Skip to main content
SpringerLink
Log in

FTIR imaging and HPLC reveal ancient painting and dyeing techniques of molluskan purple

  • Original Paper
  • Published:
Archaeological and Anthropological Sciences Aims and scope Submit manuscript

Abstract

Fourier transform infrared spectroscopy and imaging coupled to optical microscopy, scanning electron microscopy coupled to energy dispersive x-ray spectroscopy and high-performance liquid chromatography (HPLC) coupled to diode-array detection are used to investigate two samples removed from a painted decoration of a burial kline and a textile fragment, both found in Koru tumulus (fifth century BCE) in Daskyleion. Tyrian purple and kaolinite were identified in both samples, thus suggesting that the aluminosilicate compound had an important role in the applied painting and dyeing processes. The textile fragment is composed of undyed cotton and silk yarns dyed with the molluskan dye. The relative compositions of the molluskan materials used in the two archaeological objects are similar and comparable with the corresponding composition measured for a purple sample originated from Murex trunculus mollusks according to the HPLC results. This result is supported by principal component analysis (PCA) which, furthermore, takes into account the relative compositions of the extracts of the three Mediterranean mollusks, published in previous reports.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

References

  • Andreotti A, Carmignani A, Colombini MP, Modugno F (2006) Characterization of paint organic materials in wall decorations of Macedonian tombs. In: Brecoulaki H (ed) La peinture funeraire de macedoine, emplois et fonctions de la couleur IVe-IIe s av J-C Vol ΙΙ: planches & tableaux, Appendix IV. National Hellenic Research Foundation, Athens

    Google Scholar 

  • Cardon D (2007) Natural dyes—sources, tradition, technology and science. Archetype Publications Ltd., London

    Google Scholar 

  • Clark RJH, Cooksey CJ (1999) Monobromoindigos: a new general synthesis, the characterization of all four isomers and an investigation into the purple colour of 6,6′-dibromoindigo. New J Chem 323–328

  • Colombini MP, Carmignani A, Modugno F, Frezzato F, Olchini A, Brecoulaki H, Vassilopoulou V, Karkanas P (2004) Integrated analytical techniques for the study of ancient Greek polychromy. Talanta 63:839–48

    Article  Google Scholar 

  • Cook JG (1993) Handbook of textile fibres I. Natural fibres. Merrow Publishing Co, Wiltshire

    Google Scholar 

  • Derrick MR, Stulik D, Landry JM (1999) Infrared spectroscopy in conservation science, scientific tools for conservation. The Getty conservation institute, Los Angeles

    Google Scholar 

  • Friedländer P (1909) Den farbstoff des antiken purpurs aus Murex brandaris. Ber Dtsch Chem Ges 42:765–770

    Article  Google Scholar 

  • Graves PH, Saville BP (1995) Microscopy of textile fibres. Bios Scientific Publishers, Oxford

    Google Scholar 

  • İren K (2012) Dascyleum. A multicultural society in the shadow of Persia. Curr World Archaeol 54:49–51

    Google Scholar 

  • İren K (2013) Daskyleion. In: Bagnall RS, Brodersen K, Champion CB, Erskine A, Huebner SR (eds) The encyclopedia of ancient history, 1st ed, Wiley-Blackwell, pp1930–31

  • Kakoulli I (2002) Late Classical and Hellenistic painting techniques and materials: a review of the technical literature. Rev Conserv 3:56–67

    Google Scholar 

  • Karapanagiotis I, Sotiropoulou S, Chryssikopoulou E, Magiatis Pr, Andrikopoulos KS, Chryssoulakis Y (2004) Investigation of Tyrian purple occurring in historical wall paintings of Thera. Dyes Hist Archaeol Proceedings of the 23rd DHA meeting, Montpellier, in press

  • Karapanagiotis I, de Villemereuil V, Magiatis P, Polychronopoulos P, Vougogiannopoulou K, Skaltsounis AL (2006) Identification of the coloring constituents of four natural indigoid dyes. J Liq Chromatogr Relat Technol 29:1491–502

    Article  Google Scholar 

  • Karapanagiotis I, Mantzouris D, Cooksey C, Mubarak MS, Tsiamyrtzis P (2013) An improved HPLC method coupled to PCA for the identification of Tyrian purple in archaeological and historical samples. Microchem J 110:70–80

    Article  Google Scholar 

  • Karydas AG (2006) In situ XRF analyses of wall-painting pigments on ancient funeral Macedonian monument. In: Brecoulaki H (ed) La peinture funeraire de macedoine, emplois et fonctions de la couleur IVe-IIe s av J-C vol ΙΙ: planches & tableaux, Appendix IV. National Hellenic Research Foundation, Athens

    Google Scholar 

  • Kavkler K, Gunde-Cimerman N, Zalar P, Demsar A (2011) FTIR spectroscopy of biodegraded historical textiles. Polym Degrad Stabil 96:574–80

    Article  Google Scholar 

  • Koren ZC (1995) High-performance liquid chromatographic analysis of an ancient Tyrian purple dyeing vat from Israel. Isr J Chem 35:117–24

    Article  Google Scholar 

  • Koren ZC (2008) Archaeo-chemical analysis of royal purple on a Darius I stone jar. Microchim Acta 162:381–92

    Article  Google Scholar 

  • Luniak B (1953) The identification of textile fibers. Sir Isaac Pitman & Sons, London

    Google Scholar 

  • Mantzouris D, Karapanagiotis I (2014) Identification of indirubin and monobromoindirubins in Murex brandaris. Dyes Pigm 104:194–96

