Factors effecting the stability field of Ca-poor pyroxene and the origin of the Ca-poor minimum in Ca-rich pyroxenes from tholeiitic intrusions

Ca-poor pyroxene ceases to crystallise towards the end of fractionation in tholeiitic intrusions and is usually replaced by Fe-rich olivine. Using the data of Nicholls et al. (1971), the \(a_{{\text{SiO}}_2 }\) at which olivine and pyroxene can coexist has been calculated at different temperatures and pressures. From these calculations it is clear that the Fe/Mg ratio of the last Ca-poor pyroxene to crystallise from a melt is increased by raising the temperature or pressure of crystallisation. The Ca-poor pyroxene-Fe-rich olivine relationship is also dependent on the \(a_{{\text{SiO}}_2 }\) of the melt. In magmas which crystallise Fe-rich olivine before quartz, inicreasing their \(a_{{\text{SiO}}_2 }\) will raise the Fe/Mg ratio of the last Ca-poor pyroxene to crystallise. If the \(a_{{\text{SiO}}_2 }\) of the magma is so high that SiO₂ saturation is reached before the appearance of cumulus Fe-rich olivine, any further increase in the \(a_{{\text{SiO}}_2 }\) of the melt will not influence the stability field of Ca-poor pyroxene. The replacement of Ca-poor pyroxene by Fe-rich olivine requires the magma to reach a high level of a _FeO late in its fractionation. If a magma fractionates with an FeO depletion trend, Ca-poor pyroxene is replaced by Ca-rich pyroxene. The reaction is initiated by the appearance of cumulus K-feldspar which results in a marked reduction in the amount of anorthite crystallising from the magma. This increases the a _CaO of the melt so that Ca-poor pyroxene is replaced by Ca-rich pyroxene.     

Polymorphic phase transition in Superhydrous Phase B

We synthesized superhydrous phase B (shy-B) at 22 GPa and two different temperatures: 1200°C (LT) and 1400°C (HT) using a multi-anvil apparatus. The samples were investigated by transmission electron microscopy (TEM), single crystal X-ray diffraction, Raman and IR spectroscopy. The IR spectra were collected on polycrystalline thin-films and single crystals using synchrotron radiation, as well as a conventional IR source at ambient conditions and in situ at various pressures (up to 15 GPa) and temperatures (down to −180°C). Our studies show that shy-B exists in two polymorphic forms. As expected from crystal chemistry, the LT polymorph crystallizes in a lower symmetry space group (Pnn2), whereas the HT polymorph assumes a higher symmetry space group (Pnnm). TEM shows that both modifications consist of nearly perfect crystals with almost no lattice defects or inclusions of additional phases. IR spectra taken on polycrystalline thin films exhibit just one symmetric OH band and 29 lattice modes for the HT polymorph in contrast to two intense but asymmetric OH stretching bands and at least 48 lattice modes for the LT sample. The IR spectra differ not only in the number of bands, but also in the response of the bands to changes in pressure. The pressure derivatives for the IR bands are higher for the HT polymorph indicating that the high symmetry form is more compressible than the low symmetry form. Polarized, low-temperature single-crystal IR spectra indicate that in the LT-polymorph extensive ordering occurs not only at the Mg sites but also at the hydrogen sites.     

Hydrothermal clinopyroxenes of the Skaergaard intrusion

Magmatic augites reacted with high temperature aqueous solutions to form secondary calcic pyroxenes during the subsolidus cooling of the Skaergaard intrusion. Secondary, hydrothermal clinopyroxenes replace wall rock igneous augites at the margins of veins filled with calcic amphibole. These veins are up to several millimeters wide and tens of meters in length. Hydrothermal clinopyroxenes are a ubiquitous and characteristic phase in the earliest veins throughout the Layered Series of the intrusion, and occur rarely in late veins that, in some places, crosscut the early veins. Associated secondary phases in early veins include amphiboles ranging in composition from actinolite to hornblende, together with biotite, Fe-Ti oxides and calcic plagioclase. Hydrothermal clinopyroxenes in late veins may be associated with actinolite, hornblende, biotite, magnetite and albite.Hydrothermal clinopyroxenes are depleted in Fe, Mg and minor elements, and enriched in Ca and Si relative to igneous augites in the Layered Series gabbros. Secondary vein pyroxenes are similar in composition to calcic pyroxenes from amphibolite facies metamorphic rocks. Clinopyroxene solvus thermometry suggests minimum temperatures of equilibration of between 500° and 750° C. These temperatures, combined with numerical transport models of the intrusion, suggest that vein clinopyroxenes could have formed during 20,000 to 60,000 year time intervals associated with a maximum in the fluid flux through fractures in the Layered Series.     

