PFOS: Perfluorooctane sulfonate
and
PFOA: Perfluorooctanoic acid
Perfluorinated chemicals
 
 

US EPA's "Children's Environmental Exposure Research Study" (CHEERS) in Jacksonville, Duval County, Florida.
A storm of controversy has engulfed this CHEERS study. The plans to conduct this 2-year study were formally ended on April 8, 2005. It was designed to monitor developmental changes in babies, from birth to age 3, who are exposed to pesticides and household chemicals in their homes. Chemicals include PFOS and PFOA.
See FAN's updates on the controvesy.

About the Teflon chemical PFOA
PFOA is not only used to manufacture Teflon, but is also a breakdown product of chemicals used to coat food packaging, including fast food like McDonald's, and stain-resistant coatings for couches, carpets, and clothing. PFOA is broadly toxic. It does not break down in the environment, and is considered to be persistent over geologic time scales. It nearly universally pollutes human blood and has a half-life in the body of more than four years.
Ref: Environmental Working Group


"The PFOS story is likely to emerge
as one of the apocryphal examples
of 20th century
experimentation

with widespread chemical exposures
: prolific use and almost no testing for safety,
until unexpectedly and almost serendipitously, it is discovered as a contaminant
virtually everywhere. And as is often the case in these stories, the company producing
PFOS products possessed information hinting at its risks but chose not to share their
data with regulators or the public for years..."
Ref: the web home for the authors of Our Stolen Future
http://www.ourstolenfuture.org/NewScience/oncompounds/PFOS/2001-04pfosproblems.htm

"PFOS accumulates to a high degree
in humans and animals. It has an estimated
half-life of 4 years in humans
. It thus appears
to combine
persistence, bioaccumulation, and
toxicity properties to an extraordinary degree
."

Ref: May 16, 2000. Phaseout of PFOS. Charles Auer, USEPA, Director,
Chemical Control Division Office of Pollution Prevention and Toxics (OPPT)

http://www.chemicalindustryarchives.org/dirtysecrets/scotchgard/pdfs/226-0629.pdf#page=

"... As more studies pour in, PFCs [perfluorinatred chemicals]
seem destined to supplant DDT, PCBs, dioxin and other chemicals
as the most notorious, global chemical contaminants ever produced.

Government scientists are especially concerned because unlike any other toxic chemicals,
the most pervasive and toxic members of the PFC family never degrade in the environment.
The U.S. EPA peremptorily forced one member of this family off the market in 2000: PFOS,
the active ingredient used for decades in the original formulation of 3M’s popular Scotchgard
stain and water repellent. Shortly thereafter, 3M also stopped manufacture of a related
perfluorochemical, called PFOA, that is now under intense regulatory pressure at EPA.
3M formerly sold PFOA to DuPont, which has used PFOA for half a century in the manufacture
of Teflon. (DuPont now makes the chemical itself at a new facility in North Carolina.)
Ref:
PFCs: a family of chemicals that contaminate the planet; online report from
the Environmental Working Group - see below under Resources.

Research into the adverse health and ecological effects
of perfluorinated chemicals is in its infancy.

The majority of animal studies were done by 3M, its major producer, and by DuPont, now the major producer of PFOA. DuPont is facing a Class Action lawsuit in Ohio for the contamination of drinking water supplies with the PFOA Ammonium Perfluorooctanoate (commonly known as C8). 3M is also at risk of lawsuits.

The following PFOS and PFOA chemicals, with some exceptions, were used as pesticides or as EPA "Inerts" in pesticide products, until they were phased out of use since the story broke in 2000. The exceptions are that some are still permitted to be used. "Inerts" are used in pesticide products and can account for more than 99% of a pesticide product. US EPA only allows the name of the "active ingredient" in a pesticide to be public information. EPA maintains strict confidentiality on the names of the "inerts" used in specific pesticides and the public is denied the right to know what food crops they are used on, or other products, used in homes, schools, parks, etc, that they are in.
EPA stated in the Dec 9, 2002 Federal Register, that sulfluramid will be phased-out by the year 2016. One rationale EPA cited was that sulfluramid is packaged in child-resistant containers. However, in August 2001, New York State Attorney General Eliot Spitzer, levied the largest pesticide penalty in NY State history - $950,000 - against S.C. Johnson for illegally distributing unsafe sulfluramid roach baits. According to Spitzer.

