High-pressure X-ray and Raman study of a ferrian magnesian spodumene

The high-pressure behaviour of a synthetic P2₁/c ferrian magnesian spodumene, ^M2 (Li_0.85Mg_0.09Fe²⁺ _0.06)^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆, has been investigated using in situ single-crystal X-ray diffraction and Raman spectroscopy. No phase transition has been observed within the pressure range investigated. The isothermal equation of state up to 7 GPa was determined. V₀, K_T0 and K, simultaneously refined with a Murnaghan equation of state, are: V₀= 415.66(7) ų, K_T0=83(1) GPa and K=9.6(6). The magnitudes of the principal unit-strain coefficients were calculated and their ratios 1:2:3=1.00:1.85:2.81 at P=6.83 GPa indicate a very strong anisotropy. Monitoring of the intensity of b-type reflections (h+k= 2n+1) confirms that from room conditions up to 7 GPa the primitive lattice is maintained. Raman spectra have been collected up to 7.4 GPa. No change in the number of observed vibrational modes occurs in the pressure range investigated. At high frequency, the Raman doublet relative to the Si–O–Si vibrations of the two distinct tetrahedral chains is a broad band at room pressure, however, the frequency difference between the two modes increases with increasing pressure.Operating system: Windows NT     

Charge-density analysis of spodumene (LiAlSi<Subscript>2</Subscript>O<Subscript>6</Subscript>), from ab initio Hartree–Fock calculations

An ab initio Hartree–Fock study of spodumene structure has been performed, and the wave function was used for a topological analysis of the electron density. The three non-equivalent oxygen atoms (O1, O2 and O3) of spodumene differed mainly in their valence shell charge concentration (VSCC). In particular, O1 shows a maximum of charge concentration along the Si–O bond path, and two other maxima, which can be regarded as lone pairs, point in the opposite direction with respect to the silicon position. O2 shows a torus of local charge concentration, whose axis is parallel to the Al–Si direction, with a bulge on the external side of the Si–O2–Al angle; even if no maximum exists in the Si direction, the valence shell of O2 appears to be strongly polarized toward the silicon; a slight polarization also exists along the Al–O bond path. A similar situation is displayed by O3, whose charge concentration has a torus-like shape, with the axis parallel to the Si–Si direction, and a bulge on the external side of the Si–O3–Si angle; as in the case of O2, a significant polarization of the valence shell of O3 is observed, towards the two Si directions. By recasting the calculated electron distribution in terms of the valence bond theory, a correlation has been found between structural details (bond lengths) and the hybridization state of the oxygen atoms.     

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.     

Crystal chemistry and OH defect concentrations in spodumene from different granitic pegmatites

Thirty spodumene samples of distinct paragenetic types (primary magmatic, secondary after petalite and hydrothermal) from variety of granitic pegmatites were characterized by electron microprobe, polarized FTIR spectroscopy and Mössbauer spectroscopy. The FTIR spectra of OH (weak sharp pleochroic bands at 3,425, 3,410, 3,395 cm⁻¹ and in the 3,500–3,470 spectral region) are strongly polarized with maximum absorption parallel to n_γ. The majority of OH dipoles are presumably generated by a partial replacement of O2 oxygen atoms with an orientation pointing above the Li vacancy site. The separation of the bands probably resulted from a replacement of the coordinating Al by Fe and Si by Al. Homogeneous spodumene mostly close to its ideal formula LiAlSi₂O₆ shows Fe (0.00–0.10 apfu as Fe³⁺; Fe³⁺ >> Fe²⁺) and Na (0.00–0.04 apfu) as the only minor cations and Fe³⁺Al₋₁ substitution up to 10 mol% of the LiFe³⁺Si₂O₆ component. Hydrogen concentrations (from 0.1 up to <5 ppm H₂O by weight) vary as a function of genetic type with the highest amounts in high-temperature magmatic spodumene. Differences among particular genetic types of spodumene are related to maximum solubility of OH in spodumene structure at given P–T conditions and at actual chemical composition of spodumene. OH defect concentrations in spodumene follow a trend, LT/LP pyroxenes containing lower hydrogen contents compared to HT/HP ones. The hydrogen contents in particular genetic types of spodumene and their decrease with decreasing T and P are consistent with petrologic models of the pegmatite (sub)types formations.     

