Uvarovite: Stability of uvarovite-grossularite solid solution at low pressure

Uvarovite (Ca₃Cr₂Si₃O₁₂) forms a complete solid solution series with grossularite (Ca₃Al₂Si₃O₁₂) below 855 ± 5 ° C at a total pressure of 1 atm. Pure uvarovite decomposes to pwo (CaSiO₃) + esk (Cr₂O₃) at 1385 ± 10 ° C. The incorporation of about 5 wt-% of Ca₃Al₂ Si₃O₁₂ component in the uvarovite structure raises the thermal stability of the garnet_ss to 1410 ± 5 ° C, and uvarovite₉₅ grossularite₀₅ melts incongruently to pwo (CaSiO₃) + coresk_ss ((Al, Cr)₂O₃) + L. Pure grossularite decomposes to wo (CaSi0₃) + geh (Ca₂Al₂SiO₇) + and (CaAl₂Si₂O₈) at 855 ± 5 ° C, grossularite thermal stability is increased by incorporation of Ca₃Cr₂Si₃O₁₂ component by 530 ° C. At 1280±5 ° C coresk_ss + L react to gar_ss + geh + an defining an invariant tequilibrium of the CaO-Cr₂O₃-Al₂O₃-SiO₂ quaternary system. Liquid reacts to gar_ss + pwo + geh + an at 1263 ±5 ° C terminating univariant and divariant liquid relations occurring along the join Ca₃Cr₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂. The unit-cell parameter for uvarovite is 11.996(2) Å, the refractive index 1.865(3). The substitution of Cr by Al decreases a and n almost linearly toward the grossularite end member which displays a unit-cell parameter of 11.848(2) Å and a refractive index of 1.732 (1).     

The Blosseville Coast basalts of East Greenland: Their occurrence,composition and temporal variations

In the system CaO-MgO-A1₂O₃-SiO₂ the tie lines connecting anorthite with other phases are sequentially broken down with increasing pressure according to the following univariant reactions: anorthite+ enstatite_ss+sillimanite pyrope-grossular_ss+quartz (3), anorthite+enstatite_ss pyrope-grossular_ss+diopside_ss+quartz (2), anorthite+pyrope-grossular_ss+ quartz diopside_ss+kyanite (4) and anorthite+diopside_ss grossular-pyrope_ss +kyanite+quartz (8). At 1,200 ° C these reactions occur at 14.5± 0.5, 15.5±0.5, 19.5±0.5 and 26.4±1 kilobar and have positive slopes (dP/dT) of 1±0.5, 2.8±0.5, 13.3±0.5 and 24±2bars/°C respectively. An invariant point involving kyanite rather than sillimanite, occurs at 850 °C±25 °C and 14.5±0.5kbar at the intersection of reactions (3), (2) and (4). Reaction(4) exhibits significant curvature with an increase in dP/dT from 13.3±0.5 to 18.5± 0.5 bars/°C between 1,050° and 850° C. The pressure at which the complete grossular-pyrope join is stable with quartz is estimated at 41 ± 1 kbar at 1,200 ° C. The pressure at which garnet appears according to reaction (2) is lowered by 5 kbar for a composition with anorthite and orthopyroxene (En_0.5Fs_0.5). Enstatite and plagioclase (An_0.5Ab_0.5) first produce garnet at 2 kbar higher pressure than enstatite and pure anorthite (reaction (2)). The calcium content of garnet in various divariant assemblages is relatively insensitive to temperature but very sensitive to pressure, it is therefore a useful geobarometer. At metamorphic temperatures of 700–850 °C pressures of 8–10 kbar are required for the formation of quartz-bearing garnet granulites containing calcic plagioclase and with (Mg/Mg+Fe) bulk = 0.5.     

