Skip to main content

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

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

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig.13
Fig. 14
Fig. 15
Fig. 16

References

  1. Price TD, Burton JH (2011) An introduction to archaeological chemistry. Springer, New York

    Book  Google Scholar 

  2. Ciliberto E, Spoto G (Eds.) (2000) Modern analytical methods in art and archaeology, Chemical Analysis, A series of monographs on analytical chemistry and its applications, J.D. Winefordner (Ed.), Wiley, New York, vol. 155

  3. Uda M, Demortier G, Nakai I eds (2005) X-rays for Archaeology, Springer, London

  4. Stuart BH (2007) Analytical techniques in art conservation. Wiley, West Sussex, UK

    Book  Google Scholar 

  5. Kockelmann W, Pantos E, Kirfel A (2000) Neutron and synchrotron radiation studies of archaeological objects. In: Creagh DC, Bradley DA, eds, Radiation in Art and Archaeometry. Elsevier Science, New York, pp 1–33

    Google Scholar 

  6. Janssens K (2011) Synchrotron radiation in art and archaeology. J Anal At Spectrom 26:833–834

    Article  Google Scholar 

  7. Abe Y, Nakai I, Takahashi K, Kawai N, Yoshimura S (2009) On-site analysis of archaeological artifacts excavated from the site on the outcrop at Northwest Saqqara, Egypt, by using a newly developed portable fluorescence spectrometer and diffractometer. Anal Bioanal Chem 395:1987–1996

    Article  CAS  Google Scholar 

  8. Vandenabeele P, Weis TL, Grant ER, Moens LJ (2004) A new instrument adapted to in situ Raman analysis of objects of art. Anal Bioanal Chem 379:137–142

    Article  CAS  Google Scholar 

  9. Brysbaert A (2008) The power of technology in the Bronze Age Eastern Mediterranean. Monographs in Mediterranean Archaeology, Equinox, London

    Google Scholar 

  10. Jones RE, Photos-Jones E (2004) Technical studies of Aegean Bronze Age wall paintings: methods, results and future prospects. In: Aegean Wall Paintings: a tribute to Mark Cameron. British School at Athens, London, pp 199–228

    Google Scholar 

  11. Dandrau A, Dubernet S (2006) Plasters from Kommos: a scientific analysis of fabrics and pigments. In: Kommos V: The monumental Minoan buildings at Kommos. Princeton University Press, Princeton, pp 236–241

    Google Scholar 

  12. Anglos D (2001) Laser-induced breakdown spectroscopy in art and archaeology. Appl Spectrosc 55:186A–205A

    Article  CAS  Google Scholar 

  13. Giakoumaki A, Melessanaki K, Anglos D (2007) Laser-induced breakdown spectroscopy (LIBS) in archaeological science—applications and prospects. Anal Bioanal Chem 387:749–760, 760

    Article  CAS  Google Scholar 

  14. Cunat J, Palanco S, Carrasco F, Simon MD, Laserna JJ (2005) Portable instrument and analytical method using laser-induced breakdown spectrometry for in situ characterization of speleothems in Karstic caves. J Anal At Spectrom 20:295–300

    Article  CAS  Google Scholar 

  15. Fortes FJ, Cunat J, Cabalin LM, Laserna JJ (2007) In situ analytical assessment and chemical imaging of historical buildings using a man-portable laser system. Appl Spectrosc 61:558–564

    Article  CAS  Google Scholar 

  16. Agresti J, Mencaglia A, Siano S (2009) Development and application of a portable LIPS system for characterising copper alloy artefacts. Anal Bioanal Chem 395:2255–2262

    Article  CAS  Google Scholar 

  17. Brysbaert A, Melessanaki K, Anglos D (2006) Pigment analysis in Bronze Age Aegean and Eastern Mediterranean painted plaster by laser-induced breakdown spectroscopy (LIBS). J Archaeol Sci 33:1095–1104

    Article  Google Scholar 

  18. Smith GD, Clark RJH (2004) Raman microscopy in archaeological science. J Archaeol Sci 31:1137–1160

    Article  Google Scholar 

  19. Vandenabeele P, Edwards HGM, Moens L (2007) A decade of Raman spectroscopy in art and archaeology. Chem Rev 107:675–686

    Article  CAS  Google Scholar 

  20. Mazzeo R, Prati S, Sandu I, Spring M (2009). Paint layers. In: Pinna D, Galeoti M, Mazzeo R. Scientific examination for the investigation of paintings. A handbook for conservator–restorers, Firenze Italy: Centro Di della Edifirmi srl

  21. Ioakimoglou E (2010) Organic materials in art and archaeology vol. B: Proteinaceous materials in painting (in Greek). Ion editions, Athens, pp. 192–195

  22. Schaefer S (1996) Fluorescent staining techniques for the characterization of binding media within paint cross-sections and digital image processing for the quantification of staining results. In: Bakkenist T et al (eds) Early Italian paintings: techniques and analysis, symposium, Maastricht, 9–10 October 1996. The Limburg Conservation Institute distributed by Archetype Publications, Maastricht, pp 57–63

