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NASA NTRS2023

Launch Complex 34, SWMU CCO542022 DNAPL Source Zone Operations, Maintenance, and Monitoring, Site-Wide Long-Term Monitoring, and Hot Spot 6 Air Sparge System Annual Performance Monitoring Report Cape Canaveral Space Force Station, Florida

This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ), Site-Wide Long-Term Monitoring (LTM), and Hot Spot (HS) 6 Air Sparge (AS) System presents the results of Year 13 operation of the hydraulic containment (HC) Interim Measure (IM), the results of performance monitoring direct-push technology (DPT) sampling and monitoring well sampling conducted in the DSZ, results of the biennial site-wide LTM event, and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. This site has been designated Solid Waste Management Unit (SWMU) CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act (RCRA) Corrective Action Program. For the site-wide biennial LTM event, a total of 55 monitoring wells were sampled for volatile organic compounds (VOCs) in February 2023 and one well was sampled for polychlorinated biphenyls (PCBs) in December 2022. One well planned for VOC sampling was found to be destroyed and could not be sampled (CW0002). The LTM wells are screened in two lithologic zones: Layer 1 (0 to 25 feet below land surface [bls]) and Layer 2 (25 to 30 ft bls), and are located in the outlying areas of LC34 to monitor groundwater conditions within the Low-Concentration Plume (LCP), defined as concentrations exceeding Groundwater Cleanup Target Levels (GCTLs), and the High-Concentration Plume (HCP), defined as concentrations exceeding Natural Attenuation Default Concentrations (NADCs). Results from the biennial sampling event indicated overall plume stability and delineation for the plume, which extends over 300 acres. The operational period for Year 13 of the HCS was from April 1, 2022 to March 31, 2023. Operational runtime for the system was 90 percent during Year 13, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2023, a total of 313,673,241 cumulative gallons of groundwater containing 88,337 pounds of VOCs have been removed by the HCS. Influent concentrations of trichloroethene (TCE) have decreased since startup from approximately 280,000 μg/L (January 2010) to 12,000 μg/L (March 2023). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in December 2022 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events between 2017 and 2021. Full vertical profile sampling was completed at each DPT from 8 to 98 feet bls, at 5-foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 μg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations and at depths ranging from 8 to 98 feet bls. In addition to DPT sampling, groundwater samples were collected from deep monitoring wells in the DSZ area (Layers 7 and 8) in December 2022 to verify vertical delineation. Layer 7/8 monitoring well results were non-detect in December 2022, with exception of three wells (IW0162, IW043D2, and IW044D2), where TCE, cis-1,2-dichloroethene (cDCE), and/or vinyl chloride (VC) were detected above GCTLs. These wells are screened 105 to 115 feet bls, which is below the existing recovery well capture zone. TCE was first detected in IW0162 in December 2021 and has since been sampled at least monthly to monitor TCE concentrations. The maximum TCE concentration during this operational period was 15,000 μg/L at IW0162 in March 2023. Because of the increased TCE concentrations in this well, a new recovery well (RW21D), screened 86 to 106 feet bls, was installed in January 2023 and incorporated into existing HCS operations. The HS 6 AS IM was initiated in 2018 with 160 AS wells, and expanded in 2019 with an additional 140 AS wells. Quarterly performance monitoring was reduced to semi-annual in 2020. The HS 6 AS system remained operational during the reporting period covered under this report. The results of the HS 6 system operation and semi-annual performance monitoring are summarized in this report. Semi-annual monitoring results collected in April and October 2022 show concentrations of contaminants of concern (cDCE, trans-1,2-dichloroethene, and vinyl chloride) are generally decreasing and not impacting the surface water drainage canal, indicating the HS 6 IM is meeting objectives. A Phase Two Expansion of the HS 6 AS IM was recently completed. As of the date of this report, the expansion became operational in August 2023 and the first quarter of monitoring was conducted in November 2023. Details of the construction, start-up, and performance monitoring will be included in a future Annual PMR. Overall, the tasks associated with Year 13 operation of the HC IM, operation of the HS 6 AS IM, and biennial site-wide sampling were performed in accordance with recommendations included in the previous 2021 LC34 (Year 12) annual report. Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives. Results from the site-wide biennial LTM program also show that the overall network of monitoring wells is adequate to continue monitoring plume-wide conditions.

