Environ Geol (2008) 56:11–18

DOI 10.1007/s00254-007-1135-6

ORIGINAL ARTICLE

Environmental research of groundwater in the urban

and suburban areas of Attica region, Greece
G. D. Bathrellos Æ H. D. Skilodimou Æ A. Kelepertsis Æ
D. Alexakis Æ I. Chrisanthaki Æ D. Archonti

Received: 27 July 2007 / Accepted: 12 November 2007 / Published online: 18 December 2007

Springer-Verlag 2007

Abstract In this study, 92 groundwater samples were to shrubby and sparsely vegetated areas, while elevated
collected from the Attica region (Greece). Moreover, values of NO-
3 are connected with urban and agricultural
geographical information system database, geochemistry of areas.
groundwater samples and statistics were applied. These
were used for studying the chemical parameters (NO- 3, Keywords Environmental research

Mg2+, Ca2+, Cl-, and Na+) and conductivity spatial dis- Geostatistical analysis
GIS
Urban and suburban areas

tribution and for assessing their environmental impact. The Greece
ranges of chemical parameters of the water samples (in
mg L-1) are: NO- 3 1–306, Mg
2+
2–293, Ca2+ 3–453, Cl-
+
5–1,988, and Na 4–475. The elevated concentrations of Introduction
sodium, Mg2+, Cl- are attributed to natural contamination
(seawater intrusion). On the other hand, NO- 3 elevated In antiquity, the city of Athens, and in general the Attica
concentrations are attributed to anthropogenic contamina- region were famous cultural centers of Greece. The study
tion (nitrate fertilizers). The results of the GIS analysis area (Fig. 1) is characterized by extensive human inter-
showed that elevated values of Na+, Mg2+, Cl- are related ventions, intensive agricultural activities and a dense road
network. The intensive urbanization, small industries and
the uncontrolled building construction represent a consid-
G. D. Bathrellos (&)
H. D. Skilodimou
A. Kelepertsis
erable threat to the environment of Attica region.
D. Alexakis In addition, western, northern as well as eastern parts of
Faculty of Geology & Geoenvironment, Attica region are characterized by agricultural activities.
National & Kapodistrian University of Athens,
These activities combined with the extensive urbanization
University Campus, Zografou, 15784 Athens, Greece
e-mail: gbathellos@geol.uoa.gr resulted in a great demand for water. Besides, the quality of
the groundwater has been affected by human interventions.
H. D. Skilodimou In many cases the lack of wastewater treatment has led to
e-mail: hskilodimou@euof.uoa.gr
the degradation of groundwater (Stamatis et al. 2006).
A. Kelepertsis Various studies (Kounis and Siemos 1987; McCartney
e-mail: kelepertsis@geol.uoa.gr et al. 1997; Alexakis and Kelepertsis 1998; Stamatis et al.
2001; Alexakis 2002; Kelepertsis and Alexakis 2004;
D. Alexakis
Makri et al. 2006; Stamatis et al. 2006) carried out on the
e-mail: dalexak@geol.uoa.gr
quality of groundwater of the Attica region showed con-
I. Chrisanthaki
D. Archonti tamination and degradation in many areas due to natural
Attica Region, 239 Mesogeion St, 11527 Athens, Greece and human parameters.
e-mail: i.hrisanthaki@attica.gr
In this study the quality of groundwater of the Attica
D. Archonti region was examined based on the various factors which
e-mail: darchodi@attica.gr define the hydrogeological conditions of the study area.

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12 Environ Geol (2008) 56:11–18

