Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “dehydration”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

Formation of Tropopause Cirrus clouds by Typhoon-induced gravity waves during the Asian Summer Monsoon: A Case Study from the BATAL 2017 Campaign

Cirrus clouds in the Tropical Tropopause Layer (TTL) have a net warming impact on Earth’s climate and they regulate the amount of water vapor entering the lower stratosphere through dehydration process near the cold-point tropopause. During the Boreal summer, Asian Summer Monsoon (ASM) is an important source of cirrus clouds and humidity in the TTL owing to frequent deep convection. However, better representation of convection and TTL cirrus clouds in global climate models is needed for accurate assessment of their response to changing climate. In this study, we investigate the mechanisms involved in the formation of a tropopause cirrus cloud layer observed during the Balloon measurement campaigns of the Asian Tropopause Aerosol Layer (BATAL) over Hyderabad (17.47 °N, 78.58 °E), India on 23 August 2017. A subvisible cirrus cloud layer (optical thickness ~0.025) was detected by a backscatter sonde (COBALD) onboard a balloon near the cold-point tropopause (CPT, temperature~ -86.4 ° C, altitude~17.9 km) which was later confirmed by the CATS lidar on the ISS. Simultaneous measurements from an optical particle counter (Boulder Counter) revealed the presence of ice crystals smaller than 50 microns in this layer. The formation mechanism responsible for this tropopause cirrus is investigated using a technique combining three-dimensional back-trajectories, satellite observations, and ERA5 reanalysis data. Satellite observations revealed that the overshooting convection associated with a category-3 typhoon Hato, which hit Macau and Hong Kong on 23 August 2017 injected ice into the lower stratosphere. This caused a hydration patch that followed the ASM anticyclone subsequently moving towards Hyderabad. The presence of tropopause cirrus cloud layers in the cold temperature anomalies and updrafts along the back-trajectories indicated towards the role of typhoon-induced gravity waves in their formation. This case study highlights the role of typhoons in influencing the formation of tropopause cirrus clouds through stratospheric hydration and gravity waves in the ASM anticyclone.

Amit Kumar Pandit↗
NASA NTRSDate not supplied

Asteroid (142) Polana at 3 µM and Its Linkage to the Primitive Asteroid (101955) Bennu

The Polana family is a low-albedo family located at a low inclination and a semimajor axis of ~2.42 au in the inner main asteroid belt. This family is likely the source of primitive near-Earth asteroids, including the OSIRIS-REx mission target (101955) Bennu. The B-type asteroid 142 Polana is the largest remnant of the "New Polana" family, and it has been spectrally (~0.5-2.5 µm) and dynamically linked to Bennu. Here, we investigate the compositional linkage of asteroids Polana and Bennu using spectra measured at longer wavelengths (~1.6-4.0 µm), which cover the 3- µm band. Polana’s spectra were measured at NASA IRTF using the LXD mode of SpeX. Bennu’s spectra were measured by OSIRIS-REx’s OVIRS spectrometer and revealed that this primitive asteroid is hydrated consistent with CM, CI, or CR carbonaceous chondrites. Polana’s LXD spectra, on the hand, show that the parent body of the Polana family is not hydrated (i.e., no absorption band at ~ 3.0 µm). Additionally, Polana’s LXD spectra do not indicate the presence of organics and/or carbonates. Polana's lack of significant water, organic, and carbonate spectral features on its surface could be related to the degree of heating in the Polana family-forming event and the reaccretion of ejecta that contributed to additional heating. The Polana family-forming event could also expose the parent body's dehydrated, organic/carbonate-poor interior. These results will be placed in the context of other low-albedo families and background objects in the inner main belt. An approved JWST program to observe Polana (with both NIRSpec and MIRI) will be able to assess if there is a Ryugu-like band and should allow a comparison of the MIR spectrum to Bennu.

