Late Wuchiapingian (Late Dzhulfian,early Late Permian) limestone olistolites within the Tertiary flysch of Glypia Unit (Mount Parnon,central–eastern Peloponnesus,Greece)

Some olistolites reworked in a Tertiary flysch of Mount Parnon (Peloponnesus, Greece) exhibit a Late Permian assemblage, dominated by Paradunbarula (Shindella) shindensis, Hemigordiopsis cf. luquensis and Colaniella aff. minima. This association corresponds to the Late Wuchiapingian (=Late Dzhulfian), a substage whose algae and foraminifera are generally little known. Contemporaneous limestones crop out in the middle part of the Episkopi Formation in Hydra, but they are rather commonly reworked in Mesozoic and Cainozoic sequences. The palaeobiogeographical affinities shared by the foraminiferal markers of Greece, southeastern Pamir, and southern China, are very strong (up to the specific level), and are congruent with the Pangea B reconstructions. To cite this article: E. Skourtsos et al., C. R. Geoscience 334 (2002) 925–931.     

Structural variation in Ca(TixSi1−x)O3 perovskites (1>x>0.65) and the ordered phase Ca2TiSiO6

High pressure perovskites in the system CaTiO₃?CaSiO₃ in the composition range from 0 to 50% CaSiO₃ have been re-examined using powder x-ray diffraction, Raman spectroscopy, and transmission electron microscopy. In runs performed at 9 GPa and 1200 °C, a solid solution is obtained with compositions ranging from CaTiO₃ to near Ca(Ti_0.65Si_0.35)O₃, and with the orthorhombic distortion in the CaTiO₃ end-member diminishing to pseudocubic for Ca(Ti_0.65Si_0.35)O₃. Raman spectra show intensity changes and band broadening which are attributed to the reduction of orthorhombic character, but still indicate lower than cubic symmetry for the entire solid solution range. An ordered intermediate, Ca₂TiSiO₆, has been recovered from a run at 14 GPa at 1200 °C. The space group is Fm3m, with a=7.410(2)?Å, and the compound has the double perovskite structure. In this structure, Si-rich octahedral sites and Ti-rich octahedral sites alternate along the three principal axes. Transmission electron microscopy confirms the presence of the Fm3m ordered structure, and also documents the presence of lesser amounts of at least three other ordered perovskite structures which are not resolved in the x-ray data. These may account for extra features observed in the Raman spectrum which are inconsistent with mode assignments for the Fm3m phase. Non face-centered ordering schemes for these regions are suggested based on modeling of the HRTEM patterns.     

Calorimetric study of the stability of high pressure phases in the systems CoOSiO2 and “FeO”SiO2, and calculation of phase diagrams in MOSiO2 systems

High temperature calorimetric measurements of the enthalpies of solution in molten if2 PbO · B₂O₃ of α- and γ-Fe₂SiO₄ and α-, β-, and γ-Co₂SiO₄ permit the calculation of phase relations at high pressure and temperature. The reported triple point involving α-, β-, and γ-Co₂SiO₄ is confirmed to represent stable equilibrium. The curvature in the α?β phase boundary in Co₂SiO₄ and of an α?γ boundary in Fe₂SiO₄ at high temperature is explained in part by the effects of compressibility and thermal expansion, but better agreement with the observed phase diagram is obtained when one considers the effect of small amounts of cation disorder in the spinel and/or modified spinel phases. The calculated ΔH⁰ and ΔS⁰ values for the α?β, α?γ, and β?γ transitions show that enthalpy and en changes both vary strongly in the series Mg, Fe, Co, and Ni, and are of equal importance in determining the stability relations. The disproportionation of Fe₂SiO₄ and Co₂SiO₄ spinel to rocksalt plus stishovite is calculated to occur in the 170–190 kbar region; cation disorder and/or changes in wüstite stoichiometry can affect the P?T slope. The calorimetric data for CoSiO₃ and FeSiO₃ are in good agreement with the observed phase boundary for pyroxene formation from olivine and quartz. The decomposition of pyroxene to spinel and stishovite at pressures near the coesite-stishovite transition is predicted in both iron and cobalt systems. The use of calorimetric data, obtained from small samples of high pressure phases, is very useful in predicting equilibrium phase diagrams in the 50–300 kbar range.     

