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.     

Planar and line defects in the sapphirine polytypes

Transmission electron microscopy of various natural and synthetic sapphirines shows the existence of extensive polytypic variation in some samples. In addition to the previously described 1Tc and 2M polytypes, 3Tc, 4M and 5Tc structures are observed. The structural principles underlying the polytypism and the associated diffraction behaviour are reviewed, and the correlation between the nature of the observed stacking faults and their origin during crystal growth, in deformation or as a result of solid-state transformation is discussed. Pairs of c/2 partial dislocations observed in synthetic material provide a likely solid-state transformation mechanism, although the evidence suggests that most observed stacking variation arises during growth.A new type of non-conservative planar defect has been found in sapphirine from Finero, Italy, suggestive of unit-cell scale intergrowth with a surinamite- or pyroxene-like structure. A polysomatic model of the sapphirine and surinamite structures as stackings of pyroxene P and spinel S modules is proposed.     

Back transformation and oxidation of (Mg,Fe)2SiO4 spinels at high temperatures

Based on the in situ and temperature-quench X-ray measurements, the back transformation in the (Mg, Fe)₂SiO₄-spinels has been characterized in terms of the transformation temperature (T _r ),mechanism and kinetics of the transformation, and of the end product(s), with specific emphasis on the effect of oxygen on this transformation. The in situ measurements were conducted to 900° C in vacuum (10^-4 to 10^-5 torr) and to 600° C in air using synchrotron radiation (SR) at Stanford Synchrotron Radiation Laboratory (SSRL). In the quench-type measurements, samples were heated in air to 1100° C, quenched and examined at ambient conditions using the conventional X-ray diffraction facilities. Important results are (1) in vacuum, all the spinels convert back into the olivine phase, with their T _r decreasing with increasing iron content; (2) the spinel olivine back transformation is a nucleation and growth type of transformation and can be described quantitatively using the Avrami equation; (3) in air, the (Mg, Fe)₂SiO₄-spinels with 0.2 mole fraction Fe or more are all oxidized, and the composition and phase of the end products depend upon the temperature and the starting composition; and (4) the oxidation of the iron-rich (Mg, Fe)₂SiO₄-spinels in air occurs at 350–400° C, which is significantly lower than its T _r ( 300° C) in vacuum.     

The elasticity of the upper mantle orthosilicates olivine and garnet to 3 GPa

The elastic moduli of single crystals of pyrope-rich garnet and San Carlos olivine have been measured over a 3 GPa pressure range at room temperature. The combination of improved ultrasonic techniques and this large pressure range provide for more reliable characterization of the pressure dependence of acoustic wave velocities than has previously been possible. First and second pressure derivatives of the velocities have been determined within 1 percent and 10 percent respectively. The Hashin-Shtrikman bounds for the pressure dependences of the bulk and shear moduli of the garnet used in this study are; K = 173.6 GPa, K = 4.93, K = –0.28 GPa^–1, G= 94.9 GPa, G = 1.56, G = –0.08 GPa^–1 and the Hashin-Shtrikman least-upper bounds and greatestlower bounds for the pressure dependences of the bulk and shear moduli of the San Carlos olivine are K=129.8 GPa, K = 4.66, K= –0.15 GPa^–1, G = 77.8 GPa, G = 1.93, G = –0.11 GPa^–1 and K = 129.2 GPa, K = 4.63, K= –0.15 GPa^–1 G = 77.3 GPa, G=1.96, G = –0.11 GPa^–1 respectively. The determination of the room-pressure elastic moduli of this pyrope-almandine garnet removes the previously observed anomaly in the predictions of systematic treatments of variations of the elastic moduli of garnets with composition. The determination of the second pressure derivatives of the moduli of garnet and olivine illustrates the importance of these terms in extrapolations to higher pressures — with K/P for these crystals being reduced by 17 percent and 9 percent respectively over the 3 GPa pressure range.     

