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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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DOE OSTI2021

A critical review of 25 years of glomalin research: a better mechanical understanding and robust quantification techniques are required

Arbuscular mycorrhizal fungi (AMF) are important contributors to both plant and soil health. Twenty-five years ago, researchers discovered ‘glomalin’, a soil component potentially produced by AMF, which was unconventionally extracted from soil and bound by a monoclonal antibody raised against Rhizophagus irregularis spores. ‘Glomalin’ can resist boiling, strong acids and bases, and protease treatment. Researchers proposed that ‘glomalin’ is a 60 kDa heat shock protein produced by AMF, while others suggested that it is a mixture of soil organic materials that are not unique to AMF. Despite disagreements on the nature of ‘glomalin’, it has been consistently associated with a long list of plant and soil health benefits, including soil aggregation, soil carbon storage and enhancing growth under abiotic stress. The benefits attributed to ‘glomalin’ have caused much excitement in the plant and soil health community; however, the mechanism(s) for these benefits have yet to be established. This review provides insights into the current understanding of the identity of ‘glomalin’, ‘glomalin’ quantification, and the associated benefits of ‘glomalin’. We invite the community to think more critically about how glomalin-associated benefits are generated. We suggest a series of experiments to test hypotheses regarding the nature of ‘glomalin’ and associated health benefits.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

The evolving role of geothermal energy for decarbonizing the United States

Geothermal energy is often referred to as a niche technology that is too localized, too small or too expensive to make much of a difference in how renewable energy will be supplied in a fully decarbonized future. As a result, geothermal energy has been undervalued in terms of what it could provide to complement, rather than compete with, electricity generation from wind, solar photovoltaic, concentrating solar power and other renewables. Geothermal energy systems are fully dispatchable and can provide baseload or load-following electric power or heat suitable for a wide range of applications including supplying district heating for communities and cities, and heating and cooling of individual buildings. The focus of our study is on the potential of utilizing geothermal energy for providing heat for buildings and industry at lower temperatures, a substitute for the combustion of fossil fuels. Because heating represents about 20% (20 EJ per year) of the annual primary energy consumption in the U.S.—with most of it coming from burning natural gas, oil and/or propane in furnaces—deploying geothermal heating on a national scale could have a significant impact on lowering carbon emissions. In heating-dominated states in the U.S. Northern Tier, heating often is among the largest contributors to the state's carbon footprint. This review begins with a discussion of the motivation and rationale behind considering geothermal as a key low-carbon heating option for the U.S. The study summarizes the U.S. geothermal resource and describes the applications and main engineering components of using geothermal energy for heating and cooling, electric power generation, and co-generation using district heating, geothermal heat pumps, and power conversion with steam flashing and organic Rankine plants. Environmental benefits and impacts are described. An extensive discussion of geologic and thermal-hydraulic aspects of the subsurface is included in the review because of their critical role in determining reservoir designs at specific sites to ensure sufficient productivity that is both safe and economically viable. Models for estimating levelized costs of district heating are used to show how costs are affected by reservoir performance, infrastructure capital costs, and financial parameters. Here, the review concludes with an assessment of technical subsurface issues associated with reservoir performance and the economic requirements for providing geothermal heating in district heating systems at a sufficient scale to have an impact on decarbonizing the U.S.

15 GEOTHERMAL ENERGY↗
DOE OSTI2023

Unbalanced Nested Random Effects Estimation of Variance Components

To investigate the contributing factors of variance in the measurement of an iodine 127 (127I) sample, we implement a nested random effects analysis of variance (ANOVA). Historically, the reported uncertainty on a measurement of 127I has been obtained by methods of forward uncertainty propagation because there is typically only one replicate of a given sample for which to estimate the uncertainty. When samples are processed there are several types of quality control (QC) standards analyzed along-side the unknown samples with two to five replicates for each. Assuming the variance observed in these replicate QC standards is representative of that of the unknown samples, we use these data in a nested random effects ANOVA to estimate the total uncertainty of a measurement. We demonstrate this approach with two sets of measurements from Idaho National Laboratory and compare the results with the forward uncertainty propagation approach. Variance component estimates for the coarsest level of the nesting structure were most imprecise because replicates were most limited at these levels. We find that the results largely agree between forward propagation and ANOVA, and the greatest contributors of variance are due to instrument variation and chemical processing, with human processing being among the smallest contributors. This analysis provides reassurance that the reported uncertainties using forward propagation are reasonable and the process is well controlled. We propose a future designed experiment to increase replicates at the coarsest level of the hierarchy to improve estimates of these variance components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Characterization of organic aerosol across the global remote troposphere: a comparison of ATom measurements and global chemistry models

