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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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17 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Apollo Next Generation Sample Analysis (ANGSA): an Apollo Participating Scientist Program to Prepare the Lunar Sample Community for Artemis

As a first step in preparing for the return of samples from the Moon by the Artemis Program, NASA initiated the Apollo Next Generation Sample Analysis Program (ANGSA). ANGSA was designed to function as a low-cost sample return mission and involved the curation and analysis of samples previously returned by the Apollo 17 mission that remained unopened or stored under unique conditions for 50 years. These samples include the lower portion of a double drive tube previously sealed on the lunar surface, the upper portion of that drive tube that had remained unopened, and a variety of Apollo 17 samples that had remained stored at -27 °C for approximately 50 years. ANGSA constitutes the first preliminary examination phase of a lunar “sample return mission” in over 50 years. It also mimics that same phase of an Artemis surface exploration mission, its design included placing samples within the context of local and regional geology through new orbital observations collected since Apollo and additional new “boots-on-the-ground” observations, data synthesis, and interpretations provided by Apollo 17 astronaut Harrison Schmitt. ANGSA used new curation techniques to prepare, document, and allocate these new lunar samples, developed new tools to open and extract gases from their containers, and applied new analytical instrumentation previously unavailable during the Apollo Program to reveal new information about these samples. Most of the 90 scientists, engineers, and curators involved in this mission were not alive during the Apollo Program, and it had been 30 years since the last Apollo core sample was processed in the Apollo curation facility at NASA JSC. There are many firsts associated with ANGSA that have direct relevance to Artemis. ANGSA is the first to open a core sample previously sealed on the surface of the Moon, the first to extract and analyze lunar gases collected in situ, the first to examine a core that penetrated a lunar landslide deposit, and the first to process pristine Apollo samples in a glovebox at -20 °C. All the ANGSA activities have helped to prepare the Artemis generation for what is to come. The timing of this program, the composition of the team, and the preservation of unopened Apollo samples facilitated this generational handoff from Apollo to Artemis that sets up Artemis and the lunar sample science community for additional successes.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

An organogel library for solution NMR analysis of nanoparticle suspensions in non-aqueous samples

Surface contrast solution NMR methods (scNMR) are emerging as powerful tools to investigate the adsorption of small molecule ligands to the surface of nanoparticles (NP), returning fundamental insight into the kinetics and thermodynamics of sorption, as well as structural information on the adsorbed species. A prerequisite for the acquisition of high quality solution NMR data is the preparation of homogeneous and stable samples that return consistent NMR spectra and allow extensive signal averaging. Unfortunately, this condition does not apply to NMR samples containing NPs that often show a tendency to sediment and accumulate at the bottom of the NMR tube over the course of the experiment. We have recently shown that preparing NMR samples in an agarose gel matrix inhibits sedimentation and allows the characterization of small molecule-NP interactions by scNMR. Unfortunately, as the agarose gel only forms in aqueous solution, this sample preparation method cannot be used to stabilize NP suspensions in a non-aqueous environment. In this work, we introduce a library of 48 organogels, based on low molecular-mass organic gelators (LMOGs), to prepare NMR samples of small molecule/NP systems in a wide range of organic solvents. In addition, we present a simple method that takes advantage of 1H transverse relaxation (1H-R2) measurements to screen the library and identify the best gelator to characterize the small molecule-NP interaction of interest in the solvent of choice. We expect the results of this study will enable the preparation of homogeneous and stable samples of NPs in non-aqueous environments, therefore dramatically increasing the applicability of scNMR to the characterization of heterogeneous interactions and to the investigation of the role played by solvent molecules in regulating the kinetics and thermodynamics of sorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

High-resolution analysis of clay minerals and amorphous materials in martian analog environments

