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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1972

Discrimination of fluoride and phosphate contamination in central Florida for analyses of environmental effects

A study was made of the spatial registration of fluoride and phosphate pollution parameters in central Florida by utilizing remote sensing techniques. Multispectral remote sensing data were collected over the area and processed to produce multispectral recognition maps. These processed data were used to map land areas and waters containing concentrations of fluoride and phosphate. Maps showing distribution of affected and unaffected vegetation were produced. In addition, the multispectral data were processed by single band radiometric slicing to produce radiometric maps used to delineate areas of high ultraviolet radiance, which indicates high fluoride concentrations. The multispectral parameter maps and radiometric maps in combination showed distinctive patterns, which are correlated with areas known to be affected by fluoride and phosphate contamination. These remote sensing techniques have the potential for regional use to assess the environmental impact of fluoride and phosphate wastes in central Florida.

Coker, A. E.↗
NASA NTRS2000

Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

NASA Discipline Exobiology↗
DOE OSTI2022

Strategies to Recover Easily-Extractable Rare Earth Elements and Other Critical Metals from Coal Waste Streams and Adjacent Rock Strata Using Citric Acid

Maximum rare earth element (REE) extractability from a sample of Middle Kittanning coal seam underclay was previously demonstrated at ~30% of the total REE content with a citric acid solution (Montross et al., 2020). This report further refines the mechanisms of citrate application for leaching of coal seam underclays using an organic acid lixiviant and evaluates strategies to begin to scale this process to industrially relevant volumes. This study evaluates the suitability of citrate leaching solutions for downstream recovery and separation of the REEs via oxalic acid precipitation. The applicability of citric acid solutions to recover ion-adsorbed metals from clay surfaces was evaluated by leaching a prepared sample of kaolinite with known amounts of ion-adsorbed lanthanum. Citrate systematics was further defined through experiments varying the solution pH. Up-scaling investigations proceeded with percolation leaching columns and stirred tank reactors. Two embodiments were run in percolation leaching: a continuous flow-through process and a multi-stage saturated process. The results showed that in certain limited scenarios, low pH citrate solutions could be used to target REEs mineralized within secondary calcium phosphate minerals. Results from the upscaling attempts encountered difficulties in extraction efficiencies. For the percolation columns, hydrodynamic flow was insufficient to recover the extractable REE content fully. For the stirred barrels, mixing inefficiencies likely inhibited the extractability of the REEs. Oxalic acid precipitation experiments also highlighted difficulties in downstream operations. The REEs were removed from the citrate solution with high efficiency, but were accompanied by equally efficient removal of calcium in orders of magnitude of greater amounts. Overall, for citrate leaching to be effective, future studies will have to: 1) carefully consider the feedstock application (i.e., likely better suited for secondary mineralization of calcium phosphate minerals), and 2) overcome the technical barriers of large-scale processing, such as inefficient hydrodynamic regimes due to small crush sizes needed and difficulties in downstream separation and purification. Alternatively, citrate solutions may be better recommended as leaching amendments to other leaching solutions to enhance REE complexation in the solution.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Prediction of the development of islet autoantibodies through integration of environmental, genetic, and metabolic markers

The Environmental Determinants of the Diabetes in the Young (TEDDY) study has prospectively followed, from birth, children at increased genetic risk of type 1 diabetes. We evaluated the potential of machine learning to identify new biomarkers that predict imminent (within 6 months) development of persistent islet autoantibodies to insulin, GAD or IA-2 in TEDDY participants through integration of time-invariant risk factors with time-varying metabolomics. The predictive modeling was initiated with over 220 potential biomarkers; through ensemble-based feature evaluation, the optimal model included 42 biomarkers, returning a cross-validated receiver operating characteristic area under the curve of 0.74. The model identified a principal set of 20 time-invariant markers, including 16 single nucleotide polymorphisms and two HLA-DR genotypes, gestational age, and exposure to a prebiotic formula. Integration of the metabolome identified 22 high-priority metabolites and lipids, including adipic acid and ceramide d42:0, that predicted development of islet autoantibodies, dependent upon the time horizon. The majority (86%) of metabolites that predicted development of islet autoantibodies belonged to 3 pathways: lipid oxidation, phospholipase A2 signaling, and pentose phosphate pathway. TEDDY data suggest that these metabolic processes may play a role in triggering islet autoimmunity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Mo-99 Concentration and processing by Solvent Extraction and Ion Exchange

