Monte Carlo simulation of mixing in Ca3Fe2Ge3O12–Ca4Ge4O12 garnets and implications for the thermodynamic stability of pyrope–majorite solid solution     

Victor L. Vinograd  Bjoern Winkler  Daniel J. Wilson  Andrew Putnis  Julian D. Gale 《Physics and Chemistry of Minerals》2006,33(8-9):533-544

Static lattice energy calculations, based on empirical pair potentials, were performed for a large set of structures differing in the arrangement of octahedral cations within the garnet 2 × 2 × 2 supercell. The compositions of these structures varied between Ca₃Fe₂Ge₃O₁₂ and Ca₄Ge₄O₁₂. The energies were cluster expanded using pair and quaternary terms. The derived ordering constants were used to constrain Monte Carlo simulations of temperature-dependent mixing properties in the ranges of 1,073–3,673 K and 0–10 GPa. The free energies of mixing were calculated using the method of thermodynamic integration. The calculations predict a wide miscibility gap between Fe-rich (cubic) and Fe-pure (tetragonal) garnets consistent with recent experimental observations of Iezzi et al. (Phys Chem Miner 32:197–207, 2005). It is shown that the miscibility gap arises due to a very strong cation ordering at the Fe-pure composition, driven by the charge difference between Ca²⁺ and Ge⁴⁺ cations. The structural and thermodynamic analogies between Ca–Ge and Mg–Si systems suggest that a similar miscibility gap should exist between pyrope and Mg–Si-majorite.  相似文献   

Aspects of diamond mineralisation and distribution at the Helam Mine, South Africa     

N. Mc Kenna  J.J. Gurney  J. Klump  J.M. Davidson 《Lithos》2004,77(1-4):193-208

The diamonds from the Swartruggens dyke swarm are mainly tetrahexahedra, with subsidiary octahedral and cuboid crystals. They are predominantly colourless, with subordinate yellows, browns, and greens. The existence of discrete cores and oscillatory growth structures within the diamonds, together with the recognition of harzburgite, lherzolite, at least two eclogitic and a websteritic diamond paragenesis, variable nitrogen contents, and both Type IaAB and Type Ib–IaA diamonds provides evidence for episodic diamond growth in at least six different environments. The predominance of plastic deformation in the diamonds, the state of nitrogen aggregation, and the suite of inclusion minerals recovered are all consistent with a xenocrystic origin for the diamonds, with the Type Ib–IaA diamonds being much younger than the rest. Mantle storage at a time-averaged temperature of ±1100 °C is inferred for the Type IaAB diamonds. The distribution of mantle xenocrysts of garnet and chromite within the high-grade Main kimberlite dyke compared to the low-grade Changehouse kimberlite dyke strongly suggests that the difference in diamond content is due to an increased eclogitic component of diamonds in the Main kimberlite dyke.  相似文献   

The trace element composition of silicate inclusions in diamonds: a review   总被引：1，自引：0，他引：1  

Thomas Stachel  Sonja Aulbach  Gerhard P. Brey  Jeff W. Harris  Ingrid Leost  Ralf Tappert  K.S. Viljoen 《Lithos》2004,77(1-4):1-19

On a global scale, peridotitic garnet inclusions in diamonds from the subcratonic lithosphere indicate an evolution from strongly sinusoidal REE_N, typical for harzburgitic garnets, to mildly sinusoidal or “normal” patterns (positive slope from LREE_N to MREE_N, fairly flat MREE_N–HREE_N), typical for lherzolitic garnets. Using the Cr-number of garnet as a proxy for the bulk rock major element composition it becomes apparent that strong LREE enrichment in garnet is restricted to highly depleted lithologies, whereas flat or positive LREE–MREE slopes are limited to less depleted rocks. For lherzolitic garnet inclusions, there is a positive relation between equilibration temperature, enrichment in MREE, HREE and other HFSE (Ti, Zr, Y), and decreasing depletion in major elements. For harzburgitic garnets, relations are not linear, but it appears that lherzolite style enrichment in MREE–HREE only occurs at temperatures above 1150–1200 °C, whereas strong enrichment in Sr is absent at these high temperatures. These observations suggest a transition from melt metasomatism (typical for the lherzolitic sources) characterized by fairly unfractionated trace and major element compositions to metasomatism by CHO fluids carrying primarily incompatible trace elements. Melt and fluid metasomatism are viewed as a compositional continuum, with residual CHO fluids resulting from primary silicate or carbonate melts in the course of fractional crystallization and equilibration with lithospheric host rocks.

