A model for C-O-H fluid in the Earth’s mantle

A model is presented for predicting the composition (H₂O, CO₂, CH₄, H₂, CO, O₂ and C₂H₆) in the C-O-H fluid system under high temperatures and pressures found in the Earth’s mantle. The model is based on a molecular dynamic equation of state, statistical mechanics calculations and non-stoichiometric global free-energy minimization. Although the model is not fitted to experimental data on C-O-H speciation, it does accurately reproduce these datasets and should extrapolate at least to the depths of ∼80-220 km. The model results suggest that (1) in the upper cratonic mantle, H₂O is the dominant fluid species in the C-O-H fluid system; (2) the abundance of CO₂ increases with decreasing depth, the trend of CH₄ is just the opposite; (3) the boundary between lithosphere and asthenosphere generally divides fluid systems into H₂O-CH₄+ minor species and H₂O-CO₂+ minor species, respectively; (4) it is entirely possible to generate methane and ethane and possibly other hydrocarbons under mantle conditions, confirming previously experimental results.     

Platinum-osmium isotope evolution of the Earth’s mantle: Constraints from chondrites and Os-rich alloys

Separation of a metal-rich core strongly depleted the silicate portion of the Earth in highly siderophile elements (HSE), including Pt, Re, and Os. To address the issues of how early differentiation, partial melting, and enrichment processes may have affected the relative abundances of the HSE in the upper mantle, ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os data for chondrites are compared with data for Os-rich alloys from upper mantle peridotites. Given that ¹⁸⁷Os and ¹⁸⁶Os are decay products of ¹⁸⁷Re and ¹⁹⁰Pt, respectively, these ratios can be used to constrain the long-term Re/Os and Pt/Os of mantle reservoirs in comparison to chondrites. Because of isotopic homogeneity, H-group ordinary and other equilibrated chondrites may be most suitable for defining the initial ¹⁸⁶Os/¹⁸⁸Os of the solar system. The ¹⁸⁶Os/¹⁸⁸Os ratios for five H-group ordinary chondrites range only from 0.1198384 to 0.1198408, with an average of 0.1198398 ± 0.0000016 (2σ). Using the measured Pt/Os and ¹⁸⁶Os/¹⁸⁸Os for each chondrite, the calculated initial ¹⁸⁶Os/¹⁸⁸Os at 4.567 Ga is 0.1198269 ± 0.0000014 (2σ). This is the current best estimate for the initial ¹⁸⁶Os/¹⁸⁸Os of the bulk solar system. The mantle evolution of ¹⁸⁶Os/¹⁸⁸Os can be defined via examination of mantle-derived materials with well-constrained ages and low Pt/Os. Two types of mantle-derived materials that can be used for this task are komatiites and Os-rich alloys. The alloys are particularly valuable in that they have little or no Re or Pt, thus, when formed, evolution of both ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os ceases. Previously published results for an Archean komatiite and new results for Os-rich alloys indicate that the terrestrial mantle evolved with Pt-Os isotopic systematics that were indistinguishable from the H-group ordinary and some enstatite chondrites. This corresponds to a Pt/Os of 2.0 ± 0.2 for the primitive upper mantle evolution curve. This similarity is consistent with previous arguments, based on the ¹⁸⁷Os/¹⁸⁸Os systematics and HSE abundances in the mantle, for a late veneer of materials with chondritic bulk compositions controlling the HSE budget of the upper mantle. It is very unlikely that high pressure metal-silicate segregation leading to core formation can account for the elemental and isotopic compositions of HSE in the upper mantle.     

Low δO in the Icelandic mantle and its origins: Evidence from Reykjanes Ridge and Icelandic lavas

