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Headwaters represent a significant fraction of the global stream length and are important for streamflow quality and quantity. Since climate change is predicted to affect runoff generation processes fundamentally, it is essential to understand potential consequences for the water availability in headwater catchments. The Lehstenbach catchment, located in the Fichtel Mountains (Germany), represents many headwater catchments in the lower mountain ranges in Central Europe. This study’s primary objective is to predict and analyze potential shifts in the catchment’s water balance, estimate periods of hydrological drought conditions, and their characteristics. For this purpose, we used an integrated process-based hydrological model to represent surface/groundwater interactions and runoff generation mechanisms for the Lehstenbach catchment until 2100, using a Regional Climate Model Ensemble. The simulations indicate decreased water availability in summer and autumn, mainly due to increased evapotranspiration rates. The Minimum Environmental Flow (MEF), a quantitative measure of aquatic species’ exposition to abnormally low streamflow conditions, implies an increase of low flow conditions towards 2100. A first estimate indicates a possible increase of hydrological drought duration and intensity in the future. These findings suggest severe impacts on ecosystem health and services, such as decreasing water availability, leading to consequences like forest and wetland degradation and declining biodiversity. These findings can be used to implement suitable mitigation strategies to reduce climate change effects on the headwater ecosystems, such as water shortage for irrigation and drinking water supply and loss of flora and fauna.

Understanding groundwater–surface water (GW–SW) interactions is vital for water management in karstic catchments due to its impact on water quality. The objective of this study was to evaluate and compare the applicability of seven environmental tracers to quantify and localize groundwater exfiltration into a small, human‐impacted karstic river system. Tracers were selected based on their emission source to the surface water either as (a) dissolved, predominantly geogenic compounds (radon‐222, sulphate and electrical conductivity) or (b) anthropogenic compounds (predominantly) originating from wastewater treatment plant (WWTP) effluents (carbamazepine, tramadol, sodium, chloride). Two contrasting sampling approaches were compared (a) assuming steady‐state flow conditions and (b) considering the travel time of the water parcels (Lagrangian sampling) through the catchment to account for diurnal changes in inflow from the WWTP. Spatial variability of the concentrations of all tracers indicated sections of preferential groundwater inflow. Lagrangian sampling techniques seem highly relevant for capturing dynamic concentration patterns of WWTP‐derived compounds. Quantification of GW inflow with the finite element model FINIFLUX, based on observed in‐stream Rn activities led to plausible fluxes along the investigated river reaches (0.265 m3 s−1), while observations of other natural or anthropogenic environmental tracers produced less plausible water fluxes. Important point sources of groundwater exfiltration can be ascribed to locations where the river crosses geological fault lines. This indicates that commonly applied concepts describing groundwater–surface water interactions assuming diffuse flow in porous media are difficult to transfer to karstic river systems whereas concepts from fractured aquifers may be more applicable. In general, this study helps selecting the best suited hydrological tracer for GW exfiltration and leads to a better understanding of processes controlling groundwater inflow into karstic river systems., Karst aquifers represent an increased complexity when aiming to measure the interaction between groundwater and river water. Combining field‐based measurements on catchment scale and modelling, the applicability of ‘classical’ environmental groundwater tracers was compared to selected organic (micro)pollutants often considered as conservative and originally arising from a wastewater treatment plant. This study demonstrates that the choice of an appropriate tracer is crucial when either aiming to quantify groundwater exfiltration into karstic river systems, or indicating hydrological processes, applying (globally) omnipresent pollutants., German Research Foundation (DFG) http://dx.doi.org/10.13039/501100001659

Microplastic (MP) residence times are currently poorly constrained in lakes, especially at a quantitative level. In this work settling experiments with pristine and biofilm-colonized MPs were combined with model calculations to evaluate settling velocities, particle distributions and residence times in the epi- meta and hypolimnion of a hypothetical stratified lake broadly based on Upper Lake Constance. Settling velocities of various biodegradable and non-biodegradable polymers of various shapes, sizes and biofilm colonization were measured in a settling column. The settling velocities ranged between ~ 0.30 and ~50 mm s-1. Particle sizes and polymer densities were identified as primary controls on settling rates. MPs that had been exposed to a lake environment for up to 30 weeks were colonized by a range of biofilms and associated extracellular polymeric substances; surprisingly, however, the settling velocity did not vary significantly between pristine and colonized MP particles. Simulated MP residence times in the model lake varied over a wide range of time scales (10-1 - 105 days) and depended mainly on the size of the particles and depth of the lake layer. Long residence times on the order of 105 days (for 1 µm MPs) imply that for small MP particles there is a high probability that they will be taken up at some stage by lake organisms. It also suggests that insignificant amounts of small MPs will be found in the lake sediment unless some process increases their settling velocity as their residence time is considerably longer than the theoretical retention time of Lake Constance (~4.5 years).

Beach faces form the interface between terrestrial and marine systems. They act as a reactive zone between these two compartments, transporting and biogeochemically modifying terrestrially sourced chemical constituents such as nutrients, pollutants and carbon towards the sea. This interface is referred to as the subterranean estuary. The subterranean estuary is important on global scales for modifying and processing dissolved and particulate matter sourced from the sea as it cycles through the beach sediments. Re-circulation of sea water through beach sediments is largely driven by tidal pumping and pressure gradients caused by tides, wave setup, and storm events that pile sea water up on the beach face. In contrast, terrestrial groundwater systems provide a source of low salinity and often nutrient rich water to the coastal zone. Mixing between these water sources is complicated by catchment morphology, variable density flow caused by saline sea water lying above and below the fresh terrestrial groundwater. Thus tracing water and nutrients fluxes through the subterranean estuary is not trivial. In this work we use a combination of temperature measurements and heat modelling to estimate water fluxes through the subterranean estuary and pore water stable isotopes and chemistry to infer the origin of this discharge in the Königshafen, on Sylt Island, Northern Germany. The results show that flow paths are complex, with dune morphology influencing the focal point for fresh groundwater discharge. Seaward, saline and brackish discharge occurs into the tidal creek draining the bay. The complexity of heat transport modelling in the coastal zone depends on the boundary conditions, with very complex boundaries requiring more complex modelling structures (e.g. steady state vs. non steady state). Overall temperature measurements and heat modelling combined with pore water chemistry show potential to understand water and chemical exchange through the subterranean estuary and thus help to understand water and material fluxes at the terrestrial-ocean interface.

Although rivers and streams are major transport vectors of microplastics into the marine environment, little research has been conducted to understand the transport behavior of microplastic particles in fluvial systems. This work contributes to the understanding of these transport processes, specifically focusing on the interface of the surface water flow and the hyporheic zone.Transport of microplastic particles in fluvial systems is currently modeled mainly at larger, river- or basin-wide scales using existing hydrodynamic and sediment transport models. To investigate the transport behavior of microplastic particles along the interface between the hyporheic zone and the open water flow domain, smaller-scale models are required so that the complex processes in this region can be adequately represented and analyzed.To this end, a novel modeling technique will be presented based on the open source CFD toolbox OpenFOAM. It combines a new coupling approach for the hydrodynamic processes in the surface water and hyporheic zone with transport modeling of microplastics.The methodology considers the latest findings regarding deposition and resuspension of microplastic particles as well as the hyporheic exchange in a fully coupled model. The model is validated by accompanying flume experiments and relevant transport processes are identified from the presented scenario simulations.

