Vibrational Spectroscopy 76 (2015) 4854

Contents lists available at ScienceDirect

Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

Infrared spectroscopic characterization of residues on archaeological

pottery through different spectra acquisition modes
Mariateresa Lettieri *
Institute of Archaeological Heritage Monuments and Sites, CNRIBAM, Prov.le Lecce-Monteroni, 73100 Lecce, Italy

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 9 September 2014
Received in revised form 16 December 2014
Accepted 17 December 2014
Available online 19 December 2014

Fourier transform infrared spectroscopy (FT-IR) is a versatile analytical method, very useful in many
elds. Although a crucial step in producing good spectra is the use of the appropriate technique, the
acquisition mode is sometimes not accurately selected and the results are partial or lacking.
In recent years, FT-IR analysis has been proposed as a screening method for characterization of
archaeological potteries and identication of the residues on these artifacts before turning to destructive,
more expensive, and time-consuming techniques.
In this study, a set of pottery shards, classied as fragments of amphorae, was subjected to FT-IR
analyses. The results obtained from different sampling procedures and different spectra acquisition
modes, were examined and compared.
The as-received ceramic fragments were subjected to micro attenuated total reectance (m-ATR)
analyses. Investigations in diffuse reectance (DRIFT) mode were performed on samples collected by
abrading the surfaces of the shards with abrasive paper. Samples scraped from either the surfaces of the
pottery fragments or the interior of the ceramic body, were analyzed in transmission mode as a powder in
KBr pellets or after extraction with acetone.
The sampling by abrasion of the surface with an abrasive disk, and consequently the analyses in DRIFT
mode, were successful only in identifying the inorganic compounds coming from the pottery and/or the
environment, while materials related to the content of the jar were not detected. Also the analyses in
transmission mode provided information mainly about inorganic materials, which, even where in a
limited amount, masked the signals of organic compounds. Just an extraction with a solvent made it
possible a more detailed, but still partial, characterization of these organic substances. On the contrary,
the content of the jar was easily detected using the m-ATR mode, even in areas where no residue was
observed.
2014 Elsevier B.V. All rights reserved.

Keywords:
Fourier transform infrared spectroscopy
Coated surfaces
Archaeometry
Residue analysis
Archaeological pottery

1. Introduction
Fourier transform infrared spectroscopy (FT-IR) has become a
very popular analytical technique, for many years now. This
method is fast, relatively cheap, and easy to use, and because of
these advantages, it is applied to the study of a wide range of
materials in many elds.
A crucial step in producing good FT-IR spectra is the use of the
appropriate technique for presenting the sample to the spectrometer [1]. The selection of the suitable analysis method should be
based on the type, form and amount of sample to be analyzed. The
physical state of the sample, its preparation, and the analysis
method have an effect on the resulting spectrum, modifying the

* Tel.: +39 0832 422219; fax: +39 0832 422225.

E-mail address: mt.lettieri@ibam.cnr.it (M. Lettieri).
http://dx.doi.org/10.1016/j.vibspec.2014.12.002
0924-2031/ 2014 Elsevier B.V. All rights reserved.

absorption pattern. In fact, the above mentioned factors inuence

the peak position, as well as the band shape and intensity.
Nevertheless, the spectra acquisition mode is sometimes not
accurately selected and, as a result, the information that can be
gleaned from the spectra are partial or lacking.
In recent years, FT-IR spectroscopy has been proposed as a
quick and cheap method to screen archaeological samples before
subjecting them to more expensive and time-consuming
methods (e.g., gas chromatographymass spectroscopy) [26].
Most of the studies concerning such research topics proved the
effectiveness of FT-IR analyses for the detection of organic
residues in archaeological materials, as well as for investigations
of the fabrication conditions [711] and for provenance studies
[1214].
Since ancient time, ceramic artifacts have been largely
employed for storing materials, as well as for preparing or
cooking food. As a result, traces of the materials which were in

