Uses of Perfluorinated Substances

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Uses of Perfluorinated Substances
Adam Walters & David Santillo
Greenpeace Research Laboratories Technical Note 06/2006
September 2006
GRL-TN-06-2006
Contents
1
2
3
4
Introduction ........................................................................................................................ 3
Terminology ....................................................................................................................... 5
PFOS and related substances.............................................................................................. 6
Perfluorocarboxylic Acids.................................................................................................. 9
4.1
Product sources of perfluorocarboxylic acids ............................................................ 9
4.1.1
Fluoropolymers .................................................................................................. 9
4.1.2
Non-stick cookware.......................................................................................... 10
4.1.3
Reported levels of PFOA from fluoropolymers............................................... 11
4.1.4
Fluorotelomer products .................................................................................... 11
5
Substitutes ........................................................................................................................ 14
6
Conclusions ...................................................................................................................... 14
7
References ........................................................................................................................ 15
2
GRL-TN-06-2006
1 Introduction
Most organic molecules contain long carbon chains with most bonding sites occupied
by hydrogen atoms. Though not exactly labile, the hydrogen atoms are available for
reaction e.g combustion, breakdown to smaller molecules etc. Whilst a lack of
polarity results in hydrophobic traits (an inability to dissolve in, and repellence of,
water) the molecules will dissolve in oils, fats, and other organic solvents. What was
discovered (serendipitously) in the 1930s by DuPont workers was that if the
hydrogen atoms in an organic molecule or polymer are replaced either entirely or
substantially by fluorine atoms then a substance with remarkably different properties
results.
Carbon - fluorine bonds are very strong and relatively short. Therefore saturation of
bonding sites on an organic molecule with fluorine prevents chemical attack resulting
in a very inert substance. As well as being hydrophobic fluorinated molecules are
also generally oelophobic (oil and fat insoluble). This sets heavily fluorinated
substances apart from heavily chlorinated or brominated substances such as
polybrominated diphenyl ethers and polychlorinated biphenyls which dissolve in fats
and oils. The unique properties are exploited in a wide range of discrete molecules,
co-polymers and homopolymeric substances for a variety of applications.
For over 50 years the novel properties of perfluorinated substances have been
utilised in a very wide range of products and applications. However in the late 1990s
it was discovered that one widely used perfluorinated compound, PFOS, was
becoming widespread in the environment, animals and humans, as a ubiquitous
pollutant. This discovery heralded the recognition of a new kind of persistent organic
pollutant (POP). Due to the unique chemical properties of perfluorinated compounds
(PFCs), their environmental behaviour, bioaccumulation, and toxicological activity all
occur via different routes to the more extensively studied POPs (eg organochlorine
and organobromine compounds). Since 2000 there has been a great deal of activity
by research laboratories, regulatory authorities and industry to classify, monitor and
regulate these pollutants.
Two compounds in particular, perfluorooctane sulphonate (PFOS) and
perfluorooctanoic acid (PFOA),represent the final environmental degradation
products of (and contaminants in) a wide range of other perfluorinated products and
have been most extensively studied. PFOS is now subject to varying but (increasing)
levels of control in a number of countries. Perfluorooctanyl sulphonic acid and its
salts (PFOS) has been added to the OSPAR list of List of Chemicals for Priority
Action (LoCfPA). The substance meets the criteria for inclusion to the Stockholm
Convention on Persistent Organic Pollutants and a draft risk profile is in production.
PFOA, also a widespread contaminant but with a far lower bioaccumulation potential
is still under evaluation. The US EPA released a draft risk assessment of the
potential human health effects of exposure to PFOA and its salts in January 2005. A
subsequent review by the EPA Science Advisory Board (SAB) concluded that there
is sufficient evidence to classify the compound as a “likely” human carcinogen,
though this has yet to be adopted as the official opinion of the EPA.
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GRL-TN-06-2006
We have previously published a review of the body of knowledge relating to the
environmental distribution and (eco) toxicity of perfluorinated compounds:
Perfluorinated compounds: an emerging concern (Allsopp et al 2005).
The current document is intended to supplement this, providing a more detailed
examination of:
i.
Products containing perfluorinated compounds especially PFOS and related
compounds
ii. Sources of PFOA and the manner in which other PFCs may act as sources of
PFOS and PFOA
4
GRL-TN-06-2006
2 Terminology
Fluorochemical:
A term used to describe broadly all chemicals containing the
element fluorine; Specifically, the term is used most commonly
to describe small (1-8 carbon length) fluorinated molecules
which are most used for refrigeration, fire suppression and as
specialty solvents.
Fluorinated chemical:
a term used synonymously with “fluorochemical”.
Fluorotelomer:
a term used to describe an oligomer created by reaction of
tetrafluoroethylene (TFE) with perfluoroethyl iodide CF3CF2I to
produce F(CF2CF2)n-I [n = 3-6, avg. 4], the term “telomer” is
often used synonymously with fluorotelomer.
Fluoropolymer:
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 (PVDF),
fluorinated ethylenepropylene (FEP), etc.
Fluorinated organic polymer: a term used to describe a polymer which has a hydrocarbon
backbone (polyamide, polyester, polyurethane, etc.) to which a
fluorinated carbon chain is attached.
