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.     

Crystal structure, Raman and FTIR spectroscopy, and equations of state of OH-bearing MgSiO3 akimotoite

MgSiO₃ akimotoite is stable relative to majorite-garnet under low-temperature geotherms within steeply or rapidly subducting slabs. Two compositions of Mg–akimotoite were synthesized under similar conditions: Z674 (containing about 550 ppm wt H₂O) was synthesized at 22 GPa and 1,500 °C and SH1101 (nominally anhydrous) was synthesized at 22 GPa and 1,250 °C. Crystal structures of both samples differ significantly from previous studies to give slightly smaller Si sites and larger Mg sites. The bulk thermal expansion coefficients of Z674 are (153–839 K) of a ₁ = 20(3) × 10^?9 K^?2 and a ₀ = 17(2) × 10^?6 K^?1, with an average of α ₀ = 27.1(6) × 10^?6 K^?1. Compressibility at ambient temperature of Z674 was measured up to 34.6 GPa at Sector 13 (GSECARS) at Advanced Photon Source Argonne National Laboratory. The second-order Birch–Murnaghan equation of state (BM2 EoS) fitting yields: V ₀ = 263.7(2) Å³, K _T0 = 217(3) GPa (K′ fixed at 4). The anisotropies of axial thermal expansivities and compressibilities are similar: α _a  = 8.2(3) and α _c  = 10.68(9) (10^?6 K^?1); β _a  = 11.4(3) and β _c  = 15.9(3) (10^?4 GPa). Hydration increases both the bulk thermal expansivity and compressibility, but decreases the anisotropy of structural expansion and compression. Complementary Raman and Fourier transform infrared (FTIR) spectroscopy shows multiple structural hydration sites. Low-temperature and high-pressure FTIR spectroscopy (15–300 K and 0–28 GPa) confirms that the multiple sites are structurally unique, with zero-pressure intrinsic anharmonic mode parameters between ?1.02 × 10^?5 and +1.7 × 10^?5 K^?1, indicating both weak hydrogen bonds (O–H···O) and strong OH bonding due to long O···O distances.     

Raman microprobe (RMP) determinations of natural and synthetic coesite

Raman microprobe (RMP) spectra of synthetic coesiste and three natural coesites from eclogite — facies rocks are provided and evaluated for characterisation purposes. The main coesite line lies at 521 cm^?1 and the other characteristic lines attributed to coesite occur at 117, 177 and 271 cm^?1. Two petrologically useful applications were (a) the confirmation of the coesite structure in very small natural crystals deduced to be coesite from petrographic observations only, and (b) the recognition of sub-microscopic crystallites of quartz in incipiently — transformed coesite in all the natural samples.     

