Thermodynamics of mixing in diopside–jadeite,CaMgSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–NaAlSi<Subscript>2</Subscript>O<Subscript>6</Subscript>, solid solution from static lattice energy calculations

Static lattice energy calculations (SLEC), based on empirical interatomic potentials, have been performed for a set of 800 different structures in a 2 × 2 × 4 supercell of C2/c diopside with compositions between diopside and jadeite, and with different states of order of the exchangeable Na/Ca and Mg/Al cations. Excess static energies of these structures have been cluster expanded in a basis set of 37 pair-interaction parameters. These parameters have been used to constrain Monte Carlo simulations of temperature-dependent properties in the range of 273–2,023 K and to calculate a temperature–composition phase diagram. The simulations predict the order–disorder transition in omphacite at 1,150 ± 20°C in good agreement with the experimental data of Carpenter (Mineral Petrol 78:433–440, 1981). The stronger ordering of Mg/Al within the M1 site than of Ca/Na in the M2 site is attributed to the shorter M1–M1 nearest-neighbor distance, and, consequently, the stronger ordering force. The comparison of the simulated relationship between the order parameters corresponding to M1 and M2 sites with the X-ray refinement data on natural omphacites (Boffa Ballaran et al. in Am Mineral 83:419–433, 1998) suggests that the cation ordering becomes kinetically ineffective at about 600°C.     

An experimental investigation of hydroxyl solubility in jadeite and Na-rich clinopyroxenes

The solubility and incorporation mechanisms of water in synthetic, water-saturated jadeite and Na-rich clinopyroxenes have been experimentally investigated. Infrared spectra for water-saturated jadeite synthesised from 2.0 to 10 GPa show two prominent sharp peaks at 3,373 and 3,613 cm^–1 together with several weaker features in the OH-stretching region, indicating that there are at least 5 distinct modes of hydrogen incorporation in the structure. Water solubility in pure jadeite reaches a maximum of about 450 ppm by weight at 2 GPa and slowly decreases with increasing pressure to about 100 ppm at 10 GPa. Solubility can be described by the function c_OH=A f_H2O^0.5 exp (–PV_Solid/RT), where c_OH is water solubility in ppm H₂O by weight, A is 7.144 ppm/bar^0.5, f_H2O is water fugacity, and V_Solid=8.019 cm³/mol is the volume change of the clinopyroxene upon incorporation of OH. Jadeite provides a good model for understanding hydrogen incorporation mechanisms in more complex omphacite compositions. Assignment of absorption bands in IR spectra verifies the importance of cation vacancies on the M2 site in providing mechanisms for hydrogen incorporation. However, results also suggest that substitution of lower valency cations onto the M1 site may also be important. Solid solution of jadeite with diopside and in particular, with Ca-Eskola component leads to a drastic increase of water solubility, and the bulk composition has a more important effect on the capacity of omphacite to store water than pressure and temperature. Omphacite is expected to be the major carrier of water in a subducted eclogite after the breakdown of hydrous minerals.Editorial responsibility: W. Schreyer     

Petrogenesis and implications of jadeite‐bearing kyanite eclogite from the Sanbagawa belt (SW Japan)

Jadeite‐bearing kyanite eclogite has been discovered in the Iratsu body of the Sanbagawa belt, SW Japan. The jadeite + kyanite assemblage is stable at higher pressure–temperature (P–T) conditions or lower H₂O activity [a(H₂O)] than paragonite, although paragonite‐bearing eclogite is common in the Sanbagawa belt. The newly discovered eclogite is a massive metagabbro with the peak‐P assemblage garnet + omphacite + jadeite + kyanite + phengite + quartz + rutile. Impure jadeite is exclusively present as inclusions in garnet. The compositional gap between the coexisting omphacite (P2/n) and impure jadeite (C2/c) suggests relatively low metamorphic temperatures of 510–620 °C. Multi‐equilibrium thermobarometry for the assemblage garnet + omphacite + kyanite + phengite + quartz gives peak‐P conditions of ~2.5 GPa, 570 °C. Crystallization of jadeite in the metagabbro is attributed to Na‐ and Al‐rich effective bulk composition due to the persistence of relict Ca‐rich clinopyroxene at the peak‐P stage. By subtracting relict clinopyroxene from the whole‐rock composition, pseudosection modelling satisfactorily reproduces the observed jadeite‐bearing assemblage and mineral compositions at ~2.4–2.5 GPa, 570–610 °C and a(H₂O) >0.6. The relatively high pressure conditions derived from the jadeite‐bearing kyanite eclogite are further supported by high residual pressures of quartz inclusions in garnet. The maximum depth of exhumation in the Sanbagawa belt (~80 km) suggests decoupling of the slab–mantle wedge interface at this depth.     

