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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.↗

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.↗

Martian Magma Evolution from Olivine-Hosted Melt Inclusions in Shergottites Using MELTS Models

Shergottites, the largest martian meteorite group, come from at least two geochemically different source reservoirs i.e. incompatible trace element (ITE)-depleted and enriched. The depleted shergottites are thought to be derived from an ITE-depleted mantle reservoir, while enriched shergottites are thought to be derived from an ITE-enriched mantle reservoir that represents late stage residual melt from a magma ocean or interaction with martian crust. Moreover, the martian crust is distinct from shergottites, by being highly oxidized, distinctly ITE-enriched, and older. The link between the crust and shergottite compositions is poorly understood. Here we model shergottite differentiation to resolve the origin of enriched shergottites and why the bulk martian crust is compositionally distinct from shergottites. Early formed olivine-hosted melt inclusions can provide primary melt composition from which the parental magma had crystallized and also information at different stages of crystallization during parent magma differentiation that leads to shergottite magma evolution as well as crustal contribution assessment. We analyzed olivine-hosted melt inclusions of two enriched poikilitic shergottites for their major, minor and trace element concentrations using electron microprobe and laser ablation ICP-MS. We corrected the melt inclusion compositions for post-entrapment re-equilibration with their host olivine. To comprehend the crystallization sequence of these rocks and whether the melt entrapment is consistent with the crystallization, we use MELTS models for equilibrium and fractional crystallization. The results of these models suggest that all the melts were trapped in a closed system progressive crystallization at 1150-1210 ⁰C within 1 kbar to 1 bar pressure that is equivalent to <8.5 km, implying melt entrapment without any additional exogenous materials.

Ferdous, J.↗

Spatial U-Pb Age Distribution in Shock-Recrystallized Zircon – A Case Study from the Rochechouart Impact Structure, France

Age determination of impact structures via the zircon U–Pb system remains challenging and often ambiguous due to highly variable effects of shock metamorphism on U-Pb geochronology. It is, therefore, crucial to link the observed zircon microtextures, including their temperature and pressure conditions associated with their formation, directly to the U–Pb ages preserved. Here, we analyzed three recrystallized zircon grains and one plastically deformed zircon crystal from the medium-sized Rochechouart impact structure in the northwestern Massif Central of France. For the Rochechouart impact structure the impact age (206.92 ± 0.32 Ma [40Ar/39Ar]) as well as the 2 tectono-themal history is well established making this study site ideal to test concepts about U-Pb systematics in shocked zircon and to differentiate between shock-driven age resetting and preimpact crystallization and metamorphic overprinting. Zircon microstructures were studied using scanning electron imaging, cathodoluminescence imaging, and electron backscatter diffraction (EBSD) mapping. Further, we conducted U–Pb Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) depth-profiling analysis, allowing us to interpret the resultant age data in discrete steps with increasing ablation time/depth. The U–Pb depth profiling data demonstrate that plastically strained grains are incompletely reset and preserve rim and interior age domains reflecting typical pre-impact (pre-Variscan and Variscan) regional tectonic ages. Our results also reveal that the granular crystals encountered contain microstructural evidence for “former reidite in granular neoblastic” (FRIGN) zircon, reflecting both high-pressure (⩾30GPa) and high temperature (⩾1200℃) conditions. This signifies that FRIGN zircon is now known from an additional, medium sized, impact structure further supporting the hypothesis that this impact induced microstructure is commonly preserved. In addition, FRIGN zircon has a high potential to preserve completely impact-reset crystal domains (~204 to 207 Ma) that can be identified by our combined analytical approach of U–Pb depth profiling and EBSD mapping, and thus are suitable for determining reliable impact ages

U-Pb depth profiling↗

Broad Compatibility Study of Polymeric Materials with Ionic Silver Biocide, Part I

