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.

Tracing and quantifying water fluxes in the hydrological cycle is crucial for understanding the current state of ecohydrological systems and their vulnerability to environmental change. Especially the interface between ecosystems and the atmosphere that is strongly mediated by plants is important to meaningfully describe ecohydrological system functioning. Many of the dynamic interactions generated by water fluxes between soil, plant and the atmosphere are not well understood, which is partly due to a lack of interdisciplinary research. This opinion paper reflects the outcome of a discussion among hydrologists, plant ecophysiologists and soil scientists on open questions and new opportunities for collaborative research on the topic “water fluxes in the soil-plant-atmosphere continuum” especially focusing on environmental and artificial tracers. We emphasize the need for a multi-scale experimental approach, where a hypothesis is tested at multiple spatial scales and under diverse environmental conditions to better describe the small-scale processes (i.e., causes) that lead to large-scale patterns of ecosystem functioning (i.e., consequences). Novel in-situ, high-frequency measurement techniques offer the opportunity to sample data at a high spatial and temporal resolution needed to understand the underlying processes. We advocate for a combination of long-term natural abundance measurements and event-based approaches. Multiple environmental and artificial tracers, such as stable isotopes, and a suite of experimental and analytical approaches should be combined to complement information gained by different methods. Virtual experiments using process-based models should be used to inform sampling campaigns and field experiments, e.g., to improve experimental designs and to simulate experimental outcomes. On the other hand, experimental data are a pre-requisite to improve our currently incomplete models. Interdisciplinary collaboration will help to overcome research gaps that overlap across different earth system science fields and help to generate a more holistic view of water fluxes between soil, plant and atmosphere in diverse ecosystems.

Water transit time is now a standard measure in catchment hydrological and ecohydrological research. The last comprehensive review of transit time modeling approaches was published 15+ years ago. But since then the field has largely expanded with new data, theory and applications. Here, we review these new developments with focus on water-age-balance approaches and data-based approaches. We discuss and compare methods including StorAge-Selection functions, well/partially mixed compartments, water age tracking through spatially distributed models, direct transit time estimates from controlled experiments, young water fractions, and ensemble hydrograph separation. We unify some of the heterogeneity in the literature that has crept in with these many new approaches, in an attempt to clarify the key differences and similarities among them. Finally, we point to open questions in transit time research, including what we still need from theory, models, field work, and community practice.

The time that water takes to travel through the terrestrial hydrological cycle and the critical zone is of great interest in Earth system sciences with broad implications for water quality and quantity. Most water age studies to date have focused on individual compartments (or subdisciplines) of the hydrological cycle such as the unsaturated or saturated zone, vegetation, atmosphere, or rivers. However, recent studies have shown that processes at the interfaces between the hydrological compartments (e.g., soil-atmosphere or soil-groundwater) govern the age distribution of the water fluxes between these compartments and thus can greatly affect water travel times. The broad variation from complete to nearly absent mixing of water at these interfaces affects the water ages in the compartments. This is especially the case for the highly heterogeneous critical zone between the top of the vegetation and the bottom of the groundwater storage. Here, we review a wide variety of studies about water ages in the critical zone and provide (1) an overview of new prospects and challenges in the use of hydrological tracers to study water ages, (2) a discussion of the limiting assumptions linked to our lack of process understanding and methodological transfer of water age estimations to individual disciplines or compartments, and (3) a vision for how to improve future interdisciplinary efforts to better understand the feedbacks between the atmosphere, vegetation, soil, groundwater, and surface water that control water ages in the critical zone.