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Riparian zones are highly‐dynamic transition zones between surface water (SW) and groundwater (GW) and function as key biogeochemical‐reactors for solutes transitioning between both compartments. Infiltration of SW rich in dissolved oxygen (DO) into the riparian aquifer can supress removal processes of redox sensitive compounds like NO3−, a nutrient harmful for the aquatic ecosystem at high concentrations. Seasonal and short‐term variations of temperature and hydrologic conditions can influence biogeochemical reaction rates and thus the prevailing redox conditions in the riparian zone. We combined GW tracer‐tests and a 1‐year high‐frequency dataset of DO with data‐driven simulations of DO consumption to assess the effects of seasonal and event‐scale variations in temperature and transit‐times on the reactive transport of DO. Damköhler numbers for DO consumption (DADO) were used to characterize the system in terms of DO turnover potential. Our results suggest that seasonal and short‐term variations in temperature are major controls for DO turnover and the resulting concentrations at our field site, while transit‐times are of minor importance. Seasonal variations of temperature in GW lead to shifts from transport‐limited (DADO > 1) to reaction‐limited conditions (DADO, Groundwater tracer‐tests are combined with 1‐year high‐frequency data of dissolved oxygen, water temperature, and water‐levels, and data‐driven simulations to assess the seasonal and event‐term variations of transport and consumption of riparian dissolved oxygen and the further implications for redox processes. image

Riparian zones are important buffer zones for streams as they are hotspots of nitrate transformation and removal in agricultural catchments. However, mixing of water from different sources and various transformation processes can complicate the quantification of nitrate turnover in riparian zones. In this study, we analyzed nitrate concentration and isotope data in riparian groundwater along a 2-km stream section in central Germany. We developed a mathematical model combining end-member mixing and isotope modeling to account for mixing of river water and groundwater and quantify nitrate transformation in riparian groundwater. This enabled us to explicitly determine the extent of denitrification (as process leading to permanent nitrate removal from riparian groundwater) and transient nitrate removal by additional processes associated with negligible isotope fractionation (e.g., plant uptake and microbial assimilation) and to perform an extensive uncertainty analysis. Based on the nitrogen isotope data of nitrate, the simulations suggest a mean removal of up to 28% by additional processes and only about 9% by denitrification. Nitrate removal from riparian groundwater by additional processes exceeded denitrification particularly in winter and at larger distance from the river, underlining the role of the river as organic carbon source. This highlights that nitrate consumption by additional processes predominates at the field site, implying that a substantial fraction of agricultural nitrogen input is not permanently removed but rather retained in the riparian zone. Overall, our model represents a useful tool to better compare nitrogen retention to permanent nitrogen removal in riparian zones at various temporal and spatial scales.

Besides gas-water-exchange in surface waters, respiratory consumption of dissolved oxygen (DO) in adjacent riparian groundwater may trigger the addition of so far hardly explored sources from the unsaturated zone. These processes also systematically influence stable isotope ratios of DO and were investigated together with Cl− as a conservative tracer for water mixing in a near-river riparian groundwater system. The study focused on a losing stream section of the Selke River at the foot of the Harz Mountains (Germany). The study area exposed steep DO gradients between the stream water and riparian groundwater between April 2016 and May 2017. Our results indicated dominant influences of microbial community respiration with observed DO concentration gradients. These observations can be explained by DO from the river that is subject to fractionation by microbial respiration with a typical fractionation factor (αr) of 0.982. However, with such respiration dominance, we expected a simultaneous enrichment of δ18ODO towards values that are more positive than the well-known atmospheric O2 signal of +23.9‰ versus the Vienna Standard Mean Ocean Water standard (VSMOW). Surprisingly, our measurements revealed much lower δ18ODO values between +22‰ and +18‰ in the near-river groundwater. Mass balance calculations revealed that the DO pool in the shallow and unconfined aquifer receives contributions of up to about 80% by diffusion of oxygen from the vadose zone with a distinctly lower isotope value than the one of the atmosphere. This finding about additional oxygen sources from the unsaturated zone has numerous ramifications for oxygen related processes in near-river environments including the oxidation of pollutants, nutrients and ecosystem health.

