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68
and 37
85
and longitudes 24
02
and 24
08
18
3
, Cl
, SO
2
4
, NO
3
, PO
3
4
,
SiO
2
, total and carbonate hardness.
After ltration and preservation with acidication with HNO
3
the water samples
were stored in plastic bottles of polyethylane (250 mL), and nally analyzed in
order to determine the following heavy metals contents: Fe, Mn, Cu, Cr, Ni, Pb,
Cd and Zn.
Cations were determined by atomic adsorption (GBS model 908AA) and the
anions, except Cl
3
L
1
and 24 = 118 mg NO
3
L
1
) exceeded the upper limit of 50 mg L
1
(EEC/80/778, 1980; WHO, 1984) for
nitrate concentration. Nitrate pollution is due to intensive use of nitrogen fertilizers
and the impact of industrial efuents.
Figures 5 and 6 present schematically a classication of groundwater hydro-
chemistry after Durov diagram. The waters from karst aquifer belong to NaCa
ClHCO
3
type and the waters from unconned aquifer to CaNaClHCO
3
, Na
Cl, NaMgCaClHCO
3
, NaClCaSO
4
types. The occurrence of CaCl facies
indicates active seawater intrusion (Gimenez and Morell, 1997). The presence of
GROUNDWATER POLLUTION BY HEAVY METALS 75
Figure 5. DUROV diagram, meq % (unconned aquifer).
NaCl groundwater in the coastal part of the study area, probably reects the initial
stage of inverse ion exchange (Appelo and Postma, 1996).
4.2. TRACE ELEMENTS
The coefcient of variation (Table I) indicates the wide dispersion of Mn, Zn,
Cd and the much smaller dispersion of Cu, Fe and Ni mainly in alluvial uncon-
ned aquifer. Metal release from waste sites may occur in response to changing
physicochemical conditions (Benvenuti et al., 1997).
The iron (Fe) concentration due to oxidation of sulde minerals is high (>0.2 mg
L
1
) at ve samples (6, 17, 19, 20, 24) from unconned aquifer. The mean man-
ganese (Mn) concentration in the groundwater from the unconned aquifer is 0.23 mg
L
1
and from the karst aquifer 0.029 mg L
1
.
As can be seen from Table I the highest values of heavy metals were recorded
at samples of the unconned aquifer (alluvial deposits and schists).
76 G. STAMATIS ET AL.
Figure 6. DUROV diagram, meq % (karst aquifer).
The lead (Pb) concentration in sixty-six percent (66%) of the collected samples
from both unconned and karst aquifer exceeds 50 ppb. These concentrations ex-
ceed the upper limit for drinking water (EEC/80.778, 1980; WHO, 1984). Highest
lead concentrations should be atributed to the presence of suldes mainly PbS and
are encountered in the Thorikon basin near to slag-heaps (samples 17, 18).
The zinc (Zn) concentration of the majority of samples (23) from both the
unconned and karst aquifers exceeds 100 ppb. The highest zinc concentrations
are encountered in the unconned aquifer of schists and are should be attributed to
oxidation of sulde minerals and the leaching of schist (Alexakis and Kelepertsis,
1998).
In fteen samples (15) from the unconned and karst aquifers the nickel (Ni)
concentration exceeds 50 ppb and in one sample (23) the copper (Cu) concentration
exceeds 100 ppb. In one sample (29) from unconned aquifer of Kamariza schist
the chromium (Cr) concentration exceeds 50 ppb.
In seventy-ve percent (75%) of the collected samples from both unconned
GROUNDWATER POLLUTION BY HEAVY METALS 77
and karst aquifers the cadmium (Cd) concentration exceeds 5 ppb. Highest cad-
mium concentrations should be attributed to mineralization.
The correlation coefcient measures the strength of the relationship between
two variables. Taking into account the correlation matrices of Tables II and III, the
following conclusions can be drawn:
4.2.1. Unconned Aquifer
Correlation coefcients >0.85 are found as following: CaCl (0.96), NaCl (0.99),
CdK (0.86). Correlation between FePb, FeNi, FeMn, FeCd, NiMn, NiCd,
MnCd, CrNi and CrCd is relatively high and signicant at p-level 0.05.
4.2.2. Karst Aquifer
High correlation (>0.85) have been obtained between: CaSO
4
(0.96), MgNa
(0.94), MgCl (0.93), MgMn (0.96), NaCl (1.00), NaMn (0.96), HCO
3
Pb
(0.85), ClMn (0.97), PO
4
Fe (0.96), PO
4
Pb (0.85), PO
4
Cr (0.86), CdFe (0.90),
CrCd (0.96). Also, correlation between Pb-Ni, FeNi, NiCd, NiCr, MnCd and
CrNi is signicant at p-level 0.05.