Oxygen isotope ratios have been determined using laser fluorination techniques on olivine and plagioclase phenocrysts and bulk glasses from the Reykjanes Ridge and Iceland. δ¹⁸O in Reykjanes Ridge olivines shows hyperbolic correlations with Sr-Nd-Pb isotope ratios that terminate at δ¹⁸O = +4.5‰ at compositions almost identical to those of moderately enriched lavas on the Reykjanes Peninsula, Iceland. Samples with low δ¹⁸O show no indication of contamination by oceanic crust such as elevated Cl/K, and are too deep to have been influenced by meteoric water hydrothermal systems. They cannot represent Icelandic melts contaminated in the crust and transferred laterally along the ridge since fissure systems are strongly oblique to the ridge axis. It follows that Icelandic mantle advected along the ridge has low δ¹⁸O. The hyperbolic ¹⁴³Nd/¹⁴⁴Nd-δ¹⁸O correlation appears to be more strongly curved than magma mixing trajectories and suggests that melt fractions are ∼4.5× greater and source Nd contents ∼9× greater in the mantle at 63°N compared with that at 60°N. Primitive lavas from the Reykjanes Peninsula show linear correlations between olivine δ¹⁸O and ¹⁴³Nd/¹⁴⁴Nd or ²⁰⁶Pb/²⁰⁴Pb, extending to δ¹⁸O of +4.3‰ at ¹⁴³Nd/¹⁴⁴Nd close to the lowest ratios observed in Icelandic magmas. These correlations cannot be produced by melt mixing or crustal contamination because these would yield strongly hyperbolic trajectories. Lower δ¹⁸O seen in more evolved samples from the Eastern Rift Zone may reflect crustal contamination, though there is some evidence of a mantle source with lower δ¹⁸O in eastern Iceland. It is very difficult to explain the low δ¹⁸O of enriched Icelandic mantle sources on current understanding of mantle and crustal oxygen isotopes. There is no obvious reason why such low-δ¹⁸O sources should not contribute to other ocean islands. No oceanic crustal lithologies exist that could produce the low-δ¹⁸O enriched sources by recycling into the mantle, and there is no evidence for changes in δ¹⁸O of ophiolite suites with time, nor of changes during high-P metamorphism. Low δ¹⁸O appears to be associated with high ³He/⁴He, and we speculate that this signature may be characteristic of the host mantle into which ocean crust was recycled.     

The Earth’s tungsten budget during mantle melting and crust formation

During silicate melting on Earth, W is one of the most incompatible trace elements, similar to Th, Ba or U. As W is also moderately siderophile during metal segregation, ratios of W and the lithophile Th and U in silicate rocks have therefore been used to constrain the W abundance of the Earth’s mantle and the Hf-W age of core formation. This study presents high-precision W concentration data obtained by isotope dilution for samples covering important silicate reservoirs on Earth. The data reveal significant fractionations of W from other highly incompatible lithophile elements such as Th, U, and Ta. Many arc lavas exhibit a selective enrichment of W relative to Th, U, and Nb-Ta, reflecting W enrichment in the sub-arc mantle via fluid-like components derived from subducting plates. In contrast, during enrichment by melt-like subduction components, W is generally slightly depleted relative to Th and U, but is still enriched relative to Ta. Hence, all arc rocks and the continental crust exhibit uniformly low Ta/W (ca. 1), whereas W/Th and W/U may show opposite fractionation trends, depending on the role of fluid- and melt-like subduction components. Further high-precision W data for OIBs and MORBs reveal a systematic depletion of W in both rock types relative to other HFSE, resulting in high Ta/W that are complementary to the low Ta/W observed in arc rocks and the continental crust. Similar to previous interpretations based on Nb/U and Ce/Pb systematics, our Ta/W data confirm a depletion of the depleted upper mantle (DM) in fluid mobile elements relative to the primitive mantle (PRIMA). The abundance of W in the depleted upper mantle relative to other immobile and highly incompatible elements such as Nb and Ta is therefore not representative of the bulk silicate Earth. Based on mass balance calculations using Ta-W systematics in the major silicate reservoirs, the W abundance of the Earth’s primitive mantle can be constrained to 12 ppb, resulting in revised ratios of W-U and W-Th of 0.53 and 0.14, respectively. The newly constrained Hf-W ratio of the silicate Earth is 25.8, significantly higher than previously estimated (18.7) and overlaps within error the Hf-W ratio proposed for the Moon (ca. 24.9). The ¹⁸²Hf-¹⁸²W model age for the formation of the Earth’s core that is inferred from the ¹⁸²W abundance and the Hf/W of the silicate Earth is therefore younger than previously calculated, by up to 5 Myrs after solar system formation depending on the accretion models used. The similar Hf/W ratios and ¹⁸²W compositions of the Earth and the silicate Moon suggest a strong link between the Moon forming giant impact and final metal-silicate equilibration on the Earth.     

High-precision Nd/Nd measurements in terrestrial rocks: Constraints on the early differentiation of the Earth’s mantle

