Catena 139 (2016) 137–166

Contents lists available at ScienceDirect

Catena

journal homepage: www.elsevier.com/locate/catena

Assessment of the environmental impact by As and heavy metals in

lacustrine travertine limestone and soil in Attica, Greece: Mapping of
potentially contaminated sites
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: Applying a geographical information system (GIS), geostatistical techniques and mapping software, a digitized
Received 22 July 2015 geological–geomorphological map and an assessment of the extent and intensity of the As and other harmful el-
Received in revised form 11 December 2015 ement contamination in travertine limestone and soil of the Neogene basins in Attica, Greece, are provided. The
Accepted 17 December 2015
presented results on the distribution of As and heavy elements in limestone and associated soil revealed (a) a sig-
Available online xxxx
nificant contamination in the uppermost travertine limestone that crops out in a significant part of Attica,
Keywords:
(b) spatial association between the distribution of As, Fe, Mn, Ni, Cr and Ba in limestone and associated soil.
Contamination The mineralogical, geochemical data and a combined approach of multivariate statistics and GIS suggest that
Arsenic major contamination sources are probably the sulfide and Fe–Mn mineralization in Attica, the basement and
Lacustrine–travertine the involved mylonitic ophiolitic blocks, and to a lesser extent human activities. The uppermost yellow–brown
Neogene-basins travertine limestone appear to be extended in many places throughout Attica, and may give rise to a significant
Greece impact on or risk to human health and ecosystems.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction composed by lacustrine and fluvial sediments, and the As contamination

The European Union has adopted maximum levels for metalloids
and heavy metals as regards food stuffs (Regulation 1881/2006/EC),
drinking water (Directive 98/83/EC), the use of sludge (Directive 86/
278/EC), air (Directive 2008/50/EC) and tail gas incineration (Directive
2000/76/EC). Arsenic (As)-contamination currently affecting millions
of people world-wide (Bhattacharyya et al., 2003), may be related to
anthropogenic sources, such as mining, pesticide application, wood
preservation and combustion of some coal deposits, or natural processes.
Arsenic by natural contamination occurs in alluvial and deltaic sediments,
in volcanic rocks, thermal springs or weathering products of such deposits
(Argyraki and Kelepertzis, 2014; Davis et al., 2009; Demetriadis, 2010;
Gamaletsos et al., 2013; Gasparatos, 2013; Kampouroglou, 2011;
Kampouroglou and Economou-Eliopoulos, 2013; Kelepertzis and
Argyraki, 2015; Komnitsas and Modis, 2006; Kontopoulos et al., 1996;
Korre et al., 2002; Liedekerke et al., 2014; Nordstrom, 2002; Smedley
and Kinniburgh, 2002; Welch et al., 2000; Xenidis et al., 2003). Recently,
elevated As contents in limestone (61–210 mg/kg As) were found
in a limestone quarry, that is exploited for a popular multicolour
building material, and in the associated soil (33 to 430 mg/kg As)
(Kampouroglou and Economou-Eliopoulos, 2013). This basin is
⁎ Corresponding author.
E-mail addresses: ekamp@geol.uoa.gr (E.E. Kampouroglou), econom@geol.uoa.gr
(M. Economou-Eliopoulos).
has been attributed to the transportation and deposition of the weathered
material from the neighboring Fe–Mn mineralization (Grammatiko), and
to a lesser extent to the marine transgressions during the evolution of the
basin.
The uppermost yellow–brown limestone of the Varnavas quarry
(Kampouroglou and Economou-Eliopoulos, 2013) appear to be extended
in other places throughout Attica, and may give rise to significant impacts
on or risks to human health and ecosystems. The present study focuses
on the investigation of: (a) the mineralogical and chemical composition,
and the mineral chemistry of the uppermost limestone formations and
associated soil, occupying almost the entirely basin of Athens (Fig. 1),
and (b) the analytical results for the metalloid As and associated metals
are presented in maps showing the contaminated and potentially
contaminated sites, in an attempt to evaluate the extent and intense
of the arsenic contamination in Attica.
1.1. Geotectonic outline—basin description
The study area of Attica (Fig. 2) is composed by the alpine basement,
both metamorphic and non metamorphic rocks, and post-alpine forma-
tions. In the eastern and southern parts of Attica the metamorphic section
of Attica-Cyclades zone occurs, which is transformed to high pressure and
low temperature conditions (Diamantopoulos, 2006; Ioakim et al.,
2005; Lozios, 1993; Mettos, 1992; Papanikolaou and Papanikolaou,
2007; Papanikolaou and Royden, 2007; Papanikolaou et al., 2004). The

http://dx.doi.org/10.1016/j.catena.2015.12.009
0341-8162/© 2015 Elsevier B.V. All rights reserved.
138 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166
Fig. 1. Topographical map showing the sampling locations in Attica (Greece).
non-metamorphic rocks of Sub-Pelagonian zone appear on the northern
and western Attica and consists of Permo-Triassic-Paleocenic sedimenta-
ry rocks and Jurassic ophiolites. The sub-Pelagonian is separated from
Attica-Cyclades with NNE–SSW Attica detachment fault, starting from
the southern Evoikos Gulf and ending in the Saronic Gulf (Papanikolaou
and Papanikolaou, 2007).
The Miocenic–Upper Pliocenic deposits (marine-coastal) in the
major basins of Attica are lacustrine formations—travertine limestone
and fluvio-lacustrine deposits (Fig. 2) accumulated all over the area
from Varnavas to Kalamos, and are characterized by an intense
synsedimentary tectonics, being bounded by major normal faults
while minor faults affect basin infillings (Ioakim et al., 2005). The
upper plate includes non-metamorphic rocks of Sub-Pelagonian zone
and the lower plate comprises metamorphic rocks of the western
extremity of the Attic-Cycladic high-P belt. The boundary between the
upper and lower plate has been interpreted as an Alpine thrust fault
(Clement, 1976; Xypolias et al., 2003). Recently, the kinematic re-
examination of this boundary demonstrated that it represents a Late
Miocene–Early Pliocene km-scale detachment fault that moved the
Sub-Pelagonian Zone, representing the upper plate, toward the
NNW and WSW/SSW and brought the HP metamorphic rocks of the
lower plate to the surface (Diamantopoulos, 2006; Papanikolaou and
Papanikolaou, 2007; Papanikolaou and Royden, 2007). Subsequently,
the lifting of Hymettus, by activation of Penteli detachment fault, results
the separation of the Athens basin from the Mesogeia basin, during
Pliocene (Mposkos, 2008). These basins display a varying thickness in
lithological types, reflecting synsedimentary tectonism and are strongly
influenced by palaeoclimatic and global sea level changes in the wider
Mediterranean environment during the last million years (Haq et al.,
1987; Ioakim et al., 2005; Rögl and Steininger, 1983). The sedimentary
infill of the Northern Attica basin consists of marls, marl limestone with
lignite intercalations and travertine, while upwards, clays, sandstones
and conglomerates are developed (Ioakim et al., 2005).
Triassic–Jurassic platform carbonates, comprising limestones and
dolomites were exposed throughout western Attica. Angular and
rounded blocks of serpentinised ophiolitic peridotites (Mesozoic age)
are common in a cataclastic zone (Marinos, 1983). There is a variation
in the orientation of brittle-deformed serpentinites, suggesting a multi-
stage formation of the shear bands. Thin skinned sheets of serpentinites
with carbonate blocks are tectonically often emplaced onto Triassic–
Jurassic limestones and dolomites (Diamantopoulos et al., 2009). Further-
more, the presence of the yellow–brown travertine limestone (Valero-
Garcés et al., 2001) of varying thickness (tens to a few meters) at the
top of the carbonate sequence and closely associated with dolomites
(Fig. 2) seems to be a common feature in all these basins, despite their
separation by the subsequent action of faults (Diamantopoulos et al.,
2009; Papanikolaou and Papanikolaou, 2007).
2. Materials and methods
2.1. Sampling and preparation
Representative rock samples, weighing about 3 kg/sample, of traver-
tine limestones (n = 55), collected from the Neogene basins (Upper Mio-
cene) of NE Attica (Kalamos, Varnavas, Drafi, Artemida) and Athens' basin
(Kaisariani, Papagou, Holargos), the travertine limestone occupying an
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166
Fig. 2. Simplified geological map of the study area in Attica (Greece).
area of approximately 30 km2, as well as Upper Cretaceous limestones
samples (n = 6), from the metamorphic basement of Athens basin
(n = 5) and Upper Miocenic marl limestone from Aghioi Anargiroi
(n = 6) were analyzed for major and trace elements (Table 1; Fig. 2).
Representative surface (0–10 cm) soil samples (n = 37) were
collected, during winter of 2012 and spring of 2013. The rock and soil
samples were stored in plastic bags for transportation and storage.
Each bag was mentioned by geographical coordinates. Also all the
sampling sites have been photographed.
Rock samples were crushed and after homogenization and splitting
they were pulverized using an agate mortar to less than 100 mesh.
This fraction was used for analysis. The precision of the method was
checked by means of these duplicate samples and was found to be
within international standards (Table 1).
Soils were dried at 50 °C, crumbled mechanically and then passed
through a sieve with a 2 mm mesh. Samples containing pebbles or
clods were first sieved on a 10 mm mesh and then a 5 mm mesh.
Then they passage through a 2 mm mesh, and grains finer than 2 mm
were pulverized and used for analysis. Furthermore, rock samples
were pulverized and were dried at 50 °C. The rock (Table 1) and soil
samples (Table 2) were analyzed by Inductively Coupled Plasma Mass
Spectroscopy (ICP/MS) after Aqua Regia Digestion at the ACME Analyt-
ical Laboratories in Canada. The detection limit of the analytical method,
the results of standard (STD) and black analysis (BLK) for all samples are
given at the end of each table.
Polished sections prepared from rock, after carbon coating were
examined by reflected light microscopy and scanning electron
microscope (SEM) and energy dispersive spectroscopy (EDS) analysis.
Microprobe analyses and SEM images were carried out at the University
139
of Athens, Department of Geology and Geoenvironment, using a JEOL
JSM 5600 scanning electron microscope, equipped with automated
energy dispersive analysis system ISIS 300 OXFORD, with the following
operating conditions: accelerating voltage 20 kV, beam current 0.5 nA,
time of measurement 50 s and beam diameter 1–2 μm. The spectra
were processed using the ZAF program (3 iterations).
The moisture content was determined by drying the samples at
105 °C and the organic matter content by igniting the oven-dried samples
(from moisture content determination) in a muffle furnace at 440 °C for
3 h (ASTM, 2000). The organic matter (Tables 1 and 2) content was
calculated as the difference between the initial and final sample weights
divided by the initial sample weight times 100%. All weights (in
duplicate) were corrected for moisture content prior to organic matter
content calculation (ASTM, 2000; Nelson and Sommers, 1996).
2.2. Statistical analysis and use of GIS
A combined approach of multivariate statistics and Geographical
Information System (ArcGIS v. 10.2) was applied for digitizing the
available and generated information of geology, geomorphology and
chemical analysis. All maps required geo-referencing to the area coordi-
nates according to the HGRS 87. Geological formations, faults and
thrusts were obtained by digitizing the scanned and geo-referenced
six geological maps (Chalkida, Eretria, Kifissia, Koropi, Rafina, Athens-
Piraieus) of Institute of Geology & Mineral Exploration (I.G.M.E.) of
scale 1:50.000.
Statistical software codes (Microsoft Excel 2007, MINITAB v. 15.0
and SPSS v. 17.0) and Esdat Environmental Database Management
Software. Soil Remediation Circular (2009) were used to study the
 140
Table 1
Major and trace element contents in rocks.

mg/kg (wt%)

E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Location Sample As Cu Pb Zn Ni Co Mn Sr Sb V Cr Ba Sc Fe Ca Mg Al Na K P organic matter

