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Although water availability and water quality are equally important for effective water resources management at various spatial and temporal scales, to date, a combined representation of soil water balance components and water quality components in Python is not available. The new RoGeR toolbox contains models that can be used for not only the quantification of hydrological processes, fluxes and stores, but also solute transport processes based on StorAge selection (SAS). This study presents the code structure and functionalities of RoGeR developed as a scientific model toolbox following defined open-source software guidelines. RoGeR uses five different computational backends covering just-in-time compilation, parallelism and graphical processing units (GPUs) that might be used for optimizing computational performance. We show that graphical processing unit computing has the greatest potential to improve computation time and energy usage, especially for large modelling experiments. A simple modelling experiment highlights the capabilities of the new RoGeR model toolbox. We simulated the soil water balance, stable water isotope (18 O) transport, and corresponding travel time distributions of the Eberbaechle catchment, Germany, for a 3-year period. Due to the current limitations of a variety of process components, further development of RoGeR as a scientific software is needed. Future modifications are easily possible due to the open software architecture of RoGeR. [ABSTRACT FROM AUTHOR]

This study investigates the contamination potential of herbicides to groundwater with the help of numerical modeling (HYDRUS‐1D) and stable carbon isotopes for characterizing biodegradation. Four herbicides, metolachlor, terbuthylazine, prosulfuron, and nicosulfuron, were applied over a period of 4.5 years on two lysimeters located in Wielenbach, Germany, and monitored by lysimeter drainage. These lysimeters contained soil cores dominated by sandy gravel (Ly1) and clayey sandy silt (Ly2) and were both cropped with maize (Zea mays). In the preceding study, we characterized flow within the lysimeters by using stable water isotopes and unsaturated flow models. Building up on these findings, models were extended for describing reactive transport of the herbicides and investigating process contributions. At the end of the experiment, 0.9%–15.9% of the applied herbicides (up to 20.9% if including metabolites) were recovered by lysimeter drainage. Metabolite formation and accumulation was observed, and biodegradation was also indicated by small changes in carbon isotope signals (δ13C) between applied and leached herbicides. Model setups could describe the dynamics of herbicide concentrations in lysimeter drainage well. Concentration peaks in drainage were partly also linked with strong precipitation events, indicating preferential flow influence. The soil core with the coarser texture (Ly1) showed less herbicide leaching than the finer texture (Ly2), which can be explained by a larger mobile phase in Ly1. Overall, our approaches and findings contribute to the understanding of multi‐process herbicide transport in the vadose zone and leaching potentials to groundwater, where δ13C can provide valuable hints for microbial degradation. Core Ideas: Leached herbicide concentrations depend on the soil texture.Concentration peaks of herbicides in lysimeter drainage can be linked with rain events.Solute transport modeling allows us to identify dominant processes affecting herbicide leaching.Stable carbon isotopes measured in drainage can identify biodegradation processes in the unsaturated zone. [ABSTRACT FROM AUTHOR]

Understanding transport and fate processes in the subsurface is of fundamental importance to identify the leaching potentials of herbicides or other compounds to groundwater resources. HYDRUS‐1D was used to simulate water flow and solute transport in arable land lysimeters. Simulations were compared to observed drainage rates and stable water isotopes (δ18O) in the drainage. Four different model setups were investigated and statistically evaluated for their model performance to identify dominant processes for water flow characterization in the vadose zone under similar cultivation management and climatic conditions. The studied lysimeters contain soil cores dominated by sandy gravel (Ly1) and clayey sandy silt (Ly2), both cropped with maize located in Wielenbach, Germany. First, a single‐porosity setup was chosen. For Ly1, modeling results were satisfactory, but for Ly2, the damping observed in the isotope signature of the drainage could not be fully covered. By considering immobile water with a dual‐porosity setup for Ly2, model performance improved. This could be due to a higher fraction of fine pores in Ly2 available for water storage, leading to mixing processes of isotopically enriched summer precipitation and lighter winter water. Accounting for isotopic evaporation fractionation processes in both model setups did not lead to improved model performance. Consequentially, the difference in soil hydraulic properties between the two lysimeters seems to impact water flow processes. Knowledge of such differences is crucial to prevent contamination and mitigate potential risks to soil and groundwater. Core Ideas: For effective model description, multi‐process modeling must be explored.Mixing processes between immobile and mobile water are of greater importance for finer soils.Evaporation fractionation effects have no clear impact on simulated stable water isotopes in lysimeter drainage. [ABSTRACT FROM AUTHOR]

Soluble reactive phosphorus (SRP) concentrations in agricultural headwaters can display pronounced seasonal variability at low flow, often with the highest concentrations occurring in summer. These SRP concentrations often exceed eutrophication levels, but their main sources, spatial distribution, and temporal dynamics are often unknown. The purpose of this study is therefore to differentiate between potential SRP losses and releases from soil drainage, anoxic riparian wetlands, and stream sediments in an agricultural headwater catchment. To identify the dominant SRP sources, we carried out three longitudinal stream sampling campaigns for SRP concentrations and fluxes. We used salt dilution tests and natural 222 Rn to determine water fluxes in different sections of the stream, and we sampled for SRP, Fe, and 14 C dissolved organic carbon (DOC) to examine possible redox-mediated mobilization from riparian wetlands and stream sediments. The results indicate that a single short section in the upper headwater reach was responsible for most of the SRP fluxes to the stream. Analysis of samples taken under summer low-flow conditions revealed that the stream water SRP concentrations, the fraction of SRP within total dissolved P (TDP), and DOC radiocarbon ages matched those in the groundwater entering the gaining section. Pore water from the stream sediment showed evidence of reductive mobilization of SRP, but the exchange fluxes were probably too small to contribute substantially to SRP stream concentrations. We also found no evidence that shallow flow paths from riparian wetlands contributed to the observed SRP loads in the stream. Combined, the results of this campaign and previous monitoring suggest that groundwater is the main long-term contributor of SRP at low flow, and agricultural phosphorus is largely buffered in the soil zone. We argue that the seasonal variation of SRP concentrations was mainly caused by variations in the proportion of groundwater present in the streamflow, which was highest during summer low-flow periods. Accurate knowledge of the various input pathways is important for choosing effective management measures in a given catchment, as it is also possible that observations of seasonal SRP dilution patterns stem from increased mobilization in riparian zones or from point sources. [ABSTRACT FROM AUTHOR]

