A NanoSIMS 50 L was used to study the relationship between the
235U/
238U atomic and
235U
16O/
238U
16O molecular uranium isotope ratios determined from a variety of uranium compounds (UO
2, UO
2F
2, UO
3, UO
2(NO
3)
2·6(H
2O), and UF
4) and silicates (NIST-610 glass and the Plesovice zircon reference materials, both containing µg/g uranium). Because there is typically a greater abundance of
235U
16O
+ and
238U
16O
+ molecular secondary ions than
235U
+ and
238U
+ atomic ions when uranium-bearing materials are sputtered with an oxygen primary ion beam, the goal was to understand whether use of
235U
16O/
238U
16O has the potential for improved accuracy and precision when compared to the
235U/
238U ratio. The UO
2 and silicate reference materials showed the greatest potential for improved accuracy and precision through use of the
235U
16O/
238U
16O ratio as compared to the
235U/
238U ratio. For the UO
2, which was investigated at a variety of primary beam currents, and the silicate reference materials, which were only investigated using a single primary beam current, this improvement was especially pronounced at low
235U
+ count rates. In contrast, comparison of the
235U
16O/
238U
16O ratio versus the
235U/
238U ratio from the other uranium compounds clearly indicates that the
235U
16O/
238U
16O ratio results in worse precision and accuracy. This behavior is based on the observation that the atomic (
235U
+ and
238U
+) to molecular (
235U
16O
+ and
238U
16O
+) secondary ion production rates remain internally consistent within the UO
2 and silicate reference materials, whereas it is highly variable in the other uranium compounds. Efforts to understand the origin of this behavior suggest that irregular sample surface topography, and/or molecular interferences arising from the manner in which the UO
2F
2, UO
3, UO
2(NO
3)
2·6(H
2O), and UF
4 were prepared, may be a major contributing factor to the inconsistent relationship between the observed atomic and molecular secondary ion yields. Overall, the results suggest that for certain bulk compositions, use of the
235U
16O/
238U
16O may be a viable approach to improving the precision and accuracy in situations where a relatively low
235U
+ count rate is expected.
Full article