[1] Nitrate pollution of surface waters is widespread in lowland catchments with intensive agriculture. For identification of effective nitrate concentration reducing measures the nitrate fluxes within catchments need to be quantified. In this paper we applied a mass transfer function approach to simulate catchment-scale nitrate transport. This approach was extended with time-varying travel time distributions and removal of nitrate along flow paths by denitrification to be applicable for lowland catchments. Numerical particle tracking simulations revealed that transient travel time distributions are highly irregular and rapidly changing, reflecting the dynamics of rainfall and evapotranspiration. The solute transport model was able to describe 26 years of frequently measured chloride and nitrate concentrations in the Hupsel Brook catchment (6.6 km 2 lowland catchment in the Netherlands) with an R 2 value of 0.86. Most of the seasonal and daily variations in concentrations could be attributed to temporal changes of the travel time distributions. A full sensitivity analysis revealed that measurements other than just surface water nitrate and chloride concentrations are needed to constrain the uncertainty in denitrification, plant uptake, and mineralization of organic matter. Despite this large uncertainty, our results revealed that denitrification removes more nitrate from the Hupsel Brook catchment than stream discharge. This study demonstrates that a catchment-scale lumped approach to model chloride and nitrate transport processes suffices to accurately capture the dynamics of catchment-scale surface water concentration as long as the model includes detailed transient travel time distributions.

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For the evaluation of action programs to reduce surface water pollution, water authorities invest heavily in water quality monitoring. However, sampling frequencies are generally insufficient to capture the dynamical behavior of solute concentrations. For this study, we used on-site equipment that performed semicontinuous (15 min interval) NO 3 and P concentration measurements from June 2007 to July 2008. We recorded the concentration responses to rainfall events with a wide range in antecedent conditions and rainfall durations and intensities. Through sequential linear multiple regression analysis, we successfully related the NO 3 and P event responses to high-frequency records of precipitation, discharge, and groundwater levels. We applied the regression models to reconstruct concentration patterns between lowfrequency water quality measurements. This new approach significantly improved load estimates from a 20% to a 1% bias for NO 3 and from a 63% to a 5% bias for P. These results demonstrate the value of commonly available precipitation, discharge, and groundwater level data for the interpretation of water quality measurements. Improving load estimates from low-frequency concentration data just requires a period of highfrequency concentration measurements and a conceptual, statistical, or physical model for relating the rainfall event response of solute concentrations to quantitative hydrological changes.

Abstract. Freely discharging lowland catchments are characterized by a strongly seasonal contracting and expanding system of discharging streams and ditches. Due to this rapidly changing active channel network, discharge and solute transport cannot be modeled by a single characteristic travel path, travel time distribution, unit hydrograph, or linear reservoir. We propose a systematic spatial averaging approach to derive catchment-scale storage and discharge from point-scale water balances. The effects of spatial heterogeneity in soil properties, vegetation, and drainage network are lumped and described by a relation between groundwater storage and the spatial probability distribution of groundwater depths with measurable parameters. The model describes how, in lowland catchments, the catchment-scale flux from groundwater to surface water via various flow routes is affected by a changing active channel network, the unsaturated zone and surface ponding. We used observations of groundwater levels and catchment discharge of a 6.6 km 2 Dutch watershed in combination with a high-resolution spatially distributed hydrological model to test the model approach. Good results were obtained when modeling hourly discharges for a period of eight years. The validity of the underlying assumptions still needs to be tested under different conditions and for catchments of various sizes. Nevertheless, at this stage the model can already improve monitoring efficiency of groundwater-surface water interactions.

Agricultural pollutants in catchments are transported toward the discharging stream through various flow routes such as tube drain flow, groundwater flow, interflow, and overland flow. Direct measurements of flow route contributions are difficult and often impossible. We developed a field‐scale setup that can measure the contribution of the tube drain flow route to the total discharge toward the surface water system. We then embedded these field‐scale measurements in a nested measurement setup to asses the value of field‐scale measurements for interpretation of catchment‐scale discharge and nitrate concentrations using a linear flow route mixing model. In a lowland catchment, we physically separated the tube drain effluent from the discharge of all other flow routes. Upscaling the field‐scale flow route discharge contributions to the subcatchment and the catchment scale with a linear flow route mixing model gave a good prediction of the catchment discharge. Catchment‐scale nitrate concentrations were simulated well for a heavy rainfall event but poorly for a small rainfall event. The nested measurement setup revealed that the fluxes at a single field site cannot be representative for the entire catchment at all times. However, the distinctly different hydrograph reaction of the individual flow routes on rainfall events at the field site made it possible to interpret the catchment‐scale hydrograph and nitrate concentrations. This study showed that physical separation of flow route contributions at the field scale is feasible and essential for understanding catchment‐scale discharge generation and solute transport processes.