Optical absorption investigation of Cr3+ ion-bearing minerals in the temperature range 77–797 K

The effect of raising temperature on spin-allowed dd-transitions of octahedral Cr³⁺ was studied for various point symmetries of the Cr³⁺-bearing structural sites, i.e. 3 m and 3 with inversion center in spinel and garnets, respectively, or 32, 3, 2 and 1, lacking the inversion centre, in beryl, corundum, diopside and topaz, respectively. For this purpose, crystals of Cr³⁺-bearing spinel, pyrope, andradite, grossular, uvarovite, emerald, ruby, diopside and topaz were analyzed by microprobe, oriented, and measured in polarized radiation (except for the cubic minerals) in the spectral range 30 000 to 11 100 cm^-1 and at temperatures between 77 and 797 K. The evaluation of the intensities, half widths, and energy positions of bands due to Cr³⁺-transitions derived from ⁴ A _2g ⁴ T _2g (F) and ⁴ T _1g (F) as well as of Dq- and B-values derived, had the following results:In all cases, red shift of the above bands and, hence, independent on the site symmetry of Cr³⁺, decreases in the Dq-values were obtained. The dependcies of Dq on T are nearly linear above room temperature and amount between -1.6% in topaz and -5.1% in pyrope in the temperature range studied. From this, values for the local thermal expansion of the Cr³⁺-centered octahedra, _loc, were derived on the basis of the R _M-0 ^-5 -proportionality of 10Dq. Such values are consistently higher than those obtained from X-ray refinements, a method averaging r_m-o for all the respective octahedral positions.     

Studies on volcanic gases and gases from hydrothermal fields in Kamchatka

This paper describes the main lines of investigation for the volcanic and geothermal research in Kamchatka. Methods of gas sampling in the field and gas extraction from rocks are also described.     

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     

Synthetic and natural chromium-bearing spinels: an optical spectroscopy study

Four samples of synthetic chromium-bearing spinels of (Mg, Fe²⁺)(Cr, Fe³⁺)₂O₄ composition and four samples of natural spinels of predominantly (Mg, Fe²⁺)(Al, Cr)₂O₄ composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr₂O₄ spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr³⁺ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed ⁴ A _2g  → ⁴ T _2g and ⁴ A _2g  → ⁴ T _1g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spinels is related to trigonal distortion of the octahedral site in the spinel structure. A small, if any, splitting of the U-band can only be resolved at curve-fitting analysis. In all synthetic high-chromium spinels, a couple of relatively narrow and weak bands of the spin-allowed transitions ⁴ A _2g  → ² E _g and ⁴ A _2g  → ² T _1g of Cr³⁺, intensified by exchange-coupled interaction between Cr³⁺ and Fe³⁺ at neighboring octahedral sites of the structure, appear at ~14,400 and ~15,100 cm^?1. A vague broad band in the range from ca. 15,000 to 12,000 cm^?1 in synthetic spinels is tentatively attributed to ^IVCr²⁺ + ^VICr³⁺ → ^IVCr³⁺ + ^VICr²⁺ intervalence charge-transfer transition. Iron, mainly as octahedral Fe³⁺, causes intense high-energy absorption edge in near UV-range (ligand–metal charge-transfer O^2? → Fe³⁺, Fe²⁺ transitions). As tetrahedral Fe²⁺, it appears as a strong infrared absorption band at around 4,850 cm^?1 caused by electronic spin-allowed ⁵ E → ⁵ T ₂ transitions of ^IVFe²⁺. From the composition shift of the U-band in natural and synthetic MgCr₂O₄ spinels, the coefficient of local structural relaxation around Cr³⁺ in spinel MgAl₂O₄–MgCr₂O₄ system was evaluated as ~0.56(4), one of the lowest among (Al, Cr)O₆ polyhedra known so far. The octahedral modulus of Cr³⁺ in MgCr₂O₄, derived from pressure-induced shift of the U-band of Cr³⁺, is ~313 (50) GPa, which is nearly the same as in natural low-chromium Mg, Al-spinel reported by Langer et al. (1997). Calculated from the results of the curve-fitting analysis, the Racah parameter B of Cr³⁺ in natural and synthetic MgCr₂O₄ spinels indicates that Cr–O-bonding in octahedral sites of MgCr₂O₄ has more covalent character than in the diluted natural samples. Within the uncertainty of determination in synthetic MgAl₂O₄ spinel, B does not much depend on pressure.     

