Environ. Sci. Technol. 2003, 37, 2634-2639

A Survey of Perfluorooctane
Sulfonate and Related PerfluorinatedOrganic Compounds in Water, Fish,
Birds, and Humans from JapanSACHI TANIYASU,†
K U R U N T H A C H A L A M K A N N A N , * ,‡YUICHI HORII,†NOBUYASU HANARI,† ANDNOBUYOSHI YAMASHITA†
National Institute of Advanced Industrial Scienceand Technology (AIST), 16-1 Onogawa, Tsukuba,
Ibaraki 305-8569, Japan, Wadsworth Center, Empire State
Plaza, New York State Department of Health, P.O. Box 509,
Albany, New York 12201-0509, and Department ofEnvironmental Toxicology and Health, State University of
New York, Albany, New York 12202-0509

Occurrence of perfluorooctane sulfonate (PFOS) in thetissues of humans and wildlife is well documented. In thisstudy, concentrations and distribution of PFOS, perfluorohexane sulfonate (PFHS), and perfluorobutane sulfonate(PFBS) were determined in samples of surface water,fish and bird blood and livers, and human blood collected
in Japan. Notable concentrations of PFOS were foundin surface water and fish from Tokyo Bay. PFOS was foundin all of the 78 samples of fish blood and liver analyzed.
Based on the concentrations of PFOS in water and in fish
livers, bioconcentration factors were calculated torange from 274 to 41 600. Concentrations of PFOS in the
blood of Japanese human volunteers ranged from 2.4 to 14
ng/mL. PFHS was detected in 33% of the fishes analyzed,
at concentrations severalfold less than those of PFOS.

Introduction
Perfluorooctane sulfonate (PFOS) and its salts are fully
fluorinated organic compounds that can be produced
synthetically or through the degradation of other perfluorochemical products. Recent studies have shown that PFOS
is a persistent and bioaccumulative global contaminant (16). Sulfonyl-based perfluoroalkylated compounds have been
produced and used for over 40 years (1) for soil/stain
resistance and surfactant applications and are used in various
textiles, upholstery, carpeting, and specialty papers, including
food-contact materials and fire-fighting foams. Perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate(PFBS) are impurities in certain fluorochemical formulations,
including aqueous film-forming foams (AFFF). Occurrenceof perfluorocarboxylates in groundwater and AFFF products
has been shown (7, 8). The 3M Company, a major manufacturer of sulfonyl-based perfluorochemicals, announced* Corresponding author phone: (518)474-0015; fax: (518)473-2895;
e-mail: kkannan@wadsworth.org. Corresponding author address:
Wadsworth Center, New York State Department of Health, Empire
State Plaza, P.O. Box 509, Albany, NY 12201-0509.
† National Institute of Advanced Industrial Science and Technology.
‡ Wadsworth Center and State University of New York.
2634 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 12, 2003

the phase-out of production of POSF-based chemicals from
December 2000, because of concerns about the persistenceof PFOS in the environment and the potential for long-term
environmental effects (9). The discovery of fluorinated organic
compounds in human serum and in the environment has
led to the initiation of studies to characterize the distribution,
dynamics, and fate of such chemicals in the environment.
PFOS and related perfluorinated chemicals are also thought
to be produced by other manufacturers in other countries.
Since July 2000, the Organization of Economic Cooperation
and Development (OECD) led an international collaborationon the scientific assessment of PFOS. Therefore, data on theoccurrence and distribution of perfluorochemicals in theenvironment are needed for accurate risk assessment in all
countries.
Studies on the occurrence of perfluorinated compounds
in wildlife have focused on samples collected from North
America and Europe (3-6). Studies describing the occurrenceof perfluorinated compounds in coastal surface waters andfishes have not been previously reported. Japan is one of themost highly industrialized nations in the world, and the useof perfluorinated compounds is expected to have occurred
there in various applications. In 2000, the first national projecton PFOS in Japan was started at the National Institute forAdvanced Industrial Science and Technology, with thesupport of New Energy and Industrial Technology Development Organization (NEDO). A preliminary survey was
conducted in 2001 to estimate PFOS in Japanese humans;
this survey showed measurable concentrations (a few tensof parts-per-billion) in blood (10-12). In the present study,
we report results of a survey of PFOS, PFHS, and PFBS in
samples of water, fish, birds, and humans, collected in Japan.
Additionally, this study provides evidence for the field-based
bioconcentration factors of PFOS in fish.

