Catena 150 (2017) 206–222

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Catena

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Assessment of arsenic and associated metals in the soil-plant-water

system in Neogene basins of Attica, Greece
Evdokia E. Kampouroglou ⁎, Maria Economou-Eliopoulos
Dept. of Geology & Geoenvironment, Section of Economic Geology & Geochemistry, National University of Athens, Panepistimiopolis, 15784 Athens, Greece

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents a study on the soil-plant-water system in the Neogene basins of Attica (Greece), where an
Received 17 February 2016 uppermost yellow-brown travertine limestone has been deposited. The principal goal of our study is to identify
Received in revised form 10 November 2016 the percentage of arsenic (As) and metal transferred into plants and crops (bio-accumulation) in order to de-
Accepted 14 November 2016
scribe the incorporation of As in plants from rocks and soils and to assess potential groundwater contamination.
Available online xxxx
The bio-accumulation factor for plants exhibits a wide range, including relatively low (1.5–7.6%) for As, Pb, Ni,
Keywords:
Mn, Cr, Ba, Sb, Fe, much higher (29–67%) for Cu, Zn, Co, Ca and Mg, and exceptionally high (265%) for P. Although
Arsenic acceptable limits for As and heavy metals for plants have not been defined, As contents (dry weight) in plants
Contamination from the Neogene basins of Attica are often higher than normal or limited values. The bio-accumulation factor
Risk for plants (Asplant / Assoil * 100) in Neogene basins of Attica exhibited a positive correlation between As and Fe,
Bio-accumulation Cr, Mn, Pb and Sb.
Ground water The estimated risk assessment maps for As, Na, Cl and Se in water are produced according to the parametric
Neogene basins values of Directive 98/83/EC, although these elements showed higher risk values in the southwest and central
Greece
part of the Mesogeia basin than in the Kalamos-Varnavas basin. The elevated Na, Cl, As, Se, Li and B concentra-
tions, measurement of salinity and factor analysis in groundwater in the Mesogeia basin were attributed to a con-
tribution by seawater in this aquifer.
The estimated risk assessment maps of As in soils and ground waters in Neogene basins of Attica may indicate a
potential human health risk and environmental significance of an integrated water-soil-plant investigation of As
contamination in similar Neogene lacustrine formations.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Arsenic (As), which is associated with igneous and sedimentary
rocks, and sulphide ores, is the 20th most common element in the
earth's crust (0.5–2.5 mg/kg) (Kabata-Pendias and Mukherjee, 2007).
Arsenic compounds are observed in rock, soil, water, air and plant and
animal tissues. The risk of As entering the food chain through water,
soil and plant/crop contaminations has been a topic of global interest
(WHO, 2004). The recommended limit of As in drinking water is
10 μgL− 1 As (USEPA, 2001), although at present, there is no known
safe limit for As. Recent research suggests that tuberous vegetables ac-
cumulate higher amount of arsenic than leafy vegetables, although
leafy vegetables accumulate higher amounts of arsenic than fruity
vegetables (Alam et al., 2002; Bhattacharya et al., 2010a, 2010b;
Roychowdhury et al., 2002; Samal, 2005). The rate of uptake and the
bio-accumulation factor of As in crops usually depends on its availability
⁎ Corresponding author.
E-mail addresses: ekamp@geol.uoa.gr (E.E. Kampouroglou), econom@geol.uoa.gr
(M. Economou-Eliopoulos).
in soils, the soil pH, organic matter, redox potential and mineral compo-
sition (Mandal and Suzuki, 2002).
In aquatic systems, inorganic arsenic occurs primarily in two oxida-
tion states, As(V) and As(III). Both forms generally co-exist, although
As(V) predominates under oxidizing conditions and As(III) predomi-
nates under reducing conditions, depending on the Eh, pH, salinity,
metal concentrations, temperature, and distribution and composition
of the biota (USEPA, 1984). Natural levels of arsenic in soil usually
range from 1 to 40 mg/kg, with a mean of 5 mg/kg. Arsenic is observed
in many foods at contents that usually range from 20 to140 μg/kg.
Elevated As contents were recently recorded for the first time in a
limestone quarry in Varnavas basin (NE Attica, Greece) that is exploited
for a popular multicolour building material and in the associated soil
(Kampouroglou and Economou-Eliopoulos, 2013). The results of a geo-
chemical investigation at Neogene basins, which cover a significant por-
tion of Attica, were presented using the geographical information
system (GIS), geostatistical techniques and mapping software to show
the extent and intensity of As contamination and other elements (Fe,
Mn, Ni, Cr and Ba) in travertine limestone and associated soils
(Kampouroglou and Economou-Eliopoulos, 2016). These researchers

http://dx.doi.org/10.1016/j.catena.2016.11.018
0341-8162/© 2016 Elsevier B.V. All rights reserved.
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222
concluded that the major contamination sources are most likely sul-
phide and Fe-Mn mineralization in Attica, basement rocks that involve
mylonitic ophiolitic blocks and, to a lesser extent, human activities.
Given that the uppermost yellow-brown travertine limestone,
which is distributed across Attica, has high contents of As and heavy
metals, our present study focused on the investigation of plants and
water samples (springs, wells and boreholes) from the major Neogene
basins of Attica. Our study aimed to assess the percentage of As and
metal transferred into plants/crops (bio-accumulation) in order to de-
scribe the incorporation of arsenic in plants from soils and potential
groundwater contamination.
1.1. Description of the site-sampling
The study area of Attica is composed of alpine basement, both
metamorphic and non-metamorphic rocks, and post-alpine forma-
tions. The metamorphic section of the Attica-Cyclades zone occurs
in the eastern and southern parts of Attica, where it is transformed
by high pressure and low temperature conditions and consists of Tri-
assic schists, metabasic, and quartz-feldspathic rocks (Papanikolaou
and Papanikolaou, 2007).
The geomorphology of the area is dominated by the Parnitha and
Aegaleo Mountains in the west, and the Penteli and Hymettus Moun-
tains in the east that, border the Athens basin. During the Upper Plio-
cene-Pleistocene, activation of the Penteli detachment fault lifted the
Hymettus Mountain and caused the separation of the Athens basin
from the Mesogeia basin (Mposkos, 2008). Maps showing contaminat-
ed and potentially contaminated sites coupled with mineralogical and
Fig. 1. Topographical map showing the sampling locations in Neogene basins of Attica (Greece).
207
geochemical data confirm the geotectonic literature data suggest the
separation of an initially single basin in Attica into smaller basins
(Kampouroglou and Economou-Eliopoulos, 2016). Three major drain-
age basins can be distinguished from the coastal zone of Oropos-
Kalamos in the southern Evoikos gulf to the Saronic gulf: 1) The
Kalamos-Varnavas basin toward the northwest, 2) The Athens basin in
the south with a NNE-SSW flow direction, and 3) The Mesogeia basin
with a major W-E flow direction between the Hymettus Mountain in
the west and the Penteli Mountain in the north (Fig. 1).
The alpine bedrock is covered by post-alpine Neogene to Quaternary
formations. These formations include 1) Upper Pliocenic deposits
(marine-coastal) of Southern Athens and Eastern Mesogeia basins,
2) Upper Miocenic deposits (lacustrine formations-travertine lime-
stone, fluvial-lacustrine, fluvial-continental and lacustrine-continental),
and 3) Quaternary alluvial deposits (I.G.M.E., 2000, 2002, 2003). The
Neogene lacustrine deposits of Kalamos-Varnavas basin consist of
marls, marl limestone with lignite intercalations of the Malakasa-
Oropos area and travertine, while upward to these, clays, sandstones
and conglomerates are developed (Ioakim et al., 2005; Mettos, 1992).
In the central part of the Mesogeia basin, alternation marls and marl
limestone with lignite intercalations of Rafina are found (Mettos, 1992).
The most important aquifers in the Kalamos-Varnavas basin are
constituted by Triassic-Jurassic limestones, Upper Cretaceous lime-
stones, marly limestones and travertine limestones, which are char-
acterized as permeable rocks. The Triassic-Jurassic limestones of the
Sub-Pelagonian zone in the Kalamos-Varnavas basin are character-
ized as karstic aquifer and with outlets through submarine and
coastal springs located in the north part of the Kalamos area. The
208 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222

