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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Stable Element Doping of Sol-gel Toward Simulating Environmental Matrix in Surrogate Explosive Nuclear Debris

Training nuclear forensic analysis personnel in post-detonation scenarios is of critical importance to nuclear threat response capabilities. Thus, realistic nuclear debris simulants which resemble the size, color, elemental composition, and radionuclide content of actual nuclear fallout from a recent detonation would be valuable for training nuclear first responders in realistic scenarios. As nuclear fallout types vary significantly in each of these parameters based on detonation environment (rural, urban, maritime etc.) and collection location, the ability to tailor each of these parameters accurately in simulated debris would be of immense benefit to the post-detonation analysis community for training both in-field collections and triage and the validation of laboratory level nuclear forensic techniques. Sol-gel synthesis techniques can provide the tunability of size, shape and composition required for producing surrogate nuclear debris of a wide variety. The sol-gel process consists of forming a metal oxide material, often silica, through polymerization of a metal-alkoxy precursor. In this work, we characterize the ability to load the sol-gel particles with secondary elemental components such as iron, aluminum, and calcium toward approximating the elemental composition of debris from various detonation environments and demonstrate the ability to produce particles with controllable size, shape, and color. We also demonstrate quantitative radionuclide encapsulation toward reproducing the radionuclide content of actual fallout from a recent detonation. Finally, we then employ these techniques in producing simulated aerodynamic debris samples with realistic elemental matrix composition and radionuclide content simulating a recent uranium-fueled detonation taking place in a rural desert environment and compare it to historic fallout from the Nevada Nuclear Security Site.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Stable Element Doping of Sol-gel Toward Simulating Environmental Matrix in Surrogate Explosive Nuclear Debris

Training nuclear forensic analysis personnel in post-detonation scenarios is of critical importance to nuclear threat response capabilities. Thus, realistic nuclear debris simulants which resemble the size, color, elemental composition, and radionuclide content of actual nuclear fallout from a recent detonation would be valuable for training nuclear first responders in realistic scenarios. As nuclear fallout types vary significantly in each of these parameters based on detonation environment (rural, urban, maritime etc.) and collection location, the ability to tailor each of these parameters accurately in simulated debris would be of immense benefit to the post-detonation analysis community for training both in-field collections and triage and the validation of laboratory level nuclear forensic techniques. Sol-gel synthesis techniques can provide the tunability of size, shape and composition required for producing surrogate nuclear debris of a wide variety. The sol-gel process consists of forming a metal oxide material, often silica, through polymerization of a metal-alkoxy precursor. In this work, we characterize the ability to load the sol-gel particles with secondary elemental components such as iron, aluminum, and calcium toward approximating the elemental composition of debris from various detonation environments and demonstrate the ability to produce particles with controllable size, shape, and color. We also demonstrate quantitative radionuclide encapsulation toward reproducing the radionuclide content of actual fallout from a recent detonation. Finally, we then employ these techniques in producing simulated aerodynamic debris samples with realistic elemental matrix composition and radionuclide content simulating a recent uranium-fueled detonation taking place in a rural desert environment and compare it to historic fallout from the Nevada Nuclear Security Site.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Oxygen isotope analysis of bacterial and fungal manganese oxidation

Abstract The ability of micro‐organisms to oxidize manganese (Mn) from Mn( II ) to Mn( III / IV ) oxides transcends boundaries of biological clade or domain. Many bacteria and fungi oxidize Mn( II ) to Mn( III / IV ) oxides directly through enzymatic activity or indirectly through the production of reactive oxygen species. Here, we determine the oxygen isotope fractionation factors associated with Mn( II ) oxidation via various biotic (bacteria and fungi) and abiotic Mn( II ) reaction pathways. As oxygen in Mn( III / IV ) oxides may be derived from precursor water and molecular oxygen, we use a twofold approach to determine the isotope fractionation with respect to each oxygen source. Using both 18 O‐labeled water and closed‐system Rayleigh distillation approaches, we constrain the kinetic isotope fractionation factors associated with O atom incorporation during Mn( II ) oxidation to −17.3‰ to −25.9‰ for O 2 and −1.9‰ to +1.8‰ for water. Results demonstrate that stable oxygen isotopes of Mn( III / IV ) oxides have potential to distinguish between two main classes of biotic Mn( II ) oxidation: direct enzymatic oxidation in which O 2 is the oxidant and indirect enzymatic oxidation in which superoxide is the oxidant. The fraction of Mn( III / IV ) oxide‐associated oxygen derived from water varies significantly (38%–62%) among these bio‐oxides with only weak relationship to Mn oxidation state, suggesting Mn( III ) disproportionation may account for differences in the fraction of mineral‐bound oxygen from water and O 2 . Additionally, direct incorporation of molecular O 2 suggests that Mn( III / IV ) oxides contain a yet untapped proxy of of environmental O 2 , a parameter reflecting the integrated influence of global respiration, photorespiration, and several other biogeochemical reactions of global significance.

