Anal Bioanal Chem (2007) 387:749–760
DOI 10.1007/s00216-006-0908-1
REVIEW
Laser-induced breakdown spectroscopy (LIBS)
in archaeological science—applications and prospects
Anastasia Giakoumaki & Kristalia Melessanaki &
Demetrios Anglos
Received: 1 June 2006 / Revised: 3 October 2006 / Accepted: 6 October 2006 / Published online: 24 November 2006
# Springer-Verlag 2006
Abstract Laser-induced breakdown spectroscopy (LIBS)
has emerged in the past ten years as a promising technique
for analysis and characterization of the composition of a
broad variety of objects of cultural heritage including
painted artworks, icons, polychromes, pottery, sculpture,
and metal, glass, and stone artifacts. This article describes
in brief the basic principles and technological aspects of
LIBS, and reviews several test cases that demonstrate the
applicability and prospects of LIBS in the field of
archaeological science.
Keywords Archaeology . Archaeometry . LIBS .
Laser ablation . Elemental analysis
Introduction
The endeavors of archaeologists to “dig” into our past are
seriously hampered by the very limited written evidence of
life and human activity in antiquity. Determining and
studying the chemical composition of materials is often
among archaeologists’ main means of shedding light on the
information contained on or in ancient artifacts and objects.
To this end sophisticated chemical analysis tools have been
A. Giakoumaki : K. Melessanaki : D. Anglos (*)
Institute of Electronic Structure and Laser,
Foundation for Research and Technology-Hellas (IESL-FORTH),
P.O. Box 1385, 71110 Heraklion, Greece
e-mail: anglos@iesl.forth.gr
A. Giakoumaki
Department of Materials Science and Technology,
University of Crete,
71409 Heraklion, Greece
used to answer questions about the composition of the
objects used in archaeological research. (Table 1) This
synergy has enabled the field of archaeometry to grow
steadily with time, relying largely on the continual
advances in modern analytical science and instrumentation
and in data-analysis techniques and statistical methods,
including chemometrics [1–4].
In this context a rather new analytical technique, laser-
induced breakdown spectroscopy (LIBS), was introduced
approximately 10 years ago [5] in the field of cultural
heritage analysis and has since been applied by several
research groups to determine the element content of
materials in a variety of objects including painted artworks,
icons, polychromes, pottery, sculpture, and metal, glass,
and stone artifacts [6–12]. Encouraging results have been
obtained and some of the advantages of the technique—
described in the next section—have been recognized. Use
of LIBS in archaeological science and archaeometry has
not, however, gained the popularity expected, with most
work to date performed mainly in physics or chemistry
research laboratories and focusing on the development of
analytical methodology and instrumentation. Routine anal-
ysis in the field of archaeological science is still based on
X-ray and ion-beam techniques, for example scanning
electron microscopy coupled with X-ray microanalysis
(SEM-EDX) [4], X-ray fluorescence spectrometry (XRF)
[13–17], proton-induced X-ray emission (PIXE) [18, 19],
and X-ray diffractometry [16, 20]. Raman [21, 22] and
FTIR microscopy [23, 24] and (laser ablation) inductively
coupled mass spectrometry (LA–ICP–MS) [25, 26] have
also increased in importance over the past decade.
In this review the basic physical principles and analytical
features of LIBS are outlined, and followed by a brief
description of instrumentation and technology. Selected test
750 Anal Bioanal Chem (2007) 387:749–760

Table 1 Analytical techniques in archaeological science

Analytical method Applications

Atomic absorption/emission spectroscopy Elemental analysis of pottery, metal and glass

Inductively coupled plasma–optical emission
spectrometry (ICP–OES)
Inductively coupled plasma-mass spectrometry
(ICP–MS)
Secondary-ion mass spectrometry (SIMS)
Scanning electron microscopy (SEM, ED X-ray
microanalysis)
X-ray fluorescence spectrometry (XRF)
Particle-induced X-ray emission (PIXE)
Neutron-activation analysis (NAA)
Isotope analysis
UV–visible absorbance/reflectance spectroscopy
Fluorescence (photoluminescence) emission
spectroscopy
Fourier transform infra-red spectroscopy (FTIR)
Raman spectroscopy/microscopy
X-ray diffraction (XRD)
Gas chromatography (GC), gas chromatography–
mass spectrometry (GC–MS), pyrolysis GC–MS
High-performance liquid chromatography (HPLC)
Mass spectrometry (MALDI–TOF, DTMS)
Nuclear magnetic resonance (NMR) spectrometry
Major and trace element analysis of metals and minerals
Trace element and isotope analysis of metals and minerals
Elemental analysis of pigments, pottery, metals, alloys, and minerals
Mapping and elemental analysis of pigments, pottery, metals and minerals
Elemental analysis of pigments, metals, and minerals
Major and trace element analysis of pigments, pottery, metals, and minerals
Analysis of major and trace elements in pigments, pottery and minerals. Provenance.