terrestrial springs are the spring of contact between the travertine
limestone and basement schists. Upper Miocene conglomerates and
marly formations with lignite intercalations (fluvial-lacustrine de-
posits) form a poor aquifer. The alluvial deposits form a phreatic
aquifer that possess low hydraulic characteristics and feed a large
number of wells and boreholes, with depths ranging from 10 to
20 m (Stamatis et al., 2011).
The main part of Mesogeia basin is occupied by Quaternary forma-
tions (gravels, sand, and clays) that characterize a low productive phre-
atic aquifer. The basis of this aquifer consists of schists, carbonate rocks
and Neogene deposits. In the Neogene formations, alternate permeable
and impermeable layers or lenses result in the development of uncon-
fined and confined aquifers (Champidi et al., 2011). The impermeable
bottom of the Neogene basin is composed of basement schists, which
controls the regional groundwater flow and causes high surface run
off. Carbonate rocks, limestone and marble are found in the schists,
and these constitute the most important aquifer of the basin by showing
high permeability due to their intense karstification and fracture poros-
ity (Stamatis et al., 2006).
2. Materials and methods
2.1. Sampling and preparation
Soil, plant and water samples have been collected from the basins
associated with the lacustrine formations of travertine limestone
(Kampouroglou and Economou-Eliopoulos, 2013, 2016). Soil samples
(n = 37) were collected from the rhizosphere of plants during the win-
ter of 2012 and spring of 2013 from a maximum depth of approximately
20 cm in order to investigate the relationship between element contents
in plants and soil. Soils were dried at 50 °C, crumbled mechanically and
passed through a sieve with a 2 mm mesh. Soil that was finer than 2 mm
was pulverized and analysed by Inductively Coupled Plasma Mass Spec-
troscopy (ICP/MS) after Aqua Regia Digestion at the ACME Analytical
Laboratories in Canada. These soil data have been previously published
(Kampouroglou and Economou-Eliopoulos, 2016). Six (6) reference
soils un-associated with travertine limestone and developed in the
close vicinity of exposed rock outcrops in the Neogene basins of Attica
(area of Holargos and the western part of the Kalamos-Varnavas
basin) were collected and considered to be unaffected soils by travertine
limestone (Tian et al., 2017).
The vegetation of Attica is composed of forests of Pinus halepensis,
Querqus coccifera, Cupressus sempervirensvar, and Olea. Phrygana
grow in the forest gaps and in newly afforested areas. Grasses
found in the region are classified as species of shrubby pseudo-
steppe derived from degradation of the natural forest vegetation
(e.g., Brachypodium ramosum, Poa bulbosa, Avena sp., and Bromus
sp.). There are also important species of geophytes such as, Cyclamen
graecum. The following plant species were collected, at the same
time with the soils, and analysed in the present study: Stachys
germanica (KAL-PL1, KAL-PL4, KAL-PL6, KAL-PL13, KAL-PL14, VAR-
PL21), Thymus sibthorpii (KAL-PL2, KAL-PL3, KAL-PL5, KAL-PL7,
KAL-PL15, VAR-PL20, VAR-PL24, DR-PL1, DR-PL5, AR-PL5), Sonchus
oleraceus (KAL-PL8, KAL-PL11, VAR-PL22, DR-PL6, AR-PL1),
Cichorium intybus (KAL-PL10, KAL-PL12, VAR-PL23), Bromus arvensis
(DR-PL3, AR-PL2), Foeniculum vulgare (DR-PL4), Malva sylvestri (AR-
PL7), Sinapis arvensis (AR-PL8), Phlomis fruticosa (DR-PL2), Inula
verbascifolia ssp. methanea (AR-PL4, AR-PL6) and Lactuca sativa
(VAR-PL26, VAR-PL30, VAR-PL31). The investigated plant species
are edible by humans and animals except for the species Phlomis
fruticosa and Inula verbascifolia ssp. methanea.
The plant sample numbers were determined by the plant's availabil-
ity and presence in the areas of interest. In certain cases, more than one
plant species growing on a single site in the same soil were collected to
estimate the role of plant physiology and metabolism to metal bioavail-
ability. Plants were cut to remove roots from stems and washed with co-
pious amounts of distilled water to remove the adhered soil and dust
particles. Washed plants were oven dried at 50 °C overnight in the lab-
oratory. A total of 32 wild and three cultivated (Lactuca sativa) plants
were powdered in an agate mortar and analysed by Inductively Coupled

Table 1
Descriptive statistics of soil samples (n = 37) from the Neogene basins of Attica. The metal and OM contents are detailed in Kampouroglou and Economou-Eliopoulos (2016). The back-
ground values in soils (n = 6) established in this study.

Soils associated with travertine limestones Reference values Background values

Units Average Min. Max. Standard deviation Curvature Asymmetry Gazette 641B/1991 Dutch limits (2009) Average Range

As mg/kg 210 16 1200 33 16 3.4 – 76 16 7–25

Cu 30 5.3 77 2.8 1.6 1.4 50–140 190 38 28–50
Pb 70 14 240 8.4 4.6 2.1 50–300 530 35 15–76
Zn 167 39 500 17 2.5 1.5 150–300 720 81 58–130
Ni 144 27 660 22 5.2 2.1 30–75 100 255 130–470
Co 23 9 64 1.6 7.4 2.1 – 190 28 19–39
Mn 776 290 1400 52 −0.7 0.3 – – 888 680–1180
Cr 172 17 1400 40 19 4.0 – 180 126 67–200
Ba 158 6 410 18 −0.7 0.6 – 8 87 54–140
Th 4.9 0.05 11 0.5 −0.3 0.2 – –
Sr 55 15 140 4.7 1.4 1.1 – – 75 18–104
Cd 0.5 0.2 1.5 0.1 3.2 1.8 – 13 0.4 0,2–0,8
Sb 5.7 0.4 21 0.7 2.8 1.6 – 22 0.6 0,2–1,4
V 58 13 160 6.2 0.1 0.9 – – 40 23–53
La 19 0.5 41 1.7 0.0 0.5 – – 11 7–16
Sc 7.3 0.3 19 0.8 −0.8 0.6 – –
Fe wt% 3.0 0.83 5.6 0.2 0.1 0.3 – – 2.9 2,2–3,3
Ca 13 0.6 36 1.5 1.5 1.0 – – 6.8 2,2–11
Mg 0.6 0.1 2.6 0.1 6.9 2.2 – – 1.4 0,5–2
Ti 0.1 0.0005 0.5 0.0 −1.0 0.6 – – 0.015 0,01–0,02
Al 3.2 0.03 9.3 0.4 −0.8 0.6 – – 1.6 1–2,3
Na 0.2 0.0005 0.7 0.0 0.1 1.0 – – 0.02 0,01–0,06
K 0.7 0.005 2.1 0.1 −1.1 0.6 – – 0.36 0,17–0,67
P 0.1 0.02 1.3 0.0 36 6.0 – – 0.11 0,06–0,22
organic matter 4.0 0.6 19.9 0.6 8.5 2.4 – – 1 0,7–1,4
pH 8.0 7.4 8.3 0.04 1.2 −1.2 – –
Eh mV −87 −111 −57 2.4 0.1 0.4 – –
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222
Table 2
Major and trace element contents in plants.

mg/kg wt%
Location Sample
Shoots As Mo Cu Pb Zn Ni Co Mn Th Sr Cd Sb La Cr Ba B Fe Ca P Mg Al Na K S

Kalamos KAL_PL1*1 0.05 0.7 11 0.4 27 0.9 40 37 0.05 5.2 0.005 0.05 0.2 2.2 2.4 4 0.03 0.4 0.1 0.1 0.02 0.3 1.2 0.2
KAL_PL2*2 5.4 0.4 7.5 1.5 36 7.6 18 54 0.1 9.3 0.05 0.1 0.8 8.1 28 12 0.1 1.2 0.09 0.1 0.1 0.04 0.6 0.1
KAL_PL3*2 30 0.4 8.7 1.1 29 18 16 58 0.2 10 0.02 0.6 0.5 37 28 10 0.2 1.2 0.08 0.1 0.1 0.04 0.7 0.09
KAL_PL4*1 3.9 2.6 3.6 0.7 19 2.8 22 39 0.03 5.1 0.005 0.1 0.1 6.9 2.8 3 0.04 0.4 0.07 0.1 0.02 0.4 1.0 0.1
KAL_PL5*2 0.9 0.2 8.4 1.1 25 2.7 12 26 0.08 9.0 0.04 0.05 0.4 3.9 8.8 11 0.06 1.2 0.05 0.1 0.05 0.03 0.8 0.1
KAL_PL6*1 0.7 0.7 3.1 1.3 44 2.3 34 53 0.07 5.1 0.03 0.06 0.3 3 9.1 3 0.05 0.4 0.04 0.06 0.04 0.01 0.6 0.1
KAL_PL7*2 1.2 0.3 6.7 2.2 27 4.1 6.2 33 0.2 12 0.07 0.09 0.7 4.9 34 10 0.09 1.3 0.05 0.1 0.09 0.06 0.3 0.1
KAL_PL8*3 0.4 0.9 11 0.5 60 1.5 8.1 47 0.02 11 0.1 0.1 0.1 3 5.8 17 0.03 1.7 0.08 0.2 0.02 0.5 2.6 0.2
KAL_PL10*4 1.0 2.7 5.4 0.4 57 3.5 4.6 50 0.03 13 0.005 0.08 0.1 4.8 6.1 26 0.04 1.7 0.2 0.2 0.02 0.5 2.0 0.3
KAL_PL11*3 1.3 0.6 4.2 0.2 26 1.4 16 23 0.01 16 0.05 0.1 0.06 2.9 6.4 17 0.02 1.2 0.09 0.2 0.01 0.9 2.4 0.2
KAL_PL12*4 0.6 0.3 5.8 0.6 18 2.8 17 27 0.06 12 0.03 0.05 0.2 3.9 26 16 0.05 1.9 0.2 0.2 0.04 0.1 1.4 0.1
KAL_PL13*1 0.2 0.6 3.5 0.5 20 1.4 33 27 0.02 2.0 0.01 0.07 0.1 3.8 1.9 3 0.02 0.2 0.2 0.07 0.02 0.2 0.8 0.08
KAL_PL14*1 0.2 0.6 3.6 0.2 26 2.1 11 52 0.005 2.1 0.01 0.03 0.03 2.4 2.2 3 0.01 0.2 0.07 0.04 0.005 0.01 1.0 0.1
KAL_PL15*2 0.4 0.2 7.1 0.7 30 1.9 24 15 0.03 8.0 0.02 0.05 0.2 3.4 9.7 11 0.03 1.2 0.07 0.1 0.02 0.08 0.9 0.07
Average 3.3 0.8 6.4 0.8 32 3.8 19 39 0.1 8.6 0.03 0.1 0.3 6.4 12 10 0.1 1.0 0.1 0.1 0.04 0.2 1.2 0.1
Varnavas VAR_PL20*2 1.9 0.5 8.2 3.0 29 2.7 35 27 0.1 7.5 0.04 0.2 0.5 4.9 13 11 0.07 1.1 0.04 0.1 0.05 0.1 0.7 0.08
VAR_PL21*1 0.3 0.8 2.9 0.5 12 1.4 11 17 0.02 2.6 0.01 0.05 0.09 2.3 3.5 2 0.02 0.2 0.04 0.03 0.01 0.04 0.7 0.05
VAR_PL22*3 0.3 1.9 12 0.5 55 0.8 21 36 0.02 9.0 0.05 0.05 0.09 4.2 3.9 27 0.03 1.5 0.1 0.2 0.01 0.4 2.6 0.2
VAR_PL23*4 1.8 0.4 7.7 1.7 48 1.6 19 26 0.07 16 0.1 0.1 0.3 3.4 12 23 0.07 2.7 0.04 0.2 0.04 1.9 2.1 0.1
VAR_PL24*2 0.2 0.4 5.2 0.7 37 0.8 10 14 0.02 7.0 0.01 0.05 0.1 2.1 8.4 11 0.02 1.0 0.05 0.1 0.02 0.02 0.9 0.1
VAR-PL26*11 4.3 1.4 11 0.4 60 2.5 0.2 250 b0.01 16 0.6 0.2 0.05 2.0 16 33 0.05 1.5 0.5 0.6 b0.01 0.4 8.7 0.3
VAR-PL30*11 6.5 1.7 12 2.6 70 1.6 0.2 130 0.02 13 0.8 0.4 0.4 3.1 11 38 0.05 1.1 0.5 0.4 0.01 0.4 7.7 0.3
VAR-PL31*11 1.4 1.2 61 3.8 170 16 5.6 240 b0.01 18 1.7 4.4 0.1 3.2 43 74 0.2 2.0 0.1 0.5 0.03 0.8 3.9 0.4
Average 2.1 1.0 15.1 1.7 60.0 3.4 12.7 92.5 0.0 11.1 0.4 0.7 0.2 3.2 13.8 27.4 0.1 1.4 0.2 0.3 0.0 0.5 3.4 0.2
Drafi DR_PL1*2 1.0 0.8 5.8 1.5 27 13 15 31 0.09 35 0.02 0.06 0.3 6.3 11 14 0.09 1.5 0.04 0.2 0.04 0.04 1.1 0.2
DR_PL2*5 2.5 0.2 3.2 1.3 44 7.7 8.9 20 0.08 19 0.06 0.07 0.3 3.8 6.4 15 0.06 1.1 0.06 0.2 0.04 0.03 0.6 0.08

