Vibrational Spectroscopy of Selected Natural Uranyl Vanadates

Raman spectroscopy has been used to study a selection of uranyl vanadate minerals including carnotite, curienite, francevillite, tyuyamunite and metatyuyamunite. The minerals are characterised by an intense band in the 800 to 824 cm-1 region, assigned to the ν1 symmetric stretching vibrations of the (UO2)2+ units. A second intense band is observed in the 965 to 985 cm-1 range and is attributed to the ν1 (VO3) symmetric stretching vibrations in the (V2O8) units. This band is split with a second component observed at around 963 cm-1. A band of very low intensity is observed around 948 cm-1 and is assigned to the ν3 antisymmetric stretching vibrations of the (VO3) units. Bands in the range 608-655 cm-1 may be attributed to molecular water librational modes or the stretching modes ￮(V2O2) units. Bands in the range 573-583 cm-1 may be connected with the ￮ (U-Oequatorial) vibrations or ￮ (V2O2) units. Bands located in the range 467-539 cm-1 may be also attributed to the ￮ (U-Oequatorial) units vibrations. The bending modes of the (VO3) units are observed in the 463 to 480 cm-1 range – there may be some coincidence with ￮ (U-Oequatorial). The bending modes of the (V2O2) in the (V2O8) units are located in a series of bands around 407, 365 and 347 cm-1 (ν2). Two intense bands are observed in the 304 to 312 cm-1 range and 241 to 264 cm-1 range and are assigned to the doubly degenerate ν2 modes of the (UO2)2+ units. The study of the vibrational spectroscopy of uranyl vanadates is complicated by the overlap of bands from the (VO3) and (UO2)2+ units. Raman spectroscopy has proven most useful in assigning bands to these two units since Raman bands are sharp and well separated as compared with infrared bands. The uranyl vanadate minerals are often found as crystals on a host matrix and Raman spectroscopy enables their in-situ characterisation without sample preparation

Raman Spectroscopic Study of the Molybdate Mineral Szenicsite and Comparison with Other Paragenetically Related Molybdate Minerals

The molybdate-bearing mineral szenicsite, Cu3(MoO4)(OH)4, has been studied by Raman and infrared spectroscopy. A comparison of the Raman spectra is made with those of the closely related molybdate-bearing minerals, wulfenite, powellite, lindgrenite, and iriginite, which show common paragenesis. The Raman spectrum of szenicsite displays an intense, sharp band at 898 cm-1, attributed to the 1 symmetric stretching vibration of the MoO4 units. The position of this particular band may be compared with the values of 871 cm-1 for wulfenite and scheelite and 879 cm-1 for powellite. Two Raman bands are observed at 827 and 801 cm-1 for szenicsite, which are assigned to the 3(Eg) vibrational mode of the molybdate anion. The two MO4 2 modes are observed at 349 (Bg) and 308 cm-1 (Ag). The Raman band at 408 cm-1 for szenicsite is assigned to the 4(Eg) band. The Raman spectra are assigned according to a factor group analysis and are related to the structure of the minerals. The various minerals mentioned have characteristically different Raman spectra

Provenance of Ordovician and Devonian sandstones from southern Peru and northern Bolivia - U-Pb and Lu-Hf isotope evidence of detrital zircons and its implications for the geodynamic evolution of the Western Gondwana margin (14° - 17° S)

