Groundwater has long been an active area of research driven by its importance both as a societal resource and as a component in the global hydrological cycle. Key issues in groundwater research include inferring rates of transport of chemical constituents, determining the ages of groundwater, and tracing water masses using chemical fingerprints. While information on the trace elements pertinent to these topics can be obtained from aquifer tests using experimentally introduced tracers, and from laboratory experiments on aquifer materials, these studies are necessarily limited in time and space. Regional studies of aquifers can focus on greater scales and time periods, but must contend with greater complexities and variations. In this regard, the isotopic systematics of the naturally occurring radionuclides in the U- and Th- decay series have been invaluable in investigating aquifer behavior of U, Th, and Ra. These nuclides are present in all groundwaters and are each represented by several isotopes with very different half-lives, so that processes occurring over a range of time-scales can be studied (Table 1⇓). Within the host aquifer minerals, the radionuclides in each decay series are generally expected to be in secular equilibrium and so have equal activities (see Bourdon et al. 2003). In contrast, these nuclides exhibit strong relative fractionations within the surrounding groundwaters that reflect contrasting behavior during release into the water and during interaction with the surrounding host aquifer rocks. Radionuclide data can be used, within the framework of models of the processes involved, to obtain quantitative assessments of radionuclide release from aquifer rocks and groundwater migration rates. The isotopic variations that are generated also have the potential for providing fingerprints for groundwaters from specific aquifer environments, and have even been explored as a means for calculating groundwater ages.