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NASA NTRS2009

Controls on Highly Siderophile Element Concentrations in Martian Basalt: Sulfide Saturation and Under-Saturation

Highly siderophile elements (HSE; Re, Au and the platinum group elements) in shergottites exhibit a wide range from very high, similar to the terrestrial mantle, to very low, similar to sulfide saturated mid ocean ridge basalt (e.g., [1]). This large range has been difficult to explain without good constraints on sulfide saturation or under-saturation [2]. A new model for prediction of sulfide saturation places new constraints on this problem [3]. Shergottite data: For primitive shergottites, pressure and temperature estimates are between 1.2-1.5 GPa, and 1350-1470 C [4]. The range of oxygen fugacities is from FMQ-2 to IW, where the amount of Fe2O3 is low and thus does not have a significant effect on the S saturation values. Finally, the bulk compositions of shergottites have been reported in many recent studies (e.g., [5]). All of this information will be used to test whether shergottites are sulfide saturated [3]. Modeling values and results: The database for HSE partition coefficients has been growing with many new data for silicates and oxides [6-8] to complement a large sulfide database [9- 11]. Combining these data with simple batch melting models allows HSE contents of mantle melts to be estimated for sulfide-bearing vs. sulfide-free mantle. Combining such models with fractional crystallization modeling (e.g., [12]) allows HSE contents of more evolved liquids to be modeled. Most primitive shergottites have high HSE contents (and low S contents) that can be explained by sulfide under-saturated melting of the mantle. An exception is Dhofar 019 which has high S contents and very low HSE contents suggesting sulfide saturation. Most evolved basaltic shergottites have lower S contents than saturation, and intermediate HSE contents that can be explained by olivine, pyroxene, and chromite fractionation. An exception is EET A79001 lithology B, which has very low HSE contents and S contents higher than sulfide saturation values . evidence for sulfide saturation during late fractional crystallization. These results show that shergottite HSE contents are controlled by silicates, oxides, and sulfides. In addition, the mantle producing the most primitive shergottites did not contain near chondritic relative ratios of the HSEs like the terrestrial mantle, and did not experience a late chondritic veneer.

Righter, Kevin↗

NASA NTRS2010

Conditions of Core Formation in the Early Earth: Single Stage or Heterogeneous Accretion?

Since approx.1990 high pressure and temperature (PT) experiments on metal-silicate systems have showed that partition coefficients [D(met/sil)] for siderophile (iron-loving) elements are much different than those measured at low PT conditions [1,2]. The high PT data have been used to argue for a magma ocean during growth of the early Earth [3,4]. In the ensuing decades there have been hundreds of new experiments carried out and published on a wide range of siderophile elements (> 80 experiments published for Ni, Co, Mo, W, P, Mn, V, Cr, Ga, Cu and Pd). At the same time several different models have been advanced to explain the siderophile elements in Earth's mantle: a) shallow depth magma ocean 25-30 GPa [3,5]; b) deep magma ocean; up to 50 GPa [6,7], and c) early reduced and later oxidized magma ocean [8,9]. Some studies have drawn conclusions based on a small subset of siderophile elements, or a set of elements that provides little leverage on the big picture (like slightly siderophile elements), and no single study has attempted to quantitatively explain more than 5 elements at a time. The purpose of this abstract is to identify issues that have lead to a difference in interpretation, and to present updated predictive expressions based on new experimental data. The resulting expressions will be applied to the siderophile element depletions in Earth's upper mantle.

Righter, Kevin↗

NASA NTRS2012

Pt, Au, Pd and Ru Partitioning Between Mineral and Silicate Melts: The Role of Metal Nanonuggets

