Nuclear Instruments and Methods in Physics Research B 213 (2004) 735740

www.elsevier.com/locate/nimb

X-ray uorescence in research on Czech cultural monuments

 ech
T. C ak a, J. Gerndt a, I. Kopeck
a b, L. Muslek a,*

a
Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University in Prague, Brehov
a 7,
115 19 Praha 1, Czech Republic
b
State Institute for Care of Historic Monuments, Valdstejnsk
e n
am. 3, 118 01 Praha 1, Czech Republic

Abstract

Radionuclide X-ray uorescence analysis (RXRFA), as a non-destructive method, relatively simple and allowing
measurements to be carried out in situ, is an excellent tool in research on various objects of art. A range of artefacts
have been investigated by our laboratory, in part for the purposes of history of art and in part as a basis for restoration
works medieval frescoes in some Czech castles and churches, metal sculptures and objects of applied art, paints and
inks of old manuscripts, paintings. Some of these are among the most valuable monuments in the Czech cultural
heritage. The contribution of the results of the tests to the investigation of their life story and, in some cases, to their
conservation, is not negligible. Later additions and repairs can be recognised, and materials and technologies that are
close to their historic counterparts can be used in restoration work.

2003 Elsevier B.V. All rights reserved.

PACS: 82.80.Ej; 89.90.+n

Keywords: Radionuclide X-ray uorescence analysis; Medieval frescoes; Metal sculptures; Old manuscripts; Paintings; Conservation

1. Introduction useful collaboration between physicists and con-

Any disturbance of the integrity of historic ar-
tefacts during their investigation, e.g. sampling of
material, is in most cases undesirable. This rein-
forces the value of non-destructive testing and
analytical methods, including radionuclide X-ray
uorescence (RXRFA). The simplicity of this
method, the possibility of carrying out measure-
ments in situ, and its high versatility make it an
excellent tool in research on various objects of art
[1]. This method is being developed and applied in
*
Corresponding author. Tel.: +420-2-24816806/2323033;
fax: +420-2-22320861.
E-mail address: musilek@fj.cvut.cz (L. Muslek).
servationists also by our laboratory at the CTU
Prague [2,3].
The former Czech Kingdom was an important
cultural centre in the Middle Ages, especially in the
14th century, and Czech Gothic art, though less
known than, e.g., French, English or German
Gothic, is very valuable in its nest art works.
Another period of ourishing arts in the Czech
lands is Baroque, with strong inuence from Italian
artists, who started to bring their ideas even earlier,
at the height of Renaissance. After the passage of
centuries, Gothic and Baroque remain the domi-
nant artistic periods, well represented in the Czech
cultural heritage, and castles, palaces and churches
from those times still contribute substantially to the
face of Czech cultural landscape.