Groundwater inflow into the Spree River and its tributaries is an important factor for the iron precipitation problem of the Spree in the Lusatian mining district (Eastern Germany). The input of dissolved iron into the Spree is difficult to estimate mainly because of unknown groundwater inflow. As part of this study, the radio-active isotope 222-Radon (222Rn) was used as a natural tracer to localize and quantify groundwater inflow into the Spree River and one of its tributaries ( Kleine Spree). Based on two 222Rn monitoring campaigns in the catchment and by applying the 222Rn mass balance model FINIFLUX, we were able to quantify local groundwater inflow for a 20 km long river section of the Kleine Spree and a 34 km long section for the Spree River. For the first campaign in May 2018 total groundwater inflow was estimated with ~3,000 m³/d for the Kleine Spree and ~20,000 m³/d for the Spree River. For the second campaign in August 2018 estimated total groundwater inflows were significantly higher with ~7,000 m3 d−1 (Kleine Spree) and ~38,000 m3 d−1 (Spree). Preferential groundwater inflow areas were identified (with up to 70% of total inflow) along the Spreewitzer Rinne, a local high permeable aquifer consisting of excavated mining materials. Based on a stoichiometric ratio calculation and by measuring instream sulfate and dissolved iron loadings, we additionally were able to estimate iron precipitation rates for the entire catchment of the Spree in the Lusatian mining area. According to our calculations, for the entire catchment of the Spree River in the Lusatian mining district total iron precipitation rates reach values as high as 120 tons/day; large quantities of iron (oxy)-hydroxides that are retained within the catchment as iron precipitates.

Rivers and streams are a primary transport vector for microplastics (MPs), connecting terrestrial sources to marine environments. While previous studies indicated that pore-scale MPs can accumulate in streambed sediments, the specific MPs transport and retention mechanisms in fluvial systems remain poorly understood. We present a novel method for a quantitative analysis of the spatiotemporal transport and retention of pore-scale MPs in an experimental flume. A continuous mass balance for MPs in surface water was achieved using two online fluorometers, while a laser-induced Fluorescence-Imaging-System was developed to track and quantify the spatial migration of MPs through the streambed sediments. The detection limit was

Groundwater represents a major component for runoff generation of large rivers systems. Its quantification is of uttermost importance during low flow periods and in the context of changing runoff dynamics due to climate change.The present study focuses on the surface water-groundwater interaction using the example of the Moselle River, the second most important tributary of the Rhine. The river is classified as a federal waterway and has 12 barrages on German territory to ensure navigability all year round.The research approach is based on the assumption that local groundwater inflow into the Moselle is detectable by increased 222-Rn concentrations in the river and that the δ18O composition of the river water approximates that of the groundwater. Therefore, we applied a numerical model for solving the 222-Rn and Tritium mass balance and a mixing model of δ18O and electrical conductivity.For this purpose, water samples were taken at intermediate flow conditions (gauge Cochem: about 220 m³/s) in October 2020 along the Moselle on a stretch of 242 kilometers at high spatial resolution (every 2 km) to measure stable water isotopes and electrical conductivity. Integrated over the same spatial resolution, in-situ 222-Rn measurements were carried out. Tributaries and selected groundwater monitoring wells were sampled for the same analysis. Precipitation was collected at the station Trier of the German Meteorological Service on a monthly basis. In agreement with this measurement concept, another sampling campaign took place for selected reaches in August/September 2021 at lower discharges (Cochem gauge: about 94 m³/s).In autumn 2020, diffuse groundwater inflow (approx. 0.17 to 0.3 m³/s) was detected for the shell limestone of the upper Moselle reaches and locally increased groundwater inflow for the middle reaches in the transition area to the Rhenish Slate Mountains and the Detzem barrage (approx. 1.4 to 2.4 m³/s). These estimates translate into groundwater contribution of the total Moselle discharge of 0.3 and 1.2 % respectively, which is much lower than those calculated by the mixing model (about 10 and 5 %, respectively). For August/September 2021, higher groundwater inflows in these areas are expected for both methods.The evaluation to date indicates that 222-Rn is the most sensitive tracer to locations with increased groundwater inflow compared to tritium and stable water isotopes. While tritium results seem to strongly depend on the current flow conditions and the propagating river wave, stable isotope results are affected by the appropriate characterization of end-member hydrochemistry.

Rivers and streams are a primary transport vector for microplastics (MPs), connecting terrestrial sources to marine environments. While previous studies indicated that pore-scale MPs can accumulate in streambed sediments, the specific MPs transport and retention mechanisms in fluvial systems remain poorly understood. As part of this technical note, we present a novel method for a quantitative analysis of the spatiotemporal transport and retention of pore-scale MPs in an experimental flume. A continuous mass balance for MPs in surface water was achieved using two online fluorometers, while a laser-induced Fluorescence-Imaging-System was developed to track and quantify the spatial migration of MPs through the streambed sediments. The detection limit was < 1 µg/L for 1 µm polystyrene microbeads with the fluorometers and 3 µg/L for the Fluorescence-Imaging-System. The system was able to quantitatively track the advective transfer of MPs into the streambed sediments: a process that has yet not been observed experimentally. Results showed that MPs infiltrated into the streambed sediments up to a depth twice the bedform amplitude. This work provides a novel experimental method to quantitatively monitor MP transport through porous media and advective exchange of MP across the streambed interface.

Endocrine-disrupting compounds (EDCs), as well as microplastics, have drawn global attention due to their presence in the aquatic ecosystem and persistence in wastewater treatment plants (WWTPs). In the present study, for simultaneous bio-removal of two EDCs, 17α-ethinylestradiol (EE2), bisphenol A (BPA), and a microplastic, polypropylene (PP) four kinds of periphytic biofilms were employed. Additionally, the effect of humic acid (HA) on the removal efficacy of these biofilms was evaluated. It was observed that EE2 and BPA (0.2 mg L

International audience; Key Points: Lumped parameter modeling of hyporheic nitrate removal by applying the exposure time concept.  Exposure time distributions are derived from analytical residence time distributions and reaction kinetics for hyporheic oxygen consumption.  Using exposure times rather than residence times is likely to lead to more realistic estimates for nutrient removal in the hyporheic zone Abstract The rate of biogeochemical processing associated with natural degradation and transformation processes in the hyporheic zone (HZ) is one of the largest uncertainties in predicting nutrient fluxes. We present a lumped parameter (LPM) model that can be used to quantify the mass loss for nitrate in the HZ operating at the scale of river reaches to entire catchments. The model is based on using exposure times (ET) to account for the effective timescales of reactive transport in the HZ. Reach scale ET distributions are derived by removing the portion of hyporheic residence times (RT) associated with flow through the oxic zone. The model was used to quantify nitrate removal for two scenarios: 1) a 100 m generic river reach and 2) a small agricultural catchment in Brittany (France). For the field site hyporheic RT are derived from measured in-stream 222 Rn activities and mass balance modelling. Simulations were carried out using different types of RT distributions (exponential, power-law and gamma type) for which ET were derived. Mass loss of nitrate in the HZ for the field site ranged from 0-0.45 kg d-1 depending on the RT distribution and the availability of oxygen in the streambed sediments. Simulations with power law ET distribution models only show very little removal of nitrate due to the heavy weighting towards shorter flow paths that are confined to the oxic sediments. Based on the simulation results, we suggest that ET likely lead to more realistic estimates for nutrient removal.

