High-pressure transformations in CaSiO3

Wollastonite transforms to a triclinic high-pressure polymorph, wollastonite II, at pressures > 25 kb. The equilibrium boundary [P(bars)=-4.7×T°C+32.810] has a rather flat negative P-T slope. The rapid reactivity of the transition over at least a 1000° C range, its insensitivity to T and its location around 30 kb are indicative of its potential for a pressure calibration curve at high T.     

High-pressure phase transformations in the MgFe2O4 and Fe2O3–MgSiO3 systems

 The crystal structure of MgFe₂O₄ was investigated by in situ X-ray diffraction at high pressure, using YAG laser annealing in a diamond anvil cell. Magnesioferrite undergoes a phase transformation at about 25 GPa, which leads to a CaMn₂O₄-type polymorph about 8% denser, as determined using Rietveld analysis. The consequences of the occurrence of this dense MgFe₂O₄ form on the high-pressure phase transformations in the (MgSi)_0.75(Fe^III)_0.5O₃ system were investigated. After laser annealing at about 20 GPa, we observe decomposition to two phases: stishovite and a spinel-derived structure with orthorhombic symmetry and probably intermediate composition between MgFe₂O₄ and Mg₂SiO₄. At pressures above 35 GPa, we observe recombination of these products to a single phase with Pbnm perovskite structure. We thus conclude for the formation of Mg₃Fe₂Si₃O₁₂ perovskite. Received: 27 March 2000 / Accepted: 1 October 2000     

High-pressure transformations of ilmenite to perovskite, and lithium niobate to perovskite in zinc germanate

In-situ X-ray powder diffraction measurements conducted under high pressure confirmed the existence of an unquenchable orthorhombic perovskite in ZnGeO₃. ZnGeO₃ ilmenite transformed into perovskite at 30.0 GPa and 1300±150 K in a laser-heated diamond anvil cell. After releasing the pressure, the lithium niobate phase was recovered as a quenched product. The perovskite was also obtained by recompression of the lithium niobate phase at room temperature under a lower pressure than the equilibrium phase boundary of the ilmenite–perovskite transition. Bulk moduli of ilmenite, lithium niobate, and perovskite phases were calculated on the basis of the refined X-ray diffraction data. The structural relations among these phases are considered in terms of the rotation of GeO₆ octahedra. A slight rotation of the octahedra plays an important role for the transition from lithium niobate to perovskite at ambient temperature. On the other hand, high temperature is needed to rearrange GeO₆ octahedra in the ilmenite–perovskite transition. The correlation of quenchability with rotation angle of GeO₆ octahedra for other germanate perovskites is also discussed.     

Phase transformations in ABO 4 type compounds under high pressure

For ABO ₄ type ternary oxides, high pressure phase transformations known up to the present are reviewed, and an attempt is made to explain and predict crystal structures of their high pressure phases. When ABO ₄ type compounds are plotted based on the two variables, k=r _A /r _B and t=(r _A +r _B )/2r _O, where r _A , r _B , and r _O are the ionic radii of A and B cations and divalent oxygen, they can be classified into the major structure types. It is found empirically that a compound basically transforms to the structure type isostructural with a compound lying in a classified area with the same k and larger t values in the diagram.     

High-pressure behaviour and equation of state of calcite, CaCO3

The high-pressure response of the cell parameters of calcite, CaCO₃, has been investigated by single crystal X-ray diffraction. The unit cell parameters have been refined from 0 to 1.435?GPa, and the linear and volume compressibilities have been measured as β _a =2.62(2)?×?10^?3?GPa^?1,β _c =7.94(7)?×?10^?3?GPa^?1, β _v =13.12?×?10^?3?GPa^?1. The bulk modulus has been obtained from a fit to the Birch-Murnaghan equation of state, giving K ₀=73.46?±?0.27?GPa and V ₀=367.789 ±?0.004?ų with K′=4. Combined with earlier data for magnesite, ankerite and dolomite, these data suggest that K ₀ V ₀ is a constant for the Ca-Mg rhombohedral carbonates.     

