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DHS National Technical Nuclear Forensics Program FY 10 Summary Report: Graduate Mentoring Assistance Program (GMAP)

This program provides practical training to DHS graduate fellows in the DOE laboratory complex. It involves coordinating students, their thesis advisors, and their laboratory project mentors in establishing a meaningful program of research which contributes to the graduate student's formation as a member of the nuclear forensics community. The summary report details the student/mentor experience and future plans after the first summer practicum.

07 ISOTOPE AND RADIATION SOURCES↗

Review of the Status of Cumulative Fission Yields from 239Pu(n,f) of Interest to Nuclear Forensics

The cumulative fission yields of the four nuclides 95 Zr, 99 Mo, 144 Ce and 147 Nd are key parameters in estimating the effects from nuclear tests and for post-detonation nuclear forensics in general. Driven particularly by differences in the fission yields from 239 Pu(n,f) that have been in use by LLNL and LANL over the years, an intensive effort has been undertaken to evaluate the current state of our knowledge of these yields and to provide a basis for projecting yields to those applicable to forensics. The neutron spectrum producing fission in the Jezebel critical assembly (< E n > ~ 1.9 MeV) may be taken as a reasonable reference. It is desired to know the cumulative fission yields to a total uncertainty (1σ) of ± 2.5%.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Analysis Code - Data Analysis in 'Leveraging Multiple Statistical Methods for Inverse Prediction in Nuclear Forensics Applications' (LMSMIPNFA) v. 1.0

R code that performs the analysis of a data set presented in the paper ‘Leveraging Multiple Statistical Methods for Inverse Prediction in Nuclear Forensics Applications’ by Lewis, J., Zhang, A., Anderson-Cook, C. It provides functions for doing inverse predictions in this setting using several different statistical methods. The data set is a publicly available data set from a historical Plutonium production experiment.

Lewis, John↗

Development of spectroscopic tools for nuclear forensics signatures development

The Savannah River National Laboratory (SRNL) has been developing advanced spectroscopic tools for the characterization of plutonium-bearing compounds with the intent to develop material and process signatures for nuclear forensics. Plutonium in a production, refining, or finishing facility will exist in many forms including oxide precursors (PuF4, PuF3, Pu oxalate, etc.), oxide, and metal. The ability to identify plutonium in each of these chemical forms and determine their processing history is crucial for the development of spectroscopic signatures. This presentation will focus on our work to develop and apply spectroscopic tools at SRNL using doubled-walled cells (DWC) to characterize the thermal decomposition of oxalates, calcination chemistry, alpha-decay-induced chemistry, age dating since last calcination, and other signatures related to plutonium processing.

Villa-Aleman, Eliel↗

Development of Spectroscopic Tools for Nuclear Forensics Signatures Development

Diversion of nuclear materialsfrom legitimate commercial processes for use by nefarious actors is a frightening and surreptitious problem. Smuggled nuclear material can be used to manufacture a simple radiological dispersion device (RDD) and potentially incorporated into the development of a nuclear weapon. With some frequency, smuggled nuclear material is interdicted in foreign countries as actors cross border checkpoints. Nuclear material interdicted in this way can be analyzed using a variety of tools. Plutonium-239 is commonly used as the fissile material in nuclear weapon production as an alternative to uranium-235. Plutonium in a production, refining, or finishing facility will exist in many forms including oxide precursors (PuF4, PuF3, Pu oxalate, etc.), oxide, and metal. The ability to identify plutonium in each of these forms and determine properties, characteristics, or history of these materials is crucial for determining if the processes occurring in a nuclear facility are legitimate or not. This presentation will focus on the development and application ofspectroscopic tools developed at SRNL using doubled-walled cells (DWC) to characterize Pu-bearing compounds. Advances in the use of vibrational spectroscopy techniques (Raman and IR), UV-VIS-SWIR diffuse reflectance spectroscopy, gamma emission spectroscopy, luminescence spectroscopy, laser-induced breakdown spectroscopy in conjunction with XRD and SEM in the characterization of Pu-bearing compounds will be presented with emphasis in material processing history.

Villa-Aleman, Eliel↗

INTRINSIC DOSIMETRY: A POTENTIAL NEW TOOL FOR NUCLEAR FORENSICS INVESTIGATIONS

Thermoluminescence (TL) dosimetry was used to measure dose effects on the raw stock material of borosilicate container glass from different geographical locations. Effects were studied at times up to 60 days post-irradiation at doses from 0.15 to 20 Gy. The minimum detectable dose using this technique was estimated to be 0.15 Gy which is roughly equivalent to a 24 hr irradiation 1 cm from a 50 ng source of 60Co. Two peaks were identified in the TL glow curve, a relatively unstable peak around 125°C and a more stable peak around 225°C. Differences in TL glow curve shape and intensity were also observed for the glasses from different geographical origins. We investigate radiation induced defects in glass to further develop the technique of intrinsic dosimetry–the measurement of the total absorbed dose received by the walls of a container holding radioactive material. Intrinsic dosimetry is intended to be used as an interrogation tool to provide enhanced pathway information on interdicted or newly discovered waste containers of unknown origin or history by considering the total absorbed dose received by a container in tandem with the physical characteristics of the radioactive material housed within that container. One hypothetical scenario is presented to illustrate the application of intrinsic dosimetry to waste management and nuclear forensics.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Chemical and Sr isotopic characterization of North America uranium ores: Nuclear forensic applications

