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At least 829 records · Page 46

Evaluations of the Fates of Alkali Metals, Actinides, Mercury, and Iodine During DWPF Recycle Diversion

The fates of alkali metals, actinides, mercury, and iodine in the Defense Waste Processing Facility Recycle Diversion process (as currently conceptualized) have been evaluated through paper studies based on available knowledge of the chemistry, physical properties, solubility, and volatility of the various species involved. The effect of pH in the range from 9 to 13 has been discussed. Recommendations for additional studies to close technology gaps have been provided, many of which are contingent upon the results of pending testing and sample characterization efforts. There is uncertainty in the amounts of soluble actinides passing through the process filter, though the bulk of the actinides should be captured on the filter with the Recycle Collection Tank solids and the total amounts of actinides should be relatively low. The Recycle Collection Tank pH could impact the fraction of actinides reaching the evaporator, but the primary factors determining the actinide fate are expected to be the amount of CO 2 sorption from air sparging or, for certain actinides (such as plutonium), oxidation and/or sorption to MnO 2 solids from permanganate additions to destroy the glycolate anion. Process optimization could minimize the amounts of actinides passing the filter. Depending upon the levels of mercury observed in recycle stream samples and because of the volatility of mercury, the evaporator should be designed with the capability to remove dense mercury phases from the condensate to avoid exceeding ETP WAC limits. The facility design must be adequate to transfer dense mercury phases and testing to confirm mercury transfer is needed. Simulant containing mercury is recommended for both filtration and evaporation testing. OLI Modeling of the various recycle streams is recommended to provide insight on the fate of iodine. Iodine-spiked simulants are recommended for upcoming evaporation tests. The pro) ect should consider the likelihood and impact of NAS scale formation in the evaporators. Process optimization may be needed to minimize the accumulation of NAS scale and possibly the sorption of actinides in the evaporator. Actual waste testing of the Recycle Diversion filtration and evaporation should include the analysis of actinides, mercury, and iodine to determine their partitioning.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

MITR Low-Enriched Uranium Conversion Fluid-Structure Interaction Preliminary Design Verification

The U.S. National Nuclear Security Administration (NNSA) Office of Material Management and Minimization (M 3 ) has developed and is pursuing an integrated approach to address the persistent threat posed by unintentional proliferation of nuclear materials. The NNSA M 3 approach reduces the risk of highly enriched uranium (HEU) and plutonium falling into the hands of non-state actors by minimizing the use of and, when possible, eliminating weapons-usable nuclear material around the world. In this geopolitical context, most research and test reactors, both domestic and international, have completed or started a program of conversion from the use of HEU to low-enriched uranium (LEU) as fuel. Conversion of civilian research reactors from HEU to LEU, and the return of the HEU to the country of origin, are important components of the NNSA non-proliferation program. Worldwide, 71 reactors have been converted to the use of LEU fuel, and an additional 32 have been confirmed to be permanently shut down. The U.S., with 20 reactor conversions, is among the 39 countries on six continents where conversions have occurred. With recent conversions in Ghana and Nigeria, an important milestone was reached in completing conversion of all reactors on the continent of Africa to LEU fuel. Africa thus becomes the third continent to have completed conversion of all HEU reactors to LEU, following Australia and South America

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Distribution of U, Pu and Np in a Mo-99 Recovery Process using Sachtopore NP (titania based) Absorbent Material

A laboratory scale mockup of a prototypical Mo-99 recovery process has been operated in a radioactive materials hood at Savannah River National Laboratory. This equipment has been operated with realistic concentrations of uranium (U-238), plutonium (94% Pu-239), neptunium (Np-237), and non-radioisotopes of common fission products (including Mo). The goal of this work was to determine the amounts of U, Pu, and Np in the liquid waste streams created by the wash streams for the production process. The key question was how the initial acid wash volume will be handled, as this solution contains residual raffinate which amounted to ~ 3% ofthe mass ofthe feed solution in this experiment. If the initial 1.9 bed volumes (BV) of acid wash were recycled as in this experiment then the combined wash solutions can be expected to contain 0.4 g U/L, 2.7 pg Pu/L and < 14 pg Np/L. If, on the other extreme, the entire acid wash solution was discarded as waste, then the combined wash solutions can be expected to contain 11 g U/L, 3.8 pg Pu/L and ~ 80 pg Np/L. The Sachtopore NP absorbent (for Mo-99 recovery) retains a minuscule fraction ofthe U (2.3 mg U per g titania or 0.03% ofthe U in the feed). The uncertainties are too large to determine how close the absorbent is to saturation with U. Less mass but a higher fraction ofthe total Np was retained by the absorbent (0.7 pg Np per g titania or ~2% of the Np in the feed). As has been reported elsewhere, a large fraction ofthe Pu fed to the titania bed was retained by the absorbent (92% of Pu in the feed or 20 pg per g titania).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