Dating and provenance
Analysis of inorganic pigments
Pigment and binder analysis
Paint analysis (pigments, binders)
Minerals, metal corrosion products, inorganic and organic pigments, and binder analysis
Pigment and mineral analysis
Analysis of organic components and residues.
Analysis of organic components, for example binders, varnishes, etc.
Analysis of organic components and residues.
Analysis of organic materials

cases, which provide an overview of representative archae-
ological science questions addressed by LIBS analysis, are
presented and future prospects of the technique are
discussed.
Physical principles and main features of LIBS
The LIBS technique, also referred to as laser-induced
plasma spectroscopy (LIPS), has emerged in the past
twenty years as a promising tool for spectrochemical
analysis of the element content of materials [27, 28].
Although the original evidence of the analytical potential of
laser-produced plasmas was demonstrated shortly after the
invention of the laser in 1962 [29, 30], it was not until the
1980s that technological advances in laser sources and
detectors enabled reliable experiments to be conducted that
demonstrated the analytical capabilities of LIBS. Since
then, significant research effort have shown the potential of
LIBS in a very broad field of applications that include
industrial process control, environmental and waste moni-
toring, and geochemical analysis. Recent important advan-
ces include the development of commercial LIBS
technology that is expected to make the technique available
to a broader user community for routine materials analysis
and specialized applications. Details on the basic aspects of
the technique, the underlying physical phenomena, and its
applications have been reported in several books and
review papers [27, 28, 31–33].
In brief, irradiation of a solid surface with a laser pulse
with a typical duration of a few nanoseconds and energy of
the order of a few millijoules (which results in a focused
intensity of approximately 109 W cm−2 or more) gives rise
to material ablation and formation of a transient, luminous
plasma that containing analytical information about the
element content of the sample. This information is captured
by resolving the radiation emitted from the plasma both
spectrally and in time. The characteristic, sharp atomic-
emission peaks in the LIB spectrum enable identification of
the elements contained in the minute amount of material
ablated, reflecting the local element composition of the
sample. An indicative LIB spectrum obtained from a bronze
sample is shown in Fig. 1. The peak intensity or the
integrated emission of individual spectral lines can, in
principle, be associated with the number density of the
corresponding emitting species in the plume and this, in
turn, can be associated with the concentration of the
elements in the sample, leading to quantitative analysis.
Anal Bioanal Chem (2007) 387:749–760
Fig. 1 LIB spectrum from a bronze sample (Cu 92%, Sn 8%, w/w)
recorded on an Echelle spectrograph with a resolution of 0.1 nm. In
the inset a detail of the spectrum is depicted, showing clearly emission
lines from Cu and Sn
This is achieved either by use of calibration plots, obtained
by analysis of appropriate reference samples, or on the
basis of a calibration-free approach [34].
Key features which make LIBS an attractive analytical
technique include its simple implementation, instrumenta-
tion which is relatively straightforward to use, the ability to
achieve high spatial resolution nearly non-invasively, the
speed of analysis, the need for no, or minimal, sample
preparation, which essentially enables analysis to be
performed in situ, and the ability to analyze solid (both
conductive and non-conductive), liquid, or gaseous sam-
ples, and provide both qualitative and quantitative multi-
elemental analysis results.
In the field of archaeological science and conservation,
in particular, several of these features are regarded as quite
important, for example the ability to perform the analysis in
situ, i.e. on the object itself, with no need for sampling or
sample preparation. This, and the fact that a typical
measurement requires a single laser pulse and the
corresponding spectrum is acquired in less than one second,
results in unparalleled speed. Because of the tight focusing
of the laser beam the lateral spatial resolution achieved is
nearly microscopic. The technique can also provide depth-
profiling information if spectra from successive laser pulses
delivered at the same point are recorded sequentially.
Although the analysis leads to removal of material from
the surface, the loss in a typical LIBS experiment, is
minimal (tens or hundreds of nanograms) and any damage
to the sample surface is practically invisible to the naked
eye. Thus LIBS can be regarded as almost non-destructive.
Finally, compact equipment can be used; this can be
“packaged” in a portable or transportable unit that enables
751
analysis to be conducted on location, for example at the
museum, the conservation laboratory, or even outdoors, for
example at an excavation site.
