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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Separation of Radionuclides from a Rare Earth-Containing Solution by Zeolite Adsorption

The increasing industrial demand for rare earths requires new or alternative sources to be found. Within this context, there have been studies validating the technical feasibility of coal and coal byproducts as alternative sources for rare earth elements. Nonetheless, radioactive materials, such as thorium and uranium, are frequently seen in the rare earths’ mineralization, and causes environmental and health concerns. Consequently, there exists an urgent need to remove these radionuclides in order to produce high purity rare earths to diversify the supply chain, as well as maintain an environmentally-favorable extraction process for the surroundings. In this study, an experimental design was generated to examine the effect of zeolite particle size, feed solution pH, zeolite amount, and contact time of solid and aqueous phases on the removal of thorium and uranium from the solution. The best separation performance was achieved using 2.50 g of 12-µm zeolite sample at a pH value of 3 with a contact time of 2 h. Under these conditions, the adsorption recovery of rare earths, thorium, and uranium into the solid phase was found to be 20.43 wt%, 99.20 wt%, and 89.60 wt%, respectively. The Freundlich adsorption isotherm was determined to be the best-fit model, and the adsorption mechanism of rare earths and thorium was identified as multilayer physisorption. Further, the separation efficiency was assessed using the response surface methodology based on the development of a statistically significant model.

58 GEOSCIENCES↗
DOE OSTI2020

Quantifying the Influence of Jupiter on the Earth’s Orbital Cycles

A wealth of Earth-sized exoplanets will be discovered in the coming years, providing a large pool of candidates from which the targets for the search for life beyond the solar system will be chosen. The target selection process will require the leveraging of all available information in order to maximize the robustness of the target list and make the most productive use of follow-up resources. Here, we present the results of a suite of n-body simulations that demonstrate the degree to which the orbital architecture of the solar system impacts the variability of Earth’s orbital elements. By varying the orbit of Jupiter and keeping the initial orbits of the other planets constant, we demonstrate how subtle changes in solar system architecture could alter the Earth’s orbital evolution—a key factor in the Milankovitch cycles that alter the amount and distribution of solar insolation, thereby driving periodic climate change on our planet. The amplitudes and frequencies of Earth’s modern orbital cycles fall in the middle of the range seen in our runs for all parameters considered—neither unusually fast nor slow, neither large nor small. This finding runs counter to the “Rare Earth” hypothesis, which suggests that conditions on Earth are so unusual that life elsewhere is essentially impossible. Our results highlight how dynamical simulations of newly discovered exoplanetary systems could be used as an additional means to assess the potential targets of biosignature searches, and thereby help focus the search for life to the most promising targets.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2000

Accretion of Moon and Earth and the emergence of life

The discrepancy between the impact records on the Earth and Moon in the time period, 4.0-3.5 Ga calls for a re-evaluation of the cause and localization of the late lunar bombardment. As one possible explanation, we propose that the time coverage in the ancient rock record is sufficiently fragmentary, so that the effects of giant, sterilizing impacts throughout the inner solar system, caused by marauding asteroids, could have escaped detection in terrestrial and Martian records. Alternatively, the lunar impact record may reflect collisions of the receding Moon with a series of small, original satellites of the Earth and their debris in the time period about 4.0-3.5 Ga. The effects on Earth of such encounters could have been comparatively small. The location of these tellurian moonlets has been estimated to have been in the region around 40 Earth radii. Calculations presented here, indicate that this is the region that the Moon would traverse at 4.0-3.5 Ga, when the heavy and declining lunar bombardment took place. The ultimate time limit for the emergence of life on Earth is determined by the effects of planetary accretion--existing models offer a variety of scenarios, ranging from low average surface temperature at slow accretion of the mantle, to complete melting of the planet followed by protracted cooling. The choice of accretion model affects the habitability of the planet by dictating the early evolution of the atmosphere and hydrosphere. Further exploration of the sedimentary record on Earth and Mars, and of the chemical composition of impact-generated ejecta on the Moon, may determine the choice between the different interpretations of the late lunar bombardment and cast additional light on the time and conditions for the emergence of life.

