@article{KumarHesseRaoetal.2020, author = {Kumar, Rohini and Hesse, Fabienne and Rao, P. Srinivasa and Musolff, Andreas and Jawitz, James and Sarrazin, Francois and Samaniego, Luis and Fleckenstein, Jan H. and Rakovec, Oldrich and Thober, S. and Attinger, Sabine}, title = {Strong hydroclimatic controls on vulnerability to subsurface nitrate contamination across Europe}, series = {Nature Communications}, volume = {11}, journal = {Nature Communications}, number = {1}, publisher = {Nature Publishing Group UK}, address = {London}, issn = {2041-1723}, doi = {10.1038/s41467-020-19955-8}, pages = {1 -- 10}, year = {2020}, abstract = {Subsurface contamination due to excessive nutrient surpluses is a persistent and widespread problem in agricultural areas across Europe. The vulnerability of a particular location to pollution from reactive solutes, such as nitrate, is determined by the interplay between hydrologic transport and biogeochemical transformations. Current studies on the controls of subsurface vulnerability do not consider the transient behaviour of transport dynamics in the root zone. Here, using state-of-the-art hydrologic simulations driven by observed hydroclimatic forcing, we demonstrate the strong spatiotemporal heterogeneity of hydrologic transport dynamics and reveal that these dynamics are primarily controlled by the hydroclimatic gradient of the aridity index across Europe. Contrasting the space-time dynamics of transport times with reactive timescales of denitrification in soil indicate that similar to 75\% of the cultivated areas across Europe are potentially vulnerable to nitrate leaching for at least onethird of the year. We find that neglecting the transient nature of transport and reaction timescale results in a great underestimation of the extent of vulnerable regions by almost 50\%. Therefore, future vulnerability and risk assessment studies must account for the transient behaviour of transport and biogeochemical transformation processes.}, language = {en} } @article{MusolffSchmidtRodeetal.2016, author = {Musolff, Andreas and Schmidt, Christian and Rode, Michael and Lischeid, Gunnar and Weise, Stephan M. and Fleckenstein, Jan H.}, title = {Groundwater head controls nitrate export from an agricultural lowland catchment}, series = {Advances in water resources}, volume = {96}, journal = {Advances in water resources}, publisher = {Elsevier}, address = {Oxford}, issn = {0309-1708}, doi = {10.1016/j.advwatres.2016.07.003}, pages = {95 -- 107}, year = {2016}, abstract = {Solute concentration variability is of fundamental importance for the chemical and ecological state of streams. It is often closely related to discharge variability and can be characterized in terms of a solute export regime. Previous studies, especially in lowland catchments, report that nitrate is often exported with an accretion pattern of increasing concentrations with increasing discharge. Several modeling approaches exist to predict the export regime of solutes from the spatial relationship of discharge generating zones with solute availability in the catchment. For a small agriculturally managed lowland catchment in central Germany, we show that this relationship is controlled by the depth to groundwater table and its temporal dynamics. Principal component analysis of groundwater level time series from wells distributed throughout the catchment allowed derivation of a representative groundwater level time series that explained most of the discharge variability. Groundwater sampling revealed consistently decreasing nitrate concentrations with an increasing thickness of the unsaturated zone. The relationships of depth to groundwater table to discharge and to nitrate concentration were parameterized and integrated to successfully model catchment discharge and nitrate export on the basis of groundwater level variations alone. This study shows that intensive and uniform agricultural land use likely results in a clear and consistent concentration-depth relationship of nitrate, which can be utilized in simple approaches to predict stream nitrate export dynamics at the catchment scale. (C) 2016 Elsevier Ltd. All rights reserved.}, language = {en} } @article{MusolffSchmidtSelleetal.2015, author = {Musolff, Andreas and Schmidt, Christian and Selle, Benny and Fleckenstein, Jan H.}, title = {Catchment controls on solute export}, series = {Advances in water resources}, volume = {86}, journal = {Advances in water resources}, publisher = {Elsevier}, address = {Oxford}, issn = {0309-1708}, doi = {10.1016/j.advwatres.2015.09.026}, pages = {133 -- 146}, year = {2015}, abstract = {Dynamics of solute export from catchments can be classified in terms of chemostatic and chemodynamic export regimes by an analysis of concentration-discharge relationships. Previous studies hypothesized that distinct export regimes emerge from the presence of solute mass stores within the catchment and their connectivity to the stream. However, so far a direct link of solute export to identifiable catchment characteristics is missing. Here we investigate long-term time series of stream water quality and quantity of nine neighboring catchments in Central Germany ranging from relatively pristine mountain catchments to agriculturally dominated lowland catchments, spanning large gradients in land use, geology, and climatic conditions. Given the strong collinearity of catchment characteristics we used partial least square regression analysis to quantify the predictive power of these characteristics for median concentrations and the metrics of export regime. We can show that median concentrations and metrics of the export regimes of major ions and nutrients can indeed be inferred from catchment characteristics. Strongest predictors for median concentrations were the share of arable land, discharge per area, runoff coefficient and available water capacity in the root zone of the catchments. The available water capacity in the root zone, the share of arable land being artificially drained and the topographic gradient were found to be the most relevant predictors for the metrics of export regime. These catchment characteristics can represent the size of solute mass store such as the fraction of arable land being a measure for the store of nitrate. On the other hand, catchment characteristics can be a measure for the connectivity of these solute stores to the stream such as the fraction of tile drained land in the catchments. This study demonstrates the potential of data-driven, top down analyses using simple metrics to classify and better understand dominant controls of solute export from catchments. (C) 2015 Elsevier Ltd. All rights reserved.