Normally derived from its transient-equilibrium parent molybdenum-99 ( 99 Mo) (t½ = 66 h), the short-lived isotope technetium-99m ( 99m Tc) (t ½ = 6.0 h) is the most widely used medical isotope in diagnostic imaging today. The National Nuclear Security Administration’s (NNSA’s) Material Management and Minimization (M3) program—established under the auspices of the American Medical Isotope Production Act—has been tasked with facilitating the work of domestic 99 Mo suppliers that do not use highly enriched uranium (HEU). Superconducting electron linear accelerators that employ high-Z converter targets can generate bremsstrahlung photons and neutron fluxes that can induce photonuclear reactions and uranium (U) fission. Argonne, in collaboration with industrial partners, has been developing the process chemistry for superconducting linear accelerator (LINAC)-irradiated triuranium octoxide (U 3 O 8 ) targets to produce 99 Mo. In short, the process involves dissolving the irradiated targets in nitric acid, which simultaneously releases valuable fission products (xenon and iodine). After adjusting the acid concentration, producers process the feed using tri-n-butyl phosphate (TBP), then mix the raffinate derived from this extraction cycle with a phosphinic acid such as Cyanex 272 or di(2-ethylhexyl) phosphoric acid (HDEHP), which is selective for Mo (molybdenum liquid liquid extraction [MoLLE]). In the next step, a concentration column comprising an anion exchange platform is used to decontaminate the remaining fission products, generating a pure 99 Mo stream in sodium hydroxide (NaOH)/sodium chloride (NaCl).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Raman Spectroscopy Based On-Line, Real-Time Monitoring to Reduce Composition Uncertainties: Enhanced sensitivity through optimization of Raman Parameters

Optical spectroscopy-based on-line monitoring of Hanford processing streams can enable real-time characterization of chemical composition of process streams and batches, ultimately enabling and enhancing process control. It can provide immediate feedback on process conditions and has the potential to reduce the needed number of grab sample collections, thereby reducing times and costs associated with laboratory processing. Here we discuss the utilization of Raman spectroscopy to quantify multiple target analytes that are common within Hanford tanks and waste processing streams. Analytes include: nitrate, nitrite, carbonate, chromate, sulfate, phosphate, hydroxide, oxalate, ammonia, and aluminate. Most notably in this work, Raman applications to low-concentration streams are explored and optimized. Raman instrument specifications are compared; specifically, the impact of utilizing three different Raman excitation wavelengths, 405, 532, and 671 nm, is discussed. Also, Raman data collection parameters such as collection time and spectral averaging are measured and discussed. Finally, optical libraries of chemical targets were collected using optimized collection parameters and chemometric models were built to automate quantification of chemical targets. These models were validated through application to simulants and real Hanford process samples. Chemometric models performed well on both training and validation sets, suggesting these approaches can be successfully applied to on-line and real-time monitoring of low concentration Hanford processing streams. The use of the combine Raman wave lengths with the enhanced chemometric models for the low concentration streams significantly improved the chemical detection levels and significantly reduced uncertainties of those measurements.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Controlled evolution of rare earth phosphate in coal ash slag

Coal ash slag as a waste by-product, is generated from commercial processes that include gasification facilities, power plants, and steelmaking industries. Some is recycled into construction materials, insulation fibers, and used as a soil neutralizer, but the majority is still discarded. Coal ash slag exhibit trace amounts of critical materials including rare earth elements (REEs). An economically viable extraction of REEs from the coal ash would lower the production costs, addressing the availability and environmental concerns. In nature, most REEs exist as phosphate such as monazite but its synthetic evolution in coal ash slag has never been reported. In industrial processes, P may originate from coal, additives, and/or refractory liners. REEs may be extracted by first concentrating REEs into phosphates, sulphide, or fluorides [1], or carbonates [2]. In this work, P-enriched coal ash slag bearing REEs was first melted above 1600 °C, then crystallization behaviors in the melt during controlled cooling was studied. REE phosphate coprecipitated with mullite and hematite with mullite being the first crystal to form on cooling. The REEs were rejected from the molten slag, mullite, and hematite, and tended to segregate only to the phosphate phase with REE concentration as high as 58 wt.% in the structure.

