Nitrogen flow and the interaction of Boston harbor with Massachusetts Bay

This paper summarizes evidence that most of the considerable nitrogen loading (～8, 470 mmol total N m^?2 yr^?1) to Boston Harbor (Massachusetts, USA) is expelled to shallow shelf waters of Massachusetts Bay, where it strongly influences ecological dynamics. Examination of nitrogen concentrations in the harbor, compared with loading, indicated that removal processes are active in the harbor. Comparison to other estuarine systems showed that the harbor’s nitrogen concentrations are consistent with its loading, if they are corrected for tidal flushing effects on the water residence time. Furthermore, extensive measurements of sediment denitrification confirmed that rates of N₂ gas loss are high in an absolute sense (～600–800 mmol N m^?2 yr^?1) but nonetheless remove only a small portion (<10%) of the annual land-derived nitrogen loading. Burial in sediments apparently removes only about 2% of the N input, implying export to offshore environments as the major removal process (～88–90% of N input). Western Massachusetts Bay receiving waters were examined for a signature of export from the harbor. Data consistently show a gradient of decreasing nitrogen concentrations from the harbor to about 10–20 km into the bay. In many cases, plots of nitrogen concentrations versus salinity show nearly conservative mixing character, which implies virtual export. Seasonally, the data suggest most of the export from the harbor in winter is as dissolved inorganic forms (NH₄ ⁺, NO₃ ^?, NO₂ ^?). In summer, export is dominated by the outflow of organic nitrogen forms. Chlorophyll export is evident as well, suggesting that the nutritional coupling of the harbor and bay in summer involves organic fertilization of the bay’s surface water. Finally, high-resolution studies over different stages of the tidal cycle help refine understanding of the advection of chlorophyll and stimulation of in situ chlorophyll growth at the seaward edge of the tidal excursion into the bay.     

Denitrification and N2O production in near-shore marine sediments

Methods were developed for determining rates of denitrification in coastal marine sediments by measuring the production of N₂ from undisturbed cores incubated in gas-tight chambers. Denitrification rates at summer temperatures (23°C) in sediment cores from Narragansett Bay, Rhode Island, were about 50μmol N₂m^?2 hr^?1. This nitrogen flux is equal to approximately one-half of the NH⁺₄flux from the sediments at this temperature and is of the magnitude necessary to account for the anomalously low N/P and anomalously high O/N ratios often reported for benthic nutrient fluxes. The loss of fixed nitrogen as N₂ during the benthic remineralization of organic matter, coupled with the importance of benthic remineralization processes in shallow coastal waters may help to explain why the availability of fixed nitrogen is a major factor limiting primary production in these areas. Narragansett Bay sediments are also a source of N₂O, but the amount of nitrogen involved was only about 0.2 μmol m^?2 hr^?1 at 23°C.     

A potential nitrogen sink discovered in the oxygenated Chukchi Shelf waters of the Arctic

The western Arctic Shelf has long been considered as an important sink of nitrogen because high primary productivity of the shelf water fuels active denitrification within the sediments, which has been recognized to account for all the nitrogen (N) removal of the Pacific water inflow. However, potentially high denitrifying activity was discovered within the oxygenated Chukchi Shelf water during our summer expedition. Based on ¹⁵N-isotope pairing incubations, we estimated denitrification rates ranging from 1.8 ± 0.4 to 75.9 ± 8.7 nmol N₂ L^?1 h^?1. We find that the spatial pattern of denitrifying activity follows well with primary productivity, which supplies plentiful fresh organic matter, and there was a strong correlation between integrated denitrification and integrated primary productivity. Considering the active hydrodynamics over the Chukchi Shelf during summer, resuspension of benthic sediment coupled with particle-associated bacteria induces an active denitrification process in the oxic water column. We further extrapolate to the whole Chukchi Shelf and estimate an N removal flux from this cold Arctic shelf water to be 12.2 Tg-N year^?1, which compensates for the difference between sediment cores incubation (~ 3 Tg-N year^?1) and geochemical estimation based on N deficit relative to phosphorous (~ 16 Tg-N year^?1). We infer that dynamic sediment resuspension combined with high biological productivity stimulates intensive denitrification in the water column, potentially creating a nitrogen sink over the shallow Arctic shelves that have previously been unrecognized.     

