Nuclear Instruments and Methods in Physics Research B 226 (2004) 172178

www.elsevier.com/locate/nimb

The application of photon, electron and proton induced

X-ray analysis for the identication and characterisation
of medieval silver coins
R. Linke a, M. Schreiner a,*
, G. Demortier b

a
Institute of Humanities, Sciences and Technologies in Art, Academy of Fine Arts, Schillerplatz 3, A-1010 Vienna, Austria
b
LARN, Facult
es Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur, Belgium
Received 21 October 2003; received in revised form 2 March 2004

Abstract

Photons, electrons and protons beams applied to the scientic investigation of archaeological materials provide
complementary information for characterising the state of preservation and the provenance of the objects. Investiga-
tions were carried out on medieval silver coins of the Friesacher Pfennig and the Tiroler Kreuzer from the
Kunsthistorisches Museum Vienna and the Oesterreichische Nationalbank. Techniques employed were EDXRF,
SEM/EDX and PIXE. By determining the trace elements of the alloys it was possible to assign coins to their mint. The
results outline advantages and disadvantages of EDXRF, SEM/EDX and PIXE when applied to corroded objects.

2004 Elsevier B.V. All rights reserved.

PACS: 78.70.E; 61.16.B; 82.80.Ej

Keywords: Energy dispersive X-ray uorescence (EDXRF); Scanning electron microscopy (SEM); Proton induced X-ray emission
(PIXE); Silver coins; Archaeometry

1. Introduction duction was already of interest for Martin Heinrich

Coins represent important objects of our cul-
tural heritage and are usually of high artistic and
cultural value. In relation to the iconography, the
archaeological issue concerns questions of dating,
provenance, technology of production or authen-
ticity. The materials (alloys) used for their pro-
*
Corresponding author. Tel.: +43-1-58816-200; fax: +43-1-
58816-121.
E-mail address: m.schreiner@akbild.ac.at (M. Schreiner).
Klaproth in the late 18th century, when he inves-
tigated the chemical composition of a number of
ancient gold and silver coins [1]. For this pioneer-
ing chemical work, he had to dissolve the coins in
nitric acid and develop analytical procedures for
the separation of Ag, Pb, Sn and Cu quantitatively.
Frequently, these questions may only be answered
by means of scientic investigations. Apart from
the identication of the composition, chemical
analyses also enable the determination of the state
of preservation in view to develop and apply suit-
able treatments for conservation and restoration.