Nakano, Jinichiro↗
DOE OSTI2021

Controlled evolution of rare earth phosphate in coal ash slag

Coal ash slag as a waste by-product, is generated from commercial processes that include gasification facilities, power plants, and steelmaking industries. Some is recycled into construction materials, insulation fibers, and used as a soil neutralizer, but the majority is still discarded. Coal ash slag exhibit trace amounts of critical materials including rare earth elements (REEs). An economically viable extraction of REEs from the coal ash would lower the production costs, addressing the availability and environmental concerns. In nature, most REEs exist as phosphate such as monazite but its synthetic evolution in coal ash slag has never been reported. In industrial processes, P may originate from coal, additives, and/or refractory liners. REEs may be extracted by first concentrating REEs into phosphates, sulphide, or fluorides [1], or carbonates [2]. In this work, P-enriched coal ash slag bearing REEs was first melted above 1600 °C, then crystallization behaviors in the melt during controlled cooling was studied. REE phosphate coprecipitated with mullite and hematite with mullite being the first crystal to form on cooling. The REEs were rejected from the molten slag, mullite, and hematite, and tended to segregate only to the phosphate phase with REE concentration as high as 58 wt.% in the structure.

Nakano, Jinichiro↗
DOE OSTI2026

Salt supplementation-induced metabolic reprogramming in Streptomyces coelicolor

Members of the genus Streptomyces are major producers of a wide variety of secondary metabolites that serve as bioactive compounds. Many secondary metabolites are produced in response to environmental signals such as biotic and abiotic stresses. In this study, we identified salt supplementation as one of the stimuli activating secondary metabolism in the model Streptomyces species, Streptomyces coelicolor. Comparative metabolomics revealed overproduction of several known secondary metabolites, most notably undecylprodigiosin and coelimycin P1, in addition to their biosynthetic intermediates and derivatives, as well as many unknown metabolites. Transcriptomic analysis revealed activation of diverse biological processes including cation uptake, compatible solute production, and the phosphate limitation stress response through conserved and species-specific mechanisms, presumably to overcome the increased salinity. This response leads to activation of a variety of regulatory and metabolic pathways required for production of secondary metabolites including activation of conserved metabolic pathways for energy and substrate supply and species-specific secondary metabolite biosynthetic gene clusters. Furthermore, several promoter sequences contributing to upregulation of secondary metabolism induced by salt supplementation were identified. Overall, our data show how S. coelicolor copes with the increased salinity and tailors the cellular metabolism toward secondary metabolism in a conserved and species-specific manner.

Otani, Hiroshi [USDOE Joint Genome Institute (JGI)↗
DOE OSTI2023

SoW for KDP Precision Cleaning System Control Sys Refurbishment

The KDP Optic Precision Cleaning System (PCS) is used is a standalone batch-process system used to clean Potassium di-Hydrogen Phosphate (KDP) optics required for the National Ignition Facility (NIF). There are two nearly identical machines owned by the US government, as provided by Lawrence Livermore National Security (LLNS). One machine is located at Lawrence Livermore National Laboratory in Livermore, CA in a Class 100 cleanroom and the other is located at the Gooch & Housego (G&H) facility in Highland Heights, OH in a Class 1,000 cleanroom.

42 ENGINEERING↗
DOE OSTI2026

Toward Sustainable Lithium Recovery: A Universal Hydrothermal Approach for Lithium Extraction

The rapid growth of lithium-ion battery (LIB) deployment presents critical challenges in sustainable end-of-life management and raw material recovery. Conventional pyrometallurgical and hydrometallurgical methods suffer from high energy demand, lithium loss, and complex wastewater treatment. This study established a universal, highly efficient, and sustainable hydrothermal route for lithium extraction and material recovery from various spent lithium-ion battery cathodes using 1,2,4,5-benzenetetracarboxylic acid (BTCA). The optimized process achieved over 99% lithium leaching efficiency for lithium iron phosphate (LFP) and LiNi x Mn y Co 1–x–y O 2 (NMC), with transition metal coleaching below 1%. It was also broadly applicable to lithium manganese oxide, lithium cobalt oxide, and black mass, achieving 98.5%, 98.95%, and 94.06% leaching efficiencies, respectively. The extracted lithium was directly converted into battery-grade lithium sources, while transition metals were recovered as oxides. Unreacted BTCA was efficiently regenerated and reused without degradation. Electrochemical evaluation confirmed that cathode materials synthesized with recovered lithium exhibit comparable performance to commercial products. Compared to conventional hydrometallurgy, the BTCA-based process increased revenue by over 40% and reduced greenhouse gas emissions by up to 39%. This closed-loop, chemistry-agnostic strategy offered a scalable and economically viable solution for industrial LIB recycling, enabling resource circularity and reducing dependency on primary critical materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Probing specific ion effects at air-aqueous dibutyl phosphate interfaces using vibrational sum frequency generation spectroscopy

