The effect of crystal field stabilization on the olivine→spinel transition in the system Mg2SiO4 - Fe2SiO4

Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe²⁺ which is a major constituent of the upper mantle. Previous calculations for Fe₂SiO₄ ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S _CFS). We have calculated free energy changes (ΔG _CFS) due to differences of crystal field splittings between Fe₂SiO₄ spinel and fayalite from: ΔG _CFS=?ΔCFSE?TΔS _CFS, as functions of P and T, for different energy splittings of t _2g orbital levels of Fe²⁺ in spinel. The results indicate that ΔG _CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe₂SiO₄, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg_1?x Fe _x )₂SiO₄ are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.     

The lattice energy of forsterite. Charge distribution and formation enthalpy of the SiO 4 4− ion

In the lattice energy expression of forsterite, based on a Born-Mayer (electrostatic+repulsive+dispersive) potential, the oxygen charge z _o, the hardness parameter ρ and the repulsive radii r _Mg and r _Si appear as unknown parameters. These were determined by calculating the first and second partial derivatives of the energy with respect to the cell edges, and equalizing them to quantities related to the crystal elastic constants; the overdetermined system of equations was solved numerically, minimizing the root-mean-square deviation. To test the results obtained, the SiO ₄ ^4? ion was assumed to move in the unit-cell, and the least-energy configuration was sought and compared with the experimental one. By combining the two methods, the optimum set of parameters was: z _o=?1.34, ρ=0.27 Å, r _Mg=0.72 Å, r _Si=0.64 Å. The values ?8565.12 and ?8927.28 kJ mol^?1 were obtained, respectively, for the lattice energy E _Land for its ionic component E _L ⁰ ,which accounts for interactions between Mg²⁺ and SiO ₄ ^4? ions only. The charge distribution calculated on the SiO ₄ ^4? ion was discussed and compared with other results. Using appropriate thermochemical cycles, the formation enthalpy and the binding energy of SiO ₄ ^4? were estimated to be: ΔH _f(SiO ₄ ^4? )=2117.6 and E(SiO ₄ ^4? )=708.6 kJ mol^?1, respectively.     

Thermodynamic properties of Fe-rich smectite-nontronite

The results of thermochemical studies are reported for nontronite samples from the Pinares-de-Majari (Eastern Cuba) (Sample I) and Kempirsai serpentine massif (South Urals, Kazakhstan) (Sample II). The enthalpies of formation of dehydrated hydroxyl-bearing nontronites from elements were determined by melt dissolution calorimetry using high-temperature heat-flux Tiana-Calvet microcalorimeter: Δ _f H _el ^o (298.15 K): ?4958 ± 13 kJ/mol for Mg_0.4(Fe _1.5 ³⁺ Mg_0.4Ni_0.1)[Si_3.7Al_0.3O₁₀](OH)₂ (I) and ?5003.6 ± 8.0 kJ/mol for Mg_0.3Na_0.1Ca_0.1(Fe _1.4 ³⁺ Mg_0.5Ni_0.1)[Si_3.7Al_0.3O₁₀](OH)₂ (II). It was determined experimentally that the enthalpy of dehydration (removal of molecular adsorption and interlayer water) of the studied nontronites is 6 ± 2 kJ per 1 mole H₂O. The enthalpy of formation of nontronite of theoretical composition Mg_0.15Fe ₂ ³⁺ [Si_3.7Al_0.3]O₁₀(OH)₂ was estimated at ?4750 kJ/mol. The Gibbs free energies of formation of the nontronites were calculated.     

Thermodynamic properties of copper carbonates — malachite Cu2(OH)2CO3 and azurite Cu3(OH)2(CO3)2

