Environment International 42 (2012) 37–46
Contents lists available at ScienceDirect
Environment International
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e n v i n t
Perfluorinated compounds in surface waters from Northern China: Comparison to
level of industrialization
Tieyu Wang a, Jong Seong Khim b, Chunli Chen a, Jonathan E. Naile c, Yonglong Lu a,⁎,
Kurunthachalam Kannan d, Jinsoon Park b, Wei Luo a, Wentao Jiao a, Wenyou Hu a, John P. Giesy c,e,f
a
State Key Lab of Urban and Regional Ecology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
Division of Environmental Science and Ecological Engineering, Korea University, Seoul 136-713, Republic of Korea
Toxicology Centre and Department of Veterinary Biomedical Sciences, University of Saskatchewan, Saskatoon, Saskatchewan, Canada
d
Wadsworth Center, New York State Department of Health and Department of Environmental Health Sciences, School of Public Health, State University of New York,
Empire State Plaza, Albany, NY 12201-0509, USA
e
Department of Zoology and Center for Integrative Toxicology, Michigan State University, East Lansing 48824, MI, USA
f
Zoology Department, College of Science, King Saud University, P. O. Box 2455, Riyadh 11451, Saudi Arabia
b
c
a r t i c l e
i n f o
Available online 4 May 2011
Keywords:
PFCs
Surface water
Occurrence
Sources
Mass flow
Risk assessment
a b s t r a c t
Inclusion of Perfluorooctane Sulfonate (PFOS) in the Stockholm Convention because of its exemptions, has resulted
in increased annual production of PFOS-containing chemicals in China to accommodate domestic and overseas
demands. Accordingly, concern about environmental contamination with perfluorinated compounds (PFCs), such
as PFOS, has arisen. However, little information is available on the status and trends in the distribution, sources or
risk of PFCs in aquatic environments of China. In the present study, forty two surface water samples collected from
five regions with different levels of industrialization were monitored for concentrations of PFCs by use of solid
phase extraction and LC/MS/MS. Mean concentrations (maximum concentration) of PFOA and PFOS, which were
the dominant PFCs, were 1.2 (2.3) and 0.16 (0.52) ng/l for Guanting, 1.2 (1.8) and 0.32 (1.1) ng/l for Hohhot, 2.7 (15)
and 0.93 (5.7) ng/l for Shanxi, 6.8 (12) and 2.6 (11) ng/l for Tianjin, 27 (82) and 4.7 (31) ng/l for Liaoning,
respectively. The greatest concentrations of PFCs (121 ng/l), PFOA (82 ng/l) and PFOS (31 ng/l) were observed in
Liaoning, which might originate from tributaries of the Liaohe River, the most polluted watershed in Northeast
China. While, concentrations of PFCs in the Guanting and Hohhot regions were 3 to 20 fold less than those from
Tianjin and Liaoning. This result is consistent with little contribution of PFCs being released from agricultural and
non-industrial activities. The magnitudes of mass flow for PFOA and PFOS in decreasing order were:
Guantingb Hohhot b Tianjinb Liaoning b Shanxi and Guanting b Hohhot b Shanxi b Tianjinb Liaoning. The larger
mass flows of PFOS were accompanied by relatively larger magnitudes of PFOA. Concentrations of both PFOA
and PFOS in waters from all regions were less than suggested allowable concentrations. However, the relatively
greater concentrations of PFCs in Tianjin and Liaoning suggest that further studies characterizing their sources and
potential risk to both humans and wildlife are needed.
© 2011 Elsevier Ltd. All rights reserved.
1. Introduction
Perfluorinated compounds (PFCs) have been manufactured since
the 1950s, and their unique properties, such as surface activity,
thermal and acid resistance, and water and oil repellency have made
them useful in a number of applications and products (Giesy et al.,
2010). PFCs have been used as surfactants and surface protectors in
carpets, leather, paper, food containers, fabric, and upholstery and as
performance chemicals in products such as fire-fighting foams, floor
polishes, and shampoos (Giesy and Kannan, 2001; Giesy and Kannan,
2002). The high energy carbon–fluorine bond renders PFCs resistant
⁎ Corresponding author. Tel.: + 86 10 62849466; fax: + 86 10 62918177.
E-mail address: yllu@rcees.ac.cn (Y. Lu).
0160-4120/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envint.2011.03.023
to hydrolysis, photolysis, microbial degradation, and metabolism by
vertebrates (Giesy and Kannan, 2001). Concern about PFCs is growing
because they are globally distributed, environmentally persistent,
bioaccumulative, and potentially harmful. Giesy and Kannan were the
first to report the global distribution of these surfactants when they
quantified perfluorooctane sulfonate (PFOS), perfluorooctanoate
(PFOA) and perfluorooctane sulfonamide (FOSA) in extracts of
blood plasma and liver samples from marine mammals, birds, fish,
as well as human blood (Giesy and Kannan, 2001, 2002). Subsequent
studies found PFCs in air (Barber et al., 2007; Chaemfa et al., 2010;
Dreyer, 2009); water (Ahrens et al., 2009; Boulanger et al., 2004;
Hansen et al., 2002; Saito et al., 2003; So et al., 2004; Yamashita et al.,
2004; Yamashita et al., 2005); sediment (Becker et al., 2008; Higgins
et al., 2005; Kumar et al., 2009; Naile et al., 2010), and wildlife
(Delinsky et al., 2010; Giesy and Kannan, 2001, 2002; Giesy et al.,
38
T. Wang et al. / Environment International 42 (2012) 37–46
2006; Houde et al., 2006; Nakata et al., 2006; Shi et al., 2010; Taniyasu
et al., 2003).