Stable isotopes of water are ideal tracers to integrate into process‐based models, advancing ecohydrological understanding. Current tracer‐aided ecohydrological modeling is mostly conducted in relatively small‐scale catchments, due to limited tracer data availability and often highly damped stream isotope signals in larger catchments (>100 km2). Recent model developments have prioritized better spatial representation, offering new potential for advancing upscaling in tracer‐aided modeling. Here, we adapted the fully distributed EcH2O‐iso model to the Selke catchment (456 km2, Germany), incorporating monthly sampled isotopes from seven sites between 2012 and 2017. Parameter sensitivity analysis indicated that the information content of isotope data was generally complementary to discharge and more sensitive to runoff partitioning, soil water and energy dynamics. Multi‐criteria calibrations revealed that inclusion of isotopes could significantly improve discharge performance during validations and isotope simulations, resulting in more reasonable estimates of the seasonality of stream water ages. However, capturing isotopic signals of highly non‐linear near‐surface processes remained challenging for the upscaled model, but still allowed for plausible simulation of water ages reflecting non‐stationarity in transport and mixing. The detailed modeling also helped unravel spatio‐temporally varying patterns of water storage‐flux‐age interactions and their interplay under severe drought conditions. Embracing the upscaling challenges, this study demonstrated that even coarsely sampled isotope data can be of value in aiding ecohydrological modeling and consequent process representation in larger catchments. The derived innovative insights into ecohydrological functioning at scales commensurate with management decision making, are of particular importance for guiding science‐based measures for tackling environmental changes. Key Points: Process‐based tracer‐aided ecohydrological modeling is upscaled to >100 km2 catchments using stable water isotopesIsotopes benefit large‐scale modeling in substantially improving model robustness and reliability of water age estimatesLarger‐scale water partitioning and drought responses are controlled by heterogeneity in catchment organization [ABSTRACT FROM AUTHOR]

Large agricultural streams receive excessive inputs of nitrogen. However, quantifying the role of these streams in nitrogen processing remains limited because continuous direct measurements of the interacting and highly time-varying nitrogen processing pathways in larger streams and rivers are very complex. Therefore, we employed a monitoring-driven modelling approach with high-frequency in situ data and the river water quality model Water Quality Analysis Simulation Program (WASP) 7.5.2 in the 27.4 km reach of the sixth-order agricultural stream called Lower Bode (central Germany) for a 5-year period (2014–2018). Paired high-frequency sensor data (15 min interval) of discharge, nitrate, dissolved oxygen, and chlorophyll a at upstream and downstream stations were used as model boundaries and for setting model constraints. The WASP model simulated 15 min intervals of discharge, nitrate, and dissolved oxygen with Nash–Sutcliffe efficiency values higher than 0.9 for calibration and validation, enabling the calculation of gross and net dissolved inorganic nitrogen uptake and pathway rates on a daily, seasonal, and multiannual scale. Results showed daily net uptake rate of dissolved inorganic nitrogen ranged from - 17.4 to 553.9 mgNm-2d-1. The highest daily net uptake could reach almost 30 % of the total input loading, which occurred at extreme low flow in summer 2018. The growing season (spring and summer) accounted for 91 % of the average net annual uptake of dissolved inorganic nitrogen in the measured period. In spring, both the DIN gross and net uptake were dominated by the phytoplankton uptake pathway. In summer, benthic algae assimilation dominated the gross uptake of dissolved inorganic nitrogen. Conversely, the reach became a net source of dissolved inorganic nitrogen with negative daily net uptake values in autumn and winter, mainly because the release from benthic algae surpassed uptake processes. Over the 5 years, average gross and net uptake rates of dissolved inorganic nitrogen were 124.1 and 56.8 mgNm-2d-1 , which accounted for only 2.7 % and 1.2 % of the total loadings in the Lower Bode, respectively. The 5-year average gross DIN uptake decreased from assimilation by benthic algae through assimilation by phytoplankton to denitrification. Our study highlights the value of combining river water quality modelling with high-frequency data to obtain a reliable budget of instream dissolved inorganic nitrogen processing which facilitates our ability to manage nitrogen in aquatic systems. This study provides a methodology that can be applied to any large stream to quantify nitrogen processing pathway dynamics and complete our understanding of nitrogen cycling. [ABSTRACT FROM AUTHOR]

