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Aragonite saturation horizon variability along North Pacific seamounts and implications for deep-sea coral reefs

The 2014 discovery of living deep-sea coral reefs along the Northwest Hawaiian Islands (NWHI) and lower Emperor Seamount Chain (ESC), despite the North Pacific’s shallow aragonite saturation horizon (ASH) and high CaCO3 dissolution rates, underscores the need to understand the local seawater chemistry that allows these reefs to persist. We investigated seawater carbonate chemistry using discrete samples along the NWHI and ESC from two cruises ~1 year apart (08/26/21 – 09/26/21, 09/09/22 – 10/24/22). Across the two cruises, ASH depth difference ranged from 15 to 77 m. Since the Pacific ASH shoals by 1–2 m yr?¹, this long-term trend cannot explain the magnitude of ASH change observed between cruises. Temperature-salinity plots similarly indicate no major shifts in intermediate water masses that could account for these changes. Instead, ASH depth variability was primarily governed by localized biogeochemical processes, namely changes in intermediate water respiration and CaCO3 dissolution. Indicators for dissolution (TA*) and respiration (AOU) suggest changes in ASH depth were driven by changes in dissolution at the northern- and southern-most sites, whereas respiration exerted stronger control at central sites. Combining 2021 and 2022 data with data from 2014 – 2019 (excluding 2018) revealed high interannual ASH variability, by as much as >200 m at one site. Deep-sea coral reefs across the NWHI and ESC currently reside close to the ASH depth and likely experience seasonal and interannual shifts between under- and supersaturation. As ocean acidification progresses however, persistent exposure to undersaturated seawater could further threaten these critical deep-sea ecosystems.

coral reefs↗

Post-Wildfire Mobilization of Organic Carbon

Wildfires significantly alter watershed functions, particularly the mobilization of organic carbon (OC). This study investigated OC mobility and the physicochemical characteristics of wildfire-impacted soils and ashes from the northern California and Nevada fires (Dixie, Beckworth, Caldor). Organic carbon in wildfire-derived ashes (9.2–57.3 mg/g) generally exceeded levels in the background soils (4.3–24.4 mg/g), except at the Dixie fire sites. The mobile OC fraction varied from 0.0093 to 0.029 in ashes and 0.010 to 0.065 in soils, though no consistent trend was observed between the ashes and soils. Notably, the ash samples displayed lower OC mobility compared with the soils beneath them. A negative correlation was found between the mobile OC fraction and bulk OC content. Wildfire increased the total amount of mobile OC substantially by 5.2–574% compared to the background soils. Electron paramagnetic resonance (EPR) spectra confirmed the presence of environmentally persistent free radicals (EPFRs), which correlated with observed redox reactivity. Additionally, X-ray absorption near edge structure (XANES) and X-ray fluorescence (XRF) imaging revealed that Fe(II) oxidation in soils beneath the ashes may have enhanced the OC mobility, likely driven by pyrogenic carbon and free radicals. These findings enhance our understanding of post-wildfire OC mobilization and the impact of ash–soil physicochemical properties on watershed health.

organic carbon↗

Differences in urban plant community compositions across an urban-rural gradient in Knoxville, TN

