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1.
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 ΘM 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 ΘM and the coordination type, or, for a given valence state and coordination type, between ΘM and the mineral type is, however, not obvious.  相似文献   

2.
Mössbauer spectroscopy has been used widely to characterize the ferric (Fe3+) and ferrous (Fe2+) proportions and coordination of solid materials. To obtain these accurately, the recoilless fraction is indispensible. The recoilless fractions (f) of iron-bearing minerals, including oxides, oxyhydroxides, silicates, carbonates, phosphates and dichalcogenides, and silicate glasses were evaluated from the temperature dependence of their center shifts or absorption area with the Debye model approximation. Generally, the resolved Debye temperature (θD) of ferric iron in minerals, except dichalcogenides, through their center shifts ranging from 400 to 550 K, is significantly larger than ferrous iron ranging from 300 to 400 K, which is consistent with the conclusion from previous work. The resolved f (Fe3+)RT with the center shift model (CSM) ranges from 0.825 to 0.925, which is larger than that obtained for f(Fe2+)RT, which ranges from 0.675 to 0.750. Meanwhile, the θD and f resolved from temperature-dependence of absorption are generally lower than from center shifts, especially for ferric iron. The significant difference between f(Fe3+) and f(Fe2+) indicates the necessity of recoilless fraction correction on the Fe3+/(Fe3++Fe2+) resolved from Mössbauer spectra.  相似文献   

3.
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   

4.
The inner nebula out to ~3 A.U. was depleted in volatile elements that included potassium and manganese at a very early stage of solar-system history. The inner planets and many meteorites inherited this element signature, the cause of which probably was early violent solar activity. Because of this evidence for elemental depletions correlated with volatility, one might also expect to find examples of fractionation, particularly among lower mass elements. Here we discuss the search for such effects among the isotopes of K, Mg, Si, and Ca in a wide variety of terrestrial, lunar, and meteoritic samples. We examine examples of vaporization without isotope fractionation, and a comparison of the effects expected between distillation and condensation. Effects attributable both to evaporation and condensation are observed in refractory inclusions (CAIs) in meteorites and reflect localized events in the early nebula. However, the lack of isotopic fractionation that is observed among a wider variety of presolar-system materials rules out the general operation of Rayleigh-type fractionation on primitive solar-nebular material. We conclude with a discussion of volatileelement behavior during the giant Moon-forming impact that shows that the material in the Moon was not subjected to Rayleigh-type distillation.  相似文献   

5.
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   

6.
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   

7.
Electric field gradient (EFG) measurements for Fe2+ in the cis- and trans-sites of a large single crystal of trioctahedral biotite of the lM polytype are described. Attempts to apply thickness and polarisation corrections are outlined. The measured EFG's are distinctly rhombic: = 0.28 and 0.42 respectively for the cis- and transsites and the EFG principal directions lie approximately along the crystallographic axes. For the cis-site V y lies close to the normal to the basal plane while for the transsite lies close to this direction.  相似文献   

8.
Electrical resistivity and 57Fe Mössbauer spectra are reported for three calcic amphiboles with different Fe concentrations. AC measurements (20?Hz–1?MHz) were performed, applying impedance spectroscopy between 100 and 785?°C in an N2 gas atmosphere. It was found that up to three semiconducting charge transport processes can be distinguished, which in part changed slightly when several runs were carried out to higher temperatures. The extrapolated DC resistivity is much smaller for an amphibole with high Fe content than for the two with lower Fe concentrations. The derived activation energies are between ~0.48 and ~1.06?eV. For temperatures ≤600?°C the results are compatible with a charge transport mechanism due to electron hopping between Fe2+ and Fe3+. Above 600?°C, dehydrogenation and/or beginning amphibole decomposition obviously alter the conduction mechanism. From Mössbauer spectra it was established that in all amphibole samples Fe2+ and Fe3+ are simultaneously present. Mössbauer parameters were derived by fitting the observed spectra to models taking the occupation of various M sites into account.  相似文献   