(continued on next page)

209
 210
Table 2 (continued)

mg/kg wt%
Location Sample
Shoots As Mo Cu Pb Zn Ni Co Mn Th Sr Cd Sb La Cr Ba B Fe Ca P Mg Al Na K S

DR_PL3*6 1.5 1.8 3.6 1.0 25 5.0 13 31 0.06 6.5 0.02 0.06 0.2 3.1 2.4 7 0.04 0.4 0.05 0.06 0.03 0.04 1.0 0.1
DR_PL4*7 0.1 0.5 8.4 0.2 41 1.4 12 39 0.005 45 0.005 0.02 0.02 2.1 5.1 21 0.02 1.8 0.2 0.3 0.005 2.0 0.9 0.2
DR_PL5*2 0.9 0.4 6.8 0.6 26 2.5 30 17 0.04 32 0.01 0.05 0.2 3 8.9 8 0.04 1.0 0.05 0.1 0.03 0.1 0.7 0.1
DR_PL6*3 1.3 0.6 8.4 0.4 29 2.5 15 17 0.02 14 0.03 0.05 0.1 3 3.6 13 0.03 0.9 0.08 0.1 0.02 1.2 2.0 0.3
Average 1.2 0.7 6.0 0.8 32 5.4 16 26 0.05 25 0.02 0.1 0.2 3.6 6.2 13 0.05 1.1 0.1 0.2 0.03 0.6 1.1 0.2
Artemida AR_PL1*3 0.8 0.6 8.5 1.5 30 1.9 8.0 33 0.07 28 0.03 0.07 0.3 3.6 7.1 26 0.07 2.3 0.06 0.2 0.04 0.3 2.4 0.2
AR_PL2*6 0.3 0.4 3.8 0.7 17 1.3 31 20 0.06 3.7 0.005 0.04 0.2 3.1 1.8 2 0.02 0.2 0.03 0.05 0.02 0.04 0.7 0.1
AR_PL4*8 0.4 0.1 2.8 0.8 18 0.9 5.6 26 0.03 16 0.04 0.05 0.2 2.6 5.5 13 0.03 0.5 0.04 0.1 0.02 0.01 0.6 0.1
AR_PL5*2 0.05 0.1 4.4 0.7 9.6 1.1 7.3 14 0.03 36 0.03 0.04 0.2 3.3 7 13 0.03 1.0 0.03 0.1 0.02 0.1 0.6 0.1
AR_PL6*8 6.4 0.5 11 4.1 32 5.0 62 63 0.2 11 0.2 0.1 0.6 5.3 7.3 19 0.1 1.0 0.05 0.1 0.09 0.3 1.1 0.1
AR_PL7*9 0.8 0.7 16 1.2 38 20 46 49 0.01 33 0.09 0.05 0.5 27 9.5 22 0.2 2.2 0.3 0.4 0.1 0.06 2.9 0.3
AR_PL8*10 0.05 0.8 8.8 0.2 11 1.3 12 15 0.005 18 0.4 0.02 0.03 3.1 4 11 0.02 1.2 0.3 0.1 0.005 0.03 1.9 0.4
Average 1.3 0.5 7.9 1.3 22 4.5 25 31 0.06 21 0.1 0.05 0.3 6.9 6.0 15 0.06 1.2 0.1 0.2 0.05 0.1 1.5 0.2
Kalamos KAL_PL2R*2 2.8 0.2 12 1.2 32 3.8 20 45 0.09 9.4 0.07 0.1 0.5 5.4 16 5 0.07 0.8 0.06 0.1 0.07 0.01 0.3 0.07

E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222

KAL_PL5R*2 2.3 0.2 13 1.2 12 3.4 26 42 0.1 4.4 0.04 0.09 0.6 4.5 6.4 4 0.07 0.4 0.03 0.07 0.07 0.04 0.5 0.06
KAL_PL15R*2 1 0.1 8.4 1.0 13 1.9 14 22 0.06 3.7 0.03 0.07 0.3 3.6 5.2 4 0.04 0.4 0.02 0.05 0.04 0.02 0.3 0.04
Average 2.0 0.2 11 1.1 19 3.0 20 36 0.09 5.8 0.05 0.09 0.4 4.5 9.3 4.3 0.06 0.5 0.04 0.07 0.06 0.02 0.3 0.06
Varnavas VAR_PL24R*2 1.5 0.2 12 2.3 31 1.2 14 17 0.04 4.8 0.03 0.2 0.3 2.7 7.7 5 0.04 0.7 0.02 0.06 0.03 0.02 0.3 0.07
Drafi DR_PL1R*2 1.6 0.7 12 1.3 16 15 68 38 0.08 17 0.02 0.08 0.3 7.9 5.4 6 0.08 0.6 0.02 0.1 0.05 0.02 0.6 0.05
DR_PL2R*5 24 0.08 51 5.3 19 4.7 0.3 23 0.01 15 0.07 0.7 0.09 3.1 6 5 0.03 0.6 0.02 0.06 0.02 0.008 0.2 0.02
DR_PL3R*6 34 0.7 8.6 17 145 72 22 169 0.7 15 0.1 0.5 2.4 27 18 5 0.5 2.0 0.04 0.2 0.4 0.007 0.6 0.1
DR_PL4R*7 2.5 0.1 11 0.8 61 4.8 7.6 37 0.1 36 0.02 0.1 0.2 3.9 8.8 11 0.06 1.0 0.06 0.3 0.04 0.9 0.2 0.09
Average 15 0.4 21 6.2 60 24 24 67 0.2 21 0.06 0.3 0.8 11 9.6 6.8 0.2 1.0 0.03 0.2 0.1 0.2 0.4 0.07
Artemida AR_PL1R*3 2.8 0.5 25 2.9 73 3.4 10 69 0.08 23 0.04 0.08 0.4 4.5 9.6 15 0.08 1.4 0.06 0.1 0.06 0.2 0.7 0.1
AR_PL4R*8 0.9 0.08 4.8 0.9 9.5 1 8.6 13 0.04 11 0.03 0.1 0.2 2.9 3.8 5 0.03 0.3 0.02 0.05 0.03 0.001 0.4 0.04
Average 1.9 0.3 15 1.9 41 2.2 9.5 41 0.1 17 0.04 0.1 0.3 3.7 6.7 10 0.1 0.9 0.04 0.1 0.05 0.1 0.5 0.1
Detection limit 0.1 0.01 0.01 0.01 0.1 0.1 0.01 1 0.01 0.5 0.01 0.02 0.01 0.1 0.1 1 0.001 0.01 0.001 0.001 0.01 0.001 0.01 0.01
Reference materials
STD V14 11 0.1 4.8 0.9 14 1.4 0.8 2103 0.01 6.6 0.2 0.1 0.03 1.1 1.5 11 0.02 0.6 0.1 0.1 0.1 0.001 0.5 0.1
STD V16 1.5 1.3 6.1 2.8 37 6.4 1.0 704 0.01 11 0.1 0.1 0.04 276 2.1 5.3 0.4 0.3 0.05 0.1 0.05 0.00 0.2 0.03
STD CDV-1 1.1 0.2 7.5 0.8 21 5.8 1.8 340 0.6 103 0.03 0.03 2.1 11 7.8 12 0.2 1.7 0.03 0.1 0.1 0.005 0.2 0.10
Excessive or toxic in shootsa 5–20 10–50 20–100 30–300 100–400 10–100 15–50 400–100 – – 5–30 150 – 5–30 – 50–200 – – – – – – – –