Hyporheic flow and nutrient turnover in hyporheic systems are strongly influenced by in-stream bedforms. An accurate representation of topographical variations of the stream-streambed interface is therefore essential in analytical models in order to represent the couplings between hydrological and biogeochemical processes correctly. The classical Toth approach replaces the streambed surface topography by a flat surface which is identical to a truncation of the original physical flow domain into a rectangle. This simplification can lead to biased estimates of hyporheic flow and nutrient cycling within hyporheic systems. We present an alternative analytical modeling approach for solving hyporheic problems without domain truncation that explicitly accounts for topographical variations of the streambed. The presented approach is based on the application of perturbation theory. Applications of the method to hyporheic systems, ranging from the centimeter-scale of rippled bedforms to riffle structures of 10 m and larger scale, indicate a high accuracy of the approach.

Microplastic particles (MPs) are a major threat to ecosystems worldwide, resulting in a great need to investigate their impacts on ecosystems. To date, most studies dealing with the effects of MPs on organisms used commercially available polystyrene spherical particles, with no to little characterization of their physicochemical properties. However, MPs occurring in the environments are a composition of various polymer types with different properties. Therefore, it is hard to tell how and if the polymer type and its associated properties determine their impact on organisms. Here we show how different polymer types of MPs in the same shape, concentration, and size range (20-120µm) affect the freshwater mussel Dreissena bugensis in comparison to mussel shell fragments as natural particle control. By using hall sensor-based real-time valvometry, we studied behavioural responses via the movement of the mussels' valves and show that mussels cannot distinguish between natural particles and MPs. Furthermore, we performed an in-depth characterization of the used MPs. Different types and quantities of additives and residual monomers were found in the different polymer types, which can be linked to polymer type-dependent adverse effects on the molecular level. Recycled PET elicited the most substantial adverse effects on D. bugensis, likely caused by anthranilamide, anthranilonitrile and butylated hydroxytoluene within the MP fragments, which have been described as toxic to aquatic organisms. Since PET is among the most abundant MPs found in nature, sublethal effects may gradually manifest at the population level, leading to irreversible ecosystem changes. In summary, adverse effects in organisms caused by MPs are dependent on specific physical and chemical properties of the particles. Also see: https://micro2022.sciencesconf.org/428254/document, In MICRO 2022, Online Atlas Edition: Plastic Pollution from MACRO to nano

Clay minerals are important constituents of porous media. To date, only little is known about the transport and retention behavior of nanoplastics in clay-containing soil. To investigate the effects of clay minerals on the mobility of nanoplastics in saturated porous media, polystyrene nanoplastics (PS-NPs) were pumped through columns packed with sand and clay minerals (kaolinite and illite) at different pH and ionic strengths (IS). Mobility of PS-NPs decreased with increasing clay content attributed to physical straining effects (smaller pore throats and more complex flow pathways). Variations in pH and IS altered the surface charges of both PS-NPs and porous media and thus affecting the interaction energy. An increase of IS from 10 mM to 50 mM NaCl decreased the maximum energy barrier and secondary minimum from 142 KBT to 84 KBT and from -0.1 KBT to -0.72 KBT, respectively. Thus, the maximum C/C0 ratio decreased from ~51% to ~0% (pH 5.9, 3% kaolinite). Among the two clay minerals, kaolinite showed a stronger inhibitory effect on PS-NPs transport compared to illite. For instance, at the same condition (3% clay content, pH 5.9, 10 mM NaCl), the (C/C0)max of PS-NPs in kaolinite was ~51%, while for illite, it was ~77%. The difference in transport inhibition was mainly attributed to amphoteric sites on the edges of kaolinite which served as favorable deposition sites at pH 5.9 (pHpzc-edge is ~2.5 for illite and ~6.5 for kaolinite). Besides, the morphology of kaolinite was more complex than illite, which may retain more PS-NPs in kaolinite. Results and conclusions from the study will provide some valuable insights to better understand the fate of NPs in the soil-aquifer system.

Bank filtration is a cost-effective and sustainable method of improving surface water quality for drinking water production. During aquifer transit, natural biodegradation and physiochemical filtration improve the quality of the raw water by removing sediments, pollutants, and pathogens. Strict regulations prohibit the use of substances that can be used to estimate aquifer residence times to define water protection areas for bank filtration. In this study, we present a novel measurement and modeling framework for deriving mean aquifer residence times for bank filtrate using the natural tracer radon-222. The method is intended for application in the drinking water sector, where extraction wells are screened over the entire aquifer and pumps are operated at high production rates. Mean aquifer residence times are estimated using composite residence time distributions that account for flow path mixing and non-uniform residence times with multiple components including bank filtrate, shallow groundwater, and deep groundwater. The mathematical framework is demonstrated for a drinking water production facility. Radon activities for the six monitored extraction wells ranged between 4,400 and 8,400 Bq/m³. Estimated mean aquifer residence times for the wells range from5 days to 110 days and strongly depend on i) the type of residence time distribution model (exponential, gamma or piston flow), ii) the mixing ratio between bank filtrate and local groundwater, and iii) the heterogeneity in the groundwater endmember. By accounting for mixing processes, we can show that radon can be used beyond the "5-fold half-life" (~20 days) commonly described in the literature as the upper limit for age dating purposes for radon. This method provides a simple and cost-efficient way to quantify residence times of bank filtrate on a regular basis without any addition of external substances to the aquifer.

