Structure and Mössbauer spectroscopy of barbosalite Fe2+Fe3+ 2 (PO4)2(OH)2 between 80 K and 300 K     

G. J. Redhammer  G. Tippelt  G. Roth  W. Lottermoser  G. Amthauer 《Physics and Chemistry of Minerals》2000,27(6):419-429

Natural barbosalite Fe²⁺Fe³⁺ ₂ (PO₄)₂(OH)₂ from Bull Moose Mine, South Dakota, U.S.A., having ideal composition, was investigated with single crystal X-ray diffraction techniques, Mössbauer spectroscopy and SQUID magnetometry to redetermine crystal structure, valence state of iron and evolution of ⁵⁷Fe Mössbauer parameter and to propose the magnetic structure at low temperatures. At 298?K the title compound is monoclinic, space group P2₁/n, a _o ?= 7.3294(16)?Å, b _o ?=?7.4921(17)?Å, c _o ?=?7.4148 (18)?Å, β?=?118.43(3)°, Z?=?2. No crystallographic phase transition was observed between 298?K and 110?K. Slight discontinuities in the temperature dependence of lattice parameters and bond angles in the range between 150?K and 180?K are ascribed to the magnetic phase transition of the title compound. At 298?K the Mössbauer spectrum of the barbosalite shows two paramagnetic components, typical for Fe²⁺ and Fe³⁺ in octahedral coordination; the area ratio Fe³⁺/Fe²⁺ is exactly two, corresponding to the ideal value. Both the Fe²⁺ and the Fe³⁺ sublattice order magnetically below 173?K and exhibit a fully developed magnetic pattern at 160?K. The electric field gradient at the Fe²⁺ site is distorted from axial symmetry with the direction of the magnetic field nearly perpendicular to V_zz, the main component of the electric field gradient. The temperature dependent magnetic susceptibility exhibits strong antiferromagnetic ordering within the corner-sharing Fe³⁺-chains parallel to [101], whereas ferromagnetic coupling is assumed within the face-sharing [1?1?0] and [?1?1?0] Fe³⁺-Fe²⁺-Fe³⁺ trimer, connecting the Fe³⁺-chains to each other.  相似文献   

Distribution of Fe2+ and Fe3+ and next-nearest neighbour effects in natural chromites: comparison between results of QSD and Lorentzian doublet analysis     

Z. Li  J. Y. Ping  M. Z. Jin  M. L. Liu 《Physics and Chemistry of Minerals》2002,29(7):485-494

The Mössbauer spectra of one chromite at 298 K and one chromite at 298, 200, 170, 140 and 90 K have been analyzed in this study. A Voigt-based quadrupole splitting distribution (QSD) method was used to analyze the spectra. The tetrahedral site Fe²⁺ and the octahedral site Fe³⁺ quadrupole splitting distributions (QSDs) were obtained from the Mössbauer spectra of chromites, and the multiple tetrahedral site Fe²⁺ Gaussian QSD components and the large widths σ _Δ of the Gaussian QSD components of the tetrahedral site Fe²⁺ QSDs for chromites were attributed to next-nearest neighbor effects. In addition, temperature dependences of the isomer shift and the quadrupole splitting were presented and discussed. Comparisons between the Mössbauer parameters for thickness-corrected folded spectra and raw-folded spectra of chromites were made, and the results show that the two sets of the Mössbauer parameters and ratios of ferric to total iron as well as χ² are very close to each other. This is because of the small absorber thickness of chromites in this study. Comparisons between the Mössbauer parameters of chromites obtained using the Voigt-based QSD method and a Lorentzian doublet method were also made. The results show that there are some differences between the two sets of the Mössbauer parameters and ratios of ferric to total iron, but not significant. However, much larger χ² were obtained when the Lorentzian doublet method was used to fit the spectra of chromites. This indicates that the Voigt-based QSD method is more adequate to analyze the Mössbauer spectra of chromites from the point of view of statistics.  相似文献   

Electrical resistivity and 57Fe Mössbauer spectra of Fe-bearing calcic amphiboles     

