· e-mail: [email protected] ... and remediation efforts in the Bohai Sea region. ... TB3 Riverside, abandoned land 1 1 1 Tanggu Yongding River

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Environmental Geochemistry andHealthOfficial Journal of the Society forEnvironmental Geochemistry andHealth ISSN 0269-4042Volume 34Number 3 Environ Geochem Health (2012)34:301-311DOI 10.1007/s10653-011-9422-2

Perfluorinated compounds in a coastalindustrial area of Tianjin, China

Tieyu Wang, Yonglong Lu, Chunli Chen,Jonathan E. Naile, Jong Seong Khim &John P. Giesy

1 23

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ORIGINAL PAPER

Perfluorinated compounds in a coastal industrial areaof Tianjin, China

Tieyu Wang • Yonglong Lu • Chunli Chen •

Jonathan E. Naile • Jong Seong Khim •

John P. Giesy

Received: 15 March 2011 / Accepted: 19 August 2011 / Published online: 1 September 2011

� Springer Science+Business Media B.V. 2011

Abstract Perfluorinated compounds (PFC) in water,

sediment, soil, and biota from the coastal industrial

area of Tianjin, China, were measured to provide

baseline information and to determine possible sources

and potential risk to wildlife. Perfluorooctanesulfonate

(PFOS) was the predominant PFC with maximum

concentrations of 10 ng/L in water, and 4.3, 9.4, and

240 ng/g dw in sediment, soil, and fish, respectively.

Perfluorooctanoate (PFOA) concentration in water

ranged from 3.0 to 12 ng/L. Perfluoroundecanoate

(PFUnA) and Perfluorododecanoate (PFDoA) were

detected in solid matrices, respectively, at concentra-

tions of\LOQ to 1.2 ng/g dw and 0.27–0.81 ng/g dw

in sediments, and \LOQ to 1.0 ng/g dw and 0.26–

0.61 ng/g dw in soils. Concentrations of PFOS, PFUnA,

and PFDoA in sediment and soil from this industrial-

ized and urbanized area were greater than those

previously reported, while PFOS and PFOA in water

and biota were both less than reported threshold

concentrations for adverse effects in wildlife.

Keywords PFC � Water � Soil � Sediment �Biota � Risk

Introduction

Because of their environmental persistence, bioaccu-

mulation, global distribution, and toxicity (Conder

et al. 2008; Schuetze et al. 2010; Zushi et al. 2010),

concern about the presence of perfluorinated chem-

icals (PFC) has been increasing since they were first

reported to be widespread in the environment (Giesy

and Kannan 2001, 2002). PFC have been used in a

variety of applications such as surfactants and surface

protectors in carpets, leather, paper, food containers,

fire-fighting foams, floor polishes, and shampoos

(Kissa 2001). These compounds are introduced in the

environment during production and use in industries,

T. Wang � Y. Lu (&) � C. Chen

State Key Lab of Urban and Regional Ecology,

Research Center for Eco-Environmental Sciences,

Chinese Academy of Sciences, Beijing 100085, China

e-mail: [email protected]

J. E. Naile � J. P. Giesy

Toxicology Centre and Department of Veterinary

Biomedical Sciences, University of Saskatchewan,

Saskatoon, SK S7N5B3, Canada

J. S. Khim

Division of Environmental Science and Ecological

Engineering, Korea University, Seoul 136-713,

Republic of Korea

J. P. Giesy

Zoology Department, College of Science, King Saud

University, P. O. Box 2455, Riyadh 11451, Saudi Arabia

J. P. Giesy

Department of Zoology and Center for Integrative

Toxicology, Michigan State University, East Lansing,

MI 48824, USA

123

Environ Geochem Health (2012) 34:301–311

DOI 10.1007/s10653-011-9422-2

Author's personal copy

in products, runoff, accidental spills, or untreated

discharges (Melissa et al. 2003). PFC have been

detected in aquatic systems (Fujii et al. 2007; Rayne

and Forest 2009; Kim et al. 2011) and wildlife

(Houde et al. 2006; Fatihah et al. 2009; Fair et al.

