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Journal of Cultural Heritage 9 (2008) 207e213 http://france.elsevier.com/direct/CULHER/

Case study

Studying wall paintings in Berati Castle (Albania): Comparative examination of materials and techniques in XIVth and XVIth century churches
Nikolla Civici a, Magdalini Anastasiou b, Triantallia Zorba b, Konstantinos M. Paraskevopoulos b,*, Teuta Dilo c, Frederik Stamati d, Mustafa Arapi e
b a Institute of Nuclear Physics, P.O. Box 85, Tirana, Albania Solid State Physics Section, Department of Physics, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece c Department of Physics, University of Tirana, Tirana, Albania d Institute of Popular Culture, Tirana, Albania e Institute of the Monuments of Culture, Tirana, Albania

Received 10 April 2007; accepted 2 August 2007

Abstract In this paper the study is focused on the continuation of the Byzantine wall painting iconography in Albania through the study of two characteristic churches of the 14th and 16th centuries situated in the Castle of Berati. The town of Berati has a long history that goes back to the Bronze Age, and the old castle, situated on top of a hill, has always been the nucleus of the town and is still inhabited. Several churches within the castle walls are decorated with beautiful wall paintings and icons, beautiful examples of Byzantine and post Byzantine art and architecture. The techniques used to analyze the samples were optical microscopy, TXRF, micro-FTIR and SEM-EDS. Similar materials were used in the construction of the wall paintings of both churches, marking a continuation in the Byzantine technology in the construction of wall paintings. The presence of calcium carbonate reveals the use of the fresco technique. Colors were rendered by the application of calcite, azurite, green earth, cinnabar, ochres and carbon black. Plaster was composed in all cases mainly of calcite with small amounts of silicates and organic bers while there were characteristic differences between the plaster samples of the church of the 16th century in the presence of gypsum, originating to its use by the painter as a constituent element. All painted samples suffered from deterioration, identied even visually. 2008 Elsevier Masson SAS. All rights reserved.
Keywords: Onoufrios; Albania; Byzantine wall paintings; Church; Fourier transform infrared spectroscopy; Total reection X-ray uorescence; 14th century; 16th century

1. Introduction 1.1. Historical Albanians are an ethnic outcropping of the Illyrians, who inhabited the country for the rst time in the 2nd millennium B.C. In the 2nd century B.C. Albania was conquered by Rome. After the division of the Roman Empire into two parts (eastern and western), the territories of modern Albania became part of
* Corresponding author. Tel.: 30 231 099 8015; fax: 30 231 099 4301. E-mail address: kpar@auth.gr (T. Paraskevopoulos). 1296-2074/$ - see front matter 2008 Elsevier Masson SAS. All rights reserved. doi:10.1016/j.culher.2007.08.004

the Eastern Roman Empire (Byzantine Empire). At 732 A.C. the entire Balkan Peninsula belonged religiously to the Eastern Church. However, by the end of the 11th century the Albanian territories were religiously divided. At that time the north Albanian territories fell under the inuence of the Roman Catholic Church while the other part of the country continued under the Eastern Orthodox Church [1]. This situation still exists although during the Ottoman occupation part of the population in all the country was converted to Muslim religion. The town of Berati is situated in central Albania. During the late Byzantine period Berati had been an important centre for the empire and often was governed by ofcials strongly

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N. Civici et al. / Journal of Cultural Heritage 9 (2008) 207e213 Table 1 List of the samples Color White Yellow Red Light red Dark red Green Dark green Blue Brown Black Plaster St. Theodori STH STH STH STH STH STH e STH STH STH STH STH STH STH STH 7-W, STH 16-W 3-Y, STH 13-Y 15-R 2-R 1-R, STH 10-R 8-G, STH 9-G 5-Bl, STH 12-Bl 4-Br, STH 6-Br, STH 14-Br, STH 17-Br 11-B 18-Pl (East wall, painted by Onoufrios), 1-Pl (North wall), 2-Pl (East WALL, painted by Onoufrios), 3-Pl (East wall), 4-Pl (South wall) St. Trinity STR5-W STR1-Y STR3-R e e STR2-G STR6-G e STR7-Br STR4-B STR8-Pl

