Al,Ge cation ordering in BaAl2Ge2O8-feldspar: monodomain ordering kinetics

The kinetics of monodomain order-disorder processes in monoclinic (I2/c) BaAl₂Ge₂O₈-feldspar have been investigated by X-ray powder diffraction, Hard Mode IR Spectroscopy, and TEM darkfield imaging on quenched samples. Compared to the behaviour predicted by the TDGL approximation ordering kinetics observed at low temperatures slow down significantly when equilibrium is approached. Such a delay is not observed in disordering experiments starting from essentially ordered cation distributions. The deviation from TDGL behaviour is interpreted in terms of partial order parameter conservation in a non-uniformly ordered phase. Modifications to the uniform TDGL rate equation are tested against the available data. An activation energy of 352 ± 28 kJ/mol is obtained for Al,Ge ordering. The mixing coefficient ξ_c ²/ξ², which describes the degree of order parameter conservation, is obtained as a function of temperature. While this coefficient vanishes in the vicinity of the transformation temperature T _tr, it saturates towards a level of ξ_c ²/ξ²≈0.4 for T→0. ξ _c ²/ξ² determines the kinetic stability of ordered clusters quenched from T≈T _tr. Received: 21 April 1999 / Revised, accepted: 19 July 1999     

Mode of formation of hibonite (CaAl12O19) within the U-Th skarns from the granulites of S-E Madagascar

 In Madagascar, hibonite occurs as a rather frequent mineral within thorianite-bearing skarns which are widespread in the Pan African granulitic formations constituting the S-E part of the Island (Tranomaro area). In these skarns, leucocratic segregations made up of CO₃-scapolite to meionite (An_equivalent=89–95% which implies T≥850° C), spinel and corundum were formed at stage 1 of metasomatism in a titanite-bearing matrix consisting of scapolite (An_eq=77–88) and aluminous diopside. During stage 2 of metasomatism, scapolite from the lenses were altered to anorthite+calcite while the less calcic scapolite remained stable which indicates T≈800° C. Hibonite crystallized at the expense of corundum and spinel. Expressed as mol% of the CaAl₁₂O₁₉/Ca(Al₁₀TiR²⁺)O₁₉/REE(Al₁₁R²⁺)O₁₉ [+Th (Al₁₀R²⁺ ₂)O₁₉] end-members (R ²⁺=Mg, Fe²⁺, Zn²⁺; Al=Al, Fe³⁺; Ti=Ti, Si), its composition varies from 26/72/2 to 50/23/27. The ideal activity of the CaAl₁₂O₁₉ component is about 0.25. Fluid inclusions in corundum, hibonite and anorthite are composed of nearly pure CO₂. In corundum, the isochores for primary inclusions are in agreement with the P-T estimates for regional metamorphism and stage 1 metasomatism (T≈850° C, P≈5 kbar). Inclusions with the highest density in hibonite and anorthite constrain P to about 3–3.5 kbar for T=800° C. Thermodynamic calculations indicate that, in addition to a low activity of CaAl₁₂O₁₉, stability of hibonite in equilibrium with anorthite and calcite implies an extremely low activity of silica (below the zircon-baddeleyite buffer). By contrast the activity of CO₂ may be high, in agreement with the observed fluid compositions. These results are corroborated by a short comparison with the other granulite occurrences of hibonite in Tanzania and South India. Received: 18 August 1994 / Accepted: 12 October 1995     

Crystal field transitions in Co2[Al4Si5]O18 cordierite and CoAl2O4 spinel determined by neutron spectroscopy

Inelastic magnetic neutron scattering has been used to determine the energy of the ⁴ A ₂→⁴ T ₂ transition in CoAl₂O₄ spinel and the δ₁ transition in Co₂[Al₄Si₅]O₁₈ cordierite. The observed crystal field splitting in Co-spinel is 485 meV (3900 cm⁻¹), which corresponds to a crystal field stabilization energy of 56.2 kJmol⁻¹. The transition energy of the δ₁ transition in Co-cordierite has been determined to be 21 meV (170 cm⁻¹). The present data demonstrate that magnetic neutron scattering can be used to measure crystal field transitions at energies of interest in the study of 3d-containing silicates. It may be used to measure transition energies when the use of optical spectroscopy is inappropriate. Received: 30 January 1997 / Accepted: 5 July 1997     

