Hydrocarbon and Ecotoxicity of Water and after the Oil Spill occurred in July… · 2016-02-20 ·...

Hydrocarbon and Ecotoxicity of Water and Sediment from Iguassu and Barigui Rivers after the Oil Spill occurred in July/2000,

Parana, Brazil

PETROBRAS RESEARCH CENTER/CENPES

Irene T. Gabardo

[email protected]

Maria de Fátima Guadalupe Meniconi Eduardo Barcelos Platte

Letícia Veiga Falcão

Gilson Cruz da Silva (Fundação Gorceix)

PETROBRAS REFINERY-REPAR

Fernando Henrique Falkiewicz

About the accident

• On the 16th. of July, 2000

• 4000 m3 crude oil spilled

• cause: peline rupture

Iguassu River oil spill - July/2000

pi


Paraná

Site of the spill

Parana - Iguassu River

Rio Barigui

Rio Iguaçu

Ponto 0

1 2

3A45

6 (17 km)

(13 km)

(28 km)

(44 km)

6a

(84 km)

GAL. LÚCIOGAL. LÚCIO

7

(174 km)

8

(314 km) 9

2A3B 3

ento


o BOOMS

IGUASSU

FALLS

Iguassu River Ecosystem


Iguassu River - Booms at P6 - Balsa Nova



Monitoring Program - Sites of samplingWater or Sediment

Codes Station North East Region

UPSTREAM SITES

W, S M Bar Barigui river – Upstream (3.5 km)

7172504 666565 Bridge near pulp industry.

W, S M Igu Iguassu River – Upstream 7162964 664537 Bridge BR116

SPILL SITES

W, S P0 av Barigui river - Point 0 (2 km down spill)

7169315 665208 Arroio Saldanha and Barigui river confluency

W, S P1 Barigui river - Point 1 7168480 665877 Booms at P1

W, S P2 Barigui river - Point 2 7166053 664977 Cachimba bridge

DOWNSTREAM SITES IN IGUASSU RIVER

W, S P3 Point 3 (7 km down spill) 7169000 655550 Iguassu river

W, S P4 Point 4 (17 km down spill) 7167712 649259 Guajuvira (bridge)

W, S P5 Point 5 – (28 km down spill) 7167550 644050 General Lucio

W, S P6 Point 6 – (44 km down spill) 7167792 637458 Balsa Nova

W, S P6A Point 6 A (approx 48 km) 7168539 636259 Balsa Nova

W, S P7 Point 7 - (84 km down spill) 7174136 611931 Porto Amazonas – (bridge)

W, S P8 Point 8 (174 km down spill) 7137827 561614 Sao Mateus do Sul (bridge)

W, S P9 Point 9 – (314 km down spill) 7097603 495168 Uniao da Vitoria

(intake station to drinking)


P 0 - Terrestrial Area (P0 adj)

oAPI: oC:

SIM DIS: <36 to 588oC residue 27% up to 588oC)

Evaporation estimative: % (up to 180oC)

SARA (% weight): 3 2 R=9.6 8

PAH: 16 mg/g (mainly naphtalenes, phenantrenes)

Spilled Oil CharacterizationSpilled Oil Characterization


Density 20/441 0,8164

(

26

S= 71. A=18. A=0.

Toxicity of the Spilled OilToxicity of the Spilled Oil


Spilled Oil Vibrio fischeri (Microtox)

Daphnia similis Brachydanio rerio

(Code 1447) CE5015min

(% WSF) CE5048h

(% WSF) CL5048h

(% WSF)

Test 1 7,13 - 28,15

Test 2 8,31 23,96 -

Test 3 7,69 49,52 -

WSF: Water soluble fraction


Water Analysis during 3 months (Jul to Aug/2000)

• 360 Chemical Analysis in 120 samples TPH (GC/FID) Biomarkers (GC/MS )

BTEX (P&T/GC/PID) Phenols (GC/MS )

PAH (UV-Fluorescence and GC/MS )

• Metals and Pesticides in 14 samples • 186 toxicity tests in 44 samples

Vibrio fisheri Daphnia similis Brachydanio rerio Ceriodaphnia dubia

TPH in the Rivers Waters


Estações

THP

-5000

0

5000

10000

15000

20000

25000

30000

35000

40000

M Bar M Igu P0 Adj P0 rio P4 P6 P7 P8 P9

MaxMin75%25%Mediana

Stations

TPH

(µg/

L)

