Lithologic controls on the mobility of Cd in mining-impacted watersheds revealed by stable Cd isotopes

Abstract

Cd-rich wastes from open-pit mining can be transported into rivers, which are often followed by deposition in river sediments and/or further transfer into agricultural soils. The lithology of bedrock exerts a huge effect on physicochemical properties (e.g., buffering capacities, metal species, mineral phases, etc.) of the river system, thereby potentially impacting the Cd mobility in watersheds. However, to date, little is known about the microscopic processes (e.g., dissolution, adsorption, and precipitation) controlling the migration of Cd from mines to varied watersheds. This study, therefore, aims to determine the controlling factors on Cd mobilization in two mining-impacted watersheds with contrasting bedrock lithology using both Cd and Pb isotopes. The Pb isotope ratios of sediments and soils in both watersheds fall into a binary mixing model with two isotopically distinct sources, i.e., mining wastes and bedrock. These results indicate that mining activities are the main sources of Cd in sediments and soils. However, the Cd isotope ratios reveal different Cd migration processes between the two watersheds. In the siliceous watershed, the δ114/110Cd values of sediments decrease from -0.116‰ in the upper reach to -0.712‰ in the lower reach, with a concomitant increase in Cd concentration, which may result from Cd adsorption by goethite due to the increased pH. In contrast, in the calcareous watershed, the Cd isotope compositions of sediments (-0.345 to -0.276‰) and the pH of river water are nearly invariable, suggesting that the adsorption and release of Cd in sediments are limited. This may result from the strong pH buffering effect due to the presence of carbonate rocks. This study highlights the different fates of Cd in siliceous and calcareous watersheds and suggests that the development of Cd pollution control policies must consider regional lithology.