Kalamos KAL-R1 16 0.4 1.9 11 0.3 2.0 96 65 0.05 1 6 10 0.05 0.1 34 0.09 0.005 0.02 0.005 0.002 n.d.
KAL-R2 21 1.1 2.2 2 3.3 3.0 52 32 0.05 1 6 7 0.05 0.2 34 0.1 0.005 0.20 0.005 0.002 n.d.
KAL-R3 11 9.9 4.3 10 38 5.8 300 100 0.4 5 87 30 1.3 0.4 32 0.5 0.3 0.02 0.06 0.01 0.09
KAL-R4 23 4.5 1.5 3 13 3.5 870 98 0.5 4 20 91 0.3 0.2 33 0.3 0.09 0.01 0.02 0.005 0.18
KAL-R5 31 1.1 1.1 30 3.7 1.8 4 53 0.05 1 6 13 0.2 0.1 32 0.1 0.005 0.009 0.005 0.003 0.10
KAL-R6 33 1.9 4.2 40 7.4 2.3 20 45 0.2 1 9 12 0.3 0.2 35 0.2 0.05 0.01 0.01 0.004 0.12
KAL-R7 29 0.8 0.7 7 2.3 2.1 23 48 0.05 1 4 11 0.1 0.2 34 0.1 0.01 0.009 0.005 0.002 0.05
KAL-R8 32 1.0 0.8 13 3.9 1.8 6 87 0.1 1 17 11 0.3 0.2 34 0.1 0.02 0.009 0.005 0.004 0.06
KAL-R9 29 0.7 0.6 19 4.0 2.6 7 39 0.05 1 6 7 0.3 0.1 35 0.07 0.01 0.01 0.005 0.005 0.25
KAL-R10 36 1.6 5.7 39 3.1 1.7 20 52 0.4 1 6 13 0.2 0.1 35 0.1 0.02 0.009 0.005 0.004 0.09
KAL-R11 32 0.7 0.7 3 4.2 3.1 20 51 0.05 1 3 11 0.05 0.1 34 0.09 0.01 0.01 0.005 0.003 0.08
KAL-R12 32 0.6 1.8 12 2.9 3.2 3 36 0.05 1 5 8 0.1 0.1 34 0.07 0.01 0.01 0.005 0.004 0.17
KAL-R13 63 2.4 0.5 31 7.6 2.6 58 170 0.1 1 7 34 0.05 0.1 34 0.2 0.01 0.02 0.005 0.003 0.06
KAL-R14 9 0.6 1.0 0.5 2.0 2.8 130 88 0.6 1 6 22 0.05 0.1 35 0.09 0.01 0.008 0.005 0.002 0.12
KAL-R15 12 0.5 7.1 2 7.4 1.6 82 33 0.3 1 7 12 0.05 0.1 29 0.06 0.005 0.008 0.005 0.002 0.18
KAL-R16 24 4.6 2.5 6 22 4.7 120 130 2.3 3 20 33 0.5 0.3 33 0.3 0.1 0.007 0.03 0.009 0.20
KAL-R17 28 4.8 71 7 18 5.7 240 140 1.8 3 16 20 0.4 0.2 34 0.3 0.1 0.006 0.03 0.008 0.18
KAL-R18 48 4.0 4.8 9 25 4.4 170 82 0.7 5 22 18 0.5 0.4 33 0.3 0.1 0.007 0.03 0.006 0.15
KAL-R19 22 3.2 1.5 5 13 3.4 43 85 0.9 2 13 10 0.3 0.2 34 0.3 0.09 0.007 0.02 0.003 0.11
KAL-R20 29 2.7 34 3 7.8 3.2 96 49 1.5 1 7 22 0.1 0.1 35 0.1 0.03 0.01 0.005 0.004 0.38
KAL-R21 38 0.7 2.6 19 4.3 2.2 11 78 0.05 1 2 12 0.05 0.1 35 0.09 0.005 0.01 0.005 0.002 0.34
KAL-R22 32 0.8 1.9 15 3.0 2.1 17 93 0.05 1 0.5 15 0.2 0.1 36 0.09 0.005 0.009 0.005 0.002 0.44
KAL_R23 48 5 12 72 2 1 3 110 3 1 3 19 0.5 0.01 39 0.2 0.01 0.01 0.01 0.001 0.06
KAL_R24 800 36 21 75 410 34 470 27 14 50 970 38 5 2.2 34 0.2 0.5 0.01 0.09 0.01 0.58
KAL_R25 5 1 28 1 1 1 37 46 3 1 7 9 0.5 0.01 37 0.1 0.08 0.01 0.01 0.001 0.07
KAL_R26 28 3 35 1 14 2 1100 97 3 4 24 47 0.5 0.2 36 0.2 0.2 0.01 0.05 0.01 0.20
KAL_R27 23 1 15 14 1 1 3 54 3 1 4 10 0.5 0.01 38 0.1 0.04 0.01 0.01 0.01 0.10
Average 57 3.5 10 17 23 3.9 150 74 1.3 3.5 48 20 0.5 0.2 34 0.2 0.1 0.02 0.02 0.005 0.2
Varnavas VAR-R4 56 16 3 77 25 19 210 69 6 32 37 71 5 1.2 30 0.3 2.4 0.2 0.6 0.03 0.24
VAR-R5 250 7 160 220 24 11 560 63 18 10 9 72 0.5 1.1 36 0.1 0.1 0.01 0.02 0.01 0.30
VAR-R6 5 2 3 58 10 4 76 52 3 8 27 38 1 0.2 36 0.1 0.5 0.03 0.1 0.01 0.05
VAR-R7 62 4 67 110 18 3 200 57 3 10 26 75 1 0.4 35 0.1 0.4 0.01 0.09 0.01 0.19
Average 93 7.3 58 120 19 9.3 260 60 7.3 15 25 64 1.9 0.7 34 0.2 0.9 0.1 0.2 0.02 0.2
Artemida AR-R1 71 1 3 12 17 5 230 120 3 4 18 18 0.5 0.2 38 0.2 0.2 0.01 0.02 0.01 0.11
AR-R2 48 1 3 12 14 1 57 310 3 1 14 38 0.5 0.05 36 0.2 0.08 0.01 0.02 0.01 0.13
AR-R3 59 1 20 20 7 1 160 240 3 3 12 32 0.5 0.1 38 0.2 0.2 0.01 0.02 0.004 0.14
AR-R4 63 1 7 1 1 1 260 120 3 3 6 35 0.5 0.07 37 0.1 0.02 0.01 0.01 0.004 0.08
AR-R5 6 1 6 1 4 1 320 120 3 1 2 16 0.5 0.01 38 0.04 0.03 0.01 0.01 0.002 0.11
AR-R6 51 1 12 49 15 3 140 48 3 4 21 17 0.5 0.2 37 0.1 0.1 0.01 0.02 0.004 0.07
 AR-R7 61 1 10 29 29 3 310 74 3 4 18 27 0.5 0.3 36 0.1 0.2 0.01 0.04 0.01 0.05
AR-R8 770 7 7 62 44 18 1200 59 3 12 21 89 0.5 1.8 37 0.1 0.2 0.01 0.04 0.01 0.21
AR-R9 3 1 3 7 3 3 22 73 3 1 4 6 0.5 0.01 39 0.1 0.03 0.01 0.01 0.003 0.02
AR-R10 10 1 19 3 2 3 25 37 3 1 4 7 0.5 0.04 37 0.1 0.03 0.01 0.01 0.001 0.07
Average 114 1.6 8.9 20 14 3.9 270 120 2.5 3.4 12 29 0.5 0.3 37 0.1 0.1 0.01 0.02 0.004 0.1

mg/kg (wt%)

Location Sample As Cu Pb Zn Ni Co Mn Sr Sb V Cr Ba Sc Fe Ca Mg Al Na K P organic matter

Drafi DR-R1 39 1 24 49 1 1 330 270 3 1 3 34 0.5 0.3 36 0.2 0.1 0.01 0.01 0.01 0.16
DR-R2 30 1 25 61 3 3 29 370 3 1 3 29 0.5 0.02 37 0.2 0.04 0.01 0.01 0.002 0.09
DR-R3 22 1 16 31 11 1 120 59 3 1 7 8 0.5 0.06 38 0.1 0.04 0.01 0.01 0.002 0.07
DR-R4 53 1 3 6 5 1 94 100 3 1 9 11 0.5 0.2 37 0.1 0.01 0.01 0.01 0.002 0.06
DR-R5 180 1 3 10 15 1 260 280 7 4 9 34 0.5 0.4 35 0.2 0.09 0.01 0.02 0.003 0.15
DR-R6 610 3 3 19 35 7 160 330 5 16 27 72 0.5 1.2 34 0.2 0.2 0.03 0.05 0.01 0.84
DR-R7 3 1 3 3 1 1 110 62 3 1 3 6 0.5 0.01 37 0.1 0.01 0.01 0.01 0.002 0.02
Average 130 1.3 11 26 10 2.1 160 210 3.5 3.6 8.7 28 0.5 0.3 36 0.1 0.1 0.01 0.01 0.003 0.2
Papagou AG.I.TH.P 110 13 84 110 530 23 1800 75 14 12 12 130 1.8 2.6 28 2.6 0.11 0.013 0.03 0.019 0.65

E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

AG.I.S.P. 14 22 9.6 38 92 17 760 76 0.1 8 10 48 2.5 2.1 17 0.2 0.21 0.016 0.06 0.022 0.77
Average 62 18 47 74 311 20 1300 76 7.0 10 11 89 2.2 2.3 22 1.4 0.2 0.01 0.05 0.02 0.7
Holargos XOL.GIP 7.5 72 13 37 35 66 510 290 0.2 30 55 21 5.9 2.2 18 0.1 0.31 0.009 0.08 0.017 0.71
XOL.GIP1 13 57 4.2 98 86 22 530 160 0.5 61 120 27 9.6 4.4 12 0.3 0.7 0.012 0.10 0.020 1.38
XOL.GIP2 8.3 2.2 21 260 260 12 170 6 1.2 6 10 7 0.5 0.8 31 0.3 0.02 0.006 0.005 0.031 0.17
XOL.GIP3 35 0.6 6.6 57 43 2.6 34 74 1.3 1 3 3 0.1 0.10 26 7.4 0.005 0.014 0.005 0.010 n.d.
XOL.NAV 8.2 1.0 35 130 290 16 390 150 1.5 1 13 15 0.4 0.9 28 3.4 0.03 0.012 0.005 0.008 0.12
Average 14 27 16 120 143 24 330 140 0.9 20 40 15 3.3 1.7 23 2.3 0.2 0.01 0.04 0.02 0.6
Kaisariani PYL1 13 22 4.4 38 230 15 470 290 0.05 22 430 84 5.4 1.7 25 1.6 0.9 0.013 0.04 0.020 0.90
PYLI3 98 38 16 88 75 17 2500 95 0.2 17 14 180 3.1 4.6 18 0.3 0.2 0.08 0.07 0.031 n.d.
ELKE2.PAR 230 6.8 78 250 970 45 340 20 3.7 23 380 9 4.8 1.7 28 0.3 0.10 0.010 0.02 0.004 0.41
AG.I.CAMP 17 1.4 20 78 1100 52 560 640 0.7 15 170 4 1.7 2.5 18 9.3 0.02 0.016 0.005 0.003 0.23
KAIS-R1 21 1.5 45 150 78 4.2 69 80 0.4 1 6 8 0.1 0.3 29 1.8 0.02 0.009 0.005 0.02 0.31
KAIS-R2 1.5 0.4 2.0 3 4.4 1.5 14 240 0.05 1 4 3 0.4 0.1 36 0.3 0.02 0.007 0.005 0.06 0.14
Average 63 12 27 100 410 22 660 230 0.9 13 170 48 2.6 1.8 26 2.3 0.2 0.02 0.02 0.02 0.4
Ag. Anargiri (marls) TR-R1 6 31 3 68 230 27 530 160 3 87 280 210 12 2.9 9.9 2.5 5.4 0.6 1.3 0.03 0.71
TR-R2 3 18 3 33 230 17 560 190 3 45 220 130 7 1.7 27 1.4 2.6 0.06 0.7 0.01 0.88
TR-R3 3 9 19 19 100 8 830 240 3 33 120 110 5 1.1 29 1.2 2.0 0.08 0.6 0.02 0.41
Average 3.7 19 8.0 40 190 17 640 200 2.5 55 210 150 8.0 1.9 22 1.7 3.3 0.2 0.8 0.02 0.7
Ag. Paraskevi AG.P-R1 9 1.3 27 2 9.0 3.1 94 360 0.4 1 3 11 0.2 0.2 35 0.3 0.005 0.02 0.005 0.07 0.16
Metamorphic basement P.RED 18 45 19 58 82 19 1500 150 0.2 10 29 140 2.2 1.8 9.6 0.3 0.2 0.07 0.07 0.033 n.d.
PYLI.SY 270 790 630 9100 66 24 10,100 21 40 1 11 270 1.0 16 22 0.3 0.05 0.010 0.03 0.010 n.d.
KAIS.RED 28 120 41 120 280 68 4700 89 6.3 360 150 95 6.5 14 8 0.1 0.4 0.008 0.14 0.028 n.d.
Average 110 318 230 3100 140 37 5400 87 15 120 63 170 3 11 13 0.2 0.2 0.03 0.1 0.02 n.d.
Jurassic limestone LIME1 4.8 0.2 0.5 3 1.1 1.4 6 83 0.05 1 1 1 0.3 0.2 33 0.2 0.005 0.007 0.005 0.009 n.d.
Triassic limestone LIME2 0.3 0.3 1.2 4 0.05 5.9 9 51 0.05 8 2 2 0.4 0.09 21 12 0.005 0.012 0.005 0.005 n.d.
Detection limit 0.5 0.1 0.1 1 0.1 0.1 1 1 0.1 2 1 1 0.1 0.01 0.01 0.01 0.01 0.001 0.01 0.001
Reference materials
STD OREAS45EA 9.1 690 14 29 380 53 400 2 0.1 300 990 150 79 22 0.06 0.09 3.2 0.02 0.05 0.0
STD DS9 27 110 130 310 43 8 590 60 4.5 40 130 340 2.5 2.4 0.7 0.6 1.0 0.1 0.4 0.1
Calcareous rocks a 1–2.5 2–10 17–63 10–25 5–20 0.1–3 200–1000 460–600 0.15–0.3 10–45 5–16 50–200 0.5–5 0.4–1.0 – – 0.4–1.3 – – –
a
After Kabata-Pendias and Pendias, 2001.

