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TEA and LCA Assessments of H2 Production from Coal, Coal/Biomass, and Biomass

This presentation was made at the "Gasification Technology Status and Pathways for Net-Zero Carbon Economy Workshop" held on November 30, 2022. The presentation primarily focuses on TEA/LCA results that NETL has developed for coal gasification w/ & w/o CCS as well as net-zero greenhouse gas coal/biomass gasification. Full reporting of these cases is publicly available in the NETL report titled "Comparison of Commercial, State-of-the-Art, Fossil-Based Hydrogen Production Technologies," April 2022. Additionally, the presentation describes current NETL work in support of the U.S. Department of Energy (DOE) Office of Fossil Energy and Carbon Management (FECM) Gasification Program in the areas of TEA/LCA/Markets analysis of biomass/MSW/waste plastics gasification to achieve cost reductions for net-zero H2 production.

Lewis, Eric↗

Probabilistic Nanomagnetic Memories for Uncertain and Robust Machine Learning

This project evaluated the use of emerging spintronic memory devices for robust and efficient variational inference schemes. Variational inference (VI) schemes, which constrain the distribution for each weight to be a Gaussian distribution with a mean and standard deviation, are a tractable method for calculating posterior distributions of weights in a Bayesian neural network such that this neural network can also be trained using the powerful backpropagation algorithm. Our project focuses on domain-wall magnetic tunnel junctions (DW-MTJs), a powerful multi-functional spintronic synapse design that can achieve low power switching while also opening the pathway towards repeatable, analog operation using fabricated notches. Our initial efforts to employ DW-MTJs as an all-in-one stochastic synapse with both a mean and standard deviation didn’t end up meeting the quality metrics for hardware-friendly VI. In the future, new device stacks and methods for expressive anisotropy modification may make this idea still possible. However, as a fall back that immediately satisfies our requirements, we invented and detailed how the combination of a DW-MTJ synapse encoding the mean and a probabilistic Bayes-MTJ device, programmed via a ferroelectric or ionically modifiable layer, can robustly and expressively implement VI. This design includes a physics-informed small circuit model, that was scaled up to perform and demonstrate rigorous uncertainty quantification applications, up to and including small convolutional networks on a grayscale image classification task, and larger (Residual) networks implementing multi-channel image classification. Lastly, as these results and ideas all depend upon the idea of an inference application where weights (spintronic memory states) remain non-volatile, the retention of these synapses for the notched case was further interrogated. These investigations revealed and emphasized the importance of both notch geometry and anisotropy modification in order to further enhance the endurance of written spintronic states. In the near future, these results will be mapped to effective predictions for room temperature and elevated operation DW-MTJ memory retention, and experimentally verified when devices become available.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

My Journey to NASA and role as a (Molecular) Biologist…

My journey to NASA started in undergrad, where I performed microbiology research and became hooked in the STEM fields. From there I earned a Ph.D. in Biochemistry and Molecular Biology from Mayo Graduate school where I performed Pancreatic Cancer research and then went on to perform postdoctoral research in Developmental Biology at the University of Miami. Trained as a biologist, I landed my first job at NASA as a mission scientist on the Rodent Research project. As a mission scientist, I led science activities associated with development, flight, and post-flight analysis of rodent research missions on the ISS in consultation with project engineers, operational specialists, mission PI(s), and mission Implementation Partner(s). I also assessed the feasibility of scientific experiments as a technical and scientific expert in rodent research on the ISS. Eager to learn more about the molecular changes that occur as a result of spaceflight exposure, I transitioned to the NASA GeneLab project where I eventually became the data processing lead. NASA’s GeneLab helps scientists understand how the fundamental building blocks of life – DNA, RNA, proteins, and metabolites – change from exposure to the space environment including microgravity and cosmic radiation exposure. GeneLab does so by providing fully coordinated epigenomics, genomics, transcriptomics, proteomics, and metabolomics data (collectively known as omics data) alongside essential metadata describing each spaceflight and space-relevant experiment. To maximize the intelligibility of these data, particularly for users with limited bioinformatics knowledge, GeneLab has started processing and analyzing these datasets to generate differential gene expression data and identify biological and physiological pathways that are dysregulated as a result of spaceflight. The user interface was designed to be accessible to a broad variety of users, including high school and college students who can use it to learn about omics data analysis and space biology. During the CA Space Grant Women in STEM Panel event, I will provide an overview of my journey to NASA including my work at NASA on both the Rodent Research and GeneLab projects. I will conclude by providing resources for opportunities to work with GeneLab and NASA at large followed by links to programs designed specifically to engage women in STEM fields.

