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Targeted Rare Earth Element Extraction from Mine Drainage Treatment Solids Informed by Advanced Characterization

In support of a clean energy transition in the U.S., National Energy Technology Laboratory (NETL) has collaborated with staff at Hedin Environmental and students at the University of Pittsburgh to characterize critical mineral content and recovery potential from acid mine drainage treatment solids (AMD solids). AMD solids in Appalachia are an unconventional feedstock of rare earth elements (REEs), with potential of suppling 1,102 tons REE/year. To inform recovery efforts, select AMD solids were examined using synchrotron microprobe analysis in conjunction with USGS-developed geochemical modeling to indicate likely phases hosting critical minerals (REE, Co, Ni, etc.) and associated metals . More than 100 AMD solids were collected from 94 passive AMD treatment systems in Pennsylvania, where limestone aggregates are used for acidity neutralization. As pH increases, dissolved metals and critical minerals in AMD are attenuated as surface coatings on limestone. The collected AMD solids contained up to 2000 mg/kg REE, up to 13,000 mg/kg transition metals (Co, Ni, Zn) and up to 440 mg/kg Li. Regardless of the diverse chemical compositions from AMD solids (Al-rich, Mn-rich, or Al,Fe,Mn-rich), REEs were mostly associated with Al and Mn (hydr)oxides, while select heavy REEs (e.g., Gd, Dy) were co-localized with Fe (hydr)oxides. Co and Ni have different distribution zones, while both co-localized with Mn (hydr)oxides. Based on this characterization, NETL developed a patent-pending innovative step-leaching protocol, “Targeted Rare Earth Extraction (TREE)” to effectively recover up to 90% REE and 60% Co in separate steps. In addition, select post-TREE solid residuals (purified Al oxides, or Mn oxides) can be further developed into functional materials (e.g., lithium and CO2 sorbents) needed for green energy transition and carbon management. This characterization-informed approach as well as TREE processing from AMD solids can be used for other legacy wastes (e.g., coal ash, oil and gas drill cutting, mine tailings), and offers an opportunity to transform waste streams into environmental and economic assets that meet U.S. Department of Energy and U.S. Environmental Protection Agency goals.

characterization and extraction of rare earth elem↗

Achieving Unprecedented CO 2 Utilization InCO 2 Concrete™: System Design, Product Development and Process Demonstration

Anthropogenic sources of carbon dioxide are generated from a number of sources, but the key among these are ordinary Portland cement (OPC) production and combustion of fossil fuels. Cement production is the largest global CO 2 source from the mineral decomposition of carbonates. This is due to the clinkering process whereby limestone (mainly consisting of CaCO 3 ) is decomposed into CaO and CO 2 , and combined with silica rich clays at high temperatures to form clinkers (i.e. the four key minerals that comprise cement). The high temperature range of 1400 – 1550°C required for this process accounts for up to 60% of the generated CO 2 from cement production. Combination of the limestone decomposition and thermal requirements of the clinkering process causes cement production to contribute 8-9% of annual global CO 2 emissions. Combustion of fossil fuels (coal, oil and gas) was shown to contribute a much larger portion of global CO 2 emissions. As of 2018, combustion of fossil fuels accounted for 65% of global CO 2 , where 41% was derived from stationary sources for electricity and heat generation and the other 24% was related to transport. To reduce these contributions, key steps forward in CO 2 utilization technologies are required. Therefore, a CO 2 mineralization technology (CO 2 mineralization concrete) to reduce the OPC content in concrete, while utilizing flue gas emissions from fossil fuel combustion has been developed to address both areas simultaneously. This Reversa™ technology utilizes low-carbon cementation agents produced by in situ CO 2 mineralization (“mineral carbonation reactions”) to offer a promising alternative to OPC. CO 2 mineralization relies upon the reaction of dissolved CO 2 with inorganic alkaline reactants to precipitate mineral carbonates (e.g., CaCO 3 ), which bind proximate particles and achieve cementation. Herein, a concrete green body, which is composed of a mixture of binder, water, and mineral aggregates, is exposed to CO 2 borne in industrial flue gas streams. This manner of CO 2 mineralization allows the production of construction components that feature equivalent engineering attributes as their OPC-based counterparts while featuring a much smaller embodied carbon intensity (eCI). The purpose of this project is to demonstrate the feasibility of the Reversa process evolving from a TRL-3 technology at the bench-scale up to TRL-6 technology at the pilot-scale. The reliability of the Reversa technology was tested to prove the effective production of three standard industrial concrete products selected during the course of the project. The results detailed herein will demonstrate the evolution of this technology to the industrial scale. The culmination of this work resulted in 9 production runs completed at the National Carbon Capture Center (NCCC), Wilsonville, AL, using natural gas (NG) flue gas as the CO 2 source. Over the course of the production runs at NCCC, the CO 2 utilization as a function of time, 24-h CO 2 uptake, electricity usage, and 28-d net area compressive strength recorded for each run. Collection of this data will be used to determine the success of the demonstration goals: (1) achieving in excess of 0.2gCO 2 /g reactant , (2) achieving greater than 50% reduction in global warming potential compared to standard produced units, and (3) ensuring compliance of carbonated concrete with industry standard specifications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Petrographic and Advanced Geologic Characterization Report on Lively Grove #1 (API# 1218924947)