Materials and Methods
Sample Collection. Twenty-two surface seawater samples
were collected from Ishikari Bay and Lake Shikotsu in
Hokkaido, Tokyo Bay, Osaka Bay, Hiroshima Bay, Ariake Bay,and Kin Bay in Okinawa (Figure 1). Three freshwater samples
were collected from Lake Biwa, the largest lake in Japan,
located in central Shiga Prefecture. Samples were collectedusing a clean stainless steel grab sampler and stored in new
1 L polypropylene containers with narrow mouths and screw
tops. The containers were rinsed with methanol, deionizedwater, and water from the particular sampling location prior
to use. Teflon bottles and Teflon-lined caps were avoided
throughout the analysis, as interference might have been
introduced into the sample extracts. The amount of suspended matter was kept to a minimum. To reduce residual
chlorine, we added 200 µL of 250 mg/mL solution of sodium
thiosulfate to each bottle. In most cases, samples wereextracted within 24 h after collection; otherwise, samples
were kept at 4 °C until analysis. All of the water samples werecollected during March to September, 2002.
Forty-eight blood samples and 30 liver samples werecollected from 23 species of fish during March-August, 2002,
from Tokyo Bay, Osaka Bay, Hiroshima Bay, Ariake Bay, Kin
Bay (Okinawa), and Lake Biwa (Figure 1). Fish were caught
by hook and line or obtained from local fisherman. All species
were coastal fishes except those from Lake Biwa. Fish were
captured alive for the collection of blood and liver samples.
Blood samples were drawn from the caudal artery of fishthat were still alive, and liver samples were obtained after
dissection. Samples from biota and seawater were placed on
dry ice and kept in the dark from the time of collection until
10.1021/es0303440 CCC: $25.00

 2003 American Chemical Society
Published on Web 05/14/2003

TABLE 1. Concentrations of Perfluoroalkane Sulfonates [ng/L]
in Surface Water Samples from Japana
location

n

PFOS

PFHS

PFBS

Ishikari Bay (Hokkaido)
Lake Shikotsu (Hokkaido)
Tokyo Bay
Osaka Bay
Lake Biwa
Hiroshima Bay
Ariake Bay
Kin Bay (Okinawa)

1
1
4
3
3
4
5
4

<2.5
<2.5
8-59 (26)b<4-21 (8.7)<4-7.4 (3.8)<4<9-11 (4.8)
<2.5

<3.1
<3.1
<7.1
<8.8
<8.8
<8.8
<11
<3.1

<27
<27
<48
<60
<60
<60
<38
<27

a Values below the detection limit were assigned a value of 2 (halfthe MDL) for calculation of the mean. b Values in parentheses indicate
the means.

