Perfluorooctanesulfonic acid

Perfluorooctanesulfonic acid

Names
Systematic IUPAC name 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-Heptadecafluoro-1-octanesulfonic acid
Other names PFOS
Identifiers
CAS Number	1763-23-1 Y
ChEBI	CHEBI:39421 Y
ChemSpider	67068 Y
EC Number	217-179-8
Jmol 3D model	Interactive image
KEGG	C18142 Y
PubChem	74483
InChI InChI=1S/C8HF17O3S/c9-1(10,3(13,14)5(17,18)7(21,22)23)2(11,12)4(15,16)6(19,20)8(24,25)29(26,27)28/h(H,26,27,28) Y Key: YFSUTJLHUFNCNZ-UHFFFAOYSA-N Y InChI=1/C8HF17O3S/c9-1(10,3(13,14)5(17,18)7(21,22)23)2(11,12)4(15,16)6(19,20)8(24,25)29(26,27)28/h(H,26,27,28) Key: YFSUTJLHUFNCNZ-UHFFFAOYAS
SMILES FC(F)(C(F)(F)S(=O)(=O)O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
Properties
Chemical formula	C8HF17O3S
Molar mass	500.13 g/mol
Boiling point	133 °C (271 °F; 406 K) at 6 torr
Acidity (pKa)	<<0
Vapor pressure	{{{value}}}
Related compounds
Related compounds	Perfluorooctanoic acid (PFOA), Perfluorobutanesulfonic acid (PFBS), Perfluorooctanesulfonamide (PFOSA), Perfluorononanoic acid (PFNA)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references

Perfluorooctanesulfonic acid or perfluorooctane sulfonate (PFOS) is a man-made fluorosurfactant and global pollutant. PFOS was the key ingredient in Scotchgard, a fabric protector made by 3M, and numerous stain repellents. It was added to Annex B of the Stockholm Convention on Persistent Organic Pollutants in May 2009. PFOS can be synthesized in industrial production or result from the degradation of precursors. PFOS levels that have been detected in wildlife are considered high enough to affect health parameters, and recently higher serum levels of PFOS were found to be associated with increased risk of chronic kidney disease in the general US population. "This association was independent of confounders such as age, sex, race/ethnicity, body mass index, diabetes, hypertension, and serum cholesterol level."

History

In 1949, 3M began producing PFOS-based compounds by electrochemical fluorination resulting in the synthetic precursor perfluorooctane sulfonyl fluoride. In 1968, organofluorine content was detected in the blood serum of consumers, and in 1976 it was suggested to be PFOA or a related compound such as PFOS. In 1997, 3M detected PFOS in blood from global blood banks. In 1999, the U.S. Environmental Protection Agency began investigating perfluorinated compounds after receiving data on the global distribution and toxicity of PFOS, the key ingredient in Scotchgard. For these reasons, and USEPA pressure, the primary American producer of PFOS, 3M, announced, in May 2000, the phaseout of the production of PFOS, PFOA, and PFOS-related products. PFOS and PFOS-related chemicals are currently produced in China.

Advances in analytical chemistry in recent years have allowed the routine detection of low- and sub-ppb levels of PFOS in food, wildlife, and humans.

Synthesis

The synthesis of PFOS uses perfluorooctanesulfonyl fluoride (POSF) as feedstock.

Properties

The C₈F₁₇ subunit of PFOS is hydrophobic and lipophobic, like other fluorocarbons, while the sulfonic acid/sulfonate group adds polarity. PFOS is an exceptionally stable compound in industrial applications and in the environment because of the effect of aggregate carbon–fluorine bonds. PFOS is a fluorosurfactant that lowers the surface tension of water more than that of hydrocarbon surfactants. Although attention is typically focused on the straight-chain isomer (n-PFOS), which is dominant in commercial mixtures and environmental samples, there are 89 linear and branched congeners that are expected to have different physical, chemical, and toxicological properties.

Uses

Perfluorooctanesulfonic acid is usually used as the sodium or potassium salts.

• PFOS was the key ingredient in Scotchgard, a fabric protector made by 3M, and numerous stain repellents.
• PFOS, together with PFOA, has also been used to make aqueous film forming foam (AFFF), a component of fire-fighting foams, and alcohol-type concentrate foams.
• PFOS compounds can also be found in some impregnation agents for textiles, paper, and leather; in wax, polishes, paints, varnishes, and cleaning products for general use; in metal surfaces, and carpets.
• In the semiconductor industry, PFOS is used in multiple photolithographic chemicals including: photoacid generators (PAGs) and anti-reflective coatings (ARCs). It has been phased out in the European Union semiconductor industry due to health concerns.
• In Skydrol, a hydraulic fluid used in commercial aviation.

The most important emission sources of PFOS are metal plating and fire-fighting foams.

Health effects in humans and wildlife

According to a 2002 study by the Environmental Directorate of the OECD "PFOS is persistent, bioaccumulative and toxic to mammalian species."

