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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Critical Minerals and Rare Earth Elements in Powder River Basin Coal and Associated Sediments, Wyoming, USA

The demand for Rare Earth Elements (REE) and other critical minerals (CM) required for consumer products, defense-related applications, and low-carbon energy technology is increasing rapidly. Unconventional sources of REE/CM, such as coal and associated sediments, could prove very important in building resilient and ethical energy supply chains. Utilization of existing infrastructure and the highly trained energy workforce in traditionally coal-producing regions in emerging REE/CM industries could provide an economic boost to coal communities. The Powder River Basin (PRB) of Wyoming and Montana, USA, is a prime candidate to investigate the feasibility of extracting REE/CM from coal and associated sediments. The PRB hosts thick (>50 ft) coal seams that are mined at the surface and more than 40% of the coal produced in the US comes from the PRB. Geochemical data from multiple locations in PRB coal systems show REE enrichments at the top and bottom margins and at internal partings in coal seams. This trend is exhibited in two cores drilled at Peabody’s North Antelope Rochelle mine in the east central PRB, the largest coal mine in the world. The two cores include the Wyodak Anderson coal zone as well as the over- and underlying shale units. The Wyodak Anderson coal zone is part of the Paleocene Tongue River Member of the Fort Union Formation in which most of the coal resources in the PRB reside. To understand REE/CM enrichment, a total of 188 samples were analyzed for their major and trace element chemistry from both cores, sampled at one foot or smaller intervals. The two cores show distinct REE enrichments in the uppermost and lowermost 3 to 12 feet of the Wyodak Anderson coal zone, as well as enrichments in bounding carbonaceous shale units. Total REE+Y (REY) concentrations as high as 2510 ppm (all concentrations reported on an ash basis), or 15 times average upper continental crust values (Taylor and McLennan, 1995), were identified in the coal. Partings within the coal zone also show relative REE enrichment, with concentrations up to 485 ppm REY. The remaining interior portions of the coal zone contain lower concentrations of REE, resulting in an average REY for all samples from both cores of 288 ppm. The proportion of high-value critical REE (Nd, Eu, Tb, Dy, Er, Y) compared to REY averages 36%, which is higher than the critical REE proportion in average upper continental crust of 33%. This finding highlights the relative enrichment of middle REE compared to light REE, in contrast to many conventional REE deposits. Other critical trace elements that show enrichments above average upper continental crust include Ga, Nb, and V. Within this sample suite, Ga concentrations range from 2.8 to 213 ppm, with an average of 29 ppm; Nb from 2.9 to 166 ppm with an average of 26 ppm; and V from 27 to 1695 ppm with an average of 188 ppm. None of these trace elements exhibit the same distinct pattern of enrichment as REE in the upper and lower bounding layers and internal partings of the coal zone. Major element chemistry indicates CaO concentrations averaging ~25% in the coal samples from both cores, which has important implications for the extractability of REE from coal. Calcium-rich PRB coal has been shown to be more amenable to REE extraction than lower calcium coals by some methods (Stuckman et al., 2019; Taggart et al., 2016), highlighting the importance of REE extractability in addition to REE concentration in assessing the value of potential feedstocks. The original coal resource in the PRB is estimated at 1.16 trillion short tons (Luppens et al., 2015). Thus, the PRB represents an important potential unconventional source for REE and other CM. Ongoing research to fully characterize the REE/CM resource, identify enrichment mechanisms, and further develop and scale extraction technologies is necessary to understand the full potential of this resource.