9.
Three chalcolithic pottery sherds, paint removed from the surface of each sherd, and an unheated red pigment (Tell-Halaf culture, Turkey) were analysed within the frame of archaeometric studies using mineralogical methods, 57Fe Mössbauer spectroscopy, magnetization and rotational hysteresis data. From mineralogical results, the individual minerals forming the cores of the sherds were determined. It was found that the sherds are lime-rich. High temperature X-ray analysis on comparable Ca-rich material showed that the established composition is consistent with a firing temperature of 750-950°C. Apart from the pigment, each Mössbauer spectrum of Fe-bearing components consists of dominating paramagnetic doublets, arising mostly from silicate phases, and of a six-line pattern with reduced intensity, due to ferri- and/or antiferromagnetic Fe-oxide phases. For three samples, an Fe3+ silicate component of the spectra is clearly dominating, which points to oxidizing conditions during firing. For the others Fe2+ and Fe3+ components occur in about equal intensities. For the pigment, the magnetic sextet is of similar intensity to the Fe3+ silicate component. From magnetic analysis of ferrimagnetic phases it follows that a low percentage of particles of solid solutions -Fe2O3 – Fe3O4 exist, probably in part 0.1 m in diameter. The ferrimagnetic particles of at least one paint are probably covered by a thin layer of hematite as found from rotational hysteresis data. An attempt is made to draw conclusions from the experimental results, regarding the firing conditions of the sherds and paints.  相似文献   

10.
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   

11.
The lepidocrocite (-FeOOH) to maghemite (-Fe2O3), and the maghemite to hematite (-Fe2O3) transition temperatures have been monitored by TGA and DSC measurements for four initial -FeOOH samples with different particle sizes. The transition temperature of -FeOOH to -Fe2O3 and the size of the resulting particles were not affected by the particle size of the parent lepidocrocite. In contrast, the -Fe2O3 to -Fe2O3 transition temperature seems to depend on the amount of excess water molecules present in the parent lepidocrocite. Thirteen products obtained by heating for one hour at selected temperatures, were considered. Powder X-ray diffraction was used to qualify their composition and to determine their mean crystallite diameters. Transmission electron micrographs revealed the particle morphology. The Mössbauer spectra at 80 K and room temperature of the mixed and pure decomposition products generally had to be analyzed with a distribution of hyperfine fields and, where appropriate, with an additional quadrupole-splitting distribution. The Mössbauer spectra at variable temperature between 4.2 and 400 K of two single-phase -Fe2O3 samples with extremely small particles show the effect of superparamagnetism over a very broad temperature range. Only at the lowest temperatures (T55 K), two distributed components were resolved from the magnetically split spectra. In the external-field spectra the mI=0 transitions have not vanished. This effect is an intrinsic property of the maghemite particles, indicating a strong spin canting with respect to the applied-field direction. The spectra are successfully reproduced using a bidimensional-distribution approach in which both the canting angle and the magnetic hyperfine field vary within certain intervals. The observed distributions are ascribed to the defect structure of the maghemites (unordered vacancy distribution on B-sites, large surface-to-bulk ratio, presence of OH- groups). An important new finding is the correlation between the magnitude of the hyperfine field and the average canting angle for A-site ferric ions, whereas the B-site spins show a more uniform canting. The Mössbauer parameters of the two hematite samples with MCD104 values of respectively 61.0 and 26.5 nm display a temperature variation which is very similar to that of small-particle hematites obtained from thermal decomposition of goethite. However, for a given MCD the Morin transition temperature for the latter samples is about 30 K lower. This has tentatively been ascribed to the different mechanisms of formation, presumably resulting in slightly larger lattice parameters for the hematite particles formed from goethite, thus shifting the Morin transition to lower temperatures.Senior Research Associate, National Fund for Scientific Research (Belgium)  相似文献   

