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Multi-analytical study of techniques and

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ia, Serbia
Article in Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy December 2015
Impact Factor: 2.35 DOI: 10.1016/j.saa.2015.11.031

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Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and Biomolecular

Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Multi-analytical study of techniques and palettes of wall paintings of the

monastery of ia, Serbia
Ivanka Holclajtner-Antunovi a, Milica Stojanovi-Mari b, Danica Bajuk-Bogdanovi a,
Radia iki c, Sneana Uskokovi-Markovi d,
a

Faculty of Physical Chemistry, University of Belgrade, P.O. Box 47, 11158 Belgrade, Serbia
National Museum Belgrade, 11000 Belgrade, Serbia
Institute for the Protection of Cultural Monuments of the Republic of Serbia, 11000 Belgrade, Serbia
d
Faculty of Pharmacy, University of Belgrade, P.O. Box 146, 11000 Belgrade, Serbia
b
c

a r t i c l e

i n f o

Article history:
Received 19 August 2015
Received in revised form 16 November 2015
Accepted 25 November 2015
Available online xxxx
Keywords:
Archaeological pigments
Wall paintings
Micro-Raman
SEMEDS
FT-IR
ED-XRF
OMUV

a b s t r a c t
The present multi-analytical study concentrates on establishing the painting techniques and the identity of the
wall painting materials used by the artists from the 13th and 14th centuries to decorate the ia monastery,
Serbia. For this purpose, we demonstrate that micro-Raman spectroscopy is an efcient, non-destructive method
with high spatial resolution which gives molecular and crystal structural information of a wide variety of both
inorganic and organic materials. It is shown that elementary composition revealed through scanning electron microscopy with energy dispersive X-ray spectroscopy and energy dispersive X-ray uorescence spectroscopy is
necessary in some cases to conrm the identity of pigments and binders identied by micro-Raman spectroscopy. It was found that a fresco technique, in combination with mainly natural earth pigments such as red ochre,
yellow ochre and green earth, was used. Expensive natural pigment lapis lazuli was exclusively used for obtaining
blue colour while pure vermilion was used by the artists from the rst period of decorations at the beginning of
the 13th century. A mixture of pigments was used for attaining different colour shades. For the gilding of saint's
haloes, thin golden foil was deposited over the tin sheet. In order to get a desirable optical and aesthetical impression, the metallic leaves were deposited over the yellow ochre preparatory layer. Deposits of gypsum on wall
paintings as well as traces of weddellite are degradation products formed as a result of exposing wall paintings
to environmental conditions.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Material's analysis performed by various analytical techniques is an
important component of archaeological research and plays an important role in our understanding of relations and knowledge in different
periods of human history. Specically, it yields compositional information that may lead to ancient artefact characterization and provides insight to technology advances and exchanges, communications between
nations and trade routes [1].
Analytical techniques are therefore important in evaluating of archaeological and art history artefacts. For example, the combination of elemental analysis with molecular characterization provided by X-ray
uorescence and UVvis spectroscopies, respectively, allowed for the in
situ non-invasive identication of a number of pigments decorating the
ceiling of the Gilded Vault of the Domus Aurea in Rome [2]. In order to

Corresponding author.
E-mail address: snezaum@pharmacy.bg.ac.rs (S. Uskokovi-Markovi).

http://dx.doi.org/10.1016/j.saa.2015.11.031
1386-1425/ 2015 Elsevier B.V. All rights reserved.

characterize the palette used by the painter and to yield information useful to restorers, the combined approach involving high-resolution breoptic reectance spectroscopy (FORS), X-ray uorescence (XRF) spectroscopy and Raman spectroscopy was applied to mural paintings of a chapel
in the Aosta Valley (Italy) [3]. Further, light microscopy and energy dispersive X-ray analysis showed the authenticity of certain pigments for
the Princely church of Curtea de Arges in Romania [4]. The combination
of laser-induced breakdown spectroscopy, micro-Raman spectroscopy,
non-destructive X-ray diffractometry, optical microscopy and scanning
electron microscopy coupled to micro-probe analysis was applied for
studying pigments on painted plaster in Minoan, Roman and Early
Byzantine Crete [5].
In this study, we demonstrate the ability of micro-Raman spectroscopy as a very efcient and non-destructive method for analysing ancient artefacts. Complementary techniques such as optical microscopy
with ultraviolet light (OMUV), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEMEDS), and energy dispersive
X-ray-uorescence spectroscopy (ED-XRF) were used in some cases to
conrm the identity of certain pigments. The elemental composition