First principles calculations in support of Pu aging: calculating the effects of lattice imperfections on thermodynamics

Plutonium (Pu) has, in theory, well defined crystal structures: its atoms are arranged in regular spatial patterns. But Pu is radioactive, and as its nuclei decay those regular spatial patterns are interrupted. The interruptions are lattice imperfections, which are known to affect how materials respond to their environment. To adequately model Pu, we need to know which lattice imperfections are present, how they interact with each other, and how they affect the material’s response to its environment. The work presented here aims to use density functional theory (DFT) calculations to begin to answer the latter, in particular, how individual lattice imperfections affect measurable effects including thermal expansion (the change in volume in response to a change in temperature), heat capacity (the amount of thermal energy needed to change a material’s temperature), and elastic moduli (a material’s resistance to applied stresses). Pu poses many computational challenges. The $\textit{f}$ electrons require special attention. Of all the elements, Pu has the largest number of electrons that must be included in the calculations. Thermal effects require calculating the phonons (the lattice vibrations), which for systems containing lattice imperfections demand large, complex computational cells - but computational resources limit the size and complexity. With careful restructuring of how the calculations are performed, all these challenges have been met to enable calculations that provide insight into how lattice imperfections affect Pu’s response to its environment. Reported here are the computational challenges and the advances developed to meet them, along with the first results showing the strong effect that one prototype lattice imperfection (an interstitial Pu atom in a delta-phase Pu lattice) has on Pu’s response to its environment.

36 MATERIALS SCIENCE↗

Effects of 18 O Exchange on Neutron Emission Rates of Aging 238 PuO 2 LWRHUs

The Lightweight Radioisotope Heater Unit (LWRHU) provides about 1 Watt of thermal power to critical electrical and mechanical systems in the extreme temperatures of space, maintaining the operating temperature of the spacecraft’s scientific and general operating equipment. Los Alamos National Laboratory (LANL) designed and tested the LWRHU in the 1970s through early 1980s. The first production campaign at LANL was in the early 1980s in support of the Galileo mission in which over 100 LWRHUs were manufactured. In the mid-1990s, almost 200 LWRHUs were manufactured in support of the Cassini mission. After the primary Cassini manufacturing campaign, the Department of Energy (DOE) approved the fabrication of more than 10 additional LWRHUs as spares in 1998. The LWRHU assembly contains the following components: a fuel pellet, a vented capsule, a pyrolytic graphite insulator, and a fine-weave pierced fabric (FWPF) graphite aeroshell. The fuel pellet is a hot-pressed 238 PuO 2 cylindrical pellet that is sintered to create a ceramic pellet. The pellet is encapsulated in a platinum-rhodium encapsulation. The welded fueled clad is placed inside a pyrolytic graphite thermal insulation to protect the fuel from the heat produced in reentry events. The exterior layer of the LWRHU assembly is the FWPF aeroshell. Before sintering, PuO 2 granules are heated in a furnace at temperatures greater than or equal to 700°C under an enriched 16 O atmosphere in order to reduce trace quantities of 18 O. Because 18 O undergoes an (α,n) reaction, 18 O needs to be removed as much as possible to meet radiation emission requirements set by the Jet Propulsion Laboratory (JPL) and the National Aeronautics and Space Administration (NASA), as well as other agencies. The relative abundances of the oxygen isotopes are indicated by neutron emission rate (NER) measurements. LWRHUs are vented with a sintered platinum frit vent (George 1986). During extraterrestrial operation, the vent in the cladding allows helium from the decay of plutonium to escape and relieves pressure from the system while preventing the solids from escaping (Rinehart 1996, Tate 1982 & 1985). This vent is protected during manufacture by a platinum-30 rhodium cover. The capsule vent is activated by milling a 0.025-inch diameter hole through the protective cover to a nominal depth of 0.015 inches, generally immediately before the LWRHU is loaded into the aeroshell (George 1986). Prior to long-term storage, LWRHUs are vented and thus potentially allow infiltration of 18 O from the ambient atmosphere. Although NER decreases with age due to the reduction in emitted alpha particles, it might be expected that NER reduction is mitigated by the exchange of 18 O. However, this is not necessarily the case and no trend was observed relating NER to age other than the natural decay of 238 Pu (Mulford 2021). The most probable and dominant factor for determining specific NER was manufacturing discrepancies between individual units. It is important to understand the lack of observed 16 O- 18 O exchange and to compare LWRHU pellets as much as possible.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Gamma Spectroscopy Detector Candidates and Radioisotope Identification Algorithms for Use in National Security Applications

