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At least 109 records · Page 6

First Analysis of Earth's Stratospheric γ ‐Ray Emission in Geographical Coordinates With Fermi LAT

Abstract From low‐Earth orbit, the Earth is an extremely bright γ ‐ray source compared to distant astrophysical objects. The high‐energy γ ‐ray emission, from the Earth's upper atmosphere, is produced by the interactions between cosmic rays (CRs) and air molecules. As CRs are predominantly charged particles, the geomagnetic field acts as a spectrometer, forbidding CRs below a certain energy to arrive and interact with the atmosphere at a given geomagnetic location from a given direction. We use photon data between 0.2 and 20 GeV as observed by the Fermi Large Area Telescope (LAT) to create, for the first time, stratospheric γ ‐ray emission maps of the Earth in the geographical coordinate system, for different viewing directions from LAT altitude. These maps confirm a strong association between measured γ ‐ray fluxes and geomagnetic cutoffs for CRs. We also report the spectrum of the Earth's stratospheric γ ‐ray emission in cardinal directions and use the geomagnetic spectrometer effect to infer the atmosphere's yield function of γ rays per incoming CR proton as a function of CR rigidity at the altitude of the Fermi spacecraft. This work is relevant to the study of near‐Earth radiation exposure for astronauts and spacecraft, modeling the geomagnetic field, and CR‐air interactions.

Madlee, S.↗

Synthesis and Stability of an Eight‐Coordinated Fe 3 O 4 High‐Pressure Phase: Implications for the Mantle Structure of Super‐Earths

Abstract Super‐Earths ranging up to 10 Earth masses (M E ) with Earth‐like density are common among the observed exoplanets thus far, but their measured masses and radii do not uniquely elucidate their internal structure. Exploring the phase transitions in the Mg‐silicates that define the mantle‐structure of super‐Earths is critical to characterizing their interiors, yet the relevant terapascal conditions are experimentally challenging for direct structural analysis. Here we investigated the crystal chemistry of Fe 3 O 4 as a low‐pressure analog to Mg 2 SiO 4 between 45–115 GPa and up to 3000 K using powder and single crystal X‐ray diffraction in the laser‐heated diamond anvil cell. Between 60–115 GPa and above 2000 K, Fe 3 O 4 adopts an 8‐fold coordinated Th 3 P 4 ‐type structure ( I ‐43d, Z = 4) with disordered Fe 2+ and Fe 3+ into one metal site. This Fe‐oxide phase is isostructural with that predicted for Mg 2 SiO 4 above 500 GPa in super‐Earth mantles and suggests that Mg 2 SiO 4 can incorporate both ferric and ferrous iron at these conditions. The pressure‐volume behavior observed in this 8‐fold coordinated Fe 3 O 4 indicates a maximum 4% density increase across the 6‐ to 8‐fold coordination transition in the analog Mg‐silicate. Reassessment of the FeO—Fe 3 O 4 fugacity buffer considering the Fe 3 O 4 phase relationships identified in this study reveals that increasing pressure and temperature to 120 GPa and 3000 K in Earth and planetary mantles drives iron toward oxidation.

Zurkowski, C. C.↗

Terrestrial atmospheric ion implantation occurred in the nearside lunar regolith during the history of Earth’s dynamo

Light volatile elements in lunar regolith are thought to be a mixture of the solar wind and Earth’s atmosphere, the latter sourced in the absence of geomagnetic field. However, the extent to which both the current and primitive geodynamo influence the transport of terres trial ions still remains unclear, and this uncertainty is further complicated by the enigmatic composition and poorly constrained location of the Eoarchean exosphere. Here we use 3-D MHD numerical simulations with contemporary magnetized and Archean unmagnetized atmospheres to investigate how Earth’s intrinsic magnetic field affects this transfer, aiming to constrain how and when the lunar isotopic signature provides a record of Earth’s pale-oatmosphere. We find that atmospheric transfer is efficient only when the Moon is within Earth’s magnetotail. The non-solar contribution to the lunar soil is best explained by implantation during the long history of the geodynamo with present-day solar wind conditions, rather than any short, putatively unmagnetized epoch of early Archean Earth. This further suggests the history of the terrestrial atmosphere, spanning billions of years, could be preserved in buried lunar soils. Our results indicate that the elemental abundances of Apollo samples are very sensitive to Earth’s hydrodynamic exobase altitude, which, at the time of ion implantation, was never smaller than 190 km.

