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VIII/2/2017
INTERDISCIPLINARIA ARCHAEOLOGICA
NATURAL SCIENCES IN ARCHAEOLOGY
homepage: http://www.iansa.eu
Analytical Assessment of Chaltasian Slag: Evidence of Early Copper
Production in the Central Plateau of Iran
Bita Sodaei
a*
, Poorya Kashani
b
a
Department of Archaeology, Varamin-Pishva Branch, Islamic Azad University, Tehran, Iran
b
Archaeological Services Incorporations, Toronto, Canada
1. Introduction
The Iranian Central Plateau is located between the
Southern Alborz Mountain and the Central Iranian desert
and most of the fertile plains are located between the two
above areas (Figure 1) (Fazeli Nashli 2013).
The study of ancient slag material plays a signifcant role in
understanding old metallurgy. The discovery of slag remains
from several sites in the Central Plateau in the 4
th
Millennium
BC has been an important clue to prove the utilization
of smelting processes. These initial developments were
centred on metallurgical-rich regions on the Iranian Plateau
(Pigott 2004): Tappeh Sialk, Tal-I Iblis, Tappeh Ghabristan,
Arisman, Tappeh Zaqeh (Pernicka 2004a; 2004b; Nezafati,
Pernicka 2006), Tepe Hissar and Hassanlo (Thornton
et al.
2009). The existence of slag material in Chaltasian shows
that the site can fall into the same category in the Early First
Millennium BC. Chaltasian is an Iron Age II site, situated
in the Asgariyeh Rural District, Central District of Pishva
County, Tehran Province. The area of this site during the Iron
Age I period was 6500 m
2
(Figure 2).
The frst season of excavation at Tappeh Chaltasian was
conducted by the Varamin-Pishva Branch of the Islamic
Azad University under the supervision of Rouhollah Yousef
Zoshk from September to December 2012 (Yousef Zoshk
2012). The Chaltasian area is located on the western edge of
the city of Pishva, about 5 km away (Figure 3).
GPS coordinates for the site’s centre (datum point) are
N: 3519176, E: 0514135, with a height of 941 metres asl.
and 5 metres above ground level. During the excavation
season, two units were dug out; a 2.5 by 2.5 metre unit in the
central mound and a 1.5 by 1.5 metre unit in the east mound
(Figures 4 and 5) (Yousef Zoshk 2012).
Slag is defned as the vitrifed waste products of pyro-
technological practices. Generally speaking, they are
composed of the glassy, solidifed melt of reacted ore and
gangue minerals, and fuel ash, as well as anything else
which had been added to the smelt (Hauptmann 2007).
Archaeometallurgy can determine old casting methods and
metalworking. It can also give us access to the cultural
and social norms that shaped technological practices and,
perhaps, to the cognitive structures that created such norms
(Smith 1965; 1978). Analytical research on ancient metals
Volume VIII ● Issue 2/2017 ● Pages 137–144
*Corresponding author. E-mail: sodaei@iauvaramin.ac.ir
ARTICLE INFO
Article history
Received: 8
th
June 2017
Accepted: 14
th
November 2017
DOI: http://dx.doi.org/ 10.24916/iansa.2017.2.3
Key words:
slag
archaeometallurgy
Chaltasian
X-Ray Flourescence (XRF)
polarized light
ABSTRACT
This study reports the archaeometallurgical analyses results on six slag remains obtained from
Chaltasian, Iron Age II, in the Central Plateau of Iran, excavated by Islamic Azad University, Varamin-
Pishva Branch. Metallurgical studies were carried out to identify oxides, Ca-rich silicates and metallic
phases in the slag material, using wavelength dispersive X-Ray fuorescence (WDXRF), followed
by an analysis of one sample under the polarizing microscope: plane polarized light (PPL) and cross
polarized light (XPL). Based on the analyses, it has been concluded that these six copper slag remains
have a considerable amount of silica, which had been added to the smelt to increase its fuidity.
Analyses showed a clinopyroxene microstructure in a glassy matrix for fve samples, and a barite
source, from a probable lead-zinc source in limestone, for the other sample. The absence of arsenic in
these copper slags could show a paradigm shift in copper production in this space-time grid. According
to the low amount of slag present on site, on the one hand, and the application of relatively advanced
extraction technology on the other, this research introduces Chaltasian as an Iron Age II small copper
production centre in the Central Plateau of Iran with a locally-developed copper extraction technology.
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Figure 1.
Map of Iran.
Figure 2.
Aerial Photo, Chaltasian (Yousef
Zoshk 2012)
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139
Figure 3.
Topographical Map, Chaltasian
(Yousef Zoshk 2012)
Figure 4.
