Silica-undersaturated sapphirine, spinel and kornerupine granulite facies rocks, NE Strangways Range, Central Australia

Small pods of silica-undersaturated Al-rich and Mg-rich granulite facies rocks containing sapphirine, pleonastic spinel, kornerupine, cordierite, orthopyroxene, corundum, sillimanite and gedrite are scattered throughout the NE Strangways Range, Central Australia. These are divided into four distinct rock types, namely orthopyroxene-rich aluminous granofels and metapelitic gneisses containing sapphirine, spinel or kornerupine. Two granulite facies metamorphic events are recognized, of which only the first (M1) is considered in this paper. Peak metamorphic mineral parageneses indicate that the M1 thermal maximum occurred at approximately 900–950 °C and 8–9 kbar. All samples are characterized by profuse and diverse coronitic and symplectic reaction textures. These are interpreted as evidence for the sequential crossing of the following reactions in the system FMAS: cordierite + spinel + corundum = sapphirine + sillimanite, cordierite + spinel = orthopyroxene + sapphirine + sillimanite, sapphirine + spinel + sillimanite = orthopyroxene + corundum, sapphirine + sillimanite = cordierite + orthopyroxene + corundum. Phase stability relationships in FMAS and MASH indicate an anticlockwise P–T path terminated by isobaric cooling. Such a path is exemplified by early low-P mineral parageneses containing spinel, corundum and gedrite and the occurrence of both prograde and retrograde corundum. Reaction textures preserve evidence for an increase in aH₂O and aB₂O₃ with progressive isobaric cooling. This hydrous retrogression resulted from crystallization of intimately associated M1 partial melt segregations. There is no evidence for voluminous magmatic accretion giving rise to the high M1 thermal gradient. The M1 P–T path may be the result of either lithospheric thinning after both crustal thickening and burial of the supracrustal terrane, or concomitant crustal thickening and mantle lithosphere thinning.     

Formation of clinopyroxene + spinel and amphibole + spinel symplectites in coronitic gabbros from the Sierra de San Luis (Argentina): a key to post-magmatic evolution

The El Arenal metagabbros preserve coronitic shells of orthopyroxene ± Fe‐oxide around olivine, as well as three different types of symplectite consisting of amphibole + spinel, clinopyroxene + spinel and, more rarely, orthopyroxene + spinel. The textural features of the metagabbros can be explained by the breakdown of the olivine + plagioclase pair, producing orthopyroxene coronas and clinopyroxene + spinel symplectites, followed by the formation of amphibole + spinel symplectites, reflecting a decrease in temperature and, possibly, an increase in water activity with respect to the previous stage. The metagabbros underwent a complex P–T history consisting of an igneous stage followed by cooling in granulite, amphibolite and greenschist facies conditions. Although the P–T conditions of emplacement of the igneous protolith are still doubtful, the magmatic assemblage suggests that igneous crystallization occurred at a pressure lower than 6 kbar and at 900–1100 °C. Granulitic P–T conditions have been estimated at about 900 °C and 7–8 kbar combining conventional thermobarometry and pseudosection analysis. Pseudosection calculation has also shown that the formation of the amphibole + spinel symplectite could have been favoured by an increase in water activity during the amphibolite stage, as the temperature of formation of this symplectite strongly depends on aH₂O (<740 °C for aH₂O = 0.5; <790 °C for aH₂O = 1). Furthermore, but not pervasive, re‐equilibration under greenschist facies P–T conditions is documented by retrograde epidote and chlorite. The resulting counterclockwise P–T path consists of progressive, nearly isobaric cooling from the igneous stage down to the granulite, amphibolite and greenschist stage.     

Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.     

