Erick C. Ramon

Magnesium isotope heterogeneity of the isotopic standard SRM980 and new reference materials for magnesium-isotope-ratio measurements

Multicollector ICP-MS has been used for the precise measurement of variations in the isotopic composition of the isotopic standard of magnesium (SRM980) provided by the National Institute of Standards and Technology (Gaithersburg, MD, USA). The SRM980 consists of metal chips weighing between 1 and 50 mg and each unit delivered by the National Institute of Standards and Technology corresponds to a bottle containing about 0.3 g. Height units were analysed. Variations in sample 25Mg/24Mg, and 26Mg/24Mg ratios are expressed as δ25Mg and δ26Mg units, respectively, which are deviations in parts per 103 from the same ratio in a standard solution. The differences in δ25Mg and δ26Mg of the SRM980 are up to 4.20 and 8.19‰, respectively, while the long-term repeatability of δ25Mg and δ26Mg are 0.09 and 0.16‰, respectively, at 95% confidence. However, when plotted in a three-isotope diagram, all the data fall on a single mass fractionation line. Overall limits of error of the SRM980 reported here fall within the previously reported overall limits of error. The isotopic heterogeneity not only corresponds to differences among units but has been found at the chip-size level. This result, due to the precision of the MC-ICP-MS technique, makes the SRM980 inappropriate for the international isotopic standard of magnesium. The SRM980 can still be used to report the excess of 26Mg, which is defined by the deviation from the mass-dependent relationship between 25Mg/24Mg, and 26Mg/24Mg ratios. Two large batches (around 10 g of Mg in each) of pure Mg solutions (in 0.3 M HNO3) have been prepared and characterised. These 2 solutions (DSM3 and Cambridge 1) are suitable reference material because they are immune to heterogeneity. DSM3 and Cambridge 1 are isotopically different (by 1.3‰ per u) and are available upon request from the first author. In addition, DSM3 has an isotopic composition very similar to the Mg-isotopic composition of carbonaceous chondrites (Orgueil and Allende). Because of the lack of heterogeneity and the cosmochemical and geochemical significance of DSM3, we urge the use of DSM3 as the primary isotopic reference material to report Mg-isotopic variations.

Oxygen Isotope Variations at the Margin of a CAI Records Circulation Within the Solar Nebula

Isotope measurements within an inclusion in a meteorite reveal a record of processes in the early solar system. Micrometer-scale analyses of a calcium-, aluminum-rich inclusion (CAI) and the characteristic mineral bands mantling the CAI reveal that the outer parts of this primitive object have a large range of oxygen isotope compositions. The variations are systematic; the relative abundance of 16O first decreases toward the CAI margin, approaching a planetary-like isotopic composition, then shifts to extremely 16O-rich compositions through the surrounding rim. The variability implies that CAIs probably formed from several oxygen reservoirs. The observations support early and short-lived fluctuations of the environment in which CAIs formed, either because of transport of the CAIs themselves to distinct regions of the solar nebula or because of varying gas composition near the proto-Sun.

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.