0168-583X/$ - see front matter
2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2004.03.084
 R. Linke et al. / Nucl. Instr. and Meth. in Phys. Res. B 226 (2004) 172178
Coins are usually of small size and sometimes of
high value or even unique. Therefore, scientic
investigation has to be non-destructive, which
means that no sample material (including patina) is
removed or that the object itself is not permanently
modied in any way during or after analysis.
Chemical analyses were carried out on two
groups of Austrian medieval silver coins (Fries-
acher Pfennig and Tiroler Kreuzer) in order to
gain information regarding their provenance. The
coins are objects of the Kunsthistorisches Museum
Vienna and the Oesterreichische Nationalbank.
Apart from silver and copper, silver coins from
these periods usually contain minor and trace
elements. These components originate from the
dierent ores or from the (geographically and
chronologically) varying manufacturing processes
used for the silver production. The chemical
composition of the silver alloys can therefore be
regarded as being characteristic for the various
mintages of the medieval period. The coins have
been selected according to obtain a statistical dis-
tribution between all groups of coins. For a sta-
tistical assignment it has to be considered that
silver was imported and that usually old silver
ware and coins were recycled.
Techniques of investigation include energy dis-
persive X-ray uorescence analysis (EDXRF) [2
4] and energy dispersive X-ray microanalysis with
a scanning electron microscope (SEM/EDX) [57].
Both techniques can be applied non-destructively
without sampling, although SEM/EDX is limited
in the sample size. The advantages of SEM/EDX
include the high spatial resolution and the ability
to analyse small sample areas. On the other hand,
SEM/EDX and EDXRF have a poor sensitivity
for trace elements and for elements with an atomic
number lower than 11 (Na). The detection limits of
SEM/EDX are approximately 0.1 wt.%, depending
on the atomic number and the matrix composi-
tion. As well as for SEM/EDX, the detection limits
of EDXRF depend very much upon the sample,
the element considered and the experimental con-
ditions, and range from 0.1 ppm to a few per-
centage for elements with low atomic numbers.
Applied to metals, better detection limits for high
Z elements (Pb, Au, Hg etc.) could be observed for
EDXRF compared to SEM/EDX.
173
Additionally, proton induced X-ray emission
(PIXE) [8,9] was applied non-destructively in
order to detect elements in the trace level. The
sensitivity of PIXE is signicantly higher com-
pared to EDXRF and SEM/EDX due to the very
low bremsstrahlung induced by protons. PIXE
oers the maximum sensitivity for elements rang-
ing approximately from Ar to Zr. The variation of
the proton beam energy enables the characterisa-
tion of layered structures at the surface [10].
Complementarily, proton induced c-ray emission
(PIGE) and Rutherford backscattering spectrom-
etry (RBS) can be used for the characterisation of
light elements and proling [11]. Drawbacks of
these ion beam analysis (IBA) techniques are the
availability of an accelerator and the correspond-
ing high costs. While EDXRF can be carried out
with portable instruments, SEM/EDX and PIXE
(PIGE, RBS respectively) analysis require objects
to be brought to the instrument.
2. Experimental
Prior to analysis the coins were cleaned with
ethanol and benzine in an ultrasonic bath in order
to remove traces of wax, which has been applied
for conservation reasons. EDXRF was carried out
using a TRACOR XRAY Inc. (Noran) instru-
ment, SPECTRACE 5000, with a Si(Li)-detector
of 155 eV resolution at the Mn-Ka line. For the
excitation, a Rh-tube with an acceleration voltage
of 50 kV and a beam current of 0.04 mA was used.
A Pd primary lter of 0.05 mm thickness was used