Role of prior exposure on anaerobic degradation of naphthalene and phenanthrene in marine harbor sediments

The anaerobic degradation of the polycyclic aromatic hydrocarbons (PAHs) naphthalene and phenanthrene was investigated in several marine harbor sediments. In sediments from Boston Harbor that were heavily contaminated with petroleum, [¹⁴C]-naphthalene and [¹⁴C]-phenanthrene were oxidized to ¹⁴CO₂ without a lag, suggesting that the microbial community was adapted for anaerobic PAH oxidation in situ. The addition of molybdate, a specific inhibitor of sulfate-reducing microorganisms, inhibited PAH mineralization which suggested that sulfate reducers were involved in the anaerobic oxidation of the PAHs. PAHs were also anaerobically oxidized at another site in Boston Harbor that was less heavily contaminated, but at a slower rate than in the most heavily contaminated sediments. Sediments not contaminated with petroleum did not significantly oxidize the PAHs. A similar correspondence between rates of anaerobic PAH oxidation and the degree of PAH contamination was observed in sediments from Tampa Bay and San Diego Bay. When relatively pristine sediments from San Diego Bay that did not have a significant capacity for anaerobic PAH oxidation were exposed to high concentrations of naphthalene, they developed a potential for naphthalene degradation that was comparable to that in sediments that had a history of PAH contamination. The increase in potential for naphthalene degradation in the sediments exposed to naphthalene was associated with an increase in naphthalene-degrading microorganisms. These results suggest that many marine harbor sediments contain microorganisms capable of anaerobically oxidizing PAHs under sulfate-reducing conditions and that these microorganisms will respond with an increase in their activity when PAHs are introduced into the sediments. Thus, if PAH inputs into harbor sediments from petroleum can be reduced there may be a widespread potential for microorganisms to remove this PAH contamination from the sediments, despite anaerobic conditions.     

Benthic metabolism and nutrient cycling in Boston Harbor, Massachusetts

To gain insight into the importance of the benthos in carbon and nutrient budgets of Boston Harbor and surrounding bays, we measured sediment-water exchanges of oxygen, total carbon dioxide (DIC), nitrogen (ammonium, nitrate+nitrite, urea, N₂O), silicate, and phosphorus at several stations in different sedimentary environments just prior to and subsequent to cessation of sewage sludge disposal in the harbor. The ratio of the average annual DIC release to O₂ uptake at three primary stations ranged from 0.84 to 1.99. Annual average DIC:DIN flux ratios were consistently greater than predicted from the Redfield ratio, suggesting substantial losses of mineralized N. The pattern was less clear for P: some stations showed evidence that the sediments were a sink for P while others appeared to be a net source to the water column over the study period. In general, temporal and spatial patterns of respiration, nutrient fluxes, and flux ratios were not consistently related to measures of sediment oxidation-reduction status such as Eh or dissolved sulfide. Sediments from Boston Harbor metabolize a relatively high percentage (46%) of the organic matter inputs from phytoplankton production and allochthonous inputs when compared to most estuarine systems. Nutrient regeneration from the benthos is equivalent to 40% of the N, 29% of the P, and more than 60% of the Si demand of the phytoplankton. However, the role of the benthos in supporting primary production at the present time may be minor as nutrient inputs from sewage and other sources exceed benthic fluxes of N and P by 10-fold and Si by 4-fold. Our estimates of denitrification from DIC:DIN fluxes suggests that about 45% of the N mineralized in the sediments is denitrified, which accounts for about 17% of the N inputs from land.     

Denitrification pathways and rates in the sandy sediments of the Georgia continental shelf,USA

Denitrification in continental shelf sediments has been estimated to be a significant sink of oceanic fixed nitrogen (N). The significance and mechanisms of denitrification in organic-poor sands, which comprise 70% of continental shelf sediments, are not well known. Core incubations and isotope tracer techniques were employed to determine processes and rates of denitrification in the coarse-grained, sandy sediments of the Georgia continental shelf. In these sediments, heterotrophic denitrification was the dominant process for fixed N removal. Processes such as coupled nitrification-denitrification, anammox (anaerobic ammonium oxidation), and oxygen-limited autotrophic nitrification-denitrification were not evident over the 24 and 48 h time scale of the incubation experiments. Heterotrophic denitrification processes produce 22.8–34.1 μmole N m^-2 d^-1 of N₂ in these coarse-grained sediments. These denitrification rates are approximately two orders of magnitude lower than rates determined in fine-grained shelf sediments. These lower rates may help reconcile unbalanced marine N budgets which calculate global N losses exceeding N inputs.     

