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Survey and environmental/health assessment of fluorinated substances in impregnated consumer products and impregnating agents

4 Occurrence in consumer products

• 4.1 Occurrence in impregnating agents
  • 4.1.1 Impregnating agents for footwear
  • 4.1.2 Impregnating agents for carpets and mats
  • 4.1.3 Impregnating agents for textiles, leathers and furniture
  • 4.1.4 Impregnating agents for car interiors (textiles)
• 4.2 Occurrence in impregnated products
  • 4.2.1 Clothes
  • 4.2.2 Waterproof clothing and all-weather clothes
  • 4.2.3 Footwear
  • 4.2.4 Furniture
  • 4.2.5 Carpets and mats
  • 4.2.6 Sunshades/awnings, tents, umbrellas and parasols
• 4.3 Occurrence in other relevant products
  • 4.3.1 Paints
  • 4.3.2 Printing inks
  • 4.3.3 Auto polish and -wax
  • 4.3.4 Floor polish
  • 4.3.5 Ski wax
  • 4.3.6 Cleaning agents for glass

The information from the Danish Product Register has been supplemented with information from different companies such as producers, importers, suppliers and stores.

Producers of fluorinated substances have been identified by searching the Internet, and the results were presented in Chapter2. Stores and companies marketing and selling consumer products with a content of fluorinated substances have been identified initially by identifying the different products that contain fluorinated substances, and then secondly identifying the sectors in which the products are sold or produced. A search for companies belonging to these sectors have been carried out by using the Internet-based program Dun & Bradstreet that contains all companies listed in Denmark under different sector codes.

The consumer products and sectors as listed in Table 4.1 below have been identified to be relevant.

When searching for companies in the identified sectors, the result was of course many thousand different companies, and it has not been possible within the budget of this project to contact them all, but a few companies within the most relevant sectors have been contacted.

Suppliers and importers of fluorinated substances or products containing fluorinated substances have mostly been identified indirectly, i.e. different shops or companies selling or producing products containing fluorinated substances were contacted and gave information about their suppliers.

It was decided to use the direct approach, i.e. telephone calls when contacting the different sources, as it was not expected to pay off in the short available time, just by sending questionnaires to the different companies.

In all 59 different companies have been contacted.

However, as this approach only gave sparse information (either they did not know the chemical content of their products or they did not want to give away any information about the use of fluorinated substances), information found on the Internet about the content of fluorinated substances in different products was combined with statistics of sales of different products in Denmark in order to estimate the use of fluorinated substances in Denmark in different product categories.

Statistics from Statistics Denmark have been used in order to collect information about the amounts used of relevant consumer products. Both import/export statistics and production statistics have been used for relevant consumer products in order to calculate the supply of products in Denmark via the equation:

Supply = Import – export + Danish production

Table 4.1: List of consumer products and matching sectors with probable uses of fluorinated compounds

* Not investigated in this project

In the following text the information regarding products containing fluorinated substances are listed. The following headlines are used:

• Occurrence in impregnating agents (for textiles and leather).
• Occurrence in impregnated products (such as clothes, footwear, furniture, carpets and sunshades).
• Occurrence in other relevant products (such as paints, inks, wax, polish, and cleaning agents).

In this Chapter 4 information from the different areas are listed and calculations are performed with use of statistics where possible, in order to estimate a total use of fluorinated compounds. Chapter 5 is a summary of the information described in this chapter 4.

4.1 Occurrence in impregnating agents

The main brands on the market for impregnating agents are:

• Boston
• Kiwi
• Imprenex
• Nikwax
• Granger

Impregnating agents are used on many different products such as shoes, textiles, carpets, furniture, tents, etc. In the following paragraphs, impregnating agents for footwear, carpets, furniture and textiles are discussed in detail.

Impregnating agents identified for general impregnating purposes (i.e. leather, textiles, furniture, tents etc.) are listed below. Whether the impregnating agents contain fluorinated compounds is, however, uncertain for some products (if the products contain fluorinated substances that are mentioned in brackets).

• TexCare Imprægneringsspray (impregnation spray) (with TexCare® fluor anti-spot system)
• Coxy Super Protector Spray (impregnation with fluor)
• NanoCover Tekstil & Læder (textile and leather). Nanotechnology has been used for this product. This product can be used for clothes, coats, skiwear, ties, cushions, furniture, tents, shoes, etc.
• NikWax impregnating products (at least one of their products contains fluorinated chemicals according to analysis carried out by the Swedish Society for Nature Conservation (Naturskyddsföreningen, 2007)).

Fluorinated levels in products

In a project carried out for the Danish EPA in 2001, perfluorodecane sulfonate was found in a concentration of 212 mg/ml in an impregnating agent for tents, sleeping bags, etc. (Vejrup et al., 2002).

In another project carried out for the Danish EPA in 2004, PFOA was found in an impregnating product used by professional dry cleaners. The impregnating product for textiles was analyzed towards artificial sweat and this resulted in levels of 0.2 µg perfluoroheptanoic acid/dm² textile and 0.44 µg perfluorooctane acid/dm² textiles (Glensvig et al., 2004).

In a third project carried out for the Danish EPA in 2004, perfluoroheptanoic acid and perfluorooctane acid were found in impregnating agents for shoes in levels of 1.1 mg/kg and 0.36 mg/kg respectively. It is stated that this probably is due to impurities in the fluorocarbon polymer, which is added in the impregnating products, i.e. the PFOS-compounds identified are the monomers of the fluorocarbon polymer/telomer used in the impregnation agent (Engelund and Sørensen, 2005).

