PFOS and PFOA
2005 Abstracts
 
 
Abstracts on PFOS and PFOA for the following years:
2005

Note: PFOS and PFOA are a class of perfluorinated chemicals that are best known for their use in the production of Teflon and other stain resistent materials. The interest of the FAN Pesticide Project in this issue is due to the use of several of the PFOS and PFOA chemicals as "inerts" in pesticides. However, most, but not all, have been deleted from use since 2001. The so-called "inerts" used in pesticides 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:

PFOS-PFOA. Jan 4, 2005. Draft Risk Assessment of the potential human health effects associated with exposure to perfluorooctanoic acid and its salts. US EPA Office of Pollution Prevention and Toxics, Risk Assessment Division. (132 pages)


Environmental Pollution
Article in Press, Corrected Proof.  Available online 21 November 2005.

Perfluorooctanesulfonate and related fluorochemicals in biological samples from the north coast of Colombia

Jesus Olivero-Verbel (a), Lin Tao (b), Boris Johnson-Restrepo(a, b), Jorge Guette-Fernández (a), Rosa Baldiris-Avila (a), Indira O'byrne-Hoyos (a) and Kurunthachalam Kannan (b)

(a) Environmental and Computational Chemistry Group, Department of Chemistry, University of Cartagena, A.A. 6541 Cartagena, Colombia
(b) Wadsworth Center, New York State Department of Health and Department of Environmental Health Sciences, State University of New York at Albany, Empire State Plaza, PO Box 509, Albany, NY 12201-0509, USA

Perfluorinated compounds are widespread pollutants of toxicological importance that have been detected in environmental matrices. However, little is known on their distribution in South America. In this study, distribution of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorohexanesulfonate (PFHxS), and perfluorooctanesulfonamide (PFOSA) was determined in the bile of mullet, Mugil incilis, and in tissues of pelicans (Pelecanus occidentalis) collected from North Colombia. Analysis was performed by HPLC mass spectrometry after ion-pair extraction. PFOS was found in all bile samples and PFOA and PFHxS were detected at lower frequency. Average concentrations of PFOS, PFOA, and PFHxS in bile of fish from Cartagena Bay, an industrialized site, and Totumo marsh, a reference site, were 3673, 370, 489 and 713, 47.4, 1.27 ng/mL, respectively. PFOS concentrations in pelican organs decreased in the order of spleen > liver > lung > kidney > brain > heart > muscle. These results suggest, for the first time, that perfluorinated compounds are also found in wildlife from Latin American countries.

Fig. 5. Average PFOS and PFOSA concentrations (ng/g, wet weight) in different tissues of pelicans from Cartagena Bay, Colombia. PFOSA values and the number of positive samples detected are underlined.

http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16221955&query_hl=7

Toxicol Sci. 2005 Oct 12; [Epub ahead of print]
 
Gene Expression Profiles in Rat Liver Treated With Perfluorooctanoic Acid (PFOA).

Guruge KS, Yeung LW, Yamanaka N, Miyazaki S, Lam PK, Giesy JP, Jones PD, Yamashita N.

Toxico-Biochemistry Section, National Institute of Animal Health, Kannondai 3-1-5, Tsukuba, Ibaraki 305-0856, Japan.

Perfluorooctanoic acid (PFOA; Pentadecafluorooctanoic acid ) is widely used in various industrial applications. It is persistent in the environment and does not appear to undergo further degradation or transformation. PFOA is found in tissues including blood of wildlife and humans, however, the environmental fate and biological effects of PFOA remain unclear. Microarray techniques of gene expression have become a powerful approach for exploring the biological effects of chemicals. Here, the Affymetrix, Inc. rat genome 230 2.0 GeneChip was used to identify alterations in gene regulation in Sprague-Dawley rats treated with five different concentrations of PFOA. Male rats were exposed by daily gavage to 1, 3, 5, 10, or 15 mg PFOA/kg, bw/d for 21 d and at the end of the exposure, liver was isolated and total liver RNA were used for the gene chip analysis. Over 500 genes, whose expression was significantly (P<0.0025) altered by PFOA at two-fold changes compared to control, were examined. The effects were dose-dependent with exposure to 10mg PFOA/kg, bw/d, causing alteration in expression of the greatest number of genes (over 800). Approximately 106 genes and 38 genes were consistently up- or down-regulated, respectively in all treatment groups. The largest categories of induced genes were those involved in transport and metabolism of lipids, particularly fatty acids. Other induced genes were involved in cell communication, adhesion, growth, apoptosis, hormone regulatory pathways, proteolysis and peptidolysis and signal transduction. The genes expression of which was suppressed were related to transport of lipids, inflammation and immunity, and especially cell adhesion. Several other genes involved in apoptosis; regulation of hormones; metabolism; and G-protein coupled receptor protein signaling pathways were significantly suppressed.

PMID: 16221955 [PubMed - as supplied by publisher]


Mutation Research/Genetic Toxicology and Environmental Mutagenesis
Volume 587, Issues 1-2 , 10 November 2005, Pages 38-44
 
Genotoxic risk and oxidative DNA damage in HepG2 cells exposed to perfluorooctanoic acid.

Yao X, Zhong L.

Department of Toxicology, Dalian Medical University, 465 Zhongshan Road, Dalian, 116027 Liaoning, China.

Perfluorooctanoic acid (C(8)HF(15)O(2), PFOA) is widely used in various industrial fields for decades and it is environmentally bioaccumulative. PFOA is known as a potent hepatocarcinogen in rodents. But it is not yet clear whether it is also carcinogenic in humans, and the genotoxic effects of PFOA on human cells have not yet been examined. In this study, the genotoxic potential of PFOA was investigated in human hepatoma HepG2 cells in culture using single cell gel electrophoresis (SCGE) assay and micronucleus (MN) assay. In order to clarify the underlying mechanism(s) we measured the intracellular generation of reactive oxygen species (ROS) using dichlorofluorescein diacetate as a fluorochrome. The level of oxidative DNA damage was evaluated by immunocytochemical analysis of 8-hydroxydeoxyguanosine (8-OHdG) in PFOA-treated HepG2 cells. PFOA at 50-400muM caused DNA strand breaks and at 100-400muM MN in HepG2 cells both in a dose-dependent manner. Significantly increased levels of ROS and 8-OHdG were observed in these cells. We conclude that PFOA exerts genotoxic effects on HepG2 cells, probably through oxidative DNA damage induced by intracellular ROS.


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16040121&query_hl=10

Ecotoxicol Environ Saf. 2005 Jul 22; [Epub ahead of print]

The bioconcentration factor of perfluorooctane sulfonate is significantly larger than that of perfluorooctanoate in wild turtles (Trachemys scripta elegans and Chinemys reevesii): An Ai river ecological study in Japan.

Morikawa A, Kamei N, Harada K, Inoue K, Yoshinaga T, Saito N, Koizumi A.

Department of Health and Environmental Sciences, Kyoto University Graduate School of Medicine, Yoshida Konoe, Sakyo, Kyoto 606-8501, Japan.

Turtles rank high in the river food chain, and are suitable for predicting the bioconcentrations of chemicals through the food chain. Trachemys scripta elegans (N=46) and Chinemys reevesii (N=51) were captured in a river in Japan, from September to October 2003 and April to June 2004. Surface water samples were collected simultaneously from the same sites at which the turtles were caught. Serum perfluorooctane sulfonate (PFOS) ranged from 2.4 to 486mug/L, while water PFOS levels ranged from 2.9 to 37ng/L. The geometric mean (GM) (geometric standard deviation, GSD) of the bioconcentration factor (BCF) of PFOS was 10,964 (2.5). In contrast, the perfluorooctanoate (PFOA) level in water ranged from 16.7-87,100ng/L, and serum PFOA ranged from <0.2 to 870mug/L. The GM (GSD) of the BCF of PFOA was 3.2 (7.9). Furthermore, the BCF of PFOA decreased as the PFOA level in the surface water increased. PFOS could be preferentially bioconcentrated in biota, and PFOA, slightly bioconcentrated.

PMID: 16040121 [PubMed - as supplied by publisher]


From Science Direct

Regulatory Toxicology and Pharmacology - 2005
Article in Press, Corrected Proof.
Available online 20 January 2005.

Toxicological profile of hydrofluoropolyethers

G. Malinverno (a), I. Colombo (b), and M. Visca (b)

(a) Solvay S.A., European Public Affairs Brussels, Belgium
(b) Solvay Solexis R&D Centre, Regulatory Affairs and Industrial Toxicology, Bollate, Italy

Hydrofluoropolyethers (HFPE) are a family of linear oligomeric fluorinated fluids comprising a chain of difluoromethoxy and tetrafluoroethoxy repeating units with terminal OCF2H end groups, each of which contains an isolated hydrogen atom. These fluids have been designed as low environmental impact substitutes for perfluorinated organic substances in a number of applications including heat transfer and fire suppression agents, and as a solvent. The toxicological profile of these new fluids has been evaluated and is presented in this paper. Acute toxicity tests have been performed on Sprague–Dawley Crl: CD (SD) BR rats using oral, dermal, and inhalation routes. No deaths were recorded even at the highest tested concentrations, and the resultant LD50/LC50 values were >5000 mg/kg (oral), >2000 mg/kg (dermal), and >26,411 ppm (inhalation: reversible anaesthetic effects, e.g., lethargy, seen at this exposure concentration). Other short-term tests (skin and eye irritation, skin sensitisation, genotoxicity tests in vitro and in vivo, cardiac sensitisation) were also performed, and no hazardous properties were identified. Effects of repeated exposure by inhalation were examined in rats over test periods of 5, 14, 28, and 90 days. Effects on embryo–foetal development in the rat have also been studied. The 28-day, 90-day and developmental studies were performed using nominal HFPE concentrations of 1000, 3300, and 10,000 ppm (6 h/day: actual exposures confirmed by test atmosphere analysis), and the highest tested concentration proved to be an NOAEL in each study. Major observed effects were elevated urinary (inorganic) fluoride levels and increased liver weights with centrilobular hepatocyte hypertrophy (considered an adaptive response, linked to hepatic metabolism of absorbed material).


Full report available at Science Direct

Toxicology . V 215, Issues 1-2 , 5 November 2005, Pages 149-169

Neonatal mortality from in utero exposure to perfluorooctanesulfonate (PFOS) in Sprague–Dawley rats: Dose–response, and biochemical and pharamacokinetic parameters

Deanna J. Luebker (a), Raymond G. York (b), Kristen J. Hansenc(c) , John A. Moore (d), and John L. Butenhoff (a)

(a) 3M Medical Department, Corporate Toxicology and Regulatory Services, 3M Center Building 220-06-E-03, St. Paul, MN 55144, USA
(b) Argus Divison, Charles River Laboratories, 905 Sheehy Drive Bldg A, Horsham, PA 19044, USA
(c) 3M Drug Delivery Systems Division, 3M Center Building 260-04-N-12, St. Paul, MN 55144, USA
dHollyhouse, Inc., P. O. Box 474, Wicomico Church, VA 22579, USA

Perfluorooctanesulfonate (PFOS) is a widely distributed, environmentally persistent acid found at low levels in human, wildlife, and environmental media samples. Neonatal mortality has been observed following PFOS exposure in a two-generation reproduction study in rats and after dosing pregnant rats and mice during gestation. Objectives of the current study were to better define the dose–response curve for neonatal mortality in rat pups born to PFOS-exposed dams and to investigate biochemical and pharmacokinetic parameters potentially related to the etiology of effects observed in neonatal rat pups. In the current study, additional doses of 0.8, 1.0, 1.2, and 2.0 mg/kg/day were included with original doses used in the two-generation study of 0.4 and 1.6 mg/kg/day in order to obtain data in the critical range of the dose–response curve. Biochemical parameters investigated in dams and litters included: (1) serum lipids, glucose, mevalonic acid, and thyroid hormones; (2) milk cholesterol; and (3) liver lipids. Pharmacokinetic parameters investigated included the interrelationship of administered oral dose of PFOS to maternal body burden of PFOS and the transfer of maternal body burden to the fetus in utero and pup during lactation, as these factors may affect neonatal toxicity. Dosing of dams occurred for 6 weeks prior to mating with untreated breeder males, through confirmed mating, gestation, and day four of lactation. Dose levels for the dose–response and etiological investigation were 0.0, 0.4, 0.8, 1.0, 1.2, 1.6, and 2.0 mg/kg/day PFOS. Statistically significant decreases in gestation length were observed in the 0.8 mg/kg and higher dose groups. Decreases in viability through lactation day 5 were observed in the 0.8 mg/kg and higher dose groups, becoming statistically significant in the 1.6 and 2.0 mg/kg dose groups. Reduced neonatal survival did not appear to be the result of reductions in lipids, glucose utilization, or thyroid hormones. The endpoints of gestation length and decreased viability were positively correlated, suggesting that late-stage fetal development may be affected in pups exposed to PFOS in utero and may contribute to the observed mortality. Benchmark dose (BMD) estimates for decreased gestation length, birth weight, pup weight on lactation day 5, pup weight gain through lactation day 5, and viability resulted in values ranging from 0.27 to 0.89 mg/kg/day for the lower 95% confidence limit of the BMD5 (BMDL5). Results of analyses for PFOS in biological matrices indicate a linear proportionality of mean serum PFOS concentration to maternal administered dose prior to mating and through the first two trimesters of gestation. However, at 21 days of gestation, mean serum PFOS concentrations were notably reduced from values measured earlier in gestation. Urinary and fecal elimination was low as expected from prior observations in adult rats. Significant transfer of PFOS from dam to fetus in utero was confirmed, and results suggest that dam and corresponding fetal body burdens, as indicated by serum and liver PFOS levels, correlate with neonatal survival.