M. Lettieri / Vibrational Spectroscopy 76 (2015) 4854

49

contact with the vessels can be found as surface deposits or as

adsorbed residues into the porous structure [15]. The characterization of these residues is very helpful to provide information on
cultural, technological, and commercial activities of ancient
societies. Chromatographic techniques are frequently employed
in identifying the organic residues [1521]. However, these
methodologies are destructive, while non-destructive or microdestructive diagnostic techniques would be preferred, and
procedures for sample preparation, usually taking a long time,
are required.
Published papers dealing with characterization of archaeological potteries and identication of the residues in ceramic
vessels, frequently discuss the application of FT-IR spectroscopy
in transmittance mode [7,8,19,2225]. Analyses performed in
diffuse reectance (DRIFT) [5,26,27] or in attenuated total
reectance (ATR) mode (sometimes coupled with a microscope,
that is, the m-ATR mode) [6,9,28] are also used in these studies.
However, despite the fact that the results depend on the
sample, on its collection and preparation, as well as on the
analysis methods, the different acquisition modes have been
frequently used with no distinction. Consequently, the characterization of the materials under study has been not comprehensive and the FT-IR technique has been undervalued and
underused.
Starting from these issues, the present research was aimed at
investigating residues on archaeological ceramic samples by
means of FT-IR spectroscopy. A set of pottery shards, classied
as fragments of amphorae, was subjected to analyses carried out in
m-ATR mode, in DRIFT mode and in transmittance mode. The
results obtained from different sampling procedures and different
spectra acquisition modes were examined and compared.

kinds of analysis. Consequently, several characterization tests can

be carried out on the same sample.
In the next step, DRIFT analyses were performed on samples
collected by abrading the surfaces of the shards with abrasive
paper, as detailed in Section 2.4.2. In this manner, small amounts of
sample can be taken from the surfaces with insignicant damage.
Furthermore, the tools for sampling are portable and can be easily
used without transferring in the laboratory the items under
investigation.
Subsequently, FT-IR analyses in transmission mode were
carried out on samples scraped from the surfaces of the pottery
fragments. This methodology made it possible to collect, and then
analyze, materials from different parts of the archaeological
fragment, with no limitation due to the original shape, dimensions
or form of the sample. In fact, the presence of residues from the
jars content was checked also inside the ceramic body. Moreover,
FT-IR analyses in transmission mode were performed after
extraction with acetone to identify the organic residues without
interferences from the ceramic material.
Finally, small akes of the residues on the internal surfaces of
the shards were analyzed in m-ATR mode. This method allows
selective examination of the residue, particularly when other
sampling procedures are difcult to perform or the archaeological
artifacts cannot be moved into the laboratory.
The analyses were carried out in the reported order, so that the
destructive or micro-destructive samplings were performed last,
because the removal of the residues from the surfaces could make
ineffective the investigations performed directly on the shards (i.e.,
the m-ATR analyses).

2. Materials and methods

A FT-IR ThermoNicolet Nexus spectrometer equipped with a

deuterated triglycine sulfate (DTGS) detector, was used to record
the FT-IR spectra in transmission mode. A 13 mm KBr die (Model
129, Thermo Spectra-Tech) and a hydraulic press (Mod 660,
Silfradent) were employed to shape the pellets for the analyses.
Following the manufacturers suggestion, 6000 kg load was
applied for approximately 1 min.
A Smart Diffuse Reectance accessory (ThermoNicolet) was
inserted in the spectrometer to perform the DRIFT analyses. This
module included a slide with a slot that can hold the sampling disk.
A kit consisting of handle and plate (which keep the adhesivebacked silicon-carbide paper used to abrade the surface) was
employed in the sampling.
The ThermoNicolet Continuum IR microscope coupled with the
spectrometer was used to acquire the FT-IR spectra. This was
equipped with a mercurycadmiumtelluride (MCT) detector,
which was cooled with liquid nitrogen. A 15 Reachromat
objective with a slide-on ATR attachment (Thermo Spectra-Tech),
using a Si crystal (refractive index = 3.4; incident angle = 45 ;
contact area = 50  50 mm), was employed to collect the m-ATR
spectra. To ensure reproducibility and uniformity, the contact
between the ATR crystal and the sample surface was automated
and computer controlled. After each analysis, the crystal was
cleaned with a soft cloth soaked in acetone.
The employed instrumentations were not purged with dry and
CO2-free air, therefore the contribute of absorption bands of both
CO2 (appearing in the spectrum as a doublet around 2340 cm 1)
and water vapor (resulting in sharp and very close peaks over
3700 cm 1) are observed in the reported spectra, although a
background spectrum was acquired before each analysis and
automatically subtracted (by software) from the sample spectrum.
All the FT-IR data were processed with the OMNIC 8.1 software
(Thermo Fisher Scientic Inc.).