This study reports major, minor, and trace element data and Sr isotope ratios for 11 uranium ore (uraninite, UO 2+x ) samples and one processed uranium ore concentrate (UOC) from various U.S. deposits. The uraninite investigated represent ores formed via different modes of mineralization (e.g., high- and low-temperature) and within various geological contexts, which include magmatic pegmatites, metamorphic rocks, sandstone-hosted, and roll front deposits. In situ trace element data obtained by laser ablation-ICP-MS and bulk sample Sr isotopic ratios for uraninite samples investigated here indicate distinct signatures that are highly dependent on the mode of mineralization and host rock geology. Relative to their high-temperature counterparts, low-temperature uranium ores record high U/Th ratios (>1000), low total rare earth element (REE) abundances (<1 wt%), high contents (>300 ppm) of first row transition metals (Sc, Ti, V, Cr, Mn, Co, Ni), and radiogenic 87 Sr/ 86 Sr ratios (>0.7200). Comparison of chondrite normalized REE patterns between uraninite and corresponding processed UOC from the same locality indicates identical patterns at different absolute concentrations. Lastly, this result ultimately confirms the importance of establishing geochemical signatures of raw, uranium ore materials for attribution purposes in the forensic analysis of intercepted nuclear materials.

07 ISOTOPE AND RADIATION SOURCES↗

Nuclear Forensics and Radiochemistry: Cross Sections

The neutron activation of components in a nuclear device can provide useful signatures of weapon design or sophistication. This lecture will cover some of the basics of neutron reaction cross sections. Nuclear reactor cross sections will also be presented to illustrate the complexity of convolving neutron energy spectra with nuclear excitation functions to calculate useful effective reactor cross sections. Deficiencies in the nuclear database will be discussed along with tools available at Los Alamos to provide new neutron cross section data.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Measuring very low radiation doses in PTFE for nuclear forensic enrichment reconstruction

Every country that has made nuclear weapons has used uranium enrichment to do so. Despite the centrality of this technology to international security, there is still no reliable physical marker of past enrichment in the open literature that can be used to perform forensic verification of historically produced weapons on gas centrifuges. We show that the extremely low radioactivity from uranium alpha emissions during enrichment leaves detectable and irreversible calorimetric signatures in the common enrichment gasket material PTFE, allowing for historical reconstruction of past enrichment activities at a sensitivity better than one weapon’s quantity of highly enriched uranium. Fast scanning calorimetry also enables the measurement of recrystallization enthalpies of sequentially microtomed slices, confirming the magnitude and the type of radiation exposure while also providing detection of tampering and a method for analyzing field samples useful for treaty verification. Furthermore, this work opens the door for common items to be turned into precise dosimeters to detect the past presence of radioactivity, nuclear materials, and related activities with high confidence.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Nuclear Forensics Scanning

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46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Resonance Ionization Mass Spectrometry for Post-Detonation Nuclear Forensics (Final Report)

Isotope ratio measurements of the actinide elements provide essential information for nuclear detonation forensics and proliferation detection. Resonance Ionization Mass Spectrometry (RIMS) is a high-sensitivity, elementally selective, laser-based form of mass spectrometry that offers the potential to determine the isotopic composition of materials without sample preparation. Due to the elementally selective approach of RIMS, basic research questions of atomic spectroscopy and the probability for producing neutral atoms in the gas phase, must be studied element by element. The studies carried out in this work represent basic research into the application and optimization of RIMS to the analysis of post-detonation debris.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid Quantification of 237 U Specific Activity for Nuclear Forensics

In the event of an unattributed nuclear explosion, rapid assessment of the short-lived uranium isotope activity and mass can provide valuable information for subsequent forensic analysis. Rapid analysis in the field is enabled by using microfluidic chemistry and deployable instrumentation. Here, this work presents a flow chemistry system, controlled in LabVIEW, that integrates three functionalities: (1) selective extraction of uranium from the sample matrix via a 3D-printed supported liquid membrane module; (2) UV–visible absorbance spectrophotometry to measure the total uranium concentration in the strip flow; and (3) a portable CdTe γ-ray spectrometer coupled to a 3D-printed flow cell to measure 237 U activity concentration in the strip solution. The system was calibrated using standard solutions, and its functionality was demonstrated using a solution of depleted uranium spiked with 237 U. Uranium concentrations of 40–5000 μg/mL were directly quantified online using a 100 mm optical flow cell, while concentrations of 0.5–10 μg/mL were quantified online using a colorimetric reagent. The mass concentration measurement takes approximately 60 min while the activity concentration via γ-ray spectrometry varies depending on the activity of 237 U, with 1 kBq/mL requiring about 30 min of acquisition time to obtain <10% uncertainty at 1σ. This platform provides a fieldable approach for quantifying uranium mass and radioactivity relevant to postdetonation nuclear debris.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nuclear Forensics