Among PFCs, PFOS and PFOA have received a great deal of attention
in recent years. PFOS and PFOA are the terminal degradation products of
several precursors, and these two are the major PFCs that have been
frequently detected in environmental samples, and often occur at the
greatest concentrations. PFOS was recently listed as a “persistent
organic pollutant”, under the Stockholm Convention, but many
exemptions were made, which allow for continued production and
use of some PFCs, especially in China (Wang et al., 2009). Relatively large
amounts of PFCs are manufactured and used in China, especially by the
textile, leather and paper industries (Chen et al., 2009). China begun
large-scale production of PFOS in 2003 with total production of less than
50 t before 2004 (Ministry of Environmental Protection of China, 2008).
Since 2005 annual production of PFOS-containing chemicals has grown
rapidly due to the sharp increase in domestic demand as well as
overseas demands resulting from the restrictions on production of PFOS
in other countries since (Bao et al., 2009).
Given their water solubility and negligible vapor pressure when
dissolved in water, most PFCs can accumulate in aquatic systems and are
readily transported by hydrological processes (Taniyasu et al., 2003;
Yamashita et al., 2005). Water and sediments are considered final sinks
of PFCs and aquatic systems are an important medium for their
transport (Hansen et al., 2002). The Yellow River system, Haihe River
system, and Liaohe River system are the most important water sources
in Northern China. The Haihe River system is the largest catchment in
Northern China with its tributaries spanning from Beijing to Tianjin, two
large municipalities of China. The Yellow River is the second longest
river in China following the Yangtze River, with a total length of
5464 km and meandering across 9 provinces (including Shanxi and
Inner Mongolia). The Liaohe River system, which is located in
Northeastern China, especially in Liaoning province, encompasses a
number of densely industrialized zones, and is recognized as one of the
most contaminated rivers in China (Zhang et al., 2006). These three river
systems eventually empty into the Bohai Sea. The rapid economic
development in this region has brought, and continues to bring about
increasing amounts of municipal, industrial and agricultural wastes into
the Bohai Sea. The environmental quality in the estuarine and nearby
coastal areas has deteriorated by intense industrial and urban activities,
and the Bohai Sea is currently one of the most polluted seas in China (Hu
et al., 2010; Luo et al., 2010; Naile et al., 2010; Wang et al., 2005b).
Some studies have been conducted on the occurrence and
distribution of PFCs in Chinese environments since 2004 (Bao et al.,
2009; Bao et al., 2010; Chen et al., 2009; Chen et al., 2011; Ju et al., 2008;
Liu et al., 2009; Mak et al., 2009; Pan et al., 2010; So et al., 2007; So et al.,
2004). However, previous surveys are limited in their scopes and the
matrices considered, and relatively few studied sources, distribution,
transportation, and potential adverse effects in aquatic environments.
The present study was conducted as a systematic investigation to
trace sources and fates of toxic substances in various environmental
media from adjacent riverine and estuarine areas including the Bohai
Sea of China and the West Sea of Korea. The objectives of the present
study were to determine concentrations, distribution, and transportation of PFCs in aquatic systems in Northern China to identify sources and
potential risks, and thus provide information for future management
and remediation efforts on watersheds in Northern China.
PFOS, perfluorodecane sulfonate (PFDS), perfluorobutyric acid (PFBA),
perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA),
PFOA, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA),
perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid
(PFDoA). HPLC grade methanol and ammonium acetate were purchased
from J.T. Baker (Phillipsburg, NJ, USA). Analytical grade sodium
thiosulfate was purchased from EMD Chemicals (Gibbstown, NJ, USA).
Nano-pure water was obtained from a Milli-Q gradient A-10 (Millipore,
Bedford, MA, USA).
2.2. Water sample collection
Five sub-regions located in Guanting Reservoir, the largest source
of water for Beijing, Hohhot, Shanxi, Tianjin and Liaoning along the
Yellow River, Haihe River, and Liaohe River in Northern China, were
included in the study area (Fig. 1). Levels of industrialization were
determined by use of a comprehensive index that included GDP per
capita, non-agricultural product, non-agricultural employment, and
the degree of urbanization, informationization and dependence on
foreign trade (Cui, 2003). Magnitudes of the index of industrialization
were as follows: Guanting b Hohhot b Shanxi b Tianjin b Liaoning. Forty
two surface water samples were collected from above mentioned
regions including 7 from Guanting Reservoir (G), 8 from Hohhot in
Inner Mongolia (H), 9 from Shanxi province (S), 8 from Tianjin Bohai
Bay (T), and 10 from Liaoning province (L) (Fig. 1). Global positioning
system (GPS) was used to locate sampling sites. Information on
sampling sites was summarized in Table 1.
One liter of surface water was collected from each sampling station
by dipping a clean, methanol-rinsed 1 l polypropylene (PP) bottle just
under the surface of water and the container was rinsed 5 times by
water from the specific location before sample collection. Residual
chlorine in each water sample was reduced by adding 200 μl of
200 mg/ml of sodium thiosulfate solution using a disposable PP
syringe. Sample duplicates and field blanks were collected daily and
kept at least 20% of the samples in duplicate, thus were analyzed along
with laboratory and procedural blanks. All samples were stored on ice
for transport to the laboratory and frozen at − 20 °C until analyses.
2.3. Extraction and cleanup
2. Materials and methods
Water samples were extracted using Oasis HLB solid phase
extraction cartridges (0.2 g, 6 cm3) (Waters Corp., Milford, MA) as
previously reported (Naile et al., 2010; So et al., 2004). Cartridges
were preconditioned by elution with 10 ml of 100% methanol
followed by 10 ml of nano-pure water at a rate of 2 drops a second.
