Fe-rich cordierites from acid volcanic rocks,an optical and x-ray single-crystal structure study

Low-cordierites from volcanic rocks of Tuscany (Italy), Lipari (Italy), and of the Cerberean Cauldron (Australia) were investigated. Both single crystal structure refinements and optical data indicate that the Italian samples contain only low concentrations of volatiles (<0.3 wt.%), whereas in the crystals from the Cerberean Cauldron more than 50% of the structural channels are occupied, preferentially by H₂O (1.6–1.9 wt.%). This high volatile concentration is in qualitative agreement with the estimated p,T-conditions (4–4.5 kbar at 750–780° C) of the magma prior to eruption. In contrast, the Italian cordierites have formed at temperatures above 950° C and pressures below 2 kbars. Low-cordierites of volcanic origin reveal the same high degree of Si, Al-ordering as observed for low-cordierites from metamorphic rocks and pegmatites. The crystals studied possess F(mol)=(Fe+Mn)/(Fe+Mn+Mg)>0.4 and provide additional information about the crystal structure of Fe-rich cordierites. With increasing FeMg substitution the mean T₁1(Al)-O distance decreases slightly, which is probably not caused by substitution of smaller cations on t₁1 but by angular distortion of the tetrahedron.     

Heavy-ion irradiation on crystallographically oriented cordierite and the conversion of molecular CO2 to CO: a Raman spectroscopic study

Crystallographically oriented sections of natural gemstone quality cordierite single-crystals have been irradiated with swift heavy ions of GeV energy and various fluences. Irradiation effects on the crystal lattice were investigated by means of Raman spectroscopy. Raman line scans along the trajectory of the ions reveal a close correlation of beam parameters (such as fluence and energy loss dE/dx along the ion path) to strain due to associated changes in lattice dimensions and defect concentration. The luminescence background also scales with the ion fluence and suggests the formation of point defects, which could also account for the macroscopically observable colouration of the irradiated samples. In addition, changes in the amount and nature of volatile species inside the structural channels are observed. They also scale with dE/dx and confirm the previously postulated irradiation-induced conversion of CO₂ to CO. Irradiations along the crystallographic a-, b- and c-axis reveal no significant anisotropy effect with respect to lattice alterations. The polarisation characteristics of the Raman-active modes confirm the preferred molecular alignment of CO and CO₂ along the a-axis direction.     

An infrared spectroscopic and single-crystal X-ray study of malayaite, CaSnSiO5

Powder infrared spectroscopy and X-ray diffraction techniques on single crystals were used to study the thermal behaviour of malayaite, CaSnSiO₅. Infrared spectra show a discontinuity in the temperature evolution of phonon frequencies and absorbance near 500 K. However, crystal structure data collected at 300, 450, 550, 670, and 750 K show no evidence of a symmetry-breaking phase transition and no split positions. The most obvious change with heating is a tumbling motion of the SnO₆ octahedra and an increase of the anisotropic displacement factors of Ca. The thermal evolution of the mean-square vibrational amplitude of the Ca atom shows a pronounced change in slope near 500 K. The evidence suggests that the 500 K anomaly in malayaite is more similar in character to the 825 K (β-γ) transition as opposed to the 496 K (α-β) transition in synthetic titanite. Received: 26 March 1998 / Revised, accepted: 23 December 1998     

High-pressure single-crystal X-ray diffraction study of jadeite and kosmochlor

The crystal structures of natural jadeite, NaAlSi₂O₆, and synthetic kosmochlor, NaCrSi₂O₆, were studied at room temperature, under hydrostatic conditions, up to pressures of 30.4 (1) and 40.2 (1) GPa, respectively, using single-crystal synchrotron X-ray diffraction. Pressure–volume data have been fit to a third-order Birch–Murnaghan equation of state yielding V ₀ = 402.5 (4) Å³, K ₀ = 136 (3) GPa, and K ₀ ^′  = 3.3 (2) for jadeite and V ₀ = 420.0 (3) Å³, K ₀ = 123 (2) GPa and K ₀ ^′  = 3.61 (9) for kosmochlor. Both phases exhibit anisotropic compression with unit-strain axial ratios of 1.00:1.95:2.09 for jadeite at 30.4 (1) GPa and 1:00:2.15:2.43 for kosmochlor at 40.2 (1) GPa. Analysis of procrystal electron density distribution shows that the coordination of Na changes from 6 to 8 between 9.28 (Origlieri et al. in Am Mineral 88:1025–1032, 2003) and 18.5 (1) GPa in kosmochlor, which is also marked by a decrease in unit-strain anisotropy. Na in jadeite remains six-coordinated at 21.5 (1) GPa. Structure refinements indicate a change in the compression mechanism of kosmochlor at about 31 GPa in both the kinking of SiO₄ tetrahedral chains and rate of tetrahedral compression. Below 31 GPa, the O3–O3–O3 chain extension angle and Si tetrahedral volume in kosmochlor decrease linearly with pressure, whereas above 31 GPa the kinking ceases and the rate of Si tetrahedral compression increases by greater than a factor of two. No evidence of phase transitions was observed over the studied pressure ranges.     

