A global survey of perfluorinated acids in oceans

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Marine Pollution Bulletin 51 (2005) 658–668

A global survey of perfluorinated acids in oceans

Nobuyoshi Yamashita a,*, Kurunthachalam Kannan b, Sachi Taniyasu a, Yuichi Horii a,Gert Petrick c, Toshitaka Gamo d

a National Institute of Advanced Industrial Science and Technology (AIST), 16-1, Onogawa, Tsukuba, Ibaraki 305-8569, Japanb Wadsworth Center, New York State Department of Health, Department of Environmental Health and Toxicology, State University of New York

at Albany, Empire State Plaza, P.O. Box 509, Albany, NY 12201-0509, USAc Leibniz-Institute of Marine Sciences, IFM-GEOMAR, West Shore Campus, Duesternbrooker Weg 20, D-24105 Kiel, Germany

d Ocean Research Institute, University of Tokyo, Nakano-ku, Tokyo 164-8639, Japan

Abstract

Perfluorinated acids and their salts have emerged as an important class of global environmental contaminants. Biological mon-

itoring surveys conducted using tissues of marine organisms reported the occurrence of perfluorooctanesulfonate (PFOS) and

related perfluorinated compounds in biota from various seas and oceans, including the Arctic and the Antarctic Oceans. Occurrence

of perfluorinated compounds in remote marine locations is of concern and indicates the need for studies to trace sources and path-

ways of these compounds to the oceans. Determination of sub-parts-per-trillion (ng/L) or parts-per-quadrillion (pg/L) concentra-

tions of aqueous media has been impeded by relatively high background levels arising from procedural or instrumental blanks.

Our research group has developed a reliable and highly sensitive analytical method by which to monitor perfluorinated compounds

in oceanic waters. The method developed is capable of detecting PFOS, perfluorohexanesulfonate (PFHS), perfluorobutanesulfo-

nate (PFBS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), and perfluorooctanesulfonamide (PFOSA) at a few pg/L

in oceanic waters. The method was applied to seawater samples collected during several international research cruises undertaken

during 2002–2004 in the central to eastern Pacific Ocean (19 locations), South China Sea and Sulu Seas (five), north and mid Atlan-

tic Ocean (12), and the Labrador Sea (20). An additional 50 samples of coastal seawater from several Asian countries (Japan, China,

Korea) were analyzed. PFOA was found at levels ranging from several thousands of pg/L in water samples collected from coastal

areas in Japan to a few tens of pg/L in the central Pacific Ocean. PFOA was the major contaminant detected in oceanic waters,

followed by PFOS. Further studies are being conducted to elucidate the distribution and fate of perfluorinated acids in oceans.

� 2005 Elsevier Ltd. All rights reserved.

1. Introduction

Perfluorinated compounds (PFCs) have emerged as a

new class of global environmental pollutants. Among

PFCs, perfluorinated sulfonates and perfluorinated

carboxylates have attracted much attention in recent

years. These compounds in general, and perfluorooctane

sulfonate (PFOS) and perfluorooctanoate (PFOA) in

particular, comprise a class of environmentally persis-tent chemicals that have a wide range of industrial appli-

0025-326X/$ - see front matter � 2005 Elsevier Ltd. All rights reserved.

doi:10.1016/j.marpolbul.2005.04.026

* Corresponding author. Tel./fax: +81 899 61 8335.

E-mail address: [email protected] (N. Yamashita).

cations, such as fire-fighting foams, pesticides, andconsumer applications including surface coatings for

carpets, furniture, and paper products (Kissa, 2001).

Although these contaminants have probably been pres-

ent in the environment and in biota for many decades,

their environmental and biological effects have been

realized only recently. The unique physicochemical

properties of perfluorinated compounds make them

highly suitable for the applications described earlier.These properties, such as high surface activity, thermal

stability, amphipathicity, resistance to acidic and alka-

line conditions, density, and weak intermolecular inter-

actions, are responsible for their industrial value, but

mailto:[email protected]

N. Yamashita et al. / Marine Pollution Bulletin 51 (2005) 658–668 659

they also contributed to the compounds� persistence inthe environment and accumulation in biota. PFOS does

not hydrolyze, photolyze, or biodegrade under environ-

mental conditions. PFOS has been shown to bioconcen-

trate and bioaccumulate in the tissues of bluegill sunfish

(3M, 2000; 3M, 2003) and rainbow trout (Martin et al.,2003). Apparent steady-state bioconcentration factor

(BCF) values for edible, non-edible, and whole bluegill

sunfish tissues were calculated to be 484, 1124, and

859, respectively. Similarly, the BCFs of PFOS in liver

and carcass of rainbow trout were 1100 and 5400,

respectively. PFOS depurates slowly, and the estimates

for the time to reach 50% clearance for edible, non-edi-

ble, and whole fish tissues were 146, 133, and 152 days,respectively, for bluegill. The half-life of PFOS in rain-

bow trout exposed to this compound under laboratory

conditions was 12–15 days (Martin et al., 2003).