These features make LIBS quite competitive compared
with other techniques commonly used in archaeological
science for obtaining elemental analysis information. For
example, although SEM-EDX has superb element-mapping
capabilities, it cannot be performed in situ and requires
removal of a small sample from the object (properly coated
to eliminate surface charging effects for non-conducting
materials) and analysis in a vacuum chamber. XRF, a non-
destructive technique, has capabilities similar to those of
LIBS, for example simultaneous multi-element analysis and
nearly microscopic resolution available in transportable
instrumentation, but fails to detect elements lighter than
sodium; its rather coarse depth resolution (10–50 μm
depending on the matrix) might also lead to confusing
results when layered surfaces are examined (total reflection
XRF is free from this problem). PIXE has sub-micrometer
lateral spatial resolution, excellent sensitivity (a few ppm to
tens of ppm), and in the external mode can be used for in-
situ analysis of real objects in the ambient atmosphere; the
requirement for an ion accelerator limits its use to
specialized facilities, however. The LODs of LA–ICP–MS
are among the lowest, so it is ideal for trace element and
isotope analysis; it does, however, require use of strictly
laboratory, non-transportable instrumentation.
It is obvious that different techniques are characterized
by their own strengths and weaknesses and that one
technique may be selected in preference to another,
depending on the analytical problem (e.g. analysis of major,
minor, or trace elements; microscopic resolution), on
possible limitations imposed by the object or sample
examined (e.g. surface heterogeneity or corrosion, shape,
need for in-situ analysis, possibility or not of sampling),
and on the technique’s capabilities.
Instrumentation and technology
Laboratory systems
As already mentioned, setting up a LIBS experiment in the
laboratory is rather straightforward (Fig. 2). A pulse from a
nanosecond laser (typically Q-switched Nd:YAG or exci-
mer) is focused on the sample surface and the light emitted
from the plasma is collected with an optical fiber placed
near the plume and fed into a spectrograph, the size and
grating of which determine the spectral resolution. Use of
Echelle spectrometers enables wide spectral coverage with
high spectral resolution, important for fast multi-element
analysis [35]. The spectrum is recorded by means of an
array-type detector (nowadays intensified-CCD) that ena-
752 Anal Bioanal Chem (2007) 387:749–760

Fig. 2 Diagrammatic represen-

tation of typical experimental
LIBS instrumentation

bles time-gating of the emission, thereby achieving dis-
crimination of the useful atomic emission signal from the
broadband continuum background present immediately
after sample irradiation.
The laboratory environment offers flexibility with choice
of laser, optics, beam positioning and focusing, and
spectrometer and detection systems. This enables system-
atic investigation of experimental conditions and optimiza-
tion in accordance with the needs of each particular
material. Variants of the basic experimental approach can
also be adopted, extending the technique’s capabilities and
enabling, for example, micro-analysis or remote measure-
ments, or even measurements under water. Some of these
variants are briefly described in the following paragraphs.
Micro-LIBS
minimum, and totally invisible to the naked eye (Fig. 3).
Although micro-LIBS is not yet a common approach, in the
same way as Raman microscopy, for instance, several
examples have already been reported with applications in
archaeological analysis, including metal and pottery anal-
ysis [12, 37].
Remote analysis
There is often a need to analyze objects or larger structures
(e.g. sculpture, monuments), which are either remote or just
not conveniently accessible. To respond to these challenges
remote sensing approaches are adopted; these are either
fiber-optic based or open-path.

Although LIBS has inherently micro-analysis capabilities,

typical reported spot (or crater) diameters fall in the range
50 to 200 μm, a size determined by the quality of the laser
beam and focusing optics, by the energy applied to the
sample, and by the thermal and mechanical response of the
surface to laser ablation. Given the value of archaeological
objects and the sensitivity and fragility of the surfaces
examined it is obvious that one wishes to reduce, as much
as possible, surface alteration and material removal during
LIBS analysis. Evidently a microscopy approach is appro-
priate. By use of special laser microscope objective lenses it
is possible to focus a high-quality laser beam to areas of
diameter as small as 10 μm while maintaining a plasma that
provides reliable spectral information [36]. This approach is Fig. 3 Image obtained on a scanning electron microscope (SEM) of a
extremely important, because it enables analysis of very crater produced during micro-LIBS analysis of a brass sample with
small features and keeps any surface damage to a one laser pulse at 532 nm (5× objective lens, f=30 mm)
Anal Bioanal Chem (2007) 387:749–760
Fiber optic LIBS
In-situ LIBS analysis is a challenge when oversize objects
must be examined. Positioning such objects, which are often
heavy, relative to the laser beam is difficult and risky. A
simple and convenient means of properly delivering the laser
beam to the surface of a large painting or sculpture is clearly
needed. In this respect transmitting the laser beam to the
object by use of an optical fiber provides the necessary
flexibility, enabling analysis of large or complex surfaces and
areas on the object that are difficult to approach otherwise.
