Crystal field and charge transfer spectrum of (Mg, Fe)SiO3 majorite     

Hans Keppler  Catherine A. McCammon 《Physics and Chemistry of Minerals》1996,23(2):94-98

Majorite of bulk composition Mg_0.86Fe_0.15SiO₃ was synthesized at 19 GPa and 1900 °C at an oxygen fugacity close to the Re/ReO₂ buffer. Optical absorption spectra of polycrystalline samples were measured from 4000 to 25000cm^?1. The following features were observed: (1) Three bands at 4554, 6005 and 8093 cm^?1 due to the ⁵E_g → ⁵T_2g transition of Fe²⁺ in a distorted dodecahedral site. (2) A band at 9340 cm^?1 due to the transition ⁵T_2g → ⁵E_g of octahedral Fe²⁺. (3) A band at 22784 cm^?1 resulting from Fe³⁺, probably in an octahedral site (⁶A_1g → ⁴A_1g, ⁴E_g). (4) A very intense system of Fe²⁺ → Fe³⁺ intervalence charge transfer bands which can be modelled by two Gaussian components centered at 16542 and 20128 cm^?1. The existence of two components in the charge transfer spectrum could be related to the fact that the tetragonal majorite structure may contain Fe³⁺ in two different octahedral sites. The crystal field splitting Δ of Fe²⁺ in dodecahedral coordination is 5717 cm^?1. If a splitting of the ground state in the order of 1000 cm^?1 is assumed, this yields a crystal field stabilization energy (CFSE) of 3930 cm^?1, comparable to the CFSE of Fe²⁺ in pyrope-rich garnet. However, the splitting of ⁵T_2g is significantly higher than in pyrope. This would be consistent with Fe²⁺ preferentially occupying the more distorted one of the two dodecahedral sites in the majorite structure. For octahedral Fe²⁺, Δ= 9340 cm^?1 and CFSE=3736 cm^?1, assuming negligible splitting of the ground state.  相似文献   

Optical spectroscopy study of natural Fe, Ti-bearing calcic amphiboles     

M. N. Taran  M. Andrut  E. V. Polshin  S. S. Matsyuk 《Physics and Chemistry of Minerals》1999,27(1):59-69

Over thirty samples of natural Ti-bearing amphiboles with Ti- and Fe-contents ranging from 0.111 to 0.729 atom per formula unit (a.p.f.u.) and from 0.479 to 2.045 a.p.f.u., respectively, were studied by means of optical absorption spectroscopy and microprobe analysis. Thirteen samples were also studied by Mössbauer spectroscopy. A strong pleochroic absorption edge, causing the dark brown colours of Ti-bearing amphiboles, is attributed to ligand-metal and metal-metal charge transfer transitions involving both iron and titanium ions (O^2?→ Fe³⁺, Fe²⁺, O^2?→ Ti⁴⁺ and Fe²⁺ + Ti⁴⁺→ Fe³⁺ + Ti³⁺). A broad intense Y-polarized band ～22?000?cm^?1 (ν_1/2?≈?3700?cm^?1) in spectra of two low iron amphiboles with a relatively low Fe³⁺/Fe_total ratio, both from eclogite-like rocks in kimberlite xenoliths, was attributed to electronic Fe²⁺(M3) + Ti⁴⁺(M2)→Fe³⁺(M3)+Ti³⁺(M2) IVCT transitions. The IVCT bands of other possible ion pairs, involving Ti⁴⁺ and Fe²⁺ in M2 and M1, M4 sites, respectively, are presumed to be at higher energies, being obscured by the absorption edge.  相似文献   

A reassessment of the role of iron in the 5,000–30,000 cm−1 region of the electronic absorption spectra of tourmaline     

