Pursuing standards strategies in nuclear forensics: investigating extraction of progeny uranium in CRM-126a as a quality control material in Pu–U chronometry

Parent–progeny isotope relationships provide critical signatures in forensic efforts designed to determine the history of interdicted nuclear materials. Unfortunately, there is substantial need for new standards and QC strategies yielding confidence in such chronometric measurements. Here, we investigate the initial isolation of progeny uranium in certified reference material-126a for use as a precision comparator in a thermal ionization mass spectrometry-based QC strategy seeking to provide improved uncertainties in isotopic and chronometric measurements for nuclear materials containing elevated U-236, such as plutonium. Application to real-world Pu either preserved or improved upon uncertainties associated with key parent–daughter ratios and further constrained associated chronometric windows.

     

Advances in the development and component recognition of latent fingerprints

Fingerprints have been used as an indispensable tool for personal identification in forensic investigations since the late 19 th century. At present, fingerprinting technology has moved away from its forensic roots and is incorporating a broader scientific range, e.g., material science, spectroscopy and spectral analysis, and even in vitro diagnosis. After a brief introduction to latent fingerprints, this mini-review presents the pioneering progresses of fingerprinting technologies including(i) material and electrochemical techniques, and(ii) spectral and spectroscopy imaging techniques and immunological techniques capable of both the visualization of a fingerprint and the detection of chemicals present in it. Finally, perspectives on this rapidly developing field are discussed.     

Advances in the development of a dissolution method for the attribution of iridium source materials

Journal of Radioanalytical and Nuclear Chemistry - To assist in nuclear forensic investigations, new techniques are required to evaluate radioactive materials that may be discovered outside of...     

Physical characterization of uranium oxide pellets and powder applied in the Nuclear Forensics International Technical Working Group Collaborative Materials Exercise 4

Journal of Radioanalytical and Nuclear Chemistry - Physical characterization is one of the most broad and important categories of techniques to apply in a nuclear forensic examination. Physical...     

Monte Carlo analysis of thermochromatography as a fast separation method for nuclear forensics

Nuclear forensic science has become increasingly important for global nuclear security, and enhancing the timeliness of forensic analysis has been established as an important objective in the field. New, faster techniques must be developed to meet this objective. Current approaches for the analysis of minor actinides, fission products, and fuel-specific materials require time-consuming chemical separation coupled with measurement through either nuclear counting or mass spectrometry. These very sensitive measurement techniques can be hindered by impurities or incomplete separation in even the most painstaking chemical separations. High-temperature gas-phase separation or thermochromatography has been used in the past for the rapid separations in the study of newly created elements and as a basis for chemical classification of that element. This work examines the potential for rapid separation of gaseous species to be applied in nuclear forensic investigations. Monte Carlo modeling has been used to evaluate the potential utility of the thermochromatographic separation method, albeit this assessment is necessarily limited due to the lack of available experimental data for validation.     

Uranium from German Nuclear Power Projects of the 1940s— A Nuclear Forensic Investigation

Here we present a nuclear forensic study of uranium from German nuclear projects which used different geometries of metallic uranium fuel. 3b , 3d , 4 Through measurement of the ²³⁰Th/²³⁴U ratio, we could determine that the material had been produced in the period from 1940 to 1943. To determine the geographical origin of the uranium, the rare‐earth‐element content and the ⁸⁷Sr/⁸⁶Sr ratio were measured. The results provide evidence that the uranium was mined in the Czech Republic. Trace amounts of ²³⁶U and ²³⁹Pu were detected at the level of their natural abundance, which indicates that the uranium fuel was not exposed to any major neutron fluence.     

Use of INAA in the homogeneity evaluation of a bovine kidney candidate reference material

Instrumental neutron activation analysis was used to evaluate the between bottle homogeneity and the minimum sample intake of a bovine kidney candidate reference material. The mass fractions of ten inorganic constituents were determined, obtaining satisfactory homogeneity results for all of them. Statistical analysis of the results was performed using a one way analysis of variance and multivariate techniques were applied as complementary techniques, confirming the usefulness of these techniques for homogeneity assessment.

     

Law enforcement tools available at the Savannah River Site

A number of nuclear technologies developed and applied at the Savannah River Site in support of nuclear weapons material production and environmental remediation can be applied to problems in law enforcement. Techniques and equipment for high-sensitivity analyses of samples are available to identify and quantify trace elements and establish origins and histories of forensic evidence removed from crime scenes. While some of these capabilities are available at local crime laboratories, state-of-the-art equipment and breakthroughs in analytical techniques are continually being developed at DOE laboratories. Extensive experience with the handling of radioactive samples at the DOE labs minimizes the chances of cross-contamination of evidence received from law enforcement. In addition to high-sensitivity analyses, many of the field techniques developed for use in a nuclear facility can assist law enforcement personnel in detecting illicit materials and operations, in retrieving of pertinent evidence and in surveying crime scenes. Some of these tools include chemical sniffers, hand-held detectors, thermal imaging, etc. In addition, mobile laboratories can be deployed to a crime scene to provide field screening of potential evidence. A variety of portable sensors can be deployed on vehicle, aerial, surface or submersible platforms to assist in the location of pertinent evidence or illicit operations. Several specific nuclear technologies available to law enforcement and their potential uses are discussed.     

