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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.

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At least 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Evaluation of SDS depletion using an affinity spin column and IMS-MS detection

While the use of detergents is necessary for a variety of protein isolation preparation protocols, often prior to mass spectral (MS) analysis, they are not compatible with MS analysis due to ion suppression and adduct formation. This manuscript describes optimization of detergent removal, using commercially available SDS depletion spin columns containing an affinity resin, providing for both increased protein recovery and thorough SDS removal. Ion mobility spectrometry coupled with mass spectrometry (IMS-MS) allowed for a concurrent analysis of both analyte and detergent. In the case of both proteins and peptides, higher detergent concentrations than previously reported provided an increase of sample recovery; however there was a limit as SDS was detected by IMS-MS at higher levels of SDS indicating incomplete detergent depletion. The results also suggest optimal conditions for SDS removal are dependent on the sample concentration. Overall, this study provides a useful guide for proteomic studies where SDS is required for efficient sample preparation.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2013

Single-crystalline CuGeO{sub 3} nanorods: Synthesis, characterization and properties

Graphical abstract: - Highlights: • Single crystalline CuGeO{sub 3} nanorods were prepared via a hydrothermal route. • The material exhibits greatly enhanced activity in photocatalytic degradation of dyes. • The magnetic susceptibility measurements indicate spin-Peierls transition properties. • CuGeO{sub 3} nanorods may be of potential application in future integrated optical devices. - Abstract: Single crystalline CuGeO{sub 3} nanorods with a diameter of 20–35 nm and a length up to 1 μm have been prepared via a facile hydrothermal route with the assistance of ethylenediamine. Some influencing factors such as the reaction time, reaction temperature, the volume of ethylenediamine were revealed to play crucial roles in the formation of the CuGeO{sub 3} nanorods. A possible growth mechanism was proposed based on the experimental results. Significantly, this is the first time that CuGeO{sub 3} was used as a photocatalyst for organic pollutant degradation under UV light irradiation. The reaction constant (k) of CuGeO{sub 3} nanorods was five times that of the sample prepared by solid-state reaction under UV light irradiation. Additionally, the optical and magnetic properties of CuGeO{sub 3} nanorods were systematically studied.

36 MATERIALS SCIENCE↗
DOE OSTI2014

In Situ Electron Microscopy of Helium Bubble Implantation in Metal Hydrides

Here we investigated the microstructural response of various Pd physically vapor deposited films and Er and ErD 2 samples prepared from neutron Tube targets to implanted He via in situ ion irradiation transmission electron microscopy and subsequent in situ annealing experiments. Small bubbles formed in both systems during implantation, but did not grow with increasing fluence or a short duration room temperature aging (weeks). Annealing produced large cavities with different densities in the two systems. The ErD 2 showed increased cavity nucleation compared to Er. The spherical bubbles formed from high fluence implantation and rapid annealing in both Er and ErD 2 cases differed from microstructures of naturally aged tritiated samples. Further work is still underway to determine the transition in bubble shape in the Er samples, as well as the mechanism for evolution in Pd films.

36 MATERIALS SCIENCE↗
DOE OSTI2020

An international laboratory comparison of dissolved organic matter composition by high resolution mass spectrometry: Are we getting the same answer?

Since the first detailed compositional analysis of dissolved organic matter (DOM) in 1995, high resolution mass spectrometry (HRMS) has become a vital tool for DOM characterization. While the upward trend in HRMS for molecular level analysis of DOM continues, so do the challenges of data comparison and interpretation between laboratories operating instruments of differing performance and user operating conditions. It is therefore essential that the community establishes whether data and trends can be compared robustly between research groups. To this end, 4 identically prepared DOM samples were each studied by 16 laboratories, representing 17 commercially-purchased instruments located across 8 countries, using positive- and negative-mode electrospray ionization (ESI) HRMS analysis. Despite the widely reported sensitivity of ESI experiments to sample matrix, preparation, ion source operation and instrument tuning parameters, the instruments used in this study showed relatively low variability between results for the same samples, particularly H/C and AI metrics. The variation in O/C and m/z metrics was relatively higher, although z-score graphs and %BCD demonstrated that the relative difference in general chemical composition between samples was the same for each instrument included in the study. As such, these metrics can be used for fingerprinting of DOM samples and as a benchmark for quality control in participating laboratories, with future strides in environmental science building upon these efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Development of direct injection/ionization mass spectrometry methods for whole molecule characterization

