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     

High-pressure phase transition and behavior of protons in brucite Mg(OH)2: a high-pressure–temperature study using IR synchrotron radiation

 Infrared absorption spectra of brucite Mg (OH)₂ were measured under high pressure and high temperature from 0.1 MPa 25 °C to 16 GPa 360 °C using infrared synchrotron radiation at BL43IR of Spring-8 and a high-temperature diamond-anvil cell. Brucite originally has an absorption peak at 3700 cm⁻¹, which is due to the OH dipole at ambient pressure. Over 3 GPa, brucite shows a pressure-induced absorption peak at 3650 cm⁻¹. The pressure-induced peak can be assigned to a new OH dipole under pressure. The new peak indicates that brucite has a new proton site under pressure and undergoes a high-pressure phase transition. From observations of the pressure-induced peak under various P–T condition, a stable region of the high-pressure phase was determined. The original peak shifts to lower wavenumber at −0.25 cm⁻¹ GPa⁻¹, while the pressure-induced peak shifts at −5.1 cm⁻¹ GPa⁻¹. These negative dependences of original and pressure-induced peak shifts against pressure result from enhanced hydrogen bond by shortened O–H···O distance, and the two dependences must result from the differences of hydrogen bond types of the original and pressure-induced peaks, most likely from trifurcated and bent types, respectively. Under high pressure and high temperature, the pressure-induced peak disappears, but a broad absorption band between 3300 and 3500 cm⁻¹ was observed. The broad absorption band may suggest free proton, and the possibility of proton conduction in brucite under high pressure and temperature. Received: 16 July 2001 / Accepted: 25 December 2001     

OH in natural orthopyroxene: an in situ FTIR investigation at varying temperatures

In situ unpolarized and polarized Fourier transform infrared spectra of a natural orthopyroxene at varying temperatures were obtained using a heating stage attached on an Infrared microscope. The three main bands (3,595, 3,520 and 3,410 cm⁻¹) at room temperature are ascribed to OH fundamental stretching bands. With increasing temperature from room temperature to 500 °C, the 3,595 cm⁻¹ band shifts 20 cm⁻¹ to lower frequency. The total integral absorbance decreases with increasing temperature. These changes are reversible. Excluding the influences of dehydration, proton migration, thermal expansion, and changes in OH dipole direction, the change of integral absorbance with temperature reflects the temperature dependence of absorption coefficient due to the anharmonicity of OH vibration. Based on the integral absorption coefficient at room temperature (14.84 ppm⁻¹ cm⁻²) from Bell et al. (Am Mineral 80:463–474, 1995), the integral absorption coefficients at other temperatures are calculated. The variation of integral absorption coefficient between room temperature and 500 °C obtained in this study is about 18.5 % and may be greater at higher temperature according to the proposed linear relationship.     

Point defects and pre-dose requirements for sensitization of the 300°C TL peak in natural quartz

This paper discusses the structural features required to stimulate a strong thermoluminescence (TL) glow peak near 300°C in clear natural quartz. For that reason, fresh TL data taken from several specimens prepared from five single crystals with known impurity content are shown. The TL emission was measured with a test dose of 10 mGy of γ-rays in the readout intervals 50–160 and 160–320°C. The readings were carried out prior and after the administration of a pre-dose of 175 kGy of γ-rays followed by heat-treatments at 400°C. For each single specimen, the OH content and the population of inclusions were evaluated by infrared spectroscopy and optical microscopy, respectively. The darkening induced by high γ dose was evaluated by optical spectroscopy. It was observed that the absorption at 475 nm and TL responses decrease with increase of the OH. It was shown that both smoky darkening and TL signals were better explained in terms of Li/Al and Li/OH content ratios rather than the absolute values of aluminum and alkali concentrations. The sensitization with high γ dose and heating is essential to create and stabilize a class of defects sites with Li⁺ ions dislodged from [AlO₄/Li]⁰ and Li-dependent OH centers. It is suggested that the defect sites formed with Li⁺ act as electron traps during test dose irradiation, whereas electron-hole recombination occurs essentially at [AlO₄]⁰ centers during the TL output near 300°C.     

