Subsolidus Phase Relations in the System MgO-SiO_2-Cr-O and Thermodynamic Properties of Related Cr~(2+)-Containing End-members     

H.St.CO'' Neill  F.Seifert 《《地质学报》英文版》1996,70(4):420-434

Subsolidus phase relations have been determined in the systems SiO2-Cr-O and MgO-SiO2-Cr-O in equilibrium with metallic Cr, at 1100 to 1500℃ and 0 to 2.88 GPa. The results show that there are no ternary phases in the SiO2-Cr-O system at these conditions, i.e., only the assemblage eskolaite-Cr-metal-quartz (or tridymite) is found. In the MgO-containing system, however, extensive substitution of Cr2+ for Mg is observed in (Mg, Cr2+)2SiO4 olivine, (Mg, Cr2+)2Si2O6 pyroxene, and (Mg, Cr2+)Cr2O4 spinel. Cr3+ levels in olivine and pyroxene are below detection limits. The pyroxene is orthohombic at XCrPx2+ < 0.2, monoclinic at higher XCrPx2+ . Thestructure of the spinels becomes tetragonally distorted at XCr2+Sp >0.2. The experimental datahave been fitted to a thermodynamic model, and the authors obtained the mixing parameter (W) of Mg-Cr2+ in olivine, pyroxene and spinel, and the relation between temperatures and free energies of formation for the end-members: Cr2+-olivine (Cr2SiO4), Cr2+-pyroxene (Cr2Si2O6)  相似文献   

Correlation of spectroscopic properties and substitutional sites of Cr3+ in aluminosilicates: II. Andalusite and sillimanite     

J. Qin  C. Rudowicz  Y. M. Chang  Y. Y. Yeung 《Physics and Chemistry of Minerals》1994,21(8):532-538

This paper is an extension of the earlier one dealing with kyanite in which the best fitting value of the oxygen ligand distance for Cr³⁺ is adopted to study the spectroscopic properties of Cr³⁺ ions doped at the two possible Al sites in the other two polymorphs of the aluminosilicate group (Al₂O₃ · SiO₂), namely, andalusite and sillimanite. The superposition model and the crystal field analysis package recently developed for 3d ions doped at arbitrary low symmetry sites in crystals are used to predict energy levels and statevectors within the whole 3d ³ configuration. Then the values of the ground state zerofield splitting for Cr³⁺ ions at each Al sites in the two crystals are obtained. The splittings of the lower excited states ² E and ⁴ T ₂ as well as the admixture of ⁴ T ₂ into ² E have also been predicted. Comparison of our results with the available experimental data enable us to correlate the optical and EPR Spectroscopic properties with the substitutional Cr³⁺ sites. The conclusion is that in andalusite and sillimanite only the Al sites with nearly-octahedral six-fold coordination seem to be occupied by Cr³⁺ ions.  相似文献   

Experimental Study on the Solubility of Cr^2 in Olivine,Orthopyroxene and Spinel Solid Solutions     

Li Jianping  Hugh St. C. O’Neill  Friedrich Seifert 《中国地球化学学报》1997,16(2):139-147

Experiments have been performed on the system MgO-SiO2-Cr-O at 0-2.88 GPa and 1100-1450℃,focusing on the stability of Cr^2 in olivine(O1),orthopyroxene(Opx) and spinel(Sp) and its partitioning between these phases.Analytical reagent grade chemicals,MgO,SiO2,Cr2O3.and Cr were used to make starting mixtures.Excess Cr(50%) was then added in these mixtures to ensure that the resultant phases were in equilibrium with the metal Cr.Flux of BaO B2O3(%) was added for facilitating experimental equilibrium and crystal growth.Cr was used as capsule material.All phases in the product were identified by X-ray and analyzed by electron microprobe,The contents of CrO in the different phases(O1,Opx and Sp)were calculated according to stoichiometry.The obtained results of calculation indicate that Cr^3 in Ol and Opx is negligible.The experimental results show;(a) with increasing temperature and decreasing pressure,Cr^2 solubility in Ol,Opx and Sp increases;(b) with in creasing temperature,the partitioning coefficient of Mg and Cr^2 between Ol and Opx decreases,that between Opx and Sp increases,and that between Ol and Sp remains almost unchanged;(c) the effect of pressure on all partitioning coefficients is negligible.  相似文献   