Phillips, Erin↗
DOE OSTI2021

Changing chemistry of particulate manganese in the near- and far-field hydrothermal plumes from 15°S East Pacific Rise and its influence on metal scavenging

Dissolved Mn(II) in the hydrothermal plume is known to be microbially oxidized to form Mn(III/IV) oxides, and the Mn oxides scavenge other trace elements in seawater. In the GEOTRACES GP16 cruise, dissolved Mn (dMn) and particulate Mn (pMn) were found to be transported over 4000 km westwards from the Southern Eastern Pacific Rise. Previous studies in this plume showed different removal rates of dMn and pMn as well as pMn size distribution between the near-field (<80 km from the ridge axis) and far-field (>80 km) plumes. In order to understand Mn cycling in these plumes, spatial distribution, oxidation states, and mineral structures of Mn in small size fraction (SSF; 0.8–51 μm) and large size fraction (LSF; >51 μm) particles from the near-field and far-field plumes were examined using micro X-ray fluorescence spectrometry (μ-XRF), X-ray absorption near-edge structure spectroscopy (XANES), chemical species mapping, and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the near-field plume, pMn in the SSF is dominated by oxidized Mn with Mn(III) fractions of ~30%. They are a mixture of δ-MnO 2 and triclinic birnessites that is known to be formed as a result of autocatalytic Mn(II) oxidation at the surface of freshly-formed δ-MnO2, suggesting that both microbial and autocatalytic Mn oxidation occur in the near-field plume. The LSF pMn in the near-field plume is also oxidized and often found in large aggregates several hundreds of μm in size. These aggregates settle out in the near-field and during transport, and are not found in the far-field plume. In the far-field plume where Mn oxides are not newly formed, pMn in the SSF is oxidized, but their Mn(III) fractions are smaller than in the near-field pMn. Unlike the SSF, the far-field plume LSF pMn is dominated by reduced Mn, implying very slow aggregation of pMn in the far-field plume. The different characteristics of pMn between the near-field and far-field plumes affect its scavenging of other trace elements. In the near-field plume, Co, Mo, 231 Pa are associated with pMn, but not in the far-field plume. 231 Pa is adsorbed to pFe rather than pMn in the far-field plume, and Pb is adsorbed to pFe in the entire plume. The result shows that freshly-formed Mn oxides in the near-field plume have higher scavenging capacity than the far-field plume pMn. Our findings suggest that the mineralogical age of Mn oxides may be an important parameter that controls the scavenging of many other trace elements and isotopes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Remote sensing of wetland plant stress

High resolution laboratory, field, and airborne spectrometer data were correlated with plant tissue chemistry in order to characterize wetland plant spectral response due to high trace element concentrations. Wavelengths found to be important for distinguishing trace element stress were extended to broadband, regional remote sensing systems. Results indicate that LANDSAT Thematic Mapper bands 2, 3, and 5 may be the most useful for distinguishing between stressed and nonstressed wetland species.

Wood, B.↗
NASA NTRS2016

Evolution of the Lunar Receiving Laboratory to the Astromaterial Sample Curation Facility: Technical Tensions Between Containment and Cleanliness, Between Particulate and Organic Cleanliness

The Lunar Receiving Laboratory (LRL) was planned and constructed in the 1960s to support the Apollo program in the context of landing on the Moon and safely returning humans. The enduring science return from that effort is a result of careful curation of planetary materials. Technical decisions for the first facility included sample handling environment (vacuum vs inert gas), and instruments for making basic sample assessment, but the most difficult decision, and most visible, was stringent biosafety vs ultra-clean sample handling. Biosafety required handling of samples in negative pressure gloveboxes and rooms for containment and use of sterilizing protocols and animal/plant models for hazard assessment. Ultra-clean sample handling worked best in positive pressure nitrogen environment gloveboxes in positive pressure rooms, using cleanable tools of tightly controlled composition. The requirements for these two objectives were so different, that the solution was to design and build a new facility for specific purpose of preserving the scientific integrity of the samples. The resulting Lunar Curatorial Facility was designed and constructed, from 1972-1979, with advice and oversight by a very active committee comprised of lunar sample scientists. The high precision analyses required for planetary science are enabled by stringent contamination control of trace elements in the materials and protocols of construction (e.g., trace element screening for paint and flooring materials) and the equipment used in sample handling and storage. As other astromaterials, especially small particles and atoms, were added to the collections curated, the technical tension between particulate cleanliness and organic cleanliness was addressed in more detail. Techniques for minimizing particulate contamination in sample handling environments use high efficiency air filtering techniques typically requiring organic sealants which offgas. Protocols for reducing adventitious carbon on sample handling surfaces often generate particles. Further work is needed to achieve both minimal particulate and adventitious carbon contamination. This paper will discuss these facility topics and others in the historical context of nearly 50 years' curation experience for lunar rocks and regolith, meteorites, cosmic dust, comet particles, solar wind atoms, and asteroid particles at Johnson Space Center.

