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Diss Bartsch Monsoonal affected dynamics of nitrate and dissolved organic carbon in a mountainous catchment under intensive land-use Dissertation to attain the academic degree of Doctor of Natural Science (Dr. rer. nat.) of the Bayreuth Graduate School of Mathematical and Natural Sciences (BayNAT) of the University of Bayreuth presented by Svenja Bartsch born 2 January 1981 in Friedrichshafen (Germany) Bayreuth, August 2013 This doctoral thesis was prepared at the department of Hydrology at the University of Bayreuth from April 2009 until August 2013 and was supervised by Dr. Jan H. Fleckenstein, Prof. Dr. Stefan Peiffer, and Dr. Christopher L. Shope. This is a full reprint of the dissertation submitted to attain the academic degree of Doctor of Natural Science (Dr. rer. nat.) and approved by the Bayreuth Graduate School of Mathematical and Natural Sciences (BayNAT) of the University of Bayreuth. Date of submission : 27.08.2013 Date of scientific colloquium : 20.12.2013 Acting director : Prof. Dr. Franz X. Schmid Doctoral committee : Dr. Johannes Lüers (chairman) Prof. Dr. Stefan Peiffer (first reviewer) Prof. John Tenhunen, Ph.D. (second reviewer) Dr. Jan H. Fleckenstein ii Abstract In recent decades, complex mountainous landscapes have been increasingly under pressure by deforestation and intensified highland agriculture. This trend not only compromises the quality of water in the highlands, but also impacts the availability of water resources downstream. Hence, an effective and sustainable management of these mountainous regions is essential and needed to mitigate this risk. Developing sustainable management principles to ensure the freshwater supply, however, requires a profound understanding of decisive factors and processes that control the water quality in mountainous landscapes. Amongst other substances, nitrate and dissolved organic carbon (DOC) play a critical role in the ecosystem health of water bodies. The major focus of this dissertation is on determining the nitrate and DOC mobilization processes and dynamics in the Haean Catchment, a mountainous watershed located in South Korea, which is agriculturally productive and strongly influenced by the prevailing East-Asian monsoon. The primary objective was to identify decisive factors that control the nitrate and DOC mobilization processes and dynamics in such catchments. To these ends, we conducted stream water quality and discharge measurements during a range of conditions, from monsoonal rainfall events to dry, baseflow conditions. Assessments were completed along the topographic elevation gradient of the catchment, from an upland deciduous forest, over areas intensively used for agriculture, down to the catchment outlet. In order to gain a better understanding of nutrient fate within the Haean Catchment, we investigated river-aquifer exchange fluxes. In addition to hydraulic gradient monitoring, we used heat as tracer. To resolve the river-aquifer exchange fluxes, we set up a two-dimensional flow and heat transport model using the numerical code HydroGeoSphere (HGS). Potential effects of river-aquifer exchange dynamics on local water quality were investigated by collecting both, river and groundwater samples. Furthermore, we determined the impact of the ridge and furrow cultivation that is commonly applied in South Korean dryland agriculture, on nitrate leaching and evaluated fertilizer best management practices (FBMPs) using a three-dimensional flow and solute transport model (HGS). Our results show that DOC and nitrate sources as well as their mobilization differ between the forest and agricultural river sites. In the forest, elevated in-stream DOC concentrations during rainfalls were due to hydrologic flushing of soluble organic matter in upper soil horizons with a strong dependency on pre-storm wetness conditions. Nitrate contributions to the stream occurred predominantly along interflow transport pathways. At the agricultural sites, in-stream DOC concentrations were considerably higher and supplied from adjacent rice paddies. The highest in-stream nitrate concentrations occurred in the lower agricultural part of the catchment. Through hydraulic gradient monitoring, we identified in this part of the catchment a distinct connection between the river and aquifer, and nitrate-rich groundwater inputs to the river elevated the in-stream nitrate concentration. In the mid-elevation portion of the catchment, however, a limited connectivity between the river and aquifer was identified and river water quality was consequently unaffected in these areas. iii The results of our HGS modeling study show a high temporal and spatial variability in river-aquifer exchange fluxes with frequent flow reversals during the monsoon season. Our results also suggest that these flow