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Levels of heavy metals in some marine organisms from the western Mediterranean area (Spain)
Marine Pollution Bulletin Marine Pollution Bulletin, Vol. 28, No. 1, pp. 50-53, 1994 Copyright © 1994 Elsevier Science Ltd Printed in Great Britain. All rights reserved 0025-326X/94 $6.00+0.00
Pergamon
Levels of Heavy Metals in Some Marine Organisms from the Western Mediterranean Area (Spain) A. PASTOR*, F. HERNANDEZt:~, M. A. PERIS*, J. BELTRANt, J. V. SANCHOt & M. T. CASTILLOt *Department of Analytical Chemistry, Faculty of Chemical Sciences, University of Valencia, C/Dr Moliner, Valencia, Spain t Environmental and Natural Resources Laboratory, Universitat Jaume I, PO Box 224, 12080 Castell6n, Spain +To whom correspondence should be addressed.
The Mediterranean Sea is subject to heavy discharges of pollutants from numerous industrial processes,
particularly on the Spanish, French, and Italian shores, where there are high concentrations of factories. The levels of heavy metals accumulated by marine organisms are a function not only of water quality, but also of seasonal factors, temperature, salinity, diet, spawning and individual variation, among other factors. The levels of metals accumulated in some marine organisms may be many orders of magnitude above background concentrations, thus demonstrating the potential of certain species as bioindicators of heavy metal pollution (Chan, 1989). In this paper, the levels of Hg, Cd, and Pb in marine organisms (fish, molluscs, and crustaceans) from Spanish Mediterranean shores are presented. The concentrations of these metals in different marine organisms are compared in order to discern their potential as bioindicators. Samples of organisms were collected in spring and summer 1988 from 25 sampling stations located on the Spanish Mediterranean coast, including the provinces of Gerona, Barcelona, Tarragona, Castell6n, Valencia and Alicante, as well as the Balearic Islands (Fig. l).
N
\
Spain
Barcelona
/
40 ° 18~'~19
23 ~ du'car ~
4
2 t 2' Estartit 1 Blanes 2 Arenys 3 Mataro 4 Barcelona 5 Tarragona 6 L'Atmella 7 San Carlos 8 Vinaroz 9 Castellon 10 Burriana 11 Sagunto 12 Valencia 13
i
I
I
I
Fig. 1 Sampling stations for biota.
50
Cullera Gandia Alicante Santa Pola Ciudadela Mahon Alcudia Pto. Colom Soller Palma Ibiza San Antonio
14 15 16 17 18 19 20 21 22 23 24 25
Volume 2 8 / N u m b e r 1/January 1994
Some 31 different species of marine organisms were analysed. Samples were stored after collection in plastic bags in a freezer at -18°C. Prior to analysis samples were classified, weighed and measured. The axial muscle of fish and whole soft tissue of molluscs and crustaceans were prepared for analysis. Each sample, composed of several specimens (generally 6 for fish and crustaceans; 12 for molluscs) was lyophilized and homogenized in a mortar. Analysis of the lyophilized samples employed nitric acid digestions. Determinations of heavy metals were performed with a Perkin-Elmer 2380 or a PerkinElmer 5000 atomic absorption spectrophotometer, equipped with a 561 recorder, deuterium background corrector or Zeeman corrector, and a heated graphite atomizer HGA-400 for Cd and Pb with 0.5% (NH4)2HPO 4 as modifier. Mercury was analysed by a system 3 0 3 - 0 3 8 2 and the mercury/hydride system MHS-10. This procedure was tested with certified sample of mussel (MA-M-2)TM from the IAEA. The values obtained (in ~tg g-1 dry wt) for the analysis of six replicates of this sample were as follows: Hg (certified 0.95; found 1.03), Cd (certified 1.32; found 1.40), Pb (certified 1.92, found 2.08). Further details on analytical protocols are given in Medina et aL (1986). Table 1 shows summary data for heavy metal levels found in the species studied in this work, expressed in
