Hydrostatic compression of γ-(Mg0.6, Fe0.4)2SiO4 to 50.0 GPa

The bulk modulus, K ₀, and its pressure derivative K₀, of -(Mg_0.6, Fe_0.4)₂SiO₄ have been accurately determined to 50.0 GPa under hydrostatic conditions at room temperature in a diamond cell using synchrotron radiation. Our results agree with Brillouin and ultrasonic measurements on -Mg₂SiO₄ at low pressure, indicating normal elastic behaviour in the metastable pressure range of this high pressure mineral. Our values of K ₀ and k₀ are 183.0 GPa and 5.4, respectively.     

Effects of Fe/Mg on the compressibility of synthetic wadsleyite: β-(Mg1-xFex)2SiO4 (x≤0.25)

Four crystals of synthetic wadsleyite, -(Mg,Fe)₂SiO₄, were mounted together in one diamond-anvil cell for the determination of unit-cell parameters as a function of pressure. The Fe/(Fe+Mg) are 0.00, 0.08, 0.16, and 0.25 (the most iron-rich stable composition). Unit-cell refinements were made at 12 pressures up to 4.5 GPa. No phase transitions were observed and all crystals remained dimensionally orthorhombic. Of the three axes, c is the most compressible (0.000239(3) GPa^-1), whereas compressibilities of a and b are both about 30% less. The Fe content has no systematic effect on volume or linear compressibilities. Bulk moduli, based on a Birch-Murnaghan equation of state (K assumed to be 4.00) are 160(3), 169(3), 164(2), and 165(3) GPa for the four crystals in order of increasing Fe. Substitution of Fe for Mg, therefore, does not appear to have a systematic effect on bulk modulus. Other factors, especially Fe³⁺/Fe²⁺ and other deviations from the strict Mg₂SiO₄-Fe₂SiO₄ binary, may have a greater influence on compressibility.     

Experimental determination of activity-composition relations in Ni2SiO4− Mg2SiO4 and Co2SiO4-Mg2SiO4 olivine solid solutions at 1200 K and 0.1 MPa and 1573 K and 0.5 GPa

Activity-composition relations in the olivine solid solutions Ni₂SiO₄⁻ -Mg₂SiO₄ and Co₂SiO₄-Mg₂SiO₄ have been determined at 1200 K and 0.1 MPa and at 1573 K and 0.5 GPa by equilibration with the corresponding oxide solutions. Both olivine solutions show small positive deviations from ideal (two site) mixing, which, within the limits of accuracy of the method, may be described by the simple regular solution model with parameters W_Ni+Mg^ol= 0.35 ± 1.0 kJ/g-atom and W_Co-Mg^ol = 1.37 ± 0.9 kJ/g-atom. The requirements of internal consistency between the two systems also show that the recent determination by Brousse et al. (1984) of the enthalpy of formation of Mg₂SiO₄is to be preferred over earlier work, and that their value is also probably more accurate than the uncertainty in their own measurements indicates; activities in the NiO-MgO system are close to ideal.     

Synthetic MgGa2O4-Mg2GeO4 spinel solid solution and β-Mg3Ga2GeO8: chemistry, crystal structures, cation ordering, and comparison to Mg2GeO4 olivine