Sutherland, K. M.↗
NASA NTRS1989

Ozone precursors and ozone photochemistry over eastern North Pacific during the spring of 1984 based on the NASA GTE/CITE 1 airborne observations

Simultaneous high-resolution measurements of O3, NO, CO, dew point temperature, and UV flux obtained during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation (GTE/CITE 1) spring 1984 airborne field exercise over the eastern North Pacific Ocean are analyzed. Mid-tropospheric CO, O3, and NO mixing ratios averaged about 120 parts per billion by volume (ppbv), 50 ppbv, and 10 parts per trillion by volume (pptv), respectively. Statistical analysis of the high-resolution data indicates the existence of two ozone sources, one related to the downward transport of ozone-rich air from the upper troposphere and stratosphere, and the other to the transport of ozone-rich air from the continents. Modeling calculations based on these average levels imply that, from the surface to about 8 km, photochemical reactions probably supplied a net sink of ozone to the region overlying the eastern North Pacific Ocean during the sampling period. However, because the NO levels measured during the flights were frequently at or near the detection limit of the instruments and because the results are very sensitive to the absolute NO levels and their temporal variability, the conclusion must be considered provisional.

Chameides, W. L.↗
DOE OSTI2023

Green Biodegradation: Analysis of Potential Polyurethane-degrading Enzymes and Their Secretion in Chlamydomonas reinhardtii

Plastic pollution is a critical global issue, with only 5% of plastics currently recycled. Polyester polyurethane (PU), a widely used plastic, can potentially be broken down using enzymatic biodegradation rather than mechanical processing that generates microplastics. This study focuses on PS5, a potential PU-degrading enzyme with esterase activity, capable of cleaving ester bonds found in PU structures. Researchers investigated the expression and secretion of PS5 in the green microalga Chlamydomonas reinhardtii, a sustainable production platform capable of generating PU precursors such as lipids and diacids while sequestering carbon. Experiments demonstrated that PS5 significantly outperformed commercial lipase in cleaving the FDA substrate, indicating high esterase activity. Algal transformants expressing PS5 also showed halo formation on Impranil®-agar plates, suggesting PU dispersion degradation. These findings highlight C. reinhardtii as a viable chassis for the production and secretion of plastic-degrading enzymes, offering a sustainable route to both upcycle and degrade PU products at the end of their lifecycle.

Diaz, Crisandra Jade↗
DOE OSTI2023

Cannabis monoterpene synthases: evaluating structure–function relationships

Terpene synthases catalyze the first committed step in the biosynthesis of terpenes, a structurally diverse class of natural products that also encompasses volatiles derived from precursors in the C10 to C15 range (termed monoterpenes and sesquiterpenes, respectively). In the review section of this article, we are providing information about all functionally characterized monoterpene synthases (MTSs) and sesquiterpene synthases (STSs) of Cannabis sativa L. We are also exploring the locations of MTSs and STSs in the chromosome-level assembly of the reference chemovar CBDRx. A follow-up computational structure–function analysis focuses on MTSs, as there is already a rich literature available on the topic. More specifically, by employing sequence comparisons and homology structural modeling, we infer which amino acid residues are likely to constrain the available space in the active site of cannabis MTSs. The emphasis of these studies was to investigate why some MTSs accept only a C10 diphosphate as substrate, while mixed MTS/STS enzymes also accommodate a C15 diphosphate. Here, by combining a literature review and computational analyses in a hybrid format, we are laying the foundation for future studies to better understand the determinants of substrate and product specificity in these fascinating enzymes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

The efficacy of Lewis affinity scale metrics to represent solvent interactions with reagent salts in all-inorganic metal halide perovskite solutions