poorly developed due to morphology, geological and tec-

Fig. 1 Map showing the studied area
These factors include lithological parameters, water quality
indicators and statistical methods.
The main objectives of this study were:
tonic structure of the area as well as the urbanization
(Antoniou 2002; Skilodimou 2002). It is a mainly dendritic
drainage pattern and comprises streams with seasonal flow.
The main rivers that flow through the study area are: Kifisos
River, which end up to Saronikos Gulf and Biotikos Asopos
that ends up to Eubean Gulf (Fig. 1).
Generally, the climate of Attica belongs to the Medi-
terranean type, where the rainy period usually begins in
October and lasts until April. The mean annual precipita-
tion in the study area is rather low and fluctuates from
286.4 to 483.1 mm (Skilodimou 2002).
The geological structure of the studied area is dominated
by alpine and post-alpine formations. The alpine forma-
tions belong to three main stratigraphic units, the sub-
Pelagonian unit, the autochthonous unit of Attica and the
nappe of Lavrio-Attica (Fig. 2). The sub-Pelagonian unit
is composed by clastic formations (arkose, greywacke,
phyllite, sandstone, and schist) limestones, dolomites
ophiolithic formations, transgression limestone, iron man-
ganese ores and flysch. The autochthonous unit of Attica
comprises mainly schists, marbles and limestones, while
the nappe of Lavrio-Attica consists of phyllite, schist and
metalliferous ores. The Neogene deposits consist of marls,
clays, sandstone, conglomerates and travertine limestone.
Pleistocene continental deposits and Holocene deposits
include unconsolidated material with sand and pebbles,

(a) to examine the spatial distribution of chemical param-

eters,
(b) to assess the most heavily contaminated areas,
(c) to correlate the contaminated areas with the urban
activities and in general the land use.

Study area

Geomophological and geological settings

The Attica region is situated at the southeastern part of

continental Greece (Fig. 1). It covers a total surface area of
2,920.89 km2 with altitudes varying from 0 to 1,413 m
above mean sea level (m.s.l.). The relief of the Attica
region is quite plain with mountains and hills, while 6% of
the area is covered by mountains, 30% by plains and 64%
by hills (Fig. 1). Also Fig. 1 shows the mountains and the
main plains of the Attica region.
The mountains of Gerania, Pateras, Kitheron, Parnis,
Penteli, Ymmitos, and Egaleo, form the relief of the area.
The main plains of the area are: Megara, Thriassio Field, Fig. 2 Geological map of the studied area (modified from Katsikat-
Athens, Marathon, and Mesogeia. The drainage network is sos et al. 1986; Jacobshagen 1986; Migiros and Antoniou 2002)

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Environ Geol (2008) 56:11–18 13

alluvial sediments debris cones and lateral deposits (Lep-

sius 1893; Marinos and Petraschek 1956; Katsikatsos et al.
1976; Gaitanakis 1982; Jacobshagen 1986; Katsikatsos
et al. 1986; Skilodimou 2002).
The polymetallic sulphide mineralization of the Lav-
reotiki Peninsula consists of Ag-bearing galena, sphalerite,
pyrite and many secondary minerals. The famous Pb-Zn
mines of Lavrion are located in the East Attica region
(Kelepertsis and Alexakis 2004).
Tectonically, the study area was affected mainly by
alpine thrusts and formed by post-alpine faulting (Fig. 2)
(Migiros and Antoniou 2002).

Hydrogeology

There are two major aquifers in the area of the western part
of Attica: a karstic formation of Mesozoic limestone and
dolomite, Neogene formations and Quaternary deposits in
which unconfined and confined aquifers are developed
(Kounis and Siemos 1991). Fig. 3 Main towns and urban pattern of the studied area
In the eastern Attica schists and phyllites as imperme-
able rocks, form a poor aquifer. The carbonate rocks,
limestones and marbles comprise the most important
aquifer of the area (Stamatis et al. 2006).

Urbanization

The Attica region is mainly an urban area and 36% of the

total Greek population lives in it. The region is divided into
two subunits of urban areas. The first one comprises the
capital city of Athens including its suburbs and covers
11.2% of the total area (Fig. 3). The second subunit covers
88.8% of the total area and includes the city of Piraeus as
well as the western, northern and eastern Attica. Figure 3
illustrates the main towns of Attica and the urban pattern
including the road network.