Raman spectroscopy, vibrational analysis, and heating of buergerite tourmaline

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

High-pressure polymorphism and structural transitions of norsethite,BaMg(CO3)2

In situ high-pressure investigations on norsethite, BaMg(CO₃)₂, have been performed in sequence of diamond-anvil cell experiments by means of single-crystal X-ray and synchrotron diffraction and Raman spectroscopy. Isothermal hydrostatic compression at room temperature yields a high-pressure phase transition at P _c ≈ 2.32 ± 0.04 GPa, which is weakly first order in character and reveals significant elastic softening of the high-pressure form of norsethite. X-ray structure determination reveals C2/c symmetry (Z = 4; a = 8.6522(14) Å, b = 4.9774(13) Å, c = 11.1542(9) Å, β = 104.928(8)°, V = 464.20(12) Å³ at 3.00 GPa), and the structure refinement (R ₁ = 0.0763) confirms a distorted, but topologically similar crystal structure of the so-called γ-norsethite, with Ba in 12-fold and Mg in octahedral coordination. The CO₃ groups were found to get tilted off the ab-plane direction by ~16.5°. Positional shifts, in particular of the Ba atoms and the three crystallographically independent oxygen sites, give a higher flexibility for atomic displacements, from which both the relatively higher compressibility and the remarkable softening originate. The corresponding bulk moduli are K ₀ = 66.2 ± 2.3 GPa and dK/dP = 2.0 ± 1.8 for α-norsethite and K ₀ = 41.9 ± 0.4 GPa and dK/dP = 6.1 ± 0.3 for γ-norsethite, displaying a pronounced directional anisotropy (α: β _a ^?1  = 444(53) GPa, β _c ^?1  = 76(2) GPa; γ: β _a ^?1  = 5.1(1.3) × 10³ GPa, β _b ^?1  = 193(6) GPa β _c ^?1  = 53.4(0.4) GPa). High-pressure Raman spectra show a significant splitting of several modes, which were used to identify the transformation in high-pressure high-temperature experiments in the range up to 4 GPa and 542 K. Based on the experimental series of data points determined by XRD and Raman measurements, the phase boundary of the α-to-γ-transition was determined with a Clausius–Clapeyron slope of 9.8(7) × 10^?3 GPa K^?1. An in situ measurement of the X-ray intensities was taken at 1.5 GPa and 411 K in order to identify the nature of the structural variation on increased temperatures corresponding to the previously reported transformation from α- to β-norsethite at 343 K and 1 bar. The investigations revealed, in contrast to all X-ray diffraction data recorded at 298 K, the disappearance of the superstructure reflections and the observed reflection conditions confirm the anticipated \(R\bar{3}m\) space-group symmetry. The same superstructure reflections, which disappear as temperature increases, were found to gain in intensity due to the positional shift of the Ba atoms in the γ-phase.     

Structural investigations of (Ca,Sr)ZrO<Subscript>3</Subscript> and Ca(Sn,Zr)O<Subscript>3</Subscript> perovskite compounds

(Ca _x ,Sr_1?x )ZrO₃ and Ca(Sn _y ,Zr_1-y )O₃ solid solutions were synthesized by solid-state reaction at high temperature before to be studied by powder X-ray diffraction and Raman Spectroscopy. Diffraction data allow the distortion of the ABO₃ perovskite structure to be investigated according to cations substitution on A and B-sites. It is shown that distortion, characterized by Φ, the tilt angle of BO₆ octahedra, slightly increases with decreasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds and strongly decreases with decreasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds. Such results are discussed in view of the relative A and B cation sizes. Raman data show that vibrational spectra are strongly affected by the cation substitution on A-site; the frequencies of most vibrational modes increase with increasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds, i.e. with the decreasing mean size of the A-cation; the upper shift is observed for the 358 cm^?1 mode (?ν/?r = ?60.1 cm^?1/Å). On the other hand, the cation substitution on B-sites, slightly affect the spectra; it is shown that in most cases, the frequency of vibrational modes increases with increasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds, i.e. with the decreasing mean size of the B-cation, but that two modes (287 and 358 cm^?1) behave differently: their frequencies decrease with the decreasing mean size of the B-cation, with a shift respectively equal to +314 and +162 cm^?1/Å. Such results could be used to predict the location of different elements such as trivalent cations or radwaste elements on A- or B-site, in the perovskite structure.     

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

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

High-pressure behavior of natural single-crystal epidote and clinozoisite up to 40 GPa