We present new ultra-high precision ¹⁴²Nd/¹⁴⁴Nd measurements of early Archaean rocks using the new generation thermal ionization mass spectrometer Triton. Repeated measurements of the Ames Nd standard demonstrate that the ¹⁴²Nd/¹⁴⁴Nd ratio can be determined with external precision of 2 ppm (2σ), allowing confident resolution of anomalies as small as 5 ppm. A major analytical improvement lies in the elimination of the double normalization procedure required to correct our former measurements from a secondary mass fractionation effect. Our new results indicate that metasediments, metabasalts, and orthogneisses from the 3.6 to 3.8 Ga West Greenland craton display positive ¹⁴²Nd anomalies ranging from 8 to 15 ppm. Using a simple two-stage model with an initial ε¹⁴³Nd value of 1.9 ± 0.6 ε-units, coupled ¹⁴⁷Sm-¹⁴³Nd and ¹⁴⁶Sm-¹⁴²Nd chronometry constrains mantle differentiation to 50-200 Ma after formation of the solar system. This chronological constraint is consistent with differentiation of the Earth’s mantle during the late stage of crystallization of a magma ocean. We have developed a two-box model describing ¹⁴²Nd and ¹⁴³Nd isotopic evolution of depleted mantle during the subsequent evolution of the crust-mantle system. Our results indicate that early terrestrial protocrust had a lifetime of ca. 0.7-1 Ga in order to produce the observed Nd isotope signature of Archaean rocks. In the context of this two box mantle-crust system, we model the evolution of isotopic and chemical heterogeneity of depleted mantle as a function of the mantle stirring time. Using the dispersion of ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios observed in early Archaean rocks, we constrain the stirring time of early Earth’s mantle to 100-250 Ma, a factor of 5 shorter than the stirring time inferred from modern oceanic basalts.     

Deep mantle storage of the Earth’s missing niobium in late-stage residual melts from a magma ocean

The origin of the observed niobium deficit in the bulk silicate Earth (BSE) compared to chondritic meteorites constitutes a long-standing problem in geochemistry. The deficit requires a large-scale process fractionating niobium from tantalum, and a super-chondritic Nb/Ta reservoir hidden in the deep silicate Earth and/or in the metallic core. The only voluminous super-chondritic Nb/Ta silicate reservoir analysed to date is found in lunar basalts that assimilated highly evolved Fe-rich rocks associated with anorthosites in the lunar crust. These Fe-rich rocks, enriched in incompatible elements, are thought to represent the last fractions of melt remaining at the end of lunar magma ocean crystallization. Here we report high-precision Nb-Ta data for a Fe-rich, late-stage rock suite associated with a terrestrial anorthosite from the Proterozoic Bolangir complex in India. The geochemical characteristics of this rock suite resemble those expected for late-stage residual melts from a terrestrial magma ocean. Samples show extreme, super-chondritic Nb/Ta up to 31.1 and highly elevated Nb concentrations up to 338 ppm. We argue that formation of an early enriched crustal reservoir (EECR) with these characteristics (high Fe, high Nb, superchondritic Nb/Ta) is likely in the course of Hadean late-stage terrestrial magma ocean solidification. Subduction and subsequent permanent deep mantle storage in the D′′ layer of a minor amount (∼0.5% of the BSE mass) of this EECR can readily explain the terrestrial Nb deficit, without the need to invoke core Nb storage. Our model is consistent with short-lived ¹⁴²Nd and long-lived ¹⁷⁶Hf-¹⁴³Nd isotope models for early differentiation of the Earth’s crust. In addition, the inferred Lu/Hf of this EECR implies that this reservoir can also balance the offset of terrestrial Hf isotope ratios compared to the chondritic reservoir. As such, late-stage magma ocean residual melts may constitute the enigmatic parental reservoir of Hadean zircons with low time-integrated Hf isotope compositions.     

Zn/Fe systematics in mafic and ultramafic systems: Implications for detecting major element heterogeneities in the Earth’s mantle

Oceanic basalts, such as mid-ocean ridge basalts (MORB) and ocean island basalts (OIB), are characterized by large isotopic and trace element variability that is hard to reconcile with partial melting of a peridotitic mantle alone. Their variability has been attributed to the presence of heterogeneities within the mantle, such as recycled crust, metasomatized material or outer core contribution. There have been few attempts to constrain the major element composition of those heterogeneities, most studies focusing on incompatible trace elements and radiogenic isotopes. Here, we report Zn, Mn and Fe systematics in mafic and ultramafic systems (whole-rocks and minerals) and we explore their use for detecting lithological heterogeneities that deviate from peridotitic mantle dominated by olivine and orthopyroxene. We suggest that Zn/Fe ratio is a particularly promising proxy. Zn/Fe fractionates equally between olivine, orthopyroxene and melt (e.g. the inter-mineral exchange coefficients  ∼  is ∼0.9-1), and the distribution of Zn/Fe between minerals appears to be temperature-independent within error. In contrast, clinopyroxene and garnet are characterized by low Zn/Fe ratios compared to co-existing melt, olivine and orthopyroxene, that is, and are both <<1. These partitioning behaviors imply that Zn/Fe ratios are minimally fractionated during partial melting of peridotite and differentiation of primitive basalts, if differentiation is dominated by olivine control. Thus, the Zn/Fe ratios of primitive basalts preserve the Zn/Fe ratio of the primary parental magma, providing insight into the signature of the mantle source region. We also infer that Zn/Fe ratios in melts are unlikely to be fractionated by modal variations in peridotitic material but are highly fractionated if garnet and/or clinopyroxene are the main phases in the source during melting. Similar Zn/Fe ratios between MORB and average upper mantle confirm the lack of fractionation during peridotite melting. However, high Zn/Fe ratios of some OIB cannot be explained by peridotite melting alone, but instead require the presence of high Zn/Fe lithologies or lithologies that have bulk exchange coefficients  < 1. All garnet-bearing or clinopyroxene-bearing lithologies, such as eclogites and garnet pyroxenites, fit the latter requirement.     