Chaltasian, central mound (Yousef Zoshk 2012).
is currently a common technique to reach an understanding
of the specialization in alloy production. Elemental analyses
are a type of characterization research in archaeometry. The
comparative assessment of chemical composition can lead
to the determination of metal manufacturing processes.
Archaeologists, therefore, prefer to employ chemical
and physical techniques to identify both the elemental
composition and production technology (Kashani
et al.
2013a). In this work, six slag remains have been analyzed
to obtain information about the quantitative elemental
composition of the slag material and its mineral resources.
2. Theoretical background
The production and use of copper and its alloys on the
Iranian Plateau might have been started in the Neolithic site
of “Ali Kosh” in the south west of Iran, where a rolled bead
of native copper was found (Moorey 1969; Pigott 1999a;
Thornton 2009). The bead from “Ali Kosh” has been dated to
between the 8
th
and 7
th
Millennium BC (Hole 2000; Thornton
2009). It has been further specifed that copper extraction
technology on the Iranian Plateau had local developments
during the Bronze Age (Dyson, Voigt 1989; Oudbashi
et al.
0 120 m
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140
2012). Consequently, at that time, there was a vast variety
of local copper production centres in several regions in west
and central Iran (Thornton 2009). Archaeometallurgical
studies on the copper production centres in Iran have been
reported for several diferent areas, such as: Lurestan,
Kerman, Yazd, Khouzestan, Sistan and the northern part of
the Central Iranian Desert (Pigott
et al.
1982; Hezarkhani,
Keesmann 1996; Emami 2005; Keesmann 2005; Thornton
2009; Roustaei 2012). The technological development of
metallurgy extended through the Central Desert, west and
southwest of the Zagros Range (in some part of today’s Iraq)
to the north and northeast of Iran (Mueller Karpe 1990).
This route might be identifed as the copper path, which still
exists in large parts of the South and Central Iranian Plateau
(Emami 2005; Frame 2010). The association of the mines
with archaeological settlements has always been of great
interest. It is an important criterion for the identifcation of
ancient metallurgical activities and might also be the main
clue for interpretation of analytical results.
The diversity in the applied technologies used in copper-
based alloy production is noticeable through the presence of
lead in bronze artefacts from “Malian” (Pigott
et al.
2003) or
arsenic-bearing copper from “Teppeh Yahya”, the arsenical
coppers from “Talmessi” and “Messkani”, close to “Anarak”
(Pigott 1999b; Chegini 2004), and the arsenic-bearing copper
artefacts from the Late Chalcolithic Meymanatabad, Central
Iranian Plateau (Kashani
et al.
2013a). Analytical studies
of several cupreous artefacts from the Middle Bronze Age
(3000 – 2000 BC) revealed that the main element is copper
with variable amounts of Zn, Pb, As and Sn (Thornton
et al.
2002; Thornton, Ehlers 2003). This diversity in elemental
constituents refects the dissimilarity in the metallurgical
process and in the fabrication of objects, and raises the
question of the source of economic ores. Recent analyses on
slag remains from Arisman proved the application of arsenic
in the smelting process (Kashani
et al.
2013a; Rehren
et al.
2012). Arisman is located close to the important site of Sialk
(3
rd
Millennium BC). This site cannot be considered as the
only metallurgical evidence in the northeastern Iranian
Desert. Based on previous literature, arsenical copper had an
important role on the Iranian Plateau during the 3
rd
Millennium
BC (De Ryck
et al.
2005). We should take into account that
arsenical copper had also been produced by adding arsenical
iron (
i.e.
Speiss) to the copper matte (Marechal 1985); a recent
publication about the appearance of tin bronze in Eurasia
deals with this question – the existence of diferent copper
alloys as accidental metallurgy or even more experimental
metallurgy (Radivojevic
et al.
2013). The disappearance of
the arsenic-copper alloy in some parts of the Iranian Plateau
at the end of the second Millennium BC suggests that this
alloy was a cultural alloy and its production must have had
an old tradition of preference for these objects and was not
purely accidental. One could claim that the beginning of
metallurgy for making a well-known prescribed arsenical
alloy was accidental, but through to the end of the second
Millennium BC this became a tradition in some parts of the
Iranian Plateau. The comparatively advanced technologies of
melting and smelting copper in Iran were established during
the Chalcolithic period in Tal-e Iblis (5500–3200 BC), as
crucibles and slags have been excavated there (Pigott 1999a;
Frame 2012). For this period, the smelting of copper ores
can be identifed through the appearance of impurities in
the extracted metal, such as, for example, arsenic, and this
gives early evidence of the use of arsenical copper (Frame
2012). From an archaeometallurgical point of view, there are
several scientifc reports of a metallurgical interest for the
south central Iranian desert (Hezarkhani, Keesmann 1996;
Matthews, Fazeli 2004; Momenzadeh 2004; Pernicka 2004;
Pigott 1999a; 2004b; Schreiner 2003). However, despite
several researchers having carried out geo-archaeological
surveys on the North Iranian Plateau, some of the ancient
mines located in the middle of the desert still remain
relatively unknown. Furthermore, their importance can be
supposed due to the accessible route to some of the key
Figure 5.
