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At least 55 records · Page 3

Continental-scale integration of soil metagenomes and organic matter chemistry reveals ubiquitous microbial capacity for chemically-recalcitrant carbon decomposition

Soil organic matter (SOM) decomposition by microorganisms is a major uncertainty in predicting terrestrial carbon–atmosphere feedbacks, partly because we lack understanding of the microbial diversity involved in depolymerizing different carbon pools across environmental gradients. We address this gap using a continental-scale dataset pairing shotgun metagenomes with high-resolution SOM chemistry, assembling 0.76 Tbp of prokaryotic MAGs (828 genomes) and identifying 66,727 SOM molecules from 47 standardized U.S. soil cores selected using respiration rates from 106 soils. Integrating these datasets reveals widespread microbial potential for depolymerizing chemically-recalcitrant SOM previously considered stable. We uncover complementary metabolic specialization between genera affiliated with two abundant bacterial orders, Rhizobiales and Chthoniobacterales, and an archaeal order, Nitrososphaerales. This metabolic partitioning is consistent across soil depths and activity levels, suggesting coordinated decomposition of complex SOM through distinct but complementary biochemical strategies. The metabolic potential for depolymerization of chemically-recalcitrant compounds is supported by the abundance of these molecules across the soils, as indicated by Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS), and by flux balance analysis of metabolic models. Our results show that a substantial portion of ostensibly stable SOM remains vulnerable to microbial decomposition, a mechanism not captured in current Earth System Models.

Song, Young C. [Pacific Northwest National Laborat↗

Coassembly and binning of a twenty-year metagenomic time-series from Lake Mendota

Abstract The North Temperate Lakes Long-Term Ecological Research (NTL-LTER) program has been extensively used to improve understanding of how aquatic ecosystems respond to environmental stressors, climate fluctuations, and human activities. Here, we report on the metagenomes of samples collected between 2000 and 2019 from Lake Mendota, a freshwater eutrophic lake within the NTL-LTER site. We utilized the distributed metagenome assembler MetaHipMer to coassemble over 10 terabases (Tbp) of data from 471 individual Illumina-sequenced metagenomes. A total of 95,523,664 contigs were assembled and binned to generate 1,894 non-redundant metagenome-assembled genomes (MAGs) with ≥50% completeness and ≤10% contamination. Phylogenomic analysis revealed that the MAGs were nearly exclusively bacterial, dominated by Pseudomonadota (Proteobacteria, N = 623) and Bacteroidota (N = 321). Nine eukaryotic MAGs were identified by eukCC with six assigned to the phylum Chlorophyta. Additionally, 6,350 high-quality viral sequences were identified by geNomad with the majority classified in the phylum Uroviricota. This expansive coassembled metagenomic dataset provides an unprecedented foundation to advance understanding of microbial communities in freshwater ecosystems and explore temporal ecosystem dynamics.

59 BASIC BIOLOGICAL SCIENCES↗

Solvent effects on extractant conformational energetics in liquid–liquid extraction: a simulation study of molecular solvents and ionic liquids

Extractant design in liquid–liquid extraction (LLE) is a research frontier of metal ion separations that typically focuses on the direct extractant–metal interactions. However, a more detailed understanding of energetic drivers of separations beyond primary metal coordination is often lacking, including the role of solvent in the extractant phase. In this work, we propose a new mechanism for enhancing metal-complexant energetics with nanostructured solvents. Using molecular dynamics simulations with umbrella sampling, we find that the organic solvent can reshape the energetics of the extractant's intramolecular conformational landscape. Here, we calculate free energy profiles of different conformations of a representative bidentate extractant, n-octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphinoxide (CMPO), in four different solvents: dodecane, tributyl phosphate (TBP), and dry and wet ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf 2 N]). By promoting reorganization of the extractant molecule into its binding conformation, our findings reveal how particular solvents can ameliorate this unfavorable step of the metal separation process. In particular, the charge alternating nanodomains formed in ILs substantially reduce the free energy penalty associated with extractant reorganization. Importantly, using alchemical free energy calculations, we find that this stabilization persists even when we explicitly include the extracted cation. These findings provide insight into the energetic drivers of metal ion separations and potentially suggest a new approach to designing effective separations using a molecular-level understanding of solvent effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Actinide oxide dissolution in tributyl phosphate

