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The Etruscan site of Populonia-Baratti (Southern Tuscany, Italy) became in the first millennium BCE one of the most important iron metalworking sites in the Mediterranean region thanks to the exploitation of nearby Elba Island iron ores. Recent studies, however, have demonstrated that, before iron, copper was smelted therein (9th–8th century BCE). The ancient Hellenistic text De mirabilibus auscultationibusby Pseudo-Aristotle states that the ancient inhabitants of Elba Island firstly exploited copper and that, later in, iron was won from the same mines by the inhabitants of Populonia. However, copper occurrences are extremely scanty on the island, while mainland southern Tuscany hosts a number of copper-rich deposits which could have been profitably exploited since Eneolithic. In order to investigate if, and to what extent, copper mining and smelting/working was practiced in this area in Final Bronze Age (FBA) to Early Iron Age (EIA), we have thus compared the lead isotope composition of copper slags found in the Populonia-Baratti area and dated to the 9th–8th century BCE with those of copper-rich ore deposits of southern Tuscany and Elba Island. In addition, few copper-based items from to FBA-EIA hoards of Elba Island have been investigated as well. All copper slag from Baratti-Populonia have lead isotope composition fully comprised within the nearby Campiglia Marittima district, but the ophiolitic copper (either form Tuscan mainland or the neighboring island of Elba) was never worked in this site. Differently, all items from the island of Elba do not show clear genetic relationship neither with Elban nor with the Tuscan mainland copper ores but display a “foreign” Pb signature, suggesting that, even before iron exploitation started, the island of Elba - one of the main crossroads of the Mediterranean Sea - was probably involved in metal trading (rather than metal working) with other regions.