Complex 34↗
NASA NTRS2024

Big Cypress Water Resources: Using Earth Observations to Assess Water Quality in Big Cypress Reservation, FL

Upstream agricultural development and runoff are driving harmful algal blooms in the Big Cypress Reservation. The Seminole Tribe of Florida Environmental Resource Management Department monitors water quality in the Big Cypress Reservation, located on the north end of Big Cypress National Preserve. The Environmental Resource Management Department aims to incorporate Earth observations into its investigative approach, which consists of Geographic Information Systems and in situ water sampling. We assessed the feasibility of using Earth observations to measure harmful algal blooms over time and identify vulnerable areas. We analyzed data from multiple remote sensing platforms and sensors, including Landsat 8 Thermal Infrared Spectrometer(TIRS), Landsat 9 TIRS-2, Landsat 9 Operational Land Imager 2, Sentinel-2 MultiSpectral Instrument, and Sentinel-3 Ocean and Land Color Instrument. We determined that it was challenging to use Sentinel-3, Landsat 8, and Landsat 9 imagery for monitoring the canals within the Reservation, and that Sentinel-2 was the most capable platform for the study area. Using Sentinel-2, we created spectral indices for the detection of algal blooms. We used these indices to measure algal blooms at 8 stations across the Big Cypress Reservation. We then created time series and seasonal decompositions of in situ water sample data and indices to visualize relationships between datasets, along with correlation matrices. Our correlations were not conclusive. However, we found that the spectral indices have the potential to detect algal blooms. Lastly, we evaluated Maxar WorldView-3 imagery and found that using data from sensors with higher spatial resolutions would improve results.

Remote sensing↗
NASA NTRSDate not supplied

Behavioral Health Benefits of the ISS Pick-and-Eat Crop Growth System

Summary: We summarize findings related to assessing the pick-and-eat salad-crop productivity and acceptability of the ISS food system as a countermeasure to maintain behavioral health in long-duration spaceflight. BACKGROUND Plants are a potential countermeasure for the stresses of living in space. Caring for plants and eating fresh food have been shown to serve as a psychological benefit for previous astronauts and for others in analogous environments such as Antarctica [1,2]. Gardening can be therapeutic in terrestrial settings [3]. These effects may carry over or be more pronounced in austere environments such as spaceflight. It can reduce stress and increase sensory stimulation and enjoyment [2]. Growing crops may offer astronauts meaningful and engaging work as they care for living things in an austere environment away from Earth’s nature and as they provide sustenance for their crew. We examined the extent to which interacting with plants (e.g., tending to, consuming) was related to behavioral health outcomes in long-duration space missions. METHOD Participants were 27 astronauts that interacted with the plant system VEG-04, VEG-05, and HRF-VEG (VEG-03 I-L, PH-04). In total, there were 106 in-flight observations. Participants completed monthly measures of mood and well-being, enjoyment and time spent performing specific crop growth and consuming the plants, meaningfulness, performance, connections with others and the Earth, desire to work with and eat plants, and experiences with struggling or dying plants. Higher ends of the 7-point Likert scale indicated more positive outcomes, lower ends of the scale were anchored with more negative outcomes, and the scale midpoints indicated neutral positions. Participants selected a specific survey version based on whether they interacted with the plant system(s) or not, and we included only the scores from the crewmembers that participated in any given activity. RESULTS & DISCUSSION Results indicated that participants generally rated tasks related to the plants and crop growth as enjoyable. Consuming the harvested plants and voluntary viewing were the most enjoyable activities. Tending to the plants was reported as moderately enjoyable, indicating BHP benefits from this work task. The BHP impacts of whether the task was engaging, meaningful, supported well-being, or was demanding for a crewmember were generally positive and increased over time. As shown in the Figure, working with plants was reported as more engaging, meaningful, and beneficial to well-being over time, while the demand from the task was moderate to low and consistent over time. Engaging, meaningful, and supporting well-being were strongly, positively correlated with each other, which is consistent with research that suggests engaging and meaningful work can support well-being. Plant activities such as voluntary viewing, watering, harvesting, and consuming, were positively related to task engagement and meaning, and enjoyment and well-being. Findings suggest that working with plants and consuming them can be a behavioral health countermeasure for long-duration spaceflight. REFERENCES [1] Schlacht I, et al. (2020) Impact of plants in isolation: The EDEN-ISS…in Antarctica. In Advances in Human Factors of Transportation, Washington DC. [2] Vessel E, Russo S (2015) Effects of reduced sensory stimulation and…countermeasures…. NASA/TM-2015-218576. [3] Odeh R, Guy C (2017) Gardening for therapeutic people-plant interactions during LDSM. Open Agriculture, 2(1), 1-13. ACKNOWLEDGEMENTS This research was supported by the Human Health and Performance Contract NNJ15HK11B, and NASA grant MTL #1075 (PI G.D. Massa).

