Exploring tracer information in a small stream to improve parameter identifiability and enhance the process interpretation in transient storage models

Abstract. The transport of solutes in river networks is controlled by the interplay of processes such as in-stream solute transport and the exchange of water
between the stream channel and dead zones, in-stream sediments, and adjacent groundwater bodies. Transient storage models (TSMs) are a powerful tool for testing hypotheses related to solute transport in streams. However, model parameters often do not show a univocal increase in model performances in a certain parameter range (i.e. they are non-identifiable), leading to an unclear understanding of the processes controlling solute transport in streams. In this study, we increased parameter identifiability in a set of tracer breakthrough experiments by combining global identifiability analysis and dynamic identifiability analysis in an iterative approach. We compared our results to inverse modelling approaches (OTIS-P) and the commonly used random sampling approach for TSMs (OTIS-MCAT). Compared to OTIS-P, our results informed about the identifiability of model parameters in the entire feasible parameter range. Our approach clearly improved parameter identifiability compared to the standard OTIS-MCAT application, due to the progressive reduction of the investigated parameter range with model iteration. Non-identifiable results led to solute retention times in the storage zone and the exchange flow with the storage zone with differences of up to 4 and 2 orders of magnitude compared to results with identifiable model parameters respectively. The clear differences in the transport metrics between results obtained from our proposed approach and results from the classic random sampling approach also resulted in contrasting interpretations of the hydrologic processes controlling solute transport in a headwater stream in western Luxembourg. Thus, our outcomes point to the risks of interpreting TSM results when even one of the model parameters is non-identifiable. Our results showed that coupling global identifiability analysis with dynamic identifiability analysis in an iterative approach clearly increased parameter identifiability in random sampling approaches for TSMs. Compared to the commonly used random sampling approach and inverse modelling results, our analysis was effective at obtaining higher accuracy of the evaluated solute transport metrics, which is advancing our understanding of hydrological processes that control in-stream solute transport.
