Systematics of the spinel structure type     

Roderick J. Hill  James R. Craig  G. V. Gibbs 《Physics and Chemistry of Minerals》1979,4(4):317-339

Systematic trends in the geometry of 149 oxide and 80 sulfide binary and ternary spinels have been examined from the standpoint of ionic radius and electronegativity. The mean ionic radii of the octahedral and tetrahedral cations, taken together, account for 96.9 and 90.5% of the variation in the unit cell parameter, a, of the oxides and sulfides, respectively, with the octahedral cation exerting by far the dominant influence in sulfides. The mean electronegativity of the octahedral cation exerts an additional, but small, influence on the cell edge of the sulfides. The equation a=(8/3√d)d _tet+(8/3)d _oct, where d _tet and d _oct are the tetrahedral and octahedral bond lengths obained from the sum of the ionic radii, accounts for 96.7 and 83.2% of the variation in a in the oxides and sulfides, respectively, again testifying to the applicability of the hard-sphere ionic model in the case of the spinel structure. Comparison of observed and calculated u values for 94 spinels indicates that up to 40% of the experimentally measured anion coordinates may be significantly in error. In addition to these compounds, u values are given for 52 spinels for which no data have previously been determined. Diagrams are presented for the rapid interpretation of the internal consistency of published data and the prediction of the structural parameters of hypothetical or partially studied spinels.  相似文献   

Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts     

R.?H.?SievwrightEmail authorView author&#;s OrcID profile  J.?J.?Wilkinson  H.?St.?C.?O’Neill  A.?J.?Berry 《Contributions to Mineralogy and Petrology》2017,172(8):62

Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO₂) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Zn²⁺) and Cu²⁺/Cu⁺ with increasing fO₂ between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO₂ implies a reciprocal relationship between a(Fe²⁺O) and a(Fe³⁺O_1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO₂ in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO₂ in silicic, but less so in mafic bulk systems.  相似文献   

The crystallisation trends of spinels in tertiary basalts from Rhum and Muck and their petrogenetic significance     

W. Ian Ridley 《Contributions to Mineralogy and Petrology》1977,64(3):243-255

Spinels are commonly observed in alkali olivine basalts and olivine basalts that form the Plateau Magma Series of the British Tertiary Province. The spinels are either partly or wholly enclosed within olivine or may have adhered to olivine surfaces, and have undergone cation exchange and reaction with the cooling basaltic melt. Detailed microprobe traverses indicate complex exchanges involving Fe-Mg, Cr-Al, Fe³⁺-R³⁺ and Fe²⁺ Ti-R³⁺ substitutions. Some of these changes are due to a reaction with liquid that produced plagioclase and resulted in Al depletion in the spinel. A complex series of solid solutions between hercynite-magnesioferrite-chromite and Al-Cr-titomomagnetite, is indicated in a combination that precludes the disappearance of spinel by a simple peritetic reaction with the melt. The initial spinels are compositionally distinct from the chromites found in the Rhum layered series and underline the great compositional variability of liquidus spinels that can crystallise from basaltic liquid. Some of this variability may relate to the changing solubility of Cr, which behaves as a trace element, in basaltic liquids in response to slight changes in the structure of the melt.LDGO Contribution no. 2575  相似文献   

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     

D.?LenazEmail author  H.?Skogby  F.?Princivalle  U.?H?lenius 《Physics and Chemistry of Minerals》2004,31(9):633-642

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.  相似文献   

Cation distribution and structure modelling of spinel solid solutions     

B. Lavina  G. Salviulo  A. Della Giusta 《Physics and Chemistry of Minerals》2002,29(1):10-18

 This paper presents an improved generalisation of cation distribution determination based on an accurate fit of all crystal-chemical parameters. Cations are assigned to the tetrahedral and octahedral sites of the structure according to their scattering power and a set of bond distances optimised for spinel structure. A database of 295 spinels was prepared from the literature and unpublished data. Selected compositions include the following cations: Mg²⁺, Al³⁺, Si⁴⁺, Ti⁴⁺, V³⁺, Cr³⁺, Mn²⁺, Mn³⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺ and vacancies. Bond distance optimisation reveals a definite lengthening in tetrahedral distance when large amounts of Fe³⁺ or Ni²⁺ are present in the octahedral site. This means that these cations modify the octahedral angle and hence the shared octahedral edge, causing an increase in the tetrahedral distance with respect to the size of the cations entering it. Some applications to published data are discussed, showing the capacity and limitations of the method for calculating cation distribution, and for identifying inconsistencies and inaccuracies in experimental data. Received: 19 February 2001 / Accepted: 1 June 2001  相似文献   