Mudrocks and mud-sized sediments (i.e., silt to clay) dominate the surface of Earth and Mars. These fine-grained sediments preserve a rich history of sedimentary processes from source to sink and shed light on ancient climates. However, both the physical and chemical nature of these materials make them difficult to fully characterize with traditional laboratory techniques. Here, we explore a cross-disciplinary and high-resolution approach using synchrotron radiation for X-ray diffraction, pair distribution function analysis, and submicrometer-scale X-ray fluorescence, combined with transmission electron microscopy, to better understand the nanostructure and composition of mud-sized sediments from a glacio-fluvial watershed in southwest Iceland. Our results demonstrate that sediments in the cold and wet climate of Iceland are more altered than previously thought, as evidenced by the identification of kaolinite and mixed-layer kaolinite-smectite. Additionally, sediments are enriched in amorphous materials and nanocrystalline phases, as determined from grain morphologies and compositions consistent with allophane, hisingerite, ferrihydrite, and halloysite. These alteration products are present as intimate mixtures that vary across depositional sites, demonstrating the dynamic nature of the secondary assemblage from source to sink. This work has implications for Mars, where, for example, basalt-sourced sedimentary rocks from Gale crater are abundant in clay minerals and amorphous materials. Finally, this work underpins the importance of using high-resolution techniques, a coordinated methodology, and developing innovative approaches for future planetary sample return missions (e.g., Mars sample return).

36 MATERIALS SCIENCE↗
DOE OSTI2026

Thermoreflectance Detection of Point Defects Resulting from Focused Ion Beam Milling

Focused ion beam (FIB) milling is a commonly used tool for nanoscale material processing, such as for transmission electron microscopy (TEM) sample preparation, or the creation of fiducial markers prior to other processes and measurements. During milling, a high energy ion beam is used to remove material via sputtering. The expelled target material may return to the sample surface however, affecting subsequent measurements. Beam spreading or irradiation due to neutral gallium may also irradiate a larger area than intended. Extensive research has explored the effects of FIB milling on the prepared TEM sample, but few have looked at the effects of milling on the properties of the sample surrounding the milled region. We use multiple pump-probe laser-based techniques (time domain thermoreflectance and steady-state thermoreflectance) to measure the spatial extent of FIB-induced surface/subsurface changes on a series of silicon wafers milled at multiple currents and doses. We supplement these measurements with high-resolution scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, stylus profilometry, and time-of-flight secondary ion mass spectroscopy. We find a sample surface affected by the FIB up to 1 mm from where milling occurred, with a notable dependence on the ion beam current. We also note remarkably high sensitivity to surface defects using the thermoreflectance metrologies, including detection where other measurements failed.

defects↗
DOE OSTI2023

Depth profiling and standardization from the back side of a sample for accurate analyses: Emphasis on quantifying low‐fluence, shallow implants in diamond‐like carbon

Rationale Back‐side thinning of wafers is used to eliminate issues with transient sputtering when analyzing near‐surface element distributions. Precise and accurate calibrated implants are created by including a standard reference material during the implantation. Combining these methods allows accurate analysis of low‐fluence, shallow features even if matrix effects are a concern. Methods Implanted Na (<2.0 × 10 11 ions/cm 2 , peaking <50 nm) in diamond‐like carbon (DLC) film on silicon (solar wind returned by NASA's Genesis mission) was prepared for measurement as follows. Implanted surfaces of samples were epoxied to wafers and back‐side‐thinned using physical or chemical methods. Thinned samples were then implanted with reference ions for accurate quantification of the solar wind implant. Analyses used a CAMECA IMS 7f‐GEO SIMS in depth‐profiling mode. Results Back‐side‐implanted reference ions reduced the need to change sample mounts or stage position and could be spatially separated from the solar wind implant even when measuring monoisotopic ions. Matrix effects in DLC were mitigated and the need to find an identical piece of DLC for a reference implant was eliminated. Accuracy was only limited by the back‐side technique itself. Conclusions Combining back‐side depth profiling with back‐side‐implanted internal standards aides quantification of shallow mono‐ and polyisotopic implants. This technique helps mitigate matrix effects and keeps measurement conditions consistent. Depth profile acquisition times are longer, but if sample matrices are homogeneous, procedural changes can decrease measurement times.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Characterizing Ocean Acidification and Atmospheric Emission caused by Methane Released from Gas Hydrate Systems along the US Atlantic Margin (Final Report)

