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NASA NTRS2014

Alteration of Basaltic Glass to Mg/Fe-Smectite under Acidic Conditions: A Potential Smectite Formation Mechanism on Mars

Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed phyllosilicates were examined by XRD analysis. Mineralogical changes were significant in Adirondack incubated with 10 mM MgCl2 at pH 4 and heated at 200 C. X-ray diffraction analysis revealed formation of phyllosilicate during 14 day incubation (Figure 1). Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. The position of 02l (4.60 A) and 060 (1.54 A) diffraction bands were indicative of trioctahedral smectite such as saponite. Analysis of solution composition demonstrated that aqueous concentration of Mg decreased from 10 mM to approx.4 mM after 7 day incubation likely due to saponite formation. Smectite also formed in Adirondack incubated with 0 mM MgCl2 at pH 4 and heated at 200 C. However, diffraction peak positions of 02l (4.52 A) and 060 (1.51 A) suggested formation of dioctahedral nontronite. The 100degC Mg and Fe(II) treated basaltic glass experiments are ongoing and results will be presented.

Peretyazhko, Tanya↗
NASA NTRS2014

Identification of Martian Regolith Sulfur Components in Shergottites Using Sulfur K Xanes and Fe/S Ratios

Based on isotopic anomalies in Kr and Sm, Sr-isotopes, S-isotopes, XANES results on S-speciation, Fe/S ratios in sulfide immiscible melts [5], and major element correlations with S determined in impact glasses in EET79001 Lith A & Lith B and Tissint, we have provided very strong evidence for the occurrence of a Martian regolith component in some impact melt glasses in shergottites. Using REE measurements by LA-ICP-MS in shergottite impact glasses, Barrat and co-workers have recently reported conflicting conclusions about the occurrence of Martian regolith components: (a) Positive evidence was reported for a Tissint impact melt, but (b) Negative evidence for impact melt in EET79001 and another impact melt in Tissint. Here, we address some specific issues related to sulfur speciation and their relevance to identifying Martian regolith components in impact glasses in EET79001 and Tissint using sulfur K XANES and Fe/S ratios in sulfide immiscible melts. XANES and FE-SEM measurements in approx. 5 micron size individual sulfur blebs in EET79001 and Tissint glasses are carried out by us using sub-micron size beams, whereas Barrat and coworkers used approx. 90 micron size laser spots for LA- ICP-MS to determine REE abundances in bulk samples of the impact melt glasses. We contend that Martian regolith components in some shergottite impact glasses are present locally, and that studying impact melts in various shergottites can give evidence both for and against regolith components because of sample heterogeneity.

Sutton, S. R.↗
NASA NTRS2015

A Procedure to Simultaneously Determine the Calcium, Chromium, and Titanium Isotopic Compositions of Astromaterials

Many elements display both linear (mass-dependent) and non-linear (mass-independent) isotope anomalies (relative to a common reservoir). In early Solar System objects, with the exception of oxygen, mass-dependent isotope anomalies are most commonly thought to result from phase separation processes such as evaporation and condensation, whereas many mass-independent isotope anomalies likely reflect radiogenic ingrowth or incomplete mixing of presolar components in the proto-planetary disk. Coupling the isotopic characterization of multiple elements with differing volatilities in single objects may provide information regarding the location, source material, and/or processes involved in the formation of early Solar System solids. Here, we follow up on the work presented in, and detail new procedures developed to make high-precision multi-isotope measurements of Calcium, Chromium, and Titanium with small or limited amounts of sample using thermal ionization mass spectrometry and multi-collector ICP-MS, and characterize a suite of chondritic and terrestrial standards.

