Per- and polyfluorinated alkyl compounds

from Wikipedia, the free encyclopedia

Per- and polyfluorinated alkyl compounds are organic compounds in which the hydrogen atoms on the carbon structure have been completely replaced by fluorine atoms on at least one carbon atom . PFAS (from English per- and polyfluoroalkyl substances ) is usually used as an abbreviation . According to the OECD, there are at least 4730 different PFAS.

Historically, the term was Perfluorinated surfactants (Engl. Fluorosurfactants , fluorinated surfactant or perfluorinated alkylated substance ) and the abbreviation PFT used which, however primarily perfluorosulfonic and perfluorocarboxylic with the two lead compounds perfluorooctane sulfonate (PFOS) and perfluorooctanoic included (PFOA). The abbreviation PFC , which stands for “per- and polyfluorinated chemicals”, is also rarely used .

PFAS do not have a natural source. They are manufactured industrially and used in a wide variety of products. Many PFAS accumulate in the environment as well as in human and animal tissue. Some PFAS are suspected of being carcinogenic. The total annual health-related costs associated with human exposure to PFASs were at least EUR 52 to 84 billion in the EEA countries . The total annual costs for environmental screening, monitoring for contamination, water treatment, soil remediation and health assessment in the EEA plus Switzerland amount to 821 million to 170 billion euros.

Classification

Non-polymers

Perfluoroalkyl acids

Perfluorooctanesulfonic acid
Perfluorooctanoic acid
Perfluoroalkyl acids
Surname Perfluorocarboxylic acids Perfluorosulfonic acids Perfluorophosphoric acids
Semi-structural formula C n F (2n + 1) COOH, (n = 4–12) C n F (2n + 1) SO 3 H, (n = 4, 6, 8) C n F (2n + 1) PO 3 H 2
example Perfluorooctanoic acid (PFOA) Perfluorooctanesulfonic acid (PFOS)  

(n = 4: perfluorobutanoic acid, n = 6: perfluorohexanoic acid, n = 8: perfluorooctanoic acid, n = 10: perfluorodecanoic acid ...)

Other perfluoroalkyl compounds

Other highly fluorinated substances

Polymers

Fluoropolymers

Side chain fluorinated polymers

  • Fluorinated methyl
    acrylic polymers (fluorotelomer acrylate (FTA)) (from the monomer methyl-2-fluoroacrylate: C 4 H 5 FO 2 ( EC number : 607-233-2))
  • Fluorinated urethane polymers
  • Fluorinated oxetane polymers

Other polymers

Chemical properties

PFAS have a high thermal and chemical stability. The carbon chain of the compound is hydrophobic , while the head group that is often present has hydrophilic properties. Its use as a surfactant results from this amphiphilic character .

In contrast to the usual surfactants, the perfluorinated carbon chain also has a lipophobic character. In addition to water, it also repels oil, grease and other non-polar compounds as well as dirt particles.

Manufacturing

For the production of perfluorinated surfactants, the processes of electrochemical fluorination (ECF) according to Simons (1941) or fluorotelomerization are mostly used in industrial synthesis . Several thousand tons of PFAS are produced annually; the country with the largest production volume is the USA (as of 2005).

use

The compounds are used in the textile industry for the production of water-repellent, breathable textiles and in the paper industry for the production of dirt, grease and water-repellent papers. Further areas of application are the photo industry, the manufacture of fire extinguishing agents, aviation and the electroplating industry . They can also be part of lubricants and impregnating agents. PFOA is used as an emulsifier in the manufacture of the fluoropolymers PTFE ( polytetrafluoroethylene , "Teflon") and PVDF ( polyvinylidene fluoride ) . In this application, PFOA occurs as a process emission and as an impurity in end products. PFAS are among other things a component of ski wax.

In the bluesign system, which advocates the sustainable production of textiles and excludes environmentally harmful substances from the manufacturing process, numerous PFAS are included in the negative list, including perfluoroalkylsulfonates, perfluorocarboxylates and fluorotelomer compounds.

Environmental and health aspects

PFAS are considered to be non-biodegradable in nature. They are therefore classified as long-lived organic pollutants . The chemicals in this group are now found worldwide; they have already been detected in the livers of polar bears .

PFOS has significantly more bioaffinity than PFOA, so the former is predominant in biological samples while the latter is dominant in the oceans. In contrast, fluorotelomer alcohols are increasingly being detected in the air. They are particularly important for the formation of perfluorocarboxylic acids such as. B. PFOA.

