Th. Fanghänel

Solid-liquid equilibria of Mg(OH)2(cr) and Mg2(OH)3Cl.4H2O(cr) in the system Mg-Na-H-OH-Cl-H2O at 25°C

Abstract The solubility of crystalline Mg(OH)2(cr) was determined by measuring the equilibrium H+ concentration in water, 0.01–2.7 m MgCl2, 0.1–5.6 m NaCl, and in mixtures of 0.5 and 5.0 m NaCl containing 0.01–0.05 m MgCl2. In MgCl2 solutions above 2 molal, magnesium hydroxide converted into hydrated magnesium oxychloride. The solid-liquid equilibrium of Mg2(OH)3Cl·4H2O(cr) was studied in 2.1–5.2 m MgCl2. Using known ion interaction Pitzer coefficients for the system Mg-Na-H-OH-Cl-H2O (25°C), the following equilibrium constants at I = 0 are calculated: Mg(OH) 2 (cr) + 2 H + ⇔ Mg 2+ + 2 H 2 O log K° s = 17.1 ± 0.2 Mg 2 (OH) 3 Cl·4H 2 O(cr) + 3 H + ⇔ 2 Mg 2+ + Cl − + 7 H 2 O log K° s = 26.0 ± 0.2 The experimental results are discussed with regard to discrepancies in frequently used databases and computer codes for geochemical modeling, such as EQ3/6, Geochemist’s Workbench and CHESS.

Site-selective time-resolved laser fluorescence spectroscopy of Eu3+ in calcite.

Three samples of calcite homogeneously doped with Eu(3+) were synthesized in a mixed-flow reactor. By means of selective excitation of the 5D0-->7F0 transition at low temperatures (T<20 K), three different Eu(3+) species (species A, B, and C, respectively) could be discriminated. For each one, the emission spectrum and lifetime were obtained after selective excitation of the single species. On the basis of these data, species C could be identified as Eu(3+) incorporated into the calcite lattice on the (nearly) octahedral Ca(2+) site. Species B was also identified as Eu(3+) incorporated into the calcite lattice, but the ligand field shows a much weaker symmetry. Species A, however, is not incorporated into the crystals bulk, having 1-2 H(2)O ligands left in its first coordination sphere and showing very little symmetry, and is considered as Eu(3+) adsorbed onto the calcite surface. The emission spectra of species C for Eu:calcite grown in the presence of Na(+) were found to differ from those of Eu:calcite synthesized in the presence of K(+). The latter revealed a strong distortion in site symmetry, which was not observed in the samples grown in Na(+) solutions. This finding provides spectroscopic evidence in favor of an incorporation mechanism based on the charge-balanced coupled substitution of Na(+)+Eu(3+)<-->2Ca(2+).

The influence of colloid formation in a granite groundwater bentonite porewater mixing zone on radionuclide speciation.

In the context of deep geological storage of high level nuclear waste the repository will be designed as multiple barrier system including bentonite as buffer/backfill material and the host rock formation as geological barrier. The engineered barrier (bentonite) will be in contact with the host rock formation and consequently it can be expected that bentonite porewater will mix with formation groundwater. We simulate in this study the mixing of Grimsel groundwater (glacial melt water) with synthetic Febex porewater (assuming already saturated state) in a batch-type study and investigate the formation of colloids by laser-induced breakdown detection (LIBD) and SEM-EDX as well as the changes in radionuclide (U, Th, Eu) speciation via ultrafiltration or via time-resolved laser fluorescence spectroscopy (TRLFS) analysis in the case of Cm(III). Based on PHREEQC saturation index (SI) calculations a precipitation of calcite might be expected at low Febex porewater (FPW) content (<20%), fluorite precipitation at FPW contents <60% and gibbsite precipitation at FPW contents above 10%. The colloids generated in the mixing zone aggregate when the synthetic FPW content exceeds 10%. LIBD analysis of the time-dependent colloid generation/aggregation revealed a low concentration of colloids to be stable with an estimated plateau value around 100-200 ppt and an average colloid diameter around 30 nm after 140 days reaction time at FPW admixture >10%. SEM/EDX mostly identifies Al/Si containing colloidal phases and some sulfates could be found under certain admixture ratios. TRLFS studies show that the Cm speciation is strongly influenced by colloid formation in all solutions. In the Febex pore water/GGW mixing zone with high groundwater contents (>80%) colloids are newly formed and Cm is almost quantitatively associated with most likely polysilicilic acid colloids.