The partition coefficients of Pt and other Pt Group Elements (PGE) between metal and silicate D(sub Metal-Silicate) and also between silicate minerals and silicate melts D(sub Metal-Silicate) are among the most challenging coefficients to obtain precisely. The PGE are highly siderophile elements (HSE) with D(sub Metal-Silicate) >10(exp 3) due to the fact that their concentrations in silicates are very low (ppb to ppt range). Therefore, the analytical difficulty is increased by the possible presence of HSE-rich-nuggets in reduced silicate melts during experiments). These tiny HSE nuggets complicate the interpretation of measured HSE concentrations. If the HSE micro-nuggets are just sample artifacts, then their contributions should be removed before calculations of the final concentration. On the other hand, if they are produced during the quench, then they should be included in the analysis. We still don't understand the mechanism of nugget formation well. Are they formed during the quench by precipitation from precursor species dissolved homogeneously in the melts, or are they precipitated in situ at high temperature due to oversaturation? As these elements are important tracers of early planetary processes such as core formation, it is important to take up this analytical and experimental challenge. In the case of the Earth for example, chondritic relative abundances of the HSE in some mantle xenoliths have led to the concept of the "late veneer" as a source of volatiles (such as water) and siderophiles in the silicate Earth. Silicate crystal/liquid fractionation is responsible for most, if not all, the HSE variation in the martian meteorite suites (SNC) and Pt is the element least affected by these fractionations. Therefore, in terms of reconstructing mantle HSE abundances for Mars, Pt becomes a very important player. In the present study, we have performed high temperature experiments under various redox conditions in order to determine the abundances of Pt, Au, Ru and Pd in minerals (olivine and diopside) and in silicate melts, but also to characterize the sizes, density and chemistry of HSE nuggets when present in the samples.

Malavergne, V.↗

NASA NTRS2012

Metasomatic Control of Water in Garnet and Pyroxene from Kaapvaal Craton Mantle Xenoliths

Fourier transform infrared spectrometry (FTIR) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) were used to determine water, rare earth (REE), lithophile (LILE), and high field strength (HFSE) element contents in garnet and pyroxene from mantle xenoliths, Kaapvaal craton, southern Africa. Water enters these nominally anhydrous minerals as protons bonded to structural oxygen in lattice defects. Pyroxene water contents (150-400 ppm in clinopyroxene; 40-250 ppm in orthopyroxene) correlate with their Al, Fe, Ca and Na and are homogeneous within a mineral grains and a xenolith. Garnets from Jagersfontein are chemically zoned for Cr, Ca, Ti and water contents. Garnets contain 0 to 20 ppm H2 Despite the fast diffusion rate of H in mantle m inerals, the observations above indicate that the water contents of mantle xenolith minerals were not disturbed during kimberlite entrainment and that the measured water data represent mantle values. Trace elements in all minerals show various degrees of light REE and LILE enrichments indicative of minimal to strong metasomatism. Water contents of peridotite minerals from the Kaapvaal lithosphere are not related to the degree of depletion of the peridotites. Instead, metasomatism exerts a clear control on the amount of water of mantle minerals. Xenoliths from each location record specific types of metasomatism with different outcomes for the water contents of mantle minerals. At pressures . 5.5 GPa, highly alkaline melts metasomatized Liqhobong and Kimberley peridotites, and increased the water contents of their olivine, pyroxenes and garnet. At higher pressures, the circulation of ultramafic melts reacting with peridotite resulted in co-variation of Ca, Ti and water at the edge of garnets at Jagersfontein, overall decreasing their water content, and lowered the water content of olivines at Finsch Mine. The calculated water content of these melts varies depending on whether the water content of the peridotite (2 wt% HO. 2O) or individual m inerals (<0.5-13 wt% H2O) are used, and also depend on the mineral-melt water partition coefficients. These metasomatic events are thought to have occurred during the Archean and Proterozoic, meaning that the water contents measured here have been preserved since that time and can be used to investigate viscocity and longevity of cratonic mantle roots.

Peslier, Anne H.↗

NASA NTRS2013

Metal-Silicate Partitioning of Bi, In, and Cd as a Function of Temperature and Melt Composition

The origin of volatile elements in the Earth, Moon and Mars is not known; however, several theories have been proposed based on volatile elements such as In, As, Se, Te and Zn which are in lower concentration in the Earth, Moon, and Mars than in chondrites. Explanations for these low concentrations are based on two contrasting theories for the origin of Earth: equilibrium core formation versus late accretion. One idea is that the volatiles were added during growth of the planets and Moon, and some mobilized into the metallic core while others stayed in the mantle (e.g., [1]). The competing idea is that they were added to the mantles after core formation had completed (e.g., [2]). Testing these ideas involves quantitative modeling which can only be performed after data is obtained on the systematic metal-silicate partitioning behavior of volatile elements with temperature, pressure and melt composition. Until now, such data for Bi, In, and Cd has been lacking. After conducting a series of high pressure, high temperature experiments, the metal-silicate partition coefficients of Bi, In, and Cd as a function of temperature and melt composition can be used to evaluate potential conditions under which terrestrial planets differentiated into core and mantle, and how they acquired volatiles.

