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. Index Headings: Laser-induced breakdown spectroscopy; LIBS; Raman microscopy; Artwork analysis; Pigment identification.

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