NASA is considering ionic silver as a residual biocide for use in potable water systems being planned for future exploration spacecraft. Compatibility of the biocide with the system’s wetted-materials of construction remains a challenge. Due to the relatively inert nature of plastics, their use in varied water system applications may offer unique opportunities to address many biocide compatibility issues. A 2020 ICES paper described a “Stage 1” assessment of several polymeric materials, in which coupons having a 2 cm 1 surface to volume ratio were exposed to solutions of 400 parts per billion (ppb) aqueous silver fluoride (AgF) for one week. In this current paper, additional Stage 1 test results are presented for select epoxies and lubricants applied on silver-inert substrates. The coupon exposure studies were also expanded to a duration of 5 weeks for the “well-behaved” Stage 1 plastics previously reported: those exhibiting silver losses above 10% and less than 50%. For this type of Stage 2 testing, silver biocide solution samples are taken from three separate (and not previously-sampled) coupon containers after 3 days, and 2, 3, 4, and 5 weeks of exposure. "Very well-behaved" Stage 1 plastics will be tested in the same manner over one year, with longer sample intervals; early-period results are included here. In addition, for select materials, the coupons were “aged” by refilling test containers with fresh AgF and observing the respective silver uptake over similar Stage 2 test durations. For all test series, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and ion-selective electrode (ISE) analyses were used to determine total and ionic silver (Ag+) concentrations, respectively. Additional sample analyses for Stage 2 tests includes total organic carbon (TOC), pH, conductivity, and oxidation-reduction potential (ORP). Ultimately, these early compatibility studies will be used to guide future material selections for developing silver biocide-compatible spacecraft water systems.

Silver Biocide↗

In Situ Geochronology for the Next Decade

Geochronology, or determination of absolute ages for geologic events, underpins many inquiries into the formation and evolution of planets and our Solar System. The bombardment chronology inferred from lunar samples has played a significant role in the development of models of early Solar System and extrasolar planet dynamics, as well as the timing of volatile, organic, and siderophile element delivery. Absolute ages of ancient and recent magmatic products provide strong constraints on the dynamics of magma oceans and crustal formation, and the longevity and evolution of interior heat engines and distinct mantle/crustal source regions. Absolute dating also relates habitability markers to the timescale of evolution of life on Earth. The number of geochronologically-significant terrains across the inner Solar System far exceeds our ability to conduct sample return to all of them. Therefore NASA has invested in the development of in situ dating techniques; several such instruments will be TRL 6 by the time of the next Decadal Survey. We formulated a set of medium-class (New Frontiers) mission concepts to three different locations (the Moon, Mars, and Vesta) with a notional payload consisting of the CDEX and KArLE instruments to measure radiometric ages, an imaging spectrometer and optical cameras to provide site geologic context and sample characterization, an ICP-MS to augment sample contextualization, and a sample acquisition and handling system. A Vesta hopper and single-site lunar and Mars landers to advance Solar System chronology fit into the New Frontiers cost cap in our study. Such missions would also enable a broad suite of geologic investigations such as basic geologic characterization, geomorphologic analysis, establishing ground truth for remote sensing analyses, analyses of major, minor, trace, and volatile elements, atmospheric and other long-lived monitoring, organic molecule analyses, and soil and geotechnical properties.

