Estimation of temperature conditions for the formation of HASP and GASP glasses from the lunar regolith

Impact cratering on the Moon’s surface was accompanied by the high-temperature melting of rocks, melt evaporation, and silicate vapor condensation. Evidence for the extensive evaporative fractionation of melts was found in HASP (High-Alumina Silica-Poor) glasses from the lunar regolith. Numerous objects of condensation origin were found in the Apollo 14 regolith breccia. They are referred to as GASP (Gas-Associated Spheroidal Precipitates). With respect to chemical characteristics, namely FeO and SiO₂ contents, GASP were subdivided into Fe-rich (FeGASP) and Si-rich (SiGASP) condensates. Based on experimental data on the evaporation of aluminous basalt sample 68415.40 from the Apollo 16 collection and the calculated compositions of residual melts and complementary vapors at various temperatures, we compared the obtained compositions with the chemical analyses of the HASP glasses and GASP condensates. The comparison was aimed at estimating the temperature conditions of HASP and GASP formation. The comparison showed that the compositions of the HASP glasses and GASP condensates are consistent with the compositions obtained in the equilibrium experiment. In accordance with the experiment, the temperature range of the evaporation of HASP glasses was estimated as ∼1750–1870°C. The temperature interval of condensation, with allowance for the effect of vapor supercooling, is ∼1700–1500°C for FeGASP and no higher than 1700–1750°C for SiGASP. This paper discusses the problems of establishing interphase thermodynamic equilibrium during the dispersion of a vapor-melt cloud, vapor supercooling during its condensation, and the influence of the curvature of melt and condensate particles on the character of evaporation and condensation.     

Lunar rock-rain: Diverse silicate impact-vapor condensates in an Apollo-14 regolith breccia

Apollo 14 regolith breccia 14076, long known to be uniquely endowed with high-alumina, silica-poor (HASP) material of evaporation-residue origin, has been found to contain a diverse suite of complementary condensates, dubbed GASP (gas-associated spheroidal precipitates). GASP occurs in two forms: as glassy or extremely fine grained quenched-melt spheroids, mostly less than 5 μm across; and as quenched textured clasts up to 200 μm across. In two of the clasts, origin by aggregation of spheroidal GASP is confirmed by the presence of relict spheroids. GASP is distinctively depleted in the same refractory major oxides that are characteristically enriched in HASP: Al₂O₃ and CaO. Among the larger GASP spheroids, Al₂O₃ is seldom >1 wt%; among the clasts, excluding two instances of apparent contamination by Na- and K-rich substrate-derived melt, bulk Al₂O₃ averages 0.3 wt%. Depletion of Al₂O₃ and CaO is also manifested by pyroxene compositions in some clasts; e.g., in the largest clast, En₈₂Wo_0.45 with 0.07 wt% Al₂O₃. Although GASP bulk compositions are nearly pure SiO₂ + MgO + FeO, they are nonetheless highly diverse. Spheroid compositions range in mg from 7 to 84 mol%, and in FeO/SiO₂ (weight ratio) from 0.002 to 0.67. Bulk compositions and textures of many GASP spheroids suggest that liquid immiscibility occurred prior to quenching; implying that these materials were, some time after condensation, at temperatures of ∼1680 °C. Textural evidence for immiscibility includes lobate boundaries between silicic and mafic domains, and a general tendency for quenched mafic silicates to be concentrated into a few limited patches rather than evenly dispersed. The parent melt of the largest clast’s pyroxene is inferred to have formed as a partial melt within the parent aggregation of GASP matter, compositionally near the pyroxene + cristobalite + melt eutectic and thus at ∼1500 °C. A few GASP spheroids show possible signs of in-flight collision-coalescence, but aggregation of the much larger clasts probably took place in mushy puddles on the lunar surface. Little mixing took place between these GASP puddles and the related HASP, probably because GASP condensation did not commence until after an intermediate stage during which, while neither net evaporation nor net condensation took place, expansion of the vapor cloud carried the eventual GASP matter well apart from the HASP. Considering the characteristic length-scale of lunar regolith mixing, the concentration of both GASP and HASP into this single unique regolith sample (14076) is most consistent with a parent crater size (diameter) of 10-100 km. I speculate that the 14076 regolith may have been unusually situated, almost directly uprange from an unusually oblique large impact. Mercurian analogs of the 14076 impact condensates may have significant implications for remote sensing.     

