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Laser microsampling and multivariate methods in provenance studies of obsidian artefacts

Lubomír Prokeš, Michaela Vašinová Galiová, Simona Hušková, Tomáš Vaculovič, Aleš Hrdlička, Andrew Zed Mason, Hector Neff, Antonín Přichystal, and Viktor Kanický

Department of Chemistry, Masaryk University, Kotlařska 2, 611 37 Brno, Czech Republic



Abstract: The provenance of obsidian artefacts and raw materials was studied by the multivariate statistical analysis of forty-five samples using elemental composition data obtained by laser ablationinductively coupled plasma-mass spectrometry (LA-ICP-MS). One ICP-MS instrument equipped with a quadrupole mass filter and the other based on a time-of-flight analyser were coupled to the same type of laser ablation device (Nd:YAG 213 nm), thereby affording a comparison of the different mass spectrometers in terms of precision and verification of the consistency of the results. The influence of surface roughness (polished raw material vs artefact) and microinhomogeneity on the LA-ICP-MS signal was studied under the optimised working conditions of the laser ablation device. Principal component analysis, correspondence analysis, independent component analysis, multi-dimensional scaling, Sammon mapping and fuzzy cluster analysis were applied and compared in order to reveal statistically significant compositional differences between particular geological sites and to disclose the provenance of the raw materials used in manufacture of the artefacts. Twenty-seven artefacts and eighteen raw material samples from natural resources in the Czech Republic, Slovakia, Italy, Greece, Syria, Iraq, Turkey, Mexico and Nicaragua were examined with special attention focused on samples from Moravia (Czech Republic) and some Near East sites (Tell Arbid, Tell Asmar). The Carpathian origin of the obsidian artefacts was investigated in the Moravian samples using the Pb, Rb and U contents. The Near East samples were classified according to their Sr, Ba, Zr and REE contents as per-alkaline obsidians (Bingöl A/Nemrut Dağ) originating from Southeast Anatolia.

Keywords: ICP-MS – laser beam sampling – principal component analysis – correspondence analysis – archaeological objects – volcanic glasses

Full paper is available at

DOI: 10.1515/chempap-2015-0019


Chemical Papers 69 (6) 761–778 (2015)

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