2010). Perfluorooctanesulfonate (PFOS) is the termi-

nal degradation product of a number of poly or

perfluorinated precursors and is detected in environ-

mental and biological samples where it is also the

predominant PFC. PFOS was recently listed as a

‘‘persistent organic pollutant’’ under the Stockholm

Convention, but exemptions were made, which allow

continued production and use in China (Wang et al.

2009b). Restrictions on production of PFOS in other

countries have resulted in increased production and

use in China as well as overseas exports. Since 2000,

annual production of PFOS-containing chemicals in

China has increased each year (Bao et al. 2009).

Rapid industrial development during the past few

decades has transformed China into one of the

world’s largest economies, especially in the Bohai

Sea region; a semi-enclosed coastal water body

located on the northeast coast of China. The Tianjin

Binhai New Area (TBNA), situated in the lower part

of the Haihe River watershed and west of Bohai Bay,

is one of the most important industrial areas in the

North of China. Intensive economic development and

urbanization in this area have severely deteriorated

environmental quality, especially along the coast.

The TBNA is comprised of three different adminis-

trative regions, Tanggu, Hangu, and Dagang. Tanggu

and Hangu have been historically known for their

chemical industry with the Dagu Chemical Industrial

Park at Tanggu and the Hangu Chemical Industrial

Park at Hangu. The Dagang region has abundant

wetlands and oil resources, and the industries that

produce or process petroleum, petrochemicals, and

fine chemicals are developing.

Organochlorine pesticides, polycyclic aromatic

hydrocarbons, and metals are present in various

environmental media in the TBNA (Jiao et al. 2009;

Wang et al. 2009a; Shi et al. 2010). However, previous

studies have focused mainly on classic persistent toxic

substances (PTS), and little information is available

for emerging PTS such as PFC. Concentrations of PFC

in environmental matrices from the TBNA are scarce.

The present study was part of a larger program to

assess contamination in various environmental media

from marine environment and adjacent riverine and

estuarine areas of the Bohai Sea and Yellow Sea. The

objectives of the present study were to determine

concentrations, distribution, and fate of PFC in envi-

ronmental matrices and to identify potential sources

and thus provide information for future management

and remediation efforts in the Bohai Sea region.

Materials and methods

Standards and reagents

A mixture of 12 PFC (purity for each PFC [ 98%)

including PFOS, perfluorooctanoate (PFOA), perfluo-

robutane sulfonate (PFBS), perfluorohexane sulfonate

(PFHxS), perfluorodecane sulfonate (PFDS), perflu-

orobutanoate (PFBA), perfluorohexanoate (PFHxA),

perfluoroheptanoate (PFHpA), perfluorononanoate

(PFNA), perfluorodecanoate (PFDA), perfluorounde-

canoate (PFUnA), and perfluorododecanoate (PFDoA)

were obtained from Wellington Laboratories (Guelph,

ON, Canada). The internal standard consisted of PFOA

[1,2,3,4 13C] and PFOS [18O2] (purity for PFOA and

PFOS [ 98%, Wellington Laboratories). HPLC grade

methanol and ammonium acetate were purchased from

J.T. Baker (Phillipsburg, NJ, USA). Analytical grade

sodium thiosulfate was purchased from EMD Chem-

icals (Gibbstown, NJ, USA). Nano-pure water was

obtained from a Milli-Q Gradient A-10 (Millipore,

Bedford, MA, USA).

Study area and sample collection

TBNA (38�400–39�000N and 117�200–118�000E) is

located at the intersection of the Beijing–Tianjin–

Hebei economic zone and the center of the Bohai

Bay Rim city belt, in Eastern Tianjin, China. TBNA

lies in the warm temperate zone, with between

maritime and continental monsoon climate. Mean

annual precipitation is between 520 and 660 mm, and

the average annual temperature is 12�C. Of the three

districts in the TBNA, Tanggu is the most urbanized

and industrialized area followed by Hangu and

Dagang.

Samples consisting of 8 sets of waters, soils, and

sediments, totaling 24, as well as three species of

biota including 21 Crucian carp (Carassius auratus),

302 Environ Geochem Health (2012) 34:301–311

123


11 swimming crabs (Portunus trituberculatus), and

44 prawn (Penaeus semisulcatus) were collected

from Tianjin Bohai Bay during May of 2008 (Fig. 1).