    Google Scholar 

  23. Eastaugh N, Walsh V, Chaplin T, Siddall R (2004) The pigment compendium: a dictionary of historical pigments. Elsevier Butterworth-Heinemann, Oxford

    Google Scholar 

  24. Burgio L, Clark RJH (2001) Library of FT-Raman spectra of pigments, minerals, pigment media and varnishes, and supplement to existing library of Raman spectra of pigments with visible excitation. Spectrochim Acta A 57:1491–1521

    Article  CAS  Google Scholar 

  25. Bailey K (1929) The Elder Pliny's chapters on chemical subjects. Part I. Edward Arnold & Co, London

    Google Scholar 

  26. Bailey K (1932) The Elder Pliny's chapters on chemical subjects. Part II. Edward Arnold & Co, London

    Google Scholar 

  27. Vitruvius (1960) The ten books on architecture. (trans: Morgan MH). Dover Publications, New York

    Google Scholar 

  28. Augusti S (1967) I colori pompeiani. De Luca Editore, Rome

    Google Scholar 

  29. Cennino D' Andrea Cennini (1960) The Craftsman's handbook. The Italian "Il Libro dell' Arte". (trans: Thompson DV). Dover Publications, New York

    Google Scholar 

  30. Mazzocchin GA, Agnoli F, Salvadori M (2004) Analysis of Roman Age wall paintings found in Pordenone, Trieste and Montegrotto. Talanta 64:732–741

    Article  CAS  Google Scholar 

  31. Calamiotou M, Siganidou M, Filippakis SE (1983) X-ray analysis of pigments from Pella, Greece. Stud Conserv 28:117–121

    Article  CAS  Google Scholar 

  32. Kakouli I (1997) Roman wall paintings: a scientific investigation of their technology. In: Bearat H et al. (eds), Roman wall painting: materials, techniques, analysis and conservation: Proceedings of the International Workshop on Roman Wall Painting, Fribourg, 7–9 March 1996. pp 131–141

  33. Siddall R (2006) Not a day without a line drawn: pigments and painting techniques of Roman artists. Proc R Microsc Soc 2:18–31

    Google Scholar 

  34. Pozza G, Ajό D, Chiari G, De Zuane F, Favaro M (2000) Photoluminescence of the inorganic pigments Egyptian blue, Han blue and Han purple. J Cult Herit 1:393–398

    Article  Google Scholar 

  35. Accorsi G, Verri G, Bolognesi M, Armaroli N, Clementi C, Miliani C, Romani A (2009) The exceptional near-infrared luminescence properties of cuprorivaite (Egyptian blue). Chem Commun 23:3392–3394

    Article  Google Scholar 

  36. Aliatis I, Bersani D, Campani E, Casoli A, Lottici PP, Mantovan S, Marino I-G, Ospitali F (2009) Green pigments of the Pompeian artists' palette. Spectrochim Acta A 73:532–538

    Article  Google Scholar 

  37. Filippakis SE, Perdikatsis B, Paradelis Th (1976) An analysis of blue pigments from Greek Bronze Age. Stud Conserv 21:143–153

    Article  CAS  Google Scholar 

  38. Perdikatsis V, Kilikoglou V, Sotiropoulou S, Chryssikopoulou E (2000) Physicochemical characterisation of pigments from Theran wall paintings. In: Sherratt S. ed., The wall paintings of Thera-vol. 1: Proceedings of the First International Symposium, Athens, 30 August–4 September 2000. pp 103–129

  39. Profi S, Perdikatsis B, Filippakis SE (1977) X-ray analysis of Greek Bronze Age pigments from Thera (Santorini). Stud Conserv 22:107–115

    Article  CAS  Google Scholar 

  40. Filippakis SE, Petrakis A, Assimenos K (1979) X-ray analysis of pigments from Vergina (second tomb). Stud Conserv 24:54–58

    Article  CAS  Google Scholar 

  41. Mirtsou E, Kesisoglou M, Michailidis K (1985) Ανάλυση χρωμάτων και κονιαμάτων μακεδονικού τάφου της περιοχής Λευκαδιών. Ανθρωπολογικά 8:47–51

    Google Scholar 

  42. Linn R (1996) Scientific investigation of the Roman and early Byzantine wall paintings of Caesarea, Israel. Unpublished MA, Courtauld Institute of Art, University of London, Israel

    Google Scholar 

  43. Bearat H (1996) Chemical and mineralogical analyses of Gallo-Roman wall painting from Dietikon, Switzerland. Archaeometry 38:81–95

    Article  CAS  Google Scholar 

  44. Gillis KM, Robinson PT (1985) Low temperature alteration of the extrusive sequence, Troodos ophiolite Cyprus. Can Miner 23:431–441

    CAS  Google Scholar 

  45. Booij E, Gallahan WE, Staudigel H (1995) Ion-exchange experiments and Rb/Sr dating on celadonites from the Troodos ophiolite. Cyprus Chem Geol 126:155–167

