OH defects in forsterite

Polarized FTIR spectra of near endmember forsterite single crystals from Pamir, Tadzikistan show the existence of sharp strongly pleochroic absorption bands in the region of the OH stretching fundamental. Bands centered at 3674/3624, 3647/3598 and 3640/ 3592 cm^-1 are attributed to OH dipoles oriented parallel to [100]. An OH band doublet at 3570/3535 cm^-1 shows both, a strong absorption parallel to [100] and a strong component parallel to [001]. On the basis of the pleochroic scheme and under the assumption of vacancies on Si- and M-sites it is proposed that O1 is partially replaced by OH defects pointing to the vacant Si-site. O3 is donator oxygen of OH dipoles lying near the O3-O1 tetrahedral edge or roughly pointing to a vacant M2-site. Also O2 can act as donator oxygen of an OH group oriented along the O2-O3 edge of a vacant M1 octahedron. The splitting of the bands is explained by the presence of Fe²⁺ in cation sites surrounding the OH defects.     

Low-temperature evolution of OH bands in synthetic forsterite, implication for the nature of H defects at high pressure

We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between ?194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm^?1 display a small frequency lowering (<4 cm^?1) and a moderate broadening (<10 cm^?1) as temperature is increased from ?194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm^?1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm^?1 respectively) and broadening (~30 cm^?1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm^?1, three broad bands are identified at 3,151, 3,178 and 3,217 cm^?1, at ?194 °C. They exhibit significant frequency increase (~20 cm^?1) and broadening (~70 cm^?1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)_Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm^?1 (type (2); 3,550 cm^?1 at room temperature). The contribution of OH bands of type (3), associated to (2H)_Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.     

FTIR spectroscopy of OH in olivine: A new tool in kimberlite exploration

Our study of olivines from Canadian kimberlites shows that the application of FTIR spectroscopy significantly improves the reliability of olivine as a kimberlite indicator mineral (KIM). We have developed an algorithm that yields the water concentration and the normalized intensity of the OH IR absorption band at 3572 cm⁻¹ from unpolished olivine grains of unknown thickness. For 80% of kimberlitic olivines these two parameters are significantly higher than those for olivines from non-kimberlitic magmas and consequently, olivines with water concentrations >60 ppm and a strong absorption band at 3572 cm⁻¹ can be reliably classified as being kimberlitic.We have identified two major spectral features in the OH absorption bands of kimberlitic olivines that allow for a more detailed classification: (a) the presence of three types of high-requency OH absorption bands (Group 1A, 1B and 1C) and (b) the proportion of low-frequency OH absorption bands (Group 2) relative to high-frequency bands (Group 1). Comparison of our results with experimental studies suggests that differences within Group 1 OH absorption bands are due to different pressures of crystallization or hydrogenation. The three identified types of Group 1 OH absorption bands approximately correspond to high (P > 2 GPa, Group 1A), moderate (2-1 GPa, Group 1B), and low (<1 GPa, Group 1C) pressures of hydrogenation. Group 2 OH IR absorption bands in olivines with NiO > 3500 ppm are interpreted to reflect olivine-orthopyroxene equilibria and hence are indicative of xenocrystic olivine derived from lherzolitic or harzburgitic mantle sources. Interaction of xenocrystic olivine with hydrous kimberlitic melts with low silica activity likely will cause a gradual increase in Group 1 absorption bands. Therefore, FTIR spectra of olivine can be used to obtain qualitative estimates of the duration of interaction between mantle material and a kimberlitic melt.In addition to applications in kimberlite and diamond exploration, FTIR spectra of olivine phenocrysts, combined with mineral chemical data, may also provide insights into kimberlite evolution. Our data suggest that in some instances the ascent of kimberlitic magmas could have been interrupted at or near the Moho, followed by olivine crystallization and exsolution of aqueous fluids.     

First-principles study of OH defects in zircon

The infrared spectroscopic properties of selected OH defects in zircon are investigated by first-principles calculations. The explicit treatment of the coupled nature of OH motions in the stretching modes, together with the calculation of the intensity and polarization of absorption bands, makes it possible to directly compare theoretical and experimental data. The bands observed at 3,420 cm^?1 (polarization parallel to c axis) and 3,385 cm^?1 (polarization perpendicular to c axis) in natural and synthetic samples correspond to the IR-active vibrational modes of the hydrozircon defect, that is, fully protonated Si vacancy. The broad band observed at 3,515 cm^?1 in the spectrum of zircon crystals grown in F-rich environments is consistent with the occurrence of composite (OH,F) tetrahedral defects. Calculations also show that the band observed at 3,200 cm^?1 in the spectrum of synthetic undoped samples can be ascribed to fully protonated Zr vacancies. The theoretical values of integrated absorption coefficients indicate that general correlations can be reasonably used to determine the concentration of OH groups in zircon.     

