Systematics of metal-silicate partitioning for many siderophile elements applied to Earth’s core formation

Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 °C, relative oxygen fugacities of IW−1.5 to IW−3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 °C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P-T-X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (∼3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P-T-fO₂ conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P-T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P-T conditions constrained by the peridotite liquidus and fixed fO₂ yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO₂ conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth’s mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.     

Metal-silicate partitioning and constraints on core composition and oxygen fugacity during Earth accretion

We present the results of new partitioning experiments between metal and silicate melts for a series of elements normally regarded as refractory lithophile and moderately siderophile and volatile. These include Si, Ti, Ni, Cr, Mn, Ga, Nb, Ta, Cu and Zn. Our new data obtained at 3.6 and 7.7 GPa and between 2123 and 2473 K are combined with literature data to parameterize the individual effects of oxygen fugacity, temperature, pressure and composition on partitioning. We find that Ni, Cu and Zn become less siderophile with increasing temperature. In contrast, Mn, Cr, Si, Ta, Nb, Ga and Ti become more siderophile with increasing temperature, with the highly charged cations (Nb, Ta, Si and Ti) being the most sensitive to variations of temperature. We also find that Ni, Cr, Nb, Ta and Ga become less siderophile with increasing pressure, while Mn becomes more siderophile with increasing pressure. Pressure effects on the partitioning of Si, Ti, Cu and Zn appear to be negligible, as are the effects of silicate melt composition on the partitioning of divalent cations. From the derived parameterization, we predict that the silicate Earth abundances of the elements mentioned above are best explained if core formation in a magma ocean took place under increasing conditions of oxygen fugacity, starting from moderately reduced conditions and finishing at the current mantle-core equilibrium value.     

Evidence for high-pressure core-mantle differentiation from the metal-silicate partitioning of lithophile and weakly-siderophile elements

Liquid Fe metal-liquid silicate partition coefficients for the lithophile and weakly-siderophile elements Ta, Nb, V, Cr, Si, Mn, Ga, In and Zn have been measured in multianvil experiments performed from 2 to 24 GPa, 2023-2873 K and at oxygen fugacities of −1.3 to −4.2 log units relative to the iron-wüstite buffer. Compositional effects of light elements dissolved in the metal liquid (S, C) have been examined and experiments were performed in both graphite and MgO capsules, specifically to address the effect of C solubility in Fe-metal on siderophile element partitioning. The results were used to examine whether there is categorical evidence that a significant portion of metal-silicate equilibration occurred under very high pressures during core-mantle fractionation on Earth. Although the depletion of V from the mantle due to core formation is significantly greater than that of Nb, our results indicate that both elements have similar siderophile tendencies under reducing conditions at low pressures. With increasing pressure, however, Nb becomes less siderophile than V, implying that average metal-silicate equilibration pressures of at least 10-40 GPa are required to explain the Nb/V ratio of the mantle. Similarly the moderately-siderophile, volatile element ratios Ga/Mn and In/Zn are chondritic in the mantle but both volatility and core-mantle equilibration at low pressure would render these ratios strongly sub-chondritic. Our results indicate that pressures of metal-silicate partitioning exceeding 30-60 GPa would be required to render these element ratios chondritic in the mantle. These observations strongly indicate that metal-silicate equilibration must have occurred at high pressures, and therefore support core-formation models that involve deep magma oceans. Moreover, our results allow us to exclude models that envisage primarily low-pressure (<1 GPa) equilibration in relatively small planetary bodies. We also argue that the core cannot contain significant U as this would require metal-silicate equilibration at oxygen fugacities low enough for significant amounts of Ta to have also been extracted from the mantle. Likewise, as In is more siderophile than Pb but similarly volatile and also quite chalcophile it would have been difficult for Pb to enter the core without reversing the relative depletions of these elements in the mantle unless metal-silicate equilibration occurred at high pressures >20 GPa.     