NASA Discipline Exobiology↗
NASA NTRS2003

Biosignatures of early earths

A major goal of NASA's Origins Program is to find habitable planets around other stars and determine which might harbor life. Determining whether or not an extrasolar planet harbors life requires an understanding of what spectral features (i.e., biosignatures) might result from life's presence. Consideration of potential biosignatures has tended to focus on spectral features of gases in Earth's modern atmosphere, particularly ozone, the photolytic product of biogenically produced molecular oxygen. But life existed on Earth for about 1(1/2) billion years before the buildup of atmospheric oxygen. Inferred characteristics of Earth's earliest biosphere and studies of modern microbial ecosystems that share some of those characteristics suggest that organosulfur compounds, particularly methanethiol (CH(3)SH, the sulfur analog of methanol), may have been biogenic products on early Earth. Similar production could take place on extrasolar Earth-like planets whose biota share functional chemical characteristics with Earth life. Since methanethiol and related organosulfur compounds (as well as carbon dioxide) absorb at wavelengths near or overlapping the 9.6-microm band of ozone, there is potential ambiguity in interpreting a feature around this wavelength in an extrasolar planet spectrum.

Earth (Planet)↗
NASA NTRS2005

Earth-Image Tracking in the IR for Deep Space Optical Communications

Sub-microradian level laser beam pointing to an Earth-based receiver is required for deep space optical communications. This requires a beacon emanated from Earth towards the spacecraft. The beacon could be a laser or reflected sunlight from Earth. Earth image tracking in the visible is hampered by significant albedo variations and/or crescent Earth image yielding large central errors. Here, we report results of Earth-image tracking in the infrared (8 to 13 micron) region of the spectrum with the aim of substantially alleviating the two challenges mentioned earlier.

earth image tracking↗
NASA NTRSDate not supplied

Constraining Venus Cloud Habitability: Earth's Aerobiosphere as an Analogue Environment

The potential habitability of Venus's cloud and haze layers has been debated for decades, with interest fueled by observations including disequilibria in atmospheric chemistry, strongly UV-absorbing particles, and (most recently) a controversial phosphine detection. Venus cloud temperature and pressure are clement by Earth standards; however, the calculated high acid activity and low water activity may exceed the limits of Earth biochemistry, based on observed life in extreme environments. A significant challenge in understanding Venus's habitability is the lack of an appropriate terrestrial analogue environment. Life has not been found in hydrothermal systems approaching Venus aerosol acidities, but these systems also contain high levels of other harsh solutes. Earth's stratospheric sulfate layer is a partial match in terms of acidity, desiccation, size, and isolation from the surface, but the few samples returned from these altitudes have yielded only sparse, inactive cells. Earth's tropospheric cloud droplets have an active microbial presence, but are larger and far more water-rich than Venus aerosols; tropospheric times aloft are also similar to microbial generation times, making Earth's aerobiosphere dependent on continuous surface replenishment. Direct detection of potential biosignatures from a single transect is challenging; Earth's cloud microbiota yields 102 - 108 viable cells per mL, equivalent to one per 103 - 109 particles, with highly dynamic and heterogeneous distribution. The most important in situ measurement for Venus cloud habitability is detailed aerosol composition: confirmation of acid and water activity, presence of potentially bioavailable nutrients and energy, and potential presence of organic matter. Modeling Venus cloud aerosol residence time in comparison to periodic influxes of water and photochemical energy, and thus the ability of an ecosystem to maintain itself over time, would also address a significant habitability constraint particular to aerobiospheres.

Venus↗
NASA NTRSDate not supplied

Application of Earth Observation Data for Improved Environmental and Disaster Monitoring in Central America

Since its establishment in 1991, the Central American Integration System (SICA, in Spanish) has served as a force for integrating the eight countries of Central America and the Dominican Republic, and in recent years, SICA’s General Secretariat and its various technical secretariats have focused on integrating Earth observations into various regional and national processes. In 2019, for instance, a joint statement was signed between SICA’s General Secretariat and NASA, toward strengthening the region’s use of Earth observations. SICA has also pursued cooperation with the Group on Earth Observations’ AmeriGEO regional initiative, the Japanese Aerospace Agency (JAXA), the United Nations Office of Outer Space Affairs (UNOOSA), and the Copernicus program, among others. Just in the framework of the NASA-SICA Joint Statement, and towards the goal of strengthening the region’s use of Earth observations across sectors, a large number of training webinars has been conducted, particularly benefiting national institutions, non-governmental organizations, and universities. Additionally, targeted support has been provided in the areas of environmental monitoring and disaster management. From 2019 through 2021, for instance, a number of feasibility studies were implemented by NASA’s DEVELOP program in collaboration with SICA technical secretariats. In 2020, in response to devastating Hurricanes Eta and Iota, the SERVIR program also provided support for extending the HYDRAFloods algorithm which had been originally developed for the Mekong to Central America. Support is also being provided toward monitoring land cover change across the Mesoamerican Biological Corridor. In the framework of the “observing the Earth for the benefit of all” theme, this presentation will also focus on how Central America can serve as a case study for the development of Earth observation capacity, applicable to other regions of the world.