Median

(µg/

g)

TPH (excluding P 0 terrestrial area)

TPH

(µg/

g)

Stations


Estações

THP

(µg/

L)

-1000

1000

3000

5000

7000

9000

M Bar M Igu P0 rio P4 6 P7 8 P9

MaxMin75%25%MedianaMedian

Stations

in the Rivers Waters

P P

BTEX and PAH rs Waters

BTEX

PAH (UV-Fluorescence)


Estações

HPA

(µg/

L

-200

200

600

1000

1400

1800

2200

2600

M Bar M Igu P0 Adj P0 rio P4 6 P7 8 9

MaxMin75%25%Mediana

Stations

PAH

(µg/

L) Median

Estações

BTE

X (µ

g/L)

-500

0

500

1000

1500

2000

2500

3000

3500

M Bar M Igu P0 Adj P0 rio P4 P6 P7 P8 P9

MaxMin75%25%Mediana

Stations

Median

in the Rive

P P P

BTEX in the Rivers Waters (excluding P 0)


Estações

BTE

X

-50

0

50

100

150


MaxMin75%25%Mediana

Stations

Median

(µg/

L)

P P

PAH in the Rivers Waters (excluding P 0)

Estações

HPA

(µg/

L)

-50

0

50

100

150

200

250

300

350

400


MaxMin75%25%Mediana

Stations

Median

PAH

(µg/

L)Iguassu River oil spill - July/2000

P P


Fingerprinting of Water Samples Extracts (TPH GC-FID) FID1 A, (D:\HPCHEM\1\REPAR\AGO\THP1608\SIG10003.D)

pA

100

80 Barigui River 60 Upstream 40

15/Aug/00 20

0 FID1 A, (C:\HPCHEM\1\2000\NOVEMBRO\07REP\SIG10008.D)

pA

800 P0 Terrestrial

600 nC12

nC13

nC14

nC15

nC16

d n

C16

nC17

Pr

ista

no

nC18

f

itano

nC19

nC

20d

nC

20

nC21

nC22

nC23

nC

24d

nC

24

nC25

nC26

nC27

nC

28

nC29

nC30

d nC

30

nC31

nC

32

nC33

nC

34

area 400

04/Oct/00 200

0 10 20 30 40 50 min0FID1 A, (C:\HPCHEM\1\2000\JULHO\23REPAR\SIG10005.D)

pA

P6 Guajuvira 175

150

125

nC12

nC13

nC14

nC15

nC16

dnC

16 nC

17

nC18

nC19

nC20

nC21

nC22

nC23

nC24

nC25

nC26

nC27

nC

28

nC29 nC

30d

nC30

nC

31

nC32

nC

33

20/Jul/00 100

75

50

25

0 10 20 30 40 50 min

Concentração (ng/L)

600400

1000 800

14001200

UPSTR

EAM

BA

RIG

UI R

IVER 20/July/2000

1600

200 0

2MN 1MN C2N C3N C4N Ace

Aceft

C1Flu C2Flu C3Flu

Fen C1Fen C2Fen C3Fen C4Fen

C1Pi C2Pi BaA

C1Cri C2Cri BbFt BkFt BaPi

DBahA BghiP

N

PA

H

by GC

-MS in

rivers water

Iguassu

River oil sp

ill -Ju

ly/20

00

Flu

Ant Ft Pi

Cri

I-Pi

PA

H

MS in

rivers water

Iguassu

River oil sp

ill -Ju

ly/20

00

P4 uvira 20/July/2000

0

500

1000

1500

2000

2500

3000

N 2MN 1MN C2N C3N C4N Ace

Aceft Flu

C1Flu C2Flu C3Flu


Ant Ft Pi

C1Pi C2Pi BaA

Cri C1Cri C2Cri BbFt BkFt BaPi I-Pi

DBahA BghiP

Concentração (ng/L)

by GC

-

Guaj

TOXICITY IN RIVERS WATER


0

1

2

3

4

5

6

Samp ling site s

TU

Mic rotox Daphnia s im ilis B rac hydanio rerio Ceriodaphnia dub ia

Up s tream S pill area Down s tream

TU= Toxic Units (express the toxicity as a inverse of CL50


Water Toxicity

• The toxicity tests indicated the impact was restrict to P0 terrestrial area;

