skip to main content


Title: Hydrogeologic Controls of Surface Water‐Groundwater Nitrogen Dynamics Within a Tidal Freshwater Zone
Abstract

Microbial processing of reactive nitrogen in stream sediments and connected aquifers can remove and transform nitrogen prior to its discharge into coastal waters, decreasing the likelihood of harmful algal blooms and low oxygen levels in estuaries. Canonical wisdom points to the decreased capacity of rivers to retain nitrogen as they flow toward the coast. However, how tidal freshwater zones, which often extend hundreds of kilometers inland, process and remove nitrogen remains unknown. Using geochemical measurements and numerical models, we show that tidal pumping results in the rapid cycling of nitrogen within distinct zones throughout the riparian aquifer. Near the fluctuating water table nitrification dominates, with high nitrate concentrations (>10 mg N/L) and consistent isotopic composition. Beneath this zone, isotopes reveal that nitrate is both denitrified and added over the tidal cycle, maintaining nitrate concentrations >3–4 mg N/L. In most of the riparian aquifer and streambed, nitrate concentrations are <0.5 mg N/L, suggesting denitrification dominates. Model results reveal that oxygen delivery to groundwater from the overlying unsaturated soil fuels mineralization and nitrification, with subsequent denitrification in low‐oxygen, high organic matter regions. Depending on flow paths, tidal freshwater zones could be sources of nitrate in regions with permeable sediment and low organic matter content.

 
more » « less
NSF-PAR ID:
10453326
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
DOI PREFIX: 10.1029
Date Published:
Journal Name:
Journal of Geophysical Research: Biogeosciences
Volume:
124
Issue:
11
ISSN:
2169-8953
Page Range / eLocation ID:
p. 3343-3355
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    In coastal rivers, tides facilitate surface water‐groundwater exchange and strongly coupled nitrification‐denitrification near the fluctuating water table. We used numerical fluid flow and reactive transport models to explore hydrogeologic and biogeochemical controls on nitrogen transport along an idealized tidal freshwater zone based on field observations from White Clay Creek, Delaware, USA. The capacity of the riparian aquifer to remove nitrate depends largely on nitrate transport rates, which initially increase with increasing tidal range but then decline as sediments become muddier and permeability decreases. Over the entire model reach, local nitrification provides a similar amount of nitrate as surface and groundwater contributions combined. More than half (~66%) of nitrate removed via denitrification is produced in situ, while the vast majority of remaining nitrate removed comes from groundwater sources. In contrast, average nitrate removal from surface water due to tidal pumping amounts to only ~1% of the average daily in‐channel riverine nitrate load or 1.77 kg of nitrate along the reach each day. As a result, tidal bank storage zones may not be major sinks for nitrate in coastal rivers but can act as effective sinks for groundwater nitrate. By extension, tidal bank storage zones provide a critical ecosystem service, reducing contributions of groundwater nitrate, which is often derived from septic tanks and fertilizers, to coastal rivers.

     
    more » « less
  2. Abstract

    Dam removals are on the increase across the US with Pennsylvania currently leading the nation. While most dam removals are driven by aquatic habitat and public safety considerations, we know little about how dam removals impact water quality and riparian zone processes. Dam removals decrease the stream base level, which results in dewatering of the riparian zone. We hypothesized that this dewatering of the riparian zone would increase nitrification and decrease denitrification, and thus result in nitrogen (N) leakage from riparian zones. This hypothesis was tested for a 1.5 m high milldam removal. Stream, soil water, and groundwater N concentrations were monitored over 2 years. Soil N concentrations and process rates andδ15N values were also determined. Denitrification rates and soilδ15N values in riparian sediments decreased supporting our hypothesis but no significant changes in nitrification were observed. While surficial soil water nitrate‐N concentrations were high (median 4.5 mg N L−1), riparian groundwater nitrate‐N values were low (median 0.09 mg N L−1), indicating that nitrate‐N leakage was minimal. We attribute the low groundwater nitrate‐N to denitrification losses at the lower, more dynamic, groundwater interface and/or dissimilatory nitrate reduction to ammonium (DNRA). Stream water nitrate‐N concentrations were high (median 7.6 mg N L−1) and contrary to our dam‐removal hypothesis displayed a watershed‐wide decline that was attributed to regional hydrologic changes. This study provided important first insights on how dam removals could affect N cycle processes in riparian zones and its implications for water quality and watershed management.

     
    more » « less
  3. Abstract

    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.

     
    more » « less
  4. 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.

     
    more » « less
  5. Abstract

    Subterranean estuaries (STEs) form at the land‐sea boundary where groundwater and seawater mix. These biogeochemically reactive zones influence groundwater‐borne nutrient concentrations and speciation prior to export via submarine groundwater discharge (SGD). We examined a STE located along the York River Estuary (YRE) to determine if SGD delivers dissolved inorganic nitrogen (DIN) and phosphorus (DIP) to the overlying water. We assessed variations in STE geochemical profiles with depth across locations, times, and tidal stages, estimated N removal along the STE flow path, measured hydraulic gradients to estimate SGD, and calculated potential nutrient fluxes. Salinity, dissolved oxygen (DO), DIN, and DIP varied significantly with depth and season (p < 0.05), but not location or tidal stage. Ammonium dominated the DIN pool deep in the STE. Moving toward the sediment surface, ammonium concentrations decreased as nitrate and DO concentrations increased, suggesting nitrification. Potential sediment N removal rates mediated by denitrification were <8 mmoles N m−2 d−1. The total groundwater discharge rate was 38 ± 11 L m−2 d−1; discharge followed tidal and seasonal patterns. Net SGD nutrient fluxes were 0.065–3.2 and 0.019–0.093 mmoles m−2 d−1for DIN and DIP, respectively. However, microbial N removal in the STE may attenuate 0.58% to >100% of groundwater DIN. SGD fluxes were on the same order of magnitude as diffusive benthic fluxes but accounted for <10% of the nutrients delivered by fluvial advection in the YRE. Our results indicate the importance of STE biogeochemical transformations to SGD flux estimations and their role in coastal eutrophication and nutrient dynamics.

     
    more » « less