Rhombohedral ilmenite group nickel titanates with Zn, Mg, and Mn: synthesis and crystal structures

Binary, ternary, and quaternary rhombohedral ordered titanates, Ni_1/2Mn_1/2TiO₃, Ni_1/2Mg_1/2TiO₃, Ni_1/3Zn_1/3Mg_1/3TiO₃, and Ni_1/4Zn_1/4Mg_1/4Mn_1/4TiO₃, were obtained by solid-state synthesis at 1095°C at ambient pressure in a nitrogen atmosphere. All of the compounds adopt ATiO₃ (A = Ni, Mn, Zn, and Mg) stoichiometry. Crystal structures were refined by the Rietveld method from powder X-ray diffraction data. Unit cell parameters and unit cell volumes decrease with decreasing average radius of the ^vi A ²⁺ cation. All the synthetic titanates adopt the space group and the ilmenite structure consisting of distorted AO₆ and TiO₆ octahedra. The divalent cations and Ti⁴⁺ are distributed in layers of octahedra alternating along c with no evidence for disorder. In common with pyrophanite, NiTiO₃, and ilmenite sensu stricto, the distortion of the AO₆ octahedra is less than that of the TiO₆ octahedra. The Ti⁴⁺ and A-site cations in the titanates are off-centred within the coordination polyhedra. Deviation of the z positional parameters from their theoretical values for the A and Ti atoms indicate that in the titanates with the larger A ²⁺ cations and Goldschmidt tolerance factors, t ≥ 0.745, the AO₆ octahedral layer is more “puckered” above and below planes parallel to (001) than that of the TiO₆ octahedra, and vice versa in the titanates with smaller R _A ²⁺ for which t≤0.745. Data are given for the volumes and distortion indices of all the coordination polyhedra. This study confirms the existence and stability of complex solid solutions between ordered rhombohedral titanates of Ni and first-row transition metals at ambient conditions over a range of t from 0.786 to 0.737. These experimental data suggest that the formation of ilmenite-type titanates enriched in Ni is possible in exotic mineral-forming systems at low pressure and/or in extraterrestrial rocks.     

Viscosity of liquid silica,silicates and alumino-silicates

Viscosity measurements are reported for amorphous silica and liquids belonging to the systems SiO₂-M, SiO₂-Al₂O₃-M, where M is an alkali-earth metal oxide, MnO, or alumina, and the systems SiO₂-“FeO”, SiO₂-FeO-Fe₂O₃-CaO, and SiO₂-Al₂O₃-N, where N = Na₂O or K₂O. The implications of these measurements concerning the coordination of Al and the structure of these liquids are briefly discussed. Stable liquids in the systems SiO₂-Al₂O₂-M show a non-Arrhenian temperature dependence of their viscosity, in general. Results obtained with empirical methods to calculate the viscosity of silicate liquids are compared with our observations.     

Silicification,silicosis, polymerization,and aluminosis in geocrystallochemistry of silicates and aluminosilicates

Quantum-chemical interpretations of differentiation of the “normal” magmatic melt (the “Bowen's fork”) show certain defects in the traditionally crystallochemical interpretations of mineral structures and of the sequence of crystallization of minerals. The “dynamic unit,” in transitions from phase to phase and from lattice to lattice, proves to be the uncharged SiO₂ molecule and not the SiO₄ tetrahedron, which is but a static architectural detail of crystal structures. Different mechanisms and types of silicification (figs. 3-8), condensation and structures of the chains (figs. 9-14), structures of zeolites and other aluminosilicates (figs. 14, 17, 18), and the quantumchemical representation of corundum, as “molecular” Al₂O₃, illustrate further reevaluations of traditionalism in mineralogy.     