Quantitative P–T–X constraints on orthopyroxene-bearing high-pressure granulites in felsic–metapelitic rocks: evidence from the Huangtuling granulite, Dabieshan Orogen

High‐pressure granulites are generally characterized by the absence of orthopyroxene. However, orthopyroxene is reported in a few high‐pressure, felsic–metapelitic granulites, such as the Huangtuling felsic high‐pressure granulite in the North Dabie metamorphic core complex in east‐central China, which rarely preserves the high‐pressure granulite facies assemblage of garnet + orthopyroxene + biotite + plagioclase + K‐feldspar + quartz. To investigate the effects of bulk‐rock composition on the stability of orthopyroxene‐bearing, high‐pressure granulite facies assemblages in the NCKFMASHTO (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃) system, a series of P–T–X pseudosections based on the melt‐reintegrated composition of the Huangtuling felsic high‐pressure granulite were constructed. Calculations demonstrate that the orthopyroxene‐bearing, high‐pressure granulite facies assemblages are restricted to low X_Al [Al₂O₃/(Na₂O + CaO + K₂O + FeO + MgO + Al₂O₃) < 0.35, mole proportion] or high X_Mg [MgO/(MgO + FeO) > 0.85] felsic–metapelitic rock types. This study also reveals that the X_Al values in the residual felsic–metapelitic, high‐pressure granulites could be significantly reduced by a high proportion of melt loss. We suggest that orthopyroxene‐bearing, high‐pressure granulites occur in residual overthickened crustal basement under continental subduction–collision zones and arc–continent collision belts.     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Bonding in silicates: an assessment of bonding in orthopyroxene

The molecular orbital and crystal field theories are compared and their applicabilities to bonding in silicates are discussed, A molecular orbital bonding model is favoured for orthopyroxene since bonding in both tetrahedral and non-tetrahedral sites within the crystal structure can be described and accommodated by the theory. It is suggested that Fe located in M₂ sites has more electron delocalisation (or covalence) associated with it than Fe located in the M₁ site. Order-disorder phenomena in orthopyroxene are discussed in relationship to Mueller's (1970) two-step exchange mechanism, whereby the first step corresponds to vacancy activation and the second step to exchange of Fe between an ‘octahedral’ site and a vacancy.     

Tetrahedral compression in (Mg,Fe)SiO3 orthopyroxenes

Single-crystal structure determinations at pressure have shown that the structural response of synthetic (Mg_0.6Fe_0.4)SiO₃ orthopyroxene to compression is the same as that previously observed in MgSiO₃ orthoenstatite. At pressure below ～4?GPa there is no significant compression of the SiO₄ tetrahedra, while above ～4?GPa the tetrahedra decrease in volume as a result of Si?O bond shortening. A study of the compressional behaviour of synthetic FeSiO₃ orthoferrosilite also shows the same behaviour below 4?GPa, but studies at higher pressures are precluded due to the transformation of the sample to the higher density C2/c high-clinoferrosilite polymorph. A further single-crystal study to 6?GPa of a Ca²⁺-containing natural orthopyroxene shows that chemical substitution of, primarily, Al³⁺ and Ca²⁺ into the structure of orthopyroxene inhibits the initial rapid compression of the M2?O3 bonds observed in the synthetic samples, and no significant tetrahedral compression is observed in this sample. Raman data collected from synthetic MgSiO₃ orthoenstatite show that there is a change in the rate of change of frequency with pressure, δν/δP, between 3.5 and 6.0?GPa, but no changes in the number of observed bands. These observations indicate a non-symmetry-breaking change in the properties of the orthoenstatite, which is associated with the change in compression mechanism observed using X-ray diffraction techniques at this pressure.     

Sapphirine parageneses from the Caraiba complex, Bahia, Brazil: the influence of Fe2+–Fe3+ distribution on the stability of sapphirine in natural assemblages

