Studying pigments on painted plaster in Minoan, Roman and Early Byzantine Crete. A multi-analytical technique approach

AbstractWall paintings spanning two millennia of Cretan painting history and technology were analysed in an effort to determine similarities and evolutions of painting materials and technology. A multi-technique approach was employed that combined the use of (a) laser-induced breakdown spectroscopy (LIBS) and Raman microspectroscopy, based on mobile instrumentation, appropriate for rapid, routine-level object characterization, and (b) non-destructive X-ray diffractometry (XRD), performed directly on the wall painting fragment, which provides detailed information on the minerals constituting the paint. Elemental analysis data obtained through LIBS were compared with molecular and crystal structure information from Raman spectroscopy and XRD. Cross-sections from selected samples were also investigated by means of optical microscopy and scanning electron microscopy coupled to micro-probe analysis and X-ray mapping that enabled identification of several mineral components of the paint confirming the results of the XRD analysis. In parallel, replica wall paintings, created with known pigments and binding media for reference purposes, were examined with optical microscopy and stain tested for organic materials. The overall study shows that the LIBS and Raman techniques offer key advantages, such as instrument mobility and speed of data collection and interpretation that are particularly important when dealing with on-site investigations. Thus, they are capable of providing important compositional information in an effective manner that enables quick surveying of wall paintings and permit targeted sample selection for further analysis by advanced laboratory techniques. FigureOptical microscopy image of painted plaster from the Minoan Palace of Knossos, Crete, showing blue paint composed of Egyptian Blue (Cuprorivaite) and Mg-riebeckite. Clockwise are shown a LIBS spectrum showing the presence of Cu along with Ca, Al and Fe, in the blue paint; b Fluorescence emission spectrum with the characteristic emission of Egyptian Blue at around 900 nm and c X-ray diffractogram confirming the presence of Cuprorivaite and Mg-riebeckite

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