Theoretical study of point defects in crystalline zircon

We present a numerical study of point defects in crystalline zircon (ZrSiO₄). Vacancies and interstitials of all the constituents of zircon have been considered. For each defect, the structure and the formation energies have been calculated. Calculations, using the supercell method, are based on the Density Functional Theory in the Local Density Approximation. Empirical potentials have also been considered for comparison with electronic structure results. We find a formation energy for the oxygen interstitial of 1.7 eV. This value is compatible with the experimental activation energy for oxygen diffusion in zircon, which proves an interstitial mechanism for the diffusion of oxygen in zircon. For all other defects the calculated formation energies lead to negligible thermal concentration at equilibrium. Received: 8 January 1999 / Revised, accepted: 14 May 1999     

Alkali ion migration in albite and K-feldspar

As part of a study of ion migration mechanisms in feldspars, the dynamical behaviour of the alkali metal cations ions in albite and K-feldspar has been investigated using a combination of dielectric spectroscopy and atomistic computer simulation techniques. The low-frequency dielectric properties of these minerals have been studied from room temperature to 1100 K. At each temperature, the dielectric constant, conductivity and dielectric loss were determined over a range of frequencies from 100 Hz to 10 MHz. At high temperatures a distinct Debye-type relaxation in the dielectric loss spectra was observed for both albite and K-feldspar; the activation energy for these processes was determined to be 1.33 eV in both albite and K–feldspar. Atomistic simulation techniques were used to elucidate the mechanism and energetics of the cation migration processes. Mechanisms involving the conventional hopping of Na⁺ and K⁺ ions between cation sites in the (010) plane were found to give calculated energy barriers in good agreement with the experimentally determined activation energies. These results assist in understanding the nature of the processes responsible for the observed dielectric behaviour.     

黑鳞云母花岗质岩浆的结晶分异及钠长花岗质岩浆的形成

以含F、过铝质、K_2O>Na_2O为特征的浅色黑鳞云母花岗岩为初始物,在P=150MPa,T=850～650℃和H_2O不饱和条件下进行熔化-结晶分异实验,结果表明:首先晶出的是石英和富钾碱性长石;随结晶温度下降和结晶相含量的增加,残余熔体中挥发份F及Na_2O、Al_2O_3含量逐渐增加,SiO_2、K_2O、CaO含量减少,显示含F浅色花岗质熔体具有向贫硅富钠的富氟钠长花岗质熔体组成演化的趋势;700℃开始,残余熔体具有天然富氟钠长花岗岩的组成特征:富Na_2O(Na_2O>K_2O)、Al_2O_3(>16％)和F(>1.5％)。上述残余熔体组成的演化特征与自然界从含氟黑鳞云母花岗岩到富氟钠长花岗岩的组成变化规律是一致的,充分证明了在本文的实验条件下,含氟黑鳞云母花岗岩能够经结晶分异演化出富氟钠长花岗岩熔体。     

Grands gisements d'albite dans le massif métamorphique de Menderes (Turquie occidentale)

Albite deposits of western Turkey occur within gneiss in the basal part of the Menderes Metamorphic Massif. The most important deposits are located along the Karadere mineralization zone, within an anticlinorium of 15-km length with a direction of N10–30E. Detailed study of the four deposits forming the northern part of this zone has allowed us to discover large reserves of 100.65 million tons, of which 78% is composed of high-grade ore with a content of 10.27% Na₂O. The remainder is formed by low-grade ore with 8.37% Na₂O and 1.11% K₂O and mixed ore with 4.61% Na₂O and 4.05% K₂O, with reserves of 14.4 and 8.2 million tons, respectively. To cite this article: U. Çak?r, C. R. Geoscience 337 (2005).     

