Pressure-induced structural modifications in Mg2GeO4-olivine: A Raman spectroscopic study

Raman spectra of Mg₂GeO₄-olivine were obtained from ambient pressure up to 34 GPa at ambient temperature. Under quasi-hydrostatic pressure conditions, the following modifications in the Raman spectra occur as pressure increases: 1) near 11 GPa, two sharp extra bands appear in the 600–700 cm^?1 frequency range, and increase in intensity with respect to the olivine bands; 2) above 22 GPa, these two bands become very intense, and the number, position and relative intensity of the other vibrational bands drastically change; 3) the intensity of sharp bands progressively decreases above 25 GPa. The transformation occurs at lower pressures under non-hydrostatic conditions. During decompression to atmospheric pressure, the high-pressure phase partially reverts to olivine. These observations can be interpreted as the progressive metastable transformation from the olivine structure to a crystalline phase with four-fold coordinated Ge, in which the GeO₄ tetrahedra are polymerized. We propose that the metastable high-pressure phase is a structurally disordered spinelloid close to the hypothethical ω- or ?^*-phase, and forms by a shear mechanism assisted by the development of a dynamical instability in the olivine structure. Implications for the transformations undergone by olivines under far-from-equilibrium conditions (e.g. in subducting lithospheric slabs and in shocks) are discussed.     

Rietveld refinement study of the cation distribution in (Co, Mg)-olivine solid solution

The Co,?Mg-cation ordering in the Mg₂SiO₄–Co₂SiO₄ solid solution series as a function of the chemical composition has been studied by X-ray powder diffraction methods. The structures of nine polycrystalline samples prepared at 1200?°C and equally cooled to room temperature within 2 minutes have been refined by the Rietveld technique. The results corroborate earlier studies showing a strong preference of Co²⁺ for the M1 site. Considering the agreement of the powder diffraction results with those of single crystal studies allows the conclusion that the powder method is well suited for investigating the cation distribution in compounds exhibiting significant ordering effects. According to the cation distributions derived from first rapid quench experiments, the cation order of the slowly cooled samples corresponds to an estimated equilibrium temperature of 800?°C.     

Determination of Fe3+ and Fe2+ concentrations in feldspar by optical absorption and EPR spectroscopy

Ferrous and ferric iron concentrations in feldspars with low total iron content (<0.32 wt% total Fe) were determined from optical and electron paramagnetic resonance (EPR) spectra to better than ±15 percent of the amount present. Optical spectra indicate that Fe²⁺ occupies two distorted M-sites in plagioclases of intermediate structural state. The linear dependence of the Fe²⁺/Fe total ratio on An content demonstrates that Fe²⁺ substitutes for Ca (not Na) so that the number of Ca-sites is a principal factor in iron partitioning in plagioclase. EPR powder spectra show that the number of sites for Fe³⁺ depends on structural state rather than on plagioclase chemistry. The observed linear correspondence of EPR double-integrated intensities with optical peak areas shows that all Fe³⁺ is tetrahedrally coordinated in both plagioclase and disordered potassium feldspar. Microcline perthites show, in addition to tetrahedral Fe³⁺, a signal due to axially coordinated ferric iron, which we associate with formation of hematite inclusions.     

Mg,Fe2+ site occupancies in coexisting pyroxenes

The separate distributions for MgSiO₃ and FeSiO₃ in coexisting pyroxenes from the Skaergaard and Bushveld intrusions and charnockites, which were introduced in an earlier communication, indicate directly that significant amounts of both Fe²⁺ and Mg were present in the M(2) site of the Ca-rich pyroxene at the temperature of final intercrystalline equilibration. The calculated Fe²⁺ M(2) site occupancy in the Ca-rich pyroxene increases markedly with decrease in total MgSiO₃ content but the corresponding Mg site occupancy appears largely independent of MgSiO₃. The mean value of the distribution constant for intracrystalline exchange in the Ca-rich pyroxene decreases, away from unity, with decreasing temperature of equilibration. Occupancy of Mg and Fe²⁺ in the M (2) site of the Ca-rich pyroxene effectively compensates for the expected variation in K _D with composition resulting from intracrystalline partition in Ca-poor pyroxene, and this largely accounts for the difference in K _D between igneous and metamorphic pyroxenes. The variation of the augite limb of the pyroxene solvus within the pyroxene quadrilateral is developed as a possible geothermometer.     