Thermal expansion,heat capacity,and entropy of MgO at mantle pressures

The pressure dependence of the Raman spectrum of forsterite was measured over its entire frequency range to over 200 kbar. The shifts of the Raman modes were used to calculate the pressure dependence of the heat capacity, C _v, and entropy, S, by using statistical thermodynamics of the lattice vibrations. Using the pressure dependence of C _v and other previously measured thermodynamic parameters, the thermal expansion coefficient, , at room temperature was calculated from = K _S (T/P) _S C _V/TVK _T, which yields a constant value of ( ln / ln V)_T= 6.1(5) for forsterite to 10% compression. This value is in agreement with ( ln / ln V)_T for a large variety of materials.At 91 kbar, the compression mechanism of the forsterite lattice abruptly changes causing a strong decrease of the pressure derivative of 6 Raman modes accompanied by large reductions in the intensities of all of the modes. This observation is in agreement with single crystal x-ray diffraction studies to 150 kbar and is interpreted as a second order phase transition.     

31P solid-state nuclear magnetic resonance spectroscopy of aluminum phosphate minerals

This study examines the links between ³¹P solidstate NMR studies of aluminum phosphate minerals and their crystallographic structures. We found that ³¹P isotropic chemical shift values, _iso, carry little information about mineral structures. There seems to be no relation between the chemical shift anisotropy, =₃₃–₁₁ (₃₃>₂₂> ₁₁), and indicies of phosphate-tetrahedra distortion. ³¹P¹H heteronuclear magnetic dipole interactions, on the other hand, carry important information about hydrous phosphate mineral structures, information that should prove to be quite valuable in studies of phosphate adsorbed on mineral surfaces. This interaction can be measured through a variety of qualitative and quantitative experiments. It appears that spin diffusion is so rapid that subtle differences in hydrogen-bonding environments cannot be resolved.     

Mineralogical variations in the Delakhari sill,Deccan trap intrusion,central India

The Delakhari sill (maximum thickness cf. 200 m) is the most extensive Deccan Trap instrusion which occurs in central India, between longitutdes 78°3835 to 78°2240 and latitudes 22°26 and 22°2230. Based on petrographic examination, the sill is divided, from bottom to top, into (1) the Lower Chilled Zone (LCZ), up to 8 m thick, marked by abundant interstitial glass and an overall fine grain size, (2) the Olivine-Rich Zone (ORZ), 27 m thick, enriched in olivine (relative to the other zones in the sill), (3) the Central Zone (CZ), 70 m thick, marked by depletion in olivine and overall coarse grain size, (4) the Upper Zone (UZ), 55 m thick, marked by the presence of two chemically and morphologically distinct olivine types and abundant interstitial granophyre, and (5) the Upper Chilled Zone (UCZ), 10–25m thick, marked by abundant interstitial glass.Compositions of the pyroxenes and olivines show an overall increase in Fe/Mg with crystallization, but extensive interzonal and intrazonal variations and overlaps exist. Olivine ranges from Fa₂₄ (ORZ) to Fa₉₅ (UZ). In the UZ and inner UCZ, an equant (Fa_44–50, called type-A olivine) and interstitial skeletal olivine (Fa_70–95, called type-B olivine) occur together. Compositions of the Ca-rich and Ca-poor pyroxenes fall in the range Wo₃₈En₃₄Fs₂₈ to Wo₃₃En₈Fs₅₉ and Wo₁₄En₄₁Fs₄₅ to Wo₁₆En₁₉Fs₆₅, respectively. Overall, the two pyroxene trends converge with Fe-enrichment except for one anomalous sample from the UZ which contains a Ca-rich (Wo₃₄En₈Fs₅₈) and a Ca-poor (Wo₁₀En₁₈Fs₇₂) pyroxene well within the Forbidden Zone of Smith (1972).Compositions of coexisting oxide minerals indicate that the sill crystallized at oxygen fugacities from 10^–10 atm (ORZ) to 10^–13 (UZ). The magma prior to intrusion appears to have been derived from a more primitive melt from which a considerable amount of olivine and plagioclase have fractionated out. A model of open, interrupted fractional crystallization in the sill is proposed to explain the compositional variations exhibited by the major mineral phases.A previous study (Crookshank 1936) concluded that the sill is actually a multiple intrusion and has given rise to the lowermost (flow I) and the topmost (flow III) lava flows in the neighboring area around Tamia (78°4015, 22°2035). The olivines of flows I and III have compositions Fo₈₇ and Fo₈₈ respectively, and are much more Mg-rich than the maximum Mg-rich olivine (Fo₇₆) of the Delakhari sill, refuting the possibility of the sill being the feeder of the lava flows I and III.Geosciences Department, University of Texas at Dallas Contribution No. 338     

