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All sourcesNASA NTRSDOE OSTI
NASA NTRS2005

The nakhlite meteorites: Augite-rich igneous rocks from Mars

The seven nakhlite meteorites are augite-rich igneous rocks that formed in flows or shallow intrusions of basaltic magma on Mars. They consist of euhedral to subhedral crystals of augite and olivine (to 1 cm long) in fine-grained mesostases. The augite crystals have homogeneous cores of Mg' = 63% and rims that are normally zoned to iron enrichment. The core-rim zoning is cut by iron-enriched zones along fractures and is replaced locally by ferroan low-Ca pyroxene. The core compositions of the olivines vary inversely with the steepness of their rim zoning - sharp rim zoning goes with the most magnesian cores (Mg' = 42%), homogeneous olivines are the most ferroan. The olivine and augite crystals contain multiphase inclusions representing trapped magma. Among the olivine and augite crystals is mesostasis, composed principally of plagioclase and/or glass, with euhedra of titanomagnetite and many minor minerals. Olivine and mesostasis glass are partially replaced by veinlets and patches of iddingsite, a mixture of smectite clays, iron oxy-hydroxides and carbonate minerals. In the mesostasis are rare patches of a salt alteration assemblage: halite, siderite, and anhydrite/ gypsum. The nakhlites are little shocked, but have been affected chemically and biologically by their residence on Earth. Differences among the chemical compositions of the nakhlites can be ascribed mostly to different proportions of augite, olivine, and mesostasis. Compared to common basalts, they are rich in Ca, strongly depleted in Al, and enriched in magmaphile (incompatible) elements, including the LREE. Nakhlites contain little pre-terrestrial organic matter. Oxygen isotope ratios are not terrestrial, and are different in anhydrous silicates and in iddingsite. The alteration assemblages all have heavy oxygen and heavy carbon, while D/H values are extreme and scattered. Igneous sulfur had a solar-system isotopic ratio, but in most minerals was altered to higher and lower values. High precision analyses show mass-independent fractionations of S isotopes. Nitrogen and noble gases are complex and represent three components: two mantle sources (Chas-E and Chas-S), and fractionated Martian atmosphere. The nakhlites are igneous cumulate rocks, formed from basaltic magma at approx.1.3 Ga, containing excess crystals over what would form from pure magma. After accumulation of their augite and olivine crystals, they were affected (to various degrees) by crystallization of the magma, element diffusion among minerals and magma, chemical reactions among minerals and magma, magma movement among the crystals, and post-igneous chemical equilibration. The extent of these modifications varies, from least to greatest, in the order: MIL03346, NWA817, Y000593, Nakhla = Governador Valadares, Lafayette, and NWA998. Chemical, isotopic, and chronologic data confirm that the nakhlites formed on Mars, most likely in thick lava flows or shallow intrusions. Their crystallization ages, referenced to crater count chronologies for Mars, suggest that the nakhlites formed on the large volcanic constructs of Tharsis, Elysium, or Syrtis Major. The nakhlites were suffused with liquid water, probably at approx.620 ma. This water dissolved olivine and mesostasis glass, and deposited iddingsite and salt minerals in their places. The nakhlites were ejected from Mars at approx.10.75Ma by an asteroid impact and fell to Earth within the last 10,000 years. Although the nakhlites are enriched in incompatible elements, their source mantle was strongly depleted. This depletion event was ancient, as the nakhlites source mantle was fractionated while short-lived radionuclides (e.g., t(sub 1/2 = 9 my) were still active. This differentiation event may have been core formation coupled with a magma ocean, as is inferred for the moon.

