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At least 505 records · Page 28

Salt Sample Statistical Study

Historically there has, at times, been large variability in measured uranium concentration amongst salt samples taken at the same time from the electrorefiner with relative standard deviations ranging from 0.59% up to a high of 114%. This has led to uncertainty in the actual uranium content of the salt. A series of surrogate experiments were performed with gadolinium to study the effects of Li2O, Gd2O3, and Gd metal additions to an LiCl-KCl-GdCl3 salt on the gadolinium content of the salt. These experiments showed no increase in salt sample variability following the additions of the mentioned species, indicating that the carryover of these species from the oxide reduction process may not lead to the historic variability issues.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Nitric oxide formation by meteoroids in the upper atmosphere

The process of nitric oxide formation during atmospheric entry of meteoroids is analyzed theoretically. An ablating meteoroid is assumed to be a point source in a uniform flow with a continuum regime evolving in its wake. The amount of nitric oxide produced by high-temperature reactions of air in the continuum regime is calculated by numerical integration of chemical-rate equations. This is accomplished by assuming that flow properties are constant across the reacting region, its radius being determined from considerations of shock-wave formation and molecular diffusion. The results, when summed over the observed mass, velocity, and entry-angle distributions of meteoroids, provide annual global production rates of nitric oxide as a function of altitude. The peak production is found to occur between 90- and 100-km altitude, the total annual rate being around 40 million kg.

Menees, G. P.↗

Nitric oxide formation by meteoroids in the upper atmosphere

The process of nitric oxide formation during atmospheric entry of meteoroids is analyzed theoretically. An ablating meteoroid is assumed to be a point source in a uniform flow with a continuum regime evolving in its wake. The amount of nitric oxide produced by high-temperature reactions of air in the continuum regime is calculated by numerical integration of chemical-rate equations. The results, when summed over the observed mass, velocity, and entry-angle distributions of meteoroids, provide annual global production rates of nitric oxide as a function of altitude. The peak production of nitric oxide is found to occur at altitudes between 90 and 100 km, the total annual rate being about 40 million kg. The present results suggest that the large concentration of nitric oxide observed below 95 km could be attributed to meteoroids instead of photodissociation of nitrogen.

Menees, G. P.↗

Nitric Oxide Formation by Meteoroids in the Upper Atmosphere

The process of nitric oxide formation during atmospheric entry of meteoroids is analyzed theoretically. An ablating meteoroid is assumed to be a point source in a uniform flow with a continuum regime evolving in its wake. The amount of nitric oxide produced by high-temperature reactions of air in the continuum regime is calculated by numerical integration of chemical-rate equations. This is accomplished by assuming that flow properties are constant across the reacting region, the radius of the region being determined from considerations of shock-wave formation and molecular diffusion. The results, when summed over the observed mass, velocity, and entry-angle distributions of meteoroids, provide annual global production rates of nitric oxide as a function of altitude. The peak production of nitric oxide is found to occur at altitudes between 9 x 10(exp 4) and 10(exp 5) m, the total annual rate being about 4 x 10(exp 7) kg. The present results suggest that the large concentration of nitric oxide observed below 9.5 x 10(exp 4) m could be attributed to meteoroids instead of photodissociation of nitrogen into metastable, 2D-state atoms, as has been previously hypothesized.

Menees, Gene P.↗

Beyond denitrification: The role of microbial diversity in controlling nitrous oxide reduction and soil nitrous oxide emissions

