Effect of humic acid on the sorption of Cm(III) onto gamma-Al2O3 studied by the time-resolved laser fluorescence spectroscopy

摘要

Sorption of Cm(III) onto gamma-alumina coated with humic acid (HA) is studied by the Time Resolved Laser Fluorescence Spectroscopy (TRLFS). The experiments are performed at 0.1 M NaClO4, 0.44 g/L gamma-Al2O3, 10 mg/L HA and at a metal ion concentration of 2 x 10(-7) mol/L. At the investigated pH range (4 to 10) HA is completely sorbed to gamma-Al2O3. The excitation spectrum of Cm(III) bound to HA/gamma-Al2O3 in the wavelength range 370-400 nm exhibits broad flat bands very different from those obtained for the Cm(III) aquo ion and the Cm(III)-gamma-Al2O3 surface complex, respectively. The spectrum, lacking distinctive structure due to intramolecular energy transfer processes, points to the predominant binding of the Cm(III) to surface-bound HA. TRLFS experiments performed at two different excitation wavelengths (lambda(ex) = 355 and 396.6 nm) allow for a differentiation of humic-bound and non-humic-bound Cm(III). Differences in fluorescence spectra obtained at the different excitation wavelengths are found at pH < 6.9. They are due to the presence of the non-complexed Cm(III) aquo ion which is not detected in the indirect excitation mode (lambda(ex) = 355 nm). At pH greater than or equal to 7, the fluorescence spectra obtained by indirect and direct excitation become congruent and again point to the existence of only humic-bound Cm(III) species. Comparison of peak maxima and fluorescence lifetimes for Cm(III)-HA and Cm(III)-HA/gamma-Al2O3, however, reveal differences. The results clearly indicate a contribution of the gamma-Al2O3 Surface to the Cm(III) binding and, thus, suggest the formation of ternary complexes such as >Al-O-Cm(III)(HA).