Journal of Cultural Heritage 13 (2012) 107113

Case study

Pigment identication in a Greek icon by optical microscopy and infrared microspectroscopy

Dimitra Kovala-Demertzi a, , Leuteris Papathanasis a , Rocco Mazzeo b , Mavroudis A. Demertzis a , Evagelia A. Varella c , Silvia Prati b
a b c

Department of Chemistry, University of Ioannina, 45110 Ioannina, Greece Universita di Bologna, sede di Ravenna, Via Tombesi dallOva 55, 48100 Bologna, Italy Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece

a r t i c l e

i n f o

a b s t r a c t
Optical microscopy, cross-section and fragment Micro-FTIR spectroscopic techniques along with microchemical tests were used for the identication of pigments in two different samples of an icon. Representing the Last Judgement, and painted by the Greek master Ioannis from the village of Kapesovo in the year 1771, the kneeling desk icon under investigation is a noteworthy contribution to the study of materials in post-Byzantine visual arts. The main components found in the ground layer of both samples were gypsum, beeswax and a proteinaceous material. Cinnabar, Prussian blue and cerussite were identied on the paint layers. The binding medium on the paint layers was weddelite. The materials used in the painting and ground layers were characterized in order to clarify the painting technique. Proteinaceous materials have been identied as binders for the pigments, indicating a tempera painting technique. 2011 Elsevier Masson SAS. All rights reserved.

Article history: Received 4 January 2011 Accepted 8 June 2011 Available online 23 August 2011 Keywords: Pigments identication Micro-infrared spectroscopy Optical microscopy Greek icon

1. Introduction and aims of the research At times neglected and often misinterpreted, post-Byzantine art denotes an interesting attempt to adopt Occidental features and methodologies, while remaining faithful to the venerable Medieval prototypes. Highly skilled professionals, with a surprisingly updated knowledge, and an intense mobility potential, are seeking their identity experimenting with novel materials and techniques, without ever abandoning the great past. The icon under consideration was donated to the Byzantine Museum of Ioannina, Greece, as part of a collection belonging to the renowned Zosimaia academy. It is representing the Last Judgement and was created as a kneeling-desk element in the year 1771 by Ioannis the painter (zographos), member of a distinguished artists line established in Kapesovo, a village in the then autonomous region of Zagori, Epirus. The unambiguous provenance is combined to a fascinating chromatic conception in red and blue, enriched with golden shades. Thus, pigment analysis turns into a challenging scientic and aesthetic question, as it is amply evaluating the multilevel signicance of the masterpiece; and subsequently providing a greater understanding on 18th century icon painting, and

post-Byzantine visual arts on the whole. In Orthodox iconography, colours bear universally accepted theological connotations; permitting thus hue and brilliance to unequivocally comment the scenes and persons depicted [1]. Being an instant of supreme joy and ultimate sorrow, the Last Judgement is typically expressed by means of the most pure and vivid tones. Thus, saturated scarlet red and pure gold are adorning the faithful in royal splendour, while alluding to the re-faced Cherubs surrounding Christ, and to the Fire River emerging from His feet. The venerated egg tempera technique is actually the sole able to meet all aesthetic and transcendental requirements of icon painting on wood. Widely available in Orthodox countries, gypsum is the traditional material employed for ground preparations, while beeswax, occasionally combined with low-cost inert our or starch, is praised as a valuable and most ancient natural protective coating [2]. Joining in the same palette, natural cinnabar and imported synthetic Prussian blue should be considered a typical response for Orthodox painters during the late Ottoman centuries, since these experienced itinerant professionals were well aware of Modern art and science, and shared quite often the difcult task of reconciling tradition and novel knowledge. 2. Experimental The analytical procedure encompassed optical microscopy, micro-FTIR spectroscopy (ATR single measurements, mapping and

Corresponding author. Tel.: +30 26 50 08 42 5. E-mail addresses: dkovala@cc.uoi.gr (D. Kovala-Demertzi), me00280@cc.uoi.gr (L. Papathanasis), rocco.mazzeo@unibo.it (R. Mazzeo), mdemert@cc.uoi.gr (M.A. Demertzis), varella@chem.auth.gr (E.A. Varella). 1296-2074/$ see front matter 2011 Elsevier Masson SAS. All rights reserved. doi:10.1016/j.culher.2011.06.003

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Fig. 1. (a) Christ-Judge post-Byzantine icon in egg tempera and (b) the same icon showing the paint samples CJB and CJR.

