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Comparing two handheld elemental analyzers for potential use in plutonium manufacturing quality control.

A compact, high-resolution Echelle spectrometer yields two orders-of-magnitude improvements in sensitivity for quantifying gallium in plutonium surrogate optical emission spectra.

A method for formulation and production of a new variety of surrogate nuclear explosive melt debris (NEMD), Nuclear UnderGround Engineered Test Surrogates (NUGETS), based on detonation of a notional improvised nuclear device in an underground environment analogous to the Nevada National Security Site is presented. Extensive statistical analyses of precursory geochemical and geophysical characteristics are combined with an augmented surrogate debris cooling technique. Comparison of NUGETS formulation to those of other NEMD surrogates is reported. Application of NUGETS methodology to future studies in urban, underground, post-detonation technical nuclear forensic analysis is suggested.

The utilization of machine learning techniques has become commonplace in the analysis of optical emission spectra. These methods are often limited to variants of principal components analysis (PCA), partial-least squares (PLS), and artificial neural networks (ANNs). A plethora of other techniques exist and are well established in the world of data science, yet are seldom investigated for their use in spectroscopic problems. In this study, machine learning techniques were used to analyze optical emission spectra of laser-induced plasma from ceria pellets doped with silicon in order to predict silicon content. A boosted regression ensemble model was created, and its predictive accuracy was compared to that of traditional PCA, PLS, and ANN regression models. Boosted regression tree ensembles yielded fits with R-squared (R2) values as high as 0.964 and mean-squared errors of prediction (MSEPs) as low as 0.074, providing the most accurate predictive model. Neural networks performed with slightly lower R2 values and higher MSEPs compared to the ensemble methods, thus indicating susceptibility to overfitting.

We present the first reported quantification of trace elements in plutonium via a portable laser-induced breakdown spectroscopy (LIBS) device and demonstrate the use of chemometric analysis to enhance the handheld device's sensitivity and precision. Quantification of trace elements such as iron and nickel in plutonium metal via LIBS is a challenging problem due to the complex nature of the plutonium optical emission spectra. While rapid analysis of plutonium alloys has been demonstrated using portable LIBS devices, such as the SciAps Z300, their detection limits for trace elements are severely constrained by their achievable pulse power and length, light collection optics, and detectors. In this paper, analytical methods are evaluated as a means to circumvent the detection constraints. Three chemometric methods often used in analytical spectroscopy are evaluated; principal component regression, partial least-squares regression, and artificial neural networks. These models are evaluated based on goodness-of-fit metrics, root mean-squared error, and their achievable limits of detection (LoDs). Partial least squares proved superior for determining content of iron and nickel in plutonium metal, yielding LoDs of 15 and 20 ppm, respectively. These results of identifying the undesirable trace elements in plutonium components are critical for applications such as fabricating radioisotope thermoelectric generators or nuclear fuel.

Cu samples were irradiated with 10 MeV Au3+ ions at 200 °C to damage levels of 5, 10, and 15 displacements per atom (dpa) as an analogue to study long term self-irradiation effects of alpha-decay in Pu. Samples were then subject to accelerated aging at 350 °C for 1 h in air resulting in mixed oxide layer growth (Cu2O and CuO). Raman spectroscopy revealed that the CuO phase fraction was gradually decreased as the damage level increased. These findings indicate that accumulated damage from self-irradiation causes quantifiable modifications in metal oxidation that could serve as a novel forensic signature.

Cu metal, surrogate for metallic actinide materials, was subject to accelerated aging through thermal treatment. A multiphase oxide-layer (Cu2O, CuO) was detected, varying with temperature (250–400 °C) and aging time (1–3.5 h). Isotope ratio mass spectrometry revealed temperature-dependent isotopic fractionation of O, evidenced by the enrichment of Cu oxide in 16O isotopes with increasing temperature. Isotopic fractionation occurred initially with atmospheric O, and later through exchange with water vapor. Raman spectra contributed insight on phase fraction and local bonding of Cu oxides. O isotopes could serve as a useful tracer for studying oxide layer growth from aging metallic systems.

