Abstract
AbstractVariscite [Al(PO4)·2H2O] is an uncommon secondary phosphate mineral but is important in a variety of environmental and technological applications. It exists in at least one monoclinic (metavariscite) and two orthorhombic polymorphs (“Lucin-type” and “Messbach-type”), but the fine-grained nature of the “Messbach-type” variscite has hampered the determination of its crystal structure. The crystal structure of the latter from Tooele County, Utah, was solved and refined using laboratory powder X-ray diffraction (XRD) data, charge-flipping, and the Rietveld method. Both variscite modifications belong to the family of framework 3D MT structures in which octahedra (M) and tetrahedra (T) are linked by bridging O atoms. Topological analysis reveals that the two structures are polytypes. Based on our results and our structural interpretations, we refer to “Lucin-type” variscite as variscite1O and the “Messbach-type” as variscite2O, to be consistent with modern polytype terminology. The similarity of these two structures suggests that 1O-2O interstratifications may exist in nature, which is consistent with observed broadening of diffraction peaks of the Tooele material. 31P and 27Al MAS/NMR measurements are consistent with the XRD-determined crystal structure, and they show distinct signals for each of the two independent P and Al positions in variscite2O.High-temperature XRD, thermal analyses, and NMR measurements were applied to study the nature of the transformation of variscite2O to a derivative AlPO4 structure above 473 K. Charge-flipping analysis showed that the crystal structure of the new anhydrous AlPO4 phase (AlPO4-var2O in analogy to its parent structure) can be described as a 3D framework of alternating AlO4 and PO4 tetrahedra linked by bridging O atoms. Thermogravimetric analyses revealed almost complete dehydration above ~450 K, and NMR results were consistent with tetrahedral Al and P atoms.
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