Journal of
Archaeological
SCIENCE
Journal of Archaeological Science 31 (2004) 1015–1028
http://www.elsevier.com/locate/jas
Provenance of archaeological limestone with EPR spectroscopy:
the case of the Cypriote-type statuettes
K. Polikreti a*, Y. Maniatis a, Y. Bassiakos a, N. Kourou b, V. Karageorghis c
b
a
Laboratory of Archaeometry, NCSR “Demokritos”, 153 10 Aghia Paraskevi, Attiki, Greece
University of Athens, Department of Archaeology, University Campus, 157 84 Zografou, Greece
c
Leventis Foundation, 40 Gladstonos Street, P.O. Box 22543, 1095 Nicosia, Cyprus
Received 9 October 2002; received in revised form 31 July 2003; accepted 20 December 2003
Abstract
The present work demonstrates the potential of EPR spectroscopy as a useful technique in provenance investigation of
archaeological finds of limestone. The case of the small, Cypriote-type limestone statuettes found in most major Archaic sanctuaries
of the Eastern Mediterranean is used as an illustrative application.
Ancient and modern limestone quarries of Cyprus, Samos, Rhodes and Egypt were sampled in order to form a reference data
bank for the likely places of origin. Samples were also taken from statuettes exhibited in the archaeological museums of Nicosia
(2 samples), Samos (14 samples) and Copenhagen (National Archaeological Museum, 19 samples).
All quarry and archaeological samples were analysed with EPR spectroscopy. The quarry samples from Rhodes were easily
distinguished from the other quarry samples and were not treated further because they produce material of low quality and
compactness. A detailed study of the EPR spectroscopy results leads to the determination of a number of parameters, which
separate the reference group of Samos from those of Cyprus and Egypt. The structure of the EPR spectra in the region around
g=2.0000 is characteristic for these different quarrying areas. Diagrams where each quarry area is represented by a field were drawn
and the archaeological samples were plotted on them.
All the analysed statuettes (except for one, which is most probably of Samian limestone) appear to be carved in Cypriote
limestone. Consequently, the results of this research offer a decisive argument in favour of the Cypriote origin for statuettes of this
type found in the Aegean.
2004 Elsevier Ltd. All rights reserved.
Keywords: Limestone; Provenance; Cyprus; Egypt; Aegean; Statuettes; EPR spectroscopy
1. Introduction
The aim of the present study is to demonstrate
the effectiveness of Electron Paramagnetic Resonance
(EPR) spectroscopy in investigating the provenance of
archaeological limestone. Only a few physicochemical
studies have been done towards this direction because
* Corresponding author. Department of Physics, Photonics and
Optoelectronics Laboratory, University of Cyprus, P.O. Box 20537,
Nicosia 1678, Cyprus.
E-mail addresses: [email protected] (K. Polikreti),
[email protected] (Y. Maniatis),
[email protected] (Y. Bassiakos), [email protected]
(N. Kourou), [email protected] (V. Karageorghis).
0305-4403/04/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jas.2003.12.013
soft limestone necessary for sculpture is rare, while the
more commonly found hard limestone, is mostly used
for building purposes and, as such, only rarely travels
far from its original source. Most of the research has
been concentrated in Neutron Activation Analysis
(NAA) and petrography. The first attempt was made by
Meyers and Van Zelst [24], who used NAA to characterise sculpture from Egypt and Spain, but without
promising results. Middleton and Bradley [25] used
petrographic examination, optical and scanning electron
microscopy and X-ray diffraction analysis of the
insoluble fraction. Around thirty archaeological samples
from Cairo, Thebes/Abydos (Egypt) and El Bersha were
analysed and the results prove that these areas can
be distinguished mineralogically and petrographically.
1016
a
K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
b
c
Fig. 1. Typical Cypriote-type statuettes from the Athena sanctuary at Lindos, Rhodes (Copenhagen, National Museum): (a) Lion crouching on a
plinth (Museum Code 10453, height: 11.5 cm), (b) Beardless, human head wearing a diadem over the forehead (Museum Code 10434, height: 9.9 cm),
(c) Male votary (Museum Code 10423, height: 15.8 cm).
Only a few quarry stones though were used for comparison. Riis et al. [31] reported that the petrographic
examination of three statuettes in the National Museum
of Copenhagen, originating from Tripolis (Lebanon),
Lindos (Rhodes) and Kition (Cyprus), proved that they
were made of the same type of limestone. This limestone
is considered Cypriote without any comparison though
with quarry samples. Bello and Martin [4] used Flame
Emission Spectroscopy (FES) and Atomic Absorption
Spectroscopy (AAS) to trace the limestone quarries
along the east bank of Guadalquivir, which were used
for the construction of the Seville Cathedral. Extended
information have also been reported by Harrell [10] on
the petrographic and geochemical characteristics of the
limestone quarries located south of Cairo and across
both Nile banks up to Luxor. In 1994, Holmes and
Harbottle [13] reported the Brookhaven Limestone
database created by applying NAA on quarry samples
from Ile-de-France, Burgundy, Perigord and samples
from museum sculptures and French monuments. This
database contained more than 2000 samples in 1999 and
is still expanding [14].