Primordial compositions of refractory inclusions

Bulk chemical and O-, Mg- and Si-isotopic compositions were measured for each of 17 Types A and B refractory inclusions from CV3 chondrites. After bulk chemical compositions were corrected for non-representative sampling in the laboratory, the Mg- and Si-isotopic compositions of each inclusion were used to calculate its original chemical composition assuming that the heavy-isotope enrichments of these elements are due to Rayleigh fractionation that accompanied their evaporation from CMAS liquids. The resulting pre-evaporation chemical compositions are consistent with those predicted by equilibrium thermodynamic calculations for high-temperature nebular condensates, but only if different inclusions condensed from nebular regions that ranged in total pressure from 10⁻⁶ to 10⁻¹ bar, regardless of whether they formed in a system of solar composition or in one enriched in dust of ordinary chondrite composition relative to gas by a factor of 10 compared to solar composition. This is similar to the range of total pressures predicted by dynamic models of the solar nebula for regions whose temperatures are in the range of silicate condensation temperatures. Alternatively, if departure from equilibrium condensation and/or non-representative sampling of condensates in the nebula occurred, the inferred range of total pressure could be smaller. Simple kinetic modeling of evaporation successfully reproduces observed chemical compositions of most inclusions from their inferred pre-evaporation compositions, suggesting that closed-system isotopic exchange processes did not have a significant effect on their isotopic compositions. Comparison of pre-evaporation compositions with observed ones indicates that 80% of the enrichment in refractory CaO + Al₂O₃ relative to more volatile MgO + SiO₂ is due to initial condensation and 20% due to subsequent evaporation for both Types A and B inclusions.     

Volatility inversion of silicon and magnesium oxides during the evaporation of HASP glasses on the moon

An inversion of SiO₂ and MgO volatility occurs during high-temperature melt evaporation in the CaO–MgO–Al₂O₃–SiO₂ (CMAS) system. This results in that SiO₂, which is usually more volatile than MgO, becomes less volatile during the evaporation of melts enriched in the refractory oxides CaO and Al₂O₃. The volatility inversion is adequately explained within the theory of acid–base interaction of silicate melt components developed by D.S. Korzhinskii. The compositions of high-Al₂O₃ and SiO₂-poor glasses (known as HASP glasses) from the lunar regolith show a systematic decrease in MgO/SiO₂ with increasing CaO content, which is a direct consequence of the influence of acid–base effects.     

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     

Valence state of iron in a condensate from the Luna 16 regolith

This paper reports the results of an X-ray photoelectron spectroscopic study of the condensate phase of regolith sample L1639 returned by the Luna 16 mission. The reduced Si⁰, Si²⁺, Al⁰, Ti²⁺, and Ti³⁺ forms were detected in the sample. Iron occurs in all valence states, and Fe³⁺ species were detected for the first time in the condensate. Minor Fe³⁺ concentrations were observed in the upper layers of the sample containing the maximum amounts of condensate products. The fraction of ferric Fe is 22%, and the Fe⁰: Fe²⁺: Fe³⁺ proportion is 33: 45: 22. The appearance of ferric Fe in the lunar condensate is explained by the reaction of FeO disproportionation occurring either at the stage of the expansion and cooling of impact-related vapor or directly in the condensed phase on the surface of regolith particles. This interpretation is supported by the results of a model experiment on augite vaporization and condensation. The experiment simulating impact vaporization was carried out on a laser set-up at a temperature of ∼3000–4000 K and a pulse duration of ∼10⁻³ s in a He atmosphere (P = 1 atm). The results of analyses provided compelling evidence that the condensate produced after augite vaporization contains Fe in all oxidation states, and the proportions of different valence forms approach the stoichiometry of the disproportionation reaction.     

Experiments on silicate melt immiscibility in the system Fe2SiO4–KAlSi3O8–SiO2–CaO–MgO–TiO2–P2O5 and implications for natural magmas

The effect of CaO and MgO, with or without TiO₂ and P₂O₅, on the two-melt field in the simplified system Fe₂SiO₄–KAlSi₃O₈–SiO₂ has been experimentally determined at 1,050°–1,240°C, 400 MPa. Despite the suppressing effect of MgO, CaO, and pressure on silicate melt immiscibility, our experiments show that this process is still viable at mid-crustal pressures when small amounts (0.6–2.0 wt%) of P₂O₅ and TiO₂ are present. Our data stress that the major element partition coefficients between the two melts are highly correlated with the degree of polymerisation (nbo/t) of the SiO₂-rich melt, whatever temperature, pressure, or exact composition. Experimental immiscible melt compositions in natural systems at 0.1 MPa from the literature (lunar and tholeiitic basalts) plot on similar but distinct curves compared to the simplified system. These relations between melt polymerisation and partition coefficients, which hold for a large range of compositions and fO₂, are extended to various volcanic and plutonic rocks. This analysis strengthens the proposal that silicate melt immiscibility can be important in volcanic rocks of various compositions (from tholeiitic basalts to lamprophyres). However, the majority of proposed immiscible compositions in plutonic rocks are at least not coexisting melts, but may have suffered accumulation of early crystallized minerals.     