Petrology of calc-silicate rocks from Koduru,Andhra Pradesh,India

Mineral assemblages, rock and mineral chemistry, and mineral reactions, in calc-silicate rocks from Koduru area, Andhra Pradesh, India are discussed. Mineralogical and bulk chemical differences indicate 3 calc-silicate rock types — type I with K feldspar+calcite+wollastonite+quartz+scapolite+diopside_ss +andradite_ss+sphene, has relatively high rock oxidation ratios. Type II is a highly calcic variety with high rock MgFe ratios, and has K feldspar+calcite+wollastonite+quartz+scapolite + diopside_ss±grossularite_ss+sphene+zoisite. Type III has K feldspar +calcite+wollastonite+quartz+scapolite+diopside_ss +sphene+hornblende+magnetite, and has relatively low oxidation ratio and low MgFe ratio. The 3 calc-silicate rock types have originated as mixtures of limestone/dolomite/marl.Diopside was produced by a reaction involving Ca-amphibole +calcite+quartz, and reversed during retrogression. Andradite_ss in type I rocks was produced at the expense of hedenbergitic component of pyroxene in a continuous reaction as a consequence of increase in the oxygen content of the original sediment relative to type III. Calcite+quartz reacted to give wollastonite. During cooling an influx of water caused scapolite to alter to zoisite.     

The system diopside-nepheline-leucite

The system diopside-nepheline-leucite, representing a join in the undersaturated part of the system nepheline (Ne)-kalsilite (Ks)-CaO-MgO-SiO₂, has been investigated at atmospheric pressure. The system is pseudoternary and cuts the primary phase volumes of forsterite solid solution (Fo_ss), diopside solid solution (Di_ss), nepheline solid solution (Ne_ss), carnegieite solid solution (Cg_ss), and leucite solid solution (Lc_ss). Melilite (Mel) occurs as a subliquidus phase. The phase diagram has two four-phase points: 1. one at 1275±5° C and Di₆₀Ne₈Lc₃₂ where liquid coexists with Fo_ss, Di_ss and Lc_ss, corresponding to olivine (Ol) leucitite; 2. the other at 1194±5° C and Di_27.5Ne_29.5Lc₄₃ where Ne_ss, Fo_ss and Lc_ss coexist with liquid, corresponding to Ol-Ne italite. With decreasing temperature, liquid moves from point (1) to a five-phase assemblage (3) where liquid is in equilibrium with Fo_ss, Di_ss, Mel and Lc_ss (1258±5°C), which is representative of Ol-Mel-leucitite. From point (2) liquid moves to a second five-phase assemblage (4), where Fo_ss, Mel, Ne_ss, Lc_ss and liquid are in equilibrium (1175±5°C, corresponding to a Lc-Ne katungite. The assemblage Fo_ss+Ne_ss+Di_ss+Mel+Lc_ss+ liquid, is reached between 1168° and 1100° C and corresponds to Ol-Mel-Ne leucitite. Fo_ss reacts with liquid and disappears. Near the point (1) it disappears at 1135±10° C, whereas near the point (2) it reacts out at 1060±10° C. Near the join Di-Ne it disappears at 950±10° C. The final assemblage in the system is representative of Mel-Ne leucitite.Presented at the symposium Recent Advances in the Studies of Rocks and Minerals at High Pressures and Temperatures held in Montreal, 1972. Jointly sponsored by the International Mineralogical Association and the Commission on Experimental Petrologie.     

On the presence of leucite in basaltic rocks from central France

The existence of interstitial leucite is demonstrated in a number of alkali-basalts and basanites from the tertiary and quaternary volcanic province of central France. This leucite occurs in nepheline-normative, K₂O-rich basaltic rocks. Available experimental data show that the assemblage nepheline_ss+leucite_ss+ alkali feldspar_ss would be a frequent one, and our observations tend to support the view that it is indeed common in basaltic rocks of appropriate composition.     

An electrochemical study of Ni2+, Co2+, and Zn2+ ions in melts of composition CaMgSi2O6

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.     