Perfluoro- /Perfluorinated:
describes a substance where all hydrogen atoms attached to
carbon atoms are replaced with fluorine atoms – CFn - where
n = 1 - 4.
Perfluoroalkylated substance: a substance which bears a perfluorocarbon, also known as a
perfluroroalkyl, functional group. F(CF2)n- R where n is an
integer and R is not a halogen, or hydrogen.
Fluorinated organic surfactant: a term to describe a surface active, low molecular weight,
substance which contains fluorinated carbons; the term
fluorosurfactant is used synonymously.
Perfluorinated surfactant:
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.
5
GRL-TN-06-2006
3
PFOS and related substances
PFOS is an environmentally persistent compound. Though not used extensively on
its own it is an essential intermediate and breakdown product of a (once) diverse
class of PFCs.
Perfluorooctyl sulphonates: Major product categories
OECD (2002)
Many of the substances shown above may potentially break down to PFOS. The
compound has a much higher bioaccumulation factor (6300-125000) (Hekster et al
2003) than most other PFCs. Unlike other POPs, which accumulate in fatty tissues
PFOS the substance binds to blood and accumulates in the liver.
A number of toxicological concerns surround this substance; these are reviewed
extensively in Perfluorinated Chemicals: an emerging concern (Allsopp et al 2005).
PFOS meets the criteria for a PBT (persistant, bioaccumulative, toxic) substance
under REACH (Annex XII of the proposed legislation details the criteria).
In 2000, the world largest producer of PFOS-related substances, 3M announced that
it intended to cease production in recognition of increasing evidence and concern
relating to its environmental distribution. Over the next couple of years the company
reformulated its entire range of “Scotch” brand products with chemistry based around
another PCF, perfluorobutane sulfonate (PFBS). This substance (like all PFCs) is
6
GRL-TN-06-2006
persistent but it appears that short chain sulfonates do not bioaccumulate (Martin et
al 2003 a) and exhibit relatively low toxicity.
Usage data for Europe are conflicting. It is to be expected that since 3M withdrew
from the market, household use of PFOS related substances ceased. Some
specialist industrial use of PFOS substances still occurs in the UK (RPA 2004). All
applications exploit the substances’ unique surfactant properties and include:
•
•
•
•
•
Chromium Plating (mist suppressant)
Aviation hydraulic fluid (PFOS compounds are used as components of this)
Photolithography and Semiconductors (surface active qualities are exploited)
Photographic industry (anti-static and cleaning properties considered essential)
Fire-fighting Foams (Since the 3M phase out this should have reduced)
Estimated current demand for PFOS-related substances in the EU
Application
Chromium plating
Anodising and Acid pickling
Photographic Industry
Paper products
Printing plates
Film products
Total
Semiconductor Industry
Photoresists
Edge bead removers
Top antireflective coatings
Bottom antireflective coatings
Developers (surfactant)
Total
Aviation
Industry Hydraulic fluids
Storage for Emergency Use (Note not annual usage)
Industry Sector
Metal Plating
Quantity (kg/year)
10 000
20-30
<50
<100
>850
1000
46
86
136
8
195
471 (assumed 500)
730
EU Total Storage (kg)
122 000
Fire fighting foam storage for emergency use
OSPAR (2005)
The UK and Swedish governments, the OECD, US EPA and a number of other
bodies have all adopted positions on PFOS and related substances. In the US, the
use of these chemicals must be notified to the EPA. During 2005, the UK government
prepared draft legislation for the phase out of PFOS by 2010, which it intended to
implement from April 2006 unless the European Commission came forward with a
draft measure in the meantime (DEFRA 2005). The proposed UK approach drew
upon aspects of the REACH model in that any continued use after that date will be
subject to specific authorisation.
In the latter part of 2005, the European Commission did propose controls, under the
so-called (Restrictions on) Marketing and Use Directive (76/769/EEC), as laid out in
paper COM (2005) 618 (EC 2005). However, the major part of the uses prohibited
under this draft measure have already been discontinued within Europe, including
use in carpets, upholstery and other textiles and in paper packaging products.
Moreover, evidence exists that many of the remaining uses which would be permitted
under the Commission’s proposed amendment, such as use in semiconductor
manufacture, industrial photographic applications, chrome-plating and in fire-fighting
foams, could also be phased-out within the next five years. Indeed, proposals for
7
GRL-TN-06-2006
national measures in the UK and Sweden explicitly expressed the desirability and
feasibility of such programmed phase-outs addressing all uses other than as
components of hydraulic fluids used in aviation, setting out, in the case of the UK, a
series of application-specific sunset dates ranging from 2007-2010.
The restrictions proposed by the Commission also fall short in other ways, such as
the allowance for 0.1% by weight of PFOS in preparations and finished articles,
which may ultimately result in continued or future use in a far broader range of
product groups in which deliberate use at concentrations below 0.1% is feasible
(OECD 2004).
A more detailed critique of the European Commission proposal, currently before the
European Parliament, is provided in the Appendix to this document.