Levels of PFCA precursors (e.g. fluorotelomers) up to 3.8% have been measured in carpet impregnating agents. (Information from the Government of Canada 2006 cited from Swedish Chemicals Agency, 2006).

Recently, Swedish Society for Nature Conservation published a report about PFAS in impregnation fluids. Thirteen commercial products were analysed for a variety of perfluoroalkylsulfonates, PFCAs, perfluorooctanesulfonamides (FOSA and FOSE), and FTOHs (in all 27 different fluorinated chemicals). Some of these impregnating products have been found on the Danish market as well. Two of the products did not contain any of the fluorinated substances that were analysed for. Six of the products contained PFOS-related chemicals. Three of the products had very high contents of FTOH, between 1 and 9 g/L. Five products had high concentrations of FTOH, between 0.2-0.9 g/L, and contained PFCAs as well in concentrations between 0.2-8.4 mg/L. Seven of the investigated products contained PFOA, varying between 45 and 692 µg/L. Additionally, other PFCAs as well as up to 1000-times higher amounts of 8:2 FTOH were detected (Naturskyddsföreningen, 2007). The results are summarised in Table 4.2 below.

Table 4.2: Amounts of fluorinated substances extracted from 13 Swedish commercial impregnation products for all-weather clothing and shoes (Naturskyddsföreningen, 2007).

We got access to confidential information from a company producing impregnating agents primarily to the Scandinavian market. Two of their products for textiles had been analysed for PFCAs and contained 2.2 mg/kg total PFCAs and 5.3 mg/kg total PFCAs, respectively. The dominating PFCA was PFOA with contents of 0.73 mg PFOA/kg and 4 mg PFOA/kg in the respective products.

According to the search in the Danish Product Register fluorinated substances in impregnating agents are used in concentrations between 0.003% and 6%. The actual span between the lowest and highest concentrations is not necessarily this large, but these intervals are given in the Product Register as the exact concentration is confidential.

Companies contacted

None of the contacted companies were willing to give any information to the project.

Danish Statistics

A total estimation for impregnating agents for textiles and leather can be calculated using statistics for the larger product group “Preparations for treatment of textiles, leather and hide” (see Table 4.3). This product group are assumed to cover all sorts of impregnating agents, but probably not what is used for furniture. Furthermore, this product group is expected to cover much more than just impregnating agents.

Table 4.3: Supply of preparations for treatment of textiles, leather and hide (tonnes) in Denmark according to Danish Statistics. The product group is most likely covering other products than just impregnating agents.

It is assumed that a maximum of 10% of the supply of impregnating agents for textiles and leather are based on fluorinated compounds but with an unknown concentration, as no information was received from producers of impregnating agents about the amount of fluorinated substances used in impregnating agents. It is necessary to know the concentration (percentage or in g/kg) of fluorinated substances to be able to calculate the total amount of fluorinated substances used in impregnating agents in Denmark.

According to the Product Register the concentration of fluorinated agents in impregnating agents for shoes is between 0.003 and 6%. This would mean a content of fluorinated compounds between 0.03 g/kg and 60 g/kg. This is intentionally a large span, as the actual concentrations are confidential.

The Swedish analysis of 13 impregnating agents, shown in Table 4.2, reported a large span of the concentrations of fluorinated substances of between 0.00008 g/L and 9.4 g/L with an average of 1.6 g/L (which is assumed to be equal to 1.6 g/kg).,

The Danish supply of preparations for treatment of textiles, leather and hide is 2089.5 tonnes, and if assuming that 10% of that amount is impregnating agents containing fluorinated substances in a concentration of 1,6 g/kg, the total use of fluorinated compounds in impregnating agents in Denmark for 2006 can be calculated to around 338 kg.

As 170 kg of fluorinated substances are reported for use in impregnating agents in Denmark according to the Product Register, this amount is regarded as a minimum use in Denmark and the 338 kg as the maximum use.

These calculations cover the entire area of impregnating agents, as the Danish Statistics is only available on this detail level. Below more detailed information on the specific types of impregnating agents is presented:

• Impregnating agents for footwear
• Impregnating agents for carpets and mats
• Impregnating agents for textiles, leather and furniture
• Impregnating agents for car interiors (textiles)

4.1.1 Impregnating agents for footwear

According to the report from the Danish EPA “Mapping and health assessment of chemical substances in shoe care products” (Engelund and Sørensen, 2005), the sale of impregnation products for shoes in Denmark in 2003 was about 29.5 tonnes. As mentioned earlier small concentrations of PFOS-compounds was found in impregnating agents for shoes on the Danish market.

By searching the Internet or visiting shoe shops it is easy to discover a number of impregnating agents for shoes and boots with a content of fluorinated compounds. The label on many products states directly that this product contains a fluorinated agent. The following impregnating products especially for footwear have been identified, and can be found in many ordinary shoe stores or in Internet trading. All the mentioned impregnating agents have a fluorinated content either according to the products or the information obtained on the Internet:

• WOLY Combo Proper (with fluorine agent)
• WOLY Velour Nubuck (with fluorine agent)
• WOLY Protector 3 x 3 (with fluorine agent)
• WOLY Multi effect (with fluorine agent)
• WOLY Oil Protector (with fluorine agent)
• Collonil Classic Waterstop (with GORE-TEX - contains fluorinated chemicals (PFCAs) according to analysis carried out by the Swedish Society for Nature Conservation (Naturskyddsföreningen, 2007)
• Ecco Universal Waterproofing spray (contains fluorinated chemicals (PFCAs) according to analysis carried out by the Swedish Society for Nature Conservation (Naturskyddsföreningen, 2007))

Companies contacted

Shoecare, which is the Danish distributor for the WOLY products, was contacted. They referred to their German supplier Melvo. Shoecare informed that they have received a declaration from their supplier that the products do not contain PFOS or PFOS-related compounds, and that the spray products contain fluorotelomer alcohols (FTOH) and traces of PFOA.