Location and quantitative analysis of OH in coesite

 The incorporation of hydrogen (deuterium) into the coesite structure was investigated at pressures from 3.1 to 7.5 GPa and temperatures of 700, 800, and 1100 °C. Hydrogen could only be incorporated into the coesite structure at pressures greater 5.0 GPa and 1100 °C . No correlation between the concentration of trace elements such as Al and B and the hydrogen content was observed based on ion probe analysis (1335 ± 16 H ppm and 17 ± 1 Al ppm at 7.5 GPa, 1100 °C). The FTIR spectra show three relatively intense bands at 3575, 3516, and 3459 cm⁻¹ (ν₁ to ν₃, respectively) and two very weak bands at 3296 and 3210 cm⁻¹ (ν₄ and ν₅, respectively). The band at 3516 cm⁻¹ is strongly asymmetric and can be resolved into two bands, 3528 (ν_2a) and 3508 (ν_2b) cm⁻¹, with nearly identical areas. Polarized infrared absorption spectra of coesite single-crystal slabs, cut parallel to (0 1 0) and (1 0 0), were collected to locate the OH dipoles in the structure and to calibrate the IR spectroscopy for quantitative analysis of OH in coesite (ɛ _{i ,tot}=190 000 ± 30 000 l mol⁻¹ _H2O cm⁻²). The polarized spectra revealed a strong pleochroism of the OH bands. High-pressure FTIR spectra at pressures up to 8 GPa were performed in a diamond-anvil cell to gain further insight into incorporation mechanism of OH in coesite. The peak positions of the ν₁, ν₂, and ν₃ bands decrease linearly with pressure. The mode Grüneisen parameters for ν₁, ν₂, and ν₃ are −0.074, −0.144 and −0.398, respectively. There is a linear increase of the pressure derivatives with band position which follows the trend proposed by Hofmeister et al. (1999). The full widths at half maximum (FWHM) of the ν₁, ν₂, and ν₃ bands increase from 35, 21, and 28 cm⁻¹ in the spectra at ambient conditions to 71, 68, and 105 in the 8 GPa spectra, respectively. On the basis of these results, a model for the incorporation of hydrogen in coesite was developed: the OH defects are introduced into the structure by the substitution Si^4+(Si2)+4O²⁻= ^[4]□^(Si2) + 4OH⁻, which gives rise to four vibrations, ν₁, ν_2a, ν_2b, and ν₃. Because the OH(D)-bearing samples do contain traces of Al and B, the bands ν₄ and ν₅ may be coupled to Al and/or B substitution. Received: 19 December 2000 / Accepted: 23 April 2001     

Structural thermal behavior of paragonite and its dehydroxylate: a high-temperature single-crystal study

 The lattice constants of paragonite-2M₁, NaAl₂(AlSi₃)O₁₀(OH)₂, were determined to 800 °C by the single-crystal diffraction method. Mean thermal expansion coefficients, in the range 25–600 °C, were: α_a = 1.51(8) × 10⁻⁵, α_b = 1.94(6) × 10⁻⁵, α_c = 2.15(7) ×  10⁻⁵ °C⁻¹, and α_V = 5.9(2) × 10⁻⁵ °C⁻¹. At T higher than 600 °C, cell parameters showed a change in expansion rate due to a dehydroxylation process. The structural refinements of natural paragonite, carried out at 25, 210, 450 and 600 °C, before dehydroxylation, showed that the larger thermal expansion along the c parameter was mainly due to interlayer thickness dilatation. In the 25–600 °C range, Si,Al tetrahedra remained quite unchanged, whereas the other polyhedra expanded linearly with expansion rate proportional to their volume. The polyhedron around the interlayer cation Na became more regular with temperature. Tetrahedral rotation angle α changed from 16.2 to 12.9°. The structure of the new phase, nominally NaAl₂ (AlSi₃)O₁₁, obtained as a consequence of dehydroxylation, had a cell volume 4.2% larger than that of paragonite. It was refined at room temperature and its expansion coefficients determined in the range 25–800 °C. The most significant structural difference from paragonite was the presence of Al in fivefold coordination, according to a distorted trigonal bipyramid. Results confirm the structural effects of the dehydration mechanism of micas and dioctahedral 2:1 layer silicates. By combining thermal expansion and compressibility data, the following approximate equation of state in the PTV space was obtained for paragonite: V/V ₀ = 1 + 5.9(2) × 10⁻⁵ T(°C) − 0.00153(4) P(kbar). Received: 12 July 1999 / Revised, accepted: 7 December 1999     

Time calibration of a P–T path from a Variscan high-temperature low-pressure metamorphic complex (Bayerische Wald, Germany), and the detection of inherited monazite

