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The Alps are a key water resource for central Europe, providing water for drinking, agriculture, and hydropower production. Thus, understanding runoff generation processes of Alpine streams is important for sustainable water management. It is currently unclear how much streamflow is derived from old water stored in the subsurface and how much stems from more recent precipitation that reaches the stream via near-surface quick flow processes. It is also unclear how this partitioning varies across different Alpine catchments in response to hydroclimatic forcing and catchment characteristics. Here, we use stable water isotope time series in precipitation and streamflow to quantify the young water fractions (Fyw; i.e., the fraction of water younger than approximately 2–3 months) and new water fractions (Fnew; here, the fraction of water younger than 1 month) in streamflow from 32 Alpine catchments. We contrast these measures of water age between summer and winter and between wet and dry periods and then correlate them with hydroclimatic variables and physical catchment properties. New water fractions varied between 3.5 % and 9.6 %, with values of 9.2 % in rainfall-dominated catchments, 9.6 % in hybrid catchments, and 3.5 % in snow-dominated catchments (mean across all catchments of 7.1 %). Young water fractions were approximately twice as large (reflecting their longer timescale) and ranged between 10.1 % and 17.6 %, with values of 17.6 % in rainfall-dominated catchments, 16.6 % in hybrid catchments, and 10.1 % in snow-dominated catchments (mean across all catchments of 14.3 %). New water fractions were negatively correlated with catchment size (Spearman rank correlation, rS, of −0.38), q95 baseflow (rS=-0.36), catchment elevation (rS=-0.37), total catchment relief (rS=-0.59), and the fraction of slopes steeper than 40° (rS=-0.48). Large new water fractions, implying faster transmission of precipitation to streamflow, are more prevalent in small catchments, at low elevations, with small elevation differences, and with large fractions of forest cover (rS=0.36). New water fractions averaged 3.3 % following dry antecedent conditions, compared with 9.3 % after wet antecedent conditions. Our results quantify how hydroclimatic and physical drivers shape the partitioning of old and new waters across the Alps, thus indicating which landscapes transmit recent precipitation more readily to streamflow and which landscapes tend to retain water over longer periods. Our results further illustrate how new water fractions may find relationships that remained invisible with young water fractions.

Stable isotopes (δ18O) 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 δ18O, 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, δ18O 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 δ18O 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 δ18O with commonly used SW and CO models are with mean transit times (MTTs) of ∼ 1–2 years substantially lower than those obtained from 3H with the same models, reaching MTTs of ∼10 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 δ18O and 3H stream signals, but water ages inferred from δ18O with these models were, with MTTs of ∼ 11–17 years, also much higher and similar to those inferred from 3H, which suggested MTTs of ∼ 11–13 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 δ18O 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 δ18O 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 δ18O 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 δ18O 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 δ18O 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.

Groundwater recharge is a key component of the hydrological cycle, yet its direct measurement is complex and often difficult to achieve. An alternative is its inverse estimation through a combination of numerical models and transient observations from distributed soil water monitoring stations. However, an often neglected aspect of this approach is the effect of model predictive uncertainty on simulated water fluxes. In this study, we made use of long-term soil water content measurements at 14 locations from the Austrian soil water monitoring program to quantify and compare local potential groundwater recharge rates and their temporal variability. Observations were coupled with a Bayesian probabilistic framework to calibrate the HYDRUS-1D model and assess the effect of model predictive uncertainty on long-term simulated recharge fluxes. Estimated annual potential recharge rates ranged from 44 to 1319 mm a−1 with a relative uncertainty (95 % interquantile range/median) in the estimation of between 1 % and 39 %. Recharge rates decreased longitudinally, with high rates and lower seasonality at western sites and low rates with high seasonality and extended periods without recharge at the southeastern and eastern Austrian sites. Higher recharge rates and lower actual evapotranspiration were related to sandy soils; however, climatic factors had a stronger influence on estimated potential groundwater recharge than soil properties, underscoring the vulnerability of groundwater recharge to the effects of climate change.

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.