The comparative compressibility and high-pressure stability of a natural epidote (0.79 Fe-total per formula unit, Fe_tot pfu) and clinozoisite (0.40 Fe_tot pfu) were investigated by single-crystal X-ray diffraction and Raman spectroscopy. The lattice parameters of both phases exhibit continuous compression behavior up to 30 GPa without evidence of phase transformation. Pressure–volume data for both phases were fitted to a third-order Birch–Murnaghan equation of state with V ₀ = 461.1(1) ų, K ₀ = 115(2) GPa, and \(K_{0}^{'}\) = 3.7(2) for epidote and V ₀ = 457.8(1) ų, K ₀ = 142(3) GPa, and \(K_{0}^{'}\) = 5.2(4) for clinozoisite. In both epidote and clinozoisite, the b-axis is the stiffest direction, and the ratios of axial compressibility are 1.19:1.00:1.15 for epidote and 1.82:1.00:1.19 for clinozoisite. Whereas the compressibility of the a-axis is nearly the same for both phases, the b- and c-axes of the epidote are about 1.5 times more compressible than in clinozoisite, consistent with epidote having a lower bulk modulus. Raman spectra collected up to 40.4 GPa also show no indication of phase transformation and were used to obtain mode Grüneisen parameters (γ _i) for Si–O vibrations, which were found to be 0.5–0.8, typical for hydrous silicate minerals. The average pressure coefficient of Raman frequency shifts for M–O modes in epidote, 2.61(6) cm^?1/GPa, is larger than found for clinozoisite, 2.40(6) cm^?1/GPa, mainly due to the different compressibility of FeO₆ and AlO₆ octahedra in M3 sites. Epidote and clinozoisite contain about 2 wt% H₂O are thus potentially important carriers of water in subducted slabs.     

Raman spectrum of natural and synthetic stishovite

Raman spectra of natural and synthetic samples of stishovite have been measured with a micro-optical spectrometer system. These spectra have a pattern that is characteristic of rutile-structured oxides. The spectrum of synthetic stishovite is characterized by well-resolved bands at 231, 589, 753, and 967 cm^?1, which are assigned as theB _1g,E _g,A _1g, andB _2g fundamentals, respectively, of the first-order Raman spectrum of the ideal, ordered structure. Natural stishovite obtained from Meteor Crater, Arizona has a first-order Raman spectrum that is fully consistent with that of the synthetic material. The observed spectrum of the natural sample, however, is weaker and has bands in addition to those identified as fundamentals in the spectrum of the synthetic material. A broad band at ～475 cm^?1 may be indicative of glass or contaminants derived from the extraction procedure. Alternatively, this band may arise from multiphonon scattering that is enhanced by poor crystallinity or structural disorder in the natural shocked sample.     

Beryl-II,a high-pressure phase of beryl: Raman and luminescence spectroscopy to 16.4 GPa

The Raman and Cr³⁺ and V²⁺ luminescence spectra of beryl and emerald have been characterized up to 15.0 and 16.4 GPa, respectively. The Raman spectra show that an E _1g symmetry mode at 138 cm^?1 shifts negatively by ?4.57 (±0.55) cm^?1/GPa, and an extrapolation of the pressure dependence of this mode indicates that a soft-mode transition should occur near 12 GPa. Such a transition is in accord with prior theoretical results. Dramatic changes in Raman mode intensities and positions occur between 11.2 and 15.0 GPa. These changes are indicative of a phase transition that primarily involves tilting and mild distortion of the Si₆O₁₈ rings. New Raman modes are not observed in the high-pressure phase, which indicates that the local bonding environment is not altered dramatically across the transition (e.g., changes in coordination do not occur). Both sharp line and broadband luminescence are observed for both Cr³⁺ and V²⁺ in emerald under compression to 16.4 GPa. The R-lines of both Cr³⁺ and V²⁺ shift to lower energy (longer wavelength) under compression. Both R-lines of Cr³⁺ split at ~13.7 GPa, and the V²⁺ R₁ slope changes at this pressure and shifts more rapidly up to ~16.4 GPa. The Cr³⁺ R-line splitting and FWHM show more complex behavior, but also shift in behavior at ~13.7 GPa. These changes in the pressure dependency of the Cr³⁺ and V²⁺ R-lines and the changes in R-line splitting and FWHM at ~13.7 GPa further demonstrate that a phase transition occurs at this pressure, in good agreement with our Raman results. The high-pressure phase of beryl appears to have two Al sites that become more regular under compression. Hysteresis is not observed in our Raman or luminescence spectra on decompression, suggesting that this transition is second order in nature: The occurrence of a second-order transition near this pressure is also in accord with prior theoretical results. We speculate that the high-pressure phase (beryl-II) might be a mildly modulated structure, and/or that extensive twinning occurs across this transition.     

