Optical absorption and mössbauer spectra of purple and green yoderite,a kyanite-related mineral

Mössbauer and polarized optical absorption spectra of the kyanite-related mineral yoderite were recorded. Mössbauer spectra of the purple (PY) and green yoderite (GY) from Mautia Hill, Tanzania, show that the bulk of the iron is Fe³⁺ in both varieties, with Fe²⁺/(Fe²⁺+Fe³⁺) ratios near 0.05. Combining this result with new microprobe data for PY and with literature data for GY gives the crystallochemical formulae: $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.95}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{0}}{\text{.01}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.34}}}^{{\text{3 + }}} {\text{Mn}}_{{\text{0}}{\text{.07}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.57}}} )_{5.97}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.98}}} {\text{P}}_{{\text{0}}{\text{.03}}} ){\text{O}}_{{\text{18}}{\text{.02}}} ({\text{OH)}}_{{\text{1}}{\text{.98}}} ] \hfill \\ \end{gathered}$$ and PY and $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.98}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{< 0}}{\text{.001}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.45}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.56}}} )_{6.02}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.91}}} {\text{O}}_{{\text{17}}{\text{.73}}} {\text{(OH)}}_{{\text{2}}{\text{.27}}} ] \hfill \\ \end{gathered}$$ for GY. The Mössbauer spectra at room temperature contain one main doublet with isomer shifts and quadrupole splittings of 0.36 (PY), 0.38 (GY) and 1.00 (PY), 0.92 (GY) mm s^?1, respectively. These values correspond to Fe³⁺ in six or five-fold coordination. The doublet components have anomalously large half widths indicating either accomodation of Fe³⁺ in more than one position (e.g., octahedraA1 and five coordinatedA2) or the yet unresolved superstructure. Besides strong absorption in the ultraviolet (UV) starting from about 25,000 cm^?1, the polarized optical absorption spectra are dominated by strong bands around 16,500 and 21,000 cm^?1 (PY) and a medium strong band at around 13,800 cm^?1 (GY). Position and polarization of these bands, in combination with the UV absorption, explain the colour and pleochroism of the two varieties. The bands in question are assigned to homonuclear metal-to-metal charge transfer transitions: Mn²⁺(A1) Mn³⁺(A1′) ? Mn³⁺(A1) Mn²⁺(A1′) and Mn²⁺(A1) Mn³⁺(A2 ? Mn³⁺(A1) Mn²⁺(A2) in PY and Fe²⁺(A1) Fe³⁺(A1′) ? Fe³⁺(A1) Fe²⁺(A1′) in GY. The evidence for homonuclear Mn²⁺ Mn³⁺ charge transfer (CTF) is not quite clear and needs further study. Heteronuclear FeTi CTF does not contribute to the spectra. In PY, additional weak bands were resolved at energies around 17,700, 18,700, 21,000, and 21,900 cm^?1 and assigned to Mn³⁺ in two positions. Weak bands around 10,000 cm^?1 in both varieties are assigned to Fe²⁺ spin-alloweddd-transitions. Very weak and sharp bands, around 15,400, 16,400, 21,300, 22,100, 23,800, and 25,000 cm^?1 are identified in GY and assigned to Fe³⁺ spin-forbiddendd-transitions.     

A second natural occurrence of yoderite

A second example of yoderite has been discovered in whiteschists from the Southern Chewore Hills of northern Zimbabwe. The mineral is pale green in colour and occurs in an equilibrium assemblage with talc+chlorite+kyanite+dravite+hematite. There is no quartz present. Recalculated microprobe analyses give a structural formula of Mg₂Al_5.7Fe_0.3Si₄O₁₈(OH)₂, similar to that obtained for the type locality at Mautia Hill, Tanzania, i.e. Mg₂Al_5.6Fe_0.4Si₄O₁₈(OH)₂. Textural relationships and relative proportions of minerals suggest that the yoderite was formed by reaction between talc, chlorite, kyanite and hematite. Experimental evidence suggests high-water-pressure metamorphic conditions at temperatures exceeding a reaction curve that extends between 13  kbar at 590  °C and 21  kbar at 650  °C. The yoderite-bearing whiteschist is associated with a 1.4  Ga dismembered ophiolite. It is proposed that this yoderite occurrence is associated with a relict subduction/suture zone.     