Full report available at Science Direct

Toxicology. V 215, Issues 1-2 , 5 November 2005, Pages 126-148

Two-generation reproduction and cross-foster studies of perfluorooctanesulfonate (PFOS) in rats

Deanna J. Luebker (a), Marvin T. Case (a), Raymond G. York (b), John A. Moore (c), Kristen J. Hansen (d), and John L. Butenhoff (a)

(a) 3M Medical Department, Corporate Toxicology and Regulatory Services, 3M Center Building 220-06-E-03, St. Paul, MN 55144, USA
(b) Argus Division, Charles River Laboratories, 905 Sheehy Drive Bldg A, Horsham, PA 19044, USA
(c) Hollyhouse, Inc., P.O. Box 474, Wicomico Church, VA 22579, USA
(d) 3M Drug Delivery Systems Division, 3M Center Building 260-04-N-12, St. Paul, MN 55144, USA

Perfluorooctanesulfonate (PFOS) is a persistent acid found widely distributed in wildlife and humans. To understand the potential reproductive and developmental effects of PFOS, a two-generation reproduction study was conducted in rats. Male and female rats were dosed via oral gavage at dose levels of 0, 0.1, 0.4, 1.6, and 3.2 mg/(kg day) for 6 weeks prior to mating, during mating, and, for females, through gestation and lactation, across two generations. Due to substantial F1 neonatal toxicity observed in the 1.6 and 3.2 mg/(kg day) groups, continuation into the second generation was limited to F1 pups from the 0, 0.1, and 0.4 mg/(kg day) groups. No adverse effects were observed in F0 females or their fetuses upon caesarean sectioning at gestation day 10. Statistically significant reductions in body-weight gain and feed consumption were observed in F0 generation males and females at dose levels of 0.4 mg/(kg day) and higher, but not in F1 adults. PFOS did not affect reproductive performance (mating, estrous cycling, and fertility); however, reproductive outcome, as demonstrated by decreased length of gestation, number of implantation sites, and increased numbers of dams with stillborn pups or with all pups dying on lactation days 1–4, was affected at 3.2 mg/(kg day) in F0 dams. These effects were not observed in F1 dams at the highest dose tested, 0.4 mg/(kg day). Neonatal toxicity in F1 pups, as demonstrated by reduced survival and body-weight gain through the end of lactation, occurred at a maternal dose of 1.6 mg/(kg day) and higher while not at dose levels of 0.1 or 0.4 mg/(kg day) or in F2 pups at the 0.1 or 0.4 mg/(kg day) dose levels tested. In addition to these adverse effects, slight yet statistically significant developmental delays occurred at 0.4 (eye opening) and 1.6 mg/(kg day) (eye opening, air righting, surface righting, and pinna unfolding) in F1 pups. Based on these data, the NOAELs were as follows: reproductive function: F0 ≥ 3.2 and F1 ≥ 0.4 mg/(kg day); reproductive outcome: F0 = 1.6 and F1 ≥ 0.4 mg/(kg day); overall parental effects: F0 = 0.1 and F1 ≥ 0.4 mg/(kg day); offspring effects: F0 = 0.4 and F1 ≥ 0.4 mg/(kg day). To distinguish between maternal and pup influences contributing to the perinatal mortality observed in the two-generation study, a follow-up cross-foster study was performed. Results of this study indicated that in utero exposure to PFOS causally contributed to post-natal pup mortality, and that pre-natal and post-natal exposure to PFOS was additive with respect to the toxic effects observed in pups.

• Pinna definition: The ear or, to be more precise, the part of the ear that projects like a little wing from the head. In Latin, pinna means wing.

 

Abstracts and Poster presentations
Fluoros 2005 Abstractbook (133 pages):
An International Symposium on Fluorinated Alkyl Organics in the Environment
August 18-20, 2005
Toronto, Canada

Topics:
Environmental Fate and Transport
Analytical Chemistry & Monitoring
Toxicology
Risk Assessment and Regulatory Policy


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16382930&query_hl=14&itool=pubmed_docsum

Environ Sci Technol. 2005 Dec 1;39(23):9101-8.

Perfluorinated compounds in the plasma of loggerhead and Kemp's ridley sea turtles from the southeastern coast of the United States.

Keller JM, Kannan K, Taniyasu S, Yamashita N, Day RD, Arendt MD, Segars AL, Kucklick JR.

Hollings Marine Laboratory, National Institute of Standards and Technology, Charleston, South Carolina 29412, USA. jennifer.keller@noaa.gov

Perfluorinated compounds (PFCs) have been measured in blood of humans and wildlife and are considered globally distributed contaminants. We examined 12 PFCs in the plasma of 73 loggerhead sea turtles (Caretta caretta) and 6 Kemp's ridley sea turtles (Lepidochelys kempii) captured from inshore waters of Core Sound, North Carolina (NC), and offshore waters of South Carolina, Georgia, and Florida (SC-FL). Perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the dominant compounds, with respective mean concentrations of 11.0 ng/mL and 3.20 ng/mL for loggerhead turtles and 39.4 ng/mL and 3.57 ng/mL for Kemp's ridley turtles. Mean PFOS concentrations were 2- to 12-fold higher than typical mean sigmaPCB concentrations (approximately 5 ng/g wet mass) measured previously in sea turtle blood. More than 79% of the samples had detectable levels of perfluorocarboxylates (PFCAs) with 8-12 carbons, whereas only 17% or less of samples had detectable levels of PFCAs with 6 or 7 carbons. No samples had detectable levels of PFCAs with 4 or 5 carbons. In loggerhead turtles, sigmaPFC concentrations were not influenced by sex (p > 0.05), but were higher in turtles captured from inshore waters of NC than in turtles from offshore waters of SC-FL (p = 0.009). A backward stepwise multiple regression model showed that sigmaPFC concentrations were (1) significantly higher in Kemp's ridley turtles than loggerhead turtles (p < 0.0001), (2) higher in larger turtles (p = 0.018; carapace length used as a proxy for age), and (3) higher in turtles captured toward the north (p = 0.006). These findings suggest that bioaccumulation of PFCs in sea turtles is influenced by species, age, and habitat.

PMID: 16382930 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16323762&query_hl=14&itool=pubmed_docsum

Environ Sci Technol. 2005 Nov 15;39(22):8678-83.

Ratio of perfluorochemical concentrations as a tracer of atmospheric deposition to surface waters.

Simcik MF, Dorweiler KJ.

Division of Environmental Health Sciences, School of Public Health, University of Minnesota, MMC 807, 420 Delaware Street SE, Minneapolis, Minnesota 55455, USA. msimcik@umn.edu

A major question regarding the global distribution of perfluorochemicals (PFCs) is one of transport. It has been suggested that atmospheric transport of volatile precursor compounds to remote areas and subsequent degradation to the nonvolatile PFCs is responsible for contamination of biota. This paper presents surface water PFC concentrations aimed at identifying tracers of atmospheric sources. Concentrations of PFCs including perfluorocarboxylates from C6 to C10 and perfluorooctane sulfonate (PFOS) are presented here from urban surface waters with presumably both atmospheric and nonatmospheric sources of PFCs, remote waters with only atmospheric sources of PFCs, and Lake Michigan. Perfluoroheptanoic acid (PFHpA) and perfluorooctanoic acid (PFOA) were detected in all surface water samples, and PFOS was detected in all but two samples. PFOS concentrations ranged from nondetect to 1.2 ng/L and from 2.4 to 47 ng/L in remote and urban surface waters, respectively. PFOA concentrations ranged from 0.14 to 0.66 ng/L and from 0.45 to 19 ng/L in remote and urban surface waters, respectively. The ratio of PFHpA to PFOA increased with increasing distance from nonatmospheric sources suggesting that it can be used as a tracer of atmospheric deposition of PFCs to surface waters. The ratio ranged from 0.5 to 0.9 in urban areas and from 6 to 16 in remote areas. Applying this tracer to measurements from Lake Michigan indicates that the primary source of PFCs to Lake Michigan is nonatmospheric, most likely inputs from wastewater treatment effluent.

PMID: 16323762 [PubMed - in process]


Full report available free at Science Direct

Chemosphere, Volume 61, Issue 7 , November 2005, Pages 974-984

Thermal degradation of fluorotelomer treated articles and related materials

Takahiro Yamada (a), Philip H. Taylor (a), Robert C. Buck (b), Mary A. Kaiser (c) and Robert J. Giraud (d)

(a) Environmental Engineering Group, University of Dayton Research Institute, 300 College Park, Dayton, OH 45469-0114, United States
(b) DuPont Chemical Solutions Enterprise, 4417 Lancaster Pike, BMP23-2233, Wilmington, DE 19805, United States
(c) DuPont Corporate Center for Analytical Sciences, P.O. Box 80402, Wilmington, DE 19880-0402, United States
(d) DuPont Engineering Technology, 1007 Market Street, Wilmington, DE 19898, United States

This study reports the first known studies to investigate the thermal degradation of a polyester/cellulose fabric substrate (“article”) treated with a fluorotelomer-based acrylic polymer under laboratory conditions conservatively representing typical combustion conditions of time, temperature, and excess air level in a municipal incinerator, with an average temperature of 1000 °C or greater over approximately 2 s residence time. The results demonstrate that the polyester/cellulose fabric treated with a fluorotelomer-based acrylic polymer is destroyed and no detectable amount of perfluorooctanoic acid (PFOA) is formed under typical municipal incineration conditions. Therefore, textiles and paper treated with such a fluorotelomer-based acrylic polymer disposed of in municipal waste and incinerated are expected to be destroyed and not be a significant source of PFOA in the environment.


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16249997&query_hl=4

Birth Defects Res B Dev Reprod Toxicol. 2005 Oct 25;74(5):405-416 [Epub ahead of print]
 
Effects of prenatal perfluorooctane sulfonate (PFOS) exposure on lung maturation in the perinatal rat.

Grasty RC, Bjork JA, Wallace KB, Lau CS, Rogers JM.

Reproductive Toxicology Division, NHEERL, Office of Research and Development, U.S. EPA, Research Triangle Park, North Carolina.

