New insights into nitrate dynamics in a karst groundwater system gained from in situ high-frequency optical sensor measurements

Understanding nitrate dynamics in groundwater systems as a function of climatic conditions, especially during contrasting patterns of drought and wet cycles, is limited by a lack of temporal and spatial data. Nitrate sensors have the capability for making accurate, high-frequency measurements of nitrate in situ, but have not yet been evaluated for long-term use in groundwater wells. We measured in situ nitrate continuously in two groundwater monitoring wells —one rural and one urban—located in the recharge zone of a productive karst aquifer in central Texas in order to resolve changes that occur over both short-term (hourly to daily) and long-term (monthly to yearly) periods. Nitrate concentrations, measured as nitrate-nitrogen in milligrams per liter (mg/L), during drought conditions showed little or no temporal change as groundwater levels declined. During aquifer recharge, extremely rapid changes in concentration occurred at both wells as documented by hourly data. At both sites, nitrate concentrations were affected by recharging surface water as evidenced by nitrate concentrations in groundwater recharge (0.8–1.3 mg/L) that were similar to previously reported values for regional recharging streams. Groundwater nitrate concentrations responded differently at urban and rural sites during groundwater recharge. Concentrations at the rural well (approximately 1.0 mg/L) increased as a result of higher nitrate concentrations in groundwater recharge relative to ambient nitrate concentrations in groundwater, whereas concentrations at the urban well (approximately 2.7 mg/L) decreased as a result of the dilution of higher ambient nitrate concentrations relative to those in groundwater recharge. Notably, nitrate concentrations decreased to as low as 0.8 mg/L at the urban site during recharge but postrecharge concentrations exceeded 3.0 mg/L. A return to higher nitrate concentrations postrecharge indicates mobilization of a localized source of elevated nitrate within the urbanized area of the aquifer. Changes in specific conductance were observed at both sites during groundwater recharge, and a significant correlation between specific conductance and nitrate (correlation coefficient [R] = 0.455) was evident at the urban site where large (3-fold) changes in nitrate occurred. Nitrate concentrations and specific conductance measured during a depth profile indicated that the water column was generally homogeneous as expected for this karst environment, but changes were observed in the most productive zone of the aquifer that might indicate some heterogeneity within the complex network of flow paths. Resolving the timing and magnitude of changes and characterizing fine-scale vertical differences would not be possible using conventional sampling techniques. The patterns observed in situ provided new insight into the dynamic nature of nitrate in a karst groundwater system.