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At least 163 records · Page 9

Improbability of Post-Closure Criticality in Compacted Criticality Control Overpacks after Room Closure at Waste Isolation Pilot Plant

As part of its periodic re-certification of the Waste Isolation Pilot Plant (WIPP), an operating repository in bedded salt for the disposal of transuranic (TRU) waste from atomic energy defense activities, the United States Environmental Protection Agency expects a re-evaluation of features, events, and processes, such as post-closure nuclear criticality. Although salt creep beneficially encapsulates the TRU waste in the closed WIPP repository, the spacing between an array of waste packages is disrupted as the salt creep closes disposal rooms and containers lose structural integrity. For most TRU waste, the possibility of post-closure criticality is exceedingly small either because the salt neutronically isolates TRU waste canisters or because closure of a disposal room from salt creep does not sufficiently compact the low mass of fissile material. The criticality evaluation was updated, however, because of the introduction of criticality control overpack (CCO) containers, which may dispose up to 380 fissile gram equivalent plutonium-239 in each container. The criticality potential is evaluated through high-fidelity geomechanical modeling of a disposal room filled with CCO containers during two representative conditions: (1) large salt block fall, and (2) gradual disposal room closure from salt creep. Geomechanical models of roof fall demonstrate three tiers of CCO containers are not greatly disrupted. Geomechanical models of gradual room closure from salt creep (without brine seepage and subsequent gas generation to permit maximum room closure) were used to predict irregular arrays of closely packed CCOs after 1000 years, when room closure has asymptotically approached maximum compaction. Models of spheres or cylinders with 380 fissile gram equivalent of plutonium (as oxide) at the predicted irregular compacted spacing demonstrate that an array of CCO containers is not critical when surrounded by salt and magnesium oxide, provided the mass of hydrogenous material shipped in CCO containers (usually plastics) is controlled or boron carbide (a neutron poison) is mixed with the fissile contents.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Study of Integrated Signal and Power Transfer for Compact Isolated SiC MOSFET Gate-Drivers

This work discusses a novel set of alternate implementations of isolated gate driver circuits for power electronic transistors. The proposed topologies for the driver have been designed specifically for SiC power MOSFET. Three different solutions are discussed, all of them providing the required gate turn-on and turn-off command signal with galvanic isolation, but also supplying power to the secondary side of the driver by means of magnetic transformers. The resulting solutions, all of them implemented with simple circuitry, enable the integration of the driver into the power cell, allowing for theoretical higher power density values in the final system. The principle of operation of the different solutions is discussed, and then the main relevant implementation details are presented. After that, the operation of the circuits is demonstrated experimentally, by testing a set of prototypes of these drivers. This provides a comprehensive design example that assesses the feasibility of the proposed solutions. Finally, the main results of the performance of the three gate drivers, on an SiC MOSFET-based prototype are presented and compared.

42 ENGINEERING↗

The Preservation of Super-Earths and the Emergence of Gas Giants after Their Progenitor Cores Have Entered the Pebble-isolation Phase

The omnipresence of super-Earths suggests that they are able to be retained in natal disks around low-mass stars, whereas exoplanets' mass distributions indicate that some cores have transformed into gas giants through runaway gas accretion at ≳1 au from solar-type stars. In this paper, we show that transition to runaway gas accretion by cores may be self-impeded by an increase of the grain opacity in their envelope after they have acquired sufficient mass (typically ~ 10M ⊕ ) to enter a pebble-isolation phase. The accumulation of approximately millimeter- to meter-sized pebbles in their migration barriers enhances their local fragmentation rates. The freshly produced submillimeter grains pass through the barrier, elevate the effective dust opacity, and reduce the radiative flux in the core's envelope. These effects alone are adequate to suppress the transition to runaway accretion and preserve super-Earths in the stellar proximity (~0.1 au), albeit entropy advection between the envelope and the disk can further reduce the accretion rate. At an intermediate distance (~1 au) from their host stars, the escalation in the dust opacity dominates over entropy advection in stalling the transition to runaway accretion for marginally pebble-isolated cores. Beyond a few astronomical unit, the transformation of more-massive cores to gas giants is reachable before severe depletion of disk gas. This requirement can be satisfied either in extended disks with large scale height via orderly accretion of migrating pebbles or through the mergers of oligarchic protoplanetary embryos, and can account for the correlated occurrence of long-period gas giants and close-in super-Earths.