FIGURE 1. Map of Japan, highlighting the sampling locations.
transport to the laboratory and then stored at -30 °C forbiota samples and 4 °C for seawater samples, until analysis.
Blood and liver samples were also collected from carrion
crow (Corvus corone corone), mallard (Anas platyrhynchos),and pintail duck (Anas acuta) (n ) 17) around Tokyo Bay inDecember 2000. In addition, blood and serum samples werecollected from two species of pets, rabbits, and domestic
duck (n ) 7). Serum was prepared by centrifugation of theblood at 2500 G for 15 min. Human blood and serum werecollected from Japanese volunteers (n ) 10, ages 23-44) inJune, 2002. Three of the blood samples were analyzed bothas whole blood and as serum after centrifugation, to allow
comparison of the concentrations in whole blood and inserum.
Extraction. The analytical procedure for the extraction ofwater samples was similar to that described elsewhere (13),with some modifications. The modifications include the useof 10-g solid-phase extraction (SPE) tC18 cartridges insteadof 1-g cartridges, and extraction of 500 mL of water insteadof 40 mL of water. C18 SPE cartridges (10 g, 35 mL, Waters
Corporation, Milford, MA) were preconditioned by passage
of 100 mL of methanol followed by 50 mL of milli-Q water,prior to passage of samples. A sample aliquot of water (500mL) was passed through the preconditioned cartridges at a
rate of 1 drop/s, and the cartridges were not allowed to go
dry at any time throughout the extraction process. The
cartridges were then washed with 20 mL of 40% methanol
in water, which was then discarded. The target analytes were
eluted with 30 mL of methanol and collected in a polypropylene tube. The solvent was evaporated under nitrogen to
0.4 mL and transferred into a vial for analysis.
The analytical procedure for the extraction of blood andliver samples was similar to that described elsewhere (2, 3).
One milliliter of 0.5 M tetrabutylammonium hydrogensulfate
solution and 2 mL of sodium carbonate buffer (0.25 M, pH10) were added to 1 mL of blood or serum sample in a
polypropylene tube and thoroughly mixed for extraction.
Five milliliters of methyl tert-butyl ether (MTBE) was added
to the above mixture and shaken for 20 min. After centrifugation, the MTBE layer was transferred into another polypropylene tube. The solvent was evaporated under nitrogen andreplaced with 0.5 mL of methanol. This extract was passed
through a nylon mesh filter (0.2 µm) into an HPLC vial. For
the extraction of liver samples, 1 g of liver was homogenizedwith 5 mL of milli-Q water. One milliliter of this homogenate
was transferred into a polypropylene tube and extracted
similarly to the procedure described for blood.
Analysis. Concentrations of PFOS in liver and bloodplasma were measured using high performance liquid
chromatography (HPLC) interfaced with an electrospray mass
spectrometer (MS), followed by confirmation with electrospray tandem mass spectrometry (MS/MS). The PFOS usedas standards and as matrix spikes were purchased from Fluka(Milwaukee, WI). HPLC-MS/MS measurement was performed using an Agilent HP1100 liquid chromatographinterfaced with LCQ TermoQuest (Finnigan, San Jose, CA)
and Micromass (Beverly, MA) Quattro II mass spectrometer
operated in the electrospray negative mode. Twenty microliters of the extract was injected onto a CAPCELL PAK C18
column (2.0 mm i.d. × 50 mm length, 3 µm; Shiseido Fine
Chemicals, Tokyo, Japan) with 2 mM ammonium acetate/methanol as mobile phase starting at 30% methanol. At aflow rate of 300 µL/min, the gradient was increased to 100%
methanol at 10 min before reversion to original conditions
at 18 min. The capillary was held between 1.6 and 3.2 kV.
Desolvation gas flow was kept at 750 L/h, and desolvation
temperature was kept at 420 °C. Cone voltage was kept at 90,
60, and 50 V for PFOS, PFHS, and PFBS, respectively. Collisionenergies were 33, 29, and 23 eV for PFOS, PFHS, and PFBS,
respectively. The MS/MS parameters were optimized totransmit the [M - K]- ion for PFOS using atmosphericpressure ionization, operated in the electrospray negative
ion mode. Ions were monitored using selected reaction
monitoring for ions 499 and 99 for quantitative determinationof PFOS, m/z 399 and 99 for PFHS, and m/z 299 and 99 for
PFBS.
Data quality assurance and quality control protocols
included matrix spikes, laboratory blanks, and continuingcalibration verification. Matrix spikes were analyzed for eachsample type and species. Blanks were analyzed with each set
of water and tissue samples as a check for possible laboratory
contamination and interferences. Blanks did not contain any
interference. Recoveries of PFOS, PFHS, and PFBS spiked
into distilled water samples and passed through the analyticalprocedures were 101, 154, and 113% (n ) 3 each), respectively.
Recoveries of PFOS, PFHS, and PFBS spiked into blood andliver matrices were 85, 87, and 61% (n ) 4 each), respectively.
Reported PFOS concentrations were not corrected forrecovery. The limit of detection (LOD) was variable, depending on the matrix used. The LODs for PFOS, PFHS, and PFBS
in water samples varied from 4 to 9, 4 to 11, and 39 to 60
ng/L, respectively. The LODs of PFOS in liver tissues varied
from 1 to 4 ng/g, wet wt. The LODs for PFHS and PFBS varied
from 2 to 200 ng/g, wet wt, depending on the sample.

