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.     

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 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.     

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.     

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.     

Crystallization of magmatic iron meteorites: The role of mixing in the molten core

Abstract— The IIIAB group is the largest of the magmatic iron meteorite groups and consequently is commonly used to test models of asteroid core crystallization. Simple fractional crystallization calculations appear to reproduce the general shape of the elemental trends observed in the IIIAB group when these trends are plotted vs. Ni, as is traditionally done. However, when the elemental trends are examined vs. another element (such as Ge vs. Ir), simple fractional crystallization fails to match a significant portion of the trend, specifically meteorites formed during the final stages of crystallization. Our simple mixing model, which attempts to account for the possibility of inhomogeneities in the molten metallic core, is able to reproduce the entire IIIAB trend observed. This model is a variant of simple fractional crystallization and involves mixing between a zone of liquid involved in the crystallization process and a second zone too far from the crystallizing solid to be actively involved in crystallization. This model does not suggest one unique solution for the method by which an asteroidal core crystallizes; rather it demonstrates that including the effects of mixing in the molten core can account for the observed IIIAB elemental trends, particularly the late-stage crystallizing members, which other models have difficulty explaining.     

Mass‐dependent fractionation of nickel isotopes in meteoritic metal

Abstract— We measured nickel isotopes via multicollector inductively coupled plasma mass spectrometry (MC‐ICPMS) in the bulk metal from 36 meteorites, including chondrites, pallasites, and irons (magmatic and non‐magmatic). The Ni isotopes in these meteorites are mass fractionated; the fractionation spans an overall range of ～0.4‰ amu^?1. The ranges of Ni isotopic compositions (relative to the SRM 986 Ni isotopic standard) in metal from iron meteorites (～0.0 to ～0.3‰ amu^?1) and chondrites (～0.0 to ～0.2‰ amu^?1) are similar, whereas the range in pallasite metal (～–0.1 to 0.0‰ amu^?1) appears distinct. The fractionation of Ni isotopes within a suite of fourteen IIIAB irons (～0.0 to ～0.3‰ amu^?1) spans the entire range measured in all magmatic irons. However, the degree of Ni isotopic fractionation in these samples does not correlate with their Ni content, suggesting that core crystallization did not fractionate Ni isotopes in a systematic way. We also measured the Ni and Fe isotopes in adjacent kamacite and taenite from the Toluca IAB iron meteorite. Nickel isotopes show clearly resolvable fractionation between these two phases; kamacite is heavier relative to taenite by ～0.4‰ amu^?1. In contrast, the Fe isotopes do not show a resolvable fractionation between kamacite and taenite. The observed isotopic compositions of kamacite and taenite can be understood in terms of kinetic fractionation due to diffusion of Ni during cooling of the Fe‐Ni alloy and the development of the Widmanstätten pattern.     

COMPOSITION AND ORIGIN OF THE UNUSUAL OKTIBBEHA COUNTY IRON METEORITE

We have analyzed Oktibbeha County, the most Ni-rich iron meteorite, for Ni, Co, Cu, Ga, Ge, As, Sb, Ir, and Au. Cu and Sb are higher than in any other iron, but other trace elements are within the ranges typically found in iron meteorites. Extrapolation of trace element trends in group IAB indicates that Oktibbeha County is a member of this group. This sheds light on the origin of groups IAB and IIICD, which are thought to be derived from impact melts on parent bodies of chondritic composition. Lafayette (iron), another sample reported in the literature to have a similarly high Ni content, is probably a pseudometeorite.     

Experimental determination of partitioning in the Fe‐Ni system for applications to modeling meteoritic metals

Experimental trace element partitioning values are often used to model the chemical evolution of metallic phases in meteorites, but limited experimental data were previously available to constrain the partitioning behavior in the basic Fe‐Ni system. In this study, we conducted experiments that produced equilibrium solid metal and liquid metal phases in the Fe‐Ni system and measured the partition coefficients of 25 elements. The results are in good agreement with values modeled from IVB iron meteorites and with the limited previous experimental data. Additional experiments with low levels of S and P were also conducted to help constrain the partitioning behaviors of elements as a function of these light elements. The new experimental results were used to derive a set of parameterization values for element solid metal–liquid metal partitioning behavior in the Fe‐Ni‐S, Fe‐Ni‐P, and Fe‐Ni‐C ternary systems at 0.1 MPa. The new parameterizations require that the partitioning behaviors in the light‐element–free Fe‐Ni system are those determined experimentally by this study, in contrast to previous parameterizations that allowed this value to be determined as a best‐fit parameter. These new parameterizations, with self‐consistent values for partitioning in the endmember Fe‐Ni system, provide a valuable resource for future studies that model the chemical evolution of metallic phases 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.     

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.     

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.     

