2004 Abstracts

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Abstracts on PFOS and PFOA for the following years:

NOTE: The interest of the FAN Pesticide Project in this issue is directly related to the fact that several PFOS and PFOA chemicals were used as "inerts" in pesticides. However, most, but not all, have been deleted from use since 2001. The so-called "inerts" are used in pesticides and can account for as much as 99%, or more, of a pesticidal formulation. US EPA's policy is to allow the public information only on the "active substance" and to deny the public the names of the chemicals used as "inerts" in specific pesticide products -- even though the majority of inerts are toxic and biologically active.

• See the molecular structure for some of these chemicals

• The following is a selected list of abstracts. For more see PubMed or Toxnet.

Reports mainly:

October 19, 2004.
UK ACTS TO BAN HAZARDOUS CHEMICAL [PFOS and the substances which break down to it]
News Release. UK Department for Environment, Food and Rural Affairs (Defra).

October 2004 (release date)
Environmental Risk Evaluation Report: Perfluorooctanesulphonate (PFOS). by D Brooke, A Footitt, T A Nwaogu. Research Contractor: Building Research Establishment Ltd., Risk and Policy Analysts Ltd. Report produced by the UK Environment Agency's Science Group. (96 pages)
September 2004
Proposal for Regulations on PFOS-Related Substances. Partial Regulatory Impact Assessment
. Prepared for the UK Department for Environment, Food and Rural Affairs (DEFRA). Chemicals and GM Policy Division by Risk & Policy Analysts Ltd. in association with BRE Environment. Project: J454/PFOS RRS. (39 pages)

August 2004
Perfluorooctane Sulphonate. Risk Reduction Strategy and Analysis of Advantages and Drawbacks
. Final Report. Prepared for Department for Environment, Food and Rural Affairs and the Environment Agency for England and Wales. (266 pages)

Environ Sci Technol. 2004 Jul 1;38(13):3698-704.

Automated solid-phase extraction and measurement of perfluorinated organic acids and amides in human serum and milk.

Kuklenyik Z, Reich JA, Tully JS, Needham LL, Calafat AM.

Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, Georgia 30341, USA.

Organic fluorochemicals are used in multiple commercial applications including surfactants, lubricants, paints, polishes, food packaging, and fire-retarding foams. Recent scientific findings suggest that several perfluorochemicals (PFCs), a group of organic fluorochemicals, are ubiquitous contaminants in humans and animals world wide. Furthermore, concern has increased about the toxicity of these compounds. Therefore, monitoring human exposure to PFCs is important. We have developed a high-throughput method for measuring trace levels of 13 PFCs (2 perfluorosulfonates, 8 perfluorocarboxylates, and 3 perfluorosulfonamides) in serum and milk using an automated solid-phase extraction (SPE) cleanup followed by high-performance liquid chromatography-tandem mass spectrometry. The method is sensitive, with limits of detection between 0.1 and 1 ng in 1 mL of serum or milk, is not labor intensive, involves minimal manual sample preparation, and uses a commercially available automated SPE system. Our method is suitable for large epidemiologic studies to assess exposure to PFCs. We measured the serum levels of these 13 PFCs in 20 adults nonoccupationally exposed to these compounds. Nine of the PFCs were detected in at least 75% of the subjects.

Perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS), 2-(N-methylperfluorooctane-sulfonamido)acetate (Me-PFOSA-AcOH), perfluorooctanoate (PFOA), and perfluorononanoate (PFNA) were found in all of the samples. The concentration order and measured levels of PFOS, PFOA, Me-PFOSA-AcOH, and PFHxS compared well with human serum levels previously reported. Although no human data are available for the perfluorocarboxylates (except PFOA), the high frequency of detection of PFNA and other carboxylates in our study suggests that human exposure to long-alkyl-chain perfluorocarboxylates may be widespread. We also found PFOS in the serum and milk of rats administered PFOS by gavage, but not in the milk of rats not dosed with PFOS. Furthermore, we did not detect most PFCs in two human milk samples. These findings suggest that PFCs may not be as prevalent in human milk as they are in serum. Additional studies are needed to determine whether environmental exposure to PFCs can result in PFCs partitioning into milk. Large epidemiological studies to determine the levels of PFCs among the U.S. general population are warranted.

PMID: 15296323 [PubMed - in process]

Environ Sci Technol. 2004 Jun 15;38(12):3316-21.

Degradation of fluorotelomer alcohols: a likely atmospheric source of perfluorinated carboxylic acids.

Ellis DA, Martin JW, De Silva AO, Mabury SA, Hurley MD, Sulbaek Andersen MP, Wallington TJ.

Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada M5S 3H6.

Human and animal tissues collected in urban and remote global locations contain persistent and bioaccumulative perfluorinated carboxylic acids (PFCAs). The source of PFCAs was previously unknown. Here we present smog chamber studies that indicate fluorotelomer alcohols (FTOHs) can degrade in the atmosphere to yield a homologous series of PFCAs. Atmospheric degradation of FTOHs is likely to contribute to the widespread dissemination of PFCAs. After their bioaccumulation potential is accounted for, the pattern of PFCAs yielded from FTOHs could account for the distinct contamination profile of PFCAs observed in arctic animals. Furthermore, polar bear liver was shown to contain predominately linear isomers (>99%) of perfluorononanoic acid (PFNA), while both branched and linear isomers were observed for perfluorooctanoic acid, strongly suggesting a sole input of PFNA from "telomer"-based products. The significance of the gas-phase peroxy radical cross reactions that produce PFCAs has not been recognized previously. Such reactions are expected to occur during the atmospheric degradation of all polyfluorinated materials, necessitating a reexamination of the environmental fate and impact of this important class of industrial chemicals.

PMID: 15260330 [PubMed - in process]

Environ Sci Technol. 2004 Oct 15;38(20):5379-85.

Perfluoroalkyl contaminants in a food web from Lake Ontario.

Martin JW, Whittle DM, Muir DC, Mabury SA.

Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada.

Perfluorooctane sulfonate (PFOS) is a persistent and bioaccumulative perfluorinated acid detectable in humans and wildlife worldwide that has alerted scientists to examine the environmental fate of other fluorinated organic contaminants. Recently a homologous series of perfluoroalkyl carboxylates (PFCAs) was detected in the Arctic, yet little is known about their sources, breadth of contamination, or environmental distribution. In this study we analyzed for PFOS, the homologous series of PFCAs ranging from 8 to 15 carbons in chain length, and the PFOS-precursor heptadecafluorooctane sulfonamide (FOSA) in various organisms from a food web of Lake Ontario. The sampled organisms included a top predator fish, lake trout (Salvelinus namaycush), three forage fish species including rainbow smelt (Osmerus mordax), slimy sculpin (Cottus cognatus), and alewife (Alosa pseudoharengus), and two invertebrates Diporeia (Diporeia hoyi) and Mysis (Mysis relicta). A striking finding was that the highest mean concentration for each fluorinated contaminant was detected in the benthic macroinvertebrate Diporeia, which occupies the lowest trophic level of all organisms analyzed. Perfluorinated acid concentrations in Diporeia were often 10-fold higher than in Mysis, a predominantly pelagic feeder, suggesting that a major source of perfluoroalkyl contaminants to this food web was the sediment, not the water. PFOS was the dominant acid in all samples, but long-chain PFCAs, ranging in length from 8 to 15 carbons, were also detected in most samples between <0.5 and 90 ng/ g. Among Mysis and the more pelagic fish species (e.g. excluding Diporeia and sculpin) there was evidence for biomagnification, but the influence of foraging on highly contaminated Diporeia and sculpin by these fish may have overestimated trophic magnification factors (TMFs), which ranged from 0.51 for FOSA to 5.88 for PFOS. By accounting for the known diet composition of lake trout, it was shown that bioaccumulation was indeed occurring at the top of the food web for all perfluoroalkyl compounds except PFOA. Future monitoring at other locations in Lake Ontario, and in other aquatic environments, is necessary to determine if these food web dynamics are widespread. Archived lake trout samples collected between 1980 and 2001 showed that mean whole body PFOS concentrations increased from 43 to 180 ng/g over this period, but not linearly, and may have been indirectly influenced by the invasion and proliferation of zebra mussels (Dreissena polymorpha) through effects on the population and ecology of forage fishes.

PMID: 15543740 [PubMed - in process]

Environ Sci Technol. 2004 Nov 1;38(21):5522-8.

Analysis of perfluorinated acids at parts-per-quadrillion levels in seawater using liquid chromatography-tandem mass spectrometry.

Yamashita N, Kannan K, Taniyasu S, Horii Y, Okazawa T, Petrick G, Gamo T.

National Institute of Advanced Industrial Science and Technology, 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan.

Perfluorinated acids (PFAs) and their salts have emerged as an important class of global environmental contaminants. Determination of sub-parts-per-trillion or parts-per-quadrillion concentrations of perfluorinated acids in aqueous media has been impeded by relatively high background levels arising from procedural or instrumental blanks. To understand the role of the oceans in the transport and fate of perfluorinated acids, methods to determine ultratrace levels of these compounds in seawater are needed. In this study, sources of procedural and instrumental blank contamination by perfluorinated acids have been identified and eliminated, to reduce background levels in blanks and thereby improve limits of quantitation. The method developed in this study is capable of detecting perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHS), perfluorobutanesulfonate (PFBS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), and perfluorooctanesulfonamide (PFOSA) at low pg/L levels in oceanic waters. PFOA is the major perfluorinated compound detected in oceanic waters, followed by PFOS. Further studies are being conducted to elucidate the distribution and fate of perfluorinated acids in oceans.

Journal of Fluorine Chemistry Volume 125, Issue 8 , August 2004, Pages 1211-1216
Fluorine in Alternative Energy Sources

Nafion® perfluorinated membranes in fuel cells

Shoibal Banerjee (a), , and Dennis E. Curtin (b)

a DuPont Fuel Cells, Chestnut Run Plaza CRP701/213, Wilmington, DE 19805-0701, USA
b DuPont Fuel Cells, 22828 NC Highway 87W, Fayetteville, NC 28306, USA

Abstract: Increasing global energy requirements, localized power issues and the need for less environmental impact are now providing even more incentive to make fuel cells a reality. A number of technologies have been demonstrated to be feasible for generation of power from fuel cells over the last several years. Proton exchange membranes (PEM) have emerged as an essential factor in the technology race. DuPont has supplied Nafion® perfluorinated membranes in fuel cells for space travel for more than 35 years and they have played an integral part in the success of recent work in portable, stationary and transportation applications. The basis for PEM fuel cell emergence and DuPont technology utilization will be discussed.

Excerpt: ... During the period 1977–1984, DuPont invested in building a monomer, polymer, and membrane fabrication plant in Fayetteville NC to meet the needs of the Chloralkali market (Fig. 2 and Fig. 3). Today, the Chloralkali industry is the largest market for our Nafion® products...

Environ Sci Technol. 2004 Dec 15;38(24):6475-81.

Fluorinated organic compounds in an eastern Arctic marine food web.

Tomy GT, Budakowski W, Halldorson T, Helm PA, Stern GA, Friesen K, Pepper K, Tittlemier SA, Fisk AT.

Department of Fisheries & Oceans Canada, 501 University Crescent, Winnipeg, Manitoba R3T2N6, Canada.

An eastern Arctic marine food web was analyzed for
perfluorooctanesulfonate (PFOS, C8F17SO3-),
perfluorooctanoate (PFOA, C7F15COO-),
perfluorooctane sulfonamide (PFOSA, C8F17SO2NH2), and
N-ethylperfluorooctane sulfonamide (N-EtPFOSA, C8F17SO2NHCH2CH3) to examine the extent of bioaccumulation.
PFOS was detected in all species analyzed, and mean concentrations ranged from 0.28 +/- 0.09 ng/g (arithmetic mean +/- 1 standard error, wet wt, whole body) in clams (Mya truncata) to 20.2 +/- 3.9 ng/g (wet wt, liver) in glaucous gulls (Larus hyperboreus).
PFOA was detected in approximately 40% of the samples
analyzed at concentrations generally smaller than those found for PFOS; the greatest concentrations were observed in zooplankton (2.6 +/- 0.3 ng/g, wet wt).
N-EtPFOSA was detected in all species except redfish with mean concentrations ranging from 0.39 +/- 0.07 ng/g (wet wt) in mixed zooplankton to 92.8 +/- 41.9 ng/g (wet wt) in Arctic cod (Boreogadus saida). This is the first report of N-EtPFOSA in Arctic biota.
PFOSA was only detected in livers of beluga (Delphinapterus leucas) (20.9 +/- 7.9 ng/g, wet wt) and narwhal (Monodon monoceros) (6.2 +/- 2.3 ng/g, wet wt), suggesting that N-EtPFOSA and other PFOSA-type precursors are likely present but are being biotransformed to PFOSA.
A positive linear relationship was found between PFOS concentrations (wet wt) and trophic level (TL), based on delta15N values, (r2 = 0.51, p < 0.0001) resulting in a trophic magnification factor of 3.1. TL-corrected biomagnification factor estimates for PFOS ranged from 0.4 to 9. Both results indicate that PFOS biomagnifies in the Arctic marine food web when liver concentrations of PFOS are used for seabirds and marine mammals. However, transformation of N-EtPFOSA and PFOSA and potential other perfluorinated compounds to PFOS may contribute to PFOS levels in marine mammals and may inflate estimated biomagnification values. None of the other fluorinated compounds (N-EtPFOSA, PFOSA, and PFOA) were found to have a significant relationship with TL, but BMF(TL) values of these compounds were often >1, suggesting potential for these compounds to biomagnify. The presence of perfluorinated compounds in seabirds and mammals provides evidence that trophic transfer is an important exposure route of these chemicals to Arctic biota.

PMID: 15669302 [PubMed - in process]

Environ Sci Technol. 2004 Dec 1;38(23):452A.

No Abstract available

Canada moves to eliminate PFOS stain repellents.

Pelley J.

PMID: 15597866 [PubMed - in process]

Environ Sci Technol. 2004 Nov 1;38(21):5522-8.

Analysis of perfluorinated acids at parts-per-quadrillion levels in seawater using liquid chromatography-tandem mass spectrometry.

Yamashita N, Kannan K, Taniyasu S, Horii Y, Okazawa T, Petrick G, Gamo T.

National Institute of Advanced Industrial Science and Technology, 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan.

Perfluorinated acids (PFAs) and their salts have emerged as an important class of global environmental contaminants. Determination of sub-parts-per-trillion or parts-per-quadrillion concentrations of perfluorinated acids in aqueous media has been impeded by relatively high background levels arising from procedural or instrumental blanks. To understand the role of the oceans in the transport and fate of perfluorinated acids, methods to determine ultratrace levels of these compounds in seawater are needed. In this study, sources of procedural and instrumental blank contamination by perfluorinated acids have been identified and eliminated, to reduce background levels in blanks and thereby improve limits of quantitation. The method developed in this study is capable of detecting perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHS), perfluorobutanesulfonate (PFBS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), and perfluorooctanesulfonamide (PFOSA) at low pg/L levels in oceanic waters. PFOA is the major perfluorinated compound detected in oceanic waters, followed by PFOS. Further studies are being conducted to elucidate the distribution and fate of perfluorinated acids in oceans.

PMID: 15575267 [PubMed - in process]

Environ Sci Technol. 2004 Nov 15;38(22):6118-24.

Decomposition of environmentally persistent perfluorooctanoic acid in water by photochemical approaches.

Hori H, Hayakawa E, Einaga H, Kutsuna S, Koike K, Ibusuki T, Kiatagawa H, Arakawa R.

National Institute of Advanced Industrial Science and Technology, 16-1 Onogawa, Tsukuba 305-8569, Japan.

