Article from e_conservation, the online magazine No. 7, October 2008, pp. 26-40/78 www.e-conservationline.

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THE CHURCH OF VORONET , MONASTERY

Technical considerations of the mural paintings
by Ioan Istudor

THE CHURCH OF VORONET MONASTERY

The church of Voronet Monastery is one of the many medieval monuments from Bukovina - a historical region located in northeast Romania that was built in 1488 by Prince Stephen the Great in only three months and three weeks, according to the commemorative inscription of the church. The church was built on a triconch plan with altar, naos and narthex and was painted in the same period. Later in 1547, the Metropolitan Bishop of Moldavia, Grigorie Rosca, added an exonarthex to the west end of the church and decorated it with mural paintings, together with all the facades. Although the number of churches from Bukovina with exterior mural paintings painted in the same period is large, many of them are only partially preserved. Among the most remarkable ones are the mural ensembles from Humor (1535), Moldovita (1537), Arbore (1541), Voronet (1547) and the most recent, Sucevita (1601).

The mural paintings from Bukovinean churches, particularly those with exterior mural paintings, have always produced a strong impression on those who have admired them. Their colours, brilliantly preserved after so many centuries, appear as a phenomenon and represent an exception due to their execution technique. Specialists were always impressed by the exceptional intensity of their colours, moreover since these monuments are located in a very harsh environment. To answer the many questions asked about the materials and techniques used in the execution of the exterior murals of churches from Bukovina, a series of technical research projects were started. The first studies started in 1963 at Voronet when samples from mortars, pigments and binders were analyzed by micro-chemical and chromatographic methods1 [1] and subsequently, in collaboration

1 Chromatographic analyses were performed according to

Margaret Hey [1]. Image 1. The church of Voronet Monastery.

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with other institutions2, through mineralogical analysis, spectroscopy and IR spectrometry. The first results on the controversial blue pigment and its alteration on the south facade - in the areas affected by moisture - were published in 1965 [2]. Until that date, there was no precise information supported by scientific research, but only speculations which have not been confirmed by subsequent studies3. The technological examination of the interior and exterior mural paintings from Voronet church focused on the technical and material elements that could explain the unusually good conservation state of the painting. The quality of materials used by the artists and the correct execution technique led to the completion of a painting that draws attention not only due to its artistic remarkable qualities but also due to its exceptional execution technique.

Research results The interior painting was executed according to the Byzantine technique, on a fresco plaster (intonaco) consisting of lime mortar with hemp tow, which was applied over another layer of plaster made of lime mortar with straw and chaff (arriccio), that had the purpose of making the wall surface even. The same traditional Byzantine technique can be seen at St. Sofia from Trebizonda (13th century) and Kariya amii (Chora) from Istanbul (1320). The same procedure was used at Voronet in the execution of the exterior painting made during Prince Stephen reign, such as the register with geometric motifs above the wall bench of the south facade (Images 2, 3). Traces of painting from the west facade of Prince Stephens church are still preserved in the porchs attic and on the eastern wall the inferior curtain decorated register. According to a fresco painting technique, the intonaco was applied in horizontal registers separated in pontate4 and giornate5 whose horizontal and vertical joint traces are visible in several places (Image 4) and constitute an undoubted proof of

2 Mineralogical and spectroscopic analyses were conducted

in 1963 by the university lecturer Dr. Dumitru Sandu and his collaborators from the Mineralogical Laboratory of the University of Bucharest and at National Research & Development Institute for Chemistry and Petrochemistry (ICECHIM) (analysis certificate No. 317 / 09.05.1966).
3 For subsequent research I benefited from the collaboration

of the architect and painter Ion Bals, whose knowledge in painting techniques was a real help in the interpretation of the chemical analyses results.
4 Pontata (Italian ponte = scaffold) is a term that defines an

area of wall painting executed in fresco, which usually corresponds to a scaffold floor, being delimited by horizontal plaster joints.
5 Giornata (Italian giornata = a day) is a term that defines a

