Environmental Pollution 199 (2015) 102e109
Contents lists available at ScienceDirect
Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol
Are levels of perfluoroalkyl substances in soil related to urbanization
in rapidly developing coastal areas in North China?
Jing Meng a, b, Tieyu Wang a, *, Pei Wang a, b, Yueqing Zhang a, b, Qifeng Li a, b,
Yonglong Lu a, John P. Giesy c
a
b
c
State Key Lab of Urban and Regional Ecology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
University of Chinese Academy of Sciences, Beijing 100049, China
Toxicology Centre and Department of Veterinary Biomedical Sciences, University of Saskatchewan, Saskatoon, Saskatchewan, Canada
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 29 September 2014
Received in revised form
18 January 2015
Accepted 20 January 2015
Available online 30 January 2015
Concentrations of 13 perfluoroalkyl substances (PFASs) were quantified in 79 surface soil samples from
P
17 coastal cities in three provinces and one municipality along the Bohai and Yellow Seas. The PFASs
concentrations ranged from less than limitation of quantification (LOQ) to 13.97 ng/g dry weight (dw),
with a mean of 0.98 ng/g dw. The highest concentration was observed along the Xiaoqing River from
Shandong province, followed by that from the Haihe River in Tianjin (10.62 ng/g dw). Among four reP
gions, PFASs concentrations decreased in the order of Tianjin, Shandong, Liaoning and Hebei, which
was consistent with levels of urbanization. Fluorine chemical industries allocated in Shandong and
Liaoning played important roles in terms of point emission and contamination of PFASs, dominated by
perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Intensive anthropogenic activities
involved in urbanization possibly resulted in increasing releases of PFASs from industrial and domestic
sources.
© 2015 Elsevier Ltd. All rights reserved.
Keywords:
PFASs
Soils
Urbanization
Sources
Bohai and Yellow Seas
1. Introduction
Due to many desirable properties such as surface activity,
thermal stability, acid resistance, and amphiphilicity (Kissa, 2001),
perfluoroalkyl substances (PFASs) have been widely used as surfactants and surface protectors in carpets, furniture, paper, food
containers, fabrics, and upholstery. They have also been applied as
performance chemicals in products such as fire-fighting foams,
floor polishes, and shampoos (Giesy and Kannan, 2001). They are
now considered emerging pollutants, whose environmental
persistency, bioaccumulation, global distribution and toxicity
(Conder et al., 2008; Giesy et al., 2010; Schuetze et al., 2010; Zushi
et al., 2010) have raised increasing concerns. PFASs were reported
to be widespread in the environment (Giesy and Kannan, 2001,
2002) and subsequently detected in aquatic systems (Fujii et al.,
2007; Rayne and Forest, 2009) and wildlife (Kannan et al., 2002;
Houde et al., 2006; Fatihah et al., 2009). PFASs in soils can be
transported to the atmosphere, surface water and groundwater
* Corresponding author.
E-mail address: wangty@rcees.ac.cn (T. Wang).
http://dx.doi.org/10.1016/j.envpol.2015.01.022
0269-7491/© 2015 Elsevier Ltd. All rights reserved.
through volatilization, diffusion, leaching and mass flow (Armitage
et al., 2009). Moreover, PFASs can biomagnify and accumulate
through the food chain to wildlife and humans. The adverse effects
of PFASs on ecosystem and human health as well as secondary
release of PFASs from soil are still of long-term public concerns.
Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid
(PFOA), two predominant PFASs frequently detected in the environment, have received great attention in recent years. PFOS and its
salts have recently been listed as “persistent organic pollutants”
(POPs) under the Stockholm Convention. However, exemptions
were made to allow their continued production and use in China
(Wang et al., 2009b). China began large-scale production of PFOS
and related chemicals in 2003. Before 2004, the total production of
PFOS and related chemicals in China was less than 50 tons, whereas
in 2006, fifteen Chinese enterprises produced a total of more than
200 tons with 100 tons exported (Bao et al., 2009).
The coastal and estuarine areas of the Bohai and Yellow Seas,
investigated in the present study, include seventeen coastal cities in
Tianjin, Hebei, Shandong, and Liaoning. The urbanization and
industrialization in the coastal regions are progressing dramatically
along with rapid economic development. These intensive anthropogenic activities have severely deteriorated environmental
J. Meng et al. / Environmental Pollution 199 (2015) 102e109
quality, especially along the coast (Qiu et al., 2009; Tan et al., 2009).
Emerging pollutants such as PFASs have become urgent environmental issues due to their extensive sources, high level of hazard,
and difficulty of monitoring and controlling. Results of previous
studies indicated that emissions of PFOS were greater in more urbanized eastern coastal regions of China (Xie et al., 2013a,b).
Intensive industries including textile, printing and electroplating
have led to releases of PFASs, especially those based on PFOS
(Huang et al., 2010). The fluorine industry parks located in Liaoning
and Shandong provinces have released PFASs (Wang et al., 2013,
2014). Since 2008, we have been conducting systematic research
of organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and heavy metals in environmental matrices along the
Bohai Sea. It was found that industrialization and urbanization
were strongly related to their pollution and distribution (Hu et al.,
2010; Chen et al., 2011; Wang et al., 2011a). The Yellow River, Haihe
River and Liaohe River systems are the most important water
sources in this region, and most of the river systems eventually flow
into the Bohai and Yellow Seas. Rapid economic development has
generated, and continues to generate increasing amounts of
municipal, industrial and agricultural wastes, which eventually
accumulate in the Bohai and Yellow Seas. Bohai Sea is currently one
of the most polluted seas in China (Zhang et al., 2006; Tan et al.,
2009; Luo et al., 2010).
Our previous studies focused mainly on classic persistent toxic
substances (PTS) such as heavy metals, PAHs, and OCPs in soils and
sediments. PFASs in water were also reported (Hu et al., 2010; Luo
et al., 2010; Chen et al., 2011; Wang et al., 2011b; Jiao et al., 2012). In
this study, the concentrations and distribution of emerging pollutants PFASs were determined in soils from coastal and estuarine
areas of the Bohai and Yellow Seas. The relationship between the
PFASs concentrations in soil and the levels of urbanization was also
analyzed. Using a systematic approach, this study may help identify
potential sources of pollutants and provide information for future
management and soil remediation. There are currently very few
studies of PFASs in soil. For the first time, we investigated spatial
distribution and potential sources of PFASs in soil samples taken
from this rapidly developing coastal region.