The thermodynamic properties of the copper carbonates malachite and azurite have been studied by adiabatic calorimetry, by heat-flux Calvet Calorimetry, by differential thermal analysis (DTA) and by thermogravimetrie (TGA) analysis. The heat capacities, C _p ⁰ of natural malachite and azurite have been measured between 3.8 and 300 K by low-temperature adiabatic calorimetry. The heat capacity of azurite exhibits anomalous behavior at low temperatures. At 298.15 K the molar heat capacities C _p ⁰ and the third law entropies S _298.15 ⁰ are 228.5±1.4 and 254.4±3.8 J mol^?1 K^?1 for azurite and 154.3±0.93 and 166.3±2.5 J mol^?1 K^?1 for malachite. Enthalpies of solution at 973 K in lead borate 2PbO·B₂O₃ have been measured for heat treated malachite and azurite. The enthalpies of decomposition are 105.1±5.8 for azurite and 66.1±5.0 kJ mol^? for malachite. The enthalpies of formation from oxides of azurite and malachite determined by oxide melt solution calorimetry, are ?84.7±7.4 and ?52.5±5.9 kJ mol^?1, respectively. On the basis of the thermodynamic data obtained, phase relations of azurite and malachite in the system Cu²⁺-H₂O-CO₂ at 25 and 75 °C have been studied.     

Supergene alteration of the Mt Windarra nickel sulphide ore deposit,Western Australia

Three main zones of progressive oxidation, termed the transition, violaritepyrite and oxide zones, can be delineated in the supergene profile of the Mt Windarra massive/matrix ore deposit. In the broad transition zone from pure primary ore, pentlandite is progressively oxidised to an iron rich violarite of composition Co_0.02Fe_1.38Ni_1.60 S₄, releasing Fe²⁺ and Ni²⁺ ions into solution. Up to 43% of this Ni²⁺ moves to nearby pyrrhotite margins which are replaced firstly by nickeliferous smythite and then by a second lamellar-textured violarite with an even higher iron content but lacking in cobalt (approximately Fe_1.6Ni_1.4S₄). On completion of violaritisation of the pentlandite, violaritisation of the pyrrhotite also ceases and the remainder of the pyrrhotite is rapidly replaced by secondary pyrite/marcasite, siderite and void space, this reaction defining the top of transition zone. Both sulphur and nickel are extracted from solution and further Fe²⁺ ions are released into solution. The violarite-pyrite zone is characterised by the absence of pentlandite and pyrrhotite and continued stability of violarite and secondary iron disulphides. Most, if not all, of the iron generated by these oxidation reactions precipitates as magnesian siderite at the expense of magnesite, giving rise to solutions containing mainly Mg²⁺ and Ni²⁺ ions. At and just above the water table atmospheric oxygen is reduced while the sulphides are oxidised to sulphate and hydroxides. Much of the iron remains in situ as characteristic goethite relicts while nickel and copper are leached, producing the enrichment below the water table. The overall genetic model proposed is electrochemical and is analogous to the corrosion of a piece of metallic iron partially immersed in differentially aerated water.     

Thermodynamic properties of Pd chloride complexes and the Pd2+(aq) ion in aqueous solutions

Based on the expert review of literature data on the thermodynamic properties of species in the Cl-Pd system, stepwise and overall stability constants are recommended for species of the composition [PdCl _n ]^{2 ? n} , and the standard electrode potential of the half-cell PdCl ₄ ^2? /Pd(c) is evaluated at E _298,15° = 0.646 ± 0.007 V, which corresponds to Δ _f G _298.15° = ?400.4 ± 1.4 kJ/mol for the ion PdCl ₄ ^2? (aq). Derived from calorimetric data, Δ _f H _298.15° PdCl ₄ ^2? (aq) = ?524.6 ± 1.6 kJ/mol and Δ _f H _298.15° Pd²⁺(aq) = 189.7 ± 2.6 kJ/mol. The assumed values of the overall stability constant of the PdCl ₄ ^2? ion and the standard electrode potential of the PdCl ₄ ^2? /Pd(c) half-cell correspond to Δ _f G _298.15° = 190.1 ± 1.4 kJ/mol and S _298.15° = ?94.2 ± 10 J/(mol K) for the Pd²⁺(aq) ion.     

