Warren J. Oldham

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.

Synthesis and structure of N-heterocyclic carbene complexes of uranyl dichloride

Treatment of UO2Cl2(thf)3 in THF with two equivalents of 1,3-dimesitylimidazole-2-ylidene (IMes) or 1,3-dimesityl-4,5-dichloroimidazole-2-ylidene (IMesCl2) yields novel monomeric uranyl N-heterocyclic carbene complexes, representing the first examples of actinyl carbon bonds.

Kläui Ligand Thin Films for Rapid Plutonium Analysis by Alpha Spectrometry

As part of a nuclear forensics capability, rapid and effective methods to analyze for plutonium and other actinide metals are needed. A key requirement of these methods is that they afford a high chemical yield while still providing isotopic information necessary for forensic evaluation. Toward this objective, a new method for binding plutonium for analysis by alpha spectrometry has been developed. Thin films of Kläui-type tripodal oxygen donor ligands were prepared by spin-casting solutions onto glass substrates. Three different ligands were evaluated for plutonium binding, and the best results were obtained using the ethyl-substituted complex Na[Cp*Co(P(O)(OEt)2)3], which bound 80-88% of the dissolved Pu under equilibrium conditions. The thin films are simple and inexpensive to prepare and exhibit excellent alpha spectral resolution, having line widths of ~33 keV. The method has been successfully applied to analyze for plutonium in both an archived nuclear debris sample and a certified environmental soil sample. The results obtained from the soil analysis are in good agreement with the certified values, demonstrating the effectiveness of the method for rapid plutonium analysis.

Concurrent determination of 237Np and Pu isotopes using ICP-MS: analysis of NIST environmental matrix standard reference materials 4357, 1646a, and 2702.

An optimized method was developed to analyze environmental soil and sediment samples for (237)Np, (239)Pu, and (240)Pu by ICP-MS using a (242)Pu isotope dilution standard. The high yield, short time frame required for analysis, and the commercial availability of the (242)Pu tracer are significant advantages of the method. Control experiments designed to assess method uncertainty, including variation in inter-element fractionation that occurs during the purification protocol, suggest that the overall precision for measurements of (237)Np is typically on the order of ± 5%. Measurements of the (237)Np concentration in a Peruvian Soil blank (NIST SRM 4355) spiked with a known concentration of (237)Np tracer confirmed the accuracy of the method, agreeing well with the expected value. The method has been used to determine neptunium and plutonium concentrations in several environmental matrix standard reference materials available from NIST: SRM 4357 (Radioactivity Standard), SRM 1646a (Estuarine Sediment) and SRM 2702 (Inorganics in Marine Sediment).

Chloroheptakis(dimethyl sulfoxide)­uranium(IV) trichloride

In the title complex, [UCl(C(2)H(6)OS)(7)]Cl(3), the uranium metal center is coordinated in a distorted bicapped trigonal prism geometry by seven O atoms from dimethyl sulfoxide ligands and by a terminal chloride ligand. Charge balance is maintained by three outer-sphere chloride ions per uranium(IV) metal center. Principle bond lengths include U-O 2.391 (2)-2.315 (2) A, U-Cl 2.7207 (9) A, and average S-O 1.540 (5) A.

Measurements of extinct fission products in nuclear bomb debris: Determination of the yield of the Trinity nuclear test 70 y later

Significance This work describes an approach to postdetonation nuclear forensics involving isotopic measurements that allows for characterization of a nuclear detonation at any time. By performing high-precision measurements of stable isotope perturbations in nuclear bomb debris, it is possible to quantify short-lived fission products long after they have decayed below radiometric detection limits and become extinct. The extinct fission product concentrations can be used to reconstruct details of the nuclear device months to years after the detonation occurred. The approach is demonstrated by analysis of debris from the Trinity nuclear test and new estimates of the efficiency and yield of the historic test are presented. This paper describes an approach to measuring extinct fission products that would allow for the characterization of a nuclear test at any time. The isotopic composition of molybdenum in five samples of glassy debris from the 1945 Trinity nuclear test has been measured. Nonnatural molybdenum isotopic compositions were observed, reflecting an input from the decay of the short-lived fission products 95Zr and 97Zr. By measuring both the perturbation of the 95Mo/96Mo and 97Mo/96Mo isotopic ratios and the total amount of molybdenum in the Trinity nuclear debris samples, it is possible to calculate the original concentrations of the 95Zr and 97Zr isotopes formed in the nuclear detonation. Together with a determination of the amount of plutonium in the debris, these measurements of extinct fission products allow for new estimates of the efficiency and yield of the historic Trinity test.