Nutrient Fluxes from Sediments in the San Francisco Bay Delta

In September 2011 and March 2012, benthic nutrient fluxes were measured in the San Francisco Bay Delta, across a gradient from above the confluence of the Sacramento and San Joaquin Rivers to Suisun Bay. Dark and illuminated core incubation techniques were used to measure rates of denitrification, nutrient fluxes (phosphate, ammonium, nitrate), and oxygen fluxes. While benthic nutrient fluxes have been assessed at several sites in northern San Francisco Bay, such data across a Delta–Bay transect have not previously been determined. Average September rates of DIN (nitrate, nitrite, ammonium) flux were net positive across all sites, while March DIN flux indicated net uptake of DIN at some sites. Denitrification rates based on the N₂/Ar ratio approach were between 0.6 and 1.0 mmol m^?2 day^?1, similar to other mesotrophic estuarine sediments. Coupled nitrification–denitrification was the dominant denitrification pathway in September, with higher overlying water nitrate concentrations in March resulting in denitrification driven by nitrate flux into the sediments. Estimated benthic microalgal productivity was variable and surprisingly high in Delta sediments and may represent a major source of labile carbon to this ecosystem. Variable N/P stoichiometry was observed in these sediments, with deviations from Redfield driven by processes such as denitrification, variable light/dark uptake of nutrients by microalgae, and adsorption of soluble reactive phosphorus.     

Sediment Nitrogen Fixation: a Call for Re-evaluating Coastal N Budgets

Coastal ocean primary productivity is often limited by nitrogen (N) availability, which is determined by the balance between N sources (e.g., N-fixation, groundwater, river inputs, etc.) and sinks (e.g., denitrification, sediment burial, etc.). Historically, heterotrophic N-fixation in sediments was excluded as a significant source of N in estuarine budgets, based on low, indirectly measured rates (e.g., acetylene reduction assay) and because it was unnecessary to achieve mass balance. Many recent studies using net N₂ flux measurements have shown that sediment N-fixation can equal or exceed N₂ loss. In an effort to quantify N₂ production and consumption simultaneously, we measured N-fixation and denitrification directly in sediment cores from a temperate estuary (Waquoit Bay, MA). N-fixation, dissimilatory nitrate reduction to ammonium, and denitrification occurred simultaneously, and the net N₂ flux shifted from uptake (N-fixation) to efflux (denitrification) over the 120-h incubation. Evidence for N-fixation included net ²⁸N₂ and ³⁰N₂ uptake, ¹⁵NH₄ ⁺ production from ³⁰N₂ additions, ¹⁵N_{organic matter} production, and nifH expression. N-fixation from ³⁰N₂ was up to eight times higher than potential denitrification. However, N-fixation calculated from ¹⁵NO₃ ^? was one half of the measured fixation from ³⁰N₂, indicating that ¹⁵NO₃-isotope labeling calculations may underestimate N-fixation. These results highlight the dynamic nature of sediment N cycling and suggest that quantifying individual processes allows a greater understanding of what net N₂ fluxes signify and how that balance varies over time.     

The role of sediment denitrification in reducing groundwater-derived nitrate inputs to Nauset Marsh estuary, Cape Cod, Massachusetts