Pressure-induced incipient amorphization of α-quartz and transition to coesite in an eclogite from Antarctica: a first record and some consequences

Monocrystalline quartz inclusions in garnet and omphacite from various eclogite samples from the Lanterman Range (Northern Victoria Land, Antarctica) have been investigated by cathodoluminescence (CL), Raman spectroscopy and imaging, and in situ X‐ray (XR) microdiffraction using the synchrotron. A few inclusions, with a clear‐to‐opalescent lustre, show ‘anomalous’ Raman spectra characterized by weak α‐quartz modes, the broadening of the main α‐quartz peak at 465 cm^?1, and additional vibrations at 480–485, 520–523 and 608 cm^?1. CL and Raman imaging indicate that this ‘anomalous’α‐quartz occurs as relicts within ordinary α‐quartz, and that it was preserved in the internal parts of small quartz inclusions. XR diffraction circular patterns display irregular and broad α‐quartz spots, some of which show an anomalous d‐spacing tightening of ～2%. They also show some very weak, hazy clouds that have d‐spacing compatible with coesite but not with α‐quartz. Raman spectrometry and XR microdiffraction characterize the anomalies with respect to α‐quartz as (i) a pressure‐induced disordering and incipient amorphization, mainly revealed by the 480–485 and 608‐cm^?1 Raman bands, together with (ii) a lattice densification, evidenced by d‐spacing tightening; (iii) the cryptic development of coesite, 520–523 cm^?1 being the main Raman peak of coesite and (iv) Brazil micro‐twinning. This ‘anomalous’α‐quartz represents the first example of pressure‐induced incipient amorphization of a metastable phase in a crustal rock. This issue is really surprising because pressure‐induced amorphization of metastable α‐quartz, observed in impactites and known to occur between 15 and 32 GPa during ultrahigh‐pressure (UHP) experiments at room temperature, is in principle irrelevant under normal geological P–T conditions. A shock (due to a seism?) or a local overpressure at the inclusion scale (due to expansion mismatch between quartz and its host mineral) seem the only geological mechanisms that can produce such incipient amorphization in crustal rocks. This discovery throws new light on the modality of the quartz‐coesite transition and on the pressure regimes (non‐lithostatic v. lithostatic) during high‐pressure/UHP metamorphism. In particular, incipient amorphization of quartz could favour the quartz‐coesite transition, or allow the growth of metastable coesite, as already experimentally observed.     

On the crystal chemistry and elastic behavior of a phlogopite 3<Emphasis Type="Italic">T</Emphasis>

The crystal chemistry and the elastic behavior under isothermal conditions up to 9 GPa of a natural, and extremely rare, 3T-phlogopite from Traversella (Valchiusella, Turin, Western Alps) [(K_0.99Na_0.05Ba_0.01)(Mg_2.60Al_0.20Fe _0.21 ²⁺ )[Si_2.71Al_1.29O₁₀](OH)₂, space group P3₁12, with a = 5.3167(4), c = 30.440(2) Å, and V = 745.16(9) ų] have been investigated by electron microprobe analysis in wavelength dispersion mode, single-crystal X-ray diffraction at 100 K, and in situ high-pressure synchrotron radiation powder diffraction (at room temperature) with a diamond anvil cell. The single-crystal refinement confirms the general structure features expected for trioctahedral micas, with the inter-layer site partially occupied by potassium and sodium, iron almost homogeneously distributed over the three independent octahedral sites, and the average bond distances of the two unique tetrahedra suggesting a disordered Si/Al-distribution (i.e., 〈T1-O〉 ~ 1.658 and 〈T2-O〉 ~ 1.656 Å). The location of the H-site confirms the orientation of the O–H vector nearly perpendicular to (0001). The refinement converged with R ₁(F) = 0.0382, 846 unique reflections with F _O > 4σ(F _O) and 61 refined parameters, and not significant residuals in the final difference-Fourier map of the electron density (+0.77/?0.37 e ^?/ų). The high-pressure experiments showed no phase transition within the pressure range investigated. The P–V data were fitted with a Murnaghan (M-EoS) and a third-order Birch-Murnaghan equation of state (BM-EoS), yielding: (1) M-EoS, V ₀ = 747.0(3) ų, K _T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V ₀ = 747.0(3) ų, K _T0 = 42.8(29) GPa, and K′ = 9.9(17). A comparison between the elastic behavior in response to pressure observed in 1M- and 3T-phlogopite is made.     