Treiman, Allan H.↗
NASA NTRS2006

History of Metal Veins in Acapulcoite-Lodranite Clan Meteorite GRA 95209

Graves Nunataks (GRA) 95209 has been hailed as the missing link of core formation processes in the acapulcoitelodranite parent asteroid because of the presence of a complex cm-scale metal vein network. Because the apparent liquid temperature of the metal vein (approximately 1500 C) is higher than inferred for the metamorphic grade of the meteorite, questions regarding the vein s original composition, temperature, and mechanism of emplacement have arisen. We have determined trace siderophile element compositions of metals in veins and surrounding matrix in an effort to clarify matters. We analyzed metals in GRA 95209 in a portion of thick metal vein and adjacent metal-rich (30-40 modal%), sulfide poor (less than 1%) matrix by EPMA and LA-ICP-MS for major and trace siderophile elements using methods described by [3]. We also examined metals from a metal-poor (approximately 15 modal%) and relatively sulfide-rich (2-5 modal%) region of the sample. Kamacite is the dominant metal phase in all portions of the sample. In comparison to matrix metal, vein metal contains more schreibersite and less tetrataenite, and is less commonly associated with Fe,Mn,Mg-bearing phosphates and graphite. Vein kamacite contains higher Co, P, and Cr and lower Cu and Ge. These minor variations aside, all metal types in GRA 95209 are fairly homogeneous in terms of their levels of enrichment of compatible siderophile elements (e.g. Pt, Ir, Os) relative to incompatible siderophile elements (e.g. As, Pd, Au), consistent with the loss of metal-sulfide partial melt that characterizes much of the clan. Whatever compositional differences between matrix and vein metal that may have originally existed, they have since largely co-equilibrated to similar restitic trace element compositions. We agree with [2] that metal veins, in their present state, do not represent a liquid composition. The original vein liquid was much more S-rich and emplaced at correspondingly lower liquid temperatures. Much of the Fe,Ni component solidified in cm scale conduits while S-rich melts were expelled and continued to migrate by percolation. The higher troilite content in metal poor regions of the sample results mostly from trapping of a small portion of these melts. The troilite is not remnant primary sulfide. Strong depletions of W, Mo, and especially Ga (greater than 50%, greater than 60%, and greater than 90% depletion, respectively) in metals of the metalpoor GRA 95209 lithology are localized at scales of 10-100 micrometers in the vicinity of graphite spherules. These depletions must have occurred below the temperatures at which cm-scale equilibration occurred, and future work will seek to determine their cause.

Herrin, J. S.↗
NASA NTRS2007

Accretion, Differentiation, and Impact Processes on the Ureilite Parent Body

Ureilites are primitive ultramafic achondrites composed largely of olivine and pigeonite, with minor augite, orthopyroxene, carbon, sulphide and metal. They represent very early material in the history of the Solar System and (in common with lodranites and acapulcoites) form a bridge between undifferentiated chondrites and fully differentiated asteroidal bodies. They show an intriguing mixture of chemical characteristics, some of which are considered to be nebula-derived (e.g. variations in Delta(sup 17)O and mg#) whereas others have been imposed by asteroidal differentiation (e.g. core formation, silicate partial melting, removal of basalt).

Downes, Hilary↗
NASA NTRS2005

The Effect of Metal Composition on Fe-Ni Partition Behavior between Olivine and FeNi-Metal, FeNi-Carbide, FeNi-Sulfide at Elevated Pressure

Metal-olivine Fe-Ni exchange distribution coefficients were determined at 1500 C over the pressure range of 1 to 9 GPa for solid and liquid alloy compositions. The metal alloy composition was varied with respect to the Fe/Ni ratio and the amount of dissolved carbon and sulfur. The Fe/Ni ratio of the metal phase exercises an important control on the abundance of Ni in the olivine. The Ni abundance in the olivine decreases as the Fe/Ni ratio of the coexisting metal increases. The presence of carbon (up to approx. 3.5 wt.%) and sulfur (up to approx. 7.5 wt.%) in solution in the liquid Fe-Ni-metal phase has a minor effect on the partitioning of Fe and Ni between metal and olivine phases. No pressure dependence of the Fe-Ni-metal-olivine exchange behavior in carbon- and sulfur-free and carbon- and sulfur-containing systems was found within the investigated pressure range. To match the Ni abundance in terrestrial mantle olivine, assuming an equilibrium metal-olivine distribution, a sub-chondritic Fe/Ni-metal ratio that is a factor of 17 to 27 lower than the Fe/Ni ratios in estimated Earth core compositions would be required, implying higher Fe concentrations in the core forming metal phase. A simple metal-olivine equilibrium distribution does not seem to be feasible to explain the Ni abundances in the Earth's mantle. An equilibrium between metal and olivine does not exercise a control on the problem of Ni overabundance in the Earth's mantle. The experimental results do not contradict the presence of a magma ocean at the time of terrestrial core formation, if olivine was present in only minor amounts at the time of metal segregation.