Urban forests, or vegetation in areas under heavy human influence, provide many ecosystem services to urban residents such as localized cooling via evapotranspiration, shade, filtering of air pollution, and the associated health benefits of natural spaces. In order to quantify the magnitude of localized cooling by trees growing in varying levels of urbanization (based on % impervious surfaces, e.g., buildings, pavement), urban forest species composition, tree size, and tree density must be characterized. As a part of Oak Ridge National Laboratory’s (ORNL) urban forest temperature study, we conducted tree censuses in five Knoxville city parks where ORNL meteorological stations are deployed. Moreover, we measured every woody plant ≥ 5 cm diameter at breast height (DBH) within a 50 m radius of each site’s meteorological station for its DBH and species identification. When possible, individuals were identified down to species. Certain genera (Quercus spp., Carya spp., Pinus spp.) were identified down to genera in interest of time. Individual and total site basal area were calculated from measured DBH data. Results show notable differences in urban plant community compositions and total woody plant basal area across sites, with more urban sites closer to downtown (West View and SEEED) having lower tree basal area than the more suburban sites (West Hills, Cumberland Estates, and Victor Ashe). We identified 54 species across all sites, with West Hills and Victor Ashe having the highest species diversity. Our results show differences in forest compositions and sizes across Knoxville, which are currently informing ORNL’s evapotranspiration estimates for each site. Data Summary: Census data for West Hills (WH), Cumberland Estates (CE), Victor Ashe (VA), West View (WV), and Socially Equal Energy Efficient Development or SEEED (SD) urban forests in Knoxville, TN, USA, including tree size based on diameter at breast height (DBH; 1.3 m), species identification (Latin and common names), and basal area per stem (BA=π×[.5*DBH]^2). Field data are summarized in this file: “Community_Composition_Data.CSV”. Site-specific data detailing each site’s coordinates, number of stems measured at DBH, average tree DBH, α-diversity (number of species present), and total site basal area (sum of individual basal areas per site) are in this file: “Site_Comparisons.CSV”.

Warren, Jeffrey [ORNL] (ORCID:0000000206804697)↗

Manganese Oxidation during Vegetation Burning

Redox recycling of manganese (Mn) plays a key role in organic matter decomposition and nutrient cycling in terrestrial vegetated ecosystems, and it is expected to be changed by fires. This study revealed how Mn is oxidized during vegetation burning, by characterizing the chemical speciation of Mn in fire ash from wildland fires and laboratory burning and evaluating the factors governing its average oxidation state (AOS) and speciation. Manganese in wildland fire ash from different ecosystems showed variable AOS that ranges from 2.5 to 3.3. Laboratory burning experiments showed that Mn oxidation was primarily controlled by fire thermal intensity (temperature × duration) and burning completeness. As heating time increased from 5 min to 5 h at 550 and 700 °C, Mn AOS in the lab-burned vegetation ash increased from 2.7 to 4.0 and the oxidation rate was faster at higher temperature. Diverse Mn species can present in wildland fire ash and differ structurally from biogenic Mn oxides. The oxidized Mn species enable fire ash to mediate oxidative degradation of catechol, demonstrating its potential in mediating organic matter decomposition. This study revealed a new paradigm of Mn redox recycling, as compared to the microbe-mediated Mn redox cycling in the absence of fires.