In an attempt to trace the provenance of sedimentary detritus and to gain information on the crustal evolution of the Early Paleozoic western Gondwana margin (14°-17°S) we applied a combined in situ U-Pb and Lu-Hf LA-ICP-MS isotope analysis on detrital zircon from 12 Ordovician and Devonian sandstones in southern Peru and northern Bolivia. The sandstones are exposed in the Eastern Cordillera, the Altiplano and the Coastal Cordillera. The sedimentary basins are part of the Peru-Bolivia trough. Few intrusive and extrusive Early Paleozoic rocks indicate that the Ordovician basins developed in a back-arc position, with the arc on the Arequipa Massif in the west and the Amazonian craton in the east. This plate-tectonic setting appears to have changed into a passive margin in the Early Devonian. The U-Pb zircon age distribution of the Ordovician sandstones from the Eastern Cordillera has the most distinctive peak between 0.7 and 0.5 Ga (Brazilian interval). Contrastingly, the most prominent U-Pb zircon age peak of the Ordovician sandstones from the Altiplano is at 1.2-0.9 Ga (Grenvillian interval) with a smaller peak at 1.85-1.7 Ga. The Devonian sandstones from the same locality on the Altiplano contain zircons with a major age peak at 0.5-0.4 Ga (Famatinian interval). Smaller U-Pb age peaks can be connected to the Brazilian, Grenvillian and Transamazonian (2.2-1.8 Ga) intervals. Zircons of the Devonian sandstones from the Coastal Cordillera have a similar age distribution but the Grenvillian ages, in one case also the Transamazonian ages are significantly more pronounced than the Brazilian ages. Zircons formed during the Brazilian interval could have been derived from various eastern sources on the Amazonian craton, those with Grenvillian ages were derived either from the Sunsas belt to the east or from the Arequipa Massif to the west of the sedimentary basin. Zircons related to the Famatinan event most probably originated in the Arequipa Massif, the closest place where respective magmatic arc rocks were available. Thus, the Ordovician sandstones of the Eastern Cordillera and the Altiplano had an eastern source, while the Altiplano locality was fed from a very limited source area, probably the Sunsas belt. The Devonian siliciclastic strata instead were mainly influenced by the Arequipa Massif. Minor influences of eastern sources are documented by the presence of Brazilian zircon ages. The in situ Lu-Hf isotope signature provides information about crustal recycling. Together with the U-Pb zircon ages, crustal evolution paths can be reconstructed. εHf(t) values of the analysed zircons spread between –20 and +12. Zircons with a very juvenile signatures (less than 5 εHf-units below the respective depleted mantle composition) we detected only in the interval between 1.5 and 0.9 Ga. Hence, of the Brazilian and Famatinian events we only find zircons derived from an evolved crust. A striking feature is the common Hf model ages (c.1.5-1.2 Ga) of zircons formed during the Grenvillian, Brazilian and Famatinian orogenies. This indicates that Famatinian-aged crystalline rocks of the Arequipa Massif and the Brazilianaged crystalline rocks of the Amazonian craton have a similar crustal origin

Raman Spectroscopy of Uranopilite of Different Origins - Implications for Molecular Structure

Uranopilite, \[(UO2)6(SO4)O2(OH)6(H2O)6](H2O)8, the composition of which may vary, can be understood as a complex hydrated uranyl oxy hydroxy sulfate. The structure of uranopilite of different localities has been studied by Raman spectroscopy at 298 and 77 K. A single intense band at 1009 cm-1 assigned to the ￮1 (SO4)2- symmetric stretching mode shifts to higher wavenumbers at 77 K. Three low intensity bands are observed at 1143, 1117 and 1097 cm-1. These bands are attributed to the (SO4)2- ν3 antisymmetric stretching modes. Multiple bands provide evidence that the symmetry of the sulphate anion in the uranopilite structure is lowered. Three bands are observed at 843 to 816 cm-1 in both 298 and 77 K spectra and are attributed to the ν1 symmetric stretching modes of the (UO2)2+ units. Multiple bands prove the symmetry reduction of the UO2 ion. Multiple OH stretching modes prove a complex arrangement of OH groupings and hydrogen bonding in the crystal structure. A series of infrared bands not observed in the Raman spectra are found at 1559, 1540, 1526 and 1511 cm-1 attributed to ￤ UOH bending modes. U-O bond lengths in uranyl and O-H…O bond lengths are calculated and compared with X-ray single crystal structure analysis. Raman spectra of uranopilites of different origin show subtle differences in spectra proving the spectra are origin and sample dependent. Hydrogen-bonding network and its arrangement in the crystal structure play an important role in the origin and stability of uranopilite

