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All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

An Examination of Issues Related to a Europa Subsurface Component for the JIMO Mission

The Galileo Europa data set served to revolutionize our view of Europa. In particular the strong evidence of a large, cold, salty Ocean beneath 5-30 km of ice has profoundly altered the significance of Europa in our thinking, especially of context of habitability in the solar system. While much remains to be learned from spacecraft observations of several sorts, there are significant questions answerable only by in-situ techniques; these relate to the formation of Europa, the nature of its ocean, and the prospects for life in its ocean, sediments, and ice. We feel that wide-ranging discussion of an in-situ subsurface mission to Europa, as part of JIMO, should proceed. The science objective of the mission is to characterize the icy shell of Europa to resolve its provenance, estimate the composition of brine of the Europa ocean, and search for evidence of Earth-like life. Probably anyone would agree that an in-situ mission to Europa would be of great value, but he or she would also immediately take the position that such a mission is utterly impractical. We take the position here of defining the least complex mission that can nonetheless justify its cost and to argue that such a mission is realistic enough that it should be seriously considered. Our mission thinking has been: 1) Soft landing. A soft lander is required on a site sufficiently flat to offer a stable platform; no further site selectivity is required. 2) Subsurface exploration. The Europa subsurface must be examined. Surficial processes on Europa arguably have exposed the upper 200 m of shell to chemical effects from the Jovian radiation belts as well as cometary infall, etc; to examine native ice we must descend below that point to, for discussion, 300 m. At that depth we argue that the ice is characteristic of ice at depth and possibly is effectively sea ice. 3) Science data. A few simple measurements at various depths and at 300 m constitute a scientifically successful mission. Measurements would include analysis of meltwater for a few inorganic ions and amino acids and an optical examination of the borehole wall. 4) Communication. Transmission of data to an orbiter is essential, but we will constrain the landed mission to a daily communication over a few days. 5) Subsurface access. Drilling to 300 m is a significant challenge; it can be addressed by several means: Thermal Probe (Cryobot) which permits water to refreeze above the vehicle. This is our tentative choice with plutonium as the fuel to generate thermal energy for drilling and electrical power for operations. Open Hole Drill, a thermal system in which the meltwater is removed for greater thermal efficiency. Meltwater removal on Europa is both a complexity and a risk, but analysis is improved. Mechanical Drilling in which cutting or grinding generates ice chips which are removed. This is too complex at Europa temperatures. The measurement objectives for the mission will be: Obj. 1: Determine the concentration of simple inorganic salts in the Europa Ice Shell and, by extrapolation, of the ocean. These data will also validate spaceborne sensors. Obj. 2: Determine the nature and abundance of amino acids in the ice such that cometary infall material in the upper ice can be compared to material at depth. Obj. 3: Optically examine the ice to resolve inclusion structure, particulate content, and stratification. Access to 300 m depth is a significant if not audacious plan; we are aware that this has not been done on any planetary body. Our approach is the use of a plutonium heat source; to overcome Europa's surface temperature and to melt ice a significant amount of plutonium is needed, and significant shielding and other protective steps will be required. The quantity of plutonium is a key concern. The mission will require subsurface collection and processing of samples for in situ analysis, calling for a miniature, high pressure micro-sampling system designed to meet needs of instruments that require low presses for operation. The inlet system itself collects a micro-sample in the external high pressure environment, then transfers it into a protected low pressure environment for analysis.

