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1.
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.  相似文献   

2.
Practically identical Mössbauer spectra have been obtained for 40 ferromanganese nodules from a wide variety of marine and fresh-water locations. None of the nodules examined contains more than one weight percent Fe2+, so no more than a few percent of the total iron in these nodules can be Fe2+. Most of the iron is present as Fe3+ in paramagnetic or superparamagnetic oxide phases, although hysteresis loops show the presence of small amounts of ferromagnetic phases not detected by the Mössbauer technique.  相似文献   

3.
In the present work, we investigate the iron oxides and oxyhydroxides behavior and evolution, related to the geochemical behavior of some metals, which could be retained as solid phases in the sediments from an urban water reservoir lake, placed in Taiaçupeba, Great São Paulo, Brazil. These tasks were performed by the establishment of a proceduring setting for environmental monitoring analysis through Mössbauer spectroscopy measurements associated to hysteresis loops measurements and chemical analysis [X-ray fluorescence (XRF)]. We inferred the possibility of goethite occurrence in broad particle size distribution (5–50 nm), and related to ferrihydrite, and small grain-size hematite (about 8 nm). The magnetometry results pointed to the paramagnetic/superparamagnetic behavior of the magnetic phases present in the samples and also suggested the occurrence of small grain-size magnetite. We also verified the presence of clay minerals related to Fe, as well as the occurrence of Fe3+ and/or Fe2+ in short-range structural order. Through a straight correlation among Mössbauer spectra data gained at T = 77 K and Al-metal, metal-Fe molar ratios, provided through XRF data, we found remarkable indications of interference on meta-stable phases evolution to its final products. Such results can be pointing for evidences about the possible isomorphic replacing and/or adsorption of Al and other metals in goethite and hematite.  相似文献   

4.
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   

5.
We investigated the valence state and spin state of iron in an Al-bearing ferromagnesian silicate perovskite sample with the composition (Mg0.88Fe0.09)(Si0.94Al0.10)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   

6.
Undisturbed core samples of Recent sediments from the Wash tidal flats, East Anglia, England, obtained using a Delft corer, were studied with special reference to the diagenesis and geochemical behaviour of iron. The Mössbauer effect in 57Fe was used to monitor the distribution of Fe between different phases as a function of depth, together with the magnetic mineralogy and palaeomagnetic properties.The cores consist of, successively downwards: 0.36 m brown clay; 1.5 m finely laminated silts and fine sands, and 7.14 m homogeneous fine sands. The dominant minerals are quartz, feldspar, calcite and clay minerals, and chemical analysis for Al, Si, Mg, Mn, Ca, Fe, Na, K showed variations closely linked to lithological changes. Illite is the most abundant clay mineral (mean 48%), followed by mixed layer illite-montmorillonite and montmorillonite, kaolinite and chlorite. Chlorite is the major iron-bearing clay mineral and represents 4 to 10% of the <2 μm fraction throughout the core. Sulphide minerals are present throughout the core, including framboidal pyrite.Computer fit analysis of the Mössbauer spectra of best quality showed contributions from Fe2+ and Fe3+ in clay minerals (essentially chlorite), low-spin Fe2+ in pyrite, and magnetically ordered iron in greigite (Fe3S4). Systematic variations, as a function of sample depth, indicate a relative increase in the amount of Fe in pyrite at the expense of the clay minerals.Magnetite and titanium-bearing magnetite are the carriers of natural magnetic remanence in these sediments.The direction and intensity of natural remanence in the samples compare well with the known secular variation of the Earth's magnetic field derived from the historic-archaeomagnetic record and this enables the samples to be dated and sedimentation rates to be determined (1.5 mm yr?1 for the upper 2 m and ~7.7 mm yr?1 for the lower 7 m).  相似文献   