Melting of the Indarch meteorite (EH4 chondrite) at 1 GPa and variable oxygen fugacity: Implications for early planetary differentiation processes

In order to derive constraints on planetary differentiation processes, and ultimately the formation of the Earth, it is required to study a variety of meteoritic materials and to investigate their melting relations and elemental partitioning at variable pressures, temperatures, and oxygen fugacities (f_O2). This study reports the first high pressure (HP) and high temperature (HT) investigation of an enstatite chondrite (Indarch). Four series of experiments exploring various f_O2 conditions have been carried out at 1 GPa in a piston-cylinder apparatus using the EH4 chondrite Indarch. We show that temperature and redox conditions have important effects on the phase equilibria of the meteorite: the solidus and liquidus temperatures of the silicate portion increase with decreasing f_O2, and the stability fields of various phases are modified. Olivine and pyroxene are stable around 1.5 log f_O2 unit below the iron-wüstite buffer (IW−1.5), whereas quartz and pyroxene is the stable assemblage under the most reducing conditions, between IW−5.0 and IW−4.0, due to reduction of the silicate. While these changes are occurring in the silicate, the metal gains Si from the silicate, (Fe, Mg, Mn, Ca, Cr)-bearing sulfides are observed at f_O2 less than IW−4, and the partitioning of Ni and Mo are both affected by the presence of Si in Fe-S-C liquids. The f_O2 has also a significant effect on the liquid metal-liquid silicate partitioning behavior of Si and S, two possible light elements in planetary cores, and of the slightly siderophile elements Cr and Mn. With decreasing f_O2, S becomes increasingly lithophile, Si becomes increasingly siderophile, and Cr and Mn both become strongly siderophile and chalcophile. The partitioning behavior of these elements places new constraints on models of core segregation for the Earth and other differentiated bodies.     

The influence of sulfur on partitioning of siderophile elements

Sulfur is a potential light element in the liquid outer core of the Earth. Its presence in segregating metal may have had an influence in distribution of metal-loving (siderophile) elements during early accretion and core formation events in the Earth. The observed “excess” abundance of siderophile elements in the terrestrial mantle, relative to an abundance expected from simple core-mantle equilibrium at low temperature and pressure, may indicate a reduction in the iron-loving tendency of siderophile elements in the presence of sulfur in the metallic phase. The present experimental partitioning study between iron-carbon-sulfur-siderophile element bearing liquid metal and liquid silicate shows that for some siderophile elements this sulfur effect may be significant enough to even change their character to lithophile. Large and intricate variations in metal-silicate partition coefficients (D^met/sil) have been observed for many elements, e.g., Ni, Co, Ge, W, P, Au, and Re as a function of sulfur content. Moderately siderophile elements Ge, P, and W show the most significant response (sulfur-avoidance) by an enhanced segregation into the associated sulfur-deficient phases. Highly siderophile elements Ir, Pt, and Re show a different style of sulfur-avoidance (alloy-preference) by segregating as sulfur-poor, siderophile element-rich alloys. Both groups are chalcophobic. D^met/sil for Ni, Co, and Au moderately decreases with increasing sulfur-content in the liquid metal. D^met/sil for chalcophile element, Cr, in contrast, increases with sulfur. Irrespective of the sulfur-content, in the presence of a carbon-saturated liquid metal, P is always lithophile. The general nonmetal-avoidance tendency of siderophile elements (and acceptance of chalcophile elements) in the liquid metal, postulated by Jones and Malvin (1990) in the FeNiS(sulfur)M (siderophile) system is found to be present in the metal-silicate system as well. A sulfur-bearning liquid metal segregation can potentially reduce the metal-loving nature of many elements to explain the excess paradox. Sulfur-bearing core segregation, however, might require an efficient draining of exsolved immiscible sulfide liquids from the molten silicate, or an increasing siderophility of sulfur at high pressure to reduce the mantle sulfur content to the observed (<300 ppm) value. Moreover, the chondritic relative abundance pattern of many moderately or highly siderophile elements in the upper mantle is not explained by the presence of sulfur in the segregating metals. Core formation is more complex and intricate than equilibrium segregation.     

Effect of pressure, temperature, and oxygen fugacity on the metal-silicate partitioning of Te, Se, and S: Implications for earth differentiation

We have measured liquid Fe metal-liquid silicate partitioning (D_i) of tellurium, selenium, and sulfur over a range of pressure, temperature, and oxygen fugacity (1-19 GPa, 2023-2693 K, fO₂ −0.4 to −5.5 log units relative to the iron-wüstite buffer) to better assess the role of metallic melts in fractionating these elements during mantle melting and early Earth evolution. We find that metal-silicate partitioning of all three elements decreases with falling FeO activity in the silicate melt, and that the addition of 5-10 wt% S in the metal phase results in a 3-fold enhancement of both D_Te and D_Se. In general, Te, Se, and S all become more siderophile with increasing pressure, and less siderophile with increasing temperature, in agreement with previous work. In all sulfur-bearing experiments, D_Te is greater than D_Se or D_S, with the latter two being similar over a range of P and T. Parameterized results are used to estimate metal-silicate partitioning at the base of a magma ocean which deepens as accretion progresses, with the equilibration temperature fixed at the peridotite liquidus. We show that during accretion, Te behaves like a highly siderophile element, with expected core/mantle partitioning of >10⁵, in contrast to the observed core/mantle ratio of ∼100. Less extreme differences are observed for Se and S, which yielded core/mantle partitioning 100- to 10 times higher, respectively, than the observed value. Addition of ∼0.5 wt% of a meteorite component (H, EH or EL ordinary chondrite) is sufficient to raise mantle abundances to their current level and erase the original interelement fractionation of metal-silicate equilibrium.     