Gordon Smith 《Physics and Chemistry of Minerals》1978,3(4):343-373

The E∥c and E ⊥ c polarized optical absorption spectra of a variety of blue/green tourmalines and a schorl were measured from room temperature down to helium temperatures. Heat treatments at 750–800° C in air and hydrogen were carried out on several green tourmalines. From the results obtained, absorptions at 7,900 and 13,800 cm^?1 in the E∥c spectra of tourmalines are assigned to Fe²⁺ in the b-site. In the same polarization, bands detected at 9,000 and 13,400 cm^?1 are attributed to Fe²⁺ in the smaller c position. In contrast to previous interpretations, the E ⊥ c polarized bands at 9,000 and 13,800 cm^?1 are not assigned to single ion transitions, but are largely associated with nearest neighbour Fe²⁺-Fe³⁺ pairs. Correlations between near-infrared band absorption coefficients and FeO concentration reinforce these assignments. The temperature dependence and the reaction to heat treatment of the strongly polarized (E⊥c?E∥c) band near 18,000 cm^?1 in blue and green tourmaline spectra are shown to be consistent with previous assignments of the band to Fe²⁺+Fe³⁺→Fe³⁺+Fe²⁺ charge transfer. Similar results are discussed for broad absorptions (also E⊥c?E∥c) found in the 22,000–25,000 cm^?1 region of the spectra of certain green and brown tourmalines. It is concluded that these absorptions are due to Fe²⁺+Ti⁴⁺→Fe³⁺+Ti³⁺ charge transfer. The proposal is made that the initial effect of heating green tourmalines in air and hydrogen is to reduce Fe³⁺ cations located in both b- and c-sites. Further heat treatment in air and hydrogen results in the oxidation of Fe²⁺→Fe³⁺ and leads to the generation of bands near 19,100 and 21,600 cm^?1. The newly formed bands are assigned to Fe³⁺-Fe³⁺ pairs.  相似文献   

Fe2+-Ti4+ charge transfer in stoichiometric Fe2+,Ti4+-minerals     

Stephanie M. Mattson  George R. Rossman 《Physics and Chemistry of Minerals》1988,16(1):78-82

Optical absorption spectra are presented for taramellite, traskite and neptunite, all of which have both Fe²⁺ and Ti⁴⁺ as major elements. The spectra of each of these minerals are dominated by a single, intense absorption band in the 415 to 460 nm region with 7000 to 9000 cm^?1 halfwidth. These transitions, assigned to Fe²⁺-Ti⁴⁺ intervalence charge transfer, showed little difference in intensity at 80 and 300 K and have molar absorptivities which range from ～100 to ～1300 M^?1 cm^?1. The Fe²⁺-Ti⁴⁺ absorptions in these standards generally compare well to other mineral spectra in which Fe²⁺ — Ti⁴⁺ intervalence absorption has previously been proposed with the exception of the most cited example, blue corundum.  相似文献   

Evidence for absorption by exchange-coupled Fe2+-Fe3+ pairs in the near infra-red spectra of minerals     

Gordon Smith 《Physics and Chemistry of Minerals》1978,3(4):375-383

Reduction of Fe³⁺ to Fe²⁺ by heating in hydrogen reduces the absorbance of the bands at 9,000 and 13,800 cm^?1 in the E ⊥ c spectrum of tourmaline, and the 9,000 and 11,000 cm^?1 bands in the E ∥ (001) spectrum of biotite. This behaviour is consistent with the presumed d-d origin of these bands (which seems well established) only if they gain much of their intensity from exchange-coupling with neighbouring Fe³⁺ ions. Intensification of spin-forbidden bands in sapphire by Fe³⁺-Fe³⁺ exchange-coupling was recognized by Ferguson and Fielding (1971, 1972), but exchange-coupling has not previously been thought to intensify spin-allowed d-d bands. Spin-allowed exchange-coupled bands resulting from Fe²⁺-Fe³⁺ pairs have features in common with both normal single ion d-d bands, which they resemble in energy, width and pressure dependence, and Fe²⁺+Fe³⁺→Fe³⁺+Fe²⁺ charge transfer bands, which they resemble in temperature-, heat treatment-, composition-, and polarization-dependence. Distinction between normal d-d, charge transfer, and pair d-d absorptions is thus complicated, and criteria for assigning these bands are discussed. Spin-allowed exchange-coupled pair bands should be sought in the spectra of transition metal clusters (trimers and polymers as well as pairs may be involved) whenever geometry favours their origin. It is possible that the bands near 10,000 and 11,500 cm^?1 in blue sapphire, and at about 5,000 cm^?1 in titanian garnets are of this type, but many other examples are likely to occur. Exchange-coupling may involve ions other than Fe³⁺ (e.g., Mn²⁺, also d ⁵), although Fe²⁺-Fe²⁺ coupling is unlikely to be important at laboratory temperatures.  相似文献   