The increasing use of plastic products and its inevitable decomposition after improper disposal has led to large numbers of nano- and microplastic in aqueous environments. There is currently a critical need to investigate the transport and retention mechanisms of nanoplastic particles in water-saturated porous media (e.g., aquifers or sediments) to better understand residence times and ecosystem exposure of these particles in aqueous environments. In this study, we performed a set of column experiments in order to investigate and understand the primary controls on the mobility of nanoplastics in a controlled laboratory environment. As part of the experiments, we used polystyrene nanoplastic particles (PS-NPs, 50 nm) in combination with iron oxyhydroxide–coated sand, which is known for its high surface reactivity and often can be found in natural systems in environmentally relevant amounts. We also adjusted pore water chemistry (pH, ionic strength, cation species) to represent non-uniform geochemical conditions in nature and to understand how these conditions quantitatively affect the transport of nanoplastics. Mobility and retention of PS-NPs were assessed by analyzing breakthrough curves. For negatively charged iron oxyhydroxide coatings (at pH > pHpzc), only little retention of PS-NPs could be observed. In contrast, positively charged iron oxyhydroxide coatings (pH < pHpzc) provided favorable deposition sites for the negatively charged PS-NPs. DLVO theory was used to show that high pH and low ionic strength increased the energy barriers between PS-NPs and the porous media. In contrast, low pH and high ionic strength decreased the barriers and thus increased retention in the columns. Finally, bridging agents, such as Ca2+ and Ba2+, resulted in the significant deposition of nanoplastics by forming bonds between O-containing functional groups on both the plastic and sediment surfaces. These findings indicate that the deposition and fate of nanoplastic particles are strongly affected by the water chemistry and soil components in subsurface environments.

Plastics are among the most widespread contaminants on Earth. They build up in fresh water bodies with high concentrations and migrate between different environmental compartments. In thermally stratified lakes, in summer, MPs pollutants can migrate between epilimnion, metalimnion and hypolimnion. This increases the probability of that microplastic will be filtered by filter feeders allowing MPs to migrate through different trophic levels. In this study, the transport of MPs in lake systems is presented through laboratory experiments as well as numerical modelling. The settling velocities of various biodegradable and non-biodegradable particles with various shapes and sizes were measured in the settling column under laminar conditions using particle image velocimetry (PIV). The particles used ranged between 150 to 2400 µm in diameter. The experimental results presented that shape, size and density of a particle are the key parameters controlling the sedimentation behavior of the particles. The measured settling velocities ranged between 0.4 to 50 mms-1. In parallel, the transport of the particles used in the laboratory experiments was simulated using CFD. The laboratory experiments and CFD have shown consistent results. Subsequently, the same MPs used in the first lab experiments were incubated in a pond at the University of Bayreuth for 6, 8 and 10 weeks. The formation of biofilm on the incubated particles was investigated using confocal laser scanning microscopy. Also, the effect of biofouling of microplastics on the physical properties and thus settling velocity was investigated experimentally. It was observed that biofilm-building organisms has only colonized few regions on the surface of MPs and the whole surface was not coated with biofilm as it was anticipated. In addition, no changes in shape, size and density of the incubated were detected. After 6, 8 and 10 weeks of incubation, no significant change in the settling velocity of the incubated particles was observed. The detected changes in the settling velocity ranged between ± 5 % which was considered as a measurement error. Finally, the residence time in suspension and the distribution of MPs throughout a virtual lake water column was simulated using a simplified model. The effect of turbulences and the temperature gradient on the settling velocity were considered during the simulations. The model presented that turbulences, water temperature and layer depth control the settling velocity and thus the residence time of the MPs.

Rivers and streams are the dominant transport vectors for microplastic (MP) input into marine environments. During transport, complex physicochemical interactions between particles, water and river sediments influence particle mobility and retention. The specific transport mechanisms of MP in fluvial systems are not yet fully understood, and the main reason lies in the limitation in reliable data derived from experimental analysis.In our subproject of the ‘CRC 1357 Microplastics’, we investigate the hydrodynamic mechanisms that control the transport and retention behavior of MP in open channel flows and streambed sediments. In an experimental flume environment, we create realistic hydrodynamic and hyporheic flow conditions by using various porous media (e.g. glass beads or sand) and bedform structures (e.g. riffle-pool sequences, ripples and dunes), modelled from real stream systems.The method developed here can quantitatively analyze the transport of pore-scale particles (1-40 µm) based on fluorometric techniques. Particle velocity distributions and particle transport are measured using Particle-Image-Velocimetry and Laser-Doppler-Velocimetry. With our setup, we can quantitatively investigate time-resolved MP transport and retention through the aqueous and solid phase in a flume scale experiment.

Our study discusses imaging results from a spectral induced polarization (SIP) survey to identify concurring processes (such as aerobic respiration, denitrification, or sulfate- and iron reduction) in a biogeochemically active peat in a wetland located in the Lehstenbach catchment in Southeastern Germany. Terrestrial wetland ecosystems such as peatlands are a critical element in the global carbon cycle. Due to their role as natural carbon sinks and ecological importance for an array of flora and fauna, there is a growing demand to conserve and restore degraded peatlands. Biogeochemical processes occur with non-uniform reaction rates within the peat, making the environment sensitive to physical disturbances. To investigate biogeochemical processes in-situ, it is important to avoid disturbing the redox-sensitive conditions in the subsurface by bringing oxygen into anoxic areas. Our previous study demonstrated that the induced polarization (IP) was able to identify biogeochemically active and inactive areas of the peat. The IP response was sensitive to the presence of carbon turnover and P release in the absence of iron sulfide. These highly polarizable areas have high iron concentrations, but most likely in an oxidized form. As most iron oxides are poor conductors, the strong polarization response is unlikely related to an electrode polarization process.Here we also analyzed the frequency dependence of the SIP data to investigate whether iron oxides and carbon-iron complexes, two possible mechanisms for the high polarization response, can be distinguished. SIP imaging data sets covered the frequency range between 0.06 and 225 Hz and were collected with varying electrode spacing (20 and 50 cm) at different locations within the Waldstein catchment characterized by different properties, e.g., saturated and non-saturated soils. Our imaging results reveal variations of the IP effect within the peat layer, indicating substantial heterogeneities in the peat composition and biogeochemical activity. The frequency dependence allowed us to resolve a sharper contrast between the different features of the peat. Geochemical analyses on a freeze core and pore water samples are used to validate our results and find correlations between the Cole-Cole parameters of the SIP response and the geochemical parameters.

Radon (222Rn) is widely used as a natural tracer to investigate surface/groundwater interactions for hydrological systems. Because 222Rn activities in groundwater are higher compared to surface water, it can be used to quantify groundwater inflow rates into rivers and streams. Here we present a process-based model to simulate 222Rn emanation and transport in groundwater to investigate surface/groundwater interactions for the Große Ohe catchment, located in the Bavarian Forest National Park (Germany). For representing surface and groundwater flow in the catchment as well as transport, decay, and emanation of 222Rn, the processed based hydrological model HydroGeosphere (HGS) is used. HGS is an integrated surface sub-surface hydrological model (ISSHM) which can simulate reactive transport in surface and sub-surface flow. The model was calibrated using measured in-stream 222Rn activities and continuous discharge observations. Main objective of this study is to investigate runoff generation in the catchment and how hydrological processes are affecting the age and residence time composition of groundwater.