In 2006, the United States Congress mandated for the Department of Homeland Security (DHS) to screen all cargo containers to protect against terrorist acts and ensure the safety and security of the nation. Containers are screened by gamma and neutron detectors to ensure threat material is not smuggled into the country. However, because commerce is radioactive, detecting the presence of radioactive materials is not sufficient in ensuring the safety and security of the nation. Radioactive materials must also be identified in real time, thus distinguishing threat sources (Uranium-235 and Plutonium-230) from non-threat sources (kitty litter, pot ash, medical isotopes). Screening cargo containers can be considered a two-step process (1) alerting to the presence of radioactive material when gamma counts exceed a threshold setting, and (2) once alerted, identifying the type of radioactive material, which is done by collecting a gamma spectra and analyzing it with an analysis tool/algorithm. For this reason, it is important to evaluate not only emerging technology in neutron and gamma detection, but also investigate new advances in algorithm development for radioisotope identification (RIID). New candidates in detection and on-board algorithm analysis might offer opportunities to make the scanning, detection, and identification process more efficient while still ensuring the health and safety of the public. This research will investigate emerging technology in radiation detection focused on gamma spectroscopy capabilities and RIID algorithms for DHS applications.

61 RADIATION PROTECTION AND DOSIMETRY↗

Prompt Gamma Analysis of ARIES Materials and Updates to the 2015 Calibration Equations

Prompt gamma (PG) analysis is a nondestructive, nuclear, elemental analysis technique that uses charged particle reactions to interrogate a sample, and elements present in the sample matrix are identified through the characteristic gamma-rays emitted from the product nuclei in alpha-p and alpha-n nuclear reactions. This technique has been applied to plutonium oxide packaged in over 4,000 individual 3013 containers, and the concentrations of certain light elements were determined from the integrated peak areas based on a calibration that was published previously. This report provides the results for a new population of 3013 containers packaged with oxide materials produced by the conversion of metal by Advanced Recovery and Integrated Extraction System (ARIES) project using the direct metal oxidation (DMO) process and muffle furnaces. New PG and analytical chemistry data collected since 2015 were added to the existing calibration data sets to refine the calibration parameters. Calibration equations were also developed for determining beryllium and fluorine at low concentrations in high-purity ARIES product oxides. The new fluorine calibration provides an order of magnitude greater sensitivity and results in an additional 1,408 containers in the original population identified as having fluorine as an impurity. Additionally, equations for calculating the lower limits of detection (LLDs) as a function of the actual counting time (live time) were obtained using WLS regression technique for samples in the calibration data set. This resulted in changes to the LLDs published previously.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flowsheet Evaluation of Dissolving Used Nuclear Fuel in PUREX Solvent

This study explores the potential benefit to the used nuclear fuel actinide recovery flowsheet of a process simplification and establish the experimental work needed to develop the simplified flowsheet. The simplification is based on replacing acid dissolution of used nuclear fuel with dissolution in the tri-butyl phosphate solvent used in the industrially mature Plutonium Uranium Reduction Extraction flowsheet. Though characterized by considerable uncertainty, simplified flowsheets appear feasible and potentially offer significant reductions in process complexity, nitrate inventory, secondary liquid effluent generation and plant footprint. Initial development of the technology should focus on key fission product and actinide dissolution as a function of process conditions and understanding the fundamental chemistry of tri-butyl phosphate solvent chemistry. Development of ancillary technologies for minor actinide separations and fuel pretreatment for tritium management is also recommended.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