141
 142
Table 2
Major and trace element contents in soils.

mg/kg (wt%)

Location Sample As Cu Pb Zn Ni Co Mn Cr Ba Th Sr Cd Sb V La Sc Fe Ca Mg Ti Al Na K P organic matter

Kalamos KAL-S1 310 59 36 370 280 31 1100 310 300 7 43 0.5 2.5 110 30 15 4.8 2.3 0.8 0.4 7.9 0.3 1.5 0.07 5.6
KAL-S2 1200 77 33 230 660 64 1200 1400 190 5 44 0.2 21 120 20 14 5.6 15 1.1 0.2 5.1 0.3 1.1 0.05 2.8
KAL-S3 110 30 98 170 160 29 1400 190 350 9 63 0.7 2.5 98 40 14 4.1 1.2 0.8 0.4 7 0.4 1.6 0.04 10.5
KAL-S4 63 20 41 90 90 15 570 130 240 6 65 0.9 2.5 83 30 11 3.2 16 0.7 0.3 5.7 0.2 1 0.05 4.6
KAL-S5 170 40 66 120 210 30 1100 330 410 11 65 0.2 14 160 41 19 5.6 1 0.8 0.5 9.3 0.3 2.1 0.04 4
KAL-S6 140 34 14 48 200 26 450 230 160 4 70 0.2 12 64 14 8 2.1 21 1 0.2 3.5 0.2 0.9 0.02 1.6

E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

KAL-S7 54 68 48 430 160 27 1300 240 320 10 72 1.4 2.5 85 39 14 3.9 4.1 0.7 0.4 6.6 0.3 1.6 1.3 7.3
KAL-S8 110 68 48 180 260 32 1100 350 300 6 33 0.6 2.5 110 27 14 4.4 0.7 1.4 0.3 6.3 0.7 1.7 0.05 5.8
Average 270 50 48 205 250 32 1030 400 284 7.3 57 0.6 7.4 104 30 14 4.2 7.7 0.9 0.3 6.4 0.3 1.4 0.2 5.3
Varnavas VAR-S10 120 24 140 170 58 17 520 82 150 4 73 0.5 14 64 21 9 2.6 13 0.4 0.2 4.7 0.3 1 0.04 5
VAR-S11 81 34 69 130 120 28 720 160 280 9 72 0.2 6 130 38 17 4.6 0.6 0.6 0.3 7.8 0.4 1.8 0.02 4.2
VAR-S12 280 26 220 500 130 29 1200 170 340 10 67 0.5 15 110 35 15 4.4 2.6 0.6 0.3 7.1 0.4 1.6 0.04 7.1
Average 160 28 140 270 100 25 810 140 260 7.7 71 0.4 12 101 31 14 3.9 5.4 0.5 0.3 6.5 0.4 1.5 0.0 5.4
Artemida AR-S1 130 26 92 76 100 19 1100 150 220 3 99 0.5 2.5 60 21 8 2.5 12 0.8 0.3 4.2 0.3 1 0.08 9
AR-S2 99 22 71 89 98 18 670 140 260 6 85 0.4 2.5 74 28 10 2.9 11 0.8 0.3 5.1 0.3 1.5 0.04 6.2
AR-S3 270 31 240 130 120 20 930 160 230 1 69 0.5 7 71 21 8 3 4.2 0.7 0.3 4.2 0.3 1.1 0.05 19.9
AR-S4 37 64 26 62 410 33 620 640 130 1 90 0.2 2.5 72 13 10 3 11 2.6 0.2 3.7 0.6 0.8 0.07 3.4
Average 130 36 110 89 180 23 830 270 210 2.8 86 0.4 3.6 69 21 9 2.9 9.6 1.2 0.3 4.3 0.4 1.1 0.1 9.6
Drafi DR-S1 310 20 43 72 380 35 700 290 170 4 81 0.2 2.5 69 16 10 3.2 13 0.7 0.2 3.9 0.2 1 0.02 4.9
DR-S2 64 22 38 63 130 22 750 130 240 6 140 0.2 2.5 69 18 9 2.8 11 0.7 0.2 4.9 0.4 1.3 0.03 4.5
Average 130 21 51 68 210 29 680 200 205 5.0 120 0.2 2.5 69 17 10 3.0 12 0.7 0.2 4.4 0.3 1.2 0.03 4.7
Ag. Anargiri TR-S1 16 27 73 74 130 22 580 190 160 2 130 0.2 2.5 55 18 7 2.3 9 1.4 0.2 3.8 0.7 0.8 0.05 4.5
Kaisariani ΕLKΕ 140 5.3 33 120 320 23 290 110 6 0.05 15 1.2 1.6 15 0.5 0.3 0.8 34 0.2 0.00 0.03 0.001 0.01 0.04 1.3
ELKE11K 150 5.8 35 130 330 25 300 120 7 0.05 17 1.5 1.8 18 0.5 0.4 0.9 36 0.3 0.00 0.04 0.001 0.01 0.05 1.5
Average 145 5.6 34 125 330 24 300 120 6.5 0.1 16 1.4 1.7 17 0.5 0.4 0.9 35 0.2 0.001 0.04 0.001 0.01 0.04 1.4
Detection limit 0.5 0.1 0.1 1 0.1 0.1 1 1 1 0.1 1 0.1 20 0.1 2 1 0.1 0.01 0.01 0.01 0.001 0.01 0.001 0.01 0.001
Reference materials
STD DS8 26 105 124 308 36 7.2 583 112 271 6.2 62 2.2 5 40 13 1.9 2.3 0.7 0.6 0.1 0.8 0.08 0.4 0.07
STD OREAS45PA 4.5 555 18 110 267 100 996 724 168 6.4 13 b0.1 0.2 194 15 38 15 0.2 0.1 0.1 3.1 0.01 0.07 0.03
Reference valuesa – 50 – 140 50 – 300 150 – 300 30 – 75 – – – – – – – – – – – – – – – – – – – –
Reference valuesb 76 190 530 720 100 190 – 180 8 – – 13 22 – – – – – – – – – – – –
Reference valuesc 12 63 70 200 50 40 – 64 750 – – 1.4 20 130 – – – – – – – – – – –
Reference valuesd 12 63 140 200 50 50 – 64 500 – – 10 20 130 – – – – – – – – – – –
Reference valuese 12 91 600 360 50 300 – 87 2000 – – 22 40 130 – – – – – – – – – – –
Global medianf – 30 35 90 50 8 1000 70 – – – 0.35 – – – – 4 1.5 0.5 – – – 1.4 0.08 –
a
Reference values according to Gazette 641B/1991.
b
Reference values according to Dutch limits (2009).
c
Reference values for agricultural land according to Canadian Council of Ministers of the Environment (2006).
d
Reference values for residential/parkland area according to Canadian Council of Ministers of the Environment (2006).
e
Reference values for industrial area according to Canadian Council of Ministers of the Environment (2006).
f
Global median according to Reimann et al. (2014).
Table 3
Correlation matrix of major and trace elements in soils.

E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

As Cu Pb Zn Ni Co Mn Cr Ba Th Sr Cd Sb V La Sc Fe Ca P Mg Ti Al Na K Organic matter

As 1.00
Cu 0.06 1.00
Pb 0.21 −0.29 1.00
Zn 0.50 0.17 0.55 1.00
Ni 0.04 0.76 −0.25 −0.05 1.00
Co −0.09 0.68 −0.31 −0.12 0.84 1.00
Mn 0.36 0.52 0.30 0.50 0.38 0.21 1.00
Cr −0.06 0.79 −0.23 −0.09 0.96 0.83 0.42 1.00
Ba −0.06 0.42 0.32 0.18 0.61 0.45 0.56 0.65 1.00
Th 0.27 0.25 −0.14 0.30 0.16 0.21 0.25 0.16 0.22 1.00
Sr −0.53 0.01 −0.01 −0.43 0.37 0.28 −0.07 0.42 0.50 −0.22 1.00
Cd 0.03 −0.10 0.42 0.54 −0.38 −0.38 0.28 −0.33 0.09 0.04 −0.35 1.00
Sb 0.67 0.01 0.40 0.43 0.02 −0.06 0.14 −0.02 0.14 0.18 −0.26 −0.08 1.00
V −0.09 0.70 −0.04 0.00 0.82 0.73 0.46 0.89 0.79 0.40 0.41 −0.18 0.02 1.00
La −0.01 0.49 0.03 0.13 0.50 0.50 0.27 0.55 0.56 0.72 0.15 0.00 0.06 0.78 1.00
Sc −0.09 0.67 −0.11 −0.04 0.80 0.72 0.36 0.87 0.72 0.48 0.43 −0.22 −0.01 0.97 0.85 1.00
Fe 0.30 0.73 −0.08 0.28 0.64 0.59 0.57 0.67 0.46 0.68 −0.09 −0.12 0.16 0.78 0.79 0.79 1.00
Ca 0.06 −0.54 −0.17 −0.22 −0.44 −0.48 −0.48 −0.47 −0.62 −0.49 −0.03 −0.02 −0.01 −0.71 −0.73 −0.68 −0.71 1.00
P −0.30 0.59 −0.11 0.20 0.29 0.31 0.33 0.38 0.27 0.18 0.14 0.41 −0.33 0.38 0.42 0.40 0.34 −0.24 1.00
Mg −0.42 0.68 −0.30 −0.34 0.83 0.76 0.19 0.90 0.55 0.05 0.55 −0.34 −0.30 0.82 0.54 0.82 0.50 −0.46 0.43 1.00
Ti −0.18 0.57 0.05 −0.08 0.79 0.62 0.42 0.86 0.88 0.20 0.64 −0.15 −0.02 0.93 0.66 0.91 0.57 −0.57 0.36 0.82 1.00
Al −0.20 0.61 −0.05 −0.08 0.77 0.71 0.30 0.84 0.76 0.42 0.51 −0.18 −0.06 0.96 0.84 0.98 0.71 −0.67 0.41 0.84 0.93 1.00
Na −0.29 0.54 0.01 −0.19 0.77 0.66 0.27 0.83 0.82 0.13 0.69 −0.22 −0.06 0.88 0.64 0.88 0.48 −0.55 0.33 0.85 0.96 0.92 1.00
K −0.17 0.58 −0.04 −0.10 0.76 0.70 0.26 0.81 0.74 0.43 0.49 −0.20 −0.02 0.93 0.86 0.97 0.68 −0.66 0.40 0.82 0.91 0.99 0.92 1.00
organic matter −0.29 0.33 −0.09 −0.18 0.47 0.54 −0.12 0.52 0.27 0.31 0.34 −0.15 −0.27 0.60 0.75 0.71 0.47 −0.42 0.40 0.66 0.54 0.75 0.60 0.77 1.00

143
144 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

geochemical data distribution and the relationships between soils and
travertine limestone in the Neogene basins of Attica. For the correlation
analysis for soils were used relationships greater than 0.50 and were
plotted diagrams for selected elements using MS Excel.
The geochemical data set was processed by the R-mode factor
analysis, applying the Varimax-raw rotational technique with Kaiser
Normalization, to separate and identify the distributions associated
with individual components. All data were logarithmically transformed
prior to factor analysis. The correct number of factors was selected by
using a combination of the common criteria. For the determination of
inter-element relationships were selected factor loadings bigger than
0.50. Negative factor scores indicate areas that are unaffected by either
natural or anthropogenic processes, and positive scores indicate the
areas that are most affected by chemical processes.
The result of the Hot Spot Analysis (Spatial Statistics Tool for
ArcMap) is a map where every feature in the dataset is symbolized
based on whether it is part of a statistically significant hot spot, a statis-
tically significant cold spot, or is not part of any statistically significant
cluster. Statistical significance is based on p-values and z-scores that
are calculated when Hot Spot Analysis is run. Inverse Distance
Weighting (IDW) interpolation method with a power of 2 was used as
a geostatistical deterministic method that can be a good way to take a
look at an interpolated surface and the spatial distribution maps using
the Geostatistical Analyst tool for ArcMap (ArcGIS) were created. The
element contents were projected on the digital map using graduated
size symbols.
3. Results
3.1. Geochemistry of rocks and soils
The travertine limestone samples in Neogene basins of Attica
(Table 1) show high average contents in As (70), Cu (19), Zn (169), Ni
(79), Co (10), Sb (3), and Cr (50) (all in mg/kg), while average values
of Sr (118 mg/kg), Ba (45 mg/kg) and Al (0.29 wt%) are lower as com-
pared to the range of world values in calcareous rocks (Kabata-Pendias
and Pendias, 2001; Table 1). The highest average contents of As were
recorded in Mesogeia basin, in particular the Drafi area (130 mg/kg).
The average Cu, Pb, Zn, Sb, V, Mn, Ba, Fe and P contents in travertine
limestone were higher in the Varnavas area compared to the Kalamos
one, while the highest contents for these elements were recorded in the
areas of Papagou, Holargos and Kaisariani, as well as in rocks of the
basement (Table 1). The Cr content ranging from 9 mg/kg in the Drafi
area to 210 mg/kg in the Aghioi Agargiri area is often accompanied by
elevated Ni, Co and Fe contents (Table 1). Samples with the highest As
contents show elevated content of organic matter (Table 1). Strontium
content is relatively low in Triassic and Jurassic limestones and dolomites
(tens of mg/kg) while travertine limestone throughout the Attica basins
exhibits a wide variation from tens to a few hundreds mg/kg, with the
highest contents recorded in the Drafi area (Table 1).
The average contents of As, Ni, Cr and Ba in soils are higher than the
parametric values of Dutch limits (2009) (Table 2). The references
values for agricultural land, for residential/parkland and industrial
area according to Canadian Council of Ministers of the Environ-
ment (CCME, 2006) are lower than the average contents of As,
Ni, and Cr in soils. There is a 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. In general, the Cu, Pb, Zn, Ni, Co, Cr, Cd, Ca, P and Mg contents
in the studied soil samples of Attica are higher than global median in
soils (Kabata-Pendias and Pendias, 2001). There is a positive correlation
between As and Zn, Sb in soils (Table 3).
The plots of As versus Ni, Fe, Zn and Sb contents for soils, rocks and
ores (Table 4) (Fig. 3a–d) show an increasing trend from travertine
limestones to soils and furthermore to ore samples from the
Grammatiko (Kampouroglou and Economou-Eliopoulos, 2013) and
Lavrion (Economou-Eliopoulos, unpublished data for ores from Plaka
and Kamariza) mines, and an enrichment in soils compared to the asso-
ciated limestone.
The organic matter in rock samples ranges from 0.02 to 1.38 wt%
(average 0.25) and in soils from 1.3 to 19.9 wt% (average 4.0). The
highest average value of organic matter in rock samples was recorded
in the Athens basin.
3.2. Mineral composition
The dominant minerals in travertine limestone are calcite, which is
Mg-free, while in the areas of Holargos, Papagou and Kaisariani, where
travertine limestone appears along discontinuities of strongly fractured
gray dolomite limestone (Fig. 4a–f, e), dolomite occurs as a residue
mineral (Fig. 4c–f; Table 5). Quartz, siderite goethite, hematite,
Mn–Fe–Ni–Co (hydro)oxides, apatite (fluor-hydroxylapatite), rutile
and rare earth element (REE)-minerals occur in a varying proportion

Table 4
Major and trace element content of ores from the Grammatiko and Lavrio mines.

mg/kg wt%

Sample As Cu Pb Zn Ni Co Mn Sb Cr Ba Fe Ca Mg Al

Fe–Mn ore deposit Grammatiko mine

G.ER.108C 920 1600 2900 3300 12 15 N10,000 1300 1 880 26 13 0.08 0.01
G.ER.101A 58 1.2 21 150 1.6 2.4 N10,000 15 0.05 36 40 5.4 0.1 0.01
G.ER.108A 1600 N10,000 7200 900 2.6 0.9 1700 400 0.05 9 5.3 20 0.04 0.20
Average 859 3867 3374 1450 5 6 7233 572 0.4 308 24 13 0.07 0.06