Al,Ge cation ordering in BaAl2Ge2O8-feldspar: monodomain ordering kinetics

The kinetics of monodomain order-disorder processes in monoclinic (I2/c) BaAl₂Ge₂O₈-feldspar have been investigated by X-ray powder diffraction, Hard Mode IR Spectroscopy, and TEM darkfield imaging on quenched samples. Compared to the behaviour predicted by the TDGL approximation ordering kinetics observed at low temperatures slow down significantly when equilibrium is approached. Such a delay is not observed in disordering experiments starting from essentially ordered cation distributions. The deviation from TDGL behaviour is interpreted in terms of partial order parameter conservation in a non-uniformly ordered phase. Modifications to the uniform TDGL rate equation are tested against the available data. An activation energy of 352 ± 28 kJ/mol is obtained for Al,Ge ordering. The mixing coefficient ξ_c ²/ξ², which describes the degree of order parameter conservation, is obtained as a function of temperature. While this coefficient vanishes in the vicinity of the transformation temperature T _tr, it saturates towards a level of ξ_c ²/ξ²≈0.4 for T→0. ξ _c ²/ξ² determines the kinetic stability of ordered clusters quenched from T≈T _tr. Received: 21 April 1999 / Revised, accepted: 19 July 1999     

Polarized electronic absorption spectra of synthetic (Mg,Fe)-orthopyroxenes,ferrosilite and Fe3+-bearing ferrosilite

The assignment of spin-allowed Fe²⁺-bands in orthopyroxene electronic absorption spectra is revised by studying synthetic bronzite (Mg_0.8 Fe_0.2)₂Si₂O₆, hypersthene (Mg_0.5 Fe_0.5)₂Si₂O₆ and ferrosilite (Fe₂Si₂O₆). Reheating of bronzite and hypersthene single crystals causes a redistribution of the Fe²⁺-ions over the M1 and M2 octahedra, which was determined by Mössbauer spectroscopy and correlated to the intensity change of the spin-allowed Fe²⁺ d-d bands in the polarized absorption spectra. The 11000 cm^-1 band is caused by Fe²⁺ in M1 (⁵B_2g→⁵A_1g) and Fe²⁺ in M2 (⁵A₁→⁵A₁), the 8500 cm^-1 band by Fe²⁺ in M1 (⁵B_2g→⁵B_1g) and the 5000 cm^-1 band by Fe²⁺ in M2 octahedra (⁵A₁→⁵B₁). The Fe²⁺-Fe³⁺ charge transfer band is identified at 12500cm^-1 in the spectra of synthetic Fe³⁺ -Al bearing ferrosilite. This band shows a strong γ-polarization and therefore is caused by Fe²⁺ -Fe³⁺-ions in edge-sharing octahedra.     

Sites occupancy of Fe3+ in Garfield Nontronite: A spectroscopic study

New data on the structure of Garfield nontronite have been produced by the use of different spectroscopic techniques: Mössbauer spectroscopy, optical spectroscopy, X-ray absorption edges and EXAFS and NMR. The tetrahedral iron content is found to be no higher than 1 percent. All iron atoms belong to the octahedral sheet excluding the possibility of the presence of non crystallized phases. Some ambiguities remain about the coherence of the octahedral sheet because of the presence of two doublets in the Mössbauer spectrum and at least two lineshapes in NMR spectra of OH which correspond to different environments.     