Results and Discussion
PFOS was found in nine of the 25 surface water samples atlevels above the LOD. PFOS was detected in all of the surface
seawater samples collected from Tokyo Bay, at concentrations
ranging from 8 to 59 ng/L (mean; 26 ng/L) (Table 1). PFHS
and PFBS were not detected in any of the water samples
analyzed. The measured concentrations of PFOS in Tokyo
Bay water samples were similar to those reported (17-54ng/L) for waters collected upstream of a fluorochemical
manufacturing facility in the Tennessee River in the UnitedStates but lower than concentrations downstream (75-144
VOL. 37, NO. 12, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 2635

ng/L) of that fluorochemical manufacturing facility (13). The
highest PFOS concentration, 144 ng/L, measured in the
Tennessee River was 2.4-fold greater than the highest
concentration found in Tokyo Bay. Similarly, PFOS concentrations in our seawater samples were 3-4 orders ofmagnitude lower than those reported (<0.1-2210 µg/L) forwater samples collected after a spill of fire-fighting foam in
Etobicoke Creek near Toronto, Canada (14). PFOS was notfound in Hiroshima Bay (Seto Inland Sea), Kin Bay (Okinawa),
Ishikari Bay (Hokkaido), or Lake Shikotsu (Hokkaido). Higher
concentrations of PFOS in Tokyo Bay relative to otherlocations in Japan indicate that the chemical sources areconcentrated in industrialized and urbanized areas. Tokyo
Bay receives discharges of waters from several rivers, including the Tama River, which flows through suburban andmetropolitan areas of Tokyo. Discharge of industrial andmunicipal wastewaters is suspected as a source of fluorochemicals found in surface and coastal waters analyzed inthis study. A nationwide survey of PFOS in freshwaters
conducted recently in Japan showed that the Tama River has
the highest concentration, 157 ng/L, whereas surface watersfrom coastal locations contained PFOS concentrations at 25
ng/L (15). The highest concentration of PFOS found in Tokyo
Bay water in our study was approximately 20-fold lower thanthe drinking water health advisory level of 1 µg/L (13).
PFOS was found in all blood and liver samples analyzed
from fish (n ) 78; Table 2). Fish collected from Tokyo Bay,
Osaka Bay, and Lake Biwa contained greater concentrationsof PFOS than those from Hiroshima Bay. Concentrations of
PFOS in blood and in liver of fishes ranged from 1 to 834
ng/mL and from 3 to 7900 ng/g, wet wt, respectively.
Concentrations of PFOS varied more than 100-fold, depending on the species and location. For instance, concentrationsof PFOS in the blood of Japanese stingfish collected from
Tokyo Bay ranged from 2 to 488 ng/mL. The highest
concentrations, 834 ng/mL in blood and 7900 ng/g in liver,were respectively found in bluegill (Lepomis macrochirus)
from Lake Biwa and ornate jobfish (Pristipomoides argyrogrammicus) from Kin Bay (Okinawa). Both of these species
are carnivorous, near-bottom feeders. An electric power plant
and an army base (U.S. Marine Corps) are located at Kin Bay.
Use of PFOS in fire-fighting operations on army bases may
provide a possible source of PFOS in Kin Bay. Perfluoroalkane
sulfonate salts and perfluorocarboxylates are present in AFFF
fire-fighting foam formulations (7). AFFFs are found atmilitary bases, fire departments, and airports, where large
volumes of flammable liquids, and the potential for a majorfire, exist. Further investigation is necessary to identify andconfirm the presence of PFOS-related sources in Kin Bay.
The coastal water samples (n ) 4) collected in Kin Bay did
not contain measurable PFOS concentrations.
The ratios of concentrations of PFOS between liver andblood samples from fish varied widely from 0.02 to 179 (mean;19). Concentrations of PFOS in livers of ornate jobfish
collected from Kin Bay were 170-fold higher than bloodconcentrations. Alternatively, fishes collected from Tokyo
Bay and Osaka Bay contained higher PFOS concentrations
in blood than in liver. This may be indicative of inequilibrium
in PFOS concentrations between liver and blood, indicating
an ongoing exposure of fish to PFOS. Liver to bloodconcentration ratios increased with increasing hepaticconcentrations of PFOS (Figure 2). Water-borne exposure of
rainbow trout to PFOS has been shown to result in a higher
accumulation in blood than in liver (16). Additionally, thedistribution of perfluorinated acids among various tissues
has been linked to the presence of fatty acid binding proteins(17).
PFHS was detected in approximately 33% of the fish blood
samples. Fishes from Tokyo Bay and Osaka Bay contained
measurable concentrations of PFHS. The maximum con2636 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 12, 2003