2. Materials and methods
2.1. Sampling design and collection
The study area included three provinces and one municipality
along the Bohai and Yellow Seas, i.e. Liaoning, Hebei, Tianjin and
Shandong. A total of seventy-nine surface soils were collected from
estuarine and coastal areas adjacent to the Bohai and Yellow Seas,
including twenty-two from Liaoning, nine from Hebei, eight from
Tianjin and forty from Shandong (Fig. S1). Surface (top 0e20 cm)
soil samples were collected using a stainless steel trowel that had
been rinsed with methanol. Each sample was a composite of five
sub-samples (each weighed about 500 g) collected from the center
and four corners of an area of 100 100 m2. Sampling information
including location, land use and detailed description were summarized in Table S1. Samples were then transferred and stored in
clean polypropylene (PP) bags. Duplicates and field blanks were
collected in each city and analyzed with laboratory and procedural
blanks. All samples were dried in air, homogenized with a porcelain
mortar and pestle, sieved with a 2 mm mesh, and stored in
250 mL PP bottles at room temperature until extraction.
2.2. Chemicals and reagents
The detailed descriptions on chemicals and reagents were
available in Supplementary Material.
103
2.3. Extraction and cleanup
PFASs were extracted using methods similar to those described
previously (Wang et al., 2013). Briefly, 2.5 g of sample was transferred to a 50 mL PP tube, and moistened by 2 mL Milli-Q water
with vortexing. Then 1 mL of 0.5 M TBAHS, 2 mL of 25 mM sodium
acetate and 1 ng mass-labeled internal standards (PFOA [1, 2, 3, 4
13
C] and PFOS [18O2]) were added into the PP tube. The mixture was
shaken at 700 r/min for 5 min. Subsequently, 5 mL of MTBE was
added and shaken for 20 min. After centrifuging for 20 min at 3500
r/min, the supernatant MTBE was collected. This process was
repeated twice which produced a final volume of 15 mL MTBE
wash. The supernatant was evaporated to dryness under a gentle
flow of high-purity nitrogen, and reconstituted in 1 mL methanol.
The 1 mL elution was transferred to 50 mL PP tube, brought to
50 mL with Milli-Q water and extracted with the SPE cartridge.
The SPE cartridge was preconditioned with 4 mL of 0.1%
ammonia in methanol, 4 mL methanol and 4 mL Milli-Q water.
50 mL sample was loaded into the cartridge. The cartridge was
washed with 20 mL Milli-Q water, 4 mL of 25 mM sodium acetate,
allowed to run dry, and eluted with 4 mL methanol and 4 mL of 0.1%
ammonia in methanol. The eluents were collected, combined, and
concentrated to 1 mL under a gentle stream of high purity nitrogen
and then filtered through a 0.2 mm nylon filter into a 1.5 mL autosampler vial fitted with PP cap for HPLC analysis.
2.4. Instrumental analysis and quantitation
All PFASs were analyzed using an Agilent HP 1200 high performance liquid chromatography system (HPLC) equipped with an
Applied Bioscience SCIEX 3000 tandem mass spectrometer (HPLCMS/MS). Quantification was performed using Analyst 1.4.1 software
provided by SCIEX. The detailed descriptions on instrumental
Table 1
QA/QC information of 13 PFASs including monitoring transitions (MT), limit of
detection (LOD), limit of quantification (LOQ), matrix spike recovery (MSR) and
detection ratio.
Analyte
MT
LOD
ng/g
LOQ
ng/g
MSR %
Detected
ratioa (%)
Perfluorobutanoic
acid (C4, PFBA)
Perfluoropentanoic
acid (C5, PFPeA)
Perfluorohexanoic
acid (C6, PFHxA)
Perfluoroheptanoic
acid (C7, PFHpA)
Perfluorooctanoic
acid (C8, PFOA)
Perfluorononanoic
acid (C9, PFNA)
Perfluorodecanoic
acid (C10, PFDA)
Perfluoroundecanoic
acid (C11, PFUdA)
Perfluorododecanoic
acid (C12, PFDoA)
Perfluorobutane
sulfonate (C4, PFBS)
Perfluorohexane
sulfonate (C6, PFHxS)
Perfluorooctane
sulfonate (C8, PFOS)
Perfluorodecane
sulfonate
(C10, PFDS)
213 / 169
0.05
0.05
100 ± 5
14 (18)
263 / 219
0.01
0.03
104 ± 3
10 (13)
313 / 269
0.01
0.01
110 ± 3
21 (27)
363 / 319
0.01
0.02
96 ± 6
20 (25)
413 / 369
0.05
0.05
100 ± 11
57 (72)
463 / 419
0.05
0.05
109 ± 2
39 (49)
513 / 469
0.01
0.01
103 ± 7
33 (42)
563 / 519
0.01
0.02
90 ± 4
41 (52)
613 / 569
0.01
0.01
89 ± 4
17 (22)
299 / 99
0.05
0.05
119 ± 4
17 (22)
399 / 99
0.01
0.01
114 ± 8
0 (0)
499 / 99
0.05
0.05
117 ± 2
49(62)
599 / 99
0.01
0.02
86 ± 6
0 (0)
a
Number of samples detected and % e occurrence in parenthesis given.
104
J. Meng et al. / Environmental Pollution 199 (2015) 102e109
analysis were available in Supplementary Material.
2.5. Quality control and quality assurance
For quality control and quality assurance, the use of Teflon
coated lab-ware was avoided during all steps of sample preparation
and analysis to minimize contamination of the samples. Field
blanks, laboratory blanks (including procedural blanks and solvent
blanks) and matrices spiked with the standard solution (2.0 ng/
g dw) were analyzed. Procedural blanks using anhydrous sodium
sulfate in place of soil were analyzed with every set of samples and
solvent blanks using 100% methanol were run every 4e5 samples
to check for carryover and background contamination. Concentrations of all target PFASs in all field and laboratory blanks were less
than the limit of detection (LOD), which was defined as 3 times of
signal-to-noise ratio (S/N). And the limit of quantification (LOQ)
was set as 5 times of S/N. Recoveries of PFASs were determined in
the range from 86 ± 6% to 119 ± 4%. Detailed QA/QC measurements
of PFASs in soil are given in Table 1.
2.6. Statistical analysis
All statistical analyses were performed with SPSS Statistics
V20.0 (SPSS Inc, USA). A statistical distribution test called PeP plots
was carried out to test the normal distribution of raw data in order
to ensure the data sufficient for further analysis (Fig. S2). Spatial
distributions of PFASs were analyzed using ArcGIS V10.0 (ESRI).
3. Results and discussion
3.1. Occurrence of soil PFASs and association with urbanization
P
Levels of PFASs in soils from coastal and estuarine areas with
different urbanization levels along the Bohai and Yellow Seas are
summarized in Table 2. Urban population ratio, GDP per capita and
tertiary industry ratio were collected to reflect the level of urbanization of each city. Higher values of the three indices tended to
represent higher levels of urbanization (Chen et al., 2013).
Commercial products were one of the important domestic sources
of PFASs in cities (Xie et al., 2013a), and the urban population ratio
and GDP per capita could be a surrogate for the extent of usage of
these products. In general, urbanization of Tianjin was apparently
higher than that of the other three regions. Mean concentrations of
P
PFASs in the four regions were as follows: Tianjin (3.55 ng/
g dw) > Shandong (0.93 ng/g dw) > Liaoning (0.52 ng/
g dw) > Hebei (0.09 ng/g dw). Soil samples from Tianjin were
collected from Binhai district, which is one of the important industrial regions with the most rapid development and relatively
greater level of urbanization. Concentrations of other pollutants,
such as heavy metals, OCPs, and PAHs were relatively higher in this
region as well (Luo et al., 2010; Wang et al., 2009a; Jiao et al., 2012).