Amanda M Saravia-Butler↗

Comparative Investigation of Benzene Steam Reforming over Spinel Supported Rh and Ir Catalysts

In a combined experimental and first-principles density functional theory (DFT) study, benzene steam reforming (BSR) over MgAl 2 O 4 supported Rh and Ir catalysts was investigated. Experimentally, it has been found that both highly dispersed Rh and Ir clusters (1-2 nm) on the MgAl 2 O 4 spinel support are stable during the BSR in the temperature range of 700-850°C. Compared to the Ir/MgAl 2 O 4 catalyst, the Rh/MgAl 2 O 4 catalyst is more active with higher benzene turnover frequency and conversion. At typical steam conditions with the steam-to-carbon ratio > 12, the benzene conversion is only a weak function of the H 2 O concentration in the feed. This suggests that the initial benzene decomposition step rather than the benzene adsorption is most likely the rate-determined step in BSR over supported Rh and Ir catalysts. In order to understand the differences between the two catalysts, we followed with a comparative DFT study of initial benzene decomposition pathways over two representative model systems for each supported metal (Rh and Ir) catalysts. A periodic terrace (111) surface and an amorphous 50-atom metal cluster with a diameter of 1.0 nm were used to represent the two supported model catalysts under low and high dispersion conditions. Our DFT results show that the decreasing catalyst particle size enhances the benzene decomposition on supported Rh catalysts by lowering both C-C and C-H bond scission. The activation barriers of the C-C and the C-H bond scission decrease from 1.60 and 1.61 eV on the Rh(111) surface to 1.34 and 1.26 eV on the Rh50 cluster. For supported Ir catalysts, the decreasing particle size only affects the C-C scission. The activation barrier of the C-C scission of benzene decreases from 1.60 eV on the Ir(111) surface to 1.35 eV on the Ir50 cluster while the barriers of the C-H scission are practically the same. The experimentally measured higher BSR activity on the supported highly dispersed Rh catalyst can be rationalized by the thermodynamic limitation for the very first C-C bond scission of benzene on the small Ir50 catalyst. The C-C bond scission of benzene on the small Ir50 catalyst is highly endothermic although the barrier is competitive with the barriers of both the C-C and the C-H bond-breakings on the small Rh50 catalyst. The calculations also imply that, for the supported Rh catalysts the C-C and C-H bond scissions are competitive, independently of the Rh cluster sizes. After the initial dissociation step via either the C-C or the C-H bond scission, the C-H bond breaking seems to be more favorable rather than the C-C bond breaking on the larger Rh terrace surface. This work was financially supported by the United States Department of Energy’s Office of Biomass Program’s. Computing time was granted by a user project at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Operational Overview of the EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) Northeast Pacific Field Deployment

The goal of the EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) field campaign is to develop a predictive understanding of the export, fate, and carbon cycle impacts of global ocean net primary production. To accomplish this goal, observations of export flux pathways, plankton community composition, food web processes, and optical, physical, and biogeochemical (BGC) properties are needed over a range of ecosystem states. Here we introduce the first EXPORTS field deployment to Ocean Station Papa in the Northeast Pacific Ocean during summer of 2018, providing context for other papers in this special collection. The experiment was conducted with two ships: a Process Ship, focused on ecological rates, BGC fluxes, temporal changes in food web, and BGC and optical properties, that followed an instrumented Lagrangian float; and a Survey Ship that sampled BGC and optical properties in spatial patterns around the Process Ship. An array of autonomous underwater assets provided measurements over a range of spatial and temporal scales, and partnering programs and remote sensing observations provided additional observational context. The oceanographic setting was typical of late-summer conditions at Ocean Station Papa: a shallow mixed layer, strong vertical and weak horizontal gradients in hydrographic properties, sluggish sub-inertial currents, elevated macronutrient concentrations and low phytoplankton abundances. Although nutrient concentrations were consistent with previous observations, mixed layer chlorophyll was lower than typically observed, resulting in a deeper euphotic zone. Analyses of surface layer temperature and salinity found three distinct surface water types, allowing for diagnosis of whether observed changes were spatial or temporal.The 2018 EXPORTS field deployment is among the most comprehensive biological pump studies ever conducted. A second deployment to the North Atlantic Ocean occurred in spring 2021, which will be followed by focused work on data synthesis and modeling using the entire EXPORTS data set.

