PFC derivatives and chemicals on which they are based alert FactSheet

derivatives what are they

Note. This factsheet brings together the content of six Alert sheets issued 2002—08.

The Alerts were reviewed and updated in January 2013.

PERFLUOROOCTANYL SULFONATE (PFOS) and PERFLUOROALKYL SULFONATE (PFAS)

Perfluorooctane sulfonate (PFOS) is a fully fluorinated organic compound—a member of a large family of perfluoroalkyl sulfonate (PFAS)-based chemicals.

PFOS refers to fully fluorinated (eight-carbon chain length) sulfonate-containing substances. The acid form of PFOS is 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-1-octanesulfonic acid (CAS No. 1763-23-1).

PFOS-related substances may be salts of PFOS e.g. potassium, lithium, ammonium or diethanolamine, or polymers that contain the PFOS as a portion of the entire structure. A PFOS-related substance is any substance which contains the PFOS moiety and may break down in the environment to give PFOS.

PFAS is a generic term used to describe any fully fluorinated carbon chain length sulfonate, including higher and lower homologues.

The majority of these chemicals are high molecular weight polymers in which PFOS or the PFAS chemical is only a fraction of the polymer and final product.

PFAS-related substances may be salts of PFAS, or polymers that contain PFAS as a portion of the entire polymer.

PFOS and PFAS chemicals have unique surfactant properties and many speciality applications. These applications include heat, chemical and abrasion resistance, and as dispersion, wetting and surface treatments.

These chemicals have been used in a variety of industrial, commercial and consumer products in Australia.

The 3M Company—which was the largest worldwide producer of PFOS chemicals—stopped manufacturing PFOS chemicals in December 2000 because of concerns about their persistence in the environment and long-term health and environmental effects. PFOS does not biodegrade in the environment.

In Australia, PFOS was a component of the Scotchgard™ range of products and an ingredient of some industrial additives, Aqueous Film Forming fire fighting Foams (AFFF™) and Alcohol-Type Concentrate (ATC™) fire fighting foams produced by the 3M Company. AFFF™ and ATC™ fire fighting foams were used to extinguish Class B fires that involve flammable fuels.

The Scotchgard™ brand continued to be used by 3M Company in the Australian market, except as described below, but replacement products did not contain PFOS chemicals. 3M Australia advised that PFOS had been removed from all consumer Scotchgard™ products in Australia except for Scotchgard™ Spot Remover. This product was to be phased out in Australia by September 2002.

There were only two industrial/commercial uses of PFOS-based Scotchgard™ in Australia: for protecting textiles and leather, and these were phased out in Australia by September 2002 and March 2003, respectively.

All other PFOS-containing products (including fire fighting foams and industrial additives) were phased out in Australia by December 2003.

Scotchban™ was a PFOS-containing product supplied by 3M to treat paper containers for fast-food and pet-food. Scotchban™ is no longer sold in Australia and has not been used to treat paper since September 2000.

To assist in a risk assessment by users of PFOS-based products, data on health effects and handling of PFOS-based products can be obtained from the relevant and most recent 3M Company (Material) Safety Data Sheets ((M)SDSs) and from 3M Australia. Specific respiratory, hand and eye protection and exposure controls are contained in the relevant (M)SDSs.

PERFLUOROOCTANOIC ACID (PFOA)

Perfluorooctanoic acid (PFOA), or pentadecafluorooctanoic acid, is a fully fluorinated eight-carbon chain carboxylic acid (CAS Registry Number 335-67-1). PFOA is also known as perfluorooctanoate and 1-octanoic acid 2,2,3,3,4,4,5,5, 6,6,7,7,8,8,8-pentadecafluoro.

PFOA is primarily a reactive intermediate, while its salts, such as ammonium perfluoroctanoate, are used as processing aids in the production of fluoropolymers and fluoroelastomers, and in other surfactant uses.

Common derivatives of PFOA include the ammonium ("APFO"), sodium, potassium and silver salts of the acid.

PFOA, a man-made substance that does not occur naturally in the environment, has unique physical and surfactant properties. Concerns have been raised that certain fluorinated telomers may break down or degrade to form PFOA in the environment. Fluorinated telomers are small fluorine-containing polymers.

PFOA-based chemicals and chemicals which may degrade to PFOA are of interest because PFOA may be hazardous to human health and the environment. The United States Environmental Protection Agency (US EPA) released a draft risk assessment of PFOA in April 2003.