Computational study of tetrahedral Al–Si ordering in muscovite

 The nature of Al–Si ordering across the tetrahedral sites in muscovite, K₂Al₄(Si₆Al₂O₂₀)(OH)₄, was investigated using various computational techniques. Values of the atomic exchange interaction parameters J _l were obtained. From these parameters, a two-dimensional Al–Si ordering scheme was deduced. The transition temperature T _c for this two-dimensional ordering is 1900 K. There are several possible ordering schemes in three dimensions, based on different stacking sequences of ordered sheets of tetrahedral sites. Monte Carlo simulations of both two-dimensional and three-dimensional ordering were performed, but in the three-dimensional simulation only the two-dimensional ordering is seen, implying that three-dimensional ordering is too slow to be attained during the timescale of the simulation. The effect of the three-dimensional interactions is to raise the two-dimensional ordering temperature to 2140 K. From the three-dimensional Monte Carlo simulation, the frequency of occurrence of 4Si0Al, 3Si1Al, 2Si2Al and 1Si3Al clusters was determined, which match those inferred by ²⁹Si MAS–NMR measurements reasonably well. In fact, the match suggests that the cation ordering seen in experiments corresponds to a configuration with considerable short-range order but no long-range order, similar to a state that is at a temperature just above an ordering phase transition. Received: 28 August 2000 / Accepted: 12 March 2001     

Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

Transformations of the stuffed cristobalites, K2MSiO4, M=Mg, Zn, Co, Cd, with temperature and composition

The effects of composition and of temperature on the orthorhombic, Pca2 ₁ to cubic, F4ˉ3m transition of the stuffed cristobalite structure are reported. A distorton index which measures the departure of the orthorhombic unit cell from a metrically cubic cell shows that at room temperature, distortion increases in the progression K₂CdSiO₄ <K₂MgSiO₄ <K₂ZnSiO₄≈K₂CoSiO₄. High temperature X-ray powder measurements document an apparently discontinuous transition to a structure of F4ˉ3m symmetry. Differential scanning calorimetry shows a sharp, reversible, first order transition to the high temperature phase at about 500–600 °C for these compounds. Measured transformation enthalpies in the range of 7 to 16 J/g correlate roughly with the distortion index. The transformation involves tetrahedral rotation to an orientationally disordered cubic structure which retains an ordered M²⁺/Si distribution. Received: 8 November 1996 / Revised, accepted: 14 October 1997     

A statistical-mechanics model of ordering in aluminosilicate solid solutions

A statistical-thermodynamic approximation for order-disorder phase transitions in aluminosilicate solid solutions is presented. The approximation involves estimating the number of configurations with long range order parameter Q and short range order parameter σ, using an approximation to the probability that a configuration with the correct amount of long range order will also have the correct amount of short range order. This estimate is then used to give a free energy F(Q, σ, x, T), where x is the concentration of Al in the structure, and hence quantities such as T _c (x) are estimated. The predictions of the model for T _c (x) and the critical concentration x _c at which T _c falls to zero are shown to be in good agreement with the results of Monte Carlo simulations. Received: 14 May 1997 / Revised, accepted: 2 June 1997     

Determination of the mechanism of cation ordering in magnesioferrite (MgFe2O4) from the time- and temperature-dependence of magnetic susceptibility