The decomposition of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water by UV-visible light irradiation, by H202 with UV-visible light irradiation, and by a tungstic heteropolyacid photocatalyst was examined to develop a technique to counteract stationary sources of PFOA. Direct photolysis proceeded slowly to produce CO2, F-, and short-chain perfluorocarboxylic acids. Compared to the direct photolysis, H2O2 was less effective in PFOA decomposition. On the other hand, the heteropolyacid photocatalyst led to efficient PFOA decomposition and the production of F- ions and CO2. The photocatalyst also suppressed the accumulation of short-chain perfluorocarboxylic acids in the reaction solution. PFOA in the concentrations of 0.34-3.35 mM, typical of those in wastewaters after an emulsifying process in fluoropolymer manufacture, was completely decomposed by the catalyst within 24 h of irradiation from a 200-W xenon-mercury lamp, with no accompanying catalyst degradation, permitting the catalyst to be reused in consecutive runs. Gas chromatography/mass spectrometry (GC/MS) measurements showed no trace of environmentally undesirable species such as CF4, which has a very high global-warming potential. When the (initial PFOA)/(initial catalyst) molar ratio was 10: 1, the turnover number for PFOA decomposition reached 4.33 over 24 h of irradiation.

PMID: 15573615 [PubMed - in process]

Drug Chem Toxicol. 2004 Nov;27(4):361-78.

13-week dietary toxicity study of ammonium perfluorooctanoate (APFO) in male rats.

Perkins RG, Butenhoff JL, Kennedy GL Jr, Palazzolo MJ.

3M Medical Department, Corporate Toxicology, St. Paul, MN 55144, USA.

Ammonium perfluorooctanoate is a perfluorinated carboxylate that is used commercially as a processing aid in the production of fluorinated polymers. Perfluorooctanoate (PFOA) has been found in human blood of the general population from exogenous sources. This report presents the results of a 13-week dietary toxicity study in male rats and was designed to identify potential target organ(s), dose response, and to explore possible relationships of PPARalpha activation to potential liver effects and hormonal changes. Rats were fed dietary levels of 0, 1, 10, 30, and 100 ppm (equivalent to 0, 0.06, 0.64, 1.94, and 6.5 mg/kg/day) for 13 weeks. A control group pair-fed adjusted to the 100 ppm level and groups allowed to recover for 8 weeks were included. Sacrifices were conducted after 4, 7, and 13 weeks of feeding and after 8 weeks of recovery. At each sacrifice, gross and histopathology was conducted on selected tissues and measurements of hepatic palmitoyl CoA oxidase (PCoAO), as well as serum estradiol, luteinizing hormone, testosterone, and PFOA were determined. There were no clinical signs or mortality. Body weight gains were reduced in the 100 ppm dose group. Liver weights (absolute and relative), PCoAO activity, and hepatocyte hypertrophy (minimal to mild) were increased in the 10 ppm dose group and above and were reversible in recovery. Under the study conditions, hormone levels appeared unchanged. PFOA serum concentrations increased in a dose-related fashion, appeared to reach steady-state by test week 5, and declined rapidly through the recovery period. Serum PFOA concentrations at the end of the treatment period were 7.1, 41, 70, and 138 microg/mL in the 1, 10, 30 and 100 ppm dose groups. The study no effect level was 1 ppm (0.06 microg/mg) with doses of 10 ppm (0.64 microg/mg) and higher producing adaptive and reversible liver changes.

PMID: 15573472 [PubMed - in process]

Drug Chem Toxicol. 2004 Nov;27(4):341-60.

Binding of perfluorooctanoic acid to rat liver-form and kidney-form alpha2u-globulins.

Han X, Hinderliter PM, Snow TA, Jepson GW.

DuPont Haskell Laboratory for Health and Environmental Sciences, Newark, Delaware 19714, USA.

Perfluorooctanoic acid (PFOA) is an organic fluorochemical and is reported to have a long half-life in human blood. Its urinary elimination in rats is markedly sex-dependent, and characterized by significantly longer plasma half-life of PFOA in male rats than in females. It has been postulated that male-specific PFOA binding protein(s) is responsible for the long half-life of PFOA in male rats. In this paper, two male rat specific proteins, liver- and kidney-form alpha2u-globulins (A2U(L) and A2U(K)), were purified from male rat urine and kidney, respectively. The binding of these two nroteins to PFOA was investigated using ligand blotting, electrospray ionization mass spectrometry and fluorescence competitive binding assay. The results revealed that both A2U(L) and A2U(K) were able to bind PFOA in vitro under physiological conditions, and that PFOA and a fluorescent-labeled fatty acid shared the same binding site on both A2U(L) and A2U(K). The binding affinities, however, are relatively weak. The estimated dissociation constants are in the 10(-3) M range, indicating that bindings of PFOA to either A2U(L) or A2U(K) cannot adequately explain the sex-dependent elimination of PFOA in rats, and it is unlikely that PFOA-A2U(K) binding would induce A2U nephropathy as seen with, for example, 1,4-dichlorobenzene.

PMID: 15573471 [PubMed - in process]

Environ Toxicol Chem. 2004 Nov;23(11):2745-55.

Partial life-cycle toxicity and bioconcentration modeling of perfluorooctanesulfonate in the northern leopard frog (Rana pipiens).

Ankley GT, Kuehl DW, Kahl MD, Jensen KM, Butterworth BC, Nichols JW.

US Environmental Protection Agency, Office of Research and Development, National Health and Environmental Effects Research Laboratory, Mid-Continent Ecology Division, Duluth, Minnesota 55804, USA.

A number of recent monitoring studies have demonstrated elevated concentrations of perfluorooctanesulfonate (PFOS) in humans and wildlife throughout the world. Although no longer manufactured in the United States, the global distribution and relative persistence of PFOS indicates a need to understand its potential ecological effects. Presently, little is known concerning toxicity of PFOS in chronic exposures with aquatic species. Therefore, we evaluated the effects of PFOS on survival and development of the northern leopard frog (Rana pipiens) from early embryogenesis through complete metamorphosis. Exposures were conducted via water at measured PFOS concentrations ranging from 0.03 to 10 mg/L. Animals exposed to 10 mg/L began dying within approximately two weeks of test initiation. Survival was not affected by PFOS at lower concentrations; however, time to metamorphosis was delayed and growth reduced in the 3-mg/L treatment group. Tadpoles readily accumulated PFOS directly from water. Using a one-compartment bioaccumulation model, growth was shown to have a modest impact on steady-state PFOS concentrations. Variability in observed growth rates and the possible contribution of a size-dependent decrease in PFOS elimination rate contributed uncertainty to modeling efforts. Nevertheless, fitted uptake and elimination rate constants were comparable to those determined in earlier studies with juvenile rainbow trout. Overall, our studies suggest that R. pipiens is not exceptionally sensitive to PFOS in terms of either direct toxicity or bioconcentration potential of the chemical.

PMID: 15559291 [PubMed - in process]

Water Sci Technol. 2004;50(5):235-42.

Perfluorooctane sulfonate--a quite mobile anionic anthropogenic surfactant, ubiquitously found in the environment.

Meesters RJ, Schroder HF.

Institut fur Siedlungswasserwirtschaft, Aachen University, Templergraben 55, D-52056 Aachen, Germany.

The biochemical degradation of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) under aerobic and anaerobic conditions in closed-loop systems was monitored in laboratory scale. Adsorptive effects of these compounds to glass and polypropylene were also examined. Liquid chromatography/mass spectrometry (LC-MS) under negative electrospray (ESI(-)) conditions was applied for determination. Elimination of PFOS was observed under anaerobic conditions whereas aerobic treatment was not effective.

PMID: 15497853 [PubMed - in process]

Environ Sci Technol. 2004 Sep 1;38(17):4489-95.

Perfluorooctanesulfonate and related fluorochemicals in human blood from several countries.

Kannan K, Corsolini S, Falandysz J, Fillmann G, Kumar KS, Loganathan BG, Mohd MA, Olivero J, Van Wouwe N, Yang JH, Aldoust KM.

Wadsworth Center, New York State Department of Health, and Department of Environmental Toxicology and Health, State University of New York, Empire State Plaza, P.O. Box 509, Albany, New York 12201-0509, USA.

Perfluorooctanesulfonyl fluoride based compounds have been used in a wide variety of consumer products, such as carpets, upholstery, and textiles. These compounds degrade to perfluorooctanesulfonate (PFOS), a persistent metabolite that accumulates in tissues of humans and wildlife. Previous studies have reported the occurrence of PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), and perfluorooctanesulfonamide (PFOSA) in human sera collected from the United States. In this study, concentrations of PFOS, PFHxS, PFOA, and PFOSA were measured in 473 human blood/serum/plasma samples collected from the United States, Colombia, Brazil, Belgium, Italy, Poland, India, Malaysia, and Korea. Among the four perfluorochemicals measured, PFOS was the predominant compound found in blood. Concentrations of PFOS were the highest in the samples collected from the United States and Poland (>30 ng/mL); moderate in Korea, Belgium, Malaysia, Brazil, Italy, and Colombia (3 to 29 ng/mL); and lowest in India (<3 ng/mL). PFOA was the next most abundant perfluorochemical in blood samples, although the frequency of occurrence of this compound was relatively low. No age- or gender-related differences in the concentrations of PFOS and PFOA were found in serum samples. The degree of association between the concentrations of four perfluorochemicals varied, depending on the origin of the samples. These results suggested the existence of sources with varying levels and compositions of perfluorochemicals, and differences in exposure patterns to these chemicals, in various countries. In addition to the four target fluorochemicals measured, qualitative analysis of selected blood samples showed the presence of other perfluorochemicals such as perfluorodecanesulfonate (PFDS), perfluoroheptanoic acid (PFHpA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid (PFDoA), and perfluoroundecanoic acid (PFUnDA) in serum samples, at concentrations approximately 5- to 10-fold lower than the concentration of PFOS. Further studies should focus on identifying sources and pathways of human exposure to perfluorochemicals.

PMID: 15461154 [PubMed - in process]

Wei Sheng Yan Jiu. 2004 Jul;33(4):481-3.

[Status of perfluorochemicals in adult serum and umbilical blood in Shenyang]

[Article in Chinese]

Jin Y, Liu X, Li T, Qin H.

Institute of Public Hygiene, China Medical University, Shenyang 110001, China.

OBJECTIVE: To study the status of perfluorooctane sulfonate (PFOS), and Perfluorooctanoic acid (FOA) pollution in serum and umbilical blood among general people in Shenyang area.
METHODS: Concentration of PFOS and PFOA in adult serum and umbilical blood samples was measured by means of liquid phase chromatography/mass spectrograph selective iron monitoring (PFOS: m/z = 499, PFOA: m/z = 413).
RESULTS: It was showed that geometric mean of serum concentration of PFOS of male was 40.73microg/L and that of female was 45.46microg/L, PFOA is 11.53microg/L and 8.97microg/L. Geometric mean concentration of PFOS and PFOA in umbilical blood was 2.214microg/L and 0.264microg/L. There was no correlativity between concentration of PFOS, PFOA and age in adult serum and umbilical blood.
CONCLUSION: It was suggested that there was PFOS contamination in common group in Shenyang. Also, fetus was exposed in PFOS and PFOA during its embryonic period. There were also PFOS and PFOA pollution in human umbilical blood samples.

PMID: 15461284 [PubMed - in process]

Toxicol Sci. 2004 Oct 6 [Epub ahead of print]
Pharmacokinetics of Perfluorooctanoate (PFOA) in Cynomolgus Monkeys.

Butenhoff JL, Kennedy GL Jr, Hinderliter PM, Lieder PH, Jung R, Hansen KJ, Gorman GS, Noker PE, Thomford PJ.

3M, St. Paul, Minnesota 55144.

The pharmacokinetics of perfluorooctanoate (PFOA) in cynomolgus monkeys were studied in a six-month oral capsule dosing study of ammonium perfluorooctanoate (APFO) and in a single-dose intravenous (iv) study. In the oral study, samples of serum, urine, and feces were collected every two weeks from monkeys given daily doses of either 0, 3, 10, or 20 mg APFO/kg. Steady-state was reached within 4 weeks in serum, urine, and feces. Serum PFOA followed first-order elimination kinetics after the last dose, with a half-life of approximately 20 days. Urine was the primary elimination route. Mean serum PFOA concentrations at steady state in the 3, 10, and 20 mg/kg-day dose groups, respectively, were: 81, 99, and 156 microg/ml in serum; 53, 166, and 181 microg/ml in urine; and, 7, 28, and 50 mg/g in feces. Mean liver concentrations reached 16, 14, and 50 mg/g in the 3, 10, and 20 mg/kg groups, respectively. In the iv study, 3 monkeys per sex were given a single dose of 10 mg/kg potassium PFOA. Samples were collected through 123 days. The terminal halflife of PFOA in serum was 13.6, 13.7, and 35.3 days in the 3 male monkeys and 26.8, 29.3, and 41.7 days in the 3 females. Volume of distribution at steady state was 181 +/- 12 and 198 +/- 69 mL/kg for males and females, respectively. Based on the result of both the oral and iv studies, the elimination half-life is approximately 14-42 days, and urine is the primary route of excretion.

PMID: 15470233 [PubMed - as supplied by publisher]

Environ Toxicol Chem. 2004 Sep;23(9):2116-23.

Toxicity of perfluorooctane sulfonic acid and perfluorooctanoic acid to Chironomus tentans.

MacDonald MM, Warne AL, Stock NL, Mabury SA, Solomon KR, Sibley PK.

Department of Environmental Biology, University of Guelph, Guelph, Ontario N1G 2W1, Canada.

Two perfluorinated surfactants, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), were evaluated for their toxicity to the aquatic midge, Chironomus tentans. Impetus for this laboratory study originated from a 10-d, in situ field assessment in which C. tentans was exposed to PFOS at concentrations ranging from 300 to 30,000 microg/L. No midges survived these exposures. Midge survival in a preliminary, acute 10-d laboratory test with nominal PFOS concentrations ranging from 0.1 to 100,000 microg/L showed similar toxicity with respect to survival (median lethal concentration [LC50], 45.2 microg/L) and growth (median effective concentration [EC50], 27.4 microg/L). A parallel test using PFOA indicated no significant impacts on survival or growth. A definitive 10-d assay with PFOS concentrations ranging from 1 to 150 microg/L produced an EC50 for growth (87.2+/-11.6 microg/L) of the same order of magnitude as that in the preliminary findings. The same was not true for survival, however, with the LC50 falling outside the range of test concentrations. To further investigate the sensitivity of C. tentans to PFOS, we conducted a chronic life-cycle test using a nominal concentration range of 1 to 100 microg/L. Three of the four endpoints measured-survival, growth, and emergence-were significantly affected, with EC50 values of 92.2+/-3.1, 93.8+/-2.6, and 94.5+/-3.2 microg/L, respectively. Reproduction was not affected by those PFOS concentrations at which females emerged. The results of the present study indicate that PFOS toxicity thresholds for C. tentans are as much as three orders of magnitude lower than those reported for other aquatic organisms but, at present, are approximately two orders of magnitude higher than those concentrations typically observed in aquatic environments.

PMID: 15378987 [PubMed - in process]

Environ Toxicol Chem. 2004 Aug;23(8):1912-9.

Impact of perfluorooctanoic acid on fathead minnow (Pimephales promelas) fatty acyl-CoA oxidase activity, circulating steroids, and reproduction in outdoor microcosms.

Oakes KD, Sibley PK, Solomon KR, Mabury SA, Van der Kraak GJ.

Department of Zoology, University of Guelph, Guelph, Ontario N1G 2W1, Canada.

This study investigates reproductive impairment and biochemical changes in fathead minnow (Pimephales promelas) exposed for 39 d to varying concentrations of perfluorooctanoic acid (PFOA) under microcosm conditions. While the concentrations tested in this study were much higher than those normally found in the environment, no mortality was associated with PFOA exposure. Only modest changes were observed in condition factor and in relative liver and gonad size. Significant declines in circulating plasma steroids were observed, but these were accompanied by only limited increases in time to first oviposition and decreases in overall egg production. Peroxisome proliferation, as quantified by fatty acyl-CoA oxidase (FAO) activity, was elevated with low PFOA concentrations but attenuated with exposure to higher PFOA doses. Little evidence was seen of differential induction of peroxisome-associated enzyme activity with sex. Oxidative stress, as quantified by the 2-thiobarbituric acid reactive substances (TBARS) assay, was only modestly influenced by PFOA exposure and is not a significant consequence of FAO activity in fathead minnow. Perfluorooctanoic acid appears to be relatively nontoxic at environmentally relevant concentrations but may impact biochemical and reproductive endpoints under conditions associated with environmental spills.

