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GROUNDWATER POLLUTION BY HEAVY METALS IN HISTORICAL

MINING AREA OF LAVRIO, ATTICA, GREECE


GEORGIOS STAMATIS
1
, KOSTAS VOUDOURIS
2
and FANIS KAREFILAKIS
1
1
Institute of Mineralogy-Geology, Agricultural University of Athens, Athens, Greece;
2
Laboratory
of Hydrogeology, Department of Geology, University of Patras, Rio, Patras, Greece
(

author for correspondence, e-mail: ggeo2stg@auadec.aua.gr)


(Received 4 May 1999; accepted 24 May 2000)
Abstract. This article deals with the impacts of past mining activities and inefcient water resources
management on groundwater quality in the Lavrio area. Thirty-three water samples were collected
during March 1998 and were analyzed for major ions (Ca, Mg, Na, K, HCO
3
, Cl, NO
3
, SO
4
,
PO
4
), trace elements (Fe, Pb, Ni, Zn, Mn, Cu, Cr, Cd) and water parameters (Temperature, pH,
conductivity, hardness and SiO
2
). High concentrations of heavy metals (lead, cadmium, zinc, nickel)
are recorded in groundwater samples in the Lavrio area. The highest concentrations are recorded in
the unconned aquifer (alluvial deposits and schists), due to mining activities. Quality deterioration
of groundwater is also decumented and attributed to seawater intrusion and nitrate pollution of ag-
ricultural origin. The data were subjected to simple correlation analysis and R-mode factor analysis
in order to examine the relationships between the parameters. There is a relationship between the
elements participating in the sulde (Pb, Zn, Cu, Cd) and iron-manganese mineralization and a strong
relationship between NiCr. In the factor analysis a four-factor model is suggested, which can explain
72.5% of the total variance. The contribution of each factor at every site is also computed and maps
showing the geographical distribution are illustrated. The areas with high concentrations of heavy
metals are dened from these maps.
Keywords: Greece, groundwater pollution, heavy metals, historical mining, hydrochemical analysis,
Lavrio, seawater intrusion, statistical analysis
1. Introduction
The area surrounding Lavrio was an area with intensive mining and metallurgical
activities dating back to 3000 B.C. and lasting up to 1989 (Marinos and Petras-
check, 1956; Konofagos, 1980; Kontopoulos et al., 1995). The aim of ancient mine
workers was the excavation of the silver-bearing galena, which was the main min-
eral among the mixed sulphurous ores, such as PbS, ZnS, FeS of Lavrio deposits.
Silver was extracted from galena and used to make silver coins in antiquity.
During the period 18641989 modern mine workers exploited not only the re-
maining deposits but also the huge piles of mineral and metallurgical wastes, rich in
Pb, Zn, Cu, Fe and other mineral elements. Enormous quantities of waste produced
from ancient mines, as well as from modern ones, were deposited in heaps around
Lavrio area, near the coastline, or even dumped into the sea.
Water, Air, and Soil Pollution 128: 6183, 2001.
2001 Kluwer Academic Publishers. Printed in the Netherlands.
62 G. STAMATIS ET AL.
The exploitation of the mineral wealth of Lavrio and the continuous spread
of the waste produced on land and sea, resulted in the natural environment being
heavily burdened. The effect on the landscape is still apparent.
Soil-chemical studies (Stavrakis et al., 1994; Kontopoulos et al., 1995; Tsaimou,
1997) carried out in the past indicated the extent of the pollution caused to toxic
metals, such as Pb, Zn, Sb, Cu, Hg, Cd, As, Fe and Mn. The increased concentration
of toxic metals is present especially in the mineral excavation area, as well as in the
processing and depositing waste areas. This phenomenon reveals the coexistence
of physical and anthropogenic pollution in these areas resulting in imminent and
serious adverse effects on man, animals and plants.
Epidemiological studies carried out in the area have shown very high concen-
trations of Pb and As in blood and urine and high concentrations of Pb, Cd and Zn
in childrens teeth. Lead poisoning is a common phenomenon in adults and elderly
men (Eikmann et al., 1991; Makropoulos et al., 1991).
Phytopathological studies (Chronopoulos and Chronopoulou-Sereli, 1986) car-
ried out on various plant species, showed a tangible decrease in their development,
in areas with high concentrations of Pb, Zn, Cu, Fe and Mn.
A recent hydrogeochemical study (Alexakis and Kelepertsis, 1998) carried out
in many sampling areas of eastern and southern Attica (Spata, Keratea, Thoriko and
Agios Konstantinos/Kamariza), has established a relationship between the quality
of groundwater and the geological environment. It has also revealed the extent of
pollution in these areas resulting from natural and man-made factors. On the basis
of the results, which have arisen from the environmental studies up to now, the
broader area of Lavrio is classied, from an environmental point of view, as a high
risk area (Stavrakis et al., 1994; Dimitriadis et al., 1994; Kontopoulos et al., 1995).
Most of the water demands are covered from the exploitation of groundwater
by numerous bored and dug wells. Due to the gradual impairment of groundwater
quality from seawater encroachment, the water supply of the area if nally achieved
by importing water. Therefore, it is easy to conclude that the effects on the health
of the population from the long-term use of the local water sources may be serious
due to high concentrations of heavy metals.
There are some industries and animal rearing activities in and around the Lavrio
area and the land is used locally for the cultivation of cereals, olives, vegetables
and vineyards. In recent decades, industrial units located in the region have also
affected groundwater quality.
This study investigates the hydrogeological conditions and especially the qual-
ity of different aquifers developing in the Lavrio area. The heavy metals distri-
bution inside the aquifers is particularly stressed and the extent of physical and
anthropogenetic activity taking place in the historical area is evaluated.
GROUNDWATER POLLUTION BY HEAVY METALS 63
2. Study Area
2.1. GEOGRAPHICAL AND GEOMORPHOLOGICAL SETTING
The study area is located between latitudes 37

