A new highly enriched 233U reference material for improved simultaneous determination of uranium amount and isotope amount ratios in trace level samples.

A highly-enriched 233U reference material (>0.99987 n(233U)/n(U)) has been prepared and characterized for use as an isotope dilution mass spectrometry spike. An ion exchange separation was performed on 1 g of high purity 233U to further reduce trace amounts of contaminant Pu in the material. The purified 233U was then prepared as a master solution which was analyzed for molality of uranium by modified Davies and Gray titration. A portion of the master solution was quantitatively diluted and dispensed for reference material units. Selected units were analyzed for verification of uranium amount and to characterize uranium isotope amount ratios by multi-collector inductively couple plasma mass spectrometry. Modelling of spike-corrected isotopic data show that the new spike will enable simultaneous measurements of uranium amount and isotope amount ratios with resulting uncertainties that are substantially less sensitive to over spiking than widely used 233U certified reference materials.

Toward a New Primary Standardization of Radionuclide Massic Activity Using Microcalorimetry and Quantitative Milligram-Scale Samples.

We present a new paradigm for the primary standardization of radionuclide activity per mass of solution (Bq/g). Two key enabling capabilities are 4π decay-energy spectrometry using chip-scale sub-Kelvin microcalorimeters and direct realization of mass by gravimetric inkjet dispensing using an electrostatic force balance. In contrast to traditional traceability, which typically relies on chemical separation of single-radionuclide samples, 4π integral counting, and additional spectrometry methods to verify purity, the system described here has both 4π counting efficiency and spectroscopic resolution sufficient to identify multiple radionuclides in the same sample at once. This enables primary standardization of activity concentrations of mixed-radionuclide samples. A major benefit of this capability, beyond metrology, is in assay of environmental and forensics samples, for which the quantification of multiplenuclide samples can be achieved where presently inhibited by interferences. This can be achieved without the need for chemical separations or efficiency tracers, thereby vastly reducing time, radioactive waste, and resulting measurement uncertainty.

A highly­enriched 244Pu reference material for nuclear safeguards and nuclear forensics measurements.

A highly-enriched 244Pu isotope dilution reference material has been prepared and characterized for metrologically traceable measurements of very small quantities of plutonium. The amount of plutonium in samples associated with nuclear safeguards and nuclear forensic measurements can be significantly less than 1 ng. Accordingly, the ability to quantify the amount and isotopic composition of plutonium from a single mass-spectrometric analysis is particularly desirable. The highly-enriched 244Pu reference material, described here, will minimize the magnitude of spike corrections necessary to obtain accurate information on plutonium isotopic composition from isotope dilution measurements.

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.

A new thorium-229 reference material.

A new reference material was characterized for 229Th molality and thorium isotope amount ratios. This reference material is intended for use in nuclear forensic analyses as an isotope dilution mass spectrometry spike. The reference material value and expanded uncertainty (k = 2) for the 229Th molality is (1.1498 ± 0.0016) × 10-10molg-1 solution. The value and expanded uncertainty (k = 2) for the n(230Th)/n(229Th) ratio is (5.18 ± 0.26) × 10-5 and the n(232Th)/n(229Th) ratio is (3.815 ± 0.092) × 10-4.

New determination of the 229Th half-life.

A new determination of the 229Th half-life was made based on measurements of the 229Th massic activity of a high-purity solution for which the 229Th molality had previously been measured. The 229Th massic activity was measured by direct comparison with SRM 4328C using 4παß liquid scintillation counting, NaI counting, and standard addition liquid scintillation counting. The massic activity was confirmed by isotope dilution alpha spectrometry measurements. The calculated 229Th half-life is (7825 ± 87) years (k = 2), which is shorter than the three most recent half-life determinations but is consistent with these values within uncertainties.

A reference material for evaluation of 137 Cs radiochronometric measurements.

A new nuclear forensic reference material has been characterized as a standard for radiochronometric determination of the model purification date for 137Cs sources. The purification date of a radioactive source is a potentially diagnostic nuclear forensic signature for determining the provenance of a radioactive material. Reference values have been measured for the attributes needed to use the 137Cs/137Ba chronometer: the molality (reported here as nmol g-1) of 137Cs and of the radiogenic portion of 137Ba in the material (hereafter referred to as 137Ba*). All measurement results were decay-corrected to represent the composition of the material on the reference date of July 7, 2011. The molality of 137Cs is (0.7915 ± 0.0073) nmol g-1; this value was calculated from the massic activity of 137Cs, (348.4 ± 3.0) kBq g-1, as measured in the NIST 4π-γ secondary standard ionization chamber (previously calibrated by 4π-(e+x)-γ-coincidence efficiency extrapolation counting) and the evaluated half-life of 137Cs, (30.05 ± 0.08) years. The molality of 137Ba*, (1.546 ± 0.024) nmol g-1, was measured by isotope dilution mass spectrometry using the measured relative proportion of 138Ba in the material to apply a correction for the 137Ba contribution from natural Ba. A model age of (47.04 ± 0.56) years, corresponding to a model purification date of June 22, 1964 with an expanded uncertainty of 200 days is calculated from the reference material values. This age is consistent with the date engraved on the capsule that contained the 137Cs starting material and with a prior independent determination of the model purification date. A full discussion of the uncertainties of the reference material values is included.