BACKGROUND: Perfluorooctane sulfonate (PFOS), found widely in wildlife and humans, is environmentally and metabolically stable. Environmental PFOS may be from its use as a surfactant, hydrolysis of perfluorooctanesulfonyl fluoride, and degradation of N-alkyl-perfluorooctanesulfonamide compounds formerly used in numerous applications. Prenatal exposure to PFOS in rodents causes neonatal mortality; treatment on gestation days (GD) 19-20 is sufficient to induce neonatal death in rats. Affected pups are born alive but present with labored breathing. Their lungs are pale and often do not expand fully on perfusion.
METHODS: Pregnant Sprague-Dawley rats received 0, 25, or 50 mg/kg/day PFOS/K(+) orally on GD 19-20. Lungs from GD 21 fetuses and neonates were prepared for histology and morphometry. Rescue experiments included co-administration of dexamethasone or retinyl palmitate with PFOS. Pulmonary surfactant was investigated with mass spectrometry in GD 21 amniotic fluid and neonatal lungs. Microarray analysis was carried out on PND 0 lungs.
RESULTS: Histologically, alveolar walls were thicker in lungs of PFOS-exposed newborns compared to controls. The ratio of solid tissue:small airway was increased, suggesting immaturity. Rescue studies were ineffective. Phospholipid concentrations and molecular speciation were unaffected by PFOS. No changes in markers of alveolar differentiation were detected by microarray analysis.
CONCLUSIONS: Morphometric changes in lungs of PFOS exposed neonates were suggestive of immaturity, but the failure of rescue agents and normal pulmonary surfactant profile indicate that the labored respiration and mortality observed in PFOS-treated neonates was not due to lung immaturity.

PMID: 16249997 [PubMed - as supplied by publisher]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16252056&query_hl=4

J Environ Monit. 2005;7(11):1074-1078. Epub 2005 Sep 19.
 
Occurrence of perfluorosulfonates and other perfluorochemicals in dust from selected homes in the city of Ottawa, Canada.

Kubwabo C, Stewart B, Zhu J, Marro L.

Health Canada, Healthy Environments and Consumer Safety Branch, Safe Environments Programme, Tunney's Pasture, Building No 8, Ottawa (Ontario) PL 0800C, CanadaK1A 0L2. Cariton_Kubwabo@hc-sc.gc.ca.

A series of perfluorinated compounds (PFCs) including perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have been recently measured in a variety of environmental samples and biological matrices. In order to better understand the human exposure routes of these chemicals, levels of PFOS, PFOA, perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS) and perfluorooctane sulfonamide (PFOSA) in house dust samples were investigated. The data revealed a correlation between the concentrations of PFCs and the percentage of carpeting in the house; older houses tended to have less carpeting, hence lower levels of these perfluorinated compounds in their dust.

PMID: 16252056 [PubMed - as supplied by publisher]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16245813&query_hl=4

Environ Sci Technol. 2005 Oct 1;39(19):7439-45.

Perfluorinated alkyl substances in plasma, liver, brain, and eggs of glaucous gulls (Larus hyperboreus) from the Norwegian arctic.

Verreault J, Houde M, Gabrielsen GW, Berger U, Haukas M, Letcher RJ, Muir DC.

Norwegian Polar Institute, Tromso, NO-9296, Norway, jonathan@npolar.no

Recent environmental surveys have ascertained the widespread occurrence of perfluorinated alkyl substances (PFAS) in tissues of wildlife from the Arctic. In the present study, we investigated the distribution of a suite of PFAS in plasma, liver, brain, and egg samples from adult glaucous gulls (Larus hyperboreus), an apex scavenger-predator seabird breeding in the Norwegian Arctic. Perfluorooctane sulfonate (PFOS) was the predominant PFAS in all samples and was present at concentrations that are the highest reported thus far in any arctic seabird species and populations. Among the body compartment/ tissue samples analyzed, PFOS was highest in plasma (48.1-349 ng/g wet weight (ww)), followed by liver approximately equal to egg > brain. Perfluorocarboxylic acids (PFCAs) with 8-15 carbon (C) atoms were found, with the highest concentrations determined in plasma (sum PFCA: 41.8-262 ng/g ww), whereas 5C- and 6C-PFCAs were below the limits of detection. Perfluorobutane sulfonate, perfluorooctane sulfonamide, and four saturated (8:2 FTCA and 10:2 FTCA) and unsaturated (8:2 FTUCA and 10:2 FTUCA) fluorotelomer carboxylic acids were not detected in any samples. Perfluorohexane sulfonate was measured at concentrations up to 2.71 ng/g ww. The accumulation profiles of PFCAs were characterized by high proportions of the long and odd-numbered carbon-chain-length compounds, namely perfluoroundecanoic (11C) and perfluorotridecanoic acid (13C), although their individual contribution differed between the matrixes analyzed. Current PFAS concentrations suggest a bioaccumulation potential in Norwegian arctic glaucous gulls that needs to be assessed as part of a broad organohalogen contaminant cocktail with potential for mediating biological processes in this vulnerable top-predator marine species.

PMID: 16245813 [PubMed - in process]


Full report available at Science Direct

Toxicology . V 176, Issue 3 , 15 July 2002, Pages 175-185

Interactions of flurochemicals with rat liver fatty acid-binding protein

Deanna J. Luebker (a), Kris J. Hansen (b), Nathan M. Bass (c), John L. Butenhoff (a) and Andrew M. Seacat (a)

(a) 3M Medical Department, Corporate Toxicology, 3M Center Building 220-2E-02, Saint Paul, MN 55144, USA
(b) 3M Environmental Technology and Safety Services, Building 02-3E-09, Saint Paul, MN 55144, USA
(c) School of Medicine, University of California, San Francisco, CA 94143, USA

Liver-fatty acid binding protein (L-FABP) is an abundant intracellular lipid-carrier protein. The hypothesis that perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and certain related perfluorooctanesulfonamide-based fluorochemicals (PFOSAs) can interfere with the binding affinity of L-FABP for fatty acids was tested. The relative effectiveness of PFOA, PFOS, N-ethylperfluorooctanesulfonamide (N-EtFOSA), N-ethylperfluorooctanesulfonamido ethanol (N-EtFOSE), and of the strong peroxisome proliferator Wyeth-14 643 (WY) to inhibit 11-(5-dimethylaminonapthalenesulphonyl)-undecanoic acid (DAUDA) binding to-L-FABP was determined. The dissociation constant (Kd) of the DAUDA-L-FABP complex was 0.47 nM. PFOS exhibited the highest level of inhibition of DAUDA-L-FABP binding in the competitive binding assays, followed by N-EtFOSA, WY, and, with equal IC50s, N-EtFOSE and PFOA. The in vitro data presented in this study support the hypothesis that these fluorochemicals may interfere with the binding of fatty acids or other endogenous ligands to L-FABP. Furthermore, this work provides evidence to support the hypothesis that displacement of endogenous ligands from L-FABP may contribute to toxicity in rodents fed these fluorochemicals.


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16245810&query_hl=4

Environ Sci Technol. 2005 Oct 1;39(19):7416-22.

Temporal and spatial trends of perfluorinated compounds in ringed seal (Phoca hispida) from Greenland.

Bossi R, Riget FF, Dietz R.

National Environmental Research Institute, Frederiksborgvej 399, 4000-Roskilde, Denmark. rbo@dmu.dk

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS) and related compounds, have been identified as global pollutants and have shown their bioaccumulation into higher trophic levels in the food chain. PFCs have been found in remote areas far from sources, such as the Arctic. In this study spatial and temporal trends in the concentrations of selected PFCs were measured using archived liver samples of ringed seal (Phoca hispida) from East and West Greenland. The samples were collected in four different years at each location, between 1986 and 2003 in East Greenland and between 1982 and 2003 in West Greenland. PFOS was the major contributor to the burden of PFCs in samples, followed by perfluoroundecanoic acid (PFUnA). Perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were also detected in most samples. Perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonamide (PFOSA) were only found sporadically. Perfluorooctanoic acid was not found in detectable concentrations in any sample. Regression analysis of logarithmic transformed PFOS, PFDA, and PFUnA median concentrations indicated a significant temporal trend with increasing concentrations at both locations. A spatial trend in PFOS concentrations (ANOVA, p < 0.0001) was observed between the two sampling locations, with significantly higher concentrations in seals from East Greenland.

PMID: 16245810 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16227186&query_hl=7

Food Addit Contam. 2005 Oct;22(10):1023-31.

Perfluorochemicals: Potential sources of and migration from food packaging.

Begley TH, White K, Honigfort P, Twaroski ML, Neches R, Walker RA.

US Food and Drug Administration, Center for Food Safety and Applied Nutrition, College Park, MD 20740, USA.

Perfluorochemicals are widely used in the manufacturing and processing of a vast array of consumer goods, including electrical wiring, clothing, household and automotive products. Furthermore, relatively small quantities of perfluorochemicals are also used in the manufacturing of food-contact substances that represent potential sources of oral exposure to these chemicals. The most recognizable products to consumers are the uses of perfluorochemicals in non-stick coatings (polytetrafluoroethylene (PTFE)) for cookware and also their use in paper coatings for oil and moisture resistance. Recent epidemiology studies have demonstrated the presence of two particular perfluorochemicals, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in human serum at very low part per billion levels. These perfluorochemicals are biopersistent and are the subject of numerous studies investigating the many possible sources of human exposure. Among the various uses of these two chemicals, PFOS is a residual impurity in some paper coatings used for food contact and PFOA is a processing aid in the manufacture of PTFE used for many purposes including non-stick cookware. Little information is available on the types of perfluorochemicals that have the potential to migrate from perfluoro coatings into food. One obstacle to studying migration is the difficulty in measuring perfluorochemicals by routine conventional analytical techniques such as GC/MS or LC-UV. Many perfluorochemicals used in food-contact substances are not detectable by these conventional methods. As liquid chromatography-mass spectrometry (LC/MS) develops into a routine analytical technique, potential migrants from perfluoro coatings can be more easily characterized. In this paper, data will be presented on the types of perfluoro chemicals that are used in food packaging and cookware. Additionally, research will be presented on the migration or potential for migration of these chemicals into foods or food simulating liquids. Results from migration tests show mg kg(-1) amounts of perfluoro paper additives/coatings transfer to food oil. Analysis of PTFE cookware shows residual amounts of PFOA in the low microg kg(-1) range. PFOA is present in microwave popcorn bag paper at amounts as high as 300 microg kg(-1).

PMID: 16227186 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16213555&query_hl=7

Chemosphere. 2005 Oct 4; [Epub ahead of print]

Perfluorinated chemicals in selected residents of the American continent.

Calafat AM, Needham LL, Kuklenyik Z, Reidy JA, Tully JS, Aguilar-Villalobos M, Naeher LP.

Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, 4770 Buford Hwy., NE, Mailstop F17, Atlanta, GA 30341, USA.

Perfluorinated chemicals (PFCs) are used in multiple consumer products. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), the most widely studied PFCs, may be potential developmental, reproductive, and systemic toxicants. Although PFCs seem to be ubiquitous contaminants found both in humans and animals, geographic differences may exist in human exposure patterns to PFCs. We measured 11 PFCs in 23 pooled serum samples collected in the United States from 1990 through 2002, and in serum samples collected in 2003 from 44 residents from Trujillo, Peru. PFOS and PFOA were detected in all the pooled samples; perfluorohexane sulfonic acid (PFHxS) was detected in 21. Median concentrations were 31.1 micrograms per liter (mug/l, PFOS), 11.6mug/l (PFOA), and 2mug/l (PFHxS). The 90th percentile concentrations of PFCs in the 44 Peruvian residents were 0.7mug/l (PFOS), 0.1mug/l (PFOA), and <0.3mug/l (PFHxS). The frequencies of detection were 20% (PFOS), 25% (PFOA), and 9% (PFHxS). The frequent detection of selected PFCs in the pooled samples from the United States and the lack of clear concentration trends based on a year of collection suggest a sustained widespread exposure to these compounds among US residents, at least since the 1990s. By contrast, the much lower frequency of detection and concentration ranges of PFCs in Peru suggest a lower exposure of Peruvians to PFCs compared with North Americans. Genetic variability, diet, lifestyle, or a combination of all these may contribute to the different patterns of human exposure to PFCs in the United States and Peru.

PMID: 16213555 [PubMed - as supplied by publisher]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16193761&query_hl=5

Environ Toxicol Chem. 2005 Sep;24(9):2316-24.

Reproductive and developmental toxicity and bioconcentration of perfluorooctanesulfonate in a partial life-cycle test with the fathead minnow (Pimephales promelas).

Ankley GT, Kuehl DW, Kahl MD, Jensen KM, Linnum A, Leino RL, Villeneuvet DA.