Although the feasibility of fiber-optic LIBS analysis has
been demonstrated [38, 39], its use in cultural heritage
analysis is rather limited [40], because of technical issues,
not yet fully addressed, for example damage to the fiber as
the laser beam is coupled to it or poor refocusing of the laser
beam on leaving the fiber. The latter results in a wider spot at
the focus which, for valuable objects, is an issue of concern.
Remote LIBS
Within the context of remote-sensing applications open-
path remote LIBS is capable of enabling rapid elemental
analysis of remote targets [41, 42]. This approach enables
scanning of large surfaces, for example, statues, monu-
ments, building facades, from as far as 50–100 m without
the need for special scaffolding.
An interesting variant employing UV femtosecond laser
radiation, which organizes itself in filaments that enable
beam propagation over long distances, was recently shown
to have potential for remote LIBS analysis of materials on
monuments. Relevant materials, for example metals and
different types of stone, were successfully analyzed at
distances as long as 20 m by using filaments produced by
UV femtosecond laser pulses (248 nm, 450 fs) [43].
Double-pulse LIBS
Recent studies have shown that LIBS with two (and, less
often, multiple) laser pulses, temporally separated by a few
microseconds, result in improved analytical performance,
with enhanced emission intensity and lower LODs [44, 45].
The signal enhancement observed in double-pulse LIBS
analysis of solids in ambient air is attributed to the fact that
the ablation plume arising from the second laser pulse
experiences a locally modified atmosphere over the sample
surface, as a result of plume expansion after irradiation with
the first laser pulse.
Recent experiments [46–48] have shown double-pulse
LIBS to be particularly attractive for underwater character-
ization of archaeological findings, important both for
recovery of valuable objects and for in-situ cataloguing
and restoration. Whereas conventional single-pulse LIBS of
753
solid surfaces in water results in weak signals, because of
plasma quenching, use of pairs of pulses substantially
improves analysis. The first laser pulse produces a
cavitation bubble inside which the second pulse ablates
the solid sample, producing a rather intense, narrow-line
spectrum. This is a result of the reduced plasma confine-
ment within the bubble environment.
Time-integrated LIBS
The high electron density of the plasma immediately
after laser ablation gives rise to a strong continuum
emission underlying the spectrum and to broadening of
the lines because of the Stark effect. By appropriate
time-resolution of the plasma emission these effects can
be largely eliminated and narrow-line, well-resolved
spectra are recorded. It has, however, been observed
that with low-energy pulses the contribution of the
continuum is drastically reduced to an extent that even
the time-integrated recording of the plasma emission
yields spectra with clean emission lines adequately
resolved. [49–52] As a result, use of non-gated detectors
seems feasible for LIBS analysis when relatively low
energy pulses are used, as often occurs in the analysis of
archaeological findings. This is very important for
potential cost (and weight) reduction, aiding the develop-
ment of compact, versatile LIBS units.
Transportable and portable LIBS systems
A major demand in scientific analysis of archaeological
objects and samples is the capability of the analytical
instrument to “travel”, enabling analysis to be performed in
the conservation laboratory, the museum, or even at the
excavation site, for rapid provision of in-situ, compositional
information about materials. This demand has created an
interest in compact, portable instrumentation and, indeed,
several examples with portable XRF [17] or (transportable)
Raman spectrometers [51] have been reported. Very few
groups have yet reported development of LIBS instruments
dedicated to or appropriate for applications in archaeolog-
ical analysis; the discipline seems quite active, however,
and results are expected in the near future. For example, in
a recent report a portable LIBS system based on a CCD
detector was described; its use was demonstrated in the
analysis of geological materials in a cave in Spain [52]. A
fully transportable laboratory LIBS system has been also
described, and is currently in use by the Conservation
Department of an Archaeology Laboratory (INSTAP Study
Center for Eastern Crete) for analysis of archaeological
objects and findings. This system is, as far as we are aware,
the only LIBS instrument dedicated to archaeological
studies [53].
