Systematics of calcium partitioning between olivine and silicate melt: implications for melt structure and calcium content of magmatic olivines

A systematic characterization of the chemical factors that control calcium partitioning between olivine and melt in a magmatic environment was undertaken using experiments performed on compositionally simple systems (CaO-MgO-SiO₂, CaO-MgO-Al₂O₃-SiO₂, CaO-MgO-Al₂O₃-SiO₂-Cr₂O₃, CaO-MgO-Al₂O₃-SiO₂-TiO₂, CaO-MgO-Al₂O₃-SiO₂-Na₂O, CaO-MgO-Al₂O₃-SiO₂-FeO, CaO-MgO-Al₂O₃-SiO₂-FeO-Na₂O) over a wide range of temperature (1050–1530 °C) at one bar pressure. The calcium concentration of olivines is shown to be dependent not only on the forsterite content of the olivine but to a large extent on melt composition. For a fixed CaO content of the melt, these results show that the CaO concentration of olivine is strongly sensitive to the amount of alumina, alkali and ferrous iron present in the coexisting melt. Oxygen fugacity and temperature are not found directly to affect Ca partitioning. It is thus proposed that the systematic variations of the calcium content of olivine may be used as an “in-situ chemical potentiometer” of the lime activity of the melt. Based upon these data in synthetic systems, an empirical model describing Ca partitioning between olivine and melt is developed. When applied to natural olivines this model reproduces their Ca content, where melt composition is known, to within ±10% relative. The model may therefore be used to predict changes in melt composition during olivine crystallization and/or to assess whether an olivine is in equilibrium with its host magma. Finally, the wide range of Ca partitioning observed at fixed crystal composition confirms that minor element partitioning between crystal and melt cannot be predicted from the physical characteristics of the crystal alone, and that the non-ideality of the melt has to be taken into account. Received: 12 June 1998 / Accepted: 1 February 1999     

Melt structural control on olivine/melt element partitioning of Ca and Mn

Relationships between mineral/silicate melt partition coefficients and melt structure have been examined by combining Ca and Mn olivine/melt partitioning data with available melt structure information. Compositions were chosen so that melts with olivine on their liquidii range in degree of polymerization, NBO/T, from ∼0.5 to ∼2.5 under near isothermal conditions (1350-1400°C). Olivine/melt Ca-Mn exchange coefficients, Ca(olivine)/CaO(melt)/MnO(olivine)/MnO(melt) (K_{D Ca-Mn}^olivine/melt), as a function of melt NBO/T have a parabolic shape with a minimum K_{D Ca-Mn}^olivine/melt-value at NBO/T near 1. Notably, published K_{D Fe2⁺-Mg}^olivine/melt versus NBO/T functions are also parabolic with a maximum in K_{D Fe2⁺-Mg}^olivine/melt near 1 (Kushiro and Mysen, 2002).The olivine/melt partitioning data are modeled in terms of structural units (Qⁿ-species) in the melt. The NBO/T-value corresponding to the minimum K_{D Ca-Mn}^olivine/melt is near that where the abundance ratio of Qⁿ-species, X_Q3/X_Q2, has its largest value. Therefore, the activity coefficient ratio in the melt, γ_Ca2⁺(melt)/γ_Mn2⁺(melt), attains a minimum where the abundance ratio of X_Q3/X_Q2 is at maximum. It is inferred from this relationship that Ca²⁺ in the melts is dominantly bonded to nonbridging oxygen (Ca-NBO) in Q³-species, whereas Mn²⁺ is bonded to nonbridging oxygen (Mn-NBO) in less polymerized Qⁿ-species such as Q².     

