CLAY-04009; No of Pages 11

Applied Clay Science xxx (2016) xxx–xxx

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Applied Clay Science

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Research paper

Late Gothic/early Renaissance gilding technology and the traditional

poliment material “Armenian bole”: Truly red clay, or rather bauxite?
David Hradil a,b,⁎, Janka Hradilová b, Petr Bezdička a, Cristina Serendan c
a
Institute of Inorganic Chemistry of the Czech Academy of Sciences, v.v.i., ALMA Laboratory, 1001 Husinec-Řež, 250 68 Řež, Czech Republic
b
Academy of Fine Arts in Prague, ALMA Laboratory, U Akademie 4, 170 22 Prague 7, Czech Republic
c
National University of Arts, General Budisteanu 19, 010773 Bucharest 1, Romania

a r t i c l e i n f o a b s t r a c t

Article history: It is generally considered that the so-called “Armenian bole” used since the Antiquity as a medicament and later
Received 25 July 2016 also as, e.g., a preparatory layer – poliment for water gilding in fine art, was the same material (both by source and
Received in revised form 25 September 2016 composition). It is possible to assume that its alkalinity and strong absorption capacity corresponding most fre-
Accepted 2 October 2016
quently to high content of smectites is beneficial for medicinal purposes, on the other hand, presence of smectites
Available online xxxx
in poliments can cause mechanical instability of the gilding due to swelling effects under increased humidity. Fur-
Keywords:
ther, pure smectites usually do not allow obtaining a compact layer. Other properties of the bole, as, e.g. elasticity,
Historical gilding technology formability and intense red colour, were sought by painters and goldsmiths and therefore, the boles were more
Poliment likely represented by mixtures of minerals. We have collected micro-samples of gildings on bole from significant
Armenian bole panel paintings and polychrome statues belonging to the most prospective period of the 15th and the early 16th
X-ray powder micro-diffraction century, when the gilding on bole was occurring most frequently in workshops connected with the most attrac-
Bauxite tive artistic centres of the Central Europe, as, e.g. Southern Germany or Danube region. Non-invasive and micro-
analytical methods were applied, with particular attention given to the collection of laboratory micro-pXRD data.
It was found out that at the turn of the 15th and the 16th century, clay-rich boles of various compositions started
to be replaced by products of intense lateritic weathering with significant contents of free Al hydro-oxides
(gibbsite, boehmite). It is the first discovery of natural Al-rich pigment (referring either to bauxite or Al-laterite)
in historical paintings ever.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
1.1. Looking for the bole
The first usage of the term “bole” (or “bolus”) had been reserved for
clays with medicinal properties which are strongly absorbing and had
been employed as antacids and antidiarrheal agents since the Antiquity
(Dehn, 2005). The bole has been denoted by several adjectives referring
to its colour, such as, e.g., “bolus alba” – white bole, or “bolus rubra” –
red bole, but the most frequently used expression has been the “Arme-
nian bole”. As recently explained by Barata et al. (2015) and in agreement
with numerous preceding literary sources, this expression is traditionally
associated not only with the bole's place of origin (former Armenia, now
most probably Eastern Turkey), but also with its specific quality. As a con-
sequence, boles from different sources were denoted as “Armenian”. Sub-
sequently, thanks to its advantageous characteristics, the Armenian bole
⁎ Corresponding author at: Institute of Inorganic Chemistry of the Czech Academy of
Sciences, v.v.i., ALMA Laboratory, 1001 Husinec-Řež, 250 68 Řež, Czech Republic.
E-mail address: hradil@iic.cas.cz (D. Hradil).
found its application not only in medicine, but also in painting technology,
particularly as a base for water gilding (Katsibiri, 2002).
In Western Europe, the technique of water gilding has been known
already in the 11th and fully established in the 12th century, i.e., the Ro-
manesque period; however, it appeared only sporadically before 1400.
In the 13th and the 14th century, the gold leaves were most commonly
attached directly to the well-polished gesso (calcium sulphate) or chalk
(calcium carbonate) grounds only by glue (as, e.g., fish or leaf) or glair
used as an intermediate adhesive layer (Buchenrieder, 1990; Whitley,
2000). Occasionally, following the Byzantine tradition, one or more pre-
paratory layers of fine yellow ochre were painted over the gesso to yield
a warmer tone (Sendler, 1988; Katsibiri, 2002). Armenian bole as a rec-
ommended base for water gilding (on paper or parchment and wooden
supports) has been mentioned for the first time in treatises published in
the turn of the 14th/15th century written by Johannes Archerius and
Cennino Cennini (Cennini, 1960; Merrifield, 1999). As mentioned by
Whitley (2000) the dark pink to red colouration of the base for water
gilding in many 14th and 15th century Italian manuscripts would result
from using a high proportion of Armenian bole.
The boles' usage reached its peak between the end of the 14th and
the 18th century, i.e., late mediaeval and Baroque periods (Serck-

http://dx.doi.org/10.1016/j.clay.2016.10.004
0169-1317/© 2016 Elsevier B.V. All rights reserved.

Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
2 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx
Dewaide, 1991). Interestingly, the same development took place also in
the Eastern tradition, where the water gilding on bole was widely intro-
duced in icon painting during the Post-Byzantine period (after 1453),
despite the existence of much earlier individual examples of icons
with bole-gilded backgrounds (Hoenigswald, 1982). As the mining of
clays has spread into many places in Europe in the 16th and especially
during the 17th and 18th centuries (Hradil et al., 2015), the import of
Mediterranean boles has most probably gradually decreased. In his fa-
mous book “Natural History of Fossils”, Emanuel Mendes da Costa (Da
Costa, 1757) lists numerous available boles of various origins (Bohemi-
an, Hungarian, Silesian, French, English, German …) with similar prop-
erties as the original Armenian bole. In the book, the Armenian bole is
mentioned on the first place alongside a note that “it is dug in Armenia,
but is seldom or never to be found genuine in our shops”. Therefore, we
can infer that during the first half of the 18th century (at the latest),
the Armenian bole has ceased to be available on the European market.
Based on the evidence given above, it seems that the imported Arme-
nian bole probably spread into the European gilding technology of the
15th and/or the 16th century. Large number of bole-gilded artworks
in this period could also be related to the increasing availability of raw
material from some new important source.
A different speculation is given by Dehn (2005): the trade with the Ar-
menian bole intensified as a result of plague epidemics in the 14th and the
15th century in Europe, as the people believed in the healing effects of
bole against this disease. It is generally considered that the Armenian
bole for medicinal purposes and for gilding was the same (by source, by
composition). However, is it really possible to assume it or is it rather a
myth? The question is not related only to what the traders offered and
promised (Barata et al., 2015), but also to what truly took root and be-
came really successful and widespread technology. It is possible to as-
sume that alkalinity and strong absorption capacity can help reduce
gastric hyperacidity or stop diarrhoea; therefore, high content of smec-
tites is beneficial for medicinal purposes. On the other hand, the presence
of smectites in preparation layer for gilding can cause mechanical instabil-
ity due to swelling effects under increased humidity. Similarly, the intense
red colour (corresponding to the relative content of hematite) is highly
valuable for the gilding, but has no healing effect and can be rather annoy-
ing for the patients, as the true bole “adheres pretty firmly to the tongue”
(Cennini, 1960). Of course, it is widely documented that not only smec-
tites were used for medicinal purposes (Carretero and Pozzo, 2009,
2010) and similarly, red-coloured boles were ingested, but the above
given simplified example wants to demonstrate that sought-after proper-
ties for medicinal and artistic purposes could be contradictory.
Perhaps under the assumption of the identical nature of Armenian
bole for medicinal and painting purposes, Dehn (2005) searched for
the Armenian bole in the currently available materials in Turkey sold
by apothecaries and herbalists as a medicament. She documented nu-
merous reference clays from Turkish sources differing in colour and
composition; most of them contained smectites as a major phase. How-
ever, she concluded that it is not possible to pinpoint the original “Ar-
menian bole” among them. The lack of knowledge about the
composition of the Armenian bole used by painters finally led to the
loss of exactness of the term “bole” and its almost complete confusion
with terms like “red earth” or even “red ochre” (Eastaugh et al., 2004).
In historical paints, one can find red earths of various compositions cor-
responding to different sources and geological origins. They were used
as pigments, fillers or grounds for paintings (particularly in the Baroque
period). To obtain a better idea of the true nature of Armenian bole in
fine art, one needs to study the technology which represents its primary
application in the field – the gilding. Unfortunately, there is a substantial
lack of analytical data.
1.2. Analytical evidence
In the Western European artistic tradition, two main gilding tech-
niques had been developed since the early Middle Ages: with water-
Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
or oil-based preparatory layers, termed as “mordants” (most frequently
in case of oil gilding) or “poliments” (solely in case of water gilding). The
preparatory layer for oil gilding contained oil (which provided adhesive
power) in combination with various siccative agents, such as Pb- or Cu-
and Fe-based pigments or shards of glass. On the other hand, the tech-
nique of water gilding, also called gilding on bole or “poliment”, consists
of the application of gold leaves on a layer of red bole bound by water
soluble binders, such as, e.g., plain egg white or animal glue with a
dash of honey or gums. Mediaeval and early Renaissance painters
used the red bole particularly in cases when gold was intended to be
subsequently polished (the so-called “polished gilding”) (Nadolny,
2000). With the aim to achieve different chromatic effects, however,
they occasionally chose to apply gold either over a layer of green, yellow
or even black earth or directly onto the white gesso or chalk ground
(Bomford et al., 1989; Dunkerton et al., 1991; Cennini, 1960). The
term “bole”, as understood by painters and conservators, describes a
fine-grained clay material, which is considered to be soft, smooth and
greasy to provide a flexible surface allowing for polishing of the gold
resulting in a brilliant and very smooth effect. The most attractive red
colour of the bole gives the gold red reflections due to transparency.
Therefore, elasticity, formability and colour seem to be the most
sought-after properties of the bole.
As the sampling of historical paintings is restricted and the obtained
micro-samples are rare, a non-destructive analytical approach generally
prevails. Routinely, description of paint micro-samples (or their cross-
sections) by the means of optical microscopy is followed by semi-quan-
titative elemental analysis (e.g., by scanning electron microscopy
coupled with energy dispersive spectroscopy – SEM/EDS or micro X-
ray fluorescence – micro-XRF), and by spectroscopic analyses of pig-
ments and binders by Raman and Fourier-transform infrared micro-
spectroscopy (micro-Raman, micro-FTIR). None of these methods
leads to the differentiation of clay minerals due to their variable chem-
ical composition further affected by numerous admixtures, structural
similarities and low Raman scattering (Košařová et al., 2013). To identi-
fy individual clay minerals, it is necessary to apply powder X-ray micro-
diffraction (micro-pXRD), whose benefits, limits and suitability for the
provenance analysis of mineral pigments have been repeatedly present-
ed (Švarcová et al., 2010, 2011). Another reason of the lack of analytical
evidence of the boles' composition is the missing motivation. To solve
the question of the regional provenance, composition of metals is fre-
quently regarded as a matter of priority (Tissot et al., 2015), while the
investigation of technology of making and materials composition of pre-
paratory layers seems to be too complicated to provide a definite an-
swer. In the scientific literature, the analytical data demonstrating the
true composition of poliments on actual objects are therefore very
fragmentary.
Unfortunately, if the preparatory layers for gilding are evaluated
only visually based on their colouring, it may cause incorrect interpreta-
tions, which further disputes the statements given in the historical liter-
ature. For example, a technical examination of a Spanish Renaissance
panel painting (originally attributed to Bartolome Bermejo (1468–
1495), but later dated to 1530) surprisingly proved the presence of
the oil-based gilding instead of water gilding, which was originally ex-
pected due to the orange colour of the preparatory layer (Rodríguez-
López et al., 2007). The colour resulted from the relatively common
practice of adding various ochres and earth pigments to the mordants
for oil gilding. This example illustrates the difficulty of distinguishing
whether the gilding was performed on bole or not. The final conclusion
cannot be drawn only based on non-invasive approaches, as shown, for
example, by the results of in situ investigation of gilded background of
the 15th century panel painting attributed to Hans Memling and assis-
tants (Van der Snickt et al., 2011). To provide a definite answer, a careful
analysis of organic binders in the preparatory layer together with a de-
tailed mineralogical analysis with particular attention given to differen-
tiation of clay and accompanying minerals are needed. Sandu et al.
(2011) summarises the already published analytical results obtained
 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx
on gilded art objects from European cultural heritage and in none of the
here-listed papers pXRD or micro-pXRD were used to determine the na-
ture of clay minerals in the preparatory layers of gildings. Yet there are
some exceptions. In a recent study, Barata et al. (2015) identified kaolin-
ite, illite and smectite in “bole” layers on Portuguese gilded Baroque re-
tables via synchrotron X-ray diffraction (SR-XRD) and discussed the
possibility of the usage of regional Portuguese clays for that purpose.
That is, of course, possible – in the Baroque period, various regional
sources of earth pigments were used in fine art, as we have already doc-
umented in a comparative study of clay-based grounds of paintings cre-
ated in the 17th and the 18th century (Hradil et al., 2015). However,
regarding the poliments, reliable comparative studies are still miss-
ing. In numerous case studies, the authors prefer to deal with easily
recognisable peculiarities, such as, e.g., the usage of metal bismuth
for bole layers' shadowing (Čechák et al., 2015), while the mineralo-
gy of the predominant clay material was left unresolved. Other
papers are focused on detailed description of organic binders in oil
gildings, which is essential for the determination of the applied tech-
nique (Fedrigo et al., 2000; Katsibiri and Howe, 2010). The issue of
the composition of the original bole which can lead to further clarifi-
cation of assumptions regarding the natural sources of artistic mate-
rials in the Middle Ages and the trade routes remains untackled and
challenging.
In order to fill this gap of knowledge, we collected micro-samples
of gildings on bole from significant panel paintings and polychrome
sculptures belonging to the most perspective period of the 15th
and the early 16th century attributed to the most relevant artistic
centres in Central Europe, such as, e.g., Southern Germany (Nurem-
berg, Ulm), Danube region, Bohemia or Upper Hungary/Lesser
Poland. For comparison, the selection was complemented by two
masterpieces of the 14th century. Non-invasive and micro-analytical
methods were applied, with particular attention given to the collec-
tion of laboratory micro-pXRD data.
2. Materials and methods
2.1. Portable ED-XRF
Non-invasive energy dispersive X-ray fluorescence (ED-XRF) mea-
surements were carried out to check the composition of red-orange
poliments used on the selected polychrome statues and panel paintings,
using Delta Premium analyser by Innov-X, U.S.A. (Rh anode, voltage
40 kV, SDD detector). This method has provided information about
the distribution of chemical elements heavier than magnesium (Z =
12). The measurements were performed in air; therefore, the identifica-
tion of lighter elements was prevented.
2.2. Sampling
Micro-samples of water gildings were collected from a total of 21
works of art dated to the 14th - 16th century with emphasis given on
the turn of the 15th and 16th century, when the gilding on red bole
was most widespread in the region of Central Europe. Gilded back-
grounds and frames, as well as gilded parts of polychrome statues
were included in the comparison. It was not important, however, if
the metal applied was gold, silver or, eventually, part-gold (Zwischgold).
Zwischgold is a metal leaf formed by beating together a layer of gold and
a thicker layer of silver (Nadolny, 2000). The list of analysed artworks
and samples collected is given in Table 1. The selection includes art-
works located in the Czech Republic, the Slovak Republic and Romania,
most of which are connected with the activities of the German-speaking
population in Spiš/Zips or Transylvania/Siebenbürgen regions, there-
fore, there is a strong link to the South-German and also the Danube re-
gion artistic schools.
Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
3
2.3. Light and electron microscopy
Olympus BX 60 light microscope equipped with Olympus DP 70 dig-
ital camera and/or Zeiss Axio Imager A.2 light microscope with the
Olympus DP 73 digital camera were employed for visual observation
of micro-samples embedded in Neukadur PE 45 polyester resin and
ground in cross-sections using the LaboPol-5 grinder (Struers GmbH).
Photographs were taken in the white reflected light as well as in the
UV light (365 and 470 nm) using Colibri 2 fluorescence module.
Scanning electron microscopes (Philips XL-30 CP and/or JEOL
JSM6510) with detectors of back-scattered electrons (SEM), coupled
with EDAX (Philips) and/or INCA (JEOL) EDS detecting unit were used
to describe the elemental composition of individual layers and grains.
Light elements performance technology (LEAPC) allowed detection of
the elements heavier than Be (Z N 4) at resolution of 135 eV (Philips)
or 125 eV (JEOL). Measurements were carried out in a low vacuum
mode, which allowed analysis of the samples without conductive coat-
ing of their surface.
2.4. Laboratory powder X-ray micro-diffraction
Micro-diffraction experiments were collected as described else-
where (Švarcová et al., 2010; Hradil et al., 2016) using a PANalytical
X'Pert PRO diffractometer. A CoKα tube with point focus, an X-ray
mono-capillary with diameter of 0.1 mm in the primary beam path,
and a multichannel detector X'Celerator with an anti-scatter shield in
the diffracted beam path were used. A sample holder was adapted by
adding z-(vertical) axis adjustment (Huber 1005 goniometric head).
X-ray patterns were measured in the range of 4 to 80° 2Θ with a step
of 0.0334° and 2200 s counting per step. 2.5 mm anti-scatter slit,
0.04 rad Soller slit and Fe beta-filter were used in the diffracted beam.
The duration of the scan was ca. 12 h. Qualitative analysis was per-
formed with the HighScorePlus software package (PANalytical, The
Netherlands, version 4.5.0) and JCPDS PDF-4 database (JCPDS, 2015).
2.5. Quantitative phase analysis - rietveld refinement
The methodology of the quantitative phase analysis of micro-sam-
ples has been described in our previous paper (Hradil et al., 2016).
Quantification of the experimental data was performed using the
Rietveld method (Rietveld, 1969). As the clay minerals (such as, e.g., ka-
olinite) exhibit a wide range of disorders (stacking faults in the layer
structure), the BGMN code was used for all calculations (Bergmann et
al., 1998). This program includes a code which permits the use of struc-
tural models correctly describing the disorder models (Ufer et al., 2004,
Ufer et al., 2008a). Structural models of minerals identified in poliment
samples were described as standard Rietveld models (ICSD 2016) with
the exception of Ca smectite. Its structural model was adopted from
Ufer et al. (2008b). Preferred orientation was refined only for illite and
kaolinite. Spherical harmonics of the 2nd degree was used (Bergmann
et al., 2001). Additional refined non-structural parameters used were
sample displacement error and a 6th degree polynomial for background
modelling.
2.6. Identification of organic binders
To achieve the basic determination of the type of the binder, histo-
chemical tests were combined with infrared micro-spectroscopy
(micro FT-IR). For the identification of the presence of proteins in the
cross-sections Fuchsin S and methylene blue were used, Lugol's Solution
was used to identify polysaccharides. Infrared spectra of cross-sections
were measured in specular reflection mode using the Continuum infra-
red microscope coupled with Nexus spectrometer (Thermo Scientific,
USA) at the Polymer Institute in Brno, Czech Republic. Spectra were re-
corded in the region of 4000–650 cm−1 with the resolution of 4 or 8
cm− 1 and analysed using Omnic 7.2 (Thermo Scientific, USA). If
4 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx

Table 1
List of analysed artworks, collected samples and methods applied.

Code Artwork, place/attribution Date of Number of Methods applied

creation samples

9651 Diptych “Man of Sorrows, Madonna and Angel” (panel painting), Karlštejn, CZ/T. da Modena 1355–1359 1 (Au) SEM-EDS, micro-pXRD
(1326–1379)
M0405 Funeral insignia of Czech kings (polychromy on wood), Prague's Castle, CZ/Bohemian master 14th 3 (Au) SEM-EDS
century
J1604 Mary Magdalene from Danišovce (polychromy on wood), Slovak National Museum - Spiš Museum 1420 1 (Au) Non-invasive ED-XRF, SEM-EDS,
Levoča, SK/Bohemian master 1 (Ag) micro-pXRD, micro FTIR, MS
1
(Zwischgold)
M0718 Madonna with Child (polychromy on wood), National Gallery in Prague, CZ/Bohemian master 1420 1 (Au) SEM-EDS
M0116 Our Lady Protectress (panel painting), National Gallery in Prague, CZ/unknown origin 1430 1 SEM-EDS
(Zwischgold)
M0348 Madonna with Child (polychromy on wood), church of St. Barbara, Horní Ves – Chomutov, 15th 1 (Au) SEM-EDS, micro-pXRD
CZ/German master century 1 (Ag)
Med High Altarpiece (panel painting) of St. Margaret Evangelical Church from Mediaș, RO/“Mediascher 1480 1 (Ag) SEM-EDS, micro FTIR
Meister” (Nurmberg?)
J1324 Triptych “Death of the Virgin Mary” and predella (panel painting), Royal chapel, Italian Court at 1497 1 (Au) SEM-EDS, micro-pXRD, micro FTIR
Kutná Hora/Kuttenberg, CZ/unknown origin
J1328 Mourning of Christ, according the engraving by Albrecht Dürer (wooden relief), Minorite Monastery 1500–1510 9 (Au) SEM-EDS, micro-pXRD. micro
at Brno, CZ/South-German workshop (Ulm?) 3 (Ag) FTIR, MS
M0013 The Altarpiece of St. Oswald (?), St. Roch and St. Wilgefortis (polychromy on wood), Moravian About 1 (Ag) SEM-EDS
Gallery in Brno, CZ/Erasmus Grasser (ca 1445/1450–1518) or workshop, Bavaria (?) 1510
M1002 Pieta (polychromy on wood), National Gallery in Prague, CZ/unknown origin Early 16th 1 SEM-EDS, micro-pXRD
century (Zwischgold)
Beia Altarpiece of Saint Ursula (panel painting), Ev. Church from Beia, RO/Sighişoara Group of Workshops 1513 1 (Au) SEM-EDS, micro-pXRD, micro FTIR
Sor Passion altarpiece (panel painting) Ev. Church from Şoroştin, RO/Sighişoara Group of Workshops About 1 (Au) SEM-EDS, micro-pXRD, micro FTIR
1520
Cund Altarpiece of Saint Nicholas (panel painting), Ev. Church in Cund, RO/Sighişoara Group of Workshops 1520–1530 1 (Au) SEM-EDS, micro-pXRD, micro FTIR
Road Altarpiece of Saints John Evangelic (panel painting), Church from Roadeş, RO/Sighişoara Group of 1520–1525 1 (Au) SEM-EDS, micro-pXRD, micro FTIR
Workshops
Fis Saint Martin Altarpiece (panel painting), Ev. Church from Fişer, RO/Sighişoara Group of Workshops 1520–1522 2 (Au) SEM-EDS, micro-pXRD, micro FTIR
Med-PR The Last Supper predella (panel painting) unknown origin, today part of the main altarpiece of 1525–1530 1 (Au) SEM-EDS, micro-pXRD, micro FTIR
Evangelic Church from Mediaş, RO/Vincencium workshop from Sibiu
J1605 Crucified Christ (polychromy on wood), Spišské Vlachy, SK/Master Paul from Levoča About 2 (Au) SEM-EDS, micro-pXRD, micro
1520 FTIR, MS
J1606 St. John Altar (panel paintings) St. James Church in Levoča, SK/Hans T. - workshop of Master Paul About 1 (Au) Non-invasive ED-XRF, SEM-EDS,
from Levoča 1520 micro-pXRD, micro FTIR, MS
J1607 St. John Altar - polychrome statue of St. John the Baptist, St. James Church in Levoča, SK, Master Paul About 1 (Au) Non-invasive ED-XRF, SEM-EDS,
from Levoča 1520 micro-pXRD, micro FTIR, MS
J0914 Altarpiece of St. Martin (panel painting), Lipany, SK/H.E.R., workshop of Master Paul from Levoča, 1526 4 (Au) SEM-EDS, micro-pXRD, micro FTIR

possible, proteinaceous binders were further differentiated at the De-
partment of Biochemistry and Microbiology of the University of Chem-
istry and Technology in Prague, via mass spectrometry methods (MS),
as, e.g. matrix-assisted lased desorption time-of-flight mass spectrome-
try (MALDI-TOF MS, Autoflex Speed instruments, Bruker-Daltonics,
Germany) and/or nano-liquid chromatography-electrospray ionization
quadrupole time-of-flight mass spectrometry (NanoLC-ESI-Q-TOF MS/
MS, Dionex Ultimate3000 RSLC nano-connected with the ESI-Q-TOF
Maxis Impact mass spectrometer, Bruker-Daltonics Germany) accord-
ing to the methodology described by Kučková et al. (2013).
3. Results and discussion
3.1. Results of non-invasive ED-XRF measurements
It can be assumed that the polished gilding on bole was performed
wherever the intention was to achieve a high shine, and where the
area was large enough for polishing. Thus, the bole can be expected to
be found especially on the gilded backgrounds or original frames of
panel paintings or also on the shiny gilded parts of polychrome statues.
(Fig. 1) To get an idea of differences in the elemental composition of
boles detectable by non-invasive way we have selected two representa-
tive objects belonging to the 15th and 16th century, respectively, and
performed measurements of gilded parts by portable ED-XRF method.
Being aware that the bole contains mainly aluminosilicates, we used
the ED-XRF analyser with improved detection of light elements to be
able to express relative contents of Al, Si and K together with Fe and
Ti. Magnesium remained below the detection limit. It was also assumed
that, when measured from the surface of the painting, all the above
mentioned elements originated only from the bole. In both cases,
white chalk (CaCO3) had been applied as a ground and there was no
other layer than the bole (layer 2 in the cross-section) between the
chalk layer (layer 1) and the metal foil (layer 3).
Even a simple comparison of the contents of Al and Si (presented at
Figs. 2 and 3) yielded surprising results. In the case of the polychrome
statue of Mary Magdalene from Danišovce, Slovakia (dated to 1420,
code J1604), all the gildings (either with Au, Ag or Zwischgold) are sup-
ported by the bole with a slight predominance of Si over Al and the con-
tents of Si and Al correlate together (R2 = 0.91). On the other hand, the
statues and the frame of the panel painting from the workshop of Mas-
ter Paul of Levoča (dated to 1520, codes J1606 and J1607) are gilded on
bole with a predominance of Al over Si and the contents of these two el-
ements does not correlate completely (R2 = 0.64). It could mean that in
the first case clays with low or even zero content of quartz were used
(correlation of Si and Al is not distorted by free SiO2) while in the second
case the material probably contained free aluminium (hydro)oxides.
Considering very close relative atomic weights of Si and Al it does not
matter if the ratio is calculated from atomic or weight percent.
The first possible explanation of the increased contents of Al in the
bole is the addition of a red organic lake, which, according to traditional
recipes, had been prepared by reaction of the dye (as, e.g., the madder)
with potash alum - Al2(SO4)3K2SO4·12H2O. The substrate links to spe-
cific functional groups of the dye molecule, lakes precipitate as insoluble
metal–dye complexes and the excess aluminium turns into solid amor-
phous hydrous aluminium oxide, which becomes the lake substrate
(Clementi et al., 2008). Such lakes were more stable than the pure

Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx
Fig. 1. Polychrome statue of crucified Christ from Spišské Vlachy, Slovakia (J1605), dated
to around 1520, attributed to Master Paul from Levoča (left, photo Š. Siváň), with gilded
veil displayed in detail (right), from which the fragment of the gilding with clearly
visible red poliment was taken (bottom right). (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)
organic dye. Although this eventuality is mentioned in the literature
(Heydenreich, 2010; Kubersky-Piredda 2010), it is very unlikely that ex-
pensive organic pigment was used in such a large extent to intensify the
colour of the bole over large areas of the frames and gilded parts of
statues. The question of the origin of aluminium cannot be solved with-
out sampling.
Fig. 2. Si/Al ratios calculated from non-invasive XRF measurements performed on different
parts of gilded objects dated to the first half of the 15th century - J1604 (full circles) and to
the first half of the 16th century - J1606 and J1607 (open circles).
Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
5
Fig. 3. Correlation of Si and Al based on non-invasive XRF measurements performed on
different parts of gilded objects dated to the first half of the 15th century - J1604 (full
circles) and to the first half of the 16th century - J1606 and J1607 (open circles).
3.2. Stratigraphy and composition of bole layers
Most of the frequently used red organic lakes exhibit a characteristic
luminescence in ultraviolet radiation of the paint layers, which is of
pinkish (or “salmon”) colour (Kirby et al., 2005). None of the samples
taken from the studied artworks, however, included bole layer having
such luminescence (either in any part of the layer or in the grains). Fur-
thermore, as can be documented by a number of measurements of his-
torical red organic glazes, conducted by us in the past, inorganic
substrates always contain set of elements characteristic for the starting
material, i.e., Al, S and K, referring to potash alum. In the case of our sam-
ples of Al-rich boles, however, these three elements do not correlate
together.
The most important results of microscopic methods, namely optical
microscopy (including UV luminescence) and scanning electron mi-
croscopy (including EDS analysis of elemental composition), obtained
by observing and measuring cross-sections of micro-samples of water
gildings taken from all studied artworks are summarised in Table 2
and Fig. 4. Based on the results we can conclude that (i) aluminium-
rich boles are not limited to a single case, but were very common in Cen-
tral European painting of the 16th century, and (ii) the composition of
boles varies chronologically, which could be associated not only with
the change of technology, but also with the availability of suitable
materials.
Within our set of samples, one can find first rare examples of clay-
rich boles in the 14th century, (9615, Fig. 4a, layer2). Simultaneously,
experiments with various red pigments, as, e.g., hematite (M0405, Fig.
4b, layer2) or cinnabar (9615, Fig. 4a, layer5) took place. In the 15th cen-
tury red-coloured clays dominated, which can be evidenced by signifi-
cant amounts of Si and Al, with a predominance of Si. (J1604, Fig. 4c,
layer2) This finding is in perfect accordance with the assumptions de-
rived from historical literature (Katsibiri, 2002). But what is not men-
tioned anywhere is the fact that technology changed at the turn of
15th and 16th century. Along with the new materials (with high Al con-
tents) applied the thickness of poliments has changed too. They became
more pronounced and they frequently exhibit features of additional
colouring (J1324, Fig. 4d, layer2), as is apparent from the detailed EDS
analysis of grains (see Table 2). This new technology was obviously
not just a local peculiarity, because the aluminium-rich boles appear si-
multaneously on numerous significant artworks occurring in distant re-
gions - in Transylvania (Romania), Spiš (North-East Slovakia), or
Bohemia (Czech Republic).
6 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx

Table 2
Results of semi-quantitative SEM-EDS analyses of poliments (values are averaged from several point measurements in the layer).

Code/metal Grounda Average analyses of the bole layer (concentrations of major elements in at.%) Grainsb

Si Al Si/Al K Ti K/Ti Mg Ca Fe P S Pb Hg

14th century
9651/Au (1) Gesso 19.4 14.1 1.4 3.1 0.7 4.6 2.0 35.9 3.1 n.d. 19.9 n.d. n.d. –
9651/Au (2) Gildingc 27.0 20.2 1.3 1.4 0.4 4.1 0.7 3.6 7.7 n.d. 22.9 n.d. 16.1 –
M0405/Au Chalk, ochre 10.9 3.7 2.9 n.d. n.d. – n.d. 1.5 78.9 n.d. n.d. n.d. n.d. –
M0405/Au,Ag Chalk, ochre 14.8 2.7 5.5 0.8 n.d. – n.d. 28.3 26.7 n.d. 1.3 n.d. n.d. –

15th century
J0604/Au Chalk 42.9 28.2 1.5 3.3 0.3 9.6 1.0 12.8 8.4 1.5 0.3 n.d. n.d. –
J0604/Ag Chalk 44.7 28.3 1.6 3.1 0.5 6.9 0.9 12.6 8.7 n.d. 0.4 n.d. n.d. –
M0718/Au Chalk 42.6 33.7 1.3 0.2 2.5 0.1 1.7 6.1 6.6 n.d. n.d. 1.0 n.d. –
M0116/Au,Ag Chalk 26.7 16.6 1.6 4.3 7.4 0.6 0.6 24.7 5.0 n.d. 2.3 n.d. n.d. –
M0348/Au Gesso 41.0 15.0 2.7 4.0 1.0 4.0 n.d. 26.0 3.5 n.d. 3.7 n.d. n.d. –
M0348/Ag Gesso 31.0 22.5 1.4 2.3 0.5 4.1 1.5 16.5 4.0 n.d. 6.7 n.d. n.d. –
Med/Ag Gesso 9.6 4.7 2.0 1.7 n.d. – n.d. 45.3 4.3 1.5 27.4 n.d. n.d. –
J1324/Au Chalk 17.6 21.1 0.8 0.8 0.8 1.0 0.8 46.1 11.0 0.1 1.1 0.2 n.d. Bi,Sb, Hg,S,C

16th century
J1328/Ag Chalk 28.6 40.4 0.7 1.6 1.2 1.3 1.5 11.8 9.6 0.4 1.6 0.9 n.d. C
J1328/Au Chalk 28.6 40.6 0.7 1.3 1.0 1.3 1.4 15.8 9.4 0.2 0.3 0.6 n.d. C
M0013/Ag Mg-chalk 16.5 55.0 0.3 0.9 1.1 0.8 4.3 7.3 13.6 n.d. n.d. n.d. n.d. –
M1002/Au,Ag Chalk 33.3 32.1 1.1 1.5 1.2 0.9 2.4 9.3 14.0 0.6 1.1 1.2 n.d. C,Bi
Beia/Au Gesso 29.1 46.0 0.6 1.4 1.0 1.4 1.6 8.8 11.9 1.5 9.5 n.d. n.d. C
Cund/Au Gesso 23.9 35.0 0.7 1.4 0.5 2.9 1.7 6.5 21.9 2.4 5.3 n.d. n.d. C
Sor/Au Gesso 20.2 27.2 0.7 1.6 0.9 1.8 1.0 16.6 11.6 n.d. 15.8 n.d. n.d. –
Road/Au Gesso 14.9 7.0 2.1 3.3 2.1 1.5 n.d. 19.5 36.9 n.d. 13.9 0.3 n.d. –
Road/Ag Gesso 12.4 8.4 1.5 0.7 0.8 0.9 0.1 17.3 13.6 n.d. 11.5 0.6 n.d. –
Fis/Au Gesso 37.2 24.5 1.5 3.6 0.2 15.5 0.9 12.1 9.0 2.3 10.0 n.d. n.d. Hg,S
Med-PR/Au Gesso 25.6 39.8 0.6 1.6 1.1 1.4 1.7 7.0 15.4 n.d. 4.7 1.0 n.d. C
J0914/Au Chalk 30.4 32.2 0.9 3.5 0.8 4.6 1.5 12.7 11.3 n.d. 1.4 0.8 n.d. –
J1606/Au Chalk 32.7 37.3 0.9 2.9 0.6 4.4 1.0 9.6 12.2 0.6 3.0 n.d. n.d. Hg,S
J1605/Au Chalk 30.7 39.1 0.8 2.7 0.7 4.0 1.0 6.8 13.7 n.d. 1.0 0.4 n.d. Sb,Hg,S
J1607/Au Chalk 37.9 38.6 1.0 2.0 0.5 3.9 0.6 8.2 11.1 n.d. 0.8 0.3 n.d. Hg,S