in order to increase the signal/noise ratio by sup-
pressing the bremsstrahlung background. The
acquisition time was 100 s real time. During the
analyses the coins were rotated with a speed of 6
rotations/min in order to average the analysis re-
sults and thus to improve the reproducibility. The
area of irradiation was of elliptical shape with a
diameter of approximately 1 cm. Due to varying
surface structures and inhomogeneities of the
surface composition analyses were performed on
both sides of the coins and mean values were cal-
culated for each element.
A main disadvantage of EDXRF is its infor-
mation depth [12]. When applied to corroded
174 R. Linke et al. / Nucl. Instr. and Meth. in Phys. Res. B 226 (2004) 172178
objects non-invasive, it has to be considered that
the results obtained from the surface do not rep-
resent the chemical composition of the core. If the
surface is corroded, the base components of the
alloy (Cu, Pb, Sn etc.) are oxidised and removed
from the surface. Consequently, the surface of the
coin is depleted of these elements and a relative
enrichment of the more noble constituents of the
alloy (Ag and Au) can be measured. In a second
phase, the leached elements combine with con-
stituents of the environment and form corrosion
products at the surface of the coins (patina). These
corrosion products have to be removed prior to
analysis.
For Ag/Cu alloys with a high content of Ag and
a low amount of Cu, the probing depth of XRF is
approximately 100 lm for Ag-Ka, whereas for Cu-
Ka the higher absorption of the specic radiation
compared to Ag-Ka results in an information
depth of approximately 10 lm. As Ag-La radia-
tion originates predominantly from a depth of up
to 2 lm in an Ag/Cu alloy, both the Ag-K and Ag-
L signals obtained in the spectrum enable the
evaluation of the depleted layer [13]. By using the
ratios of Ag-K/Ag-L intensities it is possible to
obtain some information about the degree of
depletion [14], and can be used as an indication
whether Ag is enriched at the surface of a coin or
not.
In order to check the results obtained by ED-
XRF, SEM/EDX measurements were carried out
using a JSM 6400 (JEOL Inc.) instrument, oper-
ated at 20 kV. Coins were selected according to
their state of preservation and polished on their
edge with SiC paper of 4.000 mesh. Due to the
high value of the coins it was not possible to apply
this destructive procedure to each object. In an Ag
matrix the electron beam range is less than 1 lm
and so this technique does not qualify for surface
analysis of corroded objects without destructive
sample preparation.
PIXE measurements were performed in air with
an external proton beam (2.9 MeV) at the Labo-
ratoire dAnalyses par R
eactions Nucl
eaires
(LARN) in Namur (Belgium). The measured area
was approximately 1 mm in diameter. The analy-
ses were carried out on obverse and reverse of the
coins and mean values were calculated. A 10 lm
Co-absorber (K-absorption edge: 7.7 keV) was
placed between the coin and the Si(Li)-detector in
order to enhance relatively the X-ray lines of ele-
ments with an atomic number lower than 29 (Cu)
(e.g. Ni-Ka: 7.5 keV) and to attenuate the inten-
sities of the Ka- and Kb-lines of Cu (Cu-Ka:
8.0 keV (attenuation factor: 20), Cu-Kb: 8.9 keV
(attenuation factor: 10)), i.e. the most abundant
element in the coins apart from Ag. The experi-
mental set-up has already been described previ-
ously [15]. For quantitative evaluation, Pixboy
[16] was applied, a self-made iterative program.
For 2.9 MeV PIXE the probe depths in a Ag
matrix, based on Gupix calculations are 25 lm for
Ag-Ka, 12 lm for Cu-Ka and 5 lm for Ag-L.
3. Friesacher Pfennig
The coinage of the Friesacher Pfennig (denarius
Frisacenses) represents one of the most success-
ful currencies in the 12th century AD in Europe