Discussion of “Thermodynamic parameters of CaMgSi<Subscript>2</Subscript>O<Subscript>6</Subscript>-Mg<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxenes based on regular solution and cooperative disordering models” by Holland,Navrotsky, and Newton

Phase equilibria in the join CaMgSi₂O₆-CaFeAlSiO₆-CaTiAl₂O₆ have been determined in air at 1 atm by the ordinary quenching method. Clinopyroxene_ss, forsterite, perovskite, magnetite_ss, spinel_ss, hibonite and an unknown phase X are present at liquidus temperatures (ss: solid solution). At subsolidus temperatures the following phase assemblages were encountered; clinopyroxene_ss+perovskite, clinopyroxene_ss +perovskite+spinel_ss, clinopyroxene_ss +perovskite+melilite (+anorthite), clinopyroxene_ss +perovskite+melilite+spinel_ss+anorthite, clinopyroxene_ss +perovskite+anorthite+spinel_ss, and clinopyroxene_ss +perovskite+anorthite+hibonite. At subsolidus temperatures the single phase field of clinopyroxene_ss extends up to 19 wt.% CaTiAl₂O₆. Even in the field of clinopyroxene_ss+perovskite, the TiO₂ content in clinopyroxene_ss continues to increase and attains 9.2 wt.% TiO₂ with 24.8 wt.% Al₂O₃. An interesting fact is that unusual clinopyroxenes which contain more Al^IV than Si^IV are present in the CaFe-AlSiO₆-rich region. The liquid coexisting with pyroxene is richer in Ti, Al, and Fe³⁺ than the coexisting pyroxene. The clinopyroxenes_ss coexisting with liquid contain less TiO₂, Al₂O₃ and Fe₂O₃ than those crystallized at subsolidus temperatures. The petrological significance of the join and the crystallization of Ti- and Al-rich clinopyroxenes are discussed on the basis of the experimental results of the join.     

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The Thermodynamics of Ordered Perovskites on the CaTiO3-FeTiO3 Join

The enthalpies of formation from ilmenite, FeTiO₃, and perovskite, CaTiO₃, of two intermediate ordered perovskite phases, CaFeTi₂O₆ and CaFe₃Ti₄O₁₂, have been measured at 801°C using oxide melt solution calorimetry. These data, in combination with experiments at high pressure and temperature, indicate that below 1518±50°C CaFe₃Ti₄O₁₂ is stable at lower pressures (∼7 GPa at 1200°C) than CaFeTi₂O₆ (∼13 GPa at 1200°C). This relationship should be reversed, and CaFeTi₂O₆ should become stable at lower pressures than CaFe₃Ti₄O₁₂, at temperatures above 1518±50°C. These intermediate phases are of petrological interest because they form as a reaction between two minerals, ilmenite and perovskite, which are commonly associated in kimberlites, and because their pressure-temperature range of formation overlaps that of origin of kimberlites. Received: 10 November 1997 / Revised; accepted: 15 January 1998     

Clinopyroxene on the join CaMgSi2O6-CaFe3+AlSiO6-CaTiAl2O6 at low oxygen fugacity

Subsolidus phase relations on the join CaMgSi₂O₆-CaFe³⁺ AlSiO₆-CaTiAl₂O₆ were studied by the ordinary quenching method at \(f_{O_2 } = 10^{ - 11} \) atm and 1,100°C. Crystalline phases encountered are clinopyroxene_ss (ss:solid solution) (Cpx_ss), melilite (Mel), perovskite (Pv), spinel_ss (Sp_ss), magnetite_ss (Mt_ss) and anorthite (An). There is no Cpx_ss single phase field, and the following assemblages were found; Cpx_ss+Mel, Cpx_ss+Mel+Sp_ss, Cpx_ss+Mel+Pv, Cpx_ss+Mel+Sp_ss+Pv, Cpx_ss+Pv+Sp_ss+An, Sp_ss+Pv+Mel+An+Cpx_ss, Mel+Mt_ss+An+Sp_ss+Cpx_ss+liquid and Mel+Mt_ss+An+Sp_ss+Cpx_ss+Pv. Mössbauer spectral study revealed that Cpx_ss contains both Fe²⁺ and Fe³⁺ in the octahedral site, and it was confirmed that the CaFe³⁺ AlSiO₆ content in the Cpx_ss at low \(f_{O_2 } \) is considerably less than that in the Cpx_ss crystallized in air, whereas the CaFe²⁺Si₂O₆ component increases. The maximum solubility of CaTlAl₂O₆ component in the Cpx_ss at low \(f_{O_2 } \) is higher than that in air. The decrease of CaFe³⁺ AlSiO₆ in the Cpx_ss at low \(f_{O_2 } \) may cause increase of CaTial₂O₆ in the Cpx_ss.     