Coexisting Ca-poor pyroxenes in the Main Zone of the Bushveld Complex

Electron microprobe analyses of Ca-poor pyroxenes in gabbroic rocks of the Main Zone of the Bushveld Complex reveal that inverted pigeonites have lower Mg/Fe ratios than coexisting hypersthenes. Textural relationships, however, indicate that the two Ca-poor pyroxenes did not crystallize simultaneously from the magma. Early pigeonite reacted with the magma to form hypersthene and the difference in the Mg/Fe ratio of these two pyroxenes reflects the difference of this ratio between early pigeonite and the magma at the time of reaction. Some of the grains of early pigeonite, now inverted to hypersthene, evidently escaped this reaction with the magma. Bulk compositions of pyroxenes intermediate between that of pigeonite and hypersthene are postulated on the grounds of varying amounts of exsolved augite in the hypersthene which has originated from pigeonite by reaction with magma.     

Bonding in eight ordered clinopyroxenes isostructural with diopside

Bond distances and angles in isostructural, ordered clinopyroxenes are compared for eight compositions, based on five new and three published crystal-structure refinements from X-ray diffraction data. Unit-cell parameters and configuration of the silicate chains are directly correlated with cation composition and distribution in the M2 and M1 sites.Publication authorized by the Director, U. S. Geological Survey.Our thanks go to D. B. Stewart, C. Milton, and C. S. Ross, U. S. Geological Survey, who supplied crystals of the minerals, to D. B. Stewart for synthesis of iron spodumene, to Dr. L. Fuchs, Argonne National Laboratory, for synthesis of ureyite, and to Dr. B. Mason, U. S. National Museum, who transmitted the ureyite crystals.     

Multiple origins of clinopyroxenes in alkali basaltic rocks

Geochemical and textural data on clinopyroxenes in individual alkali basaltic flows from provinces in eastern Australia and the Massif Central can be used to differentiate four different modes of origin (three at high pressure) for these clinopyroxenes. Many single flows from the two provinces contain clinopyroxenes of three, or even four, of these origins. Rare flows contain core clinopyroxene with overgrowths of clinopyroxenes of two distinct generation. Each of the overgrowth is compositionally analogous to clinopyroxenes occurring in xenoliths or as discrete crystals in the same host lava. Such rimming relationships provide evidence that the host magma has undergone high pressure crystallisation and confirm that some xenoliths and megacrysts are cognate. With decreasing pressure the major changes in clinopyroxene chemistry are an increase in the ratio Al^lv/Al^vi, a linear increase of atomic proportions of Ti and Al with decreasing Si, and an increase in the Ti: (100 Mg/(Mg + Σ Fe)) ratio of the pyroxenes. Al₂O₂ wt, % is an unreliable potential geobarometric indicator; consideration of tetrahedral and octahedral site occupancies by Al (Al^lv/Al^vl ratio) is necessary. High-pressure fractionation dominated by clinopyroxene is postulated for some basaltic-composition, resulting in SiO₂ depletion, alkali enrichment and decrease in the Mg/(Mg + Fe²⁺) value of the host magma.     

