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The application of LIBS for the analysis of archaeological

ceramic and metal artifacts


Kristalia Melessanaki
a,*
, Maripaz Mateo
a,1
, Susan C. Ferrence
b
,
Philip P. Betancourt
b
, Demetrios Anglos
a
a
Foundation for Research and Technology-Hellas (FORTH), Institute of Electronic Structure and Laser,
P.O. Box 1527, 71110 Heraklion, Crete, Greece
b
Department of Art History, Temple University, Philadelphia, PA 19122, USA
Abstract
A bench-top laser-induced breakdown spectroscopy (LIBS) system has been used in the examination of pottery, jewelry and
metal artifacts found in archaeological excavations in central and eastern Crete, Greece. The objects date from the Middle and
Late Minoan periods (ca. 20th13th century B.C.) through Byzantine and Venetian to Ottoman times (ca. 5th19th century A.D.).
The spectral data indicates the qualitative and often the semi-quantitative elemental composition of the examined materials. In the
case of colored glazed ceramics, the identity of pigments was established while in the case of metal and jewelry analysis, the type of
metal or metal alloy used was determined. The analyses demonstrate the potential of the LIBS technique for performing routine,
rapid, on-site analysis of archaeological objects, which leads to the quick characterization or screening of different types of objects.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Laser-induced breakdown spectroscopy (LIBS); Archaeological artifacts; Minoan; Pottery analysis; Metal analysis
1. Introduction
The analysis of ancient artifacts provides archaeol-
ogists and historians with meaningful information
about the use and origin of archaeological objects as
well as the materials that were used. For example,
identication of compositional materials in pottery
found on a particular site could determine whether it
was originally created in a different location, allowing
researchers to draw conclusions relative to commu-
nication, trade and partnerships. Also, important tech-
nological insight is provided by means of systematic
chemical and structural analysis, which reveals infor-
mation about the techniques available for processing
materials in order to obtain the nal product.
Various analytical techniques have been used exten-
sively in the study of archaeological and art objects
providing important physical and chemical insight to
the structure of objects and materials. For example,
polarized light optical microscopy and scanning elec-
tron microscopy (SEM), X-ray uorescence (XRF),
proton induced X-ray emission (PIXE), X-ray diffrac-
tion (XRD), inductively coupled plasma coupled to
optical emission or mass spectrometry (ICPOES,
ICPMS) and Raman microscopy [114] are among
the most widely used techniques in archaeological
analysis and art conservation. However, one concern
with most laboratory techniques relates to the require-
ment for special sample preparation and handling
procedures and to limitations imposed by instrumen-
Applied Surface Science 197198 (2002) 156163
*
Corresponding author.
1
Present address: Department of Analytical Chemistry, Uni-
versity of Malaga, 29071 Malaga, Spain.
0169-4332/02/$ see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S0 1 6 9 - 4 3 3 2 ( 0 2 ) 0 0 4 5 9 - 2
tation factors. In addition, transportation of archae-
ological samples and works of art to specialized
analytical laboratories is often subject to strict regula-
tions and as a result requires lengthy procedures.
In this context, laser-induced breakdown spectro-
scopy (LIBS) is a potential alternative to other spectro-
scopic, mass spectrometric, or X-ray techniques used in
art conservationandarchaeologyrelatedapplications. It
is a practically non-destructive as well as rapid elemen-
tal analysis technique with the critical advantage of
being applicable in situ, thereby avoiding sampling
and sample preparation. Indeed, LIBS has been used
for the analysis of pigments in easel paintings, icons,
polychromes and pottery [1520] and demonstrates the
prospects of the technique to become a useful analytical
tool in art and archaeology. Furthermore, quantitative
LIBS analysis leading to absolute concentration values
for each element is ideal for the accurate compositional
characterization of the materials analyzed, and several
papers have addressed this problem in the literature
proposing different methodologies [1820].
In this paper, we present results from studies per-
formed on different pottery and metal samples in
excavations in the central and eastern parts of the
island of Crete (Greece) from ve different time
periods: Middle Bronze age (ca. 20th18th century
B.C.), Late Bronze age (ca. 17th13th century B.C.),
Byzantine (ca. 5th14th century A.D.), Venetian (ca.