Understanding of the environmental dynamics of

PFCs is not straight forward, due to the unique charac-

teristics of these molecules, their widespread applica-

tions, and the range of substituted polar moieties in

the various compounds. All of the perfluoroctanesulfo-nyl fluoride (POSF)-based perfluorochemicals (such as

perfluorooctanesulfonamide ethanol and perfluoro-

octanesulfonamide) biologically break down or become

metabolized to PFOS. In addition to its production

and use as a surfactant, PFOA is also formed as a

degradation product of several fluoropolymers and

fluorotelomer alcohol. It is clear that pollution by per-

fluorinated acids, particularly PFOS and PFOA, is aglobal issue, given the trans-boundary movement of

these compounds (Giesy and Kannan, 2001, 2002; Kan-

nan et al., 2001a,b; Kannan et al., 2002a,b,c,d; Taniyasu

et al., 2003; Martin et al., 2004; Van de Vijver et al.,

2003). Despite the existence of studies reporting the

occurrence of PFCs in biological matrices, very few

studies have reported these compounds� occurrence inabiotic matrices such as air and water (Stock et al.,2004; Shoeib et al., 2004; Hansen et al., 2002; Moody

et al., 2002). Analysis of perfluorinated acids in ambient

waters requires sensitive and accurate methods, due to

the occurrence of these compounds at parts-per-trillion

or lower levels. Initially, we conducted a survey of ocean

water samples collected from selected coastal environs

in order to measure concentrations of perfluorinated

acids in surface waters (Taniyasu et al., 2003; Yamash-ita et al., 2003). These studies showed that PFOS and

PFOA occur at parts-per-quadrillion (ppq) levels and

that the level of analysis required improvements in the

current analytical techniques enabling lower detection

limits through reduction of the instrumental and proce-

dural background. We developed a reliable and sensi-

tive analytical and sampling method for ultra-trace

level analysis of PFCs that is applicable to global sur-vey of PFCs in open ocean waters (Yamashita et al.,

2004).

Analysis of PFCs in open ocean waters is challeng-

ing because of the need for an analytical method capa-

ble of measuring these compounds at ppq levels.

Details regarding the improvements in the analytical

methods and monitoring of oceanic waters for PFCs

are discussed below. The aim of this article is to providean overview of analytical methods and concentrations

of perfluorinated acids in oceanic ecosystems. The per-

fluorinated acids targeted in our study were PFOS,

PFOA, perfluorohexanesulfonate (PFHS), perfluorono-

nanoic acid (PFNA), and perfluorooctanesulfonamide

(PFOSA).

2. Biomonitoring of PFCs in oceans

Since the oceans play a major role as a sink for many

persistent organic pollutants, studies on the fate of PFCs

in the oceans are important. PFCs such as PFOS,

PFHS, PFOA, and PFOSA have been found in oceanic

organisms collected from a number of locations, includ-

ing remote marine locations such as the Arctic and theAntarctic Oceans (Table 1). This suggests the transport

of PFCs to remote marine locations by long-range

atmospheric transport and/or oceanic currents. PFOS

was the predominant perfluorinated acid among several

that were measured in oceanic organisms (Kannan et al.,

2001b; Martin et al., 2004). Concentrations as great as a

few parts-per-million, (lg/g, on a wet weight basis) werefound in livers of several marine mammal species fromthe North Sea, the Baltic Sea and the Mediterranean

Sea, and Gulf of Mexico (Kannan et al., 2001b). Among

various marine animals analyzed, polar bears collected

from the Canadian Arctic contained the highest concen-

trations of PFOS (Martin et al., 2004). These results

highlight the need to study sources and pathways of

exposure of these animals to perfluorinated acid. Moni-

toring of perfluorinated acids in oceanic water and airprovide information on the relative importances of

atmospheric transport and hydrospheric (current) move-

ments of these compounds from continental source

regions.

