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Study on the behavior of the heavy metals Cu, Cr, Ni, Zn, Fe, Mn and 137Cs in an estuarine ecosystem using
Mytilus galloprovincialis asa bioindicator species: the case of
Thermaikos gulf, Greece
Presented by :
Fiddy Semba Prasetiya
ECOMAMA, Vrije University of Brussels
Thermaikos GulfThermaikos Gulf
General IntroductionGeneral Introduction
Anthropogenic activities :Anthropogenic activities :
- Sewage and Industrial discharges- Sewage and Industrial discharges
- Harbour activities- Harbour activities
- Agricultural activities- Agricultural activities
Pollution on marine ecosystemPollution on marine ecosystem
Marine pollutionMarine pollution
Strategy and routine monitoring of contaminant in Strategy and routine monitoring of contaminant in marine environmentmarine environment
Mussels as pollution bio-indicatorMussels as pollution bio-indicator
Benthos as pollution bio-indicatorBenthos as pollution bio-indicator
Benthos as pollution Benthos as pollution bio-indicator bio-indicator (Regoli, 1998)(Regoli, 1998)
Mytilus galloprovincialis Mytilus galloprovincialis as a local bio-indicator as a local bio-indicator (Farrington (Farrington et al.et al., 1983), 1983)
Objective of the studyObjective of the study
To elucidate the seasonal behavior of metals To elucidate the seasonal behavior of metals (Cu, Cr, Ni, Zn, Fe, Mn and (Cu, Cr, Ni, Zn, Fe, Mn and 137137Cs) in mussels Cs) in mussels from an estuarine ecosystem, from an estuarine ecosystem,
To provide information on the interrelation of To provide information on the interrelation of metals, as well as to confirm the use of metals, as well as to confirm the use of cultivated cultivated MytilusMytilus galloprovincialisgalloprovincialis as bio- as bio-indicator for heavy metals and indicator for heavy metals and 137137Cs pollutionCs pollution
MethodologyMethodology
Sampling:Sampling:
-- 94 composite samples of 94 composite samples of M. galloprovincialisM. galloprovincialis (82 (82 for metals and 12 for for metals and 12 for 123123Cs) collected from Cs) collected from stat.LOU and stat.XAstat.LOU and stat.XA
-- Sampling period: April to October 2000 (monthly)Sampling period: April to October 2000 (monthly)
Location of sampling stationsLocation of sampling stations
MethodologyMethodology Heavy metal analyses:Heavy metal analyses:- A total of 1640 mussel specimens were examinedA total of 1640 mussel specimens were examined- Five to six replicates of composite samples consisting of the Five to six replicates of composite samples consisting of the
soft parts 20 specimens of similar size were preparedsoft parts 20 specimens of similar size were prepared- Each month the size of the specimens was similar, but Each month the size of the specimens was similar, but
differed inter-monthly (with length varying from 3.5 – 7.0 cm)differed inter-monthly (with length varying from 3.5 – 7.0 cm)- After freeze-drying with a CHRIST GAMMA 1-20 After freeze-drying with a CHRIST GAMMA 1-20
lyophilisator, 1 g of dried tissue was digested with 10 ml lyophilisator, 1 g of dried tissue was digested with 10 ml HNOHNO3 3
- Dry weight was 22-25% of the fresh weight. After digestion, Dry weight was 22-25% of the fresh weight. After digestion, sample was diluted with distilled water to 20 mlsample was diluted with distilled water to 20 ml
- A VS AA 20 plus flame AAS was used to determine Cu, Cr, A VS AA 20 plus flame AAS was used to determine Cu, Cr, Ni, Zn, Fe and Mn concentrationsNi, Zn, Fe and Mn concentrations
MethodologyMethodology 123123Cs analyses:Cs analyses:- Composite samples of at least 80-200 specimens (total Composite samples of at least 80-200 specimens (total
weight about 8-10 kg each sample) were prepared by weight about 8-10 kg each sample) were prepared by adding soft partsadding soft parts
- Each month the size of the specimens was similar, but Each month the size of the specimens was similar, but differed inter-monthly (with length varying from 2.3 – 8.5 cm)differed inter-monthly (with length varying from 2.3 – 8.5 cm)
- Samples were ashed using the “dry ashing procedure” for Samples were ashed using the “dry ashing procedure” for caesium and natural radionuclide measurementcaesium and natural radionuclide measurement
- The “ashing factor” factor was 7.1-14.6% of the fresh weight The “ashing factor” factor was 7.1-14.6% of the fresh weight - A quantity of 14-45 g of the ash sample was measured by A quantity of 14-45 g of the ash sample was measured by
gamma-spectroscopy measurement gamma-spectroscopy measurement
Results and discussionResults and discussion The levels of the measured metals, both radioactive and