I. Holclajtner-Antunovi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 156 (2016) 7888

of shiny metal leaves which were used for decoration of the saint's
haloes was determined too.
2. Background
Our study focuses on wall paintings of the monastery of ia (Fig. 1),
one of the most important Serbian orthodox monasteries, located in the
central part of Serbia for demonstrating the applied analytical techniques.
We describe here its history, placing in context the required analyses performed. The main church, dedicated to the Holy Salvation, was constructed between 1207 and 1219 as the rst seat of the Serbian Archbishopric
[6]. Its founder Stefan Nemanji, was crowned here in the year 1221. It
was built according to the Raska school in the Romanesque style.
Fresco paintings of the ia monastery have a multilayered and complex structure that follows the history of this monumental building. Initial layer of Zia wall painting was done from 1220 to 1221. According to
the written records by Theodosious, St. Sava, the rst archbishop,
brought for this work one of the famous artists from Constantinople
[7]. These frescos can be found today only in the lower zones of the
choir and lunettes above the entrance into the lateral chapels, but
they are very pale and much damaged. For that reason, the archaeological excavations done between 1988 and 1991 are of special importance.
These excavations brought to light the nds of fragments of wall paintings preserved in an empty grain pit beneath the oor of exonartex and
in a pit deliberately dug in the diaconicon of the temple. The fresco's
fragments have been carefully buried into the pits, with the painted
side down and separated by layers of send. These fragments have very
clean surfaces with fresh paints and without any trace of damage,
chart or dirt and they present the best saved evidence of the rst monastery decoration [8]. Archaeologists suppose that painters from the
rst renovation period, before the renovation and re-painting, removed
the rest of frescoes from the monastery walls and treated them as holy
objects. They buried these fragments after consecration. The remains of
ceramic vessels with traces of pigments were found above the fresco
fragments. It is assumed that these vessels served for preparing the
paint for the renovation process and that artists have put them on the
top of the pits along with other archaeological objects after the renovation has been completed [9].
Unfortunately considered as the center of the state and the church,
ia was cruelly demolished during the 13th century by the attacks of
enemies. The territory where ia is situated is seismically very active
as the mountain Kopaonik the most tectonically active region in Serbia
is nearby, on the south of ia. Multiple strong earthquakes shook the

79

walls of ia causing great damages on the fabric of the building through

the forthcoming centuries. At the beginning of Second World War, ia
was bombarded and part of the north chapel with parts of the dome,
vault and north wall were casted down. Therefore, wall paintings
were frequently exposed to the outdoor environmental conditions and
today's appearance of the church is a result of multiple rebuilding and
restorations in the 14th, 16th, the rst half of 18th, middle of 19th,
through 20th and at the beginning of 21st centuries.
The present multi-analytical method study concentrates on establishing the techniques and the identities of the wall painting pigments
used by the artists from the rst period of decoration in the 13th century
and from the period of the renovation in the 14th century. The analysed
samples include the fragments of the frescoes from the 13th century
and traces of pigments from the ceramic vessels, used by renovators
from the beginning of the 14th century. These results are compared
with the analyses of the pigments of the wall paintings which cover
monastery walls these days. The pigments used by the present day conservators were analysed for comparison. The elemental composition of
shiny metal leaves which were used for decoration of the saint's haloes
was determined too.
3. Experimental
3.1. Samples
All the analysed samples were divided into four groups based on
their origin.
From a total of more than 300 wall painting fragments from the 13th
century excavated from the pits, 6 fragments were selected for analysis
based on stylistic decoration and colours. The wall painting fragments
are of small dimensions, in average 10 15 cm, thus not enabling the
reconstruction of the original composition. They indicate that both the
preparatory and painted layers are well preserved. The samples for
analysis were chosen according the characteristic colours (blue, red, yellow and green) from places considered as containing the pure pigments
and from sections where mixing of pigments is obvious (different
shades of brown, purple and pink) or where the pigments were deposited in a few layers as blue and green over black and yellow over white
layer.
The small layers or particles were extracted from fragments and
analysed in situ by micro-Raman spectroscopy. Samples were also prepared as cross-sections, by embedding into epoxy polymeric resin
Araldite 2020 and then polishing with grinding paper (mesh 500, 800
and 1000). All cross-sections were subjected to examination by optical
microscopy (OM), scanning electron microscopy with energy dispersed
X-ray spectrometry (SEMEDS) and micro-Raman spectroscopy.
The second group of samples contains pigment powders taken from
the ceramic vessels or their fragments, presented in Fig. 2. It is supposed
that renovation painters from the 14th century used these vessels for
mixing and keeping colour paint.
A total of 27 samples (the third group) were carefully removed using
a surgical scalpel from the monastery wall paintings. They were also
prepared as cross-sections. They belong to the different phases of
church construction in the 13th century and big renovation in the
14th century.
The last (4th) group of samples contains pigments used by present
day conservators. From a total of 17 pigments, 13 were identied
based on their Raman spectra.
The traces of shiny metal leaves, found on fragments of wall paintings, were analysed by SEMEDS and micro-Raman microscopy.
3.2. Instrumentation

Fig. 1. The ia monastery near Kraljevo, Serbia.

Detection of the preparatory layer was made by Fourier transform

infra red (FTIR) and micro-Raman spectroscopy, while inspection of
the cross-sections was completed by means of an optical microscope

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I. Holclajtner-Antunovi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 156 (2016) 7888

Fig. 2. Ceramic vessels and their fragments from the rst renovation of the monastery in the 14th century.