Determining uranium isotopic and concentration information from environmental samples typically involves extensive chemical and physical processing prior to analysis. Harsh sample preparation results in the loss of the original uranium chemical speciation (i.e. what the uranium was bonded to/with when found in the environment) as well as the mixing of anthropogenic uranium with background material contained within the collection media (e.g. a swipe or soil). The objective of this work is to adapt a bioanalytical mass spectrometry technology called paper spray ionization mass spectrometry for the rapid analysis of intact uranium complexes. Soft ionization facilitates detection of whole molecule uranyl complexes including uranyl acetate, uranyl nitrate, and uranyl-tributylphosphate complex. Cotton swipe samples doped with a multi-element standard containing μg levels of U, Bi, Pb, Cd, Fe, and Zn were directly analyzed without purification, representing a major improvement over existing methods. Uranium quantitation is demonstrated using internal standards to obtain linear calibration curves. Limits of detection were determined to be approximately 100 ng for UO 2 and uranyl acetate through measurement of ppb level solutions. The development and qualification of PSI-MS techniques could lead to significant safeguards-related cost reduction and timeliness by facilitating the triage and queueing of swipe samples for more sensitive and time-consuming analyses.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Regioselective Generation of Single‐Site Iridium Atoms and Their Evolution into Stabilized Subnanometric Iridium Clusters in MWW Zeolite

Abstract Preparation of supported metal catalysts with uniform particle size and coordination environment is a challenging and important topic in materials chemistry and catalysis. In this work, we report the regioselective generation of single‐site Ir atoms and their evolution into stabilized subnanometric Ir clusters in MWW zeolite, which are located at the 10MR window connecting the two neighboring 12MR supercages. The size of the subnanometric Ir clusters can be controlled by the post‐synthesis treatments and maintain below 1 nm even after being reduced at 650 °C, which cannot be readily achieved with samples prepared by conventional impregnation methods. The high structure sensitivity, size‐dependence, of catalytic performance in the alkane hydrogenolysis reaction of Ir clusters in the subnanometric regime is evidenced.

Liu, Lichen↗
DOE OSTI2020

Regioselective Generation of Single‐Site Iridium Atoms and Their Evolution into Stabilized Subnanometric Iridium Clusters in MWW Zeolite

Abstract Preparation of supported metal catalysts with uniform particle size and coordination environment is a challenging and important topic in materials chemistry and catalysis. In this work, we report the regioselective generation of single‐site Ir atoms and their evolution into stabilized subnanometric Ir clusters in MWW zeolite, which are located at the 10MR window connecting the two neighboring 12MR supercages. The size of the subnanometric Ir clusters can be controlled by the post‐synthesis treatments and maintain below 1 nm even after being reduced at 650 °C, which cannot be readily achieved with samples prepared by conventional impregnation methods. The high structure sensitivity, size‐dependence, of catalytic performance in the alkane hydrogenolysis reaction of Ir clusters in the subnanometric regime is evidenced.

Liu, Lichen↗
DOE OSTI2014

Optimization of excess Bi doping to enhance ferroic orders of spin casted BiFeO{sub 3} thin film