Marin, Nicole↗

NASA NTRS2014

Chromium Oxidation State in Planetary Basalts: Oxygen Fugacity Indicator and Critical Variable for Cr-Spinel Stability

Cr is a ubiquitous and relatively abundant minor element in basaltic, planetary magmas. At the reduced oxidation states (<FMQ) of many planetary basalts Cr is present in melts as both divalent and trivalent forms. The ratio of trivalent to divalent Cr present in the melt has many consequences for the stability and Cr concentration of magmatic phases such as spinel, clinopyroxene, and olivine. However, understanding the Cr valence in quenched melts has historically been plagued with analytical issues, and only recently has reliable methodology for quantifying Cr valence in quenched melts been developed. Despite this substantial difficulty, the pioneering works of Hanson and Jones and Berry and O'Neill provided important insights into the oxidation state of Cr in in silicate melts. Here we present a series of 1-bar gas mixing experiments performed with a Fe-rich basaltic melt in which have determined the Cr redox ratio of the melt at over a range of fO2 values by measuring this quantity in olivine with X-ray Absorption Near Edge Spectroscopy (XANES). The measured Cr redox ratio of the olivine phenocrysts can be readily converted to the ratio present in the conjugate melt via the ratio of crystal-liquid partition coefficients for Cr3+ and Cr2+. We have applied these results to modeling Cr spinel stability and Cr redox ratios in a primitive, iron-rich martian basalt.

Bell, A. S.↗

NASA NTRS2015

REE Partitioning in Lunar Minerals

Rare earth elements (REE) are an extremely useful tool in modeling lunar magmatic processes. Here we present the first experimentally derived plagioclase/melt partition coefficients in lunar compositions covering the entire suite of REE. Positive europium anomalies are ubiquitous in the plagioclase-rich rocks of the lunar highlands, and complementary negative Eu anomalies are found in most lunar basalts. These features are taken as evidence of a large-scale differentiation event, with crystallization of a global-scale lunar magma ocean (LMO) resulting in a plagioclase flotation crust and a mafic lunar interior from which mare basalts were subsequently derived. However, the extent of the Eu anomaly in lunar rocks is variable. Fagan and Neal [1] reported highly anorthitic plagioclase grains in lunar impact melt rock 60635,19 that displayed negative Eu anomalies as well as the more usual positive anomalies. Indeed some grains in the sample are reported to display both positive and negative anomalies. Judging from cathodoluminescence images, these anomalies do not appear to be associated with crystal overgrowths or zones.

Rapp, J. F.↗

NASA NTRS2015

The Combined Strength of Thermodynamics and Comparative Planetology: Application of Activity Models to Core Formation in Terrestrial Bodies