Static elasticity of cordierite I: Effect of heavy ion irradiation on the compressibility of hydrous cordierite

The effect of ion beam irradiations on the elastic properties of hydrous cordierite was investigated by means of Raman and X-ray diffraction experiments. Oriented single crystals were exposed to swift heavy ions (Au, Bi) of various specific energies (10.0–11.1 MeV/u and 80 MeV/u), applying fluences up to 5 × 10¹³ ions/cm². The determination of unit-cell constants yields a volume strain of 3.4 × 10^?3 up to the maximum fluence, which corresponds to a compression of non-irradiated cordierite at ~480 ± 10 MPa. The unit-cell contraction is anisotropic (e ₁ = 1.4 ± 0.1 × 10^?3, e ₂ = 1.5 ± 0.1 × 10^?3, and e ₃ = 7 ± 1 × 10^?4) with the c-axis to shrink only half as much as the axes within the ab-plane. The lattice elasticity for irradiated cordierite (? = 1 × 10¹² ions/cm²) was determined from single-crystal XRD measurements in the diamond anvil cell. The fitted third-order Birch–Murnaghan equation-of-state parameters of irradiated cordierite (V ₀ = 1548.41 ± 0.16 Å³, K ₀ = 117.1 ± 1.1 GPa, ?K/?P = ?0.6 ± 0.3) reveal a 10–11 % higher compressibility compared to non-irradiated cordierite. While the higher compressibility is attributed to the previously reported irradiation-induced loss of extra-framework H₂O, the anomalous elasticity as expressed by elastic softening (β _a ^?1 , β _b ^?1 , β _c ^?1  = 397 ± 9, 395 ± 28, 308 ± 11 GPa, ?(β ^?1)/?P = ?4.5 ± 2.7, ?6.6 ± 8.4, ?5.4 ± 3.0) appears to be related to the framework stability and to be independent of the water content in the channels and thus of the ion beam exposure.     

Oxydation expérimentale de Fe-tourmalines et corrélation avec une déprotonation des groupes hydroxyleAnnealing in oxidising conditions of Fe-tourmalines and correlated deprotonation of OH groups

Annealing at 400?T?600 °C (40?P?60 MPa and HM buffer-controlled f(O₂)) of tourmalines synthesised at the same T and P with NNO buffer induces an oxidation of Fe²⁺ into Fe³⁺ in some Y sites only (Mössbauer Spectroscopy data). Annealing in the same conditions of natural tourmalines is consistent with these results. FTIR spectroscopy shows that oxidation of Fe²⁺ into Fe³⁺ is charge-balanced by deprotonation of the external OH₍₃₎ groups. To cite this article: Y. Fuchs et al., C. R. Geoscience 334 (2002) 245–249.     

Stability and P–V–T equation of state of KAlSi3O8-hollandite determined by in situ X-ray observations and implications for dynamics of subducted continental crust material

