Neptunium and Uranium Reduction Chemistry [Slides]
Various characterizations are shown.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
SEARCH · Search NASA
Results for “neptunium”
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.
Measuring Neptunium Concentration using Optical Spectrometry for the Pu-238 Supply Program
Targets containing 237 Np are irradiated at the High Flux Isotope Reactor at Oak Ridge National Laboratory to produce 238 Pu, as plutonium dioxide (PuO 2 ), a heat source material for use in future NASA space missions. Kilogram quantities of Np are processed yearly and developing methods to efficiently characterize and monitor the Np processing streams with optical spectroscopy and real-time monitoring software is a critical aspect of this effort. Here, we evaluate how ultraviolet/visible/near-infrared (UV-Vis-NIR) absorbance and Raman spectroscopic techniques are applicable to characterizing concentrated Np solutions and provide proof-of-principle and proof-of-concept results for each technique. Both techniques were tested in lab-scale studies and should improve the timeliness of production efforts. However, spectrophotometry is the more mature option and has been successfully demonstrated in a hot cell environment. An overview of the initial findings, a brief demonstration, and areas for future work will be highlighted in this report.
07 ISOTOPE AND RADIATION SOURCES↗
Recommended Updates to Solubility Controls for Modeling Leaching of Technetium, Uranium, Neptunium, Plutonium, and Iodine from the Residual Waste Layer of Closed Savannah River Site High Level Waste Tanks
The objective of this report is to relate waste leaching experiments by the Savannah River National Laboratory (SRNL) to performance assessment modeling of release of several radionuclides from residual waste in closed high-level waste tanks. SRNL leached residual waste from Tanks 18F and 12H with solutions simulating the modeled evolution of pore fluids in residual waste layers of closed tanks through various stages of grout degradation. Tc-99, uranium isotopes, Np-237, plutonium isotopes, and I-129 were analyzed in the leachate multiple times over 90 days.
07 ISOTOPE AND RADIATION SOURCES↗
Neptunium (V) Solubility in the Presence and Absence of WIPP Relevant Ligands
CRA (Compliance Recertification Application)-2024 will update the oxidation state specific model used to calculate actinide solubility in the WIPP (Waste Isolation Pilot Plant). The pentavalent Np(V) ion is the most stable ion in solution within the An(V) series. This valence stability of Np(V) in aqueous solution makes Np a useful representative element for studying the aqueous complex chemistry of all An(V), but in the predicted WIPP scenario, this is the only TRU component that increases in the inventory with time as it is the main daughter product of 241 Am decay (alpha, n) so its relative importance increases throughout the 10,000-year performance period of the WIPP, it is only used to represent itself. This work is focused on confirming organic, borate and carbonate effects on solubility of Np(V) in WIPP simulated brines and 5 M NaCl and reassessing the predicted model speciation to strengthen the overall WIPP An(V) model.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Quantifying neptunium oxidation states in nitric acid through spectroelectrochemistry and chemometrics
Controlled-potential in situ thin-layer spectropotentiometry was leveraged to generate visible/near-infrared (VIS/NIR) absorption spectral data sets for the development of chemometric models to quantify Np(III/IV/V/VI) oxidation states in HNO 3 . This technology would be valuable in laboratory studies and when monitoring process solutions to guide feed adjustments for radiochemical separations—the performance of which depends on oxidation state. This approach successfully isolated and stabilized Np species in pure (~99%) oxidation states without compromising solution optical properties. Multivariate curve resolution–alternating least squares models were evaluated to resolve spectral and component concentrations from a scan that sequentially produced Np(VI), Np(V), Np(IV), and Np(III) spectra with mixtures of two valences at a time. Although it provided a useful approximation, the method was not able to quantitively resolve each component likely because of rotational ambiguity. Additionally, partial least squares regression models were built from artificial and electrochemically generated VIS/NIR spectral training sets to study the effect of interionic interactions on spectral characteristics. Models built with true Bi-chemical mixtures of coexisting Np oxidation states and spectra generated from additive combinations of pure end points had similar prediction performance. This methodology can be used to directly quantify Np concentration and the ratio of Np oxidation states and other actinides in remote settings such as hot cells.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Source Data for Calculations, UV-vis-NIR, and NMR for A Tetrahedral Neptunium(V) Complex
Data associated with the Nature Chemistry publication (DOI: 10.1038/s41557-024-01529-6 ) was made publicly available in a FigShare repository (10.6084/m9.figshare.24309463) to ensure reproducibility and support the PI's commitment to open-science that was included in the data management plan of the project
Niklas, Julie E.↗
Neptunium transition probabilities estimated through laser induced breakdown spectroscopy (LIBS) measurements
Explore the source record for details and available documents.