    Article  Google Scholar 

  • Mantzouris D, Karapanagiotis I, Valianou L, Panayiotou C (2011) HPLC-DAD-MS analysis of dyes identified in textiles from Mount Athos. Anal Bioanal Chem 399:3065–79

    Article  Google Scholar 

  • Maravelaki-Kalaitzaki P, Kallithrakas-Kontos N (2003) Pigment and terracotta analyses of Hellenistic figurines in Crete. Anal Chim Acta 497:209–25

    Article  Google Scholar 

  • Margariti C, Protopapas S, Allen N, Vishnyakov V (2013) Identification of purple dye from molluscs on an excavated textile by non-destructive analytical techniques. Dyes Pigm 96:774–80

    Article  Google Scholar 

  • McGovern PE, Michel RH (1990) Royal purple dye: the chemical reconstruction of the ancient Mediterranean industry. Accounts Chem Res 23:152–58

    Article  Google Scholar 

  • Michel RH, Lazar J, McGovern PE (1992a) The chemical composition of the indigoid dyes derived from the hypobranchial glandular secretions of Murex mollusks. J Soc Dyers Colour 108:145–50

    Article  Google Scholar 

  • Michel RH, Lazar J, McGovern PE (1992b) Indigoid dyes in Peruvian and Coptic textiles of the University Museum of Archaeology and Anthropology. Archeomaterials 6:69–83

    Google Scholar 

  • Nour WMN, Awad HM (2008) Effect of MgO on phase formation and mullite morphology of different Egyptian clays. J Aust Ceram Soc 44:27–37

    Google Scholar 

  • Nowik W, Marcinowska R, Kusyk K, Cardon D, Trojanowicz M (2011) High performance liquid chromatography of slightly soluble brominated indigoids from Tyrian purple. J Chromatogr A 1218:1244–52

    Article  Google Scholar 

  • Serrano A, Sousa MM, Hallett J, Lopes JA, Oliveira MC (2011) Analysis of natural red dyes (cochineal) in textiles of historical importance using HPLC and multivariate data analysis. Anal Bioanal Chem 401:735–43

    Article  Google Scholar 

  • Sotiropoulou S, Karapanagiotis I (2006) Conchylian purple investigation in prehistoric wall paintings of the Aegean area. In: Meijer L, Guyard N, Skaltsounis AL, Eisenbrand G (eds) Indirubin the red shade of indigo. Life in Progress Editions. Roscoff, pp 71–78

    Google Scholar 

  • Sousa MM, Melo MJ, Parola AJ, de Melo JSS, Catarino F, Pina F, Cook FEM, Simmonds MSJ, Lopes JA (2008) Flavylium chromophores as species markers for dragon’s blood resins from Dracaena and Daemonorops trees. J Chromatogr A 1209:153–61

    Article  Google Scholar 

  • Westenholz JG, Stolper MW (2002) A stone jar with inscriptions of Darius I in four languages. Arta 005:1–13

    Google Scholar 

  • Wouters J (1992) A new method for the analysis of blue and purple dyes in textiles. Dyes Hist Archaeol 10:17–21

    Google Scholar 

  • Wouters J (2001) The dye of Rubia peregrina—preliminary investigations. Dyes Hist Archaeol 16(17):145–57

    Google Scholar 

  • Wouters J, Verhecken A (1989) The coccid insect dyes: HPLC and computerized diode-array analysis of dyed yarns. Stud Conserv 34:189–200

    Google Scholar 

  • XiaoMei Z, Paul W (2010) Using FTIR spectroscopy to detect sericin on historic silk. Sci China Chem 53:626–31

    Google Scholar 

Download references

Acknowledgement

The authors would like to thank Dimosthenis Kechagias for his help in the identification of cotton.

Author information

Authors and Affiliations

  1. Elettra Sincrotrone Trieste S.C.p.A., AREA Science Park, Basovizza, Trieste, Italy

    Zoi Eirini Papliaka

  2. Department of Management and Conservation of Ecclesiastical Cultural Heritage Objects, University Ecclesiastical Academy of Thessaloniki, Thessaloniki, Greece

    Alexandros Konstanta & Ioannis Karapanagiotis

  3. Laboratory for Natural Dyes, Marmara University, Istanbul, Turkey

    Recep Karadag

  4. Turkish Cultural Foundation, Cultural Heritage Preservation and Natural Dyes, Istanbul, Turkey

    Recep Karadag

  5. Department of Conservation & Restoration of Cultural Properties, Gazi University-Faculty of Fine Arts, Ankara, Turkey

    Ali Akin Akyol

  6. Ormylia Foundation, Art Diagnosis Center, Ormylia, Greece

    Dimitrios Mantzouris

  7. Department of Statistics, Athens University of Economics and Business, Athens, Greece

    Panagiotis Tsiamyrtzis

Authors
  1. Zoi Eirini Papliaka
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Alexandros Konstanta
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ioannis Karapanagiotis
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Recep Karadag
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ali Akin Akyol
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dimitrios Mantzouris
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Panagiotis Tsiamyrtzis
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ioannis Karapanagiotis.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Papliaka, Z.E., Konstanta, A., Karapanagiotis, I. et al. FTIR imaging and HPLC reveal ancient painting and dyeing techniques of molluskan purple. Archaeol Anthropol Sci 9, 197–208 (2017). https://doi.org/10.1007/s12520-015-0270-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12520-015-0270-3

Keywords

Search

Navigation