High pressure fluids in the system MgO–SiO2–H2O under upper mantle conditions

Fluids and melts have been trapped and analysed in high pressure experiments in the model mantle system MgO-SiO₂-H₂O at 6 to 10.5 GPa and 900 to 1,200 °C. The fluid/melt traps consisted of a diamond layer that was added to the experimental charge and was separate from the silicate phases. The recovered diamond traps were analysed by laser ablation - ICP - MS. Starting materials were synthetic mixtures of brucite, talc and silica with variable Mg/Si containing 11-31 wt% H₂O. Experiments on a serpentine starting composition [Mg₃Si₂O₅(OH)₄] result in MgO/SiO₂ weight ratios in the subsolidus fluids close to 1 at 6 GPa and close to 2 at 9 GPa. Melt compositions at 6 and 9 GPa have MgO/SiO₂ ratios close to that of forsterite. At a single pressure the amount of dissolved silicate in the fluid increases steadily with increasing temperature up to 1,150 °C, where a sudden increase of both SiO₂ and MgO is observed. This discrete step marks the solidus, which is more clearly developed at 6 than at 9 GPa. Thus, hydrous melts within the model mantle subsystem Mg₂SiO₄-Mg₂Si₂O₆-H₂O are chemically distinct from aqueous fluids up to at least 9 GPa, corresponding to 300 km depth. Extrapolation of the current data set implies that total convergence between fluid and melt along the solidus probably occurs at 12-13 GPa (~400 km), i.e. close to the Earth's mantle transition zone. Beneath cratons, interactions of hydrous fluids with upper mantle lithologies cause relative silica depletion (olivine enrichment) at depths greater than 200 km and silica (orthopyroxene) enrichment at shallower depths.     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

Beginning of melting and subsolidus relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt.The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K₂O-CaO-Al₂O₃-SiO₂-H₂O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al₂O₃-SiO₂-H₂O.The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al₂O₃-SiO₂-H₂O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper.The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al₂SiO₅ polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.     

Phase relationships in the system KAlSiO4-Mg2SiO4-SiO2-H2O as a model for hybridization between hydrous siliceous melts and peridotite

The system KAlSiO₄-Mg₂SiO₄-SiO₂-H₂O includes model representatives of (1) hydrous siliceous magma from subducted oceanic crust — the eutectic liquid in KAlSi₃O₈-SiO₂-H₂O, and (2) the overlying mantle peridotite — the assemblage forsterite+enstatite (Fo+En). In a series of partly schematic isobaric isothermal sections, the products of hybridization between the model materials at pressures between 20 and 30 kbar have been determined. The liquid dissolves peridotite components with little change in composition. Hybridization is not a simple mixing process, because of the incongruent melting of peridotitic assemblages with phlogopite (Ph). Hybridization causes solidification of the liquid, with products a sequence of three mineral assemblages: Ph, Ph+quartz (Qz), and Ph+En. The products represent an absolute geochemical separation and local concentration of all potassium from the liquid. Hybridization is accompanied by H₂O-saturation of melts, and evolution of aqueous fluid. Although there are significant differences between the melt composition and that of the magma rising from subducted oceanic slab, and between Fo+En and the mantle rock, extrapolation of the results suggests that the conclusions can probably be extended to mantle conditions with sodium in the melt, and jadeitic clinopyroxene included in the hybrid products.     

Composition of aqueous fluid coexisting with mantle minerals at high pressure and its bearing on the differentiation of the Earth’s mantle

In order to understand the role of aqueous fluid on the differentiation of the mantle, the compositions of aqueous fluids coexisting with mantle minerals were investigated in the system MgO-SiO₂-H₂O at pressures of 3 to 10 GPa and temperatures of 1000 to 1500°C with an MA8-type multianvil apparatus. Phase boundaries between the stability fields of forsterite + aqueous fluid, forsterite + enstatite + aqueous fluid, and enstatite + aqueous fluid were determined by varying the bulk composition at constant temperature and pressure. The composition of aqueous fluid coexisting with forsterite and enstatite can be defined by the intersection of these two phase boundaries. The solubility of silicate components in aqueous fluid coexisting with forsterite and enstatite increases with increasing pressure up to 8 GPa, from about 30 wt% at 3 GPa to about 70 wt% at 8 GPa. It becomes almost constant above 8 GPa. The Mg/Si weight ratio of these aqueous fluids is much higher than at low pressure (0.2 at 1.5 GPa) and almost constant (1.2) at pressures between 3 and 8 GPa. At 10 GPa, it becomes about 1.4. Aqueous fluid migrating upward through the mantle can therefore dissolve large amounts of silicates, leaving modified Mg/Si ratios of residual materials. It is suggested that the chemical stratification of Mg/Si in the Earth may have been formed as a result of aqueous fluid migration.     