Observation of reactions in synthetic Ca-poor pyroxene single crystals at elevated temperatures by X-ray diffraction

Diffuse streaks in diffraction patterns of synthetic pyroxene single crystals at elevated temperatures are used to determine which reactions are initiated and how they proceed. The samples investigated are a) a host orthopyroxene (Wo₄En₈₃Fs₁₃) containing oriented pigeonite (Wo₆En₇₈Fs₁₆) parallel to (100) and b) a pigeonite (Wo₈En₇₅Fs₁₇). The maximum temperatures were 820° C and 1,015° C, respectively. No partial melting occurs at these temperatures, all reactions are in the subsolidus. In case a) augite is formed parallel to the (001) plane of pigeonite, but the augite is not exsolved by the pigeonite. This is proved by the absence of the obligatory streaks between corresponding reflections in highly resolved precession photographs. Instead, there are streaks from augite to the corresponding reflections of the host orthopyroxene. Example b) demonstrates that the temperature of the high-low transformation of pigeonite is very sensitive to the Ca content and clearly depends on the exsolution of augite. This augite is oriented parallel to (100) of pigeonite, not to (001). Both the high and the low pigeonite are present over a range of ～150° C, while the exsolution of augite continues. Simultaneously, orthopyroxene is also formed sharing (100) of pigeonite. There seems to be an indication that only low pigeonite inverts to orthopyroxene.     

Five clinopyroxenes in the Hareidland eclogite,Western Norway

Five clinopyroxenes can be distinguished on petrographic and chemical grounds in the Hareidland eclogite. Of these, three are omphacites. It is suggested that all three were originally of the same composition and that their present chemical differences are due to differences in their immediate chemical environments during retrograde metamorphism of the eclogite. The other two clinopyroxenes are symplectitic, and chemically vary from sodic augite to jadeite-poor omphacite. They were formed by exsolution of a sodic component (sodic plagioclase) from a parental omphacite.Publication no. 49 in the Norwegian Geotraverse Project.     

Phase transitions in leucite: Dielectric properties and transition mechanism

To investigate the mechanisms for the cubic-tetragonal phase transition in leucite (KAlSi₂O₆), the frequency dependence of the dielectric constant (), and of the electric conductivity (), have been measured as a function of temperature. The dielectric loss function, tan , contains two main features: (i) a classical Debye peak, with activation energy of 0.77 eV, ascribed to hopping of K-atoms between their channel (W) sites, via the vacant side-channel (S) sites; (ii) a heavily-overdamped relaxational mode which softens when the crystal is cooled towards the phase transition temperature. The latter relaxational mode shows a critical behaviour, and is thus directly correlated with the transition mechanism. As it is only the potassium ions that could relax at frequencies well below the optical phonon branches, it appears that their movement is relaxational (i.e. heavily overdamped) rather than phonon-like. At temperatures above the transition point, the relaxation of K⁺ in an electric field is analysed in terms of collective motions within tetragonal domains. Direct evidence for the existence of such domains follows from the presence of diffuse intensity in single-crystal X-ray diffraction experiments.     

Phase transition of zircon at high P-T conditions

Abstract In situ observations of the zircon-reidite transition in ZrSiO₄ were carried out using a multianvil high-pressure apparatus and synchrotron radiation. The phase boundary between zircon and reidite was determined to be P (GPa) = 8.5+0.0017×(T-1200) (K) for temperatures between 1100–1900 K. When subducted slabs, including igneous rocks and sediments, descend into the upper mantle, the zircon in the subducted slab transforms into reidite at pressures of about 9 GPa, corresponding to a depth of 270 km. Reidite found in an upper Eocene impact ejecta layer in marine sediments is thought to have been transformed from zircon by a shock event. The peak pressure generated by the shock event in this occurrence is estimated to be higher than 8 GPa.Editorial responsibility: J. Hoefs     