Multiferroic Bismuth Ferrite (BiFeO{sub 3}) thin films with varying excess bismuth (Bi) concentration were grown by chemical solution deposition technique. Room temperature multiferroic properties (ferromagnetism, ferroelectricity, and piezoelectricity) of the deposited BiFeO{sub 3} thin films have been studied. High resolution X-ray diffraction and Raman spectroscopy studies reveal that the dominant phases formed in the prepared samples change continuously from a mixture of BiFeO{sub 3} and Fe{sub 2}O{sub 3} to pure BiFeO{sub 3} phase and, subsequently, to a mixture of BiFeO{sub 3} and Bi{sub 2}O{sub 3} with increase in the concentration of excess Bi from 0% to 15%. BiFeO{sub 3} thin films having low content (0% and 2%) of excess Bi showed the traces of ferromagnetic phase (γ-Fe{sub 2}O{sub 3}). Deterioration in ferroic properties of BiFeO{sub 3} thin films is also observed when prepared with higher content (15%) of excess Bi. Single-phased BiFeO{sub 3} thin film prepared with 5% excess Bi concentration exhibited the soft ferromagnetic hysteresis loops and ferroelectric characteristics with remnant polarization 4.2 μC/cm{sup 2} and saturation magnetization 11.66 emu/g. The switching of fine spontaneous domains with applied dc bias has been observed using piezoresponse force microscopy in BiFeO{sub 3} thin films having 5% excess Bi. The results are important to identify optimum excess Bi concentration needed for the formation of single phase BiFeO{sub 3} thin films exhibiting the improved multiferroic properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Ambient aromatic hydrocarbon measurements at Welgegund, South Africa

Aromatic hydrocarbons are associated with direct adverse human health effects and can have negative impacts on ecosystems due to their toxicity, as well as indirect negative effects through the formation of tropospheric ozone and secondary organic aerosol that affect human health, crop production and regional climate. Measurements were conducted at the Welgegund measurement station (South Africa) that is considered to be a regionally representative background site. However, the site is occasionally impacted by plumes from major anthropogenic source regions in the interior of South Africa, which include the western Bushveld Igneous Complex (e.g. platinum, base metal and ferrochrome smelters), the eastern Bushveld Igneous Complex (platinum and ferrochrome smelters), the Johannesburg-Pretoria metropolitan conurbation (>10 million people), the Vaal Triangle (e.g. petrochemical and industries), the Mpumalanga Highveld (e.g. coal-fired power plants and petrochemical industry) and also a region of anti-cyclonic recirculation of air mass over the interior of South Africa. The aromatic hydrocarbon measurements were conducted with an automated sampler on Tenax-TA and Carbopack-B adsorbent tubes with heated inlet for one year. Samples were collected twice a week for two hours during daytime and two hours 1 during night-time. A thermal desorption unit, connected to a gas chromatograph and a mass 2 selective detector was used for sample preparation and analysis. Results indicated that the 3 monthly median total aromatic hydrocarbon concentrations ranged between 0.01 to 3.1 ppb. 4 Benzene levels did not exceed local air quality standards. Toluene was the most abundant 5 species, with an annual median concentration of 0.63 ppb. No statistically significant 6 differences in the concentrations measured during daytime and night-time were found and no distinct seasonal patterns were observed. Air mass back trajectory analysis proved that the lack of seasonal cycles could be attributed to patterns determining the origin of the air masses sampled. Aromatic hydrocarbon concentrations were in general significantly higher in air masses that passed over anthropocentrically impacted regions. Interspecies correlations and ratios gave some indications of the possible sources for the different aromatic hydrocarbons in the source regions defined in the paper. The highest contribution of aromatic hydrocarbon concentrations to ozone formation potential was also observed in plumes passing over anthropocentrically impacted regions.

Jaars, K.↗
NASA NTRS1996

In Situ Mineralogical Analysis of Planetary Materials Using X-Ray Diffraction and X-Ray Fluorescence

