Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “MINERALS”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ 57/54 Fe observations

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57 Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.

mineral alteration↗
DOE OSTI2014

Global changes in mineral transporters in tetraploid switchgrasses ( Panicum virgatum L.)

Switchgrass (Panicum virgatum L) is perennial, C4 grass with great potential as a biofuel crop. An in-depth understanding of the mechanisms that control mineral uptake, distribution and remobilization will benefit sustainable production. Nutrients are mobilized from aerial portions to below-ground crowns and rhizomes as a natural accompaniment to above-ground senescence post seed-set. Mineral uptake and remobilization is dependent on transporters, however, little if any information is available about the specific transporters that are needed and how their relative expression changes over a growing season. Using well-defined classes of mineral transporters, we identified 520 genes belonging to 40 different transporter classes in the tetraploid switchgrass genome. Expression patterns were determined for many of these genes using publically available transcriptomic datasets obtained from both greenhouse and field grown plants. Certain transporters showed strong temporal patterns of expression in distinct developmental stages of the plant. Gene-expression was verified for selected transporters using qRT-PCR. By and large these analyses confirmed the developmental stage-specific expression of these genes. Mineral analyses indicated that K, Fe, Mg, Co, and As had a similar pattern of accumulation with apparent limited remobilization at the end of the growing season. These initial analyses will serve as a foundation for more detailed examination of the nutrient biology of switchgrass.

switchgrass↗
DOE OSTI2022

Pore-Scale Modeling of Mineral Growth and Nucleation in Reactive Flow

A fundamental understanding of mineral precipitation kinetics relies largely on microscopic observations of the dynamics of mineral surfaces exposed to supersaturated solutions. Deconvolution of tightly bound transport, surface reaction, and crystal nucleation phenomena still remains one of the main challenges. Particularly, the influence of these processes on texture and morphology of mineral precipitate remains unclear. This study presents a coupling of pore-scale reactive transport modeling with the Arbitrary Lagrangian-Eulerian approach for tracking evolution of explicit solid interface during mineral precipitation. It incorporates a heterogeneous nucleation mechanism according to Classical Nucleation Theory which can be turned “on” or “off.” This approach allows us to demonstrate the role of nucleation on precipitate texture with a focus at micrometer scale. In this work precipitate formation is modeled on a 10 micrometer radius particle in reactive flow. The evolution of explicit interface accounts for the surface curvature which is crucial at this scale in the regime of emerging instabilities. The results illustrate how the surface reaction and reactive fluid flow affect the shape of precipitate on a solid particle. It is shown that nucleation promotes the formation of irregularly shaped precipitate and diminishes the effect of the flow on the asymmetry of precipitation around the particle. The observed differences in precipitate structure are expected to be an important benchmark for reaction-driven precipitation in natural environments.

58 GEOSCIENCES↗
DOE OSTI2025

Reactivity of Shale to Supercritical CO 2 : Insights from Microstructural Characterization and Mineral Phase Evolution in Caney Shales for CCUS Applications

Understanding mineral–fluid interactions in shale under supercritical CO 2 (scCO 2 ) conditions is relevant for assessing long-term geochemical containment. This study characterizes mineralogical transformations and elemental redistribution in five Caney Shale samples serving as proxies for reservoir (R1, R2, R3) and caprock (D1, D2) facies, subjected to 30-day static exposure to pure scCO 2 at 60 °C and 17.23 MPa (2500 psi), with no brine or impurities introduced. SEM-EDS analyses were conducted before and after exposure, with mineral phases classified into silicates, carbonates, sulfides, and organic matter. Initial compositions were dominated by quartz (38–47 wt.%), illite (16–23 wt.%), carbonates (12–18 wt.%), and organic matter (8–11 wt.%). Post-exposure, carbonate loss ranged from 15 to 40% in reservoir samples and up to 20% in caprock samples. Illite and K-feldspar showed depletion of Fe 2+ , Mg 2+ , and K + at grain edges and cleavages, while pyrite underwent oxidation with Fe redistribution. Organic matter exhibited scCO 2 -induced surface alteration and apparent sorption effects, most pronounced in R2 and R3. Elemental mapping revealed Ca 2+ , Mg 2+ , Fe 2+ , and Si 4+ mobilization near reactive interfaces, though no secondary mineral precipitates formed. Reservoir samples developed localized porosity, whereas caprock samples retained more structural clay integrity. The results advance understanding of mineral reactivity and elemental fluxes in shale-based CO 2 sequestration.