14th16th century A.D.) and Ottoman (ca. 16th19th
century A.D.) and ve different locations: Knossos,
Chrysokamino, Hagia Photia, and the islands of Pseira
and Mochlos. Analytical information from the LIBS
measurements was used in order to characterize
painted pottery (pigment identication), metal objects,
and jewelry. This work is part of a broader project
whose main goal has been to develop, optimize, and
test a compact and transportable prototype LIBS work-
station. This integrated, user-friendly system will pro-
vide on-site, rapid, analytical information about the
qualitative and quantitative elemental composition of a
wide variety of materials aiding the quick character-
ization of archaeological objects and/or samples.
Table 1
Analytical emission lines used for identifying elements in LIBS spectra
Element Wavelength (nm)
Ag 272.177 (I), 328.068 (I), 338.289 (I)
Al 257.510 (I), 265.248 (I), 266.039 (I), 308.215 (I), 309.271 (I), 394.400 (I), 396.152 (I)
As 274.50 (I), 278.022 (I), As 286.044 (I), As 289.87 (I)
Au 264.148 (I), 267.595 (I), 274.825 (I), 288.345 (I) (290.704291.352) (II), 293.219, 302.920 (I), 312.278 (I),
320.472 (I), 323.063 (I)
Ca 315.887 (II), (317.933318.128) (II), 393.366 (II), 396.847 (II), 422.673 (I)
Cr 357.869 (I), 359.349 (I), 360.533 (I), 375.766 (I), 427.480 (I), 428.972 (I)
Cu 261.837 (I), 276.637 (I), 282.437 (I), 296.116 (I), 301.084 (I), 303.610 (I), 306.341 (I), 309.993 (I), 310.860 (I),
312.611 (I), 324.754 (I), 327.396 (I), 329.054 (I), 330.795 (I)
Fe 258.454 (II), (259.837259.940) (II), (260.651 (II)260.683 (I)260.709 (II)), 261.187 (II), 261.382 (II),
(261.762 (II)261.802 (I)), 262.567 (II), 262.829 (II), (263.105263.132) (II), (271.903272.090) (I), (274.948
(II)275.014 (I)), 296.689 (I), 298.357 (I), 299.443 (I), 302.064 (I)
Mg 279.553 (II), 280.270 (II), 285.213 (I)
Mn 370.608 (I), 371.893 (I), 380.672 (I), 382.351 (I), 383.436 (I), 384.108 (I), (403.076403.307403.449) (I),
404.136 (I), (407.924407.942408.294408.363) (I), (413.112413.504) (I), (423.514423.529) (I), 446.202
(I)
Pb 257.726 (I), (261.365261.417) (I), 266.315 (I), 280.199 (I), 282.319 (I), 283.305 (I), 287.331 (I), 357.273 (I),
363.957 (I), 368.346 (I), 373.993 (I), 401.963 (I), 405.781 (I)
Si 263.128 (I), 288.158 (I), 390.552 (I)
Sn 266.124 (I), 270.651 (I), 277.981 (I), 281.358 (I), 283.999 (I), 286.332 (I), 291.354 (I), 300.914 (I), 303.412 (I),
317.505 (I), 326.234 (I), 333.062 (I)
Ti 323.452 (II), 334.188 (I), 334.941 (II), 336.121 (II), (337.044 (I), 337.145 (I), 337.280 (II)), 338.376 (II)
Wavelengths in parentheses indicate two or more lines not adequately resolved in low-resolution spectra. The wavelengths refer to emission
from neutral atoms when followed by (I) and to emission from singly charged ions when followed by (II).