Solvents employed in the solution processing of metal halide perovskites are known to play a key role in defining the morphology and properties of the resulting thin film, and thus the performance of perovskite solar cell devices. Accurate metrics are needed that are capable of differentiating among candidates, finding solvents that adequately solubilize the various precursor species in solution and facilitate the nucleation and growth of these materials. Existing metrics such as the unsaturated Mayer bond order (UMBO) and the Gutmann donor number (DN) have been tested for lead iodide perovskite systems; but there has yet to be a comprehensive study on their transferability to lead-free perovskite solutions. Here, we use ab initio methods (density functional theory) and regression analysis tools to study the usefulness of DN and BF 3 affinity scales in this regard. We compared the relative effectiveness of these scales to describe interactions between solvents and BXn perovskite salts of lead (Pb 2+ ), tin (Sn 2+ and Sn 4+ ), germanium (Ge 2+ ), bismuth (Bi 3+ ), and antimony (Sb 3+ and Sb 5+ ). The DN proved to be a better representation than the BF 3 of such interactions, reflecting the closer similarity of these species to the “parent” SbCl 5 Lewis acid than to BF 3 . In addition, we have uncovered the usefulness of the lithium cation affinity metric (LCA) to describe the strength of interactions between solvents and A-site cations (e.g. Na + , K + , Rb + and Cs + ) in all-inorganic metal halide perovskite solutions. We find that the coordination strengths of solvents towards species in all-inorganic metal halide perovskite solutions are best described by two different metrics with distinct modes of action: DN differentiates among BX n salt complexes, and LCA among A-site cation species. This revelation can help guide the choice of solvent to optimize processing conditions. It also emphasizes the importance of selecting solvents whose DN and LCA optimize coordination to key Lewis acid species in all-inorganic perovskite solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

A Shuttle Imaging Spectrometer Experiment for the late 1980's

The Shuttle Imaging Spectrometer Experiment (SISEX), proposed as a next experimental step in the development of advanced earth remote sensing technology, is capable of imaging the earth's surface simultaneously in 128 spectral bands covering the range from 0.4 to 2.5 micrometers. Laboratory and field measurements have suggested the utility of high-spectral-resolution remote sensing, and an aircraft-borne precursor to the SISEX has demonstrated the ability to distinguish among differing vegetation and rock types - in certain cases making unique identifications. The SISEX instrument utilizes an area-array focal plane, populated by visual- and infrared-sensitive detectors, to acquire simultaneous spatial and spectral information on a line-by-line basis. The spectrum is dispersed by means of a prism spectrometer. The performance analysis indicates that the scientific requirements for radiometric precision can be achieved using optics with an effective circular aperture of 11 cm.

Wellman, J. B.↗
DOE OSTI2026

Biochemical Conversion of Herbaceous Biomass to Renewable Diesel: Biorefinery Marginal Air Quality Impacts and Comparison to Feedstock Production

This study assesses the air quality impacts of an advanced biorefinery that produces renewable diesel blendstock (RDB) from lignocellulosic biomass via aerobic respiration (Davis et al. 2022) by estimating fine particulate matter (PM2.5) impacts from biorefinery emissions. It continues a prior analysis that used a geospatial assessment to identify source regions for biomass feedstocks and studied the impact of feedstock production emissions on air quality (Thind et al. 2022). Thind et al. (2022) identified RDB biorefineries that can use corn stover feedstocks of 2,000; 5,200; and 9,100 dry metric tons per day (DMT/day), based in Iowa, and suggested 7 unique counties can serve as hosts for a biorefinery that draws biomass feedstock from neighboring counties. Given 13 unique county-biorefinery size combinations and two waste lignin end uses at the biorefinery (lignin as a fuel for electricity generation and lignin for pellet production), the air-quality-related sustainability aspects of each of these 26 scenarios are assessed by estimating the annual average impacts of biorefinery emissions on the dispersion and formation of secondary PM2.5 in the atmosphere using a novel reduced-complexity air quality model called the Intervention Model for Air Pollution (InMAP). The 26 biorefinery design combinations help capture how a biorefinery's emissions of air pollutants and their resulting impact on local and regional air quality are influenced by the magnitude of production scale, lignin utilization strategy, and location of a proposed biorefinery. Methods developed in Thind et al. (2022) are applied to estimate the constraints on primary PM2.5 and secondary PM2.5 precursor emissions based on compliance with U.S. Environmental Protection Agency's (EPA's) annual primary National Ambient Air Quality Standard (NAAQS) of PM2.5 (i.e.12.0 micrograms per cubic meter (microgram/m3)) at downwind receptors of a biorefinery. Incremental PM2.5 concentrations caused by the emission of biorefining corn stover into RDB are assessed and compared to those of corn stover production. To illuminate which upstream supply chain stage of renewable diesel production contributes most to air quality impacts, marginal PM2.5 concentrations are compared between both stages at multiple downwind air quality monitor locations. In addition, through a hotspot analysis, we identify the primary contributing factors of emissions within the feedstock production and biorefinery stage operations. In doing so, we provide insights for improving the air pollutant emission-related sustainability of advanced lignocellulosic biofuel production.