In conclusion, a signicant relationship is observed in the major ions having
the same charge but a different valence (CaNa, MgNa), in the ions having the
different charge but a same valence (NaCl, CaSO
4
) and in the ions having the
same charge and the same valence (CaMg) from the karst aquifer.
There is a relationship between the elements participating in the sulde min-
eralization (Pb, Zn, Cu, Cd) and iron-manganese mineralization. There is also
a strong relationship between NiCr in groundwater samples, as in soil samples
(Dimitriadis et al., 1994).
Using factor analysis (R-mode), the element distribution in the samples is ex-
plained in terms of four factors. The selected factors explain more than 72% of
the total variance of the data set. The rotated factor matrix is shown in Table IV.
From this table can be seen that the communalities of all the parameters are >0.62,
indicating that the 4-factors model explains adequately the variance of almost all
the parameters.
Factor I accounts for 29.7% of total variance with high loadings in the elements
K, Fe, Mn, Pb, Ni, Cd. Figure 7 shows the areal distribution of factor scores for
factor I. It can be seen that large part of the study area falls above the zero line
and in NW part of study area falls above the 0.4 line. That indicates that the study
area is affected by the process of this factor, which can be associated with the rich
mineralized basement of the Lavrio area and the mining activities. The high loading
of K in this factor should be attributed to seawater intrusion and to K-feldspar
schists dissolution (Rosen and Sarah, 1998).
Factor II accounts for 22.5% of total variance with high loadings in the elements
Mg, Na, Cl, SO
4
. This factor can be associated with the intrusion of seawater into
both aquifers, which increases the concentration of those ions (Ruiz et al., 1990;
Voudouris et al., 1997). The areal distribution of factor II (Figure 8) shows that high
78 G. STAMATIS ET AL.
Figure 7. Distribution of factor I scores.
positive scores (affected by the process of this factor) enclose mainly the coastal
part (marbles) and the Lavrio basin (alluvial deposits) of the study area.
Factor III accounts for 11.2% of total variance with high loadings in the ele-
ments Cu, PO
4
. This factor could be explained by the phosphate fertilizers and the
copper-bearing mineral of the recent Lavrio slags. The areal distribution of this
factor is limited in the northern part of Thotikon basin and in the northern part of
Lavrio area (Figure 9).
GROUNDWATER POLLUTION BY HEAVY METALS 79
Figure 8. Distribution of factor II scores.
Factor IV accounts for 9.1% of total variance with high loading in the element
Zn and can be associated with the rich mineralized basement of the Lavrio area
and the mining activities (Kwong et al., 1997). The areal distribution of this factor
shows that high positive scores enclose the northern part of the study area and the
Thorikon basin (Figure 10).
80 G. STAMATIS ET AL.
Figure 9. Distribution of factor III scores.
5. Conclusions
From the analysis of hydrochemical data from the Lavrio area, the following con-
clusions can be drawn:
There is wide dispersion of values of Mn, Zn, Cd in groundwater and much
smaller dispersion of Cu, Fe and Ni, mainly in alluvial unconned aquifer.
GROUNDWATER POLLUTION BY HEAVY METALS 81
Figure 10. Distribution of factor IV scores.
High concentrations of heavy metals are recorded at groundwater samples in
Lavrio area, the highest from the unconned aquifer (alluvial deposits and
schists). The concentration of lead and cadmium is higher than the upper limit
for drinking waters for 66 and 75% of the collected samples from both uncon-
ned and karst aquifers, respectively.
High zinc concentrations were detected in most groundwater samples from the
unconned aquifer of schists, related to oxidation of sulde minerals and the
82 G. STAMATIS ET AL.
leaching of schist. Nickel concentration is high in both the unconned and
karst aquifers.
Quality deterioration of groundwater is documented and attributed to seawater
intrusion and nitrate pollution due to intensive agricultural activities.
A signicant relationship is observed between the major ions CaNa, Mg
Na, NaCl, CaSO
4
and CaMg (karst aquifer). There is a close relationship
between the elements participating in the sulde (Pb, Zn, Cu, Cd) and iron-
manganese mineralization and a strong relationship between NiCr.
Application of factor analysis showed that four factors, which explain 72.5%
of the total variance, could describe the main hydrogeochemical processes,
which took place in the Lavrio area aquifers. From the maps of geographical
distribution of factor scores are determined areas of high mineralized basement
of the Lavrio area and the mining activities (factors I, II, III, IV), and zones of
high salinity, which is attributed to seawater intrusion (factor II).
The intensive mining activities that were carried out for centuries and the in-
tensied exploitation of aquifers resulted in the groundwater pollution. The area of
Lavrio is classied, from an environmental view, as a high risk area. In view of the
alarming conditions an integrated water resources management should be applied
for the confrontation of the environmental problem of Lavrio.
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