Atmospheric Pb pollution in N Iberia during the late Iron Age/Roman times reconstructed using the high-resolution record of La Molina mire (Asturias, Spain)

Extensive mining took place in Spain during the Iron Age and Roman times, although a detailed chronology is still lacking due to the inherent difficulties in dating mining structures. In this study we sampled and analyzed a core from La Molina mire in the Asturias region, northern Spain. Because more than 100 Roman mines have thus far been found within 20 km of the mire, our aim was to shed light on local mining history, which we can then compare to the wider narrative of early mining pollution in Spain. We focus on the section from ~500 BC to AD ~600, which has a high temporal resolution of 6-15 year per sample. Geochemical analyses included the determination of major, minor and trace lithogenic elements (Si, Al, Fe, Ti, Ga, Rb, Y, Zr, Th) as markers of mineral content of the peat, and trace metals/metalloids (Mn, Cu, Ni, As, Pb) as well stable Pb isotopes, as potential markers of atmospheric metal pollution. The use of principal components analysis enabled the identification of a dominant geogenic component and a secondary pollution component. The earliest pollution signal of the covered period was recorded by ~300 BC, coinciding with the late local Iron Age. Average Pb/Pb ratios of samples with ages older than this date was 1.204 ± 0.002, while all samples with a younger age had a less radiogenic ratio. Based on the metal pollution component four phases were identified: I, ~500 to 300 BC; II, ~300 to 20 BC; III, ~20 BC-AD 480; IV, AD ~480 to 600. The lowest isotopic ratio and highest proportion of pollution Pb (Pb/Pb ratio of 1.157 and 89 % of total accumulated Pb) was reached at peak Pb production during Roman times (AD ~180 to 340), indicating that this was the period of most intense metal contamination in the area over the studied period. It is remarkable that the La Molina record shows a more extended period (two centuries) of active mining in comparison with other areas in Iberia, and a pattern of repeated shifts in Pb pollution of short duration, which is likely related to the local history of exploitation and exhaustion of mines within the area.