Both petrography and compositional analysis, thus,
have given satisfactory results, sometimes used together
as complementary techniques. However, we applied
EPR spectroscopy in limestone provenance investigation
because EPR measurements are cheaper, less time consuming and the powder samples used are not destroyed
and can also be analysed by other techniques. Finally,
the technique has shown a high distinguishing provenance potential in the case of marble provenance
investigation and, as such, has been used with great
success in the Laboratory of Archaeometry since 1987
[21,22,29,30].
In order to illustrate the potential of the technique,
we chose to present here the problem of provenance
determination of the so-called Cypriote-type statuettes
of the Archaic Period (Fig. 1 [20]). This case is unique,
not only due to the systematic use of limestone in
small object production but also due to the extended
distribution of the Cypriote type statuettes in the
Archaic world. Outside Cyprus, they are found, in larger
or smaller numbers, in most major sanctuaries of
Eastern Greece, such as those on the islands of Samos
and Rhodes, Miletus on the opposite Turkish coast,
Naucratis in Egypt and Amrit on the Syro-palestinian
coast (Fig. 2). Their appearance spans from the last
quarter of the 7th to the middle of the 6th century BC
[8,15,34]. The size of the statuettes averages from 10 to
20 cm, but larger pieces reaching up to 40 or even 70 cm
have also been found [16]. They are made of a very soft
and homogenous limestone with colour varying from
creamy-white to yellowish. The origin of this material
has been a controversial issue between scholars for many
years [8,11,15,31].
Our project is concentrated on statuettes found in the
Aegean (Samos and Rhodes), of the so-called Aegean
class but comparative material from Cyprus was also
included (two statuettes from the Cypriote class). In
strict scientific terms, we should compare the analysis
results of the statuettes with a databank of limestone
samples from quarries located at the vicinity of all sites
K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
Fig. 2. Simple sketch of Eastern Mediterranean with sampling areas (in
rectangles) and major sites where Cypriote-type statuettes have been
found.
where statuettes of such type were found. The extended
distribution of the archaeological material (Aegean,
Cyprus, Syro-palestinian coast, Egypt), however, makes
this project rather difficult to be achieved. We decided
thus to take archaeological evidence into account and
concentrate our investigation on quarrying areas
pointed out by the numerous scholars who have studied
the material. According, thus, to stylistic, historical
and archaeological evidence, three places have been
suggested as possible production sites: Cyprus [15,31],
Aegean (Samos or Rhodes) [11,12] and Egypt (Naucratis)
[8,9]. These are the areas where our fieldwork was
concentrated.
2. Experimental techniques and samples
The statuette and quarry samples were analysed by
Electron Paramagnetic Resonance (EPR) spectroscopy.
EPR involves the absorption of microwaves by the
sample in powder form in a resonating cavity inside an
external magnetic field, which sweeps from 0 to 6000
Gauss. This technique has been extensively used in the
Laboratory of Archaeometry of NCSR “Demokritos”
for the provenance of marble and considerable experience has been accumulated. It can provide useful and
unique information about the concentration of certain
ions and their crystal symmetry in the structure of
limestone and marble. The features which can be
detected include: the concentration of Mn2+ and Fe3+ in
the CaCO3 crystal, the concentration of Fe3+ in other
accessory minerals existing in the limestone, various
compounds of organic origin and various defects in
the crystal lattice. The above features depend on the
geological conditions that prevailed during the formation
of the limestone deposit.
1017
Our project concentrated on the so-called “Aegean
class” of statuettes, which includes statuettes of Cypriote
type found in the Aegean and is characterised by a
mixed Greek–Cypriote style (Table 1). Fifteen statuettes
were sampled from the Archaeological Museum of
Vathy, Samos, 19 from the Archaeological Museum of
Copenhagen (from Lindos and Vroulia sites on Rhodes)
and another two from the Museum of Nicosia belonging
to the Cypriote class. In an attempt to ensure that
our sampling was representative, our study included
statuettes from all distinct typological classes, as seen
in Table 1. Small flakes were taken with a fine chisel,
preferably from points on the statuette where a
previous break existed, ensuring negligible damage to
the object.