Siderophile elements in Martian meteorites and implications for core formation in Mars

Noble metals, Mo, W, and 24 other elements were determined in six SNC meteorites of presumably Martian origin. Based on element correlations, representative siderophile element concentrations for the silicate mantle of Mars were inferred. From a comparison with experimentally determined metal/silicate partition coefficients of the moderately siderophile elements: Fe, Ni, Co, W, Mo, and Ga, it is concluded that equilibrium between core forming metal and silicates in Mars has occurred at high temperatures (around 2200°C) and low pressures (<1 GPa). This suggests that metal segregation occurred concurrently with rapid accretion of Mars, which is consistent with the inference from excess ¹⁸²W in Martian meteorites (Lee and Halliday, 1997). Concentrations of Ir, Os, Ru, Pt, and Au in the analyzed Martian meteorites, except ALH84001, are at a level of approximately 10⁻²–10⁻³ × CI. The comparatively high abundances of noble metals in Martian meteorites require the addition of chondritic material after core formation. The similarity in Au/La and Pt/Ca ratios between ALH84001 and the other Martian meteorites suggests crystallization of ALH84001 after complete accretion of Mars.     

Core formation and the oxidation state of the Earth: Additional constraints from Nb, V and Cr partitioning

We have combined metal-silicate partitioning data from the literature with new experimental results at 1.5-8 GPa and 1480-2000 °C to parameterize the effects of pressure, temperature and composition on the partitioning of V, Cr and Nb between liquid Fe metal (with low S and C content) and silicate melt.Using information from the steelmaking literature to correct for interactions in the metal phase, we find that, for peridotitic silicate melts, metal-silicate partition coefficients are given by:

     

Trace element partitioning in the Fe-S-C system and its implications for planetary differentiation and the thermal history of ureilites

Element partitioning in metal-light element systems is important to our understanding of planetary differentiation processes. In this study, solid-metal/liquid-sulfide, liquid-metal/liquid-sulfide and solid-metal/troilite partition coefficients (D) were determined for 18 elements (Ag, As, Au, Co, Cr, Cu, Ge, Ir, Ni, Os, Pd, Pt, Mo, Mn, Re, Ru, Se and W) in the graphite-saturated Fe-S-C system at 1 atm. Compared at the same liquid S concentration, the solid/liquid partition coefficients are similar to those in the Fe-S system, but there are systematic differences that appear to be related to interactions with carbon dissolved in the solid metal. Elements previously shown to be “anthracophile” generally have larger solid/liquid partition coefficients in the Fe-S-C system, whereas those that are not have similar or smaller partition coefficients in the Fe-S-C system. The partitioning of trace elements between C-rich and S-rich liquids is, in most cases, broadly similar to the partitioning between solid metal and S-rich liquid. The highly siderophile elements Os, Re, Ir and W are partitioned strongly into the C-rich liquid, with D ? 100. The partition coefficients for Pt, Ge and W decrease significantly at the transition to liquid immiscibility, while the partition coefficient for Mo increases sharply. The bulk siderophile element patterns of ureilite meteorities appear to be better explained by separation of S-rich liquid from residual C-rich metallic liquid at temperatures above the silicate solidus, rather than by separation of S-rich liquid from residual solid metal at lower temperatures.     

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.     