Tappa, M. J.↗
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 NTRS2018

The Contrast in Outgassing of Germanium Between Shergottites and Nakhlites

Final Paper and not the abstract is attached. Introduction: Germanium is generally thought to follow Si in its geochemical behavior, but little data has existed to rigorously understand the behavior of Ge in the Martian mantle. Germanium is known to be more siderophile than Si, and its partitioning into the martian core has been studied by. Typical abundances in igneous martian meteorites range from 0.5-3 ppm, a larger range than what is observed in terrestrial basalts (1.5 +/- 0.1 ppm). In situ measurements by the MER and MSL rovers have revealed a surprisingly large range in Ge abundances in surface rocks (30-650 ppm), but many igneous rocks and soils are shown to have greater than 30 ppm Ge (the detection limit of the APXS). Recently, reported that shergottite minerals showed a depletion of Ge with increasing fractionation, while nakhlites and chassignites exhibited Ge behavior compatible with closed system igneous differentiation. They interpreted their observations as tentatively indicating volcanic outgassing of Ge from shergottites (but not from nakhlite-chassignites) with recondensation of the Ge vapor into soils and breccias. Recent experimental studies show that Ge is significantly volatile from magmas. In this study, we followed up on those results by analyzing minerals in five nakhlites and five shergottites by laser ablation ICP-MS (LA-ICP-MS). See Attached

Yang, S.↗
NASA NTRS2019

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.↗
NASA NTRSDate not supplied

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↗
NASA NTRSDate not supplied

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↗
NASA NTRSDate not supplied