The abundance and isotopic composition of Cd in iron meteorites

Cadmium is a highly volatile element and its abundance in meteorites may help better understand volatility‐controlled processes in the solar nebula and on meteorite parent bodies. The large thermal neutron capture cross section of ¹¹³Cd suggests that Cd isotopes might be well suited to quantify neutron fluences in extraterrestrial materials. The aims of this study were (1) to evaluate the range and magnitude of Cd concentrations in magmatic iron meteorites, and (2) to assess the potential of Cd isotopes as a neutron dosimeter for iron meteorites. Our new Cd concentration data determined by isotope dilution demonstrate that Cd concentrations in iron meteorites are significantly lower than in some previous studies. In contrast to large systematic variations in the concentration of moderately volatile elements like Ga and Ge, there is neither systematic variation in Cd concentration amongst troilites, nor amongst metal phases of different iron meteorite groups. Instead, Cd is strongly depleted in all iron meteorite groups, implying that the parent bodies accreted well above the condensation temperature of Cd (i.e., ≈650 K) and thus incorporated only minimal amounts of highly volatile elements. No Cd isotope anomalies were found, whereas Pt and W isotope anomalies for the same iron meteorite samples indicate a significant fluence of epithermal and higher energetic neutrons. This observation demonstrates that owing to the high Fe concentrations in iron meteorites, neutron capture mainly occurs at epithermal and higher energies. The combined Cd‐Pt‐W isotope results from this study thus demonstrate that the relative magnitude of neutron capture‐induced isotope anomalies is strongly affected by the chemical composition of the irradiated material. The resulting low fluence of thermal neutrons in iron meteorites and their very low Cd concentrations make Cd isotopes unsuitable as a neutron dosimeter for iron meteorites.     

Genesis of the IIICD iron meteorites: Evidence from silicate-bearing inclusions

Abstract— Our studies of the silicate-bearing inclusions in the IIICD iron meteorites Maltahöhe, Carlton and Dayton suggest that their mineralogy and mineral compositions are related to the composition of the metal in the host meteorites. An inclusion in the low-Ni Maltahöhe is similar in mineralogy to those in IAB irons, which contain olivine, pyroxene, plagioclase, graphite and troilite. With increasing Ni concentration of the metal, silicate inclusions become poorer in graphite, richer in phosphates, and the phosphate and silicate assemblages become more complex. Dayton contains pyroxene, plagioclase, SiO₂, brianite, panethite and whitlockite, without graphite. In addition, mafic silicates become more FeO-rich with increasing Ni concentration of the hosts. In contrast, silicates in IAB irons show no such correlation with host Ni concentration, nor do they have the complex mineral assemblages of Dayton. These trends in inclusion composition and mineralogy in IIICD iron meteorites have been established by reactions between the S-rich metallic magma and the silicates, but the physical setting is uncertain. Of the two processes invoked by other authors to account for groups IAB and IIICD, fractional crystallization of S-rich cores and impact generation of melt pools, we prefer core crystallization. However, the absence of relationships between silicate inclusion mineralogy and metal compositions among IAB irons analogous to those that we have discovered in IIICD irons suggests that the IAB and IIICD cores/metallic magmas evolved in rather different ways. We suggest that the solidification of the IIICD core may have been very complex, involving fractional crystallization, nucleation effects and, possibly, liquid immiscibility.     

Metal‐saturated sulfide assemblages in NWA 2737: Evidence for impact‐related sulfur devolatilization in Martian meteorites

NWA 2737, a Martian meteorite from the Chassignite subclass, contains minute amounts (0.010 ± 0.005 vol%) of metal‐saturated Fe‐Ni sulfides. These latter bear evidence of the strong shock effects documented by abundant Fe nanoparticles and planar defects in Northwest Africa (NWA) 2737 olivine. A Ni‐poor troilite (Fe/S = 1.0 ± 0.01), sometimes Cr‐bearing (up to 1 wt%), coexists with micrometer‐sized taenite/tetrataenite‐type native Ni‐Fe alloys (Ni/Fe = 1) and Fe‐Os‐Ir‐(Ru) alloys a few hundreds of nanometers across. The troilite has exsolved flame‐like pentlandite (Fe/Fe + Ni = 0.5–0.6). Chalcopyrite is almost lacking, and no pyrite has been found. As a hot desert find, NWA 2737 shows astonishingly fresh sulfides. The composition of troilite coexisting with Ni‐Fe alloys is completely at odds with Chassigny and Nahkla sulfides (pyrite + metal‐deficient monoclinic‐type pyrrhotite). It indicates strongly reducing crystallization conditions (close to IW), several log units below the fO₂ conditions inferred from chromites compositions and accepted for Chassignites (FMQ‐1 log unit). It is proposed that reduction in sulfides into base and precious metal alloys is operated via sulfur degassing, which is supported by the highly resorbed and denticulated shape of sulfide blebs and their spongy textures. Shock‐related S degassing may be responsible for considerable damages in magmatic sulfide structures and sulfide assemblages, with concomitant loss of magnetic properties as documented in some other Martian meteorites.     