2.1. Archaeological samples

The investigated samples were collected from a set of pottery
shards discovered in the archaeological site of Hierapolis (modern
Pamukkale, Turkey) [29]. Archeologists classied these ceramic
objects as fragments of amphorae manufactured and used in the
early-Byzantine period (VVI century A.D.) [30,31]. The unearthed
shards were only unsoiled with a soft brush, while washing with
either water or any other cleaning agent, was avoided.
The examined fragments have different shapes and dimensions
(not exceeding 5  5 cm2), with an average thickness of 0.5 cm.
Their concave side (hereinafter called internal side) always was the
interior surface of the jar.
Shards with residues distinguishable to the naked-eye onto the
internal side, were chosen. The observed residues were blackish
and/or brownish in color and exhibited a quite good adhesion to
the shards, but they never fully coated the pottery surface.
An example of the pottery shards under investigation is shown
in Fig. 1.
2.2. Sequence of the analyses
A preliminary visual inspection of the pottery surfaces was
performed through a binocular stereomicroscope (Zeiss, mod.
Stemi SV11) at magnications of up to 100. This examination was
aimed at distinguishing the residues from the pottery material, in
order to optimize the sampling.
The as-received ceramic fragments were rstly subjected to the
m-ATR analyses. The shape and the limited dimension of the shards
examined in this study allowed a direct analysis. In this case,
sampling or preparation procedures are not required, hence the
specimen is not damaged at all and it can be used later for other

2.3. FT-IR instrumentation

50

M. Lettieri / Vibrational Spectroscopy 76 (2015) 4854

[(Fig._1)TD$IG]

Fig. 1. A shard of amphora from Hierapolis: (a) internal side; (b) external side.

2.4. Sampling and analytical procedures

2.4.1. m-ATR mode
The m-ATR analyses were performed on both the intact pottery
shards and the akes taken from the surfaces, placing the samples
directly under the m-ATR objective. The spectra were collected
with the Si crystal in the range of 4000650 cm 1, with a resolution
of 4 cm 1 and 200 scans for each measurement; the background
spectrum was acquired in air.
In the case of the shards, the spectra were acquired on the
visible residues, as well as on apparently clean areas. Furthermore,
the analyses were carried out on both the internal and external side
of the shard, in order to avoid misinterpretation due to the
presence of substances coming from the deposition soils.
2.4.2. DRIFT mode
The samples for the tests in DRIFT mode were gathered by
gentle abrasion with a small circle of abrasive paper (320 grit SiCarb, Thermo Spectra-Tech) mounted on a stick. The DRIFT analysis
was carried out soon after the sampling. The spectra were acquired
in the range of 4000400 cm 1, with a resolution of 4 cm 1 and
200 scans per measurement; the background spectrum was
collected on the same abrasive paper disk afterwards used for the
sampling. For comparison, the sampling and the analyses were
performed on both the internal and external sides of the pottery
fragment.
2.4.3. Transmission mode
The internal and the external surfaces of the shards were
scraped with a scalpel to collect the samples as a powder to be used
for the analyses in transmission mode. In the same way, the matter
was taken also from the lateral side of the shard, at different
depths, to investigate the presence of residues due to the jars
content inside the ceramic body. These samples were nely ground
with a pestle in an agate mortar, then mixed with KBr (suitable for

infrared analysis and provided by Mallinckrodt Baker Chemical

Inc.) and compacted in a pellet 13 mm in diameter.
The material gathered from the internal surface of the shard
was divided in two parts. The rst one was used to prepare KBr
pellets. The second part, placed in a vial, was extracted with
acetone (analytical grade, provided by Carlo Erba Reagents), using
1 ml of solvent per 5 mg of sample. Sonication was carried out for
22 min in an ultrasonic bath (FALC Instruments), followed by
standing for 24 h in laboratory conditions. A drop of the obtained
liquid fraction was placed on a KBr pellet, previously prepared,
which was stored for 5 min at 40  C to enhance the solvent
evaporation.
All the KBr pellets were analyzed in transmission mode,
immediately after the preparation. The spectra were acquired in
the range of 4000400 cm 1, with a resolution of 4 cm 1 and 200
scans per measurement; the background spectrum was collected
on a pellet made of KBr only.
3. Results and discussion
The observations through the stereomicroscope, preliminary to
the samplings, allowed to identify residues having dissimilar
features. Areas different in appearance were noticed on the
surfaces, as described below:
a Brown coatings;
b Dark-brown residues lling holes and gaps of the surface;
c Surfaces with no visible residue, where the ceramic body was

easily recognized;
d Whitish incrustations.

In all the examined archaeological samples, the rst three types

of residues (13) were observed on the internal surface of the
shards, as shown in Fig. 2a. Instead, the whitish incrustations (4)
were mainly found on the external side (see Fig. 2b).

