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Andrew Loh1,2, Un Hyuk Yim1,2, Sung Yong Ha1 , Joon Geon An1 and Won Joon Shim1,2
1Korea Institute of Ocean Science and Technology (KIOST)2University of Science and Technology, Korea (UST)
OSA as an unknown route of exposure to filter feeding bivalve in the turbid
environment
� Introduction
�Materials and method
�Results and Discussion
�Conclusion
�Q & A
Content
� The Hebei Spirit Oil Spill: The Largest Oil Spill in Korea
� Collision of MV Hebei Spirit with a barge on7th December 2007 released approximately12,547 kL (10,900 M/T) of crude oil.
� The MV Hebei Spirit was carrying three kindsof crude oil, namely UAE Upper Zakum (UZC),Kuwait export crude (KEC) and Iranian heavycrude (IHC).
� Due to the strong westerly wind, spilled oilpolluted most of west coast of Korea, 375 kmcoastlines.
� More than one million of volunteers joined forinitial oil cleanup.
� Oil spill compensation process is still underway.
Introduction
Seawater Bivalves Sediments
Multi-media monitoring for oil contamination
16 PAHs
2007 Dec
2008 Jan
2008 Feb
2008 Mar
2008 Apr
2008 May
2008 Jun
2008 Jul
2008 Aug
2008 Sep
2008 Oct
2008 Nov
2008 Dec
2009 Feb
2009 Apr
2009 Jun
2009 Sep
2009 Dec
2010 Mar
2010 Jun
2010 Sep
2010 Dec
2011 Mar
2011 Jun
2011 Sep
2011 Dec
2012 Apr
2013 Apr
16 P
AH
s in
Oyst
er (
ng
/g d
w.)
0
200
400
600
800
1000
1200
1400
Alkylated PAHs
2007 Dec
2008 Jan
2008 Feb
2008 Mar
2008 Apr
2008 May
2008 Jun
2008 Jul
2008 Aug
2008 Sep
2008 Oct
2008 Nov
2008 Dec
2009 Feb
2009 Apr
2009 Jun
2009 Sep
2009 Dec
2010 Mar
2010 Jun
2010 Sep
2010 Dec
2011 Mar
2011 Jun
2011 Sep
2011 Dec
2012 Apr
2013 Apr
Alk
yl
PA
Hs
in O
yst
er
(ng/g
dw
.)
100
101
102
103
104
105
106
GC/FID Chromatogram
OysterDec 2007
Oyster Jan 2008
Oyster Apr 2008
Long-Term Monitoring Oil Fingerprinting
Stranded Oil
Dec 2007
min5 10 15 20 25 30
pA
0
200
400
600
800
1000
1200
- Initial: oil droplet- Persistent source
- 16 PAHs decreased rapidly- Alkyl PAHs persisted
- PAH double ratio- Manila clam: same with oyster
Oyster
Clam
� Route of exposure using exposure media� Traditional route of exposures; Water Accommodated Fractions (WAF) and Mechanically
Dissolved Oil (MDO).� Traditional methods could not match the Petroleum Derived Hydrocarbon distributions in
oysters from spill site.� Tests of unknown mode of exposure; Oil SPM Aggregates (OSA)
� Research objectives� To compare the fate of oil in the traditionally used exposure
methods.� To identify the continuous source of oil contamination to bivalves
in the HSOS.� To identify the fate of spilled oil in high turbidity environments
such as intertidal areas.
� OSA formation as the output of oil and particle interactions
� When oil and suspended particles interact, OSA is formed.� OSA formation has been observed in several large spills;
Exxon Valdez (1989), Sea Empress (1996) and Deep WaterHorizon (2010).
� OSA is formed in 2 main steps;(1) Breaking of surface oil by wave actions(2) Interaction of oil and particles
10µm
A B
100µm
100 µm
C
100 µm
D
� Formation of WAF� Method following CROSERF with slight modification(1) 1 L filtered seawater + magnetic stirrer(2) Addition of 25 g of Iranian Heavy Crude Oil(3) Magnetic stirred at 120 rpm for 24 hours(4) 900 ml of solution excluding surface oil was collected
� Formation of MDO(1) 1 L filtered seawater placed in separatory funnel(2) Addition of 25 g of Iranian Heavy Crude Oil(3) Vertical shaking at 50 rpm for 15 minutes(4) Settled for 1 hour(5) 900 ml of solution excluding surface oil was collected
� Formation of OSA� Method following Khelifa et a., 2002 with slight modification.(1) 1 L filtered seawater + 200 mg of particle(2) Solution + 600 mg of Iranian Heavy Crude oil
(Approxi. 1/40 of MDO and WAF)(3) Reciprocal shaking for 24 hours(4) Solution settled for 24 hours(5) 900 ml of solution excluding surface oil was collected
Materials and Method
� Exposure of media to oysters� Prior to exposure, oysters were acclimated in filtered seawater for 3 days.� Oysters are placed into the beaker filled with 700 ml of exposure media and a small
magnetic stirrer.� 10-AU fluorometer equipped with oil kit was used to quantify total petroleum
hydrocarbons before and after exposure.� After 24 hours of exposure, exposure media was replaced with newly prepared
exposure media.� After 48 hours of exposure, oysters were collected and prepared for chemical analysis
using GC/FID and GC/MS.