Abstract Sapphirine-bearing rocks occur in three conformable, metre-size lenses in intrusive quartzo-feldspathic orthogneisses in the Curaçà valley of the Archaean Caraiba complex of Brazil. In the lenses there are six different sapphirine-bearing rock types, which have the following phases (each containing phlogopite in addition): A: Sapphirine, orthopyroxene; B: Sapphirine, cordierite, orthopyroxene, spinel; C: Sapphirine, cordierite; D: Sapphirine, cordierite, orthopyroxene, quartz; E: Sapphirine, cordierite, orthopyroxene, sillimanite, quartz; F: Sapphirine, cordierite, K-feldspar, quartz. Neither sapphirine and quartz nor orthopyroxene and sillimanite have been found in contact, however. During mylonitization, introduction of silica into the three quartz-free rocks (which represent relict protolith material) gave rise to the three cordierite and quartz-bearing rocks. Stable parageneses in the more magnesian rocks were sapphirine–orthopyroxene and sapphirine–cordierite. In more iron-rich rocks, sapphirine–cordierite, sapphirine-cordierite–sillimanite, cordierite–sillimanite, sapphirine–cordierite–spinel–magnetite and quartz–cordierite–orthopyroxene were stable. The iron oxide content in sapphirine of the six rocks increases from an average of 2.0 to 10.5 wt % (total Fe as FeO) in the order: C,F–A,D–B,E. With increase in Fe there is an increase in recalculated Fe₂O₃ in sapphirine. The four rock types associated with the sapphirine-bearing lenses are: I: Orthopyroxene, cordierite, biotite, quartz, feldspar tonalitic to grandioritic gneiss; II: Biotite, quartz, feldspar gneiss; III: Orthopyroxene, clinopyroxene, hornblende, plagioclase meta-norite; IV: Biotite, orthopyroxene, quartz, feldspar, garnet, cordierite, sillimanite granulite gneiss. The stable parageneses in type IV are orthopyroxene–cordierite–quartz, garnet–sillimanite–quartz and garnet–cordierite–sillimanite. Geothermobarometry suggests that the associated host rocks equilibrated at 720–750°C and 5.5–6.5 kbar. Petrogenetic grids for the FMASH and FMAFSH (FeO–MgO–Al₂O₃–Fe₂O₃–SiO₂–H₂O) model systems indicate that sapphirine-bearing assemblages without garnet were stabilized by a high Fe³⁺ content and a high X_Mg= (Mg/ (Mg+Fe²⁺)) under these P–T conditions.     

On local structural changes in lizardite-1T: {Si4+/Al3+}, {Si4+/Fe3+}, [Mg2+/Al3+], [Mg2+/Fe3+] substitutions

Geometrical changes induced by cation substitutions {Si⁴⁺/Al³⁺}[Mg²⁺/Al³⁺], {2Si⁴⁺/2Al³⁺} [2Mg²⁺/2Al³⁺], {Si⁴⁺/Fe³⁺} [Mg²⁺/Al³⁺] or [Mg²⁺/Fe³⁺], where {} and [] indicate tetrahedral and octahedral sheet in lizardite 1T, are studied by ab-initio quantum chemistry calculations. The majority of the models are based on the chemical compositions reported for various lizardite polytypes with the amount of Al in the tetrahedral sheets reported to vary from 3.5% to 8% in the 1T and 2H ₁, up to ~30% in the 2H ₂ polytype. Si⁴⁺ by Fe³⁺ substitution in the tetrahedral sheet with an Al³⁺ (Fe³⁺) in the role of a charge compensating cation in the octahedral sheet is also examined. The cation substitutions result in the geometrical changes in the tetrahedral sheets, while the octahedral sheets remain almost untouched. Substituted tetrahedra are tilted and their basal oxygens pushed down from the plane of basal oxygens. Ditrigonal deformation of tetrahedral sheets depends on the substituting cation and the degree of substitution.     

Sapphirine II

The crystal structure of aP2₁/a polymorph of sapphirine (a=11.286(3),b=14.438(2),c=9.957(2) Å, β=125.4(2) °) of composition [Mg_3.7Fe _0.1 ²⁺ Al_4.1- Fe _0.1 ³⁺ ]^IV[Si_1.8Al_4.2]^IVO₂₀ was refined using structure factors determined by both neutron and x-ray diffraction methods to conventionalR factors of 0.067 and 0.031. respectively, forF _obs>2σ. The results of the two refinements agree reasonably well, but a half-normal probability plot (Abrahams, 1974) comparing the two data sets indicates that the pooled standard deviations of the atomic coordinates have been underestimated by a factor of two. The structure of sapphirine, solved initially by Moore (1969), consists of cubic closest packed oxygens with octahedral and predominantly tetrahedral layers alternately stacked along [100]. The layer in which 70% of the octahedral sites are occupied has an Mg-Al distribution characterized by Mg-rich octahedra sharing edges mainly with Al-rich octahedra. Mean octahedral bond lengths correlate well with Al occupancy determined by neutron site refinement if the relative number of shared octahedral edges is taken into account (see Table 1). The predominantly tetrahedral layer has 10% of the octahedral sites occupied by Al and 30% of the tetrahedral sites occupied by Al-Si in the ratio 2.33∶1. There are single chains of Al-Si tetrahedra parallel toz with corner-sharing wing tetrahedra (T5 andT6) on either side in the (100) plane. The meanT-O distance is highly correlated with Al occupancy, X_Al, as determined from the neutron site refinement: $$\langle T - O\rangle = 1.656 + 0.105X_{Al} (r^2 = 0.995).$$ Details of the neutron refinement are summarized below.     

