STATUS AND TRENDS OF CONTAMINANTS
IN BOHAI BAY AND THE YELLOW SEA:
AN INTERNATIONAL PERSPECTIVE
JP Giesy1-3, Y.L. Lu 4, T. Wang4, W. Luo4, J.
Park5, J.S. Khim5
1Dept.
Biomedical Veterinary Sciences and Toxicology Centre, University of Saskatchewan, Saskatoon,
Saskatchewan, Canada
2 Department of Biology and Chemistry, and State Key Laboratory in Marine Pollution, City University
of Hong Kong, Kowloon, Hong Kong, SAR, PR China
3 School of Biological Sciences, University of Hong Kong, Hong Kong, SAR, PR China
4 Research Center for Eco-environmental Science, Chinese Academy of Science, Beijing, PR China
5 School of Earth and Environmental Sciences, Seoul National University, Seoul, South Korea
7TH INTERNATIONAL CONFERENCE ON
MARINE POLLUTION AND ECOTOXICOLOGY
Hong Kong, 17-21 June, 2013
City University
of Hong Kong
Affiliations- Thanks for the support
Professor & Canada Research Chair
University of Saskatchewan
Emeritus Distinguished Professor of Zoology
Michigan State University
Honorary Professor, School of Biological Sciences
University of Hong Kong
Chair Professor at Large, Dept. Biology and Chemistry
City University of Hong Kong
Concurrent Professor, School of the Environment
Nanjing University
Guest Professor
Xiamen University
Support
 Marine Pollution Conference
 Canada Research Chair program
 Program of 2012 "High Level Foreign Experts"
(#GDW20123200120) funded by the State Administration of
Foreign Experts Affairs, the P.R. China to Nanjing University
 Einstein Professor Program of the Chinese Academy of
Sciences
 Visiting Distinguished Professorship in the Department of
Biology and Chemistry and State Key Laboratory in Marine
Pollution, City University of Hong Kong
International Collaboration
Recent Publications from
Pollution Study of Yellow Sea
AECT-2010
59:71-79
EP-2011
159:907-917
EP-2012
171:216-225
C&E-2011
27:165-176
EST-2012
46:1406-1411
EP-2010
158:1237-1244
BECT-2011
87:74-79
EGH-2012
34:301-311
AMBIO-2010
39:367-375
TEC-2011
3:59-68
MPB-2011
62:1905-1914
EI-2012
42:37-46
C&E-2010
26:339-352
EST-2011
45:7481-7488
EGH-2012
34:445-456
International Publications from the Yellow Sea Study
17 Journal Articles (SCI) since 2010
HERA-2011
17:1279-1291
CHEM-2013
90:387-394
Recognition: Highly Cited Recent Works
•Recent 5 papers have been cited >20 times each
1) PFCs reported in multimedia from Korea
2) Review: Aquatic Toxicology of PFCs
3) Health risk of PBDEs & metabolites
4) Chronic exposure of ibuprofen to organisms
5) PFCs reported in marine organisms in Korea
published in
EP
10
RECT
10
EST
10
AT
10
AECT
09
times cited
38
28
24
22
20
Recently published 5 papers are collectively cited over 130 times
during the last 2 years
Outline
1
Research
Overview
2 Marine Ecosystem
Study
Research
3
Highlights
• Research Area
• Activities
• Yellow Sea
• Viewpoints
• Approach
• Taean Oil Spill
• Topics
4
Activities
5
Future
Summary
Challenges
• Research Efforts
• Something New?
• Perspectives
• Promising?
• Goals & Vision?
Overview: Viewpoints
Marine Ecosystem Study
benthicbenthic
pelagic
flora
coupling
natural
Who?
Where?
When?
ecosystem
sediment
health
Interdisciplinary
aspect
benthos environ
aspect
zonation
benthic
interaction
fauna
What?
How?
Why?
science
managevs.
policy
ment
Overview: Topics
Aspect of Marine
Benthic flora
Organisms
Benthic fauna
(since 2002)
(since 2003)
• species composition
• species composition
• biogeography
• zonal distribution
• benthic-pelagic coupling
• ecological modeling
• tidal resuspension
• community structure
• primary production
• community change
Studies of Marine
Benthic Ecology
• sediment properties
• bioaccumulation
• sediment organics
• community responses
• sediment inorganics
• benthic re-colonization
• material fate and flux
• ecol-risk assessment
• sediment assessment
• marine protected area
Sediment (water) quality
(since 1998)
Aspect of Marine
Benthic response
(since 2009)
Benthic Environments
Marine Ecosystem Study: Approach
Marine Ecosystem Study
Chemistry
Ecology
Toxicology
Community indices
Instrumental analyses using
LC (PFCs, Hormones)
GC (PAHs, APs, BPA)
HRGC (PCDD/DFs, co-PCBs, PBDEs)
CIC (Total F)
ICP-MS & AA (heavy metals)
Synchrotron (organics or metals)
=
>
<
Natural
Sciences
cooperation
Social
Sciences
Bioassays using
Dioxin-like activities (HII4E-luc)
Estrogenicity (MVLN)
Steroidogenesis (H295R)
Mutagenicity (Mutatox®)
Other in vivo tests
(microorganisms, fish, bivalve etc.)
