Si and O self-diffusion in hydrous forsterite and iron-bearing olivine from the perspective of defect chemistry

We discuss the experimental results of silicon and oxygen self-diffusion coefficients in forsterite and iron-bearing olivine from the perspective of defect chemistry. Silicon diffusion is dominated by V_O ^··-associated V_Si″″, whereas oxygen diffusion is dominated by hopping of V_O ^·· under anhydrous conditions, and by (OH)_O ^· under hydrous conditions. By considering the charge neutrality condition of [(OH)_O ^·] = 2[V_Me″] in hydrous forsterite and iron-bearing olivine, we get D _Si ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))^1/3 and D _O ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))⁰, which explains the experimental results of water effects on oxygen and silicon self-diffusion rates (Fei et al. in Nature 498:213–215, 2013; J Geophys Res 119:7598–7606, 2014). The \(C_{{{\text{H}}_{2} {\text{O}}}}\) dependence of creep rate in the Earth’s mantle should be close to that given by Si and O self-diffusion coefficients obtained under water unsaturated conditions.     

Hydrogen sites in the dense hydrous magnesian silicate phase E: a pulsed neutron powder diffraction study

Hydrogen site positions and occupancy in the crystal structure of dense hydrous magnesium silicate (DHMS) phase E were determined for the first time by pulsed neutron powder diffraction. A fully deuterated pure phase E powder sample, which had space group \(R\overline{3} m\) and lattice parameters of a = 2.97065(8) Å and c = 13.9033(4) Å, was synthesized at 15 GPa and 1100 °C. Through quantitative evaluation of refined structure parameters obtained with sufficient spatial resolution and very high signal-to-background ratio, we conclude that the O–D dipoles in the refined phase E structure are tilted by 24° from the direction normal to the layers of edge-shared MgO₆ octahedra (octahedral layers). The tilted dipole structure of phase E is in remarkable contrast to that of brucite, Mg(OH)₂, which has dipoles exactly normal to the octahedral layer. This contrast exists because the O–Si–O bonding unique in the phase E structure connects two adjacent octahedral layers and thereby reduces the interlayer O···O distance. This shrinkage of the interlayer distance induces the tilting of the O–D dipole and also generates unique O–D···O hydrogen bonding connecting all the layers in the phase E structure.     

Thermal equation of state of natural tourmaline at high pressure and temperature

Synchrotron-based in situ angle-dispersive X-ray diffraction experiments were conducted on a natural uvite-dominated tourmaline sample by using an external-heating diamond anvil cell at simultaneously high pressures and temperatures up to 18 GPa and 723 K, respectively. The angle-dispersive X-ray diffraction data reveal no indication of a structural phase transition over the P–T range of the current experiment in this study. The pressure–volume–temperature data were fitted by the high-temperature Birch–Murnaghan equation of state. Isothermal bulk modulus of K ₀ = 96.6 (9) GPa, pressure derivative of the bulk modulus of \(K_{0}^{\prime } = 12.5 \;(4)\), thermal expansion coefficient of α ₀ = 4.39 (27) × 10^?5 K^?1 and temperature derivative of the bulk modulus (?K/?T) _P  = ?0.009 (6) GPa K^?1 were obtained. The axial thermoelastic properties were also obtained with K _a0 = 139 (2) GPa, \(K_{a0}^{\prime }\) = 11.5 (7) and α _a0 = 1.00 (11) × 10^?5 K^?1 for the a-axis, and K _c0 = 59 (1) GPa, \(K_{c0}^{\prime }\) = 11.4 (5) and α _c0 = 2.41 (24) × 10^?5 K^?1 for the c-axis. Both of axial compression and thermal expansion exhibit large anisotropic behavior. Thermoelastic parameters of tourmaline in this study were also compared with that of the other two ring silicates of beryl and cordierite.     

Ionic conductivity in gem-quality single-crystal alkali feldspar from the Eifel: temperature,orientation and composition dependence

We measured the ion conductivity of single-crystal alkali feldspar originating from two different locations in the Eifel/Germany, named Volkesfeld and Rockeskyller sanidine and having potassium site fractions \(C_\mathrm{K}\) of 0.83 and 0.71, respectively. The dc conductivities resulting from electrochemical impedance spectroscopy over the temperature range of 300–900 \(^{\circ }\hbox {C}\) show a weak composition dependence but pronounced differences between the b-direction [\(\perp (010)\)] and \(c^{*}\)-direction [\(\perp (001)\)] of the monoclinic feldspar structure. Conductivity activation energies obtained from the observed linear Arrhenius plots are close to 1.2 eV in all cases, which is closely similar to the activation energies of the \(^{22}\mathrm{Na}\) tracer diffusivity in the same crystals. Taking into account literature data on K tracer diffusion and diffusion correlation effects, the present results point to a predominance of the interstitialcy mechanism over the vacancy mechanism in mass and charge transport on the alkali sublattice in potassium-rich alkali feldspar.     

