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LEVELS OF NICKEL AND VANADIUM IN SEAWATER FROM AREAS AFFECTED BY THE PRESTIGE SHIPWRECK ONE YEAR AFTER THE DISASTER. J uan Santos Echeandía, Ricardo Prego and Antonio Cobelo-García Departamento de Biogeoquímica Marina Instituto de Investigaciones Marinas (CSIC) Vigo, 13th July 2005. INDEX. - PowerPoint PPT Presentation
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LEVELS OF NICKEL AND VANADIUM IN SEAWATER LEVELS OF NICKEL AND VANADIUM IN SEAWATER
FROM AREAS AFFECTED BY THE PRESTIGE FROM AREAS AFFECTED BY THE PRESTIGE
SHIPWRECK ONE YEAR AFTER THE DISASTERSHIPWRECK ONE YEAR AFTER THE DISASTER
JJuanuan Santos Santos Echeandía, Ricardo Prego and Antonio Cobelo-GarcíaEcheandía, Ricardo Prego and Antonio Cobelo-García
Departamento de Biogeoquímica MarinaDepartamento de Biogeoquímica Marina
Instituto de Investigaciones Marinas (CSIC)Instituto de Investigaciones Marinas (CSIC)
Vigo, 13th July 2005Vigo, 13th July 2005
INDEX
INTRODUCTION
EXPERIMENTAL DEVELOPMENT
MARINE CAMPAIGNS: Material & Methods
PRACTICAL APPLICATION OF THE METHOD: Results & Discussion
CONCLUTIONS
INTRODUCTION
1
2
3
4
4
4
678
5
Atmospheric inputs:1. Wet deposition2. Dry deposition
Terrestial inputs:3. Rivers and run off4. Industrial waste5. Sewages
Other inputs:6. Ship spills7. Tanker sinks8. Oil refineries
INTRODUCTION
INTRODUCTION
• High concentrations of V (382 μg/g) and Ni (96.5 μg/g) in the fuel (nº 6, UK classification)
• Fuel emulsion releasing metals to the water
- High levels of copper in the waters from the sinking area(Prego & Cobelo-García, 2004 )
- Lost of Cu (32%), Ni (34%) y V (18%) in the fuel arriving the coast in comparison with the fuel coming from the tanker sunk.
OBJECTIVES
• Development of a method for the simultaneous determination of Cu, Ni and V in water
• Study and evaluation of the possible contamination by Ni and V derived from the Prestige fuel in galician coastal areas
EXPERIMENTAL DEVELOPMENT
- Development of a method by means of an electroanalytical technique (voltammetry) based in the cathodic redisolution (ACSV) for the simultaneous determination of Cu, Ni and V.
- The voltammetric techniques give us a ratio between the metal concentration in the sample and the peak height obtained from a potentials scan and it consists in three main steps:
- Preconcentration
- Rest
- Redisolution
EXPERIMENTAL DEVELOPMENT
EXPERIMENTAL DEVELOPMENT• Variable optimization:
- Variation of the ligand concentrations
- Influence of the solution´s pH
- Study of he deposition potential
- Effect of the deposition time
• Aplication range
• Detection Limit
• Reference Material
Catecol (mM) 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Ip (
nA)
0
1
2
3
4
5
Cu V Ni
Variable optimization: Variation of the ligand concentration
DMG (mM)
0.0 0.2 0.4 0.6 0.8 1.0
Ip (
nA
)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Cu V Ni
pH
6 7 8 9
Ip (
nA)
0
1
2
3
4
5
6
CuVNi
Variable optimization: Influence of thesolution´s pH
Udep (-V)
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Ip (
nA)
0
1
2
3
4
5
6
Cu V Ni
Variable optimization: Study of the deposition potential
Tiempo de deposición (min)
0 2 4 6 8 10
Ip C
u(n
A)
0
2
4
6
8
10
12
14
Ip N
i,V (
nA)
0
1
2
3
4
Cu V Ni
Variable optimization: Effect of the deposition time
Aplication Range
After making standard additions it was observed that the linear range arrived until:
Cu: 80 nM
Ni: 150 nM
V: 100 nM
[Cu] nM
0 20 40 60 80 100 120 140 160
Ip C
u (n
A)
0
10
20
30
40
50
Detection limitBlanks analysis:
Cu Ni V
Deposition time (seg)
200 200 900
Blank concentration
(x ±σ , nM)
0.46 ± 0.16 0.79 ± 0.13 0.31 ± 0.11
Detection limit
(3σ , nM)
0.5 0.4 0.3
Reference Material
Determination by means of ACSV of Cu, Ni and V in the reference material CASS-4 of coastal waters.
CASS-4
Element Obtained Concentration Certified Concentration
Copper
x σ , nM 9.7 0.9 9.4 0.9
Nickel
x σ , nM 5.4 ± 0.8 5.4 ± 0.5
Vanadium
x σ , nM 22.1 1.3 23.2 3.1
U (-V)
Ip (
nA)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
2
4
6
8
10
12
14
16
18
20
Cu
V
Ni
Resultant voltammogram
MARINE CAMPAIGNS: Material & Methods
Galician continental shelf
Sinking area
PRACTICAL APPLICATION OF THE METHOD: Results & Discussion
Analysis of Cu, Ni and V in the fuel.
Ratio of Ni/Cu in the
fuel: 29
Ratio of Ni/Cu in the fuel: 86
Cu Ni
32% Cu
34% Ni
18% V
1. Prestige sinking area
L a C o ru ñ a
V ig o
O p o rto
N
W1 3 º 1 2 º 1 1 º 1 0 º 9 º 8 º
4 1 º
4 2 º
4 3 º
4 4 º
P ro fu n d id a d e n m
4 5 7 3
1 8 2 9
3 6 5 8
9 1 52 7 4 4
1 8 2 9 9 1 51 8 3
Punto de muestreo
Banco de Galicia
PRACTICAL APPLICATION OF THE METHOD: Results & Discussion
Dep
th (
m)
Concentration (nM)
0 5 10 15 20 25 30 35 40 0
50
100
150
1000
2000
3000
4000
190
Ni V
2. Galician continental shelf
PRACTICAL APPLICATION OF THE METHOD: Results & Discussion
42º5´
9º
Finisterre Cape
Ria Muros
Ria Arousa
Ria Pontevedra
Ria Vigo
11º 0º
38º
8º 25’
Cies
Ons
1
2
3 4
5
6
7
8
43º
42º
43º
0 5
10
20
30 Km
Cornide de Saavedra
42º00´ N 43º00´ N 42º30´ N
42º 00´ N 43º 00´ N 42º 30´ N
1
2
3
4
5
6 dissolved total
Ni [nM]
1
2
3
4
5
6 dissolved total
V [nM]
Distance (km) 0 20 40 60 80 100
5
10
15 20
25 30
35
40 dissolved total
Distance (km) 0 20 40 60 80 100
10
20
30
40 dissolved total
35
25
15
5
SURFACE BOTTOM
CONCLUSIONS
A. Method set up for a wide range analysis of Cu, Ni and V in various types of waters (estuaric, coastal, oceanic, etc.), suitable for areas exposed to fuel dumps or other pollutants.
B. Determination of Ni and V levels in waters from the western galician continental shelf and the water column above the Prestige tanker sunk area. These metals are released from the fuel but only Ni seems to increase water levels punctually (sinking area). The mixing of the waters results in an attenuation of its levels in the Galician continental shelf.
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