Raman spectroscopy, vibrational analysis, and heating of buergerite tourmaline

Polarized Raman spectra were collected for single crystal buergerite (NaFe₃Al₆(BO₃)₃Si₆O₁₈(O_0.92(OH)_0.08)₃F) from room temperature to near 1,375°C. Vibrational assignments to features in the room temperature spectra were determined by lattice dynamics calculations, where internal BO₃ motions dominate modes near 1,300 cm⁻¹, internal SiO₄ displacements dominate modes between 900 and 1,200 cm⁻¹, while less localized displacements within the isolated Si₆O₁₈ ring mix with motions within Na, Fe, Al, F, and BO₃ environments for fundamental modes below 780 cm⁻¹. At elevated temperatures, most buergerite Raman features broaden and shift to lower frequencies up to 900°C. Above this temperature, the lattice mode peaks evolve into broad bands, while OH stretch modes near 3,550 cm⁻¹ disappear. According to Raman spectroscopy, X-ray diffraction, differential thermal analysis, and scanning electron microscopy, buergerite undergoes a complex transition that starts near 700°C and extends over a 310°C interval, where initially, Al and Fe probably become disordered within the Y- and Z-sites, and most F and all OH are later liberated. A reversible crystal-to-amorphous transition is seen by Raman for buergerite fragments heated as high as 930°C. Buergerite becomes permanently altered when heated to temperatures greater than 930°C; after cooling to room temperature, these altered fragments are comprised of mullite and Fe-oxide crystals suspended in an amorphous borosilicate matrix.     

Raman spectroscopic studies of carbonates part I: High-pressure and high-temperature behaviour of calcite,magnesite, dolomite and aragonite

The room-temperature Raman spectra of aragonite, magnesite and dolomite have been recorded up to 30 GPa and 25 GPa, respectively and no phase changes were observed during compression, unlike calcite. The effect of temperature on the room-pressure Raman spectra of calcite, aragonite, magnesite and dolomite is reported up to 800–1100 K. The measured relative pressure and temperature-shifts of the Raman lines are greater for the lattice modes than for the internal modes of the CO₃ groups. These shifts are used to calculate the mode anharmonic parameters of the observed Raman modes; they are negative and their absolute values are smaller (close to 0) for the internal CO₃ modes than for the lattice modes (4–17 10^?5 K^?1). The temperature shifts of the lattice modes in calcite are considerably larger than those for dolomite and magnesite, and a marked non-linear increase in linewidth is observed above 400° C for calcite. This is consistent with an increasing relaxational component to the libration of the CO₃ groups about their threefold axes, premonitory to the rotational order-disorder transition at higher temperature. This behaviour is not observed for the other calcite structured minerals in this study. We examine systematic variations in the lattice mode frequencies and linewidths with composition, to begin to understand these differences in their anharmonic behaviour. Finally, we have used a simple Debye-Waller model to calculate atomic displacements in calcite, magnesite and dolomite with increasing temperature from the vibrational frequency data, to provide a direct comparison with atomic positional data from high-temperature structure refinements.     

A raman spectroscopic study of Al-Si ordering in synthetic magnesium cordierite

A number of previous investigations have examined the ordering behavior of magnesium cordierite using X-ray diffraction, transmission electron microscopy, infrared spectroscopy and solution calorimetry. In the present investigation, one series of samples from the above studies has been examined by Raman spectroscopy. Systematic modifications in the spectra with annealing time at 1,200° C are consistent with a continuous ordering of the average Al/Si distribution from 4 h to at least 64 h, and which may begin earlier. Spectral changes are first definitely observed when the ordered domains are around 100 Å across, suggesting that Raman spectroscopy is sensitive to this distance scale. The spectra of samples annealed at 1,200° C are compared with samples annealed at 1,400°; C where ordering proceeds much faster, and the possible use of Raman spectroscopy in characterization of Al/Si order in cordierite is discussed. Finally, the Raman spectrum of Mg₂Al₄Si₅O₁₈ with a stuffed β-quartz structure has been obtained. Comparison of its spectrum with that of cordierite glass suggests similar structures for both, which seem different to that of disordered cordierite.     