Partition of Mg and Fe2+ in coexisting pyroxenes

A general theory for the partition of elements between coexisting, multicomponent phases is outlined and applied to data for Ca-rich pyroxene (Cap) — Ca-poor pyroxene (Op) assemblages from the Skaergaard and Bushveld intrusions and from charnockites. The intercrystalline partition of Mg and Fe²⁺ are studied separately rather than through the exchange reaction, MgSiO ₃ ^Cap +FeSiO ₃ ^Op FeSiO ₃ ^Cap +MgSiO ₃ ^Op .The separate distributions for x_MgSiO3> and x_FeSiO3> are quite distinct and demonstrate directly that solutions of both Mg and Fe²⁺ in the two pyroxenes are nonideal.     

The spin-forbidden absorption spectrum of Fe2+ in orthopyroxene

In this article, we have established the energy matrices of the strong-field terms SΓ of the d ⁴ (d ⁶) electron configuration in a crystal-field with C _2v symmetry. When we used this procedure to calculate the spin-forbidden absorption bands of Fe²⁺ in the M(2) site in orthopyroxene, we substituted the single-electron crystal-field energy levels (determined by the experimental results of the spinallowed spectrum) into the energy matrices instead of the single-electron crystal-field matrix elements. Thus, by means of only one parameter B (C=4B), most of the spin-forbidden bands of Fe²⁺ have been determined. Furthermore, when a similar treatment was made of the M(1) site of O _h symmetry, the entire spin-forbidden spectrum of Fe²⁺ in orthopyroxenes could be semiquantitatively explained. This shows that the method is particularly useful for the calculation of spin-forbidden spectra of complexes with the d ⁴ (d ⁶) configuration in a low-symmetry site.     

Crystal chemistry of Fe3+-bearing (Mg,Fe)SiO3 perovskite: a single-crystal X-ray diffraction study

Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO₃ perovskite more accurately, we synthesized single crystals of Mg_0.946(17)Fe_0.056(12)Si_0.997(16)O₃ perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe²⁺ and Fe³⁺) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O₃ perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations.     

Raman spectroscopic features of Al- Fe3+- poor magnesiochromite and Fe2+- Fe3+- rich ferrian chromite solid solutions

Mineralogy and Petrology - Naturally occurring Al- Fe3 +- poor magnesiochromite and Fe2+- Fe3 +- rich ferrian chromite solid solutions have been analyzed by micro-Raman spectroscopy....     

Temperature,composition, and f O2 effects on intersite distribution of Mg and Fe2+ in olivines

Single-crystal X-ray structure refinement of natural olivines equilibrated at high temperature under controlled oxygen fugacity (f _O2) conditions, coupled with a structure-energy model were used to establish the influence of T, f _O2 and bulk chemistry on intracrystalline disorder.The results are: 1) The k _D (k _D = [(Fe M1·Mg M2)/(Fe M2·Mg M1)]) factor describing site population on M1, M2 polyhedra increases from values lower than 1 at T below 400–600° C (depending on composition) to values higher than 1 at higher temperature. 2) The increase of k _D with T is quite regular. 3) At constant temperature and pressure, k _D increases with increasing fayalite content in the mixture; 4) Contrary to previous observations (Will and Nover 1979; Nover and Will 1981) varying f _O2, within the stability range of the substance, has a negligible influence on intracrystalline disorder. 5) As ancillary results, the model confirms the defect scheme of Nakamura and Schmalzried (1983) for the investigated solids. Moreover, it shows that cationic vacancies are always created on M 1 site at the expense of Mg ions, while trivalent iron is always stabilized on M2 site. This explains the marked anisotropies observed in Fe-Mg interdiffusion (Buening and Busek 1973; Misener 1974; Schock et al. 1989).     

