Kevin P. Carney

Application of mass spectrometric isotope dilution methodology for 90Sr age-dating with measurements by thermal-ionization and inductively coupled-plasma mass spectrometry

Application of an isotope-dilution method for determining 90Zr and 90Sr in a 90Sr source material spiked with 86Sr and 92Zr is described. A miniature gas pressurized extraction chromatography (GPEC) system with a column containing Eichrom Sr Resin™ was used for separating the elements so isobaric isotopes could be measured by mass spectrometry. Zirconium was rinsed through the column with 3 M HNO3/trace HF and strontium was eluted with 1% acetic acid. Two mass spectrometric techniques, inductively coupled plasma mass spectrometry (ICP-MS) and thermal ionization mass spectrometry (TIMS), were used for measuring isotope ratios. Data were obtained with 90Sr from a blood-irradiator source. Results from the TIMS measurements gave a decay time of 45.16 ± 0.26 years, and those from the ICP-MS gave 45.24 ± 0.20 years (uncertainties are expanded uncertainty, k = 2). Quadrupole ICP-MS is preferable to TIMS in this application if the ICP-MS data are suitably corrected for non-linearity and mass discrimination.

Extraction chromatographic separations of tantalum and tungsten from hafnium and complex matrix constituents

Tantalum (Ta), hafnium (Hf), and tungsten (W) analyses from complex matrices require high purification of these analytes from each other and major/trace matrix constituents, however, current state-of-the-art Ta/Hf/W separations rely on traditional anion exchange approaches that show relatively similar distribution coefficient (Kd) values for each element. This work reports an assessment of three commercially available extraction chromatographic resins (TEVA, TRU, and UTEVA) for Ta/Hf/W separations. Batch contact studies show differences in Ta/Hf and Ta/W Kd values of up to 106 and 104 (respectively), representing an improvement of a factor of 100 and 300 in Ta/Hf and Ta/W Kd values (respectively) over AG1×4 resin. Variations in the Kd values as a function of HCl concentration for TRU resin show that this resin is well suited for Ta/Hf/W separations, with Ta/Hf, Ta/W, and W/Hf Kd value improvements of 10, 200, and 30 (respectively) over AG1×4 resin. Analyses of digested soil samples (NIST 2710a) using TRU resin and tandem TEVA-TRU columns demonstrate the ability to achieve extremely high purification (>99%) of Ta and W from each other and Hf, as well as enabling very high purification of Ta and W from the major and trace elemental constituents present in soils using a single chromatographic step.

Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates

Production of certified reference materials in support of domestic nuclear forensics programs require volatile precursors for introduction into electromagnetic isotopic separation instruments. β-Diketone chelates of tetravalent actinides are known for their high volatility, but previously developed synthetic approaches require starting material (NpCl4) that is prohibitively difficult and hazardous to prepare. An alternative strategy was developed here that uses controlled potential electrolysis to reduce neptunium to the tetravalent state in submolar concentrations of hydrochloric acid. Four different β-diketone ligands of varying degrees of fluorination were reacted with an aqueous solution of Np4+. Products of this reaction were characterized via X-ray diffraction and infrared spectroscopy, and were found to be neutral 8-coordinate complexes that adopt square antiprismatic crystal geometry. Synthesis of Np β-diketonates by this approach circumvents the necessity of using NpCl4 in tetravalent Np coordination compound synthesis. The volatility of the complexes was assessed using thermogravimetric analysis, where the temperature of sublimation was determined to be in the range of 180° to 205 °C. The extent of fluorination did not appreciably alter the sublimation temperature of the complex. Thermal decomposition of these compounds was not observed during sublimation. High volatility and thermal stability of Np β-diketonates make them ideal candidates for gaseous introduction into isotopic separation instruments.

The development of radioactive sample surrogates for training and exercises

Source term information is required for to reconstruct a device used in a dispersed radiological dispersal device. Simulating a radioactive environment to train and exercise sampling and sample characterization methods with suitable sample materials is a continued challenge. The Idaho National Laboratory has developed and permitted a radioactive response training range (RRTR), an 800 acre test range that is approved for open air dispersal of activated KBr, for training first responders in the entry and exit from radioactively contaminated areas, and testing protocols for environmental sampling and field characterization. Members from the Department of Defense, Law Enforcement, and the Department of Energy participated in the first contamination exercise that was conducted at the RRTR in the July 2011. The range was contaminated using a short lived radioactive 82Br isotope (activated KBr). Soil samples contaminated with KBr (dispersed as a solution) and glass particles containing activated potassium bromide that emulated dispersed radioactive materials (such as ceramic-based sealed source materials) were collected to assess environmental sampling and characterization techniques. This presentation summarizes the performance of a radioactive materials surrogate for use as a training aide for nuclear forensics.

A composite position independent monitor of reactor fuel irradiation using Pu, Cs, and Ba isotope ratios

When post-irradiation materials from the nuclear fuel cycle are released to the environment, certain isotopes of actinides and fission products carry signatures of irradiation history that can potentially aid a nuclear forensic investigation into the materials provenance. In this study, combinations of Pu, Cs, and Ba isotope ratios that produce position (in the reactor core) independent monitors of irradiation history in spent light water reactor fuel are identified and explored. These position independent monitors (PIMs) are modeled for various irradiation scenarios using automated depletion codes as well as ordinary differential equation solutions to approximate nuclear physics models. Experimental validation was performed using irradiated low enriched uranium oxide fuel from a light water reactor, which was sampled at 8 axial positions from a single rod. Plutonium, barium and cesium were chemically separated and isotope ratio measurements of the separated solutions were made by quadrupole and multi-collector inductively coupled mass spectrometry (Cs and Pu, respectively) and thermal ionization mass spectrometry (Ba). The effect of axial variations in neutron fluence and energy spectrum are evident in the measured isotope ratios. Two versions of a combined Pu and Cs based PIM are developed. A linear PIM model, which can be used to solve for irradiation time is found to work well for natural U fuel with <10% 240Pu and known or short cooling times. A non-linear PIM model, which cannot be solved explicitly for irradiation time without additional information, can nonetheless still group samples by irradiation history, including high burnup LEU fuel with unknown cooling time. 137Ba/138Ba is also observed to act as a position independent monitor; it is nearly single valued across the sampled fuel rod, indicating that samples sharing an irradiation history (same irradiation time and cooling time) in a reactor despite experiencing different neutron fluxes will have a common 137Ba/138Ba ratio. Modeling of this Ba PIM shows it increases monotonically with irradiation and cooling time, and a confirmatory first order analytical solution is also presented.