applied sciences↗
NASA NTRS2023

The Planetary Protection Strategy of Mars Sample Return’s Earth Return Orbiter Mission

The Mars Sample Return campaign aims to use three flight missions and one ground element to safely bring rock cores, regolith and atmospheric samples from the surface of Mars to Earth to answer key questions about the geologic and climate history of Mars, including the potential for ancient life. Since its landing in Jezero Crater in 2021, the first mission, NASA’s Mars 2020, has collected a number of samples on the crater floor and on the delta using the Perseverance rover. Subsequent missions would recover the sealed sample tubes, launch them into Mars orbit, and transport them back to Earth. The ground element would be a high-containment facility that would isolate and protect the samples during initial sample characterization, which would include sample safety assessments and time-sensitive scientific investigations. These elements are currently in the planning and design stages of development, and represent an international effort of NASA, the European Space Agency (ESA), and many industry partners. The work presented here provides an overview of the planetary protection strategy of the third flight mission, the ESA-led Earth Return Orbiter (ERO), which hosts the NASA-provided Capture, Containment, and Return System (CCRS). ERO-CCRS would capture the container with up to 30 sealed tubes previously put in Martian orbit, contain them in redundant containers to ensure that no potentially hazardous Mars particles are released, and return them to Earth through an entry vehicle. Both NASA and ESA policies comply with the United Nations’ Outer Space Treaty by planning to protect Earth’s biosphere from any potential adverse effects from material returned from solar system bodies beyond the Earth-Moon system. In the conduct of Mars Sample Return, the two agencies have agreed to apply approaches consistent with their own planetary protection standards to the campaign elements each provides.

Mars Sample Return↗
NASA NTRSDate not supplied

The Planetary Protection Strategy of Mars Sample Return Earth Return Orbiter Mission

The Mars Sample Return campaign aims to use three flight missions and one ground element to safely bring rock cores, regolith and atmospheric samples from the surface of Mars to Earth to answer key questions about the geologic and climate history of Mars, including the potential for ancient life. Since its landing in Jezero Crater in 2021, the first mission, NASA’s Mars 2020, has collected a number of samples on the crater floor and on the delta using the Perseverance rover. Subsequent missions would recover the sealed sample tubes, launch them into Mars orbit, and transport them back to Earth. The ground element would be a high-containment facility that would isolate and protect the samples during initial sample characterization, which would include sample safety assessments and time-sensitive scientific investigations. These elements are currently in the planning and design stages of development, and represent an international effort of NASA, the European Space Agency (ESA), and many industry partners. The work presented here provides an overview of the Planetary Protection strategy of the third flight mission, the ESA-led Earth Return Orbiter (ERO), which hosts the NASA-provided Capture, Containment, and Return System (CCRS). ERO-CCRS would detect and capture the container with up to 30 sealed tubes previously put in Martian orbit, contain them in redundant containers to ensure that no potentially hazardous Mars particles are released, and return them to Earth through an entry vehicle. Both NASA and ESA policies comply with the United Nations’ Outer Space Treaty by planning to protect Earth’s biosphere from any potential adverse effects from material returned from solar system bodies beyond the Earth-Moon system. In the conduct of Mars Sample Return, the two agencies have mutually agreed to apply approaches consistent with their own planetary protection standards to the campaign elements they each provides.

mars sample return↗
NASA NTRSDate not supplied

Earth System Digital Twins (ESDT) Definition and Science Use Cases

NASA AIST Program is now designing and developing Digital Twins of the Earth and/or Earth systems. Organized around interconnected, multi-domain, high-scale modeling capabilities, the three major components of an Earth System Digital Twin are a continuously updated Digital Replica of the Earth System of interest, dynamic Forecasting models, and Impact Assessment capabilities. In order to define ESDT's benefits to Earth Science, as well as the AIST capabilities required to develop such systems, the AIST Program has been developed 6 science use cases corresponding to 6 of the main Earth Science domains.