High-temperature metamorphic imprint on calc-silicate granulites of Rayagada,Eastern Ghats,India: implication for the isobaric cooling path

 Calc-silicate granulites from Rayagada, north-central sector of Eastern Ghats granulite belt show a wide range of mineral assemblages and chemical compositions, which can be grouped as Gr. I (grossular- rich garnet-wollastonite-scapolite-calcite-clinopyroxene), Gr. II (andradite-rich garnet-scapolite-calcite-clinopyr- oxene), and Gr. III (scapolite-calcite-clinopyroxene-plagioclase) assemblages. Petrographic features suggest the following several reactions in the CaO–Al₂O₃–SiO₂-vapor system: Mei+4Wo+Cal=3Grs+Qtz +2CO₂, Mei+3Wo+2Cal=3Grs+CO₂, Mei= 3An+Cal, Wo+CO₂=Cal+Qtz, Mei+5Wo =3Grs+2Qtz+CO₂, An+Wo=Grs+Qtz, Mei+ 5Cal+3Qtz=3Grs+6CO₂, and the following reactions in the CaO–FeO–MgO–Al₂O₃–SiO₂-vapor system: Cpx_ss+Scp+Wo=Grt_ss+Qtz+CO₂, 4Hd+ 2Cal+O₂=2Adr+2Qtz+2CO₂, Cpx_ss+Scp= Grt_ss+Cal+Qtz. These reactions have been used to estimate peak T-X _CO2 condition for these granulites. A maximum temperature of ∼920 °C has been calculated at an estimated pressure of 9 kbar. A T-X _CO2 diagram shows an isobaric cooling from ∼920 °C to ∼815 °C. A range of X _CO2 (0.50 at 920 °C to 0.25 at 815 °C) has been observed for Gr. I calc-silicate granulites based on the reaction sequences including coronal garnet-forming reactions. This sequence is suggestive of internal fluid buffering rather than external fluid influx and the differences in X _CO2 conditions has been thought to be due to local buffering of fluid phases. Group II and Gr. III calc-silicate granulites, on the other hand, exhibit relatively lower temperature conditions. Received: 11 September 1995/Accepted: 20 June 1996     

Experimentelle Bestimmung der P-T-Stabilitätsbereiche in der Mischkristallreihe Tremolit-Tschermakit

The join tremolite (Tr)—tschermakite (Ts) was studied at temperatures of 450 to 900° C under water vapour pressure of 2 kbar. Solid solution between the end members is restricted to composition range Tr₁₀₀-Tr₄₅. Reconnaissance runs at 800°C and 10 kbar indicated that no further substitution of Al in the tremolite structure is possible by an increase of pressure. In the composition range Ts₅₅-Ts₁₀₀ tremolite-tschermakite solid solution Tr₄₅Ts₅₅ is formed with anorthite, forsterite and enstatite above 700°C and with anorthite and chlorite below 700° C. No amphibole could be synthezised from a material of composition Ts₁₀₀. Materials of composition Ts₁₀₀ crystallized to anorthite, enstatite and frosterite above 700°C and to anorthite and chlorite below 700°C. The high temperature breakdown curve for tremolite-tschermakite solid solutions drops from 870°C for pure tremolite to 826°C for Tr₄₅Ts₅₅. Additional experiments at 1 and 3 kbar indicate that the pressure effect on breakdown temperatures amounts to about 35°C/kbar. The formation of natural amphiboles belonging to the tremolite-tschermakite series is discussed in the light of the experimental data.     