A temperature–time path was constructed for high-temperature low-pressure (HT–LP) migmatites of the Bayerische Wald, internal zone of the Variscan belt, Germany. The migmatites are characterised by prograde biotite dehydration melting, peak metamorphic conditions of approximately 850 °C and 0.5–0.7 GPa and retrograde melt crystallisation at 800 °C. The time-calibration of the pressure–temperature path is based on U–Pb dating of single zircon and monazite grains and titanite separates, on ⁴⁰Ar/³⁹Ar ages obtained by incremental heating experiments on hornblende separates, single grains of biotite and K-feldspar, and on ⁴⁰Ar/³⁹Ar spot fusion ages of biotite determined in situ from sample sections. Additionally, crude estimates of the duration of peak metamorphism were derived from garnet zoning patterns, suggesting that peak temperatures of 850 °C cannot have prevailed much longer than 2.5 Ma. The temperature–time paths obtained for two areas approximately 30 km apart do not differ from each other considerably. U–Pb zircon ages reflect crystallisation from melt at 850–800 °C at 323 Ma (southeastern area) and 326 Ma (northwestern area). The U–Pb ages of monazite mainly coincide with those from zircon but are complicated by variable degrees of inheritance. The preservation of inherited monazite and the presence of excess ²⁰⁶Pb resulting from the incorporation of excess ²³⁰Th in monazite formed during HT–LP metamorphism suggest that monazite ages in the migmatites of the Bayerische Wald reflect crystallisation from melt at 850–800 °C and persistence of older grains at these temperatures during a comparatively short thermal peak. The U–Pb ages of titanite (321 Ma) and ⁴⁰Ar/³⁹Ar ages of hornblende (322–316 Ma) and biotite (313–309 Ma) reflect cooling through the respective closure temperatures of approximately 700, 570–500 and 345–310 °C published in the literature. Most of the feldspars' ages (305–296 Ma) probably record cooling below 150–300 °C, while two grains most likely have higher closure temperatures. The temperature–time paths are characterised by a short thermal peak, by moderate average cooling rates and by a decrease in cooling rates from 100 °C/my at temperatures between 850–800 and 700 °C to 11–16 °C/my at temperatures down to 345–310 °C. Further cooling to feldspar closure for Ar was probably even slower. The lack of decompressional features, the moderate average cooling rates and the decline of cooling rates with time are not easily reconciled with a model of asthenospheric heating, rapid uplift and extension due to lithospheric delamination as proposed elsewhere. Instead, the high peak temperatures at comparatively shallow crustal levels along with the short thermal peak require external advective heating by hot mafic or ultramafic material. Received: 7 July 1999 / Accepted: 28 October 1999     

Interlayer proton transfer in brucite under pressure by polarized IR spectroscopy to 5.3 GPa

In order to investigate the behaviour of proton in brucite under pressure, polarized IR absorption spectra and polarized absorbance distributions of (001) and (110) oriented single crystal of brucite under high pressure were measured by Fourier transform polarized infrared microspectroscopy with diamond anvil cell. A pressure-induced absorption peak at 3645 cm⁻¹ observed under pressures over 2.9 GPa was confirmed to be due to a secondarily formed OH dipole. Polarized absorbance distribution measured under pressure of (110) suggests that the secondary OH dipole is oriented 136.0° to c-axis under 5.3 GPa. Isotropic absorbance distribution of (001) suggests that the secondary OH dipole is disorderly trifurcated. Abrupt onset of the secondary peak and its reverse pleochroism suggest that the process of secondary OH dipole formation is due to proton transfer between layers in brucite. The calculated orientation of the secondary OH dipole consistent with the O-H···O′ angle revealed by neutron diffraction supports the existence of proton transfer along H···O′. The secondary OH dipole implies a new site of proton in brucite under pressure. Received: 6 March 1997 / Revised, accepted: 9 June 1997     

Location of OH groups and oxidation processes in triclinic chloritoid

Triclinic Fe²⁺ and Fe³⁺-chloritoid end members, as well as Fe²⁺-Fe³⁺-chloritoid solid solutions were synthesized in order to determine the location of the OH groups in the structure and to investigate the possibility of Fe³⁺ incorporation on the M1B site and the corresponding oxidation mechanism. The samples were analyzed using transmission electron microscopy, electron energy-loss and ⁵⁷Fe Mössbauer spectroscopy, polarized single-crystal, KBr powder and in situ high-pressure infrared spectroscopy. The structure of a natural triclinic chloritoid was refined by single-crystal X-ray diffraction in order to locate the proton-accepting oxygens in the triclinic structure. The results of valence bond calculations, polarized single-crystal and in situ high-pressure IR spectroscopy revealed that the orientations of the OH dipoles are the same as those in monoclinic chloritoid. The annealing experiments in air show that the incorporation of Fe³⁺ on M1B increases with temperature. After 3?h at 530?°C all Fe²⁺ was oxidized to Fe³⁺ without decomposition of the structure. This also holds true for a heating duration of 24?h. The incorporation of Fe³⁺ at M1B sites is coupled with a dehydration process starting at about 350?°C during which the H1A protons leave first.     