related to the emperor himself. By the 14th century, Berati fell under the inuence of the Serbian King Stefan Dushan and some years later turned under the dominion of the Musachi. In 1417 Berati was conquered by the Ottomans who held it until the beginning of the 20th century when Albania was proclaimed independent. Several old churches that still exist within the castle are an indication of the cultural and artistic development of the city. They belong to the period from the 13th to 19th centuries. The most important school of Albanian iconographers, known as the Berati School, was created in Berati at the beginning of the 16th century. This school is related with the name of the famous painter Onoufrios from Neokastra (Onufri in Albanian language). Onoufrios is considered as one of the best icon painters of the whole Balkan region and the best painter that had ever worked in Albanian territory [2]. He managed to combine the local painting tradition with the best tradition of the eastern (Paleologian) and western (Italian) schools, resulting in a realistic and natural drawing. 1.2. The monuments The rst church, the church of Saint Trinity, is situated in the south-eastern part of the castle of Berati, within its surrounding walls. It is a single aisle basilica with narthex (7.5 12.5 m), built in the form of a Greek cross with dome, not later than the rst half of 14th century [3]. This small but beautiful church reects the features of Byzantine architecture and is one of the best-preserved monuments of this kind in Albania. The remaining fragments of the wall paintings indicate that the whole interior of the church had been decorated with beautiful wall paintings of an anonymous author. The wall paintings, being of the Byzantine style, are attributed to the period of construction of the church. The second church, the church of Saint Theodori, is a single aisle chapel (9 3.6 m) with undecorated stone walls, low tiled timber roof and no architectural value compared to the church of St. Trinity. Although the foundations belong to an earlier period, the present church was built during the rst half of the 16th century when the famous painter Onoufrios decorated it with wall paintings [2,4]. The work of Onoufrios is partly preserved on the eastern wall. Some wall painting fragments on the northern and southern walls indicate that part of the church would have been painted by an anonymous painter, whose work cannot be compared with the artistry of Onoufrios. 2. Experimental 2.1. Sampling A total number of 30 samples were accumulated from the two churches. In the church of St. Trinity the samples were collected from the dome, while in that of St. Theodori all samples were collected from the eastern wall except two plaster samples collected from the north and south wall. A list of the samples is given in Table 1, where STR stands for St. Trinity and STH for St. Theodori.

In each of the sampling points two types of samples were collected. The rst one consisted of small pieces of pigment and plaster (about 5 mm2), carefully chosen from areas with less iconographic value, these being the samples for Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy/energy-dispersive spectroscopy (SEM-EDS) and optical microscopy. From the same sampling points, pigment microsamples for total reection X-ray uorescence (TXRF) analysis were collected according to the method proposed by Klockenkamper et al. [5], these being the second type of samples. 2.2. Methodologies Samples were examined by optical microscopy using an Olympus BX60M optical microscope equipped with an Olympus DP10 digital camera. The TXRF analysis system is composed of a total reection module (Vienna Atominstitut [6]) attached to a tube excitation system (Philips PW 1729 X-ray generator and PW 2215/20 Mo anode X-ray tube), an X-ray spectrometer (Canberra Si(Li) detector) and spectrum acquisition system (Canberra Mod 2024 fast spectroscopy amplier, Mod 8076 ADC, Mod 3105 high voltage power supply and Genie 2000 MCA) together with quantication software (QAES package [7]). The substitution of the cut-off reector by a tungsten/ carbon multilayer monochromator (Osmic Inc., USA.) allowed us to achieve a spectrum with low background in the region 2e15 keV. During the measurements the generator was operated at 40 kV and 40 mA, the samples being measured for times varying from 200 to 1000 s. FTIR spectra were obtained using a PerkineElmer FTIR microscope model i-series equipped with a nitrogen-cooled MCT detector, connected with a PerkineElmer FTIR spectrometer model Spectrum1000. For the FTIR measurements tiny species from the painted surface or from the substrate of the samples were removed with a sharp tip of a microscalpel and placed on a freshly prepared KBr pellet. The IR spectra, in transmittance mode, were obtained from different areas of the specimens with an aperture 20e100 mm in the MIR spectral region.

