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Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

King, C.↗

Comparative Magma Oceanography

The question of whether the Earth ever passed through a magma ocean stage is of considerable interest. Geochemical evidence strongly suggests that the Moon had a magma ocean and the evidence is mounting that the same was true for Mars. Analyses of martian (SNC) meteorites have yielded insights into the differentiation history of Mars, and consequently, it is interesting to compare that planet to the Earth. Three primary features of Mars contrast strongly to those of the Earth: (i) the extremely ancient ages of the martian core, mantle, and crust (about 4.55 b.y.); (ii) the highly depleted nature of the martian mantle; and (iii) the extreme ranges of Nd isotopic compositions that arise within the crust and depleted mantle. The easiest way to explain the ages and diverse isotopic compositions of martian basalts is to postulate that Mars had an early magma ocean. Cumulates of this magma ocean were later remelted to form the SNC meteorite suite and some of these melts assimilated crustal materials enriched in incompatible elements. The REE pattern of the crust assimilated by these SNC magmas was LREE enriched. If this pattern is typical of the crust as a whole, the martian crust is probably similar in composition to melts generated by small degrees of partial melting (about 5%) of a primitive source. Higher degrees of partial melting would cause the crustal LREE pattern to be essentially flat. In the context of a magma ocean model, where large degrees of partial melting presumably prevailed, the crust would have to be dominated by late-stage, LREE-enriched residual liquids. Regardless of the exact physical setting, Nd and W isotopic evidence indicates that martian geochemical reservoirs must have formed early and that they have not been efficiently remixed since. The important point is that in both the Moon and Mars we see evidence of a magma ocean phase and that we recognize it as such. Several lines of theoretical inference point to an early Earth that was also hot and, perhaps, mostly molten. The Giant Impact hypothesis for the origin of the Moon offers a tremendous input of thermal energy and the same could be true for core formation. And current solar system models favor the formation of a limited number of large (about 1000 km) planetesimals that, upon accreting to Earth, would cause great heating, being lesser versions of the Giant Impact. Several lines of geochemical evidence do not favor this hot early Earth scenario. (i) Terrestrial man-tle xenoliths are sometimes nearly chondritic in their major element compositions, suggesting that these rocks have never been much molten. Large degrees of partial melting probably promote differentiation rather than homogenization. (ii) Unlike the case of Mars, the continental crust probably did not form as a highly fractionated residual liquid from a magma ocean (about 99% crystallization), but, rather, formed in multiple steps. [The simplest model for the formation of continental crust is complicated: (a) about 10% melting of a primitive mantle, making basalt; (b) hydrothermal alteration of that basalt, converting it to greenstone; and (c) 10% partial melting of that greenstone, producing tonalite.] This model is reinforced by the recent observation from old (about 4.1 b.y.) zircons that the early crust formed from an undepleted mantle having a chondritic Lu/Hf ratio. (iii) If the mantle were once differentiated by a magma ocean, the mantle xenolith suite requires that it subsequently be homogenized. The Os isotopic compositions of fertile spinel lherzolites place constraints on the timing of that homogenization. The Os isotopic composition of spinel lherzolites approaches that of chondrites and correlates with elements such as Lu and Al. As Lu and Al concentrations approach those of the primitive mantle, Os isotopic compositions approach chondritic. The Re and Os in these xenoliths were probably added as a late veneer. Thus, the mantle that received the late veneer must have been nearly chondritic in terms of its major elements (excluding Fe). If the mantle that the veneer was mixed into was not al-ready homogenized, then Os isotopes should not correlate with incompatible elements such as Al. Consequently, either early differentiation of the mantle did not occur or the homogenization of this differentiation must have occurred before the late veneer was added. The timing of the late veneer is itself uncertain but presumably postdated core formation at about 4.45 b.y. and did not postdate the 3.8-3.9 b.y. late bombardment of the Moon. This timing based on siderophile elements is consistent with the Hf isotopic evidence cited above. If the Earth, Moon and Mars had magma oceans, the Earth subsequently rehomogenized whereas the Moon and Mars did not. The simplest solution to this observation is that homogenization of igneous differentiates was never necessary on Earth, either because the hypothetical magma ocean never occurred or because this event did not produce mantle differentiation.