Holzheid, Astrid↗
NASA NTRS2008

Duration of a Magma Ocean and Subsequent Mantle Overturn in Mars: Evidence from Nakhlites

It is now generally accepted that the heat produced by accretion, short-lived radioactive elements such as Al-26, and gravitational energy from core formation was sufficient to at least partially melt the silicate portions of terrestrial planets resulting in a global-scale magma ocean. More particularly, in Mars, the geochemical signatures displayed by shergottites, are likely inherited from the crystallization of this magma ocean. Using the short-lived chronometer Sm-146 - Nd-142 (t(sup 1/2) = 103 Myr), the duration of the Martian magma ocean (MMO) has been evaluated to being less than 40 Myr, while recent and more precise ND-142/ND-144 data were used to evaluate the longevity of the MMO to approximately 100 Myr after the solar system formation. In addition, it has been proposed that the end of the crystallization of the MMO may have triggered a mantle overturn, as a result of a density gradient in the cumulate layers crystallized at different levels. Dating the mantle overturn could hence provide additional constraint on the duration of the MMO. Among SNC meteorites, nakhlites are characterized by high epsilon W-182 of approximately +3 and an epsilon Nd-142 similar to depleted shergottites of +0.6-0.9. It has hence been proposed that the source of nakhlites was established very early in Mars history (approximately 8-10 Myr). However, the times recorded in HF-182-W-182 isotope system, i.e. when 182Hf became effectively extinct (approximately 50 Myr after solar system formation) are less than closure times recorded in the Sm-146-Nd-142 isotope system (with a full coverage of approximately 500 Myr after solar system formation). This could result in decoupling between the present-day measured epsilon W-182 and epsilon Nd-142 as the SM-146 may have recorded later differentiation events in epsilon ND-142 not observed in epsilon W-182 values. With these potential complexities in short-lived chronological data for SNC's in mind, new Hf-176/Hf-177, Nd-143/Nd-144 and Nd-142/Nd-144 were obtained for three nakhlites (Nakhla, MIL03346 and Yamato000593). These new data are combined with previous epsilon W-182 data, to investigate potential discrepancies between the Hf-182-W-182 and Sm-146-Nd-142 systematics, and the relationship between the source of nakhlites and a crystallizing magma ocean

Debaille, V.↗
NASA NTRS2006

Depletion of Vandium in Planetary Mantles: Controlled by Metal, Oxide, or Silicate?

Vanadium concentrations in planetary mantles can provide information about the conditions during early accretion and differentiation. Because V is a slightly siderophile element, it is usually assumed that any depletion would be due to core formation and metal-silicate equilibrium. However, V is typically more compatible in phases such as spinel, magnesiowuestite and garnet. Fractionation of all of these phases would cause depletions more marked than those from metal. In this paper consideration of depletions due to metal, oxide and silicate are critically evaluated.

Righter, Kevin↗
NASA NTRS2009

Constraining the Depth of a Martian Magma Ocean through Metal-Silicate Partitioning Experiments: The Role of Different Datasets and the Range of Pressure and Temperature Conditions

Mars accretion is known to be fast compared to Earth. Basaltic samples provide a probe into the interior and allow reconstruction of siderophile element contents of the mantle. These estimates can be used to estimate conditions of core formation, as for Earth. Although many assume that Mars went through a magma ocean stage, and possibly even complete melting, the siderophile element content of Mars mantle is consistent with relatively low pressure and temperature (PT) conditions, implying only shallow melting, near 7 GPa and 2073 K. This is a pressure range where some have proposed a change in siderophile element partitioning behavior. We will examine the databases used for parameterization and split them into a low and higher pressure regime to see if the methods used to reach this conclusion agree for the two sets of data.