Melvo was contacted in order to learn more about content and concentration of fluorinated compounds in their products. However, this German company would not participate in the project with information about the content of the fluorinated compounds. They referred to the MSDS of the products, which did not reveal anything about the fluorinated compounds other than the products can decompose to HF (hydrogen fluoride), which means that they do contain fluorinated substances. However, the supplier of the fluorinated compounds is DuPont and therefore the product would probably be based on their “X Platform”, “Zonyl“ or “Foraperle” products.

Danish Statistics

It was impossible to find information about the use of impregnating agents for shoes via Statistics Denmark. The statistics are not available at sufficient detail level. A product code can be found for “Shoe polish and similar products for footwear and leather” and for “Preparations for treatment of textiles, leather and hide”. However, the sale of impregnation products for shoes of 29.5 tonnes for 2003 from the Danish EPA study can be used for the calculations, assuming that the annually use has not changed.

When using the average content of 1.6 g fluorinated substances per kg impregnating agents as found in the impregnating agents on the Swedish market (see Table 4.2), the annual use of fluorinated substances amounts to between 12 and 24 kg fluorinated substances for use in impregnating agents for shoes only, if it is assumed that around 25-50% of the impregnating agents for shoes are based on fluorinated compounds (others may be silicone-based).

4.1.2 Impregnating agents for carpets and mats

By searching the Internet or visiting carpet stores it is easy to discover a number of impregnating agents for carpets. Whether the impregnating agents contain fluorinated compounds is, however, uncertain for most products. The following impregnating products for carpets have been identified:

• Ditog imprægnering (contains fluorocarbons)
• Juhlin’s Textil og Tæppeimprægnering
• Stainshield
• Pure Guard
• TM-Textil og Tæppeimprægnering (textile and carpet impregnation)
• Baygard SF-A 02, Baygard SPT(contains fluorocarbons).

Visits to carpet stores showed that impregnation agents for carpets are easily accessible for consumers, but no information have been received, whether they are based on fluorinated compounds or about the amounts sold. This has not been investigated further. It is, however, assumed that this market is small, as not all consumers have carpets in their homes, and as most carpets today already are impregnated from the factory, when new carpets are bought (see 4.2.5 Carpets and mats). The use in industry (impregnation) and service (cleaning of mats) may be greater.

The contacted carpet factories and –stores informed that carpets made by man-made fabrics (nylon etc.) often are impregnated at the production. Carpets made by wool are seldom imprægnated

It is not possible to find information about the use of impregnating agents for carpets via Statistics Denmark. The statistics are not available at sufficient detail level.

4.1.3 Impregnating agents for textiles, leathers and furniture

By searching the Internet a number of impregnating agents for furniture and textiles have been identified. It is, however, uncertain for most products whether the impregnating agents contain fluorinated compounds. The following impregnating products for furniture and textiles have been identified:

• Point2you textil & læder (textile and leather). Nanotechnology has been used for this product.
• Cetox KWI used as impregnating agent for textiles at dry cleaning services in Denmark^[13] (contains a fluoroalkyl polymer).
• Matas stofimprægnering (fabric impregnation)
• Guardian Textil Imprægnering (fluor anti-spot system)
• Granger´s XT Spray (contains fluorinated chemicals (FTOHs, PFAS and Pica’s) according to analysis carried out by the Swedish Society for Nature Conservation (Naturskyddsföreningen, 2007).

Companies contacted

Point2you and Guardian Protection Products were contacted, but no information was received. Furthermore, the firm using the impregnating agent Cetox KWI containing a fluoroalkyl polymer (used before 2003 for impregnating textiles at dry cleaners) was contacted, but it was not possible to get information about any continuous use of impregnating agents with fluorinated substances. The rest was not contacted.

Ecolab has developed a product called Saprit protect plus in order to protect garments from water, dirt and oils^[14]. It is a professional impregnation product used for finishing in the textile industry. It is used as the final step in an industrial washing process of textiles, e.g. washing of work-wear^[15]. It contains fluorocarbon chemicals according to their website^[16]. Ecolab was contacted and informed that there is not content of PFOS, and the fluorocarbon content is below 2 ppm.

Danish Statistics

It is not possible to find information about the use of impregnating agents for furniture and textiles via Statistics Denmark. The statistics are not available at sufficient detail level.

4.1.4 Impregnating agents for car interiors (textiles)

The Danish EPA is carrying out a project with the title “Mapping and health assessment of products for indoor car care” (2007). In this project different products for indoor car care have been examined, among other impregnating agents for textiles. Two products seem to have a content of fluorinated substances in the concentration of 0.01 mg/kg (ppm). The concentration is, however, uncertain, as it was measured by use of a screening technique (headspace analysis), and the identification of the fluorinated substance was also uncertain. Nevertheless, one of the products: “SONAX Textil Imprægnering” is containing a fluorocarbon resin according to the MSDS.