Assessing thermochromatography as a separation method for nuclear forensics: current capability vis-à-vis forensic requirements

Nuclear forensic science has become increasingly important for global nuclear security. However, many current laboratory analysis techniques are based on methods developed without the imperative for timely analysis that underlies the post-detonation forensics mission requirements. Current analysis of actinides, fission products, and fuel-specific materials requires time-consuming chemical separation coupled with nuclear counting or mass spectrometry. High-temperature gas-phase separations have been used in the past for the rapid separation of newly created elements/isotopes and as a basis for chemical classification of that element. We are assessing the utility of this method for rapid separation in the gas-phase to accelerate the separations of radioisotopes germane to post-detonation nuclear forensic investigations. The existing state of the art for thermochromatographic separations, and its applicability to nuclear forensics, will be reviewed.     

An Integration Method for Enzyme Multiplied Immunoassays

Abstract

Integration methods for measuring substrates via homogeneous immunoassays are presented along with their theoretical bases. Integrals of differences in measured responses over time are used with enzyme multiplied immunoassay techniques and show unique relationships between the net integral data and analyte concentrations. Changes in indicator response signals are integrated over several minutes for drugs of forensic interest, and results for integrations of both published response curve data and laboratory assays are evaluated.     

Structural,spectral, experimental,and theoretical investigations of (E)-4-fluoro-N′-(pyridin-2-ylmethylene)benzohydrazide monohydrate

The structural and nonlinear optical properties of the Schiff base material, (E)-4-fluoro-N′-(pyridin-2-ylmethylene)benzohydrazide monohydrate (FPMBH) were studied. The experimental investigations were performed using Fourier transform infrared (FTIR), ultraviolet (UV) and nuclear magnetic resonance (NMR) spectral techniques. The computational analyses were made by DFT method. A comparison between experimental and theoretical predictions was made and interpreted. The maximum absorption wavelength was found by both experimental and theoretical analyses. The Hirshfeld surface analysis was performed to understand the various molecular interactions. Highest occupied and lowest unoccupied molecular orbitals (HOMO–LUMO) analysis was performed for the title molecule to know about the possible charge transfer taking place within the molecule. Reactivity features were also determined by molecular electrostatic potential (MEP) analysis. The third-order nonlinear optical studies were done by z-scan experiment, and the results were discussed.

     

元素成像技术在核法证中的应用研究进展

核法证学是打击非法贩卖核材料和放射性物质的重要工具,可用于对截获的材料进行分析溯源。过去的研究主要集中于元素和同位素特征的总体分析表征。近年来,随着微分析技术的发展,微米尺度和纳米尺度元素和同位素空间分布特征、微观形态学特征研究正成为核法证学研究的热点。本文基于近年来国内外核法证学的研究成果,详细介绍了元素成像技术在核法证学材料分析领域元素和同位素成像、微观形态学方面的应用研究进展。     

Sensitivity study on modeling radioxenon signals from radiopharmaceutical production facilities

As part of the Comprehensive Nuclear Test-Ban Treaty (CTBT), the International Monitoring System (IMS) was established to monitor the world for nuclear weapon explosions. As part of this network, systems are in place to monitor the atmosphere for radioxenon. The IMS routinely detects radioxenon from sources other than nuclear explosions. One of these radioxenon sources is radiopharmaceutical production facilities. This is a sensitivity study on the nuclear forensic signals possible from such facilities. A fission process model was produced to calculate the activity of ^131mXe, ^133mXe, ¹³³Xe and ¹³⁵Xe in the process utilized to produce ⁹⁹Mo and ¹³¹I for medical applications through high enriched uranium fission. The computer model accounts for fractionation of radionuclides within a decay chain that may result from filtering or chemical procedures. Ratios of the radioxenon isotopes are calculated as a function of decay time after the release. The ratios are then compared to those expected from nuclear explosions. The main conclusion from this work is that the two main factors that affect the nuclear forensic signal from radiopharmaceutical production facilities are the sample irradiation time and the use of emission gas storage tanks.     

Preparation and calibration of a 231Pa reference material

A ²³¹Pa reference material has been characterized for amount of protactinium. This reference material is primarily intended for calibration of ²³³Pa tracers produced for ²³⁵U–²³¹Pa model age measurements associated with nuclear forensics and nuclear safeguards. Primary measurements for characterization were made by isotope dilution mass spectrometry of a purified ²³¹Pa solution using a ²³³Pa isotopic spike. The spike was calibrated by allowing multiple aliquots of the ²³³Pa spike solution to decay to ²³³U and then measuring the ingrown ²³³U by isotope dilution mass spectrometry using a certified uranium assay and isotopic standard as a reverse-spike. The new ²³¹Pa reference material will simplify calibration of the ²³³Pa isotope dilution spikes, provide metrological traceability, and potentially reduce the overall measurement uncertainty of model ages.

