Carbonation and decarbonation of eclogites: the role of garnet

Carbonates are potentially significant hosts for primordial and subducted carbon in the Earth's mantle. In addition, the coexistence of carbonate with silicates and reduced carbon (diamond or graphite), allows constraints to be placed on the oxidation state of the mantle. Carbonate-silicate-vapor reactions control how carbonate + silicate assemblages may form from carbon-bearing vapor + silicate assemblages with increasing pressure. In olivine-bearing rocks such as peridotite, considered the dominant rock type in the upper mantle, the lowest-pressure carbonate-forming reactions involve olivine (±clinopyroxene) reacting with CO₂ (e.g., Wyllie et al. 1983). In eclogitic rocks, the essential mineral assemblage is omphacitic clinopyroxene + garnet, without olivine. Therefore, alternative carbonate-forming reactions must be sought. The carbonation of clinopyroxene via the reaction dolomite + 2 coesite = diopside + 2 CO₂ was studied experimentally by Luth (1995). The alternative possibility that garnet reacts with CO₂ is explored here by determining the location of the reaction 3 magnesite + kyanite + 2 coesite = pyrope + 3 CO₂ between 5 and 11 GPa in multi-anvil apparatus. At the temperatures ≥1200 °C, carbonation of eclogitic rocks with increasing pressure will proceed initially by reaction with clinopyroxene, because the pyrope-carbonation reaction lies at higher pressures for a given temperature than does the diopside-carbonation reaction. Diluting the pyrope component of garnet and the diopside component of clinopyroxene to levels appropriate for mantle eclogites does not change this conclusion. At lower temperatures, appropriate for “cold” slabs, it is possible that the converse situation will hold, with initial carbonation proceeding via reaction with garnet, but this possibility awaits experimental confirmation. Decarbonation of an eclogite under “normal mantle” geothermal conditions by a decrease in pressure, as in an ascending limb of a mantle convection cell, would be governed by the formation of clinopyroxene + CO₂. At higher pressure than this reaction, any CO₂ produced by the breakdown of magnesite reacting with kyanite and coesite would react with clinopyroxene to produce dolomite + coesite. Release of CO₂ from eclogite into mantle peridotite would form carbonate at sub-solidus conditions and produce a dolomitic carbonate melt if temperatures are above the peridotite-CO₂ solidus. Received: 4 May 1998 / Accepted: 23 December 1998     

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.     

Carbonation and melting reactions in the system CaO–MgO–SiO2–CO2 at mantle pressures with geophysical and petrological applications

Bowen's petrogenetic grid was based initially on a series of decarbonation reactions in the system CaO-MgO-SiO₂-CO₂ with starting assemblages including calcite, dolomite, magnesite and quartz, and products including enstatite, forsterite, diopside and wollastonite. We review the positions of 14 decarbonation reactions, experimentally determined or estimated, extending the grid to mantle pressures to evaluate the effect of CO₂ on model mantle peridotite composed of forsterite(Fo)+orthopyroxene(Opx)+clinopyroxene(Cpx). Each reaction terminates at an invariant point involving a liquid, CO₂, carbonates, and silicates. The fusion curves for the mantle mineral assemblages in the presence of excess CO₂ also terminate at these invariant points. The points are connected by a series of reactions involving liquidus relationships among the carbonates and mantle silicates, at temperatures lower (1,100–1,300° C) than the silicate-CO₂ melting reactions (1,400–1,600° C). Review of experimental data in the bounding ternary systems together with preliminary data for the system CaO-MgO-SiO₂-CO₂ permits construction of a partly schematic framework for decarbonation and melting reactions at upper mantle pressures. The key to several problems in the peridotite-CO₂ subsystem is the intersection of a subsolidus carbonation reaction with a melting reaction at an invariant point near 24 kb and 1,200°C. There is an intricate series of reactions between 25 kb and 35 kb involving changes in silicate and carbonate phase fields on the CO₂-saturated liquidus surfaces. Conclusions include the following: (1) Peridotite Fo+Opx+Cpx can be carbonated with increasing pressure, or decreasing temperature, to yield Fo+Opx+Cpx+Cd (Cd=calcic dolomite), Fo+Opx+Cd, Fo+Opx+Cm (Cm=calcic magnesite), and finally Qz+Cm. (2) Free CO₂ cannot exist in subsolidus mantle peridotite with normal temperature distributions; it is stored as carbonate, Cd. (3) The CO₂ bubbles in peridotite nodules do not represent free CO₂ in mantle peridotite along normal geotherms. (4) CO₂ is as effective as H₂O in causing incipient melting, our preferred explanation for the low-velocity zone. (5) Fusion of peridotite with CO₂ at depths shallower than 80 km produces basic magmas, becoming more SiO₂-undersaturated with depth. (6) The solubility of CO₂ in mantle magmas is less than about 5 wt% at depths to 80 km, increasing abruptly to about 40 wt% at 80 km and deeper. (7) Deeper than 80 km, the first liquids produced are carbonatitic, changing towards kimberlitic and eventually, at considerably higher temperatures, to basic magmas. (8) Kimberlite and carbonatite magmas rising from the asthenosphere must evolve CO₂ at depths 100-80 km, which contributes to their explosive emplacement. (9) Fractional crystallization of CO₂-bearing SiO₂-undersaturated basic magmas at most pressures can yield residual kimberlite and carbonatite magmas.     

