John H. Duff

The role of water exchange between a stream channel and its hyporheic zone in nitrogen cycling at the terrestrial-aquatic interface

The subsurface riparian zone was examined as an ecotone with two interfaces. Inland is a terrestrial boundary, where transport of water and dissolved solutes is toward the channel and controlled by watershed hydrology. Streamside is an aquatic boundary, where exchange of surface water and dissolved solutes is bi-directional and flux is strongly influenced by channel hydraulics. Streamside, bi-directional exchange of water was qualitatively defined using biologically conservative tracers in a third order stream. In several experiments, penetration of surface water extended 18 m inland. Travel time of water from the channel to bankside sediments was highly variable. Subsurface chemical gradients were indirectly related to the travel time. Sites with long travel times tended to be low in nitrate and DO (dissolved oxygen) but high in ammonium and DOC (dissolved organic carbon). Sites with short travel times tended to be high in nitrate and DO but low in ammonium and DOC. Ammonium concentration of interstitial water also was influenced by sorption-desorption processes that involved clay minerals in hyporheic sediments. Denitrification potential in subsurface sediments increased with distance from the channel, and was limited by nitrate at inland sites and by DO in the channel sediments. Conversely, nitrification potential decreased with distance from the channel, and was limited by DO at inland sites and by ammonium at channel locations. Advection of water and dissolved oxygen away from the channel resulted in an oxidized subsurface habitat equivalent to that previously defined as the hyporheic zone. The hyporheic zone is viewed as stream habitat because of its high proportion of surface water and the occurrence of channel organisms. Beyond the channels hydrologic exchange zone, interstitial water is often chemically reduced. Interstitial water that has not previously entered the channel, groundwater, is viewed as a terrestrial component of the riparian ecotone. Thus, surface water habitats may extend under riparian vegetation, and terrestrial groundwater habitats may be found beneath the stream channel.

Denitrification in nitrate-contaminated groundwater: Occurrence in steep vertical geochemical gradients

A relatively narrow vertical zone (5–6 m thick) of NO3− containing groundwater was identified using multilevel sampling devices in a sand and gravel aquifer on Cape Cod, MA, USA. The aquifer has been chronically contaminated by surface disposal of treated sewage 0.3 km upgradient from the study area. The NO3− zone was anoxic and contained high concentrations of N2O (16.5 μM), suggesting that it was a zone of active denitrification. Denitrifying activity was confirmed with direct measurement using acetylene block incubations with aquifer core material; the peak rate was 2.4 nmol N reduced (g sed)−1 day−1. Concentrations of dissolved inorganic carbon and N2 were close to atmospheric equilibrium in uncontaminated groundwater, but were more than 2 times higher within the contaminant plume. Excess CO2 and N2 suggested in situ formation with a stoichiometry of C and N mineralized via denitrification of 0.8 (C/N). Denitrification within the aquifer resulted in an increase in the natural δ15N of NO3− (from +13.6 to +42.0%.) and the N2 produced, with an isotopic enrichment factor, ϵ, of −13.9%.. Vertical profiles of NH4+ and δ15N of NH4+ indicated that dissimilatory reduction of NO3− to NH4+ was also occurring but mass balance calculations indicated that denitrification was the predominant process. These results demonstrate that a combination approach using field mass balance, stable isotope analysis, and laboratory incubations yields useful insight as to the significance of denitrification in aquifer sediments and that closely spaced vertical sampling is necessary to adequately quantify the processes controlling C and N transport and transformation within these environments.

Inorganic N and P dynamics of Antarctic glacial meltwater streams as controlled by hyporheic exchange and benthic autotrophic communities

Abstract The McMurdo Dry Valleys of South Victoria Land, Antarctica, contain numerous glacial meltwater streams that drain into lakes on the valley floors. Many of the streams have abundant perennial mats of filamentous cyanobacteria. The algal mats grow during streamflow in the austral summer and are in a dormant freeze-dried state during the rest of the year. NO3 and soluble reactive P (SRP) concentrations were lower in streams with abundant algal mats than in streams with sparse algal mats. NO3 and SRP concentrations were higher in the hyporheic zone of a stream with abundant algal mats than in the stream itself. An experimental injection of LiCl, NaNO3, and K3PO4 was conducted in Green Creek, which has abundant algal mats. Substantial hyporheic exchange occurred. The NO3 and PO4 concentrations at 50 m below the injection were 55 μM and 18 μM, respectively, during the experiment. NO3 and PO4 concentrations were below the detection limit of 1 to 2 μM at a site 497 m below the injection during the Cl tracer arrival, indicating a high capacity for nutrient uptake by algal communities. NO2 and NH4 were present at sites 226 and 327 m below the injection, indicating that, in addition to denitrification and algal uptake, dissimilatory NO3 reduction to NO2 and NH4 may be a NO3 sink during transport. Transport modelling with nutrient uptake represented as a 1st-order process yielded reach-scale parameters of 4.3 × 10−5 to 3.9 × 10−4/s and 1.4 × 10−4 to 3.8 × 10−4/s for uptake of NO3 and PO4, respectively. The best match with the observed data was a model in which PO4 uptake occurred only in the main channel and NO3 uptake occurred in the main channel and in the hyporheic zone. Hyporheic NO3 uptake was 7 to 16% of the total uptake for the different stream reaches. These results demonstrate that nutrient flux to the lakes is controlled by hyporheic exchange and nutrient uptake by algal mats in dry valley streams. Streams without algal mats contribute more nutrients to the lakes than streams with algal mats.