“SONAX Textil Imprægnering” has it primarily use on indoor car upholstery, but is also usable for tents, backpacks and and other textiles with climate membrane.

The German producer of SONAX, Salzenbrodt GmbH, has been contacted, and they have confirmed that their textile impregnation agents are containing fluorinated substances. SONAX themselves do not have information about the content of fluorinated compounds in their product. However, the supplier to Salzenbrodt GmbH informed that the product “SONAX Textil Imprægnering” contains the DuPont product Foraperle 225, which contains the compound 2-Propenoic acid, 2-methyl-, hexadecyl ester, polymers with 2-hydroxyethyl methacrylate, g-w-perfluoro-C₁₀-C₁₆-alkyl acrylate and stearyl methacrylate (CAS 203743-03-7). Salzenbrodt GmbH estimated that a total of 1.8 kg of this fluorinated polymer was used in products sold to Denmark in 2006. Additional questions were asked about their content and sales amount on the Danish market, but no information was received.

4.2 Occurrence in impregnated products

Chapter 4.1 focused on impregnating agents, i.e. chemical products. This chapter focuses on products/articles that are being impregnated by the producer before being sold on the market. It is somewhat easier to find information about the content of fluorinated substances in chemical products, as e.g. Material Safety Data Sheets exist. Information about the content of chemicals in consumer articles/consumer products is not easily accessible.

This survey does not focus on the use of fluorinated compounds within the area of food, as this product area is not the responsibility of the Danish EPA.

4.2.1 Clothes

Three companies trading normal daily clothes have been contacted. None of the contacted companies are using fluorinated compounds in their products to their knowledge. No products are sold with water- or stain proof properties.

4.2.2 Waterproof clothing and all-weather clothes

Fluorinated levels in products

A Swedish and Norwegian study from 2006 states that the annual global fluorotelomer production is around 10000 tonnes, and that about 50% of this production goes to the impregnation of textile consumer products, e.g. in all-weather clothing, carpets and upholstery (Schulze and Norin, 2006; Berger and Herzke, 2006). In the same study six all-weather jackets for children from five different brands (Gore-Tex Paclite, HellyTech, FineTex/DuPont Teflon, TCS Water and Dermizax) bought in the Nordic countries were investigated for the content of fluorinated substances. The study analysed the unbound content of fluorinated compounds in the jackets: unbound content of fluorotelomer alcohols (FTOH) between 25 and 1000 µg/m² of textile, an unbound content of PFCA between <5 and 400 µg/m² of textile and an unbound content of PFOS related compounds between <5 and 100 µg/m² of textile.

Companies contacted

Three different “sportswear” companies were contacted on the matter. One company claimed that their products produced in China did not contain fluorinated compounds. The two other companies informed that many of their products are Gore-Tex products, i.e. they are based on fluorochemistry.

Helly Hansen, Norway, confirmed the use of fluorocarbons in their products, such as e.g. breathable jackets. No information has been received with respect to total amounts used in their products today. Helly Hansen informed that they have been monitoring the discussions around PFOS and PFOA usage in textiles and have concluded that from ultimo 2008 or during summer 2009 the latest, all HH products will be free from fluorocarbons or fluorotelomers.

A supplier of fluorinated impregnating products to the Danish textile market was contacted. They reported an annual sale of around 650-700 kg of their products. These products contain fluoropolymers with an average content of 17%. This results in an annual sale of 111-119 kg fluoropolymers to textile industries in Denmark. The supplier estimated their market share to be about 30%. This will result in an estimation of about 400 kg fluorinated substances being used for impregnation of textiles in Denmark (excluding carpets).

Danish Statistics

In the Danish statistics it is possible to find some product groups that specifically mention impregnated clothing. However, it is not possible to distinguish the type of impregnation, i.e. it can be other types of impregnation than with fluorinated compounds – for example silicones. The product groups are:

• 6113 0090 ”Beklædningsgenstande, trikotage, konfektioneret af imprægneret, belagt eller lamineret tekstilstof, undtagen gummieret” (Clothing, hosiery, ready-made clothing impregnated, covered or laminated textile fabric, but not rubberised) exist.
• 62101010 “Beklædningsgenstande konfektioneret af filt, også imprægneret, overtrukket, belagt eller lamineret” (Ready-made apparel of felt, also impregnated, coated, covered or laminated).
• 62104000 “Konfektioneret tekstilbeklædning, imprægneret, overtrukket, belagt eller lamineret, til mænd/drenge, ej trikotage, i.a.n^[17].” (Ready-made textile clothing, impregnated, coated, covered or laminated, for men/boys, not hosiery, not mentioned elsewhere).
• 62105000 “Konfektioneret tekstilbeklædning, imprægneret, overtrukket, belagt el lamineret, til kvinder/piger, ej trikotage, i.a.n.” (Ready-made textile clothing, impregnated, coated, covered or laminated, for women/girls, not hosiery, not mentioned elsewhere).

The import and export are given in both currency and kg whereas the production is given in currency and in pieces, which makes it difficult to estimate the total use of impregnated clothing in Denmark. As the production is close to 15-20% of the imported amount, the production amount is estimated by using the ratio of tonnes per DKK for the imported amount for the different years. These estimations give the following values (see Table 4.4):

Table 4.4: Supply of clothing impregnated (tonnes) in Denmark according to Danish Statistics

It has not been possible to identify use concentrations for different fluorinated impregnating agents for clothes. However, some of the Zonyl products can be used for both textiles and carpets. It is therefore assumed in the calculations that the use concentrations are about the same. The unbound measured figures for total content of fluorinated substances in the Norwegian and Swedish study cannot be used, as it is not measured for the total content but for the unbound chemicals, which are probably only about less than 1‰ of the total content.