Ore deposit Lavrio mines

Plaka1 970 1300 N10,000 N10,000 8 23 N10,000 52 1 15 15 13 2.4 0.02
Plaka2 N10,000 570 N10,000 N10,000 18 13 N10,000 6100 1 280 15 8.4 1 0.4
Plaka3 1800 920 N10,000 N10,000 22 20 N10,000 4500 1 38 15 6.5 0.8 0.02
Kamariza1 2200 700 N10,000 N10,000 14 17 1800 240 2 75 7.8 14 0.4 0.04
Kamariza2 N10,000 N10,000 N10,000 N10,000 115 69 1780 1400 1 1 15 7.9 0.05 0.01
Kamariza3 960 2800 N10,000 2040 12 12 2800 1560 4 1 1.8 15 0.2 0.01
Kamariza4 930 3500 N10,000 N10,000 10 14 1430 370 1 1 9.3 8.7 0.1 0.01
Kamariza5 N10,000 1600 N10,000 N10,000 22 10 4700 400 1 1 6.7 15 0.6 0.01
Kamariza6 N10,000 N10,000 700 370 15 51 2 360 1 1 15 0.6 0.01 0.01
Kamariza7 2830 880 N10,000 5500 4 7 14 4300 1 1 0.9 0.4 0.01 0.01
Kamariza8 N10,000 3000 N10,000 1600 12 10 160 2300 2 1 5.2 0.4 0.01 0.02
Kamariza9 610 600 N10,000 N10,000 7 9 9600 8700 1 1 12 2.4 0.7 0.02
Average 5025 2989 9225 7459 22 21 4357 2524 1.4 35 9.9 7.7 0.5 0.05
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 145

Fig. 3. Variation of the As and metal content in soils and rocks from the Attica basins and ores from the Grammatiko and Lavrion mines (3a): Plot of the As versus Ni content; (3b): As vs. Fe
content; (3c): As vs. Zn content and (3d): As vs. Sb content. Data from Tables 1 and 2; Kampouroglou and Economou-Eliopoulos (2013).

and chemical composition in the studied areas of Attica (Tables 5–8).
Siderite (Fig. 6a,b; Table 5) with significant contents of Cr, Ni and As
(up to 3.0 wt% As2O3), chromite (Fe–chromite), muscovite, chlorite,
sphene, zircon, barite, galena and sphalerite are present in lesser
amounts in the Kalamos area.
In the Varnavas area (Fig. 6) siderite shows significant Cr, P
and Ti contents, while bacteriomorphic aggregates of goethite
(Fig. 6e,f) contain As (up to 3.4 wt% As 2 O 3 ), Fe–(hydro)oxides
and Mn–Ba–(hydro)oxides (hollandite) contain As (up to 1.7 wt%
As 2 O 3 ), REE-minerals are phosphate minerals and contain As
(up to 2.5 wt% As 2 O 3 ), and apatite is fluorapatite (Tables 5, 6).
Muscovite, sphene, zircon, enargite and pyrite are present in smaller
amounts.
In the Holargos area siderite and goethite contain significant
amounts of As (up to 8.7 wt% As2O3 in goethite), Ni and Zn (Tables 5,
6). In the Papagou area the spinel (Fe–chromite), tennantite, chalcopy-
rite, pyrrhotite and barite were identified. In the Kaisariani area siderite
contains significant amounts of Mn, Mg, Zn, Cr, As and Ni (Table 5), Mn–
Fe (hydro)oxides contain Pb, Zn, Mg, Co and Ni, goethite contains Zn,
Mn and Cr, and chromite contains Zn, Fe and Mg (Tables 6, 7). Minor
minerals are rutile, zircon and sphene. Apatite is fluorapatite in Athens
basin.
3.3. Elemental spatial distribution patterns
The maps of Hot Spot Analysis showing both the surface and the true
out coming results at the same time is a great way to present both the
statistical results and the more approachable visualization. Hot Spot
Analysis in rocks (Fig. 7a–f) is presented. Hot spots cause spatial trends
in the mean value of the random field and a non-Gaussian data distribu-
tion (Komnitsas and Modis, 2009). Thus, the Athens basin is a hot spot
area for all elements (Fe, Cr, Ni, Mn, Ba) except As, which appears in
Mesogeia basin and the east part of Kalamos–Varnavas basin. The
south part of Kalamos–Varnavas basin is also a hot spot area for Ba.
146 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Fig. 4. Photos of strongly fragmented gray limestone filled by brown travertine limestone (4a–b) from the Holargos area. Representative backscattered SEM images from the Holargos area
(Athens basin) showing dark grey dolomite and light grey calcite (4c–e), siderite (4c–e), angular fragments of chromite (4c), apatite (4d) and goethite (4f). Abbreviations: Dol = dolomite;
Cal = calcite; Sd = siderite; Chr = chromite; Ap = apatite; Gth = goethite. Mineral compositions are given in Tables 6–9.

Arsenic and iron in soils (Fig. 8a–f) show a hot spot area in northern
part of the map in Kalamos–Varnavas basin and the faults of Zefiri-Ag.
Paraskevi and Dionysos divide the area from Athens basin in southwest
and from Mesogeia basin in southeast. Hot spot areas of Cr, Ni and Ba
are shown mainly in the Mesogeia basin and to a lesser extent in the
Athens basin. The hot spot area of Ba exhibits an arc from Kalamos–
Varnavas basin and furthermore to southeast part of Mesogeia basin
(Artemida).
Geochemical maps of predictable spatial distribution of selected
major and trace elements in rocks are presented (Fig. 9a–f). These
maps are in a good agreement with the hypothesis of the presence of
hot spots. Arsenic shows higher values in east part of the map in areas
of Kalamos, Varnavas and Artemida. Iron, Mn, and Ni show high
contents in the SW part of the map in the basin of Athens and an inter-
mediate content in the areas of Kalamos, Varnavas, Drafi and Artemida.
Chromium has high values both in NE Attica and Athens basin and
smaller in Drafi and Artemida. Medium to high of Ba find in the area
of Varnavas and in Athens basin. There is a positive correlation
between As versus Cu, Zn, Ni, Co, V, and Fe in travertine limestone of
Kalamos–Varnavas basin and As versus Cu, Ni, Mn, V, Cr, Ba, Fe, P, Mg,
Al, Na, K and organic matter in travertine limestone of Mesogeia basin
(Artemida, Drafi).
The predictable spatial distribution of As, Fe, Mn, Ba, Cr and Ni in
soils is presented as well (Fig. 10a–f). The elements As, Cr, Ni, Mn, and
Ba are enrichment in Mesogeia basin (Artemida, Drafi) and in Asopos
basin up to coastal zone of Oropos–Kalamos and low up to intermediate
in Athens basin.
3.4. Statistics-factor analysis
The element distribution in the travertine limestone of Kalamos–
Varnavas basin is explained in terms of five factors, accounting for
82.3% of the total variance of the geochemical dataset (Table 9). Factor
1, explaining 36.9% of the total variability, is a factor with high positive
loadings (N+0.75) for Cu, Sb, V, Sc, Al, and K, moderate positive loadings
for Pb, Ni, Co, Mn, Cr, Ba and P. The second factor explaining 15.5% of the
total variability includes Ni, Co, Mn and Fe. The third factor shows high
positive loading for As and Zn. Factor 4, explaining 10.9% of variance, is a
factor with moderate positive loadings of Pb and organic matter. The
fifth factor explaining 8.5% of total variance is a factor with high positive
loadings for Sr and Mg.
The results of multivariate analysis (factor) in the travertine lime-
stone of Mesogeia basin (Drafi, Artemida) are presented in Table 10.
Five components were identified accounting for 85.4% of total variance.
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 147

Factor 1, explaining 26% of the total variability, is a factor with high

49.9

61.7
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.
5.8
1.4

1.2

1.3

0.5
1.6
positive loadings for Ni, Cr, Al, and K and moderate positive loadings for
As, Zn, Co, V, Fe, P, and Mg. The second factor includes As, Sr, Sb, Ba, Mg,

49.0

61.9
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.

n.d.
5.3
1.4

2.1
1.0

1.5

1.6
Na and organic matter. The third factor explaining 15.3% of the total

Siderite
variability includes As, Mn, Ba, Fe, and P. Factor 4 explaining 11.6% of

47.7

61.8
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.

n.d.
5.2
1.5

1.6
0.8

3.4

1.6
variance, is a factor with moderate positive loadings of Cu and Co. The
fifth factor explaining 9% of the total variability includes Pb and Zn.
Dolomite

The factor analysis of travertine limestone in Athens basin (Table 11)

28.7

19.9

52.5
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.

n.d.
n.d.
is explained in terms of five factors. The first factor explaining 36.4% of
0.4

3.2

0.4
Kaisariani

total variance is a factor with high positive loading for Cu, Mn, V, Ba,
Calcite

Sc, Fe, Al, Na, K and moderate positive loading for Cr and moderate

52.7

52.9
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
0.3

negative loading of Ca. Factor 2, explaining 20.9% of variance, is a factor

with high positive loading of As, Pb, Zn and moderate positive loadings
41.6

12.1

61.8
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
3.3
0.6

3.4
0.8
of Ni and Co. Factor 3 accounts for 11.9% of variance and shows positive
Siderite

loading for Cr and organic matter. Factor 4, accounting 10.4% of the total
50.8

61.9
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
4.5
1.3

3.7
1.2
0.5
variance, is a factor with high positive loading for Mg and moderate
positive loading for Sb. The fifth factor explaining 7.4% of the total
Papagou

Calcite

variability includes Sr.

49.6

51.6
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.
n.d.
0.4

1.0

0.7

4. Discussion
27.2

23.7

61.4
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
0.6
1.9

3.8

1.2
3
Siderite

Triassic and Jurassic limestones are exposed throughout Attica

42.4

61.1
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
2.1
0.9

4.5

6.3

0.6
2.8
1.5

(Diamantopoulos et al., 2009; Marinos, 1983; Papanikolaou et al.,

2004). They differ from the uppermost yellow–brown travertine lime-
29.7

18.5

50.8
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.
n.d.
2.6

stone (Valero-Garcés et al., 2001) of varying thickness (tens to a few

meters) in the arsenic and other trace element contents (Table 1). The
28.7

20.9

53.8
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.
n.d.
2.9

1.3
Dolomite

relatively high As, Fe, Mn, Ni and Ba contents in limestone of travertine

type and the associated soil throughout Attica (Tables 1 & 2; Fig. 4) may
28.8

23.4

52.5
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.
n.d.
0.3

provide geochemical evidence for the environmental significance of

Holargos

travertine limestone and associated soil in the Attica basins and an

Calcite

assessment of the environmental risk, since arsenic is toxic and poten-

51.9

53.9
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.
Representative microprobe analyses of calcite, dolomite and siderite from the travertine limestone of the Neogene basins of Attica.

0.3

1.0

0.7

tially dangerous to humans, animals and plants (Bhattacharyya et al.,

2003; Gasparatos, 2013; Komnitsas and Modis, 2009).
45.7

62.5
n.d.
n.d.

n.d.
n.d.

n.d.
n.d.
5.6
3.6

0.3
0.2
0.4

5.1
0.2
1.4

The average contents of the As, Ni, Cr and Ba in soils (Table 2) are
higher than in travertine limestone and the parametric values of
58.7

62.2
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.
n.d.
2.2

0.7

0.6

Dutch limits (2009) and the Canadian guideline for agricultural land,
residential/parkland area and industrial area (2006), while the Cu, Pb,
43.1

62.7
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.

n.d.
n.d.
4.3
3.0

0.6

0.2
9.8

1.7

Zn, Ni, Co, Cr, Cd, Ca, P and Mg contents in soils are higher than the
global median in soils (Reimann et al., 2014). At the eastern part of the
44.9

10.2

62.3
n.d.
n.d.
n.d.

n.d.
n.d.

n.d.

n.d.
n.d.
3.6
2.2

0.2

0.3

0.9

Athens Basin, Alepovouni Unit, which is bounded by two west-dipping

Siderite

low angle normal faults, is correlated to the allochthonous Lavrion Unit

52.8

61.7
n.d.
n.d.

n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
4.2
2.3

0.4

0.6

0.6
0.8

that tectonically overlies the autochthonous Attica Unit in SE Attica

Varnavas

(Papanikolaou et al., 2004). The WNW–ESE fault Zefiri—Ag. Paraskevi

Calcite

(Fig. 10a) delineates the distribution of arsenic in soils with high contents
47.1

52.1
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
0.5

4.5

(N 300 mg/kg) in the northern part and low to intermediate contents in

the southern part of the Athens basin. This great fault zone has been
36.5

61.9
n.d.

n.d.

n.d.

n.d.

n.d.
9.3
4.7

2.5
2.2

0.1

0.5

4.7

0.9
0.5

interpreted as a barrier for the sea water transgression to form seasonal

lakes in the northern part of the Athens basin (Papanikolaou and
40.8

61.8
n.d.
n.d.
n.d.

n.d.

n.d.

n.d.
7.3
4.6

1.9
2.8

0.4

3.1

0.5
0.5

Papanikolaou, 2007) and may be a controlling factor of travertine

limestone deposition in small thickness, overlying or along fractures of
11.0

36.3

62.1
n.d.

n.d.
n.d.
n.d.

n.d.

n.d.
5.7

0.8
2.6

0.4

3.8

0.8
0.7

gray dolomitic limestone in the Holargos–Papagou–Kaisariani basin

(Fig. 4a–b), in contrast to the Varnavas–Kalamos basin where the traver-
22.1

26.3

62.5
n.d.

n.d.
n.d.
n.d.

n.d.
6.4

0.5
1.2

0.4

3.6
0.5
1.0
0.6

tine limestone displays a thickness greater than 100 m.

