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.     

OH point defects in olivine from Pakistan

The infrared (IR) spectra of gem-quality olivine crystals from Pakistan, formed in serpentinised dunitic rocks, are characterised by strongly pleochroic absorption bands at 3,613, 3,597, 3,580 and 3,566 cm^?1. These bands are assigned to O-H stretching vibrations of OH point defects corresponding to H₂O concentrations of about 35 wt ppm. Unlike other olivine spectra, the dominating bands are strongly polarised parallel to the b-axis. The unusual spectra type, excludes the presence of planar defects. This finding is supported by transmission electron microscopy. The 3,613 cm^?1 band is related to vacant Si sites, the slightly lower energetic bands preferentially to vacant M2 sites. The exclusive presence of these bands is not only a characteristic feature of olivines treated under high P,T conditions equivalent to mantle environment, the presence of these bands in untreated natural olivine also indicates formation conditions equivalent to crustal rocks.     

Single-crystal polarized FTIR spectroscopy and neutron diffraction refinement of cancrinite

We relate a single-crystal FTIR (Fourier transform infrared) and neutron diffraction study of two natural cancrinites. The structural refinements show that the oxygen site of the H₂O molecule lies off the triad axis. The water molecule is almost symmetric and slightly tilted from the (0001) plane. It is involved in bifurcated hydrogen bridges, with Ow···O donor–acceptor distances >2.7 Å. The FTIR spectra show two main absorptions. The first at 3,602 cm^?1 is polarized for E ⊥ c and is assigned to the ν₃ mode. The second, at 3,531 cm^?1, is also polarized for E ⊥ c and is assigned to ν₁ mode. A weak component at 4,108 cm^?1 could possibly indicate the presence of additional OH groups in the structure of cancrinite. Several overlapping bands in the 1,300–1,500 cm^?1 range are strongly polarized for E ⊥ c, and are assigned to the vibrations of the CO₃ group.     

Theoretical study of OH-defects in pure enstatite

The infrared spectroscopic properties of selected defects in orthoenstatite are investigated by first-principles calculations. The considered defects include doubly protonated Mg vacancies at M1 and M2 sites, fully protonated SiA and SiB vacancies (hydrogarnet defects), and doubly protonated SiA and SiB vacancies associated with interstitial Mg²⁺ cations. The bands observed at 3,070 and 3,360 cm^?1 in the spectrum of synthetic enstatite samples are ascribed to O2A–H and O2B–H groups, respectively, associated with M2 vacancies. The theoretical models suggest that bands observed at 3,590 and 3,690 cm^?1 in the spectrum of enstatite samples synthesized under low silica-activity conditions correspond to O2H and O1H groups associated with SiB vacancies partially compensated by interstitial Mg²⁺ cations in fivefold coordination. The theoretical relation between the integrated absorption coefficient of OH-defects and vibrational frequencies is consistent with previous observations indicating that the absorption coefficients of OH-defects are comparatively stronger in enstatite than in the olivine polymorphs.     

Contribution of interstitial OH groups to the incorporation of water in forsterite

Water incorporation in forsterite samples synthesized under low to medium silica-activity conditions mostly occurs via a substitutional mechanism in which a Si vacancy is compensated by four protons. Corresponding IR absorption spectra display a cluster of narrow and weakly anharmonic OH-stretching bands at wavenumbers above 3,500 cm^?1. However, this diagnostic spectrum is often superimposed to one broader absorption band, rarely two, displaying pronounced temperature-dependent properties and tentatively assigned to H atoms in interstitial position (Ingrin et al. in Phys Chem Miner 40:499–510, 2013). Here, we investigate the structural and vibrational properties of selected interstitial H-bearing defects in forsterite using a first-principles modeling approach. We show that the broad bands discussed by Ingrin et al. (Phys Chem Miner 40:499–510, 2013) are most likely related to interstitial OH groups in the vacant octahedral sites alternating with the M2 sites along the c axis of the forsterite structure. The corresponding OH defects lead to the formation of fivefold coordinated Si species. Their peculiar thermal properties stem from the vibrational phase relaxation due to the anharmonic coupling of the high-energy local OH-stretching mode with a low-energy vibrational mode. This “exchange mode” corresponds to the hindered longitudinal translation of the OH group. These results suggest that at high pressure, hydrogen incorporation in forsterite is dominated by coexisting interstitial OH groups and (4H)_Si defects.     

