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1.
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.  相似文献   

2.
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.  相似文献   

3.
The high-pressure behavior of Keokuk kaolinite has been studied to 9.5 GPa by infrared spectroscopy using synchrotron radiation. The kaolinite-I → kaolinite-II and kaolinite-II → kaolinite-III transformations have clear spectroscopic expression, with discontinuities coinciding with the transformation pressures bracketed by X-ray diffraction (Welch and Crichton in Am Mineral 95:651–654, 2010). The experimental spectra have been interpreted from band assignments derived from density functional theory for the structures of kaolinite-II and kaolinite-III, using as starting models the ab initio structures reported by Mercier and Le Page (Acta Crystallogr A B64:131–143, 2008, Mater Sci Technol 25:437–442, 2009) and unit-cell parameters from Welch and Crichton (Am Mineral 95:651–654, 2010). The relaxed theoretical structures are very similar to those reported by Mercier and Le Page (Acta Crystallogr A B64:131–143, 2008, Mater Sci Technol 25:437–442, 2009) in their theoretical investigation of kaolinite polytypes at high pressure. The vibrational spectra calculated from the quantum-mechanical analysis allow band assignments of the IR spectra to be made and provide insights into the behavior of different OH environments in the two high-pressure polytypes. The single perpendicular-interlayer OH group of kaolinite-III has a distinctive spectroscopic signature that is diagnostic of this polytype (ν = 3,595 cm−1 at 9.5 GPa) and is sensitive to the compression/expansion of the interlayer space. This OH group also has a distinctive signature in the calculated spectra. The spectra collected on decompression are those of kaolinite-III and persist largely unchanged to 4.6 GPa, except for a continuous blue shift of the 3,595 cm−1 band to 3,613 cm−1. Finally, kaolinite-I is recovered at 0.6 GPa, confirming the kaolinite-III → kaolinite-I transformation previously observed by X-ray diffraction, and the irreversibility of the kaolinite-II → kaolinite-III transformation. The ambient spectra collected at the start and finish of the experiment are those of kaolinite-I, and start/finish band frequencies agree to within 6 cm−1.  相似文献   

4.
 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  相似文献   

5.
The infrared (IR) spectra of gem-quality baryte crystals from different occurrences are characterized by relatively weak but strongly pleochroic absorption bands at 3,280, 3,220, 3,155, and 3,115 cm−1. These bands are assigned to anti-symmetric and symmetric OH stretching vibrations of two types of H2O molecules localized on vacant Ba sites. The H–H axis of the H2O I molecule is slightly tilted from the a-axis direction, its twofold axis being nearly parallel to the b-axis, thus defining the plane of the H2O molecule practically parallel to (001). The H2O II molecule has its H–H axis parallel to the b-axis direction, with its plane lying approximately parallel to (101). The values of the total water contents of the baryte crystals, calculated on the basis of IR spectroscopic data, are ranging from about 1.7–3.8 wt.ppm. The possible presence of H3O+ ions is also discussed.  相似文献   

6.
Vibrational properties of diaspore, α-AlOOH, have been re-investigated using room-temperature single-crystal Raman spectroscopy and low-temperature powder infrared (IR) transmission spectroscopy. First-principles harmonic calculations based on density functional theory provide a convincing assignment of the major Raman peaks and infrared absorption bands. The large width of the Raman band related to OH stretching modes is ascribed to mode–mode anharmonic coupling due to medium-strength H-bonding. Additional broadening in the powder IR spectrum arises from depolarization effects in powder particles. The temperature dependence of the IR spectrum provides a further insight into the anharmonic properties of diaspore. Based on their frequency and temperature behavior, narrow absorption features at ~2,000 cm−1 and anti-resonance at ~2,966 cm−1 in the IR spectrum are interpreted as overtones of fundamental bending bands.  相似文献   

7.
The structure and vibrational spectrum of boehmite have been investigated at the quantum-mechanical level with the CRYSTAL code, using a Gaussian-type basis set and the B3LYP Hamiltonian. Three space groups are considered in this study: Cmcm, Cmc21, P21/c. Cmcm turns out to correspond to a transition state, whereas Cmc21 and P21/c are minimum energy structures. The difference among them is the position of H atoms only, the Al-O frame being essentially the same. Harmonic frequencies at the Γ point have been computed. The comparison between calculated and experimental frequencies shows a good agreement for the Al-O part of the spectrum (under 790 cm−1). For the Al-OH bending modes (800–1,300 cm−1) an absolute differences of 50–100 cm−1 is observed; for the OH stretching modes (3,200–3,500 cm−1) it increases to 120–200 cm−1: anharmonicity is large because OH groups are involved in strong hydrogen bonds.  相似文献   