Calculated optical absorption spectra of Ni2+-bearing compounds

The transition energies responsible for optical absorption spectra can be obtained by crystal-field analysis, but the transition intensities are notoriously difficult to calculate. This paper examines the basic ingredients of the calculation of optical spectrum intensities. Magnetic dipole and electric quadrupole transitions intensities are evaluated, as well as the direct d(Ni²⁺) to p(O²⁻) electric dipole transitions. All these contributions are shown to be small in the optical range, so that spectral intensities are due to the mixing of odd orbitals with the Ni²⁺ 3d ⁿ states. Received: 11 November 1997 / Revised, accepted: 6 September 1999     

Structure, ordering and cation interactions in Ca-free P2 1 /c clinopyroxenes

A suite of 14 synthetic Ca-free P2 ₁ /c low-clinopyroxenes of compositions across the enstatite-ferrosilite (En-Fs) join have been studied by X-ray powder diffraction and Mössbauer spectroscopy. The crystal structure of one sample with composition X _Fs=0.39 was determined by single-crystal X-ray diffraction. The powder diffraction data show that there is no significant (<0.25% at X _Fs=0.5) excess volume of mixing on the enstatite-ferrosilite join. The molar volumes are described by V=31.261(17)+1.677(23) X _Fs cm³.mol(MSiO₃)^–1. The linear behaviour of volume with composition arises from the compensating effects of non-linear changes in the unit-cell parameters with composition. Unweighted fits to the data yielded the relationships: a=9.6100(15)+0.105(2)X _Fs, b=8.8156(28)+0.218(12)X _Fs+0.0481(117)X ² _Fs , c?=5.1702(4)+0.0879(21)X _Fs–0.0214(21)X ² _Fs , β=108.345(8)+0.947(30)X _Fs–0.805(26)X ² _Fs . The strong positive deviation of β from linearity is directly correlated to the difference in site occupancies between M1 and M2 as determined by Mössbauer spectroscopy and arises directly from the expansion of M2-O1 and M2-O3 bonds upon initial substitution of Fe for Mg in enstatite. The hyperfine parameters from Mössbauer spectra are consistent with variations in the average local environment as recorded by the X-ray data. Asymmetric line broadening of the Mössbauer spectra provides evidence for next-nearest neighbour effects, and is consistent with no significant clustering of Fe or Mg within the samples.     

The distribution of Fe2+ and Fe3+ in iron-bearing tourmalines: A Mössbauer study

Summary Room-temperature Mössbauer spectra of five iron-bearing tourmalines were measured and analyzed. The Fe²⁺/Fe³⁺ ratio and the iron occupancy of the Y and Z positions could be assigned to all samples, with the help of two previously well characterized samples, from Mexico and Madagascar. Ferric or ferrous ions or both partially occupy the Z as well as the Y octahedra. This fact of observation is interpreted as the chemical response, during crystal growth, to the requirement of size matching for the edge-sharing Y and Z oxygen octahedra. It accounts for the inexistence of solid solution between the Mg and (Li, Al) tourmalines.

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Die Verteilung von Fe²⁺ und Fe³⁺ in eisenhaltigen Turmalinen: Eine Mössbauer-Untersuchung

Zusammenfassung Mössbauer-Spektren von fünf eisenhaltigen Turmalinen wurden gemessen und analysiert. Das Verhältnis Fe²⁺/Fe³⁺ und die Eisenverteilung konnten mit Hilfe von zwei gut identifizierten Turmalin-Kristallen von Mexiko und Madagascar für die Y-und Z-Lagen aller Exemplare bestimmt werden. Zweiwertiges sowie dreiwertiges Eisen findet sich sowohl in der Z-als auch in der Y-Lage. Da sich die Y-und Z-Oktaeder in einer gemeinsamen Kante treffen, wird diese Beobachtung als chemische Antwort des Kristalles auf die erforderte Größenanpassung der Y-und Z-Oktaeder während seines Wachstums erklärt. Die Abwesenheit der festen Lösung zwischen Dravit und Elbait kann somit erklärt werden.