Conditions of core formation in the earth: Constraints from Nickel and Cobalt partitioning

The abundances of Ni and Co in the Earth’s mantle are depleted relative to chondrites due to terrestrial core formation. Recently, the observed mantle depletions of these elements have been explained by liquid metal-liquid silicate equilibrium during core formation in a high pressure, high temperature magma ocean on the early Earth. However, different magma ocean models, which would be expected to give consistent results, have proposed vastly different pressures (24 to 59 GPa), temperatures (2200 to >4000 K) and oxygen fugacities (−0.15 to −2.4 ΔIW) for the Earth’s magma ocean. In an attempt to resolve the contradictory results from different magma ocean models and determine the thermodynamic conditions appropriate for core formation in the Earth, experiments were conducted to better constrain the influences of temperature and C on the partitioning behaviors of Ni and Co. Results of experiments at 7 GPa with temperatures of 1923-2673 K show that the metal-silicate partition coefficients for both Ni and Co decrease with increasing temperature, with the effect being more significant for Ni. Little change in the partitioning behaviors of either Ni or Co with varying C-content of the metallic liquid was found. By combining the new temperature data with previous results from pressure and oxygen fugacity studies, we parameterized the partitioning behavior of Ni and Co and applied the parameterizations to core formation in a terrestrial magma ocean. Multiple combinations of pressure, temperature, and oxygen fugacity can explain the observed mantle depletions of Ni and Co, and all of the very different previously proposed magma ocean conditions are generally consistent with valid solutions. By using the FeO content of the Earth’s mantle as an additional constraint on the oxygen fugacity, magma ocean conditions of 30-60 GPa, > 2000 K, and −2.2 ΔIW are suggested. Similar systematic approaches and studies of other moderately siderophile elements could further constrain the magma ocean conditions on the early Earth.     

Oxygen fugacity dependence of Ni,Co, Mn,Cr, V,and Si partitioning between liquid metal and magnesiowüstite at 9–18 GPa and 2200°C

The oxidation states of Ni, Co, Mn, Cr, V and Si in magnesiowüstite have been determined in metal-oxide distribution experiments using a multi anvil apparatus at 9 and 18 GPa and 2200°C as a function of oxygen fugacity. Despite limitations to control oxygen fugacity by applying conventional buffering methods in high pressure experiments, a wide range of redox-conditions (3 log bar units) has been imposed to the metal-oxide partitioning experiments by varying the Si/O ratio of the starting material. The oxygen fugacity was calculated according to the Fe-FeO equilibrium between the run products. The ability to impose different oxygen fugacities by varying the starting material is confirmed by the large variation of element partitioning coefficients obtained at constant pressure and temperature. The calculated valences at both pressures investigated are divalent for Co, Mn, V and 4+ for Si. The results for Cr (∼2.5+) and Ni (∼1.5+) indicate non-ideal mixing of Ni and Cr in at least one of the product phases. Because the application of 1 bar activity coefficients for Ni and Cr in metal alloys does not change these valences, non-ideal mixing in magnesiowüstite or significantly larger non-ideal mixing properties of Ni and Cr in metal alloys at high pressure are likely to be responsible for the apparent valences. Omitting such non-ideal mixing properties when extrapolating high-pressure element partitioning data may be significant. The elements Cr, V and Mn become siderophile (D_M^met/ox > 1) at 9–18 GPa and 2200°C at oxygen fugacities below IW-2.7 to IW-3.7. Considering, in addition, the influence of temperature, the depletion of Cr, Mn and V in the Earth’s mantle may be due, at least partly, to siderophile behavior at high pressure and temperature.     

High pressure equilibrium of nickel and cobalt between metal and mantle minerals

In order to test the effect of very high pressures on the siderophile behaviour of two elements, Ni and Co, we have carried out diamond anvil cell experiments on Ni- and Co-bearing systems, up to 70 GPa. Observation of recovered samples by analytical transmission electron microscopy shows that Ni and Co remain siderophile at least up to 70 GPa, but that their siderophile character decreases with pressure, as already observed in previous studies at lower pressures. Our results also suggest that the abundances of Ni and Co observed in the Earth’s upper mantle cannot be explained by very high pressure equilibrium between silicate perovskite, magnesiowüstite, and metal.     

