Sorption of selenium oxyanions on TiO2 (rutile) studied by batch or column experiments and spectroscopic methods.

Selenium is a known toxic element released in the environment by anthropogenic activities. The present study is devoted to the aqueous sorption behaviour of selenium oxyanions (selenate and selenite) on a reference oxide surface, namely rutile TiO(2). Batch sorption kinetics and isotherms have been studied using different physico-chemical conditions of the solution (changes of pH and ionic strength). The sorption was favoured for both anions in acidic conditions, in agreement with a surface complexation mechanism and CD-MUSIC predictions. Spectroscopic investigations of the sorbed rutile powder were also consistent with such a mechanism. EXAFS spectra confirmed that for selenite anions, an inner-sphere mechanism was the most probable process observed. Dynamic sorption experiments using a column filled with rutile powder also substantiated that a part of the surface complexes follows the inner-sphere mechanism, but also evidenced that an outer-sphere mechanism cannot be excluded, especially for selenate anions.

Comparison between batch and column experiments to determine the surface charge properties of rutile TiO2 powder.

This paper reports a comparative study of three methods for determining the surface charge and acid-base behavior of a TiO(2) rutile material. Electrophoretic mobility measurements were performed using two different batch protocols: (i) a "static" mode that consisted of immersing the rutile powder in aqueous solutions of given pH's and ionic strengths for 10 h, and (ii) a "dynamic" mode that consisted of using an automatic titrator to continuously adjust the solution pH with a contact time of 15 min. The same apparatus (a Nanosizer from Malvern) was used to measure the zeta potential of the particles in both methods. These batch experiments were next compared to the determination of the surface charge of rutile using nonlinear chromatography in column experiments. In that case, the rutile powder was compacted to enable the formation of a proper column bed. Therefore, Raman scattering and X-ray photoelectron spectra were used, as well as other physical information such as specific surface area and morphology of the particles, to verify that the rutile powder and compacted form were identical. The three approaches were then compared and discussed in relation to the acid-base behavior of the rutile material.

Local heterogeneity for a Eu3+-doped glass evidenced by time-resolved fluorescence spectroscopy coupled to scanning near-field optical microscopy.

Time-resolved fluorescence spectroscopy (TRFS) was applied to an aluminate glass sample doped with Eu3+ cation as a fluorescent probe of the chemical environment and local symmetry. Conventional far-field experiments revealed the presence of two different phases: an amorphous phase featured by a highly disordered environment surrounding the Eu3+ cation and a more ordered polycrystalline phase that exhibits a significant increase in the Eu3+ fluorescence decay time compared to that of the amorphous phase. Near-field fluorescence spectra and decay kinetics were recorded in the frontier region between the two phases using a home-built scanning near-field optical microscope. SNOM-TRFS experiments confirmed the presence of local heterogeneities in this part of the glass at a sub-micrometric spatial scale. Polycrystalline sites featured an important shear-force interaction with the probing fiber optic tip, a longer fluorescence decay time, and a higher Stark splitting of the 5D0 --> 7FJ (J = 1-4) electronic transitions of the Eu3+ cations.

Sorption of uranyl cations on a rutile (001) single crystal monitored by surface second-harmonic generation.

The rotational anisotropy of second-harmonic generation at the surface of a (001) single-crystal rutile is obtained in the presence of uranyl cations sorbed at the surface from acidic solutions at various concentrations. Surface second-harmonic generation appears to be sensitive to the presence of uranyl cations on the rutile samples. Evolution of the anisotropy pattern with initial uranyl concentration is analyzed through a phenomenological model. The elements obtained for the nonlinear susceptibility tensor Chi(2) for each sample significantly constrain the geometry of the possible sorption complexes between uranyl cations and rutile and lead to the proposition of two sorption sites involving different oxygen atoms of the rutile surface.