The distribution of Fe3+ and Ga3+ between two tetrahedral sites in melilites,Ca2(Mg,Fe3+, Ga,Si)3O7     

Masahide Akasaka  Haruo Ohashi  Isamu Shinno 《Physics and Chemistry of Minerals》1986,13(3):152-155

The distribution of Fe³⁺ and Ga³⁺ between the two tetrahedral sites in three synthetic melilites has been studied by using ⁵⁷Fe Mössbauer spectroscopy. In the melilite, (Ca₂Ga₂SiO₇)₅₀ (Ca₂Fe³⁺GaSiO₇)₅₀ (mol %), the distribution of Fe³⁺ and Ga³⁺ in T1 and T2 sites is apparently random, which can be explained in terms of the electrostatic valence rule. However in the melilites, (Ca₂MgSi₂O₇)₅₂ (Ca₂Fe³⁺GaSiO₇)₄₂ (Ca₂Ga₂SiO₇)₆ and (Ca₂MgSi₂O₇)₆₂ (Ca₂Fe³⁺GaSiO₇)₃₆ (Ca₂Ga₂SiO₇)₂ (mol %), Fe³⁺ shows preference for the more ionic T1 site and Ga³⁺ for the more covalent T2 site. If the electronegativity of Ga³⁺ is assumed to be larger than that of Fe³⁺, the mode of distribution of Fe³⁺ and Ga³⁺ can be explained in terms of our previous hypothesis that a large electronegativity induces a stronger preference for the more covalent T2 site.  相似文献   

Study of structural and valence state of Cr and Fe in chrysoberyl and alexandrite with EPR and M?ssbauer spectroscopy     

V. S. Urusov  N. A. Gromalova  S. V. Vyatkin  V. S. Rusakov  V. V. Maltsev  N. N. Eremin 《Moscow University Geology Bulletin》2011,66(2):102-107

Data on the structural and valence distribution of Cr and Fe in chrysoberyl and in alexandrite, its gem variety, are given. It is shown that the Cr³⁺ line in the natural Ural and Tanzania samples is the strongest in the M1 site and for the synthetic stones, in the M2 site. During the annealing of the alexandrite crystals, Cr³⁺ passes from the smaller M1 site into the larger M2 site. The M?ssbauer spectroscopy quantitatively determined the distribution of different valence Fe ions. The various proportions of both Fe²⁺ and Fe³⁺ ions isomorphically entering the octahedral sites in the BeAl₂O₄ crystal structure were established.  相似文献   

Distribution of cations at two tetrahedral sites in Ca2MgSi2O7-Ca2Fe3+AlSiO7 series synthetic melilite and its relation to incommensurate structure     

Maki Hamada  Masahide Akasaka 《Physics and Chemistry of Minerals》2013,40(3):259-270