In situ X-ray diffraction measurements of KAlSi₃O₈-hollandite (K-hollandite) were performed at pressures of 15–27 GPa and temperatures of 300–1,800 K using a Kawai-type apparatus. Unit-cell volumes obtained at various pressure and temperature conditions in a series of measurements were fitted to the high-temperature Birch-Murnaghan equation of state and a complete set of thermoelastic parameters was obtained with an assumed K′_300,0=4. The determined parameters are V _300,0=237.6(2) Å³, K _300,0=183(3) GPa, (?K _T,0/?T) _P =?0.033(2) GPa K^?1, a ₀=3.32(5)×10^?5 K^?1, and b ₀=1.09(1)×10^?8 K^?2, where a ₀ and b ₀ are coefficients describing the zero-pressure thermal expansion: α _T,0 = a ₀ + b ₀ T. We observed broadening and splitting of diffraction peaks of K-hollandite at pressures of 20–23 GPa and temperatures of 300–1,000 K. We attribute this to the phase transitions from hollandite to hollandite II that is an unquenchable high-pressure phase recently found. We determined the phase boundary to be P (GPa)=16.6 + 0.007 T (K). Using the equation of state parameters of K-hollandite determined in the present study, we calculated a density profile of a hypothetical continental crust (HCC), which consists only of K-hollandite, majorite garnet, and stishovite with 1:1:1 ratio in volume. Density of HCC is higher than the surrounding mantle by about 0.2 g cm^?3 in the mantle transition zone while this relation is reversed below 660-km depth and HCC becomes less dense than the surrounding mantle by about 0.15 g cm^?3 in the uppermost lower mantle. Thus the 660-km seismic discontinuity can be a barrier to prevent the transportation of subducted continental crust materials to the lower mantle and the subducted continental crust may reside at the bottom of the mantle transition zone.     

Structure and cation disorder of hydrous ringwoodite, γ-Mg1.89Si0.98H0.30O4

The structure of a single crystal hydrous ringwoodite, Mg_1.89Si_0.98H_0.30O₄ synthesized at conditions of 1300?°C and 20?GPa has been analyzed. Crystallographic data for hydrous ringwoodite obtained are; Cubic with Space group: Fd3m (no. 227). a= 8.0693(5)?Å, V=526.41(9)?ų, Z=8, D_calc= 3.48?g?cm^?3. The results of site occupancy refinement using higher angle reflections showed the existence of a small degree of Mg²⁺-Si⁴⁺ disorder in the structure such as (Mg_1.84Si_0.05□_0.11)(Si_0.93Mg_0.05□_0.02)H_0.30O₄. The IR and Raman spectra were measured and OH vibration spectra were observed. A broad absorption band was observed in the IR spectrum and the maxima were observed at 3160?cm^?1 in the IR and at 3165?cm^?1 and 3685?cm^?1 in relatively sharp Raman spectra, which suggest that locations between O-O pairs around the octahedral 16c and 16d sites are possible sites for hydrogen.     

Polarized electronic absorption spectra of colourless chalcocyanite,CuSO4, with a survey on crystal fields in Cu2+ minerals

Polarized electronic absorption spectra of colourless chalcocyanite, CuSO₄, have been measured using microscope-spectrometric techniques. The spectra are characterized by a structured and clearly polarized band system in the near-infrared spectral range with components centred at 11,720, 10,545, 9,100, and 7,320 cm^?1, which have been assigned to crystal field d–d transitions of Cu²⁺ cations in pseudo-tetragonally elongated CuO₆ polyhedra with point symmetry C _i ( \(\bar{1}\) ). The polarization behaviour is interpreted based on a D ₂(C ₂″) pseudo-symmetry. Crystal field calculations were performed for the actual triclinic point symmetry by applying the Superposition Model of crystal fields, as well as in terms of a ‘classic’ pseudo-tetragonal crystal field approach yielding the parameters Dq _(eq) = 910, Dt = 395, and Ds = 1,336 cm^?1, corresponding to a cubically averaged Dq _cub = 679 cm^?1. A comparative survey on crystal fields in Cu²⁺ minerals shows that the low overall crystal field strength in chalcocyanite, combined with a comparatively weak pseudo-tetragonal splitting of energy levels, is responsible for its unique colourless appearance among oxygen-based Cu²⁺ minerals. The weak crystal field in CuSO₄ can be related to the lower position of the SO₄ ^2? anion compared to, e.g. the H₂O molecule in the spectrochemical series of ligands.     

