| http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15296323
Environ
Sci Technol. 2004 Jul 1;38(13):3698-704.
Automated
solid-phase extraction and measurement of perfluorinated
organic acids and amides in human serum and milk.
Kuklenyik Z, Reich JA, Tully JS,
Needham LL, Calafat AM.
Division of Laboratory Sciences, National Center for
Environmental Health, Centers
for Disease Control and Prevention, Atlanta,
Georgia 30341, USA.
Organic fluorochemicals are used in multiple commercial
applications including surfactants, lubricants, paints,
polishes, food packaging, and fire-retarding foams.
Recent scientific findings suggest that several perfluorochemicals
(PFCs), a group of organic fluorochemicals, are ubiquitous
contaminants in humans and animals world wide. Furthermore,
concern has increased about the toxicity of these compounds.
Therefore, monitoring human exposure to PFCs is important.
We have developed a high-throughput method for measuring
trace levels of 13 PFCs (2 perfluorosulfonates, 8 perfluorocarboxylates,
and 3 perfluorosulfonamides) in serum and milk using
an automated solid-phase extraction (SPE) cleanup followed
by high-performance liquid chromatography-tandem mass
spectrometry. The method is sensitive, with limits of
detection between 0.1 and 1 ng in 1 mL of serum or milk,
is not labor intensive, involves minimal manual sample
preparation, and uses a commercially available automated
SPE system. Our method is suitable for large epidemiologic
studies to assess exposure to PFCs. We
measured the serum levels of these 13 PFCs in 20 adults
nonoccupationally exposed to these compounds. Nine of
the PFCs were detected in at least 75% of the subjects.
Perfluorooctanesulfonate (PFOS),
perfluorohexanesulfonate (PFHxS),
2-(N-methylperfluorooctane-sulfonamido)acetate (Me-PFOSA-AcOH),
perfluorooctanoate (PFOA),
and perfluorononanoate (PFNA)
were found in all of the samples.
The concentration order and measured levels of PFOS,
PFOA, Me-PFOSA-AcOH, and PFHxS compared
well with human serum levels previously reported.
Although no human data are available for the perfluorocarboxylates
(except PFOA), the high frequency
of detection of PFNA and
other carboxylates in our study suggests that human
exposure to long-alkyl-chain perfluorocarboxylates may
be widespread. We also
found PFOS in the serum and milk of rats administered
PFOS by gavage, but not in the milk of rats not dosed
with PFOS. Furthermore, we did not detect most
PFCs in two human milk samples. These findings suggest
that PFCs may not be as prevalent in human milk as they
are in serum. Additional studies are needed to determine
whether environmental exposure to PFCs can result in
PFCs partitioning into milk. Large
epidemiological studies to determine the levels of PFCs
among the U.S. general population are warranted.
PMID:
15296323 [PubMed - in process]
|
| http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15260330
Environ
Sci Technol. 2004 Jun 15;38(12):3316-21.
Degradation
of fluorotelomer alcohols: a likely atmospheric source
of perfluorinated carboxylic acids.
Ellis
DA, Martin JW, De Silva AO, Mabury SA, Hurley MD, Sulbaek
Andersen MP, Wallington TJ.
Department
of Chemistry, University of Toronto, 80 St. George Street,
Toronto, Ontario, Canada M5S 3H6.
Human
and animal tissues collected in urban and remote global
locations contain persistent and bioaccumulative perfluorinated
carboxylic acids (PFCAs). The source of PFCAs was previously
unknown. Here we present smog chamber studies that indicate
fluorotelomer alcohols (FTOHs) can degrade in the atmosphere
to yield a homologous series of PFCAs. Atmospheric degradation
of FTOHs is likely to contribute to the widespread dissemination
of PFCAs. After their bioaccumulation potential is accounted
for, the pattern of PFCAs yielded from FTOHs could account
for the distinct contamination profile of PFCAs observed
in arctic animals. Furthermore, polar bear liver was
shown to contain predominately linear isomers (>99%)
of perfluorononanoic acid (PFNA), while both branched
and linear isomers were observed for perfluorooctanoic
acid, strongly suggesting a sole input of PFNA from
"telomer"-based products. The
significance of the gas-phase peroxy radical cross reactions
that produce PFCAs has not been recognized previously.
Such reactions are expected to occur during the atmospheric
degradation of all polyfluorinated materials, necessitating
a reexamination of the environmental fate and impact
of this important class of industrial chemicals.
PMID:
15260330 [PubMed - in process]
|
| http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15543740
Environ
Sci Technol. 2004 Oct 15;38(20):5379-85.
Perfluoroalkyl contaminants in a food web from
Lake Ontario.
Martin
JW, Whittle DM, Muir DC, Mabury SA.
Department
of Chemistry, University of Toronto, Toronto, Ontario
M5S 3H6, Canada. jwmartin@ualberta.ca
Perfluorooctane
sulfonate (PFOS) is a persistent and bioaccumulative
perfluorinated acid detectable in humans and wildlife
worldwide that has alerted scientists to examine the
environmental fate of other fluorinated organic contaminants.
Recently a homologous series of perfluoroalkyl carboxylates
(PFCAs) was detected in the Arctic, yet little
is known about their sources, breadth of contamination,
or environmental distribution. In this study we analyzed
for PFOS, the homologous series of PFCAs ranging from
8 to 15 carbons in chain length, and the PFOS-precursor
heptadecafluorooctane sulfonamide (FOSA) in various
organisms from a food web of Lake Ontario. The sampled
organisms included a top predator fish, lake trout (Salvelinus
namaycush), three forage fish species including rainbow
smelt (Osmerus mordax), slimy sculpin (Cottus cognatus),
and alewife (Alosa pseudoharengus), and two invertebrates
Diporeia (Diporeia hoyi) and Mysis (Mysis relicta).
A striking finding was
that the highest mean concentration for each fluorinated
contaminant was detected in the benthic macroinvertebrate
Diporeia, which occupies the lowest trophic level of
all organisms analyzed. Perfluorinated acid concentrations
in Diporeia were often 10-fold higher than in Mysis,
a predominantly pelagic feeder, suggesting
that a major source of perfluoroalkyl contaminants to
this food web was the sediment, not the water. PFOS
was the dominant acid in all samples, but long-chain
PFCAs, ranging in length from 8 to 15 carbons, were
also detected in most samples between <0.5
and 90 ng/ g. Among Mysis and the more pelagic fish
species (e.g. excluding Diporeia and sculpin) there
was evidence for biomagnification, but the influence
of foraging on highly contaminated Diporeia and sculpin
by these fish may have overestimated trophic magnification
factors (TMFs), which ranged from 0.51 for FOSA to 5.88
for PFOS. By accounting for the known diet composition
of lake trout, it was shown that
bioaccumulation was indeed occurring at the top of the
food web for all perfluoroalkyl compounds except PFOA.
Future monitoring at other locations in Lake Ontario,
and in other aquatic environments, is necessary to determine
if these food web dynamics are widespread.
Archived lake trout samples
collected between 1980 and 2001 showed that mean whole
body PFOS concentrations increased from 43 to 180 ng/g
over this period, but not linearly, and
may have been indirectly influenced by the invasion
and proliferation of zebra mussels (Dreissena polymorpha)
through effects on the population and ecology of forage
fishes.
PMID:
15543740 [PubMed - in process]
|
| http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15575267
Environ
Sci Technol. 2004 Nov 1;38(21):5522-8.
Analysis of perfluorinated acids at parts-per-quadrillion
levels in seawater using liquid chromatography-tandem
mass spectrometry.
Yamashita
N, Kannan K, Taniyasu S, Horii Y, Okazawa T, Petrick
G, Gamo T.
National
Institute of Advanced Industrial Science and Technology,
16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan.