09 BIOMASS FUELS↗
NASA NTRSDate not supplied

Zircon, Baddeleyite, and Reidite Found in Ries Crater Suevite

Introduction: Impact events can generate superheated impact melts and even vapor [1]. In the past decade, evidence of the high temperatures and high pressures of the impact process has been found in the impact melt from terrestrial craters (e.g., Mistastin Lake [2], Meteor Crater [3]) and even on the Moon [4–5]. Often, these studies involve zircon or zirconium-bearing phases. Zircon is a particularly useful mineral, due to its robustness and durability against weathering. It is used principally for chronology, but it has a multitude of geologic applications, including geothermometry and fingerprinting magma sources. Here we focus on its capability of recording impact conditions. Grains of zircon (ZrSiO4) are converted at high temperature and/or pressure during an impact event to reidite (a high-pressure polymorph of ZrSiO4) or to tetragonal-ZrO2 + SiO2 [6]. Reidite and tertragonal-ZrO2 leave identifying relicts in the rocks, markers of the high pressures and/or temperatures these rocks underwent. Ries Crater is a 26-km-diameter peak ring crater in southern Germany that formed approximately 15 Ma [7–9]. Ries is the type locality of the polymict impact breccia known as suevite. Here, we report a microanalytical study of suevite from the Ries impact structure. These analyses are used to inform our understanding of the pressure and temperature conditions involved in creating a polymict impact breccia such as suevite in a peak ring crater. Sample Description: The sample, denoted 16RS08, originates from Otting Quarry, at 48.8777° N, 10.7921° E, approximately 17 km from the center of the Ries Crater in Germany (approximately 4 km outside the crater rim). The material recorded in sample 16RS08 is therefore considered an outer suevite. The outer suevite is a discontinuous layer of polymict impact breccia that occurs outside the central ring of Ries, up to 22 km from the center of the crater [9]. Lithic clasts in the outer suevite consist primarily of crystalline basement rocks (gneiss, granite, amphibolite), with less than 5% of lithic clasts being overlying sedimentary rocks (limestone, sandstone, shale) [9]. The thin section studied contains variably shocked lithic and mineral clasts, impact glass, and interstitial minerals that make up the matrix of the breccia (Fig. 1) [9]. Methods: We used a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona to obtain 15 elemental X-ray maps of 16RS08. We next used the JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC) to obtain electron backscatter diffraction (EBSD) maps and energy dispersive X-ray spectroscopy (EDS) maps of select portions of the section. The EBSD data were collected under beam conditions of 20 kV, and ~9 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We used the elemental X-ray maps to identify the areas of interest in the section, particularly phosphates and Zr-bearing grains. These areas of interest were then targeted for follow up EBSD and EDS analyses. We have identified, through combined EBSD and EDS analysis, the presence of zircon, reidite, and monoclinic-ZrO2 (baddeleyite) in 16RS08. In 16RS08, we have found singular grains of zircon, zircon with a vermicular baddeleyite halo (Fig. 2a), and granular zircon with reidite (Fig. 2b). The different Zr-rich phases and their corresponding textures signifies that this sample underwent a broad spectrum of pressure and temperature conditions during the impact event. For example, zircons surrounded by a vermicular baddeleyite and SiO2 intergrowth (i.e., Fig. 2a) have been shown to preserve evidence of the extremely high temperatures of impact melt, upwards of 2370 °C [2, 6]. Similarly, reidite and granular zircon (i.e., Fig. 2b) have been shown to preserve evidence of high pressure, as the transition to reidite occurs >30 GPa [3, 6]. Future Work: Next, we will process the EBSD and EDS data for these Zr-rich grains, specifically looking for indicators of cubic- or tetragonal-ZrO2 in the baddeleyite remnants and of shock-precursors to the reidite. To further inform our work, we will also obtain BSE images of these grains using a Hitachi S-4800 SEM in KMICF at the University of Arizona, as well as geochemical spot analyses via EPMA. The data collected will be used to constrain the formation conditions of the Ries Crater outer suevite. Acknowledgments: We thank Ken Domanik and Jerry Chang for their support with data collection. This work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. TME thanks A. Cavosie and N. Timms for assistance during field sampling. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Melosh H. J. (1989) Oxf. U. Press. [2] Timms et al. (2017) EPSL 477, 52–58. [3] Cavosie et al. (2016) Geology 44:9, 703–706. [4] White et al. (2020) Nature Astr. 4, 974–978. [5] Crow C. A. et al. (2017) GCA 202, 264–284. [6] Timms et al. (2017) Earth-Sci. Rev. 165, 185–202. [7] Schmieder M. et al. (2018) GCA 220, 146–157. [8] Schwarz W. H. et al. (2020) M&PS 55:2, 312–325. [9] Stöffler et al. (2013) M&PS 43:4, 515–589.