behavioral health↗
NASA NTRSDate not supplied

Behavioral Health Benefits of the ISS Pick-and-Eat Crop Growth System

Summary: We summarize findings related to assessing the pick-and-eat salad-crop productivity and acceptability of the ISS food system as a countermeasure to maintain behavioral health in long-duration spaceflight. BACKGROUND Plants are a potential countermeasure for the stresses of living in space. Caring for plants and eating fresh food have been shown to serve as a psychological benefit for previous astronauts and for others in analogous environments such as Antarctica [1,2]. Gardening can be therapeutic in terrestrial settings [3]. These effects may carry over or be more pronounced in austere environments such as spaceflight. It can reduce stress and increase sensory stimulation and enjoyment [2]. Growing crops may offer astronauts meaningful and engaging work as they care for living things in an austere environment away from Earth’s nature and as they provide sustenance for their crew. We examined the extent to which interacting with plants (e.g., tending to, consuming) was related to behavioral health outcomes in long-duration space missions. METHOD Participants were 27 astronauts that interacted with the plant system VEG-04, VEG-05, and HRF-VEG (VEG-03 I-L, PH-04). In total, there were 106 in-flight observations. Participants completed monthly measures of mood and well-being, enjoyment and time spent performing specific crop growth and consuming the plants, meaningfulness, performance, connections with others and the Earth, desire to work with and eat plants, and experiences with struggling or dying plants. Higher ends of the 7-point Likert scale indicated more positive outcomes, lower ends of the scale were anchored with more negative outcomes, and the scale midpoints indicated neutral positions. Participants selected a specific survey version based on whether they interacted with the plant system(s) or not, and we included only the scores from the crewmembers that participated in any given activity. RESULTS & DISCUSSION Results indicated that participants generally rated tasks related to the plants and crop growth as enjoyable. Consuming the harvested plants and voluntary viewing were the most enjoyable activities. Tending to the plants was reported as moderately enjoyable, indicating BHP benefits from this work task. The BHP impacts of whether the task was engaging, meaningful, supported well-being, or was demanding for a crewmember were generally positive and increased over time. As shown in the Figure, working with plants was reported as more engaging, meaningful, and beneficial to well-being over time, while the demand from the task was moderate to low and consistent over time. Engaging, meaningful, and supporting well-being were strongly, positively correlated with each other, which is consistent with research that suggests engaging and meaningful work can support well-being. Plant activities such as voluntary viewing, watering, harvesting, and consuming, were positively related to task engagement and meaning, and enjoyment and well-being. Findings suggest that working with plants and consuming them can be a behavioral health countermeasure for long-duration spaceflight. REFERENCES [1] Schlacht I, et al. (2020) Impact of plants in isolation: The EDEN-ISS…in Antarctica. In Advances in Human Factors of Transportation, Washington DC. [2] Vessel E, Russo S (2015) Effects of reduced sensory stimulation and…countermeasures…. NASA/TM-2015-218576. [3] Odeh R, Guy C (2017) Gardening for therapeutic people-plant interactions during LDSM. Open Agriculture, 2(1), 1-13. ACKNOWLEDGEMENTS This research was supported by the Human Health and Performance Contract NNJ15HK11B, and NASA grant MTL #1075 (PI G.D. Massa).

countermeasure↗
DOE OSTI2020

The Locus Algorithm IV: Performance metrics of a grid computing system used to create catalogues of optimised pointings

This paper discusses the requirements for and performance metrics of the the Grid Computing system used to implement the Locus Algorithm to identify optimum pointings for differential photometry of 61,662,376 stars and 23,779 quasars. Initial operational tests indicated a need for a software system to analyse the data and a High Performance Computing system to run that software in a scalable manner. Practical assessments of the performance of the software in a serial computing environment were used to provide a benchmark against which the performance metrics of the HPC solution could be compared, as well as to indicate any bottlenecks in performance. These performance metrics indicated a distinct split in the performance dictated more by differences in the input data than by differences in the design of the systems used. This indicates a need for experimental analysis of system performance, and suggests that algorithmic complexity analyses may lead to incorrect or naive conclusions, especially in systems with high data I/O overhead such as grid computing. Further, it implies that systems which reduce or eliminate this bottleneck such as in-memory processing could lead to a substantial increase in performance.

