A modified iterative sandwich method for determination of near-solidus partial melt compositions. II. Application to determination of near-solidus melt compositions of carbonated peridotite

We performed modified iterative sandwich experiments (MISE) to determine the composition of carbonatitic melt generated near the solidus of natural, fertile peridotite + CO₂ at 1,200–1,245°C and 6.6 GPa. Six iterations were performed with natural peridotite (MixKLB-1: Mg# = 89.7) and ∼10 wt% added carbonate to achieve the equilibrium carbonatite composition. Compositions of melts and coexisting minerals converged to a constant composition after the fourth iteration, with the silicate mineral compositions matching those expected at the solidus of carbonated peridotite at 6.6 GPa and 1,230°C, as determined from a sub-solidus experiment with MixKLB-1 peridotite. Partial melts expected from a carbonated lherzolite at a melt fraction of 0.01–0.05% at 6.6 GPa have the composition of sodic iron-bearing dolomitic carbonatite, with molar Ca/(Ca + Mg) of 0.413 ± 0.001, Ca# [100 × molar Ca/(Ca + Mg + Fe*)] of 37.1 ± 0.1, and Mg# of 83.7 ± 0.6. SiO₂, TiO₂ and Al₂O₃ concentrations are 4.1 ± 0.1, 1.0 ± 0.1, and 0.30 ± 0.02 wt%, whereas the Na₂O concentration is 4.0 ± 0.2 wt%. Comparison of our results with other iterative sandwich experiments at lower pressures indicate that near-solidus carbonatite derived from mantle lherzolite become less calcic with increasing pressure. Thus carbonatitic melt percolating through the deep mantle must dissolve cpx from surrounding peridotite and precipitate opx. Significant FeO* and Na₂O concentrations in near solidus carbonatitic partial melt likely account for the ∼150°C lower solidus temperature of natural carbonated peridotite compared to the solidus of synthetic peridotite in the system CMAS + CO₂. The experiments demonstrate that the MISE method can determine the composition of partial melts at very low melt fraction after a small number of iterations.     

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     

Continuous Gradations among Primary Carbonatitic, Kimberlitic, Melilititic, Basaltic, Picritic, and Komatiitic Melts in Equilibrium with Garnet Lherzolite at 3-8 GPa

Multianvil melting experiments in the system CaO–MgO–Al₂O₃–SiO₂–CO₂(CMAS–CO₂) at 3–8 GPa, 1340–1800°C, involvingthe garnet lherzolite phase assemblage in equilibrium with CO₂-bearingmelts, yield continuous gradations in melt composition betweencarbonatite, kimberlite, melilitite, komatiite, picrite, andbasalt melts. The phase relations encompass a divariant surfacein P–T space. Comparison of the carbonatitic melts producedat the low-temperature side of this surface with naturally occurringcarbonatites indicates that natural magnesiocarbonatites couldbe generated over a wide range of pressures >2·5 GPa.Melts analogous to kimberlites form at higher temperatures alongthe divariant surface, which suggests that kimberlite genesisrequires more elevated geotherms. However, the amount of waterfound in some kimberlites has the potential to lower temperaturesfor the generation of kimberlitic melts by up to 150°C,provided no hydrous phases are present. Compositions resemblinggroup IB and IA kimberlites are produced at pressures around5–6 GPa and 10 GPa, respectively, whereas the compositionsof some other kimberlites suggest generation at higher pressuresstill. At pressures <4 GPa, an elevated geotherm producesmelilitite-like melt in the CMAS–CO₂ system rather thankimberlite. Even when a relatively CO₂-rich mantle compositioncontaining 0·15 wt % CO₂ is assumed, kimberlites andmelilitites are produced by <1% melting and carbonatitesare generated by even smaller degrees of melting of <0·5%. KEY WORDS: carbonatite; CO₂; kimberlite; melilitite; melt generation     

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.     

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     

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     

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.     

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.     