Structural relaxation and crystal field stabilization in Cr3+-containing oxides and silicates

The effect of crystal structure relaxation in oxygen-based Cr³⁺-containing minerals on the crystal field stabilization energy (CFSE) is considered. It is shown that the dependence of \textCFSE_{\textCr ³⁺} {\text{CFSE}}_{{{\text{Cr}}^{ 3+ } }} , which is found from optical absorption spectra, on the average interatomic distances is described by the power function with a negative exponent c \mathord

High-pressure polymorphism and structural transitions of norsethite,BaMg(CO3)2

In situ high-pressure investigations on norsethite, BaMg(CO₃)₂, have been performed in sequence of diamond-anvil cell experiments by means of single-crystal X-ray and synchrotron diffraction and Raman spectroscopy. Isothermal hydrostatic compression at room temperature yields a high-pressure phase transition at P _c ≈ 2.32 ± 0.04 GPa, which is weakly first order in character and reveals significant elastic softening of the high-pressure form of norsethite. X-ray structure determination reveals C2/c symmetry (Z = 4; a = 8.6522(14) Å, b = 4.9774(13) Å, c = 11.1542(9) Å, β = 104.928(8)°, V = 464.20(12) Å³ at 3.00 GPa), and the structure refinement (R ₁ = 0.0763) confirms a distorted, but topologically similar crystal structure of the so-called γ-norsethite, with Ba in 12-fold and Mg in octahedral coordination. The CO₃ groups were found to get tilted off the ab-plane direction by ~16.5°. Positional shifts, in particular of the Ba atoms and the three crystallographically independent oxygen sites, give a higher flexibility for atomic displacements, from which both the relatively higher compressibility and the remarkable softening originate. The corresponding bulk moduli are K ₀ = 66.2 ± 2.3 GPa and dK/dP = 2.0 ± 1.8 for α-norsethite and K ₀ = 41.9 ± 0.4 GPa and dK/dP = 6.1 ± 0.3 for γ-norsethite, displaying a pronounced directional anisotropy (α: β _a ^?1  = 444(53) GPa, β _c ^?1  = 76(2) GPa; γ: β _a ^?1  = 5.1(1.3) × 10³ GPa, β _b ^?1  = 193(6) GPa β _c ^?1  = 53.4(0.4) GPa). High-pressure Raman spectra show a significant splitting of several modes, which were used to identify the transformation in high-pressure high-temperature experiments in the range up to 4 GPa and 542 K. Based on the experimental series of data points determined by XRD and Raman measurements, the phase boundary of the α-to-γ-transition was determined with a Clausius–Clapeyron slope of 9.8(7) × 10^?3 GPa K^?1. An in situ measurement of the X-ray intensities was taken at 1.5 GPa and 411 K in order to identify the nature of the structural variation on increased temperatures corresponding to the previously reported transformation from α- to β-norsethite at 343 K and 1 bar. The investigations revealed, in contrast to all X-ray diffraction data recorded at 298 K, the disappearance of the superstructure reflections and the observed reflection conditions confirm the anticipated \(R\bar{3}m\) space-group symmetry. The same superstructure reflections, which disappear as temperature increases, were found to gain in intensity due to the positional shift of the Ba atoms in the γ-phase.     

High-pressure generation in the Kawai-type multianvil apparatus equipped with tungsten-carbide anvils and sintered-diamond anvils,and X-ray observation on CaSnO3 and (Mg,Fe)SiO3

We extended the attainable pressure of the Kawai-type multianvil apparatus to 71.3 GPa and 120.3 GPa at room temperature by equipping it with tungsten carbide (WC) and sintered diamond (SD) cubic anvils, respectively. In the experiments with WC anvils, pressure decreased largely, ΔP ∼−20 GPa, on heating from room temperature to 1500 K. In the experiments with SD anvils, pressure also dropped to 105 GPa from 120 GPa at 1673 K. In order to generate higher pressure and temperatures, therefore, innovation of SD material in both quality and size are essential, together with improvements of cell assembly. Besides pressure generation, we conducted in situ energy-dispersive X-ray diffraction observations on CaSnO₃ and (Mg,Fe)SiO₃ in the experiments with WC and SD anvils, respectively. We observed the growth of new peaks, which can be assigned to the post-perovskite phase, transformed from a starting material of CaSnO₃ perovskite at 48.4 GPa and 1500 K, although they are not clearly identified. In contrast, we could not observe the post-perovskite phase of (Mg,Fe)SiO₃ in the present P–T conditions generated by experiments with SD anvils.     