geochemical CO2 sequestration↗
NASA NTRSDate not supplied

The Complex Refractive Indices of Mineral Aerosols and Why They Matter

Aerosol refractive indices are fundamental parameters that are generally measured by spec-troscopists with specialized knowledge. We in the Earth science community frequently utilizethese refractive indices because they are essential for computing aerosol radiative effects andretrieving aerosol composition. Unfortunately, there are a wide variety of refractive indiceswith significant differences for some aerosol species (e.g., hematite) and a lack of refractiveindex choices for other aerosols (e.g., clay minerals, goethite), and this hinders our ability toaccurately compute the radiative effect of mineral dust. Additionally, the mineral refractiveindices used in atmospheric science are not necessarily linked to the mineral reflectancesused to identify surface mineralogy; this creates a disconnect between the atmosphere andthe surface that frustrates closure analyses.In this talk, we will present an overview of some refractive indices of radiative importancein aeolian dust (illite, kaolinite, montmorillonite, hematite, goethite). We will discuss howmineral refractive indices are used in aerosol retrievals, and how we can use remote sensingretrievals to narrow the range of viable choices. We will also discuss how we can use pub-lished spectroscopic measurements to extrapolate the refractive indices that are inferred ata handful of visible and near-infrared wavelengths to the longwave regime. Finally, we willdiscuss how working groups like MIRA (Models, In situ, and Remote sensing of Aerosols;https://science.larc.nasa.gov/mira-wg/) and community repositories like TAO (Tables ofAerosol Optics) can improve radiative closure by enhancing interactions between the threedisciplines.1

aerosols↗
DOE OSTI2013

Carbon Footprint of Biofuel Sugarcane Produced in Mineral and Organic Soils in Florida

Ethanol produced from sugarcane is an existing and accessible form of renewable energy. In this study, we applied the Life Cycle Assessment (LCA) approach to estimate the Carbon Footprint (CFP) of biofuel sugarcane produced on mineral (sandy) and organic (muck) soils in Florida. CFP was estimated from greenhouse gas (GHG) emissions (CO2, CH4, and N2O) during the biofuel sugarcane cultivation. The data for the energy (fossil fuels and electricity), equipment, and chemical fertilizers were taken from enterprise budgets prepared by the University of Florida based on surveys and interviews obtained from local growers during the cropping years 2007/2008 and 2009/2010 for mineral soils and 2008/2009 for organic soils. Emissions from biomass burning and organic land use were calculated based on the IPCC guidelines. The results show that the CFP for biofuel sugarcane production is 0.04 kg CO2e kg-1y-1 when produced in mineral soils and 0.46 kg CO2e kg-1y-1 when produced in organic soils. Most of the GHG emissions from production of biofuel sugarcane in mineral soils come from equipment (33%), fertilizers (28%), and biomass burning (27%); whereas GHG emissions from production in organic soils come predominantly from the soil (93%). This difference should be considered to adopt new practices for a more sustainable farming system if biofuel feedstocks are to be considered.

09 BIOMASS FUELS↗
DOE OSTI2023

Advanced Mineral Separations with Novel Simulated Moving Beds

Lithium is a critical mineral that is widely used in batteries and energy storage applications, making it increasingly important in the next few decades. To meet the growing demand for lithium and secure domestic supply chains, there is a need to exploit unconventional lithium resources. However, utilizing current lithium extraction processes is challenging due to the high salinity in those resources. Thus, it is essential to develop energy-efficient, and less chemical-intensive separation processes that can exploit high-salinity lithium resources. Accordingly, this project aims to design a novel zwitterionic stationary phase and use it to develop a continuous chromatography process to recover LiCl minerals from traditionally unexploited domestic saline resources. The developed zwitterionic stationary phase allows fractionating minerals based on their different sorbent affinities under water elution. A systematically designed continuous process can separate lithium from other minerals, reducing the risk of material fouling and the overall chemical consumption to produce battery-grade lithium. This approach is expected to significantly enhance the efficiency and sustainability of the lithium extraction process while also reducing the environmental impact associated with traditional processes. At the end of the project, the technology will be demonstrated in continuous mode using a simulated moving bed (SMB) to recover >100 g of LiCl from real resource waters. The U.S.-based resources that this project targets for LiCl recovery are formation water, oil-produced water, and geothermal brines, supplied by Standard Lithium Ltd. and Shell Inc, respectively.