Infrared spectroscopic investigation of hydroxyl in β-(Mg,Fe)2SiO4 and coexisting olivine: Implications for mantle evolution and dynamics

Wadsleyite (β-(Mg,Fe)₂SiO₄) is a major constituent of the Earth's transition zone and is known to accommodate OH. The portion of the transition zone between 400–550 km could be an important source or sink for hydroxyl in plumes and slabs intersecting this region. Micro-infrared spectroscopy has been carried out on the β-phase and coexisting metastable olivine synthesized in a multianvil apparatus at 14 GPa and 1550–1650 K under hydrous conditions. Single-crystal and polycrystal specimens of both phases were analyzed in the 1800–8500 cm^?1 frequency region to determine the speciation, abundances, and partitioning behavior of the hydrous components in coexisting β-phase and olivine. β-phase spectra consistently show three distinct OH bands at 3329, 3580, and 3615 cm^?1. OH concentrations range from 10000–65000 H/10⁶ Si. A strong positive correlation of grain size and extent of transformation with OH concentration in the β-phase indicates that grain-growth and transformation rates are enhanced in a hydrous environment. Olivine spectra are variable, but consistently show a prominent broad-band absorbance representing molecular H₂O, consistent with the infrared signature of the starting material. OH concentrations in olivine range from <300–1400 H/10⁶ Si. The highest OH concentrations measured for olivine and the β-phase may represent solubility limits, in which case the OH solubility ratio between these two phases is approximately 1∶40. Where both phases coexist and are undersaturated with OH, the partitioning ratio of OH between them is about 1∶100. The large solubility contrast between olivine and the β-phase suggests a mechanism for hydrating the transition zone via olivine carried down in subducting slabs. Plumes impinging on an OH-rich upper transition region could cause H₂ or H₂O to be released upon transformation of the β-phase to olivine, resulting in initiation of secondary upwellings. If dissolution of OH weakens the β-phase, and if OH is present in the mantle, the region between 400–550 km could be a zone of low viscosity.     

Implications of liquid-liquid distribution coefficients to mineral-liquid partitioning

The effect of silicate liquid structure upon mineral-liquid partitioning has been investigated by determining element partitioning data for coexisting immiscible granitic and ferrobasaltic magmas. The resulting elemental distribution patterns may be interpreted in terms of the relative states of polymerization of the coexisting magmas. Highly charged cations (REE, Ti, Fe, Mn, etc.) are enriched in the ferrobasaltic melt. The ferrobasaltic melt is relatively depolymerized due to its low $\text{Si}\text{O}$ ratio. This allows highly charged cations to obtain stable coordination polyhedra of oxygen within the ferrobasaltic melt. The granitic melt is a highly polymerized network structure in which Al can occupy tetrahedral sites in copolymerization with Si. The substitution of Al⁺³ for Si⁺⁴ produces a local charge imbalance in the granitic melt which is satisfied by a coupled substitution of alkalis, thus explaining the enrichment of low charge density cations, the alkalis, in the granitic melt. P₂O₅ increases the width of the solvus and, therefore, the values of the distribution coefficients of the trace elements. This effect is attributed to complexing of metal cations with PO₄^?3 groups in the ferrobasaltic melt.The values of ferrobasalt-granite liquid distribution coefficients are reflected in distribution coefficients for a mineral and melts of different compositions. The mineral-liquid distribution coefficient for a highly charged cation is greater for a mineral coexisting with a highly polymerized melt (granite) than it is for that same mineral and a depolymerized melt (ferrobasalt). The opposite is true for low charge density cations. Mineralliquid and liquid-liquid distribution coefficients determined for the REE's indicate that fractionated REE patterns are due to mineral selectivity and not the state of polymerization of the melt.     

Element partitioning between olivine and silicate melt under high pressure

Element partitioning between olivine and silicate melt has been investigated at pressures 1–14 GPa, by using a 6–8 type multi-anvil high pressure apparatus. In order to observe systematics in the partitioning of trivalent ions, Li was added to the starting materials in order to increase the concentration of trivalent ions in olivine. With increasing pressure, it was found that partition coefficients of most of the elements gradually decreased. Trivalent ions generally showed parabolic pattern on partition coefficient — ionic radius diagram. When pyrolite-like material was used as the starting material, partition coefficient of Al, D_Al, gradually increased with increase in pressure while the partition coefficients of the other elements decreased, and the D_Al deviated from the parabolic pattern of other trivalent ions. The deviation of D_Al from the D pattern of the other trivalent ions was also found when olivine was employed as main component of the starting material. This result may be ascribed to the compositional change of coexisting silicate melt with increase in pressure.     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in ⁵⁶Fe/⁵⁴Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ⁵⁶Fe_{clinopyroxene-olivine} fractionation and the δ⁵⁶Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.     