Thermodynamic parameters of CaMgSi2O6-Mg2Si2O6 pyroxenes based on regular solution and cooperative disordering models

Thermodynamic parameters for the reaction: $$\begin{gathered} Mg_2 Si_2 O_6 = Mg_2 Si_2 O_6 \hfill \\ enstatite clinopyroxene \hfill \\ \end{gathered} $$ in the system CaO-MgO-SiO₂ have been deduced from phase equilibrium and enthalpy of solution data. From the regular solution theory, the seventeen currently available reversed experimental compositions of coexisting enstatite and clinopyroxene, presumed to be ordered diopside, lead, by a statistical regression, to the following best fit parameters: ΔH ^o=6.80 kJ ΔS ^o=2.75 J/K W _H ^Cpx =24.47 kJ (regular solution enthalpy parameter) W _V ^Cpx =0.105 J/bar (regular solution volume parameter). The derived parameters are not significantly affected by the (necessary) choice of W ^Opx in the range 20–50 kJ. The above values are in very good agreement with deductions from the solution calorimetry on synthetic CaMgSi₂O₆-Mg₂Si₂O₆ clinopyroxenes of Newton et al. (1979), which also places bounds on possible departures from the optimal values of these parameters. The calorimetric data may also be interpreted in terms of a Bragg-Williams cooperative-disordering model (Navrotsky and Loucks, 1977), in which diopside-structure clinopyroxene and a ‘relaxed’ low-Ca clinopyroxene (‘Fe-free pigeonite’) approach each other in composition, structural state, and stability with increasing temperature. The ΔH ^o parameter deduced from the regular solution theory is reinterpreted as the enthalpy change of enstatite to Mg₂Si₂O₆ pigeonite; the ΔH ^o of the transformation of enstatite to the diopside structure would, in this case, be considerably larger than 6.8 kJ. The curvature of the enthalpy of solution data, explained by the regular solution theory in terms of M2-site energetics (involving W _H ^cpx ), is reinterpreted as due to disordering and ‘relaxation’ in the Navrotsky-Loucks model. Although the regular solution theory with the best-fit parameters accounts for all of the reversed enstatite and diopside compositions to within 18 ° C, and is a convenient representation of the phase equilibria for purposes of geothermometry, the disordering model is, at the present level of knowledge, equally valid and allows for a region of stability of two coexisting clinopyroxenes.     

Calorimetric study of high-pressure polymorphs of MnSiO3

With increasing pressure, MnSiO₃ rhodonite stable at atmospheric pressure transforms to pyroxmangite, then to clinopyroxene and further to tetragonal garnet, which finally decomposes into MnO (rocksalt) plus SiO₂ (stishovite). High temperature solution calorimetry of synthetic rhodonite, clinopyroxene and garnet forms of MnSiO₃ was used to measure the enthalpies of these transitions. ΔH ₉₇₄ ⁰ for the rhodonite-clinopyroxene and ΔH ₂₉₈ ⁰ for the clinopyroxene-garnet transition are 520±490 and 8,270±590 cal/mol, respectively. The published data on the enthalpy of the rhodonite-pyroxmangite transition, phase equilibrium boundaries, compressibility and thermal expansion data are used to calculate entropy changes for the transitions. The enthalpy, entropy and volume changes are very small for all the transitions among rhodonite, pyroxmangite and clinopyroxene. The calculated boundary for the clinopyroxene-garnet transition is consistent with the published experimental results. The pyroxene-garnet transition in several materials, including MnSiO₃, is characterized by a relatively small negative entropy change and large volume decrease, resulting in a small positiveP – T slope. The disproportionation of MnSiO₃ garnet to MnO plus stishovite and of Mn₂SiO₄ olivine to garnet plus MnO are calculated to occur at about 17–18 and 14–15 GPa, respectively, at 1,000–1,500 K.     

Thermodynamics of plagioclase II: Temperature evolution of the spontaneous strain at the I\bar 1 \leftrightarrow P\bar 1 phase transition in anorthite

The temperature dependence of the lattice parameters of pure anorthite with high Al/Si order reveals the predicted tricritical behaviour of the \(I\bar 1 \leftrightarrow P\bar 1\) phase transition at T _c ^* =510 K. The spontaneous strain couples to the order parameter Q° as x _i∝S _xQ ⁱ Q°² with S _xQ ¹ =4.166×10^?3, S _xQ ² =0.771×10^?3, S _xQ ³ =?7.223×10^?3 for the diagonal elements. The temperature dependence of Q° is $$Q^{\text{o}} = \left( {1 - \frac{T}{{510}}} \right)^\beta ,{\text{ }}\beta = \tfrac{{\text{1}}}{{\text{4}}}$$ A strong dependence of T _c ^* , S _xQ ⁱ and β is predicted for Al/Si disordered anorthite.     