The biogeochemical composition of stream water and the surrounding riparian water is mainly defined by the exchange of water and solutes between the stream and the riparian zone. Short-term fluctuations in near stream hydraulic head gradients (e.g., during stream flow events) can significantly influence the extent and rate of exchange processes. In this study, we simulate exchanges between streams and their riparian zone driven by stream stage fluctuations during single stream discharge events of varying peak height and duration. Simulated results show that strong stream flow events can trigger solute mobilization in riparian soils and subsequent export to the stream. The timing and amount of solute export is linked to the shape of the discharge event. Higher peaks and increased durations significantly enhance solute export, however, peak height is found to be the dominant control for overall mass export. Mobilized solutes are transported to the stream in two stages (1) by return flow of stream water that was stored in the riparian zone during the event and (2) by vertical movement to the groundwater under gravity drainage from the unsaturated parts of the riparian zone, which lasts for significantly longer time (> 400 days) resulting in long tailing of bank outflows and solute mass outfluxes. We conclude that strong stream discharge events can mobilize and transport solutes from near stream riparian soils into the stream. The impact of short-term stream discharge variations on solute exchange may last for long times after the flow event.

In this study, we investigate the impact of single stream discharge events on water exchange, solute transport, and reactions in the hyporheic zone below a natural in-stream gravel bar. We set up a reactive transport groundwater model with streamflow scenarios that vary by event duration and peak discharge. A steady ambient groundwater flow field is assumed that results in losing, neutral, or gaining stream conditions depending on the stream stage. Across the streambed dissolved oxygen, organic carbon, and nitrate are transported into the subsurface. Additional nitrate is received from upwelling groundwater. Aerobic respiration and denitrification are simulated for scenarios with different stream solute concentrations. Results show that hyporheic exchange flux, solute transport, and consumption increase during events. However, their intensities depend highly on the interplay between event characteristics and ambient groundwater conditions. During events where reversals in the hydraulic gradient occur stream water and solutes infiltrate deeper into the aquifer where they have more time to react. For those events, the reactive efficiency of the hyporheic zone (solute consumption as fraction of influx) for aerobic respiration and denitrification is up to 2.7 and 10 times higher compared to base flow conditions. The fraction of stream nitrate load consumed in the hyporheic zone increases with stream discharge (up to 150 mg/m2/h), but remains below the value under base flow conditions for weak events. Events also increase denitrification of groundwater borne nitrate, but groundwater nitrate flux to the stream decreases by up to 33% due to temporary gradient reversals.

Riffle-pool sequences are fundamental, ubiquitous morphological features of alluvial rivers that are thoroughly studied in general and commonly incorporated into river restoration projects. Most previous investigations on the effect of riffle-pool sequences on hyporheic exchanges focused on solely bed undulation, because that is widely thought to be the defining feature of riffle-pool sequences. However, riffle- pool sequences also have significant width undulations that are vital to riffle-pool sequences morphodynamics, yet relatively few studies exist on the effect of such undulations on hyporheic exchanges. Thus, in this study based on laboratory experiments and numerical simulations, we investigate the effect of bed and width undulations on hyporheic zone characteristics for various ratio of width amplitude to bed amplitude. The variation of hyporheic exchange characteristics (i.e. hyporheic exchange flux and residence time) for different riffle-pool designs were also assessed by creating prescribed topography of synthetic river valleys. The results showed that due to pressure variation along width undulations, the upwelling and downwelling patterns can also be observed for only width undulations in rivers, in the absence of bed undulations, and as width undulation amplitude decreases, the normalized hyporheic exchanges (Q*HZ) increase and normalized median residence time (RT*) decreases. Also, simultaneous channel bed and width undulations result in higher Q*HZ especially when a pool is located in an expansion (aka “oversized” cross-section) and a riffle in a constriction (“nozzle”). Our results suggest that river restoration project that artificially construct wide pools and constricted riffles will achieve maximum Q*HZ and RT*, though they will not be geomorphically self-sustainable.