The Nauset Marsh estuary is the most extensive (9.45 km²) and least disturbed salt marsh/estuarine system within the Cape Cod National Seashore, even though much of the 19 km² watershed area of the estuary is developed for residential or commercial purposes. Because all of the Nauset watershed is serviced by on-site individual sewage disposal systems, there is concern over the potential impact of groundwater-derived nutrients passing from these systems to the shallow receiving waters of the estuary. The purpose of this study was to determine whether denitrification (the bacterial conversion of nitrate to gaseous nitrogen) in estuarine sediments could effectively remove the nitrate from contaminated groundwater before it passed from the watershed to the estuary. Rates of denitrification were measured both in situ and in sediment cores, in areas of active groundwater discharge, in relatively pristine locations, and in areas situated down-gradient of moderate to heavily developed regions of the watershed. Denitrification rates for 47 sediment cores taken over an annual cycle at 5 stations ranged from non-detectable to 47 μmol N₂ m⁻² h⁻. Mean denitrification rates were positively correlated with sediment organic content, and varied seasonally due to changes in sediment organic content and to the effect of water temperatures on sediment oxygen penetration depths. There was no correlation between observed denitrification rates and corresponding nitrate concentrations in groundwater. A comparison of in situ denitrification rates (supported by groundwater nitrate) with denitrification rates observed in sediment cores (supported by remineralized nitrate) showed that groundwater-driven denitrification rates were small, and not in excess of denitrification rates supported by remineralized nitrate. Most of the denitrification in Nauset sediments was apparently fueled by remineralized nitrate through coupled nitrification/denitrification. Denitrification did not contribute significantly to the direct loss of nitrate from incoming groundwater at Nauset Marsh estuary. Groundwater flow was rapid, and much of it occurred in freshwater springs and seeps through very coarse, sandy, well-oxygenated sediments of limited organic content. There was little opportunity for denitrification to occur during groundwater passage through these sediments. These results have important management implications because they suggest that the majority of nitrogen from contaminated groundwater crosses the sediment/water interface and arrives at Nauset Estuary, where it is available to primary producers. Preliminary budget calculations suggest that while denitrification was not an effective mechanism for the direct removal of nitrate in contaminated groundwater flowing to Nauset Marsh estuary, it may contribute to significant nitrogen losses from the estuary itself.     

Anaerobic Carbon Mineralisation Through Sulphate Reduction in the Inner Shelf Sediments of Eastern Arabian Sea

Monsoon-induced coastal upwelling, land run-off, benthic and atmospheric inputs make the western Indian shelf waters biologically productive that is expected to lead to high rates of mineralisation of organic matter (OM) in the sediments. Dissimilatory sulphate reduction (SR) is a major pathway of OM mineralisation in near-shore marine sediments owing to depletion of other energetically more profitable electron acceptors (O₂, NO₃ ^?, Mn and Fe oxides) within few millimetres of the sediment-water interface. We carried out first ever study to quantify SR rates in the inner shelf sediments off Goa (central west coast of India) using the ³⁵S radiotracer technique. The highest rates were recorded in the upper 10 cm of the sediment cores and decreased gradually thereafter below detection. Despite significant SR activity in the upper ～12 to 21 cm at most of the sites, pore water sulphate concentrations generally did not show much variation with depth. The depth integrated SR rate (0.066–0.46 mol m^?2 year^?1) decreased with increasing water depth. Free sulphide was present in low concentrations (0–3 μM) in pore waters at shallow stations (depth <30 m). However, high build-up of sulphide (100–600 μM) in pore waters was observed at two deeper stations (depths 39 and 48 m), 7–11 cm below the sediment-water interface. The total iron content of the sediment decreased from ～7 to 5 % from the shallowest to the deepest station. The high pyrite content indicates that the shelf sediments act as a sink for sulphide accounting for the low free sulphide levels in pore water. In the moderately organic rich (2–3.5 %) sediments off Goa, the measured SR rates are much lower than those reported from other upwelling areas, especially off Namibia and Peru. The amount of organic carbon remineralised via sulphate reduction was ～0.52 mol m^?2 year^?1. With an estimated average organic carbon accumulation rate of ～5.6 (±0.5) mol m^?2 year^?1, it appears that the bulk of organic matter gets preserved in sediments in the study region.     

Ammonium excretion by benthic invertebrates and sediment-water nitrogen flux in the Gulf of Mexico near the Mississippi River outflow

Benthic macroinvertebrate biomass and ammonium excretion rates were measured at four stations in the Gulf of Mexico near the Mississippi River mouth. Calculated areal excretion rates were then compared to sediment-water nitrogen fluxes measured in benthic bottom lander chambers at similar stations to estimate the potential importance of macroinvertebrate excretion to sediment nitrogen mineralization. Excretion rates for individual crustaceans (amphipods and decapods) was 2–21 nmoles NH₄ ⁺ (mg dry weight)^?1 h^?1. The mean excretion rates for the polychaetes, Paraprionaspio pinnata [6–12 nmoles NH₄ ⁺ (mg dry weight)^?1h^?1] and Magelona sp. [27–53 nmoles NH₄ ⁺ (mg dry weight)^?1h^?1], were comparable or higher than previous measurements for similar size benthic or pelagic invertebrates incubated at the same temperature (22±1°C). Although the relatively high rates of excretion by these selective feeders may have been partially caused by experimental handling effects (e.g., removal from sediment substrates), they probably reflected the availability of nitrogen-rich food supplies in the Mississippi River plume. When the measured weight-specific rates were extrapolated to total areal biomass, areal macroinvertebrate excretion estimates ranged from 7 μmole NH₄ ⁺ m^?2h^?1 at a 40-m deep station near the river mouth to 18 μmole NH₄ ⁺ m^?2h^?1 at a shallower (28-m deep) station further from the river mouth. The net flux of ammonium and nitrate from the sediments to the water measured in bottom lander chambers in the same region were 15–53 μmole NH₄ ⁺ m^?2h^?1 and ?25–21 μmole NO₃ ^? m^?2h^?1. These results suggest that excretion of NH₄ ⁺ by macroinvertebrates could be a potentially important component of benthic nitrogen regeneration in the Mississippi River plume-Gulf shelf region.     