A thermodynamic model of Fe–Cr spinels     

Viktor?A.?KurepinEmail author 《Contributions to Mineralogy and Petrology》2005,149(5):591-599

A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe₃O₄–FeCr₂O₄ spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe_1-x²⁺ Fe_x³⁺)[Fe_x²⁺Fe_2-2y-x³⁺Cr_2y]O₄, and their thermodynamic properties depend strongly on Fe²⁺–Cr³⁺ cation mixing. Mixing of Fe²⁺–Fe³⁺ and Fe³⁺–Cr³⁺ can be accepted as ideal. If Fe²⁺, Fe³⁺ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x²/((1–x)(2–2y–x)))= G₁₃^* + (1–2x)W₁₃+y(W₁₄–W₁₃–W₃₄) where G₁₃^* is the difference between the Gibbs energy of inverse and normal magnetite, W_ij is a Margules parameter of cation mixing and G₁₃^*, J/mol =–23,000+13.4 T, W₁₄=36 kJ/mol, W₁₃=W₃₄=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe₃O₄–FeCr₂O₄ spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.  相似文献   

The crystal structure of CaFe3+SiAlO6 and the crystal chemistry of Fe3+—Al3+ substitution in calcium Tschermak's pyroxene     

Subrata Ghose  Fujio P. Okamura  Haruo Ohashi 《Contributions to Mineralogy and Petrology》1986,92(4):530-535

The crystal structure of a synthetic CaFe³⁺Al-SiO₆ pyroxene (20 kb, 1,375° C) with unit cell dimensions a=9.7797(16), b=8.7819(14), c=5.3685(5) Å, =105.78(1), space group C2/c has been refined by the method of least squares to an R-factor of 0.025 based on 812 reflections measured on an automatic single crystal diffractometer. The octahedral M1 site is occupied by 0.82 Fe³⁺ and 0.18 Al³⁺. Within the tetrahedral T site, Si⁴⁺ (0.50), Al³⁺ (0.41) and Fe³⁺ (0.09) ions are completely disordered, although submicroscopic domains with short-range order are very likely. The octahedral site preference energy of the Fe³⁺ ions with respect to Al³⁺ ions in CaFe³⁺AlSiO₆ is about 10 kcal/mole, which is much higher than that found in Y₃Al _x Fe_5–2O₁₂ garnets. Topologically the structure of CaFe³⁺AlSiO₆ is intermediate between that of diopside and calcium Tschermak's pyroxene, CaAlAlSiO₆. For CaM³⁺ AlSiO₆ clinopyroxenes an increase in the size of the M1 octahedron is accompanied by an increase in the average M2-0, bridging T-0 and 03-03 distances and kinking of the tetrahedral chain.  相似文献   

The uptake of cobalt into ferromanganese nodules,soils, and synthetic manganese (IV) oxides     

Roger G Burns 《Geochimica et cosmochimica acta》1976,40(1):95-102

Strong enrichments of cobalt occur in marine manganese nodules, soils, wads, and natural and synthetic minerals such as hollandite, cryptomelane, psilomelane, lithiophorite, birnessite, and δ-MnO₂. Previously, it was suggested that Co³⁺ ions in these minerals replace either Mn³⁺ or substitute for Fe³⁺ in incipient goethite epitaxially intergrown with δ-MnO₂. Neither of these interpretations is now considered to be satisfactory on account of the large discrepancy of ionic radius between octahedrally coordinated low-spin Co³⁺ and high-spin Mn³⁺ or Fe³⁺ in oxide structures. The close agreement between the ionic radii of Co³⁺ and Mn⁴⁺ suggests that some cobalt substitutes for Mn⁴⁺ ions in edge-shared [MnO₆] octahedra in many manganese(IV) oxide mineral structures. It is proposed that hydrated cations, including Co²⁺ ions, are initially adsorbed on to the surfaces of certain Mn(IV) oxides in the vicinity of essential vacancies found in the chains or sheets of edge-shared [MnO₆] octahedra. Subsequently, fixation of cobalt takes place as a result of oxidation of adsorbed Co²⁺ ions by Mn⁴⁺ and replacement of the displaced manganese by low-spin Co³⁺ ions in the [MnO₆] octahedra or vacancies.  相似文献   

