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Riparian zones are key ecotones that buffer aquatic ecosystems through removal of nitrogen (N) via processes such as denitrification. However, how dams alter riparian N cycling and buffering capacity is poorly understood. Here, we hypothesized that elevated groundwater and anoxia due to the backup of stream water above milldams may enhance denitrification. We assessed denitrification rates (using denitrification enzyme assays) and potential controlling factors in riparian sediments at various depths upstream and downstream of two relict U.S. mid‐Atlantic milldams. Denitrification was not significantly different between upstream and downstream, although was greater per river km upstream considering deeper and wider geometries. Further, denitrification typically occurred in hydrologically variable shallow sediments where nitrate‐N and organic matter were most concentrated. At depths below 1 m, both denitrification and nitrate‐N decreased while ammonium‐N concentrations substantially increased, indicating suppression of ammonium consumption or dissimilatory nitrate reduction to ammonium. These results suggest that denitrification occurs where dynamic groundwater levels result in higher rates of nitrification and mineralization, while another N process that produces ammonium‐N competes with denitrification for limited nitrate‐N at deeper, more stagnant/poorly mixed depths. Ultimately, while it is unclear whether relict milldams are sources of N, limited denitrification rates indicate that they are not always effective sinks; thus, milldam removal—especially accompanied by removal of ammonium‐N rich legacy sediments—may improve riparian N buffering.

How milldams alter riparian hydrologic and groundwater mixing regimes is not well understood. Understanding the effects of milldams and their legacies on riparian hydrology is key to assessing riparian pollution buffering potential and for making appropriate watershed management decisions. We examined the spatiotemporal effects of milldams on groundwater gradients, flow directions, and mixing regime for two dammed sites on Chiques Creek, Pennsylvania (2.4 m tall milldam), and Christina River, Delaware (4 m tall dam), USA. Riparian groundwater levels were recorded every 30 min for multiple wells and transects. Groundwater mixing regime was characterized using 30‐min specific conductance data and selected chemical tracers measured monthly for about 2 years. Three distinct regimes were identified for riparian groundwaters—wet, dry, and storm. Riparian groundwater gradients above the dam were low but were typically from the riparian zone to the stream. These flow directions were reversed (stream to riparian) during dry periods due to riparian evapotranspiration losses and during peak stream flows. Longitudinal (parallel to the stream) riparian flow gradients and directions also varied across the hydrologic regimes. Groundwater mixing varied spatially and temporally between storms and seasons. Near‐stream groundwater was poorly flushed or mixed during storms whereas that in the adjacent swales revealed greater mixing. This differential groundwater behavior was attributed to milldam legacies that include: berm and swale topography that influenced the routing of surface waters, varying riparian legacy sediment depths and hydraulic conductivities, evapotranspiration losses from riparian vegetation, and runoff input from adjoining roads.

The compounding effects of anthropogenic legacies for environmental pollution are significant, but not well understood. Here, we show that centennial‐scale legacies of milldams and decadal‐scale legacies of road salt salinization interact in unexpected ways to produce hot spots of nitrogen (N) in riparian zones. Riparian groundwater and stream water concentrations upstream of two mid‐Atlantic (Pennsylvania and Delaware) milldams, 2.4 and 4 m tall, were sampled over a 2 year period. Clay and silt‐rich legacy sediments with low hydraulic conductivity, stagnant and poorly mixed hydrologic conditions, and persistent hypoxia in riparian sediments upstream of milldams produced a unique biogeochemical gradient with nitrate removal via denitrification at the upland riparian edge and ammonium‐N accumulation in near‐stream sediments and groundwaters. Riparian groundwater ammonium‐N concentrations upstream of the milldams ranged from 0.006 to 30.6 mgN L⁻¹while soil‐bound values were 0.11–456 mg kg⁻¹. We attribute the elevated ammonium concentrations to ammonification with suppression of nitrification and/or dissimilatory nitrate reduction to ammonium (DNRA). Sodium inputs to riparian groundwater (25–1,504 mg L⁻¹) from road salts may further enhance DNRA and ammonium production and displace sorbed soil ammonium‐N into groundwaters. This study suggests that legacies of milldams and road salts may undercut the N buffering capacity of riparian zones and need to be considered in riparian buffer assessments, watershed management plans, and dam removal decisions. Given the widespread existence of dams and other barriers and the ubiquitous use of road salt, the potential for this synergistic N pollution is significant.