3. Toxicity of PFCs to aquatic organisms

Ecotoxicological studies of PFOS in several aquatic

organisms have been conducted under laboratory condi-

tions (3M, 2003; OECD, 2002). PFOS has been shown

to be acutely toxic to fish in short-term studies, at con-

centrations below the limit of its solubility in fresh water

(approximately 370 mg/L). The most susceptible species

tested thus far was Pimephales promelas (fathead min-

now), with a 96-h LC50 of 4.7 mg/L (Table 2; 3M,2003). PFOS was also acutely toxic to fish in salt water

(3M, 2003). A 96-h LC50 value of 13.7 mg/L has been

Table 1

Concentrations of PFOS and PFOA (ng/g, wet weight) in livers of various marine mammals and in sera of albatrosses collected during 1995–2004

from various seas and oceans

Species Location PFOS PFOA Remarks Reference

Polar skua liver Antarctica <15 <19 Giesy and Kannan (2001)

Penguina Antarctica <8 <19

Polar bear Alaskan Arctic <10–678 <38 Kannan et al. (2001a)

California sealions,

seals and sea otters

Pacific coast of California <5–133 <38 Kannan et al. (2001a)

Whales and dolphins Gulf of Mexico 6.6–1520 (489) <38 Kannan et al. (2001a)

Gray and ringed seals Baltic Sea 130–1100 <19–39 Kannan et al. (2002b)

Striped and common

dolphins, pilot whale

Mediterranean Sea 16–940 <38 PFOSA was found Kannan et al. (2002b)

Bottlenose dolphin Mediterranean Sea <1.4–110 <38 PFOSA was found Kannan et al. (2002b)

Polar bear Canadian Arctic 1700–4000 (3100) 2.9–13 (8.6) PFNA, PFDA, PFUA,

PFDoA were found

Martin et al. (2004)

Ringed seal Canadian Arctic 8.6–23 (16) <2 PFNA, PFDA, PFUA,

PFDoA were found

Martin et al. (2004)

Harbor porpoise North Sea 12–395 (93) <62 PFUA, PFDA, PFDoA

were present

Van de Vijver et al. (2003)

Several species

(whales, seals,

dolphins, porpoise)

North Sea <10–821 <62 PFUA, PFDA, PFDoA

were present

Van de Vijver et al. (2003)

Black-footed/

Laysan albatrosses

North Pacific Ocean 3–34 (11) <10 Kannan et al. (2001b)

a Eggs rather than livers were analyzed for penguins.

Table 2

Toxic effect of PFOS in aquatic organismsa

Test organisms: Acute/chronic Species Effective concentration (mg/L)

Fish freshwater

Acute Pimephales promelas (fathead minnow) 96-h LC50 = 10

96-h NOEC = 3.6

Lepomis macrochirus (bluegill sunfish) 96-h LC50 = 7.8

96-h NOEC = 4.5

Chronic Pimephales promelas (fathead minnow) 42-day NOECsurvival = 0.33

47-day early life LOEC = 0.65

Freshwater invertebrates

Acute Daphnia magna (water flea) 48-h EC50 = 66

Unio complamatus (freshwater mussel) 96-h LC50 = 59

96-h NOEC = 20

Chronic Daphnia magna (water flea) 28-day NOECreproduction = 7

Invertebrates—salt water

Acute Mysidopsis bahia (mysid shrimp) 96-h EC50 = 4.0

96-h NOEC = 1.2

Crassostrea virginica (eastern oyster) 96-h EC50 = > 3.0

96-h NOEC = 1.9

Sub-chronic/chronic Mysidopsis bahia (mysid shrimp) 35-day NOECreproduction/growth = 0.25

Acute Oyster shell deposition 96-h NOEC = 2.1

Algae—freshwater

Selenastrum capricornutum 96-h EbC50(biomass) = 71

96-h ErC50(growth rate) = 126

96-h NOECbiomass/growth rate = 48

a Data from 3M, 2000; 3M, 2003.

660 N. Yamashita et al. / Marine Pollution Bulletin 51 (2005) 658–668

determined for Oncorhynchus mykiss (rainbow trout)

acclimated to salt water. In longer-term PFOS exposure

studies of fish in freshwater, the lowest no observed ef-

fect concentration (NOEC) determined in tests with

Pimephales promelas was 0.3 mg/L over 42 days, based

on growth and survival. PFOS was acutely toxic to

freshwater and saltwater invertebrates in short-term

studies, at concentrations below the limit of its water

solubility. The most sensitive freshwater species in acute

toxicity studies was the crustacean Daphnia magna


(water flea), with a 48-h EC50 value of 27 mg/L. The

most sensitive saltwater species was Mysidopsis bahia

(mysid shrimp), with a 96-h LC50 value of 3.6 mg/L.