Driss Takir↗
NASA NTRSDate not supplied

Validation of A Sensorimotor Disorientation Ground Analog

INTRODUCTION Simulating the sensorimotor disorientation effects of gravity transitions after prolonged stays in microgravity is exceedingly challenging on Earth. In a previous study [1], a Sensorimotor Disorientation Analog (SDA) was developed based on subjective feedback from previously flown astronauts. The purpose of this study was to validate this SDA by comparing performance in movement tasks that have a wealth of spaceflight data against task performance while using the SDA. METHODS Thirty healthy non-astronaut subjects (17 males, 13 females; Mean ± SD, Age: 33.5 ± 7.2 years, Height: 68.0 ± 3.4 in, Weight: 164 ± 26 lbs.) volunteered to participate in this study. Subjects performed three movement tasks: computerized dynamic posturography (CDP), obstacle walk, and tandem walk. For CDP, subjects maintained an upright stance for 20s with eyes closed on an unstable pitch sway-referenced platform with head erect (sensory organization test (SOT)-5) and with head pitch ±20° to an auditory cue(SOT-5M). The obstacle walk involved a sit-to-stand with 10s of quiet stance followed by walking to and around a cone placed 4m away while navigating a 30cm obstacle to the cone and back. The tandem walk involved walking heel-to-toe for approximately 10-12 steps with eyes open and eyes closed. Subjects performed the three movement tasks under three levels of the SDA replicating different time points of recovery: none (preflight), low (Return (R)+24- 48hours), and high (R+0- 24hours). The SDA included galvanic vestibular stimulation (GVS) to disorient the vestibular system and a weighted suit (trunk, wrists, and ankles) to alter proprioceptive feedback and replicate subjective heaviness. RESULTS As the SDA magnitude increased, overall performance outcomes decreased. However, the ability of the SDA to replicate the range of astronaut postflight performance was task dependent. CDP SOT-5 performance across SDA levels closely replicated astronaut performance at all time points. SOT-5M, however, had minimal performance changes across SDA levels and was unable to replicate astronaut performance. The obstacle walk showed performance changes across SDA levels and matched astronaut performance preflight and at R+24-48hrs (low). Obstacle walk performance at the high SDA level was reduced in comparison to the low level; however, it was not replicative of astronaut performance immediately after landing. Last, tandem walk had distinct groupings of performance across SDA levels and was able to elicit a high level of disorientation consistent with R+0-24 hours (high) postflight performance for eyes open and eyes closed. The low SDA level for both eyes open and eyes closed was more disruptive than previous crewmember performance at the R+24-48 hours timepoint. CONCLUSION The SDA was developed to replicate postflight sensorimotor disruptions. However, it is well-known that immediately post-landing, astronauts can experience motion sickness, dehydration, fatigue, orthostatic intolerance, illusory sensations, lumbar pain, etc. This multi-system response to return to 1G varies widely across astronauts and, as such, it was not unexpected that the extreme ends of responses in the R+0-24hrs time period were the most difficult to replicate. These results suggest that the SDA levels are able to elicit distinct performance groupings and, although not able to perfectly replicate R+0-24hrs, the SDA did replicate a large range of performance after return to Earth.

S C Moudy↗
NASA NTRS2023

Phyllosilicate Decomposition on Bennu Due to Prolonged Surface Exposure

The Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission to carbonaceous asteroid (101955) Bennu performed detailed mapping with a suite of instruments to characterize the composition and geology of its surface. Here we use data from the OSIRIS-REx Thermal Emission Spectrometer (OTES) instrument to investigate the relationship of OTES-derived spectral indices to other derived data products from OTES, the OSIRIS-REx Camera Suite (OCAMS), and the OSIRIS-REx Visible and InfraRed Spectrometer (OVIRS) at global and local scales. We quantitatively confirm that high values of the OTES silicate stretching slope (from ∼10 to ∼12 μm) in midday spectra that are indicative of thin and/or patchy dust cover are strongly associated with low thermal inertia (high porosity), low albedo boulders on Bennu. These high porosity boulders have brecciated textures with embedded clasts that likely originated on Bennu's parent body or during its disruption. The high porosity of these boulders is a key factor in the local production of the dust or its entrapment, as some large, brecciated boulders with a lower porosity have little evidence of dust. A second OTES spectral parameter, the silicate bending band depth near 22.7 μm applied to early evening spectra, is not correlated to thermal inertia, but is weakly to strongly correlated to albedo, OVIRS-derived 1.05 μm and 2.74 μm band depths, OVIRS-derived hydrogen abundance, and modeled nanophase troilite abundance. In several regions on Bennu there is a strong spatial relationship between these parameters, whereby areas with shallower silicate bending bands also have shallower 1.05 μm and 2.74 μm bands and lower albedo with higher nanophase troilite abundances. These correlations, combined with analysis of the silicate bending band in laboratory experiments of space weathered and mildly heated carbonaceous chondrites, suggests that decreased silicate bending band depths signify decomposition of phyllosilicates, likely Fe-bearing, due to space weathering or mild heating (<600 °C) via solar radiation during Bennu's time in near-Earth space. There is a strong association of larger silicate bending band depths in areas dominated by small rocks and unresolved material and in areas with small (≤ 25 m) craters identified as the spectrally reddest on Bennu, suggesting that this material has been more recently exposed due to impact and/or mass wasting processes. The shallowest silicate bending depths are associated with larger rocks and boulders that appear to have the longest surface exposure history, although there is band depth variation among them suggesting either initial composition variation that resulted in different responses to space weathering or heating, or varied exposure history of individual boulders themselves. We predict that any grains returned from Bennu with a significant surface exposure history will be characterized by shallower 22.7 μm, 1.05 μm and 2.7 μm band depths and increased sulfide (troilite) abundance, as well as textural and chemical evidence for phyllosilicate dehydration.