Origin and differentiation of picritic arc magmas,Ambae (Aoba), Vanuatu

Key aspects of magma generation and magma evolution in subduction zones are addressed in a study of Ambae (Aoba) volcano, Vanuatu. Two major lava suites (a low-Ti suite and high-Ti suite) are recognised on the basis of phenocryst mineralogy, geochemistry, and stratigraphy. Phenocryst assemblages in the more primitive low-Ti suite are dominated by magnesian olivine (mg 80 to 93.4) and clinopyroxene (mg 80 to 92), and include accessory Cr-rich spinel (cr 50 to 84). Calcic plagioclase and titanomagnetite are important additional phenocryst phases in the high-Ti suite lavas and the most evolved low-Ti suite lavas. The low-Ti suite lavas span a continuous compositional range, from picritic (up to 20 wt% MgO) to high-alumina basalts (<5 wt% MgO), and are consistent with differentiation involving observed phenocrysts. Melt compositions (aphyric lavas and groundmasses) in the low-Ti suite form a liquid-line of descent which corresponds with the petrographically-determined order of crystallisation: olivine + Cr-spinel, followed by clinopyroxene + olivine + titanomagnetite, and then plagioclase + clinopyroxene + olivine + titanomagnetite. A primary melt for the low-Ti suite has been estimated by correcting the most magnesian melt composition (an aphyric lava with 10.5 wt% MgO) for crystal fractionation, at the oxidising conditions determined from olivine-spinel pairs (fo₂ FMQ + 2.5 log units), until in equilibrium with the most magnesian olivine phenocrysts. The resultant composition has 15 wt% MgO and an mg ^Fe2 value of 81. It requires deep (3 GPa) melting of the peridotitic mantle wedge at a potential temperature consistent with current estimates for the convecting upper mantle (T _p 1300°C). At least three geochemically-distinct source components are necessary to account for geochemical differences between, and geochemical heterogeneity within, the major lava suites. Two components, one LILE-rich and the other LILE- and LREE-rich, may both derive from the subducting ocean crust, possibly as an aqueous fluid and a silicate melt respeetively. A third component is attributed to either differnt degrees of melting, or extents of incompatible-element depletion, of the peridotitic mantle wedge.     