Recent models for accretion of terrestrial bodies involve metal-silicate equilibrium as the metallic core formed during growth. Most elements considered are either refractory or well studied elements for which effects of pressure, temperature, oxygen fugacity, and metallic liquid composition are well known. There are a large number of elements that are both siderophile and volatile, whose fate in such models is unknown, largely due to a lack of data at comparable conditions and com-positions (FeNi core with light elements such as S, C, Si, and O). We have focused on Ge, In, As, Sb and determined the effect of Si and C on metal-silicate partitioning, and developed a thermo-dynamic model that allows application of these new data to a wide range of planetary bodies. New experiments: We have previously carried out experiments with FeSi metallic liquid at C-saturated conditions at 1600 and 1800 C [4]. In a new series of experiments we investigate the effect of Si in carbon-free systems at 1600 C for comparison. Experiments were carried out at 1 GPa in MgO capsules using the same basaltic starting composition as in previous studies. The MgO capsule reacts with the silicate melt to form more MgO-rich liquids that have 22-26 wt% MgO. Experimental met-als and silicates were analyzed using a combination of electron microprobe analysis and laser ablation ICP-MS. Results: The new results can be interpreted by considering Ge as an example, in the simple exchange equilibrium Fe + GeO = FeO + Ge, where the equilibrium constant Kd can be examined as a function of Si content of the metal. The slope of lnKd vs. (1-XSi) for this new series allows derivation of the epsilon interaction parameter for each of these four elements and Si (both C-saturated and C-free).All four elements have positive epsilon values, indicating that Si causes a decrease in the partition coefficients; values are 6.6, 6.5, 27.8 and 25.2 for In, Ge, As, and Sb, respectively, at 1 GPa and 1600 C. As an example of how large the effect of Si can be, these epsilon values correspond to activity coefficients (gamma) for As of 0.01 when XSi = 0, and up to gamma = 23 when XSi = 0.2. Combining these new results with previous determinations [5,6] of epsilon parameters for S and C for these elements allows us calculate activity of Ge, In, As, and Sb in Fe-Ni-Si-S-C-O metallic liquids. We apply this new model to sever-al terrestrial bodies such as Earth (Si-rich core), Mars (S-rich core), Moon (S-, C-, and Si-poor core), and Vesta, and examine the resulting core and mantle concentrations of these elements. Mantle concentrations of these four elements are well explained for Earth and Mars in models that call for mid-mantle equilibration between Si-bearing and S-bearing FeNi cores, respectively. Modeling results for the Moon and Vesta will also be presented.

Righter, K.↗

NASA NTRS2016

Evidence for a Heterogeneous Distribution of Water in the Martian Interior

The abundance and distribution of H2O within the terrestrial planets, as well as its timing of delivery, is a topic of vital importance for understanding the chemical and physical evolution of planets and their potential for hosting habitable environments. Analysis of planetary materials from Mars, the Moon, and the eucrite parent body (i.e., asteroid 4Vesta) have confirmed the presence of H2O within their interiors. Moreover, H and N isotopic data from these planetary materials suggests H2O was delivered to the inner solar system very early from a common source, similar in composition to the carbonaceous chondrites. Despite the ubiquity of H2O in the inner Solar System, the only destination with any prospects for past or present habitable environments at this time, outside of the Earth, is Mars. Although the presence of H2O within the martian interior has been confirmed, very little is known regarding its abundance and distribution within the martian interior and how the martian water inventory has changed over time. By combining new analyses of martian apatites within a large number of martian meteorite types with previously published volatile data and recently determined mineral-melt partition coefficients for apatite, we report new insights into the abundance and distribution of volatiles in the martian crust and mantle. Using the subset of samples that did not exhibit crustal contamination, we determined that the enriched shergottite mantle source has 36-73 ppm H2O and the depleted shergottite mantle source has 14-23 ppm H2O. This result is consistent with other observed geochemical differences between enriched and depleted shergottites and supports the idea that there are at least two geochemically distinct reservoirs in the martian mantle. We also estimated the H2O content of the martian crust using the revised mantle H2O abundances and known crust-mantle distributions of incompatible lithophile elements. We determined that the bulk martian crust has approximately 1400 ppm H2O, which is likely distributed toward the martian surface. This crustal water abundance would equate to a global equivalent layer (GEL) of water at a depth of-229 m, which can account for at least some of the surface features on Mars attributed to flowing water and may be sufficient to support the past presence of a shallow sea on Mars' surface.