and SEMEDS. Inorganic pigments were identied by micro-Raman

spectroscopy and the gold leaves and organic binders were assessed
using SEMEDS and FTIR spectroscopy.
FTIR spectra of the powdered samples, dispersed in potassium bromide and compressed into pellets, were recorded in the range of
1600400 cm1 at 64 scans per spectrum, at 2 cm1 resolution using
a Nicolet 6700 Spectrometer (Thermo Scientic).
Prior to the spectroscopic analysis, cross-sections of the samples
taken from the wall paintings were observed under OM. Cross-sections
of investigated samples were recorded by an Olympus Camedia digital
camera mounted on an Olympus BX51M microscope equipped with
UV lamp Olympus U-RFL-T and U-MWUS3 and U-MWBS3 lters. Magnications were 50, 100 and 200.
The cross-sections of the samples were also analysed with a scanning electron microscope (JEOL JSM 6460 LV) equipped with an Oxford
EDS analyser. Samples were carbon-coated to eliminate charging
effects.
Micro-Raman spectra were recorded on a DXR Raman Microscope
(Thermo Scientic). The 532 nm line of a diode-pumped solid state
high brightness laser was used as the exciting radiation and the power
of illumination at the sample surface ranged between 2 and 6 mW. Collection of the scattered light was made through an Olympus microscope
with innity corrected confocal optics, 25 mm pinhole aperture, standard working distance objective 50, grating of 1800 lines/mm and resolution of 2 cm1. Acquisition time was 10 s with 10 scans. The laser
spot diameter on the sample was 1 m. Thermo Scientic OMNIC software was used for spectra collection and manipulation.
The identication of pigments was performed by comparison of recorded spectra with spectra of standard pigments from a homemade
database or from literature [10,11].
Energy dispersive X-ray uorescence (ED-XRF) spectroscopy measurements were performed on the ED-XRF spectrometer with Canberra
Si(Li) semiconductor detector and MCA analyser S35+. MicroSAMPO
software was used for the spectra acquisition, and measurement time
was 120 s for all the samples. For the excitation, annular radioisotope
source 109Cd (manufactured by Isotope Products) with nominal activity
of 740 MBq was used.

4. Results and discussion

4.1. Preparatory layer
The fresco technique, the most common technique used for decorative paintings of wall surfaces in antiquity, was used for making all the
wall paintings in the monastery of ia. It is concluded based on the
presence of calcite (CaCO3) in Raman spectra of the surface plaster
and preparatory layer, as well as in almost all painted layers (Fig. 3).
Below the ne, smooth and lustrous surface of outer plaster made of
solely calcite (about 1 mm thick), there is the preparatory layer (up to
3 cm tick) composed of slaked lime mixed with quartz sand, straw
and hemp. Micrograph and electron back scattered image of a fragment
of hemp found in the preparatory layer is presented in Fig. 4.
Calcium carbonate was used both as substrate (plaster and preparatory layer), binder and as a white pigment. The Raman spectrum of calcite revealed essentially a characteristic vibration band centred at
1086 cm1, assigned to the symmetric stretching mode of carbonate
ion, the lattice-translation vibration at 281 cm1 and the in-plane bending vibration at 712 cm1 (Fig. 3a).
Raman spectra of some samples give evidence for gypsum and
weddellite, besides calcite. The spectra and characteristic bands of gypsum and weddellite are presented in Fig. 3b and c. Gypsum could be a
degradation product of calcite, formed from reaction of calcite with sulphur dioxide from humidied atmospheric air. Calcium oxalate,
weddellite (CaC2O42H2O) may have chemical or even biological origin,
may be a pollutant or degradation product of organic matter such as
hemp and straw or may originate from restorations [12].
4.2. Analysis of pigments on wall paintings
In ia's wall paintings, colour layers are superimposed one above
the other. Table 1 reports the wavenumbers of the characteristic
Raman peaks of all mineral species identied in analysed samples. Pigments of wall painting fragments from the 13th century identied by
Raman spectroscopy and SEMEDS are given in Table 2. Table 3 presents
a list of powdered pigments from ceramic vessels identied by Raman

I. Holclajtner-Antunovi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 156 (2016) 7888

81

from all analysed groups. As a very efcient Raman scatterer, TiO2

present even in traces gives a very intensive spectrum. Therefore, the
occurrence of this TiO2 polymorph on wall paintings can be explained
by their trace occurrence in natural earth pigments.
The characteristic features of -quartz, trigonal SiO2, a natural silica
polymorph, were identied in Raman spectra of many samples. Quartz
is a common constituent of earth pigments or can originate from preparatory layer.
4.4. Red colour

Fig. 3. Raman spectra of a) preparatory layer of wall paintings (calcite), b) of gypsum and
of c) weddellite from wall paintings in ia, asterisk indicates signals of calcite.

spectroscopy, while Table 4 gives results of analysis of cross-sections of

wall paintings from the 13th and 14th centuries, which cover the monastery walls today, by Raman and SEMEDS spectroscopies. Fourteen
from the total of seventeen pigments from the conservator's collection
were identied based on their Raman spectra and are presented in
Table 5.
4.3. White colour
Calcite was used as white pigment but also in mixture with other
pigments to make lighter shades of different colours.
The conservator's collection (Table 5) contained barium white
(BaSO4) and zinc white (ZnO) besides calcite as white pigment, but
analysis of samples revealed the presence of barium white only in
some wall paintings which can be indication of restoration process or
of traces present in mineral pigments and preparatory layer [5,13].
Anatase, one of the three titanium (IV) oxide polymorphs, used as
white pigment since the 20th century, was identied in many samples

