Ion beam analysis of elemental signatures in uranium dioxide samples: importance for nuclear forensics

In this paper the suitability of two non-destructive analytical techniques for identification of elemental signatures in samples containing uranium of different enrichments was studied. The measurements were based on particle induced X-ray emission (PIXE) and particle induced gamma-ray emission (PIGE) methods. The samples were irradiated by 3 and 5 MeV protons at the 3 MV Tandetron™ of Horia Hulubei National Institute for Physics and Nuclear Engineering. The characteristic X and gamma rays were measured using high purity germanium (HPGe) detectors. The GUPIX software was applied for processing the PIXE spectra, while a relative standardization was applied for PIGE analysis by using certified comparator standards and proton stopping powers calculated by SRIM.

     

A highly-enriched 244Pu reference material for nuclear safeguards and nuclear forensics measurements

Journal of Radioanalytical and Nuclear Chemistry - A highly-enriched 244Pu isotope dilution reference material has been prepared and characterized for metrologically traceable measurements of very...     

Environmental monitoring as an important tool for safeguards of nuclear material and nuclear forensics

Summary The use of environmental monitoring as a technique to identify activities related to the nuclear fuel cycle has been proposed by international safeguards organizations. The elements specific for each kind of nuclear activity, or “nuclear signatures”, inserted in the ecosystem can be intercepted by different live organisms. This work demonstrates the technical viability of using pine needles as bioindicators of nuclear signatures associated with uranium enrichment activities. Additionally, it proposes the use of HR-ICP-MS to identify the signature corresponding to that kind of activities in the ecosystem. Nitric acid solutions, used to wash pine needles sampled near nuclear facilities and containing only 0.1 mg ^. kg^-1 of uranium, exhibit a n(²³⁵U)/n(²³⁸U) isotopic abundance ratio of 0.0092±0.0002, while solutions originated from samples collected at places located more than 200 km far from activities related to the nuclear fuel cycle exhibit a value of 0.0074±0.0002. Similar results were obtained for sample solutions prepared using the acid leaching process. The different values of n(²³⁵U)/n(²³⁸U) isotopic abundance ratio obtained permit to confirm the presence of anthropogenic uranium and demonstrate the viability of using the methodology proposed in this work.     

New methodology for uranium analysis in swipe samples for nuclear safeguards purposes

Environmental swipe sampling for safeguards purpose has been used by International Atomic Energy Agency since 1997, being a powerful tool to detect undeclared materials and activities. This work describes a new methodology for swipe samples analysis based on ultrasound-assisted acid leaching and compares it with traditional total digestion bulk analysis. The proposed method requires few preparation steps, decreasing the risk of contamination, reduced amounts of reagents and a good option to extract uranium from swipe sample. In a real case study, the swipe samples were collected in a conversion plant at IPEN/CNEN, Brazil. The measurements were carried out by ICP-MS and the results showed relative error lower than 0.96 % for uranium isotopic ratios for the certified reference material (NBS U200). The uncertainties were estimated by following the ISO GUM, with a confidence level of 95 %. The uncertainties percentage for n(²³⁵U)/n(²³⁸U) ratio of the samples ranged from 2.5 to 4.3 %. The values of uranium isotopic ratio obtained for each method demonstrate the viability of using the methodology proposed in this work.     

The urgent requirement for new radioanalytical certified reference materials for nuclear safeguards, forensics, and consequence management

