Appl. Phys.
A 83, 605–609 (2006)
DOI: 10.1007/s00339-006-3552-x
g. quartau An integrated accelerator mass spectrometry
m. d’elia
k. butalag radiocarbon dating and ion beam analysis
l. maruccio
g. demortier
approach for the study
l. calcagnile of archaeological contexts
CEDAD, Centro di datazione e diagnostica, Dipartimento di Ingegneria dell’Innovazione,
Università di Lecce, 73100, Lecce, Italy
Received: 15 June 2005/Accepted: 18 January 2006
Published online: 24 March 2006 • © Springer-Verlag 2006
ABSTRACT The integration in the accelerator-based facility at
CEDAD (Centro di Datazione e Diagnostica), University of
Lecce, of a state-of-the art AMS (accelerator mass spectrome-
try) 14 C dating system, and three different beam lines for IBA
(ion beam analysis) compositional investigations, has given the
possibility of developing an integrated IBA-AMS approach to
the study of a wide range of archaeological problems. Here we
present three cases where in air IBA methods were involved
for the elemental characterisation of objects found in archae-
ological contexts, chronologically defined on the basis of high
resolution AMS14C measurements.
In particular we report on the identification of cinnabar
(HgS) on Neolithic bones, the compositional analysis of a set of
golden artefacts dated at the final Bronze age, and the analysis
of red decorations on Neolithic pottery.
PACS 32.30.Rj; 34.50.Dy; 82.80.Ms
1 Introduction
The possibility of carrying out, in the same accel-
erator-based facility, accelerator mass spectrometry radiocar-
bon dating and compositional characterisation based on ion
beam analysis techniques, represents a unique possibility for
the development of a versatile tool for the diagnostics of cul-
tural heritage.
The availability of such a facility at the University of
Lecce has allowed a highly integrated approach to a wide
range of archaeological problems where the potentialities of
the AMS dating method (precision of 0.2% – 0.3% and dat-
able range of 45 – 50 ka) are coupled with the advantages of the
IBA techniques, namely the possibility of performing multi-
elemental, non destructive, quantitative analyses in air.
The effectiveness of this approach is demonstrated here on
three different archaeological problems: the study of a set of
golden artefacts from the Bronze age, the study of red pig-
ment found on human bones in a Neolithic burial site, and the
study of red pigment used for decorative purposes on a “Serra
u Fax +39-083-150-7408, E-mail: gianluca.quarta@unile.it
Applied Physics A
Materials Science & Processing
d’Alto” pot found in Serra Cicora, a Neolithic site in Southern
Italy.
2 The AMS-IBA facility at CEDAD
The AMS-IBA facility of the University of Lecce
is based on a 3 MV Tandetron accelerator manufactured by
High Voltage Engineering Europa, equipped so far, with three
experimental lines for:
– accelerator mass spectrometry radiocarbon dating;
– high energy ion implantation;
– in vacuum ion beam analysis (Rutherford backscattering
spectrometry) and channelling.
The experimental potentials of the facility have been sig-
nificantly enhanced recently, by the installation of a new
beam line dedicated to in air compositional characterisation
by PIXE (particle induced X-ray emission). The new beam
line will be mainly involved in studies concerning the diag-
nostics of objects of archaeological or artistic relevance as
well as in environmental studies.
A nuclear microprobe beam line, based on an Oxford Mi-
crobeam focusing triplet lens, is currently under installation.
The experimental chamber of this line will be integrated with
an optical system able to deliver a tunable, high power laser
beam on the sample during its irradiation with the highly spa-
tially resolved proton beam, in order to perform nuclear and
optical characterisations at the same time.
2.1 Optimised performances of the AMS apparatus
A complete and detailed description of the AMS
radiocarbon dating facility installed at the University of
Lecce, in operation since 2003, has been given elsewhere [1].
The possibility of performing measurements in the new facil-
ity with a precision of 0.2% – 0.3% and 0.05% – 0.1% on the
14
C/12 C and 13 C/12 C ratio determinations, respectively, has
been also shown [2].
As an indication of the routine performances of the fa-
cility, Fig. 1 shows the uncertainty (1 standard deviation) in
the measurement of the radiocarbon age of a set of 570 sam-
ples measured in 2004, no distinction is made with respect
to the sample material (charcoals, wood, human and animal
606 Applied Physics A – Materials Science & Processing
FIGURE 1 Uncertainty (one standard deviation) in the measurement of the
14 C age of a set of 570 measurements carried out at CEDAD in 2004. No
distinction is made with respect to sample age, mass and material
bones, marine carbonates, sediments), sample mass (ranging
between 0.2 and 2 mg of purified elemental carbon), and age
(ranging between the modern and 42 000 years BP in the ra-
diocarbon timescale). The figure shows that an uncertainty of
40 years is routinely achieved while high precision measure-
ments are also possible with an uncertainty down to 20 years.