Earth Science Remote Sensing; Information Systems↗
NASA NTRS2024

The Planetary Protection Strategy of Mars Sample Return’s Earth Return Orbiter Mission

The Mars Sample Return campaign aims to use three flight missions and one ground element to safely bring rock cores, regolith and atmospheric samples from the surface of Mars to Earth to answer key questions about the geologic and climate history of Mars, including the potential for ancient life. Since its landing in Jezero Crater in 2021, the first mission, NASA’s Mars 2020, has collected a number of samples on the crater floor and on the delta using the Perseverance rover. Subsequent missions would recover the sealed sample tubes, launch them into Mars orbit, and transport them back to Earth. The ground element would be a high-containment facility that would isolate and protect the samples during initial sample characterization, which would include sample safety assessments and time-sensitive scientific investigations. These elements are currently in the planning and design stages of development, and represent an international effort of NASA, the European Space Agency (ESA), and many industry partners. The work presented here provides an overview of the planetary protection strategy of the third flight mission, the ESA-led Earth Return Orbiter, which hosts the NASA-provided Capture, Containment, and Return System. The orbiter would detect and capture the container with up to 30 sealed tubes previously put in Martian orbit, contain them in redundant containers to ensure that no potentially hazardous Mars particles are released, and return them to Earth through an entry vehicle. Both NASA and ESA policies comply with the United Nations’ Outer Space Treaty by planning to protect Earth’s biosphere from any potential adverse effects from material returned from solar system bodies beyond the Earth-Moon system. In the conduct of Mars Sample Return, the two agencies have mutually agreed to apply approaches consistent with their own planetary protection standards to the campaign elements they each provide.

Mars Sample Return↗
NASA NTRSDate not supplied

NASA Earth System Digital Twins (ESDT) For a Sustainable Future

An Earth System Digital Twin (or ESDT) is an Information System for Understanding, Forecasting, and Conjecturing the complex interconnections among Earth systems, including anthropomorphic forcings and impacts to humanity. More specifically, an Earth System Digital Twin is a dynamic and interactive information system that first provides a digital replica of the past and current states of the Earth or Earth system, as accurately and timely as possible (i.e., the “What Now”); second allows for computing forecasts of future states under nominal assumptions and based on the current replica (i.e., the “What Next”); and third offers the capability to investigate many hypothetical scenarios under varying impact assumptions (i.e., the “What If”). The full power of digital twins is that, through an integrated representation and standardized tools and software technologies, the same digital replica can address the needs of multiple users at various resolutions (spatial and temporal) and for various applications (science, economic, policy, etc.) – “from farmer to scientist”. Since 2020, NASA’s Earth Science Technology’s Intelligent Systems Programs have started defining and investigating ESDTs. After several workshops, more than 15 projects have been funded to develop technologies and components as well as a few prototype ESDT systems. An ESDT architecture framework has been defined, and it is now being used to develop a Coastal Zone Digital Twin (CZ-DT), in coordination with NOAA and CNES. Additional projects have also just been selected to build additional ESDT technologies and prototypes. The details of these Programs will be detailed at the conference.

Earth Science Remote Sensing; Information Systems↗
DOE OSTI2021

Pilot-Scale Testing of an Integrated Circuit for the Extraction of Rare Earth Minerals and Elements from Coal and Coal Byproducts Using Advanced Separation Technologies