If it is assumed that between 5 and 50% of the impregnated clothing are impregnated with fluorinated substances, and that the total use of fluorinated substances are between 0.27 and 2.7 g/kg textile as used for carpets (according to use instructions for Zonyl products), then the content of fluorinated compounds in clothing in Denmark would be between 35 kg and 3.5 tonnes (density assumed to be 0.5 kg/m²)^[18].

The minimum value is set to 400 kg based on the information from a supplier (as described above). The maximum value used is the 3.5 tonnes, as the estimate based on the market share for the one company giving information is too uncertain.

For comparison, the above-mentioned Swedish and Norwegian study estimates that the total global use of fluorotelomer compounds for impregnated products (textiles, carpets, etc.) is around 5,000 tonnes globally.

To sum up the minimum use of fluorinated compounds used for impregnated clothings is estimated to be 400 kg and the maximum use is estimated to 3.5 tonnes.

4.2.3 Footwear

The footwear category covers a range of different kind of footwear, such as slippers, boots, shoes, footwear for sports, etc. It is assumed that mainly boots are being coated with fluorinated products such as Teflon. Visits to shoe stores in Denmark show that especially boots for children are treated with Teflon.

Companies contacted

Two producers of footwear were contacted. One company informed that they do use an impregnating agent (MI 1113) with a content of a fluorine compound for finishing of their product. The production is however carried out abroad, and it is only for a special type of product for a special customer abroad, i.e. no fluorinated compounds are used for impregnating the products for the Danish market.

The Danish supplier of this MI 1113 impregnating agent was contacted and they could inform that the impregnating agent is not sold to any other companies in Denmark.

The other footwear producing company did not want to participate with information. It is supposed that fluorinated compounds are used.

Danish Statistics

The Danish Statistics on footwear are divided in different categories dependant on the type of footwear, e.g. waterproof (rubber), upper section of textile, leather, etc. These footwear categories cover a range of different kind of footwear, such as slippers, boots, shoes, footwear for sports, etc.

It is, however, impossible to perform a calculation for content of fluorinated substances in footwear, as:

• No information can be found regarding the content of fluorinated substances per pair of shoes/boots.
• The Danish supply of footwear cannot easily be calculated, as the import/export statistics is calculated in kilos, and the Danish production is calculated either in pair of shoes or 1,000 pieces dependant on the product code, i.e. the numbers cannot be added.

To sum up: We know that especially childrens boots are being treated with Teflon, but have not any information about amounts. The statistics in this area cannot be used for any educated guess, i.e. the amount of fluorinated substances used in this area is unknown.

4.2.4 Furniture

Companies contacted

Five companies selling furniture were contacted. Three of the companies were not interested in participating in the project. The two other companies informed that they did not use any kind of fluorinated compounds to impregnate their furniture. IKEA answered that they had been using Scotchgard in some of their furniture fabrics before 2000, but decided to phase out the use before the 3M Company withdrew their products from the market. Instead, IKEA is now using the concept of removable and washable covers for their furniture. The only Teflon-treated products to be found in IKEA are in non-stick cookware.

4.2.5 Carpets and mats

Two carpet stores were visited in order to learn about the sale of impregnated carpets in Denmark. The information provided varied. In one store we were told that almost every carpet sold today are impregnated (99%). Some are impregnated with Teflon, and carpets for sale in both stores were marked Scotchgard™. However, in the other store, we were told that the use of Teflon impregnated carpets is on its way out, as the coating is expensive.

Fluorinated levels in carpets (see also Section 6.2.4.)

In a study PFOS and PFOA were found in all 16 tested vacuum cleaner dust samples from different Japanese households and offices. The levels found varied between 11-2500 ng/g dust for PFOS and 69-3700 ng/g dust for PFOA. These findings could be an indication of use of fluorinated compounds in carpets, but other products in the homes are of course also possible sources. (Moriwaki et al., 2003).

Dinglasan-Panlilio and Mabury (2006) have investigated seven different commercially available and industrial applied polymeric and surfactant materials, i.e. the chemical products that are applied to impregnated consumer products. Two investigated chemical products were carpet protectors. They identified the presence of between 0.04 and 3.8% residual unbound fluorotelomer alcohols in varying chain lengths.

Companies contacted

One of the major Danish carpet producers was contacted. They are according to their environmental report 2005/2006 producing around 6 million m² carpets. They are using fluorinated compounds for impregnation, but not PFOS or PFOS-related compounds. They are using a DuPont product for their carpets. They are impregnating 100% of the carpets they are producing. It was not possible to get more detailed information. The company referred to the trade union Federation of Danish Textile and Clothing Industry (Dansk Tekstil og Beklædning), but they could not give any information about the use of fluorinated compounds in carpets (did not have that kind of information).

Another large producer of carpets was contacted. They are producing around 7.5 million m² carpets yearly. Only about 20% of these carpets are being impregnated with a Zonyl product from DuPont. Around 50% of the carpets in total were exported; the rest was for the Danish market. It is only specific fibres that are being impregnated. Nylon fibres are always impregnated, whereas carpets based on wool fibres are never impregnated. Primarily carpets for industrial uses (offices etc.) are impregnated. In average for these two contacted carpet producers around 56% of the carpets produced in Denmark are impregnated with fluorinated compounds.