Fe-Li云母化学成分的解释和分类   总被引：3，自引：0，他引：3       下载免费PDF全文

孙世华 《地质科学》1988,(3):213-228

用置换矢量概念解释了115个天然 Fe-Li 云母化学成分的变化。Fe-Li 云母是三八面体 Li-Fe-Al 云母,其基本置换是四锂云母置换。由于 Al-Li 白云母置换和白云母置换的影响,其化学组成变化的基本趋势呈明显的非线性,因而 Fe-Li 云母不是真正的二元系。作为 Fe-Li 云母,富铁黑云母和铁叶云母都是最富铁的成员,因而建议称 Fe-Li 云母为黑云母-锂云母系列。根据化学成分,晶胞参数和折光率的异常变化还提出了该系列自然分类的方案。  相似文献   

Single crystal absorption spectra of synthetic Ti,Fe-substituted pyropes     

V. M. Khomenko  K. Langer  M. Andrut  M. Koch-Müller  A. A. Vishnevsky 《Physics and Chemistry of Minerals》1994,21(7):434-440

Synthetic pyrope crystals up to 0.5 mm in diameter, substituted by titanium or by titanium plus iron, were grown under defined conditions of P, T, $f_{O_2 }$ in the presence of water using a piston-cylinder device. The crystals were characterized by X-ray and microprobe techniques. Their single-crystal optical absorption spectra were measured by means of a microscope-spectrometer. Two absorption bands at 16100 and 22300 cm{cm-1} in the spectra of pale-blue Fe-free Ti-bearing pyropes, grown under reduced conditions, were identified as originating from spin-allowed transitions, derived from ² T _2g → ² E _g of octahedral Ti³⁺ ions. The splitting value of the excited ²E _g state, 6200 cm^-1, and the crystal field parameter of Ti³⁺ in pyrope Δ ₀ = 19 200 cm^-1 are both in agreement with literature data. In spectra of brown Fe, Ti-bearing garnets, a broad band at 23000 cm^-1 was interpreted as a Fe^2+[8] → Ti^4+[6] charge-transfer band. The spectral position and width of this band agree with those observed for a FeTi charge transfer band in natural garnets. Fe, Ti-containing garnets synthesized at relatively high oxygen fugacity (10^-11,0 atm), which permits a fraction of Fe³⁺ to enter the garnet, show an additional Fe^2+[8] → Fe^3+[6] charge transfer band at 19800 cm^-1.  相似文献   

Measurement of the polarized absorption spectra of synthetic transition metal-bearing silicate microcrystals in the spectral range 44,000-4,000 cm−1     

K. Langer  R. M. Abu-Eid 《Physics and Chemistry of Minerals》1977,1(3):273-299

A new single beam microtechnique has been developed for measuring the polarized absorption spectra in the region 44,000-4,000 cm^?1. Spectra of a natural garnet (Spess₇₀Alm₃₀), measured by the microtechnique and by conventional macrotechniques, are consistent and thus prove the applicability of the microtechnique described. It is possible to obtain well resolved spectra down to about 13,000 cm^?1 with crystals as small as about 10 μm. Thus spectra of crystals obtained in routine high-pressure high-temperature silicate syntheses can be measured. The polarized spectra of Mn³⁺, Fe³⁺, Fe²⁺, and Cr³⁺ in the following synthetic silicate minerals are presented: piemontite (I), acmite (II), orthoferrosilite (III), and kyanite (IV) or uvarovite (V), respectively. O-Cr³⁺, O-Mn³⁺, and O-Fe²⁺ charge transfer band maxima in the UV region are identified at 38,700 cm^?1, in V; at 33,200, 35,300, and 39,000 cm^?1, in I; and at 32,800, 35,200, and 37,300 cm^?1, in III, respectively. Bands in the region ≦25,000 cm^?1 are assigned to spin-allowed and spin-forbidden dd transitions as predicted from crystal field theoretical considerations for the foregoing ions in the respective structures.  相似文献   