 Structural parameters and cation ordering are determined for four compositions in the synthetic MgGa₂O₄-Mg₂GeO₄ spinel solid solution (0, 8, 15 and 23 mol% Mg₂GeO₄; 1400 °C, 1 bar) and for spinelloid β-Mg₃Ga₂GeO₈ (1350 °C, 1 bar), by Rietveld refinement of room-temperature neutron diffraction data. Sample chemistry is determined by XRF and EPMA. Addition of Mg₂GeO₄ causes the cation distribution of the MgGa₂O₄ component to change from a disordered inverse distribution in end member MgGa₂O₄, ^[4]Ga = x = 0.88(3), through the random distribution, toward a normal cation distribution, x = 0.37(3), at 23 mol% Mg₂GeO₄. An increase in a_o with increasing Mg₂GeO₄ component is correlated with an increase in the amount of Mg on the tetrahedral site, through substitution of 2 Ga³⁺⇄ Mg²⁺+Ge⁴⁺. The spinel exhibits high configurational entropy, reaching 20.2 J mol⁻¹ (four oxygen basis) near the compositional upper limit of the solid solution. This stabilizes the spinel in spite of positive enthalpy of disordering over the solid solution, where ΔH _D  = αx + βx ², α = 22(3), β = −21(3) kJ mol⁻¹. This model for the cation distribution across the join suggests that the empirically determined limit of the spinel solid solution is correlated with the limit of tetrahedral ordering of Mg, after which local charge-balanced substitution is no longer maintained. Spinelloid β-Mg₃Ga₂GeO₈ has cation distribution ^M1[Mg_0.50(2)Ga_0.50(2)] ^M2[Mg_0.96(2)Ga_0.04(2)] ^M3[Mg_0.77(2) Ga_0.23(2)]₂ (Ge_0.5Ga_0.5)₂O₈ (tetrahedral site occupancies are assumed). Octahedral site size is correlated to Mg distribution, where site volume, site distortion, and Mg content follow the relation M1<M3<M2. The disordered cation distribution provides local electrical neutrality in the structure, and stabilization through increased configurational entropy (27.6 J mol⁻¹; eight oxygen basis). Comparison of the crystal structures of Mg_{1+ N} Ga_{2−2 N} Ge _N O₄ spinel, β-Mg₃Ga₂GeO₈, and Mg₂GeO₄ olivine reveals β-Mg₃Ga₂GeO₈ to be a true structural intermediate. Phase transitions across the pseudobinary are necessary to accommodate an increasing divergence of cation size and valence, with addition of Mg₂GeO₄ component. Octahedral volume increases while tetrahedral volume decreases from spinel to β-Mg₃Ga₂GeO₈ to olivine, with addition of Mg and Ge, respectively. Furthermore, M-M distances increase regularly across the join, suggesting that changes in topology reduce cation-cation repulsion. Received: 9 November 1998 / Revised, accepted: 3 August 1999     

Electronic state of Fe2+ in (Mg,Fe)(Si,Al)O3 perovskite and (Mg,Fe)SiO3 majorite at pressures up to 81 GPa and temperatures up to 800 K

Despite a large number of studies of iron spin state in silicate perovskite at high pressure and high temperature, there is still disagreement regarding the type and P–T conditions of the transition, and whether Fe²⁺ or Fe³⁺ or both iron cations are involved. Recently, our group published results of a Mössbauer spectroscopy study of the iron behaviour in (Mg,Fe)(Si,Al)O₃ perovskite at pressures up to 110 GPa (McCammon et al. 2008), where we suggested stabilization of the intermediate spin state for 8- to 12-fold coordinated ferrous iron (^[8–12]Fe²⁺) in silicate perovskite above 30 GPa. In order to explore the behaviour in related systems, we performed a comparative Mössbauer spectroscopic study of silicate perovskite (Fe_0.12Mg_0.88SiO₃) and majorite (with two compositions—Fe_0.18Mg_0.82SiO₃ and Fe_0.11Mg_0.88SiO₃) at pressures up to 81 GPa in the temperature range 296–800 K, which was mainly motivated by the fact that the oxygen environment of ferrous iron in majorite is quite similar to that in silicate perovskite. The ^[8–12]Fe²⁺ component, dominating the Mössbauer spectra of majorites, shows high quadrupole splitting (QS) values, about 3.6 mm s^?1, in the entire studied P–T region (pressures to 58 GPa and 296–800 K). Decrease of the QS of this component with temperature at constant pressure can be described by the Huggins model with the energy splitting between low-energy e _g levels of ^[8–12]Fe²⁺ equal to 1,500 (50) cm^?1 for Fe_0.18Mg_0.82SiO₃ and to 1,680 (70) cm^?1 for Fe_0.11Mg_0.88SiO₃. In contrast, for the silicate perovskite dominating Mössbauer component associated with ^[8–12]Fe²⁺ suggests the gradual change of the electronic properties. Namely, an additional spectral component with central shift close to that for high-spin ^[8–12]Fe²⁺ and QS about 3.7 mm s^?1 appeared at ~35 (2) GPa, and the amount of the component increases with both pressure and temperature. The temperature dependence of QS of the component cannot be described in the framework of the Huggins model. Observed differences in the high-pressure high-temperature behaviour of ^[8–12]Fe²⁺ in the silicate perovskite and majorite phases provide additional arguments in favour of the gradual high-spin—intermediate-spin crossover in lower mantle perovskite, previously reported by McCammon et al. (2008) and Lin et al. (2008).     