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↗

Evaluation of Electrical Resistivity Tomography to Monitor the Transport of Past Releases Beneath Tank Farms

Underground storage tanks at the Hanford Site, in southeastern Washington State, hold radioactive waste generated from four decades of plutonium production. The 149 single-shell tanks and the 28 double-shell tanks have all exceeded their initial design life of approximately 25 years. At least 67 tanks are assumed to have leaked in the past, resulting in radioactive releases into the vadose zone. Gamma ray logging within dry monitoring wells is currently the primary method for tracking the migration of leaked tank waste through the vadose zone. While this approach provides an accurate assessment of radioactive contamination, that information is only provided near (within ~1m) the borehole, leaving most of the vadose zone unmonitored, particularly the important region directly beneath the tank. This report describes a numerical study that investigates the feasibility and performance of time-lapse 3D electrical resistivity tomography (ERT) for long-term monitoring of a hypothetical tank waste location and migration through the vadose zone. ERT is a method of remotely imaging the bulk electrical conductivity (EC) of the subsurface, which is significantly impacted by the presence of conductive solid and liquid tank waste. The release of liquid tank wastes increases subsurface fluid conductivity and saturation over time, creating a target to use time-lapse ERT for long-term monitoring. Although the presence of metallic infrastructure can cause ERT interference, recent advancements in ERT data processing enable the deleterious effects of buried metallic infrastructure (e.g. pipes, wellbore casings, tanks) to be removed to better determine the liquid tank waste migration over time. Three hypothetical realistic scenarios were simulated in the ERT evaluation. The first two scenarios assume the same leak amount and rate (i.e., between 1/1/1951 and 12/31/1951 at the rate of 347 m 3 per year) but different leaky tanks. Scenario 1 assumes leaks under tank B-102, which is located on the edge of the B-tank farm and surrounded by a few metallic infrastructure including cased pipes/wells/tanks. Scenario 2 assumes leaks under tank B-108, which is located near the center of the B-tank farm and surrounded by larger amount of metallic infrastructure than B-102. Scenario 3 assumes the same metallic infrastructure as B-102, with a more recent contaminant leak that was simulated to have occurred between 1/1/2018 and 12/31/2023 at a rate of 1.89 m 3 per year. The leak time in Scenarios 1 and 2 corresponds to a historical overfill event in 1951 and Scenario 3 corresponds to a recent found tank leak in 2019. In each scenario, a “true” bulk EC model vs. time reflecting contaminant migration was generated. ERT data was simulated from these “true” bulk EC models and a time-lapse ERT inversion produced “imaged” bulk EC vs. time. Three electrode configurations in two, four and eight boreholes surrounding the leak tank were used in the ERT simulations in each scenario. These borehole configurations were considered logistically feasible and cost-effective for monitoring. The hypothetical ERT boreholes are assumed to have non-metallic casing. By comparing the “imaged” bulk EC with the “true” bulk EC, it was demonstrated that the three configurations of wells used (two, four, and eight wells) were able to successfully monitor the migration of tank leaks through the vadose zone, with bulk EC resolution increasing with the number of down borehole ERT arrays for all scenarios. Therefore, the use of eight boreholes to perform ERT monitoring beneath the tanks provided the best spatiotemporal information.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

LLNL International Working Group on Gamma Spectrometry - Preparation of IDB Dataset

