NIM B

Beam Interactions
with Materials & Atoms
Nuclear Instruments and Methods in Physics Research B 263 (2007) 5457
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X-ray uorescence in investigations of archaeological nds

T. Cechak a, M. Hlozek b, L. Muslek a,*
, T. Trojek a

a
Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University in Prague, Brehova 7, 115 19 Praha 1, Czech Republic
b
Institute of Archaeology and Museology, Masaryk University, Arna Novaka 1, 602 00 Brno, Czech Republic

Available online 22 April 2007

Abstract

X-ray uorescence can be successfully used for analysing the elemental composition of the supercial layers of a measured object,
especially for investigating surface coatings, deposits of adventitious materials on the surface, etc. An energy dispersive version of X-
ray uorescence analysis is used in our investigations for analysing various historic objects, art works and archaeological nds. Examples
of the application of X-ray uorescence to various archaeological nds from excavations in the Czech Republic are presented shards of
ancient glazed ceramics, moulds for casting metal products, the remains of a human nger with traces of brass, probably from a ring, etc.
 2007 Elsevier B.V. All rights reserved.

PACS: 82.80.Ej

Keywords: X-ray uorescence; Archaeology; Ceramics; Metals; Casting moulds; Bones

1. XRF methodology for exciting radiation enables the irradiated area to be

X-ray uorescence (XRF), a very sensitive non-destruc-
tive method for analysing the content of various chemical
elements in materials, is an excellent tool for investigations
of historic relics, works of art and archaeological nds
[1,2]. Being based on photon excitation of the electron
shells of atoms and subsequent qualitative and quantitative
spectrometry of the emitted characteristic X-rays, it is fully
non-destructive and non-invasive. Our laboratory deals
with XRF measurements of many types of artefacts [3,4].
Two versions of instrumentation are used in these inves-
tigations. An XRF analyser with changeable radionuclide
sources in the measuring head and with a semiconductor
Si(Li) detector serves preferentially for in situ measure-
ments. The radionuclide sources 55Fe, 238Pu and 241Am
are used. 55Fe enables excitation of elements with low Z
up to 23, 238Pu is used for excitation of elements with Z
from 20 up to 39, and 241Am is used for excitation of K-
shells of elements with higher Z up to 68. Heavier elements
are detected through their L-lines. The collimator system
selected with its size down to a few square millimetres.
The holder of the measuring head enables area mapping
or line scans within a square of 250 250 mm in parallel
with the measured surface.
An energy dispersive analyser with a miniaturised X-ray
tube serves for measurements where higher spatial resolu-
tion is needed. The size of the spot can be reduced below
1 mm2. The tube employs a Mo anode and can operate
with a maximum current of 0.1 mA at a maximum voltage
of 30 kV. The detection module consists of the AMPTEK
Si-PIN detector, cooled by a Peltier stage and sealed with
a Be window.
The AXIL-QXAS code (IAEA Vienna) is used for peak
area determination, and this is supplemented by calcula-
tions for suppressing the matrix eect, assessing inhomoge-
neities or layered structures, and estimating possible
sources of errors and inaccuracies.
2. X-ray uorescence for analysis of archaeological materials
pottery

*
Corresponding author. Tel.: +420 224358247; fax: +420 224816806. X-ray uorescence analysis is suitable for determining
E-mail address: musilek@fj.cvut.cz (L. Muslek). chemical elements in many materials of archaeological