68

and 37

85

and longitudes 24

02

and 24

08

and covers about 36 km


2
in the southeastern part of the Lavreotiki
peninsula and it is 60 km along from Athens. The area runs along the western
coast of the Aegean sea. The landscape is characterized as hilly or semi-hilly with
medium highs, from 0 to 373 m. In some parts of the basin the relief becomes
intense with the appearance of some ravines. To the north is located the Thorikos-
Plaka basin which dominated from agricultural activities and to the south the study
area is surrounded from smaller basins with more intense relief.
The Lavrio region is characterized by the typical Mediterranean climate of At-
tica. The mean annual temperature is 18.9

C, whereas the absolute maximum
temperature reaches 41.9

C and the absolute minimum 3.3

C. The mean an-
nual rainfall is 385 mm with dry periods usually extending from May to October
(National Meteorological Service, Elliniko station, period 19461995).
2.2. GEOLOGY
The Lavrio area, from a geotectonical point of view, is part of the Attic-Cycladic
massif and is composed of metamorphic rocks such as schists, phyllites and marbles.
The Attic-Cycladic massif in southern Attica consists of two main units (Lepsius,
1893; Marinos and Petrascheck, 1956).
(a) The autochthonous unit: It consists of marbles, dolomites and schists with
visible thickness greater than 1000 m (Figure 1). This unit comprises three sub-
units, from bottom to top:
(i) the lower marble (the thickness exceeds 600 m).
(ii) the mica schist of Kamariza-Kaisariani (the thickness is approximately 600 m).
(iii) the upper marble (the thickness is approximately 100 m).
(b) The overthrust nappe unit: It consists mainly of phyllites with marble intercal-
ations, quartzites, prasinites and serpentinites. The phyllitic nappe is assumed to
be a part of the Neohellenic tectonic nappe, according to Jacobshagen (1986) and
Katsikatsos (1992).
The older basic igneous rocks were metamorphosed, under high P/T conditions
to prasinites, metabasites, which are found as intercalations inside the phyllites.
After the high P/T metamorphism a granodioritic (granodiorite of Plaka) intruded
into both units (autochthon and overthrust nappe). This intrusion caused intensive
contact metamorphism in the surrounding area.
The mixed sulphurous ore-bearing of the broader area of Lavrio are composed
of silver-bearing galena, sphalerites and silica. The ores occur mainly inside marbles
64 G. STAMATIS ET AL.
Figure 1. Geological structure of the study area (Marinos and Petrascheck, 1956, modied by
Stamatis, 1999). 1) Quarternary deposits, 2) marbles, 3) mica-schists, 4) hornfels contactmeta-
morphic, 5) acid igneous rocks, granodiorites and 6) phyllites nappe with marbles and prasinites,
7) line of geologic section.
and close to their contact with schists. The origin of ore is hydrothermal apomag-
matic. The metalliferous liquids have resulted from granodioritic batholith known
as the granodiorite of Plaka (Marinos and Petrascheck, 1956).
The Quaternary deposits, located in the valleys, are composed mainly of clays,
gravels and coastal coarse-grained sandstones alternations. In the Thorikon basin
unconsolidated sediments overlaid the mica schists to the NE and the upper marble
GROUNDWATER POLLUTION BY HEAVY METALS 65
to the SE, and their thickness is up to 10 m. In the northern part of the area the
loose deposits overlaid phyllites and schists of the nappe unit and their thickness
reaches 5 m (Figure 1).
The lower marble forms an anticlinal structure, west of Lavrio with an almost
NS trending axis, traversing the hilly area of Sounio-Kamariza-Plaka. WNW
ESEto WE trending folds have been also encountered across the above-mentioned
large-scale structures. In the eastern part of the Lavrio area, the bedding planes of
the nappe unit dip gently to the East with a 10