Chaltasian, eastern mound 2
(Yousef Zoshk 2012).
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141
archaeological sites and to the ancient mines in the northern
part of the central desert (Thornton
et al.
2009; Roustaei
2012).
3. Material and methods
In this work, six pieces of slag have been analyzed to obtain
information about their quantitative elemental composition
and minerals. Considering the historical and/or artefcial
signifcance of each artefact, it seems logical to use, as far
as possible, non-destructive analytical methods (Guerra
1998; Kashani
et al.
2013a; 2013b; Sodaei, Kashani 2013)
(Figure 6).
However, slag, which is defned as a glass-like, leftover
by-product, does not belong to the category of archaeological
artefacts. Therefore, it was decided to prepare small samples
in order to reduce the damage to the historical material.
The samples were taken by scalpel from the metal cores
of marginal parts of the slag. Thereafter, they were cleaned
and powdered to 200 mesh in disc form. Two devices
were used to characterize these slag samples. First, XRF,
a well-established method in archaeometry, was applied.
Elemental analyses of the selected slag samples were
carried out by wavelength dispersive X-Ray fuorescence
(WDXRF), model Philips PW 2404, with a detection limit
of ±1 ppm
in Tarbiat Modarres University
, Tehran, Iran.
The tube’s high voltage was 40 kV with a tube current of
30 mA. The samples were also studied under a polarizing
microscope (Olympus BX41 Trinocular Pol) equipped with
a digital Olympus 7.1 Mp C-7070 digital camera, in the
metallography laboratory located in the Cultural Heritage,
Handicrafts and Tourism Organization of Iran. In this case,
samples were analyzed under plane polarized light (PPL) and
cross polarized light (XPL). The technique has a long history
of use in a range of polarizing microscopy applications, from
optical crystallography and petrography to fbre analysis
(Rochow, Tucker 1994). It is also applied in chemistry
for distinguishing between isomorphs and polymorphs.
However, the technique is only useful for those samples with
sufcient optical diferences (Stoiber, Morse 1994).
4. Results and discussion
Based on the results of the XRF analysis, all the studied
samples are mixtures of silica (silicon dioxide) and metal
oxides: Al
2
O
3
, K
2
O, Cl, CaO, Ti
2
O
3
, MnO, Fe
2
O
3
, Cu
2
O,
Na
2
O, MgO, ZnO, SO
3
, PbO, SrO, and BaO (Table 1).
Surprisingly, no traces of arsenic was detected in the XRF
results. The slag samples are quite distinct in their glassy
appearance, high density and sharp edges. A high amount
of silica (silicone dioxide) is noticeable in all six samples
(Table 1). This high percentage (37.93–44.64%) could not be
accidental or unintentional. Silica was added to the smelt in
order to improve the slag’s fuidity. Silica is usually found in
nature as quartz. However, in many parts of the world, silica
is the major constituent of sand (Iler 1979). The percentages
of calcium oxide in the frst fve samples are relatively high.
Therefore, one can claim that in the case of these fve slag
samples, which in their composition have a close similarity, a
calcium-rich silicate had been applied. Regarding these slag
samples’ compositions, this silicate might be a metamorphic
and igneous rock in the pyroxenes group. In this group,
the chemical composition shows a high amount of SiO
2
and FeO, MgO, and MnO. However, pyroxenes show a
variable composition with diferent proportions of elements
by weight (Emami 2014). Major elements in the samples
are Si, Al, Fe, Mg and Ca, and minor elements are Na, K.
Mn, Ti and Zn. Trace elements are considered as indicators
of orogeny and deposits formation. Through the chemical
analyses of the clinopyroxene slag material (samples 1 to 5),
it has been verifed that with increasing content of CaO and
MgO, the sum of SiO
2
and Al
2
O
3
also increased. In addition,
the amount of Fe
2
O
3
depends largely on the sum of SiO
2
and
Al
2
O
3
.
To have a better view, sample 1 was also studied under a
petrographic microscope. Microscopic analysis of polished
Figure 6.
Slag samples found at the site.
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Bita Sodaei, Poory Kashani: Analytical Assessment of Chaltasian Slag: Evidence of Early Copper Production in the Central Plateau of Iran
142
sections can provide information about their petrographic
features, original ore, added gangue materials, fuels used,
and conditions within the smelt. A thin and polished section
was prepared from sample 1 and thinned down to 30 μm.
