The effect of Ni on element partitioning during iron meteorite crystallization

Abstract— ‐Iron meteorites exhibit a large range in Ni concentrations, from only 4% to nearly 60%. Most previous experiments aimed at understanding the crystallization of iron meteorites have been conducted in systems with about 10% Ni or less. We performed solid metal/liquid metal experiments to determine the effect of Ni on partition coefficients for 20 trace elements pertinent to iron meteorites. Experiments were conducted in both the end‐member Ni‐S system as well as in the Fe‐Ni‐S system with intermediate Ni compositions applicable to high‐Ni iron meteorites. The Ni content of the system affects solid metal/liquid metal partitioning behavior. For a given S concentration, partition coefficients in the Ni‐S system can be over an order of magnitude larger than in the Fe‐S system. However, for compositions relevant to even the most Ni‐rich iron meteorites, the effect of Ni on partitioning behavior is minor, amounting to less than a factor of two for the majority of trace elements studied. Any effect of Ni also appears minor when it is compared to the large influence S has on element partitioning behavior. Thus, we conclude that in the presence of an evolving S‐bearing metallic melt, crystallization models can safely neglect effects from Ni when considering the full range of iron meteorite compositions.     

The parameterization of solid metal‐liquid metal partitioning of siderophile elements

Abstract— Many solar system processes involve a metallic liquid, and the composition of the metallic liquid, such as the liquid's concentrations of S, P, and C, will influence the partitioning of elements during such processes. We present a method for parameterizing solid metal‐liquid metal partition coefficients for siderophile (metal‐loving) elements as a function of the metallic liquid composition. Our parameterization method is based on an older theory of Jones and Malvin (1990), which stated that the metallic liquid is composed of metal and non‐metal‐bearing domains, and the domains are the dominant influence on the partitioning behavior. By revising the means by which the metal domains are calculated, our revised parameterization method is able to match experimental partitioning data from the Fe‐Ni‐S, Fe‐Ni‐P, Fe‐Ni‐S‐P, and Fe‐Ni‐C systems. Mathematical expressions were derived for the solid metal‐liquid metal partitioning of 13 siderophile elements. Elements that are chalcophile (S‐loving), P‐loving, or C‐loving prefer the non‐metal‐bearing domains in the metallic liquid and, consequently, aren't fit by the parameterization method presented here. Possible applications for our parameterization method include modeling the crystallization of iron meteorites, planetary differentiation, and the solidification of Earth's inner core.     

Effect of silicon on trace element partitioning in iron‐bearing metallic melts

Abstract– Despite the fact that Si is considered a potentially important metalloid in planetary systems, little is known about the effect of Si in metallic melts on trace element partitioning behavior. Previous studies have established the effects of S, C, and P, nonmetals, through solid metal/liquid metal experiments in the corresponding Fe binary systems, but the Fe‐Si system is not appropriate for similar experiments because of the high solubility of Si in solid metal. In this work, we present the results from 0.1 MPa experiments with two coexisting immiscible metallic liquids in the Fe‐S‐Si system. By leveraging the extensive available knowledge about the effect of S on trace element partitioning behavior, we explore the effect of Si. Results for 22 trace elements are presented. Strong Si avoidance behavior is demonstrated by As, Au, Ga, Ge, Sb, Sn, and Zn. Iridium, Os, Pt, Re, Ru, and W exhibit weak Si avoidance tendencies. Silicon appears to have no significant effect on the partitioning behaviors of Ag, Co, Cu, Cr, Ni, Pd, and V, all of which had similar partition coefficients over a wide range of Si liquid concentrations from Si‐free to 13 wt%. The only elements in our experiments to show evidence of a potentially weak attraction to Si were Mo and Rh. Applications of the newly determined effects of Si to problems in planetary science indicate that (1) The elements Ni, Co, Mo, and W, which are commonly used in planetary differentiation models, are minimally affected by the presence of Si in the metal, especially in comparison to other effects such as from oxygen fugacity. 2) Reduced enstatite‐rich meteorites may record a chemical signature due to Si in the metallic melts during partial melting, and if so, elements identified by this study as having strong Si avoidance may offer unique insight into unraveling the history of these meteorites.     