[(Fig._2)TD$IG]

Fig. 2. Images of the potsherd taken by means of the stereomicroscope: (a) internal side; (b) external side.

M. Lettieri / Vibrational Spectroscopy 76 (2015) 4854

3.1. m-ATR mode

The investigations carried out in m-ATR mode on the internal
surfaces of the shards were very signicant. As previously stated,
spectra were acquired directly on visible residues, as well as on
apparently clean areas, where the visual inspection, either to the
naked-eye or through the stereomicroscope, did not reveal any
residue.
The most of the analyses of the visible residues gave rise to
spectra where the bands at 2952, 2928, 2863, 1710, 1448, and
1172 cm 1 indicated the presence of vegetable resins [1,6,32], even
if the peak around 1033 cm 1, due to the silicate compounds of the
pottery, was the strongest signal (Fig. 3a-1). In these spectra,
signicant signals at 1584, 1385, and 1229 cm 1 were also
detected. In other cases, actually less frequent, the spectra of
the residues on the internal side of the shards exhibited bands
around 1572, 1386 and 1228 cm 1 as main peaks (Fig. 3b). Other
researchers attributed similar signals to crystals of tartrate salts
[26,3335]. In fact, tartrates, usually as calcium or potassium salts,
can derive from tartaric acid occurring in large amounts in grapes
and have been proposed in many studies as a marker of wine in
archaeological potteries [3638].
The results of the analyses performed in m-ATR mode on akes
of residues are reported in Fig. 3a-2. These spectra resulted very
similar to those collected directly on visible residues (area (1) in
Fig. 2a).
These ndings were supported by the results of the GCMS
analyses on the same samples as discussed in another study [39].
Abietic acid, dehydroabietic acid and 7-oxo-dehydroabietic acid
were identied in the residues, indicating the presence of a pine
resin and/or a pitch obtained from resinous materials of Pinaceae
trees [25,38,4042]. Tartrates was not detected, but it is to take into
account that GCMS technique can be not suitable to unambiguously prove the existence of tartaric compounds in archaeological
samples [21].
The m-ATR spectrum acquired on clean areas is shown in Fig. 4.
Although the main peak was due to silicate compounds of the
ceramic body, organic matter ascribable to the content of the jar
was recognized. Vegetable resins can be identied from the signals
at 2960, 2925, 2866, 1712, and 1449 cm 1, while the peaks around
1586 and 1385 cm 1 could account for the presence of calcium
tartrate. Traces of carbonates were also detected (1416 and
872 cm 1).
On the outside of the shards greater amounts of carbonates
(1415 and 872 cm 1) and no evidence of organic materials, were

51

found (Fig. 5). In addition, peaks at 3620 and 3690 cm 1, due to the
OH stretching modes [43] of clay minerals belonging to the
kaolinite-group [44], were detected. Analogous signals were not
noticed in the spectra of the inner surface.
Finally, it is to remark that the broad band around 3400 cm 1
and the peak centered at 1625 cm 1, both related to HOH
vibrations of adsorbed water [44], were weaker in the spectra of
the external side.
Using the FT-IR analyses in m-ATR mode, the supercial
substances were mainly recognized, while the absorption bands
deriving from the ceramic body were not strong in intensity. As a
consequence, the signals due to residues were not masked and the
related substances were quite easily identied. Furthermore,
residues from the content of the jar were detected even in areas
where no residue was revealed by the visual observation. Shape
and dimensions of the investigated object could impede a suitable
spectral acquisition, but the ATR technique gave meaningful results
also in analyzing selected small pieces of materials taken from the
shard. This latter result makes the technique valuable when the
sampling is carried out on unbroken artifacts.
3.2. DRIFT mode
The results of the analyses performed in DRIFT mode are
reported in Fig. 6.
The bands due to silicate (1025 cm 1) and carbonate (1450 and
874 cm 1) compounds are the main peaks in the spectra of the
material sampled from the internal surface of the shards. The peaks
at 2960, 2920, and 2850 cm 1 suggest the presence of organic
substances, even if no further information can be inferred from
these data. However, these signals cannot be unambiguously
attributed to organic materials, because peaks between 2850 and
3000 cm 1, similar in shape, are observed also in the standard
reference DRIFT spectrum (HR Nicolet Sampler Library, Thermo
Fisher Scientic Inc.) of calcium carbonate.
Reasonably the external side of the potsherds did not have
contact with the content, therefore, for comparison purpose,
analyses in DRIFT mode were performed on specimens taken from
these surfaces.
In comparing the spectra (Fig. 6), peaks in the range of 2850
2960 cm 1 were still noticed, even if some differences can be
observed. Greater amounts of carbonates were found on the
external surfaces, because the peaks at 1450 and 874 cm 1 were
stronger in intensity. Furthermore, in both cases the overtone
bands of the carbonate group were observed at 2516 and

[(Fig._3)TD$IG]

Fig. 3. m-ATR spectra of residues on the internal surfaces: (a) 1 = recurrent result in areas with visible residues, 2 = spectrum acquired on a ake of residue (shown in the inset
box) taken from the internal side of a shard; (b) less frequent result in areas with visible residues.

