Submarine groundwater discharge (SGD) into the ocean is of general interest because it acts as vehicle for the transport of dissolved contaminants and/or nutrients into the coastal sea and because it may be accompanied by the loss of significant volumes of freshwater. Due to the large-scale and long-term nature of the related hydrological processes, environmental tracers are required for SGD investigation. The water parameters of electrical conductivity and temperature, the naturally occurring radionuclides of radon and radium as well as the stable water isotopes ¹⁸O and ²H have proven in previous studies their general suitability for the detection and quantification of SGD. However, individual hydrogeological settings require a site-specific application of this “tool box”. This study evaluates and compares the applicability of the abovementioned tracers for investigating SGD from a distinct submarine source in a karst environment at Cabbé, southern France. The specific advantages and disadvantages of each individual parameter under the given hydrogeological conditions are discussed. Radon appeared to be the most suitable environmental tracer in the site specific context. The water temperature was less reliable due to the little temperature difference between seawater and groundwater and since the diurnal variation of the air temperature masks potential SGD signals. Radium isotopes are less applicable in the studied region due to the lack of a well-developed subterranean estuary. The stable water isotopes showed results consistent with the salinity and radon data; however, the significantly higher effort required for stable isotope analyses is disadvantageous. A multi-temporal thermal remote sensing approach proved to be a powerful tool for initial SGD surveying.

Tritium is one of the most important environmental tracers in isotope hydrology for understanding the dynamics of groundwater and connected surface water and has been used in a wide range of applications at different scales. A key requirement for using tritium as a tracer is the knowledge of its spatial and temporal distribution in different water types. As a fundamental input, quantity long‐term time series of tritium in precipitation are of particular importance. In this paper, the authors present an overview of tritium data sets of the Federal Institute of Hydrology (BfG), the Helmholtz Zentrum München (HMGU) and the German Weather Service (DWD). Since the 1970s, all three institutions have monitored the tritium concentration at 53 surface water and 37 precipitation stations on a monthly basis. The primary purpose of the data set was to provide baseline information for different water types all over Germany as an integral part of the German radiation protection monitoring system. Additionally, as geochemically inert tracer, tritium provides a unique tool to different user groups in a wide range of research questions and applications.

The potentially detrimental impact of groundwater discharge into rivers on the ecosystem services provided by the river makes the localization of groundwater discharge areas as well as the quantification of the associated mass fluxes an issue of major interest. However, localizing groundwater discharge zones and evaluating their impact are challenging tasks because of (i) the limited number of suitable tracers and (ii) the high spatio-temporal variability of groundwater/river water interaction in general. In this study, we applied the ubiquitous naturally occurring radioactive noble gas radon (²²²Rn) as an aqueous tracer to localize and quantify groundwater discharge along a 60 km reach of the upper German part of the major river Elbe under drought conditions. All radon data processing was executed with the numerical implicit finite element model FINIFLUX, a radon mass balance-based approach, which has been developed specifically to quantify the groundwater flux into rivers. The model results were compared to the tritium (³H) distribution pattern in the studied river reach. The results of the study proved the applicability of both (i) the methodical approach (i.e., radon as tracer) and (ii) the application of FINIFLUX to drought conditions (with river discharge rates as low as 82 m³/s vs. a long time mean of 300 m³/s). Applying the model, the recorded dataset allowed differentiating between groundwater baseflow, on the one hand, and interflow and surface water runoff distributions to the river, on the other. Furthermore, the model results allowed assessing the location and the intensity of groundwater discharge into the river under low flow conditions. It was also shown that analysing discrete river water samples taken from distinct points in a major stream might lead to slightly incorrect results because of an incomplete mixing of river water and locally discharging groundwater. An integrating sampling approach (as applied for radon) is preferable here.

In Germany, river monitoring for tritium started in the early 1970s. Today this monitoring network consists of 50 stations and includes stable isotopes. The stable isotope time series to the end of 2021 are at least four years and for some stations up to 30 years long. Daily river water samples were collected during an extraordinary dry season from October 2018 until end of January 2019 from six selected stations of the Rhine and five stations of the Elbe basin. The most dominating stable isotope effects in river water are the seasonal and altitude effects, but also a continental effect is visible. The isotopes indicate snow and ice melt contributions in the Rhine and Danube during the summer months and a consecutive dilution of these signals by mixing with tributary rivers. Close to the coasts in northern Germany, stable isotope patterns reflect influence of seawater and tides. Daily patterns during the dry season 2018/2019 surprisingly do not exhibit extreme changes but rather trends of enhanced groundwater contribution. Long-term continual data across scales are important for comparing and identifying hydrological processes in German river basins of different size and mean catchment altitudes, and highlight the benefits of a co-organized national network.