Mössbauer spectra and magnetic features of ilvaites

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.     

A neutron powder diffraction study of the crystal and magnetic structures of ilvaite from 305 K to 5 K — a mixed valence iron silicate with an electronic transition

The crystal and magnetic structures of ilvaite Ca(Fe²⁺, Fe³⁺)Fe²⁺Si₂O₇O(OH) have been obtained by profile refinement of high resolution neutron powder data from a natural sample from Seriphos, Greece. Below about 400 K an electronic transition from an itinerant to an ordered state is expected, with the structure changing from orthorhombic to monoclinic. The structure remains monoclinic P2 ₁/a down to 5 K, with Fe²⁺ almost completely ordered on one of the A-sites and Fe³⁺ on the other: the ordering may increase with decreasing temperature. The B-site contains Fe²⁺ plus a small amount of Mn²⁺ impurity. There are two magnetic transitions, at 116 K and 40 K: at 80 K the Fe²⁺ and Fe³⁺ spins on the A-sites along one infinite c-axis chain are parallel, and antiparallel to those along the adjoined edge-sharing centrosymmetrically related chain. The spin vectors are all perpendicular to the plane of these chains, i.e. almost parallel to the crystallographic b-axis. At 5 K, this order is maintained, but the Fe²⁺ spins on the B-sites order antiferromagnetically as well, again almost along the b-axis. These results explain the earlier Mössbauer and magnetisation measurements.     

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

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.     

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

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.     

Mössbauer and molecular orbital study of chlorites

The different Fe²⁺ lattice sites in iron-rich chlorites have been characterized by Mössbauer spectroscopy and molecular orbital calculations in local density approximation. The Mössbauer measurements were recorded at 77?K within a small velocity range (±3.5?mm?s^?1) to provide high energy resolution. Additionally, measurements were recorded in a wider velocity range (±10.5?mm?s^?1) at temperatures of 140, 200, and 250?K in an applied field (7?T) parallel to the γ-beam. The zero-field spectra were analyzed with discrete Lorentzian-shaped quadrupole doublets to account for the Fe²⁺ sites M1, M2, and M3 and with a quadrupole distribution for Fe³⁺ sites. Such a procedure is justified by the results obtained from MO calculations, which reveal that different anion (OH^?) distributions in the first coordination sphere of M1, M2, and M3 positions have more influence on the Fe²⁺ quadrupole splitting than cationic disorder. The spectra recorded in applied field were analyzed in the spin-Hamiltonian approximation, yielding a negative sign for the electric field gradient (efg) of Fe²⁺ in the M1, M2, and M3 positions. The results of the MO calculations are in quantitative agreement with experiment and reveal that differences in the quadrupole splittings (ΔE _Q ), their temperature dependence and in the isomer shifts (δ) of Fe²⁺ in M1, M2, and M3 positions can theoretically by justified. Therefore, the combined Mössbauer and MO investigation shows that the three Fe²⁺ lattice sites in the chlorites investigated here can be discriminated according to their ΔE _Q -δ parameter pairs. With the calculated average iron-oxygen bond strength, the MO study provides an explanation for the observed trend that the population of the three lattice sites by Fe²⁺ increases according to the relation M1?相似文献   

The MgCr2O4–MgFe2O4 solid solution series: effects of octahedrally coordinated Fe3+ on T–O bond lengths

The influence on the spinel structure of Fe³⁺ → Cr substitution was studied in flux-grown synthetic single crystals of the magnesiochromite–magnesioferrite (MgCr₂O₄–MgFe₂O₄) solid solution series. Samples were analysed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption and Mössbauer spectroscopy. With the exception of iron-poor samples (3–12 mol-% MgFe₂O₄), optical absorption and Mössbauer spectra show that iron occurs almost exclusively as trivalent Fe in the present samples. A very intense and broad absorption band at ca 7,800 cm^?1 dominates the optical absorption spectra of samples with higher Fe-contents. The appearance of this band is related to a distinct structural disorder of Fe³⁺ and a development of magnetic ordering as demonstrated by Mössbauer spectra. Profound composition-related changes are observed in the Mössbauer spectra, which are magnetically unsplit in the range 2–41 mol-% magnesioferrite, but become magnetically split in the range 59–100 mol-% magnesioferrite. Structural parameters a ₀ and M–O increase with magnesioferrite content and inversion degree, while u and T–O decrease. Our study confirms the previously reported (Lavina et al. 2002) influence of Fe³⁺ at the M site on T–O bond lengths in the spinel structure.     

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

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.     

Mössbauer spectra of Fe x O (x>0.95)

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.     

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

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.     