The stone material used for carving most of the
statuettes, from Cyprus, Samos and Rhodes, is a porous,
chalky-limestone, with a very large amount of microfossils. The material is homogenous with a limited
degree of variation in colour, from creamy-white to light
buff-yellow. They are quite homogenous in texture and
easily workable by sculpturing tools. The strategy for
sampling quarries on Cyprus, Samos, Rhodes and in
Egypt was based on information for their possible use in
the past but also in covering the geological varieties of
limestone resembling the statuettes. In addition to the
quarry samples, archaeological finds of local origin
were also sampled, in order to increase the reliability
of our reference material and ensure that it includes
the majority of the limestone types used in Archaic
sculpturing.
2.1. Cypriote reference material
Most of the ancient Cypriote quarries reported in
the bibliography are situated near the archaeological
sites and were used for the production of building
materials. The vast majority of these quarries, however,
have been used during either Classical or Hellenistic
to Roman period, while the few Archaic quarries
reported (Afentrika etc.), produce very different material
from that of our statuettes [7].
During a careful survey of the Pachna and Lefkara
chalks (Late Cretaceous to lower Miocene and Miocene
period respectively), it became evident that the former
could provide homogenous blocks of a soft creamy
chalk suitable for carving. The Lefkara chalks on the
other hand are generally more brittle, fractured and
harder to carve. The area around ancient Idalion (recent
village of Dali, Fig. 3) has been suggested as the source
of the raw material for these statuettes [8,15] on the
basis of its softness and workability. More recently,
Xenophontos [35] has traced chalk statuettes from
Amrit in Syria (Fig. 2) to the nearby Kossi–Lympia
quarry area based on micro-paleontological analysis.
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K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
Table 1
Origin and description of the samples consisting the reference groups
Laboratory
code
Quarry location
Stone type
Creamy white, fossiliferous, chalky limestone
CY2-1
CY2-2
CY2A-1
CY2A-2
CY3-1
CY3-2
LY1
LY2
LY3
LY4
LY5
LY6
LY7
LY8
LY9
CYA1
CYA2
CYA3
CYA4
CYA5
CYA6
CYA7
CYA8
CYA9
CYA10
CYA11
CYA12
Nicosia–Larnaca motorway, near Kossi village,
Quarry 1 (the northest one)
Nicosia–Larnaca motorway, near Kossi village,
Quarry 1 (the northest one)
Quarry 2
Quarry 2
Quarry 2
Quarry 2
Quarry 3
Quarry 3
Quarry 6
Quarry 7
Quarry 5
Quarry 4
Quarry 8
Quarry 9
Quarry 10
Quarry 11
Quarry 12
Large Archaic statue—Nicosia Museum court yard
Large Archaic statue—Nicosia Museum court yard
Large Archaic statue—Nicosia Museum court yard
Large Archaic statue—Nicosia Museum court yard
Large Archaic statue—Nicosia Museum court yard
Large Archaic statue—Larnaca Museum, Achna Temple
Large Archaic statue—Larnaca Museum, Achna Temple
Large Archaic statue—Larnaca Museum, Achna Temple
Large Archaic statue—Larnaca Museum, Athienou
Large Archaic statue—Paphos Museum
Large Archaic statue—Paphos Museum
Large Archaic statue—Palaepaphos Museum
Samos
SM2
SM4
SM5
SM7
SM8
SM9
SM10
SM11
SM12
SA16
SA17
SA18
SA19
SA20
Monastery of Panagia Spiliani
Katarouga—Koutsogianni (1nd cave)
Katarouga—Koutsogianni (2nd cave)
Katarouga (cave at Ag. Ioannis level)
Katarouga (on the road to Ag. Ioannis)
Aspros Kavos (1st cave)
Aspros Kavos (1st cave, outside)
Aspros Kavos
Aspros Kavos (cave at the beach)
Architectural frieze (Heraion)
Column drum (Heraion, 733)
Column drum (Heraion, 733A)
Column drum (Heraion, 734)
Column drum (Heraion, 735)
Greyish, compact, marly limestone
Greyish, hard, marly limestone
Greyish, compact, marly limestone
Greyish, compact, marly limestone
Greyish, compact, marly limestone
White-pinkish, compact, marly limestone
White-pinkish, compact, marly limestone
White-pinkish, compact, marly limestone
White-pinkish, compact, marly limestone
Compact, marly limestone
Brown, grainy, marly limestone
Greyish, compact, marly limestone
Orange patina, compact marly limestone
Brownish, compact, marly limestone
Egypt
AL11
AL22
AL24
AL25
AL26
AL27
AL28
Cidatel Qait Bay
Formation of the Sphinx
Arabic Quarries Company, 23 km from Cairo (Giza)
Mokhatam—Citadel of M. Ali
Mokhatam—Citadel of M. Ali
Cheops’ Pyramid
Copenhagen Museum, False door (Saqqara Ptah-Uash, 5129)
Yellowish, dense, homogenous, oolithic limestone
Yellowish, dense, homogenous, oolithic limestone
Yellowish, grainy, oolithic limestone, fragmented texture
Yellow, dense, homogenous, oolithic limestone
Yellow, dense, homogenous, oolithic limestone
Yellow, dense, homogenous, oolithic limestone
Yellow, dense, homogenous, oolithic limestone
Cyprus
CY1-1
CY1-2
Around twenty quarries, most now abandoned, are
present in the Kossi—Lympia area on both sides of the
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Yellowish, fossiliferous, chalky limestone
Yellowish, fossiliferous, chalky limestone
Yellowish, fossiliferous, chalky limestone
Nicosia–Larnaca highway and roughly 15 km northwest of Larnaca (Fig. 3). The area has been known for a
K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
1019
Fig. 3. Simple sketch of Cyprus with sampling locations.
