Challenges in correlating oxygen stable isotope ratios of hydrates on uranium ore concentrates to process waters

Abstract

Exchange of oxygen stable isotopes (δ18O values) between precipitation waters and uranium oxides is governed by thermodynamics or kinetics. It has been assumed that meteoric waters can be related to precipitation waters in uranium ore concentrates and their calcined and reduced uranium oxide products. With this assumption, the δ18O values of uranium materials could provide forensic signatures that identify the production history and geolocation of nuclear materials. To further exploit the potential of δ18O values in nuclear material analysis, this study examines the oxygen stable isotope exchange in two UOCs, magnesium diuranate (MDU) and sodium diuranate (SDU). MDU and SDU were synthesized from solutions of uranyl nitrate hexahydrate using precipitation waters with unique oxygen isotope compositions. The structures of the MDU and SDU were analyzed using powder X-ray diffraction (p-XRD) and thermal mass loss curves, while the δ18O values of waters generated during thermal decomposition were analyzed using a thermogravimetric analyzer coupled to an isotope ratio infrared spectrometer (TGA-IRIS). By p-XRD, the MDU was uniform and amorphous across all syntheses with residual crystalline material incorporated as a minor component. Combined with the TGA results, all of the MDU is likely amorphous MgU2O7·3H2O with MgO impurities present throughout. In contrast, the SDU synthesis resulted in multiple phases with many samples exhibiting crystalline phases including a combination of Na(UO2)4O2(OH)5·5H2O and Na2(UO2)6O4(OH)6·8H2O with a Na2U2O7 minor phase. A small fraction of the SDU samples were amorphous with no crystalline XRD peaks observed. Mass loss curves of the SDU samples revealed that the amorphous samples contained inclusions of similar crystalline phases compared to the crystalline materials. The uniformity of the MDU samples enabled highly reproducible measurements of δ18O values of the water vapor yielded from two dehydration events at 170 °C and 500 °C. In contrast, the multiphase composition of the SDU samples resulted in poor reproducibility in δ18O values. Neither system revealed any correlation between the δ18O values of precipitation water and the waters released during dehydration of the UOCs.

Oxygen Isotope and Fluorine Impurity Signatures during the Conversion of Uranium Ore Concentrates to Nuclear Fuel

“…A 2001 study by Pajo et al found that δ 18 O values of collected UO 2 pellets matched closely that of the local meteoric waters (rain and snow) where the pellets originated. 14 More recently, Klosterman et al examined the fractionation between uranyl peroxide and ADU with the water, from which these compounds were precipitated, along with the changes in δ 18 O values after calcination in dry air and an inert nitrogen atmosphere. 12 preferentially exchanged oxygen with water vapor at 400 °C.…”

“…15 More recently, Assulin et al studied oxygen isotope exchange between U 3 O 8 and atmospheric O 2 at a range of temperatures and found that oxygen exchange between U 3 O 8 and O 2 was minimal below 100 °C, partial exchange occurred between 100 and 200 °C, and isotopic equilibrium was reached above 400 °C. 16 They also found that preferential incorporation of 16 O by U 3 O 8 led to U 3 O 8 attaining δ 18 O values lower than O 2 . Expanding this work, they calcined three U 3 O 8 samples of differing δ 18 O values to UO 2 between 500 and 700 °C for 2, 4, and 6 h. 17 From these experiments, they found that the final δ 18 O values of the UO 2 were dictated by the isotopic equilibrium between the water generated during the reduction and the resultant UO 2 .…”

“…16 They also found that preferential incorporation of 16 O by U 3 O 8 led to U 3 O 8 attaining δ 18 O values lower than O 2 . Expanding this work, they calcined three U 3 O 8 samples of differing δ 18 O values to UO 2 between 500 and 700 °C for 2, 4, and 6 h. 17 From these experiments, they found that the final δ 18 O values of the UO 2 were dictated by the isotopic equilibrium between the water generated during the reduction and the resultant UO 2 . 17 They also found that the UO 2 products were slightly more depleted in 18 O content than the starting U 3 O 8 materials, while the water vapor formed was around 11‰ more enriched.…”

“…Expanding this work, they calcined three U 3 O 8 samples of differing δ 18 O values to UO 2 between 500 and 700 °C for 2, 4, and 6 h. 17 From these experiments, they found that the final δ 18 O values of the UO 2 were dictated by the isotopic equilibrium between the water generated during the reduction and the resultant UO 2 . 17 They also found that the UO 2 products were slightly more depleted in 18 O content than the starting U 3 O 8 materials, while the water vapor formed was around 11‰ more enriched. 17 Collectively, these experiments provide valuable information about the oxygen isotope fractionation of UOCs during calcination in inert or atmospheric conditions at elevated temperatures.…”

“…O/ 16 O stable isotope ratios (or δ 18 O values, equivalent to [R measured /R VSMOW − 1] where R = 18 O/ 16 O, and VSMOW stands for Vienna Standard Mean Ocean Water, where δ 18 O VSMOW = 0‰) of U-oxide materials has garnered attention due to the possibility of these ratios providing information about their process history and provenance. A 2001 study by Pajo et al found that δ 18 O values of collected UO 2 pellets matched closely that of the local meteoric waters (rain and snow) where the pellets originated. 14 More recently, Klosterman et al examined the fractionation between uranyl peroxide and ADU with the water, from which these compounds were precipitated, along with the changes in δ 18 O values after calcination in dry air and an inert nitrogen atmosphere.…”