FIGURE 2. Relationship between hepatic PFOS concentrations andliver:blood concentration ratios in fish.

FIGURE 3. Spatial distribution of PFOS in fish and surface water
samples collected in Japan.
centrations of PFHS found in blood and liver, respectively,
were 121 ng/mL and 19 ng/g, wet wt. However, no PFBS was
found in any of the fishes analyzed. Concentrations of PFOS
in fish from Tokyo Bay were relatively higher than levels thathave been found (<17-380 ng/g, wet wt, in livers) in somefish samples from the Great Lakes region of the United States(1). Similarly, the concentrations of PFOS in livers of fishes
from Tokyo Bay were greater than those that have beenreported for bluefin tuna and swordfish from the Mediterranean Sea (6).
The spatial distribution in the concentrations of PFOS in
Japanese fish and water samples is shown in Figure 3. To
calculate the bioconcentration factor (BCF: ratio of concentration in fish to concentration in water) for PFOS in fish
liver tissue, we utilized the data for the water samples that
had been collected simultaneously with the fish to be sampledfrom various locations. Although concentrations in whole
fish are appropriate for the calculation of BCF, whole fish
were not analyzed in this study. Nevertheless, the fact thatPFOS is preferably concentrated in liver together with theavailability of laboratory-derived liver BCFs (16), enabled an

TABLE 2. Concentrations of Perfluoroalkane Sulfonates in Liver (ng/g, wet wt) and Blood (ng/mL) of Fishes Collected in Japan
location
Tokyo Bay

speciesCommon seabass(Lateolabrax japonicus)
Conger eel(Conger myriaster)
Flatfish(Pleuronectiformes pleuronectidae)
Japanese stingfish(Sebastiscus marmoratus)
Rockfish(Sebastes inermis)

Osaka Bay

Black seabream(Acanthopagrus schlegeli)
Common seabass(Lateolabrax japonicus)
Japanese scad
(Trachurus japonicus)
White croaker(Argyrosomus argentatus)

Lake Biwa

Blue gill(Lepomis macrochirus)
Largemouth bass
(Micropterus salmoides)
Carp(Cyprinus carpio)

Hiroshima Bay

Ariake Bay

Okinawa (Kin Bay)

Black scraper(Thamnaconus modestus)
Blake seabream(Acanthopagrus schlegeli)
Filefish(Stephanolepis cirrhifer)
Gizzard shad(Konosirus punctatus)
Japanese scad
(Trachurus japonicus)
Redlip mullet(Liza haematocheila)
Red seabream(Pagrus major)
Yellowfin sea bream(Acanthopagrus schlegeli)
Lefteye flounder(Paralichthys olivaceus)
Giant trevally(Caranx ignobilis)
Ornate jobfish(Tropidinius amoenus)
Perth herring(Nematalosa come)
Yellowfin tuna(Thunnus albacares)

tissue

n

PFHS

PFBS

liver

3

37-144 (85)a4-10 (7)

<138

blood
liver

3
1

30-146 (91)
558

4 (4)
18

<16
<151

blood
liver

1
2

489
158-198 (178)121
7-19 (13)

<61
<142

blood
liver

2
2

74-194 (134)38-192 (115)

28-38 (33)
<11 (8.8)

<21
<67

blood
liver

2
3

2-488 (245)62-70 (64)<2-4 (2.5)
9b

<13
<85

blood
liver

3
1

63-176 (123)6

2-5 (4.1)
<6.1

<11
<43

blood
liver

1
2

29
3-4 (4)