In order to model the activated isotopes and resulting dose from a nuclear detonation in an urban environment, the Activation and Transmutation of Isotopes in an Unstructured Mesh (ACTIUM) Python t...

Analytical spectroscopy methods have shown many possible uses for nuclear material diagnostics and measurements in recent studies. In particular, the application potential for various atomic spectroscopy techniques is uniquely diverse and generates interest across a wide range of nuclear science areas. Over the last decade, techniques such as laser-induced breakdown spectroscopy, Raman spectroscopy, and x-ray fluorescence spectroscopy have yielded considerable improvements in the diagnostic analysis of nuclear materials, especially with machine learning implementations. These techniques have been applied for analytical solutions to problems concerning nuclear forensics, nuclear fuel manufacturing, nuclear fuel quality control, and general diagnostic analysis of nuclear materials. The data yielded from atomic spectroscopy methods provide innovative solutions to problems surrounding the characterization of nuclear materials, particularly for compounds with complex chemistry. Implementing these optical spectroscopy techniques can provide comprehensive new insights into the chemical analysis of nuclear materials. In particular, recent advances coupling machine learning methods to the processing of atomic emission spectra have yielded novel, robust solutions for nuclear material characterization. This review paper will provide a summation of several of these recent advances and will discuss key experimental studies that have advanced the use of analytical atomic spectroscopy techniques as active tools for nuclear diagnostic measurements.

Californium (Cf) is currently the heaviest element accessible above microgram quantities. Cf isotopes impose severe experimental challenges due to their scarcity and radiological hazards. Consequently, chemical secrets ranging from the accessibility of 5f/6d valence orbitals to engage in bonding, the role of spin–orbit coupling in electronic structure, and reactivity patterns compared to other f elements, remain locked. Organometallic molecules were foundational in elucidating periodicity and bonding trends across the periodic table1–3, with a twenty-first-century renaissance of organometallic thorium (Th) through plutonium (Pu) chemistry4–12, and to a smaller extent americium (Am)13, transforming chemical understanding. Yet, analogous curium (Cm) to Cf chemistry has lain dormant since the 1970s. Here, we revive air-/moisture-sensitive Cf chemistry through the synthesis and characterization of [Cf(C5Me4H)2Cl2K(OEt2)]n from two milligrams of 249Cf. This bent metallocene motif, not previously structurally authenticated beyond uranium (U)14,15, contains the first crystallographically characterized Cf–C bond. Analysis suggests the Cf–C bond is largely ionic with a small covalent contribution. Lowered Cf 5f orbital energy versus dysprosium (Dy) 4f in the colourless, isoelectronic and isostructural [Dy(C5Me4H)2Cl2K(OEt2)]n results in an orange Cf compound, contrasting with the light-green colour typically associated with Cf compounds16–22.

This work describes the use of a laser-induced breakdown spectroscopy (LIBS) system to conduct macroscopic elemental mapping of uranium and iron on the exterior surface and interior center cross-section of surrogate nuclear debris for the first time. The results suggest that similar LIBS systems could be packaged for use as an effective instrument for screening samples during collection activities in the field or to conduct process control measurements during the production of debris surrogates. The technique focuses on the mitigation of chemical and physical matrix effects of four uranium atomic emission lines, relatively free of interferences and of good analytical value. At a spatial resolution of 0.5 mm, a material fractionation pattern in the surrogate debris is identified and discussed in terms of constituent melting temperatures and thermal gradients experienced.