Electronic absorption spectra of chromium-bearing sapphirine

Violet, non-pleochroic and greenish-blue, pleochroic chromium-substituted sapphirines were found in corundum-bearing spinel-websterite xenolites from the Yakutian kimberlite pipes Noyabrskaya (N) and Sludyanka (Sl), respectively. The crystallochemical formulae of sapphirine crystals from such xenolites were determined by EMP to be (Mg_3.40Fe_0.23Al_3.25Cr_0.16)^[6] Al _1.00 ^[6] [O₂/Al_4.53Si_1.47O₁₈] (N) and (Mg_2.53Fe_0.55 Mn_0.04Ti _0.03 ⁴⁺ Al_3.55Cr _0.08 ³⁺ )^[6]Al _1.00 ^[16] [O₂/Al_4.28Si_1.73O₁₈] (Sl). Single crystal spectra in the range 35000–6000 cm^1- showed a slightly polarization dependent absorption edge near 3200 cm^1- (N) or 30000 cm^1- (Sl) and unpolarized bands at 25300 and 17300 cm^1-, typical of spin-allowed transitions, derived from ⁴A_2g→⁴T_1g and ⁴A_2g→⁴T_2g, of Cr³⁺ in octahedral sites, with point symmetry C₁, of the structure. Another weak band at 23000 cm^?1 in the sapphirine-N spectra is attributed to low symmetry splitting of the excited ⁴T₁ (F)-State of Cr³⁺. These assignments lead to crystal field parameters Dq=1730cm^?1 and B= 685cm^?1 of Cr³⁺ in sapphirine. Crystallochemical and spectroscopic arguments suggest that Cr³⁺ subsitutes for Al in the M(1) or M(8) sites of the sapphirine structure. In addition to Cr³⁺-transitions, spectra of Sl exhibit weak dd-bands of Fe²⁺ at 10000 and 7700 cm^1-, which are unpolarized in consistency with the C₁ site symmetry of the octahedra in the structure. Spectra of Sl show also prominent, broad bands (Δv_1/2～-5000 cm^1-) at 15000 and 11000 cm^1-, which occur in E//Y(//b) and E//Z(//_c=12°) only and exhibit an intensity ratio α_Y∶α_z close to 1∶3. This result, the large half width, as well as band energy — MM distance considerations suggest that these bands originate from Fe^2+[6]-Fe^3+[6] charge-transfer transitions in wall octahedra M(1)M(2), M(6)M(7) etc., forming MM vectors of 30° with the c-axis. The lack of Fe²⁺-Fe³⁺ charge-transfer bands in sapphirine N might indicate a lower oxygen fugacity during the formation of the websterite from the Noyabrskaya pipe compared to that from the Sludyanka pipe.     

Electron density and polarized absorption spectra of fayalite

The maxima of the electron difference densities of Fe²⁺ atM(1) andM(2) positions of fayalite, Fe₂SiO₄, determined by x-ray diffraction are considered to correspond to atomic dipoles. Provided the selection rules of dipole radiation are satisfied and the energy of the incident radiation lies within the appropriate range, the interaction of incident radiation with these atomic dipoles should lead to three absorption bands of which two originate from Fe²⁺ atM(1), one from Fe²⁺ atM(2). The relative intensities of the three bands, dependent on the polarization direction, are estimated. The result ist in excellent agreement with the interpretation of olivine spectra given by Burns (1970).     

Optical absorption spectra of iron ions in vivianite

Absorption bands are determined in polarized optical spectra of vivianite Fe₃(PO₄)₂·8H₂O, recorded at room and low temperatures. These bands are caused by spin-allowed d-d transitions in structurally nonequivalent Fe _A ²⁺ (～11000 cm^-1 (γ-polarization) (and) ～12000 cm^-1 (β-polarization)) (and) Fe _B ²⁺ (～8400 cm^-1 (γ, α-polarization) and ～11200 cm^-1 (α-polarization)) ions. A charge transfer band (CTB) Fe _B ²⁺ +Fe _B ³⁺ →Fe _B ²⁺ +Fe _B ²⁺ (～15000 cm^-1) also determined, has polarizing features giving evidence of a change in the Fe _B ²⁺ -Fe _B ³⁺ bond direction, when compared with Fe _B ²⁺ -Fe _B ²⁺ . Bands of exchange-coupled Fe³⁺-Fe³⁺ pairs (～19400, ～20400, ～21300 and ～21700 cm^-1) which appear on oxidation of Fe²⁺ in paired Fe _B octahedra are also characterized.     