Five hundred milliliters of water was spiked with 500 μl of 5 ng/ml
internal standard (isotopically labeled PFOS and PFOA, PFOS [18O2]
and PFOA [1,2,3,413C]) and then loaded onto the cartridge, at a rate of
1 drop per second. Cartridges were then washed with 5 ml of 40%
methanol in water and allowed to run dry. Eluents were discarded.
Target compounds were eluted with 10 ml of methanol at a rate of 1
drop per second and collected in a 15 ml PP tube. The eluate was then
reduced to 1 ml under a gentle stream of nitrogen, and filtered using a
disposable PP syringe, which had been fitted with a disposable nylon
membrane Millex filter unit (pore diameter 0.2 μm, Whatman,
Maidstone, United Kingdom). Samples were stored and analyzed in
PP auto-sampler vials fitted with PP septa (Canadian Life Science,
Peterborough, ON, Canada).
2.1. Standards and reagents
2.4. Instrumental analysis
PFOA [1,2,3,413C] (N98%, Wellington Laboratories, Guelph, Ontario,
Canada) and PFOS [18O2] (RTI International, N.C., USA) were used as
internal standards. The external standard used for all matrix spikes was
a mixture of 12 PFCs (N98%, Wellington Laboratories) including
perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS),
An HP 1200 high performance liquid chromatography system
(HPLC) by Agilent Technologies was used for separation of all target
analytes. The HPLC was fitted with a Thermo Scientific Betasil C18
(100× 2.1 mm, 5 μm particle size) analytical column, and a guard
column was used for separation of background from analytes in
T. Wang et al. / Environment International 42 (2012) 37–46
39
Fig. 1. Map showing sampling locations in Northern China including Guanting Reservoir (G), Hohhot (H), Shanxi (S), Tianjin (T) and Liaoning (L).
samples. An aliquant of 2 mM ammonium acetate was used as an
ionization aid. Water and methanol were used as mobile phases.
Gradient conditions were: a 300 ml/min flow rate and 10 μl of the
sample was injected, starting with 60% A (2 mM ammonium acetate)
and 40% B (100% methanol). Initial conditions were held for 2 min and
then ramped to 20% A at 18 min, held until 20 min, decreased to 0% A at
21 min, increased to 100% A at 22 min, held until 22.5 min, returned to
initial conditions at 23 min, and finally held constant until 26 min. The
temperature of the column oven was kept constant at 35 °C.
Mass spectra were collected using an Applied Bioscience SCIEX 3000
(Foster City, CA) tandem mass spectrometer, fitted with an electrospray ionization source, operated in negative ionization mode.
Chromatograms were recorded in multiple reaction monitoring mode
(MRM) with a dwell time of 40 ms. The following instrument
parameters were used: desolvation temperature (450 °C), desolvation
(curtain) gas 6.0 arbitrary units (AU); nebulizer gas flow 5 AU; ion spray
voltage −3500 V; and collision gas 12 AU. Optimal settings for collision
energies and declustering potential were determined for each analyte's
MRM transitions. Quantification using these transitions was performed
using Analyst 1.4.1 software (Applied Bioscience, Foster City, CA).
2.5. Quality assurance and control
In order to ensure the accuracy of sampling, extraction, and
analytical procedures, field blanks were collected with each set of
water samples analyzed. Procedural blanks and recoveries were
determined for each set of extractions. Quantification was performed
using the internal standard method based on 18O2-PFOS and 13C4-PFOA,
as the surrogate. To reduce instrument background contamination
arising from HPLC or solvents, a ZORBEX (Thermo Scientific,
50× 2.1 mm, 5 μm particle size) column was inserted directly before
the injection-valve, as adapted from Benskin et al. (2007). All field and
laboratory blanks were less than the limit of quantification (LOQ), which
was defined as 5 times the background signal of solvent blanks. The use
of Teflon coated lab-ware was avoided during all steps of sample
preparation and analysis to minimize contamination of the samples. The
ions monitored, method detection limit (MDL), and matrix spike
recoveries for all the target chemicals are summarized (Table 2).
2.6. Statistical analysis
All statistical analyses were preformed with SPSS Statistics V17.0.
Concentrations below LOQ were assigned as LOQ/sqrt(2) during
summary statistics. Spatial distributions of PFCs were analyzed using
ArcGIS V9.0 software (ESRI).
3. Results and discussion
3.1. Occurrence of PFCs in surface water
Concentrations and relative proportions of PFCs in surface waters from locations with
five different indices of industrialization in Northern China are summarized (Table 3,
Fig. 2). Among the seven detectable PFCs, PFOA and PFOS occurred at the greatest
concentrations in all sub-regions. Respective ranges of concentrations of PFOA and PFOS
were 0.55 to 2.3 ng/l and bLOQ to 0.52 ng/l in Guanting, 0.80 to 1.8 ng/l and bLOQ to
1.1 ng/l in Hohhot, 0.43 to 15 ng/l and b LOQ to 5.7 ng/l in Shanxi, 3.0 to 12 ng/l and 0.09 to
11 ng/l in Tianjin, 2.6 to 82 ng/l and b LOQ to 31 ng/l in Liaoning. Mean concentrations of
PFOA and PFOS in rivers of Northern China were as follows: Guanting (1.2 ng/l)= Hohhot
40
T. Wang et al. / Environment International 42 (2012) 37–46
Table 1
Sampling information including location, flow rate and detailed description.
