High temperature structural and thermoelastic behaviour of mantle orthopyroxene: an in situ neutron powder diffraction study

The temperature induced structural evolution and thermoelastic behaviour of a natural (Pbca) orthopyroxene (Opx), with chemical formula ^M2(Mg_0.856Ca_0.025Fe²⁺ _0.119) ^M1(Mg_0.957Fe²⁺ _0.011Fe³⁺ _0.016Cr_0.011Al_0.005)Al_0.032Si_1.968O₆, from a suite of high pressure ultramafic nodules of mantle origin, have been investigated by in-situ neutron powder diffraction at several temperatures starting from 1,200°C down to 150°C. Unit-cell parameter variations as a function of T show no phase transition within this temperature range. The volume thermal expansion coefficient, α = V ⁻¹(∂V/∂T) _P0, varies linearly with T. The axial thermal expansion coefficients, α_j = l _j⁻¹(∂l _j/∂T)_P0, increase non-linearly with T. The principal Lagrangian unit-strain coefficients (ɛ//a, ɛ//b, ɛ//c), increase continuously with T. However, the orientation of the unit-strain ellipsoid appears to change with T. With decreasing T, the values of the unit-strain coefficients along the b and c axes tend to converge. The orientation at ΔT = 1,080°C is maintained down to the lowest temperature (150°C). The two non-equivalent tetrahedral chains, TA _n OA_3n and TB _n OB_3n , are kinked differently. At room-T, the TB _n OB_3n chain is more strongly kinked by about 23° than the TA _n OA_3n chain. With increasing T, the difference decreases by 3° for the TB _n OB_3n chain. The intersite cation exchange reaction between M1 and M2 (Mg²⁺ and Fe²⁺) shows a slight residual order at 1,200°C followed by reordering with decreasing temperature although seemingly not with a definite progressive trend. At the lowest temperature reached (150°C), reordering has occurred with the same value of partitioning coefficient K _D as that before heating. The absence of the expected phase transition is most likely due to the presence of minor amounts of Fe³⁺, Al, Ca and Cr which must play a crucial role on the thermoelastic behaviour and phase stability fields in natural Opx, with consequent important petrologic and geological implications.     

Cation partitioning versus temperature in (Mg0.70Fe0.23)Al1.97O4 synthetic spinel by in situ neutron powder diffraction

Neutron powder diffraction experiments in the temperature range 300–1770 K were performed at BENSC, Berlin, Germany, on synthetic (Mg_0.70Fe_0.23) Al_1.97O₄. The cation partitioning over the crystallographic tetrahedral and octahedral sites was determined as a function of temperature through joint Rietveld refinements and advanced minimization techniques. The thermal expansion coefficients of the lattice parameter and inter-atomic bond lengths were also obtained from the full-profile structure refinements. The behaviour of the polyhedral bond-lengths, especially the T−O distances, and of the cell constant upon heating, clearly indicate that the interdiffusion of tetrahedral and octahedral Mg/Al cations starts at about 950 K. This result is straightforwardly supported by the direct analysis of the neutron site scattering factors: Fe always retains tetrahedral coordination at all temperatures, and the cation rearrangement is entirely due to Mg and Al diffusion. Received: 18 November 1997 / Revised, accepted: 23 August 1998     

Crystal chemistry, cation ordering and thermoelastic behaviour of CoMgSiO4 olivine at high temperature as studied by in situ neutron powder diffraction

The thermal expansion, structural changes and the site partitioning of Co and Mg in synthetic CoMgSiO₄ olivine have been studied by in situ time-of-flight neutron powder diffraction as a function of temperature, between 25 and 1,000°C. Thermal expansion of the unit cell dimensions and volume are linear within this temperature range and give no indications of a phase transition, although the thermoelastic behaviour indicates a slight strain minimum around 700°C. Co²⁺ shows a strong preference for the M1 site throughout this temperature range with an oscillatory behaviour; it decreases slightly at about 300°C, climbing up to nearly its original value at around 800°C and then decreasing by about 30% at 1,000°C. This behaviour is in contrast with that of (Fe, Mg)₂SiO₄ olivine, in which the initial Fe²⁺ site preference for the M1 site switches to the M2 site beyond a cross-over temperature. The oscillatory site preference in (CoMg)-olivine as a function of temperature is reflected in the M–O polyhedral volume changes and M–O bond lengths, as well as, thermoelastic strain and atomic thermal displacement parameters. The imbalance between the increasing vibrational and decreasing configurational entropy contributions, together with covalent bonding effects rather than crystal field contributions, seem to drive the cation partitioning in (CoMg)-olivine.     