High-pressure and high-temperature Raman spectroscopic study of hydrous wadsleyite (β-Mg2SiO4)

In situ Raman spectra of hydrous wadsleyite (β-Mg₂SiO₄) with ~1.5 wt% H₂O, synthesized at 18 GPa and 1,400°C, have been measured in an externally heated diamond anvil cell up to 15.5 GPa and 673 K. With increasing pressure (at room temperature), the three most intense bands at ~549, 720 and 917 cm⁻¹ shift continuously to higher frequencies, while with increasing temperature at 14.5 GPa, these bands generally shift to lower frequencies. The temperature-induced frequency shifts at 14.5 GPa are significantly different from those at ambient pressure. Moreover, two new bands at ~714 and ~550 cm⁻¹ become progressively significant above 333 and 553 K, respectively, and disappear upon cooling to room temperature. No corresponding Raman modes of these two new bands were reported for wadsleyite at ambient conditions, and they are thus probably related to thermally activated processes (vibration modes) at high-pressure and temperature conditions.     

The crystal structure of bøgvadite (Na2SrBa2Al4F20)

The crystal structure of bøgvadite, Na₂SrBa₂Al₄F₂₀, has been solved and refined to a R₁ factor of 4.4 % from single-crystal data (MoKα X-ray diffraction, CCD area detector) on a sample from the cryolite deposit at Ivittuut, SW Greenland. Bøgvadite is monoclinic, P2₁/n space group, with unit cell parameters a?=?7.134(1), b?=?19.996(3) and c?=?5.3440(8) Å, β?=?90.02(1)^o. A close proximity of the crystal structure to an orthorhombic symmetry and the presence of the two twin components in a nearly 1:1 ratio suggest that the investigated bøgvadite crystal has originally formed as a high-temperature orthorhombic polymorph which on cooling transformed to the stable low temperature monoclinic structure. The bøgvadite crystal structure has groupings of cation-fluoride coordination polyhedra similar to those found in the crystal structures of the genetically closely associated minerals jarlite and jørgensenite. However, its structure type is different from the latter two. The fluoridoaluminate framework of bøgvadite consists of infinite zig-zag chains of cis-connected AlF₆ coordination octahedra. The ¹ _∞[AlF₅] chains are interconnected by infinite chains of Na-F coordination polyhedra which extend in the same direction. Na is coordinated by nine F atoms if its full surrounding is taken in consideration, but makes significant chemical bonds only to closest five. The chains of AlF₆ and NaF₉ coordination polyhedra form double layers. In the centre of layers, relatively large voids in the form of pentagonal antiprisms are occupied by Sr atoms which make chemical bonds with the closest six F atoms. Between the SrF₁₀ coordinations in the centre of layers run empty channels. The double layers are interconnected by Ba atoms which are coordinated by eight F atoms and fill the spaces between the layers. Bøgvadite belongs to the group of fluoridoaluminates with infinite chains of cis-connected AlF₆ coordination octahedra, alike those found in the crystal structures of Ba-fluoridoaluminates.     

