Spectroscopic active IVFe3+–VIFe3+ clusters in spinel–magnesioferrite solid solution crystals: a potential monitor for ordering in oxide spinels

Optical absorption spectra (OAS) of synthetic single crystals of the solid solution spinel sensu stricto (s.s.)–magnesioferrite, Mg(Fe³⁺Al_1???y)₂O₄ (0?y?≤ 0.3), have been measured between 12 500 and 28 500?cm^?1. Chemical composition and Fe³⁺ site distribution have been measured by electron microprobe and Mössbauer spectroscopy, respectively. Ferric iron is ordered to the tetrahedral site for samples with small magnesioferrite component, and this ordering is shown to increase with magnesioferrite component. The optical absorption spectra show a strong increase in band intensities with Fe³⁺→Al substitution. Prominent and relatively sharp absorption bands are observed at 25 300 and 21 300?cm^?1, while less intense bands occur at 22 350, 18 900, 17 900 and 15 100?cm^?1. On the basis of band energies, band intensities and the compositional effect on band intensity, as well as structural considerations, we assign the observed bands to electronic transitions in ^IVFe³⁺–^VIFe³⁺clusters. A linear relationship (R ²= 0.99) between the α_net value of the absorption band at 21 300?cm^?1 and [^IVFe³⁺]?·?[^VIFe³⁺] concentration product has been defined: α_net=2.2?+?15.8 [^IVFe³⁺]?·?[^VIFe³⁺]. Some of the samples have been heat-treated between 700 and 1000?°C to investigate the relation between Fe³⁺ ordering and absorption spectra. Increase of cation disorder with temperature is observed, which corresponds to a 4% reduction in the number of active clusters. Due to the high spatial resolution (??～?10?μm), the OAS technique may be used as a microprobe for determination of Fe³⁺ concentration or site partitioning. Potential applications of the technique include analysis of small crystals and of samples showing zonation with respect to total Fe³⁺ and/or ordering.     

Characterization of a natural magnetite

Single crystals of a rock magnetite were separated from steatite cobbles collected in a geological site near the city of Serro (18° 36′ 47′′ S 43° 22′ 46′′ W), Minas Gerais, Brazil. A typically well-shaped magnetite single crystal was characterized by chemical analysis, ⁵⁷Fe Mössbauer spectrometry at 300, 77 and 4 K and under an applied magnetic field of 6 T at 10 K, magnetization measurements and electronic microprobe. From Mössbauer data, the sample is stoichiometric with a tetrahedral and octahedral site occupancy ratio of 1:2. Elemental chemical analysis and point-to-point electron microscope probing show some inclusions of lamellar ilmenite (≤ 1 mass%) randomly distributed throughout the magnetite matrix, and also that the magnetite matrix is constituted only by Fe²⁺ and Fe³⁺, with no isomorphic substitution. Results are discussed on the basis of the magnetization curve and of the temperature dependence of the AC magnetic susceptibility. The Verwey transition occurs in the temperature range of 100–115 K, observed by a sudden change in the temperature dependence of the magnetization.     

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

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.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.     

Influence of cation distribution on the optical absorption spectra of Fe3+-bearing spinel s.s.–hercynite crystals: evidence for electron transitions in VIFe2+–VIFe3+ clusters

Flux-grown Fe³⁺-bearing spinel s.s.–hercynite solid-solution crystals, (Mg _1-y Fe²⁺ _y )Al₂O₄ (0 < y≤ 1), have been investigated by means of electron microprobe technique and Mössbauer and electronic spectroscopy. Obtained results show that different electronic processes cause intense optical absorption bands in the near-infrared spectral region. In addition to an electronic d–d transition in single-ion ^IVFe²⁺, observed at 5200 cm^?1, intense and broad bands at 9500 and 14 500 cm^?1 are assigned to exchange-coupled pair (ECP) and intervalence charge-transfer (IVCT) transitions in ^VI Fe ^{2+ VI} Fe³⁺clusters, respectively. The net linear extinction coefficients of these bands (α) were calibrated against Fe²⁺ and Fe³⁺ concentrations and site distributions previously defined by combined microchemical, Mössbauer, and XRD structural refinement data. The following expressions were obtained: where α is measured in cm^?1 and concentrations are expressed in mol?l^?1. The present results show that optical absorption spectroscopy may be used as a probe to obtain high spatial resolution (?～ 10 μm) information on Fe²⁺ ordering as well as on Fe³⁺ concentrations in minerals belonging to the spinel group.     