McCubbin, Francis↗

NASA NTRS2017

Volatile Content of 4-Vesta: Evidence from Unequilibrated Eucrites

Eucrites are a class of basaltic meteorites that, along with the howardites and diogenites, likely derive from the asteroid 4-Vesta. This asteroid is depleted in moderately volatile elements relative to the Earth and carbonaceous chondrites. Extrapolation of this depletion trend predicts that bulk silicate 4-Vesta (BSV) contains at most 250-1000 μg/g H2O, which is approximately a factor of two lower than the H2O content of Earth. To obtain more accurate H2O and F estimates for BSV, we examined four unequilibrated antarctic meteorites, Yamato(Y)-793548, Y-82210, Y-75011, and Y-74450, by EPMA and SIMS. Pyroxenes contain MgO-rich cores and FeO-rich rims, consistent with primary magmatic zoning. Volatile concentrations generally follow patterns expected for growth zoning with lower values in the cores and higher in the rims. These features indicate that thermal metamorphism and other post-crystallization processes did not significantly perturb the volatile contents of these unequilibrated eucrite pyroxenes. We used these data to derive best estimates for the BSV H2O and F content based on experimentally determined pyroxene-melt partition coefficients and models for magma generation on Vesta. In addition, we measured D/H in the early crystallizing pyroxenes and late crystallzing apatites. We find that the D/H of pyroxene and apatite are within error of one another as well as previous measurements of apatite in equilibrated eucrites. These results imply that degassing was minimal or did not fractionate D/H. Degassing may have been limited if eucrites were shallowly emplaced sills or dykes, or the total H2O content of the magmas was too low for vapor saturation. An alternative mechanism for limited D/H fractionation is that degassing did occur, but the H2/H2O of the exsolved vapor was approximately 15:85, as predicted from experiments.

Sarafian, A. R.↗

NASA NTRS2019

Trace Element Abundances of Olivine-Hosted Melt Inclusions in Shergottites Northwest Africa 7397 and Robert Massif 04262

Olivine-hosted melt inclusions (MIs) may retain trapped parent magma compositions as well as record progressive differentiation while magmas crystallize and ascend towards the surface [1,2 and references therein]. Major element compositions of the MIs, especially Fe and Mg, can be affected by post-entrapment re-equilibration with their host olivine [1,2]. Therefore, Fe/Mg ratio correction is required to obtain MI bulk compositions following equilibrium with their host olivine. Partition coefficients of most of the trace elements in olivine are very low (i.e. DOL/melt<0.001). Thus, ratios of trace elements of olivine-hosted MIs are unlikely to be affected by post-entrapment re-equilibration and no correction is necessary [2]. Hence, tracking trace element behavior in MIs may constrain the composition of the parent magma and its evolution yielding insights on magma differentiation of shergottites. However, analyzing MIs for chemical compositions is a challenging task due to their low abundances and small sizes. Using a highly sensitive and precise micro-beam technique is essential to examine olivine-hosted MIs in order to measure trace element abundances. For this purpose, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is an excellent tool due to its wide range of laser spot sizes (1-150 μm), ability to obtain raster analysis (several mm2) and lower detection limits (0.1 ppb) [3].

Ferdous, J.↗

NASA NTRSDate not supplied

Deciphering Extreme Mineral Records; Microstructural Phase Heritage of Shocked Materials

High-pressure minerals such as coesite, stishovite, and reidite are often used as indicators of shock metamorphism. However, high-pressure and high-temperature phases are metastable at ambient conditions and, therefore, often revert to a more energetically favorable phase. During solid-state transformations, the crystallographic orientations of the stable polymorph are controlled by the transformation pathway from the parent. Microstructural orientation analysis using electron backscatter diffraction (EBSD) of the stable phase can reveal systematic intercrystalline orientation relationships (OR) diagnostic of solid-state transformations from these high-pressure or high-temperature polymorph phases (Cayron et al., 2006). Knowledge of polymorph stability fields for a given system can thus be used to infer minimum shock P and/or T conditions that rocks have experienced, which are otherwise unavailable using traditional thermobarometers such as element partition coefficients. Using orientation relationships to infer the former presence of mineral phases has been termed microstructural “phase heritage”, and has successfully been used to probe for evidence of extreme pressures and temperatures resulting from hypervelocity impacts. The reconstruction of polymorphs of ZrSiO4 (zircon, reidite) and ZrO2 (baddeleyite) have further elucidated the behavior of these phases under hypervelocity impact conditions (Timms et al., 2017a; White et al., 2018), and OR analysis of shocked monazite has identified a previously unrecognized tetragonal high-P polymorph (Erickson et al., 2019). Zircon will convert to the low tetragonal polymorph reidite at shock stresses above ~21 GPa. However, upon decompression at temperatures above 1200 °C reidite will revert to zircon (Kusaba et al., 1985). Recrystallized zircon neoblasts encased in impact melt often show systematic misorientation relationships of 90° about <110> indicative of reversion from the reidite (Fig. 1), and preserving cryptic evidence of the high-P history that is often erased by the post shock thermal spike (Cavosie et al., 2016). Microstructural OR analysis of a dissociated zircon corona composed of baddeleyite (monoclinic-ZrO2) has identified the former presence of cubic zirconia within impact melt glass from the Mistastin Lake impact structure, Labrador, CA. Based on stability fields in the ZrO2-SiO2 binary phase diagram, cubic zirconia records thermal conditions in excess of 2370 °C at ambient P, indicating that the Mistastin impact melt is the hottest rock identified on Earth’s surface (Timms et al., 2017b). Shock-deformed monazite (monoclinic La,Ce,ThPO4) containing lamellae comprised of interlocking laths has been identified from the Haughton Dome impact structure, Nunavut, Canada and Nördlinger-Ries Crater, southern Germany. The lath-structured lamellae are composed of four systematic orientation variants, which OR analyses indicate originate from a tetragonal parent whereby the [010]monoclinic aligns with either [100] or [010]tetragonal (Erickson et al., 2019). These results highlight utility of microstructural phase heritage analyses for the identification of unstable high-P or high-T polymorphs that uniquely record the extremely transient shock conditions produced by hypervelocity impacts.