Experimental study on the phase equilibria in the join CaMgSi2O6-CaCrCrSiO6 with special reference to the blue diopside     

Ko Ikeda  Kenzo Yagi 《Contributions to Mineralogy and Petrology》1977,61(1):91-106

The behaviour of tetrahedrally coordinated and octahedrally coordinated Cr³⁺ ions in diopside is discussed from the study on the join CaMg-Si₂O₆-CaCrCrSiO₆. The molecule CaCrCrSiO₆ decomposes into uvarovite+eskolaite and its maximum solubility in diopside is 6.7 wt percent at 940 ° C. Crystalline phases are diopside ss (ss is abbreviation of solid solution), uvarovite ss, wollastonite ss, spinel and eskolaite. The diopside ss is blue in colour. Its optical spectra were measured in the wavelenght range of 325–2600 nm, and assigned after tetrahedral configuration Td and octahedral configuration Oh. It is estimated that octahedral Cr³⁺ ions are in high spin state, while tetrahedral Cr³⁺ ions may be probably in low spin state. The _t and B are 10,300–10,370 cm^–1 and 429–432 cm^–1. The CFSE for tetrahedral low spin Cr³⁺ ions is nearly the same as that for octahedral high spin Cr³⁺ ions. The ionic radii of tetrahedral low spin Cr³⁺ ions calculated are 0.47–0.53 Å, shrinked from the radius of octahedral high spin Cr³⁺ ion (0.615 Å) as much as 14–24 percent. Petrologic implications of the result are also discussed.The first half of the D. Sc. dissertation of K. Ikeda presented to Hokkaido University in June, 1976  相似文献   

Mössbauer spectra of kyanite,aquamarine, and cordierite showing intervalence charge transfer     

Kathleen M. Parkin  Bruce M. Loeffler  Roger G. Burns 《Physics and Chemistry of Minerals》1977,1(3):301-311

The blue colors of several minerals and gems, including aquamarine (beryl, Be₃Al₂Si₆O₁₈) and cordierite (Al₃(Mg, Fe)₂Si₅AlO₁₈), have been attributed to charge transfer (CT) between adjacent Fe²⁺ and Fe³⁺ cations, while Fe²⁺→Ti⁴⁺ CT has been proposed for blue kyanites (Al₂SiO₅). Such assignments were based on chemical analyses and on polarization-dependent absorption bands measured in visible-region spectra. We have attempted to characterize the Fe cations in each of these minerals by Mössbauer spectroscopy (MS). In blue kyanites, significant amounts of both Fe²⁺ and Fe³⁺ were detected with MS, indicating that Fe²⁺→Fe³⁺ CT, Fe²⁺→Ti⁴⁺ CT, and Fe²⁺ and Fe³⁺ crystal field transitions each could contribute to the electronic spectra. In aquamarines, coexisting Fe²⁺ and Fe³⁺ ions were resolved by MS, supporting our assignment of the broad, relatively weak band at 16,100 cm^?1 in E∥c spectra to Fe²⁺→Fe³⁺ CT between Fe cations replacing Al³⁺ ions 4.6Å apart along c. A band at 17,500 cm^?1 in E⊥c spectra of cordierite is generally assigned to Fe²⁺ (oct)→Fe³⁺ (tet) CT between cations only 2.74 Å apart. However, no Fe³⁺ ions were detected in the MS at 293K of several blue cordierites showing the 17,500 cm^?1 band and reported to contain Fe³⁺. A quadrupole doublet with parameters consistent with tetrahedral Fe³⁺ appears in 77K MS, but the Fe³⁺/Fe²⁺ ratios from MS are much smaller than values from chemical analysis. These results sound a cautionary note when correlating Mössbauer and chemically determined Fe³⁺/Fe²⁺ ratios for minerals exhibiting Fe²⁺→Fe³⁺ CT.  相似文献   

The structural state of iron in oxidized vs. reduced glasses at 1 atm: A57Fe Mössbauer study     