The kinetics of non-convergent cation ordering in MgFe₂O₄ have been studied by measuring the Curie temperature (T _c) of synthetic samples as a function of isothermal annealing time. The starting material was a synthetic sample of near-stoichiometric MgFe₂O₄, synthesised from the oxides in air and quenched from 900 °C in water. Ordering experiments were performed using small chips of this material and annealing them at temperatures between 450 °C and 600 °C. The chips were periodically removed from the furnace, and their Curie temperatures were determined from measurements of alternating-field magnetic susceptibility (χ) as a function of temperature (T) to 400 °C. The Curie temperature of MgFe₂O₄ is very sensitive to the intracrystalline distribution of Fe³⁺ and Mg cations between tetrahedral and octahedral sites of the spinel crystal structure, and hence provides a very sensitive probe of the cation ordering process. The χ-T curve for the starting material displays a single sharp magnetic transition at a temperature of 303 °C. During isothermal annealing, the χ-T curve develops two distinct magnetic transitions; the first at a temperature corresponding to T _c for the disordered starting material and the second at a higher temperature corresponding to T _c for the equilibrium ordered phase. The size of the magnetic signal from the ordered phase increases smoothly as a function of time, until equilibrium is approached and the shape of the χ-T curve corresponds to a single sharp magnetic transition for the homogeneous ordered phase. These observations demonstrate that cation ordering in MgFe₂O₄ proceeds via a heterogeneous mechanism, involving the nucleation and growth of fine-scale domains of the ordered phase within a matrix of disordered material. Disordering experiments were performed by taking material equilibrated at 558 °C and annealing it at 695 °C. The mechanism of isothermal disordering is shown to involve nucleation and growth of disordered domains within an ordered matrix, combined with continuous disordering of the ordered matrix. This mixed mechanism of disordering may provide an explanation for the difference between the rates of ordering and disordering observed in MgFe₂O₄ using X-ray diffraction. The origin of the heterogeneous ordering/disordering mechanism is discussed in terms of the Ginzburg-Landau rate law. It is argued that heterogeneous mechanisms are likely to occur in kinetic experiments performed far from equilibrium, whereas a homogeneous mechanism may operate under slow equilibrium cooling. The implications of these observations for geospeedometry are discussed. Received: 12 May 1998 / Accepted: 25 June 1998     

The cubic-tetragonal phase transition in the system majorite (Mg4Si4O12) – pyrope (Mg3Al2Si3O12), and garnet symmetry in the Earth's transition zone

 Garnets along the join Mg₄Si₄O₁₂ (majorite end member) – Mg₃Al₂Si₃O₁₂ (pyrope) synthesized at 2000 °C, 19 GPa are, after quench, tetragonal in the compositional range up to 20 mol% pyrope, but cubic at higher Al contents. Lattice constants a _tet and a _tet in the tetragonal compositional range converge with increasing pyrope contents towards the lattice constant of the cubic garnets. The elastic strain and the intensity of the (222) reflection as a function of composition indicate a second-order phase transition near 20 mol% pyrope. From the wedge-like shape of pseudomerohedral twins and their interaction near 90° twin-boundary corners, as well as from the absence of growth-induced dislocations, it is concluded that the Al-poor garnets are also cubic at synthesis conditions but invert by (Mg,Si) ordering on the octahedral sites into tetragonal phases of space group I4₁/a upon quench. This implies that the cubic-to-tetragonal phase transition in Mg₄Si₄O₁₂ garnet occurs below 2000 °C at 19 GPa and at even lower temperatures in more aluminous compositions. A composition-dependent Landau model is consistent with a direct transformation from Ia3d to I4₁/a. Comparison of the T-X stability field of majorite-pyrope garnets with the chemistry of majorite-rich garnets expected to occur in the Earth's transition zone shows that the latter will be cubic under all conditions. Softening of elastic constants, which commonly accompanies ferroelastic phase transitions, may affect the seismic velocities of garnets in the deeper transition zone where majorite contents are highest. Received July 5, 1996 / Revised, accepted September 24, 1996     

Compressibility of calcium ferrite-type MgAl2O4

 In situ X-ray diffraction experiments of calcium ferrite-type MgAl₂O₄ have been carried out using a diamond anvil cell combined with synchrotron radiation and an imaging plate X-ray detector under hydrostatic pressures up to 9 GPa. The observed unit-cell volumes at various pressures were fitted to the Birch-Murnaghan equation of state, yielding a bulk modulus of K _{T 0}= 241(3) GPa when K′ _{T 0}=4 is assumed. This relatively large bulk modulus of calcium ferrite-type MgAl₂O₄ is consistent with that expected from the systematic relation between bulk modulus and molar volume for the most compounds possessing fcc oxygen packing. Received March 5, 1996/Revised, accepted October 15, 1996     