Creaner, Oisín↗
DOE OSTI2020

Combined shipping protection and impingement detection wrap

A packaging material comprised of a gas-impermeable base layer, an indicator layer, and a gas-impermeable top layer is disclosed. The top layer is selected to rupture upon experiencing an impingement or impact that exceeds a predetermined threshold. The indicator layer is configured to change visual appearance upon exposure to ambient air. The top layer further may be configured into a plurality of cells, with each cell filled with a gas that is inert with respect to the indicator layer. The cells may be of a size and shape configured to indicate the location and shape of an impingement or impact, to alert a recipient of an item protected by the packaging material of an area that may require further inspection.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Big Sky Regional Carbon Sequestration Partnership (Phase III Final Scientific/Technical Report)

The Big Sky Carbon Sequestration Partnership (BSCSP) pursued a Phase III demonstration project at Kevin Dome in north central Montana. Kevin Dome covers approximately 700 square miles and is a naturally occurring CO 2 reservoir that is flanked by oil and gas fields. The carbon dioxide (CO 2 ) is in the upper Devonian Duperow (carbonate) formation and does not reach the spill point of the dome; therefore, the dome has potential as a CO 2 sequestration reservoir, a CO 2 supply, or as both if anthropogenic sources and enhanced oil recovery (EOR) operations are associated with the dome. Kevin Dome could potentially act as a buffer to continue accepting anthropogenic CO 2 when EOR flooding operations are interrupted or completed. The project objective was to produce one million tonnes of CO 2 from the gas cap of Kevin Dome, pipe it laterally, inject, and re-store it in the brine leg of the same formation to test the hub / buffer storage concept. This was to be accomplished by drilling up to five production wells, building a short pipeline and compression facilities, and drilling an injection well and several monitoring wells. BSCSP commenced outreach and site characterization activities including acquiring baseline data for near-surface insurance monitoring, acquiring 3-dimensional, 9-component surface seismic over the project area, drilling two test wells (one in the production area and one in the injection area), coring key intervals, and performing comprehensive logging. Well tests of those wells revealed two barriers to the project. The production (Danielson 33-17) well was perforated in multiple zones but failed to produce any significant CO 2 . This was despite being drilled in the near vicinity of a historic well that had produced 3700 MCF per day in a drill stem test. Modeling indicated that this was likely due to a phase change during production causing a temperature drop resulting in hydrate and/or water ice formation that clogged the formation. Tests of the injection zone (Wallewein 22-1) well indicated total dissolved solids (TDS) slightly below the EPA required 10,000 parts per million (ppm) for a Class VI underground injection control permit. While the project was initiated before Class VI rules were promulgated, and this was an experimental project (seemingly qualified for a Class V permit), the Environmental Protection Agency (EPA) indicated that injection would require a Class VI permit. The low salinity result was unexpected as contours plotted based on regional formation water quality data indicated an expected TDS above 20,000 ppm, and wells between the recharge zone and the Wallewein well tested above 10,000 ppm. Faced with the inability to obtain an injection permit, the demonstration project could not proceed. However, the project had generated valuable samples and data on a large natural analog including 32 sq. mi. of 3-D, 9-C seismic, 430 ft. of carbonate core covering seven different depositional environments taken from areas with, and without the presence of CO 2 , 30 ft. of core of two caprocks, a tight carbonate and an anhydrite, a full set of modern logs on both wells, and well tests. DOE decided to re-scope the project around completing studies utilizing this data. This report covers both the initial scope and the re-scope (Task / Section numbers preceded with an R). While the report covers a wide range of project activities, highlights of this work include: Development of a geostatic model using neural nets to match well logs to facies and using multi-waveform seismic to inform reservoir heterogeneity; Unique mechanical testing of permeability – stress relationship in two caprock materials; Development of full waveform inversion to generate a high resolution velocity model; Model development for dual permeability (fracture and matrix) systems to better account for matrix-matrix interactions; Joint seismic wave inversion (including the first quadr-joint inversion) exhibiting better imaging of a challenging reservoir zone in stiff rock; Core flow and core flood results on a reactive carbonate; and Innovative laboratory measurements of seismic response of fractured core as a function of fluid fill.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

EERC Final Topical Report – Findings on Subtask 3.2 – Produced Water Management Through Geologic Homogenization, Conditions, and Reuse

