Olivine flow mechanisms at 8 GPa

The mechanisms responsible for high-temperature olivine deformation are investigated at a pressure of 8 GPa and temperatures up to 1780 K. San Carlos olivine specimens of different average grain sizes (0.5 and 5 μm) were deformed simultaneously between hard-alumina pistons during relaxation experiments. These experiments are carried out in a multi-anvil high-pressure apparatus coupled with synchrotron X-ray radiation. The different grain-size specimens experienced identical P-T-stress condition at any given time. A new method for measuring strains and strain rates (≥10⁻⁶ s⁻¹) of specimens at high pressure is documented. This method uses time-resolved in situ X-ray imaging and an image-analysis computation. The microstructures of run products, recovered after being quenched at different temperatures were characterized by transmission electron microscopy (TEM). We find that high-temperature olivine flow is grain-size insensitive at 8 GPa, which suggests that dislocation creep dominates olivine deformation at high pressure. This result is confirmed by the TEM investigation of our deformed specimens in which we find evidences of the activation of olivine dislocation slip systems. Specimen microstructures are consistent with dynamic recrystallization as an assisting process in olivine deformation during the high-pressure experiments. Extrapolation of our results to the low stress level and large grain size expected in the mantle suggests that dislocation creep assisted by dynamic recrystallization may also dominate natural olivine deformation in the upper mantle.     

鼻咽癌CT影像特点分析

目的是加深对鼻咽癌（NPC）CT征象的认识，提高对其影像诊断水平。方法：搜集经病理证实的NPC69例，详细分析其放疗前CT表现。结果：本组病例，鼻咽侧壁增厚最多见（87．0％），咽旁间隙变窄次之（68．1％），其余依次为茎内软组织增厚致密（59．4％），其他部位受侵则相对少见。结论：NPC累及鼻咽侧壁多见，突破咽频底筋膜后，肿瘤多侵犯咽旁间隙和茎内软组织。     

Equation of state of hexagonal aluminous phase in basaltic composition to 63 GPa at 300 K

A laser-heated diamond-anvil cell that is capable of operating up to a pressure of 63 GPa, with X-ray diffraction facilities using a synchrotron radiation source at the SPring-8, has been developed to observe the compressibility of a hexagonal aluminous phase, [K_0.15Na_1.66Ca_0.11Mg_1.29Fe²⁺ _0.86Al_3.13Ti_0.09Si_1.98] _Σ9.27O₁₂. The hexagonal aluminous phase is a potassium host mineral from the subducted oceanic crust in the Earth's lower mantle. A sample was heated using a YAG laser at each pressure increment to relax the deviatoric stress in the sample. X-ray diffraction measurements were carried out at 300 K using an angle-dispersive technique. Pressure was measured using an internal platinum pressure calibrant. The observed unit-cell volumes were used to obtain a third-order Birch–Murnaghan equation of state: unit-cell volume V _o=185.94(±16) ų, density ρ _o=4.145 g/cm³, and bulk modulus K _o=198(±3) GPa when the first pressure is derivative of the bulk modulus K ^′ _o is fixed to 4. The density of hexagonal aluminous phase is lower than that of coexisting Mg-perovskite in the subducted oceanic crust.     

In situ X-ray observations of the decomposition of brucite and the graphite–diamond conversion in aqueous fluid at high pressure and temperature

 An experimental technique to make real-time observations at high pressure and temperature of the diamond-forming process in candidate material of mantle fluids as a catalyst has been established for the first time. In situ X-ray diffraction experiments using synchrotron radiation have been performed upon a mixture of brucite [Mg(OH)₂] and graphite as starting material. Brucite decomposes into periclase (MgO) and H₂O at 3.6 GPa and 1050 °C while no periclase is formed after the decomposition of brucite at 6.2 GPa and 1150 °C, indicating that the solubility of the MgO component in H₂O greatly increases with increasing pressure. The conversion of graphite to diamond in aqueous fluid has been observed at 7.7 GPa and 1835 °C. Time-dependent X-ray diffraction profiles for this transformation have been successfully obtained. Received: 17 July 2001 / Accepted: 18 February 2002     

