POLYCYCLIC AROMATIC HYDROCARBONS POLYCYCLIC AROMATIC HYDROCARBONS MONITORING IN TERRESTRIAL PLANT BIOTA MONITORING IN TERRESTRIAL PLANT BIOTA

AFTER ERIKA OIL SPILLAFTER ERIKA OIL SPILL

N. Poupart, A. Meudec, F. Poncet, J. DussauzeLaboratoire d’Ecophysiologie et de Biotechnologie des Laboratoire d’Ecophysiologie et de Biotechnologie des

Halophytes et des Algues MarinesHalophytes et des Algues Marines

VERTIMARVERTIMARSymposium of Marine Accidental Oil SpillsSymposium of Marine Accidental Oil Spills

Vigo, 13th-16th july 2005Universidade de Vigo, Spain I.U.E.M.

Université Brest

EA 3877

CEDRECEDREPôle Analytique des EauxPôle Analytique des Eaux

Erika tanker oil spill and coastal terrestrial vegetation

20,000 tons of heavy fuel20,000 tons of heavy fuel400 km of coastline polluted400 km of coastline polluted

All tide levels reached, including supralittoral and terrestrial areasSoils and halophytic plants covered at different degrees All habitats: salt marshes, dunes and rocky sites

Medium tide

High tide

Supralittoral level

Aerohalin level

High slikke

SchorreLow tide

- Photosynthesis - Respiration - Mineral nutrition- Ion homeostasis

Direct effects:Direct effects:

Plant harmfuls: Growth decrease and flowering reduction, …, mortality.

Film fuel deposit: first cause of short term effects

- Gas-exchange

What’s for new shoots and survival plants?

Indirect effects:Indirect effects:

Pollution of plant substratum Rooting zone of littoral plant in contact with petroleum compounds

- PAHs, most studied and toxic organic group

Survival halophytic plant

Polluted susbtratum

PAHs

?

Soil to plant transfer of PAHs ?

-Chemical characteristic: hydrophobic

Five years monitoring Five years monitoring on terrestrial vegetationon terrestrial vegetation

Ecology Ecotoxicology

Phytosociological method GC-MS assays of PAHs

Uptake, Bioaccumulation and Effects Uptake, Bioaccumulation and Effects of of

PAHs in halophytic plantsPAHs in halophytic plants ?PAHs

Survival halophytic plant

Polluted susbtratum

Localization of Localization of

surveyed and collected sitessurveyed and collected sites

Kerliguit

Kerliguit

Le Collet

Parracaud

Bellevue

Bellevue

Glaux maritima

Juncus maritimus

Armeria maritima Sarcocornia perennis

Salicornia fragilis

PAHs contamination of halophytic plant?PAHs contamination of halophytic plant?

No significant value of total PAHs in all control sampled plants : 0,5 < ∑ PAHs < 19,2 ng.g-1 d.w.

High contamination of total PAHs in the first year following the oil spill :714,5 < ∑ PAHs < 6834,2 ng.g-1 d.w.

Total PAHs contents of halophytic plants in 2000 :

Cri

thm

um

Gla

ux

Arm

eria

Inul

a

Sper

gula

ria

Junc

us

Sarc

ocor

nia

Salic

orni

a

Bet

a

Tot

al P

AH

s (1

6) n

g.g-

1 dw

0

2000

4000

6000

8000

Source of PAHs contaminationSource of PAHs contamination ? ?

CG-MS Chromatogram of Crithmum collected in a polluted site:

Presence of BeP and Perylene = petrogenic origin

33.00 33.10 33.20 33.30 33.40 33.50 33.60 33.70 33.80 33.90 34.00 34.10 34.20 34.300

1000

2000

3000

4000

5000

6000

7000

8000

Time-->

Abundance

Ion 252.00 – criste polluée

PeryleneBenzo(a)pyrene

Benzo(e)pyrene

33.00 33.10 33.20 33.30 33.40 33.50 33.60 33.70 33.80 33.90 34.00 34.10 34.20 34.300

1000

2000

3000

4000

5000

6000

7000

8000

Time-->

Ion 264.00

Benzo(a)pyrene perdeuterted

Ratio Flu/Pyr < 1

PAHs molecular ratios: similar between plants and with Erika fuel oil

Petrogenic origine of PAHs present in shoot plants

Molecular ratios of specific PAHs :

Source of PAHs contaminationSource of PAHs contamination ? ?