To assess the environmental impact of decomposing gas hydrates, this project characterized the atmospheric emission and ocean acidification associated with seafloor-released methane along the U.S. Atlantic Margin. This project leveraged the newly discovered seafloor seeps in this region, many of which are located near the landward limit of gas hydrate stability, to investigate the fate and environmental impact of methane once released from the seafloor. Several research directions were pursued during these investigations. First, high-spatial resolution surface surveys were conducted to characterize the degree to which sea-to-air emission of methane is correlated with acoustically detected seafloor bubble emissions. Second, the natural isotopic signatures of both radiocarbon and δ 13 C were measured throughout the water column to observe if seafloor-released methane was detected in surface waters or if it was replaced by a different source. Third, the extent of methane oxidation in the water column was constrained to assess the ability of this process to mitigate atmospheric methane emissions. Fourth, since aerobic methane oxidation ultimately converts methane to carbon dioxide, the extent of ocean acidification relating to this process was assessed. Ultimately, this project was conducted in four stages. Stage one involved preparations for the research expedition along the U.S. Atlantic Margin. This involved calibrating, modifying, and validating equipment needed for sample and data collection in this unique environment. Stage two involved executing the at-sea science. This research was conducted from 25 August to 5 September 2017 on the R/V Hugh R. Sharp. This expedition left from Lewes, Delaware and investigated the continental slope from approximately this latitude down to Cape Hatteras, North Carolina. Third, any samples unanalyzed on the research vessel were returned to the laboratory and measured. Fourth, the data were interpreted, and publications and presentations were prepared.

03 NATURAL GAS↗
DOE OSTI2025

Dual aging pathways of Cu-SSZ-13 SCR catalysts: Hydrothermal vs. sulfur-induced deactivation

Hydrothermal aging (HTA) and chemical poisoning are two primary factors contributing to the real-world degradation of Cu-SSZ-13 SCR catalysts. Investigating field-returned samples offers valuable insights into performance degradation caused by these mechanisms. However, the simultaneous presence of both deactivation pathways complicates the isolation of their individual effects in post-mortem analyses. In this study, we separately prepared model Cu-SSZ-13 SCR catalysts subjected to hydrothermal-aging and sulfur-induced chemical poisoning. Using various characterization techniques, we elucidated the specific role of each aging process in catalyst deactivation and compared the results to real-world field-aged catalysts. Our findings show that hydrothermal aging at 650 °C for 100 h caused dealumination of the zeolite framework but no significant CuO x cluster formation. In contrast, sulfur aging (via sulfur exposure, calcination at 550 °C, and desulfation up to 750 °C) led to CuO x formation without any observable dealumination. On model catalysts, sulfur poisoning was found to reduce Cu mobility and the amount of active Cu sites, thus degrading catalyst activity. Although some activity was recovered upon desulfation, a portion of the initial catalyst activity remained irreversibly lost due to CuO x formation. We demonstrate that this occurs because sulfated species impede the ability of multi-nuclear Cu species (e.g., Cu dimers) to split back into their isolated form, leading to CuSO 4 -clusters that oxidatively desulfate to CuO x species. This degradation pathway explains the significant reduction in activity of field-aged samples, where substantial CuSO 4 -cluster accumulation leads to reduced active Cu and subsequent conversion to CuO x . Furthermore, the conclusions from model catalysts were extended directly to field-aged commercial samples, elucidating the decline in activity and chemical properties during field deployment.

Catalyst Deactivation↗
DOE OSTI2024

Plutonium-238 Loadout Calorimeter Return To Service

The calorimeter in the transfer area in Building 7920 at the US Department of Energy’s Oak Ridge National Laboratory is used to measure the amount of 238 Pu in the Plutonium Heat Source Oxide. The calorimetry measurement is taken after the oxide is packaged in an ORISC (Oak Ridge Inner Shipping Capsule)/FSO (Fuel Storage Outer) assembly before loading into the Containment Vessel and shipping container. The equipment is used in three specific configurations: zero measurement (nothing in the sample cup), FSO measurement (actual measurement of 238 Pu), and reference calibration measurement (using the reference FSO as a known heat source). System checks were performed in July 2023 in preparation for scheduled material loadout. During these checks, personnel discovered that the reference FSO had experienced an electrical short in the heater cable and was no longer functional. The calorimeter was in the reference calibration measurement configuration at this time. Facility management was notified when the damage was discovered. The data from the Yokogawa recorder were pulled and analyzed for a span of time between September 2022 and July 2023. An unusual spike was found in the sample cup temperature data that started on October 19, 2022, and ended on October 20, 2022. The sample cup reached a temperature of 191.1°C. The maximum allowable temperature for the calorimeter thermopile to reach is 220°C based on the manufacturer statement provided in Appendix B of this report [1]. The calorimeter thermopile and the sample cup thermocouple are physically close to each other; therefore, the data suggest that the calorimeter itself never saw a temperature in excess of 191.1°C. Physical damage present on the cable, tape, and insulation suggests that the temperature reached a higher value in some locations within the sample cup than the data shows. Because of this discrepancy, testing of the calorimeter was required to confirm that the calorimeter is functioning the same as it was before the electrical short. The intent of this report is to assess the functionality of the calorimeter and determine if it is acceptable to use for 238 Pu loadout material measurement. Testing showed that the calorimeter is functionally equivalent to the initial calibration that was performed in the summer of 2021, and thus, the calorimeter was cleared to be used for its intended purposes.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Capture of Iodine from Nuclear-Fuel-Reprocessing Off-Gas: Influence of Aging on a Reduced Silver Mordenite Adsorbent after Exposure to NO/NO 2