The spatial distribution and properties of submicron organic aerosol (OA) are among the key sources of uncertainty in our understanding of aerosol effects on climate. Uncertainties are particularly large over remote regions of the free troposphere and Southern Ocean, where very few data have been available and where OA predictions from AeroCom Phase II global models span 2 to 3 orders of magnitude, greatly exceeding the model spread over source regions. The (nearly) pole-to-pole vertical distribution of non-refractory aerosols was measured with an aerosol mass spectrometer onboard the NASA DC-8 aircraft as part of the Atmospheric Tomography (ATom) mission during the Northern Hemisphere summer (August 2016) and winter (February 2017). This study presents the first extensive characterization of OA mass concentrations and their level of oxidation in the remote atmosphere. OA and sulfate are the major contributors by mass to submicron aerosols in the remote troposphere, together with sea salt in the marine boundary layer. Sulfate was dominant in the lower stratosphere. OA concentrations have a strong seasonal and zonal variability, with the highest levels measured in the lower troposphere in the summer and over the regions influenced by biomass burning from Africa (up to 10 µg sm -3 ). Lower concentrations (~0.1–0.3 µg sm -3 ) are observed in the northern middle and high latitudes and very low concentrations (<0.1 µg sm -3 ) in the southern middle and high latitudes. The ATom dataset is used to evaluate predictions of eight current global chemistry models that implement a variety of commonly used representations of OA sources and chemistry, as well as of the AeroCom-II ensemble. The current model ensemble captures the average vertical and spatial distribution of measured OA concentrations, and the spread of the individual models remains within a factor of 5. These results are significantly improved over the AeroCom-II model ensemble, which shows large overestimations over these regions. However, some of the improved agreement with observations occurs for the wrong reasons, as models have the tendency to greatly overestimate the primary OA fraction and underestimate the secondary fraction. Measured OA in the remote free troposphere is highly oxygenated, with organic aerosol to organic carbon (OA/OC) ratios of ~2.2–2.8, and is 30 %–60 % more oxygenated than in current models, which can lead to significant errors in OA concentrations. The model–measurement comparisons presented here support the concept of a more dynamic OA system as proposed by Hodzic et al. (2016), with enhanced removal of primary OA and a stronger production of secondary OA in global models needed to provide better agreement with observations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Source Characterization of Volatile Organic Compounds at Carlsbad Caverns National Park

Carlsbad Caverns National Park (CAVE), located in southeastern New Mexico, experiences elevated ground-level ozone (O 3 ) exceeding the National Ambient Air Quality Standard (NAAQS) of 70 ppbv. It is situated adjacent to the Permian Basin, one of the largest oil and gas (O&G) producing regions in the US. In 2019, the Carlsbad Caverns Air Quality Study (CarCavAQS) was conducted to examine impacts of different sources on ozone precursors, including nitrogen oxides (NO x ) and volatile organic compounds (VOCs). Here, we use positive matrix factorization (PMF) analysis of speciated VOCs to characterize VOC sources at CAVE during the study. Seven factors were identified. Three factors composed largely of alkanes and aromatics with different lifetimes were attributed to O&G development and production activities. VOCs in these factors were typical of those emitted by O&G operations. Associated residence time analyses (RTA) indicated their contributions increased in the park during periods of transport from the Permian Basin. These O&G factors were the largest contributor to VOC reactivity with hydroxyl radicals (62%). Two PMF factors were rich in photochemically generated secondary VOCs; one factor contained species with shorter atmospheric lifetimes and one with species with longer lifetimes. RTA of the secondary factors suggested impacts of O&G emissions from regions farther upwind, such as Eagle Ford Shale and Barnett Shale formations. The last two factors were attributed to alkenes likely emitted from vehicles or other combustion sources in the Permian Basin and regional background VOCs, respectively.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Protist diversity and community complexity in the rhizosphere of switchgrass are dynamic as plants develop