Crystallization of magmatic iron meteorites: The effects of phosphorus and liquid immiscibility

Abstract— Magmatic iron meteorites are commonly thought to have formed by fractional crystallization of the metallic cores of asteroid‐sized bodies. As fractional crystallization proceeds, light elements such as P and S become enriched in the molten portion of the core. The light element content of the metallic liquid influences the partitioning behavior of trace elements and may cause liquid immiscibility to occur. The elemental trends observed in magmatic iron meteorites may have been affected by both of these processes. We have examined experimentally the effect of P on the solid‐metal‐liquid‐metal partitioning behavior of Ag and Pd, Re and Os, two element pairs used to date iron meteorite processes. Phosphorus has no effect on the partition coefficient of either Ag or Pd, which are incompatible and identical within experimental error. Compatible Re and Os also have identical partitioning behavior, within experimental error, and show increasing compatibility in the solid metal with increasing P content of the metallic liquid. Including the effects of both S and P on the partitioning behavior of Re and Os, simple fractional crystallization calculations can reproduce the large variation of Re and Os concentrations observed in four magmatic iron meteorite groups but have difficulty matching the later crystallizing portions of the trends. We have also conducted experiments with three phases—solid metal and two immiscible metallic liquids—to determine the location of the liquid immiscibility field near conditions thought to be relevant to magmatic iron meteorites. Our results show a significantly smaller liquid immiscibility field as compared to the previously published Fe‐P‐S phase diagram. Our revised phase diagram suggests that liquid immiscibility was encountered during the crystallization of asteroidal cores, but much later during the crystallization process than predicted by the previously published diagram.     

An experimental test of Henry's Law in solid metal‐liquid metal systems with implications for iron meteorites

Abstract— Experimental solid metal‐liquid metal partition coefficients have been used to model the crystallization of magmatic iron meteorites and understand the evolution of asteroid cores. However, the majority of the partitioning experiments have been conducted with trace elements doped at levels that are orders of magnitude higher than measured in iron meteorites. Concern about Henry's Law and the unnatural doping levels have been cited as one reason that two recent iron meteorite studies have dismissed the experimental partition coefficients in their modeling. Using laser ablation ICP‐MS analysis, this study reports experimentally determined solid metal‐liquid metal trace element partition coefficients from runs doped down to the levels occurring in iron meteorites. The analyses for 12 trace elements (As, Co, Cr, Cu, Ga, Ge, Ir, Os, Pd, Pt, Re, and W) show no deviations from Henry's Law, and these results support decades of experimental work in which the partition coefficients were assumed to be independent of trace element concentration. Further, since our experiments are doped with natural levels of trace elements, the partitioning results are directly applicable to iron meteorites and should be used when modeling their crystallization. In contrast, our new Ag data are inconsistent with previous studies, suggesting the high Ag‐content in previous studies may have influenced the measured Ag partitioning behavior.     

Moderately and slightly siderophile element constraints on the depth and extent of melting in early Mars

The thermal history of Mars during accretion and differentiation is important for understanding some fundamental aspects of its evolution such as crust formation, mantle geochemistry, chronology, volatile loss and interior degassing, and atmospheric development. In light of data from new Martian meteorites and exploration rovers, we have made a new estimate of Martian mantle siderophile element depletions. New high pressure and temperature metal–silicate experimental partitioning data and expressions are also available. Using these new constraints, we consider the conditions under which the Martian mantle may have equilibrated with metallic liquid. The resulting conditions that best satisfy six siderophile elements—Ni, Co, W, Mo, P, and Ga—and are consistent with the solidus and liquidus of the Martian mantle phase diagram are a pressure of 14 ± 3 GPa and temperature of 2100 ± 200 K. The Martian mantle depletions of Cr and V are also consistent with metal–silicate equilibration in this pressure and temperature range if deep mantle silicate phases are also taken into account. The results are not consistent with either metal–silicate equilibrium at the surface or at the current‐day Martian core–mantle boundary. Recent measurements and modeling have concluded that deep (～17 GPa or 1350 km) mantle melting is required to explain isotopic data for Martian meteorites and the nature of differentiation into core, mantle, and crust. This is in general agreement with our estimates of the conditions of Martian core formation based on siderophile elements that result in an intermediate depth magma ocean scenario for metal–silicate equilibrium.     