Lively Grove #1 (LG1 API number 1218924947) well was drilled to a depth of 5,758 feet, from the Glen Dean Limestone to the top of the Precambrian unit. In total, 49 thin sections were taken from Rotary Sidewall Core (RSWC), and one thin section was taken from Whole Core (2,918 feet, New Albany Shale) from 1,700 to 5,872 feet for this report. This report details specifically thin section point-counting analysis that includes mineralogical and pore space analysis, including grain size analysis annotated thin section photomicrographs, scanning electron microscopy (SEM) with Energy Dispersive x-ray Spectroscopy (EDS), X-ray Diffraction (XRD), statistics of grain size analysis on St. Peter Sandstone thin sections, and Argon-Argon (Ar-Ar) dating on Precambrian samples from LG1. Characterized units include the Salem Limestone, New Albany Shale, Trenton Group, Joachim Dolomite, St. Peter Sandstone, Everton Formation, Eminence Formation, Davis Member, Eau Claire Formation, and Precambrian Basement.

01 COAL, LIGNITE, AND PEAT↗

Development of Calcined Clay/Calcium Sulfate Blends for Robust Performance of LC3 Concrete

This report documents the development of robust blends of calcined clays (CCs) with calcium sulfate (gypsum) for application in limestone calcined clay cement (LC3) systems. The U.S. cement industry faces supply chain constraints and high energy intensity, motivating the need for alternative supplementary cementitious materials. Calcined clays are abundant and highly reactive when properly processed, but their variable physical and chemical characteristics can negatively impact hydration balance, rheology, and admixture demand in LC3 concretes. To address this, five calcined clays, two Portland cements, ground limestone, gypsum, and a polycarboxylate dispersant were procured. Isothermal calorimetry and mini-cone flow tests were used to determine sulfate and dispersant demand. Results show that the addition of approximately 6.7% gypsum, relative to the calcined clay weight, consistently balanced sulfate consumption across the LC3 systems studied. Dispersant demand, however, varied significantly with clay source, demonstrating the need for tailored admixture strategies. These findings confirm that supplying CC–gypsum blends directly to concrete producers is a viable approach to overcoming current manufacturing constraints, enabling reliable fresh and hardened performance of LC3 concretes, and supporting broader adoption of calcined clays in the U.S. market.

36 MATERIALS SCIENCE↗

Multiscale Assessment of Caprock Integrity for Geologic Carbon Storage in the Pennsylvanian Farnsworth Unit, Texas, USA

Leakage pathways through caprock lithologies for underground storage of CO2 and/or enhanced oil recovery (EOR) include intrusion into nano-pore mudstones, flow within fractures and faults, and larger-scale sedimentary heterogeneity (e.g., stacked channel deposits). To assess multiscale sealing integrity of the caprock system that overlies the Morrow B sandstone reservoir, Farnsworth Unit (FWU), Texas, USA, we combine pore-to-core observations, laboratory testing, well logging results, and noble gas analysis. A cluster analysis combining gamma ray, compressional slowness, and other logs was combined with caliper responses and triaxial rock mechanics testing to define eleven lithologic classes across the upper Morrow shale and Thirteen Finger limestone caprock units, with estimations of dynamic elastic moduli and fracture breakdown pressures (minimum horizontal stress gradients) for each class. Mercury porosimetry determinations of CO2 column heights in sealing formations yield values exceeding reservoir height. Noble gas profiles provide a “geologic time-integrated” assessment of fluid flow across the reservoir-caprock system, with Morrow B reservoir measurements consistent with decades-long EOR water-flooding, and upper Morrow shale and lower Thirteen Finger limestone values being consistent with long-term geohydrologic isolation. Together, these data suggest an excellent sealing capacity for the FWU and provide limits for injection pressure increases accompanying carbon storage activities.