Iodine radioisotopes released during nuclear fuel reprocessing must be removed from the off-gas stream before discharge. One promising material for iodine capture is reduced silver mordenite (Ag 0 Z). Nevertheless, the adsorbent’s capacity will degrade, or age, over time when the material is exposed to other off-gas constituents. Though the overall impact of aging is known, the underlying physical and chemical processes are not. To examine these processes, Ag 0 Z samples were prepared and aged in 2% NO 2 in dry air and in 1% NO in N 2 gas streams at 150 °C for up to six months. Aged samples were then characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray absorption spectroscopy. These techniques show that aging involves two overarching processes: (i) oxidation of the silver nanoparticles present in Ag 0 Z and (ii) migration of oxidized silver into the mordenite’s inner network. Silver on the nanoparticle’s surface is oxidized through adsorption of O 2 , NO, and NO 2 . Additionally, Raman spectroscopy and X-ray absorption spectroscopy indicate that nitrates are the primary products of this adsorption. Most of these nitrates migrate into the interior of the mordenite and exchange at framework binding sites, returning silver to its unreduced state (AgZ). The remaining nitrates exist at a persistent concentration without aggregating into bulk-phase AgNO 3 . X-ray absorption spectroscopy results further indicate that iodine adsorption occurs on not just Ag 0 Z but also on AgZ and a portion of the nitrates in the system. AgZ adsorbs a sizable quantity of iodine early in the aging process, but its capacity drops rapidly over time. For well-aged samples, nitrates are responsible for up to 95% of mordenite’s iodine capacity. Overall, these results have enhanced our understanding of the aging process in silver mordenite and are expected to guide the development of superior adsorbents for the capture of radioactive iodine from reprocessing off-gas.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

STOCHASTIC OPTIMIZATION FOR LONG TERM CAPITAL STRUCTURES, SYSTEMS, AND COMPONENTS REFURBISHMENT AND REPLACEMENT

As commercial nuclear power plants (NPPs) pursue extended plant operations in the form of Second License Renewals (SLRs), opportunities exist for these plants to provide capital investments to ensure long-term, safe, and economic performance. Several utilities have already announced their intention to pursue extended operations for one or more of their NPPs via SLR2. The goal of this research is to develop a riskinformed approach to evaluate and prioritize plant capital investments made in preparation for, and during the period of, extended plant operations to support decisions in NPP operations. In order to prioritize project selection via a riskinformed approach we developed a single decision-making tool that integrates safety/reliability, cost, and stochastic optimization models to provide users with data analysis capabilities to more cost effectively manage plant assets. Both stochastic analysis methods—such as Monte Carlo-based sampling strategies—and multi-stage stochastic optimization strategies are employed to provide priority lists to decisionmakers in support of risk-informed decisions. We applied the proposed method to a trial application of projected replacement/refurbishment expenditures for plant capital assets (i.e., Structures, Systems, and Components [SSCs]). The objective is to optimize the SSC replacement/refurbishment schedule in terms of economic constraints, data uncertainties, and SSC reliability data, as well to generate a priority list for maximizing returns on investment.

