Low transient storage and uptake efficiencies in seven agricultural streams: implications for nutrient demand.

We used mass load budgets, transient storage modeling, and nutrient spiraling metrics to characterize nitrate (NO), ammonium (NH), and inorganic phosphorus (SRP) demand in seven agricultural streams across the United States and to identify in-stream services that may control these conditions. Retention of one or all nutrients was observed in all but one stream, but demand for all nutrients was low relative to the mass in transport. Transient storage metrics (/, , , and ) correlated with NO retention but not NH or SRP retention, suggesting in-stream services associated with transient storage and stream water residence time could influence reach-scale NO demand. However, because the fraction of median reach-scale travel time due to transient storage () was ≤1.2% across the sites, only a relatively small demand for NO could be generated by transient storage. In contrast, net uptake of nutrients from the water column calculated from nutrient spiraling metrics were not significant at any site because uptake lengths calculated from background nutrient concentrations were statistically insignificant and therefore much longer than the study reaches. These results suggest that low transient storage coupled with high surface water NO inputs have resulted in uptake efficiencies that are not sufficient to offset groundwater inputs of N. Nutrient retention has been linked to physical and hydrogeologic elements that drive flow through transient storage areas where residence time and biotic contact are maximized; however, our findings indicate that similar mechanisms are unable to generate a significant nutrient demand in these streams relative to the loads.

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).

Experimental acidification of two biogeochemically-distinct neotropical streams: buffering mechanisms and macroinvertebrate drift.

Research into the buffering mechanisms and ecological consequences of acidification in tropical streams is lacking. We have documented seasonal and episodic acidification events in streams draining La Selva Biological Station, Costa Rica. Across this forested landscape, the severity in seasonal and episodic acidification events varies due to interbasin groundwater flow (IGF). Streams that receive IGF have higher concentrations of solutes and more stable pH (~6) than streams that do not receive IGF (pH ~5). To examine the buffering capacity and vulnerability of macroinvertebrates to short-term acidification events, we added hydrochloric acid to acidify a low-solute, poorly buffered (without IGF) and a high-solute, well buffered stream (with IGF). We hypothesized that: 1) protonation of bicarbonate (HCO(3)(-)) would neutralize most of the acid added in the high-solute stream, while base cation release from the sediments would be the most important buffering mechanism in the low-solute stream; 2) pH declines would mobilize inorganic aluminum (Ali) from sediments in both streams; and 3) pH declines would increase macroinvertebrate drift in both streams. We found that the high-solute stream neutralized 745 µeq/L (96% of the acid added), while the solute poor stream only neutralized 27.4 µeq/L (40%). Protonation of HCO(3)(-) was an important buffering mechanism in both streams. Base cation, Fe(2+), and Ali release from sediments and protonation of organic acids also provided buffering in the low-solute stream. We measured low concentrations of Ali release in both streams (2-9 µeq/L) in response to acidification, but the low-solute stream released double the amount Ali per 100 µeq of acid added than the high solute stream. Macroinvertebrate drift increased in both streams in response to acidification and was dominated by Ephemeroptera and Chironomidae. Our results elucidate the different buffering mechanisms in tropical streams and suggest that low-solute poorly buffered streams might be particularly vulnerable to episodic acidification.

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.

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.

Whole-stream response to nitrate loading in three streams draining agricultural landscapes.

Physical, chemical, hydrologic, and biologic factors affecting nitrate (NO3(-)) removal were evaluated in three agricultural streams draining orchard/dairy and row crop settings. Using 3-d "snapshots" during biotically active periods, we estimated reach-level NO3(-) sources, NO3(-) mass balance, in-stream processing (nitrification, denitrification, and NO3(-) uptake), and NO3(-) retention potential associated with surface water transport and ground water discharge. Ground water contributed 5 to 11% to stream discharge along the study reaches and 8 to 42% of gross NO3(-) input. Streambed processes potentially reduced 45 to 75% of ground water NO3(-) before discharge to surface water. In all streams, transient storage was of little importance for surface water NO3(-) retention. Estimated nitrification (1.6-4.4 mg N m(-2) h(-1)) and unamended denitrification rates (2.0-16.3 mg N m(-2) h(-1)) in sediment slurries were high relative to pristine streams. Denitrification of NO3(-) was largely independent of nitrification because both stream and ground water were sources of NO3(-). Unamended denitrification rates extrapolated to the reach-scale accounted for <5% of NO3(-) exported from the reaches minimally reducing downstream loads. Nitrate retention as a percentage of gross NO3(-) inputs was >30% in an organic-poor, autotrophic stream with the lowest denitrification potentials and highest benthic chlorophyll a, photosynthesis/respiration ratio, pH, dissolved oxygen, and diurnal NO3(-) variation. Biotic processing potentially removed 75% of ground water NO3(-) at this site, suggesting an important role for photosynthetic assimilation of ground water NO3(-) relative to subsurface denitrification as water passed directly through benthic diatom beds.

Nitrate retention in riparian ground water at natural and elevated nitrate levels in north central Minnesota.

The relationship between local ground water flows and NO(3)(-) transport to the channel was examined in three well transects from a natural, wooded riparian zone adjacent to the Shingobee River, MN. The hillslope ground water originated as recharge from intermittently grazed pasture up slope of the site. In the hillslope transect perpendicular to the stream, ground water NO(3)(-) concentrations decreased from approximately 3 mg N L(-1) beneath the ridge (80 m from the channel) to 0.01 to 1.0 mg N L(-1) at wells 1 to 3 m from the channel. The Cl(-) concentrations and NO(3)/Cl ratios decreased toward the channel indicating NO(3)(-) dilution and biotic retention. In the bankside well transect parallel to the stream, two distinct ground water environments were observed: an alluvial environment upstream of a relict beaver dam influenced by stream water and a hillslope environment downstream of the relict beaver dam. Nitrate was elevated to levels representative of agricultural runoff in a third well transect located approximately 5 m from the stream to assess the effectiveness of the riparian zone as a NO(3)(-) sink. Subsurface NO(3)(-) injections revealed transport of up to 15 mg N L(-1) was nearly conservative in the alluvial riparian environment. Addition of glucose stimulated dissolved oxygen uptake and promoted NO(3)(-) retention under both background and elevated NO(3)(-) levels in summer and winter. Disappearance of added NO(3)(-) was followed by transient NO(2)(-) formation and, in the presence of C(2)H(2), by N(2)O formation, demonstrating potential denitrification. Under current land use, most NO(3)(-) associated with local ground water is biotically retained or diluted before reaching the channel. However, elevating NO(3)(-) levels through agricultural cultivation would likely result in increased NO(3)(-) transport to the channel.