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GRL-TN-06-2006
4 Perfluorocarboxylic Acids
PFOA (known as C8- ie 8 carbon atoms) is by far the most extensively studied
perfluorocarboxylic acid (PFCA). Attention has focused primarily on PFOA due to the
use of it and its ammonium salt as polymerisation aids in the manufacture of
polytetrafluoroethylene (PTFE). This has resulted in major point source releases of
the compound for 50 years (Paustenbach et al 2005). Issues relating to
contamination caused by these compounds has led to class action lawsuits against
DuPont in the United States. However, the longer chain acids (C9-C14) have
bioconcentration factors orders of magnitude greater to that of PFOA (Martin et al
2003 a,b) and may exhibit similar modes of toxicity (Martin et al 2004). Martin et al
2004 report the presence of the longer chain acids in Canadian Artic biota at higher
concentrations than PFOA itself, combined with sparse toxicological information on
these longer chain acids.
Perfluorocarboxylic acids are the final degradation products (under normal conditions)
of a wide range of other perfluorinated compounds. Whilst levels in urban
environments are likely to result from point sources, processing or producing
perfluorinated substances (Stock et al 2004, Paustenbach et al 2005) or fugitive
emissions of residual material present in fluoropolymers and perfluorinated products,
the compounds’ low atmospheric mobility (Simcik 2005) has led to the theory that the
levels found in remote areas result from the degradation of more mobile precursors
such as telomer alcohols and sulfonated perfluorocarbons (Martin et al 2004, Simcik
2005, Stock et al 2004). This theory remains to be confirmed but represents the most
likely explanation to date for the widespread environmental presence of PFOA.
4.1 Product sources of perfluorocarboxylic acids
4.1.1 Fluoropolymers
The only direct use of PFOA (and its ammonium salt APFO) is as a non-reactive
polymerisation aid in the production of fluoropolymers. PTFE, the first and probably
most widely used fluoropolymer, has a number unique properties including:
• Extreme resistance to chemical attack
• Stability up to 250 oC
• Very high electrical resistance
• One of the lowest coefficients of friction of any substance
• UV resistance
Applications of PTFE include: electrical wire insulation, specialist circuit boards,
plumbers tape, waterproof membranes for garments (such as Gore-Tex), surgical
implants, dental floss, engine protector additives, non-stick coatings, moulded parts
and coatings for use in a wide range of chemically hostile environments. Whilst
manufacturers state that PFOA/APFO may be present in polymer pastes,
membranes and mouldings the concentration in final products depends upon the
processing techniques employed. Heat has been shown to volatize PFOA leaving
finished products relatively free of the contaminant.
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4.1.2 Non-stick cookware
Manufacturers claim that PFOA present in pastes used for producing non stick pan
coatings is entirely driven off in the curing process (conducted at >300 oC)
(Washburn et al 2005).
It has been known since the 1950s that PTFE degrades at high temperatures to
release toxins. At lower temperatures (still greater than 250 oC) particulate matter is
released that is known to be fatally toxic to birds. Generally temperatures greater
than 300 oC are required for chemical decomposition of PTFE to occur. DuPont state
that their Teflon PTFE coating systems can withstand up to 260 oC safely. The only
paper found in this search of the literature that directly analysed the toxic effects of
particles and compounds evolved from a heated non-stick pan was published in 1975.
The study (Waritz 1975) involved heating pans to various temperatures and passing
the evolved products through a chamber containing live rats, parakeets or Japanese
quails for 4 hours. The gases were subsequently chemically analysed. The PTFE
pan evolved lethally toxic agents at high temperatures, a phenomena known as
“polymer fume fever” (mortality was observed in parakeets at 280 oC, quails at 330
o
C, and rats at 425-450 oC). It was suggested that particulate matter was the principle
toxic agent in each case. At 450 oC, tetrafluoroethylene itself was the only identified
compound produced, higher temperatures yielded heavier fluorinated compounds
(hexafluoropropylene and perfluoroisobutylene). Interestingly if non-PTFE coated
pans are left to heat containing either corn oil or butter lethal pyrolysis products are
produced at much lower temperatures.
Ellis et al (2001) published an analysis of the temperature dependant thermolysis of
PTFE polymer. The analysis methods employed allowed for a wider range of
compounds to be identified. The main product identified-hexafluoropropylene- may
react in the atmosphere to form trifluoroacetic acid. Other compounds isolated
included perfluoroacids (eg PFOA). The paper also reports that the same range of
compounds was found in tests with Teflon coated pans.
Overall there is clear evidence that a dry PTFE treated pan left on the heat to reach
temperatures greater than those used for cooking will result in the release of harmful
compounds and particles. However, PTFE can be expected to endure temperatures
up to 260 oC more than 2 years without significant degradation (Dupont 2005). It is
unlikely therefore that harmful substances derived from the pans will be detected in
food cooked in non-stick pans. The temperatures required for this would ensure that
the food itself constituted a greater health hazard.