Aerobic respiration is an important component of in-stream metabolism. The larger part occurs in the streambed, where it is difficult to directly determine actual respiration rates. Existing methods for determining respiration are based on indirect estimates from whole-stream metabolism or provide time invariant results estimated from oxygen consumption measurements in enclosed chambers that do not account for the influence of hydrological changes. In this study we demonstrate a simple method for determining time-variable hyporheic respiration. We use a windowed cross-correlation approach for deriving time-variable travel times from the naturally changing electrical conductivity signal that is transferred into the sediment. By combining the results with continuous in situ dissolved oxygen measurements, variable oxygen consumption rate coefficients in the streambed are obtained. An empirical temperature relationship is derived and used for standardizing the respiration rate coefficients to isothermal conditions. For demonstrating the method, we compare two independent measurement spots in the streambed, which were located upstream and downstream of an in-stream gravel bar and thus exposed strongly diverse travel times. The derived respiration rate results are in accordance with findings of other stream studies. By comparing the travel time and respiration rate coefficient (i.e., Damkohler number) we estimate the contribution of each to the oxygen consumption in the streambed.

The interaction of the water residence time (RT) in hyporheic sediments with the sediment metabolic rates is believed to be a key factor controlling whole stream metabolism. However, due to the methodological difficulties, there is little data that investigates this fundamental theory of aquatic ecology. Here, we report on progress made to combine numerical modelling with a series of modification to laboratory flumes overcoming methodological difficulties e.g. by creating steady flow paths for assessment of metabolic rates. To model the biogeochemical performance and to validate the model results, sediment structures were introduced in both, the model and the flumes, leading to differing RT distributions. Furthermore, the DOC supply in the flumes was manipulated to test the whole stream metabolic response with regard to RT distributions. In the flumes, hydraulic conditions were assessed using conservative tracer and heat as tracer. Metabolic activity was assessed using oxygen dynamics as a proxy of community respiration (CR). Residence time and metabolic processes were modelled using a multicomponent reactive transport code called MIN3P and calibrated with regard to the hydraulic conditions using the results obtained from the flume experiments. Monod type expressions were used to implement metabolic activity terms in the model. Using the results of the hydrological process model, a sensitivity analysis of the impact of RT distributions on the metabolic activity could yield supporting proof of an existing link between the two.

Besides gas-water-exchange in surface waters, respiratory consumption of dissolved oxygen (DO) in adjacent riparian groundwater may trigger the addition of so far hardly explored sources from the unsaturated zone. These processes also systematically influence stable isotope ratios of DO and were investigated together with Cl

Hydrochemical solute concentrations in the shallow subsurface can be spatially highly variable within small scales, particularly at interfaces. However, most monitoring systems fail to capture these small scale variations. Within this study, we developed a high resolution multilevel well (HR-MLW) with which we monitored water across the interface of the unsaturated and saturated zone with a vertical resolution of 0.05-0.5 m. We installed three of these 4 m deep HR-MLWs in the riparian zone of a third-order river and analyzed for hydrochemical parameters and stable water isotopes. The results showed three distinct vertical zones (unsaturated zone, upper saturated zone, lower saturated zone) within the alluvial aquifer. A 2 m thick layer influenced by river water (upper saturated zone) was not captured by existing monitoring wells with higher screen length. Hydrochemical data (isotopes, total ions) were consistent in all HR-MLWs and showed similar variation over time emphasizing the reliability of the installed monitoring system. Further, the depths zones were also reflected in the NO

Streams are significant sources of CO2 to the atmosphere. Estimates of CO2 evasion fluxes (fCO2) from streams typically relate to the free flowing water but exclude geomorphological structures within the stream corridor. We found that gravel bars (GBs) are important sources of CO2 to the atmosphere, with on average more than twice as high fCO2 as those from the streamwater, affecting fCO2 at the level of entire headwater networks. Vertical temperature gradients resulting from the interplay between advective heat transfer and mixing with groundwater within GBs explained the observed variation in fCO2 from the GBs reasonably well. We propose that increased temperatures and their gradients within GBs exposed to solar radiation stimulate heterotrophic metabolism therein and facilitate the venting of CO2 from external sources (e.g. downwelling streamwater, groundwater) within GBs. Our study shows that GB fCO2 increased f CO2 from stream corridors by [median, (95% confidence interval)] 16.69%, (15.85–18.49%); 30.44%, (30.40–34.68%) and 2.92%, (2.90–3.0%), for 3rd, 4th and 5th order streams, respectively. These findings shed new light on regional estimates of fCO2 from streams, and are relevant given that streamwater thermal regimes change owing to global warming and human alteration of stream corridors.