Analysis of red grains led to the identication of three different compounds, iron(III) oxide, vermilion HgS and litharge PbO.
Iron(III) oxide, -Fe2O3, known as hematite, a mineral with the same
composition, was identied by its Raman bands at 225 (vs), 244 (m),
290 (vs), 410 (s), 496 (m), 611 (s) and 1319 (s, br) cm1 in the majority
of samples (Fig. 5a). The band at 662 (m) cm1, observed in some samples, can be attributed to magnetite, Fe3O4. This mineral was found in
spectra of samples with dark red shades. The mineral red ochre (red
ochre, sienna or umber, all of which have hematite as the main tinting
component) could be identied on wall paintings from early period in
the 13th or from the 14th century (Tables 2 and 3).
The highly intense red pigment on many wall painting fragments
found in the pits (originating from the period of initial paintings in the
13th century), was identied as vermilion with characteristic Raman
bands at 252 (vs), 283 (w) and 342 (m) cm1 (Table 2). Cinnabar, the
natural form, has been used as a pigment since ancient times while vermilion, the synthetic form, has been known since the 8th century.
Therefore, both forms could have been used for decoration of wall paintings in ia. In red sections of samples from the 13th century, vermilion
is applied for attaining intensive red colour as in samples 6-2 and 16-3
(Table 2). Vermilion was identied in one of the vessels (A-81) used
by painters from the rst renovation period. The characteristic band of
vermilion at 252 cm1 appears in Raman spectra of some wall paintings
from the 14th century, but always followed by an intensive spectrum of
hematite (Table 4). It is possible that vermilion was added to hematite
for obtaining desired red shades. However, pure vermilion was not
identied on the wall paintings from this period.
Red pigment litharge was identied only in one of the ceramic vessels from the 14th century, but not on the wall paintings. It is possible
that litharge was added to hematite but in low concentrations.
4.5. Yellow colour
The analysis of yellow grains led to identication of iron(III)
oxyhydroxide, -FeOOH, also known by the name of the mineral goethite. Its Raman spectrum reveals bands at 203 (vw), 244 (w), 298
(m), 390 (m), 479 (w) and 550 (w) cm1 (Fig. 6a). As the pigment
grains studied were found to be of different sizes and shapes, it indicates
that a natural form of pigment was used. However, in some cases the

Fig. 4. Micrograph and back scattered image of hemp fragment in preparatory layer.

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I. Holclajtner-Antunovi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 156 (2016) 7888

Table 1
Some physical and chemical characteristics and Raman spectral data of minerals (or pigments) of wall painting fragments from 13th century (WPF), powdered pigments from ceramic
vessels (CV) used for the rst renovation in 14th century, samples from wall paintings (WP) which cover monastery walls today and pigments of present day conservators (CoP) materials.
Colour

Mineral or pigment Chemical formula

White
White
White
White
White
White
White
Red

Calcite (chalk)
Barium white
Zinc white
Anatase
Lead white
Gypsum
Weddellite
Hematite
Red ochre
Red
Vermilion
Red
Litharge
Red
Madder (alizarin)
Blue
Lapis lazuli
Blue
Prussian blue
Yellow
Goethite
Yellow
Yarosite
Green
Terre verte
Colourless Quartz
Black
Lamp black

CaCO3
BaSO4
ZnO
TiO2
2PbCO3Pb(OH)2
CaSO42H2O
Ca(C2O4)2H2O
-Fe2O3
Fe2O3 + clay + SiO2
HgS
PbO
C14H8O4
Na810[Al6Si6O29]S24
Fe4[Fe(CN)6]31416H2O
-FeO(OH)
Pb0.5Fe3+3 (SO4)2(OH)6
K[(AlIII,FeIII)(FeII,MgII)], (AlSi3,Si4)O10(OH)2
-SiO2
C

Raman bands (cm1) and relative intensities

Sample type

155 w, 281 w, 713 w, 1086 vs

453 w, 461 w, 616 w, 647 w, 988 vs
331 w, 383 w, 438 vs
145 vs, 399 vw, 477 vw, 518 vw, 639 vw
667 vw; 665 vw; 687 vw; 829 vw; 1050 vs
415, 492, 1008 vs, 1134
197, 502, 896, 1462, 1490
224 s, 242 w, 291 vs, 407 m, 494 w, 610 m, 1310 m
220 vs, 286 vs, 402 m, 491 w, 601 w
252 vs, 282 w (sh), 343 w
145 vs, 285 vw, 336 w
480 w, 657 w, 841 w, 902 w, 1162 m, 1296 m, 1323 m, 1476 s, 1633 w (br)
258 w, 547 vs, 822 w, 1096 w
274 vw, 530 vw, 2155 vs
300 m, 390 s, 479 w, 550 w
213 s, 332 w, 436 s, 615 w, 996 m, 1011 m, 1170 w
145 vs, 399 w, 510 w, 636 m, 685 m, 820 vw, 1007 m, 1084 m
148 w, 200 m, 462 vs
1325 s (br), 1580 s, (br)

WPF, CV, WP, CoP

WP, CoP
CoP
WPF, CV, WP, CoP
WP
WP
WP
WPF, CV, WP, CoP
WPF, CV, WP, CoP
WPF, CV, WP, CoP
WPF, CV, WP, CoP
CoP
WPF, WP, CoP
CoP
WPF, CV, WP, CoP
CV
WPF, WP, CoP
CV, WP
WPF, CV, WP, CoP

The most intensive bands are bolded.

Relative intensity: vw (very weak), w (weak) m (medium), s (strong), vs (very strong), br (broad), and sh (shoulder).

SEMEDS analysis identied impurities of clay and grains of quartz in

goethite, thus conrming application of yellow ochre for yellow colour.
Yellow ochre is one of the basic pigments in Byzantine iconography.

