Spinel-garnet lherzolite transition in the system CaO-MgO-Al2O3-SiO2 revisited: an in situ X-ray study

Large discrepancies are reported for the near-solidus, pressure-temperature location of the spinel to garnet lherzolite univariant curve in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS). Experimental data obtained previously from the piston-cylinder apparatus indicate interlaboratory pressure differences of up to 30% relative. To investigate this disparity—and because this reaction is pivotal for understanding upper mantle petrology—the phase boundary was located by means of an independent method. The reaction was studied via in situ X-ray diffraction techniques in a 6-8 type multianvil press. Pressure is determined by using MgO as an internal standard and is calculated from measured unit cell volume by using a newly developed high-temperature equation of state for MgO. Combinations of real-time and quenched-sample observations are used to bracket the phase transition. The transition between 1350 and 1500°C was reversed, and the reaction was further constrained from 1207 to 1545°C. Within this temperature range, the transition has an average dT/dP slope of ∼40 ± 10°C/kbar, consistent with several previous piston-cylinder studies. Extrapolation of our curve to 1575°C, an established temperature of the P-T invariant point, yields a pressure of 25.1 ± 1.2 kbar. We also obtained a real-time reversal of the quartz-coesite transition at 30.5 ± 2.3 kbar at 1357°C, which is about 2 to 4 kbar lower in pressure than previously determined in the piston-cylinder apparatus.     

Direct determination of the quartz-coesite transition by in situ X-ray measurements

The quartz-coesite transition has been determined over the temperature range 600–1100° C by in Situ X-ray measurements with NaCl as internal pressure standard. An internally heated high-pressure X-ray apparatus (Belt-type) was used which is based on the principle developed by Freud and Sclar (1969). The obtained quartz-coesite equilibrium line may be represented by the equation P=31±1+0.0075 T where P is in kb and T in ° C.     

Al/Si interdiffusion in albite: effect of pressure and the role of hydrogen

The effect of pressure on the rate of Al/Si disorder in albite has been determined at temperatures from 800° C to 1050° C and at pressures up to 24 kbar, using dried samples in welded Pt containers, in piston-cylinder devices and internally-heated gas apparatus. In the piston-cylinder device with NaCl medium, the effect of pressure is profound. A pure low albite from Clear Creek, California reaches the equilibrium state of disorder at 850° C and 22 kbar in 10 h, whereas at 6 kbar it has not equilibrated in three weeks, and at one bar it probably cannot be disordered at 850° C in the laboratory. The enhancement of Al/Si interdiffusion takes place under dry conditions: any H₂O penetrating the samples would have produced melting, and none was observed. Hydrogen, however, is produced by dissociation of moisture in the pressure medium and can penetrate the Pt sample capsules. If the samples are deprived of hydrogen by replacing NaCl with glass or by embedding the samples in a hydrogen getter such as Fe₂O₃ or ZnO, the order-disorder reaction is greatly inhibited.A mechanism is suggested in which OH^– groups are formed by hydrogen hopping in albite. The smaller charge on the tetrahedral complex induces transient coordination of Al greater than four at elevated pressures, facilitating Al/Si interchange during the bond-breaking process. This results in an exponential pressure dependence of diffusion. It is also suggested that the presence of hydrogen at high pressures can greatly effect the mechanical properties and reactivity of deep crustal and mantle rocks. In nature, as well as in the laboratory, equilibration at elevated pressures may be as much dependent on the availability of hydrogen as on time or temperature.     

Experimental phase relations of hydrous peridotites modelled in the system H2O-CaO-MgO-Al2O3,-SiO2

