Study of the fate of the Prestige oil
spill in the marine environment by
chemical fingerprinting
Sergi Diez, Josep M. Bayona, Joan Albaigés
Dep. de Química Ambiental. CSIC. Barcelona
Laura de la Tore, Gracia Albuquerque
Área de Medio Ambiente. SASEMAR. Madrid
OBJETIVES
of oil fingerprinting
 Characterize the spilled oil in
order to assess its weathering and
persistence
in
the
marine
environment.
 Identify some potential illegal oil
discharges at the affected area.
December – 2002
August – 2003
(IEO)
September – 2004
(IEO)
April – 2005
Prestige
oil spill identification
1
Oil fractionation
Aliphatic fraction
(GC)
100
15
Aromatic fraction
(GC)
100
Phen.
20
Naph.
30
%
%
22%
0
rt
6.0008.00010.000
12.000
14.00016.000
18.000
20.000
22.000
24.00026.000
28.000
30.000
32.000
34.00036.000
38.000
40.000
42.000
44.000
50%
0
rt
6.0008.00010.00012.00014.00016.000
18.00020.00022.00024.00026.00028.00030.00032.00034.00036.00038.00040.00042.00044.000
Prestige
oil spill identification
2
GC-MS computerized peak integration
4
100
90
3
80
191
100
70
10
60
12
80
7
50
9 11 5
2
8
40
27Ts
27Tm
29ab
30ab
32abS
32abR
100
P2
P3
206+220
%
6
40
60
30
1
2
3
4
5
6
1
20
10
20
Source identification
indices
0
27
0
100
28
29
30
31
32
Time (min)
33
17
R
13 14
80
34
18
15 16
60
218
40
35
13
14
15
16
17
18
36
27bbR
27bbS
28bbR
28bbS
29bbR
29bbS
0
37
Weathering
assessment
D2
D3
indices
FUEL-F2
100
S
212+226
%
20
0
25
26
27
28
29
30
31
32
33
0
14.000 15.000 16.000
17.000 18.000 19.000 20.000 21.000 22.000 23.000
24.000 25.000
Prestige
oil spill identification
Multivariate data-analysis
Source Index
Pr/Ph
%27Ts
%29ab
%27d
%29aaS
%29bb(R+S)
%27bb
%28bb
%29bb
D2/P2
D3/P3
Diagnostic Prestige
ion
(n=3)
Pristane/phytane
113
0.98
100*Ts/(Ts+Tm)
191
24.4
191
43.7
100*29ab/(29ab+30ab)
217
37.7
100*27d(R+S)/[27d(R+S)+27bb(R+S)]
217
47.4
100*29aaS/(29aaS+29aaR)
217
47.2
100*29bb(R+S)/[29bb+ 29aa]
100*[27bbR+S)]/[27bb(R+S)+
218
37.1
28bb(R+S)+ 29bb(R+S)]
100*[28bb(R+S)]/[27bb(R+S)+
218
27.4
28bb(R+S)+ 29bb(R+S)]
100*[29bb(R+S)]/[27bb(R+S)+
218
35.6
28bb(R+S)+ 29bb(R+S)]
100*C2-DBT/(C2-DBT+C2-P)
206/212
34.0
100*C3-DBT/(C3-DBT+C3-P)
220/226
40.0
Definition
3
Prestige
oil spill identification
3
Multivariate data-analysis
Weather. Index
Definition
Diagnostic
ion
Prestige
(n=3)
Alkanes
(C13+C14)/(C25+C26)
85
1.1
C17/Pr
n-C17/pristane
85
2.0
C18/Ph
n-C18/phytane
85
1.8
N2
(N+N1)/N2
128/142/156
0.93
2MP/1MP
100*2MP/(1MP+2MP)
192
67
1MP/9MP
100*1MP/(1MP+9MP)
192
44
4MD/1MD
100*4MD/(1MD+4MD)
198
68
2+3MD/1MD
100*2+3MD/(2+3MD+1MD)
198
66
D2/C2
100*C2-DBT/(C2-DBT+C2-C)
212/256
67
D3/C3
100*C3-DBT/(C3-DBT+C3-C)
226/270
70
Surveillance network
2003-04
Source indicators
20
100
Prestige fuel-oil
80
60
40
20
100
80
60
40
20
0
5
10
15
20
25
30
Time (min)
35
40
45
50
100
80
20
60
40
20
100
Tanker washings
80
60
40
20
0
5
10
15
20
25
30
Time (min)
35
40
45
50
27
d
29
bb
28
bb
27
bb
+S
)
D3
/P
3
D2
/P
2
%
%
%
29
bb
(R
29
aa
S
%
32
ab
S
29
ab
27
Ts
10
%
%
%
%
%
Source indicators
70
60
50
40
30
20
Oil residues
0
%
27
d
29
bb
28
bb
27
bb
D3
/P
3
D2
/P
2
%
%
%
)
29
aa
S
%
32
ab
S
29
ab
27
Ts
29
bb
(R
+S
%
%
%
%
Source indicators
70
60
50
40
30
20
Other oil residues
10
0
Surveillance network
2003-04
Estaca
de Bares
30
10
32
29
171
61
Cedeira
64-65
Burela 33
Ferrol
69
O Vicedo
68
22-24
A Coruña
44°
41-42
40
43°
111
159-160
156 7 19
8
6 Muxia
C. Touriñan
Corcubión
C. Finisterre Carnota
104
20
51-53 27 Muros
21
Arousa
133-134 95 O Grove