Mechanisms of exsolution in sodic pyroxenes

The free energy curves for simple binary solid solutions with limited miscibility or atomic ordering have been combined to predict the phase relations and exsolution mechanisms for a system in which both ordering and exsolution are possible. The nature of the ordering process affects which exsolution mechanisms may be used. If the ordering is second (or higher) order in character then continuous mechanisms predominate and a ‘conditional spinodal’ (Alien and Cahn, 1976) can be described which operates between ordered and disordered end members. For a first order case, the ordered phase can only precipitate a disordered phase by nucleation and growth. Microstructures in omphacites observed by transmission electron microscopy include exsolution lamellae and antiphase domains and the relations between them in selected specimens have been used to interpret the exsolution mechanisms which operated under geological conditions. It appears that most omphacites undergo cation ordering, and then remain homogeneous or exsolve a disordered pyroxene by spinodal decomposition. The predominance of continuous mechanisms has been used to indicate that the C2/c→P2/n transformation may be second (or higher) order in character. A possible phase diagram for jadeite-augite is presented. It is based on the idea that there should be limited miscibility between the disordered end members at low temperatures and that the cation ordering at intermediate compositions (omphacite) is superimposed on a solvus. It is adequate to explain many of the observed microstructures and fits with petrographic evidence of broad two phase fields between impure jadeite and omphacite and between omphacite and sodic augite. The effect of adding acmite is analogous to increasing temperature so that the phase relations for jadeite-acmite-augite can also be predicted.     

The local structure of Ca-Na pyroxenes. II. XANES studies at the Mg and Al K edges

X-ray absorption spectra at the Mg and Al K edges have been recorded using synchrotron radiation on synthetic end member diopside (Di) and jadeite (Jd) and on a series of natural Fe-poor Ca-Na clinopyroxenes compositionally straddling the Jd-Di join. The spectra of C2/c end members and intermediate members of the solid solution series (C-omphacites) are different from those of the intermediate members having P2/n symmetry (P-omphacites). Differences can be interpreted and explained by comparing the experimental spectra with theoretical spectra calculated via the full multiple-scattering formalism, starting from the atomic positional parameters determined by single-crystal X-ray diffraction structure refinement on the same samples. Atomic clusters with at least 89 atoms, extending to more than 0.60 nm away from the Mg or Al absorbers, are needed to reproduce the experimental spectra. This shows that in the clinopyroxene systems XANES detects medium- rather than short-range order-disorder relationships. Theoretical spectra match the experimental ones well for all features in the regions from 16 to 60 eV above threshold. Experimental near-edge features in the first 16 eV are also reproduced, albeit less accurately. Certain near-edge features of C-omphacites reflect the octahedral arrangement of the back-scattering six O atoms nearest neighbours of the probed atom (Mg or Al) located at site M1 of the crystal structure, thus being indicators of short-range order. Others arise again from medium-range order. P-omphacites show more complicated spectra than C-omphacites. Their additional features reflect the increased complexity of the structure and the greater local disorder around the probed atom induced by the two alternative M1, M11 configurations of the six O atoms forming the first coordination shells. Mg and Al are confirmed to be preferentially partitioned in the M1 and M11 site of the P-omphacite crystal structure, however with a certain degree of local disorder. The relative heights of certain prominent features are directly related to sample composition in terms of Di:Jd ratio in the Al K-edge spectra, whereas they show abrupt variations in the Mg K-edge spectra. They demonstrate that XANES is directly related to composition and may be used to distinguish C- from P-omphacites. Received: 24 November 1998 / Revised, accepted: 10 June 1999     

A theoretical study of the absorption spectra of Pb+ and Pb3+ in site K+ of microcline: application to the color of amazonite

