Global Environmental Geochemistry and Molecular Speciation of Heavy Metals in Soils and Groundwater from Abandoned Smelting Sites: Analysis of the Contamination Dynamics and Remediation Alternatives in Karst Settings

Abstract

Abandoned smelting sites in karst terrain pose a serious environmental problem due to the complex relationship between specific hydrogeological elements and heavy metal contamination. This review combines work from across the globe to consider how karst-specific features (i.e., rapid underground drainage, high permeability, and carbonate mineralogy) influence the mobility, speciation, and bioavailability of “metallic” pollutants, such as Pb, Cd, Zn, and As. In some areas, such as Guizhou (China), the Cd content in the surface soil is as high as 23.36 mg/kg, indicating a regional risk. Molecular-scale analysis, such as synchrotron-based XAS, can elucidate the speciation forms that underlie toxicity and remediation potential. Additionally, we emphasize discrepancies between karst in Asia, Europe, and North America and synthesize cross-regional contamination events. The risk evaluation is complicated, particularly when dynamic flow systems and spatial heterogeneity are permanent, and deep models like DI-NCPI are required as a matter of course. The remediation is still dependent on the site; however, some technologies, such as phytoremediation, biosorption, and bioremediation, are promising if suitable geochemical and microbial conditions are present. This review presents a framework for integrating molecular data and hydrogeological concepts to inform the management of risk and sustainable remediation of legacy metal pollution in karst.