Molecular properties at air–liquid and liquid–liquid interface hold the key to many processes involving molecular transport across phase boundaries from aerosol formation to carbon cycling and material separation using solvent extraction techniques. Using dibutyl phosphate (DBP) as a representative for partially aqueous soluble surfactants, the specific ion effect (SIE) of the Hofmeister series cations Cs + , Na + , Li + , and Mg 2+ on the partition and interaction between surfactant molecules and water molecules in the air–aqueous interface are investigated using vibrational sum frequency generation spectroscopy and surface tension measurements. In the presence of 1 mM and 1M bulk aqueous phase ionic strength salt concentrations, fundamental qualitative relationships are observed for the salting out of DBP relative to bulk aqueous phase nitrate salt concentrations and the specific cations species. At 1 mM ionic strength, the interfacial charge and hence the interfacial potential modulates the electrostatic interactions; in particular, the counter cations partially screen the negatively charged interface induced by the DBP in a direct Hofmeister order. At 1M ionic strength, the electric field at the interface or interfacial potential is effectively neutralized, and the counter cations promote the partitioning of DBP to the interface depending on their specific interaction with the DBP head group and metal ion hydration properties. The present results lay a foundation to study SIEs of heavier metals on hydrophobic-aqueous DBP interfaces.

Louie, Christina [Washington State University, Pul↗
DOE OSTI2024

Selective phosphate removal with manganese oxide composite anion exchange membranes in membrane capacitive deionization

The discharge of excessive phosphorous into water bodies can lead to serious eutrophication threatening aquatic ecosystem. Membrane capacitive deionization (MCDI) is an effective platform for deionizing aqueous streams; however, conventional MCDI is unable to selectively remove targeted ions from a liquid mixture. Here, in this work, we fabricated manganese oxide composite anion exchange membranes (AEMs) for MCDI to enhance phosphate removal selectivity from sodium chloride-sodium dihydrogen phosphate (10:1 M ratio) aqueous mixtures. We systematically investigated several critical factors, such as constant current or voltage operation, applied voltage amount, process stream pH, and manganese oxide (Mn 2 O 3 ) content in the AEM, on phosphate removal efficiency and phosphate selectivity. A trade-off was observed between phosphate removal and selectivity when increasing the cell voltage. Under the best conditions, a MCDI unit with a 20 wt% Mn 2 O 3 composite AEM and a bipolar membrane facilitated high phosphate removal efficiency of ≥ 31.8 % and a phosphate over chloride selectivity of 1.1 while showing stability for at least 30 cycles. To help understand how Mn 2 O 3 composite AEM boosts phosphate selectivity, static electronic structure calculations were performed, and they revelated that hydrogen phosphate absorption on Mn 2 O 3 composite AEM was 314 kcal/mol more exothermic than that on pristine AEM while chloride adsorption on Mn 2 O 3 composite AEM was 2.2 kcal/mol less exothermic than that on a pristine AEM. Overall, this work presents an effective strategy for selectively removing phosphate from model wastewater solutions and the mechanistic understanding that governs ion selectivity in composite ion-exchange membranes used in MCDI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Development and Advanced Testing of DPC Cement Fillers

The fillers research and development (R&D) program, mostly experimental, is part of a broader R&D program that includes new process modeling and performance assessment of criticality effects and the overall importance of criticality to repository performance (consequence screening). A literature research and consultation effort with experts by Hardin and Brady (2018) identified several potentially effective and workable filler materials including cements (primarily phosphate based), moltenmetal alloys, and low-temperature glasses. Filler attributes were defined, and the preliminary lists were compared qualitatively. Further comparative analysis will be done (e.g., cost estimates) after experimental screening has narrowed the list of alternatives. The research presented here is focused Sandia’s efforts for the development of phosphate-based cement fillers. Molten metal filler research is an ongoing activity at Oak Ridge National Laboratories and is not discussed herein. After the completion of the FY20 research effort the following cement filler compositions were selected for further experimental development work and advanced testing in FY21: 1. Aluminum phosphate cements (APCs); more specifically aluminum oxide / aluminum phosphate (Al 2 O 3 / AlPO 4 ) cements in which Al 2 O 3 serves as the filler material bound by an AlPO 4 binder formed by the reaction of Al 2 O 3 with various phosphate sources; 2. Wollastonite phosphate cements (WPCs), specifically wollastonite and aluminum or calcium aluminum phosphates in which CaSiO 3 serves as the filler material bound by a calcium phosphate that serves as the binder; and 3. Calcium aluminate phosphate cements (CAPCs) specifically grossite (CaAl 4 O 7 ) and hibonite (CaAl 11 O 18 ) fillers bound by an aluminum phosphate that serves as the binder. This effort focused on the optimization and subsequent processing of these three cements to achieve dense and well-consolidated monolithic samples. Upon completion of the FY21 effort the aluminum phosphate cements (APCs) and the calcium aluminate phosphate cements (CAPCs) show the most promise for advanced testing and scale up. We will begin the work in FY22 focused on testing the performance of these two cements in small scale DPCs as well as advanced materials testing to evaluate cement performance under expected radiation doses and representative post-closure geochemical environments.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2003

