The immobilization of soluble Cs from spent fuel elements by ion exchange and direct chemical reaction with clay minerals or shales was investigated under hydrothermal conditions. Various clay minerals or shales were reacted with likely Cs sources and water at 300 bars pressure and 100°, 200°, and 300°C for 4, 2, and 1 months, respectively. Pollucite was the principal product, but CsAlSiO4 was also observed, along with unreacted or hydrothermally altered aluminosilicates. From Cs concentrations of the product solutions partition of Cs between liquid and solids was found to vary depending on the Cs source, the clay or shale phase, temperature, and run duration. For example, illite-Cs2MoO4 interactions resulted in 19, 32, and 95% fixation of added Cs at 100°, 200°, and 300°C respectively. Fixation of as much as 97% of the Cs in some solids was observed. In addition to Cs-aluminosilicates, Cs was fixed on cation-exchange sites by interlayer collapse in montmorillonite. Reactions with Cs2MoO4 also produced powellite because Ca was available in the reaction mixture. The U6+ from β-Cs2U2O7 was reduced to form uraninite by sulfide- and/or organic-rich shales. (Cs,Na)2(UO2)(Si2O5)3·4H2O, an analog of weeksite, was produced in reactions with β-Cs2U2O7. The reaction products pollucite and uraninite can immobilize much of the Cs and U from spent fuel elements because Cs in pollucite is extremely difficult to exchange and U in uraninite is insoluble.

The Cs selectivity of several natural zeolitic tuffs and synthetic zeolites was measured. Phillipsite-rich tuffs from California and Nevada exchanged 13.5 and 23.7%, respectively, of the Cs present in simulated alkaline defense waste containing 0.00025 M CsCl in 5.5 M NaCl-NaOH solution from the Savannah River Plant, Aiken, South Carolina; whereas mordenite-rich tuffs from Arizona and Nevada exchanged less than 12.7%. The immobilization or fixation of Cs in phillipsite unlike other zeolites can be achieved by heating the zeolite at 600°C for 4 hr in air and collapsing the silicate (aluminate) tetrahedral rings around the Cs ions to produce a Cs-feldspar-type phase. Treatment of the Cs-exchanged phillipsite-rich tuff at 800° to 1000°C resulted in pollucite, CsAlSi2O6, which also “locks in” the Cs ions in its structure. The fixation of Cs exchanged in phillipsite can also be achieved by the formation of pollucite upon hydrothermal treatment at 300°C and 30 MPa pressure within 12 hr. These results suggest that phillipsite-rich tuffs are good candidates for Cs immobilization by heat treatment at low temperatures after they have been used as sorbents in waste decontamination.

Pollucite is a silicate mineral of the rare element caesium, occurring in granitic pegmatites. Experiments have been carried out at 450, 600, and 750°C, 1.5 kbar, to study the equilibrium between pollucite, albite and the co-existing hydrothermal solution. When pollucite co-exists with albite, the alkaline composition of the solution is buffered. The Cs/Na ratio of the solution has been determined to be 0.11 at 450°C 0.22 at 600°C and 0.23 at 750°C. Pollucite contains about 15 mol.% of sodium, whereas albite is almost purely sodic. In nature, pollucite with more than 82 mol.% caesium has never been found. This can be explained by the absence of solutions in granitic pegmatites having a higher Cs/Na ratio than those determined by us.

We report a single-crystal Fourier-transform infrared (FTIR) study of a sample of pollucite from Maine, USA. Prior to our work, the sample had been characterized by single-crystal X-ray diffraction, neutron diffraction and electron-probe microanalysis. It is cubic Ia3d, with a crystal-chemical formula Na1.93(Cs10.48Rb0.31K0.04)Σ=10.83(Al14.45Si33.97)Σ=48.42O96·3.92H2O, and an H2O content, determined by thermogravimetric analysis, of 1.6 wt.%. The single-crystal FTIR spectrum has a doublet of intense bands at 3670 and 3589 cm–1, which are assigned to the ν3 and ν1 stretching modes of the H2O molecule, respectively. A very intense and sharp peak at 1620 cm–1 is assigned to the ν2 bending vibration. In the near-infrared region there is a relatively intense peak at 5270 cm–1, which is assigned to a combination (ν2 + ν3) mode of H2O, and a weak but well defined doublet at 7118 and 6831 cm–1, which is assigned to the first overtones of the fundamental stretching modes. A relatively weak but extremely sharp peak at 2348 cm–1 shows that the pollucite contains CO2 molecules in structural cavities. Mapping the sample using FTIR indicates that both H2O and CO2 are homogeneously distributed. Secondary ion mass spectrometry yielded an average CO2 content of 0.09±0.02 wt.%. On the basis of this value, we determined the integrated molar absorption coefficient for the spectroscopic analysis of CO2 in pollucite to be εiCO2 = 11,000±3000 l mol–1 cm–2; the linear molar absorption coefficient for the same integration range is εlCO2 = 1600±500 l mol–1 cm–1.

The structure of a synthetic end-member wairakite (CaAl2Si4O12·2H2O) has been determined using Rietveld analysis of high-resolution, synchrotron X-ray powder diffraction data, and 29Si and 27Al magic angle spinning nuclear magnetic resonance spectroscopy. The framework in the synthetic sample is more disordered than that in natural wairakite. Ca is distributed over the cavity cation sites M2, M12A, M12B in the approximate proportions 0.8:0.1:0.1, respectively, with M11 being vacant. 29Si MAS NMR data are consistent with about 80% of the Si occupying tetrahedral T11 and T12 sites linked to two Al atoms [Q4(2Al) silicons]. Tetrahedral and cavity cation site disorder are coupled so that Al mainly occupies T2 sites, with Ca in M12A and M12B being balanced by Al in T12A and T12B; T11A and T11B sites appear to only contain Si, in agreement with the M11 site being vacant. The crystal chemistries of the wide range of stoichiometries which crystallize with the leucite/pollucite structure-type are also reviewed, with particular attention being paid to the tetrahedral ordering configurations present in these phases, and the implications to crystallographic phase transitions.