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FromByzantinetopost-Byzantineart:ThepaintingtechniqueofStStephen'swallpaintingsatMeteora,Greece

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Journal of Archaeological Science 35 (2008) 2474–2485

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Journal of Archaeological Science

journal homepage: ht tp: / /www.elsevier .com/locate/ jas

From Byzantine to post-Byzantine art: the painting techniqueof St Stephen’s wall paintings at Meteora, Greece

Sister Daniilia a,*, Elpida Minopoulou a, Konstantinos S. Andrikopoulos a,b,Andreas Tsakalof a,c, Kyriaki Bairachtari a,d

a ‘Ormylia’ Art Diagnosis Centre, Sacred Convent of the Annunciation, 63071 Ormylia, Chalkidiki, Greeceb Physics Division, School of Technology, Aristotle University of Thessaloniki, GR-54124 Thessaloniki, Greecec University of Thessaly, Department of Medicine, Papakiriazi 22, 41222 Larisa, Greeced National Centre for Scientific Research ‘Demokritos’, Aghia Paraskevi, GR-15310 Attiki, Greece

a r t i c l e i n f o

Article history:Received 27 June 2007Received in revised form 26 February 2008Accepted 21 March 2008

Keywords:Post-Byzantine artMeteoraEggFresco–seccoSmaltEfflorescenceSpectroscopiesGC/MS

Abbreviations: PCA, principle component analysis;valine; Leu, leucine; Ile, isoleucine; Ser, serine; Met,Phe, phenylalanine; Asp, aspartic acid; Glu, glutamicline; Hyp, hydroxyproline.

* Corresponding author. Tel.: þ30 23710 98400; faxE-mail address: ormylia@artdiagnosis.gr (S. Daniil

0305-4403/$ – see front matter � 2008 Elsevier Ltd.doi:10.1016/j.jas.2008.03.017

a b s t r a c t

The old katholikon of St Stephen’s monastery at the Meteora (site of the most important complex ofmonasteries in Greece after Mount Athos) is decorated with wall paintings that date from the beginningof 17th century. In terms of style, the artistic ensemble is altogether characteristic of the period. Thepainting technique has been examined by means of mRaman and mFTIR spectroscopies, gas chromatog-raphy–mass spectroscopy (GC/MS), optical microscopy (OM) and scanning electron microscopy (SEM).Prior to the commencement of restoration treatment, and in order to optimise its effect, it was con-sidered prudent to identify the materials and ascertain the techniques that had been used to apply theplaster and the paint layers. It was noted that whereas the ariccio consists of yellow clay and straw, theintonaco contained calcite. The painter’s palette is made up of eight pigments: calcite, carbon black,yellow ochre, haematite, green earth, cinnabar, smalt and malachite. The stratigraphy and the scale of theshades differ significantly from those in works of the Palaeologan period (1261–1453) – indicative both ofevolution in Byzantine iconography as a result of gradually changing religious and social circumstances,and of the skill and vision of the painter.In addition, some decay products, such as gypsum, were detected. In that they conceal important artisticdetails, this necessitates proper consolidation, cleaning and conservation treatment in order to restore tosome degree the original splendour of the wall paintings.

� 2008 Elsevier Ltd. All rights reserved.

1. Introduction

Meteora (Greek: M3s�eura, ‘suspended in the air’) is one of thelargest and the most important complexes of monasteries in Greeceafter Mount Athos. Its edifices are constructed on spectacular nat-ural sandstone rock megaliths at the northwestern edge of the plainof Thessaly. The history of these monasteries was first mentionedfrom the 11th century when the first hermits settled on these‘columns of the sky’. Although more than 20 monasteries were builtat the time of the great 14th century revival of the monastic life,only six remain today: the Great Meteoron (or Holy Trans-figuration), Varlaam, St Stephen, Holy Trinity, St Nicholas Anapafsas

Ala, alanine; Gly, glycine; Val,methionine; Thr, threonine;acid; Tyr, tyrosine; Pro, pro-

: þ30 23710 98402.ia).

All rights reserved.

and Rousanou. Their 16th–17th century murals mark a key stage inthe development of post-Byzantine art. The rock monasteries havebeen regarded by UNESCO as a unique phenomenon of the world’scultural heritage and they form one of the most important stationson the cultural map of Greece.

Built in the 14th century, the monastery of St Stephen is locatednear the outskirts of modern Kalambaka (Fig. 1). Its old katholikon,dedicated to St Stephen the Protomartyr, was probably built at thetime of the monastery’s foundation or shortly thereafter. In 1545, itwas rebuilt by St Philotheos, second founder of the monastery. Thissecond building phase is a small, low, timber-roofed, single-navedbasilica with a narthex. During the World War II (1939–1945) andthe Civil War (1946–1949) the church suffered more damage thanin the five previous centuries together, for example, the defacing ofall the saints, especially their eyes.

