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Abstract The seasonal controls of hydrology, temperature, hypoxia, and biogeochemical conditions for groundwater ammonium–N (NH₄⁺) concentrations are not well understood. Here we investigated these controls for riparian groundwaters located upstream of two milldams over a period of 4 years. Groundwater chemistry was sampled monthly while groundwater elevations, hydraulic gradients, and temperatures were recorded sub‐hourly. Distinct seasonal patterns for NH₄⁺were observed which differed among the wells. For wells that displayed a strong seasonal pattern, NH₄⁺concentrations increased through the summer and peaked in October–November. These elevated concentrations were attributed to ammonification, suppression of nitrification, and/or dissimilatory nitrate reduction to ammonium (DNRA). These processes were driven by high groundwater temperatures, low hydraulic gradients (or long residence times), hypoxic/anoxic groundwater conditions, and increased availability of dissolved organic carbon as an electron donor. In contrast, NH₄⁺concentrations decreased in the riparian groundwater from January to April during cool and wet conditions. A groundwater well with elevated total dissolved iron (TdFe) concentrations had elevated NH₄⁺concentrations but displayed a muted seasonal response. In addition to hydrologic controls, we attributed this response to additional NH₄⁺contribution from Fe‐driven autotrophic DNRA and/or ammonification linked to dissimilatory Fe reduction. Understanding the temporal patterns and factors controlling NH₄⁺in riparian groundwaters is important for making appropriate watershed management decisions and implementing appropriate best management practices. 

Introduction Damming has substantially fragmented and altered riverine ecosystems worldwide. Dams slow down streamflows, raise stream and groundwater levels, create anoxic or hypoxic hyporheic and riparian environments and result in deposition of fine sediments above dams. These sediments represent a good opportunity to study human legacies altering soil environments, for which we lack knowledge on microbial structure, depth distribution, and ecological function. Methods Here, we compared high throughput sequencing of bacterial/ archaeal and fungal community structure (diversity and composition) and functional genes (i.e., nitrification and denitrification) at different depths (ranging from 0 to 4 m) in riparian sediments above breached and existing milldams in the Mid-Atlantic United States. Results We found significant location- and depth-dependent changes in microbial community structure. Proteobacteria, Bacteroidetes, Firmicutes, Actinobacteria, Chloroflexi, Acidobacteria, Planctomycetes, Thaumarchaeota, and Verrucomicrobia were the major prokaryotic components while Ascomycota, Basidiomycota, Chytridiomycota, Mortierellomycota, Mucoromycota, and Rozellomycota dominated fungal sequences retrieved from sediment samples. Ammonia oxidizing genes ( amo A for AOA) were higher at the sediment surface but decreased sharply with depth. Besides top layers, denitrifying genes ( nos Z) were also present at depth, indicating a higher denitrification potential in the deeper layers. However, these results contrasted with in situ denitrification enzyme assay (DEA) measurements, suggesting the presence of dormant microbes and/or other nitrogen processes in deep sediments that compete with denitrification. In addition to enhanced depth stratification, our results also highlighted that dam removal increased species richness, microbial diversity, and nitrification. Discussion Lateral and vertical spatial distributions of soil microbiomes (both prokaryotes and fungi) suggest that not only sediment stratification but also concurrent watershed conditions are important in explaining the depth profiles of microbial communities and functional genes in dammed rivers. The results also provide valuable information and guidance to stakeholders and restoration projects. 

Abstract Groundwater nitrate‐N isotopes (δ¹⁵N‐) have been used to infer the effects of natural and anthropogenic change on N cycle processes in the environment. Here we report unexpected changes in groundwater δ¹⁵N‐ for riparian zones affected by relict milldams and road salt salinization. Contrary to natural, undammed conditions, groundwater δ¹⁵N‐ values declined from the upland edge through the riparian zone and were lowest near the stream. Groundwater δ¹⁵N‐ values increased for low electron donor (dissolved organic carbon) to acceptor ratios but decreased beyond a change point in ratios. Groundwater δ¹⁵N‐ values were particularly low for the riparian milldam site subjected to road‐salt salinization. We attributed these N isotopic trends to suppression of denitrification, occurrence of dissimilatory nitrate reduction to ammonium (DNRA), and/or effects of road salt salinization. Groundwater δ¹⁵N‐ can provide valuable insights into process mechanisms and can serve as “imprints” of anthropogenic activities and legacies. 