Mineral and chemical composition of the new iron meteorite Javorje from Slovenia

Abstract– The single‐piece iron meteorite Javorje, with a mass of 4920 g, is the heaviest and largest meteorite found in the territory of Slovenia. The meteorite Javorje is a medium octahedrite with kamacite bandwidth of 0.85 ± 0.26 mm. The bulk composition of Ni (7.83 wt%), Co (0.48 wt%) and trace elements Ga (25 μg/g), Ge (47 μg/g), Ir (7.6 μg/g), As (5.8 μg/g), Au (0.47 μg/g), and Pt (13.4 μg/g) indicates that the meteorite Javorje belongs to the chemical group IIIAB. Mineral and bulk chemical compositions are consistent with other reported group IIIAB meteorites. The presence of numerous rhabdites, carlsbergite, sparse troilite, and chromite and abundance of daubréelites are in accordance with low‐Ni and low‐P IIIAB iron meteorites. The severely weathered surface and secondary weathering products in the interior of the meteorite suggest its high terrestrial age.     

Magmatic inclusions and felsic clasts in the Dar al Gani 319 polymict ureilite

Abstract— Magmatic inclusions occur in type II ureilite clasts (olivine‐orthopyroxene‐augite assemblages with essentially no carbon) and in a large isolated plagioclase clast in the Dar al Gani (DaG) 319 polymict ureilite. Type I ureilite clasts (olivine‐pigeonite assemblages with carbon), as well as other lithic and mineral clasts in this meteorite, are described in Ikeda et al.(2000). The magmatic inclusions in the type II ureilite clasts consist mainly of magnesian augite and glass. They metastably crystallized euhedral pyroxenes, resulting in feldspar component‐enriched glass. On the other hand, the magmatic inclusions in the large plagioclase clast consist mainly of pyroxene and plagioclase, with a mesostasis. They crystallized with a composition along the cotectic line between the pyroxene and plagioclase liquidus fields. DaG 319 also contains felsic lithic clasts that represent various types of igneous lithologies. These are the rare components not found in the common monomict ureilites. Porphyritic felsic clasts, the main type, contain phenocrysts of plagioclase and pyroxene, and their groundmass consists mainly of plagioclase, pyroxene, and minor phosphate, ilmenite, chromite, and/or glass. Crystallization of these porphyritic clasts took place along the cotectic line between the pyroxene and plagioclase fields. Pilotaxitic felsic clasts crystallized plagioclase laths and minor interstitial pyroxene under metastable conditions, and the mesostasis is extremely enriched in plagioclase component in spite of the ubiquitous crystallization of plagioclase laths in the clasts. We suggest that there are two crystallization trends, pyroxene‐metal and pyroxene‐plagioclase trends, for the magmatic inclusions and felsic lithic clasts in DaG 319. The pyroxene‐metal crystallization trend corresponds to the magmatic inclusions in the type II ureilite clasts and the pilotaxitic felsic clasts, where crystallization took place under reducing and metastable conditions, suppressing precipitation of plagioclase. The pyroxene‐plagioclase crystallization trend corresponds to the magmatic inclusions in the isolated plagioclase clast and the porphyritic felsic clasts. This trend developed under oxidizing conditions in magma chambers within the ureilite parent body. The felsic clasts may have formed mainly from albite component‐rich silicate melts produced by fractional partial melting of chondritic precursors. The common monomict ureilites, type I ureilites, may have formed by the fractional partial melting of alkali‐bearing chondritic precursors. However, type II ureilites may have formed as cumulates from a basaltic melt.     

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.     

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.     

Nitrogen‐isotopic compositions of IIIE iron meteorites

Abstract— The (compositionally) closely related iron meteorite groups IIIE and IIIAB were originally separated based on differences in kamacite bandwidth, the presence of carbides only in the IIIE group, and marginally resolvable differences on the Ga‐Ni and Ge‐Ni diagrams. A total of six IIIE iron meteorites have been analyzed for C and N using secondary ion mass spectrometry, and three of these have also been analyzed for N, Ne, and Ar by stepped combustion. We show that these groups cannot be resolved on the basis of N abundances or isotopic compositions but that they are marginally different in C‐isotopic composition and nitride occurrence. Cosmic‐ray exposure age distributions of the IIIE and IIIAB iron meteorites seem to be significantly different. There is a significant N‐isotopic range among the IIIE iron meteorites. A negative correlation between δ15N and N concentration suggests that the increase in s?15N resulted from diffusional loss of N.