Polarized single-crystal FTIR-spectra of natural staurolite

Polarized infrared absorption spectra of thin single-crystal slabs parallel to (010) and (001) of a staurolite from Pizzo Forno, Ticino, with analyzed composition (Fe_2.9Mg_0.9Zn_0.1Mn_0.1)Al_17.5Ti_0.1(Si_7.7Al_0.3)O₄₈H₃ have been measured in the range of 3000–4000 cm^?1. From the pleochroitic behaviour of the OH-vibrations three groups of bands can be distinguished: the bands of group I, a strong band at 3445 cm^?1 plus a weak shoulder at 3358 cm^?1, and the bands of group II, a weak band centered at 3677 cm^?1 plus a shoulder at 3635 cm^?1, are assigned to the H1 and H2 protons, respectively. The bands of group III, a weak band at 3577 cm^?1 plus a shoulder, cannot be interpreted on the basis of the proton positions known so far. We assign them to an additional proton H3, which is bonded to O1 and shows a bifurcated hydrogen bridge to two O5 in a vacant T2 site.     

Crystal field spectra and jahn teller effect of Mn3+ in clinopyroxene and clinoamphiboles from India

Blanfordite (I), winchite (II), and juddite (III), all showing vivid colors and pleochroism, from highly oxidized parageneses of Indian gondites were studied by microprobe, Mössbauer, and microscope-spectrophotometric techniques and by X-ray structure refinements. The compositions of the Mn-bearing minerals were close to diopsideacmite (I) and magnesio-arfvedsonite to magnesio-riebeckite (II and III). Transition metal ions are located inM(1)-octahedra (I) or predominantlyM(2)-octahedra (II, III). Mössbauer spectra of⁵⁷Fe(IS, ΔE _Q) are typical of octahedral Fe³⁺ only. Polarized absorption spectra in the UV/VIS/NIR ranges explain color and pleochroism of the minerals. The position of the UV-“edge” is correlated with Fe³⁺-contents of the minerals, except for judditeE ∥Z, where the edge shows an unusual low energy position. This is most likely due to Mie-scattering of submicroscopic inclusions of braunite with nearly uniform dimensions. In the VIS range, the spectra are dominated by a complex band system between 15,000 and 20,000 cm^?1. Energies and ?-values of component bands are compatible with those of Mn³⁺ d-d transitions in other Mn³⁺-bearing silicates. The polarization behavior of component bands can best be explained by aC ₂(C2″) symmetry of the crystal field. The Jahn-Teller splitting (<9,000 cm^?1) of the⁵ E _g ground state of Mn³⁺ inO _h crystal fields is appreciably smaller than in other Mn³⁺-silicates. Crystal field parameters 10Dq, (I) 13,650, (II) ca. 11,640, and (III) 11,925 cm^?1, are near to that in piemontite. The crystal field stabilization energy of Mn³⁺, (I) 146, (II) ca. 140, (III) 142 \({{{\text{kJ}}} \mathord{\left/ {\vphantom {{{\text{kJ}}} {\text{g}}}} \right. \kern-0em} {\text{g}}}{\text{ - atom}}_{{\text{Mn}}^{{\text{3 + }}} } \) , is appreciably smaller than that found in other Mn³⁺-silicates (piemontites and manganian andalusites, viridines and kanonaite).     

Electronic absorption spectra of Fe2+ ions in oxygen-based rock-forming minerals at temperatures between 297 and 600 K

 Polarized electronic single crystal spectra of natural Fe²⁺ ion-bearing oxygen-based minerals, in which ferrous ions enter octahedral sites of different symmetry and distortion (olivine, cordierite, ortho- and clinopyroxene, amphibole), eightfold sites in garnet (almandine) and clinopyroxene (M2), and tetrahedral sites in spinel, were studied at temperatures from 300 to ca. 600 K. In the minerals studied, the spin-allowed bands of Fe²⁺ display rather variable temperature behaviour. In most cases, due to the thermal expansion of the Fe²⁺-bearing polyhedra, bands shift to lower energies upon increasing temperature, though there are some exceptions to this rule: in cases of other than sixfold octahedral or close to octahedral coordination, in almandine and spinel the bands shift to higher energies, which can be explained by an increase in distortions of the Fe²⁺-bearing polyhedra. Splitting of the excited ⁵ E _g-level of Fe²⁺ ions usually, but not always, increases with temperature, reflecting thermally induced increase in distortion of the Fe²⁺-bearing sites in the minerals studied. Integral intensities of the bands in question do not always obey the general rule, according to which intensity should increase with temperature, when the 3d ^N-centred site is centrosymmetric, or should remain unchanged when the 3d ^N site lacks an inversion centre. The experimental results show that the response of the characteristics of absorption bands such as width, intensity and energy caused by dd transitions of Fe²⁺ in oxygen-based minerals to increasing temperature is not always uniform and is at variance with expectation. This temperature dependence cannot be used directly to solve band assignment problems, as earlier proposed in the literature. Received: 22 December 1999 / Accepted: 30 October 2000     

Effect of Fe3+-bearing point defects on the UV-spectra of two natural olivines

Polarized near-UV spectra have been recorded on 20 μm diameter spots on oriented crystals of microprobe-analyzed olivines from Baikhal Rift, Fa_8.8 (I) and Seberget, Fa_9.3 (II), which have formed under different fO₂ and, therefore, are expected to contain Fe³⁺-bearing point defects in different concentrations. These should be reflected in the UV-spectra of such minerals (Cemic et al. 1986). The spectra obtained confirm these predictions: The difference in α _{Y, 26500} in both samples indicates a difference in Fe³⁺-site fractions of ΔX_Fe. = 1.78-10⁻⁴, which may be related to an fO₂ about ten times higher for the formation of olivine II compared to I.     

