SCARCE Course

Valencia 7-8 February 2011

Case study: The Guadalquivir River (estuary)

Julián Blasco, Ethel Eljarrat, Damiá Barceló

• General description of the Guadalquivir river

basin

• Studies carried out in the past (focusing to the

estuary)

• Aznalcollar disaster, an event in the estuary

• The Guadalquivir estuary project

• The SCARCE project, new approach to the

study of the river basin

•Length 657 km

•Main water resource

•Subjected to many

inputs

•Navigable up as far as

Seville (90 km

upstream). Pollution

and erosion problems

•The estuary has

additional ecological

value due to the

presence of the

Doñana National Park

(Biosphere reserve)

Contamination studies in the Guadalquivir river estuary

1970-1980

Lack of information. Grey literature

Two research groups from CSIC, IQOG and IRNASE. Studies related to

the levels of organochlorine pesticides, PCBs and mercury in eggs of

birds.

Hernández et al., 1976 study of the river basin (11 sampling stations

between Mogon and Sanlúcar de Barrameda). Organochlorine

contamination and mercury (low levels)

1980-1998

Group of UCO (Rincon, Zurera et al. 1986; Rincón 1986; Jodral et al. 1987; Rincon et al. 1987; Rincón

1987; Zurera 1987; Rincon-Leon et al. 1988).

River basin study but it is focused to metals in the biotic compartment.

Studies about the availability of metals. High levels for Cu and Pb and

intermediate levels for Zn.

The main entry of metals in the Guadalquivir and Doñana

National Park is associated to the Guadiamar river

• Organic contamination was homogenous for Guadiamar river (PCBs

and DDTs levels) were higher than recomended values and it was

related to agriculture and industrial activities. Levels of both

chemcial compounds were detected in aquatic species.

• The presence of pesticides in the Guadalquivir estuary was related

to a seasonal component.

• In 1998, the Regional Governement establish a plan for control

quality of the water in the estuary area (abiotic compartment water

and sediment, organochlorine and organophosphorous compounds;

in sediments PAHs, PCBs 7, 52 153 and180, DDT and DDE)

Aznalcóllar disaster 1998

- One of the main environmental catastrophes in Spain

Reasons

- Magnitud

- Close to the Doñana National Park

The figures of the disaster

•50 m of the dam were broken

• 6 million de cubic meters of muds and

acid waters were dumping to the

Guadiamar river

•3 m of muds were deposited close to the

mine

•25 millones million de cubic meters of

muds and acid waters stayed in the mining

pool

•pH acid waters close to 3

•2.5 Hm3 of acid water went into the

Guadalquivir estuary

Ecosystem impact

•Atmospheric contamination (490 µg/m3)

•Soils (Cu, Zn, As, Cd, Sb, Tl, Pb)

•Groundwater

•Guadiamar (Zn concentrations increased 300

times)

•The Guadalquivir river estuary

Metal levels in“Entremuros”

Zn 230 mg/L

Cd 0,5 mg/L

Tl, Mn, Co y Ni

Without treatment= 300 metric tonns of Zn

2.5 Hm3 acid waters were into the

Guadalquivir river estuary

Zn is the key element

Initial environmental assessment

•Lack of information

•Monitoring of the contamination in environmental

compartments.

Environmental compartments

-Estuary vertically homogenous

-No conservative behaviour

Peninsula Iberica

Rio Agrio

Mine Guadiamar

River

Aznalcóllar

Entremuros Balsa

tratamiento

Sanlúcar de Barrameda

N

5 Km

Parque Nacional De Doñana

Sevilla

1

2 3

4 5 6

1 2 3

4 5 6

Metal Low salinity High salinity

Zn

Cd

Pb

Cu

125 µg/L

0.40 µg/L

15 µg/L

10 µg/L

50 µg/L

0.20 µg/L

7 µg/L

5 µg/L

9.4

2.3

3.2

-0.09

11.9

0.2

3.3

3.6

-53.9

-0.3

-12.2

-15.4

2.5 0.29 1.0 0.4

Metals are accumulated in the lower part of the estuary

BONANZA EL PUNTALETE EL YESO

Zn Cd Pb Cu

Zn

Cd

Pb

Cu

Zn

Pb

Cu

Cd

Zn

Pb

Cu

Cd

Flux of metals in g.s-1

Sediments

Fecha Zn Cd Pb Cu Fe Mn

May 98

St. 2

St. 6

Sept 98

St. 2

St. 6

166

395

109

157

0.58

1.38

0.27

0.46

28.7

33.8

18.4

22.5

18.5

13.1

9.8

11.1

23697

14660

8769

12828

535

412

173

351

mg/kg dry weight

4846

1094

7590

1219

0

1000

2000

3000

4000

5000

6000

7000

8000

pp

m (

dry

weig

ht)