E. Schmidbauer  Th. Kunzmann  Th. Fehr  R. Hochleitner 《Physics and Chemistry of Minerals》2000,27(5):347-356

Electrical resistivity and ⁵⁷Fe Mössbauer spectra are reported for three calcic amphiboles with different Fe concentrations. AC measurements (20?Hz–1?MHz) were performed, applying impedance spectroscopy between 100 and 785?°C in an N₂ gas atmosphere. It was found that up to three semiconducting charge transport processes can be distinguished, which in part changed slightly when several runs were carried out to higher temperatures. The extrapolated DC resistivity is much smaller for an amphibole with high Fe content than for the two with lower Fe concentrations. The derived activation energies are between ～0.48 and ～1.06?eV. For temperatures ≤600?°C the results are compatible with a charge transport mechanism due to electron hopping between Fe²⁺ and Fe³⁺. Above 600?°C, dehydrogenation and/or beginning amphibole decomposition obviously alter the conduction mechanism. From Mössbauer spectra it was established that in all amphibole samples Fe²⁺ and Fe³⁺ are simultaneously present. Mössbauer parameters were derived by fitting the observed spectra to models taking the occupation of various M sites into account.  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   

Ilvaite: A study of temperature dependent electron delocalization by the mössbauer effect     

D. A. Nolet  R. G. Burns 《Physics and Chemistry of Minerals》1979,4(3):221-234

The mixed valence iron silicate ilvaite, CaFe ₂ ²⁺ Fe³⁺Si₂O₈(OH), displays electron delocalization associated with Fe²⁺→Fe³⁺ charge transfer as observed by Mössbauer spectroscopy. Previous studies report the observation of an ‘electron hopping phenomenon’ with resolution of discrete valence states below 320 K. Mössbauer spectra of a suite of naturally occurring ilvaites were recorded over a temperature range, 80 K to 575 K. Five quadrupole doublets were resolved by computer fitting and assigned to Fe²⁺(A), Fe²⁺(B), Fe³⁺(A), and Fe²⁺(A)→Fe³⁺(A)‖c and ⊥c. Contrary to prior work, doublets associated with electron delocalization are resolved at 80 K and preclude the use of a Verwey-type order-disorder model. We propose a thermal activation model and discuss its criteria from molecular orbital and mineralogical viewpoints.  相似文献   

A Mössbauer and X-ray diffraction study of annites synthesized at different oxygen fugacities and crystal chemical implications     

G. J. Redhammer  A. Beran  E. Dachs  G. Amthauer 《Physics and Chemistry of Minerals》1993,20(6):382-394

A refined set of Mössbauer parameters (isomer shifts, quadrupole splittings, Fe²⁺/Fe³⁺ ratios) and lattice parameters were obtained from annites synthesized hydrothermally at pressures between 3 and 5 kbars, temperatures ranging from 250 to 780° C and oxygen fugacities controlled by solid state buffers (NNO, QMF, IM, IQF). Mössbauer spectra showed Fe²⁺ and Fe³⁺ on both the M1 and the M2 site. A linear relationship between Fe³⁺ content and oxygen fugacity was observed. Towards low Fe³⁺ values this linear relationship ends at ≈10% of total iron showing that the Fe³⁺ content cannot be reduced further even if more reducing conditions are used. This indicates that in annite at least 10% Fe²⁺ are substituted by Fe³⁺ in order to match the larger octahedral layer to the smaller tetrahedral layer. IR spectra indicate that formation of octahedral vacancies plays an important role for charge balance through the substitution 3 Fe²⁺ → 2 Fe³⁺ + ?_(oct).  相似文献   

The Mössbauer spectrum of 57Fe in titanium-bearing andradites     

G. Amthauer  H. Annersten  S. S. Hafner 《Physics and Chemistry of Minerals》1977,1(4):399-413

Mössbauer spectra of ⁵⁷Fe in 2 schorlomite garnets reveal 5 distinct quadrupole-split doublets: dodecahedral Fe²⁺, octahedral Fe²⁺ and Fe³⁺, and tetrahedral Fe²⁺ and Fe³⁺. The isomer shifts and nuclear quadrupole splittings of the 5 doublets were studied between 15 and 500 K. The site occupancies for iron were determined. Reference of the chemical analyses to a basis of 12 oxygens and the Mössbauer data show that in the 2 schorlomites titanium is exclusively quadruvalent within the experimental error. The isomer shift of tetrahedral Fe²⁺ between 15 and 295 K seems to be rather small. The shift is interpreted in terms of localized chemical bonding. Above 295 K the shift cannot be evaluated because of overlapping peaks. If electronic transfer processes (e.g. “electron hopping”) between cations are present their relaxation times must be longer than ～10^?7 s.  相似文献   