18

dip (Marinos and Petrascheck,


1956).
2.3. HYDROGEOLOGY
The hydrogeological conditions of the study area, are directly related to the litholo-
gical composition of geological formations and the intense tectonism. The Lavrio
area is composed of geological formations with differing hydrogeological behavi-
ous. There are similar hydrogeological properties among the massive rocks, schists
and phyllites. These rocks are particularly impermeable, because their fracture
system is blocked by ner-grained material. Weathered subsurface zones of schists
and phyllites form an unconned aquifer exploited by the inhabitants, mostly in
the southern area of Lavrio and Kamariza (Ag. Konstantinos) from shallow wells
(Figure 2). The water supply from these wells is not adequate to cover the wa-
ter demands and most of them dry up during prolonged periods of drought. The
limited permeability, characterizing these formations, results in high runoff. This
is reected in the drainage pattern development, which is of the dendritic type.
On the contrary, in carbonate rock areas the typical parallel pattern is developed.
Consequently, the distinction between the two prevailing hydrolithological units of
the study area is feasible (Figure 3).
Carbonate formations, the lower and upper marbles, compose the main aquifer
of the study area. These rocks have high permeability due to intense fracturing
and especially great karstication. The lower marbles crop out in restricted areas
located South of Kamariza and southwest of Lavrio (Figure 2). On the contrary, in
the western area of the Lavrio peninsula the development of lower marble is more
extensive and constitutes the coastline. The lack of an impermeable horizon (base-
level) results in groundwater seeping under the lower marble towards sea level.
The upper marble has overlaid the mica schists of Kamariza and is widespread
in the study area. Its thickness can reach as much as 100 m and varies either
because the upper marble overlays the lower one, without any schist intercalation,
or because it has undergone intense erosion and weathering. The inltrating water
following the general Eastward dip of the beds, decant partially lateral toward the
loose quaternary deposits or they nd a possible submarine outlet.
In the alluvial deposits, which cover the greater part of the plain in the Thorikon
basin and parts of the Lavrio basin, an unconned aquifer has developed. This
aquifer displays limited permeability and poor hydraulic characteristics due to ne
6
6
G
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S
T
A
M
A
T
I
S
E
T
A
L
.
Figure 2. Simplied geological cross section of the Kamariza-Lavrio area. 1) Lower marble, 2) upper marble, 3) mica-schists, 4) phyllites nappe with
marbles and prasinites, 5) marbles of overthrusted nappe and 6) quarternary deposits.
GROUNDWATER POLLUTION BY HEAVY METALS 67
Figure 3. Drainage patterns of study area and groundwater sampling locations. 1) Drainage divide,
2) torrents and 3) water sampling points.
grain compositions. The impervious bedrock in the Thorikon basin is formed by
mica schists of Kamariza. On the contrary, in the Lavrio basin the impermeable
bedrock consists of phyllites and schists of the overthrust nappe. The replenish-
ment of unconned aquifer in alluvial deposits is ensured, both from the direct
inltration of rainfall throughout the alluvial deposits and also from lateral seepage
of karst water of upper marble and of groundwater from weathered schists.
The hydraulic connection of both karst and unconned aquifer with the sea
in combination with their intensive exploitation for irrigation have contributed to
68 G. STAMATIS ET AL.
the deterioration of groundwater quality, due to seawater intrusion. The seawater
intrusion is exceptionally intense in both the Thorikon and Lavrio basins.
3. Methods
3.1. SAMPLING ANALYSIS
The water samples were collected from wells and boreholes during March 1996.
The inventory of wells and boreholes had been made previously and the collected
samples represent all the lithological formations of the study area (Figure 3).
Samples 1, 3, 11, 11a, 12, 13, 14 and 30 were collected from the karst aquifers
(the upper and the lower marbles). Samples 2, 4, 5, 6, 7, 8, 9 and 10 were collected
from the Lavrio basin representing the alluvial unconned aquifer, hosted in the
weathered zone of phyllites and schists of the nappe. Sample 24 was collected
from the same formations also developed Northeast of the Thorikon basin. Samples
17, 18, 19, 20, 21, 22, 23, 25, 26, 26a and 27 were collected from the alluvial
unconned aquifer of the Thorikon basin, hosted in the weathered zone of mica
schists. Samples 15, 16, 28 and 29 were collected from the wells located on schists
of Kamariza. Sample 31 represents the metamorphic schists and hornfels of the
study area.
In Figure 4 are presented the main lithological and hydrogeological features of
wells and boreholes sampled.
The temperature, the electric conductivity and pH of water samples were meas-
ured in situ by portable apparatus (Hanna HI-8414 and HI-8733). The water
samples were stored in plastic bottles (2 L) of polyethylane. The following para-
meters were determined: Ca
2+
, Mg
2+
, Na
+
, K
+
, HCO