Biological pump↗

Incorporation of measured photosynthetic rate in a mathematical model for calculation of non-structural saccharide concentration

A simple mathematical model for calculating the concentration of mobile carbon skeletons in the shoot of soya bean plants [Glycine max (L.) Merrill cv. Ransom] was built to examine the suitability of measured net photosynthetic rates (PN) for calculation of saccharide flux into the plant. The results suggest that either measurement of instantaneous PN overestimated saccharide influx or respiration rates utilized in the model were underestimated. If neither of these is the case, end-product inhibition of photosynthesis or waste respiration through the alternative pathway should be included in modelling of CH2O influx or efflux; and even if either of these is the case, the model output at a low coefficient of leaf activity indicates that PN still may be controlled by either end-product inhibition or alternative respiration.

NASA Program CELSS↗

My Journey to NASA and Role as a (Molecular) Biologist…

My journey to NASA started in undergrad, where I performed microbiology research and became hooked in the STEM fields. From there I earned a Ph.D. in Biochemistry and Molecular Biology from Mayo Graduate school where I performed Pancreatic Cancer research and then went on to perform postdoctoral research in Developmental Biology at the University of Miami. Trained as a biologist, I landed my first job at NASA as a mission scientist on the Rodent Research project. As a mission scientist, I led science activities associated with development, flight, and post-flight analysis of rodent research missions on the ISS in consultation with project engineers, operational specialists, mission PI(s), and mission Implementation Partner(s). I also assessed the feasibility of scientific experiments as a technical and scientific expert in rodent research on the ISS. Eager to learn more about the molecular changes that occur as a result of spaceflight exposure, I transitioned to the NASA GeneLab project where I eventually became the data processing lead. NASA’s GeneLab helps scientists understand how the fundamental building blocks of life – DNA, RNA, proteins, and metabolites – change from exposure to the space environment including microgravity and cosmic radiation exposure. GeneLab does so by providing fully coordinated epigenomics, genomics, transcriptomics, proteomics, and metabolomics data (collectively known as omics data) alongside essential metadata describing each spaceflight and space-relevant experiment. To maximize the intelligibility of these data, particularly for users with limited bioinformatics knowledge, GeneLab has started processing and analyzing these datasets to generate differential gene expression data and identify biological and physiological pathways that are dysregulated as a result of spaceflight. The user interface was designed to be accessible to a broad variety of users, including high school and college students who can use it to learn about omics data analysis and space biology. During the NASA Ames ECN at Lincoln HS Virtual Panel event, I will provide an overview of my journey to NASA including my work at NASA on both the Rodent Research and GeneLab projects. I will conclude by providing resources for opportunities to work with GeneLab and NASA at large followed by links to programs designed specifically to engage women in STEM fields.

Amanda M Saravia-Butler↗

Competitive binding of STATs to receptor phospho-Tyr motifs accounts for altered cytokine responses