Wüstite in the fusion crust of Almahata Sitta sulfide‐metal assemblage MS‐166: Evidence for oxygen in metallic melts

Meteorite fusion crusts form during the passage of a meteoroid through the Earth's atmosphere and are highly oxidized intergrowths as documented by the presence of e.g., oxides. The porous and irregular fusion crust surrounding the Almahata Sitta sulfide‐metal assemblage MS‐166 was found highly enriched in wüstite (Fe_1‐xO). Frictional heating of the outer portions of the assemblage caused partial melting of predominantly the Fe‐sulfide and minor amounts of the outer Ni‐rich portions of the originally zoned metal in MS‐166. Along with melting significant amounts of oxygen were incorporated into the molten fusion crust and mainly FeS was oxidized and desulfurized to form wüstite. Considerable amounts of FeS were lost due to ablation, whereas the cores of the large metal grains appear largely unmelted leaving behind metal grains and surrounding wüstite‐rich material (matte). Metal grains along with the surrounding matte typically form an often highly porous framework of globules interconnected with the matte. Although textures and chemical composition suggest that melting of Fe,Ni metal occurred only partially (Ni‐rich rims), there is a trace elemental imprint of siderophile element partitioning influenced by oxygen in the metallic melt as indicated by the behavior of W and Ga, the two elements significantly affected by oxygen in a metallic melt. It is remarkable that MS‐166 survived the atmospheric passage as troilite inclusions in iron meteorites are preferentially destroyed.     

Effect of silicon on activity coefficients of Bi,Cd, Sn,and Ag in liquid Fe‐Si,and implications for differentiation and core formation

The depletion of volatile siderophile elements (VSE) Sn, Ag, Bi, Cd, and P in mantles of differentiated planetary bodies can be attributed to volatile‐depleted precursor materials (building blocks), fractionation during core formation, fractionation into and retention in sulfide minerals, and/or volatile loss associated with magmatism. Quantitative models to constrain the fractionation due to core formation have not been possible due to the lack of activity and partitioning data. Interaction parameters in Fe‐Si liquids have been measured at 1 GPa, 1600 °C and increase in the order Cd (~6), Ag (~10), Sn (~28), Bi (~46), and P (~58). These large and positive values contrast with smaller and negative values in Fe‐S liquids indicating that any chalcophile behavior exhibited by these elements will be erased by dissolution of a small amount of Si in the metallic liquid. A newly updated activity model is applied to Earth, Mars, and Vesta. Five elements (P, Zn, Sn, Cd, and In) in Earth's primitive upper mantle can largely be explained by metal‐silicate equilibrium at high PT conditions where the core‐forming metal is a Fe‐Ni‐S‐Si‐C metallic liquid, but two other—Ag and Bi—become overabundant during core formation and require a removal mechanism such as late sulfide segregation. All of the VSE in the mantle of Mars are consistent with core formation in a volatile element depleted body, and do not require any additional processes. Only P and Ag in Vesta's mantle are consistent with combined core formation and volatile‐depleted precursors, whereas the rest require accretion of chondritic or volatile‐bearing material after core formation. The concentrations of Zn, Ag, and Cd modeled for Vesta's core are similar to the concentration range measured in magmatic iron meteorites indicating that these volatile elements were already depleted in Vesta's precursor materials.     

An investigation of the behavior of Cu and Cr during iron meteorite crystallization

Abstract— The measured Cu and Cr contents in magmatic iron meteorites appear to contradict the behavior predicted by experimental fractional crystallization studies currently available. To investigate the origin of Cu and Cr concentrations observed in these meteorites, a thorough set of solid metal/liquid metal experiments were conducted in the Fe‐Ni‐S system. In addition to Cu and Cr, partitioning values were also determined for As, Au, Bi, Co, Mo, Ni, Pb, Rh, Ru, Sb, Sn, V, and Zn from the experiments. Experimental results for Cu and Cr showed similar chalcophile partitioning behavior, whereas these elements have differently sloped trends within magmatic iron meteorite groups. Thus, fractional crystallization alone cannot control both the Cu and Cr concentrations in these iron meteorite groups. A simple fractional crystallization model based on our experimental Cu partitioning results was able to match the Cu versus Au trend observed in the S‐poor IVB iron meteorite group but not the decreasing Cu versus Au trends in the IIAB and IIIAB groups or the unique S‐shaped Cu versus Au trend in the IVA group. However, the crystallization model calculations were found to be very sensitive to the specific choice for the mathematical expression of D(Cu), suggesting that any future refinement of the parameterization of D(Cu) should include a reassessment of the Cu fractional crystallization trends. The Cr versus Au trends in magmatic iron meteorite groups are steeper than those of Cu and not explained by fractional crystallization. Other influences, such as the removal of chromite from the crystallizing system or sampling biases during iron meteorite compositional analyses, are likely responsible for the Cr trends in magmatic iron meteorite groups.     