Experimental investigation of the origin of majoritic garnet inclusions in diamonds

 Multianvil experiments were carried out at 10–15 GPa and 1600–1700 °C to match the compositions of majoritic garnet inclusions from diamonds, and to determine the compositions of other phases potentially coexisting with these inclusions in the source. Most experiments produced coexisting majoritic garnet, diopsidic clinopyroxene, one or more (Mg,Fe)₂SiO₄ polymorphs, and quenched carbonatic melt. The experimental garnets had relatively high Ca and Fe contents similar to the observed Ca and Fe contents of the inclusions. The resulting Si contents confirmed that the depth of origin of the inclusion with the highest Si content did not exceed 410 km, thus none of the majoritic garnet inclusions found so far originated in the transition zone (410–660 km). The evidence from inclusions and experiments is consistent with the presence of an eclogite layer occurring globally between 200 and 410 km. Compositional variations observed among more than 100 majoritic garnet inclusions with their Si content, which is a measure of pressure and depth, are consistent with the origin of the eclogite layer by crystal fractionation in a magma ocean. The compositions of olivine coexisting with majoritic garnet in the experimental products had the average Fe/(Fe + Mg) ratios between 0.16 and 0.28. Inclusions with such high Fe contents have not been found; the Fe/(Fe + Mg) ratio of the olivine inclusions in diamonds usually varies between 0.05 and 0.09. Hence, the mantle between 200 and 410 km may not contain olivine. In the absence of olivine, the discontinuity at 410 km is most likely a chemical boundary between the 200-km-thick eclogite layer and a more mafic transition zone. Received: 15 March 2001 / Accepted: 14 September 2001     

Evidence for heterogeneous enriched shergottite mantle sources in Mars from olivine-hosted melt inclusions in Larkman Nunatak 06319

Larkman Nunatak (LAR) 06319 is an olivine-phyric shergottite whose olivine crystals contain abundant crystallized melt inclusions. In this study, three types of melt inclusion were distinguished, based on their occurrence and the composition of their olivine host: Type-I inclusions occur in phenocryst cores (Fo_77-73); Type-II inclusions occur in phenocryst mantles (Fo_71-66); Type-III inclusions occur in phenocryst rims (Fo_61-51) and within groundmass olivine. The sizes of the melt inclusions decrease significantly from Type-I (∼150-250 μm diameter) to Type-II (∼100 μm diameter) to Type-III (∼25-75 μm diameter). Present bulk compositions (PBC) of the crystallized melt inclusions were calculated for each of the three melt inclusion types based on average modal abundances and analyzed compositions of constituent phases. Primary trapped liquid compositions were then reconstructed by addition of olivine and adjustment of the Fe/Mg ratio to equilibrium with the host olivine (to account for crystallization of wall olivine and the effects of Fe/Mg re-equilibration). The present bulk composition of Type-I inclusions (PBC1) plots on a tie-line that passes through olivine and the LAR 06319 whole-rock composition. The parent magma composition can be reconstructed by addition of 29 mol% olivine to PBC1, and adjustment of Fe/Mg for equilibrium with olivine of Fo₇₇ composition. The resulting parent magma composition has a predicted crystallization sequence that is consistent with that determined from petrographic observations, and differs significantly from the whole-rock only in an accumulated olivine component (∼10 wt%). This is consistent with a calculation indicating that ∼10 wt% magnesian (Fo_77-73) olivine must be subtracted from the whole-rock to yield a melt in equilibrium with Fo₇₇. Thus, two independent estimates indicate that LAR 06319 contains ∼10 wt% cumulate olivine.The rare earth element (REE) patterns of Type-I melt inclusions are similar to that of the LAR 06319 whole-rock. The REE patterns of Type-II and Type-III melt inclusions are also broadly parallel to that of the whole-rock, but at higher absolute abundances. These results are consistent with an LAR 06319 parent magma that crystallized as a closed-system, with its incompatible-element enrichment being inherited from its mantle source region. However, fractional crystallization of the reconstructed LAR 06319 parent magma cannot reproduce the major and trace element characteristics of all enriched basaltic shergottites, indicating local-to-large scale major- and trace-element variations in the mantle source of enriched shergottites. Therefore, LAR 06319 cannot be parental to the enriched basaltic shergottites.     