Righter, K.↗
NASA NTRS2009

Seeing the Missing Half

The Moon is our closest planetary neighbor and the only extraterrestrial body to which humans have traveled, yet many questions about its origin and early history remain unanswered. Four papers published in this issue by scientific teams of the Japanese SELENE (Kaguya) mission offer a new global view of the Moon that helps to elucidate how the Moon evolved to its present state. The Moon is lopsided: Its visible nearside (tidally locked to face the Earth) is covered with smooth, dark volcanic mare, whereas the farside mainly consists of more heavily cratered, bright highland material. The differences in crustal thickness and density, apparent surface age, composition, and volcanic activity between the two sides are variously ascribed to external causes (such as a giant impact) or to internal causes (such as core formation, mantle convection, and crustal differentiation). The key to resolving these questions will be better data.

Neumann, Gregory A.↗
NASA NTRS2012

Experimental Study of the Partitioning of Siderophile Elements in a Crystallizing Lunar Magma Ocean

The distributions of trace elements between the lunar interior and pristine crustal rocks were controlled by the composition of starting materials, lunar core formation, and crystallization of the lunar magma ocean (LMO) [1]. This study focuses on the partitioning of highly siderophile elements (HSE) including Re, Os, Ir, Ru, Pt, Rh, Pd and Au as well as the moderately siderophile elements Mo and W, and the lithophile elements of Hf and Sr. Our experiments also include Ga, which can be slightly siderophile, but is mostly considered to be chalcophile. Partitioning of these elements is not well known at the conditions of a crystallizing LMO. Previous studies of HSE partitioning in silicate systems have yielded highly variable results for differing oxygen fugacity (fO2) and pressure [2-4]. For example, under certain conditions Pt is compatible in clinopy-roxene [2] and Rh and Ru are compatible in olivine [3]. The silicate compositions used for these experiments were nominally basaltic. Ruthenium, Rh, and Pd are incompatible in plagioclase under these conditions[4]. However, this latter study was done at extremely oxidizing conditions and at atmospheric pressure, possibly limiting the applicability for consideration of conditions of a crystallizing LMO. In this study we address the effects of pressure and oxygen fugacity on the crystal/liquid partition coefficients of these trace elements. We are especially interested in the plagioclase/melt partition coefficients so that it may be possible to use reverse modeling to constrain the concentrations of these elements in the lunar mantle through their abundances in pristine crustal rocks.

Galenas, M.↗
NASA NTRS2013

Chemical Composition of Four Shergottites from Northwest Africa (NWA 2800, NWA, 5214, NWA 5990, NWA 6342)

Shergottites represent the majority of recovered Martian meteorites. As basic igneous rocks, they formed from magmas that were emplaced in the Martian crust [1]. Due to the low ambient pressure of the Martian atmosphere, subaerial lavas and shallow magma chambers are expected to outgas volatile metals (e.g., Cd, Te, Re, Bi) [2]. The planetary abundances of the volatile siderophile and chalcophile elements are important at establishing the depth of core formation for Mars, and must be known as a baseline for understanding volcanic outgassing on Mars, particularly the large enrichments of S and Cl observed in modern Martian soils [3]. There is little data on volatile siderophile and chalcophile elements from Martian meteorites, excluding a few well-analyzed samples [2]. Further, a large number of shergottites being recovered from North West Africa are in need of chemical analysis. All of the shergottites are in need of state-of-the art analysis for such ratios as Ge/Si and Ga/Al, which can now be accomplished by LA-ICP-MS [2].