Experimental partitioning of trace elements into schreibersite with applications to IIG iron meteorites

Some of the defining characteristics of the IIG iron meteorite group are their high bulk P contents and massive, coarse schreibersite, which have been calculated to make up roughly 11–14 wt% of each specimen. In this study, we produced two data sets to investigate the formation of schreibersites in IIG irons: measurements of trace elements in the IIG iron meteorite Twannberg and experimental determinations of trace element partitioning into schreibersite. The schreibersite‐bearing experiments were conducted with schreibersite in equilibrium with a P‐rich melt and with bulk Ni contents ranging from 0 to 40 wt%. The partitioning behavior for the 20 elements measured in this study did not vary with Ni content. Comparison of the Twannberg measurements with the experimental results required a correction factor to account for the fact that the experiments were conducted in a simplified system that did not contain a solid metal phase. Previously determined solid metal/P‐rich melt partition coefficients were applied to infer schreibersite/solid metal partitioning behavior from the experiments, and once this correction was applied, the two data sets showed broad similarities between the schreibersite/solid metal distribution of elements. However, there were also differences noted, in particular between the Ni and P contents of the solid metal relative to the schreibersite inferred from the experiments compared to that measured in the Twannberg sample. These differences support previous interpretations that subsolidus schreibersite evolution has strongly influenced the Ni and P content now present in the solid metal phase of IIG irons. Quantitative attempts to match the IIG solid metal composition to that of late‐stage IIAB irons through subsolidus schreibersite growth were not successful, but qualitatively, this study corroborates the striking similarities between the IIAB and IIG groups, which are highly suggestive of a possible genetic link between the groups as has been previously proposed.     

Effects of liquid immiscibility on trace element fractionation in magmatic iron meteorites: A case study of group IIIAB

Abstract— Magmatic iron meteorites are generally agreed to represent metal that crystallized in asteroidal cores from a large pool of liquid. Estimates suggest that the metallic liquid contained significant amounts of S and P, both of which are incompatible and exert a strong effect on trace element partitioning. In tandem, S and P are also prone to cause immiscibility between sulfide liquid and P-rich metal liquid. The liquid immiscibility field occupies ～70% of the portion of the Fe-Ni-S-P system in which Fe is the first phase to crystallize. In spite of this, previous fractional crystallization models have taken into account only one liquid phase and have encountered significant discrepancies between the meteorite data and model values for the key elements Ni, Ir, Ga, Ge and Au at even moderate degrees of fractionation. For the first time, a model for trace element partitioning between immiscible liquids in the Fe-Ni-S-P system is presented in order to assess the effects on fractionation in magmatic iron meteorite groups. The onset of liquid immiscibility causes a significant change in the enrichment patterns of S and P in both liquids; so elements with contrasting partitioning behavior will show trends deviating clearly from one-liquid trends. A trend recorded in the solid metal will either be a smooth curve as long as equilibrium is maintained between the two liquids or the trend may diverge into a field limited by two extreme curves depending on the degree of disequilibrium. Bulk initial liquids for most magmatic groups have S/P (wt%) ratios well below 25. In these cases and due to the constitution of the Fe-Ni-S-P system, most of the metal will crystallize from the rapidly decreasing volume of metal liquid and only a subordinate amount from the sulfide liquid. Because of the strong extraction of P into the metal liquid, P will have a much larger influence on trace element partitioning than a low initial P content might suggest. My model calculations suggest that liquid immiscibility played a significant role during the solidification of the IIIAB parent body's core. The two-liquid model reproduces the IIIAB trends more closely than previous one-liquid models and can account for: (a) the general widening of the IIIAB trend with increasing Ni and decreasing Ir contents, (b) the occurrence of high-Ni members that are not strongly depleted in Ir, Ga and Ge; and (c) an upper limit at ～11 wt% Ni where the metal liquid was almost consumed.     