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.     

Structural changes in sodium tetrasilicate glass around the liquid-glass transition: a neutron diffraction study

The structure of sodium tetrasilicate (Na₂Si₄O₉) glass and melt was studied in the range from 300 to 950?K by neutron diffraction. Increasing temperature leads to gradual decrease of the peak intensities in the static structure factors possibly with a change in the slope at the glass transition temperature (T _g?773?K), but no shift and broadening of the peaks is observed. Especially, the position of the first sharp diffraction peak (FSDP) at 1.6?Å^–1 remains constant in the whole temperature range studied. The corresponding pair correlation functions g(r) are very similar at all temperatures. Only a slight broadening of the Si-O and O-O first nearest-neighbour peaks with temperature is observed, which can be attributed to temperature enhanced dynamic distortions of the SiO₄ tetrahedra. All these results suggest that there is little change not only in the short- but also in the medium-range order of the sodium tetrasilicate glass and melt around the glass-liquid transition.     

In situ neutron diffraction study of deuterated portlandite Ca(OD)2 at high pressure and temperature

The structure of deuterated portlandite, Ca(OD)₂, has been investigated using time-of-flight neutron diffraction at pressures up to ∼4.5 GPa and temperatures up to ∼823 K. Rietveld analysis of the data reveals that with increasing pressure, unit-cell parameter c decreases at a rate about 4.5 times larger than that for a, which is largely due to rapid contraction of the interlayer spacing in this pressure range. Fitting of the determined cell volumes to the third-order Birch–Murnaghan equation of state yields a bulk modulus (K ₀) of 32.2 ± 1.0 GPa and its first derivative (K ₀′) of 4.4 ± 0.6. Moreover, on compression, hydrogen-mediated interatomic interactions within the interlayer become strengthened, as reflected by decreases in interlayer D···O and D···D distances with increasing pressure. Correspondingly, D–D, the distance between the three equivalent sites over which D is disordered, increases, suggesting a pressure-induced hydrogen disorder. This behavior is similar to that reported in brucite at elevated pressure. On heating at ∼2.1 GPa, cell parameter c increases more rapidly than a, as expected. However, because of the pressure effect, the thermal expansion coefficients, particularly along c, are much smaller than those at ambient pressure. With increasing temperature, the three partially occupied D sites become further apart, and the D-mediated interactions, mainly the interlayer D···D repulsion, become weakened.     

The role of iron in tetrahedrite and tennantite determined by Rietveld refinement of neutron powder diffraction data

Rietveld refinement of neutron powder diffraction data on four samples of synthetic, iron-bearing tetrahedrite (Cu_12?xFe_xSb₄S₁₃) with x = 0.28, 0.69, 0.91, 2.19 and four samples of synthetic tennantite (Cu_12?xFe_xAs₄S₁₃) with x = 0.33, 0.38, 0.86, 1.5 indicate unambiguously that iron is incorporated into tetrahedral M1 (12d) sites and not into triangular M2 (12e) sites in the cubic crystal structure (space group I $ \ifmmode\expandafter\bar\else\expandafter\=\fi{4} Rietveld refinement of neutron powder diffraction data on four samples of synthetic, iron-bearing tetrahedrite (Cu_12−xFe_xSb₄S₁₃) with x = 0.28, 0.69, 0.91, 2.19 and four samples of synthetic tennantite (Cu_12−xFe_xAs₄S₁₃) with x = 0.33, 0.38, 0.86, 1.5 indicate unambiguously that iron is incorporated into tetrahedral M1 (12d) sites and not into triangular M2 (12e) sites in the cubic crystal structure (space group I 3 m). The refinement results also confirm that M2 is a split (24g), flat-pyramidal site situated statistically on both sides of the S1−S1–S2 triangle. In tetrahedrite, this split is about 0.6 ?, in tennantite about 0.7 ?. Trends in bond lengths and magnitude of the M2 split were evaluated by means of linear regression with Fe concentration as the independent variable.     