The α-β phase transition in cristobalite,SiO2

Cristobalite, a high temperature phase of silica, SiO₂, undergoes a (metastable) first-order phase transition from a cubic, , to a tetragonal, P4₃2₁2 (or P4₁2₁2), structure at around 220° C. The cubic C9-type structure for -cristobalite (Wyckoff 1925) is improbable because of two stereochemically unfavorable features: a 180° Si-O-Si angle and an Si-O bond length of 1.54 Å, whereas the corresponding values in tetragonal -cristobalite are 146° and 1.609 Å respectively. The structure of the -phase is still controversial. To resolve this problem, a symmetry analysis of the (or P4₁2₁2) transition in cristobalite has been carried out based on the Landau formalism and projection operator methods. The starting point is the ideal cubic ( ) C9-type structure with the unit cell dimension a (7.432 Å) slightly larger than the known a dimension (7.195 Å at 205° C) of -cristobalite, such that the Si-O-Si angle is still 180°, but the Si-O bond length is 1.609 Å. The six-component order parameter driving the phase transition transforms according to the X₄ representation. The transition mechanism essentially involves a simultaneous translation and rotation of the silicate tetrahedra coupled along 110. A Landau free-energy expression is given as well as a listing of the three types of domains expected in -cristobalite from the transition. These domains are: (i) transformation twins from a loss of 3-fold axes, (ii) enantiomorphous twins from a loss of the inversion center, and (iii) antiphase domains from a loss of translation vectors 1/2 110 (FP). These domains are macroscopic and static in -cristobalite, and microscopic and dynamic in -cristobalite. The order parameter , couples with the strain components as ², which initiates the structural fluctuations, thereby causing the domain configurations to dynamically interchange in the -phase. Hence, the - cristobalite transition is a fluctuation-induced first-order transition and the -phase is a dynamic average of -type domains.     

Dynamics of the α-β phase transitions in quartz and cristobalite as observed by in-situ high temperature 29Si and 17O NMR

Relaxation times (T₁) and lineshapes were examined as a function of temperature through the - transition for ²⁹Si in a single crystal of amethyst, and for ²⁹Si and ¹⁷O in cristobalite powders. For single crystal quartz, the three ²⁹Si peaks observed at room temperature, representing each of the three differently oriented SiO₄ tetrahedra in the unit cell, coalesce with increasing temperature such that at the - transition only one peak is observed. ²⁹Si T₁'s decrease with increasing temperature up to the transition, above which they remain constant. Although these results are not uniquely interpretable, hopping between the Dauphiné twin related configurations, ₁ and ₂, may be the fluctuations responsible for both effects. This exchange becomes observable up to 150° C below the transition, and persists above the transition, resulting in -quartz being a time and space average of ₁ and ₂. ²⁹Si T₁'s for isotopically enriched powdered cristobalite show much the same behavior as observed for quartz. In addition, ¹⁷O T₁'s decrease slowly up to the - transition at which point there is an abrupt 1.5 order of magnitude drop. Fitting of static powder ¹⁷O spectra for cristobalite gives an asymmetry parameter () of 0.125 at room T, which decreases to <0.040 at=" the=" transition=" temperature.=" the=" electric=" field=" gradient=" (efg)=" and=" chemical=" shift=" anisotropy=" (csa),=" however,=" remain=" the=" same,=" suggesting=" that=" the=" decrease=" in="> is caused by a dynamical rotation of the tetrahedra below the transition. Thus, the mechanisms of the - phase transitions in quartz and cristobalite are similar: there appears to be some fluctuation of the tetrahedra between twin-related orientations below the transition temperature, and the -phase is characterized by a dynamical average of the twin domains on a unit cell scale.     

Partition of Ni between olivine and sulfide: equilibria with sulfide-oxide liquids

The partition of Ni between olivine and monosulfide-oxide liquid has been investigated at 1300–1395° C, =10^–8-9–10^–6.8, and =10^–2.0–10^–0.9, over the composition range 20–79 mol. % NiS. The product olivine compositions varied from Fo98 to Fo59 and from 0.06 to 3.11 wt% NiO. The metal/sulfur ratio of the sulfide-oxide liquid increases with increase in , decrease in , and increase in NiS content. The Ni/Fe exchange reaction has been perfectly reversed using natural olivine and pure forsterite as starting materials. The FeO and NiO contents of olivine from runs equilibrated at the same and form isobaric distributions with NiS content, which, to a first approximation, are dependent at constant temperature and total pressure on a variable term, –0.5 log ( / ). The Ni/Fe distribution coefficient (K _D3) exhibits only a weak decrease from 35 to 29 with increase in from the IW buffer to close to the FMQ buffer. At values higher than FMQ, the sulfide-oxide liquid has the approximate composition (Ni,Fe)₃±_xS₂K _D358. The present K _D3 vs O/(S+O) data define a trend which extrapolates to K _D320 at 10 wt% oxygen in the sulfide-oxide liquid. The compositions of olivine and Ni-Cu sulfides associated with early-magmatic basic rocks and komatiites are consistent, at 1400° C, with a value of -log ( / ) of about 7.7, which is equivalent to 0.0 wt% oxygen in the hypothesized immiscible sulfide-oxide liquid. Therefore, K _D3 would not be reduced significantly from the 30 to 35 range for sulfide-oxide liquids with low oxygen contents.     