Biogeochemical hot spots are defined as areas where biogeochemical processes occur with anomalously high reaction rates relative to their surroundings. Due to their importance in carbon and nutrient cycling, characterization of hot spots is critical to accurately predict carbon budgets in the context of climate change. However, biogeochemical hot spots are difficult to identify in the environment, as sampling resolutions are often too coarse to find these areas in the subsurface. Here, we present imaging results of a geophysical survey using the non-invasive induced polarization (IP) method to identify biogeochemical hot spots of carbon turnover in a minerotrophic wetland. To interpret the field-scale IP signatures, geochemical analyses were performed on freeze-core samples obtained in areas characterized by anomalously high and low IP responses. Our results reveal large variations in the electrical response, with the highest IP phase values (> 20 mrad) corresponding with high concentrations of phosphates (> 4000 μM), an indicator of carbon turnover. Moreover, analysis of the freeze core reveal negligible concentrations of iron sulfides. The extensive geochemical and geophysical data presented in our study demonstrates that IP images can assess changes in the biogeochemical activity in peat, and identify hot spots.

Summary We demonstrate the application of the induced polarization (IP) imaging method to map biogeochemical hot-spots at the catchment scale. Measurements were collected at the Hydrological Open Air Laboratory (HOAL), a 66 ha. research field. Data collected across the entire site reveal relative modest electrical conductivity values (between 60 and 80 mS/m) and low polarization values (quadrature conductivity 1 mS/m and conductivity phase above 20 mrads). Mapping IP lines permitted to delineate the geometry of the IP anomaly and select the location for the drilling of boreholes. Analysis of the sediments revealed high carbon and iron concentrations, as expected for a biogeochemically active area; however, negligible concentration of sulfides or magnetite which are the common IP targets. Although the polarization mechanism is open to debate, our results demonstrate the applicability of the IP method as a diagnosis tool to delineate in-situ biogeochemical activity in metal-free media.

Although a major part of marine microplastic (MP) pollution originates from rivers and streams, the mechanistic behavior of MP in fluvial systems is only poorly understood. MP enter fluvial systems from e.g. waste water treatment plant (WWTP) effluents, sewer overflows during heavy rain events, agricultural runoff, aerial input/atmospheric fallout, road runoff or via fragmentation of plastic litter. As part of this project we want to investigate the hydrodynamic transport mechanisms that control the behavior and re-distribution of MP in open channel flow and the streambed sediments. Hydrodynamic conditions in open channel flow are represented in an experimental flume environment. Different porous media materials (e.g. aqua beads, glass beads and sand) are used in the flume experiments to shape typical bed form structures such as riffle-pool sequences, ripples and dunes. The aim of this experimental setup is to create hydrodynamic flow conditions such as hydraulic jumps, low and high flow velocity environments for which the transport and sedimentation behavior of MP can be investigated under realistic conditions. Hydrodynamic flow conditions in the flume are characterized using a Laser-Doppler-Anemometry (LDA) and Particle Image Velocimetry (PIV). Detection and tracking of fluorescent MP-particles in open channel flow and in porous media will be achieved with a fluorescence-camera-system.

Headwater catchments with wetlands represent important buffer areas by decreasing peak discharges and providing water in meteorological droughts. Wetlands act also as key feature of the riverine carbon cycle and are able to store significant amounts of carbon. Therefore, understanding and predicting discharge generating processes in the context of climate change is essential for such catchments. We use a Regional Climate Model (RCM) Ensemble to study possible changes in discharge patterns due to climate change at the Lehstenbach catchment, located in the Fichtelgebirge Mountains. Our aim is to quantitatively estimate periods of hydrological droughts and floods, their temporal length and intensity, their recurrence intervals as well as possible connections to snow melt. In order to achieve this goal, we use the process-based model HydroGeoSphere to simulate discharge until 2100 based on the RCM Ensemble. Statistical Analysis, including Trend and Wavelet Analysis aids us in detecting changing discharge conditions. Discharge seems to follow an increasingly variable pattern making droughts and floods more likely in the future. Since the overall length of drought conditions increases although precipitation amounts remain fairly stable, we identified evapotranspiration and altered precipitation patterns as main driving forces of droughts in this headwater. Snow conditions and subsequent spring floods seem to decrease in likelihood until 2100.

The two primary problems currently facing agriculture are drought and the availability of mineable phosphorus minerals used for fertilization. More frequent and longer drought periods are predicted to threaten agricultural yields in future. The capacity of soils to hold water is a highly important factor controlling drought stress intensity for plants during the growing phase. High phosphorus availability in soils is necessary for high agricultural yield. For both drought and phosphorus availability in soils amorphous silica (ASi) has been suggested to be able to mitigate these problems. Amorphous silica pools in natural soils are in the range of 0-6%. However ASi pools have declined in agricultural soils since the development of high intensity agriculture to values of 40% and >60%, respectively. Additionally, we fertilized soils with ASi and measured phosphorus mobilization from the solid phase into the soil pore waters. We found a strong mobilization of phosphorus by ASi. In a lysimeter experiment we found that ASi strongly increased the WHC of soils. Furthermore, as expected from the batch experiments the ASi is decreased phosphorus sorption to soil minerals and consequently increased its mobilization. Our results suggest that ASi addition to soils enhances the water availability, potentially decreases drought stress for plants as well as increasing phosphorus mobility in soil of terrestrial ecosystems.

With the increasing use of nanoplastic products in our daily life, these particles will invariably enter into the subsurface environment. It is, therefore, vital to understand the transport and retention of nanoplastic particles in groundwater systems. Surface charge heterogeneity is one of the basic chemical-physical characteristics of aquifer materials, but little research has been conducted on this topic. This study aimed to understand how the interaction between the porous media, solution chemistry, and NP surface charge influences the transport and retention of PS-NPs in the subsurface. 25 mg/L polystyrene nanoplastic particles (PS-NPs) were injected into columns packed with iron oxyhydroxide-coated sand. In addition, factors such as the content of iron oxyhydroxide-coated sand (λ), pH, ionic strength (IS), and cation valence were systematically studied. DLVO theory was used to evaluate the interactions between PS-NP and the porous media. By comparing the breakthrough curves (BTCs) of PS-NPs, it was clear that all these variables exerted a significant influence on the mobility of PS-NPs in the columns. These effects could be explained by the following: Firstly, by applying the DLVO theory, it was possible to model the electrostatic interaction between quartz sand and PS-NPs. For instance, at different IS (NaCl), the maximum energy barrier (Φmax) decreased with an increase in IS, which meant PS-NPs could more easily overcome the energy barrier to deposited on the sand surface at higher IS. Secondly, the positively charged iron oxyhydroxide coating provided additional favorable deposition sites for negatively charged PS-NPs. However, when the pH of the solution exceeded the iron oxyhydroxide pHpzc (~pH 9), the iron coating became negative and increased the mobility of PS-NPs. Finally, bridging agents, such as Ca2+ and Ba2+, resulted in the significant deposition of PS-NPs on the sand due to the bridging effect connecting the porous media and PS-NPs through the O-containing functional groups on both plastic and mineral surfaces. This study provides a better understanding of how the charge heterogeneity on aquifer materials and groundwater hydrochemistry affect the transport of PS-NPs in aquifers.

