Sampling and Characterizing Rare Earth Elements in Groundwater in Deep-Lying Fractures in Granitoids Under In Situ High-Pressure and Low-Redox Conditions

Several countries are preparing to dispose of radioactive nuclear waste deep underground in crystalline rock. This type of bedrock is commonly extensively fractured and consequently carries groundwater that serves as a medium for transporting metals and radionuclides. A group of metals of particular interest in this context is the rare earth elements (REEs), because they are analogues of actinides contained within radioactive waste and are tracers of hydrological pathways and geochemical processes. Concentrations of REEs are commonly low in these groundwaters, leading to values below detection limits of standard monitoring methods, particularly for the heavy REEs. We present a new technical set-up for monitoring REEs (and other trace metals) in groundwater in fractured crystalline rock. The technique consists of passing the fracture groundwater, commonly under high pressure and containing reduced chemical species, through a device that maintains the physicochemical character of the groundwater. Within the device, diffusive gradient in thin-film (DGT) discs are installed in triplicate. With this set-up, we studied REEs in groundwater in fractures at depths of approximately ?144, ?280, and ?450 m in granitoids in the Äspö Hard Rock Laboratory in southern Sweden. The entire REE suite was detected (concentrations down to 0.1 ng L^?1) and was differently fractionated among the groundwaters. The shallowest groundwater, composed of dilute modern Baltic Sea water, was enriched in the heavy REEs, whereas the deeper groundwaters, dominated by old saline water, were depleted in the heavy REEs. Deployment periods varying from 1 to 4 weeks delivered similar REE concentrations, indicating stability and reproducibility of the experimental set-up. The study finds that 1 week of deployment may be enough. However, if the overall setting and construction allow for longer deployment times, 2–3 weeks will be optimal in terms of reaching reliable REE concentrations well above the detection limit while maintaining the performance of the DGT samplers.