The wall paintings of the interior, initially retouched andrestored three decades ago, form an interesting ensemble of post-Byzantine painting. Scenes of the Virgin ‘Platytera’ and of theCommunion of the Apostles (above the sanctuary), the full-length

Fig. 1. The Holy monastery of St Stephen at the Meteora, Greece.

Table 1Description of sampling position

Sr. Daniilia et al. / Journal of Archaeological Science 35 (2008) 2474–2485 2475

portraits of the saints and the representations in the nave of the 24stanzas of the Akathistos Hymn are all equally arresting. Finally, inthe narthex, the holy founders Anthony and Philotheos and of theDormition of the Virgin Mary are depicted.

While no attribution to the founder (the righteous Philotheos)or to the artist of the paintings’ first stage is noted in themonastery’s dedicatory inscription, commemorations do exist forthe patrons of the earliest artwork – the abbot Mitrophanis and thehieromonk Grigorios (Fig. 2). The same inscription refers to thename of the second painter, the priest Nikolaos from Kalambaka,who completed the subsequent phase of the wall paintings.

On the bases first, of the manner in which the iconographicprogramme is worked out and secondly, of the stylistic and mor-phological features of the figures portrayed in the wall paintings, itis likely that the first phase of the artwork dates from between thesecond and third decade of the 17th century. The second phase wascompleted soon after, that is to say, around the middle of the samecentury. The wall painting complex in St Stephen’s katholikonclearly belongs to a tradition known to us from a great manypainted churches in Epirotic Greece and beyond (Vitaliotis, 1998).

The present study concerns itself with two important aspects ofthe wall paintings in St Stephen’s monastery: (a) disclosure andclassification of their painting techniques as they relate to traditionalpractices of the Byzantine era proper and (b) description of theirstate of preservation aiming at the consolidation, removal of sootand salts, and restoration of the aesthetic integrity of the murals.

Analyses were undertaken by means of mRaman and mFTIR spec-troscopies, gas chromatography–mass spectroscopy (GC/MS), opticalmicroscopy (OM) and scanning electron microscopy (SEM/EDS).

Fig. 2. The dedicatory inscription above the transom of St Stephen’s west door.

Given the absence both of bibliographic resources and of recentstudies on the painting techniques in the wider region of Epirus of thepost-Byzantine period (17th century), the results of this researchachieve their anticipated significance. Finally, comparison of the re-sults with those from the Protaton (1290), Mount Athos (a repre-sentative monument of the Byzantine era) reveals significant stylisticand technical differences.

2. Experimental

2.1. Samples

The samples under investigation were acquired from a variety ofscenes and zones in the church (Table 1) and were chosen for thepurpose of identifying the material elements that make up theplaster, the pigments, the binding media, and the residual salts onthe wall painting surface. Moreover, attention was given to locateand describe the painting techniques (stratigraphy, pigment mix-ture, colour combinations) and more generally the particularartistic features in post-Byzantine wall paintings of this period.

2.2. Methodology

2.2.1. Optical microscopySamples were mounted in polyester transparent resin and the

cross-sections were ground and polished using a Struers Planopol-V machine. Observation and photography of the samples’ surfacebefore embedding and of their cross-sections were achieved usinga Zeiss Axiotech 100 HD polarising microscope, equipped withwhite reflected and ultraviolet light as well as with a SPOT 2 1.4digital cooled camera (res.: 1315�1033 pixels, 12 bits per colour).

2.2.2. mFTIR spectroscopyFTIR spectra were measured with a Biorad FTS 175 FTIR spec-

trophotometer equipped with a UMA 500 microscope. Powderedsamples pressed into KBr pellets and micro-samples placed in a DC-2 Graseby-Specac diamond compression cell were analysed inabsorbance mode at 4 cm�1 resolution.