In 2008, it was shown to affect the immune system of male mice at a blood serum concentration of ~90 parts per billion, raising the possibility that highly exposed people and wildlife are immunocompromised. Chicken eggs dosed at 1 milligram per kilogram (or 1000 parts per billion) of egg weight developed into juvenile chickens with an average of ~150 parts per billion in blood serum—and showed brain asymmetry and decreased immunoglobulin levels. Occupationally exposed individuals may have an average level of PFOS over 1000 parts per billion, and a small segment of individuals in the upper range of the general population may be over the 91.5 parts per billion level. A variety of wildlife species have had PFOS levels measured in egg, liver, kidney, serum, and plasma samples and some of the highest recorded values as of January 2006 are listed below.

Species	Geography	Year	Sample	PFOS (ppb)
Bald eagle	Midwestern USA	1990–93	plasma	2,200
Brandt's cormorant	California, USA	1997	liver	970
Guillemot	Baltic Sea	1997	egg	614
Carrion crow	Tokyo Bay, Japan	2000	liver	464
Red-throated loon	North Carolina, USA	1998	liver	861
Polar bear	Sanikiluaq, Nunavut	2002	liver	3,100
Harbor seal	Dutch Wadden Sea, Denmark	2002	muscle	2,725
Bottlenose dolphin	Charleston, South Carolina, USA	2003	plasma	1,315
Common dolphin	Mediterranean Sea, Italy	1998	liver	940
Mink	Michigan, USA	2000–01	liver	59,500

The levels observed in wild animals are considered sufficient to "alter health parameters". In people, the highest exposures to PFOS in blood have been 12,830 parts per billion for occupational exposure and 656 parts per billion—or possibly 1,656 parts per billion—in a consumer.

In animal studies PFOS can cause cancer, delays in physical development, stunted growth, endocrine disruption, and neonatal mortality; Neonatal mortality might be the most dramatic result of laboratory animal tests with PFOS. Female mice with blood levels of PFOS at ranges found in wildlife and humans demonstrated higher mortality when infected with influenza A. PFOS reduces the birth size of animals; in humans, correlations between PFOS levels and reduced fetal growth are inconsistent.

PFOS is detected in the blood serum of almost all people in the U.S., and concentrations have been decreasing over time. In contrast, PFOS blood levels appear to be rising in China. PFOS levels in pregnant women have been associated with preeclampsia. Increased levels have been associated with altered thyroid hormone levels in adults and an increased risk of elevated cholesterol. Levels in US children aged 12–15 were associated with an increased risk (60% over the interquartile range) of attention deficit hyperactivity disorder (ADHD).

Precursors

Volatile sulfonamide PFOS precursors include N-methyl perfluorooctane sulfonamidoethanol (N-MeFOSE), a carpet stain repellent, and N-ethyl perfluorooctane sulfonamidoethanol (N-EtFOSE), a paper treatment. Perfluorooctanesulfonamide is a precursor. About 50 precursors were named in the 2004 proposed Canadian ban on PFOS. Later, the OECD came up with a document containing a list of 20 pages with potential precursors to PFOS.

Regulation

In May 2009, PFOS was included in Annex B of the Stockholm Convention on persistent organic pollutants by the Fourth Conference of Parties. In 2008 Canada proposed a ban on PFOS, only the second chemical proposed for a complete ban under the Canadian Environmental Protection Act.

Based on an OECD study on PFOS and a risk assessment by Europe's Scientific Committee on Health and Environmental Risks the European Union practically banned the use of PFOS in finished and semi-finished products in 2006 (maximum content of PFOS: 0.005% by weight). However, PFOS use for industrial applications (e.g. photolithography, mist suppressants for hard chromium plating, hydraulic fluids for aviation) was exempted. In 2009 this directive was incorporated into the REACH regulation. In the summer of 2010 PFOS was added to the regulation on persistent organic pollutants and the threshold was lowered to max. 0.001% by weight (10 mg/kg).

See also

• 2005 Hertfordshire Oil Storage Terminal fire
• Fluorocarbons
• Perfluorinated alkylated substances

External links

• Mason Chemical Company, Fluorosurfactant Structure/Function page
• PFOS risk assessment report
• The Environmental Working Group, PFC page
• Centers for Disease Control and Prevention, Polyfluorochemicals fact sheet
• Perfluorinated substances and their uses in Sweden
• Perfluoroalkylated substances, Aquatic environmental assessment
• Chain of Contamination: The Food Link, Perfluorinated Chemicals (PFCs) Incl. PFOS & PFOA
• Provisional evaluation of PFT in drinking water with the guide substances perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) as examples
• OECD Hazard Assessment

• http://Chemspider.com/Chemical-structure.67068.html
• Aziz Ullah. "The Fluorochemical Dilemma: What the PFOS/PFOA fuss is all about" Cleaning & Restoration. www.ascr.org, (October, 2006). Accessed October 25, 2008.
• 3M: "PFOS-PFOA Information: What is 3M Doing?" Accessed October 25, 2008.
• http://www.environment-switzerland.ch/uw-0922-e
• Supporting Information (PDF).
• Peden-Adams et al. (June 2008). In PFAA Days II (PDF). p. 28.
• Environmental Defence: "Stain Repellant Chemical, PFOS, Listed for “Virtual Elimination”" News Release. (April 21, 2008). Accessed October 26, 2008.
• DIRECTIVE 2006/122/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 12 December 2006
• COMMISSION REGULATION (EC) No 552/2009 of 22 June 2009
• COMMISSION REGULATION (EU) No 757/2010 of 24 August 2010