Characterization of beryl (aquamarine variety) by Mössbauer spectroscopy     

R. R. Viana  G. M. da Costa  E. De Grave  H. Jordt-Evangelista  W. B. Stern 《Physics and Chemistry of Minerals》2002,29(1):78-86

The Mössbauer spectra of several blue beryls have been obtained in the temperature range of 4.2–500 K. A common feature observed in all room-temperature spectra is the presence of an asymmetric Fe²⁺ doublet (ΔE _Q ?～?2.7?mm?s^?1, δ?～?1.1?mm?s^?1), with a very broad low-velocity peak. This asymmetry seems to be related to a relaxation process involving ferrous ions and water molecules in the structural channels, as suggested by Price et?al. (1976). Surprisingly, the spectrum at 500?K also shows a broad, but symmetrical, doublet, with a clear splitting of the lines indicating the presence of at least two Fe²⁺ components. The room-temperature spectrum obtained after the 500?K run shows the same features as prior to the heating. At 4.2?K the spectrum of a deep blue beryl was well fitted with four symmetrical doublets, one of which could be related to Fe²⁺ in the structural channels. Ferrous ion was also found to occupy the octahedral and tetrahedral sites, whereas ferric ion is most probably located in the octahedral site. A meaningful fit of the room-temperature spectrum, as well as an explanation for the temperature dependence of the Mössbauer spectra, are discussed. Finally, it is believed that the color in beryl will be dictated by the relative proportions of Fe³⁺ in the octahedral sites and of Fe²⁺ in the channels.  相似文献   

Pressure effect on the electronic structure of iron in (Mg,Fe)(Si,Al)O3 perovskite: a combined synchrotron Mössbauer and X-ray emission spectroscopy study up to 100 GPa     

J. Li  W. Sturhahn  J. M. Jackson  V. V. Struzhkin  J. F. Lin  J. Zhao  H. K. Mao  G. Shen 《Physics and Chemistry of Minerals》2006,33(8-9):575-585

We investigated the valence state and spin state of iron in an Al-bearing ferromagnesian silicate perovskite sample with the composition (Mg_0.88Fe_0.09)(Si_0.94Al_0.10)O₃ between 1 bar and 100 GPa and at 300 K, using diamond cells and synchrotron Mössbauer spectroscopy techniques. At pressures below 12 GPa, our Mössbauer spectra can be sufficiently fitted by a “two-doublet” model, which assumes one ferrous Fe²⁺-like site and one ferric Fe³⁺-like site with distinct hyperfine parameters. The simplest interpretation that is consistent with both the Mössbauer data and previous X-ray emission data on the same sample is that the Fe²⁺-like site is high-spin Fe²⁺, and the Fe³⁺-like site is high-spin Fe³⁺. At 12 GPa and higher pressures, a “three-doublet” model is necessary and sufficient to fit the Mössbauer spectra. This model assumes two Fe²⁺-like sites and one Fe³⁺-like site distinguished by their hyperfine parameters. Between 12 and 20 GPa, the fraction of the Fe³⁺-like site, Fe³⁺/∑Fe, changes abruptly from about 50 to 70%, possibly due to a spin crossover in six-coordinate Fe²⁺. At pressures above 20 GPa, the fractions of all three sites remain unchanged to the highest pressure, indicating a fixed valence state of iron within this pressure range. From 20 to 100 GPa, the isomer shift between the Fe³⁺-like and Fe²⁺-like sites increases slightly, while the values and widths of the quadruple splitting of all three sites remain essentially constant. In conjunction with the previous X-ray emission data, the Mössbauer data suggest that Fe²⁺ alone, or concurrently with Fe³⁺, undergoes pressure-induced spin crossover between 20 and 100 GPa.  相似文献   

Mössbauer spectra of Fe x O (x>0.95)     