The crystal structure of galgenbergite-(Ce), CaCe2(CO3)4∙H2O

Galgenbergite-(Ce) from the type locality, the railroad tunnel Galgenberg between Leoben and St. Michael, Styria, Austria, was investigated. There it occurs in small fissures of an albite-chlorite schist as very thin tabular crystals building rosette-shaped aggregates associated with siderite, ancylite-(Ce), pyrite and calcite. Electron microprobe analyses gave CaO 9.49, Ce₂O₃ 28.95, La₂O₃ 11.70, Nd₂O₃ 11.86, Pr₂O₃ 3.48, CO₂ 30.00, H₂O 3.07, total 98.55 wt.%. CO₂ and H₂O calculated by stoichiometry. The empirical formula (based on Ca + REE ∑3.0) is $ \mathrm{C}{{\mathrm{a}}_{1.00 }}{{\left( {\mathrm{C}{{\mathrm{e}}_{1.04 }}\mathrm{L}{{\mathrm{a}}_{0.42 }}\mathrm{N}{{\mathrm{d}}_{0.42 }}\mathrm{P}{{\mathrm{r}}_{0.12 }}} \right)}_{2.00 }}{{\left( {\mathrm{C}{{\mathrm{O}}_3}} \right)}_4}\cdot {{\mathrm{H}}_2}\mathrm{O} $ , and the simplified formula is $ \mathrm{CaC}{{\mathrm{e}}_2}{{\left( {\mathrm{C}{{\mathrm{O}}_3}} \right)}_4}\cdot {{\mathrm{H}}_2}\mathrm{O} $ . According to X-ray single crystal diffraction galgenbergite-(Ce) is triclinic, space group $ P\overline{1},a=6.3916(5) $ , b?=?6.4005(4), c?=?12.3898(9) Å, α?=?100.884(4), β?=?96.525(4), γ?=?100.492(4)°, V?=?483.64(6) ų, Z?=?2. The eight strongest lines in the powder X-ray diffraction pattern are [d _calc in Å/(I)/hkl]: 5.052/(100)/011; 3.011/(70)/0-22; 3.006/(66)/004; 5.899/(59)/-101; 3.900/(51)/1-12; 3.125/(46)/-201; 2.526/(42)/022; 4.694/(38)/-102. The infrared absorption spectrum reveals H₂O (OH-stretching mode at 3,489 cm^?1, HOH bending mode at 1,607 cm^?1) and indicates the presence of distinctly non-equivalent CO₃-groups by double and quadruple peaks of their ν1, ν2, ν3 and ν4 modes. The crystal structure of galgenbergite-(Ce) was refined with X-ray single crystal data to R1?=?0.019 for 2,448 unique reflections (I?>?2σ(I)) and 193 parameters. The three cation sites of the structure Ca(1), Ce(2) and Ce(3) have a modest mixed site occupation by Ca and small amount of REE (Ce, La, Pr, Nd) and vice versa. The structure is based on double layers parallel to (001), which are composed of Ca(1)Ce(2)(CO₃)₂ single layers with an ordered chessboard like arrangement of Ca and Ce, and with a roof tile-like stacking of the CO₃ groups. Perpendicular to (001) the double layers are connected to a triclinic framework structure with good cleavage parallel to (001) by a differently organized and more open part of the structure formed by Ce(3)(CO₃)₂(H₂O). Based on the topology of the CaCe(CO₃)₂ single layer in galgenbergite-(Ce), structural relationships to rutherfordine, to aragonite and ancylite type minerals, and to lanthanite are outlined.     

Description and crystal structure of albrechtschraufite, MgCa4F2[UO2(CO3)3]2⋅17-18H2O

Albrechtschraufite, MgCa₄F₂[UO₂(CO₃)₃]₂?17-18H₂O, triclinic, space group Pī, a?=?13.569(2), b?=?13.419(2), c?=?11.622(2) Å, α?=?115.82(1), β?=?107.61(1), γ?=?92.84(1)° (structural unit cell, not reduced), V?=?1774.6(5) ų, Z?=?2, D _c?=?2.69 g/cm³ (for 17.5 H₂O), is a mineral that was found in small amounts with schröckingerite, NaCa₃F[UO₂(CO₃)₃](SO₄)?10H₂O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca₂[UO₂(CO₃)₃]??~?11H₂O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX?=?1.511(2), nY?=?1.550(2), nZ?=?1.566(2), 2?V?=?65(1)° (λ?=?589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO₂ and H₂O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1?=?0.0206 and wR2?=?0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO₂(CO₃)₃]^4? anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF₂(O_carbonate)₃(H₂O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO₆, CaF₂O₂(H₂O)₄, CaFO₃(H₂O)₄ and CaO₂(H₂O)₆ coordination polyhedra. The crystal structure is built up from MgCa₃F₂[UO₂(CO₃)₃]?8H₂O layers parallel to (001) which are linked by Ca[UO₂(CO₃)₃]?5H₂O moieties into a framework of the composition MgCa₄F₂[UO₂(CO₃)₃]?13H₂O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a total water content of 17-18H₂O per formula unit. The MgCa₃F₂[UO₂(CO₃)₃]?8H₂O layers are pseudosymmetric according to plane group symmetry cmm. The remaining constituents do not sustain this pseudosymmetry and make the entire structure truly triclinic. A characteristic paddle-wheel motif Ca[UO₂(CO₃)₃]₄Ca relates the structure of albrechtschraufite partly to that of andersonite and two synthetic alkali calcium uranyl tricarbonates.     