Global positioning (GPS) was used to locate sam-

pling sites, and information on sampling sites was

summarized in Table l. One liter of surface water was

collected by dipping a clean, methanol-rinsed 1-L

polypropylene (PP) bottle just under the surface of

the water. Residual chlorine in water samples was

reduced by adding 200 lL of 200 mg sodium thio-

sulfate/mL. Surface (top 0–10 cm) soil and sediment

samples were collected by use of a clean, methanol-

rinsed stainless steel trowel, then freeze-dried,

homogenized, and passed through a 2.0-mm sieve

in laboratory prior to extraction. Biological samples

were collected by hand-catch or netting from coastal

tidal pools and along the shores of inland water

bodies. Fish were thawed and filleted (skin-on).

Composite samples from each sampling location

were made by combining fillets of several fish before

homogenization. Duplicate samples and field blanks

were collected daily and were analyzed along with

laboratory and procedural blanks. All samples were

Fig. 1 Map showing the sampling locations for water, sedi-

ment, soil, and biota samples collected along Tianjin coast,

China

Table 1 Sampling details including location description and type of samples collected in the present study

Sampling Sample details (# of samples)

Area Riverine Location Geological characteristics Water Sediment Soil Biologicala (# of indiv.)

Hangu Chaobai

River

TB1 Near to high-tech industrial park 1 1 1 3: carp (7), crab (5), and

prawn (21)

Yongding

River

TB2 Near to a reservoir 1 1 1

Yongding

River

TB3 Riverside, abandoned land 1 1 1

Tanggu Yongding

River

TB4 Coastal area, vicinity of oil plant 1 1 1 3: carp (9), crab (6), and

prawn (23)

Haihe River TB5 Sewage drainage, near chem-

industrial plant

1 1 1

Haihe River TB6 Coastal area, inside of harbor 1 1 1

Dagang Duliujian

River

TB7 Coastal area, near to garment

factories

1 1 1 1: carp (5)

Ziya River TB8 Coastal area, near to oil production

plant

1 1 1

No. of location 8 8 8 3

No. of samples 8 8 8 7 (76 individuals)

a Biological samples were collected from the middle of rivers in each area of Hangu, Tanggu, and Dagang, respectively (see precise

locations in Fig. 1, species name in Table 3)

Environ Geochem Health (2012) 34:301–311 303

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stored on ice for transportation and frozen at -20�C

before treatment.

Extraction and cleanup

Water was extracted by solid-phase extraction (SPE)

with Oasis HLB cartridges (Waters Corp., Milford,

MA, 0.2 g, 6 cm3), as described previously (Naile

et al. 2010). Prior to extraction, samples were spiked

with 500 lL of 5 ng/mL internal standard (PFOS

[18O2] and PFOA [1,2,3,4 13C]). After precondition-

ing with 10 mL methanol and nano-pure water, the

cartridge was loaded with 500 mL sample at approx-

imately 1 drop per second. The cartridge was washed

with 5 mL of 40% methanol in water and allowed to

run dry and then eluted with 10 mL of methanol at

the same rate. Eluates were collected and then

reduced to 1 mL under a high purity gentle stream

of nitrogen gas.

Extraction of PFCs in soil and sediment was

accomplished by use of a method similar to that

described by Naile et al. (2010). In brief, 1.0 g of

sample was transferred to a 50-mL PP tube with

10 mL of a 1% acetic acid solution and spiked

with 500 lL of 5 ng/mL internal standard mixtures.

The sample was vortexed and placed in a heated

sonication bath for 15 min at 60�C and then centri-

fuged for 3 min, after which the acetic acid solution

was decanted into a new clean 50-mL PP tube. An

aliquant of 2.5 mL of a 90:10 (v/v) methanol and 1%

acetic acid mixture was added to the original vial,

vortex mixed again, and sonicated for 15 min. This

process was repeated once more, and a final 10 mL

acetic acid wash was preformed. All extracts were

combined in the second tube before being passed

through the SPE cartridge in a similar fashion as

described above in the water extraction procedure.