Table 2
Analysed wall painting fragments from the 13th century, compounds identied by Raman
spectroscopy, elemental composition obtained by SEMEDS.
Sample code

Photography of samples

Colour

Compounds identied by
Raman spectroscopy and
elemental composition
obtained from SEMEDS

62

Red
Blue

HgS, C
Na810[Al6Si6O29]S24

141

White
Black
Blue
Pink

CaCO3
C (Lampblack)
Na810[Al6Si6O29]S24
Fe2O3, CaCO3

142

Green

K[(Al3+,Fe3+)(Fe2+,Mg2+)],
(AlSi3Si4)O10(OH)2

144

Black
Grey
Yellow

C (Lampblack)
C (graphite), CaCO3, TiO2
-FeO(OH)

163

Violet
Red
Dark red

HgS, Na810[Al6Si6O29]S24
HgS
Fe2O3, Fe3O4

4.6. Blue colour

In the samples collected from blue regions of the wall paintings, we
obtained Raman spectra of only one pigment. This pigment is lapis lazuli
(ultramarine blue), extracted from expensive and precious mineral
lazurite of approximate formula Na8[Al6Si6O24]Sn. No evidence of azurite (basic copper(II) carbonate), a blue pigment cheaper than natural
lapis lazuli in any sample was found. The Raman spectrum of the blue
grain is presented in Fig. 6b.
On studying the cross-sections of the blue painted regions, it was
established that they consists of three different layers of different thickness, Fig. 7. The rst (lower) layer is composed of iron containing pigments (spectrum 3). The second (middle) layer (spectrum 2) contains
black and white grains attributed to carbon black and calcite respectively. From the irregular shape of black grains and their Raman spectra, it is
deduced that this is made of wood coal (Fig. 6d). Over this layer, there
are blue grains with variable particle size and inclusions. The Raman
spectra of these blue grains are identied as lapis lazuli and inclusions
as calcite. In contrast to synthetic pigment characterized by uniformly
sized pigment particles, blue particles of this layer are of variable sizes
and shapes, with a large concentration of inclusions. The inclusions
show intensive uorescence when observed under OMUV. These
facts conrm natural origin of this pigment applied for blue colour in
wall paintings of ia monastery [14].
The application of a carbon black layer below a blue one was a common method in Byzantine hagiography. The purpose of the black layer is
to enhance the blue colour tone. This study showed that the same method was applied for intensifying green colour.
The natural pigment lapis lazuli was found on Greek wall paintings
from the thirteenth century BC [15], on European wall paintings from
the 8th century as an early example of oriental inuence in San Saba

Table 3
Powdered pigments from ceramic vessels identied by Raman spectroscopy.
161

Main coloured compounds are in bold.

Brown

Fe, Ca, Mg, Si, Al, K, S, P, Cl

Colour

Sample code

Compounds identied

White
Red
Red
Yellow
Yellow

A88
A81
A82
A80
A67

CaCO3
HgS
Fe2O3, PbO, SiO2
-FeO(OH)
KFe3(OH)6(SO4)2

I. Holclajtner-Antunovi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 156 (2016) 7888

83

Table 4
Cross-sections of wall paintings which cover monastery walls today analysed by micro-Raman and SEMEDS spectroscopy.
Colour

Sample code

Location on the wall painting

Compounds identied by micro-Raman spectroscopya

and elemental composition obtained from SEMEDS

Blue
Black
Blue
Dark violet
Red
Dark red
White
Yellow
Red
Dark red
Green
Yellow
Green
Blue
Blue
Red
Dark violet
Yellow

Ornament in crown of St. Helena

2
4
5

Blue stripe surrounding JC

Stripe under the feet of St. Helena
St Constantine

Stripe next to the window

7
8
9
10

Southern wall St. Demetrios

Southern wall St. Demetrios
Green background under the foot of St. Simon the Zealot
St Simon the Zealot

11
12

Yellow

13

Violet

14

Southern wall of the S. choir stripe on the window

Southern wall of the choir
Ornament in the window
Northern side Northern wall
Saint monk (?) and St. Theodore of Stoudios
St. Theodore of Stoudios

Na810[Al6Si6O29]S24
C, 2PbCO3Pb(OH)2
Na810[Al6Si6O29]S24
Fe, Ca, Si, Al, Mg, Mn, P, S, Ni
Fe2O3, Fe3O4, CaCO3
Fe2O3, Fe3O4, C, CaCO3
Ca(C2O4)2H2O, CaCO3
Fe, Ca, Si, Al, Mg, P, Ni
Fe2O3, BaSO4, C
Fe3O4, Fe2O3, TiO2
K[(Al3+,Fe3+)(Fe2+,Mg2+)], (AlSi3Si4)O10(OH)2
-FeO(OH), TiO2
Ca, Si, Fe, K, Mg, Al, S, P, Cl
Na810[Al6Si6O29]S24,Fe2O3,Fe3O4, C
Ca, Na, Si, Al, S, Mg, K, P
Fe2O3, Fe2O3, Fe3O4, C
Fe2O3, Fe3O4, Fe2O3, CaCO3, C, TiO2
-FeO(OH), CaCO3, TiO2