The accuracy of the measurements is constantly moni-
tored in the frame of an internal quality assurance protocol,
through the analysis of samples dated by other techniques
(mainly dendrochronology) or in other AMS or β counting
radiocarbon laboratories or in the frame of international in-
tercomparison exercises (like VIRI: Fifth International Radio-
carbon Intercomparison). A complete report on a large set of
these accuracy tests is reported in [1].
The main applications of the facility cover a wide range
of research fields from archaeology and the history of art,
geomorphology, environmental sciences and forensic sci-
ences [3–5].
The throughput of the whole facility has been increased
as well, by the installation of new sample processing lines.
Nowadays up to 50 samples are prepared and dated per week.
A new protocol for assessing bone preservation and for de-
termining the purity and the amount of collagen, based on
a FTIR (Fourier transform infrared) spectroscopy system is
also under development.
2.2 The external beam PIXE set up
The external beam PIXE beam line, 6 m long, is
connected to the −15◦ port of the high energy switching mag-
net. A fast closing valve manufactured by VAT, Switzerland
with a closing time < 10 ms separates the beam line from
the rest of the system, thus protecting the accelerator from
vacuum problems resulting from the breakdown of the beam
extraction window.
At the external beam end stage, the beam is collimated by
a high-purity 1 mm graphite collimator before its extraction in
air through an aluminium window. The use of different extrac-
tion windows, such as Mylar or silicon nitride, is being tested.
Currently, in typical experimental conditions (50 nA, 3 MeV
proton beam) a lateral resolution in air of ∼ 2 mm is achieved.
Two detectors are currently employed for the X-ray de-
tection: a Canberra SSL30150, Si(Li) detector (30 mm2 active
area, 3 mm thickness, 0.025 mm Be window) with a reso-
lution of 160 eV FWHM at 5.9 keV (Mn K α ) and a Canberra
Germanium detector with a resolution of 140 eV FWHM at
5.9 keV. The position of both the detectors can be adjusted by
two mobile tables in order to regulate the distance from the
sample and the angles. The X-ray spectra are acquired by the
Canberra Genie 2000 Data Acquisition and Analysis software
allowing the contemporary acquisition of up to eight detectors
and off-line analysis by using the GUPIX code.
3 Results and discussion
Three cases in which an integrated AMS-IBA ap-
proach has been used are presented for the study of a set of
golden discs from the bronze age, a red pigment found on the
bones from a Neolithic burial site and on the decoration of
a Neolithic pot.
3.1 The gold discs of Roca Vecchia
The archaeological site of Roca Vecchia, is located
on the Adriatic coast of the Salento peninsula in Apulia,
Southern Italy. The site is an object of systematic excava-
tions since 1987 by the Department of Cultural Heritage of the
University of Lecce which brought to light testimonies of the
use of the site for a wide time range from the Bronze to the
Middle age. Over the last few years a large campaign of 14 C
AMS dating has been carried out at CEDAD for the absolute
chronological definition of the different occupation phases.
Here we report on the non destructive compositional charac-
terisation of two golden discs found in Roca Vecchia, whose
age has been, although indirectly, determined by carrying out
high resolution AMS 14 C measurements.
The two discs still had their original circular shape
(10 334.28 and 10 334.68) (Fig. 2), and were found in a pit
associated with other discs which were (most likely inten-
tionally) torn into two or more pieces and folded into four or
more layers. Most likely two of these finely carved discs were
joined together by riveting in order to form a type of convex
lens, probably representing the sun. The complete set of all the
discs has already been investigated by external PIXE, and the
results are given in [6].
In order to chronologically define the archaeological con-
text, four different short living samples (Vicia Faba Minor)
archaeologically associated with the two discs were selected
to carry out 14 C AMS analysis.