Fuel oil polluted “soil to plant transfer” occurrence

Ratio Flu/Pyr

0 1 2 3

Ra

tio P

he/

Ant

0

10

20

30

40

2000Erika fuel oil

Pyrolytic zone

Pet

roge

nic

zone

How are PAHs profiles in plant biotaHow are PAHs profiles in plant biota ? ?N

ap A

Ace F

Phe

Ant Flu

Pyr

BaA Chr

BbF

BkF

BaP

ID

ahA BP

BeP Pe

% T

otal

PA

Hs

0

10

20

30

40Crithmum

Nap A

Ace F

Phe

Ant Flu

Pyr

BaA Chr

BbF

BkF

BaP

ID

ahA BP

BeP Pe

% T

otal

PA

Hs

0

10

20

30

40Glaux

Nap A

Ace F

Phe

Ant Flu

Pyr

BaA Chr

BbF

BkF

BaP

ID

ahA BP

BeP Pe

% T

otal

PA

Hs

0

10

20

30

40Armeria

Nap A

Ace F

Phe

Ant Flu

Pyr

BaA Chr

BbF

BkF

BaP

ID

ahA BP

BeP Pe

% T

otal

PA

Hs

0

10

20

30

40

50Inulis

Nap A

Ace F

Phe

Ant Flu

Pyr

BaA Chr

BbF

BkF

BaP

ID

ahA BP

BeP Pe

% T

otal

PA

Hs

0

10

20

30

40Sarcocornia

Nap A

Ace F

Phe

Ant Flu

Pyr

BaA Chr

BbF

BkF

BaP

ID

ahA BP

BeP Pe

% T

otal

PA

Hs

0

10

20

30

40Beta

Nap A

Ace F

Phe

Ant Flu

Pyr

BaA Chr

BbF

BkF

BaP

ID

ahA BP

BeP Pe

% T

otal

PA

Hs

0

10

20

30

40

50Juncus

Nap A

Ace F

Phe

Ant Flu

Pyr

BaA Chr

BbF

BkF

BaP

ID

ahA BP

BeP Pe

% T

otal

PA

Hs

0

10

20

30

40Spergularia

Different profiles between speciesPhe, Pyr and Chr= dominant PAHs Erika fuel oil

Pattern molecular distributions in 2000:

Distribution of PAHs categories Distribution of PAHs categories ? ?

Crithmum & Inula: PAHs2-3 > PAHs4 > PAHs5-6

Other species: Dominant = PAHs4

Large variations between plant species in PAHs bioaccumulation Inherent properties of plants, dosage and weathering of pollutant, climatic conditions

Crit

hmum

Inul

a

Spe

rgul

aria

Junc

us

Sar

coco

rnia

Sal

icor

nia

Bet

a

Gla

ux

Arm

eria

% T

ota

l PA

Hs

0

20

40

60

80

100

% of PAHs with 2-3 rings % of PAHs with 4 rings % of PAHs with 5-6 rings

Monitoring of Total PAHs in plant biota to 2004 Monitoring of Total PAHs in plant biota to 2004 ? ?

Species Sites 2000 2002 2003 2004

Crithmum maritimum ker 6834,2 ± 114,1 2598,4 ± 58,1 570,2 ± 13,7 386,2 ± 5,8

Armeria maritima ker 5597,7 ± 14,3 2567,5 ± 65,4 549,2 ± 16,8 457,4 ± 15,1

Glaux maritima ker 5820,2 ± 62,5 2897,1 ± 54,3 619,9 ± 24,2 942,3 ± 20,1

Inula crithmoides ker 4033,7 ± 37,0 1579,6 ± 20,9 49,9 ± 2,3 166,0 ± 9,8

Juncus maritimus ker 1171,6 ± 21,0 332,6 ± 15,3 49,5 ± 3,1 79,8 ± 4,2

Sarcocornia perennis parr 1026,9 ± 31,8 532,8 ± 11,9 127,6 ± 2,3 270,4 ± 27,6

Salicornia sp parr 987,5 ± 21,8 326,1 ± 4,9 73,1 ± 12,7 349,1 ± 26,4

Salicornia sp bell 467,8 ± 34,5 224,0 ± 4,9 63,2 ± 12,1 161,8 ± 28,2

Salicornia sp coll 278,6 ± 12,8 55,9 ± 16,2 35,2 ± 1,5 95,1 ± 7,3

Persistence of PAHs in plant biota during several years

Gradual decrease of PAHs content over time

Conclusion & Further studiesConclusion & Further studies

How long PAHs compounds will persist in vegetation ? What is the effect of PAHs on plant in the long term?

• High inner contaminations of PAHs on the first year : Total PAHs > 1 mg.kg-1 d.w.

• Persistence of PAHs into plants overtime

• Uptake, transfert and bioaccumulation of PAHs by plants

• PAHs contents depend both on species and polluted sites

• Relative strong hardiness despite significant level of PAHs in plant tissues

Artificial experimental bioassays to characterize PAHs accumulation in plant model ? Similarity with Prestige oil spill ?

Malpica – Playa de Beo - 2003

Camariñas: Cabo Vilán to Cabo Trece