Asteroids, surfaces↗
NASA NTRSDate not supplied

Insights Into the CM Parent Body's Interior: A Comparative Study With Bennu's Bright Boulders

CM (Mighei-like) chondrites, primitive and water-rich asteroid samples from the early solar system, are significant for their potential role in delivering water and organic compounds to Earth [1-2]. Their resemblance to near-Earth asteroids Bennu and Ryugu, the targets of recent sample return missions, highlights their importance. What we learn from CM chondrites can be applied to these intriguing celestial bodies. Initial studies indicated that phyllosilicate-rich C chondrites underwent low-temperature aqueous alteration (<150°C) [3-5]. Subsequent research revealed that some experienced post-hydration thermal metamorphism at temperatures between ∼200°C and >750°C, resulting in dehydrated minerals and reduced volatile elements [6-9].This finding challenged the previous assumption that these chondrites had not undergone significant thermal metamorphism.

I Kerraouch↗
NASA NTRS2024

Evidence Report: Risk of Renal Stone Formation

Kidney stone formation and passage has the potential to greatly impact mission success and crewmember health, especially for long-duration missions. Alterations in hydration state (relative dehydration), spaceflight-induced changes in urine biochemistry (urine super-saturation), and bone metabolism (increased calcium excretion) during exposure to microgravity may increase the risk of kidney stone formation. There are possible countermeasures and treatments available that are used terrestrially that may then be applied to spaceflight. Directed Acyclic Graphs (DAGs) are used throughout this document to communicate spaceflight conditions that may lead to renal stone formation, the countermeasures that may be used to prevent their formation, and possible treatment modalities. The DAGs are sorted by strength of evidence, according to Table 6. Additionally, for the full Renal Stone Evidence Report Content: Directed Acyclic Graphs and Evidence Report, please see Appendix A, Expanded Directed Acyclic Graphs (DAGs) and Evidence. Additionally, a proposed Concept of Operations for the Prevention, Diagnosis, and Treatment of Renal Stones for a Mars Mission was created in conjunction with and to complement this Evidence Report update. Please see Appendix B, Proposed Expanded Concept of Operations for the Prevention, Diagnosis and Treatment of Renal Stones for Mars Missions, for the full report. Areas in the following Evidence Report will be cross-linked to scenarios from the Concept of Operations.

Emily Stratton↗
NASA NTRSDate not supplied

BioNutrients-3: Precision Fermentation, Pasteurization, and Pathogen Detection - Towards Safe Fermentation and Production of Nutrients in Space

The BioNutrients (BN) project is developing a microbial manufacturing approach to supplement the NASA food system to address known nutrient degradation associated with long-term storage. BN uses synthetic biology to deliver high-value nutrients and therapeutics through genetic engineering of microbes and production of fermented food products like yogurt and kefir, in a fully dehydrated system. On-demand production of nutrients for human consumption requires rigorous safety protocols to ensure contaminants are not introduced during the fermentation process. The third iteration of the BN flight project, BN-3, further develops the BN project by investigating strategies for pathogen detection and pasteurization in microgravity. BN-3 will test the limits of pathogen detection using whole genome sequencing, standard microbial assays and the NASA Ames E-Nose, a volatile carbon nano tube-based sensor array, to detect unwanted microbes. BN-3 also expands on the number of nutrients produced in a single bioreactor to enhance efficiency of the system by combining production of B vitamins in conjunction with the carotenoids, beta-carotene and zeaxanthin. Serial production of food products through yogurt passaging, new updates to the fluorinated ethylene propylene bags to allow crew access via a straw, as well as use of a food safe pH indicator dye to indicate readiness of the food product, will further enhance the useability of this system. This presentation will provide status of the BN-3 flight project with the aim of advancing in-space biomanufacturing for on-demand microbially based food production for future space exploration.