42 ENGINEERING↗
DOE OSTI2023

Experiment Design and Preparation for a Shielding Benchmark Utilizing Godiva-IV

An experiment is currently being designed to provide a high-quality shielding benchmark for Criticality Accident Alarm System (CAAS) modeling. Previous benchmarks have suffered from uncertainty primarily due to two factors. The first factor is radiation that is not directly coming from the source, also known as room return. Room return is notoriously difficult to account for in experimental data and to model in benchmarks. The second factor is uncertainty associated with the source term itself. In order to reduce these two sources of uncertainty, this experiment will utilize a room return shield [1] that will reduce the effect of room return and previous work performed to ensure the reproducibility of the source term. The experiment will use the Godiva IV [2] assembly located at the National Criticality Experiments Research Center (NCERC) to provide a neutron source representative of a criticality accident. Previous experiments [3]-[4] have shown that Godiva IV is capable of producing both bursts and steady-state emissions of equal magnitude which will allow for reduced uncertainty in the source term. The room return shield will house and isolate the shielding samples, neutron activation foils, and other detectors. Data collected will provide a comparison of the neutron and gamma dose for shielded and unshielded configurations. This data will be used to validate shielding data used for modeling criticality accident alarm systems. Shielding samples included in this benchmark are C, Fe, NaCl, Pb, high density polyethylene, and SiO 2 . This paper details the design of the room return shield, the experimental plan, challenges, and mitigation strategies.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2020

Photophysics of graphene quantum dot assemblies with axially coordinated cobaloxime catalysts

We report a study of chromophore-catalyst assemblies composed of light harvesting hexabenzocoronene (HBC) chromophores axially coordinated to two cobaloxime complexes. The chromophore-catalyst assemblies were prepared using bottom-up synthetic methodology and characterized using solid-state NMR, IR, and x-ray absorption spectroscopy. Detailed steady-state and time-resolved laser spectroscopy was utilized to identify the photophysical properties of the assemblies, coupled with time-dependent DFT calculations to characterize the relevant excited states. The HBC chromophores tend to assemble into aggregates that exhibit high exciton diffusion length (D = 18.5 molecule 2 /ps), indicating that over 50 chromophores can be sampled within their excited state lifetime. We find that the axial coordination of cobaloximes leads to a significant reduction in the excited state lifetime of the HBC moiety, and this finding was discussed in terms of possible electron and energy transfer pathways. By comparing the experimental quenching rate constant (1.0 × 10 9 s -1 ) with the rate constant estimates for Marcus electron transfer (5.7 × 10 8 s -1 ) and Förster/Dexter energy transfers (8.1 × 10 6 s -1 and 1.0 × 10 10 s -1 ), we conclude that both Dexter energy and Marcus electron transfer process are possible deactivation pathways in CoQD-A. No charge transfer or energy transfer intermediate was detected in transient absorption spectroscopy, indicating fast, subpicosecond return to the ground state. Finally, these results provide important insights into the factors that control the photophysical properties of photocatalytic chromophore-catalyst assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Fluid Induced Elemental and Mineralogy Alterations of Caney Shale

ABSTRACT: Studies were conducted on cores and rock cuttings recovered from two wells drilled in Caney shale in the Southern Oklahoma. Mineralogical compositions of these samples were obtained by X-Ray Diffraction (XRD) measurements using two methods of sample preparation: conventional powder (by crushing and grinding of rock fragments) and spray-drying of micronized rock powder method. Microstructure and microanalysis were acquired by Scanning Electron Microscopy/Energy Dispersive Spectroscopy (SEM/EDS). Batch experiments were then conducted using selected rock samples and fracturing fluid whilst deionized water was used as control sample for fluid/rock interaction. These were conducted at 95°C and ambient pressure for various time periods to assess the geochemical reactivity of the Caney shale. The rock samples were subsequently recovered from fluid, dried and analysis repeated using identical XRD and SEM/EDS measurements, following the same conditions. Preliminary experimental results show rock mineralogical compositions are predominantly quartz with relatively high clay content. The clay minerals are mainly illite. Carbonate content is less than 10% by weight for most samples, with other non-clay minerals pyrite, albite, dolomite, and some apatite. In general, sprayed samples showed more intense peaks and less full width at half maxima (FWHM) relative to conventional rock-powder samples. Post-experimental mineralogical changes were observed in samples with clay portions breaking down to amorphous entities. As expected, dissolution of carbonates (calcite and dolomite) was observed and newly detected dissolution of biogenic micro quartz resulted in formation of amorphous silica. 1.0 INTRODUCTION Formation of sedimentary rocks involves processes where rock sediments are emplaced with fluids starting interactions that persist over long periods. During the lithification process, sediments and fluids react and attain equilibrium state. This equilibrium is disturbed during drilling, completion, hydraulic fracturing and other operations that involve the introduction of engineered fluids into the subsurface. To return to equilibrium, dissolution and precipitation of minerals may occur. These reactions have implications on the petrophysical properties of the reservoir. Whiles dissolution and precipitation of minerals can enhance porosity and permeability, the reverse can also be true. For example, when acidic fluids are introduced into formations with high carbonate contents, carbonate minerals dissolve into solution thus increasing the porosity and permeability of the formation. In contrast, when alkaline fluids with pH above 11 are introduced into an illite-rich shale formation, the rock-fluid interaction leads to de-flocculation of illite platelets causing substantial increase in clay fines migration, consequently significant reduction in permeability (Salles et al., 2008).

