trials of in situ bioremediation on the beach of sorrizo (spain)

TRIALS OF IN SITU BIOREMEDIATION ON THE

BEACH OF SORRIZO (SPAIN)

P. Fernández-Álvarez, J.M. Garrido and J.M. Lema

Department of Chemical Engineering

Universidade de Santiago de Compostela (Spain)

VERTIMAR 2005Vigo, July 14th 2005

J. Vila and M. Grifoll

Department of Microbiology

Universitat de Barcelona (Spain)

1. OBJECTIVE

2. INTRODUCTION

3. MATERIALS AND METHODS

4. RESULTS AND DISCUSSION

5. CONCLUSIONS

Vigo, July 14th 2005VERTIMAR 2005

Paula Fernández ÁlvarezUniversidade de Santiago de Compostela (Spain)



Trials of in situ bioremediation on the beach of Sorrizo (Spain) 1. OBJECTIVE

Who: Department of Chemical Engineering of the University of

Santiago de Compostela (Spain). Department of Microbiology of the University of Barcelona

(Spain). When:

From April 2003 on. Where:

Beach of Sorrizo (A Coruña, NW Spain).

The assessment of the efficiency of several bioremediation strategies on a beach

seriously affected by the oil spill of the Prestige.

Field experiments with several bioremediation agents following the Prestige accident 1. INTRODUCTION

Shoreline clean-up



Trials of in situ bioremediation on the beach of Sorrizo (Spain) 2. INTRODUCTION

SANDY BEACHES Manual recovery. Specialist beach

cleaning machinery

ROCKY SHORES Manual recovery. Low/high pressure

flushing.

These techniques are frequently expensive and

aggresive to the fauna and flora.

Field experiments with several bioremediation agents following the Prestige accident 1. INTRODUCTION

Definition: Act of adding materials to contaminated

environments to cause an acceleration of the natural

biodegradation processes.

Approaches:

Bioaugmentation: oil-degrading bacteria are added to

supplement the existing microbial population.

Biostimulation: the growth of indigenous oil degraders is

stimulated by the addition of nutrients.

Requirements:

Establish and maintain conditions that favour enhanced

oil biodegradation rates.

A large percentage of oil components are readily

biodegradable.Vigo, July 14th 2005VERTIMAR 2005



Bioremediation

Composition of the fuel of the Prestige




Saturates23%

Aromatics53%

Resins13%

Asphaltenes11%

Field experiments with several bioremediation agents following the Prestige accident 3. MATERIALS AND METHODS

The experimental site: the beach of Sorrizo

SPAIN

GALICIA

Arteixo

Galicia

Beach of Sorrizo

Beach of Sorrizo (Arteixo, A Coruña, NW Spain)

43º18’N, 8º34’ WVigo, July 14th 2005VERTIMAR 2005


Trials of in situ bioremediation on the beach of Sorrizo (Spain) 3. MATERIALS AND METHODS


The experimental site: the beach of Sorrizo





Nitrophoska Supreme (NPK): commercial nutrients formulation (Compo, Germany; 20% N, 5% P205).

B350: commercial bioaugmentation product (Bio-systems, USA).

L1800: commercial bioaugmentation product with biodegradable surfactants (Bio-systems Co, USA).

Autochthonous culture (UB): obtained by enrichment of fuel-degrading populations from a beach affected by the oil spill of the Prestige. Developed by the Department of Microbiology of the University of Barcelona (Spain).

Assessed products

The applications took place between April and October 2003, after a preliminary clean-up of the beach.





Assessed products

Zone

Treatment

1 Nitrophoska

2 Blank

3 B350

4 B350 + L1800

5Autochtonous culture

6 Blank

The beach was divided into six sections that were treated with the different products.





Experiments with granite tiles

Experiments with granite tiles were performed to minimize the heterogeneity of the environmental

samples.






