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Obsidians are natural glasses wildly used in prehistoric lithic industry. We studied the structure by Raman spectroscopy of four obsidians representing calc-alkaline and peralkaline compositions. Silicate networks appear particularly well defined, remarkably polymerised even if various amounts of alkali allow one to establish various degrees of Structural signatures obtained are especially sensitive to compositional variations whereas heat treatments performed show a great stability of the vitreous structure. Micro-Raman spectroscopy also allowed us the mineralogical determination of many micro-inclusions, present however in a very vitreous obsidian. The parameters provided by Raman spectroscopy makes it possible to consider structural signatures applied to provenance studies.
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