130
94 Pontevedra
46-47 38 117
Vigo
25
26
42°
10°
59 166
C.Peñas
58
101
60
87 119 80
136
152
92
75
45
166 112
77
91
56
78-79
76
83
54
141
Avilés Gijón
55
Laredo
Ribadesella
Bilbao
S.Vicente de Santander
Castro Urdiales Mundaka
la Barquera
Prestige oil residues
Miño
9°
8°
7°
6°
5°
4°
3°
2°
Bidasoa
Surveillance network
2003-04
44°
Estaca
de Bares
40
63
57 111
159-160
156
43°
59 C.Peñas
Cedeira
Burela
Ferrol
O Vicedo
Avilés Gijón
A Coruña
C. Touriñan Muxia
Corcubión
C. Finisterre Carnota
Muros
46-47
48-49
Arousa
133-134 95 O Grove
130
Pontevedra
117 94
Vigo
42°
10°
50-62
64-69
58-60
152
Laredo
Ribadesella
Bilbao
S.Vicente de Santander
Castro Urdiales Mundaka
la Barquera
Other oil residues
Miño
9°
8°
7°
6°
5°
4°
3°
2°
Bidasoa
Surveillance network
2003-04
Weathering indicators
Dissolution, evaporation & biodegradation
Water washing of PAHs
S
Temporal evolution of alkyl-naphthalenes
1800
Original oil
3 months later
1500
1200
900
600
300
0
N-0
N-1
N-2
N-3
Dissolution index
1,00
0,90
0,80
0,60
0,50
0,40
0,30
0,20
0,10
M
17
4
M
15
3
M
12
7
M
10
0
M
81
M
54
M
44
M
37
M
25
M
10
M
7
0,00
FO
(N+N1)/N2
0,70
Evaporation
1,0
■ Original fuel
% normalized C 26
0,8
0,6
0,4
0,2
0,0
12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35
n-alkanes (0-12 months)
M3
720
FO
-F
e
M3 brer
o
9Ma
M4
r
2- z o
M4 2-A
b
524 ril
M6 A br
il
7M
M8
a
0- y o
1
M8 -jun
io
32
M8 -ju
n
611 io
-ju
M8
nio
81
M1
3
05 -jun
io
-2
6M1
ju
03 nio
M1 1-ju
lio
12
-4
-ju
M1
lio
13
M1 916 julio
M1 10ju
1
M1 5-1 lio
5
35
-1 -juli
o
M1
2
48 -ag
o
M1 20- s to
49 ago
-2
st
3o
M1 ago
62
s
-4 to
M1 Sep
74 t.
-S
ep
t.
(C13+C14)/(C25+C26)
Evaporation index
1,2
1,0
0,8
0,6
0,4
0,2
0,0
Biodegradation
n-C18
100
Phytane
15
20
30
40
%
Prestige fuel-oil
0
rt
6.000
8.000
10.000
12.000
14.000
16.000
18.000
20.000
22.000
24.000
26.000
28.000
30.000
32.000
34.000
36.000
38.000
40.000
42.000
44.000
Biodegradation
Temporal evolution of the n-C18/phytane ratio
3,0
2,5
2,0
1,5
1,0
0,5
0,0
M 20
M 25
M 30
M 35
Nov. 02
M 42
M 47
M 55
M 60
M 65
May
M 70
M 75
M 80
M 85
M 90
M 95 M 100 M 105 M 110
M 115 M 120 M 125 M 130 M 135 M 140 M 145 M 150
M 155 M 160 M 165 M 170
Nov. 03
Biodegradation
BIO-AM~1
Scan EI+
192
3.59e3
100
BIO-AM~1
Scan EI+
198
1.39e3
biodegraded
100
S
%
%
0
0
M37-F2
Scan EI+
192
3.14e4
100
M37-F2
Scan EI+
198
100
1.18e4
*
*
%
%
0
0
BIO-CO~1
Scan EI+
192
5.22e4
2-
100
3-
9- 1-
%
0
15.0 00
20 months
*
15.4 00
15.6 00
15.8 00
16.0 00
16.2 00
16.4 00
16.6 00
16.8 00
Scan EI+
198
2.19e4
100
4-
2/3-
original
1-
%
rt
15.2 00
BIO-CO~1
17.0 00
17.2 00
17.4 00
17.6 00
17.8 00
0
14.400
rt
14.600
14.800
15.000
15.200
15.400
15.600
15.800
16.000
16.200
16.400
16.600
16.800
17.000
17.200
17.400
Conclusions
-The chemical characterization of the
Prestige fuel-oil, at molecular level, has
provided
suitable
information
for
identifying the sources of oil residues
collected at sea or along the coast, and
understanding
the
environmental
weathering processes of the spilled oil.
Conclusions
- Most of the oil samples collected in the
area of the spill derived from the Prestige
oil.
However,
residues
from
tanker
deballasting operations (10%) and
bilge residues (7%) were incidentally
found.
Conclusions
-The samples collected during the year
after the spill did not show evidence of
significant weathering.
Dissolution, since the first weeks
(max. 2%)
Evaporation, from 3-4 months
(max. 5%)
Biodegradation, from 6-8 months
(max. 1%)