H. B. Andrews↗
Correction: Neptunium transition probabilities estimated through laser induced breakdown spectroscopy (LIBS) measurements
Explore the source record for details and available documents.
H. B. Andrews↗
Crystallization of a Neptunyl Oxalate Hydrate from Solutions Containing Np V and the Uranyl Peroxide Nanocluster U 60 Ox 30
Uranyl peroxide nanoclusters are an evolving family of materials with potential applications throughout the nuclear fuel cycle. While several studies have investigated their interactions with alkali and alkaline earth metals, no studies have probed their interactions with the actinide elements. This work describes a system containing U 60 Ox 30 , [((UO 2 )(O 2 )) 60 (C 2 O 4 ) 30 ] 60- , and neptunium(V) as a function of neptunium concentration. Ultra-small and small angle X-ray scattering were used to observe these interactions in the aqueous phase, and X-ray diffraction was used to observe solid products. The results show that neptunium induces aggregation of U 60 Ox 30 when the neptunium concentration is ≤ 10 mM, whereas (NpO 2 ) 2 C 2 O 4 ·6H 2 O(cr) and studtite ultimately form at 15–25 mM neptunium. Finally, the latter result suggests that neptunium coordinates with the bridging oxalate ligands in U 60 Ox 30 , leaving metastable uranyl peroxide species in solution, and is an important finding given the potential application of uranyl peroxide nanoclusters in the recycling of used nuclear fuel.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Neptunyl Pyrrophen Complexes: Exploring Schiff Base Chemistry with Multidentate Acyclic Ligands and Transuranics
Here we report the synthesis, structure, and characterization of two novel neptunyl complexes (NpO 2 L1 and NpO 2 L2) constructed from phenylene-substituted benzyl ester bis(pyrrole)phenylenediamine (named “pyrrophen”) ligands. In both cases, the neptunium center exists in the +6 oxidation state,. As our specific interest is in exploring the chemistry of neptunium compounds containing the linear neptunyl ion (NpO 2 2+ ) through equatorially coordinating the metal by multidentate organic ligands, we have identified the differences that are likely to cause discrepancy between the two complexes by examining the ions and their coordinative environments through single-crystal X-ray crystallography, diffuse reflectance, and Raman spectroscopy. This is the first time pyrrophen has been utilized in Np chemistry and demonstrates a new platform to study 5 f electron participation and coordination.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Improving understanding of NpO 2 and Np 2 O 5 through vibrational spectroscopy
Raman spectra of three NpO 2 samples and two samples produced from a modified direct denitration (MDD) process were collected. The spectral features of the NpO 2 samples were consistent and indicated only NpO 2 . The spectra of the MDD samples indicated the presence of NpO 2 and an additional phase attributed to the neptunium binary oxide Np 2 O 5 . These Raman spectra are the first reported of Np 2 O 5 , and the proportions of these neptunium oxide phases varied within the samples, suggesting significant sample inhomogeneity. Peaks in the Raman spectra of Np 2 O 5 at 569 and 782 cm –1 were tentatively assigned to concerted, symmetric stretches of the neptunyl cations. Finally, laser-induced heating of regions in the MDD samples that were rich in Np 2 O 5 showed spectral features that indicated conversion to NpO 2 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Gamma-ray imaging of Np-237 metal using an organic glass imager
Neutron and gamma-ray imaging systems are deployed within the field of nuclear safeguards for the detection and localization of special nuclear materials and other materials of interest. 237 Np is one of these materials of interest due its presence in spent nuclear fuel and potential for use in nuclear weapons when purified. Here, for the first time, a 6 kg neptunium sphere (98.8 wt% 237 Np) was measured using a dual-particle imager, from the University of Michigan, consisting of organic glass and inorganic scintillators. The novel composition of organic glass scintillator was recently developed at Sandia National Labs and has been used in particle imaging systems due to its time resolution and particle discrimination capabilities. Gamma-ray energy spectra from single and coincident events were extracted and the sequencing of Compton scatter and photoelectric absorption gamma-ray events was used to generate images using simple backprojection. The emissions of interest in this work are the 312 keV and 416 keV gamma rays from 233 Pa, a daughter isotope from the neptunium decay series. The results of this work show that there is close agreement between the true source location in angular space and the converged location from the gamma ray images created using the system. The gamma spectroscopy from single and coincident events also identified the characteristic emission from the daughter isotope and could be used to assist with the identification of 237 Np. Furthermore, successful localization of the source with 5 s of data demonstrates the practical application of the imaging system for imaging and detection of material in weapons-useable quantities.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Vibrational and electronic properties of Np 2 O 5 from experimental spectroscopy and first principles calculations