The role of oxidation-reduction and C-H-O fluids in determining melting conditions and magma compositions in the upper mantle

High pressure experimental studies of the melting of lherzolitic upper mantle in the absence of carbon and hydrogen have shown that the lherzolite solidus has a positive dP/dT and that the percentage melting increases quite rapidly above the solidus. In contrast, the presence of carbon and hydrogen in the mantle results in a region of ‘incipient’ melting at temperatures below the C,H-free solidus. In this region the presence or absence of melt and the composition of the melt are dependent on the amount and nature of volatiles, particularly the CO₂, H₂O, and CH₄ contents of the potential C-H-O fluid. Under conditions of low (IW to IW + 1 log unit atP ∼ 20–35kb), fluids such as CH₄+H₂O and CH₄+H₂ inhibit melting, having a low solubility in silicate melts. Under these conditions, carbon and hydrogen are mobile elements in the upper mantle. At slightly higher oxygen fugacity (IW+2 log units,P∼20–35 kb) fluids in equilibrium with graphite or diamond in peridotite C-H-O are extremely water-rich. Carbon is thus not mobile in the mantle in this range and the melting and phase relations for the upper mantle lherzolite approximate closely to the peridotite-H₂O system. Pargasitic amphibole is stable to solidus temperatures in fertile lherzolite compositions and causes a distinctive peridotite solidus, the ‘dehydration solidus’, with a marked change in slope (a ‘back bend’) at 29–30kb due to instability of pargasite at high pressure. Intersections of geothermal gradients with the peridotite-H₂O solidi define the boundary between lithosphere (subsolidus) and asthenosphere (incipient melt region). This boundary is thus sensitive to changes in [affecting CH₄:H₂O:CO₂ ratios] and to the amount of H₂O and carbon (CO₂, CH₄) present. At higher conditions (IW + 3 log units), CO₂-rich fluids occur at low pressures but there is a marked depression of the solidus at 20–21 kb due to intersection with the carbonation reaction, producing the low temperature solidus for dolomite amphibole lherzolite (T∼925°C, 21 to >31kb). Melting of dolomite (or magnesite) amphibole lherzolite yields primary sodic dolomitic carbonatite melt with low H₂O content, in equilibrium with amphibole garnet lherzolite. The complexity of melting in peridotite-C-H-O provides possible explanations for a wide range of observations on lithosphere/asthenosphere relations, on mantle melt and fluid compositions, and on processes of mantle metasomatism and magma genesis in the upper mantle.     

Carbonatitic melts along the solidus of model lherzolite in the system CaO-MgO-Al2O3-SiO2-CO2 from 3 to 7 GPa

We have experimentally determined the solidus position of model lherzolite in the system CaO-MgO-Al₂O₃-SiO₂-CO₂ (CMAS.CO₂) from 3 to 7 GPa by locating isobaric invariant points where liquid coexists with olivine, orthopyroxene, clinopyroxene, garnet and carbonate. The intersection of two subsolidus reactions at the solidus involving carbonate generates two invariant points, I_1A and I_2A, which mark the transition from CO₂-bearing to dolomite-bearing and dolomite-bearing to magnesite-bearing lherzolite respectively. In CMAS.CO₂, we find I_1A at 2.6 GPa/1230 °C and I_2A at 4.8 GPa/1320 °C. The variation of all phase compositions along the solidus has also been determined. In the pressure range investigated, solidus melts are carbonatitic with SiO₂ contents of <6 wt%, CO₂ contents of ˜45 wt%, and Ca/(Ca+Mg) ratios that range from 0.59 (3 GPa) to 0.45 (7 GPa); compositionally they resemble natural magnesiocarbonatites. Volcanic magnesiocarbonatites may well be an example of the eruption of such melts directly from their mantle source region as evidenced by their diatremic style of activity and lack of associated silicate magmas. Our data in the CMAS.CO₂ system show that in a carbonate-bearing mantle, solidus and near-solidus melts will be CO₂-rich and silica poor. The widespread evidence for the presence of CO₂ in both the oceanic and continental upper mantle implies that such low degree SiO₂-poor carbonatitic melts are common in the mantle, despite the rarity of carbonatites themselves at the Earth's surface. Received: 9 April 1997 / Accepted: 25 November 1997     

