Sorption behavior and long-term retention of reactive solutes in the hyporheic zone of streams

This paper analyzes the transport of sorbing solutes by extending the advective storage path model developed for longitudinal transport of inert solutes in streams coupled with flow-induced uptake in the hyporheic zone. Independent observations of a conservative (H-3) and a reactive (Cr-51) tracer in both the stream water and the hyporheic zone were used to differentiate between hydraulic and sorption processes. The method of temporal moments was found to be inadequate for parameter determination, whereas fitting versus the entire tracer breakthrough curves with special emphasis on the tail indicates that the proposed model could be used to represent both conservative and reactive transport. Information on the tracer inventory of the conservative tracer in the hyporheic zone was found to be of vital importance to the evaluation of the hydraulic exchange. A model evaluation based on stream water data alone can yield predictions of a wash-out in the hyporheic zone that deviates markedly from the observed wash-out. This prohibits long-term predictions of the wash-out from the hyporheic zone as well as the evaluation of sorption properties. The sorption in the hyporheic zone was found to follow a two-step model, where the first step is instantaneous and the second kinetic. A model with a single-step sorption process could not reproduce the observed breakthrough curves. An evaluation of the relative importance of including sorption kinetics in solute stream transport models is elucidated by means of the analytical expressions for the temporal moments. The omission of the kinetics in the second sorption step in the hyporheic zone will result in relative errors in the moments of second order or higher. The error will increase with decreasing residence time in the hyporheic zone. Especially, long-term predictions of the wash-out from the hyporheic zone require consideration of the rate-limited sorption.