Jones, J. H.↗

Magma oceanography. I - Thermal evolution

Fractional crystallization and flotation of cumulate plagioclase in a cooling 'magma ocean' provides the simplest explanation for early emplacement of a thick feldspar-rich lunar crust. The complementary mafic cumulates resulting from the differentiation of such a magma ocean have been identified as the ultimate source of mare basalt liquids on the basis or rare-earth abundance patterns and experimental petrology studies. A study is conducted concerning the thermal evolution of the early differentiation processes. A range of models of increasing sophistication are considered. The models developed contain the essence of the energetics and the time scale for magma ocean differentiation. Attention is given to constraints on a magma ocean, modeling procedures, single-component magma oceans, fractionating magma oceans, and evolving magma oceans.

Solomon, S. C.↗

The origin of KREEP

KREEP is a lunar material having very high concentrations of incompatible elements; its name is an acronym for the incompatibles K, rare-earth elements (REE), and P. Although a few pristine (endogenously igneous) KREEPy samples were returned from the Apollo 15 and 17 sites, most KREEPy samples are polymict breccias. Most models of KREEP petrogenesis have been based on partial melting of a variety of sources. Such models fail to explain the veritable absence of variations in incompatible element patterns over the sampled portion of the moon. We have defined a KREEP component based on the average composition of Apollo 14 breccias having extremely high concentrations of incompatible elements. Normalization of accurate incompatible data for KREEPy samples from the Apollo 12, 14, 15, 16, and 17 sites to this component virtually always shows no resolvable fractionation (e.g., <10% variation in the La/Lu ratio), whereas partial melting models typically produce larger fractionations (±20–25% in La/Lu) from a factor of 2 difference in degree of partial melting. Required is a single major source that could provide KREEP to widely separated locations on the nearside of the moon. The anorthositic crust of the moon is commonly attributed to the flotation of plagioclase on a deep, moon-wide magma ocean. Fractional crystallization of this magma ocean would have produced large enrichments of incompatibles in a residual liquid. No other plausible major source of incompatibles has been proposed. We borrow the German prefix ur—meaning primeval and designate this residual liquid ‘urKREEP.’ We propose that all KREEPy rocks originated by dilution of urKREEP with crustal or mantle materials during assimilation, or zone-refining (pristine samples), or impact-induced brecciation (breccias and melt rocks). The formation of urKREEP cannot be dated precisely. Correction of breccia Rb-Sr model ages for Rb loss or gain during the early intense bombardments yields ages that cluster in the range 4.4–4.5 Gy. This implies that crystallization of the magma ocean was essentially complete at this time and is in general agreement with U-Pb evidence indicating crustal formation at 4.4 Gy. Assuming that the moon had the composition of an H-group chondrite depleted in Fe-Ni and FeS and that half the incompatibles fractionated into materials other than urKREEP, the thickness of a moon-wide urKREEP layer was <2 km. Thorium concentrations determined by gamma ray spectroscopy indicate that about 4% of the incompatibles in an H chondritic moon are now in the outermost kilometer.

Paul H. Warren↗

Implications of Convection in the Moon and the Terrestrial Planets

The early evolution of the Moon and its implications for the early evolution of the Earth was studied. The study is divided into two parts: (1) studies of core formation. Cosmochemical studies strongly favor a near-homogeneous accretion of the Earth. It is shown that core segregation probably occurred within the first 10,000 years of Earth history. It is found that dissipative heating may be a viable mechanism for core segregation if sufficiently large bodies of liquid iron can form; (2) early thermal evolution of the Earth and Moon. The energy associated with the accretion of the Earth and the segregation of the core is more than sufficient to melt the entire Earth. The increase in the mantle liquidus with depth (pressure) is the dominant effect influencing heat transfer through the magma ocean. It is found that a magma ocean with a depth of 100 km would have existed as the Earth accreted. It is concluded that this magma ocean zone refined the earth resulting in the simultaneous formation of the core and the atmosphere during accretion. The resulting mantle was a well-mixed solid with a near pyrolite composition.