This work reports thermodynamic characterizations of lanthanide β-diketonates for use in nuclear fission product separation. Adsorption and sublimation enthalpies have been shown to be linearly correlated, therefore there is motivation to determine sublimation thermodynamics. An isothermal thermogravimetric analysis method is employed on fourteen lanthanide chelates for the ligands 2,2,6,6-tetramethyl-3,5-heptanedione and 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione to determine sublimation enthalpies. No linear trend is seen across the series; values show a cyclical nature, possibly indicating a greater influence of chemisorption for some complexes and less of a role of physisorption in dictating adsorption differences between lanthanides in the same series. This is in line with previous reports in terms of the chromatographic separation order of the lanthanides. The results reported here can be used to manipulate separations parameters and column characteristics to better separate these lanthanide chelates. Fourteen chelates of the ligand 1,1,1-trifluoro-2,4-pentanedione are also thermally characterized but found to not sublime and be undesirable for this method. Additionally, all chelates are characterized by constant heating thermogravimetric analysis coupled with mass spectrometry, melting point analysis, elemental analysis and FTIR.

Efficient predictive capabilities are essential for the actinide series since regulatory constraints for radioactive work, associated costs needed for specialized facilities, and the short half-lives of many actinides present great challenges in laboratory settings. Improved predictive accuracy is advantageous for numerous applications including the optimization and design of separation agents for nuclear fuel and waste. One limitation of calculations in support of these applications is that the large variations observed from predictions obtained with currently available methods can make comparisons across studies uncertain. Benchmarking currently available computational methodologies is essential to establish reliable practices across the community to guarantee an accurate physical description of the systems studied. To understand the performance of a variety of common theoretical methods, a systematic analysis of differences observed in the prediction of structural characteristics, electron withdrawing ...

This work investigates and applies machine learning paradigms seldom seen in analytical spectroscopy for quantification of gallium in cerium matrices via processing of laser-plasma spectra. Ensemble regressions, support vector machine regressions, Gaussian kernel regressions, and artificial neural network techniques are trained and tested on cerium-gallium pellet spectra. A thorough hyperparameter optimization experiment is conducted initially to determine the best design features for each model. The optimized models are evaluated for sensitivity and precision using the limit of detection (LoD) and root mean-squared error of prediction (RMSEP) metrics, respectively. Gaussian kernel regression yields the superlative predictive model with an RMSEP of 0.33% and an LoD of 0.015% for quantification of Ga in a Ce matrix. This study concludes that these machine learning methods could yield robust prediction models for rapid quality control analysis of plutonium alloys.

Since no nuclear weapon surface detonations have occurred in urban harbor environments, the nuclear forensic community has no actual debris from which to develop and validate analytical methods for radiochemistry analysis, making the development of surrogate debris representative of this a marine-urban detonation a vital undertaking. This work seeks to build a robust model that accounts for natural and manmade environmental variations in harbor environments and vessel compositions to statistically define the elemental composition of vaporized debris from a marine-urban nuclear detonation. This initial work is necessary for follow-on neutron-activation and debris formation analysis.

Newly-established adsorption enthalpy and entropy values of 12 lanthanide hexafluoroacetylacetonates, denoted Ln[hfac]4, along with the experimental and theoretical methodology used to obtain these values, are presented for the first time. The results of this work can be used in conjunction with theoretical modeling techniques to optimize a large-scale gas-phase separation experiment using isothermal chromatography. The results to date indicate average adsorption enthalpy and entropy values of the 12 Ln[hfac]4 complexes ranging from −33 to −139 kJ/mol K and −299 to −557 J/mol, respectively.

A portable LIBS device was used for rapid elemental impurity analysis of plutonium alloys. This device demonstrates the potential for fast, accurate m-sfiw chemical analysis and could significantly reduce the fabrication time of plutonium alloys.

Although the eminent threat of a terrorist group detonating an improvised nuclear device (IND) in an urban environment is low, it is crucial that countries develop modern nuclear forensic capabilities to expedite response in a post-detonation scenario. In particular, new instruments need to be created to shorten dissolution time, expedite chemical separation, and improve forensic analysis of the nuclear melt glass that is created during the detonation of the device. To expedite this process, an instrument was designed to thermally couple a gas chromatograph (GC) to a time-of-flight inductively coupled plasma time-of-flight mass spectrometer (ICPTOFMS) In order to couple these two instruments, another instrument was designed to provide an isothermal atmosphere between the GC and TOFICPMS to expedite rapid gas separations processes. By using gas separations instead of the current wet chemistry processes, the required separation and analysis time of the melt glass significantly decreases. The new instrument would also provide a more detailed analysis of the elemental and isotopic composition of the melt glass. By completing these tasks simultaneously, this significantly decreases the required time to conduct these separations and improves the elemental and isotopic analysis.