Crystal-chemical and energetic systematics of wadeite-type phases A2BSi3O9 (A = K, Cs; B = Si, Ti, Zr)

Wadeite K₂ZrSi₃O₉ and its analogues K₂TiSi₃O₉ and Cs₂ZrSi₃O₉, synthesized by high-temperature solid-state sintering, have been investigated using powder X-ray diffraction coupled with Rietveld analysis and high-temperature oxide melt solution calorimetry. The crystal chemistry and energetics of these phases, together with K₂Si^VISi₃ ^IVO₉, a high-pressure wadeite analogue containing both tetrahedral and octahedral Si, are discussed in term of ionic substitutions. As the size of the octahedral framework cation increases, Si⁴⁺ → Ti⁴⁺ → Zr⁴⁺, the cell parameter c increases at a much higher rate than a. In contrast, increasing the interstitial alkali cation size (K⁺ → Cs⁺) results in a higher rate of increase in a compared with c. This behavior can be attributed to framework distortion around the interstitial cation. The enthalpies of formation from the constituent oxides (ΔH_f,ox⁰) and from the elements (ΔH_f,el⁰) have been determined from drop-solution calorimetry into 2PbO·B₂O₃ solvent at 975 K. The obtained values (in kJ/mol) are as follows: ΔH_f,ox⁰ (K₂TiSi₃O₉) = −355.8 ± 3.0, ΔH_f,el⁰ (K₂TiSi₃O₉) = −4395.1 ± 4.8, ΔH_f,ox⁰ (K₂ZrSi₃O₉) = −374.3 ± 3.3, ΔH_f,el⁰ (K₂ZrSi₃O₉) = −4569.9 ± 5.0, ΔH_f,ox⁰ (Cs₂ZrSi₃O₉) = −396.6 ± 4.4, and ΔH_f,el⁰ (Cs₂ZrSi₃O₉) = −4575.0 ± 5.5. The enthalpies of formation for K₂Si^VISi₃ ^IVO₉ were calculated from its drop-solution enthalpy of an earlier study (Akaogi et al. 2004), and the obtained ΔH_f,ox⁰ (K₂SiSi₃O₉) = −319.7 ± 3.4 and ΔH_f,el⁰ (K₂SiSi₃O₉) = −4288.7 ± 5.1 kJ/mol. With increasing the size of the octahedral framework cation or of the interstitial alkali cation, the formation enthalpies become more exothermic. This trend is consistent with the general behavior of increasing energetic stability with decreasing ionic potential (z/r) seen in many oxide and silicate systems. Further, increasing the size of the octahedral framework cation appears to induce more rapid increase in stability than increasing the interstitial alkali cation size, suggesting that framework cations play a more dominant role in wadeite stability.     

Effects of defect and pressure on the thermal expansivity of Fe x O

Pressure–volume–temperature measurements have been carried out using synchrotron X-ray diffraction for wüstite at static pressures of 1.9, 2.6, and 5.4 GPa. Our results revealed that the composition change of wüstite and, hence, rearrangements of defect structures are primarily caused by the magnetite (Fe₃O₄) exsolution at temperatures of 523–723 K. Based on the isobaric volume–temperature data collected during cooling, the contribution of compositional variations to the unit-cell volumes of wüstite in the ranges of 300–673 K and 723–1073 K is negligibly small, within the experimental uncertainties. These observations suggest that the measured volume changes in the range of 300–673 K and 723–1,073 K can be attributed to the metal–oxygen bond expansion. Owing to the magnetite exsolution, thermal expansion data are obtained in each experiment at 1.9, 2.6, and 5.4 GPa for wüstite of two different compositions, Fe_0.987O and Fe_0.942O. At all three pressures, Fe_0.942O shows a thermal expansion that is about 30% larger than Fe_0.987O. Such findings represent the first experimental evidence of a substantial effect of nonstoichiometry on thermal expansivity, and based on previous thermodynamic calculations of the defect formation and interaction, this effect is likely associated with the distinct defects arrangements in iron-rich and more iron-deficient wüstite. This study also presents thermal equations of state for wüstite of two different compositions. Such volume-related properties at high temperatures are experimentally difficult to obtain in wüstite but important for thermodynamic studies in the binary Fe–O system.     

