Mössbauer spectroscopy of minerals

We compare two different approaches to fitting the Fe-57 Mössbauer spectra of paramagnetic state minerals: the widespread practice of using Lorentzian line doublets with adjustable Γ widths and a new method (Rancourt and Ping, 1991) based on quadrupole splitting distributions (QSDs). We argue that there is no physical justification for the former and that the latter is a theoretically correct approach. With the same number of free parameters, the QSD method performs better. The Lorentzian doublet method 1) significantly overestimates the background, 2) puts overly large wings or tails on the main absorption peaks, and 3) gives unphysically large values of Γ. Whereas Lorentzian doublets are often arbitrarily (and incorrectly) assigned to model sites in the average unit cell, QSDs represent the most information that can be distilled from the spectra and are caused by the various local and long-range structural and chemical environments acting concomitantly.     

Spectroscopic standard for tetrahedrally coordinated ferric iron: γ LiAlO2:Fe3+

γ LiAlO₂ doped with Fe³⁺ in the tetrahedral site has been examined by extended X-ray absorption fine structure (EXAFS) analysis, and Mössbauer and optical spectroscopy. The isomer shift (IS) is ?0.026 mm/s (Fe-Pd); the quadrupole splitting (QS) is 0.62 mm/s. Anisotropic optical absorption is prominent at ～391, 452, and 463 nm. The K-edge absorption spectrum shows a prominent absorption near 7,113 ev typical of tetrahedrally coordinated Fe³⁺.     

<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.     

The Mössbauer spectrum of 57Fe in titanium-bearing andradites

Mössbauer spectra of ⁵⁷Fe in 2 schorlomite garnets reveal 5 distinct quadrupole-split doublets: dodecahedral Fe²⁺, octahedral Fe²⁺ and Fe³⁺, and tetrahedral Fe²⁺ and Fe³⁺. The isomer shifts and nuclear quadrupole splittings of the 5 doublets were studied between 15 and 500 K. The site occupancies for iron were determined. Reference of the chemical analyses to a basis of 12 oxygens and the Mössbauer data show that in the 2 schorlomites titanium is exclusively quadruvalent within the experimental error. The isomer shift of tetrahedral Fe²⁺ between 15 and 295 K seems to be rather small. The shift is interpreted in terms of localized chemical bonding. Above 295 K the shift cannot be evaluated because of overlapping peaks. If electronic transfer processes (e.g. “electron hopping”) between cations are present their relaxation times must be longer than ～10^?7 s.     

Mössbauer effect and X-ray diffraction studies of synthetic iron bearing trioctahedral micas

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.     

Jahn-Teller configurations in natural spinels

The local configurations and related hyperfine interactions of the tetrahedrally coordinated Fe²⁺ in two natural spinels were investigated. A special fitting procedure of the Mössbauer spectra is proposed in order to cover the involved mechanisms over the whole temperature range. The behavior of the quadrupole splitting vs temperature was successfully explained in terms of the split of the electronic 3d ground state doublet under a non-cooperative Jahn-Teller effect also providing estimates of the splitting energy for each configuration.     

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

A refined set of Mössbauer parameters (isomer shifts, quadrupole splittings, Fe²⁺/Fe³⁺ ratios) and lattice parameters were obtained from annites synthesized hydrothermally at pressures between 3 and 5 kbars, temperatures ranging from 250 to 780° C and oxygen fugacities controlled by solid state buffers (NNO, QMF, IM, IQF). Mössbauer spectra showed Fe²⁺ and Fe³⁺ on both the M1 and the M2 site. A linear relationship between Fe³⁺ content and oxygen fugacity was observed. Towards low Fe³⁺ values this linear relationship ends at ≈10% of total iron showing that the Fe³⁺ content cannot be reduced further even if more reducing conditions are used. This indicates that in annite at least 10% Fe²⁺ are substituted by Fe³⁺ in order to match the larger octahedral layer to the smaller tetrahedral layer. IR spectra indicate that formation of octahedral vacancies plays an important role for charge balance through the substitution 3 Fe²⁺ → 2 Fe³⁺ + ?_(oct).     

The crystal chemistry of ferric iron in Fe0.05Mg0.95SiO3 perovskite as determined by Mössbauer spectroscopy in the temperature range 80–293 K

Mössbauer spectra were recorded at multiple temperatures between 80 and 293 K to study the nature of Fe³⁺ in Fe_0.05Mg_0.95SiO₃ 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: Θ_M (Fe²⁺)=365±52 K and Θ_M (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.     

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.     

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.     