<3
<5.7

<11
<40

blood
liver

2
2

104-142 (123)4-14 (9)3.6-3.8 (3.7)
<7.6

<8
<53

blood
liver

2
2

108-238 (170)
12-16 (14)

<2.7
<5.7

<15
<40

blood
liver

2
2

33-50 (42)254-310 (282)

<2.8
<5.2

<10
<36

blood
liver

2
2

455-834 (645)
159-309 (234)

<4.3
<5.8

<15
<40

blood

2

<4.3

<15

liver

2

322-317(320)
3-4 (4)

<6.2

<43

blood
blood

2
2

<4.3
<5.5

<15
<14

blood

2

<5.5

<14

blood

2

<5.5

<14

blood

1

68-77 (73)
31-35
(33)
30-31
(31)
33-66
(35)
23

<5.5

<14

blood

2

1 (1)

<9

blood

2

1c

<14

blood

2

<5.5

<14

blood

1

7-19
(13)
23-47
(35)
17-41
(29)
27

<5.5

<14

liver

2

30-199 (115)

NAd

NA

blood

2

<0.7-11 (5.7)

<7.5

blood

3

<1.93

<23

liver

4

7-50
(29)
15-24
(19)
593-7900 (3250)

NA

NA

blood
blood

3
1

4-21 (9.7)
1

NA
<4.4

NA
<53

blood

1

1

<2.2

<27

PFOS

a Values in parentheses indicate the means. b One sample above the detection limit; others had detection limits of 14 and 26 ng/g. c One sample
above the detection limit, another sample with an LOD of 5.5 ng/mL. d NA ) not analyzed.

approximate comparison. Concentrations of PFOS measured
in the livers of fishes collected from Tokyo Bay, Osaka Bay,and Lake Biwa, and the corresponding mean concentrationsof PFOS in water, were used for the calculation (Figure 3).

Based on these data, BCF for PFOS in livers of fishes ranged
from 274 to 41 600 (mean; 8540). The corresponding log BCF
values in fishes were 2.4-4.6 (mean; 3.9). BCFs of PFOS inthe livers of common shiner (Notropus cornutus) collected
VOL. 37, NO. 12, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 2637

TABLE 3. Concentrations of Perfluoroalkane Sulfonates in Liver (ng/g, wet wt) and Blood or Serum of [ng/mL] Birds, Pet Animals,and Human Volunteers Collected from the Tokyo Bay Area
speciescarrion crow
(Corvus corone)
mallard(Anas platyrhynchos)pintail duck(Anas acuta)sea gull (Larus crassirostris)c
black-eared kite (Milvus lineatus)
common cormorant (Phalacrocorax carbo)
domestic duck (pet bird)(Anas platyrhynchos var. domestica)
rabbit (pet animal)(Oryctolagus cuniculus)
humantissue

n

PFOS

liver

6

blood

5

liver

1

68-1200(464)a11-150
(56)
493

blood
liver

1
2

blood

2

liver
liver
liver
blood

PFHS

PFBS

<5.7

<45

<1

NAd

<5.5

<44

9
2.6b

NA
<45

6-20
(13)
<7.5
<7.5
<7.5-10b
NA

NA

1
1
10
2

130
239-497(368)
84-167
(126)
230
180
390 (170-650)
0.3-1 (0.65)

serum
serum

2
3

6-9 (7.5)<0.1-0.4 (0.17)

NA
NA

NA
NA

blood
serum
blood
blood

3/
3/
5/
2?