Policy
Studies
cooperation
Yellow Sea Study
Exposure Assessment of Trace Pollutants
Yellow Sea
Launched in 2007
•analyzed Korea & China samples
•river and estuarine locations
•water, soil, sediment, biota samples
•>50 locations and >200 samples
Main Targets
•metals
•trace organic pollutants
•in vitro bioassays
•benthic community responses
11
Marine Ecosystem Study: Activities
Marine Ecosystem Study
Research
in Estuaries and Open Ocean
Research
in Tidal flats
Chemical-Pollution Study
Macrozoobenthos Study
Remote Sensing Study
Microphytobenthos Study
Synchrotron Study
Macroalgae Study
Yellow Sea Study
Distribution & Fate of PCDD/Fs
13
Yellow Sea Study
Distribution & Sources of PCDD/Fs
14
Taean Study: Threatening our Ecosystem
ghost shrimp
bird
sea urchin
starfish
15
dolphin
Taean Study
Chemistry-Toxicology-Ecology: Combined
16
Taean Study: Summary
In vitro response (%-TCDDmax)
Two years after the Hebei Spirit oil spill, Taean, South Korea
Potential Toxic Effects of
Oil-contaminated Sediments
More toxic?
Dose-dependent
increase
Batillaria spp.
∑PAHs (log ng g-1 dry weight)
17
Visual Sign of Recovery
in Benthic Community Responses
Research Highlights: Taean Oil Spill
Part-I
Part-II
18
PBDEs, OH-BDEs and MeO-BDEs
in Liaodong Bay
19
Sampling Locations
样品名
short-necked
clam
Mactra
quadrangularis
Invetebrate
rock shell
Chinese
mitten-handed
crab
mole cricket
redeye mullet
goby
Small yellow
croaker
China anchovy
Fish
Japanese
spanish
mackerel
half-smooth
tongue-sole
Spotted maigre
Liaodong Bay
:sediment;
:fish; :bird
Black spotfed
bass
flathead fish
Bird
black-tailed
gull
black-headed
gull
n
3
3
3
3
3
3
3
3
3
3
3
3
3
3
7
16
Biota
samples in Liaodong Bay
：
黄姑鱼
鲅鱼
鲈鱼
黑尾鸥
舌鳎
Homeotherm
鲬鱼
梭鱼
小黄鱼
红嘴鸥
蝼蛄虾
四角蛤蜊
脉红螺
中华绒螯蟹
白蛤
浮游植物
鳀鱼
鰕鯱鱼
浮游动物
Major organisms
collected in Liaodong Bay
Trophic levels
Trophic levels of fish and
invertebrates

Tlconsumer = 2 ＋ (δNconsumer–δNclam )/3.8
Trophic levels of birds

δ Nbird = δ Nconsumer ＋ 2.4

TLbird = 3 + (δNbird - 2.4 - δNclam ) /3.8
TL of invertebrates: 1.12-3.14
TL of fish: 1.93-3.41
TL: Trophic levels
TL of bird: 2.77-4.15
Conc. (pg/g lw)
Trophodynamics of OH-PBDEs
2’-OH-BDE68
6-OH-BDE47
TLs
OH-PBDEs exhibited trophic dilution in the food web
Conc. (pg/g lw)
Trophodynamics of MeO-PBDEs
2’-MeO-BDE68
6-MeO-BDE47
TLs
No significant trophic magnification of MeO-PBDEs
were observed in the food web
Occurrences in Sediments
310 pg/g dw
BDE209
Concentrations of
tri-hepa PBDEs were
< detection limits.
Concentrations of
BDE209:
0.40±0.15ng/g dw,
which is less than
those in other areas
of Bohai (1.75-15.1
ng/g dw)
Comparison with other areas worldwide
Areas
n
∑PBDEs
BDE209
References
Liaodong Bay, China
23
nd
0.40±0.15
The present study
Zhujiang estuary, China
10
0.3-21.8
0.7-111.9
Mai et al. (2005)
Tianjin, China
8
0.05-0.5
nd-15
Wang et al. (2007)
12
nd-0.55
0.16-94.6
Chen et al. (2006)
Korean
20
0.05-0.90
0.22-493
Moon et al. (2007)
Tokyo Bay, Japan
8
0.051-3.6
0.89-85
Minh et al. (2007)
Netherland
13
14-22
240-1650
Verslycke et al. (2005)
Yangtse River estuary,
China
Concentrations of PBDEs in Liaodong Bay
were lesser than those in other areas
Concentration of 6-OH-BDE47
(pg/g dw)
Occurrences of OH-PBDEs and MeO-PBDEs
120
80
40
0
0
20
40
60
Concentration of 6-MeO-BDE47
(pg/g dw)
Concentrations of OHPBDEs: <4-116 pg/g dw,
concentrations of MeOPBDEs: 3.8-56 pg/g dw
Significant correlation was observed between OHPBDEs and MeO-PBDEs in sediment
Biotransformation relationships in sediments
1g sediment+4ml sea water+chemicals
(BDE47/6-OH-BDE47/6-MeO-BDE47)
Degradation
time (day)
0
1
4
25
42
66
Incubation 120 rpm 30 dergee
Chemical analysis
Degradation test
Biotransformation relationships in sediments
6-MeO-BDE47 exposure
6-OH-BDE47 exposure
6-MeO/OH-BDE47 were not detected in BDE47 incubation group；
0.010 ± 0.002 of 6-MeO-BDE47 was transformed to 6-OH-BDE47；
0.824 ± 0.052 of 6-OH-BDE47 was transformed to 6-MeO-BDE47。
In Liaodong Bay, interconversion of MeO-PBDEs and OH-PBDEs were observed in
sediments MeO-PBDEs and OH-PBDEs in sediments were not from PBDEs
Per- and poly-fluorinated Chemicals in Bohai Bay,
Yellow Sea and Northern China
30
Why Monitoring?