Electron paramagnetic resonance study of iron(III) and manganese(II) in the glassy and crystalline environments of synthetic fayalite and tephroite

Crystals of the olivine minerals, tephroite (Mn₂SiO₄) and fayalite (Fe₂SiO₄) containing manganese(II) and iron (II and trace of III), respectively, were synthesized. Glasses were prepared from these crystalline materials by a splat-quench technique. Measurement of electron paramagnetic resonance (EPR) of all these powdered samples at room temperature show that the g-factors of Mn²⁺ in both glassy and crystalline environments (g_eff = 2.004) are the same, although the EPR linewidths (for glass, ΔH_pp = 200 G; for crystals ΔH_pp = 287 G) suggest less clustering of paramagnetic Mn²⁺ ions in the glass. Mn²⁺ probably occupies a distorted octahedral site in the tephroite crystal structure, although a four-fold coordination is suggested from other spectroscopic investigation on this glass. The EPR parameters of Fe³⁺ in synthetic fayalite glass (g_eff = 2.01 and 6.00; ΔH_pp=150 and 1375 G, respectively, for the high and low field resonances) and powdered crystals (g_eff = 3.31 and ΔH_pp = 900 G) indicated that Fe³⁺ ion in the crystals, is probably located in a distorted tetragonal site M2 and an axial environment has been proposed in the glassy system.     

Thermodynamic calculation of peridotite phase relations in the system MgO-Al2O3-SiO2-Cr2O3, with some geological applications

The system MgO-Al₂O₃-SiO₂(MAS) comprises 88–90% of the bulk composition of an average peridotite. The MAS ternary is thus a suitable starting point for exploring peridotite phase relations in multicomponent natural systems. The basic MAS phase relations may be treated in terms of the reactions (see list of symbols etc).

1. py (in Gt)=en (in Opx)+mats (in Opx),
2. en (in Opx)+sp (in Sp)=mats (in Opx)+fo (in Ol), and
3. py (in Gt)+fo (in Ol)=en (in Opx)+sp (in Sp).

Extensive reversed phase equilibria data on these three reactions by Danckwerth and Newton (1978), Perkins et al. (1981), and Gasparik and Newton (1984) employing identical experimental methods in the same laboratory have been used by us to deduce the following internally consistent thermodynamic data applying the technique of linear programming:ΔH ₂₉₈₍₁₎ ⁰ = 2536 J, ΔS ₂₉₈₍₁₎ ⁰ =? 6.064 J/K;ΔH ₂₉₈₍₂₎ ⁰ = 29435 J, ΔS ₂₉₈₍₂₎ ⁰ = 8.323 J/K; andΔH ₂₉₈₍₃₎ ⁰ =?26899 J, ΔS ₂₉₈₍₃₎ ⁰ =?14.388 J/K.These data are also found to be consistent with results of calorimetry. Figure 2 shows the calculated phase relations based on our thermodynamic data; they are consistent with the phase equilibria experiments. Successful extension of the MAS phase relations to multicomponent peridotites pivots on the extent to which the effects of the “non-ternary” (i.e. other than MAS) components can be quantitatively handled. Particularly hazardous in this context is Cr₂O₃, although it barely makes up 0.2 to 0.5 wt% of such rocks. This is because Cr⁺³ fractionates extremely strongly into Sp. This study focuses on the peridotite phase relations in the MgO-Al₂O₃-SiO₂-Cr₂O₃ (MASCr) quaternary. Thermodynamic calculations of the MASCr phase relations have been accomplished by using ΔH ₂₉₈ ⁰ and ΔS ₂₉₈ ⁰ values for the reactions (1) through (3) indicated above, in conjunction with data on thermodynamic mixing properties of

1. binary Sp (sp-pc) crystalline solution (Oka et al. 1984),
2. ternary Opx (en-mats-mcts) crystalline solution (this study), and
3. binary Gt (py-kn) crystalline solution (this study).