Barbara A Cohen↗

Trace Elemental Abundances in Calcium-Aluminum-Rich Inclusions in CV Chondrites

Introduction: Calcium-aluminum-rich inclusions (CAIs), are the first formed solids that define the age of the Solar System [1,2]. CAIs are thought to have condensed from nebular gas [3,4] within the first <1 Ma of Solar System formation [5,6]. CAIs have experienced numerous early Solar System processes including condensation, evaporation, melting, recrystallization, and aqueous alteration [e.g., 7]. The chemical, mineralogical, and textural diversity among CAIs results from a range of chemical and physical processes recorded during nebular and parent body epoch. This study aims to explore the mineralogical, textural, and chemical compositions of CAIs including the trace elemental abundances in CAI phases to determine the early Solar System processes recorded in them. Samples and Analytical Methods: We analyzed one CAI each from CV3 chondrites Northwest Africa (NWA) 5508 designated as ‘Saguaro’, and Northwest Africa (NWA) 12772 designated as ‘Hoopoe’. Back-scatter electron (BSE) images were collected using a Phenom XL scanning electron microscope (SEM) at the Lunar and Planetary Institute (LPI) and the JEOL JXA-8530F electron probe microanalyzer (EPMA) at Johnson Space Center (JSC)-NASA. Additionally, energy dispersive X-ray spectrometry (EDS) elemental maps of select areas for these samples were collected using a 15.0kV beam energy and a 40µA emission current. Using the EPMA, wavelength-dispersive X-ray spectroscopy (WDS) quantitative data were collected. In-situ trace element measurements for both CAIs were determined at JSC-NASA using a Photon Machines 193nm laser ablation system and a Thermo-Scientific Element-XR inductively coupled plasma mass spectrometer (ICP-MS). Analyses consisted of 30s ablations at 10Hz, spot sizes of 20-25µm, and a fluence of 6.0 J/cm2 for anorthite and melilite, and a 3.5 J/cm2 fluence for all other phases. NIST612 was used to correct for instrument drift, while BHVO-2g was used as a primary calibration standard. BCR-2g and in-house mineral standards were regularly measured as unknowns to ensure accuracy. Results: Saguaro is a coarse-grained CAI, ~11 x 6 mm in dimensions. Saguaro contains spinel, Al-rich pyroxene, anorthite, Mg-rich melilite, and minor perovskite in its interior and is therefore classified as a Type B CAI. Individual melilite grains shows normal compositional zoning with an Ak content ranging from ~24 to 54 with no apparent trend from the core to the edge of the CAI. The spinel appears euhedral and occurs both as clusters and as spinel palisades [8]. Two rim sequences surround most of the sample: the inner rim being a Wark-Lovering (WL) rim (~10-35 µm) containing pyroxene, spinel, and melilite (or anorthite), and the outer rim is a finer-grained, thicker (~100 µm), accretionary rim (Fig. 1). The mineral phases in Saguaro record an overall flat REE pattern with an average negative Eu anomaly in pyroxene, and an average positive Eu anomaly in anorthite and melilite respectively. Anorthite, melilite, and pyroxene have a minor depletion in Tm (Fig. 2). The Hoopoe CAI is a compact, coarse-grained ~6 × 4 mm in size. The major mineralogy includes hibonite, spinel, melilite, anorthite, and perovskite. Therefore, it is classified as a compact transitional type A and B. (?)zoning was observed in some hibonites. Individual melilite grains show both reverse and normal zoning, where the Ak content ranges from ~6- to 28. Melilite shows two distinct textures. One texture consisted of smooth melilite that appeared homogenous, while the second appeared to consist of many fine fractures. The spinel also often appears clustered. The WL-rim sequence surrounding Hoopoe is ~25 µm thick and composed of spinel, perovskite, hibonite, and melilite/anorthite. It is then partially surrounded by an outer accretionary rim (~75µm). Like before, refractory metal nuggets appeared concentrated near the WL rims. Other metal assemblages rich in Fe and Ni were also observed. All major mineral phases in Hoopoe display relatively flat REE patterns, except for varying Eu and Tm between phases (Fig. 2). There is a prominent negative Eu anomaly in perovskite and an average positive Eu anomaly in spinel, anorthite, and hibonite respectively (Fig. 2, 3). The mixed phases along the rim of the CAI also display a negative Eu anomaly, and all phases the CAI were depleted in Pb. Discussion: The CV3 CAIs analyzed in this study were classified based on their mineralogy and textures into Type A versus Type B CAIs [10]. Hibonite appears to be pseudomorphically replacing the spinel, (i.e., is hibonite in composition, but appears in the shape of spinel). Spinel palisades. The presence of spinel palisades present in Saguaro are consistent with the melting and recrystallization experienced by this CAI. Trace elemental analyses. Saguaro and Hoopoe display similar trace element patterns to each other, with both appearing generally flat, with anomalies in Eu, and Tm. Melilite and anorthite display positive Eu anomalies in both CAIs, in addition to the hibonite in Hoopoe (Fig. 2). The phases that are depleted in Eu are pyroxene and perovskite in both Saguaro and Hoopoe, respectively (Fig. 3). Given that Eu is volatile in reducing environments [11], this could possibly indicate reducing conditions at the time anorthite and melilite crystallized, with the gas they formed from containing Eu. As these CAIs continued to form, this gas as a result would become depleted in Eu. This also could be supported by the propensity of anorthite and melilite to take up Eu from its surroundings and incorporate it into their structure [12]. In addition, analyzing the assemblage of the phases in the Saguaro, melilite and anorthite (Eu enriched) often surround the pyroxene (Eu depleted) as they are crystallized. This intergrowth of phases and the proximity of the phases would support that the Eu is being incorporated into some phases, preventing it from incorporating into other. Trace elemental analyses of the CAI rims will be evaluated in more detail, as they are complicated by the transient signal being composed of a mixture of mineral phases. Broadly, however, the patterns in the rims of both CAIs are comparable to each other, and for Hoopoe, to the mixed phase patterns in the core (Fig. 3). Other studies have found that CAI rims can be depleted in Ce and Yb [13], however we did not observe these anomalies in the two CAIs discussed here. Given their similarity, the trace elemental analyses of the mixed interior (i.e. core) and rim phases could be interpreted as forming from similar, if not the same, reservoirs. The REE abundance between the rim and core of Hoopoe are also similar, indicating they may have formed from a gas of the same or similar composition. Acknowledgments: We thank the ASU Center for Meteorite Studies for loaning the samples used in this work and Tabb Prissel for his assistance with the analysis. Mouti Al-Hashimi thanks Sam Crossley and Cyrena Goodrich for their help with the LPI SEM training. This work was supported by the LPI Summer Intern Program in Planetary Science and the LPI Cooperative Agreement. References: [1] Connelly J.N. (2012) Science, 338, 651-655. [2] MacPherson G. J. (2014) Treatise on Geochem., 2, 139-179. [3] Grossman L. (1972) GCA, 36, 597-619. [4] Ebel, D.S. (2006) Meteorites and the Early Solar System II (D. S. Lauretta & H. Y. McSween, Eds.) 253-277. [5] MacPherson G. J. (2012) Earth Planet. Sci. Lett., 331-332, 43-54. [6] MacPherson G.J. (2017) GCA, 201, 65-82. [7] Krot A.N. (1995) Meteoritics & Planet. Sci., 30, 748-775. [8] Wark and Lovering (1982) GCA, 46, 2595-2607. [9] Palme H. and Jones A. (2003) Treatise on Geochemistry (H. D. Holland and K. K. Turekian Eds.), 1, 41-61. [10] Grossman L. (1980) Ann. Rev. Earth Planet. Sci., 8, 559-608. [11] Floss C. et al. (1996) GCA, 60, 1975-1997. [12] Mason B. and Martin P. M. (1974) Earth Planet. Sci. Lett., 22, 141-144. [13] Wark B. and Boynton W. V. (2001) Meteoritics & Planet. Sci., 36, 1135-1166.