The hydration of peridotites modelled by the system H₂O-CaO-MgO-Al₂O₃-SiO₂ has been treated theoretically after the method of Schreinemakers, and has been investigated experimentally in the temperature range 700°–900° C and in the pressure range of 8–14 kbar. In the presence of excess forsterite and water, the garnet- to spinel-peridotite transition boundary intersects the chlorite dehydration boundary at an invariant point situated at 865±5° C and 15.2±0.3 kbar. At lower pressures, a model spinel lherzolite hydrates to both chlorite- and amphibole-bearing assemblages at an invariant point located at 825±10° C and 9.3±0.5 kbar. At even lower pressures the spinel-to plagioclase-peridotite transition boundary intersects the dehydration curve for amphibole+forsterite at an invariant point estimated to lie at 855±10° C and 6.5±0.5 kbar.Both chlorite and amphibole were characterized along their respective dehydration curves. Chlorite was found to shift continuously from clinochlore, with increasing temperature, to more aluminous compositions. Amphibole was found to be tremolitic with a maximmum of 6 wt.% Al₂O₃.The experimentally determined curves in this study were combined with the determined or estimated stability curves for hydrous melting, plagioclase, talc, anthophyllite, and antigorite to obtain a petrogenetic grid applicable to peridotites, modelled by the system H₂O-CaO-MgO-Al₂O₃-SiO₂, that covers a wide range of geological conditions. Direct applications of this grid, although quite limited, can be made for ultramafic assemblages that have been extensively re-equilibrated at greenschist to amphibolite facies metamorphism and for some highgrade ultramafic assemblages that display clear signs of retrogressive metamorphism.     

Experimental determination of the spinel peridotite to garnet peridotite reaction in the system MgO-Al2O3-SiO2 in the range 900 °–1100 °C and Al2O3 isopleths of enstatite in the spinel field

The univariant high-pressure reaction of aluminous enstatite and spinel to pyrope and forsterite in the MgO-Al₂O₃-SiO₂ system has been determined in the temperature range 900 °–1100 °C by hydrothermal reversals in the piston-cylinder apparatus using the low-friction NaCl pressure medium. A mixture of synthetic minerals, including an enstatite with 6 wt% Al₂O₃, with product and reactant assemblages in nearly equal amounts, was the starting material. The equilibrium pressure of 19.3±0.3 kbar at 1000 ° C and average dP/dT slope of 8.0 bars/ ° C confirm the strong curvature of the equilibrium below 1200 ° C deduced by Obata (1976) from a theoretical study of experimental Al₂O₃ isopleths of enstatite in the garnet field. His prediction of an absolute minimum pressure near 18 kbar of the garnet peridotite assemblage in the ternary system is undoubtedly correct.Three reversed determinations of the equilibrium Al₂O₃ content of enstatite in the presence of spinel +forsterite were made at points adjacent to the univariant curve. The points are 5.5 wt% Al₂O₃ at 950 ° C and 20 kbar, 6.2 wt% at 1000 ° C and 20 kbar and 7.2 wt% at 1080 ° C and 20 kbar. These values are somewhat higher than given by the MacGregor (1974) isopleth set and quite close to those predicted by Fujii (1976) from experimental synthesis data at higher temperatures, using the Wood and Banno (1973) model of ideal solution of the Mg₂Si₂O₆ and MgAl₂SiO₆ components in enstatite to reduce the data.All of the available spinel-field isopleth data can be systematized with the use of the ideal solution model. A value of H ⁰ of 9000 cal fits the reduced data well, and is in agreement with the calorimetrically determined value of 8500±1900 calories. An accurate calculation of the dP/dT slope of the univariant equilibrium at 1000 ° C based on calorimetry gives 7±2bars/ °C, also in good agreement with experiment. Thus, all of the available experimental and calorimetric data are consistent with the ideal-solution aluminous enstatite model.The dP/dT slopes of the spinel-field isopleths are too large to permit their use as an accurate geobarometric scale. They do have considerable potential as a thermometric indicator for certain natural peridotites, however. The southwestern Oregon overthrust peridotite masses of Cretaceous age have enstatite of 5.6 wt% Al₂O₃ with spinel of nearly 80 mole% MgAl₂O₄. The present reduced isopleth data directly give 930 ° C for the equilibration, assuming 12 kbar pressure. A first order correction based on ideal solution departures from the ternary system, as suggested by Stroh (1976) gives 1000 ° C. Thus, the high temperatures deduced by Medaris (1972) are confirmed. The pressure cannot be deduced independently from the pyroxene Al₂O₃ contents.     

The calcite-aragonite transition,reinvestigated

The calcite-aragonite equilibrium has been investigated between 200 and 600° C both in a carefully calibrated hydrothermal apparatus and in a piston-cylinder device of high precision. The equilibrium pressure is 5 kb at 180° C, 7 kb at 300° C, 9 kb at 400° C, and 11 kb at 480° C.The calcite-aragonite transition boundary which has been bracketed is continuously curved between 300 and 500° C and is more or less straight above and below this temperature range. It is shown that the calcite I-calcite II reaction is probably a second (and not a first) order transition.The experimental result shows that aragonite may already be formed out of calcite at a depth of 15 km if the temperature is not much higher than 100° C. The calcitearagonite and the albite-jadeite-quartz curves intersect at about 750° C and 20 kb. There is a P-T-field (up to 3.5 kb broad) where aragonite and albite coexist.     