Carsey, F. D.↗
DOE OSTI2012

EXPERIMENTAL METHODS TO ESTIMATE ACCUMULATED SOLIDS IN NUCLEAR WASTE TANKS

The Department of Energy has a large number of nuclear waste tanks. It is important to know if fissionable materials can concentrate when waste is transferred from staging tanks prior to feeding waste treatment plants. Specifically, there is a concern that large, dense particles, e.g., plutonium containing, could accumulate in poorly mixed regions of a blend tank heel for tanks that employ mixing jet pumps. At the request of the DOE Hanford Tank Operations Contractor, Washington River Protection Solutions, the Engineering Development Laboratory of the Savannah River National Laboratory performed a scouting study in a 1/22-scale model of a waste tank to investigate this concern and to develop measurement techniques that could be applied in a more extensive study at a larger scale. Simulated waste tank solids and supernatant were charged to the test tank and rotating liquid jets were used to remove most of the solids. Then the volume and shape of the residual solids and the spatial concentration profiles for the surrogate for plutonium were measured. This paper discusses the overall test results, which indicated heavy solids only accumulate during the first few transfer cycles, along with the techniques and equipment designed and employed in the test. Those techniques include: Magnetic particle separator to remove stainless steel solids, the plutonium surrogate from a flowing stream; Magnetic wand used to manually remove stainless steel solids from samples and the tank heel; Photographs were used to determine the volume and shape of the solids mounds by developing a composite of topographical areas; Laser rangefinders to determine the volume and shape of the solids mounds; Core sampler to determine the stainless steel solids distribution within the solids mounds; Computer driven positioner that placed the laser rangefinders and the core sampler over solids mounds that accumulated on the bottom of a scaled staging tank in locations where jet velocities were low. These devices and techniques were very effective to estimate the movement, location, and concentrations of the solids representing plutonium and are expected to perform well at a larger scale. The operation of the techniques and their measurement accuracies will be discussed as well as the overall results of the accumulated solids test.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Developing a New Criticality Safety Hands-On Training Utilizing ZPPR Plates

Nuclear criticality safety is an extremely important part of the work at Los Alamos National Laboratory (LANL). As part of the work LANL performs to continue to keep criticality safety a top priority, LANL has developed and regularly teaches nuclear criticality safety training classes for both the United States Department of Energy Nuclear Criticality Safety Program as well as internal trainings for LANL employees. A portion of the training classes is comprised of hands-on demonstrations, where students get the opportunity to handle special nuclear material at the National Criticality Experiments Research Center (NCERC). One hands-on demonstration uses the “Class foils,” thin HEU foils which are stacked with lucite moderator plates. A hand-stack is performed until the multiplication reaches the “three-quarters rule,” where the demonstration is continued remotely on a vertical lift assembly up until the system is critical. This hands-on demonstration eventually achieves a critical configuration and follows the ANS-1 guidelines on an approach to critical. Another hands-on demonstration involves handling clad plutonium and neptunium spheres, and follows procedures using criticality safety evaluations to ensure that the hands-on demonstrations remain subcritical.This hands-on demonstration also involves the use of polyethylene shells around the plutonium sphere to demonstrate how additional reflector increases the criticality of a system. This paper is focused on developing a new hands-on demonstration using Zero Power Physics Reactor (ZPPR) plates. This new hands-on demonstration will follow the ANS-8 standards as it is not desired to achieve criticality with the ZPPR plates during the hands-on demonstration. A hands-on demonstration using multiple plutonium parts will likely be more applicable to personnel who handle plutonium on a daily basis, such as LANL glovebox operators.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2019

Evaluation of Experimental Studies in the U-Rich Region of the U-Pu Phase Diagram

Upon the re-examination of two experimental studies, additional thermophysical data pertaining to the uranium-rich portion of the uranium-plutonium binary phase diagram have been elucidated. The first study involved the analysis of solidification cooling curves following the processing of U-Pu alloys. Two phase transitions (liquidus and bcc) were evaluated and the results agreed very well with the established boundaries. The second study was actually performed over sixty years ago but still warrants recognition due to the paucity of thermodynamic data on the U-Pu system to date. From the investigation, the activity coefficients of plutonium in liquid uranium from 1813 K to 2042 K were derived assuming Henry’s law from which the partial molar excess Gibbs energy change of plutonium was obtained: Δ G-bar {sup ex}=R∗T∗ln γ{sub Pu}{sup o}=− 76694+39.2∗T(J/mol).

36 MATERIALS SCIENCE↗
DOE OSTI2026

High sensitivity measurement of femtogram-level 238 Pu by thermal ionization mass spectrometry with correction of background 238 U