A multi-agency workshop was held from 25 to 27 August 2009, at the National Institute of Standards and Technology (NIST), to identify and prioritize the development of radioanalytical Certified Reference Materials (CRMs, generally provided by National Metrology Institutes; Standard Reference Materials, a CRM issued by NIST) for field and laboratory nuclear measurement methods to be used to assess the consequences of a domestic or international nuclear event. Without these CRMs, policy makers concerned with detecting proliferation and trafficking of nuclear materials, attribution and retribution following a nuclear event, and public health consequences of a nuclear event would have difficulty making decisions based on analytical data that would stand up to scientific, public, and judicial scrutiny. The workshop concentrated on three areas: post-incident Improvised Nuclear Device (IND) nuclear forensics, safeguard materials characterization, and consequence management for an IND or a Radiological Dispersion Device detonation scenario. The workshop identified specific CRM requirements to fulfill the needs for these three measurement communities. Of highest priority are: (1) isotope dilution mass spectrometry standards, specifically ²³³U, ^236gNp, ²⁴⁴Pu, and ²⁴³Am, used for quantitative analysis of the respective elements that are in critically short supply and in urgent need of replenishment and certification; (2) CRMs that are urgently needed for post-detonation debris analysis of actinides and fission fragments, and (3) CRMs used for destructive and nondestructive analyses for safeguards measurements, and radioisotopes of interest in environmental matrices.     

The use of LA-SF-ICP-MS for nuclear forensics purposes: uranium isotope ratio analysis

This work describes the utilization of the laser ablation sector field inductively coupled plasma mass spectrometry (LA-SF-ICP-MS) technique for the determination of uranium isotopic composition in a highly enriched uranium sample. The measurements were performed on a continuous ablation with low energy density and defocusing, which demonstrated to be the optimum to reach the best signal stability. The measurements were improved by adjusting the following parameters: RF power, laser beam diameter, defocusing of laser beam, laser energy, laser energy density, auxiliary gas and sample gas. The ²³⁵U/²³⁸U isotope ratio with its respective uncertainty was 16.36 ± 0.15 and its precision was 1.12 % relative standard deviation. The uncertainties were estimated following the ISO GUM, with a confidence level of 95.45 % (k = 2.00). When compared the isotope abundances to the Round Robin Exercise Number 3’s average results a difference of 0.46 % has been found and when compared to supplier’s value, the difference was 0.41 %. The results presented by the measurements revealed that the LA-ICP-MS technique offers a rapid and accurate alternative to measure uranium isotope ratios without any sample preparation, since it allows carrying out the measurements straight on the sample. Moreover, it preserves the testimony—very important for safeguards and nuclear forensics purposes.     

The use of lead isotopic abundances in trace uranium samples for nuclear forensics analysis

Secondary ion mass spectrometry (SIMS), secondary electron microscopy (SEM) and X-ray analysis have been applied to the measurement of U-bearing particles with the intent of gleaning information concerning their history and/or origin. The lead isotopic abundances are definitive indicators that U-bearing particles have come from an ore-body, even if they have undergone chemical processing. SEM images and X-ray analysis can add further information to the study that may allude to the extent of chemical processing. The presence of “common” lead that does not exhibit a radiogenic signature is clear evidence of anthropogenic origin.     

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.

     

Halides as potential signatures for geolocation of uranium phosphate rocks for nuclear forensic applications

Journal of Radioanalytical and Nuclear Chemistry - An analytical approach for halides determination in uranium-bearing phosphate rocks, based on halides extraction from natural calcium phosphate by...     

Trace analysis of uranium ore concentrates using laser ablation inductively coupled plasma mass spectrometry for nuclear forensics

Journal of Radioanalytical and Nuclear Chemistry - We present a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method for trace-element analysis of uranium ore concentrates...     

International cooperation in age-dating uranium standards for nuclear forensics using the 231Pa/235U radiochronometer

Journal of Radioanalytical and Nuclear Chemistry - During 2017–2018 Los Alamos National Laboratory, Lawrence Livermore National Laboratory and the China Institute of Atomic Energy...     