Time-temperature-transformation (TTT) analysis of cation disordering in omphacite

The kinetics of cation disordering in a natural ordered (P2/n) omphacite have been followed at P=18 and 30 kb, T= 750–1,260° C, for times of between 1.5 min and 16 days in a piston-cylinder apparatus. Time-temperature-transformation (TTT) analysis of the experimental data, using the presence or absence of the 11¯1 reflection in single crystal X-ray precession photographs to indicate the extent of reaction, yields an equilibrium order/disorder temperature (T _ord) of 865±10° C, an activation enthalpy (1 bar) of 71±6 kcal mole^–1 and an activation volume of 9±4 cm³ mole^–1 (plus and minus figures represent the precision of a best fit between experimental data and TTT theory rather than absolute errors). The activation volume is consistent with a vacancy mechanism of cation diffusion. H₂O, added in the form of oxalic acid, appears to speed the process up slightly. The overall transformation mechanism is continuous, involving neither the nucleation of a disordered phase nor a change in antiphase-domain distribution. This is consistent with both first- and non-first-order character for the C2/cP2/n transformation, though a range of ordered states below T _ord is indicated by the weakening of h+k=odd reflections. A simple extrapolation of the disordering rates to geological conditions leads to the first estimate of how long disordered omphacites would take to order in nature, ranging from less than one year at T800° C to more than 10⁷ years at T<350° C.     

Carbon isotopic fractionation between CO2 vapour,silicate and carbonate melts: an experimental study to 30 kbar

The carbon isotopic fractionation between CO₂ vapour and sodamelilite (NaCaAlSi₂O₇) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag₂C₂O₄ was the source of CO₂ and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the ¹³C of coexisting vapour was determined directly by capsule piercing. CO₂ solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO₂ dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO₂ reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO₂ solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO₂ vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring¹³C enrichment in CO₂ vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO₂ vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.     

Melting relations of basalt-andesile-rhyolite-H2O and a pelagic red clay at 30 kb

An olivine basalt, a tonalite (andesite), a granite (rhyolite), and a red clay (pelagic sediment) were reacted, with known quantities of water in sealed noble metal capsules, in a piston-cylinder apparatus at 30 kb pressure. For the pelagic sediment, with H₂O+=7.8% and no additional water, the liquidus temperature is 1240°C, the primary phases are garnet and kyanite. The subsolidus phase assemblage is phengite mica+garnet+clinopyroxene+coesite+kyanite. With 5 wt.% water added, the liquidus temperatures and primary phases for the calc-alkaline rocks are 1280°-1180°-1080°, garnet+clinopyroxene, garnet, and quartz respectively. Garnet and clinopyroxene occur throughout the melting interval of the olivine tholeiite for all water contents. Garnet is joined by clinopyroxene 80° below the andesite plus 5% H₂O liquidus, quartz is joined by clinopyroxene 180° below the rhyolite plus 5% H₂O liquidus. The subsolidus phase assemblage is garnet+clinopyroxene+coesite+minor kyanite for all the calc-alkaline compositions. We conclude that calc-alkaline andesites and rhyolites are not equilibrium partial melting pruducts of subducted oceanic crust consisting of olivine tholeiite basalt and siliceous sediments. Partial melting in subduction zones produces broadly acid and intermediate liquids, but these liquids lie off the calc-alkaline basalt-andesite-rhyolite join and must undergo modification at lower pressures to produce calcalkaline magmas erupted in overlying island arcs.     