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.     

Infrared spectroscopic properties of goethite: anharmonic broadening,long-range electrostatic effects and Al substitution

The infrared spectrum and its temperature dependence (20–320 K) were collected on a synthetic goethite sample (α-FeOOH). In addition, the infrared powder absorption spectrum of goethite and aluminum-substituted goethite was computed using ab initio quantum mechanical calculations based on density functional theory. This combined experimental and theoretical approach allows (1) the unequivocal assignment of absorption bands to the corresponding vibrational modes, (2) separate identification of the effects of the particle shape and of the aluminum substitution on the infrared spectrum, and (3) a discussion of the anharmonic properties and the origin of the line broadening in goethite. In particular, the two well-resolved OH bending absorption bands show different temperature evolution. Their detailed analysis suggests that the broadening of the band at ~800 cm^?1 cannot be described solely by a usual three-phonon process. The strong anharmonic behavior of this mode implies the addition of a four-phonon process, such as a pure dephasing process. In our calculations, the effect of the Hubbard U correction is also investigated and found to be most visible on the OH stretching and bending modes, in relation to the associated structural relaxation. The OH stretching frequencies decrease, leading to a better agreement with experimental frequencies, while the OH bending frequencies increase.     

Experimental partitioning of halogens and other trace elements between olivine, pyroxenes, amphibole and aqueous fluid at 2 GPa and 900–1,300 °C

We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D _Cl ^{olivine/fluid} varying between 10^?5 and 10^?3, whereas D _Cl ^{orthopyroxene/fluid} and D _Cl ^{clinopyroxene/fluid} are ~10^?4 and D _Cl ^{amphibole/fluid} is ~5 × 10^?3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D ^amph/fluid ≈ D ^cpx/fluid > D ^opx/fluid > D ^ol/fluid but that D ^{mineral/fluid} for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm^?1. In F ± TiO₂-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm^?1. Absorption bands at ~3,530 and ~3,570 cm^?1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.     

A reassessment of the role of iron in the 5,000–30,000 cm−1 region of the electronic absorption spectra of tourmaline

The E∥c and E ⊥ c polarized optical absorption spectra of a variety of blue/green tourmalines and a schorl were measured from room temperature down to helium temperatures. Heat treatments at 750–800° C in air and hydrogen were carried out on several green tourmalines. From the results obtained, absorptions at 7,900 and 13,800 cm^?1 in the E∥c spectra of tourmalines are assigned to Fe²⁺ in the b-site. In the same polarization, bands detected at 9,000 and 13,400 cm^?1 are attributed to Fe²⁺ in the smaller c position. In contrast to previous interpretations, the E ⊥ c polarized bands at 9,000 and 13,800 cm^?1 are not assigned to single ion transitions, but are largely associated with nearest neighbour Fe²⁺-Fe³⁺ pairs. Correlations between near-infrared band absorption coefficients and FeO concentration reinforce these assignments. The temperature dependence and the reaction to heat treatment of the strongly polarized (E⊥c?E∥c) band near 18,000 cm^?1 in blue and green tourmaline spectra are shown to be consistent with previous assignments of the band to Fe²⁺+Fe³⁺→Fe³⁺+Fe²⁺ charge transfer. Similar results are discussed for broad absorptions (also E⊥c?E∥c) found in the 22,000–25,000 cm^?1 region of the spectra of certain green and brown tourmalines. It is concluded that these absorptions are due to Fe²⁺+Ti⁴⁺→Fe³⁺+Ti³⁺ charge transfer. The proposal is made that the initial effect of heating green tourmalines in air and hydrogen is to reduce Fe³⁺ cations located in both b- and c-sites. Further heat treatment in air and hydrogen results in the oxidation of Fe²⁺→Fe³⁺ and leads to the generation of bands near 19,100 and 21,600 cm^?1. The newly formed bands are assigned to Fe³⁺-Fe³⁺ pairs.     