8.
High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm−1 at ambient temperature for hydrous Mg-ringwoodite (γ-Mg2SiO4) up to 30 GPa. The main feature in the OH− stretching region is an extremely broad band centred at 3,150 cm−1. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm−1 and an absorption plateau persist with a maximum wavenumber of 3,800 cm−1. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.  相似文献   

9.
Six synthetic NaScSi2O6–CaNiSi2O6 pyroxenes were studied by optical absorption spectroscopy. Five of them of intermediate (Na1−x , Ca x )(Sc1−x , Ni x )Si2O6 compositions show spectra typical of Ni2+ in octahedral coordination, more precise Ni2+ at the M1 site of the pyroxene structure. The common feature of all spectra is three broad absorption bands with maxima around 8,000, 13,000 and 24,000 cm−1 assigned to 3 A 2g → 3 T 2g, 3 A 2g → 3 T 1g and →3 T 1g (3 P) electronic spin-allowed transitions of VINi2+. A weak narrow peak at ∼14,400 cm−1 is assigned to the spin-forbidden 3 A 2g → 1 T 2g (1 D) transition of Ni2+. Under pressure the spin-allowed bands shift to higher energies and change in intensity. The octahedral compression modulus, calculated from the shift of the 3 A 2g → 3 T 2g band in the (Na0.7Ca0.3)(Sc0.7Ni0.3)Si2O6 pyroxene is evaluated as 85±20 GPa. The Racah parameter B of Ni2+(M1) is found gradually changing from ∼919 cm−1 at ambient pressure to ∼890 cm−1 at 6.18 GPa. The Ni end-member pyroxene [(Ca0.93 Ni0.07)NiSi2O6] has a spectrum different from all others. In addition to the above mentioned bands of Ni2+(M1) it displays several new relatively intense and broad extra bands, which were attributed to electronic transitions of Ni2+ at the M2 site. In difference to CaO8 polyhedron geometry of an eightfold coordination, Ni2+(M2)O8 polyhedra are assumed to be relatively large distorted octahedra. Due to different distortions and different compressibilities of the M1 and M2 sites the Ni2+(M1)- and Ni2+(M2)-bands display rather different pressure-induced behaviors, becoming more resolved in the high-pressure spectra than in that measured at atmospheric pressure. The octahedral compression modulus of Ni2+(M1) in this end-member pyroxene is evaluated as 150 ± 25 GPa, which is noticeably larger than in Ni0.3 pyroxene. This is due to a smaller size and, thus, a stiffer character of Ni2+(M1)O6 octahedron in the (Ca0.93Ni0.07)NiSi2O6 pyroxene compared to (Na0.7Ca0.3)(Sc0.7Ni0.3)Si2O6.
Monika Koch-MüllerEmail:
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10.
There are significant advantages in using indirect pedo-transfer functions, (PTFs) for the estimation of unsaturated soil properties. The pedo-transfer functions can be used for the estimation of the soil–water characteristic curve (SWCC) which in turn is used for the estimation of other unsaturated soil properties. The accuracy of the indirect pedo-transfer function method for the estimation of the SWCC depends on the PTF and the equation used to best-fit the particle-size distribution (PSD) data. The objectives of this study are to: (1) evaluate the performance of the Fredlund et al. (Can Geotech J 37:817–827, 2000) equation for best-fitting the particle-size distribution, (PSD) data, and, (2) compare the predictions made by two of the commonly used PTFs; namely, Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) and Fredlund et al. (Can Geotech J 39:1103–1117, 2002), for estimating the SWCC from the PSD. The authors used 258 measured PSDs and SWCC datasets from the Loess Plateau, China, for this study. The dataset consisted of 187 silt–loam soils, 41 loam soils, 11 silt–clay–loam soils, 10 sand–loam soils, 6 silt–clay soils, and 3 loam–sand soils. The SWCC and PSD datasets were measured using a Pressure Plate apparatus and the pipette method, respectively. The comparison between the estimated and measured particle-size distribution curves showed that the Fredlund et al. (Can Geotech J 37:817–827, 2000) equation closely prepresented the PSD for all soils in the Loess Plateau, with a lower root mean square error (RMSE) of 0.869%. The comparison between the estimated and measured water contents at the same suction showed that the Fredlund et al. (Can Geotech J 39:1103–1117, 2002) PTF performed somewhat better than the Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) function. The Fredlund et al. method had RMSE value of 0.039 cm3 cm−3 as opposed to 0.046 cm3 cm−3 for the Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) method. The Fredlund et al. (Can Geotech J 39:1103–1117, 2002) PTF produced the closest predictions for sand–loam, loam–sand, and loam soils, with a lower RMSE for gravimetric water content ranging from 0.006 to 0.036 cm3 cm−3. There were consistent over-estimations observed for silt–loam, silt–clay–loam, and slit–clay soils with RMSE values for gravimetric water content ranging from 0.037 to 0.043 cm3 cm−3. The measured and estimated air-entry values were closest when using the Fredlund et al. (Can Geotech J 39:1103–1117, 2002) PTF. The measured and estimated maximum slopes on the SWCC were closest when using the Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) PTF.  相似文献   

