Precipitation fate and transport in a Mediterranean catchment through models calibrated on plant and stream water isotope data

To predict hydrologic responses to inputs and perturbations, it is important to understand how precipitation is stored in catchments, released back to the atmosphere via evapotranspiration (ET), or transported to aquifers and streams. We investigated this partitioning of precipitation using stable isotopes of water (O-18) at the Can Vila catchment in the Spanish Pyrenees mountains. The isotope data covered four years of measurements, comprising > 550 rainfall and > 980 stream water samples, capturing intra-event variations. They were complemented by fortnightly plant water isotope data sampled over eight months. The isotope data were used to quantify how long it takes for water to become evapotranspiration or to be discharged as streamflow using StorAge Selection (SAS) functions. We calibrated the SAS functions using a conventional approach fitting the model solely to stream water isotope data and a multi-objective calibration approach in which the model was simultaneously fitted to tree xylem water isotope data. Our results showed that the conventional model-fitting approach was not able to constrain the model parameters that represented the age of water supplying ET. Consequently, the ET isotope ratios simulated by the conventionally calibrated model failed to adequately simulate the observed xylem isotope ratios. However, the SAS model was capable of adequately simulating both observed stream water and xylem water isotope ratios, if those xylem water isotope observations were used in calibration (i.e., the multi-objective approach). The multi-objective calibration approach led to a more constrained parameter space facilitating parameter value identification. The model was tested on a segment of data reserved for validation showing a Kling-Gupta Efficiency of 0.72 compared to the 0.83 observed during in the calibration period. The water-age dynamics inferred from the model calibrated using the conventional approach differed substantially from those inferred from the multi-objective calibration model. The latter suggested that the median ages of water supplying evapotranspiration is much older (150-300 d) than what was suggested by the former (50-200 d). Regardless, the modeling results support recent findings in ecohydrological field studies that highlighted both subsurface heterogeneity of water storage and fluxes and the use of relatively old water by trees. We contextualized the SAS-derived water ages by also using young-water-fraction and endmember-splitting approaches, which respectively also showed the contribution of young water to streamflow was variable but sensitive to runoff rates and that ET was largely sourced by winter precipitation that must have resided in the subsurface across seasons.