Among the seven cities in Shandong province, the highest
P
concentration of PFASs was observed in Dongying, with a mean
of 2.60 ng/g dw. The GDP per capita of Dongying ($21,162) was
higher than that of other cities as well. The secondary industry
contributed greatly to the higher GDP of Dongying, while its tertiary industry ratio (24.7%) was smaller as compared to other cities
in Shandong. The local dominant industries, including textile and
papermaking, might be the largest industrial sources of PFASs
(Davis et al., 2007; Xie et al., 2013b). The highest concentration of
P
PFASs (13.97 ng/g dw) in all 79 soil samples was also observed in
Dongying, which further proved the impacts of textile and paperP
making industries. Concentration of PFASs in soils from Binzhou
(0.91 ng/g dw) ranked the second. One of the largest Chinese
chemical plants is situated in Binzhou, which discharges massive
P
pollutants to the environment. Concentrations of
PFASs from
Dongying and Binzhou were only lower than those from the Binhai
district of Tianjin, but higher than those from other cities. As the
second largest city in Shandong province, Qingdao is highly urbanized. The urban population ratio and tertiary industry ratio are
P
as high as 63.1% and 47.8%, respectively. Concentrations of PFASs
in soils of Qingdao were relatively high, with a mean of 0.73 ng/
g dw. Compared with Dongying and Binzhou, secondary industries
contributed a smaller proportion to pollution in Qingdao. However,
intensive human activities possibly resulted in releases of PFASs
from domestic sources such as packing materials, domestic
Table 2
P
Soil PFASs (ng/g dw) and urbanization levels in coastal and estuarine areas of the Bohai and Yellow Seas.
P
Province
City
Type of area
PFASs
Indicator of urbanization
Liaoning
Hebei
Tianjin
Shandong
a
b
c
Dandong
Dalian
Yingkou
Panjin
Jinzhou
Huludao
Total
Qinhuangdao
Tangshan
Total
Binhai
Total
Dezhou
Binzhou
Dongying
Weifang
Yantai
Weihai
Qingdao
Total
Urban
Suburban
Rural
PFOA
PFOS
Total
Urban population
ratio (%)
GDP per capita (USD)
Tertiary industry ratio (%)
0.43(1)a
e
1.26(1)
0.23(1)
0.71(1)
0.33(1)
0.59(5)
0.27(1)
e
0.27(1)
6.15(2)
6.15(2)
0.59(1)
e
0.40(2)
0.22(1)
0.44(3)
e
e
0.41(7)
eb
e
e
e
0.41(1)
0.21(1)
0.31(2)
0.39(1)
0.03(2)
0.15(3)
6.98(1)
6.98(1)
e
0.94(2)
e
0.85(1)
0.33(1)
e
0.34(1)
0.74(5)
0.26(3)
0.12(4)
1.02(2)
0.23(1)
0.68(3)
1.20(2)
0.53(15)
0.23(1)
0.05(4)
0.09(5)
1.82(5)
1.82(5)
0.56(2)
0.95(4)
3.50(5)
0.65(4)
0.48(9)
0.33(2)
0.97(2)
1.11(28)
ndc
nd
0.08
0.05
0.21
0.20
0.10
0.09
nd
0.03
0.41
0.41
0.25
0.58
2.32
0.33
0.14
0.06
0.26
0.63
nd
nd
0.26
nd
0.01
0.11
0.06
nd
nd
nd
1.88
1.88
0.15
0.11
0.10
0.12
0.13
0.11
0.17
0.12
0.30
0.12
1.10
0.23
0.63
0.74
0.52
0.30
0.04
0.09
3.55
3.55
0.55
0.91
2.60
0.59
0.42
0.31
0.73
0.93
43.0
62.5
48.2
66.8
40.5
31.6
5412
15368
7382
12074
5265
3632
35.1
41.5
37.0
22.8
35.1
37.2
41.6
33.5
5221
10529
47.3
31.0
71.7
40206
31.0
30.7
37.7
43.3
52.4
50.1
51.4
63.1
4985
7103
21162
5706
10338
12235
12691
33.9
36.7
24.7
34.5
34.9
37.9
47.8
Sample number in corresponding urbanization gradient.
No sample in corresponding urbanization gradient.
Not detectable, means concentration less than LOQ.
J. Meng et al. / Environmental Pollution 199 (2015) 102e109
wastewater and daily commodities.
In Liaoning province, soils were collected from six cities near the
Bohai Sea. Intensity of urbanization in Dalian was the greatest with
an urban population ratio of 62.5% and a tertiary industry ratio of
41.5%. Dalian is the pioneer city to adopt environmentally friendly
urban planning and strict environmental management. By adjusting industrial structures, heavy-polluting sections are constantly
eliminated and the proportion of chemical industry is decreasing.
P
These activities resulted in lower concentrations of
PFASs in
Dalian when compared with those of other coastal cities in LiaonP
ing. In Liaoning province, the highest concentration of
PFASs
(1.10 ng/g dw) was observed in Yingkou, one main area of the
Liaohe River Basin. As a major water-receiving body, the Liaohe
River system is influenced by sewage from the surrounding cities,
and receives about 2 billion tons of industrial and domestic
wastewater annually (Huang et al., 2012).
In Hebei, soils from Qinhuangdao and Tangshan, had relatively
P
lower concentrations of
PFASs, with mean values of 0.21 and
0.04 ng/g dw, respectively. Although Tangshan is an important industrial city, dominated by the iron and steel industry, its industries
do not cause as much PFAS pollution as the chemical industry.
Generally, higher level of urbanization usually represents a
decreasing industry ratio via the adjustment of industrial structure,
and the pollution of PFASs usually reduces accordingly. Meanwhile,
urban population increases with urbanization leading to domestic
emissions of PFASs. However, the domestic sources of emission
account for only a small proportion (<10%) of the gross sources (Xie
et al., 2013a,b).
3.2. PFASs in soils along the urbanization gradients
P
PFASs varied
Spatial patterns of relative concentrations of
among urban, suburban and rural areas, and among the four reP
gions (Fig. 1). Proportions of PFASs in soils from the urban (39.0%)
and rural (36.4%) areas in Liaoning province were relatively higher
than those in suburban soils (24.6%). Liaoning is an important base
of the northeast traditional industries, currently at the transitional
stage of industrial development. Jinzhou and Huludao have been
two cities with the most intensive chemical industry in China since
the 1960s. There are still oil refining plants, chemical plants, and
smelting plants in these regions (Wang et al., 2011b). PFASs have
Fig. 1. Concentrations of
gradients.
