Adsorption of several metal ions onto a model soil sample: equilibrium and EPR studies.

Soils play an important role in the control of metallic cations in the environment. Therefore, knowledge of the adsorption properties of soil is crucial in understanding and solving pollution problems. Adsorption isotherms provide a macroscopic view of the retention phenomena. The aim of this paper is to study iron, manganese, and chromium adsorption onto a soil sample as a function of the reaction time, pH, and metal concentration. The adsorption isotherms allow the determination of the affinity order of metals for the surface of the soil sample as such: Fe(3+)>Cr(3+)>Mn(2+). The equilibrium data fit well with the Langmuir and Freundlich models and confirm the affinity order of the soil sample for these metals. These adsorption data are combined with EPR spectroscopy to obtain structural information about the surface complexes formed. Iron is held in inner-sphere complexes. Manganese is simultaneously held in outer- and inner-sphere complexes. Due to poor resolution, chromium was not detected by EPR and thus it is impossible to infer coordination sphere and coordination number. Iron and manganese are in an octahedral environment.

Surface complexation of copper(II) on soil particles: EPR and XAFS studies.

The interactions of transition metals with natural systems play an important role in the mobility and the bioavailability of these metals in soils. In this study, the adsorption of copper(II) onto natural soil particles was studied as a function of pH and metal concentration. The retention capacity of soil particles was determined at pH 6.2 to be equal to 6.7 mg of copper/g of solid. The Langmuir and Freundlich isotherm equations were then used to describe the partitioning behavior of the system at different pH values. A combination of EPR, extended X-ray absorption fine structure (EXAFS), and X-ray absorption near-edge structure (XANES) spectroscopies was used to probe the Cu atomic environment at the soil particles/aqueous interface. The spectroscopic study revealed that copper(II) ions are held in inner-sphere surface complexes. It also revealed that Cu was in an octahedral coordination with first-shell oxygen atoms. A weak tetragonal distortion was pointed out due to the Jahn-Teller effect, with a mean Cu-Oequatorial bond distance of 1.96 A and a Cu-Oaxial bond distance of 2.06 A. A detailed analysis of the spectroscopic data suggested that Cu(II) was bonded to organic matter coated onto the mineral fraction of soil particles.