2.2.3. mRaman spectroscopyA Renishaw System 1000 micro-Raman spectrometer compris-

ing an Olympus BH-2 imaging microscope, a grating mono-chromator and a charged-coupled device (CCD) Peltier-cooleddetector were employed for Raman spectra acquisition. An HeNelaser (632.8 nm) served as the excitation source and the beam

Sample Point in the church Scene Sampling position

STA1 Northern wall, sanctuary St Germanus Flesh tone in righthand

STA2 Northern wall, sanctuary St Peter ofAlexandria

Brown background

STA5 Eastern facet, north pessary The Virgin ofSupplication

Flesh tone in neck

STA6 Western wall, nave (1st zone) Archangel Gabriel Red sticharionSTA8 Northern wall, nave (2nd zone) Resurrection Christ’s purple tunicSTA10 Southern wall, nave (3rd zone) Palm Sunday Brown backgroundSTA11 Eastern wall, sanctuary St Basil the Great Grey backgroundSTA12 Southern facet, north pessary St Orestes Plaster in right handSTA13 Western facet, south pessary Yellowish plasterSTA14 Western facet, south pessary Grey backgroundSTB1 Northern wall, nave (1st zone) St Mercurius Light in olive-green

tunicSTB2 Western wall, nave (2nd zone) The Dormition of

the VirginGreen background

STB3 Eastern facet, north pessary The Virgin ofSupplication

Red light in mantle

STB4 Northern wall, nave (1st zone) St Demetrius Blue tunic

Sr. Daniilia et al. / Journal of Archaeological Science 35 (2008) 2474–24852476

emitted was focused using a 100�microscope objective. Low laserpower (up to 1 mW) was used for spectra accumulation. A set oftwo notch filters with a cut-off edge of wþ100 cm�1 was employedfor the rejection of Rayleigh scattered light. The resolution was keptat w5 cm�1.

2.2.4. Gas chromatography–ion trap mass spectrometry (GC/MS)A Polaris gas chromatograph–ion trap mass spectrometer pro-

vided with an AS2000 autosampler (ThermoFinnigan, San Jose,USA) was used for amino acid quantification in reference and realsamples. The gas chromatographer was equipped with split/split-less injector and AT�-5MS 30 m� 0.25 mm column with 0.25 mmfilm thickness of 5% phenyl–95% methylpolysiloxane stationaryphase (Alltech Associates, USA).

The samples ware extracted twice with CHCl3 in order to sep-arate possible natural resins, lipids and free fatty acids from theproteinaceous fraction. The solid residue, once dried, was extractedtwice with 2.5 N ammonia solution for 3 h at 60 �C in an ultrasonicbath. The extract was subsequently subjected to acid hydrolysisassisted by microwaves in order to free the amino acids, whichwere derivatised with N-tert-butyldimethylsilyl-N-methyltri-fluoroacetamide and then 1 ml (of each derivatised solution) wasanalysed by GC/MS (Daniilia et al., 2007).

2.2.5. Scanning electron microscopy–energy dispersive system(SEM/EDS)

Scanning electron microscopy (SEM) was carried out usinga JEOL 6300 scanning microscope equipped with an energy dis-persive X-ray spectroscopy (EDS) ISIS 2000 microanalytical system.The elemental composition was determined using the preparedcarbon coated cross-sections, which were bombarded by a stronglyaccelerated and focalised electron beam in a vacuum (10�5 torr).

3. Results and discussion

3.1. The plaster

Macroscopic investigation of the wall paintings’ surface atpoints of extensive damage and detachment permitted thedetection of two layers of plaster of differing composition. The first,ariccio, of a yellowish shade, contains a considerable amount ofstraw; the second, superficial intonaco has a whitish hue (Fig. 3).

Fig. 3. Detail of St Orestes’s right hand (detection of two layers of plaster and strands of str100� and 200�).

The stratigraphy of the plaster is clearly made out in the cross-section of the sample taken from St Orestes’s right hand (STA12).The high degree of diffusion in the interface of the two layers in-dicates that the intonaco was probably applied while the underlyingariccio was damp. Here, the presence of yellow clay in the ariccio isimpressive; it replaces lime which, as is well known, constitutedthe chief ingredient of plaster in most Byzantine monumentalpainting. It is likely that yellow clay existed abundantly in thesurrounding area and was therefore preferred for financial reasons.

For the identification of plaster compounds mFTIR spectra wereacquired from two homogenous, pulverized samples: (a) theyellowish ariccio and (b) the whitish intonaco. mRaman spectros-copy was applied additionally for the identification of certaincompounds.

In the FTIR spectrum of ariccio (STA13) (Fig. 4, Table 2) thecharacteristic peaks of kaolin and calcite were recorded denotingthe presence of yellow ochre (Ganitis et al., 2004; Pavlidou et al.,2006; Zorba et al., 2006). mRaman spectroscopy, on the other hand,revealed the presence of goethite (main compound of yellow ochre)(Fig. 4, Table 2) (Koszowska et al., 2005). The FTIR spectrum ofintonaco (STA14) consisted of calcite (Gilbert et al., 2000) andquartz (a natural admixture) (Fig. 5, Table 2) (Goodall et al., 2006).