Animal tissues were extracted using a method

described previously (Naile et al. 2010) that com-

bines an alkaline digestion followed by SPE. Approx-

imately 1.0 g of homogenized tissue sample (dry

powder) was transferred to a 50-mL PP centrifuge

tube and spiked with 500 lL of 5 ng/mL internal

standard, and 30 mL of 0.01 N KOH/methanol was

added to the tube. The mixture was shaken at room

temperature for 16 h. After digestion, 5.0 mL of the

water–tissue mixture was transferred to a new PP

tube and then extracted using SPE cartridges as

previously stated above as water.

Quantitative analyses and quality control

Quantitative analyses were performed by a high-

performance liquid chromatography equipped with an

electrospray tandem mass spectrometer (HPLC–MS/

MS). Quantification was performed using the internal

standard method based on 18O2-PFOS and 13C4-

PFOA as the surrogate. Concentrations of all analytes

in all field and laboratory blanks were less than the

limit of quantification (LOQ), where the LOQ was

defined as 5 times the background signal of the

solvent blank. The MDL was defined as the amount

of chemical which could be detected in a given

amount of sample after the entire method was

preformed. Details of the analytical conditions,

quality assurance, and quality control measures have

been described elsewhere previously (Naile et al.

2010).

Results and discussion

PFC distribution in environmental matrices

and biota

Of the 12 examined analytes, seven were found in

water, sediment, and soil. PFC quantified included

PFOS, PFOA, PFHpA, PFNA, PFDA, PFUnA,

and PFDoA (Table 2). Of the 12 PFC investigated,

PFOS and PFOA consistently occurred at the greatest

concentrations. All water samples contained detect-

able concentrations of PFOS and PFOA, while

PFDoA and PFUnA were found to be ubiquitous

compounds in sediments and soils. As for biological

samples, PFOS was found to be predominant fol-

lowed by PFDA and PFUnA, and no other com-

pounds were detected (Table 3).

PFC in surface water

Concentrations of the sum PFC in surface waters

ranged from 4.4 to 25 ng/L, with the greatest

concentrations observed at location TB5. This loca-

tion, which was near a sewage effluent on the Haihe

River, exhibited the greatest concentrations of PFOS

and PFOA. The dominant compound of the perfluo-

rinated sulfonates (PFSAs) was PFOS with concen-

trations ranging from 0.10 to 10 ng/L. Perfluorinated

carboxylates (PFCAs) were dominated by PFOA with


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concentrations ranging from 3.0 to 12 ng/L. In

general, PFOS and PFOA were the predominant

waterborne PFC accounting for about 77% of the

total PFC (Fig. 2). PFHpA, PFDA, and PFNA were

detected in approximately 70% of the samples

analyzed at concentrations greater than the respective

LOQ values. Concentrations of PFHpA, PFDA, and

PFNA ranged from \LOQ to 2.6 ng/L, \LOQ to

Table 2 Concentrations of PFC in waters, sediments, and soils from Tianjin coast

Items PFOS PFOA PFHpA PFNA PFDA PFUnA PFDoA PFC

Water (ng/L)

TB1 0.74 7.8 0.96 nda 0.22 nd nd 9.8

TB2 0.10 5.0 0.87 2.2 2.9 nd nd 11

TB3 2.4 5.1 0.61 nd 0.27 nd nd 8.4

TB4 3.3 6.6 nd nd 0.32 nd nd 11

TB5 10 12 0.63 1.6 nd nd nd 25

TB6 1.5 4.4 0.54 nd 0.28 nd nd 6.7

TB7 1.6 11 2.6 4.9 3.8 nd nd 24

TB8 0.29 3.0 nd nd 0.63 nd nd 4.4

Sediment (ng/g dw)

TB1 nd 1.5 nd nd 0.95 1.2 0.81 4.4

TB2 nd nd nd nd nd 0.56 0.42 1.5

TB3 0.94 nd nd nd nd 1.1 0.42 2.7

TB4 nd nd nd nd nd nd 0.42 1.5

TB5 4.3 0.81 nd 1.0 0.87 0.55 0.27 7.8

TB6 1.2 nd nd nd nd nd 0.52 1.9

TB7 0.53 nd nd nd 0.44 0.72 0.57 2.8

TB8 2.0 0.94 0.56 nd 2.3 nd 0.38 7.3

Soil (ng/g dw)