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

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

Preferential dissolution of SiO<Subscript>2</Subscript> from enstatite to H<Subscript>2</Subscript> fluid under high pressure and temperature

Stability and phase relations of coexisting enstatite and H₂ fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO₂ grains were found at the margin of the heating hot spot, suggesting that the SiO₂ component dissolved in the H₂ fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH₄ and H₂O molecules formed through the reaction between dissolved SiO₂ and H₂. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO₂ components of enstatite in H₂ fluid, as well as that observed in the forsterite H₂ system and the quartz H₂ system, implies that H₂-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.     

Effect of KCl on melting in the Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>–MgSiO<Subscript>3</Subscript>–H<Subscript>2</Subscript>O system at 5 GPa

To examine the effect of KCl-bearing fluids on the melting behavior of the Earth’s mantle, we conducted experiments in the Mg₂SiO₄–MgSiO₃–H₂O and Mg₂SiO₄–MgSiO₃–KCl–H₂O systems at 5 GPa. In the Mg₂SiO₄–MgSiO₃–H₂O system, the temperature of the fluid-saturated solidus is bracketed between 1,200–1,250°C, and both forsterite and enstatite coexist with the liquid under supersolidus conditions. In the Mg₂SiO₄–MgSiO₃–KCl–H₂O systems with molar Cl/(Cl + H₂O) ratios of 0.2, 0.4, and 0.6, the temperatures of the fluid-saturated solidus are bracketed between 1,400–1,450°C, 1,550–1,600°C, and 1,600–1,650°C, respectively, and only forsterite coexists with liquid under supersolidus conditions. This increase in the temperature of the solidus demonstrates the significant effect of KCl on reducing the activity of H₂O in the fluid in the Mg₂SiO₄–MgSiO₃–H₂O system. The change in the melting residues indicates that the incongruent melting of enstatite (enstatite = forsterite + silica-rich melt) could extend to pressures above 5 GPa in KCl-bearing systems, in contrast to the behavior in the KCl-free system.     

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni–NiO–H₂O (ΔFMQ = ??0.21 to ??1.01), employing a double-capsule setting. Fluids, binary H₂O–CO₂ mixtures at the P, T, and fO₂ conditions investigated, were generated from graphite, oxalic acid anhydrous (H₂C₂O₄) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO₂-bearing fluids. The experimental data show that forsterite?+?enstatite solubility in H₂O–CO₂ fluids is higher compared to pure water, both in terms of dissolved silica (mSiO₂?=?1.24 mol/kg_H2O versus mSiO₂?=?0.22 mol/kg_H2O at P?=?1 GPa, T?=?800 °C) and magnesia (mMgO?=?1.08 mol/kg_H2O versus mMgO?=?0.28 mol/kg_H2O) probably due to the formation of organic C–Mg–Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H₂O–CO₂ fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO₂ ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO₂ ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P–T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle.     

Fractionation of major elements between coexisting H2O-saturated silicate melt and silicate-saturated aqueous fluids in aluminosilicate systems at 1-2 GPa