Synthesis and properties of Mn-bearing yoderite and of Mn-bearing kornerupine as by-product

Summary Yoderite with compositions close to those of the natural purple variety were synthesized from gels at high water pressures (15–16 kbar) and temperatures (650, 800°C) at the oxygen fugacities of the Mn₂O₃/MnO₂-buffer with yields up to 95%. Chemical formulae based on microprobe data and water analyses are Mg_1.90(Al_6.01Fe³⁺ _0.28Mn³⁺ _0.11)_=6.40Si_3.8O_18.21(OH)_1.79 and Mg_1.86(Al_5.77Fe³⁺ _0.36Mn³⁺ _0.04)_=6.17Si₄O_18.20(OH)_1.80. Manganiferous, but iron-free yoderite with the formula Mg_1.85(Al_6.26Mn³⁺ _0.10)_=6.36Si_3.91O_18.15(OH)_1.85 was also obtained and proves that Mn³⁺ alone may stabilize the yoderite structure, although this does not necessarily imply thermodynamic-stability. All these synthetic yoderites exhibit the typical purple color known from the natural mineral with pleochroism of dark blue b to colorless b, which confirms the earlier spectroscopic conclusion that Mn is responsible for the purple color of yoderite. Compared to ferric iron, Mn³⁺ is incorporated into yoderite in much smaller amounts, although the maximum attained here (0.11 p.f.u.) is still below the 0.15 found in new analyses of natural yoderite from Tanzania.In some runs yoderite coexisted with kornerupine containing Mn and Fe as well and showing spectacular pleochroism from dark green b to light red c. Relative to yoderite Mn is fractionated into kornerupine. The analytical data suggest that most of the manganese is incorporated as Mn²⁺, although some Mn³⁺ may be the reason for the color. Coexisting braunite contains high amounts of Mg and Al substituting for Mn²⁺ and Mn³⁺, respectively. Garnet obtained from the Fe-free gel contains only Mn²⁺ and has the end member composition Pyrope₇₉Spessartine₂₁ despite high oxygen fugacity.

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Synthese und Eigenschaften von Mn-haltigem Yoderit und Mn-haltigem Kornerupin als Nebenprodukt

Zusammenfassung Die Synthese von Yoderiten mit chemischen Zusammensetzungen nahe denjenigen der natürlichen, blau gefärbten Varietät gelang in Ausbeuten bis zu 95% aus Gelen bei hohen Versuchsdrücken (15, 16 kbar) und Temperaturen von 650 bzw. 800°C. Die Sauerstoffugazität wurde durch den Puffer Mn₂O₃/MnO₂ kontrolliert. Aus Mikrosondenanalysen und Wasserbestimmungen wurden folgende chemische Formeln von Yoderit bestimmt: Mg_1.90(Al_6.01Fe³⁺ _0.28Mn³⁺ _0.11)_=6.40Si_3.80O_18.21(OH)1.79 and Mg_1.86(Al_5.77Fe³⁺ _0.36Mn³⁺ _0.04)_=6.17Si₄O_18.20(OH)_1.80. Die Stabilisierung der Yoderitstruktur allein durch Mangan wurde durch die Synthese manganhaltigen, aber eisenfreien Yoderits, Mg_1.85(Al_6.26Mn³⁺ _0.10)_=6.36Si_3.91O_18.15(OH)_1.85 belegt. Sämtliche synthetisierten Yoderite besitzen die typische dunkelblaue Farbe, wie sie vom natürlichen Mineral bekannt ist, und zeigen einen Pleochroismus von dunkelblau b zu farblos b. Dies unterstützt die ursprüngliche auf spektroskopischen Untersuchungen basierende Vermutung, daß Mangan für die blaue Farbe von Yoderit verantwortlich ist. Im Vergleich zu Eisen wird Mn³⁺ in geringerem Ausmaß in die Yoderit-struktur eingebaut, wobei die hier erreichte maximale Menge von 0.11 Mn³⁺ p.F.E. unter derjenigen der natürlichen Yoderite von Mautia Hill, Tansania, liegt (dort 0.15 Mn³⁺ p.F.E.).In einigen Versuchsprodukten koexistierte mit Yoderit auch Fe-Mn haltiger Kornerupin, der einen ausgeprägten Pleochroismus von dunkelgrün b zu hellrot c besitzt. Kornerupin enthält im Vergleich zu Yoderit mehr Mangan. Chemische Analysen dieser Phase belegen den Einbau von zweiwertigem Mangan, obwohl wahrscheinlich Spuren von Mn³⁺ die Farbe von Kornerupin verursachen. Mit Yoderit koexistierender Braunit besitzt Mg und Al, die für Mn²⁺ bzw. Mn³⁺ substituiert wurden. Trotz hoher Sauerstoffugazität enthält Granat, der aus einem Fe-freien Gel erhalten wurde, ausschließlich zweiwertiges Mangan und stellt einen Mischkristall zwischen Pyrop und Spessartin dar (Py₇₉Spess₂₁).