TB1 nd nd nd nd nd 0.94 0.26 1.3

TB2 nd nd 0.10 nd 0.84 nd 0.42 2.5

TB3 nd nd nd nd nd 1.0 0.46 2.0

TB4 4.7 0.63 nd nd 0.18 0.82 0.61 7.0

TB5 9.4 0.93 nd nd nd nd 0.26 11

TB6 nd nd nd nd nd 0.57 0.43 1.7

TB7 nd nd nd nd nd 0.54 0.47 1.3

TB8 nd nd 0.10 nd 0.29 0.70 0.39 2.1

a nd: Less than the limit of quantification

Table 3 Concentrations of PFC (ng/g dw) in biological samples from Tianjin coast (the values in bracket indicate the ranges)

Area Species PFOS PFDA PFUnA

Hangu Crucian carp: Carassius auratus 57 (50–65) 1.9 (1.1–2.8) nd

Swimming crab: Portunus trituberculatus 60 (38–82) 1.5 (1.3–1.8) nd

Prawn: Penaeus semisulcatus nd 0.26 (nd–0.42) nd

Tanggu Crucian carp: Carassius auratus 100 (59–240) 1.3 (nd–1.8) nd

Swimming crab: Portunus trituberculatus 11 (nd–18) 0.70 (nd–1.1) 1.6 (nd–2.1)

Prawn: Penaeus semisulcatus 2.8 (nd–4.2) nd nd

Dagang Crucian carp: Carassius auratus 34 (21–46) 1.7 (1.0–2.1) nd


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3.8 ng/L, and \LOQ to 4.9 ng/L, respectively. The

greatest concentrations of PFHpA, PFDA, and PFNA

were all observed at location TB7, on the Duliujian

River in Dagang. This indicates that other PFC, in

addition to PFOS and PFOA, should be considered in

future monitoring and risk assessments.

PFC in sediments

Concentrations of PFC in sediments from TBNA were

generally less than their corresponding MDLs. Total

concentrations of PFC ranged from 1.5 to 7.8 ng/g dw

with a mean of 3.7 ng/g dw. PFDoA was detected in

all samples at concentrations ranging from 0.27 to

0.81 ng/g dw, with a mean of 0.48 ng/g dw. PFOS and

PFOA were observed in fewer samples with concen-

trations ranging from\LOQ to 4.3 ng/g dw and from

\LOQ to 1.5 ng/g dw, respectively. When both were

detected, concentrations of PFOS were generally

greater than those of PFOA. The greatest concentra-

tions of PFOS (4.3 ng/g dw) and corresponding

greater concentrations of PFOA (0.81 ng/g dw) were

observed in sediments from TB5, which was also an

area where some of the greatest waterborne concen-

trations were detected.

PFC in soils

Releases of PFC from various sources not only

contaminate water systems but also do soils. Also,

PFC can be released to the atmosphere and then

precipitated onto soils. PFOS and PFOA can easily

absorb onto sediment and sludge that can be depos-

ited on land (Sinclair and Kannan 2006; Skutlarek

et al. 2006). Thus, soils could be another sink for

PFC. Few studies have previously reported the

occurrence, distribution, sources, and risks of PFC

in soils (Higgins and Luthy 2006; Naile et al. 2010).

In the presented study, PFC concentrations in soils

were generally found to be less than their respective

LOQs. Only 2 sites, TB4 and TB5, exhibited detectable

concentrations of PFOS and PFOA. However, it should

be noted that PFDoA and PFUnA were detected in 100

and 75% of soils, respectively. This was similar to the

rate of detection of PFC in sediments. Total concen-

trations of PFC were in the range of 1.3–11 ng/g dw

with a mean of 3.5 ng/g dw. Concentrations of PFOS

and PFOA in soils ranged from\LOQ to 9.4 ng/g dw

and from\LOQ to 0.93 ng/g dw, while concentrations

of the other two routinely detected PFC, i.e., PFDoA

and PFUnA, were comparable each other with con-

centrations ranging from 0.26 to 0.61 ng/g dw and

\LOQ to 1.0 ng/g dw, respectively.