K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163 157
2. Experimental
In the present study, the output of a nanosecond Q-
switched Nd:YAG laser operating at its fundamental
wavelength (1064 nm, 15 ns, 25 mJ per pulse) was
focused with a planoconvex lens (f 100 mm) on the
sample surface inducing the formation of a transient
plasma plume. The focused beam intensity was in the
range of 0.54 GW/cm
2
. The plume emission was
collected with a quartz optical ber and analyzed in
a 0.32 m imaging spectrograph (TRIAX-320, Jobin
Yvon/Spex) with gratings of 600 and 2400 grooves/
mm (spectral resolution 0.04 and 0.01 nm, respec-
tively) and the LIBS spectrum was recorded on an
intensied charge coupled device (ICCD) detector
(DH520-18F, Andor Technology). The detector was
gated by means of a digital delay/pulse generator
(DG535, Stanford Research Systems) in order to
discriminate the atomic emission from the continuum
background present. Delay time of 100500 ns and
gate time of 500 ns were used in the measurements
reported herein. For the analysis, each sample was
placed on a translation stage and positioned within
2 mm from the focal point of the lens. This way, high
spatial resolution was achieved which allowed analy-
sis of minor features, such as inclusions in pottery,
with sizes as low as 100 mm. The analysis can be
characterized as practically non-destructive because
the laser beam is focused on a tiny spot of typical
diameter in the range of 100150 mm. In a few cases,
depending on the material probed, more extended
effects (up to 500 mm) were observed resulting either
from thermal discoloration of the paint or from ejec-
tion of poorly adhered material induced by the laser
shock wave which accompanies the ablation process.
Emission spectra were recorded for a single laser
pulse and were subsequently analyzed. In cases a
depth proling study was required, spectra were col-
lected separately for each one of several successive
laser pulses. Elements were identied on the basis of
the comparison between the emission lines in the
obtained spectra and the distinctive lines of metals
listed in Table 1. In general, the spectra were clear
enough to allow an immediate identication despite
the use of the low-resolution grating for light disper-
sion. In certain cases, the use of the high-resolution
grating claried or simply conrmed the results
obtained at low-resolution.
3. Results and discussion
A broad variety of archaeological ndings were
examined including painted and glazed pottery, dif-
ferent types of metal objects, and jewelry. Some of the
objects examined are shown in Fig. 1. LIBS analyses
were carried out in order to identify pigments or
characterize metal alloys, and selected spectral data
are presented to show the type of analytical questions
addressed and the information extracted.
3.1. Pottery analysis
Ceramic objects are ubiquitous in antiquity and
have been employed as storage containers, serving
dishes, and votive gurines, among other uses. They
are often made from local clay sources, although it is
known that Minoan towns often traded goods includ-
ing pottery. In the analysis of ceramic sherds, ques-
tions are related to the characterization of pigments,
the determination of elemental composition of clay,
and the characterization of surface encrustation. For
example, systematic PIXE analysis of the white paint
on pottery sherds from various locations in central and
eastern Crete has shown large but non-random varia-
tions in the elemental content of Mg, Ca, Si, and Al
which appear to correlate quite well with the location
of ceramic production [8,21].
Several types of ceramic objects were analyzed by
LIBS. One of the objects was a polychromed pottery
sherd (Fig. 1a) from an offering table dating to the
Middle Minoan IIB period (ca. 18th century B.C.),
found at Knossos (Minoan palace outside Heraklion,
Crete). White, black and red paint has been used in
decorating the surface of the object. Selected spectra
from the black pigment are shown in Fig. 2a. As seen
by the characteristic emission lines marked in the
spectrum, the paint contains substantial amounts of
Mg, Si and Al with a relatively high content of Fe, but
low content of Ca. Ti is also detected in this paint. In
order to further clarify the presence and identify the
emission lines of Fe, a high-resolution spectrum,
shown in Fig. 2a (inset), was taken. Iron-rich minerals,
with the iron primarily in the form of hematite
(Fe
2
O
3
), goethite (FeOOH) and other oxides, have
been extensively used as pigments in antiquity. Upon
ring, they undergo transformations to different dark
minerals, such as magnetite, a mixed iron oxide
158 K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163
(Fe
3
O
4
) [7]. The rest of the elements originate from
the clay co-existing with the pigment, which is a
mixture of aluminosilicate minerals.
Other ceramic sherds analyzed date from the
Byzantine, Venetian, and Ottoman periods on Crete
and were found at two locations, the small island of
Pseira and the metallurgy site at Chrysokamino. These
were differently painted glazed ceramics most likely
from household items (Fig. 1b and c). Glaze is a silica-
based mixture often containing pigment applied on the
surface of a ceramic vessel and then red over 1200 8C
producing a decorative, impermeable, glassy coating.
The black paint, used for decorating a white dish
(Fig. 1b) was analyzed, and the LIBS spectrum
showed the presence of manganese suggesting that
MnO has been employed (Fig. 2b). The intense lead
signal indicates the presence of lead white, which was
also detected in other areas of the object and was the
primary white pigment used throughout the Byzantine
era. Calcium, aluminum and silicon detected originate
from the glaze.