Atmospheric dynamics↗

Purple is the new green: biopigments and spectra of Earth-like purple worlds

ABSTRACT With more than 5500 detected exoplanets, the search for life is entering a new era. Using life on Earth as our guide, we look beyond green landscapes to expand our ability to detect signs of surface life on other worlds. While oxygenic photosynthesis gives rise to modern green landscapes, bacteriochlorophyll-based anoxygenic phototrophs can also colour their habitats and could dominate a much wider range of environments on Earth-like exoplanets. Here, we characterize the reflectance spectra of a collection of purple sulfur and purple non-sulfur bacteria from a variety of anoxic and oxic environments. We present models for Earth-like planets where purple bacteria dominate the surface and show the impact of their signatures on the reflectance spectra of terrestrial exoplanets. Our research provides a new resource to guide the detection of purple bacteria and improves our chances of detecting life on exoplanets with upcoming telescopes. Our biological pigment data base for purple bacteria and the high-resolution spectra of Earth-like planets, including ocean worlds, snowball planets, frozen worlds, and Earth analogues, are available online, providing a tool for modellers and observers to train retrieval algorithms, optimize search strategies, and inform models of Earth-like planets, where purple is the new green.

Coelho, Lígia Fonseca (ORCID:0000000150081249)↗

Earth's water reservoirs in a changing climate

Progress towards achieving a quantitative understanding of the exchanges of water between Earth's main water reservoirs is reviewed with emphasis on advances accrued from the latest advances in Earth Observation from space. These exchanges of water between the reservoirs are a result of processes that are at the core of important physical Earth-system feedbacks, which fundamentally control the response of Earth's climate to the greenhouse gas forcing it is now experiencing, and are therefore vital to understanding the future evolution of Earth's climate. The changing nature of global mean sea level (GMSL) is the context for discussion of these exchanges. Different sources of satellite observations that are used to quantify ice mass loss and water storage over continents, how water can be tracked to its source using water isotope information and how the waters in different reservoirs influence the fluxes of water between reservoirs are described. The profound influence of Earth's hydrological cycle, including human influences on it, on the rate of GMSL rise is emphasized. The many intricate ways water cycle processes influence water exchanges between reservoirs and thus sea-level rise, including disproportionate influences by the tiniest water reservoirs, are emphasized.

54 ENVIRONMENTAL SCIENCES↗

Perspectives on AI Architectures and Codesign for Earth System Predictability

Abstract Recently, the U.S. Department of Energy (DOE), Office of Science, Biological and Environmental Research (BER), and Advanced Scientific Computing Research (ASCR) programs organized and held the Artificial Intelligence for Earth System Predictability (AI4ESP) workshop series. From this workshop, a critical conclusion that the DOE BER and ASCR community came to is the requirement to develop a new paradigm for Earth system predictability focused on enabling artificial intelligence (AI) across the field, laboratory, modeling, and analysis activities, called model experimentation (ModEx). BER’s ModEx is an iterative approach that enables process models to generate hypotheses. The developed hypotheses inform field and laboratory efforts to collect measurement and observation data, which are subsequently used to parameterize, drive, and test model (e.g., process based) predictions. A total of 17 technical sessions were held in this AI4ESP workshop series. This paper discusses the topic of the AI Architectures and Codesign session and associated outcomes. The AI Architectures and Codesign session included two invited talks, two plenary discussion panels, and three breakout rooms that covered specific topics, including 1) DOE high-performance computing (HPC) systems, 2) cloud HPC systems, and 3) edge computing and Internet of Things (IoT). We also provide forward-looking ideas and perspectives on potential research in this codesign area that can be achieved by synergies with the other 16 session topics. These ideas include topics such as 1) reimagining codesign, 2) data acquisition to distribution, 3) heterogeneous HPC solutions for integration of AI/ML and other data analytics like uncertainty quantification with Earth system modeling and simulation, and 4) AI-enabled sensor integration into Earth system measurements and observations. Such perspectives are a distinguishing aspect of this paper. Significance Statement This study aims to provide perspectives on AI architectures and codesign approaches for Earth system predictability. Such visionary perspectives are essential because AI-enabled model-data integration has shown promise in improving predictions associated with climate change, perturbations, and extreme events. Our forward-looking ideas guide what is next in codesign to enhance Earth system models, observations, and theory using state-of-the-art and futuristic computational infrastructure.

