Underground production of 81Kr detected in subsurface fluids

Abstract Radiokrypton dating using the long-lived natural isotope 81Kr has been developed for determining the age of ancient groundwater. 81Kr is attractive for this purpose because it is generally thought to be produced solely in the upper atmosphere. Its 229,000-year half-life, a spatially homogeneous distribution in the atmosphere, and the absence of anthropogenic sources makes it an ideal tracer to determine ages up to ∼1.3 million years. As a noble gas, it is inert and thus not subject to interfering geochemical reactions that may alter the age information. We sought to date groundwater samples collected from deep (0.6–1.9 km) rock fractures in the Kaapvaal Craton, South Africa. Previous studies using other dating methods have estimated groundwater ages at these sites in the 1–100 million year range. Surprisingly, three of the four samples collected from flowing boreholes in gold and diamond mines showed 81Kr isotopic abundances at 2–5 times the atmospheric value. This is the first time that underground production of 81Kr has been detected, indicating that 81Kr can be generated underground in measurable quantities in contrast to the long-held paradigm that such production is insignificant in natural rocks. A radionuclide production and release model is proposed in order to quantify the importance of different factors that affect the concentrations of 81Kr in the groundwater. It is not only the high effective uranium content of the rock but also a higher 81Kr fission yield than previously anticipated that are likely causing the elevated 81Kr values in this case. In less extreme environments with average crustal composition (i.e. moderate U concentration), however, we anticipate that the underground production minimally affects groundwater 81Kr dating as demonstrated.