0168-583X/$ - see front matter
2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0168-583X(03)01695-1
736  echak et al. / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 735740
T. C
Research on the monuments in the Czech Lands
is a never-ending story, in which our contribution
represents only a small chapter. However, some of
the objects investigated are among the most valu-
able artefacts in the Czech cultural heritage. The
contribution of the results of the tests to the in-
vestigation of their life story and, in some cases,
to their conservation, is not negligible. Later ad-
ditions and repairs can be recognised, and mate-
rials and technologies that are close to their
historic counterparts can be used in restoration
work.
2. Instrumentation
The equipment for RXRFA is relatively simple
and cheap. For characteristic X-ray excitation our
laboratory uses three ring sources 55 Fe, 238 Pu and
241
Am (activities in the order of hundreds of
MBq). The ORTEC Si(Li) detector with an eec-
tive diameter of 6 mm and a thickness of 5 mm
(FWHM 170 eV for the line 5.9 keV of 55 Fe) is
used for detection and spectra recording, which
enables photons up to 60 keV to be detected with
good eciency. This detector is cooled by liquid
nitrogen in a small transportable Dewar vessel
with a volume of 5 l for in situ measurements
(Fig. 1). The CANBERRA 35+ multichannel ana-
lyser is used for laboratory measurements and the
ORTEC DART for measurements in situ.
For qualitative analyses, integration of total
absorption peaks is carried out and the spectra are
processed graphically. When quantitative analysis
is needed for a particular measurement, the AXIL-
Fig. 1. The Si(Li) detector with the Dewar vessel (measurement of the head from the Holy Trinity Column in Olomouc).
QXAS computer code (L. Markovic IAEA lab-
oratory in Seibersdorf) serves for determining the
peak areas. Finally, our own code, based on the
method of empirical coecients, serves for sup-
pressing the matrix eects and calculating the
concentrations.
The following elements were identied in vari-
ous pigments during our measurements of metal
objects of art, medieval frescoes and other arte-
facts: S, Ar, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Zn, As, Sr, Ag, Cd, Sn, Ba, Au, Hg, Pb.
3. Measurement of medieval frescoes
The pigments in frescoes can be recognised only
from the presence of various chemical elements.
Quantitative measurement by RXRFA in situ is
not possible because of badly dened layers of
paints. Nevertheless, even in this way valuable
conclusions can be drawn [4]. Three important sets
of Gothic frescoes have been measured and eval-
uated up to now, in Z  irovnice and Karlstejn castles
and in the Church of Our Lady before Tyn in
Prague.
 irovnice is a Gothic castle from the 13th cen-
Z
tury in S.E. Bohemia, of more or less local im-
portance. After a re in 1964 the castle was restored
and valuable Gothic frescoes from the rebuilding in
the 2nd half of the 15th century were brought to
light. Our measurements were carried out in three
rooms the Chapel, the anteroom, and the Green
Chamber. An example of these frescoes is shown
in Fig. 2. Various characteristic paints were iden-
tied, e.g. azurite, malachite and minium. The most
  echak et al. / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 735740
T. C
 irovnice castle.
Fig. 2. Detail of the fresco from Z
interesting information was found while investi-
gating the red pigments. A dierent type of red
pigment was used according to the importance of
the object painted. Less important objects ele-
ments of architecture or ornaments were painted
with cheap iron-containing mineral pigments from
local sources; for major saints and benefactors,
minium was used; and for the most important ob-
jects, e.g. arrays of Jesus and of one of the three
Kings, vermilion, which was extremely expensive at
that time, because imported from the Mediterra-
nean, was applied. The artistic quality of the fres-
coes is very variable, the most valuable being those
in the Chapel. This indicates that they were not
painted by a single artist. Nevertheless, they
probably originated simultaneously. This conclu-
sion can be conrmed by the results of XRFA
measurements, which have identied the same se-
lection of paints, including the less obviously used
ones (massicot, specic mixtures of pigments of
737
various colours) and the same type of minor min-
eral impurities in the paints.
In contrast to Z irovnice, Karlstejn is one of the
most important and representative Czech castles.
Built between 1348 and 1357 by Emperor Charles
IV as a fortress to protect the crown jewels, the
treasures, documents and relics of the Holy Roman
Empire, it was intended as a symbol of the power,
spirituality and religious faith of the Empire. The
castle twice underwent major rebuilding. One re-
construction was carried out in the late Renais-
sance period and the second between 1887 and
1889. This last extensive restoration was, however,
problematic, as it was carried out too much in the
spirit of 19th century Neo-Gothic purism.
The frescoes in the Chapel of Our Lady in the
central building and on the staircase to the Holy
Cross Chapel in the big tower were measured
mainly in order to distinguish the original parts
from those that were over-painted during the res-
toration works in the 19th century. Medieval pig-
ments are usually rich in lead, and the red
pigments are also rich in mercury. Moreover, a
remarkable peak of sulphur can be seen in some of
the spectra. Neither heavy metals nor sulphur are
present in the pigments from the 19th century
restoration. This fact can serve for distinguishing
the parts of the original frescoes from those re-
stored in the 19th century. Examples of spectra
measured with 238 Pu as the excitation source are
shown in Fig. 3 a well-pronounced K line of
copper and L line of lead can be seen in the
spectrum from the medieval paint.
The Church of Our Lady before Tyn is the
central church in the Old Town of Prague. It is of
Gothic origin from the 2nd half of the 14th cen-
tury, but its construction was interrupted by the
Hussite wars, and the last part was not nished
until 1511. Many Baroque supplements were later
added to the interior. A well-preserved medieval
fresco of St. Hieronymus was recently found be-
hind the wooden Baroque altar on the side of the
church. All the pigments found were typical for
medieval paintings in the Czech Lands, e.g. iron-
containing ochre, malachite, azurite or lead white.
All these paints also contained calcium from the
plaster, which is as may be expected for frescoes.
The remains of the neighbouring painting poses a
738  echak et al. / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 735740
T. C

question about the time sequence and the work-

shops taking part in the decoration of the church,
as the minium found does not correspond to the
selection of pigments used by the author of the St.
Hieronymus fresco.

4. Metal objects of art

The reliquary of St. Maurus, an outstanding

Fig. 3. Comparison of XRF spectra from Karlstejn: black
paint, upper part from the restoration in 19th century, lower
part is original.
example of Romanesque goldsmith work from the
rst quarter of the 13th century, is one of the most
valuable recent nds of medieval works of art in
the Czech Lands. Since the end of World War II it
had been hidden in the oor ballast in the chapel
of Becov Castle in west Bohemia, until it was
discovered heavily damaged in 1985. The reliquary
is composed of independent parts beaten from
silver alloys, gold-plated on the outer side (Fig. 4)
and xed on the wooden case. Various parts of the
plastic decoration were analysed by RXRFA, the
composition of the silver alloy, especially the ratio
of copper to silver, being the main subject of in-
terest. Analyses enabled the decorations to be di-
vided provisionally into ve groups:

Fig. 4. Statue of St. Maurus from the reliquary.

  echak et al. / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 735740
T. C
The bas-reliefs contain between 30 and 33.3
mass percent of copper.
Most of the sculptures of the apostles, includ-
ing the larger statues of Christ and St. Maurus
from the front sides of the reliquary, are purer
than the rst group and have between 18.7%
and 23% of copper.
The third group consists of the statues of St. Pe-
ter and St. Paul, with 14.2% of copper. The re-
lief of Salome is also close to them, having
11.1% of copper.
The ornament and pinnacle on the ridge of the
reliquary are made of gold-plated copper.
Some later repairs and additions have a dier-
ent composition, e.g., the hand of St. Matthew
contains more copper than silver (61%), the
cross is made of brass, and the verication plate
of the relics is made of lead.
The alloy for making the reliquary was proba-
bly obtained by melting down various gifts, jewels,
coins, etc. It seems that several dierent meltings
were used in the same period in order to produce
it. Additional measurements referred to the com-
position of the solders, which can in some cases
provide information about the approximate date
of repairs to the reliquary.
Another example of the application of RXRFA
in restoration works is the Holy Trinity Column in
Fig. 5. Measurement of samples of various inks for studies of manuscripts and books.
739
Olomouc, which is the largest Baroque sculptural
complex in Central Europe. It is 35 m high, with
rich sculptural decoration made partly of stone,
partly of gold-plated brass. It was consecrated in
1754 and 4 years later damaged during the Prus-
sian bombardment of the city. It was subsequently
restored just after the bombardment and then a
few times in the 19th and 20th centuries. The latest
very complex restoration started in 1999. During
the most recent restoration, the brass statues were
also measured by RXRFA. The composition of
the solders based on copper and lead used in the
historic repairs was a major subject of interest of
both art historians and restorers, mainly with the
aim to use materials of similar composition for the
restoration. Measurement of a part of the statue of
the Holy Trinity from the top of the column
(Christs head) can be seen in Fig. 1.
Other recent major restoration works were
carried out on the so-called Golden Gate of
St. Vitus Cathedral in Prague Castle. The Cathe-
dral was founded in the 14th century, but was not
completed in its present-day form until 1928. The
grating in the entrance is from the Renaissance
period. The older parts of the Cathedral were, of
course, also repaired and restored during the Neo-
Gothic completion. Our RXRFA measurement
attempted to nd some remains of the original
polychromy of the grating. Unfortunately, the
740  echak et al. / Nucl. Instr. and Meth. in Phys. Res. B 213 (2004) 735740
T. C
results were negative and only iron, lead and small
amounts of zinc and gold were detected. This
conrms the hypothesis that during the restoration
at the turn of the 20th century the grating was
carefully sand blasted and then gilded.
5. Old books and manuscripts
Collaboration has recently begun with the State
Library, involving RXRFA of various documents
from the collections of the Library. Fragments of
parchments, even from around the 8th century, the
manuscript of the Homiliary of the Opatovice
Monastery from the 12th century, and some other
documents have been measured in an attempt to
identify the composition of inks, printers inks,
binding materials, papers, etc. A part of this on-
going work involves forming a database of the
composition of the various materials that were
used (Fig. 5).
Some other measurements have been made, e.g.
paintings and ancient bricks, but these have been
reported elsewhere (e.g. [2]).
6. Conclusion
RXRFA, though relatively simple and for some
types of artefacts only a qualitative method (e.g.
pigments on frescoes), can provide valuable in-
formation, which can serve for obtaining a deeper
knowledge about the history of particular works of
art, later restorations, etc. The information ob-
tained can also be a matter of interest during new
restorations. The Czech cultural heritage oers
many opportunities to use it.
Acknowledgements
The authors would like to express their grati-
tude to all colleagues who have taken part in the
measurements and in preparing this paper for
publication, namely to Mrs. Jindra Niederlova,
Mr. Vaclav Spevacek and Mr. Tomas Trojek.
Special thanks are oered to the Ministry of Edu-
cation, Youth and Sports of the Czech Republic
for grant no. VS 96052.
References
[1] M. Ferretti, in: D.C. Creagh, D.A. Bradley (Eds.), Radia-
tion in Art and Archeometry, Elsevier, Amsterdam, 2000,
p. 285.
[2] T. C echak, J. Gerndt, M. Kubelk, L. Muslek, M. Pavlk,
Appl. Radiat. Isot. 53 (2000) 565.
[3] L. Muslek, T. C  echak, I. Kopecka, in: Proc. 1st iTRS Int.
Symp. Radiation Safety and Detection Technology, Korean
Nuclear Society, Seoul, 2001, J. Korean Assoc. Radiat. Prot.
26 (2001) 321.
 echak, J. Gerndt, L. Muslek, I. Kopecka, Radiat. Phys.
[4] T. C
Chem. 61 (2001) 717.