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

Abstract

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 soils 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 (-0.69 ±0.03‰ 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. Highlights: • δPb, Zn, Cu in soils impacted by emissions 100 y ago from a smelter • Pb contamination was detected 7 km away from the smelter and down the soil profiles • Light δ 66 Zn values were measured in the chimney and in soil surface horizons • Precipitation of Zn-Layered Double Hydroxide prevented downwards migration of anthropogenic Zn • Cu isotopes indicate its geogenic origin and redistribution in soils by pedogenesis

Advances and limits of two model species for ecotoxicological assessment of carbamazepine, two by-products and their mixture at environmental level in freshwater

“…This activity generated massive Pb and Zn-rich slags (Gelly et al, 2019;Testiati et al, 2013) and atmospheric emissions of highly metal-concentrated particles, specifically with Pb, As and Sb (Laffont-Schwob et al, 2016;Testiati et al, 2013). Previous studies highlighted the metal and metalloid contaminations of the smelter surroundings, in particular by Pb, As, Sb and Zn (Heckenroth et al, 2016;Affholder et al, 2013;Testiati et al, 2013;Gelly et al, 2019). Eight sites were selected having similar soil characteristics, vegetation and climatic conditions and included in the National Park of Calanques.…”

“…Pseudo-metallophytes are plants found both in TMM polluted and non-polluted areas, but the phenotypic adaptations to TMM are far less understood (Salducci et al, 2019). Rosmarinus officinalis L., a perennial plant species native to the Mediterranean is able to grow in soils with high levels of TMM contamination (Testiati et al, 2013;Gelly et al, 2019;Madejon et al, 2009). Chemical investigations are therefore necessary to improve understanding of the TMM tolerance mechanisms of this wild plant species.…”

“…Our results also highlighted that even after 95 years since the former factory's closure, diffuse soil pollution is still significant, and TMM mobility is not negligible. The soil diffuse pollution in this area is widespread (Laffont-Schwob et al, 2016;Gelly et al, 2019) and since the area is now within a protected area (namely, the Calanques National Park), phytostabilisation with native plant species would likely be favoured (Heckenroth et al, 2016). This could include colonization of wild R. officinalis in areas of non-vegetated TMM contaminated soils for this study area.…”

Exploring heavy element distribution in soil profiles to assess the geochemical background and contamination extent in soils of a metallurgical and industrial area in Kosovo

“…Several authors have investigated the vertical distribution of heavy elements in soils of metallurgical sites, showing a common pattern consisting in a signi cant enrichment in the upper part of the soil pro le and a decline in concentrations with depth (Kabala and Singh 2001;Yuan et al 2017;Gelly et al 2019). However, few studies have established the surface and in-depth level and extent of soil contamination by heavy elements around smelting plants in relation to the local geochemical background, usually represented by the element concentrations in selected subsoil layers (Sterckeman et al 2000;Kribek et al 2010;Lienard and Colinet 2016;Lee et al 2020).…”

Atmospheric deposition of arsenic, cadmium, copper, lead, and zinc near an operating and an abandoned lead smelter

“…Lead smelting techniques have improved in recent years, and thus ore recovery has improved. However, due to past environmental pollution and the concern regarding heavy metal(loid)s pollution effects on local soils, crops, and residents, some nonferrous metal smelters have been closed (Douay, Roussel, Pruvot, & Waterlot, 2008; Gelly et al., 2019; Lee et al., 2020; Van Pelt et al., 2020). Regardless of site closures or improved smelting techniques at existing facilities, areas near former/current smelters continue to contain elevated soil heavy metal(loid)s concentrations.…”