Net sediment N2 fluxes in a southern New England estuary: variations in space and time

Over the past three decades, Narragansett Bay has undergone various ecological changes, including significant decreases in water column chlorophyll a concentrations, benthic oxygen uptake, and benthic nutrient regeneration rates. To add to this portrait of change, we measured the net flux of N₂ across the sediment–water interface over an annual cycle using the N₂/Ar technique at seven sites in the bay for comparison with measurements made decades ago. Net denitrification rates ranged from about 10–90 μmol N₂–N m^?2 h^?1 over the year. Denitrification rates were not significantly different among sites and had no clear correlation with temperature. Net nitrogen fixation (?5 to ?650 μmol N₂–N m^?2 h^?1) was measured at three sites and only observed in summer (June–August). Neither denitrification nor nitrogen fixation exhibited a consistent relationship with sediment oxygen demand or with fluxes of nitrite, nitrate, ammonium, total dissolved inorganic nitrogen, or dissolved inorganic phosphate across all stations. In contrast to the mid-bay historical site where denitrification rates have declined, denitrification rates in the Providence River Estuary have not changed significantly over the past 30 years.     

Influence of hydrological connectivity of riverine wetlands on nitrogen removal via denitrification

Wetland ecosystems in agricultural areas often become progressively more isolated from main water bodies. Stagnation favors the accumulation of organic matter as the supply of electron acceptors with water renewal is limited. In this context it is expected that nitrogen recycling prevails over nitrogen dissipation. To test this hypothesis, denitrification rates, fluxes of dissolved oxygen (SOD), inorganic carbon (DIC) and nitrogen and sediment features were measured in winter and summer 2007 on 22 shallow riverine wetlands in the Po River Plain (Northern Italy). Fluxes were determined from incubations of intact cores by measurement of concentration changes or isotope pairing in the case of denitrification. Sampled sites were eutrophic to hypertrophic; 10 were connected and 12 were isolated from the adjacent rivers, resulting in large differences in nitrate concentrations in the water column (from <5 to 1,133 μM). Benthic metabolism and denitrification rates were investigated by two overarching factors: season and hydrological connectivity. SOD and DIC fluxes resulted in respiratory quotients greater than one at most sampling sites. Sediment respiration was coupled to both ammonium efflux, which increased from winter to summer, and nitrate consumption, with higher rates in river-connected wetlands. Denitrification rates measured in river-connected wetlands (35–1,888 μmol N m^?2 h^?1) were up to two orders of magnitude higher than rates measured in isolated wetlands (2–231 μmol N m^?2 h^?1), suggesting a strong regulation of the process by nitrate availability. These rates were also significantly higher in summer (9–1,888 μmol N m^?2 h^?1) than in winter (2–365 μmol N m^?2 h^?1). Denitrification supported by water column nitrate (D_W) accounted for 60–100% of total denitrification (Dtot); denitrification coupled to nitrification (D_N) was probably controlled by limited oxygen availability within sediments. Denitrification efficiency, calculated as the ratio between N removal via denitrification and N regeneration, and the relative role of denitrification for organic matter oxidation, were high in connected wetlands but not in isolated sites. This study confirms the importance of restoring hydraulic connectivity of riverine wetlands for the maintenance of important biogeochemical functions such as nitrogen removal via denitrification.     

Longevity of simultaneous operation of aquaculture and mangrove forestry as explained in terms of water and sediment qualities