Perfluorinated surfactants are toxic to humans and animals and are suspected of causing cancer. In the body, perfluorinated surfactants accumulate in the blood and organ tissue and are only excreted slowly (in humans in 4.4 years about half for PFOA, for PFOS in about 8.7 years). The first evidence in the blood of chemical workers was provided in the 1960s. It was not until 2001 that correspondingly sensitive measurement methods were published that also enabled the detection of PFT exposure in the general population. In 2006, PFT was also detected in higher concentrations in breast milk in Lower Saxony.

PFAS and other substances are suspected of influencing thyroid hormones and thereby contributing to neurodevelopmental disorders .

Health effects of exposure to PFAS

PFT in German waters

Drainage of the area contaminated with perfluorinated surfactants near Scharfenberg
Field in Rüthen , after removing the topsoil

Lower Saxony

In 2019 fish from the Ochtum were examined for PFAS. Due to the high exposure to PFOA, we do not recommend consuming the fish.

North Rhine-Westphalia

In March 2006, as part of a study by the Institute for Hygiene and Public Health (IHÖG) at the University of Bonn, elevated concentrations of PFT in various surface waters in Germany were found in the Ruhr and then also in the Möhne . The reason for this investigation was a series of tests regarding high PFT values ​​in water bodies in the USA, the German researchers also wanted to examine German soils for the carcinogenic substance in order to check the drinking water quality. In the district of Arnsberg-Neheim a concentration of 0.56 µg / l was found in the drinking water, the drinking water commission of the Federal Environment Agency is aiming for a value of 0.1 µg / l. It was found that the pollution came from manure made from industrial waste that was applied to fields in the river basin. Some areas were subsequently renovated. Depending on the degree of contamination and the geology of the subsoil, a decision was made in favor of drainage with subsequent activated carbon treatment of the seepage water or for the removal and disposal of the topsoil (see pictures).

In November 2006, research has on the wastewater treatment plant in Rhede shown that in the inlet of the treatment plant are present high levels of PFT in the wastewater. Significantly higher concentrations were also measured in the effluent of the sewage treatment plant. These studies suggest that PFT accumulates in sewage sludge .

Due to their widespread use, perfluorinated surfactants also find their way into the environment via municipal sewage treatment plants and are particularly detectable below main settlements on receiving waters with comparatively weak drainage . One example of this is the Itter below Solingen, in which up to 0.7 µg / l PFT was detected.

Harald Friedrich , at that time the responsible department head in the Ministry of the Environment , suggested, due to the possible previous pollution of the Ruhr water, to fundamentally improve the treatment of the drinking water obtained from it in the waterworks on the Ruhr through further measures.

The PFT load of the Ruhr near Essen was determined for the sum of PFOA and PFOS in the annual average of only 0.044 micrograms per liter. Compared to 2007, the average daily freight at the mouth of the Ruhr decreased by a total of 59 percent.

Bavaria

In 2006, conspicuous PFT values ​​were also measured in southeast Upper Bavaria below the discharge from the industrial park Werk Gendorf into the Alz, which is approved by water law (total PFT about 8 µg / l, of which PFOA 7.5 µg / l). According to the further dilution, concentrations of 0.1 and 0.05 µg / l were measured for PFOA downstream on the Inn and Danube.

For the start of construction of the northern connection of Nuremberg Airport to the A3 motorway ( Bundesstraße 4f ) with tunneling under the runway, the government of Central Franconia made a condition in its planning approval of February 15, 2012 that the construction had no impact on those found in the airport area Has PFT residue. The planned lowering of the groundwater level by 22 meters when building the tunnel requires extensive water diversion measures. This means that the PFT residues in the soil cannot be ruled out. These were caused by the seepage of extinguishing foam during fire brigade exercises on the airport premises. Since methods for eliminating PFT in the soil must first be found and tested, the start of construction can be delayed by many years.

2012 were also in the lake Stoiber mill of the north of Munich airport and the Lindacher lake north of the airfield Ingolstadt / Manching detected elevated levels of PFT.

In 2015, increased PFT values ​​were measured in Birkensee near Röthenbach in the Nürnberger Land district.