Symbols: *1: Stachys germanica; *2: Thymus sibthorpii; *3: Sonchus oleraceus; *4: Cichorium intybus; *5: Phlomis fruticosa; *6: Bromus arvensis; *7: Foeniculum vulgare; *8: Inula verbascifolia ssp. Methanea; *9: Malva sylvestri; *10: Sinapis arvensis; *11: Lactuca
sativa (cultivated plants).
a
After Kabata-Pendias and Pendias, 2001.
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222
Plasma Mass Spectroscopy (ICP/MS), after Aqua Regia Digestion, at the
ACME Analytical Laboratories in Canada. Roots were analysed separate-
ly from the shoots.
Water samples (n = 20) were collected from the surface discharges
of springs, agricultural and domestic wells, and boreholes. The springs
were characterized as the contact between the travertine limestone
and basement schists. The water of wells and boreholes are associated
with unconfined and confined aquifers, which develop in Neogene for-
mations. A single round of groundwater samples was collected from 20
locations within the study area in October 2012 (wet period). Measure-
ments of T, pH, Eh, electric conductivity (EC), TDS and salinity were per-
formed in the field at the time of groundwater sampling with Consort
C561 portable multiparameter analyzer. The measurement of T was
conducted in the wet period (October 2012) and ranged from 16 to
18 °C for boreholes, 13 to 14 °C for springs and 14 to 16 °C for wells.
The samples were collected and divided in two portions, and one por-
tion was stored in polyethylene containers at 4 °C in a portable refriger-
ator. The second portion of each sample was acidified by addition of
concentrated HNO3 acid and also stored at 4 °C. The groundwater sam-
ples were analysed by inductively coupled plasma mass spectroscopy
(ICP-MS) at the ACME Analytical Laboratories Ltd., Vancouver, Canada.
The detection limit of the analytical method and results of standard
(STD) and black analysis (BLK) for all samples are provided at the end of
each table.
2.2. Statistical analysis and geochemical mapping
Statistical software codes (Microsoft Excel 2007, MINITAB v. 15.0
and SPSS v. 17.0) were used to represent the spatial distribution of
ground water parameters and bio-accumulation in the Neogene basins
of Attica. For the correlation analysis, selected elements with relation-
ships N0.50 were plotted in diagrams using Microsoft Excel software.
The R-mode factor analysis was conducted by applying the Varimax-
raw rotational technique with Kaiser Normalization processing to the
geochemical data set. The correct number of factors was selected
using a combination of common criteria as to be expressed higher per-
centage variation of geochemical data (% of variance) after using the
Scree plot method. For determination of inter-element relationships,
factor loadings N 0.50 were selected.
A geographical information system (GIS) of ArcGIS v. 10.2 is used to
digitize available and generated information of geomorphology and
chemical analysis. All maps required geo-referencing to the area coordi-
nates according to the HGRS 87.
Hot Spot Analysis (Getis-Ord Gi*) is a tool of Spatial Statistics for
ArcMap that identifies statistically significant spatial clusters of high
values (hot spots) and low values (cold spots). This analysis creates a
new Output Feature Class with a z-score and p-value for each feature
in the Input Feature Class.
Kriging (Geostatistical Analyst for ArcMap) is an interpolator that
can be exact or smoothed depending on the measurement error
model. Kriging is very flexible and allows a user to investigate graphs
for spatial auto- and cross-correlation. Kriging uses statistical models
that allow a variety of output surfaces including prediction map by ordi-
nary Cokriging and probability maps by indicator Kriging. In ordinary
Cokriging, statistical weighting is based on the distance between mea-
sured points and the overall spatial relationships between locations.
This method also enable for assessment of multiple variables (z-score
of hot spots analysis) that have an effect on the variable of interest (con-
centration of the plant or water samples). Indicator Kriging assumes an
unknown constant mean. The specified threshold (value from a guide-
line) is an important parameter that determines which predictions
will receive a 0 or 1.
Saturation indices for selected minerals were calculated using the
software code Aquachem 2012.1 by Schlumberger Water Services to
better understand the hydrochemical processes that occur in the
aquifers.
211
3. Results
3.1. Trace element contents in plants and soils
Kampouroglou and Economou-Eliopoulos (2016) presented
that the average contents of As, Ni, Cr and Ba in soils is higher
than the parametric values of Dutch limits (2009). The soil pH
ranges from 7.4 to 8.3 and Eh from − 111 to − 57 mV (Table 1).
There is significant variation in the contents of As (16–1200 mg/kg),
Cu (5.3–77 mg/kg), Pb (14–240 mg/kg), Ni (58–660 mg/kg), Co
(15–64 mg/kg), Mn (290–1400 mg/kg), Cr (82–1400 mg/kg), Ba
(6–410 mg/kg), Sb (1.6–21 mg/kg), V (15–160 mg/kg), Sc (0.3–19
mg/kg), Fe (0.83–5.6 wt% ), and P (0.02–1.3 wt%) in soils, which
are commonly higher than in rock samples. Compared with the back-
ground values, the average contents of As, Pb, Zn, Cr, Ba, Sb, V, La, Ca,
Ti, Al, Na, K and organic matter are the highest, whereas the average
contents of Cd and Fe are only slightly higher than or similar to the
background values (Table 1).
The arsenic content in roots (Table 2) ranges from 0.8 to 34 mg/kg
and from 0.05 to 30 mg/kg in shoots. The highest values for As, Mo,
Pb, Zn, Ni, Mn, Th, Cd, La, Cr, Ba, Ti, Fe, Ca, Al and S in roots belong to
the sample DR_PL3R (Bromus arvensis). This plant showed low values
of elements in shoots. The cultivated plants of lettuce had higher values
of As, Mo, Cu, Pb, Zn, Mn, Cd, Sb, Ba, B, Fe, Ca, P, Mg, Na, K and S in shoots
than the average values of shoot samples in Neogene basins of Attica.
The highest contents of As were found in samples coming from the
Kalamos-Varnavas basin, particularly Thymus sibthorpii of the Kalamos
area and cultivated Lactuca sativa of the Varnavas area. The percentage
of soil metals in plants [(metal in plant × 100) / metal in soil] or bio-
accumulation factor for As, Pb, Ni, Mn, Cr, Ba, Sb and Fe ranging from
1.5% to 7.6% is lower than that for Cu, Zn, Co, Ca and Mg, ranging from
29% to 67%, and the exceptionally high average of 265% for P (Table
3). Of these elements, Mn, Fe, Cu, Zn, Ca, P and Mg are characterized
as essential for plant growth. There is a positive correlation concerning
the bio-accumulation factor for As versus Νi, Fe and Cr for plants in all
Neogene basis of Attica (Fig. 2; Table 4). Any relationship between the
bio-accumulation factor for As and P is not obvious (r = 0.2), but
there is a strong positive correlation (r N 0.8) between As and P contents
in plant roots from the Kalamos and Artemida basins, and a negative
correlation (r = − 0.8) in plant shoots from the Drafi basin (Fig. 2d).
There is also a positive correlation between As and Pb, Mn, Ba and Sb
and a negative correlation between As and Ca and Co (Table 4).
3.2. Elemental spatial distribution patterns of bioaccumulation
The predictable spatial distribution of the bio-accumulation factor
for As and Fe in the Neogene basins of Attica are presented (Fig. 3a–
b). Cr, Ni and Mn bio-accumulation factor showed similar spatial distri-
bution, as expected by the correlation analysis (Table 4). After Hot Spot
analysis, these maps are in a good agreement with the hypothesis that
hot spots are present in the Varnavas area. Arsenic, Fe, Cr, Ni show
high contents in the Varnavas area up to the northern part of the
Mesogeia basin (Drafi area). Manganese shows higher values in the
Varnavas area up to the N site of Penteli Mount. The Kalamos basin
presents lower to intermediate values of As, Fe, Cr, Ni and Mn. The low-
est values were found in the Mesogeia basin.
3.3. Health risk assessment in soils
The spatial maps of Fig. 4a-c indicate the probability that As, Ni and
Cr in soils to exceed the corresponding Dutch Guideline (2009). There is
a high probability of health risks from arsenic contamination for the
Kalamos-Varnavas basin. There is a medium probability of arsenic and
nickel contamination in the eastern part of Mesogeia basin (Fig. 4a-b).
In Fig. 4b, the western part of the Attica detachment has a high probabil-
ity for health risks associated with nickel. Chromium shows high risk
212 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222