PMID: 15352480 [PubMed - in process]

Environ Sci Technol. 2004 Aug 1;38(15):4064-70.

Detection of perfluorooctane surfactants in Great Lakes water.

Boulanger B, Vargo J, Schnoor JL, Hornbuckle KC.

University of Iowa, Department of Civil and Environmental Engineering, SC 4105, Iowa City, Iowa 52240, USA.

Widespread use of perfluorooctane surfactants has led to ubiquitous presence of these chemicals in biological tissues. While perfluorooctane surfactants have been measured in blood and liver tissue samples of fish, birds, and mammals in the Great Lakes region, data for the aqueous concentrations of these compounds in the Great Lakes or other ambient waters is lacking. Sixteen Great Lakes water samples were analyzed for eight perfluorooctane surfactants. The monitored perfluorooctane surfactants were quantitatively determined using single quadrupole HPLC/MS and qualitatively confirmed using ion trap MS/MS. Additionally, PFOS was quantitatively confirmed using triple quadrupole LC/MS/MS. Concentrations of PFOS and PFOA in the two lakes ranged from 21-70 and 27-50 ng/L, respectively. Analysis also showed the presence of PFOS precursors, N-EtFOSAA (range of 4.2-11 ng/L) and FOSA (range of 0.6-1.3 ng/L), in all samples above the LOQ. PFOSulfinate, another precursor, was identified at six of eight locations with a concentration range, when present, of <2.2-17 ng/L. Other PFOS precursors, N-EtFOSE, PFOSAA, and N-EtFOSA were not observed at any of the sampling locations. These are the first reported concentrations of perfluorooctane surfactants in Great Lakes water and the first report of PFOS precursors in any water body.

PMID: 15352442 [PubMed - in process]

Environ Sci Technol. 2004 Aug 1;38(15):4056-63.

Perfluorinated compounds in coastal waters of Hong Kong, South China, and Korea.

So MK, Taniyasu S, Yamashita N, Giesy JP, Zheng J, Fang Z, Im SH, Lam PK.

Centre for Coastal Pollution and Conservation, Department of Biology and Chemistry, City University of Hong Kong.

Perfluorinated compounds (PFCs), such as perfluorooctanesulfonate (PFOS) and related compounds, have recently been identified in the environment. PFOS, the terminal degradation product of many of the PFCs, has been found globally in many wildlife species, as well as open ocean waters, even in remote regions far from sources. In this study, a solid-phase extraction procedure coupled with high-performance liquid chromatography interfaced to high-resolution mass spectrometry was used to isolate, identify, and quantify small concentrations of PFCs in seawater. These techniques were applied to investigate the local sources of PFCs in several industrialized areas of Asia and provide information on how the PFCs are circulated by coastal currents. Ranges of concentrations of PFOS in coastal seawaters of Hong Kong, the Pearl River Delta, including the South China Sea, and Korea were 0.09-3.1, 0.02-12, and 0.04-730 pg/mL, respectively, while those of perfluorooctanoic acid (PFOA) were 0.73-5.5, 0.24-16, and 0.24-320 pg/mL, respectively. Potential sources of PFCs include major industrialized areas along the Pearl River Delta of southern China and major cities of Korea, which are several of the fastest growing industrial and economic regions in the world. Detectable concentrations of PFOS and PFOA in waters of southern China were similar to those in the coastal marine environment of Japan and certain regions in Korea. Concentrations of PFCs in several locations in Korean waters were 10-100-fold greater than those in the other locations on which we report here. The spatial and seasonal variations in PFC concentrations in surface seawaters in the Pearl River Delta and South China Sea indicate the strong influence of the Pearl River discharge on the magnitude and extent of PFC contamination in southern China. All of the concentrations of PFOS were less than those that would be expected to cause adverse effects to aquatic organisms or their predators except for one location in Korea adjacent to an industrialized area. Hazard quotients were from <0.001 to 0.002 for aquatic animals and ranged from <0.001 to 17 for predatory birds.

PMID: 15352441 [PubMed - in process]

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4004-4008.

Perfluorinated compounds in human serum and seminal plasma from an urban and rural population in Sri Lanka

Keerthi Guruge (1), Sachi Taniyasu (2), Nobuyoshi Yamashita (2), Shigeru Miyazaki (1),
Noriko Yamanaka (1), Sumedha Wijeratna (3), Harsha Seneviratne (3)

1 National Institute of Animal Health, Tsukuba, Japan
2 National Institute of Advance Industrial and Technology, Tsukuba, Japan
3 University of Colombo, Colombo, Sri Lanka
4 Tea Research Institute of Sri Lanka, Talawakele, Sri Lanka

Introduction. Fluorinated organic compounds (FOCs) have been used for variety of industrial applications such as surfactants, adhesives, insecticides, and their global production increase since 1970s. These compounds repel both water and oil. The high-energy carbon-fluorine covalent bonds in FOCs are strong enough to have high persistency in the environment. These compounds emerged as priory environmental pollutants since they are found in various biota throughout the world.1-2 Human contamination of some FOCs was reported mostly in developed countries such as USA, Japan and from Europe.3--7 In the present study, we report 10 FOCs in human serum including seminal plasma for the first time, collected from volunteers from Sri Lanka ...
... We observed an increasing trend of PFOS and PFOA accumulation between seminal plasma and sera (Figures 3 & 4), while no age trend.
The accumulation of PFOS in sera was positively correlated with PFHS, PFNA, PFUnA and PFOA suggesting that these compounds have similar accumulation properties (Figure 5) in human body fluids.
All the FOCs concentrations in sera and seminal plasma in urban location were significantly higher than those from the rural location. The greater exposure levels found in Colombo revealed that wide variety of applications with perfluoroalkylated compound such as paper, packing products, carpet spray, stain-resistant textiles, cosmetics, electronics and fire-fighting foams, are readily existing for urban community compared to the rural population in Sri Lanka
Overall, these data are indicated that human contamination of FOCs was widespread even in developing countries similar to those in industrialized ones. Exposure to organohalogen compounds may be associated with human reproductive failiers.8 Several FOC compounds were found in seminal plasma have long half-lives (> 1 year) suggesting that those compounds might pose adverse health effects including male fertility associated with long-term exposure. Since these compound had greater accumulations in higher trophic positions, they should be considered in future risk assessments of chemical exposure in human.

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4058-4062.


Anna Kärrman (1), Bert van Bavel (1), Ulf Järnberg (2), Lennart Hardell (1), Gunilla Lindström (1)

1 Man-Technology-Environment Research Centre, Örebro University
2 Institute of Applied Environmental Research, Stockholm University

Introduction. Historically the reports on perfluoroalkylated (PFA) compounds have been limited to mainly perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) but recently a number of other, potentially bioaccumulating, perfluorinated acids were reported in wildlife and in human blood (1,2,3,4). PFOS is the PFA compound that has been reported most frequently and in the < 1-82 pg/µl range in human serum from the general population of several countries (5,6,7,8). PFOS and its salts represents only a fraction of the total fluoroproduction but can occur as an impurity in other products and is suspected to be the stable degradation product from other perfluorinated compounds, for example derivatives of perfluorooctane sulfonamide (PFOSA) (9,10). Recent studies indicate that more volatile fluorotelomer alcohols (FTOHs) and sulfonamidoethanols can degrade biotic to different PFA compounds (11). FTOHs and sulfonamidoalcohols are used in both industrial and household applications and have been found in the trophospere (12). Since possible degradation pathways, distribution and exposure routes for this group of compounds are still under investigation; information of human exposure to a larger number of PFAs is valuable. In this study we analysed 66 whole blood samples from the Swedish general population with respect to 12 perfluorinated sulfonates and carboxylates (including perfluorooctane sulfonamide) with carbon chain length between 4 and 14 ...
... Discussion. The results shows that the Swedish population is exposed to a large number of PFAs in conformity with the study performed on European parliament members
(4). The concentrations of PFOS (18.2 pg/µl) and PFOA (2.9 pg/µl) in whole blood samples from Sweden are about a factor two lower than previously reported (34.9 and 4.6 pg/µl respectively) in serum samples of the USA population (13). Assuming that PFAs bind to plasma proteins (14,15) and that whole blood consist of about 50% plasma, the concentrations of PFOS and PFOA in the general population from Sweden and USA can be regarded as similar. The relationship between different compounds was studied in order to find eventual exposure patterns. The association between PFOS and PFOA was strongest (R 2 0,3-0,5), demonstrated in Figure 1. ...

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4035-4040.


Sachi Taniyasu (1), Nobuyoshi Yamashita (1), Kurunthachalam Kannan (2), Yuichi Horii (1), Ewan Sinclair (2), Gert Petrick (3), Toshitaka Gamo 4

1 National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba
2 Wadsworth Center, New York State Department of Health, Albany
3 Institute for Marine Research, University of Kiel, Kiel
4 Ocean Research Institute, University of Tokyo, Tokyo

... Our studies have shown that part per quadrillion (ppq) level analysis of PFCs is necessary to obtain reliable information of open ocean pollution ...
Results and Discussion. Table 1 shows the concentration of PFOS, PFHS, PFNA, and PFOA in open ocean water samples from the Pacific and Atlantic Oceans and several coastal seawaters from Asian countries. PFOS and PFOA were found in 80% of the surface seawater and some regions showed characteristic composition of PFCs. There were some similarities between PFCs composition in coastal and open ocean waters in some regions. It appeared that the hydrologic information such as tidal and/or water current was necessary to explain the discharge of PFCs from coastal water to open ocean.
Relatively high concentrations of PFOS, PFHS, and PFOA were detected in Tokyo Bay waters. PFOA is the predominant fluorochemical, ranging in concentration from 1,800 – 192,000 pg/L, followed by PFOS (338 - 57,700 pg /L). Concentration of PFHS was an order of magnitude lower than the concentration of PFOS. High concentrations of PFCs in Tokyo Bay waters suggest sources associated with urban and industrial areas in Tokyo. The higher concentration of PFOA than of PFOS in water samples is an interesting observation. In wildlife samples collected from several locations, PFOS was the predominant compound, rather than PFOA (2). This discrepancy suggests that the bioaccumulation potential of PFOA is relatively lower than that of PFOS.
Concentrations of PFOS, PFHS, PFOA, and PFOSA in offshore waters of the Pacific Ocean were approximately three orders of magnitude lower than those in Tokyo Bay. Concentrations of all of the target fluorochemicals in offshore waters were in the pg/L range. Similar to what was observed for coastal waters, PFOA was the predominant fluorochemical found in the offshore waters of Japan. Variability in the concentrations of PFOA or PFOS in offshore waters was rather lower than for coastal waters, suggesting a generalized source such as atmospheric or hydrospheric transport. PFOSA was also found in these samples, at concentrations comparable to those of PFHS.
Open-ocean water samples collected in the mid-Atlantic Ocean showed the presence of all target PFCs at pg/L levels. Concentrations of PFOA and PFOS were comparable to those in offshore waters collected in the South China and Sulu Seas. The concentrations of PFOA and PFOS in the central to eastern Pacific Ocean waters were from 15 to 62 and 1.1 to 20 pg/L, respectively. These concentrations were an order of magnitude lower than concentrations in offshore waters, and four orders of magnitude lower than concentrations in Tokyo Bay water. These values appear to be the background values for remote marine waters far from local sources. Figure 4 illustrates the spatial trend of PFOS, PFHS, and PFOA from coastal Japan to the central Pacific Ocean. Concentrations of PFCs decreased dramatically by 2-4 orders of magnitude from coastal area to the offshore area.
It appears that PFOA pollution is more ubiquitous than PFOS in oceanic waters. This may be similar to trifluoroacetic acid (TFA) pollution in oceans. Scott et al. reported widespread distribution of TFA in open ocean waters (6). Our result suggests that several perfluorinated acids are following similar environmental dynamics as TFA.
The other aim of our survey is to understand three-dimensional distribution of PFCs in marine environment. Although the marine environment is three-dimensional, very few studies have investigated persistent organic pollutants (POPs) including PFCs in deep seawaters. We have collected more than thirty deep seawater samples from the above mentioned locations and detected some PFCs. Presence of PFCs in deep-sea water shows the need for comprehensive survey of not only surface water but also vertical profile of PFCs in water column as well as open ocean air. Deep-sea water samples, collected at depths of >1000 m in the Pacific Ocean and the Sulu Sea contained trace levels of PFOS and PFOA. The deep seas play a major role in the dynamics of several POPs and therefore their role in the global fate of PFCs must be examined.

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4063-4068.


Nobuyoshi Yamashita (1), Kurunthachalam Kannan (2), Sachi Taniyasu (1), Yuichi Horii (1), Nobuyasu Hanari (1), Tsuyoshi Okazawa (1), Gert Petrick (3)

1 National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba
2 Wadsworth Center, New York State Department of Health, Albany
3 Institute for Marine Research, University of Kiel, Kiel

Introduction. On September 26, 2003, a magnitude (M) 8.3 offshore earthquake struck Hokkaido, Japan. The earthquake and ensuing tsunami injured hundreds of people and resulted in significant damage to port and coastal communities. Immediately following the earthquake, a major fire occurred at an oil storage facility of a refinery (Idematsu Kosan Company Ltd) located in the west part of Tomakomai, a Pacific coast city in southern Hokkaido. Idemitsu Kosan Company is the second largest oil refinery in Japan, with a capacity of 140,000 barrels per day (bpd) in Tomakomai. Forty-five of the 105 oil storage tanks were damaged following the earthquake and resulted in release of petroleum naphtha, which ignited accidentally. The first fire was reported immediately after the earthquake on 26 September 2003 and was extinguished after 7 hours. The second fire occurred on 28 September and lasted for 44 h. More than three hundred fireman and about one hundred fire engines were brought from several prefectures by air carriers to extinguish the fire. More than 130,000 L of fire fighting foams (FFF) was delivered to extinguish these fires and at least 40,000 L was used. Detailed information regarding the type of FFF used was not available, but aqueous film forming foams (AFFF) have been used in the control of fuel-related fires. Perfluorooctane sulfonate (PFOS) and related perfluorinated acids are a component of AFFF (1). The issue of environmental pollution by perfluorinated compounds (PFCs) including perfluorinated carboxylates and sulfonates has received much attention in the last four years (2,3). PFCs possess unique physicochemical properties and exhibit a wide range of volatility/ water solubility depending on the functional group. Environmental dynamics of PFCs is complex due to their unique characteristics and to their release from multitude of sources with various compositions. Previous studies have reported on environmental contamination by PFCs due to accidental release of AFFF (4,5). Large amount of release of AFFF in Tomakomai oil refinery fire provided an opportunity to study environmental dynamics of PFCs in the environment. A monthly monitoring survey of the environmental levels of PFCs in the Tomakomai region was conducted since October 2003. This study presents the results of initial survey conducted between October and December 2003.
... Results and Discussion ... Water samples collected in October, approximately a month after the Tomakomai fire, showed two to six times higher concentrations of PFOS, PFHS and PFOSA than those from Tokyo Bay, a most contaminated waterbody in Japan. However, concentrations of perfluorinated carboxylates and PFBS were low in water samples collected in and around the oil refinery in Tomakomai than in Tokyo Bay. Fig 2 and 3 show the concentrations of PFOS and PFOA in water samples collected from Tomakomai and several other locations in Japan. Typical ratio of PFOS to PFOA concentrations in water samples around Japan was less than 0.7 (7,8). Water samples collected in December, approximately two months after the fire, showed a PFOS/PFOA ratio of 10 suggesting greater composition of PFOS in AFFF. After two months of AFFF usage, concentrations of all PFCs decreased dramatically, from 2- to 13- fold, compared to the samples collected in October except for PFHpA. Only at station 8 concentrations of PFOS and PFOA were similar. Relatively high concentrations of PFCs were found in in snow. This suggests that significant amount of PFCs in AFFF were released into the air and deposited to land through wet deposition process. Concentrations of PFCs in soil (pg/g dry weight basis) were also high for most PFCs; however, concentrations of PFBS were low. It may be due to that PFBS concentrations are low in AFFF. The highest concentration of any PFCs detected in Tomakomai samples was 3,680ng/L of PFOS in run-off water collected in October. Run-off water contained all PFCs at the highest concentrations except PFDoA.
Figures 4 and 5 show the composition of perfluorinated sulfonate and carboxylates, respectively, in several water, snow and soil samples from Japan and open ocean. Composition of PFCs in central to eastern Pacific Ocean water represent background profiles of PFCs. North Atlantic Ocean profile reflects relatively contaminated open ocean water. Tokyo Bay water shows typical contaminated coastal water profiles in Japan. Compound specific composition of perfluorinated sulfonates and PFOSA provides several insights. High percentage of PFBS may be suggestive of non-contaminated water samples. Differences in the composition of PFCs between October and December may have been caused by dramatic decrease in PFOS concentrations.
From the above results, following hypothesis regarding environmental dynamics of PFCs can be made. PFCs released from AFFF into coastal water were at highest concentrations in October but removed readily by dilution and exchange of coastal and offshore waters. PFCs released into the atmosphere (gas phase and particulated matters) during AFFF usage was trapped by snow and deposited onto soil and water. PFCs deposited on soils can continue to be a source of exposure in the environment because of the high concentrations observed in soils in December. Soil contamination was also caused by the highly contaminated run-off water...