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

, by a spectrophotometer (Hack model DR/3000). In order to


measure total and carbonate hardness, as well as Cl

content, titration methods


were applied using Titriplex-Lsung A, HCl 0.1 N and AgNO
3
0.1 N, respectively,
(Hoell, 1979). T.D.S. was calculated using the results of chemical analyses.
All the analyses of water samples were carried out in the Laboratory of Miner-
alogy and Geology of the Agricultural University of Athens.
G
R
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B
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H
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V
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M
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L
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6
9
Figure 4. Main features of boreholes and wells sampled. 1) quarternary deposits, 2) carbonates, 3) mica-schists, 4) phyllites, 5) hornfels.
70 G. STAMATIS ET AL.
TABLE I
Statistical summary of chemical parameters (mg L
1
) of groundwater samples
Variable Unconned aquifer Karst aquifer
Mean Min Max S.D. V Mean Min Max S.D. V
(m) () ( m
1
) (m) ( m
1
)
pH 7.52 6.90 8.20 0.33 0.04 7.25 7.0 7.8 0.24 0.03
E.C.
a
3.732 795 8.470 2.130 0.57 3.700 1.535 11.260 3.230 0.87
T.D.S. 2.328 845 5.063 1.290 0.54 2.360 1.169 6.702 1.883 0.79
T.H.
b
787 286 1.557 340 0.43 770 430 1.521 698 0.90
Ca 198 92 396 85 0.42 200 128 352 74 0.37
Mg 76 12 176 45.7 0.60 63 7.1 212 77 1.22
Na 504 23 1200 377 0.74 496 170 1862 588 1.18
K 14 1 54 12 0.85 12.7 5.6 25 7 0.55
HCO
3
353 219 524 82 0.23 351 244 555 100 0.28
Cl 990 99 2.198 716 0.72 889 355 3.298 1023 1.15
SO
4
220 70 850 170 0.77 309 92 915 314 1.01
NO
3
26 1.8 118 25 0.96 24.5 4 48 13.7 0.56
PO
4
0.23 0.04 1.6 0.35 1.52 0.09 0.05 0.3 0.09 1.00
SiO
2
17 10 31 5.7 0.33 17.6 10 35 8.3 0.47
Fe 0.12 0.02 0.455 0.10 0.84 0.065 0.02 0.2 0.05 0.76
Pb 0.07 0.03 0.144 0.03 0.42 0.06 0.4 0.13 0.03 0.50
Ni 0.05 0.003 0.189 0.04 0.80 0.05 0.02 0.09 0.02 0.40
Zn 0.57 0.07 5.02 1.02 1.80 0.23 0.07 0.98 0.30 1.30
Mn 0.23 0.001 4.21 0.85 3.70 0.029 0.002 0.15 0.05 1.72
Cu 0.03 0.009 0.124 0.025 0.83 0.030 0.02 0.045 0.01 0.33
Cr 0.02 0.007 0.052 0.01 0.50 0.031 0.019 0.057 0.013 0.42
Cd 0.01 0.002 0.043 0.009 0.90 0.011 0.001 0.027 0.008 0.72
a
S cm
1
.
b
mg L
1
CaCO
3
.
3.2. STATISTICAL ANALYSIS
Summary statistics e.g. mean (m) standard deviation (), minimum-maximum val-
ues and coefcient of variation (V ) of the hydrochemical data are listed in Table I.
The coefcient of variation (V) which is a measure of the relative dispersion of a
parameter (Saager and Esselaar, 1969) was computed using the formula: V =
m
1
.
The interrelationships between the constituents of the groundwater are import-
ant, from a hydrochemical point of view. For this purpose the data were subjected
to simple correlation analysis and R-mode factor analysis in order to examine the
relationships between the parameters. The simple correlation coefcient (Douglas
GROUNDWATER POLLUTION BY HEAVY METALS 71