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The same pellets used in FTIR measurements were studied by EDS analysis after being coated with carbon, using a Jeol JEE-4X vacuum evaporator. EDS was realized using a Jeol 840A scanning microscope with an energy dispersive spectrometer attached by Oxford, model ISIS 300. 3. Results and discussion The strong presence of the characteristic peaks of calcium carbonate in all FTIR spectra, in combination with the TXRF and SEM-EDS results, where the Ca was identied as the main element in all measurements, conrm the use of a kind of fresco technique for the construction of the wall paintings in both churches. 3.1. Plaster In both churches the wall paintings are applied on doublelayered substrate. The rst layer, arriccio, is 10e15 mm thick while the ner second layer, intonaco, has a thickness of several millimeters [8]. The plaster from the wall paintings of St. Theodori dissolves in diluted hydrochloric acid solution (5%), a fact that indicates that it should be calcite. Thin linen bers observed under the microscope indicate that these were used for binding the plaster. The plaster from St. Trinity church gives similar results about the composition of the plaster (calcite) with the difference that here thin straw bers are used for binding. The vibrations of calcium carbonatedat 1445, 866 and 712 cm1dwere identied in all FTIR analyzed plaster samples (Fig. 1). The spectra are also characterized with a more or less participation of silicon compounds, the presence of which are identied through the bands of the SiO4 tetrahedra at the spectral regions 1200e900 cm1 and 500e400 cm1 [9,10]. The bending and stretching modes of the SO4 group of gypsum at 602, 668, 1146, 3406 and 3550 cm1 are indicative of a concentration of gypsum, comparatively high in the sample STH18-Pl. The above results are in agreement with the results of SEMEDS analysis, shown in Table 2. Similar results were obtained

Table 2 EDS results for plaster samples Sample STH1-Pl STH2-Pl STH18-Pl STR8-Pl % Ca 82.4e89 35.1e69.2 32e62 3.5e33.3 %S e 0e0.3 0.5e9.2 e % Al 4e7.1 0e0.2 0e1 0.6e2.6 % Si 1.2e1.7 0.4e1.7 0.5e5.3 0.4e9.9 % Mg 0.8e1.5 0.4e2.9 0.3e1.6 0.5e0.9

from TXRF measurements. Calcium with smaller amounts of Fe and Sr were the only elements detected. Strontium associates with calcium while iron can be part of the silicates or an impurity of calcite. Amounts of sulfur were also detected in the spectrum of sample STH18-Pl. As mentioned above, relatively high amounts of gypsum have been detected in the plaster sample STH18-Pl. The amount of gypsum in this sample exceeded by far the typical amount of gypsum found in all other samplesda quantity attributed to deterioration which is described in the next sectiondso the hypothesis was formed as to whether gypsum was added as an ingredient of the plaster and whether this could be connected to the technique of the artist Onoufrios. Plaster samples taken from the churches of St. Nikolaos in Shelcan, Albania and St. Paraskevi in Valsh, Albania, two churches that have been painted by Onoufrios as inscriptions testify, contained equally high amounts of gypsum, suggesting that the painter Onoufrios used gypsum in the plaster. However, this is not the case for sample STH2-Pl, collected from an area painted by Onoufrios, which contained a small quantity of gypsum. Sample STH3-Pl, collected from an area below the wall paintings of Onoufrios, was not expected to contain gypsum. Further analyses into Onoufrios plaster showed that measurements from the same samples but from different areas did not always demonstrate the relatively high amounts of gypsum, leading thus to the suggestion of the creation by the painter of a mixture of gypsum, calcite and aggregates for the making of plaster and not of a separate layer of gypsum. SEM-EDS analysis found the grains of gypsum to be larger that the calcite ones [11]. Gypsum grains range between 8 and 10 mm in diameter while calcite ones vary between 2 and 3 mm (Fig. 2). 3.2. Deterioration Regarding the state of preservation of the churches, the paintings in both of them are found to be discolored, as a white thin layer having a crystalline texture has been formed above the nal color surface of the paintings. Furthermore, except for the existence of the gypsum as a main component in the Onoufrios plaster, it should be mentioned that the presence of gypsum in relatively small amounts is observed in almost all analyses of plasters and pigments in both churches. In some pigment samples the presence of oxalates is also identied (band at w1322 cm1 in the spectra). In Fig. 3, typical FTIR spectra from these affected surfaces are presented. The literature mentions two main processes that lead to the deterioration of the wall paintings [12]. The rst is related to