Abstract Background Despite their widespread distribution and ecological importance, protists remain one of the least understood components of the soil and rhizosphere microbiome. Knowledge of the roles that protists play in stimulating organic matter decomposition and shaping microbiome dynamics continues to grow, but there remains a need to understand the extent to which biological and environmental factors mediate protist community assembly and dynamics. We hypothesize that protists communities are filtered by the influence of plants on their rhizosphere biological and physicochemical environment, resulting in patterns of protist diversity and composition that mirror previously observed diversity and successional dynamics in rhizosphere bacterial communities. Results We analyzed protist communities associated with the rhizosphere and bulk soil of switchgrass (SG) plants ( Panicum virgatum ) at different phenological stages, grown in two marginal soils as part of a large-scale field experiment. Our results reveal that the diversity of protists is lower in rhizosphere than bulk soils, and that temporal variations depend on soil properties but are less pronounced in rhizosphere soil. Patterns of significantly prevalent protists groups in the rhizosphere suggest that most protists play varied ecological roles across plant growth stages and that some plant pathogenic protists and protists with omnivorous diets reoccur over time in the rhizosphere. We found that protist co-occurrence network dynamics are more complex in the rhizosphere compared to bulk soil. A phylogenetic bin-based null model analysis showed that protists’ community assembly in our study sites is mainly controlled by homogenous selection and dispersal limitation, with stronger selection in rhizosphere than bulk soil as SG grew and senesced. Conclusions We demonstrate that environmental filtering is a dominant determinant of overall protist community properties and that at the rhizosphere level, plant control on the physical and biological environment is a critical driver of protist community composition and dynamics. Since protists are key contributors to plant nutrient availability and bacterial community composition and abundance, mapping and understanding their patterns in rhizosphere soil is foundational to understanding the ecology of the root-microbe-soil system.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Position Papers for the ASCR Workshop on Cybersecurity and Privacy for Scientific Computing Ecosystems

At the request of the Department of Energy's (DOE) Office of Advanced Scientific Computing Research (ASCR), this program committee has been tasked with organizing a workshop to identify basic research needs in cybersecurity and privacy to better support DOE's science and energy mission. As part of the process, the program committee is soliciting community input in the form of position papers to help identify significant use cases, facility issues, and other barriers to enabling verifiably trustworthy computational science while preserving data confidentiality as appropriate for scientific workflows of interest to DOE. The program committee will review these position papers and based on the fit of their area of expertise and interest, selected contributors will have the opportunity to participate in the workshop currently planned as a virtual event November 3-5th, 2021. The thrust areas that will be explored by this workshop are the following: (1) Algorithms for secure, scalable, privacy-enhancing technologies and frameworks, including: Federated AI/ML, Differential privacy, Randomized algorithms, Adversarial modeling & simulation, Graph algorithms, and Formal methods; (2) Platforms to support the entire scientific-computing ecosystem, including edge computing for large-scale experiments, focusing on heterogeneous systems and distributed systems, including: Heterogeneous computing systems, Distributed computing systems, and Secure data architectures; and (3) Data workflows to allow agile use of data while preserving integrity and privacy, making the important properties verifiable either at runtime or post-computation, including: Integrity and provenance and Data management infrastructure. Topics that are out-of-scope for the workshop include discussing specific proposed solutions or areas that are clearly out of DOE's fundamental and applied-sciences mission scope, e.g., cryptography, enterprise security, and general-operations technology.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

The rise and fall of stretched bond errors: Extending the analysis of Perdew–Zunger self-interaction corrections of reaction barrier heights beyond the LSDA