Spectroscopic studies on natural chloritoids     

Ulf Hålenius  Hans Annersten  Klaus Langer 《Physics and Chemistry of Minerals》1981,7(3):117-123

Room temperature and low temperature Mössbauer and optical absorption spectroscopic data on six natural chloritoids characterized by means of electron microprobe and X-ray powder diffraction techniques are presented. Two narrow quadrupole doublets with widths of 0.25–0.29 mm/s assigned to Fe²⁺ in a relatively large octahedral site and Fe³⁺ in a smaller octahedral site, are observed in the Mössbauer spectra. Polarized optical absorption spectra reveal three main absorption bands. A broad absorption band at 16,300 cm^?1, which is strongly polarized in E‖X and E‖Y and shows a linear increase in integral absorption with increasing [Fe²⁺] [Fe³⁺] concentration product, is assigned to a Fe²⁺+Fe³⁺→Fe³⁺+Fe²⁺ charge transfer transition. This band displays also a temperature dependence different from that of single ion d?d transitions. Two absorption bands at 10,900 cm^?1 and 8,000 cm^?1 are, on the basis of compositional dependence and energy, assigned to Fe²⁺ in the large M(1B) octahedra of the brucite-type layer in chloritoid. Combined spectroscopic evidence and structural and chemical considerations support a distribution scheme for ferrous and ferric iron which orders the Fe²⁺ ions in the M(1B) octahedra and the Fe³⁺ ions in the small M(1A) octahedral sites. Both types of octahedra are found in the brucite type layer of chloritoid.  相似文献   

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods   总被引：1，自引：0，他引：1  

M. Koch-Müller  I. Abs-Wurmbach  D. Rhede  V. Kahlenberg  S. Matsyuk 《Physics and Chemistry of Minerals》2007,34(9):663-678

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.  相似文献   

Magnetic properties of sheet silicates; 2:1 layer minerals     

O. Ballet  J. M. D. Coey 《Physics and Chemistry of Minerals》1982,8(5):218-229

Susceptibility, magnetisation and Mössbauer measurements are reported for a representative selection of 2:1 layer phyllosilicates. Eight samples from the mica, vermiculite and smectite groups include examples diluted in iron which are paramagnetic at all temperatures, as well as iron-rich silicates which order magnetically below 10 K. Anisotropic susceptibility of crystals of muscovite, biotite and vermiculite is quantitatively explained with a model where the Fe²⁺ ions lie in sites of effective trigonal symmetry, the trigonal axis lying normal to the sheets. The ferrous ground state is an orbital singlet. Ferric iron gives an isotropic contribution to the susceptibility. Fe²⁺-Fe²⁺ exchange interactions are ferromagnetic with y ～ 2 K, whereas Fe³⁺-Fe³⁺ coupling is antiferromagnetic in the purely ferric minerals. A positive paramagnetic Curie temperature for glauconite may be attributable to Fe²⁺ → Fe³⁺ charge transfer. Magnetic order was found to set in inhomogeneously for glauconite at 1–7 K. One biotite sample showed an antiferromagnetic transition at T _N =7 K marked by a well-defined susceptibility maximum. Its magnetic structure, consisting of ferromagnetic sheets with moments in their planes coupled antiferromagnetically by other, weak interactions, resembles that found earlier for the 1:1 mineral greenalite.  相似文献   

