Magmatic evolution of the material of the Earth’s lower mantle: Stishovite paradox and origin of superdeep diamonds (Experiments at 24–26 GPa)

The ultrabasic–basic magmatic evolution of the lower mantle material includes important physicochemical phenomena, such as the stishovite paradox and the genesis of superdeep diamonds. Stishovite SiO₂ and periclase–wüstite solid solutions, (MgO · FeO)_ss, associate paradoxically in primary inclusions of superdeep lower mantle diamonds. Under the conditions of the Earth’s crust and upper mantle, such oxide assemblages are chemically impossible (forbidden), because the oxides MgO and FeO and SiO₂ react to produce intermediate silicate compounds, enstatite and ferrosilite. Experimental and physicochemical investigations of melting phase relations in the MgO–FeO–SiO₂–CaSiO₃ system at 24 GPa revealed a peritectic mechanism of the stishovite paradox, (Mg, Fe)SiO₃ (bridgmanite) + L = SiO₂ + (Mg, Fe)O during the ultrabasic–basic magmatic evolution of the primitive oxide–silicate lower mantle material. Experiments at 26 GPa with oxide–silicate–carbonate–carbon melts, parental for diamonds and primary inclusions in them, demonstrated the equilibrium formation of superdeep diamonds in association with ultrabasic, (Mg, Fe)SiO₃ (bridgmanite) + (MgO · FeO)_ss (ferropericlase), and basic minerals, (FeO · MgO)_ss (magnesiowüstite) + SiO₂ (stishovite). This leads to the conclusion that a peritectic mechanism, similar to that responsible for the stishovite paradox in the pristine lower mantle material, operates also in the parental media of superdeep diamonds. Thus, this mechanism promotes both the ultrabasic–basic evolution of primitive oxide–silicate magmas in the lower mantle and oxide–silicate–carbonate melts parental for superdeep diamonds and their paradoxical primary inclusions.     

Subsolidus and melting phase relations of basaltic composition in the uppermostlower mantle

The phase relations and the element partitioning in a mid-oceanic ridge basalt composition were determined for both above-solidus and subsolidus conditions at 22 to 27.5 GPa by means of a multianvil apparatus. The mineral assemblage at the solidus changes remarkably with pressure; majorite and stishovite at 22 GPa, joined by Ca-perovskite at 23 GPa, further joined by CaAl₄Si₂O₁₁-rich CAS phase at 25.5 GPa, and Mg-perovskite, stishovite, Ca-perovskite, CF phase (approximately on the join NaAlSiO₄-MgAl₂O₄), and NAL phase ([Na,K,Ca]₁[Mg,Fe²⁺]₂[Al,Fe³⁺,Si]_5.5-6.0O₁₂) above 27 GPa. The liquidus phase is Ca-perovskite, and stishovite, a CAS phase, a NAL phase, Mg-perovskite, and a CF phase appear with decreasing temperature at 27.5 GPa. Partial melt at 27 to 27.5 GPa is significantly depleted in SiO₂ and CaO and enriched in FeO and MgO compared with those formed at lower pressures, reflecting the narrow stability of (Fe,Mg)-rich phases (majorite or Mg-perovskite) above solidus temperature. The basaltic composition has a lower melting temperature than the peridotitic composition at high pressures except at 13 to 18 GPa (Yasuda et al., 1994) and therefore can preferentially melt in the Earth’s interior. Recycled basaltic crusts were possibly included in hot Archean plumes, and they might have melted in the uppermost lower mantle. In this case, Ca-perovskite plays a dominant role in the trace element partitioning between melt and solid. This contrasts remarkably with the case of partial melting of a peridotitic composition in which magnesiowüstite is the liquidus phase at this depth.     