Numerical modeling of coupled nitrification-denitrification in sediment perfusion cores from the hyporheic zone of the Shingobee River, MN

Abstract Nitrification and denitrification kinetics in sediment perfusion cores were numerically modeled and compared to experiments on cores from the Shingobee River MN, USA. The experimental design incorporated mixing groundwater discharge with stream water penetration into the cores, which provided a well-defined, one-dimensional simulation of in situ hydrologic conditions. Ammonium (NH 4 + ) and nitrate (NO 3 − ) concentration gradients suggested the upper region of the cores supported coupled nitrification–denitrification, where groundwater-derived NH 4 + was first oxidized to NO 3 − then subsequently reduced via denitrification to N 2 . Nitrification and denitrification were modeled using a Crank–Nicolson finite difference approximation to a one-dimensional advection–dispersion equation. Both processes were modeled using first-order reaction kinetics because substrate concentrations (NH 4 + and NO 3 − ) were much smaller than published Michaelis constants. Rate coefficients for nitrification and denitrification ranged from 0.2 to 15.8 h −1 and 0.02 to 8.0 h −1 , respectively. The rate constants followed an Arrhenius relationship between 7.5 and 22 °C. Activation energies for nitrification and denitrification were 162 and 97.3 kJ/mol, respectively. Seasonal NH 4 + concentration patterns in the Shingobee River were accurately simulated from the relationship between perfusion core temperature and NH 4 + flux to the overlying water. The simulations suggest that NH 4 + in groundwater discharge is controlled by sediment nitrification that, consistent with its activation energy, is strongly temperature dependent.

Ammonium sorption to channel and riparian sediments: A transient storage pool for dissolved inorganic nitrogen

Sediment (0.5 mm–2.0 mm grain size) was incubated in nylon bags (200 μm mesh) below the water table in the channel and in two transects of shallow wells perpendicular to the banks (to 18 m) of a third-order stream during August, 1987. One transect of wells drained steep old-growth forest, and the other a steep 23 year-old clear-cut partially regenerated in alder. At approximately 6-week intervals between October, 1987, and June, 1988, bags were retrieved. Total exchangeable ammonium was determined on sediment, and dissolved oxygen, nitrate and ammonium were determined in stream and well water. Exchangeable ammonium ranged from 10 μeq/100 g of sediment in the stream where nitrification potential and subsurface exchange with stream water were high, to 115 μeq/100 g sediment 18 m inland where channel water-groundwater mixing and nitrification potential were both low. Sorbed ammonium was highest during summer/autumn base flow and lowest during winter storm flow. Both channel and well water contained measurable dissolved oxygen at all times. Ammonium concentration was typically < 10 μg-N/L in channel water, increased with distance inland, but did not exceed 365 μg-N/L at any site. Nitrate concentration was typically higher in well water than channel water. Nitrate levels increased dramatically in wells at the base of the clear-cut following the onset of autumn rains. The results indicate a potential for temporary storage of ammonium on riparian sediments which may influence biotic nitrogen cycling, and alter the timing and form of dissolved inorganic nitrogen transport from the watershed.

Vulnerability of Streams to Legacy Nitrate Sources

The influence of hydrogeologic setting on the susceptibility of streams to legacy nitrate was examined at seven study sites having a wide range of base flow index (BFI) values. BFI is the ratio of base flow to total streamflow volume. The portion of annual stream nitrate loads from base flow was strongly correlated with BFI. Furthermore, dissolved oxygen concentrations in streambed pore water were significantly higher in high BFI watersheds than in low BFI watersheds suggesting that geochemical conditions favor nitrate transport through the bed when BFI is high. Results from a groundwater-surface water interaction study at a high BFI watershed indicate that decades old nitrate-laden water is discharging to this stream. These findings indicate that high nitrate levels in this stream may be sustained for decades to come regardless of current practices. It is hypothesized that a first approximation of stream vulnerability to legacy nutrients may be made by geospatial analysis of watersheds with high nitrogen inputs and a strong connection to groundwater (e.g., high BFI).