Characterization of synthetic hedenbergite (CaFeSi2O6)–petedunnite (CaZnSi2O6) solid solution series by X-ray single crystal diffraction

Clinopyroxenes of the solid solution series hedenbergite (CaFeSi₂O₆)–petedunnite (CaZnSi₂O₆) were synthesized at temperatures of 825–1200°C and pressures of 0.5–2.5 GPa. Compositions were determined by electron microprobe analysis. Selected crystals were investigated by means of single crystal diffraction and structure refinement and the structural distortion was studied depending on the substitution of iron by zinc on the octahedral M1 site. It is shown that the coordination of the M1 site has the most significant effect on M–O bond lengths, with changes on the other sites accommodating this distortion. The mean quadratic elongation and the octahedral angle variance as quantitative measures of the distortion of the coordination polyhedron were correlated with former results of ⁵⁷Fe Mössbauer spectroscopy at 298 K. The results presented now complete an earlier work on synthetic, crystalline powders of the same material and deliver exact structural data that were not possible to obtain by Rietveld refinements on powder data.     

The role of dewatering in the progressive deformation of a sandy accretionary wedge: constraints from direct imagings of fluid flow and void structure

Geological investigation of the deformation structures and sedimentary setting of the Emi Group, a Miocene sand-rich accretionary complex, central Japan, revealed a six stage-structural evolution during shallow level accretion in a subduction zone. The early deformation (stage 1) is characterized by independent particulate flow in layer parallel faults, scaly cleavages and web structures, and upward dewatering in dish-and-pillar structures and breccia injections, while later deformation (stages 2–6) involve mappable scale folding, meso- to macro-scopic thrusts and web structures with cataclastic flow. Based on microscopic analyses of these structures, the early faulting with independent particulate flow (stage 1 deformation) is associated with dilatancy and preferred orientation of void space, whereas the later faulting with cataclastic flow (stage 2 deformation) occurs with compaction and crude preferred orientation. The former features imply more permeable fluid migration pathways, supported by the permeability measurements and direct imaging of fluid flow by X-ray CT. On the other hand, the later fault zone has lower permeability and porosity than intact rock, and plays as fluid sealing. Thus, in the early stage (stages 1), fluid flow occurs as focused flow through dilatant fault zones with independent particulate flow or fluid migration by upward dewatering forming dish-and-pillar structures and breccia injections, whereas no evidence of fluid flow is recognized at the later stages (stages 2–6). Namely the fault zones focus fluid flow during primary accretion in shallow levels, and the fluid flow is strongly controlled by the deformation mechanism. Furthermore, the change of the deformation mechanism could be effected by progressive increment of the confining pressure, accompanied with accretion and lithification in the accretionary prism. In the shallow, dilatant-faulting regime where the deformation mechanism is independent particulate flow, focused flow dominates, whereas in the deep, cataclastic regime distributed flow may play a main conduit rather than the focused flow.     

Monitoring of weathering and conservation of building materials through non-destructive X-ray computed microtomography

X-ray computed microtomography (µCT) is a promising non-destructive imaging technique based on measurements of the attenuation of X-rays. It provides information on the internal structure of small samples with a maximum resolution of 10 µm. For this study, two porous local natural building stones, the sandstone of Bray and the limestone of Maastricht, were selected. Possible applications of the µCT-technique for qualitative monitoring of changes comprise (1) to non-destructively determine porosity based on 3-D images, (2) to visualise weathering phenomena at the micron-scale, (3) to understand the rationale of weathering processes, (4) to visualise the presence of water repellents and consolidation products, (5) to monitor their protective effects during decay in order to understand the operating mechanisms and (6) to provide advise on the suitability of products for the treatment of a particular rock type. The µCT-technique proves to be a powerful monitoring tool for the future as the combination of 3-D visualisation and 3-D data provide new insights that could optimise conservation and restoration techniques of building materials.