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[1] End member mixing analysis (EMMA) is a commonly applied method to identify and quantify the dominant runoff producing sources of water. It employs tracers to determine the dimensionality of the hydrologic system. Many EMMA studies have been conducted using two to six tracers, with some of the main tracers being Ca, Na, Cl À , water isotopes, and alkalinity. Few studies use larger tracer sets including minor trace elements such as Li, Rb, Sr, and Ba. None of the studies has addressed the question of the tracer set size and composition, despite the fact that these determine which and how many end members (EM) will be identified. We examine how tracer set size and composition affects the conceptual model that results from an EMMA. We developed an automatic procedure that conducts EMMA while iteratively changing tracer set size and composition. We used a set of 14 tracers and 9 EMs. The validity of the resulting conceptual models was investigated under the aspects of dimensionality, EM combinations, and contributions to stream water. From the 16,369 possibilities, 23 delivered plausible results. The resulting conceptual models are highly sensitive to the tracer set size and composition. The moderate reproducibility of EM contributions indicates a still missing EM. It also emphasizes that the major elements are not always the most useful tracers and that larger tracer sets have an enhanced capacity to avoid false conclusions about catchment functioning. The presented approach produces results that may not be apparent from the traditional approach and it is a first step to add the idea of statistical significance to the EMMA approach.

Abstract. Weekly samples from surface waters, springs, soil water and rainfall were collected in a 76.9 km2 mountain rain forest catchment and its tributaries in southern Ecuador. Time series of the stable water isotopes δ18O and δ2H were used to calculate mean transit times (MTTs) and the transit time distribution functions (TTDs) solving the convolution method for seven lumped-parameter models. For each model setup, the generalized likelihood uncertainty estimation (GLUE) methodology was applied to find the best predictions, behavioral solutions and parameter identifiability. For the study basin, TTDs based on model types such as the linear–piston flow for soil waters and the exponential–piston flow for surface waters and springs performed better than more versatile equations such as the gamma and the two parallel linear reservoirs. Notwithstanding both approaches yielded a better goodness of fit for most sites, but with considerable larger uncertainty shown by GLUE. Among the tested models, corresponding results were obtained for soil waters with short MTTs (ranging from 2 to 9 weeks). For waters with longer MTTs differences were found, suggesting that for those cases the MTT should be based at least on an intercomparison of several models. Under dominant baseflow conditions long MTTs for stream water ≥ 2 yr were detected, a phenomenon also observed for shallow springs. Short MTTs for water in the top soil layer indicate a rapid exchange of surface waters with deeper soil horizons. Differences in travel times between soils suggest that there is evidence of a land use effect on flow generation.

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