Solubility of the assemblage albite+K-feldspar+andalusite+quartz in supercritical aqueous chloride solutions at 650 °C and 2 kbar

The solubility of the high grade pelite assemblage albite+K-feldspar+andalusite+quartz at 650 °C and 2 kbar was determined in aqueous solutions over a total chloride range of 0.01–3 m_Cl^tot using rapid-quench hydrothermal technique. The concentration of Na, K, Si, and Al was determined in the fluid phase after quench. The K/Na ratio was determined by approaching the equilibrium from below and above. It is 0.34 at low chloride concentrations and decreases slightly to 0.31 with increasing total chloride. Silica and aluminum concentrations were determined only from undersaturation. The silica solubility is found to be independent of chloride concentration and is 0.13 molal. Aluminum is nearly independent of chloride concentration decreasing only slightly from 0.0015 to 0.0007 molal. Comparison of the experimental data with thermodynamic model calculations demonstrates that the silica concentrations are well predicted, while significant differences exist between individual databases for Al speciation and its total concentration. Al concentrations are underestimated by up to 10 to 15 orders of magnitude using the SUPCRT92 database. Predicted K/Na ratios are underestimated by up to 30%. The best predictions achieved for this simplified high-grade pelite assemblage are those using the SUPCRT92 database with revised thermodynamic data for feldspars and K- and Na-species (J. Phys. Chem. Ref. Data 24 (1995) 1401) and additional Al-species (Am. J. Sci. 295 (1995) 1255; Geochim. Cosmochim. Acta 61 (1997) 2175). The use of ideal mixing for neutral complexes in combination with the extended Debye–Hückel activity model for the charged species yields the most compatible speciation model.     

Experimental deformation of sintered albite above and below the order-disorder transition

Abstract

Purified albite powder (44-53 μm) has been sintered to form an albite polycrystal suitable for deformation studies close to the melting temperature. Experiments have been carried out in Griggs solid medium deformation apparatus at 800, 1020 °C and 700 MPa pressure in a dehydrating pyrophyllite confining medium at constant strain rates of 10^?4, 10^?5, 10^?6 and 10^?7/s. At 800 °C the samples were brittle-ductile whereas at 1020 °C they were ductile with a rheology well described by a power law with a stress exponent of 3. The transition from brittle-ductile to ductile also coincided with the order-disorder or low-high albite transition, as indicated by the marked increase in mechanical twinning on the albite law at high temperature. At 1020 °C high dislocation densities (10^?10 - 10^?11/cm² and mechanical twinning characterised the original high albite grains, whereas fine recrystallised grains ( < 5 цm) had low dislocation densities (10⁷ - 10⁸/cm²) and often contained polysynthetic albite and pericline (M-type) twins. It is suggested that the recrystallized grains were monalbite (monoclinic) under test conditions which have inverted to high albite (triclinic) and in so doing produced M-twins, and that the recrystallization mechanism involved grain-boundary bulging to nucleate new high angle boundaries. The implications of the order-disorder transition for twinning and grain boundary migration are discussed and it is suggested that the data cannot be simply extrapolated to natural deformation in the low albite field.     

陕西二台子铜金床钠长石碳酸（角砾）岩类特征及形成构造背景分析

从岩石学、矿物学、岩石化学、地球化学、稀土元素等方面研究了二台子铜金矿内长石炭酸（角砾）岩类地质地球化学特征。晚泥盆世－石炭纪,在区域幔羽构造作用下,深部热流体沿先存在构造通道上升进入镇安二台子三级热水沉积盆地之中,形成了石英重晶石炭酸角砾岩、碳酸角砾岩、复成分角砾岩、钠长岩、钠长石碳酸岩,受同性断裂及层位控制明显,并构成了金的矿源层及普遍金矿化。燕山期,具有幔源特征的深部含矿热流体在北东、北西向     

Transport properties of high albite crystals,near-endmember feldspar and pyroxene glasses,and their melts to high temperature