Flow ratea (m3/d)
Code
Province or city
Riverine
G01
G02
G03
G04
G05
G06
G07
H01
H02
H03
H04
H05
H06
H07
H08
S01
S02
S03
S04
S05
S06
S07
S08
S09
T01
T02
T03
T04
T05
T06
T07
T08
L01
L02
L03
L04
L05
L06
L07
L08
L09
L10
Yanqing
Huailai
Guishui River
Guanting Lake
773 000
383 600
Yanghe River
Sanggan River
2 898 600
1 932 400
Xiaohei River
Dahei River
191 800
1 175 100
a
Hohhot
Shilawusu River
Yellow River
164 400
69 863 000
Lishi
Yellow River
92 301 400
Taiyuan
Fen River
Linfen
Yuncheng
Yellow River
92 301 400
Tianjin
Chaobai River
3 616 400
Yongding River
5 062 900
Haihe River
7 232 800
Duliujian River
Ziya River
Liugu River
2 411 000
3 888 000
792 000
Jinzhou
Xiaoling River
Daling River
2 155 200
3 780 800
Panjin
Liaohe River
4 843 800
Yingkou
Taizi River
2 421 900
Huludao
4 027 400
Characteristics
Sampling date
Natural park and touristic
Orchard and town
Agriculture and touristic
Water treatment pool
River mouth, agriculture
River mouth, agriculture
Dam and bridge
Midstream, agriculture
Upstream, near a industrial
Midstream, agriculture
River mouth, urban and industrial
Midstream, agriculture
Downstream, industrial
River mouth, sewage drainage
Downstream, agriculture
Upstream, agriculture
Midstream, agriculture
Midstream, Touristic
River mouth, agriculture
Upstream, urban and industrial
Midstream, agriculture and urban
Downstream, sewage drainage
Downstream, agriculture
Downstream, urban and industrial
Downstream, industrial
River mouth, coastal, industrial
Midstream, industrial
Downstream, industrial
Downstream, sewage treatment plant
River mouth, coastal, harbor
River mouth, sewage drainage
Downstream, agriculture
Downstream, industrial
River mouth, harbor
Downstream, pre-industrial
Midstream, oil plant
Midstream, chemical industry
River mouth, sewage drainage
Midstream, industrial
River mouth and coastal, harbor
Downstream, industrial
River mouth, coastal, industrial
05/2007
05/2007
05/2007
05/2007
05/2007
05/2007
05/2007
08/2006
08/2006
08/2006
08/2006
08/2006
08/2006
08/2006
08/2006
04/2008
04/2008
04/2008
04/2008
04/2008
04/2008
04/2008
04/2008
04/2008
05/2007
05/2007
05/2007
05/2007
05/2007
05/2007
05/2007
05/2007
05/2008
05/2008
05/2008
05/2008
05/2008
05/2008
05/2008
05/2008
05/2008
05/2008
Data obtained from website of the Ministry of Water Resources of China.
(1.2 ng/l) b Shanxi (2.7 ng/l) b Tianjin (6.8 ng/l) b Liaoning (27 ng/l), and Guanting
(0.16 ng/l)b Hohhot (0.32 ng/l)b Shanxi (0.93 ng/l)b Tianjin (2.6 ng/l)b Liaoning (4.7 ng/
l). Concentrations of PFOS and PFOA in surface waters were directly proportional to the
magnitude of the index of industrialization.
Although PFOS and PFOA were the dominant PFCs found in waters during the
present study, PFHpA, PFDA, PFDoA, and PFHxS were also detected in approximately
60% of samples at concentrations greater than the respective LOQ, but concentrations
of these PFCs were less than those of PFOA and most concentrations of PFOS, except
for the concentration of PFHpA in Liaoning (5.9 ng/l). Concentrations of PFHpA, PFDA,
PFDoA and PFHxS were comparable in Guanting and Hohhot, but less than those in
Shanxi, Tianjin and Liaoning. The greatest concentrations of these PFCs were
observed in Liaoning with maximum concentrations of PFHpA (35 ng/l), PFDA
(5.7 ng/l), PFDoA (0.24 ng/l) and PFHxS (2.3 ng/l). This indicates that other PFCs, not
just PFOS and PFOA, should be considered in future monitoring and risk assessment.
However, it should be noted that the reported concentrations of waterborne PFCs
were based on a single survey, thus temporal variations could not be addressed at this
time. Further studies should investigate the monthly or seasonal variations in PFC
concentrations.
Table 2
Limit of quantification (LOQ), method detection limit (MDL) and matrix spike recovery (MSR) of target compounds.
Analyte
Acronym
LOQ (ng/l)
MDLa (ng/l)
MSR (%)
Detected ratiob (%)
Perfluorobutane sulfonate
Perfluorohexane sulfonate
Perfluorooctane sulfonate
Perfluorodecane sulfonate
Perfluorobutanoic acid
Perfluorohexanoic acid
Perfluoroheptanoic acid
Perfluorooctanoic acid
Perfluorononanoic acid
Perfluorodecanoic acid
Perfluoroundecanoic acid
Perfluorododecanoic acid
PFBS
PFHxS
PFOS
PFDS
PFBA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUnA
PFDoA
0.5
0.1
0.1
0.1
1.0
0.5
0.5
0.5
1.0
0.1
1.0
1.0
1.0
0.2
0.2
0.2
2.0
1.0
1.0
1.0
2.0
0.2
2.0
2.0
94 ± 40
137 ± 15
101 ± 22
101 ± 21
120 ± 19
85 ± 58
103 ± 16
88 ± 25
132 ± 23
93 ± 13
112 ± 22
77 ± 17
0(0)
13(31)
29(69)
0(0)
0(0)
0(0)
26(62)
42(100)
5(12)
26(62)
0(0)
24(24)
a
b
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.
Number of samples detected and % — occurrence in parenthesis given.
T. Wang et al. / Environment International 42 (2012) 37–46
41
Table 3
Concentrations (ng/l) of PFCs in waters from Northern China (the values in bracket indicate the standard errors and ranges).