Many biotic and abiotic processes contribute to nitrous oxide (N 2 O) production in the biosphere, but N 2 O consumption in the environment has heretofore been attributed primarily to canonical denitrifying microorganisms. The nosZ genes encoding the N 2 O reductase enzyme, NosZ, responsible for N 2 O reduction to dinitrogen are now known to include two distinct groups: the well-studied Clade I which denitrifiers typically possess, and the novel Clade II possessed by diverse groups of microorganisms, most of which are non-denitrifiers. Clade II N 2 O reducers could play an important, previously unrecognized role in controlling N 2 O emissions for several reasons, including: (1) the consumption of N 2 O produced by processes other than denitrification, (2) hypothesized non-respiratory functions of NosZ as an electron sink or for N 2 O detoxification, (3) possible differing enzyme kinetics of Clade II NosZ compared to Clade I NosZ, and (4) greater nosZ gene abundance for Clade II compared to Clade I in soils of many ecosystems. Despite the potential ecological significance of Clade II NosZ, a census of 800 peer-reviewed original research articles discussing nosZ and published from 2013 to 2019 showed that the percentage of articles evaluating or mentioning Clade II nosZ increased from 5% in 2013 to only 22% in 2019. The census revealed that the slowly spreading awareness of Clade II nosZ may result in part from disciplinary silos, with the percentage of nosZ articles mentioning Clade II nosZ ranging from 0% in Agriculture and Agronomy journals to 32% in Multidisciplinary Sciences journals. In addition, inconsistent nomenclature for Clade I nosZ and Clade II nosZ, with 17 different terminologies used in the literature, may have created confusion about the two distinct groups of N 2 O reducers. Furthermore, we provide recommendations to accelerate advances in understanding the role of the diversity of N 2 O reducers in regulating soil N 2 O emissions.

59 BASIC BIOLOGICAL SCIENCES↗

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↗

Revealing the etching process of water-soluble Au 25 nanoclusters at the molecular level

Etching (often considered as decomposition) is one of the key considerations in the synthesis, storage, and application of metal nanoparticles. However, the underlying chemistry of their etching process still remains elusive. Here, we use real-time electrospray ionization mass spectrometry to study the reaction dynamics and size/structure evolution of all the stable intermediates during the etching of water-soluble thiolate-protected gold nanoclusters (Au NCs), which reveal an unusual “recombination” process in the oxidative reaction environment after the initial decomposition process. Interestingly, the sizes of NC species grow larger and their ligand-to-metal ratios become higher during this recombination process, which are distinctly different from that observed in the reductive growth of Au NCs (e.g., lower ligand-to-metal ratios with increasing sizes). The etching chemistry revealed in this study provides molecular-level understandings on how metal nanoparticles transform under the oxidative reaction environment, providing efficient synthetic strategies for new NC species through the etching reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlled decomposition and oxidation: A treatment method for gaseous process effluents

The safe disposal of effluent gases produced by the electronics industry deserves special attention. Due to the hazardous nature of many of the materials used, it is essential to control and treat the reactants and reactant by-products as they are exhausted from the process tool and prior to their release into the manufacturing facility's exhaust system and the atmosphere. Controlled decomposition and oxidation (CDO) is one method of treating effluent gases from thin film deposition processes. CDO equipment applications, field experience, and results of the use of CDO equipment and technological advances gained from the field experiences are discussed.

Mckinley, Roger J. B., Sr.↗

Development of high Tc (greater than 100 K) Bi, Tl and Y-based materials as superconducting circuit elements

Experimental work on this project over the last four years has resulted in establishing processing and characterization techniques for producing both the Bi-based and Tl-based superconductors in their high temperature (2223) forms. In the bulk, dry pressed form, maximum critical temperatures (Tc) of 108.2 K and 117.8 K, respectively, were measured. Results have further shown that the Bi and Tl-based superconducting materials in bulk form are noticeably different from the Y-based 123 material in that superconductivity is considerably harder to achieve, maintain, and reproduce. This is due primarily to the difficulty in obtaining the higher Tc phase in pure form since it commonly co-exists with other undesirable, lower Tc phases. In particular, it has been found that long processing times for calcining and firing (20 - 200 hrs.) and close control of temperatures which are very near the melting point are required in order to obtain higher proportions of the desirable, high Tc (2223) phase. Thus far, the BSCCO bulk materials has been prepared in uniaxially pressed, hot pressed, and tapecast form. The uniaxially pressed material has been synthesized by the mixed oxide, coprecipitation, and melt quenching processes. The tapecast and hot pressed materials have been prepared via the mixed oxide process. In addition, thick films of BSCCO (2223 phase) have been prepared by screen printing on to yttria and magnesia stabilized zirconia with only moderate success; i.e., superconductivity was achieved in these thick films, but the highest Tc obtained in these films was 89.0 K. The Tc's of the bulk hot pressed, tapecast, and screen printed thick film materials were found to be 108.2, 102.4, and 89.0 K, respectively.