An alternative to dissolving used nuclear fuel (UNF) in an acidic solution during reprocessing is direct dissolution in an organic solution, which would eliminate an aqueous dissolution step, decrease the amount of nitrate needed, and reduce the facility size. The flowsheet for this potentially less expensive alternative is first to voloxidize the UNF to remove fission product gases and form an oxide. After voloxidation, the UNF is then dissolved in an organic solution containing an extractant mixed with an aliphatic diluent and pre-equilibrated with nitric acid. The organic solution then goes through a solvent extraction process to recover the uranium and/or other desired radionuclides. This work qualitatively studied the dissolution of actinide oxides (UO2, NpO2, and PuO2) in tributyl phosphate using UV-Vis-NIR absorbance spectroscopy to ascertain dissolution behavior. Initial studies included material that is otherwise difficult to dissolve in only nitric acid, specifically CeO2, that is sometimes used as a dissolution surrogate for PuO2. This work confirmed that CeO2, NpO2, and PuO2 are difficult to dissolve in 30 vol% TBP-dodecane pre-equilibrated with 10 M HNO3 and will readily dissolve when co-precipitated with U (i.e., the mixed oxides U-Ce, U-Np, and U-Pu), surrogates for voloxidized nuclear fuel.

Gogolski, Jarrod [Savannah River National Laborato↗

Synthesis, characterization, and computational modeling of 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) modified group 4 metal alkoxides

The coordination behavior of the tridentate alkoxy ligand 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene)) bis(2,4-di-tert-butylphenol) (termed H 3 -AM-DBP 2 ) with group 4 metal alkoxides ([M(OR) 4 ]) in a 1:1 ratio was previously found to generate [(ONep)Ti(κ 4 (O,O’,O”,N)-AM-DBP2)] and [(OR)Zr(κ 4 (μ-O,O’,O”,N)-AM-DBP 2 )] 2 (M = Zr, Hf). Additional studies revealed that increasing the stoichiometric ratio to 1:2 H3-AM-DBP 2 :[M(OR) 4 ] led to the isolation of [(ONep)Ti(κ 4 (μ-O,O’,O”,N)-AM-DBP2)(μ-ONep)Ti(ONep) 3 ] (1)•tol, [(OBu t)Zr(κ 4 (μ-O,O’,O”,N)-AM-DBP2)(μ-OBu t)Zr(OBu t )3] (2) and [(OBu t)Hf(κ 4 (μ-O,O’,O”,N)-AM-DBP2)(μ-OBu t )Hf(OBu t ) 3 ] (3). The asymmetric dinuclear complexes of 1-3 resemble the chelation of a [M(OR) 4 ] moiety to a “(OR)M(κ 4 (O,O’,O”,N)-AM-DBP 2 )” fragment. The metal complexed by the AM-DBP 2 ligand has a pseudo octahedral geometry while the other metal adopts an intermediate trigonal bipyramidal (TBP-5)/square base pyramidal (SBP-5) geometry for 1 but a distorted SBP-5 for both 2 and 3. The structure and properties of 1-3 were analyzed by computational modeling and fully characterized by standard analytical methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Extraction of Uranium-Lanthanide Oxides in Tributyl Phosphate

