Adsorption of uranyl ions on kaolinite, montmorillonite, humic acid and composite clay material

Campos Bruno, Aguilar-Carrillo Javier, Algarra Manuel, Gonçalves Mário A., Rodríguez-Castellón Enrique, Esteves da Silva Joaquim C.G., Bobos Iuliu
Applied Clay Science, Vol. 85, Pag. 53-63, 2013.


Adsorption of uranyl ions onto kaolinite, montmorillonite, humic acid and composite clay material (both clays and humic acid) was studied by measuring the system response to clay suspensions (pre-equilibrated with or without uranyl) and to perturbations of the solution chemistry. Adsorption behavior of selected materials under the frame of batch experiments was tested at high uranyl concentrations (6–1170 μg/mL; 2.5 × 10− 2 to 4.9 μM), whereas that under flow through continuous stirred reactor experiments was tested at low concentrations (1.00 × 10− 4 to 1.18 × 10− 4 M). Both experiments were developed at pH 4.5 and ionic strength 0.2 mM. The adsorption experiments follow a Langmuir isotherm model with a good correlation coefficient (R2 > 0.97). The calculated amount of adsorbed and desorbed uranyl was carried out by numeric integration of the experimental data, whereas the desorption rates were determined from the breakthrough curve experiments. Kaolinite with highly disordered structure adsorbed less uranyl (3.86 × 10− 6 mol/g) than well-ordered kaolinite (1.76 × 10− 5 mol/g). Higher amount of uranyl was adsorbed by montmorillonite (3.60 × 10− 5 mol/g) and only half of adsorbed amount was desorbed (1.85 × 10− 5 mol/g). The molecular interactions between kaolinite, montmorillonite, humic acid, composite material and saturated uranyl ion solutions were studied by molecular fluorescence, infrared and X-ray photoelectron spectroscopy. The Stern–Volmer constant obtained for montmorillonite (2.6 × 103 M− 1) is higher than for kaolinite (0.3 × 103 M− 1). Molecular vibrations of Sisingle bondO stretching and Alsingle bondOH bending related to hydroxylated groups (triple bond; length of mdashSiOH or triple bond; length of mdashAlOH) of kaolinite and montmorillonite show structural changes when uranyl ions are adsorbed. X-ray photoelectron spectroscopy shows that the U 4f7/2 core level signals occur at 380.5 eV in either kaolinite or montmorillonite that resulted from the interaction of aluminol surface sites with the (UO2)3(OH)5+.