Transmittance

o o

Si-O STH 1-Pl STH 2-Pl STH 3-Pl STH 4-Pl STH 18-Pl 2000 2500 3000

*
Si-O

* *
o 1500 1000

o 4000

3500

Wavenumber (cm-1)
Fig. 1. FTIR spectra of the plaster samples from the church of St. Theodori. (O for gypsum and * for calcite)

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Fig. 2. SEM image of a plaster sample showing large gypsum grains in the center (a). EDS analysis of the same sample and of the same area showing sulfur (b) and calcium (c).

the alteration of calcite (CaCO3) to gypsum (CaSO4.2H2O) due to acid air pollution (sulfur oxides), while the second is related to the presence of biodeteriogens, which by the excretion of oxalic acid convert calcite to calcium oxalatedthe peak of calcium oxalate at w1322 cm1 at most FTIR spectra is a strong indication that there is a mixture of weddellite and whewellite calcium oxalate crystals [13]. Both processes could have been developed in the studied churches. On the one hand, close to Berati there was an industrial site emitting a lot of gases into the atmosphere, mainly from an oil-burning thermoelectric power station. On the other hand the churches have been closed for a long period of time, so the accumulated humidity and the acid gases could have affected the wall paintings. FTIR measurements of small fragments of plaster taken from below the painted layer on the St. Trinitys wall paintings showed an absence of gypsum and oxalates, a fact indicating the deterioration of the wall paintings and the need for special measures to be taken for their preservation. 3.3. Pigments 3.3.1. Black pigments Two black-colored samples were collected but all methods failed in giving any information. The main element detected in

all these samples by TXRF (Table 3) is Ca associated with minor amounts of Sr and Fe. In the FTIR spectra of the samples there are no bands except the calcite, gypsum, calcium oxalate and few silicates. The most common black pigments in that era were carbon black and bone black. As P was absent from EDS and TXRF results, we conclude that probably carbon black (amorphous carbon) was used for the black pigment. 3.3.2. White pigments Three white samples were examined. The TXRF results of these samples resemble those of the plaster, with high amounts of Ca and small amounts of Sr and Fe. The EDS results also show Ca in great quantities while also from the FTIR spectra the white samples can be characterized as pure calcite (Fig. 4a). 3.3.3. Blue pigments Two samples of dark blue color were collected from the church of St. Theodori. Copper is the main element detected by TXRF and SEM-EDS (Table 4), suggesting that a copper-based blue pigment would have been used. By the FTIR measurements the pigment is identied as azurite (Fig. 4b) [14]. The dark hue of the color is probably due to the mixture of azurite with carbon black.
Table 3 TXRF results for colored samples Pigment Identied elements St. Theodori Black Blue Brown Ca (Fe, Sr) Cu, Al, Si Ca (Fe, Sr) Fe, Ca (Hg, Sr, Pb) Si, Mg, Fe, Ca (K, Ti, Mn, Sr) Fe, Ca (Sr, Pb) Fe, Ca (Sr, Hg) Hg (Ca, Fe) Ca (Fe, Sr, S) St. Trinity Ca (Fe, Sr) Probably Carbon black Azurite Red ochre Fe, Hg, Ca (Sr) Si, Mg, Fe, Ca (K, Ti, Mn, Sr) Fe, Ca (Sr) Cinnabar red ochre Green Earth (Celadonite) Yellow ochre Red ochre /or cinnabar Red ochre Calcite Identied pigments

Transmittance

* oo
o o STH1-R STR1-Y + o

Green

*
4000 3500 3000 2500 2000 1500 1000

Wavenumber (cm-1)
Fig. 3. Typical FTIR spectra from affected surfaces of two samples (o for gypsum, for calcium oxalate and * for calcite).