Transmission mode with microdiamond compression cell) and microchemical tests. An optical microscope Olympus BX51 M was used, and photomicrographs were recorded with a scanner digital camera Olympus DP70. Samples were embedded in a polyester resin support, then cross-sectioned and polished with conventional methods using silicon carbide card with successive grid from 120, 400, 800, to 1000. Dark eld observation of the cross-sectioned samples has been performed, and reected light microscopy was utilized to study the structure of the cross-sections under visible and ultraviolet light. Sample cross-sections were excited at 313 nm, while the uorescence emission was acquired in the whole visible spectrum. A Thermo-Nicolet Avatar 370 spectrometer was used combined with a Thermo Continuum IR microscope, tted with a MCT type A detector cooled by liquid nitrogen. Micro-FTIR analyses of the paint samples were performed by placing fragments of the paint samples and the cross-sectioned samples on the microscope motorized stage and selecting the area through a 15 Thermo-Electron
Table 1 Results of the studies in Optical Microscopy. Sample CJB (0) CJB (1) OM stratigraphy Ground, brownish-yellow Paint, blue Thickness 500 35 m Comments Vis

Innity Reachromat objective. Spectra were acquired in the range of 4000650 cm1 . For ATR measurements, a micro slide-on ATR with a silicon crystal was connected to the objective. ATR mapping was performed on selected area with a total of 35 (CJB) spectra collected with a step size of 20 microns. For transmittance measurements microdiamond compression cell was used. In accordance to the historical and documentary research, two paint samples (Christ Judge Blue [CJB], and Christ Judge Red [CJR]) were collected from the icon, Fig. 1a red (CJR) and Fig. 1b blue (CJB) paint samples were taken, as illustrated in Fig. 1. Microchemical analytical tests have been used to identify the nature of pigments. 3. Results and discussion 3.1. Optical Microscopy Both samples are characterized by a brownish-yellow ground, consisting of several preparation layers with yellowish

UV Yellowish uorescence, more evident between the different layers Blue particles show no uorescence, slightly uorescent matrix Layer uorescence white, a thin brown layer is also visible near the surface (3) Yellowish uorescence

Several preparation layers Dark blue particles (irregular shape and size 520 m) mixed with nely ground white pigment particles Layer barely seen Between the ground and the red layer black particles are visible, probably traces of preliminary drawing (indicated by arrows) Presence of darker crystals

CJB (2) CJR (0)

Surface, transparent layer Ground, brownish- yellow

12

CJR (1)

Paint, red-orange

68

CJR (2)

Surface, dark red

10

Layer not present in the entire section

Where the layer is fractured, a light yellow uorescence is visible probably caused by the inltration of a varnish layer (3) Dark pink uorescence

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Fig. 2. (a) and (b). Cross-sections of samples CJB and CJR respectively: optical photomicrograph under visible and UV uorescence (200 and 500 original magnication respectively): (0) ground layer, (1) paint layer, (2) surface layer and (3) outermost surface.

uorescence. On sample CJR, red orange crystals indicating yellow uorescence are visible, while the black particles present probably allude to traces from a preparatory drawing, a practice commonly used in post-Byzantine icon painting. On the paint layer of sample CJB, the irregular dark blue particles measure 520 m, are mixed with a nely ground white pigment, and indicate no uorescence. Photomicrographs are displaying a dark red surface layer bearing pink uorescence for sample CJR, and a transparent surface layer bearing white uorescence for sample CJB. The light yellow uorescence at CJR layer fragmentations is probably caused by the inltration of a varnish layer (Table 1, Fig. 2).
Table 2 Characteristic Infrared Bands on the sample Christ Judge Red (CJR) in cm1 . Sample CJR CJR-ground Materials Gypsum Beeswax Protein Binding medium Impurities Binding medium Red lake Weddellite Deposits

3.2. Micro-FTIR Spectroscopy Cross-section and fragment micro-FTIR spectroscopic analyses were performed on different layers of the two samples CJB and CJR. ATR measurements were performed stratigraphically on different points of the ground layer, Tables 2 and 3. The ground materials and the binding medium in the preparation layer proved to have the same composition in both samples, Fig. 3. The preparation layer was composed of gypsum (3540, 3402, 1682, 1620, 1148, 1100, 672 cm1 ) [3], and beeswax (2955, 2918, 2849, 1736, 1462, 1463, 1379, 730, 720 cm1 ), with further traces of proteinaceous