754
Commercial systems
Soon after the first demonstration of the potential for
spectrochemical analysis after laser ablation of materials
LIBS-type instruments were developed in (the former East)
Germany by Zeiss, in the USA by Jarell Ash, and in Japan
by Jeol. These instruments combined laser ablation with
spark excitation but their analytical performance was
clearly inferior to that of conventional spark spectrochem-
ical analysis instruments. It is worth mentioning that the
LMA-1 (“laser microspectral analysator”) instrument de-
veloped by Zeiss in Germany was used for several years for
analysis of pigments in samples taken from paintings in the
conservation department of the National Gallery in London
[54].
With advances in laser and detector technology in the
1980s and 1990s and after successful development of
integrated prototypes in research laboratories, several
manufacturers have presented commercial versions of both
bench-type and compact transportable LIBS instruments.
Their use remains rather limited but over the last five years
there have clearly been significant attempts to promote
LIBS sensor technology to potential user communities in
industry, environmental laboratories, and even in military
and public safety organizations. Apart from limited dem-
onstration measurements no use of commercial LIBS
instruments in routine archaeological analysis has yet been
reported.
Combining LIBS with other spectroscopies
The combined use of LIBS with other spectroscopic or
imaging techniques has generated interest among research
groups that have tried to investigate means of exploiting the
complementary analytical information provided by the
different methods. Raman microscopy, laser-induced fluo-
rescence (LIF) spectroscopy, laser time-of-flight mass
spectrometry, diffuse reflectance spectroscopy, and hyper-
spectral imaging are among the techniques that have been
used in combination with LIBS [6, 55–60].
Although different experimental systems or instruments
have been used, it has also been shown that hybrid
instruments, i.e. systems that make use of a single optical
arrangement for performing measurements with two differ-
ent techniques, are feasible. For example, in recent work a
hybrid LIBS-Raman unit that makes use of a nanosecond-
pulsed laser at 532 nm to obtain both Raman and LIBS
spectra was proposed and tested for pigment analysis [50].
The system comprises a relatively simple arrangement of
components including the laser source, beam-guiding and
signal-collection optics, and a spectrograph–ICCD detec-
tion system. If the laser is operated at low power (pulse
energy <0.1 mJ) a Raman spectrum can be collected from
Anal Bioanal Chem (2007) 387:749–760
the sample surface. Increasing the pulse energy above the
ablation threshold enables LIBS analysis by use of a single
pulse. The sequence can be repeated if depth-profile
information is required. With minor changes but maintain-
ing the same hybrid-system approach LIBS and LIF
measurements can be made by using a UV laser (for
example at 355 nm) [6].
LIBS in archaeological science
Analysis of metals and metal alloys
LIBS is an excellent technique for analysis of metals and
metal alloys and is thus suitable for analysis and character-
ization of archaeological metallic artifacts such as sculp-
ture, tools, weapons, home utensils, jewelry, and coins. The
main metallic materials used in antiquity include copper
and bronze, i.e. copper–tin alloys (in the Bronze Age), and
later iron. Other metals used include lead and zinc, and
precious metals such as silver or gold alloys have been used
in jewelry and for decorating different objects.
Qualitative LIBS analysis is the first step and enables
rapid identification of the type of metal or alloy used in the
making of the object, enabling classification and screening
of different artifacts. LIBS has, for example, been used in
metal-screening analysis of several objects found in recent
excavations in Crete, Greece, helping the archaeologists to
determine whether cuprous objects were made of pure
copper, arsenical copper, or bronze, and whether jewelry
was pure or contained substantial amounts of other metals
[9]. It is not rare for simple qualitative information about
elemental composition to prove very valuable to an
archaeologist requiring information about an object. For
example, analysis of a rivet (a piece of metal used to hold
the blade in the handle of a dagger) found in the
excavations mentioned above gave important insight into
the coating of bronze with noble metals. By probing a few
representative points around the cylindrical surface of the
rivet it was found that copper was the main component.
Surprisingly, when the flat sides were examined intense
emission from silver was recorded in the LIB spectrum,
strongly suggesting the presence of a silver coating. This
simple chemical finding was extremely important archaeo-
logically [9].
Quantitative determination of the different metals pres-
ent, particularly minor and trace elements, can reveal
valuable information about metallurgical technology, period
of manufacture, and, possibly, the provenance of the raw
materials. In a recent study [61], chronological classifica-
tion of a series of bronze objects from the Bronze to the
Iron Age, from the Iberian peninsula, was achieved on the
basis of quantitative determination of the element content of
Anal Bioanal Chem (2007) 387:749–760
the alloys and, particularly, on the concentration of arsenic
(As), the presence of which is a key indicator of the Early
Bronze Age. Cluster analysis enabled reliable sorting of the
objects across the different periods. In a similar study [12]
archaeological bronze artifacts from a burial site in
Southern Tuscany, Italy, from the period 2500–2000 BC
were examined by calibration-free micro-LIBS analysis to
determine the concentrations of the elements in the alloy.