54 ENVIRONMENTAL SCIENCES↗

Annual Scientific Focus Area Report for the Energy Exascale Earth System Model Project: Phase II

The project's long-term goal is to assert and maintain an international scientific leadership position in the development of Earth system models that address the grand challenge of actionable predictions of Earth system variability and change, with an emphasis on the most critical scientific questions facing the nation and DOE. The grand challenge will be addressed by overcoming three major limitations: Pushing the high-resolution frontier of Earth system modeling through a combination of strategic model development and computational advances targeting exascale computers and beyond. Bridging the gap in scales and processes by developing a new class of models that couple the natural, managed, and man-made systems across scales to address energy sector vulnerability to variability and change. The project will achieve its goal through four intersecting project elements: A series of prediction and simulation experiments addressing scientific questions and mission needs; A well-documented and tested, continuously advancing, evolving, and improving system of model codes that comprise the E3SM Earth system model; The ability to use effectively leading (and “bleeding”) edge computational facilities soon after their deployment at DOE national laboratories; and An infrastructure to support code development, hypothesis testing, simulation execution, and analysis of results. To achieve the Grand Challenge of actionable Earth system predictions to address the most critical scientific questions facing our nation and DOE, the E3SM project defined its strategy in a fifteen-year roadmap with four intersecting project elements: A series of prediction and simulation experiments addressing scientific questions and mission needs; A well-documented and tested, continuously advancing, evolving, and improving system of model codes that comprise the E3SM Earth system model ; The ability to use effectively leading (and “bleeding”) edge computational facilities soon after their deployment at DOE national laboratories; and An infrastructure to support code development, hypothesis testing, simulation execution, and analysis of results. Figure 1 depicts the E3SM Project Roadmap, showing the relationships among the first three major project elements: the simulations, the modeling system to perform those simulations, and the machines on which they will be executed. Unlike the other three elements that have distinct but overlapping phases, the fourth element, the infrastructure, will evolve continuously based on the requirements imposed by project needs.

54 ENVIRONMENTAL SCIENCES↗

Design and Optimization of Processes for Recovering Rare Earth Elements from End-of-Life Hard Disk Drives

In this poster, we first provide motivation for why rare earth elements as rare earth permanent magnets (REPM) are increasing in demand. We then highlight some of the recent work that has been done by several national labs (National Renewable Energy Laboratory (NREL), Environmental Protection Agency (EPA), Critical Minerals Institute (CMI)) on recycling rare earth elements from end-of-life hard disk drives (EOL). Then, we mention our long-term plan to design a feedstock agnostic process to recover rare earth elements as rare earth oxides from many different EOL products at once. Next, we discuss how we quantified the rare earth elements available for recycling from EOL hard disk drives from consumer desktops and laptops. We then discuss how we used superstructure optimization to design the optimal pathway. The proposed superstructure was modeled as a MILP optimization problem, selecting the net present value as the objective function. Costing data from the literature was used to inform this model whenever possible. However, due to the novelty of this research area, data were often unavailable, thus requiring the generation of flowsheets implemented in Aspen Plus.