NOECs of 12 and 7 mg/L have been determined for

PFOS to D. magna (fresh water) in 21- and 28-day

reproduction tests, respectively. A NOEC of 0.25 mg/Lhas been determined for growth and reproduction of

M. bahia (salt water) in a 35-day test. PFOS was toxic

to freshwater unicellular algae in short-term studies, at

concentrations below the limit of its solubility in fresh

water. Tests with Pseudokirchneriella subcapitata yielded

the lowest 96-h EC50 (growth rate) of 71 mg/L and a

NOEC (growth rate) of 35 mg/L. No effects on growth

rate of the diatom Skeletonema costatum were deter-mined at 3.2 mg/L (3M, 2003). This concentration was

close to the reported solubility of PFOS in unfiltered

seawater. PFOS was also toxic to freshwater higher

plants. A growth-inhibition test with Lemna gibba

(duckweed) yielded a 7-day IC50 of 108 mg/L for inhibi-

tion of frond production and a 7-day NOEC of 15.1 mg/

L based on the inhibition of frond production and evi-

dence of sub-lethal effects. The results of an amphibianteratogenesis study carried out with Xenopus laevis

(African clawed frog) showed PFOS to be acutely toxic

(96-h LC50 = 13.8 mg/L), and cause malformations in

frog embryos (96-h EC50 = 12.1 mg/L) (3M, 2003). The

minimum concentration that inhibited growth of the

embryos was determined to be 7.97 mg/L. A commu-

nity-level zooplankton NOEC of 3.0 mg/L was deter-

mined for PFOS in a 35-day study (Boudreau et al.,2003). The 42-day 50% inhibition concentration (IC50)

of PFOS for L. gibba frond number was 19.1 mg/L,

and the NOEC was 0.2 mg/L. Studies on the aquatic

toxicity of PFOA and other perfluorinated acids are

few in number.

4. Analytical issues in the monitoring of oceanic samples

The analytical methods for the measurement of per-

fluorinated acids in environmental matrices are at vari-

ous stages of development. The compounds� uniquephysico-chemical properties present several challenges

to analytical chemists who endeavor to measure PFCs

at trace levels, particularly in oceanic samples. One of

the major problems associated with trace-level analysisof perfluorinated acids, particularly PFOS and PFOA,

is background contamination in the analytical blanks.

Because of the contamination in blanks, the limits of

detection (LOD) of PFCs in water samples are high, in

the range of several 10s to 100s of ng/L, to a few lg/L(Moody and Field, 2000; Hansen et al., 2002; Hebert

et al., 2002; Moody et al., 2001; Taniyasu et al., 2003).

However, concentrations of PFOS in ambient waterscollected from various lakes and rivers within continen-

tal areas are in the lower to upper ng/L range (Taniyasu

et al., 2002, 2003; Saito et al., 2003). At LOD of 25 ng/L,

PFOS and PFOA could not be detected in surface water

samples collected from various lakes and rivers in Mich-

igan, USA (Kannan, unpublished data).

Contamination sources of PFCs in laboratories have

not been well characterized. Two distinct sources of con-tamination, instrumental and procedural, are expected

in PFC analysis. One known source of procedural con-

tamination is fluoropolymers, such as polytetrafluoro-

ethylene and perfluoroalkoxy compounds, which are

present in a variety of laboratory products (for details

please see Yamashita et al., 2004). During the analysis

of perfluorinated acids in environmental or biological

matrices, samples or extracts are not allowed to comein contact with such fluoropolymers. However, post-

injection contamination, not related to injection-port

carryover, has been observed in high performance liquid

chromatography–mass spectrometry (HPLC–MS) anal-

ysis of perfluorinated acids. This impedes the analysis of

sub ppt (ng/L) or ppq (pg/L) concentrations of perfluo-

rinated acids expected to be found in ocean waters. We

have identified sources of contamination in proceduralblanks and eliminated them in order to develop ultra

trace analysis of perfluorinated acids in oceanic waters.