3.2. Pigments and layer structure

3.2.1. The background

3.2.1.1. Blue. The background of Byzantine wall paintings is habit-ually divided into two zones of unequal height, the upper one blue(larger) and the other of an olive-green shade. In post-Byzantinemonuments, however, one sees a penchant for separating the fieldinto three zones: the upper blue, the middle green (larger) and thelower brown. This artistic particularity – aside from its symboliccharacter – is most probably motivated by the practical need torestrict the space allotted to the especially costly pigments in theblue field.

The grey-blue background in St Stephen’s wall paintings isexecuted with a familiar, traditional technique that had been usedfor centuries in murals of the Comnenian, Palaeologan and Cretanstyles (Daniilia et al., 2000; Zorba et al., 2006; Pavlidou et al., 2006).Applied over the uppermost white plaster is a primary, dark cov-ering – a grey layer from carbon black with a very small amount of

aw in the yellowish one) and cross-section of the underlying plaster (magnification at

Fig. 4. mFTIR and mRaman spectra of ariccio indicating the characteristic peaks of (a) kaolin and calcite and (b) goethite.

Sr. Daniilia et al. / Journal of Archaeological Science 35 (2008) 2474–2485 2477

lime – in which scattered grains of haematite, cinnabar and yellowochre could be traced. Above this the blue pigment exhibits angularcrystalline grains in a variety of sizes, in hues from deep blue togreyish azure (Fig. 6). This technique has also been reported inmedieval wall paintings (Mugnainia et al., 2006).

Table 2Materials identified with FTIR and Raman spectroscopies

Technique Sample Material P

FTIR STA13 ariccio Calcite 148

Kaolin 3106

STA14 intonaco Calcite 148

Quartz 10

STA14 paint layer Calcite 2148

Smalt 107

STB2 Calcite 2148

Green earth 10

STA11 Gypsum 31611

Wax 31714

Raman STA13 ariccio Goethite 3

STA10 Goethite 3Red ochre 2

4Carbon black 13

STB2 Celadonite 215

STB1 Malachite 314532

STB3 Calcite 10Cinnabar 2

vs, very strong; s, strong; m, medium; w, weak; br, broad.

Smalt and calcite were initially identified with mFTIR spectros-copy (Gilbert et al., 2000; Ganitis et al., 2004).

Smalt is an artificial, glass-like potash silicate pigment, which isstrongly coloured with cobalt oxide and reduced to a powder. Ev-idence of its use as a painter’s pigment dates from the 15th to early

eaks (cm�1) Assignments

24w CO32�, stretching

74w CO32�, bending

698br, 3619br O–H, stretching32br, 1011br, 913m Aluminosilicates, stretching

93w, 527m, 467s, 430s Aluminosilicates, bend

16br CO32�, stretching

74s CO32�, bending

34br, 800w Si–O–Si, stretching and bending

516w, 1796w CO32�, overtone and combination bands

30br CO32�, stretching

74s, 712m CO32�, bending

84w Si–O, stretching81w, 464w Si–O, bending

514w, 1800w CO32�, overtone and combination

37br CO32�, stretching

74s, 714m CO32�, bending

36br, 976m, 453m Silicates, stretching and bending

544m, 3403m, 3363s, 3197m O–H stretching61s, 1634s O–H bending38m, 1117m S–O stretching

008w, 2923s, 2853m C–H stretching42w C]O stretching70m, 1424m C–H bending

04w, 401br, 563m Fe–O bands

03w, 407br, 560m Fe–O bands25m, 245w, 292s, 411m,99w, 611m, 661w

Fe–O bands

21br, 1600br C–C stretching

5m, 271m, 393m, 457w,51br, 700m, 908w

R–O–H bands (R: Al, Feþ2, Feþ3, Mg)

350br, 1052m O–H stretching86w, 1085m CO3

2� stretching33w, 431s Cu–O stretching54w Cu–O bending65m, 217w, 178m O–Cu–OH bending

86w CO32� stretching

53vs, 344m Hg–S stretching

Fig. 5. mFTIR spectrum from the intonaco with the characteristic peaks of calcite andquartz.

Sr. Daniilia et al. / Journal of Archaeological Science 35 (2008) 2474–24852478

19th century, notwithstanding the employment of cobalt ores inancient Egypt and in classical times for colouring glass. In the early17th century smalt is mentioned as being of widespread use in oilpainting, substituting lapis lazuli and azurite as they became moreand more scarce (Gettens and Stout, 1966; Muhlethaler and This-sen, 1993).

