Pressure dependence of color of natural uvarovite: the barochromic effect

The electronic absorption spectra of natural uvarovite containing 62 mole% of the Cr³⁺ end-member were studied at pressures between 10⁻⁴ and ca. 13 GPa using DAC techniques combined with microscope spectrometric device. With increasing pressure, a barochromic effect with change from green to red color of the garnet specimen was observed. This change could be interpreted on the basis of the spectra and the data points derived in an ICE color card. The evaluation of crystal field data from the spectra showed that 10Dq of chromium increases on pressure while the Racah parameter B, and thus the nature of the chemical bond of Cr–O does not change significantly.     

Compressional origin of the Aegean Orogeny,Greece

The Aegean Sea area is thought to be an actively extending back-arc region, north of the present day Hellenic volcanic arc and north-dipping subduction zone in the Eastern Mediterranean. The area shows extensive normal faulting, ductile ‘extensional’ shear zones and extensional S-C fabrics throughout the islands that have previously been related to regional Aegean extension associated with slab rollback on the Hellenic Subduction Zone. In this paper, we question this interpretation, and suggest the Cenozoic geodynamic evolution of the Aegean region is associated with a Late Cretaceous–Eocene NE-dipping subduction zone that was responsible for continent-continent collision between Eurasia and Adria-Apulia/Cyclades. Exhumation of eclogite and blueschist facies rocks in the Cyclades and kyanite-sillimanite grade gneisses in the Naxos core complex have pressures that are far greater than could be accounted for purely by lithospheric extension and isostatic uplift. We identify four stages of crustal shortening that affected the region prior to regional lithospheric extension, herein called the Aegean Orogeny. This orogeny followed a classic Wilson cycle from early ophiolite obduction (ca. 74 Ma) onto a previously passive continental margin, to attempted crustal subduction with HP eclogite and blueschist facies metamorphism (ca. 54–45 ?Ma), through crustal thickening and regional kyanite – sillimanite grade Barrovian-type metamorphism (ca. 22–14 ?Ma), to orogenic collapse (<14 ?Ma). At least three periods of ‘extensional’ fabrics relate to: (1) Exhumation of blueschists and eclogite facies rocks showing tight-isoclinal folds and top-NE, base-SW fabrics, recording return flow along a subduction channel in a compressional tectonic setting (ca. 50–35 ?Ma). (2) Extensional fabrics within the core complexes formed by exhumation of kyanite- and sillimanite gneisses showing thrust-related fabrics at the base and ‘extensional’ fabrics along the top (ca. 18.5–14 ?Ma). (3) Regional ductile-brittle ‘extensional’ fabrics and low-angle normal faulting related to the North Cycladic Detachment (NCD) and the South(West) Cycladic Detachment (WCD) during regional extension along the flanks of a major NW–SE anticlinal fold along the middle of the Cyclades. Major low-angle normal faults and ductile shear zones show symmetry about the area, with the NE chain of islands (Andros, Tinos, Mykonos, Ikaria) exposing the NE-dipping NCD with consistent top-NE ductile fabrics along 200 ?km of strike. In contrast, from the Greek mainland (Attica) along the SE chain of islands (Kea, Kythnos, Serifos) a SW-dipping low-angle normal fault and ductile shear zone, the WCD is inferred for at least 100 ?km along strike. Islands in the middle of the Cyclades show deeper structural levels including kyanite- and sillimanite-grade metamorphic core complexes (Naxos, Paros) as well as Variscan basement rocks (Naxos, Ios). The overall structure is an ~100 ?km wavelength NW–SE trending dome with low-angle extensional faults along each flank, dipping away from the anticline axis to the NE and SW. Many individual islands show post-extensional large-scale folding of the low-angle normal faults around the domes (Naxos, Paros, Ios, Sifnos) indicating a post-Miocene late phase of E–W shortening.     