The HPLC tubing, internal fluoropolymer parts, and

autosampler vial septa have been identified as potential

sources of perfluorinated acids detected in instrumental

blanks (Fig. 1). Replacement of the HPLC tubing with

stainless steel and polyetheretherketone (PEEK) tubing

eliminated some of the interferences that had been intro-duced from the Teflon tubing. Degasser and solvent-

selection valves, which have fluoropolymer coatings

and seals, were isolated from the HPLC system. Solvent

inlet filters were replaced with stainless steel filters. Fol-

lowing these modifications, instrumental blank concen-

trations decreased considerably (Fig. 1).

Autosampler vial caps made of Teflon� or Viton�

fluoropolymers are a source of perfluorinated acidsfound in blanks (Yamashita et al., 2004). Viton�-lined

caps contain the highest concentrations of several PFCs,

followed by Teflon�-lined vial caps. The lowest concen-

trations were found in polyethylene caps. No target ana-

lytes were detected in the polypropylene tubes used in

the analysis (Table 3). The contamination of instrumen-

tal blanks was considerably reduced by changing the flu-

oropolymer tubing and autosampler vial septa.We also examined the sources of blank contamina-

tion in various sample processing steps, including collec-

tion, storage, extraction, and treatment of samples prior

to instrumental analysis. Polypropylene sample bottles

have been used for the collection and storage of water

samples. Analysis of polyethylene containers, by extrac-

tion of the inner surface with methanol showed the pres-

ence of trace levels of PFOA, but not other PFCs (Table3). Two types of solid phase extraction (SPE) cartridges

were tested for the presence of target analytes through

x 1

x 1

x 1

x 1

PFOS

PFOA

PFHS

PFBS x 13

x 34

x 266

x 133

Before After

Fig. 1. PFOS, PFOA, PFHS and PFBS in HPLC–MS/MS instrumental blanks, before and after methodological modifications: (Before) 10 lLmethanol was injected with Teflon tubing, degasser, solvent mixer, plastic suction filter. No vial septum was used and (after) 10 lL methanol was

injected without degasser, and solvent mixer. Stainless steel, PEEK tubing, suction filter and polyethylene vials and caps were used.

Table 3

Contamination levels (ng/L of methanol) of perfluorinated compounds in several materials used in the analysis of water

PFOS PFHS PFBS PFNA PFOA PFOSA THPFOS

Vial septuma

A <3.0 <2.0 <2.9 <9.2 <9.3 <3.8 <2.1

B 74 <2.0 <2.9 <9.2 764 56 139

C 367 15 6.0 <9.2 210 40 <2.1

D 74 2.4 2.6 <9.2 145 38 <2.1

E 32,000 965 237 87 4600 40 <2.1

Sodium thiosulfate solution

Sodium thiosulfate (DW)b <10 <16 <9.8 n.a.d <12 n.a. <4.4

Sodium thiosulfate (Milli-Q)c <10 <16 <9.8 n.a. <12 n.a. <4.4

Polypropylene bottle

1000 mL <10 <16 <9.8 n.a. 27 n.a. <4.4

500 mL <10 <16 <9.8 n.a. 24 n.a. <4.4

50 mL <10 <16 <9.8 n.a. 16 n.a. <4.4

15 mL <10 <16 <9.8 n.a. 26 n.a. <4.4

Nylon filter

Nalgene Washed <10 <16 <9.8 n.a. <12 n.a. <4.4

Not washed 117 <16 <9.8 n.a. 63 n.a. <4.4

Millipore Washed <10 <16 <9.8 n.a. <12 n.a. <4.4

Not washed <10 <16 <9.8 n.a. 25 n.a. <4.4

Iwaki Washed <10 <16 <9.8 n.a. <12 n.a. <4.4

Not washed 37 <16 <9.8 n.a. 75 n.a. <4.4

a (A) Snap cap with polyethylene septum; (B) Crimp cap with Teflon/silicon/Teflon septum; (C) Screw cap with Teflon/silicon/Teflon septum;

(D) Screw cap with Teflon/rubber septum and (E) Crimp cap with Viton septum.b DW: HPLC-grade distilled water.c Milli-Q: Milli-Q water.d n.a.: Not analyzed.


the entire analytical procedure. PFOS and PFOA were

detected at 12 and 46 pg/L, respectively, in Sep-pak�

cartridges, but in Oasis� cartridges, PFOS and PFOA

concentrations were ten fold lower than the level that

was found in the Sep-pak� cartridge (Yamashita et al.,

2004). After the extraction, samples are generally passed

through nylon syringe filters to remove particles, prior

to HPLC–MS/MS injection. We analyzed nylon filtersfrom three commercial sources, by passing 2 mL of

methanol through the filters. Trace amounts of PFOA

(25–75 pg) were found in all three brands (Table 3).