Long‐term nitrogen (N) transport and retention dynamics across catchments are not well understood. Using a process‐based model for 89 German catchments, results across study catchments reveal that most N surplus (during 1950–2014) was removed by denitrification (mean ± standard deviation: 58 ± 15%) while the remaining fraction was mostly stored in the soil (14% ± 11%). The mean groundwater transit times in these catchments varied from 3.2 to 20.3 years. These results indicate that past N inputs could continue to affect surface and groundwater quality in the coming years. We identified four catchment groups with distinct archetypal N transport and retention dynamics, which are linked to the catchments' climate, topographic, and geological conditions. Overall, our results shed light on long‐term N dynamics in German catchments and how they are linked to catchment characteristics, emphasizing the role of long‐term N accumulation and transport for water quality management and evaluation programs. Plain Language Summary: High nitrate concentrations in German water bodies are quite common. It is unclear to what degree current nitrogen levels in water bodies are due to current or past nitrogen (N) application on agricultural fields. What happened to excess N (N was not taken up by plants) in catchments has not been fully understood. In this study, we modeled the fate of excess N in 89 German catchments during the period 1950–2014. Our results suggest that most of the excess N was removed from the catchment in gaseous form (denitrification), and a substantial portion of the remaining excess N was stored in the soil zone. This soil N can leach into the deeper zone (groundwater) where it may travel for 3–20 years to reach the catchment outlet. We also identified four distinct groups of catchments with different behavior in terms of N transport and storage, which further exhibited different climatic, topographic, and subsurface conditions, suggesting that these factors could play a role in catchment N transport and retention. Overall, our results show that there could be a substantial delay between implemented management practices and resulting changes in surface or groundwater quality, which should be considered in water quality management. Key Points: We provided insights into the long‐term (1950–2014) nitrogen (N) transport and retention across various German catchmentsLarge‐sample assessment shows that 57% of N surplus was removed by denitrification and 15% of N surplus was accumulated in the soil zoneFour catchment clusters with distinct nitrogen transport and retention dynamics were linked to climatic, topographic, and geological factors [ABSTRACT FROM AUTHOR]

Excess export of nitrate to streams affects ecosystem structure and functions and has been an environmental issue attracting worldwide attention. The dynamics of catchment-scale solute export from diffuse nitrogen sources can be explained by the changes of dominant flow paths, as solute attenuation (including the degradation of nitrate) is linked to the age composition of outflow. Previous data-driven studies suggested that catchment topographic slope has strong impacts on the age composition of streamflow and consequently on in-stream solute concentrations. However, the impacts have not been systematically assessed in terms of solute mass fluxes and solute concentration levels, particularly in humid catchments with strong seasonality in meteorological forcing. To fill this gap, we modeled the groundwater flow and nitrate transport for a small agricultural catchment in Central Germany. We used the fully coupled surface and subsurface numerical simulator HydroGeoSphere (HGS) to model groundwater and overland flow and nitrate transport. We computed the water ages using numerical tracer experiments. To represent various topographic slopes, we additionally simulated 10 synthetic catchments generated by modifying the topographic slope from the real-world scenario. Results suggest a negative correlation between the young streamflow fraction and the topographic slope. This correlation is more pronounced in flat landscapes with slopes <1:60. Flatter landscapes tend to retain more N mass in the soil (including mass degraded in soil) and export less N mass to the stream, due to reduced leaching and increased degradation. The mean in-stream nitrate concentration shows a decreasing trend in response to a decreasing topographic slope, suggesting that a large young streamflow fraction is not sufficient for high in-stream concentrations. Our results improve the understanding of nitrate export in response to topographic slope in a temperate humid climate, with important implications for the management of stream water quality. [ABSTRACT FROM AUTHOR]

Environmental data are the key to defining and addressing water quality and quantity challenges at the catchment scale. Here, we present the first large-sample water quality data set for 1386 German catchments covering a large range of hydroclimatic, topographic, geologic, land use, and anthropogenic settings. QUADICA (water QUAlity, DIscharge and Catchment Attributes for large-sample studies in Germany) combines water quality with water quantity data, meteorological and nutrient forcing data, and catchment attributes. The data set comprises time series of riverine macronutrient concentrations (species of nitrogen, phosphorus, and organic carbon) and diffuse nitrogen forcing data (nitrogen surplus, atmospheric deposition, and fixation) at the catchment scale. Time series are generally aggregated to an annual basis; however, for 140 stations with long-term water quality and quantity data (more than 20 years), we additionally present monthly median discharge and nutrient concentrations, flow-normalized concentrations, and corresponding mean fluxes as outputs from Weighted Regressions on Time, Discharge, and Season (WRTDS). The catchment attributes include catchment nutrient inputs from point and diffuse sources and characteristics from topography, climate, land cover, lithology, and soils. This comprehensive, freely available data collection with a large spatial and temporal coverage can facilitate large-sample data-driven water quality assessments at the catchment scale as well as mechanistic modeling studies. QUADICA is available at 10.4211/hs.0ec5f43e43c349ff818a8d57699c0fe1 (Ebeling et al., 2022b) and 10.4211/hs.88254bd930d1466c85992a7dea6947a4 (Ebeling et al., 2022a). [ABSTRACT FROM AUTHOR]