Perfluorinated
acids (PFAs) and their salts have emerged as an important
class of global environmental contaminants. Determination
of sub-parts-per-trillion or parts-per-quadrillion concentrations
of perfluorinated acids in aqueous media has been impeded
by relatively high background levels arising from procedural
or instrumental blanks. To understand the role of the
oceans in the transport and fate of perfluorinated acids,
methods to determine ultratrace levels of these compounds
in seawater are needed. In this study, sources of procedural
and instrumental blank contamination by perfluorinated
acids have been identified and eliminated, to reduce
background levels in blanks and thereby improve limits
of quantitation. The method developed in this study
is capable of detecting perfluorooctanesulfonate (PFOS),
perfluorohexanesulfonate (PFHS), perfluorobutanesulfonate
(PFBS), perfluorooctanoate (PFOA), perfluorononanoate
(PFNA), and perfluorooctanesulfonamide (PFOSA) at low
pg/L levels in oceanic waters. PFOA
is the major perfluorinated compound detected in oceanic
waters, followed by PFOS. Further studies are
being conducted to elucidate the distribution and fate
of perfluorinated acids in oceans.
|
Journal
of Fluorine Chemistry Volume 125, Issue 8 , August
2004, Pages 1211-1216
Fluorine in Alternative Energy Sources
Nafion®
perfluorinated membranes in fuel
cells
Shoibal
Banerjee (a), , and Dennis E. Curtin (b)
a
DuPont Fuel Cells, Chestnut Run Plaza CRP701/213, Wilmington,
DE 19805-0701, USA
b DuPont Fuel Cells, 22828 NC Highway 87W, Fayetteville,
NC 28306, USA
Abstract: Increasing global energy requirements, localized
power issues and the need for less environmental impact
are now providing even more incentive to make fuel cells
a reality. A number of technologies have been demonstrated
to be feasible for generation of power from fuel cells
over the last several years. Proton exchange membranes
(PEM) have emerged as an essential factor in the technology
race. DuPont has supplied Nafion®
perfluorinated membranes in fuel cells for space travel
for more than 35 years and they have played an
integral part in the success of recent work in portable,
stationary and transportation applications. The basis
for PEM fuel cell emergence and DuPont technology utilization
will be discussed.
Excerpt:
... During the period 1977–1984, DuPont invested
in building a monomer, polymer, and membrane fabrication
plant in Fayetteville NC to meet the needs of the Chloralkali
market (Fig. 2 and Fig. 3). Today,
the Chloralkali industry is the largest market for our
Nafion® products...
|
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15669302
Environ Sci Technol.
2004 Dec 15;38(24):6475-81.
Fluorinated organic compounds in an eastern
Arctic marine food web.
Tomy
GT, Budakowski W, Halldorson T, Helm PA, Stern GA, Friesen K,
Pepper K, Tittlemier SA, Fisk AT.
Department of Fisheries
& Oceans Canada, 501 University Crescent, Winnipeg, Manitoba
R3T2N6, Canada. tomyg@dfo-mpo.gc.ca
An eastern Arctic
marine food web was analyzed for
perfluorooctanesulfonate (PFOS, C8F17SO3-),
perfluorooctanoate (PFOA, C7F15COO-),
perfluorooctane sulfonamide (PFOSA, C8F17SO2NH2),
and
N-ethylperfluorooctane sulfonamide (N-EtPFOSA,
C8F17SO2NHCH2CH3) to examine the extent of bioaccumulation.
PFOS was detected in
all species analyzed, and mean concentrations ranged
from 0.28 +/- 0.09 ng/g (arithmetic mean +/- 1 standard error,
wet wt, whole body) in clams (Mya truncata) to 20.2 +/- 3.9
ng/g (wet wt, liver) in glaucous gulls (Larus hyperboreus).
PFOA was detected
in approximately 40% of the samples analyzed at concentrations
generally smaller than those found for PFOS; the
greatest concentrations were observed in zooplankton
(2.6 +/- 0.3 ng/g, wet wt).
N-EtPFOSA
was detected in all species except redfish with mean concentrations
ranging from 0.39 +/- 0.07 ng/g (wet wt) in mixed zooplankton
to 92.8 +/- 41.9 ng/g (wet wt) in Arctic cod (Boreogadus saida).
This is the first report of N-EtPFOSA
in Arctic biota.
PFOSA was only
detected in livers of beluga (Delphinapterus leucas) (20.9 +/-
7.9 ng/g, wet wt) and narwhal (Monodon monoceros) (6.2 +/- 2.3
ng/g, wet wt), suggesting that N-EtPFOSA and other PFOSA-type
precursors are likely present but are being biotransformed to
PFOSA. A positive linear relationship was found between
PFOS concentrations (wet wt) and trophic level (TL), based on
delta15N values, (r2 = 0.51, p < 0.0001) resulting in a trophic
magnification factor of 3.1. TL-corrected biomagnification
factor estimates for PFOS ranged from 0.4 to 9. Both
results indicate that PFOS biomagnifies in the Arctic marine
food web when liver concentrations of PFOS are used for seabirds
and marine mammals. However, transformation
of N-EtPFOSA and PFOSA and potential other perfluorinated compounds
to PFOS may contribute to PFOS levels in marine mammals and
may inflate estimated biomagnification values. None of
the other fluorinated compounds (N-EtPFOSA, PFOSA, and PFOA)
were found to have a significant relationship with TL, but BMF(TL)
values of these compounds were often >1, suggesting
potential for these compounds to biomagnify. The presence of
perfluorinated compounds in seabirds and mammals provides evidence
that trophic transfer is an important exposure route of these
chemicals to Arctic biota.
PMID: 15669302 [PubMed
- in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15597866
Environ Sci Technol.
2004 Dec 1;38(23):452A.
No
Abstract available
Canada
moves to eliminate PFOS stain repellents.
Pelley
J.
PMID: 15597866
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15575267
Environ Sci Technol.
2004 Nov 1;38(21):5522-8.
Analysis of perfluorinated acids at parts-per-quadrillion
levels in seawater using liquid chromatography-tandem mass spectrometry.
Yamashita
N, Kannan K, Taniyasu S, Horii Y, Okazawa T, Petrick G, Gamo
T.
National Institute
of Advanced Industrial Science and Technology, 16-1 Onogawa,
Tsukuba, Ibaraki 305-8569, Japan.
Perfluorinated acids
(PFAs) and their salts have emerged as an important class of
global environmental contaminants. Determination of sub-parts-per-trillion
or parts-per-quadrillion concentrations of perfluorinated acids
in aqueous media has been impeded by relatively high background
levels arising from procedural or instrumental blanks. To understand
the role of the oceans in the transport and fate of perfluorinated
acids, methods to determine ultratrace levels of these compounds
in seawater are needed. In this study, sources of procedural
and instrumental blank contamination by perfluorinated acids
have been identified and eliminated, to reduce background levels
in blanks and thereby improve limits of quantitation. The method
developed in this study is capable of detecting perfluorooctanesulfonate
(PFOS), perfluorohexanesulfonate (PFHS), perfluorobutanesulfonate
(PFBS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA),
and perfluorooctanesulfonamide (PFOSA) at low pg/L levels in
oceanic waters. PFOA is the major perfluorinated
compound detected in oceanic waters, followed by PFOS.
Further studies are being conducted to elucidate the distribution
and fate of perfluorinated acids in oceans.
PMID: 15575267
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15573615
Environ Sci Technol.
2004 Nov 15;38(22):6118-24.
Decomposition of environmentally persistent perfluorooctanoic
acid in water by photochemical approaches.
Hori
H, Hayakawa E, Einaga H, Kutsuna S, Koike K, Ibusuki T, Kiatagawa
H, Arakawa R.
National Institute
of Advanced Industrial Science and Technology, 16-1 Onogawa,
Tsukuba 305-8569, Japan. h-hori@aist.go.jp
The decomposition
of persistent and bioaccumulative perfluorooctanoic acid (PFOA)
in water by UV-visible light irradiation, by H202 with UV-visible
light irradiation, and by a tungstic heteropolyacid photocatalyst
was examined to develop a technique to counteract stationary
sources of PFOA. Direct photolysis proceeded slowly to produce
CO2, F-, and short-chain perfluorocarboxylic acids. Compared
to the direct photolysis, H2O2 was less effective in PFOA decomposition.