The origin and evolution of the parental magmas of frontal volcanoes in Kamchatka: Evidence from magmatic inclusions in olivine from Zhupanovsky volcano

The paper presents data on naturally quenched melt inclusions in olivine (Fo 69–84) from Late Pleistocene pyroclastic rocks of Zhupanovsky volcano in the frontal zone of the Eastern Volcanic Belt of Kamchatka. The composition of the melt inclusions provides insight into the latest crystallization stages (∼70% crystallization) of the parental melt (∼46.4 wt % SiO₂, ∼2.5 wt % H₂O, ∼0.3 wt % S), which proceeded at decompression and started at a depth of approximately 10 km from the surface. The crystallization temperature was estimated at 1100 ± 20°C at an oxygen fugacity of ΔFMQ = 0.9–1.7. The melts evolved due to the simultaneous crystallization of olivine, plagioclase, pyroxene, chromite, and magnetite (Ol: Pl: Cpx: (Crt-Mt) ∼ 13: 54: 24: 4) along the tholeiite evolutionary trend and became progressively enriched in FeO, SiO₂, Na₂O, and K₂O and depleted in MgO, CaO, and Al₂O₃. Melt crystallization was associated with the segregation of fluid rich in S-bearing compounds and, to a lesser extent, in H₂O and Cl. The primary melt of Zhupanovsky volcano (whose composition was estimated from data on the most primitive melt inclusions) had a composition of low-Si (∼45 wt % SiO₂) picrobasalt (∼14 wt % MgO), as is typical of parental melts in Kamchatka and other island arcs, and was different from MORB. This primary melt could be derived by ∼8% melting of mantle peridotite of composition close to the MORB source, under pressures of 1.5 ± 0.2 GPa and temperatures 20–30°C lower than the solidus temperature of “dry” peridotite (1230–1240°C). Melting was induced by the interaction of the hot peridotite with a hydrous component that was brought to the mantle from the subducted slab and was also responsible for the enrichment of the Zhupanovsky magmas in LREE, LILE, B, Cl, Th, U, and Pb. The hydrous component in the magma source of Zhupanovsky volcano was produced by the partial slab melting under water-saturated conditions at temperatures of 760–810°C and pressures of ∼3.5 GPa. As the depth of the subducted slab beneath Kamchatkan volcanoes varies from 100 to 125 km, the composition of the hydrous component drastically changes from relatively low-temperature H₂O-rich fluid to higher temperature H₂O-bearing melt. The geothermal gradient at the surface of the slab within the depth range of 100–125 km beneath Kamchatka was estimated at 4°C/km.     

Cumulate xenoliths from St. Vincent, Lesser Antilles Island Arc: a window into upper crustal differentiation of mantle-derived basalts