Improving nitrogen (N) status in European water bodies is a pressing issue. N levels depend not only on current but also past N inputs to the landscape, that have accumulated through time in legacy stores (e.g., soil, groundwater). Catchment‐scale N models, that are commonly used to investigate in‐stream N levels, rarely examine the magnitude and dynamics of legacy components. This study aims to gain a better understanding of the long‐term fate of the N inputs and its uncertainties, using a legacy‐driven N model (ELEMeNT) in Germany's largest national river basin (Weser; 38,450 km2) over the period 1960–2015. We estimate the nine model parameters based on a progressive constraining strategy, to assess the value of different observational data sets. We demonstrate that beyond in‐stream N loading, soil N content and in‐stream N concentration allow to reduce the equifinality in model parameterizations. We find that more than 50% of the N surplus denitrifies (1480–2210 kg ha−1) and the stream export amounts to around 18% (410–640 kg ha−1), leaving behind as much as around 230–780 kg ha−1 of N in the (soil) source zone and 10–105 kg ha−1 in the subsurface. A sensitivity analysis reveals the importance of different factors affecting the residual uncertainties in simulated N legacies, namely hydrologic travel time, denitrification rates, a coefficient characterizing the protection of organic N in source zone and N surplus input. Our study calls for proper consideration of uncertainties in N legacy characterization, and discusses possible avenues to further reduce the equifinality in water quality modeling. Plain Language Summary: Lowering nitrogen (N) amounts in European surface waters is a pressing issue. N levels largely result from fertilizer application in agricultural areas, and deposition of atmospheric N coming from fossil fuel combustion. These N inputs to the landscape can accumulate below the ground surface in so‐called legacy stores (including the soil and aquifer), from which they can be released progressively through time. Therefore, N levels depend not only on the recent N inputs, but also on their history. Our modeling study aims to improve our understanding of the long‐term fate of the N inputs and its uncertainties in Germany's largest national river basin (Weser) over the period 1960–2015. It suggests that more than 50% of the N inputs to land is lost to the atmosphere (denitrification, 1480–2210 kg ha−1) and the stream export amounts to around 18% (410–640 kg ha−1), leaving behind as much as around 16% (264–820 kg ha−1) in the landscape (legacy). However, the uncertainties in these estimates remain large, partly due to a lack of observational data on internal (legacy) components and uncertainties in N inputs. Overall, our study calls for proper consideration of uncertainties in N legacy characterization, and discusses possible avenues to further reduce them. Key Points: We use a parsimonious model to examine the long‐term (1960–2015) fate of nitrogen inputs to the landscape including the legacy buildupMore than 50% of the nitrogen surplus denitrifies and around 491 kg ha−1 accumulates in legacy stores in Germany's largest river basinHydrologic travel time and denitrification rates largely contribute to the residual uncertainty in the simulated nitrogen legacies [ABSTRACT FROM AUTHOR]

Lower‐order streams (first‐ and second‐order) define the initial, landscape‐related, chemical signature of stream water in catchments. To date, first‐order streams have been perceived as predominantly draining systems, which collect water and solutes from the surrounding groundwater and surface runoff and simply mirror the chemical composition of the inputs. In this study, the impact of stream‐groundwater exchange fluxes on water chemistry of a first order agricultural stream (Schönbrunnen) and its connected groundwater in south‐western Germany was assessed combining 222Rn, dissolved ions (chloride, sulphate, nitrate), and salt tracer tests with investigations of stream discharge and groundwater hydraulic gradients. The findings suggest that stream‐water chemistry in lower‐order streams is governed by an intricate interplay between dynamic, bidirectional water and solute exchange between groundwater and the stream leading to a pronounced hydrologic turnover along the studied reaches. High nitrate concentrations (up to 79 mg/L as NO3−) in stream water were attenuated in downstream direction (a mean value of 39 mg/L) without an increase in discharge, suggesting that redox processes occurring during sediment passage in sequential infiltration and exfiltration zones affect stream water chemistry. Nitrate in stream water infiltrating into the aquifer at distinct losing spots was subject to denitrification within the first few decimetres of the streambed, while concurrent exfiltration of low‐nitrate groundwater into the stream at gaining spots compensated for flow losses and in turn diluted instream nitrate concentrations. In summary the findings imply that (1) instream mixing resulting from the bidirectional exchange of water between groundwater and the stream (hydrologic turnover) affects instream nitrate concentrations, (2) denitrification in the streambed of losing reaches and the near‐stream aquifer significantly contributes to reactive nitrate turnover and elimination, and (3) oxidation of ammonium could be a secondary source of nitrate inputs into the stream. [ABSTRACT FROM AUTHOR]