Incorporating self-interaction corrections (SIC) significantly improves chemical reaction barrier height predictions made using density functional theory methods. We present a detailed orbital-by-orbital analysis of these corrections for three semi-local density functional approximations (DFAs) situated on the three lowest rungs of Jacob’s ladder of approximations. The analysis is based on Fermi–Löwdin Orbital Self-Interaction Correction (FLOSIC) calculations performed at several steps along the reaction pathway from the reactants (R) to the transition state (TS) to the products (P) for four representative reactions selected from the BH76 benchmark set. For all three functionals, the major contribution to self-interaction corrections of the barrier heights can be traced to stretched bond orbitals that develop near the TS configuration. The magnitude of the ratio of the self-exchange–correlation energy to the self-Hartree energy (XC/H) for a given orbital is introduced as an indicator of one-electron self-interaction error. XC/H = 1.0 implies that an orbital’s self-exchange–correlation energy exactly cancels its self-Hartree energy and that the orbital, therefore, makes no contribution to the SIC in the FLOSIC scheme. For the practical DFAs studied here, XC/H spans a range of values. Here, the largest values are obtained for stretched or strongly lobed orbitals. We show that significant differences in XC/H for corresponding orbitals in the R, TS, and P configurations can be used to identify the major contributors to the SIC of barrier heights and reaction energies. Based on such comparisons, we suggest that barrier height predictions made using the strongly constrained and appropriately normed meta-generalized gradient approximation may have attained the best accuracy possible for a semi-local functional using the Perdew–Zunger SIC approach.

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

Techno-economic performances and life cycle greenhouse gas emissions of various ammonia production pathways including conventional, carbon-capturing, nuclear-powered, and renewable production

Ammonia (NH 3 ) is conventionally produced using fossil natural gas (NG) for hydrogen production through steam reformation and synthesis in the Haber–Bosch (HB) process. The global conventional ammonia production contributes more than 420 million tons of CO 2 emissions annually. Here, in this work, we investigated the techno-economics and well-to-plant-gate (WTG) greenhouse gas (GHG) emissions of conventional NG-based, carbon-capturing, nuclear-powered, and renewable ammonia production by developing an engineering process model for each. Carbon-capturing ammonia production refers to the NG-based ammonia production while capturing CO 2 and transporting it via pipelines for storage or utilization. Nuclear-powered and renewable ammonia production represents an alternative ammonia production through water electrolysis, air separation, and the HB process using carbon-free energy sources. Nuclear and renewable energy sources are assumed to be used for nuclear-powered and renewable ammonia production, respectively. Sensitivity analyses are performed for CO 2 pipeline transport distances, potential carbon capture tax credits, and clean H 2 production cost. Carbon-capturing ammonia production reduces WTG GHG emissions by 55–70% compared to conventional NG-based ammonia production methods. Nuclear-powered and renewable ammonia production almost eliminate GHG emissions since energy supply is either zero carbon or near-zero carbon. However, when $4.16–4.83 per kg is the cost assumed for clean H 2 production using state-of-the-art electrolysis technologies, the levelized costs of nuclear-powered and renewable ammonia are calculated to be $0.92–1.06 per kg NH 3 , which are approximately four times higher than the conventional NG-based ammonia production cost. The cost of CO 2 emission avoidance is estimated in the range of $266–318 per metric ton of CO 2 for nuclear-powered and renewable ammonia production. The clean H 2 production cost is the major contributor to the levelized costs of nuclear-powered and renewable ammonia production. A lower production cost, near $1 per kg H 2 , for clean H 2 is required for nuclear-powered and renewable ammonia production to be cost-competitive with conventional NG-based ammonia production.

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

Tailoring the structure and electrochemical performance of sodium titanate anodes by post-synthesis heating

Sodium titanate anodes synthesized via “chimie-douce” methods generally require a post-synthesis dehydration step. Their crystal structures are sensitive to the heating conditions such as temperature, resulting in distinct sodium storage performance. Herein, using in situ and ex situ high-temperature X-ray diffraction, we studied in detail the structural changes of Na 0.74 Ti 1.815 $\square$ 0.185 O 4 ·1.27H 2 O (NTO) under various heating conditions. Electrochemical characterization revealed that NTOs heated at lower temperatures with layered structures deliver larger capacities than those heated at high temperatures with tunnel structures. Heat treatment at moderate temperatures greatly improves the capacity retention of NTO, especially stabilizing the high voltage processes that are major contributors to the capacity fading, because of the modified crystal structure and surface chemistry. As a result, our findings suggest that post-synthesis heating is a simple and effective strategy to tailor the crystal structure, surface chemistry, and electrochemical properties of sodium titanate anodes.