Characteristic Infrared Bands in cm1 1147, 1100, 672 2952, 2917, 2849, 1737, 1473, 1460, 1377, 729 1655, 1543 3304, 2953, 2916, 2848, 1730,1642, 1531, 1457, 1407, 1380, 1318, 723 1166, 1113, 1068, 786 3340, 2953, 2919, 2850, 1652, 1549, 1535, 1463, 1453, 1379, 1260, 1243, 1162, 720 3286, 2919, 2850, 1652, 1567, 1473, 1411, 1080, 898, 852 16501321 1111, 1061, 1035, 781

CJR-layer CJR-Dark red layer

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Table 3 Characteristic Infrared Bands on the sample Christ Judge Blue (CJB) in cm1 . Sample CJB CJB-ground Materials Gypsum Beeswax Protein Gypsum Beeswax Prussian Blue Cerussite Binding Medium Whewellite Varnish Oil Weddellite Cerussite Binding medium Characteristic Infrared Bands in cm1 3540, 3402, 1682, 1620, 1148, 1100, 672 2955, 2917, 2849, 1736, 1472, 1463, 1379, 730 1658, 1547 1148, 1100, 673 2955, 2918, 2849, 1462, 1737, 729, 719 2087 1412, 837, 676 3387, 2955, 2918, 2849, 1737, 1643, 1548 1324 2918, 2850, 1707, 1447, 1378, 1227, 1160, 1116, 1039, 959 2918, 2850, 1731, 1447, 1378, 1160, 720 1648, 1318 837, 676 3340, 2918, 2850, 1648, 1553

CJB-layer

CJB-surface

material [4]. The presence of gypsum, CaSO4 .2H2 O, is indicated by the appearance of stretching bands v(OH) at 3540 and 3402 cm1 , bending vibrations at 1682 and 1620 cm1 , and two bands at 1110 and 672 cm1 , assignable respectively to the stretching and bending modes of sulphate anions [3]. Occurrence of beeswax is suggested by the stretching bands v(CH2 ) and v(CH3 ) at 2955, 2918, and 2849 cm1 and the bending vibrations (CH2 ) and (CH3 ) at 1472 and 1463 cm1 ; the shoulder at 1736 cm1 corresponds to the

CO stretching band of the ester function. All these data are consistent with the presence of a waxy substance. The doublet at 730 and 720 cm1 is attributed to beeswax. Proteinaceous materials have relevant peaks at 1658 and 1547 cm1 [4]. The red pigment cannot be identied, since possible compounds absorb outside the detector range, thus the red layer spectrum is showing sole the absorbance of the organic materials, e.g. egg tempera, bearing characteristic amide bands at 1643 and 1548 cm1 .

Fig. 3. -FT-IR spectra by ATR mode on the ground layer of the (a) CJB and (b) CJR. Designated as B bands corresponding to Beeswax, as P to proteinaceous materials and as G to gypsum.

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Fig. 4. -FT-IR spectra, mATR on cross-section, on the CJR paint layer (a) CJR-Red Layer and (b) CJR-Dark Red Layer. Designated as M bands corresponding to binding medium, as B to beeswax, as W to whewellite, as L to red lake and as I to impurities.

Since relevant microchemical tests proved the pigment to be cinnabar, the broad band in the 12001000 cm1 region can be attributed to sulphate impurities in it, implying the presence of the natural mineral rather than vermillion. The dark red particles are characterized by the absorptions of the binding medium, weddellite Ca(COO)2 .5H2 O, and some deposition material; a red lake (glaze) has been also identied in low concentration, Fig. 4, Table 2. The layer of glaze (Table 2, Fig. 4b) seems to contain proteinaceous material, most probably oxidized egg. This type of result needs additional information in order to interpret the data with surety. This probably was an egg tempera glaze. As indicated in Fig. 5, ATR measurements of the paint layer on sample CJB suggest the presence of Prussian blue, Fe4 [Fe(CN)6 ]3 .nH2 O, since the cyanide stretching vibration at 2087 cm1 is highly specic for this pigment [5]. The bands at 1412, 837 and 676 cm1 are associated to mineral lead carbonate cerussite, PbCO3 [6]. The ATR spectrum yields no unequivocal information for the binding medium, the ester group (1737 cm1 ) being attributable to egg yolk, as well as to beeswax contaminations, with further bands at 730, 720 cm1 . Several dark blue particles of the layer were analyzed in transmission mode, and the results conrmed the presence of Prussian blue, cerussite and the binding medium; the ester shoulder at 1740 cm1 is clearly assignable to egg tempera [7,8], while the absence of beeswax is denitely conning it to the ground layer. A layer of oil varnish is displaced in Fig. 5b, Table 3. The absorption peak in the surface coating is