Haertling, Gene↗

Insights into the Electrochemical Oxidation and Reduction of Nickel Oxide Surfaces

Surface oxidation/reduction processes, driven by varying electrochemical potentials, can substantially impact catalyst effectiveness and, consequently, electrolyzer performance. Here, this study combines theoretical and experimental approaches to explore the surface redox behavior of nickel oxides, which are cost-effective and efficient catalysts for many electrochemical reactions. Surface Pourbaix diagrams for three different phases of nickel oxides, i.e., nickel hydroxide (Ni(OH) 2 ), nickel oxyhydroxide (NiOOH), and nickel dioxide (NiO 2 ), were constructed using density functional theory-based simulations. Various experimental methods, including cyclic voltammetry, in situ Raman spectroscopy, and electrochemical titration, were employed to probe the surface redox processes of nickel oxide thin films. Our findings indicate that the ABAB stacking sequence of Ni(OH) 2 lacks stability under oxidizing conditions to host the surface oxidation (deprotonation) events, while the AABBCC stacking sequence of NiOOH is energetically favorable due to the presence of interlayer hydrogen bonding. Rapid charge transfer facilitated by interlayer hydrogen bonding accounts for the higher reactivity of partially oxidized/reduced NiOOH (001) surfaces compared to Ni(OH) 2 (001) and NiO 2 (001) surfaces with the same stoichiometry, where interlayer hydrogen bonding is absent. Insights presented in this work can offer guidelines for optimizing operational conditions and tailoring the surface structures and oxidation states of nickel oxides to enhance performance in applications such as electrocatalysis and supercapacitors.

36 MATERIALS SCIENCE↗

Electrochemical chlor-iron process for iron production from iron oxide and salt water

The iron and steel industry accounts for ~8% of global greenhouse gas emissions. Electrochemical reduction of iron ore to metal for electric arc furnaces can enable sustainable steel production, but existing electrochemical processes require expensive capital or electrolytes. Here we report a low-temperature, electrochemical cell that consumes low-cost and abundant iron oxide and aqueous sodium chloride, while co-producing sodium hydroxide and chlorine. Industrially relevant current densities and Faradaic efficiencies for iron production were demonstrated, with 94% selectivity to iron metal at an applied current density of 200 mA cm –2 . Freestanding films of phase-pure iron were formed after 4h of continuous, stable electrolysis. The process can lead to levelized costs of iron that are competitive with iron produced in fossil-fuel-powered blast furnaces, and the co-produced sodium hydroxide can be used for CO 2 capture from the air or ocean, creating a net-negative-emission process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plant-specific features of respiratory supercomplex I + III2 from Vigna radiata

Abstract The last steps of cellular respiration—an essential metabolic process in plants—are carried out by mitochondrial oxidative phosphorylation. This process involves a chain of multi-subunit membrane protein complexes (complexes I–V) that form higher-order assemblies called supercomplexes. Although supercomplexes are the most physiologically relevant form of the oxidative phosphorylation complexes, their functions and structures remain mostly unknown. Here we present the cryogenic electron microscopy structure of the supercomplex I + III 2 from Vigna radiata (mung bean). The structure contains the full subunit complement of complex I, including a newly assigned, plant-specific subunit. It also shows differences in the mitochondrial processing peptidase domain of complex III 2 relative to a previously determined supercomplex with complex IV. The supercomplex interface, while reminiscent of that in other organisms, is plant specific, with a major interface involving complex III 2 ’s mitochondrial processing peptidase domain and no participation of complex I’s bridge domain. The complex I structure suggests that the bridge domain sets the angle between the enzyme’s two arms, limiting large-scale conformational changes. Moreover, complex I’s catalytic loops and its response in active-to-deactive assays suggest that, in V. radiata , the resting complex adopts a non-canonical state and can sample deactive- or open-like conformations even in the presence of substrate. This study widens our understanding of the possible conformations and behaviour of complex I and supercomplex I + III 2 . Further studies of complex I and its supercomplexes in diverse organisms are needed to determine the universal and clade-specific mechanisms of respiration.

