Time lags of nitrate, chloride, and tritium in streams assessed by dynamic groundwater flow tracking in a lowland landscape

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.