On the other hand, the heteropolyacid photocatalyst led to efficient
PFOA decomposition and the production of F- ions and CO2. The
photocatalyst also suppressed the accumulation of short-chain
perfluorocarboxylic acids in the reaction solution. PFOA in
the concentrations of 0.34-3.35 mM, typical of those in wastewaters
after an emulsifying process in fluoropolymer manufacture, was
completely decomposed by the catalyst within 24 h of irradiation
from a 200-W xenon-mercury lamp, with no accompanying catalyst
degradation, permitting the catalyst to be reused in consecutive
runs. Gas chromatography/mass spectrometry (GC/MS) measurements
showed no trace of environmentally undesirable species such
as CF4, which has a very high global-warming potential. When
the (initial PFOA)/(initial catalyst) molar ratio was 10: 1,
the turnover number for PFOA decomposition reached 4.33 over
24 h of irradiation.
PMID: 15573615
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15573472
Drug Chem Toxicol.
2004 Nov;27(4):361-78.
13-week dietary toxicity study of ammonium perfluorooctanoate
(APFO) in male rats.
Perkins
RG, Butenhoff JL, Kennedy GL Jr, Palazzolo MJ.
3M
Medical Department, Corporate Toxicology,
St. Paul, MN 55144, USA. rgperkins@mmm.com
Ammonium perfluorooctanoate
is a perfluorinated carboxylate that is used commercially as
a processing aid in the production of fluorinated polymers.
Perfluorooctanoate (PFOA) has been
found in human blood of the general population from exogenous
sources. This report presents the results of a 13-week dietary
toxicity study in male rats and was designed to identify potential
target organ(s), dose response, and to explore possible relationships
of PPARalpha activation to potential liver effects and hormonal
changes. Rats were fed dietary levels of 0, 1, 10, 30, and 100
ppm (equivalent to 0, 0.06, 0.64, 1.94, and 6.5 mg/kg/day) for
13 weeks. A control group pair-fed adjusted to the 100 ppm level
and groups allowed to recover for 8 weeks were included. Sacrifices
were conducted after 4, 7, and 13 weeks of feeding and after
8 weeks of recovery. At each sacrifice, gross and histopathology
was conducted on selected tissues and measurements of hepatic
palmitoyl CoA oxidase (PCoAO), as well as serum estradiol, luteinizing
hormone, testosterone, and PFOA were determined. There were
no clinical signs or mortality. Body weight gains were reduced
in the 100 ppm dose group. Liver weights (absolute and relative),
PCoAO activity, and hepatocyte hypertrophy (minimal to mild)
were increased in the 10 ppm dose group and above and were reversible
in recovery. Under the study conditions, hormone levels appeared
unchanged. PFOA serum concentrations increased in a dose-related
fashion, appeared to reach steady-state by test week 5, and
declined rapidly through the recovery period. Serum
PFOA concentrations at the end of the treatment period were
7.1, 41, 70, and 138 microg/mL in the 1, 10, 30 and 100 ppm
dose groups. The study no effect level was 1 ppm (0.06
microg/mg) with doses of 10 ppm (0.64 microg/mg) and higher
producing adaptive and reversible liver changes.
PMID: 15573472
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15573471
Drug Chem Toxicol.
2004 Nov;27(4):341-60.
Binding of perfluorooctanoic acid to rat liver-form
and kidney-form alpha2u-globulins.
Han
X, Hinderliter PM, Snow TA, Jepson GW.
DuPont
Haskell Laboratory for Health and Environmental Sciences,
Newark, Delaware 19714, USA. xing.han@usa.dupont.com
Perfluorooctanoic
acid (PFOA) is an organic fluorochemical
and is reported to have a long half-life in human blood. Its
urinary elimination in rats is markedly sex-dependent, and characterized
by significantly longer plasma half-life of PFOA in male rats
than in females. It has been postulated that male-specific PFOA
binding protein(s) is responsible for the long half-life of
PFOA in male rats. In this paper, two male rat specific proteins,
liver- and kidney-form alpha2u-globulins (A2U(L) and A2U(K)),
were purified from male rat urine and kidney, respectively.
The binding of these two nroteins to PFOA was investigated using
ligand blotting, electrospray ionization mass spectrometry and
fluorescence competitive binding assay. The results revealed
that both A2U(L) and A2U(K) were able to bind PFOA in vitro
under physiological conditions, and that PFOA and a fluorescent-labeled
fatty acid shared the same binding site on both A2U(L) and A2U(K).
The binding affinities, however, are relatively weak. The estimated
dissociation constants are in the 10(-3) M range, indicating
that bindings of PFOA to either A2U(L) or A2U(K) cannot adequately
explain the sex-dependent elimination of PFOA in rats, and it
is unlikely that PFOA-A2U(K) binding would induce A2U nephropathy
as seen with, for example, 1,4-dichlorobenzene.
PMID: 15573471
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15559291
Environ Toxicol Chem.
2004 Nov;23(11):2745-55.
Partial
life-cycle toxicity and bioconcentration modeling of perfluorooctanesulfonate
in the northern leopard frog (Rana pipiens).
Ankley
GT, Kuehl DW, Kahl MD, Jensen KM, Butterworth BC, Nichols JW.
US
Environmental Protection Agency,
Office of Research and Development, National Health and Environmental
Effects Research Laboratory, Mid-Continent Ecology Division,
Duluth, Minnesota 55804, USA. ankley.gerald@epa.gov
A number of recent
monitoring studies have demonstrated elevated concentrations
of perfluorooctanesulfonate (PFOS) in humans and wildlife throughout
the world. Although no longer manufactured in the United States,
the global distribution and relative persistence of PFOS indicates
a need to understand its potential ecological effects. Presently,
little is known concerning toxicity of PFOS in chronic exposures
with aquatic species. Therefore, we evaluated the effects of
PFOS on survival and development of the northern leopard frog
(Rana pipiens) from early embryogenesis through complete metamorphosis.
Exposures were conducted via water at measured PFOS concentrations
ranging from 0.03 to 10 mg/L. Animals
exposed to 10 mg/L began dying within approximately two weeks
of test initiation. Survival was not affected by PFOS
at lower concentrations; however, time
to metamorphosis was delayed and growth reduced in the 3-mg/L
treatment group. Tadpoles readily accumulated PFOS directly
from water. Using a one-compartment bioaccumulation model, growth
was shown to have a modest impact on steady-state PFOS concentrations.
Variability in observed growth rates and the possible contribution
of a size-dependent decrease in PFOS elimination rate contributed
uncertainty to modeling efforts. Nevertheless, fitted uptake
and elimination rate constants were comparable to those determined
in earlier studies with juvenile rainbow trout. Overall, our
studies suggest that R. pipiens is not exceptionally sensitive
to PFOS in terms of either direct toxicity or bioconcentration
potential of the chemical.
PMID: 15559291
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15497853
Water Sci Technol.
2004;50(5):235-42.
Perfluorooctane sulfonate--a quite mobile anionic anthropogenic
surfactant, ubiquitously found in the environment.
Meesters
RJ, Schroder HF.
Institut fur Siedlungswasserwirtschaft,
Aachen University, Templergraben 55, D-52056 Aachen, Germany.
meesters@isa.rwth-aachen.de
The biochemical degradation
of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid
(PFOA) under aerobic and anaerobic conditions in closed-loop
systems was monitored in laboratory scale. Adsorptive effects
of these compounds to glass and polypropylene were also examined.
Liquid chromatography/mass spectrometry (LC-MS) under negative
electrospray (ESI(-)) conditions was applied for determination.
Elimination of PFOS was observed under anaerobic conditions
whereas aerobic treatment was not effective.
PMID: 15497853
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15461154
Environ Sci Technol.
2004 Sep 1;38(17):4489-95.
Perfluorooctanesulfonate
and related fluorochemicals in human blood from several countries.
Kannan
K, Corsolini S, Falandysz J, Fillmann G, Kumar KS, Loganathan
BG, Mohd MA, Olivero J, Van Wouwe N, Yang JH, Aldoust KM.
