Significance: Although groundwater is a critical source of drinking water and irrigation, it has been polluted worldwide by agriculture, industry, and domestic activity. Because assessing groundwater quality and recovery rates is challenging, we developed a method for determining where and how quickly nitrate is removed in aquifers using just a few point measurements of groundwater chemistry. This methodology opens new avenues for characterizing catchment-scale nutrient dynamics, including nitrogen, carbon, and silica, with existing datasets for ecosystems around the globe. Understanding the subsurface structure of reactivity would also improve estimates of recovery time frames for polluted ecosystems and inform sustainable limits for anthropogenic activity.

Direct and indirect effects from human activity have dramatically increased nutrient loading to aquatic inland and estuarine ecosystems. Despite an abundance of studies investigating the impact of agricultural activity on water quality, our understanding of what determines the capacity of a watershed to remove or retain nutrients remains limited. The goal of this study was to identify proximate and ultimate controls on dissolved organic carbon and nutrient dynamics in small agricultural catchments by investigating the relationship between catchment characteristics, stream discharge, and water chemistry. We analyzed a 5-year, high-frequency water chemistry data set from three catchments in western France ranging from 2.3 to 10.8 km². The relationship between hydrology and solute concentrations differed between the three catchments and was associated with hedgerow density, agricultural activity, and geology. The catchment with thicker soil and higher surface roughness had relatively invariant carbon and nutrient chemistry across hydrologic conditions, indicating high resilience to human disturbance. Conversely, the catchments with smoother, thinner soils responded to both intra- and interannual hydrologic variation with high concentrations of phosphate (PO₄³⁻) and ammonium (NH₄⁺) in streams during low flow conditions and strong increases in dissolved organic carbon (DOC), sediment, and particulate organic matter during high flows. Despite contrasting agricultural activity between catchments, the physical context (geology, topography, and land-use configuration) appeared to be the most important determinant of catchment solute dynamics based on principle components analysis. The influence of geology and accompanying topographic and geomorphological factors on water quality was both direct and indirect because the distribution of agricultural activity in these catchments is largely a consequence of the geologic and topographic context. This link between inherent catchment buffering capacity and the probability of human disturbance provides a useful perspective for evaluating vulnerability of aquatic ecosystems and for managing systems to maintain agricultural production while minimizing leakage of nutrients.