David Virgo  Bjørn O. Mysen 《Physics and Chemistry of Minerals》1985,12(2):65-76

A general model for the structural state of iron in a variety of silicate and aluminosilicate glass compositions in the systems Na₂O-Al₂O₃-SiO₂-Fe-O, CaO-Al₂O₃-SiO₂-Fe-O, and MgO-Al₂O₃-SiO₂-Fe-O is proposed. Quenched melts with variable Al/Si and NBO/T (average number of nonbridging oxygens per tetrahedrally coordinated cation), synthesized over a range of temperatures and values of oxygen fugacity, are analyzed with⁵⁷Fe Mössbauer spectroscopy. For oxidized glasses with Fe³⁺/∑Fe>0.50, the isomer shift for Fe³⁺ is in the range ～0.22–0.33 mm/s and ～0.36 mm/s at 298 K and 77 K, respectively. These values are indicative of tetrahedrally coordinated Fe^3?. This assignment is in agreement with the interpretation of Raman, luminescence, and X-ray,K-edge absorption spectra. The values of the quadrupole splitting are ～0.90 mm/s (298 K and 77 K) in the Na-aluminosilicate glasses and compare with the values of 1.3 mm/s and 1.5 mm/s for the analogous Ca- and Mg-aluminosilicate compositions. The variations in quadrupole splittings for Fe³⁺ are due to differences in the degree of distortion of the tetrahedrally coordinated site in each of the systems. The values of the isomer shifts for Fe²⁺ ions in glasses irrespective of Fe³⁺/∑Fe are in the range 0.90–1.06 mm/s at 298 K and 1.0–1.15 mm/s at 77 K. The corresponding range of values of the quadrupole splitting is 1.75–2.10 mm/s at 298 K and 2.00–2.35 mm/s at 77 K. The temperature dependence of the hyperfine parameters for Fe²⁺ is indicative of noninteracting ions, but the values of the isomer shift are intermediate between those values normally attributable to tetrahedrally and octahedrally coordinated Fe²⁺. The assignment of the isomer-shift values of Fe²⁺ to octahedral coordination is in agreement with the results of other spectral studies. For reduced glasses (Fe³⁺/∑Fe≈<0.50), the value of the isomer shift for Fe³⁺ at both 298 K and 77 K increases and is linearly correlated with decreasing Fe³⁺/∑Fe in the range of \(f_{O_2 } \) between 10^?3 and 10^?6 atm when a single quadrupole-split doublet is assumed to represent the absorption due to ferric iron. The increase in value of the isomer shift with decreasing \(f_{O_2 } \) is consistent with an increase in the proportion of Fe³⁺ ions that are octahedrally coordinated. The concentration of octahedral Fe³⁺ is dependent on the \(T - f_{O_2 } \) conditions, and in the range of log \(f_{O_2 } \) between 10^?2.0 and 10^?5 a significant proportion of the iron may occur as iron-rich structural units with stoichiometry similar to that of inverse spinels such as Fe₃O₄, in addition to isolated Fe²⁺ and Fe³⁺ ions.  相似文献   

Der Einfluß verschiedener Substitutionen auf die Gitterkonstanten von koexistierenden Biotiten und Muskowiten     

Georg Müller 《Contributions to Mineralogy and Petrology》1966,13(1):59-74

Structural formulas were calculated for 8 analysed coexisting biotite-muscovitepairs from granitic rocks. Characteristic components of these structural formulas were plotted against the unit cell dimensions of these micas.In accordance with the results of Gower (1957) the substitution of OH^– by F^– in trioctahedral micas was found to reduce c ₀ · . However, in contrast to his statements, octahedral alumina was found to reduce c ₀ · sin also and to an even larger extent than fluorine. This observation is in agreement with the commonly encountered compacting of the mica structure through replacement of 3 large cations (Fe²⁺, Mg²⁺, Mn²⁺) by two smaller ones (Al³⁺, Fe³⁺).Concerning b ₀ the combined amounts of octahedral Al and tetrahedral Si cause a reduction of this value, which means indirectly that tetrahedral Al alone would increase b ₀.Reductions of b ₀ and c ₀ · sin by Al in synthetic micas were also found by Crowley and Roy (1964) and Seifert (1966) for the substitution Mg + Si by two Al in trioctahedral micas.In an earlier paper the author (Müller, 1966) has already shown with the same mica samples that the substitutions of M²⁺ by Al³⁺ and of OH^– by F^– also have the strongest effects of all substitutions on the refractive indices, densities, and specific refractive energies of these micas. Therefore it is evident that the latter effects as well as the changes of lattice constants described in this paper are interrelated.