In order to shed light on upper crustal differentiation of mantle-derived basaltic magmas in a subduction zone setting, we have determined the mineral chemistry and oxygen and hydrogen isotope composition of individual cumulus minerals in plutonic blocks from St. Vincent, Lesser Antilles. Plutonic rock types display great variation in mineralogy, from olivine–gabbros to troctolites and hornblendites, with a corresponding variety of cumulate textures. Mineral compositions differ from those in erupted basaltic lavas from St. Vincent and in published high-pressure (4–10 kb) experimental run products of a St. Vincent high-Mg basalt in having higher An plagioclase coexisting with lower Fo olivine. The oxygen isotope compositions (δ¹⁸O) of cumulus olivine (4.89–5.18‰), plagioclase (5.84–6.28‰), clinopyroxene (5.17–5.47‰) and hornblende (5.48–5.61‰) and hydrogen isotope composition of hornblende (δD = −35.5 to −49.9‰) are all consistent with closed system magmatic differentiation of a mantle-derived basaltic melt. We employed a number of modelling exercises to constrain the origin of the chemical and isotopic compositions reported. δ¹⁸O_Olivine is up to 0.2‰ higher than modelled values for closed system fractional crystallisation of a primary melt. We attribute this to isotopic disequilibria between cumulus minerals crystallising at different temperatures, with equilibration retarded by slow oxygen diffusion in olivine during prolonged crustal storage. We used melt inclusion and plagioclase compositions to determine parental magmatic water contents (water saturated, 4.6 ± 0.5 wt% H₂O) and crystallisation pressures (173 ± 50 MPa). Applying these values to previously reported basaltic and basaltic andesite lava compositions, we can reproduce the cumulus plagioclase and olivine compositions and their associated trend. We conclude that differentiation of primitive hydrous basalts on St. Vincent involves crystallisation of olivine and Cr-rich spinel at depth within the crust, lowering MgO and Cr₂O₃ and raising Al₂O₃ and CaO of residual melt due to suppression of plagioclase. Low density, hydrous basaltic and basaltic andesite melts then ascend rapidly through the crust, stalling at shallow depth upon water saturation where crystallisation of the chemically distinct cumulus phases observed in this study can occur. Deposited crystals armour the shallow magma chamber where oxygen isotope equilibration between minerals is slowly approached, before remobilisation and entrainment by later injections of magma.     

The Effect of Cr2O3 on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2-Cr2O3 at 1{middle dot}1 GPa

Chromium as Cr³⁺ substitutes for octahedrally coordinated Alin upper-mantle minerals, thereby reducing the activity of Al₂O₃in the system and hence the concentration of Al₂O₃ in partialmelts. The effect of Cr₂O₃ on melt compositions multiply saturatedwith the spinel lherzolite phase assemblage has been quantifiedin the system CaO–MgO–Al₂O₃–SiO₂–Cr₂O₃at 1·1 GPa as a function of 100 Cr/(Cr + Al) in the spinel(Cr#_sp). The decrease of Al₂O₃ in the melt with increasing Cr#_spis accompanied by increasing MgO and SiO₂, whereas CaO remainsalmost constant. Consequently, the CaO/Al₂O₃ ratio of the meltincreases with Cr#_sp, and the melt becomes richer in normativediopside, hypersthene and quartz. The effect may explain certainmantle melts with unusually high CaO/Al₂O₃ ratios. The concentrationof Cr₂O₃ in the melt remains low even at high Cr#_sp, which meansthat the strong effect of Cr₂O₃ on partial melting equilibriais not readily apparent from its concentration in the melt itself.The existence of a highly refractory major component such asCr₂O₃ nullifies simplified conclusions from the ‘inverseapproach’ in the experimental study of basalt petrogenesis,as there is insufficient information in the composition of thepartial melt to reconstruct the conditions of melting. KEY WORDS: basalt petrogenesis; partial melting; reversal experiment; spinel lherzolite; system CMAS–Cr₂O₃; CaO/Al₂O₃ of melt; effect of Cr₂O₃     

Phase equilibria constraints on melting of stromatic migmatites from Ronda (S. Spain): insights on the formation of peritectic garnet

Stromatic metatexites occurring structurally below the contact with the Ronda peridotite (Ojén nappe, Betic Cordillera, S Spain) are characterized by the mineral assemblage Qtz+Pl+Kfs+Bt+Sil+Grt+Ap+Gr+Ilm. Garnet occurs in low modal amount (2–5 vol.%). Very rare muscovite is present as armoured inclusions, indicating prograde exhaustion. Microstructural evidence of melting in the migmatites includes pseudomorphs after melt films and nanogranite and glassy inclusions hosted in garnet cores. The latter microstructure demonstrates that garnet crystallized in the presence of melt. Re‐melted nanogranites and preserved glassy inclusions show leucogranitic compositions. Phase equilibria modelling of the stromatic migmatite in the MnO–Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂–O₂–C (MnNCaKFMASHOC) system with graphite‐saturated fluid shows P–T conditions of equilibration of 4.5–5 kbar, 660–700 °C. These results are consistent with the complete experimental re‐melting of nanogranites at 700 °C and indicate that nanogranites represent the anatectic melt generated immediately after entering supersolidus conditions. The P–T estimate for garnet and melt development does not, however, overlap with the low‐temperature tip of the pure melt field in the phase diagram calculated for the composition of preserved glassy inclusions in garnet in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCKFMASH) system. A comparison of measured melt compositions formed immediately beyond the solidus with results of phase equilibria modelling points to the systematic underestimation of FeO, MgO and CaO in the calculated melt. These discrepancies are present also when calculated melts are compared with low‐T natural and experimental melts from the literature. Under such conditions, the available melt model does not perform well. Given the presence of melt inclusions in garnet cores and the P–T estimates for their formation, we argue that small amounts (<5 vol.%) of peritectic garnet may grow at low temperatures (≤700 °C), as a result of continuous melting reactions consuming biotite.     