Wadsworth Center,
New York State Department of Health, and Department of Environmental
Toxicology and Health, State University of New York, Empire
State Plaza, P.O. Box 509, Albany, New York 12201-0509, USA.
Kkannan@wadsworth.org
Perfluorooctanesulfonyl
fluoride based compounds have been used in a wide variety of
consumer products, such as carpets, upholstery, and textiles.
These compounds degrade to perfluorooctanesulfonate (PFOS),
a persistent metabolite that accumulates in tissues of humans
and wildlife. Previous studies have reported the occurrence
of PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate
(PFOA), and perfluorooctanesulfonamide (PFOSA) in human sera
collected from the United States. In this study, concentrations
of PFOS, PFHxS, PFOA, and PFOSA were measured
in 473 human blood/serum/plasma samples collected from the United
States, Colombia, Brazil, Belgium, Italy, Poland, India, Malaysia,
and Korea. Among the four perfluorochemicals measured, PFOS
was the predominant compound found in blood. Concentrations
of PFOS were the highest in the samples collected from the United
States and Poland (>30 ng/mL); moderate in Korea, Belgium,
Malaysia, Brazil, Italy, and Colombia (3 to 29 ng/mL); and lowest
in India (<3 ng/mL). PFOA was
the next most abundant perfluorochemical in blood samples, although
the frequency of occurrence of this compound was relatively
low. No age- or gender-related differences in the concentrations
of PFOS and PFOA were found in serum samples. The degree of
association between the concentrations of four perfluorochemicals
varied, depending on the origin of the samples. These results
suggested the existence of sources with varying levels and compositions
of perfluorochemicals, and differences in exposure patterns
to these chemicals, in various countries. In addition to the
four target fluorochemicals measured, qualitative analysis of
selected blood samples showed the presence of other perfluorochemicals
such as perfluorodecanesulfonate (PFDS), perfluoroheptanoic
acid (PFHpA), perfluorononanoic acid (PFNA), perfluorodecanoic
acid (PFDA), perfluorododecanoic acid (PFDoA), and perfluoroundecanoic
acid (PFUnDA) in serum samples, at concentrations approximately
5- to 10-fold lower than the concentration of PFOS. Further
studies should focus on identifying sources and pathways of
human exposure to perfluorochemicals.
PMID: 15461154
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15461284
Wei Sheng Yan Jiu.
2004 Jul;33(4):481-3.
[Status
of perfluorochemicals in adult serum and umbilical blood in
Shenyang]
[Article in Chinese]
Jin
Y, Liu X, Li T, Qin H.
Institute of Public
Hygiene, China Medical University, Shenyang 110001, China.
OBJECTIVE: To study
the status of perfluorooctane sulfonate (PFOS), and Perfluorooctanoic
acid (FOA) pollution in serum and umbilical blood among general
people in Shenyang area.
METHODS: Concentration of PFOS and PFOA in adult serum and umbilical
blood samples was measured by means of liquid phase chromatography/mass
spectrograph selective iron monitoring (PFOS: m/z = 499, PFOA:
m/z = 413).
RESULTS: It was showed that geometric mean of serum concentration
of PFOS of male was 40.73microg/L and that of female was 45.46microg/L,
PFOA is 11.53microg/L and 8.97microg/L. Geometric mean concentration
of PFOS and PFOA in umbilical blood was 2.214microg/L and 0.264microg/L.
There was no correlativity between concentration of PFOS, PFOA
and age in adult serum and umbilical blood.
CONCLUSION: It was suggested that there
was PFOS contamination in common group in Shenyang. Also, fetus
was exposed in PFOS and PFOA during its embryonic period. There
were also PFOS and PFOA pollution in human umbilical blood samples.
PMID: 15461284
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15470233
Toxicol Sci. 2004
Oct 6 [Epub ahead of print]
Pharmacokinetics of Perfluorooctanoate (PFOA) in Cynomolgus
Monkeys.
Butenhoff
JL, Kennedy GL Jr, Hinderliter PM, Lieder PH, Jung R, Hansen
KJ, Gorman GS, Noker PE, Thomford PJ.
3M,
St. Paul, Minnesota 55144.
The pharmacokinetics
of perfluorooctanoate (PFOA) in cynomolgus monkeys were studied
in a six-month oral capsule dosing study of ammonium perfluorooctanoate
(APFO) and in a single-dose intravenous (iv) study. In the oral
study, samples of serum, urine, and feces were collected every
two weeks from monkeys given daily doses of either 0, 3, 10,
or 20 mg APFO/kg. Steady-state was reached within 4 weeks in
serum, urine, and feces. Serum PFOA followed first-order elimination
kinetics after the last dose, with a half-life of approximately
20 days. Urine was the primary elimination route. Mean serum
PFOA concentrations at steady state in the 3, 10, and 20 mg/kg-day
dose groups, respectively, were: 81, 99, and 156 microg/ml in
serum; 53, 166, and 181 microg/ml in urine; and, 7, 28, and
50 mg/g in feces. Mean liver concentrations reached 16, 14,
and 50 mg/g in the 3, 10, and 20 mg/kg groups, respectively.
In the iv study, 3 monkeys per sex were given a single dose
of 10 mg/kg potassium PFOA. Samples were collected through 123
days. The terminal halflife of PFOA in serum was 13.6, 13.7,
and 35.3 days in the 3 male monkeys and 26.8, 29.3, and 41.7
days in the 3 females. Volume of distribution at steady state
was 181 +/- 12 and 198 +/- 69 mL/kg for males and females, respectively.
Based on the result of both the oral and iv studies, the elimination
half-life is approximately 14-42 days, and urine is the primary
route of excretion.
PMID: 15470233
[PubMed - as supplied by publisher]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15378987
Environ Toxicol Chem.
2004 Sep;23(9):2116-23.
Toxicity
of perfluorooctane sulfonic acid and perfluorooctanoic acid
to Chironomus tentans.
MacDonald
MM, Warne AL, Stock NL, Mabury SA, Solomon KR, Sibley PK.
Department of Environmental
Biology, University of Guelph, Guelph, Ontario N1G 2W1, Canada.
Two perfluorinated
surfactants, perfluorooctanoic acid (PFOA) and perfluorooctane
sulfonic acid (PFOS), were evaluated for
their toxicity to the aquatic midge, Chironomus tentans.
Impetus for this laboratory study originated from a 10-d, in
situ field assessment in which C. tentans was exposed to PFOS
at concentrations ranging from 300 to 30,000 microg/L. No midges
survived these exposures. Midge survival in a preliminary, acute
10-d laboratory test with nominal PFOS concentrations ranging
from 0.1 to 100,000 microg/L showed similar toxicity with respect
to survival (median lethal concentration [LC50], 45.2 microg/L)
and growth (median effective concentration [EC50], 27.4 microg/L).
A parallel test using PFOA indicated no significant impacts
on survival or growth. A definitive 10-d assay with PFOS concentrations
ranging from 1 to 150 microg/L produced an EC50 for growth (87.2+/-11.6
microg/L) of the same order of magnitude as that in the preliminary
findings. The same was not true for survival, however, with
the LC50 falling outside the range of test concentrations. To
further investigate the sensitivity of C. tentans to PFOS, we
conducted a chronic life-cycle test using a nominal concentration
range of 1 to 100 microg/L. Three of the four endpoints measured-survival,
growth, and emergence-were significantly affected, with EC50
values of 92.2+/-3.1, 93.8+/-2.6, and 94.5+/-3.2 microg/L, respectively.
Reproduction was not affected by those PFOS concentrations at
which females emerged. The results of
the present study indicate that PFOS toxicity thresholds for
C. tentans are as much as three orders of magnitude lower than
those reported for other aquatic organisms but, at present,
are approximately two orders of magnitude higher than those
concentrations typically observed in aquatic environments.
PMID: 15378987
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15352480
Environ Toxicol Chem.
2004 Aug;23(8):1912-9.
Impact
of perfluorooctanoic acid on fathead minnow (Pimephales promelas)
fatty acyl-CoA oxidase activity, circulating steroids, and reproduction
in outdoor microcosms.