Lattice vibrational modes in synthetic tremolite-Sr-tremolite and tremolite-richterite solid solutions

Powder IR spectra of synthetic richterite-tremolite and Sr-tremolite-tremolite solid solutions were obtained in the spectral range between 1400 and 600?cm^?1. Under the consideration of the crystal structure and the Wykoff positions of the atoms in the primitive unit cell, the number, type and symmetry of vibrational modes were deduced. The space group of tremolite C_2h was used as the factor group leading to 16 theoretical stretching vibrations in the IR range caused by the Si₄O₁₁ ^∞-ribbon. The energy of the internal vibrations of the Si₄O₁₁ ^∞-ribbon is a function of the relative bond strengths and masses of nearby ions. For the amphiboles a one-mode behavior was observed for all the Si-O, Si-O-Si and O-Si-O stretching vibrations, indicating no clustering in the two solid solution series. In both solid solution series the vibrational energy of the stretching vibrations is a linear function of composition. In the system richterite-tremolite a shift of the stretching frequencies of the Si₄O₁₁ ^∞-ribbon over the whole compositional range of up to 30?cm^?1 was observed. In contrast, for Sr-tremolite-tremolite the maximum shift was only 5?cm^?1. These quite small band shifts allow the (Si₄O₁₁)^∞-ribbon to be treated as an isolated entity for factor group analysis. Nevertheless, by the two exchange mechanisms, Ca(M4)???Sr(M4) and □(A) Ca(M4)???Na(A)Na(M4), the FWHHs increased and the amplitudes decreased, indicating a slight distortion of the ribbon. For Sr-tremolite-tremolite only a linear expansion of the lattice was observed. In the series richterite-tremolite individual bond angles of the SiO₄ tetrahedra are additionally changed, causing the higher energy shift of the bands. The strongest and sharpest bands were observed for the end member tremolite. The one-mode behavior of the Si₄O₁₁-double chain indicates that there is no short-range order of Na/Ca and Ca/Sr at the M4 sites of these amphiboles.     

Distinguishing natural from synthetic amethyst: the presence and shape of the 3595 cm−1 peak

Summary The infrared absorption spectrum of amethyst in the region of stretching vibrations of X–OH groups reveals several bands that have been used for the separation of natural from synthetic amethyst. The intensity and shape of these bands have been measured as a function of crystallographic orientation. Using a resolution of 0.5 cm⁻¹ the 3595 cm⁻¹ band is present in all infrared spectra of natural amethyst and in some rare synthetic ones. If present in synthetic amethyst, its full width at half maximum (FWHM) is about 7 cm⁻¹ whereas it is about 3 cm⁻¹ in all natural samples. This new criterion, unlike the previous ones, seems appropriate to separate natural from synthetic amethyst in all cases.     

OH incorporation in nearly pure MgAl2O4 natural and synthetic spinels

Four nearly pure MgAl₂O₄ spinels, of both natural and synthetic occurrence, have been studied by means of X-ray single crystal diffraction and FTIR spectroscopy in order to detect their potential OH content. Absorption bands that can be assigned to OH incorporated in the spinel structure were only observed in spectra of a non-stoichiometric synthetic sample. The absorption intensity of two bands occurring at 3350 and 3548 cm⁻¹ indicate an OH content of 90 ppm H₂O. Based on correlations of OH vibrational frequencies and O-H?O distances, the observed absorption bands correspond to O-H?O distances of 2.77 and 2.99 Å, respectively, which is close to the values obtained by the structure refinements for ^VIO-O_unsh (2.825 Å) and ^IVO-O (3.001 Å). This indicates that one probable local position for hydrogen incorporation is the oxygens coordinating a vacant tetrahedral site. The present spectra demonstrate that the detection limit for OH in Fe-free spinels is in the range 10-20 ppm H₂O. However, at appreciable Fe²⁺ levels, the detection of OH bands becomes hampered due to overlap with strong absorption bands caused by electronic d-d transitions in Fe²⁺ in the tetrahedral position.     