MDO OSA WAF
10-AU Fluorometer GC-MS GC-FID
Acclimation
MDO
WAF
Results and Discussion
OSA
Visual observation of oyster uptake
Exposure mediaBefore exposure
(ppm)After 24 hrs exposure
(ppm)Total loss (ppm)
MDO 238.0 109.0 129.0 (highest)
OSA 48.0 44.4 4.4 (middle)
WAF 0.92 0.67 0.25 (lowest)
Befo
re e
xposu
re
After
exp
osu
re
MDO
OSA
WAF
TPH Changes of Exposure Media
MDO
OSA
WAF
GC/FID chromatograms of petroleum hydrocarbons in oysters
Control
MDO
WAF
OSA
� TPH, UCM, n-alkane and Alkyl PAHs have concentration trend;MDO>OSA>WAF.
� But n-alkane for WAF exposed oyster was similar with control oyster.
� 16 PAHs have similar concentrations for all oysters, however, theconcentration of Alkylated PAHs was highest from MDO>OSA>WAF.
� This shows that, monitoring 16 PAHs alone is not suitable.
� Monitoring Alkylated PAHs could provide more accurate evaluation.
Control MDO (highest)
OSA
(middle)
WAF (lowest)
TPH 18.5 113.0 ± 52.0 66.2 ± 15.9 35.8 ± 6.9
UCM 8.7 66.9 ± 39.9 28.1 ± 10.6 12.7 ± 0.6
n-Alkane 0.5 7.1 ± 6.3 1.1 ± 0.6 0.3 ± 0.0
16 PAHs 0.1 3.0 ± 0.5 2.8 ± 0.6 2.4 ± 0.9
Alkyl
PAHs
0.360.2 ± 19.9
35.2 ± 6.113.8 ± 1.8
Accumulation of Petroleum Derived Hydrocarbons in oysters
Comparison of PAH profiles
CN
0
CN
1
CN
2
CN
3
CN
4
Acn
l
Acn
t
C0
F
C1
F
C2
F
C3
F
C0
P
An
th
C1p
C2
P
C3
P
C4
P
C0
D
C1
D
C2
D
C3
D
Flr
t
Py
r
Ba
A
C0
C
C1
C
C2
C
C3
C
Bb
F
Bk
F
Ba
P
Icd
P
Da
hA
Bg
hiPP
AH
s C
om
posi
tio
n i
n o
yst
ers
at
Sp
ill
Sit
e (
%)
0
5
10
15
20
25
30
Oyster Dec. 2007
CN
0
CN
1
CN
2
CN
3
CN
4
Acn
l
Acn
t
C0
F
C1
F
C2
F
C3
F
C0
P
An
th
C1
p
C2
P
C3
P
C4
P
C0D
C1D
C2D
C3D
Flr
t
Py
r
BaA
C0C
C1C
C2C
C3C
Bb
F
Bk
F
BaP
Icd
P
Da
hA
Bgh
iPPA
Hs
Co
mp
osi
tion
in
oy
ster
s at
Sp
ill
Sit
e (%
)
0
10
20
30
40
50
Oyster Dec. 2008
CN
0
CN
1
CN
2
CN
3
CN
4
Acn
l
Acn
t
C0
F
C1
F
C2
F
C3
F
C0
P
An
th
C1p
C2
P
C3
P
C4
P
C0
D
C1
D
C2
D
C3
D
Flr
t
Pyr
Ba
A
C0
C
C1
C
C2
C
C3
C
Bb
F
Bk
F
Ba
P
Icd
P
Da
hA
Bg
hiPPA
Hs
Co
mp
osi
tion
in
sea
wate
r o
f sp
ill
site
(%
)
0
5
10
15
20
25
30
Seawater Dec. 2007
CN
0
CN
1
CN
2
CN
3
CN
4
Acn
l
Acn
t
C0
F
C1
F
C2
F
C3
F
C0
P
An
th
C1p
C2
P
C3
P
C4
P
C0
D
C1
D
C2
D
C3
D
Flr
t
Pyr
Ba
A
C0
C
C1
C
C2
C
C3
C
Bb
F
Bk
F
Ba
P
Icd
P
Da
hA
Bg
hiPPA
Hs
Co
mp
osi
tion
in
Ira
nia
n H
eav
y C
rud
e (%
)
0
5
10
15
20
25
30
Iranian Heavy Crude
Field Samples
Exposure Media Oysters
OSA
C0
NC
1N
C2
NC
3N
C4
NB
iPA
cnl
Acnt
C0
FC
1F
C2
FC
3F
C0
PA
nth
C1
PC
2P
C3
PC
4P
C0
DC
1D
C2
DC
3D
Flr
tP
yr
BaA
C0C
C1C
C2C
C3C
Bb
FB
kF
BeP
BaP
Icd
PD
ahA
Bg
hiP
PerP
AH
Co
mp
osi
tio
n i
n O
yst
er
