Materials Characterization 158 (2019) 109957

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Materials Characterization
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Microstructure and chemical composition of a Sardinian bronze axe of the T

Iron Age from Motya (Sicily, Italy)
Martina Bernabalea, Lorenzo Nigrob, Daria Montanarib, Ana Maria Niveau-de-Villedaryc,
Caterina De Vitoa,∗
a
Department of Earth Sciences, Sapienza University of Rome, P.le Aldo Moro 5, 00185, Rome, Italy
b
Department Italian Institute of Oriental Studies - ISO, Sapienza University of Rome, Circonvallazione Tiburtina 4, 00185, Rome, Italy
c
Departamento de Historia, Geografía y Filosofía, Universidad de Cadiz, Avda. Dr. Gómez Ulla, 11003, Cádiz, Spain

ARTICLE INFO ABSTRACT

Keywords: A bronze axe of the Iron Age found in Motya (Sicily, Italy), in prehistoric strata dating from the 10th century BC
Sardinian axe (before the foundation of the Phoenician colony), has been characterised using Scanning Electron Microscopy
Motya (SEM-EDX), X-ray diffraction (XRD) and Electron Microprobe Analysis (EMPA). The axe was studied using
SEM-EMPA-XRD micro-and invasive analyses, aiming to explore microstructure, corrosive process and to acquire quantitative
Alloy composition
chemical analysis. The results revealed that the axe is composed by a leaded-Cu-Sn alloy. The external layer is
Microstructure
affected by a moderate porosity, decuprification and destannification processes, and Pb enrichment. The X-ray
Corrosion
maps pictured the distribution of Cu, Pb, Sn, As, Cl, S and O and showed the features of the matrix, containing
globules of Pb with different size. The corrosion products were examined using X-ray diffraction (XRD), that
revealed the occurrence of cuprite (Cu2O), cassiterite (SnO2), laurionite (PbClOH), cerussite (PbCO3), litharge
(PbO), anglesite (PbSO4) and plumbonacrite (Pb5O(OH)2(CO3)3). The matrix is composed by Cu 86.9–95.4 wt%
and Sn 2.8–6.9 wt% with arsenic impurities (0.6–1.3 wt%).

1. Introduction of the Mediterranean.

Motya before the establishment of a proper Phoenician colony was a
major berthing place in the sea-routes across the Mediterranean.
Levantine traders and seamen navigated across the “Middle Sea” [1]
and the routes to metals, connecting the great Mediterranean islands,
from Cyprus to Sardinia and the Iberian Peninsula through Crete, Malta
and Sicily, are reflected in finds distribution all over the Mediterranean
basin [2,3]. This flows of artefacts from the East continued with
Phoenician traders, prospectors and colonists in the first centuries of the
1st millennium BC.
During the last centuries of the 2nd and the beginning of the 1st
Millennium BC [4], the role of the Phoenicians as the main traders
entangled the populations of Western territories such as Italy, Iberian
Peninsula and other regions [4].
Phoenicians founded in Western Sicily the colonies of Motya, Solus
and Panormos (8th–7th century BC) promoting very important im-
provements on metal technology [5,6].
The relatively big island of Motya (45 ha) facing the western tip of
Sicily (Capo Boeo, nowadays the city of Marsala), was a strategic har-
bour and an ideal point of connection of navigation routes at the centre
Motya has provided abundant archaeometallurgical material from
different areas of the island, especially from the necropolis [7], the city-
walls, the Tophet and the dwelling quarters. However, only a few ar-
chaeometric studies were made up to now on such class of artefacts. No
data at all are available for the time span to which this axe is dated –
that is just before the foundation of the colony (Motya IIIB, 1100-900
BC).
The study of the axe helps us to gain a better comprehension of
technology and provenance of metalworks found in Sicily between the
end of the 2nd and the beginning of the 1st millennium BC.
Up to now, large-scale analyses in Mediterranean have been carried
out on Greek and Etruscan materials [8,9] and on Iberian and Portu-
guese metal artefacts [10–14]. Recent studies show that during Late
Bronze Age (LBA) metallic artefacts from European regions around the
Mediterranean Sea, i.e., Iberian Peninsula, Sardinia, Sicily, Italy and
Greece, were produced using the technology of binary bronze [15,16];
whereas metal works from Atlantic Europe, such as the British Isles,
Western France and North-Western Iberia, were made mainly of leaded
bronzes [17].
In particular, studies of Bronze and Early Iron Age bronze artefacts