Yang, S.↗
NASA NTRS2014

The Ancient Martian Climate System

Today Mars is a cold, dry, desert planet. The atmosphere is thin and liquid water is not stable. But there is evidence that very early in its history it was warmer and wetter. Since Mariner 9 first detected fluvial features on its ancient terrains researchers have been trying to understand what climatic conditions could have permitted liquid water to flow on the surface. Though the evidence is compelling, the problem is not yet solved. The main issue is coping with the faint young sun. During the period when warmer conditions prevailed 3.5-3.8 Gy the sun's luminosity was approximately 25% less than it is today. How can we explain the presence of liquid water on the surface of Mars under such conditions? A similar problem exists for Earth, which would have frozen over under a faint sun even though the evidence suggests otherwise. Attempts to solve the "Faint Young Sun Paradox" rely on greenhouse warming from an atmosphere with a different mass and composition than we see today. This is true for both Mars and Earth. However, it is not a straightforward solution. Any greenhouse theory must (a) produce the warming and rainfall needed, (b) have a plausible source for the gases required, (c) be sustainable, and (d) explain how the atmosphere evolved to its present state. These are challenging requirements and judging from the literature they have yet to be met. In this talk I will review the large and growing body of work on the early Mars climate system. I will take a holistic approach that involves many disciplines since our goal is to present an integrated view that touches on each of the requirements listed in the preceding paragraph. I will begin with the observational evidence, which comes from the geology, mineralogy, and isotopic data. Each of the data sets presents a consistent picture of a warmer and wetter past with a thicker atmosphere. How much warmer and wetter and how much thicker is a matter of debate, but conditions then were certainly different than what they are today. I will then discuss the origin and evolution of the early atmosphere from accretion and core formation to the end of the late heavy bombardment, including estimates of the volatile inventory, outgassing history, and potential escape mechanisms. This sets the stage for a comprehensive look at the climate system of early Mars and the attempts to solve the faint young sun problem. I will review the basic physics involved and then step through the different ideas highlighting their strengths and weaknesses. I will then conclude with a summary and a discussion of potentially promising avenues of future research

Mars↗
NASA NTRS2015

Origin of Volatiles in Earth: Indigenous Versus Exogenous Sources Based on Highly Siderophile, Volatile Siderophile, and Light Volatile Elements

Origin of Earth's volatiles has traditionally been ascribed to late accretion of material after major differentiation events - chondrites, comets, ice or other exogenous sources. A competing theory is that the Earth accreted its volatiles as it was built, thus water and other building blocks were present early and during differentiation and core formation (indigenous). Here we discuss geochemical evidence from three groups of elements that suggests Earth's volatiles were acquired during accretion and did not require additional sources after differentiation.

Righter, K.↗
NASA NTRS2016

The Germanium Dichotomy in Martian Meteorites

Germanium is a moderately volatile and siderophile element that follows silicon in its compatibility during partial melting of planetary mantles. Despite its obvious usefulness in planetary geochemistry germanium is not analyzed routinely, with there being only three prior studies reporting germanium abundances in Martian meteorites. The broad range (1-3 ppm) observed in Martian igneous rocks is in stark contrast to the narrow range of germanium observed in terrestrial basalts (1.5 plus or minus 0.1 ppm). The germanium data from these studies indicates that nakhlites contain 2-3 ppm germanium, while shergottites contain approximately 1 ppm germanium, a dichotomy with important implications for core formation models. There have been no reliable germanium abundances on chassignites. The ancient meteoritic breccia, NWA 7533 (and paired meteorites) contains numerous clasts, some pristine and some impact melt rocks, that are being studied individually. Because germanium is depleted in the Martian crust relative to chondritic impactors, it has proven useful as an indicator of meteoritic contamination of impact melt clasts in NWA 7533. The germanium/silicon ratio can be applied to minerals that might not partition nickel and iridium, like feldspars. We report germanium in minerals from the 3 known chassignites, 2 nakhlites and 5 shergottites by LAICP- MS using a method optimized for precise germanium analysis.

Humayun, M.↗
NASA NTRS2020

Activity Coefficients of Siderophile Elements in Fe-Si Liquids at High Pressure

Metallic core formation in differentiated bodies in the inner solar system can takeplace between low pressures (near 1 bar) to much higher pressures (up to 100 GPa). Mostthermodynamic models of metal-silicate equilibria utilize activity coefficients for metallic tracersin Fe liquids, nearly all of which have been carried out at low pressures. This study focuses onthe effect of pressure on activity coefficients for Au, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb inliquid Fe-Si alloys. From a series of experiments at 10 GPa, 2373 K containing variable Sicontent in a metallic liquid we have derived epsilon interaction parametersin FeSi liquids (εMSi). Comparison of 1 GPa and 10 GPa data shows no difference except for Nb. Epsilonparameters derived from low pressure experiments can thus be used to calculate activitycoefficients for application to higher pressure processes (at least to 10 GPa).