Some clinopyroxenes from ultramafic inclusions in Dreiser Weiher,Eifel

Eight clinopyroxenes from wehrlites and clinopyroxenites and three clinopyroxenes of crystal lapilli in tuff of Dreiser Weiher in Eifel, Germany, have been separated and chemically analysed. One hornblende and two phlogopites from a wehrlite and clinopyroxenites have also been analysed. The rocks enclosing these inclusions are alkali basalts of basanite composition. The analysed clinopyroxenes contain considerable amounts of Al₂O₃ (3.87–10.84 wt%). The calculated Tschermak's component ranges from 5.9 to 18.4 mol per cent. All of the analysed clinopyroxenes are clearly different from chromian diopsides in lherzolite inclusions in basaltic rocks in Dreiser Weiher and other localities; the former has higher contents of total FeO, CaO and TiO₂ and lower contents of MgO and Cr₂O₃ than the latter. Two clinopyroxenes separated from apatite-bearing clinopyroxenites show high contents of Fe₂O₃ with about 2 per cent of Na₂O, indicating the presence of considerable amounts of acmite component in addition to Tschermak's component. The relative proportions of Al in the tetrahedral site and that in the octahedral site in the analysed clinopyroxenes are clearly different from those of the common igneous clinopyroxenes and eclogites, and similar to those of the clinopyroxenes from other inclusions in basaltic rocks and granulites. It is suggested that all the analysed clinopyroxenes and their host inclusions have crystallized from alkali basalt magmas in relatively deep levels of the continental crust.     

Phase transition and compression behavior of gibbsite under high-pressure

In situ high-pressure synchrotron X-ray diffraction and infrared absorption experiments for gibbsite were performed at room temperature up to 53 and 25 GPa, respectively. A phase transition was confirmed at about 2.5 GPa. The high-pressure phase is indexed as an orthorhombic structure, rather than a triclinic structure as reported in previous studies. The compressibility of gibbsite and its high-pressure polymorph were studied, and their bulk moduli K₀ were determined to be 49 and 75 GPa, respectively with K₀ as 4. The in situ high-pressure infrared absorption spectra revealed the gradual disordering of hydrogen substructure above 15 GPa in quasihydrostatic compression.     

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     

Computer modelling of hydrogen defects in the clinopyroxenes diopside and jadeite

Atomistic computer simulation techniques have been employed to model mechanisms of hydrogen incorporation in the clinopyroxenes diopside and jadeite. Calculation of solution reaction energies for the pure phases indicates that hydrogen is most easily incorporated via the formation of [V_Si(OH)₄] ^x hydrogarnet type defects. When components of the two phases are mixed, then solution energies can become exothermic. The substitution of Al for Si in diopside and of Mg or Ca for Al in jadeite, provides favourable routes for hydrogen incorporation, with exothermic values of solution energy. Thus the amount of water present in these minerals in the Earth’s upper mantle will vary with composition. Simulation of IR frequencies associated with O–H stretching at specific defect clusters has also been carried out. An analysis of hydrogen–oxygen bond lengths gives good agreement, although comparison of experimental and calculated IR frequencies are problematic. This is partly due to the complexity of experimental spectra, but may also be due in part to deficiencies in the ability of the model to accurately describe the O–H stretching frequency.     

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.     

SR-isotopic composition of clinopyroxenes from some mediterranean alpine lherzolites

Clinopyroxenes in the metamorphic alpine peridotites from Ronda, Béni Bouchera, Lanzo and Othris have ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios in the range of 0.70228 – 0.70370, similar to ocean ridge tholeiitic rock. Insofar as these lherzolites represent mantle sources, the present data allows simple evolutionary models relating basalt genesis and alpine peridotite. The highly radiogenic Sr reported in many whole rock alpine peridotites may be due to contamination in olivine and thus, earlier models that deny a simple relationship between alpine peridotite and the oceanic gabbros and basalts need a re-evaluation.     

Inter-diffusion coefficients parallel to the C-Axis in iron-rich clinopyroxenes calculated from microstructures

Subsolidus marginal zoning in calcium-poor clinopyroxenes and intermediate zoning in discontinuously zoned subcalcic- to calcium-rich clinopyroxenes from ironrich igneous rocks is used to calculate the interdiffusion coefficient, D_Ca?(Fe,Mg), parallel to the crystallographic caxis. Wagner's mathematical models describing the displacement of interfaces in solids as the result of isothermal diffusion are adopted. The steady-state heat flow equation is used to approximate the diffusion times. The calculated interdiffusion coefficients are of a reasonable order of magnitude, viz. 6.0×10^?20?2.0×10^?17cm²· sec^?1 at about 900° C.