Abstract
Hydropyrochlore, ideally (H2O,☐)2Nb2(O,OH)6(H2O), is a cubic mineral (space group Fd3m, a = 10.56–10.59 Å, Z = 8) belonging to the pyrochlore supergroup (general formula: A2–mB2X6–wY1–n). The K-rich variety of this species is unique to the Lueshe syenitic-carbonatitic deposit (D.R. Congo), where it occurs as the alteration product of primary (Ca,Na)2Nb2O6F pyrochlores. The structure of this mineral is made of a B2X6 (B = Nb, Ti; X = O, OH) framework that generates tunnels along the [110] direction, where the interstitial sites are partially occupied by water molecules and minor amounts of different cations. These features form the basis for the ion-exchange properties of hydropyrochlore, making it a promising candidate as a mineral sink for heavy metals (e.g., Tl+) dispersed in aqueous matrices, with interesting environmental implications.
Tl+ incorporation was induced through imbibition experiments in a diluted Clerici solution using single crystals of hydropyrochlore from Lueshe (D.R. Congo); the modifications induced by Tl+ incorporation were then evaluated using single-crystal X-ray diffraction (SCXRD), electron microprobe analyses (EMPA), and Fourier transform infrared (FTIR) spectroscopy.
After Tl+ imbibition, a dramatic increase of the A-site electron density (n.e– from ~4 to ~60) confirms the entry of a substantial amount of Tl+ at this site (up to about 70%), leading to a lengthening of the A-X distances and the consequent expansion of the unit cell. A decrease of the site scattering at the Y′ site (from ~9 to ~4 e–) also occurs, suggesting a loss of aqueous species. Although the predominance of neutral H2O molecules at the interstitial sites of hydropyrochlore from Lueshe is widely accepted by the mineralogical community, our crystal-chemical and FTIR data provide evidence that the dominant species might be the hydronium ion, with significant implications on the nomenclature of the pyrochlore supergroup.
Understanding the crystallographic aspects of hydropyrochlore as a potential waste form for monovalent thallium immobilization not only addresses a pressing environmental concern but also contributes to the broader field of waste management.