52

[(Fig._4)TD$IG]

M. Lettieri / Vibrational Spectroscopy 76 (2015) 4854

3.3. Transmission mode

Fig. 4. m-ATR spectrum collected in an area of the internal surface without visible
residues.

1796 cm 1 [3]. Other researchers attributed similar results to

carbonate compounds in a powdered state [5] from layers covering
the outside of the shards, realistically due to deposition from
circulating uids taking place in the burial conditions [45,46]. In
the spectra collected on samples from the external side, peaks
around 3620 and 3690 cm 1, due to clay minerals, were identied.
This result is indicative of the presence of unred raw material
from the environment; in fact, these peaks are usually not
observed in red archaeological ceramics, where the high ring
temperatures cause the dehydroxylation of the clays [12,47,48]. As
already found in ATR spectra, the signals related to HOH
vibrations of adsorbed water, that is, the band centered at
3400 cm 1 and the peak at 1630 cm 1, were stronger in the
spectra of the internal side.
The analyses carried out using the DRIFT technique allowed to
detect just the most abundant compounds, that is, carbonates and
silicates. Substances from both the pottery and the environment
were detected, but evidence of the jars content was not clearly
found. However, these results could be the consequence of the
sampling method. The abrasion of the surface with an abrasive disk
could be not able to collect the appropriate amount of residues. It is
worth reminding that the substances contained in the jar could
have been absorbed into the porous structure of the ceramic fabric,
while residues remained on the surfaces only in a limited amount.

[(Fig._5)TD$IG]

Fig. 5. m-ATR spectrum collected on the external surface.

In the spectra acquired in transmission mode (Fig. 7a), the

strong absorption band at 1032 cm 1 allowed to recognize silicate
minerals as the main constituents of samples scraped off from the
internal surfaces of the shards. The presence of quartz and iron
oxide minerals was inferred from the characteristic doublet at
795 and 773 cm 1 and the signal around 520 cm 1, respectively.
The peaks at 1420, 872 and 710 cm 1 indicated carbonate
compounds in the samples.
The presence of organic substances was identied by the peaks
at 2954, 2925, 2850, 1730, 1457, and 1381 cm 1. The band at
1381 cm 1 could also be due to nitrate salts coming from burial
soils. This hypothesis was not conrmed because the same peak
was not observed in the spectra acquired on samples from the
external surface. Therefore, the absorption band at 1381 cm 1
arose from a compound in contact only with the internal side of the
amphora. On the outside of the shards greater amounts of
carbonates and no evidence of organic materials, were found. In
addition, as already observed in the spectra acquired in both ATR
and DRIFT mode, peaks at 3616 and 3692 cm 1 testied to the
presence of unred clay minerals from the environment.
Regarding the nature of the organic residues, position and
shape of the related peaks suggested the presence of a vegetable
resin [1]. The CH stretching vibration modes of the methyl and
the methylene group accounted for the peaks between 2850 and
2960 cm 1 [25]; the bands at 1457 and 1381 cm 1 were due to CH2
and CH3 bending; nally, the signal around 1730 cm 1 (ascribable
to ketone groups) suggested the presence of resin derivatives [2], a
likely result of aging processes that took place naturally or as a
consequence of intended actions (such as the thermal treatment
used in preparing pitch). Actually, rather than from substances in
contact with the pottery during its use or preparation, organic
matter can also be deposited throughout the burial period. The
absence of signicant signals due to organic compounds in the
spectra of the samples collected on the external side excluded this
event. Similar signals, that is, the same organic materials were
identied inside the ceramic body, although only near the internal
side of the shards.
Quartz and iron oxides were constituent materials, because
these minerals were recognized with no distinction between the
inside and the outside of the ceramic body. Very low amounts of
carbonates were identied in the ceramic material; their presence
only on the outside surfaces indicated formation and deposition
during the burial period.

[(Fig._6)TD$IG]

Fig. 6. Spectra collected in DRIFT mode.