Thermal diffusivity (D) was measured using laser-flash analysis (LFA) from oriented single-crystal albite and glasses near LiAlSi₃O₈, NaAlSi₃O₈, CaAl₂Si₂O₈, LiAlSi₂O₆ and CaMgSi₂O₆ compositions. Viscosity measurements of the supercooled liquids, over 2.6 × 10⁸ to 8.9 × 10¹² Pa s, confirm strongly non-Arrhenian behavior for CaAl₂Si₂O₈, and CaMgSi₂O₆, and near-Arrhenian behavior for the others. As T increases, D _glass decreases, approaching a constant near 1,000 K. Upon crossing the glass transition, D decreases rapidly. For feldspars, D for the melt is ~15% below D of the bulk crystal, whereas for pyroxenes, this difference is ~40%. Thermal conductivity (k _lat = ρC _P D) of crystals decreases with increasing T, but k _lat of glasses increases with T because heat capacity (C _P ) increases with T more strongly than density (ρ) and D decrease. For feldspars, k _lat for the melt is ~10% below that of the bulk crystal or glass, whereas this decrease for pyroxene is ~50%. Therefore, melting substantially impedes heat transport, providing positive thermal feedback that could promote further melting.     

Experimental multipole-refined and theoretical charge density study of LiGaSi<Subscript>2</Subscript>O<Subscript>6</Subscript> clinopyroxene at ambient conditions

The synthetic LiGaSi₂O₆ clinopyroxene is monoclinic C2/c at room-T. Its experimental electron density, ρ(r), has been derived starting from accurate room-T single-crystal diffraction data. Topological analysis confirms an intermediate ionic-covalent character for Si–O bonding, as found by previous electron-density studies on other silicates such as diopside, coesite and stishovite. The non-bridging Si–O bonds have more covalent character than the bridging ones. The Ga–O bonds have different bonding characters, the Ga–O2 bond being more covalent than the two Ga–O1 bonds. Li–O bonds are classified as pure closed-shell ionic interactions. Similar to spodumene (LiAlSi₂O₆), Li has sixfold coordination, but the bond critical points associated to the two longest bonds are characterized by very low electron density values. Similar to what previously found in spodumene and diopside, O···O interactions were detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. In particular, this kind of interaction has been obtained for the O1···O1 edge shared between two Ga octahedra. Integration over the atomic basins gives net charges of −1.39(10), 2.82(10), 1.91(10) and 0.82(8) e for O (averaged), Si, Ga and Li atoms, respectively. Periodic Hartree–Fock and DFT calculations confirm the results obtained by multipole refinement of the experimental data. Moreover, the theoretical topological properties of the electron density distribution on the Si₂O₆ group are very similar to those calculated for spodumene. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Cathodoluminescence of authigenic albite

Authigenic albites in carbonate rocks typically grow in a high-grade diagenetic to low-grade metamorphic environment and often show Roc-Tourné-twinning sensu Füchtbauer. Based on an investigation of four Middle to South European occurrences, they show Mn²⁺- and Fe³⁺-activated cathodoluminescence (CL), as revealed by combined high resolution spectroscopy of cathodoluminescence emission (HRS-CL), electron paramagnetic resonance (EPR), and proton-induced X-ray emission (μPIXE).     

Point defects in crystalline zircon (zirconium silicate), ZrSiO<Subscript>4</Subscript>: electron paramagnetic resonance studies

This article outlines the present state of knowledge of paramagnetic defects in crystalline zircon as obtained mainly, but not exclusively, from electron paramagnetic resonance (EPR) studies in crystalline zircon (zirconium silicate, ZrSiO₄). The emphasis is on single-crystal studies where, in principle, unambiguous analysis is possible. Firstly, the crystallography of zircon is presented. Secondly, the relationships between available crystal-site symmetries and the symmetries of observed paramagnetic species in zircon, and how these observations lead to unambiguous assignments of point-group symmetries for particular paramagnetic species are detailed. Next, spin-Hamiltonian (SH) analysis is discussed with emphasis on the symmetry relationships that necessarily exist amongst the Laue classes of the crystal sites in zircon, the paramagnetic species occupying those sites and the SH itself. The final sections of the article then survey the results of EPR studies on zircon over the period 1960–2002.     