11.
Polarized absorption spectra, σ and π, in the spectral range 30000–400 cm−1 (3.71–0.05 eV) were obtained on crystal slabs // [001] of deep blue rutile at various temperatures from 88 to 773 K. The rutile crystals were grown in Pt-capsules from carefully dried 99.999% TiO2 rutile powder at 50 kbar/1500 °C using graphite heating cells in a belt-type apparatus. Impurities were below the detection limits of the electron microprobe (about 0.005 wt% for elements with Z≥13). The spectra are characterized by an unpolarized absorption edge at 24300 cm−1, two weak and relatively narrow (Δν1/2≈3500–4000 cm−1), slightly σ-polarized bands ν1 at 23500 cm−1 and ν2 at 18500 cm−1, and a complex, strong band system in the NIR (near infra red) with sharp weak peaks in the region of the OH stretching fundamentals superimposed on the NIR system in the σ-spectra. The NIR band system and the UV edge produce an absorption minimum in both spectra, σ and π, at 21000 cm−1, i.e. in the blue, which explains the colour of the crystals. Bands ν1 and ν2 are assigned to dd transitions to the Jahn-Teller split upper Eg state of octahedral Ti3+. The NIR band system can be fitted as a sum of three components. Two of them are partly π-polarized, nearly Gaussian bands, both with large half widths 6000–7000 cm−1, ν3 at 12000 cm–1 and the most intense ν4 at 6500 cm−1. The third NIR band ν5 of a mixed Lorentz-Gaussian shape with a maximum at 3000 cm−1 forms a shoulder on the low-energy wing of ν4. Energy positions, half band widths and temperature behaviour of these bands are consistent with a small polaron type of Ti3+Ti4+ charge transfer (CT). Polarization dependence of CT bands can be explained on the basis of the structural model of defect rutile by Bursill and Blanchin (1983) involving interstitial titanium. Two OH bands at 3322 and 3279 cm−1 in σ-spectra show different stability during annealing, indicating two different positions of proton in the rutile structure, one of them probably connected with Ti3+ impurity. Total water concentration in blue rutile determined by IR spectroscopy is 0.10 wt-% OH. The EPR spectra measured in the temperature interval 20–295 K show the presence of an electron centre at temperatures above 100 K and Ti3+ ions in more than one structural position, but predominantly in compressed interstitial octahedral sites, at lower temperatures. These results are in good agreement with the conclusions based on the electronic absorption data. Received: 24 March 1997 / Revised, accepted: 14 October 1997  相似文献   

12.
Infrared (IR) and nearinfrared (NIR) absorption spectra of hydrous and F-rich topazes were measured to assign an OH bending mode of topaz. Three absorption peaks at 1165, 3650, and 4803 cm−1 are assigned to OH related absorption peaks. Since a peak at 4803 cm−1 can be assigned to a combination mode of 1165 and 3650 cm−1, the 1165 cm−1 peak is harmonic with the 3650 cm−1 peak. Polarized IR absorption spectra of (100), (010), and (001) planes of the hydrous topaz were measured to examine IR active orientation of the 1165 cm−1 OH related mode. Three pleochroic distributions of the absorption peak at 1165 cm−1 on (100), (010), and (001) planes indicate an active orientation of the 1165 cm−1 OH related mode. The IR active orientation of the 1165 cm−1 OH related mode in topaz is normal to the OH dipole. The orthogonality and harmonic combination mode indicate that the 1165 cm−1 peak is OH bending mode. The active orientation of OH bending mode is polarized in the plane normal to the OH dipole. The polarization suggests that anisotropic thermal vibration of protons on the hydroxyl is maximum along the IR active orientation. Received: August 16, 1996 / Revised, accepted: April 20, 1997  相似文献   