The effect of oxygen as a light element in metallic liquids on partitioning behavior

Oxygen has been considered a potentially important light element in metallic liquids during a range of planetary processes, yet the influence of O in a metallic melt on element partitioning behavior is largely unknown. To investigate the effect of O in such systems, we conducted experiments in the Fe‐S‐O system, doped with 25 trace elements, which produced two immiscible metallic liquids. Our results indicate that the presence of O in the metallic liquid produces a distinctive chemical signature for W and Ga in particular. Tungsten shows an affinity for O in the metallic liquid and partitions more strongly into the metallic melt in the presence of O. The partitioning of Ga is relatively constant despite the presence of O, which is in contrast to the majority of the other siderophile elements in the study. Our experiments from 1400 to 1600 °C show no significant effect from temperature on the partitioning behavior of any trace elements over this limited temperature range. This distinctive chemical signature due to the presence of O in the metallic liquid has potential implications for modeling core formation, evaluating isotopic signatures produced by core crystallization, and interpreting chemical assemblages observed in meteorites.     

Differentiation of metal‐rich meteoritic parent bodies: I. Measurements of PGEs,Re, Mo,W, and Au in meteoritic Fe‐Ni metal

Abstract— We describe an analytical technique for measurements of Fe, Ni, Co, Mo, Ru, Rh, W, Re, Os, Ir, Pt, and Au in bulk samples of iron meteorites. The technique involves EPMA (Fe, Ni, Co) and LA‐ICP‐MS analyses of individual phases of iron meteorites, followed by calculation of bulk compositions based on the abundances of these phases. We report, for the first time, a consistent set of concentrations of Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in the iron meteorites Arispe, Bennett County, Grant, Cape of Good Hope, Cape York, Carbo, Chinga, Coahuila, Duchesne, Gibeon, Henbury, Mundrabilla, Negrillos, Odessa, Sikhote‐Alin, and Toluca and the Divnoe primitive achondrite. The comparison of our LA‐ICP‐MS data for a number of iron meteorites with high‐precision isotope dilution and INAA data demonstrates the good precision and accuracy of our technique. The narrow ranges of variations of Mo and Pd concentrations within individual groups of iron meteorites suggest that these elements can provide important insights into the evolution of parent bodies of iron meteorites. Under certain assumptions, the Mo concentrations can be used to estimate mass fractions of the metal‐sulfide cores in the parent bodies of iron meteorites. It appears that a range of Pd variations within a group of iron meteorites can serve as a useful indicator of S content in the core of its parent body.     

The formation of eucrites: Constraints from metal‐silicate partition coefficients

Abstract— This study explores the controls of oxygen fugacity and temperature on the solubilities of Fe, Ni, Co, Mo, and W in natural eucritic liquids to better constrain the formation of eucritic melts. The solubilities of all five elements in molten silicate in equilibrium with FeNiCo‐, FeMo‐, and FeW‐ alloys increase with increasingly oxidizing conditions and decrease with decreasing temperatures. In applying these data to formation scenarios of the eucrite parent body, we find that the siderophile element abundances in eucrites (meteoritic basalts) cannot be explained by a single‐step partialmelting process from a chondritic, metal‐containing source. The Ni content of the partial melt is too high, and the W and Mo contents are too low compared to the abundances in eucritic meteorites. But Fe, Ni, and Co concentrations in eucrites can be modeled by metal‐silicate equilibrium during more or less complete melting of the eucrite parent body with subsequent fractional crystallization of olivine and orthopyroxene. However, the computed values of Mo are still too low and those of W too high when compared with Mo and W abundances in eucritic meteorites. One possibility is that the Mo and W partition coefficients strongly depend on pressure, although the howardite‐eucrite‐diogenite (HED) parent body only had a minimal pressure gradient (maximum interior pressure = 0.1 GPa). Alternatively, sulfides may have played some role in establishing Mo abundances.     