Abstract Direct extraction of used nuclear fuel (UNF) in an organic solution could be more efficient than the previous practice with aqueous solutions. However, the UNF would need to be treated via voloxidiation before being processed using solvent extraction. The voloxidation process can form oxide and/or nitrate compounds. This work investigated the dissolution of uranium/lanthanide oxides in 30 vol % TBP diluted in dodecane (pre-equilibrated with 4 M nitric acid) in a glass reactor with air sparging to ascertain the uranium/lanthanide oxide dissolution behavior prior to scaling the process. The uranium/lanthanide oxides were prepared by co-precipitating uranium/lanthanide nitrates with hydroxide and then calcined to form a mixed oxide. While the relative concentrations of the lanthanides are not representative of used nuclear fuel, the neodymium and erbium allowed ease of tracking dissolution with visible spectroscopy. Cerium was used as a surrogate for plutonium. The dissolution rate of the oxides was similar but incomplete. A miniscule amount of cerium, as cerium oxide, took several months to slowly dissolve; however, when co-precipitated with uranium and other lanthanides, a significant amount of cerium dissolved readily.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

High-quality genome of the basidiomycete yeast Dioszegia hungarica PDD-24b-2 isolated from cloud water

The genome of the basidiomycete yeast Dioszegia hungarica strain PDD-24b-2 isolated from cloud water at the summit of puy de $D\hat{o}me$ (France) was sequenced using a hybrid PacBio and Illumina sequencing strategy. The obtained assembled genome of 20.98 Mb and a GC content of 57% is structured in 16 large-scale contigs ranging from 90 kb to 5.56Mb, and another 27.2 kb contig representing the complete circular mitochondrial genome. In total, 8,234 proteins were predicted from the genome sequence. The mitochondrial genome shows 16.2% cgu codon usage for arginine but has no canonical cognate tRNA to translate this codon. Detected transposable element (TE)-related sequences account for about 0.63% of the assembled genome. A dataset of 2,068 hand-picked public environmental metagenomes, representing over 20 Tbp of raw reads, was probed for D. hungarica related ITS sequences, and revealed worldwide distribution of this species, particularly in aerial habitats. Growth experiments suggested a psychrophilic phenotype and the ability to disperse by producing ballistospores. The high-quality assembled genome obtained for this D. hungarica strain will help investigate the behavior and ecological functions of this species in the environment.

59 BASIC BIOLOGICAL SCIENCES↗

Decomposing a San Francisco estuary microbiome using long-read metagenomics reveals species- and strain-level dominance from picoeukaryotes to viruses

ABSTRACT Although long-read sequencing has enabled obtaining high-quality and complete genomes from metagenomes, many challenges still remain to completely decompose a metagenome into its constituent prokaryotic and viral genomes. This study focuses on decomposing an estuarine metagenome to obtain a more accurate estimate of microbial diversity. To achieve this, we developed a new bead-based DNA extraction method, a novel bin refinement method, and obtained 150 Gbp of Nanopore sequencing. We estimate that there are ~500 bacterial and archaeal species in our sample and obtained 68 high-quality bins (>90% complete, <5% contamination, ≤5 contigs, contig length of >100 kbp, and all ribosomal and tRNA genes). We also obtained many contigs of picoeukaryotes, environmental DNA of larger eukaryotes such as mammals, and complete mitochondrial and chloroplast genomes and detected ~40,000 viral populations. Our analysis indicates that there are only a few strains that comprise most of the species abundances. IMPORTANCE Ocean and estuarine microbiomes play critical roles in global element cycling and ecosystem function. Despite the importance of these microbial communities, many species still have not been cultured in the lab. Environmental sequencing is the primary way the function and population dynamics of these communities can be studied. Long-read sequencing provides an avenue to overcome limitations of short-read technologies to obtain complete microbial genomes but comes with its own technical challenges, such as needed sequencing depth and obtaining high-quality DNA. We present here new sampling and bioinformatics methods to attempt decomposing an estuarine microbiome into its constituent genomes. Our results suggest there are only a few strains that comprise most of the species abundances from viruses to picoeukaryotes, and to fully decompose a metagenome of this diversity requires 1 Tbp of long-read sequencing. We anticipate that as long-read sequencing technologies continue to improve, less sequencing will be needed.

