An EXAFS investigation of the mechanism of competitive sorption between Co(Ⅱ) and Ni(Ⅱ) at γ-alumina/solution interface

Co(Ⅱ)and Ni(Ⅱ)are two common toxic heavy metals,and may simultaneously exist in contaminated water,soil,and sediment systems in Earth’s surface environment.Under this circumstance,competitive adsorption between the two metals may influence their migration,toxicity,and bioavailability.In this research,the competitive sorption of Co(Ⅱ)and Ni(Ⅱ)on γ-Al_2O_3was studied using both macroscopic sorption experiments and extended X-ray absorption fine structure(EXAFS)spectroscopy.Results suggest that Ni(Ⅱ)reduced the amount of Co(Ⅱ)sorption in a binary-solute system at pH 6.0.This is because both Co(Ⅱ)and Ni(Ⅱ)form inner-sphere surface complexes during sorption on γ-Al_2O_3and compete for the surface reactive sites.However,Co(Ⅱ)exhibited a negligible influence on sorption amount of Ni(Ⅱ)under the same conditions,which suggests Ni(Ⅱ)has a stronger affinity to alumina surface.At pH 7.5,Co(Ⅱ)and Ni(Ⅱ)sorption density were much higher than that at pH 6.0,but there no mutual competitive effect was observed.EXAFS analysis further revealed that formation of layered double-hydrated precipitates was the dominant sorption mechanism for both Co(Ⅱ)and Ni(Ⅱ)at pH 7.5.Because this type of sorption does not rely on surface reactive sites,there was no competition between Co(Ⅱ)and Ni(Ⅱ).This finding sheds light on risk assessment and remediation of Ni/Co pollution.

A review of cadmium sorption mechanisms on soil mineral surfaces revealed from synchrotron-based X-ray absorption fine structure spectroscopy:Implications for soil remediation

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.,113 Cd 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.