Phase transformations in descending plates and implications for mantle dynamics

The role of phase transformations in a mantle of pyrolite composition is reviewed in the light of recent experimental data. The pyroxene component of pyrolite transforms to the garnet structure at 300–350 km whilst olivine transforms to beta-Mg₂SiO₄ near 400 km. Between about 500 and 550 km, beta-Mg₂SiO₄ probably transforms to a partially inverse spinel structure whilst the CaSiO₃ component of the complex garnet solid solution exsolves and transforms to the perovskite structure. The major seismic discontinuity near 650–700 km is probably caused by disproportionation of Mg₂SiO₄ spinel into periclase plus stishovite. At a slightly greater depth, the remaining magnesian garnet transforms to the corundum or ilmenite structure. Finally, at a depth probably in the vicinity of 800–1000 km, the (Mg,Fe)SiO₃ component of the ilmenite phase transforms to a perovskite structure whilst stishovite and some of the periclase recombine to form perovskite also. The mineral assemblage so formed is about 4% denser than mixed oxides (MgO + FeO + A1₂O₃ + CaO + stishovite) isochemical with pyrolite. The above sequence of phase transformations in pyrolite provides a satisfactory general explanation of the elastic properties and density distribution in the mantle. In particular, there is no evidence requiring an increase of FeO/(FeO + MgO) ratio with depth.The depths at which major phase transformations occur in subducted lithosphere differ from those in ‘normal’ mantle. These differences are caused by two factors: (1) Temperatures within sinking plates are much lower than in surrounding mantle to depths of 700 km or more. (2) Irreversible chemical differentiation of pyrolite occurs at oceanic ridges. Lithosphere plates so formed consist of a layer of basaltic rocks underlain successively by layers of harzburgite, lherzolite, and pyrolite slightly depleted in highly incompatible elements (e.g. La, Ba, Rb, U). The phase-transformation behaviour of the first three of these layers differs from that of pyrolite.The effects of these and other factors connected with phase transformations on the dynamics of plate subsidence are discussed. It appears quite likely that plates penetrate the 650–700 km discontinuity, largely because the slope of the spinel disproportionation is probably positive, not negative as generally supposed. The former basaltic oceanic crust probably sinks deeply into the lower mantle, whilst the former harzburgite component of the plate may collect above the perovskite transition boundary. Phase transformations may thus serve as a kind of filter, leading to increased and irreversible mantle heterogeneity with time.The possible roles of phase transformations in causing deep-focus earthquakes and introducing water into the mantle in subduction zones are also briefly discussed.     

Fluids in the peridotite–water system up to 6 GPa and 800°C: new experimental constrains on dehydration reactions

The phase assemblages and compositions in a K-free lherzolite + H₂O system were determined between 4 and 6 GPa and 700–800°C, and the dehydration reactions occurring at subarc depth in subduction zones were constrained. Experiments were performed on a rocking multi-anvil apparatus using a diamond-trap setting. The composition of the fluid phase was measured using the recently developed cryogenic LA–ICP–MS technique. Results show that, at 4 GPa, the aqueous fluid coexisting with residual lherzolite (~85 wt% H₂O) doubles its solute load when chlorite transforms to the 10-Å phase between 700 and 750°C. The 10-Å phase breaks down at 4 and 5 GPa between 750 and 800°C and at 6 GPa between 700 and 750°C, leaving a dry lherzolite coexisting with a fluid phase containing 58–67 wt% H₂O, again doubling the total dissolved solute load. The fluid fraction in the system increases from 0.2 when a hydrous mineral is present to 0.4 when coexisting with a dry lherzolite. Our data do not reveal the presence of a hydrous peridotite solidus below 800°C. The directly measured fluid compositions demonstrate a fundamental change in the (MgO + FeO) to SiO₂ mass ratio of fluid solutes occurring at a depth of ca. 120–150 km (in the temperature window of 700–800°C), from (MgO–FeO)-dominated at 4 GPa [with (MgO + FeO)/SiO₂ ratio of 1.41–1.56] to SiO₂-dominated at 5–6 GPa (ratios of 0.61–0.82). The mobility of Al₂O₃ increases by more than one order of magnitude across this P–T interval and demonstrates that Al₂O₃ is compatible in an aqueous fluid coexisting with the anhydrous ol-opx-cpx ± grt assemblage. This shift in the fluid composition correlates with changes in the phase assemblage of the residual silicates. The hitherto unknown fundamental change in (MgO + FeO)/SiO₂ ratio and prominent increase in Al₂O₃ of the aqueous fluid with progressive subduction will likely inspire novel concepts on mantle wedge metasomatism by slab fluids.     

