The benthic biolayer is a reaction hotspot that contributes disproportionately to whole-stream reactions, including aerobic respiration and contaminant transformation. Quantifying the relative contribution of the biolayer to whole-stream mass transformation remains challenging because it requires that hyporheic zone solute transport and reaction heterogeneity are explicitly captured within a single upscaled modeling framework. Here, we use field experiments and modeling to quantify mass transformation in the biolayer relative to other stream compartments. We co-injected and monitored several fluorescent tracers, including the reactive tracer resazurin, into a controlled experimental stream whose 8.5 cm hyporheic zone is isolated from groundwater. We characterized reactive transport in the water column and at multiple hyporheic zone depths by simultaneously fitting concentration time series measured at these locations to a new mobile-immobile model, using resazurin-to-resorufin transformation as an indicator of aerobic bioreactivity. Results show that the biolayer transformed 2× more resazurin to resorufin than all other stream compartments combined, and over half of all reactions occurred within 2 advective travel times through the reach. This hotspot and hot moment behavior is attributed to the biolayer’s propensity to rapidly acquire, transiently retain, and rapidly degrade stream-borne solutes. Model analysis shows that mass transformation is highest in the biolayer across a wide range of biolayer structural properties, including scenarios when the biolayer is less reactive than deeper regions of the hyporheic zone. Together, our results point to the biolayer as a common feature of streams and rivers that should be considered in network-scale models of river corridor biogeochemistry.

Hyporheic zone reaction rates are highest just below the sediment-water interface, in a shallow region called the benthic biolayer. Vertical variability of hyporheic reaction rates leads to unexpected reaction kinetics for stream-borne solutes, compared to classical model predictions. We show that deeper, low-reactivity locations within the hyporheic zone retain solutes for extended periods, which delays reactions and causes solutes to persist at higher concentrations in the stream reach than would be predicted by classical approaches. These behaviors are captured by an upscaled model that reveals the fundamental physical and chemical processes in the hyporheic zone. We show how time scales of transport and reaction within the biolayer control solute retention and transformation at the stream scale, and we demonstrate that accurate assessment of stream-scale reactivity requires methods that integrate over all travel times.

By filtering the incoming climate signal when producing streamflow, river basins can attenuate – or amplify – projected increases in rainfall variability. A common perception is that river systems dampen rainfall variability by averaging spatial and temporal variations in their watersheds. However, by analyzing 671 watersheds throughout the United States, we find that many catchments actually amplify the coefficient of variation of rainfall, and that these catchments also likely amplify changes in rainfall variability. Based on catchment-scale water balance principles, we relate that faculty to the interplay between two fundamental hydrological processes: water uptake by vegetation and the storage and subsequent release of water as discharge. By increasing plant water uptake, warmer temperatures might exacerbate the amplifying effect of catchments. More variable precipitations associated with a warmer climate are therefore expected to lead to even more variable river flows – a significant potential challenge for river transportation, ecosystem sustainability and water supply reliability.