Safeguarding water resources for society and ecosystems requires a comprehensive understanding of hydrological fluxes within the Critical Zone, Earth's living skin where the atmosphere, hydrosphere, biosphere, and lithosphere meet. For decades, tracer-aided mixing models have been used to track water flow paths through the Critical Zone, mapping the journey of water particles from atmospheric moisture to groundwater. Recent advances in novel tracer measurements and modeling methodologies offer new insights into hydrological partitioning within the Critical Zone, enabling improved quantification of water fluxes across scales ranging from microscopic to macroscopic. Advanced tracer-aided modeling approaches enable more rigorous testing of assumptions and improved quantification of uncertainties. In this review, we (a) summarize state-of-the-art tracer and modeling techniques, with an emphasis on stable water isotope tracers, (b) synthesize insights emerging from new approaches, and (c) highlight opportunities to apply these methods in interdisciplinary Critical Zone research.

The event runoff coefficient (i.e. the ratio between event runoff and precipitation that originated the runoff) is a key factor for understanding basin response to precipitation events. Runoff coefficient depends on precipitation intensity and duration but also on specific basin geohydrology attributes (including soil type, geology, land cover, topography) and last but not least, antecedent (or pre-storm) conditions (i.e., the amount of water stored in the different hydrological compartments, like the river, groundwater, soil and snowpack). The relation between runoff coefficient and basin pre-storm conditions is critical for flood forecasting, yet, the understanding of where, when and how much basin pre-storm conditions control runoff coefficients is still an open question. Here, we tested the control of basin pre-storm conditions on runoff coefficient for 60620 flood events across 284 basins in Europe. To do so, we derived basin pre-storm conditions from different proxies, namely: antecedent precipitation; surface and root zone soil moisture from hydrological models, reanalyses and land surface models also ingesting satellite observations; pre-storm river discharge, and pre-storm total water storage anomalies. We evaluated the coupling strength between runoff coefficient and pre-storm conditions proxies in relation to five classes of European basins, defined based on land use and soil type (as indexed by the Soil Conservation Service curve number CN), topography, hydrology and long-term climate and tested their ability to explain stormflow volume variability. We found that precipitation explains relatively well the stormflow volumes for both small and large events but not very well the peak discharge, especially for large floods. The runoff coefficient of events shows different distributions for the five different classes and correlates well with deep soil storages (such as root-zone soil moisture and pre-storm total water storage anomalies), pre-storm river discharge, and pre-storm snow water equivalent. Overall, these correlations depend on the class. Poor correlations are found against antecedent precipitation index despite its wide use in the hydrological community. Seasonal and interannual climate variability exert a key role on the coupling strength between runoff coefficient and pre-storm conditions by inducing sharp changes in the correlation with season and climate. These results increase our understanding of the coupling between pre-storm conditions and runoff coefficients. This will aid flood forecasting, hydrological and land surface model calibration, and data assimilation. Furthermore, these findings can help us to better interpret future flood projections in Europe based on expected changes in long and short-term climatic drivers.