∗
Corresponding author.
E-mail address: caterina.devito@uniroma1.it (C. De Vito).

https://doi.org/10.1016/j.matchar.2019.109957
Received 25 July 2019; Received in revised form 7 October 2019; Accepted 7 October 2019
Available online 09 October 2019
1044-5803/ © 2019 Elsevier Inc. All rights reserved.
M. Bernabale, et al.
from Italy and Sicily have shown that before the Early Iron Age, lead
had been employed for cast on parts of fibulae as early as in the Late
Bronze Age [18], but it was present in trace amounts in the majority of
bronzes, with amounts more than 1% lead.
Only from the Early Iron Age (1200-900 BC) bronze artefacts re-
vealed a definite increase in lead content, higher than 2%. This seems to
suggest a voluntary addition of lead, which improves the fluidity of the
molten bronze alloy and rises the temperature of the solidification
range, in order to facilitate the casting of larger or of a certain com-
plexity objects [11].
However, there were differences in metallurgical techniques and tin
content throughout the Mediterranean area. For instance, Italian
bronzes contain similar tin percentages (∼6 wt% Sn), except for
Sardinian bronzes in which Sn range from 8 to 9 wt%. Iberian alloys
present a high content of Sn due to extensive ore deposits of such metal
in the area. Some examples can be found in the artefacts from El
Palomar (12.6 ± 6.2 wt% Sn), Medellin (11.7 ± 7.5 wt% Sn) and El
Risco (11.8 ± 5.4 wt% Sn) [12].
Differences between these metallurgical practices are presumably
related to the abundance and supply of tin or to the recycle of bronze
scraps. In fact, during the melting operation tin undergoes a pre-
ferential oxidation which leads to a depletion of Sn in the alloy [11].
The corrosion of Cu based alloy is associated with decuprification
and destannification processes, which can occur for several micron in
depth, depending on severe conditions in burial environments; there-
fore, to evaluate the degree of corrosion it is necessary to analyse cross
section of samples “from rim-to core” [19].
A very limited number of studies about pre-Phoenician and
Phoenician metal artefacts and their corrosion process are reported and,
above all, these contributions are based on the use of qualitative data or
semi-quantitative data [20,21].
Nowadays, the most common techniques applied to investigate
ancient alloys are Scanning Electron Microscope [22] and X-Ray
Fluorescence [23]. Fourier Transform Infrared Spectroscopy (FTIR) and
μ- Raman Spectroscopy give exhaustive information on the corrosion
products of the surface, useful for restoration and conservation
[24–27].
Recent studies explore the performance of the application of the
Voltammetry of Immobilized Micro Particle (VMP) and other electro-
chemical techniques, which help to know the state of conservation of
the patina and to identify the corrosion products [28–31].
Some authors applied non-destructive and micro-invasive techni-
ques to investigate both corroded and not-corroded alloy composing
samples [27,32–34]. However, the error related to major and minor
elements is too high to be helpful to give fully exhaustive answers to
archaeological issues.
The most suitable way to investigate the corrosion process in deep is
to analyse cross sections of samples. Therefore, in some rare cases,
destructive analysis should be preferred to evaluate the composition of
not-corroded metal artefacts [19].
Recently, EMPA technique was used, obtaining quantitative che-
mical analysis for Roman alloys [19].
The main challenges in studies concerning valuable samples was
based on bringing out new information with non-invasive, or at least,
micro-destructive analysis [19].
However, it is clear that surface analyses cannot give proper or
complete answers in some critic questions as technologies of manu-
facturing and post-manufacturing processes, raw materials and prove-
nance. In order to answer to all these questions, it seems necessary to
apply a multi-analytical strategy that combines non-invasive, nano-in-
vasive and destructive techniques [19].
The aim of this work is to characterize the composition and the
metallurgical techniques of the Sardinian bronze axe named
MCM.18.200, comparing also the results with those obtained for coeval
2
Materials Characterization 158 (2019) 109957
artefacts from different areas of the Italian peninsula and from other
European contexts (e.g. Sardinia and Iberian peninsula) in order to
investigate whether or not there are differences in the composition of
these artefacts.