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

Thermal Process Intensification: Transforming the Way Industry Uses Thermal Process Energy (Workshop Report)

The US Department of Energy’s (DOE’s) Advanced Manufacturing Office held the virtual workshop entitled “Thermal Process Intensification: Transforming the Way Industry Uses Thermal Process Energy” in November and December 2020. The workshop brought together participants from universities/laboratories, industries, equipment manufacturers, technology vendors, nongovernmental organizations, and subject-matter experts to discuss transformative technologies and strategies to substantially improve the performance (e.g., energy productivity, thermal efficiency, reduced greenhouse gas [GHG] emissions, reduced number of process steps) of thermal processing systems in the industrial sector. The US industrial sector accounts for 32% of the nation’s primary energy use (including feedstocks), and refining, chemicals, pulp and paper, iron and steel, and food products represent the top energy-consuming sectors. Thermal processing or process heating represents the largest energy use category; it accounts for 63% of all energy use in manufacturing. Additionally, thermal processing is the largest contributor of carbon dioxide (CO2) generation, resulting from combustion of fuels and process related chemical reactions, such as in the case of cement and lime production. The challenge of achieving net-zero industrial GHG emissions is colossal considering the established industrial base that depends mainly on carbon-based processes and energy sources; the time frame and cost to replace carbon-based energy sources and feedstocks; and the long-term outlook for development with large-scale adaptation of alternative non carbon–based technologies. The goals of the DOE Advanced Manufacturing Office Thermal Process Intensification Workshop were as follows: (1) Identify R&D gaps and opportunities to facilitate transformative improvement in industrial thermal processes beyond current technologies and allow for entirely new methods for processing materials; (2) Gain insight into new and innovative approaches to thermally intensify processes, reduce heat demand, harness waste heat, and use fuels and hydrocarbon feedstocks more efficiently; (3) Identify the R&D pathways to thermal process intensification (TPI) with the highest potential for impact and adoption by the industrial sector; (4) Define areas of research, development, and demonstration (RD&D) activities to accelerate development and application of emerging and transformative technologies to intensify thermal processes in industry. The scope and focus of the workshop were defined to meet these goals. Based on the available data for energy use and GHG emissions, the industries that collectively use more than 80% of the total process heating energy consumption were selected as primary focus areas. The chosen industries were combined into the following four groups based on similarities in their thermal processes: high-temperature metal processing (iron and steel industry, alumina-aluminum industry); high-temperature nonmetal and mineral processing (cement and glass industry); medium- to low-temperature thermal processing (food processing and pulp and paper industry as part of forest products sector); and hydrocarbon processing (petroleum refining and chemical industry). Furthermore, all potential TPI technologies associated with the processes defined were considered as part of the workshop. Different types of TPI technologies possible in industrial in the document.

42 ENGINEERING↗
DOE OSTI2025

Burning conditions and transportation pathways determine biomass-burning aerosol properties in the Ascension Island marine boundary layer

Abstract. African biomass-burning aerosol (BBA) in the southeast Atlantic Ocean (SEA) marine boundary layer (MBL) is an important contributor to Earth's radiation budget, yet its representation remains poorly constrained in regional and global climate models. Data from the Layered Atlantic Smoke Interactions with Clouds (LASIC) field campaign on Ascension Island (7.95° S, 14.36° W) provide insight into how burning conditions, fuel type, transport pathways, and atmospheric processing affect the chemical, microphysical, and optical properties of BBA between June and September 2017. A total of 10 individual plume events characterize the seasonal evolution of the BBA properties. Early-season inefficient fires, determined by low refractory black carbon to above-background carbon monoxide mixing ratios (rBC : ΔCO), led to enhanced concentrations of organic- and sulfate-rich aerosols. Mid-season efficient fires, determined by higher rBC : ΔCO values, led to rBC-enriched BBA. A mix of efficient and inefficient fires later in the season resulted in conflicting BBA properties. Prolonged transport (∼ 10 d) through the MBL and lower free troposphere (FT) facilitated chemical and aqueous-phase processing, which led to a reduction in organic aerosol mass concentrations. This resulted in lower organic aerosol (OA) to rBC (OA : rBC) mass ratios (2–5) in the MBL compared to higher values (5–15) in the nearby FT. These atmospheric and cloud oxidation processes yield more light-absorbing BBA and explain the notably low single-scattering albedo at 530 nm (SSA530) values (< 0.80) observed in the MBL. This study establishes a robust correlation between SSA530 and OA : rBC across the MBL and FT, underscoring the dependency of optical properties on chemical composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structural basis for heparan sulfate co-polymerase action by the EXT1–2 complex