P
PFASs (ng/g dw) in soils along different urbanization
105
been reported with higher concentrations in urban areas than in
rural areas, which indicates that apart from industrial activities,
releases from consumer products in urban areas are potential
sources of PFASs as well (Kim and Kannan, 2007; Ju et al., 2008).
P
Proportion of PFASs in soils from Hebei province was greater
in urban (60.0%), than suburban (26.7%) or rural areas (13.3%), with
mean concentrations of 0.27 ng/g dw, 0.12 ng/g dw and 0.06 ng/
g dw, respectively. Hebei province has been relatively less urbanized than the other three provinces. Most industries are still situated in urban areas, and agricultural nonpoint source is still the
main source in rural areas. Local industries are unlikely to cause
serious pollution of PFASs, while domestic emission is also a main
source comparing with other industrial regions.
P
Concentration of PFASs was the highest (6.97 ng/g dw) in soils
of suburban area of Tianjin and a relatively higher mean concentration of 6.15 ng/g dw was observed in soils of urban area. The
suburban area provides service facilities, e.g. wastewater treatment
plants, for the urban area, and many emerging industrial zones,
especially for the high tech industries. The Tianjin Binhai district is
one of the most important industrial areas in Northern China.
Intensive economic development and urbanization in this area
have severely deteriorated environmental quality (Guo et al., 2011;
Wang et al., 2011b). However, Shandong province exhibited
completely different distribution of PFASs. Rural soils had the
P
highest concentration of PFASs (1.11 ng/g dw, 49.1%), while the
proportions in urban and suburban soils were only 18.1% and 32.7%.
Shandong is one of the fastest developing provinces. After intensive
development of urban areas, more industries are moving from urban to rural and/or suburban areas in order to obtain adequate and
cheaper land and labors. This has led to the industrial emissions of
PFASs, which gradually become the main source of pollution in
rural and suburban areas (Kim et al., 2012).
3.3. PFASs in soils along the coastal and estuarine rivers
For areas along the coastal and estuarine rivers adjacent to the
P
north Bohai Sea, the highest concentration of
PFASs (1.81 ng/
g dw) was observed in soil from Huludao (Fig. 2). The four detected
PFASs, including perfluorononanoic acid (PFNA), PFOA, perfluoroundecanoic acid (PFUdA) and PFOS, had relatively similar
P
concentrations. The second highest concentration of PFASs was
1.26 ng/g dw, which was dominated by PFNA (0.96 ng/g dw). This
site is located in the city of Yingkou and sample was collected from
the estuary of the Liaohe River, which flows through the Bayuquan
district of Yingkou. The Bayuquan district is one of the most rapidly
developing regions in the Liaodong Bay with several large industrial parks. The industries in these parks include textile, chemistry,
machinery, home appliances, etc. Some PFASs may be released in
the production activities.
Soil samples along the five rivers adjacent to the Tianjin coast
P
were severely polluted. Concentrations of PFASs along these river
systems were as follows: Haihe River (6.16 ng/g dw) > Yongding
River (3.83 ng/g dw) > Ziya River (2.07 ng/g dw) > Chaobai River
(1.31 ng/g dw) > Duliujian River (1.27 ng/g dw). Haihe River was
found to be one of the most polluted rivers in terms of PFASs or
other pollutants (Luo et al., 2010; Wang et al., 2009a; Jiao et al.,
2012; Li et al., 2011). The intense pollution was derived from
rapid development of the Beijing-Tianjin metropolitan region,
especially the Tianjin Binhai district. The highest concentration of
P
PFASs (10.63 ng/g dw) was observed in the estuary of the Haihe
River and the Bohai Bay, with a large contribution of 88.15% by
PFOS. The Binhai district has been subjected to anthropogenic influences as a result of rapid urbanization and industrialization. The
P
relatively great concentrations of PFASs indicated an input from
industrial effluent as well as atmospheric deposition. Furthermore,
106
J. Meng et al. / Environmental Pollution 199 (2015) 102e109
Fig. 2. Spatial distributions of sample locations and related concentrations of
the Haihe Watershed contains a variety of industries including
chemical and biochemical products manufacturing, and receives
industrial and domestic discharges mainly from Tianjin and Beijing.
For samples of soils along the coastal and estuarine rivers
adjacent to the south Bohai Sea and Yellow Sea, mainly from
P
Shandong province, the concentrations of
PFASs along the
Xiaoqing River (5.53 ng/g dw), Tuhai River (1.25 ng/g dw), Shahe
River (0.98 ng/g dw) and Jiaolai River (0.98 ng/g dw) were higher
than those along the other 14 rivers. The Xiaoqing, Shahe and Jiaolai
Rivers flow into the Laizhou Bay and contribute greatly to pollution.
The most severely polluted area occurred in the downstream of the
Xiaoqing River, with a concentration of 13.97 ng/g dw. PFOA was
the dominant pollutant and accounted for more than 98.7% of
P
PFASs. PFOA is used as the surfactant in the treatment of paper
and textile and directly causes serious pollution locally. Simultaneous investigation indicated that facilities along the Xiaoqing
River and its tributaries exhibited the greatest emissions of wastes
(Wang et al., 2014; Zhu et al., 2014). However, samples of soil and
other media such as water and sediments could not be collected
directly from the manufacturing facilities to verify the presumed
source of PFOA. Therefore, more research is needed to determine its
exact origin.
3.4. Patterns of relative concentrations of
P
PFASs in soils
P
The compositions of PFASs in soils along the coast and estuary
of the Bohai and Yellow Seas are summarized in Fig. 3. The compositions of the four regions were completely different. Generally,
PFOA and PFOS were the dominant PFASs. Other detected PFASs
were mainly longer-chain perfluorocarboxylic acids (PFCAs),
including PFNA, PFUdA and perfluorododecanoic acid (PFDoA).
P
PFASs (ng/g dw) along coastal and estuarine areas of the Bohai and Yellow Seas.
Longer-chain PFCAs are more easily adsorbed to solids (Higgins
et al., 2005; Li et al., 2010). In Liaoning province, PFNA and PFUdA
P
contributed 39.1% and 30.8% of PFASs, respectively, while PFOS
and PFOA only accounted for 12.9% and 17.2%, respectively. While in
Hebei province, only longer-chain PFCAs such as PFOA, PFNA and
PFUdA, were detected. In this region, releases of PFASs were mainly
from domestic products. In the Tianjin municipal region, PFOS
P
accounted for 53.1% of PFASs. In general, PFOS is derived from
industrial emission, indicating that factories in Tianjin discharged
relatively large amounts of PFOS. In addition, PFOA, PFUdA and
PFDoA accounted for approximately half of the concentration of
P
PFASs. In Shandong province, PFOA (66.3%) and PFOS (13.2%)
P
were the major components of
PFASs, especially PFOA. The
greater detection ratio of PFOA was mainly contributed by pollutants from the Xiaoqing River. Meanwhile, other PFASs were
detected in Tianjin and Shandong, which were released from
different types of industries, especially chemical industry. The difference among the four regions revealed that the pollution was
mainly caused by industrial sources, because there was not much
difference in domestic sources under current urbanization.