During the flow of stream water from losing reaches through aquifer sediments, aerobic and anaerobic respiration (denitrification) can deplete dissolved oxygen and nitrate (NO3−), impacting water quality in the floodplain and downstream gaining reaches. Such processes, which vary in time with short and long‐term changes in stream flow and temperature, need to be assessed at the stream corridor scale to fully capture their effects on net turnover, but this has rarely been done. To address this gap, we combine a fully‐integrated 3D transient numerical flow model with temperature‐dependent reactive transport along advective subsurface flow paths to assess aerobic and anaerobic respiration dynamics at the stream corridor scale in a predominantly losing stream. Our results suggest that given carbon availability (as an electron donor), complete NO3− removal occurred further away from the stream after complete oxygen depletion and was relatively insensitive to variations in temperature and transit‐times. Conversely, transit‐times and oxygen concentrations constrained nitrate removal along short hyporheic flow paths. Even under limited carbon availability and low‐temperatures, NO3− removal fractions (RNO3) will be greater at locations further from the stream than along shorter hyporheic flow paths (RNO3 = 0.4 and RNO3 = 0.1, respectively). With increasing temperature, the relative effects of stream flow and solute concentrations on biogeochemical turnover and the redox zonation around the stream decreased. The study highlights the importance of seasonal variations of stream flow and temperature for water quality at the stream‐corridor scale. It also provides an adaptive framework to assess and quantify reach‐scale biogeochemical turnover around dynamic streams. Plain Language Summary: Nitrate pollution is a widespread problem in many catchments with intense agricultural activities. Denitrification is a redox process that removes nitrate from the aquatic system via its transformation to nitrogen gas. Denitrification is difficult to assess at larger scales since it depends on multiple factors, such as solute concentrations, temperature variations, and also the time that water resides in the subsurface, where reactions can take place. To evaluate how these factors can influence denitrification, we employed a coupled modeling approach representing the riparian zone of a 4th order stream in central Germany. We found that temperature variations strongly regulate the process and that during the winter the aerobic (oxygen rich) zone around the stream expands, which further inhibits denitrification in the near stream groundwater. However, even in the winter denitrification occurs, but at larger distance from the stream where oxygen has been depleted sufficiently. With increasing temperature, the influence of other factors on denitrification and on the redox zonation around the stream decreases. Coupled numerical models can provide further insights into the occurrence and interrelations of the multiple processes controlling water quality patterns in river corridors. Key Points: Fully‐integrated 3D transient flow model coupled to a temperature‐dependent flow path‐reaction model to assess riparian solutes turnoverTurnover mainly controlled by high temperature in summer; in winter solute concentrations and transit‐times variations become more importantAssessments of riparian turnover restricted to near stream areas might overlook processes affecting overall downstream water quality [ABSTRACT FROM AUTHOR]

The analysis of concentration‐discharge (C‐Q) relationships from low‐frequency observations is commonly used to assess solute sources, mobilization, and reactive transport processes at the catchment scale. High‐frequency concentration measurements are increasingly available and offer additional insights into event‐scale export dynamics. However, only few studies have integrated inter‐annual and event‐scale C‐Q relationships. Here, we analyze high‐frequency measurements of specific conductance (EC), nitrate (NO3‐N) concentrations and spectral absorbance at 254 nm (SAC254, as a proxy for dissolved organic carbon) over a two year period for four neighboring catchments in Germany ranging from more pristine forested to agriculturally managed settings. We apply an integrated method that adds a hysteresis term to the established power law C‐Q model so that concentration intercept, C‐Q slope and hysteresis can be characterized simultaneously. We found that inter‐event variability in C‐Q hysteresis and slope were most pronounced for SAC254 in all catchments and for NO3‐N in forested catchments. SAC254 and NO3‐N event responses in the smallest forested catchment were closely coupled and explainable by antecedent conditions that hint to a common near‐stream source. In contrast, the event‐scale C‐Q patterns of EC in all catchments and of NO3‐N in the agricultural catchment without buffer zones around streams were less variable and similar to the inter‐annual C‐Q relationship indicating a homogeneity of mobilization processes over time. Event‐scale C‐Q analysis thus added key insights into catchment functioning whenever the inter‐annual C‐Q relationship contrasted with event‐scale responses. Analyzing long‐term and event‐scale behavior in one coherent framework helps to disentangle these scattered C‐Q patterns. Key Points: We compare event‐scale and inter‐annual concentration‐discharge relationships in four adjoined catchments with contrasting land useThe variability of event‐scale C‐Q relationships was shaped by land use and antecedent conditions for biogeochemically reactive but not for geogenic solutesFor biogeochemically reactive solutes, event‐scale C‐Q patterns can contrast the inter‐annual pattern obtained from all observations [ABSTRACT FROM AUTHOR]

Understanding the controls on event-driven dissolved organic carbon (DOC) export is crucial as DOC is an important link between the terrestrial and the aquatic carbon cycles. We hypothesized that topography is a key driver of DOC export in headwater catchments because it influences hydrological connectivity, which can inhibit or facilitate DOC mobilization. To test this hypothesis, we studied the mechanisms controlling DOC mobilization and export in the Große Ohe catchment, a forested headwater in a mid-elevation mountainous region in southeastern Germany. Discharge and stream DOC concentrations were measured at an interval of 15 min using in situ UV-Vis (ultraviolet–visible) spectrometry from June 2018 until October 2020 at two topographically contrasting subcatchments of the same stream. At the upper location (888 m above sea level, a.s.l.), the stream drains steep hillslopes, whereas, at the lower location (771 m a.s.l.), it drains a larger area, including a flat and wide riparian zone. We focus on four events with contrasting antecedent wetness conditions and event size. During the events, in-stream DOC concentrations increased up to 19 mg L -1 in comparison to 2–3 mg L -1 during baseflow. The concentration–discharge relationships exhibited pronounced but almost exclusively counterclockwise hysteresis loops which were generally wider in the lower catchment than in the upper catchment due to a delayed DOC mobilization in the flat riparian zone. The riparian zone released considerable amounts of DOC, which led to a DOC load up to 7.4 kg h -1. The DOC load increased with the total catchment wetness. We found a disproportionally high contribution to the total DOC export of the upper catchment during events following a long dry period. We attribute this to the low hydrological connectivity in the lower catchment during drought, which inhibited DOC mobilization, especially at the beginning of the events. Our data show that not only event size but also antecedent wetness conditions strongly influence the hydrological connectivity during events, leading to a varying contribution to DOC export of subcatchments, depending on topography. As the frequency of prolonged drought periods is predicted to increase, the relative contribution of different subcatchments to DOC export may change in the future when hydrological connectivity will be reduced more often. [ABSTRACT FROM AUTHOR]