"This product was marketed for home use and was labeled as child resistant when it was not."
"... According to an EPA assessment, if a child ingested the bait, he or she could suffer irreversible reproductive damage, and boys could be rendered infertile."
Ref: August 22, 2001 Press Release. Office of the New York State
Attorney General Eliot Spitzer.

http://www.fluorideaction.org/pesticides/sulfluramid.largest.fine.01.htm

Activity

CAS No.
Name of Inert used in pesticides Comments

INERT LIST 3

2991-51-7

Potassium N-ethyl-N-
[(heptadecafluorooctyl)sulfonyl] glycinate

EPA calls it:
Glycine, N-ethyl-N- [(heptadecafluorooctyl)sulfonyl]-, potassium salt

See December 9, 2002, Federal Register: FINAL RULE.
Perfluoroalkyl Sulfonates; Significant New Use Rule.

INERT LIST 3

1652-63-7

3-(((Heptadecafluorooctyl)
sulfonyl)amino)-N,N,N- trimethyl-1-
propanaminium iodide

EPA calls it:
1-Propanaminium, 3- [[(heptadecafluorooctyl)sulfonyl]am ino]-N,N,N-trimethyl-, iodide

See December 9, 2002, Federal Register: FINAL RULE.
Perfluoroalkyl Sulfonates; Significant New Use Rule.

US EPA lists this as an active inert in March 2005

PESTICIDE

29457-72-5

Lithium perfluorooctane sulfonate

EPA calls it:
1-Octanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- heptadecafluoro-, lithium salt

See December 9, 2002, Federal Register: FINAL RULE.
Perfluoroalkyl Sulfonates; Significant New Use Rule.

Insecticide

No CAS No.

PAN Data

Perfluorooctane sulfonate

Insecticide
Breakdown product

INERT LIST 3

No CAS No.

2-[Methyl (polyfluoroalkylsulfonyl )
amino]ethyl methacrylate, polym. w. heptyl
methacrylate, butyl methacrylate and N-
methylolacrylamide

These are the names that US EPA used to describe these "inerts".

When it comes to "inerts" EPA generally uses the least common name for a chemical.

In the Federal Registers that pertain to PFAS, EPA used the chemical names as listed in the "
Ninth Collective Index."

These PFAS chemicals cannot be identified in EPA lists published in the Federal Register.

EPA Inert
used as a
Water Repellant
Agent

No CAS No.

2-[Methyl [(perfluoroalkyl)alkyl(C2-
C8)sulfonyl] amino]alkyl(C2-C8)
acrylate„alkyl(C2-C8) methacrylates- N-
methylolacrylamide copolymer

EPA INERT
used as a
Defoaming Agent

No CAS No.

Mono- and bis-(1 H, 1 H,2 H, 2 H-perfluoroalkyl)
phosphates where the alkyl group is even
numbered and in the C6-C12 range

Acaricide
Insecticide

4151-50-2

Sulfluramid

1-Octanesulfonamide, N-ethyl- 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- heptadecafluoro-

See December 9, 2002, Federal Register: FINAL RULE.
Perfluoroalkyl Sulfonates; Significant New Use Rule.

In this Final Rule, EPA states: "All pesticide products containing sulfluramid are under a specific timeline to be phased out by 2016."

Insecticide
Adjuvant

No CAS No.