Thermodynamic constraints on the textural evolution of eucrite, EET 90020

Basaltic eucrites, which are possibly parts of the Vestan crust, formed as either lava flows or intrusions, and can offer insights into early crust formation. However most eucrites have experienced thermal metamorphism, which exacerbates the challenges of understanding these samples. A variety of petrogenetic models such as, partial melting of a primitive source, fractional crystallization of magmas emplaced in a primitive crust, and/or partial melting of a eucritic source coupled with melt mixing and assimilation have been proposed in order to explain observed petrologic and chemical characteristics of eucrites. EET 90020 is an unbrecciated eucrite that has experienced significant thermal metamorphism, with temperatures of metamorphic equilibration calculated to be ~840-1040°C. Its petrologic history remains contentious, in part due to differences in trace element analyses [10,17, this work], which has led to multiple metamorphic interpretations [8,10-11]. Here, we combined petrologic observations, chemical analyses, and thermodynamic modeling, to interpret micro-domain textures identified in EET 90020 and better constrain its petrologic history. Ultimately, the development of such textures is a direct result of the geologic processes operating on a young Vesta or similar asteroid. Sample description: We identified three textural domains in EET 90020 (Figure 1); (I) A coarse grain domain with granoblastic plagioclase and pyroxene, (II) a medium grain domain with curved grain boundaries between plagioclase and pyroxene, and (III) a fine grain domain dominated by tridymite that fills in interstitial space between spherical plagioclase. Major element chemistry in phases is consistent across domains. Pyroxene have distinctive high Ca lamellae (Wo40.92En28.1Fs31.0) forming from the low-Ca pigeonite host (Wo3.5En33.7Fs62.8). There are small amounts of fayalitic olivine along pyroxene/oxide grain boundaries, where pyroxenes have reacted with ilmenite/chromite clasts. Plagioclase is anorthitic (Avg ~An88), with little variation (An86-92.5). Trace element bulk rock analyses were collected via ICP-MS and individual mineral analyses with LA-ICP-MS (Figure 2). The bulk sample has an observable enrichment in light rare earth elements, with a notable depletion in Eu. Plagioclase is enriched in LREEs, depleted in HREEs, and has a positive Eu anomaly while pyroxene is enriched in HREEs with a negative Eu anomaly. Variations in trace element analyses is likely influenced by the presence of phosphates because are highly enriched in REEs and have a dramatic effect on the bulk domain compositions. Thermodynamic modeling: The software package, Perple_X, was used to calculate mineral phase equilibria over a range of conditions using a Gibbs free energy minimization approach [12]. Models used all major/minor elements except P2O5. Thermodynamic properties from [13] were used to constrain endmember phase stabilities. Activity models were used to describe mixing in phases with solid solution. Isochemical P-T phase diagrams were constructed for the bulk thin section, and the coarse, medium and fine grain domain compositions. Domain compositions were determined using microprobe analyses of phases identified in each domain and observed modal mineral abundancies. Thermodynamically stable pyroxene compositions were extracted from model results and compared to pyroxene compositions collected via EMPA, allowing us to calculate temperatures for metamorphic equilibrium. Results: Results that use the coarse domain composition (Fig. 3a) demonstrate overlap at T ~ 1020°C indicating high T equilibration. There was no overlap for the medium and fine grain domains, or the bulk composition (e.g., Fig. 3b) indicating that these are not equilibrium assemblages. These results were replicated using data from [8,20]. Discussion: The disequilibrium results from the bulk rock, fine grain and medium grain models imply that EET 90020 was modified during and/or after peak metamorphism (open system behavior). However, this is in contrast to the coarse domain where it appears as if equilibrium was maintained. We suggest that this conflict is explained by highly localized equilibrium occurring at millimeter length-scales, which has been observed in terrestrial metamorphism where aqueous fluid infiltrate [14] or melt loss occurs [15]. It is unlikely that aqueous alteration was significant in modifying the bulk composition of EET 90020, because it lacks hydrated minerals. However, the presence of melt is supported by the presence of an abundance of curved grain boundaries and spherical grains in the medium and fine grain domains This contrasts the coarse domain, where grain boundaries are angular. Given the evidence for disequilibrium in the medium and fine grain domains, it would be inappropriate to draw additional conclusions about textural evolution using thermodynamic models of those domains. However, modeling results of the coarse grain domain, where equilibrium was maintained, can provide useful insights into the geologic evolution of EET 90020. We approximate maximum metamorphic temperatures, using the Ca component in pyroxene, at ~1020°C (Fig. 4), which is consistent with previous two-pyroxene thermometry [11]. At this temperature, up to 10 vol % melt can be produced in the coarse grain domain, which is at the boundary of minimum melt needed in order to segregate and form a melt network [16]. Tridymite and plagioclase would be the first minerals to melt out during heating starting ~990°C. This is consistent with the observed melt textures formed by tridymite and plagioclase in the fine grain domain. We suggest that a partial melting model best explains the textural development of EET 90020. Upon heating, melt generated was either trapped, resulting in no net change in the localized rock composition, or migrated, resulting in disequilibrium between pyroxene and the surrounding matrix. A positive Eu anomaly in plagioclase indicates that all of the plagioclase was melted previously. This is consistent with previous studies that have suggested that EET 90020 represents a residual eucrite that experienced partial melting and subsequent melt loss [8]. We speculate that partial melting could have occurred when EET 90020 was heated in the asteroid’s lower crust or adjacent to an intrusion [7]. Future work will study other, texturally heterogeneous samples to see if EET 90020 presents a unique circumstance or whether crustal partial melting was ubiquitous on the eucrite asteroid.