13.
The high-pressure behavior of three synthetic amphiboles crystallized with space group P21/m at room conditions in the system Li2O–Na2O–MgO–SiO2–H2O has been studied by in situ synchrotron infrared absorption spectroscopy. The amphiboles have compositions ANa B(Na x Li1 − x Mg1) CMg5 Si8 O22(OH)2 with x = 0.6, 0.2 and 0.0, respectively. The high-P experiments up to 32 GPa were carried out on the U2A beamline at Brookhaven National Laboratory (NY, USA) using a diamond anvil cell under non-hydrostatic or quasi-hydrostatic conditions. The two most intense absorption bands in the OH-stretching infrared spectra can be assigned to two non-equivalent O–H dipoles in the P21/m structure, bonded to the same local environment M1M3Mg3–OH–ANa, and pointing toward two differently kinked tetrahedral rings. In all samples these bands progressively merge to give a unique symmetrical absorption with increasing pressure, suggesting a change in symmetry from P21/m to C2/m. The pressure at which the transition occurs appears to be linearly correlated to the aggregate B-site dimension. The infrared spectra collected for amphibole B(Na0.2Li0.8Mg1) in the frequency range 50 to 1,400 cm−1 also show a series of changes with increasing pressure. The data reported here support the inference of Iezzi et al. (Am Miner 91:479–482, 2006a) regarding a new high-pressure amphibole polymorph.  相似文献   

14.
 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  相似文献   

15.
The synthetic amphibole Na0.95(Li0.95Mg1.05)Mg5Si8O22(OH)2 was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P21 /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm−1, respectively, and two minor bands at 3,667 and 3,687 cm−1. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (A□0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P21 /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ANa0.8B(Na0.8Mg1.2)CMg5Si8O22(OH)2 indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.  相似文献   

16.
We have studied the polarized optical absorption and the EPR spectra of Ni-doped beryls grown by hydrothermal, flux and gas-transport methods, and chrysoberyl grown by the Czochralski and flux methods. In beryls, three groups of bands belonging to three various Ni centres were distinguished by analysis of the absorption band intensities. The first group, bands with maximums at 21740 (E ⊥ c), 17240 (E || c) and 9260 (E ⊥ + || c), 7140 (E || + ⊥ c) cm−1, are due to Ni3+ in octahedral Al3+ site. The second group is bands at 25640 (E ⊥ c), 22220 (E || c) and 13520 (E || + ⊥ c), 13160 (E ⊥+ || c) cm−1 and 8930 (E ⊥ + || c), 7460 (E || c) cm−1, which are caused by Ni2+ in octahedral Al3+ site. Weak wide bands at 17540 (E ⊥ c), 15500 (E || c) cm−1 and 6580 (E || + ⊥ c), 5950 (E || c) cm−1 are related to Ni2+ in tetrahedral Be2+ site. The occurrence of Ni ions in Be2+ site is proved by the EPR spectra of 1VNi+ in γ-irradiated samples. According to the spectra of optical absorption of Ni-doped chrysoberyl, two types of Ni centres have been established: Ni3+ and Ni2+ ions in octahedral Al3+ sites. From the EPR spectra of the X-ray irradiated crystals BeAl2O4: Ni, it follows that 68% of Ni+ ions occupy octahedral Al3+ sites with mirror symmetry and 32% are in Al3+ sites with inversion symmetry. In the approximation of trigonal field with regard to Trees correction, the energy levels of Ni3+ and Ni2+ have been calculated in octahedral and tetrahedral coordination. There is good agreement between the obtained experimental and calculated data. The polarization dependence of the optical absorption bands is well explained in terms of the spin–orbit interaction.  相似文献   