Potassium N-ethyl perfluoro octane sulfonamide acetate -


FAN's Pesticide Project compilation of

Adverse Effects for PFOS and PFOA

Listed
at this site:
Due to length,
see separate effect pages

Apoptosis - (PFOA)

Bladder -
(PFOS - PFOA)

Endocrine:
Adrenal Gland
-
(PFOS - PFOA)
Breast - (PFOS)
Hypthalamus - (PFOS)
Ovary (Estrous) - (PFOS)
Pancreas
- (PFOS - PFOA)
Prostrate
- (PFOA)
Thymus -
(PFOS - PFOA)
Uterine - (PFOS)

Eye
- (PFOS - PFOA)

Genotoxic
- (PFOA)

Heart -
(PFOS)

Kidney
- (PFOA)
Mesenteric Lymph Nodes - (PFOS)

Salivary Gland
- (PFOS)
Spleen -
(PFOS - PFOA)
Teratogenic
- (PFOS - PFOA)

Body Weight Decrease - (PFOS - PFOA)

Blood - (PFOS - PFOA)

Bone
- (PFOS - PFOA)

Brain
- (PFOS - PFOA)

Cholesterol - (PFOS - PFOA)

Endocrine: Testes
- (PFOS - PFOA)

Endocrine: Thyroid
- (PFOS - PFOA)

G-Protein
- (PFOA)

Liver
- (PFOS - PFOA)

Lung - (PFOS - PFOA)

Reproduction / Developmental

Environmental - (PFOS)

Class Action Suit - (PFOA)

Contaimination Incident - (PFOA)


PFOS

Exposure to PFOS is ubiquitous, found in human and wildlife tissues around the world.

• PFOS is remarkably persistent. For example, PFOS does not show the slightest sign of degradation when boiled in nitric acid for an hour.

• PFOS is known to be toxic in laboratory animals (rats, mice, monkeys) at levels close to the range already found in animals and people in the real world.
Ref: Environmental Science and Technology, report by Rebecca Renner

The biological half-life (t1/2) of perfluorooctanoic acid (PFOA) in male rats is 70 times longer than that in female rats.
Ref: 2002 Chem Biol Interact Mar 20;139(3):301-16. Sex hormone-regulated renal transport of perfluorooctanoic acid; by Kudo N, Katakura M, Sato Y, Kawashima Y.

US EPA uses these terms:

PFAS
to refer to any chain length, including higher and lower homologues as well as C8

PFOS
to represent only those chemicals which are predominantly C8 - with an eight-carbon chain length.

PFAS include PFOSH, PFOSS, POSF, higher and lower homologues of PFOSH and POSF, and certain other chemical substances, including polymers, that are derived from PFOSH and its homologues.

All of the chemical substances listed in EPA's supplemental proposed Significant New Use Rule (SNUR) have the potential to degrade to PFOSH in the environment. Information also suggests that these chemical substances may be converted to PFOSH via incomplete oxidation during the incineration of PFAS-containing materials. Once PFOSH has been released to the environment, it does not undergo further chemical (hydrolysis), microbial, or photolytic degradation. PFOSH is highly persistent in the environment and has a strong tendency to bioaccumulate...
Ref 1. Federal Register. March 11, 2002. Perfluoroalkyl Sulfonates; Proposed Significant New Use Rule. Supplemental proposed rule.


PFOA

In June 2000, EPA indicated that it was expanding its investigation of PFOS to encompass other fluorochemicals, including PFOA, in order to determine whether these other fluorochemicals might present concerns similar to those found with PFOS.

...PFOA is used primarily to produce its salts, which are used as essential processing aids in the production of fluoropolymers and fluoroelastomers.

... PFOA is persistent in the environment. It does not hydrolyze, photolyze, or biodegrade under environmental conditions. Based on recent human biomonitoring data provided by industry, which found PFOA in the blood of workers and the general population in all geographic regions of the United States, exposure to PFOA is potentially nationwide, although the routes of exposure for the general population are unknown.

... APFO [the chemical of concern in the Class Action suit in Ohio] is the most widely used salt of PFOA, and most animal toxicity studies have been conducted with APFO. An extensive array of animal toxicity studies have been conducted in rodents and monkeys. These studies have shown that APFO exposure can result in a variety of toxic effects in animals including liver toxicity, developmental toxicity, and immunotoxicity. In addition, rodent bioassays have shown that chronic APFO exposure is associated with a variety of tumor types. The mechanisms of APFO tumorigenesis are not clearly understood....