The primary objective of this project was to develop and demonstrate an integrated pilot-scale circuitry for recovering high-value rare earth elements (REEs) from coal and coal byproducts. The target performance was to produce a mixed REE product with content of at least two percent by weight on a dry mass basis in a cost-effective and environmentally benign manner. During the first nine months of the project period (Phase 2 Budget Period 2), pilot plant construction was completed including all field site startup activities such as permitting, engineering design, procurement/bidding, unit fabrication, site construction, equipment installation, module assembly, safety training, and circuit shakedown. During the remaining 21 months of project period (Phase 2 Budget Period 3), detailed field-testing activities were performed including feedstock sample collection and preparation, exploratory testing, circuit modification, detailed parametric study, and performance optimization. A detailed techno-economic analysis was performed based on the pilot plant testing findings which provided various scenarios for REE production. The project successfully accomplished the proposed target performance by producing mixed rare earth oxide (REO) with greater than 90% purity by weight in a continuous pilot scale operation from two distinctly different coarse refuse materials (i.e., West Kentucky No. 13 and Fire Clay coal seams), and at least three secondary sources (i.e., heap leach process and naturally formed acid mine drainage system). Project partners included the University of Kentucky, Virginia Tech, West Virginia University, Alliance Coal, Blackhawk Mining, Mineral Refining Company, and Mineral Separation Technologies. The pilot scale test facility was constructed at a former mining complex owned by Alliance Natural Resource Partners (Alliance Coal). The site was rehabilitated to accommodate the equipment installation, construction and fabrication, electrical power requirement, water line management and containment. The process units constructed and installed included X-ray sorting unit, crushing and grinding unit, physical separation unit, acid leaching unit, solvent extraction unit, and wastewater management unit. A rare earth mineral concentration unit was constructed as a standalone unit for flexible operation. A detailed environmental assessment and control plan was carried out to identify and quantify any potential impacts of the pilot-scale processing circuitry on the human and eco-system health and well-being. Corresponding mitigation strategies and control measures were provided. A conceptual flowsheet was developed to effectively remove thorium and uranium from high purity rare earth oxide mix or any potential radionuclide enriched stream. The two distinct feedstock materials were secured from the Blackhawk Mining Complex in eastern Kentucky where the Fire Clay (Hazard No. 4) seam is processed. The West Kentucky No. 13 (Baker) coarse refuse material was collected from an active process stream at an Alliance coal preparation plant located in western Kentucky. Characterization analysis indicated that both of feed materials generated from the two sources contained >300 ppm of TREEs on a dry whole mass basis which met the requirements for a qualified feed stock. The two feedstocks were further upgraded using a dual x-ray sorter to prepare the feed material for hydrometallurgical circuit. Thermal treatment on feed material prior to leaching was found to: 1) improve the leaching recovery of REEs, 2) increase the leaching kinetics, and 3) allow the leaching reaction to occur at lower acidity. Roasting at 600°C was selected as the pre-treatment condition for both West Kentucky No. 13 and Fire Clay coarse refuse material. Over 40% of leaching recovery was achieved by roasting West Kentucky No. 13 material having a top particle size of 3 mm in the pilot scale operation using 1.2M sulfuric acid leaching at 75OC. Initial pilot scale testing involved continuous operation of the pilot plant for 94 hours. The leaching unit was operated at solid-to-liquid ratio of 1 to 10 (w/v) using 0.5M sulfuric acid solution at a temperature of 75°C. The continuous solvent extraction circuit utilized rougher and cleaner units with DEHPA and TBP as the extractants. An innovative stripping circuit was developed to accumulate the REE concentration in the stripping solution to a level above 600 ppm. A bleed stream from the recycled strip solution was treated using oxalic acid precipitation which produced a high grade rare earth oxalate. The oxalate product was roasted to remove the oxalate which produced a rare earth oxide product having a purity greater 90%. Due to high concentrations of contaminant ions in the pregnant leach solution (PLS), a modified flowsheet was developed that involved pre-concentration of the REEs using multiple stages of precipitation and redissolution. The advantage of this process was improved removal of contamination before the downstream purification process and a significant cost reduction relative to the circuit that utilized the solvent extraction process. The modified circuitry included processes involving leaching, multistage precipitation, redissolution, and oxalate precipitation followed by