The Raman spectra of plattnerite [lead(IV) oxide, PbO₂] and of the lead pigments red lead (Pb₃O₄), lead monoxide [PbO, litharge (tetragonal) and massicot (orthorhombic)], lead white [basic lead carbonate, 2PbCO₃·Pb(OH)₂] and of their laser-induced degradation products were recorded using a range of different excitation lines, spectrometer systems and experimental conditions. The degradation of PbO₂ is more extensive along the pathway PbO₂ → Pb₃O₄ → PbO (litharge) → PbO (massicot) the shorter the wavelength of the excitation line and the higher its power. The Raman spectrum of PbO₂, which is black and of the rutile structure, is particularly difficult to obtain but three bands, at 653, 515 and 424 cm⁻¹, were identified as arising from the b_2g, a_1g and e_g modes respectively, by analogy with the corresponding modes of isostructural SnO₂ (776, 634 and 475 cm⁻¹). A further oxide was identified, PbO_1.55, the Raman spectrum of which does not correspond to that of any of the laser-induced degradation products of PbO₂ at any of the wavelengths used. The Raman results are critical to the future use of Raman microscopy for the identification of lead pigments on artworks.

The combined application of two laser-based analytical techniques—laser-induced breakdown spectroscopy (LIBS) and Raman microscopy—for pigment identification on painted artworks is demonstrated. Detailed spectral data are presented from analyses performed on a 19th century Byzantine icon, which was examined in order to identify the pigments used in the original painted structure, as well as in interventions carried out subsequently for restorative purposes. LIBS measurements yielded elemental analytical data which suggest the presence of certain pigments and, in addition, provide information on the stratigraphy of the paint layers. Identification of most pigments and of the materials used in the preparation layer was performed by Raman microscopy.

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. Copyright © 2002 John Wiley & Sons, Ltd.