High-valence actinide oxides are critical to understanding the behavior of 5f-electrons, yet their structural and electronic properties remain poorly understood due to challenges in synthesis and handling. We report the first Raman spectroscopic study of single-crystalline Np 2 O 5 and the first scanning tunneling spectroscopy (STS) measurement on any neptunium-containing material. Hydrothermally synthesized crystals were structurally verified by X-ray diffraction. Raman spectra revealed sharply resolved vibrational features, including previously unreported low-frequency modes. STS measurements revealed a band gap of 1.5 eV. Density functional theory (DFT) enables vibrational mode assignments, reveals neptunium-dominated low-frequency phonons, oxygen-dominated high-frequency modes, and predicts an indirect band gap of 1.68 eV. This predicted value is in excellent agreement with the experimentally measured STS gap. This combined Raman, DFT, and STS approach provides a robust framework for correlating lattice dynamics and electronic structure in actinide materials, providing benchmark data for Np 2 O 5 , and opening new avenues for probing structure–property relationships in complex f-electron materials.
36 - MATERIALS SCIENCE↗
New reference materials for trace-levels of actinide elements in plutonium
In this report two plutonium oxides were prepared as unique reference materials for measurement of actinide elements present as trace constituents. Each reference material unit is approximately 200 mg of PuO 2 powder in a quartz glass bottle. Characterized attributes of the oxides included mass fractions of plutonium, americium, neptunium, and uranium. Isotope-amount ratios were also determined for plutonium and uranium, but neptunium and americium were observed to be monoisotopic 237 Np and 241 Am. Measurements for characterization and verification of the attributes show that plutonium and trace actinides are homogeneous with the exception of limited heterogeneity for uranium, primarily observed for the 238 U isotope. Model purification ages calculated from measured americium and uranium attribute values are consistent with material histories and indicate that these impurities are predominantly due to the decay of plutonium isotopes.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Influencing Bonding Interactions of the Neptunyl (V, VI) Cations with Electron-donating and -withdrawing Groups
Neptunium makes up the largest percentage of minor actinides found in spent nuclear fuel, yet separations of this element have proven difficult due to its rich redox chemistry. Developing new reprocessing techniques should rely on understanding how to control the Np oxidation state and its interactions with different ligands. Designing new ligands for separations requires understanding how to properly tune a system toward a desired trait through functionalization. Emerging technologies for minor actinide separations focus on ligands containing carboxylate or pyridine functional groups, which are desirable due to their high degree of functionalization. So we use DFT calculations to study the interactions of carboxylate and polypyridine ligands with the neptunyl cation [Np(V/VI)O2] +/2+ . A systematic study is performed by varying the electronic properties of the carboxylate and polypyridine ligands through the inclusion of different electron-withdrawing and electron-donating R groups. We focus on how these groups can affect geometric properties, electronic structure, and bonding characterization as a function of the metal oxidation state and ligand character and discuss how these factors can play a role in neptunium ligand design principles.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides
The trivalent actinides are produced in the nuclear fuel cycle during power production and provide the largest long-term radiation dose in used nuclear fuel. It is ideal for these elements to be removed from used nuclear fuel for disposal and a necessity for fuel recycling. A key challenge to this is the similarity of chemical behavior of the trivalent actinides to the lanthanides that are also present as fission products in used fuel. Thus far, some of the most effective separations of actinides from lanthanides utilise chelating agents containing sulfur moieties such as dithiophosphinates that selectively bind to actinide ions because of a greater bond covalency relative to lanthanide ions. Typically, greater differences between actinide and lanthanide ions are observable the more ligands and chelators bonds have a covalent character. Here, a series of complexes of the trivalent actinides Np(III) through Cf(III) (excluding Bk(III)) with maleonitrile-1,2-dithiolate (mnt 2– ) are synthesized along with their lanthanide counterparts (La(III) – Nd(III), Sm(III) – Gd(III), Dy(III)), in order to characterize the nature of chemical bonds with these metal ions and a polarizable, non-innocent, sulfur-donor ligand. The metal-sulfur bonds in these complexes trend shorter than measured for lanthanides with equivalent ionic radii. However, particularly large deviations are observed in the neptunium and plutonium complexes in both structure and bonding, resulting in a nonlinear bond length trendline for the actinide series. Density Functional Theory (DFT) calculations with Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Order (NBO) analyses indicate that for the neptunium and plutonium complexes, the presence of increased 5f-orbital participation, energy degeneracy of the metal and ligand orbitals, and the structure packing result in shortened M–S bonds. The stabilization of the energy of the 5f-orbitals and the decrease in f-contribution to bonding orbitals in the later actinides results in structural properties more similar to the lanthanide complexes.
