Perfluorinated Compounds in Surface Waters Industrialization

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Perfluorinated Compounds in Surface Waters
from Northern China: Comparison to Level of
Industrialization
Tieyu Wang
Research Center for Eco-environmental Sciences,
Chinese Academy of Sciences
Nov. 13-17, 2011
Perfluorinated Compounds (PFCs)
• Compounds with C-F bond. C-F bond is the
strongest of known covalent bonds.
• Perfluorinated compounds (PFCs) are fully
fluorinated, and are all anthropogenic.
• However, Total production of carboxylated and
sulfonated PFCs is unknown.
• Relatively large amounts of PFCs are
manufactured and used in China, especially by
the textile, leather and paper industries.
Perfluorinated Compounds (PFCs)
• PFOS was listed as a POPs under the Stockholm
Convention in 2009, but with many exemptions.
• Recently, Annual production of PFOS-containing
chemicals has grown rapidly in China, due to
domestic and oversea demands.
• PFOS and PFOA have received a great deal of
attention, which are the terminal degradation
products of several precursors,
• and they have been frequently detected in
environment with higher concentrations.
Applications of PFCs
Adhesives: Wetting agents
Antifogging: Glass surfaces
Antistatic agents: Microchip manufacture
Cleaners for hard surfaces: Floor Polishes
Coatings: Paint additives, waxes
Cosmetics: Hair-conditioning
Electronics: Insulators, microchips
Electroplating: Chromium, copper and nickel
Fire-Fighting Foams: Formulated to float on flammable
liquids
Herbicides and Insecticides: Wetting agents
Leather: Provide water and oil repellency
Paper: Oil and water repellency
Textiles: Polyester etc. to impart soil, oil and water
repellency.
Major use is in carpeting.
Production and Survey in China
PFCs in Water of China
Rivers of China
Groundwater
Tap water
Sample Locations
Level of Industrialization
Guanting
Reservoir, limited
development
Hohhot, Inner
Mongolia, grassland
and agriculture,
lower development
Shanxi, Fenhe
River, fossil fuel,
coal, extensive
industrial
Guanting<Hohhot<Shanxi
Tianjin, Haihe
<Tianjin<Liaoning River, fossil oil
Liaoning, chemical
and smelt industry,
heavy industrial
and high-tech
industrial
A integrated index: included GDP per capita, non-agricultural
product, non-agricultural employment, degree of urbanization,
informationization and foreign trade
Sample collection
Guanting Lake, Yanghe River and
Guishui River
Dahei River, Xiaohei River and
Shilawusu River
Fenhe River and Yellow River
Haihe River system
Liaohe River system, Daling River
Why Monitoring?
 to determine concentrations, distribution,
and transportation of PFCs in aquatic
systems in Northern China
 To establish baseline environmental
concentrations for identifying sources and
potential risks
 To provide information for future
effectiveness of control measures
PFCs in Water from Northern China
PFCs in Water from Guanting
Concentrations of PFOA and
PFOS were 0.55 to 2.3 ng/l
and <LOQ to 0.52 ng/l in
Guanting area.
PFCs in Water from Hohhot
Concentrations of PFOA and
PFOS were 0.80 to 1.8 ng/l
and <LOQ to 1.1 ng/l in
Hohhot.
PFCs in Water from Shanxi
Concentrations of PFOA and PFOS were 0.43 to 15 ng/l and
< LOQ to 5.7 ng/l in Shanxi.
The higher concentrations of PFCs were found at
downstream of the rivers , indicating an increasing
concentration from upstream to downstream.
PFCs in Water from Tianjin
Concentrations of PFOA and PFOS were 3.0 to 12 ng/l and
0.09 to 11 ng/l in Tianjin.
T05 from the Haihe River, near a sewage treatment plant
PFCs in Water from Liaoning
Concentrations of PFOA and
PFOS were 2.6 to 82 ng/l and
<LOQ to 31 ng/l in Liaoning.