Lui, Lauren M.↗

Videos of Chemically Activated Frontal Polymerization of Thermosets

Video recordings of the frontal ring-opening metathesis polymerization (FROMP) of thermoset polymer specimens in 10mm glass test tubes were collected in order to measure the front speed resulting from varied front initiation methods. Maximum front temperature was also measured. Polymerization resins comprised of dicyclopentadiene (DCPD) with 5 wt% 5-ethylidene-2-norbornene (ENB) added, grubbs’ second generation catalyst, and tributyl phosphite (TBP) inhibitor (8000:1:1 monomer:initiator:inhibitor ratio). Polymerization fronts were triggered using concentrated solutions of grubbs’ third generation catalyst in various solvents.

Cramblitt, Anna C.↗

Generation and Characteristics of Plutonium and Americium Contaminated Soils Underlying Waste Sites at Hanford

In 2012, a Hanford site-wide review on plutonium and americium geochemistry (Cantrell and Felmy 2012) identified remaining research challenges associated with defining scientifically defensible end-states and supporting remediation decisions. Three research challenges were identified in this review: 1. Determine the transformations of Hanford Site sediments in response to changes in waste/groundwater composition. Significant mineralogical transformations can take place when wastes contact Hanford sediments. These transformations can significantly impact the solubility and acidic adsorption of plutonium and americium and possibly result in the generation of pseudo colloids that could facilitate plutonium/americium migration. 2. Assess the impact of changes in waste/groundwater chemistry on the potential for plutonium/americium solubilization or colloid formation. Changes in waste or groundwater chemistry can greatly impact the chemical form or speciation of plutonium and americium. Knowledge of plutonium and americium speciation will be crucial in terms of evaluating the potential for solubilization, adsorption or remobilization of adsorbed complexes, colloid formation, and colloid interactions with sedimentary minerals. 3. Establish the role of organic complexants and/or non-aqueous solvents in the transport of plutonium/americium in the deep subsurface. Plutonium has been found to be associated with TBP and the presence of non-aqueous solvents, at least in certain Z-9 sediments. It will be important to establish the role of non-aqueous solvent in past movement of plutonium and its potential role in future mobility. This report provides the technical basis for interpreting data obtained from field samples and will allow waste chemistry impacts on plutonium/americium re-mobilization mechanisms to be assessed. This report helps address the three previously identified research challenges – sediment transformations, solution chemistry impacts, and the role of organic complexants and solvents – in plutonium and americium contaminated Hanford sediments. Ultimately, these and potential future studies will lead to a defensible description of plutonium and americium mobility in relation to waste site conditions that can be interpreted to balance the risks posed by their migration and envisioned remediation activities.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Crystallization of Ammonium Heptamolybdate for Reduction to Mo Metal

The 100 Mo/ 98 Mo recycle process developed by Argonne National Laboratory in collaboration with Oak Ridge National Laboratory (ORNL) and supported by the U.S. Department of Energy (DOE) National Nuclear Security Agency’s (NNSA’s) Office of Material Management & Minimization (M3) is vital to sustaining the economic production of 99 Mo. The high-yield molybdenum solution extraction (MOEX) process recovers enriched Mo by acidifying spent generator solutions, extracting Mo using tri-n-butyl phosphate (TBP), and stripping Mo into ammonium hydroxide, where it is later converted to solid (NH 4 ) 6 M 07 O 24 (ammonium heptamolybdate or AHM) by crystallization. It is important to produce the AHM product with consistent particle size and morphology before its thermal treatment and reduction to Mo metal in a furnace. AHM particles that are too small (< 50 µm) result in Mo metal powder that is much too fine to properly fabricate into targets with optimum properties.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Solvent Recovery and Management at the Savannah River Site H-Canyon Facility