The results are shown in P-T projections (Figs. 3a and b) and isobaric-isothermal sections of MASCr in a projection through the component fo onto the SiO₂-Al₂O₃-Cr₂O₃ ternary (Figs. 4a and b). The most important results of this work may be summarized as follows:

1. With increasing incorporation of Cr⁺³ into Sp and Gt, the X _mats isopleths of the reactions (1) and (2) are shifted to higher temperatures (Fig. 3a); simultaneously, the spinel-peridotite to garnet-peridotite phase transition is moved to higher pressures (Fig. 3b).
2. At identical P and T, the X _mats values of Opx coexisting in equilibrium with Ol and Sp is strongly dependent upon the X _pc value in the latter phase (Figs. 4a and b). Accurate correction for the composition of Sp is, therefore, a necessary precondition for geothermometry of the spinelperidotites.
3. The discrepant temperatures reported by Sachtleben und Seck (1981, Fig. 5) from the spinel-peridotites of the Eifel area (systematically too high temperatures as a function of X _pc in Sp) are demonstrated to be the result of ignoring the nonideality in the chromian spinels.

     

On the nonstoichiometry and point defects of olivine

This paper presents the point-defect thermodynamics for fayalite and olivine solid solutions (Fe _x Mg_1?x )₂SiO₄. By means of thermogravimetry, the metal-to-oxygen ratio of these silicates has been determined as a function of oxygen potential, compositionx and temperature. Experiments were performed in the range of 1,000° C≦T≦1,280° C and 0.2≦x≦1.0. It is found that V _Me ^″ , Fe _Me ^· and the associate {Fe′ _Si ^′ Fe _Me ^· } are the majority defects. With this knowledge it is possible to calculate the nonstoichiometry at given temperature as a function of \(p_{O_2 } \) and \(a_{SiO_2 } \) . The cation vacancy concentration shows a \(p_{O_2 }^{1/5} \) -dependence (forx≧0.2) and increases at givenT and \(p_{O_2 } \) almost exponentially with compositionx. In the composition range studied here, the silicates show an oxygen excess, and FeO is more soluble in the olivine than SiO₂.     

Cancrinite and cancrisilite in the Khibina-Lovozero alkaline complex: Thermochemical and thermal data

The paper presents the results of a thermochemical and thermal study of cancrinite, (Na_6.93Ca_0.545K_0.01)_Σ7.485[(Si_6.47Al_5.48Fe_0.05)_Σ12O₂₄](CO₃)_1.25 · 2.30 H₂O, and cancrisilite, (Na_7.17 Ca_0.01)_Σ7.18[(Si_7.26Al_4.70Fe_0.04)_Σ12O₂₄][(CO₃)_1.05(OH)_0.21(PO₄)_0.04(SO₄)_0.01] · 2.635 H₂O, from the Khibina-Lovozero Complex, Kola Peninsula, Russia. Stages of the thermal decomposition of these minerals were studied using IR spectroscopy. The enthalpies of formation of the minerals from elements were determined by melt drop solution calorimetry: Δ _f H _el ⁰ (298.15 K) = ?14 490 ± 16 kJ/mol for cancrinite and ?14302 ± 17 kJ/mol for cancrisilite. The values of Δ _f H _el ⁰ (298.15 K), S ^o(298.15 K), and Δ _f H _el ⁰ (298.15 K) are determined for cancrinite and cancrisilite of theoretical composition.     

Thermodynamics and crystal chemistry of the hematite–corundum solid solution and the FeAlO3 phase

