Abstract

ABSTRACT The sorption of cadmium (Cd) is one of the most important chemical processes in soil, affecting its fate and mobility in both soil and water and ultimately controlling its bioavailability. In order to fundamentally understand the sorption/desorption of Cd in soil systems, X-ray absorption fine structure spectroscopy (XAFS) has been applied in numerous studies to provide molecular-level information that can be used to characterize the surface adsorption and precipitation reactions that Cd can undergo. This information greatly improves our current knowledge of the possible chemical reactions of Cd in soil. This paper critically reviews the mechanisms of Cd sorption/desorption at the mineral-water interface based on XAFS studies performed over the past twenty years. An introduction to the basic concepts of sorption processes is provided, followed by a detailed interpretation of XAFS theory and experimental data collection and processing, ending finally with a discussion of the atomic/molecular-scale Cd sorption mechanisms that occur at the soil mineral-water interface. Particular emphasis is placed on literature that discusses Cd adsorption and speciation when associated with iron, manganese, and aluminum oxides and aluminosilicate minerals. Multiple sorption mechanisms by which Cd is sorbed by these minerals have been found, spanning from outer-sphere to inner-sphere to surface precipitation, depending on mineral type, surface loading, and pH. In addition, the application of complementary techniques (e.g., 113Cd nuclear magnetic resonance (NMR) and molecular dynamics simulation) for probing Cd sorption mechanisms is discussed. This review can help to develop appropriate strategies for the environmental remediation of Cd-contaminated soils.

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