Images 2 and 3. South facade. Decorative geometric motif located above the wall bench (painting from 1488).

wall painting area painted a fresco "in a day". The horizontal succession of giornate distinguished by vertical joints constitute a pontata.
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a fresco execution. The colours were applied after the intonaco layer was well compacted and the design was marked by incisions. Traces of these preliminary operations (trowel traces and incision) can be observed on the surface of the plaster in grazing light6 (Images 5-8). The durability of Byzantine frescoes is mainly due to the procedure of compacting the plaster previous to the colour application.
Image 4. Narthex, north wall. Decorative ornament painted on a 'pontata' joint. Images 5, 6. Narthex, north wall. Photos in direct light (left) and grazing light (right). Traces of compacted plaster and drawing incision.

6 In Byzantine technique, the compacting of plasters had the purpose of breaking the superficial crust of calcium carbonate that forms on intonaco, bringing to the surface the calcium hydroxide solution for a good pigment carbonatation. This provides the gloss and depth of tones but also a greater resistance of the fresco painting.

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Image 7. Narthex, south wall. Photo in grazing light showing the relief of the surface.

Image 8. Details regarding the execution technique.

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THE CHURCH OF VORONET MONASTERY

minium (red lead)

charcoal black

green earth

1 2 3 4 5 6

Altar Naos Narthex Exonarthex Exterior (1488) Exterior (1547)

+ + + + + +

+ + + + + +

+ + + +

+ + + +

+ + + +

+ + + +

+ + + + + +

gold + + + + +

No.

Location

Wall preparation (mortar composition for intonaco and arriccio plasters)

Arriccio: lime, straw, chaff; Intonaco: lime, tow, 3-6 mm arriccio lime, straw, chaff; Intonaco:lime, tow, 10-15 mm Arriccio: lime, straw, chaff; Intonaco: lime, tow Arriccio: lime, straw, chaff; Intonaco: lime, tow Arriccio: lime, straw, chaff; Intonaco: lime, tow Intonaco 3-13 mm, lime mortar, sand and brick dust, 32-62%

+ + + + +

Table 1. Pigments and plaster mortars.

Colours were obtained by mixing pigments with water, lime water or lime milk in order to obtain more transparent or matte layers. Pigments used are shown in Table 1. Except the black pigment obtained from charcoal, all the other pigments used are mineral substances, natural or synthetic: coloured earth with iron oxide hydrate (ochre), or anhydrous (red ochre), Fe, Al, Mg and K (green earth) hydrosilicate, red lead oxide (minium), copper minerals (azurite and malachite)7 [3], mercury sulphide (cinnabar), silicates (smalt)8 and calcium carbonate9 (white).

Cinnabar pigment was greatly used in the altar, naos and narthex, for both the garments and decorations curtains and red strips. In the painting of the exonarthex (added in 1547), predominant is the use of minium (red lead). Minium (Pb3O4) suffered here, as everywhere else where it was used in wall paintings (frescoes and temperas), a microbiological alteration transforming into lead dioxide (PbO2) of dark brown colour [4] (Image 9). Red ochre pigment was greatly used in all church compartments and is the only red pigment used in the exterior painting.

7 Azurite is a natural mineral substance, basic copper carbonate

[2CuCO3.Cu(OH)2] which is found in secondary deposits of copper minerals, associated with malachite, which is also a basic copper carbonate [CuCO3.Cu(OH)2] [3].
8 Smalt pigment is a synthetic silicate, a potassium glass

content. The smalt used at Voronet is slightly coloured and has a refractive index between 1.535 and 1.540. Smalt particles size range from 0,05 m to 0,19 m.
9 It has been determined by chemical analysis that the white

coloured with cobalt minerals that has been produced in various workshops according to local recipes, having in consequence different durability and various colours, more or less intense. Its colour varies according to its cobalt
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pigment is calcium carbonate. According to the handbooks, this could be obtained from rich lime dried in the sun, or from recovered old fresco plaster, in dust. Rich lime whitens the colours with which it is mixed thus its mixture with other pigments was avoided, being only used as pure white.