The influence of water on melting of mantle peridotite

This experimental study examines the effects of variable concentrations of dissolved H₂O on the compositions of silicate melts and their coexisting mineral assemblage of olivine + orthopyroxene ± clinopyroxene ± spinel ± garnet. Experiments were performed at pressures of 1.2 to 2.0 GPa and temperatures of 1100 to 1345 °C, with up to ∼12 wt% H₂O dissolved in the liquid. The effects of increasing the concentration of dissolved H₂O on the major element compositions of melts in equilibrium with a spinel lherzolite mineral assemblage are to decrease the concentrations of SiO₂, FeO, MgO, and CaO. The concentration of Al₂O₃ is unaffected. The lower SiO₂ contents of the hydrous melts result from an increase in the activity coefficient for SiO₂ with increasing dissolved H₂O. The lower concentrations of FeO and MgO result from the lower temperatures at which H₂O-bearing melts coexist with mantle minerals as compared to anhydrous melts. These compositional changes produce an elevated SiO₂/(MgO + FeO) ratio in hydrous peridotite partial melts, making them relatively SiO₂ rich when compared to anhydrous melts on a volatile-free basis. Hydrous peridotite melting reactions are affected primarily by the lowered mantle solidus. Temperature-induced compositional variations in coexisting pyroxenes lower the proportion of clinopyroxene entering the melt relative to orthopyroxene. Isobaric batch melting calculations indicate that fluid-undersaturated peridotite melting is characterized by significantly lower melt productivity than anhydrous peridotite melting, and that the peridotite melting process in subduction zones is strongly influenced by the composition of the H₂O-rich component introduced into the mantle wedge from the subducted slab. Received: 7 April 1997 / Accepted: 9 January 1998     

High-pressure and high-temperature stability of chlorite and 23-Å phase in the natural chlorite and synthetic MASH system

A series of experiments was conducted on the decomposition of natural and chemically mixed chlorites to examine the stable hydrous phases in the MgO–FeO–Al₂O₃–SiO₂–H₂O (MFASH) system under 5–12 GPa and 700–1100 °C. The upper pressure and temperature limits of the stability region of chlorite are consistent with those observed in previous studies. The hydrous aluminum bearing pyroxene (phase HAPY) and Mg-sursassite (Sur) were observed just above the temperature stability region of chlorite (Chl); clinohumite (cHm) was observed coexisting with phase HAPY at 6 GPa and 800 °C and coexisting with the 23-Å phase at 7 GPa and 800 °C, which may suggest the transportation of water through Chl → (HAPY → cHm) → 23-Å phase along a relatively warm slab. The 23-Å phase has a wider stability region in the pure MASH system (up to 12 GPa and 1100 °C) than it does in the MFASH system (7–10 GPa, up to 1000 °C). The stability of the 23-Å phase beyond the chlorite breakdown pressure indicates that it may play an important role in transporting water into the deep Earth and even into the mantle transition zone.     

Fractional crystallization and mantle-melting controls on calc-alkaline differentiation trends

The phase relations of primitive magnesian andesites and basaltic andesites from the Mt. Shasta region, N California have been determined over a range of pressure and temperature conditions and H₂O contents. The experimental results are used to explore the influence of H₂O and pressure on fractional crystallization and mantle melting behavior in subduction zone environments. At 200-MPa H₂O-saturated conditions the experimentally determined liquid line of descent reproduces the compositional variation found in the Mt. Shasta region lavas. This calc-alkaline differentiation trend begins at the lowest values of FeO*/MgO and the highest SiO₂ contents found in any arc magma system and exhibits only a modest increase in FeO*/MgO with increasing SiO₂. We propose a two-stage process for the origin of these lavas. (1) Extensive hydrous mantle melting produces H₂O-rich (>4.5--6 wt% H₂O) melts that are in equilibrium with a refractory harzburgite (olivine + orthopyroxene) residue. Trace elements and H₂O are contributed from a slab-derived fluid and/or melt. (2) This mantle melt ascends into the overlying crust and undergoes fractional crystallization. Crustal-level differentiation occurs under near-H₂O saturated conditions producing the distinctive high SiO₂ and low FeO*/MgO characteristics of these calc-alkaline andesite and dacite lavas. In a subset of Mt. Shasta region lavas, magnesian pargasitic amphibole provides evidence of high pre-eruptive H₂O contents (>10 wt% H₂O) and lower crustal crystallization pressures (800 MPa). Igneous rocks that possess major and trace element characteristics similar to those of the Mt. Shasta region lavas are found at Adak, Aleutians, Setouchi Belt, Japan, the Mexican Volcanic Belt, Cook Island, Andes and in Archean trondhjemite--tonalite--granodiorite suites (TTG suites). We propose that these magmas also form by hydrous mantle melting.Editorial responsibility: J. Hoefs     