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4.1.3 Reported levels of PFOA from fluoropolymers
Washburn et al (2005) report levels of perfluorooctanoate (the anion of PFOA)
extracted from finished fluoropolymer products:
Article Group
Membranes for apparel
Nonstick cookware
Thread seal (plumbers)
tape
Extraction test result for finished
consumer article (ng of PFO/cm2
article)
0.008 - 0.07
Not detected (<0.1)
0.02 - 0.08
Extractant used
Water
10% or 95% ethanol in
water
Water, simulated
perspiration
Interpretation of these data is difficult. Generated to form part of an exposure
assessment and risk characterisation, it does not report levels of perfluorooctanoate
per unit mass but only per unit area. This combined with the varying solvent system
used, prevents any detailed comparative overview being gained on either the levels
of total contamination for each article type or the relative levels of contamination in
different article types.
4.1.4 Fluorotelomer products
Fluorotelomer alcohols (FTOH) are used are used as surfactants and intermediates
in the manufacture of a variety of products with a wide range of applications including
polymers, paints, adhesives and cleaning agents. The link between fluorotelomer
alcohols and prefluorocarboxylic acids occurs on two levels. Firstly, production of 2perfluorodecylethanol (C8F17CH2CH2OH or 8:2 FTOH) causes unintended production
of PFOA (C8F17CO2H) (Washburn et al 2005). Though no substantiating information
is readily available it may be assumed that production of other telomer alcohols also
leads to perfluorocarboxylic acid contamination. Secondly, due to the stability of
perfluorocarboxylic acids, these are the likely final environmental degradation
products of telomer alcohols.
One application of particular relevance in terms of consumer exposure is the use of
FTOH to produce polymers for use on fabrics and in paper. For textile applications
FTOH derived polymers are used to impart water/grease repellence and anti-soiling
properties to fabric, leather or carpets. These (commonly) acryate/methacrylate
polymers are sold under a variety of trade marks and may either be impregnated as
part of finishing or sold as after-care products:
•
•
•
•
•
Baygard – Lanxess formally part of Bayer
Zonyl – DuPont
Nuva – Clariant
Unidyne – Daikin
Stainmaster – DuPont
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GRL-TN-06-2006
The diagram above illustrates how PFC (perfluorocarbon) chains form a flexible
repelling barrier and prevent anything from interacting with the fibre surface.
Impregnation of paper/cardboard with either FTOH derived polymers or additives can
provide both grease and water repellence. Products treated this way are used for
both food contact (plates, food containers, bags, and wraps) and non food contact
(folding cartons, carbonless forms, and masking papers) applications (Poulsen et al
2005). Common brand names include:
•
•
•
•
•
Zonyl – DuPont
Foraperle – Atofina/Dupont
Baysize-S (some formulations) – Lanxess (formally Bayer)
Cartafluor – Clariant
Lodyne – Ciba
Exposure to PFOA from articles treated with these products may occur through a
variety of routes. Industry sources (Boese et al 2005) state that FTOH derived
polymers contain less that 0.1% unbound However, FTOH. 8:2 FTOH, a commonly
used telomer alcohol building block of many products has been shown to breakdown
to PFOA through oxidative radical mechanisms in the atmosphere (Ellis et al 2005),
through microbial metabolism (Dinglasan et al 2004) and through the metabolic
activity of isolated rat hepatocytes (chief functional cells of the liver) (Martin et al
2005).
Direct releases of contaminant perfluorocarboxylic acids present a quantifiable
source of exposure (Barton et al 2005). The degradation polymers and subsequent
release of PFCA precursors cannot be eliminated as a further potential source. Given
the types of chemical linkage attaching the perfluorinated moiety to the polymeric
backbone, release is possible. A limited number of inconclusive industry studies,
however, refute this hypothesis (Boese et al 2005, Berti et al 2005). DinglasanPanlilio & Mabury (2006) report that the commonly used monomer, 8:2 telomer
methacrylate, may degrade in sewage sludge to metabolites similar to those of 8:2
FTOH.
A limited body of evidence is available reporting concentrations of the PFOA in
consumer articles. Washburn et al (2005) report levels extracted from a number of
articles treated with fluorotelomer based products. Limitations to interpretation and
inter-comparison of those data have already been noted above.
Article Group
Extraction test result
for finished consumer
article (ng of PFO/cm2
article)
Extractant used
Mill-treated carpeting
Treated upholstery
Treated apparel
Carpet-care solution-treated carpeting
ND(<0.2) – 23
0.4 – 4
ND (<0.01) – 12
28 – 50
Water,
Simulated saliva,
Simulated sweat
Water
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GRL-TN-06-2006
The data presented below, also from Washburn et al (2005) estimates concentrations
in consumer product formulations based on assumptive dilutions of the FTOH
ingredient.
Article group
Concentration in
fluorotelomer product
formulation
(mg of PFO/kg of
article)
Calculated total conc.
in finished consumer
article (mg of PFO/kg
of article)
Industrial floor waxes and wax
removers
Latex paint
Home and office cleaners
5 – 120
0.0005 – 0.06
50 – 150
50 – 150
0.02 – 0.08
0.005 – 0.05
No information is reported concerning the levels of unbound FTOH present in the
articles.
In another recent study, Buck et al (2005) report that, under simulated processing
conditions, all of the residual 8:2 FTOH and 95% of the PFOA present in a product
used to treat a polyester garment were emitted to air during subsequent drying at 190
o
C representing a source of perfluorinated compounds in the atmosphere. This
information, though useful, should be treated with caution as it seems to contradict
the direct reported concentrations found in garments elsewhere (Washburn et al
2005).