In terms of urbanization gradients, the detected PFASs were
mostly consistent in the same region, but the proportions were
distinct among the three gradients of urbanization. Major industries caused the differences among the four regions. The locations of these factories led to the differences among urban,
suburban and rural areas. In Tianjin and Shandong, concentrations
of PFOS decreased from urban, to suburban to rural areas, but
concentrations of PFOA increased along the same gradient. The
trend of PFOS indicated that chemical industry was the primary
source. However, the increased trend of PFOA in Shandong was
mainly caused by the increasing number of papermaking and
J. Meng et al. / Environmental Pollution 199 (2015) 102e109
107
Fig. 3. Compositions of individual PFASs in soils according to urbanization and river.
textile factories.
The most important source of contaminants in soils along rivers
is irrigation with river water. Polluted rivers are likely to increase
the contamination of soils. Thus, investigation of PFASs in soils
could be useful for a long-term, integrative measure of the status of
PFASs in rivers (Naile et al., 2010; Wang et al., 2011b; Meng et al.,
2013). Concentrations of PFASs in rivers are mainly derived from
upstream regions of rivers and surrounding domestic and industrial sources. Transport of PFASs along rivers in Shandong was the
most obvious, which can be exemplified by the variation of PFOA
and PFOS. This indicated the contribution of PFASs from upstream.
Contributions of PFASs from upstream areas in Liaoning, Hebei and
Tianjin were relatively smaller than the surrounding sources.
3.5. PFASs in soils under different land uses
Soil samples were classified into six groups according to land
use, including grain (n ¼ 27), grass (n ¼ 13), barren (n ¼ 18), woods
(n ¼ 11), cotton (n ¼ 7) and fruit (n ¼ 3) (Table S5). Concentrations
P
of PFASs in soils under different land uses showed obvious difP
ference (Fig. 4). In Tianjin, PFASs (6.16 ng/g dw) in barren land
P
were the highest, followed by PFASs in grassland (3.09 ng/g dw).
These barren lands were located in surroundings of factories, so the
P
industrial emissions may be the main contributor.
PFASs in
grassland were detected with much higher levels in Liaoning
P
(0.71 ng/g dw) and Shandong (2.11 ng/g dw). PFASs in grain land
(nd-2.07 ng/g dw) and wood land (nd-2.51 ng/g dw) showed
P
similar levels in the four regions. The relatively low PFASs levels
in most grain lands (with the exception of those from the Haihe
River and the Xiaoqing River) indicated no serious pollution to food
source. Therefore, it is necessary to change the type of land use or
prohibit river irrigation at these sites with relatively high levels of
P
PFASs. Cotton soils and fruit soils were only collected in ShanP
dong. PFASs from the two different lands were 0.93 and 0.42 ng/
g dw, respectively.
4. Conclusion
Fig. 4. Concentrations of
P
PFASs (ng/g dw) in soils under different land uses.
The urbanization and industrialization in the coastal region are
growing dramatically along with the rapid economic development
in China. As a result, emerging pollutants such as PFASs produced in
the processes of production and consumption, have become new
and urgent environmental issues. Plenty of old industrial areas
coexist with rapidly urbanized areas along the coastal region of the
108
J. Meng et al. / Environmental Pollution 199 (2015) 102e109
Bohai and Yellow Seas, which result in increasing pollution of
PFASs. PFASs in soils from Tianjin and Shandong with higher levels
of urbanization showed relatively higher concentrations. With the
development of urbanization, factories are constantly moving from
urban areas to rural areas, which can raise emission of PFASs in
rural areas as well. Rural areas, being important bases for crop
production, deserve more attention. In general, PFOA and PFOS
were the dominant PFASs in the studied area, especially in Tianjin
and Shandong. PFOS was mainly emitted from chemical plants, and
PFOA mainly came from paper-making and textile industries. This
study would provide valuable information for management and
control of the emerging pollutants in the rapidly developing coastal
region. Further detailed work with more intensive sampling effort
over time is recommended to identify any shifts in production to
shorter chained or lesser fluorinated PFASs. Such approach would
help identify trends and sources, and evaluate control measures to
reduce soil and riverine discharge of PFASs into the coastal and
marine ecosystem.
Acknowledgments
This study was supported by the National Natural Science
Foundation of China under Grant No. 41171394 and 41371488, the
National Fundamental Field Study Program with Grant No.
2013FY11110, and the Key Research Program of the Chinese Academy of Sciences under Grant No. KZZD-EW-TZ-12. Prof. Giesy was
supported by the Canada Research Chair Program and the Einstein
Professor Program of the Chinese Academy of Sciences. Finally, we
would like to thank the editors and reviewers for their valuable
comments and suggestions.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.envpol.2015.01.022.
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<Supplemental Materials>
Are levels of perfluoroalkyl substances in soil related to urbanization
in rapidly developing coastal areas in North China?
Tieyu Wang 1*, Jing Meng
1,2
, Pei Wang
1,2
, Yueqing Zhang
1,2
, Qifeng Li
Yonglong Lu1, John P. Giesy3
1. State Key Lab of Urban and Regional Ecology, Research Center for Eco-Environmental
Sciences, Chinese Academy of Sciences, Beijing 100085, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China;
3. Toxicology Centre and Department of Veterinary Biomedical Sciences, University of
Saskatchewan, Saskatoon, Saskatchewan, Canada
* Corresponding author:
* Tieyu Wang
Tel: +86 10 62849466; Fax: +86 10 62918177
E-mail address: wangty@rcees.ac.cn (T. Wang)
1,2
,
Details of materials and methods
Chemicals and reagents
The external standards of 13 PFASs, including perfluorobutanoic acid (PFBA),
perfluoropentanoic
perfluoroheptanoic
perfluorodecanoic
perfluorododecanoic
acid
acid
(PFPeA),
(PFHpA),
acid
acid
perfluorohexanoic
PFOA,
(PFDA),
(PFDoA),
acid
perfluorononanoic
acid
perfluoroundecanoic
acid
perfluorobutane
sulfonate
(PFHxA),
(PFNA),
(PFUdA),
(PFBS),
perfluorohexane sulfonate (PFHxS), PFOS, perfluorodecane sulfonate (PFDS), and
the international standard consisted with PFOA [1, 2, 3, 4
13
C] and PFOS [18O2] had
purities of >98% (Wellington Laboratories, Canada). HPLC grade methanol,
tetrabutylammonium hydrogensulfate (TBAHS), methyl tert-butyl ether (MTBE),
ammonium acetate and ammonium acetate were purchased from J.T. Baker
(Phillipsburg, NJ, USA). Milli-Q water was obtained from a Milli-Q gradient A-10
(Millipore, Bedford, MA, USA).