58 GEOSCIENCES↗

Deep Learning and Photogrammetric Reconstruction for Automated Crack Detection and Dimensional Measurement in Mining Operations

Surface crack detection and dimensional measurement at active mining sites present significant safety and operational challenges. Manual inspection methods are labor-intensive, spatially incomplete, and expose personnel to hazardous environments, while existing automated approaches have been developed primarily for concrete civil infrastructure and have not been validated on the complex, variable surfaces characteristic of mining environments. This dissertation presents an automated pipeline that integrates deep learning semantic segmentation with Structure-from-Motion photogrammetry to detect surface cracks and measure their aperture, length, and vertical displacement from standard RGB imagery acquired during routine Uncrewed Aerial Vehicle (UAV) survey operations, without requiring additional sensor hardware or manual measurement. The pipeline combines a U-Net architecture with an EfficientNet-B0 encoder, pretrained on the SDNET2018 concrete crack dataset and fine-tuned on a mining-specific dataset spanning laboratory concrete specimens, coal refuse impoundment embankments, and post-blast limestone quarry benches. Photogrammetric reconstruction is performed using COLMAP Structure-from-Motion and Multi-View Stereo, with crack segmentation masks projected into the reconstructed point cloud to enable three-dimensional vertical displacement measurement through local plane fitting and bimodal surface detection. The pipeline was validated across 36 controlled laboratory specimens at three imaging distances and four vertical displacement levels, achieving aperture measurement RMSE of 0.047 cm and R² of 0.954, and vertical displacement RMSE of 0.140 cm and R² of 0.966, against independent caliper measurements. Field application at a coal refuse impoundment in southwestern Pennsylvania detected 71 crack components across the embankment crest, with a dominant longitudinal crack exhibiting aperture values reaching 28 cm and a 95th percentile vertical displacement of 35.53 cm, consistent in magnitude and spatial distribution with simultaneously acquired LiDAR-derived estimates. Application across four post-blast limestone quarry bench datasets in California successfully characterized blast-induced fracture networks at ground sampling distances ranging from 0.59 to 1.23 cm/pixel, with detected crack geometries physically consistent with observable surface conditions at each site. The results demonstrate that deep learning-based crack detection and photogrammetric measurement can be integrated into routine UAV inspection workflows at mining sites, providing repeatable, scalable, and quantitative crack characterization across surface types, crack scales, and displacement magnitudes not previously addressed in the literature. The pipeline requires no dedicated surveying equipment beyond the UAV platforms already deployed at mine sites for survey and monitoring purposes, supporting practical adoption within existing operational workflows.

Crack detection, Dimensional Measurement↗

Identification of geostructures of continental crust particularly as they relate to mineral resource evaluation

The author has identified the following significant results. Preliminary examination of ERTS-1 imagery in central and northern Alaska substantiates the existence of a conjugate set of northeast and northwest faults suggested by linears noted on Nimbus 4 images. Linears of both trends are well expressed and several have been mapped as faults, including the Shaw Creek fault. Imagery provides new data to support the interpretation that the Kobuk Trench is the northern margin of a broad west-trending fault zone bounded on the north and south by strike-slip faults. In northwestern Alaska, MSS band 5 imagery shows Mississippian limestone as white, while shale, sandstone, and chert of other ages appear dark. As the limestone is the basal formation of the numerous thrust plates stacked in the area, images of band 5 will assist significantly in depicting the distribution of the thrust plates. In south-central Alaska the newly described Totshunda fault is readily identified and extends into areas not yet mapped. Also shown is another fault parallel to the south of the Totshunda which has not yet been recognized in the field.

Gryc, G.↗

Geophysical aspects of remote sensing

Results obtained through the NASA Earth Resources Aircraft Program at Mill Creek, Oklahoma, provide a case history example of the application of remote sensing to the identification of geologic rock units. Thermal infrared images are interpreted by means of a sequence of models of increasing complexity. The roles of various parameters are examined: rock properties (thermal inertia, albedo, emissivity), site location (latitude), season (sun's declination), atmospheric effects (cloud cover, transmission, air temperature), and topographic orientation (slope, azimuth). The results obtained at this site also illustrate the development of an important application of remote sensing in geologic identification. Relatively pure limestones and dolomites of the Mill Creek test area can be differentiated in nighttime infrared images, and facies changes between them can be detected along and across strike. The predominance on the earth's surface of sedimentary rocks, of which limestone and dolomite are major members, indicates the importance of this discrimination.