PFOS was detected in two of the three brands analyzed.

However, washing of the filters with methanol (2 mL)

prior to filtration of the samples eliminated the residues

of PFOS and PFOA arising from the filters. It appeared

that the trace levels of PFOS or PFOA found in some of

the laboratory ware used in the analysis are explained by

the choice of procedural blanks used. Milli-Q water orHPLC-grade water is generally used as a procedural

blank and is processed along with experimental samples.


HPLC-grade water appeared to contain lower concen-

trations of PFCs than did distilled water or Milli-Q

water. It would be appropriate to purify HPLC-grade

water by passage through a cartridge or an adsorbent,

before it is used for a procedural blank.

Following our improvements in the analytical andinstrumental procedures, the blank/background levels

of target perfluorinated acids were reduced significantly.

In addition, matrix spikes, field blanks, procedural

blanks, instrumental blanks, and continuing calibration

verification with every set of 20–25 samples were used to

determine the LOD, and to check for possible contami-

nation and interferences. Field blanks contained 800 mL

of HPLC-grade water were taken in a polypropylenebottle and transported to sampling locations. 200 lLof sodium thiosulfate solution was added to the field

blanks. Although the concentrations of target fluoro-

chemicals in field blanks were similar to those in proce-

dural blanks in most cases, any sample sets that were

found to have notable contamination in field blanks

were eliminated from further analysis.

5. Analytical methods for PFC monitoring in oceanic

waters

The analytical procedure for the extraction of water

samples was similar to that described elsewhere (Hansen

et al., 2002) with some modifications (Taniyasu et al.,

2003). Modifications include the use of 10-g SPE Sep-pak� tC18 cartridges instead of 1-g cartridges, and

extraction of 500 to 1000 mL water instead of 40 mL

water. However, Sep-pak� tC18 cartridges were used

only in the beginning of the study (Japanese inland

and coastal waters; see Taniyasu et al., 2003), before

we determined that Oasis� HLB cartridges performed

better, in terms of lower background levels and im-

proved recoveries. Therefore, Oasis� HLB cartridgeswere used for open ocean water samples. Several other

modifications and the use of new cartridges are detailed

below.

In general, the SPE cartridges were pre-conditioned

by the passage of 100 mL of methanol followed by

50 mL of HPLC-grade water, prior to the passage of

samples. A sample aliquot of water (500–1000 mL)

was passed through the pre-conditioned cartridges at arate of 1 drop/s, and the cartridges were not allowed

to dry out at any time during 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 were

collected in a polypropylene tube. The solvent was evap-

orated under a gentle stream of pure nitrogen gas to 0.2–

0.5 mL for ocean waters. Particles that appeared in thefinal solution of a few of the water samples were re-

moved by filtration using a nylon syringe filter.

Analysis of trace levels of PFCs was performed using

an HPLC–MS/MS; an Agilent HP1100 liquid chromato-

graph interfaced with a Micromass� (Beverly, MA,

USA) Quattro Ultima Pt mass spectrometer operated

in an electrospray negative ionization mode was used.

A 5- or 10-lL aliquot of the sample extract was injectedinto a guard column (XDB-C8, 2.1 mm i.d. · 12.5 mm,5 lm; Agilent Technologies, Palo Alto, CA) connected

sequentially to a Betasil C18 column (2.1 mm

i.d. · 50 mm length, 5 lm; Thermo Hypersil-Keystone,

Bellefonte, PA) with 2 mM ammonium acetate/metha-

nol as mobile phase, starting at 10% methanol. At a flow

rate of 300 mL/min, the gradient was increased to 30%

methanol at 0.1 min, 75% methanol at 7 min, and100% methanol at 10 min, and was held there until

12 min before reversion to original conditions, at

20 min. The capillary was held at 1.2 kV. Cone-gas

and desolvation-gas flows were held at 60 and 650 L/h,

respectively. Source and desolvation temperatures were

kept at 120 and 420 �C respectively. MS/MS parameters

were optimized so as to transmit the [M–K]- or [M–H]-

ions. Eight calibration curve points bracketing the con-centrations in samples were prepared routinely, to check

for linearity.

