Abstract. Surface waters are under pressure from diffuse pollution from agricultural activities, and groundwater is known to be a connection between the agricultural fields and streams. This paper is one of the first to calculate long-term in-stream concentrations of tritium, chloride, and nitrate using dynamic groundwater travel time distributions (TTDs) derived from a distributed, transient, 3D groundwater flow model using forward particle tracking. We tested our approach in the Springendalse Beek catchment, a lowland stream in the east of the Netherlands, for which we collected a long time series of chloride and nitrate concentrations (1969–2018). The Netherlands experienced a sharp decrease in concentrations of solutes leaching to groundwater in the 1980s due to legislations on the application of nitrogen to agricultural fields. Stream measurements of chloride and nitrate showed that the corresponding trend reversal in the groundwater-fed stream occurred after a time lag of 5–10 years. By combining calculated TTDs with the known history of nitrogen and chloride inputs, we found that the variable contribution of different groundwater flow paths to stream water quality reasonably explained the majority of long-term and seasonal variation in the measured stream nitrate concentrations. However, combining only TTDs and inputs underestimated the time lag between the peak in nitrogen input and the following trend reversal of nitrate in the stream. This feature was further investigated through an exploration of the model behaviour under different scenarios. A time lag of several years, and up to decades, can occur due to (1) a thick unsaturated zone adding a certain travel time, (2) persistent organic matter with a slow release of N in the unsaturated zone, (3) a long mean travel time (MTT) compared to the rate of the reduction in nitrogen application, (4) areas with a high application of nitrogen (agricultural fields) being located further away from the stream or drainage network, or (5) a higher presence of nitrate attenuating processes close to the stream or drainage network compared to the rest of the catchment. By making the connection between dynamic groundwater travel time distributions and in-stream concentration measurements, we provide a method for validating the travel time approach and make the step towards application in water quality modelling and management.
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.
In recent years, DNA-tagged silica colloids have been used as an environmental tracer. A major advantage of this technique is that the DNA-coding provides an unlimited number of unique tracers without a background concentration. However, little is known about the effects of physio-chemical subsurface properties on the transport behavior of DNA-tagged silica tracers. We are the first to explore the deposition kinetics of this new DNA-tagged silica tracer for different pore water chemistries, flow rates, and sand grain size distributions in a series of saturated sand column experiments in order to predict environmental conditions for which the DNA-tagged silica tracer can best be employed. Our results indicated that the transport of DNA-tagged silica tracer can be well described by first order kinetic attachment and detachment. Because of massive re-entrainment under transient chemistry conditions, we inferred that attachment was primarily in the secondary energy minimum. Based on calculated sticking efficiencies of the DNA-tagged silica tracer to the sand grains, we concluded that a large fraction of the DNA-tagged silica tracer colliding with the sand grain surface did also stick to that surface, when the ionic strength of the system was higher. The experimental results revealed the sensitivity of DNA-tagged silica tracer to both physical and chemical factors. This reduces its applicability as a conservative hydrological tracer for studying subsurface flow paths. Based on our experiments, the DNA-tagged silica tracer is best applicable for studying flow routes and travel times in coarse grained aquifers, with a relatively high flow rate. DNA-tagged silica tracers may also be applied for simulating the transport of engineered or biological colloidal pollution, such as microplastics and pathogens.
Abstract. The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.