The axe here studied belongs to an Iberian typology, even if it was
produced in Sardinia and, brought to light at Motya. The opportunity to
perform invasive sampling allows us to obtain valuable information on
the manufacturing process and post-manufacturing history. This con-
tribution can provide new insight about the skill of the local artisans
and the relationship concerning cultural exchange and the trade of raw
materials between Motya and other Mediterranean areas.
Archaeological metal-artefacts with very similar shape and typology
can differ in alloying composition as suggested by [35]. In addition, the
lack of correlation between metal composition and spatial and temporal
distribution of types seems to depend on the availability of metal or
may be due to different metalworking workshops [36].
Nonetheless, the identification of the provenance of metal used to
produce metal weapons found in Motya is made difficult due to the
central location of this island in the Mediterranean Sea, with material
elements ascribable and coming from the Sicilian autochthonous pre-
historic, Phoenician-Punic and Greek cultures.
2. Archaeological context
Since the first half of the 2nd Millennium BC, before the Phoenician
stable settlement on the island, Motya was a landing place for Levantine
seamen on the route to Sardinia and its mines. A prehistoric village
occupied the acropolis on the eastern shallow mound of the island, with
dwelling and communal building sparse over an area of about 10 ha
[37]. Around 800 BC, a group of Phoenicians founded the colony which
prospered and became a city within the first quarter of the 7th century
BC [38].
Since this period, the Phoenician centre had important commercial
relationships with the motherland and the other colonies of the central
and western Mediterranean fully included in the exchange network
arisen on the routes to metals [39].
Since 2002, the Archaeological Expedition to Motya of the
University of Rome “La Sapienza”, directed by Lorenzo Nigro, resumed
the excavations on the island [40], and provided hundreds of Phoeni-
cian artefacts in their specific stratigraphic archaeological context [41].
The axe here analysed was unearthed in the 2018 season of ex-
cavations in a stratigraphic sounding beneath the structures of the
House of Mosaics [38,40]. The axe was embedded in a burnt layer
buried under several strata of the Phoenician colony, attributed to
Period Motya IIIB, dating from about 1100 to 900 BC [42]. The ap-
proximate date of the context should be the 10th century BC.
3. Materials and methods
3.1. Materials
In this work, the attention was focused on a bronze two-looped
socketed axe known from specimens found in Sardinia (see below)
dating back to the final phase of the 2nd millennium BC [43], and to the
very beginning of 1st millennium BC (more precisely 12th-10th century
BC [44]) (Fig. 1). The type is Iberian ancestry [45–48], falling within
the formal classification of types 41 and 42 of Monteagudo [49]. It can
find convincing comparisons in Sardinia, at the site of “Monte Sa Idda
de Decimoputzu” (Cagliari) [50], and with an axe with middle grooves,
found on the Acropolis of Lipari [51]. This kind of weapons is usually
employed in ritual and cult contexts, such as deposits and treasures and
is technologically characterized by the presence of surface lead globules
functional to facilitated loops.
M. Bernabale, et al.
3.2. Methods
Microstructure and semi-quantitative chemical analyses were per-
formed by scanning electron microscopy using a FEI-Quanta 400 (SEM-
EDS) instrument, operating at 20 kV, equipped with X-ray energy-dis-
persive spectroscopy (Department of Earth Sciences, Sapienza
University, Rome, Italy). SEM imaging was collected both in the sec-
ondary electron (SE) and back scattered electron (BSE) modes. Energy-
dispersive X-ray spectroscopy (EDS) spectra and X-ray maps were also
acquired to highlight the elemental distribution through the sample,
aiming to disclose enrichments and/or depletion of the elements from
rim to core following corrosion process and metal exsolution at low
temperature.
In order to evaluate the mineralogical composition of the patina,
XRD analysis was directly performed on the surface of the object, using
a Bruker D8 FOCUS diffractometer, with Cu Kα radiation on a Bragg-
Brentano θ/2θ geometry, equipped with a Si(Li) solid-state detector,
Sol-X (Department of Earth Sciences, Sapienza University of Rome,
Italy). Acquisition conditions were 40 kV and 40 mA. Scans were ob-
tained from 20 to 80° 2θ with a count time of 2 s. XRD data were