Low-concentration plutonium isotopic measurements provide a valuable fingerprint to identify possible material origins in the context of environmental contamination monitoring, environmental tracing, nuclear safeguards, nuclear forensics, and treaty monitoring. Thermal ionization mass spectrometry (TIMS) has long been recognized as one of the most sensitive techniques for plutonium isotopic measurement, but has not generally been utilized for 238 Pu determination, especially at low concentrations, due to an isobaric interference from 238 U, prevalent as background. Here, this work demonstrates a new analytical technique for correction of background 238 U from the 238 Pu counts collected during a TIMS analysis. The technique takes advantage of the higher ionization temperature of U relative to Pu and uses a 235 U tracer added after plutonium purification chemistry for 238 U semi-quantitative determination. This technique has been successfully applied to the determination of 238 Pu concentration and the 238 Pu/ 239 Pu ratio in sample types including single-isotope standards, isotopic certified reference materials, matrix-containing environmental reference materials, and simulated nuclear detonation debris. The results have been directly compared on a sample-by-sample basis to alpha spectrometry results. The detection limit by this new technique is 0.23 fg 238 Pu, which was previously unachievable by mass spectrometry and is possible in around 1 h of analysis time post-chemistry compared to weeks of required counting time by alpha spectrometry (at the same atom amount). We also present original, high precision data for Pu isotope concentrations in IAEA-384, Fangataufa Sediment, including 242 Pu results for the first time. The new technique allows measurement of a key isotope, 238 Pu, that was previously not measured in small environmental or nuclear forensics collections.

238Pu↗
DOE OSTI2012

Literature Review of PuO 2 Calcination time and Temperature Data for Specific Surface Area

The literature has been reviewed in December 2011 for calcination data of plutonium oxide (PuO 2 ) from plutonium oxalate Pu(C 2 O 4 ) 2 precipitation with respect to the PuO 2 specific surface area (SSA). A summary of the literature is presented for what are believed to be the dominant factors influencing SSA, the calcination temperature and time. The PuO 2 from Pu(C 2 O 4 ) 2 calcination data from this review has been regressed to better understand the influence of calcination temperature and time on SSA. Based on this literature review data set, calcination temperature has a bigger impact on SSA versus time. However, there is still some variance in this data set that may be reflecting differences in the plutonium oxalate preparation or different calcination techniques. It is evident from this review that additional calcination temperature and time data for PuO 2 from Pu(C 2 O 4 ) 2 needs to be collected and evaluated to better define the relationship. The existing data set has a lot of calcination times that are about 2 hours and therefore may be underestimating the impact of heating time on SSA. SRNL recommends that more calcination temperature and time data for PuO 2 from Pu(C 2 O 4 ) 2 be collected and this literature review data set be augmented to better refine the relationship between PuO 2 SSA and its calcination parameters.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Project 57 Air Monitoring Report: (Jan 1 - Dec 31 2018)

During the late 1950s, the Atomic Energy Commission (AEC) (now the U.S. Department of Energy [DOE]) conducted a series of safety experiments to determine if a nuclear device subjected to a large conventional explosives detonation would result in a nuclear yield. The AEC obtained temporary use of a large portion of western Emigrant Valley from the U.S. Department of Defense (DOD) for one of these experiments: Project 57. Following the Project 57 safety experiment, the AEC fenced the contaminated area and returned control of the surrounding land to the DOD. Emigrant Valley is part of the Nevada Test and Training Range (NTTR). For safety and security reasons, access to the NTTR is controlled using both physical (i.e., fences) and administrative (e.g., signs and postings) controls. Therefore, the public cannot access the Project 57 site and there are no known human receptors that routinely access the site. Project 57 was detonated on April 24, 1957, in Emigrant Valley approximately 13 mi (21 km) northeast of the north end of Yucca Flat. This test was undertaken to develop: (1) a means of estimating immediate distribution and long-term redistribution of plutonium dispersed during a nonnuclear detonation; (2) biomedical evaluation techniques for use in likely plutonium-laden environments; (3) methods of decontaminating ground areas, pavements, and building materials; and (4) alpha survey instruments and field monitoring procedures to promptly estimate contaminant deposition. Although the test did not result in the fission of nuclear materials, it did disseminate plutonium across the ground surface. Various radiological surveys have been performed in the area since Project 57 was conducted. The AEC delineated the area containing radioactive material based on radioactivity surveys performed shortly after the test was conducted. A designated Contamination Area (CA), marked by a fence, was established later. The distribution of americium-241 (Am-241) in the area was determined again in a 1997 flyover, which showed Am-241 ranging from as much as 70,000 counts per second (cps) at ground zero to background (<70 cps). This survey also documented Am-241 radioactivity on the ground surface beyond the east side CA fence at levels of up to 150 cps. In 2007, the DOE expanded the CA by posting “Contamination Area” signs 200 ft to 400 ft (60 m to 120 m) beyond the original fence, which formed a new CA boundary.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2012

Application of wavelet scaling function expansion continuous-energy resonance calculation method to MOX fuel problem