四川攀西地区层状侵入体中堆晶岩成因的矿物学约束

火成岩中可以包含多种晶体群这一发现具有重要意义,使得成因矿物学重新成为揭示岩浆系统演化的基本指导思想。但是,这种重要性在许多文献中都没有得到反映,其典型实例就是镁铁质层状侵入体中堆晶岩的成因。争论在于堆晶矿物是循环晶还是母岩浆的液相线相。因此,本文致力于探讨四川攀西地区镁铁质层状侵入体中堆晶岩的形成过程,重申成因矿物学的重要意义。显微镜观察表明,堆晶单斜辉石富含Fe-Ti氧化物出溶叶片(含叶片辉石),表明其形成环境明显不同于与斜长石呈共结关系的单斜辉石(无叶片辉石);无叶片辉石和斜长石中的橄榄石包裹体呈浑圆状,表明了橄榄石与结晶环境间的热力学不平衡。橄榄石与熔体间Fe-Mg分配关系分析表明,根据母岩浆成分推测的橄榄石Fo值远低于岩体中观测橄榄石化学成分变化范围(Fo₆₁-Fo₈₁)的高限,表明至少部分橄榄石不是寄主侵入体的液相线相。橄榄石的Mg^#值(100×Mg/(Mg+Fe))与微量元素(特别是Ni)的相关关系表明存在多种橄榄石晶体群,它们形成于不同的热力学环境中。晶体沉降过程分析表明,寄主岩浆析出的晶体几乎不可能发生快速重力沉降来形成堆晶岩。所有这些证据都表明,形成堆晶岩的矿物主要来自岩浆系统深部不同的岩浆房中,是被岩浆携带输运到终端岩浆房的循环晶。     

Thermodynamic analysis of Fe and Mg partitioning between plagioclase and silicate liquid

 Thermodynamic analysis of Fe- and Mg-bearing plagioclase and silicate liquid was carried out based on reported element partitioning data between plagioclase and silicate liquid in reduced conditions, solution properties of ternary feldspar, standard state properties of plagioclase endmembers and solution properties of multicomponent silicate liquid. Derived mixing properties of Fe- and Mg-bearing plagioclase are in harmony with estimated results from synthetic experiments in the systems CaAl₂Si₂O₈-CaFeSi₃O₈ and CaAl₂Si₂O₈-CaMgSi₃O₈. Based on the determined solution properties of the plagioclase, a computer program to calculate the element partition relationships between Fe- and Mg-bearing plagioclase and multicomponent silicate liquid was developed. The FeO, MgO and MgO/(MgO + FeO) in plagioclase predicted from known liquid compositions and pressure are in agreement with measurements within 0.2 wt%, 0.1 wt% and 0.1 (mol ratio), respectively. The Fe³⁺ content in plagioclase crystallized at high oxygen fugacity can be estimated with this program. The Fe³⁺/total Fe ratio in plagioclase crystallized near the quartz-fayalite-magnetite buffer ranges from 0 to 0.5, which is consistent with previous study on natural plagioclase in submarine basalt. Derived solution properties of the Fe- and Mg-bearing plagioclase are also used to calculate equilibrium composition relationship between olivine and plagioclase. Change of X _Fo in olivine coexisting with plagioclase affects MgO and FeO contents in plagioclase greatly. The present model predicts X _Fo of coexisting olivine from the chemical composition of plagioclase to ±0.1 accuracy at given pressure and temperature. Received: 27 March 1998 / Accepted: 30 September 1999     