Dissolution of orthopyroxene in basanitic magma between 0.4 and 2 GPa: further implications for the origin of Si-rich alkaline glass inclusions in mantle xenoliths

A large body of recent work has linked the origin of Si-Al-rich alkaline glass inclusions to metasomatic processes in the upper mantle. This study examines one possible origin for these glass inclusions, i.e., the dissolution of orthopyroxene in Si-poor alkaline (basanitic) melt. Equilibrium dissolution experiments between 0.4 and 2 GPa show that secondary glass compositions are only slightly Si enriched and are alkali poor relative to natural glass inclusions. However, disequilibrium experiments designed to examine dissolution of orthopyroxene by a basanitic melt under anhydrous, hydrous and CO₂-bearing conditions show complex reaction zones consisting of olivine, ± clinopyroxene and Si-rich alkaline glass similar in composition to that seen in mantle xenoliths. Dissolution rates are rapid and dependent on volatile content. Experiments using an anhydrous solvent show time dependent dissolution rates that are related to variable diffusion rates caused by the saturation of clinopyroxene in experiments longer than 10 minutes. The reaction zone glass shows a close compositional correspondence with natural Si-rich alkaline glass in mantle-derived xenoliths. The most Si-and alkali-rich melts are restricted to pressures of 1 GPa and below under anhydrous and CO₂-bearing conditions. At 2 GPa glass in hydrous experiments is still Si-␣and alkali-rich whereas glass in the anhydrous and CO₂-bearing experiments is only slightly enriched in SiO₂ and alkalis compared with the original solvent. In the low pressure region, anhydrous and hydrous solvent melts yield glass of similar composition whereas the glass from CO₂-bearing experiments is less SiO₂ rich. The mechanism of dissolution of orthopyroxene is complex involving rapid incongruent breakdown of the orthopyroxene, combined with olivine saturation in the reaction zone forming up to 60% olivine. Inward diffusion of CaO causes clinopyroxene saturation and uphill diffusion of Na and K give the glasses their strongly alkaline characteristics. Addition of Na and K also causes minor SiO₂ enrichment of the reaction glass by increasing the phase volume of olivine. Olivine and clinopyroxene are transiently stable phases within the reaction zone. Clinopyroxene is precipitated from the reaction zone melt near the orthopyroxene crystal and redissolved in the outer part of the reaction zone. Olivine defines the thickness of the reaction zone and is progressively dissolved in the solvent as the orthopyroxene continues to dissolve. Although there are compelling reasons for supporting the hypothesis that Si-rich alkaline melts are produced in the mantle by orthopyroxene – melt reaction in the mantle, there are several complications particularly regarding quenching in of disequilibrium reaction zone compositions and the mobility of highly polymerized melts in the upper mantle. It is considered likely that formation of veins and pools of Si-rich alkaline glass by orthopyroxene – melt reaction is a common process during the ascent of xenoliths. However, reaction in situ within the mantle will lead to equilibration and therefore secondary melts will be only moderately siliceous and alkali poor. Received: 24 August 1998 / Accepted: 2 December 1998     

Mantle Degassing and Diamond Genesis：A Carbon Isotope Perspective

The effect of Co2 and CH4 degassing from the mantle on the carbon isotopic composition of diamond has been quantitatively modeled in terms of the principles of Rayleigh distillation.Assuming the δ^13 C value of -5‰ for the mantle,the outgassing of CO2 can result in the large negative δ^13 C values of diamond,whereas the outgassing of CH4 can drive the δ^13C values of diamond in the positive direction.The theoretical expectations can be used to explain the full range of δ^13 C values from-34.4‰5 to 5‰ observed for natural diamonds.It is possible that diamond formation was triggered by the degassing of Co2 and/or CH4 from the mantle and the associated fractional crystallization of carbonate-bearing melt.     