东昆仑石榴石闪长玢岩的形成机制及其对埃达克岩成因的制约

本文报道在东昆仑地区发现的一种较为稀少的含石榴石英云闪长玢岩,这也是此类岩石在中国的首次发现。该次火山岩形成于晚三叠纪,主要由富钙(CaO5 wt%)、贫锰(MnO3 wt%)的石榴石,富铝的角闪石(15.9 wt%),中性斜长石和石英等斑晶以及基质物质组成。岩石含有中等的SiO_2(61.1～62.2wt%),低的MgO(2.0 wt%),K_2O(1.3 wt%)以及较高的Al_2O_3(17 wt%)含量,呈现出次铝质至轻微过铝质的特征(ACNK=0.89～1.05)。在微量元素方面,该岩石富集大离子亲石元素和轻稀土元素,同时亏损Nb-Ta-Ti,显示出典型的消减带特征。而异常低的重稀土(Yb0.8×10~(-6))和相对高的Sr/Y比值(约38)表明石榴石是一个残留相,而较高的Al_2O_3含量,大多为正的铕异常反映了斜长石因结晶受到抑制而在岩浆演化晚期的聚集,同时表明岩浆具有较高的水含量。Nd-Sr同位素组成(ε_(Nd)(t)=-2.33～-1.38;~(87)Sr/~(86)Sr=0.706 5～0.706 7)和斜长石的反向分带显示,壳幔间岩浆混合作用在岩体的形成过程中扮演了重要角色。石榴石斑晶和其中的钛铁矿包体均含有较低的MgO,且包裹石榴石的角闪石形成于较高的压力(8～10 kb)条件下,显示这些矿物结晶自一个长英质岩浆中,且很可能形成于壳幔过渡带附近。尽管该岩石在富铝、低重稀土、高Sr/Y等很多方面均类似于埃达克岩石,但其中等含量的Sr(260×10~(-6))和La/Yb比值(16～21)却明显低于典型的埃达克岩和太古代的TTG。结合石榴石斑晶中广泛存在的磷灰石包体以及其较高的Sr和轻稀土分配系数,本文提出在岩浆演化早期结晶的磷灰石有效地降低了残余熔体中的Sr和轻稀土。这进一步表明,即使在高水逸度的条件下,磷灰石在岩浆早期的大量结晶可以有效地阻止一些弧岩浆演化成为埃达克质岩石。     

安多地区高压麻粒岩的发现及其意义

本文以班公湖-怒江板块缝合带所夹的聂荣微陆块中新近发现的高压麻粒岩为研究对象,通过岩石学、矿物学以及变质作用等的较详细研究,确定其早期矿物组合主要为石榴石、单斜辉石和斜长石等,后期发生了较强烈的退变质作用,出现大量角闪石和斜长石,并发育典型的"白眼圈"结构。利用相关的地质温压计估算其麻粒岩相变质峰期T=790～840℃,P=11～15kbar,角闪岩相退变质阶段T=700～730℃,P=4.6kbar。它可能是燕山期班公湖-怒江板块缝合带闭合过程的产物,也可能反映更早期的碰撞事件,进一步的研究工作将对班公湖-怒江板块缝合带的构造演化或者重新认识青藏高原特别是冈底斯地块的构造格局具有重要意义。     

Thermodynamic data of the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite)

 Calorimetric and P–V–T data for the high-pressure phase Mg₅Al₅Si₆O₂₁(OH)₇ (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B₂O₃) at T=700 ^∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets; they range from −221.1 to −259.4 kJ mol⁻¹ (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol⁻¹ (formation from the elements). The heat capacity of Mg₅Al₅Si₆O₂₁(OH)₇ has been measured from T=50 ^∘C to T=500 ^∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents the heat capacity over the entire temperature range to within the experimental uncertainty: C _P (Mg-sursassite) =(1571.104 −10560.89×T ^−0.5−26217890.0 ×T ⁻²+1798861000.0×T ⁻³) J K⁻¹ mol⁻¹ (T in K). The P V T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ^∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the bulk modulus was determined as 116.0±1.3 GPa, (K ^′=4), V _T,0 =446.49 ³ exp[∫(0.33±0.05) × 10⁻⁴ + (0.65±0.85)×10⁻⁸ T dT], (K _T/T) _P  = −0.011± 0.004 GPa K⁻¹. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg 1998); the best agreement was obtained with Δ_f H ⁰ ₂₉₈ (Mg-sursassite) = −13901.33 kJ mol⁻¹, and S ⁰ ₂₉₈ (Mg-sursassite) = 614.61 J K⁻¹ mol⁻¹. Received: 21 September 2000 / Accepted: 26 February 2001     

宣化-赤城高压麻粒岩带中蓝晶石-正条纹长石组合的发现及地质意义

宣化－赤城的高压麻粒岩带的变质泥质岩中存在“蓝晶石＋正条纹长石”的特征高压组合，形成条件为Ｐ≥１．０ＧＰａ，表明变质泥质岩同变质基性岩一样经历了高压麻粒岩相变质作用。     

Stable isotope geochemistry of Alpine ophiolites: a window to ocean-floor hydrothermal alteration and constraints on fluid–rock interaction during high-pressure metamorphism