Oakes
KD, Sibley PK, Solomon KR, Mabury SA, Van der Kraak GJ.
Department of Zoology,
University of Guelph, Guelph, Ontario N1G 2W1, Canada.
This study investigates
reproductive impairment and biochemical changes in fathead minnow
(Pimephales promelas) exposed for 39 d to varying concentrations
of perfluorooctanoic acid (PFOA) under microcosm conditions.
While the concentrations tested in this study were much higher
than those normally found in the environment, no mortality was
associated with PFOA exposure. Only modest changes were observed
in condition factor and in relative liver and gonad size. Significant
declines in circulating plasma steroids were observed,
but these were accompanied by only limited increases in time
to first oviposition and decreases in overall egg production.
Peroxisome proliferation, as quantified by fatty acyl-CoA oxidase
(FAO) activity, was elevated with low PFOA concentrations but
attenuated with exposure to higher PFOA doses. Little evidence
was seen of differential induction of peroxisome-associated
enzyme activity with sex. Oxidative stress, as quantified by
the 2-thiobarbituric acid reactive substances (TBARS) assay,
was only modestly influenced by PFOA exposure and is not a significant
consequence of FAO activity in fathead minnow. Perfluorooctanoic
acid appears to be relatively nontoxic at environmentally relevant
concentrations but may impact biochemical and reproductive endpoints
under conditions associated with environmental spills.
PMID:
15352480 [PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15352442
Environ Sci Technol.
2004 Aug 1;38(15):4064-70.
Detection
of perfluorooctane surfactants in Great
Lakes water.
Boulanger
B, Vargo J, Schnoor JL, Hornbuckle KC.
University of Iowa,
Department of Civil and Environmental Engineering, SC 4105,
Iowa City, Iowa 52240, USA.
Widespread use of
perfluorooctane surfactants has led to ubiquitous presence of
these chemicals in biological tissues. While perfluorooctane
surfactants have been measured in blood and liver tissue samples
of fish, birds, and mammals in the Great Lakes region, data
for the aqueous concentrations of these compounds in the Great
Lakes or other ambient waters is lacking. Sixteen Great Lakes
water samples were analyzed for eight perfluorooctane surfactants.
The monitored perfluorooctane surfactants were quantitatively
determined using single quadrupole HPLC/MS and qualitatively
confirmed using ion trap MS/MS. Additionally, PFOS was quantitatively
confirmed using triple quadrupole LC/MS/MS. Concentrations
of PFOS and PFOA in the two lakes ranged from 21-70 and 27-50
ng/L, respectively. Analysis also showed the presence of PFOS
precursors, N-EtFOSAA (range of 4.2-11 ng/L) and FOSA (range
of 0.6-1.3 ng/L), in all samples above the LOQ. PFOSulfinate,
another precursor, was identified at six of eight locations
with a concentration range, when present, of <2.2-17 ng/L.
Other PFOS precursors, N-EtFOSE, PFOSAA, and N-EtFOSA were not
observed at any of the sampling locations. These
are the first reported concentrations of perfluorooctane surfactants
in Great Lakes water and the first report of PFOS precursors
in any water body.
PMID: 15352442
[PubMed - in process]
http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=pubmed&dopt=Abstract&list_uids=15352441
Environ Sci Technol.
2004 Aug 1;38(15):4056-63.
Perfluorinated
compounds in coastal waters of Hong Kong,
South China, and Korea.
So
MK, Taniyasu S, Yamashita N, Giesy JP, Zheng J, Fang Z, Im SH,
Lam PK.
Centre for Coastal
Pollution and Conservation, Department of Biology and Chemistry,
City University of Hong Kong.
Perfluorinated compounds
(PFCs), such as perfluorooctanesulfonate (PFOS) and related
compounds, have recently been identified in the environment.
PFOS, the terminal degradation product of many of the PFCs,
has been found globally in many wildlife species, as well as
open ocean waters, even in remote regions far from sources.
In this study, a solid-phase extraction procedure coupled with
high-performance liquid chromatography interfaced to high-resolution
mass spectrometry was used to isolate, identify, and quantify
small concentrations of PFCs in seawater. These techniques were
applied to investigate the local sources of PFCs in several
industrialized areas of Asia and provide information on how
the PFCs are circulated by coastal currents. Ranges of concentrations
of PFOS in coastal seawaters of Hong Kong, the Pearl River Delta,
including the South China Sea, and Korea were 0.09-3.1, 0.02-12,
and 0.04-730 pg/mL, respectively, while those of perfluorooctanoic
acid (PFOA) were 0.73-5.5, 0.24-16, and 0.24-320 pg/mL, respectively.
Potential sources of PFCs include major industrialized areas
along the Pearl River Delta of southern China and major cities
of Korea, which are several of the fastest growing industrial
and economic regions in the world. Detectable concentrations
of PFOS and PFOA in waters of southern China were similar to
those in the coastal marine environment of Japan and certain
regions in Korea. Concentrations of PFCs
in several locations in Korean waters were 10-100-fold greater
than those in the other locations on which we report here. The
spatial and seasonal variations in PFC concentrations in surface
seawaters in the Pearl River Delta and South China Sea indicate
the strong influence of the Pearl River discharge on the magnitude
and extent of PFC contamination in southern China. All
of the concentrations of PFOS were less than those that would
be expected to cause adverse effects to aquatic organisms or
their predators except for one location in Korea adjacent to
an industrialized area. Hazard quotients were from <0.001
to 0.002 for aquatic animals and ranged from <0.001 to 17
for predatory birds.
PMID: 15352441
[PubMed - in process]
Full
free report available at http://dioxin2004.abstract-management.de/pdf/p134.pdf
Paper presented
at Dioxin 2004: 24th International Symposium on Halogenated
Environmental Organic Pollutants and POPs. Berlin, September
6 - 10, 2004.
ORGANOHALOGEN COMPOUNDS
– Volume 66 (2004) 4004-4008.
Perfluorinated
compounds in human serum and seminal plasma from an urban and
rural population in Sri Lanka
Keerthi
Guruge (1), Sachi Taniyasu (2), Nobuyoshi Yamashita (2), Shigeru
Miyazaki (1),
Noriko Yamanaka (1), Sumedha Wijeratna (3), Harsha Seneviratne
(3)
1 National Institute
of Animal Health, Tsukuba, Japan
2 National Institute of Advance Industrial and Technology, Tsukuba,
Japan
3 University of Colombo, Colombo, Sri Lanka
4 Tea Research Institute of Sri Lanka, Talawakele, Sri Lanka
Introduction. Fluorinated
organic compounds (FOCs) have been used for variety of industrial
applications such as surfactants, adhesives, insecticides, and
their global production increase since 1970s. These compounds
repel both water and oil. The high-energy carbon-fluorine covalent
bonds in FOCs are strong enough to have high persistency in
the environment. These compounds emerged as priory environmental
pollutants since they are found in various biota throughout
the world.1-2 Human contamination of some FOCs was reported
mostly in developed countries such as USA, Japan and from Europe.3--7
In the present study, we report 10 FOCs in human serum including
seminal plasma for the first time, collected from volunteers
from Sri Lanka ...
... We observed an increasing trend of PFOS and PFOA accumulation
between seminal plasma and sera (Figures 3 & 4), while no
age trend.
The accumulation of PFOS in sera was positively correlated with
PFHS, PFNA, PFUnA and PFOA suggesting that these compounds have
similar accumulation properties (Figure 5) in human body fluids.
All the FOCs concentrations in sera and
seminal plasma in urban location were significantly higher than
those from the rural location. The greater exposure levels
found in Colombo revealed that wide variety of applications
with perfluoroalkylated compound such as paper, packing products,
carpet spray, stain-resistant textiles, cosmetics, electronics
and fire-fighting foams, are readily existing for urban community
compared to the rural population in Sri Lanka
Overall, these data are indicated that human contamination of
FOCs was widespread even in developing countries similar to
those in industrialized ones. Exposure to organohalogen compounds
may be associated with human reproductive failiers.8 Several
FOC compounds were found in seminal plasma have long half-lives
(> 1 year) suggesting that those compounds might pose adverse
health effects including male fertility associated with long-term
exposure. Since these compound had greater accumulations
in higher trophic positions, they should be considered in future
risk assessments of chemical exposure in human.