Quantitative analyses were performed by monitoring

a single product ion selected from a primary ion charac-

teristic of a particular fluorochemical, using HPLC–ES/

MS/MS. For example, molecular ion m/z = 499, selected

as the primary ion for PFOS (C8F17SO3–) analysis, was

fragmented further to produce ion m/z = 99 (FSO3-).The characteristic product ion (m/z = 99) was monitored

for quantitative analysis. Quantitation of the target ana-

lytes was based on quadratic regression fit analysis

weighted 1/x of a single unextracted curve for each

group of tissue samples. High or low points on the curve

were deactivated, if necessary, to provide a better linear

fit over the curve range most appropriate to the samples.

Low points on the curve with peak areas less than thatof the average response from the procedural blanks were

deactivated, to disqualify a data range that may have

been significantly affected by background levels of the

analyte. Quantitation of each analyte was based on

the response of one specific product ion using the multi-

ple reaction-monitoring mode of the instrument. Un-

extracted calibration standards were prepared at

approximately 0.001–100 ng/mL for analysis. The coeffi-cient of determination (r2) of each standard curve was

>0.99.

Specificity for analyte identification was demon-

strated by chromatographic retention time and mass

spectral daughter ion characterization. Additional con-

firmatory tests were performed by selecting more transi-

tions. Typically, m/z 498.6 > 98.6 and 498.6 > 79.6

transitions were monitored for PFOS, 412.9 > 368.7for PFOA, 462.7 > 418.8 for PFNA, 398.6 > 79.7 for

PFHS and 497.6 > 77.7 for PFOSA.


The highest concentrations of target compounds in

procedural blanks, which were passed through the entire

analytical procedure involving the SPE cartridges, were

0.8 pg of PFOS, 0.4 pg of PFHS, 0.6 pg of PFBS, 5.2 pg

of PFOA, 1.8 pg of PFNA, 1 pg of PFOSA, and 1.1 pg

of THPFOS in 1 L of water sample. The LOQs of targetchemicals were evaluated for each sample based on the

maximum blank concentration, the concentration fac-

tors, the sample volume and a signal-to-noise ratio of

3. Details of the analytical procedures have been re-

ported elsewhere (Yamashita et al., 2004).

We applied this method to all seawater samples col-

lected from several international joint cruises. We have

conducted six open ocean cruises from 2002 to 2004 asfollows: the central to eastern Pacific Ocean (19 loca-

tions), the South China Sea and Sulu Seas (5), north

and middle Atlantic Ocean (12), and the Labrador Sea

(20). Samples of 50 coastal seawater were also collected

from Asian countries (Japan, China, Hong Kong,

Korea).

6. Concentrations of PFCs in oceanic waters

Concentrations of PFOS, PFHS, PFNA, and PFOA

in open ocean water samples from the Pacific and Atlan-

tic Oceans, and from several coastal seawaters from

Asian countries, are shown in Table 4 and Figs. 2–5.

PFOS and PFOA were found in 80% of the surface sea-

water samples analyzed. There were similarities betweenPFCs composition in coastal and open ocean waters in

some regions. It appeared that tidal and/or water cur-

rent movements play a major role in the transport of

these compounds from coastal locations; therefore,

information on oceanic currents appeared necessary to

explain the transport of PFCs from coastal waters to

the open ocean.

Table 4

Concentrations (pg/L) of PFOS, PFHS, PFNA, and PFOA in coastal and o

Location Na

Tokyo Bay 8

Offshore of Japan 4

Coastal area of Hong Kong 12

Coastal area of China 14

Coastal area of Korea 10

Sulu Sea (surface water) 3

Sulu Sea (deep water; 1000–3000 m) 2

South China Sea 2

Western Pacific Ocean 2

Central to Eastern Pacific Ocean (surface water) 12

Central to Eastern Pacific Ocean (deep water; 4000–4400 m) 2

North Atlantic Ocean 9

Mid Atlantic Ocean 7

n.a. = not analyzed.a Number of samples analyzed.

Relatively high concentrations of PFOS, PFHS, and

PFOA were detected in Tokyo Bay waters. PFOA was

the predominant fluorochemical detected, ranging in

concentration from 1800 to 192,000 pg/L, followed by

PFOS (338–57,700 pg/L). Concentration of PFHS was

an order of magnitude lower than the concentration ofPFOS. High concentrations of PFCs in Tokyo Bay

waters suggest sources associated with urban and indus-

trial areas in Tokyo. The higher concentration of PFOA

than of PFOS in water samples is an interesting observa-

tion. In wildlife samples collected from several locations,

PFOS was the predominant compound, rather than

PFOA (Kannan et al., 2001a,b). This suggests that the

bioaccumulation potential of PFOA is relatively lowerthan 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 inthe concentration of PFOA or PFOS in offshore waters

was somewhat lower than for coastal waters, suggesting

a generalized source such as atmospheric or hydro-

spheric transport. PFOSA was also found in these sam-

ples, 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 werecomparable to those in offshore waters collected in the