PFOA is persistent in the environment and has been found in humans. Concerns were raised about other effects of PFOA in laboratory animals.

The US EPA report, however, was unable to determine whether PFOA poses an unreasonable risk to the public because considerable scientific uncertainties remain about PFOA.

PFOA is an industrial chemical processing aid typically used to make certain fluoro-polymers which have a variety of consumer and industrial applications. PFOA may also have specialised surfactant uses. Applications of PFOA are characteristically high-performance coatings on fabrics, metal surfaces and fabricated parts and may include coatings on articles such as non-stick cookware, specialized garments and textiles and electronics components.

Potential exposure routes for PFOA include PFOA production and use, PFOA contamination in other products, and degradation of certain fluoropolymers to PFOA.

NICNAS has noted that it was likely that some importers and users may not know if products contain PFOA and its derivatives (including, fluoropolymers which may degrade to PFOA) because such chemical ingredients may not be mentioned on (M)SDSs and labels.

PERFLUOROCARBOXYLIC ACID (PFCA)

Perfluorocarboxylic acid (PFCA) is a generic term used to describe any fully fluorinated carbon chain length carboxylic acid, including PFOA. This group includes PFCA and PFCA-related substances with a fully fluorinated four or more carbon chain length.

Both PFOA and PFCA-related substances may be salts of PFOA/PFCA or polymers that contain PFOA/PFCA as a portion of the entire polymer.

PFOA/PFCA-related substances also include their precursors, which are the chemicals that can break down to form PFOA/PFCA. For example, some residual monomer chemicals from the telomer manufacturing process such as telomer alcohols and telomer iodides may remain in the final product and break down into PFOA/PFCA. In addition, fluorotelomers may potentially degrade to PFOA/PFCA from their polymer backbones via metabolism or environmental degradation.

ALERT 2002: PERFLUOROOCTANYL SULFONATE (PFOS)

The Australian Government Department of Health, through the National Industrial Chemicals Notification and Assessment Scheme (NICNAS) was actively involved in the Organisation for Economic Co-operation and Development (OECD) assessment of PFOS .

From July 2000, the OECD led an international collaboration on the scientific assessment of PFOS chemicals. This involved Australia and approximately 40 other parties including Canada, Japan, the US and the European Union (EU) and will facilitate a consistent approach worldwide to the concerns presented by PFOS chemicals.

The OECD assessment of PFOS chemicals addressed the human, animal and environmental hazards of PFOS. It contained environmental exposure and fate, human monitoring and health hazard information. Occupational exposure, non-occupational exposure, epidemiology and animal toxicology studies of PFOS were also addressed.

In November 2002, the OECD finalised the PFOS assessment report and addressed risk-based management of the chemical. NICNAS then considered regulatory actions to be taken on PFOS chemicals in Australia.

In addition to the current OECD assessment of PFOS, NICNAS notes similar international concerns for PFOA and telomer chemistries which are utilised by a number of manufacturers. Both PFOA and telomers may be affected by ongoing reviews of these related chemistries. NICNAS recommends that users consider these comments when investigating PFOS alternatives.

ALERT 2003: PERFLUOROOCTANYL SULFONATE (PFOS)- AND PERFLUOROALKYL SULFONATE (PFAS)-BASED CHEMICALS

Australian data

Information collected by NICNAS to 2003 indicated that:

  • PFOS- and PFAS-based chemicals were not manufactured in Australia, however products containing these chemicals had been made and were used in Australia. PFOS had been the favoured PFAS chemical used in Australia.
  • Voluntary phase out agreements by Australian industries since 2000 resulted in a rapid decrease in the use of PFOS chemicals in Australia.
  • Only two remaining uses of PFOS chemicals existed in Australia. These uses were in some Class B fire-fighting foam, in specialised industrial products used for processing rubber and in the production of paints and coatings. These PFOS products were no longer available in Australia after December 2003.
  • There was only one other use of a PFAS chemical currently identified by NICNAS in Australia—an adhesive which was expected to be phased out by 2004 when the existing stock was exhausted. The adhesive was used to bond timber for use in the building and construction industry. The timber product could also be used by domestic consumers.
  • The phase out in Australia meant old stock of PFOS- and PFAS-based products could still be found in Australia or be held by consumers and industrial users.
  • NICNAS believed it had identified all the applications of PFOS in Australia. It was likely that some importers and users may not have known if products contained these chemicals because PFOS- and PFAS-based chemical ingredients may not have been mentioned on (M)SDSs.