Table 3
Percentage of soil metals in plants (mplant/msoil * 100) from Neogene basins of Attica. Data from Table 1; Kampouroglou and Economou-Eliopoulos (2016), soils *: Kampouroglou and
Economou-Eliopoulos (2013).

mp/ms * 100

Location Description As Cu Pb Zn Ni Co Mn Cr Ba Sb Fe Ca P Mg

Kalamos PL1-S1 0.02 19 1.1 7.2 0.3 130 3.4 0.7 0.8 2 0.5 19 186 14
PL2-S1 1.7 13 4.3 9.6 2.7 59 4.9 2.6 9.4 4 2.7 53 126 12
PL3-S2 2.5 11 3.4 13 2.8 25 4.8 2.6 15 2.9 3.2 7.7 159 13
PL4-S2 0.3 4.7 2.2 8.0 0.4 34 3.3 0.5 1.5 0.5 0.6 2.7 129 9.4
PL5-S3 0.8 28 1.1 15 1.7 42 1.9 2.1 2.5 2 1.4 97 112 12
PL6-S3 0.6 10 1.3 26 1.4 118 3.8 1.6 2.6 2.4 1.1 31 90 7.0
PL7-S4 1.9 33 5.2 30 4.6 41 5.8 3.8 14 3.6 3.0 7.9 91 18
PL8-S5 0.2 27 0.8 50 0.7 27 4.3 0.9 1.4 1 0.6 177 231 18
PL10-S6 0.7 16 2.8 119 1.8 18 11 2.1 3.8 0.7 2 8.2 678 21
PL11-S6 0.9 12 1.5 53 0.7 62 5.1 1.3 4 0.8 1.1 5.8 404 18
PL12-S7 1.1 8.6 1.3 4.2 1.8 61 2.1 1.6 8.1 2 1.4 45 15 24
PL13-S7 0.4 5.1 1.1 4.5 0.9 124 2.1 1.6 0.6 2.8 0.5 5.8 13 9.2
PL14-S8 0.2 5.3 0.4 15 0.8 33 4.7 0.7 0.7 1.2 0.2 29 149 3.1
PL15-S8 0.4 10 1.5 16 0.7 76 1.4 1.0 3.2 2 0.8 182 147 9.1
Varnavas PL20-S10 1.6 34 2.2 17 4.7 204 5.2 6.0 8.7 1.5 2.8 8.5 108 28
PL21-S10 0.3 12 0.4 6.8 2.4 63 3.3 2.8 2.3 0.4 0.6 1.9 110 8.5
PL22-S11 0.4 37 0.7 42 0.7 75 5 2.6 1.4 0.8 0.6 238 430 27
PL23-S12 0.6 30 0.8 9.6 1.2 64 2.2 2 3.4 0.8 1.6 104 102 30
PL24-S12 0.1 20 0.3 7.5 0.6 36 1.2 1.2 2.5 0.3 0.5 37 124 18
Drafi PL1-S1 0.3 29 3.4 37 3.4 43 4.4 2.2 6.5 2.4 2.7 12 186 33
PL2-S1 0.8 16 3.0 62 2.0 25 2.9 1.3 3.8 2.8 1.9 9.0 255 23
PL3-S1 0.5 18 2.3 34 1.3 37 4.4 1.1 1.4 2.4 1.2 2.9 223 8.8
PL4-S2 0.2 38 0.5 65 1.1 54 5.2 1.6 2.1 0.8 0.7 16 540 43
PL5-S2 1.4 31 1.4 42 1.9 135 2.3 2.3 3.7 2 1.4 8.8 173 19
PL6-S2 2.0 38 1.0 46 1.9 70 2.3 2.3 1.5 2 1.0 8.0 280 17
Artemida PL1-S1 0.6 33 1.6 40 1.9 42 3 2.4 3.2 2.8 2.7 19 76 30
PL2-S1 0.2 15 0.7 23 1.3 166 1.8 2.1 0.8 1.6 0.9 1.8 36 6.5
PL4-S2 0.4 13 1.1 20 0.9 31 3.9 1.9 2.1 2 1.0 4.5 88 15
PL5-S2 0.1 20 1.0 11 1.1 41 2.1 2.4 2.7 1.6 0.9 8.9 72 15
PL6-S3 2.4 35 1.7 24 4.2 309 6.8 3.3 3.2 1.6 3.7 23 91 14
PL7-S4 2.2 25 4.4 61 4.8 140 7.9 4.3 7.3 2 5.7 20 381 16
PL8-S4 0.1 14 0.7 18 0.3 36 2.4 0.5 3.1 0.8 0.6 11 422 5.2
Drazaiza* EV1 -ES1 3.3 42 17 74 8.8 21 8.9 5.3 19 20 3.9 18 164 23
Pourithi* EV2 -ES2 2.9 72 2.6 89 3.5 17 10 5.3 7.7 6 2.5 13 428 82
EV4 - ES4 6.1 161 6.8 83 6.3 20 11 12 13 12 6.3 10 371 59
Varnavas quarry* EV5 - ES5 2.9 40 2.3 33 13 41 17 6.8 11 5.1 2.7 5 417 31
EV7 - ES7 9 95 17 62 14 40 45 15 19 19 11 11 568 76
EV8 - ES8 1.7 30 2 22 3.8 28 11 3.8 25 4.6 2.4 26 1329 81
PL31 - ES5 0.5 320 6 95 30 39 34 7.8 59 61 7.9 14 648 195

Symbols: mp = metal content in plant; ms = metal content in soil.

values in the northwestern to northern part of Kalamos-Varnavas basin
and in the north side of Athens basin. In the central part of the Mesogeia
basin, there is a medium risk for chromium. Arsenic accumulates in veg-
etables, fruits, and other plants that grow in contaminated soils, sug-
gesting that this is an important pathway for the transfer of arsenic to
the food chain (Meharg and Hartley-Whitaker, 2002).
3.4. Trace element concentrations in water
Concentrations of As, B, Cr, Cu, Mn, Ni, Sb, Se, Na and SO4 in water
samples were lower than the parametric values established by the Euro-
pean Community (Council Directive 98/83/EC). In contrast, the ele-
ments Ag, Al, Au, Bi, Cd, Ce, Co, Er, Eu, Fe, Ga, Hf, Hg, Ho, In, La, Lu, Nd,
Pd, Pr, Pt, Sm, Ta, Tb, Te, Th, Ti and Tm were lower than the detection
limit, so were not presented in Table 5. In water, pH ranges from 6.6
to 7.8 and Eh ranges from −83 to 23 mV (Table 5). The water samples
of Artemida (Mesogeia basin) are characterized as brackish water be-
cause of salinity values that are 0.8 to 0.9‰. The salinity values of the
water samples are between 0.2 and 0.4‰ in the Kalamos-Varnavas
basin and described as fresh water. Arsenic and sulphur showed higher
values in the southern and southwestern part of the Mesogeia basin. In-
termediate to high concentrations of Na and Cr were also measured in
the Mesogeia basin. There is a significant positive correlation between
As and Li, Se, K, Mg, Na and S (Fig. 5). In Fig. 5, groundwater values
from the Mesogeia basin of the present study were compared to
published data (wet period) for the same basin in the area of Koropi
(n = 31) (Chrisanthaki, 2010; Pavlopoulos et al., 2011).
The water samples from the areas of Kalamos, Varnavas and
Kaisariani are classified as a Ca\\HCO3 water type, while samples from
Artemida are a Ca\\Cl water type (Fig. 6).
The mineralogical composition of water-bearing formations in
combination with the calculation for thermodynamic equilibrium
conditions of ground waters (Table 6) showed that the main min-
erals present in the aquifers are: anhydrite (CaSO4 ), aragonite
(CaCO3), barite (BaSO4), calcite (CaCO3), chalcedony (SiO2), dolo-
mite (CaMg(HCO3) 2), gypsum (CaSO4 2H2O), halite (NaCl), quartz
(SiO 2), talc (Mg3 Si4 O10(OH) 2) and witherite (BaCO 3). The ground
water of the study area is saturated in quartz and unsaturated in an-
hydrite, aragonite, chalcedony, gypsum, halite, talc and witherite.
Aragonite is saturated only in agricultural wells of the Varnavas
area. Barite is saturated in agricultural wells of the Artemida area.
Calcite is saturated in springs of Varnavas and in agricultural wells
of Varnavas and Artemida. Dolomite is unsaturated in all sample
sites except from the area of Artemida.
3.5. Statistics-factor analysis in waters
The results of multivariate analysis (factor) in the ground water of
Kalamos-Varnavas and Mesogeia basin are presented in Table 7 and
Fig. 7a-c. Three factors were identified that account for 71.7% of the
total variance. The first factor explained 52.5% of the total variability
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222 213

16 a 18
b
14 16
R² = 0,77 14 R² = 0,90
12

Cr mp/ms*100
Ni mp/ms*100 12
10
10
8
8
6
6
4
4
2
2
0 0
0 2 4 6 8 10 0 2 4 6 8 10
As mp/ms*100 As mp/ms*100

12 c 1,00
d
10
R² = 0,87
Fe mp/ms*100

P (wt%)
6 0,10

0
0,01
0 2 4 6 8 10
0,01 0,10 1,00 10,00 100,00 1000,00
As mp/ms*100 As (mg/kg)
Roots Kalamos-Varnavas Roots Drafi Roots Artemida
Kalamos Varnavas Drafi Artemida Shoots Kalamos-Varnavas Shoots Drafi Shoots Artemida