South China Sea and the Sulu Sea. The concentrations

of PFOA and PFOS in central and eastern Pacific Ocean

waters ranged from 15 to 62 and from 1.1 to 20 pg/L,

respectively. These concentrations were an order of

magnitude lower than the concentrations found in off-

shore waters, and four orders of magnitude lower than

pen ocean water samples from the Pacific and Atlantic Oceans

PFOS PFHS PFNA PFOA

338–57,700 17–5600 163–71,000 1,800–192,000

40–75 3.0–6.1 n.a. 137–1060

70–2600 <5–311 22–207 673–5450

23–9680 <5–1360 2.0–692 243–15,300

39–2530 <5–1390 15–518 239–11,350

<17–109 <0.2 n.a. 88–510

<17–24 <0.2 n.a. 76–117

8–113 <0.2 n.a. 160–420

54–78 2.2–2.8 n.a. 136–142

1.1–20 0.1–1.6 1.0–16 15–62

3.2–3.4 0.4–0.6 n.a. 45–56

8.6–36 4.1–6.1 15–36 160–338

37–73 2.6–12 n.a. 100–439

Fig. 2. Concentrations of PFOS and PFOA in surface seawater from Tokyo Bay and coastal Japan.

PACIFIC OCEAN

Sulu Sea

South ChinaSea

0

100

200

300

400

500

600

700

800

900

1000

PFOA

PFOS

Con

cent

ratio

ns [

pg/L

]

500 km

0

100

200

300

400

500

600

700

800

900

1000

PFOA

PFOSPhilippine Sea

0

100

200

300

400

500

600

700

800

900

1000

PFOA

PFOS

0

100

200

300

400

500

60

700

800

900

1000

PFOA

PFOS

0

100

200

300

400

500

600

700

800

900

1000

PFOA

PFOS

500 kmkm

Fig. 3. Concentrations of PFOS and PFOA in surface seawater from the South China Sea, and from the Sulu Sea.


Fig. 4. Concentrations of PFOS and PFOA in surface seawater of the Atlantic Ocean and Eastern Pacific Ocean.


Fig. 5. Spatial trends in the concentrations of PFOS and PFOA in surface seawater from coastal Japan to the central Pacific Ocean.

the concentrations measured in Tokyo Bay waters.These values appear to be the background values for re-

mote marine waters far from local sources. In fact, their

concentrations were just above the LOD of the analyti-

cal method. Fig. 5 illustrates the spatial concentrations

of PFOS, PFHS, and PFOA, from coastal Japan to

the central Pacific Ocean. Concentrations of PFCs de-

creased dramatically, by 2–4 orders of magnitude, from

coastal to offshore. It appears that PFOA pollution is

more ubiquitous than that of PFOS in oceanic waters.This pattern may be similar to trifluoroacetic acid

(TFA) pollution in oceans. Widespread distribution of

TFA in open ocean waters has been reported (Scott

et al., submitted). It is probable that several perfluori-

nated carboxylates display environmental dynamics

similar to those of TFA.

We have also examined the distribution of PFCs in

marine waters in a third dimension. We have collected


more than 30 deep-sea water samples from the above-

mentioned locations and detected some PFCs. Presence

of PFCs in deep-sea water shows the need for a compre-

hensive survey of not only surface water but also the

vertical profiles of PFCs in the water column, as well

as the open ocean air. Deep-sea water samples, collectedat depths >1000 m in the Pacific Ocean and the Sulu

Sea, contained trace levels of PFOS and PFOA. The

deep seas play a major role as a sink for several POPs;

accordingly, their role in the global dynamics of PFCs

is worthy of investigation.

Acknowledgement

We are thankful to many staff members at Leibniz-

Institute of Marine Sciences, IFM-GEOMAR, Ger-

many, and Hokkaido University, Marine Institute of

Tokyo University, and Ibaraki University in Japan, City

University of Hong Kong, South China Normal Univer-

sity, 4DK Science R&D Center in Korea, and Prof. J. P.

Giesy (Michigan State University) for their support inthe collection of ocean water samples. Collaborative

work with several of the staff at the Wadsworth Center,

New York State Department of Health, Albany, NY,

helped in the development of these analytical methods.

Part of this study was supported by a research grant

from the Environment Agency (2003), Japan.

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