Timmons Erickson↗

NASA NTRSDate not supplied

Mantle Source Mineralogy Inferred from Incompatible Element Ratios in Shergottites

The mineralogy of the martian mantle is a poorly known but vital compositional parameter. In the absence of samples of martian mantle peridotites, the mineralogy has been inferred from bulk composition constrained by a mix of cosmochemical and martian meteoritic constraints. Such a mineralogy reflects the primordial mantle composition, but mantle source regions that differentiated from a magma ocean are not likely to have the same mineralogy as bulk silicate Mars. An alternative approach is to infer source mineralogy of the martian mantle from the analysis of incompatible elements in shergottites. In a recent study, we showed that the general compatibility order of trace lithophile elements in martian mantle is similar to that of MORB mantle, with some exceptions. Compared to MORB mantle, in martian mantle: (1) highly incompatible elements (Th, Nb, Ta and U) are less incompatible relative to La; (2) K is significantly more compatible with respect to other elements; and (3) the HREEs are more compatible. In this study, we calculated effective partition coefficients of trace elements directly from martian igneous meteorites and used this data to infer the source mineralogy of the martian mantle.

Mars↗

NASA NTRS2022

Historically inconsistent productivity and respiration fluxes in the global terrestrial carbon cycle

The terrestrial carbon cycle is a major source of uncertainty in climate projections. Its dominant fluxes, gross primary productivity (GPP), and respiration (in particular soil respiration, RS), are typically estimated from independent satellite-driven models and upscaled in situ measurements, respectively. We combine carbon-cycle flux estimates and partitioning coefficients to show that historical estimates of global GPP and RS are irreconcilable. When we estimate GPP based on RS measurements and some assumptions about RS:GPP ratios, we found the resulted global GPP values (bootstrap mean 149^(+29)_(−23) Pg C/yr) are significantly higher than most GPP estimates reported in the literature (113^(+18)_(−18) Pg C/yr). Similarly, historical GPP estimates imply a soil respiration flux (Rs(_GPP), bootstrap mean of 68^(+10)_(−8) Pg C/yr) statistically inconsistent with most published RS values (87^(+9)_(−8) Pg C/yr), although recent, higher, GPP estimates are narrowing this gap. Furthermore, global R_(S):GPP ratios are inconsistent with spatial averages of this ratio calculated from individual sites as well as CMIP6 model results. This discrepancy has implications for our understanding of carbon turnover times and the terrestrial sensitivity to climate change. Future efforts should reconcile the discrepancies associated with calculations for GPP and Rs to improve estimates of the global carbon budget.

