Non-Equilibrium Uranium as an Indicator of Global Climate Variations—The World Ocean and Large Lakes

In natural water, as a rule, there is a violation of radioactive equilibrium in the chain 238U … → 234U → 230Th →. Groundwater usually has a 234U/238U ratio in the range of 0.8–3.0 (by activity). However, in some regions, the 234U/238U ratio reaches >10 and up to 50. Ultrahigh excesses of 234U can be explained by climatic variations. During a cold period, minerals accumulate 234U as a normal component of the radioactive chain, and after the melting of permafrost, it is lost from the mineral lattice faster than 238U due to its higher geochemical mobility. This hypothesis was tested using data on the isotopic composition of uranium in the chemo- and bio-genic formations of the World Ocean and large lakes, which are reservoirs that accumulate continental runoff. The World Ocean has the most significant 234U enrichments in the polar and inland seas during periods of climatic warming in the Late Pleistocene and Holocene. In the bottom sediments of Lake Baikal, the 234U/238U ratio also increases during warm periods and significantly exceeds the 234U excess of the World Ocean. Furthermore, the 234U/238U ratio in the water of Lake Baikal and its tributaries increases from north to south following a decrease in the area of the continuous permafrost and has a seasonal variation with a maximum 234U/238U ratio in summer. The behavior of 234U in large water reservoirs is consistent with the hypothesis about the decisive influence of permafrost degradation on the anomalies in 234U/238U ratios in groundwater.

Unifying the U–Pb and Th–Pb methods: joint isochron regression and common Pb correction

The actinide elements U and Th undergo radioactive decay to three isotopes of Pb, forming the basis of three coupled geochronometers. The 206Pb ∕238U and 207Pb ∕235U decay systems are routinely combined to improve accuracy. Joint consideration with the 208Pb ∕232Th decay system is less common. This paper aims to change this. Co-measured 208Pb ∕232Th is particularly useful for discordant samples containing variable amounts of non-radiogenic (“common”) Pb. The paper presents a maximum likelihood algorithm for joint isochron regression of the 206Pb ∕238Pb, 207Pb ∕235Pb and 208Pb ∕232Th chronometers. Given a set of cogenetic samples, this total-Pb/U-Th algorithm estimates the common Pb composition and concordia intercept age. U–Th–Pb data can be visualised on a conventional Wetherill or Tera–Wasserburg concordia diagram, or on a 208Pb ∕232Th vs. 206Pb ∕238U plot. Alternatively, the results of the new discordia regression algorithm can also be visualised as a 208Pbc ∕206Pb vs. 238U ∕206Pb or 208Pbc ∕207Pb vs. 235U ∕206Pb isochron, where 208Pbc represents the common 208Pb component. In its most general form, the total-Pb/U-Th algorithm accounts for the uncertainties of all isotopic ratios involved, including the 232Th ∕238U ratio, as well as the systematic uncertainties associated with the decay constants and the 238U ∕235U ratio. However, numerical stability is greatly improved when the dependency on the 232Th ∕238U-ratio uncertainty is dropped. For detrital minerals, it is generally not safe to assume a shared common Pb composition and concordia intercept age. In this case, the total-Pb/U-Th regression method must be modified by tying it to a terrestrial Pb evolution model. Thus, also detrital common Pb correction can be formulated in a maximum likelihood sense. The new method was applied to three published datasets, including low Th∕U carbonates, high Th∕U allanites and overdispersed monazites. The carbonate example illustrates how the total-Pb/U-Th method achieves a more precise common Pb correction than a conventional 207Pb-based approach does. The allanite sample shows the significant gain in both precision and accuracy that is made when the Th–Pb decay system is jointly considered with the U–Pb system. Finally, the monazite example is used to illustrate how the total-Pb/U-Th regression algorithm can be modified to include an overdispersion parameter. All the parameters in the discordia regression method (including the age and the overdispersion parameter) are strictly positive quantities that exhibit skewed error distributions near zero. This skewness can be accounted for using the profile log-likelihood method or by recasting the regression algorithm in terms of logarithmic quantities. Both approaches yield realistic asymmetric confidence intervals for the model parameters. The new algorithm is flexible enough that it can accommodate disequilibrium corrections and intersample error correlations when these are provided by the user. All the methods presented in this paper have been added to the IsoplotR software package. This will hopefully encourage geochronologists to take full advantage of the entire U–Th–Pb decay system.

A NanoSIMS 50 L Investigation into Improving the Precision and Accuracy of the 235U/238U Ratio Determination by Using the Molecular 235U16O and 238U16O Secondary Ions

A NanoSIMS 50 L was used to study the relationship between the 235U/238U atomic and 235U16O/238U16O molecular uranium isotope ratios determined from a variety of uranium compounds (UO2, UO2F2, UO3, UO2(NO3)2·6(H2O), and UF4) and silicates (NIST-610 glass and the Plesovice zircon reference materials, both containing µg/g uranium). Because there is typically a greater abundance of 235U16O+ and 238U16O+ 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 235U16O/238U16O has the potential for improved accuracy and precision when compared to the 235U/238U ratio. The UO2 and silicate reference materials showed the greatest potential for improved accuracy and precision through use of the 235U16O/238U16O ratio as compared to the 235U/238U ratio. For the UO2, 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 235U16O/238U16O ratio versus the 235U/238U ratio from the other uranium compounds clearly indicates that the 235U16O/238U16O ratio results in worse precision and accuracy. This behavior is based on the observation that the atomic (235U+ and 238U+) to molecular (235U16O+ and 238U16O+) secondary ion production rates remain internally consistent within the UO2 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 UO2F2, UO3, UO2(NO3)2·6(H2O), and UF4 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 235U16O/238U16O may be a viable approach to improving the precision and accuracy in situations where a relatively low 235U+ count rate is expected.