A reassignment of the optical absorption bands in biotites     

W. Kliem  G. Lehmann 《Physics and Chemistry of Minerals》1979,4(1):65-75

The electronic absorption spectra of three biotites with largely differing Fe²⁺/Fe³⁺ ratios were studied before and after thermal dehydration and oxidation of divalent iron. Three absorption bands near 17,100, 20,500 and 24,100 cm^?1 and an absorption edge at slightly higher energies are assigned to trivalent iron present in clusters of strongly interacting ions. The presence of additional broad absorption bands due to intervalence transfer between Fe²⁺ and Fe³⁺ or Ti⁴⁺ in this region cannot be excluded for biotites with high Fe²⁺ concentrations. Three bands at lower energies show a satisfactory correlation with concentration of divalent iron and decrease in the same proportions with oxidation. We therefore assign them to split components of the spin-allowed ligand field transition of Fe²⁺ at the M ₁ and M ₂ sites. This contradicts the assignment of one of these bands to an intervalence charge transfer between Fe²⁺ and Fe³⁺ by previous authors. It is shown that there is no indisputable evidence against our assignment.  相似文献   

Natural occurrence of a (Fe,Mn, Mg) tetrasilicic potassium mica     

J. -L. Robert  R. C. Maury 《Contributions to Mineralogy and Petrology》1979,68(2):117-123

A mica whose structural formula: (K_1.76Na_0.31)(Fe_2.22Mn_1.29Mg_0.99Ti_0.28Al_0.240.98) ·(Si_7.33Al_0.67)O_20.26(F_2.16OH_1.58) closely approximates that of tetrasilicic potassium mica K₂(M ₅ ²⁺ )Si₈O₂₀(OH,F)₄ where M²⁺ represents Mg²⁺, Fe²⁺, Mn²⁺, ..., has been discovered in the matrix of a peralkaline rhyolite (comendite) of the Mont-Dore massif (France). These micas had been obtained previously by synthesis only. In the groundmass of the rock, the micaceous phase is accompanied by a manganoan arfvedsonite, pyrophanite, magnetite, apatite, sphene, zircon and fluorite. The crystallographic properties of the mica are typically that of a tetrasilicic mica, with d ₀₆₀ = 1.533Å and space group C2/m. There is a regular decrease of d ₀₆₀ (parameter b) with the ionic radius of the octahedral cation in synthetic micas containing Fe²⁺, Co²⁺, Mg²⁺, Ni²⁺. The purely Mn²⁺ end-member could not be synthesised; its instability is discussed on the basis of structural considerations. The conditions of crystallization of the micaceous phase are estimated to be 760 ° C, 800 bars with a f _{o 2}=10^–14.7 bar. This mica has crystallized from a residual liquid, with high activity of silica and low activity of alumina, whose origin is discussed. The name MONT-DORITE is proposed for this natural tetrasilicic mica having Fe/Fe+Mg >1/2 and Fe/Fe+Mn >1/2. This name is from the stratovolcano Mont-Dore.  相似文献   

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

G. Steffen  K. Langer  F. Seifert 《Physics and Chemistry of Minerals》1988,16(2):120-129

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.  相似文献   

Celadonite mica: Solid solution and stability     

Bruce Velde 《Contributions to Mineralogy and Petrology》1972,37(3):235-247

Phase relations for the bulk compositions of the celadonites between the MgAl, MgFe³⁺ and Fe²⁺Fe³⁺ types (celadonite = KR²⁺R³⁺ Si₄O₁₀ (OH)₂) under magnetite-iron and nickel-nickel oxide solid-fluid buffers indicate the extent of solid solution possible in this potassic mica series at temperatures between 300° and 430° C at 2 Kb total pressure. Other possible combinations of Mg, Al, Fe ions in octahedrally coordinated sites did not produce single-phase mica products. The ferrous celadonite micas are stable only under oxygen fugacities where magnetite is the stable oxide—where both Fe²⁺ and Fe³⁺ can coexist. However the celadonite with the highest thermal stability at 2 Kb total pressure, nickel-nickel oxide buffer conditions is the KMgFe³⁺Si₄O₁₀(OH)₂ phase which is stable up to 420°C, well into low grade metamorphic conditions. It is thus apparent that the presence of celadonite or glauconite mica will not be indicative of changing diagenetic conditions.  相似文献   