Concentrations of PFC were found to be within

the similar range between soils and sediments. The

greatest concentrations of total PFC (11 ng/g dw),

PFOS (9.4 ng/g dw), and PFOA (0.93 ng/g dw) in

soils were all observed at location TB5, which is also

the location where concentrations were greatest in

both water and sediment. The result indicated that

local sources of certain PFC near TB5 were evident.

In general, however, soils and sediments in TBNA

Fig. 2 Compositions of PFC in surface water, sediment, and soil collected from Tianjin coast, China


123


contain only small amounts of PFC. In terms of

matrix-dependent accumulation of PFC, the results

of the present study were similar to those observed

previously in South Korea (Naile et al. 2010).

PFC in biota

Concentrations of PFC in aquatic animals from the

TBNA are given (Table 3). Only three compounds,

namely PFOS, PFDA, and PFUnA, were detected

in biota. The result was somewhat different from that

of earlier study by Pan et al. (2010), where PFOA

was detected in biota from other areas of China.

Concentrations of PFOS in Crucian carp were 100,

57, and 34 ng/g dw in three subdistricts of TBNA

with a trend of decreasing concentrations of Tanggu [Hanggu [ Dagang. These concentrations were com-

parable to those previously reported in China and the

Netherlands (Gulkowska et al. 2006; Kwadijk et al.

2010), but generally less than those observed in South

Korea, Japan, Brazil, and Germany (Taniyasu et al.

2003; Quinete et al. 2009; Becker et al. 2010; Naile

et al. 2010). Concentrations of PFDA in Crucian carp

were not significantly different among districts with

1.9 ng/g dw at Hangu, 1.3 ng/g dw at Tanggu, and

1.7 ng/g dw at Dagang. Concentrations of PFOS in

swimming crab and prawn, respectively, were 60 ng/

g dw and\LOQ at Hangu and 11 and 2.8 ng/g dw at

Tanggu, while concentrations of PFDA, respectively,

were 1.5 and 0.26 ng/g dw at Hangu and 0.70 ng/g

dw and \LOQ at Tanggu. PFUnA was detected

only in prawn from Tanggu with a concentration of

1.6 ng/g dw.

Comparison to other coastal areas

When concentrations of PFC were compared to those

in other coastal industrial areas of China and the

world, concentrations of PFOS in waters from the

TBNA were comparable to or greater than those from

the Dalian coast, Hong Kong, Shanghai and Pearl

River Delta (Table 4) and less than those from the

Yangtze River Estuary and the Nanmen River in

Taiwan. Concentrations of PFOA were generally less

than those reported in previous studies (see references

in Table 4). Significantly greater concentrations of

PFOA were observed in waters from the Shanghai

coast in mainland China and the Nanmen River in

Taiwan. Greater concentrations of PFOS and PFOA

were frequently observed in the densely populated

Table 4 Global comparison of PFOS and PFOA concentrations (ng/L) in waters with other studies in coastal areas

Location Year PFOS PFOA Reference

China Tianjin coast 2008 (May) 0.10–10 3.0–12 Present study

Dalian coast 2006 (Oct) nd–2.3 0.17–38 Ju et al. (2008)

Shanghai 2005 (Jan) 0.62–14 22–260 So et al. (2007)

Yangze River estuary 2008 (Nov) 42–700 Na Pan and You (2010)

Pearl River Delta 2003 (Sep) 0.02–12 0.24–16 So et al. (2004)

Hong Kong 2003 (Jun) 0.09–3.1 0.73–5.5 So et al. (2004)

Nanmen River, Taiwan 2009 210–6,100 16–520 Lin et al. (2010)

Japan Tokyo Bay 2004–2006 0.78–17 2.7–63 Sakurai et al. (2010)

Oskas 2003 (Apr) 1.5–28 4.5–560 Saito et al. (2004)

Yodo River basin 2004–2005 0.40–120 4.2–2,600 Lein et al. (2008)

Kyoto 2005 (May) 7.9–110 5.1–10 Senthilkumar et al. (2007)

South Korea Korea coast 2008 (May) 4.1–450 3.0–69 Naile et al. (2010)

Gyeonggi Bay 2004 (Dec) 2.2–650 0.90–62 Rostkowski et al. (2006)

India Southern coast 2008 (Feb) 0.05–3.9 0.05–23 Yeung et al. (2009)