A low temperature X-ray single-crystal diffraction and polarised infra-red study of epidote

The effects of low-temperature on the crystal structure of a natural epidote [Ca_1.925Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6)? and β = 115.396(8)° at room conditions, Sp. Gr. P2₁ /m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe³⁺ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000–2,500 cm⁻¹ are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)–O(4). Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and Fe³⁺ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to protonation of O(10)–O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected for “rigid body motions”. A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra, especially when corrected for “non-correlated motion”. The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction of the magnitude of the thermal displacement ellipsoids, with a variation of U _eq (defined as one-third of the trace of the orthogonalised U _ij tensor) by ~40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U _eq of the octahedral and oxygen sites decrease similarly by ~35%, whereas those of the tetrahedral cations by ~22%.     

First-principles study of (MgH2SiO4)? n (Mg2SiO4) hydrous olivine structures. I. Crystal structure modelling of hydrous olivine Hy-2 a (MgH2SiO4) ? 3(Mg2SiO4)

 Recently, the Hy-2a hydrous olivine (MgH₂ SiO₄)·3(Mg₂SiO₄) occurring as nanometre-sized inclusions in mantle olivines has been found by TEM, and has been suggested to be a new DHMS phase (Khisina et al. 2001). A model of the crystal structure of Hy-2a has been proposed as a 2a-superstructure of olivine with one Me²⁺ -vacant octahedral layer in the (1 0 0) plane per Hy-2a unit cell (Khisina and Wirth 2002). In the present study the crystal structure of Hy-2a hydrous olivine is optimized by ab initio calculations. The aims of this study are: (1) verification of the suggested models of Hy-2a hydrous olivine structure; (2) calculation of the most stable configurations for Hy-2a structure with minimum static lattice energy, by assuming a possible formation of Me²⁺ vacancies in either M1 or M2 octahedral sites; (3) determination of the position of protons and hydrogen bonds in the Hy-2a structure. Several different possible configurations of the Hy-2a structure are optimized. The results support the idea of a stable olivine structure with ordered planar-segregated OH-bearing defects oriented parallel to (1 0 0). The data obtained indicate a preferred stability of the Hy-2a structure with the protons associated with M1 vacancies and bonded with O1 and O2 oxygen sites. The relative energy values of the optimized Hy-2a structure configurations correlate as a rule with the average shifts of atoms from their positions in pure forsterite structure. Received: 7 February 2002 / Accepted: 23 October 2002     

The influence of crystal field stabilization energy on Fe2+ partitioning in paragenetic minerals

In order to explore possible quantitative relations between crystal field stabilization energy, CFSE, and partitioning behaviour of the 3d ⁶-configured Fe²⁺ ion, a suite of 29 paragenetic rock-forming minerals from 12 high-grade metamorphic rock samples of the Ukrainian shield, including the parageneses garnet/orthopyroxene/clinopyroxene (2x), orthopyroxene/clinopyroxene, garnet/clinopyroxene, garnet/orthopyroxene/biotite, garnet/biotite, garnet/cordierite, garnet/cordierite/biotite, garnet/orthopyroxene/clinopyroxene/Ca-amphibole, Ca-amphibole/biotite (retrograde), was studied by electron microprobe analysis to obtain the respective K _D Fe^{2+ (Ph1/Ph2)} values and by polarized single crystal electronic absorption spectroscopy to evaluate the respective CFSE_Fe2+ values. Other than in the case of Cr³⁺, a clear quantitative relation between K _D ^(Ph1/Ph2) and the ΔCFSE^(Ph1/Ph2) was only observed when geometrical factors, mainly the volume of crystallographic sites and ionic radii of ions competing in the partitioning process, are similar in the respective two paragenetic phases to within 15–20%. In such cases, the ΔCFSE_Fe2+ contribution to K _D ^(Ph1/Ph2) amounts to 0.1 to 0.2 log K _D per 100 cm⁻¹ΔCFSE. The conclusion is that ΔCFSE_Fe2+ plays only a secondary role after geometrical factors, in the partitioning behaviour of Fe²⁺. The reason for this is seen in the facts that, compared to the 3d ³-configured Cr³⁺ ion, CFSE of the 3d ⁶-configured Fe²⁺ amounts only to 20–25%, and that the former ion enters only octahedral sites with similar geometrical properties in the paragenetic mineral phases. Received: 17 November 1998 / Accepted: 28 June 1999     