Jinshi Jian↗

NASA NTRS2023

The H Content of Aubrites: An Evaluation of Bulk Versus in Situ Methods for Quantifying Water in Meteorites

Aubrites and enstatite chondrites (ECs) are isotopically similar to the Earth and therefore may resemble the primary materials that accreted to form our planet. Recent bulk H elemental and isotopic analyses of ECs and the Norton County aubrite suggest that enstatite-rich materials are H-rich and may represent a significant source of terrestrial water, with measured values of 3000±2000 μg/g H2O and 5300±900 μg/g H2O in the bulk and enstatite fractions of Norton County (Piani et al., Science, 2020). Here, we present a detailed investigation of in situ H2O concentrations in enstatite, diopside, forsterite, and plagioclase from a suite of main group aubrites, including Norton County, and Shallowater. We find that enstatite (4±2 μg/g H2O), diopside (4.8±0.5 μg/g H2O), and forsterite (5±3 μg/g H2O) have similar H2O concentrations, and all are significantly lower than plagioclase (24±3 μg/g H2O). We combine our in situ analyses of H2O contents with equilibrium partition coefficients and bulk mineralogies to estimate the bulk H2O content of our samples. We compare these first order estimates with bulk volatile analyses conducted using sample pyrolysis and find that the previous bulk H2O analyses of aubrites predominantly reflect terrestrial contamination and alteration. If our conclusion that the reported bulk H2O analyses of Norton County primarily reflect terrestrial contamination and alteration extends to bulk analyses of ECs, then EC-like material may not be a significant source of terrestrial water. Our results support the hypothesis that thermal metamorphism, melting, and differentiation leads to efficient desiccation of planetesimals relative to chondrites, and that differentiated planetesimals contributed, at most, trace amounts to Earth's water budget.

Achondrite↗

NASA NTRSDate not supplied

A New Era of H-O-C-S Magma Solubility Modeling: Better, Faster, Stronger

H 2 O, CO 2 , and S are the most abundant volatiles in magmatic systems and are critical to understanding magma storage, phase equilibria, and volcanic eruptions. Models that consider all three of these components, however, may not allow for critical examination and adjustment of assumptions underlying the model, or provide benchmark testing or extensible interfaces. Thus, understanding why models produce different results can be challenging. We have gathered authors of established (D-Compress) and recent (VolFe, EVo, Sulfur_X, MAGEC) H-O-C-S volatile solubility models to work together to understand how and why our models diverge. We present a series of benchmark basalt degassing scenarios revealing that often understated model assumptions such as fO 2 buffer equations, fO 2 -Fe 3+ /ΣFe relationships, and even major element normalization routines have outsized effects on model results. All models consider S 2- and S 6+ melt species but with different approaches to sulfate/sulfide capacities, partition coefficients, and species fugacities, leading to divergence in the evolution of modeled gas compositions, melt S and Fe speciation, and fO 2 , with the extent of divergence depending on melt composition. Such scenarios enable meaningful intercomparison of existing models and lay the groundwork for a user-friendly yet powerful solubility modeling framework. Given our wealth of existing solubility literature, we suggest that the field of magmatic volatiles should focus now on the creation of modern tools and the modular implementation of existing model equations or methods, and that the evaluation of code usability, transparency, and benchmarking should be codified pillars of the peer-review process. As an example of such an endeavor, we present early work coupling these sulfur solubility models with VESIcal, an extensible and rigorously tested python library containing seven existing H 2 O-CO 2 solubility models. VESIcal includes the ability to extract, edit, and even interchange assumptions underlying any model. For example, users may combine or swap separately published H 2 O, CO 2 , and S models, as well as underlying model choices, such as Equations of State and redox models.

volatiles in magmas↗

NASA NTRS1980

Actinide crystal-liquid partitioning for clinopyroxene and Ca3/PO4/2

Coefficients for the partitioning of the actinide elements Th, U and Pu, which are used as indicators of r-process nucleosynthesis and the ages of meteorite and lunar samples, between diopsidic clinopyroxene, whitlockite and silicate liquid at 20 kbar are measured. Fission and alpha track radiography techniques are employed to detect element concentrations in synthetic crystals made using spiked starting materials, under the assumptions of equilibrium partitioning at the crystal-liquid interface and actinide zoning. Analysis of the data indicates results to be consistent with interface equilibrium except at high cooling rates. Th/U/Pu partition coefficients of about 0.002/0.002/O.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. The greater incorporation of Pu into the crystalline phases is attributed to the importance of trivalent Pu, and the similarity of its partition coefficient into clinopyroxene to that of the light rare earths supports the concept of Pu/rare earth dating.

Benjamin, T.↗

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↗