Modelling the sulfate capacity of simulated radioactive waste borosilicate glasses

The capacity of simulated high-level radioactive waste borosilicate glasses to incorporate sulfate has been studied as a function of glass composition. Combined Raman, 57Fe Mössbauer and literature evidence supports the attribution of coordination numbers and oxidation states of constituent cations for the purposes of modelling, and results confirm the validity of correlating sulfate incorporation in multicomponent borosilicate radioactive waste glasses with different models. A strong compositional dependency is observed and this can be described by an inverse linear relationship between incorporated sulfate (mol% SO42−) and total cation field strength index of the glass, Σ(z/a2), with a high goodness-of-fit (R2 ≈ 0.950). Similar relationships are also obtained if theoretical optical basicity, Λth (R2 ≈ 0.930) or non-bridging oxygen per tetrahedron ratio, NBO/T (R2 ≈ 0.919), are used. Results support the application of these models, and in particular Σ(z/a2), as predictive tools to aid the development of new glass compositions with enhanced sulfate capacities

Speciation, Luminescence, and Alkaline Fluorescence Quenching of 4-(2-methylbutyl)aminodipicolinic acid (H2MEBADPA)

4-(2-Methylbutyl)aminodipicolinic acid (H2MEBADPA) has been synthesized and fully characterized in terms of aqueous phase protonation constants (pKa\u27s) and photophysical measurements. The pKa\u27s were determined by spectrophotometric titrations, utilizing a fully sealed titration system. Photophysical measurements consisted of room temperature fluorescence and frozen solution phosphorescence as well as quantum yield determinations at various pH, which showed that only fully deprotonated MEBADPA2– is appreciably emissive. The fluorescence of MEBADPA2– has been determined to be quenched by hydroxide and methoxide anions, most likely through base-catalyzed excited-state tautomerism or proton transfer. This quenching phenomenon has been quantitatively explored through steady-state and time-resolved fluorescence measurements. Utilizing the determined pKas and quenching constants, the fluorescent intensity of MEBADPA2– has been successfully modeled as a function of pH

Reactivity of NH4H2PO4 toward LaCl3 in LiCl-KCl Melt Flux. Step by Step Formation of Monazite-Like LaPO4.

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Americium and trivalent Lanthanides incorporation in high-level waste glass-ceramics

International audienceThe incorporation and partitioning of americium and trivalent lanthanides were investigated in aluminoborosilicate glass-ceramics with apatite-like silicate crystals of general formula Ca$_2$(Ln,Am)$_8$(SiO$_4$)$_6$O$_2$. A microstructural and structural study of two glass-ceramics containing Am$_2$O$_3$ - La$_2$O$_3$ or Nd$_2$O$_3$ - La$_2$O$_3$, respectively, was carried out by XRD, SEM-EDS and EMPA so as to assess a comparison of Lanthanides and Actinides partitioning into apatite crystals and residual glass. Moreover, Raman analyses of residual glasses were performed to compare the role of Am and Nd on the glassy structure. Results put forward that shape, composition, Ln-Am stoichiometry and cell parameters of apatite crystals of both (Am-La) and (Nd-La) glass-ceramics are very close. This paper thus shows similar results for (Am-La) and (Nd-La) glass-ceramics in terms of apatite - glass partitioning and in terms of structural role on glassy structure. It can be therefore put forward that Nd$^{3+}$ and Am$^{3+}$ behaviors are close, either in the glass or in the crystalline structure

Ground-state proton transfer of 7-hydroxyquinoline confined in biologically relevant water nanopools

The ground-state reverse proton transfer of 7-hydroxyquinoline catalyzed by water confined in AOT reverse micelles has been investigated by measuring time-resolved transient-absorption spectra and kinetic profiles. The transfer time is profoundly retarded in water nanopools compared with that in bulk water (26 ??s) although it diminishes with the size increase of the water nanopool. The spectral-shift time of tautomeric transient absorption agrees well with the proton transfer time. The probe molecule is subject to the local gradient of polarity, whose magnitude is altered with the sizes of water nanopools. Accordingly, the observations made in this study indicate the multidimensional character of reaction coordinates, in which solvent polarization coupled to charge transfer plays a seminal role in the control of overall proton-transfer dynamics. The retardation of proton transfer in water nanopools is ascribed to the increased formation energy of a charge-transferred optimal configuration, which is prerequisite to facile intrinsic proton transfer via tunneling.close201