     

Evaluating uranium radiochronometry by single-collector mass spectrometry for nuclear forensics: a multi-instrument investigation

Radiochronometric data, a key signature in evaluating the provenance and process history of nuclear material out of regulatory control, are conventionally acquired via multi-collector mass spectrometry. Here we explore the potential of age-dating by single-collector mass spectrometry. To evaluate model age accuracy/precision across different instrument designs, we performed ²³⁰Th–²³⁴U and ²³¹Pa–²³⁵U radiochronometry of CRM 125-A using two single-collector and one multi-collector plasma source mass spectrometers. Single-collector instruments produce accurate model ages for this uranium standard and thus hold promise for nuclear forensics radiochronometry. Increased acquisition of age information via multiple instrument designs will bolster the global response to nuclear interdictions.

     

Nuclear, chemical, and physical characterization of nuclear materials

The goal of nuclear forensics is to establish an unambiguous link between illicitly trafficked nuclear material and its origin. The Los Alamos National Laboratory (LANL) Nuclear Materials Signatures Program has implemented a graded “conduct of operations” type analysis flow path approach for determining the key nuclear, chemical, and physical signatures needed to identify the manufacturing process, intended use, and origin of interdicted nuclear material. This analysis flow path includes both destructive and non-destructive characterization techniques and has been exercized against different nuclear materials from LANL’s special nuclear materials archive. Results obtained from the case study will be presented to highlight analytical techniques that offer the critical attribution information.     

Purification of an Endogenous Modulator for Voltage-Sensitive Calcium Channels Using the Eccentric Multi-Layer Coil Planet Centrifuge

Abstract

High-speed countercurrent chromatography using a two-phase solvent system was found to be the method of choice for purifying an endogenous Ca2+ channel modulator. The solvent system composed of n-butanol, acetic acid and water (4:1:5) was most suitable for resolving the active material from other unknown substances of low molecular weight. Countercurrent chromatography proved useful in validating the presence in rat brain of an endogenous ligand for dihydropyridine-sensitive Ca²⁺ channels. Moreover, the degree of purity of the active material obtained by countercurrent chromatography is suitable for consecutive analysis by mass spectrometry or nuclear magnetic resonance.     

Determination of rare-earth elements in uranium-bearing materials by inductively coupled plasma mass spectrometry

A novel and simple analytical procedure has been developed for the trace-level determination of lanthanides (rare-earth elements) in uranium-bearing materials by inductively coupled plasma sector-field mass spectrometry (ICP-SFMS). The method involves a selective extraction chromatographic separation of lanthanides using TRU™ resin followed by ICP-SFMS analysis. The limits of detection of the method proposed is in the low pg g⁻¹ range, which are approximately two orders of magnitude better than that of without chemical separation. The method was validated by the measurement of reference material and applied for the analysis of uranium ore concentrates (yellow cakes) for nuclear forensic purposes, as a potential application of the methodology.     

Uncertainty measurement evaluation of WDXRF and EDXRF techniques for the Si and U<Subscript>total</Subscript> determination in U<Subscript>3</Subscript>Si<Subscript>2</Subscript> nuclear fuel

Uranium silicide (U₃Si₂), 20% ²³⁵U enriched powder, is an intermetallic compound used as nuclear fuel material, which is the state-of-the-art among nuclear fuel materials used in modern research reactors. It is produced by IPEN and used as nuclear fuel of the IEA-R1 reactor (IPEN/CNEN, São Paulo, Brazil); U₃Si₂ has 92.3 wt% U_total and 7.7 wt% Si. The qualification of this material requires chemical and physical tests such as Si and U_total content, isotope ratio, impurities, density, specific surface area and particle size determination. The Si and U_total were determined by gravimetric and volumetric procedures. Usually, these classical methods require a long time for analyses and are expensive. The objective of this study was to establish a fast and efficient analytical method to meet ISO/IEC 17025:2005 requirements in the Si and U_total determination. The X-ray fluorescence techniques (XRF) were chosen to allow a direct and non-destructive analysis, what is the main advantage compared to other instrumental techniques, since previous chemical treatments are not necessary. In this study, the performance of the wavelength dispersive (WDXRF) and energy dispersive (EDXRF) X-ray fluorescence techniques was evaluated. Furthermore, two different sample preparation procedures, plain powdered and pressed powdered, were evaluated. Statistical tools were used to evaluate the results and a comparison between these results and the conventional methods was done.     

Nuclear forensic analysis of thorium

A comprehensive radiochemical isolation procedure and data analysis/interpretation method for the nuclear forensic investigation of Th has been developed. The protocol includes sample dissolution, chemical separation, nuclear counting techniques, consideration of isotopic parent-daughter equilibria, and data interpretation tactics. Practical application of the technology was demonstrated by analyses of a questioned specimen confiscated at an illegal drug synthesis laboratory by law enforcement authorities.