Green

15

Red

16

White

18

Black

19

Green

20

Red

21

Brown

23

Violet

24

Green

25

Grey
Red

26 Upper layer
Middle layer

Western wall
Archangels holding Christ's bust in a medallion
Western wall
Painted socle zone
Western wall
Archangels holding Christ's bust in a medallion
White pearl on ochre background
Western wall
Painted socle zone
Northern wall
St. Nikolas of Myra and St. Stephen the Protomartyr
Northern wall
St. Nikolas of Myra and St. Stephen the Protomartyr
Northern wall
St. Nikolas of Myra and St. Stephen the Protomartyr
Northern wall
St. Nikolas of Myra and St. Stephen the Protomartyr
Northern wall
St. Nikolas of Myra and St. Stephen the Protomartyr
Dark green background
Northern wall
St. Tarasios of Constantinople

-FeO(OH), CaCO3
Fe2O3, Fe3O4, C
Ca, Fe, Na, Si, Al, S, Mg, K
K[(Al3+,Fe3+)(Fe2+,Mg2+)], (AlSi3Si4)O10(OH)2
Fe2O3, Fe3O4, C
Fe, Ca, Si, Al, Mg, K, S, P, Cl
CaCO3, -FeO(OH)
Fe, Ca, K, Mg, Al, Si, S, P, Cl
C, CaCO3
Ca, Si, Fe, K, Mg, Al
Fe2O3, Fe3O4, HgS (tr.?), CaCO3
Fe2O3, MnO2, HgS (tr.?)
Fe2O3, MnO2, Fe2O3, C
Fe, Ca, Mg, Mn, Si, S, Cl,
Ca, Si, Fe, K, Mg, Al, S, Cr, Pb, Zn, Ba, Bi

CaCO3, C, Fe2O3
Fe2O3, Fe3O4

Samples 16 are from the room in the tower (XI in Fig. 1), belonging to the second phase of decoration in 13th century.
Samples 712 are from the southern choir (IV in Fig. 1), belonging to the rst phase of decoration in 13th century.
Samples 1326 are from the second western bay of the naos (VII in Fig. 1), belonging to the phase of renovation in the 14th century.
a
Main coloured compounds (micro-Raman) and main elements (SEMEDS) are in bold.

Table 5
Pigments collected from present day conservator's collection identied by Raman
spectroscopy.
Colour

Sample code

Compounds identied by micro-Raman

spectroscopy

White
Red
Red
Blue
Blue
Green

C1
C2
C3
C4
C5
C6

White
Yellow
White
Black
Black
White
White

C7
C8
C9
C10
C11
C12
C13

BaSO4
Fe2O3
C14H18O5
Na810[Al6Si6O29]S24
Fe4[Fe(CN)6]31416H2O
K[(Al3+,Fe3+)(Fe2+,Mg2+)],
(AlSi3Si4)O10(OH)2
ZnO
-FeO(OH)
CaCO3
MnO2
C
CaCO3, BaSO4
TiO2 (anatase)

church in Rome [16], while there is evidence that in Byzantine hagiography lapis lazuli was found on manuscripts known as Vienna Dioskurides
and Vienna Genesis from the 6th century [17]. In Serbia, until now this
expensive pigment was exclusively used in blue coloured paintings in
ia, but also in the monastery of Mileseva [18]. Due to the great spiritual and national importance of these monasteries, the expensive pigments such as lapis lazuli and vermilion were used for decorations.
According to historical sources, many orthodox monasteries and
churches were constructed under the nancing of great potentates
and kings, as in the case of the ia monastery which was founded by
the king Stefan Nemanji. In the later periods when the number of sacral
objects was growing, the cheaper, widespread materials were used for
decoration. For example, black over the white layer was used often for
attaining blue colour impression.
The violet lines deposited over the dark red colour were identied
on fragments from the initial paintings of the 13th century as being
composed of red pigment vermilion and blue pigment lapis lazuli. The
Raman spectrum obtained from mixture of these minerals is presented

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4.7. Green colour

Celadonite, a green clay mineral of approximate chemical composition K(Mg,Fe2+)(Fe3+,Al)[Si4O10](OH)2, was identied by Raman spectroscopy as the green pigment used on wall paintings, Fig. 6c. Celadonite
is one of the main colouring agents of green earth, other is glauconite, a
green clay mineral with approximate chemical composition (K,Na)
(Fe3+,Al,Mg)2(Si,Al)4O10(OH)2. Celadonite is a well-crystallized mineral of volcanic origin while glauconite is formed gradually from sedimentary minerals and can vary widely in composition. As a consequence of
origin, they occur in different localities, celadonite in vesicular cavities
or fractures in volcanic rocks and glauconite in sandstones and marls
deposited as marine sediments. Raman reference spectra of celadonite
has characteristic bands at 174 (s), 273 (m), 381 (w), 393 (m), 445
(w), 460 (w), 551 (s), 701 (m), 768 (vw), 797 (vw), 961 (w), 1017
(sh), 1056 (w), 1086 (w), 1132 (w), and 1597 (w, br) cm 1, while
bands of glauconite are at 592 (m) and 701 (w) cm1 [19].
Green earth pigment was also identied by elemental composition
obtained by the complementary SEMEDS method (Tables 2 and 4).
This pigment was deposited over the layer of charcoal black in green regions of all the samples. This is a frequent method in Byzantine hagiography for attaining intensive green colour impression.
4.8. Black colour

Fig. 5. Raman spectra of red pigments: a) red, hematite, b) intensive red, litharge,
c) vermilion, d) dark red, hematite, magnetite, vermilion and e) pink, hematite and calcite.

in Fig. 6f. The manufacturing process produces a mixture of ne particles, and the individual grains could be resolved under high magnication of microscope.