Experiments on the kinetics of partial melting of a leucogranite at 200 MPa H<Subscript>2</Subscript>O and 690–800°C: compositional variability of melts during the onset of H<Subscript>2</Subscript>O-saturated crustal anatexis

We have experimentally investigated the kinetics of melting of an aplitic leucogranite (quartz+sodic plagioclase of ≈Ab₉₀+K-feldspar+traces of biotite) at 690, 740, and 800°C, all at 200 MPa H₂O. Leucogranite cylinders, 3.5 mm in diameter and 7 mm in length, were run in the presence of excess H₂O using cold-seal pressure vessels for 11–2,925 h. At 690 and 740°C and any experimental time, and 800°C and short run times, silicate glass (melt at run conditions) occurs as interconnected films along most of the mineral boundaries and in fractures, with the predominant volume occurring along quartz/feldspars boundaries and quartz/plagioclase/K-feldspar triple junctions. Glass film thickness is roughly constant throughout a given experimental charge and increases with experimental temperature and run duration. The results indicate that H₂O-saturated partial melting of a quartzo-feldspathic protolith will produce an interconnected melt phase even at very low degrees (<5 vol%) of partial melting. Crystal grain boundaries are therefore completely occluded with melt films even at the lowest degrees of partial melting, resulting in a change in the mechanism of mass transport through the rock from advection of aqueous vapor to diffusion through silicate melt. At 690 and 740°C the compositions of glasses are homogeneous and (at both temperatures) close to, but not on, the H₂O-saturated 200 MPa haplogranite eutectic; glass compositions do not change with run duration. At 800°C glasses are heterogeneous and plot away from the minimum, although their molar ratios ASI (=mol Al₂O₃/CaO+Na₂O+K₂O) and Al/Na are constant throughout the entire charge at any experimental time. Glass compositions within individual 800°C experiments form linear trends in (wt%) normative quartz–albite–orthoclase space. The linear trends are oriented perpendicular to the 200 MPa H₂O haplogranite cotectic line, reflecting nearly constant albite/orthoclase ratio versus variable quartz/feldspar ratio, and have endpoints between the 800°C isotherms on the quartz and feldspar liquidus surfaces. With increasing experimental duration the trends migrate from the potassic side of the minimum toward the bulk rock composition located on the sodic side, due to more rapid (and complete) dissolution of K-feldspar relative to plagioclase. The results indicate that partial melting at or slightly above the solidus (690–740°C) is interface reaction-controlled, and produces disequilibrium melts of near-minimum composition that persist metastably for up to at least 3 months. Relict feldspars show no change in composition or texture, and equilibration between melt and feldspars might take from a few to tens of millions of years. Partial melting at temperatures well above the solidus (800°C) produces heterogeneous, disequilibrium liquids whose compositions are determined by the diffusive transport properties of the melt and local equilibrium with neighboring mineral phases. Feldspars recrystallize and change composition rapidly. Partial melting and equilibration between liquids and feldspars might take from a few to tens of years (H₂O-saturated conditions) at these temperatures well above the solidus.     

Silicate globules in kyanite from grospydites of the Zagadochnaya kimberlite pipe,Yakutia: The problem of the origin

The results of complex study of silicate globules and α-quartz paramorphs after coesite in kyanite from grospydites from the Zagadochnaya kimberlite pipe, Yakutia, using optical and scanning electron spectroscopy, electron and ion microprobes, LA ICP MS and Raman spectroscopy, are presented. The existence of radial fractures diverging from silicate globules into the matrix (kyanite) attests to the fact that the content of the globules is extremely condensed. A zonal structure is usually typical for globules: a coat and a core, which can be explicitly distinguished under the electron microscope, can be differentiated in them. Compositionally, the coat of the globule corresponds to potassium feldspar (wt %: 66.4 SiO₂; 16.9 Al₂O₃; 0.4 FeO; 0.1 CaO; 0.2 Na₂O; 14.7 K₂O). The globules were also detected in which along with K, a high content of Na and Ca was also ascertained in the silicate coat. The globule coat is considerably enriched with Ba, La, Ce, Nb, and a number of other noncompatible elements as compared with xenolith minerals. The water content in globules is ∼0.6 wt %. As compared with the host mineral (kyanite), the core part of the globules is also enriched with Co, Ni, Zn, and Cu; their content in kyanite is negligibly low. The entire data collection attests to the fact that the formation of silicate globules could have been caused by interaction of the conservated fluid and/or water-silicate melt with the host mineral and crystalline inclusions of clinopyroxene and garnet with decreasing pressure during the transportation of grospydite xenoliths by the kimberlite melt to the Earth’s surface.     