1968 1998

Año

Zn

Cu

1/1/1998 1/7/1998 1/1/1999 1/7/1999 1/1/2000 1/7/2000 1/1/2001 1/7/2001

Zn

(u

g/g

dry

we

igh

t)

0

5000

10000

15000

20000

1/1/98 1/7/98 1/1/99 1/7/99 1/1/00 1/7/00 1/1/01 1/7/01 1/1/02

Cu

(u

g/g

dry

we

igh

t)

-500

0

500

1000

1500

2000

2500

3000

3500

1/1/98 1/7/98 1/1/99 1/7/99 1/1/00 1/7/00 1/1/01 1/7/01 1/1/02

Cd

(ug

/g d

ry w

eig

ht)

0

2

4

6

8

10

12

C. angulata

Zn: 9134 ug/g

dw

Cu: 1460 ug/g

dw.

Cd: 5.45 ug/g

dw

1/1/98 1/7/98 1/1/99 1/7/99 1/1/00 1/7/00 1/1/01 1/7/01 1/1/02

Zn (

ug/g

dry

weig

ht)

0

200

400

600

800

1000

1200

1400

1/1/98 1/7/98 1/1/99 1/7/99 1/1/00 1/7/00 1/1/01 1/7/01 1/1/02

Cu (

ug/g

dry

weig

ht)

0

10

20

30

40

50

60

70

Scrobicularia

plana

Organic compounds

• Presence of mono and dichlorinated and brominated

triphenylamines in the sludge and contaminated soils

• Range 29 ug/g (close to the mine) to 0.14 ug/g (30 km)

• More halogenated compounds were not recorded in water

bodies-high lipophilicity

• Substituted carbazoles were found widespread in surface

water-hydrophilic

• Source of the products –use in ore processing or industrial

waste dumped.

Year 2000

Environmental impact assessment dredging activities Seville harbour

(CIS) • Contamination in sediments of Guadalquivir ( from dock of Seville harbour

to mouth of the Guadalquivir river

• Low levels of metals, high values in the inner of the dock

• Organic contaminants (PCBs and organochlorine pesticides) were found in

the dock and the Guadalquivir river , source agriculture.

• PAHs low levels in all samples

• Evaluation criteria CEDEX recomendations (Action Levels I, II and III)

Estación Boya 9 Boya 13 Boya 14 Boya 18 Boya 28 Boya 34 Boya D.Isaías

Localización 36º 53.357 6º 20.634

36º 54.508 6º 16.444

36º 53.435 6º 14.766

36º 53.435 6º 14.786

37º 01.917 6º 7.817

37º 04.928 6º 7.219

37º 19.064 6º 0.989

Fechas Profundidades 1 2 3 5 7 10 15 20 30

7/03/08 4/06/08 26/11/08 X X X X X X X X X

7/03/08 4/06/08 26/11/08 X X X X X X X X X

7/03/08 4/06/08 26/11/08 X X X X X X X X X

7/03/08 4/06/08 26/11/08 X X X X X X X X X

7/03/08 4/06/08 26/11/08 X X X X X X X X X

7/03/08 4/06/08 26/11/08 X X X X X X X X X

7/03/08 4/06/08 26/11/08 X X X X X X X X X

Organic compounds

Pesticidas organoclorados

HCHs α-HCH, β-HCH, γ-HCH, δ-HCH

DDXs 2,4-DDE, 4,4-DDE, 2,4-DDD, 4,4-DDD,

2,4-DDT, 4,4-DDT

Policlorobifenilos PCBs PCB-28, PCB-52, PCB-101, PCB-118,

PCB-138, PCB-153, PCB-180

Retardantes de llama bromados

PBDEs

di-BDEs (7,10,15), tri-BDEs (17,28,30),

tetra-BDEs (47,49,66,71,77), penta-BDEs

(85,99,100,119,126), hexa-BDEs

(138,139,140,153,154,156,169),

hepta-BDEs (171,180,183,184,191), octa-

BDEs (196,197,201,203,204,205), nona-

BDEs (206,207,208), deca-BDE (209)

non-PBDEs

pentabromoethylbenzene (PBEB),

hexabromobenzene (hexaBBz),

decabromodiphenylethane (deBDethane)

SCARCE project – new approach

• 25 sampling stations in the

river basin

• Priority and emergent

contaminants

• Improve of the knowledge

at river basin level

• Forcing variables related to

global change-effects

• Gaps about occurence and levels of pollutants in the

Guaadlquivir river basin

• Tool for water managers-quality RBMP and PoMs

Acknowledgements

• University of Cádiz (Dpt. Physical-Chemistry and Physical Oceanography

• Ecology of saltmarshes and Intertidal systems and Ecosystem

Oceanography teams from ICMAN (CSIC)

• CSIC and Consejería Medio Ambiente Junta Andalucía

• Autoridad Portuaria Puerto Sevilla

Thank you for you attention