Dolomite-bearing orogenic garnet peridotites witness fluid-mediated carbon recycling in a mantle wedge (Ulten Zone,Eastern Alps,Italy)

We document the presence of dolomite ± apatite in orogenic peridotites from the Ulten Zone (UZ, Italian Alps), the remnants of a Variscan mantle wedge tectonically coupled with eclogitized continental crust. These dolomite peridotites are associated with dominant carbonate-free amphibole peridotites, which formed in response to infiltration of aqueous subduction fluids lost by the associated crustal rocks during high-pressure (HP) metamorphism and retrogression. Dolomite-free and dolomite-bearing peridotites share the same metamorphic evolution, from garnet- (HP) to spinel-facies (low-pressure, LP) conditions. Dolomite and the texturally coexisting phases display equilibrium redistribution of rare earth elements and of incompatible trace elements during HP and LP metamorphism; clinopyroxene and amphiboles from carbonate-free and carbonate-bearing peridotites have quite similar compositions. These features indicate that the UZ mantle rocks equilibrated with the same metasomatic agents: aqueous CO₂-bearing fluids enriched in incompatible elements released by the crust. The P–T crystallization conditions of the dolomite peridotites (outside the field of carbonatite melt + amphibole peridotite coexistence), a lack of textures indicating quench of carbonic melts, a lack of increase in modal clinopyroxene by reaction with such melts and the observed amphibole increase at the expense of clinopyroxene, all suggest that dolomite formation was assisted by aqueous CO₂-bearing fluids. A comparison of the trace element compositions of carbonates and amphiboles from the UZ peridotites and from peridotites metasomatized by carbonatite and/or carbon-bearing silicate melts does not help to unambiguously discriminate between the different agents (fluids or melts). The few observed differences (lower trace element contents in the fluid-related dolomite) may ultimately depend on the solute content of the metasomatic agent (CO₂-bearing fluid versus carbonatite melt). This study provides strong evidence that C–O–H subduction fluids can produce ‘carbonatite-like’ assemblages in mantle rocks, thus being effective C carriers from the slab to the mantle wedge at relatively low P–T. If transported beyond the carbonate and amphibole solidus by further subduction, dolomite-bearing garnet + amphibole peridotites like the ones from Ulten can become sources of carbonatite and/or C-bearing silicate melts in the mantle wedge. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. In memory of Lauro Morten 1941–2006.     

Carbonation of alkaline paper mill waste to reduce CO2 greenhouse gas emissions into the atmosphere

The global warming of Earth’s near-surface, air and oceans in recent decades is a direct consequence of anthropogenic emission of greenhouse gases into the atmosphere such as CO₂, CH₄, N₂O and CFCs. The CO₂ emissions contribute approximately 60% to this climate change. This study investigates experimentally the aqueous carbonation mechanisms of an alkaline paper mill waste containing about 55 wt% portlandite (Ca(OH)₂) as a possible mineralogical CO₂ sequestration process. The overall carbonation reaction includes the following steps: (1) Ca release from portlandite dissolution, (2) CO₂ dissolution in water and (3) CaCO₃ precipitation. This CO₂ sequestration mechanism was supported by geochemical modelling of final solutions using PHREEQC software, and observations by scanning electron microscope and X-ray diffraction of final reaction products. According to the experimental protocol, the system proposed would favour the total capture of approx. 218 kg of CO₂ into stable calcite/ton of paper waste, independently of initial CO₂ pressure. The final product from the carbonation process is a calcite (ca. 100 wt%)-water dispersion. Indeed, the total captured CO₂ mineralized as calcite could be stored in degraded soils or even used for diverse industrial applications. This result demonstrates the possibility of using the alkaline liquid–solid waste for CO₂ mitigation and reduction of greenhouse effect gases into the atmosphere.     