Today, unlike the grey background underpaint in the church’swall paintings which is visible, the upper layer of smalt is preservedin but a few areas. Larger smalt grains have become detached fromthe painting and this may be attributed either to accidental removalduring the several rescue interventions undertaken for the pur-poses of conservation or to a weakening of the binding power of themedium. Analogous detachment occurs in many medieval artmonuments where azurite is used as the blue pigment (Daniiliaet al., 2006; Sotiropoulou et al., 2007).

3.2.1.2. Green. In the background’s olive zone the paint layers areapplied directly onto the white plaster without the intermediarygrey layer commonly found in earlier wall paintings (Fig. 7b)(Daniilia et al., 2000). In the cross-section two paint layers can bediscerned (Fig. 7a). In the first, green earth is mixed with small

Fig. 6. (a) Photomicrograph of the background sample where smalt is applied over a grey

amounts of carbon black, yellow ochre, haematite and cinnabar,while the second contains green earth and lime, with the result thatthe final shade is more luminous. Green earth could be detectedwith both mFTIR and mRaman spectroscopic techniques (Fig. 7c, d,Table 2) (Daniilia et al., 2000; Zorba et al., 2006; Pavlidou et al.,2006; Daniilia and Andrikopoulos, 2007).

3.2.1.3. Brown. The background’s lower brown zone is rendered incarbon black with red and yellow ochres (Table 2).

3.2.2. The garments

3.2.2.1. Blue. The grey-blue hues of the garments are executed ina technique similar with that seen in the blue background. Carbonblack and gains of haematite were found in the underpaint (thetunic of St Demetrius, STB4), whereas the lights were rendered withmixture of smalt and calcite (Fig. 8). Furthermore, many micro-scopic, almost colourless, grains of smalt, were recorded mostclearly under ultraviolet light, allowing the charting of theirdistribution throughout the paint layer.

The identification of smalt used at St Stephen’s was carried outby SEM/EDS analysis on a cross-section, verifying the resultsobtained by mFTIR spectroscopy (Fig. 6). In the EDS spectrum thepeaks of Co, Si and K, main elements of smalt, as well as Al, Ca andFe (in some cases As), were recorded (Fig. 8c). Elements such as Feand As indicate the origin of CoO from the mineral cobaltite(Co,Fe)AsS, given the fact that there is no evidence of Ni (anelement contained in the mineral smaltite [Co,Ni]As3–2) in the EDSspectrum (Muhlethaler and Thissen, 1993).

According to scholarly opinion the composition of smalt variesconsiderably in SiO2 (65–71, 66–72), K2O (16–21, 10–21), CoO (6–7,2–18) and in impurities of other oxides (Al, Ba, Ca, Cu, Fe, Mg, Mn,Ni, Na) (Muhlethaler and Thissen, 1993). EDS microanalyses of twograins of smalt show the following mean composition: (a) silicon(68.93%), potassium (22.59%), cobalt (4.09%), calcium (2.16%) andiron (2.492%); (b) silicon (85.42%), potassium (3.89%), cobalt(3.25%), calcium (1.11%), iron (2.05%), aluminium (1.63%) and arse-nic (2.66%). The remarkable variations between the composition ofthe two types of smalt used suggest the existence of two differentsupplies of the pigment. The painter used a low quality, finely-ground smalt in the underlayers, whereas the better quality, largeblue grains were applied on the uppermost layers.

Notably, recent studies have shown that smalt, when used in oilpaint, gradually discolours owing to the loss of potassium (this is

underpaint and (b) mFTIR spectrum depicting characteristic peaks of smalt and calcite.

Fig. 7. Cross-section from the olive-green zone in the background in (a) St Stephen’s and (b) the Protaton. (c, d) mRaman spectrum of green earth and mFTIR spectrum of green earthand calcite.

Fig. 8. Cross-section from St Demetrius’s grey-blue tunic in (a) reflected and (b) UV light. (c) SEM spectrum from the blue pigment.

Sr. Daniilia et al. / Journal of Archaeological Science 35 (2008) 2474–2485 2479

Fig. 10. mRaman spectrum of malachite.

Sr. Daniilia et al. / Journal of Archaeological Science 35 (2008) 2474–24852480

designated as a leaching process) (Boon et al., 2001). Althoughanalogous smalt deterioration has been identified in 16th centuryRoman wall paintings (whether fresco or secco is not reported)(Santopadre and Verita, 2006), and whereas smalt discolourationalso occurs in 17th century wall paintings executed both in fresco orfresco–secco technique (Ajo et al., 2004), no indication of thisphenomenon has been noted in St Stephen’s church.