Microplastics (MPs) have been found ubiquitously in oceanic and terrestrial environments. As the production and consumption of plastic polymers increases the amount of plastic evading accepted disposal pathways and entering natural systems is also expected to increase. To date the focus of plastic and MP research in particular has been on the ocean, there has recently been a rapid increase in interest in MP levels and distribution in terrestrial systems. However, the focus of existing studies has mostly been on the quantification and distribution of MP contamination in the sediment or on the water column of rivers and lakes. The aim of this project is to investigate the fundamental physical and biological influences on the transport of microplastics (MPs) in lake systems. In particular, we will focus on an understanding of the migration and distribution of MPs, and a systematic investigation on transport and sedimentation of MP in the lake water column. Lab and field experiments are planned to investigate the behavior of different MPs polymers, shapes and sizes under different conditions and determine how this influence the MP transport.The settling velocity of MPs in stationary water was measured in the laboratory using particle image velocimetry (PIV) which was then compared to manual timing of the sinking velocity. The trajectories of the settling MPs have also been tracked during weak turbulences. In addition, the results were compared with theoretical calculations.To investigate microbial colonization and biofilm formation on the surface of MPs, samples were exposed on a natural lake environment for varying time periods. The colonization of MP surfaces by microorganisms and their excretion of extracellular polymeric substances (EPS) were examined by laser microscopic techniques and subsequently the effect of the microbiological colonization of settling velocity was determined. In this work we show that the transport of MP is complex, as it is influenced by plastic type, shape, and biological colonization as well as the hydrodynamic conditions in the lake water column.

Biogeochemical hot spots are spatially confined areas where biogeochemical processes take place with anomalously high reaction rates. On the landscape scale, biogeochemical hot spots are of major interest due to the possible emission of greenhouse gases (carbon dioxide) and high nutrient turnover. Such hot spots are sensitive environments and given their environmental impact, there is a growing demand for noninvasive methods to investigate such hot spots without disturbing the biogeochemical settings. Classical geochemical sampling methods (e.g., piezometers or suction cups) often disturb the redox-sensitive settings by bringing oxygen into anoxic areas. Induced polarization (IP) is a noninvasive geophysical method that was initially developed to explore metal-ore deposits but more recently developed into a versatile tool for environmental studies. Here, we present imaging results from a geophysical survey using the IP method to characterize hot spots in a wetland located in the Lehstenbach catchment in Southeastern Germany. We collected IP imaging data sets along 64 profiles using 64 electrodes deployed with a spacing of 20 cm. Our highly resolved measurements aimed at delineating hot spots within a thin layer (approximately 20 cm) heterogeneous peat material on top of the local granite bedrock. To validate the field-scale IP signatures, geochemical analyses (e.g., dissolved and solid iron concentration) were performed on freeze-core samples obtained in areas characterized by anomalous high and low IP responses. Furthermore, the thickness of the peat was measured with a dipstick along every fifth profile to evaluate the IP imaging results. Our imaging results reveal an increase in the IP response within the upper 20 cm of the subsurface, which correlates with the variations in the iron concentrations and variations in the geochemical composition of groundwater accompanying microbial activity within the biogeochemical hot spots observed in the soil samples. The IP response decreases in the deeper regions, which can be associated with the granite bedrock.

Changing climatic drivers significantly endanger the function of the hyporheic zone (HZ). Increased temperature leads to an increase in respiration and expansion of anoxic areas in river sediments. Under conditions of low stream discharge (with high proportion of groundwater) reduced substances enter the upper parts of the HZ and surface water. Contact with dissolved oxygen (DO) leads to formation of areas of preferential oxidation of reduced substances (e.g. iron precipitation and clogging of pore spaces, nitrification). Thus oxygen levels in the hyporhic zone are an important parameter for understanding biogeochemical cycles in the stream sediments. However, oxygen measurements are time consuming, prone to error and instruments are expensive.In this work we hypothesize that iron nails can be used as a very simple and inexpensive tool for mapping the depth of oxygen penetration into hyporheic sediments. The experiments compared iron oxidation of nails inserted in a laboratory scale sand tank model for hyporheic flow as well as a riffle-pool sequence in northern Bavaria, Germany. We have combined this with a mathematical model that simulates flow and biogeochemical reactions in the subsurface and with direct oxygen measurements in the sediment.Oxygen measurements showed that oxygen concentrations decrease from over 8 mg l-1 to less than 1 mg l-1 in the first 15 cm of the tank model. This agreed well with the mathematical model, which predicted the decrease of oxygen to approximately the same depth. The nails showed a clear rust (iron oxide) crust down to sub-oxic DO levels (at ~11 cm) while below this we observed a black precipitate indicating reducing conditions. In some cases, we found an area between the oxic and anoxic zones where there were no obvious signs of reaction on the nails surface. The mathematic model indicated that the water residence time in the oxic part of the tank was ~5 h while it took up to 19 h to pass through the anoxic zone and out of the tank.The field results confirms that rust on the nails can be used to indicate oxic depths, but with a somewhat more complex pattern along the riffle-pool sequence.Iron oxidation and associated rust on the metal nails gives us only qualitative data on the presence or absence of Oxygen. Quantitative data may be derived by determining the iron mineral phases on the nails (using e.g. Raman spectroscopy). Overall this appears to be a very inexpensive method for gaining high spatial resolution information of oxygen levels in the hyporheic zone, which is important for stream ecosystems as well as biogeochemistry.

The spatial distribution and temporal dynamics of groundwater inflow to rivers is often poorly defined but central to understanding water and matter fluxes. This is especially true for the Spree River which drains the Lusatia mining district, Brandenburg Germany. In the Spree catchment iron and sulphate fluxes to the river stem from the pyrite rich groundwater system, and the area’s history of open-pit lignite mining and re-flooding of many of these mines at the end of their lifetime. This iron flux threatens the river ecosystem, tourism in downstream communities (Spreewald) and the drinking water of Berlin. Iron is often observed as precipitates along the river bed, as well as colouring the river water yellow-brown, indicating the presence of iron (oxy)hydroxides such as ferrihydrite and goethite. In this work we have used radon as a natural groundwater tracer to delimited areas of active groundwater discharge to both the main Spree River and the Kleine Spree River to better understand the spatial destitution of groundwater input to the system. This was combined with mass-balance modelling to quantify the groundwater flux along the river using the FINIFLUX model. This was complemented by measurement of iron and sulphate concentrations in the steam and stream-near groundwater. During two measurement campaigns during 2018 the total groundwater inflow for a 20 km long reach of the Kleine Spree and a 34 km long reach of the Spree ranged between ~3,000 and ~7,000 m³ d-1 (Kleine Spree) and ~20,000 and ~38,000 m³ d-1 (Spree). Particularly high groundwater inflow was identified (up to 70% of total inflow) along the Spreewitzer Rinne, a local aquifer consisting of excavated mining materials. For the Kleine Spree the dominant groundwater and Fe flux occurred shortly before the confluence with the Spree. For these river reaches large amounts of dissolved iron and sulphate enters the rivers with inflowing groundwater as calculated from the radon data. Using the measured iron and sulphate loadings we calculated that up to 120 tons/day of iron (oxy)hydroxide was retained in the combined Spree and Klein Spree catchments, a large amount of which remains in the mining lakes.