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With 2 Figures     

Optical absorption spectra and Fe distribution in the structures of Li-Fe micas

The paper proposes pioneering data on the polarized optical absorption spectra of Li-Fe micas: intermediate members of the siderophyllite-zinnwaldite-polylithionite and annite-protolithionite-zinnwaldite-trilithionite series with variable Fe and Li proportions and Li- and Fe-bearing muscovite (phengite). Based on the analysis of structural data, the complicated structure of the Fe²⁺ → Fe³⁺ charge transfer band in the mica structures is explained, and arguments are presented to justify the ascribing of its shortwave component (CTB-1, ν = 17200-14900 cm^?1) to charge transfer in the pair Fe²⁺(M2) → Fe³⁺(M2) and the longwave component (CTB-2, ν = 14200-13600 cm^?1) to charge transfer in the pair Fe²⁺(M1) Fe³⁺(M2). It is demonstrated that the anomalous shift of the superposition of two-component CTB toward the shortwave region, to 17000 cm^?1, results from a decrease in the length of oxygen edges between adjacent M2M2 and M1M2 tetrahedrons when Li is accommodated in the mica structure. The first data are presented on the spectrum of Fe²⁺ ions in large distorted M3(M1) tetrahedrons (OAC Fe²⁺ II) in hetero-octahedral Li micas (zinnwaldite), and the behavior of the corresponding absorption bands at 11400 and 8000 cm^?1 is determined. It is proved that characteristics of the optical spectra of Fe²⁺ ions can be used as an indicator of the structure of the octahedral layer in the mica structures. Results of the comparative analyses of spectral parameters of the Fe²⁺ → Fe³⁺ charge transfer, crystal field spectra of Fe²⁺ ions, and the crystal-chemical characteristics controlling them in micas of the polylithionite-siderophyllite series are completely consistent with the character of cation ordering in the crystal structures of these micas determined by X-ray diffraction analysis.     

Single crystal absorption spectra of synthetic Ti,Fe-substituted pyropes

Synthetic pyrope crystals up to 0.5 mm in diameter, substituted by titanium or by titanium plus iron, were grown under defined conditions of P, T, $f_{O_2 }$ in the presence of water using a piston-cylinder device. The crystals were characterized by X-ray and microprobe techniques. Their single-crystal optical absorption spectra were measured by means of a microscope-spectrometer. Two absorption bands at 16100 and 22300 cm{cm-1} in the spectra of pale-blue Fe-free Ti-bearing pyropes, grown under reduced conditions, were identified as originating from spin-allowed transitions, derived from ² T _2g → ² E _g of octahedral Ti³⁺ ions. The splitting value of the excited ²E _g state, 6200 cm^-1, and the crystal field parameter of Ti³⁺ in pyrope Δ ₀ = 19 200 cm^-1 are both in agreement with literature data. In spectra of brown Fe, Ti-bearing garnets, a broad band at 23000 cm^-1 was interpreted as a Fe^2+[8] → Ti^4+[6] charge-transfer band. The spectral position and width of this band agree with those observed for a FeTi charge transfer band in natural garnets. Fe, Ti-containing garnets synthesized at relatively high oxygen fugacity (10^-11,0 atm), which permits a fraction of Fe³⁺ to enter the garnet, show an additional Fe^2+[8] → Fe^3+[6] charge transfer band at 19800 cm^-1.     