Location
Guanting
Hohhot
Shanxi
Tianjin
Liaoning
Sample size
7
8
9
8
10
PFOS
PFOA
PFHpA
PFNA
PFDA
PFDoA
PFHxS
∑ PFCs
0.16
1.2
0.06
0.02
0.10
0.11
0.03
1.7
0.93 (0.64, nd–5.7)
2.7 (1.5, 0.43–15)
0.32 (0.12, nd–0.96)
nd
0.07 (0.01, 0.03–0.13)
0.06 (0.02, nd–0.14)
0.78 (0.63, nd–5.8)
4.8 (1.8, 0.55–16)
2.6 (1.2, 0.09–11)
6.8 (1.1, 3.0–12)
0.87 (0.26, 0.37–2.6)
1.1 (0.61, nd–4.9)
1.1 (0.51, 0.06–3.8)
0.10 (0.02 0.05–0.20)
0.01 (0.01, nd–0.06)
13 (2.7, 4.4–25)
4.7 (3.0, nd–31)
27 (10, 2.6–82)
5.9 (3.3, 0.34–35)
0.14 (0.13, nd–1.4)
0.68 (0.56, nd–5.7)
0.03 (0.02, nd–0.24)
0.90 (0.28, nd–2.3)
39 (12, 3.2–121)
(0.08,
(0.23,
(0.04,
(0.01,
(0.03,
(0.04,
(0.03,
(0.36,
nd–0.52)
0.55–2.3)
nd–0.22)
nd–0.06)
0.04–0.23)
nd–0.29)
nd–0.19)
0.75–3.1)
0.32
1.2
0.04
0.02
0.07
0.21
0.02
1.8
(0.12,
(0.12,
(0.02,
(0.02,
(0.02,
(0.01,
(0.01,
(0.15,
nd–1.1)
0.80–1.8)
nd–0.11)
nd–0.14)
0.03–0.18)
0.16–0.27)
nd–0.08)
1.1–2.5)
nd: less than limit of quantification.
Since PFOA and PFOS were the dominant PFCs found in water samples accounting for
over 70% of the total concentrations of PFCs in all study areas and detected in most of the
samples at concentrations greater than the LOQ (Table 2), the subsequent discussion will
be focused on PFOA and PFOS. When compared to values for other regions of China,
concentrations of PFOA in waters from Guanting and Hohhot were comparable to or less
than those from Wuhan, Nanjing, Yichang, Dongguan and Hong Kong, but less than those
from Shanghai and Dalian. Concentrations of PFOA in Shanxi and Tianjin were greater than
those from most Chinese cities, but still less than those from Shanghai (260 ng/l).
Moreover, the concentration of PFOA in Shanghai was higher than those from Liaoning,
which showed the highest concentration of PFOA (82 ng/l) (Table 4, see therein
references). Concentrations of PFOS in waters in Guanting and Hohhot were comparable
to those from Chongqing, Yichang, Nanjing, and Dalian. Concentrations of PFOS in Shanxi
and Tianjin were similar to those from Beijing, Shenyang, Wuhan, Hong Kong and Pearl
River Delta. However, even the greatest concentration of PFOS in Liaoning (31 ng/l) was
less than those from Dongguan (99 ng/l), which has several electronic industries such as
printed circuit boards and electroplating that could be local sources of PFOS.
A comparison of the results obtained in the present study with those of previous
studies conducted in adjacent areas is presented (Table 4). In general, concentrations
determined in this study were greater than those found in offshore waters of Japan and
oceanic samples from the Western Pacific Ocean, Central to Eastern Pacific Ocean and
North Atlantic Ocean (Yamashita et al., 2005). Concentrations of PFOA in Shanxi and
Tianjin were comparable to or less than those detected in coastal waters of Korea
(Yamashita et al., 2005), Kyoto River in Japan (Senthilkumar et al., 2007), and Cooum
River in India (Yeung et al., 2009), but much less than those from the Yodo River basin
(Lein et al., 2008). In the present study, the maximum concentration of PFOA (82 ng/l),
which was measured in Liaoning, was comparable to those observed in coastal areas of
Korea (Naile et al., 2010) including Gyeonggi Bay (Rostkowski et al., 2006), and the
Chao Phraya River in Thailand (Kunacheva et al., 2009), but less than the greatest
concentrations of PFOA (2600 ng/l) measured in the Yodo River Basin (Lein et al.,
2008), which is one of the most polluted areas in Japan. Concentrations of PFOS in
Shanxi, Tianjin and Liaoning were comparable to or less than those reported from South
Korea, Japan, India and Thailand. The maximum concentration of PFOS (31 ng/l) was
measured in Liaoning, which was much less than the greatest concentrations of PFOS
measured in the Yodo River Basin (123 ng/l), Kyoto (110 ng/l) in Japan, and the Korean
coast (450 and 730 ng/l) including Gyeonggi Bay (651 ng/l) in Korea (Table 4, see
references therein).
3.2. Spatial distribution of PFCs in surface water
Spatial patterns of PFOA and PFOS as well as total PFC concentrations in surface
waters from five industrial regions in Northern China were plotted using ArcGis
software (ESRI) (Fig. 3). The greatest concentration of PFCs (3.1 ng/l) was found at
location G02 in Guanting Reservoir, with the highest values of PFOA (2.3 ng/l) and
second highest value of PFOS (0.34 ng/l). That sample was collected from a river
adjacent to the Beixinpu region, which has intensive agricultural activities (orchard and
facility agriculture) with significant pesticide consumption every year (Wang et al.,
2007). Greater concentrations of HCH, DDT and heavy metals were observed in soils
throughout the Guanting area as well (Luo et al., 2007; Wang et al., 2005a), which
suggests local sources of pollution from agricultural run-off. Meanwhile, this catchment
area is the major water source for Beijing and is considered unpolluted with industrial
chemicals. Concentrations of PFOA and PFOS in Guanting Reservoir water are generally
less than those from Shanxi, Tianjin and Liaoning.