Cation distribution in amphiboles synthesized along the Ga analogue of the tremolite–aluminotschermakite join

 Amphiboles were synthesized from bulk compositions prepared along the join Ca_1.8Mg_5.2Si₈O₂₂(OH)₂–Ca_1.8Mg₃Ga₄Si₆O₂₂(OH)₂ hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca₂Mg₅Si₈O₂₂F₂–Ca₂Mg₃Ga₄Si₆O₂₂F₂, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: ^[6]Ga³⁺+2^[4]Ga³⁺+1/2^[A] Ca²⁺ = ^[6]Mg²⁺+2^[4]Si⁴⁺+1/2^[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001     

High-temperature study and thermal expansion of phlogopite

 Unit-cell dimensions of a natural phlogopite from Pargas, Finland, have been determined in the temperature interval of 27–1050 °C by X-ray powder diffraction technique. Expansion rates vary discontinuously with temperature with a break at 412 °C. Below this temperature, the linear expansions (α) for a, b and c axis lengths are 3.74 × 10⁻⁵ K⁻¹, 1.09 × 10⁻⁵ K⁻¹, and 1.19 × 10⁻⁵ K⁻¹, respectively, and above that they are 0.86 × 10⁻⁵ K⁻¹, 0.80 × 10⁻⁵ K⁻¹, and 1.93 × 10⁻⁵ K⁻¹. The volume thermal expansion coefficients are 6.26 × 10⁻⁵ K⁻¹ and 3.71 × 10⁻⁵ K⁻¹ for low-temperature and high-temperature intervals, respectively. The observed kink in the rate of thermal expansions with temperature could be due to the different mode of structural changes. Thermogravimetric analysis of the sample indicates the oxidation of iron in the temperature range of 500–600 °C and dehydroxylation as well as decomposition of phlogopite in the temperature range of 900–1200 °C. Received: 8 September 1998 / Accepted: 28 February 2000     

Anelasticity and microcreep in polycrystalline MgO at high temperature: an exploratory study

 The frequency dependence of the shear modulus and dissipation in polycrystalline MgO has been determined at high temperature using both microcreep (ɛ = 10⁻⁴) and seismic frequency forced-oscillation (ɛ = 10⁻⁵) measurements. The frequency-dependent and time-dependent data have been described in terms of the elastic, anelastic and viscous components of deformation using the Andrade model. The forced-oscillation measurements show that for temperatures above 700 °C the shear modulus begins to decrease dramatically and the modulus becomes frequency-dependent with increasing temperature. This is accompanied by an increase in dissipation, which also becomes frequency-dependent. The microcreep measurements resolve this frequency-dependent behaviour into an anelastic regime from 700–1050 °C, and a viscoelastic regime from 1100–1300 °C. At 1300 °C, the seismic frequency shear wave speed is ∼60% of the extrapolated low-temperature frequency-independent value, and the dissipation has risen to Q ⁻¹ = 10⁻¹ from 10⁻³ at temperatures below 600 °C. The mechanism by which this frequency-dependent rheology occurs appears to be diffusional creep, which produces viscous slip on the grain boundaries. It is proposed that the anelastic behaviour is due to viscous slip occurring on segments of grain boundaries, with the viscous deformation being accommodated by elastic distortion of adjacent unslipped regions of the grain boundary. At higher temperatures, slippage occurs across the entire grain boundary and viscoelastic behaviour begins to occur. Received: 11 April 2002 / Accepted: 9 January 2003 Acknowledgements Samples were precision-ground by Andrew Wilson, and polished sections prepared by Harri Kokkonen, who also did the SEM work. Uli Faul calculated the volume fraction of grain sizes. The density measurements were done by Lara Weston.     