critical minerals↗
DOE OSTI2025

The CO2 mineralization potential of New Mexico basalts and associated critical element behavior and mobility.

This presentation reports on laboratory experiments assessing the carbon dioxide (CO₂) mineralization potential of New Mexico basalts, including trachybasalt and basalt lithologies. Using simulated groundwater and controlled conditions, the study evaluates the kinetics of CO₂ sequestration, mineral saturation indices, and secondary mineral formation. It also investigates the mobility of critical and trace elements such as Ni, Zn, Cu, and Li during basalt dissolution. Results indicate that New Mexico basalts can effectively sequester CO₂ through carbonate formation, with grain size and mineral composition influencing reaction rates and elemental behavior. These findings support the viability of geologic carbon storage in mafic volcanic terrains and inform strategies for critical element recovery.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Policy Reforms to Unleash Domestic Critical Minerals Mining and Processing

The United States faces growing strategic and economic risks due to its limited ability to mine, process, and refine the minerals required for national defense, energy systems, advanced manufacturing, and emerging technologies. Although the country possesses significant geological resources, development has been slowed by long and unpredictable permitting timelines, fragmented regulatory responsibilities, limited midstream processing capacity, and a shrinking technical workforce. These structural barriers have created supply chain vulnerabilities that constrain industrial growth and reduce national resilience. This report presents a comprehensive set of reforms intended to modernize the nation’s approach to critical minerals. The recommendations address federal permitting, environmental review processes, the legal framework governing mining activities, interagency coordination, domestic processing and refining capacity, and the education and workforce systems needed to support long term industry development. The analysis emphasizes practical steps to shorten project timelines, improve regulatory clarity, expand processing infrastructure, enable recovery from both conventional and nontraditional sources, and update outdated requirements that hinder the development of essential materials. Taken together, the recommended reforms would strengthen domestic supply chains, improve investment certainty, and reduce dependence on external minerals and processing infrastructure. By aligning policy, regulatory frameworks, and workforce capabilities with national needs, the United States can build a more resilient and secure critical minerals ecosystem that supports long term economic competitiveness and technological leadership.

29 - ENERGY PLANNING, POLICY AND ECONOMY↗
DOE OSTI2021

Hydrothermal mineral alterations in the Brady and Desert Peak geothermal fields

Results of the analysis of HyMap's spectra against know hydrothermally altered minerals in the Brady-Desert Peak Geothermal Areas. The analysis was performed using ENVI's Target Detection process against USGS library spectra for Chalcedony, Kaolinite, Gypsum, Hematite and Epsomite. Each compressed file includes three raster images created after fusing the target detection results for all minerals: _fusion_all - Contains the 8 layers resulting from target detection and fusion of the 5 minerals _fusion_all_normal - Contains each layer as above, after Winsorization (99% percentile on the positive side only due to skewness of results), and normalization of each layer to achieve a range between [0-1] _fusion_final - Contains a fused raster by sub-setting the normalized layers, with the results of MTMF, MTTCIMF, OSP and SAM. Both CEM and MF were discarded as being less accurate than MTMF, and TCIMF is less accurate than MTTCIMF, ACE results were discarded because they were notably different from the rest of the analyses. The base_names are: brady - Brady geothermal area only desert - Desert Peak geothermal area only hymap - Full image analysis comprising both the Brady and Desert Peak geothermal areas

15 GEOTHERMAL ENERGY↗
DOE OSTI2021

Fleetite, Cu 2 RhIrSb 2 , a New Species of Platinum-Group Mineral from the Miass Placer Zone, Southern Urals, Russia

