Ultrahigh pressure macro diamonds from Copeton (New South Wales, Australia), based on Raman spectroscopy of inclusions

Mining of Cenozoic alluvial deposits at Copeton and Bingara (Eastern Australia) has produced two million macrodiamonds (0.25 ct median size). Raman spectroscopy is used to identify included minerals within uncut Copeton diamonds, with sealed chamber remnant pressures of 31.7 to 35.6 kbar for coesite, 13.6 and 22.7 kbar for clinopyroxene, and 7.6 kbar for grossular garnet. Assuming elastic behaviour, these values generate inclusion entrapment PT loci which intersect, restricting diamond formation conditions: from 250 °C, 43 kbar to 800 °C, 52 kbar. Larger than error (± 100 °C and ± 4 kbar), this range shows a systematic variation in inclusion composition with diamond zoning and N properties. Published research shows 1) Copeton and Bingara diamonds are unique, and 2) modern alluvium in the Bingara district carries mantle-formed garnet, captured by post-tectonic alkali basalt from an extensive diamondiferous ultrahigh pressure (UHP) terrane that stalled at depth because it is dominated by mafic eclogite. The combined Raman and geological results indicate two sets of subduction UHP diamond formation conditions/protolith are required, firstly cooler oceanic slab and secondly including higher temperature continental crust. The Copeton and Bingara stones are UHP macrodiamonds, and Carboniferous ⁴⁰Ar/³⁹Ar age dates on clinopyroxene inclusions should be interpreted as ages of crystallisation, representing the termination of subduction. The characteristic features of ruptured inclusions and etched percussion marks on Copeton and Bingara diamond indicate volcanic delivery to the earth's surface. Alluvial deposits elsewhere in Eastern Australia may carry similar diamond along with diamond of different origin.     

Melting of β-quartz up to 2.0 GPa and thermodynamic optimization of the silica liquidus up to 6.0 GPa

Melting relations of β-quartz were experimentally determined at 1.0 GPa (1900±20 °C), 1.5 GPa (2033±20 °C), and 2.0 GPa (2145±20 °C) using a new high-pressure assembly in a piston–cylinder apparatus and substantial differences were found with data previously reported. The new melting data of β-quartz were combined and optimized with all available thermodynamic, volumetric, and phase equilibria data for β-cristobalite, β-quartz and coesite to produce a P–T liquidus diagram for silica valid up to 6.0 GPa. Using the new optimized thermodynamic parameters, the invariant point β-cristobalite+β-quartz+liquid and β-quartz+coesite+liquid were determined to lie at 1687±17 °C and 0.457 GPa, and 2425±25 °C and 5.00 GPa, respectively.     

Compression mechanisms of coesite

 The structure of coesite has been determined at ten pressures up to a maximum of 8.68 GPa by single-crystal X-ray diffraction. The dominant mechanism of compression is the reduction of four of the five independent Si–O–Si angles within the structure. There is no evidence of the fifth linkage, Si1–O1–Si1, deviating from 180°. Some Si–O bond distances also decrease by up to 1.6% over the pressure range studied. The pattern of Si–O–Si angle reduction amounts to a rotation of the Si2 tetrahedron around the [001] direction. This rotation induces significant internal deformation of the Si1 tetrahedron. Comparison of the experimental data with rigid-unit distance least-squares simulations of coesite suggests that this pattern of compression, the anomalous positive values of both s₂₃ and K′′ in the equation of state of coesite, its high elastic anisotropy and the unusual straight Si1–O1–Si1 linkage within the structure are all consequences of the connectivity of the tetrahedral framework. Received: 11 July 2002 / Accepted: 14 January 2003 Acknowledgements The help of Christian Baerlocher of ETH Zurich in providing both the DLS-76 software and advice in its use is gratefully acknowledged, as are discussions with Paul Ribbe of Virginia Tech and the comments of two anonymous reviewers. The data analysis was supported by the National Science Foundation under grant EAR-0105864 to N.L. Ross and R.J. Angel.     