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Mein Dank gilt den Herren Dr.W. Harre und Dr. H. Gundlach, Bundesanstalt für Bodenforschung, Hannover, für die Ausführung der chemischen Glimmeranalysen, sowie der Deutschen Forschungsgemeinschaft, Bad Godesberg, für ihre finanzielle Beihilfe. Herrn Dr. F. Seifert, Kiel, danke ich für zahlreiche sachliche Diskussionen und Hinweise und für die Überlassung seines Algol-Rechenprogramms, mit welchem 4 der 16 Strukturformeln elektronisch berechnet wurden. Herrn Prof. Dr. F. Liebau, Kiel, verdanke ich einige freundliche Ratschläge.  相似文献   

Oriented transformation of grunerite to clinoferrosilite at 775° C and 500 bars Argon pressure     

Subrata Ghose  Jerry R. Weidner 《Contributions to Mineralogy and Petrology》1971,30(1):64-71

A member of the grunerite series (Fe_6.685Mn_0.142Ca_0.110Mg_0.096) (Si_7.968Al_0.016)O₂₂(OH)₂, has been transformed to clinoferrosilite, amorphous silica and water at 775° C and 500 bars Argon pressure. Single crystal photographs of an oriented intergrowth of the amphibole and pyroxene show that the clinoferrosilite retains the cristallographic a, b and c axes of the original grunerite in the I2/m orientation and has the cell dimensions: a=9.77, b=9.08, c=5.30 Å, =109.5°; space group P2₁/c. Mössbauer resonance spectroscopy confirmed the identity of the olinoferrosilite.A transformation mechanism requires a minimum of ionic movements in an acceptor region (7/8 of the total crystal), where pyroxene is formed by expulsion of protons and acceptance of Fe²⁺ ions; simultaneous destruction of donor regions provide the Fe²⁺ ions, the residue being silica and water. The formation of metastable clinoferrosilite rather than fayalite and quartz indicates the strong structural control imposed by the host grunerite structure on the nature of the transformation products.  相似文献   

Electronic absorption spectroscopy of natural (Fe2+, Fe3+)-bearing spinels of spinel s.s.-hercynite and gahnite-hercynite solid solutions at different temperatures and high-pressures     

Michail N. Taran  Monika Koch-Müller  Klaus Langer 《Physics and Chemistry of Minerals》2005,32(3):175-188

Natural Fe²⁺, Fe³⁺-bearing spinel solid solutions from the spinel s.s.-hercynite and gahnite-hercynite series were analyzed and studied by electronic absorption spectroscopy in the spectral range 30000–3500 cm^–1 in the temperature and pressure ranges 77 T_K 600 and 10^–4 P_GPa 11.0. Two crystals were light-violet in color (type I) and six green or bluish-green (type II). The spectra of both types of spinels are dominated by an UV-absorption edge near 28000 to 24000 cm^–1, depending on the iron contents, and a very intense band system in the NIR centered around 5000 cm^–1, which is caused by spin-allowed dd-transition of tetrahedral Fe²⁺, derived from ⁵ E⁵ T₂. The strong band is in all spinels studied, split into four sub-bands, which can only be observed in very thin platelets. Between the UV-edge and the high-energy wing of the NIR-band there occur a number of very weak bands in type I spinels while the green type II spinels show some of these with significantly enhanced intensity. The intensity of the very weak bands is nearly independent from temperature. Such bands are attributed to spin-forbidden electronic transitions of ^IVFe²⁺. Temperature and pressure dependence of the intensity enhanced bands of spinels type II indicate that they are caused by ^IVFe²⁺ and ^VIFe³⁺. They are attributed to spin-forbidden transitions ⁶A_1g⁴A_1g, ⁴E_g, ⁴T_2g and ⁴T_1g of ^VIFe³⁺, the two latter being strongly intensified by exchange-coupling interaction with adjacent ^IVFe²⁺. The pressure dependence of ^IVFe²⁺ dd-band system in the NIR caused by spin-allowed ⁵ E⁵ T₂ transition noticeably differs from that of octahedral Fe²⁺, an effect which is attributed to a dynamic Jahn-Teller effect of ^IVFe²⁺ in the spinel structure.