Laliwala, Chris↗

Quantifying Uncertainties in Earth's Energy Budget by Cloud Feedback and Ocean Heat Uptake Using E3SM-Slab Ocean Configurations

In order to improve predictive skills of Earth System Model, we need to better understand processes that control Earth's energy budget via ocean, atmosphere, and cryosphere interactions. Simulated energy budget in comprehensive Earth System Models shows a wide range, leading to large uncertainties in predicting Earth system dynamic and thermodynamic variations and associated social-economic impacts. Uncertainties in cloud feedbacks have been identified as the main cause of the large inter-model spread, but oceanic adjustments, especially those associated with ocean heat uptake (OHU) and the Atlantic Meridional Overturning Circulation (AMOC), also play an important role. In this proposed work, we focus on understanding the individual and combined roles of cloud feedbacks and ocean adjustments on modulating Earth's energy balance. This research is motivated by our overarching hypothesis that oceanic adjustment is a key source of uncertainty, in addition to those associated with the cloud feedbacks; further, the ocean adjustment and associated OHU work through the cloud feedbacks to modulate Earth's energy budget and temperature variations. We test this hypothesis using numerical experiments where we systematically enable and disable cloud feedbacks in conjunction with perturbations to OHU.

58 GEOSCIENCES↗

Plasma Imaging, LOcal Measurement, and Tomographic Experiment (PILOT): A Mission Concept for Transformational Multi-Scale Observations of Mass and Energy Flow Dynamics in Earth’s Magnetosphere

We currently do not understand the fundamental physical processes that govern mass and energy flow through the Earth’s magnetosphere. Knowledge of these processes is critical to understanding the mass loss rate of Earth’s atmosphere, as well as for determining the role that a planetary magnetic field plays in atmospheric retention, and therefore habitability, for Earth-like planets beyond the solar system. Mass and energy flow processes are challenging to determine at Earth in part because Earth’s planetary magnetic field creates a complex “system of systems” composed of interdependent plasma populations and overlapping spatial regions that perpetually exchange mass and energy across a broad range of temporal and spatial scales. Further, the primary mass carrier in the magnetosphere is cold plasma (as cold as ~0.1 eV), which is invisible to many space-borne instruments that operate in the inner magnetosphere. The Plasma Imaging LOcal and Tomographic experiment (PILOT) mission concept, described here, provides the transformational multi-scale observations required to answer fundamental open questions about mass and energy flow dynamics in the Earth’s magnetosphere. PILOT uses a constellation of spacecraft to make radio tomographic, remote sensing, and in-situ measurements simultaneously, fully capturing cold plasma mass dynamics and its impact on magnetospheric systems over an unprecedented range of spatial and temporal scales. This article details the scientific motivation for the PILOT mission concept as well as a potential mission implementation.

79 ASTRONOMY AND ASTROPHYSICS↗

Acid digestion processes for recovery of rare earth elements from coal and coal byproducts

A system for recovering rare earth elements from coal ash includes a leaching reactor, an ash dryer downstream of the leaching reactor, and a roaster downstream of the ash dryer that is cooperatively connected to both the leaching reactor and the ash dryer. Coal ash is mixed with an acid stream such that rare earth elements present in the coal ash are dissolved in the acid stream, thereby creating (i) a leachate containing the rare earth elements and (ii) leached ash. The leachate is heated to obtain acid vapor and an acid-soluble rare earth concentrate. Mixing of the coal ash with the acid stream can occur in a leaching reactor and heating of the leachate can occur in a roaster. The acid-soluble rare earth concentrate can be fed to a hydrometallurgical process to separate and purify the rare earth elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dissolution and separation of rare earth metals

A chemical dissolution method is provided for use in recycling rare earth metal-containing material such as permanent magnet material including end-of-life magnet shapes, magnet scrap and Terfenol-D alloy material by mixing the rare earth metal-containing material and an aqueous solution of a copper (II) salt to dissolve the material in the solution. The dissolved rare earth metal is then precipitated from the aqueous solution as a rare earth metal compound, such as a rare earth metal oxalate, sulfate or phosphate from which rare earth metal oxide can be obtained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reactive Grinding of Coal Ash For Enhanced Rare Earth Extraction

Monazite and coal ash contain varying trace amounts of Rare Earth Elements (REE). Rare earth elements are considered to be the elements in the lanthanide series. These elements be categorized into two separate groups, light and heavy rare earth groups. Rare Earth Elements play an essential role to society and industry and can be found in a spectrum of applications such as Capacitors, Power Generation, and Catalysts for Petroleum Refining. Due to the abundance of Coal Ash and ongoing production, there is an increasing interest from the scientific community to develop renewable source of energy by extracting rare earth elements from within its contents. Commercial and experimental reactive grinding and leaching procedures have been created to help to maximize the recovery of Rare Earth Elements from Coal Ash.