By principal-components analysis the identities and con-
centrations of the metallic elements were correlated with
typological grouping of the objects. It is important to note
that some of the LIBS results were indicative of classifica-
tion different from that suggested by traditional typology.
Other studies making use of quantitative LIBS analysis
have been used for characterization of ancient Roman
sculpture and coins [10] and of Renaissance bronze art from
Florence [62]. In the latter study the results were compared
with those obtained by standard analytical techniques,
including ICP–OES, PIXE, XRF, and AAS, and found to
be in good agreement. Quantitative analysis of metals can
clearly be extended to studies of jewelry also [63, 64].
Use of quantitative analysis, based on calibration plots
(obtained by use of reference standards) or on the
calibration-free LIBS approach, to monitor laser cleaning
of copper artifacts was examined in a recent study [65]. The
objective of the study was to establish a reliable method for
removal of different types of patina from ancient Roman
coins, which were subjected to laser cleaning. It was found
that the best results were obtained when a type of double-
pulse approach was used, with the LIBS analysis pulse (at
355 nm) 15 μs after the cleaning pulse (at 266 nm). In
similar work [66], results from laser cleaning of a heavily
corroded bronze gun (16th to 17th century AD) found on
the Adriatic seabed were evaluated by qualitative LIBS
analysis. It was concluded that significant reduction of
calcium emission indicated successful removal of the
encrustation layer.
Finally, use of double-pulse LIBS for analysis of objects
submerged in water, including iron, copper-based alloys, and
precious alloys of composition resembling that of archaeo-
logical objects, has been performed with very encouraging
results [46–48]. Standard bronze samples (quaternary alloys
of Cu, Sn, Zn, and Pb) were also examined in an attempt to
conduct quantitative analysis [46].
Studies of pottery
Ceramic objects, among the most common remnants of
ancient life, have been uncovered in numerous excavations.
Their analysis may reveal information about fabrication
technology and firing conditions, decoration techniques,
and provenance. Pigments and decorative layers, luster and
glaze, and the bulk material can be analyzed by LIBS. Even
755
clay inclusions, which may be characteristic of the clay
source or the technique employed, can be analyzed.
In recent studies [67] ancient Roman pottery sherds,
Hispanic Terra Sigillata, that originated from different
production sites and dated back to the 1st to 5th century AD
were examined. On the basis of the element content and
linear spectra correlation analysis it was possible to classify
the sherds according to their production location. Depth-
profiling studies were conducted to distinguish between the
slip and the body of the ceramic, and elements such as
calcium and iron were used as markers for the transition
from the one layer to the other [68]. In a similar study [37]
linear and rank correlation methods were used to identify a
variety of ceramic samples (archaeological and modern)
originating from Spain and Italy. A comparative study has
shown that straightforward determination of Al in archae-
ological clays can be achieved rapidly by LIBS, with
accuracy and precision not inferior to that obtained by use
of LA–ICP–MS [69].
LIBS has also been used for rapid identification of
pigments in a series of ancient ceramic and polychromed
pottery sherds, excavated in Eastern Crete, spanning the
period from 1500 BC to 1800 AD, enabling archaeologists
to correlate the type of pigment used with dating estimates
based on pottery style and excavation data [9]. Likewise,
ceramic samples (15th to 16th century AD) from Italy were
analyzed semi-quantitatively by LIBS and the compositions
of the glaze, luster, and pigment decorations were deter-
mined [10, 59]. In a similar study [70] the glaze on Chinese
pottery sherds were examined by LIBS and quantitative
analysis was performed on the basis of calibration plots
obtained by use of reference samples with silica as the main
matrix component. Color differences among the sherds
were correlated with the concentration of Fe.
Marble and stone
The analysis of stone materials, used extensively in monu-
ments, sculpture, and tools throughout antiquity, may
provide valuable information about the identity of the
mineral and possibly the origin of the stone or the type of
weathering deterioration—it is important to know this
before any conservation and restoration is planned. Most
conventional methods for characterizing bulk stone and
encrustations involve sampling from the monument or
sculpture followed by laboratory microscopic examination
and spectroscopic or chemical analysis. In this respect
LIBS, as a transportable unit, is a tool for the conservator or
restorer and is appropriate for in-situ characterization of
different types of stone and crust.