More and more MOX fuels are used in all over the world in the past several decades. Compared with UO{sub 2} fuel, it contains some new features. For example, the neutron spectrum is harder and more resonance interference effects within the resonance energy range are introduced because of more resonant nuclides contained in the MOX fuel. In this paper, the wavelets scaling function expansion method is applied to study the resonance behavior of plutonium isotopes within MOX fuel. Wavelets scaling function expansion continuous-energy self-shielding method is developed recently. It has been validated and verified by comparison to Monte Carlo calculations. In this method, the continuous-energy cross-sections are utilized within resonance energy, which means that it's capable to solve problems with serious resonance interference effects without iteration calculations. Therefore, this method adapts to treat the MOX fuel resonance calculation problem natively. Furthermore, plutonium isotopes have fierce oscillations of total cross-section within thermal energy range, especially for {sup 240}Pu and {sup 242}Pu. To take thermal resonance effect of plutonium isotopes into consideration the wavelet scaling function expansion continuous-energy resonance calculation code WAVERESON is enhanced by applying the free gas scattering kernel to obtain the continuous-energy scattering source within thermal energy range (2.1 eV to 4.0 eV) contrasting against the resonance energy range in which the elastic scattering kernel is utilized. Finally, all of the calculation results of WAVERESON are compared with MCNP calculation. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2013

Overview of reductants utilized in nuclear fuel reprocessing/recycling

The most widely used reductant to partition plutonium from uranium in the Purex process was ferrous sulfamate, other alternates were proposed such as hydrazine-stabilized ferrous nitrate or uranous nitrate, platinum catalyzed hydrogen, and hydrazine, hydroxylamine salts. New candidates to replace hydrazine or hydroxylamine nitrate (HAN) are pursued worldwide. They may improve the performance of the industrial Purex process towards different operations such as de-extraction of plutonium and reduction of the amount of hydrazine which will limit the formation of hydrazoic acid. When looking at future recycling technologies using hydroxamic ligands, neither acetohydroxamic acid (AHA) nor formohydroxamic acid (FHA) seem promising because they hydrolyze to give hydroxylamine and the parent carboxylic acid. Hydroxyethylhydrazine, HOC{sub 2}H{sub 4}N{sub 2}H{sub 3} (HEH) is a promising non-salt-forming reductant of Np and Pu ions because it is selective to neptunium and plutonium ions at room temperature and at relatively low acidity, it could serve as a replacement of HAN or AHA for the development of a novel used nuclear fuel recycling process.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2013

Advanced nuclear fuel cycles - Main challenges and strategic choices

A graphical conceptual model of the uranium fuel cycles has been developed to capture the present, anticipated, and potential (future) nuclear fuel cycle elements. The once-through cycle and plutonium recycle in fast reactors represent two basic approaches that bound classical options for nuclear fuel cycles. Chief among these other options are mono-recycling of plutonium in thermal reactors and recycling of minor actinides in fast reactors. Mono-recycling of plutonium in thermal reactors offers modest savings in natural uranium, provides an alternative approach for present-day interim management of used fuel, and offers a potential bridging technology to development and deployment of future fuel cycles. In addition to breeder reactors' obvious fuel sustainability advantages, recycling of minor actinides in fast reactors offers an attractive concept for long-term management of the wastes, but its ultimate value is uncertain in view of the added complexity in doing so,. Ultimately, there are no simple choices for nuclear fuel cycle options, as the selection of a fuel cycle option must reflect strategic criteria and priorities that vary with national policy and market perspectives. For example, fuel cycle decision-making driven primarily by national strategic interests will likely favor energy security or proliferation resistance issues, whereas decisions driven primarily by commercial or market influences will focus on economic competitiveness.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

Preparation and Characterization of Pu and Hf Bearing Lanthanide Borosilicate and Alumino-borosilicate Glasses - 15667

Eight borosilicate glasses with LaBS and ABS compositions containing plutonium and/or hafnium as a plutonium surrogate were prepared in Pt ampoules (Pu-bearing) and alumina or Pt crucibles (Hf-bearing) and characterized by X-ray diffraction, optical and scanning electron microscopy, infrared and Raman spectroscopy. Hf-bearing LaBS glasses were found to be amorphous whereas Pu-bearing glasses contained trace of plutonium dioxide and britholite. Hf and Fe bearing ABS glasses contained minor spinel structure phase. As followed from optical and SEM studies Hf-bearing LaBS glasses were more homogeneous than Pu-bearing and ABS glasses. The structure of the anionic motif of the glasses investigated by IR and Raman spectroscopy is typical of the glasses with relatively low silica content. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