A silvofishery system (SFS) of 5.2 ha, simultaneously combining aquaculture (shrimp, crab, and fish) and forestry, was studied to understand how the water/sediment qualities had remained viable for 30 years. The long life of this SFS pond contrasts sharply with a short life of many conventional, intensively managed shrimp ponds (5 years on average). Total ammonia nitrogen in the SFS water (0.06 mg l^?1) was much lower than the Thai environmental safety standard for shrimp ponds (1.0 mg l^?1) and approximately 0.05 % of an average conventional, intensively managed shrimp pond. Total organic nitrogen of the pond sediment was 1.47 mg g^?1 which was almost half of conventional, intensively managed shrimp ponds. The flux study revealed that NH₄–N was the dominant form of nitrogen, with lesser amounts of NO₂–N and NO₃–N, and that NH₄–N was being released from the sediment into the water. Nitrogen loss from the pond, which was regarded as the denitrification rate, was estimated to be 71.5 mgN m^?2 d^?1, corresponded to 55 % of the total nitrogen input. As the average denitrification rate in a conventional, intensively managed shrimp pond is 13.4 %, the SFS was shown to be relatively efficient in removing accumulated nitrogen from the pond. Assuming accepted feed conversion rates, 3,340 kg of feed would have been necessary for the amount of fishery production recorded during 5 May 2005 and 22 March 2006. However, only 380 kg of trash fish was added, representing a saving of 2,960 kg of feed. Such a saving could be attributed to detritus from the mangrove trees that have been growing within the pond and algae encouraged to bloom by the shallow water depth. Therefore, it is suggested that the efficient nitrogen removal due to the high denitrification rate as well as the reduced feed input from mangrove detritus substitution, have contributed to maintaining favourable water and sediment qualities, resulting in the longevity of SFS pond.     

Woody Vegetation Removal Stimulates Riparian and Benthic Denitrification in Tallgrass Prairie

Expansion of woody vegetation into areas that were historically grass-dominated is a significant contemporary threat to grasslands, including native tallgrass prairie ecosystems of the Midwestern United States. In tallgrass prairie, much of this woody expansion is concentrated in riparian zones with potential impacts on biogeochemical processes there. Although the effects of woody riparian vegetation on denitrification in both riparian soils and streams have been well studied in naturally wooded ecosystems, less is known about the impacts of woody vegetation encroachment in ecosystems that were historically dominated by herbaceous vegetation. Here, we analyze the effect of afforestation and subsequent woody plant removal on riparian and benthic denitrification. Denitrification rates in riparian soil and selected benthic compartments were measured seasonally in naturally grass-dominated riparian zones, woody encroached riparian zones, and riparian zones with woody vegetation removed in two separate watersheds. Riparian soil denitrification was highly seasonal, with the greatest rates in early spring. Benthic denitrification also exhibited high temporal variability, but no seasonality. Soil denitrification rates were greatest in riparian zones where woody vegetation was removed. Additionally, concentrations of nitrate, carbon, and soil moisture (indicative of potential anoxia) were greatest in wood removal soils. Differences in the presence and abundance of benthic compartments reflected riparian vegetation, and may have indirectly affected denitrification in streams. Riparian soil denitrification increased with soil water content and NO₃ ^?. Management of tallgrass prairies that includes removal of woody vegetation encroaching on riparian areas may alter biogeochemical cycling by increasing nitrogen removed via denitrification while the restored riparian zones return to a natural grass-dominated state.     

Denitrification in a meromictic lake and its relevance to nitrogen flows within a moderately impacted forested catchment

We analysed the spatial and temporal variability of benthic nitrogen fluxes and denitrification rates in a sub-alpine meromictic lake (Lake Idro, Italy), and compared in-lake nitrogen retention and loss with the net anthropogenic nitrogen inputs to the watershed. We hypothesized a low nitrogen retention and denitrification capacity due to meromixis. This results from nitrate supply from the epilimnion slowing down during stratification and oxygen deficiency inhibiting nitrification and promoting ammonium recycling and its accumulation. We also hypothesized a steep vertical gradient of sedimentary denitrification capacity, decreasing with depth and oxygen deficiency. These are important and understudied issues in inland waters, as climate change and direct anthropic pressures may increase the extent of meromixis. Nearshore sediments had high denitrification rates (87 mg m^?2 day^?1) and efficiency (~ 100%), while in the monimolimnion denitrification was negligible. The littoral zone, covering 10% of the lake surface, contributed ~50% of total denitrification, while the monimolimnion, which covered 70% of the sediment surface, contributed to < 13% of total denitrification. The persistent and expanding meromixis of Lake Idro is expected to further decrease its nitrogen removal capacity (31% of the incoming nitrogen load) compared to what has been measured in other temperate lakes. Values up to 60% are generally reported for other such lakes. Results of this study are relevant as the combination of anthropogenic pressures, climate change and meromixis may threaten the nitrogen processing capacity of lakes.     