• it was observed toxicity in other parts of the rivers not related to the oil spill (caused by other sources)

Vibrio fisheri Daphnia similis Brachydanio rerio Ceriodaphnia dubia


CONCLUSIONS ABOUT RIVER WATER

⇒ No contamination was observed at Iguassu river at P7 (84 km), P8

(174 km), P9 (314km) stations during the monitoring after the spill;

⇒ The BTEX, TPH, PAH results indicated:

• the high concentrations were obtained at P0 terrestrial region;

• the upstream stations demonstrated high level of hydrocarbon;

• the downstream stations at Barigui and Iguassu rivers showed

background hydrocarbon levels after 1 week of the accident;

� No match with the Biomarkers of the spilled oil was observed

for the downstream stations even in Barigui or Iguassu river.


14 Sediment Samples (1 month after spill)

Chemical Analysis TPH (GC/FID)

BTEX (P&T/GC/PID)

PAH (GC/MS )

Metals Toxicological assays (Microtox and Daphnia similis)

n-Alkanes (GC/FID)

UCM (GC/FID)

Phenols (GC/MS )

Pesticides

Hydrocarbons in River Sediments µg/g ( ppm)

Iguaç

u Mo

nt

Barig

ui Mo

nt

P 0

-bar

1

P 0

-bar

2

P 1

P 2

P 3B

P 4

P 5

P 6

P 6A

P 7

P 8

P 9

n-a lc a nos

P AH

BTEX

UCM

TP H0

100

200

300

400

500

600

700

800

900

1000

Hydr

ocar

bons

( g

/g)

Stations


-

Iguaç

u Mo

nt

Barig

ui Mo

nt

P 0

-bar

1

P 0

-bar

2

P 1

P 2

P 3B

P 4

P 5

P 6

P 6A

P 7

P 8

P 9

B TEX PAH (1 6 )

PAH (3 2 )

0

100

200

300

400

500

600

700

800

900

1000

Hydr

ocar

bons

(ng

/g)

Stations

Hydrocarbons in River Sediments ng/g ( ppb)


-

0

Total extract (TEM)

n-alkan

es (after cleanu

p)10

20 30

40 50

m0

1020

3040

50m

P4 -

Gu

ajuvira

22/Au

g/00 m

0 10

20 30

40 50

pA

20

30

40

50

60

70

80

90

nC10 nC11

nC12 nC13

nC14 nC15

nC16d nC16 nC17Pristano

nC18fitano nC19nC20dnC20

nC21 nC22 nC23nC24d nC24

nC25 nC26

nC27 nC28

nC29nC30d nC30nC31

nC32nC33

nC34

m0

10 20

30 40

50

pA

20

40

60

80

100

nC13 nC14

nC15 nC16d nC16

nC17Pristano nC18fitano

nC19 nC20d nC20

nC21 nC22

nC23 nC24

nC25 nC26

nC27 nC28

nC29nC30d nC30 nC31 nC32nC33

nC34

pA

20

30

40

50

60

70

80

90 FID1 A,

nC13

nC15 nC16dnC16

nC17Pristano nC18fitano

nC19 nC20

nC21 nC22

nC23nC24d nC24

nC25 nC26

nC27 nC28

nC29nC30dnC30 nC31

nC32 nC33

nC34

pA

20

30

40

50

60

70

80

90 FID1 A,

nC12dnC12 nC13

nC14 nC15

nC16dnC16 nC17Pristano

nC18fitano nC19

nC20dnC20 nC21

nC22 nC23nC24dnC24 nC25 nC26 nC27 nC28 nC29nC30dnC30

nC31 nC32 nC33

nC34

Barigu

i

upstream

24/Au

g/00

(E:\UC

M-2000\O

UT\18ALL2\SIG

10005.D)

(C:\H

PCH

EM\1\2000\N

OVEM

BRO

\14ALL\SIG10024.D

)

River

FID1 A,

(E:\UC

M-2000\O

UT\18ALL2\SIG

10011.D)

FID1 A,

(C:\H

PCH

EM\1\2000\N

OVEM

BRO

\14ALL\SIG10045.D

)