(%)
0
5
10
15
20
25
30
WAF
C0N
C1N
C2N
C3N
C4N
BiP
Acn
lA
cnt
C0
FC
1F
C2
FC
3F
C0
PA
nth
C1
PC
2P
C3
PC
4P
C0D
C1D
C2D
C3D
Flr
tP
yr
BaA
C0C
C1C
C2C
C3C
Bb
FB
kF
BeP
BaP
Icd
PD
ahA
Bg
hiP
Per
PA
H C
om
po
siti
on
in
Oy
ster
(%)
0
10
20
30
40
50
MDO
C0N
C1N
C2N
C3N
C4N
BiP
Acn
lA
cnt
C0
FC
1F
C2
FC
3F
C0
PA
nth
C1
PC
2P
C3
PC
4P
C0D
C1D
C2D
C3D
Flr
tP
yr
BaA
C0C
C1C
C2C
C3C
Bb
FB
kF
BeP
BaP
Icd
PD
ahA
Bg
hiP
PerP
AH
Co
mp
osi
tio
n i
n O
yst
er (
%)
0
5
10
15
20
25
WAF
C0
NC
1N
C2
NC
3N
C4
NB
iPA
cnl
Acn
tC
0F
C1F
C2F
C3F
C0P
Anth
C1P
C2P
C3P
C4P
C0
DC
1D
C2
DC
3D
Flr
tP
yr
BaA
C0
CC
1C
C2
CC
3C
BbF
BkF
BeP
BaP
IcdP
Dah
AB
gh
iPP
erPA
H C
om
po
siti
on
in
Sea
wa
ter (
%)
0
10
20
30
40
50
MDO
C0
NC
1N
C2
NC
3N
C4
NB
iPA
cnl
Acn
tC
0F
C1F
C2F
C3F
C0P
Anth
C1P
C2P
C3P
C4P
C0
DC
1D
C2
DC
3D
Flr
tP
yr
BaA
C0
CC
1C
C2
CC
3C
BbF
BkF
BeP
BaP
IcdP
Dah
AB
gh
iPP
er
PA
H C
om
po
siti
on
in
Seaw
ate
r (%
)
0
10
20
30
40
OSA
C0N
C1N
C2N
C3N
C4N
BiP
Acn
lA
cnt
C0
FC
1F
C2
FC
3F
C0
PA
nth
C1
PC
2P
C3
PC
4P
C0D
C1D
C2D
C3D
Flr
tP
yr
BaA
C0C
C1C
C2C
C3C
Bb
FB
kF
BeP
BaP
Icd
PD
ahA
Bg
hiP
PerPA
H C
om
posi
tio
n i
n S
eaw
ate
r (%
)
0
10
20
30
40
50
60
Y D
ata
Y D
ata
Y D
ata
Route of Exposure Tests
노노노
ControlWAF OSA MDO
16
PA
Hs
Co
nc.
in
Oy
ster
(n
g/g
dw
.)
100
101
102
103
104
105
106
노노노
ControlWAF OSA MDO
Alk
yl
PA
Hs
Co
nc.
in
Oy
ster
(n
g/g
dw
.)
100
101
102
103
104
105
106
PAH double ratio plots
C2D/C2P ratio
0.0 0.5 1.0 1.5 2.0 2.5 3.0
C3
D/C
3P
ra
tio
0.0
0.5
1.0
1.5
2.0
2.5
3.0 IHC(SGS)
ControlWAF1WAF2
WAF3
OSA1OSA2OSA3
MDO1
MDO2
MDO3
� 16 PAHs concentrations could not distinguish their route of exposure but alkyl PAHscould.
� Alkyl PAHs could be used in double ratio plots to identify their relativity with source oil.� Double ratios using alkylated Phenanthrene and alkylated Dibenzothiophene has been
widely used for oil fingerprinting.� Double ratios of MDO and OSA matched more with the source oil but WAF did not
match.� Double ratio plots are very useful fingerprinting tool.
WAF OSA MDO
� To explain persistency of PAHs in oysters after the Hebei Spirit oil spill,available exposure method including WAF, MDO, and OSA were tested.
� Among three exposure media, OSA showed higher accumulationefficiency than others.
� Alkylated PAHs in oyster well exhibited accumulation of petroleumderived hydrocarbons.
� PAHs double ratio in oyster was proved to be useful for oilfingerprinting.
� OSA could be used as a new route of exposure to study thebioaccumulation of oil.
Conclusion
End of Presentation