Micro-Raman spectroscopic analysis of inks and pigments in illuminated medieval old-Slavonic manuscripts

Micro-Raman spectroscopy was applied in characterisation of inks and pigments used in the text, illuminations and miniatures of two old-Slavonic manuscripts: Vrutok four gospels (13th14th centuries) and Benche four gospels (16th century). They were written in old-Slavonic language with old Cyrillic alphabet. Both were decorated with ornaments in so called Balkan style characterised with intertwined rings and floral motifs. Only four colours/pigments were used in the simple miniature and ornaments in Vrutok book: orpiment, vermilion, organo-copper complex and mixed ink. Much richer palette of pigments was revealed in the Benche book: calcite, gypsum, lead white, yellow ochre, pararealgar/realgar, vermilion, red lead, red ocra, organo-copper complex, malachite, indigo, iron gall ink, carbon black and pure metallic gold. The use of pigments in ornaments compared with miniatures is somewhat different in Benche book, suggesting that either handwriting and ornamenting on one side and miniatures, on the other, were done by different persons/painters or depiction of sacral themes of the miniatures canonically required the use of more expensive/elaborate pigments. Micro-Raman spectroscopy allowed in situ, non-destructive, rapid and unambiguous identification of the majority of pigments used in the text, ornamentations and miniatures in the Vrutok and Benche four gospels. In case of uncertainty in identification of pigments, scanning electron microscopyenergy dispersive X-ray analysis was applied. Copyright (C) 2012 John Wiley & Sons, Ltd.