Monika Koch-MüllerEmail: Phone: +49-331-288-1492/1402Fax: +49-331-288-1492/1402

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Fe2+–Fe3+ ordered distribution in chromite spinels     

Y. L. Chen  B. F. Xu  J. G. Chen  Y. Y. Ge 《Physics and Chemistry of Minerals》1992,19(4):255-259

Mossbauer measurements have been carried out on three natural chromite minerals from different locations in China over the temperature range 50 to 750 K. The experiments showed these samples to be magnesioferrochromites. The Mossbauer spectra measured could be decomposed into three doublets: two attributed to the tetrahedral T-site Fe²⁺ ions and the third to the octahedral M-site Fe³⁺ ions. Thus for the chromite spinels the results strongly supported the ordered distribution with Fe²⁺ in the T-site and Fe³⁺ in M-site.  相似文献   

Intracrystalline relationships in olivine,orthopyroxene, clinopyroxene and spinel from a suite of spinel lherzolite xenoliths from Mt. Noorat,Victoria, Australia     

A. Cundari  A. Dal Negro  E. M. Piccirillo  A. Della Giusta  L. Secco 《Contributions to Mineralogy and Petrology》1986,94(4):523-532

A detailed crystal chemical study of coexisting olivine, orthopyroxene, clinopyroxene and spinel from selected Victorian (Australia) lherzolite suites was carried out by means of single crystal x-ray diffraction and electron probe microanalysis to obtain actual site occupancies. The aim of this study was primarily to characterise the intracrystalline configurations and related cation ordering on sites in major mantle constituents. The results demonstrate that cation ordering on sites is subject to distinctive crystallographic controls which depend on the petrological evolution of the suite. Mg-Fe²⁺ ordering in M1–M2 pyroxene sites depends on variations of the smaller cations, mainly Al^vi, Ti⁴⁺, Fe³⁺, and related configurations of M 1. Pressuresensitive Al^vi is crucial to Fe²⁺, the more ordered clinopyroxene showing high Al^vi configurations which tend to exclude the larger bivalent cations and yield small polyhedral volumes for M 1, M 2, T sites and the unit cell. Conversely, the coexisting orthopyroxene, characterised by lower Al^vi configuration and higher M 1 and unit cell volumes, is relatively more disordered. Olivine is consistent with the coexisting clinopyroxene, the more disordered crystals coexisting with more disordered clinopyroxene, while Al-Mg order in the coexisting spinel shows the reverse relationship. Estimated temperatures of apparent equilibration based on current geothermometers are not considered realistic. Assumptions of ideal cation mixing on sites in pyroxene and spinel are not supported.  相似文献   

Synthesis, crystal structure and crystal chemistry of ferri-clinoholmquistite, ?Li ₂Mg ₃Fe ³⁺ ₂Si ₈O ₂₂(OH) ₂     

G. Iezzi  F. Cámara  R. Oberti  G. Della Ventura  G. Pedrazzi  J-L Robert 《Physics and Chemistry of Minerals》2004,31(6):375-385

This work reports the synthesis of ferri-clinoholmquistite, nominally _Li2(Mg₃Fe³⁺₂)Si₈O₂₂(OH)₂, at varying f_O2 conditions. Amphibole compositions were characterized by X-ray (powder and single-crystal) diffraction, microchemical (EMPA) and spectroscopic (FTIR, Mössbauer and Raman) techniques. Under reducing conditions ( NNO+1, where NNO = Nickel–Nickel oxide buffer), the amphibole yield is very high (>90%), but its composition, and in particular the FeO/Fe₂O₃ ratio, departs significantly from the nominal one. Under oxidizing conditions ( NNO+1.5), the amphibole yield is much lower (<60%, with Li-pyroxene abundant), but its composition is close to the ideal stoichiometry. The exchange vector of relevance for the studied system is ^M2(Mg,Fe²⁺) ^M4(Mg,Fe²⁺) ^M2Fe³⁺_–1 ^M4Li_–1, which is still rather unexplored in natural systems. Amphibole crystals of suitable size for structure refinement were obtained only at 800 °C, 0.4 GPa and NNO conditions (sample 152), and have C2/m symmetry. The X-ray powder patterns for all other samples were indexed in the same symmetry; the amphibole closest to ideal composition has a = 9.428(1) Å, b = 17.878(3) Å, c = 5.282(1) Å, = 102.06(2)°, V = 870.8(3) ų. Mössbauer spectra show that Fe³⁺ is strongly ordered at M2 in all samples, whereas Fe²⁺ is disordered over the B and C sites. FTIR analysis shows that the amount of ^CFe²⁺ increases for increasingly reducing conditions. FTIR data also provide strong evidence for slight but significant amounts of Li at the A sites.  相似文献   

Hydrogen incorporation in orthopyroxene: interaction of different trivalent cations     

