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Hyporheic zones increase freshwater ecosystem resilience to hydrological extremes and global environmental change. However, current conceptualizations of hyporheic exchange, residence time distributions, and the associated biogeochemical cycling in streambed sediments do not always accurately explain the hydrological and biogeochemical complexity observed in streams and rivers. Specifically, existing conceptual models insufficiently represent the coupled transport and reactivity along groundwater and surface water flow paths, the role of autochthonous organic matter in streambed biogeochemical functioning, and the feedbacks between surface-subsurface ecological processes, both within and across spatial and temporal scales. While simplified approaches to these issues are justifiable and necessary for transferability, the exclusion of important hyporheic processes from our conceptualizations can lead to erroneous conclusions and inadequate understanding and management of interconnected surface water and groundwater environments. This is particularly true at the landscape scale, where the organizational principles of spatio-temporal dynamics of hyporheic exchange flow (HEF) and biogeochemical processes remain largely uncharacterized. This article seeks to identify the most important drivers and controls of HEF and biogeochemical cycling based on a comprehensive synthesis of findings from a wide range of river systems. We use these observations to test current paradigms and conceptual models, discussing the interactions of local-to-regional hydrological, geomorphological, and ecological controls of hyporheic zone functioning. This improved conceptualization of the landscape organizational principles of drivers of HEF and biogeochemical processes from reach to catchment scales will inform future river research directions and watershed management strategies.

Long-term, high-frequency time series of passive tracers in precipitation and streamflow are essential for quantifying catchment transport and storage processes, but few such data sets are publicly available. Here we describe, present, and make available to the public two extensive data sets of stable water isotopes in streamflow and precipitation at the Plynlimon experimental catchments in central Wales. Stable isotope data are available at 7-hourly intervals for 17 months, and at weekly intervals for 4.25 years. Precipitation isotope values were highly variable in both data sets, and the high temporal resolution of the 7-hourly streamwater samples revealed rich isotopic dynamics that were not captured by the weekly sampling. We used ensemble hydrograph separation to calculate new water fractions and transit time distributions from both data sets. Transit time distributions estimated by ensemble hydrograph separation were broadly consistent with those estimated by spectral fitting methods, suggesting that they can reliably quantify the contributions of recent precipitation to streamflow. We found that on average, roughly 3 % of streamwater was made up of precipitation that fell within the previous 7 h, and 13 %–15 % of streamwater was made up of precipitation that fell within the previous week. The contributions of recent precipitation to streamflow were highest during large events, as illustrated by comparing new water fractions for different discharges and precipitation rates. This dependence of new water fractions on water fluxes was also reflected in their seasonal variations, with lower new water fractions and more damped catchment transit time distributions in spring and summer compared to fall and winter. We also compared new water fractions obtained from stable water isotopes against those obtained from concentrations of chloride, a solute frequently used as a passive tracer of catchment transport processes. After filtering the chloride data for dry deposit

Although most field and modeling studies of river corridor exchange have been conducted at scales ranging from tens to hundreds of meters, results of these studies are used to predict their ecological and hydrological influences at the scale of river networks. Further complicating prediction, exchanges are expected to vary with hydrologic forcing and the local geomorphic setting. While we desire predictive power, we lack a complete spatiotemporal relationship relating discharge to the variation in geologic setting and hydrologic forcing that is expected across a river basin. Indeed, the conceptual model of Wondzell (2011) predicts systematic variation in river corridor exchange as a function of (1) variation in baseflow over time at a fixed location, (2) variation in discharge with location in the river network, and (3) local geomorphic setting. To test this conceptual model we conducted more than 60 solute tracer studies including a synoptic campaign in the 5th-order river network of the H. J. Andrews Experimental Forest (Oregon, USA) and replicate-intime experiments in four watersheds. We interpret the data using a series of metrics describing river corridor exchange and solute transport, testing for consistent direction and magnitude of relationships relating these metrics to discharge and local geomorphic setting. We confirmed systematic decrease in river corridor exchange space through the river networks, from headwaters to the larger main stem. However, we did not find systematic variation with changes in discharge through time or with local geomorphic setting. While interpretation of our results is complicated by problems with the analytical methods, the results are sufficiently robust for us to conclude that space-for-time and time-for-space substitutions are not appropriate in our study system. Finally, we suggest two strategies that will improve the interpretability of tracer test results and help the hyporheic community develop robust datasets that will e

Time-variable discharge is known to control both transport and transformation of solutes in the river corridor. Still, few studies consider the interactions of transport and transformation together. Here, we consider how diurnal discharge fluctuations in an intermittent, headwater stream control reach-scale solute transport and transformation as measured with conservative and reactive tracers during a period of no precipitation. One common conceptual model is that extended contact times with hyporheic zones during low discharge conditions allows for increased transformation of reactive solutes. Instead, we found tracer timescales within the reach were related to discharge, described by a single discharge-variable StorAge Selection function. We found that Resazurin to Resorufin (Raz-to-Rru) transformation is static in time, and apparent differences in reactive tracer were due to interactions with different ages of storage, not with time-variable reactivity. Overall we found reactivity was highest in youngest storage locations, with minimal Raz-to-Rru conversion in waters older than about 20 h of storage in our study reach. Therefore, not all storage in the study reach has the same potential biogeochemical function and increasing residence time of solute storage does not necessarily increase reaction potential of that solute, contrary to prevailing expectations.