Studying sample 1 under the petrographic microscope
revealed a clinopyroxene microstructure in a glassy matrix
(Figures 7a, 7b and 7c). The glassy texture in Figures 7a
through 7c demonstrates the over-abundance of crushed,
partially-reacted quartz and feldspar gangue (so-called “free
silica”) in the smelt. In these Figures, the dark colours are
associated with Fe-rich varieties, while titan augite is more
distinctly coloured from brown/pink to violet. In Figures 7a
Figure 7.
a) Plane polarized light (PPL)
(10x), Pyroxene microstructure in sample 1.
b) Plane polarized light (PPL) (10x),
Pyroxene microstructure in sample 1.
c) Cross polarized light (XPL) (10×),
Pyroxene microstructure in sample 1.
d) Plane polarized light (PPL), sample 1,
10X. e) Petrographic microscope , Sample 1,
10X. f) Petrographic microscope, Sample 1,
4X.
to 7c, a dark layer shows Fe
2
O
3
, while this layer is shown in a
white colour in Figures 7d to 7f. Table 1 shows a considerable
amount of Fe
2
O
3
in the samples (8.24–13.51%). The high
percentage of Fe illustrates that the copper was mostly
extracted, while Fe and small amounts of Cu, as parts of the
waste product, remained in the slag. Hence, all the samples
under study are copper slag samples. Depending on their
composition, these copper slag samples could be molten at
about 1300ºC.
XRF analysis proved the presence of lead (Pb), zinc (Zn)
and barium in sample 6. Based on the strong correlation
between lead and barium, a lead ore source with barite
Table 1.
X-Ray Fluorescence (XRF) – results.
SampleNa
2
OMgOAl
2
O
3
SiO
2
Cl
K
2
OCaOTi
2
O
3
Fe
2
O
3
Cu
2
OZnOSO
3
SrOBaOPbOMnO
1
1.552.557.7844.640.252.6026.250.569.413.160.140 00 01.11
2
2.612.328.1144.35 0.472.6426.530.769.11 3,05 0 0 0 0 00 .05
3
3.762.457.5943.04 1.953.9124.470.828.24 2.95 0 0 0 0 00.82
4
3.912.517.7141.081.923.9223.580.898.9 3.95 00.84 0 0 00.79
5
4.892.187.8641.58 1.942.8524.320.968.84 3.200 00.49 00 0.89
6
3.87 0 037.930.582.787.990.5913.514.6216.46 00 5.156.350.17
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143
(BaSO
4
) could be suggested for this sample. In fact, barite
commonly occurs in lead-zinc veins in limestones (Rubin
1997). Barite is a mineral consisting of barium sulfate. It
is generally white or colourless, and is the main source of
barium (Hanor 2000).
5. Conclusion
This study shows that all the samples under study are from
copper slag material. In copper production, Fe was not
extracted. This element together with the remaining Cu,
Si, Al, Mg, and Ca are major elements in these samples of
copper waste products. The minor elements found are Na,
K. Mn, Ti and Zn. The considerable amount of silica, which
can be seen in the XRF results and with the petrographic
microscope, indicates the intentional process of adding silica
to the smelt in order to increase fuidity. The XRF results,
together with the photos taken under the plane polarized light
(PPL) and cross polarized light (XPL) microscope, prove
that the frst fve samples are calcium-rich silicates with a
clinopyroxene microstructure in a glassy matrix. Based on
the XRF results, sample 6 difers from the other fve samples:
regarding its composition, this sample has a probable lead-
zinc ore source with barite (BaSO
4
). The adding of arsenic to
copper, which was common during the Chalcolithic Period
and Bronze Age in this region, was not happening here in
Chaltasian. This could show a paradigm shift in copper
production in Iron Age II in this part of the Central Iranian
Plateau. The slag material under study, as waste products of
pyro-technological practices, can provide sufcient evidence
for an Iron Age II copper production and extraction at this
site. The application of diferent techniques, as discussed
in this study, makes it possible to elucidate knowledge of
the copper-extracting technologies that metalworkers of
that time possessed. However, based on the low quantities
of slag material present at Chaltasian, this production did
not occur on a large scale during the Early First Millennium
BC. Therefore, during this period of time, one can say that
Chaltasian fell into the category of small copper production
centres in the Central Plateau of Iran.
Acknowledgments
This research was supported by Dr. Yousef Zoshk, who
kindly helped us in the analysis and study of the Chaltasian
slag samples. We would also like to extend our thanks to
Mr. Beheshti, Metallurgical Laboratory, Cultural Heritage,
Handicrafts and Tourism Organization of Iran for his
valuable comments on the polarizing microscope results.
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