processed using XPowder12 software combined with PDF2 database of
ICCD.
The EMP analysis has been carried out using a Cameca SX50 elec-
tron microprobe equipped with five wavelength-dispersive spectro-
meters (CNR–IGAG, Rome, c/o Department of Earth Sciences, Sapienza
University of Rome). The operating conditions were: accelerating vol-
tage 15 kV, beam current 15 nA and beam size 15 μm. Gallium arsenide
was used as a reference standard for As (TAP, thallium (acid) phthalate
crystal), antimony trisulfide for Sb (PET, penta-erythriol crystal),
magnetite for Fe (LIF, lithium fluoride crystal), copper for Cu (LIF),
galena for Pb (PET), tin for Sn (PET), nickel for Ni (LIF), cobalt for Co
(LIF), manganese for Mn (LIF), zinc for Zn (LIF) and gold alloy (20%)
for Au and Ag.
The analytical error was ∼1% rel. for the major elements, and it
increases as their concentration decreases. The detection limit under
the specified working condition range between 0.01 and 0.1 wt%.
4. Results and discussion
To examine the distribution of the elements that compose the axe's
alloy and to explore the microstructure of both the corroded surface and
Fig. 1. Macroscopic photos of the axe from Motya (MCM.18.200), brought to light in the 'House of Mosaics' Area, 10th century BC.
3
Materials Characterization 158 (2019) 109957
inner core, a combination of SEM-EDX and EMPA analysis was em-
ployed. In our case to study manufacturing processes, we prepared
cross-sections from rim to core of the axe, opportunely selected, taking
into account the preservation of the weapon (see Fig. 1).
BSE images of the axe (Figs. 2 and 3b) show a metallic matrix with
numerous brighter inclusions elongated in the longitude of the cross
section. These inclusions with different shape and size (1 μm–200 μm)
are heterogeneously distributed in the alloy and are dispersed along α-
phase boundaries, as suggested by the observation of the figure at high
magnitude (Fig. 2c). SE image (Fig. 3a) shows the morphology and
topography of the cross-section, highlighting the high porosity of Pb
areas, associated with the presence of chloride, giving rise to a pre-
ferential loss of material and corrosion products. As shown in Fig. 3c,
the Cu content in the matrix is quite homogenous; however, its con-
centration in the external layer of the sample, corresponding to the
patina, is highly depleted for decuprification. This process involves the
corrosion morphologies which occurs in archaeological bronzes in
several environments such as soil [52,53].
During the decuprification process part of the Cu is dissolved and
leached from metallic structures, reacting with soil anions such as
chloride and carbonate, and depositing outward or on the surface of the
objects. The nature of neoformation corrosion products on the surface
of artefact depends on the type of soil soluble anions and their reactivity
[52,53]. From an exclusively scientific point of view, a comparison can
be made with Roman fibula from Marocco, where a marked decupri-
fication has been reported [54]. Unlike most bronze artefacts studied in
many works [54–57], where the process of decuprification is accom-
panied by an enrichment in tin on the surface, the analysed axe shows a
similar dissolution mechanism also for the tin content (i.e, destannifi-
cation process), as shown in Fig. 3d. These selective corrosion patterns
depend on electrochemical potentials of the alloy constituents and
thermodynamic stabilities of the corrosion products [58].
Fig. 3e shows the distribution of Pb content in the cross section.
SEM-EDS analyses indicate the presence of large Pb-globules with
stretched morphologies in the copper-tin matrix. Lead does not parti-
cipate to the formation of the alloy with Cu and Sn but occurs as glo-
bules in the structure of the matrix due to the low miscibility of Pb in
copper. Indeed, during solidification process of leaded bronze, first a
solid solution of Cu–Sn begins to solidify, while Pb remains in the liquid
state [59].When the temperature reaches the eutectic temperature
(326 °C in the Cu–Pb system [60,61]), Pb also solidifies, placing in the
M. Bernabale, et al.
Fig. 2. BSE images showing the microstructure of the alloy with Pb-globules at different magnification: a) 2 mm, b) 200 μm and c) 100 μm.
grain boundaries of the alloy or within the grains of Cu –Sn solid so-
lution. The number and distribution of the Pb inclusions in the matrix
depend on the content of Pb and casting parameters [62]. The cooling