Transient storage zones (TSZs) are located at the interface of rivers and their abutting aquifers and play an important role in hydrological and biogeochemical functioning of rivers. The natural radioactive tracer Rn is a particularly well-suited tracer for studying TSZ water exchange and age. Although Rn measurement techniques have developed rapidly, there has been less progress in modeling Rn activities. Here, we combine field measurements with the numerical model HydroGeoSphere (HGS) to simulate Rn emanation, decay and transport during steady state (riffle-pool sequence) and transient (bank storage) conditions. Comparing the HGS mean water ages with the conventional Rn apparent ages during steady state showed a systemic underestimation of apparent age with increasing dispersion and especially where large concentration gradients exist within the subsurface. A large underestimation of apparent water age was also observed at the advective front during bank storage where regional high Rn groundwater mixes with newly infiltrated surface water. The explicit modeling of radiogenic tracers such as Rn offers a physical interpretation of this data as well as a useful way to test simplified apparent age models.

Quantifying and upscaling chemical turnover in the hyporheic zone (HZ) is difficult due to limited reaction rate data, unknown carbon quality, and few methods for upscaling local measurements to river networks. Here we develop a method for quantifying reaction kinetics in situ in the HZ and upscaling biogeochemical turnover to catchment scales. Radon-222 was used to quantify water residence times in the HZ of the Roter Main River (RM), Germany. Residence times were then combined with O2, NO3−, CO2, DOC, and carbon quality (EEMs, SUVA) data to estimate Monod and first-order reaction rates. Monod parameters µmax and ksat for NO3− reduction were 11 µmol l−1 h−1 and 52 µmol l−1, respectively, while the first-order rate was 0.04 h−1. Carbon quality was highly bioavailable in the HZ and is unlikely to be limiting. Reaction kinetics was incorporated into the FINIFLUX model to upscale NO3− mass loss over a 32 km reach of the RM. The aims were to (1) to estimate hyporheic efficiency using Damkohler numbers (Da), and (2) calculate NO3− mass loss in the HZ over the reach. The Da analysis suggests that the hyporheic zone is inefficient for NO3− processing, however, this is somewhat misleading as the largest NO3− mass loss occurs at the shortest residence times where Da ≪ 1. This is due to the largest water flux occurring in the uppermost part of the sediment profile. Nitrate processing in the HZ accounted for 24 kg NO3− h−1 over the reach, which was 20% of the NO3− flux from the catchment.

Radon (R86222n) as a hydrological tracer offers a method for studying short to medium term groundwater - surface water interactions. These high frequency processes play an important role in wetland hydrology and biogeochemistry and may influence their contribution to the global carbon cycle. Therefore, there is a definite need for robust methods to measure high resolution

Coastal ecosystem health and sustainability is tightly coupled to submarine groundwater discharge (SGD) and associated nutrient, carbon and pollutant fluxes. However, there are few studies that systematically analyse the interaction between the terrestrial aquifer system, catchment morphology and coastal SGD. The objective of this study was to evaluate the role of catchment morphology and how this influences the spatial distribution, timing and volume of the SGD flux to a branched tidal creek system, on the barrier island Spiekeroog, Germany. The subsurface salinity was mapped using electrical resistivity tomography (ERT) and a hydrogeochemical survey of the shallow groundwater. Temporal and spatial analysis of geochemical tracers (radon-222, chloride) in the tidal creek water was integrated into a transient 222Rn mass balance model for quantification of SGD rates during two field campaigns that encompassed spring and neap tides. The ERT mapping indicated that fresh groundwater dominated under the dune ridges down to about 15 m depth, but became progressively more brackish seawards. This is likely due to frequent tidal and storm flooding of low-lying areas. The highest groundwater fluxes into the creek were indicated by high 222Rn activities (average 468 Bq m−3) towards the dune ridge. Chloride concentrations (up to 17.3 g L−1) increased seawards showing the progressive salinization of water in the creek. The freshwater component of SGD was highly variable in time but was highest at low tide, while the total SGD flux (saline + fresh) was highest when tides changed from inflow to outflow as the rapid pressure release on the local aquifer caused a large hydraulic gradient towards the creek. Comparing the freshwater component of mean daily SGD to the creek with estimated groundwater recharge rates in the catchment (665 m3 d−1) shows that the fresh groundwater discharge exceeds fresh recharge during spring tides (~120%) but is was lower than recharge during neap tides (~27%). In this study we show that tidal creeks and their relation to catchment morphology are relevant for understanding the spatial and temporal exchange of fresh and saline water between the catchment and coastal zone.

The flux of water, nutrients, carbon and salt through the subsurface at the land-sea interface is an important control on coastal nutrient processes, salinization of coastal aquifers and carbon balances of the coastal zone. However, these fluxes are often spatially and temporally complex and difficult to quantify, especially in high-energy mesotidal systems. Here we use vertical temperature profiles along a morphologically complex mesotidal high-energy beachface to map and quantify water infiltration and exfiltration on the island of Spiekeroog, Germany. Water fluxes were quantified using heat transport calculations from three solutions to the 1D heat transport equation, and include 1) a steady state analytical solution, 2) a non-steady state numerical model and 3) a non-steady state analytical solution. The temperature profiles could clearly map areas of upwelling warm (up to 10 °C) groundwater during the winters of 2018 and 2019. These upwelling zones were focused on an intertidal runnel system and at the low water line, consistent with the current understanding of the site based on visual observations and hydrogeological models. The steady state model provided good fits to the measured data in the winter when the seawater temperatures were not changing significantly, but was less able to reproduce the measured profiles in spring when seawater was warming. The steady state flux rates ranged from −110 to −43 mm d−1 in the runnel and low water line to +43 mm d−1 towards the high water line. The dynamic numerical model successfully captured the propagation of the seawater temperature signal into the subsurface and was able to reproduce the temperature profiles during both seasons. The flux estimates tended to be larger with the numerical model, with up to −150 mm d−1 in the runnel and +110 mm d−1 towards the high water line. The non-steady state analytical solution could only be applied to a limited time series due to the difficulty of logging temperatures in the subsurface at this highly dynamic site. Up to 1.5 days of data suggested fluxes that were considerably higher than the other two methods with best-estimates of −400 to −900 mm d−1. Thermal Peclet numbers ranged from 0.2 to 2 suggesting that both conduction and advection of heat is important. This study demonstrates that the morphology of the beach face is an important control on spatial distribution of down-welling and upwelling zones along the beach and that temperature measurement combined with heat modelling are potentially useful methods for understanding the interactions between groundwater and the sea.