Synthetic melilites on the join Ca₂MgSi₂O₇ (åkermanite: Ak)-Ca₂Fe³⁺AlSiO₇ (ferrialuminium gehlenite: FAGeh) were studied using X-ray powder diffraction and ⁵⁷Fe Mössbauer spectroscopic methods to determine the distribution of Fe³⁺ between two different tetrahedral sites (T1 and T2), and the relationship between ionic substitution and incommensurate (IC) structure. Melilites were synthesized from starting materials with compositions of Ak₁₀₀, Ak₈₀FAGeh₂₀, Ak₇₀FAGeh₃₀ and Ak₅₀FAGeh₅₀ by sintering at 1,170–1,350 °C and 1 atm. The average chemical compositions and end-member components, Ak, FAGeh and Geh (Ca₂Al₂SiO₇), of the synthetic melilites were Ca_2.015Mg_1.023Si_1.981O₇ (Ak₁₀₀), Ca_2.017Mg_0.788Fe _0.187 ³⁺ Al_0.221Si_1.791O₇ (Ak₇₈FAGeh₁₉Geh₃), Ca_1.995Mg_0.695Fe _0.258 ³⁺ Al_0.318Si_1.723O₇ (Ak₆₉FAGeh₂₅Geh₆) and Ca_1.982Mg_0.495Fe _0.449 ³⁺ Al_0.519Si_1.535O₇ (Ak₄₉FAGeh₄₄Geh₇), respectively. Rietveld refinements using X-ray powder diffraction data measured using CuK _α -radiation at room temperature converged successfully with goodness-of-fits of 1.15–1.26. The refined Fe occupancies at the T1 and T2 sites and the Mg and Si contents determined by electron microprobe analysis gave the site populations of [0.788Mg + 0.082Fe³⁺ + 0.130Al]_T1[0.104Fe³⁺ + 0.104Al + 1.792Si]_T2 for Ak₇₈FAGeh₁₉Geh₃, [0.695Mg + 0.127Fe³⁺ + 0.178Al]_T1[0.132Fe³⁺ + 0.144Al + 1.724Si]_T2 for Ak₆₉FAGeh₂₅Geh₆ and [0.495Mg + 0.202Fe³⁺ + 0.303Al]_T1[0.248Fe³⁺ + 0.216Al + 1.536Si]_T2 for Ak₄₉FAGeh₄₄Geh₇ (apfu: atoms per formula unit), respectively. The results indicate that Fe³⁺ is distributed at both the T1 and the T2 sites. The mean T1–O distance decreases with the substitution of Fe³⁺ + Al³⁺ for Mg²⁺ at the T1 site, whereas the mean T2–O distance increases with substitution of Fe³⁺ + Al³⁺ for Si⁴⁺ at the T2 site, causing decrease in the a dimension and increase in the c dimension. However, in spite of the successful Rietveld refinements for the X-ray powder diffraction data measured using CuK _α-radiation at room temperature, each Bragg reflection measured using CuK _α1-radiation at room temperature showed weak shoulders, which were not observed in those measured at 200 °C. The Mössbauer spectra of the melilites measured at room temperature consist of two doublets assigned to Fe³⁺ at the T1 site and two or three doublets to Fe³⁺ at the T2 site, implying the existence of multiple T1 and T2 sites with different site distortions. These facts can be interpreted in terms of the IC structure in all synthetic melilites at room temperature, respectively. The results of Mössbauer analysis indicate that the IC structure in melilite is caused by not only known multiple T1 site, but also multiple T2 site at room temperature.  相似文献   

Polarized electronic absorption spectra of Cr2SiO4 single crystals     

A. Furche  K. Langer 《Physics and Chemistry of Minerals》1998,25(5):393-400

Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000–5000?cm^–1 were obtained for the orthorhombic thenardite-type phase Cr₂SiO₄, unique in its Cr²⁺-allocation suggesting some metal-metal bonding in Cr²⁺Cr²⁺ pairs with Cr-Cr distance 2.75?Å along [001]. The spectra were scanned at 273 and 120?K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6?μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20?μm and 1?nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr₂SiO₄, synthesized at 35?kbar, above 1440?°C from high purity Cr₂O₃, Cr (10% excess) and SiO₂ in chromium capsules. The Cr₂SiO₄-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm^–1, in the absorption spectra of Cr₂SiO₄ single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr²⁺ in a distorted square planar coordination of point symmetry C₂. The crystal field parameter of Cr²⁺ is estimated to be 10?Dq?10700?cm^–1. A relatively intense, sharp band at 18400?cm^–1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr²⁺. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000?cm^–1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr₂ ⁴⁺, whereas the latter alone would be in conflict with the strong polarization of bands I and II parallel [100]. Therefore, it is concluded that the spectra obtained can best be interpreted assuming both dd-transitions of localized d-electrons at Cr²⁺ as well as δ-δ* transitions of Cr₂ ⁴⁺ pairs with metal-metal interaction. To explain this, a dynamic exchange process 2 Cr_loc ²⁺?Cr_{2, cpl} ⁴⁺ is suggested wherein the half life times of the ground states of both exchanging species are significantly longer than those of the respective optically excited states, such that the spectra show both dd- and δ-δ*-transitions.  相似文献   

Correlation of spectroscopic properties and substitutional sites of Cr3+ in aluminosilicates: I. Kyanite     

Y. Y. Yeung  J. Qin  Y. M. Chang  C. Rudowicz 《Physics and Chemistry of Minerals》1994,21(8):526-531

Using the superposition model in conjunction with our crystal field analysis package recently developed for 3d ions doped at arbitrary low symmetry sites in crystals, the energy levels and statevectors have been predicted within the whole 3d ³ configuration of Cr³⁺ at the four possible triclinic sites in kyanite (Al₂O₃∶SiO₂). The values of the ground state zero-field splitting for each of the four Al sites are evaluated. The splittings of the lower excited state ² E as well as the admixture of ⁴ T ₂ state into ² E have also been determined. The predicted results are compared with the available experimental data on the four possible, but so far not uniquely identified, substitutional Cr³⁺ sites in kyanite thus enabling correlation of the spectroscopic properties and substitutional sites.  相似文献   