The spectral information and associated metadata, including source information, detector setup, and shielding configuration is described in human readable, comma-separated text files (csv). Five csv files are associated with each material type and include the following information (where [Isotope] is U, Pu, and MOX): [Isotope]_measurement_metadata - Metadata of the measurement configuration, including material composition at time of acquisition (decay corrected from certificate date). Data that is unique to a measurement configuration e.g. detector geometry, source-detector distance, analyzer and other electronics used, attenuating materials are provided in this file. [Isotope]_spectrum_metadata - The information that is unique to the spectrum. This includes detector specifications (e.g. date of acquisition, number of channels, gain (keV/channel), energy range, real and live time, full width half-maximum (FWHM) of the 186 or 208 peak for uranium or plutonium measurements, respectively. [Isotope]_source_metadata - The source material used for the measurement, this includes the ratio and uncertainties of isotopes present and processing information of the material. In addition, the certificate information for the source material is listed. [Isotope]_spectrum_counts_metadata - The counts per channel for each spectrum. This data is linked via the UID.spectrum index to the measurement_metadata file. [Isotope]_spectrum_checksum_metadata The MD5 checksum for the original spectrum file. This data is linked via the UID.spectrum index to the measurement_metadata file. This information is provided to prevent duplication of entries in the database.

42 ENGINEERING↗

ALDWP Operational Highlights 2021

The Weapons Pit production manufacturing team completed pit build 21-1 assembly operations on December 23, 2020. This build utilized all essential flow sheet steps and included the second -01 long tube cut off extension and welding activity. This is the best build produced in the MC4597-01 pit program to date. Final out-of-line operations, non-destructive evaluation, and radiography was completed during the week of January 4. Depending on the results from high energy radiography, this pit will be considered to be a candidate for CERT-02 and shipment to Lawrence Livermore National Laboratory in support of pit certification. It is notable that this build was completed while concurrently making Plutonium (Pu) metal, producing additional castings, machining Pu parts for Build 22, completing disassembly of two pits, supporting Nightshade B Pu target characterization, and precision machining of Jasper certification base plates.

42 ENGINEERING↗

Nuclear Data to Reduce Uncertainties in Reactor Antineutrino Measurements

The large quantities of antineutrinos produced through the decay of fission fragments in nuclear reactors provide an opportunity to study the properties of these particles and investigate their use in reactor monitoring. The reactor antineutrino spectra are measured using specialized, large area detectors that detect antineutrinos through inverse beta decay, electron elastic scattering, or coherent elastic neutrino nucleus scattering; although, inverse beta decay is the only demonstrated method so far. Reactor monitoring takes advantage of the differences in the antineutrino yield and spectra resulting from uranium and plutonium fission providing an opportunity to estimate the fissile material composition in the reactor. Recent experiments reveal a deviation between the measured and calculated antineutrino flux and spectra (the reactor anomaly) indicating either the existence of yet undiscovered neutrino physics, uncertainties in the reactor source term calculation, incorrect nuclear data, or a combination of all three. To address the nuclear data that impact the antineutrino spectrum calculations and measurements, an international group of over 180 experts in antineutrino physics, reactor analysis, detector development, and nuclear data came together during the Workshop on Nuclear Data for Reactor Antineutrino Measurements (WoNDRAM) to discuss nuclear data needs and achieve concordance on a set of recommended priorities for nuclear data improvements. Three topical sessions focused on the reactor source term, the antineutrino spectrum, and the detector response, provided a forum to gain consensus amongst the participants on the most important data improvements to address two goals: 1) understand the reactor anomaly and 2) improve the ability to monitor reactors using antineutrinos. This report summarizes the outcomes of the workshop discussions and the recommendations for nuclear data efforts that reduce reactor antineutrino measurement uncertainties.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Machine Learning Modeling Pipeline for Extracting Nuclear Proliferation Events of Interest from Open Data Sources (U)