3.2.2.2. Green. Of particular interest is the painting technique dis-played in the olive-green garments. The dark olive tone of theunderpaint is combined with intense green highlights that tail offinto fine white brushstrokes (Fig. 9a). In the cross-section of thesample from St Mercurius’ short tunic (STB1) and above the layer ofthe preliminary drawing – a mixture of lime and carbon black – onedetects the layer of the underpaint, a mixture of yellow ochre andcarbon black (Fig. 9b). In the first light gradation use is made ofcoarse-grained malachite, which contains natural admixtures ofazurite grains, haematite and yellow ochre.

The mRaman spectrum of the green pigment was indicative ofmalachite (Fig. 10, Table 2) (Frost, 2006; Frost et al., 2007;Bordignon et al., 2007).

The particular combination of cool green highlights and warmolive-green underpaints is a technique known to painters from alleras. In Byzantine times, however, monumental painting mainlyemploys green earth in unmixed gradations (Fig. 9c, d) (Daniiliaet al., 2000). Again in the post-Byzantine period copper pigments(malachite, verdigris), which offer more intense and more saturatedgreen shades (Lelekova, 2006), are introduced to painters’ palettes.

3.2.2.3. Red. For the underpaint of the chestnut-red garments(Virgin’s mantle, STB3) pure haematite, mixed with cinnabar in thefirst light, is used whereas the final highlight is executed in thickbrushstrokes of pure cinnabar (Figs. 11a, b and 12, Table 2) (Van-denabeele et al., 2005; Daniilia and Andrikopoulos, 2007). Thepresence of grains of lime indicates the presence of lime waterwhich is used as a binder, following fresco painting technique.Applying this particular stratigraphy in the red garments at StStephen’s the painter underscores one of the most significant dif-ferences between this and the artistic style of the Byzantine period.In the latter, red ochre is found in the underpaints, while for the

Fig. 9. (a, b) Detail of St Mercurius’s olive-green tunic in St Stephen’s church and cross-sectiofrom a highlight.

two gradations of the lights pure cinnabar and minium are used,respectively (Fig. 11c, d).

The bright red tones of the clothing are rendered in cinnabarwhich, for the highlights, is mixed with lime (Fig. 13). In the variedchestnut and pink shades of the different garments mixtures ofhaematite and yellow ochre are used in dissimilar proportions,with, in certain instances, the further addition of lime and carbonblack.

3.2.3. The flesh tonesThe artist of the St Stephen wall paintings follows faithfully the

traditional manner of fashioning the flesh areas, but withdeviations in his choice of pigments and, accordingly, in the finalshading. The tones both of the underpaint and of the flesh (Fig. 14a)vary significantly from those found in 14th century Byzantine wallpaintings (Fig. 14c), and are characteristic of the style not only of theperiod but also of this particular painter (Daniilia et al., 2000, 2008).

n from the green light. (c, d) Detail of a green garment in the Protaton and cross-section

Fig. 11. (a, b) Detail of the Virgin’s mantle in St Stephen’s church and cross-section of a highlight. (c, d) Detail of a red garment in the Protaton and cross-section of a highlight.

Sr. Daniilia et al. / Journal of Archaeological Science 35 (2008) 2474–2485 2481

Unlike the mixture of green earth and yellow ochre used for theunderpaint of the Protaton’s wall paintings (Fig. 14d), here, the darkbrown underpaint consists of haematite, yellow ochre, carbon blackand grains of cinnabar (Fig. 14b). Similarly, the characteristic pinkshade for the flesh in St Stephen’s (a mix of lime and cinnabar) issignificantly different from that used in Protaton (a mix of lime andyellow ochre). At the same time, it is noteworthy that differences inthe thickness of the paint layers between the wall paintings of theProtaton and those in St Stephen’s katholikon – both for theunderpaint and for the flesh – result not only from the kind ofpigments used (their hiding power, granulometry) but also fromthe desired aesthetic effect and fingerprint of each artist.

3.3. Binding medium

In order to introduce the section on binding media, it is useful toclarify certain specific terminology: al fresco indicates a technique

Fig. 12. mRaman spectrum of cinnabar (Fig. 11a). The characteristic peak of calcite at1086 cm�1 is also recorded.

of painting on damp plaster whereby a restricted number of pig-ments (chiefly earthy) is mixed simply with water or limewater; alsecco, on the other hand, denotes painting executed on dry plasterusing pigments that are blended with one or another organicbinder (Winfield, 1968; Daniilia et al., 2007).

Macroscopic examination of the wall paintings’ surface textureand of the modelling of the brushstrokes leads to the hypotheticalconclusion that the St Stephen painter employed a mixed techniqueof fresco–secco. On the other hand, microscopic observation of thecross-sections together with mFTIR spectroscopy have verified (a)

Fig. 13. Detail of Archangel Gabriel’s garment and cross-section from the redunderpaint.