大别山超高压榴辉岩带榴辉岩的特征和变质作用

大别山超高压柯石英榴辉岩带中多处产出含柯石英榴辉岩,岩石中广泛分布柯石英假象。它们产在片麻岩和大理岩中,并有不同的特征矿物组合。与鄂北等地高压型榴辉岩比较,超高压(柯石英)榴辉岩的绿辉石富硬玉组分,而石榴石为一般的富铁铝榴石贫镁铝榴石的石榴石。钙质角闪石和钠钙质冻蓝闪石是超高压(柯石英)榴辉岩中主要的次生角闪石类型。榴辉岩的原岩是陆内拉张过程中形成的广义拉斑玄武岩,它们在中朝一扬子大陆板块汇聚造山的俯冲大地构造背景中,发生渐进变质。变质时地热增温率极低。造山运动后期,榴辉岩随构造运动抬升又经历两阶段迭加变质。     

Location and quantitative analysis of OH in coesite

 The incorporation of hydrogen (deuterium) into the coesite structure was investigated at pressures from 3.1 to 7.5 GPa and temperatures of 700, 800, and 1100 °C. Hydrogen could only be incorporated into the coesite structure at pressures greater 5.0 GPa and 1100 °C . No correlation between the concentration of trace elements such as Al and B and the hydrogen content was observed based on ion probe analysis (1335 ± 16 H ppm and 17 ± 1 Al ppm at 7.5 GPa, 1100 °C). The FTIR spectra show three relatively intense bands at 3575, 3516, and 3459 cm⁻¹ (ν₁ to ν₃, respectively) and two very weak bands at 3296 and 3210 cm⁻¹ (ν₄ and ν₅, respectively). The band at 3516 cm⁻¹ is strongly asymmetric and can be resolved into two bands, 3528 (ν_2a) and 3508 (ν_2b) cm⁻¹, with nearly identical areas. Polarized infrared absorption spectra of coesite single-crystal slabs, cut parallel to (0 1 0) and (1 0 0), were collected to locate the OH dipoles in the structure and to calibrate the IR spectroscopy for quantitative analysis of OH in coesite (ɛ _{i ,tot}=190 000 ± 30 000 l mol⁻¹ _H2O cm⁻²). The polarized spectra revealed a strong pleochroism of the OH bands. High-pressure FTIR spectra at pressures up to 8 GPa were performed in a diamond-anvil cell to gain further insight into incorporation mechanism of OH in coesite. The peak positions of the ν₁, ν₂, and ν₃ bands decrease linearly with pressure. The mode Grüneisen parameters for ν₁, ν₂, and ν₃ are −0.074, −0.144 and −0.398, respectively. There is a linear increase of the pressure derivatives with band position which follows the trend proposed by Hofmeister et al. (1999). The full widths at half maximum (FWHM) of the ν₁, ν₂, and ν₃ bands increase from 35, 21, and 28 cm⁻¹ in the spectra at ambient conditions to 71, 68, and 105 in the 8 GPa spectra, respectively. On the basis of these results, a model for the incorporation of hydrogen in coesite was developed: the OH defects are introduced into the structure by the substitution Si^4+(Si2)+4O²⁻= ^[4]□^(Si2) + 4OH⁻, which gives rise to four vibrations, ν₁, ν_2a, ν_2b, and ν₃. Because the OH(D)-bearing samples do contain traces of Al and B, the bands ν₄ and ν₅ may be coupled to Al and/or B substitution. Received: 19 December 2000 / Accepted: 23 April 2001     

A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

Prograde high- to ultrahigh-pressure metamorphism and exhumation of oceanic sediments at Lago di Cignana, Zermatt-Saas Zone, western Alps

Pelagic metasediments and MORB-type metabasalts of the former Tethyan oceanic crust at Cignana, Valtournanche, Italy, experienced UHP metamorphism and subsequent exhumation during the Early to Late Tertiary. Maximum PT conditions attained during UHP metamorphism were 600–630 °C, 2.7–2.9 GPa, which resulted in the formation of coesite-glaucophane-eclogites in the basaltic layer and of garnet-dolomite-aragonite-lawsonite-coesite-phengite-bearing calc-schists and garnet-phengite-coesite-schists with variable amounts of epidote, talc, dolomite, Na-pyroxene and Na-amphibole in the overlying metasediments. During subduction the rocks followed a prograde HP/UHP path which in correspondance with the Jurassic age of the Tethyan crust reflects the thermal influence of relatively old and cold lithosphere and of low to moderate shear heating. Inflections on the prograde metamorphic path may correspond to thermal effects that arise from a decrease in shear heating due to brittle-plastic transition in the quartz-aragonite-dominated rocks, induced convection in the asthenospheric mantle wedge and/or heat consumption by endothermic reactions over a restricted PT segment during subduction. After detachment from the downgoing slab some 50–70 Ma before present, the Cignana crustal slice was first exhumed to ca. 60 km and concomitantly cooled to ca. 550 °C, tracing back the UHP/HP prograde path displaced by 50–80 °C to higher temperatures. Exhumation at this stage is likely to have occurred in the Benioff zone, while the subduction of cool lithosphere was going on. Subsequently, the rocks were near-isothermally exhumed to ca. 30 km, followed by concomitant decompression and cooling to surface conditions (at < 500 °C, < 1 GPa). During this last stage the UHPM slice arrived at its present tectonic position with respect to the overlying greenschist-facies Combin zone. In contrast to the well-preserved HP/UHPM record of the coesite-glaucophane eclogites, the HP/UHP assemblages of the metasediments have been largely obliterated during exhumation. Relics from which the metamorphic evolution of the rocks during prograde HP metamorphism and the UHP stage can be retrieved are restricted to rigid low-diffusion minerals like garnet, dolomite, tourmaline and apatite.     