X Mouti↗

Acid Alteration of Clay Minerals With Implication for Mars’ Surface Processes

The co-occurrence of phyllosilicates (clays) and sulfate stratigraphies at many locations on Mars are associated with a sharp change in surface conditions from neutral/alkaline pH during the Noachian (4.1-3.7 Ga) which favored the formation of clays to acidic conditions during the Hesperian (3.7-2.9 Ga) which favored the formation of sulfates. Yet, if these two contrasting geosystems were temporarily sequential, it is unknown how the Hesperian acidic conditions altered the previously formed clay units. We performed laboratory batch experiments to fingerprint the diagnostic features produced during interactions of Mars-analog clays and acidic solutions. Two clays, and silicon (IV) oxide, were reacted with solution of either sulfuric acid or filtered natural acid rock drainage (ARD) in plastic bottles. The solutions were adjusted at four pH values (1, 3, 5, and 7) and reacted at 4, 30, and 80°C for 3, 7, and 14 days. At the end of the experiments, the filtered supernatants were analyzed by ICP-MS while the solids were characterized by X-Ray Diffraction; Energy-Dispersive X-Ray Fluorescence analyses; Raman and Short-Wave Infrared spectroscopies and Scanning Electron Microscopy. Results show that the solution chemistry played a key role in the evolution of the clay-solution systems. In H2SO4 systems, the solution pH steadily increased due to partial clay dissolution with no secondary phase formation detected. Contrary, in the ARD systems, the pH decreased due to the ample presence of Fe which controlled both the reactivity of clays by the growth of protecting surface coatings and the solution pH by the precipitation of Fe nanophases; secondary phase detected included goethite, jarosite, gypsum, and siderite. These results indicate that, on Mars, the chemical interaction between clays and acidic solutions was complex and dependent on the solution chemistry. Acidic, sulfate-rich solutions have a high dissolution capacity and could have induced widespread clay disintegration. Notably, if Fe-rich ARD was involved, the clays on Mars could have remained stable during acidic Hesperian period due to formation of protective coatings. Comparison of our results with martian observations will be performed to determine how acidic conditions could potentially affect clays in sedimentary settings, including the Gale crater.