Mantle melting in equilibrium with an Iron–Wüstite–Graphite buffered COH-fluid

Partial melting experiments on a San Carlos peridotite were done in a Walker type multi-anvil press at pressures from 5 to 12.5 GPa. Experiments were done in the presence of a COH-fluid and at oxygen fugacity controlled by the Fe–FeO buffer. Olivine, clinopyroxene, garnet and orthopyroxene are stable in all but the highest temperature 10 GPa experiments where olivine and garnet coexist, and the highest temperature 5 GPa experiments where olivine is the single crystalline phase. The solidus at 5 GPa was found to be at approximately 1,200°C and the liquidus was estimated to be at 1,325°C, which is ∼500°C lower than has been reported for dry melting of peridotite. The aluminum concentration of the melts decreases with increasing melt fraction and decreases also with increasing pressure. At 5 GPa the melts have a CaO/Al₂O₃-ratio of 0.85–1.0, which is similar to that of undepleted komatiites; major element concentrations are also identical to those of undepleted komatiites such as the Munro komatiites. At 10 and 12.5 GPa the partial melts have CaO/Al₂O₃-ratios above 1.5 and major element composition almost identical to aluminum depleted komatiites such as the Barberton komatiites. We therefore conclude that in the presence of a reducing COH-fluid both aluminum-depleted and -undepleted komatiites could have formed at temperatures much lower than generally accepted.     

An experimental study of anorthosite dissolution in lunar picritic magmas: Implications for crustal assimilation processes

Experiments characterizing the kinetics of anorthosite dissolution in lunar picritic magmas (very low-Ti, low-Ti, and high-Ti picritic glasses) were conducted at 0.6 GPa and 1250-1400 °C using the dissolution couple method. Reaction between the anorthosite and lunar picritic magmas at 1250-1300 °C produced a spinel + melt layer. Reaction between the anorthosite and an olivine-saturated low-Ti magma at 1250-1300 °C produced a crystal-free region between the spinel + melt layer and the olivine-saturated magma. The anorthosite dissolution experiments conducted at 1400 °C simply dissolved anorthosite and did not result in a crystal-bearing region. The rate of anorthosite dissolution strongly depends on temperature and composition of the reacting melt. Concentration profiles that develop during anorthosite dissolution are nonlinear and extend from the picritic glass compositions to anorthite. These profiles feature a large and continuous variation in melt density and viscosity from the anorthosite-melt interface to the initial picritic magmas. In both the low-Ti and high-Ti magmas the diffusive fluxes of TiO₂, Al₂O₃, and SiO₂ are strongly coupled to the concentration gradients of CaO and FeO. Anorthosite dissolution may play an important role in producing the chemical variability of the lunar picritic magmas, the origin of spinel in the lunar basalts and picritic glasses, and the petrogenesis of the high-Al basalts.     

Coexistence of two distinct mantle sources during formation of ophiolites: a case study of primitive pillow-lavas from the lowest part of the volcanic section of the Troodos Ophiolite, Cyprus