(Fig. 1). Its wide area of circulation included
Austria, North-Italy, Croatia, Hungary and Slo-
vakia, and the coins were produced at dierent
mints. Coins of the early period (1125/11301168),
which are particularly unique or at least very rare
and of high value, have no marks or legends,
which support numismatists to assign them to a
certain mint. Essential requirements for the
assignment are the rich Ag deposits especially in
Carinthia in former times and that each mint had
its own silver mine. Analyses of coins with known
origin reveal that alloys from these mints show
variations in the trace element levels. Dierences in
Fig. 1. Friesacher Pfennig: Archbishop Konrad I. v. Abensberg
(11061147), mint: Friesach.
 R. Linke et al. / Nucl. Instr. and Meth. in Phys. Res. B 226 (2004) 172178
the chemical composition originate from the
technology of rening or from the ore itself.
EDXRF analyses were carried out on 221 coins
in order to enable geographical or chronological
assignments. Mints included in this survey are the
towns of Friesach, St. Veit, Salzburg, Laufen,
Aquileia and Cologne. Elements measured are Ag,
Cu, Pb, Bi, Hg, Au, Fe and Sb. The Ag concen-
tration in the coins varies from 63.2 1.6 wt.% to
89.0 2.2 wt.%, the mean value is 80.4 2.0 wt.%.
The Ag values appeared independent from any
chronology.
SEM/EDX investigations revealed a homoge-
neous elemental distribution and no leaching of
the surface layer has been measured. Ag-K/Ag-L
ratios were calculated for all coins leading to re-
sults comparable with uncorroded Ag/Cu stan-
dards of varying composition. Therefore, it can be
assumed that the results obtained by EDXRF were
a good approximation of the core composition of
the coins.
For multivariate data evaluation it was not
possible to obtain signicant dierences between
all 221 coins within a single statistical data treat-
ment. Therefore, the data were clustered and
evaluated separately according to the specic
question of provenance. Detailed results have been
published elsewhere [17]. For example the e-
ciency of statistical data evaluation is stressed by
Fig. 2. Comparison of coins from Archbishop Adalbert II.
(M) with coins from the mints of Laufen (L) and Salzburg
(S). Factor 1 and Factor 2 refer to the elements Pb, Bi,
Hg and Au.
175
the results obtained on the mintage of Archbishop
Adalbert II (11831200). There exist no hints in
the archives concerning the identication of the
mint producing this coinage. However, potential
locations could be Salzburg or Laufen, which is
just 60 km next to Salzburg. As shown in Fig. 2, a
clear separation between the coins from Laufen
(L followed by the coin number) and Salzburg
(S) were obtained by means of factor analysis.
The coins of Adalbert II (M) appear to have a
similar composition to coins from Salzburg. In the
project, nearly 80% of all (221) coins investigated
could be assigned to a mint on the base of their
chemical composition by means of multivariate
data treatment.
4. Tiroler Kreuzer
The Tiroler Kreuzer represents one of the
main currencies in the 15th century AD (Fig. 3).
Initially, the coins were produced in the mints of
Merano (Italy) and in 1477 the mint was trans-
ferred to Hall (Austria). Analyses were carried out
on 180 coins in order to compare coins minted in
Merano with those produced in Hall and to assign
coins with an unknown mint. The coins investi-
gated included 44 objects, which have been minted
in Merano, 103 coins which have been minted in
Hall and 33 coins of uncertain origin.
EDXRF was applied non-destructively in order
to determine the Ag contents as well as minor
constituents (Cu, Pb and Bi) and trace elements
(Fe, Au, Hg and Ni). The Ag concentrations vary
Fig. 3. Coin of the Tiroler Kreuzer by Archduke Sigismund
of Tyrol, mint: Merano.
176 R. Linke et al. / Nucl. Instr. and Meth. in Phys. Res. B 226 (2004) 172178