Electrorecovery of Actinides at Room Temperature

There are a large number of purification and processing operations involving actinide species that rely on high-temperature molten salts as the solvent medium. One such application is the electrorefining of impure actinide metals to provide high purity material for subsequent applications. There are some drawbacks to the electrodeposition of actinides in molten salts including relatively low yields, lack of accurate potential control, maintaining efficiency in a highly corrosive environment, and failed runs. With these issues in mind we have been investigating the electrodeposition of actinide metals, mainly uranium, from room temperature ionic liquids (RTILs) and relatively high-boiling organic solvents. The RTILs we have focused on are comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and mainly the {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anion [bis(trif1uoromethylsulfonyl)imide {equivalent_to} {sup -}NTf{sub 2}]. These materials represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. In order to ascertain the feasibility of using RTILs for bulk electrodeposition of actinide metals our research team has been exploring the electron transfer behavior of simple coordination complexes of uranium dissolved in the RTIL solutions. More recently we have begun some fundamental electrochemical studies on the behavior of uranium and plutonium complexes in the organic solvents N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO). Our most recent results concerning electrodeposition will be presented in this account. The electrochemical behavior of U(IV) and U(III) species in RTILs and the relatively low vapor pressure solvents NMP and DMSO is described. These studies have been ongoing in our laboratory to uncover conditions that will lead to the successful bulk electrodeposition of actinide metals at a working electrode surface at room temperature or slightly elevated temperatures. The RTILs we have focused on thus far are based on 1,3-dialkylimidazolium or quaternary ammonium cations and {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anions. Our results from XPS studies of e1ectrooxidized uranium metal surfaces indicate that uranium metal reacts with the anion from the RTIL, most likely through an initial f1uoride abstraction, forming decomposition products that inhibit the bulk electrodeposition of uranium metal. Similar results were found when the organic solvents were used with TBA[B(C{sub 6}F{sub 5}){sub 4}] as the supporting electrolyte, although the voltammetric data of uranium ions in these solutions is more encouraging in relation to electrodeposition of uranium metal. Preliminary results on the voltammetric behavior and bulk electrodeposition of plutonium species are also presented.

Sequential chemical separations and multiple ion counting ICP-MS for 241Pu–241Am–237Np dating of environmental collections on a single aliquot

We have developed a combined sequential chemical separation procedure and multiple ion counting ICP-MS measurement method for isotopic measurements of Am in environmental samples. This, in conjunction with established resin bead TIMS measurements for Pu and Np, allows us to measure long-lived Pu–Np–Am nuclides in environmental samples on a single solution aliquot. This single aliquot method reduces time lines and maximizes sample utility for the measurements, improving sensitivity, precision, and accuracy over prior methods. We have evaluated this new method with environmental reference materials and have obtained accurate results on samples with > 3E6 atoms 241Am.

Measurements of plutonium, 237Np, and 137Cs in the BCR 482 lichen reference material

Abstract Select anthropogenic radionuclides were measured in lichen reference material, BCR 482. This material was originally collected in Axalp, Switzerland in 1991 and is composed of the epiphytic lichen Pseudevernia furfuracea. Samples from three separate bottles of BCR 482 were analyzed for uranium, neptunium, and plutonium isotopes by inductively coupled plasma mass spectrometry and analyzed for 137Cs by gamma-ray spectrometry. The isotopic composition of the radionuclides measured in BCR 482 suggests contributions from both global fallout resulting from historical nuclear weapons testing and more volatile materials released following the Chernobyl accident.

Actinide chemistry in room temperature ionic liquids: actinide chemistry in RTIL systems (why?)

Room temperature ionic liquids (RTILs) have potential throughout the nuclear industry in the recovery and purification of actinide elements, as reactor components, as waste disposal forms, and potentially as media for the storage and/or separation of spent nuclear fuels. Due to their unique dissolution properties, RTILs can be used as substitutes for solvents currently used in the extraction of uranium from native ores, and in the dissolution and reprocessing of spent nuclear fuels. Research efforts in our laboratory focus on determining the chemical properties (i.e., solubility, complexation, redox properties, etc.) of actinide species in RTIL systems. We are currently involved in RTIL projects ranging from the spectroscopic characterization of actinide complexes by O17NMR, low temperature UV-Vis, and EXAFS, to the enhanced dissolution and separation of actinide oxides in room temperature ionic liquids.