Lead, zinc, and copper redistributions in soils along a deposition gradient from emissions of a Pb-Ag smelter decommissioned 100 years ago.

Sourcing and understanding the fate of anthropogenic metals in a historical contamination context is challenging. Here we combined elemental and isotopic (Pb, Zn, Cu) analyses with X-ray Absorption Spectroscopy (XAS) measurements (Zn) to trace the fate, in undisturbed soil profiles, of historical metal contamination emitted by a 167-year-old Pb-Ag smelter decommissioned 100 years ago located in the Calanques National Park (Marseilles, France). Lead isotopic measurements show that entire soil profiles were affected by 74 years of Pb emissions up to ~7 km from the smelter under the main NNW wind, and indicate particulate transfer down to 0.8 m at depth. This vertical mobility of anthropogenic Pb contrasts with previous studies where Pb was immobilized in surface horizons. The contribution of anthropogenic Pb to the total Pb concentration in soil was estimated at 95% in surface horizons, and 78% in the deepest horizons. Zinc isotopic signatures of past emissions that are enriched in light isotopes compared to the natural geological background (-0.70 ± 0.04‰ and -0.15 ± 0.02‰, respectively), were detected only in the surface horizons of the studied soils. Using XAS analyses, we showed that anthropogenic Zn was transformed and immobilized in surface horizons as Zn-Layered Double Hydroxide, thus favoring the enrichment in heavy isotopes in these surface horizons. No clear evidence of copper contamination by the smelter was found and Cu isotopes point to a bedrock origin and a natural distribution of Cu concentrations.