Zircon↗
DOE OSTI2024

Size-Resolved Shape Evolution in Inorganic Nanocrystals Captured via High-Throughput Deep Learning-Driven Statistical Characterization

Precise size and shape control in nanocrystal synthesis is essential for utilizing nanocrystals in various industrial applications, such as catalysis, sensing, and energy conversion. However, traditional ensemble measurements often overlook the subtle size and shape distributions of individual nanocrystals, hindering the establishment of robust structure–property relationships. In this study, we uncover intricate shape evolutions and growth mechanisms in Co 3 O 4 nanocrystal synthesis at a subnanometer scale, enabled by deep-learning-assisted statistical characterization. By first controlling synthetic parameters such as cobalt precursor concentration and water amount then using high resolution electron microscopy imaging to identify the geometric features of individual nanocrystals, this study provides insights into the interplay between synthesis conditions and the sizedependent shape evolution in colloidal nanocrystals. Utilizing population-wide imaging data encompassing over 441,067 nanocrystals, we analyze their characteristics and elucidate previously unobserved size-resolved shape evolution. This high-throughput statistical analysis is essential for representing the entire population accurately and enables the study of the size dependency of growth regimes in shaping nanocrystals. Our findings provide experimental quantification of the growth regime transition based on the size of the crystals, specifically (i) for faceting and (ii) from thermodynamic to kinetic, as evidenced by transitions from convex to concave polyhedral crystals. Additionally, we introduce the concept of an “onset radius,” which describes the critical size thresholds at which these transitions occur. This discovery has implications beyond achieving nanocrystals with desired morphology; it enables finely tuned correlation between geometry and material properties, advancing the field of colloidal nanocrystal synthesis and its applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2017

Alternative High-Performance Ceramic Waste Forms

This final report (M5NU-12-NY-AU # 0202-0410) summarizes the results of the project titled “Alternative High-Performance Ceramic Waste Forms,” funded in FY12 by the Nuclear Energy University Program (NEUP Project # 12-3809) being led by Alfred University in collaboration with Savannah River National Laboratory (SRNL). The overall focus of the project is to advance fundamental understanding of crystalline ceramic waste forms and to demonstrate their viability as alternative waste forms to borosilicate glasses. We processed single- and multiphase hollandite waste forms based on simulated waste streams compositions provided by SRNL based on the advanced fuel cycle initiative (AFCI) aqueous separation process developed in the Fuel Cycle Research and Development (FCR&D). For multiphase simulated waste forms, oxide and carbonate precursors were mixed together via ball milling with deionized water using zirconia media in a polyethylene jar for 2 h. The slurry was dried overnight and then separated from the media. The blended powders were then subjected to melting or spark plasma sintering (SPS) processes. Microstructural evolution and phase assemblages of these samples were studied using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersion analysis of x-rays (EDAX), wavelength dispersive spectrometry (WDS), transmission electron spectroscopy (TEM), selective area x-ray diffraction (SAXD), and electron backscatter diffraction (EBSD). These results showed that the processing methods have significant effect on the microstructure and thus the performance of these waste forms. The Ce substitution into zirconolite and pyrochlore materials was investigated using a combination of experimental (in situ XRD and x-ray absorption near edge structure (XANES)) and modeling techniques to study these single phases independently. In zirconolite materials, a transition from the 2M to the 4M polymorph was observed with increasing Ce content. The resulting powders were consolidated via SPS. Ce was reduced to the trivalent oxidation state and the zirconolite was converted into undesirable perovskite. The zirconolite polymorphs found in the synthesized powders were recovered after a post-SPS heat treatment in air. These results demonstrated the potential of processing in controlling the phase assemblage in these waste forms. Hollandites with Cr 3+ trivalent cations were identified as potential hosts for Cs immobilization and are being investigated for Cs retention properties. Series of compositions Ba 1.15-x Cs 2x Cr 2.3 Ti 5.7 O 16 , with increasing Cs loadings, were prepared by sol-gel process and characterized for structural parameters. Structural characterization was performed by a combination of powder XRD and neutron powder diffraction. Phase pure hollandite adapting monoclinic symmetry (I2/m) was observed for 0 ≤ x ≤ 0.55. These results were used to develop a new structural model to interpret Cs immobilization in these hollandites. Performance of these waste forms were evaluated for chemical durability and radiation resistance. Product consistency testing (PCT) and vapor hydration testing (VHT) were used for testing of chemical durability. Radiation resistance was tested using He + ions to simulate $\alpha$ particles and heavy ions such as Au 3+ to simulate a recoil. These results showed that these waste forms were chemically durable. The waste forms also amorphized to various degrees on exposure to simulated radiation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