59 BASIC BIOLOGICAL SCIENCES↗

Removal of Residual Chromium from Aluminum Oxide by Containerless Liquid-phase Processing

Berneuil sapphire was purified of Cr 3+ by containerless melting and processing at ca. 2550 K in high purity argon, dry air and pure oxygen. Recovered material was examined by laser induced fluorescence and Raman spectroscopy. The Cr 3+ fluorescence intensity decreased in processed specimens at rates proportional to the chromium concentration and p(O 2 ) 0.21 . The initial chromium concentration was ca. 5 ppm and decreased by factors of ca. 50, 3000, and 2x10 5 after processing for 300 seconds in argon, air and oxygen, respectively. Evidence is presented that the Cr 3+ was removed predominantly as CrO 2 (g) and not by conversion to other oxidation states of chromium in the condensed phase. A comparison of the Raman peak shifts for as-received and processed samples indicates that considerable stress was retained during containerless solidification of the highly undercooled melts.

sapphire↗

Characterization Techniques Investigated for Characterization of Anomalous Materials in Plutonium Oxide – 25666

The DOE has adopted a Dilute and Dispose approach for processing surplus plutonium which consists of blending plutonium oxide with adulterants and packaging it in a form which is acceptable for disposal at the Waste Isolation Pilot Plant. The feed material for the downblend process is intended to be pure plutonium oxide powder, however other objects are occasionally encountered within the oxide, particularly with legacy material. Potential technologies which could assist in the resolution of incidents where such anomalies are encountered have been investigated. Resolution of these incidents requires characterization of the anomalous object so that plutonium oxide processing can resume and so that a disposition pathway can be determined for the anomalous material. Technologies including gamma ray spectroscopy, alpha-gamma coincidence, LiDAR volumetric measurements, and surface conductivity measurements were investigated for this purpose, with a focus on systems which can be easily introduced into the processing environment when an anomaly is encountered, then removed from the environment after resolution to avoid impeding normal processing activities. This places an emphasis on small and portable measurement systems and systems that can operate in a high-background, oxide-processing environment. Gamma ray systems investigated include the GR1™a CZT detector and the MicroGe™a germanium detector, with a focus on detecting characteristic gamma rays from Pu-239 and other actinides. A gamma ray and alpha particle coincidence method was investigated with the goal of identifying actinides in the presence of a gamma ray background produced by adjacent plutonium oxide material. Leica™b BLK360 G1 and Keyence™c LJ-X8300 LiDAR systems were investigated for use in conjunction with mass measurements to gain accurate material density values, and a Foerster Sigmatest™d 2.070 was tested to determine surface conductivity. The combination of these properties would allow improved identification and characterization of a wide variety of potential anomalous material.

Munson, Justin M.↗

Mars - Chemical weathering as a massive volatile sink

The amounts of volatiles incorporated in the Martian regolith by photostimulated oxidation weathering of Fe(2+)-bearing minerals are estimated. The process of photostimulated oxidation weathering is described, and it is noted that all the necessary constituents for this process are present on Mars. The rates at which oxygen and hydrogen are irreversibly removed from the Martian atmosphere by the present process are determined, irreversible and reversible water losses are considered, and the loss of CO2 by carbonate formation is shown to be irreversible. The results suggest that photostimulated oxidation weathering has irreversibly consumed 100 to 100,000 g/sq cm of H2O and 10 to 10,000 g/sq cm of CO2, assuming a uniform rate over geologic time. It is concluded that if the amounts of H2O and CO2 actually removed by photostimulated oxidation are close to the upper limits of the present estimates, then that process may have had a major effect in limiting the amount of H2O and CO2 trapped in the regolith and polar caps.

Huguenin, R. L.↗