Eclogitic garnet inclusions show “normal” REE_N patterns, with LREE at about 1× and HREE at about 30× chondritic abundance. Clinopyroxenes approximately mirror the garnet patterns, being enriched in LREE and having chondritic HREE abundances. Positive and negative Eu anomalies are observed for both garnet and clinopyroxene inclusions. Such anomalies are strong evidence for crustal precursors for the eclogitic diamond sources. The trace element composition of an “average eclogitic diamond source” based on garnet and clinopyroxene inclusions is consistent with derivation from former oceanic crust that lost about 10% of a partial melt in the garnet stability field and that subsequently experienced only minor reenrichment in the most incompatible trace elements. Based on individual diamonds, this simplistic picture becomes more complex, with evidence for both strong enrichment and depletion in LREE.

Trace element data for sublithospheric inclusions in diamonds are less abundant. REE in majoritic garnets indicate source compositions that range from being similar to lithospheric eclogitic sources to strongly LREE enriched. Lower mantle sources, assessed based on CaSi–perovskite as the principal host for REE, are not primitive in composition but show moderate to strong LREE enrichment. The bulk rock LREE_N–HREE_N slope cannot be determined from CaSi–perovskites alone, as garnet may be present in these shallow lower mantle sources and then would act as an important host for HREE. Positive and negative Eu anomalies are widespread in CaSi–perovskites and negative anomalies have also been observed for a majoritic garnet and a coexisting clinopyroxene inclusion. This suggests that sublithospheric diamond sources may be linked to old oceanic slabs, possibly because only former crustal rocks can provide the redox gradients necessary for diamond precipitation in an otherwise reduced sublithospheric mantle.  相似文献   

Thermal equation of state of majorite with MORB composition     

Yu Nishihara  Ichiro Aoki  Eiichi Takahashi  Ken-ichi Funakoshi 《Physics of the Earth and Planetary Interiors》2005,148(1):73-84

In situ synchrotron X-ray diffraction experiments were conducted using the SPEED-1500 multi-anvil press at SPring-8 on majoritic garnet synthesized from natural mid-ocean ridge basalt (MORB), whose chemical composition is close to the average of oceanic crust, at 19 GPa and 2200 K. Pressure-volume-temperature data were collected using a newly developed high-pressure cell assembly to 21 GPa and 1273 K. Data were fit to the high-temperature Birch-Murnaghan equation of state, with fixed values for the ambient cell volume (V₀ = 1574.14(4) Å³) and the pressure derivative of the isothermal bulk modulus (K^′T = 4). This yielded an isothermal bulk modulus of K_T0 = 173(1) GPa, a temperature derivative of the bulk modulus (∂K_T/∂T)_P = −0.022(5) GPa K⁻¹, and a volumetric coefficient of thermal expansivity α = a + bT with values of a = 2.0(3) × 10⁻⁵ K⁻¹ and b = 1.0(5) × 10⁻⁸ K⁻². The derived thermoelastic parameters are very similar to those of pyrope. The density of subducted oceanic crust compared to pyrolitic mantle at the conditions in Earth's transition zone (410-660 km depth) was calculated using these results and previously reported thermoelastic parameters for MORB and pyrolite mineral assembledges. These calculations show that oceanic crust is denser than pyrolitic mantle throughout the mantle transition zone along a normal geotherm, and the density difference is insensitive to temperature at the pressures in lower part of the transition zone.  相似文献   

Decompression and unmixing of crystals included in diamonds from the mantle transition zone   总被引：3，自引：0，他引：3  

Ben Harte  Nicola Cayzer 《Physics and Chemistry of Minerals》2007,34(9):647-656

A suite of exceptional mineral inclusions in diamonds from the São Luiz river, Juina province, Brazil, shows a wide range of garnet/majorite mineral compositions co-existing with clinopyroxene; the overall bulk compositions are eclogitic. The inclusions have a wide variety of textural arrangements, but crystallographic data obtained by EBSD shows that each inclusion consists of a single garnet with constant crystallographic orientation whilst clinopyroxene grains have preferred orientation with relation to garnet {110} and <111>. This suggests that the inclusions were originally single phase majoritic garnets, and that they preserve various states of progressive unmixing (exsolution) into lower pressure garnet and clinopyroxene compositions during transport of the host diamonds towards the Earth’s surface. On the basis of high pressure–temperature experimental data some of the original majoritic garnets must have come from depths of 450 km or more, and therefore resided in the transition zone and asthenospheric upper mantle. Particularly extensive re-equilibration of many inclusions took place at depths of ca 180–200 km (probably close to the base of the continental lithosphere). The partially unmixed state of the inclusions provides a unique opportunity for using mineral diffusion data to roughly estimate the rate of transport through the asthenospheric upper mantle, and within error this rate is found to be broadly compatible with expected transport rates by upper mantle convection or plume flow.  相似文献   

The CaGeO3–Ca3Fe2Ge3O12 garnet join: an experimental study     

Gianluca Iezzi  Tiziana Boffa-Ballaran  Catherine McCammon  Falko Langenhorst 《Physics and Chemistry of Minerals》2005,32(3):197-207

