FATES-COMARC 1 Riverine transport of polycyclic aromatic hydrocarbons from Kaoping River (Taiwan) to...

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FATES-COMARCFATES-COMARC

Riverine transport of polycyclic aromatic hydrocarbons from Kaoping River

(Taiwan) to coastal ocean

Chon-Lin Lee1*, Bing-Sian Lin1, and James T. Liu2

1 Department of Marine Environment and Engineering2 Institute of Marine Geology and Chemistry

National Sun Yat-sen University

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Introduction

What are Polycyclic Aromatic Hydrocarbons (PAHs)?

Hydrophobic Organic Compounds (HOC) Persistent Organic Pollutants (POPs)

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Naphthalene Acenaphthylene Acenaphthene Fluorene Anthracene

Phenanthrene Fluoranthene Pyrene Benzo(a)anthracene Chrysene

Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene

Dibenz(a,h)anthracene Benzo(g,h,i)perylene Indeno(1,2,3-cd)pryene

Ring structure of PAHs

4


Introduction

Suspect carcinogens

Endocrine disruptors

Bioaccumulation

Source identification

Why PAHs?

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Petrogenic sources

Oil spillIndustrial waste

PAHs inenvironment

Pyrogenic sources

Industrial emissionVehicles emission

Open-burning emission

Diagenetic source

Diagenesis of biogenic precursorsRetene

Perylene

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FATES-COMARCFATES-COMARCSource identification

Phenanthrene

Fluorene

Benzo(g,h,i)perylene

Anthracene

Acenaphthene

Pyrene

Benzo(a)pyrene

Fluoranthene

Chrysene

Indeno(1,2,3-cd)pryene

Benzo(a)anthracene

Alkyl- phenanthrenesCH3

Naphthalene

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-2.5

-2

-1.5

-1

-0.5

0

0.5

1

1.5

2

2.5

-3 -2 -1 0 1 2

PC3(17.3% )

PC4(1

6.5

%)

surface trap

bottom trap

S. shelf

canyon sediment

N. shelf

PC3 vs PC4

Oil source

Gasoline vehicle source

Down-canyon heading samples

Up-canyon heading sample

00

9090

180180

270270

UpcanyonUpcanyonUpcanyonUpcanyon

Down-Down-canyoncanyonDown-Down-canyoncanyon

T4KP

M-D Fang, W-K Chang, C-L Lee, James T. Liu, 2009, J. Mar. Syst. (76) 457-467

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-2.5

-2

-1.5

-1

-0.5

0

0.5

1

1.5

2

2.5

-2 -1 0 1 2 3 4

PC1(33.5% )

PC2(2

4.6

%)

surface trap

bottom trap

S. shelf

canyon sediment

N. shelf

PCA score plot – PC1 versus PC2

M-D Fang, W-K Chang, C-L Lee, James T. Liu, 2009, J. Mar. Syst. (76) 457-467

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Fate of anthropogenic HOCs and fluvial particles?

N. Shelf

S. ShelfCanyonOuter Shelf

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Objectives

• To estimate the annual fluvial discharges of polycyclic aromatic hydrocarbons and particulate organic carbons from Gaoping River

• To deploy PAH diagnostic ratios and statistical tools (e.g. principal component analysis) for source recognition

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FATES-COMARCFATES-COMARCSampling Map

From：

To：

NOV 06

NOV 07

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FATES-COMARCFATES-COMARCMethods

(1) Soxhlet extraction

(2) liquid-liquid extraction (3) rotary evaporation

(4) Clean up

(5) GC-MS

M-D Fang, F-C Ko, J. E. Baker, C-L Lee, 2008, Sci. Total Environ. (407) 548-565

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NO

V 0

6

DE

C 0

6

JAN

07

FEB

07

MA

R 0

7

APR

07

MA

Y07

JUN

07

JUL

07

OC

T 0

7

NO

V 0

7

PAH

con

cent

ratio

ns (

ng/L

)

0

200

400

600

800particulate phasedissolved phase

TSP

(m

g/L

)

0

50

100

150

200

250

300

350

400

700750800

TSP

PAH concentrations (ng/L)

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TSP ( mg/ L )0 200 400 600 800

part

icula

te P

AH

s (n

g/L

)

0

100

200

300

400

500

600Dry seasonWet season

R=0.95 (p < 0.05 )

0 10 20 30 40 50 60

0

10

20

30

40

50

60

R=0.69

Particulate PAHs(ng/L) VS TSP

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Particulate PAHs(ng/g) VS POC

POC (%)

0 2 4 6 8 10

par

ticu

late

PA

Hs

(ng/

g)

0

500

1000

1500

2000

NOV06

DEC06

JAN07

FEB07

MAR07

APR07

MAY07

JUN07

JUL07

OCT07

NOV07

R=0.584

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Source Identification

BaA/228

0.1 0.2 0.3 0.4 0.5

IP/I

P+

Bgh

i

0.0

0.2

0.4

0.6

0.8

1.0

Straw burningDry seasonWet season

UnburnedPetroleum

PetroleumCombustion

Mixed Sources Combustion

Grass,Wood & Coal Combustion

UnburnedPetroleum

NOV06

DEC06JAN07

FEB07APR07

MAR07

MAY07

JUN07JUL07

OCT07

Petrogenic

Pyrogenic

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1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31