Application of Inductively Coupled Plasma Mass Spectrometry to the determination of uranium isotope ratios in individual particles for nuclear safeguards

The capability of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of uranium isotope ratios in individual particles was determined. For this purpose, we developed an experimental procedure including single particle transfer with a manipulator, chemical dissolution and isotope ratio analysis, and applied to the analysis of individual uranium particles in certified reference materials (NBL CRM U050 and U350). As the result, the ²³⁵U/²³⁸U isotope ratio for the particle with the diameter between 0.5 and 3.9 μm was successfully determined with the deviation from the certified ratio within 1.8%. The relative standard deviation (R.S.D.) of the ²³⁵U/²³⁸U isotope ratio was within 4.2%. Although the analysis of ²³⁴U/²³⁸U and ²³⁶U/²³⁸U isotope ratios gave the results with inferior precision, the R.S.D. within 20% was possible for the measurement of the particle with the diameter more than 2.1 μm. The developed procedure was successfully applied to the analysis of a simulated environmental sample prepared from a mixture of indoor dust (NIST SRM 2583) and uranium particles (NBL CRM U050, U350 and U950a). From the results, the proposed procedure was found to be an alternative analytical tool for nuclear safeguards.     

Development of ultrahigh energy resolution gamma spectrometers for nuclear safeguards

We are developing superconducting ultrahigh resolution gamma-detectors for non-destructive analysis (NDA) of nuclear materials, and specifically for spent fuel characterization in nuclear safeguards. The detectors offer an energy resolution below 100 eV FWHM at 100 keV, and can therefore significantly increase the precision of NDA at low energies where line overlap affects the errors of the measurement when using germanium detectors. They also increase the peak-to-background ratio and thus improve the detection limits for weak gamma emissions from the fissile Pu and U isotopes at low energy in the presence of an intense Compton background from the fission products in spent fuel. Here we demonstrate high energy resolution and high peak-to-background ratio of our superconducting Gamma detectors, and discuss their relevance for measuring actinides in spent nuclear fuel.     

Development of a data-mining methodology for spent nuclear fuel forensics

The purpose of this study is to categorize the type of spent nuclear fuels using simulation data-based classification methods. Considering the practical conditions making the full analysis of radioactive nuclides difficult, the classification methods were designed to be robust to noise and missing information. The strength and weakness of three classifiers, linear discriminant analysis, quadratic discriminant analysis and support vector classification were compared, which is developed by the history information such as burnup, enrichment, and cooling type generated from ORIGEN-ARP upon fuel assembly types. Auto-Associative Kernel Regression improved outlier management as a pre-processing technique.     

Primary studies on particle recovery of swipe samples for nuclear safeguards

Environmental sampling plays a significant role in nuclear safeguards. Isotopic ratio in uranium-bearing particles from swipe samples provides important information for detecting undeclared activities. Particle recovery which is the primary step of particle analysis, would affect the following analysis. The particle recovery efficiency of ultrasoneration recovery and vacuum suction-impact recovery were measured by alpha spectrometer with standard particles produced via aerosol spray pyrolysis method. The conditions of ultrasoneration were optimized and both recovery methods were evaluated. Finally, a procedure of particle recovery for unknown swipe samples was set up.     

Radioanalytical chemistry for nuclear forensics in China: Progress and future perspective

A relatively new branch of science - nuclear forensics, aiming at providing the nature, origin, history and possible trafficking route of seized nuclear materials/devices, has been established and rapidly developed over decades to screen illicit nuclear activities. This highly interdisciplinary science is built upon a foundation of analytical chemistry, radiochemistry, nuclear physics, material sciences, geology, and other scientific disciplines, within which radiochemical methodologies and radioanalytical techniques play a key role. The present review provides a brief overview about the crucial aspects of nuclear forensics, including basic content, procedure, concerned elements, common separation, analytical method, and so on. The state of the art and recent progresses of nuclear forensics by research communities in China are reviewed, while selected examples and practical applications are emphasized. The challenges associated with this new area and on-going developments are highlighted and discussed.     

Development of a data-driven classification algorithm for fresh nuclear fuel forensics

Journal of Radioanalytical and Nuclear Chemistry - According to the Incident and Trafficking Database of the International Atomic Energy Agency, incidents involving illegal transactions or...