Anthropogenic salt inputs have impacted many streams in the U.S. for over a century. Urban stream salinity is often chronically elevated and punctuated by episodic salinization events, which can last hours to days after snowstorms and the application of road salt. Here, we investigated the impacts of freshwater salinization on total dissolved nitrogen (TDN) and NO3−/NO2− concentrations and fluxes across time in urban watersheds in the Baltimore-Washington D.C. metropolitan area of the Chesapeake Bay region. Episodic salinization from road salt applications and snowmelt quickly mobilized TDN in streams likely through soil ion exchange, hydrologic flushing, and other biogeochemical processes. Previous experimental work from other studies has shown that salinization can mobilize nitrogen from sediments, but less work has investigated this phenomenon with high-frequency sensors and targeted monitoring during road salt events. We found that urban streams exhibited elevated concentrations and fluxes of TDN, NO3−/NO2−, and specific conductance that rapidly peaked during and after winter road salt events, and then rapidly declined afterwards. We observed plateaus in TDN concentrations in the ranges of the highest specific conductance values (between 1000 and 2000 μS/cm) caused by road salt events. Plateaus in TDN concentrations beyond a certain threshold of specific conductance values suggested source limitation of TDN in watersheds (at the highest ranges in chloride concentrations and ranges); salts were likely extracting nitrogen from soils and streams through ion exchange in soils and sediments, ion pairing in soils and waters, and sodium dispersion of soils to a certain threshold level. When watershed transport was compared across land use, including a forested reference watershed, there was a positive relationship between Cl− loads and NO3−/NO2− loads. This relationship occurred across all sites regardless of land use, which suggests that the mass transport of Cl− and NO3−/NO2− are likely influenced by similar factors such as soil ion exchange, ion pairing, sodium dispersion of soils, hydrologic flushing, and biogeochemical processes. Freshwater salinization has the potential to alter the magnitude and timing of total dissolved nitrogen delivery to receiving waters during winter months following road salt applications, and further work should investigate the seasonal relationships of N transport with salinization in urban watersheds. 

ABSTRACT Controls of hydrology, landscape and soil characteristics on redox potentials, particularly at fine spatial and temporal scales, are poorly quantified and understood. Using high‐frequency sensors (30 min), the variability of redox potentials (Eh) in riparian soils was investigated for multiple depths and across diel, event and seasonal time scales over a period of 2 years. Sampling was performed for two riparian sites upstream of dams with contrasting soil textures. Incremental changes in soil moisture triggered abrupt and disproportionately large shifts in soil Eh values, a threshold‐like behaviour that has not been reported before. Contrary to expectations, Eh values initially decreased as the soil dried and then abruptly increased with further drying and oxidation of soil. Diel Eh patterns differed between sites, with the sand‐rich site oxidising by day and reducing at night, while the clay‐ and silt‐rich site showed the opposite pattern. These differences were attributed to differential oxygen diffusion and consumption by processes such as photosynthesis, evapotranspiration and microbial respiration. Sharp Eh shifts also occurred at soil depths with textural discontinuities. These redox hot spots and hot moments were attributed to differences in site topography, hydrology and soil characteristics such as texture, moisture, organic matter content and microbial biomass. Identifying and understanding these fine‐scale spatial and temporal patterns of Eh is critical for improved characterisation and quantification of biogeochemical processes in redox‐sensitive environments. This study underscores the value of high‐frequency redox sensors in making such assessments. 

Abstract 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. 

Abstract 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. 

Abstract Understanding the balance between denitrification and dissimilatory nitrate reduction to ammonium (DNRA) in riparian systems is essential for managing watershed nitrogen (N) budgets and evaluating restoration practices. This balance is influenced by several factors including concentrations and ratio of various organic and inorganic electron donors (dissolved organic carbon [DOC], Fe²⁺) to acceptor (NO₃⁻). In riparian sediments, these factors can change rapidly over space and time, complicating measurement and quantification. We used a PFLOTRAN batch reactor model calibrated to laboratory microcosm experiments where the denitrification and DNRA rates in riparian sediments were measured using¹⁵N stable isotopes. Although DOC/NO₃⁻ratios influenced the relative proportions of denitrification and DNRA, the processes were also affected by elemental concentrations. For a starting DOC concentration of 0.12 mgL⁻¹, DNRA exceeded denitrification at DOC/NO₃⁻ = 6; however, this shift was not observed within a range of DOC/NO₃⁻ = 30 at higher DOC concentration of 12 mgL⁻¹. Heterotrophic pathways dominated NO₃‐N reduction with smaller contribution from autotrophic pathways. These findings suggest that although heterotrophic pathways are important in carbon‐rich sediments, autotrophic pathways can be significant in carbon‐depleted conditions in the presence of inorganic electron donors such as Fe²⁺. Our simulations also highlighted key challenges with constraining model rate constants and parameters and the need for site specific calibrations. This work highlights the value of process‐based modeling in quantifying denitrification‐DNRA partitioning and the variable controls of electron donors and acceptors. Such simulations could be extended to riparian buffers to determine if they are effective management sinks for N mitigation.