In FY2020, the Savannah River National Laboratory (SRNL) and the Sanghani Center for Artificial Intelligence and Data Analytics at Virginia Polytechnic Institute and State University entered a collaboration funded by Department of Energy’s (DOE) Office of Defense Nuclear Nonproliferation Research and Development. The project’s mission was to take the first steps toward developing a demonstration prototype system that uses multiple machine learning and data analytics methods on largescale open data sources to identify new, developing, and/or undeclared nuclear programs. Given the SRNL team’s on-site perspective of events culminating in the DOE’s decision to pursue the Savannah River Plutonium Processing Facility (SRPPF), the team targeted the identification of events and indicators in retrospective datasets that pointed to the activity of “fissile core fabrication at the Savannah River Site” prior to the official announcement in May of 2018. A preliminary modeling pipeline was developed in FY20 that showed the datasets contained adequate signal for continuation of efforts. In FY21, a modular demonstration prototype modeling pipeline has continued in development for two text-based data sources: a broad internet archive (Webhose Ltd.) and a decahose Twitter database (i.e., a global sampling of one in every ten Tweets). The techniques that have been developed rely on graph theory and anomaly detection to identify contextual shifts in key words and phrases at various points in time such that indicators of events of interest could be identified and subsequently, events could be extracted from the corpuses. The foundational concept behind the approaches is that contextual shifts in key words and phrases can act as indicators of events of interest. Both datasets have proven successful in extracting events of interest related to pit production at the Savannah River Site prior to the official announcement. In addition, the pipelines have generated a wide range of events broadly summarized as: the awarding of DOE contracts at major sites, DOE investments in various programs, accidents at DOE national laboratories, speculations about the fate of pit production in the DOE complex, domestic and international shipments and receipts of nuclear materials at DOE sites, termination of non-proliferation agreements with Russia, termination of MOX, new weapons development approvals/testing, nuclear posture reviews, major DOE cleanup/production milestones, political opinions, and nuclear watch groups’ opinions, among many others.

97 MATHEMATICS AND COMPUTING↗

CoDCon Project (Final Report)

The co-decontamination (CoDCon) project was established in FY 2016 with the objectives of (a) evaluating the uncertainty in the uranium (U)/plutonium (Pu) ratio in a mixed U/Pu product from a tributyl phosphate (TBP)–based solvent extraction flowsheet, and (b) developing and demonstrating on-line optical spectroscopy for real-time monitoring of key components (e.g., Pu, U, and HNO 3 concentrations) in the process solutions. We were interested in assessing the accuracy and precision to which a specific uranium-to-plutonium (U/Pu) ratio can be achieved, which for the purposes of this project was set at a U/Pu mass ratio of 7/3. The uncertainty associated with achieving this specific target U/Pu ratio was investigated during five flowsheet tests using laboratory-scale solvent extraction equipment. In addition, optical spectroscopic techniques were incorporated into the CoDCon solvent extraction testing system, allowing real time monitoring of all input and output process streams. Two CoDCon flowsheet tests were performed in FY 2018 using a simple dissolved fuel simulant containing only U (~1 M) and Pu (~15 mM) in nitric acid (HNO 3 ; ~3 M). In FY 2019, two additional flowsheet tests were performed. For the first of these (CoDCon Run 3), the dissolved fuel simulant was similar to that used in the first two tests, with the inclusion of 1 mM neptunium (Np). The second test conducted in FY 2019 (CoDCon Run 4) used a more representative dissolved fuel simulant, including addition of non-radioactive fission product elements. A fifth CoDCon flowsheet test (CoDCon Run 5) was conducted in FY 2020, with the following additional objectives: (1) routing of the technetium (Tc) in the simulated dissolved fuel solution to the solvent extraction raffinate, and (2) routing of the Np in the simulated dissolved fuel solution to the U/Pu product. All tests used a bank of sixteen 2 cm centrifugal contactors. The tests involved first loading the solvent (30 vol% TBP dissolved in n-dodecane) with U and Pu (and Np, for Run 5), then the Pu (and Np) was stripped from the loaded solvent with a U(IV) solution (~50 mM) and the flowsheet conditions were adjusted such that some U partitioned into the Pu-containing product stream. The amount of U accompanying the Pu was monitored in real time using optical spectroscopic techniques coupled with chemometric modeling. Based on the real-time spectroscopic measurement of the U/Pu ratio, adjustments were made to the flowrate of the fresh TBP solvent phase used to scrub U from the aqueous Pu-containing product. This proved to be a very effective way to control the U/Pu mass ratio in the product. This report presents the results of the CoDCon Run 5 test. The flowsheet tested in Run 5 was substantially different than that run in the prior tests, especially the solvent loading section of the flowsheet. Two key changes were made. First, based on the objective to extract all the Np and route it with the U/Pu product, pentavalent vanadium [V(V)] was added to the feed and scrub solutions. The purpose of the V(V) was to convert all the Np to the +6 oxidation state, which is extractable by TBP. Second, a high acid (8 M HNO 3 ) scrub was added to the flowsheet to scrub the Tc from the solvent. This was followed by a low acid scrub (0.05 M HNO 3 ) to reduce the residual HNO 3 concentration in the solvent prior to the Pu stripping step. The output from the low acid scrub was collected separately, rather than routing towards the raffinate. The modifications to the solvent loading part of the flowsheet were only partially successful. The treatment with V(V) was effective at converting the Np to Np(VI). Only 1.3% of the Np remained in the raffinate solution. However, ~40% of the Np stripped out of the solvent in the low acid scrub step; nearly 20% of the Pu also was stripped from the solvent during the low acid scrub. For further development, either modifications to the flowsheet, or concentration and recycle of the low acid stream into the