The four samples were prepared for the AMS analysis
by using conventional AAA (acid–alkaly–acid) sample pro-
cessing procedures [7, 8], and dated to 2964 ± 55 BP, 2929 ±
45 BP, 2923 ± 50 BP, 2930 ± 40 BP, respectively. The scat-
tering of the data (Fig. 3) shows that they are normally dis-
tributed (χ 2 = 0.1) and thus a weighted average of 2934 ±
25 BP can be calculated.
The weighted conventional radiocarbon age has been then
calibrated in calendar years by using the software OxCal 3.10
based on the last atmospheric radiocarbon calibration data set
(INTCAL 04), obtaining a calendar age of the samples and
QUARTA et al. An integrated 14 C AMS-IBA approach in archaeology
FIGURE 2 One of the golden discs (sample 10 334.68) of the Bronze Age
found in Roca Vecchia, Lecce
FIGURE 3 Results of the AMS 14 C measurements carried out on four short
lived samples found in association with the golden discs in Roca Vecchia,
Lecce
thus, although indirectly, of the golden discs between 1220
and 1040 cal BC (2σ confidence level) [9].
The composition of the two discs has been determined by
carrying out in air PIXE analyses, and using the set-up pre-
viously described. In particular the detector formed an angle
of 45◦ with the proton beam and a 50 mg/cm2 cellulose fil-
607
ter was placed in front of it in order to cut off the low energy
component of the X-ray spectrum.
The PIXE analysis showed that the samples are formed
by a ternary (Au, Ag, Cu) alloy and that the two discs have
a quite homogeneous elemental composition with an Au con-
centration of 79.65 ± 0.21 and 83.10 ± 0.55 wt., and an Ag
concentration of 18.24 ± 0.14 and 14.72 ± 0.03 wt. for disc
10 334.28 and 10 334.68, respectively. This compositional ho-
mogeneity can be seen as a hint of a common origin of the raw
material and a uniform metalworking.
The in depth homogeneity was estimated by comparing
the ratios between the intensities of the Au L and Au K lines
measured for the samples and for a homogeneous gold stan-
dard. The results show that the Au- L/Au- K lines ratio for the
samples are respectively 280 ± 90 for sample 10 334.28 and
283 ± 82 for sample 10 334.68, and is comparable with that
obtained for the gold homogeneous standard 274 ± 35, indi-
cating that the objects are homogeneous in depth, at least for
the analyzed depth (∼ 15 µm).
3.2 The use of cinnabar (HgS)
in the Neolithic burial
site in Carpignano, Lecce, Italy
During the restoration work of a private house in
Carpignano Salentino, Lecce, Southern Italy, a burial was
brought to light. The anthropological analysis of the rests led
to the identification of seven inhumated individuals (3 adults
male, 3 children between 6 and 12 years old, and a child
younger than 6 years) [10]. In particular one of the adults
was in an anatomical natural position. The objects found in
association with the bones such as flint and obsidian tools,
ashes, a bone fish hook, allowed the archaeological dat-
ing of the burial to the late Neolithic era. What was par-
ticularly interesting about this burial was that some of the
bones were covered by a red pigment whose nature was
unknown.
The two main archaeological problems concerning this
burial were, its absolute chronological definition and the iden-
tification of the red pigment.
In order to obtain an absolute date for the burial, a bone
sample (CS 273.4) from the individual in the anatomic con-
nection was selected for AMS radiocarbon analysis. This indi-
vidual was, most likely, the last one to be buried representing,
thus, the last moment of the use of the burial.
The sample was treated with the conventional protocol
in use at CEDAD for the processing of bone samples and is
described in detail elsewhere [7], in particular, collagen was
extracted from the bone by using the method described by
Longin [11]. Table 1 shows the results obtained for the sam-
ple: the radiocarbon age, the δ13 C term and the calibrated time
Sample Radiocarbon Age δ13 C (‰) Calibrated time range
CS 273.4 5665 ± 30 BP −19.7 ± 0.1 4560–4440 cal BC
(LTL048A)
TABLE 1 Radiocarbon age and δ13 C term measured for the sample
CS173.4 of one of the individuals buried in the cave in Carpignano, Lecce
608 Applied Physics A – Materials Science & Processing
range are indicated. The δ13 C term was measured on-line with
the accelerator and the calibration was done by using the soft-
ware OxCal 3.10.
The measurement shows that the sample can be dated
(with a 2σ confidence level) in the range 4560– 4440 cal BC,
in the phase called middle-late Neolithic.
The red pigment was identified by carrying out a PIXE
characterisation in air. The non destructiveness and the possi-
bility of performing the analysis at atmospheric pressure were
mandatory in this case. The sample was irradiated, without
any previous processing, by using a 3 MeV proton beam and
the characteristic X-ray radiation collected by mean of the
Si(Li) detector.
Figure 4 shows the PIXE spectrum obtained for the red
area and for comparison the spectrum obtained from the back-
side of the same bone not showing any coloration, and which
was supposed to be “free” from pigment.