Geochemical zoning and magnetic mineralogy at Fe,Ni‐alloy–troilite interfaces of three iron meteorites from Morasko,Coahuila II,and Mundrabilla

We combined high‐resolution and space‐resolved elemental distribution with investigations of magnetic minerals across Fe,Ni‐alloy and troilite interfaces for two nonmagmatic (Morasko and Mundrabilla) IAB group iron meteorites and an octahedrite found in 1993 in Coahuila/Mexico (Coahuila II) preliminarily classified on Ir and Au content as IIAB group. The aim of this study was to elucidate the crystallization and thermal history using gradients of the siderophile elements Ni, Co, Ge, and Ga and the chalcophile elements Cr, Cu, and Se with a focus on magnetic minerals. The Morasko and Coahuila II meteorite show a several mm‐thick carbon‐ and phosphorous‐rich transition zone between Fe,Ni‐alloy and troilite, which is characterized by magnetic cohenite and nonmagnetic or magnetic schreibersite. At Morasko, these phases have a characteristic trace element composition with Mo enriched in cohenite. In both Morasko and Coahuila II, Ni is enriched in schreibersite. The minerals have crystallized from immiscible melts, either by fractional crystallization and C‐ and P‐enrichment in the melt, or by partial melting at temperatures slightly above the eutectic point. During crystallization of Mundrabilla, the field of immiscibility was not reached. Independent of meteorite group and cooling history, the magnetic mineralogy (daubreelite, cohenite and/or schreibersite, magnetite) is very similar to the troilite (and transition zone) for all three investigated iron meteorites. If these minerals can be separated from the metal, they might provide important information about the early solar system magnetic field. Magnetite is interpreted as a partial melting or a terrestrial weathering product of the Fe,Ni‐alloy under oxidizing conditions.     

Silicon in iron meteorite metal

Abstract– We report Si concentrations in the metal phases of iron meteorites. Analyses were performed by secondary ion mass spectrometry using a CAMECA 1270 ion probe. The Si concentrations are low (0.09–0.46 μg g^?1), with no apparent difference in concentration between magmatic and nonmagmatic iron meteorites. Coexisting kamacite and Ni‐rich metal phases have similar Si contents. Thermodynamic calculations show that Fe,Ni‐metal in equilibrium with silicate melts at temperatures where metal crystallizes should contain approximately 100 times more Si than found in iron meteorites in this work. The missing Si may either occur as tiny silicate inclusions in metal or it may have diffused as Si‐metal into surrounding silicates at low temperatures. In both cases, extensive low‐temperature diffusion of Si in metal is required. It is therefore concluded that low Si in iron meteorites is a result of subsolidus reactions during slow cooling.     

Parent body histories recorded in Rumuruti chondrite sulfides: Implications for the onset of oxidized,sulfur-rich core formation

Models of planetary core formation beginning with melting of Fe,Ni metal and troilite are not readily applicable to oxidized and sulfur-rich chondrites containing only trace quantities of metal. Cores formed in these bodies must be dominated by sulfides. Siderophile trace elements used to model metallic core formation could be used to model oxidized, sulfide-dominated core formation and identify related meteorites if their trace element systematics can be quantified. Insufficient information exists regarding the behavior of these core-forming elements among sulfides during metamorphism prior to anatexis. Major, minor, and trace element concentrations of sulfides are reported in this study for petrologic type 3–6 R chondrite materials. Sulfide-dominated core-forming components in such oxidized chondrites (ƒO₂ ≥ iron-wüstite) follow metamorphic evolutionary pathways that are distinct from reduced, metal-bearing counterparts. Most siderophile trace elements partition into pentlandite at approximately 10× chondritic abundances, but Pt, W, Mo, Ga, and Ge are depleted by 1–2 orders of magnitude relative to siderophile elements with similar volatilities. The distribution of siderophile elements is further altered during hydrothermal alteration as pyrrhotite oxidizes to form magnetite. Oxidized, sulfide-dominated core formation differs from metallic core formation models both physically and geochemically. Incongruent melting of pentlandite at 865°C generates melts capable of migrating along solid silicate grains, which can segregate to form a Ni,S-rich core at lower temperatures compared to reduced differentiated parent bodies and with distinct siderophile interelement proportions.     