The thermal equation of state of FeTiO_3 ilmenite based on in situ X-ray diffraction at high pressures and temperatures

We present in situ measurements of the unit-cell volume of a natural terrestrial ilmenite (Jagersfontein mine, South Africa) and a synthetic reduced ilmenite (FeTiO_3) at simultaneous high pressure and high temperature up to 16 GPa and 1273 K. Unit-cell volumes were determined using energy-dispersive synchrotron X-ray diffraction in a multi-anvil press. Mössbauer analyses show that the synthetic sample contained insignificant amounts of Fe^(3+) both before and after the experiment. Results were fit to Birch-Murnaghan thermal equations of state, which reproduce the experimental data to within 0.5 and 0.7 GPa for the synthetic and natural samples, respectively. At ambient conditions, the unit-cell volume of the natural sample [V_0 = 314.75 ± 0.23 (1 ) Å^3] is significantly smaller than that of the synthetic sample [V_0 = 319.12 ± 0.26 Å^3]. The difference can be attributed to the presence of impurities and Fe^(3+) in the natural sample. The 1 bar isothermal bulk moduli K_(T0) for the reduced ilmenite is slightly larger than for the natural ilmenite (181 ± 7 and 165 ± 6 GPa, respectively), with pressure derivatives K_0' = 3 ± 1. Our results, combined with literature data, suggest that the unit-cell volume of reduced ilmenite is significantly larger than that of oxidized ilmenite, whereas their thermoelastic parameters are similar. Our data provide more appropriate input parameters for thermo-chemical models of lunar interior evolution, in which reduced ilmenite plays a critical role

A vibrational spectroscopic study of plancheite Cu 8Si 8O 22(OH) 4-H2O

Planchéite Cu8Si8O22(OH)4•H2O is a hydrated copper hydroxy silicate. The objective of this work is to use Raman and infrared spectroscopy to determine the molecular structure of planchéite. Raman bands of planchéite at around 1048, 1081 and 1127 are described as the ν1 –SiO3 symmetric stretching vibrations; Raman bands at 828, 906 are attributed to the ν3 –SiO3 antisymmetric stretching vibrations. The Raman band at 699 cm-1 is assigned to the ν4 bending modes of the -SiO3 units. The intense Raman band at 3479 cm-1 is ascribed to the stretching vibration of the OH units. The Raman band at 3250 cm-1 is evidence for water in the structure. A comparison of the spectra of planchéite with that of shattuckite and chrysocolla

High-Pressure Phase Transition of the Oxonitridosilicate Chloride Ce4[Si4O3+xN7-x]Cl1-xOx with x = 0.12 and 0.18

The high-pressure behaviour of the oxonitridosilicate chlorides Ce4[Si4O3þxN7-x]Cl1-xOx, x = 0.12 and 0.18, is investigated by in situ powder synchrotron X-ray diffraction. Pressures up to 28 GPa are generated using the diamond-anvil cell technique. A reversible phase transition of first order occurs at pressures between 8 and 10 GPa. Within this pressure range the high- and the low-pressure phases are observed concomitantly. At the phase transition the unit cell volume is reduced by about 5%, and the cubic symmetry (space group P213) is reduced to orthorhombic (space group P212121) following a translationengleiche group-subgroup relationship of index 3. A fit of a third-order Birch-Murnaghan equation of state to the p-V data results in a bulk modulus B0 = 124(5) GPa with its pressure derivative B0 = 5(1) at V0 = 1134.3(4) Å3 for the low-pressure phase and in B0 = 153(10) GPa with B0 = 3.0(6) at V0 = 1071(3) Å3 for the high-pressure phase. The orthorhombic phase shows an anisotropic axial compression with the a axis (which is the shortest axis) being more compressible (k(a) = 0.0143(4) 1/GPa) than the b and c axes (k(b) = 0.0045(2), k(c) = 0.0058(2) 1/GPa). The experimental results confirm an earlier prediction of the pressureinduced instability of isotypic Ce4[Si4O4N6]O, and also show that the bulk modulus was predicted reasonably well