Metamorphic reactions between fluid inclusions and mineral hosts. I. Progress of the reaction calcite+quartz=wollastonite+CO2 in natural wollastonite-hosted fluid inclusions

 At the Bufa del Diente contact-metamorphic aureole, brine infiltration through metachert layers embedded in limestones produced thick wollastonite rims, according to Cc+Qz=Wo+CO₂. Fluid inclusions trapped in recrystallized quartz hosts include: (1) high salinity four phase inclusions [Th(V-L)=460–573° C; Td(salts)=350–400° C; (Na+K)_Cleq=64–73 wt%; X _{CO 2}≤0.02]; (2) low density vapour-rich CO₂-bearing inclusions [Th(L-V)≈500±100° C; X _{CO 2}=0.22–0.44; X _NaCl≤0.01], corresponding to densities of 0.27± 0.05 gcm⁻³. Petrographical observations, phase compositions and densities show that the two fluids were simultaneously trapped in the solvus of the H₂O-CO₂-salts system at 500–600° C and 700±200 bars. The low density fluid was generated during brine infiltration at the solvus via the wollastonite producing reaction. Identical fluid types were also trapped as inclusion populations in wollastonite hosts 3 cm adjacent to quartz crystals. At room temperature, both fluid types additionally contain one quartz and one calcite crystal, generated by the back-reaction Wo+CO₂=Cc+Qz of the host with the CO₂-proportion of the fluid during retrogression. All of the CO₂ was removed from the fluid. On heating in the microstage, the reaction progress of the prograde reaction was estimated via volume loss of the calcites. In vapour-rich fluids, 50% progress is reached at 490–530° C; 80% at 520–560° C; and 100% at 540–590° C, the latter representing the trapping temperatures of the original fluid at the two fluid solvus. The progress is volume controlled. With knowledge of compositions and densities from unmodified inclusions in quartz and using the equation of state of Duan et al. (1995) for H₂O-CO₂-NaCl, along with f _{CO 2}-values extracted from it, the reaction progress curve was recalculated in the P-T-X-space. The calculated progress curve passes through the two fluid solvus up to 380° C/210 bars, continues in the one fluid field and meets the solvus again at trapping conditions. The P-T slope is steep, most of the reaction occurs above 450° C and there is high correspondence between calculated and measured reaction progress. We emphasize that with the exception of quartz, back-reactions between inclusion fluids and mineral hosts is a common process. For almost any prograde metamorphic mineral that was formed by a devolatilization reaction and that trapped the equilibrium fluid or any peak metamorphic fluid as an inclusion, a fluid-host back-reaction exists which must occur somewhere along the retrograde path. Such retrograde reactions may cause drastic changes in density and composition of the fluid. In most cases, however, evidence of the evolving mineral assemblages is not given for they might form submicroscopical layers at the inclusion walls. Received: 15 March 1995 / Accepted: 1 June 1995     

Electronic absorption and luminescence spectroscopic studies of kyanite single crystals: differentiation between excitation of FeTi charge transfer and Cr3+ dd transitions