In 2003 NICNAS made a further call for information about the importation, manufacture, use and health effects of the PFOS alternatives PFOA and perfluorinated telomer chemicals and products in Australia.

International activities

PFOS was the subject of an international environmental and human health hazard assessment by the OECD. The OECD hazard assessment concluded that PFOS is persistent, bioaccumulative and toxic to mammals.

Due to concerns over PFOS, the PFOS alternatives PFOA and perfluorinated telomers were being investigated internationally to identify potential environmental and health hazards.

There were significant concerns that PFOA, like PFOS, was persistent, bioaccumulative and toxic. Little was known about perfluorinated telomers, however international investigations of these telomers were under way and scheduled for completion in 2003 and 2004.

The OECD assessment of the hazards of PFOS and a preliminary risk assessment by the US EPA of the developmental toxicity of PFOA were available.

NICNAS recommendations

Because of concerns over PFOS, PFOA and perfluorinated chemicals, NICNAS recommended that:

  • PFOS- and related PFAS-based chemicals be restricted to only essential uses, for which no suitable and less hazardous alternatives were available such as certain Class B fire fighting foams.
  • PFOS-based fire fighting foam not be used for fire training purposes to limit environmental release.
  • PFOS users exercise caution in selecting PFOA as an alternative, as PFOA may have the same environmental and health concerns as PFOS.
  • All labels and (M)SDSs include details of the PFAS and PFOS chemicals in the product.
  • Information on the safe use and handling of all these chemicals of concern be provided to fire fighters in the relevant and most recent (M)SDSs available from the suppliers of these chemicals.

ALERT 2004: PERFLUOROOCTANOIC ACID (PFOA) AND ITS DERIVATIVES

Australian data

Information collected by NICNAS showed the following:

Manufacture

No manufacture of PFOA, PFOA derivatives or fluoropolymers that may degrade to PFOA had been reported in Australia.

Importation and use
  • Primer for non-stick metal cookware

The import of a liquid fluoropolymer surfactant dispersion product was reported. The importation equated to approximately 50 gm and 25 gm of PFOA in 2003 and 2004, respectively.

The factory-applied, oven-baked dispersion coating was used for coating metal cookware and was intended to impart a continuous solid non-stick coating to the metal surface. Volatilisation and destruction of PFOA was reported during the manufacturing process which fuses the fluoropolymer to the metal surface and involves a thermal step at 350-400ºC.

  • Fluoropolymer dispersion polymer in paints

The import of a fluoropolymer dispersion polymer for use in paints was reported. The importation equated to 10 kg annually of PFOA.

  • Fire-fighting foam

The import in the past of two fluorosurfactant products

for use in the manufacture of Class B fire fighting foam was reported. The importation equated to approximately 48 gm and 0.6 gm of PFOA in 2002 and 2003, respectively. The importation and sale of the products in Australia was discontinued in 2003.

  • Textile and carpet protection

Textile and carpet protection products containing some fluoropolymers were imported into Australia. Information was received from importers and suppliers that research was being undertaken internationally via the Telomer Research Program (in conjunction with the US EPA) to determine whether these products may degrade to PFOA.

  • Other uses of telomers

Additional polymers that include monomers based on perfluorinated telomers were reported. These chemicals were assessed by the NICNAS New Chemicals program and were in use under certificate. These chemicals had applications in fabric protection, surface coating and printing. Under section 64(2)(e) of the Industrial Chemicals Notification and Assessment Act 1989. there was a requirement that introducers of these chemicals must notify the Director, NICNAS of any additional information that had become available (within 28 days of the occurrence) as to adverse health or environmental effects of these chemicals.

National and international activities

There was ongoing national and international activity in relation to PFOA. The OECD was collating data on the uses of PFOA manufactured and used globally. NICNAS assisted and provided information to the OECD with regard to this activity.

The US EPA provided regular updates on their activities for PFOA and fluorinated telomers to NICNAS, and released a revised draft hazard assessment of PFOA and its salts and preliminary risk assessment on PFOA and its salts in 2002 and 2003, respectively.

On-going scientific investigations of PFOA and the potential sources and pathways of PFOA in the environment were used to update these assessments. The investigations included studies to determine the potential for generation of PFOA and characterization of release of PFOA from articles such as garments, household cookware, textiles and carpets.