Bottom-water Hypoxia Effects on Sediment–Water Interface Nitrogen Transformations in a Seasonally Hypoxic,Shallow Bay (Corpus Christi Bay,TX, USA)

Bottom-water hypoxia effects on sediment–water interface nitrogen (N) transformations in Corpus Christi Bay (TX, USA) were examined using continuous-flow intact sediment core incubations. Sediment cores were collected from three sites in August 2002 (summer hypoxia) and April 2003 (normoxia). Oxygen (O₂) and hydrogen sulfide (H₂S) depth profiles were generated with microelectrodes. Membrane inlet mass spectrometry was used to measure sediment O₂ demand and net N₂ flux and combined with isotope pairing to determine potential denitrification and N fixation. Potential dissimilatory nitrate reduction to ammonium (DNRA) was measured using high-performance liquid chromatography. Sediment O₂ penetration depths ranged from 5 to 10 mm. H₂S ranged from being present in overlying water and throughout the sediment column in August to not detectable in overlying water or sediment in April. Sediment O₂ demand was higher during bottom-water normoxia conditions versus hypoxia. Sediments were a significant source of \textNH_\text4^{\text +} {\text{NH}}_{\text{4}}^{\text{ + }} to overlying water during hypoxia but not during normoxia. Net N₂ fixation was observed at one station in August and all stations in April. Denitrification rates were significantly higher during hypoxia at two of three sites. Potential DNRA was observed during both oxic states, but rates were significantly higher during hypoxia, which may reflect sulfide enhancement and absence of cation exchange with ^\text14 \textNH_\text4^{\text +} ^{{\text{14}}} {\text{NH}}_{\text{4}}^{\text{ + }} . DNRA may contribute to formation and maintenance of bottom-water hypoxic events in this system. These results show that N transformation pathways and rates change when bottom-water O₂ concentrations drop to hypoxic levels. Since south Texas is a semiarid region with few episodic runoff events, these results indicate that Corpus Christi Bay sediments are a N source most of the year, and denitrification may drive N limitation between episodic runoff events.     

Microbial nitrogen removal in a developing suburban estuary along the South Carolina coast

The conversion of undisturbed coastal regions to commercial and suburban developments may pose a threat to surface and groundwater quality by introducing nitrate-nitrogen (NO₃ ^?-N) from runoff of land-applied wastewater and fertilizers. Microbial denitrification is an important NO₃ ^?-N removal mechanism in coastal sediments. The objective of this study was to compare denitrification and nitrate conversion rates in coastal sediments from a golf course, suburban site, undeveloped marsh, and nonmarsh area near rapidly developing Hilton Head Island, South Carolina. Nitrous oxide was measured using gas chromatography and nitrate and ammonium concentrations were measured using a flow injection autoanalyzer in microcosms spiked, with 50 μg NO₃ ^?-N gdw^?1. The two marsh sites had the greatest ammonium production, which was correlated with fine sediment particle size and higher background sediment nitrate and surface water sulfate concentrations. The golf course swale had greatest denitrification rates, which were correlated with higher total carbon and organic nitrogen in sediments. Nitrate was consumed in golf course sediments to a greater extent than in the undeveloped marsh and upland freshwater sites, suggesting that the undeveloped sites and receiving estuaries may be more susceptible to nitrate contamination than the golf course swale and marsh under nonstorm conditions. Construction of swales and vegetated buffers using sediments with high organic carbon content as best management practices may aid in removing nitrate and other contaminants from runoff prior to its transport to the receiving marsh and estuary.     