Biomanufacturing↗
DOE OSTI2021

Measuring accurate optical constants of uranium minerals for use in optical modeling of infrared spectra

Knowledge of the bulk optical constants n and k of solids or liquids allows researchers to accurately predict the absorption, reflection, and scattering properties of materials for different physical forms. Indeed, chemically complex materials such as minerals can have an almost limitless variety of morphologies, particle sizes, shapes, and compositions, but the optical properties of such species can be predicted if the optical constants are known. For species such as minerals, however, there can be additional challenges due to e.g. hydration or dehydration during the course of the optical constants measurement. Here, we describe the protocols to obtain the bulk optical constants n and k of uranium-bearing minerals and ores such as uraninite or autunite. If quality n and k data are at hand, the (infrared) reflectance spectra can be predicted for different particle sizes and morphologies and the modeling results for various scenarios can be derived.

infrared (IR) spectroscopy, optical constants, ura↗
DOE OSTI2021

Enhanced heavy oil recovery by low salinity polymer flood combined with microgel treatment

“Heavy oil resources account for a large portion of the total oil reserves around the world. The target heavy oil reservoir is located on Alaska’s North Slope (ANS). Advantages of low-salinity HPAM polymer (LSP) over high-salinity polymer (HSP) were demonstrated. LSP could recover more oil with 40% less polymer consumption. No additional oil was recovered by HSP after LSP flood. The first-ever polymer flood pilot on ANS showed remarkable success regarding water cut reduction, oil production increase, delayed breakthrough, and projected oil recovery improvement. Polymer alone was insufficient to achieve satisfactory recovery as the reservoirs were highly heterogeneous. Microgels could improve the effectiveness of polymer flood by reducing water cut and increasing oil recovery. Favorable working conditions were identified. Microgel transport behavior was studied using superpermeable sandpacks (27-221 darcies) with multiple pressure sensors. The particle-to-pore matching size ratio significantly impacted the effectiveness of the gels. A threshold differential pressure (ΔPth) and critical pressure gradient (∇Pcr) were required to push the gels to penetrate and propagate through the channels. The ΔPth and ∇Pcr revealed the underlying mechanisms of selective penetration/placement behavior of microgels in heterogeneous reservoirs. Diagrams were developed to estimate the maximum propagation distance of the gels in channels in conceptual field applications. Sandwich-like channel models and methodologies were developed to comprehensively evaluate the effectiveness of gel materials. Gel retention in the channels was quantified. Results also indicated that the retained gels were dehydrated. Fluid diversion and sweep improvement after gel treatments were evaluated by tracer tests”--Abstract, page iv.

Zhao, Yang↗
DOE OSTI2023

Process Intensification for Direct Conversion of Biomass-Based Syngas to High Octane Gasoline

The conversion of lignocellulosic-derived carbon sources via the creation of a CO2 rich syngas stream provides means to produce liquid hydrocarbon fuels, with advancements intended to create a cost-competitive method of sequential conversion via methanol and dimethyl ether intermediates. Previously developed methods with Cu/Beta zeolites enabled the conversion of dimethyl ether to linear and branched hydrocarbons, with high selectivities towards products with high-octane fuel properties. Through process intensification, use of a single reactor to convert syngas to methanol and DME, then further to hydrocarbons, allows for reduced capitol and operation cost for the same chemistries that typically use 3 reactors instead of one. Utilization of commercially available methanol synthesis catalyst (Megamax 800, Clariant, CZA) and methanol dehydration catalyst with the Cu/Beta catalyst allowed for conversion into hydrocarbon products in this single reactor set up. Reactor configuration with CZA and alumina catalysts mixed with or stacked in a bed physically above the Cu/Beta catalyst provided a system for the direct conversion of the syngas to hydrocarbons with improved yields and selectivities with higher net C1 conversions for stacked bed configurations. Through control of the process conditions, greater conversion of C1 oxygenate intermediates (i.e., methanol and dimethyl ether) was achieved with concomitant increase in selectivities towards gasoline and jet fuel range olefin and paraffin products. Lower hydrocarbon number products and less naphthenes were observed for the conversion of syngas compared to DME conversion on only the Cu/Beta system with prominent selectivities observed for C4, C5, and C7 hydrocarbons. The DME and methanol formation rates, with understanding of the equilibria for both processes, were determined as important factors to allow for improved performance of the Cu/Beta. Determination of the factors which allow for tuning of selectivities and yields created an intensified process which allows for a "market-responsive" biorefinery design, which can produce high octane gasoline or jet fuel range hydrocarbons to meet demands for a more sustainable route to liquid fuels.