NICNAS advice

Because of concerns over PFOA and fluorinated telomers that may degrade to PFOA, NICNAS advised that:

  • Importers and users of these chemicals remain vigilant to the ongoing international activities regarding PFOA and related chemicals. Updates about these activities can be accessed from NICNAS.
  • Information on the safe use and handling of these chemicals be provided to all users in the relevant and most recent (M)SDSs available from the suppliers of these chemicals.
  • On completion of the scientific investigation of PFOA and potential sources and pathways of PFOA in the environment, NICNAS will, if needed, make recommendations on appropriate regulatory activities

ALERT 2007 (1): PERFLUOROOCTANE SULFONATE (PFOS) and

PERFLUOROALKYL SULFONATE (PFAS)

Australian data

In July 2006, NICNAS collected information through a national survey, on production, importation and use of perfluorinated chemicals including PFOS, PFAS and their related substances, and products/mixtures containing these substances for the calendar years 2004 and 2005.

Information provided to NICNAS indicated that:

  • PFOS and PFAS related chemicals are not manufactured in Australia.
  • No PFOS or PFOS related substances were imported in the calendar years 2004 and 2005.
  • A PFOS-containing product was imported prior to 2003 and used for the formulation of leather treatment products. The product had been used at volumes of 47 and 13 kg in 2004 and 2005, respectively, and was reported as no longer being used in 2006.
  • The only identified use of PFOS substances in Australia was in Class B fire-fighting foam products. In 2007, about 180,000 litres of Class B fire-fighting foam products containing 0.1-7% PFOS-related substances were held in stock at some end-user sites. NICNAS was advised that these PFOS based fire-fighting products had been purchased prior to 2003 and were to be replaced on reaching the product expiry date. Some non-PFOS based fire-fighting foam products containing fluoroalkyl surfactants or alcohol resistant film-forming fluoroprotein had been imported as replacements.
  • In 2004 and 2005, the total volumes of PFAS related substances imported both as technical grade chemicals and in products were approximately 1630 kg and 1740 kg, respectively.
  • Three high volume PFAS related substances identified from the NICNAS survey were all perfluorobutane sulfonate (PFBS) based compounds. The NICNAS assessment report on PFBS (2006) showed that they were less hazardous than PFOS chemicals. The combined volumes for the three PFBS based substances imported in 2004 and 2005 were 813 kg and 877 kg, respectively. These PFBS compounds were used in Australia for formulating industrial coating products, rubber moulding products and acid mist suppressants. Products containing these PFBS based compounds were also imported in 2004 and 2005 at total PFBS volumes of 810 kg and 860 kg, respectively.
  • Uses in low volume of another two products containing PFAS substances were also reported from the survey. A mixture of C9 and C10 PFAS substances was used to formulate floor sealers with combined PFAS volumes of 1.1 kg and 0.9 kg in 2004 and 2005, respectively. An alcohol resistant fire-fighting foam product containing a C6-8 PFAS substance was used in quantities of 4.5 kg in 2004 and 0.6 kg in 2005. The uses of both products had been phased out.
  • It was likely that some importers and users may not have known if products contained these chemicals because PFOS- and PFAS-based chemical ingredients may not be disclosed or listed on (M)SDSs.
International activities

NICNAS recommended that:

  • PFOS- and related PFAS-based chemicals be restricted to only essential uses, for which no suitable and less hazardous alternatives are available.
  • The existing PFOS-based fire fighting foam not be used for fire training purposes to limit environmental release.
  • PFOS not be replaced by PFOA as an alternative, as PFOA may have the same environmental and health concerns as PFOS.
  • All labels and (M)SDSs include details of the PFOS and PFAS chemicals in the product.
  • Information on the safe use and handling of all these chemicals of concern be provided in the relevant and most recent (M)SDSs available from the suppliers of these chemicals.

ALERT 2007 (2): PERFLUOROOCTANOIC ACID (PFOA) and

PERFLUOROCARBOXYLIC ACID (PFCA)

Australian data
PFOA and related substances

In July 2006, NICNAS collected information on manufacture, importation and uses of perfluorinated chemicals including PFOA-related substances and products/mixtures containing these substances for the calendar years 2004 and 2005. Information provided to NICNAS indicated that:

  • No PFOA related chemicals are manufactured in Australia.
  • An antifoam product containing <10% of a PFOA-related chemical was imported in 2005 for use in a dyeing process with sulfur dyes. The total quantity imported was approximately 10 kg.
  • A de-dusting product for industrial use and a consumer paint product, both containing less than 100 ppm PFOA salt, were imported. The total volumes of PFOA salt in both products were 10 and 71 kg in 2004 and 2005, respectively. The concentrations of PFOA salt in these products were reduced to less than 10 ppm in 2006.
  • PFOA could be present as an impurity in polytetrafluoroethylene (PTFE) products and in some fire-fighting foam products imported into Australia. These products also include industrial painting/coating products, and some wiring products. The concentrations of PFOA in these products are at trace levels ranging from parts per billion (ppb) to less than one part per million (ppm).