Keller, Murphy↗

Initial Testing of Alkaline Earth Metal Ion Absorption on Crystalline Silicotitanate - 20440

The Tank Closure Cesium Removal process at the Savannah River Site (SRS) has processed aqueous tank waste using the inorganic ion exchange media IONSIV{sup TM} R9120-Ba (which is also known as Crystalline Silicotitanate (CST)). Salt-cake in Tank 10H at SRS was dissolved and processed through filters and ion exchange columns. The primary purpose of the process is to remove Cs-137 from the aqueous waste so that it can be disposed as low level waste. It is known that this inorganic media also absorbs strontium from solution, and that strontium competes with cesium ions for absorption sites. The strontium ion is actually more strongly absorbed than the cesium ion from typical tank waste. However, strontium is typically present in low concentrations so does not normally cause a significant impact. Strontium is present as both non-radioactive isotopes and the radioactive Sr-90 isotope; with the non-radioactive isotopes being much more abundant. Although the total strontium solubility is usually much lower than cesium, some tank waste compositions can have a high enough soluble strontium concentration to decrease the cesium absorption. Relatedly, some testing at SRS suggested that another alkaline earth metal, calcium, may also absorb onto CST and may decrease cesium absorption. Barium is also an important species in treatment of tank waste, but is also usually present at low concentrations. However, after the Cs-137 is absorbed onto CST, it emits a beta particle and converts to Ba-137m, which then decays to non-radioactive Ba-137 by emission of a gamma ray. If the Ba-137m were to desorb quickly, it could impact the dose rate in down-stream equipment. In order to understand the impact of these alkaline earth metals on CST, SRNL performed testing using simulants of SRS tank waste that contain soluble barium, strontium, and calcium. Testing examined both removal of the alkaline earth metals and their impact on removal of cesium. Testing involved first developing realistic waste simulant formulations and dissolving the alkaline earth metals to high enough concentrations to potentially impact the Cs absorption. Once the formulations were developed and prepared, computer modeling was used to calculate the expected Cs absorption behavior to determine if the alkaline earth metals impact the performance. Measurements of the alkaline earth metals absorption by the media is also important for disposition of spent media because of the added radionuclide inventory from the Sr-90. These initial tests are examining the general impact and will be used to determine if further testing or measurements are needed. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Separation of thorium, uranium, and rare earths from a strip solution generated from coarse coal refuse

This work systematically evaluated the separation performance of thorium, uranium, and rare earths when coal and coal byproduct were utilized as a non-traditional feedstock for rare earth production. A synthetic solution was prepared following the elemental composition of a strip solution generated from coarse coal refuse and used throughout the study. Various separation techniques including selective precipitation, solvent extraction, and a modified experimental protocol incorporating the two were applied to extract rare earths while minimizing the non-selective recovery of thorium and uranium into the product stream. Test results indicate that selective precipitation was effective for the removal of thorium at a pH value approaching 5 while solvent extraction preferentially removed uranium from rare earths. Therefore, a modified experimental protocol consisting of both selective precipitation and solvent extraction was subsequently developed and implemented. The findings following the modified experimental protocol indicate that extractant concentration, solvent extraction feed pH, and organic to aqueous (O/A) ratio all played a significant role in the removal of uranium. Among all the tests conducted, the best separation performance was achieved using a one-stage precipitation at a pH value of 4.8, 50 v% TBP, solvent extraction feed pH of 3.5, and an O/A ratio of 3, which corresponded to an overall rare earth, thorium, and uranium recovery of 79.6%, 0%, and 3.1%, respectively.