and Leo, 1977; Srinivasa-Rao et al., 1977; Ratha and Venkataraman, 1997) meas-
ures the strength of two parameters, when the dependent parameter is inuenced
only by independent parameter and vice versa.
The correlation matrices of chemical data for groundwater of unconned (allu-
vial deposits of Lavrio and Thorikon basin and schists) and karst aquifers are given
in Tables II and III.
The factor analysis is a branch of multivariate analysis and is useful tool for
interpreting commonly collected groundwater quality data relating them to specic
geochemical processes (Hakli, 1970). The principal aim of factor analysis is to
reduce the complex pattern of correlations among many parameters to simpler sets
of factors which are then interpretable. The method consists of the following steps
(Saager and Esselaar, 1969; Ruiz et al., 1990; Voudouris et al., 1997): The data
were standardized (with mean = 0 and standard deviation = 1) using the formula:
z
i
= (x
i
x
m
)/
where z
i
is the ith value of the standardized variable z, x
i
is the concentration of
variable i and x
m
, are the mean and standard deviation of all x
i
.
After this transformation the correlation coefcient matrix were computed. Ei-
genvalues and eigenvectors were calculated for the matrix. The data were trans-
formed into factors. The factor extraction has been done with a minimum eigen-
value as greater than 1 (Kaiser, 1958).
Next the factor loading matrix is rotated according to varimax scheme (Davis,
1987). This procedure renders a new factor loading matrix (Table IV), which af-
fords greater ease for interpretation. And lastly the contribution of each factor at
every site (factor scores) was computed. This step is important for the mapping of
the geographical distribution of each factor.
4. Results
4.1. GROUNDWATER QUALITY
The high mineralised bedrock of the study area, in conjunction with the increas-
ing number of wells and deep boreholes and the inefcient water resources man-
agement, has gradually resulted in groundwater quality deterioration. Taking into
account the data of Table I, the following conclusions can be drawn.
pH values are greater than 7 indicating the alkaline character of groundwater.
Highest conductivity and TDS values were recorded at samples of the unconned
aquifer of Thorikon basin, related to seawater intrusion, as result the intensied
exploitation.
Localised high phosphate concentrations (>0.2 mg L
1
) can be attributed to the
use of fertilizers and minerals dissolution originating from apatite erosion (Mari-
nos and Petrascheck, 1956). The coefcient of variation shows clearly the wide
dispersion of phosphate.
7
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TABLE II
Correlation matrix of chemical data for groundwater of the unconned aquifer of Lavrio area (alluvial deposits and schists)
Ca Mg Na K HCO
3
Cl SO
4
NO
3
PO
4
SiO
2
Fe Pb Ni Zn Mn Cu Cr Cd
Ca 1.00
Mg 0.56 1.00
Na 0.83 0.76 1.00
K 0.15 0.04 0.15 1.00
HCO
3
0.29 0.29 0.14 0.17 1.00
Cl 0.86 0.75 0.99 0.20 0.15 1.00