The German Ökotest consumer magazine reports levels of PFOA in both waterproof
Gore-Tex jackets and water repellent sprays (Ökotest 2005). The garments from
brands Arc'teryx, Berghaus, Mammut, Millet and Salewa contained PFOA at
concentrations between 0.08 and 0.6 mg/kg. These values appear to be higher than
those reported by Washburn et al (2005). However the different reporting units and
potentially different experimental methodologies prevent direct comparison.
Three Water repellant spays produced by Granger's Ltd, Salzenbrodt, and Erdal Rex
were tested for perfluorinated acids. The Grangers product was found to not contain
any of the compounds tested for within the reporting range. The other two sprays
contained levels of PFOA between 0.24 and 0.48 mg/kg and perfluorononanoic acid
(PFNA) between 0.25 and 0.77 mg/kg.
One Danish study (Engelund and Sørensen 2005) report the presence of both
perfluoroheptanoic acid (1.1 mg/kg) and PFOA (3.6 mg/kg) in one of four shoe care
products analyzed probably indicating the presence of a FTOH based polymer in the
product.
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GRL-TN-06-2006
5 Substitutes
For some applications substitutes for fluorinated compounds/polymers are available
(Poulsen & Jensen 2005). However many of these are either other fluorinated
substances or novel chemistries for which there is a lack of toxicological information.
It may be the case that in many cases substitution would involve significant product
redesign or, even more fundamentally, questioning of the necessity of the particular
technical performance feature imparted by fluorinated chemistry.
Alternative compound
Product trade
Company
Used in / used for
Perfluorobutanesulfonate
(PFBS) - C4
or based on different C4 perfluorocompounds
Novec®
3M
Dodecafluoro-2methylpentan-3-one
(CF3-CF2-C(O)-CF(CF3)2)
Novec®
3M
Paint and coatings industry. As
electronic coating. Industrial and
commercial cleaning. Cleaner for
solder flux residue. Degreasing
applications.
Fire-fighting fluid
C6fluorocompounds
(predominantly ∼80%)
FORAFAC®
DuPont
Fire-fighting foam
CF3or C2F5 pendant
fluoroalkyl polyethers
PolyFox®
OMNOVA
Solutions
Inc.
Propylated aromatics
(naphthalenes or
biphenyls)
Ruetasolv®
Rütgers
Kureha
Solvents
Gmbh
Surfactant and flow, level, and
wetting additive for coating
formulations. Also used in floor
polish.
Water repelling agents for rust
protection systems, marine paints,
coatings, etc.
Aliphatic alcohols
(sulphosuccinate and fatty
alcohol ethoxylates)
Sulfosuccinate
Emulphor®,
Lutensit®
BASF
Levelling and wetting agents
(EDAPLAN®LA 451)
Münzing
Chemie
Sulfosuccinate
(HYDROPALAT® 875)
Cognis
Silicone polymers
WorléeAdd®
WorléeChemie
Paint and coating industry: Wetting
agents for water based applications –
e.g. wood primers
Paint and coating industry: Wetting
and dispersing agents
Wetting agents in the
paint and ink industry
name
(Poulsen et al 2005)
6 Conclusions
No other published data regarding levels of PFOA (and precursors) in products was
available at the time of writing. However as the limited information presented here
shows there is reason to suspect that all PTFE (and possibly other fluoropolymers)
may be contaminated with PFOA unless it has been subjected to a high temperature
processing stage. The same applies to many fluorotelomer based and treated
products currently available. In any case, manufacturing results in substantial
releases to the environment.