Phase relations and chemistry of Ti-rich K-richterite-bearing mantle assemblages: an experimental study to 8.0 GPa in a Ti-KNCMASH system

Experiments have been conducted in a peralkaline Ti-KNCMASH system representative of MARID-type bulk compositions to delimit the stability field of K-richterite in a Ti-rich hydrous mantle assemblage, to assess the compositional variation of amphibole and coexisting phases as a function of P and T, and to characterise the composition of partial melts derived from the hydrous assemblage. K-richterite is stable in experiments from 0.5 to 8.0 GPa coexisting with phlogopite, clinopyroxene and a Ti-phase (titanite, rutile or rutile + perovskite). At 8.0 GPa, garnet appears as an additional phase. The upper T stability limit of K-richterite is 1200–1250 °C at 4.0 GPa and 1300–1400 °C at 8.0 GPa. In the presence of phlogopite, K-richterite shows a systematic increase in K with increasing P to 1.03 pfu (per formula unit) at 8.0 GPa/1100 °C. In the absence of phlogopite, K-richterite attains a maximum of 1.14 K pfu at 8.0 GPa/1200 °C. Titanium in both amphibole and mica decreases continuously towards high P with a nearly constant partitioning while Ti in clinopyroxene remains more or less constant. In all experiments below 6.0 GPa ΣSi + Al in K-richterite is less than 8.0 when normalised to 23 oxygens+stoichiometric OH. Rutiles in the Ti-KNCMASH system are characterised by minor Al and Mg contents that show a systematic variation in concentration with P(T) and the coexisting assemblage. Partial melts produced in the Ti-KNCMASH system are extremely peralkaline [(K₂O+Na₂O)/Al₂O₃ = 1.7–3.7], Si-poor (40–45 wt% SiO₂), and Ti-rich (5.6–9.2 wt% TiO₂) and are very similar to certain Ti-rich lamproite glasses. At 4.0 GPa, the solidus is thought to coincide with the K-richterite-out reaction, the first melt is saturated in a phlogopite-rutile-lherzolite assemblage. Both phlogopite and rutile disappear ca. 150 °C above the solidus. At 8.0 GPa, the solidus must be located at T≤1400 ^°C. At this temperature, a melt is in equilibrium with a garnet- rutile-lherzolite assemblage. As opposed to 4.0 GPa, phlogopite does not buffer the melt composition at 8.0 GPa. The experimental results suggest that partial melting of MARID-type assemblages at pressures ≥4.0 GPa can generate Si-poor and partly ultrapotassic melts similar in composition to that of olivine lamproites. Received: 23 December 1996 / Accepted: 20 March 1997     

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.     

The near-solidus transition from garnet lherzolite to spinel lherzolite

The position of the transition from spinel lherzolite to garnet lherzolite in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS) has been determined experimentally at near-solidus temperatures. In reversed experiments, the transition occurs between 18 and 20 kbar at 1200 °C and between 26 and 27 kbar at 1500 °C, corresponding to higher pressures than previously envisaged. A position for the transition deeper within the Earth further complicates the explanation of the so-called garnet signatures in the trace element and isotope patterns of mid-ocean ridge basalts. If melting during adiabatic upwelling beneath a mid-ocean ridge begins at the depth required for the stability of garnet in peridotitic compositions, simple melting models predict that the amount of melt produced should be much greater than the observed thickness of the oceanic crust. A partial solution to the apparent conflict might be that (1) the rather simplistic melting models are in error, (2) that melting begins in garnet pyroxenite veins that are believed to be stable at lower pressures than garnet lherzolite or (3) that melting does not involve garnet at all, but it is clinopyroxene causing the trace element patterns observed in basalts erupted at mid-ocean ridges. A second set of reversal experiments were conducted to investigate the solubility of alumina in both orthopyroxenes and clinopyroxenes at the high temperatures near the solidus in the system CMAS. The results are compatible with most previous studies, and may be used as a starting point to calibrate thermodynamic models for pyroxenes in chemical systems, approximating upper mantle chemistry. Received: 9 August 1999 / Accepted: 29 October 1999     

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

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

The effect of bulk composition on the solidus of carbonated eclogite from partial melting experiments at 3 GPa

