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 ±â€¯0.04‰ and -0.15 ±â€¯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.

Tracing contamination sources in soils with Cu and Zn isotopic ratios.

Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case.