Partitioning of manganese between forsterite and silicate liquid

Partition coefficients for Mn between forsterite and liquid in the system MgO-CaO-Na₂O-Al₂O₃-SiO₂ (+ about 0.2% Mn) were measured by electron microprobe for a variety of melt compositions over the temperature range 1250–1450°C at one atm pressure. The forsterite-liquid partition coefficient of Mn (mole ratio, MnO in Fo/MnO in liquid, designated D_mn^fo?Liq) depends on liquid composition as well as temperature: at 1350°C, D_Mn^Fo?Liqranges from 0.60 (basic melt, SiO₂ = 47wt%) to 1.24 (acidic melt, SiO₂ = 65wt%). At lower temperatures, the partition coefficient is more strongly dependent on melt composition.The effects of melt composition and temperature on D_Mn^fo?Liq can be separately evaluated by use of the Si:O atomic ratio of the melts. A plot of D_mn^Fo?Liq measured at various temperatures vs melt Si:O for numerous liquid compositions reveals discrete, constant-temperature curves that are not well defined by plotting D_Mn^Fo?Liq against other melt composition parameters such as melt basicity or MgO content. For constant Si:O in the melt, In D_Mn^Fo?Liq vs reciprocal absolute temperature is linear; however, the slope of the plot becomes more positive for higher values of Si:O, indicating a higher energy state for Mn²⁺ ions in acidic melts than in basic melts.Comparison of Mn partitioning data for the iron-free system used in this study with data of other workers on iron-bearing compositions suggests that the effect of iron on Mn partitioning between olivine and melt is small over the range of basalt liquidus temperatures.     

The system Mg2SiO4-Ca2SiO4-CaAl2O4-NaAlSiO4-SiO2: one atmosphere liquidus equilibria of analogs of alkaline mafic lavas

One atmosphere liquidus relationships in the system Mg₂SiO₄ (Fo)–Ca₂SiO₄ (La)–NaAlSiO₄ (Ne)–CaAl₂O₄ (CA)–SiO₂ (Sil) are presented as analogs for alkaline mafic lavas. Liquidus diagrams are constructed from electron microprobe analyses of quenched liquids and coexisting mineral phases produced in melting experiments and they are depicted in terms of sub-projections within the pseudo-quaternary system Fo–La–[Ne,CA]–Sil. The Ne and CA components are combined to create a normative feldspathoid component defined as Ne#=Ne/[Ne+CA]. Liquidus relations at Ne#=0.5 from this study are compared to relations at Ne#=0.0 and 1.0 from previous studies. In general, liquidus temperatures decrease and positions of liquidus boundaries involving feldspathic phases shift toward the [Ne, CA] component as Ne# increases. The pseudoinvariant points fo+di+pl+mel+l and fo+pl+mel+sp+l exist at Ne#=0.5. These equilibria between forsterite-plagioclase-melilite-liquid are not present in the system when Ne#=1.0 because a boundary curve (fo+di+ne+l) separates the plagioclase and melilite liquidus fields. The liquidus diagrams provide useful analogs for the crystallization sequences of natural primary alkali olivine basalts, basanitoids, basanites, olivine nephelinites, olivine-melilite nephelinites and olivine melilitites.     

Melt inclusions in scoria and associated mantle xenoliths of Puy Beaunit Volcano,Chaîne des Puys,Massif Central,France

In order to characterize the composition of the parental melts of intracontinental alkali-basalts, we have undertaken a study of melt and fluid inclusions in olivine crystals in basaltic scoria and associated upper mantle nodules from Puy Beaunit, a volcano from the Chaîne des Puys volcanic province of the French Massif Central (West-European Rift system). Certain melt inclusions were experimentally homogenised by heating-stage experiments and analysed to obtain major- and trace-element compositions. In basaltic scoria, olivine-hosted melt inclusions occur as primary isolated inclusions formed during growth of the host phase. Some melt inclusions contain both glass and daughter minerals that formed during closed-system crystallisation of the inclusion and consist mainly of clinopyroxene, plagioclase and rhönite crystals. Experimentally rehomogenised and naturally quenched, glassy inclusions have alkali-basalt compositions (with SiO₂ content as low as 42 wt%, MgO>6 wt%, Na₂O+K₂O>5 wt%, Cl~1,000–3,000 ppm and S~400–2,000 ppm), which are consistent with those expected for the parental magmas of the Chaîne des Puys magmatic suites. Their trace-element signature is characterized by high concentration(s) of LILE and high LREE/HREE ratios, implying an enriched source likely to have incorporated small amounts of recycled sediments. In olivine porphyroclasts of the spinel peridotite nodules, silicate melt inclusions are secondary in nature and form trails along fracture planes. They are generally associated with secondary CO₂ fluid inclusions containing coexisting vapour and liquid phases in the same trail. This observation and the existence of multiphase inclusions consisting of silicate glass and CO₂-rich fluid suggest the former existence of a CO₂-rich silicate melt phase. Unheated glass inclusions have silicic major-element compositions, with normative nepheline and olivine components, ~58 wt% SiO₂, ~9 wt% total alkali oxides, <3 wt% FeO and MgO. They also have high chlorine levels (>3,000 ppm) but their sulphur concentrations are low (<200 ppm). Comparison with experimental isobaric trends for peridotite indicates that they represent high-pressure (~1.0 GPa) trapped aliquots of near-solidus partial melts of spinel peridotite. Following this hypothesis, their silica-rich compositions would reflect the effect of alkali oxides on the silica activity coefficient of the melt during the melting process. Indeed, the silica activity coefficient decreases with addition of alkalis around 1.0 GPa. For mantle melts coexisting with an olivine-orthopyroxene-bearing mineral assemblage buffering SiO₂ activity, this decrease is therefore compensated by an increase in the SiO₂ content of the melt. Because of their high viscosity and the low permeability of their matrix, these near-solidus peridotite melts show limited ability to segregate and migrate, which can explain the absence of a chemical relationship between the olivine-hosted melt inclusions in the nodules and in basaltic scoria.     

