Stable isotopic evidence of cadmium enrichment in soils of black shale distribution areas

Black shale-derived soils exhibit significant heavy metal enrichment, notably cadmium (Cd) enrichment. This study pioneered the reporting of δ¹¹⁴/¹¹⁰Cd isotopic values within a black shale-soil system, offering novel insights into the geochemical behaviors and enrichment mechanisms of Cd during soil formation processes influenced by weathering. Systematic rock‒soil sampling was conducted on the lower Cambrian Hetang Formation in western Zhejiang, China, which is characterized by Cd-rich black shale. Employing analytical methods, including principal component analysis and multiple linear regression, we investigated the factors influencing heavy metal content in soil, such as element dissolution during weathering, soil pH, and the presence of iron-manganese oxides, sulfides, organic matter, and clay minerals. Our findings revealed a compositional range of δ¹¹⁴/¹¹⁰Cd in black shale (1.93‰–3.31‰) contrasting with that in adjacent soils (0.31‰–1.82‰), illustrating significant Cd isotopic fractionation during weathering, where heavier Cd isotopes are preferentially leached, and lighter isotopes are enriched in the soil in association with iron-manganese oxides. This research not only deepens the understanding of Cd enrichment mechanisms within the rock‒soil system against a black shale geological background but also elucidates the formation processes of soil Cd pollution in areas with a high geochemical background.