}, language = {en} } @article{MusolffSelleButtneretal.2017, author = {Musolff, Andreas and Selle, Benny and Buttner, Olaf and Opitz, Michael and Tittel, J{\"o}rg}, title = {Unexpected release of phosphate and organic carbon to streams linked to declining nitrogen depositions}, series = {Global change biology}, volume = {23}, journal = {Global change biology}, publisher = {Wiley}, address = {Hoboken}, issn = {1354-1013}, doi = {10.1111/gcb.13498}, pages = {1891 -- 1901}, year = {2017}, abstract = {Reductions in emissions have successfully led to a regional decline in atmospheric nitrogen depositions over the past 20 years. By analyzing long-term data from 110 mountainous streams draining into German drinking water reservoirs, nitrate concentrations indeed declined in the majority of catchments. Furthermore, our meta-analysis indicates that the declining nitrate levels are linked to the release of dissolved iron to streams likely due to a reductive dissolution of iron(III) minerals in riparian wetland soils. This dissolution process mobilized adsorbed compounds, such as phosphate, dissolved organic carbon and arsenic, resulting in concentration increases in the streams and higher inputs to receiving drinking water reservoirs. Reductive mobilization was most significant in catchments with stream nitrate concentrations < 6 mg L-1. Here, nitrate, as a competing electron acceptor, was too low in concentration to inhibit microbial iron(III) reduction. Consequently, observed trends were strongest in forested catchments, where nitrate concentrations were unaffected by agricultural and urban sources and which were therefore sensitive to reductions of atmospheric nitrogen depositions. We conclude that there is strong evidence that the decline in nitrogen deposition toward pre-industrial conditions lowers the redox buffer in riparian soils, destabilizing formerly fixed problematic compounds, and results in serious implications for water quality.}, language = {en} } @article{NguyenKumarMusolffetal.2022, author = {Nguyen, Tam and Kumar, Rohini and Musolff, Andreas and Lutz, Stefanie R. and Sarrazin, Fanny and Attinger, Sabine and Fleckenstein, Jan H.}, title = {Disparate Seasonal Nitrate Export From Nested Heterogeneous Subcatchments Revealed With StorAge Selection Functions}, series = {Water resources research}, volume = {58}, journal = {Water resources research}, number = {3}, publisher = {American Geophysical Union}, address = {Washington}, issn = {0043-1397}, doi = {10.1029/2021WR030797}, pages = {20}, year = {2022}, abstract = {Understanding catchment controls on catchment solute export is a prerequisite for water quality management. StorAge Selection (SAS) functions encapsulate essential information about catchment functioning in terms of discharge selection preference and solute export dynamics. However, they lack information on the spatial origin of solutes when applied at the catchment scale, thereby limiting our understanding of the internal (subcatchment) functioning. Here, we parameterized SAS functions in a spatially explicit way to understand the internal catchment responses and transport dynamics of reactive dissolved nitrate (N-NO3). The model was applied in a nested mesoscale catchment (457 km(2)), consisting of a mountainous partly forested, partly agricultural subcatchment, a middle-reach forested subcatchment, and a lowland agricultural subcatchment. The model captured flow and nitrate concentration dynamics not only at the catchment outlet but also at internal gauging stations. Results reveal disparate subsurface mixing dynamics and nitrate export among headwater and lowland subcatchments. The headwater subcatchment has high seasonal variation in subsurface mixing schemes and younger water in discharge, while the lowland subcatchment has less pronounced seasonality in subsurface mixing and much older water in discharge. Consequently, nitrate concentration in discharge from the headwater subcatchment shows strong seasonality, whereas that from the lowland subcatchment is stable in time. The temporally varying responses of headwater and lowland subcatchments alternate the dominant contribution to nitrate export in high and low-flow periods between subcatchments. Overall, our results demonstrate that the spatially explicit SAS modeling provides useful information about internal catchment functioning, helping to develop or evaluate spatial management practices.}, language = {en} } @article{SarrazinKumarBasuetal.2022, author = {Sarrazin, Fanny J. and Kumar, Rohini and Basu, Nandita B. and Musolff, Andreas and Weber, Michael and Van Meter, Kimberly J. and Attinger, Sabine}, title = {Characterizing catchment-scale nitrogen legacies and constraining their uncertainties}, series = {Water resources research}, volume = {58}, journal = {Water resources research}, number = {4}, publisher = {American Geophysical Union}, address = {Washington}, issn = {0043-1397}, doi = {10.1029/2021WR031587}, pages = {32}, year = {2022}, abstract = {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 km(2)) 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.}, language = {en} }