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1.
57Fe Mössbauer spectra of iron bearing alumino-silicate glasses are analysed by two complementary methods (SID and x-VBF) especially adapted for the analysis of disordered systems by taking into account distributions of hyperfine Mössbauer parameters. Qualitative and quantitative information about the oxidation state of iron are obtained as well as information about the distribution of local environments of iron. The possibility to separate the signal of ferric iron from that of ferrous iron allows to derive precise redox ratio in favourable cases but also to analyse more sharply the different contributions to Mössbauer spectra. Using two different glass series (feldspar composition, haplo-tonalitic composition), the characteristics of the two methods are described and employed to study the effect of composition, water incorporation and oxidation state on the glass structure. Optical absorption spectroscopy is used to support the interpretation of the Mössbauer spectra in case of the feldspar glasses.  相似文献   

2.
Herein we report on synthetic iron-intercalated vermiculites prepared from a Mg-vermiculite mineral from Santa Olalla, Huelva, Spain, by means of an ion exchange process from aqueous solutions of FeCl2 and FeCl3. Thermogravimetric, X-ray diffraction, magnetic susceptibility and Mössbauer spectral studies have been used to characterize the synthetic iron-intercalated vermiculites. The results suggest that the intercalation process employed induces modifications in both the interlayer spacing and in the octahedral sheet; the disordered structure of the Mg-vermiculite mineral is not altered. The presence of solvated Fe(H2O) n 2+ ions has been shown by the Mössbauer spectroscopy. No magnetic order has been observed between 2 and 300 K neither in the Mg-vermiculite mineral nor in the two synthetic iron-intercalated vermiculites.  相似文献   

3.
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   

4.
A well crystallized and homogeneous specimen of lizardite from Monte Fico, Elba, Italy, has been studied by Mössbauer and Fourier transform infrared (FTIR) spectrometries. One of the aims was the determination of the oxidation state and the distribution of iron in the structure of this reference sample. Mössbauer data indicate the presence of octahedral ferrous iron, octahedral ferric iron and tetrahedral ferric iron (59.9, 31.3 and 8.8% of total iron, respectively). The existence of only one octahedral site, previously suggested by X-ray structure refinement, is confirmed. The occurrence of tetrahedrally coordinated iron is indicated also by FTIR spectrometry, in particular by the presence of an absorption band at 790 cm–1. Based also on new electron microprobe data, the improved crystal chemical formula for lizardite from Monte Fico is: (Mg2.74Fe2+ 0.10Fe3+ 0.05Al0.11)Σ=3.00 ?· (Si1.94Al0.05Fe3+ 0.01)Σ=2.00O5.05(OH)3.95.  相似文献   

5.
Tektite glasses are investigated using 57Fe Mössbauer spectroscopy. Room temperature spectra analysis is performed using two complementary analytical methods based on two-dimensional distributions of both isomer shift and quadrupole splitting. No a priori correlation between the two hyperfine parameters is considered. The first method, based on a shape independent distribution, provides the justification for the Gaussian distribution shape used in the second method. No ferric iron contribution is evidenced by Mössbauer spectra analysis in these samples, although several criteria are used. Ferrous iron sites are shown to be continuously distributed between four- and five-fold co-ordinated sites.  相似文献   

6.
On the basis of a lack of Mössbauer evidence and of a vague interpretation of some i.r. absorptions, Dicksonet al. (1979) conclude that no iron directly bound to humic materials persists after the usually accepted extraction and separation procedures. Many statements in the paper by Dicksonet al. (1979) appear to be contradictory with this conclusion.In this comment the author has tried to demonstrate that Mössbauer spectroscopy alone cannot give an answer to the problem, but needs further spectroscopic and chemical evidence. Mössbauer data, overinterpreted by Dicksonet al. (1979). have been critically discussed, in comparison with similar data previously obtained by various authors. Large spectroscopic—mainly Mössbauer, ESR and i.r.—evidence have been given in order to demonstrate the already well ascertained existence of organically bound iron in natural and synthetic complexes with humic substances.  相似文献   

7.
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   

8.
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   

9.
57Fe Mössbauer spectra have been obtained from samples of humic acid, fulvic acid and kerogen and from the organic material extracted from bituminous chalk with benzene-methanol. The spectra indicate that iron occurs in a trivalent form in the silicate residue of the humic acid fraction, as hydrated ferrous ions associated with the fulvic acid fraction, as pyrite in kerogen and in a form not detectable by Mössbauer spectroscopy in the benzene-methanol extract.  相似文献   