... The major fluoropolymers manufactured using PFOA salts are polytetrafluoroethylene (PTFE) and polyvinylidine fluoride (PVDF). PTFE has hundreds of uses in many industrial and consumer products, including soil, stain, grease, and water resistant coatings on textiles and carpet; uses in the automotive, mechanical, aerospace, chemical, electrical, medical, and building/construction industries; personal care products; and non-stick coatings on cookware. PVDF is used primarily in three major industrial sectors: Electrical/electronics, building/construction, and chemical processing.

... PFOA can be commercially manufactured by two major alternative processes: The Simons Electro-Chemical Fluorination (ECF) process, and a telomerization process. Releases from manufacturing processes are one source of PFOA in the environment. Historically, most U.S. production was by 3M using the ECF process. 3M discontinued its manufacture of PFOA between 2000 and 2002, and other domestic producers are using the telomerization process exclusively.

...EPA has also received data which indicate that the 8-2 telomer alcohol... (CAS No. 678-39-7)) although not itself made with PFOA, can be metabolized by living organisms or biodegrade under environmental conditions to produce PFOA (Refs. 8 and 9). Other telomer chemicals have not been tested to determine whether they may also metabolize or degrade to form PFOA. Telomers are used widely in a range of commercial products, including some that are directly released into the environment, such as fire fighting foams, as well as soil, stain, and grease resistant coatings on carpets, textiles, paper, and leather. The extent to which these telomer-containing products might degrade to release PFOA is unknown. However, anecdotal evidence of the atmospheric presence of telomer alcohols in a multi-city North American survey suggests that telomers may be one source of environmental PFOA

The members of the FMG [Fluoropolymer Manufacturing Group] --Asahi Glass Fluoropolymers USA, Inc.; Daikin America, Inc.; E.I. duPont de Nemours & Company; and Dyneon LLC--indicated that they and their parent companies represent most of the known use of APFO for the production of fluoropolymers both in the United States and worldwide.

The members of the TRP [Telomer Research Program] --AGA Chemicals (Asahi Glass); Clariant GmbH; Daikin America, Inc.; and E.I. duPont de Nemours & Company--indicated that they comprise the major telomer producers, and that they are evaluating telomer products sold in the United States to determine whether they contribute to significant human or environmental exposure
to PFOA.

Ref: April 16, 2003. Federal Register. Perfluorooctanoic Acid (PFOA), Fluorinated Telomers; Request for Comment, Solicitation of Interested Parties for Enforceable Consent
Agreement Development, and Notice of Public Meeting. Docket Number
OPPT-2003-0012


The PFOA derivative of greatest concern and most wide spread
use is the ammonium salt (commonly known as C8, C-8, or APFO).
C
AS No: 3825-26-1. The molecular structure is:


Resources:

Class Action lawsuit against Dupont and a local water company in Ohio, for the contamination of drinking water supplies with the PFOA Ammonium perfluorooctanoate (commonly known as C8). The C8 contamination originated from DuPont's Washington Works facility in Wood County, West Virginia.

The Environmental Working Group (EWG) produced an online expose of perfluorochemicals (PFCs) titled: PFCs: a family of chemicals that contaminate the planet. EWG highlighted the PFOS/PFOA issue by associating it with the production of Teflon. They state:

"Teflon itself is not PFOA (C8), but PFOA is used to manufacture Teflon and is released to the air, along with other PFCs, when Teflon cookware is heated to broiling temperatures. PFOA is also emitted to air and water at Teflon manufacturing plants."

EWG's online report provides the most comprehensive online accessibility to studies, data, and reports. The report is available in the following sections:

4 important reports:

PFOS. Nov 21, 2002: Hazard Assessment of Perfluorooctane Sulfonate (PFOS) and its Salts. Organisation for Economic Co-operation and Development (OECD). 362 pages. ENV/JM/RD(2002)17/FINAL

PFOA. April 10, 2003: Preliminary Risk Assessment of the Developmental Toxicity associated with Exposure to Perfluorooctanoic Acid and its Salts. US EPA Office of Pollution Prevention and Toxics. 63 pages.