Hydration and phase relations of grossular-spessartine garnets at P H 2O=2 Kb

The phase relations in the system grossular-spessartine-H₂O were investigated at 2.0 Kb aqueous fluid pressure and at subsolidus temperatures down to 420 ° C. Despite metastable persistence of a compositional gap found in some intermediate members, a complete solid solution between grossular and spessartine exists.Linear relations between the unit cell edge, a ₀, and composition were readily observed down to 620 ° C with a ₀=11.849(2) Å and 11.613(2) Å for grossular and spessartine, respectively. Hydrated garnets began to appear at higher temperature for the Ca-rich members. Grossular and spessartine formed at 420 ° C have a ₀=11.901(2) Å and 11.632(2) Å, indicating the presence of 0.6 and 0.2 mol H₂O, respectively. Intermediate members show varying degrees of hydration. Infrared spectra of the more hydrated members show a major and minor absorption bands at 3,620 cm^–1 and 3,660 cm^–1, respectively, in addition to a broad band around 3,430 cm^–1. All the hydrogarnets formed at 420 ° C were proven to be metastable.The rare occurrence of the intermediate grossular-spessartine garnets may be attributed to the lack of appropriate bulk chemistry of the rock rather than to the P-T conditions to which the rock is subjected. There may be a stability field for hydrogrossular below 420 ° C at 2 Kb, but not for hydrospessartine. Any occurrence of hydrogarnet may be used as a temperature indicator setting the maximum of formation for the hydrogarnet-bearing assemblage below 420 ° C at 2 Kb.     

Phase relations and mineral assemblages in the Ag-Bi-Pb-S system

Phase relations within the Ag-Bi-S, Bi-Pb-S, and Ag-Pb-S systems have been determined in evacuated silica tube experiments. Integration of experimental data from these systems has permitted examination and extrapolation of phase relations within the Ag-Bi-Pb-S quaternary system. — In the Ag-Bi-S system liquid immiscibility fields exist in the metal-rich portion above 597±3°C and in the sulfur-rich portion above 563±3°C. Ternary phases present correspond to matildite (AgBiS₂) and pavonite (AgBi₃S₅). Throughout the temperature range 802±2°C to 343±2°C the assemblage argentite (Ag₂S) + bismuth-rich liquid is stable; below 343°C this assemblage is replaced by the assemblage silver + matildite. — Five ternary phases are stable on the PbS-Bi₂S₃ join above 400°C — phase II (18 mol-% Bi₂S₃), phase III (27 mol-% Bi₂S₃), cosalite (33.3 mol-% Bi₂S₃), phase IV (51 mol-% Bi₂S₃), and phase V (65 mol-% Bi₂S₃). Phase IV corresponds to the mineral galenobismutite and is stable below 750±3°C. Phases II, III, and V do not occur as minerals, but typical lamellar and myrmekitic textures commonly observed among the Pb-Bi sulfosalts and galena evidence their previous existence in ores. Phase II and III are stable from 829±6°C and 816±6°C, respectively, to below 200°C; Phase V, stable only between 730±5°C and 680±5°C in the pure Bi-Pb-S system is stabilized to 625±5°C by the presence of 2% Ag₂S. Experiments conducted with natural cosalites suggest that this phase is stable only below 425±25°C in the presence of vapor. — In the Ag-Pb-S system the silver-galena assemblage is stable below 784±2°C, whereas the argentite + galena mineral pair is stable below 605±5°C. — Solid solution between matildite and galena is complete above 215±15°C; below this temperature characteristic Widmanstätten structure-like textures are formed through exsolution. Schematic phase relations within the quaternary system are presented at 1050°C, at 400°C, and at low temperature.