The Liaoning region had the greatest total PFC concentrations (121 ng/l) and PFOA
at L06 (82 ng/l), as well as greatest PFOS at L09 (31 ng/l), where one of the largest
chemical industrial areas of China has been since the 1960s. There still exist many oil
refining plants, chemical plants, and smelting plants in this region. In the present study,
Fig. 2. Total concentrations of PFCs and relative compositions in surface waters of Northern China.
42
T. Wang et al. / Environment International 42 (2012) 37–46
Table 4
Comparison of PFOS and PFOA concentrations (ng/l) in waters with other studies in these adjacent areas.
China
Japan
South Korea
India
Thailand
Ocean
Location
PFOS
PFOA
Reference
Guanting
Hohhot
Shanxi
Tianjin
Liaoning
Coastal area of China
Beijing
Dongguan
Chongqing
Yichang
Wuhan
Nanjing
Shanghai
Pearl River Delta
Dalian Coast
Hong Kong
Tokyo Bay
Tokyo Bay
Survey of Japan
Yodo River basin
Kyoto
offshore of Japan
Coastal of Korea
Coastal of Korea
Korea coast
Gyeonggi Bay
Cooum River
Chao Phraya River
Western Pacific Ocean
Central to Eastern Pacific Ocean
North Atlantic Ocean
nd–0.52
nd–1.1
nd–5.7
0.10–11
nd–31
0.02–9.68
1.75–4.09
0.90–99
nd–0.35
0.29–0.61
2.3–5.3
0.33–0.38
0.62–14
0.02–12
nd–2.25
0.09–3.1
12.7–25.4
0.78–17
0.89–5.73
0.4–123
7.9–110
0.04–0.07
0.04–2.53
0.04–730
4.11–450
2.24–651
0.04–3.91
0.7–17.9
0.054–0.078
0.001–0.020
0.009–0.036
0.55–2.3
0.80–1.8
0.43–15
3.0–12
2.6–82
0.24–15.3
5.51–7.85
0.85–4.4
nd–35
4.1–4.9
2.8–5.6
2.1–2.4
22–260
0.24–16.
0.17–37.6
0.73–5.5
154–192
2.7–63
0.97–21.5
4.2–2600
5.12–10
0.14–1.06
0.24–11.4
0.24–320
2.95–68.6
0.9–62
0.04–23.1
0.7–64.3
0.136–0.142
0.015–0.062
0.160–0.338
Present study
Yamashita et al., 2005
Zhao et al., 2007
So et al., 2007
So et al., 2007
So et al., 2007
Jin et al.,2006
So et al., 2007
So et al., 2007
So et al., 2004
Ju et al., 2008
So et al., 2004
Yamashita et al., 2004
Sakurai et al., 2010
Saito et al., 2003
Lein et al., 2008
Senthilkumar et al., 2007
Yamashita et al., 2005
Yamashita et al., 2005
So et al., 2004
Naile et al., 2010
Rostkowski et al., 2006
Yeung et al., 2009
Kunacheva et al., 2009
Yamashita et al., 2005
Yamashita et al., 2005
Yamashita et al., 2005
water samples were collected mainly from the Liaohe River system, which is one of the
most contaminated water bodies in China. The watershed encompasses a number of
densely industrialized zones, which specialize in machinery, electronics, metal refining,
and petroleum and chemical industries (Zhang et al., 2006). The Liaohe River system is
influenced by discharge of sewage from the surrounding cities, and receives about
2 billion t of industrial and domestic wastewater annually (Zhang et al., 2009).
There are significant differences in the types of industries between Shanxi and
Tianjin, with traditional heavy industries such as coking plants and smelting plants in
Shanxi, and high technology industries such as petrochemicals and electronic plants in
Tianjin. The greatest concentrations of PFCs, PFOA and PFOS were found at locations S09
(16 ng/l), S09 (15 ng/l) and S07 (5.7 ng/l) in Shanxi, respectively, which are located
downstream of the rivers including the Yellow River and the Fen River. The results
indicate an increasing concentration from upstream to downstream of the rivers except
for some point sources. The greatest concentrations of PFCs, PFOA and PFOS were
observed at same location T05 with 25 ng/l, 12 ng/l and 11 ng/l in Tianjin, respectively.
This sample was collected from the Haihe River, near a sewage treatment plant;
moreover, the Haihe River receives abundant industrial and domestic wastewater from
nearby cities (Shi et al., 2005; Zhang et al., 2009).
As for Hohhot, the capital city of Inner Mongolia, concentrations of PFCs, PFOA and
PFOS were generally very low, ranging from 1.1 to 2.5 ng/l, 0.80 to 1.8 ng/l, and b LOQ to
1.1, respectively. The greatest concentrations of PFCs (2.5 ng/l) and PFOA (1.8 ng/l)
were observed in location H04. Elevated concentrations of PFOA (1.3 ng/l) and PFOS
(1.1 ng/l) were found in upstream locations (H02 and H03). These sites, located along
the Dahei River, near an emerging industrial zone, were influenced by local sources of
PFOS and PFOA from industrial effluents. In general, the rivers in the Hohhot region
surveyed in this study flow are mostly in grasslands, forests, agricultural and rural
areas. These areas are considered as background areas with less industrialization and
urbanization. Concentrations of PFCs, especially PFOA and PFOS in water from the sites
surveyed in this region were less than those of Tianjin and Liaoning.
enter the Bohai Sea and higher concentrations of PFOS and PFOA were found at sites
T07, L06, L08 and L10 (Fig. 3). Concentrations of PFCs in waters from Guanting and
Hohhot were 3- to 20-fold less than those from Tianjin and Liaoning, which is
consistent with little contribution of PFCs from agricultural and non-industrial
activities.