Intracrystalline fractionation of Fe in synthetic (Fe, Mg, Zn) - bearing staurolite: a Mössbauer spectroscopic study

⁵⁷Fe-Mössbauer spectra of eleven Fe-Mg-bearing staurolite samples, synthesized at 5, 20 and 25 kbar and 680°C, ranging in composition from x_Fe?=1.00 to x_Fe?=0.15, and of two Zn-Fe-bearing staurolite samples, synthesized at 20 kbar and 700°C with x_Fe?=0.10 and x_Fe?=0.32 were collected at room temperature. The spectra reveal that about 80% of Fe_tot (in case of Fe-Mg-bearing staurolite) and about 70% of Fe_tot (in case of Fe-Zn-bearing staurolite) are located as Fe²⁺ at the three subsites Fe1, Fe2 and Fe3 of the tetrahedral T2-site. The refinement of the spectra results in almost identical values for the isomer shift (IS) (±1.0 mm/s) but significantly different values for the quadropole splitting (QS) for the three subsites which is in accordance with the different distortions of these sites. About 8% of Fe_tot (in case of Fe-Mg-bearing staurolite) and 13% of Fe_tot (in case of Fe-Zn-bearing staurolite) are located as Fe²⁺ at the octahedral M4 site, while the remainder percents of Fe_tot indistinguishably occur as Fe²⁺ at the octahedral M1 and M2 sites of the kyanite-like part of the structure. Within the whole Fe-Mg-staurolite solid solution series the Mössbauer parameters QS of the sites M4 and (M1, M2) vary systematically with composition whereas IS remains constant. There is a high negative correlation of the total Mg-content with Fe-occupation of all the Fe-bearing sites indicating a continuous substitution of Fe²⁺ by Mg on all these sites. Synthetic Fe-staurolites show no increasing occupation of the octahedral sites by two-valent cations with pressure, as was assumed by several authors.     

Temperature-dependent Fe2+–Mn2+ order–disorder behaviour in amphiboles

The partitioning of Fe and Mn between the large M(4) site and the octahedral sites, M(1,2,3) in the amphibole structure has been investigated in two natural manganogrunerites of compositions Ca_0.1Mn_1.9 Mg_1.25Fe²⁺ _3.56Fe³⁺ _0.38Si_7.81O₂₂(OH)₂ and Ca_0.24Mn_1.57 Mg_2.27 Fe²⁺ _2.76Fe³⁺ _0.32Si_7.84O₂₂(OH)₂. The long-range cation distribution in the two samples has been elucidated by in situ neutron powder diffraction revealing that Mn is preferentially ordered onto M(4) ? M(2) >M(1) >M(3) in both samples. Partitioning of Mn from M(4) into the octahedral sites begins at 350 °C, with site exchange energies of ?16.6 kJ mol^?1 and ?14.9 kJ mol^?1, in samples containing 1.90 and 1.57 Mn apfu, respectively. Mössbauer and infrared spectroscopy have been used to study the samples at room temperature, and Mössbauer data agree well with the diffraction results, confirming that high-temperature cation distributions are retained during cooling. The fine structure in the hydroxyl-stretching region of the IR absorption spectra has been used to discuss qualitatively the site occupancies of the coordinating M(1)M(3)M(1) triplet, linked by O(3). On the basis of such modelling, we conclude that a degree of local clustering is present in both samples.     

Mixed valence of iron in minerals with cation clusters

The valence and distribution of iron in vivianite, lazulite, babingtonite, rockbridgeite, acmite, aegirine-augite, hedenbergite, and ilvaite were studied with optical and Mössbauer spectroscopy. Optically activated intervalence charge transfer between Fe²⁺ and Fe³⁺ in neighboring sites through common edges or faces is observed in all these minerals irrespective of the polymerization of the iron-oxygen polyhedra ranging from finite clusters to infinite structural units. However, a distinct decrease occurs in the energy of the corresponding optical absorption band with increasing number of Fe²⁺ and Fe³⁺ ions involved in the charge transfer process. Thermally activated electron delocalization between Fe²⁺ and Fe³⁺ occurs only if Fe²⁺ and Fe³⁺ occupy crystallographically equivalent or geometrically very similar neighboring sites which share common edges to form extended structural units such as the ribbon in ilvaite. If the Fe-O polyhedra form finite clusters of two, three, or four polyhedra (e.g., in vivianite, lazulite, and babingtonite, respectively) no thermally-activated mixed-valence states of iron are observed. In aegirine, extended regions of the M1 chain are statistically occupied by Fe²⁺ and Fe³⁺ giving rise to thermally-activated electron delocalization in addition to the intervalence band in the optical absorption spectrum. The intensity of the optical intervalence absorption has been measured in a number of systems: ? values range from 60 to 210.     

Determination of [Fe2+]/[Fe3+]-ratios in arfvedsonite by Mössbauer spectroscopy

The Mössbauer absorption spectra of arfvedsonite are composed of three quadrupole doublets which are ascribed to Fe²⁺ in M₁ and M₂ sites and to Fe³⁺ in M₂ sites. The relative intensities of the resonances are a measure of the distribution of iron at the different sites, but it is necessary to correct for a difference between the recoil-free fractions. At room temperature [Fe²⁺] seems detected with an efficiency of only about 85% of that of [Fe³⁺]. Results of [Fe²⁺]/[Fe³⁺] determinations by Mössbauer spectroscopy and by wet chemical analysis of a series of arfvedsonite samples, separated from various rocks from the Ilimaussaq intrusion, south Greenland, are compared and agree reasonably well.     