Electron Density distribution and bonding in silicates

This paper summarizes the recent results of the investigation of bonding in silicates obtained by precision X-ray diffraction. The experimental electron density distribution is compared with theoretical electron density maps calculated for model silicate molecules. The characteristic features of the chemical bonds in ortho-, ring-, chain- and framework silicates are discussed.     

Aluminum silicates in the Mount Raleigh pendant, British Columbia

In regionally metamorphosed pelites of the Mount Raleigh pendant, the fibrolite isograd occurs 5km downgrade from the sillimanite isograd. Fibrolite formed from the decomposition of biotite, a reaction that probably resulted from the late-stage influx of acidic volatiles. In contrast, sillimanite formed by the direct,'volume-for-volume'replacement of andalusite. Andalusite and sillimanite coexist in a 3 km-wide zone above the sillimanite isograd. Electron probe analyses of these phases reveal low minor element contents and yield K _D [= X ] values close to unity; the low Fe₂O₃ contents are compatible with reducing conditions implied by the ubiquity of graphite. Because K _D → 1.0, the zone of coexisting andalusite + sillimanite cannot be attributed to multivariancy resulting from partitioning of minor elements between these phases. Rather, the metastable persistence of andalusite into the sillimanite P-T stability field is suggested. The modal proportions of sillimanite versus andalusite imply that minimal (<5%) and alusitesillimanite reaction occurred in a zone 1.5km above the sillimanite isograd; in contrast, there was a marked increase in reaction progress immediately above this zone. With an estimated thermal gradient (in the plane of exposure) of approximately 20°C/km, the 1.5 km-wide zone of nil reaction suggests that the andalusite-sillimanite equilibrium boundary was overstepped by about 30 °C before significant reaction occurred. Inclusion-rich areas in andalusite provided favourable sites for sillimanite nucleation ; however, the growth of sillimanite may have been impeded by'pinning'of sillimanite grain boundaries by inclusions.     

High-pressure behavior of MnGeO3 and CdGeO3 perovskites and the post-perovskite phase transition

The stability and high-pressure behavior of perovskite structure in MnGeO₃ and CdGeO₃ were examined on the basis of in situ synchrotron X-ray diffraction measurements at high pressure and temperature in a laser-heated diamond-anvil cell. Results demonstrate that the structural distortion of orthorhombic MnGeO₃ perovskite is enhanced with increasing pressure and it undergoes phase transition to a CaIrO₃-type post-perovskite structure above 60 GPa at 1,800 K. A molar volume of the post-perovskite phase is smaller by 1.6% than that of perovskite at equivalent pressure. In contrast, the structure of CdGeO₃ perovskite becomes less distorted from the ideal cubic perovskite structure with increasing pressure, and it is stable even at 110 GPa and 2,000 K. These results suggest that the phase transition to post-perovskite is induced by a large distortion of perovskite structure with increasing pressure.     

High-pressure phase transition in MnTiO3 from the ilmenite to the LiNbO3 structure

Crystals of a high-pressure phase of MnTiO₃ have been synthesized at pressures of 60 kbar using the SAM-85 cubic-anvil high pressure apparatus. Although all crystals examined were twinned on (10 \(\bar 1\) \(\bar 2\) ), a set of diffraction intensities that are essentially unaffected by the twinning were obtained. Three possible structure models were considered: (1) the corundum (completely disordered Mn and Ti), (2) the partially-disordered ilmenite, and (3) the LiNbO₃ structures. The R factors of the corundum and the disordered ilmenite models were much larger than that of LiNbO₃. Using structure factors unaffected by twinning, the final LiNbO₃-type refinement gave R _w=0.037 and R=0.034. The averaged bond lengths for Mn-O and Ti-O were consistent with ones calculated using Shannon and Prewitt's (1969) radii. The study concludes that MnTiO₃ II actually has an ordered LiNbO₃-type structure rather than the disordered one as reported previously. From the analysis of the two MnTiO₃ structures, the transition can be related to a cation reordering process, in which half of the cations participate, accompanied by the rotation of oxygens to accommodate the cations.     