11.7

34.4

60.0
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.
5.9

1.4
2.4

2.8

0.8
0.5

4.1. Potential source for As and heavy metals in rocks and soils
Siderite

11.2

36.0

61.2
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.

n.d.
5.5

1.4
3.0

2.6

0.6
0.9

The sources of As contamination may be related with both

anthropogenic activities and natural processes, such as thermal springs
46.7

51.2
n.d.
n.d.
n.d.

n.d.
n.d.
n.d.

n.d.
n.d.
n.d.
1.5
0.8
1.6

0.2

0.4

(geothermal waters) and mining areas. Greece is included among the

As-contaminated “hot spots” in a worldwide scale (Demetriadis, 2010;
47.7

52.3
n.d.
n.d.
n.d.

n.d.
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
1.6
0.4
2.4

0.2

Gamaletsos et al., 2013; Nriagu, 1994; Salminen et al., 2005). As-bearing

Kalamos

Calcite

ores (Economou-Eliopoulos and Eliopoulos, 2000, Winkel et al., 2013)

52.1

52.3
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
0.2

and highly As-contaminated soils are mainly located in northern Greece

and Attica (Demetriadis, 2010; Salminen et al., 2005; Skarpelis, 2005,
As2O3
Cr2O3
Al2O3
Table 5

Na2O

Total
MnO
MgO
P2O5

TiO2
SiO2

ZnO
wt%

CaO
K2 O
FeO

NiO

2007; Voudouris et al., 2008). The Triassic–Jurassic limestones and dolo-

SO4

mites throughout Attica differ in terms of their negligible As and heavy

148 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Table 6
Representative microprobe analyses of Mn–Fe ± Ba ± Pb ± Ni (hydro)oxides, hematite and bacterio-morphic aggregates of goethite from the travertine limestone of the Neogene basins
of Attica.

Kalamos Varnavas

wt% Mn–Fe Hematite Mn–Ba (hydro)oxides Mn–Fe Bacterio-morphic Goethite

(hydro)oxides (hydro)oxides

SiO2 0.6 1.0 0.9 1.1 0.6 1.2 1.2 3.7 2.2 2.4 2.8 2.4 2.9 3.8 2.4 3.1 3.4
Al2O3 5.6 5.3 n.d. 17.1 n.d. 15.5 3.4 7.6 13 4.9 4.7 4.9 4.7 4.3 2.3 0.5 1.2
As2O3 n.d. n.d. n.d. 1.3 n.d. 1.7 1.4 n.d. n.d. 2.3 3.4 2.3 3.3 2.2 n.d. n.d. n.d.
Fe2O3 3.9 6.9 91.1 6 2.8 5.8 1.2 8.1 7.2 65.9 60.8 65.9 60.8 63.7 81.3 79.1 78.7
TiO2 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.7 1.1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Na2O n.d. n.d. n.d. n.d. n.d. n.d. n.d. 4.3 3.5 n.d. n.d. n.d. n.d. n.d. n.d. 2.4 2.1
SO4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.8 0.7 n.d. n.d. n.d. n.d. 0.3 n.d. n.d. n.d.
CoO 4.1 2.0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
CaO 2.8 3.0 1.6 2.5 2.1 2.7 3.4 3.4 1.6 2.1 3.6 2.1 3.6 n.d. 0.5 0.5 1.2
MnO 30.5 28.6 n.d. ### 35.3 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.3
MnO2 55.2 74.4 58.1 72.6
MgO 2.9 3.8 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.1 0.9 0.6
NiO 10.3 9.4 n.d. 2.3 n.d. 2.1 1.1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
ZnO n.d. n.d. n.d. 2.5 n.d. 2.1 0.8 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
BaO n.d. n.d. n.d. 1.8 13 2.1 5.8 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
P2O5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.0 0.8 n.d. n.d. 0.6 0.5
Total 60.8 59.9 93.5 89.8 92.5 91.3 90.9 ### 65.0 77.6 75.3 78.6 76.1 74.3 87.6 87.1 88.0

Papagou Holargos Kaisariani

wt% Mn–Ba (hydro)oxides Mn–Pb (hydro)oxides Goethite Goethite Mn–Ba Mn–Pb Mn–Fe–Ni Hematite Goethite
(hydro)oxides (hydro)oxides (hydro)oxides

SiO2 2.3 6.2 3.3 4.0 1.8 1.5 1.1 0.8 0.4 0.4 0.8 0.9 1.7 0.5 1.8 4.1 3.9
Al2O3 1.3 3.6 n.d. n.d. 0.6 2.2 n.d. 1.0 n.d. n.d. 3.5 3.0 5.4 n.d. 0.5 1.3 n.d.
As2O3 n.d. 0.7 0.9 n.d. 3.0 8.7 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.7 n.d. n.d.
Fe2O3 2.9 9.2 81.5 77.6 74 61.5 n.d. 5.8 2.0 2.7 12.6 9.2 3.11 98.0 82.9 78.8 79.8
TiO2 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.5 n.d.
K2O 0.5 1.2 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
CoO 0.7 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2.8 2.5 3.4 n.d. n.d. n.d. n.d.
CaO 1.3 1.6 0.6 2.5 6.1 6.8 1.0 2.2 1.4 0.9 2.6 2.7 2.9 n.d. 1.0 1.0 1.0
MnO n.d. 2.9 n.d. n.d. 26.9 30.8 31.0 n.d. n.d. n.d. 1.2
MnO2 68.8 50.8 71 70 75 63
MgO 0.7 0.6 1.4 n.d. n.d. n.d. 1.3 n.d. n.d. n.d. 1.4 1.9 3.3 n.d. n.d. 0.7 n.d.
NiO 1.2 0.6 n.d. 0.8 1.6 4.4 n.d. n.d. n.d. n.d. 12.5 14.2 14.6 n.d. n.d. n.d. n.d.
ZnO n.d. n.d. n.d. n.d. 0.8 2.1 n.d. n.d. 1.3 1.8 n.d. n.d. n.d. n.d. n.d. n.d. 1.4
BaO 12.1 3.7 n.d. n.d. n.d. n.d. 11.1 ### n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
P2O5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.8 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.7 n.d.
PbO n.d. 13.5 n.d. n.d. n.d. n.d. n.d. n.d. 17.9 26.6 n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Sb2O3 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.6 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Total 91.6 91.6 87.7 87.8 88.1 87.2 85.4 ### 98.5 95.4 63.1 65.2 65.4 98.5 87.9 87.1 87.4

metal contents as compared to travertine limestone, suggesting con- enclosed tectonically emplaced into Triassic–Jurassic limestones and do-
tamination source(s) during their evolution. Potential sources of As lomites (Diamantopoulos et al., 2009; Marinos, 1983) point to a signifi-
and other uncommon for limestone metals may be: cant contribution of ultramafic rocks to the Miocenic–Upper Pliocenic
carbonate deposits in the major basins of Attica. Arsenic contents, ranging
from 6 to 280 mg/kg have been determined in serpentinites representing
4.1.1. Ophiolites
hydrated peridotites at the base of the mantle wedge beneath Eurasia
The presence of chromite (Figs. 4c, 5c, e), the relatively high Cr
(Hattori et al., 2005), which may be released from subducted sediments
contents, with an increasing trend from the Mesogeia basin towards the
(Bebout et al., 1999). Thus, a portion of As found in travertine limestone
Athens basin (Table 1) and the presence of serpentinized peridotites
may be derived from the ophiolitic serpentinites enclosed tectonically
in limestones (Diamantopoulos et al., 2009; Marinos, 1983).
Table 7
Representative microprobe analyses of chromite from the travertine limestone of Athens
basin.
4.1.2. Sulfide Pb–Zn–Ag mineralization
The carbonate-hosted massive sulfide Pb–Zn–Ag ores are well known
Holargos Papagou Kaisariani from the Lavrion mines to Grammatiko Fe–Mn mineralization. Although
wt% Chromite Chromite Chromite any continuity between Grammatiko and Lavrion famous ancient mine is
Al2O3 0.2 0.2 0.2 1.1 0.3 10.0 20.0 13.0 4.9 15.0 not obvious, underground mining at Grammatiko revealed geological
Cr2O3 18.6 22.1 14.3 18.5 20.2 50.2 52.2 61.1 55.5 57.4 and structure relationships between hosting rocks and the ferromanga-
MgO 8.0 7.8 8.8 8.1 0.6 7.0 9.8 7.9 2.6 11.7 nese formation or gossans (Kampouroglou and Economou-Eliopoulos,
FeO 16.8 18.2 4.3 18.9 30.4 22.7 17.8 17.7 36.8 15.5
2013; Marinos and Petrascheck, 1956; Skarpelis and Argyraki, 2009).
Fe2O3 54.6 50.6 57.5 54.2 48.3 9.9 0.1 0.1 0.1 0.1
NiO 2.4 0.9 14.8 0.5 n.d. n.d. n.d. n.d. n.d. n.d. Both carbonate replacement- and vein-type mineralization are spatially
Total 100.6 99.8 99.9 101.3 99.8 99.8 99.8 99.9 100.0 99.7 related to the detachment fault, that brings the blueschist Unit into
Cr≠ 1.0 1.0 1.0 0.9 1.0 0.8 0.6 0.8 0.9 0.7 contact with the Upper and Lower marbles, the “Kaesariani schists”
Mg≠ 0.5 0.4 0.8 0.4 0.0 0.4 0.5 0.4 0.1 0.6 (Marinos and Petrascheck, 1956) shear bands within marbles, and
Symbols: Cr≠ = Cr / (Cr + Al), Mg≠ = Mg / (Mg + Fe2+); n.d. = not detected. the shear contact between marbles and the intercalated metaclastics
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 149

Table 8
Representative microprobe analyses of rare earth element minerals from the travertine limestone of Kalamos–Varnavas basin and Athens basin.

Kalamos Varnavas Kaisariani

wt% REE REE REE

SiO2 0.6 n.d. 0.5 n.d. 1.1 5.2 4.5 n.d. 1.0 36.0 0.5 3.3 n.d.
Al2O3 n.d. n.d. n.d. 0.6 0.6 4.6 2.4 n.d. n.d. 0.4 n.d. 0.6 n.d.
As2O3 n.d. n.d. n.d. n.d. n.d. 1.5 1.7 n.d. 2.5 0.7 n.d. n.d. n.d.
Fe2O3 n.d. n.d. n.d. n.d. n.d. 0.6 0.4 n.d. n.d. 0.8 n.d. n.d. n.d.
Na2O 1.5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2.2 n.d. n.d. n.d.
K2O 0.2 n.d. n.d. n.d. n.d. 0.7 0.6 n.d. n.d. n.d. n.d. n.d. n.d.
P2O5 12.0 28.2 7.8 26.0 7.5 11.4 11.3 28.7 37.6 20.0 27.9 29.1 28.0
CaO 31.9 10.7 37.7 7.1 38.2 28.6 30.0 1.4 0.9 1.9 1.4 1.0 1.1
NiO n.d. n.d. n.d. n.d. n.d. n.d. 0.4 n.d. n.d. n.d. n.d. n.d. n.d.
TiO2 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.5 n.d. n.d. n.d. n.d.
SO4 0.5 0.8 n.d. 0.6 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
MgO 0.5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Y2O3 n.d. n.d. n.d. n.d. n.d. 15.1 14.7 n.d. 49.6 26.8 n.d. n.d. n.d.
Dy2O3 n.d. n.d. n.d. n.d. n.d. 2.7 2.8 n.d. 4.8 4.0 n.d. n.d. n.d.
ThO2 n.d. n.d. n.d. n.d. n.d. 2.4 2.2 n.d. n.d. n.d. n.d. n.d. n.d.
Gd2O3 n.d. n.d. n.d. n.d. n.d. 1.3 n.d. n.d. n.d. n.d. n.d. n.d. n.d.
La2O3 7.6 13.3 4.6 16.5 4.7 n.d. n.d. 22.5 n.d. n.d. 16.7 18.5 17.2
CeO2 14.3 29.1 9.3 31.5 9.1 n.d. n.d. 37.3 n.d. n.d. 29.3 30.8 34.0
Nd2O3 4.7 9.4 3.6 9.9 3.0 n.d. n.d. 8.0 n.d. n.d. 12.7 12.4 10.0
Er2O3 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 3.2 n.d. n.d. n.d. n.d.
Total 73.7 91.6 63.5 92.2 64.2 74.1 71.0 98.0 96.9 92.7 88.4 95.7 90.3

of the Basal Unit (Skarpelis, 2005). The detachment faults and asso-
ciated faults in the footwall and extensional listric faults in the
hanging-wall, may facilitate the ore forming fluid circulation and de-
position of mixed sulphide (pyrite, galena and sphalerite), ore bodies
enriched in Cu–Au, sulphide and sulphosalt species, containing sig-
nificant Fe, Mn, Ag, As, Pb, Bi, Cd and Sb contents (Skarpelis, 2007;
Voudouris et al., 2008). Thus, the recorded mineralogical and geo-
chemical evidence, in particular the determined Fe–Mn–hydroxides
and minor base metal sulphides, such as pyrrhotite, pyrite, chalcopy-
rite, sphalerite, barite, galenite, enargite, tennantite, as well as F-
apatite, quartz, Ti-oxides, zircon, sphene, rutile, REE-phosphate min-
erals in all travertine limestones studied here in (Tables 5–8), and
the factor analysis data (Tables 9–11) may provide evidence for a
contribution of their detrital and chemical components, from the ero-
sion of the Grammatiko Fe–Mn and Lavrion mineralization and host
rocks (Marinos and Petrascheck, 1956; Skarpelis, 2007; Voudouris
et al., 2008).
4.1.3. Volcanic rocks
Hydrothermal alteration by hot, mineral-laden water can lead to
high contents of arsenic in rocks, such as in the geothermal system in
the Yellowstone area of Wyoming, the Jemez Mountains of northern
New Mexico, Greek travertine in northern Greece, Quaternary traver-
tine sites in the Denizli extensional basin based on their depositional
and geochemical data and elsewhere (Kalogeropoulos et al., 1989;
Özkul et al., 2013; Winkel et al., 2013 and references therein). In com-
parison to those travertines associated with thermal spring water, Fe,
As, and Sr contents in travertine limestone in Neogene basins of Attica
are relatively low (Table 1).