from 55.5 6.1 to 81.3 1.2 wt.%; a detailed re-

port has been published elsewhere [18]. The results
for the Ag-K/Ag-L ratio reveal values 13.1%
4.4% lower compared to Ag/Cu standards,
indicating that Ag is relatively enriched at the
surfaces of the coins due to corrosion processes
(Table 1).
Therefore, investigations of cross-sections were
carried out using SEM/EDX in order to determine
the stage of corrosion and the Ag concentration of
the core of the coins. The results showed dier-
ences up to 50% between the composition of the
core and the surface.
In the backscattered electron image (Fig. 4) the Fig. 4. Backscattered electron image of a cross-section of a
corroded Tiroler Kreuzer coin in the SEM.
domains where Cu was leached out can be ob-
served, which is obviously due to corrosion pro-
cesses. The dark areas show the originally Cu-rich and the bright areas represent the Ag-rich phase.
The surface of the coins shows cavities, black in
Table 1 the image, which have been caused by leaching and
Ag concentrations of a selection of the Tiroler Kreuzer coins diusion of oxidised Cu during the corrosion
obtained non-destructively by EDXRF and on cross-sections process. Area 1 in Fig. 4 has an Ag concentration
by SEM/EDX
of 74.3 3.5 wt.%, while in area 2 an Ag content of
Coin EDXRF SEM/EDX Ag-K/Ag-L 95.8 2.3 wt.% could be measured. Due to the
no. Ag (wt.%) Ag (wt.%) (%)
dissolution and diusion of Cu, the coin became
S29 77.3 1.2 74.8 2.5 )5.5 brittle leading to a crack, as shown in Fig. 4.
S30 78.4 1.4 76.0 1.6 )2.2
S31 76.5 4.5 71.6 4.6 )6.3
Compared to EDXRF, no minor and trace ele-
S32 72.7 3.1 41.7 3.1 )11.8 ments could be determined apart from Cu because
S33 73.1 1.5 45.3 4.5 )15.7 of the high background of the bremsstrahlung in-
S34 79.6 2.1 40.6 1.6 )13.8 duced by the electron bombardment. Therefore,
S35 67.8 0.8 35.3 1.5 )20.0 no provenance assignment could be performed for
S36 79.0 0.8 44.0 4.0 )9.6
S37 71.4 2.4 38.9 1.3 )17.3
the coins investigated on the basis of the EDXRF
S39 74.4 2.6 36.5 2.0 )13.2 measurements. As shown in Table 1, a number of
S40 79.9 0.9 38.9 1.9 )7.3 coins shows signicant deviations in the Ag con-
S41 73.4 2.0 41.6 2.6 )15.7 centrations between measurements carried out by
S42 71.9 3.6 39.9 2.0 )14.1 means of EDXRF and SEM/EDX due to corro-
S43 75.0 1.6 40.6 3.1 )10.0
S44 72.5 0.2 41.5 2.3 )16.5
sion processes.
S45 64.5 1.8 38.9 2.1 )20.4 Finally, PIXE measurements were carried out in
S46 67.7 0.7 38.1 2.3 )16.7 order to measure trace elements (Pb, Bi, Fe, Ni, Sb,
S47 76.4 0.6 35.9 5.0 )13.4 Au and Hg). PIXE, applied at 2.9 MeV, has the
S50 69.4 2.9 35.5 1.4 )15.1 disadvantage of low penetration depths of just up
S51 76.7 0.6 41.2 4.3 )13.8
S52 78.5 2.3 41.6 3.2 )10.4
to approximately 525 lm in metals. Therefore,
S53 73.5 1.8 43.3 1.6 )11.8 this technique cannot provide quantitative analysis
S54 77.0 0.7 41.1 2.5 )14.5 when applied to corroded objects without sample
S55 71.1 1.0 39.6 2.4 )18.9 preparation. However, as only very low brems-
S56 75.6 1.9 38.1 2.7 )14.1 strahlung is induced by the protons, this tech-
Mean 74.1 1.6 44.0 2.4 )13.1 4.4 nique enables lower detection limits compared
Ag-K/Ag-L values reveal the deviation from non-corroded Ag/ to EDXRF and SEM/EDX. Therefore, Ni, an ele-
Cu standards of similar composition. ment, which could be analysed neither by EDXRF
 R. Linke et al. / Nucl. Instr. and Meth. in Phys. Res. B 226 (2004) 172178
Fig. 5. The comparison of a coin produced in the mint of Hall
(continuous line) and one from the mint of Merano (dotted
line) reveals a clear dierence regarding the content of Ni.
nor by SEM/EDX, could be detected. The better
detection limits for Ni (<100 ppm) originate from
the application of a Co-absorber between the
sample and the detector, as mentioned previously
(Fig. 5). The concentration of Ni shows a clear
dierence between the coins from Merano
(approximately 0.1% Ni) and Hall (approximately
0.01% Ni). As shown in Fig. 6, a comparison of the
concentrations of the elements Ni and Bi (limit of
detection <100 ppm) relative to the Ag concen-
tration yields a denite dierentiation of coins
minted in Merano from those minted in Hall. Both
elements are characteristic accompanying elements
in Cu ores. Additionally, coins of unknown prov-
Fig. 6. The scatter plot of concentration ratios of Ni/Ag and Bi/
Ag enables a clear distinction between coins from Merano and
from Hall.
177
enance could clearly be identied as being minted
in Merano.
5. Conclusion
The investigations carried out on medieval sil-
ver coins (Friesacher Pfennig and Tiroler
Kreuzer) have shown that XRF is a valuable tool
for the identication and characterisation of coins,
which were produced from Ag gained directly
from ores and which have a high Ag content. Sil-
ver coins with a high amount of Cu and excavated
are usually heavily corroded, where the chemical
composition of the near-surface domain markedly
diers from the chemical composition of the core.
Additionally, the low X-ray intensities of most
XRF instruments commercially available hampers
the use of selective X-ray lters such as Co, to
reduce the high X-ray intensity of Cu. PIXE,
thanks to its high X-ray yields and low back-
ground has enabled a clear dierentiation of Ti-
roler Kreuzer coins produced in the mints of
Merano and Hall.
Acknowledgements
The authors express their thanks to M. Alram
and H. Winter, coin-cabinet, Kunsthistorisches
Museum Vienna for their fruitful co-operation.
The Jubilaumsfonds der Oesterreichischen Na-
tionalbank (Project No. 7026) is gratefully
acknowledged for nancial support. PIXE mea-
surements were carried out within a short term
scientic mission of COST G1-Action.
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