The bioremediation

agents were applied with the same frequency and doses used

on the beach

Supra-littoral tiles

NPKBlankB350L1800UB









B350

UB

B350 UB

Intertidal tiles


Monitoring of the beach




Seawater and interstitial water: Nutrients Hydrocarbon-degrading

populations PAH

Sand: Residual oil PAH Percentages of

degradation

Rocks: Percentages of

degradation

Granite tiles: Percentages of

degradation Oxygen monitoring

Field experiments with several bioremediation agents following the Prestige accident 4. RESULTS AND DISCUSSION

Level of nutrients

Ammonia

0.00.10.20.30.40.50.60.70.80.91.01.11.21.3

14/0

5/20

03

14/0

6/20

03

14/0

7/20

03

14/0

8/20

03

14/0

9/20

03

14/1

0/20

03

14/1

1/20

03

14/1

2/20

03

14/0

1/20

04

14/0

2/20

04

14/0

3/20

04

14/0

4/20

04

14/0

5/20

04

14/0

6/20

04

14/0

7/20

04

14/0

8/20

04

14/0

9/20

04

Co

nc

en

tra

tio

n (

pp

m N

-NH 4

) Zone 1

Zone 2

Zone 3

Zone 4

Zone 5

Zone 6

Seaw ater

Freshw ater

Applications



Trials of in situ bioremediation on the beach of Sorrizo (Spain) 4. RESULTS AND DISCUSSION


Level of nutrients

Nitrate

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

14/0

5/20

03

14/0

6/20

03

14/0

7/20

03

14/0

8/20

03

14/0

9/20

03

14/1

0/20

03

14/1

1/20

03

14/1

2/20

03

14/0

1/20

04

14/0

2/20

04

14/0

3/20

04

14/0

4/20

04

14/0

5/20

04

14/0

6/20

04

14/0

7/20

04

14/0

8/20

04

14/0

9/20

04

Co

nc

en

tra

tio

n (

pp

m N

-NO 3

)

Zone 1

Zone 2

Zone 3

Zone 4

Zone 5

Zone 6

Seaw ater

Freshw ater

Applications





Hydrocarbon-degrading populations

Alkane degraders

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

1.0E+07

14/0

4/20

03

28/0

4/20

03

12/0

5/20

03

26/0

5/20

03

09/0

6/20

03

23/0

6/20

03

07/0

7/20

03

21/0

7/20

03

04/0

8/20

03

18/0

8/20

03

01/0

9/20

03

15/0

9/20

03

29/0

9/20

03

MP

N/m

L

Zone 1

Zone 2

Zone 3

Zone 4

Zone 5

Zone 6

Seaw ater

Freshw ater




10-40%


Hydrocarbon-degrading populations

Zone 1

Zone 2

Zone 3

Zone 4

Zone 5

Zone 6

Seaw ater

Freshw ater

PAH degraders

1.0E+01

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

14/0

4/20

03

28/0

4/20

03

12/0

5/20

03

26/0

5/20

03

09/0

6/20

03

23/0

6/20

03

07/0

7/20

03

21/0

7/20

03

04/0

8/20

03

18/0

8/20

03

01/0

9/20

03

15/0

9/20

03

29/0

9/20

03

MP

N/m

L




5-20%


Polycyclic aromatic hydrocarbons




DateConcentration of PAH (g/L)

SeawaterZone

1Zone

2Zone

3Zone

4Zone

5

14/04/03 0.107 - 0.041 0.055 7.149 -

30/04/03 0.161 0.049 0.127 2.054 3.426 0.15

28/05/03 0.048 0.287 0.04 0.105 0.737 0.33

18/06/03 0.162 0.214 0.328 0.262 1.35 0.323

21/07/03 0.085 0.075 0.103 0.202 0.45 0.072

25/08/03 0 0 0 0.04 0.015 0

24/09/03 0 0 0 0.07 0.015 0

24/10/03 0 0 0 0.031 0.055 0

10/12/03 0 0 0 0 0 0

12/02/04 0 0 0 0 0 0


Concentration of residual oil in sand

0

0.5

1

1.5

2

2.5

3

3.5

apr-0

3

may

-03

jun-0

3

aug-

03

oct-0

3

dec-0

3

feb-

04

may

-04

sep-

04

Co

nce

ntr

atio

n o

f o

il (

g/k

g o

f d

ry s

and

)

Zone 1

Zone 2

Zone 3

Zone 4

Zone 5

Zone 6





Concentration of PAH in sand




0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

apr-0

3

may

-03

jun-0

3

aug-

03

oct-0

3

dec-

03

feb-

04

may

-04

Co

nce

ntr

atio

n o

f P

AH

(m

g/k

g o

f d

ry s

and

)

