Abstract. The storage and release of water in soils is critical for sustaining plant transpiration and groundwater recharge. However, how much subsurface mixing of water occurs, and how much of the water is available for plants or otherwise percolates to streams and the groundwater is not yet understood. Based on stable isotope (2H and 18O) data, some studies have found that water infiltrating into soils can bypass older pore water. However, the mechanisms leading to the separation of water routed to the streams and water held tightly in smaller pores are still unclear. Here, we address the current limitations of the understanding of subsurface mixing and their consequences regarding the application of stable isotopes in ecohydrological studies. We present an extensive data set, for which we sampled the isotopic composition of mobile and bulk soil water in parallel with groundwater at a fortnightly temporal resolution and stream water and rainfall at a much higher resolution in a Mediterranean long-term research catchment, in Vallcebre, Spain. The data reveal that the mobile and tightly bound water of a silty loam soil in a Scots pine forest do not mix well; however, they constitute two disjunct subsurface water pools with little exchange, despite intense rainfall events leading to high soil wetness. We show that the isotopic compartmentalization results from the rewetting of small soil pores by isotopically depleted winter/spring rain. Thus, stable isotopes, and, in turn, water residence times, do not only vary across soil depth, but also across soil pores. Our findings have important implications for stable isotope applications in ecohydrological studies assessing the water uptake by plants or the process realism of hydrological models, as the observed processes are currently rarely implemented in the simulation of water partitioning into evapotranspiration and recharge in the critical zone.

Stemflow, despite being a small proportion of the gross rainfall, is an important and understudied flux of water in forested areas. Recent studies have highlighted its complexity and relative importance for the understanding of soil and groundwater recharge. Stemflow dynamics offer an insight into the rain water that is stored and released from the stems of trees to the soil. Different attempts have been made to understand the variability of stemflow under different types of vegetation, but rather few have focused on the combined influence of both biotic and abiotic factors that affect the inter and intra-storm stemflow variability, and none known in Mediterranean climates. This study presents stemflow data collected at high temporal resolution for two species with contrasting canopy and bark structures: Quercus pubescens Willd.(downy oak) and Pinus sylvestris L. (Scots pine) in the Vallcebre research catchments (NE of Spain, 42º 12'N, 1º 49'E). The main objective was to understand how the interaction of biotic and abiotic factors affected stemflow dynamics. Mean stemflow production was low for both species (~1% of incident rainfall) and increased with rainfall amount. However, the magnitude of the response depended on the combination of multiple biotic and abiotic factors. Both species produced similar stemflow volumes, but funneling ratios of some trees diverged significantly. The combined analysis of biotic and abiotic factors showed that, for events of the same rainfall amount, funneling ratios and stemflow dynamics in each species were highly controlled by the interaction of rainfall intensity and tree diameter (DBH).

The young water fraction (Fyw), the proportion of water younger than 2-3 months, was investigated in soil-, ground-and stream waters in the 0.56 Km 2 sub-humid Mediterranean Can Vila catchment. Rain water was sampled at 5-mm rainfall intervals. Mobile soil water and groundwater were sampled fortnightly, using suction lysimeters and two shallow wells, respectively. Stream water was dynamically sampled at variable time intervals (30 minutes to 1 week), depending on flow. A total of 1,529 18 O determinations obtained during 58 months were used. The usual hypothesis of rapid evapotranspiration of summer rainfall could not be maintained, leading to discard the use of an "effective precipitation" model. Soil mobile waters had Fyw up to 34%, while in ground and stream were strongly related to water table and discharge variations, respectively. In stream waters, due to the highly skewed flow duration curve, the flow-averaged young water fraction (F*yw) was 22.6%, whereas the time-averaged Fyw was 6.2%. Nevertheless, both F*yw and its exponential discharge sensitivity (S d) showed relevant changes when different 12-month sampling periods were investigated. The availability of S d and a detailed flow record allowed us to simulate the young water fraction that would be obtained with a virtual thorough sampling (F**yw). This showed that underestimation of F*yw is associated with missing the sampling of highest discharges and revealed underestimations of F*yw by 25% for the dynamic sampling and 66% for the weekly sampling. These results confirm that the young water fraction and its discharge sensitivity are metrics that depend more on precipitation forcing than on physiographic characteristics, so the comparisons between catchments should be based on mean annual values and inter-annual variability. They also support the dependence of the young water fraction on the sampling rate and show the advantages of flow-weighted F*yw. Water age investigations should be accompanied by the analysis of flow duration curves. In addition, the simulation of F**yw is proposed as a method for checking the adequacy of the sampling rate used.