Mid-Continent Ecology Division, National Health and Environmental Effects Research Laboratory, U.S. Environmental Protection Agency, 6201 Congdon Boulevard, Duluth, Minnesota 55804, USA. ankley.gerald@epa.gov

Perfluorooctanesulfonate (PFOS) is a widespread environmental contaminant emanating from the production and/or metabolism of fluorinated chemicals with a variety of applications. The goal of this work was to assess the toxicity and bioconcentration of PFOS in the fathead minnow (Pimephales promelas). Sexually mature fish were exposed via the water for 21 d to 0 (control), 0.03, 0.1, 0.3, or 1 mg PFOS/L, and effects on reproductive capacity and endocrinology were assessed. To determine possible developmental effects, a subset of embryos from parental exposures at each test concentration were held for an additional 24 d in the same PFOS treatments. A concentration of I mg PFOS/L was lethal to adults within two weeks. The 21-d 50% effect concentration (95% confidence interval) for effects on fecundity of the fish was 0.23 (0.19-0.25) mg PFOS/L. Exposure to PFOS caused various histopathological alterations, most prominently in ovaries of adult females. Adult males exposed to 0.3 mg PFOS/L for 21 d exhibited decreased aromatase activity and elevated concentrations of plasma 11-ketotestosterone and testosterone. No significant adverse effects on survival or growth were observed in developing fathead minnows held for 24 d at PFOS concentrations up to 0.3 mg/L. Adult fathead minnows readily accumulated PFOS from the water. The largest concentrations of PFOS were in blood, followed by liver and then gonad; for all tissues, females accumulated higher concentrations than males. Water and tissue concentrations of PFOS associated with effects in this study exceeded those reported for samples collected from the field by two to three orders of magnitude, suggesting that the current risk of PFOS on aspects of fish reproduction and development assessed in this study would be small.

PMID: 16193761 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16190216&query_hl=5

Environ Sci Technol. 2005 Sep 1;39(17):6591-8.

Polyfluoroalkyl compounds in free-ranging bottlenose dolphins (Tursiops truncatus) from the Gulf of Mexico and the Atlantic Ocean.

Houde M, Wells RS, Fair PA, Bossart GD, Hohn AA, Rowles TK, Sweeney JC, Solomon KR, Muir DC.

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

Polyfluoroalkyl compounds (PFAs) have been used for decades in industrial and commercial products and are now detected worldwide. Concentrations of two major PFA groups, carboxylic acids (PFCAs) and sulfonic acids (PFSAs), were assessed in plasma of bottlenose dolphins from the Gulf of Mexico (Sarasota Bay, FL) and the Atlantic Ocean (Delaware Bay, NJ, Charleston, SC, Indian River Lagoon (IRL), FL, and Bermuda). Eight PFAs were detected in the plasma of all dolphins. Perfluorooctane sulfonate (PFOS) was the predominant compound at all locations (range from 49 ng/g wet weight (w.w.) in dolphins from Bermuda to 1171 ng/g w.w. in plasma of animals from Charleston). Sum of PFA concentrations were significantly higher in animals from Charleston compared to IRL, Sarasota Bay, and Bermuda. Concentrations of several PFAs were negatively associated with age in animals from IRL and Charleston. No differences between gender were observed for all compounds at all locations. An increase in PFA concentrations was associated with a decrease of blubber thickness in animals from Sarasota Bay and IRL. Fluorotelomer 8:2 and 10:2 unsaturated carboxylic acids (FTUCAs), known degradation products of fluorotelomer alcohols and suspected precursors to PFCAs, were detected for the first time at low concentrations in plasma of dolphins.

PMID: 16190216 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16170448&query_hl=5

Arch Environ Contam Toxicol. 2005 Sep 16; [Epub ahead of print]
 
Alkaline Digestion and Solid Phase Extraction Method for Perfluorinated Compounds in Mussels and Oysters from South China and Japan.

So MK, Taniyasu S, Lam PK, Zheng GJ, Giesy JP, Yamashita N.

Centre for Coastal Pollution and Conservation, Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong SAR, Peoples Republic of China, bhpksl@cityu.edu.hk.

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS), have been identified in the coastal waters of China and Japan. An alkaline digestion method, coupled with solid-phase extraction (SPE), and high-performance liquid chromatography interfaced with high-resolution electrospray tandem mass spectrometry was developed to determine PFCs in mussel and oyster samples from coastal waters of south China and Japan. These techniques produced adequate recoveries and reporting limits with small quantities of PFCs. Concentrations of individual PFCs in mussels and oysters from south China and Japan ranged from 113.6 to 586.0 pg/g, wet weight (ww) for PFOS, 63.1 to 511.6 pg/g, ww for perfluorohexane sulfonate, 9.3 to 30.1 pg/g, ww for perfluorobutane sulfonate and 37.8 to 2957.0 pg/g, ww for perfluorooctane sulfonamide. The quantification of perfluorinated carboxylates was compromised by interferences from carboxylates in the procedural blanks. Perfluoroundecanoate and perfluorononanoate had relatively great blank interferences, which resulted in relatively poor limits of quantification for these compounds. Some PFCs were only identified in a limited number of samples: perfluorododecanoate in samples from Tokyo Bay, Japan (195.9 pg/g, ww); and perfluorodecanoate in Fuzhou, China (131.7 pg/g, ww) and Tokyo Bay (118.6 pg/g, ww). The greatest concentrations of perfluorooctanoate, perfluoroheptanoate, and perfluorohexanoate were observed in samples from Tokyo Bay and Bei Hai, south China.

PMID: 16170448 [PubMed - as supplied by publisher]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16201619&query_hl=5

Environ Sci Technol. 2005 Sep 15;39(18):6978-84.

Tissue distribution of perfluorinated chemicals in harbor seals (Phoca vitulina) from the Dutch Wadden Sea.

Van de Vijver KI, Hoff P, Das K, Brasseur S, Van Dongen W, Esmans E, Reijnders P, Blust R, De Coen W.

Department of Biology, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerpen, Belgium. inneke.vandevijver@ua.ac.be

Perfluorinated acids (PFAs) are today widely distributed in the environment, even in remote arctic areas. Recently, perfluorooctane sulfonate (PFOS) has been identified in marine mammals all over the world, but information on the compound-specific tissue distribution remains scarce. Furthermore, although longer perfluorinated carboxylic acids (PFCAs) are used in industry and were shown to cause severe toxic effects, still little is known on potential sources or their widespread distribution. In this study, we report for the first time on levels of longer chain PFCAs, together with some short chain PFAs, perfluorobutane sulfonate (PFBS) and perfluorobutanoate (PFBA), in liver, kidney, blubber, muscle, and spleen tissues of harbor seals (Phoca vitulina) from the Dutch Wadden Sea. PFOS was the predominant compound in all seal samples measured (ranging from 89 to 2724 ng/g wet weight); however, large variations between tissues were monitored. Although these are preliminary results, it is, to our knowledge, the first time that PFBS could be found at detectable concentrations (2.3 +/- 0.7 ng/g w wt) in environmental samples. PFBS was only detected in spleen tissue. PFCA levels were much lower than PFOS concentrations. The dominant PFCA in all tissues was PFNA (perfluorononanoic acid), and concentrations generally decreased in tissues for all other PFCA homologues with increasing chain length. No clear relationship between PFOS levels in liver and kidney was observed. Furthermore, hepatic PFDA (perfluorodecanoic acid) levels increased with increasing body length, but in kidney tissue, PFDA levels showed an inverse relationship with increasing body length. These data suggest large differences in tissue distribution and accumulation patterns of perfluorinated compounds in marine organisms.

PMID: 16201619 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15973506&query_hl=4

Inflamm Res. 2005 Jun;54(6):235-42.
 
Central administration of perfluorooctanoic acid inhibits cutaneous inflammation.

Taylor BK, Kriedt C, Nagalingam S, Dadia N, Badr M.

Department of Pharmacology, Tulane University Health Sciences Center, New Orleans, LA 70112, USA.

OBJECTIVE: To elucidate the site of action of perfluorooctanoic acid (PFOA) in the carrageenan model of peripheral inflammation.
SUBJECTS: Male Sprague-Dawley rats.
TREATMENT: We first compared the anti-edema effects of systemic PFOA (50-150 mg/kg) with prototypical nonsteroidal (acetylsalicylic acid, ASA, 50-200 mg/kg) and steroidal (dexamethasone, 0.5-5.0 mg/kg) drugs after the intraplantar injection of carrageenan (1%). We then compared the anti-edema effects of systemic PFOA with local intraplantar (10 mg/kg), and intracerebroventricular (i.c.v., 0.1-50 mug) routes of administration.
RESULTS: Systemic PFOA was at least as or more efficacious than ASA or dexamethasone in reducing carrageenan-induced edema. RU-486 did not change the anti-edema effect of PFOA, ruling out a contribution of endogenous release of glucorticoids. I. c. v. PFOA, but not perfluorooctanes, dramatically reduced multiple signs of inflammation at doses well below the systemically-effective dose. We conclude that the anti-edema effect of high systemic doses of PFOA (> or =100 mg/kg, i. p.) is mediated in part by actions in the brain.

PMID: 15973506 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16040121&query_hl=4

Ecotoxicol Environ Saf. 2005 Jul 22; [Epub ahead of print]
 
The bioconcentration factor of perfluorooctane sulfonate is significantly larger than that of perfluorooctanoate in wild turtles (Trachemys scripta elegans and Chinemys reevesii): An Ai river ecological study in Japan.

Morikawa A, Kamei N, Harada K, Inoue K, Yoshinaga T, Saito N, Koizumi A.

Department of Health and Environmental Sciences, Kyoto University Graduate School of Medicine, Yoshida Konoe, Sakyo, Kyoto 606-8501, Japan.

Turtles rank high in the river food chain, and are suitable for predicting the bioconcentrations of chemicals through the food chain. Trachemys scripta elegans (N=46) and Chinemys reevesii (N=51) were captured in a river in Japan, from September to October 2003 and April to June 2004. Surface water samples were collected simultaneously from the same sites at which the turtles were caught. Serum perfluorooctane sulfonate (PFOS) ranged from 2.4 to 486mug/L, while water PFOS levels ranged from 2.9 to 37ng/L. The geometric mean (GM) (geometric standard deviation, GSD) of the bioconcentration factor (BCF) of PFOS was 10,964 (2.5). In contrast, the perfluorooctanoate (PFOA) level in water ranged from 16.7-87,100ng/L, and serum PFOA ranged from <0.2 to 870mug/L. The GM (GSD) of the BCF of PFOA was 3.2 (7.9). Furthermore, the BCF of PFOA decreased as the PFOA level in the surface water increased. PFOS could be preferentially bioconcentrated in biota, and PFOA, slightly bioconcentrated.

PMID: 16040121 [PubMed - as supplied by publisher]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15984763&query_hl=4

Environ Sci Technol. 2005 Jun 1;39(11):3904-10.

Exposure assessment and risk characterization for perfluorooctanoate in selected consumer articles.

Washburn ST, Bingman TS, Braithwaite SK, Buck RC, Buxton LW, Clewell HJ, Haroun LA, Kester JE, Rickard RW, Shipp AM.

ENVIRON International Corporation, 6001 Shellmound Street, Suite 700, Emeryville, California 94608, USA. swashburn@environcorp.com

An exposure assessment and risk characterization was conducted to better understand the potential human health significance of trace levels of perfluorooctanoate (PFO) detected in certain consumer articles. PFO is the anion of perfluorooctanoic acid (PFOA). Concentrations of PFO in the consumer articles were determined from extraction tests and product formulation information. Potential exposures during consumer use of the articles were quantified based on an assessment of behavior patterns and regulatory guidance. Health benchmarks were developed and then compared to the exposure estimates to yield margins of exposure (MOEs). A simple one-compartment model was also developed to estimate contributions of potential consumer exposures to PFO concentrations in serum. While there are considerable uncertainties in this assessment, it indicates that exposures to PFO during consumer use of the articles evaluated in this study are not expected to cause adverse human health effects in infants, children, adolescents, adult residents, or professionals nor result in quantifiable levels of PFO in human serum.

PMID: 15984763 [PubMed - indexed for MEDLINE]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16194675&query_hl=26

Environ Res. 2005 Oct;99(2):253-61. Epub 2005 Jan 18.
 
Renal clearance of perfluorooctane sulfonate and perfluorooctanoate in humans and their species-specific excretion.

