Geochemical accumulation and source tracing of heavy metals in arable soils from a black shale catchment, southwestern China

Heavy metal enrichment in soils has been linked to the weathering of lithologies with high geochemical backgrounds, such as black shale. Therefore, this study conducted a typical sampling of surface soils in a black shale catchment in southwestern China to characterize the accumulation and sources of the heavy metals As, Cd, Co, Cr, Cu, Ni, Pb, Zn, Mo and Tl. Elevated concentrations of most heavy metals in the soils underlain by black shale are determined to exceed the regional soil background values, even the risk screening values, especially for Mo, As and Cd. Sequential extraction analysis, together with previous results, reveals that most heavy metals in soils are mainly bound in the residual fraction (> 65 %) as a result of the fixation of stable aluminosilicates (e.g., clay minerals). In contrast, Cd mainly occurs in relatively labile proportions as exchangeable (24.42 %), carbonate (24.48 %) and Fe/Mn oxide fractions (26.60 %) due to the non-specific adsorption of soil colloids and the precipitation of carbonates and Fe/Mn oxides. Pb isotopic tracing and APCS/MLR receptor model suggest that heavy metals in the urban surface soils (SG1) have a mixed source of black shale weathering, vehicle exhaust and agricultural input, while heavy metals in the rural surface soils (SG2) are a geogenic source of black shale weathering. Overall, this study provides new insights into contamination management, land use planning and health risk assessment in regions with high geochemical backgrounds.