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

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).     

Iron in hibonite: a spectroscopic study

A combined polarized optical absorption and ⁵⁷Fe Mössbauer spectroscopy study of inhomogeneous, Fe and Ti-bearing terrestrial hibonite (Madagascar) has been carried out. Mössbauer data were also obtained on synthetic material prepared under different fo₂ inconditions. A strong band at 5400 cm^-1 in the near-infrared spectra is attributed to spin-allowed d-d transitions of Fe²⁺ occupying tetrahedral sites within the spinel blocks of the hibonite crystal structure. There is agreement with the Mössbauer results, showing that ferrous iron orders onto a single, low-coordinated crystallographic site. Ferric iron is distributed over several positions, but shows strongest preference for the large bipyramidal site located outside the spinel blocks. The colour and pleochroism of hibonite in thin section is related to a prominent UV absorption edge, and several broad absorption bands in the visible spectrum ascribed to charge-transfer transitions involving Fe²⁺, Fe³⁺ and Ti⁴⁺.     

Structural variation of babingtonite depending on cation distribution at the octahedral sites

Babingtonite, Ca₂Fe²⁺Fe³⁺[Si₅O₁₄(OH)] (Z?=?2, space group $ P\overline{1} $ ) from Yakuki mine (Japan), Grönsjöberget (Sweden), Kandivali Quarry (India), Baveno Quarry (Italy), Bråstad Mine (Norway), and Kouragahana (Japan), and manganbabingtonite, Ca₂(Mn²⁺, Fe²⁺)Fe³⁺[Si₅O₁₄(OH)], from Iron Cap mine (USA) were studied using electron-microprobe analysis (EMPA), ⁵⁷Fe Mössbauer analysis and single-crystal X-ray diffraction methods to determine the cation distribution at M1 and M2 and to analyze its effect on the crystal structure of babingtonite. Although all studied babingtonite crystals are relatively homogeneous, chemical zonation due to mainly Fe ? Mn substitution is observed in manganbabingtonite. Mössbauer spectra consist of two doublets with isomer shift (I.S.)?=?1.16–1.22 mm/s and quadrupole splitting (Q.S.)?=?2.33–2.50 mm/s and with I.S.?=?0.38–0.42 mm/s and Q.S.?=?0.82–0.90 mm/s, assigned to Fe²⁺ and Fe³⁺ at the M1 and M2 octahedral sites, respectively. The determined ratio of Fe²⁺/total Fe in manganbabingtonite (0.26) was smaller than that in the others (0.35–0.44) because of high Mn²⁺ content instead of Fe²⁺. The unit-cell parameters of babingtonite are a?=?7.466–7.478, b?=?11.624–11.642, c?=?6.681–6.690 Å, α?=?91.53–91.59, β?=?93.86–93.94, γ?=?104.20–104.34º, and V?=?560.2–562.3 Å³, and those of manganbabingtonite are a?=?7.4967(3), b?=?11.6632(4), c?=?6.7014(2) Å, α?=?91.602(2), β?=?93.989(2), γ?=?104.574(3)º, and V =565.09(5) ų. Structural refinements converged to R ₁ values of 1.64–3.16 %. The <M1-O> distance was lengthened due to the substitution of large octahedral cations such as Mn²⁺ for Fe²⁺. The increase of the M1-O8, M1-O8’ and M1-O13 lengths with mean ionic radii is slightly more pronounced than of the other M1-Oi lengths. The lengthened M1-O13 distance leads the positive correlation between Si5-O15-Si1 angle and M1-O13 distance. The increase of Si2-O3-Si1 and Si5-O12-Si4 angles due to the increase of mean ionic radius of M2 is also observed.     

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

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.     

Evaluation of ferrous and ferric Mössbauer fractions. Part II

Mössbauer fractions f are reported for various ferrous- and/or ferric-containing oxides, hydroxides, silicates, and phosphates to extend the list previously reported by De Grave and Van Alboom (1991). The f fractions were evaluated from the experimental temperature dependencies of their center shifts, assuming the Debye model for the lattice vibrations. For most Fe²⁺ sites the characteristic Mössbauer or lattice temperatures Θ_M are in the range 300–400 K, while those for Fe³⁺ sites are close to or exceed 500 K, implying significantly higher f fractions for Fe³⁺ than for Fe²⁺, in particular at room temperature. A correlation between Θ_M and the coordination type, or, for a given valence state and coordination type, between Θ_M and the mineral type is, however, not obvious.     

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

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.     

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

(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.