Fleetite, Cu 2 RhIrSb 2 , a new species of platinum-group mineral (PGM), was discovered intergrown with an Os–Ir–Ru alloy in the Miass Placer Zone (Au–PGE), southern Urals, Russia. A single grain 50 μm across was found. Osmium, ruthenium, and iridium are the main associated minerals; also present are Pt–Fe alloys, laurite, Sb-rich irarsite, Rh-rich tolovkite, kashinite, anduoite, ferronickelplatinum, heazlewoodite, PGE-bearing pentlandite and digenite, as well as micrometric inclusions of forsterite (Fo 93.7 ), chromite–magnesiochromite, and Mg-rich edenite. In reflected light, fleetite is light gray; it is opaque, isotropic, non-pleochroic, and non-bireflectant. We report reflectance values measured in air. A mean of seven point-analyses (wavelength-dispersive spectrometry) gave Cu 13.93, Ni 8.60, Fe 0.10, Ir 28.07, Rh 7.91, Ru 1.96, Sb 39.28, total 99.85 wt.%, corresponding to (Cu 1.41 Ni 0.58 Fe 0.01 ) Σ2.00 (Rh 0.49 Ni 0.36 Ru 0.12 ) Σ0.97 Ir 0.95 Sb 2.08 on the basis of six atoms per formula unit, taking into account the structural results. The calculated density is 10.83 g/cm 3 . Single-crystal X-ray studies show that fleetite is cubic, space group Fdm (#227), a = 11.6682(8) Å, V = 1588.59(19) Å 3 , and Z = 16. A least-squares refinement of X-ray powder-diffraction data gave a = 11.6575(5) Å and V = 1584.22(19) Å 3 . The strongest five reflections in the powder pattern [d in Å(I)(hkl)] are: 6.70(75)(111), 4.13(100)(220), 3.52(30)(311), 2.380(50)(422), 2.064(40)(440). Results of synchrotron micro-Laue diffraction experiments are consistent [a = 11.66(2) Å]. The crystal structure of fleetite was solved and refined to R = 0.0340 based upon 153 reflections with F o > 4σ(F o ). It is isotypic with Pd 11 Bi 2 Se 2 and best described as intermetallic, with all metal atoms in 12-fold coordination. Fleetite and other late exotic phases were formed by reaction of the associated alloy phases with a fluid phase enriched in Sb, As, and S in circulation in the cooling ophiolite source-rock. The mineral is named after Michael E. Fleet (1938–2017) in recognition of his significant contributions to the Earth Sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Evaluation of preservation protocols for oxygen-sensitive minerals within laminated aquatic sediments

Laminated sediments can record seasonal changes in sedimentation of material from anoxic waters, including minerals of the redox-sensitive elements Fe, Mn, and S that form under varying oxygen levels, mineral saturation conditions, and from microbial metabolism. However, preserving the oxygen-sensitive minerals for identification is challenging when preservation of the spatial arrangement of laminae is also required. In this study, we compare methods for embedding sedimentary materials from anoxic waters and sediments from Brownie Lake, Minnesota, USA for analysis of the speciation for Fe, Mn, and S using synchrotron-based X-ray absorption near edge spectroscopy (XANES). We found that acetone dehydration and resin replacement in a 100% N 2 glovebox successfully preserved the speciation of Fe and Mn minerals within laminated sediments. However, acetone removed some sulfur species from sediments, and epoxies contained sulfur species, which challenged identification of native sulfur species. Results from this study will aid researchers who are interested in spatial analysis of oxygen sensitive sediments, soils, or microbial mats in choosing a preservation method.