ng g-1 fresh wt. Comparisons with the results obtained in previous years reveal interesting conclusions. We have compared data obtained in the monitoring carried out in 1983 in the Castell6n and Valencia coasts (Medina et al., 1986)--selecting only spring and summer data--with the concentrations obtained in this paper for the same area (data from sampling stations 10 to 14). This reveals an increasing trend in Cd and Pb concentrations. The Cd concentrations found in Mytilus galloprovincialis in 1983 varied from 43.5 to 81.2 ng g-1 (Medina et al., 1986) compared to 50 to 497 ng g-l in 1988. Similar increases in Cd levels were noted in Mullus barbatus and M. surmuletus, from 0.4-4.4 ng g-1 wet wt in 1983 to 33-135 ng g-1 in 1988. Pb levels ranged from 369 to 2296 ng g-I in Mytilus galloprovincialis in 1983, but from 154 to 867 ng g-~ in 1988. In Mullus barbatus and M. surmuletus values of Pb varied from 6.1 to 225 ng g-1 in 1983 and from 55 to 3094 ng g-1 in 1988. These comparisons are affected to some extent by the precise locations of sampling, which varied somewhat between the two studies. Figure 2 shows the mean levels of Pb found in the crustaceans Aristeomorpha antennatus and A. foliacea, the mullet Mullus barbatus and M. surmuletus, and the mussel Mytilus galloprovincialis. Elevated levels of Pb are seen at Estartit, San Carlos, Cullera and Alicante. This is probably due to the fact that these stations are
TABLE 1 Metal levels in marine organisms.
Cd mean
ng g-1 range
Pb mean
7 18 14 6 3 2 9 1 3 3 2 1 2 5
49 43 67 43 53 19 24 13 33 24 601 11 40 21 312 38 32
10-510 10-107 12-207 10-110 10-274 10-58 10-30 10-20 10-55 10-87
402 105 960 163 543 90 74 53 108 114 241 55 139 383 215 63 169
4 5 1 2 2 1 23
28 46 10 40 35 40 80
1 12 4 28 14 3 2 1
nd 171 41 222 3500 759 450 40
Species
n
Mullusbarbatus-M. surmuletus Sardinapilchardus Micromessistiuspoutassou Thunnusthynnus Engmulis encrasicolus Lithognatus mormirus Maena Xiphiasgladius Trisopterusfuscus Merlucciusmerluccius Chamalea gallina Scorpaenaporcus Trigla lineata Serranuscabrilla
59 38
Boopsboops
Citharus linguatula Pagellus centrodontusP. erithynnus Naucrates ductor Seriola dumerili Charax puntazzo Trachinus draco Diplodus sargus
Lepidorhombus Aristeomorpha antennatus-
5
10-12 10-80 10-32 30-46 10-51 10-50 10-170 10-70 30-40 20-180
210 126 50 70 2220 50 157
ng g-1 range 50-11 189 50-463 50-3238 50-350 50-8296 50-301 50-125 50-60 50-166 10-414 50-64 50-450 50-715 50-77 50-350 50-450 50-420 50-90 50-4390 50-790
Hg Org. mean 113 84 160 399 49 87 81 347 117 54 nd 59 79 107 53 66 132 nd 34 60 nd 95 320 364
ng g-1 range 30-1162 30-890 30-356 40-1120 30-111 30-293 30-194 280-410 114-121 30-110 30-90 40-110 30-183 30-102 40-240
30-40
80-110 31-820
Hg Total mean 139 105 191 499 60 104 99 417 142 66 nd 66 100 129 75 71 168 nd 42 9O 45 110 32O 460
n g g -1 range 30-1387 30-1000 42-406 68-1359 30-125 30-321 30-238 340-470 122-163 30-140 30-100 40-130 49-210 30-112 50-280
30-60 40-50 90-130 40-1000
A. foliacea
Nephrops norvegicus Macropipusdepurator Pennaeus kerathurus Mytilusgalloprovincialis Murexbrandaris Trunculariopsistrunculus Patella caerulea Donax vittatus
10-500 30-50 10-1037 2 7 0 - 1 3 581 520-1225 150-750
nd 582 56 743 375 116 980 360
50-1656 50-74 50-2830 50-430 62-220 670-1290
390 270 352 96 118 81 nd nd
30-1414 36-1110 30-1310 30-430 55-130
480 307 400 122 158 120 nd nd
30-1462 42-1240 30-1730 45-520 84-180
nd: Not detected.