The exchange of water and solutes between the stream and groundwater along a stream network affects the source composition of discharge and solute load in the stream. To date, this hydrologic turnover has only been analyzed with respect to the exchange of water. In this study, we extend the concept of hydrologic turnover to solutes and analyze the effects of different hydrologic conditions on the spatial patterns and magnitude of exchange fluxes. Based on a coupled stream‐groundwater model built in MODFLOW using the Streamflow‐routing package, we simulated stream‐groundwater exchange along a stream of 30 km in length and evaluated the evolution of stream water source composition under different precipitation and streamflow conditions. Results show that even for highly variable hydrologic conditions, the direction of stream‐groundwater exchange (loss/gain) remained unchanged in consistently gaining or losing reaches, but changed in interspersed transitional reaches. The comparison between the source composition of discharge and nitrate load in stream water revealed a decoupling of discharge and solute load contribution from groundwater to the stream, as zones of high water gains do not necessarily coincide with zones of high solute concentrations. Overall, nearly 80% of total groundwater contributions to the outflow of water from the catchment were generated over only 20% of the total stream length. Our research highlights the importance of distinguishing water and solute load contributions to streams. This in turn implies that to reduce groundwater‐borne nutrient loads to streams, measures need to focus on the specific reaches with highest load contributions. Plain Language Summary: Streams and groundwater are connected and continuously exchange water and solutes. For example, the inflow of groundwater into streams not only increases streamflow, but also influences the chemical composition of stream water if the groundwater contains different solutes than the stream. Therefore understanding the spatial patterns of water and solute contributions from groundwater to the stream is important for the management of stream water quality. Taking the lower Selke River in central Germany as an example, we investigated the influence of stream gains and losses on the source composition of discharge and solute loads along the stream network as well as the influence of different precipitation and streamflow conditions. We found that higher precipitation and the associated elevated groundwater recharge or lower stream flows can increase the total length of gaining reaches, decreasing the relative importance of the source water from the upper stream. Due to the heterogeneous distribution of groundwater and solute gains, the magnitude of solute contribution from groundwater to stream can be quite different from the associated discharge contribution. However, both water and solute contributions are typically dominated by focused groundwater gains along only a few key reaches. Key Points: Across a wide range of hydrologic scenarios, at least 37% of the stream length is characterized by losing conditionsHeterogeneous solute concentrations in groundwater induce a different solute source composition from stream water source compositionMost of the groundwater contributions to stream water are generated over only a small fraction of total stream length [ABSTRACT FROM AUTHOR]

Elevated nutrient inputs challenge the health and functioning of aquatic ecosystems. To improve riverine water quality management, it is necessary to understand the underlying biogeochemical and physical processes, anthropogenic drivers and their interactions at catchment scale. We hypothesize that the spatial heterogeneity of nutrient sources dominantly controls the variability of in‐stream concentration dynamics among catchments. We investigated controls of mean nitrate (NO3−), phosphate (PO43−), and total organic carbon (TOC) concentrations and concentration‐discharge (C‐Q) relationships in 787 German catchments of a newly assembled data base, covering a wide range of physiographic and anthropogenic settings. We linked water quality metrics to catchment characteristics using partial least squares regressions and random forests. We found archetypal C‐Q patterns with enrichment dominating NO3− and TOC, and dilution dominating PO43− export. Both the mean NO3− concentrations and their variance among sites increased with agricultural land use. We argue that subsurface denitrification can buffer high nitrogen inputs and cause a decline in concentration with depth, resulting in chemodynamic, strongly positive C‐Q patterns. Mean PO43− concentrations were related to point sources, though the low predictive power suggests effects of unaccounted in‐stream processes. In contrast, high diffuse agricultural inputs explained observed positive PO43−C‐Q patterns. TOC levels were positively linked to the abundance of riparian wetlands, while hydrological descriptors were important for explaining TOC dynamics. Our study shows a strong modulation of anthropogenic inputs by natural controls for NO3− and PO43− concentrations and dynamics, while for TOC only natural controls dominate observed patterns across Germany. Plain Language Summary: Phosphorus, nitrogen, and organic carbon are key elements of plants and all living organisms. Humans are altering the nutrient cycles especially, to improve agricultural productivity and through domestic and industrial wastewater. Excess nutrients in surface waters have harmed many aquatic ecosystems by causing toxic algal blooms and a loss of biodiversity. Low nutrient concentrations and habitat variability are similarly important to those ecosystems, but human interference with natural drivers is not yet fully understood. To better understand and disentangle natural or human controls, we investigated nutrient concentrations and their variability across German catchments with varying landscapes and anthropogenic conditions. The human impact is clearly visible for mean nitrate concentrations, while the (natural) subsurface properties mainly controlled the variability of riverine nitrate. In the past, phosphate inputs were usually linked to wastewater, yet we found the control of agricultural activities on concentration dynamics to be unexpectedly high. Organic carbon was mainly associated with natural sources related to riparian wetlands where interactions with other nutrients are possible. This understanding of dominant controls is important in order to adapt management strategies to ensure healthy aquatic ecosystems. Key Points: Riverine NO3− dynamics are controlled by vertical concentration heterogeneity, which can result from subsurface denitrificationDiffuse P sources exert a strong control on the spatial variability of PO43− export patterns in contrast to point sourcesShare of riparian wetlands controls the mean TOC concentrations in German catchments [ABSTRACT FROM AUTHOR]