 The subduction of hydrated oceanic lithosphere potentially transports large volumes of water into the upper mantle; however, despite its potential importance, fluid–rock interaction during high-pressure metamorphism is relatively poorly understood. The stable isotope and major element geochemistry of Pennine ophiolite rocks from Italy and Switzerland that were metamorphosed at high pressures are similar to that of unmetamorphosed ophiolites, suggesting that they interacted with little pervasive fluid during high-pressure metamorphism. Cover sediments also have oxygen isotope ratios within the expected range of their protoliths. In the rocks that escaped late greenschist-facies retrogression, different styles of sub-ocean-floor alteration may be identified using oxygen isotopes, petrology, and major or trace element geochemistry. Within the basalts, zones that have undergone high- and low-temperature sub-ocean-floor alteration as well as relatively unaltered rocks can be distinguished. Serpentinites have δ¹⁸O and δ²H values that suggest that they were formed by hydration on or below the ocean floor. The development of high-pressure metamorphic mineralogies in metagabbros occurred preferentially in zones that underwent sub-ocean-floor alteration and which contained hydrated, fine-grained, reactive assemblages. Given that the transformation of blueschist-facies metabasic rocks to eclogite-facies assemblages involves the breakdown of hydrous minerals (e.g. lawsonite, zoisite, and glaucophane), and will thus liberate considerable volumes of fluids, metamorphic fluid flow must have been strongly channelled. High-pressure (quartz+calcite±omphacite±glaucophane±titanoclinohumite) veins that cut the ophiolite rocks represent one possible channel; however, stable isotope and major element data suggest that they were not formed from large volumes of exotic fluids. Fluids were more likely channelled along faults and shear zones that were active during high-pressure metamorphism. Such strong fluid channelling may cause fluids to migrate toward the accretionary wedge, especially along the slab–mantle interface, which is probably a major shear zone. This may preclude all but a small fraction of the fluids entering the mantle wedge to flux melting. Additionally, because fluids probably interact with relatively small volumes of rock in the channels, they cannot "scavenge" elements from the subducting slab efficiently. Received: 28 January 1999 / Accepted: 2 February 1999     

Space group and hydrogen sites of δ-AlOOH and implications for a hypothetical high-pressure form of Mg(OH)<Subscript>2</Subscript>

The space group and hydrogen positions of -(Al_0.84Mg_0.07Si_0.09)OOH are investigated using a single crystal synthesized using a multi-anvil apparatus under conditions of 1000 °C and 21 GPa. The space group determined by single-crystal X-ray diffraction is to Pnn2, with unit-cell parameters of a=4.6975(8) Å, b= 4.2060(6) Å, c=2.8327(4) Å, and V=55.97(1) ų. Partial occupancy of the Al site by Mg and Si suggests the possibility of a limited solid solution between -AlOOH, stishovite, and a hypothetical CaCl₂-type Mg(OH)₂ that is 16% denser than brucite. Difference-Fourier maps reveal two small but significant Fourier peaks attributable to hydrogen atoms. Atomic distances and angles around the first peak indicate a hydrogen bond with O···O distances of 2.511 Å, while those around the second peak are suggestive of a bifurcated hydrogen bond with O···O distances of 2.743 and 2.743 Å.     

Calorimetric study on high-pressure transitions in KAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript>

KAlSi₃O₈ sanidine dissociates into a mixture of K₂Si₄O₉ wadeite, Al₂SiO₅ kyanite and SiO₂ coesite, which further recombine into KAlSi₃O₈ hollandite with increasing pressure. Enthalpies of KAlSi₃O₈ sanidine and hollandite, K₂Si₄O₉ wadeite and Al₂SiO₅ kyanite were measured by high-temperature solution calorimetry. Using the data, enthalpies of transitions at 298 K were obtained as 65.1 ± 7.4 kJ mol^–1 for sanidine wadeite + kyanite + coesite and 99.3 ± 3.6 kJ mol^–1 for wadeite + kyanite + coesite hollandite. The isobaric heat capacity of KAlSi₃O₈ hollandite was measured at 160–700 K by differential scanning calorimetry, and was also calculated using the Kieffer model. Combination of both the results yielded a heat-capacity equation of KAlSi₃O₈ hollandite above 298 K as C_p=3.896 × 10²–1.823 × 10³T^–0.5–1.293 × 10⁷T^–2+1.631 × 10⁹T^–3 (C_p in J mol^–1 K^–1, T in K). The equilibrium transition boundaries were calculated using these new data on the transition enthalpies and heat capacity. The calculated transition boundaries are in general agreement with the phase relations experimentally determined previously. The calculated boundary for wadeite + kyanite + coesite hollandite intersects with the coesite–stishovite transition boundary, resulting in a stability field of the assemblage of wadeite + kyanite + stishovite below about 1273 K at about 8 GPa. Some phase–equilibrium experiments in the present study confirmed that sanidine transforms directly to wadeite + kyanite + coesite at 1373 K at about 6.3 GPa, without an intervening stability field of KAlSiO₄ kalsilite + coesite which was previously suggested. The transition boundaries in KAlSi₃O₈ determined in this study put some constraints on the stability range of KAlSi₃O₈ hollandite in the mantle and that of sanidine inclusions in kimberlitic diamonds.     

Thermal equation of state of majorite with MORB composition

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.