Specific exemptions vs. acceptable purposes
Annex A with Specific exemptions
Need to register (except for PCBs)
Exemption open for 5 years from the date of entry into force
When all registrations have expired, no new registrations possible
Exemptions may be extended by the COP based on a report by the Party justifying the continuing need for the exemption.
Annex B with Specific exemptions and Acceptable purposes
Specific exemptions: same as Annex A
Acceptable purpose: need to register, no expiration unless otherwise decided by the COP

24. NOTE: Persistent Organic Pollutants Review Committee (POPRC)
Subsidiary body to the Convention, mandated to review proposals submitted by Parties for listing new chemicals in Annex A, B, or C.
31 government-designated members
Terms of reference, conflict of interest procedure: SC-1/7,SC-1/8, SC-4/20