Summary The concept of Damkohler numbers have been extensively used in the discipline of chemical engineering and lately increasingly found its application into environmental science in order to describe the integrated behavior of hydrological systems with respect to their physical transport and biogeochemical transformation capabilities. Defining characteristic time scales of transport and reaction, as part of the Damkohler concept, however is not trivial especially for non-well mixed systems like catchments where physically controlled transport and biogeochemical moderated reactions can be highly variable among individual flow paths. Often, system specific residence times alone are not useful to describe the timescales of transport in the Damkohler concept, because it neglects that degradation of redox-sensitive compounds depend on dynamically changing and non-uniformly distributed hydro-biogeochemical boundary conditions that either facilitate or suppress biogeochemical reactions. In this study an approach is presented that highlights the importance to specifically distinguish between residence and exposure times if system specific transformation efficiencies are evaluated. We investigate the inter-relationship between residence and exposure time distributions for different biogeochemical processes in a virtual wetland environment that is exposed to different hydrological conditions. The relationship between exposure and residence times is mathematically described by a composition matrix that linearly relates the two identities to each other. Composition matrices for different hydrological conditions are analyzed by using the singular value decomposition technique. Results show that especially the type of couplings between the surface and subsurface flow domain control how exposure and residence times are related to each other in the wetland system and that timescales of residence and exposure typically differ by orders of magnitude. Finally, results also indicate that the assessment of system specific transformation efficiencies can be very error-prone if residence instead of exposure times are being used to derive system specific Damkohler numbers.

The highly dynamic processes within a hillslope-riparian-stream (HRS) continuum are known to affect streamflow generation, but are yet not fully understood. Within this study, we simulated a headwater HRS continuum in western Luxembourg with an integrated hydrologic surface subsurface model (HydroGeoSphere). The model was set up with thorough consideration of catchment-specific attributes and we performed a multi criteria model evaluation (4 years) with special focus on the temporally varying spatial patterns of surface saturation. We used a portable thermal infrared (TIR) camera to map surface saturation with a high spatial resolution and collected 20 panoramic snapshots of the riparian zone (approx. 10 m x 20 m) under different hydrologic conditions. Qualitative and quantitative comparison of the processed TIR panoramas and the corresponding model output panoramas revealed a good agreement between spatiotemporal dynamic model and field surface saturation patterns. A double logarithmic linear relationship between surface saturation extent and discharge was similar for modeled and observed data. This provided confidence in the capability of an integrated hydrologic surface subsurface model to represent temporal and spatial water flux dynamics at small (HRS continuum) scales. However, model scenarios with different parameterizations of the riparian zone showed that discharge and surface saturation were controlled by different parameters and hardly influenced each other. Surface saturation only affected very fast runoff responses with a small volumetric contribution to stream discharge, indicating that the dynamic surface saturation in the riparian zone does not necessarily imply a major control on runoff generation. This article is protected by copyright. All rights reserved.

Summary Coupling surface and subsurface water flow in fully integrated hydrological codes is becoming common in hydrological research; however, the coupling of surface–subsurface solute transport has received much less attention. Previous studies on fully integrated solute transport focus on small scales, simple geometric domains, and have not utilised many different field data sources. The objective of this study is to demonstrate the inclusion of both flow and solute transport in a 3D, fully integrated catchment model, utilising high resolution observations of dissolved organic carbon (DOC) export from a wetland complex during a rainfall event. A sensitivity analysis is performed to span a range of transport conditions for the surface–subsurface boundary (e.g. advective exchange only, advection plus diffusion, advection plus full mechanical dispersion) and subsurface dispersivities. The catchment model captures some aspects of observed catchment behaviour (e.g. solute discharge at the catchment outlet, increasing discharge from wetlands with increased stream discharge, and counter-clockwise concentration–discharge relationships), although other known behaviours are not well represented in the model (e.g. slope of concentration–discharge plots). Including surface–subsurface solute transport aids in evaluating internal model processes, however there are challenges related to the influence of dispersion across the surface–subsurface interface, and non-uniqueness of the solute transport solution. This highlights that obtaining solute field data is especially important for constraining integrated models of solute transport.

The dynamic response of groundwater discharge to external influences such as rainfall is an often neglected part of water and solute balances in wetlands. Here we develop a new field platform for long-term continuous 222 Rn and electrical conductivity (EC) measurements at Sale Wetland, Australia to study the response of groundwater discharge to storm and flood events. The field measurements, combined with dynamic mass-balance modelling, demonstrate that the groundwater flux can increase from 3 to ∼20 mm d −1 following storms and up to 5 mm d −1 on the receding limb of floods. The groundwater pulses are likely produced by activation of local groundwater flow paths by water ponding on the surrounding flood plains. While 222 Rn is a sensitive tracer for quantifying transient groundwater discharge, the mass-balance used to estimate fluxes is sensitive to parameterisation of gas exchange ( k ) with the atmosphere. Comparison of six equations for calculating k showed that, based on parameterisation of k alone, the groundwater flux estimate could vary by 58%. This work shows that neglecting transient processes will lead to errors in water and solute flux estimates based on infrequent point measurements. This could be particularly important for surface waters connected to contaminated or saline groundwater systems.

A quantitative understanding of groundwater-surface water interactions is vital for sustainable management of water quantity and quality. The noble gas radon-222 (Rn) is becoming increasingly used as a sensitive tracer to quantify groundwater discharge to wetlands, lakes, and rivers: a development driven by technical and methodological advances in Rn measurement. However, quantitative interpretation of these data is not trivial, and the methods used to date are based on the simplest solutions to the mass balance equation (e.g., first-order finite difference and inversion). Here we present a new implicit numerical model (FINIFLUX) based on finite elements for quantifying groundwater discharge to streams and rivers using Rn surveys at the reach scale (1–50 km). The model is coupled to a state-of-the-art parameter optimization code Parallel-PEST to iteratively solve the mass balance equation for groundwater discharge and hyporheic exchange. The major benefit of this model is that it is programed to be very simple to use, reduces nonuniqueness, and provides numerically stable estimates of groundwater fluxes and hyporheic residence times from field data. FINIFLUX was tested against an analytical solution and then implemented on two German rivers of differing magnitude, the Salzach (∼112 m3 s−1) and the Rote Main (∼4 m3 s−1). We show that using previous inversion techniques numerical instability can lead to physically impossible negative values, whereas the new model provides stable positive values for all scenarios. We hope that by making FINIFLUX freely available to the community that Rn might find wider application in quantifying groundwater discharge to streams and rivers and thus assist in a combined management of surface and groundwater systems.

The interplay between precipitation and evapotranspiration determines the input into the hydrological system of a catchment. Annual values of precipitation, evapotranspiration, and runoff measured at the catchment outlet for the 2002–2009 period were available. Annual precipitation clearly surmounted the sum of evapotranspiration and runoff. Part of the observed discrepancy might be due to the heterogeneity of precipitation and evapotranspiration within the catchment which has not been studied in sufficient detail. Annual evapotranspiration fluxes were remarkably constant during this period, whereas precipitation and runoff exhibited much larger interannual variability.