Some indicators including ratios of PFOS to PFOA and PFHpA to PFOA have been
applied to identify potential sources of PFCs (Simcik and Dorweiler, 2005; So et al.,
2004). The PFOS/PFOA ratios in the present study were generally less than 1.0, but some
samples such as H02 (1.34) from Hohhot, S06 (1.77) and S07 (9.66) from Shanxi, and
L09 (8.86) from Liaoning, exhibited higher PFOS concentrations than PFOA (Table 5),
which is indicative of potential point sources of PFOS. It is noteworthy that above
mentioned sites are close to industrial areas; especially S07 which was collected in the
vicinity of sewage outfall along the Fen River. Ratios calculated in our study are
generally consistent with findings in Lake Michigan and the Tennessee River in the
United States, and coastal waters of China and Korea (Hansen et al., 2002; Simcik and
Dorweiler, 2005; So et al., 2004).
PFHpA was detected in most surface waters (detected ratio: 62%) and in some cases
PFHpA was the dominant PFC in water. PFHpA concentrations ranged from b LOQ to
35 ng/l at L06 in Liaoning. Few studies have reported the dominance of this PFC in
surface waters. However, Simcik and Dorweiler (2005) described relatively higher
concentrations due to atmospheric deposition of PFHpA to surface waters. Therefore,
the ratio of PFHpA to PFOA was used as a tracer of atmospheric deposition. This ratio
varied among regions in Northern China with a range of 0.02 (S09) to 0.99 (L10), for all
water samples the ratio is less than unity indicating that PFOA concentrations exceeded
the PFHpA concentrations (Table 5). This result was expected since there are non
atmospheric sources of PFOA and also PFOS to these surface waters.
The greater concentrations of PFHxS at Shanxi (S07 = 5.8 ng/l), PFNA at Tanjin
(T07 = 4.9 ng/l) and PFDA at Liaoning (L09 = 5.7 ng/l) were consistent with some local
sources of these PFCs, which generally occurred at much smaller concentrations.
3.3. Industrial sources of PFCs
3.4. Mass flow of PFCs
Greater concentrations of PFCs in waters from Tianjin and Liaoning may have
originated from tributaries, of which the Haihe River and Liaohe River are the two
major tributaries. These watersheds contain a variety of industries including chemical
and biochemical product manufacturing, petrochemicals, printed circuit boards,
bleaching, dyeing, pharmaceuticals, electroplating, and fire-fighting foams. The Haihe
River receives industrial and domestic discharges mainly from Tianjing and Beijing,
which are highly urbanized cities with increasing industrial and commercial activities.
The Liaohe River receives industrial and domestic contaminants mainly from Jinzhou,
Huludao, Panjin, Yingkou and Shenyang, the important industrial bases of Liaoning
province, with highly industrialized and urbanized cities. Discharges from these rivers
Riverine transport is the major mode for the transport and mobilization of contaminants
to the sea. Rivers receive the input of treated or untreated sewage effluents and industrial
discharges and agricultural run-off. Estimated mass flows of PFOA and PFOS in rivers in
Northern China are presented (Table 5). For this estimation, the single point measurements of
concentrations were multiplied by average daily discharges of water. The magnitudes of mass
flow for PFOA and PFOS in the five industrial regions in decreasing order were:
Guanting b Hohhotb Tianjinb Liaoningb Shanxi and Guantingb Hohhotb Shanxib Tianjinb
Liaoning.
The mass flow of PFOS generally increased from upstream to downstream in Hohhot,
Shanxi and Liaoning, whereas the increasing mass flow of PFOS was accompanied by a
T. Wang et al. / Environment International 42 (2012) 37–46
Fig. 3. Spatial distribution of PFCs in surface waters of Northern China.
43
44
T. Wang et al. / Environment International 42 (2012) 37–46
Table 5
Parameters for sources, mass flow and potential risk of PFOS and PFOA.
Code
PFOS
PFOA
ng/l
G01
G02
G03
G04
G05
G06
G07
H01
H02
H03
H04
H05
H06
H07
H08
S01
S02
S03
S04
S05
S06
S07
S08
S09
T01
T02
T03
T04
T05
T06
T07
T08
L01
L02
L03
L04
L05
L06
L07
L08
L09
L10
nd
0.34
nd
0.52
0.14
nd
0.15
nd
1.1
0.06
0.30
0.39
0.35
0.25
0.14
0.12
nd
nd
nd
nd
2.3
5.7
0.16
0.15
0.74
3.3
0.10
2.4
11
1.5
1.6
0.29
3.7
nd
nd
4.5
nd
nd
nd
6.7
31
1.4
1.1
2.3
1.2
1.8
0.88
0.68
0.55
1.2
0.82
1.3
1.8
0.99
1.0
1.4
0.80
1.1
0.64
0.43
0.77
3.1
1.3
0.59
1.4
15
7.8
6.6
5.0
5.1
12
4.4
11
3.0
9.1
2.6
2.9
68
72
82
7.8
7.6
3.5
11
Mass flow
Sources indicators
PFOS/PFOA
PFHpA/PFOA
PFOS (g/d)
0.15
0.10
0.1
0.29
0.16
0.11
0.2
0.4
0.27
0.3
1.34
0.05
0.17
0.39
0.35
0.18
0.17
0.11
1.2
0.1
0.4
0.5
0.1
17.4
9.6
10.6
1.77
9.66
0.11
0.01
0.10
0.50
0.02
0.47
0.92
0.34
0.15
0.10
0.41
0.07
0.88
8.86
0.13
0.06
0.10
0.07
0.72
0.12
0.74
0.10
0.33
0.02
0.12
0.06
0.17
0.12
0.05
0.12
0.24
0.12
0.05
0.65
0.12
0.02
0.04
0.43
0.35
0.38
0.46
0.99
decrease in conductivity towards the estuarine mouth (H08, S08, T06 and L10) due to
dilution by the tributary or seawater such as the Yellow River in Hohhot and Shanxi, Bohai
Sea in Tianjin and Liaoning. The larger mass flows of PFOS in H07 (17.4 g/d), S09 (14.0 g/d),
and T05 (75.6 g/d) were accompanied by corresponding larger mass flows of PFOA, due to
local sources from the discharge of sewage drainage and industrial effluents. The larger
mass flows of PFOA at locations H07 (100.8 g/d), S09 (1346.0 g/d), T05 (86.6 g/d), and L04
(257.5 g/d), L05 (273.0 g/d) and L06 (308.9 g/d) can be explained by influences of
different types of sources. Locations H07, T05 and L06 are influenced by the discharge of
sewage, which had the greatest concentrations of PFOA. Locations S09, L04 and L05 are
influenced by industrial effluents (Table 1). A large industrial park is located between
locations L04 and L06, near the city of Jinzhou, which consists of a variety of chemical
factories such as petroleum, textile-coloring and polymer industries. Each facility has its
own wastewater treatment plants, thus, the larger mass flow at location L06 is likely
caused by industrial discharges. Multiple sources of PFCs have been identified, indicating
that they are common and widespread.