NORTH DAKOTA CARBONSAFE PHASE III: SITE CHARACTERIZATION AND PERMITTING OF GEOLOGIC STORAGE OF CARBON DIOXIDE

The Energy & Environmental Research Center (EERC), in partnership with Minnkota Power Cooperative Inc. (Minnkota), SLB, and Computer Modelling Group Ltd. (CMG), supported wide-scale deployment of carbon capture and storage (CCS) as part of the U.S. Department of Energy (DOE) National Energy Technology Laboratory Carbon Storage Assurance Facility Enterprise (CarbonSAFE) Initiative Phase III. This phase included the acquisition, analysis, and development of information to fully characterize two storage complexes to demonstrate viable storage resources for commercial volumes of CO2 (defined by DOE as a minimum of 50 million tonnes [MMt] of CO2 within a 30-year period) (National Energy Technology Laboratory, 2024). Phase III also involved the preparation, submission, and approval of North Dakota underground injection control (UIC) Class VI storage facility permits (SFPs)—required precursors to applications for Class VI injection well permits. The presumed viability of commercial-scale CCS, situated adjacent to Minnkota’s Milton R. Young Station (MRYS), is validated by Minnkota’s continued pursuit of Project Tundra—an initiative to build the world’s largest lignite-based CCS project in central North Dakota (www.projecttundrand.com). Project Tundra comprises two scopes of work, Tundra Capture (installation of postcombustion CO2 capture at MRYS) and Tundra SGS (secure geologic storage). The efforts of North Dakota CarbonSAFE Phase III, Site Characterization and Permitting, supported Tundra SGS. Extensive site-specific characterization activities included a successful multimeasurement geophysical approach and drilling a stratigraphic test well (J-ROC 1, subsequently renamed Liberty-1) adjacent to MRYS. Core collection and analyses, downhole testing and fluid sampling, and geophysical logging were performed on J-ROC 1 and on a nearby stratigraphic test well (known as J-LOC 1), which was drilled, cored, and tested under a complementary project funded by the North Dakota Lignite Research Program. The injection tests performed on J-LOC 1 positively impacted the CarbonSAFE project, resulting in fewer proposed injection wells and significant construction, operations, and monitoring cost savings. The characterization data collected and analyses performed were integrated into geologic models, and successive numerical simulations were run to determine CO2 plume extent and subsurface pressure buildup associated with the planned CO2 injection rate of nearly 4 MMt per year. The latter doubles the CarbonSAFE Initiative goal with an estimated 100 MMt of CO2 stored in 20 years. Application of the U.S. Environmental Protection Agency’s (EPA’s) method for estimating the Class VI Rule area of review (AOR) to the overpressurized Broom Creek Formation inspired an alternative method of calculation, called risk-based AOR delineation. This peer-reviewed method was applied for the first time during the storage facility-permitting process. The two SFP applications submitted in 2021 successfully resulted in North Dakota Industrial Commission (NDIC) orders in 2022 authorizing the creation of the storage facility areas and amalgamation of pore space as well as establishing financial responsibility requirements. After approval of the SFPs, Minnkota filed in 2022 applications for permits to reenter the J-ROC 1 well and to drill two new wells—all with the intended purpose to become Class VI injection wells. To establish eligibility under the Internal Revenue Code for Section 45Q tax incentives, a monitoring, reporting, and verification (MRV) plan was prepared and submitted by Minnkota to EPA in 2022, resulting in the first such plan approved in North Dakota. Also in 2022, under the National Environmental Policy Act (NEPA), Minnkota prepared and submitted an environmental information volume (EIV) describing the proposed CCS project and associated potential environmental impacts. Based on the EIV, DOE determined that the proposed construction project required an environmental assessment, and Minnkota submitted the first draft in 2023 and a revised draft in 2024. Both submissions were followed by a public comment period. Subsequently, DOE issued a finding of no significant impact (FONSI) on September 13, 2024. A successful outreach program, strongly based in the production, presentation, and dissemination of informational material, fostered an environment to aid stakeholders in making informed decisions regarding the planned project. Opportunities for public input were provided at various steps along the way, including at county planning and zoning meetings, before and during the SFP administrative hearing, and during environmental assessment public comment periods. In addition, land/pore space owners and mineral owners had various points of contact, including granting access rights, securing pore space leasing, and mineral owner notifications. Based upon the successful storage facility permitting issued by NDIC, approval of the MRV plan by EPA, and receipt of a FONSI under the NEPA, Minnkota is continuing its pursuit of Project Tundra. In December 2023, the Office of Clean Energy Demonstrations under its Carbon Capture Demonstrations Projects Program announced funding for the capture system (Office of Clean Energy Demonstrations, 2023) and a proposal for CarbonSAFE Phase IV: Construction funding was submitted in March 2024 for the storage project. A go/no-go decision to proceed with construction and operations in the Broom Creek Formation is anticipated in 2024. References National Energy Technology Laboratory, CarbonSafe Initiative, https://netl.doe.gov/carbon-management/carbon-storage/carbonsafe (accessed August 2024). Office of Clean Energy Demonstrations, 2023, OCED selects three projects in CA, ND, and TX to reduce harmful carbon pollution, create new economic opportunities, and advance carbon reducing technologies, December, www.energy.gov/oced/articles/oced-selects-three-projects-ca-nd-and-tx-reduce-harmful-carbon-pollution-create-new (accessed August 2024).