Cytokines elicit pleiotropic and non-redundant activities despite strong overlap in their usage of receptors, JAKs and STATs molecules. We use IL-6 and IL-27 to ask how two cytokines activating the same signaling pathway have different biological roles. We found that IL-27 induces more sustained STAT1 phosphorylation than IL-6, with the two cytokines inducing comparable levels of STAT3 phosphorylation. Mathematical and statistical modeling of IL-6 and IL-27 signaling identified STAT3 binding to GP130, and STAT1 binding to IL-27Rα, as the main dynamical processes contributing to sustained pSTAT1 levels by IL-27. Mutation of Tyr613 on IL-27Rα decreased IL-27-induced STAT1 phosphorylation by 80% but had limited effect on STAT3 phosphorgylation. Strong receptor/STAT coupling by IL-27 initiated a unique gene expression program, which required sustained STAT1 phosphorylation and IRF1 expression and was enriched in classical Interferon Stimulated Genes. Interestingly, the STAT/receptor coupling exhibited by IL-6/IL-27 was altered in patients with systemic lupus erythematosus (SLE). IL-6/IL-27 induced a more potent STAT1 activation in SLE patients than in healthy controls, which correlated with higher STAT1 expression in these patients. Partial inhibition of JAK activation by sub-saturating doses of Tofacitinib specifically lowered the levels of STAT1 activation by IL-6. Our data show that receptor and STATs concentrations critically contribute to shape cytokine responses and generate functional pleiotropy in health and disease.

59 BASIC BIOLOGICAL SCIENCES↗

Integrated Risk Management Within NASA Programs/Projects

As NASA Project Risk Management activities continue to evolve, the need to successfully integrate risk management processes across the life cycle, between functional disciplines, stakeholders, various management policies, and within cost, schedule and performance requirements/constraints become more evident and important. Today's programs and projects are complex undertakings that include a myriad of processes, tools, techniques, management arrangements and other variables all of which must function together in order to achieve mission success. The perception and impact of risk may vary significantly among stakeholders and may influence decisions that may have unintended consequences on the project during a future phase of the life cycle. In these cases, risks may be unintentionally and/or arbitrarily transferred to others without the benefit of a comprehensive systemic risk assessment. Integrating risk across people, processes, and project requirements/constraints serves to enhance decisions, strengthen communication pathways, and reinforce the ability of the project team to identify and manage risks across the broad spectrum of project management responsibilities. The ability to identify risks in all areas of project management increases the likelihood a project will identify significant issues before they become problems and allows projects to make effective and efficient use of shrinking resources. By getting a total team integrated risk effort, applying a disciplined and rigorous process, along with understanding project requirements/constraints provides the opportunity for more effective risk management. Applying an integrated approach to risk management makes it possible to do a better job at balancing safety, cost, schedule, operational performance and other elements of risk. This paper will examine how people, processes, and project requirements/constraints can be integrated across the project lifecycle for better risk management and ultimately improve the chances for mission success.

Connley, Warren↗

Natural and Engineered Features Supporting Environmental Performance of Idaho National Laboratory’s Remote-Handled Low-Level Waste Disposal Facility

The Idaho National Laboratory’s (INL’s) Remote-Handled Low-Level Waste (RH LLW) Disposal Facility has been designed and constructed to receive waste generated at the INL site in support of the U.S. Department of Energy (DOE) Office of Nuclear Energy (NE) and Naval Reactors (NR) missions. The facility has been designed to receive legacy RH LLW currently in storage at INL facilities and new waste generated by nuclear research programs. RH LLW to be received at the facility is solid waste consisting of surface contaminated debris; ion exchange resins used to purify cooling and canal water; activated metals generated during reactor core change outs and Naval spent fuel management; and nuclear Research & Development. Disposal of INL's RH LLW poses unique disposal challenges due to high radiation levels (contact rates up to 600 Sv/hr [60,000 Rem/hr]) that require remote handling and adequate shielding for transportation and disposal. The facility has been designed to meet the requirements of DOE Order 435.1 [1], including the all-pathways dose, air pathway dose, inadvertent intruder doses, and radon emissions limits. This paper presents an overview of natural and engineered design features that support the safety case and enhance the environmental performance of the facility. These include location selection, use of reinforced pre-cast concrete vaults; a robust hydraulic drainage system; use of steel waste canisters for waste disposal; the facility monitoring system; facility layout; and crediting waste forms. The facility performance assessment (PA) [2] developed to meet the requirements of DOE Order 435.1 “Radioactive Waste Management” credits each of these protective features. Releases from waste forms disposed of at this facility are limited by corrosion of the steel waste canisters which will ultimately allow contact with infiltrating water followed by transport of radionuclides from the vault system. The steel waste canisters were credited for their ability to limit water contact with the waste based on the demonstrated ability of the reinforced pre-caste concrete vaults to provide long-term structural protection of the steel waste canisters. Verification of hydraulic and concrete performance was conducted through laboratory data, field infiltration tests supported by a robust monitoring system, and numerical modeling. Releases into the vault system from activated metals are based on site-specific corrosion data. Radionuclide transport from the vault system from all waste forms is based on site-specific climatological, hydrologic, and stratigraphic data. At INL, the groundwater pathway historically and appropriately has received the most attention. By crediting aspects of the natural system, the engineered vault system, and the waste, estimated radiologic doses via the groundwater pathway are minimal. Air pathway doses were reduced by differentially crediting corrosion of aluminum and stainless steel activated metals resulting in the pathway being screened out of the PA. Groundwater and inadvertent intruder doses were reduced through selective facility layout. This paper provides an overview of the system-wide protective features incorporated into the facility design along with an extensive reference list to supporting technical papers and analyses that provide data and interpretation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Materials for Advanced Ultra-Supercritical (AUSC) Steam Turbines – AUSC Component Demonstration