51
Marine Pollution Bulletin
Pb (ng g-1 fresh weight) Aristeomorpha Mullus 400
Mytilus 1600 3094
2278
300
1400 1200 100 8O0
200
600
rl
100
4O0 200
0 Esta~it Barcelona Gandia Vinaroz Valencia (5) (1) Mataro San Carlos(9)Castellon (13).Cullera (15) Alicante / / " (14) / ! (16) (8) (10) (4) / Sampling stations Aristeomorpha ~ Mullus ~ Mytilus /
Mouth of polluted rivers
Fig. 2 Concentrations of lead in three species from selected sampling stations.
Cd (ng g-1 fresh weight) Aristeomorpha Mullus 120[
Mytilus 600
100
5OO
80
40O
,o1 1
300
60
200 100
0
, , il 0 Estartit Barcelona Vinaroz Valencia Gandia / I (1) Mataro (5) .San Carlos (9) Castellon (13) Cullera (15) Alicante (4) /" (8) (10) / (14) / 1151 Sampling stations ~] Mullus ~ Mytilus
/ I Mouth of polluted rivers Fig. 3 Concentrations of cadmium in three species from selected sampling stations.
located near the mouths of rivers (see Fig. 1), which carry industrial discharges of pollutants to the offshore waters. The highest levels of Cd were found in samples collected in Estartit, Barcelona and Valencia, the last two of these being areas with high populations and considerable industrial activity (Fig. 3). The mean levels of Hg varied without any apparent relation to industrial areas or polluted rivers (Fig. 4). This can be explained by the fact that Mediterranean 52
Sea is characterized by a high overall level of Hg (Bacci, 1989). Comparing the different species studied, the highest mean levels of total Hg were found in crustaceans, including Aristeomorpha antennatus and A. foliacea (mean value 460 ng g-l), Nephrops norvegicus (480 ng g-l) and Pennaeus kerathurus (400 ng g-l) and the fish Thunnus thynnus (499 ng g-t) and Xiphias gladius (417 ng g-l); see Table 1. The greatest concentrations of Cd were obtained in molluscs, particularly Murex brandaris (mean 3500 ng
Volume 28/Number 1/January 1994
Hg (ng g-1fresh weight) Aristeomorpha Mullus
Mytilus
F
t
6001
100
500~-
8O
100
~
0 Estartit
/ (1)
Barcelona
'
Vinaroz
EI!~:I: 20 I~:i:i:
Valencia
Gandia
0
Mataro (5)'San(Carl°s78)(9) Castellon (13)"Cullera/'(14) (15) Alicante (4) (10) / I (16) Sampling stations Aristeomorpha ~ Mullus ~ Mytilus // Mouth of polluted rivers
Fig. 4 Concentrations of mercury in threespecies from selected sampling stations.
g-l). The highest values of Pb were also found in molluscs in general (980 ng g-1 in Patella caerulea and 743 ng g-i in Mytilus galloprovincialis), although some of the pelagic fish analysed also contained elevated levels of this metal (Micromessistius poutassou, with 960 ng g-1 and Engraulis encrasicoluswith 543 ngg-l). It may be concluded that both rivers carrying industrial discharges and urbanized areas produce heavy metal pollution in the coastal zone of the western Mediterranean Sea. The molluscs studied here appear to be useful bioindicators of Cd and Pb, while Thunnidae and some crustaceans may be appropriate
bioindicators for Hg due to their high accumulation of this element. We are very grateful to MOPU for their financial support to carry out the MEDPOL Programme. Bacci, E. (1989). Mercury in the Mediterranean. Mar. Pollut. BulL 20, 59-63. Chan, H. M. (1989). Temporal and spatial fluctuations in the trace metal concentration in transplanted mussels in Hong Kong. Mar. Pollut. Bull. 20, 82-86. Medina, J., Hern~indez, F., Pastor, A., Beferull, J. B. & Barberfi, J. C. (1986). Determination of mercury, cadmium, chromium and lead in marine organisms by flameless atomic absorption spectrophotometry. Mar. Pollut. Bull. 17, 41-44.