Thermal expansion and crystal structure of FeSi between 4 and 1173 K determined by time-of-flight neutron powder diffraction

The thermal expansion and crystal structure of FeSi has been determined by neutron powder diffraction between 4 and 1173?K. No evidence was seen of any structural or magnetic transitions at low temperatures. The average volumetric thermal expansion coefficient above room temperature was found to be 4.85(5)?×?10^?5?K^?1. The cell volume was fitted over the complete temperature range using Grüneisen approximations to the zero pressure equation of state, with the internal energy calculated via a Debye model; a Grüneisen second-order approximation gave the following parameters: θ_D=445(11)?K, V ₀=89.596(8)?ų, K ₀′=4.4(4) and γ′=2.33(3), where θ_D is the Debye temperature, V ₀ is V at T=0?K, K ₀′ is the first derivative with respect to pressure of the incompressibility and γ′ is a Grüneisen parameter. The thermodynamic Grüneisen parameter, γ_th, has been calculated from experimental data in the range 4–400?K. The crystal structure was found to be almost invariant with temperature. The thermal vibrations of the Fe atoms are almost isotropic at all temperatures; those of the Si atoms become more anisotropic as the temperature increases.     

High temperature dehydroxylation of muscovite-2M1: a kinetic study by in situ XRPD

Muscovite-2M₁ shows a major phase transition at about 800°C, which is generally attributed in the literature to the structural dehydroxylation process, although a number of structural models have been proposed for the dehydroxylated phase, and different transformation mechanisms have also been put forward. The observed first order transformation involves an increase in the cell volume, and it is not clear to date how the cell expansion is related to the loss of hydroxyl groups. The phase change has been re-investigated here by in situ high temperature powder diffraction, both in non-isothermal and isothermal modes, to combine for the first time the structural and the kinetic interpretation of the transformation. The results unequivocally confirm that the reaction taking place in the temperature range 700–1000°C is truly a dehydroxylation process, involving the nucleation and growth of the high temperature dehydroxylated phase, having Al in 5-fold coordination. Structural simulations of the basal peaks of the powder diffraction patterns indicate that the model originally proposed by Udagawa et al. (1974) for the dehydroxylated phase correctly describes the high temperature phase. The kinetic analysis of the isothermal data using an Avrami-type model yields values for the reaction order compatible with a reaction mechanism limited by a monodimensional diffusion step. Apparent activation energy of the process in vacuum is about 251 kJ/mol. Experiments carried out at temperatures much higher than the onset temperature of the reaction show that the dehydroxylation reaction overlaps with the reaction of formation of mullite, the final product in the reaction pathway. Received: 24 April 1998 / Revised, accepted: 12 October 1998     

Thermal behaviour and kinetics of dehydration of gypsum in air from in situ real-time laboratory parallel-beam X-ray powder diffraction

Thermal behaviour and kinetics of dehydration of gypsum in air have been investigated using in situ real-time laboratory parallel-beam X-ray powder diffraction data evaluated by the Rietveld method. Thermal expansion has been analysed from 298 to 373 K. The high-temperature limits for the cell edges and for the cell volume, calculated using the Einstein equation, are 4.29 × 10⁻⁶, 4.94 × 10⁻⁵, 2.97 × 10⁻⁵, and 8.21 × 10⁻⁵. Thermal expansion of gypsum is strongly anisotropic being larger along the b axis mainly due to the weakening of hydrogen bond. Dehydration of gypsum has been investigated in isothermal conditions within the 348–403 K range with a temperature increase of 5 K. Dehydration proceeds through the CaSO₄·2H₂O → CaSO₄·0.5H₂O → γ-CaSO₄ steps. Experimental data have been fitted with the Avrami equation to calculate the empirical activation energy of the process. No change in transformation mechanism has been observed within the analysed temperature range and the corresponding E _a is 109(12) kJ/mol.     