This study presents the first known detection of fission products commonly found in post-detonation nuclear debris samples using solid sample introduction and a uniquely coupled gas chromatography inductively-coupled plasma time-of-flight mass spectrometer. Rare earth oxides were chemically altered to incorporate a ligand that enhances the volatility of the samples. These samples were injected (as solids) into the aforementioned instrument and detected for the first time. Repeatable results indicate the validity of the methodology, and this capability, when refined, will prove to be a valuable asset for rapid post-detonation nuclear forensic analysis.

Evaluating the efficiency of predictive methods is critical to the processes of upscaling laboratory processes to full-scale operations on an industrial scale. With regard to separation of lanthanoids, there is a considerable motivation to optimize these processes because of immediate use in nuclear fuel cycle operations, nuclear forensics applications, and rare-earth metal recovery. Efficient predictive capabilities in Gibbs free energies of reaction are essential to optimize separations and ligand design for selective binding needed for various radiochemical applications such as nuclear fuel disposition and recycling of lanthanoid fission products into useful radioisotope products. Ligand design is essential for selective binding of lanthanoids, as separating contiguous lanthanoids is challenging because of the similar behavior these elements exhibit. Modeling including electronic structure calculations of lanthanoid-containing compounds is particularly challenging because of the associated computational cost encountered with the number of electrons correlated in these systems and relativistic considerations. This study evaluates the predictive capabilities of various ab initio methods in the calculation of Gibbs free energies of reaction for [Ln(NO3)]2+ compounds (with Ln = La to Lu), as nitrates are critical in traditional separation processes utilizing nitric acid. The composite methodologies evaluated predict Gibbs free energies of reaction for [Ln(NO3)]2+ compounds within 5 kcal mol–1 in most cases from the target method [CCSD(T)-FSII/cc-pwCV∞Z-DK3+SO] at a fraction of the computational cost.

The ability to perform rapid separations in a post nuclear weapon detonation scenario is an important aspect of national security. In the past, separations of fission products have been performed using solvent extraction, precipitation, etc. The focus of this work is to explore the feasibility of using thermochromatography, a technique largely employed in superheavy element chemistry, to expedite the separation of fission products from fuel components. A series of fission product complexes were synthesized and the thermodynamic parameters were measured using TGA/DSC methods. Once measured, these parameters were used to predict their retention times using thermochromatography.

The University of Tennessee formed its Radiochemistry Center of Excellence (RCoE) in 2013 with support from the U.S. National Nuclear Security Administration. One of the major thrusts of the RCoE is to develop deeper understanding of rapid methods for radiochemical separations that are relevant to both general radiochemical analyses as well as post-detonation nuclear forensics. Early work has included the development and demonstration of rapid separations of lanthanide elements in the gas phase, development of a gas-phase separation front-end for ICP-TOF-MS analysis, and the development of realistic analytical surrogates for post-detonation debris to support methods development.

Eu2+-activated strontium iodide is an excellent single crystal scintillator used for gamma-ray detection, and significant effort is currently focused on the development of large-scale crystal growth techniques. A new approach of molten-salt pumping or so-called melt aging was recently applied to optimize the crystal quality and scintillation performance. Nevertheless, a detailed understanding of the underlying mechanism of this technique is still lacking. The main purpose of this paper is to conduct an in-depth study of the interplay between microstructure, trap centers, and scintillation efficiency after melt aging treatment. Three SrI2:2 mol % Eu2+ single crystals with 16 mm diameter were grown using the Bridgman method under identical growth conditions with the exception of the melt aging time (e.g., 0, 24, and 72 h). Using energy-dispersive X-ray spectroscopy, it is found that the matrix composition of the finished crystal after melt aging treatment approaches the stoichiometric composition. The mecha...