Spectroscopic studies of synthetic and natural ringwoodite, γ-(Mg,Fe)<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

Synthetic ringwoodite γ-(Mg_1?x Fe _x )₂SiO₄ of 0.4 ≤ x ≤ 1.0 compositions and variously colored micro-grains of natural ringwoodite in shock metamorphism veins of thin sections of two S6-type chondrites were studied by means of microprobe analysis, TEM and optical absorption spectroscopy. Three synthetic samples were studied in addition with Mössbauer spectroscopy. The Mössbauer spectra consist of two doublets caused by ^VIFe²⁺ and ^VIFe³⁺, with IS and QS parameters close to those established elsewhere (e.g., O’Neill et al. in Am Mineral 78:456–460, 1993). The Fe³⁺/Fe_total ratio evaluated by curve resolution of the spectra, ranges from 0.04 to 0.1. Optical absorption spectra of all synthetic samples studied are qualitatively very similar as they are directly related to the iron content. They differ mostly in the intensity of the observed absorption features. The spectra consist of a very strong high-energy absorption edge and a series of absorption bands of different width and intensity. The three strongest and broadest absorptions of them are attributed to splitting of electronic spin-allowed ⁵ T _2g → ⁵ E _g transitions of ^VIFe²⁺ and intervalence charge-transfer (IVCT) transition between ferrous and ferric ions in adjacent octahedral sites of the ringwoodite structure. The spin-allowed bands at ca. 8,000 and 11,500 cm^?1 weakly depend on temperature, whilst the Fe²⁺/Fe³⁺ IVCT band at ~16,400 cm^?1 displays very strong temperature dependence: i.e., with increasing temperature it decreases and practically disappears at about 497 K, a behavior typical for bands of this type. With increasing pressure the absorption edge shifts to lower energies while the spin-allowed bands shift to higher energy and strongly decreases in intensity. The IVCT band also strongly weakens and vanishes at about 9 GPa. We assigned this effect to pressure-induced reduction of Fe³⁺ in ringwoodite. By analogy with synthetic samples three broad bands in spectra of natural (meteoritic) blue ringwoodite are assigned to electronic spin-allowed transitions of ^VIFe²⁺ (the bands at ~8,600 and ~12,700 cm^?1) and Fe²⁺/Fe³⁺ IVCT transition (~18,100 cm^?1), respectively. Spectra of colorless ringwoodite of the same composition consist of a single broad band at ca. 12,000 cm^?1. It is assumed that such ringwoodite grains are inverse (Fe, Mg)₂SiO₄-spinels and that the single band is caused by the split spin-allowed ⁵ E → ⁵ T ₂ transition of ^IVFe²⁺. Ringwoodite of intermediate color variations between dark-blue and colorless are assumed to be partly inversed ringwoodite. No glassy material between the grain boundaries in the natural colored ringwoodite aggregates was found in our samples and disprove the cause of the coloration to be due to light scattering effect (Lingemann and Stöffler in Lunar Planet Sci 29(1308), 1998).     

Crystal chemistry, thermal expansion, and Raman spectra of hydroxyl-clinohumite: implications for water in Earth’s interior