Mineral/melt partitioning of trace elements during hydrous peridotite partial melting

This experimental study examines the mineral/melt partitioning of incompatible trace elements among high-Ca clinopyroxene, garnet, and hydrous silicate melt at upper mantle pressure and temperature conditions. Experiments were performed at pressures of 1.2 and 1.6 GPa and temperatures of 1,185 to 1,370 °C. Experimentally produced silicate melts contain up to 6.3 wt% dissolved H ₂O, and are saturated with an upper mantle peridotite mineral assemblage of olivine+orthopyroxene+clinopyroxene+spinel or garnet. Clinopyroxene/melt and garnet/melt partition coefficients were measured for Li, B, K, Sr, Y, Zr, Nb, and select rare earth elements by secondary ion mass spectrometry. A comparison of our experimental results for trivalent cations (REEs and Y) with the results from calculations carried out using the Wood-Blundy partitioning model indicates that H ₂O dissolved in the silicate melt has a discernible effect on trace element partitioning. Experiments carried out at 1.2 GPa, 1,315 °C and 1.6 GPa, 1,370 °C produced clinopyroxene containing 15.0 and 13.9 wt% CaO, respectively, coexisting with silicate melts containing ~1–2 wt% H ₂O. Partition coefficients measured in these experiments are consistent with the Wood-Blundy model. However, partition coefficients determined in an experiment carried out at 1.2 GPa and 1,185 °C, which produced clinopyroxene containing 19.3 wt% CaO coexisting with a high-H ₂O (6.26±0.10 wt%) silicate melt, are significantly smaller than predicted by the Wood-Blundy model. Accounting for the depolymerized structure of the H ₂O-rich melt eliminates the mismatch between experimental result and model prediction. Therefore, the increased Ca ²⁺ content of clinopyroxene at low-temperature, hydrous conditions does not enhance compatibility to the extent indicated by results from anhydrous experiments, and models used to predict mineral/melt partition coefficients during hydrous peridotite partial melting in the sub-arc mantle must take into account the effects of H ₂O on the structure of silicate melts.     

Geochemical and mineralogical evidence for the occurrence of at least three distinct magma types in the ‘famous’ region