Chromium mineralization in the Khibiny alkaline massif (Kola Peninsula,Russia)     

O. S. Yakovleva  I. V. Pekov  I. A. Bryzgalov 《Moscow University Geology Bulletin》2009,64(4):220-229

This paper presents new data on chromium mineralization in a fenitized xenolith in Mt. Kaskasnyunchorr in the Khibiny alkaline massif (Kola Peninsula, Russia) and summarizes data on Cr mineralogy in the Khibiny Mountains. Protolith silicates that contained Cr³⁺ admixture are believed to be the source of this element in the fenite. Cr-bearing (maximum Cr₂O₃ concentrations, wt %, are in parentheses) aegirine (5.8), crichtonite-group minerals (2.1), muscovite (1.3), zirconolite (1.1), titanite (1.0), fluorine-magnesioarfvedsonite (0.8), biotite (0.8), ilmenite (0.6), and aenigmatite (0.6) occur in the fenite. The late-stage spinellides of the FeTi-chromite-CrTi-magnetite series, which are very poor in Mg and Al and which formed after Crrich aegirine and ilmenite, are the richest in Cr (up to 42% Ct₂O₃). Cr concentrations grew with time during the fenitization process. Unlike minerals in the Khibiny ultramafic rocks where Cr is associated with Mg, Al (it is isomorphic with Cr), and with Ca, chromium in the fenites is associated with Fe, Ti, and V (with which Cr³⁺ is isomorphic) and with Na in silicate minerals. Cr³⁺ Mobility of Cr³⁺ and the unique character of chromium mineralization in the examined fenites were caused by high alkalinity of the fluid.  相似文献   

Polarized optical absorption spectra of synthetic chromium doped Mg2SiO4 (forsterite)     

H. Rager  M. Taran  V. Khomenko 《Physics and Chemistry of Minerals》1991,18(1):37-39

Polarized optical absorption measurements were carried out on three single crystals of Mg₂SiO₄ (forsterite), differently doped with Cr. Two crystals containing average 0.013 and 0.027 weight% Cr, respectively, were pulled from the melt in air, whereas one crystal containing average 0.08 weight% Cr was pulled from the melt in an argon atmosphere. The absorption spectra of the three crystals agree with each other although the intensity of single absorption bands varies significantly. In all -polarized patterns a sharp absorption line around 18000cm^-1 (550 nm) appears. Conjectures are presented to assign this line to the lasing center in Cr doped forsterite which very likely exists as Cr⁴⁺ at the fourfold coordinated Si site.  相似文献   

A commensurate-incommensurate phase transition in iron-bearing åkermanites     

F. Seifert  M. Czank  B. Simons  W. Schmahl 《Physics and Chemistry of Minerals》1987,14(1):26-35

Synthetic melilites on the join Ca₂MgSi₂O₇ (åkermanite) — Ca₂FeSi₂O₇ (iron åkermanite) with Fe/(Fe+Mg) from 0.0 to 0.7 exhibit, at room temperature, an incommensurate phase with a rectangular modulation of a wavelength of about 19 Å in the [110] direction. Upon increase of temperature, they transform to a commensurate melilite structure at about 80° C for Fe/(Fe+Mg)=0.0 and about 250° C for Fe/(Fe+Mg)=0.6. In addition to the T(2) positions of the melilite structure filled by Si, the incommensurate phase exhibits two distinguishable T(1) sites containing the Mg and Fe²⁺. These two sites merge into one site during the phase transition from the incommensurate to the commensurate phase. A structural model for the incommensurate phase is based on the misfit between the tetrahedral (Mg, Fe²⁺)Si₂O ₇ ^4? sheets and the Ca²⁺ ions.  相似文献   

Structure of Cr2SiO4 and possible metal-metal interactions in crystal and melt     

W. A. Dollase  F. Seifert  H. St. C. O'Neill 《Physics and Chemistry of Minerals》1994,21(1-2):104-109

Cr₂SiO₄ has been prepared both as quench crystals and as an apparently stable subsolidus phase, at T=1600 and 1650 °C, P=37 kbar on Cr₂SiO₄ and Cr-SiO₃ bulk compositions. Crystal structure determination by Rietveld analysis of X-ray powder data from 3 samples show the structure, in space group Fddd, to be related to that of Cd₂SiO₄ (thenardite Na₂SO₄-V structure) but with approximately “square planar” coordination of the Cr²⁺ (d ⁴) atom. In one of the axial ligand positions, normal to the strongly bonded CrO₄ equatorial plane, is found a Cr atom (Cr-Cr=2.75 Å). Stereochemistry permits this contact to be a weak metal-metal bond, though it cannot be ruled out to be a non-bonded result of polyhedral connectivity.  相似文献   