Highly siderophile element composition of the Earth’s primitive upper mantle: Constraints from new data on peridotite massifs and xenoliths

Osmium, Ru, Ir, Pt, Pd and Re abundances and ¹⁸⁷Os/¹⁸⁸Os data on peridotites were determined using improved analytical techniques in order to precisely constrain the highly siderophile element (HSE) composition of fertile lherzolites and to provide an updated estimate of HSE composition of the primitive upper mantle (PUM). The new data are used to better constrain the origin of the HSE excess in Earth’s mantle. Samples include lherzolite and harzburgite xenoliths from Archean and post-Archean continental lithosphere, peridotites from ultramafic massifs, ophiolites and other samples of oceanic mantle such as abyssal peridotites. Osmium, Ru and Ir abundances in the peridotite data set do not correlate with moderately incompatible melt extraction indicators such as Al₂O₃. Os/Ir is chondritic in most samples, while Ru/Ir, with few exceptions, is ca. 30% higher than in chondrites. Both ratios are constant over a wide range of Al₂O₃ contents, but show stronger scatter in depleted harzburgites. Platinum, Pd and Re abundances, their ratios with Ir, Os and Ru, and the ¹⁸⁷Os/¹⁸⁸Os ratio (a proxy for Re/Os) show positive correlations with Al₂O₃, indicating incompatible behavior of Pt, Pd and Re during mantle melting. The empirical sequence of peridotite-melt partition coefficients of Re, Pd and Pt as derived from peridotites () is consistent with previous data on natural samples. Some harzburgites and depleted lherzolites have been affected by secondary igneous processes such as silicate melt percolation, as indicated by U-shaped patterns of incompatible HSE, high ¹⁸⁷Os/¹⁸⁸Os, and scatter off the correlations defined by incompatible HSE and Al₂O₃. The bulk rock HSE content, chondritic Os/Ir, and chondritic to subchondritic Pt/Ir, Re/Os, Pt/Re and Re/Pd of many lherzolites of the present study are consistent with depletion by melting, and possibly solid state mixing processes in the convecting mantle, involving recycled oceanic lithosphere. Based on fertile lherzolite compositions, we infer that PUM is characterized by a mean Ir abundance of 3.5 ± 0.4 ng/g (or 0.0080 ± 0.0009*CI chondrites), chondritic ratios involving Os, Ir, Pt and Re (Os/Ir_PUM of 1.12 ± 0.09, Pt/Ir_PUM = 2.21 ± 0.21, Re/Os_PUM = 0.090 ± 0.002) and suprachondritic ratios involving Ru and Pd (Ru/Ir_PUM = 2.03 ± 0.12, Pd/Ir_PUM = 2.06 ± 0.31, uncertainties 1σ). The combination of chondritic and modestly suprachondritic HSE ratios of PUM cannot be explained by any single planetary fractionation process. Comparison with HSE patterns of chondrites shows that no known chondrite group perfectly matches the PUM composition. Similar HSE patterns, however, were found in Apollo 17 impact melt rocks from the Serenitatis impact basin [Norman M.D., Bennett V.C., Ryder G., 2002. Targeting the impactors: siderophile element signatures of lunar impact melts from Serenitatis. Earth Planet. Sci. Lett, 217-228.], which represent mixtures of chondritic material, and a component that may be either of meteoritic or indigenous origin. The similarities between the HSE composition of PUM and the bulk composition of lunar breccias establish a connection between the late accretion history of the lunar surface and the HSE composition of the Earth’s mantle. Although late accretion following core formation is still the most viable explanation for the HSE abundances in the Earth’s mantle, the “late veneer” hypothesis may require some modification in light of the unique PUM composition.     