Rain

fall (

mm

)

0

20

40

60

80

100

Dis

charg

e (

m3/s

ec

)

0

50

100

150

200

250

Pingtung RainfallGaoping River Discharge

Dry season Wet season

Sampling

Precipitation

May 07

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FATES-COMARCFATES-COMARCPC1 score plot

PC1 scores

Pyrogenic source

Petrogenic source

M-D Fang, P-C Hsieh, F-C Ko, J. E. Baker, C-L Lee, 2007, Mar. Pollut. Bull. (54), 1179-1189. & J-J Jiang, C-L Lee, M-D Fang, James T. Liu, Mar. Pollut. Bull. In

Press

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HCA cluster

• Canyon and Southern shelf Ⅰ

• Northern shelf

• Wet season

• Canyon and Southern shelf Ⅱ

• Dry season

• Straw burning

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FATES-COMARCFATES-COMARCP

AH

s %

0

5

10

15

20

Canyon and Southern shelf ¢¹Northern shelfCanyon and Southern shelf ¢º

Flu

o

MeF

1

DB

T Ph

An

MeP

3

MeP

2

MeA

2

MeP

45

MeP

1

DM

D46

DM

P36 Flt Py

BaF

l

Bb

Fl

BaA

Ch

ryT

riP

he

Bb

Fa

Bk

Fa

BeP

y

BaP

y

Per

y IP

Bgh

iP

Cor

o

0

5

10

15

20

Wet seasonDry season

HCA Compositional pattern

Methyl-PAHs

S

CH3

CH3 S

Pyrogenic

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PC1 (25%)-1 0 1

FluoMeF1DBT

PhAn

MeP3MeP2MeA2

MeP45MeP1

DMD46DMP36

FltPy

BaFlBbFlBaA

ChryTriPheBbFaBkFaBePyBaPyPery

IPBghiPCoro

PC2 (20%)-1 0 1

PC3 (19%)-1 0 1

PCA LoadingS

CH3

CH3 S

Mixed Sources

pyrolysis

Petroleum

pyrolysis

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PC1 (25% )

-2 -1 0 1 2

PC

2 (

20%

)

-3

-2

-1

0

1

2

3Canyon & S. shelf¢¹Canyon & S. shelf ¢ºN. shelfDry seasonWet season

River Suspended Particles

Coastal Surface Sediments

Between wet and dry season ： Mixed Sources

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PC2 (20% )

-3 -2 -1 0 1 2 3

PC

3 (

19%

)

-2

-1

0

1

2

3

Petrogenic

pyrogenic

Pyrogenic

Biomass/petroleum combustion

Unburned Petroleum

Diesel oil

Canyon & S. shelf¢¹Canyon & S. shelf ¢ºN. shelfDry seasonWet season

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Estimate PAHs FluxN

OV 0

6

DEC 0

6

JAN

07

FEB 0

7

MAR

07

APR

07

MAY 0

7

JUN

07

JUL

07

Aug 0

7

Sep 0

7

OCT 0

7

NO

V 0

7

PA

H F

lux

(kg/

mon

th)

40

80

120

5001000150020002500

Dis

char

ge (

CM

S)

500100015002000

4000

5000

2500

20000

40000

60000

Particulate FluxDissolved FluxDischarge

Total Flux: 4.3 ton/year

Wet season : 99.0%

Krosa typhoon:

Particulate phase : 12.8%

Dissolved phase : 6.7%

Typhoon:

Aug : Pabuk, Wutip, Sepat

Sep : Wipha

Oct : Krosa

Nov : MitagOct 07

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31

Dis

charg

e (

m3/s

ec

)

0

1000

2000

3000

4000

5000

6000

Gaoping River Discharge

Krosa typhoon

sampling

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Koc=0.715Kow+2.418 R2=0.85

Kow

4.0 4.5 5.0 5.5 6.0 6.5

Koc

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

Means et al., 1980This studyFernandes et al., 1997

Koc=Kow-0.317

Koc=0.70Kow+2.75

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Wet season Dry season

Sources petrogenic pyrogenic

PAH concentration 85- 196 ng/L 200- 515 ng/L

Dissolved phase 13- 41 ng/L 57- 152 ng/L

Particulate phase 160- 592 ng/L 12- 49 ng/L

397-1144 ng/g 790-1797 ng/g

Summary

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Sediment discharge 18.7 MT/year

organic carbon discharge 95 kT/year

PAH fluvial discharge 4.3 ton/year

Wet season Dry season

Dissolved phase 85.4 % 14.6 %

Particulate phase 99.7 % 0.3 %

Wet season Dissolved phase Particulate phase

Typhoon 48.1 % 67.0 %

Summary

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Acknowledgements

• National Science Council for funding support

• Prof. H-L Lin for the precious samples

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Thank youand

your comments are welcomed

FATES-COMARC 1 Riverine transport of polycyclic aromatic hydrocarbons from Kaoping River (Taiwan) to...

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