The development of realistic nuclear melt glass surrogates is important to the nuclear forensics community in order to establish analytical protocols for post-detonation analysis. In addition to creating surrogates that are accurate with regard to physical morphology and chemical composition, it is important to develop surrogates that also have similar radiological characteristics. A synthetic melt glass sample was irradiated at the High-Flux Isotope Reactor at Oak Ridge National Laboratory. This sample was counted twice using a semiconductor radiation detector to capture both fission-product signatures as well as those from neutron activation. A qualitative and quantitative analysis was performed to make recommendations for the next irradiation campaign.

A method is developed for predicting and formulating realistic synthetic post-detonation debris relevant to a nuclear surface detonation in arbitrary urban settings. Using these methods guides the development of synthetic debris that serves as a tool for developing and validating novel rapid forensic analysis methods. In order to accurately fabricate realistic homogenous surrogate material, the method incorporates regional soil compositions, land use data, and vehicle contributions to the urban environment.

A method for producing synthetic debris similar to the melt glass produced by nuclear surface testing is demonstrated. Melt glass from the first nuclear weapon test (commonly referred to as trinitite) is used as the benchmark for this study. These surrogates can be used to simulate a variety of scenarios and will serve as a tool for developing and validating forensic analysis methods.

Around the world, current energy and climate change concerns have led to more nations adopting nuclear technology as an option for electricity generation. However, one of the challenges to the peaceful application of this technology is the possibility that it will be misused, or that terrorists with global reach may acquire nuclear materials. Nigeria is one country that has embraced the technology to solve its energy challenges, but the country is now faced with an upsurge in terrorism and uprisings staged by various ethnic groups. In addition, corruption is continually becoming a hindrance to national development. These challenges are critical factors to be considered when vetting and recruiting reliable personnel for peaceful nuclear-related applications. It is important to understand how these human elements and other factors can impact global threats or undermine both Nigeria’s national security as well as international security. Knowledge of these matters will help Nigerian bureaucrats anticipate and correct deficiencies that might evolve from current procedures being degraded by these emerging threats and will prevent any catastrophe that any of the highlighted challenges could bring about. Being aware of these challenges and introducing appropriate policy will provide critical guidance to Nigeria and other emerging nuclear countries in a way that could lead to significant long-term improvements in management, procedures, and overall security of the facilities and materials. The challenge is to establish a Human Reliability Program (HRP) in order to detect and prevent aberrant behavior, thus effecting the safe, secure, and unhindered application of nuclear technology in Nigeria. In addition, this research suggests a strategy for conducting a national threat assessment and evaluation as a first step that precedes the development of an HRP; such a strategy must consider the range of threats present across the country.

Suppressing afterglow is important for extending the application of high-light-yield, high-density metal halides in sensor technology, from homeland security to medical imaging, but is thwarted by our limited understanding of the photophysics involved. This study uses codoping to successfully diminish afterglow in a high-performance halide scintillator. Its experimental results and theoretical calculations show why this approach works: Introducing a small cation to intentionally form a positively charged interstitial can reduce the formation of halogen vacancies, which act as deep electron traps that promote the undesirable afterglow.

This work identifies analytical lines in laser-induced plasma for chemical analyses of major elements found in surrogate nuclear debris. These lines are evaluated for interferences and signal strength to insure they would be useful to measure relative concentrations. Compact, portable instruments are employed and can be included as part of a mobile nuclear forensics laboratory for field screening of nuclear debris and contamination. The average plasma temperature is measured using the well-established Boltzmann plot technique, and plasma’s average electron density is determined using empirical formulae based on Stark broadening of the H-alpha line. These measurements suggest existence of partial local thermal equilibrium.