A TEM and microprobe study of a two-perthite alkali gabbro: Implications for the ternary feldspar system

An unusual magmatic three-feldspar syenogabbro occurs 3 m inside the contact of the Klokken gabbro-syenite stock. It contains plagioclase, mesoperthite and cryptoperthite, together with a low temperature symplectite intergrowth. Textural relationships have been investigated by cathodoluminescence, bulk chemistry by microprobe, and exsolution microtextures and intracrystalline boundaries by TEM. The mesoperthite has a bulk composition around Or₂₆Ab₅₂An₂₂, well outside accepted limits of ternary feldspar solid solution. It is a mainly coherent, lamellar intergrowth of sodic andesine and orthoclase with incipient Mtwinning. The cryptoperthite, bulk composition around Or₆₁Ab₃₃An₆, is a coherent lamellar intergrowth of orthoclase and sodic low oligoclase. The compositions of the exsolved phases have been estimated. The meso- and cryptoperthite crystals have sharp boundaries with each other. Plagioclase (zoned An 55-35, with 2–3% Or) defines a solidus fractionation path. It behaved as an inert phase during crystallization of the perthites, which grew as homogeneous monoclinic phases in equilibrium on the strain-free ternary solvus, defining a solvus isotherm at ～ 950° C. Both of the monoclinic phases exsolved on reaching the coherent ternary spinodal at temperatures estimated to be close to 800–850° C and 700–830° C respectively. Lamellar periodicities (529±149 nm and 148±18 nm respectively) are considerably finer scale than predicted by coarsening experiments, suggesting that An and/or Al-Si order greatly inhibit coarsening. The symplectite is a coarse, incoherent intergrowth of sodic andesine and nearly pure K-feldspar, probably produced by simultaneous crystallization at <400° C. The new data and literature analyses are used to construct the geometry of the ternary feldspar system. Solvus isotherms implied by existing experimental data approach the Ab apex too closely at high temperature. The critical solution curve becomes slightly more albitic after leaving the binary Ab-Or join, and then turns sharply towards the An-Or join. It intersects the proposed new limit of feldspar solid solution near Or₃₆Ab₄₄An₂₀ at 1,060° C. This probably approximates to the highest temperature on the ternary critical curve at 1 bar.     

Subsolidus and melting relationships for calcite,magnesite and the join CaCO3-MgCO3 36 kb

Subsolidus and melting relations for the CaCO₃-MgCO₃ join at 30 kb have been determined using piston-cylinder apparatus. Data are also presented for the melting curve of CaCO₃ to 30 kb, the decomposition and melting curves of MgCO₃ to 36 kb, and the calcite-aragonite transition at 800°C, 950°C and 1100°C. At 30kb, the melting loop for the CaCO₃-MgCO₃ join extends from 1610°C (CaCO₃) to 1585°C (MgCO₃) through a liquidus minimum at 1290°C (near 42 mole% MgCO₃). The dolomite-magnesite solvus barely intersects the 30 kb melting loop to produce a peritectic reaction at 1385°C. Integration of the new experimental data with other published data permits construction of a complete P-T projection and a sequence of isobars for the CaCO₃-MgCO₃ join for pressures between 5 and 30 kb. The phase relations for this join provide part of the essential framework of the model peridotite system CaO-MgO-SiO₈-CO₂-H₂O, which has particular application to the origin of carbonatitic and kimberlitic magmas. In light of the accumulating evidence for CO₂ in various forms within the upper mantle and of its effect on magmatic processes, analysis of the melting relations in this system is of considerable importance.     