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Zusammenfassung Die Phasenbeziehungen in den Systemen Ag-Bi-S, Bi-Pb-S und Ag-Pb-S wurden durch Versuche in evakuierten Quarzglasröhrchen bestimmt. Die Auswertung aller experimentellen Daten gestattete eine Extrapolation der Phasenbeziehungen im quaternären System Ag-Bi-Pb-S. — Im System Ag-Bi-S besteht ein Zwei-Schemlzenfeld im metallreichen Teil über 597±3°C und im schwefelreichen Teil über 563±3°C. Die ternären Phasen entsprechen den Mineralien Schapbachit (AgBiS₂) und Pavonit (AgBi₃S₅). Zwischen 802±2°C und 343±2°C ist die Paragenese Silberglanz (Ag₂S) + Bi-reiche Schmelze stabil; unterhalb 343°C wird sie jedoch ersetzt durch die Paragenese Silber + Schapbachit. — Fünf ternäre Phasen sind stabil im Schnitt PbS-Bi₂S₃ oberhalb von 400°C: Phase II (18 Mol-% Bi₂S₃), Phase III (27 Mol-% Bi₂S₃), Cosalite (33.3 Mol-% Bi₂S₃), Phase IV (51 Mol-% Bi₂S₃) und Phase V (65 Mol-% Bi₂S₃). Phase IV entspricht dem Mineral Galenobismutit und ist stabil unterhalb 750±3°C. Die Phasen II, III und V kommen zwar nicht in der Natur vor, jedoch weisen typische myrmekitische und lamellare Gefüge, die man häufig in Pb-Bi-Sulfosalzen und deren Verwachsungen mit Bleiglanz beobachtet, auf die ehemalige Existenz solcher Phasen in diesen Erzen hin. Die Phasen II und III sind stabil von 829±6°C bzw. 816±6°C bis unter 200°C. Die Phase V, die im reinen System Bi-Pb-S zwischen 730±5°C und 680±5°C auftritt, wird in Gegenwart von 2% Ag₂S stabilisiert bis herab zu 625±5°C. Versuche mit natürlichen Cosaliten lassen darauf schließen, daß diese Phase nur unterhalb 425±25°C in Gegenwart einer Gasphase stabil ist. — Im System Ag-Pb-S ist die Paragenese Silber-Bleiglanz unterhalb von 784±2°C stabil, die Paragenese Silberglanz-Bleiglanz dagegen unterhalb 605±5°C. — Die Mischkristallreihe von Schapbachit und Bleiglanz ist vollständig oberhalb 215±15°C; unterhalb dieser Temperatur entstehen charakteristische Entmischungsgefüge ähnlich den Widmannstättenschen Figuren. Für das quaternäre System werden schematische Phasenbeziehungen für 1050°C, 400°C und eine noch tiefere Temperatur gegeben.

     

Synthesis and stability relations of wairakite,CaAl2 Si4 O12·2H2O

Hydrothermal investigation of the bulk composition CaO·Al₂O₃·4SiO₂ + excess H₂O has been conducted using conventional techniques over the temperature range 200–500° C and 500–5,000 bars P _fluid. The fully ordered wairakite was synthesized unequivocally in the laboratory, probably for the first time.The gradual, sluggish and continuous transformation from disordered to ordered wairakite evidently accounts for failure by previous investigators to synthesize ordered wairakite in runs of week-long duration. The dehydration of metastable disordered wairakite to metastable hexagonal anorthite, quartz and H₂O has been determined; this reaction takes place at temperatures exceeding 400° C, even at fluid pressures of 500 bars or less. The upper P _fluid-T boundary of the disordered phase is equivalent to the maximum temperature curve of synthetic wairakite presented by previous investigators. The hydrothermal breakdown of natural wairakite above its stability limit appears to be a very slow process.The equilibrium dehydration of wairakite to anorthite, quartz and H₂O occurs at 330±5° C at 500 bars, 348±5° C at 1,000 bars, 372±5° C at 2,000 bars and 385±5° C at 3,000 bars. Where fluid pressure equals total pressure, the thermal stability range of wairakite is about 100° C wide. At lower temperatures wairakite reacts with H₂O to form laumontite. Reconnaissance experiments dealing with the effect of CO₂ on stabilities of calcium zeolites suggest that wairakite or laumontite may be replaced by the assemblage calcite + montmorillonite in the presence of a CO₂-bearing fluid phase.The determined P _fluid -T field of wairakite is compatible with field observations in some metamorphic terrains where it is related to the shallow emplacement of granitic magma and with direct pressure-temperature measurements in certain active geothermal areas. Under inferred conditions of higher _CO2/_H2O ratios, essentially unmetamorphosed rocks grade directly into those characteristic of the greenschist facies; moderately high values of _CO2 in carbonate-bearing rocks result in the downgrade extension of the greenschist facies at the expense of zeolite-bearing assemblages.     