0168-583X/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2007.04.176
 T. Cechak et al. / Nucl. Instr. and Meth. in Phys. Res. B 263 (2007) 5457
artefacts, the most important being pottery, metals, slags,
glass, faience, bones, pigments, minerals, mortars and plas-
ters. However, interpretation of the measurements is not
always simple, as the nds do not have a well known prov-
enance and have been buried for long centuries in an envi-
ronment that is not well dened. Materials of various
origin and age can be found within a single object. Further-
more, various artefacts may chemically aect each other,
when buried in their original position.
The XRF method has been broadly applied in our lab-
oratory to mediaeval and post-mediaeval pottery with
glazed surfaces. A wide range of examinations of various
colours can provide quite full information about the time
and origin categorisation of the nd. For example, a set
with a colour spectrum of glazes containing green, brown,
yellow, blue and others, was found in an object with layers
of 16th19th century pottery in Pardubice, East Bohemia.
Lead oxides were the basic component of all the studied
glazes. The original positions in the excavation site had
often been disturbed; therefore the dating of some of the
pieces was not fully clear. However, the chemical composi-
tion of some glazes helped to determine the age. The blue-
glazed pottery with white decorations contains Co and Zn
as the coloring component in the glazes. The detected spec-
trum is shown in Fig. 1, and it characterizes production in
the 19th century. Glazes with a high gloss containing light
brown manganese can also be assigned to this period. Some
vessels were glazed only on the inside (bowls, bowl-shaped
forms). Measurements were also carried out in places with-
out glaze. Surprisingly high concentrations of lead were
detected (Fig. 2). They indicate probable hygienic malig-
nancy of this pottery.
XRF measurements can also serve for interpreting spe-
cic technological phenomena of prehistoric pottery. On
Neolithic pottery with a Terra Nigra surface from the Kra-
moln excavation site in South Moravia, 1 mm sized
black spots were found in the pottery material. Measure-
Fig. 1. Spectrum of characteristic X-rays of blue glaze from the 19th
century.
55
Fig. 2. Spectrum of characteristic X-rays of ceramics with a high lead
content.
ments proved that these are traces of manganese, which
could have been a natural part of the clay that was used.
The other possible interpretation that manganese might
be connected with the specic black surface of this pottery
was not conrmed, as only higher concentrations of iron
were detected in these surfaces. At the same site, Eneolithic
pottery with a red surface reminiscent of Samian ware
occurs together with this black pottery. Again, higher con-
centrations of iron were detected there. It can be deduced
that the surfaces of both these types were nished with eng-
obe enriched with Fe-hydroxides. The colour dierences
were caused by the oxidative or reducing environment of
ring.
XRF has also been widely applied for examining techni-
cal pottery. Ceramic crucibles, moulds, casting beds, stools,
etc., can be included in this group. A set of 15th century
crucibles from Brno was examined. The surface layers were
covered with varicoloured glass layers and locally with
strongly corroded remnants of alloys. The advantage of
the method was that it enabled us to carry out measure-
ments non-destructively at any place on the surfaces while
alternating the dierently coloured glass layers with corro-
sive layers. Traces from castings of Cu, Pb, Ag and Zn were
found. The red-coloured glass of one crucible brought a
surprising discovery that gold had been melted in this
pot. Small black spheres were examined on the surface of
another specimen. The presence of bromine was found.
Its presence can probably be connected with the processing
of silver or silver ore. High concentrations of silver were
detected in all of the examined crucibles. Thus XRF mea-
surement conrmed the suppositional existence of a medi-
aeval mint in the location of the excavations.
A surface of a vessel with a clay coat from the 15th cen-
tury (see Fig. 3) was covered with glass layers. An unusu-
ally high zinc concentration of about 0.5% was apparent
in the X-ray spectrum. The vessel can probably be consid-
ered as a retort for brass production. In the Middle Ages,
56 T. Cechak et al. / Nucl. Instr. and Meth. in Phys. Res. B 263 (2007) 5457
Fig. 3. Vessel with a clay coat from the 15th century, from Opava.
brass was produced by annealing copper with zinc oxide
under a layer of charcoal. In this way, the zinc was deoxi-
dated, its vapours dissolved in the copper, and the alloy
was drained into a prepared ceramic vessel. The vessel from
Opava represents a unique artefact documenting this tech-
nological process.
As can be seen, even this simple version of the XRF
technique can provide useful information about archaeo-
logical artefacts. However, can be further rened. Though
XRF is usually considered as a method for surface analysis,
a surface layer (e.g. a glaze or paint) is often thin enough
and the layers of materials responding to the excitation
