Background: The commercial obsidian trade played an important role during Neolithic period. Its characteristics favoured the exchange network. In this way the Mediterranean area was fundamental. The availability of significant numbers of obsidian samples has allowed to improve the knowledge about the trade and commercial routes. Obsidian samples from the Mediterranean (Aegean, Flegrean, North Latium, Sicily, Sardinia) and Near East (Anatolia) areas were directly collected on the sites and considered as reference. Almost 30 elements were analyzed by Instrumental Neutron Activation Analysis (INAA). Results: The approach based on the source discrimination analysis allowed to identify clearly different obsidian deposits, except the reference samples coming from Flegrean and Sicily areas, quite similar for their geochemical origin. The obtained data were used for assigning the provenance of 71 obsidian artefacts found during archaeological excavations in Tuscany. Two different groups were found: 16 artefacts were attributed to Sicily/Flegrean area whereas 55 items seemed to show a provenance from Aegean. Conclusions: The results are important because they represents a confirmation about the hypothesis of the existence of a large exchange network in the Mediterranean area since 3000 B.C.
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