Allton, J. H.↗
NASA NTRS2018

Novel Applications of Focused Ion Beam Technique for Planetary Sample Analyses

We are using innovative FIB techniques to prepare samples of planetary materials for different types of coordinated analyses using ion microprobes, synchrotron beamlines, and specialized transmission electron microscopy (TEM) techniques. In these cases, the FIB sample preparation is the critical step in enabling these specialized analyses. We discuss several examples below utilizing the FEI Quanta3D instrument at the NASA Johnson Space Center. Trace element analyses utilizing synchrotron x-ray fluorescence. The trace element content of mineral grains in comet dust provides important clues on their formation and processing in the early solar system. We preformed coordinated analyses of a comet dust particle that had been prepared using ultramicrotomy for TEM analysis. Following the TEM analyses, we extracted a 70 nm thick section from a region of the carbon (C) film of the TEM grid, for additional analyses. A carbon ring ~2-3 μm thick was deposited on top of the C film using the FIB. The C film on the outer rim of the ring was milled away using various patterns to uniformly release the stresses on the film, preventing rupture and collapse, and was attached to the micromanipulator needle. We then isolated the ring completely and transferred the section to a silicon sample holder for analysis using the HXN (hard X-ray nanoprobe) beamline at NSLSII at Brookhaven National Lab. Coordinated Analyses of Presolar Grains. Rare sub-m presolar grains that originate in evolved stars and supernovae, occur in primitive astromaterials and are identified by their exotic isotopic compositions. Coordinated analyses of these grains using NanoSIMS, TEM, and other techniques on the same grain is enabled by innovative FIB sample preparation. In order to obtain subsequent isotopic analyses of Mg and Fe, contributions from surrounding grains were minimized. We precisely deposited a protective cap of Pt on top of the grain to preserve the grain of interest and then milled away about 5 μm diameter of the surrounding material. Following the isotopic analyses, the spindle was extracted and thinned to electron transparency for TEM microstructural analyses. In situ heating TEM experiments on lunar samples. We extracted a FIB thin section from Apollo 17 lunar rock 76015. To avoid ion-beam damage, e-beam deposition was used to deposit the first 500 nm of the C strap, followed by ion beam-assisted deposition of ~3 μm carbon. We performed an ex situ lift-out of the section and placed the section on one of the elements of a microelectromechanical systems (MEMS) - specialized heating substrate and attached the section to the substrate by depositing small C straps with the FIB. The heating chips utilize silicon nitride windows to support the samples and provide uniform heating while enabling TEM imaging. The heating chip was loaded into a Hitachi “Blaze” heating holder and analyzed using a Hitachi HF5000 at the University of Arizona.

Rahman, Z.↗
DOE OSTI2023

Activity model for 36 elements in Fe-Ni-Si-S-C liquids with application to terrestrial planet accretion and mantle geochemistry: New data for Ru, Re, Pt, Os, Ti, Nb, and Ta