On the occurrence and stability of divalent chromium in olivines included in diamonds   总被引：1，自引：0，他引：1  

Roger G. Burns 《Contributions to Mineralogy and Petrology》1975,51(3):213-221

Olivine inclusions in diamonds from kimberlites originating from the deep Upper Mantle contain significant amounts of chromium. It has been suggested that divalent chromium occurs in these olivines. This hypothesis is supported by recent Mössbauer and electronic spectral measurements at high pressures, which demonstrate that pressure-induced reduction takes place in compounds and minerals initially containing Fe³⁺, Mn³⁺, and Cu²⁺ ions. The process is facilitated at high temperatures. Low oxidation states of other metals such as Cr(II) are expected to be stabilized under the very high pressures and elevated temperature conditions in the Mantle. Since Cr²⁺ ions are susceptible to the Jahn-Teller effect, they are predicted by crystal field theory to be stabilized in certain distorted coordination sites, such as the olivine Ml site, all three sites of the -spinel phase, and the 7-coordinated site of the strontium plumbate structure-type. The Cr²⁺ ions in olivines are stabilized in kimberlites intruded into the Crust by the high confining pressures in the diamond inclusions.  相似文献   

57Fe mössbauer study of synthetic Fe3+-melilites     

Masahide Akasaka  Haruo Ohashi 《Physics and Chemistry of Minerals》1985,12(1):13-18

Synthetic Fe³⁺-melilites containing NaCaFe³⁺-Si₂O₇-, Ca₂Fe³⁺AlSiO₇- or Sr₂Fe³⁺AlSiO₇-components have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectrum of åkermanite containing an NaCaFe³⁺Si₂O₇-component consists of one doublet identified to belong to Fe³⁺ in T1 sites. The spectra of åkermanite and gehlenite containing Ca₂Fe³⁺ AlSiO₇- or Sr₂Fe³⁺ AlSiO₇-component consist of two doublets. The inner and outer doublets are identified to belong to Fe³⁺ in the less distorted T1 and that in the more distorted T2 sites, respectively. The area ratios of the spectra show that the site occupancy of Fe³⁺ (T1) in gehlenite is less than that in åkermanite in which the distribution of Fe³⁺ in T1 and T2 sites is apparently random. The different distributions can be explained in terms of competition between minimizing the deficiency in the electrostatic valence and the preference of Al for T1 sites which the isomer shift measurements show to be more ionic.  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   

The configurational entropies of Ca2MgSi2O7-Ca2SiAl2O7 melilites and related minerals     

D. R. Waldbaum 《Contributions to Mineralogy and Petrology》1973,39(1):33-54

Equations for the configurational entropy and homogeneous equilibria in Ca₂MgSi₂O₇-Ca₂SiAl₂O₇ melilites are derived for a site constraint that does not permit Mg on the smaller T₂ tetrahedral sites. This constraint leads to one ordering parameter and one composition parameter. The maximum configurational entropy for perfectly ordered crystalline solutions is 3.795 cal K^–1 mol^–1, corresponding to the structural formula Ca₂(Mg_0.33Al_0.67) (Si_0.67Al_0.33)₂O₇ and not the equimolar composition Ca₂(Mg_0.5Al_0.5)(Si_0.75Al_0.25)₂O₇. Similarly, the configuration Ca₂(Si_0.33Al_0.67)(Si_0.33Al_0.67)₂O₇ has the maximum entropy for the gehlenite end-member composition. The tabulated entropy of end-member gehlenite at 298.15 K must be corrected by at least 2Rln2, which corresponds to a substantial correction to its Gibbs energy at high temperature. The same corrections are applicable to other minerals having two crystallographically distinct sites in a 21 ratio and where the same configurational entropy equation applies: MgFe₂O₄ (magnesioferrite), NiFe₂O₄ (trevorite), TiFe₂O₄ (ulvospinel), TiMg₂O₄, TiZn₂O₄, CuFe₂O₄, and TiFe₂O₅ (pseudobrookite) inasmuch as these substances prefer the same inverse ordered state as gehlenite at low temperatures. The effects of the ideal enthalpy and entropy on temperatures of homogeneous equilibria in gehlenite and MgTi₂O₅ are evaluated. Geological-thermometer phase diagrams of the long-range ordering parameter plotted against temperature have a sigmoidal shape for these minerals owing to the fact that this type of disordering is non-convergent.  相似文献   