roasting of the oxalate product. The circuit produced a mixed REO that was 92.96% pure from the initial test. A detailed parametric test plan was carried out which involved varying key parameters including solids feed rate, acid flowrate, acid concentration, multistage precipitation pH, redissolution pH, oxalate precipitation dosage and pH. The response variables included REE recovery, contaminant recovery, REO product grade and overall chemical consumption. Test results indicated that the acid-to-solid ratio is the key parameter to leaching efficiency as performance deteriorated with an increase in solids concentration. The optimal pH determined for REE precipitation and redissolution was 6.5 and 2.5, respectively. Additional tests were conducted to further improve the flowsheet. Recirculating a portion of the PLS to the feed of the leach tanks improved the leaching performance by lowering the pH of the leaching system and reducing the contamination recovery by shortening the residence time. Moreover, the removal of Al prior to REE precipitation significantly reduced the oxalic acid consumption in the oxalate precipitation circuit. The modified circuit produced over 90% grade REO by weight from both West Kentucky No. 13 and Fire Clay coarse refuse material in pilot scale continuous test programs. A case analysis model was developed to project the REE and major contaminants concentration in each PLS stream based on the leaching condition, pH cut point, and oxalic acid dosage. A correlation was established using empirical and semi-empirical models. Using the models, chemical consumption required for each stage was predicted based on the projected performance of the hydrometallurgy circuit. After identifying the optimum conditions, validation tests were carried out for the treatment of both West Kentucky No. 13 and Fire Clay coarse refuse materials in the pilot plant. The actual circuit performance and chemical consumptions were very close to the model predictions. Other than the two coarse refuse sources, several secondary feedstocks were also tested in the pilot plant facility. A “heap leach” system was constructed using the coarse refuse material generated from cleaning the West Kentucky No. 13 seam coal. Using the two stage SX rougher and cleaner circuit, a concentrate with a grade >90% REO was produced while recovering >97% of the REEs from the heap leach PLS. Naturally generated acid mine drainage (AMD) from West Kentucky No.13 mine was processed using the multistage precipitation circuit in the pilot plant in a test conducted for a period of 32 hours. The final grade of the mix RE oxide produced from the AMD was 90.84% with an overall circuit recovery of 64%. The primary source of REE was the selective precipitation steps involving iron and aluminum rejection. The hydrophobic-hydrophilic separation (HHS) process was proven to effectively recover coal from fine waste materials. For REM recovery, the HHS process was able to produce concentrates at grades of approximately 1.8% REE on an ash basis; however, recovery values were typically low, <10%, under the optimal conditions determined in the laboratory-scale testing. Staged testing of the pilot-scale HHS process for coal recovery and semi-continuous laboratory testing for REM testing showed that a total concentration ratio of more than 15x was observed for the REM recovery process. A circuit simulation package was developed for REE extraction and purification using a spreadsheet-based platform (Microsoft Excel). The REESim circuit simulation package is configured to track the mass and volume flows of components passing through a series of unit operations specified and configured by the user. The mass rates can then be utilized by the user to determine important performance indicators such as product mass yields, concentrate purity levels, element-by-element recoveries, and so forth. The techno-economic analysis showed that the roasting and leaching operations were the most expensive capital items, each contributing approximately 30% to the total capital cost. One notable contributor to the high production costs was the low REE recovery observed in the pilot scale trials. The product basket price was shown to have a strong influence on the economic viability of the scenarios, with the scandium price being the most significant influencer. Operating cost was shown to be extremely sensitive to REE recovery, REE feed grade, and leaching acid consumption. An analysis of ten different scenarios for a 500 t/h commercial operation revealed that three were economically favorable, producing internal rates of return varying from 27.7% to 33.1% and payback periods of 4 to 5 years. The project successfully developed and demonstrated a process to recover REEs from coal and coal byproducts in a pilot-plant operation which consistently produced over 90% grade REO mix from varies types of feedstocks. Commercialization analysis showed that the technology readiness level successfully achieved TRL 6 at the end of the project and demonstrated the need and the potential for scaling the process to further advance the technologies toward the goal of providing a domestic supply of REEs at a commercial scale.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