53
Pergamon
Levels of Heavy Metals in Some Marine Organisms from the Western Mediterranean Area (Spain) A. PASTOR*, F. HERNANDEZt:~, M. A. PERIS*, J. BELTRANt, J. V. SANCHOt & M. T. CASTILLOt *Department of Analytical Chemistry, Faculty of Chemical Sciences, University of Valencia, C/Dr Moliner, Valencia, Spain t Environmental and Natural Resources Laboratory, Universitat Jaume I, PO Box 224, 12080 Castell6n, Spain +To whom correspondence should be addressed.
The Mediterranean Sea is subject to heavy discharges of pollutants from numerous industrial processes,
particularly on the Spanish, French, and Italian shores, where there are high concentrations of factories. The levels of heavy metals accumulated by marine organisms are a function not only of water quality, but also of seasonal factors, temperature, salinity, diet, spawning and individual variation, among other factors. The levels of metals accumulated in some marine organisms may be many orders of magnitude above background concentrations, thus demonstrating the potential of certain species as bioindicators of heavy metal pollution (Chan, 1989). In this paper, the levels of Hg, Cd, and Pb in marine organisms (fish, molluscs, and crustaceans) from Spanish Mediterranean shores are presented. The concentrations of these metals in different marine organisms are compared in order to discern their potential as bioindicators. Samples of organisms were collected in spring and summer 1988 from 25 sampling stations located on the Spanish Mediterranean coast, including the provinces of Gerona, Barcelona, Tarragona, Castell6n, Valencia and Alicante, as well as the Balearic Islands (Fig. l).
N
\
Spain
Barcelona
/
40 ° 18~'~19
23 ~ du'car ~
4
2 t 2' Estartit 1 Blanes 2 Arenys 3 Mataro 4 Barcelona 5 Tarragona 6 L'Atmella 7 San Carlos 8 Vinaroz 9 Castellon 10 Burriana 11 Sagunto 12 Valencia 13
i
I
I
I
Fig. 1 Sampling stations for biota.
50
Cullera Gandia Alicante Santa Pola Ciudadela Mahon Alcudia Pto. Colom Soller Palma Ibiza San Antonio
14 15 16 17 18 19 20 21 22 23 24 25
Volume 2 8 / N u m b e r 1/January 1994
Some 31 different species of marine organisms were analysed. Samples were stored after collection in plastic bags in a freezer at -18°C. Prior to analysis samples were classified, weighed and measured. The axial muscle of fish and whole soft tissue of molluscs and crustaceans were prepared for analysis. Each sample, composed of several specimens (generally 6 for fish and crustaceans; 12 for molluscs) was lyophilized and homogenized in a mortar. Analysis of the lyophilized samples employed nitric acid digestions. Determinations of heavy metals were performed with a Perkin-Elmer 2380 or a PerkinElmer 5000 atomic absorption spectrophotometer, equipped with a 561 recorder, deuterium background corrector or Zeeman corrector, and a heated graphite atomizer HGA-400 for Cd and Pb with 0.5% (NH4)2HPO 4 as modifier. Mercury was analysed by a system 3 0 3 - 0 3 8 2 and the mercury/hydride system MHS-10. This procedure was tested with certified sample of mussel (MA-M-2)TM from the IAEA. The values obtained (in ~tg g-1 dry wt) for the analysis of six replicates of this sample were as follows: Hg (certified 0.95; found 1.03), Cd (certified 1.32; found 1.40), Pb (certified 1.92, found 2.08). Further details on analytical protocols are given in Medina et aL (1986). Table 1 shows summary data for heavy metal levels found in the species studied in this work, expressed in