Mechanisms of OH defect incorporation in naturally occurring,hydrothermally formed diopside and jadeite

The IR spectrum of an alpine, hydrothermally formed diopside containing 17 wt ppm H₂O consists of three main OH absorption bands centred at 3647, 3464 and 3359 cm⁻¹. Jadeite from a Californian vein occurrence is characterised by bands at 3616 and 3557 cm⁻¹ and contains about 197 wt ppm H₂O. Based on the pleochroic scheme of the OH absorption bands in diopside, OH defect incorporation models are derived on the basis of fully occupied cation sites and under the assumption of M1 and M2 site vacancies; OH defects replacing O2 oxygen atoms are most common. The less pronounced OH pleochroism and the broad band absorption pattern of jadeite indicate a high degree of OH defect disordering. The pleochroic scheme of the main absorption bands at 3616 and 3557 cm⁻¹ implies partial replacement of O2 oxygen atoms by OH dipoles pointing to vacant Si sites. Under the assumption of M1 and M2 site vacancies, O1–H and O2–H defects are also derivable. OH incorporation modes assuming Si-vacancies should be considered for jadeite-rich clinopyroxenes formed in deep crust and upper mantle regions.     

The effect of “A” site occupancy upon the hydroxyl stretching frequency in clinoamphiboles

The electric field arising from K⁺ or Na⁺ in the A sites of synthetic hydroxyamphiboles of the richterite-tremolite series raises the stretching frequency of adjacent OH groups by about 60 cm^–1. In natural amphiboles, however, the increase in frequency is generally only 20–40 cm^–1, due, probably, to the effects of such substitutions as F for OH and Al for Si.     

Hydroxyl in mantle olivine xenocrysts from the Udachnaya kimberlite pipe

The incorporation of hydrogen in mantle olivine xenocrysts from the Udachnaya kimberlite pipe was investigated by Fourier-transform infrared spectroscopy and secondary ion mass spectrometry (SIMS). IR spectra were collected in the OH stretching region on oriented single crystals using a conventional IR source at ambient conditions and in situ at temperatures down to −180°C as well as with IR synchrotron radiation. The IR spectra of the samples are complex containing more than 20 strongly polarized OH bands in the range 3,730–3,330 cm⁻¹. Bands at high energies (3,730–3,670 cm⁻¹) were assigned to inclusions of serpentine, talc and the 10 Å phase. All other bands are believed to be intrinsic to olivine. The corresponding point defects are (a) associated with vacant Si sites (3,607 cm⁻¹ E || a, 3,597 E || a, 3,571 cm⁻¹ E || c, 3,567 E || c, and 3,556 E || b), and (b) with vacant M1 sites (most of the bands polarized parallel to a). From the pleochroic behavior and position of the OH bands associated with the vacant M1 sites, we propose two types of hydrogen—one bonded to O1 and another to O2, so that both OH vectors are strongly aligned parallel to a. The O2–H groups may be responsible for the OH bands at higher wavenumbers than those for the O1–H groups. The multiplicity of the corresponding OH bands in the spectra can be explained by different chemical environments and by slightly different distortions of the M1 sites in these high-pressure olivines. Four samples were investigated by SIMS. The calculated integral molar absorption coefficient using the IR and SIMS results of 37,500±5,000 L mol H₂O cm⁻² is within the uncertainties slightly higher than the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003) (28,450±1,830 L mol H₂O cm⁻²). The reason for the difference is the different distributions of the absorption intensity of the spectra of both studies (mean wavenumber 3,548 vs. 3,570 cm⁻¹). Olivine samples with a mean wavenumber of about 3,548 cm⁻¹ should be quantified with the absorption coefficient as determined in this study; those containing more bands at higher wavenumber (mean wavenumber 3,570 cm⁻¹) should be quantified using the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003).

Dehydration kinetics of antigorite using in situ high-temperature infrared microspectroscopy

The dehydration kinetics of serpentine was investigated using in situ high-temperature infrared microspectroscopy. The analyzed antigorite samples at room temperature show relatively sharp bands at around 3,655–3,660 cm^?1 (band 1), 3,570–3,595 cm^?1 (band 2), and 3,450–3,510 cm^?1 (band 3). Band 1 corresponds to the Mg–OH bond, and bands 2 and 3 correspond to OH associated with the substitution of Al for Si. Isothermal kinetic heating experiments at temperatures ranging from 625 to 700 °C showed a systematic decrease of the OH band absorbance with heating duration. The one-dimensional diffusion was found to provide the best fit to the experimental data, and diffusion coefficients were determined with activation energies of 219 ± 37 kJ mol^?1 for the total water band area, 245 ± 46 kJ mol^?1 for band 1, 243 ± 57 kJ mol^?1 for band 2, and 256 ± 53 kJ mol^?1 for band 3. The results indicate that the dehydration process is controlled by one-dimensional diffusion through the tetrahedral geometry of serpentine. Fluid production rates during antigorite dehydration were calculated from kinetic data and range from 3 × 10^?4 to 3 × 10^?5  $ {\text{m}}_{\text{fluid}}^{ 3} \,{\text{m}}_{\text{rock}}^{ - 3} \,{\text{s}}^{ - 1} $ . The rates are high enough to provoke hydraulic rupture, since the relaxation rates of rocks are much lower than these values. The results suggest that the rapid dehydration of antigorite can trigger an intermediate-depth earthquake associated with a subducting slab.     