Thermochemistry of the new silica polymorph moganite

Samples of microcrystalline silica varieties containing variable amounts of the new silica polymorph moganite (up to R~82 wt.%) have been studied by a combination of high temperature solution calorimetry using lead borate (2 PbO · B₂O₃) solvent and transposed temperature drop calorimetry near 977 K, in order to investigate the thermochemical stability of this new silica mineral. The enthalpy of solution at 977 K and the heat content (H₉₇₇ — H₂₉₈) of “pure” moganite phase were estimated to be -7.16 ± 0.35 kJ/mol and 43.62 ± 0.50 kJ/mol, respectively. The standard molar enthalpy of formation is-907.3 ± 1.2 kJ/mol. Thus, calorimetry strongly supports results of previous X-ray and Raman spectroscopic studies that moganite is a distinct silica polymorph. Its thermochemical instability relative to quartz at 298 K of 3.4 ± 0.7 kJ/mol is marginally higher than those of cristobalite and tridymite. Structurally, this instability may be related to the presence of distorted 4-membered rings of SiO₄ tetrahedra, which are not found in the quartz structure. The metastability relative to quartz may also explain the apparent scarcity of moganite in altered rocks and in rocks that are older than 130 my.     

The effect of Fe on the crystal structure of wadsleyite β-(Mg1 − x Fe x )2SiO4, 0.00≤x≤0.40

Single crystals of five wadsleyite compositions, β-(Mg,Fe)₂SiO₄ with Fe/(Fe+Mg)=0.00, 0.08, 0.16, 0.25 and 0.40, have been synthesized at high temperature and pressure in a uniaxial, split-sphere apparatus. Crystal structures of these samples, determined by x-ray diffraction techniques, reveal that iron is significantly ordered: Fe is depleted in the M2 octahedron, while it is enriched in M1 and M3. The most iron-rich synthetic sample, which falls well outside previous estimates of wadsleyite stability, raises questions regarding published Mg₂SiO₄-Fe₂SiO₄ phase diagrams at transition zone conditions.     

Characterizing anthropic sediments in north European Neolithic settlements: An assessment from Skara Brae,Orkney

The creation of anthropic sediments, traditionally referred to under the blanket term midden, through the utilization of settlement waste materials in domestic settlement construction was first recognized during early excavations at the Orcadian Neolithic site of Skara Brae (V.G. Childe, 1931a; 1931b). Prior to the present study there has been no systematic attempt to identify the nature of these sediments at Skara Brae, whose likely occupation dates between ˜3100 and 2500 B.C., or to assess whether different materials were incorporated into construction or varied with different phases of site formation. The opportunity to begin addressing these issues arose with the location of undisturbed sediment samples held in storage since the last site excavations of 1972–1973 (D.V. Clarke, 1976). Ten thin sections were manufactured from these samples, representing earlier and later phases of Neolithic settlement at Skara Brae. Observations using thin‐section micromorphology, supported by total phosphorus and particle‐size distribution analyses, suggest that both earlier and later settlement phases show accumulation of household waste dominated by fuel residues. These wastes may have been used to help stabilize wind‐blown sand deposits during the later settlement phases. In addition, the use of clay material tempered with household waste is associated with wall construction. Animal manures are only evident in anthropic deposits on the edge of the main settlement site where composting may have been taking place, and there is no evidence for their use in site construction. The authors conclude by drawing attention to possible diverse uses of anthropic sediments in settlement construction at other Neolithic settlements in Orkney. © 2006 Wiley Periodicals, Inc.