Table 9
Varimax rotated component loadings of 5 factors and variance explained for 21 elements Table 10
in travertine limestone of Kalamos–Varnavas basin. Varimax rotated component loadings of 5 factors and variance explained for 20 elements
in travertine limestone of Mesogeia basin.
Variable Factor Communality
Variable Factor Communality
1 2 3 4 5
1 2 3 4 5
As 0.17 0.29 0.76 0.34 −0.05 0.82
Cu 0.77 0.24 0.35 0.15 0.31 0.89 As 0.51 0.51 0.52 0.30 0.07 0.89
Pb 0.62 −0.18 0.03 0.54 −0.28 0.79 Cu 0.26 0.23 0.40 0.72 0.04 0.80
Zn 0.32 −0.06 0.83 0.04 −0.08 0.81 Pb −0.12 −0.15 0.03 0.03 0.90 0.85
Ni 0.59 0.58 0.31 0.26 0.18 0.89 Zn 0.66 0.15 −0.02 0.11 0.59 0.82
Co 0.57 0.58 0.32 0.18 −0.04 0.80 Ni 0.80 0.17 0.14 0.33 −0.18 0.84
Mn 0.64 0.50 −0.28 0.33 0.08 0.85 Co 0.50 0.01 0.03 0.75 0.11 0.82
Sr 0.01 −0.14 −0.14 0.14 0.92 0.90 Mn 0.16 0.00 0.93 0.14 −0.05 0.92
Sb 0.86 −0.12 0.06 0.34 0.00 0.87 Sr 0.11 0.78 0.10 −0.51 0.14 0.91
V 0.84 0.39 0.30 0.05 0.02 0.94 Sb 0.09 0.75 0.04 0.10 −0.39 0.74
Cr 0.72 0.43 0.12 −0.03 0.04 0.73 V 0.55 0.30 0.49 0.49 −0.17 0.90
Ba 0.65 0.23 0.11 0.40 0.17 0.68 Cr 0.84 0.14 0.23 0.26 −0.21 0.88
Sc 0.85 0.01 0.37 0.09 0.05 0.86 Ba 0.38 0.57 0.63 0.10 0.20 0.91
Fe 0.35 0.84 0.27 0.02 0.02 0.90 Fe 0.55 0.37 0.52 0.35 0.06 0.84
Ca −0.04 −0.78 0.10 0.29 −0.04 0.71 Ca −0.08 −0.82 −0.16 −0.28 0.03 0.78
P 0.71 0.29 0.35 −0.02 0.06 0.72 P 0.66 0.08 0.63 −0.04 0.05 0.84
Mg 0.38 0.32 0.08 −0.17 0.79 0.90 Mg 0.50 0.69 0.02 −0.28 0.22 0.85
Al 0.93 0.19 0.08 0.05 0.11 0.92 Al 0.76 0.26 0.29 0.07 0.26 0.80
Na 0.01 0.22 −0.05 −0.85 0.01 0.77 Na 0.23 0.84 −0.05 0.17 −0.35 0.91
K 0.87 0.32 0.14 −0.11 0.18 0.93 K 0.80 0.28 0.32 0.25 −0.17 0.92
Organic matter 0.20 0.19 0.32 0.64 0.12 0.60 Organic matter 0.27 0.75 0.39 0.21 0.18 0.86
Variance 7.74 3.25 2.29 2.21 1.78 17.28 Variance 5.21 4.69 3.06 2.33 1.80 17.08
% of variance 36.86 15.50 10.91 10.53 8.47 82.26 % of variance 26.03 23.47 15.30 11.64 8.98 85.41
150 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Table 11 converter attrition is responsible for the elevated abundances along

Varimax rotated component loadings of 5 factors and variance explained for 21 elements highways that may be washed by rain and concentrated into local
in travertine limestone of Athens basin.
water systems and soils (Dahlheimer et al., 2007; Ely et al., 2001). Besides
Variable Factor Communality the presence of small (PM10 and PM2.5) particles with dominant
1 2 3 4 5 minerals quartz, calcite, barite, Al, Mg, K, Na-silicates, Fe, Ti, Mn-oxides,
and metal Fe or their oxidation products, significant Zr, Ce, Cr, Cu, Zn,
As 0.00 0.84 −0.28 −0.04 0.13 0.80
Cu 0.84 0.12 0.18 −0.36 0.22 0.93 and Mn contents (Economou-Eliopoulos and Sfendoni, 2010) may be
Pb −0.24 0.82 0.05 0.04 −0.20 0.77 related to brake wear emissions (Schaller, 1991).
Zn 0.04 0.89 −0.01 0.07 −0.09 0.81 Therefore, although the dominant source of As in soils is related with
Ni 0.22 0.72 0.38 0.44 −0.04 0.91 the geology, and hence dependent to some extent on the content in the
Co 0.49 0.55 0.47 0.01 0.39 0.91
Mn 0.76 0.46 0.12 0.00 0.16 0.83
parent rocks, additional inputs derived from human activities, such as
Sr 0.17 −0.53 0.16 0.40 0.57 0.82 traffic emissions and agricultural sources (pesticides and/or additives/
Sb 0.23 0.48 0.10 0.50 −0.55 0.84 fertilizers) in cultivated areas (Komnitsas, and Zaharaki, 2014) could
V 0.84 0.08 0.41 −0.04 0.16 0.91 not be excluded.
Cr 0.55 0.06 0.65 0.25 0.21 0.84
Ba 0.92 −0.01 −0.02 −0.02 −0.15 0.87
Sc 0.82 −0.01 0.45 −0.12 0.22 0.95 4.2. Mobility and precipitation of elements
Fe 0.76 0.40 0.28 −0.13 0.32 0.93
Ca −0.63 −0.02 0.07 −0.01 −0.54 0.70
P 0.25 −0.53 −0.34 −0.58 −0.27 0.87 The occurrence of siderite with significant As, Cr and Mn contents
Mg −0.12 0.05 −0.13 0.93 −0.01 0.91 (Table 5) and its association with veins crosscutting low-Mg calcite
Al 0.89 −0.25 0.34 −0.02 −0.05 0.97 matrix indicate its formation during a subsequent stage of the basin
Na 0.81 −0.21 −0.23 0.38 −0.08 0.91
infilling. In addition, it is suggested that these elements were available
K 0.92 −0.26 0.17 0.03 −0.11 0.95
Organic matter 0.21 −0.10 0.87 −0.12 −0.09 0.82
in significant concentrations in the lake and/of fluid circulation, under
Variance 7.64 4.38 2.49 2.19 1.56 18.26 favourable physico/chemical conditions, due probably to season changes,
% of variance 36.36 20.86 11.86 10.42 7.44 86.95 and in turn changes in the lake chemistry. Also, it has been suggested that
during diagenesis, the precipitation of the cement involves the degrada-
tion by the action of organic matter resulting in an increase in [Ca2+] and
4.1.4. Metamorphic basement
[Mg2+] and sulphate reduction, resulting in the increase of alkalinity
Arsenic content in metamorphic rocks tend to reflect its content in
(Müller and Wagner, 1978) and the formation of siderite in an anaerobic
the precursors igneous and sedimentary rocks (around 5 mg/kg or
environment with low redox potential (Berner, 1981).
less). Pelitic rocks (phyllites) typically have the highest contents (aver-
In a thermodynamic approach, crystal formation of carbonates by
age 18 mg/kg) (Boyle and Jonasson, 1973). Mostly Kaisariani schists
nucleation and growth is a free energy driven phenomenon and solution
within marbles and phyllites, which are often present as a major com-
supersaturation. Saturation is reached when concentrations (activities)
ponent in the basement of the Neogene basins (Diamantopoulos et al.,
of reactant components in the initial solution equal their equilibrium
2009; Marinos, 1983; Marinos and Petrascheck, 1956; Skarpelis, 2007;
concentrations (activities) or solubility product (Ksp) and the change
Voudouris et al., 2008) may be potential source for As.
in free energy (per mole) ΔG = −RTlnKsp (R is the gas constant, and T
is the absolute temperature) (Radha et al., 2013). Thus, factors such as
4.1.5. Organic matter formation of intermediate metastable phases, surface adsorbed water/
Organic matter appears to control the adsorption of Ca, Fe, Th, U and ions or presence of foreign substrates are known to alter nucleation,
REE, even at depths in the soil profile where organic matter content is crystal growth, and phase transformation processes. The observed
low (0.5%) (Achyuthan, 2003). The occurrence of marl limestone with formation of Ca-rich dolomite in the travertine limestone in Attica
lignite intercalations and travertine in basins of Northern Attica (Fig. 4) may indicate that it is controlled by kinetics (Radha et al.,
(Ioakim et al., 2005; Stamatis et al., 2011), the presence of organic mat- 2013) rather than by thermodynamics, since the substitution of Ca
ter in travertine limestone (Table 1), in particular, the elevated As con- for Mg in the Mg layer of dolomite is energetically unfavorable
tents with increasing content of the organic matter (Table 1), the (Burton, 1987; Capobianco et al., 1987).
presence of As-bearing bacterio-morphic aggregates of goethite
(Table 6; Figs. 5 & 6), and the presence of the elevated As contents in
4.2.1. Arsenic
groundwater affected by lignite mining (Kalaitzidis et al., 2010;
Arsenic through Attica travertine limestone was not detected (SEM/
Komnitsas and Modis, 2009; Neumann et al., 2002; Stamatis et al.,
EDS method) in calcite and dolomite. It was mainly hosted in hydrous
2011) suggest that As may be related to the occurrence of organic
siderite and Fe (hydro)oxides and that it is higher in the former that
matter, reflecting repeated transgression and regression of seawater
in the latter (Tables 5, 6). The translocation factor (percentage of metals
and bio-accumulation of arsenic (marine algae, phytoplankton and
translocated from roots to shoots of plants) is relatively low (average
other organisms) during a sea transgression stage (Kalaitzidis et al.,
0.33%) while the significant correlation between the translocation fac-
2010; Mposkos, 2008; Rose et al., 1979; Valeton et al., 1987).
tors for Fe and As may confirm that Fe–Mn oxides/hydroxides represent
the major sorbing agents for As in soils (Kampouroglou and Economou-
4.1.6. Anthropogenic activities Eliopoulos, 2013). The accumulation factor for As, Cr, Ni, Mn, Fe, Sb, Zn,
The investigation of trace elements, including the Platinum (Pt), Cu and Hg in plants (percentage of metals in plants/metal in soil)
palladium (Pd), rhodium (Rh) and gold (Au) in dust samples along exhibits a wide range from relatively low (5.2 to 9%) for As, Fe, Cr, Ni
highways of Attica, with varying traffic, like Katehaki, Messoghion, the and Pb, higher for Cu and Zn (67% to 56%, respectively), to exceptionally
intersection between Katehaki, Messoghion and Acharnon avenues high for Mo (average 160%). The presented data, due to As contamina-
indicated ranges between 160 and 650 (average 380) mg/kg Cu, tion in travertine limestone and associated soil suggest a potential envi-
230 and 660 (470) mg/kg Pb, 290 and 480 (380) mg/kg Mn, 9 and ronmental risk not only for that part of Greece but in general for similar
15 (12) mg/kg As, 71, 140 (110) mg/kg Cr, 63 and160 (82) mg/kg Ni, depositional environments. In addition, the analysis of urban top-soil
110 and 960 (550) ppb Pt, 90 and 1300 (680) ppb Pd and 14 to 990 samples from Athens indicated that Ni, Cr, Co and As are relatively less
(230) ppb Au (Economou-Eliopoulos and Sfendoni, 2010). Although the available than typical tracers such as Pb, Zn, Cu and Cd of anthropogenic
roadside dust is derived by various sources, they confirm that the catalytic contamination (Kelepertzis and Argyraki, 2015).
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 151

Fig. 5. Representative backscattered SEM images from the travertine limestone of the Kaisariani (UK) and Papagou (P) areas (Athens basin) showing light grey calcite (5a–e),
Fe–(hydro)oxides growing over bacteria cells (bacterio-morphic) (5a), Mn–Fe–(hydro)oxides (5c), Mn–Fe–Ni (hydro)oxides (5d), dark grey dolomite (5e), Fe–(hydro)oxides (5a,e),
Mn–Ba (hydro)oxides (5b, f), quartz (5b–c), chromite (5c,e) and Mn–Pb (hydro)oxides (5f). The composition of the samples is given in Tables 6–9.