High-temperature oxide-melt calorimetry and Rietveld refinement of powder X-ray diffraction patterns were used to investigate the energetics and structure of the hematite–corundum solid solution and ternary phase FeAlO₃ (with FeGaO₃ structure). The mixing enthalpies in the solid solution can be described by a polynomial ΔH_mix=WX _hem(1?X _hem) with W=116 ± 10 kJ mol^?1. The excess mixing enthalpies are too positive to reproduce the experimental phase diagram, and excess entropies in the solid solution should be considered. The hematite–corundum solvus can be approximately reproduced by a symmetric, regular-like solution model with ΔG _excess=(W _H ?TW _S )X _hem X _cor, where W _H= 116 ± 10 kJ mol^?1 and W _S =32 ± 4 J mol^?1 K^?1. In this model, short-range order (SRO) of Fe/Al is neglected because SRO probably becomes important only at intermediate compositions close to Fe:Al=1:1 but these compositions cannot be synthesized. The volume of mixing is positive for Al-hematite but almost ideal for Fe-corundum. Moreover, the degree of deviation from Vegard's law for Al-hematite depends on the history of the samples. Introduction of Al into the hematite structure causes varying distortion of the hexagonal network of oxygen ions while the position of the metal ions remains intact. Distortion of the hexagonal network of oxygen ions attains a minimum at the composition (Fe_0.95Al_0.05)₂O₃. The enthalpy of formation of FeAlO₃ from oxides at 298 K is 27.9 ± 1.8 kJ mol^?1. Its estimated standard entropy (including configurational entropy due to disorder of Fe/Al) is 98.9 J mol^?1 K^?1, giving the standard free energy of formation at 298 K from oxides and elements as +19.1 ± 1.8 and ?1144.2 ± 2.0 kJ mol^?1, respectively. The heat capacity of FeAlO₃ is approximated as C _p (T in K)= 175.8 ? 0.002472T ? (1.958 × 10⁶)/T ²? 917.3/T ^0.5+(7.546 × 10^?6) T ² between 298 and 1550 K, based on differential scanning calorimetric measurements. No ferrous iron was detected in FeAlO₃ by Mössbauer spectroscopy. The ternary phase is entropy stabilized and is predicted to be stable above about 1730 ± 70 K, in good agreement with the experiment. Static lattice calculations show that the LiNbO₃-, FeGaO₃-, FeTiO₃-, and disordered corundum-like FeAlO₃ structures are less stable (in the order in which they are listed) than a mechanical mixture of corundum and hematite. At high temperatures, the FeGaO₃-like structure is favored by its entropy, and its stability field appears on the phase diagram.     

Mechanism and kinetics of pseudomorphic mineral replacement reactions: A case study of the replacement of pentlandite by violarite

Although pseudomorphic mineral replacement reactions are common in all geological environments, and have long been considered important to many geological processes such as metamorphism, metasomatism, diagenesis, and chemical weathering, their mechanisms are still not well known. We present a combined textural and kinetic study of the replacement of pentlandite, (Fe,Ni)₉S₈, by violarite (NiFe)₃S₄, and describe the mechanisms and kinetic behavior of this reaction by considering the role of the fluid phase, the causes of coupling between pentlandite dissolution and violarite precipitation, the rate-limiting steps controlling the kinetic behavior, and the origin of the length scale of the features preserved during pseudomorphism.The experiments were conducted under mild hydrothermal conditions (80-210 °C, vapor saturated pressures). Reaction kinetics shows a complex behavior depending on various physical and chemical parameters including temperature, pH, concentrations of various reaction species, solid-weight-to-fluid-volume-ratio and specific surface area. The rate of replacement (i) increases with temperature from 80 to 125 °C, then decreases as temperature further increases to 210 °C, (ii) first increases then decreases with decreasing pH from pH 6 to 1, (iii) increases with increasing concentration of oxidants such as O_2(aq), H₂O₂, and KMnO₄, but decreases with increasing concentration of Ni²⁺ and Fe³⁺, and with increasing solid-weight-to-fluid-volume ratio, (iv) increases linearly with the specific surface area. This kinetic behavior as well as the resulting textures revealed a coupled dissolution-reprecipitation reaction mechanism.Nanometer-scale pseudomorphic replacement, through which the crystallographic orientation of pentlandite is inherited by violarite, occurs only between 1 < pH < 6, and spatial coupling between dissolution and reprecipitation is controlled by the local solution chemistry as well as by epitaxial nucleation mediated by the pentlandite substrate. The kinetic results show that pentlandite dissolution is rate-limiting under mild acidic to neutral conditions (1 < pH < 6), while violarite precipitation is rate-limiting under strong acidic conditions (pH 1). The difference in rate-limiting steps influences the coupling mechanism and causes the different degrees of preservation (length scale of pseudomorphism) and different morphologies observed at high and low pHs: pentlandite dissolution being rate-limiting results in nanoscale coupling between dissolution and precipitation and thus nanoscale pseudomorphism (length scale <20 nm), in which the replacement precisely preserves the morphology and internal details, resembling remarkably the natural pentlandite/violarite assemblages. In contrast, violarite precipitation being rate-limiting results in microscale pseudomorphism (length scale ∼10 μm): the morphology of the pentlandite grains is only roughly preserved and internal details are not preserved.This case study illustrates some general principles of replacement reactions proceeding via the coupled dissolution-reprecipitation mechanism: (i) primary mineral dissolution needs to be rate-limiting compared to the secondary mineral precipitation in order to achieve a high degree pseudomorphic replacement; (ii) the effects of solution composition on reaction kinetics can be qualitatively rationalized by considering the rate-limiting step reaction.     