rate of the original casting plays a fundamental role in the distribution
of lead in the alloy. If the cooling rate is very slow there is time for the
bulk of the lead to be refused from the solid ahead of the freezing front.
On the contrary, if the cooling rates is quick the freezing is so fast that
the lead is immobilized as small particles throughout the matrix [63].
The corrosion process of the Pb bearing-areas, enriched on and or
near the surface, involves the formation of a white layer as showed in
the BSE image (Fig. 3b).
The presence of high Pb content involves drawbacks as it is not a
performing metal for weapons productions (knives, swords, rasps, axes,
etc.) that should have high mechanical properties. Indeed, Pb is com-
pletely immiscible in the solid phase Cu–Sn, forming structural dis-
continuities and lines of weakness which cause possible fracture points
in the metal artefact. In fact, bronze items which necessitate hard me-
chanical working should mainly be manufactured with binary alloy
[64]. On the contrary, during the production of symbolic weapons, the
need of a series and easy manufacture requires alloys high Pb content,
which involves low temperatures.
The X-ray map of Fig. 3f shows the distribution of arsenic in the
matrix. The presence of the As in the solid solution involves a strain
hardening effect, which can give mechanical properties in the produc-
tion of peculiar artefacts as those with cutting edges [14].
Fig. 4 shows the presence and distribution of contaminant elements
from soil such as S and Cl and O. The presence of chlorine in the soil of
Fig. 3. Combination of figures: morphological image in SE (a), compositional image in BSE (b) and X-ray maps of Cu, Sn, Pb, As (c, d, e, f).
4
Materials Characterization 158 (2019) 109957
Motya could be explained taking into account that this archaeological
site is located in a marine environment. These results indicate an in-
teraction between soil constituents and bronze components which
produces insoluble products.
As shown in Fig. 4, Cl and S occur in Pb-reach globules, formed
when the alloy was cast and also in the patina. Indeed, the axe was
covered with a layer thin of corrosion, which is the result of redox re-
actions between the alloying elements and species from environment.
In particular, as suggested by X-ray maps, the presence of the oxidized
lead compounds such as oxides, sulphates, chloride, are detected.
X-ray diffraction, performed on the surface of leaded bronze axe,
confirms the presence of these corrosion products. As shown in dif-
fractogram (Fig. 1S), carbonates (cerussite and plumbonacrite), chlor-
ides (laurionite) and sulphate (anglesite) and oxides of the main alloy's
elements, such as cuprite, cassiterite and litharge are found in the
whole patina.
In addition, a large quantity of Pb occurred as isolated phase in the
matrix, during time, diffuse and migrate to the surface through porosity
of the alloy and the capillary channels formed during the corrosion
process [65]. Here, the Pb-globules react with water, oxygen and
chloride ions from environment acting as an anode and pitting corro-
sion. This anodic pit can preserve charge neutrality by pulling chloride
ions from the outside, forming lead chloride [66].
The intermittent salt-rich marine environment provides an ideal
medium for galvanic reactions between the Cu matrix and the Pb glo-
bules, being in a good electrical contact in the bronze alloy. On the
basis of the different standard potential of the two redox couples Cu2+/
M. Bernabale, et al.
Fig. 4. X-ray maps showing the distribution of S, Cl and O in Pb-rich areas.
Cu (E°=+0.330 V) and Pb2+/Pb (E°=−0.126 V), the loss of Pb, the
less noble metal, involves a selective corrosion, giving rise to the for-
mation of a porous structure, which is the main cause of the loss of
mechanical properties of the alloy [67]. A similar corrosion behaviour
was found in some artefacts studied by Ingo [67] in which Pb occurs
mainly as cerussite (PbCO3), only in some areas of the patina as an-
glesite (PbSO4) and very scarce cotunnite-like (PbCl2) compounds.
These Pb-mineral species were formed during the long-term interaction
between the artefact and the environmental species in sea water
[68,69].
Quantitative chemical analyses were performed by EPMA in se-
lected areas of metal matrix as reported in Table 1. The Pb content is
due to the occurrence of Pb-rich micro-areas disseminated in the ma-
trix; therefore, it was impossible to select a Pb-free area.
The matrix is a bronze alloy with 92 wt% Cu and about 5 wt% Sn.