PFCs in Water from Northern China
Locat
Samp
Guanting
7
Hohhot
8
Shanxi
9
Tianjin
8
Liaoning
10
PFOS
0.16±0.08 0.32±0.12 0.93±0.64
2.6±1.2
4.7±3.0
PFOA
1.2±0.23
6.8±1.1
27±10
1.2±0.12
2.7±1.5
PFHpA 0.06±0.04 0.04±0.02 0.32±0.12 0.87±0.26
PFNA 0.02±0.01 0.02±0.02
nd
5.9±3.3
1.1±0.61 0.14±0.13
PFDA 0.10±0.03 0.07±0.02 0.07±0.01 1.1±0.51 0.68±0.56
PFDoA 0.11±0.04 0.21±0.01 0.06±0.02 0.10±0.02 0.03±0.02
PFHxS 0.03±0.03 0.02±0.01 0.78±0.63 0.01±0.01 0.90±0.28
∑PFCs
1.7±0.36
1.8±0.15
4.8±1.8
13±2.7
39±12
Comparison with Other Studies in China
Location
Guanting
Hohhot
Shanxi
Tianjin
Liaoning
PFOS
nd-0.52
nd-1.1
nd-5.7
0.10-11
nd-31
PFOA
0.55-2.3
0.80-1.8
0.43-15
3.0-12
2.6-82
Reference
Coastal area of China
0.02-9.68
0.24-15.3
Yamashita et al., 2005
Beijing
Dongguan
Chongqing
Yichang
Wuhan
Nanjing
Shanghai
Pearl River Delta
Hong Kong
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
0.09-3.1
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
0.73-5.5
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
So et al., 2004
Present study
Comparison with Studies in Adjacent Countries
China
Location
Guanting
Hohhot
Shanxi
Tianjin
Liaoning
PFOS
nd-0.52
nd-1.1
nd-5.7
0.10-11
nd-31
PFOA
0.55-2.3
0.80-1.8
0.43-15
3.0-12
2.6-82
Tokyo Bay
12.7-25.4
154-192
South
Korea
India
Survey of Japan
Yodo River basin
Coastal of Korea
Korea coast
Cooum River
0.89-5.73
0.4-123
0.04-730
4.11-450
0.04-3.91
0.97-21.5
4.2-2600
0.24-320
2.95-68.6
0.04-23.1
Thailand
Chao Phraya River
0.7-17.9
0.7-64.3
Japan
Reference
Present study
Yamashita et al.,
2004
Saito et al., 2004
Lein et al., 2008
So et al., 2004
Naile et al., 2010
Yeung et al., 2009
Kunacheva et al.,
2009
General Conclusions
 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.
 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 are
needed.
PFCs in Estuarine and Coast of North Bohai Sea
Heavy polluted areas, North Bohai
Bay, especially Liaoning Province
Sample Collection and Treatment
Type
Amount
Water
36
Sediment
35
Soil
31
Biota
25
FB
12
PFCs in Water from North Bohai Bay
PFCs in Sediment from North Bohai Bay
PFCs in Soil from North Bohai Bay
PFCs in Biota from North Bohai Bay
Potential Ecological Risk to Aquatic Animals
General Conclusions
 Significant concentrations of PFCs were found in
water (mean: 18.4 ng/l) and biological samples (fish:
265 ng/g dw).
 While concentrations of PFCs in soils and sediments
were less.
 The predominately detected compound was PFOS,
with a maximum of 30.9 ng/l in water and 791 ng/g dw
in fish.
 PFCs were significantly greater in Liaohe River
system, which suggests point sources in this urbanized
and industrialized region.
 PFOS concentrations in water and biota were both less
than the reported threshold concentrations.
Acknowledgements
 Dr. John Giesy, Professor and Canada Research Chair
from University of Saskatchewan for assistance in
sample analyzing.
 Dr. Jong Seong Khim of Korea University for
collecting sample in 2008.
 Dr. Kannan K., Professor of State University of New
York at Albany for collecting sample in 2006.
 Special thanks give to KC Wong Education
Foundation for supporting my travel and expense of
this conference.
 Funding from the National Basic Research Program of
China.
Dr. Tieyu Wang
Environmental Management and Policy Group
State Key Lab of Urban and Regional Ecology
Research Center for Eco-Environmental Sciences, CAS
Tel:86-10-62849466; E-mail:wangty@rcees.ac.cn
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