58 GEOSCIENCES↗
DOE OSTI2023

A large nitrogen supply from the stable mineral-associated soil organic matter fraction

Soil organic matter (SOM) mineralization and nitrogen (N) release are key biogeochemical processes for which the relative contribution of particulate (POM) and mineral-associated organic matter (MAOM) fractions is poorly understood. MAOM is generally considered to be a more stable fraction that contains most of the soil organic N, whereas POM is more readily decomposable and contains less N. We measured variations in the potentially mineralizable N from each SOM fraction across three contrasting land uses (forest, pasture, and croplands) and two different grazing managements (rotational and continuous grazing). Contrary to expectations, we found that the MAOM fraction consistently supplied more N than the POM fraction during SOM mineralization in all land-uses evaluated. Across our environmental gradient, potentially mineralizable N from POM increased with the carbon (C) concentration and C/N ratio of POM, while potentially mineralizable N from MAOM increased with the C concentration of MAOM but decreased with clay content. Our work suggests that MAOM contributions to short-term N mineralization and N supply to plants have been undervalued.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Evidence linking calcium to increased organo-mineral association in soils

Geochemical indicators are emerging as important predictors of soil organic carbon (SOC) dynamics, but evidence concerning the role of calcium (Ca) is scarce. This study investigates the role of Ca prevalence in SOC accumulation by comparing otherwise similar sites with (CaCO 3 -bearing) or without carbonates (CaCO 3 -free). We measured the SOC content and indicators of organic matter quality (C stable isotope composition, expressed as δ 13 C values, and thermal stability) in bulk soil samples. We then used sequential sonication and density fractionation (DF) to separate two occluded pools from free and mineral-associated SOC. The SOC content, mass, and δ 13 C values were determined in all the fractions. X-ray photoelectron spectroscopy was used to investigate the surface chemistry of selected fractions. Our hypothesis was that occlusion would be more prevalent at the CaCO 3 -bearing site due to the influence of Ca on aggregation, inhibiting oxidative transformation, and preserving lower δ 13 C values. Bulk SOC content was twice as high in the CaCO 3 -bearing profiles, which also had lower bulk δ 13 C values, and more occluded SOC. Yet, contrary to our hypothesis, occlusion only accounted for a small proportion of total SOC (< 10%). Instead, it was the heavy fraction (HF), containing mineral-associated organic C, which accounted for the majority of total SOC and for the lower bulk δ 13 C values. Overall, an increased Ca prevalence was associated with a near-doubling of mineral-associated SOC content. Future investigations should now aim to isolate Ca-mediated complexation processes that increase organo-mineral association and preserve organic matter with lower δ 13 C values.

58 GEOSCIENCES↗
DOE OSTI2021

Low soil phosphorus availability triggers maize growth stage specific rhizosphere processes leading to mineralization of organic P

Phosphorus (P) is one of the essential nutrients for all living organisms. High-quality mineral P fertilizer is a finite resource with only an estimated 80-100 years of reserves remaining globally. Both plants and microbes have developed several mechanisms such as secretion of organic acids, acidification of the rhizosphere, and production of extracellular enzymes to enhance the acquisition of P from soils. Increased activity of phosphatase occurs in response to P deficiency as part of P starvation responses which catalyze the hydrolysis of P o from soil organic matter (SOM) and release inorganic P (P i ). However, the specific interactions between plants and microbial communities in the rhizosphere soil triggered by P deficiency are largely unknown. In a greenhouse study we grew maize plants in low and high P containing soils and examined the role of rhizosphere processes on mineralization of organic P (P o ) in soils with low and high P availability and different P speciation 23 (Po dominated versus P i dominated) and determine its effect on plant growth. Plant biomass was determined and rhizosphere soils, and soil samples from pots with and without plants were collected at key vegetative growth stages (VGS). A variety of biogeochemical parameters (e.g. microbial biomass C and P, potential phosphatase activities, plant biomass P, soil P species etc.) were determined using both conventional (sequential chemical extraction) and advanced (e.g. high resolution mass spectrometry (FTICR-MS) and 3129 P solution NMR) techniques. Here, we used phospholipid fatty acid (PLFA) and DNA based microbial community analysis to track changes in microbial community structure and diversity. Low P availability induced changes in biogeochemical processes and microbial community composition in the rhizosphere soils of plants grown in low P containing soil. At early VGS, the plants in low P soil were visually struggling which correlated with greater rhizosphere potential acid phosphatase activity and a reduction in P o fractions. At late VGS, the plants appeared to recover which correlated with a decrease in Meh (III) extractable P, an increase in microbial biomass C and P and greater total P in the plant biomass (roots, shoots and leaves). In high P containing soil, on the other hand, greater P availability masked these rhizosphere processes. Our results confirmed the degradation of SOM and Po mineralization in rhizosphere soils driven by microbe and plant need for P. P deficiency may have favored the abundance of fungi which utilized easily degradable root exudates for the production of extracellular enzymes responsible for the mineralize of SOM P o . This study highlights the intertwined mechanisms involved, and emphasizes the importance of, P o sources for plant nutrition and survival in marginal soils.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Mineral and fluid transformation of hydraulically fractured shale: case study of Caney Shale in Southern Oklahoma