K Righter↗
NASA NTRS2022

The Abundances of F, Cl, and H2O in 4Vesta from Eucrites

The abundance and distribution of magmatic volatiles (i.e., H, C, N, F, S, and Cl) within the silicate portion of a differentiated planetary body has important consequences on its thermochemical evolution. However, the abundances of magmatic volatiles within differentiated bodies are difficult to quantify, and they are often depleted by varying degrees relative to CI chondrites. The mechanisms of depletion are not well constrained and could relate to intrinsic volatile depletion of the building blocks that formed the bodies, high temperature processes that result from accretion, post-accretion loss through parent body geological processes and large-scale impacts, and/or redistribution within a parent body through processes like core formation [1–4]. In the present study, we aim to constrain the abundances of F, Cl, and H2O in eucrites to better understand the magnitude of volatile depletion on 4Vesta. To accomplish this objective, we report electron microprobe analyses of apatite from seven unbrecciated, non-cumulate eucrites (i.e., CMS 04049,GRA 98098, LEW 88010, MAC 02522, MAC 041169,QUE 94484, and QUE 97053) and two monomict, non-cumulate eucrites (i.e., Berthoud and Stannern). In combination with previously published data on eucrite-hosted apatite, we determine Cl/F and H2O/F ratios in bulk rock eucrites through the application of apatite-based melt hygrometry and chlorometry [e.g., 5–7].Additionally, we estimate the bulk rock abundances of F in six non-cumulate eucrites (i.e., GRA 98098, MAC041169, PCA 91078, QUE 97053, Stannern, and Berthoud), which we combine with previously published bulk rock F data on non-cumulate eucrites[8] to constrain the abundances of F, Cl, and H2O in 4Vesta using appropriately paired volatile/refractory element ratios for F, followed by Cl/F and H2O/F ratios for Cl and H2O, respectively.

F M McCubbin↗
NASA NTRSDate not supplied

Effect of Pressure on Trace Element Activity Coefficients in Metal-Silicate Systems

The partitioning of trace elements between metal and silicate melts serves as the foundation for understanding the differentiation of a planetary body into a metallic core and silicate mantle. Element activity influences metal-silicate partitioning behavior. Activity coefficients are directly dependent on composition and temperature, and can be indirectly dependent on oxygen fugacity and pressure. Distinguishing the effect of pressure from other variables on the activity coefficients and partitioning is important for understanding the chemical evolution of different planetary bodies during differentiation. In this study, we investigated the influence of pressure on the activity coefficients of Cu, Mo, Pd, Pt, As, Sb, and Bi in Fe-Si metallic liquids. All of these elements exhibit moderate to high activity coefficients in Fe-Si liquids at low pressure, which significantly controls their metal-silicate partitioning behavior. Identifying whether this strong dependence persists at higher pressures is critical to modeling and understanding the chemical consequences of core formation. New experiments at 10 GPa were used to derive activity coefficients for these metals which can be compared to activity coefficients determined at 1 GPa. Experiments were conducted at 10 GPa and 2373K using a 10/5 assembly in the 880-ton multi-anvil press at NASA Johnson Space Center. The standard 10/5 COMPRES assembly was slightly modified to accommodate a sample capsule machined from single-crystal MgO that minimizes melt percolation out of the sample volume during the experiment. Experiment starting materials were comprised of 70 wt.% Knippa basalt and 30 wt.% metal. The metal mixture (~85 wt.% Fe) was created by adding the elements of interest (Cu, Mo, Pd, Pt, As, Sb, Bi) to Fe metal powder. Varied amounts of Si metal (0-10 wt.% Si) were added to the metal-silicate mixtures to generate a systematic series of starting materials. For each element, an epsilon interaction parameter in Fe-Si liquid was derived from the results of our 0-10 wt.% Si metal series. To investigate whether pressure influences the trace element activity coefficients in the 1-10 GPa pressure range, we compared our results at 10 GPa to those at 1-4 GPa [1-3]. Our results can also be directly compared to interaction parameters for Au, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb previously determined at 10 GPa and 2373K following the same methods [4]. Combined, this suite of interaction parameters will directly inform metal-silicate partitioning between 1 and 10 GPa, and assess whether these values can be extrapolated to modeling differentiation processes at pressures >10 GPa.