Modeling denitrification in a tile-drained, corn and soybean agroecosystem of Illinois, USA

Denitrification is known as an important pathway for nitrate loss in agroecosystems. It is important to estimate denitrification fluxes to close field and watershed N mass balances, determine greenhouse gas emissions (N₂O), and help constrain estimates of other major N fluxes (e.g., nitrate leaching, mineralization, nitrification). We compared predicted denitrification estimates for a typical corn and soybean agroecosystem on a tile drained Mollisol from five models (DAYCENT, SWAT, EPIC, DRAINMOD-N II and two versions of DNDC, 82a and 82h), after first calibrating each model to crop yields, water flux, and nitrate leaching. Known annual crop yields and daily flux values (water, nitrate-N) for 1993–2006 were provided, along with daily environmental variables (air temperature, precipitation) and soil characteristics. Measured denitrification fluxes were not available. Model output for 1997–2006 was then compared for a range of annual, monthly and daily fluxes. Each model was able to estimate corn and soybean yields accurately, and most did well in estimating riverine water and nitrate-N fluxes (1997–2006 mean measured nitrate-N loss 28 kg N ha^?1 year^?1, model range 21–28 kg N ha^?1 year^?1). Monthly patterns in observed riverine nitrate-N flux were generally reflected in model output (r ² values ranged from 0.51 to 0.76). Nitrogen fluxes that did not have corresponding measurements were quite variable across the models, including 10-year average denitrification estimates, ranging from 3.8 to 21 kg N ha^?1 year^?1 and substantial variability in simulated soybean N₂ fixation, N harvest, and the change in soil organic N pools. DNDC82a and DAYCENT gave comparatively low estimates of total denitrification flux (3.8 and 5.6 kg N ha^?1 year^?1, respectively) with similar patterns controlled primarily by moisture. DNDC82h predicted similar fluxes until 2003, when estimates were abruptly much greater. SWAT and DRAINMOD predicted larger denitrification fluxes (about 17–18 kg N ha^?1 year^?1) with monthly values that were similar. EPIC denitrification was intermediate between all models (11 kg N ha^?1 year^?1). Predicted daily fluxes during a high precipitation year (2002) varied considerably among models regardless of whether the models had comparable annual fluxes for the years. Some models predicted large denitrification fluxes for a few days, whereas others predicted large fluxes persisting for several weeks to months. Modeled denitrification fluxes were controlled mainly by soil moisture status and nitrate available to be denitrified, and the way denitrification in each model responded to moisture status greatly determined the flux. Because denitrification is dependent on the amount of nitrate available at any given time, modeled differences in other components of the N cycle (e.g., N₂ fixation, N harvest, change in soil N storage) no doubt led to differences in predicted denitrification. Model comparisons suggest our ability to accurately predict denitrification fluxes (without known values) from the dominant agroecosystem in the midwestern Illinois is quite uncertain at this time.     

Interaction of benthic microalgae and macrofauna in the control of benthic metabolism, nutrient fluxes and denitrification in a shallow sub-tropical coastal embayment (western Moreton Bay, Australia)

Benthic biogeochemistry and macrofauna were investigated six times over 1 year in a shallow sub-tropical embayment. Benthic fluxes of oxygen (annual mean ?918 μmol O₂ m^?2 h^?1), ammonium (NH₄ ⁺), nitrate (NO₃ ^?), dissolved organic nitrogen, dinitrogen gas (N₂), and dissolved inorganic phosphorus were positively related to OM supply (N mineralisation) and inversely related to benthic light (N assimilation). Ammonium (NH₄ ⁺), NO₃ ^? and N₂ fluxes (annual means +14.6, +15.9 and 44.6 μmol N m^?2 h^?1) accounted for 14, 16 and 53 % of the annual benthic N remineralisation respectively. Denitrification was dominated by coupled nitrification–denitrification throughout the study. Potential assimilation of nitrogen by benthic microalgae (BMA) accounted for between 1 and 30 % of remineralised N, and was greatest during winter when bottom light was higher. Macrofauna biomass tended to be highest at intermediate benthic respiration rates (?1,000 μmol O₂ m^?2 h^?1), and appeared to become limited as respiration increased above this point. While bioturbation did not significantly affect net fluxes, macrofauna biomass was correlated with increased light rates of NH₄ ⁺ flux which may have masked reductions in NH₄ ⁺ flux associated with BMA assimilation during the light. Peaks in net N₂ fluxes at intermediate respiration rates are suggested to be associated with the stimulation of potential denitrification sites due to bioturbation by burrowing macrofauna. NO₃ ^? fluxes suggest that nitrification was not significantly limited within respiration range measured during this study, however comparisons with other parts of Moreton Bay suggest that limitation of coupled nitrification–denitrification may occur in sub-tropical systems at respiration rates exceeding ?1,500 μmol O₂ m^?2 h^?1.     