12.
The interaction of γ-rays with smectite clays induces noticeable changes in the structure and physicochemical properties of the minerals. For sodium-montmorillonite, Mössbauer spectra show that γ-irradiation causes a partial reduction of trivalent iron to the divalent state due to hydrogen radicals production from the radiolysis of interlayer water. The XRD results show no change in the interlayer space upon irradiation and therefore the radiolysis of interlayer water causes no measurable changes in the architectural organization of the interlayer environment. Intercalation of simple organic molecules (ethylene glycol, tert-butanol and tetraalkylammonium salts) causes partial oxidation of structural divalent iron and affects the Mössbauer parameters of the M1 and M2 ferric components. Irradiation of ethylene glycol- or tert-butanol-clay composites indicates reduction of trivalent iron to the divalent state. XRD data show that the irradiation of clay-ethylene glycol complex causes collapse of the initial double layer of glycol molecules to a single layer complex. Finally, XRD results show that the effects of γ-irradiation on clay-tetraalkylammonium complexes depend upon the chain length of the organic cations.  相似文献   

13.
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   

14.
Mössbauer measurements on synthetic iron orthosilicate Fe2SiO4 (fayalite) were carried out in the antiferromagnetic spin state below T N 65 K. The Mössbauer parameters isomer shift , inner magnetic field H(0), angle between H(0) and the z-component of the electric field gradient (efg), quadrupole splitting QS and asymmetry parameter were determined as a function of temperature. These parameters could be attributed to the two crystallographic sites M1 and M2.The smaller isomer shift on M1 with respect to M2 displays the more covalent character of the Fe-O bond on M1, which is supported by previous neutron diffraction experiments. H(0) shows a Brillouin-type behaviour with different fields on the two crystallographic sites (stronger on M1) and a small discontinuity at T = 23 K which corresponds with previous magnetic measurements. The quadrupole splitting is equal on both sites within error bars, in agreement with previous theoretical results and in contradiction to previous Mössbauer refinements published elsewhere.  相似文献   

15.
The forms of non-pyritic Fe in a suite of Victorian brown coals have been determined by 57Fe Mössbauer analysis. The dominant Fe phase is a poorly-ordered ferric oxyhydroxide with a magnetic ordering temperature of (530 ± 50) K and particle size of approximately 50 Å. Upon exposure of the coal to air, this phase slowly crystallises to goethite. Most of the remaining Fe occurs as a high-spin Fe(II) species attributed to dissolved and hence mobile, Fe(II) humate, which precipitates as the ferric oxyhydroxide to an extent determined by the pH. A third species, present in a much lower concentration, appears to exhibit a transition from low-spin to high-spin Fe(II) as water is removed from the coal.  相似文献   

16.
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.  相似文献   

17.
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   

18.
Although the electron microprobe has become the standard microanalytical tool in modern geosciences, conventional electron microprobe analysis does not allow determination of the valence states of elements such as Fe. The correct classification of minerals and interpretation of reaction microfabrics and grain zonation require high-quality information on ferric/ferrous ratios on a scale of micrometers. The flank method developed by Höfer et?al. (1994, Eur J Mineral 6:407–418) has revived new interest in electron-induced X-ray-spectroscopy to resolve oxidation states in minerals with high spatial resolution. We have recharacterized well-documented sodic amphiboles of the glaucophane–ferroglaucophane–riebeckite–magnesioriebeckite series by electron probe microanalysis and combined the microanalytical data with ferric/ferrous ratios from Mössbauer spectroscopy, Li data from bulk ICP-AES analysis and H2O data from bulk Karl–Fischer titration. The combination of microanalysis and high-quality analysis on the bulk materials results in a data set that allows comparison of model-based stoichiometric calculations and the calibration of the high-resolution flank method. The calibration obtained allows ferric/ferrous ratios to be determined within an error of ±5%. We have found it necessary to apply an empirical correction for absorption phenomena. The advantages of the method must be weighed against the complex calibration procedures necessary and thus the flank method will probably not find use as a routine method. However, in cases where high-resolution data in terms of valence state are needed, the flank method will provide useful data on ferric/ferrous ratios down to minimum FeOtotal content of 6–8 wt%.  相似文献   

19.
20.
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   

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