Dehydration dynamics of Ba-phillipsite: an in situ synchrotron powder diffraction study

 The stepwise dehydration process of the Ba-exchanged form of the zeolite phillipsite was studied by in situ synchrotron X-ray powder diffraction. A series of structure refinements were performed using the Rietveld method on powder diffraction data measured in the interval between 332 and 712 K. At 482 K, more than half of the water molecules were lost. The continuous water loss causes the Ba cations to migrate inside the zeolite channels in order to achieve a stable coordination with the framework oxygens. The dehydration process was completed at 663 K, where a new, completely dehydrated stable phase was detected. The temperature range of stability of this phase was more than 100 K, thanks to the stable coordination of the Ba cations with the framework oxygens. This phase is the first example of completely dehydrated zeolite containing divalent (barium) cations. Received: 8 January 2001 / Accepted: 1 November 2001     

Structural properties of (Mn1-x Fe x )Nb2O6 columbites from X-ray diffraction and IR spectroscopy

A suite of (Mn_1-x Fe _x )Nb₂O₆ (x=0, 0.05, 0.25, 0.50, 0.75, 1) columbite samples has been prepared by solid-state reaction from oxides. X-ray diffraction and spectroscopic investigations have been carried out in order to gain different perspectives on how the solid solution adapts at different length scales to cation mixing. X-ray powder diffraction and powder absorption IR spectroscopy data are presented. The powder diffraction data show that there is no significant excess volume of mixing on the Fe–Mn columbite join. All the unit-cell parameters decrease linearly as a function of increasing Fe content. Substitution of Fe²⁺ for the larger Mn²⁺ cation causes a decrease in the volume of the A polyhedron, which also becomes more regular with respect to both bond-length and edge-length distortion parameters. No significant variation of the B site has been observed. Wavenumber shifts of the IR peaks nearly all vary linearly with composition, consistent with linear variations of the lattice parameters. Line broadening has been quantified by autocorrelation analysis of the IR spectra. This is interpreted as suggesting that there is some element of local strain or positional disorder at the length scale of second or third nearest neighbours around sites occupied by Fe.     

Pressure–volume–temperature equation of state of andradite and grossular, by high-pressure and -temperature powder diffraction

 The thermoelastic parameters of natural andradite and grossular have been investigated by high-pressure and -temperature synchrotron X-ray powder diffraction, at ESRF, on the ID30 beamline. The P–V–T data have been fitted by Birch-Murnaghan-like EOSs, using both the approximated and the general form. We have obtained for andradite K ₀=158.0(±1.5) GPa, (dK/dT )₀=−0.020(3) GPa K⁻¹ and α₀=31.6(2) 10⁻⁶ K⁻¹, and for grossular K ₀=168.2(±1.7) GPa, (dK/dT)₀=−0.016(3) GPa K⁻¹ and α₀=27.8(2) 10⁻⁶ K⁻¹. Comparisons between the present issues and thermoelastic properties of garnets earlier determined are carried out. Received: 7 July 2000 / Accepted: 20 October 2000     

Structural and vibrational behaviour of fluorapatite with pressure. Part I: in situ single-crystal X-ray diffraction investigation

Using single-crystal X-ray diffraction from a diamond anvil cell, the compressibility of a synthetic fluorapatite was determined up to about 7?GPa. The compression pattern was anisotropic, with greater change along a than c. Unit cell parameters varied linearly with β _a =3.32(8)?10^?3 and β _c =2.40(5)?10^?3 GPa^?1, giving a ratio β _a :β _c =1.38:1. Data fitted with a third-order Birch-Murnaghan EOS yielded a bulk modulus of K ₀=93(4)?GPa with K′=5.8(1.8). The evolution of the crystal structure of fluorapatite was analysed using data collected at room pressure, at 3.04 and 4.72?GPa. The bulk modulus of phosphate tetrahedron is about three times greater than the bulk modulus of calcium polyhedra. The values were 270(10), 100(4) and 86(3) GPa for P, Ca1 (nine-coordinated) and Ca2 (seven-coordinated) respectively. While the calcium polyhedra became more regular with pressure, the distortion of the phosphate tetrahedron remained unchanged. The size of the channel extending along the [001] direction represented the most compressible direction. The Ca2–Ca2 distance decreased from 3.982 to 3.897?Å on compression from 0.0001 to 4.72?GPa. The anisotropic compressional pattern may be understood in terms of the greater compressibility of the channel size over the polyhedral units. The reduction of the channel volume was measured by the evolution of the trigonal prism, having the Ca2–Ca2–Ca2 triangle as its base and the c lattice parameter as its height. This prism volume changed from 47.3?ų at room pressure to 44.78?ų at 4.72?GPa. Its relatively high bulk moduli, 86(3) GPa, indicated that the channel did not collapse with pressure and the apatite structure could remain stable at very high pressure.     