Understanding siderophile element partitioning between metal and silicate melts under diverse conditions can be used to place important constraints on the materials and conditions of planetary accretion and core formation, as well as post core formation processes. However, the effects of Si on the partitioning and activity coefficients for these elements are not well known, despite Si likely being one of the dominant light elements in Earth’s core. To address this gap in understanding, we have undertaken a systematic study of the highly siderophile elements Re, Pt, Os, and Ru, and the refractory lithophile elements Nb, Ta and Ti at 1600 °C and 1 GPa, to derive epsilon interaction parameters for these elements in FeSi metallic liquids. Positive epsilon interaction parameters were measured for Nb, Ta, Ti, Ru, Re, Pt, and Os, indicating that dissolved Si in Fe liquids causes a decrease in their metal/silicate partition coefficients (or ‘silicophobic’ behavior). Furthermore, ε$_{Re, Os, or Ru}^{Si}$ > ε$_{Re, Os, or Ru}^{S}$ which means Si causes a larger decrease in D(metal/silicate) than S, and the chalcophile behavior expected from some elements will be completely masked by the presence of Si in a metallic liquid. The new parameters are used to update an activity model that now includes 36 siderophile elements in Fe-Ni-Si-S-C liquids (27 trace elements considered here). Systematic assessment of these 27 elements shows which have the strongest affinity for Si, C, and S, and also how activity coefficients for these elements would vary during accretion and core formation in Earth, Mars, and Mercury of widely differing fO 2 and core compositional conditions. The activity model is combined with new partitioning expressions for Mo, W, Cr, Re Ru, Pt, and Os and applied to aspects of post core formation mantle geochemistry of Earth, Mars, and Mercury. Our updated expressions show that the BSE Mo/W ratio can easily be achieved with metal/silicate partitioning during growth of the Earth, whereas Re, Os and Ru become lower than and highly fractionated compared with BSE values during core formation and accretion, and thus nearly 99% of their BSE abundances are likely contributed by late accretion. Ru isotopes should be a very good indicator of the source material for the late accretion. The high Pt/Os and Re/Os developed in a deepening magma ocean during the growth of the Earth, indicates 186 Os and 187 Os isotopes could be coupled if this ancient material remained isolated and subsequently became entrained in mantle plumes and measured in surficial lavas. The extent to which this occurred will be limited by the low Os content of this ancient material, thus requiring mixing as a major component in plume sources. Martian mantle Hf/W ratio stays low during accretion and core formation modelling, suggesting that W isotope anomalies are more likely due to solid/liquid silicate fractionation than to core formation. Finally, Ti contents measured by MESSENGER at Mercury’s surface can be explained by segregation of either a metallic core (IW-6 to -8) or metallic core + sulfide (IW-4 to -7.5) followed by mantle melting.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1976

Petrogenesis of KREEP

Solid/liquid distribution coefficients were experimentally determined for a number of trace elements for olivine, orthopyroxene, plagioclase and ilmenite. Major- and trace-element partitioning and relevant phase equilibria are used to study possible parent-daughter relationships between a number of highland samples and highly evolved KREEP-rich materials. A model is proposed in which low-K Fra Mauro basalt type material was produced by fractionation of large amounts of olivine and lesser amounts of plagioclase from undifferentiated lunar material at about 4.4 AE.

Mckay, G. A.↗
NASA NTRS1993

Basaltic magmatism on the Moon. A perspective from volcanic picritic glasses

It is widely accepted that basaltic magmas are products of partial fusion of peridotite within planetary mantles. As such they provide valuable insights into the structure and processes of planetary interiors. Those compositions which approach primary melt compositions provide both a clearer vision of planetary interiors and a starting point at which to understand basaltic evolution. Within the collection of lunar samples returned by the Apollo and Luna missions are homogeneous, picritic glass beads of volcanic origin. These glass beads provide a unique perspective concerning the origin of mare basalts, the characteristics of the lunar interior, and processes culminating in the early differentiation of the moon. In this presentation, we report our ion microprobe derived trace element data from all picritic glasses previously identified. We place this trace element data and literature isotopic and experimental data on the picritic glasses with the framework of mare basaltic magmatism.