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

Department of Health and Environmental Sciences, Kyoto University, Graduate School of Medicine, Yoshida Konoecho, Kyoto 606-8501, Japan.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are detected in the environment, as well as more specifically in wildlife and humans. However, the toxicokinetic aspects of perfluorochemicals in humans are unclear. In this study, we measured concentrations of PFOA and PFOS in subjects who had lived in Kyoto city for more than 10 years. The serum concentrations of PFOA and PFOS were higher in females who menstruated than those who did not menstruation (P<0.01), but in males this did not change by age; the levels in females reached those in males at an age of 60 years. We then determined the renal clearances of PFOA and PFOS in young (20-40 years old, N=5 for each sex) and old (60 years old, N=5 for each sex) subjects of both sexes. All young females were menstruating, while all old females were not. The renal clearances were 10(-5)-fold smaller than the glomerular filtration rate in humans, suggesting the absence of active excretion in human kidneys. The renal clearances of PFOA and PFOS were approximately one-fifth of the total clearance based on their serum half-lives, assuming a one-compartment model. The sex differences in renal clearance that have been reported in rats and Japanese macaques were not found in our human subjects. We tried to build a one-compartment pharmacokinetic model using the reported half-lives in human. The model was simple but could predict the serum concentrations in both males and females fairly well. We therefore suggest that an internal dose approach using a pharmacokinetic model should be taken because of the large species differences in kinetics that exist for PFOA and PFOS.

PMID: 16194675 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15984769&query_hl=13

Environ Sci Technol. 2005 Jun 1;39(11):3946-56.

Quantitative determination of perfluorochemicals in sediments and domestic sludge.

Higgins CP, Field JA, Criddle CS, Luthy RG.

Department of Civil and Environmental Engineering, Stanford University, Stanford, California 94305-4020, USA.

Perfluorochemicals (PFCs) are the subject of increasingly intense environmental research. Despite their detection both in biota and in aqueous systems, little attention has been paid to the possible presence of this class of compounds in solid environmental matrixes. The limited available data indicate that some PFCs such as perfluorooctane sulfonate (PFOS) may strongly sorb to solids, and sewage sludge is widely suspected as a major sink of PFCs entering municipal waste streams. A quantitative analytical method was developed that consists of liquid solvent extraction of the analytes from sediments and sludge, cleanup via solid-phase extraction, and injection of the extracts with internal standards into a high-performance liquid chromatography (HPLC) system coupled to a tandem mass spectrometer (LC/MS/MS). The limits of detections of the method were analyte and matrix dependent, but ranged from 0.7 to 2.2 ng/g and 0.041 to 0.246 ng/g (dry weight) for sludge and sediment, respectively. A demonstration of the method was performed by conducting a limited survey of domestic sludge and sediments. The concentration of PFCs in domestic sludge ranged from 5 to 152 ng/g for total perfluorocarboxylates and 55 to 3370 ng/g for total perfluoroalkyl sulfonyl-based chemicals. Data from a survey of San Francisco Bay Area sediments suggest widespread occurrence of PFCs in sediments at the low ng/g to sub-ng/g level. Furthermore, substances that may be transformed to PFOS, such as 2-(N-ethylperfluorooctanesulfonamido) acetic acid (N-EtFOSAA) and 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA), are present in both sediments and sludge at levels often exceeding PFOS.

PMID: 15984769 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15982707&query_hl=13

Chemosphere. 2005 Jun 24; [Epub ahead of print]
 
Evaluation of biochemical effects related to perfluorooctane sulfonic acid exposure in organohalogen-contaminated great tit (Parus major) and blue tit (Parus caeruleus) nestlings.

Hoff PT, Van de Vijver K, Dauwe T, Covaci A, Maervoet J, Eens M, Blust R, De Coen W.

Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium.

A perfluorooctane sulfonic acid (PFOS) biomonitoring survey was conducted on great tit (Parus major) and blue tit (Parus caeruleus) nestlings from Blokkersdijk, a bird reserve in the proximity of a fluorochemical plant in Antwerp (Belgium) and Fort IV, a control area. PFOS, together with 11 organochlorine pesticides, 20 polychlorinated biphenyl congeners and 7 polybrominated diphenyl ethers were measured in liver tissue. The hepatic PFOS concentrations at Blokkersdijk (86-2788 and 317-3322ng/g wet weight (ww) for great and blue tit, respectively) were among the highest ever measured and were significantly higher than at the control area (17-206 and 69-514ng/g ww for great and blue tit, respectively). The hepatic PFOS concentration was species- and sex-independent and correlated significantly and positively with the serum alanine aminotransferase activity and negatively with the serum cholesterol and triglyceride levels in both species but did not correlate with condition or serum protein concentration. In the great tit, a significant positive correlation was observed between the liver PFOS concentration and the relative liver weight. In the blue tit, the hepatic PFOS concentration correlated positively and significantly with hematocrite values. None of the investigated organohalogen pollutants except for PFOS were suggested to be involved in the observed biological alterations.

PMID: 15982707 [PubMed - as supplied by publisher]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15963371&query_hl=13

Environ Pollut. 2005 Sep;137(2):324-33.
 
Perfluorooctane sulfonic acid and organohalogen pollutants in liver of three freshwater fish species in Flanders (Belgium): relationships with biochemical and organismal effects.

Hoff PT, Van Campenhout K, Van de Vijver K, Covaci A, Bervoets L, Moens L, Huyskens G, Goemans G, Belpaire C, Blust R, De Coen W.

Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Groenenborgerlaan 171, B-2020 Antwerp, Belgium.

A perfluorooctane sulfonic acid (PFOS) assessment was conducted on gibel carp (Carassius auratus gibelio), carp (Cyprinus carpio), and eel (Anguilla anguilla) in Flanders (Belgium). The liver PFOS concentrations in fish from the Ieperlee canal (Boezinge, 250-9031 ng/g wet weight, respectively) and the Blokkersdijk pond (Antwerp, 633-1822 ng/g wet weight) were higher than at the Zuun basin (Sint-Pieters-Leeuw, 11.2-162 ng/g wet weight) and among the highest in feral fish worldwide. Eel from the Oude Maas pond (Dilsen-Stokkem) and Watersportbaan basin (Ghent) had PFOS concentrations ranging between 212 and 857 ng/g wet weight. The hepatic PFOS concentration was significantly and positively related with the serum alanine aminotransferase activity, and negatively with the serum protein content in eel and carp. The hepatic PFOS concentration in carp correlated significantly and negatively with the serum electrolyte concentrations whereas a significant positive relation was found with the hematocrit in eel. Although 13 organochlorine pesticides, 22 polychlorinated biphenyl (PCB) congeners and 7 polybrominated diphenyl ethers (PBDEs) were also measured in the liver tissue, only PCB 28, PCB 74, gamma-hexachlorocyclohexane (gamma-HCH) and hexachlorobenzene (HCB) were suggested to contribute to the observed serological alterations in eel.

PMID: 15963371 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15896450&query_hl=33

Regul Toxicol Pharmacol. 2005 Jun;42(1):145. Epub 2005 Feb 24.
 
Human health risks from exposures to perfluorooctanoic acid: A critique of Butenhoff et al. 2004.

Kropp T, Houlihan J.

Environmental Working Group, Toxics Division, 1436 U St NW, STE 100, Washington, DC 20009, USA.

Publication Types:
• Letter

PMID: 15896450 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15926594&query_hl=28

Environ Sci Technol. 2005 May 1;39(9):3388-92.

Sonochemical decomposition of perfluorooctane sulfonate and perfluorooctanoic acid.

Moriwaki H, Takagi Y, Tanaka M, Tsuruho K, Okitsu K, Maeda Y.

Osaka City Institute of Public Health & Environmental Sciences, 8-34, Tojo-cho, Tennoji-ku, Osaka 543-0026, Japan. hiroshi.moriwaki@iphes.city.osaka.jp

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are shown to be globally distributed, environmentally persistent, and bioaccumulative. Although the toxicities of these compounds were reported, the cleanup procedure from the environment is not developed because of their inertness. In this report the sonochemical degradations of PFOS and PFOA to the products through the fission of the perfluorocarbon chains were observed and the half-life times of the PFOS and PFOA degradations under an argon atmosphere determined to be 43 and 22 min, respectively. The shortening of perfluorocarbon chain of PFOS and PFOA leads to the lowering of the toxicity in view of the decrease of the persistence, and the technique would contribute to the remediation of the environmental pollution by these compounds.

PMID: 15926594 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15865257&query_hl=21

Drug Chem Toxicol. 2005;28(2):135-58.

Subchronic toxicity of a fluoroalkylethanol mixture in rats.

Ladics GS, Stadler JC, Makovec GT, Everds NE, Buck RC.

DuPont Company Haskell Laboratory for Health and Environmental Sciences, Newark, Delaware 19714, USA. Gregory.S.Ladics@usa.dupont.com

The objective of this study was to evaluate the subchronic toxicity of a commercial fluoroalkylethanol mixture, which is an intermediate in the production of fluoroorganic compounds that are used as protectants and surfactants. The test substance was administered daily by gavage to Sprague-Dawley rats as a suspension in aqueous methylcellulose. The dosages were 0, 25, 100, or 250 mg kg(-1) day(-1). A 1- and 3-month recovery period was included to evaluate the reversibility of toxic effects. No test substance-related mortality or neurotoxicity occurred. Body weights and/or nutritional parameters were significantly reduced at 100 and 250 mg kg(-1) day(-1), and these effects were reversible. Broken and absent teeth were observed in rats dosed with 250 mg kg(-1) day(-1), and microscopic tooth lesions (ameloblast degeneration/disorganization) occurred at 100 and 250 mg kg(-1) day(-1) and persisted with decreased severity throughout recovery. Decreased red cell mass parameters occurred at 90 days in the 250 mg kg(-1) day(-1) group, but red cell counts were normal thereafter during recovery. A persistent elevation of liver weights was seen in groups given > or =100 mg kg(-l) day(-1). The increased weights correlated with microscopic hepatocellular hypertrophy only in males and females administered 250 mg kg(-1) day(-1). Hepatic beta-oxidation was increased in a dose-dependent manner and persisted through 1 month of recovery at 250 mg kg(-1) day(-1). Increased kidney weights were observed at 25 (females only), 100, and 250 mg kg(-1) day(-1). These elevated weights persisted in the high dose after recovery and correlated with microscopic tubular hypertrophy (males only). Thyroid follicular hypertrophy was present at 100 and 250 mg kg(-1) day(-1) but was not present after recovery. Total fluorine in whole blood increased with continuous dosing and achieved steady state in approximately 42 days. Both plasma and urine fluoride levels were elevated in a dose-dependent manner. Under the conditions of the study, the no-observed adverse effect level for this mixture was 25 mg kg(-1) day(-1) for subchronic toxicity.

PMID: 15865257 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15913661&query_hl=4

Mar Pollut Bull. 2005 May 20; [Epub ahead of print]
 
A global survey of perfluorinated acids in oceans.

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

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

Perfluorinated acids and their salts have emerged as an important class of global environmental contaminants. Biological monitoring surveys conducted using tissues of marine organisms reported the occurrence of perfluorooctanesulfonate (PFOS) and related perfluorinated compounds in biota from various seas and oceans, including the Arctic and the Antarctic Oceans. Occurrence of perfluorinated compounds in remote marine locations is of concern and indicates the need for studies to trace sources and pathways of these compounds to the oceans. Determination of sub-parts-per-trillion (ng/L) or parts-per-quadrillion (pg/L) concentrations of aqueous media has been impeded by relatively high background levels arising from procedural or instrumental blanks. Our research group has developed a reliable and highly sensitive analytical method by which to monitor perfluorinated compounds in oceanic waters. The method developed is capable of detecting PFOS, perfluorohexanesulfonate (PFHS), perfluorobutanesulfonate (PFBS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), and perfluorooctanesulfonamide (PFOSA) at a few pg/L in oceanic waters. The method was applied to seawater samples collected during several international research cruises undertaken during 2002-2004 in the central to eastern Pacific Ocean (19 locations), South China Sea and Sulu Seas (five), north and mid Atlantic Ocean (12), and the Labrador Sea (20). An additional 50 samples of coastal seawater from several Asian countries (Japan, China, Korea) were analyzed. PFOA was found at levels ranging from several thousands of pg/L in water samples collected from coastal areas in Japan to a few tens of pg/L in the central Pacific Ocean. PFOA was the major contaminant detected in oceanic waters, followed by PFOS. Further studies are being conducted to elucidate the distribution and fate of perfluorinated acids in oceans.