long time as the source of the “Larnaca chalk” or of
“Petra tis Athienou” [32]. No traces of ancient quarrying
activity were found.
Apart from the quarry samples, another group of
twelve samples, taken from large Archaic statues, was
used as a reference material. These statues exhibited at
the museums of Nicosia, Larnaca and Paphos are expected to be of local Cypriote origin due to their size and
stylistic characteristics. The description of the samples is
given in Table 1 (no museum codes are available).
All Cypriote samples can be characterised as finegrained creamy white chalks with foraminifera shells
(globigerinids), easily seen with a hand lens [35], giving the
rock a “pock-marked or burst-bubbled” appearance [15].
2.2. Samian reference material
Our sampling on Samos was finally concentrated in
the south-eastern part of the island around the modern
town of Pythagoreion and the site of Aspros Kavos
(Fig. 4). The surveyed geological formation of the area,
corresponding to Neogene deposits of the so-called
“Lower Series of Mitiline Basin Formation” [27], has
been extensively exploited from antiquity until today for
building and decorative purposes. All the Samian quarries reported below, show clear evidence of extensive
quarrying, i.e. tool marks, exploitation that forms caves
and thousands of tons of waste material creating
extended artificial hills. The material quarried in such
quantities, is a whitish to white-yellowish, porous but
quite compact marly limestone of the Upper Miocene
(about 8 Ma), bearing a small amount of microfossils.
The overall texture and appearance are similar to those
of the statuettes but some slight differences can be
observed in certain cases. They appear slightly darker in
colour and in certain cases show a higher degree of
crystallisation.
The sampling sites are given in Fig. 4 and include
quarries near and around the ancient and modern city of
Pythagoreion, on the hills above the Heraion, at the site
of Aspros Kavos (near the coastal line), at the site of
Katarouga and above Moni Spilianis near Pythagoreion
(underground cave-quarries). Twenty-five samples were
collected, but only those showing a certain similarity in
colour, density, compactness and workability with the
archaeological ones were analysed and described in
Table 1.
Five large architectural pieces from the Heraion (a
frieze and four column drums, Table 1) were also
sampled and the material was included in our Samos
reference group.
2.3. Rhodian reference material
Our systematic fieldwork on the island of Rhodes
(Fig. 5, Monte Smith, Paradisi, Kolimbia, Panagia
Tsampika, Haraki, Archagelos, Lardos, Lindos,
Katavia) showed that Rhodian limestones are generally
more fragmented, less compact and present different
coloration from the Cypriote and Samian ones (dark
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K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
Fig. 4. Simple sketch of Samos with sampling locations.
yellow with dark stains or veins). The examination of the
samples revealed a great heterogeneity between different
quarrying areas, concerning not only the colour and the
compactness but also the inclusions (quartz etc) and the
presence of microfossils. As a result we conclude that
none of the limestone quarries sampled on Rhodes can
produce the high quality material of the statuettes. For
this reason the results of the analysis of the collected
material (31 samples) will not be presented here.
Samples were taken from a huge modern quarry of
Mokhatam area, near the Citadel of M. Ali (nummulitic
limestone, 2 km south of Cairo), from the modern
quarries of the Arabic Quarries Company (23 km south
of Cairo) and the formation of the Sphinx and Cheop’s
pyramid. A sample from a False door (Saqqara PtahUash, 5129) exhibited in the Copenhagen Museum was
also included in our reference material.