Eucrites↗
NASA NTRSDate not supplied

Center for Isotope Cosmochemistry and Geochronology at NASA Johnson Space Center

Ten years in the making the Center for Isotope Cosmochemistry and Geochronology (CICG) at NASA Johnson Space Center is designed to be a cooperative analytical facility where novel techniques are developed and performed. Our team works collaboratively to operate this integrated lab suite comprising sample preparation, metal-free clean chemistry, and mass spectrometers to measure a wide variety of elements and isotopes in astromaterials. Contamination control is enacted throughout by a positive pressure cascade of HEPA filtered air, weekly surface cleaning and particle counting. Astromaterials processing is performed with application-specific mortar and pestles, heavy liquid separation, a Frantz magnetic separator, as well as hand-picking using optical microscopes in laminar flow boxes. Microsampling is also carried out using a New Wave MicroMill. Elements for isotopic analysis are isolated from acid-digested samples using ion-exchange chromatography. Cross-contamination is minimized with dedicated laminar flow boxes and labware for different purification protocols. Instrumentation includes a ThermoFisher Element XR inductively coupled plasma mass spectrometer (ICP-MS) for quantification of elemental concentrations in dissolved sample solutions. For in situ analysis, a Teledyne Photon Machines Analyte Excite+ laser ablation system is coupled to the Element XR. The ThermoFisher Triton thermal ionization mass spectrometer (TIMS) is used to measure the isotopic composition of elements such as CA, K, Cr, Rb, Sr, Sm, Nd at high precision in processed samples. For a more diverse range of isotopic analyses, CICG houses a Nu Sapphire 1700 multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS), which is a large geometry instrument with a multi-pole collision cell for interference removal. An Applied Spectra Instruments J200 femto-second laser is planned for install this Fall and will be coupled to the Nu Sapphire 1700. NASA’s Internal Scientist Funding Model (ISFM)supports this facility. Advanced analytical geochemistry techniques are applied to targeted astromaterials to address important problems in planetary sciences, with a longer-term goal of preparing for samples collected and returned by space missions. CICG is open to collaborations on projects that utilize the facility’s unique capabilities and are within its research scope. We are particularly eager to support and share expertise with the next generation of planetary scientists.

Justin I Simon↗
NASA NTRSDate not supplied

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↗
NASA NTRSDate not supplied

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↗
NASA NTRS2024

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↗
NASA NTRSDate not supplied

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↗
DOE OSTI2025

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↗
DOE OSTI2025

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 OSTI2025

High Pressure DME-Driven Fractional Crystallizations

Rare Earth Elements (REEs), include the 15 lanthanides plus yttrium and scandium and are crucial for various technologies and applications. Their low concentrations in the earth's crust require alternative sources. This study explores antisolvent fractional crystallization (FC) using dimethyl ether (DME) under high pressures to extract REEs from secondary sources such as mining waste, coal byproducts, and e-waste. DME's properties, including its solubility in water, small molecular size, and high vapor pressure, make it an effective antisolvent that can be easily recovered and reused. The method involves pressurizing DME to 1000-2000 psi in a reaction chamber with the test solution, followed by sample collection and analysis using ICP-MS and ICP-OES. This approach aims to address the limitations of current extraction methods, such as high energy consumption, chemical usage, and waste production, offering a potentially more efficient and sustainable solution for REE extraction.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2025

Isotopic analysis of Nd nanoparticles using single particle MC-ICP-MS: A comparative study with single particle-ICP-TOF-MS

Single particle - inductively coupled plasma - mass spectrometry (SP-ICP-MS) is a powerful technique for characterization of the elemental and isotopic composition of individual particles. In this work, the capabilities of the newest generation of MC-ICP-MS with acquisition rates down to 50 ms were evaluated for single particle analysis, with a focus on isotopic precision achievable on a single-particle level. Nd (NdVO 4 ) nanoparticles (~120 nm in diameter) were used as case study and were first characterized in terms of mass (respective size) and particle number concentration by SP-ICP-TOF-MS and then by SP-MC-ICP-MS for isotopic precision. For the isotopic ratio measurements, the MC-ICP-MS performance was compared to the ICP-TOF-MS and it was found that the isotope ratio precision was increased (R 2 between 0.98 and 0.99) compared to ICP-TOF-MS (R 2 between 0.88 and 0.97). The accuracy attained on a single particle level, was compared to bulk digestion followed by MC-ICP-MS analysis, and the SP-MC-ICP-MS technique was able to determine the particle population average to be <4 %, percent relative differences for the 142 Nd/ 144 Nd, 143 Nd/ 144 Nd, 145 Nd/ 144 Nd, 146 Nd/ 144 Nd, and 148 Nd/ 144 Nd ratios The detection limit for the SP-MC-ICP-MS approach was also assessed. Here, when utilizing an all Faraday-cup based detection scheme the determined LOD for the measurements was 0.2fg for Nd, per particle. Based on these results, the newest generation of MC-ICP-MS has demonstrated its utility for performing SP measurement, particularly when high precision isotopic determination is warranted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