Materials and methods

Sampling, sample preparation and chemical analysis

A network of 92 sampling sites (drills and wells) distributed
evenly all over the study area was sampled once during
May–June 2006, covering an area of *2,920.89 km2.
Groundwater sample locations were recorded in the field by
using GPS (Fig. 4).
All possible precautions were taken during collection
and handling of samples to minimize contamination. The
groundwater samples were collected in polyethylene con-
tainers; 1,000 ml of sample was vacuum-filtered through
Fig. 4 Map showing the sampling location
0.45 lm pore size membrane filters and stored in a poly-
ethylene container. All the samples were preserved in a
refrigerator.
Nitrate and chloride were measured photometrically
using a Hach DR/4000 apparatus. Chemical analyses of
Mg2+, Ca2+, Na+ were performed at the Laboratory of the
Economic Geology and Geochemistry Section of the Geol-
ogy Department of National and Kapodistrian University of

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Athens. Mg2+ and Ca2+ were measured by atomic absorption
spectroscopy (AAS/Perkin Elmer 1100B) and Na+ was
measured by flame photometry (JENWAY PFP7). The data
quality was assured by the introduction of internal reference
samples and by analyzing the duplicates of two samples. The
electrical conductivity was measured in the field.
In order to measure the degree to which Na in irrigation
water replaces the adsorbed (Ca2+, Mg2+) in the soil clays
the sodium adsorption ratio (SAR), introduced by Richards
(1969), was calculated by the following formula:
meqNa
SAR ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi :
meqCa + meqMg=
2
A milliequivalent is one thousand of a compound’s or an
element’s equivalent weight; abbreviated meq, where:
mg of ion solution
meq ¼
atomic weight of ion
: by Directive 98/83/EC concentration of nitrate in drinking
ion charge
Statistical analysis
Correlation analysis was used to define the underlying rela-
tionships of the elements and to link any relationships
between elements with geological or anthropogenic sources.
Interpolation of analytical data using GIS
A GIS database was developed using ArcGIS Ver. 9.2
software. The following data layers were digitized and
saved in the database:
types of land use were classified as follows: urban areas
(including continuous urban fabric, industrial, commercial
and transport activities, construction sites), agricultural
areas (including non-irrigated arable land, permanent crops
and heterogeneous agricultural areas) forest areas and
39.9% by shrubby and sparsely vegetated areas (Fig. 5).
About 15.2% of the total area of Attica is covered by urban
areas, 33.1% by agricultural areas, 11.8% by forest areas,
and 39.9% by shrubby and sparsely vegetated areas.
The evaluation of groundwater samples for drinking use
was carried out by comparing their parametric values given
by the Directive 98/83/EC (EC 1998). Table 1 summarizes
the maximum and minimum values of the studied chemical
parameters of the Attica groundwater in comparison with
the parametric values.
The NO- 3 content of the groundwater studied varies
from 0.2 to 306 mg L-1, while the parametric value given
water is 50 mg L-1. The high nitrate concentration
([50 mg L-1) in the area of Kifisia, Piraeus, Voula, Spata,
and Agia Paraskevi (Fig. 6) may be the result of the dis-
solution of fertilizers and the leakage of municipal sewage
rich in ammonia which subsequently oxidizes to nitrate.
The Mg2+ content of the studied water samples varies
from 5 to 393 mg L-1, while the parametric value given by
Directive 98/83/EC for concentration of magnesium in
drinking water is 50 mg L-1. Figure 7 shows three areas
with magnesium concentration [50 mg L-1. These areas

• sampling locations with the analytical data,

• land use,
• drainage network, road network, towns, contours of the
area.
Using the geostatistical analyst extension of ArcGIS the
initial values of each parameter were interpolated in grid
layers with cell size 20 9 20m2. The inverse distance
weighted (IDW) was used for interpolation. The IDW is
similar to Kriging interpolation method (ESRI 2007), while
the application of the two methods led to the same results.
Moreover, the zonal statistics tool of ArcGIS was used
in order to calculate the percentage proportion of each land
use area lain on every zone of the spatial distribution of the
studied chemical parameters.

