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Autunite, Ca[[(U[O.sub.2])(P[O.sub.4]).sub.2]][([H.sub.2]O).sub.11], is amongst the most abundant and widely distributed of the uranyl phosphate minerals, yet because of its pseudo-tetragonal symmetry and rapid dehydration in air, the details of its symmetry, stoichiometry, and structure were previously uncertain. The crystal structure of synthetic autunite was solved by direct methods and refined by full-matrix least-squares techniques to agreement indices [R.sub.1] = 0.041, calculated for the 1497 unique observed reflections (|[F.sub.o]| [greater than or equal to] 4[[sigma].sub.F]), and w[R.sub.2] = 0.119 for all data. Autunite is orthorhombic, space group Pnma, Z = 4, a = 14.0135(6), b = 20.7121(8), c = 6.9959(3) [Angstrom], V = 2030.55(15) [[Angstrom].sup.3]. The structure contains the well-known autunite type sheet with composition [[(U[O.sub.2])(P[O.sub.4])].sup.-], resulting from the sharing of equatorial vertices of the uranyl square bipyramids with the phosphate tetrahedra. The calcium atom in the interlayer is coordinated by seven [H.sub.2]O groups and two longer distances to uranyl apical O atoms. Two symmetrically independent [H.sub.2]O groups are held in the structure only by hydrogen bonding. Bond-length-constrained refinement provided a crystal-chemically reasonable description of the hydrogen bonding.

A Microsoft Excel spreadsheet has been programmed that allows users to calculate with ease the molar proportions of garnet end-members from chemical analyses. Recent advances in the understanding of the crystal chemistry of natural garnets, especially of the Ti-bearing garnets, are used to evaluate 29 end-members (15 species and 14 hypothetical end-members) for each analysis. The amounts of Fe2+ and Fe3+ (and Mn3+, if necessary) are calculated by stoichiometric constraints if these quantities have not been measured. The input data can include: SiO2, TiO2, ZrO2, SnO2, Y2O3, Al2O3, Sc2O3, Cr2O3, V2O3, FeO, Fe2O3, MnO, MgO, CaO, Na2O, H2O+ and F. The spreadsheet can be used with large data sets (up to 100 analyses at a time), and is accompanied by results calculated for 470 garnet analyses taken from the literature. The spreadsheet employs a simple scoring algorithm to measure the quality of a garnet analysis. The propagation of error from the input chemical data to the calculation of end-member proportions is also discussed briefly. [Copyright &y& Elsevier]

The crystal structures of synthetic hallimondite and synthetic parsonsite have been refined by full-matrix least-squares techniques to agreement indices (hallimondite, parsonsite) wR2 of 5.5, and 7.6% for all data, and R1 of 2.7 and 3.4%, calculated for 3391 and 3181 unique observed reflections (¦Fo¦ ≥ 4σF), respectively. Hallimondite is triclinic, space group P1, Z = 2, a = 7.1153(8), b = 10.4780(12), c = 6.8571(8) Å, α = 101.178(3)°, β = 95.711(3)°, γ = 86.651 (3)°, V = 498.64(3) ų, and is isostructural with parsonsite, triclinic, space group P1, Z = 2, a = 6.8432(5), b = 10.4105(7), c = 6.6718(4) Å, α = 101.418(1)°, β = 98-347(2)°, γ = 86.264(2)°, V = 460.64(5) ų. In both structures, hexavalent uranium occurs as a uranyl pentagonal bipyramid. The uranyl polyhedra share an edge, forming dimers that are linked by edge- and vertex-sharing with arsenate or phosphate tetrahedra to form chains along [001]. Two symmetrically distinct Pb positions connect the chains. In hallimondite, a partially occupied oxygen atom is located in the cavity between the uranyl arsenate chains and Pb positions, and is attributed to an H2O group. The crystal of synthetic parsonsite investigated does not have appreciable electron density at this position, but its structural cavity is large enough to contain H2O. The presence of H2O in synthetic hallimondite, and its absence in synthetic parsonsite, are supported by the results of FTIR spectroscopy. In conjunction with thermogravimetric results from the literature, we suggest that the formula of parsonsite should be considered Pb2[(UO2)(PO4)2](H2O)n, and hallimondite, Pb2[(UO2)(AsO4)2](H2O)n with 0 ≤ n ≤ 0.5 in each case. [ABSTRACT FROM AUTHOR]

Three homeotypic hydrated alkali metal uranyl phosphates, A2(UO2)[(UO2)(PO4)]4(H2O)2, A=Cs (CsUP), Rb (RbUP), K (KUP), were synthesized by hydrothermal methods. Intensity data were collected at room temperature using MoKα radiation and a CCD-based area detector. Their crystal structures were solved by Patterson (CsUP) and direct (RbUP, KUP) methods and refined by full-matrix least-squares techniques to agreement indices (CsUP, RbUP, KUP) wR2=0.048, 0.230, 0.072 for all data, and R1=0.023, 0.078, 0.038 calculated for 5338, 4738, 4514 unique observed reflections (∣Fo∣≥4σF), respectively. The compound CsUP is orthorhombic, space group Cmc21, Z=4, a=14.854(1), b=13.879(1), c=12.987(1) A˚, V=2677.5(3) A˚3. Both RbUP and KUP are monoclinic, space group Cm, but are presented in the unconventional pseudo-orthorhombic space group Fm11 to facilitate comparison with CsUP and to allow a model for RbUP that includes the effects of pseudo-merohedral twinning. RbUP is monoclinic, space group Fm11, Z=4, a=15.72(2), b=13.84(1), c=13.05(1) A˚, α=90.39°(2), V=2839(5) A˚3; KUP is monoclinic, space group Fm11, Z=4, a=15.257(1), b=13.831(1), c=13.007(1) A˚, α=91.760°(1), V=2743.4(3) A˚3. The structures consist of sheets of phosphate tetrahedra and uranyl pentagonal bipyramids, with composition [(UO2)(PO4)]−, that are topologically identical to the uranyl silicate sheets in uranophane-beta. These sheets are connected by a uranyl pentagonal bipyramid in the interlayer that shares corners with two phosphate tetrahedra on each of two adjacent sheets and whose fifth equatorial vertex is an H2O group, resulting in an open framework with alkali metal cations in the larger cavities of the structures. Where CsUP and RbUP have two alkali metal positions and a H2O group in these cavities, KUP has four K atoms and two H2O groups, all of which are partially occupied, in the interstitial sites. [Copyright &y& Elsevier]