Denitrification in the river network of a mixed land use watershed: unpacking the complexities

River networks have the potential to permanently remove nitrogen through denitrification. Few studies have measured denitrification rates within an entire river network or assessed how land use affect rates at larger spatial scales. We sampled 108 sites throughout the network of the Fox River watershed, Wisconsin, to determine if land use influence sediment denitrification rates, and to identify zones of elevated sediment denitrification rates (hot spots) within the river network. Partial least squares regression models identified variables from four levels of organization (river bed sediment, water column, riparian zone, and watershed) that best predicted denitrification rates throughout the river network. Nitrate availability was the most important predictor of denitrification rates, while land cover was not always a good predictor of local-scale nitrate concentrations. Thus, land cover and denitrification rate were not strongly related across the Fox River watershed. A direct relationship between denitrification rate and watershed land cover occurred only in the Wolf River sub-watershed, the least anthropogenically disturbed of the sub-watersheds. Denitrification hot spots were located throughout the river network, regardless of watershed land use, with hot spot location being determined primarily by nitrate availability. In the Fox River watershed, when nitrate was abundant, river bed sediment character influenced denitrification rate, with higher denitrification rates at sites with fine, organic sediments. These findings suggest that denitrification occurring throughout an entire river network, from headwater streams to larger rivers, can help reduce nitrogen loads to downstream water bodies.

     

Influence of Potamogeton pectinatus and microphytobenthos on benthic metabolism,nutrient fluxes and denitrification in a freshwater littoral sediment in an agricultural landscape: N assimilation versus N removal

The influence of Potamogeton pectinatus colonisation on benthic nitrogen dynamics was studied in the littoral zone of a lowland pit lake with high nitrate concentration (~200 μM). Our hypothesis was that in aquatic environments where nitrogen availability is not limiting, colonisation by rooted macrophytes changes the dynamics of the benthic nitrogen cycle, stimulating N assimilation and denitrification and increasing the system capacity to take up external nitrogen loads. To test this hypothesis, we quantified and compared seasonal variations of light and dark benthic metabolism, dissolved inorganic nitrogen (DIN) fluxes, denitrification and N assimilation rates in an area colonised by P. pectinatus and a reference site colonised by microphytobenthos. In both areas, the benthic system was net autotrophic and a sink for DIN (2,241–2,644 mmol m^?2 y^?1). Plant colonisation increased nitrogen losses via denitrification by 30% compared to the unvegetated area. In contrast to what is generally observed in coastal marine systems, where the presence of rooted macrophytes limits denitrification rates, under the very high nitrate concentrations in the studied lake, both denitrification (1,237–1,570 mmol m^?2 y^?1) and N assimilation (1,039–1,095 mmol m^?2 y^?1) played important and comparable roles in the removal of DIN from the water column.     

Nitrification and denitrification in a midwestern stream containing high nitrate: in situ assessment using tracers in dome-shaped incubation chambers