Mössbauer effect study of anapaite, Ca2Fe2+(PO4)2 · 4H2O, and of its oxidation products

Mössbauer spectra (MS) of anapaite (Ca₂ Fe²⁺(PO₄)₂?·?4H₂O) and of a sample after being immersed in a 4% H₂O₂ solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420?K and 11 to 300?K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe²⁺ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370?K?±?25?K and 340?K?±?25?K, and the intrinsic isomer shifts as 1.427?±?0.005?mm/s and 1.418?±?0.005?mm/s respectively. From the external-field (60?kOe) MS recorded at 4.2 and 189?K for the non-treated sample, the principal component V _zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η?≈?0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE _Q(T), cannot be interpreted on the basis of the thermal population of the ⁵ D electronic levels resulting from the tetragonal compression of the O₆ co-ordination. The low-temperature linear behaviour of ΔE _Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2?K produces magnetic hyperfine splitting with effective hyperfine fields of ?136, ?254 and ?171?kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H₂O₂ concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe²⁺ (～6.5%) is converted into Fe³⁺.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural sinhalites

Natural sinhalites, MgAlBO_4, from the Ratnapura District, Sri Lanka, and from Bodnar Quarry near Hamburg, Sussex Co., New Jersey, USA, have been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine the oxidation state and site occupancy of iron in the sinhalite structure. The samples contain about 3.35 and 1.46 wt% of total iron oxide, respectively. The structure refinement is successful and reproduces the total iron content provided that the substitution of Mg²⁺ by Fe²⁺ on the M2 position only is assumed. The ⁵⁷Fe Mössbauer spectra at 77, 293, 573 and 773 K can be resolved into two doublets with hyperfine parameters common for octahedrally coordinated high-spin Fe²⁺. There is no evidence for iron in the tetrahedral site. Electronic structure calculations in local spin density approximation yield hyperfine parameters for Fe²⁺ on the M2-site at 0, 293, 573 and 773 K in quantitative agreement with experiments. Calculated spectroscopic properties for Fe²⁺ on the M1-site are at variance with the experimental data and, thus, indicate that substitution of Al³⁺ by Fe²⁺, if occurring at all, must be accompanied by considerable local expansion and distortion of the M1-octahedron.     

Characterization of beryl (aquamarine variety) by Mössbauer spectroscopy

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.     

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.     

Mössbauer milliprobe studies of small mineral samples with a silicon drift detector

Analysis of ⁵⁷Fe transmission Mössbauer spectra collected on a system where the proportional counter has been replaced with a silicon drift detector (SDD) to test milliprobing of mineral samples is described. In the region of the 14.4 keV Mössbauer line the detector has about 70% efficiency and is capable of delivering spectroscopic information with a high energy resolution and high counting rate. Satisfactory results are obtained from a phase analysis of mixtures of olivine and ilmenite in the proportion 97:3, 99:1 wt%, where in the latter case 2.4 μg of Fe³⁺ in the form of hematite was found in the ilmenite. New perovskite-type minerals (Pb_1.33Ba_0.67Fe₂O₅, Pb_1.33Sr_0.67Fe₂O₅ and Pb_1.33Ba_0.33Sr_0.33Fe₂O₅), synthesised by a combustion method, were studied by X-ray diffraction and Mössbauer spectroscopy as well. The advantage of the system with SDD compared to a conventional Mössbauer spectrometer equipped with a proportional counter as a detector is demonstrated for the perovskite samples. The Mössbauer set-up with the silicon drift detector may be successfully used for a wide range of materials containing a negligible amount of iron.     

Low temperature magnetism and Mössbauer spectroscopy study from natural goethite

In this work a magnetic characterization was made of natural goethite from Burkina Faso, Africa, by using low temperature magnetization curves, hysteresis loops, Mössbauer spectroscopy at room temperature and 4.2 K, and AC susceptibility from 10 to 400 K. The samples are from two distinct geological sites that underwent different weathering processes. All measurements point to the occurrence of typical high coercivity goethite. Through Mössbauer spectroscopy sample BL44, from Gangaol, northeast Burkina Faso showed relaxation effects due to a wide distribution of grain size, including superparamagnetism threshold. AC susceptibility also supports this interpretation. The sample BL50 from Bonga in Burkina Faso is associated with lateritic Ni and in addition to goethite this sample also contained magnetite, as determined by Verwey transition in low temperature measurements as well as a small content of hematite identified by Mössbauer spectroscopy.     

<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.     

Characterization of a chalcopyrite from Brazil by Mössbauer spectroscopy and other physicochemical techniques

We studied a chalcopyrite from a Cu ore deposit in Rio Grande do Sul, Brazil, by Mössbauer spectroscopy at room temperature and 110 K. Supporting methods to check for sample purity and to characterize further sample properties were slow-scanning X-ray powder diffraction and optical and microprobe analyses of polished sections of selected grains. Chemical analyses obtained using a scanning electron microscope equipped with an energy-dispersive X-ray spectrometer showed the sample to consist of homogeneous and essentially stoichiometric chalcopyrite (CuFeS₂). Mössbauer spectra taken at both the above temperatures consist of asymmetric magnetically ordered patterns with unequal intensities of the line pairs 1–6 and 2–5, pointing to the existence of non-equivalent or multiple Fe sites. Least-squares fittings evidenced that the resonance intensity ratio of subspectrum with lower quadrupole shift (indicative of a more symmetric environment) to that with higher shift is 69:31, at room temperature, and 68:32, at 110 K. Rietveld refinement of the XRD data indicates the existence of tetragonal [a = 0.52855(1) and c = 1.0412(1) nm] and cubic [a ₀ = 0.5273(2) nm] modifications in a proportion of 74:26, in good agreement with the Mössbauer data. The saturation magnetization of the sample was 32.7 J/(T kg), confirming the oxidation state of Fe as trivalent and pointing to little to no spin canting.     