March 1,2000. Sulfornated Perfluorochemicals in the Environment: Sources, Dispersion, Fate and Effects. Prepared by 3M. This report is part of Federal Register Docket [OPPT-2002-0043] for US EPA's Dec 9, 2002, Final Rule on Perfluoroalkyl Sulfonates; Significant New Use Rule.

3M. February 5, 1999. The Science of Organic Fluorochemistry 12 pages.

Selected Statements, Studies and Reports

US Federal Register : 2000-2003.

After the announcement by 3M to phase-out PFOS chemicals on May 16, 2000, the story is presented to the public through several EPA Notices in the Federal Register. The first was published on October 18, 2000, and provided highly disturbing data on significant severe adverse health effects from animal experiments. It also provided EPA's list of the chemicals to be regulated. As this drama unfolds, EPA extends the comment period on several occasions to accomodate requests from various industries for. The requests for exemptions, from companies in semiconductors, imaging industries (such as Kodak), Boeing, Exxon, etc., are based on the lack of available alternatives. At the end of this 2 year comment period, EPA agrees to the majority of these exemptions, albeit the levels should be greatly reduced compared to what was produced in 2000. See a brief review of the comments EPA received.

Abstracts on PFOS and PFOA for the following years:

Timeline for PFOS and PFOA chemicals

List of Chemicals cited by EPA

Molecular structures for some PFOS / PFOA chemicals

3M produces sulfonated perfluorochemicals by an electrochemical fluorination process. This process creates a complex and variable mix of chemicals in which fluorine atoms replace hydrogen atoms on the organic feedstock and carbon-carbon bonds are rearranged. Because of the carbon-fluorine bond formed by this process, the compounds created are considered to be very stable. Perfluorochernicals have complete substitution of fluorine for hydrogen... Fluorine's high electonegativity confers a strong polarity to carbon-fluorine bonds, contributing to the stability and nonreactive character of perfluorochemical molecules. They are unusual as that perfluoroalkyl chains are both oleophobic and hydrophobic. The addition of charged moieties to the chain may affect the water solubility of the shorter chains.
The highest volume sulfonated pduorochemical produced by 3M is perfluorooctanesulfonyl fluoride (POSF). After synthesis, it is used to create several product lines. During their life cycles, POSF and POSF-based products may degrade. If degradation occurs, current research suggests peduorooctane sulfonate, (PFOS) and a few other perfluorinated forms are degradation products... Degradation of sulfonated perfluorochemicals is not complete but results in production of other fluorochemicals. Studies suggest that compounds made from POSF, a commercially important perfluorochemical product and intermediate, are transformed during metabolism to another sulfonated perfluomchemical, PFOS. PFOS does not appear to further degrade except by incineration.

... The largest production of flurochemicals occurs at the 3M mmufacturing plant in Decatur, Alabama, and this plant is the focus of current studies. During production, many byproductc and waste products are formed. The volatile waste products have been vented to the atmosphere in the past but improvements are underway to capture and destroy these releases by thermal oxidation. The tars are disposed at hazardous waste landfills or treated by incinerattion. The byproducts, many of which are incompletely fluorinated with hydrogen atoms still present, are recycled back into processes or partially degraded in stabilization processes and discharged to wastewater treatment systems. The treatment sludge is landfilled. Some of the non-POSF-based brproducts are recovered and sold for secondary uses.

Note from FAN:
• Oleophobic = [adj] lacking affinity for oils
• Hydrophobic = [adj] lacking affinity for water; tending to repel and not absorb water; tending not to dissolve in or mix with or be wetted by water
• At this time it is not known if incineration "degrades" PFOS chemicals. From what we know it is unlikely that it does.

Table 5. Estimated 1998 Wastes Generated (in PFOS Equivalents) at the Decatur [Alabama] Manufacturing Plant (page 21)
Waste type Estimated PFOS Equivalents, lbs
Air Emissions

19,000

Wastes sent off-site to Incineration

657,000

Wastes sent off-site to Landfills

380,000

Discharge to River after Wastewater Treatment

10,000

Total Wastes

1,066,000

Note: The 10,000 lb/ryr of PFOS equivalents in the discharge to the river are estimated releases to the environment after wastewater treatment, not the lbs/yr generated prior to treatment.