L. Lefticariu↗

Microstructural Changes and Pb Mobility During the Zircon to Reidite Transformation: Implications for Planetary Impact Chronology

Impact events modify and leave behind a complex history of rock metamorphism on terrestrial planets. Evidence for an impact event may be recorded in physical changes to minerals, such as mineral deformation and formation of high P-T polymorphs, but also in the form of chemical fingerprints, such as enhanced elemental diffusion and isotopic mixing. Here we explore laboratory shock-induced physical and chemical changes to zircon and feldspar, the former of which is of interest because its trace elements abundances and isotope ratios are used extensively in geochemistry and geochronology. To this end, a granular mixture of Bishop Tuff sanidine and Kuehl Lake zircon, both with well characterized Pb isotope compositions, was prepared and then shocked via a flat plate accelerator. The peak pressure of the experiment, as calculated by the impedance matching method, was ~24 GPa although a broader range of P-T conditions is anticipated due to starting sample porosity. Unshocked and shocked materials were characterized via scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and Raman spectroscopy. These methods show that the starting zircon material had abundant metamict regions, and the conversion of the feldspar to glass in the post-shock material. Analyses of the shocked product also yielded multiple occurrences of the high-pressure ZrSiO 4 polymorph reidite, with some domains up to 300 μm across. The possibility of U-Pb system disturbance was evaluated via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and secondary ion mass spectrometry (SIMS). The isotopic data reveal that disturbance of the U-Pb geochronometer in the reidite was minimal (<2% for the main U-Pb geochronometers). To better constrain the P-T conditions during the shock experiment, we complement impedance matching pressure calculations with iSALE2D impact simulations. The simulated results yield a range of P-T conditions experienced during the experiment and show that much of the sample may have reached >30 GPa, which is consistent with formation of reidite. In the recovered shocked material, we identified lamellae of reidite, some of which interlock with zircon lamellae. Reidite {112} twins were identified, which we interpret to have formed to reduce stress between the crystal structure of the host zircon and reidite. These two findings support the interpretation that shear transformation enabled the transition of zircon to reidite. The size and presence of reidite found here indicate that this phase is probably common in impact-shocked crustal rocks that experienced ~25 to ~35 GPa, especially when the target material has porosity. Additionally, shock loading of the zircon and transformation to reidite at these pressures in porous materials is unlikely to significantly disturb the U-Pb system in zircon and that the reidite inherits the primary U and Pb elemental and isotopic ratios from the zircon.

Bishop Tuff↗

Bulk Elemental Composition of Aggregate Material From Asteroid Bennu

On September 24, 2023, NASA’s OSIRIS-REx mission returned pristine carbonaceous material from asteroid Bennu. One key aspect required to understand this returned material is to establish its bulk chemical composition. This is primarily due to each chondrite group having a distinct elemental composition, which is important both as a classification tool and for establishing the connections between the different chondrite groups. As the carbonaceous and non-carbonaceous chondrites are thought to have formed in the inner and outer protoplanetary disk, respectively, measuring the bulk elemental composition of Bennu material will help test the mission hypothesis that “Bennu's parent body formed beyond the snow line by accretion of material in the protoplanetary disk”. In addition, two further mission hypotheses — paraphrased as Bennu’s bulk elemental composition reflects that of its parent asteroid and is similar to the composition of the Sun and Bennu’s dominant lithologies are comparable in composition to the most aqueously altered carbonaceous chondrites — can be directly tested by bulk elemental analyses. Elemental analyses were undertaken on sample OREX-803015-0, a 20.66 mg aggregate sourced from inside the sample collector. All analyses were conducted using an iCAP Q ICP-MS. Overall, all 54 elements analyzed for the Bennu aggregate sample show similar abundances to those of the average CI chondrite, and thus the solar photosphere composition and some of the most aqueously altered carbonaceous chondrites. The elemental data also show that Bennu is indeed a carbonaceous asteroid that formed beyond the snow line by accretion of material in the protoplanetary disk. This Bennu aggregate sample appears similar in elemental composition to samples of asteroid Ryugu, yet without the small refractory element enrichments seen in Ryugu.