The time precipitation needs to travel through a catchment to its outlet is an important descriptor of a catchment's susceptibility to pollutant contamination, nutrient loss, and hydrological functioning. The fast component of total water flow can be estimated by the fraction of young water (Fyw), which is the percentage of streamflow younger than 3 months. Fyw is calculated by comparing the amplitudes of sine waves fitted to seasonal precipitation and streamflow tracer signals. This is usually done for the complete tracer time series available, neglecting annual differences in the amplitudes of longer time series. Considering inter-annual amplitude differences, we employed a moving time window of 1 year in weekly time steps over a 4.5-year δ18O tracer time series to calculate 189 Fyw estimates and their uncertainty. They were then tested against the following null hypotheses: (1) at least 90 % of Fyw results do not deviate more than ±0.04 (4 %) from the mean of all Fyw results, indicating long-term invariance. Larger deviations would indicate changes in the relative contribution of different flow paths; (2) for any 4-week window, Fyw does not change more than ±0.04, indicating short-term invariance. Larger deviations would indicate a high sensitivity of Fyw to a 1-week to 4-week shift in the start of a 1-year sampling campaign; (3) the Fyw results of 1-year sampling campaigns started in a given calendar month do not change more than ±0.04, indicating seasonal invariance. In our study, all three null hypotheses were rejected. Thus, the Fyw results were time-variable, showed variability in the chosen sampling time, and had no pronounced seasonality. We furthermore found evidence that the 2015 European heat wave and including two winters into a 1-year sampling campaign increased the uncertainty of Fyw. Based on an increase in Fyw uncertainty when the mean adjusted R2 was below 0.2, we recommend further investigations into the dependence of Fyw and its uncertainty to goodness-of-fit measures. Furthermore, while investigated individual meteorological factors did not sufficiently explain variations of Fyw, the runoff coefficient showed a moderate negative correlation of r=-0.50 with Fyw. The results of this study suggest that care must be taken when comparing Fyw of catchments that were based on different calculation periods and that the influence of extreme events and snow must be considered.

For more than two decades, research groups in hydrology, ecology, soil science, and biogeochemistry have performed cryogenic water extractions (CWEs) for the analysis of δ2H and δ18O of soil water. Recent studies have shown that extraction conditions (time, temperature, and vacuum) along with physicochemical soil properties may affect extracted soil water isotope composition. Here we present results from the first worldwide round robin laboratory intercomparison. We test the null hypothesis that, with identical soils, standards, extraction protocols, and isotope analyses, cryogenic extractions across all laboratories are identical. Two standard soils with different physicochemical characteristics along with deionized (DI) reference water of known isotopic composition were shipped to 16 participating laboratories. Participants oven-dried and rewetted the soils to 8 and 20 % gravimetric water content (WC), using the deionized reference water. One batch of soil samples was extracted via predefined extraction conditions (time, temperature, and vacuum) identical to all laboratories; the second batch was extracted via conditions considered routine in the respective laboratory. All extracted water samples were analyzed for δ18O and δ2H by the lead laboratory (Global Institute for Water Security, GIWS, Saskatoon, Canada) using both a laser and an isotope ratio mass spectrometer (OA-ICOS and IRMS, respectively). We rejected the null hypothesis. Our results showed large differences in retrieved isotopic signatures among participating laboratories linked to soil type and soil water content with mean differences compared to the reference water ranging from +18.1 to −108.4 ‰ for δ2H and +11.8 to −14.9 ‰ for δ18O across all laboratories. In addition, differences were observed between OA-ICOS and IRMS isotope data. These were related to spectral interferences during OA-ICOS analysis that are especially problematic for the clayey loam soils used. While the types of cryogenic extraction lab construction varied from manifold systems to single chambers, no clear trends between system construction, applied extraction conditions, and extraction results were found. Rather, observed differences in the isotope data were influenced by interactions between multiple factors (soil type and properties, soil water content, system setup, extraction efficiency, extraction system leaks, and each lab's internal accuracy). Our results question the usefulness of cryogenic extraction as a standard for water extraction since results are not comparable across laboratories. This suggests that defining any sort of standard extraction procedure applicable across laboratories is challenging. Laboratories might have to establish calibration functions for their specific extraction system for each natural soil type, individually.

Lagoons are important ecosystems occupying large coastal areas worldwide. Lagoons contain various mixtures of marine and freshwater sources which are highly dynamic in time. However, it often remains a challenge to identify and quantify dynamic changes of water sources, particularly in heterogeneous lagoon systems like the Köycegiz–Dalyan lagoon (KDL), which is located at the south-west of Turkey on the Mediterranean Sea coast. The objective of this study was to quantify different contributions of potential water sources i.e. surface water, groundwater and seawater in the lagoon and how these water sources changed over time and space. In the wet- and dry-season stable isotopes of water, chloride concentration (Cl-) and salinity were measured in two depths in the lagoon and surrounding water bodies (sea, lake, groundwater). Different components of water sources were quantified with a three component endmember mixing analysis. Differences in Cl- and stable isotopes over time indicated the dynamic behaviour of the system. Generally, none of the groundwater samples was impacted by water of the Mediterranean Sea. During the wet season, most of the lagoon water (> 95%) was influenced by freshwater and vertically well mixed. During the dry season, high Cl- in the deeper sampling locations indicated a high contribution of marine water throughout the entire lagoon system due to saltwater intrusion. However, a distinct layering in the lagoon was obvious from low Cl- and depleted isotope contents close to the surface supporting freshwater inflow into the system even during the dry season. Besides temporal dynamics also spatial heterogeneities were identified. Changes in water sources were most evident in the main lagoon channel compared to more isolate lagoon lakes, which were influenced by marine water even in the wet season, and compared to side branches indicating slower turnover times. We found that environmental tracers helped to quantify highly dynamic and heterogeneous contributions of different water sources in the Köycegiz–Dalyan lagoon.