The work by the United States Department of Energy (U.S. DOE)/Ohio Coal Development Office (OCDO) Advanced Ultra-Supercritical (AUSC) Steam Boiler and Turbine Materials Consortia from 2001 through September 2015 was primarily focused on lab scale and pilot scale materials testing. The field testing included air-cooled probes and steam-cooled “loops” that were installed into existing utility boilers to gain exposure of these materials to realistic conditions of high temperature and corrosion due to the constituents in the coal ash. Successful research and development resulted in identification of metallic alloy materials and fabrication processes suited for power generation applications with metal temperatures up to approximately 1472°F (800°C). These materials or alloys have shown, in extensive laboratory tests and shop fabrication studies, to have excellent applicability for high-efficiency low CO2 transformational power generation technologies. However, as valuable as these material field tests have been for obtaining information, their scale is significantly below that required to minimize the risk associated with a power company building a multi-billion-dollar AUSC power plant. To decrease the identified risk barriers to full-scale implementation of these advanced materials, the U.S. DOE/OCDO AUSC Steam Boiler and Turbine Materials Consortia identified the key areas of the technology that need to be tested at a larger scale. Based upon the recommendations and outcome of a Consortia-sponsored workshop with the U.S.’s leading utilities, a Component Test (ComTest) Program for AUSC was proposed. The AUSC ComTest program would define materials performance requirements, plan for overall advanced system integration, design critical component tests, fabricate components for testing from advanced materials, and carry out the tests. A Pre-FEED evaluation of the test facility including the evaluation of three potential sites has been completed and previously reported. This report describes the Front-End Engineering Design (FEED), Detailed Engineering and the Environmental Assessment of the ComTest project. A significant amount of work was accomplished during Phase 1 to identity the components, as well as the component size, that would be manufactured from advanced alloys such as INCONEL 740H or HAYNES 282 alloys. Pathways to supply these components for ComTest have been identified as well as any further development that would be required. Every project of this nature has challenges and this project was no exception. The greatest challenge has been the project cost. Largely due to the infrastructure and balance of plant equipment upgrades required for Youngstown Thermal, the estimated project cost for the “base case” project was greater than originally budgeted. The project team spent a significant amount of time exploring opportunities for reducing the project cost. These options included: • Youngstown Thermal was exploring building a Combined Heat and Power (CHP) unit at their facility. The Youngstown Thermal staff, supported by Thermal Engineering Group, worked with the project team to determine whether it was economically desirable to supply ComTest with steam and other utilities, which would be supplied by the CHP project. • The project team also evaluated opportunities to optimize the project scope to reduce cost, such as reducing project scope by eliminating the Superheater Outlet Header test. • Southern Company had offered two sites as possible host locations for ComTest. Both sites had infrastructure in place such as steam from an existing unit, natural gas, cooling water and ample electrical power that would be required to be added at the Youngstown Thermal site. Utilizing this existing infrastructure could reduce the project cost. An additional project challenge was the departure of Babcock and Wilcox from the project in September 2016. This project setback was overcome by GE Power’s willingness to assume the design of the ComTest superheater. Since the project could not proceed without the superheater, this was a very positive project development. The merger of the GE Power and Alstom Power steam turbine divisions created synergies leading to the conclusion that instead of building a small-scale turbine, a more practical and useful endeavor would be to validate the manufacturing technology and supplier readiness for fabricating and machining full scale steam turbine components. Consequently, in March 2017, GE Power decided that a steam turbine test would not be necessary as part of the ComTest demonstration. Removing the operational testing of the steam turbine from ComTest further reduced the total project cost. Additionally, there was an opportunity to move ComTest from Youngstown Thermal to one of the Southern Company sites and operate ComTest at supercritical steam conditions and test the steam turbine main stop/control valve at a temperature and pressure that would be representative of the conditions of a high pressure steam turbine inlet valve. The steam could also possibly be returned to the host boiler so there would be no economic penalty of using this steam for ComTest. Relocating the project could further reduce the project cost due to the infrastructure already in place, including high pressure natural gas and cooling water, and the potential for heat integration, allowing a reduction of operating costs. Due to these potential cost reductions, it was decided to move the project away from Youngstown Thermal in March 2017. As integrating ComTest at the Southern Company site was explored, an issue was raised regarding the integration of the ComTest cycle with the plant steam cycle. Steam would be supplied to ComTest at nominally ~3865 psia and 775°F. The steam would be heated with natural gas to 1400°F for the valve test and then cooled to 1000°F so that the steam would be returned to the host boiler at the same conditions as their high pressure steam turbine inlet. However, there were concerns raised that the addition of the energy (natural gas) to the steam could trigger a New Source Review on the unit. Southern Company did not want ComTest to cause this review, so condensing all of the steam exiting ComTest and returning it to the host steam cycle as condensate was explored to insure there would be no implication that ComTest was adding energy to the host plant’s steam cycle. Ultimately, Southern Company decided that they wanted to “decouple” ComTest from the operating unit, making ComTest self-supporting, similar to the Youngstown Thermal “base case.” Without the steam turbine, the project team reached a consensus that operating the ComTest Superheater and steam turbine valves at the typical pressure of a package boiler (~1000 psig) would not generate enough useful technical information to justify the cost of the test. Therefore, it was decided in the December 2017 project quarterly meeting to cancel the operational phase of ComTest. Throughout the engineering phase of ComTest, manufacturing and supply chain challenges were identified. When GE Power recommended dropping the steam turbine test from ComTest, they identified many important manufacturing issues that should be evaluated and demonstrated. Other challenges had been raised by the GE Power group designing the superheater as well as those engineering components such as pressure relief and steam turbine bypass valves. In the December 2017 meeting, the project team decided that it was more beneficial to the AUSC technology to pursue these manufacturing and supply chain issues as Phase 2 of the ComTest project. This report is organized in the following manner: • Section 2 discusses the ComTest project background and organization. • Section 3 discussed project management. • Section 4 discusses the design of the ComTest AUSC components – the Superheater, steam turbine and Superheater Outlet Header. • Section 5 discusses the implementation of ComTest at Youngstown Thermal and the Southern Company site. • Section 6 discusses the development of the AUSC Supply Chain • Section 7 discusses the recommended plan for Phase 2 of ComTest