5-14 (11)19-41 (27)
2.4-8.6 (5.9)
9.1-11<2.7<2.7<1-3.8 (2.0)
<1-1

<19
<19
NA
NA

NA
NA
NA
NA

a Values in parentheses indicate the means. b One sample above the LOD, another sample with a LOD of 5.5 ng/g, wet wt. c From ref 22. d NA
) not analyzed.

from Etobicoke Creek in Toronto, Canada, ranged between
6300 and 125 000 (14). The highest BCF in our study, 41600,
was found in bluegill collected from Lake Biwa. The averagewater concentration of PFOS in Lake Biwa was 7.4 ng/L,
whereas the concentrations in the livers of bluegill from thatlake ranged from 254 to 310 ng/g, on a wet weight basis. The
mean BCF for PFOS in fishes from Tokyo Bay was 5500 (140021 100), which is similar to the laboratory-derived value of5400 that has been reported for the liver of rainbow trout
exposed to PFOS (16). The calculated field-based BCFs for
PFOS were greater than those reported for chlorophenols
and PAHs but less than those obtained for more highly
chlorinated PCBs and DDT (18, 19). BCFs for PFOS werecomparable to, or greater than, values that have been reported
for anionic linear alkylbenzene sulfonates (6-990; laboratory
based) in fathead minnows (20). Nevertheless, it should be
noted that the mechanisms of bioconcentration and thecompartments of accumulation of neutral organic pollutants
such as PCBs and DDT are different from those of ioniccompounds such as PFOS.
PFOS was also found in the blood of Japanese humanvolunteers, at concentrations ranging from 2.4 to 14 ng/mL(Table 3). The mean PFOS concentration in blood samples
from adult females was 10 ng/mL (n ) 2), whereas the levelin males (n ) 8) was 8 ng/mL. There was no significant
correlation between PFOS concentration in blood and ageof the donor (Figure 4). Concentrations of PFOS were
measured in the serum of three individuals and were 1.44-fold (mean; 2.5) greater than concentrations in the corresponding whole blood samples. The measured range of
PFOS concentrations was similar to the range of 2-20 ng/
mL that has been reported previously (21). Concentrationsof PFOS ranging from 6.7 to 82 ng/mL have been reported
in the sera of United States citizens (2). Assuming thatconcentrations of PFOS in serum were 2.5-fold greater thanconcentrations in whole blood, the mean PFOS concentrationin sera of Japanese volunteers can be estimated to be 21
ng/mL. This is slightly lower than the average concentrationof 28 ng/mL, that was reported for United States citizens (2).
PFHS was also found in the humans in our study atconcentrations ranging from 1 to 3.8 ng/mL. These results
2638 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 12, 2003

FIGURE 4. Relationship between age of human volunteer subjects
and PFOS concentrations in their blood in Japan.
provide baseline data on the extent of PFOS exposure ofJapanese citizens; however, the number of human samples
in our study was small, and the results may not reflect
exposures in general Japanese population. Further studies
with larger numbers of samples are necessary to understandthe sources and pathways of exposures and the levels of risk.
Birds (carrion crow, mallard, and pintail duck) and pets
(rabbit and domestic duck) contained detectable concentrations of PFOS in liver and blood. In the birds, concentrations
in livers were greater than those determined in corresponding
blood samples. Occurrence of PFOS in pet animals suggests
exposure from food sources. Mallard ducks may be exposed
to PFOS via fish meal, which may be incorporated in theirdiet. Perfluorinated compounds, as perfluoroalkylated organophosphates, have been reported to be impregnated/
used in folding cartons used for pet food supplies (9). Carrion
crows, which are omnivorous birds, that consume a dietranging from worms, insects, fruits, and seeds to kitchen
scraps, had PFOS concentrations ranging from 11 to 150 ng/
mL (mean; 56) in their blood and from 68 to 1200 ng/g (mean;
464) in liver samples. These concentrations of PFOS in liversof carrion crows were similar to the liver concentrations
reported for several fish-eating water bird species collectedfrom around Tokyo Bay (22). Overall, these results provide
the first evidence of the presence of PFOS in surface seawaterand in coastal fishes from various locations in Japan.
Furthermore, field-based BCFs of PFOS in livers of fisheshave been reported. Additional studies are needed tocharacterize the exposure routes and fate of perfluorochemicals in the environment.

Acknowledgments
This study was carried out with the financial support of the
New Energy and Industrial Technology Development Organization (NEDO) of Japan.