79 ASTRONOMY AND ASTROPHYSICS↗

Isolating the Electrocatalytic Activity of a Confined NiFe Motif within Zirconium Phosphate

Unique classes of active-site motifs are needed for improved electrocatalysis. Herein, the activity of a new catalyst motif is engineered and isolated for the oxygen evolution reaction (OER) created by nickel–iron transition metal electrocatalysts confined within a layered zirconium phosphate matrix. It is found that with optimal intercalation, confined NiFe catalysts have an order of magnitude improved mass activity compared to more conventional surface-adsorbed systems in 0.1 m KOH. Interestingly, the confined environments within the layered structure also stabilize Fe-rich compositions (90%) with exceptional mass activity compared to known Fe-rich OER catalysts. Through controls and by grafting inert molecules to the outer surface, it is evidenced that the intercalated Ni/Fe species stay within the interlayer during catalysis and serve as the active site. After determining a possible structure (wycherproofite), density functional theory is shown to correlate with the observed experimental compositional trends. It is further demonstrated that the improved activity of this motif is correlated to the Fe and water content/composition within the confined space. This work highlights the catalytic enhancement possibilities available through zirconium phosphate and isolates the activity from the intercalated species versus surface/edge ones, thus opening new avenues to develop and understand catalysts within unique nanoscale chemical environments.

36 MATERIALS SCIENCE↗

Trichoderma species isolated from grapevine with tolerance towards common copper fungicides used in viticulture for plant protection

Abstract BACKGROUND Copper‐containing fungicides are applied broadly in organic viticulture against downy mildew caused by Plasmopara viticola . Although long‐term application of copper‐based fungicides is associated with ecotoxic effects on the environment, their use in viticulture is required until sustainable alternatives are available. Trichoderma spp. might be a promising approach to fungicide reduction while promoting plant growth and development and displaying biocontrol activity. This study aims to examine the tolerance and compatibility of Trichoderma spp. to copper fungicides. This work contributes to the development of a spray application consisting of a copper‐tolerant Trichoderma sp. combined with a downscaled copper fungicide rate against P. viticola . RESULTS Trichoderma spp. isolated from grapevine wood in vineyards were identified and used for tolerance screening in various concentrations of copper fungicides. Copper hydroxide was identified as being highly compatible with Trichoderma . Two Trichoderma candidates, T. koningiopsis and T. harzianum , showed high copper tolerance in mycelial growth and germination tests, and were adapted to 2.85 g Cu L −1 of the selected fungicide. Microscopic investigations showed the attachment of copper compounds to fungal cell walls and copper uptake within the cytoplasm. In the case of high tolerance, large‐scale copper uptake was prevented. CONCLUSION Our findings identified two highly copper‐tolerant Trichoderma isolates with natural adaptation to the vineyard ecosystem, which could be further tested as biostimulants and biocontrol agents, combined with a reduced fungicide rate for sustainable plant protection. © 2022 Society of Chemical Industry.

Küpper, Verena↗

Isolation and Structural Elucidation of 15–Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two–Electron Copper Superatom

Highly reactive copper-dihydride clusters, [Cu 15 (H) 2 (S 2 CNR 2 ) 6 (C 2 Ph) 6 ](PF 6 ) {R = n Bu (1 H ), n Pr (2 H ), i Bu (3 H )}, are isolated during the reaction of [Cu 28 H 15 {S 2 CN n Bu 2 } 12 ](PF 6 ) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two-electron superatom [Cu 13 (S 2 CNR 2 ) 6 (C 2 Ph) 4 ] + . Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH 3 CN) 4 ](PF 6 ), BH 4 – and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu 15 (D) 2 (S 2 CNR 2 ) 6 (C 2 Ph) 6 ] + , and a single-crystal neutron structure of 2 H . Structural characterization of 1 H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH 2 ) – unit. In conclusion, reaction of 3 H with Au(I) salts yields a highly luminescent [AuCu 12 (S 2 CNiBu 2 ) 6 (C 2 Ph) 4 ] + cluster.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Genesis of Active Pt/CeO 2 Catalyst for Dry Reforming of Methane by Reduction and Aggregation of Isolated Platinum Atoms into Clusters