P Koefoed↗

Investigating Commercial Off-The-Shelf (COTS) Glovebox and Support Components Compared to Custom Curatorial Laboratories

There is a need envisioned to investigate the application of commercial off-the-shelf (COTS) systems as tools that could be used within commercial preliminary curation as the expected space economy is supported and begins to take flight. NASA is involved with supporting and developing the space economy [1] and therefore it’s feasible that at some point, a commercial space company would bring back materials and either store initially, or permanently, within COTS equipment as a stand-in for custom curation laboratories. While utilizing opportunities to explore this capability at NASA-Johnson Space Center (JSC) during the establishment of other laboratories [2] it was realized that cleanliness and/or other properties could be evaluated for these COTS systems during their installation in advanced research facilities that are not ISO-class rated clean rooms. Several aspects of a COTS-Curation system were explored including various gloves for curation manipulation within a negative pressure glovebox (Fig.1), Balazs organic and inorganic contaminant levels testing prior to glovebox ever being used, mode swapping comparison of recirculation vs. single pass, constant monitoring of oxygen (O2) and moisture (H2O) levels in various conditions, etc. To acquire inorganic and organic compound loads inside the glovebox, Balazs wafer testing and gas sampling were implemented. These are standardized analytical tests provided by Balazs™ NanoAnalysis, a division of Air Liquide USA. Deployment of 8-inch silicon wafer witness plates for 24-hours in an undisturbed environment capture the organic compound load and inorganic trace metal contents which can be obtained by Vapor Phase Decomposition Inductively Coupled Plasma Mass Spectrometry (VPD ICP-MS). Balazs gas sample analysis was also performed for better measurements of volatile organic compounds (VOC) in glovebox air analyzed by Thermal Desorption Gas Chromatography Mass Spectrometry (TD GC-MS). These analytical testings were carried out in a controlled ultra high pure (UHP) gaseous nitrogen (N2)-purged environment where oxygen and moisture contents were continuously monitored at certain temperature and pressure. The preliminary outcomes of these testings are promising. The COTS systems appear to maintain the steady-state controlled environment for days, if not weeks, with uninterrupted gaseous N2-supply which was operated from a standard medium pressure LN2 250L 230L dewar, exchanged as needed. The outgassing load can be maintained by selecting the glove materials that have the least outgassing and particle shedding performances. Further experiments will be considered to validate the preliminary findings. While this project is exploratory, it is not intended as an endorsement by NASA Curation for approved materials or usage for advanced curatorial activities. NASA does not endorse nor promote any one particular product or company. References: [1] McCubbin F. M. et al. (2019) Space Science Reviews 215:A48. [2] Lewis, E.K. et. al (2024) LPSC LV, Abstract #2457.

Curation↗

Spatially-Resolved Characterization Techniques and Their Implications for Nuclear Debris Formation.

Debris from nuclear tests has a complex formation process and can inform multiple fields of study such as geology, atmospheric science, shock physics, and chemistry under extreme conditions. Macroscopic nuclear debris forms as the result of fireball interaction with surrounding materials (e.g., structural and environmental component), which rapidly undergo melting and vaporization followed by condensation, convective/diffusive mixing, and solidification over the course of seconds. In atmospheric events, some of this material may disperse over long distances, but much of the material is deposited close-in to ground zero, often in multicomponent, partially (or entirely) amorphous debris formations. During the U.S. nuclear testing program, this material was collected and analyzed, particularly for radionuclide composition. Fallout formation models were developed from nuclear test data based on such radionuclide compositional analyses. These models were not just used to understand fallout dispersion (i.e. the spread of radioactivity over geographical regions) but also guide radiochemical interpretations of historical nuclear tests.6 Developments in analytical techniques over the past several decades have made it possible to make new analyses on historical debris, some of which may be more than a half-century old. For example, inductively-coupled plasma mass spectrometry (ICP-MS) has been used to look at the trace elements in glassy fallout material from aboveground nuclear tests (including the Trinity test). Advanced analyses using X-ray absorption allowed for the measurement of oxidation state of fallout constituents, including actinides. The ability to measure trace actinides and their subsequent oxidation state is important to understanding how the surrounding environment may have influenced the resultant fallout composition and may have implications for why certain fractionation trends have been observed. Here we present data from historic nuclear test debris illustrating the power of spatially resolved methods to connect interaction of the near-field environment with the explosion and provide new insights into nuclear debris formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CRITICAL MINERAL RESOURCE ASSESSMENT OF COALS FROM THE POWDER RIVER BASIN, WYOMING, USA