Fig. 2. Correlation analysis diagrams for selected elements in the percentage of bioaccumulation (a–c) and As versus P content in shoots and roots (d). Data from Tables 1 and 3.

that includes As, B, Cr, Li, Se, Cl, K, Mg, Na and S. This factor (Fig. 7a),
which could be considered the salinity factor, expresses the total salt
concentration of the groundwater samples and is determined by these
ions. Factor 2 explains 10.2% of the total variance and has positive load-
ings for Li and Si. This factor explains the dissolution of silicates from the
metamorphic basement (Fig. 7b). Factor 3, which explains 9.0% of the
variance, has high positive loading (N 0.75) on Zn, and may be
interpreted as leaching from the lignite intercalations found in the Neo-
gene lacustrine deposits (Fig. 7c).
3.6. Health risk assessment in waters
The estimated risk assessment maps for As and Na in water show
that these elements exceed the corresponding Directive 98/83/EC
(Fig. 8a–b). Similar risk values were presented for Cl and Se. These
four elements showed high risk values in the southwestern and cen-
tral part of the Mesogeia basin. In contrast, our results showed that
the Kalamos-Varnavas basin is safe.
4. Discussion
4.1. Bioaccumulation of As
Based on the presented data, the level of accumulated elements
differs between and within species, most likely due to genetic dif-
ferences (Meharg and Hartley-Whitaker, 2002). As contents in
roots, are often higher than normal or limited values (Kabata-
Pendias and Pendias, 2001). Additionally, Co and Cr in shoots and
Ni, Co and Cr in roots are often higher than normal or limited values
(Kabata-Pendias and Pendias, 2001). Acceptable limits for As and
heavy metals for plants, however, have not been established. Arse-
nic content appears to be elevated in green vegetables and plants
grown in the most contaminated soils. The bio-accumulation factor
for As (As plant / As soil * 100), ranges from 0.02 to 9.0% and it has a
positive correlation with that for Fe, Cr, Ni, Mn, Pb and Sb, suggest-
ing that even low As/metal contents in the soil can be significant in
plants.

Table 4
Correlation matrix of selected major and trace elements in the percentage of soil metals in plants from the Neogene basins of Attica. Data from Table 3.

As Cu Pb Zn Ni Co Mn Cr Ba Sb Fe Ca P Mg
mp/ms * 100

As mp/ms * 100 1
Cu 0.41 1
Pb 0.71 0.47 1
Zn 0.42 0.64 0.47 1
Ni 0.74 0.68 0.73 0.44 1
Co −0.12 −0.16 −0.26 −0.31 −0.11 1
Mn 0.59 0.61 0.69 0.56 0.77 −0.27 1
Cr 0.74 0.74 0.65 0.42 0.91 −0.06 0.73 1
Ba 0.66 0.61 0.75 0.36 0.82 −0.31 0.67 0.73 1
Sb 0.58 0.63 0.79 0.41 0.79 −0.21 0.69 0.71 0.7 1
Fe 0.77 0.67 0.86 0.48 0.87 −0.11 0.71 0.83 0.85 0.74 1
Ca −0.09 0.08 −0.15 −0.05 −0.18 0.03 −0.17 −0.13 −0.01 −0.06 −0.13 1
P 0.24 0.53 0.31 0.67 0.3 −0.41 0.62 0.29 0.41 0.24 0.33 0.04 1
Mg 0.44 0.82 0.5 0.5 0.65 −0.28 0.65 0.71 0.7 0.6 0.68 0.07 0.51 1
214 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222

Fig. 3. Prediction maps showing the spatial distribution pattern of the bio-accumulation factor for (a): As and (b): Fe in Neogene basins of Attica. Data from Table 3.
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222 215

a b

Fig. 4. Estimated risk assessment maps for (a): As; (b): Ni; (c): Cr in soils corresponding Dutch Guideline (2009). Data from Table 1; Kampouroglou and Economou-Eliopoulos (2016).

Table 5
The concentrations of major and trace elements in waters from the Neogene basins of Attica and sea-water from the Evoikos Gulf.

μg/l mg/l
mV μS/cm ‰
Location Samples As B Cr Zn Li Se U Si Ca Cl K Mg Na S HCO3 SO4 TDS pH Eh EC sal

Kalamos KAL W1*1 6.4 31 19 1.8 9.8 1.4 0.4 12 120 77 1.5 14 29 6 366 18 350 7.2 −1 654 0.3
KAL G01*2 6.2 16 6.5 1300 17 1.1 0.4 8.3 93 50 1.4 18 24 3 283 9 312 6.6 23 582 0.3
KAL G02*2 1.6 12 8.6 2.7 1.8 0.0 0.4 5.6 96 17 0.7 18 10 2 293 6 251 7.1 5 469 0.2
KAL_W10*1 6.3 31 12 b0.5 9.2 1.4 0.4 7.4 73 60 1.3 15 39 16 223 48 343 7.8 −83 640 0.3
Varnavas VAR R100*1 1.3 105 6.0 1.4 2.4 1.3 0.3 10 110 70 3.2 11 37 16 336 48 350 7.3 −13 648 0.3
VAR R101*1 1.2 89 6.2 0.7 3.0 0.7 0.3 11 130 78 2.5 12 39 17 397 51 375 7.4 −16 704 0.3
VAR R102*1 1.5 29 5.1 b0.5 6.1 1.3 0.2 11 130 82 0.8 15 40 24 397 72 413 7.5 −19 776 0.4
KAPA F1*3 2.6 12 7.0 500 2.5 1.3 0.5 7.5 140 46 0.8 8 24 12 427 36 368 7.2 −4 686 0.3
KAPA F2*3 3.2 15 6.0 400 1.6 0.5 0.6 6.5 140 42 0.8 7 23 15 427 45 344 7.2 −7 644 0.3
KAPA F3*3 2.3 17 6.9 80 2.3 0.9 0.4 7.8 140 41 1.3 8 25 17 427 51 370 7.1 2 692 0.3
KPW 100*1 3.6 25 7.3 0.7 3.5 1.0 0.4 8.3 120 48 0.9 10 28 9 366 27 327 7 6 605 0.3
KPW 101*1 2.2 18 6.1 0.5 3.3 1.2 0.4 9.4 130 59 0.8 10 33 14 397 42 261 6.9 11 489 0.2
KAPR2000*1 3.7 23 6.1 b0.5 4.5 0.9 0.3 9.7 100 48 0.8 11 31 8 305 24 319 7.3 −11 594 0.3
KAP G1*2 0.3 15 5.6 b0.5 3.2 0.8 0.5 7.8 120 45 0.7 6 25 8 366 24 340 7.2 −3 638 0.3
MET_W1*4 2.0 24 15 b0.5 14 1.5 1.0 13 71 46 1.4 30 42 12 216 36 480 7.6 −72 900 0.4
MET_W2*4 2.2 15 13 380 6.7 0.7 0.2 7.4 97 26 1.6 5.7 16 11 295 33 268 7.7 −78 502 0.2
Artemida AR_W1*3 9.2 130 17 b0.5 12 5.0 3.3 12 140 310 5.6 64 120 34 427 102 900 7.4 −64 1670 0.8
AR_W2*3 5.3 96 17 b0.5 14 6.6 1.8 12 160 370 2.7 47 130 26 488 78 950 7.2 −53 1770 0.9
AR_W3*3 4.7 120 14 b0.5 12 5.5 3.2 11 120 300 5.4 62 120 34 366 102 880 7.5 −71 1650 0.8
Kaisariani W·UN·CAM*2 2.5 62 8.3 b0.5 7.8 1.8 2.6 8.5 85 71 1.9 45 42 9 259 27
Evoikos Gulf sea water 80 4200 60 b50 160 360 b2 2 390 490 1200 6400 1200 1190 3600
Detection Limit 0.5 5 0.5 0.5 0.1 0.5 0.02 0.04 0.05 1 0.05 0.05 0.05 1
Reference Materials
STD TMDA-70 42 17 404 497 23 26 59 0.4 22 13 1.0 5.8 8.8 7
STD TMDA-70 43 18 414 504 21 26 62 0.5 24 13 1.0 6.1 8.7 b1
Reference values a 10 1000 50 – – 10 – – – 250 – – 200 – – 250 2500

Symbols: *1: spring; *2: borehole; *3: agricultural well; *4: domestic well.
a
Reference values according to Directive 98/83/EC.
216 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222

1000 1000,00

R² = 0,94
100,00
100 R² = 0,66
Li (µg/l)

10,00

Se (µg/l)
10 1,00

0,10
1
0 20 40 60 80 100 0,01
As (µg/l)
0 20 40 60 80 100
Koropi Kalamos Varnavas Artemida Kaisariani Sea water As (µg/l)

1000,0 10000

R² = 0,90
100,0 1000
R² = 0,86

Mg (mg/l)
K (mg/l)

10,0 100

1,0 10

0,1 1
0 20 40 60 80 100 0 20 40 60 80 100
As (µg/l) As (µg/l)

10000 10000

R² = 0,35
1000 1000
R² = 0,84
S (mg/l)
Na (mg/l)

100 100

10 10

1 1
0 20 40 60 80 100 0 20 40 60 80 100
As (µg/l) As (µg/l)

Fig. 5. Correlation analysis diagrams for selected elements in water samples. Data from Table 5; Chrisanthaki (2010), for the Koropi area.