Novel water-soluble 6Li loaded copolymer scintillation films have been designed and fabricated to detect thermal neutrons. Styrene and maleic anhydride were copolymerized to form an alternating copolymer, then the anhydride functionality was hydrolyzed using 6Li hydroxide. The resulting poly(styrene-co-lithium maleate) was mixed with salicylic acid as a fluor and cast as a thin film from water. The maximum 6Li loading obtained that resulted in a transparent film was 4.36% by mass (6Li to polymer). The optimum fluorescence output was obtained for 11.7% salicylic acid by mass, presumably in the form of lithium salicylate, resulting in an optimum film containing 3.85% by mass of 6Li. A facile and robust synthesis method, film fabrication protocol, photoluminescence results, and scintillation responses are reported herein.

Deterring nuclear terrorism is a critical national asset to support the preclusion of non-state actors from initiating a nuclear attack on the United States. Successful attribution of a detonated nuclear weapon allows for timely responsive measures that prove essential in the period following a nuclear event. In conjunction with intelligence and law enforcement evidence, the technical nuclear forensics (TNF) post-detonation community supports this mission through the development and advancement of expertise to characterize weapon debris through a rapid, accurate, and detailed approach. Though the TNF field is young, numerous strides have been made in recent years toward a more robust characterization capability. This work presents modern advancements in post-detonation expertise over the last ten years and demonstrates the need for continued extensive research in this field.

Triplet sets of replaceable graphite rod collector probes (CPs), each with collection surfaces on opposing faces and oriented normal to the magnetic field, were inserted at the outboard mid-plane of DIII-D to study divertor tungsten (W) transport in the Scrape-Off Layer (SOL). Each CP collects particles along field lines with different parallel sampling lengths (determined by the rod diameters and SOL transport) giving radial profiles from the main wall inward to R-Rsep ∼ 6 cm. The CPs were deployed in a first-of-a-kind experiment using two toroidal rings of distinguishable isotopically enriched, W-coated divertor tiles installed at 2 poloidal locations in the divertor. Post-mortem Rutherford backscatter spectrometry of the surface of the CPs provided areal density profiles of elemental W coverage. Higher W content was measured on the probe side facing along the field lines toward the inner target indicating higher concentration of W in the plasma upstream of the CP, even though the W-coated rings were in the outer target region of the divertor. Inductively coupled plasma mass spectroscopy validates the isotopic tracer technique through analysis of CPs exposed during L-mode discharges with the outer strike point on the isotopically enriched W coated-tile ring. The contribution from each divertor ring of W to the deposition profiles found on the mid-plane collector probes was able to be de-convoluted using a stable isotope mixing model. The results provided quantitative information on the W source and transport from specific poloidal locations within the lower divertor region.

A hand-held device for laser-induced breakdown spectroscopy has been investigated for the determination of uranyl fluoride surface contamination. This research demonstrates the ability to successfully detect uranium on surfaces when using a low resolving power (λ/Δλ=4000) spectrograph, with a 5 mJ energy per 1 ns pulsed laser radiation, available as a commercially packaged hand-held system. Sand/uranyl fluoride mixtures are prepared to simulate residue likely encountered during decontamination efforts at facilities that handle uranium hexafluoride. Detection limits are described for four uranium lines with one revealing the capability to detect uranium at a level of 250 parts per million. Advantages of the studied compact device include that location specific information can be obtained on-site to augment contamination identification.

Thin film polystyrene composite scintillators containing and organic fluors have been fabricated and tested as thermal neutron detectors. Varying fluorescence emission intensities for different compositions are interpreted in terms of the Beer-Lambert law and indicate that the sensitivity of fluorescent sensors can be improved by incorporating transparent particles with refractive index different than that of the polymer matrix. Compositions and thicknesses were varied to optimize the fluorescence and thermal neutron response and to reduce gamma-ray sensitivity. Neutron detection efficiency and neutron/gamma-ray discrimination are reported herein as functions of composition and thickness. Gamma-ray sensitivity is affected largely by changing thickness and unaffected by the amount of in the film. The best neutron/gamma-ray discrimination characteristics are obtained for film thicknesses in the range 25–150 μm.