Thermochemistry of yavapaiite KFe(SO4)2: Formation and decomposition

Yavapaiite, KFe(SO₄)₂, is a rare mineral in nature, but its structure is considered as a reference for many synthetic compounds in the alum supergroup. Several authors mention the formation of yavapaiite by heating potassium jarosite above ca. 400°C. To understand the thermal decomposition of jarosite, thermodynamic data for phases in the K-Fe-S-O-(H) system, including yavapaiite, are needed. A synthetic sample of yavapaiite was characterized in this work by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermal analysis. Based on X-ray diffraction pattern refinement, the unit cell dimensions for this sample were found to be a = 8.152 ± 0.001 Å, b = 5.151 ± 0.001 Å, c = 7.875 ± 0.001 Å, and β = 94.80°. Thermal decomposition indicates that the final breakdown of the yavapaiite structure takes place at 700°C (first major endothermic peak), but the decomposition starts earlier, around 500°C. The enthalpy of formation from the elements of yavapaiite, KFe(SO₄)₂, ΔH°_f = −2042.8 ± 6.2 kJ/mol, was determined by high-temperature oxide melt solution calorimetry. Using literature data for hematite, corundum, and Fe/Al sulfates, the standard entropy and Gibbs free energy of formation of yavapaiite at 25°C (298 K) were calculated as S°(yavapaiite) = 224.7 ± 2.0 J.mol⁻¹.K⁻¹ and ΔG°_f = −1818.8 ± 6.4 kJ/mol. The equilibrium decomposition curve for the reaction jarosite = yavapaiite + Fe₂O₃ + H₂O has been calculated, at pH₂O = 1 atm, the phase boundary lies at 219 ± 2°C.     

Self-diffusion of Si and O in diopside-anorthite melt at high pressures

Self-diffusion coefficients for Si and O in Di₅₈An₄₂ liquid were measured from 1 to 4 GPa and temperatures from 1510 to 1764°C. Glass starting powders enriched in ¹⁸O and ²⁸Si were mated to isotopically normal glass powders to form simple diffusion couples, and self-diffusion experiments were conducted in the piston cylinder device (1 and 2 GPa) and in the multianvil apparatus (3.5 and 4 GPa). Profiles of ¹⁸O/¹⁶O and ^29,30Si/²⁸Si were measured using secondary ion mass spectrometry. Self-diffusion coefficients for O (D(O)) are slightly greater than self-diffusion coefficients for Si (D(Si)) and are often the same within error. For example, D(O) = 4.20 ± 0.42 × 10⁻¹¹ m²/s and D(Si) = 3.65 ± 0.37 × 10⁻¹¹ m²/s at 1 GPa and 1662°C. Activation energies for self-diffusion are 215 ± 13 kJ/mol for O and 227 ± 13 kJ/mol for Si. Activation volumes for self-diffusion are −2.1 ± 0.4 cm³/mol and −2.3 ± 0.4 cm³/mol for O and Si, respectively. The similar self-diffusion coefficients for Si and O, similar activation energies, and small, negative activation volumes are consistent with Si and O transport by a cooperative diffusion mechanism, most likely involving the formation and disassociation of a high-coordinated intermediate species. The small absolute magnitudes of the activation volumes imply that Di₅₈An₄₂ liquid is close to a transition from negative to positive activation volume, and Adam-Gibbs theory suggests that this transition is linked to the existence of a critical fraction (∼0.6) of bridging oxygen.     

Determination of the second critical end point in silicate-H2O systems using high-pressure and high-temperature X-ray radiography

To determine the second critical end point in silicate-H₂O systems, a new method for the direct observations of immiscible fluids has been developed using a synchrotron X-ray radiography technique. High-pressure and high-temperature experiments were carried out with a Kawai-type, double-stage, multi-anvil high-pressure apparatus (SPEED-1500) installed at BL04B1, SPring-8, Japan. The Sr-plagioclase (SrAl₂Si₂O₈)-H₂O system was used as an illustrative example. A new sample container composed of a metal (Pt) tube with a pair of lids, made of single crystal diamonds, was used under pressures between 3.0 and 4.3 GPa, and temperatures up to ∼1600°C. The sample in the container could be directly observed through the diamond lids with X-ray radiography. At around 980 to 1060°C and pressures between 3.0 and 4.0 GPa, light gray spherical bubbles moving upward through the dark gray matrix were observed. The light gray spheres that absorb less X-rays represent an aqueous fluid, whereas the dark gray matrix represents a silicate melt. These two immiscible phases (aqueous fluid and silicate melt) were observed up to 4.0 GPa. At 4.3 GPa, no bubbles were observed. These observations suggest that the second critical end point in the Sr-plagioclase-H₂O system occurs at around 4.2 ± 0.2 GPa and 1020 ± 50°C. Our new technique can be applied to the direct observations of various systems with two coexisting fluids under deep mantle conditions.     