Phase relations of phlogopite with magnesite from 4 to 8 GPa

To evaluate the stability of phlogopite in the presence of carbonate in the Earth’s mantle, we conducted a series of experiments in the KMAS–H₂O–CO₂ system. A mixture consisting of synthetic phlogopite (phl) and natural magnesite (mag) was prepared (phl₉₀-mag₁₀; wt%) and run at pressures from 4 to 8 GPa at temperatures ranging from 1,150 to 1,550°C. We bracketed the solidus between 1,200 and 1,250°C at pressures of 4, 5 and 6 GPa and between 1,150 and 1,200°C at a pressure of 7 GPa. Below the solidus, phlogopite coexists with magnesite, pyrope and a fluid. At the solidus, magnesite is the first phase to react out, and enstatite and olivine appear. Phlogopite melts over a temperature range of ~150°C. The amount of garnet increases above solidus from ~10 to ~30 modal% to higher pressures and temperatures. A dramatic change in the composition of quench phlogopite is observed with increasing pressure from similar to primary phlogopite at 4 GPa to hypersilicic at pressures ≥5 GPa. Relative to CO₂-free systems, the solidus is lowered such, that, if carbonation reactions and phlogopite metasomatism take place above a subducting slab in a very hot (Cascadia-type) subduction environment, phlogopite will melt at a pressure of ~7.5 GPa. In a cold (40 mWm⁻²) subcontinental lithospheric mantle, phlogopite is stable to a depth of 200 km in the presence of carbonate and can coexist with a fluid that becomes Si-rich with increasing pressure. Ascending kimberlitic melts that are produced at greater depths could react with peridotite at the base of the subcontinental lithospheric mantle, crystallizing phlogopite and carbonate at a depth of 180–200 km.     

Diffusion gradients in an eclogite xenolith from the Roberts Victor kimberlite pipe: (2) kinetics and implications for petrogenesis

In a bimineralic eclogite xenolith (sample JJG41) from the Roberts Victor kimberlite, compositional gradients in clinopyroxene are related to garnet exsolution. Two principal reactions involving clinopyroxene and garnet occur: (i) The net-transfer Al₂Si^-1Mg^-1 which is responsible for garnet growth according to the equation 2Di+Al₂Si^-1Mg^-1=Grossular+MgCa^-1 (reaction 1). This has created substantial compositional gradients in Al, Si and Mg within clinopyroxene. (ii) The exchange of Fe–Mg between garnet and clinopyroxene (reaction 2). During the stage of garnet growth (reaction 1) the lamellae crystallized sequentially as a result of a temperature decrease from around 1400 to 1200° C. This exsolution growth-stage was under the control of Al diffusion in clinopyroxene and at around 1200° C further growth of garnet lamellae became impeded by the sluggishness of Al diffusion in the clinopyroxene host. However, reaction 2 continued during further cooling down to about 1000° C; this temperature being inferred from the constant Fe–Mg partitioning at clinopyroxene-garnet interfaces for the whole set of lamellae. The initial clinopyroxene in JJG41 was probably formed by crystallization from a melt in Archaean time. The cessation of Fe–Mg exchange between garnet and clinopyroxene at about 1000° C may well predate the eruption of the eclogite in kimberlite at around 100 Ma. Kinetic models of reaction are examined for both reactions. Modelling of reaction 1, involving both diffusion and interface migration, allows several means of estimating the diffusion coefficient of Al in clinopyroxene; the estimates are in the range 10^-16-10^-20 cm²/s at 1200° C. These estimates bracket the experimentally determined data for Al diffusion in clinopyroxene, and from these experimental data a preferred cooling rate of about 300° C/Ma is obtained for the period of growth of garnet exsolution lamellae. A geospeedometry approach (Lasaga 1983) suitable for a pure-exchange process (reaction 2) is used to estimate the cooling rate in the later stages of the thermal history (after garnet growth); values 4–40° C/Ma are consistent with the shape of the Fe-diffusion gradients in the clinopyroxene. The extensive thermal history recorded by JJG41, including probable melt involvement at ca. 1400° C, demonstrates the complex evolution of rocks within the mantle. Whilst the notion of formation of mantle eclogites from subducted oceanic crust has become fashionable, it is clear that tracing eclogite geochemical and P-T characteristics backwards from their nature at the time of xenolith eruption, through high-temperature mantle events to the characteristics of the original subducted oceanic crust, will be very complex.     