Instrumental analysis and quantitation
A 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 Aglient ZORBAX Eclipse Plus C18 (2.1×100 mm, 3.5 μm particle size) analytical
column, and a suitable guard column (Agilent 1290 Infinity In-line filter with 0.3μm
SS frit) was used to prevent instrument background contamination. An aliquant of 2
mM ammonium acetate as an ionization aid and methanol were used as mobile phases.
Gradient conditions were used at 300 μl/min flow rate and 10 μl of the sample was
injected, starting with 60% A (2 mM ammonium acetate) and 20% B (100%
methanol). Initial conditions were held for 2 min and then ramped to 20% A at 18 min,
held till 20 min, decreased to 0% A at 21 min, increased to 100% A at 22 min, held
until 22.5 min, returned to initial condition at 23 min, and finally held constant until
26 min. The temperature of the column oven was kept constant at 35 ℃.
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 using a multiple
reaction monitoring mode (MRM) with a dwell time of 40 ms. The following
instrument parameters were used: desolvation temperature (450 ℃), desolvation
(curtain) gas 6.0 arbitrary units (AU); nebulizer gas flow 5 AU; ion spray voltage
-3500 V; and collision gas 12 AU. The optimal settings for collision energies and
declustering potential were determined for each analyte’s transitions. Quantification
using these transitions was performed using Analyst 1.4.1 software provided by
SCIEX (Applied Bioscience, Foster City, CA).
Table S1 Sampling information including location, landuse and detailed description
Site
Province
City
River
Type of area
Landuse
Characteristics
DD1
Liaoning
Dandong
Dayang River
Rural
Grass
Close to wetland, agricultural filed nearby
DD2
Yalu River
Urban
Grain
Small park nearby, Yalu River
DD3
Yalu River
Rural
Grain
Downstream of industrial plants, rice field
DD4
Yalu River
Rural
Barren
Open land for future development
Fuzhou River
Rural
Grass
Changxing Island, yellow soil
DL2
Fuzhou River
Rural
Woods
Women washed cloths nearby, no industry
DL3
Biliu River
Rural
Woods
Sandy soil, no point sources
DL4
Beach
Rural
Grain
Potato field, salt or shrimp ponds nearby
Liugu River
Suburban
Grain
Newly planted corn, lots of trash nearby
HL2
Liugu River
Rural
Grain
Freshly tilled, corn field
HL3
Wuli River
Urban
Grain
Newly planted corn, lots of mining and coal plants nearby
HL4
Beach
Rural
Grass
Close to harbor, on cliff
Xiaoling River
Rural
Grain
Corn field, close to salt/shrimp ponds
JZ2
Xiaoling River
Urban
Grass
Dark brown soil, river flows through Jinzhou City
JZ3
Daling River
Rural
Grain
Daling River, corn field, close to one busy bridge
JZ4
Daling River
Suburban
Grain
Daling River, steel factory nearby, light brown soil, corn field
JZ5
Daling River
Rural
Grain
Mouth of Daling River, lots of oil wells nearby, corn field
Beach
Urban
Grain
Paper plant in the upstream, rice field
Beach
Rural
Barren
Close to open sea
Daliao River
Rural
Woods
Midstream of Daliao River, some large housing projects
Daliao River
Urban
Woods
Mouth of Daliao River, red soil
DL1
HL1
JZ1
PJ1
Dalian
Huludao
Jinzhou
Panjin
PJ2
YK1
YK2
Yingkou
YK3
Erdao River
Rural
Grain
Bayuquan District, chemical plant in the south
Beach
Suburban
Grass
Sandy, long grass covering
QH2
Beach
Urban
Barren
Close to beach
QH3
Qinglong River
Rural
Barren
Sandy, close to a dam
Dou River
Suburban
Grain
Agricultural field, newly tilled, small river nearby
TS2
Shuanglong River
Suburban
Grain
Rice field, soils was turned over, small river
TS3
Shuanglong River
Rural
Barren
Salty soil, no factories
TS4
Luan River
Rural
Barren
Close to harbor, sandy soil
TS5
Luan River
Rural
Barren
Sandy soil
TS6
Luan River
Rural
Grain
Close to highway
Chaobai River
Rural
Barren
Near to high-tech industrial park
TB2
Yongding River
Rural
Woods
Near to a reservoir
TB3
Yongding River
Rural
Barren
Riverside, abandoned land
TB4
Yongding River
Suburban
Barren
Coastal area, vicinity of oil plant
TB5
Haihe River
Urban
Barren
Sewage drainage, near chem-industrial plant
TB6
Haihe River
Urban
Barren
Coastal area, inside of harbor
TB7
Duliujian River
Rural
Barren
Coastal area, near to garment factories
TB8
Ziya River
Rural
Grain
Coastal area, near to oil production plant
Majia River
Urban
Grain
Drinking water source
DZ2
Zhangweixin River
Rural
Cotton
Famous large chemical plant nearby
DZ3
Zhangweixin River
Rural
Grain
Many chemical plants and paper mills in the south
Zhangweixin River
Rural
Barren
Clay soil, lots of biological residues
Majia River
Rural
Cotton
One leather factory in the west
QH1
Hebei
TS1
TB1
DZ1
BZ1
BZ2
Qinhuangdao
Tangshan
Tianjin
Shandong
Binhai New Area
Dezhou
Binzhou
BZ3
Tuhai River
Rural
Cotton
Two factories, a variety of species nearby
BZ4
Tuhai River
Suburban
Woods
There is one domestic wastewater drain
BZ5
Yellow River
Rural
Woods
Sandy soil, no industry nearby
BZ6
Yellow River
Suburban
Grain
Close to Yellow River Ecological Garden
Yellow River
Suburban