川西甲基卡稀有金属矿集区伟晶岩脉矿化统计特征及地质找矿意义

四川川西甲基卡地区伟晶岩脉在地表有数量多、分布广的特征。通过对498条伟晶岩脉的统计表明,含锂辉石矿化伟晶岩脉体数量超过1/5,但达到大型矿床规模以上的概率仅为0.42%左右。因此,按照传统的地表填图,发现矿化露头—探槽揭露—深部钻探验证规模的勘查流程往往易陷入周期长、勘查成本高、找矿成功率低局面。该文以甲基卡新三号超大型锂辉石伟晶岩的发现过程为实例,探讨找矿方法巧妙组合,在找矿过程中的重要性。新三号脉综合了中大比例尺的地质、物、化探等手段,并不断对新方法、新手段进行工作方法试验,建立了物探定体化探定性对勘查对象作出远景评价,再结合地表掩盖区第四系寻根溯源转石法充分确定钻探验证位置,以达到经济-有效-找矿效果好的目的,对区域上开展同类型稀有矿床找矿工作勘查部署提供参考。     

锂辉石:巨型花岗伟晶岩锂-铯-钽矿床中关键含锂矿物SCIEI北大核心CSCD

寻找传统化石燃料的替代能源已成为全球性议题。受动力电池消费的拉动,锂资源需求急剧上升,伟晶岩型锂矿勘查热度持续攀升。虽然众多伟晶岩型锂矿地质特征尚不清晰,已有证据表明锂辉石是大多数大型-巨型伟晶岩型锂矿床的主要含锂矿物。与许多近直立的伟晶岩脉群不同,世界范围内大多数太古代伟晶岩矿脉往往呈近水平或缓倾斜在角闪岩相围岩中产出,它们往往具有复杂的三维形态并发育明显的矿物和地球化学分带。这些太古代伟晶岩脉通常形成于挤压或压剪构造体制下同变质环境中,成岩期最小主应力(σ;)近竖直。因此,伟晶岩常常侵位于近水平的构造局部引张区而形成复杂的几何学形态。压性的构造环境为富锂熔体多次脉动式注入和富含挥发分熔体垂向结晶分异提供了充足的时间;锂辉石在中高温压条件下结晶成为缓倾富锂带中最为常见的含锂矿物。     

Displacive phase transitions in C-centred clinopyroxenes: spodumene, LiScSi2O6 and ZnSiO3

The clinopyroxenes spodumene (LiAlSi₂O₆), LiScSi₂O₆ and ZnSiO₃, all with space group C2/c at ambient conditions, were studied under high pressures by single-crystal X-ray diffraction in a diamond-anvil cell. Changes in the evolution of the unit-cell parameters, optical properties and the appearance of h + k odd reflections characteristic of a primitive lattice, indicate that all three pyroxenes undergo phase transitions. The transitions are mostly displacive in character, and are non-quenchable. Transition pressures are 3.19 GPa in spodumene, ∼0.6 GPa in LiScSi₂O₆ and 1.92 GPa in ZnSiO₃. The space group of all three high-pressure phases was determined to be P2₁/c by structure refinement to single-crystal X-ray intensity data collected in the DAC. In the ZnSiO₃ clinopyroxene the intermediate P2₁/c phase further transforms to a second C2/c phase (HP-C2/c) at 4.9 GPa (confirmed by structure refinement). The volume change at this transition is about 2.6%, three times larger than in the first phase transition, and typical of the P2₁/c→ HP-C2/c phase transitions found previously in MgSiO₃, FeSiO₃, etc. These results therefore provide the first direct evidence that the HP-C2/c and the HT-C2/c structures of pyroxenes are distinct polymorphs with the same space group. The phase transition from C2/c to P2₁/c symmetry in spodumene and LiScSi₂O₆ therefore occurs because the polymorphs stable at ambient conditions are isotypic to the high-temperature C2/c phases of clinopyroxenes such as pigeonite and clinoenstatite. Received: 22 December 1999 / Accepted: 7 June 2000     

珠峰地区热曲锂辉石伟晶岩的发现及对喜马拉雅稀有金属成矿作用研究的启示

目前研究已经显示，喜马拉雅淡色花岗岩具有良好的铍-铌钽-锂等稀有金属成矿潜力。其中珠穆朗玛峰（后文简称珠峰）西侧的普士拉一带，是喜马拉雅地区锂辉石伟晶岩集中的区域。本文报道在普士拉东北的珠峰北侧热曲地区，发现有含锂辉石伟晶岩脉，这些伟晶岩呈透镜体状集中赋存于肉切村群"黄带层"大理岩与北坳组钙质硅酸岩的接触界线部位，同围岩一起经历了强烈的变形，且未出现明显内部分带结构，矿物组成中包含锂辉石、透锂长石、绿柱石、铌钽铁矿、锡石等锂-铍-铌钽-锡稀有金属矿物，其Li₂O含量达1.30%~2.15%，显示经历过高程度分异演化的岩浆结晶特征。热曲含锂辉石伟晶岩的发现表明珠峰地区具有锂成矿的良好前景，是未来锂矿产勘查的重点靶区，而藏南拆离系韧性剪切带中的肉切村群"黄带层"下部与北坳组顶部位置，是锂辉石伟晶岩的重要富集层位，值得今后在锂资源寻找过程中予以充分关注。