Bulk rock major and trace element variations in selected basalts from the Famous area, in conjunction with a detailed study of the chemical compositions of phenocryst minerals and associated melt inclusions are used to place constraints on the genetic relationship among the various lava types. The distribution of NiO in olivine and Cr-spinel phenocrysts distinguishes the picritic basalts, plagioclase phyric basalts and plagioclase-pyroxene basalts from the olivine basalts. For a given Mg/Mg+Fe²⁺ atomic ratio of the mineral, the NiO content of these phenocrysts in the former three basalt types is low relative to that in the phenocrysts in the olivine basalts. The Zr/Nb ratio of the lavas similarly distinguishes the olivine basalts from the plagioclase phyric and plagioclase pyroxene basalts and, in addition, distinguishes the picritic basalts from the other basalt types. These differences indicate that the different magma groups could not have been processed through the same magma chamber, and preclude any direct inter-relationship via open or closed system fractional crystallization.The Fe-Mg partitioning between olivine and host rock suggests that the picritic basalts represent olivine (±Cr-spinel) enriched magmas, derived from a less MgO rich parental magma. The partitioning of Fe and Mg between olivine, Cr-spinel and coexisting liquid is used to predict a primary magma composition parental to the picritic basalts. This magma is characterized by relatively high MgO (12.3%) and CaO (12.6%) and low FeO^* (7.96%) and TiO₂ (0.63%).Least squares calculations indicate that the plagioclase phyric basalts are related to the plagioclase-pyroxene basalts by plagioclase and minor clinopyroxene and olivine accumulation. The compositional variations within the olivine basalts can be accounted for by fractionation of plagioclase, clinopyroxene and olivine in an open system, steady state, magma chamber in the average proportions 453223. It is suggested that the most primitive olivine basalts can be derived from a pristine mantle composition by approximately 17% equilibrium partial melting. Although distinguished by its higher Zr/Nb ratio and lower NiO content of phenocryst phases, the magma parental to the picritic basalts can be derived from a similar source composition by approximately 27% equilibrium partial melting. It is suggested that the parental magma to the plagioclase-pyroxene and plagioclase phyric basalts might have been derived from greater depth resulting in the fractionation of the Zr/Nb ratio by equilibration with residual garnet.C.O.B. Contribution No. 722     

Volatiles H2O,CO2, and Cl in a subduction related basalt

The products of the 1974 eruption of Fuego, a subduction zone volcano in Guatemala, have been investigated through study of silicate melt inclusions in olivine. The melt inclusions sampled liquids in regions where olivine, plagioclase, magnetite, and augite were precipitating. Comparisons of the erupted ash, groundmass, and melt inclusion compositions suggest that the inclusions represent samples of liquids present in a thermal boundary layer of the magma body. The concentrations of H₂O and CO₂ in glass inclusions were determined by a vacuum fusion manometric technique using individual olivine crystals (Fo77 to Fo71) with glass inclusion compositions that ranged from high-alumina basalt to basaltic andesite. Water, Cl, and K₂O concentrations increased by a factor of two as the olivine crystals became more iron-rich (Fo77 to Fo71) and as the glass inclusions increased in SiO₂ from 51 to 54 wt.% SiO₂. The concentration of H₂O in the melt increased from 1.6 wt.% in the least differentiated liquid to about 3.5% in a more differentiated liquid. Carbon dioxide is about an order of magnitude less abundant than H₂O in these inclusions. The gas saturation pressures for pure H₂O in equilibrium with the melt inclusions, which were calculated from the glass inclusion compositions using the solubility model of Burnham (1979), are given approximately by P(H₂O)(Pa)=(SiO₂−48.5 wt.%) × 1.45 × 10⁷. The concentrations of water in the melt and the gas saturation pressures increased from about 1.5% to 3.5% and from 300 to 850 bars, respectively, during pre-eruption crystallization.     

AuPdFe ternary solution model and applications to understanding the fO2 of hydrous, high-pressure experiments

This study provides an experimental calibration of the equilibrium constant for AuPdFe alloys with Fe-bearing silicate melts. The ideal metal capsules for H₂O-bearing experiments are pure Au, because of its slow hydrogen diffusivity. However, above the melting point of Au, other materials must be used. The solution to this problem is to use AuPd alloy capsules. However, under most relevant fO₂ conditions, this alloy absorbs Fe from the coexisting silicate melt, thus changing the bulk composition of the experimental charge. This study combines previous work on the Au–Pd, Pd–Fe, and Au–Fe binary systems to develop a ternary thermodynamic solution model for AuPdFe. This solution model is used with experiments to calculate an equilibrium reaction coefficient for the FeO_melt → Fe_alloy + 1/2O₂ exchange reaction. Using a non-ideal ternary solution model, the fO₂ conditions of hydrous, piston cylinder experiments can be estimated by analyzing the sample capsule alloy and the coexisting liquid composition.     