From experimental data in the systems Na₂O-Al₂O₃-SiO₂-H₂O, K₂O-Al₂O₃-SiO₂-H₂O at 1100°C, and CaO-Al₂O₃-SiO₂-H₂O at 1200°C in the 1-2 GPa pressure range, the solution behavior of the individual oxides in coexisting H₂O-saturated silicate melts and silicate-saturated aqueous fluids appears to be incongruent. Recalculated on an anhydrous basis, in the CaO-Al₂O₃-SiO₂-H₂O system, CaO^fluid/CaO^melt < 1, whereas in the Na₂O-Al₂O₃-SiO₂-H₂O and K₂O-Al₂O₃-SiO₂-H₂O systems, K₂O^fluid/K₂O^melt and Na₂O^fluid/Na₂O^melt both are greater than 1. The aqueous fluids are depleted in alumina relative to silicate melt.In the Na₂O-Al₂O₃-SiO₂-H₂O, K₂O-Al₂O₃-SiO₂-H₂O, and CaO-Al₂O₃-SiO₂-H₂O systems, fluid/melt partition coefficients for the individual oxides range between ∼0.005 and 0.35 depending on oxide, bulk composition and pressure. The alkali partition coefficients are about an order of magnitude higher than that of CaO. Alumina and silica partition coefficient values in the CaO-Al₂O₃-SiO₂-H₂O system are 10-20% of the values for the same oxides in the Na₂O-Al₂O₃-SiO₂-H₂O and K₂O-Al₂O₃-SiO₂-H₂O systems.Positive correlations among individual partition coefficients and oxide concentrations in the aqueous fluids are consistent with complexing in the fluid that involves silicate polymers associated with alkalis and alkaline earths and aluminosilicate complexes where alkalis and alkaline earths may serve to charge-balance Al³⁺, which is, perhaps, in tetrahedral coordination. Alkali aluminosilicate complexes in aqueous fluid appear more stable than Ca-aluminosilicate complexes.     

Solubility behavior of alkali aluminosilicate components in aqueous fluids and silicate melts at high pressure and temperature

The solubility behavior of K₂O, Na₂O, Al₂O₃, and SiO₂ in silicate-saturated aqueous fluid and coexisting H₂O-saturated silicate melts in the systems K₂O-Al₂O₃-SiO₂-H₂O and Na₂O-Al₂O₃-SiO₂-H₂O has been examined in the 1- to 2-GPa pressure range at 1100°C. Glasses of Na- and K-tetrasilicate compositions with 0, 3, and 6 mol% Al₂O₃ were used as starting materials. In both systems, the oxides dissolve incongruently in aqueous fluid and silicate melt. When recalculated to an anhydrous basis, the aqueous fluids are enriched in alkalis and depleted in silica and alumina relative to their proportions in the starting materials. The extent of incongruency is more pronounced in the Na₂O-Al₂O₃-SiO₂-H₂O system than in the K₂O-Al₂O₃-SiO₂-H₂O system.The partition coefficients of the oxides, D_oxide^fluid/melt, are linear and positive functions of the oxide concentration in the fluid for each composition. There is a slight dependence of the partition coefficients on bulk composition. No effect of pressure could be discerned. For alkali metals, the fluid/melt partition coefficients range from 0.06 to 0.8. For Al₂O₃ this range is 0.01 to 0.2, and for SiO₂, it is 0.01 to 0.32. For all compositions, D_K2O^fluid/melt∼D_Na2O^fluid/melt>D_SiO2^fluid/melt>D_Al2O3^fluid/melt for the same oxide concentration in the fluid. D_K2O^fluid/melt, D_Na2O^fluid/melt, and D_SiO2^fluid/melt correlate negatively with the Al₂O₃ content of the systems. This correlation is consistent with a solubility model of alkalis that involve associated KOH°, NaOH°, silicate, and aluminate complexes.     

Liquidus phase relationships on the join anorthite-forsterite-quartz at 10 kbar with applications to basalt petrogenesis

Liquidus phase relationships determined on the join CaAl₂Si₂O₈ (anorthite)-Mg₂SiO₄ (forsterite)-SiO₂ (quartz) at 10 kbar show that increasing pressure causes the forsterite and anorthite primary phase fields to shrink and the spinel, enstatite and silica fields to expand. The boundary line between the enstatite and forsterite fields and that between the enstatite and quartz fields both move away from the SiO₂ apex as pressure increases. Therefore, simplified source peridotite would yield simplified basaltic partial melts with decreasing silica as pressure increases, as has been found in other studies. Also, increasing pressure decreases the amount of silica enrichment in residual liquids produced by fractional crystallization. Although anorthite is unstable in simplified peridotite above 9 kbar in the system CaO-MgO-Al₂O₃-SiO₂, it is an important phase in the fractional crystallization of simplified basalts at 10 kbar and probably also in natural basalts.Contribution no. 419, Department of Geosciences, University of Texas at Dallas     

Effect of oxygen fugacity on the H2O storage capacity of forsterite in the carbon-saturated systems