NIOWAVE, Inc. is a domestic supplier of medical and industrial isotopes from uranium and radium. The Savannah River National laboratory (SRNL) is currently providing support to NIOWAVE, which plans to deploy a superconducting electron linear accelerator (LINAC) to fission uranium for Mo-99 production without the need for a nuclear reactor or HEU. The uranium from the Mo-99 production targets will be purified using a modified PUREX (Plutonium Uranium Reduction Extraction) solvent extraction process to recover the uranium in the product stream. The uranium will then be precipitated as an oxalate which is calcined to U 3 O 8 to fabricate pellets for new Mo-99 targets. In previous support provided to NIOWAVE, the SRNL demonstrated a solvent washing process to remove degradation products from the tributyl phosphate (TBP) solvent used in the modified PUREX process under development for uranium recovery. To supplement this technology demonstration, NIOWAVE requested the SRNL to provide summary information on the solvent recovery and management activities which are used at the Savannah River Site (SRS) H-Canyon facility. An existing reference document for the reprocessing of irradiated HEU fuels at the SRS was used as the primary reference for the solvent management activities; although, other reference documents were used to provide supplementary information. The information provided includes a brief summary of the solvent degradation issues which have been observed in the H-Canyon solvent extraction cycles and resulting process safety concerns. The solvent recovery processes for the three cycles of solvent extraction used in the H-Canyon were subsequently described including the process equipment which consists of the continuous and batch solvent washers, pumps, and tanks. A final section is provided on the monitoring and analysis of solvent quality based on the previous work performed at the SRNL for NIOWAVE and past research and development activities performed to support the solvent extraction processes in both the SRS F-Canyon and H-Canyon facilities.

07 ISOTOPE AND RADIATION SOURCES↗

Purification and Concentration of 99 Mo from a UREX raffinate

The medical isotope 99m Tc ( t ½ = 6.0 h) accounts for over 80% of isotopes used in diagnostic nuclear medicine today and is normally derived from its transient equilibrium parent 99 Mo ( t ½ = 66 h). To reduce U.S. dependence on 99 Mo derived from HEU by foreign suppliers, the NNSA/M3 program—under the American Medical Isotope Production Act—has been tasked with facilitating the work of domestic 99 Mo suppliers that do not utilize HEU. Superconducting electron linear accelerators with high-Z converter targets can generate bremsstrahlung photons and neutron fluxes that can induce photonuclear reactions and LEU fission. After sufficient production intervals, targets can be rotated out and processed while another batch is irradiated. The process flow chemistry is shown in Figure 1. The irradiated U 3 O 8 targets are retrieved and dissolved in HNO 3 ; the volatile fission products are expelled and captured during this step. The HNO 3 liquor bearing the uranyl, fission and activation products is injected into the UREX suite of liquid-liquid extraction banks. The uranyl is partitioned in typical fashion using tri-$\textit{n}$-butyl phosphate (TBP) in a hydrocarbon diluent. The raffinate—comprising mainly 99 Mo and fission products—is then injected into the MoLLE (Molybdenum Liquid-Liquid Extraction) flowsheet, where the Mo is selectively extracted by an organophosphorous acid extractant such as di-(2-ethylhexyl phosphoric acid) (HDEHP). Trace amounts of Nb, Zr, Np, I, and Te are co-extracted. The Mo is stripped using acetohydroxamic acid (AHA) and fed onto an anion exchange column. Following a series of hydroxide, HCl, and oxalic acid wash steps, the Mo can be recovered in NaOH/NaCl. A manuscript describing this process chemistry in more detail was recently published.

07 ISOTOPE AND RADIATION SOURCES↗

Kinetics and Mechanism of Tetravalent Cerium Extraction by Di-2-Ethylhexyl Isobutyramide (DEHiBA)