Calculated optical absorption spectra of Ni2+-bearing compounds

The transition energies responsible for optical absorption spectra can be obtained by crystal-field analysis, but the transition intensities are notoriously difficult to calculate. This paper examines the basic ingredients of the calculation of optical spectrum intensities. Magnetic dipole and electric quadrupole transitions intensities are evaluated, as well as the direct d(Ni²⁺) to p(O²⁻) electric dipole transitions. All these contributions are shown to be small in the optical range, so that spectral intensities are due to the mixing of odd orbitals with the Ni²⁺ 3d ⁿ states. Received: 11 November 1997 / Revised, accepted: 6 September 1999     

Electronic absorption spectra of Cr3+ ions in natural clinopyroxenes

The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr₂O₃), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr³⁺ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C ₂ or C _2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C _3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D _q increases from diopside (1542 cm^?1) through omphacite (1552 cm^?1), jadeite (1574 cm^?1) to spodumene (1592 cm^?1). The parameter B which is a measure of covalency for Cr³⁺-O bonds at M1 sites in clinopyroxene depends on the Cr³⁺ concentration and the cations at M2 sites.     

Determination of quantitative cation distribution in orthopyroxenes from electronic absorption spectra

Electronic and Mössbauer absorption spectra and electron microprobe data are correlated for iron-bearing orthopyroxenes. The correlation provides a means of quantitatively determining the distribution of Fe²⁺ between the M(1) and M(2) sites of orthopyroxene crystals from electronic spectra and electron microprobe analysis. The electronic spectra are used to analyze the changes in the Fe²⁺ distribution produced during heating experiments and confirm earlier results from Mössbauer spectra. Two components of the spin-allowed transition of Fe²⁺ in the M(1) site are identified at about 13,000 cm^?1 and 8,500 cm^?1 in γ. Molar absorptivity (?) values for all spin-allowed Fe²⁺ absorption bands in the near-infrared region are determined. The M(2) Fe²⁺ band at ～5,000 cm^?1 in β is the analytically most useful for site occupancy determinations. It remains linear with concentration (?=9.65) over the entire compositional range. The band at ～10,500 cm^?1 in α is the most sensitive to M(2) Fe²⁺ concentration (?=40.8), but deviates from linearity at high iron concentrations. The origins of spin-forbidden transitions in the visible region are examined.     

The possibility of observing resonance gamma-ray absorption in the spectra of active galactic nuclei

The Geant 4.8.1 program package has been used to carry out Monte Carlo simulations of resonance features arising in gamma-ray spectra due to the passage of the photons through a large amount of neutral, stationary material under conditions corresponding to those in active galactic nuclei (AGNs). The dependences of the depth and shape of resonance features on the optical depth and geometry of the absorbing material, as well as parameters of the initial spectrum, are analyzed. Special attention is paid to the dependence of the spectrum on the viewing angle for the observations relative to the symmetry axis of a beam of gamma-rays, for viewing angles from fractions of a degree to several tens of degrees. It is shown that Δ-resonance absorption with appreciable depths (>10%) can appear in the gamma-ray spectra of AGNs only if observations are made at small angles (<0.2°) to the beam axis.     

Synthesis and optical absorption spectra of Cr2+-containing orthosilicates

By reacting chromium metal with appropriate oxides in a neutral atmosphere at high temperature it is possible to prepare Mg₂SiO₄ with the olivine structure containing Cr⁺⁺ and also Cr₂SiO₄. X-ray powder diffraction data for chromous orthosilicate may be indexed on an orthorhombic cell with a=5.690, b=11.262, and c=9.584 Å. The compound is not isotructural with olivine. Optical absorption spectra of Cr²⁺ in both hosts have been obtained and also indicate large differences between the two structures.     