PMID: 15913661 [PubMed - as supplied by publisher]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15888668&query_hl=4

Toxicol Sci. 2005 May 11; [Epub ahead of print]
 
Induction of hepatic peroxisome proliferation by 8-2 telomer alcohol feeding in mice: Formation of perfluorooctanoic acid in the liver.

Kudo N, Iwase Y, Okayachi H, Yamakawa Y, Kawashima Y.

Faculty of Pharmaceutical Sciences, Josai University, Keyakidai 1-1, Sakado, Saitama 350-0295, Japan.

The effects of dietary administration of 1H, 1H, 2H, 2H-perfluorodecanol (8-2 telomer alcohol), on peroxisome proliferation in the liver of mice were studied. Male ddY mice were fed on a diet containing 8-2 telomer alcohol at concentrations of 0, 0.025, 0.05, 0.1 and 0.2% (w/w) for 7, 14, 21 and 28 days. These treatments with 8-2 telomer alcohol caused liver enlargement in a dose- and duration-dependent manner. Peroxisome proliferation in the liver of mice was confirmed by electron microscopic examination. Peroxisomal acyl-CoA oxidase was induced by these treatments with 8-2 telomer alcohol in a dose- and time-dependent manner. The concentration of perfluorooctanoic acid (PFOA) and related compounds were determined in the liver and plasma, since PFOA had been shown to be a possible metabolite of 8-2 telomer alcohol and to cause significant peroxisome proliferation in rodents. Five metabolites, namely, perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), 2H, 2H-perfluorodecanoic acid (8-2 telomer acid), and two unidentified metabolites, were present in the liver and serum. PFOA was confirmed to be accumulated in the liver of mice following the administration of 8-2 telomer alcohol in a dose- and duration-dependent manner. A linear relationship was observed between the concentration of PFOA and the activity of peroxisomal acyl-CoA oxidase in the liver of mice. These results strongly suggest that PFOA, but not 8-2 telomer alcohol itself, caused peroxisome proliferation in the liver. The present study provided evidence that 8-2 telomer alcohol is converted into PFOA in vivo and that the PFOA formed produces biological effects in the liver of mice.

PMID: 15888668 [PubMed - as supplied by publisher]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16110997&query_hl=5

Environ Toxicol Chem. 2005 May;24(5):1172-81.

Short-term exposures of fish to perfluorooctane sulfonate: acute effects on fatty acyl-coa oxidase activity, oxidative stress, and circulating sex steroids.

Oakes KD, Sibley PK, Martin JW, MacLean DD, Solomon KR, Mabury SA, Van Der Kraak GJ.

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

This study investigated the effects of exposure to waterborne perfluorooctane sulfonate (PFOS) on oxidative stress and reproductive endpoints in fish. Exposures utilized species commonly used in toxicological testing, including the fathead minnow (Pimephales promelas) and rainbow trout (Oncorhynchus mykiss), as well as relatively insensitive taxa such as creek chub (Semotilus atromaculatus), spottail shiner (Notropis hudsonius), and white sucker (Catostomus commersoni). In all fish species, short-term (14-28 d) exposure to PFOS produced only modest mortality at concentrations consistent with environmental spill scenarios. However, PFOS consistently increased hepatic fatty acyl-CoA oxidase activity and increased oxidative damage, as quantified using the 2-thiobarbituric acid-reactive substances assay. Plasma testosterone, 11-ketotestosterone, and 17beta-estradiol titers were often elevated with PFOS exposure. Vitellogenin, the egg yolk precursor protein, was occasionally altered in the plasma with PFOS exposure, but responses varied with maturity. Oviposition frequency and egg deposition in fathead minnow were not significantly impaired with PFOS exposure, despite a trend toward progressive impairment with increasing exposure concentrations. Although short-term PFOS exposure produced significant impacts on biochemical and reproductive endpoints in fish at concentrations consistent with environmental spills, the impact of long-term exposure to environmentally relevant concentrations of PFOS is unclear.

PMID: 16110997 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15883668&query_hl=4

Arch Environ Contam Toxicol. 2005 May;48(4):559-66.
 
Perfluorinated compounds in aquatic organisms at various trophic levels in a great lakes food chain.

Kannan K, Tao L, Sinclair E, Pastva SD, Jude DJ, Giesy JP.

Wadsworth Center, New York State Department of Health and Department of Environmental Health and Toxicology, School of Public Health, State University of New York at Albany, Empire State Plaza, 509, Albany, New York, 12201-0509, USA, kkannan@wadsworth.org.

Trophic transfer of perfluorooctanesulfonate (PFOS) and other related perfluorinated compounds was examined in a Great Lakes benthic foodweb including water-algae-zebra mussel-round goby-smallmouth bass. In addition, perfluorinated compounds were measured in livers and eggs of Chinook salmon and lake whitefish, in muscle tissue of carp, and in eggs of brown trout collected from Michigan. Similarly, green frog livers, snapping turtle plasma, mink livers, and bald eagle tissues were analyzed to determine concentrations in higher trophic-level organisms in the food chain. PFOS was the most widely detected compound in benthic organisms at various trophic levels. Concentrations of PFOS in benthic invertebrates such as amphipods and zebra mussels were approximately 1000-fold greater than those in surrounding water, which suggested a bioconcentration factor (BCF; concentration in biota/concentration in water) of 1000 in benthic invertebrates. Concentrations of PFOS in round gobies were two- to fourfold greater than those in their prey organisms such as zebra mussels and amphipods. Concentrations of PFOS in predatory fishes (Chinook salmon and lake whitefish) were 10 to 20-fold greater than those in their prey species. Concentrations of PFOS in mink and bald eagles were, on average, 5- to 10-fold greater than those in Chinook salmon, carp, or snapping turtles. Because of the accumulation of PFOS in liver and blood, the biomagnification factor (BMF) of perfluorinated compounds in higher trophic-level organisms such as salmonid fishes, mink, and eagles were based on the concentrations in livers or plasma. Overall, these results suggest a BCF of PFOS of approximately 1000 (whole-body based) in benthic invertebrates, and a BMF of 10 to 20 in mink or bald eagles, relative to their prey items. Eggs of fish contained notable concentrations of PFOS, suggesting oviparous transfer of this compound. PFOA was found in water, but its biomagnification potential was lower than that of PFOS.

PMID: 15883668 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15871280&query_hl=4

Environ Sci Technol. 2005 Apr 1;39(7):2383-8.

Efficient decomposition of environmentally persistent perfluorocarboxylic acids by use of persulfate as a photochemical oxidant.

Hori H, Yamamoto A, Hayakawa E, Taniyasu S, Yamashita N, Kutsuna S, Kiatagawa H, Arakawa R.

National Institute of Advanced Industrial Science and Technology, AIST Tsukuba West, 16-1 Onogawa, Tsukuba 305-8569, Japan. h-hori@aist.go.jp

Photochemical decomposition of persistent perfluorocarboxylic acids (PFCAs) in water by use of persulfate ion (S2O8(2-)) was examined to develop a technique to neutralize stationary sources of PFCAs. Photolysis of S2O8(2-) produced highly oxidative sulfate radical anions (SO4-), which efficiently decomposed perfluorooctanoic acid (PFOA) and other PFCAs bearing C4-C8 perfluoroalkyl groups. The major products were F- and CO2; also, small amounts of PFCAs with shorter than initial chain lengths were detected in the reaction solution. PFOA at a concentration of 1.35 mM (typical of that in untreated wastewater after an emulsifying process in fluoropolymer manufacture) was completely decomposed by a photochemical system with 50 mM S2O8(2-) and 4 h of irradiation from a 200-W xenon-mercury lamp. The initial PFOA decomposition rate was 11 times higher than with photolysis alone. All sulfur-containing species in the reaction solution were eventually transformed to sulfate ions by this method. This method was successfully applied to the decomposition of perfluorononanoic acid contained in a floor wax solution.

PMID: 15871280 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15866760&query_hl=4

Environ Health Perspect. 2005 May;113(5):539-45.
 
Historical comparison of perfluorooctanesulfonate, perfluorooctanoate, and other fluorochemicals in human blood.

Olsen GW, Huang HY, Helzlsouer KJ, Hansen KJ, Butenhoff JL, Mandel JH.

Medical Department, 3M Company, Mail Stop 220-6W-08, St. Paul, MN 55144, USA. gwolsen@mmm.com

The purpose of this investigation was to determine whether there has been a change in the human blood concentration of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and five other fluorochemicals since 1974. Blood samples were collected in 1974 (serum) and 1989 (plasma) from volunteer participants of a large community health study. The study included a total of 356 samples (178 from each time period). These samples were analyzed by high-pressure liquid chromatography/tandem mass spectrometry methods. The median 1974 and 1989 fluorochemical concentrations, respectively, were as follows: PFOS, 29.5 ng/mL vs. 34.7 ng/mL; PFOA, 2.3 ng/mL vs. 5.6 ng/mL; perfluorohexanesulfonate (PFHS), 1.6 ng/mL vs. 2.4 ng/mL; and N-ethyl perfluorooctanesulfonamidoacetate (PFOSAA), less than the lower limit of quantitation (LLOQ; 1.6 ng/mL, vs. 3.4 ng/mL). For N-methyl perfluorooctanesulfonamidoacetate (M570), perfluorooctanesulfonamide, and perfluorooctanesulfonamidoacetate, median serum concentrations in both years were less than the LLOQ values (1.0, 1.0, and 2.5 ng/mL, respectively). Statistical analysis of 58 paired samples indicated that serum concentrations of PFOS, PFOSAA, PFOA, PFHS, and M570 were significantly (p < 0.001) higher in 1989 than in 1974. The data from 1989 were then compared with geometric mean fluorochemical concentrations of serum samples collected in 2001 from 108 American Red Cross adult blood donors from the same region. Except for M570, there were no statistically significant (p < 0.05) geometric mean fluorochemical concentration differences between the 1989 and 2001 samples. In conclusion, based on this study population, PFOS and other serum fluorochemical concentrations have increased between 1974 and 1989. Comparison with other regional data collected in 2001 did not suggest a continued increase in concentrations since 1989.

PMID: 15866760 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15865261&query_hl=4

Drug Chem Toxicol. 2005;28(2):197-209.

Subcellular distribution and protein binding of perfluorooctanoic acid in rat liver and kidney.

Han X, Kemper RA, 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 its elimination in rats is markedly sex-dependent. Liver and kidney are two primary tissues of distribution of PFOA in rats. In this study, the subcellular distribution of PFOA in male and female rat liver and kidney was examined. The results demonstrated that PFOA content in the liver cytosol of the female rat was significantly higher (49 +/- 6% of total radioactive residues, TRR) than in the male liver (26 +/- 5% TRR), whereas PFOA distribution in the heavier subcellular fractions, especially the nuclei and cell debris fraction, was marginally higher in male rat liver. In rat kidney, more than 70% of PFOA was distributed in the cytosolic fraction, with no significant difference between sexes. The degree of protein binding of PFOA in rat liver and kidney cytosol was analyzed by two different chromatographic methods. The percentage of protein-bound PFOA in the liver cytosol was found to be approximately 55% in both male and female rats. In contrast, significantly more PFOA was bound to cytosolic proteins in the kidney of male rats (42 +/- 6% TRR) than in females (17 +/- 5% TRR). Ligand blotting analysis revealed that multiple proteins from the liver cytosol, nuclei, and mitochondria fractions were capable of specific binding to PFOA.

PMID: 15865261 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=16124282&query_hl=5

Environ Sci Technol. 2005 Aug 1;39(15):5517-23.

Circumpolar study of perfluoroalkyl contaminants in polar bears (Ursus maritimus).

Smithwick M, Mabury SA, Solomon KR, Sonne C, Martin JW, Born EW, Dietz R, Derocher AE, Letcher RJ, Evans TJ, Gabrielsen GW, Nagy J, Stirling I, Taylor MK, Muir DC.