NICNAS will continue to monitor the importation and use of PFOA-related substances in Australia.

PFCA and related substances

The information collected for PFCA-related substances in July 2006 was likely to be incomplete because the Call for Information did not specifically include the PFCAs group. Information obtained by NICNAS indicated that:

  • No manufacture, importation or use of PFCA was reported.
  • Two PFCA precursors were imported into Australia in 2005. One is a perfluorinated furan compound (0.25 kg) used as an analytical reagent. The other substance was a polymer containing a perfluoroalkylethyl ester moiety imported at 150 kg in 2005 and used to formulate coatings for wood boards of internal wall cladding.
  • Eight products containing PFCA precursors were imported into Australia during 2004 and 2005. Five of them were water/oil repellent products used for textiles, carpets, and masonry/cement surfaces. The remaining three products were used for automotive painting, glass treatment and ink cartridges. These eight PFCA precursors included five perfluoroalkylethyl chemicals and three fluorinated acrylate polymers. The total volume of the eight products was up to 33,300 kg per annum. The concentration of PFCA precursors in the products ranged from <0.1% to 50%.
International activities
  • The US EPA provides regular updates on their activities for PFOA and fluorinated telomers to interested parties globally including NICNAS. The USEPA released a revised report Draft risk assessment of the potential human health effects associated with exposure to perfluooctanoic acid and its salts in January 2005. On-going scientific investigations of PFOA and the potential sources and pathways of PFOA in the environment will be used to update the assessment. The investigations include studies to determine PFOA, the potential for generation of PFOA and characterisation of release of PFOA from articles such as garments, household cookware, textiles and carpets.
  • In December 2005, Health Canada and Environment Canada proposed temporary prohibitions on the introduction of four new polymers containing fluorinated carbon chains based on the toxicological effects of their breakdown products, perfluorocarboxylic acids (PFCAs). In February 2006, the two Canadian agencies published a position paper Perfluorinated carboxylic acid (PFCAs) and precursors: A proposed action plan for assessment and management .
  • On January 25, 2006, US EPA invited fluoropolymer and telomer manufacturers to participate in a Global Stewardship Program on PFOA and related chemicals. The Stewardship Program required voluntary corporate commitment to two goals:

(1) to commit to achieve, no later than 2010, a 95% reduction, measured from a year 2000 baseline, in both: facility emissions to all media of PFOA, precursor chemicals that can break down to PFOA, and related higher homologue chemicals, and product content levels of PFOA, precursor chemicals that can break down to PFOA, and related higher homologue chemicals;

(2) to commit to working toward the elimination of PFOA, PFOA precursors, and related higher homologue chemicals from emissions and products by five years thereafter, or no later than 2015.

NICNAS advice

Because of concerns over PFOA, certain PFCAs and fluorinated telomers that may degrade to PFCA, NICNAS advised that:

  • Industry should actively seek alternatives to PFOA and precursors that may degrade to PFOA and aim to phase out the use of these chemicals.
  • Importers and users of these chemicals remain vigilant of the ongoing international activities regarding PFOA and related chemicals.
  • Information on the safe use and handling of these chemicals be provided to all users in the relevant and most recent (M)SDSs available from the suppliers of these chemicals.
  • On completion of the present scientific investigation of PFOA and potential sources and pathways of PFOA in the environment, NICNAS will, if needed, make recommendations on appropriate regulatory activities.

ALERT 2008: PERFLUOROOCTANE SULFONATE (PFOS) and

PERFLUOROALKYL SULFONATE (PFAS)

Australian data

In May 2008, NICNAS collected information, through a national survey, on production, importation, stocks held and use of PFOS, PFAS and their related substances, and products/mixtures containing these substances for the calendar years 2006 and 2007.

Information provided to NICNAS indicated:

It is likely that some importers and users did not know if their products contained PFOS- and PFAS-based chemical ingredients because these chemicals may not have been disclosed or listed on (M)SDSs.

Source: www.nicnas.gov.au

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