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4079-4085.

Perfluorooctanesulfonate and Related Fluorochemicals in Several Organisms Including Humans from Italy

Simonetta Corsolini (1), Kurunthachalam Kannan (2)

1 University of Siena, Siena, Italy
2 State University of New York, Albany, NY, USA

... Mediterranean Sea organisms. PFOS was the most predominant fluorochemical in the tissues analyzed (Tables 1-2). PFOS was found in blood of captive bottlenose dolphins at concentrations ranging from 42 to 210 ng/mL (Table 1). The greatest PFOS concentration found in the liver of a common dolphin was 940 ng/g wet wt; muscle tissue from the same individual contained a PFOS concentration that was 12-fold less than that in liver (Table 1). Four of five livers of bottlenose dolphins collected from the Adriatic and Thyrrenian Seas contained quantifiable concentrations of PFOS. The mean????SD concentration of PFOS in livers of striped dolphins was 26????9 ng/g wet wt. Concentrations of PFOS in livers of bottlenose and striped dolphins were less than those found in cetaceans from the coastal waters of Florida 9 . Nevertheless, the concentration of PFOS measured in common dolphin liver was similar to those reported for dolphins from the Florida coast. Among the other fluorochemicals measured, FOSA was a prominent compound in livers of dolphins and whales.
Livers of most of the cetaceans (except striped dolphin) contained quantifiable concentrations of FOSA (Table 1). The greatest FOSA concentration was found in the liver of a common dolphin (878 ng/g wet wt). Occurrence of FOSA in marine mammals from the Mediterranean region indicates the presence of specific and current sources. PFOA and PFHxS were found in blood of a few individuals of bottlenose dolphins at concentrations ranging from <2.5 to 6.1 ng/mL. PFHxS was detected in a striped dolphin and swordfish liver at concentrations of 6.8 and 10 ng/g, wet wt, respectively.
Concentrations of PFOS in cormorant livers collected from Cabras Lagoon in Sardinia ranged from 32 to 150 ng/g wet wt (mean: 61 ng/g) (Table 1). Mean PFOS concentrations in juvenile birds were not significantly different from those in adults (p < 0.05). This is similar for bald eagles collected from the midwestern U.S.13 . In general, PFOS concentrations in cormorants were similar to or less than those found in cormorants and other fish-eating water birds collected from the North American Great Lakes 13 . PFOA was consistently found in all the livers of cormorants at concentrations ranging from 29 to 450 ng/g wet wt.
Concentrations of PFOS in blood of bluefin tuna and swordfish ranged from 27 to 52 (mean: 40) and 4 to 21 ng/mL (mean: 10), respectively (Table 1). The PFOS concentration in livers of bluefin tuna was 21-87 ng/g wet wt (mean: 47), greater than that determined in swordfish (<1-13 ng/g; mean: 7) (Table 1). The ratios of concentrations of PFOS in liver to blood of bluefin tuna and swordfish were 0.85 and 1.4, respectively. These ratios are 7-12-fold less than those calculated for polar bears from Alaska 9 . Although the PFOS concentrations in bottlenose dolphins blood were 4 to 14-fold greater than those in bluefin tuna and swordfish, blood-to-liver ratios of PFOS were less in dolphins than in fishes. This suggests that the distribution of PFOS between liver and blood in fishes is different than in mammals. Concentrations of FOSA in the bluefin tuna blood (mean: 15 ng/mL) were 2 to 4-fold less than those of PFOS (40 ng/mL), which was different from that observed in bottlenose dolphins. FOSA concentrations in swordfish blood was 1.5-fold greater than that of PFOS. FOSA was not found in the fish livers at the quantitation limit of 38 ng/g, wet wt.
Human blood samples. Mean, median, and range of PFOS, PFHxS, PFOA, and PFOSA
concentrations in serum samples are shown in Table 2; their concentrations were 4.4 ng/mL, 1.3 ng/mL, <3 ng/mL and 1.7 ng/mL respectively in female and 4.3 ng/mL, 1.7 ng/mL, <3 ng/mL and 1.8 ng/mL respectively in male donors. PFOS was found in most of the samples collected (87.5% in female and 90.5% in male). PFHxS and PFOSA were found in the blood of Italian donors. Samples did not contain PFOA, at a detection limit of 3 ng/mL. In general, no significant difference (p>0.05) in the concentration of either PFOS or PFOA was found between the sexes.

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4009-4014.

Presence of Anionic Perfluorinated Organic Compounds in Serum Collected from Northern Canadian Populations

Sheryl Tittlemier (1), John J. Ryan (1), Jay Van Oostdam (2)

1 Food Research Division, Health Canada, Ottawa
2 Management of Toxic Substances Division, Health Canada, Ottawa

Introduction. Perfluorinated organic compounds are used in a wide variety of consumer and industrial products and applications, ranging from personal care products and cleaning solutions, to grease resistant coatings for fabric and paper and emulsifiers in the production of polymers.1 Perfluorinated compounds such as perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are persistent and bioaccumulative. PFOS and PFOA have been detected in biota sampled from around the world 2 , including the Canadian Arctic.3,4 Evidence from various laboratory experiments suggest that these perfluorinated compounds can elicit negative effects, including peroxisome proliferation 5 and possibly hepatocarcinogenesis.6 PFOA and PFOS also appear to biomagnify in marine food webs, in a similar fashion as traditional organohalogenated POPs like the recalcitrant PCB congeners.4,7
Indigenous northern Canadian populations such as the Inuit and Inuvialuit often hunt and
consume marine mammals, including beluga, narwhal, and seal, as part of their traditional diet. Thus, segments of these populations are often exposed to higher levels of POPs than southern populations and other consumers of market foods. This higher exposure is reflected in plasma concentrations of traditional POPs such PCBs.8 There is a question of whether a similar situation occurs for PFOS, PFOA, and similar perfluorinated compounds. This preliminary survey analyzed a suite of perfluorinated sulfonates and carboxylates in 23 pooled archived samples of human plasma collected from various northern Canadian populations...
The results of this preliminary survey demonstrate that populations residing in the Northwest and Nunavut Territories in northern Canada are exposed to FOCs. The presence of FOCs in cord blood plasma also indicates that exposure occurs in utero. This limited data set shows that FOC levels in these northern samples are very similar to FOC concentrations in southern population, and that there are no marked differences between the various ethnic groups (Inuit, Dene/Metis, Caucasian). The low samples numbers are insufficient to confidently examine whether or not there are differences in FOC exposure and body burdens amongst various ethnic groups within regions that consume different diets, but these preliminary data do not support such a conclusion...

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4074-4078.

Occurrence of Perfluorinated Organic Acids in the Water of the North Sea

Christina Caliebe (1), Wolfgang Gerwinski (1), Heinrich Hühnerfuss (2), Norbert Theobald (1)

1 Bundesamt für Seeschiffahrt und Hydrographie, Hamburg
2 Universität Hamburg, Inst. für Organische Chemie, Hamburg

Introduction. Perfluorinated organic acids (PFC) and their derivatives are industrially produced since many years in very large quantities and are used for many purposes 1 : Perfluoroalkyl sulfonates are applied, e.g., as surfactants and surface protectors to carpets, leather, paper, fabrics and many more. In addition, some sulfonated and carboxylated PFCs have been utilized in or as fire fighting foams, alkaline cleaners, shampoos, and insecticide formulations. Due to the large production quantities and the persistence in the environment, perfluorinated compounds are meanwhile globally
distributed. Perfluorooctanesulfonic acid (PFOS) and other long chain perfluorinated chemicals have been detected in blood of ringed seals, in polar bears, arctic foxes, mink, birds, and fishes collected in the USA, at the coasts of the Baltic and Mediterranean Sea and in the Arctic 1,2,3,4,5,6 . Because of the findings of perfluorinated compounds in Arctic biota samples, it is of special interest to investigate their long range transport. Due to their high polarity, a transport by the water phase is likely. However up till now, only few studies report on the occurrence in surface or ground water and none in sea water 7 . The aim of this work was, therefore, to develop a method for the determination of perfluorinated organic acids in seawater and to study their occurrence and distribution in the North Sea...
... The occurrence of PFC in the North Sea has not been described before. The concentrations of the major occurring PFOA and PFOS determined on the two cruises are within a similar range as other polar pollutants such as phenylurea, triazine or phenoxyacetic acid herbicides. They are present in part well above classical contaminants like chlorinated hydrocarbons (HCH, DDT group, PCB) 10 . The investigations demonstrated, that the developed method is suitable for the study of the distribution of perfluorinated organic acids in the coastal and open sea water. For extended studies into more remote areas, however, some improvements concerning the LOD are necessary.

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4029-4034.

Age dependent accumulation of perfluorinated chemicals in beef cattles

Keerthi Siri Guruge (1), Sachi Taniyasu (2), Shigeru Miyazaki (1), Noriko Yamanaka (1), Nobuyoshi Yamashita (2)

1 National Institute of Animal Health, Tsukuba, Japan
2 National Institute of Advance Industrial and Technology, Tsukuba, Japan

Introduction. Occurrences of perfluorinated chemicals (FOCs) in the environment recently have brought public concerned as a new group of pollutants. Perfluoroalkylsulfonates and perfluoroalkylacids were found in many environmental compartments including water, sediment and biota. It was reported that FOCs were detected in several species of wild life in various locations including some remote areas.1 Fish and aquatic animals were to be accumulated greater concentrations of PFOS and PFOA with no clear age- or sex-related differences.2,3 Consumption of fish and farm animal products were to be the main human exposure route to organohalogen pollutants. It is important to know the human exposure to FOCs, since some of these compounds have high degrees of bioaccumulation and long half-lives in the human body. However, accumulations of FOCs in farm animals are not documented. In this study we examine the age related presence of FOCs in blood plasma collected from 3 beef cattle from Japan.
... The Age (months) related accumulation of selected fluorinated contaminants (pg/ml) are given in figures 1 to 9. The concentrations of PFBS, PFDoA, PFOSA and THPFOS in bovine plasma were similar or less than those in blank. Hence, those data are not presented. PFOS was the most prominent contaminant detected in few hundred pg/ml levels in bovine plasma (Fig 1). Among the perflourinated acids, PFHxA (Fig 7) concentration was higher than others. The concentrations of PFDA (Fig 4), PFNA (Fig 5), PFOA (Fig 6) and PFPeA (Fig 9) were found at least in few ten pg/ml levels, while others were less than 10 pg/ml. Reports of long chain FOCs contaminants such as PFUnA, PFDA, and PFNA were few in biological matrices.5 The mean PFOS concentration in age of 27 months (530 pg/ml) was nearly 1.5 folds greater than the animals were 9 months (370 pg/ml) old. However, the accumulation trend of most perflourinated acids such as PFUnA, PFDA and PFHxA seems to be decreasing with the aging of cattle. Nevertheless, the number of animals was not sufficient to conclude age related accumulation of FOCs in cattle. According to earlier reports, no significant associations were observed between FOCs concentration and age.

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4069-4073.

Perfluorooctanoic Acid and Perfluorooctane Sulfonate in Michigan and New York Waters

Ewan Sinclair (1), Sachi Taniyasu (2), Nobuyoshi Yamashita (2), Kurunthachalam Kannan (1)

1 Wadsworth Center, Albany
2 National Institute of Advanced Industrial Science and Technology, Tsukuba

Introduction. Perfluorooctane sulfonate (PFOS), a perfluorinated organic contaminant, has become the subject of many recent investigations. PFOS and its precursor compounds have been used in a wide variety of consumer and industrial products. Other related perfluorinated compounds have also been reported to occur in the environment. For example, perfluorohexane sulfonate (PFHxS) is an impurity associated with PFOS. Perfluorooctanoic acid (PFOA) has found widespread use as an emulsifier for polymerization of fluoropolymers. These perfluorinated alkylated substances (PASs) are known to be resistant to degradation 1 .
PFOS and PFOA have been detected in the blood of occupationally exposed workers at a few mg/L concentrations (mean 1.32 mg/L and 1.78 mg/L, respectively), and in the general population at µg/L concentrations (mean 28.4 µg/L PFOS) 2,3 . PFOS and PFOA have been detected in biota globally 4 . There is strong evidence to suggest that these PASs can bioaccumulate in the trophic levels of a food chain. Higher concentrations of PFOS are generally detected in fish eating predators than in the fish. The production of certain PASs, particularly those that are PFOS-related, has been phased out because of this concern of bioaccumulation, their detection in human serum and sparse knowledge of their toxicology 5 . Due to their persistence, these compounds will continue to be of concern for years. This highlights a need for accurate analysis of environmental samples for effective risk assessment 5 .
Water analysis of PFOS and PFOA has been carried out with several methods. The most commonly used methods involve solid phase extraction (SPE) followed by HPLC-MS-MS. Method detection limits for PFOS and PFOA varied between 5 and 17 ng/L and 9 and 25 ng/L respectively 6,7 . Generally PFOS and PFOA concentrations in ambient waters, with no point source of pollution, are less than 5 ng/L 5 . We have developed a method using the Oasis HLB solid phase cartridge to achieve the required method detection limits. We have measured PFOS and PFOA concentration in surface waters collected from Michigan and New York. PFOS and PFOA have been detected in the blood and liver of fish at µg/L concentrations both in Japan and the USA 5,6 . The current ion-pairing, liquid/liquid extraction method is suitable for these concentrations and we have measured PFOS and PFOA in the livers of fish from Michigan and New York waters. We have compared the data for fish and water concentrations and calculated bioaccumulation factors.
... Michigan Fish. PFOS was detected in the livers of chinook salmon, lake whitefish, and various other fish (see Table 1). Brown trout livers had significantly lower PFOS concentrations. Brown trout feed mainly on zooplankton, and less on small fish and invertebrates, than chinook salmon or lake whitefish. This explains the lower bioaccumulation of PFOS in brown trout liver tissue. Further, brown trout was collected from Lake Superior, which is relatively less polluted than other great lakes. PFOA, PFHS and FOSA were not detected in any fish liver samples at the detection limit of 19 ng/g (wet weight), for FOSA and PFHS, and 72 ng/g for PFOA.
These results are consistent with concentrations reported for the livers of fish from Tokyo Bay (62 – 198 ng/g)5 . PFOS concentrations reported for fish liver from Lake Biwa, Japan, ranged from 3 to 310 ng/g. The data shows species specific concentration ranges and are likely determined by the diet of each species. PFOS was detected in the muscle tissue of chinook salmon, lake whitefish, and various other fish (see Table 1). These concentrations are comparable or slightly higher than those detected in the liver of the same fish species. PFOA, PFHS and FOSA were not detected in any fish muscle samples. PFOS was detected in the eggs of chinook salmon, lake whitefish, and various other fish (see Table 1). These concentrations are approximately twice as high as concentrations found in the livers of the same fish species. This suggests that PFOS is actively transferred from adult female fish to their eggs. Occurrence of PFOS in eggs has implications for early life stage effects. In addition, these results suggest that PFOS can bind to specific proteins found in eggs, which could be the reason for high levels in eggs than in muscle or liver.