Results and discussion

The land use of the Attica region was derived by using the
program CORINE (Bossard et al. 2000). In addition, the Fig. 5 Land use of the studied area

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Environ Geol (2008) 56:11–18 15

Table 1 Chemical parameters and conductivity values of Attica

groundwater in comparison with parametric values (in mg L-1)
Minimum Maximum Parametric values
value value (Dir 98/83/EC)

NO-
3 1 306 50
Mg2+ 2 393 –
Ca2+ 3 453 –
Cl- 5 1,988 250
Na+ 4 475 200
Conductivity 292 9,100 2,500
(lS cm-1)

Fig. 7 Concentrations of Mg2+ of the Attica groundwater

Fig. 6 Nitrate concentrations of the Attica groundwater

occur in the northern, western, and southeastern parts of the

studied area.
The Ca+2 content of the water samples of the studied
area ranges between 3 and 452 mg L-1. Figure 8 shows a
wide area occupying the half eastern part of the studied
area with some small complexes with Ca+2 values
exceeding 200 mg L-1.
The Cl- concentrations show a wide range (5– Fig. 8 Calcium concentrations of the Attica groundwater
1,988 mg L-1) with high concentrations ([250 mg L-1)
occurring in the area of Anavyssos, Lavrion, Piraeus,
Elefsis, and Megara (Fig. 9). Finally, the conductivity values range between 292 and
The Na+ content varies from 4 to 474 mg L-1, while the 9,100 and are related to the total dissolved solids (Fig. 11).
parametric value given by the Directive 98/83/EC in Moreover, the Attica groundwater was classified in
drinking water is 200 mg L-1. Figure 10 shows high terms of salinity hazard (conductivity) and sodium hazard
concentrations of sodium in the areas of Lavrion, Ana- (SAR). The SAR of Attica groundwater samples ranges
vyssos, Voula, and Megara. from 0 to 11.5; while the mean value is 2.06. The Attica

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Fig. 9 Concentrations of Cl- of the Attica groundwater
Fig. 10 Concentrations of Na+ of the Attica groundwater
groundwater samples were classified according to SAR
categories as follows: C3–S1 (72.9%), C2–S1 (7.6%), C3–
S2 (6.5%), C4–S1(8.7%), C4–S2 (3.3%), and C3–S3(1.0%)
(Fig. 12).
According to correlation analyses (Table 2) the fol-
lowing parameters are intercorrelated: Mg2+, Na+, Cl- and
conductivity. The association of these parameters may be
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Environ Geol (2008) 56:11–18
Fig. 11 The spatial distribution of conductivity of the Attica
groundwater
attributed to the seawater intrusion in the area of Megara,
Elefsis, Piraeus, and Anavyssos (Fig. 13). The high con-
ductivity and the total dissolved salts in some of the
groundwater samples and the association of Mg2+, Na+,
Cl- as basic constituents of seawater (Hem 1985; Alexakis
and Kelepertsis 1998; Alexakis 2002; Kelepertsis 2007)
certify the seawater intrusion.
Calcium shows a low positive correlation with sodium
(+0.38) and a medium positive correlation with NO- 3
(+0.48) suggesting a contribution from two sources; the
first source may be the wide extent of carbonate rocks
(limestones and dolomites) and their weathering products
and the second one is the seawater intrusion. The medium
correlation between calcium and nitrate may be attributed
to the wide extent of calcareous soils, covering the most
part of cultivated and fertilized areas.
There is not any correlation between NO- 3 and the ele-
ments Mg2+, Na+, Cl-, and this is an indication of the use of
fertilizers in the study area. According to Pachero et al.
(2001) if the correlation coefficient between NO- -
3 and Cl is
greater than +0.35, this is an indication of a common origin of
these parameters such as industrial or civic wastes. Since the
correlation between NO- 3 and Cl
-
is -0.04, there is no
common origin of these elements in the studied area.
The results of geostatistical analyses showed the fol-
lowing relationship between Mg2+, Ca2+, Na+, Cl-,
conductivity, NO- 3 and the land use (Table 3).
From Table 3 it is obvious that the elements Na+, Mg2+,
Cl- and conductivity are highly positively intercorrelated
Environ Geol (2008) 56:11–18 17

Fig. 13 The spatial distribution of seawater intrusion zones of Attica

region

to 50 mg L-1 are mainly related both to agricultural

(36.7%) and shrubby and sparsely vegetated areas (36.7%),
while concentrations [50 mg L-1 are mainly related to
urban (39.2%) and agricultural (28.1%) areas. This is an
indication that nitrate pollution is mainly attributed to
urban and agricultural areas covered by calcareous soils.