Pressure-volume-temperature behavior of γ-Fe2SiO4 (spinel) based on static compression measurements at 400° C

Thirteen energy-dispersive x-ray diffraction spectra for -Fe₂SiO₄ (spinel) collected in situ at 400° C and pressures to 24 GPa constitute the basis for an elevated-temperature static compression isotherm for this important high-pressure phase. A Murnaghan regression of these molar volume measurements yields 177.3 (±17.4) GPa and 5.4(±2.5) for the 400° C, room pressure values of the isothermal bulk modulus (K _{P 0}) and its first pressure derivative (K _{P 0}), respectively. When compared to the room-Tdeterminations of K _{P 0} available in the literature, our 400° C K _{P 0} yields -4.1 (±6.2)×10^-2 GPa/degree for the average value of (K/T) _{P 0} over the temperature interval 25° C<><400°>A five-parameter V(P, T) equation for -Fe₂SiO₄ based on simultaneous regression of our data combined with the elevated P-Tdata of Yagi et al. (1987) and the extrapolated thermal expansion values from Suzuki et al. (1979) yields isochores which have very little curvature [(² T/P ²) _v 0], in marked contrast to the isochores for fayalite (Plymate and Stout 1990) which exhibit pronounced negative curvature [(T/P ²) _v <0]. along=" the=">-Fe₂SiO₄ reaction boundary V_Rvaries from a minimum of approximately 8.3% at approximately 450° C to approximately 8.9% at 1200° C. Extrapolation of the fayalite and -Fe₂SiO₄ V(P, T) relationships to the temperature and pressure of the 400 km discontinuity suggests a V _R of approximately 8.4% at that depth, approximately 10% less than the 9.3% V _R at ambient conditions.     

Diffusion models for corona formation in metagabbros from the Western Grenville Province,Canada

Metagabbro bodies in SW Grenville Province display a variety of disequilibrium corona textures between spinel-clouded plagioclase and primary olivine or opaque oxide. Textural evidence favours a single-stage, subsolidus origin for the olivine coronas and diffusive mass transfer is believed to have been the rate-controlling process. Irreversible thermodynamics have been used to model two different garnet symplectite-bearing corona sequences in terms of steady state diffusion. In the models the flux of each component is related to the chemical potential gradients of all diffusing species by the Onsager or L-coefficients for diffusion. These coefficients are analogous to experimentally determined diffusion coefficients (d), but relate the flux of components to chemical potential rather than concentration gradients.The major constraint on the relative values of Onsager coefficients comes from the observed mole fraction, X, of garnet in the symplectites; in (amph-gt) symplectites X _Gt ^Sym 0.80, compared with 0.75 in (cpx-gt) symplectites. Several models using simple oxide components, and two different modifications of the reactant plagioclase composition, give the following qualitative results: the very low mobility of aluminium appears to control the rate of corona formation. Mg and Fe have similar mobility, and Mg can be up to 6–8 times more mobile than sodium. Determination of calcium mobility is problematical because of a proposed interaction with cross-coefficient terms reflecting uphill Ca-diffusion, i.e., calcium diffusing up its own chemical potential gradient. If these terms are not introduced, it is difficult to generate the required proportions of garnet in the symplectite. However, at moderate values of the cross-coefficient ratios, Mg can be up to 4–6 times more mobile than calcium (L _MgMg/L_CaCa<4–6) and="" calcium="" must="" be="" 3–4="" times="" more="" mobile="" than="" aluminium="">L _CaCa/L_AlAl>3).     