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7 References
Allsopp M, Santillo D, Walters A & Johnston P (2005) Perfluorinated Chemicals: an emerging
concern Technical Note: 04/2005 Available from:
http://www.greenpeace.to/publications_pdf/perfluorinated_chemicals_2005.pdf
Barton CA, Butler LE, Zarzecki CJ, Flaherty JM, Botelho M, Kaiser MA (2005) Comparing
modelled and monitored values: Characterizing perfluorooctanoate in ambient air
near the fence line of a monitoring facility. Poster ANA027 presented at Fluoros
symposium 2005
Berti WR, Szostek B, Buck RC, Schaefer E, Van Hoven RL, Wang N Gannon JT (2005)
Biodegradation studies of fluorotelomer-based polymers to assess their potential to
contribute to perfluorinated carboxylic acids in the environment. . Poster ENV 18
presented at Fluoros symposium 2005
Boese W, Ho C, Knaup W, Koch V (2005) Biodegradation potential of a Clariant
fluorotelomer-based acrylate polymer- Results from a test on inherent
biodegradability (OECD 302B) Poster EVN 004 presented at Fluoros symposium
2005
Buck RC, Kaiser MA, Knaup W, Bose W, Schafer T, Thoma B (2005) Determining the fate of
fluorotelomer alcohol and PFOA in the textile finishing process. Poster ENV009
presented at Fluoros symposium 2005
DEFRA (2005) UK plan national action on perfluorooctane sulphonate (PFOS) and
substances that degrade to it. DEFRA Press release October 2005 available from
http://www.defra.gov.uk/environment/chemicals/pdf/pfos-note0510.pdf
Dinglasan-Panlilio MJ, Mabury SA (2005) Evidence of 8:2 FTOH production from the
biodegradation of 8:2 telomer methacrylate under aerobic conditions . Poster ENV023
presented at Fluoros symposium 2005
Dinglasan-Panlilio MJ, Mabury SA (2006) Significant residual fluorinated alcohols present in
various fluorinated materials. Environmental Science & Technology 40(5): 1447-1453
Dinglasan-Panlilio MJ, Ye Y, Edwards EA, Mabury SA. (2004) Fluorotelomer Alcohol
Biodegradation Yields Poly- and Perfluorinated Acids. Environmental Science and
Technology, 38: 2857-2864
EC (2005) Proposal for a Directive of the European Parliament and of the Council relating to
restrictions on the marketing and use of perfluorooctane sulfonates (amendment of
Council Directive 76/769/EEC)”, COM(2005) 618 final, 5.12.2005
Ellis D.A., Mabury S.A., Martin J.W. and Muir D.C.G. (2001). Thermolysis of fluoropolymers
as a potential source of halogenated organic acids in the environment. Nature 412:
321-324
Engelund B and Sørensen H (2005) Mapping and health assessment of chemical
substances in shoe care products. Danish Toxicology Centre. Survey of Chemical
Substances in Consumer Products, No. 52 2005
Hekster FM, de Voogt P, Pijnenburg AMCM, & Laane RWPM (2002) Perfluoroalkylated
Substances: Aquatic environmental assessment. Report RIKZ/2002.043
Hekster FM, Laane RWPM, & de Voogt P (2003) Environmental and toxicity effects of
perfluoroalkylated substances. Reviews of Environmental Contamination and
Toxicology 179:99-121
Imbalzano JF (1991) Combat corrosion with fluoroplastics and fluoroelastomers. Chemical
Engineering Progress 30: 69 - 73 Cited in llis D.A., Mabury S.A., Martin J.W. and Muir
D.C.G. (2001). Thermolysis of fluoropolymers as a potential source of halogenated
organic acids in the environment. Nature 412: 321-324
Martin J, Mabury SA, Solomon KS, & Muir DCG (2003a) Bioconcentration and Tissue
Distribution of Perfluorinated Acids in Rainbow Trout (Oncorhynchus mykiss)
Environmental Toxicology and Chemistry 22: 189-195
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Martin J, Mabury SA, Solomon KS, & Muir DCG (2003b) DietaryAccumulation of
Perfluorinated Acids in Rainbow Trout (Oncorhynchus mykiss. Environmental
Toxicology and Chemistry 22:196-204
Martin JW, Mabury SA and O’Brien PJ. (2005) Metabolic Products and Pathways of
FluorotelomerAlcohols in Isolated Rat Hepatocytes. Chemico-Biological Inter. In
press.
Martin JW, Smithwick MM, Braune BM, Hoekstra PF, Muir DCG, and Mabury SA (2004).
Identification of long-chain perfluorinated acids in biota from the Canadian
Arctic.Environmental Science and Technology 38 : 373-380
OECD (2002) Hazard Assessment of perfluorooctane sulfonate (PFOS) and its salts
Organisation for Economic Co-operation and Development
ENV/JM/RD(2002)17/FINAL , JT00135607
OECD (2004) Results of survey on production and use of PFOS, PFAS and PFOA, related
substances and products/ mixtures containing these substances. OECD
Environment, Health and Safety Publications Series on Risk Management No. 19,
JT00176885, Paris 2004: 59 pp. Available from:
http://www.olis.oecd.org/olis/2005doc.nsf/LinkTo/env-jm-mono(2005)1
Ökotest (2005) Test: Gore-Tex-Jacken. Ökotest Magazine May edition (in German)
OSPAR (2005) Hazardous Substances Series: OSPAR Background Document on
Perfluorooctane Sulphonate (PFOS) OSPAR Commission ISBN 1-904426-64-6
Publication Number: 2005/227
Paustenbach DJ, Panko JM, Scott P, Unice K (2005) Retrospective modelling of potential
residential exposure to perfluorooctanoic acid (PFOA) releases from a manufacturing
facility . Poster EVN019 presented at Fluoros symposium 2005
Poulsen PB, Jensen AA (2005) More environmentally friendly alternatives to PFOScompounds and PFOA Danish Environmental Protection Agency Environmental
Project No. 1013 Miljøprojekt
RPA (2004) Perfluorooctane Sulfonate: Risk Reduction Strategy and Analysis of Advantages
and Drawbacks. Prepared for DEFRA by Risk & Policy Analysts Ltd J454/PFOS RRS
Simcik M (2005) Global Transport and Fate of Perfluorocemicals Journal of Environmental
Monitoring 7:759-763
Stock NI, Lau FK, Ellis DA, Martin J W, Muir DCG, Mabury SC (2004) Perfluorinated telomer
alcohols in the North American troposphere Environmental Science and Technology
38: 991-996
Waritz RS (1975) An Industrial Approach to Evaluation of Pyrolysis and Combustion Hazards.