Unit-cell dimensions and tetrahedral-site ordering in synthetic gallium albite (NaGaSi3O8)

The tetrahedral-site order-disorder transformation in gallium albite (NaGaSi₃O₈) has been investigated using Rietveld structure refinement. Study of gallium-substituted albite (in contrast to pure albite [NaAlSi₃O₈]) is facilitated by a relatively rapid order-disorder transformation and the large difference in X-ray scattering efficiencies of gallium and silicon. High albite-structure NaGaSi₃O₈, grown in a Na₂WO₄ flux, was ordered by hydrothermal annealing below 820° C and dry annealing above 820° C, to avoid melting, using a load pressure of approximately 1 kbar. Equilibration of the order-disorder reaction has been verified by three independent reversals of ordering. The transformation between low gallium albite and high gallium albite occurs over the temperature range 890° C 970° C. The gallium content of the T ₁o site increases continuously with decreasing temperature. The gallium contents of the T ₁m and T ₂m sites decrease smoothly with increasing ordering while the gallium content of the T ₂o site decreases, then increases and then decreases again with decreasing temperature. Unit-cell parameters and the triclinic obliquity vary throughout the order-disorder transformation and undergo abrupt changes at 913±3° C and 937±3° C. These abrupt changes correlate with changes in the gallium content of the T ₂o site, the X and Z ordering parameters and the configurational entropy. The order-disorder transformation in gallium-aluminum albite (NaGa_0.5Al_0.5Si₃O₈) occurs in the temperature range 765° C-850° C, at a temperature intermediate to the transformation in albite (50% order at about 680±20° C) and gallium albite.     

H<Subscript>2</Subscript>O storage capacity of olivine and low-Ca pyroxene from 10 to 13 GPa: consequences for dehydration melting above the transition zone

The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H₂O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H₂O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because simpler systems do not account for enhanced hydrous melt stability and reduced H₂O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline phases have maximal H₂O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C, the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation C_{\textH2 \textO}^\textolivine ( \textppm ) = 57.6( ±16 ) ×P( \textGPa ) - 169( ±18 ). C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations of D_{\textH2 \textO}^{\textpyx/olivine} D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} from this study and estimates of D_{\textH2 \textO}^{\textgt/\textolivine} D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} , allows for estimation of peridotite H₂O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm bulk H₂O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues of subducted slabs, which contain 300–1,000 ppm bulk H₂O, can exceed the peridotite H₂O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values of D_{\textH2 \textO}^{\textpyx/\textolivine} D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H₂O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence on viscosity and other transport properties.     

Experimental study of Pd hydrolysis in aqueous solutions at 25–70°C

The hydrolysis of the Pd²⁺ ion in HClO₄ solutions was examined at 25–70°C, and the thermodynamic constants of equilibrium K ₍₁₎⁰ and K ₍₂₎⁰were determined for the reactions Pd²⁺ + H₂O = PdOH⁺ + H⁺ and Pd²⁺ + 2H₂O = Pd(OH)₂⁰ + 2H⁺, respectively. The values of log K ₍₁₎⁰ = −1.66 ± 0.5 (25°C) and −0.65 ± 0.25 (50°C) and log K ₍₂₎⁰ = −4.34 ± 0.3 (25°C) and −3.80 ± 0.3 (50°C) were derived using the solubility technique at 0.95 confidence level. The values of log K ₍₁₎⁰ = −1.9 ± 0.6 (25°C), −1.0 ± 0.4 (50°C), and −0.5 ± 0.3 (70°C) were obtained by spectrophotometric techniques. The palladium ion is significantly hydrolyzed at elevated temperatures (50–70°C) even in strongly acidic solutions (pH 1–1.5), and its hydrolysis is enhanced with increasing temperature.     

Tracing exhumation record in high-pressure micaschists: A new tectonometamorphic model of the evolution of the eastern part of the Fore Sudetic Block,Kamieniec Metamorphic Belt,NE Bohemian Massif,SW Poland