MC{sup 2}-3/DIF3D Analysis of the ZPPR-15 Axial Expansion Experiments

The Zero Power Physics Reactor (ZPPR) fast critical facility at the Argonne National Laboratory-West (ANLW) site in Idaho was built in 1969 to obtain neutron physics information necessary for the design of fast breeder reactors. The ZPPR-15 phases A through D were part of a series of cores intended to model a 330 MWt Integral Fast Reactor (IFR) concept. The ZPPR-15 assembly consisted of an inner core zone, an outer core zone of higher fissile content, a thin radial blanket and a thick steel reflector. The inner and outer core zones were of approximately equal volumes. The core zones simulated a sodium-cooled, metal-fueled fast reactor with approximately 10 wt.% zirconium in the target fuel composition. Phases A and B simulated an equilibrium cycle UPu-Zr fuel core where plutonium created in the blankets was sufficient to negate the need for enriched {sup 235}U feedstock. Phase D simulated a beginning of life U-Zr fuel core with enriched uranium fuel although approximately 10% of the fuel in the outer zone of the Phase D core was plutonium because {sup 240}Pu was required to provide a neutron source for the modified source multiplication technique used for many reactivity worth measurements such as sodium void worth in ZPPR. Phase C simulated the intermediate state between beginning of life and equilibrium cycle conditions with 50% enriched uranium fuel and 50% plutonium fuel in the inner and outer core zones. These configurations represent the various stages of reactor operating conditions. Phase A did not contain zirconium (metal fuel is typically alloyed with Zr) while Phases B, C and D did contain zirconium although the limited plate inventory restricted the zirconium zone to the inner core zone. This set of experiments was performed between April 1985 and July 1986 and focused on validation of both the concept and modeling. In each phase, there were multiple loadings for sub-critical, critical, and with regard to this manuscript, axial expansion worth measurements. Combined, these cores can be used to assess the accuracy of physics codes and evaluated cross section data for IFR concept reactors. This paper presents a recent effort that was made on retrieving validation data from the ZPPR-15 experiments and on deterministic modeling and analysis using MC{sup 2}-3/DIF3D for code validation. Axial expansion experiments and ZPPR-15D loading 206 were selected for this analysis. An explicit modeling of the axial expansion (introduction of gaps between sections of drawer) of ZPPR-15D loading 206 yielded a 32% over-prediction in the worth of the axial expansion with the MC2-3/DIF3D models. This indicates a consistent bias between ZPPR-15B and ZPPR-15D with regard to the deterministic modeling of the experiments. As part of future work, we intend on investigating whether the cross section processing or homogenization model is to blame, but we note with such small changes in k-effective in a large model, it is rather difficult to obtain zero errors as is typical for other worth measurements. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2019

Stabilization of Residual Contamination with Alternative Materials - 19404

Since 2015, Savannah River National Laboratory (SRNL) in conjunction with Florida International University (FIU) have been investigating the applicability of intumescent coatings as radiological contamination fixatives for stabilization of residual materials after decontamination efforts have concluded. Intumescent coatings are designed to prevent heat transfer to a protected substrate and are typically used in both the aerospace industry to protect components from thermal shock and in building design to protect building joints that may fail in the event of a fire. For this work, these materials are examined for their ability to reduce worker risk by fixating residual contamination and lower the impact of a release in a scenario that breaches containment of a contaminated building and subsequently induces a large-scale fire by crediting their fire-retardant attributes. Initial studies of intumescent coatings and commercial fixatives included performance in direct flame, varied environmental conditions (20-110 F or -6.67 C, 10-95% relative humidity), adhesion studies to stainless steel after curing in varied environmental conditions, and radiological exposure. Of all the materials tested, many were found to be inadequate in one or more of these areas. These materials failed in one or more of three characteristic ways: 1) through delamination at reduced temperatures (≤40 F or 4.44 C) or from even moderate handling, 2) melting off the substrate at elevated temperatures (≥90 F or 32.22 C), 3) proving to be flammable and promote smoke propagation. Failure in these ways results in the potential for a subsequent release of the fixated contamination in the event of water presence/absence or direct flame. Using these results as a platform for the best in class identified material that did not experience failure in any of these tests, SRNL and FIU targeted the plutonium-238 contaminated hot cells within Savannah River Site (SRS) Building 235-F as a characteristic test bed to benchmark an intumescent coating used as a contaminant fixative. Through discussion with the SRS 235-F Risk Reduction personnel, appropriate hazards and performance metrics were discussed and a cold demonstration was performed in a hot cell mockup located at SRS. The application methods were proven functional in the cold mock up, and these intumescent coatings were subsequently utilized in the Savannah River Site Building 235-F's Plutonium Fuel Form (PuFF) Facility to aid in stabilization of plutonium-238 in both a contaminated hot cell and Entry Hood in September 2018. Presented in this work is the overview of the application process, associated working considerations for introduction of equipment and materials into the facility, lessons learned, and lifetime monitoring data to date. (authors)