2.4. Egyptian reference material
3. EPR results for the reference material
The region of the wider area around the ancient site
of Naucratis, in the sanctuaries of which Cypriote-type
statuettes were found [8] (now in The British Museum)
was searched in detail, both physically and from geological maps but no limestone outcrops or quarries were
found. The nearest quarries, which have been identified
as ancient [10,18], are across the coast of Alexandria and
near the city of Cairo (Fig. 6). A systematic sampling of
the quarries near the city of Alexandria was done up to
40 km across the coastal zone (Fig. 6, Mex, Dikheila,
El Agami, Abu-Jusef, Abu-Sir, Burg El Arab). The
material sampled though (20 samples), is a very distinct,
oolitic limestone, composed of small spheres or ellipsoidal aggregates (ooliths), about 0.25 to 2.0 mm in diameter. This type of limestone does not resemble at all the
material of the studied statuettes and, as such, their EPR
analysis results will not be presented here.
Going south of Alexandria along the Nile valley and
towards Cairo the limestone appears similar to the
material of the statuettes. Compact, homogenous, finegrained, marly limestone is the most typical appearance.
According to the EPR spectrum recording protocol
followed in the Laboratory of Archaeometry for marble
provenance investigation [29], three different magnetic
field regions were recorded, which will be described in
detail below: the Mn2+ sextet, the low field region (Fe3+
peaks) and the region around g=2.0000. The results are
given in Table 3.
3.1. Mn2+ sextet
The most prevailing feature in a limestone EPR
spectrum is the six double lines originating from the
Mn2+ ions substituting for Ca2+ in the CaCO3 lattice. A
typical Mn2+ sextet of a limestone sample can be seen
in Fig. 7a. This spectral structure is common in polycrystalline carbonates (marble, calcite etc) and has been
discussed by several authors [5,17]. The intensity of these
lines depends on the concentration of Mn2+ in the
carbonate phase and is used for discriminating between
ancient quarries in marble provenance investigation
[1,5,29].
K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
1021
Fig. 5. Simple sketch of Rhodes with sampling locations.
3.2. Fe3+ in carbonate and non-carbonate parts of
limestone
In the low magnetic field region (Fig. 7b) four peaks
at g=14.25, 5.9, 3.7 and g=2.9 are observed in all
carbonate (calcitic) rocks (marble, limestone, dolomite).
They are attributed to Fe3+ substituting for Ca2+ in the
calcium carbonate lattice [23,28]. The peak at g=4.3
corresponds to a strong component due to Fe3+ in
orthorhombic symmetry (silicates and oxides, [19]) and a
weak one due to Fe3+ in the carbonate lattice.
3.3. Defects and radicals in the region around g=2.0000
This spectral region shows great differences between
quarrying areas. The structure of the spectrum, i.e. the
number of the peaks occurring in this region, the peak
intensity ratios, their g-value and width, are characteristic for each limestone formation. Variations in Mn2+
and Fe3+ and other defect concentrations, range from
20 to 45% in the same formation, while the spectrum
structure is identical throughout the formation (checked
in 17 samples collected from the Pachna formation at
Kossi–Lympia, Cyprus, Table 3). Besides, this spectral
structure is characteristic for each quarry. Analysis has
been done on over 150 limestone samples from different
areas, collected from ancient or recent quarries exploited
for building or decorative purposes. Comparison of the
spectra from different quarries in Albania (Butrint),
Thrace (ancient Mesimvria), Fokida (Hossios Loucas),
Rhodes, Samos, Cyprus and Egypt shows that small or
large-scale differences exist, while the cases of very close
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Fig. 6. Simple sketch of Egypt with sampling locations.
similarities are very rare. The region around g=2.0000
will be thus presented for each quarry separately.
3.4. Cyprus
All quarry samples from Cyprus show the same
spectral structure seen in Fig. 8. The peaks at g=2.0057
and g=2.0036 together, which prevail in this spectrum
are typically produced by foraminifera. A foraminifera
spectrum is seen in Fig. 8 and is characterised by three
peaks: at g=2.0057 and g=2.0036, which have been
attributed to SO
2 and SO3 radicals respectively and at
radicals [2,3,6]. The
g=2.0006 correlated with CO
2
signals at g=2.0036 and 2.0006 grow on -irradiation
and therefore can be used in EPR dating [26,33]. The
Cypriote reference material shows the peaks at g=2.0057
and 2.0036 in high intensities indicating the presence of
foraminifera in large concentrations. Foraminifera are
amoeba-like, single-celled protists, that can be found as
microfossils in sediments as old as the earliest Cambrian
(about 545 million years ago). The majority of the
fossilised forms secrete a shell (or test) of calcium
carbonate, in various shapes, ranging from 0.1 mm to
1 mm in size. Almost all foraminifera species are marine
and they can be divided in two groups, planktonic
(marine floaters), and benthic (sea floor dwellers). In our
case the foraminifera are planktonic [35]. Many of these
species are geologically short-lived or only found in
specific environments and therefore can be used as a
paleontological tool for determining the geologic age
and the formation environment of the rock. The peaks
observed by EPR spectroscopy are created by paramagnetic centres existing in the foraminifera shell (calcium
carbonate).