Estimation of the composition of the Earth’s primary aqueous phase. 2. Synthesis from the mantle and igneous rock material. Comparison with synthesis from the carbonaceous chondrite material

Simulation results of the equilibrium state of systems water-carbonaceous chondrite material, water-primary mantle material, water-ultramafic rock material, and water-mafic rock material open with respect to carbon dioxide and methane at 25°C, 1 bar indicate that highly alkaline reduced aqueous solutions with K/Na > 1 can be formed only if water is in equilibrium with compositions close to those of continental crust and primitive mantle. Yu.V. Natochin’s hypothesis that the living cell can be formed only in an aqueous environment with K/Na > 1 leads to the conclusion that terrestrial life could arise and further evolve on the Earth during the differentiation of primary chondritic material into the Earth’s core and mantle (during the first few million years of the planet’s lifetime) in an alkaline (pH 9–10) reduced (Eh = −400–500 mV) aqueous solution at a temperature of 50–60°C, in equilibrium with an N₂-bearing atmosphere, which also contained CH₄ (partial pressure from 10⁻² to 10⁻⁸ bar), CO₂ (partial pressure from 10⁻⁵ to 10⁻⁸ bar), NH₃, H₂, H₂S, CO, and other gases.     

Greenhouse gases and greenhouse effect

Conventional theory of global warming states that heating of atmosphere occurs as a result of accumulation of CO₂ and CH₄ in atmosphere. The writers show that rising concentration of CO₂ should result in the cooling of climate. The methane accumulation has no essential effect on the Earth’s climate. Even significant releases of the anthropogenic carbon dioxide into the atmosphere do not change average parameters of the Earth’s heat regime and the atmospheric greenhouse effect. Moreover, CO₂ concentration increase in the atmosphere results in rising agricultural productivity and improves the conditions for reforestation. Thus, accumulation of small additional amounts of carbon dioxide and methane in the atmosphere as a result of anthropogenic activities has practically no effect on the Earth’s climate.     

Melts in the mantle modeled in the system CaO-MgO-SiO2-CO2 at 2.7 GPa

The effect of CO₂ on mantle peridotites is modeled by experimental data for the system CaO-MgO-SiO₂-CO₂ at 2.7 GPa. The experiments provide isotherms for the vapor-saturated liquidus surface, bracket piercing points for field boundaries on the surface, and define the positions and compositions of isobaric invariant liquids on the boundaries (eutectics and peritectics). CO₂-saturated carbonatitic liquids (>80% carbonate) exist through approximately 200 °C above the solidus, with a transition to silicate liquids (>80% silicate) within ∼75 °C across a plateau on the liquidus. Carbonate-rich magmas cannot cross the silicate-carbonate liquidus field boundary, so the carbonate liquidus field is therefore a forbidden volume for liquid magmas. This confirms the fact that rounded, pure carbonates in mantle xenoliths cannot represent original liquids. A P-T diagram is constructed for the carbonation and melting reactions for mineral assemblages corresponding to lherzolite, harzburgite, websterite and wehrlite, with carbonate, CO₂ vapor (V), or both. The changing compositions of liquids in solidus reactions on the P-T diagram are illustrated by the changing compositions of eutectic and peritectic liquids on the liquidus surface. At an invariant point Q (∼2.8 GPa/1230 °C), all peridotite assemblages coexist with a calcite-dolomite solid solution (75 ± 5% CaCO₃) and a dolomitic carbonatite melt [57% CaCO₃ (CC), 33% MgCO₃ (MC), 10% CaMgSi₂O₆ (Di)], with 63% CC in the carbonate component. At higher pressures, dolomite-lherzolite, dolomite-harzburgite-V, and dolomite-websterite-V melt to yield similar liquids. Magnesian calcite-wehrlite is the only peridotite melting to carbonatitic liquids (more calcic) at pressures below Q (∼70 km). Dolomitic carbonatite magma rising through mantle to the near-isobaric solidus ledge near Q will begin to crystallize, releasing CO₂ (enhancing crack propagation), and metasomatizing lherzolite toward wehrlite. Received: 20 March 1998 / Accepted: 7 July 1999     

Experimental study of the CaMgSi2O6–CO2 system at 3–8 GPa

The melting relationships in the system CaMgSi₂O₆ (Di)–CO₂ have been studied in the 3–8 GPa pressure range to determine if there is an abrupt decrease in the temperature of the solidus accompanying the stabilization of carbonate as a subsolidus phase. Such a decrease has been observed previously in peridotitic and some eclogitic systems. In contrast, the solidus in the Di–CO₂ system was found to decrease in a gradual fashion from 3 to 8 GPa. This decrease accompanies an evolution in the composition of the melt at the solidus from silicate-rich with minor CO₂ at 3 GPa to carbonatitic at 5.5 GPa, where the carbonation reaction Diopside + CO₂ = Dolomite (Dol) + Coesite (Cst) intersects the solidus. The near-solidus melt remains carbonatitic at higher pressure, consistent with carbonate being the dominant contributor to the melt. Based on previous studies in both eclogitic and peridotitic systems, this conclusion can be extended to more complicated systems: once carbonate is a stable subsolidus phase, it plays a major role in controlling both the temperature of melting and the composition of the melt produced.     