Topologic symmetry and real symmetry in framework silicates

Summary The topologic symmetry of a framework silicate is reduced to topochemical symmetry by an ordering inside the tetrahedra; each further reduction of symmetry may be due to one of the following three causes: 1 ordered distribution of extraframework cations, 2 squeezing of the framework, 3 repulsion of extraframework cations.

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Topologische Symmetrie und reelle Symmetrie in Gerüstsilikaten

Zusammenfassung Die topologische Symmetrie von einem Gerüstsilikat wird zu topochemischer Symmetrie durch die Ordnungsverteilung in den Tetrahedern reduziert; jede weitere Reduktion der Symmetrie kann mit einer von drei Ursachen in Zusammenhang gebracht werden: 1 geordnete Verteilung der Nichtgerüstkationen, 2 Gerüstdeformation, 3 Abstoßkräfte zwischen Nichtgerüstkationen.

     

Denitrification and the stoichiometry of nutrient regeneration in Waquoit Bay, Massachusetts

To determine the removal of regenerated nitrogen by estuarine sediments, we compared sediment N₂ fluxes to the stoichiometry of nutrient and O₂ fluxes in cores collected in the Childs River, Cape Cod, Massachusetts. The difference between the annual PO₄ ³⁻ (0.2 mol P m⁻² yr⁻¹) and NH₄ ⁺ (1.6 mol N m⁻² yr⁻¹) flux and the Redfield N∶P ratio of 16 suggested an annual deficit of 1.5 mol N m⁻² yr⁻¹. Denitrification predicted from O₂∶NH₄ ⁺ flux ratios and measured as N₂ flux suggested a nitrogen sink of roughly the same magnitude (1.4 mol N m⁻² yr⁻¹). Denitrification accounted for low N∶P ratios of benthic flux and removed 32–37% of nitrogen inputs entering the relatively highly nutrient loaded Childs River, despite a relatively brief residence time for freshwater in this system. Uptake of bottom water nitrate could only supply a fraction of the observed N₂ flux. Removal of regenerated nitrogen by denitrification in this system appears to vary seasonally. Denitrification efficiency was inversely correlated with oxygen and ammonium flux and was lowest in summer. We investigated the effect of organic matter on denitrification by simulating phytoplankton deposition to cores incubated in the lab and by deploying chambers on bare and macroaglae covered sediments in the field. Organic matter addition to sediments increased N₂ flux and did not alter denitrification efficiency. Increased N₂ flux co-varied with O₂ and NH₄ ⁺ fluxes. N₂ flux (261±60 μmol m⁻² h⁻¹) was lower in chambers deployed on macroalgal beds than deployed on bare sediments (458±70 μmol m⁻² h⁻¹), and O₂ uptake rate was higher in chambers deployed on macroalgal beds (14.6±2.2 mmol m⁻² h⁻¹) than on bare sediments (9.6±1.5 mmol m⁻² h⁻¹). Macroalgal cover, which can retain nitrogen in the system, is a link between nutrient loading and denitrification. Decreased denitrification due to increasing macroalgal cover could create a positive feedback because decreasing denitrification would increase nitrogen availability and could increase macroalgae cover.     

Ion dynamics studies of liquid and glassy silicates,and gas-in-liquid solutions

We give a brief review of ion dynamics studies of liquid and glassy states of SiO₂ and silicate colutions which have been carried out in recent years in this laboratory. We summarize studies on SiO₂, Na⁺ migration in Na₂O·SiO₂ in the “glassy state”, and ionic coordination in multicomponent framework silicates. We present new results on the coordination of Al³⁺ in albite as a function of pressure and show that it is consistent with results of laboratory studies on albite glasses formed at high pressure. We compare calculated PVT data for jadeite, albite and diopside and relate the behavior of the low pressure compressibility to the spinodal limit at negative pressures. Some preliminary studies of inert gas solution in jadeite and of CO₂ solution in a glass having a composition of approximately Na₂O·3SiO₂ are described.