Polarized electronic absorption spectra of Cr2SiO4 single crystals

Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000–5000?cm^–1 were obtained for the orthorhombic thenardite-type phase Cr₂SiO₄, unique in its Cr²⁺-allocation suggesting some metal-metal bonding in Cr²⁺Cr²⁺ pairs with Cr-Cr distance 2.75?Å along [001]. The spectra were scanned at 273 and 120?K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6?μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20?μm and 1?nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr₂SiO₄, synthesized at 35?kbar, above 1440?°C from high purity Cr₂O₃, Cr (10% excess) and SiO₂ in chromium capsules. The Cr₂SiO₄-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm^–1, in the absorption spectra of Cr₂SiO₄ single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr²⁺ in a distorted square planar coordination of point symmetry C₂. The crystal field parameter of Cr²⁺ is estimated to be 10?Dq?10700?cm^–1. A relatively intense, sharp band at 18400?cm^–1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr²⁺. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000?cm^–1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr₂ ⁴⁺, whereas the latter alone would be in conflict with the strong polarization of bands I and II parallel [100]. Therefore, it is concluded that the spectra obtained can best be interpreted assuming both dd-transitions of localized d-electrons at Cr²⁺ as well as δ-δ* transitions of Cr₂ ⁴⁺ pairs with metal-metal interaction. To explain this, a dynamic exchange process 2 Cr_loc ²⁺?Cr_{2, cpl} ⁴⁺ is suggested wherein the half life times of the ground states of both exchanging species are significantly longer than those of the respective optically excited states, such that the spectra show both dd- and δ-δ*-transitions.     

Temperature dependence of the polarized electronic absorption spectra of olivines. Part I – fayalite

 Polarized electronic absorption spectra of orthorhombic fayalite, Fe₂SiO₄, [E || a(|| Z),E || b(|| X), E || c(|| Y)], space group Pbnm, have been studied in the temperature range 293 ≤T/K ≤ 1273. The spectra were analysed into component bands originating from spin-allowed dd transitions of iron(II) at the different sites, M1 and M2, in the structure. The assignments of bands, made on the basis of the polarization dependence of the spectra and considerations of transition energies, were confirmed by the analysis of the temperature-dependent spectra. The temperature dependencies of integral intensities, half band widths and energy positions of absorptions bands caused by Fe²⁺ on the different octahedral sites, M1 and M2, were evaluated for the individual transitions. Independent of the site symmetry, absorption bands shift to lower energies and half band widths increase on rising temperature. The temperature dependence of band intensities depends on site symmetry. The integral intensities are found to increase with temperature for the transition metal ion on a centrosymmetric site, or remain constant when the site is missing an inversion centre. This is consistent with the general conclusion of Taran et al. (1994). Received: 11 October 2001 / Accepted: 17 January 2002     

On yoderite: Using calculated phase equilibria to investigate its rarity in the geological record of whiteschists

A new activity–composition model is presented for green (Mn³⁺‐absent) yoderite for use in the latest internally consistent thermodynamic data set used by THERMOCALC, for calculations primarily in MgO–Al₂O₃–SiO₂–H₂O–O system, where O is a proxy for Fe₂O₃. P–T grids calculated with our model in the MASH and MASHO system feature invariant points and univariant reaction bundles that are consistent with existing experimental results. Using this new model, we have explored the stability of yoderite in whiteschists, a rare type of high‐pressure rock that conforms closely to the MASHO system. Using a series of calculated models in which composition varies, it is shown that yoderite stability is a function of bulk‐rock SiO₂, MgO and Al₂O₃, where the most important component for stabilizing yoderite is a function of pressure and temperature. The rarity of yoderite in naturally occurring whiteschists is largely related to these compositional factors, with most whiteschists having rock compositions that are too SiO₂‐rich and Al₂O₃‐poor to allow yoderite formation. However, in addition to compositional factors, the calculated P–T stability field of yoderite occurs over thermal gradients that are generally too high to occur in modern‐style subduction zones. As nearly all known whiteschist occurrences are Phanerozoic in age, the near‐complete absence of yoderite in late Neoproterozoic–Phanerozoic whiteschists may be at least partially due to modern subduction systems failing to produce the hotter thermal gradients needed to stabilize yoderite. The provision of this new a–x model for green yoderite allows for more rigorous P–T–X investigations of all whiteschists.     

Metamict transformations in some niobates and zircons according to X-ray absorption spectra

The niobium and zirconium L _III-absorption spectra in some niobates and zircons were obtained with a vacuum focusing crystal spectrometer. The effective charges of Nb and Zr in these minerals were derived from the X-ray absorption spectra. The fine structure of the absorption spectra and effective charges Nb and Zr in metamict, partly-metamict minerals and crystalline analogues made it possible to draw a conclusion as to the nature of the first coordination sphere of Nb and Zr during metamict decay and subsequent recrystallization under annealing of these minerals.