Atomically dispersed metal catalysts offer the advantages of efficient metal utilization and high selectivities for reactions of technological importance. Such catalysts have been suggested to be strong candidates for dry reforming of methane (DRM), offering prospects of high selectivity for synthesis gas without coke formation, which requires ensembles of metal sites and is a challenge to overcome in DRM catalysis. However, investigations of the structures of isolated metal sites on metal oxide supports under DRM conditions are lacking, and the catalytically active sites remain undetermined. Data characterizing the DRM reaction-driven structural evolution of a cerium oxide- supported catalyst, initially incorporating atomically dispersed platinum, and the corresponding changes in catalyst performance are reported. X-ray absorption and infrared spectra show that the reduction and agglomeration of isolated cationic platinum atoms to form small platinum clusters/nanoparticles are necessary for DRM activity. Density functional theory calculations of the energy barriers for methane dissociation on atomically dispersed platinum and on platinum clusters support these observations. Here the results emphasize the need for in-operando experiments to assess the active sites in such catalysts. The inferences about the catalytically active species are suggested to pertain to a broad class of catalytic conversions involving the rate-limiting dissociation of light alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Genetic mapping of sorghum resistance to an Illinois isolate of Colletotrichum sublineola

Anthracnose leaf blight (ALB) is an economically important disease of sorghum [Sorghum bicolor (L.) Moench] caused by the fungal pathogen Colletotrichum sublineola Henn. ex Sacc. & Trotter. Although qualitative and quantitative resistance have been identified for ALB, the usefulness of resistance loci differs depending on the pathogen pathotype. Identifying resistance effective against unique pathogen pathotypes is critical to managing ALB, as the disease is managed primarily through the deployment of host resistance. We isolated C. sublineola from ALB-infected leaves collected in Illinois and found that the strain was a novel pathotype, as it produced a unique combination of virulence against a set of differential lines. Using this isolate, we inoculated 579 temperate-adapted sorghum conversion lines in 2019 and 2020. We then conducted a genome-wide association study (GWAS) and a metabolic pathway analysis using the Pathway Associated Study Tool (PAST). We identified 47 significant markers distributed across all chromosomes except chromosome 8. We identified 32 candidate genes based on physical proximity with significant markers, some of which have a known role in host defense. We identified 47 pathways associated with ALB resistance, indicating a role for secondary metabolism in defense to ALB. Our results are important to improve the understanding of the genetic basis of ALB resistance in sorghum and highlight the importance of developing durable resistance to ALB.

59 BASIC BIOLOGICAL SCIENCES↗

Application of the metabolic modeling pipeline in KBase to categorize reactions, predict essential genes, and predict pathways in an isolate genome

The DOE Systems Biology Knowledgebase (KBase) platform offers a range of powerful tools for the reconstruction, refinement, and analysis of genome-scale metabolic models built from microbial isolate genomes. In this chapter, we describe and demonstrate these tools in action with an analysis of isoprene production in the Bacillus subtilis DSM genome. Two different methods are applied to build initial metabolic models for the DSM genome, then the models are gapfilled in three different growth conditions. Next, flux balance analysis (FBA) and flux variability analysis (FVA) techniques are applied to both study the growth of these models in minimal media and classify reactions within each model based on essentiality and functionality. The models are applied with the FBA method to predict essential genes, which are then compared to an updated list of essential genes obtained for B. subtilis 168, a very similar strain to the DSM isolate. The models are also applied to simulate Biolog growth conditions, and these results are compared with Biolog data collected for B. subtilis 168. Finally, the DSM metabolic models are applied to explore the pathways and genes responsible for producing isoprene in this strain. These studies demonstrate the accuracy and utility of models generated from the KBase pipelines, as well as exploring the tools available for analyzing these models.

DOE knowledgebase↗

The production of isolated photons in PbPb and pp collisions at $\sqrt{s_\mathrm{NN}} =$ 5.02 TeV

The transverse energy ($ {E}_{\mathrm{T}}^{\upgamma} $) spectra of photons isolated from other particles are measured using proton-proton (pp) and lead-lead (PbPb) collisions at the LHC at $ \sqrt{s_{\mathrm{NN}}} $ = 5.02 TeV with integrated luminosities of 27.4 pb$^{−1}$ and 404 μb$^{−1}$ for pp and PbPb data, respectively. The results are presented for photons with 25 <$ {E}_{\mathrm{T}}^{\upgamma} $< 200 GeV in the pseudorapidity range |η| < 1.44, and for different centrality intervals for PbPb collisions. Photon production in PbPb collisions is consistent with that in pp collisions scaled by the number of binary nucleon-nucleon collisions, demonstrating that photons do not interact with the quark-gluon plasma. Therefore, isolated photons can provide information about the initial energy of the associated parton in photon+jet measurements. The results are compared with predictions from the next-to-leading-order jetphox generator for different parton distribution functions (PDFs) and nuclear PDFs (nPDFs). The comparisons can help to constrain the nPDFs global fits.[graphic not available: see fulltext]

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Chemical and structural characterization of particulate fallout isolated from air-filters