下地幔温压下(Mg,Fe)SiO3钙钛矿的相稳定性

在69~100 GPa冲击压力(估算温度为2600~4300 K)范围内进行了初始样品为(Mg0.92,Fe0.08)SiO3顽火辉石和MgO+SiO2的冲击压缩回收实验.对回收样品进行的X射线衍射(XRD)分析结果表明:两发顽火辉石回收样品的主相均是单链状结构硅酸盐,而非钙钛矿结构;另外,回收样品中均未观察到氧化物SiO2和(Mg0.92,Fe0.08)O的XRD特征谱线;两发MgO+SiO2回收样品中均观察到SiO2和镁橄榄石(Mg2SiO4)而没有氧化物MgO.实验结果表明:在冲击压缩过程中样品处于钙钛矿结构,在冲击卸载过程中样品发生了由钙钛矿结构向单链状结构的逆转相变;在实验的温压范围内,不可能发生由(Mg0.92,Fe0.08)SiO3向SiO2和(Mg0.92,Fe0.08)O的化学分解相变,顽火辉石的高压相--钙钛矿结构是稳定的.高压加载或卸载过程引起的晶格畸变导致回收样品和原始样品的谱线差异,而高压加载导致钙钛矿型(Mg0.92,Fe0.08)SiO3晶格畸变的可能性更大.     

Synthesis and crystal structure of gold–silver sulfoselenides: morphotropy in the Ag3Au(Se,S)2 series

Gold–silver sulfoselenides of Ag₃Au(Se,S)₂ series—Ag₃AuSe_1.5S_0.5, Ag₃AuSeS, and Ag₃AuSe_0.5S_1.5—have been synthesized by fusing the elements in the required stoichiometric amounts in evacuated quartz ampoules. The single crystal X-ray diffraction data indicate the existence of two solid-solution series: petzite-type cubic Ag₃AuSe₂—Ag₃AuSeS (space group I4₁32) and trigonal Ag₃AuSe_0.5S_1.5—Ag₃AuS₂ (space group $ R\overline{3} c $ ). Both crystal structures differ in the distribution of Ag⁺/Au⁺ cations in the same distorted body-centered cubic sublattice of chalcogen anions. The morphotropic transformation results from the shrinkage of anion packing accompanied by the shortening of Ag–Ag distances. The structure of uytenbogaardtite mineral, earlier incorrectly interpreted as a tetragonal or cubic cell, is similar to that of the trigonal Ag₃AuS₂ end-member.     

Hydrogen incorporation into forsterite in Mg2SiO4–K2Mg(CO3)2–H2O and Mg2SiO4–H2O–C at 7.5–14.0 GPa

Experiments on water solubility in forsterite in the systems Mg₂SiO₄–K₂Mg(CO₃)₂–H₂O and Mg₂SiO₄–H₂O–C were conducted at 7.5–14.0 GPa and 1200–1600 °C. The resulting crystals contain 448 to 1480 ppm water, which is 40–70% less than in the forsterite–water system under the same conditions. This can be attributed to lower water activity in the carbonate-bearing melt. The water content of forsterite was found to vary systematically with temperature and pressure. For instance, at 14 GPa in the system forsterite–carbonate–H₂O the H₂O content of forsterite drops from 1140 ppm at 1200 °C to 450 ppm at 1600 °C, and at 8 GPa it remains constant or increases from 550 to 870 ppm at 1300–1600 °C. Preliminary data for D-H-bearing forsterite are reported. Considerable differences were found between IR spectra of D-H- and H-bearing forsterite. The results suggest that CO₂ can significantly affect the width of the olivine-wadsleyite transition, i.e., the 410-km seismic discontinuity, which is a function of the water content of olivine and wadsleyite.     

The nonlinear elasticity and related properties of anhydrous and hydrous γ-Mg2SiO4: a theoretical study