Exhumation of oceanic eclogites: thermodynamic constraints on pressure,temperature, bulk composition and density

The exhumation mechanism of high‐pressure (HP) and ultrahigh‐pressure (UHP) eclogites formed by the subduction of oceanic crust (hereafter referred to as oceanic eclogites) is one of the primary uncertainties associated with the subduction factory. The phase relations and densities of eclogites with MORB compositions are modelled using thermodynamic calculations over a P–T range of 1–4 GPa and 400–800 °C, respectively, in the NCKFMASHTO (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃) system. Our modelling suggests that the mineral assemblages, mineral proportions and density of oceanic crust subducted along a cold P–T path are quite different from those of crust subducted along a warm P–T path, and that the density of oceanic eclogites is largely controlled by the stability of low‐density hydrous minerals, such as lawsonite, chlorite, glaucophane and talc. Along a cold subduction P–T path with a geotherm of ~6 °C km^?1, lawsonite is always present at 1.1 to >4.0 GPa, and chlorite, glaucophane and talc can be stable at pressures of up to 2.3, 2.6 and 3.6 GPa respectively. Along such a P–T path, the density of subducted oceanic crust is always lower than that of the surrounding mantle at depths shallower than 110–120 km (< 3.3–3.6 GPa). However, along a warm subduction P–T path with a geotherm of ~10 °C km^?1, the P–T path is outside the stability field of lawsonite, and the hydrous minerals of chlorite, epidote and amphibole break down completely into dry dense minerals at relatively lower pressures of 1.5, 1.85 and 1.9 GPa respectively. Along such a warm subduction P–T path, the subducted oceanic crust becomes denser than the surrounding mantle at depths >60 km (>1.8 GPa). Oceanic eclogites with high H₂O content, oxygen fugacity, bulk‐rock X_Mg [ = MgO/(MgO + FeO)], X_Al [ = Al₂O₃/(Al₂O₃ + MgO + FeO)] and low X_Ca [ = CaO/(CaO + MgO + FeO + Na₂O)] are likely suitable for exhumation, which is consistent with the bulk‐rock compositions of the natural oceanic eclogites on the Earth's surface. On the basis of natural observations and our calculations, it is suggested that beyond depths around 110–120 km oceanic eclogites are not light enough and/or there are no blueschists to compensate the negative buoyancy of the oceanic crust, therefore explaining the lack of oceanic eclogites returned from ultradeep mantle (>120 km) to the Earth's surface. The exhumed light–cold–hydrous oceanic eclogites may have decoupled from the top part of the sinking slab at shallow depths in the forearc region and are exhumed inside the serpentinized subduction channel, whereas the dense–hot–dry eclogites may be retained in the sinking slab and recycled into deeper mantle.     

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.     

Decarbonation reaction of magnesite in subducting slabs at the lower mantle

High-pressure and temperature experiments (28–62 GPa, and 1,490–2,000 K, corresponding to approximately 770–1,500 km depth in the mantle) have been conducted on a MgCO₃ + SiO₂ mixture using a laser-heated diamond anvil cell combined with analytical transmission electron microscope observation of the product phases to constrain the fate of carbonates carried on the subducting basalt into the lower mantle. At these conditions, the decarbonation reaction MgCO₃ (magnesite) + SiO₂ (stishovite) → MgSiO₃ (perovskite) + CO₂ (solid) has been recognized. This indicates that above reaction takes place as a candidate for decarbonation of the carbonated subducting mid ocean ridge basalts in the Earth’s lower mantle.     