C. A. McCammon  D. C. Price 《Physics and Chemistry of Minerals》1985,11(6):250-254

The Mössbauer spectra of five samples of Fe _x O with compositions in the range 1.00>x>0.95 have been recorded at 298 K and 4.2 K. The spectrum of Fe _x O at 298 K consists of an asymmetric doublet which was fitted to one Fe²⁺ singlet, two Fe²⁺ doublets and 1 Fe³⁺ singlet. The Mössbauer parameters vary consistently with the increasing density of defects as x decreases. The Mössbauer spectrum of Fe _x O at 4.2 K consists of a large number of unresolved lines. The data were fitted to a series of singlets to enable the rough calculation of quantities relating to the mean Fe²⁺ and Fe³⁺ environments. The results of the fits to the 298 K spectra are briefly discussed in terms of a physical model for the defect structure of Fe _x O.  相似文献   

The crystal chemistry of ferric iron in Fe0.05Mg0.95SiO3 perovskite as determined by Mössbauer spectroscopy in the temperature range 80–293 K     

C. A. McCammon 《Physics and Chemistry of Minerals》1998,25(4):292-300

Mössbauer spectra were recorded at multiple temperatures between 80 and 293 K to study the nature of Fe³⁺ in Fe_0.05Mg_0.95SiO₃ perovskite that had been synthesised in a multianvil press at 1650 °C and 25 GPa at its mimimum stability limit. The Mössbauer data were fitted to a model with quadrupole splitting distributions (Fe²⁺) and Lorentzian lineshapes (Fe³⁺ and Feⁿ⁺). The centre shift data were fitted to a Debye model with the following results: Θ_M (Fe²⁺)=365±52 K and Θ_M (Fe³⁺)=476±96 K. Hyperfine parameter data for Fe³⁺ suggest occupation of the octahedral site only. The average valence seen by the Mössbauer effect in rapid electron exchange that occurs between Fe²⁺ and Fe³⁺ is calculated from the hyperfine parameters to be 2.50±0.07. Correction of area fractions for site-dependent recoil-free fractions gives a value for Fe³⁺/∑Fe of 9.4±1.4%, which is independent of temperature. A perovskite phase of similar composition synthesised in the multianvil press at higher oxygen fugacity gives a value for Fe³⁺/∑Fe of 16±3%, where Fe³⁺ appears to occupy both sites in the perovskite structure.  相似文献   

Mössbauer spectra and magnetic features of ilvaites     

Takamitsu Yamanaka  Yoshio Takéuchi 《Physics and Chemistry of Minerals》1979,4(2):149-159

Ilvaite samples from six different localities in Japan are found to be members of a solid-solution series varying from Ca(Fe²⁺,Fe³⁺)₂Fe²⁺(OH)O Si₂O₇ to approaximately Ca(Fe²⁺,Fe³⁺)₂Fe _0.5 ²⁺ Mn _0.5 ²⁺ (OH)O Si₂O₇, and have been studied by Mössbauer spectrometry and magnetic measurements. The variation in intensity of Mössbauer doublets confirms that Mn substitutes for Fe²⁺ in the M(B) cation site. An temperatures decreasing from 300 K to 4K, an abrupt change in the reciprocal mass magnetic susceptibility, 1/x _g, occurs about 120 K; 1/x _g depends linearly upon temperature above 120 K. This change, which is characterized by an unusual mode of decrease in 1/x _g, has been interpreted based on Mössbauer spectra at 80 K: the spectra of Fe²⁺ and Fe³⁺ in the M(A) site show Zeeman splitting, whereas those of Fe²⁺ in the M(B) site do not show the effect. This Mössbauer evidence suggests that magnetic spins of Fe in M(A) are in an ordered state, very likely of antiparallel coupling, whereas those of Fe in M(B) are randomly oriented, showing that below 120 K ilvaite has two different magnetic states for Fe ions. As there is a line of evidence that the spins of Fe in M(B) would take an ordered state at extremely low temperatures, ilvaite magnetism may be regarded as basically antiferromagnetic. The magnetic spins of Fe in M(A) and M(B) undergo magnetic transitions at different specific temperatures, thus giving as a whole unusual features of magnetism.  相似文献   