Notes:
a
The composition of the ground layer beneath the bole may affect the analysis, if, for example, the bole layer is very thin or partly soaked to the ground. Particularly, contents of Ca or
Ca + S can be increased in the case of chalk (calcium carbonate) or gesso (calcium sulphate) grounds.
b
Includes information about what elements are present in minor heterogeneities representing colourants intentionally added to the bole in low concentration.
c
In the sample 9651, two gildings are overlaid (Fig. 4a); both of them are considered to be a genuine work by T. de Modena, who was experimenting with the final tonality of the gilding
and applied it twice, using different compositions of the poliment and also various thicknesses of the gold leaves.

The aim of this intentional colouring of boles was either to intensify
the deep red colour (by adding cinnabar or extra hematite), or, on the
contrary, to darken the hue by adding a black pigment. Considering
this fact it is interesting that materials with metallic lustre were selected
– most frequently graphite (C), but alternatively also metallic bismuth
and/or stibnite (Sb2S3) (Table 2, Fig. 4d). Particularly in the case of bis-
muth we can assume a chronological correlation with the onset of min-
ing of the so called five element Ag-Co-Ni-Bi-U mineralisation during
the 15th and the 16th century. The highly significant mining sites in-
clude especially those in Ore Mountains (Erzgebirge) on the boundary
of Bohemia and Saxony with probably the largest Schneeberg deposit
in Germany, which is most frequently mentioned as a source of Bi for
the painting purposes (Spring et al., 2003). Bismuth is mined as a by-
product initially accompanying the exploitation of silver and later also
cobalt. Although the mining of Bi and stibnite is documented mainly
from Germany, these two pigments have appeared in Italian art as
well – e.g. in the paintings by Rafael (Bi), Correggio and Fra Bartolom-
meo (stibnite) (Spring et al., 2003; Ferreti et al., 1991). These seemingly
unrelated issues enable us to understand that neither graphite, nor stib-
nite and bismuth were parts of genuine bole material, but they were
added later respecting a customary technology of that time.
Another interesting interpretation follows from the varying K/Ti
ratio (Table 2). This ratio is one of the indicators pointing both to the in-
tensity of weathering and to the composition of the parent rock during
the clay formation. When we look, for example, at the K/Ti ratio togeth-
er with the contents of Fe, we can assume that (i) the same clays were
used under the gold and silver within the same artwork (M0348,
J0604, J1328), and (ii) the composition of boles significantly differs
from case to case (or place to place). In the 15th century the differences
are so great that they can hardly be associated only with the heteroge-
neity of the material. While the statue of Mary Magdalene from
Danišovce (J1604) contains K-rich clays in the bole (K/Ti = 6.9–9.6),
the composition of the samples M0718 and M0116 indicates using of
Ti-rich clays (K/Ti = 0.1–0.6) from seemingly different source. All
these artworks, however, belong to the same period (1420–1430) and
to the same region (Bohemia). Similarly in the 16th century, the boles
belonging to the workshop of Master Paul from Levoča (J0914, J0605,
J0606, J0607) can be distinguished from other Al-rich boles (Si/Al b 1)
of the same period by substantially higher K/Ti ratios (3.9–4.6). The
ratio differences may indicate not only the different sources, but also
the possibility that the bole material was mixed from multiple sources.
Organic binders in all studied poliments contain proteinaceous com-
ponents, which were, in some cases, further specified as collagens (indi-
cating use of animal glue in the samples J1604, J1328, J1605, J1606 and
J1607). Together with the glue, which was dominant in the layer, very
thin adhesive interlayer of glair was identified in the samples J1606
and J1607. On the other hand, presence of fatty components of the bind-
er (indicating use of emulsion, as, e.g. the whole egg) was evidenced in
some of the Transylvania samples (Beia, Cund). It should be noted, how-
ever, that this information might be inaccurate with regard to the fact
that the poliment is a very thin layer and a contamination may occur ei-
ther from the ground or from later surface treatments. The waxing of
frames, for example, could complicate the identification of oils due to
the overlaps of characteristic lines. An additional information, which
could help distinguish between oil-based and water-based gilding,
might be obtained from the presence or absence of lead pigments. How-
ever, none of the studied samples contains significant amounts of lead,
which could indicate the presence of Pb-based siccatives accelerating

Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx 7

Fig. 4. Simplified stratigraphy of layers in the cross-section showing four types of the water gilding on poliment from the 14th to 16th century: (a) 9651 - thick layer of gold leaves (+3) on
a thin layer of a clay-rich bole (+2, thickness 7–10 μm) overlaid by isolation layer (+4) and secondary gilding - a thin foil of gold (+6) on a very thick layer of cinnabar and red earths with
an organic adhesive on the top (+5, thickness 27–30 μm), followed by varnish and later over-paintings (+7); both the gildings belong to the 14th century and was performed by the same
artist and with the same gold (with admixtures of Ag and Cu); (b) M0405 -gold leaves (+3) on the fine-grained hematite with an organic adhesive on the top (+2, thickness 4–5 μm) from
the 14th century, covered by varnish (+4); (c) J1604 - Zwischgold (+3) on the red clay-rich bole with an organic adhesive on the top (+2, thickness 7–10 μm) from the 15th century,
covered by varnish (+4); (d) J1324 - gold leaves (+3) on the Al-rich bole with an organic adhesive on the top (+2, thickness 10–11 μm) from the 16th century with additional
colouring by metal bismuth (Bi), stibnite (Sb, S) and graphite (C), covered by over-paintings and varnish (+4). (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)

the drying of oils, in the preparatory layer (Table 2). It can be, thus, con-
cluded that the method of water gilding was used in all of the studied
cases.
3.3. Mineralogy of boles
Not all of the poliment gilding samples were suitable for measure-
ments by laboratory micro-pXRD. The main limiting factor was the in-
sufficient thickness of the layer of the poliment, which prevented to
analyse the layer separately in the cross-section. The only possible
way was analysing untreated fragments from above through the layer
of the metal leaves, which was, however, quite frequently breached,
therefore, the red bole showed through. On the contrary, when the gild-
ing was later covered with over-paintings, the analysis was not possible.
Finally we managed to get XRD data from one poliment of the 14th cen-
tury, four poliments of the 15th century and twelve poliments of the
16th century. Estimation of quantitative representations of individual
minerals in analysed samples is given in Table 3.
On the panel painting by T. de Modena (9615, dated to 1355–1359)
we confirmed that cinnabar (HgS) was used as a major component in
the poliment (beside clays). On the paintings from the 15th century,
clay materials were prevailing, but each one of a different composition.
The poliment on the polychrome sculpture of Mary Magdalene from
Danišovce (J1604, dated to 1420), Slovakia, is probably the best corre-
sponding to the definition of Armenian bole (=red greasy montmoril-
lonitic clay) provided by Kužvart (1984). There is no quartz present,
which is in agreement with data obtained by non-invasive ED-XRF. In-
stead of pure smectite, however, the bole contains mixed-layered
structures exhibiting basal spacing at d = 1.3 and 1.1 nm, respectively
(Fig. 5). Their exact determination is not an easy task. In agreement
with already published results of mock-up experiments (Hradil et al.,
2016) we can assume that after the interaction with proteinaceous
binders the basal spacing has slightly increased and, therefore, it was
presumably lower before. Theoretically it could increase from 1.2 to
1.3, which corresponds to illite/smectite structure with approx. 40% of
smectite. The interaction cannot be recognised by pXRD in interstrati-
fied structures, if the content of expandable layers is lower than 30%
(Hradil et al., 2016). Together with the predominant illite/smectite the
bole further contains kaolinite and illite (Fig. 5).
Other two boles from the 15th century (on the polychrome statue of
Madonna with Child by an unknown German Master - M0348 and on
the altarpiece from Mediaş, Transylvania - Med) contained mostly kao-
linite and illite, but no expandable clay structures. It could indicate that
even in the beginning of use of clay-rich boles their sources differed. On
the other hand, a common feature was a low or even no content of
quartz. However, this information should be considered as very prelim-
inary because the number of relevant diffraction data is still very small.
At the turn of the 15th and 16th century the mineralogical composi-
tion of boles has significantly changed. Beside kaolinite, illite, chlorite,
anatase, and quartz, that can be considered as common minerals of
clays, significant amounts of gibbsite (Al(OH)3) and/or boehmite
(AlO(OH)) were evidenced in boles of the end 15th and the beginning
of 16th century (Table 3). The best correlation can be made among
the gildings belonging to the Sighișoara (Schässburg) group of work-
shops (SGOW) in Transylvania, where we know about the activity of
Johann Stoss, one of the sons of the famous German sculptor Veit

Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
8 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx

Table 3 two clearly discernible groups differ, however, in relative contents of

Estimation of mineralogical composition of poliments based on micro-pXRD data. gibbsite (Table 3, Fig. 7).
14th and 15th century Among the artworks attributed to SGOW, there are two other altar-
Code of the sample (metal) 9651 (Au) J0604 (Au) Med (Ag) M0348 (Ag)
pieces having significantly different composition of poliments. On the al-
tarpiece of Fiser, content of Al hydro-oxides is very low, while on the
Grounda Gildingb Chalk Gesso Gesso
altarpiece of Roades gibbsite and/or boehmite are completely missing.
Kaolinite - Al2Si2O5(OH)4 15 5 29 22 Specific composition can also be found on the poliment used on the gilded
K-mica group mineral 2 17 15
decoration of The Last Supper predella of an unknown origin in the St.
Expandable clay structures 42
Quartz - SiO2 3
Margaret Ev. Church from Mediaş, Transylvania, which was recently at-
Hematite - Fe2O3 3 tributed not to SGOW, but to simultaneously acting workshop of master
Anatase - TiO2 2 Vincencium from Sibiu (Serendan et al., 2013; Sarkadi, 2008). Although
Calcite - CaCO3 47 this bole contains Al hydro-oxides, chlorites are missing and instead of
Gypsum - CaSO4·2H2O 3 2 29 34
them expandable clay structures can be recognised at d(001) = 1.3 nm.
Anhydrite - CaSO4 19 17
Bassanite - CaSO4·0.5H2O 12 Most of the studied boles from Transylvania and Slovakia contain main-
Cinnabar - HgS 82 ly gibbsite; boehmite is less abundant. In two cases (J1605, Med-PR),
however, boehmite significantly prevails. Variability in the content of
End of 15th and 16th century (chalk grounds) major minerals appears to be rather accidental. What was mentioned
Code of the sample J1324 J1328 M1002 J0914 J0605 J0606 J0607 above for boehmite applies also to chlorite, which is, for example, enriched
(metal)
(Au) (Ag) (Au,Ag) (Au) (Au) (Au) (Au) in the bole used for gilded parts of Early Renaissance relief of “Mourning of
Christ” (1500–1510) from Minorite Monastery in Brno, Czech Republic.
Ground Chalk Chalk Chalk Chalk Chalk Chalk Chalk
This relief is considered to be attributed to a South-German workshop
Kaolinite - Al2Si2O5(OH)4 12 14 26 12 13 11 20
(most probably Ulm), without any more detailed specification. The earliest
K-mica group mineral 2 5 7 7 8 6 5
Chlorite group mineral 3 12 2 4 4 4
finding of Al-rich bole comes from the Late Gothic altarpiece of the “Death
Quartz - SiO2 2 7 16 4 6 11 3 of the Virgin Mary” from Kutná Hora (Kuttenberg), Czech Republic, which is
Hematite - Fe2O3 3 2 6 3 9 5 6 dated to 1497 (Fig. 8). Both the “Mourning of Christ” (1500–1510) and
Anatase - TiO2 4 2 5 4 4 3 “Death of the Virgin Mary” (1497) contain poliments, which are similar to
Gibbsite - Al(OH)3 3 13 3 5 3 10 8
those used also by Master Paul from Levoča.
Boehmite - γ-AlO(OH) 6 1 1 3 14 3 4
Calcite - CaCO3 61 37 39 40 30 33 43 Although the number of studied artworks is not too broad, it allows
Gypsum - CaSO4·2H2O 3 7 12 9 4 4 us to determine that the occurrence of gibbsite and boehmite in boles is
Bismuth - Bi 1 1 not a local phenomenon relating to a solitary workshop, but was associ-
Alunite - 9 ated with more widely applied technology of gilding, which emerged in
KAl3(SO4)2(OH)6
the late 15th century in German-speaking regions of Central and East-
16th century (gesso grounds) ern Europe.
From the geological point of view, gibbsite and boehmite indicate
Code of the sample (metal) Beia Cund Sor Road Fis Med-PR
use of lateritic materials rich in aluminium, as, e.g., bauxite or Al-laterite,
(Au) (Au) (Au) (Au) (Au) (Au)
as a source material for the boles. An alternative possibility, namely, that
Ground Gesso Gesso Gesso Gesso Gesso Gesso aluminium hydroxide (gibbsite) may be a synthetic substrate for the
Kaolinite - Al2Si2O5(OH)4 10 14 12 31 21 2 precipitation of red organic dye (organic lake), is not easy to prove di-
K-mica group mineral 2 10 6 11 10 18 rectly and non-destructively on the precious micro-samples of works
Expandable clay structures 8 of art. However the amount of the material available was limited, there-
Chlorite group mineral 10 3 3 4
fore, it was not possible to apply separation techniques, as, e.g., GC–MS.
Quartz - SiO2 6 6 3 13 29 26
Hematite - Fe2O3 8 11 5 3 1 On the other hand, not to be able to identify organic dyes by non-de-
Anatase - TiO2 2 4 2 2 structive approaches (as, e.g., by FTIR or Raman spectroscopy) cannot
Gibbsite - Al(OH)3 23 19 22 5 be considered a definite proof of their absence due to their generally
Boehmite - γ-AlO(OH) 2 8 2 2 14
low concentrations in painting layers.
Gypsum - CaSO4·2H2O 35 25 37 29 25 27
Anhydrite - CaSO4 2 8 8 11
The only way was to try to identify inorganic phases in the layers
Cinnabar - HgS 1 with independently proven presence of organic dyes and to compare
the results with the composition of Al-rich boles. For this purpose, we
Notes:
a
The composition of the ground layer beneath the poliment affect the analysis, because have selected a layer of Al-rich organic glaze probably containing red or-
all the measurements were performed from the surface of the fragment and not from its ganic lakes in higher concentrations and performed comparative XRD
cross-section; particularly, contents of calcite or gypsum and anhydrite can be increased measurements. It was important that both the organic glaze and the
in the case of chalk (calcium carbonate) or gesso (calcium sulphate) grounds; metals
Al-rich poliment were of the same age (late Gothic) and found on the
(Au, Ag) were not included to the calculation.
b
In the sample 9651, two gildings are overlaid (Fig. 4a).
same object – a late Gothic altarpiece of the “Death of the Virgin
Mary” from Kutná Hora, Czech Republic (J1324). The measurement
has confirmed that while the Al-rich bole contained both gibbsite and
boehmite, these minerals were completely missing on the diffraction
Stoss (before 1450–1533) (Serendan et al., 2013), and the gildings be- pattern of Al-rich organic glaze. It is due to the fact that, in agreement
longing to the workshop of Master Paul from Levoča/Leutschau with historical recipes of organic lake preparations, Al(OH)3 precipitat-
(1475–1480?–1537–1542?) acting in Spiš/Zips region in Northern Slo- ed as amorphous (Clementi et al., 2008). This experiment allowed us to
vakia, who was also a contemporary of Veit Stoss (Figs. 6 and 7). Both definitively conclude that there really is a lateritic material present in
of the regions were inhabited by German-speaking communities (com- our samples of boles and that it is not an organic lake.
monly referred to as Saxons) in the studied period. Particularly,
poliments from altarpieces of Beia, Cund and Sorostin (all belonging to 3.4. Question of provenance
SGOW) are closely similar by relative representations of individual
phases and the same applies for all samples attributed to the workshop When considering a question of possible provenance, we must ask
of Master Paul from Levoča, Slovakia (J1605, J1606, J1607, J1914). These whether the mineralogical composition corresponds to a single source

Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx 9

Fig. 5. Part of micro-diffraction pattern of the bole layer under the gilding (“poliment”) on the polychrome statue of Mary Magdalene from Danišovce (dated to 1420) showing the presence
of expandable interstratified clay structures (ECM) of probably two types, which, however, cannot be further specified because of low quality of the pattern.