Phase relation of CaSO<Subscript>4</Subscript> at high pressure and temperature up to 90 GPa and 2300 K

Calcium sulfate (CaSO₄), one of the major sulfate minerals in the Earth’s crust, is expected to play a major role in sulfur recycling into the deep mantle. Here, we investigated the crystal structure and phase relation of CaSO₄ up to ~90 GPa and 2300 K through a series of high-pressure experiments combined with in situ X-ray diffraction. CaSO₄ forms three thermodynamically stable polymorphs: anhydrite (stable below 3 GPa), monazite-type phase (stable between 3 and ~13 GPa) and barite-type phase (stable up to at least 93 GPa). Anhydrite to monazite-type phase transition is induced by pressure even at room temperature, while monazite- to barite-type transition requires heating at least to 1500 K at ~20 GPa. The barite-type phase cannot always be quenched from high temperature and is distorted to metastable AgMnO₄-type structure or another modified barite structure depending on pressure. We obtained the pressure–volume data and density of anhydrite, monazite- and barite-type phases and found that their densities are lower than those calculated from the PREM model in the studied P–T conditions. This suggests that CaSO₄ is gravitationally unstable in the mantle and fluid/melt phase into which sulfur dissolves and/or sulfate–sulfide speciation may play a major role in the sulfur recycling into the deep Earth.     

In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.     

Anisotropic mechanical properties of zircon and the effect of radiation damage

This study provides new insights into the relationship between radiation-dose-dependent structural damage due to natural U and Th impurities and the anisotropic mechanical properties (Poisson’s ratio, elastic modulus and hardness) of zircon. Natural zircon samples from Sri Lanka (see Muarakami et al. in Am Mineral 76:1510–1532, 1991) and synthetic samples, covering a dose range of zero up to 6.8 × 10¹⁸ α-decays/g, have been studied by nanoindentation. Measurements along the [100] crystallographic direction and calculations, based on elastic stiffness constants determined by Özkan (J Appl Phys 47:4772–4779, 1976), revealed a general radiation-induced decrease in stiffness (~54 %) and hardness (~48 %) and an increase in the Poisson’s ratio (~54 %) with increasing dose. Additional indentations on selected samples along the [001] allowed one to follow the amorphization process to the point that the mechanical properties are isotropic. This work shows that the radiation-dose-dependent changes of the mechanical properties of zircon can be directly correlated with the amorphous fraction as determined by previous investigations with local and global probes (Ríos et al. in J Phys Condens Matter 12:2401–2412, 2000a; Farnan and Salje in J Appl Phys 89:2084–2090, 2001; Zhang and Salje in J Phys Condens Matter 13:3057–3071, 2001). The excellent agreement, revealed by the different methods, indicates a large influence of structural and even local phenomena on the macroscopic mechanical properties. Therefore, this study indicates the importance of acquiring better knowledge about the mechanical long-term stability of radiation-damaged materials.     

华南壳幔结构与动力学的宽频地震观测研究

了解华南各岩石圈块体壳幔结构和各向异性方面的差异是揭示华南深部构造演化的基础。本文利用布设于华南的两条宽频地震测线观测数据,采用多种地震学方法对华南的地壳上地幔结构和各向异性进行了研究。接收函数结果表明,华南地区地壳厚度和岩石圈厚度都较薄,地壳厚度自东南沿海向西北内陆增厚,扬子克拉通的泊松比(波速比)低于华夏块体,表明扬子克拉通地壳较华夏块体更偏长英质。约北纬29°以北的扬子克拉通地幔转换带厚度明显增厚,可能是由地幔转换带底部停滞的冷的古太平洋板片或中生代克拉通碰撞残留造成的。层析成像结果显示华南上地幔具有很强的横向差异性,上地幔中的强烈低速异常体可能对应了晚中生代发生广泛岩浆作用时的岩浆房和岩浆通道。台湾下方的上地幔存在南北横向差异明显的高速异常,分别对应台湾南部向东俯冲的欧亚板块及台湾北部向北俯冲的菲律宾海板块。俯冲的欧亚板块在台湾南部是连续的,而在台湾中北部,由于与菲律宾海板块的相互作用,俯冲的欧亚板块被折断。剪切波分裂结果显示,以江绍断裂为界,华夏块体与扬子克拉通的岩石圈地幔各向异性存在明显的横向变化,表明两者的构造演化过程有显著差异。     

乌南油田滨浅湖砂体储层构型及其油气意义

基于Miall储层构型研究思想,结合岩心、测井、测试等资料,对乌南油田砂坝砂体储层构型界面特征进行了研究,确定了储层构型界面识别标志;在此基础上,将砂坝内部构型分为坝主体和坝侧缘,同时通过动、静态结合,明确砂坝外部构型存在孤立、视连通、左侧向叠置和右侧向叠置4种模式;纵向上发育湖退（进积）和湖进（退积）两种砂体发育模式。坝主体是主力储层,具有良好油气显示;坝主体分布面积大、出现频率高为油气有利区域。