01 COAL, LIGNITE, AND PEAT↗

Prediction of alkaline earth metal ion adsorption on goethite for various background electrolytes with the CD-MUSIC model

As water scarcity drives the use of more saline water sources, contaminant fate and transport models must capture the impact of high concentrations of alkaline earth metal ions (AEMs) and background electrolytes in these more complex waters. By utilizing macroscopic adsorption data from various electrolyte systems, a Charge Distribution – Multisite Complexation (CD-MUSIC) model, capable of incorporating electrolyte adsorption, was able to accurately simulate the adsorption behavior of alkaline earth metal ions onto goethite. The modeling effort was guided by previous spectroscopic and surface complexation modeling of alkaline earth metal adsorption and built on previous CD-MUSIC modeling that accounted for changes in crystal face contributions to the surface site density as a function of specific surface area. Further, the model was constrained to consider only two dominant surface complex species for each metal ion adsorption reaction. These two species were selected from 44 possible species through objective curve fitting of single-solute macroscopic adsorption data. While most of the alkaline earth metal surface complexes formed outer-sphere complexes at the goethite surface, an inner-sphere species was utilized for Mg 2+ . With the surface complex species and equilibrium constants obtained from this study, the calibrated model successfully predicted alkaline earth metal ion adsorption over a wide range of solution and surface conditions; the model predictions encompassed a wide range of pH (5–11), solute/solid ratio (1.37 × 10 -5 – 8.33 × 10 -4 mol -solute /g -solid ), ionic strengths (0.01 M – 0.7 M), and background electrolytes (Na + , Cs + , Rb + , Cl - , and NO 3 - ) using the same crystal face contribution methodology for site density, capacitance values, and surface acidity constants adopted for proton and cadmium adsorption in previous work (Han and Katz, 2019). Model simulations for a range of background water chemistries demonstrated the potential for Mg 2+ to reduce Cd 2+ adsorption to goethite in model seawater and oil- and gas-produced waters.

42 ENGINEERING↗

Controlling Extraction of Rare Earth Elements Using Functionalized Aryl-vinyl Phosphonic Acid Esters

Ligands that can discriminate between individual rare earth elements are important for production of these critical elements. A set of aryl-vinyl phosphonic acid ligands for extracting rare earth elements were designed and synthesized under the hypothesis that the strength of the rare earth-ligand interactions could be tuned by changing the dipole moment of the ligand. The ligands were synthesized via a two-step reaction procedure using a Heck coupling reaction to functionalize vinyl phosphonic acid, followed by Steglich esterification to obtain high-purity styryl phosphonic acid monoesters with varying dipole moments along the P-C bond. The metal binding strength and composition of the rare earth complexes formed with these styryl phosphonic acid monoesters were experimentally studied by liquid-liquid extraction techniques, while DFT calculations were performed to determine the dipole moments of the free and complexed ligands and the electronic structure of the complexes formed. All three prepared ligands were much stronger extracting agents for europium(III) than the dialkylphosphonic acids usually used for this separation. However, the order of increasing extraction strength was found to match the order of the decreasing calculated dipole moment along the P-C bond of the three styryl-based ligands, rather than correlating with increasing ligand basicity, as reflected by the pK a of the ligands. Finally, these findings suggest that this approach can be used to systematically alter the extraction strength of aromatic phosphonic monoesters for rare earth element purification.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microcavity-Modified Emission from Rare-Earth Ion-Based Molecular Complexes

Despite the remarkable optical properties of rare-earth ion materials, their applications as light sources and in quantum technologies are often hindered by their long lifetimes and weak emission. Leveraging the natural compatibility of rare-earth ion molecular complexes with photonic structures, here we modify their photoluminescence properties by coupling them to a flexible open Fabry-Perot cavity. The full in situ tunability of the Fabry-Perot cavity allows fine control over its cavity modes and the achievement of resonant coupling between the rare-earth ion emission and the cavity modes. This configuration allows us to achieve a maximum photoluminescence enhancement factor of 30 and accelerate the decay rate up to two orders of magnitude. Our pump-power-dependent spectroscopic studies of the emitter-cavity system suggest that the cavity-modified emission is primarily caused by amplified spontaneous emission. These results suggest that integrating rare-earth ion molecular complexes with photonic structures could be a viable approach for the effective tuning of their optical properties. This natural compatibility, together with their versatile molecular structures and the resultant electronic states, renders rare-earth ion molecular complexes a potential alternative material platform for lighting and quantum applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