OH incorporation in nearly pure MgAl2O4 natural and synthetic spinels

Four nearly pure MgAl₂O₄ spinels, of both natural and synthetic occurrence, have been studied by means of X-ray single crystal diffraction and FTIR spectroscopy in order to detect their potential OH content. Absorption bands that can be assigned to OH incorporated in the spinel structure were only observed in spectra of a non-stoichiometric synthetic sample. The absorption intensity of two bands occurring at 3350 and 3548 cm⁻¹ indicate an OH content of 90 ppm H₂O. Based on correlations of OH vibrational frequencies and O-H?O distances, the observed absorption bands correspond to O-H?O distances of 2.77 and 2.99 Å, respectively, which is close to the values obtained by the structure refinements for ^VIO-O_unsh (2.825 Å) and ^IVO-O (3.001 Å). This indicates that one probable local position for hydrogen incorporation is the oxygens coordinating a vacant tetrahedral site. The present spectra demonstrate that the detection limit for OH in Fe-free spinels is in the range 10-20 ppm H₂O. However, at appreciable Fe²⁺ levels, the detection of OH bands becomes hampered due to overlap with strong absorption bands caused by electronic d-d transitions in Fe²⁺ in the tetrahedral position.     

Variation of infrared absorption spectra in the system Bi2Al4−x Fe x O9 (x = 0–4), structurally related to mullite

The crystal structure of Bi₂Al_4−x Fe _x O₉ compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe³⁺ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi₂M₄O₉ compounds (M = Al, Fe³⁺) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm⁻¹ region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm⁻¹ band group, which is assigned to Al(Fe³⁺)–O stretching vibrations of the corner-sharing MO₄ tetrahedra. The Bi₂Al₄O₉ and Bi₂Fe₄O₉ endmembers display single bands with maxima centred at 922 and 812 cm⁻¹, respectively. Intermediate Bi₂Al_4−x Fe _x O₉ compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm⁻¹ range are assigned to low-energy stretching vibrations of the MO₄ tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm⁻¹ range are essentially determined by M–O stretching modes of the M cations in octahedral coordination.     

The influence of the Jahn–Teller effect at Fe<Superscript>2+</Superscript> on the structure of chromite at high pressure

The crystal structure of chromite FeCr₂O₄ was investigated to 13.7 GPa and ambient temperature with single-crystal X-ray diffraction techniques. The unit-cell parameter decreases continuously from 8.3832 (5) to 8.2398 (11) Å up to 11.8 GPa. A fit to the Birch–Murnaghan equation of state (EoS) based on the P–V data gives: K ₀ = 209 (13) GPa, K′ = 4.0 (fixed), and V ₀ = 588 (1) ų. The FeO₄ tetrahedra and CrO₆ octahedra are compressed isotropically with pressure with their Fe–O and Cr–O bond distances decreasing from 1.996 (6) to 1.949 (7) Å and from 1.997 (3) to 1.969 (7) Å, respectively. The tetrahedral site occupied by the Fe²⁺ cation is more compressible than the octahedral site occupied by the Cr³⁺ cation. The resulting EoS parameters for the tetrahedral and the octahedral sites are K ₀ = 147 (9) GPa, K′ = 4.0 (fixed), V ₀ = 4.07 (1) ų and K ₀ = 275 (24) GPa, K′ = 4.0 (fixed), V ₀ = 10.42 (2) ų, respectively. A discontinuous volume change is observed between 11.8 and 12.6 GPa. This change indicates a phase transition from a cubic (space group Fd-[`3]{\overline{3}} m) to a tetragonal structure (space group I4₁ /amd). At the phase transition boundary, the two Cr–O bonds parallel to the c-axis shorten from 1.969 (7) to 1.922 (17) Å and the other four Cr–O bonds parallel to the ab plane elongate from 1.969 (7) to 1.987 (9) Å. This anisotropic deformation of the octahedra leads to tetragonal compression of the unit cell along the c-axis. The angular distortion in the octahedron decreases continuously up to 13.7 GPa, whereas the distortion in the tetrahedron rises dramatically after the phase transition. At the pressure of the phase transition, the tetrahedral bond angles along the c-axis direction of the unit cell begin decreasing from 109.5° to 106.6 (7)°, which generates a “stretched” tetrahedral geometry. It is proposed that the Jahn–Teller effect at the tetrahedrally coordinated Fe²⁺ cation becomes active with compression and gives rise to the tetrahedral angular distortion, which in turn induces the cubic-to-tetragonal transition. A qualitative molecular orbital model is proposed to explain the origin and nature of the Jahn–Teller effect observed in this structure and its role in the pressure-induced phase transition.     