Coal and associated sediments are potential sources of Rare Earth Elements (REE) and other critical minerals necessary for many consumer and defense-related products and development of energy technologies. For this study, 15 samples were sourced from Dry Fork Mine within the Powder River Basin near Gillette, Wyoming, to determine REE content along with select transition metals (t-metals) of interest in non-combusted coals and associated sediments. An excavator collected samples along a mine highwall, within benched intervals representing a foot to a few feet of coal strata. Homogenized sample subsets were crushed in an aluminum-ceramic vial, then passed through a 106-micron sieve. Sieved samples were pyrolyzed by a LECO TGA-108, which concurrently measured sample moisture, volatile, and ash content. Residual ash was then fused into a glass bead with lithium metaborate at a 6:1 Li-metaborate to sample ratio and then dissolved in 20% nitric acid. The nitric acid solutions containing digested beads were then diluted and passed through a 0.45 micron syringe filter. Filtered samples were analyzed by ICP-MS for REE and select t-metals. Reagent blanks were analyzed to assess for any potential contamination. Total REE plus Y (REE+Y) concentrations across the 15 samples range from 52 ppm to 1015 ppm with an average of 477 ppm on a dry ash basis. When normalized to upper continental crust (UCC; Taylor and McLennan, 1985) values, 13 of the 15 samples show average enrichment factors (EF) for REE+Y greater than 1. EF values indicate M-type enrichment (Sm through Er), as opposed to distinct preferential enrichment of light or heavy REE. T-metals with the highest average concentrations are V, Cu, Ni, and Zr at 215, 243, 123, and 118 ppm, respectively. Multiple t-metals had EF>1; however, Cu, Ge, and Sb have the highest average EF relative to UCC for t-metals, at 9.7, 8.0, and 17.0, respectively.

Copeland, Grant↗

Fundamental Data Supporting Novel Radiochemical Separations

Rapid chemical separation of actinide, lanthanide, and other radioactive elements is an important pursuit in the field of radioanalytical and nuclear chemistry. Vital to the development of advanced systems to achieve such separations is the determination of elements’ distribution coefficients (Kd values) for chromatographic resins. In this study, batch contacts of 68 elements were performed with various commercially available resins, and the resulting distribution coefficients were determined by Inductively Coupled Plasma – Mass Spectrometry Analysis (ICP-MS). An evaluation of the resulting Kd data for elements on the resins was performed. Finally, this work presents prototype flowsheets for streamlined separation of radioisotopes from a variety of complex matrices.

Distribution Coefficient↗

Analysis of Extracted Ingredients from Dairy Byproduct Using Dimethyl Ether

Whey permeate is a byproduct created in large quantities from the dairy industry with limited applications due to transportation and stability. Whey permeate is primarily comprised of water, carbohydrates, and minerals with minimal contribution of proteins. Various biomasses in food processing have utilized liquid dimethyl ether (DME) as a form of extraction for high-value ingredients and dewatering. DME is a growing interest in wastewater and biomass treatment due to it being a green solvent, ability to dissolve organic solvents, and miscibility with water. The current study is to determine if DME can effectively dewater whey permeate as well as recover components that can be further used in the food industry as a value-added ingredient. Analysis of the liquid extract and solid extract was evaluated with inductively coupled plasma-mass spectrometry (ICP-MS) and solid extracts were further characterized with the application of a scanning electron microscope (SEM).

