Recharge rates of nitrate (NO3-) to groundwater beneath agricultural land commonly are greater than discharge rates of NO3- in nearby streams, but local controls of NO3- distribution in the subsurface generally are poorly known. Groundwater dating (CFC, 3H) was combined with chemical (ions and gases) and stable isotope (N, S, and C) analyses to resolve the effects of land use changes, flow patterns, and water-aquifer reactions on the distributions of O2, NO3-, SO4=, and other constituents in a two-dimensional vertical section leading from upland cultivated fields to a riparian wetland and stream in a glacial outwash sand aquifer near Princeton, Minnesota. Within this section a "plume" of oxic NO3--rich groundwater was present at shallow depths beneath the fields and part of the wetland but terminated before reaching the stream or the wetland surface. Groundwater dating and hydraulic measurements indicate travel times in the local flow system of 0 to >40 years, with stratified recharge beneath the fields, downward diversion of the shallow NO3--bearing plume by semiconfining organic-rich valley-filling sediments under the wetland and upward discharge across the valley and stream bottom. The concentrations and ??15N values of NO3- and N2 indicate that the NO3- plume section was bounded in three directions by a curvilinear zone of active denitrification that limited its progress; however, when recalculated to remove the effects of denitrification, the data also indicate changes in both the concentrations and ??15N values of NO3- that was recharged in the past. Isotope data and mass balance calculations indicate that FeS2 and other ferrous Fe phases were the major electron donors for denitrification in at least two settings: (1) within the glacial-fluvial aquifer sediments beneath the recharge and discharge areas and (2) along the bottom of the valley-filling sediments in the discharge area. Combined results indicate that the shape and progress of the oxic NO3- plume termination were controlled by a combination of (1) historical and spatial variations in land use practices, (2) contrast in groundwater flow patterns between the agricultural recharge area and riparian wetland discharge area, and (3) distribution and abundance of electron donors in both the sand aquifer and valley-filling sediments. The data are consistent with slow migration of redox zones through the aquifer in response to recharging oxic groundwater during Holocene time, then an order-of-magnitude increase in the flux of electron acceptors as a result of agricultural NO3- contamination in the late twentieth century, to which the redox zone configuration still may be adjusting. The importance of denitrification for NO3- movement through formerly glaciated terrains should depend on the source areas and depositional environments of the glacial sediments, as well as geomorphology and recent stream-valley sediment history.
Additional publication details
Denitrification in the recharge area and discharge area of a transient agricultural nitrate plume in a glacial outwash sand aquifer, Minnesota