Abstract: The long-lived radio-krypton isotope 81Kr (t1/2 = 2.29 × 105 yr) is an ideal tracer for old groundwater age dating in the range of 105–106 years which goes beyond the reach of radio-carbon (14C) age dating. Analytical breakthrough made over the last two decades in Atom Trap Trace Analysis (ATTA) has enabled the use of this isotope with extremely low abundance (81Kr/Kr = 6 × 10−13) to be used as a practical dating tool for very old groundwater. The International Atomic Energy Agency aims to provide this new isotope tool for better groundwater resource management of Member States and developed a field sampling device to collect dissolved gas samples from groundwater and a system to separate and purify trace amounts of krypton from the gas samples for the ATTA analysis. The design, setup and performances of our sampling and purification systems are described here. Our system can produce a high purity aliquot of about 5 μL of krypton from 5 L of air sample (recovery yield of >90%). The samples made by our system were confirmed to be acceptable for the ATTA analysis.

Abstract: A complete hydrogeological understanding of the deep Upper Jurassic carbonate aquifer in the South German Molasse Basin is essential for the future development of this important drinking water resource and geothermally used system. Water chemistry data, δ13CDIC, 14C of the dissolved inorganic carbon (14CDIC) and stable water isotope (δ18O and δD) measurements have been used to evaluate a promising groundwater dating approach with 14C of dissolved organic carbon (14CDOC). The pre-concentration of dissolved organic matter (DOM) was performed by the easy applicable solid phase extraction (SPE) with a styrene-divinylbenzene copolymer sorbent (PPL). Based on the sampling campaign of seven groundwater wells conducted between 2017 and 2019, it was shown that the groundwater is mainly of Ca–HCO3 type with some evidence of ion exchange between Ca2+ and Na+ at two of the investigated wells. The δD values ranged from −89.4‰ to −70.9‰ while δ18O values varied between −12.5‰ and −9.8‰. The obtained stable water isotope signatures indicated that the groundwater is of meteoric origin and was recharged during warm climate (Holocene), intermediate climate and cold climate (Pleistocene) infiltration conditions. The measured 14CDOC activities varied from 5.7 pmC to 51.1 pmC and the calculated piston-flow water ages (ORAs) ranged from 4200 years to 25,248 years using an initial 14C0DOC of 85 pmC. The calculated ORAs showed a very good correlation to the infiltration temperature-sensitive δ18O values which were affirmed with noble gas infiltration temperatures for two wells after Weise et al. (1991) and were also in good accordance with the atmospheric temperature record of the northern hemisphere from Dokken et al. (2015). The results reflect a consistent hydrogeological picture of the carbonate aquifer, which also supports the applicability of the SPE-PPL method for 14CDOC dating in groundwater with a low DOC content (<1 mg/l). In contrast, 14CDIC activities of 1.4 pmC to 21.3 pmC led to geochemically corrected piston-flow ages between 8057 years and >30,000 years and generally to an overestimation of the apparent water ages. This study gives insights into the promising approach of 14CDOC groundwater dating in carbonate aquifers with low DOC contents and allows future sustainable groundwater resource management of the investigated aquifer system.

Abstract: Travel time distributions (TTDs) provide an effective way to describe the transport and mixing processes of water parcels in a subsurface hydrological system. A major challenge in characterizing catchment TTD is quantifying the travel times in deep groundwater and its contribution to the streamflow TTD. Here, we develop and test a novel modeling framework for an integrated assessment of catchment scale TTDs through explicit representation of 3D-groundwater dynamics. The proposed framework is based on the linkage between a flux tracking scheme with the surface hydrologic model (mHM) for the soil-water compartment and a particle tracking scheme with the 3D-groundwater model OpenGeoSys (OGS) for the groundwater compartment. This linkage provides us with the ability to simulate the spatial and temporal dynamics of TTDs in these different hydrological compartments from grid scale to regional scale. We apply this framework in the Nägelstedt catchment in central Germany. Simulation results reveal that both shape and scale of grid-scale groundwater TTDs are spatially heterogeneous, which are strongly dependent on the topography and aquifer structure. The component-wise analysis of catchment TTD shows a time-dependent sensitivity of transport processes in soil zone and groundwater to driving meteorological forcing. Catchment TTD exhibits a power-law shape and fractal behavior. The predictive uncertainty in catchment mean travel time is dominated by the uncertainty in the deep groundwater rather than that in the soil zone. Catchment mean travel time is severely biased by a marginal error in groundwater characterization. Accordingly, we recommend to use multiple summary statistics to minimize the predictive uncertainty introduced by the tailing behavior of catchment TTD.