Minerals with Brackebuschite-Like Structures: A Novel Solid Solution System Involving Cr<Superscript>6+</Superscript> and V<Superscript>5+</Superscript>     

D.?A.?KhaninEmail author  I.?V.?Pekov 《Geology of Ore Deposits》2017,59(7):642-651

A novel complex continuous system of solid solutions involving vauquelinite Pb₂Cu(CrO₄)(PO₄)(OH), bushmakinite Pb₂Al(VO₄)(PO₄)(OH), ferribushmakinite Pb2Fe³⁺(VO₄)(PO₄)(OH), and a phase with the endmember formula Pb₂Cu(VO₄)(PO₄)(H₂O) or Pb₂Cu(VO₄)(РО₃ОН)(ОН) is studied based on samples from the oxidation zone of the Berezovskoe, Trebiat, and Pervomaisko-Zverevsky deposits in the Urals, Russia. This is the first natural system in which chromate and vanadate anions show a wide range of substitutions and the most extensive solid solution system involving (CrO₄)^2– found in nature. The major couple substitution is Cr⁶⁺ + Cu²⁺ ? V⁵⁺ + M³⁺, where M = Fe, Al. The correlation coefficients calculated from 125 point analyses are: 0.96 between V and (Fe + Al), 0.96 between Cr and (Cu + Zn),–0.96 between V and (Cu + Zn),–0.97 between Cr and (Fe + Al), and–0.97 between (Fe + Al) and (Cu + Zn). The substitutions V⁵⁺ ? Cr⁶⁺ (correlation coefficient–0.98) and to a lesser extent P⁵⁺ ? As⁵⁺ (correlation coefficient–0.86) occur at two types of tetrahedral sites, whereas the metal–nonmetal/metalloid substitutions, i.e., V or Cr for P or As, are minor. The substitution Fe³⁺ ? Al³⁺ is also negligible in this solid solution system.  相似文献   

Exsolution Lamellae in Olivine Grains of Dunite Units from Different Types of Mafic‐Ultramafic Complexes     

LIANG Zi  XIAO Yan  Joyashish THAKURTA  SU Benxun  CHEN Chen  BAI Yang  Patrick A. SAKYI 《《地质学报》英文版》2018,92(2):586-599

Exsolution microstructures in olivine grains from dunite units in a few selected tectonic environments are reported here. They include lamellae of clinopyroxene and clinopyroxene-magnetite intergrowth in the Gaositai and Yellow Hill Alaskan-type complexes, clinopyroxene-magnetite intergrowth in the K?z?lda? ophiolite, and chromite lamellae in the Hongshishan mafic-ultramafic intrusive complex. These lamellae commonly occur as needle-or rod-like features and are oriented in olivine grains. The host olivine grains have Fo contents of 92.5–92.6 in the Gaositai complex, 86.5–90.1 in the Yellow Hill complex, 93.2–93.4 in the K?z?lda? ophiolite and 86.9–88.3 in the Hongshishan complex. Clinopyroxene in the rod-like intergrowth exsolved in olivine grains in the Gaositai and Yellow Hill is diopside with similar major element compositions of Ca O(23.6–24.3 wt%), SiO_2(52.2–54.0 wt%), Al_2O_3(0.67–2.15 wt%), Cr_2O_3(0.10–0.42 wt%) and Na_2O(0.14–0.26 wt%). It falls into the compositional field of hydrothermal clinopyroxene and its origin is thus probably related to reaction between dunite and fluids. The enrichment of the fluids in Ca~(2+), Fe~(3+), Cr~(3+) and Na+, resulted in elevated concentrations of these cations in olivine solid solutions via the reaction. With decreasing temperature, the olivine solid solutions altered to an intergrowth of magnetite and clinopyroxene. The Fe~(3+) and Cr~(3+) preferentially partitioned into magnetite, while Ca~(2+) and Na+ entered clinopyroxene. Since the studied Alaskan-type complexes and ophiolite formed in a subduction environment, the fluids were probably released from the subducted slab. In contrast, the exsolved chromite in olivine grains from the Hongshishan complex that formed in post-orogenic extension setting can be related to olivine equilibrated with Cr-bearing liquid. Similarly, these lamellae have all been observed in serpentine surrounding olivine grains, indicating genetic relations with serpentinization.  相似文献   