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With 4 Figures     

A raman spectroscopic study of Al-Si ordering in synthetic magnesium cordierite

A number of previous investigations have examined the ordering behavior of magnesium cordierite using X-ray diffraction, transmission electron microscopy, infrared spectroscopy and solution calorimetry. In the present investigation, one series of samples from the above studies has been examined by Raman spectroscopy. Systematic modifications in the spectra with annealing time at 1,200° C are consistent with a continuous ordering of the average Al/Si distribution from 4 h to at least 64 h, and which may begin earlier. Spectral changes are first definitely observed when the ordered domains are around 100 Å across, suggesting that Raman spectroscopy is sensitive to this distance scale. The spectra of samples annealed at 1,200° C are compared with samples annealed at 1,400°; C where ordering proceeds much faster, and the possible use of Raman spectroscopy in characterization of Al/Si order in cordierite is discussed. Finally, the Raman spectrum of Mg₂Al₄Si₅O₁₈ with a stuffed β-quartz structure has been obtained. Comparison of its spectrum with that of cordierite glass suggests similar structures for both, which seem different to that of disordered cordierite.     

Transmission electron microscope study of dislocations in orthopyroxene (Mg,Fe)2Si2O6

The orthopyroxene crystal structure can be viewed as the stacking of alternating tetrahedral and octahedral layers parallel to the (100) plane. Easy glide occurs in the (100) plane at the level of the octahedral layer to prevent breakage of the strong Si-O bonds. Dislocations with c and b Burgers vectors have been activated in (100) by room temperature indentation in an orthoenstatite gem quality single crystal. Investigations in transmission electron microscopy show that the b dislocations (b?9 Å) are not dissociated while the c's (c=5.24 Å) are dissociated into four partials. This result is interpreted by considering the oxygen sublattice as a distorted FCC one. The four c partials are thus Shockley partials bounding three stacking faults. For the two outer ones, synchroshear of the cations is necessary to keep unchanged their sixfold coordination; the oxygen sublattice is locally transformed into a HCP lattice. This accounts for the observed low splitting (?100 Å) of these faults as compared to the median one (?500 Å) which does not affect the oxygen sublattice and does not require cation synchroshear. In a Fe rich orthopyroxene (eulite), semi coherent exsolution lamellae have been studied. Either only c edge dislocations or both b and c edge dislocations occur in the phase boundaries depending upon the thickness of the lamellae. Only the c dislocations are dissociated. From the observed spacing between these mismatch dislocations a crude estimate of the exsolution temperature is proposed T _ex ? 700° C.     

Synthesis and optical absorption spectra of Cr2+-containing orthosilicates

By reacting chromium metal with appropriate oxides in a neutral atmosphere at high temperature it is possible to prepare Mg₂SiO₄ with the olivine structure containing Cr⁺⁺ and also Cr₂SiO₄. X-ray powder diffraction data for chromous orthosilicate may be indexed on an orthorhombic cell with a=5.690, b=11.262, and c=9.584 Å. The compound is not isotructural with olivine. Optical absorption spectra of Cr²⁺ in both hosts have been obtained and also indicate large differences between the two structures.     

Fe2+, Mg-distribution among non-equivalent structural sites M1 and M2 in natural olivines: an optical spectroscopy study

Analysis of E||X-polarized optical absorption spectra of natural olivines of various origin in the range of electronic spin-allowed dd-transitions of Fe²⁺ evidences that in some crystals, there is a weak ordering of Fe²⁺ as in M1, as in M2 structural sites. The samples of three different depth facies seem showing a vague tendency of lowering of k _D -values from spinel-pyroxene (Sp-Px) through graphite-pyrope (G-Py) to diamond-pyrope (D-Py) facies, but the statistics are too poor (24 samples only) to be certain of it. Weak relations between Mg, Fe²⁺-distribution and iron content were found for the samples of Sp-Px- and G-Py-facies, while there is practically no one for those of the deepest D-Py facie.