36 MATERIALS SCIENCE↗

Woody Feedstock 2022 State of Technology Report

The U.S. Department of Energy promotes production of advanced liquid transportation fuels from lignocellulosic biomass by funding fundamental and applied research that advances the state of technology (SOT). As part of its involvement in this mission, Idaho National Laboratory completes an annual SOT report for n th -plant and 1 st -plant woody biomass feedstock logistics. The purpose of the SOT is to provide the status of feedstock supply system technology development for woody biomass to biofuels relative to technical targets and cost goals from specific design cases, based on data and experimental results. Conventional feedstock supply systems need to be modified to meet the demands of conversion pathways, specifically to have the ability to adjust the quality of the raw biomass materials. Advanced systems incorporate innovative methods of material handling, preprocessing and supply chain configuration. In advanced designs, variability of the raw biomass can be reduced to produce feedstocks of a uniform format, moving toward biomass commoditization. Against this backdrop, the 2022 Woody SOT for low-ash woody feedstocks utilizes feedstock fractionation by incorporating technologies that can separate the biomass into its anatomical fractions (wood, bark, needle, and extrinsic ash) to reduce impurities and attempt to maximize the retention of usable fractions that satisfy downstream quality considerations. By using a series of air classification steps, this strategy can reduce the extrinsic ash in forest residues, separate out a majority of the incoming needles (which can be supplied to alternate markets), and maximize the retention of whitewood in the usable fraction. The fractionated forest residues are then mixed with clean-pine chips in a 50-50 blend to prepare the feedstock for the desired conversion pathway. The n th -plant analysis estimated the delivered cost for the feedstock at $\$$69.23/dry ton (2016$\$$) which represents a $\$$6.64/dry ton decrease compared to the cost estimate of the 2021 Woody SOT supply system for low-ash woody feedstocks. The quality requirements in the 2022 Woody SOT were identical to those of the 2021 Woody SOT at = 1.00 wt % ash and = 50.51 wt% carbon. The cost savings derive primarily from reductions in dry matter losses during air classification. The GHG emissions for the n th -plant analysis were estimated at 178.39 kg CO2e/dry ton compared to 178.71 kg CO 2 e/dry ton in the 2021 Woody SOT, a decrease of 0.32 kg CO2e/dry ton. The small change stems from an increase in emissions attributed to preprocessing and slightly larger savings in emissions from transportation. In the 1 st -plant analysis of the 2022 Woody SOT system, the average throughput was estimated to be approximately 2,128 dry tons/day or 96.51% of the name plate capacity. During the simulation the daily throughput ranged from 1,090 dry tons/day to 2,200 dry tons/day, or 49.43% to 99.75% of the daily nameplate capacity. After the year of operation 722,403 tons of processed feedstock were produced in total without regard to quality considerations (99.64% of the annual nameplate capacity). The variability in throughput was primarily caused by equipment failures in the system. Regular failures, downtime caused by routine maintenance per manufacturer guidelines, contributed to a majority 62.50% of failures and 62.60% of downtime. Failures due to wear were the other cause of disruption within the system, impacting the rotary shear and orbital screen and accounting for 37.50% of the failures and 37.40% of the total downtime. Ultimately the system was on stream for 87.84% during the simulation period, which is only 2.16 percentage points below the nth-plant assumption for on-stream time. The production cost of the system averaged $\$$71.66/dry ton. The costs ranged from a minimum of $\$$71.23/dry ton to a maximum of $\$$2,115.30/dry ton. When dry matter losses (disposed low-quality fractions as well as other losses such as in grinders) were considered the costs increased to an average of $\$$75.11/dry ton with a minimum of $\$$74.69/dry ton and a maximum of $\$$2,136.86/dry ton...

09 BIOMASS FUELS↗

Coal-Waste-Enhanced Filaments for Additive Manufacturing of High-Temperature Plastics and Ceramic Composites

In the United States, coal waste from over a century of mining and burning coal for heat and electricity has accumulated as mountains of coal fly ash and bottom ash and acre-size ponds, coal fines and gob. These materials can be a problem for local communities and water systems. A cost-effective process to utilize high volumes of these coal wastes in a high-value product would be beneficial to those communities by reducing the amount of waste and providing jobs, manufacturing components, and materials from the waste. Many coal-to-products technologies (e.g., carbon fibers, graphene, carbon foam) rely on carefully choosing the starting material and then altering it chemically or thermally to make the products work. Due to the wide variability of composition and coal content in typical coal waste streams, many high-volume coal waste streams are likely to be unsuitable for use in those technologies. Semplastics’ technology has been shown to utilize most types of coal waste successfully without any pre-selection or pre-processing requirements other than a nominal particle-size reduction for wastes like bottom ash. This characteristic of Semplastics’ solution may enable the use of much larger volumes of a wider range of coal wastes than other coal-to-products technologies. In this project, Semplastics leveraged its unique experience with both coal waste (fly ash or coal combustion residuals), resin materials, and 3D printing to develop 3D printer filaments using common coal wastes – bituminous coal fines and fly ash – and researched the feasibility of using other forms of coal waste as fillers. Simple 3D-printed parts were successfully produced from the coal waste enhanced filaments, which were found to have improved strength and stiffness.