The second-order elastic constants up to 30 GPa, which encompass the stability field of the spinel forms, their pressure derivatives and the third-order elastic constants of both hydrous and anhydrous -Mg₂SiO₄ have been obtained theoretically. A combination of deformation theory and finite strain elasticity theory has been employed to arrive at the expressions for second-order and third-order elastic constants from the strain energy of the lattice. The strain energy is calculated by taking into account the interactions up to second nearest neighbours in the -Mg₂SiO₄ lattice. This is then compared with the strain-dependent lattice energy from continuum model approximation to obtain the expression of elastic constants. The second-order elastic constants C_ij compare favourably with the measurements in the case of anhydrous as well as hydrous -Mg₂SiO₄ and with other calculations on the anhydrous phase. All the third-order elastic constants of both the compounds are negative. The third-order elastic constant C₁₄₄(–52.41 and –45.07 GPa for anhydrous and hydrous -Mg₂SiO₄, respectively) representing the anisotropy of shear mode has a smaller value than C₁₁₁ (–2443.94 and –2101.25 GPa for anhydrous and hydrous phases, respectively), which corresponds to the longitudinal mode. The pressure-induced variations in the longitudinal elastic constants (i.e.,dC₁₁/dp) are relatively large (4.08 and 4.09 for dry and hydrous ringwoodite, respectively) compared with those for the shear (0.22 and 0.32 for dry and hydrous ringwoodite, respectively) and off-diagonal constants (1.40 and 1.41 for dry and hydrous ringwoodite, respectively). The variation of the shear moduli C_s and anisotropy factor A with pressure have also been studied. The average value of elastic anisotropy is 0.835 in the case of anhydrous -Mg₂SiO₄ and 0.830 in the hydrous phase. The reversal of sign of the Cauchy pressure C₁₂ – C₄₄, which describes the angular character of atomic bonding in metals and other compounds, at around 21 GPa for both the compounds may be a precursor to the phase transition from ringwoodite to periclase and perovskite at an elevated temperature. The aggregate elastic properties like the adiabatic bulk modulus K (175.4 and 150.2 GPa for anhydrous and hydrous phases, respectively), and the isotropic compressional (P) and shear (S) wave velocities were calculated and the mode Grüneisen Parameters (GPs) of the acoustic waves were determined based on the quasi-harmonic approximation. The low temperature limit of both hydrous and anhydrous phases of -Mg₂SiO₄ are positive (1.69 and 1.78, respectively, for hydrous and anhydrous phases) and hence we expect the thermal expansion to be positive down to absolute zero. The Anderson–Grüneisen parameter obtained for hydrous as well as anhydrous phases of -Mg₂SiO₄ from the second-order and third-order elastic constants are 2.30 and 2.29, respectively.     

Influence of hydrogen on Fe–Mg interdiffusion in (Mg,Fe)O and implications for Earth’s lower mantle

Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of MgO in contact with (Mg_0.73Fe_0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in Fe _x Mg_1−x O with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol⁻¹. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the lower mantle.

Mechanisms of the transformations between the α, β and γ polymorphs of Mg2SiO4 at 15 GPa

Data on the mechanisms of mantle phase transformations have come primarily from studies of analogue systems reacted experimentally at low pressures. In order to study transformation mechanisms in Mg₂SiO₄ at mantle pressures, forsterite () has been reacted in the stability field of -phase, at 15 GPa and temperatures up to 900° C, using a multianvil split-sphere apparatus. Transmission electron microscope studies of samples reacted for times ranging from 0.25–5.0 h show that forsterite transforms to -phase by an incoherent nucleation and growth mechanism involving nucleation on olivine grain boundaries. This mechanism and the resultant microstructures are very similar to those observed at much lower pressures in analogue systems (Mg₂GeO₄ and Ni₂SiO₄) as the result of the olivine to spinel () transformation. Metastable spinel () also forms from Mg₂SiO₄ olivine at 15 GPa, in addition to -phase, by the incoherent nucleation and growth mechanism. With time, the spinel progressively transforms to the stable -phase. After 1 h, spinels exhibit a highly striated microstructure along {110} and electron diffraction patterns show streaking parallel to [110] which indicates a high degree of structural disorder. High resolution imaging shows that the streaking results from thin lamellae of -phase intergrown with the spinel. The two phases have the orientation relationship [001]//[001] and [010]//[110] so that the quasi cubic-close-packed oxygen sublattices are continuous between both phases. These microstructures are similar to those observed in shocked meteorites and show that spinel transforms to -phase by a martensitic (shear) mechanism. There is also evidence that the mechanism changes to one involving diffusion-controlled growth at conditions close to equilibrium.     

Batagayite,CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O,a new phosphate mineral from Këster tin deposit (Yakutia,Russia): occurrence and crystal structure

Mineralogy and Petrology - Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O, is a new secondary phosphate mineral from the Këster deposit, Arga-Ynnykh-Khai massif, NE Yakutia, Russia. It is...     