Identifying pathways and processes affecting nitrate and orthophosphate inputs to streams in agricultural watersheds

Understanding nutrient pathways to streams will improve nutrient management strategies and estimates of the time lag between when changes in land use practices occur and when water quality effects that result from these changes are observed. Nitrate and orthophosphate (OP) concentrations in several environmental compartments were examined in watersheds having a range of base flow index (BFI) values across the continental United States to determine the dominant pathways for water and nutrient inputs to streams. Estimates of the proportion of stream nitrate that was derived from groundwater increased as BFI increased. Nitrate concentration gradients between groundwater and surface water further supported the groundwater source of nitrate in these high BFI streams. However, nitrate concentrations in stream-bed pore water in all settings were typically lower than stream or upland groundwater concentrations, suggesting that nitrate discharge to streams was not uniform through the bed. Rather, preferential pathways (e.g., springs, seeps) may allow high nitrate groundwater to bypass sites of high biogeochemical transformation. Rapid pathway compartments (e.g., overland flow, tile drains) had OP concentrations that were typically higher than in streams and were important OP conveyers in most of these watersheds. In contrast to nitrate, the proportion of stream OP that is derived from ground water did not systematically increase as BFI increased. While typically not the dominant source of OP, groundwater discharge was an important pathway of OP transport to streams when BFI values were very high and when geochemical conditions favored OP mobility in groundwater.

Role of the fish Astyanax aeneus (Characidae) as a keystone nutrient recycler in low-nutrient Neotropical streams

Nutrient recycling by animals is a potentially important biogeochemical process in both terrestrial and aquatic ecosystems. Stoichiometric traits of individual species may result in some taxa playing disproportionately important roles in the recycling of nutrients relative to their biomass, acting as keystone nutrient recyclers. We examined factors controlling the relative contribution of 12 Neotropical fish species to nutrient recycling in four streams spanning a range of phosphorus (P) levels. In high-P conditions (135 microg/L soluble reactive phosphorus, SRP), most species fed on P-enriched diets and P excretion rates were high across species. In low-P conditions (3 microg/L SRP), aquatic food resources were depleted in P, and species with higher body P content showed low rates of P recycling. However, fishes that were subsidized by terrestrial inputs were decoupled from aquatic P availability and therefore excreted P at disproportionately high rates. One of these species, Astyanax aeneus (Characidae), represented 12% of the total population and 18% of the total biomass of the fish assemblage in our focal low-P study stream but had P excretion rates > 10-fold higher than other abundant fishes. As a result, we estimated that P excretion by A. aeneus accounted for 90% of the P recycled by this fish assemblage and also supplied approximately 90% of the stream P demand in this P-limited ecosystem. Nitrogen excretion rates showed little variation among species, and the contribution of a given species to ecosystem N recycling was largely dependent upon the total biomass of that species. Because of the high variability in P excretion rates among fish species, ecosystem-level P recycling could be particularly sensitive to changes in fish community structure in P-limited systems.

Nitrate reduction in sediments of lowland tropical streams draining swamp forest in Costa Rica: An ecosystem perspective

Nitrate reduction and denitrification were measured in swamp forest streams draining lowland rain forest on Costa Ricas Atlantic slope foothills using the C2H2-block assay and sediment-water nutrient fluxes. Denitrification assays using the C2H2-block technique indicated that the full suite of denitrifying enzymes were present in the sediment but that only a small fraction of the functional activity could be expressed without adding NO3−. Under optimal conditions, denitrification enzyme activity averaged 15 nmoles cm−3 sediment h−1. Areal NO3− reduction rates measured from NO3− loss in the overlying water of sediment-water flux chambers ranged from 65 to 470 umoles m−2 h−1. Oxygen loss rates accompanying NO3− depletion averaged 750 umoles m−2 h−1. Corrected for denitrification of NO3− oxidized from NH4+ in the sediment, gross NO3− reduction rates increase by 130 umoles m−2 h−1, indicating nitrification may be the predominant source of NO3− for NO3− reduction in swamp forest stream sediments. Under field conditions approximately 80% of the increase in inorganic N mass along a 1250-m reach of the Salto River was in the form of NO3− with the balance NH4+ . Scrutiny of potential inorganic N sources suggested that mineralized N released from the streambed was a major source of the inorganic N increase. Despite significant NO3− reduction potential, swamp forest stream sediments appear to be a source of inorganic N to downstream communities.

Phosphorus and Nitrogen Legacy in a Restoration Wetland, Upper Klamath Lake, Oregon

The effects of sediment, ground-water, and surface-water processes on the timing, quantity, and mechanisms of N and P fluxes were investigated in the Wood River Wetland 5–7 years after agricultural practices ceased and seasonal and permanent wetland hydrologies were restored. Nutrient concentrations in standing water largely reflected ground water in winter, the largest annual water source in the closedbasin wetland. High concentrations of total P (22 mg L−1) and total N (30 mg L−1) accumulated in summer when water temperature, air temperature, and evapotranspiration were highest. High positive benthic fluxes of soluble reactive P and ammonium (NH4+-N) were measured in two sections of the study area in June and August, averaging 46 and 24 mg m−2 d−1, respectively. Nonetheless, a wetland mass balance simultaneously indicated a net loss of P and N by assimilation, denitrification (1.1–10.1 mg N m−2 h−1), or solute repartitioning. High nutrient concentrations pose a risk for water quality management. Shifts in the timing and magnitude of water inflows and outflows may improve biogeochemical function and water quality by optimizing seed germination and aquatic plant distribution, which would be especially important if the Wood River Wetland was reconnected with hyper-eutrophic Agency Lake.