Full
free report available at http://dioxin2004.abstract-management.de/pdf/p350.pdf
Paper presented
at Dioxin 2004: 24th International Symposium on Halogenated
Environmental Organic Pollutants and POPs. Berlin, September
6 - 10, 2004.
ORGANOHALOGEN COMPOUNDS
– Volume 66 (2004) 4058-4062.
LEVELS
OF PERFLUOROALKYLATED COMPOUNDS IN WHOLE BLOOD FROM SWEDEN
Anna
Kärrman (1), Bert van Bavel (1), Ulf Järnberg (2),
Lennart Hardell (1), Gunilla Lindström (1)
1 Man-Technology-Environment
Research Centre, Örebro University
2 Institute of Applied Environmental Research, Stockholm University
Introduction. Historically
the reports on perfluoroalkylated (PFA) compounds have been
limited to mainly perfluorooctane sulfonate (PFOS) and perfluorooctanoate
(PFOA) but recently a number of other, potentially bioaccumulating,
perfluorinated acids were reported in wildlife and in human
blood (1,2,3,4). PFOS is the PFA compound that has been reported
most frequently and in the < 1-82 pg/µl range in human
serum from the general population of several countries (5,6,7,8).
PFOS and its salts represents only a fraction
of the total fluoroproduction but can occur as an impurity in
other products and is suspected to be the stable degradation
product from other perfluorinated compounds, for example derivatives
of perfluorooctane sulfonamide (PFOSA) (9,10). Recent
studies indicate that more volatile fluorotelomer alcohols (FTOHs)
and sulfonamidoethanols can degrade biotic to different PFA
compounds (11). FTOHs and sulfonamidoalcohols are used in both
industrial and household applications and have been found in
the trophospere (12). Since possible degradation pathways, distribution
and exposure routes for this group of compounds are still under
investigation; information of human exposure to a larger number
of PFAs is valuable. In this study we analysed 66 whole blood
samples from the Swedish general population with respect to
12 perfluorinated sulfonates and carboxylates (including perfluorooctane
sulfonamide) with carbon chain length between 4 and 14 ...
... Discussion. The results shows
that the Swedish population is exposed to a large number of
PFAs in conformity with the study performed on European parliament
members
(4). The concentrations of PFOS (18.2 pg/µl) and PFOA
(2.9 pg/µl) in whole blood samples from Sweden are about
a factor two lower than previously reported (34.9 and 4.6 pg/µl
respectively) in serum samples of the USA population (13). Assuming
that PFAs bind to plasma proteins (14,15) and that whole blood
consist of about 50% plasma, the concentrations of PFOS and
PFOA in the general population from Sweden and USA can be regarded
as similar. The relationship between different compounds was
studied in order to find eventual exposure patterns. The association
between PFOS and PFOA was strongest (R 2 0,3-0,5), demonstrated
in Figure 1. ...
Full
free report available at http://dioxin2004.abstract-management.de/pdf/p304.pdf
Paper presented
at Dioxin 2004: 24th International Symposium on Halogenated
Environmental Organic Pollutants and POPs. Berlin, September
6 - 10, 2004.
ORGANOHALOGEN COMPOUNDS
– Volume 66 (2004) 4035-4040.
PERFLUORINATED
CARBOXYLATES AND SULFONATES IN OPEN OCEAN WATERS OF THE PACIFIC
AND ATLANTIC OCEANS
Sachi
Taniyasu (1), Nobuyoshi Yamashita (1), Kurunthachalam Kannan
(2), Yuichi Horii (1), Ewan Sinclair (2), Gert Petrick (3),
Toshitaka Gamo 4
1 National Institute
of Advanced Industrial Science and Technology (AIST), Tsukuba
2 Wadsworth Center, New York State Department of Health, Albany
3 Institute for Marine Research, University of Kiel, Kiel
4 Ocean Research Institute, University of Tokyo, Tokyo
... Our
studies have shown that part per quadrillion (ppq) level analysis
of PFCs is necessary to obtain reliable information of open
ocean pollution ...
Results
and Discussion.
Table 1 shows the concentration of PFOS, PFHS, PFNA, and PFOA
in open ocean water samples from the Pacific and Atlantic Oceans
and several coastal seawaters from Asian countries.
PFOS and PFOA were found in 80% of the surface seawater and
some regions showed characteristic composition of PFCs.
There were some similarities between PFCs composition in coastal
and open ocean waters in some regions. It appeared that the
hydrologic information such as tidal and/or water current was
necessary to explain the discharge of PFCs from coastal water
to open ocean.
Relatively high concentrations of PFOS,
PFHS, and PFOA were detected in Tokyo Bay waters. PFOA is the
predominant fluorochemical, ranging in concentration from 1,800
– 192,000 pg/L, followed by PFOS (338 - 57,700 pg /L).
Concentration of PFHS was an order of magnitude lower than the
concentration of PFOS. High concentrations of PFCs in Tokyo
Bay waters suggest sources associated with urban and industrial
areas in Tokyo. The higher concentration
of PFOA than of PFOS in water samples is an interesting observation.
In wildlife samples collected from several locations, PFOS was
the predominant compound, rather than PFOA (2). This discrepancy
suggests that the bioaccumulation potential of PFOA is relatively
lower than that of PFOS.
Concentrations of PFOS, PFHS, PFOA, and PFOSA in offshore waters
of the Pacific Ocean were approximately three orders of magnitude
lower than those in Tokyo Bay. Concentrations of all of the
target fluorochemicals in offshore waters were in the pg/L range.
Similar to what was observed for coastal waters, PFOA was the
predominant fluorochemical found in the offshore waters of Japan.
Variability in the concentrations of PFOA or PFOS in offshore
waters was rather lower than for coastal waters, suggesting
a generalized source such as atmospheric or hydrospheric transport.
PFOSA was also found in these samples, at concentrations comparable
to those of PFHS.
Open-ocean water samples collected in
the mid-Atlantic Ocean showed the presence of all target PFCs
at pg/L levels. Concentrations of PFOA and PFOS were
comparable to those in offshore waters collected in the South
China and Sulu Seas. The concentrations of PFOA and PFOS in
the central to eastern Pacific Ocean waters were from 15 to
62 and 1.1 to 20 pg/L, respectively. These concentrations were
an order of magnitude lower than concentrations in offshore
waters, and four orders of magnitude lower than concentrations
in Tokyo Bay water. These values appear to be the background
values for remote marine waters far from local sources. Figure
4 illustrates the spatial trend of PFOS, PFHS, and PFOA from
coastal Japan to the central Pacific Ocean. Concentrations of
PFCs decreased dramatically by 2-4 orders of magnitude from
coastal area to the offshore area.
It appears that PFOA pollution is more
ubiquitous than PFOS in oceanic waters. This may be similar
to trifluoroacetic acid (TFA) pollution in oceans. Scott et
al. reported widespread distribution of TFA in open ocean waters
(6). Our result suggests that several perfluorinated acids are
following similar environmental dynamics as TFA.
The other aim of our survey is to understand three-dimensional
distribution of PFCs in marine environment. Although the marine
environment is three-dimensional, very few studies have investigated
persistent organic pollutants (POPs) including PFCs in deep
seawaters. We have collected more than thirty deep seawater
samples from the above mentioned locations and detected some
PFCs. Presence of PFCs in deep-sea water shows the need for
comprehensive survey of not only surface water but also vertical
profile of PFCs in water column as well as open ocean air. Deep-sea
water samples, collected at depths of >1000 m in the Pacific
Ocean and the Sulu Sea contained trace levels of PFOS and PFOA.
The deep seas play a major role in the
dynamics of several POPs and therefore their role in the global
fate of PFCs must be examined.
Full
free report available at
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Paper presented
at Dioxin 2004: 24th International Symposium on Halogenated
Environmental Organic Pollutants and POPs. Berlin, September
6 - 10, 2004.
