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

Koupadi Kyriaki

Abstracts

This poster presents the physicochemical analysis results of the organic residues from copper alloy artifacts dated between 5th and 7th cent. A.D. FT-IR and GC–MS were used to identify the composition of the residues. Biomarkers of pine resins were identified in one sample, while a broad range of oils and fats, along with their degradation products, were identified in all samples and associated with the presence of vegetable oil extracted from plants of the Brassicaceae family.

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Full text

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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Bibliography

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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Attachment

  • kyriaky (application/pdf – 1.1M)
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List of illustrations

Title Fig.1 Table and scheme
Caption Left: table summarizing information about the objects and the samples (Table 1). Right: scheme showing the adopted methodology (Figure 1).
URL http://ceroart.revues.org/docannexe/image/5127/img-1.jpg
File image/jpeg, 260k
Title Fig.2 Summary
Caption 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://ceroart.revues.org/docannexe/image/5127/img-2.jpg
File image/jpeg, 621k
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References

Electronic reference

Koupadi Kyriaki, « Study of organic residues in vessels of archaeological origin with physicochemical analytical techniques », CeROArt [Online], HS | 2017, Online since 01 June 2017, connection on 25 September 2017. URL : http://ceroart.revues.org/5127

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About the author

Koupadi Kyriaki

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

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Copyright

Licence Creative Commons
CeROArt – Conservation, exposition, restauration d'objets d'arts est mis à disposition selon les termes de la licence Creative Commons Attribution - Pas d'Utilisation Commerciale - Pas de Modification 4.0 International.

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