lime white + +

malachite

red ochre

cinnabar

azurite

smalt

ochre

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Regarding the blue surfaces (the famous 'Voronet blue'), they were executed with azurite pigment (basic copper-carbonate) on black background consisting of charcoal for two reasons: optical properties (to enhance the colour intensity) and isolation10 against the excessive lime alkalinity (Images 10 and 11). In the interior painting from Voronet, a mixture between azurite and smalt pigments was also used (Image 12 and 13). In the steeple, the quantity of smalt used varies, being predominant especially on the registers depicting cherubim, seraphs, prophets and liturgical angels. On the walls of all church compartments it can be observed that the amount of smalt mixed with azurite is very small. The presence of smalt in azurite does not appear to be accidental as a similar case was noted by the Italian researcher Paolo Benzi [5], quoting Dell Serra. Studying the work of Sodoma painter for the Monte Oliveto Magiore monastery (1505 - 1508), he considers that it does not correspond to the "canonical"
Image 10 (left). Stratigraphic section from "Tree of Jesse" scene. The azurite blue pigment applied over the black charcoal background can be seen. Image 11 (right). Azurite pigment, OM photography.

Image 9. Exonarthex vault. The alteration of minium (red lead) into dark brown lead dioxide.

10 The layer of black (charcoal) has a thickness between 30

and 60 m (measures performed in the non-degraded areas). Azurite particles size varies between 10 and 30 m. The actual thickness of the colour layer of the interior painting varies between 30 and 50m (and reaches over 100m in the exterior painting, in the superior registers which are more protected by eaves).

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Image 12. OM photography, smalt pigment structure.

a fresco technique and notes that "azurite, mixed with smalt was probably applied a fresco on an intonaco not completely dry (quasi completamente secco), perhaps with the addition of an organic binder" [5]. Traces of smalt in azurite are also present in the exterior painting from Voronet and Moldovita. It is possible that the initial amount of smalt has been higher, but its compatibility with the binder is smaller than that of azurite and thus it was mostly lost under climatic influences.
Image 13. Naos steeple (interior). Smalt pigment.

The green colour was obtained from malachite or green earth pigments. Malachite was used in the exterior and in the porch, while the earth green has been used very much in the interior as well as exterior painting. Again, its preponderant use for certain areas can be noticed: backgrounds, garments and floral decorative motifs, and its application was done mainly over a charcoal black background but also pure or mixed with charcoal black. The earth green used on the south facade 1488 exterior painting, register depicting geometric decorative motifs, shows a yellowishgreen11 [6] shade due to the influence of the capillarity humidity. This shade may belong to the original pigment colour or could have appeared as result of a partial alteration.

11 The pigment known as "earth green" contains glauconite

(green-yellow) and celadonite (green-blue) minerals. The colour of the pigment depends on its mineral content. At the same time the alteration of these minerals in goethite (yellow iron oxide, FeO(OH)) is possible [6].