07 ISOTOPE AND RADIATION SOURCES↗
Thermal decomposition of neptunyl ammonium nitrate: mechanistic insights and structural characterization of the Np 2 O 5 intermediate phase
Neptunium (Np) possesses a rich and unique chemistry that often diverges from other actinide elements yet remains relatively underexplored compared with the other light actinides. A resurgence of interest in Np has been spurred by the application of 237 Np for plutonium-238 ( 238 Pu) production for use in radioisotope thermoelectric generators (RTGs), necessitating evaluation of Np chemical reactions and materials. The work presented here studied the thermal decomposition of neptunyl ammonium nitrate (NH 4 Np VI O 2 (NO 3 ) 3 ) for synthesis of neptunium dioxide (NpO 2 ), which is the target material used for production of 238 Pu. Additionally, structural characterization of the intermediate solid Np pentoxide (Np 2 O 5 ) was performed. Advanced solid-state characterization techniques, including simultaneous thermal analysis (STA), powder X-ray diffraction (pXRD), Raman spectroscopy, and density functional theory (DFT) modeling have been combined to study the reaction pathways. Analysis revealed that NH 4 Np VI O 2 (NO 3 ) 3 thermally decomposes to a proposed neptunyl nitrate intermediate, followed by Np 2 O 5 and finally NpO 2 , all within the temperature range of 150 °C–600 °C. Further characterization of the pentoxide intermediate provided the first Raman spectra of pure-phase Np 2 O 5 and associated DFT modeling confirmed Raman peak assignments for this phase. These findings provide mechanistic information to advance production of the critical radioisotope 238 Pu and advance the state of knowledge on Np materials chemistry using modern characterization techniques.
Lawson, Kathryn M. [Oak Ridge National Laboratory ↗
National Criticality Experiments Research Center (NCERC) - capabilities and recent measurements
The National Criticality Experiments Research Center (NCERC) located at the Device Assembly Facility (DAF) at the Nevada National Security Site (NNSS) and operated by Los Alamos National Laboratory (LANL) is home to four critical assemblies which are used to support of range of missions, including nuclear criticality safety and nuclear nonproliferation. Additionally, subcritical systems can also be assembled at NCERC. NCERC is providing critical and subcritical experiments valuable to the nuclear data community and experiments performed at NCERC are often published as benchmarks in the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbook. This manuscript will give a broad overview of recent experiments performed at NCERC, upcoming experiments, and why integral measurements are important and useful to the nuclear data community. The four critical assemblies are GODIVA IV, FLATTOP, COMET, and PLANET. GODIVA IV is a cylindrical metal fast burst reactor, the fourth in the GODIVA series that dates back to the 1950’s. FLATTOP is an highly enriched uranium (HEU) or Pu core reflected by natural uranium. COMET and PLANET are vertical lift assemblies, where one half of the reactor can be lifted to the upper half of the reactor to create a critical system. Some recent experiments include various critical intermediate energy assemblies with lead, and subcritical measurements of plutonium reflected by copper, tungsten, and nickel. Work is also underway to make a better measurement of the critical mass of neptunium, using a neptunium sphere surrounded by nickel shells. Additionally, measurements will be performed next year with HEU shells from Rocky Flats. These HEU shells will be stacked together to make larger systems, allowing for a large range of criticality (from subcritical to delayed critical). Other upcoming measurements include an HEU critical assembly sensitive to intermediate energy neutrons.
98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