A selected set of five different kyanite samples was analysed by electron microprobe and found to contain chromium between <0.001 and 0.055 per formula unit (pfu). Polarized electronic absorption spectroscopy on oriented single crystals, R₁, R₂-sharp line luminescence and spectra of excitation of λ₃- and λ₄-components of R₁-line of Cr³⁺-emission had the following results: (1) The Fe²⁺–Ti⁴⁺ charge transfer in c-parallel chains of edge connected M(1) and M(2) octahedra shows up in the electronic absorption spectra as an almost exclusively c(||Z′)-polarized, very strong and broad band at 16000 cm⁻¹ if <, in this case the only band in the spectrum, and at an invariably lower energy of 15400 cm⁻¹ in crystals with  ≥ . The energy difference is explained by an expansion of the O_f–O_k, and O_b–O_m edges, by which the M(1) and M(2) octahedra are interconnected (Burnham 1963), when Cr³⁺ substitutes for Al compared to the chromium-free case. (2) The Cr³⁺ is proven in two greatly differing crystal fields a and b, giving rise to two sets of bands, derived from the well known dd transitions of Cr^{3+ 4}A_2g→⁴T_2g(F)(I), →⁴T_1g(F)(II), and →⁴T_1g(P)(III). Band energies in the two sets a and b, as obtained by absorption, A, and excitation, E, agree well: I: 17300(a, A), 17200(a, E), 16000(b, A), 16200(b, E); II: 24800(a, A), 24400(a, E); 22300(b, A), 22200(b, E); III: 28800(b,A) cm⁻¹. Evaluation of crystal field parameters from the bands in the electronic spectra yield Dq(a)=1730 cm⁻¹, Dq(b)=1600 cm⁻¹, B(a)=790 cm⁻¹, B(b)=620 cm⁻¹ (errors ca. ±10 cm⁻¹), again in agreement with values extracted from the λ³, λ⁴ excitation spectra. The CF-values of set a are close to those typical of Cr³⁺ substituting for Al in octahedra of other silicate minerals without constitutional OH⁻ as for sapphirine, mantle garnets or beryl, and are, therefore, interpreted as caused by Cr³⁺ substituting for Al in some or all of the M(1) to M(4) octaheda of the kyanite structure, which are crystallographically different but close in their mean Al–O distances, ranging from 1.896 to 1.919 A (Burnham 1963), and slight degrees of distortion. Hence, band set a originates from substitutive Cr³⁺ in the kyanite structural matrix. The CF-data of Cr³⁺ type b, expecially B, resemble those of Cr³⁺ in oxides, especially of corundum type solid solutions or eskolaite. This may be interpreted by the assumption that a fraction of the total chromium contents might be allocated in a precursor of a corundum type exsolution. Received: 3 January 1997 / Revised, accepted: 2 May 1997     

High-pressure and high-temperature in situ X-ray diffraction study of iron and corundum to 68 GPa using an internally heated diamond anvil cell

Using powder X-ray diffraction of heated solids to pressures reaching 68 GPa, the pressure-volume-temperature (PVT) data on corundum Al₂O₃ and ɛ-Fe were determined with the following results: *Corundum,*Iron, *Al₂O₃*ɛ-Fe Isothermal bulk*258 (2)*164 (3)  modulus K'_{300, 1} (GPa) Pressure derivative K_{300, 1}*4.88 (4)*5.36 (16) Temperature derivative*–0.020 (2)*–0.043 (3)  (∂K _T,1 /∂T) _P (GPa/K) Molar volume V_300,1*25.59 (2)*6.76 (2)  (cm³/mol) Isobaric thermal expansion at 1 atm (0.101 MPa) is given by (K^–1): α _T =2.6 (2) 10^–5+1.81 (9) 10^–9 T–0.67 (6)/T ² for corundum, and α _T =5.7 (4) 10^–5+4.2 (4) 10^–9 T–0.17 (7)/T ² for iron ɛ-Fe. Received: 1 March 1997 / Revised, accepted: 21 August 1997     

Oxygen deficient perovskites in the system CaSiO3–CaAlO2.5 and implications for the Earth’s interior