Chemical composition and origin of the earth's primitive mantle

An attempt has been made to estimate the chemical composition of the earth's primitive mantle by a critical evaluation of data derived from ultramafic mantle samples and partial melting model calculations for mafic and ultramafic magmas of various ages.Compatible (Al, Ca, Si, Mg, Fe) and moderately incompatible (Ti, Zr, heavy and middle rare earth) elements in basaltic magma sources have not changed significantly since the early Archaean (~3.5 Byr). Estimated abundances for refractory lithophile elements (such as Al, Ca, Ti, Zr, Y, Se, REE etc.) in the primitive mantle are about 2.0 times ordinary chondrites (~ 1.1 times Cl chondrites relative to Mg). Highly incompatible volatile elements (K, Rb, Cs, Tl, Pb etc.) are depleted in the mantle throughout geological time. Abundances of Fe, Ni and Co are obtained on the basis of values for ultramafic nodules and model calculations using komatiites of various ages. The results show little (? 20%?) dispersion and there is no obvious secular variation since 3.5 Byr. Noble metals show similar effects. These data permit constraints to be placed on the timing of core formation.The estimated elemental abundances for the primitive mantle are normalized to Cl chondrites relative to Mg and plotted against the solar condensation temperature at 10^?4 atm. Above 700 K there are two parallel trends which are defined by lithophile elements (Al, Ca, REE, Ti, Mg, Si, Cr, Mn, Na, K, Rb, F, Zn etc.) and siderophile elements (W, Ni, Co, P, As, Ag, Sb and Ge) respectively. The depletion factor for the siderophile trend relative to the lithophile trend is about 0.085. Within each trend there is a continuous depletion towards lower temperature. A third trend is defined by noble metals (Ir, Os, Re, Pd, Pt and Au) with a depletion factor of about 0.003 relative to Cl chondrites. These trends are interpreted in terms of core-mantle differentiation and volatility-controlled processes operating before and during earth accretion.     

Minor and trace elements in some meteoritic minerals

The mineral phases including olivine, orthopyroxene, clinopyroxene, troilite, nickel-iron, plagioclase, chromite and the phosphates were separated from several meteorites. These were a hypersthene chondrite (Modoc), a bronzite chondrite (Guareña), an enstatite chondrite (Khairpur), and two eucrites (Haraiya and Moore County); diopside was separated from the Nakhla achondrite. The purified minerals were analyzed for trace and minor elements by spark source mass spectrometry and instrumental neutron activation analysis. On the meteorites examined our results show that Co, Ni, Cu, Ge, As, Ru, Rh, Pd, Sn, Sb, W, Re, Os, Ir, Pt and Au are entirely or almost entirely siderophile; Na, Rb, Sr, Y, Ba and the rare earth elements lithophile; Se chalcophile. The transition elements So, Ti, V, Cr and Mn are lithophile in most stony meteorites, but show chalcophile affinities in the enstatite chondrites (and enstatite achondrites), as do Zn, Zr and Nb. In the ordinary chondrites Ga shows both lithophile and siderophile affinities, but becomes entirely siderophile in the enstatite chondrites. Molybdenum and tellurium show strong siderophile and weaker chalcophile affinity. The lithophile elements are distributed among the minerals according to the crystallochemical factors, the most effective controlling factor being ionic size.     

Group IVA irons: New constraints on the crystallization and cooling history of an asteroidal core with a complex history

We report analyses of 14 group IVA iron meteorites, and the ungrouped but possibly related, Elephant Moraine (EET) 83230, for siderophile elements by laser ablation ICP-MS and isotope dilution. EET was also analyzed for oxygen isotopic composition and metallographic structure, and Fuzzy Creek, currently the IVA with the highest Ni concentration, was analyzed for metallographic structure. Highly siderophile elements (HSE) Re, Os and Ir concentrations vary by nearly three orders of magnitude over the entire range of IVA irons, while Ru, Pt and Pd vary by less than factors of five. Chondrite normalized abundances of HSE form nested patterns consistent with progressive crystal-liquid fractionation. Attempts to collectively model the HSE abundances resulting from fractional crystallization achieved best results for 3 wt.% S, compared to 0.5 or 9 wt.% S. Consistent with prior studies, concentrations of HSE and other refractory siderophile elements estimated for the bulk IVA core and its parent body are in generally chondritic proportions. Projected abundances of Pd and Au, relative to more refractory HSE, are slightly elevated and modestly differ from L/LL chondrites, which some have linked with group IVA, based on oxygen isotope similarities.Abundance trends for the moderately volatile and siderophile element Ga cannot be adequately modeled for any S concentration, the cause of which remains enigmatic. Further, concentrations of some moderately volatile and siderophile elements indicate marked, progressive depletions in the IVA system. However, if the IVA core began crystallization with ∼3 wt.% S, depletions of more volatile elements cannot be explained as a result of prior volatilization/condensation processes. The initial IVA core had an approximately chondritic Ni/Co ratio, but a fractionated Fe/Ni ratio of ∼10, indicates an Fe-depleted core. This composition is most easily accounted for by assuming that the surrounding silicate shell was enriched in iron, consistent with an oxidized parent body. The depletions in Ga may reflect decreased siderophilic behavior in a relatively oxidized body, and more favorable partitioning into the silicate portion of the parent body.Phosphate inclusions in EET show Δ¹⁷O values within the range measured for silicates in IVA iron meteorites. EET has a typical ataxitic microstructure with precipitates of kamacite within a matrix of plessite. Chemical and isotopic evidence for a genetic relation between EET and group IVA is strong, but the high Ni content and the newly determined, rapid cooling rate of this meteorite show that it should continue to be classified as ungrouped. Previously reported metallographic cooling rates for IVA iron meteorites have been interpreted to indicate an inwardly crystallizing, ∼150 km radius metallic body with little or no silicate mantle. Hence, the IVA group was likely formed as a mass of molten metal separated from a much larger parent body that was broken apart by a large impact. Given the apparent genetic relation with IVA, EET was most likely generated via crystal-liquid fractionation in another, smaller body spawned from the same initial liquid during the impact event that generated the IVA body.     