We present a detailed mineralogical, petrological and melt inclusion study of unusually fresh, primitive olivine + clinopyroxene phyric Lower Pillow Lavas (LPL) found near Analiondas village in the northeastern part of the Troodos ophiolite (Cyprus). Olivine phenocrysts in these primitive LPL show a wide compositional range (Fo_82–92) and have higher CaO contents than those from the Upper Pillow Lavas (UPL). Cr-spinel inclusions in olivine are significantly less Cr-rich (Cr/Cr + Al = 28–67 mol%) compared to those from the UPL (Cr# = 70–80). These features reflect differences in melt compositions between primitive LPL and the UPL, namely higher CaO and Al₂O₃ and lower FeO* compared to the UPL at a given MgO. LPL parental melts (in equilibrium with Fo₉₂) had ∼10.5 wt% MgO and crystallization temperatures ∼1210 °C, which are significantly lower than those previously published for the UPL (14–15 wt% MgO and ∼1300 °C for Fo₉₂). The fractionation path of LPL parental melts is also different from that of the UPL. It is characterized initially by olivine + clinopyroxene cotectic crystallization joined by plagioclase at ∼9 wt% MgO, whereas UPL parental melts experienced a substantial interval of olivine-only crystallization. Primitive LPL melts were formed from a mantle source which was more fertile than that of tholeiites from well-developed intra-oceanic arcs, but broadly similar in its fertility to that of Mid-Ocean Ridge Basalt (MORB) and Back Arc Basin Basalts (BABB). The higher degrees of melting during formation of the LPL primary melts compared to average MORB were caused by the presence of subduction-related components (H₂O). Our new data on the LPL coupled with existing data for the UPL support the existing idea that the LPL and UPL primary melts originated from distinct mantle sources, which cannot be related by progressive source depletion. Temperature differences between these sources (∼150 °C), their position in the mantle (∼10 kbar for the colder LPL source vs 15–18 kbar for the UPL source), and temporal succession of Troodos volcanism, all cannot be reconciled in the framework of existing models of mantle wedge processes, thermal structure and evolution, if a single mantle source is invoked. Possible tectonic settings for the origin of the Troodos ophiolite (forearc regions of intra-oceanic island arc, propagation of backarc spreading into arc lithosphere) are discussed. Received: 20 May 1996 / Accepted: 25 March 1997     

A preferred method for the determination of bulk compositions of coarse-grained refractory inclusions and some implications of the results

Analyses of coarse-grained refractory inclusions typically do not have the solar CaO/Al₂O₃ ratio, probably reflecting nonrepresentative sampling of them in the laboratory. Many previous studies, especially those done by instrumental neutron activation analysis (INAA), were based on very small amounts of material removed from those restricted portions of inclusions that happened to be exposed on surfaces of bulk meteorite samples. Here, we address the sampling problem by studying thin sections of large inclusions, and by analyzing much larger aliquots of powders of these inclusions by INAA than has typically been done in the past. These results do show convergence toward the solar CaO/Al₂O₃ ratio of 0.792. The bulk compositions of 15 coarse-grained inclusions determined by INAA of samples >2 mg have an average CaO/Al₂O₃ ratio of 0.80 ± 0.18. When bulk compositions are obtained by modal recombination based on analysis of thin sections with cross-sections of entire, large, unbroken inclusions, the average of 11 samples (0.79 ± 0.15) also matches the solar value. Among those analyzed by INAA and by modal recombination, there were no inclusions for which both techniques agreed on a CaO/Al₂O₃ ratio deviating by >∼15% from the solar value. These results suggest that: individual inclusions may have the solar CaO/Al₂O₃ ratio; departures from this value are due to sample heterogeneity and nonrepresentative sampling in the laboratory; and it is therefore valid to correct compositions to this value. We present a method for doing so by mathematical addition or subtraction of melilite, spinel, or pyroxene. This yields a set of multiple, usually slightly different, corrected compositions for each inclusion. The best estimate of the bulk composition of an inclusion is the average of these corrected compositions, which simultaneously accounts for errors in sampling of all major phases. Results show that Type B2 inclusions tend to be more SiO₂-rich and have higher normative Anorthite/Gehlenite component ratios than Type B1s. The inclusion bulk compositions lie in a field that can result from evaporation at 1700-2000K of CMAS liquids with solar CaO/Al₂O₃, but with a wide range of initial MgO (30-60 wt%) and SiO₂ (15-50 wt%) contents.     