Experimental reconstruction of sodic dolomitic carbonatite melts from metasomatised lithosphere

 Investigations of peridotite xenolith suites have identified a compositional trend from lherzolite to magnesian wehrlite in which clinopyroxene increases at the expense of orthopyroxene and aluminous spinel, and in which apatite may be a minor phase. Previous studies have shown that this trend in mineralogy and chemical composition may result from reaction between sodic dolomitic carbonatite melt and lherzolite at pressures around 1.7 to 2 GPa. This reaction results in decarbonation of the carbonatite melt, releasing CO₂-rich fluid. In this study, we have experimentally reversed the decarbonation reaction by taking two natural wehrlite compositions and reacting them with CO₂ at a pressure of 2.2 GPa and temperatures from 900 to 1150° C. Starting materials were pargasite-bearing wehrlites, one with minor apatite (composition 71001^*) and one without apatite (composition 70965^*). At lower temperatures (900° C) the products were apatite+pargasite+magnesite harzburgite for runs using composition 71001^*, and pargasite+dolomite lherzolite for runs using composition 70965^*. At and above 1000° C, carbonatite melt with harzburgite residue (olivine+orthopyroxene+spinel) and with lherzolite residue (olivine+orthopyroxene+clinopyroxene+ spinel) were produced respectively. Phase compositions in reactants and products are consistent with the documented carbonatite/lherzolite reactions, and also permit estimation of the carbonatite melt compositions. In both cases the melts are sodic dolomitic carbonatites. The study supports the hypothesis of a significant role for ephemeral, sodic dolomitic melts in causing metasomatic changes in the lithosphere at P≤2 GPa. The compositions of wehrlites imply fluxes of CO₂, released by metasomatic reactions, which are locally very large at around 5 wt% CO₂. Received: 15 December 1995/Accepted: 14 February 1996     

The influence of crystal field stabilization energy on Fe2+ partitioning in paragenetic minerals

In order to explore possible quantitative relations between crystal field stabilization energy, CFSE, and partitioning behaviour of the 3d ⁶-configured Fe²⁺ ion, a suite of 29 paragenetic rock-forming minerals from 12 high-grade metamorphic rock samples of the Ukrainian shield, including the parageneses garnet/orthopyroxene/clinopyroxene (2x), orthopyroxene/clinopyroxene, garnet/clinopyroxene, garnet/orthopyroxene/biotite, garnet/biotite, garnet/cordierite, garnet/cordierite/biotite, garnet/orthopyroxene/clinopyroxene/Ca-amphibole, Ca-amphibole/biotite (retrograde), was studied by electron microprobe analysis to obtain the respective K _D Fe^{2+ (Ph1/Ph2)} values and by polarized single crystal electronic absorption spectroscopy to evaluate the respective CFSE_Fe2+ values. Other than in the case of Cr³⁺, a clear quantitative relation between K _D ^(Ph1/Ph2) and the ΔCFSE^(Ph1/Ph2) was only observed when geometrical factors, mainly the volume of crystallographic sites and ionic radii of ions competing in the partitioning process, are similar in the respective two paragenetic phases to within 15–20%. In such cases, the ΔCFSE_Fe2+ contribution to K _D ^(Ph1/Ph2) amounts to 0.1 to 0.2 log K _D per 100 cm⁻¹ΔCFSE. The conclusion is that ΔCFSE_Fe2+ plays only a secondary role after geometrical factors, in the partitioning behaviour of Fe²⁺. The reason for this is seen in the facts that, compared to the 3d ³-configured Cr³⁺ ion, CFSE of the 3d ⁶-configured Fe²⁺ amounts only to 20–25%, and that the former ion enters only octahedral sites with similar geometrical properties in the paragenetic mineral phases. Received: 17 November 1998 / Accepted: 28 June 1999     

Evolution of parental magmas of Miocene shield basalts of Gran Canaria (Canary Islands): constraints from crystal,melt and fluid inclusions in minerals