Fig. 14. (a, b) Detail of the Virgin’s face in St Stephen’s church and cross-section of the flesh tone. (c, d) Detail of a face in the Protaton’s wall paintings and cross-section of the fleshtone.

Sr. Daniilia et al. / Journal of Archaeological Science 35 (2008) 2474–24852482

extensive use of lime both as a white pigment and as a binder (inthe form of lime water) and (b) different degrees of diffusion be-tween the paint layers and the underlying plaster (Daniilia et al.,2007). In a few circumstances the grains penetrate the plaster(Fig. 15, left), a fact that reinforces the aforementioned opinionabout painting on damp plaster, while at other times the paintlayers separate conspicuously, which is an indication of painting

Fig. 15. Cross-sections of several shades in the St Stephen wall paintings. Left: the first paintimplies the application of al secco technique.

employing al secco technique, that is, with the use of an organicbinder (Fig. 15, right).

According to received tradition and supported by scholarshipand data stemming from analyses carried out on samples fromByzantine monuments, proteinaceous materials (egg, animal glue,casein) were used as binders (Winfield, 1968; Dionysios of Fourna,1996; Pavlidou et al., 2006; Daniilia et al., 2007). Recent

layer has been applied on wet plaster (intense diffusion). Right: the absence of diffusion

Table 4Amino acid concentration ratios in samples from St Stephen’s

Amino acidratios of reference egg

Gly/Glu <1 Gly/Asp <1 Pro/Asp <1 Glu/Pro >2

STB4 0.9 2.7 0.6 4.9STA5 1.3 2.7 0.4 4.9STB3a 1.2 2.4 0.4 4.9STB3b 0.9 2.3 0.4 6.8x 1.1 2.5 0.5 5.4SD 0.2 0.2 0.1 1.0

Sr. Daniilia et al. / Journal of Archaeological Science 35 (2008) 2474–2485 2483

publications have presented the results achieved by employinganalytical methods both to identify organic materials in artworksand to measure the effect of ageing of those materials in theiridentification (Colombini et al., 1998, 1999a; Rampazzi et al., 2002).

In order to study the GC/MS results of St Stephen’s wall paint-ings (samples STB3a, STB3b, STB4, STA5) it was first necessary toanalyse the reference substances of egg, animal glue and casein(Daniilia et al., 2007). Recognition of the nature of the proteinbinding medium was achieved by a quantitative determination ofamino acids (Table 3); their characteristic ratios were examined(Table 4) and principle component analysis (PCA) was applied inthe percentage content of the amino acids (Fig. 16).

Table 3 summarises the amino acids’ content, which fluctuatedbetween 0.08–0.81% (w/w). The characteristic ratios (Pro/Asp andGlu/Pro) concur with those of egg. The small differentiations (Gly/Glu, Gly/Asp) are most probably due to the presence of inorganicpigments in the St Stephen samples (Halpine, 1992; Colombiniet al., 1998, 1999b; Daniilia et al., 2007). It is noticeable that in theanalysed samples there is evidence neither of animal glue (absenceof hydroxyproline) (Casoli et al., 1996; Halpine, 1992), nor of casein(ratio of Pro/Asp is <1) (Daniilia et al., 2007).

In the PCA score plot of the relative percentage amino acids, theSt Stephen samples are found nearest to the cluster of pure egg(Fig. 16). This observable shift is probably due to the influence of theinorganic pigment content in the samples (Daniilia et al., 2007).Apart from the inorganic pigments, the shift can also be attributedto natural ageing of the egg protein (Rampazzi et al., 2002), giventhat the wall paintings were completed at the beginning of the 17thcentury. Colombini et al. (2000) have demonstrated that artificialageing does not significantly affect the amino acid profile of proteinbinders; consequently, protein binders in old paintings can bereliably identified by comparing the amino acid composition withthat of reference paint materials which have not aged.

In conclusion, the results of the entire analysis have shown thategg was used not only as a binding medium for the paint layers butalso as a component of the final plaster (intonaco), a fact that con-curs with the surviving oral tradition in the wider region of Thessaly.