Effects of non-stoichiometry on the spinel structure at high pressure: Implications for Earth’s mantle mineralogy

A non-stoichiometric sample of spinel with composition ^T(Mg_0.4Al_0.6)^M(Al_1.8□_0.2)O₄ was investigated by single-crystal X-ray diffraction in situ up to about 8.7 GPa using a diamond anvil cell. The P(V) data were fitted using a third-order Birch-Murnaghan equation of state and the unit-cell volume V₀, the bulk modulus K_T0 and its first pressure derivative K′ were refined simultaneously providing the following coefficients: V₀ = 510.34(6) Å³, K_T0 = 171(2) GPa, K′ = 7.3(6). This K_T0 value represents the lowest ever found for spinel crystal structures. Comparing our data with a stoichiometric and natural MgAl₂O₄ (pure composition) we observe a decrease in K_T0 by about 11.5% and a strong increase in K′ by about 33%. These results demonstrate how an excess of Al accompanied by the formation of significant cation vacancies at octahedral site strongly affects the thermodynamic properties of spinel structure. If we consider that the estimated mantle composition is characterized by 3-5% of Al₂O₃ this could imply an Mg/Al substitution with possible formation of cation vacancies. The results of our study indicate that geodynamic models should take into account the potential effect of Mg/Al substitution on the incompressibility of the main mantle-forming minerals (olivine, wadsleyite, ringwoodite, Mg-perovskite).     

Composition of aqueous fluid coexisting with mantle minerals at high pressure and its bearing on the differentiation of the Earth’s mantle

In order to understand the role of aqueous fluid on the differentiation of the mantle, the compositions of aqueous fluids coexisting with mantle minerals were investigated in the system MgO-SiO₂-H₂O at pressures of 3 to 10 GPa and temperatures of 1000 to 1500°C with an MA8-type multianvil apparatus. Phase boundaries between the stability fields of forsterite + aqueous fluid, forsterite + enstatite + aqueous fluid, and enstatite + aqueous fluid were determined by varying the bulk composition at constant temperature and pressure. The composition of aqueous fluid coexisting with forsterite and enstatite can be defined by the intersection of these two phase boundaries. The solubility of silicate components in aqueous fluid coexisting with forsterite and enstatite increases with increasing pressure up to 8 GPa, from about 30 wt% at 3 GPa to about 70 wt% at 8 GPa. It becomes almost constant above 8 GPa. The Mg/Si weight ratio of these aqueous fluids is much higher than at low pressure (0.2 at 1.5 GPa) and almost constant (1.2) at pressures between 3 and 8 GPa. At 10 GPa, it becomes about 1.4. Aqueous fluid migrating upward through the mantle can therefore dissolve large amounts of silicates, leaving modified Mg/Si ratios of residual materials. It is suggested that the chemical stratification of Mg/Si in the Earth may have been formed as a result of aqueous fluid migration.     

The geochemistry of the volatile trace elements As, Cd, Ga, In and Sn in the Earth’s mantle: New evidence from in situ analyses of mantle xenoliths

The abundances of 30 trace elements, including the volatile chalcophile/siderophile elements As, Cd, Ga, In and Sn were determined by laser ablation ICP-MS in minerals of 19 anhydrous and 5 hydrous spinel peridotite xenoliths from three continents. The majority of samples were fertile lherzolites with more than 5% clinopyroxene; several samples have major element compositions close to estimates of the primitive mantle. All samples have been previously analysed for bulk-rock major, minor and lithophile trace elements. They cover a wide range of equilibration temperatures from about 850 to 1250 °C and a pressure range from 0.8 to 3.0 GPa. A comparison of results from bulk-rock analyses with concentrations obtained from combining silicate and oxide mineral data with modal mineralogy, gave excellent agreement, with the exception of As. Arsenic is the only element analysed that has high concentrations in sulphides. For all other elements sulphides can be neglected as host phases in these mantle rocks. The major host phase for Cd, In and Sn is clinopyroxene and if present, amphibole. Cadmium and In appear to behave moderately incompatibly during mantle melting similar to Yb.The data yield new and more reliable mantle abundances for Cd (35 ± 7 ppb), In (18 ± 3 ppb) and Sn (91 ± 28 ppb). The In value is similar to the Mg and CI-normalized Zn abundance of the mantle, although In is cosmochemically more volatile than Zn. The high In content suggests a high content of volatile elements in general in proto-Earth material. The lower relative abundances of volatile chalcophile elements such as Cd, S, Se and Te might be explained by sulphide segregation during core formation. The very low relative abundances of volatile and highly incompatible lithophile elements such as Br, Cl and I, and also C, N and rare gases, imply loss during Earth accretion, arguably by collisional erosion from differentiated planetesimals and protoplanets.     

