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)