Remote observations of Mars have led scientists to believe that its early climate was similar to that of the early Earth, having had abundant liquid water and a dense atmosphere. One of the most fascinating questions of recent times is whether simple bacterial life developed on Mars (as it did on the Earth) during this early element period. Analyses of SNC meteorites have broadened considerably our knowledge of the chemistry of certain types of Martian rocks, underscoring the tantalizing possibility of early hydrothermal systems and even of ancient bacterial life. Detailed analyses of SNC meteorites in Terrestrial laboratories utilize the most sophisticated organic, isotopic and microscopic techniques in existence. Indeed; it is unlikely that the key biogenic indicators used in McKay et al (ibid) could be identified by a remote instrument on the surface of Mars. As a result, it is probable that any robotic search for evidence of an ancient Martian biosphere will have as its focus the identification of key minerals in likely host rocks rather than the direct detection of organic or isotopic biomarkers. Even on a sample return mission, mineralogical screening will be utilized to choose the most likely candidate rocks. X-ray diffraction (XRD) is the only technique that can provide a direct determination of the crystal structures of the phases present within a sample. When many different crystalline phases are present, quantitative analysis is better constrained if used in conjunction with a determination of elemental composition, obtainable by X-ray fluorescence (XRF) using the same X-ray source as for XRD. For planetary surface analysis, a remote instrument combining XRD and XRF could be used for mineralogical characterization of both soils and rocks. We are designing a remote XRD/XRF instrument with this objective in mind. The instrument concept pays specific attention to constraints in sample preparation, weight, volume, power, etc. Based on the geometry of a pinhole camera (transmission geometry, flat two-dimensional detector perpendicular to the direct beam), the instrument (which we call CHEMIN, for Chemistry and Mineralogy) uses an X-ray sensitive CCD detector which will allow concurrent positional and energy-dispersive analysis of collected photons. Thus XRF (energy) and XRD (geometry) analysis of transmitted X-rays will be performed at the same time. Tests performed with single minerals and simple mixtures give promising results. Refinements of the prototype promise interpretable results on complex samples.

Sarrazin, P.↗
DOE OSTI2011

Surfactant-assisted hydrothermal crystallization of nanostructured lithium metasilicate (Li{sub 2}SiO{sub 3}) hollow spheres: (I) Synthesis, structural and microstructural characterization

Lithium metasilicate (Li{sub 2}SiO{sub 3}) was successfully synthesized using a hydrothermal process in the presence of different surfactants with cationic, non-ionic and anionic characters. The samples obtained were compared to a sample prepared by the conventional solid-state reaction method. The structural and microstructural characterizations of different Li{sub 2}SiO{sub 3} powders were performed using various techniques. Diffraction analyses revealed the successful crystallization of pure Li{sub 2}SiO{sub 3} single phase by hydrothermal technique, even without further heat-treatments and independent of the surfactant used. Electron microscopy analyses revealed that Li{sub 2}SiO{sub 3} powders were composed of uniform micrometric particles with a hollow sphere morphology and nanostructured walls. Finally, different thermal analyses showed that Li{sub 2}SiO{sub 3} samples preserved their structure and microstructure after further thermal treatments. Specific aspects regarding the formation mechanism of the spherical aggregates under hydrothermal conditions are discussed, and there is a special emphasis on the effect of the synthesis pathway on the morphological characteristics. -- Graphical abstract: Li{sub 2}SiO{sub 3} was synthesized using a hydrothermal process in the presence of different surfactants. Li{sub 2}SiO{sub 3} powders were composed of uniform micrometric particles with a hollow sphere morphology and nanostructured walls. Display Omitted Highlights: {yields} Pure Li{sub 2}SiO{sub 3} was synthesized by the hydrothermal method. {yields} Surfactant addition produced microstructural and morphological variations. {yields} TEM reveled the generation of nanostructured hollow spheres.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS2022