No mushy zones in the Earth’s core

Mushy zones, assemblages of crystals and their pore-space liquids, have been invoked for both the upper and lower boundaries of the liquid outer core. The timescale of very slow accumulation compared with solidification at either of these interfaces militates against such zones, where instead hard ground should be expected to form by solidification at the interface. Such adcumulus growth involves isothermal, isocompositional solidification by successful exchange of evolving solute with fresh melt from an infinite reservoir. At both boundaries of the outer core, the removal of rejected material is significantly aided by compositional convection. The accumulation rates at the outer core boundaries are orders of magnitude slower than required for adcumulus growth, as calibrated both by field and experimental evidence in silicate melts. A conceptual phase diagram for the core-mantle boundary helps to visualize the relevant equilibria. Capture of core metal into the mantle has been suggested to occur via a mushy zone, to explain a high electrical conductivity there, as plausibly required by the secular behavior of the Earth’s nutation. One conjecture is that the rejected light elements from the freezing of the inner core might be able to congregate as a porous flotation sediment at the top of the core. The idea of porosity in such a mushy zone must be rejected from experience with solidification of cumulates from magmas.A high electrical conductivity might instead be caused by solution of core metal by mantle, followed by exsolution. The hottest part of the mantle lies in contact with the molten outer core, where the maximum solubility of Fe must occur in the major mantle phases. On leaving the core-mantle boundary, the mantle must cool and may exsolve metal on the metal-silicate solvus. If the iron-rich metal resides chiefly in the rheologically weaker metal oxide phase, which coats the deforming perovskite grains, it may furnish a short circuit for mantle conductivity in the basal mantle. At still cooler and higher levels, the mantle encounters more normal mantle redox conditions, and any exsolved Fe metal should oxidize to FeO in the metal oxide and perovskite phases, ceasing to be a conductor.     

Carbon solubility in core melts in a shallow magma ocean environment and distribution of carbon between the Earth’s core and the mantle

The solubility of carbon in Fe and Fe-5.2 wt.% Ni melts, saturated with graphite, determined by electron microprobe analysis of quenched metal melts was 5.8 ± 0.1 wt.% at 2000 °C, 6.7 ± 0.2 wt.% at 2200 °C, and 7.4 ± 0.2 wt.% at 2410 °C at 2 GPa, conditions relevant for core/mantle differentiation in a shallow magma ocean. These solubilities are slightly lower than low-pressure literature values and significantly beneath calculated values for even higher pressures [e.g., Wood B. J. (1993) Carbon in the core. Earth Planet. Sci. Lett.117, 593-607]. The trend of C solubility versus temperature for Fe-5.2 wt.% Ni melt, within analytical uncertainties, is similar to or slightly lower (∼0.2-0.4 wt.%) than that of pure Fe. Carbon content of core melts and residual mantle silicates derived from equilibrium batch or fractional segregation of core liquids and their comparison with our solubility data and carbon content estimate of the present day mantle, respectively, constrain the partition coefficient of carbon between silicate and metallic melts, in a magma ocean. For the entire range of possible bulk Earth carbon content from chondritic to subchondritic values, of 10⁻⁴ to 1 is derived. But for ∼1000 ppm bulk Earth carbon, is between 10⁻² and 1. Using the complete range of possible for a magma ocean at ∼2200 °C, we predict maximum carbon content of the Earth’s core to be ∼6-7 wt.% and a preferred value of 0.25 ± 0.15 wt.% for a bulk Earth carbon concentration of ∼1000 ppm.     

LA-ICP-MS study of apatite- and K feldspar-hosted primary carbonatite melt inclusions in clinopyroxenite xenoliths from lamprophyres, Hungary: Implications for significance of carbonatite melts in the Earth’s mantle

We report the results of LA-ICP-MS analyses of rock forming minerals in clinopyroxene-apatite-K feldspar-phlogopite (CAKP) metasomatic xenoliths and primary carbonatite melt inclusions (CMI) hosted in apatite (Ap) and K feldspar (Kfs). The xenoliths are from the Cretaceous lamprophyre dikes of the Transdanubian Central Range, Hungary. The CMI in Ap have phosphorus dolomitic composition as opposed to CMI in Kfs, which display dolomitic alkali-aluminosiliceous character. The melts found in CMI in Ap and in Kfs likely formed by liquid-liquid separation from an originally carbonate- and phosphorous-rich melt. Primitive mantle (PM) normalized trace element distributions of both Ap- and Kfs-hosted CMI (n = 60 and 20, respectively) reveal a strong negative Ti-anomaly, and an extreme enrichment in incompatible elements (U, Th, LILE and LREE) relative to HREE, Sc, V, Ni and Cr. Rarely, apatites contain unique CMI, which show major- and trace-element signature transitional to K feldspar-hosted CMI. This is due to heterogeneous entrapment of an immiscible phosphorous-bearing carbonatite melt and a carbonate-bearing alkali aluminosiliceous melt, which is a further evidence for their co-existence. CMI reveal that U, Th, Pb, Nb, Ta, P, Sr, Y and REE partitioned into the phosphorous-bearing carbonatite melt, whereas Cs, Rb, Na, K, B, Al, Zr and Hf preferred the silicate-bearing liquid.PM normalized REE pattern (high LREE/HREE), elevated Zr and Hf contents and negative Ti anomaly of clinopyroxene (Cpx) indicate that its formation is genetically linked to carbonatite metasomatism attested by CMI. Trace element partitioning between the studied Cpx and CMI is in accordance with experimentally determined trace element distributions between Cpx and carbonatite melt. Cpx, which occur in samples with high modal proportion of apatite represent mantle section, which interacted with a higher amount of “initial” carbonatite melt than Cpx from apatite-poor xenoliths. This is confirmed by higher Cr, Ni, V, Sc, Ti and lower Zr, as well as Hf concentration in Cpx from xenoliths with low modal abundance of Ap. CMI reveal that Ti, V, Ni and Cr were in lower concentration in the “initial” carbonatite melt than in PM. Contrarily, Zr and Hf were more abundant in this melt than in PM. Consequently, a continuously migrating “initial” carbonatite melt, increased Zr and Hf concentration, and decreased Ti, Sc, V, Ni and especially Cr in the clinopyroxenes. Our findings suggest that the studied CAKP rocks were formed by carbonatite melt metasomatism, which occurred in an open system in the upper mantle.     