Germanate garnets are often used as isostructural analogues of silicate garnets to provide insight into the crystal chemistry and symmetry of the less accessible natural garnet solid solutions. We synthesised two series of germanate garnets at 3 GPa along the join^VIIICa₃^VI(CaGe)^IVGe₃O₁₂–^VIIICa₃^VIFe₂^IVGe₃O₁₂ at 900 °C and 1,100 °C. Samples with compositions close to the CaGeO₃ end-member consist of tetragonal garnet with a small amount of triclinic CaGe₂O₅. Samples with nominal compositions between X_Fe=0.4 and 1.0 consist of a mixture of tetragonal and cubic garnets; whereas, single-phase cubic garnets were obtained for compositions with X_Fe>1.2 (X_Fe gives the iron content expressed in atoms per formula unit, and varies between 0 and 2 along the join). Run products which were primarily single-phase garnet were investigated using Mössbauer spectroscopy. Spectra from samples synthesised at 1,100°C consist of one well-resolved doublet that can be assigned to Fe³⁺ in the octahedral site of the garnet structure. A second doublet, present primarily in samples synthesised at 900°C, can be assigned to Fe²⁺ at the octahedral sites of the garnet structure. The relative abundance of Fe²⁺ decreases with increasing iron content. Transmission electron microscopy analyses confirm this tendency and show that the garnets are essentially defect-free. The unit-cell parameters of tetragonal ^VIIICa₃^VI(CaGe)^IVGe₃O₃ garnet decrease with increasing synthesis temperature, and the deviation from cubic symmetry becomes smaller. Cubic garnets show a linear decrease of unit-cell parameter with increasing iron content. The results are discussed in the context of iron incorporation into ^VIIIMg₃^VI(MgSi)^IVSi₃O₃ majorite.  相似文献   

中国辽宁金刚石中高硅钙铁榴石(Majorite)等超高压矿物包裹体的发现及地质意义   总被引：2，自引：0，他引：2  

陆琦  刘惠芳  肖平  施倪承  李国武  汤中道 《地质科技情报》2012,(5):1-7

在中国辽宁金刚石中获得的高硅钙铁榴石(Majorite)为一单晶碎片包裹体,与其共存的金刚石包裹体还有刚玉、碳化钛、红色金刚石碎片、钙钛矿、二氧化硅等。通过电子探针成分分析,确定该高硅钙铁榴石(Majorite)成分超硅高钙缺镁,8个分析点平均值计算的矿物分子式为(Ca2.35Fe0.49Mn0.15Mg0.02)3.01(Al1.08Fe0.48Si0.44)2.00(SiO4)3,根据Kenneth等(2000)提出的计算压力的公式得到该包裹体高硅钙铁榴石(Majorite)形成的压力为14GPa,估算形成深度达400km。用四圆单晶衍射仪测定了该石榴石的晶体结构,a=1.195 15(4)nm,求得了各原子的座标、占位度和各向异性温度因子,用I>2σ(I),计算得到R1=0.077 9,WR2=0.141 6,Goodness-of-fit(F2)=1.382。在该高硅钙铁榴石包裹体中还存在微米级二氧化硅(呈四边形断面)和氧化铁(含钠)的包裹体(析离体),它们可能是斯石英和方铁矿(或似沂蒙矿)。从高硅钙铁榴石(Majorite)的成分判断,其物质来源具壳源性质,由此推断的大陆壳俯冲深度要超过400km,这与地球物理探测郯庐断裂已切穿了上地幔、进入软流圈的看法相一致。  相似文献   

The high-pressure and temperature equation of state of a majorite solid solution in the system of Mg4Si4O12-Mg3Al2Si3O12     

H. Morishima  E. Ohtani  T. Kato  T. Kubo  A. Suzuki  T. Kikegawa  O. Shimomura 《Physics and Chemistry of Minerals》1999,27(1):3-10

The high-pressure and temperature equation of state of majorite solid solution, Mj_0.8Py_0.2, was determined up to 23 GPa and 773 K with energy-dispersive synchrotron X-ray diffraction at high pressure and high temperature using the single- and double-stage configurations of the multianvil apparatuses, MAX80 and 90. The X-ray diffraction data of the majorite sample were analyzed using the WPPD (whole-powder-pattern decomposition) method to obtain the lattice parameters. A least-squares fitting using the third-order Birch-Murnaghan equation of state yields the isothermal bulk modulus, K _T0  = 156 GPa, its pressure derivative, K′ = 4.4(±0.3), and temperature derivative (∂K _T /∂T) _P = −1.9(±0.3)× 10⁻² GPa/K, assuming that the thermal expansion coefficient is similar to that of pyrope-almandine solid solution. Received: 5 October 1998 / Revised, accepted: 24 June 1999  相似文献