Sorption of arsenic oxyanions on Fe-oxide/hydroxides solid colloid
surface is considered to be common mechanisms leading to As co-
precipitation in sediments and soils (Plant et al., 2005 and references
therein). Arsenic can remain relatively mobile under a wide range of
redox potentials, particularly at the neutral to slightly alkaline pH values
typically found in surface and groundwater (Brookins, 1988). Ca-
carbonates may account for arsenic immobilization where Fe (and Mn)
oxides lose their adsorbing effectiveness (Smedley and Kinniburgh,
2002). Studies of the As immobilization and formation of Ca–As precipi-
tates have shown that CaHAsO3 is very stable under the high (12–13) pH
values (Dutré and Vandercasteele, 1995, 1998; Dutré et al., 1999;
Vandercasteele et al., 2002). Sorption of As(III) by calcite was investigated
as a function of As(III) concentration, time and pH (Cheng et al., 1999).
The sequestration of As by calcite has been subject of a number of
studies (Alexandratos et al., 2007; Bardelli et al., 2011; Cheng et al.,
1999; Di Benedetto et al., 2006; Fernández-Martínez et al., 2006;
Goldberg and Glaubig, 1988; Le Guern et al., 2003; Román-Ross et al.,
2006; Sadiq, 1997; Yokoyama et al., 2009, 2012). Alexandratos et al.
(2007) were the first to show that cal-arsenate As(V) can replace
carbonate in the calcite lattice in batch sorption experiments carried out
at pH 8.3, without changing the tetrahedral geometry or oxidation state
of As(V). Recently, Yokoyama et al. (2012) confirmed this result over a
wide range of pH (7–12) and furthermore showed that incorporation of
As(V) can also occur from As(III) in solution following an oxidation step
and the via formation of calcium arsenate complexes.
A salient feature is the presence of goethite and hematite growing
over fossilized vestiges of bacteria cells (Figs. 5a, 6f, and c, respectively)
and exhibiting elevated contents of aluminum and arsenic (Table 6),
which may be related with sorption and replacement processes. The
metastable oxyhydroxide ferrihydrite with respect to goethite is exclu-
sively nanoparticulate under typical surface conditions, and has high
specific surface area and significant reactivity toward the sorption of
aqueous contaminants AsO3−, 4 SO2−
4 (Gasparatos, 2013), among others
(Navrotsky et al., 2008; Pinney and Morgan, 2013). In addition, the
negative Gibbs free energy (ΔGo) values for arsenite and arsenate sorp-
tion on Fe-rich soil concretions are consistent with spontaneous reaction
between the species and the medium (Gupta, 2003).
Recently, travertines formed at the western part (Katsikas moun-
tains) of the Chalkidiki peninsula in northern Greece were found to con-
tain exceptionally high As levels (up to 3760 μg/kg) as they were formed
from As-rich geothermal alkaline groundwater and that As is closely
associated with the calcite matrix (Winkel et al., 2013). In addition,
XANES and EXAFS As spectra of travertine samples showed that As in
the studied travertine is exclusively As(V). In general, although
As(V) is thermodynamically stable under oxidizing conditions, and
As(III) is stable under more reducing conditions, As(V) and As(III)
152 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Fig. 6. Representative backscattered SEM images from the travertine limestone from the Kalamos (K)–Varnavas (V) basin, showing calcite (cal) forming fine uniform micritic aggregates
(6a–f), Mn–Fe (hydro)oxides (6a), siderite (6a, b, d–f), hematite (6a–c), muscovite (6d), rutile (6d), quartz (6d) and goethite, showing growing over vestiges of bacteria cells (bacterio-
morphic) (6d–f) in the calcite matrix. The chemical composition of minerals is given (Tables 6–9). Abbreviations: Cal = calcite; Sd = siderite; Hem = hematite; Ms = muscovite; Rt =
rutile; Qz = quartz; Gth = goethite.

(more dangerous for environmental and human health) are often found
to co-occur in both oxic and anoxic waters and sediments due to redox
kinetics (Anderson and Bruland, 1991; Nriagu, 1994).
4.2.2. Fe–Mn-oxides
Fe–Mn- and Mn–Fe-oxides are present as fine-grained aggregates
(Figs. 5b–d; 4f; 6a), in all travertine samples and appear to be strong
scavengers of heavy metals (Table 6). Among Mn-oxides identified in
the Varnavas, Papagou and Kaisariani travertine limestones are minerals
of the cryptomelane group, defined on the basis of the predominant
cation, such as hollandite (Ba) and coronadite (Pb) (Table 6). They are
commonly present as botryoidal masses (Post, 1999). These minerals
are isostructural and form isomorphous mixtures. Coronadite is fairly
rare mineral of the oxidation zone and mainly is the product of simulta-
neous weathering of Mn and Pb-minerals, Pb-replacement deposits in
Mn-rich limestones (Al-Malabeh and El-Hasan, 2009).
4.2.3. REE-minerals
It is found that the fractionation and mobilisation of REEs take place
during pedogenesis and calcretisation. Fractionation changes in the REE
concentration within the calcrete profiles can be accounted mainly to
different pedogenic processes such as mineral weathering, neoformation
of clays, clay illuviation, generation of Fe–Mn hydroxides and their
movement within the profile. Zircon is a possible host for Hf, Th and Yb
and there is an association of these elements with Zr in some samples
(Al-Malabeh and El-Hasan, 2009).
5. Conclusions
The compilation of mineralogical, geochemical and a combined
approach of multivariate statistics and GIS data on travertine limestone
and soil samples from the Neogene basins of Attica led to the following
conclusions:
• Maps showing the contaminated and potentially contaminated sites,
coupled with the mineralogical and geochemical data confirm the
geotectonic literature data, suggesting the separation of an initially
single basin in Attica into smaller basins.
• Major contamination sources are probably the sulfide and Fe–Mn
mineralization in Attica, the basement rocks the involved mylonitic
ophiolitic blocks, and to a lesser extent human activities (catalytic
converter attrition/traffic emissions and/or agricultural sources).
• The distribution of As and other harmful element contamination in
travertine limestone and soil of the Neogene basins in Attica provide
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 153

Fig. 7. Maps of Hot Spot Analysis for (a): As; (b): Fe; (c): Cr; (d): Ni; (e) Mn and (f): Ba in rocks of Neogene basins of Attica. Data from Table 1.
154 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Fig. 7 (continued).
E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 155

Fig. 7 (continued).
156 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Fig. 8. Maps of Hot Spot Analysis for (a): As; (b): Fe; (c): Cr; (d): Ni; (e) Mn and (f): Ba in soils of Neogene basins of Attica. Data from Table 2.
E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 157

Fig. 8 (continued).
158 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Fig. 8 (continued).
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 159

Fig. 9. Geochemical maps showing the spatial distribution patterns of selected major and trace elements in rocks. Prediction map for (a): As; (b): Fe; (c): Cr; (d): Ni; (e) Mn and (f): Ba in
basins of Attica, Greece. Data from Table 1.
160 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Fig. 9 (continued).
E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 161

Fig. 9 (continued).
162 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Fig. 10. Geochemical maps showing the spatial distribution patterns of selected major and trace elements in soils. Prediction map for (a): As; (b): Fe; (c): Cr; (d): Ni; (e): Mn and (f): Ba in
basins of Attica, Greece. Data from Table 2.
E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166 163

Fig. 10 (continued).
164 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166