Awejori, G.↗
DOE OSTI2022

Analysis of solid uranium particulates on cotton swipes with an automated microextraction-ICP-MS system

Here, an automated microextraction method coupled to an inductively coupled plasma – mass spectrometer (ICP-MS) was developed for the direct analysis of solid uranium particulates on the surface of cotton swipes. The microextraction probe extracts particulates from the sample surface, in a flowing solvent, and directs the removed analyte to an ICP-MS for isotopic determination. The automated system utilizes a mechanical XY stage that is software controlled with the capability of saving and returning to specific locations and a camera focused to the swipe surface for optimal viewing of the extracted locations (i.e., material present). Here, particulates (n = 135) were extracted and measured by ICP-MS, including 35 depleted uranyl nitrate hexahydrate (UN) (used for mass bias corrections), 50 uranyl fluoride (UO 2 F 2 ), and 50 uranyl acetate (UAc) particulates. Blank extractions were performed on the cotton swipes between triplicate sample analyses. Between each swipe extraction, the probe was sent between two wells containing 10% and 5% HNO 3 to clean the probe head and to eliminate any analyte carryover between particulates. The measured 235 U/ 238 U and 234 U/ 238 U isotope ratios for the UO 2 F 2 particulates were 0.00725(8) and 0.000054(4), a percent relative difference (% RD) of –0.041% and –1.7% from the reference isotope ratios determined in-lab through multi-collector ICP-MS analysis of dissolved aliquots of the U material. The UAc samples had a measured 235 U/ 238 U isotope ratio of 0.00206(7), a –0.96% relative difference from the reference value of 0.00208(1). The 234 U/ 238 U and 236 U/ 238 U isotope ratios were 0.000008(1) and 0.000031(4), –5.1% RD and –4.3% RD, respectively. The automated sample stage enabled seamless and rapid particle analysis, leading to a significant increase in throughput versus what was previously possible. Additionally, the saved location capability reduced user sampling error as sampling locations were easily stored and recalled. Analysis of U particles on the swipe surface – including blanks, mass bias, and triplicate extractions – was completed in less than an hour without any sample preparation necessary.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Datasets and U-Net Model for "A Deep Learning Based Framework to Identify Undocumented Orphaned Oil and Gas Wells from Historical Maps: a Case Study for California and Oklahoma"