We report particulate nuclear fallout is the radioactive byproduct of a nuclear event formed by the mixture of proximate environmental materials with vaporized bomb debris. The fallout debris can be transported into the atmosphere during cloud rise, raining out locally and dispersing globally constituting a radiation hazard and contributing to the distribution of anthropogenic radionuclides in the environment. Questions remain on how entrainment of environmental material in the fireball affects fallout formation processes and radionuclide incorporation and distribution during cooling. To inform the characterization of fallout including the development of fallout size distributions and how radionuclides are incorporated into fallout debris where entrainment plays a role, we analyzed an archived historic US air-filter collected by aircraft in the aftermath of ground interacting nuclear tests. Particulate fallout collected on the filter was isolated and analyzed using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and NanoSIMS (Secondary Ion Mass Spectrometry) to determine chemistry, structure, morphology, and size of the particles. Results demonstrate that the particles isolated from the filter have spherical shape, display complex internal structures, and are mainly composed of Fe and Si oxides. In these spherical particles, Pu is preferentially associated with Fe-rich composition. The characterization of fallout particulate samples can provide information on nucleation and particle growth from the vapor phase to improve modeling and simulation of fallout hazards.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Biomass and salt-dependent effects of Bacillus spores on radionuclide migration from the Waste Isolation Pilot Plant

Spores of a Bacillus sp., isolated from radioactive waste, were tested for their ability to influence the fate and transport of neodymium (Nd3+) under high salt conditions expected at the Waste Isolation Pilot Plant (WIPP) nuclear waste repository. Spores were suspended in neodymium-spiked saline solutions up to 4 M NaCl, and concentrations of Nd and the complexing agent dipicolinic acid (DPA), a component of spores, were monitored along with optical densities and spore numbers. Overall, results support neodymium bioassociation that is dependent upon biomass, with more apparent adsorption occurring at higher spore concentrations. However, probable spore lysis in 2 and 4 M NaCl solutions and possible germination at 0.15 M NaCl appear to drive the release of DPA and subsequent return of Nd to solution. The implications of this work for the WIPP will depend on actual biomass levels and the ionic strength of the repository brines.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Complete genome of Polaromonas vacuolata KCTC 22033 T isolated from beneath Antarctic Sea ice

Polaromonas vacuolata KCTC 22033 T is an obligate aerobic, Gram-negative, psychrophilic and rod-shaped bacterium isolated from beneath the sea ice off the coast of the Palmer Peninsula, Anvers Islands, Antarctica. P. vacuolata is the type species of Polaromonas genus and the first example of gas vacuolate Betaproteobacteria isolated from marine habitats. In this study, we report a complete genome of P. vacuolata KCTC 22033 T , which consists of 3,837,686 bp (G + C content of 52.07%) with a single chromosome, 3461 protein-coding genes, 56 tRNAs and 6 rRNA operons. Genomic analysis revealed the presence of genes involved in bacterial adaptation under saline conditions, cold adaptation via the production of gas vesicles and cell adhesion proteins, and a photoheterotrophic lifestyle when challenged by starvation. Intriguingly, several of these genes were likely acquired from species outside the Polaromonas genus. The genomic information therefore describes the unique evolution and adaptation of P. vacuolata to its extraordinary habitat, i.e., beneath the Antarctic sea ice.

59 BASIC BIOLOGICAL SCIENCES↗

Reactions of Studtite UO 4 ·4H 2 O in Alkali Hydroxides: Isolation of Single-Crystal Uranate Phases under Mild Hydrothermal Conditions

Uranyl peroxide complexes, particularly studtite (UO 4 ·4H 2 O), are important phases within the nuclear fuel cycle, forming through radiolysis-induced reactions on the surfaces of spent fuel and in waste environments. Studtite has been identified in Hanford’s irradiated fuel storage basins, Chornobyl’s corium lavas, and is anticipated on Fukushima’s fuel debris. While its formation and stability have been extensively studied, the reactivity of UO 4 ·4H 2 O in highly alkaline environments such as those encountered in high-level nuclear waste remains underexplored. These environments contain molar concentrations of [OH - ] and present a chemically dynamic and reactive environment where actinide behavior is not well understood. Reported here are investigations of uranium reactions in concentrated alkali hydroxides under mild hydrothermal conditions (<200 °C) that have resulted in the isolation of the alkali metal uranates Li 2 UO 4 , α-Na 2 UO 4 , γ-Na 2 U 2 O 7 , and K 2 U 2 O 7 . In contrast to conventional solid-state methods (>800 °C) that typically yield polycrystalline powders, our approach enables the isolation of these uranates as single crystals, allowing us to provide single-crystal structure solutions of certain uranates for the first time. Our findings match the results of high-level waste tank sampling, confirming that sodium diuranate (Na 2 U 2 O 7 ) is the most persistent uranium phase, potentially forming through reactions of uranyl peroxide intermediates with NaOH under radiolytic and highly alkaline conditions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Quantifying the Reactivity of Isolated Li x Si Domains in Si Anodes Using Operando NMR