Major questions are the thickness of the crust and the
distribution of pollutants as a function of depth from the
surface. A depth-profiling study is obviously needed to
756
address such questions, as has been described for marble,
limestone, and sandstone [71–75] in relation to the use of
LIBS as a potential tool for on-line control of laser
cleaning. For example, for pentelic marble changes in the
concentration of specific elements can be used to profile the
encrustation and identify different layers. More specifically
iron and titanium, the main transition metals involved in the
marble sulfation process, can be used as indicators of the
outer gypsum layer.
In a recent study [71] LIBS was used to determine the
element composition of different types of white marble
(from Naxos in Greece, Proconnesos in Turkey, and Carrara
in Italy) both in the bulk stone and on the surface
encrustation. Quantitative data were obtained for the main
constituents (Ca, C, Al, and Si) and, at ppm levels, for
impurity elements (Fe, Mg, Mn, Ti, Ba, and Cu), by use of
reference samples based on CaCO3 matrices doped with
certified soils. By use of proper correction factors, extracted
from plasma-temperature and electron-density measure-
ments and applied to the raw spectral data, it became
feasible to achieve good quantitative analysis.
In a broader context LIBS can be a valuable tool for
analysis of different geological materials and minerals and
discrimination among them [52, 76, 77]. If differences
between element content are significant, rapid screening
can be achieved on the basis of qualitative analysis.
Quantitative analysis can be also important in uncovering,
for example, the sources of the raw materials used to make
objects, by comparison of the compositional patterns (of
minor and trace elements) of the object in question and the
original raw materials.
Glass and faience
Vitreous materials (faience, glass, glaze) are made of quartz
(or quartz sand), lime, alkalis (soda or potash), and metal
oxides. Chemical analysis of ancient glass is one way of
revealing composition, selection of raw materials, and
coloring agents. Analysis of weathered glass also aids the
study of decay processes and understanding of the
mechanisms of these.
Archaeological glass has been examined by X-ray
microanalysis (coupled with electron microscopy) and X-
ray fluorescence or PIXE. LIBS may be quite promising,
however, because, in contrast with other non-destructive
techniques, for example XRF, even light elements can be
detected. One example of this is the light element boron
(B), which can be used as a dating marker in investigation
of authenticity; boron is detectable by LIBS but not by
XRF. In a systematic study LIBS was evaluated as a
potential tool for analysis of historical glasses [11].
Measurements on a series of certified standard glass
samples, using a commercial LIBS instrument based on
Anal Bioanal Chem (2007) 387:749–760
an Echelle spectrometer (and using nanosecond laser pulses
at 266 nm), resulted in satisfactory LOD values for most
elements but the precision was rather poor (3–20%). More
research is clearly required to improve precision by
optimizing measurement conditions and corrections related
to plasma temperature and electron density variations,
given that glasses absorb rather weakly, even in the UV.
In a recent study [78] artificially weathered glass
samples (similar in composition to original glasses from
Medieval and Renaissance periods) and commercially
available ‘‘antique’’ glasses with modern chemical compo-
sition and coloring components (the chromophores) were
examined by LIBS. Analysis of their main components was
performed successfully and the presence of elements such
as cobalt, copper, manganese, iron, and chromium was
attributed to different types of chromophore, on the basis of
ions of these transition metals. Weathered glass consists of
the unaltered bulk glass material, a hydration layer created
by exchange of the alkali ions with hydrogen ions, as a
consequence of diffusion of water from the environment,
and, sometimes, a layer of corrosion salts formed external-
ly. Depth profiling by LIBS gave a qualitative indication of
the profile of the different corrosion layers of the artificially
weathered glass samples.
In an interesting application, LIBS was used to monitor
the cleaning of medieval stained glass [74]. In parallel, the
element composition of the crust and underlying material
was determined. An increase of magnesium and silicon and
a synchronous decrease of calcium were observed as the
ablation proceeded toward the glass material. The ratio of
the emission intensity of Si over that of Al was therefore
selected as a critical indicator of the end point of the
cleaning process.
Several bronze-age artifacts, for example beads, vessels,
and decorative objects made of faience were analyzed by
LIBS to identify glaze colorants and surface decorations
[79]. Faience is the oldest artificial substance, first
produced in Mesopotamia in the 5th millennium BC. The
color of the glaze was correlated with the presence of
metals, for example manganese for brown, and copper and
manganese for green, and noble metal coatings made of
gold or silver were also identified. For one of the faience
beads, examined to identify the pigment used to decorate its
surface, the emission recorded (Fig. 4) was indicative of the
presence of silver on the surface, proving that the grey
material covering the bead was not a pigment but the
remains of a corroded silver coating.