01 COAL, LIGNITE, AND PEAT↗

Thermochemical Transformation of Calcium during Biomass Burning and the Effects on Postfire Aqueous Dissolution of Macronutrients

Calcium is commonly the most abundant element in fire residues and its speciation largely determines the geochemical properties of fire residues and their effects on postfire soil chemistry. To explore the effects of biomass composition and fire conditions on ash Ca speciation, this study characterizes the speciation of Ca in charcoal and ash samples that were derived from different plant compartments and thermal conditions, using Ca K-edge X-ray absorption near edge spectroscopy. Results showed that biomass contains abundant organic Ca complexes, which were mineralized into fairchildite and calcite after heating at 450 to 600 °C and then CaO, as temperature increased to 750 °C. Apatite could be an abundant Ca species in fire residues if the Ca/P molar ratio of the biomass is small (<2). The mineralization of organic Ca to the identified Ca minerals during burning was negligibly affected by the oxygen level. Calcium speciation in prescribed fire residues resembled that of biomass ash burned at 550 °C with similar Ca/P molar ratios. Batch experiments showed that macronutrients (Ca, Mg, K, and P) were differentially released, as a result of different solubility of minerals in ashes and reprecipitation of minerals. The aqueous solubility of Ca, Mg, and P decreased as pH increased from 5 to 9, while K showed no pH dependency and was almost completely soluble. Results from this study improve our understanding of the chemistry of fire residues and their geochemical behaviors, which can help evaluate the impact of fire on postfire soil properties and macronutrient cycling.

36 MATERIALS SCIENCE↗

Wildfire Produces Transient Minerals: Speciation, Reactivity, and Fate of Iron and Manganese in Surface Soils Post Wildfire

Wildfire leads to the deposition of an ash layer at the land surface. This material typically has alkaline properties, abundant pyrogenic carbon, and elevated metal concentrations compared to surface soils. Here, we compare ash and surface soils collected three weeks and two years after the Glass Fire (St. Helena, California, USA) to determine how wildfire affects the speciation and reactivity of iron (Fe) and manganese (Mn), two micronutrients that influence many soil processes. Synchrotron-based analyses revealed that wildfire generated stable Fe oxides like maghemite (γ-Fe 2 O 3 ) and hematite (α-Fe 2 O 3 ) that likely derived from surface soil or mineral dust rather than the vegetation, and Mn oxides such as hausmannite (Mn 3 O 4 ) and bixbyite (Mn 2 O 3 ) that derived primarily from aboveground biomass. However, these pyrogenic minerals were absent in soils collected two years after the fire. Their loss from the soil surface may result from a combination of erosion, translocation to deeper soil layers, and chemical weathering. The latter hypothesis is supported by the enhanced mobilization of Fe and Mn from ash upon the addition of pyoverdine, a model biogenic ligand. The increased mobility of micronutrients from fire-derived minerals in ash in response to microbial and root exudation may facilitate postfire soil and vegetation recovery.

bixbyite↗

Incorporation of Oxygen Carrier Recycle into Large-Scale Production of Cu-Based Oxygen Carriers

One of the greatest challenges in the chemical looping combustion (CLC) of solid fuels is developing an oxygen carrier material that is reactive and attrition resistant and can be prepared at a reasonable cost. Recent efforts in oxygen carrier development have followed two primary approaches: (1) using natural ores, such as ilmenite, or (2) developing highly attrition-resistant and reactive synthetic materials. Both approaches have shortcomings, namely, the low reactivity and incompatibility of ores with solid fuel CLC and the high cost and low durability of synthetic materials. Here, a different approach is taken where attrition is assumed inevitable and the recycling of spent oxygen carrier materials is incorporated into oxygen carrier manufacture. For solid fuel CLC, Cu-based oxygen carriers are attrited and are collected with fly ash. Copper oxides are more reactive with nitric acid than most ash materials, meaning that a copper-nitrate-rich leachate can be generated. This copper nitrate stream could then be reused in oxygen carrier synthesis by impregnation. For proof of concept, leaching experiments were conducted to verify that copper oxides are selectively leached from ash-containing spent oxygen carriers. Several cases for process design are proposed based on the composition of spent materials, as the degree of copper oxidation and type of solid fuel dictate leaching residence times and general processing intensity. The four stages proposed here include impurity removal, copper leaching and recovery, solid–liquid separation, and evaporation/concentrating. The resulting process should be able to recover up to 95% of copper while minimizing inclusion of undesirable ash-based impurities.