Peck, Wesley↗
DOE OSTI2015

Evolution of plant δ 1 -pyrroline-5-carboxylate reductases from phylogenetic and structural perspectives

Proline plays a crucial role in cell growth and stress responses, and its accumulation is essential for the tolerance of adverse environmental conditions in plants. Two routes are used to biosynthesize proline in plants. The main route uses glutamate as a precursor, while in the other route proline is derived from ornithine. The terminal step of both pathways, the conversion of δ 1 -pyrroline-5-carboxylate (P5C) to L-proline, is catalyzed by P5C reductase (P5CR) using NADH or NADPH as a cofactor. Since P5CRs are important housekeeping enzymes, they are conserved across all domains of life and appear to be relatively unaffected throughout evolution. However, global analysis of these enzymes unveiled significant functional diversity in the preference for cofactors (NADPH vs. NADH), variation in metal dependence and the differences in the oligomeric state. In our study we investigated evolutionary patterns through phylogenetic and structural analysis of P5CR representatives from all kingdoms of life, with emphasis on the plant species. We attempted to correlate local sequence/structure variation among the functionally and structurally characterized members of the family.

3-D structures of P5CRs↗
DOE OSTI2016

Effective reduction in the nanoparticle sizes of NiO obtained via the pyrolysis of nickel malonate precursor modified using oleylamine surfactant

Nickel oxide nanoparticles were synthesized via thermal decomposition of two precursors, the first, a simple nickel malonate and the second, a nickel malonate modified by oleylamine, a surfactant, both having been synthesized by precipitation. While FTIR, TGA and ToF-SIMS were used to characterize the two precursors and to show the presence of oleylamine in the modified precursor, XRD, SEM, TEM and BET were employed to investigate the structure, the morphology and the specific surface area of the decomposition products obtained after pyrolysis. The results showed that the modification of nickel malonate by oleylamine was effective. The XRD results, which showed a cubic structure for the NiO obtained, suggest with SEM an important particle size reduction (at least 54%) when oleylamine was used to modify the nickel malonate precursor. The SEM images also showed a well-defined spherical nanoparticle morphology in both cases, not affected by the presence of oleylamine. The TEM also confirmed the reduction of particle size and their spherical nature but at the same time showed that, in the presence of oleylamine, there was no agglomeration resulting in a more uniform particle size distribution. The specific surface area of the NiO obtained by the oleylamine-modified precursor was 4.7 times larger than that obtained with the regular precursor. This again confirms the particle size reduction. - Highlights: • Nickel malonate precursor has been synthesized by precipitation method. • This precursor was successfully modified by a surfactant (oleylamine). • NiO was identified as the decomposition products of the previous precursors. • Oleylamine has provoked around 54% of particle size reduction of the NiO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