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Exterior wall painting practiced since the end of the 15th century in Bukovina, as the former western facade from the time of Stephan the Great proves, reached its highest glory in the 16th century during the reign of Peter Rares. The exceptional paintings conservation state in the severe climate of Bukovina surprises even more as it is known that the blue pigment is the first one to fade away under the influence of climatic factors. The good conservation state of the azurite, malachite and relief decorative pearls on the garments should be primarily attributed to the use of binders and a special execution technique, different than that of traditional Byzantine fresco. The blue colour intensity shows on the one hand that the binder can not be lime (calcium carbonate) which turns white during the drying of the colours with which it is mixed. On the other hand, the glossy aspect and hardness of the mortars used for the pearls, in contrast to the plaster surfaces of the wall, also show evidence of use of other binder than pure lime. Most existing scientific studies as well as handbook descriptions refer to the interior painting technique. Known cases of outdoor murals, especially in Central Europe - with a milder climate than Bukovina, were executed with binders containing proteins (calcium caseinate) besides pure lime. This binders use is reported by Alexander Eibner (quoted by Mora and Philippot) [7, 8], especially in the 16th century, but their conservation state, particularly that of the blue pigment under the influence of climatic factors, is not yet known [8]. As previously mentioned the 1547 painting from Voronet was executed on a plaster based on lime, sand and brick dust12 that distinguishes itself by a special resistance to environmental conditions. The painting technique was certainly a mixed one: beginning with the application of a fresco backgrounds and continuing with the application of colours that contain organic, proteinaceous binders [9, 10], on a not completely dry plaster
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(intonaco). Among the proteins used as binder, casein-lime combination is the one conferring a superior resistance. The mixture, called calcium caseinate, was made of fresh lime and cow cheese. To the superior resistance of the paintings have also contributed: - The special compatibility of the crystalline pigments (azurite, malachite, calcium carbonate) with the binder, compared with colloidal earth pigments (ochre, ochre red, green earth); - The fungicide effect of copper pigments (malachite and azurite) which prevent the development of micro-organisms that deteriorate the organic binders in wall paintings in favourable environments; - The superior mechanical resistance of calcium caseinate than the one of calcium carbonate. The use of a proteinaceous binder is proved by the formation of a specific reaction, known as biuret reaction, in which proteins in strong alkaline environment in the presence of copper ions show violet colour [11]. Copper ions can result from azurite or traces of other copper minerals that can be found sometimes with the pigment and that react chemically easier (Image 14). Regarding the application of azurite, it is possible that it was applied as described in Paolo Benzis article [5, 11]. Examining the stone inscription

12 The results of the chemical analyses performed in 1964 at

the Institute of Design and Research of Building Materials (IPCMC) on some samples of fresco plaster from the exterior painting of Voronet, sampled from the inferior register of the south and north facades are the following: 28.16 - 28.67% loss in calcination, 34.5 - 37.18% insoluble substances in HCl, 1.63 - 2.54% SiO2, 32.98 - 35.12% CaO, 0.06 - 0.24 % MgO, 1.11 - 1.67% R2O3. From the discussion had on that date with Prof. Dr. Al. Steopoe, it was concluded that due to the very small quantities of taken mortar samples (2-5 grams), the results have a local significance. Only average samples obtained from greater quantities of mortars can give results to characterize the properties of the plasters.
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Image 14. The north facade (to west), above the door. On the white stripe the violet colour can be observed (biuret reaction), which proves the presence of an organic binder.

Images 15 and 16. Exonarthex, east wall. Stone inscription, 1488 (left) and visible traces of azurite on the background of the letters (right).

above the entrance of the narthex (originally on the west facade of Stefans church), traces of blue colour can be seen on the background of the letters. The colour is azurite applied directly onto the stone, which was only possible by adding an organic binder in the colour (Images 15, 16). On the south facade (west to the entrance door) the presence of an organic binder in the colour layer is also demonstrated by the black colour of the Bishop Grigorie Roscas headcovering, which shows an intense and glossy aspect and is very resistance to exposure. This colour effect can not be obtained in fresco technique (Image 17, 18). Analysing the conservation state of the colour layers from the facades it can be observed that the deterioration prevails on the areas exposed to the wind - north and north-east. At Voronet, as well as in other churches with exterior painting from Bukovina, it can be seen that the
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Image 17. South facade, portrait of Bishop Grigorie Rosca. The headcovering of intense black tone can be noticed.

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Image 18. Detail of Bishop Grigorie Rosca portrait. The intense tone of headcovering can be noticed.