Fe2+ -F avoidance in silicates     

Philip E. Rosenberg  Franklin F. Foit 《Geochimica et cosmochimica acta》1977,41(2):345-346

Fe²⁺-F avoidance, reported in the literature in micas and amphiboles, can be accounted for by crystal field theory. The crystal field splitting parameter, Δ_O, of Fe²⁺ octahedrally coordinated to F^? is significantly smaller than its value when (OH)^? is the coordinating anion. Thus, the presence of Fe²⁺ is not favored at sites where F^? substitutes for (OH)^? due to smaller crystal field stabilization energy.  相似文献   

Micas from the Khaluta carbonatite deposit,western Transbaikal region     

G. S. Ripp  A. G. Doroshkevich  N. S. Karmanov  S. V. Kanakin 《Geology of Ore Deposits》2009,51(8):812-821

The Khaluta carbonatite deposit located in the western Transbaikal region was formed during the Late Mesozoic rifting in the southern framework of the Siberian Craton. Carbonatite is associated with shonkinite and syenite and is accompanied by fenitization. The composition of mica in more than 160 samples of country rocks, carbonatites, silicate rocks, and fenites was studied. The Fe³⁺ and Fe²⁺ contents, as well as oxygen isotopic composition, were determined. The Mg and Fe contents increase, whereas the Ti and Al contents decrease in micas when passing from silicate rocks and fenites to carbonatites. Micas from carbonatites are depleted in Al, enriched in Fe³⁺, and distinguished by high Si and F contents. According to our calculations, in some cases Al replaces Si in the tetrahedral site instead of replacement of Fe³⁺ as is characteristic of tetraferriphlogopite. Formally, the mica from carbonatites falls within the tetraferriphlogopite field, but typical inverse pleochroism is not always observable. The δ¹⁸O values of micas from carbonatite, shonkinite, syenite, and fenite are similar to those of mantle-derived silicate minerals. The δ¹⁸O values in the minerals coexisting with phlogopite testify to their isotopic equilibrium and make it possible to calculate the crystallization temperature of carbonatite.  相似文献   

Electrical conductivity, thermopower and 57Fe Mössbauer spectroscopy of an Fe-rich amphibole, arfvedsonite     

E. Schmidbauer  Th. Kunzmann  Th. Fehr  R. Hochleitner 《Physics and Chemistry of Minerals》1996,23(2):99-106

The electrical charge transport was examined in an Fe-rich amphibole, arfvedsonite, using frequency dependent AC resistivity (impedance spectroscopy) and thermopower Θ measurements in the temperature range 30–800°C. Two different semiconducting charge transfer mechanisms were observed which are due to volume conduction for measurements parallel and perpendicular to the [001] direction; they arise probably from a conduction mechanism related to lattice defects, both with activation energies E_A ≈ 0.4 eV. The extrapolated DC conductivity, for a fixed temperature, along [001] is about 5–6 times higher than that perpendicular to [001]. From the temperature independent positive Θ values it follows that hole conduction occurs, and a hopping-type charge transport is acting, probably effected by electron hopping Fe²⁺ → Fe³⁺. Possible charge transfer paths are discussed. ⁵⁷Fe Mössbauer spectra enabled to determine the relative concentrations of Fe²⁺ and Fe³⁺. From a comparison of these data and from Θ results it is concluded that the main fraction of Fe²⁺ and Fe³⁺ take part in long range charge transport.  相似文献   

多硅白云母中Fe²⁺的高压有序效应          下载免费PDF全文

应育浦  宋仁奎 《地质科学》1995,30(4):355-362

21个多硅白云母来自4个低温高压变质带。用电子探针、X射线粉末衍射及穆斯堡尔谱测定其化学成分、b0值及Fe²⁺占位。建立Fe²⁺(M1)/Fe²⁺(M2)对b0值相关图,发现Fe²⁺在八面体晶位有序化并解释其有序机理。  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