To explore the effect of bulk composition on the solidus of carbonated eclogite, we determined near-solidus phase relations at 3 GPa for four different nominally anhydrous, carbonated eclogites. Starting materials (SLEC1, SLEC2, SLEC3, and SLEC4) were prepared by adding variable proportions and compositions of carbonate to a natural eclogite xenolith (66039B) from Salt Lake crater, Hawaii. Near-solidus partial melts for all bulk compositions are Fe–Na calcio-dolomitic and coexist with garnet + clinopyroxene + ilmenite ± calcio-dolomitic solid solution. The solidus for SLEC1 (Ca#=100 × molar Ca/(Ca + Mg + Fe_T)=32, 1.63 wt% Na₂O, and 5 wt% CO₂) is bracketed between 1,050°C and 1,075°C (Dasgupta et al. in Earth Planet Sci Lett 227:73–85, 2004), whereas initial melting for SLEC3 (Ca# 41, 1.4 wt% Na₂O, and 4.4 wt% CO₂) is between 1,175°C and 1,200°C. The solidus for SLEC2 (Ca# 33, 1.75 wt% Na₂O, and 15 wt% CO₂) is estimated to be near 1,100°C and the solidus for SLEC3 (Ca# 37, 1.47 wt% Na₂O, and 2.2 wt% CO₂) is between 1,100°C and 1,125°C. Solidus temperatures increase with increasing Ca# of the bulk, owing to the strong influence of the calcite–magnesite binary solidus-minimum on the solidus of carbonate bearing eclogite. Bulk compositions that produce near-solidus crystalline carbonate closer in composition to the minimum along the CaCO₃-MgCO₃ join have lower solidus temperatures. Variations in total CO₂ have significant effect on the solidus if CO₂ is added as CaCO₃, but not if CO₂ is added as a complex mixture that maintains the cationic ratios of the bulk-rock. Thus, as partial melting experiments necessarily have more CO₂ than that likely to be found in natural carbonated eclogites, care must be taken to assure that the compositional shifts associated with excess CO₂ do not unduly influence melting behavior. Near-solidus dolomite and calcite solid solutions have higher Ca/(Ca + Mg) than bulk eclogite compositions, owing to Ca–Mg exchange equilibrium between carbonates and silicates. Carbonates in natural mantle eclogite, which have low bulk CO₂ concentration, will have Ca/Mg buffered by reactions with silicates. Consequently, experiments with high bulk CO₂ may not mimic natural carbonated eclogite phase equilibria unless care is taken to ensure that CO₂ enrichment does not result in inappropriate equilibrium carbonate compositions. Compositions of eclogite-derived carbonate melt span the range of natural carbonatites from oceanic and continental settings. Ca#s of carbonatitic partial melts of eclogite vary significantly and overlap those of partial melts of carbonated lherzolite, however, for a constant Ca-content, Mg# of carbonatites derived from eclogitic sources are likely to be lower than the Mg# of those generated from peridotite.     

Phase relations and melting of carbonated peridotite between 10 and 20 GPa: a proxy for alkali- and CO<Subscript>2</Subscript>-rich silicate melts in the deep mantle

We determined the melting phase relations, melt compositions, and melting reactions of carbonated peridotite on two carbonate-bearing peridotite compositions (ACP: alkali-rich peridotite + 5.0 wt % CO₂ and PERC: fertile peridotite + 2.5 wt % CO₂) at 10–20 GPa and 1,500–2,100 °C and constrain isopleths of the CO₂ contents in the silicate melts in the deep mantle. At 10–20 GPa, near-solidus (ACP: 1,400–1,630 °C) carbonatitic melts with < 10 wt % SiO₂ and > 40 wt % CO₂ gradually change to carbonated silicate melts with > 25 wt % SiO₂ and < 25 wt % CO₂ between 1,480 and 1,670 °C in the presence of residual majorite garnet, olivine/wadsleyite, and clinoenstatite/clinopyroxene. With increasing degrees of melting, the melt composition changes to an alkali- and CO₂-rich silicate melt (Mg# = 83.7–91.6; ~ 26–36 wt % MgO; ~ 24–43 wt % SiO₂; ~ 4–13 wt % CaO; ~ 0.6–3.1 wt % Na₂O; and ~ 0.5–3.2 wt % K₂O; ~ 6.4–38.4 wt % CO₂). The temperature of the first appearance of CO₂-rich silicate melt at 10–20 GPa is ~ 440–470 °C lower than the solidus of volatile-free peridotite. Garnet + wadsleyite + clinoenstatite + carbonatitic melt controls initial carbonated silicate melting at a pressure < 15 GPa, whereas garnet + wadsleyite/ringwoodite + carbonatitic melt dominates at pressure > 15 GPa. Similar to hydrous peridotite, majorite garnet is a liquidus phase in carbonated peridotites (ACP and PERC) at 10–20 GPa. The liquidus is likely to be at ~ 2,050 °C or higher at pressures of the present study, which gives a melting interval of more than 670 °C in carbonated peridotite systems. Alkali-rich carbonated silicate melts may thus be produced through partial melting of carbonated peridotite to 20 GPa at near mantle adiabat or even at plume temperature. These alkali- and CO₂-rich silicate melts can percolate upward and may react with volatile-rich materials accumulate at the top of transition zone near 410-km depth. If these refertilized domains migrate upward and convect out of the zone of metal saturation, CO₂ and H₂O flux melting can take place and kimberlite parental magmas can be generated. These mechanisms might be important for mantle dynamics and are potentially effective metasomatic processes in the deep mantle.     