Oxygen deficient perovskites of the system CaSiO₃–CaAlO_2.5 have been synthesised at high-pressure and -temperature conditions relevant to the Earth’s transition zone in order to investigate their stabilities in the Earth’s mantle and determine structural properties associated with vacancy incorporation. Two polysomes of thermodynamically stable defect perovskites with Ca(Al_0.4Si_0.6)O_2.8 and Ca(Al_0.5Si_0.5)O_2.75 stoichiometry have been identified. The ordering of oxygen defects into pseudo-cubic (111) layers results in well-ordered ten- or eightfold superstructures, respectively. At all other compositions examined, a metastable formation of perovskites has been observed instead, which are assumed to grow initially disordered. These are now characterised by tiny domains, formed due to subsequent ordering of vacancies along various pseudo-cubic {111} layers. Both ordered defect perovskites show a large P–T stability field ranging from about 9–18 GPa and 4–12 GPa, respectively. Microstructural TEM analyses revealed the presence of growth and ferroelastic twins, which indicate a phase transition from rhombohedral to monoclinic symmetry during quenching. Electron energy loss spectroscopy of Si and Al K edges point at the presence of tetrahedral, octahedral and maybe some pentacoordinated silicon, whereas aluminium is predominantly octahedrally coordinated with minor fractions in lower coordination. Observed properties are interpreted in terms of a new structural model, explaining the observed phase transition and formation of different twin laws as well as giving reasons for the development of such large superstructures. With respect to phase relations of the transition zone, the potential occurrence of such defect perovskites in the Earth’s interior is discussed.     

The low-pressure stability of phase A,Mg7Si2O8(OH)6

 Phase A, Mg₇Si₂O₈(OH)₆, is a dense hydrous magnesium silicate whose importance as a host of H₂O in the Earth’s mantle is a subject of debate. We have investigated the low-pressure stability of phase A in experiments on the reaction phase A=brucite+forsterite. Experiments were conducted in piston-cylinder and multi-anvil apparatus, using mixtures of synthetic phase A, brucite and forsterite. The reaction was bracketed between 2.60 and 2.75 GPa at 500° C, between 3.25 and 3.48 GPa at 600° C and between 3.75 and 3.95 GPa at 650^° C. These pressures are much lower than observed in the synthesis experiments of Yamamoto and Akimoto (1977). At 750^° C the stability field of brucite + chondrodite was entered. The enthalpy of formation and entropy of phase A at 1 bar (10⁵ Pa), 298 K, were derived from the experimental brackets on the reaction phase A=brucite+forsterite using a modified version of the thermodynamic dataset THERMOCALC of Holland and Powell (1990), which includes a new equation of state of H₂O derived from the molecular dynamics simulations of Brodholt and Wood (1993). The data for phase A are: ΔH ^o _f =−7126±8 kJ mol^-1, S ^o=351 J K^-1 mol^-1. Incorporating these data into THERMOCALC allows the positions of other reactions involving phase A to be calculated, for example the reaction phase A + enstatite=forsterite+vapour, which limits the stability of phase A in equilibrium with enstatite. The calculated position of this reaction (753° C at 7 GPa to 937° C at 10 GPa) is in excellent agreement with the experimental brackets of Luth (1995) between 7 and 10 GPa, supporting the choice of equation of state of H₂O used in THERMOCALC. Comparison of our results with calculated P-T paths of subducting slabs (Peacock et al. 1994) suggests that, in the system MgO–SiO₂–H₂O, phase A could crystallise in compositions with Mg/Si>2 at pressures as low as 3 GPa. In less Mg rich compositions phase A could crystallise at pressures above approximately 6 GPa. Received: 3 July 1995/Accepted: 14 December 1995     

High-T phase transition of synthetic ANaB(LiMg)CMg5Si8O22(OH)2 amphibole: an X-ray synchrotron powder diffraction and FTIR spectroscopic study

The synthetic amphibole Na_0.95(Li_0.95Mg_1.05)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 ^ANa_0.8^B(Na_0.8Mg_1.2)^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.     

Thermobarometry of mafic igneous rocks based on clinopyroxene-liquid equilibria, 0–30 kbar