Calcium isotope fractionation in coccoliths of cultured Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa

Four species of marine calcifying algae, the coccolithophores Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa were grown in laboratory cultures under temperatures varying between 14 and 23 °C, and one species, C. leptoporus, under varying [CO₃²⁻], ranging from 105 to 219 μmol/kg. Calcium isotope compositions of the coccoliths resemble in both absolute fractionation and temperature sensitivity previous calibrations of marine calcifying species e.g. Emiliania huxleyi (coccolithophores) and Orbulina universa (planktonic foraminifera) as well as inorganically precipitated CaCO₃, but also reveal small species specific differences. In contrast to inorganically precipitated calcite, but similar to E. huxleyi and O. universa, the carbonate ion concentration of the medium has no statistically significant influence on the Ca isotope fractionation of C. leptoporus coccoliths; however, combined data of E. huxleyi and C. leptoporus indicate that the observed trends might be related to changes of the calcite saturation state of the medium. Since coccoliths constitute a significant portion of the global oceanic CaCO₃ export production, the Ca isotope fractionation in these biogenic structures is important for defining the isotopic composition of the Ca sink of the ocean, one of the key parameters for modelling changes to the marine Ca budget over time. For the present ocean our results are in general agreement with the previously postulated and applied mean value of the oceanic Ca sink (Δ_sed) of about − 1.3‰, but the observed inter- and intra-species differences point to possible changes in Δ_sed through earth history, due to changing physico-chemical conditions of the ocean and shifts in floral and faunal assemblages.     

Electronic absorption and luminescence spectroscopic studies of kyanite single crystals: differentiation between excitation of FeTi charge transfer and Cr3+ dd transitions

A selected set of five different kyanite samples was analysed by electron microprobe and found to contain chromium between <0.001 and 0.055 per formula unit (pfu). Polarized electronic absorption spectroscopy on oriented single crystals, R₁, R₂-sharp line luminescence and spectra of excitation of λ₃- and λ₄-components of R₁-line of Cr³⁺-emission had the following results: (1) The Fe²⁺–Ti⁴⁺ charge transfer in c-parallel chains of edge connected M(1) and M(2) octahedra shows up in the electronic absorption spectra as an almost exclusively c(||Z′)-polarized, very strong and broad band at 16000 cm⁻¹ if <, in this case the only band in the spectrum, and at an invariably lower energy of 15400 cm⁻¹ in crystals with  ≥ . The energy difference is explained by an expansion of the O_f–O_k, and O_b–O_m edges, by which the M(1) and M(2) octahedra are interconnected (Burnham 1963), when Cr³⁺ substitutes for Al compared to the chromium-free case. (2) The Cr³⁺ is proven in two greatly differing crystal fields a and b, giving rise to two sets of bands, derived from the well known dd transitions of Cr^{3+ 4}A_2g→⁴T_2g(F)(I), →⁴T_1g(F)(II), and →⁴T_1g(P)(III). Band energies in the two sets a and b, as obtained by absorption, A, and excitation, E, agree well: I: 17300(a, A), 17200(a, E), 16000(b, A), 16200(b, E); II: 24800(a, A), 24400(a, E); 22300(b, A), 22200(b, E); III: 28800(b,A) cm⁻¹. Evaluation of crystal field parameters from the bands in the electronic spectra yield Dq(a)=1730 cm⁻¹, Dq(b)=1600 cm⁻¹, B(a)=790 cm⁻¹, B(b)=620 cm⁻¹ (errors ca. ±10 cm⁻¹), again in agreement with values extracted from the λ³, λ⁴ excitation spectra. The CF-values of set a are close to those typical of Cr³⁺ substituting for Al in octahedra of other silicate minerals without constitutional OH⁻ as for sapphirine, mantle garnets or beryl, and are, therefore, interpreted as caused by Cr³⁺ substituting for Al in some or all of the M(1) to M(4) octaheda of the kyanite structure, which are crystallographically different but close in their mean Al–O distances, ranging from 1.896 to 1.919 A (Burnham 1963), and slight degrees of distortion. Hence, band set a originates from substitutive Cr³⁺ in the kyanite structural matrix. The CF-data of Cr³⁺ type b, expecially B, resemble those of Cr³⁺ in oxides, especially of corundum type solid solutions or eskolaite. This may be interpreted by the assumption that a fraction of the total chromium contents might be allocated in a precursor of a corundum type exsolution. Received: 3 January 1997 / Revised, accepted: 2 May 1997