The Kamieniec Metamorphic Belt comprises a volcano-sedimentary succession exposed within a collision zone between the Saxothuringian and Brunovistulian crustal domains of the European Variscides. The studied rocks recorded two metamorphic episodes. The first episode, M₁, occurred at conditions of c. 485 ± 25 °C and 18 ± 1.8 kbar related to burial within a subduction zone. The subsequent episode, M₂, was linked to the final phases of exhumation to mid-crustal level, associated with pressure and temperature (P–T) conditions ranging from c. 520 ± 26 °C and 6 ± 0.6 kbar through 555 ± 28 °C and 7 kbar ± 0.7 to ~590 ± 30 °C and 3–4 ± 0.4 kbar. The documented deformation record is ascribed to three events, D₁ to D₃, interpreted as related to the burial and subsequent exhumation of the Kamieniec Metamorphic Belt. The D₁ event must have witnessed the subduction of the Kamieniec Metamorphic Belt rock succession whereas the D₂ event was associated with the exhumation and folding of the Kamieniec Metamorphic Belt in an E-W-directed shortening regime. A subsequent folding related to the D₂ event was initiated at HP conditions, however, the planar fabric produced during a late stage of the D₂ event, defined by a low-pressure mineral assemblage M₂, indicates that the D₂ final stage was synchronous with the onset of the M₂ episode. Consequently, the entire D₂ event seems to have been associated with the exhumation of the Kamieniec Metamorphic Belt to mid crustal level. The third deformation event D₃, synchronous with the M₂ episode, marked the last stage of the exhumation, and was linked to emplacement of granitoid veins and lenses. The latter resulted in heating and rheological weakening of the entire rock succession and in the formation of non-coaxial shear zones.     

Thermochemistry of monazite-(La) and dissakisite-(La): implications for monazite and allanite stability in metapelites

Thermochemical properties have been either measured or estimated for synthetic monazite, LaPO₄, and dissakisite, CaLaMgAl₂(SiO₄)₃OH, the Mg-equivalent of allanite. A dissakisite formation enthalpy of ?6,976.5 ± 10.0 kJ mol^?1 was derived from high-temperature drop-solution measurements in lead borate at 975 K. A third-law entropy value of 104.9 ± 1.6 J mol^?1 K^?1 was retrieved from low-temperature heat capacity (C _p) measured on synthetic LaPO₄ with an adiabatic calorimeter in the 30–300 K range. The C _p values of lanthanum phases were measured in the 143–723 K range by differential scanning calorimetry. In this study, La(OH)₃ appeared as suitable for drop solution in lead borate and represents an attractive alternative to La₂O₃. Pseudo-sections were calculated with the THERIAK-DOMINO software using the thermochemical data retrieved here for a simplified metapelitic composition (La = ∑REE + Y) and considering monazite and Fe-free epidotes along the dissakisite-clinozoïsite join, as the only REE-bearing minerals. Calculation shows a stability window for dissakisite-clinozoïsite epidotes (T between 250 and 550°C and P between 1 and 16 kbar), included in a wide monazite field. The P–T extension of this stability window depends on the bulk-rock Ca-content. Assuming that synthetic LaPO₄ and dissakisite-(La) are good analogues of natural monazite and allanite, these results are consistent with the REE-mineralogy sequence observed in metapelites, where (1) monazite is found to be stable below 250°C, (2) around 250–450°C, depending on the pressure, allanite forms at the expense of monazite and (3) towards amphibolite conditions, monazite reappears at the expense of allanite.     

Phase equilibria in the KFeS<Subscript>2</Subscript>–Fe–S system at 300–600 °C and bartonite stability

The article deals with phase relations in the KFeS₂–Fe–S system studied by the dry synthesis method in the range of 300–600 °C and at a pressure of 1 bar. At the temperature below 513?±?3 °C, pyrite coexists with rasvumite and there are pyrite–rasvumite–KFeS₂ and pyrite–rasvumite–pyrrhotite equilibria established. Above 513?±?3 °C pyrite and rasvumite react to form KFeS₂ and pyrrhotite, limiting the pyrite–rasvumite association to temperatures below this in nature. The experiments also outline the compositional stability range of the copper-free analog of murunskite (K _x Fe_2?yS₂) and suggest that mineral called bartonite is not stable in the Cl-free system, at least at atmospheric pressure and the temperature in the experiments. Chlorbartonite could be easily produced after adding KCl in the experiment. Possible parageneses in the quaternary K–Fe–S–Cl system were described based on the data obtained in this research and found in the previous studies. The factors affecting the formation of potassium–iron sulfides in nature were discussed.