Francesca Cannizzaroa, Lorenzo Cucinottaa, Giuseppe Micalizzia, Valentina Chiaiaa, Paola Cardianob, Danilo Sciarronea, Luigi Mondelloa,c

aMessina Institute of Technology c/o Department of Chemical, Biological, Pharmaceutical and Environmental Sciences, former Veterinary School, University of Messina, Viale G. Palatucci snc 98168, Messina, Italy
bDepartment of Chemical, Biological, Pharmaceutical and Environmental Sciences, University of Messina, Viale Ferdinando Stagno d'Alcontres, 31 98166, Messina, Italy
cChromaleont S.R.L., C/O Department of Chemical, Biological, Pharmaceutical and Environmental Sciences, Former Veterinary School, University of Messina, Viale G. Palatucci snc 98168, Messina, Italy

In the field of archaeological investigation, the analysis of organic residues from vessels can provide a variety of archaeological information about diet, food storage, and processing. According to the literature [1], lipids represent the most common class of organic residue observed in archaeological pottery. The resistance to decay makes lipids ideal candidates as “archaeological biomarkers” that can provide valuable information about past human activity. In this study, sixteen samples retrieved from the Bobinac-Kozerina Cave (Lika, Croatia) underwent the lipid extraction step followed by the derivatization before gas chromatographic analyses.  In the first step, total fatty acids composition was elucidated by using gas chromatographic techniques coupled to mass spectrometry (GC-MS). Secondly, a heart-cutting multidimensional gas chromatography (MDGC) approach was implemented, before isotopic ratio mass spectrometry (IRMS) and MS detection, for the analysis of the δ13C values of the major trimethylsilyl (TMS) derivatized fatty acids (C16:0 and C18:0) on selected vessels. Since the TMS group introduced into each fatty acid during derivatization contributes to the isotopic composition, a correction was applied to determine the true δ13C value of each fatty acid. Due to the reduced sensitivity of IRMS, this work aimed to overload the first chromatographic dimension in order to select only the peaks of interest by heart-cut and transfer them to the second chromatographic dimension. Investigations of the δ13C values of the most abundant fatty acids in ancient pottery provided a clear distinction between ruminant and non-ruminant fats. In detail, lipid residue results from MDGC-C-IRMS/qMS analyses suggested that eleven of the sixteen vessels analysed were predominantly used to process ruminant dairy products. Four further samples clustered near the range of the ruminant adipose fats value and only one sample showed isotopic values of C16:0 and C18:0 that match those of non-ruminants.

Acknowledgements: This project is part of the PhD scholarship in Chemical Sciences, funded on the basis of the former Ministerial Decree 118/2023, in the field of Cultural Heritage, awarded to Dr. Francesca Cannizzaro, currently in the first year of her PhD.

Keywords: pottery, organic residue, multidimensional gas chromatography, isotopic ratio mass spectrometry

References

1. Evershed R.P., Archaeometry, 50 (2008), pag. 895-924. DOI: 10.1111/j.1475-4754.2008.00446.x