reversals may enhance the natural attenuation of nitrate in the shallow groundwater below the stream. The simulation results on evaluating FBMPs demonstrate that applying a combination of several FBMPs such as an adapted placement and timing is recommended to minimize the risk of groundwater nitrate contamination. Overall, this dissertation demonstrates that the hydrologic pathways resulting from the monsoon climate drive the in-stream DOC dynamics in the forested catchment, whereas sources and mobilization of DOC in downstream agricultural areas are mainly controlled by the specific land-use type. In particular, the widely used rice paddy “plot-to-plot” irrigation system in Korean highlands was shown to control in-stream DOC concentrations. Nitrate dynamics in streams and aquifers in the agricultural areas of the catchment reflect the combined effects of land-use type and monsoonal hydrology. Particularly, the highly variable river-aquifer exchange fluxes with frequent flow reversals, which may enhance the nitrate attenuation, are driven by monsoonal extreme precipitation events. Since it has been forecasted that global warming will increase the frequency and the intensity of extreme precipitation events also in other regions of the world, our results will become increasingly important in future water quality assessments and research. iv Zusammenfassung In den letzten Jahrzehnten sind komplexe Bergregionen durch Kahlschläge zugunsten einer intensivierten Landwirtschaft im Hochland zunehmend unter Druck geraten. Diese Entwicklung gefährdet nicht nur die Wasserqualität im Hochland, ferner sind die natürlichen Ressourcen stromabwärts einem erhöhten Risiko ausgesetzt. Um dieses Risiko möglichst effektiv einzudämmen, bedarf es einer nachhaltigen Bewirtschaftung von Bergregionen. Die Entwicklung nachhaltiger Management-Prinzipien zur Sicherung der Trinkwasserversorgung erfordert jedoch profunde Kenntnisse über entscheidende Faktoren und Prozesse, die die Wasserqualität regulieren. Neben anderen Substanzen spielen Nitrat und gelöster organischer Kohlenstoff (DOC) eine wichtige Rolle für die ökosystemare Gesundheit von Gewässern. Das Hauptaugenmerk dieser Arbeit liegt auf der Ermittlung von Nitrat- und DOC Dynamiken und Mobilisierungsprozessen in Haean, ein landwirtschaftlich intensiv genutztes sowie stark durch das ostasiatische Monsunklima beeinflusstes Einzugsgebiet im Hochland Südkoreas. Primäres Ziel dieser Arbeit war es die entscheidenden Faktoren, die die Nitrat- und DOC Mobilisierungsprozesse und Dynamiken steuern, zu identifizieren. Zu diesem Zweck führten wir vorwiegend während monsunaler Regenereignisse Fluss- wasserqualitäts- und Abflussmessungen entlang des topographischen Höhengradienten des Einzugsgebietes durch, beginnend auf den bewaldeten Hängen, über landwirtschaftlich intensiv genutzte Flächen bis hin zum Einzugsgebietsauslass. Um ein besseres Verständnis über den Nährstoffverbleib im Einzugsgebiet zu gewinnen, untersuchten wir die Austausch- dynamiken zwischen Fluss und Grundwasserleiter. Neben der Überwachung hydraulischer Gradienten verwendeten wir Wärme als „Tracer“. Die Berechnung der Austauschflüsse erfolgte anhand eines zweidimensionalen Strömungs- und Wärmetransportmodells, unter der Verwendung des numerischen Codes HydroGeoSphere (HGS). Mögliche Auswirkungen der Grundwasser-Fluss-Interaktionen auf die Wasserqualität ermittelten wir anhand von Fluss- und Grundwasserbeprobungen. Zudem untersuchten wir die Auswirkung des dort weitver- breiteten Dammkultivierungssystems auf die Nitratauswaschung und evaluierten „Fertilizer- Best-Management Practices“ (FBMPs) mittels eines dreidimensionalen Strömungs- und Stofftransportmodells (HGS). Unsere Ergebnisse zeigen, dass die Nitrat und DOC Quellen und deren Mobilisierung sich im Wald deutlich von denen in den landwirtschaftlich genutzten Flächen unterscheiden. Im Wald führten während monsunaler Niederschläge hydrologische Auswaschungsprozesse von gelösten organischen Substanzen aus dem Oberboden zu erhöhten DOC-Konzentrationen im Flusswasser. Nitrat wurde im Wald vorwiegend über den Zwischenabfluss in den Fluss eingetragen. In den landwirtschaftlich dominierten Flüssen höherer Ordnung identifizierten wir wesentlich höhere DOC-Konzentrationen, welche auf den DOC-Eintrag aus Reisfeldern zurückzuführen sind. Die höchsten Nitratkonzentrationen im Flusswasser wurden in der landwirtschaftlich genutzten Beckenebene gemessen und beruhen auf nitratbelastetem Grundwasserzustrom. Durch die Überwachung der hydraulischen Gradienten identifizierten wir hier eine gute Anbindung des Flusses an das Grundwasser, wohingegen in mittlerer v Höhenlage des Einzugsgebiets lediglich eine eingeschränkte Verbindung zwischen Fluss und Aquifer vorliegt. Generell zeigen unsere HGS-Simulationen
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