Mg tracer diffusion in synthetic forsterite and San Carlos olivine as a function of P,T and fO2

We present new experimental data on Mg tracer diffusion in oriented single crystals of forsterite (Fo₁₀₀) and San Carlos olivine (Fo₉₂) between 1000–1300° C. The activation energies of diffusion are found to be 400 (±60) kJ/mol (96 kcal/mol) and 275 (±25) kJ/mol (65 kcal/ mol) in forsterite and San Carlos olivine, respectively, along [001] at a fO₂ of 10^–12 bars. There is no change in activation energy of Mg tracer diffusion within this temperature range. Mg tracer diffusion in a nominally pure forsterite is found to be anisotropic (D_c > D_a > D _b) and a function of fO₂. This fO₂ dependence is different from that in olivine containing Fe as a major element, which suggests that the diffusion mechanism of Mg in forsterite is different from that in Fe-bearing olivine at least over some range of fO₂. The diffusion mechanism in nominally pure forsterites may involve impurities present below the limits of detection or alternately, Si or Fe³⁺ interstitial defects, Fe being present as impurity (ppm level) in forsterite. Pressure dependence of Mg tracer diffusivity in forsterite measured to 10 GPa in a multianvil apparatus yields an activation volume of approximately 1–3.5 cm³/ mol. It is found that presence of small amounts of hydrogen bearing species in the atmosphere during diffusion anneal (f_H2 0.2 bars, f_H20 0.24 bars) do not affect Mg tracer diffusion in forsterite within the resolution of our measurement at a total pressure of 1 bar. The observed diffusion process is shown to be extrinsic; hence extrapolation of the diffusion data to lower temperatures should not be plagued by uncertainties related to change of diffusion mechanism from intrinsic to extrinsic.     

Systematic study of liquidas phase relations in olivine melilitite +H2O +CO2 at high pressures and petrogenesis of an olivine melilitite magma

Near-liquidus phase relationships of a spinel lherzolite-bearing olivine melilitite from Tasmania were investigated over a P, T range with varying , , and . At 30 kb under MH-buffered conditions, systematic changes of liquidus phases occur with increasing ( = CO₂/CO₂ +H₂O+olivine melilitite). Olivine is the liquidus phase in the presence of H₂O alone and is joined by clinopyroxene at low . Increasing eliminates olivine and clinopyroxene becomes the only liquidus phase. Further addition of CO₂ brings garnet+orthopyroxene onto the liquidus together with clinopyroxene, which disappears with even higher CO₂. The same systematic changes appear to hold at higher and lower pressures also, only that the phase boundaries are shifted to different . The field with olivine- +clinopyroxene becomes stable to higher with lower pressure and approaches most closely the field with garnet+orthopyroxene+clinopyroxene at about 27 kb, 1160 °C, 0.08 and 0.2 (i.e., 6–7% CO₂+ 7–8% H₂O). Olivine does not coexist with garnet+orthopyroxene+clinopyroxene under these MH-buffered conditions. Lower oxygen fugacities do not increase the stability of olivine to higher and do not change the phase relationships and liquidus temperatures drastically. Thus, it is inferred that olivine melilitite 2927 originates as a 5% melt (inferred from K_{2 O} and P₂O₅ content) from a pyrolite source at about 27kb, 1160 dg with about 6–7% CO₂ and 7–8% H₂O dissolved in the melt. The highly undersaturated character of the melt and the inability to find olivine together with garnet and orthopyroxene on the liquidus (in spite of the close approach of the respective liquidus fields) can be explained by reaction relationships of olivine and clinopyroxene with orthopyroxene, garnet and melt in the presence of CO₂.     