M. Lettieri / Vibrational Spectroscopy 76 (2015) 4854

[(Fig._7)TD$IG]

53

Fig. 7. Spectra of powder scraped off from either the shards surfaces or different depths into the ceramic body, collected in transmission mode: (a) the spectra in the full range
of acquisition (4004000 cm 1); b) the comparison in the range of 30003800 cm 1.

As can be seen from Fig. 7b, where the range between 3000 and
3800 cm 1 is expanded and compared, the band at 3425 cm 1
gradually decreased from the inside to the outside of the shards.
Actually, a similar trend was observed for the peak at 1630 cm 1.
These signals, due to water, very probably originated from
hydration of minerals in the ceramic body. Since the exposure
to water/humidity in the burial environment can be supposed
identical for the whole shard, the stronger intensity could arise
from a more prolonged contact of the internal surfaces with
aqueous substances during the use of the vessels.
The FT-IR spectra of liquid obtained by extraction with acetone
from residues on the interior surfaces of the shards is reported in
Fig. 8. Signals usually ascribed to terpenic compounds of vegetable
resins [19,40] were observed. The CH2 and CH3 groups of the
hydrocarbon skeleton in these resins gave rise to strong stretching
vibrations at 2956, 2927 and 2854 cm 1 [3,23]. The bands at
1452 and 1381 cm 1 due to the CH bending modes [24], were also
recognized. The peaks in the range of 12651120 cm 1 addressed
to different CO vibration modes, while the stretching bands of
carbonilic groups were observed at 1699 and 1722 cm 1. This latter
(i.e., the peak at 1722 cm 1) suggested the presence of ketone
groups, which were typically found in pitch [2,3,23]. The absence of
peaks in the range of 17351745 cm 1, indicative of methyl esters
of resin acids, should exclude the presence of wood tar [2].

[(Fig._8)TD$IG]

Fig. 8. Spectrum of liquid obtained by extraction with acetone from the residues,
collected in transmission mode.

Actually, the lack of these signals would not be a conclusive test

because methyl esters could have been hydrolyzed in free acids in
the burial conditions [2]. Finally, the very strong absorption at
3450 and 1640 cm 1 can be due to water molecules soaked up
during the tests or absorbed in the clay structure [5]. As previously
stated, the GCMS analyses, performed in another study [39],
conrmed the presence of pine resin and/or pitch.
he FT-IR analyses performed in transmission mode were
successful in characterizing the constituent materials of the
pottery. Also the residues from both the content of the jar and
the burial environment were distinguished. Moreover, this
technique allowed to have information about the distribution of
the different compounds along the thickness of the shard. The
presence of inorganic substances, even in small amounts, made
difcult the exact identication of organic materials in the sample.
A partial characterization of these compounds was possible only
after extraction with a solvent. However, this procedure (i.e., the
extraction) and the used solvent strongly affect the results. In fact,
the analyses in transmission mode did not reveal the presence of
tartrate salts which were easily identied by the m-ATR analyses.
4. Conclusions
In this study a set of pottery shards classied as fragments of
amphorae was analyzed by FT-IR spectroscopy. The results
obtained from different sampling procedures and different
analytical methodologies were examined and compared.
Among the procedures used in this research, the sampling by
abrasion of the surface with an abrasive disk, and consequently the
spectroscopic analyses performed in DRIFT mode, were successful
only in identifying the inorganic compounds coming from the
pottery and the environment. The materials related to the content
of the jar were not detected. These substances were trapped for the
most part into hollows, gaps and pores of the pottery. Therefore,
the sampling method used in this case allowed to collect the
samples without damage, but precluded from taking a proper
amount of material.
Also the analyses in transmission mode on samples scraped as a
powder provided information mainly about inorganic materials
(i.e., constituent materials of the pottery, substances from the
burial environment). The sampling inside the ceramic body was
useful to investigate the distribution of the different compounds
along the thickness of the shard. However, the presence of
inorganic materials, even where in a limited amount, masked the
signals of other organic compounds, usually found in traces. Just an