BIOMASS FUELS↗
DOE OSTI2022

Method for making porphyrin covalent organic framework-based interface

A porphyrine organic framework (“POF”) material is introduced with a one-pot method for photothermal material fabrication. The POF material may be deposited on a support scaffold by reacting a pyrrole by acid-catalyzed dehydration forming a plurality of porphyrin-based covalent organic frameworks particles on the support scaffold.

42 ENGINEERING↗
DOE OSTI2023

Economic and Sustainability Assessment on Bio-Based 2,3-BDO Separation Approaches for Sustainable Aviation Fuel Production

Sustainable aviation fuel (SAF) plays a critical role in aviation decarbonization. SAF can be derived from lignocellulosic biomass, such as corn stover, via 2,3-butanediol (BDO) intermediate. BDO undergoes downstream upgrading, including dehydration, oligomerization, and hydrotreating, to make the hydrocarbon blend stock like SAF. Separating BDO from a fermentation broth is challenging. Water is more volatile than BDO, so energy consumption for ordinary distillation is prohibitively high. For BDO to be a feasible intermediate for sustainable biofuels such as SAF, the total energy usage for the BDO separation target was set to be no greater than 30% of its lower heating value (LHV). We have developed and explored less energy intensive separation technologies for processing dilute fermentation BDO broth into suitable feed for downstream upgrading. The combined economic and sustainability assessment was performed to assess the feasibility of select cost-effective process designs and comparisons with baseline technology (i.e., cascade vacuum distillation).

BIOMASS FUELS↗
DOE OSTI2020

Iodine Co-Precipitation with Calcium Carbonate in the Presence of Silica Ions - 20360

Historical releases of I-129 to the subsurface at the U.S. Department of Energy Hanford Site have resulted in large dilute plumes that cover an area of over 50 km{sup 2}. The most concentrated I-129 plume is associated with the 200 West Area in the 200-UP-1 operable unit of the Hanford Central Plateau, where peak concentrations have been measured up to 30 times the drinking water standard of 1 pCi/L. The mobility of iodine depends on many factors, including chemical speciation, pH, redox conditions, as well as the presence of organic matter, calcium carbonate minerals and microbial activities. Speciation measurements estimate that the majority of the iodine (∼76%) in Hanford groundwater exists as iodate. Information on processes that affect iodate mobility in the Hanford subsurface support evaluation of environmental management options for the I-129 plumes. Iodate can be incorporated into calcium carbonate, which is a potential mechanism of naturally attenuating radioiodine in groundwater. However, the silica content in porewater may impact the contaminant-calcium carbonate incorporation process. Silica is one of the most abundant elements in nature and can have an impact on chemical weathering of alkaline-earth carbonates in the environment. Hence, this research aims to advances knowledge of the iodine co-precipitation process with calcium carbonate in the presence of silica. This information supports the technical basis evaluation of natural attenuation for I-129. Samples for these studies were prepared using calcium carbonate-forming solutions that included certified grade sodium meta-silicate nonahydrate (Na{sub 2}SiO{sub 3}), calcium chloride dehydrate (CaCl{sub 2}.2H{sub 2}O), sodium carbonate (NaCO{sub 2}), and sodium hydroxide (NaOH) solutions for pH adjustments. Triplicate samples were prepared with silica concentrations in the solution of 0 mM, 0.5 mM and 20 mM, mixed with an iodate standard (1000 ppm of IO{sub 3}{sup -} in H{sub 2}O) and sampled over a one-week period. Preliminary data analyses suggest that less iodine remains in solution in the presence of silica (average remaining aqueous fraction 0.23±0.03 at 20 mM of Si) relative to samples without silica (0.52±0.06); an indication that more iodine has been sorbed or incorporated into precipitates. However, the mechanisms for this behavior are still under investigation and need to be interpreted relative to pore water compositions that are representative of Hanford site-specific conditions. Scanning electron microscope equipped with energy dispersive spectroscopy (SEM-EDS) analyses were performed to observe the solid phase morphology in these experiments and showed rhombohedral calcite crystals covered with amorphous Si floccules. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Technology Development for Dry Storage of Aluminum-Clad Spent Nuclear Fuel - 20490