Raman study of MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 synthetic series: the effects of Fe2+ and Fe3+ on Raman shifts

Two synthetic series of spinels, MgCr₂O₄–Fe²⁺Cr₂O₄ and MgCr₂O₄–MgFe₂ ³⁺O₄ have been studied by Raman spectroscopy to investigate the effects of Fe²⁺ and Fe³⁺ on their structure. In the first case, where Fe²⁺ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A_1g and E_g toward lower wavenumbers with the increase of the chromite component into the spinel, while the F_2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe³⁺ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe³⁺ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm^?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe³⁺ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm^?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm^?1, when observed, show little or negligible Raman shift.     

Influence of structural factors on 29Si and 27Al NMR chemical shifts of phyllosilicates 2:1

The ²⁹Si and ²⁷Al nuclear magnetic resonance (NMR) analysis of synthetic trioctahedral phyllosilicates 2:1, with tetrahedral ratios Al _T/(Si + Al _T) ranging from 0 to 0.5, has shown that the ditrigonal distortion of tetrahedral rings (angle ) is the main factor controlling chemical shift values of tetrahedral components in both signals. The increase of ditrigonal rotation angle shifts these components towards more positive values. For each sample, the composition of tetrahedral and octahedral sheets determine the value of , and from this parameter, the mean tetrahedral Tot angle and the chemical shift values of components are deduced. For a given environment, variations on ditrigonal angle are responsibles for the observed evolution of chemical shift values with bulk composition. The comparative analysis of micas and saponite samples has demonstrated that the location of compensating charge (interlayer and octahedral sheet) does not affect chemical shift values.     

Mg-Cr~(2+)橄揽石、辉石和尖晶石的晶胞参数测定及Cr~(2+)在各晶体结构中的占位

本文用Mg－Cr2+做榄石、辉石、尖晶石的粉晶X射线衍射数据，采取“整体图谱最小二乘Rietveld”方法计算了上述矿物的晶胞参数和摩尔体积，并对Cr2+在各晶体结构中的占位情况进行了研究。结果显示，各矿物的晶胞参数随含Cr2+量的增大而增大。据Vegard定律，推算出各端元组分铬橄榄石（Cr2SiO1）、铬辉石（Cr2SiO2O6）及立方铬尖晶石（Cr3O4）的摩尔体积分别为47．7，68．0，44．9cm3。精化结构参数指示，在橄榄石中，Cr2+随机分配在两个八面体（M1，M2）位置；在辉石中，Cr2+优先选择八面体M2位置；在尖晶石中，Cr2+占置四面体位置。这种晶体内离子分配可从离子半径差别或晶体场稳定能大小得到解释。     

The crystal chemistry of lithium and Fe3+ in synthetic orthopyroxene

Lithian ferrian enstatite with Li₂O = 1.39 wt% and Fe₂O₃ 7.54 wt% was synthesised in the (MgO–Li₂O–FeO–SiO₂–H₂O) system at P = 0.3 GPa, T = 1,000°C, fO₂ = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å³. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula ^M2(Mg_0.59Fe _0.21 ²⁺ Li_0.20) ^M1(Mg_0.74Fe _0.20 ³⁺ Fe _0.06 ²⁺ ) Si₂O₆. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe³⁺ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe²⁺) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe³⁺, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe²⁺-Mg ordering process in octahedral sites.