The ecosystem function of vegetation to attenuate export of nutrients is of substantial importance for securing water quality. This ecosystem function is at risk of deterioration due to an increasing risk of large‐scale forest dieback under climate change. The present study explores the response of the nitrogen (N) cycle of a forest catchment in the Bavarian Forest National Park, Germany, in the face of a severe bark beetle (Ips typographus Linnaeus) outbreak and resulting large‐scale forest dieback using top‐down statistical‐mechanistic modeling. Outbreaks of bark beetle killed the dominant tree species Norway spruce (Picea abies (L.) H.Karst.) in stands accounting for 55% of the catchment area. A Bayesian hierarchical model that predicts daily stream NO3 concentration (C) over three decades with discharge (Q) and temperature (T) (C‐Q‐T relationship) outperformed alternative statistical models. A catchment model was subsequently developed to explain the C‐Q‐T relationship in top‐down fashion. Annually varying parameter estimates provide mechanistic interpretations of the catchment processes. Release of NO3 from decaying litter after the dieback was tracked by an increase of the nutrient input parameter cs0. The slope of C‐T relation was near zero during this period, suggesting that the nutrient release was beyond the regulating capacity of the vegetation and soils. Within a decade after the dieback, the released N was flushed out and nutrient retention capacity was restored with the regrowth of the vegetation. Key Points: Pulse of nitrate export from a forest catchment in response to bark beetle infestation followed by recovery of nutrient retention capacityTop‐down, data‐driven Bayesian hierarchical model assists mechanistic interpretation of hydrochemical processesConcentration‐discharge‐temperature relationship is shaped by spatial heterogeneity of nutrient and seasonality of biogeochemical reactions [ABSTRACT FROM AUTHOR]

Defining effective measures to reduce nitrate pollution in heterogeneous mesoscale catchments remains challenging when based on concentration measurements at the outlet only. One reason for this is our limited understanding of the subcatchment contributions to nitrate export and their importance at different time scales. While upstream subcatchments often disproportionally contribute to runoff generation and in turn to nutrient export, agricultural areas (which are typically found in downstream lowlands) are known to be a major source of nitrate pollution. To examine the interplay of different subcatchments, we analyzed seasonal long‐term trends and event dynamics of nitrate concentrations, loads, and the concentration–discharge relationship in three nested catchments within the Selke catchment (456 km2), Germany. The upstream subcatchments (40.4% of total catchment area, 34.5% of N input) had short transit times and dynamic concentration–discharge relationships with elevated nitrate concentrations during wet seasons and events. Consequently, the upstream subcatchments dominated nitrate export during high flow and disproportionally contributed to overall annual nitrate loads at the outlet (64.2%). The downstream subcatchment was characterized by higher N input, longer transit times, and relatively constant nitrate concentrations between seasons, dominating nitrate export during low‐flow periods. Neglecting the disproportional role of upstream subcatchments for temporally elevated nitrate concentrations and net annual loads can lead to an overestimation of the role of agricultural lowlands. Nonetheless, constantly high concentrations from nitrate legacies pose a long‐term threat to water quality in agricultural lowlands. This knowledge is crucial for an effective and site‐specific water quality management. Plain Language Summary: To efficiently remove nitrate pollution, we need to understand how it is transported, mobilized, and stored within large and heterogeneous catchments. Previous studies have shown that upstream catchments often have a disproportional impact on nutrient export, while agriculture (a major nitrate source) is often located in downstream lowlands. To understand which parts of a catchment contribute most to nitrate export and when, we analyzed long‐term (1983–2016) and high‐frequency (2010–2016) data in the Selke catchment (Germany) at three locations. The mountainous upstream part dominated nitrate transport during winter, spring, and rain events. It had a surprisingly high contribution to annual nitrate loads. The agricultural downstream part of the catchment dominated nitrate export during summer and autumn, with relatively constant concentrations between seasons. Here, nitrogen inputs needed more than a decade to travel through the subsurface of the catchment, which causes a time lag between measures to reduce nitrate pollution and their measurable effect. The resulting storage of nitrate in the groundwater threatens drinking water quality for decades to come. While the role of agricultural lowlands for nitrate export can be overestimated if neglecting the disproportional role of upstream subcatchments, their impact poses a long‐term threat to water quality. Key Points: Analyzing the CQ relationship across time scales allows the disentanglement of the impact of catchment heterogeneity on nitrate exportMountainous upstream subcatchments can dominate nitrate export during high flows and disproportionally contribute to nitrate loadsAgricultural downstream subcatchments can dominate nitrate export during low flow and pose a long‐term threat to water quality [ABSTRACT FROM AUTHOR]

Spatially distributed parameterization is preferable in capturing the heterogeneity of catchment properties and in allowing a better model representation of catchment responses. In hydrological modeling, sensitivity analysis is recommended to address the high‐dimensional parametric problems. However, less has been focused on water quality modeling, presumably due to the lack of suitable fully distributed models. Based on the newly developed mesoscale hydrological‐nitrate model, we investigated for the first time the spatially distributed sensitivity of nitrate model parameters and correlated the sensitivity indices with multiple catchment characteristics. The study was conducted in the highly heterogeneous Selke catchment, central Germany. Three nested catchments were defined based on the heterogeneous catchment responses (gauged by three nested stations). Results showed that parameters of soil denitrification, in‐stream denitrification, and in‐stream assimilatory uptake were the most sensitive parameters throughout the catchment. They all showed high spatial variability, which also varied when different gauging stations were considered. Spearman rank correlation indicated that the sensitivity of soil denitrification was controlled mainly by the relative limitations between the terrestrial hydrological transport capacity and the soil nitrate availability; the sensitivity of in‐stream processes was predominated by the spatial variability within the river network (e.g., the proximity to the gauging station), rather than the local biogeochemical factors. Based on the insights gained from the spatial sensitivity and correlation analyses, we suggested that an appropriate monitoring scheme is important in reflecting actual catchment responses, and a cautious statistical correlation is informative in benefiting future parameter regionalization of water quality models. Key Points: For the first time, sensitivity analysis of spatially distributed parameterization was conducted in catchment nitrate modelingParameter sensitivity showed high spatial variability and correlated significantly with varying controlling factors at different locationsResults revealed insights into heterogeneous nitrate behaviors and provided implications for future water quality model parameterization [ABSTRACT FROM AUTHOR]