A candidate disposition pathway for the > 13 MTHM of aluminum-clad spent nuclear fuel (ASNF), owned and managed by the U.S. Department of Energy, is the drying and placement of the SNF into sealed-canister dry storage, with the ASNF-in- canisters 'road-ready' for transportation to and final direct disposal in a repository waste package. Technical information gaps in fuel drying, and fuel dry storage behavior, have previously challenged the declaration of technology readiness for drying and placement of this fuel into the DOE Standard Canister design for > 50 years of safe dry storage. The principal technical information gaps included: i) characterization and thermal dehydration behavior of aluminum (oxy)hydroxide films attendant on the cladding due to film formation during reactor operation and during post-discharge up to long-term wet storage histories; and ii) G-value data to enable estimation of the radiolytic gas generation from the cladding with its (oxy)hydroxide films. Thus, the oxide films on the ASNF challenged the safety of a sealed storage canister with thermal and radiolytic decomposition of the waters on the films that can lead to corrosion, pressurization, and flammability issues. These gaps in the technical information base have largely been closed. This paper discusses the investigations at the Idaho National Laboratory (INL) and the Savannah River National laboratory (SRNL), and outlines the pending technology development work for input to an engineering design to enable a road-ready dry storage system for ASNF. The ASNF inventory considered for road-ready dry storage is stored at the Savannah River Site (SRS) and at the Idaho Nuclear Technology and Engineering Center (INTEC) at the INL. The ASNF inventory in the SRS L Basin is from foreign and domestic research reactors (FRR and DRR), and is diverse in terms of design, irradiation, and post-reactor-discharge storage conditions; these factors yield a range of characteristics of cladding oxide films on ASNF. Mixed aluminum (oxy)hydroxide (boehmite and bayerite/gibbsite) films, non-uniform in thicknesses up to a maximum local thickness bounded by 25 μm, were observed on ASNF materials removed from wet storage in the L Basin and in non-sealed dry storage at the SRS following reactor service and a long-term (up to 40+ years) interim storage history. The ASNF inventory at INTEC, in both wet and vented dry storage, is predominantly from the Advanced Test Reactor (ATR), but it also includes DRR and FRR fuel. To address a profound behavior of these films, radiolysis testing of aluminum specimens with mixed type boehmite/bayerite oxide films was performed to develop basic data on G-values for production of radiolytic hydrogen under dry storage conditions with nominal relative humidity, temperature, and cover gas. Modeling and simulation of canister internal environments with postulated inventories of oxide films provides estimation of the evolution of the conditions of the canister loaded with ASNF. Simultaneous Thermal Analysis (TGA/DSC) of hydrated oxide powders, and laboratory-scale aluminum specimens with a bayerite film (∼10 μm) using TGA methods, inform drying time/temperature conditions to be used for the ASNF. A demonstration project is recommended for Verification and Validation of the drying and storage of the ASNF. Remaining major tasks leading up to the hot demonstration include scale-up radiolysis testing and scale-up drying testing. Engineering design with the information from the technology program will establish the safety basis and enable long-term (> 50 years) dry storage compatibility with ASNF in the DOE Standard Canister pending its transportation to and disposal in a repository. This full capability would show the ASNF-in-canister storage system to be road-ready. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Preliminary Evidence of Gas-Phase Water Splitting on Holmium Nitrogen Oxide Clusters