The extent to which in-stream processes alter or remove nutrient loads in agriculturally impacted streams is critically important to watershed function and the delivery of those loads to coastal waters. In this study, patch-scale rates of in-stream benthic processes were determined using large volume, open-bottom benthic incubation chambers in a nitrate-rich, first to third order stream draining an area dominated by tile-drained row-crop fields. The chambers were fitted with sampling/mixing ports, a volume compensation bladder, and porewater samplers. Incubations were conducted with added tracers (NaBr and either ¹⁵N[NO₃ ^?], ¹⁵N[NO₂ ^?], or ¹⁵N[NH₄ ⁺]) for 24–44 h intervals and reaction rates were determined from changes in concentrations and isotopic compositions of nitrate, nitrite, ammonium and nitrogen gas. Overall, nitrate loss rates (220–3,560 μmol N m^?2 h^?1) greatly exceeded corresponding denitrification rates (34–212 μmol N m^?2 h^?1) and both of these rates were correlated with nitrate concentrations (90–1,330 μM), which could be readily manipulated with addition experiments. Chamber estimates closely matched whole-stream rates of denitrification and nitrate loss using ¹⁵N. Chamber incubations with acetylene indicated that coupled nitrification/denitrification was not a major source of N₂ production at ambient nitrate concentrations (175 μM), but acetylene was not effective for assessing denitrification at higher nitrate concentrations (1,330 μM). Ammonium uptake rates greatly exceeded nitrification rates, which were relatively low even with added ammonium (3.5 μmol N m^?2 h^?1), though incubations with nitrite demonstrated that oxidation to nitrate exceeded reduction to nitrogen gas in the surface sediments by fivefold to tenfold. The chamber results confirmed earlier studies that denitrification was a substantial nitrate sink in this stream, but they also indicated that dissolved inorganic nitrogen (DIN) turnover rates greatly exceeded the rates of permanent nitrogen removal via denitrification.     

The potential effect of sustained hypoxia on nitrogen cycling in sediment from the southern North Sea: a mesocosm experiment

The potential effect of sustained hypoxia (up to 70 days) on the production of N₂ gas through denitrification and anammox, as well as sediment–water exchange of nitrite, nitrate and ammonia, oxygen consumption and penetration, were measured in mesocosms using sediment collected from the southern North Sea (north of Dogger Bank). As expected, both the penetration of oxygen into, and consumption of oxygen by, the sediment decreased by 42 and 46 %, respectively, once hypoxia was established. Importantly, the oxygen regime did not change significantly (P > 0.05) during the experiment, suggesting that organic carbon was not depleted. During the first 10 days, the exchange of NO₃ ^?, NO₂ ^? and NH₄ ⁺ between the sediment and water was erratic but once a steady state was established the sediment acted as either a sink for fixed nitrogen under hypoxia or as a source in the controls. Over the course of the mesocosm experiment the rate of both anammox and denitrification increased, with anammox increasing disproportionately under hypoxia relative to the controls, whereas the rate of increase in denitrification was the same for both. Under sustained hypoxia the production of N₂ gas increased by 72 % relative to the controls, with this increase in N₂ production remaining constant regardless of the duration of hypoxia. Longer periods of stratification and oxygen depletion are predicted to occur more regularly in the bottom waters of shallow coastal seas as one manifestation of climate change. Under sustained hypoxia the potential for nitrogen removal by the production of N₂ gas in this region of the southern North Sea was estimated to increase from 2.1 kt N 150 days^?1 to 3.6 kt 150 days^?1, while the efflux of dissolved inorganic nitrogen ceased altogether; both of which could down regulate the productivity of this region as a whole.     

Co-occurrence of in-stream nitrogen fixation and denitrification across a nitrogen gradient in a western U.S. watershed

It is frequently assumed that nitrogen (N₂) fixation and denitrification do not co-occur in streams because each process should be favored under different concentrations of dissolved inorganic nitrogen (DIN), and therefore these processes are rarely quantified together. We asked if these processes could co-exist by conducting a spatial survey of N₂ fixation using acetylene reduction and denitrification using acetylene block [with and without amendments of carbon (C) as glucose and nitrogen (N) as nitrate]. Rates were measured on rocks and sediment in 8 southeastern Idaho streams encompassing a DIN gradient of 26–615 µg L^?1. Sampling at each site was repeated in summer 2015 and 2016. We found that both denitrification and N₂ fixation occurred across the gradient of DIN concentrations, with N₂ fixation occurring primarily on rocks and denitrification occurring in sediment. N₂ fixation rates on rocks significantly decreased 100× across the DIN gradient in 1 year of the study, and amended (with N and C) denitrification rates increased 10× across the DIN gradient in both years. Multiple linear regression and partial least squares models with environmental characteristics measured at the scale of entire stream reaches showed that C and phosphorus were positive predictors of amended and unamended denitrification rates, but no significant model could explain N₂ fixation rates across all streams and years. This, coupled with the observation that detectable rates of N₂ fixation occurred primarily on rocks and denitrification occurred primarily on sediment, suggests that microhabitat scale factors may better predict the co-occurrence of these processes within stream reaches. Overlooking the potential co-occurrence of N₂ fixation and denitrification in stream ecosystems will impede understanding by oversimplifying the contribution of each process to the N cycle.     