Thailand Chao Phraya River 2006–2007 0.70–18 0.70–64 Kunacheva et al. (2009)

Brazil Guanabara Bay 2008 (Aug) 0.40–0.92 0.70–3.3 Quinete et al. (2009)

Germany German bight 2007 (Aug) 0.69–4.0 2.7–7.8 Ahrens et al. (2009)

Poland Gdansk coast 2005 (May) nd–19 nd–1.1 Rostkowski et al. (2009)


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and/or industrialized zones. Concentrations of PFOS

and PFOA observed in water in the present study

were less than those found in most coastal rivers of

Japan, South Korea, and Thailand, especially in Yodo

River basin in Japan and Gyeonggi Bay of Korea,

while greater than those from the Southern coast of

India, the Guanabara Bay of Brazil, German Bight in

Germany and Gdansk coast of Poland.

Concentrations of PFOS in sediments from TBNA

were similar to those from the Zhujiang River China

(\LOQ to 3.10 ng/g dw) (Bao et al. 2010), but

less than those from the Yangtze River Estuary,

China (72.9–536.7 ng/g dw), Nanman River, Taiwan

(\LOQ to 159 ng/g dw), and Kyoto River, Japan

(\LOQ to 11.0 ng/g dw) (Senthilkumar et al. 2007;

Lin et al. 2010; Pan and You 2010). The maximum

concentration of PFOS in sediments (4.3 ng/g dw)

observed in the present study was greater than

those reported from the Daliao River system, China

(0.37 ng/g dw) (Bao et al. 2009), the Huangpu River,

China (0.46 ng/g dw) (Bao et al. 2010), and the tidal

flat areas of the Ariake Sea, Japan (0.14 ng/g dw)

(Nakata et al. 2006). Concentrations of PFOA in

sediments of this watershed were slightly greater than

or comparable to those of the Daliao River system

(\LOQ to 0.17 ng/g dw), Huangpu River (0.20–0.64

ng/g dw), and Zhujiang River (0.09–0.29 ng/g dw),

China (Bao et al. 2009, 2010), whereas they were less

than those of the Kyoto River (\LOQ to 3.9 ng/g dw)

(Senthilkumar et al. 2007). Concentrations of PFOA

in the present study varied among locations. This

indicates that multiple sources across the estuarine

and coastal areas of the Tianjin Bohai Bay were

present.

Compositions and sources

Samples from the TBNA exhibited different patterns

of relative concentrations of 7 detectable PFC among

water, sediment, and soil (Fig. 2). PFOA was pre-

dominant PFC in water, with a composition of 45%

(TB7 and TB2) to 79% (TB1), followed by PFOS

(1–42%), PFDA (0.3–26%), and PFNA (0.1–20%).

Meanwhile, PFOS was the predominant PFC in

sediment and soil, as well as biota, contributing as

much as 62% (TB6) in sediment and 86% (TB5) in

soil. Greater contributions of PFUnA and PFDoA

were observed in sediment ranging from 5.7 to 41%

and 3.5 to 28%, and in soil ranging from 3–72 and

2–37%, respectively, while concentrations of PFDoA

and PFUnA were less than those of PFOS or PFOA.

This result indicates the existence of potential sources

of PFDoA and PFUnA in the study area.

The ratio of PFOS to PFOA has been applied to

identify potential sources of PFC (So et al. 2004).

The PFOS/PFOA ratios in the present study were

generally less than 1.0, with values ranging from 0.02

(TB2) to 0.87 (TB5) in water. Ratios calculated in our

study were generally consistent with previous find-

ings in Lake Michigan and the Tennessee River in

the United States, and coastal waters of China and

Korea (Hansen et al. 2002; So et al. 2004; Simcik and

Dorweiler 2005). However, the ratios were different

from those reported by Naile et al. (2010) and

Rostkowski et al. (2006), which were typically

greater than 1.0. Simcik and Dorweiler (2005)

described greater concentrations of PFHpA due to

atmospheric deposition to surface waters than from

other sources. Therefore, the ratio of PFHpA to

PFOA was used as a tracer of atmospheric deposition.