Raman spectra and X-ray diffraction of tuite at various temperatures

High-temperature Raman spectra and thermal expansion of tuite, γ-Ca₃(PO₄)₂, have been investigated. The effect of temperature on the Raman spectra of synthetic tuite was studied in the range from 80 to 973 K at atmospheric pressure. The Raman frequencies of all observed bands for tuite continuously decrease with increasing temperature. The quantitative analysis of temperature dependence of Raman bands indicates that the changes in Raman frequencies for stretching modes (ν₃ and ν₁) are faster than those for bending modes (ν₄ and ν₂) of PO₄ in the present temperature range, which may be attributed to the structural evolution of PO₄ tetrahedron in tuite at high temperature. The thermal expansion of tuite was examined by means of in situ X-ray diffraction measurements in the temperature range from 298 to 923 K. Unit cell parameters and volume were analyzed, and the thermal expansion coefficients were obtained as 3.67 (3), 1.18 (1), and 1.32 (3) × 10^?5 K^?1 for V, a, and c, respectively. Thermal expansion of tuite shows an axial anisotropy with a larger expansion coefficient along the c-axis. The isothermal and isobaric mode Grüneisen parameters and intrinsic anharmonicity of tuite have been calculated by using present high-temperature Raman spectra and thermal expansion coefficient combined with previous results of the isothermal bulk modulus and high-pressure Raman spectra.     

High-temperature phase transition and local structure of a hydrous anorthoclase

The in situ Raman spectra of a hydrous anorthoclase at temperatures of 20–800 °C have been measured using a LABRAM-HR spectrometer and Linkam TS 1500 heating stage. The frequencies of modes at 54, 99, 130 and 162 cm^?1 related to M–O vibrations decrease sharply and then increase drastically or keep steady at temperatures above 200 °C. A knee point can be clearly seen at about 200 °C for those modes. The frequency of the mode at 282 cm^?1 shows little temperature dependence. However, for the two strongest modes at 471 and 512 cm^?1, the frequencies decrease linearly with increasing temperature. From evolution of the frequencies of modes at 54, 99, 130 and 162 cm^?1 with temperature, the following conclusions can be drawn: (1) The distance of the local M–O bond shortens rather than lengthens at temperatures above 200 °C; (2) The abrupt changes of the local structure of M site induce a collapse of the framework structure and displacive phase transition at 200 °C; and (3) The H atoms incorporated in anorthoclase are located at the M site. These results are indicative for the structure and properties of anorthoclase at deep earth conditions.     

Raman scattering and lattice vibrations of Ni2SiO4 spinel at elevated temperature

Raman spectra of Ni₂SiO₄ spinel (O _h ⁷ Z=8) have been measured in the temperature range from 20 to 600 °C and the Raman active vibrations (A _1g +E _g +3F _2g ) have been assigned. A calculation of the optically active lattice vibrations of this spinel has been made, assuming a potential function which combines general valence and short range force constants. The values of the force constants at 20 and 500 °C have been calculated from the vibrational frequencies of the observed Raman spectra and infrared (IR) spectral data. The Ni spinel at 20 °C has a prominently small Si-O bond stretching force constant of K(SiO)=2.356 ～ 2.680 md/Å and a large Ni-O bond stretching constant of K(NiO)=0.843 ～ 1.062 md/Å and these force constants at 500 °C decrease to K(SiO)=2.327 ～ 2.494 md/Å and K(NiO)=0.861 ～ 0.990 md/Å. The Si-O bond is noticeably weakened at high temperatures, despite the small thermal expantion from 1.657 Å (20 °C) to 1.660 Å (500 °C). These changes of the interatomic force constants of the spinel at high temperatures are in accord with the thermal structure changes observed by X-ray diffraction study. The weakened Si-O bond is consistent with the fact that Si atoms in the spinel lattice can diffuse at significant rates at elevated temperature.     