Image 19. East facade. Erosion of the colour layer executed with earth pigments in the background and garments area.

number of well preserved colours decreases gradually from east to north, azurite and malachite pigments being the best preserved ones, both in backgrounds and garments, while earth pigments (ochre, ochre red, green earth) have a smaller resistance (Image 19). The detachment of the colour layer, observed at all churches with exterior painting, occurs as a result of humidity migration from plasters, favouring soluble salts - especially calcium sulphate - to evaporate on the surface. Recrystallisation of calcium sulphate close to the surface in pores or microfissures, and the formation of dehydrated gypsum (CaSO4.2H2O), occurs with cca. 1.6 times increase in volume. This exerts pressure on the mortar particles, breaking their cohesion and the calcium carbonate crust from the surface, resulting in the detachment and exfoliation of the colour layer.
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Also, the inferior registers are more deteriorated than the superior ones which have been protected by eaves. This phenomenon was the reason of eaves enlargement during the restoration works carried out in the 60s of the last century. The natural aging of materials can be seen at Voronet, as in other churches with exterior painting, by the particular exfoliation tendency of the layers containing organic binders. Examining the conservation state of the exterior painting it becomes obvious that the last three registers of the exonarthex added in 1547 (south and north facades) are better preserved than the areas painted in 1488 (Image 20). We believe the different behaviour of the paintings executed in 1547 is due to the colour layer formation conditions and not to the execution technique, otherwise impeccable. A possible explanation may be that the painting executed
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Image 20. North facade. The conservation state of the paintings from the exonarthex added in 1547 is superior to the areas built and painted in 1488.
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on the freshly built facades of the porch had benefited of a greater quantity of moisture and lime which allowed a slow pigment carbonatation, while the facades of the old walls had available only the environmental humidity and the intonaco lime (Image 20). Unfortunately the azurite, pigment with beautiful colour and great resistance in normal conditions, has been exposed to high humidity (by capillarity) and altered, transforming in malachite (green).

This phenomenon is the result of a change in the copper carbonate - copper hydroxide ratio from 2/1 (in azurite) to 1/1 (in malachite)13 [12]. A very important part from the inferior area of the scene "Tree of Jesse" on the south facade became green [2, 3] due to the long period of exposure to capillarity humidity (Images 21, 22). Another phenomenon of azurite alternation, this time due to the chlorine ions content in the intonaco (accidentally), can be observed as green

13 Under normal circumstances, azurite is stable if the

partial pressure of carbon dioxide in the air is greater than 2.4 mm Hg. Since the partial pressure of carbon dioxide in air is 0.24 mm Hg, azurite transforms in malachite in the presence of humidity [12].

Images 21 and 22. Cross-section of a sample from the area where azurite transformed in malachite (left) and south facade, azurite transformed in malachite in the inferior area of the scene "Tree of Jesse" due to capillarity moisture (down).

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Images 23, 24. Porch vault. Green spots of alteration (atacamite) are visible on the azurite sky background.

spots of atacamite14 ([CuCl2.3Cu(OH)2], basic copper chloride) [3] (or paratacamite) on azurite background, on a few scenes in the porchs vault (St. Apostle Filimon scene, Synaxarium day 22 November and others) (Images 23, 24). Conclusions The conservation works of the mural paintings from Voronet started in the last decades of the last century under the coordination of Prof. Dr. Oliviu Boldura and offered the opportunity of collaboration between researchers from various interdisciplinary fields (analytical chemistry, instrumental analysis, microbiology, art history) with conservators, for the application of scientific methods to conservation. The chemical analyses have determined the nature and composition of the materials used in the painting process (mortars, pigments, binders), have identified the causes of physical and chee_conser vation

