Colloids control the mobilization of released zinc- and cadmium- species in calcite-rich soils

Cadmium (Cd)-bearing sphalerite (SP, ZnS) and smithsonite (SM, ZnCO₃) particulate matter (PM) is deposited on soils near carbonate-hosted Zn ore deposits. Whether and how carbonate rocks such as limestone influence the mobility of Cd and Zn in soils is largely unknown. For this reason, we conducted a soil incubation experiment to investigate the chemical and mineralogical changes in soil–soil solution samples, including the occurrence of Cd- and Zn-bearing colloids and nanoparticles. Here the addition of calcite to SP- and SM-spiked soils promoted the formation of Cd- and Zn- bearing nanoparticles and colloids and thus significantly decreased the concentrations of Cd and Zn in soil solutions. Transmission electron microscope and extended X-ray absorption fluorescence spectroscopy showed that the addition of calcite resulted in the formation of Fe-OM-Ca colloids (OM = organic matter), sequestrating Cd and Zn. Furthermore, the release of Ca²⁺ during the dissolution of calcite promoted the aggregation of colloids and thus decreased the mobility of Cd- and Zn-bearing colloids in the soil column. The addition of calcite also decreased the amount of Cd and Zn released from the dissolution of SP and SM through the formation of calcite nano-layers armoring particles of the SP and SM phases. This study provides new insights into the environmental fate of particulate Cd and Zn in soils around carbonate-hosted Pb-Zn ore deposits. Specifically, it shows that the formation and aggregation of Cd- and Zn-bearing colloids decrease the mobility and bioavailability of both elements.