BMP4 signaling in NPCs upregulates Bcl-xL to promote their survival in the presence of FGF-2

Highlights: • BMP4 promoted survival of neural stem/progenitor cells (NPCs) in the presence of FGF-2. • BMP4 activated Smad1/5/8 signaling and promoted Id1 and Bcl-xL expression. • BMP4 inhibited cytochrome c release from mitochondria via Bcl-xL expression. We previously reported that BMP4 does not promote proliferation or differentiation of CD44-positive astrocyte precursor cells (APCs) but greatly promotes their survival in the presence of fibroblast growth factor-2 (FGF-2). In this study, we examined if BMP4 acts as a survival factor also for neural stem/progenitor cells (NPCs) isolated from ganglionic eminence of neonatal mouse brain. We found BMP4 promotes survival but not proliferation or differentiation of these cells, just as in the case for CD44-positive APCs. Microarray analysis revealed some candidate molecules in the signaling pathway downstream of BMP4. Among them, we focused on Id1 (inhibitor of DNA-binding 1) and Bcl-xL in this study. Expression of both genes was promoted in the presence of BMP4, and this promotion was reduced by dorsomorphin, an inhibitor of BMP4 signaling. Furthermore, cytochrome c release from mitochondria was significantly reduced in the presence of BMP4, suggesting up-regulation of Bcl-xL activity by BMP4. Id1 siRNA reduced the expression of Bcl-xL, and negated survival promoting effect of BMP4. These data suggest that BMP4 promotes survival of NPCs by enhancing the anti-apoptotic function of Bcl-xL via BMP4-Smad1/5/8-Id1 signaling.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Aircraft measurements of aerosol and trace gas chemistry in the eastern North Atlantic

The Aerosol and Cloud Experiment in the Eastern North Atlantic (ACE-ENA) investigated properties of aerosols and subtropical marine boundary layer (MBL) clouds. Low subtropical marine clouds can have a large effect on Earth's radiative budget, but they are poorly represented in global climate models. In order to understand their radiative effects, it is imperative to understand the composition and sources of the MBL cloud condensation nuclei (CCN). The campaign consisted of two intensive operation periods (IOPs) (June–July 2017 and January–February 2018) during which an instrumented G-1 aircraft was deployed from Lajes Field on Terceira Island in the Azores, Portugal. The G-1 conducted research flights in the vicinity of the Atmospheric Radiation Measurement (ARM) Eastern North Atlantic (ENA) atmospheric observatory on Graciosa Island. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and Ionicon proton-transfer-reaction mass spectrometer (PTR-MS) were deployed aboard the aircraft, characterizing chemistry of non-refractory aerosol and trace gases, respectively. The eastern North Atlantic region was found to be very clean, with an average non-refractory submicrometer aerosol mass loading of 0.6 µg m −3 in the summer and 0.1 µg m −3 in the winter, measured by the AMS. Average concentrations of the trace reactive gases methanol and acetone were 1–2 ppb; benzene, toluene and isoprene were even lower, <1 ppb. Mass fractions of sulfate, organics, ammonium and nitrate in the boundary layer were 69 %, 23 %, 7 % and 1 % and remained largely similar between seasons. The aerosol chemical composition was dominated by sulfate and highly processed organics. Particulate methanesulfonic acid (MSA), a well-known secondary biogenic marine species, was detected, with an average boundary layer concentration of 0.021 µg m −3 , along with its gas-phase precursor, dimethyl sulfide (DMS). MSA accounted for no more than 3 % of the submicron, non-refractory aerosol in the boundary layer. Examination of vertical profiles of aerosol and gas chemistry during ACE-ENA reveals an interplay of local marine emissions and long-range-transported aged aerosol. A case of transport of biomass burning emissions from North American fires has been identified using back-trajectory analysis. In the summer, the non-refractory portion of the background CCN budget was heavily influenced by aerosol associated with ocean productivity, in particular sulfate formed from DMS oxidation. Episodic transport from the continents, particularly of biomass burning aerosol, periodically increased CCN concentrations in the free troposphere. In the winter, with ocean productivity lower, CCN concentrations were overall much lower and dominated by remote transport. These results show that anthropogenic emissions perturb CCN concentrations in remote regions that are sensitive to changes in CCN number and illustrate that accurate predictions of both transport and regional aerosol formation from the oceans are critical to accurately modeling clouds in these regions.

54 ENVIRONMENTAL SCIENCES↗