In situ spectroscopic identification of neptunium(V) inner-sphere complexes on the hematite-water interface.

Hematite plays a decisive role in regulating the mobility of contaminants in rocks and soils. The Np(V) reactions at the hematite-water interface were comprehensively investigated by a combined approach of in situ vibrational spectroscopy, X-ray absorption spectroscopy and surface complexation modeling. A variety of sorption parameters such as Np(V) concentration, pH, ionic strength, and the presence of bicarbonate was considered. Time-resolved IR spectroscopic sorption experiments at the iron oxide-water interface evidenced the formation of a single monomer Np(V) inner-sphere sorption complex. EXAFS provided complementary information on bidentate edge-sharing coordination. In the presence of atmospherically derived bicarbonate the formation of the bis-carbonato inner-sphere complex was confirmed supporting previous EXAFS findings.1 The obtained molecular structure allows more reliable surface complexation modeling of recent and future macroscopic data. Such confident modeling is mandatory for evaluating water contamination and for predicting the fate and migration of radioactive contaminants in the subsurface environment as it might occur in the vicinity of a radioactive waste repository or a reprocessing plant.

Temperature impact on the sorption of selenium(VI) onto anatase.

The impact of temperature (298 K, 313 K, and 333 K) on the sorption of selenium(VI) onto anatase was investigated for the first time. At a macroscopic level, batch experiments showed a decrease of selenium(VI) retention with both increasing pH (3.5-7.0) and temperature. The thermodynamic parameters of the sorption reaction, i.e. the enthalpy Δ(R)H, entropy Δ(R)S, and the Gibbs free energy Δ(R)G, were determined from the temperature dependence sorption data using the van't Hoff equation. The sorption process was found to be exothermic. Neither significant phase transformation nor a significant increase of anatase solubility could be detected with increasing temperature by XRD and ICP-MS. However, electrophoretic mobility measurements showed that both the zeta potential as well as the isoelectric point (pH(IEP)) of anatase were shifted to lower values with increasing temperature, leading to a decreased selenium(VI) sorption. At a microscopic level, the sorption mechanism of selenium(VI) onto anatase was elucidated at the three investigated temperatures by means of in situ Attenuated Total Reflection Fourier-Transform Infrared spectroscopy (ATR FT-IR). Results evidenced the formation of outer-sphere surface complexes, with no significant structural changes within the investigated temperature range.