Compositions of group IVB iron meteorites and their parent melt

The concentrations of P, V, Cr, Fe, Co, Ni, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in the group IVB iron meteorites Cape of Good Hope, Hoba, Skookum, Santa Clara, Tawallah Valley, Tlacotepec, and Warburton Range have been measured by laser ablation inductively coupled plasma mass spectrometry. The data were fitted to a model of fractional crystallization of the IVB parent body core, from which the composition of the parent melt and metal/melt distribution coefficients for each element in the system were determined, for a chosen value of D(Ni). Relative to Ni and chondritic abundances, the parent melt was enriched in refractory siderophiles, with greatest enrichment of 5× chondritic in the most refractory elements, and was strongly volatile-depleted, down to 0.00014× chondritic in Ge. Comparison to an equilibrium condensation sequence from a gas of solar composition indicates that no single temperature satisfactorily explains the volatility trend in the IVB parent melt; a small (<1%) complement of ultrarefractory components added to metal that is volatile-depleted but otherwise has nearly chondritic abundances (for Fe, Co and Ni) best explains the volatility trend. In addition to this volatility processing, which probably occurred in a nebular setting, there was substantial oxidation of the metal in the IVB parent body, leading to loss of Fe and other moderately siderophile elements such as Cr, Ga, and W, and producing the high Ni contents that are observed in the IVB irons. By assuming that the entire IVB parent body underwent a similar chemical history as its core, the composition of the silicate that is complementary to the IVB parent melt was also estimated, and appears to be similar to that of the angrite parent.     

The influence of carbon on trace element partitioning behavior

Carbon has been proposed as a potential light element in planetary cores, included in models of planetary core formation, and found in meteoritic samples and minerals. To better understand the effect of C on the partitioning behavior of elements, solid/liquid partition coefficients (D = (solid metal)/(liquid metal)) were determined for 17 elements (As, Au, Co, Cr, Cu, Ga, Ge, Ir, Ni, Os, Pd, Pt, Re, Ru, Sb, Sn, and W) over a range of C contents in the Fe-Ni-C system at 1 atm. The partition coefficients for the majority of the elements increased as the C content of the liquid increased, an effect analogous to that of S for many of the elements. In contrast, three of the elements, Cr, Re, and W, were found to have anthracophile (C-loving) preferences, partitioning more strongly into the metallic liquid as the C content increased, resulting in decreases to their partition coefficients. For half of the elements examined, the prediction that partitioning in the Fe-Ni-S and Fe-Ni-C systems could be parameterized using a single set of variables was not supported. The effects of S and C on elemental partitioning behavior can be quite different; consequently, the presence of different non-metals can result in different fractionation patterns, and that uniqueness offers the opportunity to gain insight into the evolution of planetary bodies.     

The great sulfur depletion of Earth’s mantle is not a signature of mantle–core equilibration

The extreme depletion of the Earth’s mantle in sulfur is commonly seen as a signature of metal segregation from Earth’s mantle to Earth’s core. However, in addition to S, the mantle contains other elements as volatile as S that are hardly depleted relative to the lithophile volatility trend although they are potentially as siderophile as sulfur. We report experiments in metal-sulfide–silicate systems to show that the CI normalized abundances of S, Pb, and Sn in Earth’s mantle cannot be reproduced by element partitioning in Fe ± S–silicate systems, neither at low nor at high pressure. Much of the volatile inventory of the Earth’s mantle must have been added late in the accretion history, when metal melt segregation to the core had become largely inactive. The great depletion in S is attributed to the selective segregation of a late sulfide matte from an oxidized and largely crystalline mantle. Apparently, the volatile abundances of Earth’s mantle are not in redox equilibrium with Earth’s core.     

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.