Danish Statistics

Data of the Danish supply of carpets from Danish Statistics can be found in the Table 4.5 below. The supply is calculated for the entire product group no. 57 called carpets and other textile floor coverings, which are covering carpets made of both natural fibres such as wool and coconut, and synthetic fibres.

Table 4.5: Supply of carpets (m²) in Denmark according to Danish Statistics

A calculation of the Danish supply of carpets that are not based on natural fibres such as wool and coconut (which most likely are not impregnated), shows that 90% (2006) of the total Danish supply of carpets are based on synthetic fibres. As the two largest carpet producers in Denmark (producing in total 13.5 million m² of carpets) in average are impregnating 56% of the carpets, this value is used as the lower value of the fraction of carpets being impregnated. 90% is used as the upper value (equals the percentage of carpets based on synthetic fibres).

According to MSDS of Scotchgard Carpet Protectors the content of fluorochemicals in the concentrated products is 1-5% or 2-10% for different examples of carpet protectors. The types of fluorinated chemicals are a trade secret. However, no information was found on, how the product should be used (in which concentration and how much per square meters).

According to MSDS of DuPont’s Teflon products for carpets (wool), the concentration of fluorochemicals in the concentrated products is 3-4%. This example product should be used in a 1:8 dilution, and be applied to carpets at the rate of 1.0 gallon of dilution for every 100 square feet area carpet. As one gallon is 3.785 litre and one square foot is 0.0929 m² each m² carpet impregnated will contain between 1.5 and 2.0 g fluorinated compounds^[19].

When using another of DuPont’s impregnation agents for carpets, e.g. Zonyl 5180 Carpet Protector, the fluorinated content per m² carpet will be between 0.1 g and 1.4 g^[20]. The MSDS and technical data sheet of this product state that the content of fluorinated compounds is between 1 and 10%, and that a 1:15 dilution should be used. One diluted litre will treat 200 square feet of carpet. It is uncertain, whether this product is used for pre- or after treatment of carpets.

If assumed that between 56 and 90% of the carpets in Denmark are impregnated with fluorinated compounds, and the content of fluorinated compounds is between 0.1 and 2 g per m² of carpet, this will amount to a yearly consumption of fluorinated compounds between 745 kg and 18.0 tonnes.

4.2.6 Sunshades/awnings, tents, umbrellas and parasols

Sunshades/awnings, tents, umbrellas and parasols are all products that can be impregnated with fluorinated compounds. As mentioned earlier some impregnating agents, e.g. the SONAX Tekstil Imprægnering (Textile Impregnation) spray may also be used for tents, backpacks and textiles with climate membrane (like e.g. umbrellas and parasols).

Companies contacted

A Danish firm selling awnings was contacted. It turns out they are getting the fabric for the awnings from a company in Sweden – they were also contacted. The Swedish company supplies impregnated awnings to 10 different companies in Denmark. The fabric for the awnings is impregnated with Oleophobol SL-A01, which contains a dispersion of fluoropolymers. There is no information about the percentage content of fluoropolymers. According to the Swedish company, they supply 30,000 m² of impregnated fabric for awnings to Danish companies. It has not been possible, neither to estimate the total use of fluorinated substances for impregnation of awnings sold in Denmark, nor to uncover how widespread the use of fluorinated substances for impregnation of awnings is in Denmark.

Another company gave the information that outside the Danish market, Teflon wax (polytetrafluoroethane, CAS 65530-85-0) is used in products that are applied to sunshades in order to make them water-repellent.

4.3 Occurrence in other relevant products

4.3.1 Paints

Fluorinated levels in products

According to DuPont the fluorotelomer-based surfactants are added to paints to improve flow, wetting and levelling, and for reducing the surface defects and craters. The fluorotelomer-based products are added in an amount between 300 and 500 mg of product/kg of paints (Washburn et al., 2005).

Dinglasan-Panlilio and Mabury (2006) have investigated seven different commercially available and industrial applied polymeric and surfactant materials, i.e. the chemical products that are applied to impregnated consumer products. Two investigated chemical products were fluorosurfactants for paint, polish and other coatings. They identified the presence of between 0.04 and 3.8% residual unbound fluorotelomer alcohols in varying chain lengths.

Companies contacted

Four paint and lacquers producing companies in Denmark have been contacted, as well as the trade organisation for paint and lacquers in Denmark (Foreningen for Danmarks Farve- og Lakindustri).

They were asked about their use of fluorinated compounds in paints and lacquers. We were told that some paint producers use a so-called Teflon wax (polytetrafluoroethane, CAS 65530-85-0). The typical content will be about 11-18% dry matter in water. The contacted paint producers do not use Teflon wax in products for the Danish market, but is certain that it is used in paints sold in Denmark. Teflon wax is added to leave the paint with a water repellent film, when the paint dries. An alternative to this is to use a polyethylene wax, however, that will not result in a water repellent film, but a scratch resistant surface. Teflon wax is, according to the contacted paint producing companies, not used for products sold in Denmark, but one of the paint producers uses Teflon wax in products sold outside of Denmark.

