Abstract

Heavy metal(loid) (Cd, Co, Cr, Ni, Cu, Zn, Pb, V, Tl, and As) and Pb isotope compositions of two black shale weathering profiles were determined to investigate the geochemical behaviors of these toxic elements during black shale weathering and the heavy metal(loid) contamination and source apportionment of Pb in black shale-associated soils. Black shale has higher heavy metal(loid) concentrations than the upper continental crust and the worldwide average shale. In contrast, the surface soils have much higher heavy metal(loid) concentrations than the profile soils. The heavy metal(loid) concentrations in black shale-associated soils are higher than the Chinese and worldwide soil background values, except for Co and Pb. Black shale-associated soils, especially the surface soils, have higher average concentrations of As, Cd, Cr, Ni, Cu, and Zn than Chinese, Dutch, and Canadian soil guidelines. The enrichment factor (EF) and geoaccumulation index (Igeo) values indicate various degrees of heavy metal(loid) contamination in these soils, particularly for the heavy metals Cd, Tl, and V and metalloid As. Co and Pb contamination in these soils is not a current concern. According to the mass transfer coefficient (τTa,j) values, Cd, Co, Ni, and Zn show overall losses, and other metals (Cr, Cu, Pb, and V) exhibit different behavior in the studied black shale weathering profiles. Based on a simple binary Pb isotopic mixing model, black shale is the dominant contributor to the Pb in black shale-associated soils (70.5-91.1% to profile soils and 81.2-88.8% to surface soils), and vehicle exhaust contributes less (8.9-29.5%) to the Pb in profile soils. Vehicle exhaust can exert an impact on the Pb isotopic evolution at depth intervals of 60-80 cm below the soil surface.

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