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

Perfluoroalkyl substances were determined in liver tissues and blood of polar bears (Ursus maritimus) from five locations in the North American Arctic and two locations in the European Arctic. Concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide, and perfluoroalkyl carboxylates with C(8)-C(15) perfluorinated carbon chains were determined using liquid chromatography tandem mass spectrometry. PFOS concentrations were significantly correlated with age at four of seven sampling locations, while gender was not correlated to concentration for any compound measured. Populations in South Hudson Bay (2000-2730 ng/g wet wt), East Greenland (911-2140 ng/g wet wt), and Svalbard (756-1290 ng/g wet wt) had significantly (P < 0.05) higher PFOS concentrations than western populations such as the Chukchi Sea (435-729 ng/g wet wt). Concentrations of perfluorocarboxylic acids (PFCAs) with adjacent chain lengths (i.e., C9:C10 and C10:C11) were significantly correlated (P < 0.05), suggesting PFCAs have a common source within a location, but there were differences in proportions of PFCAs between eastern and western location sources. Concentrations of PFOS in liver tissue at five locations were correlated with concentrations of four polychlorinated biphenyl congeners (180, 153, 138, and 99) in adipose tissue of bears in the same populations, suggesting similar transport pathways and source regions of PFOS or precursors.

PMID: 16124282 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15839574&query_hl=4

Environ Toxicol Chem. 2005 Apr;24(4):981-6.

Perflouroalkyl contaminants in liver tissue from East Greenland polar bears (Ursus maritimus).

Smithwick M, Muir DC, Mabury SA, Solomon KR, Martin JW, Sonne C, Born EW, Letcher RJ, Dietz R.

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

Perfluoroalkyl substances were determined in polar bears (Ursus maritimus) collected in East Greenland (69 degrees 00'N to 74 degrees 00"N) to compare with other populations and to examine effects of age and gender on concentrations of these contaminants. Hepatic tissue (n = 29) was analyzed for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide (PFOSA), and perfluoroalkyl carboxylates (PFCAs) with C9-C15 perfluorinated carbon chains by liquid chromatography tandem mass spectrometry. Concentrations of PFOS found in samples from East Greenland (mean = 2,470+/-1,320 ng/g wet weight) were similar to Hudson Bay, Canada, and both populations had significantly greater concentrations than those reported for Alaska, suggesting a spatial trend. Male bears showed a significant increase in concentration up to age six for PFCAs with C10-C14 carbon chains (r2 > or = 0.50, p < or = 0.05). Significant correlations were found between adjacent chain length PFCAs, (e.g., PFNA to PFDA: p < 0.05; r2 = 0.90). This may indicate a common source for these chemicals, although the specifics of source and mode of transport are unknown. No significant correlations were found between concentrations of PFCAs in liver tissue and previously reported polychlorinated biphenyl (PCB) congeners analyzed in fat samples from the same bears.

PMID: 15839574 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15862018

Wei Sheng Yan Jiu. 2005 Jan;34(1):37-9.

[Effects of perfluorooctane sulfonate on spermiogenesis function of male rats]

[Article in Chinese]

Fan YO, Jin YH, Ma YX, Zhang YH.

School of Public Health, China Medical University, Shenyang 110001, China.

OBJECTIVE: To evaluate the effects of administration of perfluorooctane sulfonate (PFOS) on spermiogenesis function of male rats.
METHODS: 36 male rats were randomly divided into 4 groups, which received 0, 0.5, 1.5, 4.5 mg x kg(-1) PFOS by food intake per day for 65 days. The testicular and epididymal viscera coefficients, the number, motility and deformity of sperm were examined. The activities of lactate dehydrogenase isoenzyme-x (LDHx), sorbitol dehydrogenase (SDH) and the generation of maglonydiadehyde (MDA) in the testes were also measured.
RESULTS: The viscera coefficients did not show any significant change ( P > 0.05) while the body weight and weight of testis decreased ( P < 0.05) in treated rats compared with the corresponding control group animals. In 1.5,4.5 mg x kg(-1) PFOS treated rats there were significant decreases in the sperm count (P < 0.05) and the mean activities of LDHx and SDH whereas obvious increases in the rate of sperm deformity ( P < 0.05). In 4.5 mg x kg(-1) PFOS group the generation of MDA increased (P < 0.05) while the motility of sperm reduced (P < 0.05) with respect to the control value.
CONCLUSION: It suggested that PFOS could elicit the impairment of sperm production and maturation of male rats.

PMID: 15862018 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15798805

J Environ Monit. 2005 Apr;7(4):371-7. Epub 2005 Mar 7.

Perfluorinated organic compounds in human blood serum and seminal plasma: a study of urban and rural tea worker populations in Sri Lanka.

Guruge KS, Taniyasu S, Yamashita N, Wijeratna S, Mohotti KM, Seneviratne HR, Kannan K, Yamanaka N, Miyazaki S.

Toxico-Biochemistry Section, National Institute of Animal Health, Kannondai 3-1-5, Tsukuba, Ibaraki 305-0856, Japan. guruge@affrc.go.jp

Concentrations and accumulation of 13 fluorinated organic compounds (FOCs) in human sera and seminal plasma were measured in an Asian developing country, Sri Lanka. Six of the FOCs, PFOS (perfluorooctanesulfonate), PFHS (perfluorohexanesulfonate), PFUnA (perfluoroundecanoic acid), PFDA (perfluorodecanoic acid), PFNA (perfluorononanoic acid) and PFOA (perfluorooctanoic acid), were detected in all of the sera samples. Measurable quantities of two main perfluorosulfonates, PFOS and PFHS, were found in all seminal plasma samples. The detection frequency of the predominant perfluoroalkylcarboxylate, PFOA, in seminal plasma was >70%. Accumulation of PFOS in sera was significantly positively correlated with PFOA, PFHS and PFNA. Positive linear regressions were also found between PFNA and PFUnA and PFNA and PFDA suggesting that these compounds may have a similar origin of exposure and accumulation. Significantly positive associations were observed for partitioning of both PFOS and PFNA between sera and seminal plasma. The accumulation of FOCs was not significantly different in sera from Colombo (urban population) and Talawakele (rural conventional tea workers). However, the Haldummulla population (rural organic tea workers) had relatively lower exposure to FOCs compared to the other two groups, urban and rural conventional tea workers. Concentrations of FOCs in Sri Lanka were similar to those reported for industrialized countries suggesting that human exposure to such chemicals is widespread even in developing countries. The novel finding of FOCs in human seminal plasma implies that further studies are needed to determine whether long-term exposure in humans can result in reproductive impairments.

PMID: 15798805 [PubMed - in process]


Toxicology - Volume 211, Issues 1-2 , 1 July 2005, Pages 139-148

Perfluorooctanoate: Placental and lactational transport pharmacokinetics in rats

Paul M. Hinderliter (a), Eve Mylchreest (a), Shawn A. Gannon (a), John L. Butenhoff (b) and Gerald L. Kennedy, Jr.(a)

(a) DuPont Haskell Laboratory for Health and Environmental Sciences, 1090 Elkton Road, P.O. Box 50, Newark, DE 19714, USA
(b) 3M Company, Medical Department, 3M Center 220-06-W-08, St. Paul, MN 55144, USA

This study was conducted to develop a quantitative understanding of the potential for gestational and lactational transfer of perfluorooctanoate (PFOA) in the rat. Time-mated female rats were dosed by oral gavage once daily at concentrations of 3, 10, or 30 mg/kg/day of the ammonium salt of PFOA (APFO) starting on gestation (G) day 4 and continuing until sacrifice. On days 10, 15, and 21G, five rats per dose level were sacrificed and blood samples were collected 2 h post-dose. Embryos were collected on day 10G, amniotic fluid, placentas, and embryos/fetuses were collected on days 15 and 21G, and fetal blood samples were collected on day 21G. Five rats per dose level were allowed to deliver and nurse their litters, and on days 3, 7, 14, and 21 post-partum (PP) milk and blood samples of maternal and pup were collected 2 h post-dose. All samples were analyzed by high-performance liquid chromatography–mass spectrometry (HPLC–MS) for PFOA concentration. Concentrations of PFOA in maternal plasma and milk attained steady state during the sampling interval. The steady-state concentrations in maternal plasma were 10–15, 25–30, and 60–75 ?g/mL in rats receiving 3, 10, and 30 mg/kg, respectively. Steady-state concentrations in milk were approximately 10 times less than those in maternal plasma. The concentration of PFOA in fetal plasma on day 21G was approximately half the steady-state concentration in maternal plasma. The milk concentrations appeared to be generally comparable to the concentrations in pup plasma. Pup plasma concentrations decreased from day 3PP to day 7PP, and were similar on days 7, 14, and 21PP at all dose levels. PFOA was detected in placenta (days 15 and 21G), amniotic fluid (days 15 and 21G), embryo (days 10 and 15G), and fetus (day 21G). These pharmacokinetics allow estimation of the dose to developing and nursing rat offspring following maternal exposure.


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15768499

Bull Environ Contam Toxicol. 2005 Jan;74(1):64-9.

Airborne perfluorooctanoate may be a substantial source contamination in Kyoto area, Japan.

Harada K, Nakanishi S, Saito N, Tsutsui T, Koizumi A.

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

No abstract available

PMID: 15768499 [PubMed - indexed for MEDLINE]


Environmental Pollution Volume 136, Issue 2 , July 2005, Pages 323-329

Preliminary screening of perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish, birds and marine mammals from Greenland and the Faroe Islands

Rossana Bossia (a), Frank F. Riget (a), Rune Dietz (a), Christian Sonne (a), Patrik Fauser (a), Maria Dam (b)and Katrin Vorkamp (a)

(a) National Environmental Research Institute, Frederiksborgvej 399, 4000-Roskilde, Denmark
(b) Food and Environmental Agency, Thorshavn, Faroe Islands

Extensive screening analyses of perfluorooctane sulfonate (PFOS) and related perfluorinated compounds in biota samples from all over the world have identified PFOS as a global pollutant and have shown its bioaccumulation into higher trophic levels in the food chain. Perfluorinated compounds have been found in remote areas as the Arctic. In this study a preliminary screening of PFOS and related compounds has been performed in liver samples of fish, birds and marine mammals from Greenland and the Faroe Islands. PFOS was the predominant fluorochemical in the biota analyzed, followed by perfluorooctane sulfonamide (PFOSA). PFOS was found at concentrations above LOQ (10 ng/g wet weight) in 13 out of 16 samples from Greenland and in all samples from the Faroe Islands. The results from Greenland showed a biomagnification of PFOS along the marine food chain (shorthorn sculpin<ringed seal<polar bear). The greatest concentration of PFOS was found in liver of polar bear from east Greenland (mean: 1285 ng/g wet weight, n=2). The geographical distribution of perfluorinated compounds in Greenland was similar to that of persistent organohalogenated compounds (OHCs), with the highest concentrations in east Greenland, indicating a similar geographical distribution to that of OHCs, with higher concentrations in east Greenland than in west Greenland. Perfluorinated acids were detected in livers of fish, birds and marine mammals from Greenland and the Faroe Islands.


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15779762

Environ Toxicol Chem. 2005 Mar;24(3):617-28.

Effects of contaminant exposure on reproductive success of ospreys (Pandion haliaetus) nesting in Delaware River and Bay, USA.

Toschik PC, Rattner BA, McGowan PC, Christman MC, Carter DB, Hale RC, Matson CW, Ottinger MA.

Marine, Estuarine, and Environmental Science Program, University of Maryland, College Park, Maryland 20742, USA.

Despite serious water-quality problems and pollutant loading and retention, Delaware River and Bay (USA) provide important wildlife habitat. In 2002, we conducted a comprehensive evaluation of contaminant exposure and reproduction of ospreys (Pandion haliaetus) breeding in Delaware River and Bay. Sample eggs were collected from 39 nests and analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), and mercury; a subset of 15 eggs was analyzed for perfluorinated compounds and polybrominated diphenyl ethers (PBDEs). The fate of each nest was monitored weekly. Concentrations of 10 organochlorine pesticides or metabolites, total PCBs, and several toxic PCB congeners were greater (p < 0.05) in eggs collected between the Chesapeake and Delaware Canal (C and D Canal) and Trenton (Delaware River and northern Bay) compared to other sites. Concentrations of p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE; 0.785-3.84 microg/g wet wt) and total PCBs (5.50-14.5 microg/g wet wt) in eggs collected between the C and D Canal and Trenton were similar to levels recently found in the Chesapeake Bay. In all study segments, at least one young fledged from 66 to 75% of nests. Productivity for Delaware Inland Bays (reference area) and southern Delaware Bay was 1.17 and 1.42 fledglings/active nest, respectively; north of the C and D Canal, productivity was 1.00 fledgling/active nest, which is marginally adequate to maintain the population. Using these data, a logistic regression model found that contaminant concentrations (p,p'-DDE, heptachlor epoxide, chlordane and metabolites, and total PCBs) were predictive of hatching success. Several perfluorinated compounds and PBDEs were detected in eggs at concentrations approaching 1 microg/g wet weight. These findings provide evidence that contaminants continue to be a significant stressor on osprey productivity in the northern Delaware River and Bay.