This general impression of the interviews with the four companies is in contrast to the information from the search in the Danish Product Register, where more than 10 substances in a total of about 3.5 tonnes are registered as used within the Danish paint & lacquer industry. The companies and the trade association were confronted with this, and the trade association made an inquiry at its members, and got the following response:

• Fluorinated compounds are only used by a few of the companies within the paint and lacquer industry.
• The members of the trade association were confronted with the CAS numbers found by the Product Register search and the members who responded could in general not recognisee the fluorinated substances.
• One company uses about 250 kg per year of Zonyl FSN. Zonyl is used for aqueous paints for indoor use. According to DuPont data sheet on Zonyl FSN^[21], the content of fluorosurfactants is 40%. This amounts to a total confirmed use of fluorinated substances of 100 kg. Zonyl FSN is according to the MSDS containing a fluorinated telomer (CAS 65545-80-4) – a compound that is also registered for use in paints by the Danish Product Register.

According to the trade organisation about two thirds of their members responded to the inquiry. It is not possible to say, what causes the difference in amounts between the information from the trade organisation and the Danish Product Register but it may, according to the trade organisation, be any of the following explanations:

• The amounts registered in the Danish Product Register have not been updated (the companies have not informed about that the substances are no longer used).
• The members that have not replied are using the substances.
• Companies outside the trade organisation are using the substances.
• The substances are used in raw materials that are imported by the paint & lacquer companies, but the amounts of the substances are reported to the Danish Product Register by the producers outside of Denmark, because of confidentiality. This means that the companies in Denmark do not know the total content of their paints.

Therefore, it is concluded that the use of fluorinated substances within the paint area is minimum 100 kg and maximum 3.5 tonnes (as registered in the Product Register). The contents of fluorochemicals in paint products not classified dangerous are not included. The total consumption may be somewhat higher, however, since information from an industru association showed a consumption of only 100 kg, it was decided to use the information in the Product Register at upper limit.

4.3.2 Printing inks

Companies contacted

The trade association for paint and lacquers in Denmark (Foreningen for Danmarks Farve- og Lakindustri) was contacted. The trade association made an inquiry at its members, and got the response that a fluorinated wax (PFTE-wax; CAS 9002-84-0) is used in printing inks. The wax is used to protect the surface and make the surface smoother. No information about amounts was received.

According to the search in the Danish Product Register, the use of fluorinated substances in printing inks is low (15 kg in total).

4.3.3 Auto polish and -wax

Fluorinated levels in products

In a project for the Danish EPA auto polish and wax products were investigated. In one sealing product a polyfluorinated compound  not on the OECD list (CAS no. 65530-65-6: 2-Propenoic acid, 2-methyl-, dodecyl ester, polymer with a-fluoro-?-[2-[(2-methyl-1-oxo-2-propenyl)oxy]
ethyl]poly(difluoromethylene) and N-(hydroxymethyl)-2-propenamide) was found in a concentration of 0.085 to 0.45%. No products were analysed specifically for the content of fluorinated substances. This content of a polyfluorinated compound was based on Material Safety Data Sheets. Other of the examined products could therefore also contain fluorinated substances (Ferdinand et al., 2004).

Contact to companies

Contact to a German producer of car care products has given the information that the auto polish and waxes they are producing do not have a content of fluorinated substances. However, the market share of these products on the Danish market is not known.

Danish Statistics

Data of the Danish supply of wax and polish from Danish Statistics can be found in Table 4.6. In the statistics auto polish and wax has its own product group. The supply is calculated for the entire product group no. 3405 30 called “Polermidler o. l. præparater til karrosserier/automobilpolermidler” (polishes and similar preparations for coachwork, other than metal polishes/polishes for automobiles).

Table 4.6: Supply of auto polish and wax (tonnes) in Denmark according to Danish Statistics

It looks like the market for auto polish and waxes is rising, especially as the similar numbers for 2000-2002 was 297, 414 and 373 tonnes, respectively (Ferdinand et al., 2004).

In the former project from the Danish EPA, the market for the consumers was judged to be about one third of the total market. It is uncertain whether this distribution is still valid for 2006, where the use of auto polish and waxes nearly has tripled. If assuming that between 33 and 50% of the used amount of auto polish and waxes are used by consumers, and that auto polish contains between 0.0025 and 0.1% fluorosurfactants (Zonyl FSO used as an example^[22]), then the content of fluorinated compounds in auto polish and wax used in Denmark in 2006 will be between 8 kg and 477 kg.

However, fluorinated substances may not necessarily be used for every polish or wax product. As limited information has been found on the prevalence of fluorinated substances in polish and wax, a minimum value of 1% and maximum value of 75% of the products on the market containing fluorinated substances are assumed. This results in a content of fluorinated substances in auto polish and wax used in Denmark in 2006 for the consumer market between 79 g and 358 kg.

4.3.4 Floor polish

Fluorinated levels in products

Moriwaki et al found PFOS and PFOA in all 16 tested vacuum cleaner dust samples from different Japanese households and offices. The levels found varied between 11-2500 ng/g dust for PFOS and 69-3700 ng/g dust for PFOA. These findings could be an indication of use of fluorinated compounds in carpets, but one of the samples was taken from a house with no carpets. The wooden floor in this home was treated 6 months before the sampling day with a floor wax coating. In this house the level of PFOA and PFOS in the vacuum cleaner dust was 250 ng/g dust and 94 ng/g dust, respectively. It was concluded that the wax-coating may be one of the sources to the PFOA and PFOS levels found, but no analysis of the wax was carried out. Other sources may be impregnated products, such as clothes/all-weather clothes and impregnating agents (Moriwaki et al. (2003).