X-ray single-crystal study of spinels: in situ heating

 Two MgAl₂O₄ stoichiometric spinel crystals, one natural and one synthetic, were heated from 25 to 950 °C and studied in situ by single-crystal X-ray diffraction. The natural crystal, quenched from 850 °C, was further heated and cooled. Thermal expansion was characterized, and cation partitioning at the various temperatures was determined according to a model purposely constructed for high-temperature bond lengths. It was found that the structural evolution of the samples with temperature depended on order–disorder at room temperature. At the temperatures lower than the beginning of cation exchange, thermal expansion was completely reversible and the oxygen coordinate remained stable in spite of varying temperatures. At the temperature at which cation exchange starts, the disordered samples first tend to order and then to disorder at higher temperatures, at variance with the ordered sample, which tends to disorder steadily. In general, the evolution of the spinel structural state on cooling and heating over the same temperature range and the same time intervals does not follow the same path. In particular, in the 600–950 °C range, only partially reversible order–disorder processes occurred in the time span used for the experiments. Received: 16 July 2001 / Accepted: 8 January 2002     

Quantitative analysis of H2O and CO2 in cordierite using polarized FTIR spectroscopy

We report a FTIR (Fourier transform infrared) study of a set of cordierite samples from different occurrence and with different H₂O/CO₂ content. The specimens were fully characterized by a combination of techniques including optical microscopy, single-crystal X-ray diffraction, EMPA (electron microprobe analysis), SIMS (secondary ion mass spectrometry), and FTIR spectroscopy. All cordierites are orthorhombic Ccmm. According to the EMPA data, the Si/Al ratio is always close to 5:4; X _Mg ranges from 76.31 to 96.63, and additional octahedral constituents occur in very small amounts. Extraframework K and Ca are negligible, while Na reaches the values up to 0.84 apfu. SIMS shows H₂O up to 1.52 and CO₂ up to 1.11 wt%. Optically transparent single crystals were oriented using the spindle stage and examined by FTIR micro-spectroscopy under polarized light. On the basis of the polarizing behaviour, the observed bands were assigned to water molecules in two different orientations and to CO₂ molecules in the structural channels. The IR spectra also show the presence of small amounts of CO in the samples. Refined integrated molar absorption coefficients were calibrated for the quantitative microanalysis of both H₂O and CO₂ in cordierite based on single-crystal polarized-light FTIR spectroscopy. For H₂O the integrated molar coefficients for type I and type II water molecules (ν₃ modes) were calculated separately and are ^[I]ε?=?5,200?±?700?l?mol^?1?cm^?2 and ^[II]ε?=?13,000?±?3,000?l?mol^?1?cm^?2, respectively. For CO₂ the integrated coefficient is $ \varepsilon_{{{\text{CO}}_{ 2} }} $ ?=?19,000?±?2,000?l?mol^?1?cm^?2.     

Very high CO2 cordierite from Norwegian Lapland: Mineralogy,petrology, and carbon isotopes

The most CO₂-rich cordierite thus far encountered in nature with about 2.2 wt.% CO₂ and 0.3 wt.% H₂O occurs as large poikiloblasts in a strange non-foliated reaction rock that dissects well-foliated granulites being part of the classical Lapland granulite area described by Eskola. The cordierite is optically positive with the highest optic angle 2V _x (106°) and birefringence (– = 0.017) ever measured on natural cordierites, but it is also optically very heterogeneous due to secondary loss of CO₂ along fractures and zones paralleling the fluid-bearing channels. Based on the optical properties of the degassed Lapland cordierite and on literature data a ternary diagram is given, which shows the variations of this cordierite in 2V _x and birefringence as a function of channel-filling with both CO₂ and H₂O.Following Losert (1971) the cordierite coexists with calcite, a thus far unique mineral assemblage that is probably only stable at very high CO₂ pressures. In the present case, the of the cordierite (0.75) indicates, on the basis of literature data, a coexisting fluid with >0.95.The carbon isotope composition ¹³C of CO₂ in cordierite lies near –7, that of the calcite is slightly lighter than about –9. Thus, at least for the CO₂ in cordierite, a deep-seated origin may be possible.Based on the geologic occurrence it is speculated that the cordierite-bearing reaction rock could perhaps represent an annealed channel of late degassing in the granulitic lower crust.     