Dehydration kinetics of muscovite by in situ infrared microspectroscopy

Dehydration behavior of muscovite flake was investigated at 760–860°C by using in situ high-temperature IR microspectroscopy for the OH absorption band around 3,620 cm⁻¹. Isothermal kinetic heating experiments at each temperature gave detailed decrease curves of the OH band area with time. These curves have been simulated by the first and second order reactions or mono- and two-dimensional diffusion processes. The mono-dimensional diffusion was found to give the best fit to the experimental data and apparent diffusion coefficients D were determined at 760–860°C with the activation energy of 290 ± 20 kJ/mol. The apparent diffusion coefficients D varied with the sample thickness L. This variation can be explained by an m layers model with a unit length of L′ with a constant diffusion coefficient D′. Therefore, the dehydration process might be rate-limited by mono-dimensional diffusion through tetrahedral silicate sheet perpendicular to (001) planes of muscovite with a unit length of L′.     

Melting of portlandite up to 6 GPa

 Using the high-pressure differential thermal analysis (HP-DTA) system in a cubic multianvil high-pressure apparatus, we measured the melting points of portlandite, Ca(OH)₂, up to 6 GPa and 1000 °C. We detected endothermic behavior at the temperature and pressure conditions of 800 °C and 2.5 GPa, 769 °C and 3.5 GPa, 752 °C and 4.0 GPa, 686 °C and 5.0 GPa, and 596 °C and 6.0 GPa, respectively, due to melting of portlandite. By in situ X-ray studies under pressure, the melting of portlandite was observed at 730 °C and 4.32 GPa and at 640 °C and 5.81 GPa, respectively. Results of both HP-DTA and X-ray studies were consistent within experimental error. The melting is congruent and has a negative Clapeyron slope, indicating that liquid Ca(OH)₂ has higher densities than crystalline portlandite in this pressure range. Received: 19 June 1999 / Revised, accepted: 11 September 1999     

The enthalpy of transformation of Ca(OH)2-I (portlandite) to Ca(OH)2-II (EuI2 structure) by low-temperature DSC

 Thermodynamic properties of high-pressure minerals that are not recoverable from synthesis experiments by conventional quenching methods (“unquenchable” phases) usually are calculated from equation of state data and phase diagram topologies. The present study shows that, with cryogenic methods of recovery and sample treatment, phases with a suitable decomposition rate can be made accessible to direct thermodynamic measurements. A set of samples of Ca(OH)₂-II has been synthesized in a multianvil device and subsequently recovered by cooling the high-pressure assembly with liquid nitrogen. Upon heating from liquid nitrogen to room temperature, the material transformed back to Ca(OH)₂-I. The heat effect of this backtransformation was measured by differential scanning calorimetry. A commercial differential scanning calorimeter (Netzsch DSC 404), modified to allow sample loading at liquid nitrogen temperature was used to heat the material from −150 to +200 °C at rates varying between 5 and 15 °C min⁻¹. The transformation started around −50 °C very gradually, and peaked at about 0 °C. To obtain a baseline correction, each sample was scanned under exactly the same conditions after the backtransformation was complete. Because of the relative sluggishness, onset and offset temperatures were not well defined as compared to fast (e.g., melting) reactions. To aid in integration, the resulting signals were successfully fitted using a generic asymmetric peak model. The enthalpy of backtransformation was determined to be ΔH =−10.37 ± 0.50 kJ mol⁻¹. From previous in situ X-ray diffraction experiments, the location of the direct transformation in P-T space has been constrained to 5.7 ± 0.4 GPa at 500 °C (Kunz et al. 1996). With the reaction volume known from the same study, and assuming that ΔC _p of the transformation remains negligible between the conditions of our measurements and 500 °C, our result gives an estimate of the entropy of transition and the P-T slope of the reaction curve. To a first approximation, the values ΔS = −16.00 ± 0.65 J(mol · K)⁻¹ and dP/dT = 0.0040 ± 0.0002 GPa/K have been determined. These results need to be refined by equation of state data for Ca(OH)₂-II. Received: 30 December 1999 / Accepted: 10 April 2000     

The effects of metamorphism on O and Fe isotope compositions in the Biwabik Iron Formation, northern Minnesota

The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ¹⁸O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ¹⁸O–δ⁵⁶Fe variations in magnetite is a strong increase in δ¹⁸O_Mt and a mild decrease in δ⁵⁶Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

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     

High temperature infrared spectra of hydrous microcrystalline quartz

A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm^?1 at 50?°C toward 3590?cm^?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm^?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm^?1 (3740?cm^?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H₂O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H₂O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.