Stable isotopes (I18O) and tritium (3H) are frequently used as tracers in environmental sciences to estimate age distributions of water. However, it has previously been argued that seasonally variable tracers, such as I18O, generally and systematically fail to detect the tails of water age distributions and therefore substantially underestimate water ages as compared to radioactive tracers such as 3H. In this study for the Neckar River basin in central Europe and based on a >20-year record of hydrological, I18O and 3H data, we systematically scrutinized the above postulate together with the potential role of spatial aggregation effects in exacerbating the underestimation of water ages. This was done by comparing water age distributions inferred from I18O and 3H with a total of 21 different model implementations, including time-invariant, lumped-parameter sine-wave (SW) and convolution integral (CO) models as well as StorAge Selection (SAS)-function models (P-SAS) and integrated hydrological models in combination with SAS functions (IM-SAS). We found that, indeed, water ages inferred from I18O with commonly used SW and CO models are with mean transit times (MTTs) of g1/4g1-2 years substantially lower than those obtained from 3H with the same models, reaching MTTs of g1/410 years. In contrast, several implementations of P-SAS and IM-SAS models not only allowed simultaneous representations of storage variations and streamflow as well as I18O and 3H stream signals, but water ages inferred from I18O with these models were, with MTTs of g1/4g11-17 years, also much higher and similar to those inferred from 3H, which suggested MTTs of g1/4g11-13 years. Characterized by similar parameter posterior distributions, in particular for parameters that control water age, P-SAS and IM-SAS model implementations individually constrained with I18O or 3H observations exhibited only limited differences in the magnitudes of water ages in different parts of the models and in the temporal variability of transit time distributions (TTDs) in response to changing wetness conditions. This suggests that both tracers lead to comparable descriptions of how water is routed through the system. These findings provide evidence that allowed us to reject the hypothesis that I18O as a tracer generally and systematically "cannot see water older than about 4 years"and that it truncates the corresponding tails in water age distributions, leading to underestimations of water ages. Instead, our results provide evidence for a broad equivalence of I18O and 3H as age tracers for systems characterized by MTTs of at least 15-20 years. The question to which degree aggregation of spatial heterogeneity can further adversely affect estimates of water ages remains unresolved as the lumped and distributed implementations of the IM-SAS model provided inconclusive results. Overall, this study demonstrates that previously reported underestimations of water ages are most likely not a result of the use of I18O or other seasonally variable tracers per se. Rather, these underestimations can largely be attributed to choices of model approaches and complexity not considering transient hydrological conditions next to tracer aspects. Given the additional vulnerability of time-invariant, lumped SW and CO model approaches in combination with I18O to substantially underestimate water ages due to spatial aggregation and potentially other still unknown effects, we therefore advocate avoiding the use of this model type in combination with seasonally variable tracers if possible and instead adopting SAS-based models or time-variant formulations of CO models.

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Deforestation can considerably affect transpiration dynamics and magnitudes at the catchment scale and thereby alter the partitioning between drainage and evaporative water fluxes released from terrestrial hydrological systems. However, it has so far remained problematic to directly link reductions in transpiration to changes in the physical properties of the system and to quantify these changes in system properties at the catchment scale. As a consequence, it is difficult to quantify the effect of deforestation on parameters of catchment-scale hydrological models. This in turn leads to substantial uncertainties in predictions of the hydrological response after deforestation but also to a poor understanding of how deforestation affects principal descriptors of catchment-scale transport, such as travel time distributions and young water fractions. The objectives of this study in the Wüstebach experimental catchment are therefore to provide a mechanistic explanation of why changes in the partitioning of water fluxes can be observed after deforestation and how this further affects the storage and release dynamics of water. More specifically, we test the hypotheses that (1) post-deforestation changes in water storage dynamics and partitioning of water fluxes are largely a direct consequence of a reduction of the catchment-scale effective vegetation-accessible water storage capacity in the unsaturated root zone (SU, max) after deforestation and that (2) the deforestation-induced reduction of SU, max affects the shape of travel time distributions and results in shifts towards higher fractions of young water in the stream. Simultaneously modelling streamflow and stable water isotope dynamics using meaningfully adjusted model parameters both for the pre- and post-deforestation periods, respectively, a hydrological model with an integrated tracer routine based on the concept of storage-age selection functions is used to track fluxes through the system and to estimate the effects of deforestation on catchment travel time distributions and young water fractions Fyw.

It was found that deforestation led to a significant increase in streamflow accompanied by corresponding reductions of evaporative fluxes. This is reflected by an increase in the runoff ratio from CR=0.55 to 0.68 in the post-deforestation period despite similar climatic conditions. This reduction of evaporative fluxes could be linked to a reduction of the catchment-scale water storage volume in the unsaturated soil (SU, max) that is within the reach of active roots and thus accessible for vegetation transpiration from ∼258 mm in the pre-deforestation period to ∼101 mm in the post-deforestation period. The hydrological model, reflecting the changes in the parameter SU, max, indicated that in the post-deforestation period stream water was characterized by slightly yet statistically not significantly higher mean fractions of young water (Fyw∼0.13) than in the pre-deforestation period (Fyw∼0.12). In spite of these limited effects on the overall Fyw, changes were found for wet periods, during which post-deforestation fractions of young water increased to values Fyw∼0.37 for individual storms. Deforestation also caused a significantly increased sensitivity of young water fractions to discharge under wet conditions from dFyw/dQ=0.25 to 0.36.

Overall, this study provides quantitative evidence that deforestation resulted in changes in vegetation-accessible storage volumes SU, max and that these changes are not only responsible for changes in the partitioning between drainage and evaporation and thus the fundamental hydrological response characteristics of the Wüstebach catchment, but also for changes in catchment-scale tracer circulation dynamics. In particular for wet conditions, deforestation caused higher proportions of younger water to reach the stream, implying faster routing of stable isotopes and plausibly also solutes through the sub-surface.@en

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.

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Biodegradation is one of the most favored and sustainable means of removing organic pollutants from contaminated aquifers but the major steering factors are still surprisingly poorly understood. Growing evidence questions some of the established concepts for control of biodegradation. Here, we critically discuss classical concepts such as the thermodynamic redox zonation, or the use of steady state transport scenarios for assessing biodegradation rates. Furthermore, we discuss if the absence of specific degrader populations can explain poor biodegradation. We propose updated perspectives on the controls of biodegradation in contaminant plumes. These include the plume fringe concept, transport limitations, and transient conditions as currently underestimated processes affecting biodegradation.@en