Turcotte, D. L.↗

A Model for the Thermal and Chemical Evolution of the Moon's Interior: Implications for the Onset of Mare Volcanism

Crystallization of the lunar magma ocean creates a chemically stratified Moon consisting of an anorthositic crust and magma ocean cumulates overlying the primitive lunar interior. Within the magma ocean cumulates the last liquids to crystallize form dense, ilmenite-rich cumulates that contain high concentrations of incompatible radioactive elements. The underlying olivine-orthopyroxene cumulates are also stratified with later crystallized, denser, more Fe-rich compositions at the top. This paper explores the chemical and thermal consequences of an internal evolution model accounting for the possible role of these sources of chemical buoyancy. Rayleigh-Taylor instability causes the dense ilmenite-rich cumulate layer and underlying Fe-rich cumulates to sink toward the center of the Moon, forming a dense lunar core. After this overturn, radioactive heating within the ilmenite-rich cumulate core heats the overlying mantle, causing it to melt. In this model, the source region for high-TiO2 mare basalts is a convectively mixed layer above the core-mantle boundary which would contain small and variable amounts of admixed ilmenite and KREEP. This deep high-pressure melting, as required for mare basalts, occurs after a reasonable time interval to explain the onset of mare basalt volcanism if the content of radioactive elements in the core and the chemical density gradients above the core are sufficiently high but within a range of values that might have been present in the Moon. Regardless of details implied by particular model parameters, gravitational overturn driven by the high density of magma ocean Fe-rich cumulates should concentrate high-TiO2 mare basalt sources, and probably a significant fraction of radioactive heating, toward the center of the Moon. This will have important implications for both the thermal evolution of the Moon and for mare basalt genesis.

Hess, Paul C.↗

Complex igneous processes and the formation of the primitive lunar crustal rocks

Crystallization of a magma ocean with initial chondritic Ca/Al and REE ratios such as proposed by Taylor and Bence (TB, 1975), is capable of producing the suite of primitive crustal rocks if the magma ocean underwent locally extensive assimilation and mixing in its upper layers as preliminary steps in formation of an anorthositic crust. Lunar anorthosites were the earliest permanent crustal rocks to form the result of multiple cycles of suspension and assimilation of plagioclase in liquids fractionating olivine and pyroxene. There may be two series of Mg-rich cumulate rocks: one which developed as a result of the equilibration of anorthositic crust with the magma ocean; the other which formed in the later stages of the magma ocean during an epoch of magma mixing and ilmenite crystallization. This second series may be related to KREEP genesis. It is noted that crystallization of the magma ocean had two components: a low pressure component which produced a highly fractionated and heterogeneous crust growing downward and a high pressure component which filled in the ocean from the bottom up, mostly with olivine and low-Ca pyroxene.

Longhi, J.↗

Liquidus Phases of the Richardson H5 Chondrite at High Pressures and Temperatures

Part of early mantle evolution may include a magma ocean, where core formation began before the proto-Earth reached half of its present radius. Temperatures were high and bombardment and accretion were still occurring, suggesting that the proto-Earth consisted of a core and an at least partially liquid mantle, the magma ocean. As the Earth accreted, pressure near the core increased and the magma ocean decreased in volume and became shallower as it began to cool and solidify. As crystals settled, or floated, the composition of the magma ocean could change significantly and begin to crystallize different minerals from the residual liquid. Therefore, the mantle may be stratified following the P-T phase diagram for the bulk silicate Earth. To understand mantle evolution, it is necessary to know liquidus phase relations at high pressures and temperatures. In order to model the evolution of the magma ocean, high pressure and temperature experiments have been conducted to simulate the crystallization process using a range of materials that most likely resemble the bulk composition of the early Earth.

Channon, M.↗

Early lunar petrogenesis, oceanic and extraoceanic

An attempt is made to ascertain which (if any) pristine nonmare rocks, other than KREEPy ones, are not cumulates from the magma ocean. It is noted that the only pristine rocks having bulk densities low enough to have formed by floating above the magma ocean are the ferroan anorthosites, which are easily recognizable as a discrete subset of pristine rocks in general, on the basis of mineral composition relationships. The other class of pristine nonmare rocks, the Mg-rich rocks, did not form from the same magma that produced the ferroan anorthosites. It is suggested that they were formed in layered noritic-troctolitic plutons. These plutons, it is noted, were apparently intruded at, or slightly above, the boundary between the floated ferroan anorthosite crust and the underlying complementary mafic cumulates. It is thought that the parental magmas of the plutons may have arisen by partial melting of either deep mafic cumulates from the magma ocean or a still deeper, undifferentiated primordial layer that was not molten during the magma ocean period.

