Although archaeological research suggests that mining/metallurgy already started in the Chalcolithic (3rd millennium BC), the earliest atmospheric metal pollution in SW Europe has thus far been dated to similar to 3500-3200 cal. yr. BP in paleo-environmental archives. A low intensity, non-extensive mining/metallurgy and the lack of appropriately located archives may be responsible for this mismatch. We have analysed the older section (>2100 cal. yr. BP) of a peat record from La Molina (Asturias, Spain), a mire located in the proximity (35-100 km) of mines which were exploited in the Chalcolithic/Bronze Age, with the aim of assessing evidence of this early mining/metallurgy. Analyses included the determination of C as a proxy for organic matter content, lithogenic elements (Si, Al, Ti) as markers of mineral matter, and trace metals (Cr, Cu, Zn, Pb) and stable Pb isotopes as tracers of atmospheric metal pollution. From similar to 8000 to similar to 4980 cal. yr. BP the Pb composition is similar to that of the underlying sediments (Pb 15 +/- 4 mu g g(-1); Pb-206/Pb-207 1.204 +/- 0.002). A sustained period of low Pb-206/Pb-207 ratios occurred from similar to 4980 to similar to 2470 cal. yr. BP, which can be divided into four phases: Chalcolithic (similar to 4980-3700 cal. yr. BP), Pb-206/Pb-207 ratios decline to 1.175 and Pb/Al ratios increase; Early Bronze Age (similar to 3700-3500 cal. yr. BP), Pb-206/Pb-207 increase to 1.192 and metal/Al ratios remain stable; Late Bronze Age (similar to 3500-2800 cal. yr. BP), Pb-206/Pb-207 decline to their lowest values (1.167) while Pb/Al and Zn/Al increase; and Early Iron Age (similar to 2800-2470 cal. yr. BP), Pb-206/Pb-207 increase to 1.186, most metal/Al ratios decrease but Zn/Al shows a peak. At the beginning of the Late Iron Age, Pb-206/Pb-207 ratios and metal enrichments show a rapid return to pre-anthropogenic values. These results provide evidence of regional/local atmospheric metal pollution triggered by the earliest phases of mining/metallurgy in the area, and reconcile paleo-environmental and archaeological records.