Heparan sulfate (HS) proteoglycans are extended (-GlcAβ1,4GlcNAcα1,4-)n co-polymers containing decorations of sulfation and epimerization that are linked to cell surface and extracellular matrix proteins. In mammals, HS repeat units are extended by an obligate heterocomplex of two exostosin family members, EXT1 and EXT2, where each protein monomer contains distinct GT47 (GT-B fold) and GT64 (GT-A fold) glycosyltransferase domains. In this study, we generated human EXT1–EXT2 (EXT1–2) as a functional heterocomplex and determined its structure in the presence of bound donor and acceptor substrates. Structural data and enzyme activity of catalytic site mutants demonstrate that only two of the four glycosyltransferase domains are major contributors to co-polymer syntheses: the EXT1 GT-B fold β1,4GlcA transferase domain and the EXT2 GT-A fold α1,4GlcNAc transferase domain. Furthermore, the two catalytic sites are over 90 Å apart, indicating that HS is synthesized by a dissociative process that involves a single catalytic site on each monomer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Burning conditions and transportation pathways determine biomass-burning aerosol properties in the Ascension Island marine boundary layer

African biomass-burning aerosol (BBA) in the southeast Atlantic Ocean (SEA) marine boundary layer (MBL) is an important contributor to Earth’s radiation budget yet its representation remains poorly constrained in regional and global climate models. Data from the Layered Atlantic Smoke Interactions with Clouds (LASIC) field campaign on Ascension Island (-7.95° N, -14.36° E) detail how fire source regions (burning conditions and fuel type), transport pathways, and longer-term chemical processing affect the chemical, microphysical, and optical properties of the BBA in the remote MBL between June and September of 2017. Ten individual plume events characterize the seasonal evolution of BBA characteristics. Inefficient burning conditions, determined by the mass ratio of refractory black carbon to above-background carbon monoxide (rBC:ΔCO), enhance organic- and sulfate-rich aerosol concentrations in June–July. In contrast, the heart of the burning season exhibited higher rBC:ΔCO values indicative of efficient burning conditions, correlating with more rBC-enriched BBA. Toward the end of the burning season, a mix of burning conditions results in increased variation of the BBA properties. The BBA transit to Ascension Island was predominantly through slow-moving pathways in the MBL and lower free troposphere (FT), facilitating prolonged chemical transformations through heterogeneous and aqueous phase processes. Heterogeneous oxidation can persist for up to 10 days, resulting in a considerable decrease in organic aerosol (OA) mass. OA to rBC mass ratios (OA:rBC) in the MBL between 2 and 5 contrast to higher values of 5 to 15 observed in the nearby FT. Conversely, early-season aqueous-phase processes primarily contributed to aerosol oxidation and some aerosol production, but not appreciable aerosol removal. These two chemical processes yield more light-absorbing BBA in the MBL than in the FT and explain the notably low scattering albedo at 530 nm (SSA 530 ) values (< 0.80) at Ascension Island. This study establishes a robust correlation between SSA 530 and OA:rBC across both MBL and FT, underscoring the dependency of optical properties on chemical composition. These findings highlight how the interplay between chemical composition and atmospheric processing can be improved in global and regional climate models. Questions remain on the mixing of aerosols with different pathway histories, and on what accounts for the doubling of the mass absorption coefficient in the boundary layer.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Unraveling Electronic Trends in O* and OH* Surface Adsorption in the MO 2 Transition-Metal Oxide Series