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

The TRANSCEND University Consortium: Theme 4: Nuclear Materials - 20431

The safe and secure management of Pu is a matter of international concern, with ∼250 t of separated Pu currently stockpiled worldwide. The UK's civil inventory of nuclear materials contains significant stocks of separated Pu from the reprocessing of Magnox and AGR spent fuels. The preferred option for the 138.5 tonnes of Pu is re-use as mixed oxide (MOx) fuel, although 5% is not suitable for re-use and is recommended for direct disposal. However, it will take more than 15 years to implement re-use, requiring that the Pu be kept in interim storage in its current state for that period, i.e. as PuO{sub 2} powder within inert steel storage cans at Sellafield. The focus of the work presented here is thus plutonium storage and the direct disposal of plutonium. The Research and Development needs of both are now pressing: in the case of storage due to it being the current default; in the case of immobilization and disposal because of a comparative lack of Research and Development on Pu conditioning and packaging due to policy uncertainty as to whether it would be disposed of in a Geologic Disposal Facility (GDF). Addressing these needs is complicated by Pu's high radioactivity, decay heat and radiotoxicity, criticality, nuclear safeguard requirements and, for some UK Pu contaminated materials targeted for disposal, poor inventory. Thus, there is also a critical requirement for underpinning research on Pu bearing materials in these two contexts. In response to these needs, the TRANSCEND Consortium (Transformative Science and Engineering for Nuclear Decommissioning, a multi-disciplinary collaboration of 11 universities and 8 key industry partners from across the UK's civil nuclear sector) is seeking to provide technical underpinning to ongoing option development for the UK's civil Pu stockpile. Whilst understanding the behaviour of plutonium during its re-use as MOx is beyond the scope of the TRANSCEND Consortium work plan, the main objectives of the work are: (1) For interim storage: to understand how the surface structure and properties of pristine and radiation damaged PuO{sub 2} change with time in the absence and presence of water; and (2) For immobilization and disposal: to understand the mechanisms of incorporation of Pu into ceramic and glass-ceramic waste-forms, as well as the effect on these of self-induced radiation damage. Each objective is being addressed through separate work packages, the details of which are discussed in this paper. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

A Rapid Sequential Separation Method for Determination of Actinides and TENORM in Fracking Wastes - 20223

With recent advances in unconventional drilling technology in the US and around the world, the risks of environmental contamination and exposure due to technologically enhanced naturally occurring radioactive materials (TENORM) from fracking wastes have also surfaced. Although the Permian Basin (southeastern New Mexico, western Texas) has long been a modest producer of oil, the advent of fracking technology a decade ago turned it into hot property for producers. A 2018 assessment of undiscovered, technically recoverable continuous oil and gas resources by the U.S. Geological Survey estimates an average 46.3 billion barrels of oil and 281 trillion cubic feet of gas. This is likely to increase the use of unconventional drilling and TENORM generation. TENORM concentrations in oil and gas exploration and production waste can be several hundred to several thousand times higher than background TENORM concentrations. Both the thorium and uranium decay chains contribute to airborne radionuclides arising from the radon gas escaping the ground and subsequently decaying as airborne particulates. Additionally, radon decay products {sup 210}Pb and {sup 210}Po can build up in scale on the internal surfaces of oil and gas handling pipes and in sludge in refineries, becoming potential inhalation and ingestion hazards for workers. Furthermore, southeastern NM is also home to world's only licensed and operating transuranic nuclear waste repository, the DoE's Waste Isolation Pilot Plant (WIPP). Plutonium isotopes ({sup 239+240}Pu) and {sup 241}Am, are expected to account for more than 99% of the total radioactivity scheduled for disposal in the WIPP repository. Thus, an improved understanding of the environmental fate and transport of TENORM, liberated by unconventional drilling, is essential to assess how best to protect individuals and the environment. In this context, accurate measurement of TENORM and actinides in environmental and biological samples is essential. In this presentation, a new sequential method for the separation and pre-concentration of actinides (Pu, Am, Np) and TENORM (Po, U and Th) derived from oil and gas exploration is proposed. The TEVA method involves a rapid co-precipitation step to remove matrix interferences from the samples, followed by plutonium oxidation state adjustment to Pu (IV) and an incubation period of ∼ 1 hour at 50-60 deg. C to allow the resultant Po (II) to oxidize into Po(IV). The polonium, neptunium, thorium and plutonium are then separated on a TEVA column, while americium and uranium are separated on a TRU column. After separation, the alpha counting source was prepared by micro-precipitation with copper sulfide (CuS) for polonium and neodymium fluoride (NdF{sub 3}) for actinides. The efficiency and reliability of the procedures were tested by analyzing filter, drinking water and frack sand samples. The method is simple, robust and can be performed quickly with excellent removal of interferences, high chemical recovery and very good alpha peak resolution. (authors)