Preliminary Evidence of Gas-Phase Water Splitting on Holmium Nitrogen Oxide Clusters Christopher A. Zarzana1, Makayla R. Baxter , Introduction: Molecular hydrogen is a potential energy carrier that could be used to help implement a clean energy economy if it is generated from splitting of water. Improvements in the efficiencies of water-splitting electrolyzers relies on development of novel materials with enhanced performance. However, research in this area is slowed due to underdeveloped understanding of the mechanisms of device performance due to challenges interrogating the fundamental chemical reactions at play in bulk materials. Studies of the intrinsic reactivity of clusters that are representative of the reactive sites of these materials can increase understanding of the fundamental reaction mechanisms involved in hydrogen production, allowing for more efficient development of new water-splitting materials. Methods: Holmium tetranitrato ([Ho(NO3)4]-) clusters were generated in gas-phase using the electrospray ionization source of a Bruker (Billerica, MA, USA) micrOTOF-Q II quadrupole time-of-flight mass spectrometer. Spray solutions consisted of aqueous holmium (Ho) nitrate solutions (at nominally 3 mM) diluted to 30 µM in acetonitrile. The holmium (Ho) tetranitrato clusters were isolated using the quadrupole and were subsequently activated and allowed to react with background water in the collision cell. High resolution, high mass accuracy spectra were recorded using the time-of-flight. Mass accuracy was ensured using external calibration with Agilent (Santa Clara, CA, USA) ESI-L Low Concentration tuning mix. Preliminary data: Collisional activation of the holmium tetranitrato complexes ([Ln(NO3)4]-) resulted in an expected series of ions resulting from the loss of ·NO and ·NO2. This included an ion at m/z = 382.885 assigned as [HoO2(NO3)3]- (theoretical m/z=382.884, error=-1.2 ppm), resulting from loss of ·NO, and an ion at m/z=366.890 assigned as [HoO(NO3)3]- (theorical m/z=366.889, error=-1.8 ppm), resulting from loss of ·NO2. Additional ions were detected that would result from more complicated losses from [Ho(NO3)4]-, including ions at m/z=320.898 assigned as [HoO2(NO3)2]- (theoretical m/z=320.896, error=-4.9 ppm), at m/z=304.904 assigned as [HoO(NO3)2]- (theoretical m/z=304.901, error=-8.1 ppm, very low signal), and at m/z=288.908 assigned as [Ho(NO3)2]- (theoretical m/z=288.907, error=-3.4 ppm). This ion series would arise from loss of some combination of ·NO, ·NO2, and ·NO3, although it is not known whether these losses occur sequentially (e.g. loss of ·NO and ·NO3 to yield [HoO2(NO3)2]-) or as a single species (e.g. direct loss of N2O4). These ions were accompanied by a complementary series representing addition of a single water molecule. This included an ion at m/z=338.908 assigned as [HoO2(NO3)2H2O]- (theoretical m/z=338.907, error=-4.1 ppm), an ion at m/z=322.912 assigned as [HoO(NO3)2H2O]- (theoretical m/z=322.912, error=1.2 ppm), and an ion at m/z=306.918 assigned as [Ho(NO3)2H2O]-, (theoretical m/z=306.918, error=-3.7 ppm). An additional hydrated ion was observed at m/z=276.921 assigned as [HoO2(NO3) H2O]- (theoretical m/z=276.919, error=-7.3 ppm), although corresponding dehydrated ion was not observed. An additional ion was observed at m/z=367.898 that has been assigned as [Ho(NO3)3OH]- (theoretical m/z=367.897, error=-2.5 ppm). It is hypothesized that this ion arises from addition of water to [Ho(NO3)3]- followed by elimination of a hydrogen radical. Neither [Ho(NO3)3]- nor [Ho(NO3)3H2O]- were detected, suggesting that, if the hypothesis is correct, addition of water to [Ho(NO3)3]- and its subsequent splitting is rapid. Elimination of HNO3 from [Ho(NO3)4H2O]- could also yield [Ho(NO3)3OH]-; however, no [Ho(NO3)4H2O]- ions were observed. Novelty: Potential evidence of water splitting on gas-phase lanthanide clusters offers a way to study the intrinsic reactivity of hydrogen-generation materials.

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

NIR Dataset and Models (Near-Infrared Spectroscopy Calibration Dataset for Butanediol Fermentation and Multivariate Calibration Models) [SWR-22-60]