Droninoite,Ni<Subscript>3</Subscript>Fe<Superscript>3+</Superscript>Cl(OH)<Subscript>8</Subscript> · 2H<Subscript>2</Subscript>O,a new hydrotalcite-group mineral species from the weathered Dronino meteorite

A new mineral, droninoite, was found in a fragment of a weathered Dronino iron meteorite (which fell near the village of Dronino, Kasimov district, Ryazan oblast, Russia) as dark green to brown fine-grained (the size of single grains is not larger than 1 μm) segregations up to 0.15 × 1 × 1 mm in size associated with taenite, violarite, troilite, chromite, goethite, lepidocrocite, nickelbischofite, and amorphous Fe³⁺ hydroxides. The mineral was named after its type locality. Aggregates of droninoite are earthy and soft; the Mohs hardness is 1–1.5. The calculated density is 2.857 g/cm³. Under a microscope, droninoite is dark gray-green and nonpleochroic. The mean (cooperative for fine-grained aggregate) refractive index is 1.72(1). The IR spectrum indicates the absence of S O ₄ ^2? and C O ₃ ^2? anions. Chemical composition (electron microprobe, partition of total iron into Fe²⁺ and Fe³⁺ made on the basis of the ratio (Ni + Fe²⁺): Fe³⁺ = 3: 1; water is calculated from the difference) is as follows, wt %: 36.45 NiO, 12.15 FeO, 17.55 Fe₂O₃, 23.78 H₂O, 13.01 Cl, ?O=Cl₂ ?2.94, total is 100.00. The empirical formula (Z = 6) is Ni_2.16Fe _0.75 ²⁺ Fe _0.97 ³⁺ Cl_1.62(OH)_7.10 · 2.28H₂O. The simplified formula is Ni₃Fe³⁺Cl(OH)₈ · 2H₂O. Droninoite is trigonal, space group R \(\bar 3\) m, R3m, or R32; a = 6.206(2), c = 46.184(18) Å; V = 1540.4(8) ų. The strong reflections in the X-ray powder diffraction pattern [d, Å (I, %) (hkl)] are 7.76(100)(006), 3.88(40)(0.0.12), 2.64(25)(202, 024), 2.32(20)(0.2.10), 1.965(0.2.16). The holotype specimen is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, registration number 3676/1.     

CO<Subscript>2</Subscript> content of andesitic melts at graphite-saturated upper mantle conditions with implications for redox state of oceanic basalt source regions and remobilization of reduced carbon from subducted eclogite

We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO₂ contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1–3 GPa, 1375–1550?°C, and fO₂ of FMQ ?3.2 to FMQ ?2.3 and the resulting experimental glasses were analyzed for CO₂ and H₂O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO₂ content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO₂ as molecular CO₂: ln(K ⁰) = ?21.79?±?0.04, ΔV ⁰?=?32.91?±?0.65 cm³mol^?1, ΔH ⁰?=?107?±?21 kJ mol^?1, and dissolution of CO₂ as CO₃ ^2?: ln(K ⁰ ) = ?21.38?±?0.08, ΔV ⁰?=?30.66?±?1.33 cm³ mol^?1, ΔH ⁰?=?42?±?37 kJ mol^?1, where K ⁰ is the equilibrium constant at some reference pressure and temperature, ΔV ⁰ is the volume change of reaction, and ΔH ⁰ is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO₂ contents and CO₂/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO₂ contents and CO₂/Nb ratios of CO₂-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO₂-enriched basalts, and suggests that fO₂ measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO₂-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.     