The blue-green color of amazonite has been assigned by various authors to ions Pb⁺ (6 s)² (6 p) and/or Pb³⁺ (6 s) in site of K⁺ of microcline. Owing to the complex which forms between the ion Pb³⁺ and the lone pairs of the oxygen atoms surrounding it, the peripheral electron of Pb³⁺ passes on the levels (6 p) of the latter, which results in a great similarity of the spectra of Pb⁺ and Pb³⁺ in amazonite (the transition energies are multiplied by a factor greater than 1), whereas, in the isolated state, these spectra are completely different from one another. An analytical development of the crystal field around a site K⁺ is established. Under the effect of the crystal field, the transition ² P _1/2→² P _3/2 (6 p) is split into two double transitions. The lower transition only falls in the visible domain (1.6–1.8 eV for Pb⁺), the second in U−V. The green color would arise from the ion Pb⁺, whereas the blue one would be attributed to the ion Pb³⁺. Received: 23 January 1997 / Revised, accepted: 10 September 1997     

P-V equation of state of portlandite, Ca(OH)2, from powder neutron diffraction data

 A high pressure neutron powder diffraction study of portlandite [Ca(OH)₂] has been performed at ISIS facility (U.K.); nine spectra have been collected increasing the pressure by steps, up to 10.9 GPa, by means of a Paris-Edinburgh cell installed on the POLARIS diffractometer. The tensorial formalism of the lagrangian finite strain theory and the Birch-Murnaghan equation of state have been used to determine, independently, two values of the bulk modulus of portlandite, obtaining K ₀=38.3(±1.1) GPa [linear incompressibilities: K _0a=188.4(±9.9), K _0c=64.5(±2.5) GPa] and K ₀=34.2(±1.4) GPa, respectively. The present results comply with values from previous measurements by X-ray diffraction [K ₀=37.8(±1.8) GPa] and Brillouin spectroscopy [K ₀=31.7(±2.5) GPa]. Reasonably, Ca(OH)₂ has revealed to be bulkly softer than Mg(OH)₂ [K ₀=41(±2), K _0a=313, K _0c=57 GPa]. The Ca(OH)₂ linear incompressibility values reflect the nature of forces acting to stabilize the (001) layer structure and, further, prove that the replacement Ca/Mg mainly affects the elastic properties in the (001) plane, rather than along the [001] direction. Data from a full refinement of the structure at room pressure are reported. Received January 12, 1996/Revised, accepted June 15, 1996     

Thermal expansion along the NaAlSi2O6–NaFe3+Si2O6 and NaAlSi2O6–CaFe2+Si2O6 solid solutions

The high temperature volume and axial parameters for six C2/c clinopyroxenes along the NaAlSi₂O₆–NaFe³⁺Si₂O₆ and NaAlSi₂O₆–CaFe²⁺Si₂O₆ joins were determined from room T up to 800°C, using integrated diffraction profiles from in situ high temperature single crystal data collections. The thermal expansion coefficient was determined by fitting the experimental data according to the relation: ln(V/V ₀) = α(T − T ₀). The thermal expansion coefficient increases by about 15% along the jadeite–hedenbergite join, whereas it is almost constant between jadeite and aegirine. The increase is related to the Ca for Na substitution into the M2 site; the same behaviour was observed along the jadeite–diopside solid solution, which presents the same substitution at the M2 site. Strain tensor analysis shows that the major deformation with temperature occurs in all samples along the b axis; on the (010) plane the higher deformation occurs in jadeite and aegirine at a direction almost normal to the tetrahedral–octahedral planes, and in hedenbergite along the projection of the longer M2–O bonds. The orientation of the strain ellipsoid with temperature in hedenbergite is close to that observed with pressure in pyroxenes. Along the jadeite–aegirine join instead the high-temperature and high-pressure strain are differently oriented.     

Electronic absorption spectra of Cr3+ ions in natural clinopyroxenes

The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr₂O₃), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr³⁺ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C ₂ or C _2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C _3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D _q increases from diopside (1542 cm^?1) through omphacite (1552 cm^?1), jadeite (1574 cm^?1) to spodumene (1592 cm^?1). The parameter B which is a measure of covalency for Cr³⁺-O bonds at M1 sites in clinopyroxene depends on the Cr³⁺ concentration and the cations at M2 sites.     

