Characterizing multiple timescales of stream and storage zone interaction that affect solute fate and transport in streams

The fate of contaminants in streams and rivers is affected by exchange and biogeochemical transformation in slowly moving or stagnant flow zones that interact with rapid flow in the main channel. In a typical stream, there are multiple types of slowly moving flow zones in which exchange and transformation occur, such as stagnant or recirculating surface water as well as subsurface hyporheic zones. However, most investigators use transport models with just a single storage zone in their modeling studies, which assumes that the effects of multiple storage zones can be lumped together. Our study addressed the following question: Can a single-storage zone model reliably characterize the effects of physical retention and biogeochemical reactions in multiple storage zones? We extended an existing stream transport model with a single storage zone to include a second storage zone. With the extended model we generated 500 data sets representing transport of nonreactive and reactive solutes in stream systems that have two different types of storage zones with variable hydrologic conditions. The one storage zone model was tested by optimizing the lumped storage parameters to achieve a best fit for each of the generated data sets. Multiple storage processes were categorized as possessing I, additive; II, competitive; or III, dominant storage zone characteristics. The classification was based on the goodness of fit of generated data sets, the degree of similarity in mean retention time of the two storage zones, and the relative distributions of exchange flux and storage capacity between the two storage zones. For most cases (>90%) the one storage zone model described either the effect of the sum of multiple storage processes (category I) or the dominant storage process (category III). Failure of the one storage zone model occurred mainly for category II, that is, when one of the storage zones had a much longer mean retention time (t(s) ratio > 5.0) and when the dominance of storage capacity and exchange flux occurred in different storage zones. We also used the one storage zone model to estimate a "single" lumped rate constant representing the net removal of a solute by biogeochemical reactions in multiple storage zones. For most cases the lumped rate constant that was optimized by one storage zone modeling estimated the flux-weighted rate constant for multiple storage zones. Our results explain how the relative hydrologic properties of multiple storage zones (retention time, storage capacity, exchange flux, and biogeochemical reaction rate constant) affect the reliability of lumped parameters determined by a one storage zone transport model. We conclude that stream transport models with a single storage compartment will in most cases reliably characterize the dominant physical processes of solute retention and biogeochemical reactions in streams with multiple storage zones.