Literature Cited(1) Giesy, J. P.; Kannan, K. Environ. Sci. Technol. 2001, 35, 13391342.
(2) Hansen, K. J.; Clemen, L. A.; Ellefson, M. E.; Johnson, H. O.
Environ. Sci. Technol. 2001, 35, 766-770.
(3) Kannan, K.; Koistinen, J.; Beckmen, K.; Evans, T.; Garzelany, J.;
Hansen, K. J.; Jones, P. D.; Giesy, J. P. Environ. Sci. Technol.
2001, 35, 1593-1598.
(4) Kannan, K.; Hansen, S. P.; Franson, C. J.; Bowerman, W. W.;
Hansen, K. J.; Jones, P. D.; Giesy, J. P. Environ. Sci. Technol.
2001, 35, 3065-3070.
(5) Kannan, K.; Newsted, J. L.; Halbrook, R. S.; Giesy, J. P. Environ.
Sci. Technol. 2002, 36, 2566-2571.
(6) Kannan, K.; Corsolini, S.; Falandysz, J.; Oehme, G.; Focardi, S.;
Giesy, J. P. Environ. Sci. Technol. 2002, 36, 3210-3216.
(7) Moody, C. A.; Field, J. A. Environ. Sci. Technol. 2000, 34, 38643870.
(8) Herbert, G. N.; Odom, M. A.; Craig, P. S.; Dick, D. L.; Strauss,
S. H. J. Environ. Monit. 2002, 4, 90-95.
(9) U.S. EPA (Environmental Protection Agency). Perfluorooctyl
Sulfonates: Proposed Significant New Use Rule. Federal Register
2000, 65, 62319-62333.
(10) Yamashita, N. NEDO project report “Methods of measurement
and risk-assessment of perfluorooctanyl sulfonate (PFOS) related

compounds (in Japanese)”; New Energy and Industrial Technology Development Organization in Japan, project no.
00X43011x, 2002.
(11) Taniyasu, S.; Kannan, K.; Horii, Y.; Yamashita, N. Organohalogen
Compds. 2002, 59, 319-322.
(12) Taniyasu, S.; Kannan, K.; Horii, Y.; Giesy, J. P.; Yamashita, N.
Fifth Annual Meeting of Japan Society of Endocrine Disrupters
Research, Hiroshima, Japan, 25-26 November 2002.
(13) Hansen, K. J.; Johnson, H. O.; Eldridge, J. S.; Butenhoff, J. L.;
Dick, L. A. Environ. Sci. Technol. 2002, 36, 1681-1685.
(14) Moody, C. A.; Martin, J. W.; Kwan, W. C.; Muir, D. C. G.; Mabury,
S. A. Environ. Sci. Technol. 2002, 36, 545-551.
(15) Saito, N.; Sasaki, K.; Nakatome, K.; Harada, K.; Yoshinaga, T.;
Koizumi, A. Arch. Environ. Contam. Toxicol. 2003, in press.
(16) Martin, J. W.; Mabury, S. A.; Solomon, K. R.; Muir, D. C. G.
Environ. Toxicol. Chem. 2003, 22, 196-204.
(17) Van der Heuvel, J. P.; Kuslikis, B. I.; Van Rafelghem, M. J.;
Peterson, R. E.; Toxicol. Appl. Pharmacol. 1991, 107, 450-459.
(18) Mackay, D. Environ. Sci. Technol. 1982, 16, 274-278.
(19) Gale, R. W.; Huckins, J. N.; Petty, J. D.; Peterman, P. H.; Williams,
L. L.; Morse, D.; Schwartz, T. R.; Tillitt, D. E. Environ. Sci. Technol.
1997, 31, 178-187.
(20) Tolls, J.; Haller, M.; Seinen, W.; Sijm, D. T. H. M. Environ. Sci.
Technol. 2000, 34, 304-310.
(21) Masunaga, S.; Kannan, K.; Doi, R.; Nakanishi, J.; Giesy, J. P.
Organohalogen Compds. 2002, 59, 319-322.
(22) Kannan, K.; Choi, J.-W.; Iseki, N.; Senthilkumar, K.; Kim, D. H.;
Masunaga, S.; Giesy, J. P. Chemosphere 2002, 49, 225-231.

Received for review February 3, 2003. Revised manuscript
received March 28, 2003. Accepted April 1, 2003.
ES0303440

VOL. 37, NO. 12, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 2639