Pigments
Pigments have been used since prehistoric times and
throughout antiquity for decorating rock shelters and caves,
for wall and floor painting, and for coloring ceramic, glass,
Anal Bioanal Chem (2007) 387:749–760
Fig. 4 Spectrum obtained from a bronze age faience bead with a
silver coating
and stone objects. A study was performed recently [80] on
a variety of pigments covering a range of colors (blue, red,
yellow, green, black, orange, and grey) on painted plasters
dating back to the Eastern Mediterranean Bronze Age from
Palaikastro-Crete and Thebes-Boeotia in Greece and from
Tell el-Dab’a in Egypt. In several instances LIBS results
provided adequate evidence for safe pigment identification
in agreement with Raman and XRD measurements. For
very thin paint layers or layers with very low pigment
content it was not possible to obtain a clear picture of the
pigment because of a substantial contribution from the
plaster matrix. LIBS also proved advantageous when two
layers were present and stratigraphic analysis could reveal
the composition of the underlying layer. Similarly, quanti-
tative stratigraphy of red and yellow iron-based pigments
on ancient Roman frescoes from St Albans (UK) has been
achieved by calibration-free LIBS [7].
Biomaterials
Analysis of biomaterials is of potential interest in archae-
ological research on human remains with the objective of
identifying diseases, nutritional habits or deficiencies, or
the presence of potentially toxic elements, or animal
remains and fossils. Characterization of calcified tissues
by LIBS, for example quantitative analysis of traces of
aluminium, strontium, and lead in human bones or teeth
[81], is an example of this. It was demonstrated in this
study that these trace elements can be detected quantita-
tively and, in fact, surface-mapped in calcified tissue
samples. These results indicate convincingly the potential
advantages of LIBS in the analysis of bioarchaeological
samples.
757
Organic analysis is more challenging, because although
light elements present in organic materials, for example
carbon, hydrogen, and oxygen, can be detected by use of
the technique, non-reliable conclusions may be reached
about their exact concentrations in the sample, because of
their parallel presence in the atmosphere and their interac-
tion with atmospheric molecules. In an interesting approach
[82], LIBS was used to examine fossilized buffalo horns
from Indonesia, 400,000 and 1,000,000 years old, under
reduced pressure (3 Torr). The low-pressure surrounding
gas is crucial for overcoming undesirable broadening and
the resulting decrease in hydrogen and carbon emission
efficiency that occurs at atmospheric pressure, conditions
common in conventional LIBS analysis. This approach is
also termed laser-induced shock-wave plasma spectroscopy
(LISPS) because of the inherent role of the shock wave in
the ionization process. The carbon and hydrogen line
intensities were used as indicators of the extent of
fossilization of the samples, and thus of their age (no
carbon signal was detected in samples 1,000,000 years old).
Using the same technique [83], analysis of fresh and
fossilized corals and shells has been performed in an
attempt to establish a method for discriminating between
original and artificial materials used for fabricating beads
used in a religious context. Emissions from carbon,
hydrogen, sodium, magnesium, and calcium were proposed
as indicators for distinguishing between original and
imitation materials or between fresh and fossilized coral
beads.
Prospects
As described in this review, LIBS is a versatile analytical
technique which combines key analytical features and has
the potential to become a useful tool in archaeological
science, as shown by the variety of test cases presented. It
provides results from multi-element analysis within sec-
onds, even for the light elements. It is free from sample
preparation and nearly non-invasive, and spatial resolution
is almost microscopic. Depth-profile analysis is also
possible. All these features can be combined in compact,
portable instruments that enable use of LIBS for the
analysis of a broad variety of objects and samples at
different locations. It can be extremely useful at several
stages of archaeological research. Early analysis during
excavation could provide immediate feedback to the
archaeologist and possibly guide an on-going excavation
campaign. At the conservation laboratory LIBS can aid
proper planning of conservation treatment by providing
information about the type and extent of corrosion or
deterioration. Detailed study of the element composition of
materials can help archaeologists place objects within a
758
certain archaeological context or chronological period and
answer questions about raw materials, manufacture, and
processing. Close collaboration between archaeological
science and laser spectroscopy communities is necessary
to exploit the potential of LIBS. To this end, technological
advances are expected to enhance the capabilities and lower
the cost of LIBS systems. This will make such instruments
attractive to small or medium-scale laboratories enabling
conservators and archaeologists to make routine use of
LIBS and assess its practical value for addressing analytical
challenges in archaeological science and conservation.
Acknowledgements AG is grateful to IKY (Hellenic Foundation of
Scholarships) for a graduate fellowship.
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