Discharge from multiple wastewater treatment plants (WWTPs) distributed in urbanized river basins contributes to impairments of river water‐quality and aquatic ecosystem integrity, with size and location of WWTPs determined by population distribution within a river basin. Here we used geo‐referenced data for WWTPs in Germany to investigate the spatial organization of three attributes of interest in this study: population, population equivalents (the aggregated population served by each WWTP), and the number/sizes of WWTPs. To this end, we selected as case studies three large urbanized river basins (Weser, Elbe, and Rhine), home to about 70% of the population in Germany. We employed fractal river networks as structural platforms to examine the spatial patterns from two perspectives: spatial hierarchy (stream order) and patterns along longitudinal flow paths (width function). Moreover, we proposed three dimensionless scaling indices to quantify (1) human settlement preferences by stream order, (2) non‐sanitary flow contribution to total wastewater treated at WWTPs, and (3) degree of centralization in WWTPs locations. Across the three river basins, we found scale‐invariant distributions for each of the three attributes with stream order, quantified using extended Horton scaling ratios. We found a weak downstream clustering of population in the three basins. Variations in population equivalent clustering among different class‐sizes of WWTPs reflected the size, number, and locations of urban agglomerations in these river basins. We discussed the applicability of this approach to other large urbanized basins to analyze spatial organization of population and WWTPs. Key Points: Spatial hierarchies for population, population equivalents, and the number of wastewater treatment plants are scale‐invariantUnique patterns for cities size and number affect clustering location and degree for different class‐sizes of wastewater treatment plantsThree scaling indices characterize correlations in spatial patterns of population, population equivalents, and wastewater treatment plants [ABSTRACT FROM AUTHOR]

Abstract: Transformation and retention of nitrogen and other biologically reactive solutes in the hyporheic zones of running water contribute to an essential ecosystem service. However, the synoptic impact of intense agricultural or urban land‐uses, elevated nutrient loading, flow alterations, riparian clear‐cutting, and channelization on the source‐sink behavior of solutes in hyporheic zones remains largely uncharacterized and unquantified. Therefore, we studied nutrient dynamics in a hydromorphologically and chemically modified stream reach using a new monitoring approach allowing the simultaneous measurement of nutrient and water flux through a screened area in the subsurface of rivers (hyporheic passive flux meter, HPFM). With HPFMs we directly assessed time‐integrated lateral hyporheic nitrate fluxes during early spring and midsummer covering different temperature and discharge regimes. Contrary to our expectations, higher stream discharge coincided with substantially lower hyporheic exchange rates. While in streams featuring a natural morphology, bed form induced exchange commonly increases with surface flow, the influence of groundwater level was dominant in this reach. Furthermore, in contrast to less impacted environments, where progressive substrate depletion with depths reduces metabolic rates in the subsurface, we identified not the upper, but the intermediate layer of the hyporheic zone as hot spot of nutrient turnover. Overall, the hyporheic zone at the study site functioned partly as nitrate source, partly as a sink. Neither of the commonly used determinants redox state and residence time could explain this source or sink function. Our results give clear evidence to carefully transfer the knowledge of hyporheic zone processes from “natural” systems to anthropologically modified streams. [ABSTRACT FROM AUTHOR]

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 27% by additional processes and only about 12% 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. Plain Language Summary: Nitrogen is an important nutrient for agricultural crops. However, excessive nitrogen input into surface water in the form of nitrate can lead to algae blooms and lack of oxygen. The riparian zones of rivers are important buffer zones where groundwater is connected to soils, which are rich in soil organisms and organic matter pools fueling reaction processes. Hence, plants and bacteria can remove nitrate from riparian groundwater before it reaches the river. Bacterial consumption of nitrate (denitrification) leads to complete removal of nitrogen via release of nitrogen gas into the atmosphere. In contrast, other biogeochemical processes such as nitrate uptake by plants merely result in nitrogen retention within riparian zones. To quantify the role of denitrification relative to other processes, we developed a novel model combining concentration and isotope data of nitrate and applied it to a groundwater study site in Central Germany. We found that nitrate removal from riparian groundwater by additional processes largely exceeded denitrification. Hence, a major fraction of nitrogen inputs was retained in the riparian zone and may eventually end up in the river. Such information is highly relevant for many river ecosystems at risk of eutrophication because of high nitrogen inputs from agriculture. Key Points: We present a model using concentration and isotope data to distinguish riparian denitrification from additional nitrate removal processesThe model was applied to concentration and dual‐element isotope data of nitrate from riparian groundwater wellsNitrate removal by additional processes greatly exceeded denitrification, particularly at larger distance from the river and in winter [ABSTRACT FROM AUTHOR]