Nitrogen removal in coastal sediments of the German Wadden Sea

Although sediments of the German Wadden Sea are suspected to eliminate a considerable share of nitrate delivered to the SE North Sea, their denitrification rates have not been systematically assessed. We determined N₂ production rates over seasonal cycles (February 2009–April 2010) at two locations with two sediments types each, the first site (Meldorf Bight) receiving nitrate during all seasons from the Elbe river plume, and a second site on the island of Sylt, where nitrate is depleted during summer months. In sediments from the Sylt site, N₂ production ranged from 15 to 32 μmol N₂ m^?2 h^?1 in the fine sand station and from 7 to 13 μmol N₂ m^?2 h^?1 in the coarse sand station; N₂ production was not detected when nitrate was depleted in May and July of 2009. N₂ production in the Meldorf Bight sediments were consistently detected at higher rates (58–130 μmol N₂ m^?2 h^?1 in the very fine sand station and between 14 and 30 μmol N₂ m^?2 h^?1 in the medium sand station). Analysis of ancillary parameters suggests that major factors controlling N₂ production in coastal sediments of the German Wadden Sea are the nitrate concentrations in the overlying water, the ambient temperature, and the organic matter content of the sediment. Extrapolating our spot measurements to the zone of nitrate availability and sediment types, we estimate an annual nitrogen removal rate around 16 kt N year^?1 for the entire northern sector of the German Wadden Sea area. This corresponds to 14% of the annual Elbe river nitrogen load.     

Potential nitrogen and carbon processing in a landscape rich in milldam legacy sediments

Recent identification of the widespread distribution of legacy sediments deposited in historic mill ponds has increased concern regarding their role in controlling land–water nutrient transfers in the mid-Atlantic region of the US. At Big Spring Run in Lancaster, Pennsylvania, legacy sediments now overlay a buried relict hydric soil (a former wetland soil). We compared C and N processing in legacy sediment to upland soils to identify soil zones that may be sources or sinks for N transported toward streams. We hypothesized that legacy sediments would have high nitrification rates (due to recent agricultural N inputs), while relict hydric soils buried beneath the legacy sediments would be N sinks revealed via negative net nitrification and/or positive denitrification (because the buried former wetland soils are C rich but low in O₂). Potential net nitrification ranged from 9.2 to 77.9 g m^?2 year^?1 and potential C mineralization ranged from 223 to 1,737 g m^?2 year^?1, with the highest rates in surface soils for both legacy sediments and uplands. Potential denitrification ranged from 0.37 to 21.72 g m^?2 year^?1, with the buried relict hydric soils denitrifying an average of 6.2 g m^?2 year^?1. Contrary to our hypothesis, relict hydric layers did not have negative potential nitrification or high positive potential denitrification rates, in part because microbial activity was low relative to surface soils, as indicated by low nitrifier population activity, low substrate induced respiration, and low exoenzyme activity. Despite high soil C concentrations, buried relict hydric soils do not provide the ecological services expected from a wetland soil. Thus, legacy sediments may dampen N removal pathways in buried relict hydric soils, while also acting as substantial sources of NO₃ ^? to waterways.     