ORGANOHALOGEN COMPOUNDS
– Volume 66 (2004) 4063-4068.
ENVIRONMENTAL CONTAMINATION BY PERFLUORINATED
CARBOXYLATES AND SULFONATES FOLLOWING THE USE OF FIRE-FIGHTING
FOAM IN TOMAKOMAI, JAPAN
Nobuyoshi
Yamashita (1), Kurunthachalam Kannan (2), Sachi Taniyasu (1),
Yuichi Horii (1), Nobuyasu Hanari (1), Tsuyoshi Okazawa (1),
Gert Petrick (3)
1 National Institute
of Advanced Industrial Science and Technology (AIST), Tsukuba
2 Wadsworth Center, New York State Department of Health, Albany
3 Institute for Marine Research, University of Kiel, Kiel
Introduction. On
September 26, 2003, a magnitude (M) 8.3 offshore earthquake
struck Hokkaido, Japan. The earthquake and ensuing tsunami injured
hundreds of people and resulted in significant damage to port
and coastal communities. Immediately following the earthquake,
a major fire occurred at an oil storage facility of a refinery
(Idematsu Kosan Company Ltd) located in the west part of Tomakomai,
a Pacific coast city in southern Hokkaido. Idemitsu Kosan Company
is the second largest oil refinery in Japan, with a capacity
of 140,000 barrels per day (bpd) in Tomakomai. Forty-five of
the 105 oil storage tanks were damaged following the earthquake
and resulted in release of petroleum naphtha, which ignited
accidentally. The first fire was reported immediately after
the earthquake on 26 September 2003 and was extinguished after
7 hours. The second fire occurred on 28 September and lasted
for 44 h. More than three hundred fireman and about one hundred
fire engines were brought from several prefectures by air carriers
to extinguish the fire. More than 130,000 L of fire fighting
foams (FFF) was delivered to extinguish these fires and at least
40,000 L was used. Detailed information regarding the type of
FFF used was not available, but aqueous film forming foams (AFFF)
have been used in the control of fuel-related fires. Perfluorooctane
sulfonate (PFOS) and related perfluorinated acids are a component
of AFFF (1). The issue of environmental pollution by perfluorinated
compounds (PFCs) including perfluorinated carboxylates and sulfonates
has received much attention in the last four years (2,3). PFCs
possess unique physicochemical properties and exhibit a wide
range of volatility/ water solubility depending on the functional
group. Environmental dynamics of PFCs is complex due to their
unique characteristics and to their release from multitude of
sources with various compositions. Previous studies have reported
on environmental contamination by PFCs due to accidental release
of AFFF (4,5). Large amount of release of AFFF in Tomakomai
oil refinery fire provided an opportunity to study environmental
dynamics of PFCs in the environment. A monthly monitoring survey
of the environmental levels of PFCs in the Tomakomai region
was conducted since October 2003. This study presents the results
of initial survey conducted between October and December 2003.
... Results and Discussion ...
Water samples collected in October, approximately a month after
the Tomakomai fire, showed two to six times higher concentrations
of PFOS, PFHS and PFOSA than those from Tokyo Bay, a most contaminated
waterbody in Japan. However, concentrations of perfluorinated
carboxylates and PFBS were low in water samples collected in
and around the oil refinery in Tomakomai than in Tokyo Bay.
Fig 2 and 3 show the concentrations of PFOS and PFOA in water
samples collected from Tomakomai and several other locations
in Japan. Typical ratio of PFOS to PFOA concentrations in water
samples around Japan was less than 0.7 (7,8). Water samples
collected in December, approximately two months after the fire,
showed a PFOS/PFOA ratio of 10 suggesting greater composition
of PFOS in AFFF. After two months of AFFF usage, concentrations
of all PFCs decreased dramatically, from 2- to 13- fold, compared
to the samples collected in October except for PFHpA. Only at
station 8 concentrations of PFOS and PFOA were similar. Relatively
high concentrations of PFCs were found in in snow. This suggests
that significant amount of PFCs in AFFF were released into the
air and deposited to land through wet deposition process. Concentrations
of PFCs in soil (pg/g dry weight basis) were also high for most
PFCs; however, concentrations of PFBS were low. It may
be due to that PFBS concentrations are low in AFFF. The
highest concentration of any PFCs detected in Tomakomai samples
was 3,680ng/L of PFOS in run-off water collected in October.
Run-off water contained all PFCs at the highest concentrations
except PFDoA.
Figures 4 and 5 show the composition of perfluorinated sulfonate
and carboxylates, respectively, in several water, snow and soil
samples from Japan and open ocean. Composition of PFCs in central
to eastern Pacific Ocean water represent background profiles
of PFCs. North Atlantic Ocean profile reflects relatively contaminated
open ocean water. Tokyo Bay water shows typical contaminated
coastal water profiles in Japan. Compound specific composition
of perfluorinated sulfonates and PFOSA provides several insights.
High percentage of PFBS may be suggestive of non-contaminated
water samples. Differences in the composition of PFCs between
October and December may have been caused by dramatic decrease
in PFOS concentrations.
From the above results, following hypothesis regarding environmental
dynamics of PFCs can be made. PFCs released from AFFF into coastal
water were at highest concentrations in October but removed
readily by dilution and exchange of coastal and offshore waters.
PFCs released into the atmosphere (gas phase and particulated
matters) during AFFF usage was trapped by snow and deposited
onto soil and water. PFCs deposited on
soils can continue to be a source of exposure in the environment
because of the high concentrations observed in soils in December.
Soil contamination was also caused by the highly contaminated
run-off water...
Full
free report available at
http://dioxin2004.abstract-management.de/pdf/p666.pdf
Paper presented
at Dioxin 2004: 24th International Symposium on Halogenated
Environmental Organic Pollutants and POPs. Berlin, September
6 - 10, 2004.
ORGANOHALOGEN COMPOUNDS
– Volume 66 (2004) 4079-4085.
Perfluorooctanesulfonate and Related
Fluorochemicals in Several Organisms Including Humans from Italy
Simonetta
Corsolini (1), Kurunthachalam Kannan (2)
1 University of Siena,
Siena, Italy
2 State University of New York, Albany, NY, USA
... Mediterranean
Sea organisms. PFOS was the most predominant
fluorochemical in the tissues analyzed (Tables 1-2).
PFOS was found in blood of captive bottlenose dolphins at concentrations
ranging from 42 to 210 ng/mL (Table 1). The
greatest PFOS concentration found in the liver of a common dolphin
was 940 ng/g wet wt; muscle tissue from the same individual
contained a PFOS concentration that was 12-fold less than that
in liver (Table 1). Four of five livers of bottlenose
dolphins collected from the Adriatic and Thyrrenian Seas contained
quantifiable concentrations of PFOS. The mean????SD concentration
of PFOS in livers of striped dolphins was 26????9 ng/g wet wt.
Concentrations of PFOS in livers of bottlenose and striped dolphins
were less than those found in cetaceans from the coastal waters
of Florida 9 . Nevertheless, the concentration
of PFOS measured in common dolphin liver was similar to those
reported for dolphins from the Florida coast. Among the other
fluorochemicals measured, FOSA was a prominent compound in livers
of dolphins and whales.
Livers of most of the cetaceans (except striped dolphin) contained
quantifiable concentrations of FOSA (Table 1). The greatest
FOSA concentration was found in the liver of a common dolphin
(878 ng/g wet wt). Occurrence of FOSA in marine mammals from
the Mediterranean region indicates the presence of specific
and current sources. PFOA and PFHxS were found in blood of a
few individuals of bottlenose dolphins at concentrations ranging
from <2.5 to 6.1 ng/mL. PFHxS was detected in a striped dolphin
and swordfish liver at concentrations of 6.8 and 10 ng/g, wet
wt, respectively.