    Article  CAS  Google Scholar 

  46. Segal I, Porat N (1997) Composition of pigments from the Hellenistic walls in Acre. In: Bearat H et al. (eds) Roman wall painting: materials, techniques, analysis and conservation: Proceedings of the International Workshop, Fribourg, 7–9 March 1996. pp 85–92

  47. Bugini R, Folli L (1997) Materials and making techniques of Roman Republican wall paintings. In: Bearat H et al. (eds) Roman wall painting: materials, techniques, analysis and conservation: Proceedings of the International Workshop, Fribourg, 7–9 March 1996. pp 121–130

  48. Brysbaert A (2004) Technology and social agency in Bronze Age Aegean and Eastern Mediterranean painted plaster. PhD Thesis, Department of Archaeology. University of Glasgow, Scotland

    Google Scholar 

  49. Brecoulaki H, Perdikatsis V (2002), Ancient Painting on Macedonian Funerary Monuments, IV-III c B.C: A comparative study on the use of color. In: Tiverios MA, Tsiafakis DS (eds), Color in Ancient Greece, pp.147-154, Aristotle University of Thessaloniki

  50. Perdikatsis V, Maniatis Y, Chr S-P (2002) Characterization of the pigments and the painting technique used on the Vergina stelae. In: Tiverios MA, Tsiafakis DS (eds), Color in Ancient Greece, Aristotle University of Thessaloniki, pp 245–258

  51. Varone A, Bearat H (1997) Pittori romani al lavoro. Materiali, strumenti, techniche: evidenze archeologiche e dati analitici de un recente scavo pompeiano lungo via dell’Abbondanza (reg. IX ins. 12). In: Bearat H et al. (eds), Roman wall painting: materials, techniques, analysis and conservation: Proceedings of the International Workshop on Roman Wall Painting, Fribourg, 7–9 March 1996.

  52. Mazzocchin GA, Agnoli F, Mazzocchin S, Colpo I (2003) Analysis of pigments from Roman wall paintings found in Vicenza. Talanta 61:565–572

    Article  CAS  Google Scholar 

  53. De La Rie E (1982) Fluorescence of paint and varnish layers (Part III). Stud Conserv 27:102–108

    Article  Google Scholar 

  54. Wolbers R, Laundrey G (1987) The use of direct reactive fluorescent dyes for the characterization of binding media in cross sectional examinations. In: AIC Preprints, American Institute for Conservation 15th annual meeting. Vancouver, British Columbia, AIC, Washinghton DC, pp 168–203

    Google Scholar 

  55. Brecoulaki H, Zaitoun C, Stocker SR, Davis JL (2008) An archer from the palace of Nestor: a new wall-painting fragment in the Chora Museum. Hesperia 77:363–397

    Article  Google Scholar 

  56. Nevin A, Osticioli I, Anglos D, Burnstock A, Cather S, Castellucci E (2008) The analysis of naturally and artificially-aged protein-based binding media using Raman spectroscopy combined with principal component analysis. J Raman Spectrosc 39:993–1000

    Article  CAS  Google Scholar 

  57. Cameron MAS, Jones RE, Filippakis SE (1977) Analysis of fresco samples from Knossos. Ann Br Sch Athens 72:123–184

    Google Scholar 

  58. Photos-Jones E, Jones RE, Hall AJ (2003) Technical report on painted plaster fragments from the Greek-Swedish excavations at Kastelli, Khania, Crete. Appendix 4. In: Hallager E, Hallager BP (eds), The Greek-Swedish excavations at the Agia Aikaterini Square, Kastelli, Khania, 1970–1987 and 2001: Results of the excavations under the direction of Y Tzedakis and C-G Styrenius, vol III. Astrom Editions, Stockholm, pp 306–320

    Google Scholar 

  59. Perdikatsis V (1995) Analysis of pigments from ancient Greek art monuments, in Proc. Scientific Symp. Art and Technology (Athens 1993), Athens, pp 272–280

    Google Scholar 

  60. Dandrau A (1999) La peinture murale minoenne. I. La palette du peintre égéen et égyptien à l'Age du Bronze. Nouvelles données analytiques. Bull de corresp hellénique 123:1–41

    Article  Google Scholar 

  61. Gettens RJ, Duell P (1942) A review of the problem of Aegean wall painting. Tech Stud Field Fine Arts 10:179–223

    Google Scholar 

  62. Jones RE (2011). Representation in the Aegean: progress towards understanding materials and technology, In J. Bennet, ed. Representation in the Aegean Bronze Age, Sheffield Archaeological Press, Sheffield, UK (in press)

  63. Seidel E, Kreuzer H, Harre W (1982) A Late Oligocene/Early Miocene high pressure belt in the External Hellenides. Geol Jb E23:165–206

    Google Scholar 

Download references

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.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Demetrios Anglos.

Additional information

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

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

ESM 1

(PDF 46.1 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

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

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-011-5281-z

Keywords

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