Experimental study of the phase and melting relations of homogeneous basalt + peridotite mixtures and implications for the petrogenesis of flood basalts

Flood basalt provinces may constitute some of the most catastrophic volcanic events in the Earth's history. A popular model to explain them involves adiabatic ascent of plumes of anomalously hot peridotite from a thermal boundary layer deep in the mantle, across the peridotite solidus. However, peridotitic plumes probably require unreasonably high potential temperatures to generate sufficient volumes of magma and high enough melting rates to produce flood volcanism. This lead to the suggestion that low melting eclogitic or pyroxenitic heterogeneities may be present in the source regions of the flood basalts. In order to constrain petrogenetic models for flood basalts generated in this way, an experimental investigation of the melting relations of homogeneous peridotite + oceanic basalt mixtures has been performed. Experiments were conducted at 3.5 GPa on a fertile peridotite (MPY90)–oceanic basalt (GA1) compositional join. The hybrid basalt + peridotite compositions crystallised garnet lherzolite at subsolidus temperatures plus quenched ne-normative picritic liquids at temperatures just above the solidus, over the compositional range MPY90 to GA1₅₀MPY90₅₀. The solidus temperature decreased slightly from ∼1500 °C for MPY90 to ∼1450 °C for GA1₅₀MPY90₅₀. Compositions similar to GA1₃₀MPY90₇₀ have 100% melting compressed into a melting interval which is approximately 50–60% smaller than that for pure MPY90, due to a liquidus minimum. During adiabatic ascent of hybrid source material containing a few tens of percent basalt in peridotite, the lower solidus and compressed solidus–liquidus temperature interval may conspire to substantially enhance melt productivity. Mixtures of recycled oceanic crust and peridotite in mantle plumes may therefore provide a viable source for some flood volcanics. Evidence for this would include higher than normal Fe/Mg values in natural primary liquids, consistent with equilibration with more Fe-rich olivine than normal pyrolitic olivine (i.e. <Fo_89–92). Modelling of fractionation trends in West Greenland picrites is presented to demonstrate that melts parental to the Greenland picrites were in equilibrium at mantle P–T conditions with olivine with Fo_84–86, suggesting an Fe-enriched source compared with normal peridotite, and consistent with the presence of a basaltic component in the source. Received: 29 October 1999 / Accepted: 3 February 2000     

Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2 {+/-} K2O at 1{middle dot}1 GPa

The compositions of multiply saturated partial melts are valuablefor the thermodynamic information that they contain, but aredifficult to determine experimentally because they exist onlyover a narrow temperature range at a given pressure. Here wetry a new approach for determining the composition of the partialmelt in equilibrium with olivine, orthopyroxene, clinopyroxeneand spinel (Ol + Opx + Cpx + Sp + Melt) in the system CaO–MgO–Al₂O₃–SiO₂(CMAS) at 1·1 GPa: various amounts of K₂O are added tothe system, and the resulting melt compositions and temperatureare extrapolated to zero K₂O. The ‘sandwich’ experimentalmethod was used to minimize problems caused by quench modification,and Opx and Cpx were previously synthesized at conditions nearthose of the melting experiments to ensure they had appropriatecompositions. Results were then checked by reversal crystallizationexperiments. The results are in good agreement with previouswork, and establish the anhydrous solidus in CMAS to be at 1320± 10°C at 1·1 GPa. The effect of K₂O is todepress the solidus by 5·8°C/wt %, while the meltcomposition becomes increasingly enriched in SiO₂, being quartz-normativeabove 4 wt % K₂O. Compared with Na₂O, K₂O has a stronger effectin depressing the solidus and modifying melt compositions. Theisobaric invariant point in the system CMAS–K₂O at whichOl + Opx + Cpx + Sp + Melt is joined by sanidine (San) is at1240 ± 10°C. During the course of the study severalother isobaric invariant points were identified and their crystaland melt compositions determined in unreversed experiments:Opx + Cpx + Sp + An + Melt in the system CMAS at 1315 ±10°C; in CMAS–K₂O, Opx + Cpx + Sp + An + San + Meltat 1230 ± 10°C and Opx + Sp + An + San + Sapph +Melt at 1230 ± 10°C, where An is anorthite and Sapphis sapphirine. Coexisting San plus An in three experiments helpdefine the An–San solvus at 1230–1250°C. KEY WORDS: feldspar solvus; igneous sapphirine; mantle solidus; partial melting; systems CMAS and CMAS–K₂O     