Table 3 Comparison of elevated concentrations of chemical

parameters with the surface of land use (%)

Fig. 12 SAR-conductivity diagram of Attica groundwater samples Chemical Land use

(n = 92) parameters
Urban Agricultural Forest Shrubby
areas areas areas and
and related to seawater intrusion. The associations of these sparsely
elements are mostly related to the shrubby and sparsely vegetated
areas
vegetated areas. The Ca2+ contents varying between 100
and 200 mg L-1 are related mainly to shrubby and sparsely Mg2+ (30–50 mg L-1) 15.8 30.4 12.8 41.0
vegetated areas, while concentration [200 mg L-1 are Mg 2+ -1
([50 mg L ) 12.5 35.6 10.5 41.4
mainly related to agricultural areas. Nitrate values from 25 Ca2+ (100–200 mg L-1) 22.0 31.6 10.4 36.0
Ca2+ ([200 mg L-1) 20.8 63.6 – 15.6
Table 2 Correlation matrix of conductivity and chemical parameters Na+ (200–400 mg L-1) 16.9 34.1 6.5 42.5
of Attica groundwater (n = 92) Na+ ([400mg/lt) 41.2 5.7 0.6 52.5
Conductivity Mg 2
Ca 2+
Na +
Cl -
NO-
3 Cl- (250–500 mg L-1) 8.6 34.2 11.2 46.0
Cl- ( [500 mg L-1) 16.6 27.9 9.4 46.1
Conductivity 1 0.74 0.41 0.49 0.93 0.04
Conductivity 20.0 28.6 8.7 42.8
Mg2+ 1 0.06 0.51 0.72 0.04 (2500–5000 lS cm-1)
Ca2+ 1 0.38 0.19 0.48 Conductivity 24.2 40.1 17.4 18.3
Na+ 1 0.84 0.20 ([5000 lS cm-1)
Cl- 1 -0.04 NO- -1
3 (25–50 mg L ) 8.7 36.7 14.9 39.7
NO-
3 1 NO- -1
3 ([50 mg L ) 39.2 28.1 8.1 24.6