10.
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   

11.
Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-ray Electron Spin Resonance(ESR) spectroscopes.The purity of the samples and the degree of their 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 persist after chemical dissolution of free iron.The Moessbauer spectra of these clays show two doublets with isomer shift and quadrupole splitting typical of octahedrally coordinated Fe^3 ,in addition to third doublet with hyperfine parameter typical of Fe^2 in the spectra of Abu-Had kaolinite (H) sample.Six-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 octahedral symmetry as well as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activation of the investigated montmorillonite samplas 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,the amount and site occupation of Fe associated with kaolinite samples show an inverse correlation with the parameters used to describe the degree of crystallinity perfection,color,brightness and vitrification range of these kaolinite samples.  相似文献   

12.
Iron-rich pyrrhotites proved to be metastable and to decompose at 70–140° C to troilite and pyrrhotite with less iron content as shown by nuclear gamma-resonance (Mössbauer) studies at high temperatures. Coherence of decomposition product lattices was established by studying powder samples textured in a magnetic field. Detailed X-ray powder diffraction and Mössbauer investigations revealed two different mechanisms of transformation in metastable associations. Kinetic phenomena are discussed in terms of a thermodynamic model of two-phase assemblage.  相似文献   

13.
《Engineering Geology》2002,63(1-2):31-38
Orange and reddish patinas developed on a dolostone of the cathedral of Lleida (Spain) have been analysed and characterised by XRD, SEM/EDX, ICP/MS, optical microscopy and Mössbauer spectroscopy. From the experimental data, a biologically induced transformation of the dolomite rock forming crystals, which form a dolomitic patina of micrite size, can be stabilised. Furthermore, the iron oxides as determined by Mössbauer spectroscopy play a role as colouring patina, together with organic matter from the bioactivity. Erosive and constructive processes, as determined through the SEM observations, lead to aesthetical and microstructural changes in the stone surface.  相似文献   

14.
The electric field gradient at the octahedral sites in biotite is calculated by use of the point charge model for the ideal crystal structure. The contribution from the overlap distortions of cation orbitals by the surrounding ligands is included. The calculated values of the ferric quadrupole splittings are in good agreement with those obtained from Mössbauer spectra of micas. The effect of the neighbouring point defects and of real structure features of biotite on the electric field gradient are computed. It has been found that various point defects in adjacent sites produce varying values of ferric quadrupole splittings, which exceed the difference between the ideal parameters at the two distinct octahedral sites. A new interpretation of the biotite Mössbauer spectra is suggested.  相似文献   

15.
The phase and spin transitions in single-crystal monoclinic ferrosilite, FeSiO3, were investigated using X-ray diffraction and Mössbauer spectroscopy up to lower-mantle pressures and room temperature in a helium pressure medium. Using single-crystal X-ray diffraction, we measured the equation of state of ferrosilite up to about 43 GPa. We observed a P21/c-to-C2/c phase transition between 1.5 and 1.7 GPa and a phase transition from C2/c to a distinct P21/c structure between 30 and 34 GPa. With time-domain Mössbauer spectroscopy, we determined the hyperfine parameters of ferrous iron up to 95 GPa. The phase transitions were correlated with discontinuities in Mössbauer spectral features. We observed the onset of high-spin-to-low-spin transitions in the M1 and M2 sites at ～37 GPa and ～74 GPa, respectively. Understanding the electronic structure of iron in a well-characterized single crystal of ferrosilite may help interpret the behavior of iron in complex dense silicate phases.  相似文献   

16.
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.  相似文献   

17.
Mössbauer effect, (ME) and powder X-ray diffraction, (XRD) have been used to study the relationship between cationic size, tetrahedral layer rotation, octahedral layer flattening, stability, and Mössbauer quadrupole splitting, qs, of iron bearing trioctahedral micas. Tetrahedral layer rotation accounts for much of the lattice adjustment but biotites that require an angle of rotation higher than 21 degrees are not stable. Both experimental and computational data show that qs for Fe3+ (IV) increases with increasing degree of tetrahedral layer rotation. A systematic increase of qs for Fe2+ (VI) is also observed, but this could be due to factors other than tetrahedral layer rotation.  相似文献   

18.
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+.  相似文献   

19.
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   

20.
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   

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