Factors that can influence the arsenic content in plants may be the
species type, the ability of arsenic to enter the plant (actively or passive-
ly), and the presence of species adhered to the outside surface of the
plant roots (Vamerali et al., 2010). Baker and Brooks (1989) classified
the plants growing in metal-contaminated soils into three categories:
i) excluders that maintain the concentration in shoots at a low level
up to the critical soil value, which is above relatively unrestricted root-
to-shoot transport results, ii) accumulators that concentrate metals in
high levels, and iii) indicators that uptake and transport the metals to
the shoot until toxicity occurs.
The mobility, transport and availability of As in soil and its mobiliza-
tion from soil to shoots of the plants (bio-accumulation factor) is mostly
dependent on the soil pH, the As content in soil and its speciation
(Mench et al., 2009). Soil pH that ranges from 7.4 to 8.3 suggests that ar-
senic must be in the form of arsenate. More specifically, inorganic arse-
nic in the form of arsenite [As(III)] is more mobile and considered to be
more toxic than arsenate [As(V)]. Nevertheless, both types of com-
pounds are characterized as harmful to living organisms (Caruso et al.,
2001; Kumaresan and Riyazuddin, 2001; Zhou et al., 2003). Negatively
charged arsenate is strongly adsorbed onto the surface of several com-
mon minerals. Arsenite adsorbs less strongly, which is a property that
enables it to be more mobile (Mandal and Suzuki, 2002).
The mineralogical and geochemical data, particularly the
Fe\\Mn-hydroxides and minor base metal sulphides, such as pyrrho-
tite, pyrite, chalcopyrite, sphalerite, barite, galenite, enargite and
tennantite, as well as F-apatite, quartz, Ti-oxides, zircon, sphene, rutile
and REE-phosphate minerals in the travertine limestones studied in Neo-
gene basins of Attica (Kampouroglou and Economou-Eliopoulos, 2016),
may provide evidence for their contribution of detrital and chemical
components from the erosion of Grammatiko Fe-Mn and Lavrion miner-
alization and host rocks (Marinos and Petrascheck, 1956; Skarpelis,
2007; Voudouris et al., 2008). Moreover, the presence of Fe and manga-
nese oxides also increases As mobility and its availability in soil (Zavala
and Duxbury, 2008).
Apart from presenting a health risk, the presence of As in irrigation
water or soil at an elevated level could hamper normal growth of plants
with toxicity symptoms such as biomass reduction (Carbonell-
Barrachina et al., 1997) and yield loss (Jiang and Singh, 1994). Although
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222 217

Fig. 6. A plot of water samples on a Piper diagram. Symbols: inverted triangles: Kalamos; triangles: Varnavas; orange circles: Artemida; green stars: Koropi; square: Kaisariani. Data from
Table 5; Chrisanthaki (2010), for the Koropi area. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

the mechanism of As bio-accumulation is not yet well understood to
date, relatively high As, Fe, Cr, Mn, Ni and Co contents in the sample of
Thymus sibthorpii are consistent with the relatively high contents of
these elements in the soil of the area. This may confirm suggestions
that As can be loaded into the xylem system (Verbruggen et al., 2009).
In addition, the positive correlation between As and Fe and Cr (Fig. 2)
may suggest that they have a common driving force for their bio-
accumulation as they are affected by the same uptake mechanisms.
With respect to Cr bio-accumulation, it may enter in plants by reduction
and/or complexation with root exudates, such as organic acids, which
increase the solubility and mobility of Cr through the root xylem
(Bluskov et al., 2005). At neutral pH, Cr(VI) compounds are tetrahedral
and transported across cell membranes through similar tetrahedral ion
channels, while Cr(III) is octahedral and transported through diffusion
across membranes (Cohen et al., 2006).
Arsenic is toxic whereas phosphorus is essential for plants, although
they are both Group VA elements in the periodic system and have
similar electron configurations and chemical properties. Due to
their similarity, arsenate competes for the same adsorption sites in the
soil, which results in a reduction of their sorption by soil and an increase
in solution concentrations (Livesey and Huang, 1981; Manning and
Goldberg, 1996; Smith et al., 2002). This assumes that arsenate can
react with the PO4 analogue present in soils and form stable insoluble
compounds (Meharg, 1994).
With respect to the plants studied from Attica, any relationship
between the bio-accumulation factor for As and P is not obvious

Table 6
Saturation indices for selected minerals in waters from the Neogene basins of Attica.

Location Samples Anhydrite Aragonite Barite Calcite Chalcedony Dolomite Gypsum Halite Quartz Talc Witherite

Kalamos KAL W1*1 −2.41 −0.083 −0.624 0.065 −0.088 −0.518 −2.173 −7.229 0.357 −5.108 −3.737
KAL G01*2 −2.779 −0.279 −0.664 −0.131 −0.249 −0.69 −2.542 −7.491 0.196 −5.36 −3.604
KAL G02*2 −2.935 −0.244 −1.632 −0.097 −0.42 −0.635 −2.698 −8.337 0.025 −6.029 −4.381
KAL_W10*1 −2.138 −0.488 −0.24 −0.341 −0.299 −1.085 −1.901 −7.198 0.146 −5.814 −4.029
Varnavas VAR R100*1 −2.013 −0.16 −0.278 −0.012 −0.167 −0.74 −1.776 −7.164 0.278 −5.755 −3.865
VAR R101*1 −1.947 −0.032 −0.295 0.116 −0.126 −0.518 −1.71 −7.1 0.319 −5.512 −3.82
VAR R102*1 −1.809 −0.041 −0.105 0.106 −0.126 −0.44 −1.572 −7.069 0.319 −5.247 −3.777
KAPA F1*3 −2.059 0.038 −0.501 0.186 −0.292 −0.586 −1.822 −7.538 0.153 −6.688 −3.844
KAPA F2*3 −1.963 0.037 −0.408 0.184 −0.354 −0.648 −1.726 −7.596 0.091 −7.118 −3.849
KAPA F3*3 −1.912 0.034 −0.361 0.181 −0.275 −0.596 −1.675 −7.571 0.17 −6.635 −3.855
KPW 100*1 −2.224 −0.08 −0.585 0.068 −0.248 −0.658 −1.987 −7.448 0.197 −6.184 −3.88
KPW 101*1 −2.02 −0.025 −0.375 0.123 −0.194 −0.583 −1.783 −7.291 0.251 −6.005 −3.82
KAPR2000*1 −2.325 −0.222 −0.529 −0.075 −0.181 −0.823 −2.088 −7.398 0.264 −5.754 −3.866
KAP G1*2 −2.265 −0.075 −0.589 0.073 −0.275 −0.87 −2.028 −7.523 0.17 −6.947 −3.839
MET_W1*4 −2.298 −0.518 −0.915 −0.371 −0.054 −0.831 −2.061 −7.284 0.391 −3.932 −4.574
MET_W2*4 −2.178 −0.241 −0.592 −0.094 −0.299 −1.134 −1.941 −7.947 0.146 −7.066 −4.095
Artemida AR_W1*3 −1.753 −0.042 0.177 0.105 0.158 −1.516 −6.04 −3.553
AR_W2*3 −1.811 0.072 0.038 0.219 −0.086 0.194 −1.574 −5.93 0.359 −3.742 −3.521
AR_W3*3 −1.798 −0.165 0.165 −0.017 −0.125 −0.035 −1.561 −6.05 0.32 −3.508 −3.636
Kaisariani W·UN·CAM*2 −2.397 −0.383 −0.622 −0.235 −0.238 −0.461 −2.16 −7.105 0.207 −4.182 −4.047

Symbols: *1: spring; *2: borehole; *3: agricultural well; *4: domestic well.
218 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222

Table 7 mobile and taken up by the plant through a P-independent mecha-

Varimax rotated component loadings of 3 factors and variance explained for 13 elements nism (Wang et al., 2002).
in waters of Neogene basins of Attica. Data from Table 5; Chrisanthaki (2010)—Koropi
area.

Factor 4.2. Variation of the trace element concentrations in groundwater

Variable 1 2 3 Communality

As 0.84 0.24 0.22 0.81 The concentrations of As and other elements (B, Cr, Cu, Mn, Ni, Sb, Se,
B 0.61 0.24 −0.41 0.6 Cl, Na, Ba, Co, Mo, Zn, Li, Ge, Cs, Be, Nb, Rb, Ru, Sc, Sr, U, Si, V, W, Ca, K, Mg,
Cr 0.67 0.2 0.25 0.55 S and REE) in water samples from the Neogene basis of Attica were
Zn −0.06 −0.1 0.85 0.74 lower than the parametric values of European Community (Council
Li 0.67 0.55 0.12 0.76
Se 0.93 −0.09 −0.03 0.87
Directive 93/83/EC) (Table 5). However, certain ground water samples
Si −0.13 0.88 −0.19 0.82 from an area extending into the broader area of Koropi-Markopoulo-
Ca 0.4 0.13 −0.14 0.2 Paiania-Spata, south of Hymettus (Chrisanthaki, 2010), that have devel-
Cl 0.77 −0.19 −0.12 0.65 oped within Quaternary and Neogene deposits have up to 68 μg/l of As
K 0.91 0 −0.02 0.84
(dry period) and a positive correlation between As and Na, Cl, Se, Li and
Mg 0.91 0.09 −0.15 0.86
Na 0.92 −0.03 −0.15 0.87 B. The variability of As, B, Cr, Li, Se, Cl, K, Mg, Na and S in Factor 1 can be
S 0.84 −0.13 −0.18 0.75 characterized by two processes: a) mixing of the groundwater with sea-
Total 6.82 1.33 1.17 9.32 water mainly in Mesogeia basin and b) dissolution and leaching of ter-
% of Variance 52.48 10.2 9.01 71.68 restrial salts present in the Neogene and Quaternary formations in the
Kalamos-Varnavas basin (Fig. 7a).
In addition, based on data for ground water from the area of Koropi
(r = 0.2). However, a strong positive correlation (r N 0.8) between As (Chrisanthaki, 2010), the water can be divided into five water types:
and P contents in plant roots from the Kalamos and Artemida basins Ca\\HCO3 (39%), Na\\Cl (29%), Ca\\Cl (19%), Na\\HCO3 (10%) and
may suggest that arsenate and phosphate are taken up into plant Mg\\SO4 (3%) (Fig. 6). In contrast, water samples from the areas of
roots by the same mechanism (Meharg and Hartley-Whitaker, Kalamos, Varnavas and Kaisariani can be classified into Ca\\HCO3
2002), whereas a negative correlation (r = − 0.8) in plant shoots water type and the samples from Artemida into Ca\\Cl water type
from the Drafi basin (Fig. 2d) may suggest that arsenite is more (Fig. 6).