Zone 1

Zone 2

Zone 3

Zone 4

Zone 5

Zone 6

Aromatics

0

10

20

30

40

50

60

70

80

90

100

Deg

rad

atio

n e

xten

t (%

)

apr-03 jun-03 aug-03 oct-03 feb-04 sep-04


Degradation in sand




Saturates

0

10

20

30

40

50

60

70

80

90

100

Deg

rad

atio

n e

xten

t (%

)

apr-03 jun-03 aug-03 oct-03 feb-04 sep-04


Degradation in rocksAromatics

0

10

20

30

40

50

60

70

80

90

100

jun-

03ju

l-03

sep-

03

dec-

03

feb-

04

apr-0

4

sep-

04D

egra

dat

ion

ext

ent

(%)

Saturates

0

10

20

30

40

50

60

70

80

90

100

jun-

03

jul-0

3

sep-

03

dec-

03

feb-

04

apr-0

4

sep-

04

Deg

rad

atio

n e

xten

t (%

)

Zone 1 Zone 2 Zone 3Zone 4 Zone 5 Zone 6





0

10

20

30

40

50

60

70

80

90

100

Deg

rad

atio

n e

xten

t (%

)

15 d 30 d 60 d 120 d 240 d

Intertidal tiles

0

10

20

30

40

50

60

70

80

90

100

0 30 60 90 120 150 180 210

Time (days)

Deg

rad

ació

n e

xten

t (%

)




Degradation of aromatics in tiles

0

1 0 0

0 3 0 6 0 9 0 1 2 0

Blank B350 UB


0

1

2

3

4

5

6

7

8

9

10

11

12

0 60 120 180 240 300 360

Time (days)

Oxy

gen

co

nte

nt

(%)

Intertidal tiles

0

1

2

3

4

5

6

7

8

9

10

0 60 120 180 240 300 360

Time (days)

Oxy

gen

co

nte

nt

(%)




Oxygen monitoring in tiles

0100

0 30 60 90 120

NPK Blank B350 L1800 UB


Persistent pollution in rocks

18 months after the oil spill the rocks were still coated

with fuel oil





Biodiesel

Sunflower oil methyl esters produced through the transesterification of

sunflower oil.

It is easily incorporated into oil and reduces its apparent viscosity, increasing the surface area of the oil and accelerating microbial degradation.

It may also induce increased microbial activity as a source of bioavailable carbon.

How it acts

It is readily biodegraded in the environment.

No long-term toxicity or damage has been documented.

It is cheap. Its spraying is a low-

cost operation.

Advantages





Biodiesel

Biodiesel-treated face

The experiments

with biodiesel started in

March 2004 on a polluted rock from the beach





Biodiesel0 days

150 days

80 days




470 days


Biodiesel

DateSaturates

(%)Aromatics

(%)Polars

(%)

Before the application

Mar-04

9.7 34.3 56.0

Non-treated face Sep-04 11.1 32.6 56.3

Biodiesel-treated face

Sep-04 9.3 24.1 66.6

It did not only acted as a cleaning agent but also as a

BIOREMEDIATION agent




Percentages of the fractions of the oil from the rock

Field experiments with several bioremediation agents following the Prestige accident 5. CONCLUSIONS



Trials of in situ bioremediation on the beach of Sorrizo (Spain) 5. CONCLUSIONS

The environmental parameters were appropriate for

biodegradation processes (nutrients,

microorganisms).

None of the products enhanced the biodegradation

rates in sand and rocks with regard to natural

attenuation.

It seemed that photooxidation significantly influenced

the degradation processes in the rocky substrate.

The application of the oleophilic agent biodiesel

improved the appearance of polluted rocks and

seemed to accelerate the biodegradation processes.




Trials of in situ bioremediation on the beach of Sorrizo (Spain) ACKNOWLEGMENTS

“FUNDACIÓN ARAO” (ARAO FOUNDATION) FOR THE FUNDS PROVIDED TO DO THIS RESEARCH

AUTHORS WISH TO THANK:




TRIALS OF IN SITU BIOREMEDIATION ON THE

BEACH OF SORRIZO (SPAIN)

THANKS FOR YOUR ATTENTION AND…

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trials of in situ bioremediation on the beach of sorrizo (spain)

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