Abundance,Activity and Community Structure of Denitrifiers in Drainage Ditches in Relation to Sediment Characteristics,Vegetation and Land-Use

Drainage ditches are ubiquitous yet understudied features of the agricultural landscape. Nitrogen pollution disrupts the nutrient balance of drainage ditch ecosystems, as well as the waterbodies in which they drain. Denitrification can help ameliorate the impact of N-fertilization by converting reactive nitrogen into dinitrogen gas. However, factors affecting denitrification in drainage ditches are still poorly understood. In this study, we tested how within-ditch and regional environmental conditions affect denitrifier activity, abundance, and community structure, to understand controls on denitrification at multiple scales. To this end, we quantified in situ denitrification rates and denitrifier abundance in 13 drainage ditches characterized by different types of sediment, vegetation and land-use. We determined how denitrification rates relate to denitrifier abundance and community structure, using the presence of nirS, nirK and nosZ genes as a proxy. Denitrification rates varied widely between the ditches, ranging from 0.006 to 24 mmol N m^?2 h^?1. Ditches covered by duckweed, which contained high nitrate concentrations and had fine, sandy sediments, were denitrification hotspots. We found highest rates in ditches next to arable land, followed by those in grasslands; lowest rates were observed in peatlands and nature reserves. Denitrification correlated to nitrate concentrations, but not to nirK, nirS and nosZ abundance, whereas denitrifier-gene abundance correlated to organic matter content of the sediment, but not to nitrate concentrations. Our results show a mismatch in denitrification regulators at its different organizational scales. Denitrifier abundance is mostly regulated at within-ditch scales, whereas N-loads, regulated by landscape factors, are most important determinants of instantaneous denitrification rates.     

Nutrient Biogeochemistry During the Early Stages of Delta Development in the Mississippi River Deltaic Plain

Nutrient biogeochemistry associated with the early stages of soil development in deltaic floodplains has not been well defined. Such a model should follow classic patterns of soil nutrient pools described for alluvial ecosystems that are dominated by mineral matter high in phosphorus and low in carbon and nitrogen. A contrast with classic models of soil development is the anthropogenically enriched high nitrate conditions due to agricultural fertilization in upstream watersheds. Here we determine if short-term patterns of soil chemistry and dissolved inorganic nutrient fluxes along the emerging Wax Lake delta (WLD) chronosequence are consistent with conceptual models of long-term nutrient availability described for other ecosystems. We add a low nitrate treatment more typical of historic delta development to evaluate the role of nitrate enrichment in determining the net dinitrogen (N₂) flux. Throughout the 35-year chronosequence, soil nitrogen and organic matter content significantly increased by an order of magnitude, whereas phosphorus exhibited a less pronounced increase. Under ambient nitrate concentrations (>60 μM), mean net N₂ fluxes (157.5 μmol N m^?2 h^?1) indicated greater rates of gross denitrification than gross nitrogen fixation; however, under low nitrate concentrations (<2 μM), soils switched from net denitrification to net nitrogen fixation (?74.5 μmol N m^?2 h^?1). As soils in the WLD aged, the subsequent increase in organic matter stimulated net N₂, oxygen, nitrate, and nitrite fluxes producing greater fluxes in more mature soils. In conclusion, soil nitrogen and carbon accumulation along an emerging delta chronosequence largely coincide with classic patterns of soil development described for alluvial floodplains, and substrate age together with ambient nitrogen availability can be used to predict net N₂ fluxes during early delta evolution.     

Enhanced biological denitrification of high concentration of nitrite with supplementary carbon source

Nitrite accumulates during biological denitrification processes when carbon sources are insufficient. Acetate, methanol, and ethanol were investigated as supplementary carbon sources in the nitrite denitrification process using biogranules. Without supplementary external electron donors (control), the biogranules degraded 200 mg l^?1 nitrite at a rate of 0.27 mg NO₂–N g^?1?VSS h^?1. Notably, 1,500 mg l^?1 acetate and 700 mg l^?1 methanol or ethanol enhanced denitrification rates for 200 mg l^?1 nitrite at 2.07, 1.20, and 1.60 mg NO₂–N g^?1?VSS h^?1, respectively; these rates were significantly higher than that of the control. The sodium dodecyl sulfate polyacrylamide gel electrophoresis of the nitrite reductase (NiR) enzyme identified three prominent bands with molecular weights of 37–41 kDa. A linear correlation existed between incremental denitrification rates and incremental activity of the NiR enzyme. The NiR enzyme activity was enhanced by the supplementary carbon sources, thereby increasing the nitrite denitrification rate. The capacity of supplementary carbon source on enhancing NiR enzyme activity follows: methanol?>?acetate?>?ethanol on molar basis or acetate?>?ethanol?>?methanol on an added weight basis.     