Mineralogy and spectroscopy (visible near infrared and Fourier Transform Infrared) of Mukundpura CM2: Implications for asteroidal aqueous alteration

We report the textures, mineralogy and mineral chemistry of the Mukundpura matrix component, a clast-bearing, brecciated, new CM2 carbonaceous chondrite. Like other CMs, Mukundpura is matrix-enriched and has experienced different degrees of aqueous alteration with evidences of fracturing and compaction of clasts due to the impact. A few relict chondrule clasts and CAIs (diopside and spinel) survived despite of the alteration amidst accessory phases of olivine, magnetite, sulphides and calcite. X-Ray Diffraction (XRD), Visible Near Infrared (VNIR) and Fourier Transform Infrared (FTIR) spectroscopic studies reveal higher phyllosilicate content (∼90 %) comprising of both Mg and Fe-serpentine and abundant serpentine-sulphide intergrowths. Even then, the presence of accessory olivine as relict clasts can be interpreted from the presence of certain typical olivine absorptions in the FTIR spectra. The non-stoichiometric, Tochilinite-Cronstedtite occurrences probably relate to broadening of XRD and FTIR spectra and can be explained by coupled Al–Si and Mg–Al substitutions in talc and serpentine. The FTIR spectra suggest widespread transformation of olivine to serpentine, unlike the largely unaltered chondrules. The correlations of mineralogical alteration index with FeO/SiO₂ and S/SiO₂ in different domains of matrix suggest different extent of alterations. Thus, the aqueous alteration is extensive but not pervasive. The majority of alteration seems to have occurred within the asteroidal parent body. The Mukundpura CM2 thus preserves a unique combination of relict chondrules and highly aqueous altered variegated matrix clasts, although the surface mineralogy resembles the C-type asteroids recently probed by OSIRIS-REx and Hayabusa-2 missions.     

Kinetic study of the dehydroxylation of chrysotile asbestos with temperature by in situ XRPD

 The kinetics of the dehydroxylation of chrysotile was followed in situ at high temperature using real-time conventional and synchrotron powder diffraction (XRPD). This is the first time kinetics parameters have been calculated for the dehydroxylation of chrysotile. The value of the order of the reaction mechanism calculated using the Avrami model indicates that the rate-limiting step of the reaction is a one-dimensional diffusion with an instantaneous nucleation or a deceleratory rate of nucleation of the reaction product. Hence, the rate-limiting step is the one-dimensional diffusion of the water molecules formed in the interlayer region by direct condensation of two hydrogen atoms and an oxygen atom. The calculated apparent activation energy of the reaction in the temperature range 620–750 °C is 184 kJ mol⁻¹. The diffusion path is along the axis of the fibrils forming the fibers. The amorphous or short-range ordered dehydroxylate of chrysotile is extremely unstable because forsterite readily nucleates in the Mg-rich regions. Moreover, it is less stable than the dehydroxylate of kaolinite, the so-called metakaolinite, which forms mullite at about 950 °C. This difference is interpreted in terms of the different nature of the two ions Mg²⁺ and Al³⁺ and their function as glass modifier and glass-forming ion, respectively. Received: 10 April 2002 / Accepted: 7 January 2003 Acknowledgements This work is part of a COFIN project (04 Scienze della Terra, NR 17, 2000) supported by MURST. Dr Dapiaggi is kindly acknowledged for help during the data collection at the Dipartimento di Scienze della Terra, University of Milan.     

Characterization of arsenate adsorption on amorphous Al gels with Keggin structure by Fourier transformed infrared spectroscopy and MAS <Superscript>27</Superscript>Al NMR

Fourier transformed infrared spectrometry (FTIR) and 27Al Magic Angle spinning (MAS) nuclear magnetic resonance spectroscopy were employed to characterize arsenate adsorption on amorphous Al gels with Keggin structure at pH =4–10. These studies have proven that: the surface complex species of arsenate show significant differences under acidic and alkaline conditions, which was deduced based on the As-O stretching vibration bands located respectively at 774 and 870 cm-1; poorly crystalline Al13 (or Al)-arsen...     