Dehydration melting of tonalites. Part II. Composition of melts and solids

 Dehydration melting of tonalitic compositions (phlogopite or biotite-plagioclase-quartz assemblages) is investigated within a temperature range of 700–1000°C and pressure range of 2–15 kbar. The solid reaction products in the case of the phlogopite-plagioclase(An₄₅)-quartz starting material are enstatite, clinopyroxene and potassium feldspar, with amphiboles occurring occasionally. At 12 kbar, zoisite is observed below 800°C, and garnet at 900°C. The reaction products of dehydration melting of the biotite (Ann₅₀)-plagioclase (An₄₅)-quartz assemblage are melt, orthopyroxene, clinopyroxene, amphibole and potassium feldspar. At pressures > 8 kbar and temperatures below 800°C, epidote is also formed. Almandine-rich garnet appears above 10 kbar at temperatures ≥ 750°C. The composition of melts is granitic to granodioritic, hence showing the importance of dehydration melting of tonalites for the formation of granitic melts and granulitic restites at pressure-temperature conditions within the continental crust. The melt compositions plot close to the cotectic line dividing the liquidus surfaces between quartz and potassium feldspar in the haplogranite system at 5 kbar and a _{H 2O} = 1. The composition of the melts changes with the composition of the starting material, temperature and pressure. With increasing temperature, the melt becomes enriched in Al₂O₃ and FeO+MgO. Potash in the melt is highest just when biotite disappears. The amount of CaO decreases up to 900°C at 5 kbar whereas at higher temperatures it increases as amphibole, clinopyroxene and more An-component dissolve in the melt. The Na₂O content of the melt increases slightly with increase in temperature. The composition of the melt at temperatures > 900°C approaches that of the starting assemblage. The melt fraction varies with composition and proportion of hydrous phases in the starting composition as well as temperature and pressure. With increasing modal biotite from 20 to 30 wt%, the melt proportion increases from 19.8 to 22.3 vol.% (850°C and 5 kbar). With increasing temperature from 800 to 950°C (at 5 kbar), the increase in melt fraction is from 11 to 25.8 vol.%. The effect of pressure on the melt fraction is observed to be relatively small and the melt proportion in the same assemblage decreases at 850°C from 19.8 vol.% at 5 kbar to 15.3 vol.% at 15 kbar. Selected experiments were reversed at 2 and 5 kbar to demonstrate that near equilibrium compositions were obtained in runs of longer duration. Received: 27 December 1995 / Accepted: 7 May 1996     

Lithosphere formation in the central Slave Craton (Canada): plume subcretion or lithosphere accretion?

Major-element compositions of minerals in peridotite xenoliths from the Lac de Gras kimberlites provide constraints on the mode of lithosphere formation beneath the central Slave Craton, Canada. Magnesia contents of reconstructed whole rocks correlate positively with NiO and negatively with CaO contents, consistent with variable partial melt extraction. Alumina and Cr₂O₃ contents are broadly positively correlated, suggestive of melt depletion in the absence of a Cr–Al phase. Garnet modes are high at a given Al₂O₃ content (a proxy for melt depletion), falling about a 7 GPa melt depletion model. These observations, combined with high olivine Mg# and major-element relationships of FeO-poor peridotites (<7.5 wt%) indicative of melt loss at pressures >3 GPa (residual FeO content being a sensitive indicator of melt extraction pressure), and similar high pressures of last equilibration (∼4.2 to 5.8 GPa), provide multiple lines of evidence that the mantle beneath the central Slave Craton has originated as a residue from high-pressure melting, possibly during plume subcretion. Apparent low melt depletion pressures for high-FeO peridotites (>7.5 wt%) could suggest formation in an oceanic setting, followed by subduction to their depth of entrainment. However, these rocks, which are characterised by low SiO₂ contents (<43 wt%), are more likely to be the result of post-melting FeO-addition, leading to spuriously low estimates of melt extraction pressures. They may have reacted with a silica-undersaturated melt that dissolved orthopyroxene, or experienced olivine injection by crystallising melts. A secular FeO-enrichment of parts of the deep mantle lithosphere is supported by lower average Mg# in xenolithic olivine (91.7) compared to olivine inclusions in diamond (92.6).     

Model evaporation of FeO-bearing liquids: Application to chondrules

Models for thermodynamic behavior of FeO-bearing liquids are required for understanding the separate roles of evaporation, condensation and crystallization in the formation of free-floating silicate liquid droplets in the early solar nebula. These droplets, frozen as chondrules, are common in chondritic meteorites. Evaporation coefficients for Fe and FeO of ∼0.2 are calculated here from existing data using silicate liquid activity models. These models, used to describe gas-liquid-solid equilibria and to constrain kinetic processes, are compared and found similar, and the effects of liquid non-ideality are assessed. A general approach is presented for predicting the evaporation behavior of FeO-bearing Al₂O₃-CaO-SiO₂-MgO liquids in H₂-rich gas above 1400 K at low total pressure. Results are vapor pressure curves for Fe, FeO and other gas species above typical chondrule liquids, suitable for predicting compositional trajectories of residual liquids evaporating in a hydrogen-dominated vapor. These predictions are consistent with chondrule formation in the protoplanetary disk in heating events of short duration, such as those expected from shock wave or current sheet models.