... Michigan Waters. PFOS was detected in 89% of Michigan water samples. The maximum concentration measured was 29 ng/L. PFOA was detected up to 36 ng/L. Background concentrations were found to be between 2 and 5 ng/L for PFOS and between <8 and 16 ng/L for PFOA. The highest concentrations were detected in the waters of south western Michigan (see Table 2). There are several paper mills located in this area which may provide a source for these high concentrations. Elevated concentrations of PFOS and PFOA were detected in and around Flint, and in Saginaw Bay waters. The highest concentration of PFOS detected in Michigan waters was between 2.5 and 4.8 times lower than those detected downstream of a fluorochemical manufacturing facility on the Tennessee River 7 (75 – 144 ng/L). The range of PFOS concentrations detected in Michigan waters was similar to those found in Japanese surface waters 5 .
The highest concentration of PFOA detected in Michigan waters was 3.8 – 14 times lower than those detected downstream of a fluorochemical manufacturing facility on the Tennessee River 7 (140 – 498 ng/L). PFOA concentrations measured in upstream of the fluorochemical manufacturing facility were reported as < 25 ng/L.

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4046-4052.

Perfluorinated Alkylated Substances (PFAS) in the European Nordic Environment

Urs Berger (1), Ulf Järnberg (2), Roland Kallenborn(3)

1 Norwegian Institute for Air Research (NILU), Tromsø
2 Institute for Applied Environmental Research (ITM), Stockholm
3 Norwegian Institute for Air Research (NILU), Kjeller

Introduction. Perfluorinated alkylated substances (PFAS) have been industrially produced for several decades and are applied as stain and water repellents for surface treatment of textiles, carpets, leather and paper products. Perfluorooctane sulfonate (PFOS), a degradation product of several PFAS, has recently gained considerable attention because of its ubiquitous distribution in the environment 1-4 and its presence in human blood plasma 5,6 . Though most of the production volume of PFOS-based chemicals has been voluntarily phased out by the manufacturers, similar compounds with perfluorinated chains, including perfluorinated carboxylic acids, continue to be employed for comparable applications. A first screening project on the distribution of PFAS in the environment of five Nordic countries was supported and financed by the Nordic Council of Ministers through the Chemicals Group and the Environmental Monitoring Group and national institutions. The aim of the study was to assess the levels and distribution of PFAS in the Nordic environment and to trace differences in contaminant concentrations and patterns between different countries and types of matrices.
... Marine mammals. The 17 marine mammal samples analyzed in this study represented top predators of the marine environment. They were considerably higher contaminated than marine and freshwater fish, which indicates bioaccumulation of PFAS in the aquatic environment. Results are shown in Figure 4. Greyseals from Denmark and Sweden were highest contaminated and characterized by dominant PFOS concentrations (up to 1 µg/g ww). A PFOS concentration gradient was observed from the northernmost site in the Baltic Sea to the more densely populated area between Sweden and Denmark. Icelandic minke whales contained relatively low PFAS levels compared to pilot whales from the Faeroe Islands, indicating correlations with the position in the food chain and feeding habits. Usually PFOS was the dominating PFAS residue also in marine mammals. However in the Faeroese pilot whales PFOSA was equally contributing to the PFAS burden, in two cases even exceeding the PFOS levels. In most marine mammal samples PFNA and PFDcS were found in considerable amounts, indicating the bioaccumulation potential for larger and hence less water soluble PFAS. The concentrations found corresponded well with values reported in literature for seal liver from the Baltic Sea and Bothnian Bay 2 .
... Marine fish. The PFAS distribution in marine fish species (Figure 3) was characterised by a surprisingly high variability reflecting differences in trophic levels, feeding habits, sampling regions as well as uptake and transformation mechanisms. Also for marine fish species, PFOS usually represented the predominant PFAS contaminant. However, in Faeroese sculpins PFOSA was higher concentrated than PFOS. In all Icelandic samples PFDcS was detected at surprisingly high levels (median 10 ng/g ww) and was usually more prominent than PFOSA. Furthermore, PFHxA was present in Icelandic marine fish samples at concentrations >1 ng/g ww. Besides, only Danish samples contained quantifiable amounts of the carboxylic acids PFHxA, PFHpA and PFOA. Marine fish samples from the Faeroe Islands were lowest contaminated. These are all indications for country specific application patterns and contamination levels. Nevertheless, marine fish species were approximately ten times lower contaminated compared to the previously described freshwater fish samples, indicating dilution effects with distance to primary sources. However, marine fish liver samples from the Western Scheldt estuary 9 (Belgium/Netherlands) and from Japan 8 were reported to contain PFOS levels up to 7.7 and 7.9 µg/g ww, respectively.
... Biota samples. PFAS concentrations found in biota were generally much higher than for abiotic samples. This is a strong indication for the bioconcentration potential of these compounds. Biota samples analyzed in this study are presented in three sub-groups: Freshwater fish, marine fish and marine mammals. The comprehensive selection of biota samples represented various biological and environmental endpoints.
Freshwater fish. In all but one freshwater fish samples, PFOS was the predominant PFAS constituent followed by PFOSA (Figure 2). Generally, the contamination levels in the Norwegian freshwater fish samples were considerably lower than found for Finnish pike and Swedish perch. Pike represented the freshwater top predator and showed the highest PFAS contamination in the analysed freshwater biota. The highest PFAS levels were found in a Finnish pike sample (PIFIN01, PFOS 551 ng/g ww, PFOSA 141 ng/g ww). Although the Swedish perch samples represent a lower trophic level than pike, the PFOS concentrations were not significantly lower. This might reflect a higher exposure to PFOS at the Swedish sampling sites. However, the PFOSA levels in perch were much lower than in pike, pointing towards food chain specific uptake or differences in transformation processes. In analogy with PCBs, PFOSA was expected to bioaccumulate in the food chain, since it is the only non-ionic and thus lipophilic PFAS analyte.

Full free report available at

Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4086-4089.


John Giesy (1), Paul Jones (1 [sic 2])

1 Michigan State University, East Lansing 2 ENTRIX Inc., East Lansing

Introduction. Perfluorinated chemicals have been widely used in commerce for the last few decades. Until recently little was known about their environmental fate and even less was known about their potential environmental effects. Since Giesy and co-workers 1 first demonstrated the widespread occurrence of perfluorooctane sulfonic acid (PFOS) in wildlife there has been renewed interest in determining the biological and possible ecological effects of these compounds. The assessment of possible effects of these chemicals has been hampered by a limited understanding of their mode of action and by a lack of toxicological data for wildlife species. Here we summarize recently obtained toxicological studies available for perfluorinated compounds (PFCs) in two avian species and use this information and environmental concentration data to evaluate the potential for environmental risk that these compounds pose.

Full free report available at

Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 3999-4003.

A Survey of Perfluoroalkyl sulfonamides in indoor and outdoor air using passive air samplers

Mahiba Shoeib (1), Tom Harner (1), Bryony Wilford (2), Kevin Jones (2), Jiping Zhu (3)

1 Meteorological Service of Canada, Environment Canada
2 Environmental Science, Lancaster University, Lancaster, UK
3 Chemistry Research Division, Health Canada, Tunney’s Pasture, Ottawa, Canada

Introduction. Perfluorooctane sulfonate (PFOS) has recently emerged as a priority environmental pollutant due to its widespread detection in biological samples from remote regions including the Arctic and the Mid-North Pacific Ocean 1,2 . Because PFOS is fairly involatile, it is hypothesized that its occurrence in remote regions is the result of atmospheric transport of more volatile precursor compounds such as the perfluoroalkyl sulfonamides (PFASs) 3 . PFASs are used in variety of consumer products for water and oil resistance including surface treatments for fabric, upholstery, carpet, paper and leather. In a recent pilot study employing high volume air samples, indoor air concentrations of PFASs were approximately 100 times greater than outdoor levels 4 . This is of significance because people typically spend about 90% of their time indoors 5 and this exposure may serve as an important uptake pathway. Indoor air also serves as a source of PFASs to the outside where PFASs are ultimately transported and distributed throughout the environment. The current study is intended to be a more comprehensive survey of indoor and outdoor air allowing more confident conclusions to be made. Passive air samplers comprised of polyurethane foam (PUF) disks were used. These are quiet, non-intrusive samplers that operate without the aid of a pump or electricity. Air movement delivers chemical to the sampler which has a high retention capacity for persistent organic pollutants (POPs). PUF disks samplers have been previously used successfully to monitor different classes of hydrophobic persistent organic pollutants POPs 6-8 ...
... In conclusion, the results of indoor air from 58 randomly selected residential homes show that some perfluoroalkyl sulfonamides exhibit very high indoor air concentrations. Since people spend majority of their time indoors, the inhalation exposure to these chemicals should be considered in the human exposure assessments. Furthermore, large indoor /outdoor gradients in air concentration exist for MeFOSE and EtFOSE. Therefore indoor air may be a key source of these chemicals to the outdoor environment. Finally, this study demonstrates the versatility of PUF disks passive samplers for surveying environmental contaminants such as Perfluoroalkylsulfonamides in indoor and outdoor air.

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4053-4057.


Anna Kärrman (1), Bert van Bavel (1), Ulf Järnberg (2), Gunilla Lindström (1)

1 Man-Technology-Environment Research Centre, Örebro University
2 Institute of Applied Environmental Research, Stockholm University

Introduction. The commercialisation of interfaced high performance liquid chromatography-mass spectrometry (HPLC-MS) facilitated selective and sensitive analysis of perfluoroalkylated (PFA) acids, a group of compounds frequently used for example as industrial surfactants and which are very persistent and biologically active, in a more convenient way than before. Since then a number of reports on PFA compounds found in humans and wildlife have been published (1,2,3,4,5). The most used technique for the analysis of perfluoroalkylated compounds has been ion-pair extraction followed by high performance liquid chromatography (HPLC) and negative electrospray tandem mass spectrometry (MS/MS). Tetrabutylammonium ion as the counter ion in the ion-pair extraction has been used together with GC-analysis (6), LC-fluorescence (7) and LC-MS/MS (8). Recently, solid phase extraction (SPE) has been used instead of ion-pair extraction for the extraction of human serum (9). Previously reported studies on human exposure have mainly been on serum, probably because there are indications that PFA acids bind to plasma proteins (10,11). We here present a fast and simple method that involves SPE and which is suitable for extracting whole blood samples. Further more, 13 PFAs (listed in Table 1) were included in the method, which uses HPLC and single quadropol mass spectrometry.

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Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4023-4028.

Identification of the isomer composition in technical perfluorooctane sulfonate solution by LC-ESI(-)-IT-MS/MS

Ingrid Langlois (1), Michael Oehme (1)

1 University Basel

Introduction. Perfluorinated compounds (PFC) have been detected in the environment worldwide. Among them, perfluorooctanesulfonate (PFOS, C8F17SO3 - ) is the most dominant contaminant 1 . Its presence in biota can be explained by the application of PFOS for more than 50 years as well as its formation by biodegradation from perfluorooctanesulfonamide 2 . PFOS is very persistent and has shown different toxicological effects such as peroxisome proliferation and inhibits gap junction intercellular communication 3 . Reversed-phase-HPLC combined with triple quadrupole (TQ) mass spectrometry (MS) is the method of choice for the quantification of PFOS 1,2,4 . PFOS contains several isomers, which are detectable in biota 4 . These are usually not completely separated and reported as an additional signal “shoulder”4 . Hundreds of structural PFOS isomers (C8F17SO3 - ) are theoretically possible. Currently, nearly no information is available about the structure and the abundance of the isomer patterns in biota and in technical product. PFOS is produced mainly by an electrochemical process 5 . It forms a main PFOS isomer with a linear chain (70 %)5 and many branched isomers. The aim of this work was to characterize the isomer composition of commercial PFOS solutions and to separate as many isomers as possible. Moreover, the fragmentation behavior of PFOS isomers was investigated using ion-trap (IT) mass spectrometry (MS) with electrospray ionization in negative mode (ESI(-)) for structure elucidation.

Full free report available at
Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4015-4022.

Nuclear Magnetic Resonance and LC/MS Characterization of Native and New Mass-labeled Fluorinated Telomer Alcohols, Acids and Unsaturated Acids

Gilles Arsenault (1), Brock Chittim (1), David Ellis (2), Thor Halldorson (3), Scott Mabury (2), Alan McAlees (1), Robert McCrindle (4), Naomi Stock (2), Gregg Tomy (3), Brian Yeo (1)

1 Wellington Laboratories Inc., Guelph
2 University of Toronto, Toronto
3 Dept. of Fisheries and Oceans, Winnipeg
4 University of Guelph, Guelph

Introduction. A variety of fluorinated compounds are used in a multitude of consumer products because of their ability to repel water and oil, resistance to heat, and chemical inertness. Recently, scientists and regulators have begun raising concerns about the potential health and environmental impact of perfluorinated compounds 1-7 . Exposure to perfluoroalkyl acids, such as Perfluorooctanoic acid (PFOA), has been identified 8 as a potential human health concern. A study has shown 9 that telomer alcohols such as 2-perfluorooctylethanol can be metabolized by living organisms or biodegrade under environmental conditions to sequentially give the saturated fluorinated telomer acid (2- perfluorooctylethanoic acid), then the unsaturated telomer acid (2H-Perfluorooct-2-enoic acid), and eventually PFOA.
Additional experimental work is necessary to determine the extent, if any, to which telomer product degradation may be a source of PFOA. The analysis for fluorinated compounds in environmental samples is performed, primarily, using LC/MS techniques. These analyses have been hindered by the lack of any commercially available mass-labeled fluorinated compounds for use as surrogates 10 and thus may be restricting the amount of research conducted in this area.
We have now synthesized the mass-labeled perfluoroalkyl telomer alcohols and the corresponding acids and unsaturated acids. We report in this study their 1 H-, 2 H-, 19 F- and 13 C-NMR characterizations along with GC/MS and LC/MS data and evaluation of their use as surrogate standards.

Full free report available at
Paper presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004.

ORGANOHALOGEN COMPOUNDS – Volume 66 (2004) 4041-4045


Jae-Ho Yang (1) , Kurunthachalam Kannan (2) , Sun-Young Kim (1) , Im-Hee Shin (1)

1 Catholic University of Daegu, School of Medicine, Dept of Pharmacololgy/Toxicology, Daegu, Korea
2 Wardsworth Center, New York State Dept of Health and Dept of Env. Health and Tox, SUNY, Albany, NY, USA

Introduction. Perfluorooctanesulfonate (PFOS) was found to be widespread in human populations and wildlife 1-2. Major applications of these POSF-based products have included surfactants in: specialty paper and packaging products, carpet, upholstery, and textile products and in certain insecticide formulation 3 . Depending on the specific functional derivatization or the degree of polymerization, such POSF-based products may degrade or metabolize to PFOS, a stable and persistent end product that has the potential to bioaccumulate in the food chain 4 . The mechanisms and pathways leading to the presence of PFOS in human blood are not well characterized but likely involve environmental and dietary exposure to PFOS or to precursor molecules of PFOS. PFOS and related perfluorinated compounds have recently been detected at low parts per billion (nanogram per milliliter) concentrations in the general population from 10 different countries including Korea 5 . In the present report, the levels of perfluoroalkylated compounds in the general population from Korea were analyzed with respect to occupation, smoking status, sex, age and socio-economic status. The degree of association between the four target fluorochemicals measured in this study (PFOS, PFHxS, PFOA, and PFOSA) were also analyzed by linear regression to determine the potential association between their sources of exposure..