SO
4
0.73 0.58 0.77 0.13 0.23 0.72 1.00
NO
3
0.19 0.08 0.35 0.17 0.24 0.33 0.20 1.00
PO
4
0.04 0.02 0.08 0.06 0.07 0.04 0.09 0.10 1.00
SiO
2
0.21 0.13 0.09 0.09 0.03 0.13 0.15 0.35 0.04 1.00
Fe 0.02 0.06 0.07 0.70 0.01 0.10 0.19 0.09 0.13 0.10 1.00
Pb 0.34 0.09 0.31 0.61 0.31 0.37 0.07 0.14 0.01 0.01 0.49 1.00
Ni 0.12 0.03 0.25 0.84 0.08 0.27 0.03 0.30 0.14 0.06 0.56 0.38 1.00
Zn 0.10 0.07 0.16 0.05 0.31 0.16 0.11 0.23 0.09 0.37 0.06 0.15 0.12 1.00
Mn 0.18 0.13 0.018 0.76 0.09 0.21 0.01 0.02 0.09 0.10 0.68 0.45 0.75 0.12 1.00
Cu 0.11 0.01 0.01 0.11 0.13 0.02 0.09 0.05 0.61 0.10 0.08 0.07 0.05 0.02 0.14 1.00
Cr 0.17 0.17 0.14 0.69 0.31 0.11 0.28 0.05 0.10 0.31 0.33 0.50 0.72 0.17 0.46 0.11 1.00
Cd 0.01 0.11 0.06 0.86 0.11 0.08 0.12 0.17 0.17 0.01 0.69 0.63 0.73 0.05 0.77 0.11 0.64 1.00
G
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3
TABLE III
Correlation matrix of chemical data for groundwater of the karst aquifer
Ca Mg Na K HCO
3
Cl SO
4
NO
3
PO
4
SiO
2
Fe Pb Ni Zn Mn Cu Cr Cd
Ca 1.00
Mg 0.84 1.00
Na 0.65 0.94 1.00
K 0.37 0.15 0.03 1.00
HCO
3
0.80 0.54 0.25 0.50 1.00
Cl 0.63 0.93 1.00 0.03 0.21 1.00
SO
4
0.96 0.92 0.76 0.19 0.72 0.74 1.00
NO
3
0.66 0.64 0.68 0.21 0.23 0.69 0.57 1.00
PO
4
0.78 0.41 0.14 0.45 0.74 0.11 0.71 0.22 1.00
SiO
2
0.11 0.11 0.14 0.76 0.03 0.13 0.03 0.04 0.43 1.00
Fe 0.76 0.34 0.07 0.58 0.80 0.04 0.64 0.28 0.96 0.45 1.00
Pb 0.70 0.32 0.03 0.30 0.85 0.01 0.63 0.17 0.85 0.04 0.90 1.00
Ni 0.71 0.51 0.24 0.38 0.83 0.20 0.72 0.03 0.83 0.22 0.76 0.72 1.00
Zn 0.13 0.29 0.22 0.18 0.16 0.21 0.23 0.35 0.19 0.24 0.02 0.13 0.51 1.00
Mn 0.46 0.83 0.96 0.08 0.06 0.97 0.57 0.64 0.07 0.08 0.12 0.20 0.03 0.20 1.00
Cu 0.69 0.75 0.66 0.68 0.63 0.66 0.64 0.52 0.37 0.23 0.44 0.33 0.42 0.26 0.66 1.00
Cr 0.59 0.14 0.11 0.71 0.68 0.13 0.41 0.13 0.86 0.65 0.89 0.67 0.78 0.22 0.25 0.33 1.00
Cd 0.67 0.27 0.59 0.76 0.73 0.02 0.51 0.26 0.84 0.63 0.90 0.68 0.74 0.12 0.09 0.45 0.96 1.00
74 G. STAMATIS ET AL.
TABLE IV
Loadings for the varimax rotated 4-factors model
Variable Factor Communalities
1 II III IV
Ca 0.14 0.85 0.06 0.02 0.76
Mg 0.00 0.87 0.19 0.03 0.79
Na 0.05 0.96 0.07 0.07 0.94
K 0.93 0.02 0.01 0.03 0.87
HCO
3
0.44 0.39 0.51 0.23 0.65
Cl 0.08 0.95 0.04 0.08 0.93
SO
4
0.01 0.86 0.02 0.12 0.76
NO
3
0.15 0.29 0.52 0.55 0.68
PO
4
0.07 0.00 0.81 0.01 0.66
SiO
2
0.08 0.20 0.45 0.61 0.62
Fe 0.77 0.03 0.16 0.03 0.62
Pb 0.65 0.28 0.40 0.14 0.68
Ni 0.84 0.15 0.04 0.18 0.76
Zn 0.01 0.15 0.10 0.79 0.67
Mn 0.80 0.07 0.07 0.20 0.69
Cu 0.13 0.03 0.80 0.07 0.66
Cr 0.68 0.09 0.10 0.42 0.67
Cd 0.92 0.01 0.01 0.11 0.87
% Total 29.7 22.5 11.2 9.1
variance
Total Hardness (T.H.) exceeds 300 mg L
1
as CaCO
3
apart from a sample (27)
originating from the unconned aquifer of Kamariza-schists.
The mean nitrate concentration in the groundwater from the unconned aquifer
is 26 mg L
1
and from the karst aquifer 24.5 mg L
1
. Two samples from the
unconned aquifer of Lavrio basin (7 = 71 mg NO

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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