3.4. Efflorescence

A close examination of the nature of the decay in wall paintingsreveals soluble salts as the main cause of deterioration. Nitrates,oxalates and sulphates are known to be among the most harmfulsoluble salts (Arnold and Zehnder, 1985; Wust and Schluchter,2000). Under the influence of environmental conditions (temper-ature, humidity, light, atmospheric pollutants, micro-organisms,etc.) these salts are subjected to cycles of crystallization–dissolu-tion, leading to mechanical stresses and chemical alterations that

Table 3Mean values of the relative percentage content of amino acids in St Stephen’ssamples

Amino acids STB4 STA5 STB3a STB3b

Ala 9.2 9.3 7.5 5.7Gly 20.2 19.9 22.1 22.1Val 4.1 4.4 3.7 5.0Leu 6.5 6.7 5.9 8.9Ile 3.4 3.5 2.9 4.6Met 0.1 0.3 0.1 0.0Ser 10.9 16.6 14.8 7.3Thr 7.8 8.5 7.6 4.9Pro 4.5 3.3 3.8 3.5Phe 3.3 4.0 3.2 4.2Asp 7.4 7.3 9.3 9.6Glu 22.1 15.9 18.8 23.6Hyp 0.0 0.0 0.0 0.0Tyr 0.4 0.3 0.3 0.6

can result in flaking and powdering of both paint layer and plaster(Mora et al., 1984). One of the most important questions that haveto be settled, when planning a conservation methodology, is how toidentify the salts present as contaminants and pollutants in thepainting. Since their removal is crucial in cleaning painted surfaces,conservators need to know precisely the kind of salts in question.

Calcium sulphate dehydrate (gypsum) is the most commonly en-countered pollutant in carbonatic wall paintings. The formation ofgypsum during sulphation involves the dry deposition reaction be-tween calcite (CaCO3) and sulphur dioxide (SO2) gas, in the presenceof high relative humidity, an oxidant and a catalyst (Fe2O3 or NO2). Inthis case gypsum is detected on the surface (Pavlidou et al., 2006).

The widespread presence of salts, visible as a whitish irregularfilm in several places in St Stephen’s wall paintings, is, in certainrepresentations, especially evident in that it screens the intensity ofthe original colour and masks details in the paint (Fig. 17a). Thenature of the salts has been identified by mFTIR on a sample takenfrom the grey background beside St Basil (STA11). The mFTIR spec-trum (Fig. 17b, Table 2) reveals the presence of gypsum(CaSO4$2H2O) (Grassi et al., 2007). The sample also contains wax(Mazzeo et al., 2006), which might have been used during a pre-vious conservation attempt.

4. Conclusions

The wall paintings in the katholikon of St Stephen’s monasteryconstitute a representative example of post-Byzantine monumen-tal art at the beginning of the 17th century. Their anonymous artistechoes in general terms the tradition of contemporary monumentalart in the wider region of central and northern Greece. He wasevidently quite familiar with previous styles, which influenced his

Fig. 16. PCA of amino acid percentage data of reference samples (egg, animal glue,casein) and wall painting samples from St Stephen’s church.

Fig. 17. (a) St Basil the Great and (b) mFTIR spectrum of the whitish film formed over the paint surface.

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productions. But in certain aspects he took an independent path.For example, he not only augmented his palette by importing newpigments of more recent circulation in Europe, but also developednew stylistic features that characterise his epoch and his own,personal elan.

Noteworthy particularities vis-a-vis medieval Byzantine paint-ings have been revealed. These relate to the materials as well astheir technical application. For the plaster, by way of example, use ismade on the one hand of the ariccio yellow clay with a modestamount of lime mixed with straw, and on the other of the intonacolime. The artist’s palette includes (besides what is customary): lime(CaCO3), carbon black (C), yellow ochre (Fe2O3$H2O), haematite(Fe2O3), green earth (K[(Al(III), Fe(III))(Fe(II), Mg(II))], [(AlSi3,Si4)O10(OH)2]), and cinnabar (HgS), smalt (CoO$SiO2$K2O) andmalachite [CuCO3$Cu(OH)2]. An interesting point is the presence ofsmalt in the blue field, instead of the more commonly used readilyavailable azurite or the rarer lapis lazuli. Moreover, aside from greenearth, employed very widely and the sole green pigment for wallpaintings in the Byzantine period, St Stephen’s representations makeuse of malachite, a pigment especially selected for highlighting thegarments in order to achieve further saturation of the shades.

The artwork begins on damp plaster and is completed by meansof secco technique which uses egg as the binding medium. It isimportant to note that egg is also seen to constitute a component ofthe intonaco.

The wall paintings under surveillance, beyond the vandalismwhich they suffered during the World War II and the Civil War,exhibit problems in preservation as a result of the salt (gypsum)that has formed on the painted surface. This whitish layer of salt,covering many areas of the wall paintings, affects significantly theaesthetic impact of the post-Byzantine, old katholikon of themonastery of St Stephen at the Meteora.

Acknowledgements

The authors would like to thank the Holy Monastery of AgiosStephanos at Meteora for the approval to analyze samples from thewall paintings, as well as Mrs Dimitra Lazidou, conservator, forsample acquisition.

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