Activation energy of annealed metamict gadolinite from 57Fe Mössbauer spectroscopy

Gadolinite, REE₂FeBe₂Si₂O₁₀, is commonly metamict. ⁵⁷Fe Mössbauer annealing studies of fully metamict gadolinite from Ytterby, Sweden, have been completed in argon atmosphere from 873 to 1473 K. This technique has rarely been employed in studies of metamict minerals. Changes in the experimental parameters of Mössbauer spectra are sensitive indicators of the thermal recrystallization process of metamict gadolinite and revealed two stages of the structural recovery: a major stage from 873 to 1073 K and a slower recovery stage from 1133 to 1473 K. These observations are confirmed by X-ray powder diffraction. In relation to the first stage, the exponential behaviour of the changes in the Mössbauer parameters can be used for deriving the activation energy E _a of the recrystallization process. The calculated value E _a =1.97 eV in argon atmosphere explains the common occurrence of gadolinite in the fully or partially metamict state. Results of Mössbauer spectroscopy suggest that the recrystallization of metamict gadolinite is a displacive transition that involves rotation and translation of SiO₄ and BeO₄ to their normal positions associated with removal of OH groups from the structure.     

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

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.     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

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.     

Study of Al-substituted hematites, prepared from thermal treatment of lepidocrocite

A study of the characteristics of the Morin transition in aluminous hematites, α-(Fe_1?xAl_x)₂O₃, produced from thermally transformed lepidocrocites, is reported. Six compositions with Al contents between 0.2 and 10 at% have been considered. It is argued that these samples present the advantage that they contain smaller amounts of hydroxyl and water as compared to hematites obtained by other preparation methods. The samples were characterised by a variety of conventional techniques, including thermal analyses, X-ray diffraction, FTIR, TEM/EDX, BET surface-area measurements and diffuse reflectance spectroscopy. All results indicate that the Al is structurally incorporated in the hematite lattices. Transmission Mössbauer spectra were recorded at various temperatures between 80?K and room temperature in order to precisely determine the Morin-transition region and the spin structure in both the low-temperature antiferromagnetic and weakly ferromagnetic states. It was found that the Morin-transition temperatures are markedly higher as compared to similar hematites made from aluminous goethites and that a transition phenomenon persists to an Al substitution of up to at least 10 at%. This different behaviour is ascribed to lower concentrations of structural hydroxyl groups in these lepidocrocite-based hematites.     

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 characteristics,mineralogy and isotopic age (Rb-Sr,K-Ar) of Upper Riphean glauconites from the UK Formation,the southern Urals

Comprehensive mineralogical analysis, Mössbauer spectroscopy and isotopic-geochronological study have been carried out for globular phyllosilicates (GPS) of glauconite group from the Uk Formation, the second one below the top of the Upper Riphean stratotype in the southern Urals. Glauconites have been sampled in the Kurtaza and Kulmas sections remote from each other in the Alatau anticlinorium that corresponds to western facies zone of the Bashkirian meganticlinorium. As is shown, size and density monomineral fractions of globules are represented by Al-glauconite according to established structural formula. The isotopic (Rb-Sr and K-Ar) dating of glauconites from the Uk Formation is performed for the first time along with computer simulation of cation arrangements in their crystal lattice and comparison of the results obtained with data of Mössbauer spectroscopy. It has been assumed by simulation that origin and transformation of the Rb-Sr and K-Ar systems in glauconite are concurrent to stages in structural evolution of this mineral, which have been controlled by geological and geochemical events in the history of sedimentary successions. The approach has been aimed at recognition of stratigraphically meaningful isotopic dates corresponding to the glauconite formation at the stage of the early diagenesis close to sedimentation time and the “rejuvenated” dates characterizing ages of subsequent geological events. The comparison of simulated cation arrangements with data of Mössbauer spectroscopy shows that the Rb-Sr (663 ± 9 Ma) and K-Ar (669 ± 16 Ma) dates established for glauconites correspond to the time of early diagenesis in their host sediments, being suitable for age assessment of the Uk Formation. The dates obtained are of interregional and wider significance, as they must be taken into consideration when constructing the general curve of Sr isotope variations in the Late Riphean oceans.     

A time-minimizing hybrid method for fitting complex Mössbauer spectra

The present study includes results of the application of a program consisting of a genetic algorithm routine and a conventional refinement part (“hybrid method”) for the evaluation of Mössbauer spectra published elsewhere. It is shown that the saving of total evaluation time compared with conventional refinement routines is very high due to the rapid finding of adequate starting parameters. Contrary to a recently published work on a similar topic our algorithm provides solutions of the combined interaction Hamiltonian with a minimum of conventional input data.