The Energy & Environmental Research Center (EERC) was awarded a contract by the North Dakota Industrial Commission (NDIC) Oil and Gas Research Program (NDIC No. G-051-101) to conduct a study on the recycling of water used in oil and gas operations, also known as produced water, from oil- and gas-producing regions of North Dakota as directed by Section 19 of North Dakota House Bill 1014. This final report provides a compilation of results of the study, which include regulatory, scientific, technological, and feasibility methods and considerations associated with North Dakota produced water management. The report provides a synopsis of this project’s previously submitted produced water assessment report entitled “Produced Water Management and Recycling Options in North Dakota” (Energy & Environmental Research Center, 2020), with updated values provided as appropriate. The report provides the results from the investigation of a novel produced water management strategy, referred to as geologic homogenization, conditioning, and reuse (GHCR), which aims to use a subsurface geologic formation as a natural medium for managing produced water recycling and reuse. Water management is a significant technical and economic challenge for sustainable oil and gas production, and water volumes are intrinsically linked to oil production volumes. North Dakota oil production rose to over 1.5 million barrels (MMbbl)/day in 2019, and despite a downturn in oil price in early 2020, North Dakota oil production has recovered to 1.1 MMbbl/day as of August 2021. Bakken petroleum system development between 2008 and 2020 has resulted in a nearly fourfold increase in produced water volumes to 642 MMbbl/yr in 2020 after peaking at 740 MMbbl/yr in 2019 and a fivefold increase in saltwater disposal (SWD) volumes to 565 MMbbl/yr in 2020 after a peak of 682 MMbbl/yr in 2019. Produced water and SWD volumes are forecasted to double by 2030. SWD is the primary method of produced water management used in North Dakota, with approximately 95% of the SWD volume occurring through subsurface injection into sandstones of the Dakota Group (Dakota). Localized pressurization of the Dakota resulting from SWD and projected increases in produced water volumes could impact the economics of North Dakota oil production. As a result, there is an emerging need to pursue alternative produced water management approaches, including recycling and reuse. While produced water recycling is not yet widespread, commercial operators are making strides in overcoming the technical challenges of using high salinity produced water in completion operations (Marathon Oil, 2020). As water management continues to be a key focal point in companies’ environmental, social, and governance (ESG) initiatives, focus on water management, including recycling, will likely continue to increase. Laboratory column testing, field sample collection, geologic modeling and numerical simulation, and techno-economic analysis all indicate that GHCR could feasibly be implemented as a potential water management option. Laboratory column testing and field sample collection indicate that the Inyan Kara sandstone and native formation fluid are capable of homogenizing with the Bakken produced water to a point where the fluid composition appears to stabilize. Extracting that stabilized fluid could be considered homogeneous and capable of providing individual batches of hydraulic fracturing fluid. Numerical simulation results indicate that extraction of fluids from the Inyan Kara in a GHCR implementation scenario is capable of reducing formation pressure, which would help ease localized pressurization of the Inyan Kara and extend the available capacity for nearby existing SWD wells. Economic analysis indicates that there are scenarios where GHCR implementation can be a competitive or even lower-cost option than a conventional water management approach. Site-specific conditions will dictate the economic potential of GHCR, but potentially attractive sites for GHCR implementation will be those that are located above a pressurized zone of the Inyan Kara, need six or more Bakken infill wells, and face high costs for conventional SWD and/or freshwater. Based on the regulatory review, drilling into the Inyan Kara for SWD and to harness as a source water for industrial use have precedent in North Dakota, and a workable regulatory solution for GHCR seems likely. However, restrictions in the state regarding surface storage and transport of produced fluids may limit some activities, which will affect how GHCR could ultimately be implemented. In summary, this study reveals pursuing GHCR can be a viable approach to water management in North Dakota. The GHCR concept addresses some of the challenges that hinder the more traditional approaches to recycling in the industry. Furthermore, an assessment of the current landscape of water management within the state reveals the ongoing trend of increasing volumes of produced water and SWD. Projections reveal that the volumes of produced water that need to be managed are expected to double over the next decade (Energy & Environmental Research Center, 2020). With the continued development of the Bakken and continuing driving factors related to ESG initiatives, implementing a practice such as GHCR is a feasible approach to adding recycling of produced water to industry within the state. This subtask was cofunded through the EERC–U.S. Department of Energy Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by the North Dakota Industrial Commission Oil and Gas Research Program. References Energy & Environmental Research Center, 2020, Produced water management and recycling options in North Dakota: Final Report for North Dakota Legislative Management Energy Development and Transmission Committee and North Dakota Industrial Commission. Marathon Oil, 2020, Sustainability report: https://cdn.sanity.io/files/ghcnw9z2/website/ 91744eb6ef8fbe59505a911c6b8d2e8dd9a537fa.pdf?dl (accessed November 2021).