Reinvestigation of fayalite+anorthite=garnet

The reaction fayalite+anorthite=garnet (GAF) has been investigated in a piston-cylinder apparatus and in an internally heated gas apparatus. Piston-cylinder reversals were obtained at 900 °C (6.0–6.4 kbar), 950 °C (6.3–6.8 kbar), 1000 °C (6.6–7.1 kbar), and 1050 °C (7.0–7.3 kbar). Gas-apparatus experiments yielded a reversal at 7 kbar (993–1049 °C). Results are consistent with earlier experimental studies. Unless garnet Ca–Fe mixing is attended by an excess entropy of at least 2–3 J/K-atom, discrepancies remain between calculated and experimentally determined slopes for GAF. The discrepancy is greater if there is no Al–Si disorder in anorthite. High temperature thermodynamic data for almandine and grossular are needed to help resolve this problem.     

A new sampling technique for fluid phases in hydrothermal experiments applied to the determination of the HF-fugacities of the WFQ-buffer

A new sampling device is described which allows the separation of a fluid phase from the solid reactants in hydrothermal experiments at run conditions. The new method has been tested at temperatures up to 1,100° C at a total vapor pressure of 1 kbar.HF-concentrations of the fluid phase in equilibrium with quartz, fluorite, and wollastonite in the reaction CaF₂+SiO₂+H₂O CaSiO₃+2 HF known as the WFQ-buffer (Munoz and Eugster 1969) have been determined by direct chemical analysis using a fluoride electrode. HF-concentrations measured in the fluid phase range from 39±3 ppm at 510° C to 1,968±98 ppm at 820° C. This is equivalent to fugacities of 0.036 bar at 510° C compared to 0.033 as calculated from thermodynamic data, and 2.238 bar at 820° C compared to 2.142 bar. Equilibrium was reversed by starting out from aqueous HF-solutions in which the HF-concentrations were above or below the equilibrium value.     

Dual speciation of nitrogen in silicate melts at high pressure and temperature: An experimental study

Solubility and speciation of nitrogen in silicate melts have been investigated between 1400 and 1700 °C and at pressures ranging from 10 to 30 kbar for six different binary alkali and alkaline-earth silicate liquids and a Ca-Mg-alumino silicate. Experiments were performed in a piston-cylinder apparatus. The nitrogen source is silver azide, which breaks down to Ag and molecular N₂ below 300 °C. At high pressure and temperature, the nitrogen content may be as high as 0.7 wt% depending on the melt composition, pressure, and temperature. It increases with T, P and the polymerization state of the liquid. Characterization by Raman spectroscopy and ¹⁵N solid state MAS NMR indicates that nitrogen is not only physically dissolved as N₂ within the melt structure like noble gases, but a fraction of nitrogen interacts strongly with the silicate network. The most likely nitrogen-bearing species that can account for Raman and NMR results is nitrosyl group. Solubility data follow an apparent Henry’s law behavior and are in good agreement with previous studies when the nitrosyl content is low. On the other hand, a significant departure from a Henry’s law behavior is observed for highly depolymerized melts, which contain more nitrosyl than polymerized melts. Possible solubility mechanisms are also discussed. Finally, a multi-variant empirical relation is given to predict the relative content of nitrosyl and molecular nitrogen as a function of P, T, and melt composition and structure. This complex speciation of nitrogen in melts under high pressure may have significant implication concerning crystal-melt partitioning of nitrogen as well as for potential elemental and isotopic fractionation of nitrogen in the deep Earth.     

Experimental determination of pargasite stability relations in the presence of orthopyroxene

The stability and partial melting of synthetic pargasite in the presence of enstatitic orthopyroxene (opx), forsterite, diopsidic clinopyroxene (cpx), plagioclase (An₅₀), and water has been studied in the range of 0.4–6.0 kb and 750–1000°C in the system Na₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O with a fixed bulk composition of pargasite+5 opx. The addition of orthopyroxene effectively reduces the stability field of pargasite by approximately 200°C at 1 kb. The invariant point involving pargasite coexisting with water-saturated liquid and anhydrous phase shifts from about 0.85 kb and 1025°C to 2.5±0.5 kb and 925±25°C with the addition of opx. Based on the solidus mineral assemblage and direct chemical analysis of quenched glass, the vapor-saturated liquid has a composition close to that of intermediate plagioclase. A layered silicate, interpreted to be Na-phlogopite, has an upper-thermal stability that nearly equals that of pargasite in the field of partial melting and coexists with liquid, pargasite, cpx, and forsterite at 6 kb, 1000°C. These results support the hypothesis that mantle metasomatism could involve formation of pargasitic amphibole from a silicate melt at depths as shallow as 8–10 km.     