Cotton
Plastic mulch
DY2
Yellow River
Suburban
Grain
Mainly green belts on both sides of Yellow River
DY3
Yellow River
Rural
Cotton
Lots of dead plant roots in soil
DY4
Yellow River
Rural
Grass
Located in Yellow River Estuary Wetland, good protection
DY5
Xiaoqing River
Rural
Grass
Sandy soil, large salt field nearby
DY6
Xiaoqing River
Rural
Cotton
Plastic mulch, one large factory nearby
DY7
Xiaoqing River
Rural
Grass
Lots of chemical plants and paper mills
Mi River
Urban
Barren
A scene of desolation nearby
WF2
Mi River
Rural
Grass
Sandy soil, one paper mill in the upstream
WF3
Mi River
Rural
Barren
Lots of chemical plants
WF4
Wei River
Rural
Cotton
Sandy soil, one industrial plant on the east coast
WF5
Wei River
Suburban
Woods
Household garbage on the shore
WF6
Wei River
Rural
Woods
One dam in the upstream
Sha River
Rural
Grain
Salt fields nearby
YT2
Sha River
Rural
Grass
One reservoir in the upstream
YT3
Wang River
Rural
Grain
Local people directly use river water to wash clothes, no pollution
YT4
Wang River
Rural
Grass
There are one factory and one industrial park in the south
YT5
Jie River
Rural
Woods
Lush herbage and poplar, one factory in the northeast
YT6
Jie River
Suburban
Grass
One leather factory nearby, acid smell in the air
DY1
WF1
YT1
Dongying
Weifang
Yantai
YT7
Huangshui River
Rural
Fruit
One reservoir in the upstream, no pollution
YT8
Huangshui River
Rural
Grass
There is one dam in the upstream
YT9
Pingchang River
Rural
Woods
Green belts on both sides of Pingchang River
YT10
Jia River
Urban
Barren
Lots of factories nearby
YT11
Jia River
Urban
Fruit
One dam in the upstream, bad smell in the air
YT12
Jia River
Urban
Fruit
One sewage outlet in the upstream, lots of household garbage
YT13
Wulong River
Rural
Grain
Large fishing and dredging activities
Wuzhu River
Rural
Grain
A variety of crops, no industrial pollution
Duo River
Rural
Grain
One pesticide factory nearby, pesticide pollution
Jiaolai River
Rural
Grain
Chemical plants and leather factories in the north
QD2
Jiaolai River
Rural
Grain
One dam in the upstream
QD3
Moshui River
Suburban
Barren
Barren soil on the river bank
WH1
Weihai
WH2
QD1
Qingdao
Table S2 Concentrations of ∑PFASs in soils along coastal and estuarine rivers of the Bohai Sea (ng/g dw)
Site
DD1
DD2
DD3
DD4
DL1
DL2
DL3
DL4
HL1
HL2
HL3
HL4
JZ1
JZ2
JZ3
JZ4
JZ5
PJ1
PJ2
YK1
YK2
YK3
QH1
PFBA
PFPeA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUdA
PFDoA
PFBS
PFOS
∑PFASs
nda
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.06
nd
nd
nd
nd
nd
nd
nd
0.02
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.07
0.09
0.16
0.47
0.14
0.18
0.50
0.21
nd
nd
0.10
0.17
0.07
nd
0.14
0.40
0.28
0.09
nd
nd
nd
0.28
0.14
nd
0.08
nd
0.43
0.45
0.22
0.16
0.07
nd
0.21
0.13
0.20
0.96
0.34
0.23
nd
nd
nd
nd
nd
nd
0.03
nd
nd
nd
nd
0.02
nd
nd
0.06
nd
nd
nd
nd
nd
nd
0.08
nd
nd
0.15
0.29
nd
nd
nd
0.03
nd
0.26
0.42
0.05
0.37
0.28
0.31
0.39
0.13
nd
0.02
nd
0.15
0.23
nd
0.02
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.04
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.25
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.46
nd
nd
0.06
nd
nd
nd
nd
0.09
nd
0.70
nd
0.40
0.43
0.38
nd
nd
nd
0.34
0.14
0.33
0.59
0.21
1.81
0.87
0.71
1.17
0.41
nd
0.23
0.23
0.88
1.26
1.16
0.39
QH2
QH3
TS1
TS2
TS3
TS4
TS5
TS6
TB1
TB2
TB3
TB4
TB5
TB6
TB7
TB8
DZ1
DZ2
DZ3
BZ1
BZ2
BZ3
BZ4
BZ5
BZ6
DY1
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.03
nd
nd
nd
0.03
0.04
0.04
nd
0.04
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.03
0.02
nd
nd
0.04
0.07
0.04
0.04
0.05
0.02
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.10
nd
nd
nd
nd
0.09
0.10
0.02
nd
nd
nd
0.05
0.06
0.02
0.03
0.05
nd
nd
0.14
nd
nd
nd
nd
nd
nd
nd
0.46
0.41
0.63
0.93
0.26
0.15
0.43
0.26
0.21
0.29
0.05
0.68
1.29
0.40
0.29
0.78
0.34
0.27
0.05
nd
0.05
0.10
nd
nd
nd
nd
0.08
nd
nd
nd
nd
nd
nd
0.06
nd
0.08
nd
0.12
0.06
0.05
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.01
0.06
0.84
nd
0.18
0.06
nd
nd
0.29
0.02
nd
0.04
nd
0.04
0.02
0.04
0.02
nd
nd
nd
0.04
nd
nd
nd
nd
nd
0.07
0.94
0.39
1.01
0.82
nd
0.57
0.54
0.70
nd
nd
0.03
nd
0.04
0.02
0.05
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.26
0.42
0.46
0.61
0.26
0.43
0.47
0.39
nd
nd
nd
nd
0.01
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.05
nd
0.05
nd
0.06
0.05
nd
0.06
0.08
0.06
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.21
0.14
4.74
9.37
0.42
nd
0.16
0.12
0.21
0.12
nd
0.23
0.11
0.07
0.13
0.09
0.07
0.27
0.23
nd
0.05
0.10
nd
nd
0.08
1.26
2.50
2.02
6.98
10.62
1.68
1.25
2.07
0.59
0.44
0.61
0.05
1.30
1.72
0.71
0.57
1.09
0.49
DY2
DY3
DY4
DY5
DY6
DY7
WF1
WF2
WF3
WF4
WF5
WF6
YT1
YT2
YT3
YT4
YT5
YT6
YT7
YT8
YT9
YT10
YT11
YT12
YT13
WH1
nd
nd
nd
nd
nd
0.13
nd
nd
nd
nd
0.12
0.15
0.12
0.13
0.12
0.11
nd
0.10
nd
0.12
nd
nd
nd
0.20
0.12
0.12
nd
0.05
nd
nd
0.07
0.05
nd
nd
nd
0.04
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.03
0.05
nd
nd
nd
0.02
0.03
0.02
0.05
0.02
nd
nd
nd
nd
0.10
0.02
nd
nd
nd
0.01
nd
nd
nd