2,3-butanediol (2,3-BDO) is an economically important platform chemical that can be used in a variety of chemical feedstocks, liquid fuels, and biosynthetic building blocks. While 2,3-BDO can be efficiently produced by fermentation, the fermentation requires continuous monitoring and control to maximize 2,3-BDO yields and minimize inhibitory coproducts. Because of the time required for sampling and at-line measurement of fermentation samples with high pressure liquid chromatography (HPLC), the ability for operators to perform real-time modification to fermentation conditions is limited. To overcome this challenge, researchers from the National Renewable Energy Laboratory (NREL) have developed a calibration model which can predict the concentration of several analytes in real-time using near-infrared (NIR) spectra of the filtered fermentation broth. While significantly reducing the need for off-line sampling, NREL expects this technology to play a critical role in maximizing 2,3-BDO production. 2,3-butanediol (2,3-BDO) is a useful chemical platform that can be used to create a variety of products. For instance, 2,3-BDO can be (1) dehydrated and converted into methyl ethyl ketone, a liquid fuel additive or (2) deoxydehydrated into 1,3-butadiene for synthetic rubber, which can also be oligomerized in high yields to gasoline, diesel, and jet fuel. In order to maximize 2,3-BDO production, frequent measurement of fermentation samples is needed, as small changes in oxygen concentration can drive the fermentation to undesired products. For example, oxygen-deficient conditions result in glycerol production, while excess oxygen concentrations result in acetoin production. This results in the need for measuring dissolved oxygen, glucose, and xylose concentrations in order to optimize the aeration rate of the fermentation. Traditional monitoring methods occurs off-line and can take up to 30 minutes per sample. With multiple fermenters and high-pressure liquid chromatography (HPLC) injectors, resulting in the need for multiple samples, the sampling process can take hours to complete. NREL’s calibration model can predict the glucose, xylose, 2,3-BDO, acetoin, and glycerol concentrations from NIR spectra of filtered fermentation liquor samples. Using a partial least-squares (PLS) calibration model, NREL’s model can monitor the concentration of these analytes during subsequent fermentations at bench- and pilot-scale, demonstrating the utility of NIR spectroscopy combined with chemometrics for real-time, at-line monitoring of 2,3-BDO fermentations.

Wolfrum, Edward↗
DOE OSTI2021

Responses of the Plant Cell Wall to Sub-Zero Temperatures: A Brief Update

Our general understanding of plant responses to sub-zero temperatures focuses on mechanisms that mitigate stress to the plasma membrane. The plant cell wall receives comparatively less attention, and questions surrounding its role in mitigating freezing injury remain unresolved. Despite recent molecular discoveries that provide insight into acclimation responses, the goal of reducing freezing injury in herbaceous and woody crops remains elusive. This is likely due to the complexity associated with adaptations to low temperatures. Understanding how leaf cell walls of herbaceous annuals promote tissue tolerance to ice does not necessarily lead to understanding how meristematic tissues are protected from freezing by tissue-level barriers formed by cell walls in overwintering tree buds. In this mini-review, we provide an overview of biological ice nucleation and explain how plants control the spatiotemporal location of ice formation. We discuss how sugars and pectin side chains alleviate adhesive injury that develops at sub-zero temperatures between the matrix polysaccharides and ice. The importance of site-specific cell-wall elasticity to promote tissue expansion for ice accommodation and control of porosity to impede ice growth and promote supercooling will be presented. How specific cold-induced proteins modify plant cell walls to mitigate freezing injury will also be discussed. The opinions presented in this report emphasize the importance of a plant’s developmental physiology when characterizing mechanisms of freezing survival.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Molecular level insight into non-bilayer structure formation in thylakoid membranes: a molecular dynamics study

In oxygenic photosynthetic organisms, the light reactions are performed by protein complexes embedded in the lipid bilayer of thylakoid membranes (TMs). The organization of the bulk lipid molecules into bilayer structures provide optimal conditions for the build-up of the proton motive force (pmf) and its utilization for ATP synthesis. However, the lipid composition of TMs is dominated by the non-bilayer lipid species monogalactosyl diacylglycerol (MGDG), and functional plant TMs, besides the bilayer, contain large amounts of non-bilayer lipid phases. Bulk lipids have been shown to be associated with lumenal, stromal-side and marginal-region proteins and proposed to play roles in the self-assembly and photoprotection of the photosynthetic machinery. Furthermore, it has recently been pointed out that the generation and utilization of pmf for ATP synthesis according to the ‘protet’ or protonic charge transfer model Kell (Biochim Biophys Acta Bioenerg 1865(4):149504, 2024), requires high MGDG content Garab (Physiol Plant 177(2):e70230, 2025). In this study, to gain better insight into the structural and functional roles of MGDG, we employed all atom and coarse-grained molecular dynamics simulations to explore how temperature, hydration levels and varying MGDG concentrations affect the structural and dynamic properties of bilayer membranes constituted of plant thylakoid lipids. Our findings reveal that MGDG promotes increased membrane fluidity and dynamic fluctuations in membrane thickness. MGDG-rich stacked bilayers spontaneously formed inverted hexagonal phases; these transitions were enhanced at low hydration levels and at elevated but physiologically relevant temperatures. It can thus be inferred that MGDG plays important roles in heat and drought stress mechanisms.

59 BASIC BIOLOGICAL SCIENCES↗