The hydrothermal system of Mendeleev Volcano,Kunashir Island,Kuril Islands: The geochemistry and the transport of magmatic components

This paper reports a detailed geochemical study of thermal occurrences as observed in the edifice and on the flanks of Mendeleev Volcano, Kunashir Island in August and September 2015. We showed that three main types of thermal water are discharged there (neutral chloride sodium, acid chloride sulfate, and acid sulfate types); these waters exhibit a zonality that is typical of volcano-hydrothermal island arc systems. Spontaneous and solfataric gases have relatively low ³He/⁴He ratios, ranging between 5.4Ra and 5.6Ra, and δ¹³C-CO₂ between –4.8‰ and –3.1‰, and contain a light isotope of carbon in methane (δ¹³C ≈ –40‰). Gas and isotope geothermometers yield relatively low temperatures around 200°C. The isotope compositions in all types of water are similar to that of local meteoric water. The distribution of microcomponents varies among different types. The isotope composition of dissolved Sr varies considerably, from 0.7034 as observed in Kunashir rocks on an average to 0.7052 in coastal springs, which may have resulted from admixtures of seawater. The total hydrothermal transport rates of magmatic Cl and SO₄, as observed for Mendeleev Volcano, are 7.8 t/d and 11.6 t/d, respectively. The natural outward transport of heat by the volcano’s hydrothermal system is estimated as 21 MW.     

Structural relaxation and crystal field stabilization in Cr3+-containing oxides and silicates

The effect of crystal structure relaxation in oxygen-based Cr³⁺-containing minerals on the crystal field stabilization energy (CFSE) is considered. It is shown that the dependence of \textCFSE_{\textCr ³⁺} {\text{CFSE}}_{{{\text{Cr}}^{ 3+ } }} , which is found from optical absorption spectra, on the average interatomic distances is described by the power function with a negative exponent c \mathord

Fe2+, Mg-distribution among non-equivalent structural sites M1 and M2 in natural olivines: an optical spectroscopy study

Analysis of E||X-polarized optical absorption spectra of natural olivines of various origin in the range of electronic spin-allowed dd-transitions of Fe²⁺ evidences that in some crystals, there is a weak ordering of Fe²⁺ as in M1, as in M2 structural sites. The samples of three different depth facies seem showing a vague tendency of lowering of k _D -values from spinel-pyroxene (Sp-Px) through graphite-pyrope (G-Py) to diamond-pyrope (D-Py) facies, but the statistics are too poor (24 samples only) to be certain of it. Weak relations between Mg, Fe²⁺-distribution and iron content were found for the samples of Sp-Px- and G-Py-facies, while there is practically no one for those of the deepest D-Py facie.     

Major and trace element geochemistry of neutral and acidic thermal springs at El Chichón volcano,Mexico: Implications for monitoring of the volcanic activity

Four groups of thermal springs with temperatures from 50 to 80 °C are located on the S–SW–W slopes of El Chichón volcano, a composite dome-tephra edifice, which exploded in 1982 with a 1 km wide, 160 m deep crater left. Very dynamic thermal activity inside the crater (variations in chemistry and migration of pools and fumaroles, drastic changes in the crater lake volume and chemistry) contrasts with the stable behavior of the flank hot springs during the time of observations (1974–2005). All known groups of hot springs are located on the contact of the basement and volcanic edifice, and only on the W–SW–S slopes of the volcano at almost same elevations 600–650 m asl and less than 3 km of direct distance from the crater. Three groups of near-neutral (pH ≈ 6) springs at SW–S slopes have the total thermal water outflow rate higher than 300 l/s and are similar in composition. The fourth and farthest group on the western slope discharges acidic (pH ≈ 2) saline (10 g/kg of Cl) water with a much lower outflow rate (< 10 l/s).