Yellow Red

White

Fe, Ca (Sr) Ca (Fe, Sr)

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a
Transmittance

b
Transmittance

* *
+

STH7-W calcite reference 1000 1500 2000 2500 3000 3500 4000

*
1000 1500 2000 2500

STH5-Bl azurite reference 3000 3500 4000

Wavenumber (cm-1)

Wavenumber (cm-1)

c
*
Transmittance

green 9

d
Transmittance

* *
1000 1500 2000 2500 STH9-G green earth reference 3000 3500 4000

*
+

*
1000 1500 2000 2500

STH3-Y yellow ochre reference 3000 3500 4000

Wavenumber (cm-1)

Wavenumber (cm-1)

Fig. 4. FTIR spectra of the samples and the respective reference materials. (a) White sample and calcite (ref.); (b) blue sample and azurite (ref.); (c) green sample and green earth (ref.); (d) yellow sample and yellow ochre (ref.). *, Calcite peaks; o, gypsum peaks; , oxalate peaks.

3.3.4. Green pigments The TXRF spectra of four collected samples of green color show Fe and Ca as the main constituents associated with minor amounts of K and Mn. The analyses of the samples by SEMEDS add to the list of the major constituents Si and Al (Table 4). The association of the color with this kind of composition leads us to the conclusion that the color can be attributed to green earth. In the FTIR spectra the four narrow OH bands stretching in the 3610e3530 cm1 region and the area 1100e900 cm1 of SieO stretching are indicative of celadonite (Fig. 4c) [15]. 3.3.5. Yellow pigments Three samples of yellow color in different hues were collected. The main elements that are present in EDS results (Table 4)dbeyond Cadare Fe, Si and Al, results conrmed
Table 4 EDS results for colored samples Color Sample % Ca % Cu % Hg % Fe % Al % Si % Mg %S Blue STH12-Bl 0.8e46.4 43.6e63.9 e 0e2.8 1.4e3.3 0.5e5.3 0.5e1.5 0e13.1 Green STH9-G 2.1e28.8 e e 5.1e43.9 0e9.3 3.0e30.2 1.1e4.5 0e5.0 Red STR3-R 22.3e24.9 e e 1.9e3.3 0.9e10.8 1.7e3.1 4.8e14.0 6.6e12.8 STH15-R 1.9e12.1 e 40.2e86.2 e 0e1.0 0e1.0 e 5.0e10.0

by TXRF that detected a main concentration of Fe. The presence of ochre in general (red or yellow) is given in FTIR spectra bands in the spectral area 1100e900 cm1 and below to 600 cm1, due to SieAleO lattice. SiO2 also gives one or two bands at about 790e760 cm1. Depending on the amount of kaolinite in the ochre we have also bands in the area above 3000 cm1. The bands of FeeO from iron oxides (Fe3O2 or FeOOH) are below 550 cm1, so it is not possible to have information with ms-FTIR (MCT detector w550 cm1). However, the high concentration of Fe associated with the bands of the FTIR spectra (Fig. 4d) in the spectral area 1100e 900 cm1 and the similarities of the FTIR spectra of the yellow samples with the spectrum of the yellow ochre of the data base (peaks of kaolinite at 3697, 3669, 3652, 3620 cm1) suggest that most probably the used pigment is yellow ochre [16].