The biogeochemical composition of stream water and the surrounding riparian water is mainly defined by the exchange of water and solutes between the stream and the riparian zone. Short-term fluctuations in near stream hydraulic head gradients (e.g., during stream flow events) can significantly influence the extent and rate of exchange processes. In this study, we simulate exchanges between streams and their riparian zone driven by stream stage fluctuations during single stream discharge events of varying peak height and duration. Simulated results show that strong stream flow events can trigger solute mobilization in riparian soils and subsequent export to the stream. The timing and amount of solute export is linked to the shape of the discharge event. Higher peaks and increased durations significantly enhance solute export, however, peak height is found to be the dominant control for overall mass export. Mobilized solutes are transported to the stream in two stages (1) by return flow of stream water that was stored in the riparian zone during the event and (2) by vertical movement to the groundwater under gravity drainage from the unsaturated parts of the riparian zone, which lasts for significantly longer time (400 days) resulting in long tailing of bank outflows and solute mass outfluxes. We conclude that strong stream discharge events can mobilize and transport solutes from near stream riparian soils into the stream. The impact of short-term stream discharge variations on solute exchange may last for long times after the flow event.

Streams are significant sources of CO2 to the atmosphere. Estimates of CO2 evasion fluxes (f CO2) from streams typically relate to the free flowing water but exclude geomorphological structures within the stream corridor. We found that gravel bars (GBs) are important sources of CO2 to the atmosphere, with on average more than twice as high f CO2 as those from the streamwater, affecting f CO2 at the level of entire headwater networks. Vertical temperature gradients resulting from the interplay between advective heat transfer and mixing with groundwater within GBs explained the observed variation in f CO2 from the GBs reasonably well. We propose that increased temperatures and their gradients within GBs exposed to solar radiation stimulate heterotrophic metabolism therein and facilitate the venting of CO2 from external sources (e.g. downwelling streamwater, groundwater) within GBs. Our study shows that GB f CO2 increased f CO2 from stream corridors by [median, (95% confidence interval)] 16.69%, (15.85–18.49%); 30.44%, (30.40–34.68%) and 2.92%, (2.90–3.0%), for 3rd, 4th and 5th order streams, respectively. These findings shed new light on regional estimates of f CO2 from streams, and are relevant given that streamwater thermal regimes change owing to global warming and human alteration of stream corridors.

Nitrate contamination in ground- and surface water is a persistent problem in countries with intense agriculture. The transition zone between rivers and their riparian aquifers, where river water and groundwater interact, may play an important role in mediating nitrate exports, as it can facilitate intensive denitrification, which permanently removes nitrate from the aquatic system. However, the in-situ factors controlling riparian denitrification are not fully understood, as they are often strongly linked and their effects superimpose each other. In this study, we present the evaluation of hydrochemical and isotopic data from a 2-year sampling period of river water and groundwater in the riparian zone along a 3rd order river in Central Germany. Based on bi- and multivariate statistics (Spearman's rank correlation and partial least squares regression) we can show, that highest rates for oxygen consumption and denitrification in the riparian aquifer occur where the fraction of infiltrated river water and at the same time groundwater temperature, are high. River discharge and depth to groundwater are additional explanatory variables for those reaction rates, but of minor importance. Our data and analyses suggest that at locations in the riparian aquifer, which show significant river water infiltration, heterotrophic microbial reactions in the riparian zone may be fueled by bioavailable organic carbon derived from the river water. We conclude that interactions between rivers and riparian groundwater are likely to be a key control of nitrate removal and should be considered as a measure to mitigate high nitrate exports from agricultural catchments.