Determination of denitrification in the Chesapeake Bay from measurements of N2 accumulation in bottom water

This study demonstrates the feasibility of using direct N₂ measurements in an estuary for determination of denitrification. High precision measurements of dinitrogen: argon ratios (N₂∶Ar) were made by membrane inlet mass spectrometry on water samples taken along the length of the Chesapeake Bay in July and October 2004. The N₂∶Ar ratio in low salinity surface water was elevated relative to air saturation by 0.3–0.5% with no systematic change along the length of the Bay. N₂∶Ar in high salinity bottom water exhibited a linear increase in the landward direction along a 144-km longitudinal section. In this section of the Bay covering 20% of the main stem, the bottom water salinity was statistically uniform and the increase in N₂∶Ar was in the direction of net residual current flow. The system was analyzed as a capped river with the assumption that N₂ entered the water from the underlying sediment where denitrification is known to take place. The rate of denitrification needed to support the measured increase in N₂ was calculated using an average residual current velocity and water column depth. The increase in N₂ with distance (0.046μmol N l⁻¹ km⁻¹) equated to an average denitrification flux of 73 μmol N m⁻² h⁻¹. N₂ fluxes determined on sediment cores taken from the source and terminus regions of the delineated water mass were 45±23 and 83±39 μmol N m⁻² hr⁻¹, respectively, which were not statistically different from the whole system estimate. The measured change in oxygen concentration within the bottom water was used to estimate nitrogen remineralization and the efficiency of denitrification. Denitrification efficiency (nitrogen denitrified/nitrogen remineralized) was estimated to be in the range of 22–28% for the bottom water sediment system and 30–37% considering the sediment zone alone.     

Denitrification and the stoichiometry of nutrient regeneration in Waquoit Bay, Massachusetts

To determine the removal of regenerated nitrogen by estuarine sediments, we compared sediment N₂ fluxes to the stoichiometry of nutrient and O₂ fluxes in cores collected in the Childs River, Cape Cod, Massachusetts. The difference between the annual PO₄ ³⁻ (0.2 mol P m⁻² yr⁻¹) and NH₄ ⁺ (1.6 mol N m⁻² yr⁻¹) flux and the Redfield N∶P ratio of 16 suggested an annual deficit of 1.5 mol N m⁻² yr⁻¹. Denitrification predicted from O₂∶NH₄ ⁺ flux ratios and measured as N₂ flux suggested a nitrogen sink of roughly the same magnitude (1.4 mol N m⁻² yr⁻¹). Denitrification accounted for low N∶P ratios of benthic flux and removed 32–37% of nitrogen inputs entering the relatively highly nutrient loaded Childs River, despite a relatively brief residence time for freshwater in this system. Uptake of bottom water nitrate could only supply a fraction of the observed N₂ flux. Removal of regenerated nitrogen by denitrification in this system appears to vary seasonally. Denitrification efficiency was inversely correlated with oxygen and ammonium flux and was lowest in summer. We investigated the effect of organic matter on denitrification by simulating phytoplankton deposition to cores incubated in the lab and by deploying chambers on bare and macroaglae covered sediments in the field. Organic matter addition to sediments increased N₂ flux and did not alter denitrification efficiency. Increased N₂ flux co-varied with O₂ and NH₄ ⁺ fluxes. N₂ flux (261±60 μmol m⁻² h⁻¹) was lower in chambers deployed on macroalgal beds than deployed on bare sediments (458±70 μmol m⁻² h⁻¹), and O₂ uptake rate was higher in chambers deployed on macroalgal beds (14.6±2.2 mmol m⁻² h⁻¹) than on bare sediments (9.6±1.5 mmol m⁻² h⁻¹). Macroalgal cover, which can retain nitrogen in the system, is a link between nutrient loading and denitrification. Decreased denitrification due to increasing macroalgal cover could create a positive feedback because decreasing denitrification would increase nitrogen availability and could increase macroalgae cover.     