Shearer, C. K.↗
NASA NTRS2013

Petrologic and In Situ Geochemical Constraints on Diogenite Genesis

Diogenites, members of the howardite, eucrite and diogenite (HED) clan, are orthopyroxenite, harzburgite and dunite meteorites [1-3]. Most are breccias, but remnant textures indicate they were originally coarse-grained rocks, with grain sizes of order of cm. Their petrography and compositions support an origin as crustal cumulates from a differentiated asteroid. Astronomical observations, and surface mineralogy and composition of Vesta determined by the Dawn spacecraft suggest that asteroid (4) Vesta is the parent object for HED meteorites [4-6]. The origin of diogenites is an unsettled issue. It is difficult to fit their bulk compositional characteristics into global magma ocean models that successfully describe the compositions of basaltic and cumulate eucrites [7]. Compositional analyses of acid-leached bulk samples have led to the hypothesis that many diogenites were formed late by interaction of their parent melts with a eucritic crust [8]. Those observations may alternatively be explained by subsolidus equilibration of trace elements between orthopyroxene and minor/ accessory phases in the rocks such as plagioclase and phosphate [7]. These competing hypotheses can be tested through in situ measurements of trace and minor elements in orthopyroxene. Our new petrologic observations and in situ minor and trace element data for a suite of diogenites are used to discuss the petrologic evolution of diogenites. Our preliminary data on two diogenites are consistent with the hypothesis that subsolidus element mobilization processes caused unusual trace element signatures seen in some diogenites [7]. We cannot stress strongly enough, however, that the sample set is too small and that additional data are required before definitive conclusions can be made.

Mittlefehldt, David W.↗
NASA NTRS1968

Geochemistry of andesites.

Trace element geochemistry of calc-alkaline andesites, discussing crustal composition models and trace elements distribution

Taylor, S. R.↗
NASA NTRS1972

The Washougal meteorite.

Optical study of the Washougal (Wash.), howardite, and determination of the ranges of composition of plagioclase and pyroxenes from measurements of densities and indices of refraction. Notable among many unique xenoliths are a round object whose morphology is that of an armored chondrule; a stratified fragment; and a centimeter-sized dunite xenolith (olivine Fa sub 12.8). The abundances of 27 elements, including all major elements and 15 trace elements are reported. To a first approximation, the composition of Washougal corresponds to a mixture of 51 wt per cent of eucritic material and 49 per cent of a diogenitic component, but excesses of some elements suggest a minor component of chondritic composition.

Jerome, D. Y.↗
NASA NTRS1981

Composition and origin of the unusual Oktibbeha County iron meteorite

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

Kracher, A.↗
NASA NTRS1984

Surface analysis of space telescope material specimens

Surface analysis by electron spectroscopy for chemical analysis (ESCA) was used to characterize a number of the material samples for the space telescope. With ESCA, the sample is irradiated with monoenergetic soft X-rays and the resulting emitted electrons are energy analyzed to determine the binding energy of electrons to the surface atoms. The major peaks were used in the quantitative determination of the surface composition. The presence of trace elements (impurities below 1% atomic composition) was also detailed. Initially a survey scan was run for each sample to deduce the elemental composition. Then the major peaks of interest and those of the trace elements were individually examined. After this, the samples were argon sputtered to etch away surface layers, and then additional measurements were carried out in order to obtain depth profile information. In this way it was possible for those species present only on the surface to be distinguished from those having a significant depth distribution within the sample.

Fromhold, A. T.↗
NASA NTRS1992

Chemical and isotopic constraints on the formation and crystallization of SA-1, a basaltic Allende plagioclase-olivine inclusion

Results are presented of a detailed petrologic, chemical, and Mg-isotope study of SA-1, a basaltic Allende plagioclase-olivine inclusion. The chemical and isotopic data were used to identify the signatures of nebular vs. planetary processes and to determine if SA-1 contains a component produced by planetary differentiation. It was found that the results of major-element and trace-element abundances in SA-1 are inconsistent with its formation as a mixture of nebular materials. It is suggested that SA-1 contains a chemically fractionated component produced by igneous differentiation.