Ref: Sulfornated Perfluorochemicals in the Environment: Sources, Dispersion, Fate and Effects. Prepared by 3M. March 1,2000.

PFOS has been detected at low levels in the blood of humans and wildlife throughout the United States, providing clear evidence of widespread exposure to the chemical. PFOS has been in commercial use since the 1950's, predominantly in soil and stain-resistant coating products on fabrics, carpets, and leather, and in grease and oil resistant coatings on paper products, including food contact papers. Other uses leading to environmental releases include fire fighting foams. The various surface treatment uses constitute the largest volume of PFOS production and are believed to present the greatest potential for widespread human and environmental exposure to PFOS. Studies are underway to determine the routes of exposure which have led to the detection of PFOS in human and animal blood. There are several potential pathways that may account for the widespread exposure to PFOS including: Dietary intake from the consumption of food wrapped in paper containing PFOS derivatives; inhalation from aerosol applications of PFOS-containing consumer products; and inhalation, dietary, or dermal exposures resulting from manufacturing, as well as industrial, commercial, and consumer use and disposal of PFOS-derived chemicals and products.
Ref: October 18, 2000. Federal Register. Perfluorooctyl Sulfonates. Proposed Significant New Use Rule (SNUR).

May 16, 2000 - 3M today announced it is phasing out... perfluorooctanyl (PFOS)
... These include many Scotchguard products, such as soil, oil and water repellent products; coatings used for oil and grease resistance on paper packaging; fire-fighting foams; and specialty components for other products. 3M said it plans to substantially phase out production by the end of the year... "Our decision anticipates increasing attention to the appropriate use and management of persistent materials," said Dr. Charles Reich, executive vice president, Specialty Material Markets.... Sophisticated testing capabilities - some developed in only the last few years -- show that this persistent compound, like other materials in the environment, can be detected broadly at extremely low levels in the environment and in people. All existing scientific knowledge indicastes that the presence of these materials at these very low levels does not pose a human health or environmental risk...
Ref: 3M phasing out some of its specialy materials. 3M press release,

Two 3M plants, located in Decatur, Alabama and Antwerp, Belgium, have produced POSF from electrochemical cell fluorination and then subsequently used POSF to produce various products through polymerization processes. These POSF-based products degrade or metabolize to PFOS. A third manufacturing plant, located in Cottage Grove, Minnesota, has not produced POSF, but has manufactured some POSF-based products...
Ref: Nov 21, 2002: Hazard Assessment of Perfluorooctane Sulfonate (PFOS) and its Salts. Organisation for Economic Co-operation and Development (OECD). 362 pages. ENV/JM/RD(2002)17/FINAL


What is the mechanicism(s) of action of perfluorinated chemicals that make them so biologically active and potent? This is what we need to know and understand. EWG states:

"So far, five different pathways have been identified that might explain how PFOA causes cancer and other types of toxicity. These include

• mitochondrial toxicity;
• cell membrane disruption that results in decreased cell communication;
• peroxisome proliferation;
• increased levels of estrogen and decreased levels of testosterone; and
• decreased thyroid hormone levels."


For the record, a 1983 abstract:

"The acute toxicities of single ip injections of perfluorooctanoic (PFOA) and perfluorodecanoic (NDFDA) acids were evaluated in male Fischer rats... NDFDA has unusually high toxic potency for a perfluorinated hydrocarbon, and some of the toxic effects caused by this acid are remarkably similar to those seen with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The acute toxicity of NDFDA may be due to an ability to interfere with fatty acid metabolism, and studies of its toxicity may be valuable in helping to understand mechanisms of action of TCDD."
Ref: 1983. Toxicol Appl Pharmacol Sep 30;70(3):362-72. The acute toxicity of perfluorooctanoic and perfluorodecanoic acids in male rats and effects on tissue fatty acids; Olson CT, Andersen ME.

 
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