02 PETROLEUM↗
DOE OSTI2022

Cybersecurity assessment and risk management tool

Techniques and apparatuses are described for a cybersecurity risk management tool to assess cybersecurity risk and prioritize cybersecurity correction plans. The cybersecurity risk management tool categorizes cybersecurity framework security controls into maturity indicator levels, identifies implementation states achieved by an entity with respect to the cybersecurity framework security controls, and determines which of the maturity indicator levels represents the implementation state achieved by the entity with respect to each of the cybersecurity framework security controls. A cost-benefit analysis for modifying from the implementation state achieved by the entity to a next implementation state to be achieved by the entity with respect to the cybersecurity framework security controls is also enabled. The cost-benefit analysis leverages factored weights including aspects indicative of security perspectives, Gaussian distributions, and the maturity indicator levels.

Gourisetti, Sri Nikhil Gupta↗
DOE OSTI2023

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

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

rare earth elements, acid baking, high-temperature↗
DOE OSTI2021

Multiscale assessment of land surface phenology from harmonized Landsat 8 and Sentinel-2, PlanetScope, and PhenoCam imagery

As the spatial and temporal resolution of remotely sensed imagery has improved over the last four decades, algorithms for monitoring and mapping seasonal changes in surface properties have evolved rapidly. Most recently, the availability of daily PlanetScope imagery has created new opportunities for monitoring the land surface phenology (LSP) of terrestrial ecosystems at high spatial resolution. However, the quality and value of LSP information from PlanetScope imagery have not been systematically examined. In this paper, we evaluate the character and quality of LSP information derived from PlanetScope by comparing time series of vegetation indices and LSP metrics from PlanetScope to corresponding time series and LSP metrics derived from Harmonized Landsat 8 and Sentinel-2 (HLS) imagery and PhenoCams at six sites that span a diverse range of land cover types and climate. Results show that vegetation index time series from all three data sources show high temporal correlation, and LSP metrics derived from HLS, PlanetScope, and PhenoCam show high agreement with negligible bias. Semi-variograms for phenometrics estimated from PlanetScope imagery indicate that the majority of spatial variance captured in PlanetScope phenometrics occurs well below the spatial resolution HLS imagery. At the same time, LSP metrics from HLS are most strongly correlated with the 50–75% quantiles of 3 m LSP metrics from PlanetScope. This indicates that HLS captures the average phenology at sub-pixel scale captured in PlanetScope imagery. Here, our results represent the first comprehensive comparison of LSP metrics estimated from PlanetScope and publicly available moderate spatial resolution imagery, and provide insights regarding: (1) the quality and character of LSP metrics derived from HLS and PlanetScope; and (2) the relative merits and trade-offs associated with the use of each data source for LSP studies.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2020

Monitoring Water-Related Ecosystems with Earth Observation Data in Support of Sustainable Development Goal (SDG) 6 Reporting

Lack of national data on water-related ecosystems is a major challenge to achieving the Sustainable Development Goal (SDG) 6 targets by 2030. Monitoring surface water extent, wetlands, and water quality from space can be an important asset for many countries in support of SDG 6 reporting. We demonstrate the potential for Earth observation (EO) data to support country reporting for SDG Indicator 6.6.1, ‘Change in the extent of water-related ecosystems over time’ and identify important considerations for countries using these data for SDG reporting. The spatial extent of water-related ecosystems, and the partial quality of water within these ecosystems is investigated for seven countries. Data from the Moderate Resolution Imaging Spectroradiometer (MODIS) and Landsat 5, 7, and 8 with Shuttle Radar Topography Mission (SRTM) are used to measure surface water extent at 250 m and 30 m spatial resolution, respectively, in Cambodia, Jamaica, Peru, the Philippines, Senegal, Uganda, and Zambia. The extent of mangroves is mapped at 30 m spatial resolution using Landsat 8 Operational Land Imager (OLI), Sentinel-1, and SRTM data for Jamaica, Peru, and Senegal. Using Landsat 8 and Sentinel 2A imagery, total suspended solids and chlorophyll-a are mapped over time for a select number of large surface water bodies in Peru, Senegal, and Zambia. All of the EO datasets used are of global coverage and publicly available at no cost. The temporal consistency and long time-series of many of the datasets enable replicability over time, making reporting of change from baseline values consistent and systematic. We find that statistical comparisons between different surface water data products can help provide some degree of confidence for countries during their validation process and highlight the need for accuracy assessments when using EO-based land change data for SDG reporting. We also raise concern that EO data in the context of SDG Indicator 6.6.1 reporting may be more challenging for some countries, such as small island nations, than others to use in assessing the extent of water-related ecosystems due to scale limitations and climate variability. Country-driven validation of the EO data products remains a priority to ensure successful data integration in support of SDG Indicator 6.6.1 reporting. Multi-country studies such as this one can be valuable tools for helping to guide the evolution of SDG monitoring methodologies and provide a useful resource for countries reporting on water-related ecosystems. The EO data analyses and statistical methods used in this study can be easily replicated for country-driven validation of EO data products in the future.