AN ACID BAKING APPROACH TO ENHANCE RARE EARTH ELEMENT RECOVERY FROM BITUMINOUS COAL SOURCES

Rare earth elements (REE) are a group of 17 elements typically classified as light and heavy rare earth elements, which play a crucial role in developing the latest technologies for energy, defense, and medical sectors. Even though REEs have been found in more than 200 minerals, only bastnaesite, monazite and xenotime are commercially exploited for REE extraction. However, the recent exponential increase in REE demand has spurred countries such as the United States into research for the extraction of REEs from secondary sources such as coal, acid mine drainage, and coal ash. Several coal sources (e.g., Fire Clay seam coal) across the United States have been identified to contain elevated concentrations of rare earth elements (>600 ppm), and various researchers have investigated the feasibility of both physical and hydrometallurgical extraction techniques for rare earth concentration and subsequent extraction. However, both physical and direct leaching were concluded to be inefficient for RE beneficiation and extraction due to low recoveries. Alternatively, thermal treatment provides promising means for RE recovery from bituminous coal sources. The positive impact of thermal treatment/calcination was established to be due to the decarbonization and dehydroxylation of the clays, which released entrapped rare earth elements within the dominant minerals and converted them into an acid-soluble form. Nonetheless, the improvement in recovery was limited to the light REEs (LREEs) with an insignificant increase in the heavy REEs (HREE). It was demonstrated that the light and heavy REEs in the material were associated with difficult-to-leach minerals such as monazite, xenotime, and zircon, which were not decomposed by simple calcination due to their high thermal stability. Hence, roasting in the presence of chemicals was necessary to ensure the decomposition of those REE-containing minerals. As such, this study was focused on the acid baking treatment of bituminous coals with an aim to enhance REE recovery, especially HREEs. Based on the presence of REE minerals like monazite and xenotime, three pre-leach treatment methods, i.e., 1) roasting, 2) direct acid baking, and 3) acid baking after roasting were investigated. Roasting tests at 600 ⁰C revealed that the recovery of light REEs (LREEs) was enhanced while the recovery of HREEs remained relatively unaffected. LREE and HREE recovery values of 38.3% and 21.3%, respectively, were achieved using a 50 g/L sulfuric acid solution at 5% solid concentration and a solution temperature of 75 ⁰C for 2 hours. Comparatively, direct acid baking at 250 °C provided substantial increased LREE and HREE recovery values to approximately 49.4% and 53.0%, respectively, using an equivalent acid dosage. Recoveries were maximized to 77.0% and 79.6% for LREE and HREE, respectively, by roasting followed by acid baking. Similar results were obtained from the treatment of a second bituminous coal source. Due to strong correlations between REE and Al recovery values, tests were performed on kaolinite and illite, which were prominent clay minerals within the source coals. These experiments revealed that the REE recovery improvements were likely a result of dehydroxylation of clays and subsequent release and decomposition of REE-bearing minerals such as monazite, xenotime and zircon. Subsequently, a parametric study was conducted to identify the impact of acid baking parameters on rare earth element recovery. The factors investigated using a three-level statistical experimental program were acid baking time, acid solution concentration, baking temperature, and acid solution-to-solids ratio which were found to significantly impact REE and contaminant element (Al, Fe, and Ca) recovery. An increase in baking temperature up to around 250 ⁰C improved the light and heavy REE recovery values by more than 50 absolute percentage points relative to performances achieved when direct leaching. As aforementioned, acid baking was needed to both decompose the clay minerals and liberate the REE minerals, which allowed access for the acid to solubilize the REEs. Acid concentration of the solution used for acid baking was studied as a means of minimizing the amount of acid needed to achieve a target REE recovery. However, thermo-gravimetric and differential scanning calorimetry analysis (TGA-DSC) of sulfuric acid under oxidizing atmosphere revealed that the addition of water decreased the evaporation temperature, which explains the lower REE recovery values obtained when using acid concentrations less than 100%. Using pure sulfuric acid at an acid-to-solid ratio of 0.8:1 resulted in recovery values of around 70% for both LREEs and HREEs. The decomposition reaction time was relatively quick with 65% of the TREEs recovered within the first 10 minutes. Following the identification of optimum operating conditions through the parametric study, a systematic leaching study was carried out to examine the impact of leaching parameters, such as solid-to-liquid (S/L) ratio, temperature, and time, on REE recovery using acid baking conditions of 1:1 acid to solids ratio at 250 °C for 30 minutes. The solid-to-liquid ratio was varied from 1-20% by weight at 25 °C, 50 °C, and 75 °C solution temperatures. The results indicated that reaction time and solution temperature considerably impacted the recovery of heavy and light REEs. Interestingly, LREE recovery reduced from 68% at 5% S/L to 58% at 20%S/L, whereas HREE recovery of 78% remained unaffected. The decrease in the LREE recovery was determined to be due to La and Ce precipitation, likely through isomorphic substitution with calcium in gypsum. The kinetic data indicated that 67% LREE and 77% HREE recovery could be obtained within the first 15 minutes of the reaction, suggesting fast reaction kinetics. Furthermore, raising the solution temperature from 25 °C to 75 °C increased the LREE and HREE recovery from 60% and 32% to 67% and 79%, respectively. The kinetic modeling results demonstrated that the rate-limiting step in the LREE dissolution was diffusion and chemical reaction, whereas the HREE extraction was controlled by only chemical reaction. The leaching study concluded that using 20% S/L at 75 °C for 15 minutes maximized LREE and HREE recovery. The lab-scale precipitation study showed that Fe and Al in solution could be removed at pH 4.5 followed by REE precipitation at pH 6.0 using 6 mol/L NaOH. Finally, the bench-scale data was used to develop a process flowsheet for REE recovery from low-grade bituminous coal sources using acid baking. Finally, based on the proposed flowsheet, a concentrated RE-cake obtained through selective precipitation at pH 6.5 was re-leached using HCl at pH 1.5. The resultant leachate was used to identify the impact of various operating parameters on REE recovery and purity with an aim to maximize REE precipitation efficiency while minimizing the oxalic acid dosage. The operating parameters for this investigation were oxalic acid dosage, iron (III) contamination, solution pH and temperature. The resultant model suggested that oxalic acid dosage and reaction pH are the most significant factors for the REE precipitation efficiency, followed by the interaction of oxalic dosage and Fe concentration. Test results indicated that increasing the oxalic acid concentration from 0g/L to 80g/L improved the REE precipitation efficiency from approximately 4.2% to 95.0%. Furthermore, raising the solution pH from 0.5 to 2.5 considerably enhanced the precipitation efficiency from 0.0% to 98.9%. A solution temperature elevation decreased REE recovery, which indicated an exothermic reaction between REEs and oxalate anions. Finally, a high level of Fe contamination adversely impacted REE precipitation efficiency. The speciation analysis revealed that the dominant iron species in the solution system were Fe-(C₂O₄)₃³⁻, Fe-(C₂O₄)²⁻, and Fe-(C₂O₄)⁺, which consumed the majority of the oxalate anions

rare earth elements, acid baking, high-temperature↗
DOE OSTI2015

Forecasting the response of Earth's surface to future climatic and land use changes: A review of methods and research needs