Polarized Raman spectra of beryl and bazzite

The polarized Raman spectra of four different beryl crystals were studied at room temperature in the range from 30 to 4000 cm^-1. The spectra show significant differences between the samples studied, and corrections are proposed for the reference Raman spectra of beryl previously reported by Adams and Gardner (1974). Type II water is observed in two crystals; the corresponding symmetric Raman stretching band at 3595 cm^-1 is extremely strong for an impurity (about 20% of the strongest beryl lattice mode). Another, sharper, band of similar intensity at 3605 cm^-1 could possibly originate from a hydroxyl stretching mode. Additional weaker bands are observed around 1600 cm^-1 and 3600–3750 cm^-1. The first polarized Raman spectra of bazzite are presented and discussed.     

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     

Optical spectroscopy study of natural Fe, Ti-bearing calcic amphiboles

Over thirty samples of natural Ti-bearing amphiboles with Ti- and Fe-contents ranging from 0.111 to 0.729 atom per formula unit (a.p.f.u.) and from 0.479 to 2.045 a.p.f.u., respectively, were studied by means of optical absorption spectroscopy and microprobe analysis. Thirteen samples were also studied by Mössbauer spectroscopy. A strong pleochroic absorption edge, causing the dark brown colours of Ti-bearing amphiboles, is attributed to ligand-metal and metal-metal charge transfer transitions involving both iron and titanium ions (O^2?→ Fe³⁺, Fe²⁺, O^2?→ Ti⁴⁺ and Fe²⁺ + Ti⁴⁺→ Fe³⁺ + Ti³⁺). A broad intense Y-polarized band ～22?000?cm^?1 (ν_1/2?≈?3700?cm^?1) in spectra of two low iron amphiboles with a relatively low Fe³⁺/Fe_total ratio, both from eclogite-like rocks in kimberlite xenoliths, was attributed to electronic Fe²⁺(M3) + Ti⁴⁺(M2)→Fe³⁺(M3)+Ti³⁺(M2) IVCT transitions. The IVCT bands of other possible ion pairs, involving Ti⁴⁺ and Fe²⁺ in M2 and M1, M4 sites, respectively, are presumed to be at higher energies, being obscured by the absorption edge.     

Fine structure in the infrared OH-stretching bands of holmquistite and anthophyllite

The principal infrared OH-stretching bands in the orthorhombic (Mg, Fe, Mn, Li) amphiboles holmquistite and anthophyllite show fine structure due to the occurrence of two symmetrically distinct OH groups in the crystal structure. There are two distinct tetrahedral double chains in the orthorhombic amphibole structure, the A chain and the B chain. The B chain is more rotated than the A chain, and the stereochemistry around each of the OH sites suggests that the hydrogen bond to the bridging anion(s) of the B chain is stronger than the hydrogen bond to the bridging anion(s) of the A chain. This difference is sufficient to shift the frequency of the principal OH2-stretching band(s) ~5 cm ^-1 to lower frequency, and allows resolution of the two bands in the infrared spectrum. This distinction could allow detection of possible OH, F ordering between the two distinct monovalent-anion sites in the orthorhombic amphibole structure.     

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     

Structural and chemical characterization of synthetic (Na,K)-richterite solid solutions by EMP, HRTEM, XRD and OH-valence vibrational spectroscopy