Assessing Nitrogen Dynamics Throughout the Estuarine Landscape

Assessing nitrogen dynamics in the estuarine landscape is challenging given the unique effects of individual habitats on nitrogen dynamics. We measured net N₂ fluxes, sediment oxygen demand, and fluxes of ammonium and nitrate seasonally from five major estuarine habitats: salt marshes, seagrass beds (SAV), oyster reefs, and intertidal and subtidal flats. Net N₂ fluxes ranged from 332?±?116 μmol?N-N₂?m^?2?h^?1 from oyster reef sediments in the summer to ?67?±?4 μmol?N-N₂?m^?2?h^?1 from SAV in the winter. Oyster reef sediments had the highest rate of N₂ production of all habitats. Dissimilatory nitrate reduction to ammonium (DNRA) was measured during the summer and winter. DNRA was low during the winter and ranged from 4.5?±?3.0 in subtidal flats to 104?±?34 μmol?¹⁵NH ₄ ⁺ ?m^?2?h^?1 in oyster reefs during the summer. Annual denitrification, accounting for seasonal differences in inundation and light, ranged from 161.1?±?19.2 mmol?N-N₂?m^?2?year^?1 for marsh sediments to 509.9?±?122.7 mmol?N-N₂?m^?2?year^?1 for SAV sediments. Given the current habitat distribution in our study system, an estimated 28.3?×?10⁶?mol of N are removed per year or 76 % of estimated watershed nitrogen load. These results indicate that changes in the area and distribution of habitats in the estuarine landscape will impact ecosystem function and services.     

Sediment-water oxygen and nutrient exchanges along the longitudinal axis of Chesapeake Bay: Seasonal patterns,controlling factors and ecological significance

Sediment-water oxygen and nutrient (NH₄ ⁺, NO₃ ^?+NO₂ ^?, DON, PO₄ ^3?, and DSi) fluxes were measured in three distinct regions of Chesapeake Bay at monthly intervals during 1 yr and for portions of several additional years. Examination of these data revealed strong spatial and temporal patterns. Most fluxes were greatest in the central bay (station MB), moderate in the high salinity lower bay (station SB) and reduced in the oligohaline upper bay (station NB). Sediment oxygen consumption (SOC) rates generally increased with increasing temperature until bottom water concentrations of dissolved oxygen (DO) fell below 2.5 mg l^?1, apparently limiting SOC rates. Fluxes of NH₄ ⁺ were elevated at temperatures >15°C and, when coupled with low bottom water DO concentrations (<5 mg l^?1), very large releases (>500 μmol N m^?2 h^?1) were observed. Nitrate + nitrite (NO₃ ^?+NO₂ ^?) exchanges were directed into sediments in areas where bottom water NO₃ ^?+NO₂ ^? concentrations were high (>18 μM N); sediment efflux of NO₃ ^?+NO₂ ^? occurred only in areas where bottom water NO₃ ^?+NO₂ ^? concentrations were relatively low (<11 μM N) and bottom waters well oxygenated. Phosphate fluxes were small except in areas of hypoxic and anoxic bottom waters; in those cases releases were high (50–150 μmol P m^?2 h^?1) but of short duration (2 mo). Dissolved silicate (DSi) fluxes were directed out of the sediments at all stations and appeared to be proportional to primary production in overlying waters. Dissolved organic nitrogen (DON) was released from the sediments at stations NB and SB and taken up by the sediments at station MB in summer months; DON fluxes were either small or noninterpretable during cooler months of the year. It appears that the amount and quality of organic matter reaching the sediments is of primary importance in determining the spatial variability and interannual differences in sediment nutrient fluxes along the axis of the bay. Surficial sediment chlorophyll-a, used as an indicator of labile sediment organic matter, was highly correlated with NH₄ ^?, PO₄ ^3?, and DSi fluxes but only after a temporal lag of about 1 mo was added between deposition events and sediment nutrient releases. Sediment O:N flux ratios indicated that substantial sediment nitrification-denitrification probably occurred at all sites during winter-spring but not summer-fall; N:P flux ratios were high in spring but much less than expected during summer, particularly at hypoxic and anoxic sites. Finally, a comparison of seasonal N and P demand by phytoplankton with sediment nutrient releases indicated that the sediments provide a substantial fraction of nutrients required by phytoplankton in summer, but not winter, especially in the mid bay region.     

Sediment Denitrification in Two Contrasting Tropical Shallow Lagoons

Sediment denitrification was monthly evaluated in two tropical coastal lagoons with different trophic states using the ¹⁵N isotope pairing technique. Denitrification rates were very low in both environments, always <5.0 μmol N₂ m^?2 h^?1 and were not significantly different between them. Oxygen consumption varied from 426 to 4248 μmol O₂ m^?2 h^?1 and was generally three times higher in the meso-eutrophic than the oligotrophic lagoon. The low denitrification activity was ascribed to both low water NO₃ ^? concentrations (<2.0 μM) and little nitrate supply from nitrification. There was no correlation of denitrification with nitrate or ammonium fluxes. Sediments in temperate environments with similar oxygen consumption rates usually presented a higher proportion of nitrification–denitrification rates. Sediment oxygen consumption was a good predictor of sediment denitrification in both studied lagoons.     

