Local Structure and Protons in Non-Stoichiometric Pseudo-Cubic Pollucite Mineral by Multinuclear NMR

Abstract

The pollucite structure is considered as a candidate ceramic crystalline matrix for the ceramic immobilization and long-term storage of 135Cs and 137Cs fission products, and thus, their structural characteristics have particular importance. However, its local structure has not been fully resolved from reciprocal-space techniques and infrared spectroscopy, and important discrepancies exist in the available literature. Two birefringent and non-stoichiometric pollucite specimens from Tanco pegmatite (Cs0.83Na0.20Al1.13Si2.56O6) and from Mt. Mica pegmatite (Cs0.94Na018Al1.23Si2.78O6), with powder X-ray diffraction patterns fully consistent with the cubic Ia-3d space-group symmetry, and with a very different degree of hydrothermal alteration, were used in this work. High-resolution magic-angle spinning multinuclear magnetic resonance (MAS NMR) spectroscopy, including 29Si, 27Al, 23Na, 133Cs, and 1H spectra at 9.4 T, as well as 1H, 27Al, 27Al{1H} dipolar evolutions and 27Al{29Si} Heteronuclear Multiple Quantum Coherence (HMCQ) spectra at 17.6 T, has been used to investigate the local structure of pollucite and the role of protons. The 29Si spectra suggest a local structure with a disordered Si/Al distribution in only one tetrahedral T site, but with a preference of Si atoms for Q41 (3Si,1Al) and Q42 (2Si,2Al) environments, in comparison with random and Loewenstein distributions, due to charge dispersion effects. However, the 27Al{1H} dipolar evolutions suggest two spectroscopically distinct T sites for Al atoms. The 23Na and 133Cs spectra indicate broad site distributions for these cavity cations. The anisotropic character of the long-range disordered pollucite structure, with a pseudo-cubic symmetry and lack of strict periodicity, can be explained from an incipient displacive transition to lower symmetry. These pollucite specimens are essentially anhydrous minerals despite the 1H and the cross-polarization experiments suggesting that some protons exist in the structure as -OH groups, whereas water molecules were only found in relation to the phyllosilicate impurities from alteration in specimen Tanco and perhaps also as liquid water in fluid inclusions.