Watson, K.↗

Material handling systems for the fluidized-bed combustion boiler at Rivesville, West Virginia

The 300,000 lbs/hr steam capacity multicell fluidized-bed boiler (MFB) utilizes complex material handling systems. The material handling systems can be divided into the following areas: (1) coal preparation; transfer and delivery, (2) limestone handling system, (3) fly-ash removal and (4) bed material handling system. Each of the above systems are described in detail and some of the potential problem areas are discussed. A major potential problem that exists is the coal drying system. The coal dryer is designed to use 600 F preheated combustion air as drying medium and the dryer effluent is designed to enter a hot electrostatic precipitator (730 F) after passage through a cyclone. Other problem areas to be discussed include the steam generator coal and limestone feed system which may have operating difficulties with wet coal and/or coal fines.

Branam, J. G.↗

Simulation of fluidized bed coal combustors

The many deficiencies of previous work on simulation of fluidized bed combustion (FBC) processes are presented. An attempt is made to reduce these deficiencies, and to formulate a comprehensive FBC model taking into account the following elements: (1) devolatilization of coal and the subsequent combustion of volatiles and residual char; (2) sulfur dioxide capture by limestone; (3) NOx release and reduction of NOx by char; (4) attrition and elutriation of char and limestone; (5) bubble hydrodynamics; (6) solids mixing; (7) heat transfer between gas and solid, and solid and heat exchange surfaces; and (8) freeboard reactions.

Rajan, R.↗

Reduction of particulate carryover from a pressurized fluidized bed

A bench scale fluidized bed combustor was constructed with a conical shape so that the enlarged upper part of the combustor would also serve as a granular bed filter. The combustor was fed coal and limestone. Ninety-nine tests of about four hours each were conducted over a range of conditions. Coal-to-air ratio varied from 0.033 to 0.098 (all lean). Limestone-to-coal ratio varied from 0.06 to 0.36. Bed depth varied from 3.66 to 8.07 feet. Temperature varied from 1447 to 1905 F. Pressure varied from 40 to 82 psia. Heat transfer area had the range zero to 2.72 ft squared. Two cone angles were used. The average particulate carry over of 2.5 grains/SCF was appreciably less than cylindrical fluidized bed combustors. The carry over was correlated by multiple regression analysis to yield the dependence on bed depth and hence the collection efficiency, which was 20%. A comparison with a model indicated that the exhaust port may be below the transport disengaging height for most of the tests, indicating that further reduction in carry over and increase in collection efficiency could be affected by increasing the freeboard and height of the exhaust port above the bed.

Patch, R. W.↗

Reduction of particulate carryover from a pressurized fluidized bed

A bench-scale pressurized fluidized bed combustor (PFBC) constructed with a conical shape to reduce the particulate carryover is examined. The combustor was fed coal and limestone with the coal to air ratio varying from 0.033 to 0.098 (all lean) and the coal to limestone ratio varying from 0.06 to 0.36. Two cone angles were used and it is shown that the average particulate carryover of 2.5 grains/SCF is appreciably less than cylindrical fluidized bed combustors. In addition the carryover was correlated by multiple regression analysis to yield the dependence on bed depth and hence the collection efficiency, which was 20%. Finally, a comparison with a model indicated that the exhaust port may be below the transport disengaging height for most of the tests showing that further improvements could be achieved by increasing the freeboard height of the exhaust port above the bed.

Patch, R. W.↗

Extraterrestrial cause for the Cretaceous-Tertiary extinction

Direct physical evidence is presented for an unusual event at exactly the time of extinctions in the planktonic realm. Deep-sea limestones exposed in Italy, Denmark, and New Zealand indicate iridium increases of about 30, 160, and 20 times, respectively, above the background level at precisely the time of the Cretaceous-Tertiary extinctions, 65 million years ago. Reasons are given that this iridium is of extraterrestrial origin, but did not come from a nearby supernova. A hypothesis is set forth which accounts for the extinctions and the iridium observations. One prediction of this hypothesis is verified, that the chemical composition of the boundary clay, which is thought to come from the stratospheric dust, is markedly different from that of clay mixed with the chemically similar Cretaceous and Tertiary limestones.