Warren, P. H.↗

Petrogenesis of lunar troctolites

Models of petrogenesis for lunar troctolites are severely constrained by the high Mg(*) (greater than 88) values of the most primitive members of the Mg-rich suite. Melts derived by partial melting of olivine cumulates to the lunar magma ocean have high Mg(*) but are strongly undersaturated with respect to plagioclase. Assimilation of lunar crust cannot bring these melts to the plagioclase liquious without unduly reducing the Mg(*) values of olivine. Partial melts derived by melting a lherzolite primitive interior have higher normative plagioclase contents but require sources with Mg(*) greater than 90. More terrestrial-like Mg(*) (approximately 88) values are permitted if rising thermal plumes are capable of entraining the most Mg-rich cumulates of the magma ocean. The Mg(*) values of lunar troctolites may, therfore, reflect a hybrid source composed of primitive mantle and Mr-rich cumulates of the magma ocean. Higher Mg(*) values may also arise from the reducction of small amounts of FeO to Fe. Alternatively, the parent magmas to lunar troctolites may be impact melts of the anorthositic crust and the Mg-rich dunites cumulates of the magma ocean; the latter were brought to the upper mantle during the overturn of the unstable cumulate pile of the magma ocean.

Hess, Paul C.↗

Core Formation in the Earth: Constraints from Ni and Co

Due to their metal-loving nature, Ni and Co were strongly partitioned into the metallic core and were left depleted in the silicate mantle during core formation in the Earth. Based on experimental liquid metal- liquid silicate partition coefficients (D), studies have suggested that core formation in an early magma Ocean can explain the observed mantle depletions of Ni and Co [l-51. However, the conditions proposed by the magma ocean models have ranged from pressures of 24 to 59 GPa and temperatures of 2200 to < 4000 K. Furthermore, the proposed magma Ocean oxygen fugacities have differed by nearly two orders of magnitude.Chabot and Agee noted that the different models predicted contradictory behaviors for D(Ni) and D(Co) as a function of temperature. With the hope of resolving the discrepancies between the magma ocean models, we conducted a systematic experimental study to constrain the effects of temperature on D(Ni) and D(Co).

Chabot, N. L.↗

Thermal structure of the accreting earth

The energy associated with the accretion of the earth and the segregation of the core is more than sufficient to melt the entire earth. In order to understand the thermal evolution of the early earth it is necessary to study the relevant heat transfer mechanisms. In this paper the existence of a global magma ocean is postulated and calculations are carried out of the heat flux through it in order to determine its depth. In the solid mantle heat is transferred by the upward migration of magma. This magma supplies the magma ocean. The increase in the mantle liquidus with depth (pressure) is the dominant effect influencing heat transfer through the magma ocean. It is found that a magma ocean with a depth of the order of 20 km would have existed as the earth accreted. It is concluded that the core segregated and an atmosphere was formed during accretion.

Turcotte, D. L.↗

Are the Clast Lithologies Contained in Lunar Breccia 64435 Mixtures of Anorthositic Magmas

The anorthositic crust of the Moon is often used as the archtypical example of a primary planetary crust. The abundance and purity of anorthosite in the Apollo sample collection and remote sensing data are generally attributed to an early global magma ocean which produced widespread floating plagioclase cumulates (the ferroan anorthosites; FANs. Recent geochronology studies report evidence of young (less than 4.4 Ga) FAN ages, which suggest that either some may not be directly produced from the magma ocean or that the final solidification age of the magma ocean was younger than previous estimates. A greater diversity of anorthositic rocks have been identified among lunar meteorites as compared to returned lunar samples. Granted that these lithologies are often based on small clasts in lunar breccias and therefore may not represent their actual whole rock composition. Nevertheless, as suggested by the abundance of anorthositic clasts with Mg# [Mg/(Mg+Fe)] less than 0.80 and the difficulty of producing the extremely high plagioclase contents observed in Apollo samples and the remote sensing data, modification of the standard Lunar Magma Ocean (LMO) model may be in order. To ground truth mission science and to further test the LMO and other hypotheses for the formation of the lunar crust, additional coordinated petrology and geochronology studies of lunar anorthosites would be informative. Here we report new mineral chemistry and trace element geochemistry studies of thick sections of a composite of FAN-suite igneous clasts contained in the lunar breccia 64435 in order to assess the significance of this type of sample for petrogenetic studies of the Moon. This work follows recent isotopic studies of the lithologies in 64435 focusing on the same sample materials and expands on previous petrology studies who identified three lithologies in this sample and worked on thin sections.

Simon, J. I.↗