Sediment-water oxygen and nutrient fluxes in a river-dominated estuary

Sediment oxygen uptake and net sediment-water fluxes of dissolved inorganic and organic nitrogen and phosphorus were measured at two sites in Fourleague Bay, Louisiana, from August 1981, through May 1982. This estuary is an extension of Atchafalaya Bay which receives high discharge and nutrient loading from the Atchafalaya River. Sediment O₂ uptake averaged 49 mg m^?2 h^?1. On the average, ammonium (NH₄ ⁺) was released from the sediments (mean flux =+129 μmol m^?2 h^?1), and NO₃ ^? was taken up (mean flux =?19 μmol m^?2h^?1). However, very different NO₃ ^? fluxes were observed at the two sites, with sediment uptake at the upper, river-influenced, high NO₃ ^? site (mean flux =?112 μmol m^?2 h^?1) and release at the lower, marine-influenced low NO₃ ^? site (mean flux =+79 μmol m^?2 h^?1). PO₄ ^3? fluxes were low and often negative (mean flux =?8 μmol m^?2 h^?1), while dissolved organic phosphorus fluxes were high and positive (mean flux =+124 μmol m^?2 h^?1). Dissolved organic nitrogen fluxes varied greatly, ranging from a mean of +305 μmol m^?2 h^?1 at the lower bay, to ?710 μmol m^?2 h^?1 at the upper bay. Total dissolved nitrogen and phosphorus fluxes indicated the sediments were a nitrogen (mean flux =+543 μmol m^?2 h^?1) and phosphorus source (mean flux =+30 μmol m^?2 h^?1) at the lower bay, and a nitrogen sink (mean flux =?553 μmol m^?2 h^?1) and phosphorus source (mean flux =+17 μmol m^?2 h^?1) in the upper bay. Mean annual O∶N ration of the positive inorganic sediment fluxes were 27∶1 at the upper bay and 18∶1 at the lower bay. Based on these data we hypothesize that nitrification and denitrification are important sediment processes in the upper bay. We further hypothesize that Atchafalaya River discharge affects sediment-water fluxes through seasonally high nutrient loading which leads to net nutrient uptake by sediments in the upper bay and release in the lower bay, where there is less river influnces.     

Oyster (<Emphasis Type="Italic">Crassostrea virginica</Emphasis>) Aquaculture Shifts Sediment Nitrogen Processes toward Mineralization over Denitrification

Filter-feeding bivalves, like oysters, couple pelagic primary production with benthic microbial processes by consuming plankton from the water column and depositing unassimilated material on sediment. Conceptual models suggest that at low to moderate oyster densities, this deposition can stimulate benthic denitrification by providing denitrifying bacteria with organic carbon and nitrogen (N). While enhanced denitrification has been found at oyster reefs, data from oyster aquaculture are limited and equivocal. This study measured seasonal rates of denitrification, as well as dissimilatory nitrate reduction to ammonium (DNRA), and dissolved inorganic N fluxes at a rack and bag eastern oyster (Crassostrea virginica) aquaculture farm. Consistent with models, denitrification was enhanced within the farm, with an average annual increase of 350% compared to a reference site. However, absolute denitrification rates were low relative to other coastal systems, reaching a maximum of 19.2 μmol m^?2 h^?1. Denitrification appeared to be nitrate (NO₃ ^?) limited, likely due to inhibited nitrification caused by sediment anoxia. Denitrification may also have been limited by competition for NO₃ ^? with DNRA, which accounted for an average of 76% of NO₃ ^? reduction. Consequently, direct release of ammonium (NH₄ ⁺) from mineralization to the water column was the most significant benthic N pathway, with seasonal rates exceeding 900 μmol m^?2 h^?1 within the farm. The enhanced N processes were spatially limited however, with significantly higher rates directly under oysters, compared to in between oyster racks. For commercial aquaculture farms like this, with moderate oyster densities (100–200 oysters m^?2), denitrification may be enhanced, but nonetheless limited by biodeposition-induced sediment anoxia. The resulting shift in the sediment N balance toward processes that regenerate reactive N to the water column rather than remove N is an important consideration for water quality.