01 COAL, LIGNITE, AND PEAT↗

Experimental Setup to Investigate Hydrogen Isotope Retention on Powder Samples as Slag/Dust Proxies for Advanced Fusion Reactors

Slag/dust formation is one of the critical issues regarding tritium retention in advanced fusion reactors. We upgraded an ultrahigh vacuum device, the sample exposure station (SES), to perform temperature-programmed desorption (TPD), also known as thermal desorption spectroscopy, to investigate deuterium (D) retention in powder samples that are utilized as proxies for slag/dust particles formed in fusion reactors. TPD analysis, calibrated for the desorption rate, was successfully performed on commercially available crystalline/amorphous boron (B) powder after D 2 neutral gas or D + ion exposure. We calibrated the B powder temperature measurement for TPD analysis utilizing a D 2 desorption peak from B-D bonding known for its desorption temperature ~700 K. We introduce a separation procedure of observed D TPD signals, convoluted for corresponding D retention pathways, that was necessary for TPD analysis. This is the first report on the retention of D 2 neutral gas to B, and this observation was enabled by utilizing the B powder sample, which has a larger surface area than films commonly used in laboratory experiments. In conclusion, the upgraded SES system will enable us to investigate hydrogen isotope behaviors for powder/dust samples of various elemental compositions, including metals.