The composition and structure of synthetic (Na,K)-richterites have been characterized by EMP, HRTEM, XRD and FTIR methods. Despite the fact that the syntheses were done on bulk compositions along the richterite-K-richterite binary, EMP analyses and FTIR spectra indicate that the amphiboles are not simple solid solutions of the two richterite endmembers richterite and K-richterite alone, but tremolite and Mg-cummingtonite components are also present in considerable amounts. HRTEM observations show that the amphiboles are structurally well ordered. Only a very few chain multiplicity faults are present. XRD examination reveals lattice parameters of 9.9055 Å, 17.9844 Å, 5.2689 Å and 104.212° for richterite and 10.0787 Å, 17.9877 Å, 5.2715 Å and 104.878° for K-richterite endmembers. The unit cell volumes are 909.90 ų and 923.61 ų for richterite and K-richterite, respectively. The lattice parameters a and β for K-richterite are considerably larger than those published previously implying that those were not determined for pure K-richterite. The positions of the characteristic OH-stretching vibrations in the IR for sodium-potassium (3729.8–3734.8 cm^?1) and vacancies (3671.1–3675.4 cm^?1) on the A-site are in agreement with earlier determinations. Using synthetic tremolite as a standard the vacancy concentration on the A-site of the synthetic (Na,K)-richterites was determined quantitatively by FTIR-spectroscopy. The OH-stretching vibration of this synthetic tremolite is at 3674.5 cm^?1. It is assigned to a local coordination with 3 Mg (2 M₁+M₃) as nearest neighbors and with 2 Ca (M₄) as next nearest neighbors. A well resolved band with a smaller intensity is located at 3669.2 cm^?1, which is attributed to a configuration including Ca+Mg on M₄ instead of only Ca.     

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.     

In-situ Moissanite in Dunite: Deep Mantle Origin of Mantle Peridotite in Luobusa Ophiolite, Tibet

We report the discovery of an in-situ natural moissanite as an inclusion in the Cr-spinel from the dunite envelope of a chromitite deposit in Luobusa ophiolite, Tibet. The moissanite occurs as a twin crystal interpenetrated by two quadrilateral signal crystals with sizes of 17 μm× 10 μm and 20 μm× 7 μm, respectively. The moissanite is green with parallel extinction. The absorption peaks in its Raman spectra are at 967-971 cm-1, 787-788 cm-1, and 766 cm-1. The absorption peaks in the infrared spectra are at 696 cm-1, 767 cm-1, 1450 cm-1, and 1551 cm-1, which are distinctly different from the peaks for synthetic silicon carbide. Moissanites have been documented to form in ultra-high pressure, high temperature, and extremely low fO2 environments and their 13C-depleted compositions indicate a lower mantle origin. Combined with previous studies about other ultra-high pressure and highly reduced minerals in Luobusa ophiolite, the in-situ natural moissanite we found indicates a deep mantle origin of some materials in the mantle sequence of Luobusa ophiolite. Further, we proposed a transformation model to explain the transfer process of UHP materials from the deep mantle to ophiolite sequence and then to the supra-subduction zone environment. Interactions between the crown of the mantle plume and mid-ocean ridge are suggested to be the dominant mechanism.     

A study of bernalite,Fe(OH)3, using Mössbauer spectroscopy,optical spectroscopy and transmission electron microscopy

To study the crystal chemistry of bernalite, Fe(OH)₃, and the nature of the octahedral Fe³⁺ environment, Mössbauer spectra were recorded from 80 to 350 K, optical spectra were recorded at room temperature and a sample was studied using transmission electron microscopy. The Mössbauer spectrum of bernalite consists of a single six-line magnetic spectrum at 80 K. A broadened six-line magnetic spectrum with significantly less intensity is observed at higher temperatures, and is attributed to a small fraction of bernalite occurring as small particles. The variation of hyperfine magnetic field data for bulk bernalite with temperature is well described by the Weiss molecular field model with parameters of H ₀ = 55.7±0.3 T and T _N = 427±5K. The centre shift data were fitted to the Debye model with parameters ₀=0.482±0.005 mm/s (relative to -Fe) and _M=492±30 K. The quadrupole shift is near zero at 300 K, and does not vary significantly with temperature. Absorption spectra in the visible and near infrared range show three crystal field bands of Fe³⁺ at 11 300, 16000 and 23 200 cm^-1, giving a crystal field splitting of 14 570 cm^-1 and Racah parameters of B=629 cm^-1 and C=3381 cm^-1. Infrared reflection spectra show two distinct OH-stretching frequencies, which could correspond to two structurally different types of OH groups. A band was also observed at 2250 cm^-1, suggesting the presence of molecular CO₂ in the large cation site. Analytical transmission electron microscopy indicates that Si occurs within the bernalite structure as well as along domain boundaries. Electron diffraction and imaging show that bernalite is polysynthetically twinned along {100} planes with twin domains ranging from 3 to 20 nm in thickness. Results are discussed with respect to the nature of the octahedral Fe³⁺ site, and compared with values for other iron oxides and hydroxides.