High pressure experiments have been performed in the systems Mg₂SiO₄-C-O-H and Mg₂SiO₄-K₂CO₃-C at 6.3 GPa and 1200 to 1600 °C using a split-sphere multi-anvil apparatus. In the Mg₂SiO₄-C-O-H system the composition of fluid was modeled by adding different amounts of water and stearic acid. The fO₂ was controlled by the Mo-MoO₂ or Fe-FeO oxygen buffers. Several experiments in the Mg₂SiO₄-C-O-H system and all experiments in the Mg₂SiO₄-K₂CO₃-C system have been conducted without buffering the fO₂. Forsterite in the system Mg₂SiO₄-K₂CO₃-C does not reveal OH absorption bands in the IR spectra, while forsterite coexisting with carbon-bearing fluid and silicate melt at logfO₂ from FMQ-2 to FMQ-5 (from 2 to 5 log units below fayalite-magnetite-quartz oxygen buffer) contains 800-1850 wt. ppm H₂O. The maximum concentrations were detected at 1400 °C and FMQ-3.5. We observed an increase in the solidus temperature in the system Mg₂SiO₄-C-O-H from 1200 to above 1600 °C with log fO₂ decreasing from FMQ-2 to FMQ-5. The increase of the solidus temperature and the broadening of the stability field of the H₂O-H₂-CH₄ subsolidus fluid phase at 1400-1600 °C explain the high H₂O storage capacity of forsterite relative to that crystallized from carbon-free, oxidized, hydrous, silicic melt. At temperatures above 1400 °C liquidus forsterite precipitated along with diamond from oxidized (FMQ-1) carbonate-silicate melt and from silicate melt dissolving the moderately reduced C-O-H fluid (from FMQ-2 to FMQ-3.5). Formation of diamond was not detected under ultra-reduced conditions (FMQ-5) at 1200-1600 °C. Olivine co-precipitating with diamond from dry carbonate-silicate or hydrous-silicic fluid/melt can provide information on the H₂O contents and speciation of the diamond-forming media in the mantle. The conditions for minimum post-crystallization alteration of olivine and its hydrogen content are discussed.     

New experimental data for the system CaO-MgO-SiO2-H2O and a synthesis of inferred phase relations

Subsolidus and vapor-saturated liquidus phase relations for a portion of the system CaO-MgO-SiO₂-H₂O, as inferred from experimental data for the composition regions CaMgSi₂O₆-Mg₂SiO₄-SiO₂-H₂O and CaMgSi₂O₆-Mg₂SiO₄-Ca₃MgSi₂O₈ (merwinite)-H₂O, are presented in pressure-temperature projection. Sixteen invariant points and 39 univariant reactions are defined on the basis of the 1 atm and 10 kbar (vapor-saturated) liquidus diagrams. Lack of experimental control over many of the reactions makes the depicted relations schematic in part.An invariant point involving orthoenstatite, protoenstatite, pigeonite, and diopside (all solid solutions) occurs at low pressure (probably between 1 and 2 kbar). At pressures below this invariant point, orthoenstatite breaks down at high temperature to the assemblage diopside + protoenstatite; with increasing temperature, the latter assemblage reacts to form pigeonite. At pressures above the invariant point, pigeonite forms according to the reaction diopside + orthoenstatite = pigeonite, and the assemblage diopside + protoenstatite is not stable. At 1 atm, both pigeonite and protoenstatite occur as primary liquidus phases, but at pressures above 6–7 kbar orthoenstatite is the only Ca-poor pyroxene polymorph which appears on the vapor-saturated liquidus surface.At pressures above approximately 10.8 kbar, only diopside, forsterite, and merwinite occur as primary liquidus phases in the system CaMgSi₂O₆-Mg₂SiO₄-Ca₃MgSi₂O₈-H₂O, in the presence of an aqueous vapor phase. At pressures between 1 atm and 10.2 kbar, both akermanite and monticellite also occur as primary liquidus phases. Comparison of the 1 atm and 10 kbar vapor-saturated liquidus diagrams suggests that melilite basalt bears a low pressure, or shallow depth, relationship to monticellite-bearing ultrabasites.     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O: corrections and additional experimental data

Melting relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been reinvestigated using Schreinemakers analysis and hydrothermal experiments. The reaction sanidine+muscovite+zoisite+quartz+vapor =melt has been bracketed at 10, 15, and 20 kbars and 670–680, 680–690, and 690–700° C, respectively and it marks the lowest solidus temperatures in the system investigated.Below 10 kbars, experimental data on the beginning of melting in zoisite- or muscovite-bearing anorthite+sanidine assemblages have been obtained, which are not showing any differences and therefore point to melt compositions close to the feldspar-quartz join.     