 Determine concentrations, distribution, and
transportation of PFCs in aquatic systems in
Northern China
 Establish baseline environmental
concentrations for identifying sources and
potential risks
 Provide information for future effectiveness
of control measures
Sampling Locations
Sample Collection and Treatment
Type
Number
Water
36
Sediment 35
Soil
31
Biota
25
FB
12
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<LiaoningRiver, 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
Annual capacity (kt) of facilities for production of TFE and PTFE
Sampling locations in South Bohai coastal rivers
of China.
Chromatogram of 17 PFCs by MRM (100 ng/mL)
Patterns of PFCs
(a) Mean contribution of individual PFC to ∑PFCs in the
Xiaoqing River and 11 other rivers.
(b) PCA using concentrations of 11 PFCs and 8 parameters
describing water quality of rivers
39
Salinity of water Samples
PFCs in Water from Northern China
PFCs in Water from Guanting Reservoir
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.
Greater concentrations of PFCs were found downstream
in rivers, which indicate increasing concentrations 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
PFCs in Estuarine and Coast of North Bohai Sea
Heavy polluted areas, North
Bohai Bay, especially Liaoning
Province
PFCs in Water from North Bohai Bay
PFCs in Sediment from North Bohai Bay
PFCs in Soil from North Bohai Bay
Potential Ecological Risk to Aquatic Animals
General Conclusions PFC-I
 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.
 Relatively greater concentrations of PFCs in Tianjin and
Liaoning suggest that further studies are needed.
General Conclusions PFCs-II
 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.
Activities Summary: Perspectives
related fields
Pollutants
Source/Stress
Environmental
Chemistry
Transport/
Transformation
Ecological
Response
Chronic &
Long-term Effect
Adverse Effect
Chemodynamics
Environmental
Characterization
Toxicological
Response
Environmental
Assessment
Exposure
Ecosystem
&
Human
Early Biological
Effect
Effect
Activities Summary: Perspectives
back & forth approach
Environmental
Chemistry
Environmental
Anal. Chemistry
source-oriented
approach
Ecological
Response
Chemodynamics
support
Toxicological
Response
Environmental
Assessment
Exposure
Ecosystem
&
Human
backsupport
Effect
Environmental
Ecotoxicology
receptor-oriented
approach
Challenge : Something New?
towards pioneering knowledge
Natural
(past work)
•A tradition of Excellence
•Honoring Public Service
•Pioneering Knowledge
Benthic
flora
(2002-)
Benthic
fauna
(2003-)
Sediment (water)
quality
(1998-)
Interdisciplinary
Something New?
(2012-)
(past work)
Benthic algal
dynamics
(continue)
Benthic
response
(2009-)
Source to outcome
pathway?
(2012-)
Biophysical
communication?
(2013-)
Coupled human
and nature?
(2015-)
Challenge: Promising?
Source to outcome
pathway?
(2012-)
Source
Community
Environmental
Contaminants
Population
Exposure
Individual
Key Events
Cellular Effects
Toxicity Pathway
Mode of Action
Adverse Outcome Pathway
Source to Outcome Pathway
Challenge: Goals & Vision
Marine Ecosystem Study
Geophysical
Chemical
(cooperating!)
(cooperating!)
Benthic
algal
dynamics
natural
Source to
outcome
pathway?
benthos
(focusing!)
Interdisciplinary
Ocean
(cooperating!)
Biophysical
communication?
Biological
(cooperating!)
towards Earth
Coupled
Human and
Nature?
Socioeconomic
(cooperating!)
& Environmental Sciences
Thank You!!!!! Questions????
 John P. Giesy, Ph.D.
 Professor & Canada Research Chair in Environmental
Toxicology
 Dept. Veterinary Biomedical Sciences & Toxicology
Centre
 University of Saskatchewan
 Saskatoon, SK, Canada
 Tel: (306) 966-2096 Fax: (306) 931-1664
 Email: John.Giesy@usask.ca
 WebSite:
http://ww.usask.ca/toxicology/faculty_profiles/giesy_john.html