the carboxylic acid stretching band at 1707 cm1 characteristic of the natural resins [9]. The spectral prole of the varnish is similar to the natural triterpenoids resins dammar or mastic, the former being introduced into the market only in 1829 [9,10]. These two resins are too similar to be distinguished by infrared spectroscopy. These two resins exhibit a multiple absorption in the region 12501000 cm1 , as well as at 1380 and a strong absorption at 1030 cm1 [9,10]. The results are conrmed by the ultraviolet light microscopic observation on a red and blue fragment, Fig. 6. The map was recorded on a representative area of the sample (80 120 m) for a better denition of the component localization. In particular, mapping permitted to conne the presence of beeswax to the ground layer, and conrmed the use of egg tempera in the paint layer. 3.3. Microchemical tests A microchemical test was carried out to elucidate the nature of the binding medium. When adding a drop of NaOH 10% to a fragment of the CJR sample, the outer dark red layer immediately starts to dissolve, due to saponication of the organic material present. This behaviour is characteristic for fatty acid compoundse.g. oilsor organic acids, including colorants. Conrming the UV uorescence, it is strongly suggesting that a red lake may have been used for glazing purposes. The red layer seems unaffected, and partial desegregation occurs only when shifting

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Fig. 5. -FT-IR spectra on the CJB paint layer: (a) mATR on cross-section and (b) mATR on surface. Designated as M bands corresponding to binding medium, as C to cerussite, as PB to Prussian Blue and as W to whewellite.

Fig. 6. (a) CJB cross section photomicrograph (original magnication 200 ) with the indication of the area selected for the ATR mapping. Chemigram mapping of (b) Prussian blue (2087 cm1 ), (c) gypsum (672 cm1 ), (d) beeswax (729 cm1 ) and (e) egg tempera (1737, 1643, 1548 cm1 ). Red and blue colours indicate areas of respectively higher and lower concentration.

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the sample with a glass rod. A similar, although less apparent, desegregation of the blue layer is observed in sample CJB, afrming the FTIR analysis conclusion that the technique used was egg tempera. Identication of cinnabar as the red pigment is based in the reactions: HgS + HNO3 Hg2+ + H2 S(g) , Hg2+ + KI HgI4 2 . A small fragment of the sample is placed on a glass slide; under the stereomicroscope several crystals of KI and 12 drops of HNO3 in 1% aqueous solution are added. The red colour gradually fades away leaving a slightly yellow solution, bearing the characteristic H2 S odour. 3.4. Conclusions The kneeling desk icon under investigation, the Last Judgement, was painted by the Greek master Ioannis from the village of Kapesovo in the year 1771. Joining in the same palette natural cinnabar and imported synthetic Prussian blue should be considered a typical response for Orthodox painters during the late Ottoman centuries, since these experienced itinerant professionals were well aware of Modern art and science, and shared quite often the difcult task of reconciling tradition and novel knowledge. For Ioannis and his numerous colleagues, natural cinnabar is an ancient colorant worth using for its smooth application, proved stability, and high aesthetic value. At the same time, Prussian blue constitutes an appealing option for those wishing a saturated radiant hue at a moderate cost. Since the chromatic result is the same, there is no reason to insist in favouring the expensive natural ultramarine proposed in the earlier tradition. Faithful to millenary concepts, Orthodox iconography is always ready to introduce improved methodologies and innovative materials, provided that the overall theological approach is not betrayed. The main components found in the ground layer of both samples were gypsum, beeswax and a proteinaceous material. Cinnabar, Prussian blue and cerussite were identied on the paint layers. The binding medium on the paint layers was weddelite. The materials used in the painting and ground layers were characterized in order to

clarify the painting technique. Proteinaceous materials have been identied as binders for the pigments, indicating a tempera painting technique. Since, there is not an extensive body of literature concerning the technique of construction of Greek icons in general [11], the present project together with art historical research could provide a greater understanding about the icon painting technique and contribute to the general body of knowledge concerning on 18th century icons. This examination contributes to the body of knowledge concerning technical information, and will be of use when put in context with existing and future studies on the subject. References
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