7.
Mössbauer effect and magnetisation measurements show strong evidence that the principal form of native and introduced iron in Victorian brown coals is as isolated Fe3+ ions octahedrally coordinated to a range of oxygen-containing ligands. The mean iron-iron separation is less than expected from a uniform distribution, but there is strong evidence against clustering. All experimental evidence is consistent with these iron ions being located in the water bridges between the coal micelles. Although the Fe3+ ions remain paramagnetic down to 4.2 K, magnetic coupling between nearby Fe3+ ions causes slow paramagnetic relaxation in the low temperature Mössbauer spectra.  相似文献   

8.
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 (Pb1.33Ba0.67Fe2O5, Pb1.33Sr0.67Fe2O5 and Pb1.33Ba0.33Sr0.33Fe2O5), 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.  相似文献   

9.
Two samples of cronstedtite, a mixed valence serpentine with ideal formula {Fe 2 2+ ,Fe3+}[Si,Fe3+]O5(OH)4, have been examined by X-ray and neutron diffraction, thermopiezic analysis, magnetization and susceptibility measurements and Mössbauer spectroscopy. The conductivity is thermally activated, with activation energies of 0.25 eV in the basal plane and 0.37 eV in the perpendicular direction. The shape of paramagnetic Mössbauer spectra above 200 K is influenced by charge fluctuations in octahedral sites and fits of spectra at temperatures up to 410 K with a stochastic relaxation model give an activation energy of 0.19 eV. Static charge ordering sets in progressively below about 100 K. Cronstedtite orders antiferromagnetically below 12 K in a structure with antiferromagnetic octahedral sheets and moments perpendicular to the a-axis. Magnetic and charge-ordered structures are proposed for the ideal composition.  相似文献   

10.
(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   

11.
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 Vzz, 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   

12.
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.  相似文献   

13.
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   

14.
The mixed valence iron silicate deerite, Fe 6 2+ Fe 3 3+ O3[Si6O17](OH)5 whose crystal structure has only recently been fully determined, had been previously examined by both susceptibility measurements and Mössbauer spectroscopy. We reinterpret the Mössbauer measurements from Frank and Bunbury and show that all contradictions between the phenomena, observed in their experiments, and the mineralogical structure disappear when one accepts a thermally activated electron delocalisation associated with Fe2+ ? Fe3+ charge transfer.  相似文献   

15.
Mössbauer spectra were recorded at multiple temperatures between 80 and 293 K to study the nature of Fe3+ in Fe0.05Mg0.95SiO3 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: ΘM (Fe2+)=365±52 K and ΘM (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   

16.
Despite a large number of studies of iron spin state in silicate perovskite at high pressure and high temperature, there is still disagreement regarding the type and P–T conditions of the transition, and whether Fe2+ or Fe3+ or both iron cations are involved. Recently, our group published results of a Mössbauer spectroscopy study of the iron behaviour in (Mg,Fe)(Si,Al)O3 perovskite at pressures up to 110 GPa (McCammon et al. 2008), where we suggested stabilization of the intermediate spin state for 8- to 12-fold coordinated ferrous iron ([8–12]Fe2+) in silicate perovskite above 30 GPa. In order to explore the behaviour in related systems, we performed a comparative Mössbauer spectroscopic study of silicate perovskite (Fe0.12Mg0.88SiO3) and majorite (with two compositions—Fe0.18Mg0.82SiO3 and Fe0.11Mg0.88SiO3) at pressures up to 81 GPa in the temperature range 296–800 K, which was mainly motivated by the fact that the oxygen environment of ferrous iron in majorite is quite similar to that in silicate perovskite. The [8–12]Fe2+ component, dominating the Mössbauer spectra of majorites, shows high quadrupole splitting (QS) values, about 3.6 mm s?1, in the entire studied P–T region (pressures to 58 GPa and 296–800 K). Decrease of the QS of this component with temperature at constant pressure can be described by the Huggins model with the energy splitting between low-energy e g levels of [8–12]Fe2+ equal to 1,500 (50) cm?1 for Fe0.18Mg0.82SiO3 and to 1,680 (70) cm?1 for Fe0.11Mg0.88SiO3. In contrast, for the silicate perovskite dominating Mössbauer component associated with [8–12]Fe2+ suggests the gradual change of the electronic properties. Namely, an additional spectral component with central shift close to that for high-spin [8–12]Fe2+ and QS about 3.7 mm s?1 appeared at ~35 (2) GPa, and the amount of the component increases with both pressure and temperature. The temperature dependence of QS of the component cannot be described in the framework of the Huggins model. Observed differences in the high-pressure high-temperature behaviour of [8–12]Fe2+ in the silicate perovskite and majorite phases provide additional arguments in favour of the gradual high-spin—intermediate-spin crossover in lower mantle perovskite, previously reported by McCammon et al. (2008) and Lin et al. (2008).  相似文献   