Two samples of hydroxyl-clinohumite, sample SZ0407B with approximate composition Mg_8.674(14)Fe_0.374(4)(Si_0.99(1)O₄)₄(OH)₂ and sample SZ0411B with composition Mg₉(SiO₄)₄(OH)₂, were synthesized at 12 GPa and 1,250 °C coexisting with olivine. Unit-cell parameters determined by single-crystal X-ray diffraction are given as follows: a = 4.7525(4) Å, b = 10.2935(12) Å, c = 13.7077(10) Å, α = 100.645(9)°, V = 659.04(9) Å³ for SZ0407B, and a = 4.7518(6) Å, b = 10.2861(12) Å, c = 13.7008(9) Å, α = 100.638(9)°, V = 658.15(9) Å³ for SZ0411B. Single-crystal X-ray intensity data were collected for crystal structure refinements of both samples. Relative to the pure-Mg sample, Fe decreases M3–OH bond lengths by ~0.010(3) Å, consistent with some ferric iron ordering into M3. Raman spectroscopy shows two strong bands in the lattice-mode region at 650 and 690 cm^?1 in the Fe-bearing sample, which are not observed in the pure-Mg sample. Spectra in the H₂O region show at least five bands, which are deconvolved into seven distinct O–H-stretching modes. Thermal expansion measurements were carried out for both samples from 153 to 787 K by single-crystal X-ray diffraction. The average a-, b-, c-axial and volumetric thermal expansion coefficients (10^?6 K^?1) are 10.5(1), 12.3(2), 12.5(2) and 34.9(5) for SZ0407B, respectively, and 11.1(1), 12.6(3), 13.7(3), 36.8(6) for SZ0411B, respectively. After heating, the unit-cell parameters were refined again for each sample at ambient condition, and no significant changes were observed, indicating no significant oxidation or dehydration during the experiment. For the DHMS phases along the brucite–forsterite join, linear regression gives a systematic linear decrease in expansivity with increasing density. Further, substitution of ferrous iron into these structures decreases thermal expansivity, making the Fe-bearing varieties slightly stiffer.     

Raman spectra of polycrystalline microdiamond inclusions in zircons,and ultrahigh-pressure metamorphism of a quartzofeldspathic rock from the Erzgebirge terrane,Germany

ABSTRACT

Polycrystalline microdiamonds are rare in ultrahigh-pressure (UHP) rocks worldwide. Among samples collected at Erzgebirge, Germany, we found abundant polycrystalline microdiamonds as inclusions in zircons from a quartzofeldspathic rock. To illuminate their origin and forming age, we investigated morphologies and Raman spectra of 52 microdiamond inclusions, and dated the zircon host. The zircons have low Th/U values (0.03–0.07) and a concordia U/Pb age of 335.8 ± 1.9 Ma. Polycrystalline diamond (10–40 µm) consists of many fine-grained crystals (1.5–3 µm) with different orientations; discrete single diamonds (2–20 µm) are rare. All measured Raman spectra show an intense diamond band at 1332–1328 cm^?1 and have a negative correlation with full width at half maximum (FWHM) of 5.8–11.3 cm^?1. These data combined with previously reported diamond band data (1331–1337 cm^?1) are compatible with those of diamond inclusions in various host minerals from other UHP terranes, but are different from those of ureilite diamonds. The Erzgebirge microdiamonds in zircon do not display visible disordered sp³-carbon, but show downshifting of the Raman band from the ideal value (1332 cm^?1), and have a broader diamond band (FWHM >3 cm^?1) than those of well-ordered diamonds. These features may reflect imperfect ordering due to rapid nucleation/crystallization during UHP metamorphism and rapid exhumation of the UHP terrane. Graphite inclusions in zircon show a typical G-band at 1587 cm^?1. Our study together with previously reported C-isotopic compositions (δ¹³C, ?17 to ?27‰) of diamond and occurrences of fluid/melt inclusions in diamond and garnet indicates that Erzgebirge microdiamonds are metamorphic, have an organic carbon source, and crystallized from aqueous fluids. Limited long-range ordering suggested by the Raman spectra is a function of the P–T time of crystallization and subsequent thermal annealing on decompression. Combined with regional geology, our work further constrains the tectonic evolution of the Erzgebirge terrane.     