54

M. Lettieri / Vibrational Spectroscopy 76 (2015) 4854

extraction with a solvent made it possible a more detailed, but still

partial, characterization of these organic substances.
The FT-IR analyses performed in m-ATR mode gave several
advantages. Supercial substances were mainly recognized, the
signals due to the ceramic body were weak in intensity and they
did not hide the presence of other materials. In fact, the content of
the jar was easily detected even in areas where no residue was
observed. The m-ATR technique is a minimally invasive methodology, hence, it allows to use the same sample for further analytical
investigations, or preserve it without damage. The m-ATR
technique resulted really effective also in analyzing selected small
pieces of materials taken from the archaeological samples. This
sampling method can be applied in case of unbroken artifacts,
when the archaeological objects cannot be moved into the
laboratory and whenever other sampling procedures are difcult
to perform.
The ndings of this study supported the FT-IR spectroscopy as a
simple, fast and economical technique. The analytical results
depend on the applied sampling method, but a limited or no
preparation is usually suitable to obtain reliable and sound data.
Finally, the versatility of the FT-IR technique is conrmed. In
fact, the methods employed here allowed to investigate samples in
different forms.
Acknowledgements
The author is grateful to Prof. Francesco DAndria (Director of
the Italian Archaeological Mission at Hierapolis) and Dr. Daniela
Cottica (Department of Humanities, Ca' Foscari University of
Venice) for the opportunity to analyze the artifacts from Hierapolis
and for providing the archaeological samples.
Thanks go to Dr. Florinda Notarstefano (Department of Cultural
Heritage, University of Salento, Lecce) for her helpful suggestions
in the interpretation of the results.
References
[1] M.R. Derrick, D.C. Stulik, J.M. Landry, Infrared Spectroscopy in Conservation
Science, The Getty Conservation Institute, Los Angeles, 1999.
[2] J. Font, N. Salvad, S. But, J. Enrich, Anal. Chim. Acta 598 (2007) 119127.
[3] L.M. Shillito, M.J. Almond, K. Wicks, L.J.R. Marshall, W. Matthews, Spectrochim.
Acta A 72 (2009) 120125.
[4] T.F.M. Oudemans, J.J. Boon, R.E. Botto, Archaeometry 49 (2007) 571594.
[5] G. Tarquini, S. Nunziante Cesaro, L. Campanella, Talanta 118 (2014) 195200.
[6] F. Mizzoni, S. Nunziante Cesaro, Spectrochim. Acta A 68 (2007) 377381.
[7] R. Ravisankar, S. Kiruba, C. Shamira, A. Naseerutheen, P.D. Balaji, M. Seran,
Microchem. J. 99 (2011) 370375.
[8] G. Velraj, R. Ramya, R. Hemamalini, J. Mol. Struct. 1028 (2012) 1621.
[9] M.J. Ayora-Caada, A. Domnguez-Arranz, A. Dominguez-Vidal, J. Raman
Spectrosc. 43 (2012) 317322.
[10] S.A. Centeno, V.I. Williams, N.C. Little, R.J. Speakman, Vib. Spectrosc. 58 (2012)
119124.
[11] G.A. Mazzocchin, F. Agnoli, I. Colpo, Anal. Chim. Acta 478 (2003) 147161.
[12] R. Ravisankar, A. Naseerutheen, G. Raja Annamalai, A. Chandrasekaran, A.
Rajalakshmi, K.V. Kanagasabapathy, M.V.R. Prasad, K.K. Satpathy, Spectrochim.
Acta A 121 (2014) 457463.

[13] G. Barone, S. Ioppolo, D. Majolino, P. Migliardo, G. Spagnolo, J. Cult. Herit. 3