Stability of the assemblage orthopyroxene-sillimanite-quartz in the system MgO-FeO-Fe2O3-Al2O3-SiO2-H2O

The stability of coexisting orthopyroxene, sillimanite and quartz and the composition of orthopyroxene in this assemblage has been determined in the system MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-H₂O as a function of pressure, mainly at 1,000° C, and at oxygen fugacities defined mostly by the hematite-magnetite buffer. The upper stability of the assemblage is terminated at 17 kbars, 1,000° C, by the reaction opx+Al-silicate gar+qz, proceeding toward lower pressures with increasing Fe/(Fe+Mg) ratio in the system. The lower stability is controlled by the reaction opx+sill+qz cord, which occurs at 11 kbars in the iron-free system but is lowered to 9 kbars with increasing Fe/(Fe+Mg). Spinel solid solutions are stabilized, besides quartz, up to 14 kbars in favour of garnet in the iron-rich part of the system (Fe/(Fe+Mg)0.30). Ferric-ferrous ratios in orthopyroxene are increasing with increasing ferro-magnesian ratio. At least part of the generally observed increase in Al content with Fe²⁺ in orthopyroxene is not due to an increased solubility of the MgAlAlSiO₆ component but rather of a MgFe³⁺AlSiO₆ component. The data permit an estimate of oxygen fugacity from the composition of orthopyroxene in coexistence with sillimanite and quartz.     

Liquidus phase relations on the join diopside-forsterite-anorthite from 1 atm to 20 kbar: Their bearing on the generation and crystallization of basaltic magma

In the system CaO-MgO-Al₂O₃-SiO₂, the tetrahedron CaMgSi₂O₆(di)-Mg₂SiO₄(fo)-SiO₂-CaAl₂ SiO₆(CaTs) forms a simplified basalt tetrahedron, and within this tetrahedron, the plane di-fo-CaAl₂Si₂O₈(an) separates simplified tholeiitic from alkalic basalts. Liquidus phase relations on this join have been studied at 1 atm and at 7, 10, 15, and 20 kbar. The temperature maximum on the 1 atm isobaric quaternary univariant line along which forsterite, diopside, anorthite, and liquid are in equilibrium lies to the SiO₂-rich side of the join di-fo-an. The isobaric quaternary invariant point at which forsterite, diopside, anorthite, spinel, and liquid are in equilibrium passes, with increasing pressure, from the silica-poor to the silica-rich side of the join di-fo-an, which causes the piercing points on this join to change from forsterite+diopside+anorthite+liquid and forsterite +spinel+anorthite+liquid below 5 kbar to forsterite +diopside+spinel+liquid and diopside +spinel+anorthite+liquid above 5 kbar. As pressure increases, the forsterite and anorthite fields contract and the diopside and corundum fields expand. The anorthite primary phase field disappears entirely from the join di-fo-an between 15 and 20 kbar. Below about 4 kbar, the join di-fo-an represents, in simplified form, a thermal divide between alkalic and tholeiitic basalts. From about 4 to at least 12 kbar, alkalic basalts can produce tholeiitic basalts by fractional crystallization, and at pressures above about 12 kbar, it is possible for alkalic basalt to be produced from oceanite by crystallization of both olivine and orthopyroxene. If alkalic basalts are primary melts from a lherzolite mantle, they must be produced at high pressures, probably greater than about 12 kbar.Department of Geosciences, University of Texas at Dallas Contribution No. 327. Hawaii Institute of Geophysics Contribution No. 814.     

