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Study of organic residues in vessels of archaeological origin with physicochemical analytical techniques

Koupadi Kyriaki

Résumés

Ce poster présente les résultats d'analyse physicochimique des résidus organiques d'artefacts en alliage de cuivre, datés entre le 5e et le 7e siècle apr. J.-C.. L'IRTF et  GC-MS ont été utilisés pour l'identification de la composition des résidus. Des marqueurs biologiques de résine de pin ont été identifiés dans un des échantillons, tandis qu’une large gamme d'huiles et des graisses, avec leurs produits de dégradation, ont été identifiées dans tous les échantillons et associées avec la présence d'huile végétale extraite des plantes de la famille des Brassicacées.    

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Texte intégral

The thesis was conducted and presented at the Dept. of Conservation of Antiquities and Works of Art, Technological Educational Institute of Athens; supervised by Prof. S. C. Boyatzis. Information on the samples and the objects were provided by Ms D. Kotzamani, conservator at the «Laboratory for Metal, Glass and Bone Artifacts Conservation» of Benaki Museum. Part of the experimental work was conducted at the Dept. of Nutrition & Dietetics of Harokopio University of Athens; supervisory assistance on GC-MS sample workup and GC-MS runs was offered by Dr. M. Roumpou and Prof. N. Kalogeropoulos.

Vessels & Samples

1A number of copper alloy vessels were selected from the Byzantine Collection of the Benaki Museum in Athens (128 artifacts, purchased from Egyptian markets by the museum’s founder, A. Benakis, during the early 20th century, Kotzamani et al. 2011) As there was no archaeological record of these objects, all information listed in the table below originates from the Doctoral Thesis of Dr Drandaki (Drandaki 2008), curator of the Byzantine Collection at the Benaki museum. (ill.1: Table1: Information about vessels and samples)

Fig.1 Table and scheme

Fig.1 Table and scheme

Left: table summarizing information about the objects and the samples (Table 1). Right: scheme showing the adopted methodology (Figure 1).

Methodology

2The scheme above illustrates the experimental procedures for sample workup and analysis. (ill.1: Figure1: Methodology of sample preparation and analysis procedures)

Results

Fig.2 Summary

Fig.2 Summary

Top, left: Summary of the results obtained through FTIR spectroscopy (Table 2). Top, right: FTIR spectra obtained after the extraction with acetone (Figure 2). Bottom, left: Bar chart illustrating the detected main components of all samples through GC-MS analysis (Figure 3). Bottom, right: Representative gas chromatogram of the sample #11622 (Figure 4).

GC-MS Results

3The identified main components using GC-MS analysis of derivatised samples are:

  • glycerol along with C16 and C18 monoacyloglycerols

  • a wide variety of even numbered saturated fatty acids ranging from C8 to C26, as well as two odd numbered saturated fatty acids (C9 and C15)

  • hydroxy- and dihydroxy- fatty acids: 2- hydroxy-heptanoic (C7(2-OH):0), 9,10-dihydroxy-octadecanoic acid (C18 (9,10-diOH):0), 13,14-dihydroxydocosanoic acid (C22 (13,14-diOH):0

  • a series of linear dicarboxylic acids, both even and odd numbered: C4 to C14.
    • β-sitosterol is also present in a number of samples

  • a wide variety of two different hydrocarbon types, Cv1H2v1 and Cv2H2v2-1, with v1 ranging from 28 to 31 and v2 ranging from 43 to 49 in some of the samples

  • markers for oxidative degradation of pine resin: dehydroabietic, 7-hydroxy-/ 7-oxo -/ dehydroabietic, in sample 11622A (Figure 4: Bar chart illustrating the main components of each sample and their quantity)

Conclusions

4The compounds found in the samples were identified as

  • Oils collected from plants (Colombini et al. 2005, Evershed 2008, Evershed et al. 2001) of the Brassicaceae family in all samples

  • Degradation products of castor oil (Colombini et al. 2005) in samples 11550, 11596,11544

  • Fats (Mills et al. 1999) of unknown origin in sample 11544

  • Pine resin biomarkers (Serpico et al. 2000) in sample11622A

  • The results provide considerable help for the conservator, in order to choose a suitable conservation treatment for the artifacts

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Bibliographie

Kotzamani D., Phoca A., Karydi G., Zacharia M., Kantarelou V., Karatasios G., Boyatzis S. C. and Perdikatsis V., “The Metallurgical Investigation of Copper-Alloys Metalwork of the Benaki Museum Dated in the 4th-7th Centuries A.D.”, History, Technology and Conservation of Ancient Metal, Glasses and Enamels International Symposium, Athens 2011, oral presentation

Drandaki Α., (2008), Bronze vessels of the Late Antiquity: technique, typology, use, terminology according to the collection of the Benaki Museum, PhD dissertation

Colombini M. P., Modugno Fr., Ribechini E, (2005), “Organic mass spectrometry in archaeology: evidence for Brassicaceae seed oil in Egyptian ceramic lamps”, Journal of Mass Spectrometry, 40, 891,892

Evershed R.P., (2008), Organic residue analysis in archaeology: the archaeological biomarker revolution, Archaeometry, 50: 7, 895–924

Evershed R. P., Dudd St N., Copley M. S., Berstan R., Stott A. W, Mottram H., Buckley St. A., Crossman Z., (2001), Chemistry of Archaeological Animal Fats, Accounts of Chemical Research, 35: 661

Mills J., White R., (1999), Organic Chemistry of Museum Objects (Conservation and Museology), Routledge, 31-55, 95-128

Serpico M., White R, (2000), Ancient Egyptian Materials and Technology, Nicholson P, Shaw I (eds). Cambridge University Press, 390-405

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Document annexe

  • kyriaky (application/pdf – 1,1M)
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Table des illustrations

Titre Fig.1 Table and scheme
Légende Left: table summarizing information about the objects and the samples (Table 1). Right: scheme showing the adopted methodology (Figure 1).
URL http://journals.openedition.org/ceroart/docannexe/image/5127/img-1.jpg
Fichier image/jpeg, 260k
Titre Fig.2 Summary
Légende Top, left: Summary of the results obtained through FTIR spectroscopy (Table 2). Top, right: FTIR spectra obtained after the extraction with acetone (Figure 2). Bottom, left: Bar chart illustrating the detected main components of all samples through GC-MS analysis (Figure 3). Bottom, right: Representative gas chromatogram of the sample #11622 (Figure 4).
URL http://journals.openedition.org/ceroart/docannexe/image/5127/img-2.jpg
Fichier image/jpeg, 621k
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Référence électronique

Koupadi Kyriaki, « Study of organic residues in vessels of archaeological origin with physicochemical analytical techniques »CeROArt [En ligne], HS | 2017, mis en ligne le 01 juin 2017, consulté le 18 avril 2024. URL : http://journals.openedition.org/ceroart/5127 ; DOI : https://doi.org/10.4000/ceroart.5127

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Auteur

Koupadi Kyriaki

Department of Antiquities and Works of Art Conservation, TEI of Athens. domkoup.k@gmail.com/ koupadikrk@gmail.com)

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