Roland?StalderEmail author  Stephan?Klemme  Thomas?Ludwig  Henrik?Skogby 《Contributions to Mineralogy and Petrology》2005,150(5):473-485

The incorporation of hydrogen into ferrosilite, Fe-bearing enstatite and orthopyroxene containing different trivalent cations (Cr³⁺ and Al³⁺, Cr³⁺ and Fe³⁺) was investigated experimentally at 25 kbar. Hydrogen concentration was determined by FTIR-spectroscopy on oriented crystal sections and by secondary ion mass spectroscopy, whereas Mößbauer spectroscopy and optical spectroscopy were used to characterise the valence state of Fe in orthopyroxene. Results suggest that hydrogen incorporation in ferrosilite is achieved by a similar mechanism as in pure enstatite. In Cr-bearing samples, however, hydrogen incorporation is reduced by the presence of other trivalent cations by an increased tendency to form Tschermaks substitutions, e.g. Si _T ⁴⁺ + Mg _M1 ²⁺ ? Al _T ³⁺ + Cr _M1 ³⁺ . Thus, hydrogen solubility in natural orthopyroxenes from the Earth’s mantle, containing significant amounts of Cr³⁺, Al³⁺, and Fe³⁺, may be much more limited than expected from their trivalent cation content, as a large fraction of the trivalent cations does not participate in H-incorporating reactions as 2 Mg _M1 ²⁺ ? M _M1 ³⁺ + V_M1 + H _i ⁺ .  相似文献   

Saturation magnetisation,coercivity and lattice parameter changes in the system Fe3O4-γFe2O3, and their relationship to structure     

C. J. Goss 《Physics and Chemistry of Minerals》1988,16(2):164-171

This study has characterised the oxidation products of a fine-grained single domain magnetite which was made synthetically by a colloidal method. Changes in the intrinsic magnetic properties (saturation magnetisation, saturation remanence, and coercive force) during progressive oxidation are correlated with lattice parameter changes and an oxidation mechanism. It is proposed that magnetite oxidises to hematite via at least two metastable maghemites. The first of these, formed on low temperature oxidation by the formation of a magnetite/maghemite solid solution, is a face centered maghemite with lattice parameter a= 8.3419±0.0006 Å. A second maghemite, produced on oxidation at higher temperatures, has a primitive cubic structure and a lattice parameter a = 8.3505±0.0005 Å. Maghemite cation distributions are derived to explain the reduced saturation magnetisations of between 56 and 74 Am² kg^-1 observed, and a maghemite structure containing an increase in tetrahedral Fe³⁺ ions and up to 3 octahedral vacancies per 32 oxygen unit cell is proposed.  相似文献   

Hydrogen bonding and vibrational properties of hydroxy groups in the crystal lattice of dioctahedral clay minerals by means of first principles calculations     

V.?Botella  V.?Timon  E.?Escamilla-Roa  A.?Hernández-Languna  C.I.?Sainz-DíazEmail author 《Physics and Chemistry of Minerals》2004,31(8):475-486

The hydroxy groups of the crystal lattice of dioctahedral 2:1 phyllosilicates were investigated by means of quantum-mechanical calculation. The standard Kohn-Sham self-consistent density functional theory (DFT) method was applied using the generalized gradient approximation (GGA) with numerical atomic orbitals and double-zeta polarized functions as basis set. Isomorphous cation substitution of different cations in the octahedral and tetrahedral sheet was included along with several interlayer cations reproducing experimental crystal lattice parameters. The effect of these substitutions and the interlayer charge on the hydroxyl group properties was also studied. These structures represent different cation pairs among Al³⁺, Fe³⁺ and Mg²⁺ in the octahedral sheet of clays joined to OH groups. The geometrical disposition of the OH bond in the crystal lattice and the hydrogen bonds and other electrostatic interactions of this group were analyzed. The frequencies of different vibrational modes of the OH group [(OH), (OH) and (OH)] were calculated and compared with experimental data, finding a good agreement. These frequencies depend significantly on the nature of cations which are joined with, and the electrostatic interactions with, the interlayer cations. Besides, hydrogen-bonding interactions with tetrahedral oxygens are important for the vibrational properties of the OH groups; however, also the electrostatic interactions of these OH groups with the rest of tetrahedral oxygens within the tetrahedral cavity should be taken into account. The cation substitution effect on the vibration modes of the OH groups was analyzed reproducing the experimental behaviour.Dr. V. Botella passed away last February  相似文献