The black pigments always gave rise to a Raman spectrum characteristic of carbon-based black. In the majority cases, two broad bands, D
band at 1340 (vs, br) and G band at 1596 (vs, br) cm1 in Raman spectrum indicate disordered carbon-based material (e.g., charcoal) Fig. 6d.
In some samples, graphite, organized carbon-based material, was identied by the characteristic sharp G peak at about 1590 cm1 and very
weak, broad D peak at about 1340 cm1. Different tones of grey colour,
found on fragments from the 13th century, were attained by mixing of
graphite and calcite (Fig. 6e) in different ratios.
4.9. Analysis of pigments from ceramic vessels

Fig. 6. Raman spectra of pigments: a) yellow, goethite, b) blue, lapis lazuli, c) green earth,
d) black, lampblack, e) grey, graphite and anatase, f) violet, vermilion, lapis lazuli, calcite.

The rst renovation of the heavily damaged church started at the beginning of the 14th century. The renovators from that period removed
almost all the painting fragments from the walls and carefully buried
them into pits lled with sand. They deposited ceramic vessels used
for paint preparing and keeping at the top of the pits.
The residues of pigments from these vessels were identied by
Raman spectroscopy and presented in Table 3. White pigment found
in vessel A88 was calcite, as the main component, with traces of carbon
black. Vessel A81 contained expensive pigment vermilion which was
applied as red pigment in the 14th century. This pigment because of
its high cost was used only in very important paintings [20].
In vessel A82, besides hematite, as the main component, and quartz,
a smaller quantity of litharge (tetragonal PbO) was identied. Litharge
has been used as a pigment since antiquity, its colour ranging from yellow to red. It is a strong Raman scatterer with characteristic bands at
145 (vs), 285 (vw) and 336 (w) cm1. The Raman spectrum of powder
from vessel A82 is presented in Fig. 8a. Presence of litharge in this vessel
is conrmed by combination of Raman and ED-XRF spectroscopy, as
mineral anatase has very strong signal at 145 cm1, thus may interfere
with the main signal of litharge. Fig. 8b presents ED-XRF spectrum of
sample from vessel A82. In this spectrum Fe and Pb are identied as
the main components with traces of As. This conrms that the strong
peak at about 145 cm1 originates from litharge and not from anatase.
It is obvious that artists from the 14th century for the rst renovation of
the church used red ochre diluted with litharge (with traces of realgar,
As4S4) for obtaining red colour, from both economic and aesthetic
reasons.
Yellow ochre with mineral goethite as the main constituent was
identied in vessel A80. This pigment was mainly used for attaining

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85

Fig. 7. Optical and backscattered SEM micrograph and SEMEDS spectra of different layers of sample 10. (For interpretation of the references to colour in this gure, the reader is referred to
the web version of this article.)

yellow colour in wall paintings in ia. In vessel A67, residua of yellow

pigment is identied as mineral Yarosite, Pb0.5Fe3 +3(SO4)2(OH)6.
Potassium-jarosite was mentioned as a yellow pigment identied in
paintings from the 4th to the 1st century BC [20]. However, as the quantity of the powder sample was insufcient, it was not possible to nd out
if this mineral was used as a pigment or it was present as a constituent
in the ceramic body of the vessel.
4.10. Analysis of gilding
In the Middle Ages, we could nd gildings on wall paintings of sacral
objects, such as churches and monasteries. The use of the precious metal
for gilding has an artistic, aesthetic, political and liturgical function; it is a

sign, mark and symbol of power and authority. Because of bad environmental conditions in such objects, the gildings very often do not resist
anymore, only traces of metal or the adhesive under-layer remain [21].
Nowadays detection of ancient gildings is performed usually by means
of the uorescence of the binders used to adhere the metallic leaves.
The saint's haloes and letters in irilica (Serbian analphabetic) of the
initial wall paintings in the monastery of ia were decorated with gold
leaves. Very scarce remains of them were preserved. The optical micrograph of such a sample (from the saint's haloes) taken from the fragment found in the pit, indicates existence of three different layers. The
golden foils are deposited over the yellow ground, with a dark layer between them. In some places, there are white deposits of calcite salting
out (Fig. 9 left top).

Fig. 8. a) Micro-Raman and b) ED-XRF spectrum of powder mixture found in ceramic vessel A82.

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Fig. 9. Optical micrograph (left top) and backscattered electron image of the cross-section of gilding sample (left bottom) and SEMEDS spectra (right) of: rst metal layer spectrum 1,
second metal layer spectrum 2, and yellow layer spectrum 3. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