Thermodynamic properties of tooeleite,Fe63+(As3+O3)4(SO4)(OH)4·4H2O

Tooeleite, nominally Fe₆³⁺(As³⁺O₃)₄(SO₄)(OH)₄·4H₂O, is a relatively uncommon mineral of some acid-mine drainage systems. Yet, if it does occur, it does so in large quantities, indicating that some specific conditions favor the formation of this mineral in the system Fe-As-S-O-H. In this contribution, we report the thermodynamic properties of synthetic tooeleite. The sample was characterized by powder X-ray diffraction, scanning electron microscopy, extended X-ray absorption fine-structure spectroscopy, and Mössbauer spectroscopy. These methods confirmed that the sample is pure, devoid of amorphous impurities of iron oxides, and that the oxidation state of arsenic is 3+. Using acid-solution calorimetry, the enthalpy of formation of this mineral from the elements at the standard conditions was determined as −6196.6 ± 8.6 kJ mol⁻¹. The entropy of tooeleite, calculated from low-temperature heat capacity data measured by relaxation calorimetry, is 899.0 ± 10.8 J mol⁻¹ K⁻¹. The calculated standard Gibbs free energy of formation is −5396.3 ± 9.3 kJ mol⁻¹. The log K_sp value, calculated for the reaction Fe₆(AsO₃)₄(SO₄)(OH)₄·4H₂O + 16H⁺ = 6Fe³⁺ + 4H₃AsO₃ + SO₄²⁻ + 8H₂O, is −17.25 ± 1.80. Tooeleite has stability field only at very high activities of aqueous sulfate and arsenate. As such, it does not appear to be a good candidate for arsenic immobilization at polluted sites. An inspection of speciation diagrams shows that the predominance field of Fe³⁺ and As³⁺ overlap only at strongly basic conditions. The formation of tooeleite, therefore, requires strictly selective oxidation of Fe²⁺ to Fe³⁺ and, at the same time, firm conservation of the trivalent oxidation state of arsenic. Such conditions can be realized only by biological systems (microorganisms) which can selectively oxidize one redox-active element but leave the other ones untouched. Hence, tooeleite is the first example of an “obligatory” biomineral under the conditions prevailing at or near the Earth's surface because its formation under these conditions necessitates the action of microorganisms.     

Thermodynamics of (Fe2+, Mn2+, Mg, Ca)3− Al2Si3O12 garnet: a review and analysis

Summary The thermodynamic properties of garnets in the system (Fe²⁺, Mn²⁺, Mg, Ca)₃A1₂Si₃O₁₂ are reviewed. The thermodynamic properties of the three end-member garnets pyrope, almandine and grossular, including their volume, enthalpy of formation, entropy, compressibility and thermal expansion have been well determined. For spessartine enthalpy of formation and heat capacity at low temperatures are needed. Pyrope's unusual behavior in some of its properties is probably related to the presence of the small, light Mg cation, which has a large anisotropic thermal vibration. The thermodynamic mixing properties of the six binaries are also discussed. Good volume of mixing data exist now for all of the binaries, but much work is still required to determine the enthalpies and third-law vibrational entropies of mixing. It is shown that the magnitude of the positive deviations in the volumes of mixing is related to the volume difference between the two end-member components. It is probable that excess entropies, if present, originate at low temperatures below 200 K. Recent²⁹Si NMR experiments have demonstrated the presence of short-range ordering (SRO) of Ca and Mg in pyrope-grossular solid solutions. Short-range order will have to be considered in new models describing the entropies of mixing. Its possible presence in all garnet solid solutions needs to be examined. The mixing properties of pyrope-grossular garnets, which are the best known for any garnet binary, can, in part, be described by the Quasi-Chemical approximation, which gives insight into the microscopic interactions which determine the macroscopic thermodynamic mixing properties. Microscopic properties are best investigated by spectroscopic and computational approaches. Hard mode IR measurements on binary solid solutions show that the range of local microscopic structural distortion is reflected in the macroscopic volumes of mixing. The nature of The contents of this contribution was presented at the IMA Meeting in Toronto in August, 1998. It precedes issues of Mineralogy and Petrology containing thematic sets of IMApapers strain tiields and site relaxation needs to be studied in order to obtain a better understanding of the solid-solution process and energetics in garnet. Critical areas for future experimentation are also addressed.[/p]

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Eine kritische Zusammenstellung und Analyse der thermodynamischen Daten der (Fe²⁺, Mn²⁺, Mg, Ca)₃Al₂Si₃O₁₂ granate