The Effect of Gravity on the Combustion Synthesis of Porous Biomaterials

Production of highly porous composite materials by traditional materials processing is limited by difficult processing techniques. This work investigates the use of self propagating high temperature (combustion) synthesis (SHS) to create porous tricalcium phosphate (Ca3(PO4)2), TiB-Ti, and NiTi in low and microgravity. Combustion synthesis provides the ability to use set processing parameters to engineer the required porous structure suitable for bone repair or replacement. The processing parameters include green density, particle size, gasifying agents, composition, and gravity. The advantage of the TiB-Ti system is the high level of porosity achieved together with a modulus that can be controlled by both composition (TiB-Ti) and porosity. At the same time, NiTi exhibits shape memory properties. SHS of biomaterials allows the engineering of required porosity coupled with resorbtion properties and specific mechanical properties into the composite materials to allow for a better biomaterial.

Castillo, M.↗
DOE OSTI2022

KVOPO 4 cathode for sodium ion batteries

An electrode comprising: NaVOPO 4 having orthorhombic crystalline symmetry and space group Pna2 1 , as an active intercalation host material, wherein the electrode is capable of electrochemical insertion and release of greater than one sodium ion per vanadium, wherein the NaVOPO 4 is formed by a solid phase synthesis process from a heated powdered mixture of ammonium metavanadate, ammonium phosphate monobasic, and potassium carbonate, to yield NaVOPO 4 having corner-sharing VO 6 octahedra and PO 4 tetrahedra, defining two types of tunnels comprising a first type of tunnel formed of rings of two PO 4 tetrahedra and a second type of tunnel formed of rings of three PO 4 tetrahedra and three VO 6 octahedra, followed by substitution of the potassium ions with sodium ions.

Whittingham, M. Stanley↗
NASA NTRS1977

The effect of carbon on phosphate reduction

Several experiments were performed in order to evaluate the effect of carbon on phosphate reduction in synthetic systems. It was attempted to simulate in the experiments conditions occurring during lunar impact processes, but without shock pressure. Temperature, oxygen fugacity, and bulk chemistry were evaluated separately in order to determine the conditions which are suitable for carbon reduction. It appears on the basis of the results of the reported investigation that carbon can be an effective reducing agent during reheating events such as those encountered by lunar soils and breccias. Phosphate reduction may be viewed as a two-step process in which carbon is mobilized as CO during heating and preferentially dissolved in the metal phase. It then acts as a reducing agent on cooling. Gas phase transport and diffusion of carbon in metal are sufficiently rapid to allow uniform carbon distribution both within and between metal grains. The availability of metal from meteorites and carbon from the solar wind is probably sufficient to make reduction by carbon a significant process on the lunar surface.

Friel, J. J.↗
NASA NTRS1999

Formation of glycolaldehyde phosphate from glycolaldehyde in aqueous solution

Amidotriphosphate (0.1 M) in aqueous solution at near neutral pH in the presence of magnesium ions (0.25 M) converts glycolaldehyde (0.025 M) within days at room temperature into glycolaldehyde phosphate in (analytically) nearly quantitative yields (76% in isolated product). This robust phosphorylation process was observed to proceed at concentrations as low as 30 microM glycolaldehyde and 60 microM phosphorylation reagent under otherwise identical conditions. In sharp contrast, attempts to achieve a phosphorylation of glycolaldehyde with cyclotriphosphate ('trimetaphosphate') as phosphorylating reagent were unsuccessful. Mechanistically, the phosphorylation of glycolaldehyde with amidotriphosphate is an example of intramolecular delivery of the phosphate group.

Non-NASA Center↗