K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
1023
a)
3100
3200
3300
3400
3500
3600
Magnetic Field (Gauss)
g=14.25
b)
g=2.9
g=5.9
Fig. 9. EPR spectra in the region around g=2.0000: (a) SAMOS A type
(Moni Spilianis or Aspros Kavos) and (b) EGYPT type.
g=4.3
g=3.7
500
1000
1500
2000
2500
Magnetic Field (Gauss)
Fig. 7. Typical EPR spectrum of limestone: (a) Mn2+ sextet and (b)
Fe3+ peaks.
Fig. 10. EPR spectra in the region around g=2.0000: SAMOS B type
(Katarouga) compared to a statuette.
3.5. Samos
Fig. 8. EPR spectra in the region around g=2.0000: Cypriote chalk
compared to a foraminifera sample.
Samos shows two different types of spectra: one for
samples from Moni Spilianis, Aspros Kavos and the
architectural pieces from the Heraion (SAMOS A, Fig.
9) and a second one for those from Katarouga (SAMOS
B, Fig. 10). Both spectra are characterised by a low
intensity peak at g=2.0036 and a peak at g=2.0052. The
peak at g=2.0057 is absent implying the absence or very
low concentration of microfossils. We have to note here
that the peak at g=2.0052, should not be confused with
the previously mentioned at g=2.0057 because the first
one is axial and the second isotropic [6].
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Table 2
Codes and description of the analysed statuettes
Museum code
Object description
Stone type
Nicosia Museum
Agilades 1938/V—10/1
Amathus Tunnel
Statuette found at Kakopetria
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Samos, Vathy Museum
A 2286
A 2277 (T 794)
A 2279
A 2278
A 2280
A 2283
A 2276
A 2260
–
A 2319
A 2326
RA
A 597
A 613
Ram offerer
Kouros of Greek type
Sphinx
Lion tamer
Lion
Enthroned figure
Male votary carrying a ram
Kouros of Greek type
Falcon
Sphinx
Falcon
Ram
Dressed kouros
Egyptian figuring of a standing man
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Yellowish, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Yellowish, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Greyish, compact, marly limestone
Copenhagen Museum
(found on Rhodes)
10.451
10.450
10.445
10.434
10.427
10.440
10.425
10.452
10.438
10.439
10.429
10.446
10.456
10.423
10.453
11.327
11.328
11.329
12.216
Sphinx
Sphinx
Enthrone beardless figure
Kouros (?) head
Kore with lotus flower
Ram offerer
Kouros
Male mermaid playing the lyre
Standing male votary carrying an animal
Standing male votary with a he-goat
Kore
Enthroned male figure
Lion
Standing male figure
Lion
Flute player
Sphinx
Falcon
Standing male figure in himation
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Yellowish, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Yellowish, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
Creamy white, fossiliferous, chalky limestone
3.6. Egypt
Egypt is characterised by a relatively low intensity
peak at g=2.0036 and both peaks at 2.0057 and 2.0052
(EGYPT, Fig. 9).
4. EPR results for the statuettes
All statuettes (except for A613, Lab. Code SA15)
show the same spectral structure in the region around
g=2.0000. This resemblance indicates the same origin
of the carved limestone. The peaks at g=2.0057 and
g=2.0036 occur together, indicating the presence of
foraminifera. The resemblance of the statuette spectra
with the spectra of Cyprus samples (Figs. 8 and 10) is
striking. Besides, the intensity of the peak at g=2.0036
is very high in both spectra implying similar, large
foraminifera concentrations (Tables 2 and 4).
The spectrum of SA15, an Egyptianising statuette, is
similar to that of the quarry samples originating from
Samos, Katarouga region (SAMOS B, Fig. 10). This
indicates that it could be made of local Samian limestone. However, certain similarities occur also with the
spectrum EGYPT (Fig. 9). We can thus conclude, that
SA15 originates most probably from Samos but an
Egyptian origin cannot be entirely ruled out.
5. Quarry separation plots
Table 3 shows a selection of different parameters
measured from the EPR spectra for all the samples
from the Cyprus, Samos and Egypt reference groups
K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
1025
Table 3
EPR spectrosopy results for the quarry samples
Laboratory code
Mn2+ (r.u.)
Cyprus
CY2-2
CY1-1
CY1-2
CY2A-1
CY2A-1
CY2-1
CY3-1
CY3-2
LY1
LY2
LY3
LY4
LY5
LY6
LY7
LY8
LY9
CYA1
CYA2
CYA3
CYA4
CYA5
CYA6
CYA7
CYA8
CYA9
CYA10
CYA11
CYA12
1015
650
785
1040
1006
688
830
1376
789.0
1024.0
992.0
681.0
1104.0
830.0
728.0
1156.0
1170.0
1244
1052
832
1410
1236
879
1270
1076
936
210
414
969
Samos
SM2
SM5
SM4
SM7
SM8
SM9
SM10
SM11
SM12
SA16
SA17
SA18
SA19
SA20
Egypt
AL11
AL22
AL24
AL25
AL26
AL27
AL28
Fe3+ (r.u.)
g=2.0057 (r.u.)
g=2.0052 (r.u.)
g=2.0036 (r.u.)
