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On their way from inland to the ocean, flowing water bodies, their constituents and their biotic communities are ex-posed to complex transport and transformation processes. However, detailed process knowledge as revealed by La-grangian measurements adjusted to travel time is rare in large rivers, in particular at hydrological extremes. To fill this gap, we investigated autotrophic processes, heterotrophic carbon utilization, and micropollutant concentrations applying a Lagrangian sampling design in a 600 km section of the River Elbe (Germany) at historically low discharge. Under base flow conditions, we expect the maximum intensity of instream processes and of point source impacts. Phy-toplankton biomass and photosynthesis increased from upstream to downstream sites but maximum chlorophyll con-centration was lower than at mean discharge. Concentrations of dissolved macronutrients decreased to almost complete phosphate depletion and low nitrate values. The longitudinal increase of bacterial abundance and production was less pronounced than in wetter years and bacterial community composition changed downstream. Molecular analyses revealed a longitudinal increase of many DOM components due to microbial production, whereas saturated lipid-like DOM, unsaturated aromatics and polyphenols, and some CHOS surfactants declined. In decomposition exper-iments, DOM components with high O/C ratios and high masses decreased whereas those with low O/C ratios, low masses, and high nitrogen content increased at all sites. Radiocarbon age analyses showed that DOC was relatively old (890-1870 years B.P.), whereas the mineralized fraction was much younger suggesting predominant oxidation of algal lysis products and exudates particularly at downstream sites. Micropollutants determining toxicity for algae (terbuthylazine, terbutryn, isoproturon and lenacil), hexachlorocyclohexanes and DDTs showed higher concentrations from the middle towards the downstream part but calculated toxicity was not negatively correlated to phytoplankton. Overall, autotrophic and heterotrophic process rates and micropollutant concentrations increased from up-to down-stream reaches, but their magnitudes were not distinctly different to conditions at medium discharges.
Increasingly available high-frequency data during storm events, when hydrological dynamics most likely activate nitrate storage-flux exchanges, reveal insights into catchment nitrate dynamics. In this study, we explored impacts of seasonality and landscape gradients on nitrate concentration-discharge (C-Q) hysteresis patterns in the Selke catchment, central Germany, which has heterogeneous combinations of meteorological, hydrogeological and land use conditions. Three nested gauging stations established along the main Selke River captured flow and nitrate export dynamics from the uppermost subcatchment (mixed forest and arable land), middle subcatchment (pure steep forest) and lowermost subcatchment (arable and urban land). We collected continuous high-frequency (15-min) discharge and nitrate concentration data from 2012 to 2017 and analyzed the 223 events detected at all three stations. A dominant hysteresis pattern in the uppermost and middle subcatchments was counter-clockwise and combined with an accretion effect, indicating many proximal and mobilized distal nitrate sources. However, 66% of all events at the catchment outlet experienced a dilution effect, possibly due to mechanisms that vary seasonally. During wetting/wet periods (October-March), it was combined mainly with a counter-clockwise pattern due to the dominance of event runoff volume from the uppermost and middle subcatchments. During drying/dry periods (April-September), however, it was combined mainly with a clockwise pattern due to occasional quick surface flows from lowland near-stream urban areas. In addition, the clockwise hysteresis occurred mainly from May-October during mostly drying/dry periods at all three sites, indicating little distal nitrate transport in response to the low terrestrial hydrological connectivity, especially in the lowermost dry and flat sub-catchment. This comprehensive analysis (i.e., clockwise vs. counter-clockwise, accretion vs. dilution) enables in-depth analysis of nitrate export mechanisms during certain periods under different landscape conditions. Specific combination of C-Q relationships could identify target locations for agricultural management actions that decrease nitrate output. Therefore, we strongly encourage long-term multisite and high-frequency monitoring strategies in heterogeneous nested catchment(s), which can help understand process mechanisms, generate data for physical-based water-quality modeling and provide guidance for water and agricultural management.
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.