anions↗

Online LIBS–ML Framework for Dynamic Characterization of Heterogeneous Waste-Derived Gasification Feedstocks

LIBS−ML framework for real time feedstock characterization during continuous conveyor transport Heterogeneous waste derived feedstocks (e.g., waste coal, biomass and blends) introduce rapid variability in heating value and ash chemistry that affect gasifier operation, yet conventional laboratory characterization techniques are too slow to support proactive control. To address this gap, this study reports on an online, in situ, dynamic characterization framework that couple’s laser-induced breakdown spectroscopy (LIBS) with leakage safe machine learning (ML) regression to deliver real time, decision quality predictions of gasifier relevant properties. A controlled sample matrix spanning two different waste coals, two different biomasses, and engineered blends under two particle size conditions were constructed and benchmarked using standardized laboratory analyses for proximate/ultimate properties and ash composition. LIBS spectra were acquired dynamically as material flowed on a conveyor belt, using high energy 1064 nm laser ablation and shot averaging to improve repeatability and precision. Supervised regression models (multi layer perceptron (MLP) /artificial neural network (ANN), random forest (RF), and support vector regression (SVR)) and an optimized weighted ensemble were trained on emission line feature sets using nested cross validation with Bayesian hyperparameter tuning and validated against an independent hold out set. The proposed LIBS−ML workflow achieves near laboratory predictive fidelity across parametric targets (including higher heating value (HHV), ash content, fixed carbon, sulfur, major ash forming oxides, and initial deformation temperature (IDT)), with the weighted ensemble providing a robust default predictor under dynamic measurement conditions. These results demonstrate a practical pathway for real time feedstock characterization that can enable feedforward adjustments and more resilient gasifier operation for variable quality waste derived fuels.

Biomass↗

Evaluation of Pozzolan-substituted Cast Stone for Pretreated Hanford Tank Waste

Portland cement. The future availability of quality Class F fly ash has come into question as coal-fired power plants are being converted to gas or taken offline. Consequently, alternative pozzolanic reagents are being evaluated for fly ash replacement in cementitious matrices for treating radioactive waste and debris. In 2023 and 2024, Savannah River National Laboratory (SRNL) was funded to evaluate natural pozzolans for the replacement of Class F fly in the Savannah River Site (SRS) Saltstone formulation. Based on the promising results and uncertain availability of Class F fly ash in the northwestern US, Hanford Tank Waste Operations & Closure, LLC (H2C) requested SRNL to evaluate the potential for substituting natural pozzolans in the Hanford West Area Pretreated Low Activity Tank Waste (PTW/LAW) Cast Stone formulation1 . Task 1 in this request was to determine the change in Cast Stone volume resulting from stabilization/solidification of 1 L of PTW/LAW tank waste. The densities of three (Hess Pumice, tephra pumice, and clinoptilolite zeolite) pozzolan-substituted Baseline Cast Stone mixes were determined, and volume changes relative to the fly ash-Baseline Mix with a water-to-dry mix = 0.40 were calculated.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

LDR Inorganic Spiked Simulants in Pozzolan-Substituted Cast Stone for Hanford Pretreated Low-Activity Tank Waste