Mixing properties and stability of jadeite-acmite pyroxene in the presence of albite and quartz

The stability of synthetic jadeite-acmite pyroxene coexisting with albite and quartz has been determined at 600, 700, and 900° C. The end-member reaction: albite = jadeite + quartz has been determined to lie between 1.67 and 1.70 GPa at 600° C, 1.88 and 1.90 GPa at 700° C, and 2.44 and 2.48 GPa at 900° C. Jd₇₈Acm₂₂ + quartz is stable above 1.58, 1.78, and 2.33 GPa at 600, 700, and 900° C, respectively. Jd₆₁Acm₃₉ + quartz is stable above 1.47, 1.67, and 2.18 GPa at 600, 700, and 900° C, respectively. Addition of as much as 40% of acmite component in jadeite extends pyroxene stability by less than 300 MPa at 900° C. Unit-cell parameters measured for synthetic jadeite-acmite pyroxenes indicate linear volume-composition relations. The data are consistent with ideal mixing in jadeite-acmite solutions.     

高温高压下黄铁矿热力学性质的第一性原理研究

黄铁矿是自然界中分布最为广泛的硫化物矿物,同时也是重要的造矿矿物,在金属矿床、沉积岩、变质岩、花岗岩、基性-超基性岩浆岩、以及地幔岩中都有大量出现。因此,研究黄铁矿在不同温度压力下的热力学性质可以为深入探讨与黄铁矿有关的成岩、成矿、成藏问题提供有用的矿物学依据。本文利用基于密度泛函微扰理论的第一性原理方法,采用准谐近似计算了黄铁矿在高温高压下的热力学性质。我们计算的黄铁矿的晶格常数、零压下的体积模量及其对压力的导数与前人的实验及理论计算结果吻合得很好,零压下等压热容和熵随温度的变化与实验结果有很好的一致性。尤其是,本文计算了直至2500K、100GPa的高温高压下黄铁矿的等温体积模量、热膨胀系数、热容和熵等热力学性质。这为在有硫参与的情况下,人们开展下地壳-岩石圈地幔深度的地球动力学模拟和建立地球物理模型提供了有用的信息。     

Mechanisms of hydrogen incorporation and diffusion in iron-bearing olivine

The incorporation and diffusion of hydrogen in San Carlos olivine (Fo₉₀) single crystals were studied by performing experiments under hydrothermal conditions. The experiments were carried out either at 1.5 GPa, 1,000°C for 1.5 h in a piston cylinder apparatus or at 0.2 GPa, 900°C for 1 or 20 h in a cold-seal vessel. The oxygen fugacity was buffered using Ni–NiO, and the silica activity was buffered by adding San Carlos orthopyroxene powders. Polarized Fourier transform infrared (FTIR) spectroscopy was utilized to quantify the hydroxyl distributions in the samples after the experiments. The resulting infrared spectra reproduce the features of FTIR spectra that are observed in olivine from common mantle peridotite xenoliths. The hydrogen concentration at the edges of the hydrogenated olivine crystals corresponds to concentration levels calculated from published water solubility laws. Hydrogen diffusivities were determined for the three crystallographic axes from profiles of water content as a function of position. The chemical diffusion coefficients are comparable to those previously reported for natural iron-bearing olivine. At high temperature, hydrogenation is dominated by coupled diffusion of protons and octahedrally coordinated metal vacancies where the vacancy diffusion rate limits the process. From the experimental data, we determined the following diffusion laws (diffusivity in m² s⁻¹, activation energies in kJ mol⁻¹): for diffusion along [100] and [010]; for diffusion along [001]. These diffusion rates are fast enough to modify significantly water contents within olivine grains in xenoliths ascending from the mantle.     

