This work is an extensive study of two post-Byzantine icons, 'Our Lady, the Life-giving Spring' and 'Saint Athanasios the Athonite,' both painted during the 16th century and now kept at Saint Modestos's Church in Kalamitsi, Chalkidiki, Greece. The icons were examined using non-destructive and microanalytical techniques, namely fluorescence photography under UV light, x-radiography and optical microscopy, in addition to micro-Raman and micro-Fourier transform IR spectroscopy. This study allowed the assessment of the current state of preservation of these icons, revealed prior damage and identified in detail the pigments and materials used in the original paintings and overpaintings. Moreover, it confirmed the usefulness of this approach to the detailed evaluation of icons in general and provided significant structural data on representative portable icons of Cretan-style religious painting. The palette for the original paintings of the two icons consists of the natural pigments caput mortuum, yellow ochre, carbon black, azurite, green earth, cinnabar, white lead, red lake and copper resinate; egg yolk was used as the binder. By contrast, the rather elementary overpaintings are of low tonality, consisting predominantly of mixtures of minium and carbon black, and also the synthetic pigments ultramarine blue, ''chrome green'' (Prussian blue + lead chromate), chrome yellow and lithopone. A blend of linseed oil and egg provided the binder for the pigments used. The same artist is understood from art historians to have overpainted both icons at the beginning of the 20th century.
A new mobile instrumentation that takes advantage of the simultaneous utilisation of two micro-analytical techniques (Raman and XRF) has already been effected within the PRAXIS European project (Competitive and Sustainable growth programme, PRAXIS: A portable Raman-X-Ray instrument. No G6RD-CT-2001-00602). The instrument permits structural characterisation of the pigments incorporated in a painting under study by evaluation of the Raman spectra together with elemental analysis of the same materials provided by XRF spectra. Although direct structural characterisation with great specificity is directly accomplished by Raman spectroscopy, the signal is often masked by strong fluorescence, a fact that imposes time consumption. On the other hand, the average signal offered by XRF over larger volumes enables unique information to be obtained from invisible under-layers. Moreover, the detection of trace elements by XRF, not influencing the Raman spectra, renders the characterisation of painting materials more comprehensive. Validation of the instrument's in situ and non-destructive capabilities was performed after its in vitroapplication on an experimental icon (painted with traditional Byzantine techniques). The data acquired by the two techniques from the same spots on the painting offer complementary results, which enable the identification of almost all pigments even in the case of over-painted art objects. Finally, the instrument's abilities on the identification of materials on specimen's cross sections are revealed.
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