Pretreated Low Activity Waste (PTW/LAW) at the Hanford Site, is currently projected for disposition through a cementitious waste form. The current standard formulation, Cast Stone, uses Class F fly ash, blast furnace slag, and Portland cement. However, the future availability of Class F fly ash is uncertain, as many coal-fired power plants—the source of this byproduct—are being decommissioned or converted to natural gas. This issue has prompted research into identifying and evaluating suitable alternative materials to replace fly ash in the cementitious waste forms used by the Department of Energy (DOE). The Savannah River National Laboratory (SRNL) successfully identified four natural pozzolans for the replacement of Class F fly ash in the current Savannah River Site (SRS) low-level waste (LLW) form, Saltstone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Waste Material Feedstocks Using Laser-Induced Breakdown Spectroscopy and Machine Learning

Predicting properties such as heating value, ash fusion temperature, and mineral ash composition from Laser-Induced Breakdown Spectroscopy (LIBS) data can make gasifiers more flexible to different feedstocks. Understanding these feedstock properties in-situ improves feedstock conversion modelling methods that allow for consistent operation, higher carbon conversion, and reduced fouling and erosion rates. The purpose of this study is to demonstrate methods for model creation that take LIBS data as predictor features and estimate higher order material properties as a function of feedstock material properties. Six samples were chosen to represent a mixture of abundant and carbon rich waste materials. LIBS measurements were performed on these samples for elemental wavelengths and intensity values. Laboratory analytical results were obtained for each sample’s heating value, proximate and ultimate analysis, mineral ash composition, ash fusion temperatures, and viscosity temperatures. Thermal conductivity was measured using a HotDisk TPS 2500S. LIBS measurements were processed and used as predictor features for machine learning (ML) models to predict the sample’s material properties. Predictor feature selection algorithms, particularly minimum redundancy maximum relevance (mRMR), reduced the dimensionality of ML models. Many modelling methods such as Gaussian process regression (GPR), regression tree, neural networks (NN), and support vector machines (SVM) were demonstrated to be effective at predicting higher order properties; however, mRMR with GPR stood out as a clear winning combination.

01 COAL, LIGNITE, AND PEAT↗

Hydrogen-rich syngas production from the steam co-gasification of low-density polyethylene and coal refuse

Gasification provides a promising pathway for transforming waste materials into valuable products, such as fuels and chemicals. Here, this study investigates the steam co-gasification of low-density polyethylene (LDPE) and compressed thickener underflow, representative of coal refuse (CR), in a drop tube reactor. The effects of feed blend ratio (0–100 wt% LDPE) and temperature (800–1000 °C) on syngas composition, tar formation, and process efficiency are examined. The high volatility of LDPE makes it more reactive than CR but also promotes the formation of 2–7 ring aromatic tars. Increasing temperature improves carbon conversion efficiency (CCE), cold gas efficiency (CGE), and syngas yield, although the lower heating value (LHV) of syngas decreases. Hydrogen is the dominant gas product, reaching 59 vol% with the H 2 /CO molar ratio ranging from 2.27 to 4.74. Synergistic effects from alkali and alkali earth metals (AAEMs), particularly K and Ca, in CR ash enhance syngas yield by catalyzing char gasification and tar cracking. Hematite (Fe 2 O 3 ) and ash from sub-bituminous/bituminous coals are explored as tar reforming catalysts. Fe 2 O 3 achieves 100 % tar reforming efficiency, while coal ash, with a lower Fe 2 O 3 content (15 wt%), is less effective at cracking polycyclic aromatic hydrocarbons, particularly naphthalene. These findings demonstrate the flexibility of co-gasification, allowing precise tuning of syngas characteristics for specific downstream applications. Further optimization of waste-derived catalysts could enhance the economic viability of gasification in waste-to-energy processes.