High-pressure and high-temperature Raman spectroscopic study of hydrous wadsleyite (β-Mg2SiO4)

In situ Raman spectra of hydrous wadsleyite (β-Mg₂SiO₄) with ~1.5 wt% H₂O, synthesized at 18 GPa and 1,400°C, have been measured in an externally heated diamond anvil cell up to 15.5 GPa and 673 K. With increasing pressure (at room temperature), the three most intense bands at ~549, 720 and 917 cm⁻¹ shift continuously to higher frequencies, while with increasing temperature at 14.5 GPa, these bands generally shift to lower frequencies. The temperature-induced frequency shifts at 14.5 GPa are significantly different from those at ambient pressure. Moreover, two new bands at ~714 and ~550 cm⁻¹ become progressively significant above 333 and 553 K, respectively, and disappear upon cooling to room temperature. No corresponding Raman modes of these two new bands were reported for wadsleyite at ambient conditions, and they are thus probably related to thermally activated processes (vibration modes) at high-pressure and temperature conditions.     

Raman scattering and X-ray diffraction study of the thermal decomposition of an ettringite-group crystal

 A Raman scattering and X-ray diffraction study of the thermal decomposition of a naturally occurring, ettringite-group crystal is presented. Raman spectra, recorded with increasing temperature, indicate that the thermal decomposition begins at ≈55 °C, accompanied by dehydration of water molecules from the mineral. This is in contrast to previous studies that reported higher temperature breakdown of ettringite. The dehydration is completed by 175 °C and this results in total collapse of the crystalline structure and the material becomes amorphous. The Raman scattering results are supported by X-ray diffraction results obtained at increasing temperatures. Received: 9 July 2001 / Accepted: 14 August 2002     

The Raman spectra of several orthorhombic calcium oxide perovskites

We have obtained Raman spectra for a number of orthorhombic perovskites CaBO₃, where B=Ti, Ge, Zr or Sn. The room temperature Raman spectrum of CaTiO₃ was compared with cubic SrTiO₃ to assign first- and second-order features. Partially polarized micro-Raman spectra were obtained for CaTiO₃ perovskite. The CaBO₃ perovskites showed a sequence of increasing complexity in their Raman spectra with increasing degree of orthorhombic distortion from the ideal cubic structure. The spectral changes cannot easily be correlated with changes in chemistry or structure of the perovskite. High temperature micro-Raman spectra for CaGeO₃ perovskite were obtained by laser-heating a 15 μm sample. None of the low frequency Raman modes were soft, but showed only normal anharmonicity up to approximately 700 K.     

Raman spectra of high-pressure polymorphs of SiO2 at various temperatures

Raman spectra of the two high-pressure polymorphs of SiO₂ (coesite and stishovite) were investigated in the temperature range 105–875 K at atmospheric pressure. Coesite remained intact after the highest temperature run, but stishovite became amorphous at temperatures above about 842～872 K. Most Raman modes exhibit a negative frequency shift with temperature for these polymorphs, but positive trends were also observed for some modes. Except for some weak modes, nonlinear temperature variation were established for these polymorphs within the experimental uncertainty and temperature range spanned. The slopes of the variation (δv_i/δT)_P for these polymorphs were compared with the published values. When compared with quartz and stishovite, the four-membered rings of SiO₄-tetrahedra in coesite exhibit very little change with both temperature and pressure. It is also suggested that temperature and pressure should have opposite effects on the Raman shift of each vibrational mode.     

Towards pyrrhotite/magnetite geothermometry in low-grade metamorphic carbonates of the Tethyan Himalayas (Shiar Khola,Central Nepal)

In Mesozoic metacarbonates of the Tethyan Himalayas (Shiar Khola area, Central Nepal) two characteristic remanent magnetisations (ChRM₁ and ChRM₂) were identified by their unblocking temperature spectra. The ChRM₁ is carried by pyrrhotite (unblocking temperature: 270–360°C) and the ChRM₂ by magnetite (unblocking temperature spectra: 430–580°C). The temperature-related formation of pyrrhotite at the expense of primary magnetite during low-grade metamorphism in marly carbonates allows the determination of thermal gradients by the pyrrhotite/magnetite ratio. This new method can be used as a geothermometer for T≤300°C in low-grade metamorphic carbonates, where other methods are not available. This method is applied for the first time in the Tethyan Himalayas of Central Nepal.In the Shiar Khola valley, systematic variations in the ferrimagnetic content of the metacarbonates along an E–W profile were detected by the ratio of remanence intensity of pyrrhotite to magnetite, derived from natural remanent magnetisation (R_PYR/MAG) and saturation magnetisation (S_PYR/MAG). Over a stretch of 10 km the R_PYR/MAG and S_PYR/MAG increase from W to E from ~0.42 to ~0.91 and ~0.48 to ~1.0, respectively. Based on temperature estimates, the eastern part experienced upper anchizone–epizone (~250–300°C) conditions, while the western part underwent only diagenesis (~200°C). The temperature gradient and the temperature ranges suggested are consistent with the findings of the calcite twin lamellae geothermometry which is a non-magnetic method.     