Environmental Health Perspectives 11:197-202
Washburn ST, Bingman TS, Braithwaite SK, Buck RC, Buxton LW, Clewell HJ, Haroun LA,
Kester JE, Rickard RW, Shipp AM (2005) Exposure assessment and risk
characterization for perfluorooctanoate in selected consumer articles. Environmental
Science and Technology 39:3904-3910
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Appendix: Comments to “Proposal for a Directive of the European
Parliament and of the Council relating to restrictions on the
marketing and use of perfluorooctane sulfonates (amendment of
Council Directive 76/769/EEC)”, COM(2005) 618 final, 5.12.2005
Prepared by Greenpeace International, January 2006
Given ever increasing recognition of the widespread environmental distribution of PFOS,
arising from its use and use of other PFOS-related chemicals to date1, coupled with its known
properties as a toxic, persistent and bioaccumulative substance (PBT) and propensity to
undergo long-range environmental transport2, regulatory measures aimed at reducing the risks
to health and the environment through restrictions on marketing and use are certainly
welcome, though long overdue.
The amendments proposed by the Commission in paper COM(2005) 618 recognise that PFOS
and many chemically-related substances which may give rise to equivalent concerns have
received a diversity of uses, some of which have recently been phased-out through voluntary
action by manufacturers but others of which continue. It is therefore right that the proposed
restrictions address not only PFOS but also what are commonly termed PFOS-related
substances. The proposed restrictions also appear to demonstrate an intent by the
Commission to take more seriously the complex and potentially irreversible risks presented
by PBT substances.
Nevertheless, the restrictions as proposed in paper COM(2005) 618 are not sufficient to
address the full extent of the known and potential risks of PFOS and related chemicals, or of
perfluorinated substances more generally. Key concerns can be summarised as follows:-
1. uses to be prohibited have already been phased-out
Although the intention of the proposed restrictions is to “cover the great part of the exposure
risks”, almost all the uses which it will prohibit have already been phased-out (as
acknowledged in the explanatory memorandum to the proposal itself), while current ongoing
uses will remain largely unaffected. Therefore, although the restrictions should be effective in
preventing future re-introduction for uses in carpets, textiles, upholstery, etc., the immediate
impact of the amendments on current use patterns seems likely to be minimal at best. The
proposals as they stand therefore have the characteristics of action which is “too little and too
late” to address the full scale of the problem.
2. most uses which will be permitted to continue indefinitely could
be phased-out within five years
1
Allsopp, M., Santillo, D., Walters, A. & Johnston, P. (2005). Perfluorinated Chemicals: an emerging concern.
Greenpeace Research Laboratories Technical Note 04/2005: 45 pp.
http://www.greenpeace.to/publications_pdf/perfluorinated_chemicals_2005.pdf
2
KemI (2005) Proposal for listing Perfluorooctane sulfonate (PFOS) in Annex A of the Stockholm Convention
on Persistent Organic Pollutants, Prepared by the Swedish Chemicals Inspectorate (KemI), Sweden, June 2005: 4
pp. http://www.pops.int/documents/meetings/poprc/meeting_docs/en/POPRC1-INF9-b.pdf
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At the same time, those uses which will be permitted by way of derogation from the general
restriction on marketing and use may, in many cases, be amenable to substitution given
sufficient time and incentives to develop and/or implement alternatives.
As the Commission proposals stand, uses in the semiconductor and photographic industries,
chromium plating operations, aviation hydraulics, fire-fighting foams and any number of
unspecified “controlled closed systems” will be permitted to continue indefinitely, with no
apparent requirement for such uses to be justified, reviewed or targeted for phase-out in the
future. Instead, all that is noted in the preamble is the recommendations from the
Commission’s own Scientific Committee on Health and Environmental Risks (SCHER)3 for
further assessment in relation to use in two of these categories, namely fire-fighting foams and
chromium plating, with no specified timeline for such assessments to be completed and no
formal process for any outcomes to be considered and, as necessary, addressed through
further amendments.
In contrast, national proposals for restrictions on PFOS and related substances developed by
Sweden4 and the UK5 recognise the desirability and feasibility of phase-out of most of these
ongoing uses (with the exception of hydraulic fluids used in aviation) through a series of
application-specific deadlines from 2007 through to the end of 2010. For example, in the UK
government’s proposed Environmental Protection (Controls on Perfluorooctane Sulphonate)
Regulations [2005]:a) use in chrome plating is permitted only until the end of 2007
b) use for specified applications in the photographic and semiconductor industries is permitted
only until the end of 2010
Thereafter, any continued use (other than in aviation hydraulics) will be permitted only on the
basis of justified case-by-case derogation, supported by evidence that efforts have been made
to find alternatives and that emissions from the process in question have been eliminated.
It would appear, therefore, that the restrictions proposed by the Commission could go much
further than those set out in COM(2005) 618, through the application of similar deadlines for
these applications, after which continued use would require case-specific justified derogation,
similar to the Authorisation procedure being developed for “substances of very high concern”
under REACH.