PFT contamination was detected at various groundwater measuring points on the premises of Allgäu Airport Memmingen . These come from the extinguishing foam of the v. a. was released during fire fighting exercises. When the fire extinguisher was dismantled, PFT-contaminated soil was moved to other areas of the former air base. In the meantime, the impurities have reached the drinking water catchment of the neighboring community of Ungerhausen . In the last published drinking water test on September 11, 2015, the PFT content was 8.7 ng per liter of drinking water. The highest PFT values ​​in the Ungerhausen municipal area are currently measured in the 11d underground hydrant. At a removal depth of 15.00 m, 360 ng PFT per liter of water were documented on May 5, 2015 and 320 ng on June 8, 2015. PFT is also found in Schmiedbach Ungerhausen. At the discharge point for surface water from the Allgäu Airport in the Schmiedbach 10.0 ng PFT per liter of water and at the Schmiedbach bridge 33.0 ng PFT (of which 16.0 ng perfluorooctanesulfonic acid , 11.0 ng perfluoronanoic acid and 4.6 ng perfluorohexanesulfonic acid) measured per liter of water. "However, the public sector currently sees no need for action, since the values ​​are still below the threshold values ​​..." The municipality complains that the Unterallgäu district office is "not very cooperative" and is considering the water network with the neighboring municipality of Sontheim (Swabia ) to participate.

In the Landsberg / Lech Air Base, extinguishing exercises with PFT / PFC-containing foam were also carried out in a fire extinguishing basin . 776.4 µg PFCA (perfluorocarboxylic acids) and 3,603 µg PFAS (perfluoroalkylsulfonic acids) per kg are measured in the sediment of the basin. The appraiser expects renovation costs for expansion and disposal i. H. v. € 4-6 million. Here, too, the PFC has made it into the drinking water. "Immediately after the increased levels of perfluorinated chemicals (PFC) in the drinking water of the seven springs in Untermühlhausen ... became known ... the drinking water was fed into the supply network of the connected municipalities and parts of the municipality (Untermühlhausen, Epfenhausen, Weil, Geretshausen, Petzenhausen, Beuerbach, Pestenacker, Mangmühle , Adelshausen). "

Saarland

An increased PFT load from an extinguishing agent entry was also found in a fish pond and receiving water, which were observed in Saarland after a "normal" fire extinguishing operation.

Remote regions

In September 2015, Greenpeace published research results showing that PFAS ( perfluorocarboxylic acids , perfluorosulfonic acids, fluorotelomersulfonic acids , perfluorooctanesulfonamide ) are present in water and ice in remote mountain regions.

Clarification of PFAS-contaminated wastewater

PFAS are not broken down in normal sewage treatment plants . These are mainly based on biodegradation by microorganisms, which PFAS cannot metabolize. The PFAS thus reach the receiving water and sewage sludge undiminished . The only way to almost completely remove PFAS from the water is to filter the wastewater through activated carbon . It is difficult to determine the origin of the PFAS contained in the wastewater. A passive collection method that has been used so far with good success is in Günther et al. (2009).

PFAS in breast milk and food

A study on French fries in several German cities commissioned by Greenpeace in 2006 and carried out by Fraunhofer IME showed a broad public that PFAS also occurs in food. The institute had previously detected PFAS in breast milk in a pilot study. International studies show that fish-based foods contain comparatively high levels of PFOS, PFHxS and perfluorocarboxylic acids.

Due to the long half-life in the human body, food intake seems to explain the PFAS blood levels of the average population in the lower ppb range. The calculation models on which the studies are based, however, show high uncertainties and cannot rule out that other sources also contribute significantly to human exposure.

Contact through military use

There are theories according to which PFAS are part of the universal fuel JP-8 used by NATO and serve there as a carrier substance for additives. It is suspected that this fuel is linked to multiple chemical intolerances.

Limit values

The German Drinking Water Ordinance does not contain any specific limit values ​​for the PFAS group (PFOA, PFOS, etc.). No limit values ​​for PFAS are available internationally either. The Federal Environment Agency recommended the following maximum values ​​in 2006:

  • 0.1 μg / l: "Health orientation value" - target value for drinking water after lifelong exposure
  • 0.3 μg / l: "Life-long tolerable guide value for all population groups"
  • 0.5 μg / l: "Precautionary measure value for infants (and pregnant women)"
  • 5.0 μg / l: "Measure value for adults" - "No longer usable" as drinking water (values ​​of 1.5 to 5 μg / l can be tolerated for up to 1 year)

The maximum values ​​apply to the sum of the various perfluorosurfactants such as PFOA, PFOS, etc. Due to incomplete data and unclear risk assessment, a general reference was made to the recommendation for "divisible or non-assessable" substances. These provide for a “pragmatic health orientation value” of generally 0.1 μg / l for “weakly to non-genotoxic substances”.