01 COAL, LIGNITE, AND PEAT↗

Upconversion of non-recycled MSW paper fractions into biochar via slow pyrolysis and life cycle analysis: Pathways to net negative GHG emission

This study presents an integrated and sustainable approach to valorizing non-recycled municipal solid waste (MSW), a heterogeneous and underutilized waste stream destined for landfilling, by converting it into valuable biochar resources. Specifically, we investigated the upcycling of nonrecycled paper waste based on compositional analysis into four major fractions: high cellulose, high lignin, high contamination, and high ash content papers. These fractions were then homogenized and subjected to slow pyrolysis. The high cellulose fraction (36.1 %) was the most abundant, and contained 66.7 % cellulose, while the high lignin fraction showed the highest lignin (12.1 %) and carbon content (44 %), resulting in highest energy value of 17.4 MJ kg −1 . Biochar yields ranged from 25.6 % to 35.6 %, with the high ash fraction producing the highest yield and alkalinity (pH ≈ 11.2) due to its higher mineral content. Elemental analysis revealed enhanced carbon content up to 76.9 % and reduced oxygen and hydrogen, confirming effective carbonization. The high lignin-derived biochar showed the highest aromatic carbon content (82.8 %) and greater structural stability, while contaminated and ash-rich fractions exhibited dense, low-porosity surfaces due to the presence of contaminants and minerals. Spectroscopic analysis revealed degradation of carbohydrates, disappearance of cellulose peaks and formation of aromatic and mineral derived phases. The scaled life cycle process yielded a global warming potential (GWP) of 119.3 kg CO 2 -eq per ton of dry paper waste, offset by soil carbon sequestration of − 556.41 kg CO 2 -eq, resulting in a net impact of − 427.36 kg CO 2 -eq. This represents a net carbon removal exceeding by ~186 % the emissions associated with landfilling paper waste with electricity generation.

09 BIOMASS FUELS↗

Computational Study of a Cryopump Design for Fusion Exhaust Gas Purification Using Direct Simulation Monte Carlo

Cryopump-based direct internal recycling (DIR) of fusion fuel is an attractive prospect because it provides pumping of helium ash from a reactor along with separation of helium and other impurities from the fuel. Previous studies have demonstrated a continuously regenerating cryopump, referred to as the Snail pump, that separates helium ash from fusion fuel for reactor-relevant flow rates. Here, in this study, a conceptual cryopump was designed as a proof-of-principle study to target other impurities, besides helium ash, from the fusion exhaust that would complement the Snail pump. The impurity-removal cryopump consists of four sets of chevron fins, two sets operating at 80 K and the other two at 30 K. A computational study using direct simulation Monte Carlo (DSMC) was performed with a gas mixture of 96.5% D2, 2.0% He, and 0.5% each of CO2, N2, and CH4. In this configuration, 80 K chevron fin sets are capable of capturing CO2 and 30 K sets capable of capturing CO2, N2, and CH4. The computational study showed that the cryopump is capable of reducing the impurity content by more than two orders of magnitude from the flow.

Adhikari, Nirajan [Oak Ridge National Laboratory (↗

Rare Earth Elements (REE) and Critical Minerals (CM) in Middle Pennsylvanian-Age Coals and Associated Sediments in the Central Appalachian Basin, Eastern U.S.A.