Calculations of pressure-induced phase transitions in mantle minerals

The crystal structures and energies of SiO₂ stishovite, MgO periclase, Mg₂SiO₄ spinel, and MgSiO₃ perovskite were calculated as a function of pressure with the polarization-included electron gas (PEG) model. The calculated pressures of the spinel to perovskite phase transitions in the Mg₂SiO₄ and MgSiO₃ systems are 26.0 GPa and 27.0 GPa, respectively, compared to the experimental zero temperature extrapolations of 27.4 GPa and 27.7 GPa. The two oxide phases are found to be the most stable form in the pressure range 24.5 GPa to 31.5 GPa, compared to the experimental zero temperature extrapolation of 26.7 GPa to 28.0 GPa. The volume changes associated with the phase transitions are in good agreement with experiment. The transition pressures calculated with the PEG model, which allows the ions to distort from spherical symmetry, are in much better agreement with experiment than those calculated with the modified electron gas (MEG) model, which constrains the ions to be spherical.     

Composition of a carbonatitic melt in equilibrium with lherzolite at 5.5–6.3 GPa and 1350°C

Generation of ultra-alkaline melts by the interaction of lherzolite with cardonatites of various genesis was simulated at the P–T parameters typical of the base of the subcratonic lithosphere. Experiments with a duration of 150 h were performed at 5.5 and 6.3 GPa and 1350°C. The concentrations of CaO and MgO in melts are buffered by the phases of peridotite, and the concentrations of alkalis and FeO depend on the composition of the starting carbonatite. Melts are characterized by a low (<7 wt %) concentration of SiO₂ and Ca# from 0.40 to 0.47. It is demonstrated that only high-Mg groups of carbonatitic inclusions in fibrous diamonds have a composition close to that of carbonatitic melts in equilibrium with lherzolite. Most likely, the formation of kimberlite-like melts relatively enriched in SiO₂ requires an additional source of heat from mantle plumes and probably H₂O fluid.     

The equation of state of Al,H-bearing SiO2 stishovite to 58 GPa

We have determined the P-V equation of state of Al-rich H-bearing SiO₂ stishovite by X-ray powder diffraction at pressures up to 58 GPa using synchrotron radiation. The sample contained 1.8 wt% Al₂O₃ and up to 500 ppm H₂O, and had a composition that would coexist with Mg-silicate perovskite in a subducted slab. By fitting a third-order Birch-Murnaghan equation of state to our compression data, we obtained a bulk modulus K _T0=298(7) GPa with K′=4.3(5). With K′ fixed to a value of 4, the bulk modulus K _T0=304(3) GPa. Our results indicate that Al³⁺ and H⁺ have a small effect on the elastic properties of stishovite. Compared with data obtained up to 43.8 GPa, peak intensities changed and we observed a decreased quality of fit to a tetragonal unit cell at pressures of 49 GPa and higher. These changes may be an indication that the rutile↔CaCl₂ transition occurs between these pressures. After laser annealing of the sample at 58.3(10) GPa and subsequent decompression to room conditions, the cell volume is the same as before compression, giving strong evidence that the composition of the recovered sample is also unchanged. This suggests that Al and H are retained in the sample under extreme P-T conditions and that stishovite can be an agent for transporting water to the deepest lower mantle.     

Stability of sapphirine + quartz in the oxidized rocks of the Wilson Lake terrane,Labrador: calculated equilibria in NCKFMASHTO

The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al₂O₃–SiO₂ (FMAS) system. However, the potential for sapphirine to contain significant Fe³⁺ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al₂O₃–SiO₂–TiO₂–O (FMASTO), expansion into K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H₂O and O contents to use in the modelled compositions are investigated using T–M_H2O and T–M_O pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.     

High-pressure phase transitions of anorthosite crust in the Earth's deep mantle

We investigated phase relations, mineral chemistry, and density of lunar highland anorthosite at conditions up to 125 GPa and 2000 K. We used a multi-anvil apparatus and a laser-heated diamond-anvil cell for this purpose. In-situ X-ray diffraction measurements at high pressures and composition analysis of recovered samples using an analytical transmission electron microscope showed that anorthosite consists of garnet, CaAl₄Si₂O₁₁-rich phase (CAS phase), and SiO₂ phases in the upper mantle and the mantle transition zone. Under lower mantle conditions, these minerals transform to the assemblage of bridgmanite, Ca-perovskite, corundum, stishovite, and calcium ferrite-type aluminous phase through the decomposition of garnet and CAS phase at around 700 km depth. Anorthosite has a higher density than PREM and pyrolite in the upper mantle, while its density becomes comparable or lower under lower mantle conditions. Our results suggest that ancient anorthosite crust subducted down to the deep mantle was likely to have accumulated at 660–720 km in depth without coming back to the Earth's surface. Some portions of the anorthosite crust might have circulated continuously in the Earth's deep interior by mantle convection and potentially subducted to the bottom of the lower mantle when carried within layers of dense basaltic rocks.     