 Picritic units of the Miocene shield volcanics on Gran Canaria, Canary Islands, contain olivine and clinopyroxene phenocrysts with abundant primary melt, crystal and fluid inclusions. Composition and crystallization conditions of primary magmas in equilibrium with olivine Fo_90-92 were inferred from high-temperature microthermometric quench experiments, low-temperature microthermometry of fluid inclusions and simulation of the reverse path of olivine fractional crystallization based on major element composition of melt inclusions. Primary magmas parental for the Miocene shield basalts range from transitional to alkaline picrites (14.7–19.3 wt% MgO, 43.2–45.7 wt% SiO₂). Crystallization of these primary magmas is believed to have occurred over the temperature range 1490–1150° C at pressures ≈5 kbar producing olivine of Fo_80.6-90.2, high-Ti chrome spinel [Mg/ (Mg+Fe²⁺)=0.32–0.56, Cr/(Cr+Al)=0.50–0.78, 2.52–8.58 wt% TiO₂], and clinopyroxene [Mg/(Mg+Fe)=0.79–0.88, Wo_44.1-45.3, En_43.9-48.0, Fs_6.8-11.0] which appeared on the liquidus together with olivine≈Fo₈₆. Redox conditions evolved from intermediate between the QFM and WM buffers to late-stage conditions of NNO+1 to NNO+2. The primary magmas crystallized in the presence of an essentially pure CO₂ fluid. The primary magmas originated at pressures >30 kbar and temperatures of 1500–1600° C, assuming equilibrium with mantle peridotite. This implies melting of the mantle source at a depth of ≈100 km within the garnet stability field followed by migration of melts into magma reservoirs located at the boundary between the upper mantle and lower crust. The temperatures and pressures of primary magma generation suggest that the Canarian plume originated in the lower mantle at depth ≈900 km that supports the plume concept of origin of the Canary Islands. Received: 23 October 1995/Accepted: 21 February 1996     

Solubility of CO2 in olivine melilitite at high pressures and role of CO2 in the earth's upper mantle

The positions of the liquidi and the near-liquidus phases of olivine-melilitite+CO₂ have been determined under MH-buffered and furnace-buffered conditions up to 40 kb. It is found that CO₂ alone lowers the liquidus compared to dry conditions, yet its influence is minor compared to H₂O. The major role of CO₂ is to favour the growth of orthopyroxene and garnet over that of olivine at least at high pressures. CO₂-contents of glasses from experiments just above the liquidus (MH-buffered) were determined as 5.1 % at 10kb; 7.5 % at 20kb, 9.3 % at 30kb and 10–11 % (estimated) at 40 kb. Experiments on (pyrolite –40 % olivine)+H₂O+CO₂ show that CO₂ occurs under mantle conditions as carbonate under subsolidus conditions and dissolved in a melt above the solidus. At 30kb, the solidus lies between 1,000 ° C and 1,050 ° C for vapour-saturated conditions, at and at .     

Electrical conductivity of hydrous basaltic melts: implications for partial melting in the upper mantle

The Earth’s uppermost asthenosphere is generally associated with low seismic wave velocity and high electrical conductivity. The electrical conductivity anomalies observed from magnetotelluric studies have been attributed to the hydration of mantle minerals, traces of carbonatite melt, or silicate melts. We report the electrical conductivity of both H₂O-bearing (0–6 wt% H₂O) and CO₂-bearing (0.5 wt% CO₂) basaltic melts at 2 GPa and 1,473–1,923 K measured using impedance spectroscopy in a piston-cylinder apparatus. CO₂ hardly affects conductivity at such a concentration level. The effect of water on the conductivity of basaltic melt is markedly larger than inferred from previous measurements on silicate melts of different composition. The conductivity of basaltic melts with more than 6 wt% of water approaches the values for carbonatites. Our data are reproduced within a factor of 1.1 by the equation log σ = 2.172 − (860.82 − 204.46 w ^0.5)/(T − 1146.8), where σ is the electrical conductivity in S/m, T is the temperature in K, and w is the H₂O content in wt%. We show that in a mantle with 125 ppm water and for a bulk water partition coefficient of 0.006 between minerals and melt, 2 vol% of melt will account for the observed electrical conductivity in the seismic low-velocity zone. However, for plausible higher water contents, stronger water partitioning into the melt or melt segregation in tube-like structures, even less than 1 vol% of hydrous melt, may be sufficient to produce the observed conductivity. We also show that ~1 vol% of hydrous melts are likely to be stable in the low-velocity zone, if the uncertainties in mantle water contents, in water partition coefficients, and in the effect of water on the melting point of peridotite are properly considered.