57Fe and 119Sn Mössbauer studies of natural tin-bearing garnets     

G. Amthauer  J. R. McIver  E. A. Viljoen 《Physics and Chemistry of Minerals》1979,4(3):235-244

The Mössbauer spectra of ¹¹⁹Sn and ⁵⁷Fe in three natural and a synthetic garnet were studied between 20 and 300 K. These spectra reveal the presence of octahedral Sn⁴⁺ as well as octahedral Fe³⁺ and Fe²⁺. Sn²⁺ could not be detected. On the basis of these results the following cation substitution can be derived for the tin-bearing Silicate garnets of this study: Sn⁴⁺ (oct)+Fe²⁺ (oct) ? 2 Fe³⁺ (oct).  相似文献   

Electric-field gradient and mean-squared-displacement tensors in hedenbergite from single-crystal Mössbauer milliprobe measurements     

W. C. Tennant  C. A. McCammon  R. Miletich 《Physics and Chemistry of Minerals》2000,27(3):156-163

We report Mössbauer milliprobe measurements on small single-crystals of a magnesium-rich hedenbergite, approximate composition CaFe_0.54Mg_0.46 (SiO₃)₂, in which each of the electric-field gradient and mean-squared displacement tensors for Fe²⁺ in the M1 site of the crystal are precisely determined. Each tensor has in common, as required of crystal symmetry, the twofold axis of the monoclinic unit cell, but the principal directions of the two tensors in the perpendicular plane are non-coincident. The mean-squared displacements determined in the Mössbauer experiment exceed those determined from the X-ray vibration ellipsoids for Fe²⁺/M1 by a factor of 1.6; the anisotropy in the mean-squared displacement tensor from the Mössbauer measurements exceeds that from X-ray by a factor of around 5. The ramifications of these differences are discussed.  相似文献   

Mössbauer and ELNES spectroscopy of (Mg,Fe)(Si,Al)O3 perovskite: a highly oxidised component of the lower mantle     

S. Lauterbach  C. A. McCammon  P. van Aken  F. Langenhorst  F. Seifert 《Contributions to Mineralogy and Petrology》2000,138(1):17-26

(Mg,Fe)(Si,Al)O₃ perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe³⁺/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe³⁺/ΣFe with Al composition of (Mg,Fe)(Si,Al)O₃ perovskite. The Fe³⁺/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O₃ perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe³⁺/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe³⁺/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O₃ perovskite.  相似文献   

Electron delocalization and magnetic behavior in a single crystal of ilvaite,a mixed valence iron silicate     

D. Ghosh  T. Kundu  S. Dasgupta  Subralā Ghose 《Physics and Chemistry of Minerals》1987,14(2):151-155

Ilvaite, Ca(Fe²⁺, Fe³⁺)Fe²⁺Si₂O₈(OH), a black mixed valence iron silicate shows considerable Fe²⁺?Fe³⁺ electron delocalization above 400 K, reminiscent of magnetite. A crystallographic phase transition from orthorhombic (Pnam) to monoclinic (P2 ₁/a) symmetry takes place on cooling at 343 K induced by electron ordering. In both phases, Fe²⁺ and Fe³⁺ occur in double octahedral chains parallel to the c axis. The thermal characteristics of the magnetic susceptibilities and their anisotropies in different crystallographic planes have been measured in the temperature range 400?21 K. Below 343±1K, a continuous rotation of the molar susceptibility K _∥ in the ab plane down to 90±2 K is observed, where the symmetry of the magnetic ellipsoid remains unchanged. X _a, X _b and X _c increase abruptly below 123±0.5 K, although antiferromagnetic ordering of Fe²⁺ and Fe³⁺ spins on A sites was suggested in previous Mössbauer and neutron powder diffraction studies. In addition, 1/X _a shows an antiferromagnetic maximum at 50±3 K, whereas 1/X _b and 1/X _c at first increase sharply below 123 K, followed by antiferromagnetic curvatures in the lowest temperature region. This behavior is consistent with the antiferromagnetic ordering of Fe²⁺ spins in the B sites. The observed magnetic phenomena suggest charge delocatization effects between adjacent Fe²⁺(A)-Fe³⁺(A) pairs not only along c, but also along a and b directions. The negative sign of the molar anisotropy (K _∥-K_⊥) suggests a singlet ground State ⁵A₁ for the Fe²⁺ ions, in agreement with previous Mössbauer studies.  相似文献   