北秦岭官坡地区柯石英榴辉岩变质作用的P－T－t轨迹

根据矿物包裹和替代关系以及共生组合规律，北秦岭官坡地区柯石英榴辉岩的变质作用演化可划分为５个阶段，即前榴辉岩相的绿帘角闪岩相、榴辉岩相、后榴辉岩相的角闪岩相、绿帘角闪岩相和绿片岩相。Ｓｍ－Ｎｄ同位素定年显示，北秦岭柯石英榴辉岩于４００±１６Ｍａ沿朱夏断裂被推覆上升，Ｐ－Ｔ－ｔ轨迹的地球动力学成因可能与扬子和华北陆块间的俯冲－碰撞作用有关。     

SiO bonded interactions in coesite: a comparison of crystalline, molecular and experimental electron density distributions

Bond critical point properties of electron density distributions calculated for representative Si₅O₁₆ moieties of the structure of coesite are compared with those observed and calculated for the bulk crystal. The values calculated for the moieties agree with those observed to within ∼5%, on average, whereas those calculated for the crystal agree to within ∼10%. As the SiOSi angles increase and the SiO bonds shorten, there is a progressive build-up in the calculated electron density along the bonds. This is accompanied by an increase in both the curvatures of the electron density, both perpendicular and parallel to each bond, and the Laplacian of the electron density distribution at the bond critical points. The cross sections of the bonds at the critical points become more circular as the angle approaches 180o. Also, the bonded radius of the oxide anion decreases about twice as much as that of the Si cation as the SiO bond length decreases and the fraction of s-character of the bond is indicated to increase. A knowledge of electron density distributions is central to our understanding of the forces that govern the structure, properties, solid state reactions, surface reactions and phase transformations of minerals. The software (CRYSTAL95 and TOPOND) used in this study to calculate the bond critical properties of the electron density and Laplacian distributions is bound to promote a deeper understanding of crystal chemistry and properties. Received: 23 February 1998 / Revised, accepted: 16 July 1998     

Petrology and U–Pb zircon dating of coesite-bearing metapelite from the Kebuerte Valley,western Tianshan,China

This paper deals with the petrology and U–Pb dating of coesite-bearing garnet–phengite schist from the Kebuerte Valley, Chinese western Tianshan. It mainly consists of porphyroblastic garnet, phengite, quartz and chlorite with minor amounts of paragonite, albite, zoisite and chloritoid. The well preserved coesite inclusions (∼100 μm) in garnet are encircled by a narrow rim of quartz. They were identified by optical microscopy and confirmed by Raman spectroscopy. Using the computer program THERMOCALC, the peak metamorphic conditions of 29 kbar and 565 °C were obtained via garnet isopleth geothermobarometry. The predicted UHP peak mineral assemblage comprises garnet + jadeite + lawsonite + carpholite + coesite + phengite. The metapelite records prograde quartz–eclogite-facies metamorphism, UHP coesite–eclogite-facies peak metamorphism, and a late greenschist-facies overprint. Phase equilibrium modeling predicts that garnet mainly grew in the mineral assemblages garnet + jadeite + lawsonite + chloritoid + glaucophane + quartz + phengite and garnet + jadeite + lawsonite + carpholite + glaucophane + quartz + phengite. SHRIMP U–Pb zircon dating of the coesite-bearing metapelite yielded the peak metamorphic age 320.4 ± 3.7 Ma. For the first time, age data of coesite-bearing UHP metapelite from the Chinese western Tianshan are presented in this paper. They are in accord with published ages obtained from eclogite from other localities in the Chinese western Tianshan and the Kyrgyz South Tianshan and therefore prove a widespread occurrence of UHP metamorphism.