57Fe Mössbauer spectroscopy and magnetization of cation-deficient Fe2TiO4 and FeCr2O4. Part I:57Fe Mössbauer spectroscopy

⁵⁷Fe Mössbauer spectra are presented for synthetic cation-deficient Fe₂TiO₄ and FeCr₂O₄ spinel particles (<1μm) at various temperatures. The spectra of ferrimagnetic cation-deficient Fe₂TiO₄ show characteristic features due to relaxation because of superparamagnetism and spin relaxation in the temperature range 5–294 K. At 5 K and 78 K, a superposition of at least two sextets is observed which appear to arise from Fe³⁺ onA-sites (Fe _A ³⁺ andB-sites (Fe _B ³⁺ ) of the spinal lattice with magnetic hyperfine fields at 5 K ofB _hf ((Fe _B ³⁺ )≈47.5 T andB _hf (Fe _B ³⁺ )≈51.0 T, respectively. Cation-deficient FeCr₂O₄ particles reveal at 78 K a fieldB _hf (Fe³⁺)≈46.9 T and exhibit relaxation spectra as a consequence of superparamagnetism in the temperature range 80 K - ～300 K. At 294 K, quadrupole splitting Δ(Fe _A ³⁺ )=0.92 mm/s and isomer shift δ(Fe _A ³⁺ )=0.29 mm/s (relative to metallic Fe) are measured. For both compounds the magnetic hyperfine fieldsB _hf are discussed in terms of supertransferred hyperfine fields involving vacancies and in the case of cation-deficient Fe₂TiO₄ also diamagnetic Ti⁴⁺ neighbours of the Fe ions.     

Crystal chemistry of a natural schorlomite and Ti-andradites synthesized at different oxygen fugacities

Ti-andradites were synthesized at a pressure of P(H₂O)=3 kbar and temperatures of 700–800° C. Oxygen fugacities were controlled by solid state buffers (Ni/NiO; SiO₂ + Fe/Fe₂SiO₄). The Fe²⁺-and Fe³⁺-distribution was determined by low temperature Mössbauer spectroscopy. The water content was measured by a solid's moisture analyzer. The chemical composition of the synthetic and the natural sample has been determined by electron microprobe. Ti-andradites from runs at high oxygen fugacities have Fe³⁺ on octahedral and tetrahedral sites; Ti-andradites from runs at low oxygen fugacities have tetrahedrally and octahedrally coordinated Fe²⁺ as well. These “reduced” garnets must also contain Ti³⁺ on octahedral sites. Charge balance is maintained due to substitution of O^2? by (OH)^? by two mechanisms: (SiO₄)^4? ? (O₄H₄)^4? and (Fe³⁺O₆)^9? ? (Fe²⁺O₅OH)^9?. FTIR spectra of the synthetic samples do show the presence of structurally bound (OH)^?. In a natural sample tetrahedrally and octahedrally coordinated Fe³⁺ are observed together with Fe²⁺ on all three cation sites of the garnet structure.     

Thermodynamic data from redox reactions at high temperatures. II. The MnO-0Mn3O4 oxygen buffer,and implications for the thermodynamic properties of MnO and Mn3O4

The \(\mu _{O_2 } \) defined by the reaction 6 MnO+O₂ =2 Mn₃O₄ has been determined from 917 to 1,433 K using electrochemical cells (with calcia-stabilized zirconta, CSZ) of the type: Steady emfs were achieved rapidly at all temperatures on both increasing and decreasing temperature, indicating that the MnO-Mn₃O₄ oxygen buffer equilibrates relatively easily. It therefore makes a useful alternative choice in experimental petrology to Fe₂O₃-Fe₃O₄ for buffering oxygen potentials at oxidized values. The results are (in J/mol, temperature in K, reference pressure 1 bar); \(\mu _{O_2 } \) (±200)=-563,241+1,761.758T-220.490T inT+0.101819T ² with an uncertainty of ±200 J/mol. Third law analysis of these data, including a correction for the deviations in stoichiometry of MnO, impliesS _298.15 for Mn₃O₄ of 166.6 J/K · mol, which is 2.5 J/K · mol higher than the calorimetric determination of Robie and Hemingway (1985). The low value of the calorimetric entropy may be due to incomplete ordering of the magnetic spins. The third law value of Δ _r H _298.15 ⁰ is-450.09 kJ/mol, which is significantly different from the calorimetric value of-457.5±3.4 kJ/mol, calculated from Δ _f H _298.15 ⁰ of MnO and Mn₃O₄, implying a small error in one or both of these latter.