Instead, Pb forms distinct micro-domains as reported in Table 2. The
total amount of elements detected in Pb-globules was normalized to
100%. The low total of the analyses can be explained due the presence
of oxygen, sulphur, chlorine and other undetected elements.
Arsenic was found in low concentration (between 0.6 and 1.3 wt%)
in the matrix. This element can be deliberate added to the alloy or
present as minor element in the raw material used for metal object
production [70]. Generally, a not voluntary addition of As is tested for
low amounts of his element (< 1% - 2%). The smelting of raw material
of Cu-ore often produced alloy that contained As, usually in the range
from 0.5 to 3% (as well as trace of other elements), depending upon
how much arsenic was present in the ore. The presence of As (from
0.5% up to 1%) involves some advantages as it improves the hardness
of the alloy; however, the brittleness of the bronze also increases. When
the content of As is above 1.5% the casting qualities of the alloy are
improved but brittleness and hardness rise in proportion as well [71].
Commonly, the iron amount gives indication about the smelting
process employed in ancient copper alloys [72]. According to [73], an
iron content average around 0.05% is an indication of a primitive
process for copper smelting with relatively poor reducing conditions
and probably non-slagging. On the contrary, the occurrence of Fe with
average around 0.3% can be considered as an indication of a more ef-
ficient smelting process [74].
Early copper smelting was probably realized at lower temperatures
using ore with high quality, whereas later these processes were carried
out at higher temperatures, for longer times, under more reducing
conditions than those involved during the early process [15].Therefore,
5
Materials Characterization 158 (2019) 109957
the low content of Fe (∼0.01%) in the bronze axe suggests that it was
made in a primitive smelting technology or that it could also be the
result of an efficient copper refining or other metallurgical process [11].
EMP analysis of the Sardinian axe showed that it is composed by Cu-
based ternary alloy, made mainly of leaded bronze with arsenic impurities.
Qualitative analysis of the BSE image allows estimating the Pb content in
the axe, which represents about 15–20 wt% of the total (Fig. 2a).
The features of the bronze axe from Motya do not fit exactly neither
into the metallurgical practices, introduced by Phoenicians in the
Orientalising Period, and neither in the LBA indigenous tradition of the
Motherland. It presents hybrid features, which reflect the geographical
position of the island in the Mediterranean Sea, being an obligatory
transit point for trade routes to Spain, Sardinia and Central Italy.
To confirm a previous assumption of Shalev, regarding the possi-
bility to find all typology of alloy in every region and over time, a
comparation with the double-loop socketed axe from Bonnanaro
(Sardinia) was reported [45]. Despite these axes have the same typol-
ogies, they show a different metal composition. Indeed, Motya's axe
presents a lower Sn and a higher Pb content than Sardinian axe (Cu
∼93 wt%, Sn ∼ 10 wt% and 0.071 wt% of Pb [45]), resulting similar to
the composition of other weapons of the Atlantic Europe.
High-leaded tin bronzes are more common in the LBA/EIA and are
mainly related to Brittany, France, British Isles, North West Iberia
(Galicia) and Northern Portugal production, due to a strong
Orientalising influence [75].
In particular, Harrison et al. [75] highlighted the presence of high
Pb content (up to 35%) in the Atlantic Bronze Age axes (1000 -700 BC)
from the Iberian Peninsula in the British Museum.
As shown in Montero et al. [76], leaded bronze was also used in
palstaves from Cármenes (16.4 wt% Pb), Pola de Laviana (48.1 wt% Pb)
and Vara (Lugo) (21.2–48.1 wt%Pb).
Another example of high leaded bronze is represented by thirteen
double looped palstaves from São Martinho de Bougado (Porto,
Portugal), in which the Pb content (43.5% Pb) is much higher than
Central Portugal's axes [76].
Regarding the Italian Peninsula and Greece, very few items made of
leaded bronze, e.g., flanged axe with about 4.9% of Pb from Terni
(Umbria, Italy) and a double edged axe having 4.80% Pb from Argolide
(Peloponneso) are found [77].
In contrast with the Atlantic Europe LBA/EIA metallurgy, in Central
and Southern Portugal and Iberian Peninsula, as well as in all
Mediterranean areas, low Pb content is a common feature. In fact,
 M. Bernabale, et al.