This study explores the geochemical reactions that can cause permeability loss in hydraulically fractured reservoirs. The experiments involved the reaction of powdered-rock samples with produced brines in batch reactor system at temperature of 95 °C and atmospheric pressure for 7-days and 30-days respectively. Results show changes in mineralogy and chemistry of rock and fluid samples respectively, therefore confirming chemical reactions between the two during the experiments. The mineralogical changes of the rock included decreases of pyrite and feldspar content, whilst carbonate and illite content showed an initial stability and increase respectively before decreasing. Results from analyses of post-reaction fluids generally corroborate the results obtained from mineralogical analyses. Integrating the results obtained from both rocks and fluids reveal a complex trend of reactions between rock and fluid samples which is summarized as follows. Dissolution of pyrite by oxygenated fluid causes transient and localized acidity which triggers the dissolution of feldspar, carbonates, and other minerals susceptible to dissolution under acidic conditions. The dissolution of minerals releases high concentrations of ions, some of which subsequently precipitate secondary minerals. On the field scale, the formation of secondary minerals in the pores and flow paths of hydrocarbons can cause significant reduction in the permeability of the reservoir, which will culminate in rapid productivity decline. This study provides an understanding of the geochemical rock–fluid reactions that impact long term permeability of shale reservoirs.

58 GEOSCIENCES↗
DOE OSTI2017

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO 2 ) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondary uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca 2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K + and Pb 2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.

58 GEOSCIENCES↗
DOE OSTI2025

LABQ3: Bayesian method for quantification of mineral compositions and nano-scale elemental mapping of 3D synchrotron XCT data

Quantitative analysis of mineral compositions is essential in understanding geochemical, mineralogical and environmental processes. Fine-resolution 3D imaging is widely done using synchrotron X-ray computed tomography (XCT), but existing analyses are limited to visualization and segmentation. This paper presents a new method, Linear Attenuation Bayesian Quantitative 3D-mapper (LABQ3), based on the linearity of X-ray attenuation with respect to elemental concentrations. To address the random variability in attenuation measurements, LABQ3 employs Bayesian decision theory to minimize classification error, using reference attenuation distributions from scans of pure mineral standards. To demonstrate LABQ3 and test its performance, we studied precipitated carbonate samples. XCT scans were done at multiple energies using the transmission X-ray microscope (TXM) at beamline 32-ID-C of the Advanced Photon Source at Argonne National Laboratory. The reconstructed 3D images have a voxel size of 20 nm. Analyses revealed rich nano-scale compositional heterogeneity within individual particles. A mixture of calcium and cadmium produced an overall stoichiometric composition of (Ca 0.78 ,Cd 0.22 )CO 3 , with some voxels containing nearly pure CdCO 3 . The addition of zinc led to an overall stoichiometric composition of 33% Ca, 28% Cd, 39% Zn, with a nearly pure CaCO 3 core and compositional zonation through the rim. These compositional gradients are related to temporal sequences of carbonate mineral formation where Cd precipitated at the beginning in (Ca,Cd)CO 3 , while Cd and Zn precipitated at the end in (Ca, Cd,Zn)CO 3 . Results differ from bulk analyses using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), showing that LABQ3 provides particle-specific insights. LABQ3 distinguishes itself by quantifying chemical compositions along a continuum, making it different from XCT analyses based on segmentation. LABQ3 allows simultaneous acquisition of morphology and chemical composition in 3D, facilitating the interpretation of chemical gradients of trace elements, quantification of solid solution compositions, inferences about temporal sequences of mineral precipitation, and addressing other concerns about solid-phase chemistry.

58 GEOSCIENCES↗