Vibrational spectroscopy of aluminate spinels at 1 atm and of MgAl2O4 to over 200 kbar

Single-crystal Raman and infrared reflectivity data including high pressure results to over 200 kbar on a natural, probably fully ordered MgAl₂O₄ spinel reveal that many of the reported frequencies from spectra of synthetic spinels are affected by disorder at the cation sites. The spectra are interpreted in terms of factor group analysis and show that the high energy modes are due to the octahedral internal modes, in contrast to the behavior of silicate spinels, but in agreement with previous data based on isotopic and chemical cation substitutions and with new Raman data on gahnite (～ ZnAl₂O₄) and new IR reflectivity data on both gahnite and hercynite (～Fe_0.58Mg_0.42Al₂O₄). Therefore, aluminate spinels are inappropriate as elastic or thermodynamic analogs for silicate spinels. Fluorescence sideband spectra yield complementary information on the vibrational modes and provide valuable information on the acoustic modes at high pressure. The transverse acoustic modes are nearly pressure independent, which is similar to the behavior of the shear modes previously measured by ultrasonic techniques. The pressure derivative of all acoustic modes become negative above 110 kbar, indicating a lattice instability, in agreement with previous predictions. This lattice instability lies at approximately the same pressure as the disproportionation of spinel to MgO and Al₂O₃ reported in high temperature, high pressure work.     

Temperature dependence of the OH-stretching frequencies in topaz-OH

Hydrogen bonding in topaz-OH, Al₂SiO₄(OH)₂, was investigated by IR spectroscopic analysis of the temperature dependence of the OH-stretching frequencies. Low-temperature spectra ranging from −196 to −160°C prove the existence of four non-equivalent H-positions in the crystal structure from the occurrence of four different OH-bands. With increasing temperature, these bands merge first, above −160°C, into two OH-bands and then above 400°C into one asymmetric broad band. Shifting of the OH-bands is caused by thermally induced hydrogen order–disorder. Low temperature fixes the protons in their positions; increasing temperature induces proton movement and allows switching between the different positions. Autocorrelation analysis of the IR spectra reveals two phase transitions, one at about −155°C from P1 to Pbn2 ₁ characterized as static–dynamic change and the second at about 380°C from Pbn2 ₁ to Pbnm caused by disordering of the protons. The increasing symmetry with temperature is due to advanced proton movement and dynamical averages over the proton distribution densities.     

Phase changes and thermodynamic properties of CaTiO3. Spectroscopic data,vibrational modelling and some insights on the properties of MgSiO3 perovskite

The effect of pressure (up to 21 GPa at room temperature) and temperature (up to 1570 K at room pressure) on the Raman spectrum of CaTiO₃ is presented. No significant changes, which could be attributed to a major structural change, are observed in the spectra up to 22 GPa. The pressure shifts of the Raman modes can be related to a significant compression of the Ti-O bond. Discontinuous changes in the spectra upon heating may be related to phase changes observed by calorimetry and X-ray diffraction. The important temperature shifts of some low-frequency modes can be related to an increase in the Ti-O-Ti angle in agreement with the X-ray data showing a decrease of the structural distortion with increasing temperature. These data are compared to those available for MgSiO₃-perovskite and show that CaTiO₃ is a good structural analogue for MgSiO₃-perovskite. The present spectroscopic data are used to calculate the specific heat and entropy of CaTiO₃. The role of the low frequency modes in the calculations is emphasized. Good agreement is observed between calculated and experimentally determined values in the 0–1300 K temperature range. A similarly defined model is proposed for MgSiO₃-perovskite. It is found that the entropy lies between 57 and 64 J/mol/K at 298 K and between 190 and 200 J/mol/K at 1000 K in agreement with the values inferred from experimental equilibrium data. Finally we briefly discuss the values of the Grüneisen parameters of both perovskites inferred from macroscopic and microscopic data.     