This ratio varied among locations with a range of

0.05 (TB5) to 0.24 (TB7) for all water samples, and

the ratio was less than 1.0, but ratios as great as 1.2

were observed in soil at location TB1. The TBNA has

been subjected to anthropogenic influences as a result

of rapid urbanization and industrialization. Thus, the

specific distribution and pattern of relative concen-

trations of PFC indicates an input from industrial

effluent as well as atmospheric deposition.

Relatively greater concentrations of individual

PFC, especially PFOS, in water, sediment, and soil

from location TB5 might have originated from

tributaries of the Haihe River because the watershed

of Haihe River contains a variety of industries,

including chemical and biochemical products manu-

facturing, and receives industrial and domestic

discharges mainly from Tianjing and Beijing, which

are urbanized areas of increasing industrial and

commercial activities.

Bioaccumulation and hazard assessment

A BCF defined as the concentration in fish divided

by the concentration in water was determined from

measured concentrations at each location. Concen-

trations of PFOS in Crucian carp from the Hangu,

Tanggu, and Dagang regions of the TBNA were used

to calculate a district-wide BCF. The mean BCF


123


for fish was 1.2 9 105 with a maximum value of

6.0 9 105 at TB2 and a minimum of 1.0 9 104 at

TB5 with corresponding log BCF values of 4.0–5.8

(Fig. 3). These BCF values were comparable to those

previously reported for the west coast of Korea (log

BCF of 3.2–5.1), the coast of Japan (log BCF of

2.4–4.6), and in Lake Ontario near Toronto, Canada

(log BCF of 3.8–5.1) (Moody et al. 2002; Taniyasu

et al. 2003; Naile et al. 2010), while greater than the

log BCF of 3.0 for a study of rainbow trout conducted

in the laboratory (Martin et al. 2003). This result is

probably due to accumulation from pathways other

than direct accumulation from water. Concentrations

of PFOA were less than the LOQ in all biological

samples. Thus, it can be concluded that PFOA was

not bioaccumulated in biota, which is in agreement

with previously reported studies (Martin et al. 2003;

Quinete et al. 2009; Yeung et al. 2009; Naile et al.

2010).

Since PFC in aquatic media may directly impact the

local ecosystem, a preliminary risk assessment for the

aquatic ecosystem could be performed by comparing

detected PFOS concentrations with the corresponding

water quality benchmark values (Giesy et al. 2010).

Concentrations of PFOS were less than both the criteria

maximum concentration (CMC = 21 lg/L) for acute

exposure and the criteria continuous concentration

(CCC = 5.1 lg/L) for chronic or continuous exposure

for aquatic organisms. Concentrations of PFOS were

also less than the avian wildlife value (AWV = 47 ng/

L) for fish-eating birds (Fig. 3). While the results of

this study indicate little risk, based on concentrations

measured in water, risk of environmental exposure to

PFC cannot be neglected because the accumulation

mechanisms and exposure routes of PFC are different

compared to those of other known POPs. Since

industries such as the semiconductor or optoelectronics

fabricators continue to use PFOS, despite bans on

PFOS use in most consumer products, more toxico-

logical and environmental exposure data would be

required to address the effect of such compound and

class in aquatic environments (Beach et al. 2006).

Acknowledgments This study was supported by the National

Natural Science Foundation of China (No. 41071355), the

Environmental Protection Welfare Program (No. 201009032),

the National S&T Support Program (No. 2008BAC32B07),

and the National Basic Research Program of China (No. 2007

CB407307). The research was partly supported by a Discovery

Grant from the National Science and Engineering Research

Council of Canada (No. 326415-07) and also from the National

Research Foundation (NRF) of Korea Grants funded by the

Korean government (MEST) (Nos. 2009-0067768 & 2010-

0015275). Prof. Giesy was supported by the Canada Research

Chair Program, an at large Chair Professorship at the Depart-

ment of Biology and Chemistry and State Key Laboratory in

Marine Pollution, City University of Hong Kong, the Einstein

Professor Program of the Chinese Academy of Sciences, and

the Visiting Professor Program of King Saud University.

Fig. 3 Bioconcentration

factor (BCF) and adverse

effect concentrations of

PFC in water from TBNA,

China. CMC, CCC, and

AWV for PFOS are given,

respectively, represent

criteria maximum

concentration, criteria

continuous concentration,

and avian wildlife value


123


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