X-ray Raman scattering for structural investigation of silica/silicate minerals

We have performed X-ray Raman scattering (XRS) measurements on the oxygen K and silicon L absorption edges of four silica minerals: α-quartz, α-cristobalite, coesite, and stishovite. We have also calculated the partial electron densities of states (DOSs) and compared these with the XRS spectra. This study demonstrates that the short-range structure around the atom of interest strongly influences the XRS spectral features. Importantly, the oxygen K-edge XRS spectra are found to reflect the p-orbital DOS while the silicon L-edge spectra reflect the s- and d-orbital DOSs, even when a product of a momentum transfer and a mean radius of a electron orbit (1s for oxygen and 2p for silicon), Qr, is close to or larger than unity. Building on this, calculations of the partial DOSs for other silica phases are presented, including ultra-high-pressure phases, which provide a good reference for further XRS study of silica and silicate minerals. XRS measurements should be performed on not only either of oxygen or silicon but also on many kinds of constituent elements to reveal the structural change of glasses/melts of silicates under extreme conditions.     

Polymorphic Zooids in Deitaic Species Populations of Conopeum seurati (CANU, 1928) (Bryozoa, Cheilostomata)

Abstract. Deltaic populations of Conopeum seurati from diverse environmental settings have variable phenotypes related to strong competitive regimes and to dissolved oxygen minima. Under extremely stressful conditions, the poorly canalized phenotype of C. seurati displays new additional features such as kleistozooids ( kleistós = closed) and chaotic celleporoid layers. Kleistozooids are clearly distinguishable polymorphs characterized by the presence of a compact, imperforate frontal membrane and by a strongly reduced lumen of the "opesium". They commonly aggregate in clusters of regularly-arranged individuals that store a large quantity of proteic material. The inferred function of these cell-like structures is to supply nutrients for basic colony activities. Celleporoid layers are, possibly, a developmental relaxation of the colony of C. seurati for a more efficient use of space in competitive interactions.
Both celleporoid layers and kleistozooids reveal the magnitude of intracolony variability of a widespread opportunistic bryozoan species.     

Experimental and theoretical bond critical point properties for model electron density distributions for earth materials

Generalized X-ray scattering factor model experimental electron density distributions and bond critical point, bcp, properties generated in recent studies for the earth materials stishovite, forsterite, fayalite and cuprite with high energy single crystal synchrotron X-ray diffraction data and those generated with high resolution diffraction data for coesite and senarmonite were found to be adequate and in relatively good agreement, ~5% on average, with those calculated with quantum chemical methods with relatively robust basis sets. High resolution low energy single crystal diffraction data, recorded for the molecular sieve AlPO₄-15, were also found to yield model electron density distribution values at the bcp points for the AlO and PO bonded interactions that are in relatively good to moderately good agreement with the theoretical values, but the Laplacian values of the distribution at the points for the two bonded interactions were found to be in relatively poor agreement. In several cases, experimental bcp properties, generated with conventional low energy X-ray diffraction data for several rock forming minerals, were found overall to be in poorer agreement with the theoretical properties. The overall agreement between theoretical bcp properties generated with computational quantum methods and experimental properties generated with synchrotron high energy radiation not only provides a basis for using computational strategies for studying and modeling structures and their electron density distributions, but it also provides a basis for improving our understanding of the crystal chemistry and bonded interactions for earth materials. Theoretical bond critical point properties generated with computational quantum methods are believed to rival the accuracy of those determined experimentally. As such the calculations provide a powerful and efficient method for evaluating electron density distributions and the bonded interactions for a wide range of earth materials.Dedicated to Professor Robert F. Stewart of Carnegie Mellon University on his retirement for his brilliant and original work modeling electron density distributions.     

Metamorphism in the Olary Block, South Australia: compression with cooling in a Proterozoic fold belt

Abstract The sedimentary and igneous rocks comprising the lower Proterozoic Olary Block, South Australia, were deformed and metamorphosed during the mid-Proterozoic 'Olarian'Orogeny. The area is divided into three zones on the basis of assemblages in metapelitic rocks, higher grade conditions occurring in the south-east. Mineral assemblages developed during peak metamorphism, which accompanied recumbent folding, include andalusite in Zones I and II and sillimanite in Zone III. Upright folding and overprinting of mineral assemblages occurred during further compression, the new mineral assemblages including kyanite in Zone II and kyanite and sillimanite in Zone III. The timing relationships of the aluminosilicate polymorphs, together with the peak metamorphic and overprinting parageneses, imply an anticlockwise P–T path for the 'Olarian'Orogeny, pressure increasing with cooling from the metamorphic peak.     

大兴安岭北段斯木科流纹质碎斑熔岩特征及成因

在大兴安岭北段斯木科地区发育一种具有独特结构特征的火山岩石类型——流纹质碎斑熔岩,其具有熔岩和熔结凝灰岩的双重结构.岩石富Si、碱,Na₂O/K₂O=0.61~0.82,轻稀土富集,Eu亏损强烈,富集Rb、Th,亏损Ba、K,与同期流纹岩的地球化学特征相同,其区别主要在岩相学上.二者均形成于造山后伸展环境,属于由于岩浆向上运移、定位过程的不同而形成的"同质异相体".     