can be heterogeneous in depth. Characteristic X-rays are
measured not only from the uppermost surface layer, but
also from deeper layers. Therefore, a more sophisticated
evaluation of the signal is possible, which can provide more
detailed information about the structure of the layers of
materials on the artefact. Furthermore, quantication
and interpretation of measured spectra can be improved
by comparing the experimental results with a Monte Carlo
calculation. These two approaches are discussed elsewhere
[5,6].
3. X-ray uorescence for analysis of archaeological materials
metals and others
XRF can also nd a range of applications in analyses of
archaeological metals. There are many metallic objects that
cannot be examined using destructive methods. For exam-
ple, a series of six metal rings was found in the burial
ground of the Unetice Culture (Early Bronze Age) in Huln
in Moravia. Prints of human skin had been preserved in
their corrosive layer (Fig. 4). Because of the importance
of the discovery, the non-destructive XRF analysis method
needed to be applied to prevent damage to the corrosive
layers carrying the negative of the nger papillary terrain.
The XRF measurement led to the conclusion that the rings
under study had been made of copper with various
amounts of arsenic. Such alloys were produced in various
parts of the world during the Eneolith Age and at the
beginning of the Bronze Age. In one of the samples, a con-
centration of about 1% of silver was detected. Other
detected elements (Fe, Ca, Cr) probably come from corro-
sive processes caused by their long-term deposition in the
ground. Analyses of other objects from this burial ground
also conrm that copper with some content of arsenic, sil-
ver, antimony and nickel was common during the Early
Bronze Age.
The assumption that the ngerprints were preserved
only in connection with the arsenic content in the bronze
was partly conrmed by an analysis of the alloy of a small
bronze horse sculpture from a burial ground from the Hall-
statt period, Early Iron Age in Brno (Fig. 5), where similar
ngerprints were found. The alloy contained Cu, Sn, As
and Pb.
XRF is also suitable for analyses of slags from alloying
of nonferrous metals. It can be used for obtaining prelimin-
ary information about slags of unknown origin. As an
example, an analysis of greenish vitreous slags from medi-
aeval furnaces of unknown origin in Vtezov, east of Pra-
gue, helped to interpret the objects as a blacksmiths forge.
In a series of measurements of archaeological materials,
attention was also paid to coloured glass from the La Tene
Period and to blue green faience rings from the Bronze
Age. It is known from similar objects that cobalt oxides
were applied as a colouring component of these materials.
Fig. 4. Fragment of the metal ring from the burial ground in Huln, with
prints of human skin preserved in the corrosive layer.
 T. Cechak et al. / Nucl. Instr. and Meth. in Phys. Res. B 263 (2007) 5457
Fig. 5. Bronze horse sculpture from a burial ground in Brno Modrice
with ngerprints.
A blue glass bracelet from the La Tene Period (Nitra-Chre-
nova, Slovakia) and a faience ring from Slatinice (Prostejov
district) were analyzed. However, in both cases, only cop-
per was detected using XRF. A very small Co concentra-
tion of 0.028% and 0.023% was measured using the
EMPA microprobe.
For bones, XRF is useful only in some specic cases. In
ordinary bone, concentrations of Ca, K and Sr can be
detected. XRF appears very suitable in cases when a bone
has been aected by corrosion products of metal artefacts,
when the metal artefacts have been decomposed during
long-term deposition in the ground. A nger element from
the 11th century burial ground in Nechvaln (Hodonn dis-
57
trict) was analyzed. Originally, a ring made of a thin metal
sheet, which did not preserve, was on the nger. It left just
a spot of colour on the surface of the bone. Analysis
proved that the original alloy of the ring contained Cu,
Pb and Zn.
4. Conclusions
It is clear that XRF analysis can provide a great deal of
useful data for interpretations in archaeology. The non-
destructiveness of the method is an irreplaceable advantage
in investigations of a wide range of objects of the cultural
heritage of mankind, including archaeological nds. The
range of analytical methods based on characteristic X-ray
emission is very broad, and very expensive and complicated
instrumentation is available. Nevertheless, the tradi-
tional method used in our investigations still has an estab-
lished and useful place, and the renements described in
[5,6] can further increase its usefulness.
References
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and Archeometry, Elsevier, Amsterdam, 2000, p. 285.
[2] M. Mantler, M. Scheiner, X-ray Spectrometry 29 (2000) 3.
[3] T. Cechak, J. Gerndt, I. Kopecka, L. Muslek, Radiat. Phys. Chem. 61
(2001) 717.
[4] T. Cechak, J. Gerndt, I. Kopecka, L. Muslek, Nucl. Instr. and Meth.
B 213 (2004) 735.
[5] T. Trojek, T. Cechak, L. Muslek, Nucl. Instr. and Meth. B, these
Proceedings, doi:10.1016/j.nimb.2007.04.064.
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Proceedings, doi:10.1016/j.nimb.2007.04.063.