Plasma-facing component debris↗

ON THE FORMATION AND ISOMER SPECIFIC DETECTION OF PROPENAL (C{sub 2}H{sub 3}CHO) AND CYCLOPROPANONE (c-C{sub 3}H{sub 4}O) IN INTERSTELLAR MODEL ICES—A COMBINED FTIR AND REFLECTRON TIME-OF-FLIGHT MASS SPECTROSCOPIC STUDY

The formation routes of two structural isomers—propenal (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—were investigated experimentally by exposing ices of astrophysical interest to energetic electrons at 5.5 K thus mimicking the interaction of ionizing radiation with interstellar ices in cold molecular clouds. The radiation-induced processing of these ices was monitored online and in situ via Fourier Transform Infrared spectroscopy and via temperature programmed desorption exploiting highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon ionization in the post irradiation phase. To selectively probe which isomer(s) is/are formed, the photoionization experiments were conducted with 10.49 and 9.60 eV photons. Our studies provided compelling evidence on the formation of both isomers—propenal (C{sub 2}H{sub 3}CHO) and cyclopropanone (c-C{sub 3}H{sub 4}O)—in ethylene (C{sub 2}H{sub 4})—carbon monoxide (CO) ices forming propenal and cyclopropanone at a ratio of (4.5 ± 0.9):1. Based on the extracted reaction pathways, the cyclopropanone molecule can be classified as a tracer of a low temperature non-equilibrium chemistry within interstellar ices involving most likely excited triplet states, whereas propenal can be formed at ultralow temperatures, but also during the annealing phase via non-equilibrium as well as thermal chemistry (radical recombination). Since propenal has been detected in the interstellar medium and our laboratory experiments demonstrate that both isomers originated from identical precursor molecules our study predicts that the hitherto elusive second isomer—cyclopropanone—should also be observable toward those astronomical sources such as Sgr B2(N) in which propenal has been detected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revitalizing Canton City Schools: A Sustainable and Cost-Effective Energy Efficiency Plan

The primary objective of this project was to focus on conducting the American Society of Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE) Level 2 Energy Audits of all the schools/school facilities in the portfolio, and on developing a comprehensive Strategic Plan for implementing energy improvements. The overall aim of budget period 1 (BP1) was to implement Energy Audits and the Strategic Plan to provide a clear pathway to prioritize energy improvements as well as allow the district to access private sector funding (if needed) and/or tax credits and realize high-impact health and safety benefits for Budget Period 2.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Nitrogen acquisition and retention pathways in sustainable perennial bioenergy grass cropping systems

Abstract Perennial tall grasses show promise as bioenergy crops due to high productivity and efficient nutrient use. Ongoing research on bioenergy grasses seeks to reduce their reliance on synthetic nitrogen (N) fertilizer, the manufacture of which relies on fossil fuel combustion. Excessive use of fertilizers also causes adverse environmental consequences and leads to the evolutionary loss of plant traits beneficial to sustainable N cycle. Notably, perennial tall grasses have exhibited the potential to maintain high biomass yield without the need for N fertilizer or causing soil N depletion. Perennial grasses can be adept at interacting with their microbial partners to facilitate N acquisition and retention via mechanisms such as biological N fixation and nitrification inhibition. These inherent N management traits should be preserved and optimized at the this early stage of bioenergy grass breeding programs. This review examines the impact of external N on bioenergy grass production and explores the potential of leveraging advantageous N‐cycling attributes of perennial tall grasses, laying groundwork for future management and research efforts. With minimized dependency on external N input, the cultivation of perennial energy grasses will pave the way toward more resilient agricultural systems and play a significant role in addressing key global energy and environmental challenges.

