The study of coastal groundwater has recently surfaced as an active interdisciplinary area of research, driven foremost by its importance as a poorly quantified pathway for subsurface material transport into coastal ecosystems. Key issue in coastal groundwater research include a complete geochemical characterization of the groundwater(s); quantification of the kinetics of subsurface transport, including rock-water interactions; determination of groundwater ages; tracing of groundwater discharge into coastal waters using radiochemical fingerprints; and an assessment of the potential ecological impact of such subsurface flow to a reviving water body. For such applications, the isotopic systemics of select naturally occurring radionucludes in the U/Th series has proven to be particularly useful. These radionuclides (e.g., U, Th, Ram and Rn) are ubiquitous in all groundwaters ad are represented by several isotopes with widely different half-lives and chemistries (Figure 1). As a result, varied biogeochemical processes occurring over a broad range of time scales can be studied.
In source rock, most U/Th series isotopes in secular equilibrium; that is, the rate of decay of a daughter isotope is equal to that of it radiogenic parent, and so will have equal activities (in this context, the specific activity is simply a measure of the amount of radioactivity per unit amount). In contrast, these nuclides exhibit strong fractionations within the surrounding groundwaters because of their respective physiochemical differences. Disequilibria in U/Th series radionuclides can thus be used to identify distinct water masses, quantify release rates from source rocks, assess groundwater migration rates, and assess groundwater discharge rates in coastal waters., Large isotopic variations also have the potential for providing precise fingerprints for groundwaters from specific aquifers and have been explored as a means for calculating groundwater ages and estuarine water mass transit times.
The highly fractionated nature of U/Th series nuclides in groundwater is illustrated by the range in some measured activities. highest activities are typically observed for 222Rn, reflecting the inert nature of this noble gas. Groundwater 222Rn (t1/2=3.8) activities are thus controlled only by rapid in situ decay (Table 1) and production within host rocks, without the added complications of reversible removal via absorption or precipitation. Uranium, which is soluble as U(VI) in oxidizing waters, is present in intermediate activities in groundwaters that are moderated by redox-initiated removal onto aquifer rocks. The alkaline earth Ra and, to a greater extent, the less soluble actinide Th are readily removed from groundwater by water -- rock interactions and so are strongly depleted. Both of these elements have very short-lived as well as longer-lived isotopes, and so isotopes compositions reflect processes over a range of time scales.
Many studies have evaluated and behavior of select radionuclides in groundwater and surface water systems. Recent advances in high-=precision mass spectrometry have opted new possibilities for more subtle interpretations in select long-lived U/Th series isotopes, such as U, Ra, Pa, and Th. However, these techniques have yet to be fully developed, ahns as a consequence, such data remain largely scarce and underutilized. Although many different approaches have been developed to study radionucluide behavior in groundwater, all are based on principles of radioactive production and decay and knowledge of source terms from weathering and recoil processes, as well as removal terms from the interaction with aquifer host rock surface by sorption and precipitation.
This review is structured to present first a brief description of the background, driving forces, scales, and ecological significance of submarine groundwater discharge. Following this, a description of the geochemistry and behavior of select radionuclides in groundwater will be presented, and their application to tracing submarine groundwater discharge will be discussed.