44.4
22.6
27.0
3.0
48.1
25.3
28.6
54.0
31.8
25.8
33.8
27.4
43.0
37.8
35.0
26.0
27.3
67.5
59.4
52.0
84.8
59.4
41.2
84.0
49.4
76.8
17.0
57.2
46.9
6.0
7.2
8.0
20.6
18.0
10.1
8.8
12.7
10.0
19.3
9.2
7.4
13.0
7.4
17.0
13.0
8.0
13.7
20.0
19.0
8.0
11.2
19.0
23.0
13.7
13.7
3.5
15.0
17.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.3
0.0
0.0
131.0
125.0
113.0
273.0
250.0
182.0
133.0
176.0
154.0
224.0
142.0
112.0
124.0
138.0
250.0
234.0
123.0
200.0
202.0
164.0
108.0
146.0
210.2
294.0
192.0
200.0
54.0
275.0
189.0
888.0
154.0
204.0
342.0
540.0
149.0
272.0
608.0
466.0
200
228
1500
1825
1008
96.2
35.6
47.3
14.0
15.2
29.8
84.8
65.6
84.8
160.0
186.0
30.0
48.3
37.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.7
4.8
2.6
2.4
3.7
1.6
3.1
1.7
1.5
4.8
4.2
0.4
0.3
1.0
19.0
8.5
4.8
14.0
35.0
1.1
4.2
0.2
0.2
28.6
18.0
0.1
0.1
0.1
155.0
407.0
325.0
305.0
123.0
86.0
175.0
14.4
20.0
6.2
12.5
10.0
5.0
3.7
0.8
1.5
1.0
1.0
1.0
1.0
1.7
5.6
6.2
6.2
4.8
4.3
3.0
6.9
0.0
41.0
89.0
6.3
7.4
9.0
8.7
(Table 4). In the following, we tried to find an easy and
tangible depiction of the previously described differences
between groups. In order to illustrate this separation,
Fig. 11 was drawn. The difference between the intensities
of the peaks at g=2.0057 and 2.0052 was used for the
vertical axis while, the intensity of the peak at g=2.0036
was used for the horizontal axis. The ellipses shown on
Figs. 11–13 were drawn with 95% statistical significance.
These ellipses therefore define a parameter field for each
region: the “Cyprus”, “Samos” and “Egypt” fields. As it
1026
K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
Table 4
EPR spectrosopy results for the statuettes (NC=Nicosia, SA=Samos, LI=Lindos, VR=Vroulia)
Laboratory code
Museum code
Mn2+ (r.u.)
Fe3+ (r.u.)
g=2.0057 (r.u.)
g=2.0052 (r.u.)
g=2.0036 (r.u.)
NC1
NC2
SA1
SA2
SA3
SA4
SA5
SA6
SA7
SA8
SA9
SA10
SA12
SA13
SA14
SA15
LI1
LI2
LI3
LI4
LI5
LI6
LI7
LI8
LI9
LI10
LI11
LI12
LI13
LI14
LI17
VR1
VR2
VR3
VR4
Agilades 1938/V—10/1
Amathus Tunnel
A 2286
A 2277 (T 794)
A 2279
A 2278
A 2280
A 2283
A 2276
A 2260
–
A 2319
A 2326
RA
A 597
A 613
10.451
10.450
10.445
10.434
10.427
10.440
10.425
10.452
10.438
10.439
10.429
10.446
10.456
10.423
10.453
11.327
11.328
11.329
12.216
1112
1156
1140
1064
1600
770
1248
1938
1031
1473
1049
826
405
660
691
172
875.0
1264.0
1112.0
926.0
754.0
1220.0
1290.0
1270.0
500.0
642.0
738.0
780.0
1280.0
990.0
1021.0
675.0
1120.0
693.0
1070.0
0.1
0.1
48.0
56.2
116.0
38.2
35.7
72.0
57.0
57.5
54.0
58.2
93.7
82.0
45.0
23.8
46.0
46.0
34.0
46.0
24.0
91.0
52.0
70.0
27.0
22.0
40.0
40.0
95.0
33.0
29.0
38.0
36.0
19.0
47.0
4.7
2.2
19.0
20.6
18.6
13.7
10.6
20.0
19.0
17.0
23.0
7.6
18.0
8.0
13.5
0.0
12.5
6.4
5.5
9.5
15.4
9.5
13.0
13.0
8.0
12.1
15.0
9.6
9.0
17.0
17.2
18.5
14.0
23.0
14.0
0.6
0.6
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
17.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
81.2
51.2
166.0
251.0
239.0
115.0
86.4
181.0
273.0
180.0
228.0
98.4
240.0
84.0
215.0
6.6
115.0
84.0
70.0
150.0
231.0
178.0
134.0
182.0
88.0
160.0
190.0
112.0
120.0
233.0
161.5
252.0
213.0
267.0
145.0
160
(50 x g=2.0058) + g=2.0036 (r.u.)
g=2.0057 - g=2.0052 (r.u.)