of the material, or a mixture from multiple sources. As already men-
tioned, boles were often coloured. Cinnabar (HgS), for example, repre-
sents with no doubt secondarily delivered material. The same applies
to bismuth and stibnite (proven in M1002, J0914 and J0605). Although
there is a possibility that Bi and Sb came directly from bauxite (He et al.,
2011), it is very unlikely. Concentrations of Bi in poliments are some-
times even so high that they can be registered by micro-pXRD (Fig. 8)
– what is not realistic to expect for laterites or bauxites. Another clearly
discernible additional admixture is gypsum. When measuring frag-
ments from the surface, we noted the presence of gypsum in all the
boles, even if the white ground layer (under the bole) was made from
pure chalk (CaCO3) and not from gesso (CaSO4). (Table 3) It is, therefore,
probable that the gypsum was added to the bole in order to increase its
formability. But what about the composition of the key material, which
can be either clay, bauxite or Al-laterite?
When taking into account only the average Si/Al ratio (=0.75 in av-
erage), we can speculatively classify the whole material as, e.g., a clayey
bauxite with relatively large contents of clay minerals. We have also
identified the phases that are typical for bauxites - gibbsite, boehmite,
kaolinite, hematite and anatase. The total content of these minerals
varies from about 60 to 80 wt% (when excluding gypsum and calcite)
(Fig. 7). On the other hand, there are other phases in the rest of the ma-
terial which cannot be expected to a greater extent in products of
intense rock weathering, such as, e.g., mica, quartz, chlorite, and some-
where also feldspars. The K/Ti ratio mostly higher than 1 (2.8 in aver-
age) is in connection with higher content of these phases, which again
is not typical for the products of intense weathering, where Ti usually
prevails. We can, therefore, imagine that materials from two different
sources were mixed together. It is not easy to support this idea, but
we can use the comparison of the altarpieces belonging to Sighișoara
group of workshops (SGOW) as an interesting indication. In majority
of them (Beia, Cund, Sorostin) we can find Al-rich boles and also a
very similar mineralogical composition. In one of them (Roades), how-
ever, boehmite and gibbsite are missing and hematite is less abundant.
It could mean that the Fe and Al oxides were just a significant part of the
material (such as bauxite), which was added to the clay-rich bole in
varying extents to improve its technological properties. On the other
hand, we cannot ignore the possibility of high heterogeneity of the
raw material, whose regional origin is still not known and no reference
materials are available yet.
It is the first discovery of Al-rich bauxite or laterite in historical
paintings ever. Up to now, there was no evidence of systematic use of
these materials for any technological purposes in pre-industrial periods
in Europe before their exploitation for aluminium since the 19th centu-
ry. Nobody has also examined this eventuality in the area, where the
“original” Armenian bole came from. In Anatolia, deposits of bauxites

Fig. 6. Comparison of micro-diffraction patterns of bole layers (“poliments”) on gilded objects of early 16th century located in Northern Slovakia (J0914 and J1605) and Transylvania,
Romania (Cund) showing their mineralogical similarity, which includes also the most significant feature, i.e. the presence of gibbsite and boehmite.

Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
10 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx

Fig. 7. Representation of major phases in Al-rich poliments from to the turn of 15th and 16th century and early 16th century, grouped to categories: 1 – Al hydro-oxides gibbsite and/or
boehmite, 2 – Fe and Ti oxides (hematite and anatase), 3 – kaolinite, 4 – quartz, 5 – mica group minerals, 6 – chlorite group minerals, 7 – expandable clay minerals.

are very abundant. The same, however, applies to the whole Mediterra-
nean region and also to Hungary, part of a former kingdom, comprising
both Transylvania/Siebenbürgen/Erdély and Spiš/Zips/Szepes counties
at that time, which are today part of Romania and Slovakia, respectively.
Question of the provenance of the material thus remains open for fur-
ther research.
4. Conclusions
For the first time bauxite (or Al-laterite) was identified as an inten-
tionally used bole material in historical painting - in here presented
cases it was applied as a poliment for polished water gilding in the
late Gothic and early Renaissance artworks, located at distant regions
of Central and Eastern Europe, which were, however, culturally linked
thanks to the German-speaking communities living there. The presence
of bauxite was proved by varying, but significant content of gibbsite and
boehmite, which systematically occur in orange-red boles along with
kaolinite, hematite and anatase. With respect to the content of other
minerals that are not typical for bauxites, it cannot be determined
whether the bole came from a single source or it is a mixture. The first
indication of occurrence of Al hydro-oxides in poliments is higher con-
tent of Al exceeding the content of Si, which can already be evidenced
by non-invasive ED-XRF measurements of gilded areas of artworks
with no need of sampling. In all cases, however, especially if the Si/Al
ratio is close to one, it is necessary to confirm the presence of crystalline
gibbsite and/or boehmite also by diffraction techniques.
Systematic use of red clay-rich boles in the European painting
started in the 15th century. However, in the period of the greatest pop-
ularity of boles (used as poliments for gilding) in Central European re-
gions, i.e. at the turn of the 15th and the 16th century, products of
intense lateritic weathering with significant contents of free Al hydro-
oxides seem to be more frequent. Apparently there was a technological
reason why these materials have become so successful - regardless of
whether they have been employed alone or as a useful ingredient in
low quality clays. It is, therefore, still difficult to say, what was the orig-
inal Armenian bole the painters in the Central part of Europe used, al-
though it is possible that it was ferruginous bauxite and not a red clay
as proposed in classical literature. It is not surprising that the colour

Fig. 8. Part of micro-diffraction pattern of poliment on the triptych “Death of the Virgin Mary” from the Italian Court at Kutná Hora, Czech Republic (J1324) showing the predominance of
boehmite and also the presence of metal Bi as an artificial admixture to the poliment.

Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004
 D. Hradil et al. / Applied Clay Science xxx (2016) xxx–xxx 11