Antigorite equation of state and anomalous softening at 6 GPa: an in situ single-crystal X-ray diffraction study

The compressibility of antigorite has been determined up to 8.826(8) GPa, for the first time by single crystal X-ray diffraction in a diamond anvil cell, on a specimen from Cerro del Almirez. Fifteen pressure–volume data, up to 5.910(6) GPa, have been fit by a third-order Birch–Murnaghan equation of state, yielding V ₀ = 2,914.07(23) Å³, K _T0 = 62.9(4) GPa, with K′ = 6.1(2). The compression of antigorite is very anisotropic with axial compressibilities in the ratio 1.11:1.00:3.22 along a, b and c, respectively. The new equation of state leads to an estimation of the upper stability limit of antigorite that is intermediate with respect to existing values, and in better agreement with experiments. At pressures in excess of 6 GPa antigorite displays a significant volume softening that may be relevant for very cold subducting slabs.     

A single-crystal neutron and X-ray diffraction study of pezzottaite, Cs(Be2Li)Al2Si6O18

The chemical composition and the crystal structure of pezzottaite [ideal composition Cs(Be₂Li)Al₂Si₆O₁₈; space group: ${\it{R}} \overline{\text{3}} $ c, a?=?15.9615(6) ?, c?=?27.8568(9) ?] from the type locality in Ambatovita (central Madagascar) were investigated by electron microprobe analysis in wavelength dispersive mode, thermo-gravimetric analysis, Fourier-transform infrared spectroscopy, single-crystal X-ray (at 298?K) and neutron (at 2.3?K) diffraction. The average chemical formula of the sample of pezzottaite resulted ^Cs1,Cs2(Cs_0.565Rb_0.027K_0.017)_Σ0.600 ^Na1,Na2(Na_0.101Ca_0.024)_Σ0.125Be_2.078Li_0.922 ^Al1,Al2(Mg_0.002Mn_0.002Fe_0.003Al_1.978)_Σ1.985 ^Si1,Si2,Si3(Al_0.056Si_5.944)_Σ6O₁₈·0.27H₂O. The (unpolarized) IR spectrum over the region 3,800–600?cm^?1 was collected and a comparison with the absorption bands found in beryl carried out. In particular, two-weak absorption bands ascribable to the fundamental H₂O stretching vibrations (i.e. 3,591 and 3,545?cm^?1) were observed, despite the mineral being nominally anhydrous. The X-ray and neutron structure refinements showed: (a) a non-significant presence of aluminium, beryllium or lithium at the Si1, Si2 and Si3 sites, (b) the absence (at a significant level) of lithium at the octahedral Al1, Al2 and Al3 sites and (c) a partial lithium/beryllium disordering between tetrahedral Be and Li sites.     

Displacement behavior of CH4 adsorbed on coals by injecting pure CO2, N2, and CO2–N2 mixture

Gas adsorption isotherms of Akabira coals were established for pure carbon dioxide (CO₂), methane (CH₄), and nitrogen (N₂). Experimental data fit well into the Langmuir model. The ratio of sorption capacity of CO₂, CH₄, and N₂ is 8.5:3.5:1 at a lower pressure (1.2 MPa) regime and becomes 5.5:2:1 when gas pressure increases to 6.0 MPa. The difference in sorption capacity of these three gases is explained by differences in the density of the three gases with increasing pressure. A coal–methane system partially saturated with CH₄ at 2.4 MPa adsorption pressure was experimentally studied. Desorption behavior of CH₄ by injecting pure CO₂ (at 3.0, 4.0, 5.0, and 6.0 MPa), and by injecting the CO₂–N₂ mixture and pure N₂ (at 3.0 and 6.0 MPa) were evaluated. Results indicate that the preferential sorption property of coal for CO₂ is significantly higher than that for CH₄ or N₂. CO₂ injection can displace almost all of the CH₄ adsorbed on coal. When modeling the CH₄–CO₂ binary and CH₂–CO₂–N₂ ternary adsorption system by using the extended Langmuir (EL) equation, the EL model always over-predicted the sorbed CO₂ value with a lower error, while under-predicting the sorbed CH₄ with a higher error. A part of CO₂ may dissolve into the solid organic structure of coal, besides its competitive adsorption with other gases. According to this explanation, the EL coefficients of CO₂ in EL equation were revised. The revised EL model proved to be very accurate in predicting sorbed ratio of multi-component gases on coals.     