mical altering processes of colour layers, have emphasized the process of azurite and minium alteration and provided knowledge on the execution technique. Based on the research results above and from literature, we can consider that the Moldavian painters, knowing the Byzantine technique and entering in contact with painters from Central Europe that used binders in lime colours, have combined the techniques of these two schools. The result of this mixed process provided the formation of a very effective protective layer of the surface and allowed a better conservation of paintings from Bukovina. We can also state that only due to the procedure employed by the Moldavian painters, the exterior decoration of Bukovinean churches is much more resistant to environmental factors when compared with Byzantine, Central Europe and all other exterior paintings, in general.
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Bibliography
1. Margaret Hey, "The Analysis of Paint Media by Paper Chromatography", Studies in Conservation, 3 (1958), pp. 183. 2. Ioan Istudor, "Un fenomen de alterare a culorilor in pictura murala de la Voronet", Revista Muzeelor, 2 (1), (1965), pp. 65 66. 3. Ioan Istudor, Notiuni de chimia picturii, Daim Publishing House, Bucharest (2007), pp. 92. 4. Julia P. Petrushkova and Natalie N. Lyalikova, "Microbiological degradation of lead - containing pigments", Studies in Conservation, 31 (1986), pp. 65-69. 5. Paolo Benzi, "La Pellicolo pittore nella pittura mural in Italia, materiali e tecnice esecutive dall Alto Medievo al XIX seccole", in Le Pitture murali (tecniche, problemi, conservatione). A cura di Cristina Danti, Mauro Matteini, Arcangelo Moles Centro Di, pp. 73 102. 6. Franois Delamare, Laurent Delamare, Bernard Guineau and Gilles-Serge Odin, "Couleur, nature et origine des pigments verts employs en peinture murale gallo-romaine", in Pigments et Colorants de lAntiquit et du Moyen ge, Colloque International du CNRS, Paris (1990), pp 103-116. 7. Paolo Mora, Laura Mora and Paul Philippot, Conservarea Picturilor Murale, Ed. Meridiane, Bucharest (1986), pp. 156. 8. Jean Rudel, Technique de la peinture, Paris (1957), pp. 16 and pp. 43. 9. Ioan Istudor and Ion Bals, "Contributii la cunoasterea materialelor folosite in pictura murala exterioara a bisericilor de secolul al XVI-lea din Bucovina si la unele probleme de tehnica", Revista Muzeelor, 5 (6), (1968), pp. 491-497. 10. C. Merticaru, I. Istudor, and Gh. Cimpeanu, "Investigation Concern the Outdoor Wall Painting on the 16th Century Monasteries from Bucovina, Romania", Art 05 8th International Conference on Nondestructive Investigations and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage, Lecce (Italy), May 1519 (2005), Book of Abstracts, pp. 184. 11. Ioan Istudor, "Alteration de la Couleur observees sur les peintures murales des eglises de Bucovine", in Colloque sur la conservation des peintures murales, Suceava, Romania, June (1977), pp. 21 25. 12. Gerhard Banik, "Green cooper pigments and their alteration in manuscripts or works of graphic art", in Pigments et Colorants de lAntiquit et du Moyen ge, Colloque International du CNRS, Paris (1990), pp. 99.

IOAN ISTUDOR
Conctact: bistudor@gmail.com

Born on November 14th 1928, Ioan Istudor graduated from the Faculty of Industrial Chemistry, the Polytechnic Institute in Bucharest in 1951 and since then, he has been continuously working as scientist in the conservation field. During almost half-century of continuous research, he performed analyses for more than 300 monuments and established the main research laboratories for conservation in Romania: in 1962 the first national conservation laboratory of the Historic Monuments Direction; in 1963 the laboratory of the National Art Museum of Romania and in 1983 the laboratory of the National Art University in Bucharest. He was certified as Expert by the Romanian Ministry of Culture in the research of several conservation domains, he was awarded several Excellency and Merit Diplomas for his entire professional activity and he was attributed the National Order, Knight Rank for his merits. From 1975 to 2002 he taught applied chemistry to Conservation-Restoration, Museology and Monumental Art departments of the National Art University in Bucharest. Since 1996 he is working as researcher for the conservation company Cerecs Art S.R.L. He has published a large number of articles and a book entitled Notions on the Chemistry of Paintings. He was granted for the patent of his discoveries: The procedure of obtaining a transparent calcium casein dispersion, Solutions for extracting and transferring mural paintings by strappo and The candle that does not produce smoke". *Part of the information in this article was presented at "Testimonies of living history" communication session, Voronet, 12-13 September 2008. Photos by Ioan Istudor, Anca Dina and Magdalena Drobota.
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No. 7, October 2008 LICENCE ISSN: 1646-9283 Registration Number Attribution-Noncommercial-No Derivative Works 2.5
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