Most hydrological studies based on stable water isotopes ( 18 O and D) use the isotopic composition of rainfall as input signal. Although stable water isotopes are conservative tracers, previous studies have shown that canopies modify the isotopic composition of rainfall. At present, there is a scientific agreement about the factors involved in isotopic modification, but the effect of each factor and the magnitude of the isotopic shift are still not clear. In this study, we analyse at an interevent and intraevent basis the spatio-temporal differences between the isotopic composition of rainfall, throughfall, and stemflow for two different species (Pinus sylvestris L. and Quercus pubescens Willd). The aim of the study is to analyse the isotopic modification that takes place in throughfall and stemflow and how meteorological variables and structural forest characteristics influence the observed changes. Rainfall and throughfall were sampled by a combination of bulk and sequential collectors, whereas stemflow was collected only by bulk collectors. Results showed that the isotopic modification occurred in both directions, although stemflow was consistently more enriched than throughfall. Despite the contrasting canopy structures, no significant differences between species were found. Moreover, the intraevent analysis suggested that all fractionation factors could occur during one event, but evaporation or isotopic exchange would have a higher impact at the beginning of rainfall, whereas canopy selection processes would be more important at the end of rainfall. Our results emphasize the importance of considering the isotopic composition of throughfall and stemflow in isotope-related studies in forested catchments.

This paper presents the main results obtained from the study of hydrological processes in the Vallcebre Research Catchments since 1988. Distributed hydrometric measurements, environmental tracers and hydrological modelling were used to understand Mediterranean catchment behaviour and to provide new data to help assess the global change effects on these catchments' water resources. Thirty years of hydrological processes observation in the Vallcebre Research Catchments have increased understanding not only of their hydrological response, but also of the main hydrological and erosion processes characteristic of Mediterranean mountain catchments. This paper briefly summarises the main results obtained since 1988 on ecohydrological processes, hydrological response, runoff generation processes, erosion and sediment transport. Some of the main findings from this research are (i) the importance of temporal variability in precipitation to determine the hydrological processes; (ii) the paramount role played by forest cover in reducing soil water content; (iii) the marked influence of antecedent wetness conditions on runoff generation that determine different runoff responses; (v) the dominant contribution of pre-existing water during floods; (vi) the importance of freezing-thawing processes in badland areas on erosion and the role of summer convective storms in controlling sediment transport.

Soil water-content (SWC) variability in forest ecosystems is affected by complex interactions between climate, topography, forest structure and soil factors. However, detailed studies taking into account the combined effects of these factors are scarce. This study's main aims were to examine the control that throughfall exerts on local spatial variation of near-surface soil water-content and to combine this information with forest structure and soil characteristics, in order to analyze all their effects together. Two stands located in the Vallcebre Research Catchments (NE Spain) were studied: one dominated by Quercus pubescens and the other by Pinus sylvestris. Throughfall and the related shallow SWC were monitored in each plot in 20 selected locations. The main characteristics of the nearest tree and soil parameters were also measured. The results indicated that mean SWC increment at the rainfall event scale showed a strong linear relationship with mean throughfall amount in both forest plots. The % of locations with SWC increments increased in a similar way to throughfall amount in both forest plots. The analyses considering all the effects together indicated again that throughfall had a significant positive effect in both forest plots, while soil litter depth showed a significant negative effect for the oak plot but lower statistical significance for the pine plot, showing a comparable -although more erratic- influence of the organic forest floor for this plot. These results, together with lower responses of SWC to throughfall than expected in rainfall events characterized by low preceding soil water-condition and high rainfall intensity, suggest that litter layer is playing an important role in controlling the soil water-content dynamics. The biometric characteristics of the nearest trees showed significant but very weak relationships with soil water-content increment, suggesting that stemflow and throughfall may act at lower distances from tree trunk than those presented in our study.

Nature-based solutions for water-resource challenges require advances in the science of ecohydrology. Current understanding is limited by a shortage of observations and theories that can further our capability to synthesize complex processes across scales ranging from submillimetres to tens of kilometres. Recent developments in environmental sensing, data, and modelling have the potential to drive rapid improvements in ecohydrological understanding. After briefly reviewing advances in sensor technologies, this paper highlights how improved measurements and modelling can be applied to enhance understanding of the following ecohydrological examples: interception and canopy processes, root uptake and critical zone processes, and up-scaled effects of land use on streamflow. Novel and improved sensors will enable new questions and experiments, while machine learning and empirical methods provide additional opportunities to advance science. The synergy resulting from the convergence of these parallel developments will provide new insight into ecohydrological processes and thereby help identify nature-based solutions to address water-resource challenges in the 21st century.

The isotopic composition of precipitation (D and 18O) has been widely used as an input signal in water tracer studies. Whereas much recent effort has been put into developing methodologies to improve our understanding and modelling of hydrological processes (e.g., transit‐time distributions or young water fractions), less attention has been paid to the spatio‐temporal variability of the isotopic composition of precipitation, used as input signal in these studies. Here, we investigated the uncertainty in isotope‐based hydrograph separation due to the spatio‐temporal variability of the isotopic composition of precipitation. The study was carried out in a Mediterranean headwater catchment (0.56 km2). Rainfall and throughfall samples were collected at three locations across this relatively small catchment, and stream water samples were collected at the outlet. Results showed that throughout an event, the spatial variability of the input signal had a higher impact on hydrograph separation results than its temporal variability. However, differences in isotope‐based hydrograph separation determined preevent water due to the spatio‐temporal variability were different between events and ranged between 1 and 14%. Based on catchment‐scale isoscapes, the most representative sampling location could also be identified. This study confirms that even in small headwater catchments, spatio‐temporal variability can be significant. Therefore, it is important to characterize this variability and identify the best sampling strategy to reduce the uncertainty in our understanding of catchment hydrological processes.