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Post-closure Nuclear Criticality Safety Evaluations for Disposition of Criticality Control Overpacks at the Waste Isolation Pilot Plant

The Waste Isolation Pilot Plant (WIPP) is a geological repository in southern New Mexico that provides for disposal of transuranic (TRU) wastes from atomic energy defense activities. The Sandia National Laboratories (Sandia) Report, Consideration of Nuclear Criticality When Disposing of Transuranic Waste at the Waste Isolation Pilot Plant, addresses nuclear criticality safety based on the projected inventory characteristics for the initial compliance certification application of WIPP in 1996. As the inventory, waste forms, and disposal package designs change, revised or new analyses are necessary to demonstrate acceptability for these configurations within the WIPP safety basis and compliance with 10,000-year post-closure standards of the US Environmental Protection Agency (EPA). Saylor and Scaglione evaluated criticality control overpacks (CCOs) in 2017 based on conservative assumptions for post-closure repository structural conditions with resulting effects on containers and container spacing, The Saylor and Scaglione evaluation of CCOs addressed a single waste configuration that represents the Surplus Plutonium Disposition Program’s dilute and dispose waste form and composition. This initial CCO study demonstrated that 50 grams of boron carbide (B 4 C) per CCO is sufficient to ensure post-closure criticality safety based on a well-mixed waste composition, and Oak Ridge National Laboratory (ORNL) subsequently determined that this amount of B 4 C does not require constraints on moisture or plastic present as moderator. The Saylor and Scaglione analysis conservatively assumes repository room closure that eliminates all space between fissile gram equivalent (FGE) 239 Pu masses. The close-packed array was selected based on limited availability of repository salt creep modeling results at that time. In 2019, Brickner provided additional evaluations for pipe overpack containers (POCs), building on the conservative basis provided by Saylor and Scaglione. Brickner’s 2019 analysis made use of new geomechanical data for post-closure spacing that rely on advances in repository modeling as documented in the work by Reedlunn and Bean. This current CCO evaluation for generic waste materials expands on earlier work performed at ORNL and includes evaluation of CCOs across a much broader range of possible waste compositions and geometries. This evaluation is intended to provide input for the required feature, event and process (FEP) screening to determine if post-closure criticality must be included as an event in the 10,000-year regulatory evaluation. As such, the approach to modeling post-closure criticality presented in this report has been coordinated with the Sandia team responsible for FEP screening. The resulting analysis supports disposition of fissile materials in the CCO containing up to 380 FGE 239 Pu and expands conditions acceptable for disposal of fissile material in CCOs. This evaluation builds on the methodology of Saylor and Scaglione and Brickner, using the most recently available geomechanical data for CCO spacing under salt creep compaction scenarios provided by Reedlunn and Bean. The broad range of fissile material configurations analyzed in this report are intended to account for configurations that may occur during the post-closure disposal time period, and it also includes waste configurations that are not physically possible to support analysis of conditions that influence neutron fluence.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Pit depth analysis using automated software for three containers with complete imaging

The 3013 surveillance program is tasked with ensuring the long term safety of plutonium storage in 3013-compliant containers. One component of this task is to understand corrosion features found on the interior sidewall of the inner container closure weld region (ICCWR). To this end, three containers were selected to have laser confocal microscope (LCM) 20X imaging of the entire ICCWR. This report describes the analysis of the LCM pit depth data using the automated corrosion analysis software. The analysis included determining maximum pit depths and distributions of pit depths, volumes, and diameters for all pit features identified on the three containers. Results provided insight into possible corrosion mechanisms and were consistent with previous pit growth model predictions.

36 MATERIALS SCIENCE↗