Hydration of mantle olivine under variable water and oxygen fugacity conditions

The incorporation of H into olivine is influenced by a significant number of thermodynamic variables (pressure, temperature, oxygen fugacity, etc.). Given the strong influence that H has on the solidus temperature and rheological behavior of mantle peridotite, it is necessary to determine its solubility in olivine over the range of conditions found in the upper mantle. This study presents results from hydration experiments carried out to determine the effects of pressure, temperature, and the fugacities of H₂O and O₂ on H solubility in San Carlos olivine at upper mantle conditions. Experiments were carried out at 1–2 GPa and 1,200 °C using a piston-cylinder device. The fugacity of O₂ was controlled at the Fe⁰–FeO, FeO–Fe₃O₄, or Ni⁰–NiO buffer. Variable duration experiments indicate that equilibration is achieved within 6 h. Hydrogen contents of the experimental products were measured by secondary ion mass spectrometry, and relative changes to the point defect populations were investigated using Fourier transform infrared spectroscopy. Results from our experiments demonstrate that H solubility in San Carlos olivine is sensitive to pressure, the activity of SiO₂, and the fugacities of H₂O and O₂. Of these variables, the fugacity of H₂O has the strongest influence. The solubility of H in olivine increases with increasing SiO₂ activity, indicating incorporation into vacancies on octahedral lattice sites. The forsterite content of the olivine has no discernible effect on H solubility between 88.17 and 91.41, and there is no correlation between the concentrations of Ti and H. Further, in all but one of our experimentally hydrated olivines, the concentration of Ti is too low for H to be incorporated dominantly as a Ti-clinohumite-like defect. Our experimentally hydrated olivines are characterized by strong infrared absorption peaks at wavenumbers of 3,330, 3,356, 3,525, and 3,572 cm^?1. The heights of peaks at 3,330 and 3,356 cm^?1 correlate positively with O₂ fugacity, while those at 3,525 and 3,572 cm^?1 correlate with H₂O fugacity.     

Transition metals in the transition zone: partitioning of Ni,Co, and Zn between olivine,wadsleyite, ringwoodite,and clinoenstatite

Ni, Co, and Zn are widely distributed in the Earth’s mantle as significant minor elements that may offer insights into the chemistry of melting in the mantle. To better understand the distribution of Ni²⁺, Co²⁺, and Zn²⁺ in the most abundant silicate phases in the transition zone and the upper mantle, we have analyzed the crystal chemistry of wadsleyite (Mg₂SiO₄), ringwoodite (Mg₂SiO₄), forsterite (Mg₂SiO₄), and clinoenstatite (Mg₂Si₂O₆) synthesized at 12–20 GPa and 1200–1400 °C with 1.5–3 wt% of either NiO, CoO, or ZnO in starting materials. Single-crystal X-ray diffraction analyses demonstrate that significant amounts of Ni, Co, and Zn are incorporated in octahedral sites in wadsleyite (up to 7.1 at%), ringwoodite (up to 11.3 at%), olivine (up to 2.0 at%), and clinoenstatite (up to 3.2 at%). Crystal structure refinements indicate that crystal field stabilization energy (CFSE) controls both cation ordering and transition metal partitioning in coexisting minerals. According to electron microprobe analyses, Ni and Co partition preferentially into forsterite and wadsleyite relative to coexisting clinoenstatite. Ni strongly prefers ringwoodite over coexisting wadsleyite with \({D}_{\text{Ni}}^{\text{Rw}/\text{Wd}}\)?=?4.13. Due to decreasing metal–oxygen distances with rising pressure, crystal field effect on distribution of divalent metal ions in magnesium silicates is more critical in the transition zone relative to the upper mantle. Analyses of Ni partitioning between the major upper-mantle phases implies that Ni-rich olivine in ultramafic rocks can be indicative of near-primary magmas.     

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.     

The formation of mantle phlogopite in subduction zone hybridization

Extrapolation and extension of phase equilibria in the model system KAlSiO₄-Mg₂SiO₄-SiO₂-H₂O suggests that at depths greater than 100 km (deeper than amphibole stability), hybridism between cool hydrous siliceous magma, rising from subducted oceanic crust, and the hotter overlying mantle peridotite produces a series of discrete masses composed largely of phlogopite, orthopyroxene, and clinopyroxene (enriched in Jadeite). Quartz (or coesite) may occur with phlogopite in the lowest part of the masses. The heterogeneous layer thus produced above the subducted oceanic crust provides: (1) aqueous fluids expelled during hybridization and solidification, which rise to generate in overlying mantle (given suitable thermal structure) H₂O-undersaturated basic magma, which is the parent of the calc-alkalic rock series erupted at the volcanic front; (2) masses of phlogopite-pyroxenites which melt when they cross a deeper, high-temperature solidus, yielding the parents of alkalic magmas erupted behind the volcanic front; and (3) blocks of phlogopite-pyroxenites which may rise diapirically for long-term residence in continental lithosphere, and later contribute to the potassium (and geochemically-related elements) involved in some of the continental magmatism with geochemistry ascribed to mantle metasomatism.