Dissociation of CAS phase in the uppermost lower mantle

The high-pressure stability limit of calcium aluminosilicate (CAS) phase has been examined in its end-member CaAl₄Si₂O₁₁ composition at 18–39 GPa and 1,670–2,300 K in a laser-heated diamond-anvil cell (LHDAC). The in-situ synchrotron X-ray diffraction measurements revealed that the CAS phase decomposes into three-phase assemblage of cubic Al-bearing CaSiO₃ perovskite, Al₂O₃ corundum, and SiO₂ stishovite above 30 GPa and 2,000 K with a positive pressure–temperature slope. Present results have important implications for the subsolidus mineral assemblage of subducted sediment and the melting phase relation of basalt in the lower mantle.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.     

High pressure transitions in the system KAlSi3O8-NaAlSi3O8

Phase relations in the system KAlSi₃O₈-NaAlSi ₃O₈ have been examined at pressures of 5–23 GPa and temperatures of 700–1200° C. KAlSi₃O₈ sanidine first dissociates into a mixture of wadeite-type K₂Si₄O₉, kyanite and coesite at 6–7 GPa, which further recombines into KAlSi₃O₈ hollandite at 9–10 GPa. In contrast, NaAlSi₃O₈ hollandite is not stable at 800–1200° C near 23 GPa, where the mixture of jadeite plus stishovite directly changes into the assemblage of calcium ferrite-type NaAlSiO₄ plus stishovite. Phase relations in the system KAlSi₃O₈-NaAlSi₃O₈ at 1000° C show that NaAlSi₃O₈ component gradually dissolves into hollandite with increasing pressure. The maximum solubility of NaAlSi₃O₈ in hollandite at 1000° C was about 40 mol% at 22.5 GPa, above which it decreases with pressure. Unit cell volume of the hollandite solid solution decreases with increasing NaAlSi₃O₈ component. The hollandite solid solution in this system may be an important candidate as a host mineral of K and Na in the uppermost lower mantle     

Quantitative phase petrology of cordierite–orthoamphibole gneisses and related rocks

Cordierite–orthoamphibole gneisses and rocks of similar composition commonly contain low‐variance mineral assemblages that can provide useful information about the metamorphic evolution of a terrane. New calculated petrogenetic grids and pseudosections are presented in the FeO–MgO–Al₂O₃–SiO₂–H₂O (FMASH), Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCKFMASH) and Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO) chemical systems to investigate quantitatively the phase relations in these rocks. Although the bulk compositions of cordierite–orthoamphibole gneisses are close to FMASH, calculations in this system do not adequately account for the observed range of mineral assemblages. Calculations in NCKFMASH and NCKFMASHTO highlight the role of minor constituents such as Ca, Na and Fe³⁺ in the mineral assemblage evolution of such rocks and these systems are more appropriate for interpreting the evolution of natural examples.     

Mg-Fe partitioning between olivine and ultramafic melts at high pressures

Precise determination of the partitioning of Mg and Fe²⁺ between olivine and ultramafic melt has been made at pressures from 5 to 13 GPa using a MA-8 type multi-anvil high-pressure apparatus (PREM) installed at Earthquake Research Institute, University of Tokyo. A very short rhenium capsule (<100 μm sample thickness) was adopted to minimize temperature variation within the sample container. Synthetic gels with the composition of the upper mantle peridotite were used as starting materials to promote the homogeneity. Analyses of quenched melts and coexisting olivines were made with an electron probe microanalyzer. The obtained partition coefficient, K_D [=(FeO/MgO)^ol/(FeO/MgO)^melt], decreases from 0.35 to 0.25 with increasing pressure from 5 to 13 GPa, suggesting a negative correlation between pressure and K_D above 5 GPa. Our result is consistent with a parabolic relationship between K_D and degree of polymerization (NBO/T) of melts reported by previous studies at lower pressures. The negative correlation between pressure and K_D suggests that olivine crystallizing in a magma ocean becomes more Mg-rich with depth and that primary magmas generated in the upper mantle become more Fe-rich with depth than previously estimated.