Mössbauer spectra of Fe x O (x>0.95)

The Mössbauer spectra of five samples of Fe _x O with compositions in the range 1.00>x>0.95 have been recorded at 298 K and 4.2 K. The spectrum of Fe _x O at 298 K consists of an asymmetric doublet which was fitted to one Fe²⁺ singlet, two Fe²⁺ doublets and 1 Fe³⁺ singlet. The Mössbauer parameters vary consistently with the increasing density of defects as x decreases. The Mössbauer spectrum of Fe _x O at 4.2 K consists of a large number of unresolved lines. The data were fitted to a series of singlets to enable the rough calculation of quantities relating to the mean Fe²⁺ and Fe³⁺ environments. The results of the fits to the 298 K spectra are briefly discussed in terms of a physical model for the defect structure of Fe _x O.     

Mössbauer studies of synthetic and natural micas on the polylithionite-siderophyllite join

Mössbauer studies of micas on the polylithionite-side-rophyllite join show the existence of a relation between the quadrupole splitting (ΔE _Q) values of Fe²⁺ high spin doublets and both cationic and anionic composition of micas. This linear relation is positive as Li₂O content increases and negative as F content increases. In the lithium iron micas, the inner ferrous quadrupole doublet is assigned to the cis-site M(2), while the outer doublet is assigned to the trans-site M(1). A random distribution of Fe²⁺ is observed in fluorine-rich compositions, while slight enrichment of the M(1) site is noticed in hydroxyl compositions, perhaps due to a more sensitive oxidation in situ in M(2) than M(1) sites. The Mössbauer spectrum of siderophyllite K₂(Fe ₄ ²⁺ Al₂)(Si₄Al₄)O₂₀(OH)₄ shows the presence of only one ferrous doublet, which is assigned to M(2) sites. Hence from Mössbauer data we must consider a clintonite (“xanthophyllite”) structure for this mica. The ordered octahedral layer has two distorted ferrous cis-sites and one, more symmetrical, aluminum trans-site.     

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

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

M?ssbauer spectroscopy of Pb-bearing minerals from the jarosite group

The minerals of the jarosite group, including the jarosite-beudantite-segnitite and jarosite-beaverite-osarizawaite isomorphic series, were studied with M?ssbauer spectroscopy. All the samples were collected from the oxidation zones of the South Urals sulfide deposits. In contrast to the jarosite containing one Fe³⁺ doublet in the M?ssbauer spectrum, the Pb-bearing members of the jarosite group—beudantite and beaverite—have two doublets in their spectra. Fe³⁺ is distributed at two sites with similar isomer shifts and different quadrupole splitting. The quantitative ratio of those doublets in the structure is roughly equal. The M?ssbauer spectra of the intermediate jarosite-beudantite and beaverite-osarizawaite members are superpositions of the jarosite and beudantite spectrum types with a prevalent jarosite doublet and larger quadrupole splitting. An admixture of antimony increases the Fe³⁺ content in the doublet with smaller quadrupole splitting. The unequal Fe³⁺ distribution in those two sites may be related to the ordering of cations in octahedrons. The appearance of two different Fe³⁺ sites probably resulted from the local coordinating role of Pb rather than from isomorphic replacement in anion groups.     

<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.     

Mössbauer and infrared spectroscopic studies of Belgian chloritoids

Three chloritoid samples from the Stavelot massif (Belgium) and one sample from the Serpont massif (Belgium) have been characterized by chemical analyses and differential X-ray diffraction. A classification of chloritoid is proposed. Mössbauer spectra at temperatures between 78 and 360 K and in external magnetic fields were obtained for a triclinic and for a monoclinic specimen. The spectra show a superposition of a weak Fe³⁺ doublet (less than 10%) and an intense Fe²⁺ doublet. It is found that a decomposition of the ferrous absorption into two distinct quadrupole doublets leads to smaller deviations between experimental and calculated line shapes, especially at low temperatures. This suggests that Fe²⁺ is present in both cis and trans O₂(OH)₄ octahedral positions in the trioctahedral layer. However, the structural data derived from the temperature dependence of isomer shifts and quadrupole splittings, are found to be inconsistent with known crystallographic data. It is therefore concluded that Fe²⁺ is present in only one type of lattice site and that the numerically imposed decomposition into two ferrous doublets is merely an artifact due to thickness saturation effects and to the distributive character of the hyperfine parameters. The negative sign of the electric field gradient further confirms the assignment of the Fe²⁺ doublet to a cis octahedral configuration. Finally, only minor differences between the Mössbauer results for triclinic and monoclinic chloritoid are observed. The infrared absorption spectra of the four samples are almost identical except in the region around 600 cm^?1 at which the monoclinic phase exhibits two absorption bands instead of one band for the triclinic samples. All absorption bands can be well assigned to the different vibrations. Inter-layer hydrogen bonding is evidenced by the occurrence of two v _O-H absorption bands. Furthermore, the specific nature of the infrared spectra enables a fast identification of chloritoid samples.     