High-pressure Raman spectroscopic study of Fo90 hydrous wadsleyite

Raman spectra of monoclinic Fo₉₀ hydrous wadsleyite with 2.4 wt% H₂O have been measured in a diamond-anvil cell with helium as a pressure-transmitting medium to 58.4 GPa at room temperature. The most intense, characteristic wadsleyite modes, the Si–O–Si symmetric stretch at 721 cm⁻¹ and the symmetric stretch of the SiO₃ unit at 918 cm⁻¹, shift continuously to 58.4 GPa showing no evidence of a first order change in the crystal structure despite compression well beyond the stability field of wadsleyite in terms of pressure. The pressure dependence of these two modes is nearly identical for Fo₉₀ hydrous and Fo₁₀₀ anhydrous wadsleyite. A striking feature in the high-pressure Raman spectra of Fo₉₀ hydrous wadsleyite is the appearance of new Raman modes above 9 GPa in the mid-frequency range (300–650 cm⁻¹ at 1-bar and shifted to 500–850 cm⁻¹ at 58.4 GPa) accompanied by a significant growth in their intensities under further compression. In the OH stretching frequency range Fo₉₀ hydrous wadsleyite exhibits a larger number of modes than the Mg end-member phase. The higher number of modes may be due to either additional protonation sites or simply that we observe a different subset of all possible OH modes for each sample. The high-pressure behaviour of the OH stretching modes of Fo₉₀ and Fo₁₀₀ hydrous wadsleyite is consistent: OH stretching modes with frequencies <3,530 cm⁻¹ decrease with increasing pressure whereas the higher-frequency OH modes show a close to constant pressure dependence to at least 13.2 GPa. The approximately constant pressure dependence of the OH modes above 3,530 cm⁻¹ is consistent with protons being located at the O1···O edges around M3.     

Thermo-elastic behaviour of Be2BO3OH (hambergite) up to 7 GPa and 1,100 K

The thermo-elastic behaviour of Be₂BO₃(OH)_0.96F_0.04 (i.e. natural hambergite, Z = 8, a = 9.7564(1), b = 12.1980(2), c = 4.4300(1) Å, V = 527.21(1) ų, space group Pbca) has been investigated up to 7 GPa (at 298 K) and up to 1,100 K (at 0.0001 GPa) by means of in situ single-crystal X-ray diffraction and synchrotron powder diffraction, respectively. No phase transition or anomalous elastic behaviour has been observed within the pressure range investigated. P?V data fitted to a third-order Birch–Murnaghan equation of state give: V ₀ = 528.89(4) ų, K _T0 = 67.0(4) GPa and K′ = 5.4(1). The evolution of the lattice parameters with pressure is significantly anisotropic, being: K _T0(a):K _T0(b):K _T0(c) = 1:1.13:3.67. The high-temperature experiment shows evidence of structure breakdown at T > 973 K, with a significant increase in the full-width-at-half-maximum of all the Bragg peaks and an anomalous increase in the background of the diffraction pattern. The diffraction pattern was indexable up to 1,098 K. No new crystalline phase was observed up to 1,270 K. The diffraction data collected at room-T after the high-temperature experiment showed that the crystallinity was irreversibly compromised. The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α ₀ + α ₁ T ^?1/2. The refined parameters for Be₂BO₃(OH)_0.96F_0.04 are: α ₀ = 7.1(1) × 10^?5 K^?1 and α ₁ = ?8.9(2) × 10^?4 K ^?1/2 for the unit-cell volume, α ₀(a) = 1.52(9) × 10^?5 K^?1 and α ₁(a) = ?1.4(2) × 10^?4 K ^?1/2 for the a-axis, α ₀(b) = 4.4(1) × 10^?5 K^?1 and α ₁(b) = ?5.9(3) × 10^?4 K ^?1/2 for the b-axis, α ₀(c) = 1.07(8) × 10^?5 K^?1 and α ₁(c) = ?1.5(2) × 10^?4 K ^?1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α ₀(a):α ₀(b):α ₀(c) = 1.42:4.11:1. The main deformation mechanisms in response to the applied temperature, based on Rietveld structure refinement, are discussed.