Nitrogen transformations at the sediment–water interface across redox gradients in the Laurentian Great Lakes

The capacity of a lake to remove reactive nitrogen (N) through denitrification has important implications both for the lake and for downstream ecosystems. In large oligotropic lakes such as Lake Superior, where nitrate (NO₃ ^?) concentrations have increased steadily over the past century, deep oxygen penetration into sediments may limit the denitrification rates. We tested the hypothesis that the position of the redox gradient in lake sediments affects denitrification by measuring net N-fluxes across the sediment–water interface for intact sediment cores collected across a range of sediment oxycline values from nearshore and offshore sites in Lake Superior, as well as sites in Lake Huron and Lake Erie. Across this redox gradient, as the thickness of the oxygenated sediment layer increased from Lake Erie to Lake Superior, fluxes of NH₄ ⁺ and N₂ out of the sediment decreased, and sediments shifted from a net sink to a net source of NO₃ ^?. Denitrification of NO₃ ^? from overlying water decreased with thickness of the oxygenated sediment layer. Our results indicate that, unlike sediments from Lake Erie and Lake Huron, Lake Superior sediments do not remove significant amounts of water column NO₃ ^? through denitrification, likely as a result of the thick oxygenated sediment layer.     

Seasonal and geomorphic controls on N and P removal in riparian zones of the US Midwest

Riparian zones are an important strategy to mitigate N and P export to streams. However, their efficiency with respect to nitrate (NO₃ ^?), ammonium (NH₄ ⁺), or soluble reactive phosphorus (SRP) in groundwater remains uncertain in the US Midwest. This study investigates water table fluctuations and NO₃ ^?, NH₄ ⁺, and SRP concentration dynamics in two riparian zone types (outwash vs. glacial till) common in the upper US Midwest. During low water table periods, NO₃ ^? removal was 93 % at WR (outwash site), and 75 % at LWD (glacial till site); but during high water table periods, NO₃ ^? removal efficiencies dropped to 50 % at WR, and 14 % at LWD. Median seasonal mass fluxes of NO₃ ^? removed at WR (9.4–21.7 mg N day^?1 m^?1 of stream length) and LWD (0.4–1.9 mg N day^?1 m^?1) were small compared to other riparian zones in glaciated landscapes. The WR site was a small SRP sink (0.114 and 0.118 mg day^?1 m^?1 during the dry period and wet period, respectively), while LWD acted as a small SRP source to the stream (0.004 mg day^?1 m^?1 during the dry period; 0.075 mg day^?1 m^?1 during the wet period). Both LWD and WR acted as sources of NH₄ ⁺ to the stream with mass fluxes ranging from 0.17 to 7.75 mg N day^?1 m^?1. Although riparian zones in the US Midwest provide many ecosystem services, results suggest they are unlikely to efficiently mitigate N and P pollution in subsurface flow.     

Restored floodplains enhance denitrification compared to naturalized floodplains in agricultural streams

Predicted changes in the timing and magnitude of storms have the potential to amplify water quality challenges associated with agricultural runoff. In agricultural streams of the Midwestern US, floodplain restoration has the potential to enhance inorganic nitrogen (N) removal by increasing the bioreactive surface area for microbially-mediated denitrification. The restoration of inset floodplains via construction of the two-stage ditch increases denitrification compared to channelized systems, however, little is known about how denitrification on restored floodplains compares to those formed naturally when stream channel management lapses. We used sacrificial microcosm incubations and membrane-inlet mass spectrometry (MIMS) to compare denitrification rates in floodplain soils collected along transects in both naturalized and restored floodplains; longitudinal transects spanned two zones in the active floodplain (near-stream, NS vs. middle, MID) and a third zone that reflected upland conditions in the riparian buffer strip (UP). Denitrification rates were 35–49% higher in the restored, inset floodplains compared to naturalized floodplains. Variation in denitrification rates were primarily explained by soil organic matter (OM) and OM was > 20% higher in restored floodplains than naturalized, highlighting the contrasts between stable, constructed floodplains with heterogeneous, depositional bars typical of naturalizing channels. Consequently, restored inset floodplains could remove > 70% more N than the naturalized floodplains during similar storm inundation events.