At the interface between stream water, groundwater, and the hyporheic zone (HZ), important biogeochemical processes that play a crucial role in fluvial ecology occur. Solutes that infiltrate into the HZ can react with each other and possibly also with upwelling solutes from the groundwater. In this study, we systematically evaluate how variations of gaining and losing conditions, stream discharge, and pool-riffle morphology affect aerobic respiration (AR) and denitrification (DN) in the HZ. For this purpose, a computational fluid dynamics model of stream water flow is coupled to a reactive transport model. Scenarios of variations of the solute concentration in the upwelling groundwater were conducted. Our results show that solute influx, residence time, and the size of reactive zones strongly depend on presence, magnitude, and direction of ambient groundwater flow. High magnitudes of ambient groundwater flow lower AR efficiency by up to 4 times and DN by up to 3 orders of magnitude, compared to neutral conditions. The influence of stream discharge and morphology on the efficiency of AR and DN are minor, in comparison to that of ambient groundwater flow. Different scenarios of O2 and NO3 concentrations in the upwelling groundwater reveal that DN efficiency of the HZ is highest under low upwelling magnitudes accompanied with low concentrations of O2 and NO3. Our results demonstrate how ambient groundwater flow influences solute transport, AR, and DN in the HZ. Neglecting groundwater flow in stream-groundwater interactions would lead to a significant overestimation of the efficiency of biogeochemical reactions in fluvial systems.

[1] Exchange of water and solutes across the stream-sediment interface is an important control for biogeochemical transformations in the hyporheic zone (HZ). In this paper, we investigate the interplay between turbulent stream flow and HZ flow in pool-riffle streams under various ambient groundwater flow conditions. Streambed pressures, derived from a computational fluid dynamics (CFD) model, are assigned at the top of the groundwater model, and fluxes at the bottom of the groundwater model domain represent losing and gaining conditions. Simulations for different Reynolds numbers (Re) and pool-riffle morphologies are performed. Results show increasing hyporheic exchange flows (m3/d) for larger Re and a concurrent decrease in residence time (RT). Losing and gaining conditions were found to significantly affect the hyporheic flow field and diminish its spatial extent as well as rates of hyporheic exchange flow. The fraction of stream water circulating through the hyporheic zone is in the range of 1 × 10−5 to 1 × 10−6 per meter stream length, decreasing with increasing discharge. Complex distributions of pressure across the streambed cause significant lateral hyporheic flow components with a mean lateral travel distance of 20% of the longitudinal flow paths length. We found that the relationship between pool-riffle height and hyporheic exchange flow is characterized by a threshold in pool-riffle amplitude, beyond which hyporheic exchange flow becomes independent of riffle height. Hyporheic residence time distributions (RTD) are log-normally distributed with medians ranging between 0.7 and 19 h.

Summary Hydrodynamic exchange between surface-water and groundwater was studied at a river located within the Rhine Valley in Germany. Piezometric pressure heads and environmental tracers such as temperature, stable isotopes, chloride, X-ray contrast media, and artificial sweetener were investigated within the hyporheic zone and river water plume. Vertical profiles of environmental tracers were collected using multi-level wells within the neutral up-gradient zone, beneath the river bed, and within the horizontal proximal and distal down-gradient zone. Infiltration velocities were calculated from pressure heads, temperature fluctuations and gradients. The amount of river water within groundwater was estimated from vertical profiles of chloride, stable isotopes, and persistent pharmaceuticals. Profiles of stable isotopes and chloride reveal the existence of down-welling within the shallow hyporheic zone that is generated by river bed irregularities. Due to down-welling an above-average migration of river water into the hyporheic zone establishes even under upward hydraulic pressure gradients. The investigated environmental tracers could not distinctively display short-time-infiltration velocities representative for flood waves, while average infiltration velocities calculated over several months are uniform displayed. Based on vertical temperature profiles the down-gradient migration of the river water plume could be observed even after long periods of effluent conditions and over a distance of 200 m from the river bank. X-ray contrast media and artificial sweeteners were observed in high concentrations within the proximal zone, but were not detected at a distance of 200 m from the river bank. Using temperature as environmental tracer within the hyporheic zone may result in overestimating the migration of pollutants within the river water plume as the process of natural attenuation will be neglected. Furthermore, temperature was not able to display the effect of down-welling. Stable isotopes and chloride were found to be suitable environmental tracers to forecast the release and fate of organic contaminants within the hyporheic zone.