Table1
Representative EMP analyses of bronze matrix (wt%)

Matrices

Point 1 Point 2 Point 3 Point 4 Point 5 Point 6 Point 7 Point 8 Point 9 Point 10 Point 11 Point 12

Ag 0.00 0.10 0.01 0.08 0.07 0.00 0.01 0.12 0.00 0.02 0.03 0.05
Au 0.03 0.01 0.07 0.00 0.03 0.03 0.08 0.02 0.04 0.10 0.00 0.00
Sb 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mn 0.00 0.01 0.00 0.00 0.00 0.00 0.03 0.02 0.00 0.00 0.02 0.03
Ni 0.11 0.02 0.08 0.13 0.08 0.14 0.06 0.15 0.15 0.04 0.17 0.05
Co 0.05 0.07 0.00 0.03 0.06 0.06 0.00 0.06 0.00 0.02 0.03 0.01
Fe 0.01 0.02 0.04 0.02 0.01 0.00 0.03 0.03 0.00 0.00 0.00 0.00
Sn 4.54 4.47 5.42 4.98 6.23 3.28 5.39 5.79 5.28 2.89 6.00 6.03
Zn 0.00 0.00 0.02 0.08 0.07 0.05 0.11 0.00 0.00 0.06 0.00 0.00
Pb 2.62 0.07 0.33 6.27 0.37 0.11 0.09 0.16 0.11 0.26 0.24 0.44
As 0.73 0.80 0.86 0.86 1.24 0.64 0.89 1.00 1.05 0.60 0.98 1.08
Cu 91.85 92.79 93.11 86.97 91.23 95.40 92.89 92.34 92.49 93.92 91.32 92.05

Total 99.95 98.37 99.94 99.43 99.38 99.70 99.57 99.69 99.13 97.92 98.79 99.74

6
Matrices

Point 13 Point 14 Point 15 Point 16 Point 17 Point 18 Point 19 Point 20 Point 21 Point 22 Point 23 Point 24 Point 25

Ag 0.04 0.06 0.07 0.05 0.00 0.04 0.08 0.09 0.05 0.02 0.04 0.13 0.05
Au 0.07 0.06 0.01 0.06 0.02 0.04 0.10 0.02 0.00 0.00 0.00 0.00 0.04
Sb 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mn 0.02 0.03 0.00 0.00 0.00 0.00 0.01 0.02 0.06 0.01 0.02 0.01 0.00
Ni 0.16 0.02 0.06 0.15 0.09 0.11 0.15 0.13 0.12 0.08 0.11 0.08 0.05
Co 0.02 0.00 0.01 0.00 0.02 0.00 0.00 0.00 0.03 0.00 0.00 0.02 0.01
Fe 0.00 0.02 0.03 0.01 0.02 0.01 0.02 0.02 0.02 0.00 0.02 0.02 0.00
Sn 6.04 5.25 4.16 5.42 6.43 6.87 5.26 5.64 6.21 4.50 4.86 6.94 4.98
Zn 0.03 0.04 0.00 0.00 0.06 0.02 0.00 0.02 0.00 0.00 0.00 0.02 0.00
Pb 0.11 0.11 0.30 0.41 0.33 0.11 0.14 0.30 0.37 0.16 0.29 0.19 0.12
As 1.04 0.93 0.81 0.97 1.13 1.38 0.95 0.91 1.03 0.80 0.85 1.28 0.84
Cu 90.78 92.25 92.01 91.43 91.24 91.02 92.74 92.11 91.02 94.38 93.37 89.55 90.46

Total 98.32 98.76 97.46 98.48 99.34 99.61 99.44 99.25 98.93 99.95 99.55 98.25 96.55
Materials Characterization 158 (2019) 109957
M. Bernabale, et al. Materials Characterization 158 (2019) 109957