water-related ecosystems; surface water extent; ma↗
NASA NTRS2022

Climate Drivers of Global Wildfire Burned Area

Wildfire is an integral part of the Earth system, but at the same time it can pose serious threats to human society and to certain types of terrestrial ecosystems. Meteorological conditions are a key driver of wildfire activity and extent, which led to the emergence of the use of fire danger indices that depend solely on weather conditions. The Canadian Fire Weather Index (FWI) is a widely used fire danger index of this kind. Here, we evaluate how well the FWI, its components, and the climate variables from which it is derived, correlate with observation-based burned area (BA) for a variety of world regions. We use a novel technique, according to which monthly BA are grouped by size for each Global Fire Emissions Database (GFED) pyrographic region. We find strong correlations of BA anomalies with the FWI anomalies, as well as with the underlying deviations from their climatologies for the four climate variables from which FWI is estimated, namely, temperature, relative humidity, precipitation, and wind. We quantify the relative sensitivity of the observed BA to each of the four climate variables, finding that this relationship strongly depends on the pyrographic region and land type. Our results indicate that the BA anomalies strongly correlate with FWI anomalies at a GFED region scale, compared to the strength of the correlation with individual climate variables. Additionally, among the individual climate variables that comprise the FWI, relative humidity and temperature are the most influential factors that affect the observed BA. Our results support the use of the composite fire danger index FWI, as well as its sub-indices, the Build-Up Index (BUI) and the Initial Spread Index (ISI), comparing to single climate variables, since they are found to correlate better with the observed forest or non-forest BA, for the most regions across the globe.

Wildfire↗
DOE OSTI2020

Suppressing Co-Crystallization of Halogenated Non-Fullerene Acceptors for Thermally Stable Ternary Solar Cells

While photovoltaic blends based on non-fullerene acceptors are touted for their thermal stability, this type of acceptor tends to crystallize, which can result in a gradual decrease in photovoltaic performance and affects the reproducibility of the devices. Two halogenated indacenodithienothiophene-based acceptors that readily co-crystallize upon mixing are studied, which indicates that the use of an acceptor mixture alone does not guarantee the formation of a disordered mixture. The addition of the donor polymer to the acceptor mixture readily suppresses the crystallization, which results in a fine-grained ternary blend with nanometer-sized domains that do not coarsen due to a high T g ≈ 200 °C. As a result, annealing at temperatures of up to 170 °C does not markedly affect the photovoltaic performance of ternary devices, in contrast to binary devices that suffer from acceptor crystallization in the active layer. The results indicate that the ternary approach enables the use of high-temperature processing protocols, which are needed for upscaling and high-throughput fabrication of organic solar cells. Further, ternary devices display a stable photovoltaic performance at 130 °C for at least 205 h, which indicates that the use of acceptor mixtures allows to fabricate devices with excellent thermal stability.

14 SOLAR ENERGY↗
DOE OSTI2022

An index to characterize gas‐solid and solid‐solid mixing from average volume fraction fields

Abstract A mixing index based on solid volume fraction fields is developed for gas‐solid flows. Conventional mixing indices are based on particle realizations of granular mixing and are applicable to experimental data or discrete element method simulations. However, these indices cannot be used as‐is for multifluid models, and an index for characterizing mixing in gas‐solid flows from continuous fields is needed. The performance of the new mixing index is tested in two applications. The first is a 3D simulation of the mixing of biomass and sand in a fluidized bed reactor, and the second is a 2D simulation of binary particle segregation in a fluidized bed. The simulations are performed using OpenFOAM®. The mixing index is used to quantify gas‐solid mixing using solid volume fractions and solid‐solid mixing using solid fractions. The formulation of conventional mixing indices is extended to be used with solid volume fractions fields, and methods for performance improvement are presented.