Kennedy, Allen K.↗
NASA NTRS1996

Lunar Meteorite Queen Alexandra Range 93069 and the Iron Concentration of the Lunar Highlands Surface

Lunar meteorite Queen Alexandra Range 93069 is a clast-rich, glassy-matrix regolith breccia of ferroan, highly aluminous bulk composition. It is similar in composition to other feldspathic lunar meteorites but differs in having higher concentrations of siderophile elements and incompatible trace elements. Based on electron microprobe analyses of the fusion crust, glassy matrix, and clasts, and instrumental neutron activation analysis of breccia fragments, QUE 93069 is dominated by nonmare components of ferroan, noritic- anorthosite bulk composition. Thin section QUE 93069,31 also contains a large, impact-melted, partially devitrified clast of magnesian, anorthositic-norite composition. The enrichment in Fe, Sc, and Cr and lower Mg/Fe ratio of lunar meteorites Yamato 791197 and Yamato 82192/3 compared to other feldspathic lunar meteorites can be attributed to a small proportion (5-10%) of low-Ti mare basalt. It is likely that the non- mare components of Yamato 82192/3 are similar to and occur in similar abundance to those of Yamato 86032, with which it is paired. There is a significant difference between the average FeO concentration of the lunar highlands surface as inferred from the feldspathic lunar meteorites (mean: approx. 5.0%; range: 4.3-6.1 %) and a recent estimate based on data from the Clementine mission (3.6%).

Korotev, Randy L.↗
NASA NTRS2006

Multifrequency Ultra-High Resolution Miniature Scanning Microscope Using Microchannel And Solid-State Sensor Technologies And Method For Scanning Samples

A miniature, ultra-high resolution, and color scanning microscope using microchannel and solid-state technology that does not require focus adjustment. One embodiment includes a source of collimated radiant energy for illuminating a sample, a plurality of narrow angle filters comprising a microchannel structure to permit the passage of only unscattered radiant energy through the microchannels with some portion of the radiant energy entering the microchannels from the sample, a solid-state sensor array attached to the microchannel structure, the microchannels being aligned with an element of the solid-state sensor array, that portion of the radiant energy entering the microchannels parallel to the microchannel walls travels to the sensor element generating an electrical signal from which an image is reconstructed by an external device, and a moving element for movement of the microchannel structure relative to the sample. Discloses a method for scanning samples whereby the sensor array elements trace parallel paths that are arbitrarily close to the parallel paths traced by other elements of the array.

Wang, Yu↗
NASA NTRS2008

Genesis of Augite-Bearing Ureilites: Evidence From LA-ICP-MS Analyses of Pyroxenes and Olivine

Ureilites are ultramafic achondrites composed primarily of coarse-grained low-Ca pyroxene and olivine with interstitial carbonaceous material, but a number of them contain augite [1]. Ureilites are considered to be restites after partial melting of a chondritic precursor, although at least some augite-bearing ureilites may be partially cumulate [1, 2]. In this scenario, the augite is a cumulus phase derived from a melt that infiltrated a restite composed of typical ureilite material (olivine+low-Ca pyroxene) [2]. To test this hypothesis, we examined the major and trace element compositions of silicate minerals in select augite-bearing ureilites with differing mg#. Polished thick sections of the augite-bearing ureilites ALH 84136 , EET 87511, EET 96293, LEW 88201, and META78008 and augite-free typical ureilite EET 90019 were examined by EPMA for major and minor elements and laser ablation ICP-MS (LA-ICP-MS) for trace elements, REE in particular. Although EET 87511 is reported to contain augite, the polished section that we obtained did not.

Herrin, J. S.↗
NASA NTRS1991

Cosmic dust: Laboratory analyses of extremely small particles

A discussion of cosmic dust, its classification, the usefulness of its analysis, and problems associated with its analysis is presented. All measurements on stratospheric dust particles presented here were made with secondary ion mass spectrometry (SIMS). The SIMS technique turns out to be an extremely useful tool in the study of very small particles and made a number of firsts possible. The isotopic composition of cosmic dust particles were measured for the first time. It was also the first time that it was possible to measure the abundances of the rare earth elements in these particles. However, the most important advance this work represents is that both trace elemental and isotopic abundances were successfully measured in the same particles. Thus, for the first time, it is possible to compare isotopic and trace element abundance data of the same cosmic dust particles.

Stadermann, Frank J.↗