In another case, the bright yellow glaze used to
decorate the interior and exterior rim of a Turkish
bowl was analyzed on a sherd from the site of
Chrysokamino. The yellow glaze was found to con-
tain Pb, Ca and Cr (Fig. 3a). A high-resolution
spectrum of the yellow pigment was also recorded
(Fig. 3a, inset), conrming the presence of chromium
on the basis of characteristic emission lines. The
combined presence of lead and chromium suggests
that chromium yellow (lead chromate, PbCrO
4
) has
been used. Chromium yellow, a synthetic pigment,
was introduced as a coloring agent approximately
1818. This implies that the pottery analyzed dates
not before the early 19th century, which is in fact in
agreement with the excavation data as the sherd was
found close to the surface of the area excavated.
Furthermore, this type of information suggests that
LIBS can be employed to determine/conrm the date
of certain types of pottery.
In several sherds examined, the green paint was
found to be rich in Cu suggesting the extended use of
Fig. 1. Pictures of selected archaeological objects analyzed. (a) Minoan polychromed ceramic sherd from Knossos (T907); (b) Byzantine
glazed ceramic sherd from Pseira (PS3048); (c) Late Byzantine/Venetian glazed ceramic sherd from Pseira (PS1079); (d) Minoan metal rivet
from Pseira (PS1004); (e) Byzantine metal ring from Pseira (PS438); (f) Minoan metal chisel from Hagia Photia (AN4666).
K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163 159
Cu based pigments. Several green as well as blue
pigments, which are copper compounds, have been
used in painting from antiquity through to the modern
era [12,13]. In a few cases, for example, in the pottery
sample shown in Fig. 1c (interior glaze decoration on
Late Byzantine/Venetian open vessel from Pseira), the
presence of tin along with copper in the green pigment
was obvious (Fig. 3b). Identifying the source of tin in
the green pigment is an important question in under-
standing the type of pigment used. One possible case is
that a bronze (coppertin alloy) object may have been
used for preparing the green pigment. It is known that
green pigments are produced from copper through a
chemical oxidation procedure. However, the presence
of large quantities of bronze from archaeological
remains may have led to the use of bronze instead
of copper in the production of pigments. Alternatively,
the presence of Sn can be due to the mixture of a lead
tin yellow pigment (Pb
2
SnO
4
or PbSn
1x
Si
x
O
3
) with a
copper based green or blue pigment. Further studies
are under way for resolving the identity of this type of
pigments.
3.2. Metal analysis
Another large class of objects in archaeological
excavations are metal artifacts ranging from tools
and weapons to home utensils and jewelry. The main
materials used in the Bronze age have been copper and
coppertin alloys (bronze). Addition of tin to copper at
the level of 510% by weight was found to produce a
slightly harder alloy, which was easier to cast. Other
metals used include lead and tin. Silver or gold alloys
have been used in jewelry and as decoration for
different objects. The rst analytical question con-
cerning a metal object is to identify the type of metal
or metal alloy. Furthermore, determination of the
quantitative content of the various metals and of the
trace elements can lead to a more complete character-
ization of the objects.
A rivet from the island of Pseira (Fig. 1d), dated to
Late Minoan IB (ca. 16th century B.C.), used to hold
the blade within the wooden handle of a dagger, was
examined. It was found to be composed of copper by
probing representative points around the cylindrical
Fig. 2. LIBS spectra of black pigments on: (a) Minoan poly-
chromed sherd (inset: high-resolution spectrum); (b) Byzantine
glazed ceramic sherd.
Fig. 3. LIBS spectra from glazed ceramic sherds. (a) Yellow glaze
(inset: high-resolution spectrum); (b) green glaze (
*
mark Sn emission
lines).
160 K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163
surface. While taking additional spectra on the at
sides of the rivet, a surprising result was found. Intense
emission from silver was recorded in the LIBS spec-
trum (Fig. 4a). This indicates the presence of silver on
the exposed at sides of the rivet, possibly from a
silver coating. This rivet is the rst of its type found on
the site of Pseira. Other parallels for this type of object
come from the Mycenaean shaft graves in mainland
Greece.