Highly siderophile element (HSE) abundances in the mantle of Mars are due to core formation at high pressure and temperature

Highly siderophile elements (HSEs) can be used to understand accretion and core formation in differentiated bodies, due to their strong affinity for FeNi metal and sulfides. Coupling experimental studies of metal–silicate partitioning with analyses of HSE contents of Martian meteorites can thus offer important constraints on the early history of Mars. Here, we report new metal–silicate partitioning data for the PGEs and Au and Re across a wide range of pressure and temperature space, with three series designed to complement existing experimental data sets for HSE. The first series examines temperature effects for D(HSE) in two metallic liquid compositions—C‐bearing and C‐free. The second series examines temperature effects for D(Re) in FeO‐bearing silicate melts and FeNi‐rich alloys. The third series presents the first systematic study of high pressure and temperature effects for D(Au). We then combine our data with previously published partitioning data to derive predictive expressions for metal–silicate partitioning of the HSE, which are subsequently used to calculate HSE concentrations of the Martian mantle during continuous accretion of Mars. Our results show that at midmantle depths in an early magma ocean (equivalent to approximately 14 GPa, 2100 °C), the HSE contents of the silicate fraction are similar to those observed in the Martian meteorite suite. This is in concert with previous studies on moderately siderophile elements. We then consider model calculations that examine the role of melting, fractional crystallization, and sulfide saturation/undersaturation in establishing the range of HSE contents in Martian meteorites derived from melting of the postcore formation mantle. The core formation modeling indicates that the HSE contents can be established by metal–silicate equilibrium early in the history of Mars, thus obviating the need for a late veneer for HSE, and by extension volatile siderophile elements, or volatiles in general.     

Unmelted cosmic metal particles in the Indian Ocean

Fe‐Ni metal is a common constituent of most meteorites and is an indicator of the thermal history of the respective meteorites, it is a diagnostic tool to distinguish between groups/subgroups of meteorites. In spite of over a million micrometeorites collected from various domains, reports of pure metallic particles among micrometeorites have been extremely rare. We report here the finding of a variety of cosmic metal particles such as kamacite, plessite, taenite, and Fe‐Ni beads from deep‐sea sediments of the Indian Ocean, a majority of which have entered the Earth unaffected by frictional heating during atmospheric entry. Such particles are known as components of meteorites but have never been found as individual entities. Their compositions suggest precursors from a variety of meteorite groups, thus providing an insight into the metal fluxes on the Earth. Some particles have undergone heating and oxidation to different levels during entry developing features similar to I‐type cosmic spherules, suggesting atmospheric processing of individual kamacites/taenite grains as another hitherto unknown source for the I‐type spherules. The particles have undergone postdepositional aqueous alteration transforming finally into the serpentine mineral cronstedtite. Aqueous alteration products of kamacite reflect the local microenvironment, therefore they have the potential to provide information on the composition of water in the solar nebula, on the parent bodies or on surfaces of planetary bodies. Our observations suggest it would take sustained burial in water for tens of thousands of years under cold conditions for kamacites to alter to cronstedtite.     

Minor and trace element concentrations in adjacent kamacite and taenite in the Krymka chondrite

We report in situ NanoSIMS siderophile minor and trace element abundances in individual Fe‐Ni metal grains in the unequilibrated chondrite Krymka (LL3.2). Associated kamacite and taenite of 10 metal grains in four chondrules and one matrix metal were analyzed for elemental concentrations of Fe, Ni, Co, Cu, Rh, Ir, and Pt. The results show large elemental variations among the metal grains. However, complementary and correlative variations exist between adjacent kamacite‐taenite. This is consistent with the unequilibrated character of the chondrite and corroborates an attainment of chemical equilibrium between the metal phases. The calculated equilibrium temperature is 446 ± 9 °C. This is concordant with the range given by Kimura et al. (2008) for the Krymka postaccretion thermal metamorphism. Based on Ni diffusivity in taenite, a slow cooling rate is estimated of the Krymka parent body that does not exceed ~1K Myr^?1, which is consistent with cooling rates inferred by other workers for unequilibrated ordinary chondrites. Elemental ionic radii might have played a role in controlling elemental partitioning between kamacite and taenite. The bulk compositions of the Krymka metal grains have nonsolar (mostly subsolar) element/Ni ratios suggesting the Fe‐Ni grains could have formed from distinct precursors of nonsolar compositions or had their compositions modified subsequent to chondrule formation events.