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Conclusions
Evaluating the results of this study the following
conclusions can be reached
The land use types of Attica Region, which were produced
by the program CORINE, were classified as follows: urban
areas (15.2%), agricultural areas (33.1%) forest areas
(11.8%) and shrubby and sparsely vegetated areas (39.9%).
The groundwater has been contaminated by seawater
intrusion (high concentrations of Na+, Mg2+, Cl-) and by
anthropogenic activities (elevated values of NO- 3 ). High
Ca2+ contents in some of the studied groundwater samples
are both related to nitrate fertilizers in calcareous soils and
to the seawater intrusion.
Only 1% of the Attica groundwater samples (Fig. 4:
sampling location no 62, town of Megara) demonstrated a
high sodium–high salinity hazard. The areas showing high-
conductivity values of groundwater relate spatially to high
SAR value areas.
The geostatistical analysis (GIS) showed that the ele-
ments Na+, Mg2+, Cl- are mostly related to the shrubby and
sparsely vegetated areas, while high nitrate values
([50 mg L-1) are mainly related to urban and agricultural
areas, which are mostly rich in calcareous soils. High con-
centrations of calcium ([200 mg L-1) are mainly related to
agricultural areas.
References
Alexakis D, Kelepertsis A (1998) The relationship between the
chemical composition-quality of groundwater and the geological
environment in the East Attiki area, Greece. Mineral Wealth
109:9–20
Alexakis D (2002) The impact of geologic and antropogenic factors
on the quality and the chemical composition of East Attica
groundwater’s. Ph.D. thesis, National and Kapodistrian Univer-
sity of Athens (in Greek with English abstract)
Antoniou V (2002) Natural and human environment of Athens basin.
Paper presented at the 6th Geographical conference of the
Hellenic Geographical Society, Thessaloniki, 3–6 October 2002,
I:311–318
Bossard M, Feranec J, Otahel J (2000) CORINE land cover technical
guide—Addendum 2000. European Environment Agency,
Copenhagen
EC (1998) Council Directive 98/83/EC of 3rd November 1998 on the
quality of water intended for human consumption. Official
Journal of the European Communities L 330
ESRI (2007) ESRI publ. Redlands, California, USA. http://
webhelp.esri.com/arcgisdesktop/9.2/index.cfm?TopicName=
An_overview_of_Geostatistical_Analyst. Cited 11 Sept 2007
Gaitanakis P (1982) Sheet ‘‘Athens-Peireus’’ geological map, scale
1:50,000. Institute of Geology and Mineral Exploration, Athens
123
Environ Geol (2008) 56:11–18
Hem J (1985) Study and interpretation of the chemical characteristics
of natural waters, 3rd edn. U.S. Geological Survey, water-
supply, paper 2,254
Jacobshagen V (1986) Geologie von Griechenland. Borntraeger,
Berlin (in German)
Katsikatsos G, Mercier JL, Vergely P (1976) La fenêtre d’ Attique-
Cyclades et les fenêtres mètamorphiques des Hellènides internes
(Grèce). C R Acad Sci Paris (D) 283:1613–1616
Katsikatsos G, Migiros G, Triantaphylis M, Mettos A (1986)
Geological structure of internal Hellenides (E. Thessaly—SW
Macedonia, Euboea—Attica- Nothern Cyclades Islands and
Lesvos). Geol Geoph Special Issue, Institute of Geological and
Mineral Exploration, Athens
Kelepertsis A (2007) Geochemistry. Symmetry, Athens, Greece
Kelepertsis A, Alexakis A (2004) The impact of mining and
metallurgical activity of the Lavrion sulfide deposits on the
geochemistry of bottom sea sediments east of the Lavreotiki
peninsula, Greece. Res J Chem Environ 8:40–46
Kounis GD, Siemos NE (1987) Pollution from petroleum hydrocar-
bons in the subsurface area of Hellenic Refinery of Aspropyrgos.
Institute of Geological and Mineral Exploration, Athens, p 8 (in
Greek)
Kounis GD, Siemos NE (1991) Hydrogeological research of the
aquifers of Thriasio Field, for the water supply of Hellenic
Refinery. Institute of Geological and Mineral Exploration,
Athens, p 38 (in Greek)
Lepsius R (1893) Geologie von Attika. Ein Beitrag zur Lehne vom
Metamorphismus der Gesteine. Dietrich Reimer, Berlin (in
German)
Makri P, Kalivas D, Bathrellos G, Skilodimou H (2006) Spatio-
temporal analysis of groundwater pollution from BTEX in
Thriassio Field, Attica, Greece. Paper presented at the 10th
IAEG Congress ‘‘Engineering Geology of Tomorrow cities’’
Nottingham, United Kingdom 6–10 September 2006, Interna-
tional Association of Engineering Geology and Geological
Society of London, paper 409 in CD:1–11
Marinos G, Petraschek W (1956) Lavrion. Institute of Geology and
Underground Research, Athens (in Greek)
McCartney K, Uhler A, Naymik T, Gidarakos E (1997) Identification
of the subsurface hydrocarbon products at the Aspropyrgos
Refinery. Hellenic Refineries S.A., Athens, Greece
Migiros G, Antoniou V (2002) The morphotectonic structure of Attica.
Paper presented at the 6th geographical conference of the Hellenic
Geographical Society, Thessaloniki, 3–6 October 2002, I:1–8
Pachero J, Marin L, Cabrera A, Steinich B, Escolero O (2001) Nitrate
temporaland spatial patterns in 12 water-supply wells, Yucatan,
Mexico. Environ Geol 40:708–715
Richards D (1969) Diagnosis and improvement of saline and alkaline
soils. United States Salinity Laboratory Staff. Agriculture
Handbook No6, Washington, DC
Skilodimou H (2002) Geomorphological and environmental study of
the coastal zone of Southwestern Attica. Ph.D. thesis, National
and Kapodistrian University of Athens (in Greek with English
abstract)
Stamatis G, Voudouris K, Karefilakis F (2001) Groundwater pollution
by heavy metals in historical mining area of Lavrio, Attica,
Greece. Water Air Soil Pollut 128:61–83. doi:10.1023/
A:1010337718104
Stamatis G, Lambrakis N, Alexakis D, Zagana V (2006) Groundwater
quality in Mesogea basin in eastern Attica (Greece). Hydrol
Process 20:2803–2818. doi:10.1002/hyp.6072