DEHiBA is a fully-incinerable, CHON extractant with a high selectivity for hexavalent actinides. However, as a recently-developed ligand, much remains unknown about its physical and chemical properties, including its extraction and phase disengagement rates. Here, we present data on the phase transfer kinetics of Ce(IV) extraction and stripping by both DEHiBA and TBP collected using microfluidic devices. Ce(IV) was selected as a surrogate for Pu(IV) and Np(IV) in the initial tests of the microfluidics system prior to testing with the actinides. Pseudo first-order reaction rate constants are determined for both systems, and the corresponding Damköhler numbers (Da) are calculated to establish whether the extraction and stripping processes are kinetically or diffusion controlled. The stoichiometry of the extracted Ce(IV)-DEHiBA complex is determined, and the phase disengagement properties under extraction conditions are assessed using the dimensionless dispersion number. A possible explanation for the favorable extraction of Ce(IV) by DEHiBA, which is known to poorly extract many tetravalent cations, is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Extraction of Lanthanide Oxides and Nitrates in Tributyl Phosphate

This work investigated the dissolution rate of lanthanide oxides and nitrates in a 30 vol % TBP-n-paraffin solvent (pre-equilibrated with various nitric acid concentrations) using visible (Vis) spectroscopy over time. Some dissolution mechanics were observed, such as an aqueous layer forming, considerably longer dissolution times for the heavier lanthanides (hours) vs. the lighter lanthanides (minutes), and the impacts of mixing lanthanide oxides or nitrates during dissolution. Neodymium, samarium, holmium, and erbium were selected due to their unique spectroscopic signatures and to represent the lighter (neodymium and samarium) and heavier (holmium and erbium) lanthanides. Even though europium does not have a strong absorbance in the range studied, europium was used in some instances to also represent the lighter lanthanides. Cerium oxide was used to representant dissolution of tetravalent lanthanides.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mo-99 Concentration and processing by Solvent Extraction and Ion Exchange

Normally derived from its transient-equilibrium parent molybdenum-99 ( 99 Mo) (t½ = 66 h), the short-lived isotope technetium-99m ( 99m Tc) (t ½ = 6.0 h) is the most widely used medical isotope in diagnostic imaging today. The National Nuclear Security Administration’s (NNSA’s) Material Management and Minimization (M3) program—established under the auspices of the American Medical Isotope Production Act—has been tasked with facilitating the work of domestic 99 Mo suppliers that do not use highly enriched uranium (HEU). Superconducting electron linear accelerators that employ high-Z converter targets can generate bremsstrahlung photons and neutron fluxes that can induce photonuclear reactions and uranium (U) fission. Argonne, in collaboration with industrial partners, has been developing the process chemistry for superconducting linear accelerator (LINAC)-irradiated triuranium octoxide (U 3 O 8 ) targets to produce 99 Mo. In short, the process involves dissolving the irradiated targets in nitric acid, which simultaneously releases valuable fission products (xenon and iodine). After adjusting the acid concentration, producers process the feed using tri-n-butyl phosphate (TBP), then mix the raffinate derived from this extraction cycle with a phosphinic acid such as Cyanex 272 or di(2-ethylhexyl) phosphoric acid (HDEHP), which is selective for Mo (molybdenum liquid liquid extraction [MoLLE]). In the next step, a concentration column comprising an anion exchange platform is used to decontaminate the remaining fission products, generating a pure 99 Mo stream in sodium hydroxide (NaOH)/sodium chloride (NaCl).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Building Performance Standards and Energy Code Alignment: Technical Brief

Building energy codes focus on building design, construction and renovation and have significantly increased building efficiency since the first national energy code was published in 1975. Most jurisdictions have energy codes based on ANSI/ASHRAE/IES Standard 90.1 (hereto referred to as Standard 90.1) and the International Energy Conservation Code (IECC). Compliance options available in these model energy codes include a prescriptive path, whole building performance paths – including IECC Total Building Performance (TBP), Standard 90.1 Energy Cost Budget (ECB) method and Performance Rating Method (PRM) – and system performance paths for envelope and heating, ventilation, and air-conditioning systems. Building performance standard (BPS) policies are an emerging policy tool used by jurisdictions to reduce the operational energy use or greenhouse gas (GHG) emissions of the existing commercial building stock. BPS policies vary widely between jurisdictions and are tailored to each location’s climate and energy goals. Intuitively, projects that met a recent edition of the energy code should comply with the BPS targets.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