A comprehensive set of measurements and calculated metrics describing physical, chemical, and biological conditions in the river corridor is presented. These data were collected in a catchment-wide, synoptic campaign in the H. J. Andrews Experimental Forest (Cascade Mountains, Oregon, USA) in summer 2016 during low-discharge conditions. Extensive characterization of 62 sites including surface water, hyporheic water, and streambed sediment was conducted spanning 1st- through 5th-order reaches in the river network. The objective of the sample design and data acquisition was to generate a novel data set to support scaling of river corridor processes across varying flows and morphologic forms present in a river network.

Novel observation techniques (e.g., smart tracers) for characterizing coupled hydrological and biogeochemical processes are improving understanding of stream network transport and transformation dynamics. In turn, these observations are thought to enable increasingly sophisticated representations within transient storage models (TSMs). However, TSM parameter estimation is prone to issues with insensitivity and equifinality, which grow as parameters are added to model formulations. Currently, it is unclear whether (or not) observations from different tracers may lead to greater process inference and reduced parameter uncertainty in the context of TSM. Herein, we aim to unravel the role of in‐stream processes alongside metabolically active (MATS) and inactive storage zones (MITS) using variable TSM formulations. Models with one (1SZ) and two storage zones (2SZ) and with and without reactivity were applied to simulate conservative and smart tracer observations obtained experimentally for two reaches with differing morphologies. As we show, smart tracers are unsurprisingly superior to conservative tracers when it comes to partitioning MITS and MATS. However, when transient storage is lumped within a 1SZ formulation, little improvement in parameter uncertainty is gained by using a smart tracer, suggesting the addition of observations should scale with model complexity. Importantly, our work identifies several inconsistencies and open questions related to reconciling time scales of tracer observation with conceptual processes (parameters) estimated within TSM. Approaching TSM with multiple models and tracer observations may be key to gaining improved insight into transient storage simulation as well as advancing feedback loops between models and observations within hydrologic science.

Stream metabolism is a fundamental, integrative indicator of aquatic ecosystem functioning. However, it is not well understood how heterogeneity in physical channel form, particularly in relation to and caused by in‐stream woody debris, regulates stream metabolism in lowland streams. We combined conservative and reactive stream tracers to investigate relationships between patterns in stream channel morphology and hydrological transport (form) and metabolic processes as characterized by ecosystem respiration (function) in a forested lowland stream at baseflow. Stream reach‐scale ecosystem respiration was related to locations (“hotspots”) with a high abundance of woody debris. In contrast, nearly all other measured hydrological and geomorphic variables previously documented or hypothesized to influence stream metabolism did not significantly explain ecosystem respiration. Our results suggest the existence of key differences in physical controls on ecosystem respiration between lowland stream systems (this study) and smaller upland streams (most previous studies) under baseflow conditions. As such, these findings have implications for reactive transport models that predict biogeochemical transformation rates from hydraulic transport parameters, for upscaling frameworks that represent biological stream processes at larger network scales, and for the effective management and restoration of aquatic ecosystems.

Shallow benthic biolayers at the top of the streambed are believed to be places of enhanced biogeochemical turnover within the hyporheic zone. They can be investigated by reactive stream tracer tests with tracer recordings in the streambed and in the stream channel. Common in-stream measurements of such reactive tracers cannot localize where the processing primarily takes place, whereas isolated vertical depth profiles of solutes within the hyporheic zone are usually not representative of the entire stream. We present results of a tracer test where we injected the conservative tracer bromide together with the reactive tracer resazurin into a third-order stream and combined the recording of in-stream breakthrough curves with multidepth sampling of the hyporheic zone at several locations. The transformation of resazurin was used as an indicator of metabolism, and high-reactivity zones were identified from depth profiles. The results from our subsurface analysis indicate that the potential for tracer transformation (i.e., the reaction rate constant) varied with depth in the hyporheic zone. This highlights the importance of the benthic biolayer, which we found to be on average 2 cm thick in this study, ranging from one third to one half of the full depth of the hyporheic zone. The reach-scale approach integrated the effects of processes along the reach length, isolating hyporheic processes relevant for whole-stream chemistry and estimating effective reaction rates.