nd
nd
nd
nd
0.04
nd
nd
nd
0.02
0.05
nd
0.07
0.02
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.02
nd
nd
0.16
0.24
0.18
0.40
1.63
13.30
0.07
0.26
0.60
0.46
0.43
0.15
0.67
0.25
0.11
nd
0.17
0.08
nd
nd
0.09
0.10
0.08
0.12
0.10
0.06
nd
nd
nd
0.06
0.06
0.10
nd
nd
nd
0.07
0.05
nd
0.10
0.07
nd
nd
nd
nd
nd
nd
nd
0.05
nd
0.06
0.07
0.05
nd
nd
nd
0.05
0.03
0.06
nd
nd
nd
0.04
0.02
nd
0.05
0.03
0.02
nd
nd
0.02
0.02
nd
nd
0.02
nd
0.02
0.02
0.06
nd
nd
nd
0.02
0.02
0.04
nd
nd
nd
0.03
nd
nd
0.03
0.02
0.02
nd
nd
nd
0.02
nd
nd
nd
nd
0.03
0.03
0.04
nd
nd
nd
nd
nd
0.02
nd
nd
nd
nd
nd
nd
0.02
nd
0.01
nd
nd
nd
nd
nd
nd
nd
nd
0.01
nd
0.01
0.06
0.06
0.06
nd
0.05
0.06
0.06
0.05
0.05
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.05
nd
nd
0.05
0.18
0.11
0.09
0.08
0.12
0.09
0.06
0.24
0.09
0.14
0.12
0.13
0.14
0.15
0.08
0.15
0.09
0.12
0.10
0.12
0.18
0.12
0.15
0.10
0.12
0.27
0.53
0.35
0.62
1.97
13.97
0.22
0.37
0.89
0.77
0.84
0.44
1.24
0.68
0.43
0.19
0.32
0.29
0.26
0.24
0.21
0.35
0.2
0.67
0.44
0.46
WH2
QD1
QD2
QD3
a
nd
0.13
0.14
nd
nd
nd
0.03
nd
nd
0.03
0.05
0.03
: not detectable, means concentration less than LOQ
nd
0.03
0.05
0.03
0.05
0.25
0.43
0.12
nd
0.06
0.10
nd
nd
0.04
0.04
0.02
nd
0.04
0.04
nd
nd
0.02
0.01
nd
nd
nd
nd
nd
0.10
0.19
0.22
0.10
0.15
0.79
1.11
0.30
Table S3 Concentrations of individual PFASs in soils from 16 coastal cities in the Bohai Economic Rim
Province
City
Liaoning
Dandong
Dalian
Yingkou
Panjin
Jinzhou
Huludao
Total
Qinhuangdao
Tangshan
Total
Binhai
Total
Dezhou
Binzhou
Dongying
Weifang
Yantai
Weihai
Qingdao
Total
Hebei
Tianjin
Shandong
PFBA
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.02
0.05
0.08
0.06
0.09
0.05
PFPeA
PFHxA
PFHpA
PFOA
PFNA
PFDA
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.01
0.03
0.02
0.01
nd
nd
0.01
0.01
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
nd
0.02
0.06
0.01
0.01
0.02
nd
0.04
0.02
nd
nd
0.01
nd
nd
0.02
nd
nd
nd
nd
0.04
0.04
0.01
0.04
0.01
0.01
0.01
nd
0.04
0.01
nd
nd
0.08
0.05
0.21
0.20
0.10
0.09
nd
0.03
0.41
0.41
0.25
0.58
2.32
0.33
0.14
0.06
0.26
0.63
0.19
0.11
0.50
0.17
0.18
0.13
0.20
0.18
0.03
0.05
0.01
0.01
0.05
0.04
0.03
0.02
0.03
0.03
0.05
0.03
nd
0.01
0.03
nd
0.01
nd
0.01
nd
nd
nd
0.18
0.18
0.02
0.02
0.02
0.01
0.02
0.03
0.03
0.02
PFUdA
0.11
0.01
0.13
0.01
0.22
0.28
0.14
0.02
0.01
0.01
0.62
0.62
0.01
0.02
0.01
nd
0.01
0.02
0.03
0.01
PFDoA
PFBS
PFOS
∑PFASs
nd
nd
0.01
nd
nd
nd
nd
nd
nd
nd
0.41
0.41
nd
nd
nd
nd
nd
nd
0.01
nd
nd
nd
0.08
nd
nd
nd
0.01
nd
nd
nd
nd
nd
0.03
0.04
0.05
0.03
nd
nd
nd
0.02
nd
nd
0.26
nd
0.01
0.11
0.06
nd
nd
nd
1.88
1.88
0.15
0.11
0.10
0.12
0.13
0.11
0.17
0.12
0.30
0.12
1.10
0.23
0.63
0.74
0.52
0.30
0.04
0.09
3.55
3.55
0.55
0.91
2.60
0.59
0.42
0.31
0.73
0.93
Table S4 Compositions of individual PFASs (%) in soils according to urbanization and river
Province
Characters
Liaoning
Urban
Suburban
Rural
Total
Urban
Suburban
Rural
Total
Urban
Suburban
Rural
Total
Urban
Suburban
Rural
Total
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
9.5
4.2
4.5
5.2
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.4
0.9
1.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.4
4.2
1.8
2.1
Upstream
Midstream
Downstream
Upstream
Midstream
Downstream
Upstream
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Hebei
Tianjin
Shandong
Liaoning
Hebei
Tianjin
PFBA
PFPeA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUdA
PFDoA
PFBS
PFOS
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
3.3
1.1
0.0
4.2
0.9
1.0
15.2
34.5
16.3
19.2
0.0
28.6
37.5
33.3
9.6
9.1
15.8
11.5
28.6
62.5
69.4
64.9
60.9
0.0
34.9
38.5
100
64.3
37.5
55.6
0.0
0.0
1.1
0.3
9.5
4.2
4.5
5.2
0.0
0.0
0.0
1.9
0.0
0.0
0.0
0.0
0.5
2.6
13.0
5.1
2.4
1.4
1.8
2.1
23.9
65.5
30.2
26.9
0.0
7.1
25.0
11.1
4.7
11.8
39.1
17.5
2.4
0.0
1.8
2.1
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
5.5
8.8
21.7
11.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.9
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
9.5
5.6
2.7
3.1
0.0
0.0
18.6
11.5
0.0
0.0
0.0
0.0
79.7
67.7
6.0
53.0
35.7
12.5
11.7
13.4
0.0
0.0
0.0
0.0
0.0
0.0
0.7
32.7
22.6
2.7
43.8
0.0
0.0
7.1
23.1
12.9
62.2
18.7
0.0
100
0.0
0.0
0.0
0.0
0.0
0.0
0.0
6.5
44.2
64.5
18.9
37.5
0.0
0.0
7.2
0.0
0.0
0.0
0.0
0.0
0.0
7.1
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
16.2
0.0
0.0
0.0
71.4
Shandong
Midstream
Downstream
Upstream
Midstream
Downstream
0.0
0.0
3.9
4.0
8.2
0.0
0.0
0.6
2.7
0.0
0.0
0.0
1.9
2.7
2.0
0.0
1.1
1.3
2.7
2.0
0.0
6.0
74.2
56.0
44.9
0.0
0.0
3.2
6.7
6.1
Table S5 Numbers of soil samples with different land use
Woods
Liaoning
Hebei
Tianjin
Shandong
a
4
1
6
Grass
4
1
8
Grain
12
3
1
11
: no corresponding soil sample in this land use
Cotton
a
7
Fruit
Barren
3
2
5
6
5
0.0
4.5
1.3
2.7
4.1
68.5
24.9
1.3
1.3
2.0
31.5
18.1
1.3
0.0
0.0
0.0
0.0
2.6
5.3
6.1
0.0
45.3
8.4
16.0
24.5
Fig. S1 Sampling sites for surface soils in coastal and estuarine areas of the Bohai and Yellow Seas
Fig. S2 Result of normal distribution test for concentrations of ∑PFASs in 79 soils