Extended X-ray absorption fine structure and time differential perturbed angular correlation study of hafnium(IV) sorbed onto amorphous silica

Abstract

Sorption of Hf(IV) onto amorphous silica at pH values between 1 and 7 is investigated by extended X-ray absorption fine structure (EXAFS) and time differential perturbed angular correlation (TDPAC) spectroscopies. Hafnium(IV) is studied as a chemical analogue for understanding the speciation of tetravalent actinides. In addition, 181Hf is a frequently investigated TDPAC probe nuclide. Spectra obtained from both techniques show that there is a change in Hf-species with sample preparation pH. Results from TDPAC measurements show that two similar surface binding sites exist for Hf(IV) on the silica surface at low pH values. At a pH above 3, a third, unspecific surface binding site for Hf(IV) begins to dominate. EXAFS investigations do not detect the presence of polynuclear surface species. Both TDPAC and Hf L3 edge EXAFS spectra of the sorption samples differ from that of a Hf(IV) solution or a Hf(IV) hydrolysis product. This indicates that the sorbed species are different from solution or simple hydrolysis species. Short Hf-O distances are obtained from theoretical fits to the EXAFS oscillations for all samples. This suggests that the primary interaction of Hf(IV) with the silica surface occurs via silanol groups. Differences in the electric field gradient surrounding sorbed Hf(IV) cations as a function of pH, observed in the TDPAC spectra, must result from changes in overall species geometry rather than a change in the primary Hf-silica surface interaction.