Conceptual modelling to assess how the interplay of hydrological connectivity, catchment storage and tracer dynamics controls nonstationary water age estimates

Although catchment storage is an intrinsic control on the rainfall-runoff response of streams, direct measurement remains a major challenge. Coupled models that integrate long-term hydrometric and isotope tracer data are useful tools that can provide insights into the dynamics of catchment storage and the volumes of water involved. In this study, we use a tracer-aided hydrological model to characterize catchment storage as a dynamic control on system function related to streamflow generation, which also allows direct estimation of the nonstationarity of water ages. We show that in a wet Scottish upland catchment dominated by runoff generation from riparian peats (histosols) with high water storage, nonstationarity in water age distributions is only clearly detectable during more extreme wet and dry periods. This is explained by the frequency and longevity of hydrological connectivity and the associated relative importance of flow paths contributing younger or older waters to the stream. Generally, these saturated riparian soils represent large mixing zones that buffer the time variance of water age and integrate catchment-scale partial mixing processes. Although storage simulations depend on model performance, which is influenced by input variability and the degree of isotopic damping in the stream, a longer-term storage analysis of this model indicates a system that is only sensitive to more extreme hydroclimatic variability.