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2018

Analysis and modeling of the equilibrium behaviors of U and Pu in molten LiCl-KCl/Cd system at 500 °C

In the field of pyroprocessing of used nuclear fuels, liquid cadmium is applied in different ways to recover transuranics from molten salt, while effecting some degree of separations between transuranics and lanthanides. In this work, a model of the separation performance between uranium and plutonium across the phase boundary between molten salt and liquid cadmium is presented. The salt is the LiCl-KCl eutectic with solute concentrations of UCl 3 and PuCl 3 . The cadmium is the liquid cadmium phase field from the Cd-U-Pu ternary alloy system. Lastly, the model used to describe the behavior of uranium and plutonium in the salt/cadmium system is applied to describe the behavior of plutonium and lanthanide in the salt/cadmium system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Computational insights into the structure of anhydrous Pu(III) oxalate

Despite the plutonium oxalate method's wide use in plutonium reprocessing, the method's mechanistic details remain unclear, particularly the identity of the plutonium oxidation state during conversion from an oxalate hydrate to the oxide. Recently, the optical vibrational spectra of Pu(III) oxalate during calcination were measured, providing an experimental reference for computational studies aimed at elucidating the oxalate structure. Here, in this work, we compare the vibrational and electronic properties of two candidate anhydrous Pu(III) oxalate structures calculated using density functional theory with recent experiments. We find that both structures are plausible and may coexist at experimental temperatures, providing insights into the broad features measured in the Raman and infrared spectra.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Production of anhydrous ƒ-element fluorides through the ionothermal treatment of ƒ-element oxalates

The pivotal role of uranium and plutonium fluorides in the nuclear fuel cycle, particularly in the pyrochemical reduction process, is well recognized. Traditionally, the fluorination of uranium and plutonium materials relies on the use of highly toxic and corrosive gases (e.g., HF (g) , F 2(g) ). Herein, we present an alternative approach using the ionic liquid 1‑butyl‑3-methylimidazolium hexafluorophosphate ([Bmim][PF 6 ] (l) ) and/or hexafluorophosphoric acid (HPF 6(aq) ) as fluorinating agents for the ƒ-element oxalates M$^{III}_{2}$(C 2 O 4 ) 3 ∙ 9H 2 O (s) M$^{III}_{2}$(C 2 O 4 ) 3 ∙ 9H 2 O (s) (M III = Ce, Pu) and M IV (C 2 O 4 ) 2 ∙ 6H 2 O (s) (M IV = Th, U). Our findings demonstrate that [Bmim][PF 6 ] (l) and HPF 6(aq) enable the ionothermal fluorination of ƒ-element oxalates, resulting in the formation of anhydrous CeF 3(s) , ThF 4(s) , and UF 4(s) within 2 hours at 200 °C. This method also facilitates the partial fluorination of plutonium(III) oxalate, yielding a mixture of anhydrous PuF 3(s) and an unidentified phase. Overall, the ionothermal treatment approach offers a safer and more efficient means of producing anhydrous ƒ-element fluorides than conventional methods involving hazardous gases. In addition, we describe the morphology of UF 4(s) materials as a function of production route and demonstrate the presence of morphological signatures that could be used during a nuclear forensic investigation.

Cerium↗