Water-related defects and oxygen diffusion in albite: a computer simulation study

 Computer simulation techniques have been used to investigate the energetics of defect formation in Albite and to calculate O and (OH) migration activation energies. We find that the Na Frenkel defect has the lowest formation energy, whilst interstitials associated with impurities are the most favourable O defects. Water can be accommodated in the albite structure as both OH groups and as H₂O molecules with solution energy of 0.73 eV and 0.9 eV respectively. The activation energies for O migration is reduced by up to 50% when the O is migrating as part of an (OH) group. In addition, we find a marked diffusional anisotropy for both O and (OH) in albite. Received: 15 September 1995 / Accepted: 29 April 1996     

The influence of multiple diffraction on the space group determination of orthopyroxene,spodumene, low omphacite and pigeonite

Forbidden reflections of some pyroxenes described as having a lower symmetry than Pbca or C2/c have been examined, mainly using the detailed ψ-scanning method of the four-circle automated diffractometer. All reflections violating the systematic absences of Pbca orthopyroxene, C2/c spodumene, P2/n omphacite and P2₁/c pigeonite were found to be due to the Umweganregung process of multiple diffraction; the Umweganregung peaks observed for the ψ azimuth were indexed in terms of a four-circle geometry. Thus, the space groups of orthopyroxene, α spodumene, low omphacite and low pigeonite were confirmed to be Pbca, C2/c, P2/n and P2₁/c, respectively.     

A clinopyroxene geobarometer for basaltic systems based on crystal-structure modeling

 The crystal chemical response of basalt clinopyroxene to increasing pressure was investigated by means of crystal-structure simulation (a procedure that enables modeling of the structural parameters of a clinopyroxene of known chemistry without requiring direct X-ray diffraction analysis) using available experimental chemical data. Pressure proved the main physical variable governing clinopyroxene behavior in a magmatic environment. The general internal consistency of the simulation data permitted construction of an empirical geobarometer based on the relationship of cell volume (Vc) vs M1-site volume (VM1). The straightforward geobarometric formulation in the absence of direct X-ray analysis is: P(kbar)=698.443+4.985⋅Al_T−26.826⋅Fe²⁺ _M1−3.764⋅Fe³⁺ +53.989⋅Al_M1+3.948⋅Ti+14.651⋅Cr −700.431⋅Ca−666.629⋅Na−682.848⋅Mg_M2−691.138⋅Fe²⁺ _M2−688.384⋅Mn−6.267⋅(Mg_M2)²−4.144⋅(Fe²⁺ _M2 where: (Fe²⁺ _M1⋅Mg_M2)/(Fe²⁺ _M2⋅Mg_M1)=e^**(0.238⋅R³⁺+0.289⋅CNM−2.315), CNM=Ca+Na+Mn, and R³⁺=Al_M1+Fe³⁺+Ti+Cr, with cations in atoms per formula unit. The geobarometer reproduces experimental pressures within ±2 kbar (=1σ; max. dev. ≤5 kbar; N=29) in the range 0–24 kbar and is applicable to near-liquidus C2/c clinopyroxenes crystallized from basaltic melts in the absence of garnet (excepting high-Al₂O₃ basalts). It is therefore suitable for many natural clinopyroxenes occurring as mega- or phenocrysts or forming well-preserved cumulate pyroxenites. If the above restrictions are not wholly satisfied, the Vc vs VM1 plot can also be used qualitatively to deduce the relative pressure conditions of clinopyroxenes forming from similar batches of magma. The structural simulation of experimental data also provided insight into the influence of minor chemical changes of the parental magma on the crystal chemistry of clinopyroxene at high pressure. Within the considered compositional space at given P-T, a _CaO and a _SiO2 in the melt have opposite effects on M2- and T-site cation populations. As a result, under similar physical conditions, clinopyroxenes from higher-CaO or more undersaturated basalts have higher VM2, VT and Vc and lower VM1. For basalts with normal contents of Al₂O₃ (<18 wt %), variations of major elements in the melt do not reduce the accuracy of the geobarometer. Received: 3 April 1994 / Accepted: 23 December 1995     

基于激光诱导离解光谱技术定量研究绿辉石的化学成分

应用中国地质大学（武汉）珠宝学院自制的激光诱导离解光谱（LIBS）设备对5块已知成分和32块未知成分的翡翠进行测量,采用优化外标法分析了LIBS测试稳定性与测量精度,测试计算结果平均值与真值偏差小于1％,测试计算结果标准偏差优于1．2％;通过测试结果计算待测样品的晶体化学通式,其不同晶位阳离子系数总数之比为（O．913±1．075）：（0．902±1．182）：（1．909±2．087）,基本上符合翡翠阳离子晶位系数1;1;2的理论值,验证了LIBS定量区分硬玉与绿辉石的可行性。试验样品的LIBS定量分析结果显示,硬玉与绿辉石中SiO2的质量分数基本上稳定在59％左右,硬玉中Na2O和Al2O。的质量分数分别在13％和23％左右,CaO,FeO2r,MgO的总质量分数低于4％,而绿辉石中Na2O和Al2O。的质量分数比硬玉的低,翡翠中CaO,FeO2,MgO的总质量分数随着绿辉石的质量分数增加而增大,可达到27％。此外,绿辉石中Na20和CaO的质量分数呈现很好的负线性相关,相关系数r1=--0．9901;Al2O2与MgO的质量分数也呈现很好的负线性相关,相关系数r2=-0．9666。     