Fingerpritin

g of Sedimen

t extracts (GC

-FID)

Iguassu

River oil sp

ill -Ju

ly/20

00

UP

STREA

M B

AR

IGU

I RIV

ER

0 10 20 30 40 50 60 70 80 90

100


Aceft Flu

C1Flu C2Flu C3Flu

DBT C1DBT C2DBT C3DBT


Ant Ft Pi

C1Pi C2Pi BaA Cri

C1Cri C2Cri BbFt BkFt BaPi I-Pi

DBahA BghiPe

Concentration (ng/g)

Iguassu

River oil sp

ill -Ju

ly/20

00

PA

H in

sedimen

t by GC

-MS

PA

H in

sedimen

t by GC

-MS

Iguassu

River oil sp

ill -Ju

ly/20

00

Station

-G

uaju

vira

0 20 40 60 80

100 120 140 160 180


Aceft Flu

C1Flu C2Flu C3Flu

DBT C1DBT C2DBT C3DBT


Ant Ft Pi

C1Pi C2Pi BaA Cri

C1Cri C2Cri BbFt BkFt BaPi I-Pi

DBahA BghiPe

Concentration (ng/g)

P4


PAHs in Sediments - Literature Comparison ....................................................................................................

Iguassu and Barigui Rivers: Upstream: 47 1028 µg/kg

Spill Area: 89 901 µg/kg Downstream: 13

.................................................................................................... Other brazilian rivers:

Tapajos River: 21 2032 µg/kg Guandu River: 8091 µg/kg

Solimoes River: 1600 µg/kg

HPLC - UV only the 16 PAH

GC-MS (sum 36 PAH)

--1590 µg/kg to

--662

-251


Toxicity of the sediments leaching Microtox

(Vibrio fischeri) Daphnia similis

SAMPLES CE505min (%) CE5048h.(%)

Barigui River - UPSTREAM NT IT

Iguassu River UPSTREAM NT NT

P 0 s 1 IT 21,43

P 0 s 2 IT IT

P1 - Barigui River IT 100

P2 - Barigui River NT IT

P3 - Iguassu River NT NT

P4 - Iguassu River NT NT

P5 –-Iguassu River IT IT

P6 - guassu River IT 10,00

P6A - guassu River IT 22,36

P7- - Iguassu River NT 70,71

P8 - - Iguassu River IT < 10,00

P9 - - Iguassu River IT 10,00

Boom

Boom

I

I

NT – non toxic

IT – incipient toxicity


CONCLUSIONS About the River Sediments UPSTREAM:

- The background levels at the upstream stations from Barigui and Iguassu rivers showed high level of contamination (metals and hydrocarbons);

- Barigui river more contaminated than Iguassu river.

DOWNSTREAM:

- The sites more contaminated (P4 and P5) suggested some oil presence but the biomarkers (terpanes and steranes) analysis showed no matches with

the spilled oil ;

- Literature comparison of PAH in sediments showed similar concentration levels for other Brazilian rivers;

- High level of toxicity was observed to stations situated far from the spill site suggesting other sources of pollutants.


GENERAL CONCLUSION

About the Rivers

- It was not observed significant contamination in water or

sediments from Barigui and Iguassu rivers after the cleanup

step;

- Same level of hydrocarbon in upstream or dowstream the

accident (exception P4 and P5);

- Literature comparison of Hydrocarbon in sediments showed

similar concentration levels for other Brazilian rivers;

- High level of toxicity was observed to stations situated far

from the spill site suggesting other sources of pollutants.


P 0 - Terrestrial Area (P0 adj)

Groundwater 90 monitoring wells

(piezometers)

Soil monitoring of approx. 80 sites


GENERAL CONCLUSIONS

About the terrestrial area

- The more contaminated site was the P0 terrestrial area

(approx. 130,000 m2);

- The TPH, BTEX in groundwater revealed significant

decrease in last campaing (Aug/2001);

- Several recovery and bioremediation methods have

been implemented in this region;

- Long term soil and groundwater monitoring is still

being conducted in this area.

Hydrocarbon and Ecotoxicity of Water and after the Oil Spill occurred in July… · 2016-02-20 ·...

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Transcript of Hydrocarbon and Ecotoxicity of Water and after the Oil Spill occurred in July… · 2016-02-20 ·...