Modeling the complexation properties of mineral-bound organic polyelectrolyte: an attempt at comprehension using the model system alumina/polyacrylic acid/M (M=Eu, Cm, Gd).

This paper contributes to the comprehension of kinetic and equilibrium phenomena governing metal ion sorption on organic-matter-coated mineral particles. Sorption and desorption experiments were carried out with Eu ion and polyacrylic acid (PAA)-coated alumina colloids at pH 5 in 0.1 M NaClO(4) as a function of the metal ion loading. Under these conditions, M interaction with the solid is governed by sorbed PAA (PAA(ads)). The results were compared with spectroscopic data obtained by time-resolved laser-induced fluorescence spectroscopy (TRLFS) with Cm and Gd. The interaction between M and PAA(ads) was characterized by a kinetically controlled process: after rapid metal adsorption within less than 1 min, the speciation of complexed M changed at the particle surface till an equilibrium was reached after about 4 days. At equilibrium, one part of complexed M was shown to be not exchangeable. This process was strongly dependent on the ligand-to-metal ratio. Two models were tested to explain the data. In model 1, the kinetically controlled process was described through successive kinetically controlled reactions that follow the rapid metal ion adsorption. In model 2, the organic layer was considered as a porous medium: the kinetic process was explained by the diffusion of M from the surface into the organic layer. Model 1 allowed a very good description of equilibrium and kinetic experimental data. Model 2 could describe the data at equilibrium but could not explain the kinetic data accurately. In spite of this disagreement, model 2 appeared more realistic considering the results of the TRLFS measurements.