title: Copper--alumina--organic matter mixed systems: alumina transformation and copper speciation as revealed by EPR spectroscopy.
abstract: The chemical forms and solubility of Cu in alumina-organic matter systems were studied separately (Cu/Al and Cu/OM) and in mixtures (Cu/Al/OM) during long-term (up to 8 years) equilibrations at pH 6 and 7.5. The transformation of alumina was monitored by XRD, while the chemical forms of Cu were probed by EPR spectroscopy. Total dissolved Cu was determined by voltammetry. Alumina transformation to gibbsite was more rapid and complete in the Cu/Al system equilibrated at pH 7.5 than at pH 6. The presence of colloidal organic matter (Cu/Al/OM) retarded the transformation of alumina. This effect was more pronounced in the system aged at pH 7.5, likely due to the higher pH that promotes formation of Al3+--organic matter coordination complexes. As expected, the systems at pH 7.5 resulted in lower dissolved Cu concentrations than corresponding systems at pH 6. After long-term equilibrations (8 and 5 years) at pH 6 and 7.5, however, the alumina-containing coprecipitates resulted in the lowest concentrations of Cu in solution (Cu/Al < Cu/Al/OM < Cu/OM). Analyses by EPR spectroscopy indicated that Cu forms inner-sphere complexes in all systems at both pH values. Changes in the chemical forms of coprecipitated Cu (Cu/Al and Cu/Al/OM systems) occurred with time and included Cu occupying discrete sites where Cu-O-Al bond formation was dominant followed by formation of clusters (Cu-O-Cu associations) and in some cases precipitates. The anisotropic EPR parameters of the Cu/OM systems suggested that stronger interactions exist between Cu and organic matter functional groups as compared to Cu interactions with alumina-containing coprecipitates; yet, Cu solubility was highest in the Cu/OM systems. The geochemical processes described in this investigation may be effective in forest soils and wastewater treatment plants where Al and Fe salts are used as flocculation agents and to remove metal contaminants from solution.
authors.affiliation: Department of Crop and Soil Sciences, The Pennsylvania State University, University Park, Pennsylvania 16802, USA. cem17@psu.edu
authors.forename: Carmen Enid
authors.initials: CE
authors.lastname: Martínez
authors.forename: Nadia
authors.initials: N
authors.lastname: Martínez-Villegas
mesh_terms: D000537:Aluminum Oxide / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods*; D014961:X-Ray Diffraction
chemical_list: D003300:Copper; D000537:Aluminum Oxide