This dataset has results and the model associated with the publication Ciulla et al., (2024). It contains a U-Net semantic segmentation model (unet_model.h5) and associated code implemented in tensorflow 2.0 for the model training and identification of oil and gas well symbols in USGS historical topographic maps (HTMC). Given a quadrangle map (7.5 minutes), downloadable at this url: https://ngmdb.usgs.gov/topoview/, and a list of coordinates of the documented wells present in the area, the model returns the coordinates of oil and gas symbols in the HTMC maps. For reproducibility of our workflow, we provide a sample map in California and the documented well locations for the entire State of California (CalGEM_AllWells_20231128.csv) downloaded from https://www.conservation.ca.gov/calgem/maps/Pages/GISMapping2.aspx. Additionally, the locations of 1,301 potential undocumented orphaned wells identified using our deep learning framework or the counties of Los Angeles and Kern in California, and Osage and Oklahoma in Oklahoma are provided in the file found_potential_UOWs.zip. The results of the visual inspection of satellite imagery in Osage County is in the file visible_potential_UOWs.zip. The dataset also includes a custom tool to validate the detected symbols in the HTMC maps (vetting_tool.py). More details about the methodology can be found in the associated paper: Ciulla, F., Santos, A., Jordan, P., Kneafsey, T., Biraud, S.C., and Varadharajan, C. (2024) A Deep Learning Based Framework to Identify Undocumented Orphaned Oil and Gas Wells from Historical Maps: a Case Study for California and Oklahoma. Accepted for publication in Environmental Science and Technology. The geographical coordinates provided correspond to the locations of potential undocumented orphaned oil and gas wells (UOWs) extracted from historical maps. The actual presence of wells need to be confirmed with on-the-ground investigations. For your safety, do not attempt to visit or investigate these sites without appropriate safety training, proper equipment, and authorization from local authorities. Approaching these well sites without proper personal protective equipment (PPE) may pose significant health and safety risks. Oil and gas wells can emit hazardous gasses including methane, which is flammable, odorless and colorless, as well as hydrogen sulfide, which can be fatal even at low concentrations. Additionally, there may be unstable ground near the wellhead that may collapse around the wellbore. This dataset was prepared as an account of work sponsored by the United States Government. While this document is believed to contain correct information, neither the United States Government nor any agency thereof, nor the Regents of the University of California, nor any of their employees, makes any warranty, express or implied, or assumes any legal responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by its trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof, or the Regents of the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof or the Regents of the University of California.

Artificial Intelligence↗
DOE OSTI2022

A Novel Process for Converting Coal to High-Value Polyurethane Products

Battelle has demonstrated a patented process for making high-value, polyurethane (PU) foam from coal, based on preparing liquefied coal via direct liquefaction, converting it to polyols as an intermediate via ozonation, and then making PU foams from these polyols. This process represents a breakthrough in innovative utilization of U.S. coals, and is applicable to bituminous as well as sub-bituminous coals. The resulting PU foam products are projected to have an extremely high value (i.e., over $\$5,000$ /ton), with nearly 100% of carbon utilization from coalderived liquid feedstock, and 31.5% to 43.5% of the carbon in the PU foam polyol product being bio-based. The targeted products represent an extremely large (i.e., over $80 billion/year), existing PU foam market, which could expand into making coatings and adhesives. The process can further help reduce petroleum imports, while improving the economics of PU foam production. This work was completed with funding from the National Energy Technology Laboratory (NETL), with cost share from the State of Ohio’s Ohio Development Services Agency (ODSA) and others, and has advanced the process to 10 kg/day continuous scale and thus to Technology Readiness Level (TRL) 5. A total of 48 coal-based polyols were prepared and evaluated. The initial 28 polyols focused on range finding for ideal conditions. The later 20 polyols were produced as part of process optimizations. These optimizations were targeted around a continuous ozonolysis process to evaluate extended time reactions and to create the necessary intermediate for production of 1-gallon samples of polyol. The most unique attribute of Battelle’s polyol is in the utilization of coal’s aromaticity to gain final foam rigidity. Typically, polyols depend on the isocyanate fraction and cross-linking to gain rigidity. By utilizing coal, we were able to maintain rigidity while reducing the overall hydroxyl value of the polyol. This is important as lower hydroxyl value leads to greater percent weight of the coal-based polyol because less isocyanate is required for foaming. This leads to greater foam cost savings. This report provides the details, process, and process cost models of the conversion of coal to polyols and further to PU foams. Battelle’s process begins with coal liquids. These liquids can be obtained by two processes: coal coking or pyrolysis to produce coal tar, and Battelle’s biobased coal-to-liquids (CTL) process to produce heavy syncrude after liquifying >85% coal. After liquification, Battelle utilizes ozonolysis to create functionalization on the polyaromatic coal structure. The functionalization is then converted to the final polyester polyol through transesterification, or to hydroxyamide polyol through amidification. Equivalent or better standard properties have been obtained for 2 lb/ft 3 density rigid, water and freon-alternative blown foams, including compressive strength, density, R-value, and dimensional stability. Target applications for these foams are insulation, packaging, and energy-absorbing foams. Some exploratory testing also showed promise for adhesives applications. A detailed economic analysis showed that Battelle’s polyol process is economical, at a 140 metric tons per day (MTD) polyol production scale. An attractive return on investment (ROI) at competitive pricing validates the process is ready for a pilot-plant demonstration. A scale-up plan is provided.

01 COAL, LIGNITE, AND PEAT↗
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↗