(in our cases rusty red) was a very important factor for the painters and
goldsmiths, while the medicinal application was predestined by other
technological properties, such as, e.g., high sorption capacity favouring,
for example, smectite-rich materials. In the light of these new findings,
it does not seem to be likely that the Armenian bole was always repre-
sented by one identical material for both applications – medicinal and
artistic.
Acknowledgement
The authors would like to thank to all collaborating restorers and art
historians (particularly Mária Novotná – director of the Spiš museum in
Levoča, Slovakia, Anna Svetková, Jaroslav Alt and Igor Fogaš) for provid-
ing samples and sharing their expertise, as well as to our colleagues in
ALMA Laboratory, particularly Vlasta Vašutová, Zdeňka Čermáková,
Silvie Švarcová and Veronika Kohútová for their versatile assistance in
this research and performing SEM-EDS and micro-FTIR measurements.
The study has been supported by Czech Science Foundation, project
no. 14-22984S and by Institutional Budgets of Research Institutions.
References
Barata, C., Rocha, F., Cruz, A.J., Andrejkovičová, S., Reguer, S., 2015. Synchrotron X-ray dif-
fraction of bole layers from Portuguese gilded baroque retables. Appl. Clay Sci. 116–
117, 39–45.
Bergmann, J., Friedel, P., Kleeberg, R., 1998. BGMN — a new fundamental parameters
based Rietveld program for laboratory X-ray sources, its use in quantitative analysis
and structure investigations. CPD Newsl. (Commission of Powder Diffraction, Interna-
tional Union of Crystallography) 20, 5–8.
Bergmann, J., Monecke, T., Kleeberg, R., 2001. Alternative algorithm for the correction of
preferred orientation in Rietveld analysis. J. Appl. Crystallogr. 34, 16–19.
Bomford, D., Dunkerton, J., Gordon, D., Roz, A., 1989. Art in the Making: Italian Painting
Before 1400: Exhibition Catalogue, London, 29 November 1989–28 February 1990.
National Gallery, London.
Buchenrieder, F., 1990. Gefasste Bildwerke, Arbeitsheft 40. Bayerisches Landesamt für
Denkmalpflege, München.
Carretero, M.I., Pozo, M., 2009. Clay and non-clay minerals in the pharmaceutical industry
part I. Excipients and medical applications. Appl. Clay Sci. 46, 73–80.
Carretero, M.I., Pozo, M., 2010. Clay and non-clay minerals in the pharmaceutical and cos-
metic industries part II. Active ingredients. Appl. Clay Sci. 47, 171–181.
Čechák, T., Trojek, T., Šefců, R., Chlumská, Š., Třeštíková, A., Kotrlý, M., Turková, I., 2015.
The use of powdered bismuth in Late Gothic painting and sculpture polychromy.
J. Cult. Herit. 16, 747–752.
Cennini, C., 1960. The Craftsman's Handbook—The Italian ‘Il Libra dell'Arte’, translated by
D.V. Thompson. Dover Publications, Inc., New York.
Clementi, C., Doherty, B., Gentili, P.L., Miliani, C., Romani, A., Brunetti, B.G., Sgamellotti, A.,
2008. Vibrational and electronic properties of painting lakes. Appl. Phys. A Mater. Sci.
Process. 92, 25–33.
Da Costa, M., 1757. Natural History of Fossils. Royal Society of London.
Dehn, E., 2005. Über Armenischen Bolus. Diplomarbeit, Technische Universität München.
Dunkerton, J., Foister, S., Gordon, D., Penny, N., 1991. Giotto to Dilrer: Early Renaissance
Painting in the National Gallery. National Gallery Publications, London.
Eastaugh, N., Walsch, V., Chaplin, T., Siddall, R., 2004. Pigment Compendium, a Dictionary
of Historical Pigments. Elsevier-Butterworth Heinemen, British Library.
Fedrigo, M.A., Favaro, M., Traldi, P., 2000. Applications of mass spectrometry in cultural
heritage: identification of ligands employed for mordant gilding. Rapid Commun.
Mass Spectrom. 14, 2203–2209.
Ferreti, M., Guidi, G., Moioli, P., Scafè, R., Seccaroni, C., 1991. The presence of antimony in
some grey colours of three paintings by Correggio. Stud. Conserv. 36, 235–239.
He, F.D., Li, H.C., Yuan, Y.X., 2011. Determination of arsenic, antimony and bismulth in lat-
erite nickel ore by hydride generation-atomic fluorescence spectrometry. Metall.
Anal. 31, 44–47.
Heydenreich, G., 2010. The Leipzig trade fairs as a market for painters' materials in the
sixteen century. In: Kirby, J., Nash, S., Cannon, J. (Eds.), Trade in Artists' Materials.
Markets and Commerce in Europe to 1700. Archetype, pp. 297–313.
Hoenigswald, A., 1982. The ‘byzantine’ Madonnas: technical investigation. Stud. Hist. Art
12, 26–27.
Hradil, D., Hradilová, J., Bezdička, P., Švarcová, S., 2015. Differentiation between anony-
mous paintings of the 17th and the early 18th century by composition of clay-
based grounds. Appl. Clay Sci. 118, 8–20.
Hradil, D., Bezdička, P., Hradilová, J., Vašutová, V., 2016. Microanalysis of clay-based pig-
ments in paintings by XRD techniques. Microchem. J. 125, 10–20.
ICSD, 2016. Database FIZ Karlsruhe, Germany, release 2016/1 .
JCPDS, 2015. PDF-4 Database, International Centre for Diffraction Data Newtown Square,
PA, U.S.A. release .
Katsibiri, O., 2002. Investigation of the Technique and Materials Used for Mordant Gilding
on Byzantine and Post-byzantine Icons and Wall Paintings Diploma thesis University
of Northumbria at Newcastle.
Katsibiri, O., Howe, R.F., 2010. Microscopic, mass spectrometric and spectroscopic charac-
terisation of the mordants used for gilding on wall paintings from three post-byzan-
tine monasteries in Thessalia, Greece. Microchem. J. 94, 83–89.
Kirby, J., Spring, M., Higgitt, C., 2005. The technology of red lake pigment manufacture:
study of the dyestuff substrate. Natl. Gallery London Tech. Bull. 26, 71–87.
Košařová, V., Hradil, D., Němec, I., Bezdička, P., Kanický, V., 2013. Microanalysis of clay-
based pigments in painted artworks by the means of Raman spectroscopy. J. Raman
Spectrosc. 44, 1570–1577.
Kubersky-Piredda, S., 2010. The market for painters' materials in Renaissance Florence. In:
Kirby, J., Nash, S., Cannon, J. (Eds.), Trade in Artists' Materials. Markets and Commerce
in Europe to 1700. Archetype, pp. 223–244.
Kučková, S., Sandu, C.A., Crhová, M., Hynek, R., Fogaš, I., Muralha, V.S., Sandu, A.V., 2013.
Complementary cross-section based protocol of investigation of polychrome samples
of a 16th century Moravian sculpture by optical, vibrational and mass spectrometric
techniques. Microchem. J. 110, 538–544.
Kužvart, M., 1984. Ložiska nerudních surovin (Non-metallic ore deposits). Academia,
Prague, In Czech.
Merrifield, M.P., 1999. Medieval and Renaissance Treatises on the Arts of Painting: Origi-
nal Texts and English Translations. Dover publications Inc., Mineola, New York.
Nadolny, J.M., 2000. The Techniques and Use of Gilded Relief Decoration by Northern Eu-
ropean Painters, c. 1200–1500 PhD dissertation Vol. I. University of London, London,
p. 159.
Rietveld, H.M., 1969. A profile refinement method for nuclear and magnetic structures.
J. Appl. Crystallogr. 2, 65–71.
Rodríguez-López, A., Khandekar, N., Gates, G., Newman, R., 2007. Materials and tech-
niques of a Spanish Renaissance panel painting. Stud. Conserv. 52 (2), 81–100.
Sandu, C.A., de Sá, H., Pereira, M.C., 2011. Ancient ‘gilded’ art objects from European cul-
tural heritage: a review on different scales of characterisation. Surf. Interface Anal. 43,
1134–1151.
Sarkadi, E., 2008. Produced for Transylvania — local workshops and foreign connections.
Studies of Late Medieval Altarpieces in Transylvania. Central European University, Bu-
dapest PhD Thesis.
Sendler, E., 1988. The Icon: Image of the Invisible, Translated by Fr. S. Bigham. Oakwood
Publications, pp. 194–196.
Serck-Dewaide, M., 1991. The history and conservation of the surface coating on Europe-
an Gilded-Wood objects. Gilded Wood: Conservation and History (Madison, CT).
Serendan, C., Hradil, D., Hradilová, J., Cannataci, J., 2013. Early Renaissance altarpieces in
Transylvania: materials and technological characteristics. In: Saunders, D., Spring,
M., Meek, A. (Eds.), The Renaissance Workshop. Archetype Publications Ltd., London,
pp. 60–71 pp 199, ISBN: 978-1-904982-93-7.
Spring, M., Grout, R., White, R., 2003. Black earths': a study of unusual black and dark grey
pigments used by artists in the sixteenth century. Nat. Gallery Tech. Bull. 24, 96–114.
Švarcová, S., Kočí, E., Bezdička, P., Hradil, D., Hradilová, J., 2010. Evaluation of laboratory
powder X-ray micro-diffraction for applications in the field of cultural heritage and
forensic science. Anal. Bioanal. Chem. 398, 1061–1076.
Švarcová, S., Bezdička, P., Hradil, D., Hradilová, J., Žižak, I., 2011. Clay pigment structure
characterisation as a guide for provenance determination — a comparison between
laboratory powder micro-XRD and synchrotron radiation XRD. Anal. Bioanal. Chem.
399 (1), 331–336.
Tissot, I., Troalen, L.G., Manso, M., Ponting, M., Radtke, M., Reinholz, U., Barreiros, M.A.,
Shawe, I., Carvalho, M.L., Guerra, M.F., 2015. A multi-analytical approach to gold in
ancient Egypt: studies on provenance and corrosion. Spectrochim. Acta B 108, 75–82.
Ufer, K., Roth, G., Kleeberg, R., Stanjek, H., Dohrmann, R., Bergmann, J., 2004. Description of
X-ray powder pattern of turbostratically disordered layer structures with a Rietveld
compatible approach. Z. Kristallogr. 219, 519–527.
Ufer, K., Kleeberg, R., Bergmann, J., Curtius, H., Dohrmann, R., 2008a. Refining real struc-
ture parameters of disordered layer structures within the Rietveld method. Z.
Kristallogr. Suppl. 27, 151–158.
Ufer, K., Stanjek, H., Roth, G., Dohrmann, R., Kleeberg, R., Kaufhold, S., 2008b. Quantitative
phase analysis of bentonites by the Rietveld method. Clay Clay Miner. 56, 272–282.
Van der Snickt, G., Miliani, C., Janssens, K., Brunetti, B.G., Romani, A., Rosi, F., Walter, P.,
Castaing, J., De Nolf, W., Klaassen, L., Labarquee, I., Wittermann, R., 2011. Material
analyses of ‘Christ with singing and music-making Angels’, a late 15th-C panel paint-
ing attributed to Hans Memling and assistants: part I. non-invasive in situ investiga-
tions. J. Anal. At. Spectrom. 26, 2216.
Whitley, P.K., 2000. The Gildet Page. The History and Technique of Manuscript Gilding.
Oak Knoll Press, The British Library.

Please cite this article as: Hradil, D., et al., Late Gothic/early Renaissance gilding technology and the traditional poliment material “Armenian
bole”: Truly red clay, or rat..., Appl. Clay Sci. (2016), http://dx.doi.org/10.1016/j.clay.2016.10.004