stable, are characterized in general as low and comparable to those from non-polluted Mediterranean areas
The analyzed samples showed lower concentrations of Cu and Cr and similar or lower concentrations of Zn, Fe and Mn when compared to the respective ones from Italy
Mussels from Turkey had similar levels of Cu, Cr, Fe and Mn and higher levels of Zn and Ni (Koklu et al., 2000; Topcuoglu et al., 2002)
Results and discussionResults and discussionTable 2. Summary statistic of contaminants in mussels from Table 2. Summary statistic of contaminants in mussels from Thermaikos gulf (in mg/kg dry weight for metals and Bq/kg wet Thermaikos gulf (in mg/kg dry weight for metals and Bq/kg wet weight for weight for 123123CsCs
NN
AverageAverage
STDSTD
MedianMedian
MinMin
MaxMax
CuCu CrCr NiNi ZnZn FeFe MnMn 123123CsCs
8282
3.913.91
1.291.29
3.553.55
1.671.67
6.356.35
8282
1.851.85
0.770.77
1.731.73
0.200.20
3.463.46
8282
4.344.34
1.391.39
4.584.58
1.161.16
7.517.51
8282
56.356.3
27.427.4
59.659.6
20.820.8
115.0115.0
8282
395395
159159
403403
8181
715715
8282
14.114.1
4.74.7
12.712.7
7.27.2
25.325.3
8282
1.231.23
0.480.48
1.201.20
0.30.3
1.901.90
Results and discussionResults and discussionTable 3. Concentration of metals in mussels from Mediterranean and Black SeaTable 3. Concentration of metals in mussels from Mediterranean and Black Sea
AreaArea CuCu CrCr NiNi ZnZn FeFe MnMn
BulgariaBulgaria
PortugalPortugal
N.ItalyN.Italy
ItalyItaly
SpainSpain
SpainSpain
Bosporus Bosporus
Black SeaBlack Sea
UKUK
0.5-10.60.5-10.6
6.2-13.46.2-13.4
6.9-33.76.9-33.7
0.53-5.960.53-5.96
1.1-31.1-3
2.97-5.652.97-5.65
7.21-9.17.21-9.1
15.1-40.915.1-40.9
5.2-31.65.2-31.6
0.18-6.520.18-6.52
0.370.37
1.80-2.011.80-2.01
<0.06-7.58<0.06-7.58
0.6-5.70.6-5.7
1.3-111.3-11
4.02-24.074.02-24.07
5.0-42.95.0-42.9
12.8-42.012.8-42.0
140-542140-542
139-381139-381
10.8-5910.8-59
17.3-75.817.3-75.8
31.9-45.431.9-45.4
78-51278-512
110-368110-368
305-1175305-1175
11.7-18011.7-180
151-598151-598
215-1072215-1072
9.8-37.89.8-37.8
1.1-14.21.1-14.2
5.7-22.85.7-22.8
8.6-27.08.6-27.0
dwdw
dwdw
dwdw
wetwet
wwww
wetwet
dwdw
dwdw
dwdw
Results and discussionResults and discussion
Levels of Cu, Cr, Ni and Zn were generally statistically Levels of Cu, Cr, Ni and Zn were generally statistically lower (compared to Saronikos and Amvrakikos Gulf and lower (compared to Saronikos and Amvrakikos Gulf and Larymna Bay) Larymna Bay)
Saronikos gulf Saronikos gulf high levels of Cu and Znhigh levels of Cu and Zn Larymna bay Larymna bay high levels of Cr, Ni and Fehigh levels of Cr, Ni and Fe Thermaikos gulfThermaikos gulf high levels of Fe and Mnhigh levels of Fe and Mn
Fig.2 Mean values and LSD confidence intervals of metals in mussels from diverse Greek areas
AMVR = Amvrakikos gulf, LAR = Larymna bay, SAR = Saronikos gulf, TH = Thermaikos gulf-current data from both sampling stations (Catsiki, 2005)
Results and discussionResults and discussion
Time period (y)Time period (y) 123123Cs (Cs (Bq/kg ww)Bq/kg ww) RemarksRemarks
1984 – 19851984 – 1985
1986 – 19871986 – 1987
1988 – 19951988 – 1995
1999 – 20011999 – 2001bb
LLDLLD
0.68 0.68 ± 0.10± 0.10
7.10 ± 1.807.10 ± 1.80
0.46 ± 0.280.46 ± 0.28
0.92 ± 0.680.92 ± 0.68
0.10.1
Excluded max.observed 3 samples Excluded max.observed 3 samples from one stationfrom one station
Mean value Mean value ± Standard deviation of ± Standard deviation of (present study)(present study)
Measurement in dried soft tissue Measurement in dried soft tissue transformed into wet weighttransformed into wet weight
Table 4. Table 4. 123123Cs activity concentrations (Bq/kg wet weight) in Cs activity concentrations (Bq/kg wet weight) in Mytillus galloprovincialis Mytillus galloprovincialis in the Eastern Mediteranean – Aegean and in the Eastern Mediteranean – Aegean and Ionian Sea, (Florou Ionian Sea, (Florou et al., et al., 2002)2002)
Levels of Levels of 123123Cs in Cs in M. galloprovincialis M. galloprovincialis from Amvakikos gulf : 1.40 from Amvakikos gulf : 1.40 ± 0.29 Bq/kg ww (slightly ± 0.29 Bq/kg ww (slightly higher if compared to Italy and if compared to Italy and Adriatic coasts)Adriatic coasts)
Fig. 3. Temporal evolution of metals (average of five to six replicates per sampling) and 137Cs activity concentrations of composite samples) in mussels
2 groups of temporal pattern in mussels:
- Cs-Ni-Fe with min. during spring (April) and autumn (October)
- Cu-Zn & Mn-Cr with max. during spring (April) and autumn (October)
Temporal patterns of heavy metals 2 groups of
temporal pattern in mussels:
- Cs-Ni-Fe with min. during spring (April) and autumn (October)
- Cu-Zn & Mn-Cr with max. during spring (April) and autumn (October)