Fig. 10 (continued).
 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166
evidence for a significant contamination in the uppermost travertine
limestone and associated soils, covering a significant part of Attica.
• Since the uppermost yellow–brown travertine limestone appear to be
extended in many places throughout Attica, it may give rise to a
significant impact on or risk to human health and ecosystems.
• The presence of As-bearing Fe(III) (hydro)oxides, such as goethite
and Fe(II)-minerals, such as siderite, indicates that they are potentially
low cost materials for As-remediation.
Acknowledgments
The University of Athens is greatly acknowledged for the financial
support (Grant No ΚΕ_11078) of this work. Mr. E. Michaelidis, University
of Athens, is thanked for the assistance with the SEM/electron probe
analyses. The Editor Dr. Lewis A. Owen and reviewers are greatly
acknowledged for their constructive criticism and suggestions for
improvement of our manuscript.
References
Achyuthan, H., 2003. Petrologic analysis and geochemistry of the late Neogene–Early
Quaternary hardpan calcretes of Western Rajasthan, India. Quat. Int. 106-107, 3–10.
Alexandratos, V.G., Elzinga, E.J., Reeder, R.J., 2007. Arsenate uptake by calcite: macroscopic
and spectroscopic characterization of adsorption and incorporation mechanisms.
Geochim. Cosmochim. Acta 71, 4172–4187.
Al-Malabeh, A., El-Hasan, T., 2009. Mineralogy and chemistry of coronadite from Middle
Cambrian manganese deposits at Wadi Dana, Southern Jordan. Am. J. Appl. Sci. 6
(4), 576–581.
Anderson, L.C.D., Bruland, K.W., 1991. Biogeochemistry of arsenic in natural waters: the
importance of methylated species. Environ. Sci. Technol. 3, 420–427.
Argyraki, A., Kelepertzis, E., 2014. Urban soil geochemistry in Athens, Greece: the importance
of local geology in controlling the distribution of potentially harmful trace elements. Sci.
Total Environ. 482-483, 366–377.
ASTM, 2000. Standard test methods for moisture, ash and organic matter of peat and
other organic soils, Method D 2974-00. American Society for Testing and Materials,
West Conshohocken, PA.
Bardelli, F., Benvenuti, M., Costagliola, P., Di Benedetto, F., Lattanzi, P., Meneghini, C.,
Romanelli, M., Valenzano, L., 2011. Arsenic uptake by natural calcite: an XAS study.
Geochim. Cosmochim. Acta 75, 3011–3023.
Bebout, G.E., Ryan, J.G., Leeman, W.P., Bebout, A.E., 1999. Fractionation of trace elements
by subduction-zone metamorphism-effect of convergent margin thermal evolution.
Earth Planet. Sci. Lett. 171, 63–81.
Berner, R.A., 1981. Authigenic mineral formation resulting from organic matter decomposi-
tion in modern sediments. Fortschr. Mineral. 59, 117–135.
Bhattacharyya, R., Jana, J., Nath, B., Sahu, S.J., Chatterjee, D., Jacks, G., 2003. Groundwater
As mobilization in the Bengal Delta Plain, the use of ferralite as a possible remedial
measure—a case study. Appl. Geochem. 18, 1435–1451.
Boyle, R.W., Jonasson, I.R., 1973. The geochemistry of arsenic and its use as an indicator
element in geochemical prospecting. J. Geochem. Explor. 2, 251–296.
Brookins, D.G., 1988. Eh–pH diagrams for geochemistry. 176. Springer, Verlag New York.
Burton, B.P., 1987. Theoretical analysis of cation ordering in binary rhombohedral carbonate
systems. Am. Mineral. 72, 329–336.
Canadian Council of Ministers for the Environment, 2006. Canadian soil quality guidelines
for the protection of environmental and human health, update 6.02, Publication no
1299. 1-896997-34-1.
Capobianco, C., Burton, B.P., Davidson, P.M., Navrotsky, A., 1987. Structural and calorimetric
studies of orderdisorder in cadmium magnesium carbonate CdMg(CO3)2). J. Solid State
Chem. 71, 214–223.
Cheng, L., Fenter, P., Sturchio, N.C., Zhong, Z., Bedzyk, M.J., 1999. X-ray standing wave
study of arsenite incorporation at the calcite surface. Geochim. Cosmochim. Acta
63, 3153–3157.
Clement, B., 1976. Essai d'interpretation structurale d'un secteur des zones internes
Helleniques: l' Attique-Beotie. Bull. Soc. Geol. Fr. 2 (7), 309–316 XVIII.
Commission Regulation (EC) No 1881/, 2006. Setting maximum levels for certain contami-
nants in foodstuffs (Text with EEA relevance).
Council Directive 86/278/EEC. On the protection of the environment, and in particular of
the soil, when sewage sludge is used in agriculture.
Council Directive 98/83/EC. On the quality of water intended for human consumption.
Dahlheimer, S.R., Neal, C., Fein, A., 2007. Potential mobilization of platinum-group
elements by siderophores in surface. Environ. Sci. Technol. 41, 870–875.
Davis, H.T., Aelion, C.M., McDermott, S., Lawson, A.B., 2009. Identifying natural and
anthropogenic sources of metals in urban and rural soils using GIS-based data, PCA,
and spatial interpolation. Environ. Pollut. 157, 2378–2385.
Demetriadis, A., 2010. Medical geology in Hellas: the Lavrion urban environmental pollution
study. In: Selimus, O., Finkelman, R.B., Centeno, J.A. (Eds.), Medical Geology: A Regional
Synthesis. Spinger, Dordrecht, pp. 355–390.
165
Di Benedetto, F., Costagliola, P., Benvenuti, M., Lattanzi, P., Romanelli, M., Tanelli, G., 2006.
Arsenic incorporation in natural calcite lattice evidence from electron spin echo
spectroscopy. Earth Planet. Sci. Lett. 246, 458–465.
Diamantopoulos, A., 2006. Non-coaxial stretching deformation dominating the Upper
Structural Plate of the Metamorphic core complex of Attica (Internal Hellenides, Central
Greece). XVIIIth Congress of the Carpathian-Balkan Geological Association, Belgrade,
Servia, pp. 101–105.
Diamantopoulos, A., Krohe, A., Mposkos, E., 2009. Kinematics of conjugate shear zones,
displacement partitioning and fragmentation of the upper rigid crust during denudation
of high-P rocks (Pelagonian and Sub-Pelagonian Zones, Greece). Tectonophysics 473,
84–98.
Directive 2000/76/EC of the European Parliament and of the Council, 2000e. On the inciner-
ation of waste.
Directive 2008/50/EC of the European Parliament and of the Council, 2008e. On ambient
air quality and cleaner air for Europe.
Dutré, V., Vandercasteele, C., 1995. Solidification/stabilisation of hazardous arsenic
containing waste from a copper refining process. J. Hazard. Mater. 40, 55–68.
Dutré, V., Vandercasteele, C., 1998. Immobilisation of arsenic in waste solidified using
cement and lime. Environ. Sci. Technol. 32, 2782–2787.
Dutré, V., Vandercasteele, C., Opdenakker, S., 1999. Oxidation of arsenic bearing fly ash as
a pretreatment before solidification. J. Hazard. Mater. B68, 205–215.
Economou-Eliopoulos, M., Eliopoulos, D., 2000. Palladium, platinum and gold concentration
in porphyry copper systems of Greece and their genetic significance. Ore Geol. Rev. 16
(1-2), 28–40.
Economou-Eliopoulos, M., Sfendoni, T., 2010. Environmental impact of Pt, Pd, Rh and Au
from catalytic converters along roadsides: the case of Attica, Greece. Proc. of XIX
Congress of the Carpathian Balkan Geological Association, Thessaloniki, Greece, 100,
pp. 47–54.
Ely, J.C., Neal, C.R., Kulpa, C.F., Schneegurt, M.A., Seidler, J.A., Jain, J.C., 2001. Implications
of platinum-group element accumulation along U.S. roads from catalytic-converter
attrition. Environ. Sci. Technol. 35, 3816–3822.
Esdat Environmental Database Management Software, 2009. Soil remediation circular.
Fernández-Martínez, A., Román-Ross, G., Cuello, G.J., Turrillas, X., Charlet, L., Johnson, M.R.,
Bardelli, F., 2006. Arsenic uptake by gypsum and calcite: modelling and probing by
neutron and X-ray scattering. Phys. B Condens. Matter 385–386, 935–937.
Gamaletsos, P., Godelitsas, A., Dotsika, E., Tzamos, E., Göttlicher, J., Filippidis, A., 2013.
Geological sources of As in the environment of Greece: a review. In: Scozzari, A.,
Dotsika, E. (Eds.), The Volume “Threats to the Quality of Groundwater Resources:
Prevention and Control”review series “The Handbook of Environmental Chemistry”.
Springer's.
Gasparatos, D., 2013. Sequestration of heavy metals from soil with Fe–Mn concretions
and nodules. Environ. Chem. Lett. 11 (1), 1–9.
Goldberg, S., Glaubig, R., 1988. Anion sorption on a calcareous, montmorillonitic
soil—arsenic. Soil Sci. Soc. Am. J. 52, 1297–1300.
Gupta, C.K., 2003. Chemical Metallurgy: Principles and Practice. John Wiley and Sons,
Weinheim.
Haq, B.L., Hardenbol, J., Vail, P.R., 1987. Chronology of fluctuating sea levels since the Triassic
(250 million years to present). Science 235, 1156–1167.
Hattori, K., Takahashi, Y., Guillot, S., Johanson, B., 2005. Occurrence of arsenic (V) in
forearc mantle serpentinites based on X-ray absorption spectroscopy study. Geochim.
Cosmochim. Acta 69, 5585–5596.
Ioakim, C., Rondoyanni, T., Mettos, A., 2005. The Miocene basins of Greece (Eastern
Mediterranean) from a paleoclimatic perspective. Rev. Paléobiol. 24 (2), 735–748.
Kabata-Pendias, A., Pendias, H., 2001. Trace Elements in Soils and Plants. CRC Press, USA.
Kalaitzidis, S., Siavalas, G., Skarpelis, N., CarlaViviane Araujo, C., Christanis, C., 2010. Late
Cretaceous coal overlying karstic bauxite deposits in the Parnassus-Ghiona Unit, Central
Greece: coal characteristics and depositional environment. Int. J. Coal Geol. 81, 211–226.
Kalogeropoulos, S.I., Kilias, S.P., Bitzios, D.C., Nicolaou, M., Both, R.A., 1989. Genesis of the
Olympias carbonate-hosted Pb–Zn(Au, Ag) sulfide ore deposit, Eastern Chalkidiki
peninsula, Northern Greece. Econ. Geol. 84, 1210–1234.
Kampouroglou, E.E., 2011. Investigation of contamination at the carbonic basin in
Varnavas, Attica from arsenic and heavy metals and their source of origin (Master)
University of Athens, Greece (in Greek).
Kampouroglou, E., Economou-Eliopoulos, M., 2013. Natural contamination by As and heavy
metals in soil, their bio-accumulation and potential sources: the case of a travertine
limestone quarry, Greece. Cent. Eur. J. Geosci. 5 (1), 174–188.
Kelepertzis, E., Argyraki, A., 2015. Geochemical associations for evaluating the availability
of potentially harmful elements in urban soils: lessons learnt from Athens, Greece.
Appl. Geochem. 59, 63–73.
Komnitsas, K., Modis, K., 2006. Soil risk assessment of As and Zn contamination in a coal
mining region using geostatistics. Sci. Total Environ. 371, 190–196.
Komnitsas, K., Modis, K., 2009. Geostatistical risk assessment at waste disposal sites in the
presence of hot spots. J. Hazard. Mater. 164 (2-3), 1185–1190.
Kontopoulos, A., Komnitsas, K., Xenidis, A., Papassiopi, N., 1996. Environmental characterisa-
tion of the sulphidic tailings in Lavrion. Miner. Eng. 8 (10), 1209–1219. http://dx.doi.org/
10.1016/0892-6875(95)00085-5.
Korre, A., Durucan, S., Koutroumani, A., 2002. Quantitative-spatial assessment of the risks
associated with high Pb loads in soils around Lavrio, Greece. Appl. Geochem. 17 (8),
1029–1045.
Le Guern, C., Baranger, P., Crouzet, C., Bodénan, F., Conil, P., 2003. Arsenic trapping by iron
oxyhydroxides and carbonates at hydrothermal spring outlets. Appl. Geochem. 18,
1313–1323.
Liedekerke, M., Prokop, G., Rabl-berger, S., Kibblewhite, M., Louwagie, G., 2014. JRC Reference
Reports; Progress in the management of Contaminated Sites in Europe. p. 72.
Lozios, S., 1993. Tectonic analysis of metamorphic formations of Northeastern Attica (PhD
thesis) University of Athens, Greece.
166 E.E. Kampouroglou, M. Economou-Eliopoulos / Catena 139 (2016) 137–166
Marinos, G.P., 1983. La position tectonique des “Schistes d'Athènes” sur le complexe
métamorphique du Mont Hymette. Compte rendu de l'Académie d'Athènes.
Marinos, G.P., Petrascheck, W.E., 1956. Laurium. Institute for Geology and Subsurface
Research, Athens, Greece.
Mettos, A., 1992. Geological and Paleogeographical study of the continental Neogene and
Quaternary formations of NE Attica and SE Boeotia (PhD thesis) University of Athens,
Greece.
Mposkos, E., 2008. Neogene and quaternary sediments of the northern part of Athens
basin and the broad area of Kapandriti. Contribution to the palaeogeographic
evolution of Athens basin from late Miocene to Present. Min. Wealth 149.
Müller, G., Wagner, F., 1978. Holocene carbonate evolution in Lake Balaton (Hungary): A
response to climate and impact of man. In: Matter, A., Tucker, M.E. (Eds.), Modern
and Ancient Lake Sediments. Special Publications of the International Association of
Sedimentologists, Blackwell Scientific Publications 2, pp. 57–81.
Navrotsky, A., Mazeina, L., Majzlan, J., 2008. Size-driven structural and thermodynamic
complexity in iron oxides. Science 319, 1635–1638.
Nelson, D.W., Sommers, L.E., 1996. Total carbon, organic carbon and organic matter. In:
Page, et al. (Eds.), Methods of Soil Analysis: Part 2—Chemical and Microbiological
Properties. ASA Monograph.
Neumann, T., Stögbauer, A., Walpersdorf, E., Stüben, D., Kunzendorf, H., 2002. Stable isotopes
in recent sediments of Lake Arendsee, NE Germany: response to eutrophication and
remediation measures. Palaeogeogr. Palaeoclimatol. Palaeoecol. 178, 75.
Nordstrom, D.K., 2002. Worldwide occurrences of arsenic in groundwater. Science 296.
Nriagu, J.O., 1994. Global inventory of natural and anthropogenic emissions of trace
metals to the atmospheres. Nature 279, 409–411.
Özkul, M., Kele, S., Gökgöz, A., Shen, C.C., Jones, B., Baykara, M.O., Fόrizs, I., Németh, T.,
Chang, Y.-W., Alçiçek, M.C., 2013. Comparison of the Quaternary travertine sites in the
Denizli Extensional Basin based on their depositional and geochemical data. Sediment.
Geol. 294, 179–204.
Papanikolaou, D., Papanikolaou, I., 2007. Geological, geomorphological and tectonic structure
of the NE Attica and seismic hazard implications for the northern edge of the Athens
plain. Bull. Geol. Soc. Greece 40, 425–438.
Papanikolaou, D., Royden, L.H., 2007. Disruption of the Hellenic arc: Late Miocene extension-
al detachment faults and steep Pliocene–Quaternary normal faults-or what happened at
Corinth? Tectonics 26, TC5003. http://dx.doi.org/10.1029/2006TC002007.
Papanikolaou, D.I., Lozios, S.G., Soukis, K., Skourtsos, E., 2004. The geological structure of
the allochthonous “Athens schists”. Bull. Geol. Soc. Greece 36, 1550–1559 [in Greek
with English abstract].
Pinney, N., Morgan, D., 2013. Thermodynamics of Al-substitution in Fe-oxyhydroxides.
Geochim. Cosmochim. Acta 120, 513–530.
Plant, J.A., Fordyce, F.M., Kinniburgh, D.G., Smedley, P.L., 2005. The metalloids-arsenic and
selenium. In: Sherwood Lollar, B. (Ed.), Treatise in Geochemistry. Elsevier.
Post, J.E., 1999. Manganese oxide minerals: crystal structures and economic and environ-
mental significance. Proc. Natl. Acad. Sci. 96, 3447–3454.
Radha, V.A., Navrotsky, A., 2013. Thermodynamics of carbonates. In: Mineralogical Society
of America (Ed.)Mineralogy & Geochemistry 77, pp. 73–121.
Reimann C, Birke M, Demetriades A, Filzmoser P, O'Connor P, (Eds), 2014. Chemistry of
Europe's agricultural soils. Geologisches Jahrbuch (Reihe B)Schweizerbarth.
Rögl, F., Steininger, E.F., 1983. Vom Zerfall der Tethys zu Mediterran und Paratethys. Die
Neogene Paleogeographie und palinspastik des zirkum-mediterranen Raumes. Ann.
Naturhist. Mus. Wien 85 (4), 135–163.
Román-Ross, G., Cuello, G.J., Turrillas, X., Fernández-Martínez, A., Charlet, L., 2006. Arsenite
sorption and co-precipitation with calcite. Chem. Geol. 233, 328–336.
Rose, W., Hawkes, E., Webb, S., 1979. Geochemistry in Mineral Exploration. second ed.
Academic Press.
Sadiq, M., 1997. Arsenic chemistry in soils: an overview of thermodynamic predictions
and field observations. Water Air Soil Pollut. 93, 117–136.
Salminen, R., Batista, M.J., Bidovec, M., Demetriades, A., De Vivo, B., De Vos, W., Duris, M.,
Gilucis, A., Gregorauskiene, V., Halamic, J., Heitzmann, P., Lima, A., Jordan, G., Klaver,
G., Klein, P., Lis, J., Locutura, J., Marsina, K., Mazreku, A., O'Connor, P.J., Olsson, S.A.,
Ottesen, R.T., Petersell, V., Plant, J.A., Reeder, S., Salpeteur, I., Sandstro, H., Siewers,
U., Steenfelt, A., Tarvainen, T., 2005. Geochemical atlas of Europe. Part 1: background
information, methodology and maps. Espoo Geological Survey of Finland, p. 526.
Schaller, K.H., 1991. Zirconium. In: Merian, E. (Ed.), Metals and their Compounds in the
Environment. Weinheim, VCH, pp. 1343–1348.
Skarpelis, N., 2005. Non-sulfide zinc ores in Lavrion, Greece. In Volume of Abstracts,
Exploratory Workshop “Non-sulfide Zn–Pb ores: Genetic Models and Exploration:
The European Deposits. European Science Foundation, Inglesias (Sardinia).
Skarpelis, N., 2007. The Lavrion deposit (SE Attica, Greece): geology, mineralogy and
minor element chemistry. Neues Jb. Mineral. Abh. 183 (3), 227–249.
Skarpelis, N., Argyraki, A., 2009. Geology and origin of supergene ore at the Lavrion
Pb–Ag–Zn deposit, Attica, Greece. Resour. Geol. 59 (1), 1–14.
Smedley, P.L., Kinniburgh, D.G., 2002. A review of the source, behavior and distribution of
arsenic in natural waters. Appl. Geochem. 17, 517–568.
Stamatis, G., Alexakis, D., Gamvroula, D., Migiros, G., 2011. Groundwater quality assessment
in Oropos-Kalamos basin, Attica, Greece. Environ. Earth Sci. 64 (4), 973–988.
Valero-Garcés, B., Arenas, C., Delgado-Huertas, A., 2001. Depositional environments of
Quaternary lacustrine travertines and stromatolites from high-altitude Andrean
lakes, northwestern Argentina. Can. J. Earth Sci. 38, 1263–1283.
Valeton, I., Biermann, M., Reche, R., Rosenberg, F., 1987. Genesis of Ni-laterites and bauxites
in Greece during the Jurassic and Cretaceous, and their relation to ultrabasic parent
rocks. Ore Geol. Rev. 2, 359–404.
Vandercasteele, C., Dutré, V., Geysen, D., Wauters, G., 2002. Solidification/stabilisation of
arsenic bearing fly ash from the metallurgical industy. Immobilisation mechanism
of arsenic. Waste Manag. 22, 143–146.
Voudouris, P., Melfos, V., Spry, P.G., Bonsall, T., Tarkian, M., Economou-Eliopoulos, M.,
2008. Mineralogy and fluid inclusion constraints on the evolution of the Plaka
intrusion-related ore system, Lavrion, Greece. Mineral. Petrol. 93, 79–110.
Welch, A.H., Westjohn, D.B., Helsel, D.R., Wanty, R.B., 2000. Arsenic in ground water of the
United States: occurrence and geochemistry. Ground Water 38, 589–604.
Winkel, H.E., Casentini, B., Bardelli, F., Voegelin, A., Nikolaidis, P.N., Charlet, L., 2013.
Speciation of arsenic in Greek travertines: co-precipitation of arsenate with calcite.
Geochim. Cosmochim. Acta 106, 99–110.
Xenidis, A., Papassiopi, N., Komnitsas, K., 2003. Carbonate rich mine tailings in Lavrion: risk
assessment and proposed rehabilitation schemes. Adv. Environ. Res. 7 (2), 207–222.
Xypolias, P., Kokkalas, S., Skourlis, K., 2003. Upward extrusion and subsequent transpression
as a possible mechanism for the exhumation of HP/LT rocks in Evia island (Aegian Sea,
Greece). J. Geodyn. 35, 303–332.
Yokoyama, Y., Mitsunobu, S., Tanaka, K., Itai, T., Takahashi, Y., 2009. A study on the
coprecipitation of arsenite and arsenate into calcite coupled with the determination
of oxidation states of arsenic both in calcite and water. Chem. Lett. 38, 910–911.
Yokoyama, Y., Tanaka, K., Takahashi, Y., 2012. Differences in the immobilization of arsenite
and arsenate by calcite. Geochim. Cosmochim. Acta 91, 202–219.
Komnitsas, K., Zaharaki, D., 2014. Assessment of human and ecosystem risk due to
agricultural waste compost application on soils: a review. Environ. Forensic 15 (4),
312–328.