Speciation, thermodynamics and structure of Np(V) oxalate complexes in aqueous solution.

The speciation, thermodynamics and structure of the Np(v) (as the NpO2+ cation) complexes with oxalate (Ox2-) are studied by different spectroscopic techniques. Near infrared absorption spectroscopy (Vis/NIR) is used to investigate complexation reactions as a function of the total ligand concentration ([Ox2-]total), ionic strength (Im = 0.5-4.0 mol kg-1 Na+(Cl-/ClO4-)) and temperature (T = 20-85 °C) for determination of the complex stoichiometry and thermodynamic functions (log ß0n(T), ΔrH0n, ΔrS0n). Besides the solvated NpO2+ ion, two NpO2+ oxalate species (NpO2(Ox)n1-2n; n = 1, 2) are identified. With increasing temperature a decrease of the molar fractions of the 1 : 1 - and 1 : 2 - complexes is observed. Application of the law of mass action yields the temperature dependent conditional stability constants log ß'n(T) at a given ionic strength which are extrapolated to IUPAC reference state conditions (Im = 0) according to the specific ion interaction theory (SIT). The log ß0n(T) values of both complex species (log ß01(25 °C) = 4.53 ± 0.12; log ß02(25 °C) = 6.22 ± 0.24) decrease with increasing temperature confirming an exothermic complexation reaction. The temperature dependence of the thermodynamic stability constants is described by the integrated van't Hoff equation yielding the standard reaction enthalpies (ΔrH01 = -1.3 ± 0.7 kJ mol-1; ΔrH02 = -8.7 ± 1.4 kJ mol-1) and entropies (ΔrS01 = 82 ± 2 J mol-1 K-1; ΔrS02 = 90 ± 5 J mol-1 K-1) for the complexation reactions. In addition, the sum of the specific binary ion-ion interaction coefficients Δε0n(T) for the complexation reactions are obtained from SIT modelling as a function of the temperature. The structure of the complexes and the coordination mode of oxalate are investigated using EXAFS spectroscopy and quantum chemical calculations. The results show, that in case of both species NpO2(Ox)- and NpO2(Ox)23-, chelate complexes with 5-membered rings are formed.

Experimental and numerical investigations on the effect of fracture geometry and fracture aperture distribution on flow and solute transport in natural fractures.

The impact of fracture geometry and aperture distribution on fluid movement and on non-reactive solute transport was investigated experimentally and numerically in single fractures. For this purpose a hydrothermally altered and an unaltered granite drill core with axial fractures were investigated. Using three injection and three extraction locations at top and bottom of the fractured cores, different dipole flow fields were examined. The conservative tracer (Amino-G) breakthrough curves were measured using fluorescence spectroscopy. Based on 3-D digital data obtained by micro-computed tomography 2.5-D numerical models were generated for both fractures by mapping the measured aperture distributions to the 2-D fracture geometries (x-y plane). Fluid flow and tracer transport were simulated using COMSOL Multiphysics®. By means of numerical simulations and tomographic imaging experimentally observed breakthrough curves can be understood and qualitatively reproduced. The experiments and simulations suggest that fluid flow in the altered fracture is governed by the 2-D fracture geometry in the x-y plane, while fluid flow in the unaltered fracture seems to be controlled by the aperture distribution. Moreover, we demonstrate that in our case simplified parallel-plate models fail to describe the experimental findings and that pronounced tailings can be attributed to complex internal heterogeneities. The results presented, implicate the necessity to incorporate complex domain geometries governing fluid flow and mass transport into transport modeling.

A closer look on the coordination of soft nitrogen-donor ligands to Cm(iii): SO3-Ph-BTBP.

We present a combined theoretical and experimental study on the recently developed hydrophilic SO3-Ph-BTBP ligand. Vibronic side band spectroscopy and time-resolved laser fluorescence spectroscopy (TRLFS) were employed to prove the theoretical prediction of the ligand's coordination mode.