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

Analytical and Bioanalytical Chemistry volume 402, pages 1413–1432 (2012)Cite this article

Abstract

Wall 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.

Optical 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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Acknowledgments

This project is carried out in the frame of collaboration between the Department of Archaeology, University of Glasgow, and IESL-FORTH, funded in part by the Leverhulme Trust, UK. We are very grateful to those who gave permission to analyse the wall painting fragments from their excavations: Dr. Sara Paton, Dr. Colin MacDonald, and Prof. Raffaella Farioli. Many thanks also to all who facilitated the study and selection of original materials: Dr. Doniert Evely, Prof. Todd Whitelaw, Dr. Evangelia Kiriatzi, Mrs. Helen Clark, and Mrs. Vicki Tzavara of the British School at Athens, Dr. Kostas Giapitsoglou and colleagues at the 13th Ephorate of Byzantine Antiquities, the 23rd Ephorate of Prehistoric and Classical Antiquities, Dr. A.G. Benvenuti and colleagues at the Scuola Archeologica Italiana di Atene. PS and AF acknowledge support from the EC Charisma project (FP7-INFRA-Grant agreement no: 228330). We thank Prof. N. Chaniotakis in the Chemistry Department at the University of Crete, Dr. Ross Stevenson and Dr. Karen Faulds in the Chemistry Department at Strathclyde University and Prof. R. J. H. Clark in the Chemistry Department at the University College London for granting access to their Raman spectroscopy instrumentation.

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Authors and Affiliations

  1. British School at Athens, Knossos Villa Ariadne Taverna, 714 09, Knossos, Crete, Greece

    Polly Westlake

  2. Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL-FORTH), P.O. Box 1385, 711 10, Heraklion, Crete, Greece

    Panayiotis Siozos, Aggelos Philippidis & Demetrios Anglos

  3. Department of Chemistry, University of Crete, P.O. Box 2208, 710 03, Heraklion, Crete, Greece

    Demetrios Anglos

  4. Department of Mineral Resources Engineering, Technical University of Crete, 731 00, Chania, Crete, Greece

    Chryssa Apostolaki & Vasilios Perdikatsis

  5. Department of Archaeology, University of Glasgow, Glasgow, G12 8QQ, UK

    Brendan Derham & Richard Jones

  6. Department of Conservation of Works of Art, National Gallery of Athens, 1 Michalacopoulou St, 116 01, Athens, Greece

    Agni Terlixi

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  1. Polly Westlake
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  2. Panayiotis Siozos
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  3. Aggelos Philippidis
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  4. Chryssa Apostolaki
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  6. Agni Terlixi
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  7. Vasilios Perdikatsis
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  8. Richard Jones
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  9. Demetrios Anglos
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Correspondence to Demetrios Anglos.

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Published in the special issue Analytical Techniques in Art, Archaeology and Conservation Science with guest editor Oliver Hahn

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Westlake, P., Siozos, P., Philippidis, A. et al. Studying pigments on painted plaster in Minoan, Roman and Early Byzantine Crete. A multi-analytical technique approach. Anal Bioanal Chem 402, 1413–1432 (2012). https://doi.org/10.1007/s00216-011-5281-z

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Keywords

  • Archaeological pigments
  • Wall paintings
  • Analysis
  • LIBS
  • Raman
  • XRD
  • SEM-EDX