Alvarez, L. W.↗

A non-catastrophist explanation for the iridium anomaly at the Cretaceous/Tertiary boundary

The iridium (Ir) anomaly at the Cretaceous/Tertiary (C/T) boundary can be explained by dissolution of normal pelagic limestones producing an insoluble clay residue containing Ir-rich meteoritic material. Further concentration of Ir and other trace metals in the clay can be explained by deposition under reducing conditions. Clay-mineral analyses indicate that the boundary clay is similar to locally derived clays in the limestones above and below the boundary, and contains no detectable exotic components. This supports a terrestrial origin for the boundary clay. The genesis of the boundary clay is attributed to changes in ocean chemistry (pH and oxygenation), leading to an interval of widespread dissolution of carbonate sequences in the oceans, and culminating in the development of submarine pyritic hardgrounds and a disconformity of global extent.

Rampino, M. R.↗

An exploitation of coregistered SIR-A, Seasat and Landsat images

Multispectral registration and classification of SIR-A, Seasat SAR, and Landsat MSS data is presented over two playas located in the northeastern Algerian Sahara. A supervised classification was made over six classes: salt, palm trees, dunes, limestones, gypsum and sand. The best classification is obtained by using all of the data. The images using radar only misclassify trees and salt, limestone and dunes, gypsum and dunes. Landsat only gives a good map but lacks the roughness information contained in the radar data. The Landsat/SIR-A combination gives a better classification than the Landsat/Seasat combination. Density number histograms computed within several classes on the Seasat and SIR-A data show the misclassification is mainly due to the Seasat data.

Rebillard, P.↗

A geological interpretation of Seasat-SAR imagery of Jamaica

Spaceborne radar imagery obtained from Seasat allows an unobscured large-scale view of Jamaica that can be used for geological interpretation. Lineaments and textures visible in these images were mapped and compared with the known geology of the Tertiary karst limestones covering the central and western parts of the island. Some of these radar textures correlate with lithological units, while others follow tectonically-controlled zones or structural blocks. Mapping of radar lineaments has led to the recognition of three new aspects of Jamaican faults: (1) a major through-going NE-SW fault system, termed here the Vere-Annotto lineament; (2) a series of curving scissor faults in the central part of the island; and (3) the related observation that the dominant NNW-SSE tectonic fabric of the central part of the island takes the form of an elongate sigmoid in plan view. During most of the Neogene Jamaica has been part of an active zone of left-lateral transform motion between the Caribbean and North American plates and is a region of anomalous uplift. The radar imagery is a sensitive recorder of the deformation undergone by the karst limestones in this tectonic regime. Some of the observations are explained with models for a complex, evolving shear zone.

Wadge, G.↗

Lithologic mapping in a forested region using remotely sensed data

Forest canopies over different sedimentary lithologies of valleys and ridges are composed of different dominant species and have significantly different reflectance and emittance. In a botanical survey of eighty-seven forest sites, sedimentary lithologies were found to differ in the species which dominate the forest canopy. Sandstone sites had abundant chestnut oak (Quercus prinus), black oak (Q. velutina), and northern red oak (Q. rubra). On shale sites chestnut oak, white oak (Q. alba), northern red oak and red pine (Pinus resinosa) were dominant. Limestone sites had a variable species composition with the most common species, northern red oak, white oak, and black locust (Robinia pseudocacia) accounting for only 30 percent of the total trees. Thematic Mapper Simulator (TMS) data obtained during the growing season were analyzed to determine if sandstones, shales, and limestones could be distinguished on the basis of forest-canopy reflectance. The observations compared in the analysis were means of the eight TMS bands for 10 x 10-pixel test sites selected from areas with complete canopy closure. In August imagery the three lithologies were separable based on differences in TMS band 3 (630-690 nm) and band 8 (10.4-12.5 microns).

Masuoka, E.↗

Geochemistry of Precambrian carbonates - 3-shelf seas and non-marine environments of the Archean

Samples from the Pangola and Ventersdorp Supergroups (Kaapvaal Craton, South Africa) and from the Fortescue and Hamersley Groups (Pilbara Block, Australia) were analyzed, using XRF, AAS, and isotope-analysis techniques to investigate the mineralogical, chemical, and isotopic features of these representatives of contemporary shelf carbonates (Pangola and Hamersley samples) and nonmarine carbonates (the Ventersdorp and Fortescue samples). Results show that, mineralogically, the shelf carbonates are almost exclusively dolostones, while the lacustrine facies are predominantly limestones. Geological, trace-element, and oxygen-isotope results of the shelf carbonates suggest that their original mineralogy may have been aragonite, and that the Pangola dolostones may represent a direct dolomitization product of this precursor. By contrast, the stabilization of the Hamersley carbonates may have involved an additional step of transformation of a metastable precursor into limestone.

Veizer, Jan↗