Agriculture↗

Systematic Technology Evaluation Program for SiC-based BWR Channel Box

Silicon carbide (SiC) –based accident-tolerant fuel (ATF) cladding of light water reactors (LWRs) has become a topic of great interest in nuclear material development since the Fukushima Dai-ichi Nuclear Power Plant accident. Extensive development of SiC cladding has identified benefits of the concept, including its inherent accident resistance and neutronic performance. Advancements achieved during the development of SiC-based ATF cladding have made it attractive for use in accident-tolerant cores of LWRs. In this document, we consider the use of SiC-based materials to replace the zirconium alloy used for the channel boxes of boiling water reactors. Both accident resistance and prevention of the bowing observed in current grades of channel boxes are needs driving the exploration of a new channel box system. To provide a pathway for channel box development, this document lays out (1) a current technology overview, (2) the technology gap, and (3) a systematic technology evaluation plan. The objectives of the technology evaluation plan are to address key feasibility issues revealed by the knowledge gap analysis and to contribute to advancing the technology readiness level. Further development will be required in the technology implementation phase. The technology evaluations include understanding the behavior of channel boxes under both normal and off-normal conditions, identifying potential mitigation strategies for the issues if necessary, and improving channel box performance based on the knowledge obtained. The structure of the technology evaluation plan and each task are shown in Figure S.1. The knowledge gap analysis identified key research areas, including irradiation effects, hydrothermal corrosion, accident behavior, and design and manufacture. These are common issues between SiC-based channel boxes and SiC-based fuel cladding, although technical evaluations specific for the channel box components are required. This document also describes details of the technical feasibility evaluation methods and plans.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Click-chemistry compatible structures, click-chemistry functionalized structures, and materials and methods for making the same

According to various embodiments, systems, methods, and computer program products for click-chemistry compatible structures, additive manufacturing resins for forming the same, and method of formation of such structures and resins, as well as techniques for functionalizing click-chemistry compatible structures are disclosed. The inventive structures generally include a plurality of photo polymerized molecules structurally arranged according to a three-dimensional pattern, while surfaces of the structure are functionalized with one or more click-chemistry compatible molecules each having one or more click-chemistry compatible functional groups. The structures may be formed from single- or dual-component resins, each having unique synthetic pathways. The resulting structures may be functionalized for utility in a wide range of applications by leveraging click chemistry to further functionalize the structure with organic additives also compatible with click-chemistry reaction schemes.

36 MATERIALS SCIENCE↗

Comparison of the Photodesorption Activities of cis-Butene, trans-Butene and Isobutene on the Rutile TiO 2 (110) Surface

The chemical and photochemical properties of three butene molecules (cis-butene, trans-butene and isobutene) were explored on the clean rutile TiO 2 (110) surface using temperature programmed desorption (TPD) and photon simulated desorption (PSD). At the low coverage limit, trans-butene was the most strongly bound butene on the TiO 2 (110) surface, desorbing at ~ 210 K, however increased intermolecular repulsions between trans-butene molecules at higher coverage diminished its binding. Both cis-butene and isobutene saturated the first layer on TiO 2 (110) at a coverage of ~0.50 ML in a single TPD feature at 184 and 192 K, respectively. In contrast, the maximum coverage that trans-butene could achieve in its 210 K peak was ~1/3 ML, with higher coverages resulting a low temperature desorption at ~137 K. Coverages of these molecules above 0.50 ML resulted in population of second layer and multilayer states. The instability of trans-butene at a coverage of 0.5 ML on the surface was linked to the inversion center in its symmetry. In the absence of coadsorbed oxygen, the primary photochemical pathway of each butene molecule on TiO 2 (110) was photodesorption. The photoactivities of these molecules on TiO 2 (110) at an initial coverage of 0.50 ML followed the trend: isobutene > cis-butene > trans-butene. In contrast, the photoactivities of low coverages of cis-butene and trans-butene exceeded those measured at 0.50 ML. These data suggest that intermolecular interactions (repulsions) play a significant role in diminishing the photoactivities of weakly bound molecules on TiO 2 photocatalysts. Work reported here was supported by the U.S. Department of Energy, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences, and Biosciences, and performed in the Williams R. Wiley Environmental Molecular Science Laboratory (EMSL), a Department of Energy user facility funded by the Office of Biological and Environmental Research. Pacific Northwest National Laboratory is a multiprogram national laboratory operated for the U.S. Department of Energy by the Battelle Memorial Institute under contract DEAC05-76RL01830.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