From backscattered electron micrograph (Fig. 9 left bottom), the occurrence of three different layers was observed too. The rst surface
layer is metallic, of few microns thickness. The second intermediate
layer is also metallic, with an average of 40 m thickness. The third is
a yellow coloured layer of 510 m thickness. From SEMEDS analysis,
the rst layer is identied as gold with traces of silver (Fig. 9 spectrum
1). The second layer is composed of tin (Fig. 9 spectrum 2). The elemental composition of the third layer (Fig. 9 spectrum 3) indicates that the
yellow pigment is yellow ochre. This means that for gilding of saint's
haloes, thin golden foil was deposited over the tin sheet. In order to
get a desirable optical and aesthetical impression, the metallic leaves
were deposited over the yellow ochre preparatory layer.
In the region between the yellow preparatory and the metallic layers,
we observed bluish uorescence in optical micrograph under UV light,
Fig. 10a. In the Raman spectrum of this layer, only a broad band at
about 600 cm1 is detected besides broad bands about 1600 and
1300 cm1 originating from amorphous carbon and organic traces. Since
no traces of sulphur, nitrogen or phosphorus were found in the SEM
EDS spectrum of this layer, we suspect that this layer is most probably
made of resin that gives the blue uorescence [22]. The FTIR spectrum
of sample from this layer is presented in Fig. 10b. Typically, OH stretching
vibrations occur as broad bands near 3400 cm1, methyl and methylene
stretches occur in the region of 28003200 cm1 and carbonyl bands are
seen at 16901750 cm1. The band appearing near 1730 cm1 is evidence for the presence of ester carbonyl groups. Due to the alternation
of organic matter, it is difcult to identify exactly the type of binder
used. A method such as gas-chromatography with mass spectrometry
should identify more precisely the binder type. The bands in the ngerprint region (below 1800 cm1) belong to calcite from the preparatory

layer as the main component and iron oxide and aluminosilicates from
yellow ochre. Nevertheless, the bluish uorescence under UV light and
characteristics of FTIR spectra indicate polyhydroxy acids as an adhesive
binder, possibly a mixture of resin and oil [22,23].
In general, there are two techniques of gilding of the fresco paintings. The rst technique with binders soluble in water includes the preparatory layer made of red or yellow bole (red or yellow earth rich in
kaolin) mixed with gum Arabic, juice from garlic or resins. A technique
that includes use of oil binder comprises preparation of oil with some
kind of driers like lead white or verdigris. The dried oil is used on the
dry bole preparatory layer. Recipes for gilding the wall and icon paintings can be found in old manuscripts like in Il Libro dell Arte by
Cennino d'Andrea Cennini from the 14th century [24]. There in
Chapter XCIX, we can nd a recipe for making a gilding based on tin
foils. Further, in Chapter CI, it is mentioned that when making haloes
with this gilded tin, one should use the varnish to stick them to the
wall. It seems that this kind of gilding technique was used in ia monastery in the 13th century, by placing gilded tin foils on the yellow ochre
ground with use of resin mixed with oil as a binder.
5. Conclusion
The chemical compositions of the materials used in the preparatory
and pictorial layers of wall paintings from the monastery of ia have
been studied by micro-Raman spectroscopy as a very efcient, nondestructive and in situ method with high spatial and spectral resolution.
In some cases, complementary techniques such as OMUV, SEMEDS,
ED-XRF and FTIR spectroscopies were used to conrm the identity of
pigments, binders and gildings.

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87

Fig. 10. a) OMUV micrograph of gilding cross-section and b) FTIR spectrum of layer between metallic and preparatory layers. (For interpretation of the references to colour in this gure,
the reader is referred to the web version of this article.)

The results have shown that all the wall paintings are made in fresco
technique using calcite as substrate (plaster and preparatory layer),
binder and as a white pigment. Calcite was also mixed with other pigments for obtaining lighter shades.
Deposits of gypsum on wall paintings as well as traces of weddellite
are degradation products formed as a result of exposing wall paintings
to the environmental conditions especially in the periods during the serious destructions of the monastery.
The pigment pallet used for decoration of ia was relatively modest,
consisting mainly of natural earth pigments, suitable for painting on wet
plaster. The pigments generally used to obtain red colours are hematite
and red ochre. Very intensive red colour on wall painting fragments
dated from the beginning of the 13th century, the period of the rst
monastery decoration was attained by application of expensive pigment
vermilion. In one ceramic vessel was identied vermilion while another
vessel contained litharge mixed with red ochre, as an evidence of use of
this pigment by the artist from the period of the rst monastery renovation. For brown colours, less pure red ochre was used in all samples.
Green earth was used identied in green coloured parts. Intensive
blue colour of all paintings was obtained by application of lapis lazuli,
a frequently mentioned pigment in Byzantine hagiography. Carbon
black or graphite was used for attaining black colour. These species
were also added to other pigments for attaining the darker tones. The
darker tones were obtained in some cases with use of earth pigments
rich in magnetite. Other mixtures of pigments were also applied: vermilion and lapis lazuli to form violet, red ochre and calcite to form
pink and carbon black or graphite and calcite to form grey. The shade
of violet depends on the relative ratio of vermilion, lapis lazuli and calcite or carbon black. A carbon black layer was often applied below a
blue or green layers in order to enhance these colours. This is a common
method in Byzantine hagiography.
Halos of the saints and letters in irilica (Serbian analphabet) were
decorated by shiny metal leaves consisting of gold and tin. In micrographs of cross-section of gildings, between the thin metal surface and
the yellow underlayer made of yellow ochre, there is a layer of uorescent organic binder. Use of pigments such as lapis lazuli and vermilion
and gildings of golden tin conrms the wish of the Serbian aristocracy
to show their economic power in the period when only few churches
were built.
Acknowledgements
The authors acknowledge the support from the Ministry of Education, Science and Technological Development, Republic of Serbia (Project No. 177021). he authors would like to thank Tatjana Mihajlovi,

curator of Archaeological collection of Museum of Kraljevo and Prof.

Dragan Vojvodi, University of Belgrade-Faculty of Philosophy, for valuable advices and discussions, Velibor Andri, University of Belgrade-Institute Vina, for ED-XRF measurements and Sran Vulovi, Kraljevo
Museum, for sample photographs.

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