The permitted daily dose (Tolerable Daily Intake TDI) for all risk groups (including infants) is specified by the Federal Environment Agency as 0.1 μg per kg body weight and day. For an adult weighing 70 kg, this means a permitted intake of 7 μg per day.

The values ​​do not take into account possible general background exposure, e.g. via food. In Great Britain alone, an average dietary intake of 0.13 μg / kg body weight per day was determined for PFOS in adults.

In December 2018, EFSA reduced the tolerable daily intake (TWI) to 13 ng per kg body weight and week for PFOS and 6 ng per kg body weight and week for PFOA. It has been found that exposure of a significant proportion of the population is higher than these values.

Prohibitions

Following a proposal from the European Commission , the Environment Committee of the European Parliament decided on July 13, 2006 to extend the ban on perfluorinated surfactants. The European Commission had initially proposed a limit of 0.1 percent. With the 11th ordinance amending chemical regulations in accordance with Directive 2006/122 / EC of the European Parliament and of the Council of December 12, 2006, which came into force on October 26, 2007 , perfluorooctanesulfonates (PFOS; perfluorooctanesulfonic acid, metal salts , halides, amides and other derivatives including polymers) and preparations with a mass content of 0.005% PFOS or more are no longer used with a few exceptions.

PFOS, its salts and perfluorooctanesulfonyl fluoride were included in Appendix B of the Stockholm Convention in 2009 , PFOA incl. Their salts and related compounds in 2019. PFHxS incl. Their salts and related compounds were evaluated for inclusion in the Convention and recommended to the Conference of the Parties .

In the EU, PFOA, PFHxS, HFPO-DA , PFBS and the C 9 –C 14 perfluorocarboxylic acids were rated as SVHC substances. Since July 4, 2020, PFOA is no longer allowed to be manufactured or marketed in the EU. In mixtures, the upper limit for PFOA is 25 ppb and for PFOA precursors is 1000 ppb.

Science policy aspirations

The Zurich Declaration emphasizes that although well-known old PFAS such as PFOS and PFOA have been extensively investigated and regulated for their identified hazardous properties over the past two decades, very little information exists about the current uses and potential dangers of many other PFAS . There will be increased collaboration in gathering information to close critical data gaps, developing novel concepts to focus on very persistent substances and conducting joint assessments for groups of PFAS. The declaration builds on previous calls by scientists to PFAS, namely the Helsingør Declaration in 2014 and the Madrid Declaration in 2015. It sets out a precautionary approach to the use of PFAS as well as a transition to the development and use of less persistent or non- chemical alternatives.

reception

See also

literature

Web links

Commons : Perfluorinated Substances  - Collection of pictures, videos and audio files

Individual evidence

  1. OECD : Toward a New Comprehensive Global Database of Per- and Polyfluoroalkyl Substances (PFASs): Summary Report on Updating the OECD 2007 List of Per- and Polyfluoroalkyl Substances (PFASs) , Series on Risk Management, No. 39, ENV / JM / MONO (2018) 7.
  2. a b Nordic Council of Ministers : THE COST OF INACTION: A socioeconomic analysis of environmental and health impacts linked to exposure to PFAS , TemaNord 2019: 516.
  3. Nordic Council of Ministers: Per- and polyfluoroalkylether substances: identity, production and use. 2020, doi: 10.6027 / NA2020-901 full text .
  4. InfoCard on methyl 2-fluoroacrylate from the European Chemicals Agency (ECHA), accessed on July 7, 2020.
  5. a b c Marc Fricke and Uwe Lahl (BMU - Federal Ministry for the Environment, Nature Conservation and Reactor Safety): Risk assessment of perfluorosurfactants as a contribution to the current discussion on the REACH dossier of the EU Commission , in: Journal for Environmental Chemistry and Ecotoxicology (UWSF), volume 17, Vol. 1, pp. 36-49, 2005, doi: 10.1007 / BF03038694 .
  6. David A. Ellis, Scott A. Mabury, Jonathan W. Martin and Derek CG Muir (2001): Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment. In: Nature 412, pp. 321-324. doi: 10.1038 / 35085548 .
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