PMID: 15779762 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15768565

Artif Cells Blood Substit Immobil Biotechnol. 2005;33(1):47-63.

Understanding the fundamentals of perfluorocarbons and perfluorocarbon emulsions relevant to in vivo oxygen delivery.

Riess JG.

MRI Institute, University of California at San Diego, San Diego, California, USA. jriess@allp.com

The unique behavior of perfluorocarbons (PFCs), including their high oxygen dissolving capacity, hydrophobic and lipophobic character, and extreme inertness, derive directly, in a predictable manner, from the electronic structure and spatial requirements of the fluorine atom. Their low water solubility is key to the prolonged in vivo persistence of the now commercially available injectable microbubbles that serve as contrast agents for diagnostic ultrasound imaging. Oxygent, a stable, small-sized emulsion of a slightly lipophilic, rapidly excreted PFC, perfluorooctyl bromide (perflubron), has been engineered. Significant oxygen delivery has been established in animal models and through Phase II and III human clinical trials. However, an inappropriate testing protocol and the lack of funding led to temporary suspension of the trials.

PMID: 15768565 [PubMed - in process]


From Science Direct

Environmental Pollution - Article in Press, Corrected Proof. Available online 5 March 2005.

Preliminary screening of perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish, birds and marine mammals from Greenland and the Faroe Islands

Rossana Bossia (a), Frank F. Riget (a), Rune Dietz (a), Christian Sonne (a), Patrik Fauser (a), Maria Dam (b) and Katrin Vorkamp (a)

(a) National Environmental Research Institute, Frederiksborgvej 399, 4000-Roskilde, Denmark
(b) Food and Environmental Agency, Thorshavn, Faroe Islands

Extensive screening analyses of perfluorooctane sulfonate (PFOS) and related perfluorinated compounds in biota samples from all over the world have identified PFOS as a global pollutant and have shown its bioaccumulation into higher trophic levels in the food chain. Perfluorinated compounds have been found in remote areas as the Arctic. In this study a preliminary screening of PFOS and related compounds has been performed in liver samples of fish, birds and marine mammals from Greenland and the Faroe Islands. PFOS was the predominant fluorochemical in the biota analyzed, followed by perfluorooctane sulfonamide (PFOSA). PFOS was found at concentrations above LOQ (10 ng/g wet weight) in 13 out of 16 samples from Greenland and in all samples from the Faroe Islands. The results from Greenland showed a biomagnification of PFOS along the marine food chain (shorthorn sculpin<ringed seal<polar bear). The greatest concentration of PFOS was found in liver of polar bear from east Greenland (mean: 1285 ng/g wet weight, n=2). The geographical distribution of perfluorinated compounds in Greenland was similar to that of persistent organohalogenated compounds (OHCs), with the highest concentrations in east Greenland, indicating a similar geographical distribution to that of OHCs, with higher concentrations in east Greenland than in west Greenland. Perfluorinated acids were detected in livers of fish, birds and marine mammals from Greenland and the Faroe Islands.


From Science Direct

Biochemical and Biophysical Research Communications - Volume 329, Issue 2 , 8 April 2005, Pages 487-494

Effects of PFOS and PFOA on L-type Ca2+ currents in guinea-pig ventricular myocytes

Kouji Harada (a), Feng Xu (b), Kyoichi Ono (b), Toshihiko Iijima (b) and Akio Koizumia (a)

(a) Department of Health and Environmental Sciences, Kyoto University Graduate School of Medicine, Kyoto, Japan
(b) Department of Pharmacology, Akita University School of Medicine, Akita, Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are amphiphiles found ubiquitously in the environment, including wildlife and humans, and are known to have toxic effects on physiological functions of various tissues. We investigated the effects of PFOS and PFOA on action potentials and L-type Ca2+ currents, ICaL, in isolated guinea-pig ventricular myocytes using whole-cell patch-clamp recording. In current-clamp experiments, PFOS significantly decreased the rate of spike, action potential duration, and peak potential at doses over 10 µM. In voltage-clamp experiments, PFOS increased the voltage-activated peak amplitude of ICaL, and shifted the half-activation and inactivation voltages of ICaL to hyperpolarization. PFOA had similar effects PFOS, but showed significantly lower potency. These findings are consistent with previous observations for anionic n-alkyl surfactants, suggesting that PFOS and PFOA may change membrane surface potential, thereby eliciting general effects on calcium channels. These findings provide further insights into the mechanisms of PFOA and PFOS toxicities.


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15667078

Environ Sci Technol. 2005 Jan 1;39(1):80-4.

Temporal trends of PFOS and PFOA in guillemot eggs from the Baltic Sea, 1968--2003.

Holmstrom KE, Jarnberg U, Bignert A.

Institute of Applied Environmental Research (ITM), Stockholm University, SE-106 91 Stockholm, Sweden. katrin.holmstrom@itm.su.se

Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have recently been identified as ubiquitous environmental contaminants. Although they have been produced for 50 years, little is known about when they first appeared in the environment and how their concentrations have changed over time, particularly in response to the phase-out of PFOS, which began in 2000. In this study temporal trends in the concentrations of PFOS and PFOA in the Baltic Sea marine environmentwere measured using archived guillemot eggs. Samples collected from Stora Karlso (Sweden) between 1968 and 2003 were received from an environmental specimen bank and concentrations of PFOS and PFOA were analyzed using HPLC coupled to ESI-MS/MS. PFOA was not detected in any of the samples (LOD 3 ng/g), but there was an almost 30-fold increase in PFOS concentrations in the guillemot eggs during the time period, from 25 ng/g in 1968 to 614 ng/g in 2003 (wet weight). Regression analysis indicated a significant trend, increasing on average between 7 and 11% per year. A sharp peak in PFOS concentrations was observed in 1997 followed by decreasing levels up to 2002, but this cannot be linked to the PFOS phase-out, which occurred at the end of this period.

PMID: 15667078 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15694468

Chemosphere. 2005 Mar;58(11):1471-96.
 
Synthesis of environmentally relevant fluorinated surfactants-a review.

Lehmler HJ.

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

In the past years there has been a growing interest in fluorinated persistent organic pollutants such as perfluorooctanesulfonic acid, perfluorooctanesulfonamides, perfluorinated carboxylic acids and fluorotelomer alcohols. Although these compounds have probably been present in the environment for many decades, we are only now beginning to realize that these environmental contaminants may have serious environmental and health effects. This article gives a state-of-the-art review of synthetic approaches that have been employed for the synthesis of these environmentally relevant fluorinated compounds. Perfluorooctanesulfonic acid derivatives, in particular, pose a problem because only a few perfluorooctanesulfonic acid derivatives are available from commercial sources-a fact that limits the ability of researchers worldwide to further study these compounds. Because of the limited literature available, this article also describes synthetic approaches for shorter chain homologues or perfluoroether analogues that can potentially be applied for the synthesis of perfluorooctanesulfonic acid derivatives. The preparation of typical starting materials for the synthesis of perfluorooctanesulfonic acid derivatives such as the perfluoroalkanesulfonyl fluorides and chlorides will be discussed. Subsequently, their conversion into relevant perfluoroalkane sulfonate salts (R(F)SO(3)M), sulfonamides (R(F)SO(2)NH(2)), N-alkyl sulfonamides (R(F)SO(2)NHR, R=alkyl), N,N-dialkyl sulfonamides (R(F)SO(2)NR(2), R=alkyl), sulfonamidoethanol (R(F)SO(2)NRCH(2)CH(2)OH, R=-H, -CH(3) or -C(2)H(5)) and sulfonamidoacetates (R(F)SO(2)NRCH(2)CO(2)H, R=-H, -CH(3) or -C(2)H(5)) will be described. Many perfluorinated carboxylic acids and fluorotelomer alcohols are available from commercial sources. The review of the synthesis of these two classes of fluorinated compounds includes a review of their industrial synthesis and the synthesis of relevant degradation products.

PMID: 15694468 [PubMed - in process]


http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15679355

Anal Chem. 2005 Feb 1;77(3):864-70.
 
Development of a Solid-Phase Extraction-HPLC/Single Quadrupole MS Method for Quantification of Perfluorochemicals in Whole Blood.

Karrman A, van Bavel B, Jarnberg U, Hardell L, Lindstrom G.

Man-Technology-Environment Research Centre, Orebro University, SE-701 82 Orebro, Sweden, and Institute of Applied Environmental Research, Stockholm University, SE-106 91 Stockholm, Sweden.

A method for the determination of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) simultaneously with 10 closely related perfluorochemicals (PFCs) in human whole blood was developed and validated. PFOS and PFOA are used in various applications, for example, as surfactants and plastic additives, and are subject to environmental and health research due to their persistence. The main part of the data on PFCs in human blood is from serum samples, analyzed mainly by ion pair extraction followed by high-performance liquid chromatography (HPLC) and negative electrospray (ESI) tandem mass spectrometry (MS/MS). The analytical method developed here is suitable for human whole blood and involves solid-phase extraction (SPE) and HPLC negative electrospray single quadrupole mass spectrometry (HPLC/ES-MS). A whole blood aliquot was treated with formic acid and extracted on a octadecyl (C18) SPE column. The PFCs were isolated with methanol, and quantification was performed using single quadrupole mass spectrometry and perfluoroheptanoic acid as internal standard. Validation was performed in the range 0.3-194 ng/mL with recovery between 64 and 112% and limit of detection in the 0.1-0.5 ng/mL range for 11 of the 12 PFCs studied. We applied this method to 20 whole blood samples collected in 1997-2000 from the Swedish population in the ages 24-72. Eleven of the 12 PFCs were detected, and they were quantitatively and qualitatively confirmed using triple quadrupole LC/MS/MS analysis. PFOS, perfluorooctanesulfonamide, perfluorohexanesulfonate, PFOA and perfluorononanoic acid were quantified in all samples. In addition, perfluorohexanoic acid, perfluorodecanoic acid, perfluorodecanesulfonate, perfluoroundecanoic acid, perfluorododecanoic acid, and perfluorotetradecanoic acid were detected in some samples. This study shows that SPE and single quadrupole MS can be applied for extraction and quantification of PFCs in human whole blood, resulting in selectivity and low detection limits.

PMID: 15679355 [PubMed - in process]


From Science Direct

Environmental Toxicology and Pharmacology - Volume 19, Issue 1 , January 2005, Pages 57-70

Identification of genes responsive to PFOS using gene expression profiling

Wenyue Hu, Paul D. Jones, Trine Celius and John P. Giesy

Department of Zoology, National Food Safety and Toxicology Center and Institute of Environmental Toxicology, Michigan State University, East Lansing, 224 National Food Safety and Toxicology Center, MI 48824-1311, USA

Perfluorooctane sulfonic acid (PFOS) is widely distributed in the environment including in the tissues of wildlife and humans, however, its mechanism of action remains unclear. Here, the Affymetrix rat genome U34A genechip was used to identify alterations in gene expression due to PFOS exposure. Rat hepatoma cells were treated with PFOS at 2–50 mg/L (4–100 ?M) for 96 h. Sprague-Dawley rats were orally dosed with PFOS at 5 mg/kg/day for 3 days or 3 weeks. Genes that were significantly (P <0.0025) induced were primarily genes for fatty acid metabolizing enzymes, cytochrome P450s, or genes involved in hormone regulation. Consistent expression profiles were obtained for replicate exposures, for short-term and long-term in vivo exposures, and for acute and chronic exposures. One major pathway affected by PFOS was peroxisomal fatty acid B-oxidation, which could be explained by the structural similarity between PFOS and endogenous fatty acids.


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