Generation of mid-ocean ridge basalts at pressures from 1 to 7 GPa

We propose a model for the generation of average MORBs based on phase relations in the CaO-MgO-Al₂O₃-SiO₂-CO₂ system at pressures from 3 to 7 GPa and in the CaO-MgO-Al₂O₃-SiO₂-Na₂O-FeO (CMASNF) system at pressures from ∼0.9 to 1.5 GPa. The MELT seismic tomography (Forsyth et al., 2000) across the East Pacific Rise shows the largest amount of melt centered at ∼30-km depth and lesser amounts at greater depths. An average mantle adiabat with a model-system potential temperature (T_p) of 1310°C is used that is consistent with this result. In the mantle, additional minor components would lower solidus temperatures ∼50°C, which would lower T_p of the adiabat for average MORBs to ∼1260°C. The model involves generation of carbonatitic melts and melts that are transitional between carbonatite and kimberlite at very small melt fractions (<0.2%) in the low-velocity zone at pressures of ∼2.6 to 7 GPa in the CMAS-CO₂ system, roughly the pressure range of the PREM low-velocity zone. These small-volume, low-viscosity melts are mixed with much larger volumes of basaltic melt generated at the plagioclase-spinel lherzolite transition in the pressure range of ∼0.9 to 1.5 GPa.In this model, solidus phase relations in the pressure range of the plagioclase-spinel lherzolite transition strongly, but not totally, control the major-element characteristics of MORBs. Although the plagioclase-spinel lherzolite transition suppresses isentropic decompression melting in the CMAS system, this effect does not occur in the topologically different and petrologically more realistic CMASNF system. On the basis of the absence of plagioclase from most abyssal peridotites, which are the presumed residues of MORB generation, we calculate melt productivity during polybaric fractional melting in the plagioclase-spinel lherzolite transition interval at exhaustion of plagioclase in the residue. In the CMASN system, these calculations indicate that the total melt productivity is ∼24%, which is adequate to produce the oceanic crust. The residual mineral proportions from this calculation closely match those of average abyssal peridotites.Melts generated in the plagioclase-spinel lherzolite transition are compositionally distinct from all MORB glasses, but do not have a significant fractional crystallization trend controlled by olivine alone. They reach the composition field of erupted MORBs mainly by crystallization of both plagioclase and olivine, with initial crystallization of either one of these phases rapidly joined by the other. This is consistent with phenocryst assemblages and experimental studies of the most primitive MORBs, which do not show an olivine-controlled fractionation trend. The model is most robust for the eastern Pacific, where an adiabat with a T_p of ∼1260°C is supported by the MELT seismic data and where the global inverse correlation of (FeO)₈ with (Na₂O)₈ is weak. Average MORBs worldwide also are well modeled. A heterogeneous mantle consisting of peridotite of varying degrees of major-element depletion combined with phase-equilibrium controls in the plagioclase-spinel lherzolite transition interval would produce the form of the global correlations at a constant T_p, which suggests a modest range of T_p along ridges. Phase-composition data for the CMASNF system are presently not adequate for quantitative calculation of (FeO)₈-(Na₂O)₈-(CaO/Al₂O₃)₈ systematics in terms of this model. The near absence of basalts in the central portion of the Gakkel Ridge suggests a lower bound for T_p along ridges of ∼1240°C, a potential temperature just low enough to miss the solidus for basalt production at ∼0.9 GPa. An upper bound for T_p is poorly constrained, but the complete absence of picritic glasses in Iceland and the global ridge system suggests an upper bound of ∼1400°C. In contrast to some previous models for MORB generation that emphasize large potential temperature variations in a relatively homogeneous peridotitic mantle, our model emphasizes modest potential temperature variations in a peridotitic mantle that shows varying degrees of heterogeneity. Calculations indicate that melt productivity changes from 0 to 24% for a change in T_p from 1240 to 1260°C, effectively producing a rapid increase to full crustal thickness or decrease to none as ridges appear and disappear.