On the presence of hydrous defects in differently coloured wulfenites (PbMoO4): an infrared and optical spectroscopic study

Several samples of wulfenite, PbMoO₄, varying in colour from colourless to yellow, orange and red, have been characterised by means of IR and optical absorption spectroscopy and by microprobe analyses. A distinct pleochroic band group with absorption maxima centred at 3,380 and 3,150 cm^?1 can be seen in the IR spectra of wulfenite single-crystals, indicating the presence of hydroxyl groups. The pleochroic and thermal behaviour of the OH stretching bands along with deuteration experiments, as well as results obtained from synthetic flux-grown samples, exclude the presence of submicroscopic hydrous mineral inclusions as their primary origin. The pleochroic scheme and the band positions were used to postulate a model for the OH incorporation mode, based on the assumption of vacancies on Mo and Pb sites in the structure of this ‘nominally anhydrous mineral’. Optical absorption spectra of coloured natural samples show a broad and polarised band around 23,000–24,000 cm^?1, preceding the fundamental UV absorption edge, which has been identified as the reason for the colour of the mineral. The comparison with synthetic PbMoO₄ single-crystals, doped with variable amounts of Cr⁶⁺, yielded conclusive evidence that trace amounts of the CrO₄ ^2? anion group, substituting for MoO₄ ^2?, determine the variable colour. Besides, in one sample, trace amounts of Nd³⁺ have been spectroscopically identified.     

OH defects in quartz in the system quartz–albite–water and granite–water between 5 and 25?kbar

The incorporation of OH defects in quartz from the systems quartz–water, quartz–albite–water and granite–water at pressures between 5 and 25?kbar and temperatures between 800 and 1,000?°C was investigated by IR spectroscopy. The two most important OH absorption features can be assigned to hydrogarnet defects (absorption band at 3,585?cm^?1) and coupled substitutions involving Al³⁺ (Al–H defects, absorption bands at 3,310, 3,378 and 3,430?cm^?1). Al incorporation in quartz is controlled by mineral/melt partitioning (D _Al ^Qz/Melt ?=?0.01) and exhibits a negative pressure dependence. This trend is not clearly reflected by the concentration of Al–H defects, which shows positive deviations from the theoretical 1:1 correlation of Al/H for some samples. In contrast to the Al–H defects, formation of hydrogarnet defects appears to be positively correlated to pressure and water activity, and may be used a petrological indicator. The overall water concentration exhibits only minor changes with pressure and temperature, but a clear correlation of water activity (controlled by various amounts of dissolved salts) and hydrogarnet substitution could be established.     

Empirical study of the infrared lattice vibrations (1100–350 cm−1) of phlogopite

A detailed evaluation of the assignments given to the infrared (IR) vibrations in the lattice stretching region is presented here based on observations of the effects of various chemical substitutions in synthetic analogues of phlogopite, KMg₃(AlSi₃)O₁₀(OH)₂. As in previous studies, this study has confirmed that the 995, 960, and 460 cm^?1 vibrations are influenced by Si, the 822 and 760 cm^?1 vibrations by Al, the 915 and 725 cm^?1 vibrations by Al and Si, and the 592 cm^?1 vibration by OH. Contrary to previous studies, it is shown here that the 690, 495, and 375 cm^?1 vibrations are strongly linked with Mg and not just Si. The 655 cm^?1 band in phlogopite is attributed to an in-plane Al-O vibration rather than an Al-O-Si vibration. As a check on the band assignments made here, IR spectra were obtained for synthetic clintonite, CaMg₂Al(Al₃Si)O₁₀(OH)₂, as well as its chemical analogues and compared with the IR spectrum of phlogopite. The band intensities for the Si-O, Al-O, and Si-O-Mg vibrations changed in accord with the composition of clintonite. The most intense band in clintonite at 660 cm^?1 appears to be associated only with Al and is assigned here to a tetrahedral Al-O-Al vibration which must be present, if not dominant, in this mineral. The near coincidence of an in-plane Al-O vibration at 655 cm^?1 (phlogopite) and an in-plane Al-O-Al vibration at 660 cm^?1 (clintonite) makes the identification of tetrahedral Al-Si order-disorder in trioctahedral layered silicates by IR spectroscopy very difficult. The ratio of the 822/995 cm^?1 bands may, however, prove to be very useful for discerning the amount of tetrahedrally coordinated Al in these types of minerals.     