CO Chondrite Parent Body Processing as Recorded by Noble Gases

**Introduction:** CO carbonaceous chondrites are among the most primitive meteorites, of which some experienced mild degrees of thermal alteration (up to 500 °C) in their parent asteroid. Previous studies on aqueously altered CM, CY and CR chondrites have shown that the noble gases preserved in those meteorites can be used to assess the extent of parent body processing. This is mostly due to an Ar-rich carrier phase being susceptible to aqueous alteration. In this study, we follow up on these findings by investigating the effects of mild thermal alteration on the noble gas content of CO chondrites. They are subclassified from petrologic subtype 3.0 (e.g., Yamato-81025) to 3.8 (e.g., Isna) according to the degree of thermal alteration experienced. Understanding these effects does not only help to distinguish the most primitive samples from the severely altered ones, but also adds to the picture of the primordial volatile composition and distribution, as preserved in the most primitive material which accreted from the solar nebula at different heliocentric distances. Additionally, we search for pairing among samples, as part of an ongoing survey of Antarctic CO chondrites. **Experimental:** Noble gas measurements were conducted on aliquots of ~20-25 mg from 16 different samples of varying petrologic subtype from 3.0 to 3.8. The gas extraction occurred in one temperature step at ~1700 °C, followed by separation into three fractions, He-Ne, Ar, and Kr-Xe, measured successively in a custom-built mass spectrometer. For each sample, complete gas extraction was verified by a re-extraction step at ~1750 °C. Details on the sample preparation and measurement protocols can be found in. **Results and Discussion:** In most cases, the gas concentrations for all five noble gases decrease with increasing petrologic subtype, and the trend is most pronounced for Ne. An exception is e.g. CO3.0 Colony, which is strongly terrestrially weathered. CO3.8 Isna shows an unusually short expo-sure time to cosmic rays (~0.15 Ma), which may be explained by a direct injection into a mean orbital resonance shortly after collision. The currently ill-defined Ar-rich carrier phase, found only in the least aqueously altered CM and CR samples, is still abundantly present in the predominately anhydrous CO chondrites, indicating that this component is less susceptible to moderately elevated temperatures. No CO chondrites examined so far contain solar wind, supporting the hypothesis that CO chondrites originate from the asteroidal interior. It thus remains enigmatic which material could account for the surface layer.

Noble gas↗
DOE OSTI2019

Study of the Effect of Pr Doping on Structural, Morphological and Magnetic Properties of Nickel Ferrite

Praseodymium rare earth ion (Pr{sup 3+}) doped nickel ferrite (NiFe{sub 2−x}Pr{sub x}O{sub 4}, 0 < x< 0.1) nanocrystals (NFPO) were synthesized by hydrothermal method. The structural, morphological and magnetic properties of the prepared samples have been studied. The x-ray diffraction (XRD) and fourier transform infrared (FTIR) techniques confirmed the phase formation of the NFPO nanocrystals. The average crystallite size of NFPO nanoparticles found to be in the range 39 to 44 nm. The presence of Pr ions in NFPO was confirmed by energy-dispersive x-ray (EDX) analysis. It has been observed that after a certain amount of Pr doping, the morphology of the nanocrystals starts changing from nano-octahedrons to nanorods shape, as confirmed by transmission electron microscopy (TEM). Also, the magnetic properties of the prepared nanocrystals were measured using physical properties measurement system (PPMS) at 10 K and 300 K. The saturation magnetization (Ms) first decreases with the increasing loading amount of Pr ions up to (x = 0.025) and later it increases at both the temperatures. However, the value of coercivity shows an increasing trend with the increasing amount of Pr ions in NFPO at room temperature.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Analysis and Testing of Parsons NGS Solvent Formulation

Three drums containing solvent used during the Next Generation Solvent Test (NGST) conducted by Parsons in 2014-2015 were received at SRNL. After homogenization, samples from each drum were removed, and a composite sample prepared. This composite was analyzed to determine current SRNL characterization method efficacy, and to determine if the 1,3-dicyclohexyl-2- (isotridecyl) guanidine (DCiTG) suppressor could be selectively removed. The results of this work indicate that the titration analytical method currently employed at SRNL is effective at quantitating the DCiTG. The nuclear magnetic resonance (NMR) method at SRNL can detect the DCiTG, as well its amine and urea decomposition products. However, further development work will be required to allow the 1 H NMR method to quantitate these species. A series of three washing tests were performed on composite samples of the solvent. The results show that up to 67% of the DCiTG was removed from the solvent by simple washing, at multiple ratios of solvent: aqueous phase. This may indicate that a simple pathway exists to wash out the DCiTG and reclaim the solvent (~150 gallons) for future use at the Salt Waste Processing Facility (SWPF).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Rapid 235 U/ 238 U determination by matrix assisted ionization–time-of-flight mass spectrometry