In the future, Earth will be warmer, precipitation events will be more extreme, global mean sea level will rise, and many arid and semiarid regions will be drier. Human modifications of landscapes will also occur at an accelerated rate as developed areas increase in size and population density. We now have gridded global forecasts, being continually improved, of the climatic and land use changes (C&LUC) that are likely to occur in the coming decades. However, besides a few exceptions, consensus forecasts do not exist for how these C&LUC will likely impact Earth-surface processes and hazards. In some cases, we have the tools to forecast the geomorphic responses to likely future C&LUC. Fully exploiting these models and utilizing these tools will require close collaboration among Earth-surface scientists and Earth-system modelers. This paper assesses the state-of-the-art tools and data that are being used or could be used to forecast changes in the state of Earth's surface as a result of likely future C&LUC. We also propose strategies for filling key knowledge gaps, emphasizing where additional basic research and/or collaboration across disciplines are necessary. The main body of the paper addresses cross-cutting issues, including the importance of nonlinear/threshold-dominated interactions among topography, vegetation, and sediment transport, as well as the importance of alternate stable states and extreme, rare events for understanding and forecasting Earth-surface response to C&LUC. Five supplements delve into different scales or process zones (global-scale assessments and fluvial, aeolian, glacial/periglacial, and coastal process zones) in detail.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

In situ X-ray and IR probes relevant to Earth science at the Advanced Light Source at Lawrence Berkeley Laboratory

Access to synchrotron X-ray facilities has become an important aspect for many disciplines in experimental Earth science. This is especially important for studies that rely on probing samples in situ under natural conditions different from the ones found at the surface of the Earth. The non-ambient condition Earth science program at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory, offers a variety of tools utilizing the infra-red and hard X-ray spectrum that allow Earth scientists to probe Earth and environmental materials at variable conditions of pressure, stress, temperature, atmospheric composition, and humidity. These facilities are important tools for the user community in that they offer not only considerable capacity (non-ambient condition diffraction) but also complementary (IR spectroscopy, microtomography), and in some cases unique (Laue microdiffraction) instruments. The availability of the ALS’ in situ probes to the Earth science community grows especially critical during the ongoing dark time of the Advanced Photon Source in Chicago, which massively reduces available in situ synchrotron user time in North America.

58 GEOSCIENCES↗
DOE OSTI2017

Solvent Extraction of Rare Earth Elements from a Nitric Acid Leach Solution of Apatite by Mixtures of Tributyl Phosphate and Di-(2-ethylhexyl) Phosphoric Acid

Solvent extraction of rare earths from nitrate leach liquor of apatite using mixtures of tributyl phosphate (TBP) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) was studied. The effects of nitrate and hydrogen ion concentration of the aqueous phase as well as the composition and concentration of extractants in the organic phase on the extraction behavior of lanthanum, cerium, neodymium, and yttrium were investigated. The distribution ratio of REEs increases by increasing the nitrate concentration in aqueous phase and concentration of extractants in organic phase, but the hydrogen ion concentration in aqueous phase has a decreasing effect. Yttrium as a heavy rare earth is more sensitive to these parameters than light rare earth elements. Although the composition of organic phase has a minor effect on the extraction of light rare earths, the percent of extraction of yttrium decreases dramatically by increasing the TBP content of organic phase. Mixtures of TBP and D2EHPA can show either synergism or antagonism extraction depending on the concentration and composition of extractants in organic phase. The best condition for separating rare earth elements in groups of heavy and light REEs can be achieved at high nitrate concentration, low H{sup +} concentration, and high concentration of D2EHPA in organic phase. Separation of Ce and La by TBP and D2EHPA is practically impossible in the studied conditions; however, low nitrate concentration and high hydrogen ion concentration in aqueous phase and low concentration of extractants in organic phase favor the separation of Nd from other light rare earth elements.

36 MATERIALS SCIENCE↗
DOE OSTI2019

The energy budget and figure of Earth during recovery from the Moon-forming giant impact

Quantifying the energy budget of Earth in the first few million years following the Moon-forming giant impact is vital to understanding Earth's initial thermal state and the dynamics of lunar tidal evolution. After the impact, the body was substantially vaporized and rotating rapidly, very different from the planet we know today. The subsequent evolution of Earth's energy budget, as the body cooled and angular momentum was transferred during lunar tidal recession, has not been accurately calculated with all relevant energy components included. In this work, we use giant impact simulations and planetary structure models to calculate the energy budget at stages in Earth's evolution. We show that the figure and internal structure of Earth changed substantially during its post-impact evolution and that changes in kinetic, potential, and internal energy were all significant. These changes have important implications for the dynamics of tidal recession and the thermal structure of early Earth.

58 GEOSCIENCES↗