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Nuclear science and engineering - Nuclear fuel cyc↗

High-Energy X-ray Diffraction Microscopy for Nuclear Forensics FY2022 Project Report

Morphological information on nuclear material has been identified using visible light and scanning electron microscopy. These identify qualitative differences in particle morphology. Three-dimensional imaging of materials through alternating scanning electron microscopy imaging and focused ion beam milling has also been used. Unfortunately, these techniques are time- and labor-intensive, with significant sample preparation required and lengthy analysis times. Further, the resulting 3D images are qualitative, require manual identification, and do not capture statistically-representative populations. High energy X-ray 3D imaging using a direct-beam or diffracted-beam (High-Energy Diffraction Microscopy) have been developed at the Advanced Photon Source and can produce quantitative information on grains (phase, location, etc.) and pores (size distribution, sphericity) in a material. These techniques require only minutes to characterize a sample volume and are non-destructive, thus suitable for a wide range of existing samples and for confirmatory analyses to be carried out using conventional microscopy techniques. In this first year of the project, all uranium oxide samples were synthesized and characterized using conventional analyses by the analytical chemistry laboratory. Conventional analysis methods included powder x-ray diffraction, scanning electron microscopy, impurity analysis via inductively coupled plasma mass spectrometry, and infrared spectroscopy. Impurity analysis shows a drop in boron content from UO 3 to the lowest U 3 O 8 calcination temperature, but otherwise no appreciable difference in any sample. Analysis of diffraction data shows a flip of peaks from UO 3 dominated for the 600 °C calcined sample to U 3 O 8 dominated at 700 °C and 800 °C. Analysis of scanning electron microscopy images shows that with increased calcination temperature the size distribution of particles seems to increase and broaden. Both of these last findings are in line with previously published data, though this work used significantly fewer particles to simply show similar trends instead of getting truly quantitative particle analysis. Infrared analysis similarly shows ingrowth of U 3 O 8 as calcination temperature is increased, along with depression of peaks associated with UO 3 and water. Samples were prepared for analysis at the Advanced Photon Source at beamline 1-ID. It is anticipated that analysis will occur in November of 2022. AI/ML techniques to de-noise data coming out of 1-ID during the analyses was also developed during this time using previously gathered data. Preliminary results using a self-supervision technique called Noise2Selfshow good de-noising of data. Once the uranium oxide samples are analyzed, real data will be used to test the de-noising and other AI/ML techniques that may be developed in the second year of the project.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High-Energy X-ray Diffraction Microscopy for Nuclear Forensics (FY23 Project Report)

Morphological information on nuclear material has been identified using visible light and scanning electron microscopy. These identify qualitative differences in particle morphology. Three-dimensional imaging of materials through alternating scanning electron microscopy imaging and focused ion beam milling has also been used. Unfortunately, these techniques are time- and labor-intensive, with significant sample preparation required and lengthy analysis times. Further, the resulting 3D images are qualitative, require manual identification, and do not capture statistically-representative populations. High energy X-ray 3D imaging using a direct-beam or diffracted-beam (High-Energy Diffraction Microscopy) have been developed at the Advanced Photon Source and can produce quantitative information on grains (phase, location, etc.) and pores (size distribution, sphericity) in a material. These techniques require only minutes to characterize a sample volume and are non-destructive, thus suitable for a wide range of existing samples and for confirmatory analyses to be carried out using conventional microscopy techniques.

36 MATERIALS SCIENCE↗

Measuring Very Low Radiation Doses in PTFE for Nuclear Forensic Enrichment Reconstruction

Every country that has made nuclear weapons has used uranium enrichment. Despite the centrality of this technology to international security, there is still no reliable physical marker of past enrichment that can be used to perform forensic verification of historically produced weapons. We show that the extremely low radioactivity from uranium alpha emissions during enrichment leaves detectable and irreversible calorimetric signatures in the common enrichment gasket material PTFE, allowing for historical reconstruction of past enrichment activities at a sensitivity better than one weapon's quantity of highly enriched uranium. Fast scanning calorimetry also enables the measurement of recrystallization enthalpies of sequentially microtomed slices, confirming the magnitude and the type of radiation exposure while also providing a detection of tampering and a method for analyzing field samples useful for treaty verification. This work opens the door for common items to be turned into precise dosimeters to detect the past presence of radioactivity, nuclear materials, and related activities with high confidence.

Connick, Rachel↗