Concentrations of PFOS in cormorant livers collected from Cabras
Lagoon in Sardinia ranged from 32 to 150 ng/g wet wt (mean:
61 ng/g) (Table 1). Mean PFOS concentrations
in juvenile birds were not significantly different from those
in adults (p < 0.05). This is similar for bald eagles collected
from the midwestern U.S.13 . In general, PFOS concentrations
in cormorants were similar to or less than those found in cormorants
and other fish-eating water birds collected from the North American
Great Lakes 13 . PFOA was consistently
found in all the livers of cormorants at concentrations ranging
from 29 to 450 ng/g wet wt.
Concentrations of PFOS in blood of bluefin tuna and swordfish
ranged from 27 to 52 (mean: 40) and 4 to 21 ng/mL (mean: 10),
respectively (Table 1). The PFOS concentration in livers of
bluefin tuna was 21-87 ng/g wet wt (mean: 47), greater than
that determined in swordfish (<1-13 ng/g; mean: 7) (Table
1). The ratios of concentrations of PFOS in liver to blood of
bluefin tuna and swordfish were 0.85 and 1.4, respectively.
These ratios are 7-12-fold less than those
calculated for polar bears from Alaska 9 . Although the
PFOS concentrations in bottlenose dolphins blood were 4 to 14-fold
greater than those in bluefin tuna and swordfish, blood-to-liver
ratios of PFOS were less in dolphins than in fishes.
This suggests that the distribution of PFOS between liver and
blood in fishes is different than in mammals. Concentrations
of FOSA in the bluefin tuna blood (mean: 15 ng/mL) were 2 to
4-fold less than those of PFOS (40 ng/mL), which was different
from that observed in bottlenose dolphins. FOSA concentrations
in swordfish blood was 1.5-fold greater than that of PFOS. FOSA
was not found in the fish livers at the quantitation limit of
38 ng/g, wet wt.
Human blood samples. Mean, median,
and range of PFOS, PFHxS, PFOA, and PFOSA
concentrations in serum samples are shown in Table 2; their
concentrations were 4.4 ng/mL, 1.3 ng/mL, <3 ng/mL and 1.7
ng/mL respectively in female and 4.3 ng/mL, 1.7 ng/mL, <3
ng/mL and 1.8 ng/mL respectively in male donors. PFOS was found
in most of the samples collected (87.5% in female and 90.5%
in male). PFHxS and PFOSA were found in the blood of Italian
donors. Samples did not contain PFOA, at a detection limit of
3 ng/mL. In general, no significant difference (p>0.05) in
the concentration of either PFOS or PFOA was found between the
sexes.
Full
free report available at
http://dioxin2004.abstract-management.de/pdf/p140.pdf
Paper presented
at Dioxin 2004: 24th International Symposium on Halogenated
Environmental Organic Pollutants and POPs. Berlin, September
6 - 10, 2004.
ORGANOHALOGEN COMPOUNDS
– Volume 66 (2004) 4009-4014.
Presence
of Anionic Perfluorinated Organic Compounds in Serum Collected
from Northern Canadian Populations
Sheryl
Tittlemier (1), John J. Ryan (1), Jay Van Oostdam (2)
1 Food Research Division,
Health Canada, Ottawa
2 Management of Toxic Substances Division, Health Canada, Ottawa
Introduction. Perfluorinated
organic compounds are used in a wide variety of consumer and
industrial products and applications, ranging from personal
care products and cleaning solutions, to grease resistant coatings
for fabric and paper and emulsifiers in the production of polymers.1
Perfluorinated compounds such as perfluorooctane sulfonate (PFOS)
and perfluorooctanoate (PFOA) are persistent and bioaccumulative.
PFOS and PFOA have been detected in biota sampled from around
the world 2 , including the Canadian Arctic.3,4 Evidence from
various laboratory experiments suggest that these perfluorinated
compounds can elicit negative effects, including peroxisome
proliferation 5 and possibly hepatocarcinogenesis.6 PFOA
and PFOS also appear to biomagnify in marine food webs, in a
similar fashion as traditional organohalogenated POPs like the
recalcitrant PCB congeners.4,7
Indigenous northern Canadian populations such as the Inuit and
Inuvialuit often hunt and
consume marine mammals, including beluga, narwhal, and seal,
as part of their traditional diet. Thus, segments of these populations
are often exposed to higher levels of POPs than southern populations
and other consumers of market foods. This higher exposure is
reflected in plasma concentrations of traditional POPs such
PCBs.8 There is a question of whether a similar situation occurs
for PFOS, PFOA, and similar perfluorinated compounds. This preliminary
survey analyzed a suite of perfluorinated sulfonates and carboxylates
in 23 pooled archived samples of human plasma collected from
various northern Canadian populations...
The results of this preliminary survey
demonstrate that populations residing in the Northwest and Nunavut
Territories in northern Canada are exposed to FOCs. The presence
of FOCs in cord blood plasma also indicates that exposure occurs
in utero. This limited data set shows that FOC levels in these
northern samples are very similar to FOC concentrations in southern
population, and that there are no marked differences between
the various ethnic groups (Inuit, Dene/Metis, Caucasian).
The low samples numbers are insufficient to confidently examine
whether or not there are differences in FOC exposure and body
burdens amongst various ethnic groups within regions that consume
different diets, but these preliminary data do not support such
a conclusion...
Full
free report available at http://dioxin2004.abstract-management.de/pdf/p489.pdf
Paper presented
at Dioxin 2004: 24th International Symposium on Halogenated
Environmental Organic Pollutants and POPs. Berlin, September
6 - 10, 2004.
ORGANOHALOGEN COMPOUNDS
– Volume 66 (2004) 4074-4078.
Occurrence of Perfluorinated Organic
Acids in the Water of the North Sea
Christina
Caliebe (1), Wolfgang Gerwinski (1), Heinrich Hühnerfuss
(2), Norbert Theobald (1)
1 Bundesamt für
Seeschiffahrt und Hydrographie, Hamburg
2 Universität Hamburg, Inst. für Organische Chemie,
Hamburg
Introduction. Perfluorinated
organic acids (PFC) and their derivatives are industrially produced
since many years in very large quantities and are used for many
purposes 1 : Perfluoroalkyl sulfonates are applied, e.g., as
surfactants and surface protectors to carpets, leather, paper,
fabrics and many more. In addition, some sulfonated and carboxylated
PFCs have been utilized in or as fire fighting foams, alkaline
cleaners, shampoos, and insecticide formulations. Due to the
large production quantities and the persistence in the environment,
perfluorinated compounds are meanwhile globally
distributed. Perfluorooctanesulfonic acid (PFOS) and other long
chain perfluorinated chemicals have been detected in blood of
ringed seals, in polar bears, arctic foxes, mink, birds, and
fishes collected in the USA, at the coasts of the Baltic and
Mediterranean Sea and in the Arctic 1,2,3,4,5,6 . Because of
the findings of perfluorinated compounds in Arctic biota samples,
it is of special interest to investigate their long range transport.
Due to their high polarity, a transport by the water phase is
likely. However up till now, only few studies report on the
occurrence in surface or ground water and none in sea water
7 . The aim of this work was, therefore, to develop a method
for the determination of perfluorinated organic acids in seawater
and to study their occurrence and distribution in the North
Sea...
... The occurrence of PFC in the North
Sea has not been described before. The concentrations of the
major occurring PFOA and PFOS determined on the two cruises
are within a similar range as other polar pollutants such as
phenylurea, triazine or phenoxyacetic acid herbicides. They
are present in part well above classical contaminants like chlorinated
hydrocarbons (HCH, DDT group, PCB) 10 . The investigations
demonstrated, that the developed method is suitable for the
study of the distribution of perfluorinated organic acids in
the coastal and open sea water. For extended studies into more
remote areas, however, some improvements concerning the LOD
are necessary.
Full
free report available at http://dioxin2004.abstract-management.de/pdf/p269.pdf
Paper presented
at Dioxin 2004: 24th International Symposium on Halogenated
Environmental Organic Pollutants and POPs. Berlin, September
6 - 10, 2004.
ORGANOHALOGEN COMPOUNDS
– Volume 66 (2004) 4029-4034.
Age dependent accumulation of perfluorinated
chemicals in beef cattles
Keerthi
Siri Guruge (