Yellow STH13-Y 4.3e21.2 e e 5.1e19.2 3.9e7.9 7.4e15.2 1.8e4.1 0e5.8

Brown STH4-Br 0e8.4 e e 2.6e61.6 0e3.1 1.6e4.0 2.0e14.9 3.1e8.9 STR7-Br 3.1e30.8 e 0e75.6 0e32.1 0e2.3 0e2.2 0e1.6 0e7.8

Black STH11-B 17.8e29.0 e e e 0e0.5 0.3e0.7 0e0.1 0e4.1

White STH16-W 9.7e53.6 e e e 1.3e4.4 0.6e5.8 2e3.0 0e12.8

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N. Civici et al. / Journal of Cultural Heritage 9 (2008) 207e213 Table 5 Summary of the identied pigments in the samples of both churches Green St. Theodori Green earth Blue Yellow Red Brown White Black Azurite Yellow ochre Red ochre /or cinnabar Red ochre Calcite Carbon black St. Trinity Green earth e Yellow ochre Red ochre Cinnabar red ochre Calcite Carbon black

3.3.6. Red pigments Five samples of red color with hues from light to dark red were collected. The TXRF and EDS analyses of the samples show that two types of red pigments were used. In the rst type, which includes samples STH1-R and STR3-R, Fe was identied along with Al and Si. This suggests that red ochre (mainly hematite) should be the main pigment in these samples. The FTIR spectra of these samples are similar to each other with bands that reect the composition of the plaster, the products of the deterioration and alumino-silicate materials. In the other three samples, all deriving from the church of St. Theodori (STH2-R, STH10-R and STH15-R), the predominant element is Hg (Fig. 5), which is the key element for the identication of cinnabar. By FTIR it is not possible to directly identify cinnabar (HgS) as the characteristic bands of HgS appear below 400 cm1. 3.3.7. Brown pigments Five samples of brown-red color were collected, four from the church of St. Theodori and one from the church of St. Trinity. The TXRF and SEM-EDS analyses of all samples show that the main elements are Fe, Al and Si, which suggests that red ochre should be the main pigment, probably mixed with carbon black, with the exception of the sample STR7Br that contained a high amount of Hg. This leads to the conclusion that the painter probably made a mixture of cinnabar, red ochre and carbon black [17]. Table 5 summarizes the results for all color samples. 4. Conclusions From the preceding analysis and discussions it is concluded that although the two churches belong to two different periods of iconography, the same application technique, fresco, and similar materials (plaster and pigments) were used for the preparation of their wall paintings. Based on these facts it can be stated that within the two centuries there is a continuation of the Byzantine technology of preparation of the wall paintings.
800 STH15-R Hg 600

Plaster samples from churches painted by Onoufrios showed that gypsum is a characteristic of Onoufrios wall painting technique. FTIR and EDS analyses showed that a small amount of gypsum was probably mixed with lime (CaO) and aggregates rather than being applied above the smoothest plaster as a separate layer. Both churches show traces of deterioration, due probably to two phenomena: (i) the alteration of calcite to gypsum and (ii) biodeterioration by the excretion of oxalic acid by biodeteriogens. The deterioration can be observed even visually, through the form of a white veil covering the Byzantine works of art. Acknowledgments This work was carried out in the framework of the Joint AlbanianeGreek Cooperation Program in the eld of Research and Technology, and the authors wish to thank the Albanian Ministry of Education and Science and the Hellenic General Secretariat of Research and Technology for their support. References
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Int

400

Hg

200

Ca Fe

0 0 200 400 600 800

Chn
Fig. 5. TXRF results for the red sample STH15-R.

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[16] D. Bikiaris, Sister Daniilia, S. Sotiropoulou, O. Katsimbiri, E. Pavlidou, A.P. Moutsatsou, Y. Chryssoulakis, Ochre differentiation through micro-Raman and micro-FTIR spectroscopies: application on wall paintings at Meteora and Mount Athos, Greece, Spectrochim, Acta 56A (2000) 3e18. [17] S. Daniilia, S. Sotiropoulou, D. Bikiaris, C. Salpistis, G. Karagiannis, Y. Chryssoulakis, B.A. Price, J.H. Carlson, Panselinos Byzantine wall paintings in the Protaton Church, Mount Athos, Greece: a technical examination, J. Cultur. Herit. 1 (2000) 91e110.