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     

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.     

Experimental comparison of trace element partitioning between clinopyroxene and melt in carbonate and silicate systems, and implications for mantle metasomatism

Experiments in the systems diopside-albite (Di-Ab) and diopside-albite-dolomite (Di-Ab-Dmt), doped with a wide range of trace elements, have been used to characterise the difference between clinopyroxene-silicate melt and clinopyroxene-carbonate melt partitioning. Experiments in Di-Ab-Dmt yielded clinopyroxene and olivine in equilibrium with CO₂-saturated dolomitic carbonate melt at 3 GPa, 1375 °C. The experiments in Di-Ab were designed to bracket those conditions (3 GPa, 1640 °C and 0.8 GPa, 1375 °C), and so minimise the contribution of differential temperature and pressure to partitioning. Partition coefficients, determined by SIMS analysis of run products, differ markedly for some elements between Di-Ab and Di-Ab-Dmt systems. Notably, in the carbonate system clinopyroxene-melt partition coefficients for Si, Al, Ga, heavy REE, Ti and Zr are higher by factors of 5 to 200 than in the silicate system. Conversely, partition coefficients for Nb, light REE, alkali metals and alkaline earths show much less fractionation (<3). The observed differences compare quantitatively with experimental data on partitioning between immiscible carbonate and silicate melts, indicating that changes in melt chemistry provide the dominant control on variation in partition coefficients in this case. The importance of melt chemistry in controlling several aspects of element partitioning is discussed in light of the energetics of the partitioning process. The compositions of clinopyroxene and carbonate melt in our experiments closely match those of near-solidus melts and crystals in CMAS-CO₂ at 3 GPa, suggesting that our partition coefficients have direct relevance to melting of carbonated mantle lherzolite. Melts so produced will be characterised by elevated incompatible trace element concentrations, due to the low degrees of melting involved, but marked depletions of Ti and Zr, and fractionated REE patterns. These are common features of natural carbonatites. The different behaviour of trace elements in carbonate and silicate systems will lead to contrasted styles of trace element metasomatism in the mantle. Received: 15 July 1999 / Accepted: 18 February 2000     

Generation and differentiation of group II kimberlites: constraints from a high-pressure experimental study to 10 GPa

Experiments have been performed in the multicomponent (natural) bulk system to constrain the conditions of generation and differentiation of a K-rich group II kimberlite (now also referred to as orangeite). The group II composition examined was saturated in olivine, orthopyroxene, and garnet at near liquidus conditions in the pressure range 4 to 10 GPa. In the range 2 to 3 GPa, the liquidus phase was olivine only. The potassic nature of the melts in the bulk compositions studied was ensured by the absence of any K-bearing phase in the residual assemblage at P > 4 GPa. Phlogopite is destabilized toward higher pressures by a carbonation reaction of the type phlogopite + CO₂ = enstatite + garnet + K₂CO₃ (liquid) + H₂O leading to alkalic, carbonatitic liquids coexisting with a garnet-peridotite (harzburgite or lherzolite) residue over a wide pressure-temperature space at pressures in excess of 4 GPa. Evidently, CO₂-bearing systems do not favor the stability of phlogopite and/or K-richterite amphibole at pressures in excess of 4 to 5 GPa, and it is suggested that the carbonate-bearing and potassic character of any mantle melt originating from this depth is most likely the product of a two-stage process: either a carbonate-bearing protolith is invaded by a potassic melt or fluid (probably supercritical), or a potassic protolith (after metasomatism) has been invaded by a carbonatite melt.