Using chemical, hydrologic, and age dating analysis to delineate redox processes and flow paths in the riparian zone of a glacial outwash aquifer‐stream system

A combination of chemical and dissolved gas analyses, chlorofluorocarbon age dating, and hydrologic measurements were used to determine the degree to which biogeochemical processes in a riparian wetland were responsible for removing NO₃⁻from groundwaters discharging to the Otter Tail River in west central Minnesota. An analysis of river chemistry and flow data revealed that NO₃⁻ concentrations in the river increased in the lower half of the 8.3 km study reach as the result of groundwater discharge to the river. Groundwater head measurements along a study transect through the riparian wetland revealed a zone of groundwater discharge extending out under the river. On the basis of combined chemical, dissolved gas, age date, and hydrologic results, it was determined that water chemistry under the riparian wetland was controlled largely by upgradient groundwaters that followed flow paths up to 16 m deep and discharged under the wetland, creating a pattern of progressively older, more chemically reduced, low NO₃⁻ water the farther one progressed from the edge of the wetland toward the river. These findings pose challenges for researchers investigating biogeochemical processes in riparian buffer zones because the progressively older groundwaters entered the aquifer in earlier years when less NO₃⁻ fertilizer was being used. NO₃⁻ concentrations originally present in the groundwater had also decreased in the upgradient aquifer as a result of denitrification and progressively stronger reducing conditions there. The resulting pattern of decreasing NO₃⁻ concentrations across the riparian zone may be incorrectly interpreted as evidence of denitrification losses there instead of in the upgradient aquifer. Consequently, it is important to understand the hydrogeologic setting and age structure of the groundwaters being sampled in order to avoid misinterpreting biogeochemical processes in riparian zones.