17.
The low-temperature heat capacity (C P) of stishovite (SiO2) synthesized with a multi-anvil device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system (PPMS) and around ambient temperature using a differential scanning calorimeter (DSC). The entropy of stishovite at standard temperature and pressure calculated from DSC-corrected PPMS data is 24.94 J mol−1 K−1, which is considerably smaller (by 2.86 J mol−1 K−1) than that determined from adiabatic calorimetry (Holm et al. in Geochimica et Cosmochimica Acta 31:2289–2307, 1967) and about 4% larger than the recently reported value (Akaogi et al. in Am Mineral 96:1325–1330, 2011). The coesite–stishovite phase transition boundary calculated using the newly determined entropy value of stishovite agrees reasonably well with the previous experimental results by Zhang et al. (Phys Chem Miner 23:1–10, 1996). The calculated phase boundary of kyanite decomposition reaction is most comparable with the experimental study by Irifune et al. (Earth Planet Sci Lett 77:245–256, 1995) at low temperatures around 1,400 K, and the calculated slope in this temperature range is mostly consistent with that determined by in situ X-ray diffraction experiments (Ono et al. in Am Mineral 92:1624–1629, 2007).  相似文献   

18.
Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) 18O/16O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233–262, 1997; Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010), these authors find variations in δ18Ool (~4.6–6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231–241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) speculate that δ18Ool values for La Palma olivine grains measured by LF (Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δ18Ool values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δ18Ool is weakly correlated (R 2 = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514–524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member δ18O values for HIMU-peridotite (δ18O = 5.3 ± 0.3 ‰) and depleted pyroxenite (δ18O = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226–234, 2011), there are significant differences in the predicted δ18O values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565–6589, 2010) proposed a mantle source for La Palma lavas with low-δ18O (<5 ‰), rather than higher-δ18O (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349–363, 2011). Here we question the approach of using weakly correlated variations in δ18Ool and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.  相似文献   

19.
Chalcedony is a spatial arrangement of hydroxylated nanometre-sized α-quartz (SiO2) crystallites that are often found in association with the silica mineral moganite (SiO2). A supplementary Raman band at 501 cm−1 in the chalcedony spectrum, attributed to moganite, has been used for the evaluation of the quartz/moganite ratio in silica rocks. Its frequency lies at 503 cm−1 in sedimentary chalcedony, representing a 2 cm−1 difference with its position in pure moganite. We present a study of the 503 cm−1 band’s behaviour upon heat treatment, showing its gradual disappearance upon heating to temperatures above 300 °C. Infrared spectroscopic measurements of the silanole (SiOH) content in the samples as a function of annealing temperature show a good correlation between the disappearance of the 503 cm−1 Raman band and the decrease of structural hydroxyl. Thermogravimetric analyses reveal a significant weight loss that can be correlated with the decreasing of this Raman band. X-ray powder diffraction data suggest the moganite content in the samples to remain stable. We propose therefore the existence of a hitherto unknown Raman band at 503 cm−1 in chalcedony, assigned to ‘free’ Si–O vibrations of non-bridging Si–OH that oscillate with a higher natural frequency than bridging Si–O–Si (at 464 cm−1). A similar phenomenon was recently observed in the infrared spectra of chalcedony. The position of this Si–OH-related band is nearly the same as the Raman moganite band and the two bands may interfere. The actually observed Raman band in silica rocks might therefore be a convolution of a silanole and a moganite vibration. These findings have broad implications for future Raman spectroscopic studies of moganite, for the assessment of the quartz/moganite ratio, using this band, must take into account the contribution from silanole that are present in chalcedony and moganite.  相似文献   

20.
A series of synthetic Ca-Tschermak–diopside (CaAlAlSiO6–CaMgSi2O6) clinopyroxenes were investigated by powder infrared spectroscopy at room temperature in the wavenumber range 80–2,000 cm−1. Measurable local structural heterogeneities in the crystals are suggested by the line broadening parameter, Δcorr that are observed for intermediate solid-solution compositions. The broadening is most pronounced in the high wavenumber region of the IR spectra that contains stretching modes involving the TO4 polyhedra. The effective line widths for three selected wavenumber regions deviate positively from linear behavior. This is also observed for the enthalpy of mixing of this solid solution. The relationship between “excess Δcorr”, δΔcorr, and heat of mixing, ΔH mix, behavior was investigated for this clinopyroxene series and for several other binary silicate solid solutions. The ΔH mix versus δΔcorr slope values show a linear relationship with respect to the integrated excess volume of the various solid solutions.  相似文献   

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