Characterization of hydrocarbon-bearing fluid inclusion in sandstones of Jaisalmer basin, Rajasthan: A preliminary approach

The quartz grains from the sandstone of Jaisalmer, Pariwar and Goru Formations of the Jaisalmer basin, Rajasthan, India, exhibits a variety of primary and secondary fluid inclusions. Most of them are hydrocarbon bearing fluid inclusions. Laser Raman studies indicate that the primary fluid inclusions were mostly having aliphatic hydrocarbons with lower degree of maturity, while the secondary fluid inclusions were generally with aliphatic as well as aromatic hydrocarbons with higher degree of maturity. This inference was consistent with their fluorescence characteristics. The homogenization temperatures of primary monophase CH₄ rich fluid inclusions varied from ?80°C to ?100°C, whereas the primary biphase fluid inclusions (CH₄-CO₂) homogenized between +80°C and +150°C. The secondary petroleum rich monophase fluid inclusions were having homogenization temperature between ?80°C to ?90°C, whereas the secondary biphase fluid inclusions homogenized between +130°C and +180°C. Most of the secondary biphase fluid inclusions were having the mixtures of H₂O-CO₂-NaCl, and were identified on the basis clathrate formation and they got homogenized between +140°C and + 250 °C. The three past events of migration of petroleum inferred in the host rock which were marked by the presence of characteristic secondary fluid inclusions. They were identified on the basis of cross-cutting relationships of different trails of fluid inclusions in the quartz. The cement generation in the basin might have been occurred in two stages as per the fluid inclusion petrography.     

Dehydration process and structural development of cordierite ceramic precursors derived from FTIR spectroscopic investigations

 Cordierite precursors were prepared by a sol-gel process using tetraethoxysilane, aluminum sec.-butoxide, and Mg metal flakes as starting materials. The precursors were treated by 15-h heating steps in intervals of 100 °C from 200 to 900 °C; they show a continuous decrease in the analytical water content with increasing preheating temperatures. The presence of H₂O and (Si,Al)–OH combination modes in the FTIR powder spectra prove the presence of both H₂O molecules and OH groups as structural components, with invariable OH concentrations up to preheating temperatures of 500 °C. The deconvolution of the absorptions in the (H₂O,OH)-stretching vibrational region into four bands centred at 3584, 3415, 3216 and 3047 cm⁻¹ reveals non-bridging and bridging H₂O molecules and OH groups. The precursor powders remain X-ray amorphous up to preheating temperatures of 800 °C. Above this temperature the precursors crystallize to μ-cordierite; at 1000 °C the structure transforms to α-cordierite. Close similarities exist in the pattern of the 1400–400 cm⁻¹ lattice vibrational region for precursors preheated up to 600 °C. Striking differences are evident at preheating temperatures of 800 °C, where the spectrum of the precursor powder corresponds to that of conventional cordierite glass. Bands centred in the “as-prepared” precursor at 1137 and 1020 cm⁻¹ are assigned to Si–O-stretching vibrations. A weak absorption at 872 cm⁻¹ is assigned to stretching modes of AlO₄ tetrahedral units and the same assignment holds for a band at 783 cm⁻¹ which appears in precursors preheated at 600 °C. With increasing temperatures, these bands show a significant shift to higher wavenumbers and the Al–O stretching modes display a strong increase in their intensities. (Si,Al)–O–(Si,Al)-bending modes occur at 710 cm⁻¹ and the band at 572 cm⁻¹ is assigned to stretching vibrations of AlO₆ octahedral units. A strong band around 440 cm⁻¹ is essentially attributed to Mg–O-stretching vibrations. The strongly increasing intensity of the 872 and 783 cm⁻¹ bands demonstrates a clear preference of Al for a fourfold-coordinated structural position in the precursors preheated at high temperatures. The observed band shift is a strong indication for increasing tetrahedral network condensation along with changes in the Si–O and Al–O distances to tetrahedra dimensions similar to those occurring in crystalline cordierite. These structural changes are correlated to the dehydration process starting essentially above 500 °C, clearly demonstrating the inhibiting role of H₂O molecules and especially of OH groups. Received: 1 March 2002 / Accepted: 26 June 2002     