Volcanic terrains such as magmatic arcs are thought to display the most complex surface environments on Earth. Ancient volcaniclastics are notoriously difficult to interpret as they describe the interplay between a single or several volcanoes and the environment. The Early Miocene Tepoztlan Formation at the southern edge of the Transmexican Volcanic Belt belongs to the few remnants of this ancestral magmatic arc, and therefore is thought to represent an example of the initial phase of evolution of the Transmexican Volcanic Belt. Based on geological mapping, detailed logging of lithostratigraphic sections, palaeocurrent data of sedimentary features and anisotropy of magnetic susceptibility, mapping of two-dimensional panels from outcrop to field scale, and geochronological data in an area of ca 1000 km 2 , three periods in the evolution of the Tepoztlan Formation were distinguished, which lasted around 4 Myr and are representative of a volcanic cycle (edifice growth phases followed by collapse) in a magmatic arc setting. The volcaniclastic sediments accumulated in proximal to medial distances on partly coalescing aprons, similar to volcanic ring plains, around at least three different stratovolcanoes. These volcanoes resulted from various eruptions separated by repose periods. During the first phase of the evolution of the Tepoztlan Formation (22AE 8t o 22 AE2 Ma), deposition was dominated by fluvial sediments in a braided river setting. Pyroclastic material from small, andesitic-dacitic composite volcanoes in the near vicinity was mostly eroded and reworked by fluvial processes, resulting in sediments ranging from cross-bedded sand to an aggradational series of river gravels. The second phase (22AE 2t o 21 AE3 Ma) was characterized by periods of strong volcanic activity, resulting in voluminous accumulations of lava and tuff, which temporarily overloaded and buried the original fluvial system with its detritus. Continuous build-up of at least three major volcanic centres further accentuated the topography and, in the third phase (21AE 3t o 18 AE8 Ma), mass flow processes, represented by an increase of debris flow deposits, became dominant, marking a period of edifice destruction and flank failures.

Hyporheic exchange transports solutes into the subsurface where they can undergo biogeochemical transformations, affecting fluvial water quality and ecology. A three-dimensional numerical model of a natural in-stream gravel bar (20 m × 6 m) is presented. Multiple steady state streamflow is simulated with a computational fluid dynamics code that is sequentially coupled to a reactive transport groundwater model via the hydraulic head distribution at the streambed. Ambient groundwater flow is considered by scenarios of neutral, gaining, and losing conditions. The transformation of oxygen, nitrate, and dissolved organic carbon by aerobic respiration and denitrification in the hyporheic zone are modeled, as is the denitrification of groundwater-borne nitrate when mixed with stream-sourced carbon. In contrast to fully submerged structures, hyporheic exchange flux decreases with increasing stream discharge, due to decreasing hydraulic head gradients across the partially submerged structure. Hyporheic residence time distributions are skewed in the log-space with medians of up to 8 h and shift to symmetric distributions with increasing level of submergence. Solute turnover is mainly controlled by residence times and the extent of the hyporheic exchange flow, which defines the potential reaction area. Although streamflow is the primary driver of hyporheic exchange, its impact on hyporheic exchange flux, residence times, and solute turnover is small, as these quantities exponentially decrease under losing and gaining conditions. Hence, highest reaction potential exists under neutral conditions, when the capacity for denitrification in the partially submerged structure can be orders of magnitude higher than in fully submerged structures.

One of the key environmental conditions controlling biogeochemical reactions in aquatic sediments like streambeds is the distribution of dissolved oxygen. We present a novel approach for the in situ measurement of vertical oxygen profiles using a planar luminescence-based optical sensor. The instrument consists of a transparent acrylic tube with the oxygen-sensitive layer mounted on the outside. The luminescence is excited and detected by a moveable piston inside the acrylic tube. Since no moving parts are in contact with the streambed, the disturbance of the subsurface flow field is minimized. The precision of the distributed oxygen sensor (DOS) was assessed by a comparison with spot optodes. Although the precision of the DOS, expressed as standard deviation of calculated oxygen air saturation, is lower (0.2-6.2%) compared to spot optodes (0.1-0.6%), variations of the oxygen content along the profile can be resolved. The uncertainty of the calculated oxygen is assessed with a Monte Carlo uncertainty assessment. The obtained vertical oxygen profiles of 40 cm in length reveal variations of the oxygen content reaching from 90% to 0% air saturation and are characterized by patches of low oxygen rather than a continuous decrease with depth.