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2004 Abstracts: PFOS and PFOA
NOTES:
Several papers in a new category "Fluorinated POPS (persistent organic pollutants)" were presented at Dioxin 2004: 24th International Symposium on Halogenated Environmental Organic Pollutants and POPs. Berlin, September 6 - 10, 2004. They are listed below.
US EPA's List of Inerts contained several PFOS. Most, but not all, have been deleted from these lists since 2001. The so-called "Inerts" are used in pesticides and can account for as much as 95%, or more, of a pesticidal formulation. US EPA's policy has been to consistently deny the public information on
Abstracts on PFOS and PFOA for the following years:
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)
104 page Report released October 2004
ENVIRONMENTAL RISK EVALUATION REPORT:
PERFLUOROOCTANESULPHONATE (PFOS)UK Environment Agency’s Science Group
Authors: D Brooke, A Footitt, T A Nwaogu
Research Contractor:
Building Research Establishment Ltd
Risk and Policy Analysts Ltd
43 page Report released October 2004
Proposal for Regulations on PFOS-Related Substances: Partial Regulatory Impact Assessment
prepared for
UK Department for Environment, Food and Rural Affairs (Defra)by
Risk & Policy Analysts Limited,
Farthing Green House, 1 Beccles Road, Loddon, Norfolk, NR14 6LTin association with:
BRE Environment
Garston, Watford, WD25 9XX, UK
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. jwmartin@ualberta.ca
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]
Journal of Fluorine Chemistry Volume 125, Issue 8 , August 2004, Pages 1211-1216
Fluorine in Alternative Energy SourcesNafion® 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, USAAbstract: 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 1;38(23):452A.
No Abstract available
Canada moves to eliminate PFOS stain repellents.
Pelley J.
PMID: 15597866 [PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15575267Environ 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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15573615Environ 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. h-hori@aist.go.jp
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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15573472Drug 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. rgperkins@mmm.com
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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15573471Drug 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. xing.han@usa.dupont.com
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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15559291Environ 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. ankley.gerald@epa.gov
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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15497853Water 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. meesters@isa.rwth-aachen.de
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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15461154Environ 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. Kkannan@wadsworth.org
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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15461284Wei 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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15470233Toxicol 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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15378987Environ 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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15352480Environ 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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15352442Environ 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]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15352441Environ 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]
Full free report available at http://dioxin2004.abstract-management.de/pdf/p134.pdf
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 LankaIntroduction. 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.
Full free report available at http://dioxin2004.abstract-management.de/pdf/p350.pdf
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.
LEVELS OF PERFLUOROALKYLATED COMPOUNDS IN WHOLE BLOOD FROM SWEDEN
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 UniversityIntroduction. 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. ...
Full free report available at http://dioxin2004.abstract-management.de/pdf/p304.pdf
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.
PERFLUORINATED CARBOXYLATES AND SULFONATES IN OPEN OCEAN WATERS OF THE PACIFIC AND ATLANTIC OCEANS
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.
Full free report available at http://dioxin2004.abstract-management.de/pdf/p387.pdf
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.
ENVIRONMENTAL CONTAMINATION BY PERFLUORINATED CARBOXYLATES AND SULFONATES FOLLOWING THE USE OF FIRE-FIGHTING FOAM IN TOMAKOMAI, JAPAN
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, KielIntroduction. 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...
Full free report available at http://dioxin2004.abstract-management.de/pdf/p666.pdf
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.
Full free report available at http://dioxin2004.abstract-management.de/pdf/p140.pdf
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, OttawaIntroduction. 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...
Full free report available at http://dioxin2004.abstract-management.de/pdf/p489.pdf
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, HamburgIntroduction. 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.
Full free report available at http://dioxin2004.abstract-management.de/pdf/p269.pdf
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, JapanIntroduction. 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.
Full free report available at http://dioxin2004.abstract-management.de/pdf/p437.pdf
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, TsukubaIntroduction. 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.
Full free report available at http://dioxin2004.abstract-management.de/pdf/p324.pdf
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), KjellerIntroduction. 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 http://dioxin2004.abstract-management.de/pdf/p684.pdf
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.
TOXICOLOGICAL PERSPECTIVES ON PERFLUORINATED COMPOUNDS IN AVIAN SPECIES
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 http://dioxin2004.abstract-management.de/pdf/p94.pdf
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, CanadaIntroduction. 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.
Full free report available at http://dioxin2004.abstract-management.de/pdf/p347.pdf
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.
DEVELOPMENT OF A METHOD FOR THE ANALYSIS OF PERFLUOROALKYLATED COMPOUNDS IN WHOLE BLOOD
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 UniversityIntroduction. 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.
Full free report available at http://dioxin2004.abstract-management.de/pdf/p148.pdf
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 http://dioxin2004.abstract-management.de/pdf/p142.pdf
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, GuelphIntroduction. 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