 Models for estimating the pressure and temperature of igneous rocks from co-existing clino-pyroxene and liquid compositions are calibrated from existing data and from new data obtained from experiments performed on several mafic bulk compositions (from 8–30 kbar and 1100–1475° C). The resulting geothermobarometers involve thermodynamic expressions that relate temperature and pressure to equilibrium constants. Specifically, the jadeite (Jd; NaAlSi₂O₆)–diopside/hedenbergite (DiHd; Ca(Mg, Fe) Si₂O₆) exchange equilibrium between clinopyroxene and liquid is temperature sensitive. When compositional corrections are made to the calibrated equilibrium constant the resulting geothermometer is (i) 10⁴ T=6.73−0.26^* ln [Jd^px*Ca^liq*Fm^liqDiHd^px*Na^liq*Al^liq] −0.86^* ln [Mg^liqMg^liq+Fe^liq]+0.52^*ln [Ca^liq] an expression which estimates temperature to ±27 K. Compared to (i), the equilibrium constant for jadeite formation is more sensitive to pressure resulting in a thermobarometer (ii) P=−54.3+299^* T10⁴+36.4^* T10⁴ ln [Jd^px[Si^liq]^2*Na^liq*Al^liq] +367^*[Na^liq*Al^liq] which estimates pressure to ± 1.4 kbar. Pressure is in kbar, T is in Kelvin. Quantities such as Na^liq represent the cation fraction of the given oxide (NaO_0.5) in the liquid and Fm=MgO+FeO. The mole fractions of Jd and diopside+hedenbergite (DiHd) components are calculated from a normative scheme which assigns the lesser of Na or octahedral Al to form Jd; any excess Al^VI forms Calcium Tschermak’s component (CaTs; CaAlAlSiO₆); Ca remaining after forming CaTs and CaTiAl₂O₆ is taken as DiHd. Experimental data not included in the regressions were used to test models (i) and (ii). Error on predictions of T using model (i) is ±40 K. A pressure-dependent form of (i) reduces this error to ±30 K. Using model (ii) to predict pressures, the error on mean values of 10 isobaric data sets (0–25 kbar, 118 data) is ±0.3 kbar. Calculating thermodynamic properties from regression coefficients in (ii) gives V^Jd _f of 23.4 ±1.3 cm³/mol, close to the value anticipated from bar molar volume data (23.5 cm³/mol). Applied to clinopyroxene phenocrysts from Mauna Kea, Hawaii lavas, the expressions estimate equilibration depths as great as 40 km. This result indicates that transport was sufficiently rapid that at least some phenocrysts had insufficient time to re-equilibrate at lower pressures. Received: 16 May 1994/Accepted: 15 June 1995     

Study of the electrical charge transport in ilvaite using impedance spectroscopy and thermopower data

The electrical conduction in the mineral ilvaite was studied between ≈170 and 450 K. A natural ilvaite from Elba (Italy) was found to be semiconducting with a DC conductivity 1.8×10^–3 (Ωcm)^–1 at 300 K, measured parallel (∥) to the [001] direction; perpendicular (⊥) to [001] it was 1.4×10^–5 (Ωcm)^–1, i.e. the conductivity is highly anisotropic. The conduction is effected by a hopping charge transport between localized levels in the energy gap associated with activation energies E _A =0.3–0.5 eV. It is concluded that impurities (Mg,Al,Mn) may play a decisive role in the charge hopping transport ∥ [001] that is basically governed by Fe²⁺-Fe³⁺ pairs on A-sites of the lattice as the source of electrons. Although the E_A-values were similar for both measured directions, the sign of thermopower is different which points to different charge transfer mechanisms. The bulk DC conductivity σ_DC ^AC for measurements ∥ [001], obtained by extrapolation of AC data using impedance spectroscopy, could only be determined at T<300 K owing to sample–electrode interfacial effects. In contrast, the bulk σ_DC ^AC⊥ [001] showed a slight break at ≈380 K that may reflect the structural phase transition monoclinic→orthorhombic at ≈345 K. From AC conductivity measurements in the frequency range 20 Hz–1 MHz at T<300 K, a dispersive character of electronic relaxation was found, resembling that of amorphous semiconductors and of impurity conduction in crystalline semiconductors where it was ascribed to charge hopping processes of electrons between localized levels of cation pairs or clusters of limited lengths. Received: 4 August 1997 / Revised, accepted: 12 January 1998     

Melting of albite and dehydration of brucite in H2O–NaCl fluids to 9 kbars and 700–900°C: implications for partial melting and water activities during high pressure metamorphism