Water diffusion in synthetic iron-free forsterite

The kinetics of hydrogenation of dry synthetic forsterite single crystals was determined by performing experiments under hydrothermal conditions. The experiments were performed at 1.5 GPa, 1000 °C for 3 h in a piston-cylinder apparatus, or at 0.2 GPa, 900–1110 °C, for 3–20 h in TZM cold-seal vessels. The oxygen fugacity was buffered using Fe–FeO or Ni–NiO powders. Polarized Fourier transform infrared spectroscopy was utilized to quantify the hydroxyl distributions in the samples after the experiments. Hydrogenation rates were measured parallel to the three crystallographic axes from profiles of water content as a function of position in the samples. The chemical diffusion coefficients are marginally slower than in natural iron-bearing olivine for the same diffusion process, but the anisotropy of diffusion is the same, with the [001] axis the fastest direction of diffusion and [100] the slowest. Fits of the diffusion data to an Arrhenius law yield similar activation energies for each of the crystallographic axes; a global fit to all the diffusion data gave 211 ± 18 kJ mol^–1, in reasonable agreement with the previous results for natural olivine. Thus hydrogenation most likely occurs by coupled diffusion of protons and octahedrally coordinated metal vacancies. The diffusion rates are fast enough to modify water contents within xenoliths ascending from the mantle, but probably too slow to permit a total equilibration of forsterite or olivine crystals.     

Hydrogen Incorporation in Crystalline Jadeite: Insight from First Principles Calculations

Hydrogen incorporation is critical for explaining defect energies, structure parameters and other physical characteristics of minerals and understanding mantle dynamics. This work analyzed the hydrogen complex defects in jadeite by the plane-wave pseudo-potential method based on density functional theory, and optimized the atomic positions and lattice constants in all configurations(different defective systems). Incorporation mechanisms considered for hydrogen(H) in jadeite include:(1) hydrogen incorporating with the O2 site oxygen and coexisting with M2 vacancy;(2) one H atom combined with an Al atom replacing Si in tetrahedron;(3) 4H atoms directly replacing Si in tetrahedron and(4) 3H atoms replacing Al on the M1 site. The four incorporation mechanisms mentioned above form the corresponding V_(Na)-H_i, Al_(Si)-H_i, V_(Si)-4H_i and V_(Al)-3H_i point defects. The molecular dynamics simulation to the ideal, V_(Na)-H_i, Al_(Si)-H_i, V_(Si)-4H_i and V_(Al)-3H_i point defects under the P-T conditions of 900 K, 2 GPa, the V_(Na)-H_i and Al_(Si)-H_i point defects under different pressures at T = 900 K, and Al_(Si)-H_i point defects under different temperatures at P = 3 GPa was performed to examine the preferential mode of hydrogen incorporation in jadeite by means of first-principles calculations. The calculations show that the averaged O–H bond-length in the hydrogen point defects system decreased in the order of Al_(Si)-H_i, V_(Na)-H_i, V_(Si)-4H_i and V_(Al)-3H_i. V_(Na)-H_i complex defects result in a contraction of the jadeite volume and the presence of Al_(Si)-H_i, V_(Si)-4H_i and V_(Al)-3H_i defects could increase the supercell volume, which is the most obvious in the V_(Al)-3H_i defects. The energy of formation of Al_(Si)-H_i and V_(Al)-3H_i complex defects was much lower than that of other defect systems. The V_(Al)-3H_i defects system has the lowest energy and the shortest O–H bond-length, suggesting that this system is the most favorable. The analytical results of vacancy formation energy, O–H bondlength, and the stability of the hydrogen defects in jadeite have suggested that the preferred hydration incorporation mode in jadeite is V_(Al)-3H_i complex defect.     