The Central Appalachian Basin (CAB) of Kentucky, Tennessee, West Virginia and Virginia has a long history of coal mining and oil and gas extraction that has empowered the regional and national economies, the development of infrastructure, and a highly trained energy resources work force. As our societal demands for advanced technologies have rapidly increased in recent years, coal-related materials are viewed as an important new unconventional domestic source of critical minerals (CM) that are required for telecommunications, aerospace and transportation industries, electronics, the transition to low-carbon emissions energy production, and many consumer products. Coal-related materials encompass coal, associated sediments, coal mining waste materials, produced waters, and ash residues from coal-fired power plants. An important objective of the Evolve Central Appalachia Project (Evolve CAPP), sponsored by the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL) is to assess the quantity and distribution of CM resources in the CAB region. The rare earth elements (REE) are considered highest priority, although other important CM such as niobium, gallium, and zirconium are known to occur in the Middle Pennsylvanian-age coals and sediments. Working with coal industry partners who provided access to drill cores, coal-related sediments and waste materials, over 600 samples have been collected for laboratory analysis, and over 730 materials have been scanned using portable x-ray fluorescence (pXRF) equipment. The application of pXRF provides the means for real-time semiquantitative analysis of CM content at very close spacings (typically 2-3 inch intervals) along drill core and in-situ channel samples that span the roof, coal seam, and floor rock. The comparison of pXRF geochemical data with laboratory results, geologic data, and downhole spectral gamma logs can provide high resolution input to lithologic and depositional models for future CM resource evaluations. The preliminary findings show that pXRF is capable of accurately measuring low concentrations of many of the CM with a high level of confidence (Ba, Cr, Ga, K, Nb, Rb, Sr, Th, Y), whereas for others (La, Ce, Co, Mn, Nd, Ni, Sc, Ti, V) the detection limits are very high or spectral interferences increase the uncertainty. Notably, the mean abundances of Y (34 ppm), La (86 ppm), Ga (40 ppm), and V (146 ppm) in coal underclays in the CAB region are up to 7X enriched compared with the overlying coal. These values also exceed the reported concentrations in published reference materials for upper continental crustal rocks (Rudnick and Gao, 2003), North American Shale Composite (Gromet et al., 1984), and North American coal (Finkelman, 1993). The pXRF data are in part verified by laboratory results that indicate the mean Y abundance (36 ppm) is highly correlated (R2 = 0.807) with total REE (ΣREE). The correlation is even higher (R2 = 0.957) with heavy REE (ΣHREE). Applying these correlations to the pXRF data for the coal underclays, the mean estimated values for ΣREE+Y and ΣHREE+Y are 270 ppm and 58 ppm, respectively. Although these average values are not considered high, the range of Y measured by pXRF in the coal underclays extended as high as 114 ppm, which would suggest ΣREE+Y equal to 847 ppm. The mean abundances of Zr (192 ppm) and Th (21 ppm) in coal underclays are also enriched compared with the overlying coal and these results likely reflect the presence of resistant detrital heavy minerals such as monazite, xenotime, and zircon in the underclay matrix. Several of the profiled coal seams and associated wall rocks contained thin volcanic ash layers up to 4-5 inches in thickness. The extent to which these ash fall layers provided a source for CM under the paleoenvironmental conditions that resulted in coal deposits in the CAB remains to be fully studied. Continuing investigations in the Evolve CAPP study area will include laboratory determinations of mineralogic and clay compositions, and evaluations of CM geochemical mobility in the coal and coal underclays.

Lassetter, Billy↗

Characterization Inform Sustainable Recovery of Critical Minerals from Fossil Energy Waste Feedstocks

Rare earth elements (REE) and other critical minerals (CM, e.g., Co, Ni, Li) have important uses in green energy and modern technologies, yet are vulnerable to potential supply chain disruptions. One potential domestic CM source is fossil energy wastes, such as acid mine drainage (AMD) and treatment solids (AMD solids), coal combustion ash, and Oil and Gas (O&G) drilling wastes (drill cuttings and produced waters). While they can contain lower CM concentrations then traditional ore, the quantity and fast availability as waste feedstock makes them a promising CM resource. To explore their promise, researchers at DOE’s National Energy Technology Laboratory (NETL) have collected and analyzed CM data for aforementioned fossil energy wastes, and utilized advanced geochemical characterization (e.g., synchrotron microprobe and sequential extraction) to identify the CM speciation and binding environments, and developed sustainable and targeted CM recovery. Successful examples include: (1) the discovery of easily mobile REE phases in Ca-rich coal combustion ash and developing a patented REE recovery process from Ca-rich Powder River Basin coal ash; (2) the successful identification of REE/Co/Ni/Zn hosting phases in acid mine drainage treatment solids (AMD solids) with diverse chemical composition (Al, Mn, or Fe-rich) informing the sequential recovery of different REE/CMs from AMD solids; (3) the recovery potential of Li and other CMs in O&G produced waters and drill cuttings. The innovations driven by characterization have the potential to offset the cost of waste management and wastewater treatments while reducing the cost and environmental footprint of CM extraction.

Stuckman, Mengling↗