3.5. Hazard assessment of PFCs
PFCs have not been regulated in China, however, maximum concentrations to
protect the most sensitive aquatic species have been suggested. Multiple approaches
are available to derive environmental quality values and the most commonly used are
the Great Lakes Initiative guidelines of the USEPA (Sanchez-Avila et al., 2010). The
values are calculated using reported acute and subacute toxicity values of PFOS and
PFOA to aquatic organisms and birds (Giesy et al., 2010). Recently, Giesy et al. (2010)
calculated suggested criteria maximum concentrations (CMC) for the most sensitive
aquatic species, such as Daphnia magna for PFOS (21 μg/l) and PFOA (25 mg/l), and
criteria continuous concentration (CCC) for PFOS (5.1 μg/l) and PFOA (2.9 mg/l), as well
as avian wildlife values (AWV) for PFOS (47 ng/l). An evaluation of the ecological risk to
aquatic animals associated with exposure to PFOA and PFOS was performed by
comparing concentrations in water with the suggested allowable concentrations.
9.2
22.9
14.6
14.0
2.7
12.1
0.5
12.1
75.6
10.5
3.9
1.1
2.9
17.2
32.6
74.8
3.5
Hazard quotient
PFOA (g/d)
0.8
0.9
0.4
0.7
2.5
1.3
1.1
0.2
1.0
1.5
2.1
1.2
0.2
100.8
56.0
102.5
58.8
39.7
71.4
12.4
5.2
2.4
132.3
1346.0
28.2
23.9
25.4
25.8
86.6
31.5
25.6
11.7
7.2
2.0
6.2
257.5
273.0
309.0
37.6
36.6
8.4
25.9
PFOS/AWV
PFOS/CCC
0.007
b0.001
0.011
0.003
b0.001
b0.001
0.003
b0.001
0.023
0.001
0.006
0.008
0.007
0.005
0.003
0.003
b0.001
b0.001
b0.001
b0.001
b0.001
b0.001
b0.001
b0.001
0.049
0.121
0.003
0.003
0.016
0.070
0.002
0.051
0.234
0.032
0.034
0.006
0.079
b0.001
0.001
b0.001
b0.001
b0.001
b0.001
b0.001
b0.001
0.002
b0.001
b0.001
b0.001
b0.001
0.096
b0.001
0.143
0.660
0.030
0.001
0.006
b0.001
PFOA/CCC
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
b 0.001
Concentrations of PFOA and PFOS measured in surface waters in present study (all
ng/l level) were less than the suggested allowable concentrations to protect aquatic life
of wildlife that would consume aquatic organisms. The observed concentrations of
PFOA and PFOS were several orders of magnitude less than their corresponding CMC
values and 150–1000 times less than the CCC values, and avian wildlife guideline values
for PFOS (Table 5). While the results indicate negligible risk to wildlife, based on
concentrations measured in water, several uncertainties on the toxicities of PFCs at less
concentrations exist. More toxicological and environmental exposure data are needed
to address the effects of PFCs on environmental systems (Beach et al., 2006). Also, to
make comparisons between concentrations in organisms associated with adverse
effects, concentration in the blood, liver and or eggs of birds would be necessary since
these are the only values available for which to calculate toxicity reference values
(TRVs) (Newsted et al., 2006; Newsted et al., 2008; Newsted et al., 2007; Newsted et al.,
2005; Yoo et al., 2008).
Acknowledgments
This study was supported by the National Natural Science Foundation
of China under Grant No. 41071355, the National Basic Research Program
of China (“973” Research Program) with Grant No. 2007CB407307, the
National S&T Support Program under Grant No. 2008BAC32B07, and
Environmental Protection Welfare Program under Grant No. 201009032.
Portions of the research were supported by a Discovery Grant from the
National Science and Engineering Research Council of Canada (Project
No. 326415-07) and a grant from the Western Economic Diversification
Canada (Project Nos. 6971 and 6807). Professor Giesy's participation in
the project was supported by the Einstein Professorship Program of the
T. Wang et al. / Environment International 42 (2012) 37–46
Chinese Academy of Sciences. This work was also supported, in part, by
the National Research Foundation (NRF) of Korea Grants funded by the
Korean Government (MEST) (Nos. 2009-0067768 and 2010-0015275).
Finally, we thank the editors and reviewers for their valuable comments
and suggestions.
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