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.
Similar content being viewed by others
References
Price TD, Burton JH (2011) An introduction to archaeological chemistry. Springer, New York
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
Uda M, Demortier G, Nakai I eds (2005) X-rays for Archaeology, Springer, London
Stuart BH (2007) Analytical techniques in art conservation. Wiley, West Sussex, UK
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
Janssens K (2011) Synchrotron radiation in art and archaeology. J Anal At Spectrom 26:833–834
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
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
Brysbaert A (2008) The power of technology in the Bronze Age Eastern Mediterranean. Monographs in Mediterranean Archaeology, Equinox, London
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
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
Anglos D (2001) Laser-induced breakdown spectroscopy in art and archaeology. Appl Spectrosc 55:186A–205A
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
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
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
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
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
Smith GD, Clark RJH (2004) Raman microscopy in archaeological science. J Archaeol Sci 31:1137–1160
Vandenabeele P, Edwards HGM, Moens L (2007) A decade of Raman spectroscopy in art and archaeology. Chem Rev 107:675–686
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
Ioakimoglou E (2010) Organic materials in art and archaeology vol. B: Proteinaceous materials in painting (in Greek). Ion editions, Athens, pp. 192–195
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
Eastaugh N, Walsh V, Chaplin T, Siddall R (2004) The pigment compendium: a dictionary of historical pigments. Elsevier Butterworth-Heinemann, Oxford
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
Bailey K (1929) The Elder Pliny's chapters on chemical subjects. Part I. Edward Arnold & Co, London
Bailey K (1932) The Elder Pliny's chapters on chemical subjects. Part II. Edward Arnold & Co, London
Vitruvius (1960) The ten books on architecture. (trans: Morgan MH). Dover Publications, New York
Augusti S (1967) I colori pompeiani. De Luca Editore, Rome
Cennino D' Andrea Cennini (1960) The Craftsman's handbook. The Italian "Il Libro dell' Arte". (trans: Thompson DV). Dover Publications, New York
Mazzocchin GA, Agnoli F, Salvadori M (2004) Analysis of Roman Age wall paintings found in Pordenone, Trieste and Montegrotto. Talanta 64:732–741
Calamiotou M, Siganidou M, Filippakis SE (1983) X-ray analysis of pigments from Pella, Greece. Stud Conserv 28:117–121
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
Siddall R (2006) Not a day without a line drawn: pigments and painting techniques of Roman artists. Proc R Microsc Soc 2:18–31
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
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
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
Filippakis SE, Perdikatsis B, Paradelis Th (1976) An analysis of blue pigments from Greek Bronze Age. Stud Conserv 21:143–153
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
Profi S, Perdikatsis B, Filippakis SE (1977) X-ray analysis of Greek Bronze Age pigments from Thera (Santorini). Stud Conserv 22:107–115
Filippakis SE, Petrakis A, Assimenos K (1979) X-ray analysis of pigments from Vergina (second tomb). Stud Conserv 24:54–58
Mirtsou E, Kesisoglou M, Michailidis K (1985) Ανάλυση χρωμάτων και κονιαμάτων μακεδονικού τάφου της περιοχής Λευκαδιών. Ανθρωπολογικά 8:47–51
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
Bearat H (1996) Chemical and mineralogical analyses of Gallo-Roman wall painting from Dietikon, Switzerland. Archaeometry 38:81–95
Gillis KM, Robinson PT (1985) Low temperature alteration of the extrusive sequence, Troodos ophiolite Cyprus. Can Miner 23:431–441
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
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
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
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
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
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
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.
Mazzocchin GA, Agnoli F, Mazzocchin S, Colpo I (2003) Analysis of pigments from Roman wall paintings found in Vicenza. Talanta 61:565–572
De La Rie E (1982) Fluorescence of paint and varnish layers (Part III). Stud Conserv 27:102–108
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
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
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
Cameron MAS, Jones RE, Filippakis SE (1977) Analysis of fresco samples from Knossos. Ann Br Sch Athens 72:123–184
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
Perdikatsis V (1995) Analysis of pigments from ancient Greek art monuments, in Proc. Scientific Symp. Art and Technology (Athens 1993), Athens, pp 272–280
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
Gettens RJ, Duell P (1942) A review of the problem of Aegean wall painting. Tech Stud Field Fine Arts 10:179–223
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)
Seidel E, Kreuzer H, Harre W (1982) A Late Oligocene/Early Miocene high pressure belt in the External Hellenides. Geol Jb E23:165–206
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
Corresponding author
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
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
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-011-5281-z