Electrical properties of opal-CT

 The electrical properties of opal-CT are validated at temperatures from 600 to 840 °C and frequencies from 5 Hz to 10 MHz. The opals are hydrothermal, containing less than 11270 ppm total of Al, Fe, Ca, Na, and K, and from 1.17 to 17.63 wt% H₂O interstitial and structural. Opal-CT shows fine crystallites, measuring from 19.4 to 22.7 μm, of an ordered tridymite-M stratification with high-cristobalite, embedded in a non-crystalline matrix. When heated to 600 °C, the non-crystalline phase devitrifies to the same stacked high-cristobalite-tridymite-M crystals. Opals containing less than 2070 ppm of cationic impurities are characterized by one single high-frequency complex impedance arc corresponding to the bulk polarization of the crystalline phase, of capacitances between 25 and 30×10⁻¹² F and resistances from 132 to 890 ohm. Opals having over 6300 ppm of cationic impurities show two superimposed high- and low-frequency complex impedance arcs. The high-frequency arc corresponds to the bulk polarization of the crystalline phase, of capacitance between 8 and 15.7×10⁻¹² F and resistance from 14 to 236 ohm, less than the capacitance of 0.25 to 0.53×10⁻⁹ F and resistance from 26 to 360 ohm of the non-crystalline minor intergranular material represented by the low-frequency impedance arc. The electric module shows one single vertex, ascribed to the bulk polarization of the crystalline phase. The conductivities are from 10⁻⁷ to 10⁻⁴ ohm⁻¹cm⁻¹, in the range of poor ionic conductors, essentially constant below 1.8 kHz, rapidly increasing at higher frequencies, due to ionic and electronic charge carriers. The activation energy changes between 0.905 and 1.003 eV for the conduction mechanism in the crystalline phase and from 0.924 to 1.087 eV in the non-crystaline phase. X-ray diffraction and impedance spectroscopy confirm that opal-CT is a crystalline stacked sequence of tridymite-M and cristobalite-high, in a non-crystalline matrix. Received October 20, 1995/Revised, accepted June 15, 1996     

White mica 40Ar/39Ar age spectra and the timing of multiple episodes of high‐P metamorphic mineral growth in the Cycladic eclogite–blueschist belt,Syros, Aegean Sea,Greece

New geochronology from Syros in the Cycladic eclogite–blueschist belt, Aegean Sea, Greece, shows that ⁴⁰Ar/³⁹Ar geochronology consistently dates microstructural events in metamorphic rocks. We demonstrate that the age spectra depend on microstructure in a predictable and systematic way. Ages can be inferred by applying the method of asymptotes and limits to data from the step ‐ heating experiments. The results are consistent with previously published estimates for the timing of a sequence of distinct and discrete episodes of high ‐ P metamorphic mineral growth observed regionally across this belt. Arrhenius plots from these experiments imply that phengitic white mica is highly retentive of argon, and therefore (if these data can be extrapolated to the natural environment) the ages can be interpreted as recording the timing of episodic deformation and metamorphism. Porphyroblastic growth begins: (i) for omphacite – jadeite–eclogite facies parageneses at c. 53 Ma; and (ii) for garnet – glaucophane facies parageneses at c. 47 Ma. The Kini Shear Zone started as an extensional post ‐ epidote–albite‐transitional–blueschist facies shear zone that had completed operation by c. 31 Ma. The scatter in ages is due to the effect of deformation, recrystallization and multiple growth events in shear zones that continued operating for 3 – 6 million years from the start of each episode.     