ng g-1 fresh wt. Comparisons with the results obtained in previous years reveal interesting conclusions. We have compared data obtained in the monitoring carried out in 1983 in the Castell6n and Valencia coasts (Medina et al., 1986)--selecting only spring and summer data--with the concentrations obtained in this paper for the same area (data from sampling stations 10 to 14). This reveals an increasing trend in Cd and Pb concentrations. The Cd concentrations found in Mytilus galloprovincialis in 1983 varied from 43.5 to 81.2 ng g-1 (Medina et al., 1986) compared to 50 to 497 ng g-l in 1988. Similar increases in Cd levels were noted in Mullus barbatus and M. surmuletus, from 0.4-4.4 ng g-1 wet wt in 1983 to 33-135 ng g-1 in 1988. Pb levels ranged from 369 to 2296 ng g-I in Mytilus galloprovincialis in 1983, but from 154 to 867 ng g-~ in 1988. In Mullus barbatus and M. surmuletus values of Pb varied from 6.1 to 225 ng g-1 in 1983 and from 55 to 3094 ng g-1 in 1988. These comparisons are affected to some extent by the precise locations of sampling, which varied somewhat between the two studies. Figure 2 shows the mean levels of Pb found in the crustaceans Aristeomorpha antennatus and A. foliacea, the mullet Mullus barbatus and M. surmuletus, and the mussel Mytilus galloprovincialis. Elevated levels of Pb are seen at Estartit, San Carlos, Cullera and Alicante. This is probably due to the fact that these stations are
TABLE 1 Metal levels in marine organisms.
Cd mean
ng g-1 range
Pb mean
7 18 14 6 3 2 9 1 3 3 2 1 2 5
49 43 67 43 53 19 24 13 33 24 601 11 40 21 312 38 32
10-510 10-107 12-207 10-110 10-274 10-58 10-30 10-20 10-55 10-87
402 105 960 163 543 90 74 53 108 114 241 55 139 383 215 63 169
4 5 1 2 2 1 23
28 46 10 40 35 40 80
1 12 4 28 14 3 2 1
nd 171 41 222 3500 759 450 40
Species
n
Mullusbarbatus-M. surmuletus Sardinapilchardus Micromessistiuspoutassou Thunnusthynnus Engmulis encrasicolus Lithognatus mormirus Maena Xiphiasgladius Trisopterusfuscus Merlucciusmerluccius Chamalea gallina Scorpaenaporcus Trigla lineata Serranuscabrilla
59 38
Boopsboops
Citharus linguatula Pagellus centrodontusP. erithynnus Naucrates ductor Seriola dumerili Charax puntazzo Trachinus draco Diplodus sargus
Lepidorhombus Aristeomorpha antennatus-
5
10-12 10-80 10-32 30-46 10-51 10-50 10-170 10-70 30-40 20-180
210 126 50 70 2220 50 157
ng g-1 range 50-11 189 50-463 50-3238 50-350 50-8296 50-301 50-125 50-60 50-166 10-414 50-64 50-450 50-715 50-77 50-350 50-450 50-420 50-90 50-4390 50-790
Hg Org. mean 113 84 160 399 49 87 81 347 117 54 nd 59 79 107 53 66 132 nd 34 60 nd 95 320 364
ng g-1 range 30-1162 30-890 30-356 40-1120 30-111 30-293 30-194 280-410 114-121 30-110 30-90 40-110 30-183 30-102 40-240
30-40
80-110 31-820
Hg Total mean 139 105 191 499 60 104 99 417 142 66 nd 66 100 129 75 71 168 nd 42 9O 45 110 32O 460
n g g -1 range 30-1387 30-1000 42-406 68-1359 30-125 30-321 30-238 340-470 122-163 30-140 30-100 40-130 49-210 30-112 50-280
30-60 40-50 90-130 40-1000
A. foliacea
Nephrops norvegicus Macropipusdepurator Pennaeus kerathurus Mytilusgalloprovincialis Murexbrandaris Trunculariopsistrunculus Patella caerulea Donax vittatus
10-500 30-50 10-1037 2 7 0 - 1 3 581 520-1225 150-750
nd 582 56 743 375 116 980 360
50-1656 50-74 50-2830 50-430 62-220 670-1290
390 270 352 96 118 81 nd nd
30-1414 36-1110 30-1310 30-430 55-130
480 307 400 122 158 120 nd nd
30-1462 42-1240 30-1730 45-520 84-180
nd: Not detected.