30
20
10
SAMOS
CYPRUS
0
EGYPT
-10
-20
-50
0
50
100
150
200
250
300
350
g=2.0036 (r.u.)
140
120
100
EGYPT
80
60
40
20
SAMOS
0
-20
-20
20
60
100
140
180
220
g=14.25 (r.u.)
Fig. 11. Quarry separation plot: Stage 1 (ellipses with 95%
significance).
Fig. 12. Quarry separation plot: Stage 2 (ellipses with 95%
significance).
can be seen from this plot, no overlapping occurs
between Cyprus and Samos or Cyprus and Egypt fields.
The “Egypt” group though overlaps with Samos. We
tried to solve this problem, by using another plot with
new complex parameters. Fig. 12 shows a diagram using
the peak with g=14.25 on one axis and a new parameter
K. Polikreti et al. / Journal of Archaeological Science 31 (2004) 1015–1028
g=2.0058 - g=2.0052 (r.u.)
30
20
10
SAMOS
CYPRUS
0
-10
EGYPT
SA15
-20
-50
0
50
100
150
200
250
300
350
g=2.0036 (r.u.)
Fig. 13. Provenance investigation plot for the sampled statuettes
(ellipses with 95% significance).
on the other axis, consisting of an algebraic expression
of simple parameters (50 times the intensity of the peak
g=2.0057 plus the intensity of the peak g=2.0036). The
expression was selected by trial and error (Principal
Component Analysis or Hierarchical Cluster Analysis
did not give satisfactory results). It is obvious from Figs.
11 and 12 that these two plots can discriminate Samian
from Egyptian limestones of the studied type. Some sort
of statistical treatment of the data would certainly be
important if additional potential sources are to be
considered.
The results for the statuettes from Nicosia Museum,
Samos Museum and Copenhagen Museum are plotted
in Fig. 13, using the same parameters as for the reference
groups. All statuettes (except SA15) fall in the Cyprus
field, indicating that these samples are carved in limestone, derived from local Cyprus quarries. Sample SA15
falls in the Samos quarter but not in the field of the
sampled quarries. We have to note here that this sample
was undersized (i.e. less than 200 mg) and the peak
intensities of its EPR spectrum are normally lower than
they should be. We can thus decide on its provenance
using the information given by the spectral structure,
and give Samos as the most probable source and Egypt
as the second, less probable one.
6. Conclusions
Three quarrying areas have been suggested by researchers as possible sources for the Cypriote-type,
limestone statuettes, of the Archaic period distributed in
the Eastern Mediterranean: the Aegean, Naucratis and
Cyprus. We concentrated our provenance investigation
in the statuettes found in the Aegean (Samos and
Rhodes). Thirty-five samples from Cypriote-type statuettes, exhibited in the Museums of Cyprus (Nicosia),
Samos and Copenhagen (originating from Rhodes) were
analysed by EPR spectroscopy. Another 90 samples
1027
were collected from ancient and modern limestone
quarries located in Cyprus, Samos, Rhodes and Egypt
but also from archaeological material of well-known
origin. The results for quarry samples from Rhodes and
the coast of Alexandria, Egypt were not presented here,
as their density, compactness, homogeneity and workability were found insufficient for statuette carving. Our
spectroscopic results exclude also Samos and Egypt
from the possible candidates. Practically all the sampled
Cypriote-type statuettes are made of Cypriote limestone
and more specifically from the “Lympia–Kossi chalk” of
the Pachna formation.
A possible theory for explaining the extended distribution of the statuettes could be that of itinerant craftsmen carrying along their own material. This approach
can certainly explain iconographic differences but it
leaves stylistic differences unexplained and shows practical problems (transfer of large quantities of limestone).
Another explanation would be to accept that Cypriote
artists working in Cyprus and using Cypriote limestone
were producing a particular class of small size statuettes
for export. However, in all cases of this practice known
to date, the exported material kept its own type and
style. Sampling and analysis of statuettes from the
Syro-palestinian coast or Naucratis would give invaluable information on the type of production and
transportation of the material.
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