Matrix-assisted ionization (MAI) of inorganic analytes is a nascent research domain that holds promise for rapid, potentially facility-deployable analytical applications. Here, we present results of MAI uranium isotopic analysis ( 235 U/ 238 U) obtained on the timescale of minutes utilizing simple sample preparation and an ambient ionization time-of-flight mass spectrometer (ToF MS). Experimental MAI-ToF MS characterization of uranium Certified Reference Materials (CRMs) was used to establish method calibration and validate quantitative 235 U/ 238 U determination spanning depleted, natural, and low-enriched uranium isotopic compositions. Secondary standard analyses with total uranium mass loadings of 5–500 ng per analysis yield accurate calibrated 235 U/ 238 U results and relative uncertainties of 4.7–17.2% (approx. ±95% confidence level), with weighted-mean uncertainties approaching 1.5%. This method permits accurate determination of uranium isotopic composition in a sample with uranium content as low as 200 pg for equal atom 235 U: 238 U. Instrument detection limits constrain the minimum uranium mass required to identify the presence of highly enriched uranium (HEU ≥20% 235 U) as only 500 pg using the method presented here. MAI-ToF MS quantitation of relatively extreme isotope ratios ( 235 U/ 238 U ≤ 0.01) is limited by detection of minor 235 U (LoD 100 pg 235 U/analysis ≈ 10 ng total U/analysis), and subsequent method optimization is anticipated to further reduce these limits. These findings underscore the potential of MAI-ToF MS for isotopic characterization of uranium and other inorganic species for both basic and applied science.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS2012

Non-Contact Conductivity Measurement for Automated Sample Processing Systems

A new method has been developed for monitoring and control of automated sample processing and preparation especially focusing on desalting of samples before analytical analysis (described in more detail in Automated Desalting Apparatus, (NPO-45428), NASA Tech Briefs, Vol. 34, No. 8 (August 2010), page 44). The use of non-contact conductivity probes, one at the inlet and one at the outlet of the solid phase sample preparation media, allows monitoring of the process, and acts as a trigger for the start of the next step in the sequence (see figure). At each step of the muti-step process, the system is flushed with low-conductivity water, which sets the system back to an overall low-conductivity state. This measurement then triggers the next stage of sample processing protocols, and greatly minimizes use of consumables. In the case of amino acid sample preparation for desalting, the conductivity measurement will define three key conditions for the sample preparation process. First, when the system is neutralized (low conductivity, by washing with excess de-ionized water); second, when the system is acidified, by washing with a strong acid (high conductivity); and third, when the system is at a basic condition of high pH (high conductivity). Taken together, this non-contact conductivity measurement for monitoring sample preparation will not only facilitate automation of the sample preparation and processing, but will also act as a way to optimize the operational time and use of consumables

Beegle, Luther W.↗
DOE OSTI2023

Understanding the effects of fabrication process on BaZr 0.9 Y 0.1 O 3– δ grain-boundary chemistry using atom probe tomography

Proton-conducting oxides, such as BaZr 0.9 Y 0.1 O 3–δ (BZY10), are receiving significant scientific attention for application in a variety of electrochemical applications. It has been shown that the synthesis route has a significant effect on the ionic behavior of these materials, especially the grain boundaries (GB). In this study, laser-pulsed atom probe tomography (APT) is used to characterize the GB chemistry of BZY10 samples prepared by four different methods: (1) spark plasma sintering (SPS), (2) conventional sintering followed by high-temperature annealing (HT), (3) conventional sintering with NiO used as a sintering aid (SSR-Ni), and (4) solid-state reactive sintering of oxide precursor powders with NiO as a reactive sintering aid (SSRS-Ni). Oxygen depletion (corresponding to oxygen vacancy accumulation) was observed at every GB in this study, consistent with the positive space-charge GB region commonly assigned to these materials. In contrast to the consistent trends associated with oxygen depletion, cation constituents showed varying segregation/depletion behaviors. The samples that used NiO revealed Ni preferentially segregating to the GB. The most common impurities in BZY10 are Al, Fe, Mg, Si, and Sr, all of which generally accumulate at GBs. In order to quantify these chemical trends, the APT method was optimized for this material supplemented with understanding from density functional theory (DFT). Finally, this APT study reveals the complexity of BZY10 GB chemistry and shows that even adjacent GBs in the same material can sometimes show surprisingly different GB chemistry.

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