Magnetic properties and neutron diffraction study of two manganese sulfosalts: monoclinic MnSb<Subscript>2</Subscript>S<Subscript>4</Subscript> and benavidesite (MnPb<Subscript>4</Subscript>Sb<Subscript>6</Subscript>S<Subscript>14</Subscript>)

Mn²⁺Sb₂S₄, a monoclinic dimorph of clerite, and benavidesite (Mn²⁺Pb₄Sb₆S₁₄) show well-individualized single chains of manganese atoms in octahedral coordination. Their magnetic structures are presented and compared with those of iron derivatives, berthierite (Fe²⁺Sb₂S₄) and jamesonite (Fe²⁺Pb₄Sb₆S₁₄). Within chains, interactions are antiferromagnetic. Like berthierite, MnSb₂S₄ shows a spiral magnetic structure with an incommensurate 1D propagation vector [0, 0.369, 0], unchanged with temperature. In berthierite, the interactions between identical chains are antiferromagnetic, whereas in MnSb₂S₄ interactions between chains are ferromagnetic along c-axis. Below 6 K, jamesonite and benavidesite have commensurate magnetic structures with the same propagation vector [0.5, 0, 0]: jamesonite is a canted ferromagnet and iron magnetic moments are mainly oriented along the a-axis, whereas for benavidesite, no angle of canting is detected, and manganese magnetic moments are oriented along b-axis. Below 30 K, for both compounds, one-dimensional magnetic ordering or correlations are visible in the neutron diagrams and persist down to 1.4 K.     

Directional dependence of P- and S-wave propagation and polarization in foliated rocks from the Kola superdeep well: Evidence from laboratory measurements and calculations based on TOF neutron diffraction

We have measured P- and S-wave velocities on two amphibolite and two gneiss samples from the Kola superdeep borehole as a function of pressure (up to 600 MPa) and temperature (up to 600 °C). The velocity measurements include compressional (Vp) and shear wave velocities (Vs1, Vs2) propagating in three orthogonal directions which were in general not parallel to inherent rock symmetry axes or planes. The measurements are accompanied by 3D-velocities calculations based on lattice preferred orientation (LPO) obtained by TOF (Time Of Flight) neutron diffraction analysis which allows the investigation of bulk volumes up to several cubic centimetres due to the high penetration depth of neutrons. The LPO-based numerical velocity calculations give important information on the different contribution of the various rock-forming minerals to bulk elastic anisotropy and on the relations of seismic anisotropy, shear wave splitting, and shear wave polarization to the structural reference frame (foliation and lineation). Comparison with measured velocities obtained for the three propagation directions that were not in accordance with the structural frame of the rocks (foliation and lineation) demonstrate that for shear waves propagating through anisotropic rocks the vibration directions are as important as the propagation directions. The study demonstrates that proper measurement of shear wave splitting by means of two orthogonal polarized sending and receiving shear wave transducers is only possible when their propagation and polarization directions are parallel and normal to foliation and lineation, respectively.     

Structural and vibrational behaviour of fluorapatite with pressure. Part II: in situ micro-Raman spectroscopic investigation

 High-pressure Raman investigations were carried out on a synthetic fluorapatite up to about 7 GPa to analyse the behaviour of the phosphate group's internal modes and of its lattice modes. The Raman frequencies of all modes increased with pressure and a trend toward reduced splitting was observed for the PO₄-stretching modes [(ν_3a(A_g) and ν_3b(A_g); ν_3a(E_2g) and ν_3b(E_2g)] and the PO₄ out-of-plane bending modes [ν_4a(A_g) and ν_4b(A_g)]. The pressure coefficients of phosphate modes ranged from 0.0047 to 0.0052 GPa⁻¹ for ν₃, from 0.0025 to 0.0044 GPa⁻¹ for ν₄, from 0.0056 to 0.0086 GPa⁻¹ for ν₂ and 0.0046 for ν₁ GPa⁻¹, while the pressure coefficients of lattice modes ranged from 0.0106 to 0.0278 GPa⁻¹. The corresponding Grüneisen parameters varied from 0.437 to 0.474, 0.428, 0.232 to 0.409 and 0.521 to 0.800 for phosphate modes ν₃, ν₁, ν₄, ν₂, respectively, and from 0.99 to 2.59 for lattice modes. The vibrational behaviour was interpreted in view of the high-pressure structural refinement performed on the same crystal under the same experimental conditions. The reduced splitting may thus be linked to the reduced distortion of the environment around the phosphate tetrahedron rather than to the decrease of the tetrahedral distortion itself. Moreover, the amount of calcium polyhedral compression, which is about three times the compression of phosphate tetrahedra, may explain the different Grüneisen parameters. Received: 25 April 2000 / Accepted: 20 December 2000