Sign of the magnetic coupling of Fe2+ and Fe3+ in biotite

Mössbauer spectra of biotite at 4 K are reported. The biotite crystals were oriented with the c-axis parallel to the γ-ray direction and some spectra were recorded with external magnetic fields of 40 kOe applied at right angles to the c-axis. Decrease of the magnetic-hyperfine field of both Fe²⁺ and Fe³⁺ ions on application of the external field shows that both Fe³⁺-Fe³⁺ pairs and Fe²⁺-Fe²⁺ pairs are coupled ferromagnetically.     

Oxidation Experiment of Natural Megacrystal Clinopyroxene: Implications for Assignment of Mössbauer Spectra

The Mössbauer spectra of natural megacrystal clinopyroxene are usually fitted by 4 sets of symmetric doublets, A‐A', B‐B', C‐C' and D‐D', respectively, in terms of increasing Qs value in literature. But the assignments of those doublets are quite different, except the D‐D' doublet assigned to Fe³⁺at the lattice site M***1 in previous papers. Particularly, the assignment and interpretation of the C‐C' doublet are diverse. The oxidation experiments of natural megacrystal clinopyroxene collected from the Hannuoba basalt, North China, were performed under controlled conditions of temperature at 1000°C and oxygen fugacity of FMQ buffer in 1, 2, ***3 and 5 days respectively. The oxidized samples were then measured by X‐ray diffraction spectrometry and Mössbauer spectrometry. The oxidation of clinopyroxene is characterized by Fe²⁺ → Fe³⁺at M1 under the subsolidus conditions, which is consistent with the increase of the area of the D‐D' doublet when the heating time increases. Accordingly, the area of the A‐A' and B‐B' doublets decreases with the increasing heating time. However, the area of C‐C' keeps almost constant. Therefore, the 4 sets of doublets can be assigned correctly as follows: A‐A' doublet to Fe⁺²at M1, B‐B' Fe²⁺at M1, C‐C' Fe²⁺at M2, and D‐D' Fe³⁺at M1. The M1 site splitting is due to the NNN (Next Nearest Neighbour) effect of the M2 site. The amount of Fe³⁺at the tetrohedral site of megacrystal clinopyroxene is negligible according to this study.     

The crystal chemistry and mössbauer study of schorlomite

Six schorlomite samples with TiO₂ contents varying between 9.70 and 15.34 weight percent were studied by means of Mössbauer spectroscopy and chemical analysis. The measured Mössbauer spectra have complex shapes. The spectra of these samples were fitted with six doublets, which can be assigned to ^VIIIFe²⁺, ^VIFe²⁺, ^VIFe³⁺, ^IVFe³⁺ and two electron delocalizations, ^IVFe³⁺ ? ^VIIIFe²⁺ and ^IVFe³⁺ ? ^VIFe²⁺, respectively. The assignment of iron absorption doublets and their Mössbauer parameters are discussed in terms of the single crystal structure data of one of the samples studied in this work. Cation distributions are also given. The occupancies of cations at the tetrahedral (Z) site are Fe³⁺>Al³⁺, Ti⁴⁺, and the relative enrichments at Z site are always Fe³⁺>Ti⁴⁺. Most of the six samples contain Ti³⁺. Ti³⁺/ΣTi ratios range from 1.43 percent to 6.40 percent. Fe²⁺/ΣFe ratios vary from 8.84 percent to 11.31 percent. Four types of substitution must be considered for Ti entering the garnet structure.     

Magnetization and 57Fe Mössbauer study of obsidians

Magnetic analysis and ⁵⁷Fe Mössbauer spectroscopy were used to find characteristic properties of obsidian samples collected from various localities in the Mediterranean area. Magnetic hysteresis parameters of ≈ 30 different obsidian samples, recorded at 294 K, and plotted in the form σ _r /σ _s versus H _c /H _cr (σ _r =saturation remanent magnetization, σ _s =saturation magnetization of ferrimagnetic phases in the obsidian samples, H _c =coercive force, H _cr =remanent coercive force) cluster in certain areas of the plot for obsidian samples of a given region. This property results from the formation of ferrimagnetic ore grains of various grain sizes, which appear to be Fe₃O₄-rich spinels (Curie temperatures T _c ≈520–580°C), during the rapid cooling process of the silica-rich magma. For single domain, pseudosingle domain and multidomain particles of magnetic minerals, corresponding to different grain sizes, the data points are usually in different areas of the plot. The results show that there is obviously a characteristic difference in the ore grain size and in the grain size distribution for obsidian samples from different regions. ⁵⁷Fe Mössbauer absorption spectra revealed two distinct kinds of patterns, characterized by contributions from Fe²⁺ and Fe³⁺ cations preferentially inside the glassy matrix. The poor resolution of the spectra precludes the application of this method for identification purposes. The Mössbauer parameters of quadrupole splitting, isomer shift and linewidth are compatible with the respective values for Fe²⁺ and Fe³⁺ cations in alkali and alkaline-earth silicate glasses.