(2002) 171176.
[14] D. Barilaro, G. Barone, V. Crupi, D. Majolino, P. Mazzoleni, M. Triscari, V. Venuti,
Vib. Spectrosc. 42 (2006) 381386.
[15] R.P. Evershed, Archaeometry 50 (2008) 895924.
[16] R.P. Evershed, C. Heron, L.J. Goad, Analyst 115 (1990) 13391342.
[17] M. Regert, Mass Spectrom. Rev. 30 (2011) 177220.
[18] S. Mitkidou, E. Dimitrakoudi, D. Urem-Kotsou, D. Papadopoulou, K. Kotsakis, J.
A. Stratis, I. Stephanidou-Stephanatou, Microchim. Acta 160 (2008)
493498.
[19] M.P. Colombini, G. Giachi, F. Modugno, E. Ribechini, Microchem. J. 79 (2005)
8390.
[20] D. Arobba, F. Bulgarelli, F. Camin, R. Caramiello, R. Larcher, L. Martinelli, J.
Archaeol. Sci. 45 (2014) 226233.
[21] K. Romanus, J. Baeten, J. Poblome, S. Accardo, P. Degryse, P. Jacobs, D. De Vos, M.
Waelkens, J. Archaeol. Sci. 36 (2009) 900909.
[22] F. Dorrego, F. Carrera, M.P. Luxn, Mater. Struct. 37 (2004) 369374.
[23] F.C. Izzo, E. Zendri, A. Bernardi, E. Balliana, M. Sgobbi, J. Archaeol. Sci. 40 (2013)
595600.
[24] E. Ribechini, F. Modugno, C. Baraldi, P. Baraldi, M.P. Colombini, Talanta 74
(2008) 555561.
[25] S. Zareva, I. Kuleff, Spectrochim. Acta A 76 (2010) 283286.
[26] P.E. McGovern, D.L. Glusker, L.J. Exner, M.M. Voigt, Nature 381 (1996) 480481.
[27] C. Cardell, I. Guerra, J. Romero-Pastor, G. Cultrone, A. Rodriguez-Navarro, Anal.
Chem. 81 (2009) 604611.
[28] J. Baeten, K. Romanus, P. Degryse, W. De Clercq, H. Poelman, K. Verbeke, A.
Luypaerts, M. Walton, P. Jacobs, D. De Vos, M. Waelkens, Microchem. J. 95
(2010) 227234.
[29] F. DAndria, M.P. Caggia, I. Hierapolis di Frigia, Le Attivita delle Campagne di
Scavo e Restauro 20002003, Ege Yayinlari, Istanbul, 2007.
[30] D. Cottica, Hierapolis di Frigia I. Le attivit delle campagne di scavo e restauro
20002003, in: F. DAndria, M.P. Caggia (Eds.), MAIERMissione Archeologica
Italiana a Hierapolis, Ege Yayinlari, Istanbul, 2007, pp. 257277.
[31] M. Lettieri, F. Notarstefano, Il Dialogo dei Saperi. Metodologie integrate per i
Beni Culturali, in: F. DAndria, D. Maltana, N. Masini, G. Scardozzi (Eds.),
Edizioni scientiche italiane, Napoli, 2010, pp. 337352.
[32] S. Prati, G. Sciutto, R. Mazzeo, C. Torri, D. Fabbri, Anal. Bioanal. Chem. 399
(2011) 30813091.
[33] P.E. McGovern, D.L. Glusker, R.A. Moreau, A. Nunez, C.W. Beck, E. Simpson, E.D.
Butrym, L.J. Exner, E.C. Stout, Nature 402 (1999) 863864.
[34] P.E. McGovern, J. Egypt. Archaeol. 83 (1997) 69108.
[35] X. Sahaya Shajan, C. Mahadevan, Cryst. Res. Technol. 40 (2005) 598602.
[36] M.R. Guasch-Jan, C. Andrs-Lacueva, O. Juregui, R.M. Lamuela-Ravents, J.
Archaeol. Sci. 33 (2006) 98101.
[37] R.H. Michel, P.E. McGovern, V.R. Badler, Anal. Chem. 65 (1993) 408A413A.
[38] A. Pecci, G. Giorgi, L. Salvini, M.A. Cau Ontiveros, J. Archaeol. Sci. 40 (2013)
109115.
[39] F. Notarstefano, Ceramica e alimentazione: l'analisi chimica dei residui
organici nelle ceramiche applicata ai contesti archeologici, Edipuglia, Bari,
2012.
[40] M.P. Colombini, G. Giachi, F. Modugno, P. Pallecchi, E. Ribechini, Archaeometry
45 (2003) 659674.
[41] M.P. Colombini, F. Modugno, E. Ribechini, J. Mass Spectrom. 40 (2005)
675687.
[42] E. Ribechini, S. Orsini, F. Silvano, M.P. Colombini, Anal. Chim. Acta 638 (2009)
7987.
[43] R.L. Frost, Clays Clay Miner. 43 (1995) 191195.
[44] J. Madejov, Vib. Spectrosc. 31 (2003) 110.
[45] M.A. Cau Ontiveros, P.M. Day, G. Montana, Modern Trends in Scientic Studies
on Ancient Ceramics, in: V. Kilikoglou, A. Hein, Y. Maniatis (Eds.),
Archaeopress, Oxford, 2002, pp. 918.
[46] E. Andaloro, C.M. Belore, A.M. De Francesco, J.K. Jacobsen, G.P. Mittica, Appl.
Clay Sci. 53 (2011) 445453.
[47] S. Shoval, Opt. Mater. 24 (2003) 117122.
[48] F. Berna, A. Behar, R. Shahack-Gross, J. Berg, E. Boaretto, A. Gilboa, I. Sharon, S.
Shalev, S. Shilstein, N. Yahalom-Mack, J.R. Zorn, S. Weiner, J. Archaeol. Sci. 34
(2007) 358373.