Table 2 Declaration of competing interest

Normalized EMPA analyses of different globules (wt%)
The authors declare no conflict or competing interests.
Pb-globules

1 2 3 4 5 6 Acknowledgements

Ag 0.00 0.08 0.00 0.00 0.00 0.00 The axe has been uncovered by the Sapienza Archaeological
Au 0.00 0.00 0.00 0.01 0.14 0.00
Expedition to Motya thanks to the fruitful cooperation with the
Sb 0.00 0.01 0.00 0.00 0.00 0.01
Mn 0.00 0.04 0.02 0.05 0.00 0.00 Superintendence of Trapani of the Sicilian Region, and the G. Whitaker
Ni 0.07 0.00 0.02 0.01 0.00 0.02 Foundation, Palermo.
Co 0.00 0.00 0.01 0.01 0.01 0.03 Financial support was provided by Sapienza University of Rome
Fe 0.00 0.00 0.05 0.00 0.00 0.02
(Great Excavation Funds; Ateneo funding, 2016, 2017) and Ministero
Sn 0.13 0.07 0.15 0.04 0.05 0.00
Zn 0.10 0.00 0.05 0.00 0.00 0.02
dell’Istruzione, dell’Università e della Ricerca (funding FFABR 2017).
Pb 96.86 99.61 98.84 99.57 99.32 99.64 PhD grants of the Department of Earth Sciences, Sapienza University of
As 0.03 0.03 0.00 0.02 0.00 0.01 Rome, are gratefully acknowledged.
Cu 2.82 0.16 0.86 0.28 0.48 0.23

Appendix A. Supplementary data

Total 100 100 100 100 100 100

Supplementary data to this article can be found online at https://

bronze axes from Coles de Samuel [78], Freixanda [79], Vila Cova de
Perrinho, Cascais da Pedreira in Central Portugal [80] and in Italian
Peninsula and Greece [77], show less than 1% Pb.
Moreover, it is highlighted that Fe content in the Motya's axe is very
low, suggesting that the metal artefact was produced before the
spreading of more sophisticated smelting technology. This is in agree-
ment with the indigenous LBA/EIA metallurgy from Central Portugal
that is characterised by Fe content below 0.05 wt%, as reported in
several researches [79–83].
This study opens new challenges because it could be applied on
other metal artefacts from the same archaeological site, improving the
knowledge about the technological background of ancient Phoenicians.
5. Conclusions
The study of the bronze axe (MCM.18.200) from Motya is a unique
opportunity to explore the metallurgical technology of bronze during
the late Iron Age. Technological features, such as the distribution of Pb
and the composition of the alloy point to the deliberate production of a
prestige weapon. The characteristics of the fusion aim at enhancing the
regularity of volumes and the shining of the metal surface, something
properly fitting with the requirements of an apparatus symbolic
weapon. Results of the experimental work can, thus, be summarized as
follows:
1. BSE images disclosed the microstructure of the bronze axe from
Motya, resulting a Cu-Sn alloy matrix with globules of Pb.
2. The large and irregular Pb globules in highly leaded bronze axe
indicate a slow cooling rate, in which the cast stays fluid and lead is
rejected by the freezing edge, thus forming lead globules of large
sizes.
3. The dissolution of both constituents of a binary alloy (Cu and Sn) in
the patina is an example of decuprification and destannification
processes, occurring in bronze artefacts during long-term burial
period in the soil.
4. Pb, migrated from the bulk to the surface, interacts with O, Cl and S,
producing lead based mineral compounds, such as PbO, PbSO4,
PbClOH, PbCO3, Pb5O(OH)2(CO3)3; other corrosion products of the
alloy are Cu2O and Sn2O.
5. EMP analyses show the matrix is a bronze alloy with 92 wt% Cu and
about 5 wt% Sn. Arsenic was probably a not intentional addition,
being in low concentration (between 0.6 and 1.3 wt%) in the bronze
matrix. Instead, Pb forms distinct domains, containing about 95% of
Pb. The low content of Fe (∼0.01%) suggests that it was made in a
prehistoric smelting technology or that was undergone an efficient
metallurgical process.
doi.org/10.1016/j.matchar.2019.109957.
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