Structure and physical property relations of Mn ilvaite     

E. Schmidbauer  Th. Fehr  R. Hochleitner  J. Schneider 《Physics and Chemistry of Minerals》2005,32(5-6):388-399

Structural and compositional data as well as ⁵⁷Fe Mössbauer parameters were determined on a natural Mn-rich monoclinic ilvaite crystal (ideal composition CaFe ₂ ²⁺ Fe³⁺Si₂O₈(OH)) which was used for electrical conductivity and thermopower measurements (part 2 of this paper). A zonar structure was found by electron microprobe analysis with a strong decrease in Mn concentration from the rim to the centre of the crystal in a plane perpendicular to the [001] direction. X-ray powder diffraction analysis of the most Mn-rich composition was performed. Mn²⁺ cations populate preferentially M2 sites of the ilvaite unit cell (space group P21/a), to a lower extent they reside on M1 and a reduced part is on Ca sites. The monoclinic angle was determined to β=90.178(4)°. The structural results are compared to literature data for other natural Mn-rich as well as low-impurity ilvaites; this concerns in particular the lattice b parameter and the undecided issue of the varying β angle. In the literature, the order parameter σ, which describes the varying degree of ordering of Fe²⁺–Fe³⁺ pairs on M11 and M12 sites in chains running parallel to the [001] direction, and structural defects are thought to be related to β. The interrelationship between β and σ with respect to a possible twin domain structure is discussed. Various ⁵⁷Fe Mössbauer spectra were recorded between 151 K and 327 K. Mössbauer parameters and Fe²⁺/Fe³⁺ concentration ratios were determined from the fits to the spectra. Fitting of subspectra was accomplished with the idea to find assignments of Fe²⁺ and Fe³⁺ doublets in agreement with X-ray results. The fraction of Mn²⁺ substituting Fe²⁺ on M1 sites could be estimated.  相似文献   

<Superscript>57</Superscript>Fe Mössbauer measurements and electronic structure calculations on natural lawsonites     

S.-U. Weber  M. Grodzicki  C. A. Geiger  W. Lottermoser  G. Tippelt  G. J. Redhammer  M. Bernroider  G. Amthauer 《Physics and Chemistry of Minerals》2007,34(1):1-9

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. ⁵⁷Fe Mössbauer spectra are consistent with the assumption that high-spin Fe³⁺ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with ⁵⁷Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe²⁺. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe³⁺ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe³⁺ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe²⁺. However, it cannot be excluded that Fe²⁺ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H₂O molecule.  相似文献   

Crystal chemistry of ferric iron in (Mg,Fe)(Si,Al)O<Subscript>3</Subscript> majorite with implications for the transition zone     

C. A. McCammon  N. L. Ross 《Physics and Chemistry of Minerals》2003,30(4):206-216

Fifteen samples of (Mg,Fe)SiO₃ majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O₃ majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe³⁺ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe²⁺–Fe³⁺ charge transfer, where band intensity increases with increasing Fe³⁺ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe³⁺ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO₃ majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe³⁺ concentration of (Mg,Fe)(Si,Al)O₃ majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O₃ perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.  相似文献   

Distribution and Influence of Iron Phases on the Physico—Chemical Properties of Phyllosilicates     

MERVATSAIDHASSAN SAYEDMAHMOUDSALEM 《中国地球化学学报》2002,21(1):29-39

Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-band Electron Spin Resonance(ESR) spectroscopies.The purity of the samples and the degree of structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm^-1 assigned as Al-OH-Fe which is present after chemical dissolution of free iron.The Moessbauer spectra of these clays sow two doublets with isomer shift and quadrupole splitting typical of octahedral coordinated Fe^3 ,in addition to third doubler with hyperfine parameter typical of Fe^2 in the spectra of Abu-Had kaolinite (H)sample.6-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octaedral symmetry and as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activaiton of investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,amounts and site occupation of Fe associated with kaolinite samples show a negative correlation with the parameters used to describe the degree of crystalline perfection,color,brightness and vitrification range of these kaolinite samples.  相似文献