与翡翠伴生的含钠长石质玉石的鉴别及定名探讨

与翡翠伴生的含钠长石质玉石的外观与传统翡翠非常相似,但成分比较复杂,宝石学参数不再典型,性质常介于钠长石玉和翡翠之间。通过对标本的观察、常规宝石学测试和红外光谱测试,对该过渡类型玉石进行仔细区域调查,总结特征,建议国家标准应加强对翡翠与岩石过渡类型具体的成分标准和物理性质的归钠总结,对相应的类型划分与种类界定提出规范性和统一的标准。     

Concentration of K-feldspar from a pegmatitic feldspar ore by flotation

Abundant reserves of Na-feldspar (albite) and K-feldspar (orthoclase or microcline) are found in granites, syenite, tracite and pegmatites. As both feldspar minerals have similar chemical structure and physicochemical properties, their separation is challenging. Flotation is known to be the only technique to enable their separation. The fundamentals on the separation of these minerals were well documented in our earlier studies. In this study, a pegmatite ore with a K₂O/Na₂O (3.78:3.37) ratio of 1.12 was studied in a Denver flotation cell both at natural and acidic pH using HF and H₂SO₄. Because of the perthitic structure of the ore no significant separation is observed at natural pH. Interestingly, a selective separation was achieved at low pH using HF and H₂SO₄ (pH 2.5–2.8). The selectivity is induced by the addition of Na⁺ ions through depression of albite. Selective separation has been carried out by stagewise flotation using the tree technique. Accordingly, a pegmatite ore composed of 3.37% Na₂O and 3.78% K₂O is upgraded to 10.51% K₂O and 3.02% Na₂O with a K₂O/Na₂O = 3.48 in HF medium and to 2.55 in H₂SO₄ medium. It is shown that products recovered in other stages are also considered as commercially significant. Especially, quartz, which is recovered in the tailings in HF medium, is suitable for glass industry. The overall results show that commercial utilization of these results is possible.     

Viscosity of albite melt at high pressure and high temperature

 The viscosity of albite (NaAlSi₃O₈) melt was measured at high pressure by the in situ falling-sphere method using a high-resolution X-ray CCD camera and a large-volume multianvil apparatus installed at SPring-8. This system enabled us to conduct in situ viscosity measurements more accurately than that using the conventional technique at pressures of up to several gigapascals and viscosity in the order of 10⁰ Pa s. The viscosity of albite melt is 5.8 Pa s at 2.6 GPa and 2.2 Pa s at 5.3 GPa and 1973 K. Experiments at 1873 and 1973 K show that the decrease in viscosity continues to 5.3 GPa. The activation energy for viscosity is estimated to be 316(8) kJ mol⁻¹ at 3.3 GPa. Molecular dynamics simulations suggest that a gradual decrease in viscosity of albite melt at high pressure may be explained by structural changes such as an increase in the coordination number of aluminum in the melt. Received: 6 January 2001 / Accepted: 27 August 2001     

Point defects and cation tracer diffusion in (Ti x Fe 1?x ) 3?δ O4 1. Non-stoichiometry and point defects

 The deviation from stoichiometry, δ, in spinel solid solutions of the type (Ti _x Fe _1−x )_3−δ O₄ with x=0.1, 0.2 and 0.25 was studied thermogravimetrically as a function of oxygen activity, a _O2, at 1100, 1200 and 1300 ^∘C. The experimental results, S-shaped curves for δ vs. log a_O2, are presented and discussed with regard to the type of point defects prevailing under different conditions in the deviation from stoichiometry. It is concluded that cation vacancies are the predominant point defects at high oxygen activities, while cation interstitials prevail at low oxygen activities. The temperature and composition dependencies of point defect concentrations are also discussed. Received: 1 October 1996 / Accepted: 15 September 2002 Acknowledgements The authors thank the US Department of Energy for support of this work under Grant no. DE-FGO2–88ER45357. This work made use of the Cornell Center of Materials Shared Experimental Facilities, supported through the National Science Foundation Materials Research Science and Engineering Centers program (DMR-0079992).