Fluid inclusion studies of the Felbertal scheelite deposit

Fluid inclusion measurements on quartz, scheelite, beryl, fluorite and calcite in the metamorphosed Felbertal scheelite deposit display two main types of fluid inclusions:

1. H₂O-CO₂ fluid inclusions are characterized by variable amounts of CO₂ up to 18 wt.%. They show two or three phases at room temperature. The bulk homogenization temperatures for the inclusions range between +269 °C and +357 °C. The calculated salinities are between 2.2 and 7.8 wt.% NaCl equivalent. For the late CO₂-bearing fluid inclusions a methane component is evident from microthermometrical data (T_mclath >10.0 °C combined with T_mCO₂
2. Aqueous, two-phase fluid inclusions with salinities in the range between 0 and 11 wt.% NaCl equivalent. Their homogenization temperatures are scattered between 100 °C and 360 °C.

Both types of fluid inclusions are of Alpine origin. They do not record the conditions of the original tungsten ore formation in pre-Alpine (Upper Proterozoic) time. However, it was possible to deduce a path for the fluid evolution and the combined ore redeposition during the retrograde Alpine metamorphism and tectonism from microthermometrical and petrographical studies.     

Fluid evolution in a slate-belt gold deposit

Auriferous quartz veins in the Hill End goldfield, NSW, Australia, comprise bedding-parallel vein sets and minor extension and fault-controlled veins which are hosted by a multiply deformed, Late Silurian slate-metagreywacke turbidite sequence. Fluid inclusions in quartz, either from bedding-parallel veins or from narrow, steeply N-dipping veins (‘leader’ veins) indicate a similar range in homogenisation temperatures (T_h) from 350°C to 110°C. Within this range, T_h data demonstrate five groupings in the temperature intervals 350–280°C, 280–250°C, 250–190°C, 190–150°C, and 150–110°C, corresponding to a variety of primary and secondary inclusions developed during five periods of vein growth under a generally declining temperature regime. Inclusion fluids are characterised by a low salinity of around 0.1 to 3.6 wt% NaCl equivalent. Laser Raman microprobe inclusion analysis indicates that gas-phase compositions relate to the paragenetic stage of the host quartz. H₂O_(g) and N₂ dominate in the primary inclusions from barren, Stage I quartz; CH₄ and CH₄ + H₂O_(g) are important in inclusions related to the early gold forming events (equivalent to Stages II and III quartz), but inclusions developed during the last episode of gold deposition are characterised by H₂O_(g), CO₂-rich and liquid-CO₂ bearing fluids. Precipitation of gold was aided by sulphidation reactions or phase separation in response to periods of vein opening. Late in the paragenesis, gold deposition may have been promoted by oxidation of the ore fluid.     

The formation of lead(II) chloride complexes to 300°C: A spectrophotometric study

The spectra of chlorolead(II) complexes in the ultraviolet region have been measured in acid chloride solutions from 0.0012 to 3.223 m and at temperatures from 25 to 300°C. The thermodynamic cumulative and stepwise formation constants as well as the spectra of the individual chlorolead(II) species have been calculated from the spectrophotometric data. At 25°C, the five species PbCl^2?n_n (0 ≤ n ≤ 4) occur, however, at 300°C the predominant species were PbCl⁺, PbCl⁰₂ and PbCl^?₃. Pb²⁺ occurs as a minor species in dilute solutions where total chloride is <0.003 m at 300°C and the presence of PbCl^2?₄ in concentrated solutions was not detected above 150°C. With increasing temperature, chlorolead(II) complex stability is characterised by large endothermic enthalpies and large positive entropies of formation. Lead(II) chloride complexes are important in the transport and deposition of lead by hydrothermal ore solutions of moderate to high salinity.