Mössbauer study of the thermal decomposition of lepidocrocite and characterization of the decomposition products

The lepidocrocite (-FeOOH) to maghemite (-Fe₂O₃), and the maghemite to hematite (-Fe₂O₃) transition temperatures have been monitored by TGA and DSC measurements for four initial -FeOOH samples with different particle sizes. The transition temperature of -FeOOH to -Fe₂O₃ and the size of the resulting particles were not affected by the particle size of the parent lepidocrocite. In contrast, the -Fe₂O₃ to -Fe₂O₃ transition temperature seems to depend on the amount of excess water molecules present in the parent lepidocrocite. Thirteen products obtained by heating for one hour at selected temperatures, were considered. Powder X-ray diffraction was used to qualify their composition and to determine their mean crystallite diameters. Transmission electron micrographs revealed the particle morphology. The Mössbauer spectra at 80 K and room temperature of the mixed and pure decomposition products generally had to be analyzed with a distribution of hyperfine fields and, where appropriate, with an additional quadrupole-splitting distribution. The Mössbauer spectra at variable temperature between 4.2 and 400 K of two single-phase -Fe₂O₃ samples with extremely small particles show the effect of superparamagnetism over a very broad temperature range. Only at the lowest temperatures (T55 K), two distributed components were resolved from the magnetically split spectra. In the external-field spectra the m_I=0 transitions have not vanished. This effect is an intrinsic property of the maghemite particles, indicating a strong spin canting with respect to the applied-field direction. The spectra are successfully reproduced using a bidimensional-distribution approach in which both the canting angle and the magnetic hyperfine field vary within certain intervals. The observed distributions are ascribed to the defect structure of the maghemites (unordered vacancy distribution on B-sites, large surface-to-bulk ratio, presence of OH^- groups). An important new finding is the correlation between the magnitude of the hyperfine field and the average canting angle for A-site ferric ions, whereas the B-site spins show a more uniform canting. The Mössbauer parameters of the two hematite samples with MCD₁₀₄ values of respectively 61.0 and 26.5 nm display a temperature variation which is very similar to that of small-particle hematites obtained from thermal decomposition of goethite. However, for a given MCD the Morin transition temperature for the latter samples is about 30 K lower. This has tentatively been ascribed to the different mechanisms of formation, presumably resulting in slightly larger lattice parameters for the hematite particles formed from goethite, thus shifting the Morin transition to lower temperatures.Senior Research Associate, National Fund for Scientific Research (Belgium)     

Formulation of the thermodynamic functions for mantle minerals: MgO as an example

The formulas for thermodynamic functions for minerals are presented, couched in terms of the important thermodynamic variable K_T= (P/T)_v, where is the volume thermal expansivity and K_T is the isothermal bulk modulus. Presenting the formulas in this way leads to simplification since K_T as a product varies only slightly with volume, and is close to being independent of temperature at high temperature. Using our equations, we present as examples some computed data in the form of graphs on the entropy, internal energy, Helmholtz free energy, and Gibbs free energy in the high temperature regime (up to 2000 K) and for high compression (up to 0.7), for MgO. For entropy, knowledge of the V, T dependence of K_T is sufficient. For enthalpy and internal energy, the equation of state is needed in addition.     

Naturally decorated dislocations in olivine from peridotite xenoliths

Dislocations decorated by hematite and magnetite have been observed optically in the olivine grains of undeformed or highly annealed peridotite xenoliths from Hawaii and Baja California ( 5 × 10⁵ cm^–2). The observed structures include loops, low-angle boundaries, and structures produced by multiple cross-glide of [100] screws. Loops are almost invariably parallel to (001). Simple arrays of parallel dislocations lie predominantly in (100), (010) and (001) with dislocation lines subparallel to low-index directions. [100] screws pinned to (100) boundaries are frequently seen to bow out on (001). Preliminary electron petrography has confirmed that all dislocations are decorated.     