Kelsey Prissel↗
NASA NTRSDate not supplied

Effect of Pressure and Oxidation State on Pnictogen Metal-Silicate Partitioning

The partitioning of trace elements between metal and silicate melts serves as the foundation for understanding the differentiation of a planetary body into a metallic core and silicate mantle. Element activity influences metal-silicate partitioning behavior. Activity coefficients are directly dependent on composition and temperature, and can be indirectly dependent on oxygen fugacity and pressure. Distinguishing the effect of pressure from other variables on the activity coefficients and partitioning is important for understanding the chemical evolution of different planetary bodies during differentiation. In this study, we investigated the influence of pressure on the activity coefficients of Cu, Mo, Pd, Pt, As, Sb, and Bi in Fe-Si metallic liquids. All of these elements exhibit moderate to high activity coefficients in Fe-Si liquids at low pressure, which significantly controls their metal-silicate partitioning behavior. Identifying whether this strong dependence persists at higher pressures is critical to modeling and understanding the chemical consequences of core formation. New experiments at 10 GPa were used to derive activity coefficients for these metals which can be compared to activity coefficients determined at 1 GPa. Experiments were conducted at 10 GPa and 2373K using a 10/5 assembly in the 880-ton multi anvil press at NASA Johnson Space Center. The standard 10/5 COMPRES assembly was slightly modified to accommodate a sample capsule machined from single-crystal MgO that minimizes melt percolation out of the sample volume during the experiment. Experiment starting materials were comprised of 70 wt.% Knippa basalt and 30 wt.% metal. The metal mixture (~85 wt.% Fe) was created by adding the elements of interest (Cu, Mo, Pd, Pt, As, Sb, Bi) to Fe metal powder. Varied amounts of Si metal (0-10 wt.% Si) were added to the metal-silicate mixtures to generate a systematic series of starting materials. For each element, an epsilon interaction parameter in Fe-Si liquid was derived from the results of our 0-10 wt.% Si metal series. To investigate whether pressure influences the trace element activity coefficients in the 1-10 GPa pressure range, we compared our results at 10 GPa to those at 1-4 GPa [1-3]. Our results can also be directly compared to interaction parameters for Au, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb previously determined at 10 GPa and 2373K following the same methods [4]. Combined, this suite of interaction parameters will directly inform metal- silicate partitioning between 1 and 10 GPa, and assess whether these values can be extrapolated to modeling differentiation processes at pressures >10 GPa. [1] Righter et al. (2018) GCA 232, 101-123 [2] Righter et al. (2019) MaPS 54, 1379-1394 [3] Steenstra et al. (2020) Icarus, 335, 113391 [4] Righter et al. (2020) Geochem. Persp. Let. 15, 44-49

Kelsey Prissel↗
DOE OSTI2023

Hard–Soft Core–Shell Architecture Formation from Cubic Cobalt Ferrite Nanoparticles

Cubic bi-magnetic hard–soft core–shell nanoarchitectures were prepared starting from cobalt ferrite nanoparticles, prevalently with cubic shape, as seeds to grow a manganese ferrite shell. The combined use of direct (nanoscale chemical mapping via STEM-EDX) and indirect (DC magnetometry) tools was adopted to verify the formation of the heterostructures at the nanoscale and bulk level, respectively. The results showed the obtainment of core–shell NPs (CoFe 2 O 4 @MnFe 2 O 4 ) with a thin shell (heterogenous nucleation). In addition, manganese ferrite was found to homogeneously nucleate to form a secondary nanoparticle population (homogenous nucleation). This study shed light on the competitive formation mechanism of homogenous and heterogenous nucleation, suggesting the existence of a critical size, beyond which, phase separation occurs and seeds are no longer available in the reaction medium for heterogenous nucleation. These findings may allow one to tailor the synthesis process in order to achieve better control of the materials’ features affecting the magnetic behaviour, and consequently, the performances as heat mediators or components for data storage devices.

36 MATERIALS SCIENCE↗