Activities of components in omphacitic solid solutions

Available experimental data on mixing of disordered C2/c clinopyroxenes in the system diopside-jadeite-hedenbergite-acmite are reviewed and evaluated. Because the methods used to determine jadeite activity suffer from severe uncertainty at high jadeite mol fractions, these data cannot be used to infer asymmetry in the jadeite-diopside or the jadeite-hedenbergite solid solutions. If the measurement uncertainties are taken into account, a single parameter (regular, or reciprocal energy) suffices to describe the mixing properties of these two solid solutions. It is argued that a two-site entropy of mixing satisfies the experiments and is consistent with the C2/c disordered nature of the solid solutions; the data in the range 600–1300° C are consistent with a temperature-independent interaction energy, implying no discernible excess entropy. The available experimental data imply W=26±2 kJ mol^–1 for jd-di, and W=25±3 kJ mol^–1 for jd-hd, solid-solutions. Landau theory for a tricritical phase transformation (C2/c-P2/n) is in good agreement with the calorimetrically determined disordering enthalpy, and may be used to derive a simple expression for the activities in ordered omphacite solid solutions. The derived activities of jadeite at 600° C in ordered omphacites are remarkably close to those reported previously for short-range ordered pyroxenes. A simple model is presented for determining the activities of end-members in the system jadeite-diopside-hedenbergite-acmite.     

Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si−O bond distances, coordination numbers and Debye-Waller factors). The mean Si−O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R≈0.172 nm and N≈5) to R≈0.167 nm and N≈4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by modelling the amorphization as a decay process. Using the EXELFS data for amorphization, a new method is developed to derive the relative amounts of Si coordinations in high-pressure minerals with mixed coordination. For the radiation-induced amorphization process of stishovite the formation of a transitory structure with Si largely in fivefold coordination is deduced. Received: 18 December 1996 / Revised, accepted: 20 June 1997     

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     

A new jadeitite jade locality (Sierra del Convento, Cuba): first report and some petrological and archeological implications

A new jadeitite jade locality has been discovered in the serpentinite-matrix subduction mélange of the Sierra del Convento (eastern Cuba) in a context associated with tectonic blocks of garnet-epidote amphibolite, tonalitic–trondhjemitic epidote gneiss, and blueschist. The mineral assemblages of jadeitite jade and jadeite rocks are varied and include combinations of jadeite, omphacite, albite, paragonite, analcime, clinozoisite-epidote, apatite, phlogopite, phengite, chlorite, glaucophane, titanite, rutile, zircon, and quartz formed during various stages in their P–T evolution. Field relationships are obscure, but some samples made almost exclusively of jadeite show evidence of crystallization from fluid in veins. In one of these samples studied in detail jadeite shows complex textural and chemical characteristics (including oscillatory zoning) that denote growth in a changing chemical medium. It is proposed that interaction of an Al–Na rich fluid with ultramafic rocks produced Al–Na–Mg–Ca fluids of varying composition. Episodic infiltration of these fluids, as a result of episodic opening of the veins, developed oscillatory zoning by direct precipitation from fluid and after reaction of fluid with pre-existing jadeite. The latest infiltrating fluids were richer in Mg–Ca, favouring the formation of omphacite and Mg–Ca rich jadeite in open voids and the replacement of earlier jadeite by fine-grained omphacite + jadeite at 550–560°C. This new occurrence of jadeite in Cuba opens important perspectives for archeological studies of pre-Columbian jade artifacts in the Caribbean region.     

Magnetic and nuclear structure and thermal expansion of orthorhombic and monoclinic polymorphs of CoGeO3 pyroxene

CoGeO₃ was synthesized at 1,273 and 1,448 K using ceramic sintering techniques in the monoclinic and orthorhombic modification, respectively. The two compounds were analysed by magnetic susceptibility measurements and neutron diffraction in order to study magnetic ordering and spin structures at low temperature. The monoclinic form of CoGeO₃ has C2/c symmetry and orders magnetically below 36 K with a small negative paramagnetic Curie temperature θ _P = −4.6 (2) K. The magnetic structure can be described with k = (1, 0, 0) in the magnetic space group C2′/c′ having a ferromagnetic spin arrangement within the chains of M1 sites, but a dominating antiferromagnetic coupling between the chains. At the M1 sites the magnetic spins are aligned within the a–c plane forming an angle of 120° with the +a-axis and they are not parallel to the spins at M2. Here spins are also ferromagnetically coupled within, but antiferromagnetically coupled between the M1/M2 site bands. The orthorhombic phase of CoGeO₃ displays Pbca symmetry and transforms to an antiferromagnetically ordered state [θ _P = −18.6(2) K] below 33 K. The magnetic spin structure can be described with k = (0, 0, 0) in space group Pbca′ and it is similar to the one of the C2/c phase except that it is non-collinear in nature, i.e. there are components of the magnetic moment along all three crystallographic axes. Small magneto-elastic coupling is observed in the orthorhombic phase.