Crit Rev Toxicol. 2004 Jul-Aug;34(4):351-84.

The toxicology of perfluorooctanoate.

Kennedy GL Jr, Butenhoff JL, Olsen GW, O'Connor JC, Seacat AM, Perkins RG, Biegel LB, Murphy SR, Farrar DG.

DuPont, Newark, Delaware, USA.

PFOA is a peroxisome proliferator (PPAR agonist) and exerts morphological and biochemical effects characteristic of PPAR agonists. These effects include increased beta-oxidation of fatty acids, increases in several cytochrome P-450 (CYP450)-mediated reactions, and inhibition of the secretion of very low-density lipoproteins and cholesterol from the liver. These effects on lipid metabolism and transport result in a reduction of cholesterol and triglycerides in serum and an accumulation of lipids in the liver. The triad of tumors observed (liver, Leydig cell, and pancreatic acinar-cell) is typical of many PPAR agonists and is believed to involve nongenotoxic mechanisms. The hepatocellular tumors observed in rats are likely to have been the result of the activation of the peroxisome proliferator activated receptor alpha (PPARalpha). The tumors observed in the testis (Leydig-cell) have been hypothesized to be associated with an increased level of serum estradiol in concert with testicular growth factors. The mechanism responsible for the acinar-cell tumors of the pancreas in rats remains the subject of active investigation. The mechanism resulting in the hepatocellular tumors in rats (PPARalpha activation) is not likely to be relevant to humans. Similarly, the proposed mechanism for Leydig-cell tumor formation is of questionable relevance to humans. Acinar tumors of the pancreas are rare in humans, and the relevance of the these tumors, as found in rats, to humans is uncertain. Epidemiological investigations and medical surveillance of occupationally exposed workers have not found consistent associations between PFOA exposure and adverse health effects.

PMID: 15328768 [PubMed - in process]

Toxicol Sci. 2004 Aug 13 [Epub ahead of print]
Mitochondrial Permeability Transition as the Critical Target of N-Acetyl Perfluorooctane Sulfonamide Toxicity in Vitro.

O'Brien TM, Wallace KB.

Department of Biochemistry and Molecular Biology, Toxicology Graduate Program, University of Minnesota School of Medicine, 1035 University Drive, Duluth, Minnesota 55812.

Perfluorooctanyl compounds with active functional groups have been shown to disrupt mitochondrial bioenergetics by three distinct mechanisms: protonophoric uncoupling of mitochondrial respiration, induction of the mitochondrial permeability transition (MPT)or a non-selective increase in membrane permeability. The purpose of this investigation was to identify the initial target and specific sequence of events associated with the N-acetyl substituted perflourooctanesulfonamides induced MPT. N-acetyl-perfluorooctanesufonamide (FOSAA), N-ethyl-N-acetyl-perfluorooctanesulfonamide (N-Et-FOSAA), perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), and N-ethyl-N-(2-ethoxy)-perfluorooctanesulfonamide (N-Et-FOSE) were added individually to liver mitochondria freshly isolated from Sprague-Dawley rats. Mitochondrial swelling and cytochrome c release were recorded spectrophotometrically, oxygen uptake was monitored with a Clark-type oxygen electrode, and reactive oxygen species (ROS) were monitored by dichlorodihydrofluorescein diacetate (H2DCFDA) fluorescence. FOSAA (45 micro M) and N-Et-FOSAA (7.5 micro M) induced calcium-dependent mitochondrial swelling, the release of cytochrome c, inhibition of uncoupled mitochondrial respiration, and ROS generation, all of which were inhibited by cyclosporin-A (CsA). PFOA (200 micro M) displayed slight CsA sensitive activity, but neither PFOS (10 micro M) nor N-Et-FOSE (70 micro M) induced the MPT. Results of this investigation demonstrate two important findings;
1) MPT induction is specific to the N-acetyl substituted perfluorooctanesulfonamides and,
2) the sequence of events is initiated by induction of the MPT, which causes the release of cytochrome c as well as other cofactors leading to inhibition of respiration and ROS generation.

The toxicity of N-acetyl perfluorooctanyl compounds may therefore reflect the mitochondrial dysfunction, which is compounded by the ensuing oxidative injury.

PMID: 15310855 [PubMed - as supplied by publisher]

Biochim Biophys Acta. 2004 Aug 30;1664(2):141-9.

Mixing of perfluorinated carboxylic acids with dipalmitoylphosphatidylcholine.

Lehmler HJ, Bummer PM.

Department of Occupational and Environmental Health, University of Iowa, 100 Oakdale Campus #124 IREH, Iowa City, IA 52242-5000 USA.

Perfluorinated acids are emerging as an important class of persistent environmental pollutant, thus raising human health concerns. To understand the behavior of these compounds in biological systems, the mixing behavior of two perfluorinated acids, perfluorododecanoic and perfluorotetradecanoic acid, with dipalmitoylphosphatidylcholine (DPPC) was studied in monolayers at the air-water interface and in fully hydrated DPPC bilayers. The mixing behavior of both acids was indicative of an attractive interaction and partial miscibility with DPPC at the air-water interface. In the bilayer studies, the fluorinated acids cause peak broadening and elimination of the pretransition of DPPC. The onset temperature of the main phase transition remains constant in the presence of the fluorinated acids suggesting immiscibilities in the gel phase. Below X(DPPC)=0.97 significant peak broadening of the main phase transition can be observed. These results suggest strong interaction between the respective acid and DPPC, and that both acids are able to partition into the lipid bilayer. However, their mixing behavior is far from ideal, thus suggesting the presence of domains or lipid aggregates with high acid concentrations which may (adversely) impact the function of biological mono- and bilayers.

PMID: 15328046 [PubMed - in process]

Anal Chem. 2004 Jul 1;76(13):3800-3.
Gas-phase NMR technique for studying the thermolysis of materials: thermal decomposition of ammonium perfluorooctanoate.

Krusic PJ, Roe DC.

Central Research and Development, E. I. Du Pont de Nemours & Company, Wilmington, DE 19880-0328, USA.

The kinetics of the thermal decomposition of ammonium perfluorooctanoate (APFO) has been studied by high-temperature gas-phase nuclear magnetic resonance spectroscopy over the temperature range 196-234 degrees C. We find that APFO cleanly decomposes by first-order kinetics to give the hydrofluorocarbon 1-H-perfluoroheptane and is completely decomposed (>99%) in a matter of minutes at the upper limit of this temperature range. Based on the temperature dependence of the measured rate constants, we find that the enthalpy and entropy of activation are DeltaH++ = 150 +/- 11 kJ mol(-1) and DeltaS++ = 3 +/- 23 J mol(-)(1) deg(-1). These activation parameters may be used to calculate the rate of APFO decomposition at the elevated temperatures (350-400 degrees C) at which fluoropolymers are processed; for example, at 350 degrees C the half-life for APFO is estimated to be less than 0.2 s. Our studies provide the fundamental parameters involved in the decomposition of the ammonium salt of perfluorooctanoic acid and indicate the utility of gas-phase NMR for thermolysis studies of a variety of materials that release compounds that are volatile at the temperature of decomposition and that contain an NMR-active nucleus.

PMID: 15228357 [PubMed - in process]

Environ Sci Technol. 2004 Jun 15;38(12):215A-216A.

No Abstract available

Arctic chemistry may explain perfluorinated mystery.

Renner R.

Publication Types:
* Comment
* News

PMID: 15260308 [PubMed - in process]

Full report available at

Environ Health Perspect. 2004 Aug;112(11):1204-7.
Perfluorooctane Sulfonate (PFOS) and Related Perfluorinated Compounds in Human Maternal and Cord Blood Samples: Assessment of PFOS Exposure in a Susceptible Population during Pregnancy.

Inoue K, Okada F, Ito R, Kato S, Sasaki S, Nakajima S, Uno A, Saijo Y, Sata F, Yoshimura Y, Kishi R, Nakazawa H.

Department of Analytical Chemistry, Faculty of Pharmaceutical Sciences, Hoshi University, Tokyo, Japan.

Fluorinated organic compounds (FOCs), such as perfluorooctane sulfonate (PFOS), perfluoro-octanoate (PFOA), and perfluorooctane sulfonylamide (PFOSA), are widely used in the manufacture of plastic, electronics, textile, and construction material in the apparel, leather, and upholstery industries. FOCs have been detected in human blood samples. Studies have indicated that FOCs may be detrimental to rodent development possibly by affecting thyroid hormone levels. In the present study, we determined the concentrations of FOCs in maternal and cord blood samples. Pregnant women 17-37 years of age were enrolled as subjects. FOCs in 15 pairs of maternal and cord blood samples were analyzed by liquid chromatography-electrospray mass spectrometry coupled with online extraction. The limits of quantification of PFOS, PFOA, and PFOSA in human plasma or serum were 0.5, 0.5, and 1.0 ng/mL, respectively. The method enables the precise determination of FOCs and can be applied to the detection of FOCs in human blood samples for monitoring human exposure. PFOS concentrations in maternal samples ranged from 4.9 to 17.6 ng/mL, whereas those in fetal samples ranged from 1.6 to 5.3 ng/mL. In contrast, PFOSA was not detected in fetal or maternal samples, whereas PFOA was detected only in maternal samples (range, < 0.5 to 2.3 ng/mL, 4 of 15). Our results revealed a high correlation between PFOS concentrations in maternal and cord blood (r(superscript)2(/superscript) = 0.876). However, we did not find any significant correlations between PFOS concentration in maternal and cord blood samples and age bracket, birth weight, or levels of thyroid-stimulating hormone or free thyroxine. Our study revealed that human fetuses in Japan may be exposed to relatively high levels of FOCs. Further investigation is required to determine the postnatal effects of fetal exposure to FOCs. Key words: cord blood, fluorinated organic compounds, human, PFOA, PFOS, PFOSA, pregnancy.

PMID: 15289168 [PubMed - in process]

J Occup Environ Med. 2004 Aug;46(8):837-846.

Analysis of Episodes of Care in a Perfluorooctanesulfonyl Fluoride Production Facility.

Olsen GW, Burlew MM, Marshall JC, Burris JM, Mandel JH.

3M Medical Company, Medical Department, St. Paul, Minnesota (Dr Olsen, Ms Burlew, Ms Burris, and Dr Mandel); and Ingenix Employer Group, New Haven, Connecticut (Ms Marshall).

The observed to expected episodes of care experience of 652 employees at a fluorochemical (perfluorooctanesulfonyl fluoride) production facility was compared with 659 film plant (nonfluorochemical) employees at the same site (Decatur, AL). Episodes of care were defined by a hierarchical analysis of health claims data from 1993 through 1998. The age- and sex-adjusted expected number of episodes of care was calculated from the company's U.S. manufacturing workforce. For a priori interests, the observed to expected episodes of care ratios were comparable for fluorochemical and film plant employees for liver tumors or diseases, bladder cancer, thyroid and lipid metabolism disorders, and reproductive, pregnancy, and perinatal disorders and higher for biliary tract disorders and cystitis recurrence. Non-a priori associations among the fluorochemical plant workers included benign colon polyps, malignant colorectal tumors, and malignant melanoma.

PMID: 15300136 [PubMed - as supplied by publisher]

Toxicol Appl Pharmacol. 2004 Jul 15;198(2):231-41.

The developmental toxicity of perfluoroalkyl acids and their derivatives.

Lau C, Butenhoff JL, Rogers JM.

Reproductive Toxicology Division, National Health and Environmental Effects Research Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, USA.

Perfluoroalkyl acids such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have applications in numerous industrial and consumer products. Although the toxicology of some of these compounds has been investigated in the past, the widespread prevalence of PFOS and PFOA in humans, as demonstrated in recent bio-monitoring studies, has drawn considerable interest from the public and regulatory agencies as well as renewed efforts to better understand the hazards that may be inherent in these compounds. This review provides a brief overview of the perfluoroalkyl chemicals and a summary of the available information on the developmental toxicity of the eight-carbon compounds, PFOS and PFOA. Although the teratological potentials of some of these chemicals had been studied in the past and the findings were generally unremarkable, results from recent postnatal studies on developmental and reproductive indices have prompted consideration of their relevance to human health risk. Based on current understanding of the developmental effects of PFOS and PFOA in rodents, several avenues of research are suggested that would further support the risk assessment of these perfluorinated organic chemicals.

PMID: 15236955 [PubMed - in process]

Chem Res Toxicol. 2004 Jun;17(6):767-75.
Biotransformation of N-Ethyl-N-(2-hydroxyethyl)perfluorooctanesulfonamide by Rat Liver Microsomes, Cytosol, and Slices and by Expressed Rat and Human Cytochromes P450.

Xu L, Krenitsky DM, Seacat AM, Butenhoff JL, Anders MW.

Department of Pharmacology and Physiology, University of Rochester Medical Center, Rochester, New York 14624, and 3M Medical Department, Corporate Toxicology, 3M Center 220-2E-02, St. Paul, Minnesota 55133.

Perfluorooctanesulfonic acid (PFOS) and its derivatives have been used in a range of industrial and commercial applications, including the manufacture of surfactants, adhesives, anticorrosion agents, and insecticides. PFOS is found at detectable concentrations in human and wildlife tissues and in the global environment. N-Substituted perfluorooctanesulfonamides are believed to be degraded to PFOS and, therefore, contribute to the accumulation of PFOS in the environment. N-Ethyl-N-(2-hydroxyethyl)perfluorooctanesulfonamide (N-EtFOSE) is converted to PFOS in experimental animals. The objective of this study was to elucidate the pathways for the biotransformation of N-EtFOSE, which is a major precursor and component of PFOS-based compounds. N-EtFOSE and several putative metabolites were incubated with liver microsomes and cytosol and with liver slices from male Sprague-Dawley rats. Microsomal fractions fortified with NADPH catalyzed the N-deethylation of N-EtFOSE to give N-(2-hydroxyethyl)perfluorooctanesulfonamide (FOSE alcohol) and of FOSE alcohol to give perfluorooctanesulfonamide (FOSA). These N-dealkylation reactions were catalyzed mainly by male rat P450 2C11 and P450 3A2 and by human P450 2C19 and 3A4/5. Rat liver microsomal fractions incubated with UDP-glucuronic acid catalyzed the O-glucuronidation of N-EtFOSE and FOSE alcohol and the N-glucuronidation of FOSA. Cytosolic fractions incubated with NAD(+) catalyzed the oxidation of FOSE alcohol to perfluooctanesulfonamidoacetate (FOSAA). The oxidation of N-EtFOSE to N-ethylperfluorooctanesulfonamidoacetate (N-EtFOSAA) was observed in liver slices but not in cytosolic fractions. FOSA was biotransformed in liver slices to PFOS, albeit at a low rate. These results show that the major pathway for the biotransformation of N-EtFOSE is N-dealkylation to give FOSA. The biotransformation of FOSA to PFOS explains the observation that PFOS is found in animals given N-EtFOSE.

PMID: 15206897 [PubMed - in process]

Regul Toxicol Pharmacol. 2004 Jun;39(3):363-80.
Characterization of risk for general population exposure to perfluorooctanoate.

Butenhoff JL, Gaylor DW, Moore JA, Olsen GW, Rodricks J, Mandel JH, Zobel LR.

Medical Department, 3M Company, Building 220-2E-02, St. Paul, MN 55144, USA.