Octahedral-site Fe2+ quadrupole splitting distributions from Mössbauer spectroscopy along the (OH, F)-annite join

We have performed a detailed Mössbauer study of synthetic annites on the (OH, F)-join. Recently developed data treatment and spectral analysis methods were used to extract true intrinsic Fe²⁺ quadrupole splitting distributions (QSDs) that represent the most information that can be resolved from the spectra. The overall room temperature (RT) QSDs can be consistently interpreted in terms of four QSD contributions (or populations) centered at: QS_HH2.55 mm/s for Fe²⁺O₄(OH)₂ octahedra (cis and trans not resolved), QS_HF 2.35 mm/s for Fe²⁺O₄(OH)F octahedra (cis and trans not resolved), QS_cFF2.15 mm/s for cis-Fe²⁺O₄F₂ octahedra, and QS_tFF 1.5 mm/s for trans-Fe²⁺O₄F₂ octahedra. Each such contribution has a width ( 0.2 mm/s) caused by distortions of the octahedra. Minor contributions due to Fe²⁺O₅(OH) and Fe²⁺O₅F octahedra probably also contribute to the overall Fe²⁺ QSDs. The ferric iron spectral components were also characterized. Here, two distinct types of octahedral Fe³⁺ contributions are seen and interpreted as being due mainly to Fe³⁺O₅OH and Fe³⁺O₅F octahedra, respectively. Tetrahedral Fe³⁺ is seen only in the OH-annite end-member and the total Fe³⁺ content drops significantly on addition of F. On leave from: Department of Materials Physics, University of Science and Technology Beijing, 100083 Beijing, China     

Mafic magma batches at Vesuvius: a glass inclusion approach to the modalities of feeding stratovolcanoes

Glass inclusions in olivine and diopside phenocrysts from pyroclasts of various eruptions of Vesuvius are representative of the magmas that supplied the volcano in the last 4–5000 years. During this interval the volcano alternated between open conduit activity (e.g. 1944 and 1906 eruptions) with long pauses interupted by Plinian and sub-Plinian eruptions (e.g. 3360 B.P. Avellino, A.D. 79 Pompei, A.D. 472 Pollena). The eruptive behaviour was conditioned in all cases by the presence of shallow reservoirs: two cases are distinguished: (1) small and very shallow, 1906-type; (2) large and deeper Plinian-sub-Plinian magma chamber. Lapilli of 1906 lava fountains contain olivine (Fo_89.5–90.4) including Cr-spinel [Cr/(Cr+Al)] (Cr#>75) and volatile-K-rich tephritic glasses, which represent the first recognized Vesuvius primary magmas. Mg-poorer olivine (Fo_83–89) also occurs in 1906 and 1944 products; it formed within the shallow reservoir, together with pyroxene and leucite, between 1200 and 1130°C, from K-tephritic melts (MgO=6–8 wt%). The Plinian and sub-Plinian pumices contain diopside, phlogopite and minor olivine (Fo_85–87) representing adcumulates wrenched from the chamber walls. Glass inclusions in diopside (and some olivine) range from K-basalt to K-tephrite (MgO=6–8 wt%), with homogenization temperature of 1130–1170°C. They have been regarded as representative of the magmas supplying the Plinian-sub-Plinian chamber(s). The Avellino glass inclusions have K-basaltic compositions, contrasting with the mostly K-tephritic Pompei and Pollena inclusions. They display lower C1 and P contents with respect to the younger tephritic melts, and these variations should reflect primary features of the mantle-derived magmas. The primary and the near-primary Vesuvius magmas, as illustrated by melt inclusions, emphasize high K, P and volatile (H₂O, Cl, F, S) contents, with high K₂O/H₂O (2–2.5), Cl/F (2.5) and Cl/S (2–3) ratios, consistent with a metasomatized mantle source, and distinguishing the Vesuvius potassic primary magmas from those of the northern part of the Roman Province.