Dinglasan-Panlilio and Mabury (2006) have investigated seven different commercially available and industrial applied polymeric and surfactant materials, i.e. the chemical products that are applied to impregnated consumer products. Two investigated chemical products were DuPont Zonyl fluorosurfactants for paint, polish and other coatings. They identified the presence of between 1.0 and 3.8% of dry weight residual unbound fluorotelomer alcohols in varying chain lengths for the Zonyl products.

According to DuPont website^[23] “almost every acrylic/wax floor polish formulation on the market contains a fluorosurfactant (100-500 ppm)”. This equals 0.01% to 0.05% of the product is a fluorosurfactant. This range of contents on wet weight basis seems to be significantly lower than the results published by Dinglasan-Panlilio and Mabury (2006), however, their results were reported on dry weight.

Danish Statistics

The supply is calculated for the entire product group no. 3405 9090 called “Pudse- og polermidler, undtagen til sko, læder, træværk, biler og metalvarer samt skurepræparater” (polishes except for shoes, leather, woodwork, cars and metal goods, and scrub agents). The supply of polish products is listed in Table 4.7.

Table 4.7: Supply of polish for other polish products (floor polish etc.) in Denmark according to Danish Statistics

When using the percentages of content of fluorinated compounds taken from the DuPont website and the supply of 240 tonnes of “other polish products” in Denmark in 2006, the content of fluorinated compounds in “other polish products” used in Denmark in 2006 is between 24 kg and 120 kg. However, as this group of “other polish products” in the Danish Statistics may cover other products than floor polish products, and as fluorinated substances may not necessarily be used for every polish product, a minimum value of 1% and a maximum value of 50% of the products on the market containing fluorinated substances are assumed. This results in a content of fluorinated substances in floor polish used in Denmark in 2006 between 0.2 kg and 60 kg.

4.3.5 Ski wax

The market for ski wax was investigated by contact to a single Norwegian producer of ski wax. Only one special type of ski wax is containing a perfluorinated alkane (CAS No. 355-49-7, perfluorohexadecane, C₁₆F₃₄). The ski wax is very expensive (around 1000 NOK per 30 g of wax) and is hence only used by top-professional skiers. The Norwegian production is just below 1 tonne of this wax that contains 80-100% of the perfluorinated compound. 50% is being exported. It is assumed that the use of this kind of product in Denmark is negligible.

4.3.6 Cleaning agents for glass

By searching the Internet a number of cleaning agents for glass have been identified. It is however uncertain for most products whether the cleaning agents contain fluorinated compounds. The following cleaning agents have been identified:

• “Percenta Glas- & Keramik Rengøring”. Nanotechnology has been used.
• “Point2you Glas & Keramikforsegling”. Nanotechnology has been used.
• “Point2you Nano-glasforsegling”. Nanotechnology has been used.
• “NanoCover basis klargøring”
• Aro, Glas universal spray.
• Ajax, Glas universal, Colgate-Palmolive.
• “Mr. Muscle Glasrengøring Professionel”, JohnsonDiversey.
• Cif Windows Spray Regular, Unilever (no content of fluorinated substances according to the ingredients on their website – fluorinated substances are not mentioned specific, but all ingredients are listed, so it is assumed that no fluorinated substances are in the products).
• Froggy Sprit Glasspray (no content of fluorinated substances according to the ingredients on their website – fluorinated substances are not mentioned specific, but all ingredients are listed, so it is assumed that no fluorinated substances are in the products).

Companies contacted

Several of the companies were contacted, but only few were interesting in giving information. JohnsonDiversey is only selling window cleaning products on the professional market, and they are not using any kind of fluorinated compounds in their products. Presently, Unilever has not any glass cleaning products on the Danish market. About two years ago they sold the product (Cif Windows Spray), which did not contain any fluorinated substances.

It seems like the “ordinary” glass cleaning products found in every day stores do not contain fluorinated compounds. It is however, uncertain whether the glass cleaning products that are based on nanotechnology contain fluorinated compounds.

Fodnoter

[13] According to the project for the Danish EPA ”Mapping of chemicals in dry-cleaned textiles from Rynex and hydrocarbon dry-cleaning shops”, Survey no. 21, 2003.

[14] http://www.ecolab.dk/html_sider/produkter/Tekster/Arbejdsbeklaedning.pdf

[15] http://www.ecolab.dk/drift/servlet/se.ibs.ns.is.ItemDetailServlet?KEY_ITEM=101664

[16] http://www.ecolab.at/website/hygiene/home/
divisions/textile-care/waschmittelsysteme/finish-produkte/

[17] i.a.n = ikke andetsteds nævnt (not mentioned elsewhere)

[18] http://www2.mst.dk/common/Udgivramme/Frame.asp?
pg=http://www2.mst.dk/udgiv/publikationer/2000/87-7944-156-4/html/kap04.htm

[19] Information found at http://www.dupont.com/teflon/carpetprotector/tech_info.html.

[20] Information found at http://www.dupont.com/teflon/carpetprotector/tech_info.html.

[21] http://www2.dupont.com/Zonyl_Foraperle/en_US/assets/downloads/Zonyl_FSN.pdf

[22] According to information on Zonyl FSO on DuPont website, Zonyl FSO contains 50% fluorosurfactants, and should be used in a solution between 0.005-0.2%.

[23] http://www2.dupont.com/Zonyl_Foraperle/en_US/uses_apps/industrial.html

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