Understanding the bond strength of O* and OH* intermediates to metal-oxide surfaces is key to predicting the catalytic activity in oxygen-based electrochemistry. Here, we uncover highly non-linear trends in O* and OH* adsorption energies across the 3d, 4d, and 5d series of MO 2 transition-metal (TM) oxide surfaces computed within Hubbard- U corrected density functional theory (DFT + U ). Investigating the electronic structure with crystal orbital Hamiltonian populations (COHP) of the relevant metal–oxygen bonds reveals that the spin-dependent coupling strength between metal-d and oxygen-2p atomic orbitals together with the extent of filling of bonding and anti-bonding orbitals are the primary contributors to the adsorption energy. Importantly, we show that the integrated COHP obtained purely from bulk calculations is a highly accurate descriptor for surface adsorption energetics that captures trends across the group 5–12 TM oxide series within 0.19–0.36 eV. Our results suggest a pathway to prediction of adsorption energies for an arbitrary metal–ligand catalyst system.

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

Assessing the sensitivity and repeatability of permanganate oxidizable carbon as a soil health metric: An interlab comparison across soils

Soil organic matter is central to the soil health framework. Therefore, reliable indicators of Soil organic matter is central to the soil health framework. Therefore, reliable indicators of changes in soil organic matter are essential to inform land management decisions. Permanganate oxidizable carbon (PDXC), an emerging soil health indicator, has shown promise for being sensitive to soil management. However, strict standardization is required for widespread implementation in research and commercial contexts. Here, we used 36 soils-three from each of the 12 USDA soil orders-to determine the effects of sieve size and soil mass of analysis on PDXC results. Using replicated measurements across 12 labs in the US and the EU (n = 7951 samples), we quantified the relative importance of 1) variation between labs, 2) variation within labs, 3) effect soil mass, and 4) effect of soil sieve size on the repeatability of PDXC. We found a wide range of overall variability in PDXC values across labs (0.03 to 171.8%; mean = 13.4%), and much of this variability was attributable to within-lab variation (median = 6.5%) independently of soil mass or sieve size. Greater soil mass (2.5 g) decreased absolute PDXC values by a mean of 177 mg kg -1 soil and decreased analytical variability by 6.5%. For soils with organic carbon (SOC) >10%, greater soil mass (2.5 g) resulted in more frequent PDXC values above the limit of detection whereas the lower soil mass (0.75 g) resulted in PDXC values below the limit of detection for SOC contents <5%. A finer sieve size increased absolute values of PDXC by 124 mg kg -1 while decreasing the analytical variability by 1.8%. In general, soils with greater SOC contents had lower analytical variability. These results point to potential standardizations of the PDXC protocol that can decrease the variability of the metric. We recommend that the PDXC protocol be standardized to use 2.5 g for soils <10% SOC. Sieve size was a relatively small contributor to analytical variability and therefore we recommend that this decision be tailored to the study purpose. Tradeoffs associated with these standardizations can be mitigated, ultimately providing guidance on how to standardize PDXC for routine analysis.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Intermediate Sr 2 Co 1.5 Fe 0.5 O 6-δ Tetragonal Structure between Perovskite and Brownmillerite as a Model Catalyst with Layered Oxygen Deficiency for Enhanced Electrochemical Water Oxidation

The generation of hydrogen in an environmentally benign way is highly essential to meet future energy demands. However, in the process of splitting water electrochemically, sluggish kinetics of the oxygen evolution reaction (OER) curtails its applicability, as it drags energy input. Herein, we synthesized SrCo-Fe-O oxides to optimize their OER activity by varying the Co/Fe ratio. Among them, Sr 2 Co 1.5 Fe 0.5 O 6-δ exhibited the best OER catalytic activity in the series, with an overpotential of 318 mV at 10 mA cm -2 and Tafel slope of 44.8 mV dec -1 . High-resolution neutron powder diffraction analysis identified an intermediate structure between the perovskite and brownmillerite, with alternating layers of disorderly orientated oxygen-deficient tetrahedra and fully stoichiometric octahedra. The unique stacking of tetrahedral and octahedral units facilitates desired interactions between the electrode surface and electrolyte. Theoretical calculations revealed that increased covalency of Co 3d and O 2p in Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide is another primary contributor to its augmented water oxidation ability. As a model for developing catalysts with such an intermediate structure, the synergetic effect of oxygen vacancy and hybridization between Co 3d and O 2p assured the Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide as a better catalyst for its enhanced OER activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