碳酸钙同质多象转变过程中氧同位素分馏的实验研究

本文通过“一步法”和“两步法”的“附晶生长法”分别合成了碳酸钙矿物，对其进行了同质多象转变过程中的氧同位素分馏行为的研究。同时通过真空条件下的同质多象转变实验，对文石和方解石的酸分馏系数的差异进行了实验验证。结果发现：①在50℃和70℃下，如果文石与水之间的氧同位素分馏未达到平衡，由母体文石经过同质多象转变生成的次生方解石完全继承的母体矿物的氧同位素组成。如果文石与水之间的氧同位素分馏达到平衡，由互过同质多象转变生成的次生方解石部分继承母体文石的氧同位素组成，并且次生方解石相对于母体文石富集^18O。②在0℃和25℃下，“一步法”的“附晶生长法”的实验结果表明，由六方方解石经过同质多象转变生成的次生方解石也完全继承母体矿物的氧同位素组成，并且在该温度下，矿物与水之间的氧同位素分馏与温度无关。     

大别山硬玉石英岩中发现α-PbO2型TiO2超高压相

大陆深俯冲深度对于了解大陆碰撞造山带中超高压变质岩的折返动力学具有重要意义.2005年笔者在中国大别山石马地区含柯石英榴辉岩绿辉石中发现了α-PbO2型TiO2晶体,最近笔者用高分辨透射电子显微镜和能量散射X-射线谱仪测试技术在中国大别山双河地区超高压硬玉石英岩硬玉中鉴别出纳米级α-PbO2型结构的TiO2天然超高压相.α-PbO2型TiO2晶体的保存,为超高压变质作用(6~7GPa,730~870°C)提供了新的证据,同时指示陆壳物质的俯冲深度大于170~200km,也指示了俯冲陆壳到地表的抬升,虽然其速率还不能确定,但可能是相当快速的.     

High Pressure Response of Rutile Polymorphs and Its Significance for Indicating the Subduction Depth of Continental Crust

α-PbO2-type TiO2 （TiO2-Ⅱ） is an important index mineral for ultrahigh-pressure metamorphism. After the discovery of a natural high-pressure phase of titanium oxide with α-PbO2- structure in omphacite from coesite-bearing eclogite at Shima in the Dabie Mountains, China, a nanoscale （〈2 nm） α-PbO2-type TiO2 has been identified through electron diffraction and high-resolution transmission electron microscopy in coesite-bearing jadeite quartzite at Shuanghe in the Dabie Mountains. The crystal structure is orthorhombic with lattice parameters a = 4.58×10-1 nm, b = 5.42×10-1 nm, c = 4.96×10-1 nm and space group Pbcn. The analysis results reveal that ruffle {011}R twin interface is a basic structural unit of α-PbO2-type TiO2. Nucleation of α-PbO2-type TiO2 lamellae is caused by the displacement of one half of the titanium cations within the {011}R twin slab. This displacement reduces the Ti-O-Ti distance and is favored by high pressure. The identification of α- PbO2-type TiO2 in coesite-bearing jadeite quartzite from Shuanghe, Dabie Mountains, provides a new and powerful evidence of ultrahigh-pressure metamorphism at 4--7 GPa, 850℃-900℃, and implies a burial of continental crustal rocks to 130-200 kilometers depth or deeper. The α-PbO2-type TiO2 may be a useful indicator of the pressure and temperature in the diamond stability field.     

The stability and compressibility of MgAl2O4 high-pressure polymorphs

High-pressure and high-temperature experiments using a laser-heated diamond anvil cell (LHDAC) and synchrotron X-ray diffraction have revealed a phase transition in MgAl₂O₄. CaTi₂O₄-type MgAl₂O₄ was found to be stable at pressures between 45 and at least 117 GPa. The transition pressure of CaTi₂O₄-type phase in MgAl₂O₄ is much lower than that in the natural N-type mid-oceanic ridge basalt composition. The Birch–Murnaghan equation of state for CaTi₂O₄-type MgAl₂O₄ was determined from the experimental unit cell parameters with K ₀=219(±6) GPa, K ₀′=4(constrained value), and V ₀=238.9(±9) ų. The observed compressibility was in agreement with the theoretical compressibility calculated in a previous study. ε-MgAl₂O₄ was observed at pressures between 40 and 45 GPa, which has not been reported in natural rock compositions. The gradient (dP/dT slope) of the transition from the ε-type to CaTi₂O₄-type MgAl₂O₄ had a positive value. These results should resolve the dispute regarding the stable high-pressure phase of MgAl₂O₄, which has been reported in earlier studies using both the multi-anvil press and the diamond anvil cell.     

High-pressure stability, structure and compressibility of Cmcm -MgAl2O4: an ab initio study

 Quantum-mechanical solid-state calculations have been performed on the highest-pressure polymorph of magnesium aluminate (CaTi₂O₄-type structure, Cmcm space group), as well as on the low-pressure (Fd3ˉm) spinel phase and on MgO and Al₂O₃. An ab initio all-electron periodic scheme with localized basis functions (Gaussian-type atomic orbitals) has been used, employing density-functional-theory Hamiltonians based on LDA and B3LYP functionals. Least-enthalpy structure optimizations in the pressure range 0 to 60 GPa have allowed us to predict: (1) the full crystal structure, the pV equation of state and the compressibility of Cmcm-MgAl₂O₄ as a function of pressure; (2) the phase diagram of the MgO–Al₂O₃–MgAl₂O₄ system (with exclusion of CaFe₂O₄-type Pmcn-MgAl₂O₄), and the equilibrium pressures for the reactions of formation/decomposition of the Fd3ˉm and Cmcm polymorphs of MgAl₂O₄ from the MgO + Al₂O₃ assemblage. Cmcm-MgAl₂O₄ is predicted to form at 39 and 57 GPa by LDA and B3LYP calculations, with K ₀=248 (K′=3.3) and 222 GPa (K′=3.8), respectively. Results are compared to experimental data, where available, and the performance of different DFT functionals is discussed. Received: 31 January 2001 / Accepted: 16 May 2001