09 BIOMASS FUELS↗
DOE OSTI2022

Sensor selection and tool wear prediction with data‐driven models for precision machining

Abstract Estimation of tool wear in precision machining is vital in the traditional subtractive machining industry to reduce processing cost, improve manufacturing efficiency and product quality. In this vein, fusion of time and frequency‐domain features of commonly sensed signals can provide an early indication of tool wear and improve its prediction accuracy for prognostics and health management. This paper presents a data‐driven methodology and a complete tool chain for the inference of precision machining tool wear from fused machine measurements, such as cutting force, power, audio and vibration signals, and quantify the usefulness of each measurement. Indicators of tool wear are extracted from time‐domain signal statistics, frequency‐domain analysis, and time‐frequency domain analysis. Correlation coefficients between the extracted features (indicators) and the tool wear are used to select the most informative features. Principal Component Analysis and Partial Least‐Squares are used to reduce the dimensionality of the feature space. Regression models, including linear regression, support vector regression, Decision tree regression, neural network regression and Gaussian process regression, are used to predict the tool wear using data from a Haas milling machine performing spiral boss face milling. The performance of the regression models based on subsets of sensors validates the preliminary estimates about the saliency of the sensors. The experimental results show that the proposed methods can predict the machine tool wear precisely, with readily available sensor measurements. Neural network and Gaussian process regression were able to achieve good estimates of tool wear at different machine operating conditions. The most informative signal in predicting tool wear was shown to be the vibration signal. Time‐frequency domain features were the most informative features among the combination of features of three domains. In addition, using partial least squares components extracted from the original features of signals led to higher prediction accuracy.

Han, Seulki↗
DOE OSTI2020

The Critical Role of Reductive Steps in the Nickel-Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C-O Bonds

Hydrogenolysis of the aromatic C-O bond in aryl ethers is catalyzed by Ni in decalin or water at 150 °C. Observations of a significant kinetic isotope effect (kH/kD = 5.7) for the reactions of diphenyl ether under H2 and D2 and a positive dependence of the rate on H2 chemical potential in decalin indicate that addition of H to the aromatic ring is the rate-limiting step rather than C-O scission. Hydrogen addition occurs on the metal before C-O bond scission. DFT calculations indicate that hydrogen atom addition to the ortho position followed by C-O scission is energetically more feasible than C-O scission followed by H addition to either phenoxyl or phenyl moieties. Hydrogenolysis initiated via H addition in water is more selective (~75 %) compared to reactions in decalin (~30 %). The high selectivity for hydrogenolysis is attributed to stabilization of polar transition state by water as a polar solvent.

Wang, Meng↗
DOE OSTI2024

Observation of Thermally Induced Piezomagnetic Switching in Cu 2 OSeO 3 Polymorph Synthesized under High-Pressure

A polymorph of Cu 2 OSeO 3 with the distorted kagome lattice is successfully obtained using the high-pressure synthesis technique (Cu 2 OSeO 3 -HP). The structural analysis using X-ray and neutron powder diffraction suggests that the tetrahedral Cu 2+ clusters [similar to those in Cu 2 OSeO 3 ambient-pressure phase (Cu 2 OSeO 3 -AP)] exist in Cu 2 OSeO 3 -HP but with three symmetry inequivalent sites. No structural change is observed between 1.5 K and the room temperature. The complex magnetic H-T phase diagram is established based on the temperature- and field-dependent magnetization data, indicating two distinct antiferromagnetic phases at low and intermediate temperatures, in addition to the higher-temperature spin-glass-like phase. The low temperature phase is identified by neutron powder diffraction refinements as a canted noncollinear antiferromagnetic order with a weak ferromagnetic component along the b-axis. Size of the refined ordered moment is ≈1.00(4) µ B in Cu 2 OSeO 3 -HP, indicating a large enhancement compared to that of Cu 2 OSeO 3 -AP (≈0.61 µ B ). By applying a uniaxial stress, finite enhancement of weak ferromagnetic component in the noncollinear antiferromagnetic phase in Cu 2 OSeO 3 -HP is observed, which is the clear evidence of the piezomagnetic effect. Interestingly, the sign of the induced magnetization changes on heating from the low-temperature to the intermediate-temperature phases, indicating a novel piezomagnetic switching effect in this compound.

36 MATERIALS SCIENCE↗