 The melting reaction: albite_(solid)+ H₂O_(fluid) =albite-H₂O_(melt) has been determined in the presence of H₂O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H₂O–CO₂ fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X _(H2O) ) melting relations in the two systems are almost coincident. By contrast, H₂O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 ^°C higher in H₂O–NaCl brines than in H₂O–CO₂ fluids for X _(H2O) =0.8 and ∼100 ^°C higher for X _(H2O) =0.5. The melting temperature of albite in H₂O–NaCl fluids of X _(H2O)=0.8 is ∼100 ^°C higher than in pure water. The P–T curves for albite melting at constant H₂O–NaCl show a temperature minimum at about 5 kbar. Water activities in H₂O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H₂O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a _(H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996     

Kornerupine parageneses in whiteschists and other magnesian rocks: is kornerupine + talc a high-pressure assemblage equivalent to tourmaline + orthoamphibole?

Kornerupine, (□,Fe,Mg)(Mg,Fe,Al)₉(Si,Al,B)₅ (O,OH,F)₂₂, has been reported with talc in rocks from six localities worldwide, but only at Chilapila Hill in the Lufilian Arc, Zambia do textural relationships imply that kornerupine (Krn) equilibrated with talc (Tlc) during a prograde metamorphic event at T≈ 640 °C, P≈ 13 kbar; a prograde Krn + Tlc assemblage has also been reported from Mautia Hill, Tanzania (P ≤ 13 kbar). In order to estimate possible constraints on the stability range for the kornerupine + talc paragenesis in nature, we constructed a P-T diagram in the model system MgO-Al₂O₃-SiO₂-H₂O (MASH) for seven phases quartz (Qtz), B-free kornerupine sensu stricto, anthophyllite (Ath), chlorite (Chl), cordierite (Crd), kyanite (Ky), and talc. The minimum pressure for Krn + Tlc + Ky stability in MASH is close to that for Ky + Tlc stability, i.e., 6–8 kbar, at T≤ 780 °C. However, in the natural system, B₂O₃ and Na₂O are major constituents in Krn and orthoamphibole (Oam), respectively, and dravitic tourmaline (Tur) is widespread. The critical assemblage alternative to Krn + Tlc in nature is Tur + Oam. The upper pressure limit of Tur + Ath is determined by the upper pressure for anthophyllite: 7.7–10.5 kbar at 682–794 °C in the MgO-SiO₂-H₂O system (Chernosky et al. 1985, Am Mineral 70:223–236), and is undoubtedly higher in the presence of Na₂O, CaO, and Al₂O₃. At three of the six localities, talc is a retrograde phase; nonetheless, it possibly equilibrated with kornerupine on the retrograde path or during a later metamorphic event at P-T conditions appropriate for Ky + Tlc. At the sixth locality (Mulvoj, southwestern Pamir Mountains, Tajikistan), Krn is found in the same thin section as talc and kyanite and all three minerals formed during a prograde metamorphic event at T≥ 650 °C, P near 7 kbar. However, Krn is restricted to a lens 4 to 6 mm thick of phlogopite + anthophyllite + Tur and it does not touch either talc or kyanite. A reaction relating the Mulvoj and Chilapila Hill (Krn + Tlc + Ky + Qtz + Tur) parageneses is calculated from compositions in the Mulvoj rock to be 0.40Tur + 2.55Ath + 1.33H₂O + 0.27F = Krn + 2.16Tlc + 0.36B₂O₃ + 0.02Rutile + 0.19Na₂O + 0.17CaO. Given the difference in metamorphic pressures estimated for Mulvoj and Chilapila Hill, Krn + Tlc is inferred to be favored by increasing pressure as well as by low Na₂O and CaO contents. Some FeO, F, Fe₂O₃, and BeO are present in measurable amounts in at least one of the phases in the Mulvoj and Chilapila Hill whiteschists (e.g., Krn contains 0.24–0.67 wt% BeO), but the effect of these constituents is subordinate to that of Na₂O, CaO and B₂O₃. The Krn + Tlc could be a more important assemblage in B-bearing whiteschists than has been reported to date, particularly at pressures where orthoamphibole is no longer stable. Received: 21 April 1997 / Accepted: 13 October 1997