Perfluorooctanoate (PFOA), an environmentally and metabolically stable perfluorinated carboxylic acid, has been detected in the serum of children, adults and the elderly from the United States with the upper bound of the 95th percentile estimate in the range of 0.011-0.014 microg/mL (ppm). In this risk characterization, margins of exposure (MOE), which can provide a realistic perspective on potential for human risk, were determined by comparison of general population serum PFOA concentrations with serum concentrations from toxicological studies that are associated with the lower 95% confidence limit of a modeled 10 percent response or incidence level (LBMIC(10)) using USEPA BMDS software. The LBMIC(10) was estimated using surrogate data from other studies or pharmacokinetic relationships if serum PFOA data were not available. Modeled dose-responses (with resulting LBMIC(10) values) included post-natal effects in rats (29 microg/mL), liver-weight increase (23 microg/mL), and body-weight change (60 microg/mL) in rats and monkeys, and incidence of Leydig cell adenoma (125 microg/mL) in rats. MOE values based on the upper bound 95th percentile population serum PFOA concentration were large, ranging from 1600 (liver-weight increase) to 8900 (Leydig cell adenoma). These MOE values represent substantial protection of children, adults, and the elderly.

PMID: 15135214 [PubMed - in process]

J Environ Monit. 2004 Jun;6(6):540-5. Epub 2004 Mar 22.

A pilot study on the determination of perfluorooctanesulfonate and other perfluorinated compounds in blood of Canadians.

Kubwabo C, Vais N, Benoit FM.

Health Canada, Safe Environments Programme, Chemistry Research Division, Environmental Health Centre, PL 0800C, Tunney's Pasture, Ottawa, Ontario K1A 0L2.

A pilot study was conducted to provide preliminary data on the concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorooctanesulfonamide (PFOSA) in the blood of Canadians. A set of 56 human serum samples was collected from non-occupationally exposed Canadians and analyzed by microbore HPLC-negative ion electrospray tandem mass spectrometry. PFOS was the main component of perfluorinated organic compounds (PFCs) and was detected in all 56 blood specimens at an average concentration of 28.8 ng mL(-1) and a range from 3.7 to 65.1 ng mL(-1). The concentration of PFOA was an order of magnitude lower than that of PFOS and was found only in 16 samples (29%) at concentrations above the limit of quantification (LOQ). PFOSA was not detected at levels above the method detection limit (MDL) in any of the samples. The levels of PFCs observed in the sample group of non-occupationally exposed humans in Canada were similar to the levels reported in a previous US study with a similar sample pool size. Two distinct PFOS isomers in human serum were identified by accurate mass determination.

PMID: 15173906 [PubMed - in process]

Environ Health Perspect. 2004 May;112(6):681-6.

Biochemical Effect Evaluation of Perfluorooctane Sulfonic Acid-Contaminated Wood Mice (Apodemus sylvaticus).

Hoff PT, Scheirs J, Van De Vijver K, Van Dongen W, Esmans EL, Blust R, De Coen W.

Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Antwerp, Belgium.

Wood mice (Apodemus sylvaticus) were captured at Blokkersdijk, a nature reserve in the immediate vicinity of a fluorochemical plant in Antwerp, Belgium, and at Galgenweel, 3 kilometers farther away. The liver perfluorooctane sulfonic acid (PFOS) concentrations in the Blokkersdijk mice were extremely high (0.47-178.55 micro g/g wet weight). Perfluorononanoic, perfluorodecanoic, perfluoroundecanoic, and perfluorododecanoic acids were found sporadically in the liver tissue of the Blokkersdijk mice. The liver PFOS concentrations at Galgenweel were significantly lower than those at Blokkersdijk (0.14-1.11 micro g/g wet weight). Further results suggest sex independence of the liver PFOS levels, increased levels of PFOS bioaccumulation in older mice, and maternal PFOS transfer to the young. Several liver end points were significantly elevated in the Blokkersdijk mice: liver weight, relative liver weight, peroxisomal ss-oxidation activity, microsomal lipid peroxidation level, and mitochondrial fraction protein content. For the mitochondrial fraction catalase activity, no significant difference between locations was found. The liver weight, relative liver weight, and liver microsomal lipid peroxidation level increased significantly with the liver PFOS concentration. No indications for PFOS-mediated effects on the serum triglyceride, cholesterol, or potassium levels were obtained. The liver PFOS concentration was negatively related to the serum alanine aminotransferase activity.

PMID: 15121511 [PubMed - in process]

Environ Sci Technol. 2004 May 15;38(10):2857-64.

Fluorotelomer alcohol biodegradation yields poly- and perfluorinated acids.

Dinglasan MJ, Ye Y, Edwards EA, Mabury SA.

Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto, Ontario, Canada M5S 3H6.

The widespread detection of environmentally persistent perfluorinated acids (PFCAs) such as perfluorooctanoic acid (PFOA) and its longer chained homologues (C9>C15) in biota has instigated a need to identify potential sources. It has recently been suggested that fluorinated telomer alcohols (FTOHs) are probable precursor compounds that may undergo transformation reactions in the environment leading to the formation of these potentially toxic and bioaccumulative PFCAs. This study examined the aerobic biodegradation of the 8:2 telomer alcohol (8:2 FTOH, CF3(CF2)7CH2CH2OH) using a mixed microbial system. The initial measured half-life of the 8:2 FTOH was approximately 0.2 days mg(-1) of initial biomass protein. The degradation of the telomer alcohol was monitored using a gas chromatograph equipped with an electron capture detector (GC/ECD). Volatile metabolites were identified using gas chromatography/ mass spectrometry (GC/MS), and nonvolatile metabolites were identified and quantified using liquid chromatography/ tandem mass spectrometry (LC/MS/MS). Telomer acids (CF3(CF2)7CH2COOH; CF3(CF2)6CFCHCOOH) and PFOA were identified as metabolites during the degradation, the unsaturated telomer acid being the predominant metabolite measured. The overall mechanism involves the oxidation of the 8:2 FTOH to the telomer acid via the transient telomer aldehyde. The telomer acid via a beta-oxidation mechanism was furthertransformed, leading to the unsaturated acid and ultimately producing the highly stable PFOA. Telomer alcohols were demonstrated to be potential sources of PFCAs as a consequence of biotic degradation. Biological transformation may be a major degradation pathway for fluorinated telomer alcohols in aquatic systems.

PMID: 15212260 [PubMed - in process]

SAR QSAR Environ Res. 2004 Feb;15(1):69-82.

Predicting the biodegradation products of perfluorinated chemicals using CATABOL.

Dimitrov S, Kamenska V, Walker JD, Windle W, Purdy R, Lewis M, Mekenyan O.

Laboratory of Mathematical Chemistry, University Prof As. Zlatarov, Yakimov Street 1, 8010 Bourgas, Bulgaria.

Perfluorinated chemicals (PFCs) form a special category of organofluorine compounds with particularly useful and unique properties. Their large use over the past decades increased the interest in the study of their environmental fate. Fluorocarbons may have direct or indirect environmental impact through the products of their decomposition in the environment. It is a common knowledge that biodegradation is restricted within non-perfluorinated part of molecules: however, a number of studies showed that defluorination can readily occur during biotransformation. To evaluate the fate of PFCs in the environment a set of principal transformations was developed and implemented in the simulator of microbial degradation using the catabolite software engine (CATABOL). The simulator was used to generate metabolic pathways for 171 perfluorinated substances on Canada's domestic substances list. It was found that although the extent of biodegradation of parent compounds could reach 60%, persistent metabolites could be formed in significant quantities. During the microbial degradation a trend was observed where PFCs are transformed to more bioaccumulative and more toxic products. Perfluorooctanoic acid and perfluorooctanesulfonate were predicted to be the persistent biodegradation products of 17 and 27% of the perfluorinated sulphonic acid and carboxylic acid containing compounds, respectively.

PMID: 15113070 [PubMed - indexed for MEDLINE]

Toxicology. 2004 Mar 1;196(1-2):95-116.
The reproductive toxicology of ammonium perfluorooctanoate (APFO) in the rat.

Butenhoff JL, Kennedy GL Jr, Frame SR, O'Connor JC, York RG.

3M Medical Department, Corporate Toxicology, 3M Center 220-2E-02, Saint Paul, MN 55133, USA.

Ammonium perfluorooctanoate (APFO) is a surfactant used primarily as an aid in processing various fluoropolymers. Many toxicology and epidemiological studies have been conducted with APFO; however, no specific information regarding functional reproduction was previously available. Therefore, the potential reproductive toxicity of APFO across two generations of offspring was studied using current EPA OPPTS 870.3800 guidelines. Male and female Sprague-Dawley rats were dosed orally with 0, 1, 3, 10, or 30 mg/kg APFO. Parental (P) generation rats (approximately 6 weeks old) were dosed at least 70 days prior to mating and until sacrificed (after mating for male rats; after weaning for female rats). F(1)-generation rats were dosed similarly, beginning at weaning. The F(2)-generation pups were maintained through 22 days of lactation. Reproductive parameters evaluated in P- and F(1)-generation rats included estrous cycling, sperm number and quality, mating, fertility, natural delivery, and litter viability and growth. Age at sexual maturation in F(1), anogenital distance in F(2), and presence of nipples (males) in F(2)-generation pups were also determined. Feed consumption, body-weight gain, selected organ-weights, gross pathology and appropriate histopathology were evaluated. Reproductive endpoints including mating, fertility, and natural delivery were not affected in either generation. P- and F(1)-generation male rats showed decreased body weight, and liver and kidney weight increases at all doses. The 30 mg/kg F(1)-generation pups had decreased birth weight. Viability was reduced in the 30 mg/kg F(1)-generation pups in apparent relationship to reduced body weight at birth and weaning; however, F(2)-generation pups at 30 mg/kg, although somewhat lighter, did not show a loss in viability. Preputial separation and vaginal opening were somewhat delayed at 30 mg/kg, but these rats went on to show normal reproductive performance. No-observed-adverse-effect-levels were >30 mg/kg for reproductive function of P- and F(1)-generation rats, 10 mg/kg for F(1)-generation pup mortality, birth weight, and sexual maturation, and less than 1mg/kg for male body-weight and organ-weight changes.

PMID: 15036760 [PubMed - indexed for MEDLINE]

Full free report available at

J Occup Health. 2004 Mar;46(2):141-7.
The influence of time, sex and geographic factors on levels of perfluorooctane sulfonate and perfluorooctanoate in human serum over the last 25 years.

Harada K, Saito N, Inoue K, Yoshinaga T, Watanabe T, Sasaki S, Kamiyama S, Koizumi A.

Department of Health and Environmental Sciences, Kyoto University Graduate School of Medicine, Kyoto, Japan.

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are important perfluorochemicals (PFCs) in various applications. Recently, it has been shown that these chemicals are widespread in the environment, wildlife and humans. But the kinds of factors that affect their levels in serum are unclear, and it is also not clear whether exposure to them is increasing or not. To investigate the impacts of time, geographical location and sex on the levels of these chemicals, we measured PFOS and PFOA concentrations in human sera samples collected both historically and recently in Miyagi, Akita and Kyoto Prefectures in Japan. The PFOS and PFOA levels in sera [Geometric Mean (Geometric Standard Deviation)] (microg/L) in 2003 ranged from 3.5 (2.9) in Miyagi to 28.1 (1.5) in Kyoto for PFOS and from 2.8 (1.5) to 12.4 (1.4) for PFOA. Historical samples collected from females demonstrated that PFOS and PFOA concentrations have increased by factors of 3 and 14, respectively, over the past 25 yr. There are large sex differences in PFOS and PFOA concentrations in serum at all locations. Furthermore, there are predominant regional differences for both PFOS and PFOA concentrations. In Kyoto the concentrations of PFOA in dwellers who had lived in the Kinki area for more than 2 yr were significantly higher than in people who had recently moved into the area, in both sexes. This finding suggests that there are sources of PFOA in the Kinki area that have raised the PFOA serum levels of its inhabitants. Further studies are needed to elucidate these sources in the Kinki area of Japan.

PMID: 15090689 [PubMed - in process]

J Occup Health. 2004 Jan;46(1):49-59.
Perfluorooctanoate and perfluorooctane sulfonate concentrations in surface water in Japan.

Saito N, Harada K, Inoue K, Sasaki K, Yoshinaga T, Koizumi A.

Research Institute for Environmental Sciences and Public Health of Iwate Prefecture, Japan.

Perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) are synthetic surfactants used in Japan. An epidemiological study of workers exposed to PFOA revealed a significant increase in prostate cancer mortality. A cross-sectional study of PFOA-exposed workers showed that PFOA perturbs sex hormone homeostasis. We analyzed their concentrations in surface water samples collected from all over Japan by LC/MS with a solid phase extraction method. The lowest limits of detection (LOD) (ng/L) were 0.06 for PFOA and 0.04 for PFOS. The lowest limits of quantification (LOQ) (ng/L) were 0.1 for both analytes. The levels [geometric mean (GM); geometric standard deviation (GS)] (ng/L) of PFOA and PFOS in the surface waters were GM (GS): 0.97 (3.06) and 1.19 (2.44) for Hokkaido-Tohoku (n=16); 2.84(3.56) and 3.69 (3.93) for Kanto (n=14); 2.50 (2.23) and 1.07 (2.36) for Chubu (n=17); 21.5 (2.28) and 5.73 (3.61) for Kinki (n=8); 1.51 (2.28) and 1.00 (3.42) for Chugoku (n=9); 1.93 (2.40) and 0.89 (3.09) for Kyushu-Shikoku (n=15). The GM of PFOA in Kinki was significantly higher than in other areas (ANOVA p<0.01). Systematic searches of Yodo and Kanzaki Rivers revealed two highly contaminated sites, a public-water-disposal site for PFOA and an airport for PFOS. The former was estimated to release 18 kg of PFOA/d. PFOA in drinking water in Osaka city [40 (1.07) ng/L] was significantly higher than in other areas. The present study confirms that recognizable amounts of PFOA are released in the Osaka area and that people are exposed to PFOA through drinking water ingestion.

PMID: 14960830 [PubMed - in process]

Ecotoxicol Environ Saf. 2004 May;58(1):68-76.
Effects of perfluorooctane sulfonate and perfluorooctanoic acid on the zooplanktonic community.

Sanderson H, Boudreau TM, Mabury SA, Solomon KR.

Centre for Toxicology, University of Guelph, Bovey Building, Gordon Street, Guelph, Toronto, Ont., Canada N1G 2W1.

This comparative survey summarizes six individual studies on the ecological effects of two common perfluorinated surfactants, PFOS and PFOA, on zooplankton. We compare the test designs and quantify the relative sensitivity and statistical power ( [Formula: see text] ). The survey compares 30-L indoor microcosm to 12,000-L outdoor microcosm experiments, with 225-mL single species laboratory tests as reference. By this we elucidate the extrapolation of ecological effects in space and complexity. Generally, zooplankton had lower tolerance toward PFOS than toward PFOA. With increasing concentrations the zooplankton community became simplified toward more robust rotifer species, which, as an indirect effect, increased their abundance due to a shift in competition and predation. The statistical power of the designs exhibits inverse proportionality between complexity and realism, indoor microcosm>outdoor microcosm. Surprisingly, the 30-L study had a lower LOEC value for Daphnia magna than the laboratory chronic test, indicating that D. magna and D. pulicaria were not the most sensitive species and that laboratory tests are not always conservative relative to microcosm experiments. Food scarcity due to phytotoxicity was not the reason for the difference.

PMID: 15087165 [PubMed - in process]

Toxicol Sci. 2004 Apr 7 [Epub ahead of print]
trans-Activation of PPAR{alpha} and Induction of PPAR{alpha} Target Genes by Perfluorooctane-Based Chemicals.

Shipley JM, Hurst CH, Tanaka SS, DeRoos FL, Butenhoff JL, Seacat AM, Waxman DJ.

Division of Cell and Molecular Biology, Department of Biology, Boston University, 5 Cummington St., Boston MA 02215.