Apparent decoupling of the He and Ne isotope systematics of the Icelandic mantle: The role of He depletion, melt mixing, degassing fractionation and air interaction

We present new He-Ne data for geothermal fluids and He-Ne-Ar data for basalts from throughout the Icelandic neovolcanic zones and older parts of the Icelandic crust. Geothermal fluids, subglacial glasses, and mafic phenocrysts are characterized by a wide range in helium isotope ratios (³He/⁴He) encompassing typical MORB-like ratios through values as high as 36.8 R_A (where R_A = air ³He/⁴He). Although neon in geothermal fluids is dominated by an atmospheric component, samples from the northwest peninsula show a small excess of nucleogenic ²¹Ne, likely produced in-situ and released to circulating fluids. In contrast, geothermal fluids from the neovolcanic zones show evidence of a contribution of mantle-derived neon, as indicated by ²⁰Ne enrichments up to 3% compared to air. The neon isotope composition of subglacial glasses reveals that mantle neon is derived from both depleted MORB-mantle and a primordial, ‘solar’ mantle component. However, binary mixing between these two endmembers can account for the He-Ne isotope characteristics of the basalts only if the ³He/²²Ne ratio of the primordial mantle endmember is lower than in the MORB component. Indeed, the helium to neon elemental ratios (⁴He/²¹Ne∗ and ³He/²²Ne_s where ²¹Ne∗ = nucleogenic ²¹Ne and ²²Ne_s = ‘solar’-derived ²²Ne) of the majority of Icelandic subglacial glasses are lower than theoretical values for Earth’s mantle, as observed previously for other OIB samples. Helium may be depleted relative to neon in high-³He/⁴He ratio parental melts due to either more compatible behavior during low-degree partial melting or more extensive diffusive loss relative to the heavier noble gases. However, Icelandic glasses show higher ⁴He/⁴⁰Ar∗ (⁴⁰Ar∗ = radiogenic Ar) values for a given ⁴He/²¹Ne∗ value compared to the majority of other OIB samples: this observation is consistent with extensive open-system equilibrium degassing, likely promoted by lower confining pressures during subglacial eruptions of Icelandic lavas. Taken together, the He-Ne-Ar systematics of Icelandic subglacial glasses are imprinted with the overlapping effects of helium depletion in the high-³He/⁴He ratio parental melt, binary mixing of two distinct mantle components, degassing fractionation and interaction with atmospheric noble gases. However, it is still possible to discern differences in the noble gas characteristics of the Icelandic mantle source beneath the neovolcanic zones, with MORB-like He-Ne isotope features prevalent in the Northern Rift Zone and a sharp transition to more primitive ‘solar-like’ characteristics in central and southern Iceland.     

Metasomatism and sulfide mobility in lithospheric mantle beneath eastern Australia: Implications for mantle Re–Os chronology

Spinel lherzolite xenoliths from Tertiary basaltic host magmas at Allyn River, eastern Australia reveal two distinct petrographic and geochemical types. One group is distinguished by xenoliths with undeformed, equilibrated microstructures and interstitial melt patches; The second group shows deformation and contains abundant fluid inclusions but no melt patches. Trace-element signatures of clinopyroxene in these xenoliths provide evidence for metasomatism by a silicate agent with hydrous component and by a carbonate-rich agent respectively.