a b

Fig. 7. Graduated symbol plots of (8a): Log Factor 1 (As, B, Cr, Li, Se, Cl, K, Mg, Na, S); (8b): Log Factor 2 (Li, Si); (8c): Log Factor 3 (Zn) scores for waters in Neogene basins of Attica in
comparison with geology. Data from Table 5; Chrisanthaki (2010), for the Koropi area.
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222 219

Fig. 8. Estimated risk assessment maps for (8a): As; (8b): Na in waters corresponding Directive 98/83/EC. Data from Table 5; Chrisanthaki (2010), for the Koropi area.
220 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 150 (2017) 206–222
Arsenic concentration in ground water may result from the natu-
ral weathering of soil and rocks and/or anthropogenic sources, in-
cluding mining, smelting, waste water, dumping of sewage sludge,
coal mining, coal burning power plants, manufacturing processes,
urban runoff and atmospheric deposition (Garbarino et al., 2003;
Francis and White, 1987; Nriagu and Pacyna, 1988; Pacyna et al.,
1995; Wadge and Hutton, 1987). Also because As and Na, Cl, Se, Li
and B are elevated in the sea-water (Table 5; Rose et al., 1979) the
relatively high concentrations of these elements in the area of Koropi
(SW part of Mesogeia basin) are attributed to a major contribution of
sea-water to aquifers, which is most likely due to their over exploitation
(Chrisanthaki, 2010; Pavlopoulos et al., 2011). Among the As-bearing
minerals in travertine limestone samples are bacterio-morphic aggre-
gates of goethite containing up to 3.4 wt% As2O3, Fe-(hydro)oxides
and Mn\\Ba-(hydro)oxides (hollandite) containing up to 1.7 wt%
As2O3 and siderite with up to 3.0 wt% As2O3 (Kampouroglou and
Economou-Eliopoulos, 2016). Proposed mechanisms of transport and
reaction pathways of arsenic into groundwater include the oxidation
of pyrite containing arsenic (Das et al., 1996; Mandal et al., 1998), re-
duction of adsorbed arsenate to arsenite (BGS and DPHE, 2001; Bose
and Sharma, 2002), competitive anion exchange of adsorbed arsenic
(Acharyya et al., 1999; Appelo et al., 2002) and reductive dissolution
of iron oxides containing arsenic (Nickson et al., 2000; McArthur et al.,
2001; Swartz et al., 2004).
Arsenic is mobilized with pH values typically found in groundwater
(pH 6.5–8.5) and under both oxidizing and reducing conditions. For our
water samples, the pH ranges from 6.6 to 7.8 and Eh from −83 to 23 mV
(Table 5). The investigation of As(III) and As(V) sorption onto Fe-rich
soil concretions demonstrated that As(V) sorption onto iron oxides
has a strong dependence on pH. In addition, the negative Gibbs free en-
ergy (ΔG°) and positive entropy (ΔS°) values for arsenite and arsenate
sorption on Fe-rich soils are consistent with spontaneous reaction be-
tween the species and medium (Gupta, 1998; Partey, 2008). The meta-
stable oxyhydroxide ferrihydrite with respect to goethite is exclusively
nano particulate under typical surface conditions, and has high specific
surface area and significant reactivity toward the sorption of aqueous
contaminants AsO34 − and SO24 − (Gasparatos, 2013; Navrotsky et al.,
2008; Pinney and Morgan, 2013). Due to chemical similarity of phos-
phorus and arsenic, the influence of phosphorus [P(V)] on As(III) and
As(V) adsorption to Fe oxides is greatly influenced by pH and P(V) con-
centration (Jain and Loeppert, 2000).
Arsenic sorption on calcite has also been studied (Memon et al.,
2009). Arsenate sorption on calcite increases from pH 6 to 10, peaks be-
tween pH 10 and 12, and decreases above pH 12 (Goldberg and Glaubig,
1988). In natural systems, arsenic may be incorporated into the lattice
structure of calcite as arsenite under alkaline pH (Di Benedetto et al.,
2006), whilst the arsenite retention mechanisms on calcite changed
from adsorption to co-precipitation with increasing As(III) concentra-
tion (Roman-Ross et al., 2006). Arsenate anions exhibit a great affinity
for calcite surface sites at pH 8.3 and form inner-sphere complexes at
the calcite surface (Alexandratos et al., 2007). Romero et al. (2004) sug-
gested that arsenic retention in carbonate-rich aquifer material could be
partly due to adsorption onto calcite.
Elevated arsenic contents are also common in coal basins. Investiga-
tion in coal basins of Czech Republic (Slejkovec and Kanduc, 2005) indi-
cated that there are unexpected organic arsenic compounds in low-rank
coals. Organic acids such as humic acid and fulvic acid may compete
strongly with As(III) and As(V) for active adsorption sites on mineral
surfaces that influence As mobility. The competition for active binding
sites on mineral surfaces between organic acids and As compounds
may result in lowering As retention levels, especially under acidic con-
ditions (Wang and Mulligan, 2006). The presence of high As concentra-
tions (from 11 to 247 μg/l) in ground water has been reported in an area
between Kalamos, Markopoulo and Mavrosouvala due to lignite inter-
calations in marly formations, marly limestone, travertines and/or to
waste piles of lignite mining (Stamatis et al., 2011).
Arsenic and heavy metals in the majority of soil samples exceeded
the parametric values of Dutch limits (2009), and the background
values from the area of Holargos and western part of Kalamos-Varnavas
basin. In contrast, parametric values of the Greek Directive are not yet
available. There is a small portion of water samples (14%) at the south-
western and central part of the Mesogeia basin that present higher con-
centrations of As than the parametric values of the European
Community (Council Directive 93/83/EC). Given that groundwater con-
tamination by As is already considered a serious global environmental
problem and crops/vegetables grown on As-contaminated soils can be
the main source of arsenic for humans (Williams et al., 2005; Meharg
and Hartley-Whitaker, 2002; Pigna et al., 2010), the As level in ground-
water in Neogene basins of Attica combined with the As content in cer-
tain soil and plant samples may point to possible health risks to human
health.
5. Conclusions
The compilation of trace element data corresponding to soils, plants
and groundwater from the Neogene basins of Attica led to the following
conclusions:
• The groundwater samples of Kalamos, Varnavas and Kaisariani are
classified as a Ca\\HCO3 water type, while those from Artemida and
Koropi are a Ca\\Cl type.
• On the basis of the calculated saturation index, the ground water is sat-
urated in quartz and aragonite only in agricultural wells of Varnavas
area, and in calcite in springs and agricultural wells of Varnavas.
• The elevated Na, Cl, As, Se, Li and B concentrations in groundwater in
the Mesogeia basin suggest a contribution of sea water to this aquifer.
• Although acceptable limits for As and heavy metals for plants are lack-
ing, the presented As contents (dry weight) in plants from Neogene ba-
sins of Attica are often higher than normal or sufficient values.
• The bio-accumulation factor for As (Asplant / Assoil * 100) in Neogene ba-
sins of Attica showed a positive correlation with that for Fe, Cr, Mn, Pb
and Sb.
• The bio-accumulation factor for plants is relatively low (1.5–7.6%) for
As, Pb, Cr, Ba and Sb, which is characterized as toxic for their growth.
• Uptake of arsenic increases with higher arsenic concentration in the soil.
• The integrated water-soil-plant investigation of the arsenic contamina-
tion in the Neogene basins of Attica may indicate a potential human
health risk in similar Neogene lacustrine formations.
Acknowledgments
The University of Athens is greatly acknowledged for the financial
support of this work (Grant No. KE_11078). The Editor Dr. Markus
Egli, the Associated Editor Dr. Christina Siebe and reviewers are greatly
acknowledged for their constructive criticism and suggestions for im-
provement of our manuscript. The Elsevier Language Editing Services
are greatly acknowledged for editing the manuscript in British English
language.
Appendix A. Supplementary data
Supplementary data associated with this article can be found in the
online version, at doi: 10.1016/j.catena.2016.11.018. These data include
the Google map of the most important areas described in this article.
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