LIBS spectra from a metal pin analyzed are shown
in Fig. 4b and c. While emission lines due to copper
are observed when the outside part of the pin is
examined, additional emission from tin is clearly
detected when the core of the object is probed by
the laser beam. This nding is quite dramatic and
indicates two possible situations. The rst is that the
pin is actually constructed from an inner part made of
bronze and an outer part made of pure copper. The
other (and more likely) possibility is that extended
metal corrosion has resulted in total loss of tin from
the heavily corroded outside layer while part of it has
been preserved in the core of the material.
In another case, a Byzantine bronze ring fromPseira
(Fig. 1e) was examined and was found to contain
copper and tin with signicant amounts of lead as seen
in the corresponding spectrum (Fig. 5a). Also, an
Early Minoan IB (ca. 27th century B.C.) metal chisel
from the cemetery at Hagia Photia (Fig. 1f) was
examined and was found to contain both lead and
arsenic in addition to copper (Fig. 5b). The presence of
arsenic in copper objects of this time period has a long
history in the literature [2225].
Finally, a spectrum from Late Minoan IIIA (ca.
14th13th century B.C.) jewelry (golden bead) from
the island of Mochlos is shown in Fig. 5c indicating
the use of a AuAgCu alloy. Other similar objects
were analyzed showing different relative intensities
of emission lines suggesting variable proportions
of Au, Ag and Cu in the alloy used. These results
indicate that LIBS analysis can quickly provide infor-
Fig. 4. LIBS spectra of Minoan metal samples obtained: (a) on the
at face of copper rivet; (b) on the outside of metal pin; (c) in the
core of the same metal pin.
Fig. 5. LIBS spectra from: (a) Byzantine metal ring; (b) Minoan
metal chisel; (c) Minoan golden bead.
K. Melessanaki et al. / Applied Surface Science 197198 (2002) 156163 161
mation on the qualitative and semi-quantitative ele-
mental content of different metal objects and aid their
characterization and classication. Quantitative ana-
lysis by LIBS is also possible using proper reference
samples or alternative approaches, such as the one
recently used for the quantitative analysis of precious
metal alloys [26].
At this point, it is important to stress two factors that
might affect the reliability of the analysis in the
identication of the chemical composition of metal
artifacts. The rst is the corrosion of metals, which
leads to material alteration and possible loss of certain
metals in the form of soluble salts. This effect was
shown in the LIBS analysis of the bronze pin as
indicated in the LIBS spectra in Fig. 4b and c. One,
therefore, has to be aware that surface examination
probes mainly the corrosion products. Conclusions
regarding the elemental composition of the original
object should be drawn with care as certain corrosion
products are known to leach out of the object, and
therefore, their lowcontent does not necessarily reect
the composition of the metal at the time of object
manufacture. For example, surface analysis techni-
ques (sensitive only to a layer depth of 10100 mm)
can give misleading results in cases where extended
metal corrosion is present. The other concern when
dealing with metals analysis is the heterogeneous
character of a metal alloy object that often results
from poor mixing of the different metal alloy compo-
nents at the time of production. These two factors can
affect both the qualitative and, more signicantly, the
quantitative analysis of metal objects. In this respect,
great care must be taken in performing the analysis
and reporting the results.
4. Conclusions
The results presented in this paper demonstrate the
advantages of LIBS analysis in obtaining elemental
analysis information about the materials used for
making and decorating ancient pottery or metal arti-
facts. An important aspect of LIBS is the speed of
analysis, which can allow the quick examination of a
large number of samples in the eld, at a museum, or
at an excavation site. Compact and user-friendly
instrumentation could make a powerful tool for the
analysis of a large variety of materials leading to quick
characterization and classication of archaeological
ndings.
Acknowledgements
The authors wish to thank the Institute for Aegean
Prehistory (INSTAP) and the Foundation of Research
and Technology-Hellas (FORTH) for funding and
collaboration on this project. They also owe many
thanks to N. Papadakis and A. Nikakis of the 24th
Ephoria of East Crete and S. Chlouveraki and T.
Brogan of the INSTAP Study Center of East Crete.
The authors would also like to thank J. Soles, director
of Mochlos excavations, and E. Hatzaki, Knossos
curator for the British School at Athens for allowing
pottery and metal samples to be analyzed.
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