Peroxisome proliferator-activated receptors (PPARs) are ligand-dependent transcription factors that activate target genes involved in lipid metabolism, energy homeostasis and cell differentiation in response to diverse compounds, including environmental chemicals. The liver-expressed receptor PPARalpha mediates peroxisome proliferative responses associated with rodent hepatocarcinogenesis. Previous studies have established that certain perfluorooctanesulfonamide-based chemicals (PFOSAs) alter lipid metabolism, are hepatic peroxisome proliferators and induce hepatocellular adenoma formation in rodents, suggesting that they activate PPARalpha. The present study investigates this question and characterizes the activation of mouse and human PPARalpha by PFOSAs. Perfluorooctanesulfonate (PFOS), an end-stage metabolite common to several PFOSAs, was found to activate both mouse and human PPARalpha in a COS-1 cell-based luciferase reporter trans-activation assay. Half-maximal activation (EC50) occurred at 13-15 micro M PFOS, with no significant difference in the responsiveness of mouse and human PPARalpha. Mouse and human PPARalpha were activated by perfluorooctanesulfonamide (FOSA) over a similar concentration range; however, cellular toxicity precluded an accurate determination of EC50 values. Studies of 2-N-ethylperfluorooctanesulfonamido ethyl alcohol were less informative due to its insolubility. These findings were verified in an FAO rat hepatoma cell line that stably expresses PPARalpha, where the endogenous PPARalpha target genes peroxisomal bifunctional enzyme and peroxisomal 3-ketoacyl-CoA thiolase were activated up to approximately 10-20-fold by PFOS and FOSA. The interactions of PPARalpha with PFOS and FOSA, and the potential of these chemicals for activation of unique sets of downstream target genes, may help explain the diverse biological effects exhibited by PFOSAs and may aid in the evaluation of human and environmental risks associated with exposure to this important class of perfluorochemicals.

PMID: 15071170 [PubMed - as supplied by publisher]

Environ Sci Technol. 2004 Feb 1;38(3):758-62.

Biotransformation of N-ethyl perfluorooctanesulfonamide by rainbow trout (Onchorhynchus mykiss) liver microsomes.

Tomy GT, Tittlemier SA, Palace VP, Budakowski WR, Braekevelt E, Brinkworth L, Friesen K.

Department of Fisheries and Oceans, Winnipeg, Manitoba R3T 2N6, Canada.

Rainbow trout (Onchorhynchus mykiss) liver microsomes were incubated with N-ethyl perfluorooctanesulfonamide [N-EtPFOSA, C8F17SO2NH(C2H5)], to examine the possibility of in vitro biotransformation to perfluorooctane sulfonate (PFOS, C8F17SO3-) and perfluorooctanoate (PFOA, C7F15COO-). Incubations were performed by exposing trout liver microsomes to N-EtPFOSA at 8 degrees C in the dark. Reaction mixtures were analyzed after incubation periods of 0, 2, 4, 8, 16, and 30 h for N-EtPFOSA, PFOS, PFOA, and perfluorooctanesulfonamide (PFOSA, C8F17SO2NH2), a suspected intermediate. Amounts of PFOS and PFOSA were found to increase with incubation time, but only background levels of PFOA were detected. Three possible reaction pathways are proposed for the conversion of N-EtPFOSA to PFOS:
(i) direct conversion of N-EtPFOSA to PFOS by deethylamination accompanied by conversion of the sulfone group to sulfonate,
(ii) deethylation of N-EtPFOSA to PFOSA, followed by deamination to form PFOS, and
(iii) direct hydrolysis of N-EtPFOSA.
These findings represent the first report indicating a possible biotransformation of a perfluorosulfonamide to PFOS in fish and may help to explain the detection of PFOS, which is relatively involatile, and thus not likely to undergo atmospheric transport, in biota from remote regions.

PMID: 14968861 [PubMed - in process]

Dis Markers. 2003-2004;19(1):19-25.

Peroxisomal enzymes and 8-hydroxydeoxyguanosine in rat liver treated with perfluorooctanoic acid.

Abdellatif A, Al-Tonsy AH, Awad ME, Roberfroid M, Khan MN.

Garyounis Faculty of Medicine, Pharmacology Department, Benghazi, Lybia.

Although peroxisome proliferators are considered non-genotoxic agents, most of them, nevertheless, were found to promote and/or induce, hepatocellular carcinoma (HCC) in rodents. The aim of the present study is, first, to investigate whether the peroxisome proliferator perfluorooctanoic acid (PFOA) possesses inherent liver cancer promoting activity, and second, to study the possible mechanisms involved. To acheive these aims two protocols have been applied, a biphasic protocol (initiation by diethyl-nitrozamine (DEN) 200 mg/kg i.p. followed by treatment with 0.005% or 0.02% perflourooctanoic acid (PFOA) for 14 and 25 weeks) and a triphasic initiation, selection-promotion (IS) protocol (initiation by giving 200 mg/kg DEN i.p. followed by a selection procedure for 2 weeks consisting of giving 0.03% 2-acetylaminofluorene (2-AAF) in diet). In the middle of this treatment a single oral dose of carbon tetrachloride (2.0 ml/kg) was given, followed by giving diet containg 0.015% of PFOA for 25 weeks. After applying both protocols, our results showed slight increase in the catalase activity while acyl CoA oxidase activity was markedly increased. Both experiments indicated that PFOA has a liver cancer promoting activity. Other groups of rats were given either basal diet or diet containing 0.02% PFOA. Five or nine weeks later they were sacrificed and the levels of 8-hydroxydeoxyguanosine in the isolated DNA were estimated. The data showed a slight nonetheless insignificant increase in 8-hydroxydeoxyguanosine. From the present data, it is concluded that PFOA is a true liver cancer promoter that may not require extensive initial DNA damage for its promoting activity.

PMID: 14757943 [PubMed - in process]

Chemosphere. 2004 Mar;54(11):1599-611.
Serum concentrations of perfluorooctanesulfonate and other fluorochemicals in an elderly population from Seattle, Washington.

Olsen GW, Church TR, Larson EB, van Belle G, Lundberg JK, Hansen KJ, Burris JM, Mandel JH, Zobel LR.

Medical Department, 3M Company, Mail Stop 220-3W-05, 55144, St. Paul, MN, USA

Perfluorooctanesulfonyl fluoride (POSF, C(8)F(17)SO(2)F) related-materials have been used as surfactants, paper and packaging treatments, and surface (e.g., carpet, textile, upholstery) protectants. A metabolite, perfluorooctanesulfonate (PFOS, C(8)F(17)SO(3)(-)), has been identified in the serum and liver of non-occupationally exposed humans and wildlife. Because of its persistence, an important question was whether elderly humans might have higher PFOS concentrations. From a prospective study designed to examine cognitive function in the Seattle (WA) metropolitan area, blood samples were collected from 238 dementia-free subjects (ages 65-96). High-pressure liquid chromatography-electrospray tandem mass spectrometry determined seven fluorochemicals: PFOS; N-ethyl perfluorooctanesulfonamidoacetate; N-methyl perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamide; perfluorooctanoate; and perfluorohexanesulfonate. Serum PFOS concentrations ranged from less than the lower limit of quantitation (3.4 ppb) to 175.0 ppb (geometric mean 31.0 ppb; 95% CI 28.8-33.4). An estimate of the 95% tolerance limit was 84.1 ppb (upper 95% confidence limit 104.0 ppb). Serum PFOS concentrations were slightly lower among the most elderly. There were no significant differences by sex or years residence in Seattle. The distributions of the other fluorochemicals were approximately an order of magnitude lower. Similar to other reported findings of younger adults, the geometric mean serum PFOS concentration in non-occupational adult populations likely approximates 30-40 ppb with 95% of the population's serum PFOS concentrations below 100 ppb.

PMID: 14675839 [PubMed - in process]

Environ Sci Technol. 2004 Jan 15;38(2):373-80.

Identification of long-chain perfluorinated acids in biota from the Canadian Arctic.

Martin JW, Smithwick MM, Braune BM, Hoekstra PF, Muir DC, Mabury SA.

Department of Chemistry, University of Toronto, 80 St. George Street, Lash Miller Building, Toronto, Ontario M5S 3H6, Canada.

Recently it was discovered that humans and animals from various urban and remote global locations contained a novel class of persistent fluorinated contaminants, the most pervasive of which was perfluorooctane sulfonate (PFOS). Lower concentrations of perfluorooctanoate, perfluorohexane sulfonate, and heptadecafluorooctane sulfonamide have also been detected in various samples. Although longer perfluoroalkyl carboxylates (PFCAs) are used in industry and have been detected in fish following a spill of aqueous film forming foam, no studies have been conducted to examine the widespread occurrence of long-chain PFCAs (e.g., CF3(CF2)xCOO-, where x > 6). To provide a preliminary assessment of fluorinated contaminants, including PFCAs, in the Canadian Arctic, polar bears, ringed seals, arctic fox, mink, common loons, northern fulmars, black guillemots, and fish were collected at various locations in the circumpolar region. PFOS was the major contaminant detected in most samples and in polar bear liver was the most prominent organohalogen (mean PFOS = 3.1 microg/g wet weight) compared to individual polychlorinated biphenyl congeners, chlordane, or hexachlorocyclohexane-related chemicals in fat. Using two independent mass spectral techniques, it was confirmed that all samples also contained ng/g concentrations of a homologous series of PFCAs, ranging in length from 9 to 15 carbons. Sum concentrations of PFCAs (sum(PFCAs)) were lower than total PFOS equivalents (sum(PFOS)) in all samples except for mink. In mink, perfluorononanoate (PFNA) concentrations exceeded PFOS concentrations, indicating that PFNA and other PFCAs should be considered in future risk assessments. Mammals feeding at higher trophic levels had greater concentrations of PFOS and PFCAs than mammals feeding at lower trophic positions. In general, odd-length PFCAs exceeded the concentration of even-length PFCAs, and concentrations decreased with increasing chain length in mammals. PFOS and PFCA concentrations were much lower for animals living in the Canadian Arctic than for the same species living in mid-latitude regions of the United States. Future studies should continue to monitor all fluorinated contaminants and examine the absolute and relative toxicities for this novel suite of PFCAs.

PMID: 14750710 [PubMed - in process]

Mech Ageing Dev. 2004 Jan;125(1):69-75.
Enhanced potential for oxidative stress in livers of senescent rats by the peroxisome proliferator-activated receptor alpha agonist perfluorooctanoic acid.

Badr MZ (a), Birnbaum LS (b)

(a) University of Missouri-Kansas City, 2411 Holmes Street, 64108, Kansas City, MO, USA
(b) National Health and Environmental Effects Research Laboratory, USEPA, Research Triangle Park, NC 27711, USA

Aging sensitizes the liver to the hepatocarcinogenic effect of PPARalpha agonists via unknown mechanisms. This study was designed to investigate age-dependent, hepatic effects of the non-metabolizable PPARalpha agonist perfluorooctanoic acid (PFOA) on the delicate balance between activities of pathways involved in H(2)O(2) production and elimination. Male Fischer-344 rats, ranging in age from juvenile (4 weeks old), post puberty (10 weeks old), mature adulthood (20 weeks old), middle age (50 weeks old), to senescence (100 weeks old), were treated intragastrically with either 150mg PFOA/kg in 0.5ml corn oil, or with corn oil alone. Animals were sacrificed at predetermined time-points ranging from 0-28 days post PFOA or oil administration. Hepatic peroxisomal beta-oxidizing activities were significantly elevated (four- to six-fold) in all age groups by PFOA. While levels declined to near basal values within 3-7 days in 4 and 10, they remained elevated for an additional week in 20-, 50- and 100-week-old rats. However, catalase activity was significantly lower in senescent livers compared with all other groups. In conclusion, aging does not appear to hinder the capacity of the liver to produce excess H(2)O(2) through peroxisomal beta-oxidation upon exposure to PPAR agonists. However, the reduced ability of the senescent liver to recover from PFOA-induced potential increase in H(2)O(2) production, coupled with the apparent diminished capacity of this liver to decompose H(2)O(2), enhances the potential for hepatic oxidative damage in aged animals. This may explain the enhanced susceptibility of the senescent liver to the hepatocarcinogenic effect of PPAR agonists.

PMID: 14706239 [PubMed - in process]

Environ Sci Technol. 2004 Mar 1;38(5):1313-20.

Indoor and outdoor air concentrations and phase partitioning of perfluoroalkyl sulfonamides and polybrominated diphenyl ethers.

Shoeib M, Harner T, Ikonomou M, Kannan K.

Meteorological Service of Canada, Environment Canada, 4905 Dufferin Street, Toronto, Ontario, Canada M3H 5T4.

Perfluoroalkyls (PFAs) and polybrominated diphenyl ethers (PBDEs) are two classes of emerging persistent organic pollutants (POPs) that are widely used in domestic and workplace products. These compounds also occur in remote locations such as the Arctic where they are accumulated in the food chain. This study makes connections between indoor sources of these chemicals and the potential and mode for their transport in air. In the case of the PFAs, three perfluoralkyl sulfonamides (PFASs) were investigated--N-methyl perfluorooctane sulfonamidoethanol (MeFOSE), N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE), and N-methyl perfluorooctane sulfonamidethylacrylate (MeFOSEA). These are believed to act as precursors that eventually degrade to perfluorooctane sulfonate (PFOS), which is detected in samples from remote regions. High-volume samples were collected for indoor and outdoor air to investigate the source signature and strength. Mean indoor air concentrations (pg/m3) were 2590 (MeFOSE), 770 (EtFOSE), and 630 (sigmaPBDE). The ratios of concentration between indoor and outdoor air were 110 for MeFOSE, 85 for EtFOSE, and 15 for sigmaPBDE. The gas and particle phases were collected separately to investigate the partitioning characteristics of these chemicals. Measured particulate percentages were compared to predicted values determined using models based on the octanol-air partition coefficient (K(OA)) and supercooled liquid vapor pressure (pL(o)); these models were previously developed for nonpolar, hydrophobic chemicals. To make this comparison for the three PFASs, it was necessary to measure their K(OA) and vapor pressure. K(OA) values were measured as a function of temperature (0 to +20 degrees C). Values of log K(OA) at 20 degrees C were 7.70, 7.78, and 7.87 for MeFOSE, EtFOSE, and MeFOSEA, respectively. Partitioning to octanol increased at colder temperatures, and the enthalpies associated with octanol-air transfer (deltaH(OA), kJ/mol) were 68-73 and consistent with previous measurements for nonpolar hydrophobic chemicals. Solid-phase vapor pressures (pS(o)) were measured at room temperature (23 degrees C) by the gas saturation method. Values of pS(o) (Pa) were 4.0 x 10(-4), 1.7 x 10(-3), and 4.1 x 10(-4), respectively. These were converted to pL(o) for describing particle-gas exchange. Both the pL(o)-based model and the K(OA) model worked well for the PBDEs but were not valid for the PFASs, greatly underpredicting particulate percentages. These results suggest that existing K(OA)- and pL(o)-based models of partitioning will need to be recalibrated for PFASs.

PMID: 15046331 [PubMed - in process]

Environ Sci Technol. 2004 Mar 1;38(5):80A.

Comment on:
* Environ Sci Technol. 2004 Mar 1;38(5):1313-20.

Perfluorinated sources outside and inside.

Renner R.

Publication Types:
* Comment
* News

PMID: 15046317 [PubMed - indexed for MEDLINE]

J Am Chem Soc. 2004 Mar 3;126(8):2308-9.
Reductive activation of carbon-fluorine bonds in perfluoroalkyl ligands: an unexpected route to the only known tetrafluorobutatriene transition metal complex: Ir(eta 5-C5Me5)(PMe3)(2,3-eta 2 -CF2[double bond]C[double bond]C[double bond]CF2).

Hughes RP, Laritchev RB, Zakharov LN, Rheingold AL.

Department of Chemistry, 6128 Burke Laboratory, Dartmouth College, Hanover, New Hampshire 03755,USA.

No Abstract available

PMID: 14982426 [PubMed - in process]

Zhongguo Wei Zhong Bing Ji Jiu Yi Xue. 2004 May;16(5):270.

[Experiences in emergency treatment for 38 cases with organofluorine]

[Article in Chinese]

Jian XJ, Yu SY.

No abstract available

Moxian Hospital, Xinjiang 841900, China.

PMID: 15132788 [PubMed - in process]

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