51
Marine Pollution Bulletin
Pb (ng g-1 fresh weight) Aristeomorpha Mullus 400
Mytilus 1600 3094
2278
300
1400 1200 100 8O0
200
600
rl
100
4O0 200
0 Esta~it Barcelona Gandia Vinaroz Valencia (5) (1) Mataro San Carlos(9)Castellon (13).Cullera (15) Alicante / / " (14) / ! (16) (8) (10) (4) / Sampling stations Aristeomorpha ~ Mullus ~ Mytilus /
Mouth of polluted rivers
Fig. 2 Concentrations of lead in three species from selected sampling stations.
Cd (ng g-1 fresh weight) Aristeomorpha Mullus 120[
Mytilus 600
100
5OO
80
40O
,o1 1
300
60
200 100
0
, , il 0 Estartit Barcelona Vinaroz Valencia Gandia / I (1) Mataro (5) .San Carlos (9) Castellon (13) Cullera (15) Alicante (4) /" (8) (10) / (14) / 1151 Sampling stations ~] Mullus ~ Mytilus
/ I Mouth of polluted rivers Fig. 3 Concentrations of cadmium in three species from selected sampling stations.
located near the mouths of rivers (see Fig. 1), which carry industrial discharges of pollutants to the offshore waters. The highest levels of Cd were found in samples collected in Estartit, Barcelona and Valencia, the last two of these being areas with high populations and considerable industrial activity (Fig. 3). The mean levels of Hg varied without any apparent relation to industrial areas or polluted rivers (Fig. 4). This can be explained by the fact that Mediterranean 52
Sea is characterized by a high overall level of Hg (Bacci, 1989). Comparing the different species studied, the highest mean levels of total Hg were found in crustaceans, including Aristeomorpha antennatus and A. foliacea (mean value 460 ng g-l), Nephrops norvegicus (480 ng g-l) and Pennaeus kerathurus (400 ng g-l) and the fish Thunnus thynnus (499 ng g-t) and Xiphias gladius (417 ng g-l); see Table 1. The greatest concentrations of Cd were obtained in molluscs, particularly Murex brandaris (mean 3500 ng
Volume 28/Number 1/January 1994
Hg (ng g-1fresh weight) Aristeomorpha Mullus
Mytilus
F
t
6001
100
500~-
8O
100
~
0 Estartit
/ (1)
Barcelona
'
Vinaroz
EI!~:I: 20 I~:i:i:
Valencia
Gandia
0
Mataro (5)'San(Carl°s78)(9) Castellon (13)"Cullera/'(14) (15) Alicante (4) (10) / I (16) Sampling stations Aristeomorpha ~ Mullus ~ Mytilus // Mouth of polluted rivers
Fig. 4 Concentrations of mercury in threespecies from selected sampling stations.
g-l). The highest values of Pb were also found in molluscs in general (980 ng g-1 in Patella caerulea and 743 ng g-i in Mytilus galloprovincialis), although some of the pelagic fish analysed also contained elevated levels of this metal (Micromessistius poutassou, with 960 ng g-1 and Engraulis encrasicoluswith 543 ngg-l). It may be concluded that both rivers carrying industrial discharges and urbanized areas produce heavy metal pollution in the coastal zone of the western Mediterranean Sea. The molluscs studied here appear to be useful bioindicators of Cd and Pb, while Thunnidae and some crustaceans may be appropriate
bioindicators for Hg due to their high accumulation of this element. We are very grateful to MOPU for their financial support to carry out the MEDPOL Programme. Bacci, E. (1989). Mercury in the Mediterranean. Mar. Pollut. BulL 20, 59-63. Chan, H. M. (1989). Temporal and spatial fluctuations in the trace metal concentration in transplanted mussels in Hong Kong. Mar. Pollut. Bull. 20, 82-86. Medina, J., Hern~indez, F., Pastor, A., Beferull, J. B. & Barberfi, J. C. (1986). Determination of mercury, cadmium, chromium and lead in marine organisms by flameless atomic absorption spectrophotometry. Mar. Pollut. Bull. 17, 41-44.
53