3. maximum limits of 0.1% by mass in preparations and articles may
not be stringent enough to prevent more widespread uses now or in
the future
3
SCHER (2005) Opinion on “RPA’s report “Perfluorooctane Sulfonates Risk Reduction Strategy and analysis
of advantages and drawbacks”, final report – August 2004”, Scientific Committee on Health and Environmental
Risks, adopted during the 4th plenary of 18th March 2005: 16 pp.
http://www.eu.int/comm/health/ph_risk/committees/04_scher/docs/scher_o_014.pdf
4
G/TBT Notification (2005) PFOS and substances that could degrade to PFOS (perflourooctyl sulphonic
derivative), G/TBT Notification Number: G/TBT/N/SWE/51, 06/07/2005: 11 pp. [in Swedish]
5
DEFRA (2005) Consultation on proposed national action to restrict the use of perfluorooctane sulphonate
(PFOS) and substances that degrade to PFOS, Annex A – Draft Regulations: 5 pp.
http://www.defra.gov.uk/corporate/consult/pfos/regulation.pdf
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Allowing 0.1% PFOS or related substance by mass in preparations or finished articles,
presumably set with the intention of preventing widespread use in consumer products, may be
too high to achieve a general prohibition on all uses other than those industrial uses specified
in the derogation. Although many uses in treatment of textiles, leather, paper and packaging
materials may require higher concentrations, recent OECD figures6 suggest that PFOS may be
present in products at levels below 0.1% by mass. It will be essential to verify:a) whether PFOS and/or related chemicals at levels below this 0.1% limit would arise
exclusively from contamination or could possibly be serving some functional purpose,
the latter implying a deliberate use and
b) what types and levels of use such a limit would permit, especially in the form of
surface coatings of bulk materials, and how significant these might be in terms of
exposure to humans and overall inputs to the environment.
4. derogation for use in “controlled closed systems” is too generic
and too lenient
Given that no examples are given, the applications intended to be covered by the general
derogation for use in “controlled closed systems” are not clear and the need for such a
derogation questionable. Moreover, permitting such a system to release up to 0.1% by mass
of the PFOS or related compounds it employs during normal operations implies that such a
system cannot be considered to be closed. Indeed, to associate this scale of permitted release
with the concept of closed systems could set a dangerous precedent for future measures
relating to other substances.
The scale of permitted releases in this case, and their likely contribution to human exposure
and environmental contamination, would depend entirely on the quantities which would be
used in these unspecified systems. Likewise, the 1ug/kg concentration limit placed on waste
discharges from such processes is not likely to provide adequate protection as the total
quantities of PFOS released will depend on the volume of waste generated and degree of
dilution achievable prior to discharge.
widespread uses of other perfluorinated chemicals will continue
unabated
While regulatory concerns to date have focused understandably on PFOS and PFOS-related
substances, scientific concerns relating to the widespread use of perfluorinated chemicals and
their potential environmental and health hazards extend well beyond this group, supported by
an increasing body of evidence on distribution and effects7,8,9,10. Concerns relating to PFOA
6
OECD (2004) Results of survey on production and use of PFOS, PFAS and PFOA, related substances and
products/ mixtures containing these substances. OECD Environment, Health and Safety Publications Series on
Risk Management No. 19, JT00176885, Paris 2004: 59 pp.
http://www.olis.oecd.org/olis/2005doc.nsf/LinkTo/env-jm-mono(2005)1
7
Martin JW, Smithwick MM, Braune BM, Hoekstra PF, Muir DCG, and Mabury SA (2004). Identification of
long-chain perfluorinated acids in biota from the Canadian Arctic.Environmental Science and Technology 38 :
373-380
8
Stock NI, Lau FK, Ellis DA, Martin J W, Muir DCG, Mabury SC (2004) Perfluorinated telomer alcohols in the
North American troposphere Environmental Science and Technology 38: 991-996
9
Simcik M (2005) Global Transport and Fate of Perfluorocemicals Journal of Environmental Monitoring 7:759763
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and related substances, and to products manufactured using PFOA (including the very
widespread fluorotelomer alcohols which are suspected, in turn, of acting as a source of
PFOA to the global environment), will ultimately also need to be addressed through timely
action.
For example. a very recent study conducted by the Norwegian Institute for Air Research, and
funded by the Swedish Society for Nature Conservation and the Norwegian Society for the
Conservation of Nature, documents the presence of perfluorinated chemicals in all-weather
clothing designed for children11, providing an illustration of just how common these
chemicals can be in consumer goods.
Therefore, although measures to address PFOS and related substances are welcome, providing
they are effective in eliminating all uses for which alternatives are available (the principle of
substitution), the Commission will ultimately also need to address a much wider range of
substances if it is effectively to protect the environment and peoples of Europe from the threat
of perfluorinated chemicals.
10
Prevedouros, K., Cousins, I.T., Buck, R.C. & Korzeniowski, S.H. (2006) Sources, fate and transport of
perfluorocarboxylates. Environmental Science & Technology 40(1): 32-44
11
SSNC FoEN (2006) Fluorinated pollutants in all-weather clothing. Norwegian Society for the Conservation
of Nature/Friends of the Earth Norway and Swedish Society for Nature Conservation, January 2005, ISBN 91
558 0721 6: 43 pp. http://www.snf.se/pdf/rap-hmv-allvadersklader-eng.pdf
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