Melt patches in the undeformed xenoliths contain secondary minerals including clinopyroxene, olivine, feldspar, Mg- and Ca-rich carbonate, apatite, ilmenite and spinel. They are interpreted to represent volatile-rich melt captured shortly prior to entrainment in the host basalt. Sulfide globules, now recrystallised to discrete sulfide phases but inferred to be molten at lithospheric mantle T and P, are closely associated with the melt patches. The close association between sulfide and highly mobile, volatile-bearing fluid has important implications for the mobility of Re and Os, the use of their isotopes in dating mantle events, and the possible effect of volatile-bearing metasomatic agents on their composition.     

Os isotopes in mantle xenoliths from the Eifel volcanic field and the Vogelsberg (Germany): age constraints on the lithospheric mantle

The effects of mantle metasomatism on the sulfide phase in mantle xenoliths in general, and on the Os isotopic system in particular, have received increased attention in recent years. Here, we report on Os isotopic systematics of metasomatized mantle xenoliths from the late Quaternary Eifel (Dreiser Weiher and Meerfelder Maar) and neighboring Vogelsberg volcanic fields, which provide insight into the effects of melt extraction and metasomatism on Os isotopes and place constraints on the evolution of the lithospheric mantle component beneath central Europe. Sixteen harzburgite, lherzolite, and pyroxenite xenoliths from the Eifel and two lherzolite xenoliths from the Vogelsberg were analyzed for Os isotopes. Samples from the anhydrous peridotite suite (Ib) are highly variable in their Os isotopes, ranging from subchondritic values (¹⁸⁷Os/¹⁸⁸Os=0.1236) to suprachondritic values (¹⁸⁷Os/¹⁸⁸Os=0.1420), indicating that some of these samples have been overprinted by the addition of radiogenic Os and have lost the primary mantle Os that was presumably present. The suprachondritic values suggest a source for this Os in a reservoir with a time-integrated Re/Os ratio greater than that of the bulk Earth. Eifel samples with Os contents >1.5 ng/g from the hydrous suite (Ia) have relatively unradiogenic Os isotope compositions (¹⁸⁷Os/¹⁸⁸Os=0.1208-0.1237) and Al₂O₃-Os isotopic systematics consistent with ancient melt depletion and isolation from the convecting asthenospheric mantle for time periods similar to the age of the overlying crust (~1.5 Ga) as well with results from peridotite massifs in the European region. The LREE-metasomatism and the enrichment of Os (up to 6.47 ng/g) and As (sulfide metasomatism?) in the hydrous suite is strongly inversely correlated with the Os isotope ratios, demonstrating that mantle processes such as metasomatism can significantly modify the Os isotope chemistry of mantle xenoliths.     

Tungsten in Hawaiian picrites: A compositional model for the sources of Hawaiian lavas

Concentrations of tungsten (W) and uranium (U), which represent two of the most highly incompatible elements during mantle melting, have been measured in a suite of Hawaiian picrites and primitive tholeiites from nine main-stage shield volcanoes. Tungsten abundances in the parental melts are estimated from correlations between sample W abundances and MgO contents, and/or by olivine correction calculations. From these parental melt determinations, along with independent estimates for the degree of partial melting at each volcanic center, we extrapolate the W content of the mantle sources for each shield volcano. The mantle sources of Hualalai, Mauna Loa, Kohala, Kilauea, Mauna Kea, Koolau and Loihi contain 9 ± 2 (2σ), 11 ± 5, 10 ± 4, 12 ± 4, 10 ± 5, 8 ± 7 and 11 ± 5 ng/g, respectively. When combined, the mean Hawaiian source has an average of 10 ± 3 ng/g W, which is three-times as enriched as the Depleted MORB Mantle (DMM; 3.0 ± 2.3 ng/g).The relatively high abundances of W in the mantle sources that contribute to Hawaiian lavas may be explained as a consequence of the recycling of W-rich oceanic crust and sediment into a depleted mantle source, such as the depleted MORB mantle (DMM). However, this scenario requires varying proportions of recycled materials with different mean ages to account for the diversity of radiogenic isotope compositions observed between Kea- and Loa-trend volcanoes. Alternatively, the modeled W enrichments may also reflect a primary source component that is less depleted in incompatible trace elements than the DMM. Such a source would not necessarily require the addition of recycled materials, although the presence of some recycled crust is permitted within our model parameters and likely accounts for some of the isotopic variations between volcanic centers.The physical admixture of ?0.5 wt.% outer core material with the Hawaiian source region would not be resolvable via W source abundances or W/U ratios; however, W isotopes may provide a more sensitive to this mixing process. Recent W isotopic studies show no indication of core-mantle interaction, indicating that either such a process does not occur, or that mechanisms other than physical mixing may operate at the core-mantle boundary.     

Depleted and enriched matter in the upper mantle of Spitsbergen: Evidence from the study of mantle xenoliths

Doklady Earth Sciences -