The use of Si anodes can greatly improve the energy density of Li-ion batteries. However, understanding and mitigation of calendar aging remains a barrier to commercialization. Here, in this short report, we utilize operando Nuclear Magnetic Resonance (NMR) spectroscopy to detect and quantify lithium silicides (Li x Si) as they form and react within Si anodes in pouch cells during calendar aging. We provide direct experimental evidence of complex aging phenomena in the Si anodes, including both SEI growth and dissolution during storage. Formation of electrochemically isolated Li x Si is also observed, as indicated by the partial persistence of highly lithiated phases after the cell is discharged. Remarkably, we show that these isolated domains can themselves self-discharge over time, suggesting that their detection can be challenging in post-mortem studies. Finally, we show that aging outcomes depend heavily on the type of silicon particles contained within the electrode, and that certain surface coatings can help decrease the reactivity between lithium silicides and the electrolyte.

Li-ion battery↗

Re-examination of the Claimed Isolation of Stable Noncyclic 1,2-Disulfoxides

Re-examination of the claimed isolation and X-ray characterization of di-p-tolyl and dimesityl 1,2-disulfoxides from thermolysis of the corresponding aryl sulfinimines and thiosulfinates showed that the isolated disulfide dioxides are instead the wellknown isomeric thiosulfonates, as confirmed by XAS, DART-MS, X-ray, IR and NMR methods. Concerns with the original X-ray structures are addressed. Our results agree with the DFT prediction of very weak diaryl 1,2-disulfoxide S–S bond dissociation enthalpies. For now, room-temperature-stable noncyclic 1,2-disulfoxides remain unknown.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Copper(III) Metallacyclopentadienes via Zirconocene Transfer and Reductive Elimination to an Isolable Phenanthrocyclobutadiene

Despite the widespread use of copper catalysis for the formation of C–C bonds, debate about the mechanism persists. Reductive elimination from Cu(III) is often invoked as a key step, yet examples of its direct observation from isolable complexes remain limited to only a few examples. In this work, we demonstrate that incorporation of bulky mesityl (Mes) groups into the α-positions of a phenanthrene-appended zirconacyclopenta- diene, Cp 2 Zr(2,5-Mes 2 -phenanthro[9,10]C 4 ), enables efficient oxidative transmetalation to the corresponding, formal Cu(III) metallacyclopentadiene dimer. The dimer was quantitatively converted to a structurally analogous anionic monomer [ n Bu 4 N]- {Cl 2 Cu(2,5-Mes 2 -phenanthro[9,10]C 4 )} upon treatment with [ n Bu 4 N][Cl]. Both metallacycles undergo quantitative reductive elimination upon heating to generate phenanthrocyclobutadiene and a Cu(I) species. Due to the steric protection provided by the mesityl groups, this cyclobutadiene was isolated and thoroughly characterized to reveal antiaromaticity comparable to that of free cyclobutadiene, which imbues it with a small highest occupied molecular orbital–lowest unoccupied molecular orbital energy gap of 1.85 eV and accessible reduced and oxidized electronic states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, Isolation, and Study of Heterobimetallic Uranyl Crown Ether Complexes

Although crown ethers can selectively bind many metal cations, little is known regarding the solution properties of crown ether complexes of the uranyl dication, UO 2 2+ . Here, in this work, the synthesis and characterization of isolable complexes in which the uranyl dication is bound in an 18-crown-6-like moiety are reported. A tailored macrocyclic ligand, templated with a Pt(II) center, captures UO 2 2+ in the crown moiety, as demonstrated by results from single-crystal X-ray diffraction analysis. The U(V) oxidation state becomes accessible at a quite positive potential (E 1/2 ) of –0.18 V vs Fc +/0 upon complexation, representing the most positive U VI /U V potential yet reported for the UO 2 n+ core. Isolation and characterization of the U(V) form of the crown complex are also reported here; there are no prior reports of reduced uranyl crown ether complexes, but U(V) is clearly stabilized by crown chelation. Joint computational studies show that the electronic structure of the U(V) form results in significant weakening of U–O oxo bonding despite the quite positive reduction potential at which this species can be accessed, underscoring that crown-ligated uranyl species could demonstrate unique reactivity under only modestly reducing conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