09 - BIOMASS FUELS↗

DOE-GENIORS Dynamic Irradiation Testing

As part of the homogeneous actinides recycling strategy, the EURO-GANEX process is one of the most promising options to achieve the goal of minor actinides recovery. Improvements made to EURO-GANEX system have resulted in the emergence of the so-called New EURO-GANEX process, where the composition of the solvent has been modified by replacing TODGA and DMDOHEMA with cis-mTDDGA in the organic phase and SO3-Ph-BTP with PyTri-Diol in the aqueous phase in order to resolve important issues. The objective of this work is twofold: evaluate the gamma radiolytic resistance of the new EURO-GANEX process by dynamic irradiation conditions simulating the three main steps of the process, and validate the design of CIEMAT Náyade, CEA Marcel and INL irradiation loop devices since each of them mimics different aspects of the real process. Náyade and the INL loops could irradiate the organic and aqueous phases together, whereas in the CEA loop, the irradiated solvent is recycled continuously inside a platform with several stages of mixer-settlers containing aqueous flows simulating the three main steps of the process. The extraction performances and changes in the composition of the solvent have been analyzed during the irradiation experiment by different techniques: gamma spectrometry and ICP-MS/OES for cations or radioactive tracer extraction, and HPLC-MS to identify and quantify the degradation compounds. Despite some differences between the three-irradiation facilities, this inter-institutional study shows that these three comparative tools provide similar trends in the radiolytic stability of a liquid-liquid extraction system. Favourable extraction results for the different steps are obtained according to the static irradiation studies found in literature. However, the degradation of cis-mTDDGA is appreciable leading to degradation compounds, some of which form precipitates and produce important changes in viscosity, important aspects that must be addressed prior to the successful industrial application of the new EURO-GANEX process.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

Rapid and automated separation of uranium ore concentrates for trace element analysis by inductively coupled plasma – optical emission spectroscopy/triple quadrupole mass spectrometry

The present study documents an automated approach to performing elemental analysis on a large group uranium ore concentrate (UOC) samples. In this work, 17 UOC samples, 2 quality control samples, and 26 process blanks were purified sequentially through a single 500 μL Uranium and TEtra Valent Actinides (UTEVA®) column. For each sample, the trace elemental impurities were separated from its dissolved uranium matrix on the UTEVA column and collected for analysis by inductively coupled plasma – optical emission spectroscopy / triple quadrupole mass spectrometry (ICP-OES/TQMS). The UTEVA column was subsequently regenerated prior to separation of the following sample. The column was efficiently regenerated, for each UOC, even after processing ~50 mg of uranium, cumulatively. The validity of the method was established by determining the trace impurities of two quality control uranium reference samples (CRM 124–1 and CUP-2). The current trace element measurements from the 17 UOC samples were compared to previously reported values from an interlaboratory comparison exercise, when available. The methodology employed here produces trace elemental analysis with excellent correlation to the previously reported data for many of the elements / samples, particularly when viewed through the context of existing geochemical comparisons tools (e.g. chondrite normalized variation plots).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

TOFHunter—unlocking rapid untargeted screening of inductively coupled plasma–time-of-flight–mass spectrometry data

This study provides an overview of a newly developed open source program written in Python, TOFHunter, which permits the rapid and untargeted screening of inductively coupled plasma (ICP)-time-of-flight (TOF)-mass spectrometry (MS) datasets. ICP-TOF-MS is an analytical tool capable of providing quasi simultaneous detection of all nuclides from Li to Pu. This capability has triggered an increase in studies investigating single-particle analysis in which the TOF-MS provides correlated elemental/isotopic signatures on a particle basis in time. Similarly, laser ablation mapping has seen rapid growth owing to ICP-TOF-MS's capacity to handle fast washout times (<10 ms) while providing a broad nuclide coverage. The caveat to this broad mass coverage and high time resolution comes in the form of large, overwhelming datasets. With datasets typically on the scale of gigabytes, it is easy for a user to only focus on very targeted analytes; however, this focus diminishes the opportunity offered by the TOF-MS detector. TOFHunter applies chemometric methods, principal component analysis (PCA), and interesting features finder (IFF) on ICP-TOF-MS data, allowing for investigation of correlations, major and minor variance sources, and sample screening. The unique spectra identified by the (IFF) are used to generate a list of mass peaks, which are then matched with both nuclides and potential interferences before being exported for the user to investigate. Several case studies are discussed herein, demonstrating TOFHunter's ability to screen aqueous injections, single-particle/single-cell analysis, and probe laser ablation mapping files for unique regions of interest.

47 OTHER INSTRUMENTATION↗