The PIXE spectrum clearly shows the presence of mercury
in the red area leading to the identification of the pigment as
mercuric sulphide (also known as cinnabar or vermillion). The
presence of HgS was evidenced also in front side areas not
showing, apparently, any colouring.
The absence in the spectrum taken from the front side
area of the P signal (typical of bones hydroxyapatite) and Ni,
which are both clearly present in the spectrum from the back-
side area of the same bone, indicates that the thickness of the
pigment is higher than the investigated depth (∼ 15 µm for
Ni).
The strong Ca signal in the spectrum from the red area can
be ascribed to surface contamination (carbonates) although
the presence of limestone as an impurity in the cinnabar ore
has been also reported [12].
From the archaeological point of view the absence of
sources of this mineral in Southern Italy opens the question of
the its provenance. Sources of cinnabar are Monte Amiata (in
Tuscany) and in the Balkans where the use of cinnabar as red
pigment on Neolithic pottery has been reported from the site
of Vinca in Serbia [13].
FIGURE 4 External beam PIXE spectra obtained from one of the bones
found (shown in the inset) in the Neolithic burial in Carpignano Salentino for
the area covered by the red pigment, and from the backside which was clear
of pigment
The aim of the use of the cinnabar on the bones is not
known as well, although some authors have recently sug-
gested its use for preservative purposes because of the bacte-
riostatic properties of mercury [14].
3.3 The Neolithic site of Serra Cicora: radiocarbon
dating and PIXE analysis on pottery
The Neolithic site of Serra Cicora lies about 50 m
from the shore line ca. 50 m above sea level on top of a small
hill about 1 km from the Ionian coast of the Salento peninsula
in Southern Italy. The site has been excavated since 1998 by
the archaeologists of the Department of Cultural Heritage of
the University of Lecce who have found many indications of
human presence since ancient times, including burials, pot-
tery, post holes and artefacts [15].
The site has been the subject of an extensive radiocarbon
dating campaign carried out at CEDAD. The radiocarbon an-
alysis of both human bones and charcoals have shown that
human occupation took place in two phases: the first in the
early Neolithic (5670– 5480 cal BC) and the second in the
Middle-Late Neolithic (4600– 4300 cal BC). A complete de-
scription of the radiocarbon dating results are given in [16, and
reference therein].
In particular, in one of the burial sites, of characteristic cir-
clular shape, found in Serra Cicora (Burial T3), one of the
buried individuals was associated with a small pot. The pot,
∼ 7 cm high and with a diameter of ∼ 9 cm, was archaeo-
logically ascribed to the “Serra D’Alto” culture, and showed
traces of a characteristic red decoration.
Again, as already described for the cinnabar, an IBA-AMS
approach was expected to give information concerning the age
of the individual and the composition of the red pigment. In
particular, with respect to this last problem, the question was
whether the red pigment was cinnabar or not.
For the AMS radiocarbon analysis, a bone sample was
selected, and prepared following the procedure already de-
scribed, and dated. The radiocarbon age of the sample
was 5960 ± 40 BP corresponding to a calendar time range
4690– 4440 cal BC (2σ confidence level). It is interesting to
FIGURE 5 External beam PIXE spectrum obtained form the red area of the
decorations on the Serra d’Alto pot (the investigated area is shown in the
inset) found in Serra Cicora, Lecce
QUARTA et al. An integrated 14 C AMS-IBA approach in archaeology
note that the individual found in Serra Cicora was a contem-
porary to that found in the burial in Carpignano Salentino, and
thus a comparison of the two red pigments appeared to be even
more important.
A fragment of the “Serra d’Alto” pot was irradiated in air
under the same experimental conditions previously described,
in order to determine the elemental composition of the red pig-
ment. The PIXE spectrum obtained is shown in Fig. 5.
The analytical data shows that the red pigment is an iron
rich material (most likely ochre), not containing mercury.
4 Conclusions
The combination of AMS high resolution radiocar-
bon analyses and of in air compositional IBA characterisation
gives unique possibilities in the study of archaeological con-
texts. We presented the results obtained by using this “inte-
grated” approach in three different cases. In all cases the AMS
measurements have given, directly or indirectly, a chronolog-
ical time frame for objects compositionally characterised by
PIXE. The possibility of installing, on the same accelerator
beam lines, 14 C AMS dating and IBA compositional charac-
terisation, has to be seen as a real key point in the development
of an accelerator-based facility devoted to studies in cultural
heritage.
ACKNOWLEDGEMENTS This work was supported by the Ital-
ian ministry for research (MIUR) through the projects SIDART (Sistema
Integrato di diagnostica dei beni artistici) and Piano Coordinato Catania-
Lecce co funded by the European Union.
609
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