The behavior of Mg, Fe, and Ni during the replacement of olivine by orthopyroxene: experiments relevant to mantle metasomatism

Replacement of olivine by orthopyroxene is a frequently observed phenomenon in mantle metasomatism. In order to study element redistribution in SiO₂ metasomatism we synthesised orthopyroxene reaction rims at the contacts between forsterite-rich olivine and quartz. The orthopyroxene rims grew from the original quartz-olivine interface into both directions implying counterdiffusion of iron/magnesium and silicon. Following local equilibrium partitioning the X_Fe is lower in the orthopyroxene than in the reactant olivine at the olivine-orthopyroxene replacement front. The resulting local iron excess is compensated by formation of orthopyroxene with a higher X_Fe at the quartz-orthopyroxene interface, which is out of equilibrium with the reactant olivine. This is facilitated through short circuit diffusion along grain boundaries within the orthopyroxene rim. Due to the low capacity of orthopyroxene to accommodate Ni, this component is forced to diffuse back into the olivine producing a Ni enriched zone ahead of the replacement front. This leads to Ni contents in the orthopyroxene rim, which are higher than what is expected in equilibrium with the unaltered olivine. Taking quartz as a proxy for a silica rich fluid or liquid metasomatising agent, we conclude that the overall element fractionation between olivine and the silica rich phase may deviate from equilibrium partitioning so that the Fe and Ni concentrations in the orthopyroxene which is in contact with quartz are higher than in equilibrium with the reactant olivine. This indicates that kinetic fractionation is important for the chemical evolution of both the mantle rocks and the metasomatising agents.     

Interaction of peridotite with Ca-rich carbonatite melt at 3.1 and 6.5 GPa: Implication for merwinite formation in upper mantle,and for the metasomatic origin of sublithospheric diamonds with Ca-rich suite of inclusions

We performed an experimental study, designed to reproduce the formation of an unusual merwinite?+?olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca?=?1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite?+?olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300–1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca#?=?molar 100?×?Ca/(Ca?+?Mg)?>?0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca?=?1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg₂SiO₄ (olivine)?+?6CaCO₃ (liquid)?=?Ca₃MgSi₂O₈ (merwinite)?+?3CaMg(CO₃)₂ (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.     

Carbonatite melt inclusions in coexisting magnetite,apatite and monticellite in Kerimasi calciocarbonatite,Tanzania: melt evolution and petrogenesis

Kerimasi calciocarbonatite consists principally of calcite together with lesser apatite, magnetite, and monticellite. Calcite hosts fluid and S-bearing Na–K–Ca-carbonate inclusions. Carbonatite melt and fluid inclusions occur in apatite and magnetite, and silicate melt inclusions in magnetite. This study presents statistically significant compositional data for quenched S- and P-bearing, Ca-alkali-rich carbonatite melt inclusions in magnetite and apatite. Magnetite-hosted silicate melts are peralkaline with normative sodium-metasilicate. On the basis of our microthermometric results on apatite-hosted melt inclusions and forsterite–monticellite phase relationships, temperatures of the early stage of magma evolution are estimated to be 900–1,000°C. At this time three immiscible liquid phases coexisted: (1) a Ca-rich, P-, S- and alkali-bearing carbonatite melt, (2) a Mg- and Fe-rich, peralkaline silicate melt, and (3) a C–O–H–S-alkali fluid. During the development of coexisting carbonatite and silicate melts, the Si/Al and Mg/Fe ratio of the silicate melt decreased with contemporaneous increase in alkalis due to olivine fractionation, whereas the alkali content of the carbonatite melt increased with concomitant decrease in CaO resulting from calcite fractionation. Overall the peralkalinity of the bulk composition of the immiscible melts increased, resulting in a decrease in the size of the miscibility gap in the pseudoquaternary system studied. Inclusion data indicate the formation of a carbonatite magma that is extremely enriched in alkalis with a composition similar to that of Oldoinyo Lengai natrocarbonatite. In contrast to the bulk compositions of calciocarbonatite rocks, the melt inclusions investigated contain significant amount of alkalis (Na₂O + K₂O) that is at least 5–10 wt%. The compositions of carbonatite melt inclusions are considered as being better representatives of parental magma composition than those of any bulk rock.