OH defects in quartz in granitic systems doped with spodumene,tourmaline and/or apatite: experimental investigations at 5–20 kbar

The incorporation of OH defects in quartz as a function of Li content in the bulk system and pressures was investigated. Quartz crystals were grown in water-saturated granitic systems, containing various amounts Li, B and P, supplied as accessory phases such as spodumene, tourmaline or apatite in the starting mixtures. High pressure experiments were performed at temperatures between 900 and 1100 °C, and pressures between 5 and 20 kbar with a piston cylinder apparatus, and the synthesized quartz crystals were analyzed by IR spectroscopy, electron microprobe and LA-ICP-MS spectroscopy. All IR absorption spectra revealed absorption features that can be assigned to AlOH (3313, 3379 and 3431 cm^?1) and (4H)_Si defects (3585 cm^?1), whereas quartz grown in the Li and B systems exhibited two additional bands related, respectively, to LiOH (3483 cm^?1) and BOH defects (3596 cm^?1). It was further observed that LiOH incorporation increases with higher spodumene content in the starting material and decreases with pressure, until no LiOH defects are observed at pressure higher than 15 kbar. Specifically, the most pronounced reduction of LiOH defects occurs in a rather narrow pressure interval (10–15 kbar) close to the high-quartz/low-quartz transition. However, the link between the transition and the defect incorporation remains unclear. Li total concentrations always exceed the Li-coupled LiOH defects, suggesting the simultaneous presence of dry AlLi defects. Results of this study suggest that LiOH defects are detectable only in quartz crystals grown from middle and upper crustal sections (such as hydrothermal quartz) and not in quartz from deep roots of orogenic granitoids.     

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.     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

Raman spectroscopy of natural silica in Chicxulub impactite,MexicoSpectroscopie Raman de silices naturelles dans l'impactite de Chicxulub,Mexique

A series of natural silica impactite samples from Chicxulub (Mexico) was investigated by Raman microprobe (RMP) analysis. The data yield evidence for high-pressure shock metamorphism in the rock. The impactite contains three polymorphs of silica: the original α-quartz, and two high-pressure varieties – coesite and disordered quartz representing various degrees of crystallinity. We found systematic changes in frequencies and half-widths of the Raman bands, caused by increasing irregularities of bond-lengths and bond-angles and a general breaking-up of the structure as a result of impact events. Therefore, RMP is an adequate tool for measuring the crystallinity of disordered quartz. The half-width Γ and the frequency ω of the symmetric SiOSi stretching vibrational band (A₁ mode) of the SiO₄ tetrahedra are the most amenable parameters for estimating the degree of crystallinity. In well-crystallized quartz, Γ=5 cm^?1 and ω=464 cm^?1, while in highly disordered quartz this line shifts up to ω=455 cm^?1 and broadens up to Γ=30 cm^?1. The Raman lineshapes appear to depend strongly on the degree of lattice disorder subsequent to impact events. To cite this article: M. Ostroumov et al., C. R. Geoscience 334 (2002) 21–26     

Cation diffusion in olivine—I. Cobalt and magnesium

Cobalt and magnesium interdiffusion coefficients in synthetic crystals of olivine have been determined by a method of couple annealing. These coefficients increase with temperature and Co concentration. The coefficients in forsterite along the c crystallographic axis range from 1.13 × 10^?12 to 6.85 × 10^{?11 cm2sec?1} at temperatures ranging from 1150 to 1400°C. The calculated activation energies for Co-Mg interdiffusion in forsterite are 526 kJmol^?1 above approximately 1300°C and 196 kJmol^?1 at lower temperatures. These results indicate that the Co-Mg mobility in olivine is relatively low compared to published results for Fe-Mg interdiffusion.