A low temperature X-ray single-crystal diffraction and polarised infra-red study of epidote

The effects of low-temperature on the crystal structure of a natural epidote [Ca_1.925Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6)? and β = 115.396(8)° at room conditions, Sp. Gr. P2₁ /m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe³⁺ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000–2,500 cm⁻¹ are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)–O(4). Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and Fe³⁺ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to protonation of O(10)–O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected for “rigid body motions”. A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra, especially when corrected for “non-correlated motion”. The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction of the magnitude of the thermal displacement ellipsoids, with a variation of U _eq (defined as one-third of the trace of the orthogonalised U _ij tensor) by ~40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U _eq of the octahedral and oxygen sites decrease similarly by ~35%, whereas those of the tetrahedral cations by ~22%.     

Chemical,optical, and X-ray analysis of an unusual muscovite-biotite intergrowth

A specimen of intergrown biotite and muscovite from a pegmatite was subjected to detailed chemical, optical, and X-ray analysis. The crystals are intergrown in such a way that certain structural elements are common to both and that parts of the crystal structure must pass unbroken through the contact between them. Numerous ‘edge dislocations’ must occur at the boundary because of the different basal spacings. Partitioning of elements between the minerals, along with the structural observations, suggest that the crystals are an equilibrium intergrowth.     

High-pressure crystal chemistry of chromous orthosilicate, Cr2SiO4. A single-crystal X-ray diffraction and electronic absorption spectroscopy study

The high-pressure behaviour of chromous orthosilicate, Cr₂SiO₄, has been studied by means of single-crystal X-ray diffraction and electronic absorption spectroscopy. X-ray diffraction data show that the structure remains orthorhombic to the highest pressure reached of 9.22?GPa. The compressibility of the unit-cell is strongly anisotropic with the c axis approximately six times more compressible than the a and b axes. A third-order Birch-Murnaghan equation of state fitted to the volume-pressure data yields V ₀?=?610.10(3)?ų, K = 94.7(4)?GPa, K′?=?8.32(14). Cr₂SiO₄ is therefore more compressible than the isostructural Cd analogue, even though its molar volume is smaller. This unusual behaviour can be attributed to the fact that the Cr atom is too small for the six-coordinated site that it occupies, and the site is therefore strongly distorted. Structure refinements indicate that under high pressures the Cr atom remains strongly displaced from the central position of the octahedron. Polarized and unpolarized electronic absorption spectra include a strong absorption band occuring at 18.300 cm^?1 for E//c (which is parallel to the shortest Cr-Cr vector in the structure) which has an unusually large half width (5000?cm^?1), indicative of electronic interaction between metal centres. Deconvolution of unpolarized high-pressure spectra show that the relative integrated intensity of this component increases linearly from 40% at 1?bar to 60% at 11.2?GPa. Both the structural changes and the absorption spectra at high pressures suggest that pairs of adjacent Cr atoms in chromous orthosilicate form chromium dimers with a weak metal-metal bond, which is consistent with the diamagnetic response found at ambient pressure.     

Pressure-induced dehydration of dioptase: A single-crystal X-ray diffraction and Raman spectroscopy study

We present a synchrotron-based, single-crystal X-ray diffraction and Raman spectroscopy study of natural green dioptase (Cu₆Si₆O₁₈·6H₂O) up to ∼30 GPa at room temperature. The lattice parameters of dioptase exhibit continuous compression behavior up to ∼14.5 GPa, whereupon a structural transition is observed. Pressure–volume data below 14.5 GPa were fitted to a second-order Birch–Murnaghan equation of state with V₀ = 1440(2) ų and K₀ = 107(2) GPa, with K₀′ = 4(fixed). The low-pressure form of dioptase exhibits anisotropic compression with axial compressibility β_a > β_c in a ratio of 1.14:1.00. Based on the diffraction data and Raman spectroscopy, the new high-pressure phase could be regarded as a dehydrated form of dioptase in the same symmetry group. Pressure-induced dehydration of dioptase contributes broadly to our understanding of the high-pressure crystal chemistry of hydrous silicates containing molecular water groups.     

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.