17.
Red Fe3+-rich and black Fe3+, Fe2+-rich tourmalines have been studied by optical and Mössbauer spectroscopies to determine the optical characteristics of Fe3+ in tourmaline. Prominent optical absorption features at 485 and 540 nm are assigned to transitions of multiple exchange-coupled Fe3+ pairs in several site combinations. These transitions are more intense than those of isolated Fe3+ and are polarized along the vector between the interacting ions, thus permitting site assignments. The 485 nm band occurs at an unusually low energy for Fe3+ in silicate minerals. Similar behavior has been observed in the spectrum of coalingite, Mg10Fe 2 3+ (OH)24CO3·2H2O, in which Fe3+ occurs in related pairs in edge-shared sheets. These lower energies are proposed to result from magnetic exchange in edge-shared geometries. Antiferromagnetic exchange has been confirmed by a variable temperature magnetic susceptibility study of a Kenyan dravite with 3.36 wt percent Fe. The Mössbauer spectrum of this sample is unusual in that it shows a pronounced decrease in width of component peaks from 298 K to 5 K.  相似文献   

18.
Natural sinhalites, MgAlBO4, 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.  相似文献   

19.
We used ‘Voltammetry of MicroParticles’ to investigate electrochemically samples from the Boda Albitic Claystone, a potential site for deep underground disposal of nuclear waste in Hungary. The samples were collected near the surface and at a depth of 1050 m. The electrochemical characterization in acidic media allowed the identification of Fe2+ and Fe3+ ions associated with clays, hematite and pyrite. The cathodic detection of pyrite does not raise special difficulties, but the anodic one is complex and depends on the time of the samples exposure to the atmosphere. This work completes a previous Mössbauer spectroscopy study by clarifying the presence, or absence, of extremely small amounts of pyrite in some samples.  相似文献   

20.
The Fe3+/Σ Fe of twenty-nine experimentally formed, iron-bearing silicate glasses has been determined by wet-chemical and Mössbauer spectroscopic methods from 5–10 mg individual splits of 20–40 mg experimental run products. The wet-chemical and Mössbauer analyses were conducted in two separate laboratories (University of California, Berkeley, and the Geophysical Laboratory, respectively). The Fe3+/Σ Fe ranges from less than 0.2 to 0.96, and the total iron oxide content of the samples, from 2.2 to 34.7 wt %, added as Fe2O3. The interlaboratory comparison shows 70% of the Fe3+/ΣFe analyses from the two methods within the quoted uncertainties (±1 σ) of each other and 83% of the analyses within ±2 σ of each other. Replicate analyses in the current data set result in variations within ±1 σ. These uncertainties are similar to those obtained from several hundred Fe3+/Σ Fe analyses of reequilibrated natural rock and simple system compositions carried out with identical analytical methods in the two laboratories. There is no systematic bias in the results from either of the two techniques. The Fe3+/Σ Fe of silicate glasses can be analyzed, therefore, with equal confidence by either the wet-chemical or the Mössbauer spectroscopic method.  相似文献   

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