Zusammenfassung In dieser Studie werden die thermodynamischen Eigenschaften der Granate im System (Fe²⁺,Mn²⁺, Mg, Ca)₃Al₂Si₃O₁₂ kritisch zusammengestellt. Die thermodynamischen Eigenschaften der drei Endglied-Granate Pyrop, Almandin und Grossular, einschließlich ihrer Volumina, Bildungswärmen, Entropien, Kompressibilitäten und thermischen Ausdehnungen wurden bereits hinreichend gut bestimmt. Dagegen müssen die Bildungswärme und Tieftemperatur-Wärmekapazität von Spessartin noch gemessen werden. Die Eigenschaften des Pyrops sind wahrscheinlich mit den großen anisotropen Schwingungen des kleinen, leichten Mg-Kations verbunden. Die thermodynamischen Mischungseigenschaften der sechs binären Mischkristallreihen werden ebenfalls diskutiert. Während die Mischungs-Volumendaten der binären Mischreihen gut bekannt sind, müssen ihre Mischungs-Enthalpien und Standard-Mischungsentropien noch ermittelt werden. Es wurde gezeigt, daß die Größe der positiven Exzeß-Volumina mit dem Volumen-Unterschied der zwei Endglied-Komponenten der jeweiligen Mischreihe verknüpft ist. Es ist wahrscheinlich, daß Exzeß-Entropien, wenn vorhanden, erst bei Tieftemperaturen unter 200 K auftreten. Neue²⁹Si NMR-Experimente belegen, daß in Pyrop-Grossular-Mischkristallen Nahordnung von Mg und Ca vorliegt. Der Effekt der Nahordnung muß in künftigen thermodynamischen Modellen berücksichtigt werden. Hieraus ergibt sich die Notwendigkeit, alle Granat-Mischreihen auf mögliche Nahordnung hin zu untersuchen. Die Mischungseigenschaften der Pyrop-Grossular-Mischreihe, die von sämtlichen Granat-Mischreihen am besten bestimmt wurden, können teilweise mit dem Quasi-Chemical-Model beschrieben werden. Dieses Modell ermöglicht die Beschreibung der mikroskopischen Wechselwirkungen, die die makroskopischen thermodynamischen Eigenschaften bestimmen. Mikroskopische Eigenschaften werden am besten mit spektroskopischen Messungen und theoretischen Berechnungen untersucht. Hard-mode IR-Spektroskopie-Messungen an binären Mischreihen zeigen, daß die lokalen mikroskopischen strukturellen Verzerrungen in den makroskopischen Mischungs-Volumina widergespiegelt werden. Die Art der Spannungsfelder und Platz-Relaxationen muß detaillierter untersucht werden, um ein besseres Verständnis des Mischkristall-Bildungsprozsses und der Energetik der Granate zu erreichen. Darüber hinaus werden wichtige künftige Forschungsgebiete diskutiert.

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With 11 Figures     

Mg-Fe partitioning between silicate spinel and magnesiowüstite at high pressure: experimental determination and calculation of phase relations in the system Mg2SiO4-Fe2SiO4

 Mg-Fe partitioning experiments between (Mg,Fe)₂SiO₄ spinel and (Mg,Fe)O magnesiowüstite were carried out at pressures of 17–21.3 GPa at temperatures of 1400 and 1600 °C, using a multi-anvil apparatus, in order to determine interaction parameters of spinel and magnesiowüstite solid solutions and also to constrain the equilibrium boundaries of the postspinel transition in the Fe-rich side in the system Mg₂SiO₄-Fe₂SiO₄. The obtained values of the interaction parameters were 3.4 ± 1.5 and 13.9 ± 1.4 kJ mol⁻¹, respectively, for spinel and magnesiowüstite solid solutions at 19 GPa and 1600 °C. The partitioning data in the system Mg₂SiO₄-Fe₂SiO₄ at 1400 and 1600 °C showed that the transition boundary between spinel and the mixture of magnesiowüstite and stishovite has a negative dP/dT slope. Using the above interaction parameters and available thermodynamic data of the Mg₂SiO₄ and Fe₂SiO₄ end members, the transition boundaries of spinel to the mixture of magnesiowüstite and stishovite were calculated. Within the uncertainties of the data used, the calculated boundaries are in good agreement with the boundaries at 1400 and 1600 °C experimentally determined in this study. The dissociation boundary of Fe₂SiO₄ spinel to wüstite and stishovite, calculated from the thermodynamic data, has a negative slope of −1.5 ± 0.6 MPa K⁻¹. Received: 18 February 1998 / Revised, accepted: 18 October 1999