Hyperfine interactions and spin transfer between Cr3+ and Al3+ in a synthetic single crystal of Mg2SiO4. A theoretical approach to the interpretation of EPR data     

S. Nagel  H. Rager 《Physics and Chemistry of Minerals》1985,12(5):291-299

The occurrence of Cr-Al pairs in Mg₂SiO₄ has been detected by EPR spectroscopy. In the case where Cr³⁺ replaces Mg at the M2 position three different neighboring Si sites may be substituted by Al³⁺, which should yield different superhyperfine interactions. A new spectrum is presented which shows the presence of two of these possible pair configurations. An assignment of the spectral features to a specific Cr-Al pair with Cr at M2 from the experimental data alone was not possible, therefore, MSX _α cluster calculations have been performed from which the differences in the superhyperfine interaction for the various pair configurations could be obtained. Best agreement with the data of the Cr³⁺(M2)-Al pair exhibiting the most intense group of lines in the EPR spectrum was obtained for the situation where Al³⁺ is at the Si position with the shortest distance to M2. The second observed Cr³⁺(M2)-Al pair, which is significantly weaker in intensity, could not yet be assigned.  相似文献   

Synthetic and natural chromium-bearing spinels: an optical spectroscopy study     

M. N. Taran  F. Parisi  D. Lenaz  A. A. Vishnevskyy 《Physics and Chemistry of Minerals》2014,41(8):593-602

Four samples of synthetic chromium-bearing spinels of (Mg, Fe²⁺)(Cr, Fe³⁺)₂O₄ composition and four samples of natural spinels of predominantly (Mg, Fe²⁺)(Al, Cr)₂O₄ composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr₂O₄ spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr³⁺ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed ⁴ A _2g  → ⁴ T _2g and ⁴ A _2g  → ⁴ T _1g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spinels is related to trigonal distortion of the octahedral site in the spinel structure. A small, if any, splitting of the U-band can only be resolved at curve-fitting analysis. In all synthetic high-chromium spinels, a couple of relatively narrow and weak bands of the spin-allowed transitions ⁴ A _2g  → ² E _g and ⁴ A _2g  → ² T _1g of Cr³⁺, intensified by exchange-coupled interaction between Cr³⁺ and Fe³⁺ at neighboring octahedral sites of the structure, appear at ~14,400 and ~15,100 cm^?1. A vague broad band in the range from ca. 15,000 to 12,000 cm^?1 in synthetic spinels is tentatively attributed to ^IVCr²⁺ + ^VICr³⁺ → ^IVCr³⁺ + ^VICr²⁺ intervalence charge-transfer transition. Iron, mainly as octahedral Fe³⁺, causes intense high-energy absorption edge in near UV-range (ligand–metal charge-transfer O^2? → Fe³⁺, Fe²⁺ transitions). As tetrahedral Fe²⁺, it appears as a strong infrared absorption band at around 4,850 cm^?1 caused by electronic spin-allowed ⁵ E → ⁵ T ₂ transitions of ^IVFe²⁺. From the composition shift of the U-band in natural and synthetic MgCr₂O₄ spinels, the coefficient of local structural relaxation around Cr³⁺ in spinel MgAl₂O₄–MgCr₂O₄ system was evaluated as ~0.56(4), one of the lowest among (Al, Cr)O₆ polyhedra known so far. The octahedral modulus of Cr³⁺ in MgCr₂O₄, derived from pressure-induced shift of the U-band of Cr³⁺, is ~313 (50) GPa, which is nearly the same as in natural low-chromium Mg, Al-spinel reported by Langer et al. (1997). Calculated from the results of the curve-fitting analysis, the Racah parameter B of Cr³⁺ in natural and synthetic MgCr₂O₄ spinels indicates that Cr–O-bonding in octahedral sites of MgCr₂O₄ has more covalent character than in the diluted natural samples. Within the uncertainty of determination in synthetic MgAl₂O₄ spinel, B does not much depend on pressure.  相似文献